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INORQANIC CHEMISTRY. ii. 149 Inorganie Chemistry. Active Chlorine. Y. VENKATARAMAIAH ( J . Physical Chem. 1923,27,74-8O).-Pure chlorine prepared by heating gold chloride was activated by the silent electric discharge by electrical discharge a t 20 mm. pressure by ultra-violet light or thermally. The active variety combines with ozone to form chlorine monoxide with sulphur to form sulphur monochloride with tellurium to form tellurium dichloride and with benzene in the dark to form benzene hexachloride. It does not react with carbon and is unstable above 50". The activation of chlorine is accompanied by a contraction in volume indicating that the activity is probably due to the presence of complex molecules. E. Moms and J. M. CLAVERA (And. Fis. Quim. 1922 20 550-554) .-Revised values are given for the atomic weights of fluorine (19*000) chlorine (35*457) bromine (79*926) nitrogen (14.008) carbon (12*000) and sodium (22.995). G.W. R. A Class of Hydrates but little Stable called Hydrates of Gases. A. BOUZAT (Compt. rend. 1923 176 253-255).-The author has calculated as accurately as possible the values of Q and q the heats of formation of the hydrates from liquid water and solid water respectively in the cases of chlorine bromine and sulphur dioxide and the values obtained give as the general formula for the hydrates M,6H,O which is in agreement with the experimental results and the hypothesis of Villard (A. 1897 ii 151). W. G. Solubility of Iodine Pentoxide in Sulphuric Acid. ARTHUR B. LAMB and A. W. P m s (J. Bmer. Chem. Soc. 1923,45 108- ll2).-The solubility of iodine pentoxide has been determined a t 24.77" in sulphuric acid of concentrations 50-106% and is found to decrease up to 77% acid and from this point upwards the initial solubility increases.However a slow transformation of the solid phase begins at this point with the formation of a less soluble solid substance. This substance has a maximum solubility a t 104% acid There is also evidence of a third solid substance in equilibrium with acids of intermediate concentrations. A possible explanation of these facts is that the main solubility curve (the initial curve) represents the solubility of iodic acid whilst the second and probably the third curves represent solubilities of iodine pentoxide and of anhydro-iodic acid (H1308). The Activation of Oxygen and Hydrogen Peroxide by Palladium Hydride.N. D. ZELINSKY and P. P. BORISSOW (Ber. 1923,56 [B] 396-406).-The decolorisation of indigotin in faintly acid solution in the presence of palladium foil saturated with hydrogen occurs after the same time whether air or oxygen is passed through the solution although the production of hydrogen J. S. G. T. Some Fundamental Atomic Weights. J. F. S.ii. 150 ABSTRACTS OF CHEMICAL PAPERS. peroxide is considerably greater in the latter circumstances. The amount of hydrogen peroxide therefore has little influence on the oxidation of indigotin. The formation of hydrogen peroxide when air or oxygen is rapidly passed through water containing palladium foil thoroughly saturated with hydrogen takes place to a greater extent than has been previously supposed and attains a maximum concentration of 0.646 g.per litre. The oxidation of indigotin however under the experimental conditions cannot be attributed to this unex- pectedly high concentration of hydrogen peroxide since the effect is produced only after a much longer period by solutions of the technical agent of considerably greater concentration. Decolorisation of indigotin proceeds much more rapidly under otherwise similar conditions in the absence of acid and is observed when solutions of technical hydrogen peroxide and indigotin are brought into contact with palladium hydride and kept agitated by a current of carbon dioxide. Under these conditions it is not possible for fission of the oxygen molecule or formation of a higher oxide of hydrogen to take place; the only possible explanation is to be found in the mutual action of palladium hydride and hydrogen peroxide.Palladium hydride by itself has a marked reducing action towards indigotin; conversely in the presence of hydrogen peroxide the oxidising action of the latter is catalytically accelerated by palladium hydride . If air is passed through water in which palladium hydride is immersed and the latter is then removed a solution is obtained which contains hydrogen peroxide but is much more active towards indigotin than a solution of similar concentration which has been prepared from the technical peroxide. A similarly active solution can be obtained from palladium hydride hydrogen peroxide and carbon dioxide. If however the passage of the carbon dioxide is prolonged the hydrogen peroxide is completely destroyed and the solution does not react with potassium permanganate or zinc iodide-starch even in the presence of ferrous sulphate; the activity is however rapidly restored by the addition of a little hydrogen peroxide.An active solution cannot be obtained from palladium and hydrogen peroxide or from palladium hydride and water. The essential condition appears to consist of the presence of palladium hydride and hydrogen peroxide. The solution does not lose its activity when it is distilled filtered or preserved in a closed vessel during eight months. The presence of traces of palladium or of its compounds cannot be detected. Apparently the effect is due to unusually minute traces of a substance with the properties of an inorganic peroxydase which for the present cannot be detected analytically. The formation and decomposition of the possible compound may conceivably be expressed as follows Pd&+H202 -+ PdZ,H2(OH) -+ O+H20+Pd3H,.The liberated oxygen atom affects the oxidation. This hypothesis explains the labile condition of hydrogen peroxide in the presence of palladium hydride. H. W.INORGANIC CHEMISTRY. ii. 151 Ozone and Allotropy. P. DE PAW (Chm. WeekbZud 1923 20 26).-The conception of m n e as an allotrope of oxygen con- flicts with the definitions of allotropy since (1) both are gases (2) their chemical reactions do not always yield identical products ; the action of ozone on unsaturated organic compounds yields ozonides which cannot be obtained from oxygen (3) their solutions are not identical.Ozone therefore should not be selected as an example of allotropy; a more suitable example would be grey tin which on heating passes over into the white form a t constant Physicolchemical Study of the Sulphur held by Carbon at High Temperatures. ALFRED R. POWELL ( J . Amer. Chem. Soc. 1923 45 1-16).-A phase- rule investigation of the carbon-sulphur complex which exists with carbon a t high temperatures shows that the sulphur is present in two forms adsorbed free sulphur and sulphur in solid solution in the carbon or held on the surface of the carbon in such a manner that it cannot be distinguished from a solid solution. Coke pro- duced in the laboratory by heating coal rapidly contains sulphur in three forms adsorbed free sulphur sulphur in solid solution in the carbonaceous mass or held on the surface in such a form as to exhibit all the properties of a solid solution and ferrous sulphide together with much smaller quantities of calcium and magnesium sulphide.When this coke is maintained a t a red heat for several hours the adsorbed sulphur slowly passes info solid solution. Coke made by the usual commercial process of carbonis- ation over a comparatively Iong period contains before it is cooled only two forms of sulphur sulphur in solid solution as above and ferrous sulphide with smaller quantities of other sulphides the absorbed sulphur being absent or present in inappreciable quantities. When coke COO^^ even with limited access to the air oxidation of ferrous sulphide takes place according to the equation 4FeS+30,= 2Pe20,+4S.When coke is quenched as in ordinary coke manu- facture the decomposition of ferrous sulphide is incomplete ; this is due to the speed with which the temperature of the coke is carried below that necessary for oxidation. Coke kept a t a tem- perature about 500° even with a limited supply of air shows an almost complete oxidation of the ferrous sulphide. When hydrogen or gas containing hydrogen is led through red-hot coke in a coking oven the sulphur removed as hydrogen sulphide comes from the decomposition of the ferrous sulphide because this compound has the highest dissociation pressure of all the forms of sulphur in coke. The Desulphuration of Metals by Lime. B. BOGITCH (Compt rend.1923,176 103-105).-1f the metal is rich in sulphur a considerable amount of the sulphur is removed by calcium oxide at 1500-1600" but if the sulphur content is low the desulphuration by lime or by a basic slag is extremely slow and at this temperature the slag ceases to absorb sulphur when the sulphur content of the slag reaches about 22% although there may still be some unaltered temperature. s. I. L. Forms of Sulphur in Coke. J. F. S.ii. 152 ABSTRACTS OF CHEMICAL PAPERS. cdcium oxide present. If the proportion of mlcium fluoride in the slag is increased the absorption of sulphur continues until the whole &.%he oxide is converted into sulphide. Vapour Pressures of Sulphur Dioxide. W. MUND (Bull. A d . roy. Belg. 1919 [v] 5 529-543).-The author has determined by the static method the vapour pressures of sulphur dioxide corresponding with temperatures between -442" and 0".The errors common to such determinations are examined and eliminated by methods for the description of which the original paper should be consulted. The vapour pressure of sulphur dioxide at 0" was found to be 1163.98 mm. or 1.53 atmos. other determinations being made a t the temperature of fusion of certain eutectic mixtures (cf. Bruylants and Mund ibid. 113). Acidity and Electrolytic Dissociation of Hydrogen Selenide. M. DE HLASKO (Bull. Acad. Polonaise Sci. Lettres 1921 [A] 18- 25 ; from Chem. Zentr. 1923 i 16).-The equivalent conductivity of the ion HSe' calculated by the Kohlrausch formula from measurements of the conductivity of aqueous solutions of hydrogen selenide is 70.The value 1 . 8 8 ~ 1 0 - ~ was obtained for the dis- sociation constant of hydrogen selenide. WILHELM STRECKER and LUDWIG CLAUS (Ber. 1923 56 [B] 362-383).-Selenium nitride SeN has been obtained previously as an amorphous pale orange-yellow extremely explosive powder by the action of gaseous ammonia on a number of compounds of selenium. In the hope of securing a better- regulated course of the change the action of liquid ammonia has now been investigated. The action of liquid ammonia on diselenium dichloride is exceedingly vigorous and results in the deposition of red selenium ; a similar result is obtained if the chloride is mixed with chloroform or anhydrous benzene only traces of the nitride being produced.In ethereal solution on the other hand a pale brown amorphous compound Se2NC1 is formed. Selenium tetrachloride in the absence of solvent behaves similarly to the lower chloride towards liquid ammonia ; in the presence of carbon disulphide it is converted into a pale yellow amorphous material which could not be satis- factorily purified. Selenyl chloride is transformed by liquid ammonia in the presence of ether in open vessels into the primary product SeOCI2,4NH which is decomposed by water into selenium selenium nitride ammonium chloride and selenite and selenious acid whereas in a sealed tube it gives selenium nitride in com- paratively good yield. Diselenium dibromide reacts with gaseous ammonia in the same manner as the corresponding chloride; with liquid ammonia in the presence of ether it gives the compound Se,N,Br.The reaction of selenium tetrabromide towards liquid ammonia resembles closely that of the tetrachloride. On the other hand the action of these substances in the presence of carbon disulphide proceeds more quietly than when the chloride is used and gives W. G. E. E. T. G. W. R. Selenium Nitride.INORGMIC CHEMISTRY. ii. 153 better yields of the nitride. The change follows a similar course in the presence of benzene. It therefore appears that the selenium tetrahalides are the best initial materials for the preparation of selenium nitride; the small amounts of the latter which are produced when the lower halides or the oxy-compounds are employed appear to be derived from intermediately formed tetrahalide.Selenium nitride is an amorphous orange-coloured powder which is considerably more sensitive than mercury fulminate to shock or blow; it explodes with certainty when heated at 160'. According to Verneuil its formation from the tetrachloride and ammonia is expressible by the equation 3SeC1,+16NH3= 3SeN+12NH4C1+N. In the case of the bromide in the presence of carbon disulphide the volume of nitrogen evolved is far in excess of t'hat required by a similar equation whereas in the presence of benzene the reaction 3SeBr4+16NH3=2SeN+Se+N2+12NH4Br appears to take place. Chlorine and bromine react explosively with selenium nitride. In the presence of carbon disulphide the action of bromine leads to the formation of a brownish-green hygroscopic substance SeN,Br,. Bromine vapour diluted with carbon dioxide trans- forms solid selenium nitride into ammonium selenohexabromide (NHa)2SeEr6 the formation of which appears to be due to the action of atmospheric moisture on a primary additive product of bromine and the nitride.Chlorine in similar circumstances gives the product SeNC1,. Bromination of the compound Se,N,Br yields the substance SeN,Br whereas exhaustive chlorination of the product Se2NC1 yields Se2NCl6 which possibly is not quite homogeneous. Selenium nitride is not affected by solid iodine or by a solution of the halogen in ether or chloroform. The constitution of selenium nitride is discussed a t some length; unfortunately a suitable solvent is not available for the determin- ation of the molecular weight but reasons are advanced in favour of a cyclic structure of the molecule Se4N4.The possibility that selenium nitride is a derivative of azoimide has been examined but this does not appear to be the case. Diselenium dibromide reacts with silver azide suspended in benzene with the formation of silver chloride and selenium ; similar changes occur with lead an4 sodium azides. Selenium tetrabromide and silver azide give a pale yellow compound which becomes bluish- black when exposed to light. Selenium oxychloride and sodium azide in the presence of a benzene gives nitrogen and the compound 2NaC1,Se02,H20. H. W. New Method of Determination of the Atomic Weight of Tellurium. P. BRUYLANTS and J. &CHIELSEN (Bull. Acad. roy. Belg. 1919 [v] 5 119-130).-The ratio Te H and Te H,O have been measured.Hydrogen telluride prepared by the electrolysis of dilute sulphuric acid using a tellurium cathode was purified by fractional distillation etc. from the accompanying hydridesii. 154 ABSTRACTS OF CHEMICAL PAPERS. of sulphur selenium and antimony and decomposed into ita elements at a temperature of 200-220°. The tellurium was weighed as such and the hydrogen oxidised to water by means of cupric oxide. A marked difference obtained between the ratio Te & measured directly and that measured indirectly through water was traced to incomplete decomposition of the hydrogen telluride and correcting for this the authors obtain the figure 127.8 for the atomic weight of tellurium. The Allotropy of Tellurium. A DAMIENS (Ann. Chim. 1922 [ix] 18 282-312).-A detailed description of work which has been previously published (A.1922 ii 498 562). The general conclusion is drawn that the analogy between the allotropy of sulphur and tellurium cannot be accepted as the latter element is clearly differentiated by the existence of a single crystalline form. H. J. E. Properties of Hydrogen Telluride. P. BRUYLANTS (Bull. A d . roy. Belg. 1920 [v] 6 472478).-hre hydrogen telluride was prepared by a modification of the process used previously Bruylants and Michielsen ibid. 1919 119-130 ; this vol. ii 153) and various constants were determined. The triple point has for co-ordinates t -45-4" p 102 mm. The vapour-pressure curve was compared with the curves for ethyl alcohol and carbon disulphide whence the b. p. at 760 mm.was calculated as -2-2" using the Ramsay-Young equation. The actual b. p. found by experiment was -14". The calculated latent heat of vaporisation was found to be L 5.7 cal. whence by Trouton's Rule L/T=20.9. The critical temperature of the hydride lies in the region of 200° if the Guldberg-Guye relation holds. E. E. T. Electrolytic Dissociation of Hydrogen Telluride. M. DE HLASKO (BuZZ. A d . Polonaise Sci. Lettres 1919 [A] 73-78; from Chem. Zentr. 1923 i 1 5 - 16) .-The electrical conductivity of aqueous solutions of hydrogen telluride was determined. The value 61 was obtained for the equivalent conductivity of the ion HTe'. The value K=2*27 x lW3 was obtained for the dissociation constant of hydrogen telluride in aqueous solution. The After-glow of Activated Nitrogen.~KARCEILO PIRANI and ELLEN LAX (Wiss. VerogeentZ. Siemens-Konxern 1922 2 203- 207; from Chem. Zentr. 1923 i 17; cf. A. 1921 ii 197-198).- Highly purified nitrogen in sealed glass vessels was submitted to high frequency discharge of about 100,000 periods per second. The discharge occurs in the form of bright threads joining up with the walls of the vessel. At pressures varying from 2-700 mm. with an optimum at 60-200 mm. a pale blue glow was produced. Contamination by gas given off from the walls of the vessels during discharge amounted to less than 5 x 10-5y0. In experiments at pressures of 150 to 180 mm. nitrogen always showed luminescence either at once or after longer discharge (ten minutes). The glow E. E. T. The density is do 2-65. Acidity of Hydrogen Telluride.G. W. R.INORGANIC CHEMISTRY. ii. 155 spreads from those parts of the walls of the vessels receiving the greatest impact of electrons. The luminescence occurs when the nitrogen is contaminated with gases evolved from the hygroscopic moisture on the glass walls of the vessels. These may amount a t 150 mm. pressure to to Inert gases and electro- positive gases such as hydrogen have little effect. Electronegative gases such as oxygen water vapour and iodine vapour give in concentration of about 1.5 x a maximum after-luminescence ; with 6 to 8~ the luminescence is inhibited. Perfectly pure nitrogen does not show luminescence. It is supposed that an active form of nitrogen is produced which decomposes in the presence of small quantities of electronegative gases with emission of light.Electronegative gases increase the point discharge and thereby the number of active molecules and the rate of decom- position. With larger amounts of impurity the point discharge is decreased whilst the rate of decomposition is so much increased that luminescence only occurs in the region of the lines of dis- charge. With still greater quantities of impurity for example of oxygen the decomposition within the region of the lines of discharge is so rapid that luminescence is no longer visible. G. W. R. The Catalytic Oxidation of Ammonia by Air in Contact with Platinum. EUGANE DECARRI~RE (Ann. Chim. 1922 [ix] 18,312-388).-A detailed description of work previously published. Fuller particulars are given of the author’s work of the action on the catalyst of certain gaseous impurities (A.1921 ii 503 546; 1922 ii 284) and also of work carried out in collaboration with Pascal on the effect of variations in the form of the catalyst (A. 1919 ii 463). The Crystal Structure of Hydrazine Dihydrochloride. RALPH W. G. WYCKOFF (Amer. J . Sci. 2923 5 15-22).-Using Laue photographic and spectrographic data the structure of hydrazine dihydrochloride has been shown to be based on the paramorphic hemihedry of the cubic system. The crystal unit consists of a cell 7.89 A. in length containing four chemical mole- cules. An approximate placing of the atoms in the unit cube has been made and the arrangement is analogous to that obtaining in crystals of the alkaline-earth nitrates the hydrazine groups occupying positions analogous to those held by the alkaline-earth metals and the chlorine atoms replacing the nitrate groups.The distance between adjacent chlorine atoms is approximately 3.96 A. ; between chlorine and nitrogen atoms about 3.14 A. These results H. J. E. are at variance with the hvypothesis .of constant atomic radii. W. E. G . The Preparation of Hydroxylamine Hydrochloride and Acetoxime. WALDO L. SEMON ( J . Amer. Chern. Soc. 1923 45 18&-190).-A modification of Divers’s method (T. 1896 69 1665)’ in which the conversion of the sodium carbonate first into a mixture of hydrogen carbonate and hydrogen sulphite and thenii. 156 ABSTRACTS OF CHEMICAL PAPERS. into hydrogen sulphite alone is carried out prior to the addition of the sodium nitrite as a result of which the time required for the complete operation and the amount of cooling necessary are considerably reduced.Further the sodium hydroxylamineiii- sulphonate is converted directly into acetoxime (cf. Raschig A. 1887 549 635) and this is then hydrolysed by hydrochloric acid and the required hydroxylamine hydrochloride obtained after distilling off the acetone (cf. Janny A. 1883 580 581). Under these conditions a product is obtained free from ammonium salts and with a yield of 53-77%. Black Colloidal Suspensions in Phosphorus. CLAUDE HAINES HALL jun. ( J . Amer. Chem. Xoc. 1923 45 67-69).- The literature relating to black phosphorus is quoted and dis- cussed and it is shown that Thhard’s black phosphorus is a colloidal suspension of mercury in the phosphorus whilst the black phosphorus obtained by Bridgman (A.1914 ii 647) is a true allotropic modification of phosphorus. Using Svedberg’s method of colloidisation the author has dispersed copper and mercury in molten phosphorus to form colloidal suspensions of these metals. The material obtained with copper and mercury was homogeneous readily inflammable and had d 1.9. When extracted with carbon disulphide tiny black crystals of copper phosphide were obtained in the case of copper but with mercury droplets of mercury; a few red flakes of amorphous phosphorus were obtained in each case. J. F. S. RAY V. MURPHY and J. HOWARD MATHEWS ( J . Amer. Chern. Xoc. 1923 45 16-22).-The effect of exposing arsenic trisulphide sols of varying concentrations to the light of a condensed filament lamp for various periods at constant temperature has been in- vestigated by measuring the electrical conductivity of the solutions after each exposure.The results show that the electrical con- ductivity increases on exposing the sols to light the rate of change increasing with decreasing concentration of the colloid. This is explained as due to the increased photochemical activity of the colloid per unit mass of arsenic trisulphide brought about by the greater dispersion of the more dilute sol. The reaction is explained according to the suggestion of fieundlich and Nathan- sohn (A. 1921 ii 494) as one of a two-stage photochemical oxid- ation of hydrogen sulphide to colloidal sulphur and a thionic acid accompanied by a reaction between hydrogen sulphide and the thionic acid which serve as stabilising electrolytes for the micella of arsenic trisulphide and sulphur respectively. Removal of the stabilising electrolytes produces a de-stabilisation of the two colloids which are consequently precipitated.The increase in electrical conductivity is explained as due to the building up of a concentration of the thionic acid sufficient to serve as the stabilising electrolyte for the colloidal sulphur the reaction between hydrogen sulphide and the thionic acid then proceeding a t such a rate that the equilibrium is maintained between the several components of W. G. Action of Light on Arsenic Trisulphide Hydrosol.INORGANIC CHEMISTRX. ii. 187 the system further change in the electrical conductivity thus being prevented.J. F. S. Estimation of the Atomic Weight of Boron. ALFRED STOCK and ERNST Kuss (Ber. 1923 56 [B] 314-316).-A pre- liminary account. The full details of the work will be published elsewhere. The method adopted consists in the decomposition of weighed amounts of diborane B2H6 (cf. Stock and Massenez A. 1913 ii 44) by water in accordance with the equation B2H6+6H,0= 2H3BO,+6H and measurement of the evolved hydrogen. As mean value of six determinations the atomic weight of boron is found to be 1043055 (H=1.0077) the mean error of the individual experiments being &0.0036 and of the average value &O-OOlS. The figure is slightly lower than that obtained (10.82-10.84) from the analysis of boron trichloride by Honigschmid and by Baxter and Scott but agrees with that predicted by Aston (10.75&0-07) from observations of the mass spectrum.The atomic weight of silicon has been estimated similarly by decomposing monosilane with sodium hydroxide. Preliminary results are 28-15 28-16 and 28.14 which however are given with reserve. It is certain that the usually adopted figure for the atomic weight of silicon (28.3) is considerably too high. H. W. Absorption of Carbon Monoxide by Cuprous Ammonium Carbonate and Formate Solutions. ALFRED T. LABSON and CLARK S. TEITSWORTH ( J . Amer. Chem. Soc. 1922 44 2878- 2885).-A static method for investigating the absorption capacity of liquid absorbents for carbon monoxide is described and has been used with various solutions of cuprous ammonium formate and cuprous ammonium carbonate for this purpose.It is shown that for equivalent concentrations the formate and carbonate solutions have essentially the same absorption capacity for carbon monoxide under the same conditions of temperature and partial pressure of carbon monoxide. At low temperatures (O") the results indicate the formation of a complex or additive compound containing 1 mol. of carbon monoxide per mol. of copper which is largely decomposed a t slightly elevated temperatures (60O). Small variations in the concentration of total carbonate or formate have no appreciable effect on the solubility of carbon monoxide but the solubility is proportional to the copper concentration of the solution. The carbonate solutions are much less stable than the formate solutions; the former deposits copper a t 60".The maximum permissible copper concentration of any solution is fixed by the temperature a t which the solution is to be regenerated. High copper concentration is accompanied by increased precipit- ation of free copper as the temperature is raised. High pressures of carbon monoxide also tend to increase the precipitation of copper. Solutions of cuprous ammonium formate are preferable to cuprous ammonium carbonate because the deposition of copper a t the regeneration temperature is very much less. J. F. S .ii. 158 ABS!CRACTS OF CHEMICAL PAPERS. Formation of Carbon Disulphide by the Action of Sulphur Dioxide on Carbon. B. RASSOW and K. HOFFUNN ( J . p. Chem. 1922 [ii] 104 207-240).-When sulphur dioxide is led over red-hot carbon the following reactions can occur (i) 2S02+ 2C=2C0,+S2.(ii) S2+CeCS2. (iii) C 0 2 + C ~ 2 C 0 . (iv) S,+ 2CO+S2e2COS. (vii) 2S02+4Ce4CO+S,. The mutual in- fluence of these reactions and the influence of temperature are discussed in detail the conclusion being that an increase in the reaction temperature can lead only to an optimum formation of carbon disulphide. This prediction has been verified experimentally. Sulphur dioxide was led over red-hot beechwood charcoal pre- viously freed from hydrogen by heating in a current of chlorine. Free sulphur in the issuing gas was collected by condensation and filtration through glass wool ; carbon disulphide vapour was next absorbed by means of ethereal triethylphosphine the precipitated additive product being collected and weighed.Carbon dioxide and carbon oxysulphide were absorbed in ammoniacal calcium chloride solution the total carbon in the liquid being determined by oxidation with hydrogen peroxide followed by filtration and titration of the precipitated calcium carbonate whilst the sulphur in the filtrate was estimated as barium sulphate. The remaining gas was finally collected over water and the carbon monoxide estimated in the usual way. At 700" only traces of carbon disulphide are produced; the amount formed increases with rising temperature the product containing also carbon oxysulphide carbon dioxide free sulphur and small amounts of carbon monoxide. The maximum formation of carbon disulphide occurs at 850-900" the sulphur from the sulphur dioxide being then distributed as follows 35% as carbon disulphide 55% as carbon oxysulphide and 10% as free sulphur whilst carbon monoxide and a small amount of carbon dioxide constitute the rest of the gas mixture.Above goo" the proportion of free sulphur increases at the expense of both carbon disulphide and carbon oxysulphide ; the oxygen from the sulphur dioxide appears almost exclusively as carbon monoxide. Above 1 loo" free sulphur and carbon monoxide are the only products. The formation of carbon oxysulphide decreases continuously with increasing temperature ; the free sulphur produced is a minimum a t about 850". It is concluded that the process is useless as a technical method 2c0 Ge= cos+co+so,. (v) s2+2c0 =+= 2cos. (vi) cs2+co =is= of making carbon disulphide. w. s. N. Absorption of Carbon Disulphide Vapour by Aqueous Solutions of Sodium Trinitride [Azide].A. J. CURRIER and A. W. BROWNE ( J . Amer. Chem. SOC. 1922 44 2849-2854).- The absorption of carbon disulphide vapour from gaseous mixtures by solutions of sodium azide in water has been investigated. It is shown that a 1% solution of sodium azide absorbs the theoretical . amount of carbon disulphide vapour from gaseous mixtures but that a further amount may also be absorbed at a much slowerINORaANIC CHEMISTRY. ii. 159 rate. The absorption of carbon disulphide by a 1% aqueous solution of sodium azide amounts to about 3.5 times the volume of the absorbing liquid and takes place irreversibly with the quanti- tative formation of sodium azidodithiocarbonate NaN,+CS,= NaS-CSN,. Various mixtures of carbon disulphide vapour with air oxygen nitrogen hydrogen methane and carbon monoxide have been analysed using a 5% or a saturated aqueous solution of sodium azide as absorbent with exceedingly good results.The solution of the salt produced by the interaction of the absorbent and vapour has been found to possess no dangerously explosive properties but to decompose very slowly after keeping for long periods with the formation of nitrogen sulphur and sodium thiocyanate. J. F. S. A Theory of the Structure and Polymorphism of Silica. ROBERT B. SOSMAN ( J . Franklin Inst. 1922 194 741-764).-A set of hypotheses is put forward to explain in a consistent manner the wide variety of experimental data on the modifications of silica. It is assumed that the silica atom triplet SiO maintains its individuality in all the forms of quartz and silicates and that the silica molecules aggregate themselves in chains in which the silicon atoms share a pair of electrons with each oxygen and the oxygen atoms share a pair of electrons between them.At the same time the silicon shares one pair of electrons with each of two neighbouring silicons. The rGsulting silica thread possesses the 0-0 0-0 \/ \/ constitution -Si-Si-Si-Si-. These threads form in the liquid state or even in the vapour. In the liquid they are in a constant state of vibration and movement with the oxygen atoms in haphazard orientation relative to the thread. On this view solid silica glass is analogous to a compressed pad of wires. The thread structure is believed to persist in the crystalline state and the three principal crystalline modifications (cristo- balite tridymite and quartz) are built up by combining the threads through the oxygen atoms.The high to low inversions (a-p) in all three forms are considered to be due to a change in the state of motion of certain electron orbits resulting from increased thermal vibration of the atoms. These changes produce sudden alterations in the shape of the silica triplet and the relative positions of the two oxygen atoms. In cristobalite the oxygen atoms of the silica threads are incompletely fixed some of the threads being capable of rotation about the silica axis. This explains the variable inversion point of this form of quartz. The theory of the poly- morphism of silica is extended to silicate systems and to the oxides of other elements in group IV of the periodic classification.This view of the structure of the silica complex is in agreement with. the minimum in the temperature volume curve of silica glass and the relations between the specific heats of the various forms of quartz. /\ /\ 0-0 0-0 W. E. G.ii. 160 ABSTRACTS OF CHEMICAL PAPERS. Silicon Hydrides. XII. Disiloxan (Si€&),O. ALFRED STOCK and CARL SOMIESKI (Ber. 1923 By [B] 132-135).- Unsuccessful attempts are described to convert disiloxan (Stock Somieski and Wintgen A. 1918 ii 110) into disilene Si,H,. Disiloxan is not sensibly affected when heated a t 300"; at 400" it yields small amounts of hydrogen monosilane and polymeric prosiloxan but the greater portion of the original substance remains unchanged.Phosphoric oxide decomposes disiloxan at the atmo- spheric temperature giving a little hydrogen much monosilane and polymeric prosiloxan. The initial reaction appears to consist in a slight hydrolysis in accordance with the equation (SiH,),O+H,O = 2Si&0+2H2 followed by a polymerisation of the volatile pro- siloxan to its non-volatile polymeride. The liberated hydrogen is largely utilised in the reduction of disiloxan to monosjlnne (SiH3),0+2H,=2SiH,+H,0. The water which is thus set free hydrolyses a further quantity of disiloxan and thus the change continues until it is brought to a gradual conclusion by the absorp- tion of water by the excess of dry phosphoric oxide. Silicon Hydrides. XIII. Some Reactions of Chloro- monosilane and Disilane.ALFRED STOCK and CARL SoMrEsKr (Ber. 1923 56 [B] 247-252).-Disilane is very stable towards heat but a t not too high a temperature (about 500") suffers decom- position which resembles the cracking of hydrocarbons. In addition to silicon large volumes of monosilane are obtained the production of which depends on the reducing action of primarily liberated hydrogen on unchanged disilane. Higher hydricles are not pro- duced in sufficient quantity to make the method practicable for their preparation. At a higher temperature the fission of disilane into silicon and hydrogen predominates. Chloromonosilane and silver cyanide at 150" yield hydrogcn cyanide and cyanogen as gaseous products. At 300° chloro- monosilane is decomposed by silver sulphide into non-volatile silicon compounds hydrogen and hydrogen sulphide. Mono- chlorosilane and hydrogen sulphide a t 150" in the presence of aluminium chloride give hydrogen dichloromonosilane and a volatile compound containing sulphur [possibly SiH,*SH or (SiH,),S] which has not been investigated completely. The main products of the action of sodium amalgam on dichloro- monosilane are monosilane and the unsaturated yellow poly- merised hydride (SiH),.The course of the reaction is represented by the equations SiH,Cl,+4Na=SiH,Na2+2NaCI ; SiH,Na,+ mercury -+ SiH,+sodium amalgam ; 3SiH -+ SiH4+2(SiH),. The following tensions have been measured for hydrogen sulphide prepared from iron sulphide and hydrochloric acid and purified by fractional distillation in a vacuum -130" 3 mm.; -120" 7 mm.; -110" 20 mm.; -lOO" 54 mm.; -go" 117 mm.; -80" 247 mm.; -70" 440 mm.; -59.1" 778 mm.The pure dry gas can .be preserved unchanged over mercury. The Densities of Dilute Solutions of Potassium Salts and the Volume Changes Occurring on Solution. HAROLD HARTLEY and WILLIAM HENRY BARRETT (T. 1923,123,398401). H. W. H. W.The Formation of m d a l Crystals by Alkali Halides. HERMANN KUNZ-KRAUSE (Bw. Deut. p h . Ges. 1922 32 329- 331).-The crystallisation of sodium chloride in pyramidal crystals previously observed from time to time by various workers has been shown to take place also with potassium iodide. Photo- graphs are shown of such crystals of both these salts and their mode of formation is indicated by diagrams of crystal growth a t the surface of a saturated solution.P. M. The Preparation of Potassium Hydroxylamineisodisul- phonate. P. RASCHIG (Ber. 1923 56 [BJ 206-208).-The preparation of potassium hydroxylamineisodisulphonate S 0,K.NH.O *SO,K has previously been a matter of some difficulty mainly owing to the poor yields and unstable nature of the intermediately formed trisulphonate. A convenient process for preparing the latter is now described. Sodium hydrogen sulphite solution (5N 1200 c.c.) is added with continuous stirring to a mixture of ice (1000 g.) and technical sodium nitrite (150 g.) whereby the temperature is not allowed to rise above 5". One C.C. of the solution when tested after the addition has been finished for ten minutes should react with about 17 C.C. of N/10-iodine solution and subsequently require 14-15 C.C.of N/lO-sodium hydroxide for neutralisation in the presence of methyl- orange. Any ice particles are removed and the solution is treated whilst being vigorously shaken with lead peroxide (600 g.). It is subsequently warmed on the water-bath frequent agitation being required to prevent the oxidising agent from becoming aggregated. The conclusion of the oxidation is reached when 1 C.C. of the solu- tion neutralises about 9 C.C. of N/IO-hydrochloric acid and subse- quently does not react with more than 1 C.C. of N/lO-iodine solution. The solution is filtered and the residue washed with hot water (200 c.c.). The filtrate is warmed with technical potassium chloride (800 9.) until the precipitated lead chloride forms coarse particles which are removed.The filtrate after remaining for three days in an ice-chest deposits potassium hydroxylaminetrisulphonate (790 9.) in large monosymmetric prisms. It is filtered dried on porous earthenware and subsequently over calcium chloride. The finely-divided dry salt (423 g.) is agitated with boiling water ($00 c.c.) containing 1 C.C. of dilute hydrochloric acid until solution is complete; the small amount of lead sulphate which separates is removed. The filtrate deposits potassium hydroxylamineisodisul- phonate in colourless crystals the yield being about 90% of that The Alkali Permanganates. M. CmsPI and E. Moms (Anal. Pis. Quim. 1922,20,555-562).-The alkali pemanganahs with the exception of sodium permanganate and ammonium per- mangttllate which are relatively unstable decompose a t temperatures which increase almost proportionally to their molecular weights.The densities are closely correlated with molecular weights. The thermal decomposition is similar throughout the series and is theoretically possible. H. w.ii. 162 ABSTRACTS OF CHEMICAL PAPERS. represented for example in the case of potassium permanganate by the equation 10KMnO,=2~O3+ (3K~04,5Mn0,)+60,. G. W. R. The Dissociation of Potassium Chloroiridiate. G. GIRE (Compt. rend. 1923 176 241-244).-The author has studied the decomposition of potassium chloroiridiate in the same manner as that used for barium chloroplatinate (A. 1922 ii 551) and from his results calculates the heat of fusion of a molecule of potassium chloride to be -4.92 cal. which is in close agreement with the value obtained by Schemtschuschny and Rambach (A 1910 ii 204).W. G. Molecular Weight of the Sodium-Tellurium Complex in Liquid Ammonia as Derived from Vapour Pressure Measure- ments. CHARLES A. KRAUS and EDWARD H. ZEITFUCHS ( J . Anaer. Chem. SOC. 1922 @ 2714-2728).-The lowering of the vapour pressure of liquid ammonia a t temperatures of 17.9" to 20° due fo the complex sodium-tellurium compound has been measured at a series of concentrations down to 0.03N. It is shown that when the values of APIP are plotted against the values of n/n+N where n is the number of atoms of sodium in the mixture a curve is obtained which for dilute solutions approaches very closely to a straight line and for which the value (APIP) / (n/n+N) is equal to 0.5.Apparently solutions of the complex telluride in liquid ammonia very nearly follow Raoult's law; and from the value of the above ratio it follows that two atoms of sodium are present in each molecule of the complex telluride present in the solution. The complex telluride-ion therefore carries two negative charges. The formation of the complex telluride consists in the addition of tellurium atoms to the normal telluride-ion the valency of the telluride-ion undergoing no change under these conditions. The bearing of this result on the present-day conceptions of the nature of other complexes in ammonia solution and of metallic alloys in general is discussed. The Position of the Atoms in the Optically Active Crystals NaClO and NaBrO,. L. VEGARD (2. Phyaik 1922 12 289- 303).-By the employment of the Debye powder method the positions of the atoms in the chlorate and bromate crystals have been determined.The parameter values lead to a very simple grouping of the atoms in space which is in agreement with the volume conditions. As was recognised by Bragg the space lattices are based on the face-centred cube but none of the atom centres themselves lies in it face-centred arrangement. The atoms lie about trigonal axes with the halogen and the three oxygen atoms forming a pyramid group. The halogen which forms the apex of this group is attached to a sodium atom along the vertical axis of the pyramid. Each oxygen atom is in contact with two other oxygen atoms and the halogen atom in the same molecule and with two sodium atoms from neighbouring molecules.The halogen atom is not in contact with the sodium atom. The following distances J. F. S.INORGANIC CHEMISTRY. ii. 163 obtain between the atoms in contact DN,-0=2.36 A. ; DBr-O= 1.89 A. ; Do-o=140 8. whereas according to Bragg these dis- tances should be 2-42 A. 1-84 8. and 1.30 d. respectively. The arrangement of the oxygen atoms is quite different from that ascribed to them by Koltmeijer Bijvoet and Karssen ( K . Akm?. Wetensch. Amsterdam 1921 23 644-653). The intensities of the lines calculated on the basis of the above structure is however in agreement with the experimental values. Both the chlorine and sodium atoms are displaced towards the angles of the unit cube and this involves a rotation of the pyramid group about the pyramidal axis.Since this rotation can occur in two directions the occurrence of optical activity is accounted for. This rotation does not occur in the isomorphous group of nitrates although these crystallise in the same system as the chlorate and bromate. These substances are however inactive. Formulae based on the assumption that contact between the atoms in the crystal indicates the positions of the valency forces are not in accordance with chemical ideas. It is therefore concluded that crystal structure gives very little clue to chemical constitution. The volume conditions governing the packing of the atoms in the crystal and not the chemical forces are the deciding factor in the atomic arrangement. W. E. G. The System Sodium Sulphate-Sodium Chromate-Water.11. YUKICHI OSAKA and RYOHEI YOSMDA (Hem. CoZZ. Sci. Kyoto 1922 6 49-54).-This work is a continuation of that of Takeuchi (A. 1916 ii 31) and the equilibrium of the sodium sulphate-sodium chromate system has now been studied a t 28" 31" and 33". At 28" and 31" the chromate exists as tetrahydrate and its solubility in the sulphate as decahydrate decreases as the temperature rises the molar fraction being 0-16 a t 28" and 0.04 at 31". The solid solution obtained by Takeuchi at 25" having the composition 2Na,S0,,Na2Cr0,,30H20 was not a definite com- pound. At 33" no solid solution of the decahydrates exists. E. H. R. Some Slags from the Clausthal Silver Furnaces. A New Family of Silicates of Composition R,Si,O,. KURT HOFMANN- DEGEN (Sitzungsber. Heidelberger A M .Wiss. 1919 [A. 141; from Chem. Zentr. 1923 iii 1248-1249).-Cavities of slag from the Clausthal silver works contain a zinc bearing iron-calcium olivine (Fe,Si04 50*9:/ Zn,SiO 2-7% Mg,SiO 5-1% Ca,SiO 41.2%) having a b c=0.4371 1 0.5768 and refractive indices yD 1-7430 PD 1.7340 and aD 1.6958 and also a tetragonal silicate mineral called '' justite." Justite has the composition (Mg,Fe,Zn,Mn,Ca),Si,O where Ca (Mg,Fe,Zn,Mn)=l 1. Its refractiveindices are cD=1.6581 and wD 1.6712. It resembles the naturally occurring hardystonite (Ca,Zn),Si,O,. A slag from Bochurn consisted of tetragonal crystals of the composition (Ca,Mg,Fe,Mn),Si,O? where Ca (Mg,Fe,Mn)=2 1. The tetragonal slag silicates includmg hardystonite form a well- defined isomorphous group of the type R,Si,O,.G. W. R.ii. 164 ABSTRACTS OR’ CHEMICAL PAPERS. Binary Lead Alloys. J. GOEBEL (2. Metullk. 1922 14 357- 366 388-394 425-432 4 4 9 4 5 6 ) .-The hardness and density of alloys of lead with sodium magnesium arsenic antimony cadmium tin mercury and bismuth have been determined. The hardening effect of small quantities of these elements decreases in the order named. Very small quantities of sodium and mag- nesium have a considerable effect in increasing the hardness of lead the solid solution of sodium in lead containing about 1% of sodium having a Brinell number of 35 against 5 for pure lead (cf. J.S.C.I. 1923 March). A. R. P. Topochemical Processes. The Conditions of Formation and the Forms of Lead Oxide. V. KOHLSCHUTTER and Ip. ROESTI (Ber. 1923 56 [BJ 275-288).-The formation of the yellow and red modifications of lead oxide during the course of the following reactions has been studied (i) precipitations in which a change in the nature of the product may be expected as a consequence of alteration of the temperature concentration and nature of the solution; (ii) the oxidation of metallic lead beneath water by oxygen ; (iii) the pseudomorphic transformation of solid lead salts; (iv) the thermal decomposition of compounds of lead oxide and (v) the oxidation of lead vapour and rapid condensation of the product.The yellow variety of lead oxide is produced when the com- pound is immediately formed from molecular solutions or by the oxidation of lead vapour. On the other hand the red modification is obtained by reactions in which water plays a part through the hydrate 3PbO,H,O and thus through a solid compound.This reaction is observed only when the hydrate is in a suitably dis- perse condition in which a certain spatial compression appears to be essential; it does not occur with the recognisably crystalline hydrate. The process therefore involves a well-marked topo- chemical factor. The formation of the red variety by the thermal decomposition of lead oxide or hydrate can be explained from the same point of view if it is assumed that the oxide molecules after rupture of the molecules more readily form complexes by reason of their proximity to one another than they arrange themselves to the elements of the yellow variety which is favoured by separation from solution or from the gaseous phase. The formation of the red variety through the hydrate appears to indicate a difference in the complexity of the molecules of the two forms.The assumption is made that the condensed molecule which is already present in the hydrate SPbO,H,O remains intact during the formation of the red oxide. When therefore the latter is produced by the dissociation of a solid compound a coales- cence of several molecules must have occurred which is favoured by topochemical conditions. In solution on the other hand the simple lead hydroxide Pb(OEI) is present and hence a simpler molecular formula may be assigned to the yellow lead oxide obtained therefrom. The simultaneous production of the two oxides from solutionINORGAN10 CHEMISTBY. ii. 165 depends on the dehydration and amphoteric ionisation of the bivalent metallic hydroxide (cf.von Euler A. 1922 ii 831 who has discussed the analogous case of copper hydroxide). The production of the yellow variety is due to the dehydration of lead hydroxide in accordance with the scheme Pb( OH),+PbO+H'+OH' whilst that of the red modification is due to the preliminary con- densation of several simple molecules to the complex 2PbO,Pb( OH),. E. MOLES and M. PAY.& (Anal. 2%. Quim. 1922 20 563-570).-The initial temperature of absorption of oxygen by copper is about 350"; a t this temperature also the dissociation of cupric oxide begins. Copper oxide wire commonly used in analysis is a solid solution of cuprous oxide in cupric oxide. Powdered cupric oxide undergoes contraction on heating and a decrease in dissociation pressure takes place.The change is superficial. Topochemical Reactions. Homologous and Substituted Forms of Production. V. KOHLSCHUTTER and VL. SEDEL- ~NOVICH (2. Elektrochem. 1923 29 3 0 4 ; cf. this vol. ii 133). -Specimens of electrolytic copper hydroxide have been examined with the object of ascertaining to what extent the form is main- tained in which the hydroxide was produced when topochemical changes take place. Nine varieties of copper hydroxide were investigated and as topochemical changes leading directly to new subshnces the following reactions were examined. Spontaneous formation of oxide conversion into sulphide by means of hydrogen sulphide and the further conversion to cuprous sulphide the action of hydrogen peroxide which through a peroxide forms cupric oxide with the liberation of oxygen the reduction to cuprous oxide with hydrazine and the formation of basic salts by the action of con- centrated solutions of potassium chloride.The various forms of copper oxide were identified by the velocity of the change into oxide and by their behaviour as suspensions. The observation of the velocity of sedimentation served also for the investigation of the products of the reactions. It is shown that there is a definite connexion between the form of the initial material the course of the reaction and the form of the product. The form of the initial material is conditioned largely by the velocity of formation. The form of a substance obtained by changing the determining con- ditions of a reaction constitute a ,form-hmoZogous series from which by means of topochemical reactions other f orm-homologous series may be produced.The members of these series correspond with those of the &st in behaviour and form. Cuprous Compounds. J. E~RERA (Bull. Amd. roy. Belg. 1921 [v] 7 361-386).-The electrolysis of solutions of chlorine-free sodium hydrogen carbonate using a copper anode gives rise to the basic carbonate 2CuCOs,2Cu( OH),&O which is superimposed upon a layer of cuprous oxide. Deville's salt Na2C0,,CuC0,,3H,0 is probably an active complex in solution during electrolysis. The VOL. CXXTV. ii. 7 H. W. The System Copper-Oxygen. G. W R. J. F. S.ii. 166 ABSTRACTS OF CHEMICAL PAPERS. change of anode potential was followed by means of a normal electrode HgIHgOlNaHCO (46 g.per litre) for which the constant potential (EE-o) is 0.433 volt at 15". The electrolysis of a solution of carbon dioxide (saturated at 20 atmospheres pressure) using a copper anode results in the formation of a green carbonate. No azurite is formed. "Black copper,.'' an unstable modification of the metal which rapidly passes mto red copper particularly in presence of acid is deposited on the cathode. The electrolysis of a solution of sodium silicate using a copper anode gives an insoluble silicate superimposed upon cuprous oxide. The formation of the latter was not prevented by using a water-cooled anode and was therefore not due to secondary changes resulting from local heating. The formation of cuprous salts by a reversible reaction occurring in solutions of cupric sulphate also occurs with cupric nitrate.The latter in the presence of metallic copper in the cold and under the influence of an electrical current or at higher temperatures in the absence of a current gives rise to a cuprous salt oxidisable with potassium permanganate. For a N/5-solution at 97" the concentration of cuprous ions is 5 ~ l O - ~ g. per litre and [C~"]/[CU*]~=~ x lo5. Such solutions regenerate the oxide 2CuNO,+H,O Cu20+2HN0,. A similar hydrolysis seems to occur when copper is in contact with the cupric salts of a weak acid which may explain the formation of cuprous oxide on the anodes as described above. When copper is left in contact with an aqueous suspension of its carbonate'in a closed vessel in complete absence of air etc.cuprous oxide is formed after a short time in the cold. (This points to the intermediate formation of cuprous salts and may explain the occurrence of cuprite in minerals containing native copper and malachite.) Copper silicate and copper under similar conditions also give rise to small but appreciable quantities of cuprous oxide. E. E. T. Surface Tension of Mercury in Contact with Oxygen. J. PALACIOS and E. LASALA (Anal. Pis. Quim. 1922 20 505- 508; cf. A. 1921 ii 304).-The surface tension of freshly-distilled mercury in contact with oxygen does not decrease and is practically the same as in a vacuum. In contact with air however the surface tension gradually decreases. Separation of Mercury into Isotopes in a Steel Apparatus. WILLIAM D.HARKINS and S. L. MADORSKY (Nature 1923 111 148).-An apparatus is figured and described by means of which long-continued and repeated fractional vaporisation from a steel trough in a vacuum a t low pressures can be effected. It has thus been found possible to obtain a difference of 0.1 unit in the atomic weight of mercury. Cooling by ice was employed. A. A. E. Dilatometric Study of the Alloys of Aluminium with Magnesium and Silicon. A. PORTEVIN and P. CHEVENARD (Compt. rend. 1923 176 296-298).-The dilatometric curves G. W. R.MORCANTC CHEMISTRP. ii. 167 have been obtained for an alloy containing 0-95y0 of magnesium and 1.25% of silicon the alloy having been originally annealed and then submitted to ten successive thermal cycles. The final tem- perature of each successive heating was increased until a t the seventh heating the alloy commenced to melt.In curves three to six at temperatures above 350° there was a contraction of the alloy due to gradual solution of magnesium silicide and on cooling precipitation of the silicide is marked by a progressive expansion which is however retarded and incomplete so that there is a residual contraction which is greater the higher the temperature to which the alloy was heated. After these thermal cycles there- fore there is in increasing amount an excess of silicide in solution resulting in a more and more accentuated tempering effect. The phenomenon of spontaneous return at the ordinary tem- perature can also be studied by means of a differential dilatometer and curves are given for the above alloy.Experiments conducted between 20" and 80" show that the velocity of precipitation of the silicide increases according to an exponential law of the tem- perature and doubles for an interval of about 10". W. G. Hydrates and Hydrogels. I. Aluminium Hydroxide. RICHARD WIUSTATTER and HEINRJCH KRAUT (Ber. 1923 56 [B] 149-162) .-During the application of aluminium hydroxide in the adsorption of enzymes variations in activity are observed which do not appear to be simply related to the dispersivity of the hydrogel. The present investigation is concerned with the possi- bility that the varieties of aluminium hydroxide obtained by precipitation from the salts are different hydrates of aluminium oxide and the relationship between the chemical properties of the varieties and their adsorptive capacity for enzymes.Aluminium hydroxide has been obtained by four different methods for the full details of which the original communication must be consulted. Variety A is prepared by precipitating alumin- ium sulphate solution with concentrated ammonia and protracted heating of the precipitate with ammonia; it is a pale yellow plastic mass. Variety B a very pale yellow plastic viscous mass is obtained similarly to A but the protracted heating is omitted. (An intermediate variety b is prepared by the dialysis of aluminium chloride with frequent addition of small quantities of ammonia against running water; it is related chemically to B but in ad- sorptive capacity more closely resembles A . ) Variety C is pure white in colour voluminous and very finely divided ; it is obtained by precipitating aluminium sulphate solution with dilute ammonia without protracted heating.Variety D which is pure white in colour and coarsely powdered is obtained by passing a slow stream of carbon dioxide into a solution of potassium aluminate. The chemical behaviour of the different varieties towards sodium hydroxide (lye) warm acetic acid (12%) and hydrochloric acid (1% 15% and 35%) is described in detail. Variety B appears to be the most decidedly acidic but loses this property to a con- siderable degree when subjected to protracted heating owing to 7-2ii. 168 ABSTRACTS OF tJHl4MICAL PAPERS. conversion into A . Basic properties are most pronounced in D. The differences in behaviour cannot be explained on purely chemical or purely chemico-colloidal grounds.Different chemical types certainly exist but their behaviour is as yet insufficiently elucidated. The desiccation of the varieties when preserved in a desiccator over sulphuric acid has been studied; the process takes place very slowly. It is only possible to state that it is thus shown that the different gels contain a number of different chemical hydrates. The step-wise dehydration a t gradually increasing temperatures has also been examined and for this purpose a special form of apparatus is figured and described in the text. Definite steps in the dehydration appear to be indicated. The adsorptive capacity of the different varieties for invertin and lipase has been examined. This appears to be affected to a very marked extent by the dilution of the solution.Invertin is accompanied by substances which greatly inhibit adsorption from concentrated solution but have a much less pronounced action in dilute solution. A similar reaction is not shown by the companions of lipase. Invertin is only adsorbed to a slight extent by variety D as would be expected from the physical properties of the micro- crystalline coarse material. Whereas however A and B are very similar with regard to dispersivity the latter which is the more active chemically is the more highly absorbent. The most surprising result is the high adsorptive capacity of C which in spite of its finely divided non-plastic character is superior to either A or B. A simple relationship does not exist between the colloidal properties of the aluminium hydroxides and Weir ad- sorptive capacities.Two different factors the surface action and the differing chemical properties of the products appear to be involved. These two factors however have not the same influence with all enzymes since the relative activity of the aluminium hydroxide preparations towards invertin is not the same as towards Cobalt Complexes. Werner's Formula? and their Experi- mental Signification. P. JOB (Bull. SOC. chim. 1923 [iv] 33 6-21).-A lecture delivered before the SociM Chimique cie France. G. F. M. The Catalytic Decomposition of Hexamminecobaltichloricle . ROBERT SCHWARZ and WALTER KRONIG (Ber. 1923 56 [B] 208-2 14) .-In a previous communication Schwarz and Bausch (A. 1921 ii 404) have drawn the conclusion that the interaction of hexamminecobalti- and chloropentamminecobalti-chloride solu- tions on alkali silicates is accompanied by the displacement of the ammine groups by the silicate complex.This conclusion is now found to be due to an analytical error. The process only causes the formation of silicates and the silicato-compounds which have been described should be deleted from the literature. Slow decom- position of hexamminecobaltichloride solutions is caused by silicic acid gels but the quantitative nature of the process is difficult to follow and the change is more readily observed in the presence of lipase. I€. w.INORGANIC CHEMISTRY. ii. 169 charcoal. The solutions are slowly decomposed in the presence of the latter a t 20° cobalt and ammonia being adsorbed leaving a mixture of unchanged hexamminecobaltichloride and chloropent- amminecobaltichloride in solution which however is free from cobaltous salts.The reactions which occur may be represented by the equations [CO(~,)~]C~,=[CO(~H,).C~]CI,+NH ; [Co(NH,),] + + + =CO + + + 6NH3 ; [Co(NH,),]C13+3H,6 -+ Co( OH) +3NH4C1+3NH,. The change indicated by the second equation occurs readily also when aqueous solutions of the luteochloride are exposed to the light of a mercury lamp. Like the action of char- c021 it is inhibited by feeble acidity of the solution. The maximum formation of the purpureochloride is observed in 1% solution ; a t higher concentrations the ion [Co(NH,!,] 1-++ becomes more stable whereas in more dilute solution reaction 111 preponderates.With an increased amount of carbon the cobalt is completely adsorbed from a 0.5% solution of the luteochloride and a solution of ammonia remains. With increasing concentration of the solution the quantities of adsorbed cobalt diminish whereas those of ammonia rapidly become constant. Contrary to the usual adsorptive process the absolute anounts of adsorbed cobalt diminish with increasing concentration of the solution ; the pheno- menon is explained by the increased extent of the hydrolysis (equation 111) in dilute solution. H. W. Effect of Masked Anions on the Magnetic Susceptibility of Chromic and Chrsrnyl Salts. B. CABRERA and S. PIEA DE RUBIES (Anal. Pis. Quim. 1922 20 509-518; cf. A. 1922 ii 612).-Solutions of chromic sulphate which when freshly pre- pared give no sulphate reaction undergo change on keeping whereby electrical conductivity and sulphate reaction show a parallel in- crease. No appreciable variation in magnetic susceptibility how- ever is observed. In the case of solutions of chromyl sulphate on the other hand an increase in magnetic susceptibility is observed.The change is supposed to consist of two successive unimolecular reactions namely [(SO,),Cr,O] -+ SO,[SO,Cr,O] -+ (SO,),[Cr,O]. The quantitative aspect of these reactions is discussed. G. W. R. Determinations of the Density of Metals and Alloys at High Temperatures. 111. The System Tin-Bismuth. K. BORNENANN and PAUL SIEBE (2. MetaZZE. 1922 14 329-334).- The specific volumes of tin bismuth and tin-bismuth alloys have been determined at temperatures up to 900".In every case the volume is directly proportional to the temperature. Tin expands 243% during melting and bismuth contracts 3% (cf. J.S.C.Z.? 1923 229~). A. R. P. The System Tin-Arsenic. QASIM ALI MANSURI (T. 1923 123 214-223). ; Complex Compounds of Tin. Hydrolysis of Stannic Chloride and Chlorostannates. J. DE LA PUENTE ( A d . Pis. Quim. 1922 28 486495).-Stannic chloride reacts with four mole-ii. 170 ABSTRACTS OF CHEMICAL PAPERS. cules of sodium hydroxide giving a complex of the composition [SnC12(0H),1N% which can also be obtained by the reaction of one molecule of orthostannic acid with two molecules of hydro- chloric acid and sodium hydroxide. Potassium chlorostannate in 1 yo solution is completely dissociated into stannic chloride and potassium chloride.The dissociation is partly prevented by the presence of a large excess of potassium chloride. Attention is directed to the possibility of a series of complexes intermediate between chlorostannic acid H,SnCl and the hydrated stannic acid H,Sn(OH),. G. W. R. Preparation of Pure Zirconium Oxide. HERMANN VON SIEMENS and HERBERT ZANDER ( Wiss. Vero#entZ. Siemens Kon- xern 1922,2,48A88 ; from Chem. Zentr. 1923 i 21).-A Brizilinn zircon mineral containing ZrO 67.8 % SiO 22.2 yo Fe,O,,TiO 8.7y0 is mixed with 25% of carbon and treated with a stream of chlorine a t 1000-1200". From the mixture of chlorides thus formed zirconium oxychloride is obtained by crystallisation from aqueous solution. Ignition of this in air yields zirconium oxide.G . W. R. Purification and Analysis of Zirconium Dioxide. F. G. JACKSON and L. I. SHAW ( J . Amer. Chem. SOC. 1922 44 2712- 2714).-With the object of purifying zirconia for the investigation of this substance as a refractory and particularly with the object of removing low melting impurities the authors have investigated methods of purification. It is found that zirconia is best dissolved by fusion with a mixture of borax and sodium carbonate. The fusion after treatment with dilute hydrochloric acid cannot be separated from the insoluble residue by direct filtration. It is found that by precipitating the zirconium and other metals as hydroxides in the unfiltered solution the insoluble residue is en- tangled in the precipitate and may then be filtered and washed.The hydroxide can then be dissolved on the filter-paper by warm dilute hydrochloric acid and on repeatedly pouring the filtrate through the filter-paper a clear filtrate may be obtained. This contains all the iron aluminium and zirconium and most of the titanium present in the original material. The solution of chlorides is diluted and treated with the calculated amount of sulphuric acid. A gelatinous precipitate of basic sulphates of zirconium and titanium is obtained whilst the whole of the iron and alumin- ium and some of the titanium and zirconium remain in solution. The solution is heated but not boiled with constant stirring to coagulate the precipitate which is filtered and washed until the washings give no reaction for iron with ammonium thiocyanate.This process which is slow and tedious is efficient for removing iron aluminium and silica but does not remove much of the titanium. J. F. S. Reaction of Methane and of Acetylene with Zirconium Tetrachloride. I?. P. VENABLE and R. 0. DEITZ ( J . Elisha MitcheZZ Sci. Xoc. 1922 38 74-75) .-Zirconium tetrachlorideINORGANIC CHEMISTRY. ii. 171 reacts with ammonia phosphine and hydrogen sulphide forming compounds which when heated yield zirconium nitride phosphide and sulphide respectively. Zirconia reacts with carbon at a high temperature forming the carbide ZrC. The interaction of zircon- ium tetrachloride with methane gives rise to three distinct solid products namely black particles light brown particles and colour- less masses with black inclusions. The first which was present in small quantity contained 32.09% C.The reaction with acetylene begins on gentle heating and is exothermic. CHEMICAL ABSTRACTS. Isolation of the Oxide of a New Element. ALEXANDER SCOTT (T. 1923 123 311-312). The New Element Hafnium. D. COSTER and G. HEVESY (Nature 1923 111 182; cf. this vol. ii 80).-In order more accurately to estimate the amount of hafnium in the samples examined a known quantity of tantalum (73) was added and the intensities of the lines were compared. A large number of zircon- ium minerals have been examined and all have been found to contain between 5 and 10% of hafnium. Moreover a chemical method of separation (details of which are not given in the present brief communication) has resulted in the production on the one hand of a substance containing about 50% of hafnium and on the other of zirconium which did not yield any hafnium lines. A.A. E. The Element of Atomic Number 72. G. URBAIN (Compt. rend. 1923 176 469-470); G. URBAIN and A. DAVVILLIER (Nature 1923 111 218; cf. this vol. ii 80 and preceding abstract).-The lines observed in the high-frequency spectra of zirconium minerals by Coster and Hevesy appear to be identical with those previously observed in the case of ytterbia by Urbain (A. 1911 ii 115; see also A. 1922 ii 505 and Dauvillier A. 1922 ii 463). Priority is therefore claimed for the name “ celtium,” then given to the element producing the lines in question as against “ hafnium.” It is however admitted that to celtium was incorrectly ascribed properties intermediate between those of lutecium and scandium. Moreover other cases are quoted in support of the contention that it is not impossible for a quadrivalent element such as that under consideration to be present in the mother-liquors after fractionation of the rare earths.A. A. E. The New Element Hafnium. D. COSTER and G. HEVESY (Nature 1923 111 252).-A reply to Urbain and Dauvillier (pre- ceding abstract).-Hafnium is considered to differ from celtium in that there is no difficulty in separating the former from contents of rare earths nor does it appear to yield the characteristic optical spectrum ascribed by Urbain to celtium. It is maintained that the X-ray spectrum of hafnium is not coincident with that de- scribed by Dauvillier. The hafnium content of the earth’s crust is estimated to be more than 1 part per 100,000. A.A. E.ii. 172 ABSTRACTS OF CHEMICAL PAPERS. Germariium. IV. Germanium Tetraiodide. L. M. DENNIS and F. E. HANCE ( J . Amer. Chem Soc. 1922 44 2854- 2860; cf. A. 1922 ii 160 302).-Germanium tetraiodide is pre- pared by passing iodine vapour in a current of carbon dioxide over crystalline germanium heated at 250-360'. The tetraiodide sublimes and a deposit of yellow and red crystals and a red liquid are formed in the cooler parts of the tube. Between the boat containing the germanium and the red iodide a small deposit of yellow crystals formed; these are germanous iodide GeI which crystallises in the hexagonal system with angles of 120". German- ium tetraiodide at the ordinary temperature is of the colour of coral when in lump form ; when powdered it has an orange colour.The colour depends on the temperature a t -185" it is canary- yellow; -50" buff; -lo" orange; +35" salmon; +50" brick- red; +90' red and +144" ruby red. It melts sharply a t 144" to a ruby-coloured liquid. It forms regular octahedra and has di$4*3215. Concentrated sulphuric acid has no action on it and since all other liquids examined either dissolve or decompose it the density was determined by means of sulphuric acid. German- ium tetraiodide sublimes a t temperatures just above the melting point without dissociation but a t 440" dissociation occurs according to the equation GeI Ge12+12. It is practically unchanged when exposed to air for five months but is decomposed by a small quantity of water giving germanium dioxide.Cold concentrated sulphuric acid produces no change in it in twenty-four hours but on heating a t 80" there is a slow liberation of iodine. It is slowly dissolved by cold 1 4-potassium hydroxide concentrated nitric acid turns it black with liberation of nitrogen dioxide and con- centrated hydrochloric acid dissolves it very slowly. Concentrated ammonia solution decomposes it to form a white solid which is soluble in water whilst dry gaseous ammonia slowly converts it into a white powder which is soluble in water. Germanium tetra- iodide dissolves in the following solvents giving solutions of the colours named; in all cases the solutions were quite unchanged after keeping for four months benzene reddish-orange ; carbon disulphide reddish-orange ; methyl alcohol deep orange ; ethylene dichloride light orange ; chlorobenzene reddish-orange ; carbon tetrachloride light orange ; ethylene glycol light yellow and ethylene chlorohydrin light yellow.It is also dissolved by the following solvents giving solutions varying in colour from deep orange to pale yellow but in every case a slow decomposition takes place hexane amyl alcohol chloroform nitrobenzene light petroleum butanol and acetic acid. Many solvents decompose it a t once. J. F. S. Measurements of the Density of Metals and Alloys,-at High Temperatures. IV. The Systems Antimony-Zmc and Aluminium-Antimony and the Metals Silver and Magnesium. P. SATTERWALD (2. Jfetallk. 1922 14 457- 461) .-The specific volumes of zinc-antimony alloys are greater than the values calculated from those of the two inetals both a tINORGANIC CHEMISTRY.5. 173 ordinary and a t elevated temperatures and a maximum value is obtained a t a composition corresponding with Zn,Sb,. Aluminium- antimony alloys show deviations from the calculated values only at the ordinary temperature an abrupt change occurring a t the composition corresponding with AlSb. At lOOO" this compound is decomposed and the specific volume of any alloy may then be calculated from those of its constituents. The specific volumes of silver at temperatures up to 1100" and of magnesium at 780" have been determined [cf. J.S.C.I. 1923 229~1. Examination of the Alleged Antimonious Hydroxides. CHARLES LEA and JOHN KERFOOT WOOD (T. 1923 123 259- 265). The Crystal Structure of Bismuth.L. W. MCKEEHAN (J. Franklin Inst. 1922 195 59-66).-New data have been obtained using the powder method and the X-rays of molybdenum. The results are best explained by means of a simple rhombohedral space lattice with a set of rhombohedral axes mutually inclined at 57' 16'. From the absence of any planes attributable to (422)' (330)' and (411)' it is deduced that the bismuth atoms are not uniformly placed along the trigonal axis. The distances between adjacent atom centres have been calculated and are shown in a diagram. W. E. G. The Anode Oxidation of Gold. 111. FR. JIRSA and OT. BURYLNEK (Chem. Listy 1922 16 328-330; cf. A. 1922 ii 713 this vol. ii 80).-It is concluded that the oxidation of gold anodes in dilute sulphuric acid takes place in four stages. The first which requires the least E.M.F. is the solution of gold in sulphuric acid to form aurous sulphate. This is hydrolysed in the second stage to auric hydroxide 2Au,S04+2H,0 -+ 2Au(OH)S0,+H2S0,+2Au ; Au(OH)SO -+ Au(OH),+H,SO,. In the third stage the gold again dissolves in the acid this time forming auric sulphate which also undergoes hydrolysis in dilute solution going first into the basic sulphate and then into auric hydroxide as before. In the fourth stage the tervalent gold becomes quadrivalent forming AuO,. Since at the ordinary temperature the dissociation pressure of this oxide is above one atmosphere it decomposes liberating oxygen and forming auric oxide. The four stages may be thus shown I. Au -+ Au' ; 11. 3Au' -+ Au"'+BAu ; 111. Au + Au"' ; IV. Au"' -+ Au"" -+ Au"'. The hydrolysis of the aurous sulphate explains why oxidation to bivalent gold does not take place. It is found generally that a gold anode in dilute sulphuric acid exhibits typical passivity and that oxidation to auric oxide proceeds without the formation to any appreciable extent of intermediate products. The speed with which gold anodes in the presence of lower degrees of oxid- ation become passive is so great that it is impossible to isolate any intermediate oxidation product. The solubility of auric hydroxide increases with the concentration of the acid whilst the passivity of a rotating gold anode decreases. Since with a stationary A. R. P. 7"ii. 174 ABSTRACTS OF CIIEMICAL PAPERS. anode the final passivity in concentrated acid is greater than in dilute it is only possible to show the existence of the intermediate stages Au' and Au"' if a rotating anode is used. The existence of auric dioxide (AuO,) is proved beyond doubt by the discharge curve and the depolarisation curve given in the original. R. T.

ISSN:0368-1769    

DOI:10.1039/CA9232405149

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

i. 162 ABSTRACTS OF CHEIIICAL PAPERS. Physiological Chemistry. Respiratory Exchange in Fresh-water Fish. IV. Further Comparison of Gold-fish and Trout. JOHN ADDYMAN GARDNER and GEORGE KING (Biochem. J. 1922,16 729-735).-The oxygen tension a t the asphyxia1 point a t various temperatures in the case of the gold-fish has been determined. This fish can stand much lower oxygen tensions for any temperature than the trout. The difference is more marked at low temperatures. Trout kept at a low temperature corresponding with a state of hibernation showed a higher glycogen content than control fish kept at higher tem- peratures which is consonant with the respiratory . coefficients obtained for these fish. Glycogen estimation in the case of the gold-fish yielded results which were in conformity with the low level of their metabolism.Respiratory Exchange in Fresh-water Fish. V. Eels. JOHN ADDYMAN GARDNER and GEORGE KING (Biochem. J. 1922 16 73&738).-Eels live a t a much lower plane of metabolism than trout. At medium temperatures trout use about four times as much oxygen as eels and a t low temperatures 10-12 times as much. s. s. z. Influence of the Introduction of Water on Blood Concen- tration Induced by Deprivation of Water. FRANK P. UNDER- HILL and ROBERT KAPSINOW ( J . Biol. Chem. 1922,54,459-464).- The experiments were performed on dogs. Deprivation of water for short intervals produced an increased blood concentration which rapidly returned to approximately the normal on adminis- tration of water. E. S. Gas and Electrolyte Equilibria in the Blood.111. The Alkali-binding and Buffer Values of Oxyhamoglobin and Reduced Haemoglobin. DONALD D. VAN SLYKE A. BAIRD HASTMGS MICHAEL HEIDELBERGER and JAMES M. NEILL ( J . Biol. Chem. 1922 54 481-506) .-The technique previously developed s. s. z.PHYSIOLOGICAL CHEMISTEY . i. 163 (A. 1922 i 1207) has been used to determine the amount of alkali bound both by recrystallised horse oxyhaemoglobin (Heidelberger A. 1922 i 962) and by reduced haemoglobin when under physio- logical conditions of concentration carbon dioxide tension and P value. At Pw 7.4 one gram-molecule of oxyhaemoglobin binds 2*15&0.10 equivalents of alkali (sodium) whilst the corresponding figure for reduced haemoglobin is 1*47&0*08. The change of one mol. of reduced haemoglobin to oxyhemoglobin thus enables it to combine with an additional 0*68*0-10 equivalent of alkali.At intermediate points the increase in base bound is directly pro- portional to the increase in oxygen content thus agreeing with Henderson’s theory (A. 1921 i 473) and with the assumption originally made by Christiansen Douglas and Haldane (A. 1914 i 1012). The molecular buffer values (cf. A. 1922 i 893) of oxyhemoglobin and reduced haemoglobin are practically constant over the physiological range of P that for the former being p0=2*64 and for the latter pR=2.45. The authors conclude from these values that the alkali taken up by haemoglobin is shared between at least five univalent acid groups. The total amount of base bound by haemoglobin at PH values varying from 7.2 to 7.5 is given by the equation B=2-64[HbO2](P,,-6*585)+ 2*45[Hb](P - 6.80).E. S. Gas and Electrolyte Equilibria in the Blood. IV. The Effect of Oxygenation and Reduction on the Bicarbonate Content and Buffer Value of Blood. DONALD D. VAN SLYKE A. BAIRD HASTINGS and JAMES M. NEILL ( J . Biol. Chern. 1922 54 507-526).-The experiments recorded in the previous paper have been extended to oxygenated and reduced horse blood (oxalated or defibrinated). Since carbonic acid and hzmoglobin are the only acids present in blood the assumption has been made in interpreting the results that changes in the amount of base present as bicarbonate are accompanied by equal and opposite changes in the amount combined with haemoglobin. The results show that each specimen of blood when at the same degree of oxygenation has a constant buffer value over the P range 7.2 to 7.5 the average values of different specimens being 25.3 for oxygenated blood and 24.4 for reduced blood (buffer values are here expressed as millimols.of base per unit change in P ; cf. A. 1922 i 893). The difference between these two values is due to the loss of buffer value which occurs when oxyhaemoglobin is reduced (cf. preceding abstract) a loss which i s partly compensated for by an increase in bicarbonate content. Thus of the total buffer value haemoglobin was responsible for 76.0% and bicarbonate for 6.9% in oxygenated blood the figures for reduced blood being 73.3 yo and 9.0yo respectively. Each additional molecule of oxygen taken up by haemoglobin at P 7.3 caused decreases in the bicarbonate content varying from 0-50 to 0.59 in different specimens.On the above assumption a mol. of haemoglobin when changed from the reduced to the oxygenated state therefore combines with an additional 0.504.59 equivalent of alkali. This value differsi. 164 ABSTRACTS OF CHEMICAL PAPERS. from that obtained with solutions of crystallised hsmoglobin and is hence probably influenced by some unknown variable factor in blood. As for solutions of hsmoglobin the amount of additional base combined with hzmoglobin in blood on oxygenation was directly proportional to the amount of oxygen combined. Over the range PH 7.2 to 7.5 a rise of PR 0.1 caused an increase of approximately 0.02 equivalent in the amount of base transferred from bicarbonate to hEmoglobin by one molecule of oxygen.E. S. Evaluation of Buffers of the B3ood. EDWAED A. DOISY A. P. BRIGCGS EMILY P. EATON and WZLLIAM H. CHAMBERS (J. BioZ. Chem. 1922 54 305-329).-The authors have investi- gated the extent to which the various known buffer systems of the blood participate in binding carbon dioxide during the change of blood from the arterial to the venous state. In the results obtained from three specimens of human blood from 87-95% of the carbon dioxide has been accounted for. Of the total amount taken up 75-80% was due to the hzemoglobin less than 1% to the inorganic phosphates and less than 5% to the buffers contained in the separated serum. CIT. 0. Gun;- LA= ( J . Pharm. Chim. 1923 [vii] 27,&23).-Por the measure- ment of the P of the blood and the alkaline reserve the methods described by Cullen ( J .Biol. Chem. 1922 52 508) with very slight modifications give accurate results with inexpensive apparatus. H. K. E. S. Measurement of the Alkalinity of the Blood. Relations Existing between Arterial and Venous Blood of the Dog with Special Reference to the Plasma Chlorides. EDWARD A. DOISY and J. W. BECKMANN (J. BioZ. Chem. 1922 54 683-691 .)-Analyses were made of arterial and venous blood drawn simultaneously from dogs. The results shorn that the migration of hydrochloric acid from plasma to corpuscles which is to a large extent responsible for the buffer action of blood in vitro (cf. A. 1922 i 963) occurs also in vivo as blood passes from the arterial to the venous state. Evidence was also obtained although the results were less consistent that the blood respiratory coefficient has a normal value that the additional carbon dioxide contained in venous blood is approximately equally distributed between plasma and corpuscles and that the corpuscles occupy a larger volume in venous than in arterial blood.Non-protein Organic Constituents in the Blood of Marine Fish. W. DENIS (J. Biol. Chem. 1922 54 693-700).-Analyses previously made (A. 1914 i 106) have been repeated using recent methods. The following are the average results expressed in mg. per 100 C.C. of blood for different species of elasmobranch and teleost fishes Elasmobranch blood-non-protein nitrogen 1000 ; urea nitrogen 800 ; amino-nitrogen 28 ; creatinine 6 ; creatine 25 ; uric acid 1.1.Teleost blood-non-protein nitrogen 65 ; urea nitrogen 9 ; amino-nitrogen 28; creatinine 1.0; creatine 6; uric acid 4. The blood of invertebrates was found frequently to contain E. S.PHYSIOLOGICAL CHEMISTRY. i. 165 no amino-nitrogen although considerable amounts were present in the muscle. E. S. The Neutrality of Blood. J. MELLANBY and C. C. WOOD (Proc. Physiol. Soc. 1922 lii-lii ; J . Physiol. 1922,58 ; from Physiol. Abstr. 1922 7 490).-Corpuscles partly freed from carbon dioxide and suspended in 0*85% sodium chloride solution have a slightly acid reaction. When exposed to alveolar air these corpuscles absorb carbon dioxide and the reaction tends to neutrality. On the other hand serum from the same blood is alkaline in reaction and on exposure to alveolar air becomes more acidic.This apparently paradoxical effect of carbon dioxide explains the approximate neutrality of the blood under varying tensions of carbon dioxide and perhaps also the divergence which exists between the calculated reaction of the blood based on the ratio of the free and combined carbon dioxide contained in it and that actually observed by direct experiment. ALICE ROHDE DAVIS ELEANOR B. NEWTON and STANLEY R. BENEDICT ( J . Biol. Chem. 1922 54 595-599).-The uric acid compound present in the corpuscles of ox blood (cf. A 1915 i 612) has been isolated. It forms square plates which do not melt under 300° and when hydrolysed with sulphuric acid yields equimolecular quantities of uric acid and d-ribose. It is apparently a monobasic acid; its sodium salt has [ay:+20-42”.Distribution of the Combined Uric Acid in the Corpuscles of Ox Blood. ELEANOR B. NEWTON and ALICE ROHDE DAVIS ( J . Biol. Chem. 1922 54 601-602).-The combined uric acid (cf. preceding abstract) is present entirely in the erythrocytes. W. 0. K. Combined Uric Acid in Ox Blood. E. S. E. S. Combined Uric Acid in Human Horse Sheep Pig Dog and Chicken Blood. ELEANOR B. NEWTON and ALICE ROHDE DAVIS ( J . Biol. Chern. 1922 54 603-605).-The combined uric acid compound (cf. preceding abstracts) seems to be present in the blood of all the above species but in much smaller amounts than in ox blood. E. S. Influenc’e of Subcutaneous Injections of Indole and Scatole on the Nitrogenous Metabolism of the Rabbit. FRANK P. UNDERHILL and ROBERT KAPSINOW ( J .Biol. Chem. 1922 54 717-72O).-Using doses of 30 mg. per kg. no influence was observed. Indole but not scatole apparently increased the excretion of ethereal sulphates. Inorganic Metabolism. I. Inter-relations between Cal- cium and Magnesium Metabolism. L. JEAN BOGERT and ELIZABETH J. MCKITTRICK ( J . Biol. Chem. 1922 54 363-374).- The addition of magnesium citrate in amounts of 6 g. per day to the diet of four subjects caused an increased excretion of magnesium both in the urine and feces. There was also an increase in each case in the total calcium excreted and in three out of the four E. S.i. 166 ABSTRACTS OF CHaMICAL PAPERS. cases in both urinary and faecal calcium. The similar addition of calcium lactate caused increase in both urinary and fscal calcium.There was probably also an increased excretion of magnesium. E. S. Inorganic Metabolism. 11. Effects of Acid-forming and Base-forming Diets on Calcium Metabolism. L. JEAN BOGERT and ELIZABETE E. KIRKPATRICK ( J . Biol. Chem. 1922 54 375-386).-Although certain irregularities occurred the results in the main indicate that acid-forming diets divert calcium from the faeces to the urine and also cause an increased total excretion. Base-forming diets on the other hand divert calcium from the urine to the faeces and produce a diminution in the total excretion. E. S. Inorganic Metabolism. 111. Influence of Yeast and Butter Fat upon Calcium Assimilation. L. JEAN BOGERT and RUTH K. TRAIL ( J . Biol. Chern. 1922 54 387-397).-1n the case of four women the addition of either yeast or butter fat to a diet which was otherwise vitamin-free produced an increased retention of calcium.The amount of calcium excreted in the faxes was diminished. E. S. Antiketogenesis. IV. The Ketogenic - Antiketogenic Balance in Man and its Significance in Diabetes. PHILIP A. SHAFFER ( J . Biol. Chem. 1922 54 399-441).-Further work on the ketolytic reaction in vitro (cf. A. 1921 i 754) has shown that under proper conditions one molecule of dextrose accomplishes the disappearance of two molecules of acetoacetic acid when the latter is in excess. On this basis the values previously assigned (A. 1922 i 83) to the antiketogenic factors must be doubled. This conclusion is supported by the results obtained by Wilder and Winter (A. 1922 i 893) but when applied to cases taken from the literature it leads to a calculated excretion of acetone substances which is considerably smaller than that actually found.The protein ketogenic factor has therefore been arbitrarily increased by 50%. With this modification moderate agreement between the calculated and actual values has been obtained. In cases of severe ketosis (where the acetoacetic acid is in excess) each molecule of dextrose appears without doubt to be equivalent ketolytic substance for two molecules of keto-acid. At the threshold of ketosis however the dextrose molecule may have a lower value owing to oxidation taking place without its coming into contact with the keto-acid. The author discusses the bearing of these results on the dietetic problem of diabetes. E. S.Colorimetric Researches on Tryptophan. VII. The Tryptophan Requirements of Growing Rats (a Contribution to the Question of Cyclopoiesis). OTTO FURTH and FRITZ LIEBEN (Biochem. Z. 1922 132 325-341).-Only a small fraction (3-8%) of the tryptophan consumed by rats is retained in thePHYSIOLOGICAL CHEMISTRY. i. 167 body the rest being destroyed. ment for rats per kg. of body weight is greater than for man. The miminal tryptophan require- W. 0. K. Physical Chemistry of Foodstuffs. Investigation of Acid- taste. THEODOR PAUL (2. Elektrochem. 1922 28 435-446).- By the employment of the methods of psychophysics and the introduction of a new terminology the measurement of acid-taste has been placed on a quantitative basis. Molecular acidity is defined as the number of mols.of hydrochloric acid dissolved in a fixed volume of water which tastes as acid as one mol. of the acid substance dissolved in the same volume of water. The molecular acidity is determined not only by the hydrogen-ion concentration but also by the capacity of the solute to yield its reserve of hydrogen- ions to the tongue and to some extent by the nature of the anion and the vapour pressure of the acid. The acids investigated have been arranged in a series of increasing molecular acidities thus carbonic acid potassium hydrogen tartrate acetic acid lactic acid a-acetoxypropionic acid hydrochloric acid and tartaric acid. In this series carbonic acid possesses the weakest and tartaric acid the strongest acid taste. This order is not in agreement with the dissociation constants of these acids.For example the two acids a-acetoxypropionic and tartaric acids although possess- ing very similar dissociation constants show very different mole- cular acidities. The molecular acidity decreases slowly with increase in concentration. The curves obtained by plotting acid taste against concentration show several points of resemblance with the “sweetness” curves of “saccharin” and dulcin. The two properties acid-taste and sweetness behave in an analogous manner with increase in concentration and this suggests that similar relationships may exist between these and the salt and bitter qualities of substances. HEINRICH WIELAND (Ber. 1922 55 [B] 3639-3648).-A lecture delivered a t the centenary of the Versammlung Deutscher Naturforscher und Aerzte.H. W. Glutathione. 11. A Thermostable Oxidation-Reduction System. F. GOWLAND HOPKINS and M. DIXON ( J . Biol. Chem. 1922 54 527-563).-A continuation of the investigation of the recently discovered glutathione (A. 1921 i 635) has shown that in its functions in the cell this dipeptide is mainly associated with insoluble thermostable agents which act as hydrogen donators and form with it the thermostable reducing system of the tissues. Thus tissue which has been extracted with water treated repeatedly with boiling water or alternatively heated for three hours at loo” dehydrated with alcohol and finally dried in a vacuum all the operations being performed anakirobically when ground and sus- pended in a phosphate buffer mixture (PH 7-8) containing oxidised glutathione is able rapidly to reduce methylene-blue that portion of its reducing power which depends on the presence of the di- W. E.G . The Course of Oxidative Processes [in the Cell].i. 168 ABSTRACTS OF CHEMICAL PAPERS. peptide being practically unaffected by this treatment. The thermostable agents are however sensitive to oxidation (for example by hydrogen peroxide) and are even slowly destroyed by molecular oxygen. The latter effect is enormously accelerated by the presence of gluatathione. When suspensions of muscular tissue prepared as above are Grated in the presence of the di- peptide oxygen is absorbed to the extent of 400 c.mm. for every gram of dry material used. At the same time carbon dioxide is given off the ‘‘ respiratory quotient ” of the process being about unity a t first and falling off considerably during the later stages.These results suggest that a thermostable mechanism for oxidations and reductions coexists with the specialised enzymic mechanism in living tissue. E. S. Proportion of Sulphur in the Skin of Children Aged Less than One Year. E. LABORDE (Bull. Soc. Chim. biol. 1922 4 584-586).-1n the skin of three children approximately 0.2 yo of sulphur was found. In the healthy skin of another who had died from poisoning by sulphuric acid there was o*15y0 whilst the burned areas of the skin contained 0.37 yo. UBALDO SAniMARTINo (Biochem. Z. 1922,132 343-351).-An analysis of the fats in horse liver shows the presence of kephalin lecithin myristic acid butyric acid and other fatty acids and certain glycerol and cholesterol esters.W. 0. K. Chemistry of the Liver. W. 0. K. The Proteolytic Enzymes of the Spleen. S. G. HEDIN ( J . Biol. Chem. 1922 54 177-202).-At least three enzymes namely a-protease P-protease and erepsin are present in the spleen of the ox (cf. A. 1904 ii 58 ; Morse A. 1917 i 606 ; Dernby A. 1918 i 464). A partial separation of these has been effected by extracting the minced spleen successively with dilute acetic acid casein and 6% sodium chloride. The acetic acid extract contains all three enzymes ; the casein extract contains mainly @-protease and erepsin ; whilst a solution in sodium hydroxide of the globulin obtained from the sodium chloride extract contains mainly a-protease. If the spleen is kept for any length of time in alkaline solution or at an acidity less than PH 5.2 the enzymes show a loss of activity which cannot be revived by acids.a-Pro- tease which acts in alkaline solution converts proteins into peptones more rapidly than peptones into amino-acids ; its action is inhibited by serum-albumin (cf. also Bradley A. 1922 i 896). E. S. The Catalytic Destruction of Carnosine in Vitro. WINIFRED MARY CLIFFORD (Biochem. J . 1922 16 792-799).-A catalyst is described which is capable of destroying carnosine in muscle extract. It is present in ox rat and cod muscle but is absent in the muscle of invertebrates such as the oyster and the lobster. It is also present in the liver of the rat and of the ox. The kidney of the rat ox or sheep does not contain it. The curve of action of this catalyst is unlike any enzyme curve The possible mechanism ofPHYS1OLOGICA.L CHEMISTRY. i.169 its action is discussed. It is also suggested that carnosine may be Excretion of Acid and Ammonia. ROGER S. HUBBARD and SAMUEL A. MUNFORD ( J . Biol. Chem. 1922 54 465-479).-From a statistical analysis of the results of a series of analyses of human urine the authors conclude that the excretion of ammonia varies with the volume and the reaction of the urine but is not directly affected by the amount of acid excreted. The relation between the reaction of the urine and the excretion of ammonia is con- cerned rather with the concentration of the ammonia than with the actual amount excreted. The latter fact is interpreted as supporting the theory (Nash and Benedict A.1922 i 191 483) that the kidney is the seat of formation of ammonia. The Influence of Fat and Carbohydrate on the Nitrogen Distribution in the Urine. EDWARD PROVAN CATHCART (Biochem. J. 1922 16 747-753).-The output of total nitrogen urea and ammonia rises on a fat diet and falls on the addition of carbohydrate. The output of uric acid is low on the fat diet and increases on the addition of carbohydrate whilst the output of total creatinine is but little affected by the change of diet. Small amounts of creatine are excreted on a carbohydrate-free diet. The output of undetermined nitrogen is greater on diets containing carbohydrate than those from which carbohydrate is absent. an intermediate product of metabolism. s. s. 2. E. S. s. s. z. Constancy of the Cseatine-Creatinine Excretion in Children on a High Protein Diet. VICTOR JOHN HARDING and OLIVER HENRY GAEBLER ( J . Biol. Chem. 1922 54 579-587).-The same amount of total creatine (creatine+creatinine) is excreted by normal children of the same age when under the same environment. The amount excreted per kg. of body weight (" total creatine coefficient '7 is constant for children of all ages and is of the same magnitude as the creatinine coefficient of an adult man. Elimination of Cholesterol in Urine. WILRELM GRUNKE (Biochem. Z. 1922 132 543-555).-Cholesterol occurs in normal urine only in traces. I n one case of icterus out of nine 10.1 mg. per day was found and in one case of diabetes out of five 12.9 mg. ; in other cases there was no more than a normal amount. E. S. W. 0. K. Comparative Toxicity of Ammonium Salts. FRANK P. UNDERHILL and ROBERT KAPSMOW ( J . Biol. Chem. 1922 54 451457).-From experiments on rats it is concluded that in general the t,oxicity of ammonium salts is directly proportional to their content of ammonia. Pharmacological Analogues of ac-2-hinotetrahydro- naphthalene. JULIUS VON BRAUN HEINRICH GRUBER and GEORG KIRSCHBAUM (Ber. 1922 55 [B] 3664-3674).4ee this vol. i 107. E. S.

ISSN:0368-1769    

DOI:10.1039/CA9232400162

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

i. 170 ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. Some Microbiological Consequences of the Oxidising Properties of Thorium-X. P. LEMAY and L. JALOUSTRE (Cmpt. rend. 1922 175 1053-1054; cf. A. 1922 ii 13 186).-In order to ascertain whether radioactive elements function as oxidation catalysts with regard to the activities of micro-organisms cultures of an&robic and aerobic organisms were submitted to the action of thorium-X. In the case of the anaerobic species (Bacillus butyricus) the radioactive material exercised an inhibiting effect on development the number of bacteria being about one-twentieth and the gas evolved about one-third of that in the control experi- ment whilst the action of the catalyst on the aerobic species (B. lacticus) appeared to be of a favourable nature.. Influence of the Culture Conditions on the Liquefaction of Gelatin and on the Production of Indole by Bacteria. OTTO ARNBECK (Biochem. Z. 1922 132 457479).-The production of indole and the liquefaction of gelatin by bacteria are inhibited by nitrogen-free foodstuffs such as glucose. Free ammonia on the other hand assists the liquefaction. Ultra-violet Absorption Spectra. of some Vitaminic Ex- tracts. HORACIO DAMIANOVICH (Anal. Asoc. Quim. Argentina 1922 10 209-214).-Yeast extracts containing vitamin-B show characteristic absorption spectra in the ultra-violet with general absorption in the extreme portion of the spectrum and a band between 2478 and 2660 A. which appears to be due to a pyrimidine or purine group.The absorption spectra of the oils from white and yellow maize respectively were also studied and a difference observed corresponding with the presence of vitamin-A in yellow maize oil and its absence from white maize oil. It is uncertain whether there is a causal connexion between presence of pigment and presence of vitamin-A in the yellow maize oil. Photospectro- graphs of the liquids examined arc appended. G. W. R. Synthesis of Water-soluble [Vitamin]-B by Yeast Grown in Solutions of Purified Nutrients. MARGARET B. MAC- DONALD ( J . Biol. Chem. 1922 54 243-248).-Using five different varieties of yeast the author confirms the conclusion of Nelson Fulmer and Cessna (A. 1921 i 386) that this organism is able to synthesise vitamin-B. E. S. TREVOR BRABY HEATON (Biochem.J . 1922 16 800-808) .-The activating substance of minimal concentrations of yeast (called by Wildiers ‘‘ bios ” and by Funk vitamin-D) is not identical with vitamin-B. Organs of pigeons rendered polyneuritic contain it in the same amount as those of normal pigeons. Its distribution differs from that of antineuric vitamin. Rats subsisting on a diet deficient in the water-soluble vitamin incur also the H. J. E. W. 0. K. Vitamin-D. deficiency of this act,ivating substance. s. s. z.VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 171 Influence of Amines on Fermentation. JULIUS ORIENT (Bioch,em. Z. 1922 132 352-361).-The various amines used show in general a retarding effect on fermentation by yeast when applied in a concentration of 4.8%. This effect however changes into one of acceleration if the concentration of the amine be either higher or lower except in the cases of methylamine and betake which inhibit the fermentation even in low concentrations.W . 0. K. Fermentation of Sugar in Presence of Sodium Sulphite following Neuberg and Reinfurth. Equivalence between Aldehyde and Glycerol. HEINRICH GEHLE (Biochem. Z. 1922 132 566-588).-1n the fermentation of sucrose by yeast in the presence of sodium sulphite there is in general rather more than one equivalent of glycerol formed for one equivalent of acet- aldehyde. This is particularly the case with small amounts of sulphite and a short fermentation time. As increased proportions of sulphite are used the rate of increase in the yields of glycerol and of acetaldehyde gradually decreases until the maximum yield is obtained using 60% of sulphite calculated on the sugar.With increasing percentage of sulphite the rate of evolution of carbon dioxide is decreased. Equivalence in the Production of Acetaldehyde and Glycerol in the Second Form of Fermentation. C . NEUBERG J. HIRSCH and E. REINFURTH (Biochem. Z. 1922 132 589-596).-Gehle’s results (preceding abstract) are vitiated by a systematic error in the estimation of the acetaldehyde. If this be estimated gravi- metrically by the “ dimedon” method (A. 1920 i 914) precise equivalence between glycerol and acetaldehyde is found. W. 0. K. W. 0. K. CARL NEU- BERG (Ber. 1922 55 [B] 3624-3658).-A lecture delivered a t the centenary of the Versammlung Deutscher Naturforscher und Aerzte. H.W. A. GORIS and P. COSTY (Cmpt. rend. 1922,175 998-999; cf. A. 1922 i 1220). -The distribution of urease in the pileus stipe and hymenium of twelve species of fungi was investigated. In all cases the hymenium contains the greatest proportion of the ferment. A brief account of the method of extraction and estimation of the urease is given. The Chemistry of Fermentative Phenomena. The Presence of Urease and Urea in Fungi. H. J. E. The Action of the Nitrogen of Hexamethylenetetramine on Plant Growth. E. BLANCH W:GEILMANN and I?. GIESECKE ( J . Landw. 1922 70 221-251).-Pot experiments are described which show that hexamethylenetetramine is as effective a fertiliser as ammonium sulphate. The soil bacteria decompose the substance into ammonia which is nitrified in the usual way.The presence of hexamethylenetetramine in liquid farmyard manure preserved by the addition of formaldehyde brings no unfavourable conse- quences A. G. 9.i. 172 ABSTRACTS OF CHEMICAL PAPERS. The Effect of the Kations of Salts on the Destruction and Synthesis of Starch in Plants. W. S. IWIN (Biochem. Z. 1922 132 494-510).-The rate of disappearance of starch from plant cells immersed in a solution of a salt is influenced by the kation of the salt. Univalent kations and also barium and glucinum effect the solution of the starch and at the same time cause an increase of the osmotic pressure in the cell whilst magnesium calcium and strontium are inactive. If on the other hand the cells be immersed in a solution of maltose the synthesis of starch is inhibited by the presence of barium caesium lithium sodium calcium potassium rubidium magnesium and strontium in order of decreasing activity.W. 0. K. Synthesis and Hydrolysis of Starch under the Influence of Anions in Plants. W. S. IUIN (Biochem. Z . 1922 132 51 1-525 ; cf . preceding abstract) .-Similar results are obtained with anions the organic anions being particularly active in raising the osmotic pressure and influencing the synthesis and hydrolysis of starch. W. 0. K. Physiological Protection in Plants against the Harmful Action of Salts. W. S. ILJIN (Biochem. Z . 1922 132 526- 542 ; cf. preceding abstracts).-The salt effects described in the preceding two abstracts would be harmful to plants but it appears that certain ions act antagonistically to each other.Calcium for instance may inhibit the effect of sodium. In this way the existence of halophytes may be understood. W. 0. K. Pigments of the Mendelian Colour Types in Maize iso- Quercitrin from Brown-husked Maize. CHARLES E. SANDO and H. H. BARTLETT ( J . Biol. Chem. 1922 54 629-645).- isoQuercitrin has been isolated from the husks of a brown-husked maize. It forms primrose-yellow needle-like plates m. p. 220- 222-5" and is probably identical with the ragweed glucoside obtained by Hey1 (A. 1919 i 615). Aqueous solutions of iso- quercitrin give an olive-green coloration with ferric chloride a yellow precipitate with lead acetate and a rose-red colour on reduction with magnesium and hydrochloric acid. The yellow colour of the substance is intensified by sodium carbonate and dilute ammonia. The spectral transmission curves of both iso- quercitrin and quercetin have been determined. E. S. Biological Adsorption from Solutions of Metallic Salts. FRIEDRTCQ PICHLER and ARTUR WOBER (Biochem. Z. 1922 132 420438).-An investigation of the adsorption particularly of copper and also of mercury and cerium from solutions of their salts by the spores of maize rust ( 2) (Maisbrandsporen). In general there is a connexion between the degree of adsorption and the toxicity of the ion. W. 0. K.

ISSN:0368-1769    

DOI:10.1039/CA9232400170

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

i. 173 0 r g anic C h 8 mist r y. New System for the Linear Representation of the Structure of all Organic Compounds. T. SHERLOCK WHEELER (Chm. News 1923 126 33-35 49-50 66-67).-A system designed to enable the structure of all organic compounds to be represented linearly by a simple arrangement of letters and figures from which with the aid of a few rules the graphical formula could be deduced easily. The original must be consulted aa the paper does not lend itself to abstraction. The Solubility of Methane in Water and Organic Solvents under Pressure. 3'. FISCHER and C. ZERBE (Brennstoff-Chem. 1922 iv 17-19).-The solubility of mine gases of the composition methane 79*4% carbon dioxide 0*7% oxygen 2.8% and nitrogen 17.1% in a large number of solvents under a pressure of about 20 atm.and also the composition of the gases evolved from the solvent were determined. The latter in most cases differed little from that of the original mixture so that the figures obtained may be taken as approximately true for pure methane. The figure for the solubility in water (0.09 C.C. per g. for 1 atm.) is however too high owing to the higher solubility of carbon dioxide. The highest figure obtained is 1.34 for light petroleum (b. p. below 65") Others include for ethyl alcohol 0.60 for chloroform 0.32 for aniline 0.16. If the product of these solubility figures and the surface tension of the solvent are calculated a series of figures which approximate to a constant is obtained as previously shown by Christoff for carbon monoxide. Water nitrobenzene aniline and chloroform are exceptions.Both surface tension and solubility however decrease with a rise in temperature and it is questionable whether a fair comparison is obtained at a uniform temperature The Constituents of the Fraction of a Borneo Petroleum which Distils between 37" and 81'. G. CHAVANNE (Bull. Xoc. chim. Belg. 1922 31 331-364).-An examination of the petrol showed that all the possible isomerides of hexane are present as are all the hydrocarbons derived from cycbpentane and cyclo- hexane the boiling points of which are included in the fraction investigated. With the exception of ethylcyclobutane all the cyclic compounds present are derived from five- or six-membered rings. Of the hexanes present normal hexane is the most abundant followed by isohexane and y-methylpentane whilst pp- dimethylbutane and py-dimethylbutane are present in much smaller proportion.The saturated cyclic hydrocarbons present in quantity are cyclohexane and methylcyclopentane. A number of physical constants are given which differ slightly if at all from those in the literature and the author states that the critical ( 2 0 O ) between liquids of widely differing b. p. c. I. VOL. CXXIV. i. hi. 174 ABSTRACTS OF CHEMICAL PAPERS. temperature of solution in aniline (cf. Chavanne and Simon A. 1919 ii 267 432 433) and the density are important factors in the experimental study of complex mixtures of hydrocarbons (cf. Chavanne and Simon A. 1919 i 380). H. J. E. The Mechanism of Thermal Decomposition of the Pentanes G CALXBGAERT ( J .Amer Chem. Sm. 1923 45 130-135).- When pentane vapour is passed through a tube at ciao" it is de- composed giving hydrogen and a mixture of hydrocarbons. Under the experimental conditions about 30% of the pentane is decom- posed and 44% of the product consists of unsaturated hydro- carbons. The product contains hydrogen 5y0 methane 12% ethane Z6% propane loyo pentane 4y0 ethylene loyo propylene 24% butylene 3y0 and 6% of a C,H hydrocarbon. These results correspond with a rupture of the pentane molecule a t the central carbon atom giving an ethyl and a propyl group one of which is then saturated at the expense of the other which becomes un- saturated the change going mainly in the direction of forming ethane and propylene. Under similar conditions isopentane is also decomposed and an analysis of the products shows that in this case the molecule breaks on one side or the other of the tertiary carbon atom.This results in a methyl and an isobutyl group which give methane and Aa- or Ap-butylene. A second reaction gives an ethyl and an isopropyl group and ethane results but never propane. There is also another reaction which occurs to a s m d extent and results in the formation of amylene and finally a part of the amylene and butylene give by a secondary Ireaction butadiene and pentadiene. W. G. Constitution of Squalene. RIKO M~JIAIA and BENNOSUK~ KUBOTA (Japun. J . Chem. 1922 i 19-33).-An English trans- lation of the paper previously published in Japanese (this vol. i 1). K. K. Preparation of Methyl Bromide. ARTUR BYGDBN (J.pr. Cherrt. 1922 [ii] 104 285-.288).-Steinkopf and Schwen (A. 1921 i 841) have obtained a 77% yield of methyl bromide calcu- lated on the bromine taken if the reagents are employed in the ratio of 1 atom Br+0.5 atom P+2.5 mol. MeOH. It is now shown (cf. A. 1911 i 43; also Holt T. 1916 109 1) that a 97.3% yield may be obtained by using the following molecular propor- tions lKBr:3H2SO,:2MeOH the acid being diluted with one- third its weight of water previously to the addition of the other reagents. The most economical preparation considering the cost of all the materials is however effected by the use of lKBr 3H,S04 1-25MeOH the yield being then 95.9%. W. S. N. The Spontaneous Decomposition of Unsaturated Aliphatic Iodochlorides. LLOYD B. HOWELL ( J . Amer. Chem.Soc. 1923 45 182-187 ; cf. Noyes A. 1920 i 469).-When p-chloroethylene iodochloride decomposes spontaneously the products are iodineORGANIC CHEMISTRY. i. 175 monochloride trichtoroiodoethane aa B-tet<mchloroethane and a dichloroiodoethane and of these the first two are formed in much larger amounts than the last two. Under similar conditions a@-dichloro- P-iodoethylene iodochloride gives no saturated com- pound except hexachloroethane. The principal products in this case are iodine monochloride and dichlorodi-iodoethylene together with some a-chloro-app-tri-iodoethylene and some trichloroiodo- ethylene. The changes consist in several rearrangements involving the splitting off of chlorine a'nd iodine monochloride from the iodo- chloride group the addition of one molecule of iodine monochloride or of chlorine to the maturated residues and the replacement of iodine by chlorine or vice versa.If the carbon atoms of the double union in an urmaturated aliphatic a-iodochloride hold hydrogen atoms the products of its decomposition are saturated halogen derivatives but if they hold only halogen atoms the decomposition leads to unsaturated products. Compounds described are a@- trichloro-cc-iodoethane b. p. 101-102"/31-32 mm. d i 2.266 ng 1.5884; ( ?) ua-dichho-P-iodoethane b. p. 146-148"/28 mm. dg2.861; ap-dichZoro-ap-di-iodoethy7leney b. p. 243.4" m. p. 2*5-3.0" d! 2.934 ; and a-chloro-ccpp-tri-iodoethylene. W. G. Synthesis by Means of Magnesium Ally1 Halides. SAMUEL COFFEY (Rec. trav. chim. 1922 41 652-654).-A repetition of Jaworsky's preparation of allyldimethylcarbinol (A 1909 i 151) showed that dime thylallylcar binyl allyl ether C,H ,*CMe,*O*C,H is obtained as a by-product the yield being about 20% calculated on the basis of the allyl chloride used.It is a pale yellow mobile oil b. p. 190-193" d: 0.8765 dj7 0.8754 niy 1.4750. Dimethyl- allylcarbinol has m. p. -73" d;; 0-83553 di7 0.83452 ng 1.430. The acetate obtained in 40% yield by modifying Houben's method (A. 1906 i 520) has m. p. -94-5" b. p. 4648"/21 mm. or 136- 138"/atmospheric pressure (decomp.) dtz 0.88797 di5 0.88720 ng 1.4230. Neither of these substances reacted with solutions of perbenzoic acid. H. J. E. The Oxidation of Propylene Glycol with Potassium Per- manganate. FVILLIAM LLOYD EVANS ( J . Amer. Chem.SOC. 1923 45 171-176; cf. A. 1912 i 743).-A study of the oxidation of propylene glycol by potassium permanganate a t 50" and 75" in the presence of various concentrations of alkali. In neutral solu- tions the products are acetic acid and carbon dioxide but above certain minimum concentrations of alkali oxalic acid is also an oxidation product. Rise in temperature causes an increase in the production of carbon dioxide and a decrease in the acetic acid. Lactic and pyruvic acids are probably two of the intermediate products the lactic acid arising either from the oxidation of lact- aldehyde or from the rearrangement of pyruvaldehyde in the presence of alkalis. The acetic acid is probably obtained either from the oxidation of acetaldehyde present as a dissociation product or from the oxidation of pyruvic acid.The oxalic acid is probably formed (a) by tbe oxidation of glycollic acid obtained h 2i. 176 ABSTRACTS OF CHEMICAL PAPERS. by the oxidation of vinyl alcohol or (b) by the oxidation of glyoxylic acid formed from pyruvic acid. Carbon dioxide may arise from the oxidation of formaldehyde pyruvic acid or glyoxylic acid. The alkali functions (a) by neutralising the acids formed ( b ) by increasing the enolisation of acetaldehyde and pyruvic acid ( c ) by causing the rearrangement of pyruvaldehyde to lactic acid. As the concentration of the alkali increases the dissociation of the three-carbon atom compounds into two other compounds is sup- pressed in that direction owing to the increased activity of the alcohol groups in propylene glycol due to the lower point of dis- sociation of the alkyloxides formed in comparison with that of the alcohol itself.W. G. The Formation of Geometrical Isomerides by the Reduc- tion of Acetylene Derivatives. JUL. SALKIND (Ber. 1923 56 [B] 187-192).-1t has been shown previously (A. 1907 i 22) that pr-dihydroxy-Pr-dimethyl-A?-hexinene OH*C&*CiC*CMe,*OH smoothly adds two atomic proportions of hydrogen in the presence of colloidal palladium and passes thereby into pc-dihydroxy- PE- dimethyl-Au-hexene OH*CMe,-CH:CH*CMe,*OH slender needles m. p. 76.5-77" (a-form). It has now been found possible to isolate the isomeric p-form monoclinic prisms m.. p. 69-695" the relationship of which to the a-variety is established by the observ- ation that either compound is smoothly hydrogenated in the presence of spongy platinum to tetramethylbutanediol. The a- and Pforms are soluble to the extent of 0.55 and 5.14 parts in 100 parts of light petroleum (d 0.644-66) at 16".Either variety is transformed by bromine in the presence of carbon tetrachloride carbon disulphide or anhydrous ether into a mixture of the solid dibromide C,H,,O,Br long thin prisms m. p. 98-5-99" and a liquid dibromzde which could not be completely purified (the relative proportions of the solid and liquid products differ according to the isomeride used). The author has endeavoured to elucidate the configuration of the glycols by a study of their conversion into tbe y-oxide gHoCMe2>0 (a liquid b. p. 102-102~5"/755 mm. d 0.8226 CH-CMe di7'5 0.8063 ng5 1*40926) which should be obtainable solely from the maleinoid form.Under the action of boiling sulphuric acid (15%) of potassium hydrogen sulphate at 160" or of a trace of iodine the oxide is however produced in good yield from either glycol so that interconversion appears to take place under these conditions. Since however it is found that the a-isomeride loses water much more readily than the p-form when heated under similar conditions with a little iodine it is considered to be maleinoid in structure whereas the fumaroid configuration is assigned to the The relative proportion of the a- and p-glycols obtained by hydrogenation of the acetylenic compound appears t o depend on the rapidity of the action; the production of the a-variety is favoured by the rapidity of the change. p-form.H. W.ORGANIC CHEMISTRY. i. 177 The Cyclic Condensation Products of Acetone with 1 3- Diols. J. BOESEKEN [with G. SCHAEFER and P. HERMANS] (Rec. truz,. chim. 1922 41 722-723; cf. Biieseken and van Loon A. 1920 i 837; Mannich and Brose A. 1922 i 1118).-Two condensation products of erythritol with acetone were prepared. Acetone-erythritol [erythritol isopropylidene ether] has m. p. 135" and is only slightly soluble in benzene. Diacetone-erythritol [erythritol diisopropylidene diether] m. p. 116O is soluble in benzene. The solubility difference affords a means of separating the sub- stances from each other. H. J. E. A New Preparation of Monochloroacetic Acid. L. J. SIMON and G. CHAVANNE (Compt. rend. 1923 176 309-311).-Mono- chloroacetic acid may readily be prepared with a yield of 90% by heating trichloroethylene with 90-93 % sulphuric acid a t 160-180".The concentration of the acid and the temperature are regulated so as to give the best yield and the greatest reaction velocity. Part of the chloroacetic acid passes over with the hydrochloric acid and unchanged trichloroethylene and a certain amount remains dissolved in the sulphuric acid. The latter may be recovered by distillation under reduced pressure or by diluting the acid and extracting it with ether. Its presence dissolved in the sulphuric acid does not prevent the further use of the acid as a hydrating agent after the addition of the necessary amount of water to replace that used in the first hydration. W. G. Hydroxystearic Acid and some of its Derivatives.L. GUY RADCLIFFE and W. GIBSON (J. Soc. Dyersand Col. 1923,39 &lo).- i-Hydroxystearic acid prepared by the action of sulphuric acid on oleic acid (ibid. 1920 36 65) and purified by repeated crystal- lisation from alcohol melted sharply at 85". The acid was further characterised by the preparation of the following derivatives Methyl hydroxystearute small white flakes m. p. 46" ; ethyl hydroxy- stearate white flakes m. p. 48.5" ; ucetoxysteuric acid a white powder m. p. 31-32'; and ethyl benxoxysteurute a yellow oil. As an attempt to introduce the -NO group into the stearic acid molecule a-bromostearic acid was prepared by Volhard's method. It is a white substance m. p. 58" and gives with silver nitrate in alcoholic solution a product free from nitrogen which seemed to be a mixture of a-hydroxy- and a-ethoxy-stearic acids.By the direct action of fuming nitric acid in acetic acid solution on the original i-hydroxystearic acid three substances were obtained a greenish- yellow crystalline compound m. p. 83-83.5" a yellow oil and a white solid m. p. 100-120". Only the first of these was further investigated. It was free from nitrogen and had a molecular formula approximating to C,,H,O,. No confirmation of this could however be obtained by a molecular-weight determin- ation. Titration with alcoholic potassium hydroxide in the cold and the analysis of the silver salt gave values of 291-293 but on warming with the alkali a further half molecule was neutralised suggesting a lactonic structure. Still no confirmationi.178 ABSTRACTS OF CHEMICAL PAPERS. of this waa forthcoming neither was it in accord with the number of oxygen atoms found by the combustion. ap-Dihydroxynonoic Acid. WALTER KROHS (Ber. Deut . pharm. Ces. 1922 32 336-338; cf. Thoms and Deckert A. 1921 i 219 ; Reinger A. 1922 i 623).-aB-DiFYydroxynonoic acid CH,Me*[CH,],*CH( OH)*CH(OH)*CO,H mas obtained by the action of 2 % potassium permanganate on the corresponding nonenoic acid (Harding and Weizmann T. 1910,97 299) and has m. p. 123" (sinters at 119"). Dehydrating agents such as 60% sulphuric acid do not convert it into an unsaturated substance and with 60% sulphuric acid and 40% acetic acid a monoacetyl compound is formed. It is considered that the stability of the hydroxyl group to dehydrating agents is due to the proximity of the carboxyl group.The acid was resolved into its optical antipodes by means of cinchonine. The Lucid has [a]: -17.44"; the dextro-acid was not obtained quite pure. On further oxidation the acid easily decomposes but a well characterised dinitrate and ap-diketononoic aczd CH2Me*[CH,]4*CO*CO*C0,H were ob- tained. The latter has m. p. 95-96" and its dihydrazone ant1 disemimrbaxide m. p. 160" were prepared. G. 3'. M. CH,Me*[CH?],*CH( O*NO,)*CH( O*NO,)*CO,H P. M. Crystalline Structure and Properties of Tartaric Acid. W. T. ASTBURY (Proc. Roy. Xoc. 1923 [A] 102 506-52S).-By X-ray analysis employing a Coolidge bulb with molybdenum anticathode the unit cell in the crystal structure of active tartaric acid has been shown to be monoclinic to contain two molecules and to have the following dimensions a = 7.693 8.b=6*037 A. and c=6-195 A. Molecules at the corners of the cell point in one direction whilst those lying along the central line of the cell parallel to the a axis point in a diametrically opposite direction. Intensity measurements of the reflections from various planes in the crystal enable the manner in which the unit cell is incorporated in the crystal structure to be ascertained and hence the structure itself to be determined. This shows only one plane of perfect cleavage viz. the plane about which lie the junctions of the hydroxyl groups i.e. the plane (100). The junctions in the =OH- linkings are of a different type from the junctions between the hydrogens of the hydroxyl groups.In the main the ascer- tained crystal structure is in accordance with known chemical and physical facts. The theory of stereoisomerism of Le Be1 and van't Hoff is in its essentials confirmed and the link between crystallographic enantiomorphs and the chemical stereoisomerides revealed. The rotatory properties of the acid are discussed with reference to the symmetry of the crystal and the spiral arrange- ment within the molecule and it is shown that the assumption by Lowry of the existence of dynamic isomerides within the structure to explain these properties is unnecessary the crystal structure itself affording a simple explanation of all the facfs. Thus the fundamental crystal cell is constructed of molecules exhibitingORGANIC CHEMISTRY. i. 179 two spiral arrangements one associated with the four carbon atoms forming the nucleus of each molecule and one o positely directed associated with the four hydroxyl groups.f n these spiral formations are located the two opposing rotatory systems adequate to explain the anomalous rotatory properties of the acid and some of its derivatives. Most probably the dexfro- rotatory property of ordinary tartaric acid is associated with the carbon nucleus of the molecule. It is shown fo be impossible by the diffraction of X-rays to discriminate between the dextro- and laevo-forms of an optically active substance. J. S. G. T. Some Complex Organic Compounds of Bismuth. E. MOLES and R. PORTILLO (Anal. F k . Quim. 1922 20 571-576).-Pre- liminary data are given on the preparation and properties of bismuthotartaric acid bismutholactic acid and bismuthocitric acid.G. W. R. A Synthesis of Derivatives of Muconic Acid. ERICH BENARY and RUDOLF SCRMKOPF (Ber. 1923,56 [B] 35&362).- The synthesis depends on the action of afklichloroethyl ether CH2C1.CHC1.0Et on ethyl sodiomalonate. ap-Dichloroethyl ether is added gradually to a suspension of ethyl sodiomalonate in boiling ether; after removal of a fraction containing chloroacetaldehyde chloroacetal unchanged dichloro- ethyl ether and malonic ester ethyl Aa-butene-aa68-tetramrboxylute C( CO,Et),:CH*CH,*CH( CO,Et) is isolated as a colourless viscous liquid b. p. 223-225"/13 mm. (some decomp.). It is reduced by zinc dust and boiling glacial acetic acid to ethyl butane-aa88- tetracarboxylate (cf.Perkin T. 1894 65 579). It is converted by cold saturated alcoholic ammonia at the atmospheric temperature into the corresponding triamide C1,H,,O,N small needles m. p. 230" (decomp.) and by concentrated aqueous ammonia into the tetra-amide CgHl2O4N4 small colourless needles m. p. 257' (decomp.) after incipient change at 238". Hydrolysis of the ester with alcoholic potassium hydroxide solution and subsequent addition of lead acetate leads to the production of the salt C1,H,,O,,Pb which seems to be derived from a tribasic acid; the ,?utter is an amorphous brittle colourless mass. The unsaturated ester is converted by bromine in the presence of chloroform in ethyl ap6-tribrmno~tane-aa88-tetracarboxylte CBr ( CO,Et),-CHBr*CH,*CBr( C0,Et ) hexagonal pyramids m. p. 61-63' which when distilled under diminished pressure or warmed with pyridine passes into ethyl AaY-~tadiene-aa66-tetracarboxylute C( CO,Et),:CH*CH:C( CO,Et) colourless matted needles m.p. 56-57'. The latter Substance is reduced by zinc dust and glacial acetic acid to ethyl butane- a&%-tetracarboxylate. The ester is converted by fuming hydro- chloric acid into a mixture of py-diethoq-n-butane- aa8S-tetra- curboxylic acid colourless needles m. p. 132' which evolve carbon dioxide at about 140" and py-diet~oxy-n-~tane-a6-dicarboxyZic acid crystalline scales m. p. 19-5" b. p. 149'113 mm. The latteri. 180 ABSTRACTS OF CHEMICAL PAPERS. acid is converted by bromine in the presence of chloroform into a6-dibromo-py-di( uf p'-dibromoethoxy)adi~ic acid CO,H*CHBr.CH( O*CHBr*CH,Br)*CH( O*CHBr-CH,Br)mCHBr*CO,H small colourless needles m.p. 77-78". The condensation of an excess of up-dichloroethyl ether with an ethereal suspension of ethyl sodiomalonate a t a low temperature leads to the production of elhyE p-chZoro-ol-ethoxyet~,yZmaZonats CH,CI*CH( OEt)*CH(CO,Et) a colourless mobile liquid b. p. 149- 152"/13 mm. H. W. Selective Hydrogenation. THOMAS PERCY HILDITCH and CHARLES WATSON MOORE (J. h'oc. Chem. Ind. 1923,42 1.5--17~).- Conclusive proof of the preferential saturation of one or more double bonds in the catalytic hydrogenation of compounds con- taining several unsaturated linkings is furnished by a study of the hydrogenation of a number of natural oils and of the esters prepared from their fatty acids. Samples were withdrawn a t intervals corresponding with a drop of 10-20 in the iodine value and the proportion of saturated and unsaturated fatty acids and of oleic to linoleic acid was calculated from the iodine values obtained.It was found that the amount of saturated derivatives present did not increase until the amount of linoleic derivatives had fallen to lo% or even less of the mixture. It is clear there- fore that linolein and linolenin are almost completely hydrogenated to olein before the unsaturated centre in olein is affected. In the case of the free acids the strong attraction between the free carboxyl group and the metal dwarfs to some extent the relative activities of the different unsaturated systems. K. H. BAUER (Chem. Umschuu 1923 30 9-11; cf. A. 1922 i 983).-The unsaturated acids obtained by debromin- ating the bromides soluble in a mixture of ether and glacial acetic acid were oxidised by Hazura's method with alkaline permanganate.The resulting mixture of hydroxy-acids was extracted successively with light petroleum ether and water. The light petroleum extract was a viscid yellow oil which slowly deposited a crystalline mass and was similar to the corresponding extract of the oxidation products of the total fatty acids from perilla oil. The crystalline deposit consisted of palmitic acid and was due to the imperfect separation of saturated and unsaturated acids given by the lead salt-benzene method. The ethereal extract consisted of a white crystalline mass of dihydroxystearic acid m. p. 131" and com- prised 5.7 yo of the debrominated acids originally oxidised. Glycer- ides of oleic acid are therefore present in perilla oil.The aqueous extract comprised only 1.5% of the original acids oxidised and its nature was not determined. Very small quantities of linusic and isolinusic acids were isolated from the insoluble residue. It appears from this that the linolenic acid from perilla oil gives the same hexabromostearic acid as that from linseed oil but on oxidation of the former with alkaline permanganate in addition to linusic and isolinusic acids an isomeric hexahydroxystearic acid is obtained which is not obtained from the linolenic acid from linseed oil. G. F. M. Perilla Oil.ORGANIC CHEMISTRY. i. 181 The linolenic acid obtained by the debromination of hexabromo- stearic acid is however different from that originally brominated and only yields 14% of its weight of insoluble bromides.It there- fore appears that conclusions as to the presence or absence of isomeric linolenic acids cannot be based only on the behaviour on bromination. H. C. R. The Equilibrium between Formaldehyde and Amino- acids in Aqueous Solution. -JULIUS SVEHLA (Ber. 1923 56 [B] 331-337) .-The reaction between amino-acids and formalde- hyde in dilute aqueous solution has been examined and the corre- sponding equilibrium constants are calculated in accordance with the equation C a d x Cacid/CAl&acid=K. The following values are observed glycine 1.73 ; alanine 14.1 ; valine 28.9 ; leucine 36.8 ; aspartic acid 25.7 ; glutamic acid 30.7. Leucylglycine appears to react with two molecular proportions of formaldehyde in dilute aqueous solution.In the cases of the simpler amino-acids the measurements are effected by determining the freezing points of solutions of the acid and formaldehyde singly and when mixed. With the more complex acids the results are deduced from determinations of their solubility in pure water and in formaldehyde solutions of various concentrations at 25". Action of Aldehydes on Mixtures of Sulphites and Hydrogen Sulphites. J. ESTALELLA (Anal. F k . Quim. 1922,20,43741).- When formaldehyde is added to a solution containing potassium sulphite and potassium hydrogen sulphite the following reactions take place successively (1) H*CHO+KHSO3=OH*CH,-SO3K and (2) HCHO +K2S03+ H20 = OH*CH2*S03K+KOH. The gradual liberation of potassium hydroxide is demonstrated by the reddening of added phenolphthalein.A similar reaction is given by a solution of potassium sulphite alone in the presence of carbon dioxide but the red colour with phenolphthalein is then non-persistent. It is suggested that the presence of carbon dioxide in the distillate may interfere with the estimation of volatile acid in wines. H. W. G. W. R. Density and the Refractive Index of Mixtures of Acet- aldehyde and Water or Ethyl Alcohol. E. VAN AUBEL (Bull. A d . roy. Belg. 1921 160-162).-Mainly a question of priority. Attention is also directed to some values for the coefficient of thermal expansion of certain mixtures of acetaldehyde and water. E. E. T. Syntheses by Means of Mixed Organo-zinc Derivatives Propylglyoxal.E. E. BLAISE (Cmpt. rend. 1922 175 1216- 1218).-The action of oxalyl chloride on a-hydroxyisobutyric acid yields oxalylbisoxyisobutyric acid. The dichloride of this acid on treatment with zinc propyl iodide forms a mixture of the biscycloacetaloxyisobutyrates of dibutyryl and of propylglyoxal. Alcoholysis of the mixture leaves the former substance unchanged and decomposes the latter into ethyl hydroxyisobutyrate and the h*i. 182 ABSTRACTS OF CHEMICAL PAPERS. acetal of propylglyoxal. The action of methyl alcohol on the mixture of acetals yields the dimethylacetul of propylglyoxal C3H,*CO*CH(OMe),. This is a mobile colourless liquid b. p. 65- 66"/l4 mm. which forms a disemicurbazone crystallising from acetic acid with one molecule of the solvent m.p. above 250° and a osazone yellow needles m. p. 105". On boiling with 3% sulphuric acid hydrolysis takes place with liberation of propyl- glyoxal a yellowish-green liquid b. p. 36"/16 mm.; the vapour is of the same colour as the liquid. On being kept in a sealed tube it becomes viscous and of paler colour; in air it is rapidly oxidised. It has a powerful reducing action and rapidly restores the colour of SchifE's reagent. H. J. E. The Nomenclature of Steric Series. A. WOHL and K. FREUDENBERG (Ber. 1923 56 [B] 309-313).-In two almost simultaneous communications (Wohl A. 1922 i 626 ; Freuden- berg A. 1922 i 623) systems of nomenclature of steric series have been proposed which difTer from one another in certain details ; in order to avoid confusion the following system is advocated.The direction of the rotation of a compound is indicated by prefixing the sign + or - to the name thus (+)-glucose or (+)- tartaric acid. This is the only possible system in the case of many substances such as tannins and alkaloids which cannot at present be brought into line with the stereochemical structure of the sugars. It is however open to the objection that it is not distinctive h cases in which the sign of rotation varies with the concentration (malic acid) or in which inversion occurs when the acid is converted into its salt (e.g. glyceric acid). The genetic relationship to glyceraldehyde is adopted as the determining factor in the nomenclature of hydroxy-acids and sugars. The d-form of the aldehyde is written as shown in the annexed YHO H.(?oH oH*CH2*yeCHo formula? I and 11.All compounds CH,*OH OH containing one asymmetric carbon (1.) (11.1 atom which are genetically related to glyceraldehyde and in which the hydroxyl group is to the right of or below the asymmetric carbon atom belong to the d-series. In the cases of compounds with several carbon atoms each of the latter is indicated in the same manner; the system is dis- tinctive for the sugars themselves and their unsymmetrical deriv- atives. If the carbonyl group is written at the top of or to the right of the formula the position of the steric model is established and also the configurative formula. The order of the single carbon atoms is from below to above or from left to right because this sequence corresponds with the relation of the sugars to glycer- aldehyde ; (+)-glucose is thus designated ddld.[This necessitates an inversion of Fischer's symbols in the cases of gulose idose xylose and threose as proposed previously by Rosanoff (A. 1906 ii 320).] The mode of formulating symmetrical derivatives of the sugars according to this system is somewhat indefinite. Thua sacchario PORGANIC CKEMISTRY. i. 183 acid is lettered ddld if regarded ~ E I derived from glucose and ZdZZ if considered as formed from gulose. In such cases it is recommended that the relationship to the more important sugar should be expressed or as this is arbitrary that merely the sign of rotation should be given (+)-saccharic acid. Optical Rotatory Power of Sugars in Hydrochloric Acid. Lisa6 ZECHMEISTER (2. physikal.Chem. 1922 103 316-336).- The optical rotation and its change with time has been determined at 0" and 10" in concentrated hydrochloric acid (40.6%) solutions for various concentrations of the following sugars dextrose galactose mannose arabinose xylose rhamnose and laemdose. The results show that aldo-hexoses and aldo-pentoses in cold fuming hydrochloric acid solution undergo a measurable reversible change which is evidenced by a large increase of the specific rotation to *a constant end-value. The position of the end-value is determined by the concentration of the hydrochloric acid and in highly concentrated acid exceeds the value of [.ID for the or-form of the sugar in water solution. In the .case of dextrose in 46.7% hydrochloric acid the value of [a]:z is +203".Lamdose shows a somewhat irregular behaviour. Possibilities for the explanation of this phenomenon are considered. The Biochemical Synthesis o an a-&Mannoside Starting from Manna. H. H~RISSEY (Compt. rend. 1922 175 1110- 1112; cf. A. 1921 i 628).-The action of dried and powdered lucerne seeds [as a source of a-d-mannosidase] on manna in presence of methyl alcohol results in the formation of a-methyl-d-mannoside. The manna was not present in pure condition but as carob seed (Ceratonicc siliqua) which contains a considerable amount of the carbohydrate. The author suggests that in such a reaction the sugar may have a t the moment of formation a different structure from that which it possesses in the crystalline form and indicates the possibility of preparing glucosides directly from starch by a suitable choice of enzymes.The Constitution of the Disaccharides. VII. Sucrose. WALTER NORMAN HAWOETH and WILFRED HERBERT LINNELL (T. 1923 123 294-301). The Constitution of the Disaccharides. VIII. Sucrose. WALTER NORMAN HAWORTH and JAMES GIBB ETCHELL (T. 1923 Pentosans. 111. Purity of Xylan from Straw Cellulose. Eim~ HEUSER and RIIBRIA BRADEN (J. pr. Chem. 1922 [ii] 104 259-264).-It is shown that the lignin content of crude xylan even if it contains methylxylan may be estimated by Zeisel's method but the method is a rough one only since it depends on a knowledge of the methoxyl content of lignin in the isolation of which loss of methoxyl occurs (cf. Heuser and Wenzel A. 1921 ii 715). A sample of xylan prepared by the modified method of Salkowski (cf.A. 1903 i 206) is in this way shown not to contain H. W. J. F. S. H. J. E. 123 301-310). h* 2i. 184 ABSTRACTS OF CHEMICAL PAPERS. lignin; the absence of methyl pentosan is demonstrated by the method of Tollens and Ellet (A. 1905 ii 210). By a modification of Schulze’s process (2. physiol. Chem. 1892 16 403) xylan is prepared from bleached straw cellulose in 19% yield containing 93.8% of pure xylan and 0.94% of ash. Precipit- ation of xylan by calcium chloride solution from a nearly neutralised alkaline solution and further purification by dialysis gives a product containing 12.2% of ash corresponding with a yield of 22% of mh-free xylan. Further purification by solution in sodium hydr- oxide solution and reprecipitation with acid reduces the ash content to 0-6% but the yield is then only 15%.These results compare unfavourably with those obtained by the more expensive Salkowski method. W. S. N. Pentosans. IV. Hydrolysis of Xylan by Dilute Acids. E m HEUSER and LUDWIG BRUNNER ( J . p. Chem. 1922 [ii] 104 264-281).-It is shown that when xylan is hydrolysed by means of hot hydrochloric acid solution (5% or 12%) or by hot dilute sulphuric acid (12y0) the xylose produced is partly converted into humin-like substances before the parallel conversion into furfuraldehyde commences ; if however the hydrolysis is continued the formation of furfuraldehyde is mainly accountable for the loss of xylose. The course of the hydrolysis is followed by a method already described (Heuser and Kurschner A.1922 i 113). W. S. N. Acetyl Derivatives of Xylan EMU HEUSER and PAUL SCEILOSSER (Ber. 1923 56 [B] 392-395).-The presence of two free hydroxyl groups in xylan established previously by the pro- duction of a dimethyl derivative (Heuser and Ruppel A. 1922 i 810) is confirmed by the isolation of a diacetate. The treatment of xylan with boiling acetic anhydride or with acetyl chloride a t the atmospheric temperature does not yield a completely acetylated product since the acetates are to some extent hydrolysed by the acetic or hydrochloric acid produced simultaneously. This action can be limited by the addition of pyridine and under these conditions the diacetate a colourless powder is obtained in 90% yield. Unlike cellulose therefore xylan may be acetylated in the absence of a catalyst but the experimental conditions can be made less drastic if such an agent is present.The most suitable substance for this purpose is con- centrated nitric acid ; sulphuric acid is objectionable on account of its tendency to yield charred products. Dry powdered xylan reacts with difficulty but can be brought into a more suitable condition by allowing it to swell in water and removing the latter by treating the product successively with acetic acid and acetic anhydride. H. W. Cellulose Chemistry. 11. The Action of Dry Hydrogen Bromide on Carbohydrates and Polysaccharides. HAROLD HIBBERT and HAROLD S. HILL ( J . Amer. Chem. Soc. 1923 45 176-182; cf. J . Ind. Eng. Chem. 1921 13 256 334).-The authors have repeated the work of Fenton and Gostling (T.1898,ORGANIC CHEMISTRY. i. 185 73 554; 1899 75 423; 1901 79 361 ; 1909 95 1334) on the action of dry hydrogen bromide on carbohydrates and polysac- charides. Contrary to the results of these workers a yield of 12 yo of w-bromomethylfurfuraldehyde was obtained from pure dextrose from a-methylglucoside the yield was 15y0 and from cellobiose 27%. In one case from a dry cotton cellulose a 56% yield was obtained. The formation of o-bromomethylfurfuralde- hyde under these conditions is not therefore alone characteristic of ketoses and ketose derivatives but also takes place with aldoses and related compounds. Its formation from cellulose is thus no criterion as to the presence of ketone groupings in this product (cf. Cross and Bevan " Cellulose," 1918). Chemical Decomposition of Cellulose by Oxidation under Pressure.FRANZ FISCHER HANS SCHRADER and WILHELM TREIBS (Ges. Abh. Kennt. Kohle 1921 5 211-220; from Chem. Zentr. 1922 iii 1185).-By oxidation of cellulose in sodium carbon- ate solution under pressure a t 200° 42% of the material used is obtained as acids. Of these about 11% consists of oxalic acid and more than 50% of acetic acid. About 25% (9% of the original cellulose) consists of non-volatile acids extractable with ether these include fumaric acid and succinic acid. Small amounts of formaldehyde are also obtained. On heating cellulose under pressure both hydrolysis and oxidation take place. Sugars may be formed which undergo oxidation. G. W. R. [Effect of] Heating under Pressure of Alkaline Solutions obtained from the Oxidation under Pressure of Cellulose and Lignin.FRANZ FISCHER HANS SCHRADER and WILHELM TREIBS (Ges. Abh. Kennt. Kohle 1921 5 311-318; from Chem. Zentr. 1922 iii 1186).-By heating the solution of sodium salts obtained by heating 100 g. of dry cellulose a t 200" in the presence of sodium carbonate solution at 400" under pressure the following were obtained gases 6.5 litres; oils 1-5 g.; tarry substances 2.7 g. ; volatile acids (acetic and formic acids) 0-28 equivalent; other acids 1.2 g. (0-014 equivalent). Similarly treated 100 g. of lignin gave gases 3.4 litres; oil 1.6 g. ; volatile acids 0.17 equivalent (including benzoic acid 0.7 g.); humic acids 2.0 g.; isophthalic acid 1.8 g.; acids extractable by ether 1.1 g. W. G. G. W. R. [Effect of] Heating Cellulose and Lignin under Pressure in the Presence of Water and Aqueous Alkalis.FRANZ FISCHER and HANS SCHRADER (Ges. Abh. Kennt. Kohle 1921 5 332-359; from Chem. Zentr. 1922 iii 1184-1 185).-Cellulose is increasingly decomposed with rising temperature when heated under pressure in the presence of water giving compounds including acids soluble in water and gaseous products principally carbon dioxide and some hydrogen ; comparatively little solid residue remains. Decomposition takes place slowly at 200" but more completely a t 300". Lignin also gives carbon dioxide but the principal product is black carbonaceous material. Sulphite liquors heated at 300",i. 186 ABSTRACTS OF CREMICAL PAPERS. give insoluble substances which are precipitated as a black powder.Probably association to larger molecules takes place. Cellulose in the presence of alkalis is more resistant than lignin when heated under pressure a t 200". At 300" strong decomposition takes place with evolution of carbon dioxide and formation of small amounts of an oil of powerful odour together with formic acid acetic acid and other decomposition products. Lignin heated under pressure with aqueous alkalis goes completely into solution at 200" with formation of humic substances. On heating the dark brown solution at 300° the humic acids associate and separate as dark brown or black masses. Wood peat bituminous coal and anthra- cite heated under pressure with potassium hydroxide solution behave according to their composition. D. COSTA (Gazxetta 1922 52 ii 362-365).-0n the basis of Green's formula for cellulose the latter in virtue of its three hydroxyl groups might be expected to react with three molecules of magnesium ethyl bromide OH*YH-YH*OH BrMg*O*yH--$!H*O*MgBr CH,*O*CH*OH CH,*O*CH*O*MgBr The author finds that at a temperature not exceeding 35" an ethereal solution of magnesium ethyl bromide acts on cellulose yielding ethane and a greenish-grey compound which shows the fibrous structure of the original cellulose and has the composition of a magnesium cellulosyl bromide C,Hg0,*MgBr,Et20.This com- pound reacts with avidity with water giving cellulose and mag- nesium bromohydroxide. It was not found possible to introduce more than the one bromomagnesium residue into the cellulose molecule. T. H. P. [Cellulose Copper Compounds.] WILHELM TRAUBE (Ber.1923 56 {B] 268-274) .-Hess and Messmer's conception (A. 1921 i 401; 1922 i 988) of the constitution of the compounds formed by the solution of cellulose in copper oxide-ammine solutions is identical in its essential features with that previously put forward by Traube (A. 1922 i 115 718). I n the author's opinion the electrolytic observations of Hess and Mesmer (Zoc. cit.) do not justify the conclusions which they have based on them and an alternative interpretation of the results is given. Physico-chemical Studies of Cellulose Nitrates in Organic Media. I and 11. I. NEWTON KUGELMASS (Rec. trav. chim. 1922 41 751-754 755-763).-A study of the physical properties of solutions of cellulose nitrate (nitrogen content 11.9%) in ether and in alcohol prepared a€ a low temperature. Estimation of the nitrogen content of the solute in each case (11.20% and 14.02% respectively) showed that the ethereal solution apparently con- tains cellulose dinitrate whilst the constituent soluble in alcohol is the trinitrate. The viscosity of the ethereal solution com- pared with that of the pure solvent is greater at temperatures G.W. R. Magnesyl Derivative of Cellulose. YH*O-YH +3MgEtBr=3C2H,+ YH*O-YH H. W.ORGANIC CHEMISTRY. i. 187 below -20" but identical above this point the maximum difference observed being in the neighbourhood of -90". Other properties of the ethereal solution are similar to those of aqueous solutions of colloids. H. J. E. Constitution of Pine Lignin. III. PETER KLASON (Ber.1923 56 [B] 300-308; cf. A. 1920 i 822; 1922 i 324).-The preparation of p-lignosulphonic acid and of its 8-nuphthylamine and calcium salts is described. New analyses lead to the formula C ,H[,,O for p-lignin in place of C,,H1,O proposed previously (A. 1920 i 822). The calcium salt is converted by molten potassium hydroxide into protocatechuic acid. or-Lignin is regarded as formed by the condensation of two molecules of coniferyl aldehyde in such a manner that two hydrogen atoms have undergone change in position and the annexed formula is assigned to it EH*CH==y*CH,-yH*CH( OH)*g*CH== S*CH:CH*CHO In this formula the skeletons of guaiacol pyrocatechol m- and p-cresols and methyl- ethyl- and n-propyl-cresols are present and all these substances are present in pine tar.The formation of methyl alcohol ally1 alcohol and 2-methylfuran is also explained. Attempts are described to effect the synthesis of coniferyl aldehyde by the condensation of vanillin with acetaldehyde in dilute aqueous solution in the presence of sodium hydroxide. In place of the desired compound however its dimeric form is obtained which in virtue of the aldehyde group can react with one mole- cular proportion of sulphite but is distinguished from acraldehyde- lignin by its inability to combine with a second molecular pro- portion of sulphite as a consequence of the presence of the double bond. or-lignin however after very mild treatment with calcium hydroxide loses the ability to become converted into a-ligno- sulphonic acid. It is considered that the synthetic dimeric coni- feryl alcohol is identical with hemi-a-lignin. Further attempts to prepare coniferyl aldehyde by the regulated oxidation of coniferin did not lead to the desired result the dimerio form being again obtained.A condensation product C,,,H,,O,N from vanillin and P-naphthyl- amine is incidentally described. Chemical Decomposition of Lignin by Oxidation under Pressure. FRANZ PISCHER HANS SCHRADER and WILHELM TREIBS (Ca. Abh. Kennt. Kohle 1921 5 221-229; from Chem. Zentr. 1922 iii 1185).-Lignin prepared by treatment of wood with concentrated hydrochloric acid (Willstafter and Zechmeister) contains 60.6% of carbon 4.5% of h drogen 12.6% of water and 3-3?/ of ash. When shaken with S&V-sodium carbonate tmlution in the presence of air a t 200° a dark coloured solution is obfained 44% of the lignin remaining undissolved a total of 0-101 equivalent of acid being obtained of which 0.0185 is volatile in steam.Carbon OH*C*C( 0Me):CH 0- -CC( 0Me):CH H. W.i. 188 ABSTRACTS OF CHEMICAL PAPERS. dioxide equivalent to 8.4% carbon 0*600/ of a neutral oil 9.6% of humic acids and 4.2:/ of ether-soluble non-volatile acids are also obhined. By oxidation for forty hours 0.55 equivalent of acids (including 0-18 equivalent volatile in steam and 0.16.equivalent of oxalic acid) lS.9y0 of non-volatile acids (by extraction with ether) 0031% of mellitic acid and 4.2% of water soluble calcium salts were formed. [Effect of] Oxidation and Heating under Pressure of Humic Substances from Sucrose. FRANZ FISCHER HANS SCHRADER and WLI;~IELM TREI~S (Ges.Abh. Kennt. Kohle 1921 5 230-234; from Chem. Zentr. 1922 iii 1186).-Humic substances obtained by the method of Conrad and Guthzeit were submitted to oxidation under pressure at 200" for eight and three-quarter hours. 2.2 Equivalents of acid were thus formed the solution obtained was clear and reddish-brown. After acidifying 0.27 equivalent of volatile acid (acetic acid) was obtained by steam distillation. The residue by extraction with ether yielded a comparatively small amount of a viscid oil. After evaporation to dryness the residue was heated with water a t 400" for three hours. The gases formed included carbon dioxide and the vapour of a substance most probably furan. The solid products were light coloured and slightly tarry. By steam distillation an oil of basic odour was obtained.The volatile acids included the lower fatty acids and benzoic acid. isoPhthalic acid and terephthalic acid were also obtained . G. W. R. Thermal Decomposition of Tetramethylammonium Fluoride. F. G O N Z ~ E Z NIEEZ (Anal. Pis. Quim. 1922 20 539-549).-Tetramethylammonium fluoride is obtained in 89% yield by exact neutralisation of the hydroxide with hydrofluoric acid. When decomposed by heating in the presence of water catalysed by metals (silver platinum or copper) the products are nitrous oxide methyl fluoride trimethylamine and methane. G. W. R. G. W. R. Mercuric Compounds with Hexamethylenetetramine. R. DOURIS and G. BEYTOUT (Compt. rend. 1923 176 107-log).- When mercuric sulphate is dissolved in water to which is added drop by drop just sufficient sulphuric acid to prevent the formation of the basic sulphate and the solution is added to an equimolecular solution of hexamethylenetetramine the double mercuric hexamethyl- enetetramine sulphate C,H,,N,,SO,Hg,H,O m.p. 177" (decornp.) is obtained. The double cyanide decomposing at 216" and the double acetate decomposing at 120" are similarly prepared. In these salts the corrosive action of the ordinary mercuric salt is considerably diminished and the therapeutic action increased. W G. Hexamethylaminetetramine-betaine. 3'. BOEDECKER and J. S ~ P (Ber. Deut. phurm. Om. 1922,32 339-344).-The reaction between hexamethylenetetramine and chloroacetic acid is so violent tihat profound decomposition ensues. The hydrochloride of theORGANIC CHEMISTRY. i.189 betaine is formed in good yield however when these substances react in chloroform solution. The well-characterised compounds of hexamethylenetetramhe-betaine with metallic halides are obtained in good yield by the action of hexamethylenetetramine on aqueous solutions of salts of chloroacetic acid. The hydrochloride of hem- methyZenetetrumine-betuine C6H12N4C1*CH2*C02H obtained as indi- cated above in chloroform solution forms large crystals which by treatment with moist silver oxide give the hydrated form of hexa- methyZenetetrumine-betuine OH*C6H,2N4*CH,*C02H lustrous plates easily soluble in water with neutral reaction and slightly sweet taste. By the action of hexamethylenetetramine on aqueous sodium chloroacetate the sodium salt C6H~2N4C1*CH,*C0,Na,H20 was obtained.Addition of aqueous cadmium chloride to its aqueous solution causes the double salt (C,Kl,N,C1*CH2*C0,),Cd,CdC~,4H20 to crystallise This on treatment mth hydrochloric acid gives the acid cadmium salt C,H,2N4C1*CH2*C02H,CdCl,,H,0. By the action of zinc chloride and mercuric chloride respectively on the solution of the sodium salt double salts C6Hl,N4C1*CH,*C02Na,ZnC1,,H,0 and (C6H,2N4C10CMeoC0,)2Hg,HgC12 were obtained. The Chlorination of Esters of Amino-acids. WILHELM TRAUBE and HEINRICH GOCKEL (Ber. 1923 56 [B] 38&391).- Ethylurethane can be smoothly converted by chlorine or hypo- chlorous acid in aqueous solution into N-chloroethylurethane NHCl*CO,Et. Under similar conditions the conversion of the esters of amino-acids into the corresponding monochlorinated derivatives does not appear to be possible the dichloro-compounds being almost invariably produced.Ethylurethane dissolved in water is converted by gaseous chlorine at the atmospheric temperature into N-chloroethylurethane b. p. 101- 102"/30 mm. the yield being 80% of that theoretically possible. It solidifies at 0". The potassium salt C3H,02NClK,2H,0 lustrous prisms which explode at 300" the hygroscopic sodium salt and the silver salt a colourless powder are described. N-ChZoro-N- methyZethyZurethune NMeCl*CO,Et a colourless liquid b. p. 57"/30 mm. is prepared by the chlorination of N-methylethylurethane or by the action of methyl sulphate and potassium hydroxide on chloroethylurethane. The latter is transformed by potassium hydroxide and benzoyl chloride into N-chZoro-N-benxoyZethyZzlrethane a pale yellow liquid which was not prepared in the homogeneous condition; its formation is established by the reduction of the product of the reaction to N-benzoylethylurethane m.p. 110". The action of ethyl chloroformate on chloroethylurethane in aqueous alkaline solution leads to the production of a mixture of N-dichloroethylurethane b. p. 73"/20 mm. and ethyl imino- dicarboxylate m. p. 50" ; the primarily formed ethyl chloroimino- dicarboxylate appears to react with a portion of the chloroethyl- urethane liberated by hydrolysis of the potassium salt in accord- ance with the scheme NC1(C02Et),+Cl*NH~C02Et -+ NH(CO,Et) +NCl,*CO,Et. The action of chlorine on an aqueous solution of ethyl amino- P.M.i. 190 ABSTRACTS OF CHEMICAL PAPERS. acetate leads to the formation of ethyl dichloroaminoacetate NCb*CH,*CO,Et a yellow liquid. Ethgl dibrmoarninoacetate is prepared from ethyl aminoacetate and sodium hypobromite; both dihalogenated compounds are unstable. Ethyl tx-dichloroamino- prophzate NC1,*CHMe*C02Et is an extremely unstable pale Synthesis of 7-Amino-p-hydroxybutyric Acid. MASAJI TOMITA (2. phy8iol. Chem. 1923 124 253-258).-y-Phthulimido- p-hydroxybutyronitrile m. p. 132" is prepared by the action of potassium cyanide on a-chloro-y-phthalimido-p-hydroxypropane. When hydrolysed with concentrated sulphuric acid a t water-bath temperature it yields y-amino-p-hydroxybutyric acid m. p. 214" which gives a marked biuret reaction and forms a crystalline copper salt.When heated just above its melting point it loses water to form 4-hydroxy-2-lryrroZidone m. p. 118" and on ex- haustive methylation the betaine is formed isolated as its chloro- aurate C,H,,O,N,HAuCl citron-yellow needles m. p. 180-182". It has been suggested that carnitine may be the betaine of 7-amino- p-hydroxybutyric acid but carnitine chloroaurate melts about 30" lower than that of the betaine described above. There remains yellow liquid. H. w. however the possibility that carnitine may be the optically active form. W. 0. K. A Polymeride of Hydrocyanic Acid. CH. BEDEL (Compt. rend. 1923 176 168-171).-When azulmin resulting from the polymerisation of hydrocyanic acid is extracted with ether a yellowish-brown crystalline substance is obtained.If this material is crystallised from aqueous solution after decolorising it with animal charcoal and the resulting mother-liquors are concentrated in the presence of charcoal a colourless crystalline substance is obtained. It ihas m. p. 179" (decomp.) and molecular-weight determinations show it to be a tetrameride of hydrogen cyanide. When decomposed by dilute mineral acids it gives for each mole- cule one molecule of hydrogen cyanide. When decomposed by barium hydroxide i t gives glycine ammonia and a small amount of barium carbonate but principally barium oxalate. With alcoholic potassium hydroxide and chloroform it gives the odour of carbylamine. From its behaviour the author considers it to be a hydrocyanide of aminopropanedinitrile (cf. Wippermann Ber. 1874 7 767).The Nitriles of Fluoro- and Difluoro-acetic Acids. FRED SWARTS (Bull. SOC. chim. Belg. 1922 31 364-365).-These sub- stances were prepared by distillation of the corresponding amides with phosphoric oxide. Fluoroacetonitrile is a colourless liquid of penetrating odour b. p. 81-8-82" d:'1.0730. It is slightly soluble in water and reacts rapidly with potassium hydroxide. DifluorDacetonitrile b. p. 22.8-23.4" is a colourless mobile liquid di4 1.1130 very sparingly soluble in water and reacting vigorously with potassium hydroxide. A specimen kept for several years did not undergo polymerisation. W. G. H. J. E.ORCA,WC CHEMISTRY. i. 191 The Action of Organomagnesium Compounds on Nitriles. n-Butyronitrile. FRANTZ BAERTS (Bull. SOC. chim. Belg. 1922 31 421-426).-The results obtained with n-butyronitrile are exactly parallel to those previously obtained by the author with propionitrile (A.1922 i 817). The chief product of n-butyro- nitrile and magnesium ethyl bromide was ethyl propyl ketone (about 40%). Diethylpropylcltrbinol was also formed together with termolecular cyanopropane (PrCN) and a substance not previously isolated which proved to be a-butyrylbutyronitrile a liquid b. p. 216" semicarbazone m. p. 88-90'. P. M. Constitution of Ally1 Cyanide. P. BRUYLANTS (Butl. Awd. roy. Belg. 1920 479-486).-Pyridine and y-chlorobutyronitrile when heated together give allyl cyanide b. p. 114-116"/757 mm. di0 0.8318 n2,0 1041438. The product is not accompanied by the nitrile of cyclopropanecarboxylic acid which however is formed by the action of dry potassium hydroxide on the above chloro- compound whilst the latter with sodium ethoxide affords a mixture of the cyclic nitrile and 7-ethoxybutyronitrile.By the removal of the elements of water from a-hydroxybutyro- nitrile a product (b. p. 115-116"/763 mm. n 1.41692) is obtained which from its convertibility into two known dibromo-amides is thought to be a mixture of crotononitrile and isocrotononitrile. Potassium cyanide and allyl bromide interact to give the same mixture. E. E. T. Prussian Blue and Turnbull's Blue. V. ERICH MULLER The insoluble Prussian blue precipitated by adding potassium ferrocyanide solution to ferric chloride solution in the proportion non-ionisable iron ionisable iron=0-75 consists of ferric ferro- cyanide which is converted by further addition of potassium ferrocyanide.into potassium ferric ferrocyanide. Equimolecular proportions of potassium ferrocyanide and ferric chloride do not however give pure potassium ferric ferrocyanide because the reaction PeY[Fe1'( CN)6]~+K,Fe1T(CN)6 4KFe111[Fe11(CN)s]1V is reversible and the further change KFe1'1[Fe"(CN)G]1V+K4Fe11(CN)6 =K,Fe111(CN)6+K2Fe11[Fen(CN)6]'V occurs so that the main pro- duct KFe1I1[FeI1(CN),IIV contains traces of potassium ferrous ferrocyanide and ferric ferrocyanide in solid solution. The in- soluble Turnbull's blue formed by adding potassium ferricyanide to ferrous chloride solution in the proportion non-ionisable iron ionisable iron=0.75 is KFe11Fe~.1[Fer1(CN)6]~ which with further amounts of potassium ferricyanide passes into potassium ferric f errocyanide KFe11Feg1[Fe11(CN)6]r + K3[Fe111((;(N)6]1"= 4KFe1n[Fe11(CN)6]1V.Again the proportion non-ionisable iron ionisable iron= 1.0 gives a solid solution consisting mainly of I~Fe1'1[1Ei'e1'(CN)6]1V with traces of KE'e11Fe~'[Fe11(CN)6]~v and also of Fez'[Fe''(CN)6]r formed according to the equation KFe11FeF[Fe11(CN)6r+ K3Fe11'(CN)6=Fe~[Fe11(cN)6]~fK,Fe11(CN),. The formation of [with HANS LAUTERBACH] ( J . pr. Chem. 1922 [ii] 104,241-258).-i. 192 ABSTRACTS OF CHEMICAL PAPERS. Prussian blue and of Turnbull’s blue when non-ionisable iron ionisable iron=l may then be expressed respectively by E’eCl,+K,E”e1L(CN)6=KE’e111[Fe11(CN)6]’V+3KC1 and FeC1,+K3Fe11r( CN) 6 = KFellr[Fell( CN) ,]IV + 2KC1. Suppose for the formation of Turnbull’s blue a ferricyanide solution is used containing 1 mol.KCl per mol. FeCl so that there can be written FeCI,+K3Fe111( CN),+Kcl=KFell‘[Fell( CN)6]1V+3KC1 then both reactions become fully identical if the primary change is FeClq+K3Fe111(CN)6+KCl=PeC13+K4Fe11(CN)6. Equimolecular solutions of (a) FeC13 and K,Fe”(CN) ( b ) FeC1 and K3Fe111(CN)6+ KCl therefore give the same end-product the Prussian blue and Turnbull’s blue formed under these conditions being identical. These views which agree with results already obtained analytic- ally (cf. A. 1909 i 142 705 706; 1911 i 844; 1914 i 504 1058) have now been fully confirmed by following the various reactions potentiometrically ; the potential of a platinum electrode immersed in one reagent is compared with that of a normal electrode (Hg,Hg,Cl,,N-KC1) after each addition of the second reagent The results are shown graphically the volume of the added consti- tuent being plotted against the compensating ohmic resistance.The formation of solid solutions is deduced from the gradual slope of the relevant curves whilst the intersection at the point “non- ionisable iron ionisable iron=l ” of all four curves corresponding with the pairs of reagents (1) FeC$ and K,FeII(CN) (2) FeCl and K3Fe111(CN)6+KC1 is considered proof of the identity of the Prussian blue and the Turnbull’s blue formed under these conditions. W. S. N. Derivatives of Semioxamazide. I. Ketonic Semioxam- FORSYTH JAMES WILSON and ERIC CHARLES PICKERING azones. (T. 1923,123 394-397). Oxidation of Cadets’ Oil.Preparation of Cacodylic Acid. HENRI GUINOT ( J . Phrm. Chim. 1923 [vii] 27 5&64).-The mixture of cacodyl and cacodyl oxide obtained by the dry dis- tillation of potassium acetate and arsenious oxide is oxidised quantitatively to cacodylic acid by aqueous hypochlorite solutions and the same reaction may be utilised for its estimation the excess of hypochlorite added being determined by the addition of potassium iodide and titration of the liberated iodine with thiosulphate. For the preparation of cacodylic acid the oil is agitated with the requisite amount of sodium hypochlorite solution in presence of hydrochloric acid the completion of the oxidation being indicated by the dis- appearance of the odour of cacodyl or by the use of potassium iodide-starch paper.The acid solution thus obtained is neutralised with sodium hydroxide using Congo-red as indicator and is then evaporated to a small bulk and the sodium chloride which separates is removed. The syrup is finally evaporated to dryness and extracted with 96% alcohol. The alcoholic extract on cooling deposits pure cacodylic acid in 70% yield and another 20% mayORGANIC CHEMISTRY. i. 193 be obtained from the mother-liquors. Alternatively cacodylic acid may be obtained in 80% yield by direct oxidation by means of oxygen of a solution of the oil in dry acetone to which slightly more than the amount of water theoretically required by the following equations is gradually added as the absorption of oxygen proceeds (AsMe2),0+H,0+0,=2AsMe20*0H and B(AsMe,),+ 2H?,0+30,~4AsMe20*OH.The absorption of oxygen is very rapid and is with advantage moderated somewhat otherwise a certain amount of arsenious acid will be formed. The cacodylic acid formed crystallises from the solution in an almost pure con- dition. The anodic oxidation of a solution of the oil in 20% sulphuric acid also gives a 70-80~0 yield of cacodylic acid but this method does not present any practical advantage. G. F. M. Permanence of the Grignard Reagent. HENRY GILMAN and CHARLES H. MEYERS ( J . Ind. Eng. Chem. 1923 15 61).- Observations extending over more than six months showed that the numerous Grignard reagents examined underwent no appreci- able deterioration or decomposition during this period when kept in ethereal solution (in some cases highly concentrated) and adequately protected from the moisture carbon dioxide and oxygen of the atmosphere by storage in glass-stoppered containers. G.F. M. The Optimum Condition for the Preparation of Magnesium Ethyl Iodide. HENRY GILMAN and CHARLES H. MEYERS ( J . Amer. Chem. Soc. 1923 45 159-165).-Using the methods of analysis previously described (ibid. 150) and a special reaction flask by means of which it was possible to withdraw aliquot portions for analysis a study was made of the factors which influence the yield of magnesium ethyl iodide and therefore to some extent the yield of other Grignard reagents. The results indicate that there is a steady increase in the percentage of Grignard reagent formed when the rate of addition of ethyl iodide is pro- gressively decreased but that no advantage is gained by extending the time for the addition of 9.5 g.of ethyl iodide beyond forty- five minutes. Stirring during the addition of the ethyl iodide and for fifteen minutes after the addition is completed is desirable and then it is not necessary to warm the mixture under a reflux condenser. Any large excess of magnesium does not affect the yield. When no precautions are taken to exclude the moisture and carbon dioxide of the air the yield is lowered. Under a standard set of conditions the finer the grade of magnesium turnings used the higher is the yield. W. G. Reducing Action of Grignard Reagents. B. A. BUY- and E. OUY (Anal. 36s. Quim. 1922 20 599-6OO).-Metallic alkyloxides react with Grignard reagents giving hydrocarbons. For example magnesium ethyl iodide and sodium methoxide in the presence of anhydrous xylene with ethyl ether or dimethyl- aniline as catalyst react as follows MgEtI+MeONa=C,H4+i.194 ABSTRACTS OF CHEMICAL PAPERS. CH4+MgO+NaI. oxide give ethylene and an unidentified liquid hydrocarbon. Ethyl magnesium iodide and sodium amyl- G. W. R. The Preparation of Methylmercuric Acetate and the Isolation of Methylmercuric Hydroxide. M. CANNON SNEED and J. LEWIS MAYNARD (J. Amer. Chem. Soc. 1922 44 2942- 2947).-The substance described by Otto (Annulen 1870 154 199) as methylmercuric acetate m. p. 142-143" could not have been pure. The authors have obtained pure methylmercuric acetate by four different methods namely (1) the action of mercuric acetate on mercurydimethyl in methyl alcohol (2) the neutralis- ation of methylmercuric hydroxide with glacial acetic acid (3) the action of methylmercuric hydroxide on ethyl acetate (4) the inter- action of silver acetate and methylmercuric iodide.So prepared i t has in all cases m. p. 128" and is very soluble in water acetic acid and ethyl alcohol. It is also one of the products of the thermal decomposition of mercurous acetate in an atmosphere of nitrogen. Methylmercuric hydroxide m. p. 95" is readily obtained by the action of moist silver oxide on methylmercuric iodide in methyl alcohol. It is a very weak base being alkaline to litmus but acid fo phenolphthalein in aqueous solution. It is a strong vesicant even in dilute solutions. W. G. Ethyl Ether- and Ethanol-mercuri-salts. K. A. HOFMANN and KURT LESCHEWSKI (Bey.1923 56 [B] 123-139).-Hofmann and Sand have assigned the constitutions X*Hg*C,H4*OH and X*Hg*C,H,*O*C,H,*HgX to the products obtained by the action of ethylene on mercury salts whereas according to Manchot (A 1920 i 519 720) they are to be regarded as additive products C,H,,HgX*OH analogous to the compound obtained from cuprous chloride and carbon monoxide. The readiness with which they evolve ethylene appears to support Manchot's conception but on the other hand the same tendency is observed with undoubtedly atomic compounds such as ethylene dibromide which yields ethylene when treated with magnesium or organomagnesium compounds and magnesium ethyl bromide which evolves the gas when treated with manganese chloride. The mercuri-salts are somewhat sharply differentiated from Manchot's compounds of cuprous chloride with ethylene or carbon monoxide by their much greater stability towards non-acidic reagents and heat.The strongest argument in favour of the conception of the existence of an alcoholic group in ethanolmercuri-compounds lies in the observa- tion that they evolve alcohol and aldehyde when boiled with potassium hydroxide solution and leave a residue of metallic mercury and mercarbide C,H,04Hg,. The change proceeds slowly when potassium hydroxide alone is used but can be greatly accelerated by the addition of potassium iodide; under the latter conditions 50 yo of the organic portion of ethanolmercuri-chloride is obtained as alcohol and aldehyde the production of the latter being attributable to the oxidising action of mercury oxide in theORGANIC CHEMISTRY.i. 195 strongly alkaline medium. The action is very difficult to explain Manchot's mode of formulation is adopted since the persistence of portions of the mercuri-compound until the conclusion of the change shows that hydratisation of ethylene does not occur previously to its evolution and an alkaline suspension of mercury oxide is found to be without appreciable action on pre-formed ethylene . H. W. Primary Tar. I. FRANZ SCHUTZ (Ber. 1923 56 [B] 162- 169).-An examination of the tar formed by the carbonisation of coal obtained from the neighbourhood of Dortmund in rotary furnaces a t 500-600". The coal yields about 23% of volatile products (about 7% tar 6% aqueous distillate and 10% gas) and about 77% of semi-coke. It is found that the most volatile portions of the neutral oils contain only very small quantities of paraffins and larger amounts of unsaturated hydrocarbons. They consist mainly of aromatic and hydroaromatic hydrocarbons.The presence of benzene toluene and xylene is established and that of their higher homologues is shown to be probable. The presence of considerable amounts of hydroaromatic hydrocarbons may be regarded as extremely probable. The absence of naphthalene is confirmed. Ketones particularly acetone are present. Phenol occurs in considerable quantity its amount being very much greater $ban in coke-oven tar. Traces of acetaldehyde and aceto- nitrile are observed. Tolyl mercaptans are present in very small amount together with a sulphide b.p. 150-160" which appears to belong to the aliphatic series. Preparation of Petroleum from Rosin. SEIJI KWAI (J. Chem. Ind. Japan 1922 25 1421-1424).-0n distilling a mixture of rosin (acid value 162.1 and saponification value 178.3) and dried Japanese acid earth (ratio 1 0.5-1 2) a t 160" to 350" under ordinary pressure an oily distillate d 0.88 wits produced; the yield being about 60% of the rosin used. This had an odour and a marked fluorescence similar to that of natural petroleum and is approximately composed of naphthenes about 50 % aromatic hydrocarbons 40 % and unsaturated hydrocarbons (probably terpenes) 10 yo. K. K. H. W. Lely's Benzene Formula. S. C. J. OLIVIER (Chem. Week- bla;d 1923 20 27).-A criticism of the triangular formula (this vol.i 99). The synchronous rotation of the hydrogen atoms or substituents attached to the secondary carbon atoms is a dangerous conception; applied to the four dissimilar atoms or groups attached to an asymmetric carbon atom i t would invalidate the possibility of optical isomerism. Further the existence of meta- and ortho- substituted benzenes is only possible if the phase of the synchronous rotation is unalterable in molecular collisions reactions etc. The facts with regard to substitution generally are only explained by Lely by arguments which could equally easily be employed to lead to exactly opposite conclusions. s. I. L.i. 196 ABSTRACTS OF CHEMICAL PAPERS. The Essentials of a Benzene Formula. H. J. PRINS (Chern. Weekblad 1923 20 28 ; see preceding abstract).-Lely's formula fails entirely to explain the characteristic properties of the aromatic as contrasted with the aliphatic compounds; if benzene contained -CH,- groups all the mono-substituted benzenes should act as if the substituent were united to a carbon atom still united to hydrogen e.g.phenol like a secondary alcohol. Quinol would have the group C<OH and ring formation as in phthalic anhydride should occur equally readily with para-substituted derivatives as terephthalic acid. s. I. L. H. A. J. SCHOUTISSEN (Chern. 'Weekbktd 1923 20 29 ; see preceding abstracts).-The four valencies of the primary carbon atoms in Lely's formula lie in one plane and in an angle of 130" 32' making with each other angles of 36" 16' and 60". The valencies of the three secondary' carbon atoms lie along the edges of a tetrahedron.Such a dis- tribution in a stable system like benzene is unthinkable. A space-model of benzene based on the Lewis-Langmuir theory is suggested which has the necessary symmetry and valency- distribution. In one phase it coincides with that of Pauly (A. 1919 i l20) whilst by a rotation of each of the carbon atoms through 90" or 270" the configuration of Armstrong Baeyer and Claus is obtained. EMIL HEUSER L. ZEH and B. ASCHAN (2. angew. Chem. 1923 36 37- 38) .-p-Cymene occurs in appreciable quantities amongst the volatile products of the hydrolysis of wood with dilute mineral acids under pressure and originates probably from the action of the acid on the or-pinene derived from the resins of the wood.It was isolated from the light oil which collects on the surface of the distillate. This was treated with sodium hydrogen sulphite to remove furfuraldehyde and with 40 yo potassium hydroxide to remove volatile acids and then fractionally distilled. The fraction boiling between 174" and 179" consisted largely of p-cymene which was identified by conversion into barium pcymenesulphonate. The total content of p-cymene in the light oil was estimated a t 475%. G. F. M. l-Methyl3-tert.-amylbenzene. G. CHARRIER [with M. GALLOTTI and E. ZAPPELLI] (Gaxzetta 1922,52 ii 317-323).-By the action of tert.-amyl chloride on toluene in presence of aluminium chloride the author has obtained the compound prepared by Essner and Gossin (A. 1885 517) by treating toluene in presence of aluminium chloride with either active or inactive amyl chloride or amylene.The conclusion drawn by these authors that this compound is 1- methyl-3-tert.-amylbenzene is confirmed its description in Beilstein (edition 111 ii 36) as m-isoamyltoluene being inaccurate. l-Methyl-3-tert.-amylbenzene is a colourless mobile refractive liquid with an odour of pine resin d-io 0-8930 di0 0.8673 d:"" 0.8082. OH The Structural Formula for Benzene. s. I. L. Cpene as a By-product of the Hydrolysis of Wood.ORQANIO CHEMISTRY. i. 197 When oxidised by either permanganate or dilute nitric acid it yields isophthalic acid. The action of fuming nitric acid at -10" gives two isomeric mononitro-derivatives which are uncrystallisable pale yellow liquids with a pungent odour of musk (1) b.p. 160- 161'/25 mm. dj 1.0675 and (2) b. p. 165-169'/23 mm. d 1.0825; the nitro-groups probably occupy the 2- 4- or 6-positions. The action of chlorine on the hydrocarbon in presence of iodine yields two monochloro-derivatives probably the 4- and 6-com- pounds (1) a mobile highly refractive liquid with a delicate odour qf aniseed b. p. 242-243"/750-25 mm. di 0.9769 and (2) a highly refractive liquid with a similar odour to the previous compound b. p. 247-248"/750*25 mm. dj 1.0111 ; neither isomeride solidifies a t -25". The action of bromine on the hydrocarbon in the dark at 0" gives 4-(or 6) brmo-l-methyl-3-tert.-amylbenxene which is a highly refractive liquid with a pleasing ethereal odour b. p. 262-264'1 752.38 mm. d,' 1.2143 and remains liquid at -25". The Influence of some Substituents in the Benzene Ring on the Mobility of the Chlorine in the Side-chain in its Rela- tion to the Problem of Substitution in the Benzene Ring.11. S. C. J. OLIVIER (Rec. trav. chim. 1922 41 646-651; cf. A. 1922 i 646).-A development of the work described in the previous paper. The influence of the position of the substituent is less pronounced the greater the retarding influence of that substituent on mobility. A table is given showing the values of the reaction constants calculated from the rate of saponification of various compounds that for benzyl chloride itself being taken as unity. From this it is seen that a t a higher temperature the reaction velocities generally tend to become of identical value the smaller increasing with temperature the greater remaining approximately constant.The retarding influence of the negative substituents is thus less pronounced a t a highe? temperature. The list of sub- stituents in their order of influence as previously given (loc. cit.) is now amplified by addition of bromine and is p-Me > 0-Me > m-Me > H>~-C1~~-Br>o-Cl>o-Br>m-C1>m-Br~m-NOz> o-NO,>p-NO,. Some Constants of Phenylchlor of orm [ Tr i- w -&lor ot oluene 3. FRED. SWARTS (Bull. doc. chim. Belg. 1922 31 375-377).-8 redetermination of some of the physical constants of tri-o-chloro- toluenegave the following values m. p. -4.75" ; b. p. 110*7"/23 mm. ; 220*7"/761 mm.; di5 1-3775. The cryoscopic constant has the notably high value 93.1. Moist air in contact with the substance causes rapid and considerable lowering of the freezing point previous values for which are -22.5" (Haas A 1893 ii 357) -17" (Altschul A.1895 ii 206) and -8.1 (Timmermans A. 1914 ii 168). E. KNOEVENAGEL and A. ROMER (Ber. 1923 56 [B] 21&217).-Sodium benzenesulphinate in the presence of ether is converted by one or less molecular proportion of phosphorus trichloride into phenyl benzenethiosulphonate T. H. P. H. J. E. H. J. E. Aromatic Sulphinic Acids.i. 198 ABSTRACTS OF CHEMICAL PAPERS. Ph*SO,*SPh m p. 45" which is reduced by an excess of the tri- chloride to diphenyl disulphide m. p. 60". Under simiIar condi- tions thionyl chloride yields benzenesulphonyl chloride phenyl benzenethiosulphonate and some nitrogen sulphide. Sulphuryl chloride gives benzenesulphonyl chloride.Salts of the type CHR:NHR'.SO,Ph are obtained by the action of molar amounts of benzenesulphinic acid and a d s in the presence of ether a t the atmospheric temperature. These are decomposed by solution in alcohol and subsequent addition of ether in accord- ance with the equations CHR:NHR'*SO,Ph+H,O=R*CHO+ R'*NH2+Ph*S02H ; 3Ph*S02H=Ph*S0,H+Ph*S02*S*Ph +H20 ; Ph*So~HfPho~,=Ph*~H,<~o~ph. The salts derived from the following anils have the melting points placed in brackets benzylideneaniline (82') ; benzoinanil (158-160') ; acetophenone- a d (136") ; dypnoneanil (130"). Acetoneanil and N-isopropenyl- N-methylaniline appear to react in a more complicated manner. Ferrous and ferric benzene sulphinates are almost insoluble in water ; the nickel cobalt copper and cadmium salts dissolve to the extent of 10-15% in boiling water the manganese salt to 20% and the lead and silver salts to 40%.Aluminium and chromium salts do not give a precipitate with benzenesulphinic acid. The manganese copper and lead salts are soluble in dilute acetic acid ; the cadmium salt dissolves in glacial acetic acid whereas the nickel cobalt and iron salts require dilute mineral acids to bring them into solution. H. W. Certain Derivatives of Anthracene. F. KEHRMANN RAOUL MONNIER and MARIE RAMM (Ber. 1923 56 [B] 169-174).- Attempts are described to obtain dyes of the type C6H4< gE2>c6H3:NH. The nitration of 9 10 lo-triphenyl-9 10-dihydroanthran-9-01 (Haller and Guyot A. 1904 i 660) could not be satisfactorily accomplished.9-Phenyl-10 10-diethyl-9 lO-dihydroanthran-9-o1 colourless needles m. p. 111-112" is prepared by the action of magnesium phenyl bromide on 10 10-diethyl-9-anthrone ; it forms coloured carbonium salts with sulphuric perchloric and nitric acids. When dissolved in concentrated sulphuric acid it is converted by alcohol into 10-phenyl-9 9-diethyl-9 10-dihydroanthracene colourless needles m. p. 135-136". 9 9-Diethyl-9 10-dihydroanthracene slender colourless needles m. p. 210' is obtained by the reduction of diethylanthrone with zinc dust and acetic acid. 9 10-Diphenyl-9 10-dihydroanthra-9 10-diol (Haller and Guyot loc. cit.) gives an intense indigo-blue solution in concen- trated sulphuric acid; it appears to be transformed thereby into anthraquinone 9 10-diphenylanthracene and an intensely reddish- yellow substance which has not been completely investigated. The nitration and reduction of the products will be described subsequently. H.W.BEQAWIC CHEMISTRY. i. 199 Preparation of Cyclic Amines. A. MAILHE (Bull. Soc. chim. 1923 [iv] 33 83-86).-The direct hydrogenation of the hydr- azones or ketazines of cyclic ketones over a nickel catalyst a t 180" leads as in the case of similar open-chain compounds to the formation of primary aniines accompanied by a small proportion of the corresponding secondary amines. Thus the hydrazone of 1 3-dimethyl-4-cyclohexanone is converted into 1 3-dimethyl-4- cyclohexylamine a colourless liquid b. p. 169-171" d14 0*8810 which rapidly absorbs carbon dioxide from the air and gives a hydrochloride m.p. 278" and a phenylcarbamide m. p. 174". Simi- larly carvylamine is obtained together with a small quantity of dicarvylamine by the hydrogenation of carvone ketazine. Carvyl- amine boils at 205-210" and forms a hydrochloride m. p. 198". Menthylamine obtained by the hydrogenation of menthonehydraxone a colourless liquid b. p. 243" over nickel at ZOO" is a strong base b. p. 212" giving a hydrochloride m. p. 274". Dimenthylamine produced a t the same time boils a t 305-310" and gives a hydro- chloride m. p. 207". Formation of Phenylcarbylamine and Nitrobenzene in Aqueous Aniline Solutions. HERMANN KUNZ-KRAUSE and PAUL MANICKE (Ber. Deut. pharrn. Ges. 1922 32 232-236).-The formation of products with an odour of carbylamine when aniline and water are exposed for several months to sunlight does not take place if the aniline is pure the products in this case being of a tarry nature and dissolving in concentrated sulphuric acid with a Bordeaux-red colour.Mono-methyl- and ethyl-anilines and toluidine behave in the same way as aniline. On the other hand minute traces of nitrobenzene are formed even with pure aniline under the above conditions. Action of Alcohols on Anilides. ALPHONSE MAILHE (Bull. SOC. chim. 1923 [iv] 33 81-83).-Although the hydrogen atom of the NH= group of secondary arylamines i s readily replaced by an alkyl group by the action of aliphatic alcohols in presence of dehydrating catalysts such as thoria or alumina the aromatic amides cannot be similarly alkylated as the water produced in the reaction causes the hydrolysis of the amides. So for example the catalysis of a mixture of acetanilide and methyl alcohol vapours over alumina at 370-380" results not in the formation of methyl- acetadde but of a mixture of aniline methylaniline and dimethyl- aniline and acetic acid together with small quantities of dimethyl ether.Other anilides and toluidides behave in a similar manner either with methyl or ethyl alcohol. With propyl alcohol propylene and water are formed and the anilide is hydrolysed; but no propyl- anilines are produced. The Action of Sodammonium on Aniline and its Homo- lopes. M. PICON (Cmpt. rend. 1922 175 1213-1216).- The action of sodammonium on cyclic amines in which the nitrogen is directly linked to the benzene ring affords a ready method of preparing the sodium derivatives of these amines.Only G. F. M. P. M. G. F. M.i. 200 ABSTRACTS OF CHEMICAL PAPERS. monosodium derivatives were obtained ; these are formed as readily with primary as with secondary amines. No reaction occurs with benzylamine. Monosodioaniline NHPhNa is a pale yellow transparent solid decomposed by water with formation of aniline and sodium hydroxide and reacting with alkyl halides yielding substituted anilines (cf. Titherley T. 1897 71 464). Sodio-ethyluniline NPhEtNa is a pale yellow solid ; monosodio- o-toluidine C,H,Me*NHNa a pale yellow solid ; sodiodiphenyl- amine NPh,Na a white solid; they all show properties similar to those of monosodioaniline. The method of preparation consists in mixing the amine with sodammonium and an excess of liquid ammonia and allowing the mixture to remain in contact under pressure at the ordinary temperature for some days.Attempts to prepare disodium derivatives were unsuccessful. H. J. E. Reaction between Aniline and Chloroacetic Acid. I. RYUZABURO NODZU and SHIGERU KOMATSU (Mem. Coll. Xci. Kyoto 1922 6 73-76).-Among the products of interaction of aniline (1.04 mol.) and chloroacetic acid (1 mol.) in a closed vessel a t 100" were isolated and identified chloroacetanilide diketodiphenylpiper- azine phenyliminodiacetic acid and its mono-anilide and phenyl- glycine. The mono-anilide is probably formed by the interaction of phenylglycine and chloroacetanilide. E. H. R. Optically Active Dyes. I. A. W. INUERSOLL and ROGER ADAMS ( J .Amer. Chem. Xoc. 1922 44 2930-2937).-1n order to investigate the question as to whether the absorption of dyes by animal or vegetable fibres is a physical or chemical phenomenon the authors propose to prepare a number of optically active dyes and to examine the rate of absorption of the optical isomerides. With this purpose in view they have prepared two such pairs of dyes. d- and l-aminoPhenylacetic acid have been condensed with p-nitrobenzoyl chloride and the products reduced to the corre- sponding amino-compounds which were then diazotised and the diazo-compounds coupled with @-naphthol and dimethylaniline respectively. Preliminary dyeing experiments have been carried out and although the d- and Z-@-naphthol dyes were absorbed in the same relative amounts over short as well as long periods the experiments with the two dimethylaniline dyes indicated that one is absorbed more rapidly than the other.The following new compounds are described r-p-Nitrobenzamidophenylucetic acid m. p. 184" (corr.) its ethy2 ester m. p. 140" (corr.). r-p-Amino- benxamidophenylacetic acid m. p. 152" (corr.) and its hydro- chloride m. p. 215" (decomp.). l-p-Nitrobenxamidophenylacetic acid m. p. 163" (corr.) [a] -86*56" its ethyl ester m. p. 155" (corr.) [a]' - 67.7". l-p-Aminobenxamidophenylacetic acid m. p. 168-169" (corr.) [a] -93*75" and its hydrochloride m. p. 220- 222" (decomp.). d-p-Nitrobenxamido~henylacetic acid m. p. 163" (corr.) [a]$ +86.13" its ethyl ester m. p. 155" (corr.) [a]'$ +67.4". d-p-Aminobenxamidophenylacetic acid m.p. 168-169" (corr.) [a12 +93*63" and its hydrochloride m. p. 220" (decomp.). TheORGANIC CHEMISTRY. i. 201 r-aminobenzoyl acid when diazotised and the produot coupled with p-naphthol gave a compnd m. p. 252" the Z-acid similarly gave a compound,'m. p. 238" [a]" -27*25" and the d-acid a com- pound m. p. 238" (con!.) [ O L ] ~ +28*50". When diazotised and the product coupled prith dimethylaniline the Z-acid gave a m ~ n d m. p. 189-190" and the &-acid a compound m. p. 188-189". W. G. Catalytic Preparation of o-Toluidine. C. 0. HENKE and 0. W. BROWNE ( J . Physical Chem. 1923 27 52-64).-1n con- tinuation of previous work on the catalytic reduction of nitro- benzene to aniline (A. 1922 i 445 535; ii 833) the authors have investigated the catalytic reduction of o-nitrotoluene to o-toluidine by means of hydrogen.A nickel catalyst is too active for this purpose a large part of the o-nitrotoluene being reduced beyond the toluidine stage. The highest yield obtained with nickel was 86*8%. Lead catalysts gave slightly higher yields of 0-toluidine than of aniline the respective yields in the two cases being 9406% and 93*4y0. Silver when first used gave a yield of 99% of o-toluidine but its activity decreased with use especially a t the higher rates of flow of o-nitrotoluene. A 97% yi$d of o-toluidine was obtained with a copper catalyst used a t 260 the activity of which had been decreased by use at too high a temperature (300"). A copper catalyst prepared by the ignition of copper nitrate at 415" and containing o.023~0 of iron gave a yield of 98.3% of o-toluidine at 260".The corresponding yield of aniline was 91.9%. The activity of copper catalysts did not decrease with use. o-Nitrotoluene is more easily reduced than nitrobenzene. J. S. G. T. The Isomerism of @-Benzylaminocrotonic Ester its Re- action with Ferric Chloride and that of Related Compounds. ERICH BENARY (Ber. 1923 56 [B] 53-55).-The constitutions CH,Ph*N:CMe*CH:C( OH)*OEt and CH,Ph*N:CMe*CH,*CO,Et have been assigned by Rugheimer (A. 1916 i 383) to the isomeric ethyl P-benzylaminocrotonates. The author considers this conception highly improbable since it involves the enolisation of the carb- ethoxyl group in a series in which enolisation occurs only with difliculty and only when there is an accumulation of negative substituents around the carbon atom.The differing behaviour of the isomerides towards ferric chloride (Riigheimer Zoc. cit.) is not directly related to their constitution since the development of the coloration depends on their fission to base and ethyl acetoacetate. A similar dependence of the production of colour on the decom- position of the compound is observed in the cases of ethyl p-amino- cro tonate e thy1 p-anilino (or p - t oluidino ) crot onate methyl p-anilinocrotonate and ethyl ethylenediaminoacetoacetate but not of their acidic derivatives as far as they have been examined. The colour is not developed if ferric acetate is substituted for ferric chloride. It is doubtful whether the existence of two forms of ethyli. 202 ABSTRACTS OF CHEMICAL PAPERS.@-benzylamiuocrotonate is to be ascribed to cis-trans-immerism or to structural isomerism. H. w. The Tertiary Amines Derived from Benzhydrylamine. MARCEL SOMIVIELET (Cmpt. rend. 1922 175 1149-1151; cf. A. 1922 i 333) .-The additive product of hexarnethylenetetramine and diphenylbromomethane is converted by the action of formic acid into dimethylbenzhydrylamine CHPh,*NMe which combines very slowly in the cold with methyl iodide in methyl alcohol to give a methiodide m. p. 211". In hot solution the hydriodide is obtained along with the methiodide and also a neutral oily com- pound. Diethylbenzhydr ylamine benz h ydrylpiperidine and ethyl- benz ylbenz hydr ylamine behave similarly towards methyl iodide but in these cases very little if any of the methiodide is formed at 100".If methyl bromide is used instead of methyl iodide it is not possible to isolate any quaternary salt but only the hydro- bromide. If dimethylbenzhydrylamine and methyl bromide are heated together in solution in methyl alcohol in a sealed tube at 100" for forty-eight hours there is an abundant evolution of methyl ether and benzhydryl methyl ether CHPh,*OMe and trimethylamine hydrobromide are obtained. If the methyl alcohol is replaced by butyl alcohol the products are methyl butyl ether and benzhydryl butyl ether. These products may result as follows MeBr+MeOH+CHPh,*NMe,=Me,O+CHPh,*NMe,,HBr ; CHPh,*NMe,Br= CHPh,Br+NMe and CHPh,Br+MeOH +NMe3= CHPh,*OMe +NMe,,HBr. W. G. Diphenyl. 111. Derivatives of Bromodiphenyl. A. GARC~A BANUS and L. MEDRANO (Anal.Fis. Quim. 1922 20 47-78; cf. A. 1922 i 333).-By methylation of 4-bromo-4'-aminodiphenyl using methyl alcohol and strong hydrochloric acid and heating in sealed tubes for ten hours a t 140-150" 4-bromo-4'-dimethylamino- diphenyl is obtained which after recrystallisation has m. p. 205- 208". The mother-liquors from the crystallisation of this com- pound yield the corresponding methochloride m. p. 180-185". By nitration 4- bromo-2-nitro-4'-dimethylaminodiphenyl is obtained ; it forms large orange-yellow plates m. p. 107". Diphenyl. 111. Derivatives of Anilinodiphenyl. A. GARC~A BANUS and J. GUITERAS (Anal. 3%. Quim. 1922 20 479- 485; cf. A. 1922 i 333).-By boiling paminodiphenyl with fused sodium and 4 1 3-chlorodinitrobenzene in a reflux apparatus 4-op-dinitroa;niZinodi~henyl C,H,Ph*NH*C,H,(N02)2 is obtained ; i b has m.p. 147" and crystallises in two forms namely orange needles from acetic acid and red crystals from toluene. The transformation point from the orange to the red form is 95-105". By reduction with sodium sulphide p-nitro-o-aminolmili~diphenyl is obtained in platelets m. p. 188". 2-op-Dinitratnilinodiphenyl is crystalline m. p. 159". The corresponding 2-p-nitry-o-amino- anilimdiphenyl obtained by reduction with sodium sulphde forms dark orange platelets m. p. 151-152". 4'-Bromo-4-op-dinitro- anilinodipherqjl from 4 4'- bromoarninodiphenyl forms yellow G. W. R.ORGANIC CHEMISTRY. i. 203 leaflets m. p. 206205". 3 4-Diaminodiphenyl gives with hydrochloric acid and sodium nitrite 5-pknyl- benziminaxole (annexed formula) ; it forms white 4'-Amino-4-op-dinitro- P h 0 - N anilinodiphenyl forms small prisms m.p. 245-247" 4'-Amino-4-p-nitro-o-aminatnilinodiphenyl forms red platelets m. p. 201 ". 4'- Amino-4-op-diaminoanilinodiphenyl forms grey platelets m. p. 197". NH /'/\fJ plates m. p. 154-155". G. W. R. The Preparation of Phenylimido-phosgene [Phenylcarbyl- amine Chloride] and the Chlorination of Formanilide. R. S. BLY G. A. PERKINS and W. LEE LEWIS ( J . Amer. Chem. Soc. 1922 44,2896-2903) .-Good yields of phenylthiocarbimide were obtained from thiocarbanilide by heating it under a reflux condenser for several hours with three parts of dilute sulphuric acid (one of acid to 2.5 volumes of water) and subsequently distilling the product with steam. When the thiocarbimide is chlorinated to saturation in solution in carbon tetrachloride or carbon disulphide a 95% yield of phenylcarbylamine chloride is obtained if the solvent is removed directly by fractional distillation a t a pressure of 30 mm. By using the phenylcarbylamine chloride itself as a solvent for subsequent chlorinations the other solvents could be dispensed with.When formanilide was chlorinated in the cold with or without solvents in the presence of sulphur chloride the product was in all cases 2 4-dichloroformanilide. If the chlorination was conducted in the presence of thionyl chloride a series of products mas obtained namely 2 4-dichloroformanilide phenylcarbylamine chloride p-c~lorop~nylca;rbylamine chloride b. p. 135-137"/30 mm. and 2 4-dichlorophenylcar~~~mine chloride b.p. 150-153"/30 mm. p-Chlorophenylcarbylamine chloride when heated with glacial acetic acid yielded p-chloroacetanilide and with aniline yielded chlorotriphenylgunidine m. p. 135-136" as its hydrochloride m. p. 247-250". Similarly 2 4-dichlorophenylcarbylamine chlor- ide gave with acetic acid 2 4-dichloroacetanilide and with aniline 2 4dichlorotriphenylguanidine m. p. 129.5-1305" (corr.) as its hydrochloride m. p. 207-209" (corr.). The specific gravity of these substituted chlorides increases with the chlorine content but the lachrymatory effect diminishes. W. G. New Derivatives of p-Phenetylcarbamide (Dulcin). Max BERGMANN FUNZESKO CA.MACHO and FERDINAND DREYER (Ber. Deut. pham. Ges. 1922 32 249-258; cf. Speckan A. 1922 i 580) .-Various derivatives of dulcin (p-phenetylcarbamide) have been prepared in an effort to find one which should be more soluble while retaining the sweet taste.more soluble and very sweet but has a very persistent unpleamnt flavour as well. The unpleasant taste is less marked in a-p-phenetyl- a-hydroxyethylcarbamide but is still sufficient to render it techni- cally useless. These and other compounds of the same type were prepared by the action of potassium cyamte on the hydrochlorides of the corresponding bases in aqueous solution. Derivatives of a-p-Phenetyl-a-methylcarbamidei. 204 ABSTRACTS OF CHEMICAL PAPERS. dulcin in which an alkyl group is introduced into the primary amino-group are sparingly soluble and have no appreciable sweet taste. The latter compounds were prepared by the action of the corresponding thiocarbimides on phenetidine whereby the thio- carbamide derivatives were formed which were converted into the corresponding carbamide compounds by the action of mercuric oxide in acetic acid.a-p- Phenet yl -a-meth yl curbamid e OEt *C,H,*NMe*CO *NH was ob- tained in good yield from potassium cyanate and N-methyl- phenetidine hydrochloride. It forms long needles m. p. 128- 129". Similarly N-hydroxyethyl-p-phenetidine gave a-p-phenetyl- a- hydroxyethylmrbamide OEt*C,H,.N( CH,*CH,DOH)*CO*NH needles m. p. 113-115". Dihydroxypropylphenetidine (Ber. 1 922 55 2796) gave a - p-phenet y l-a-dih ydrox yprop ylcarbamide OEt*C6H4*N[ CH,*CH (OH)* CH,*OH] *CO*NH crystals m. p. 138- 139" without sweet taste. By the action of ethyl chloroacetate on p-phenetidine p-phenetylglycine ethyl ester 0Et.C ,H4*NH*CH,*Co,Et is formed leaflets m. p.38" b. p. 152"/1 mm. (amide m. p. 146"). The ester is converted by potassium cyanate into methyl-a-p- phenetylcarbamido-a-acetate OEt*C6H4*N(CH2*CO,Et)*CO0~H col- ourless needles m. p. 86-47" of slightly bitter taste. With alcoholic ammonia it gives the corresponding amide m. p. 236- 237" without distinctive taste. p-Phenetidine and allylthiocarbimide gave a-p-phenetyl-b-allyl- thiocarbarnide crystals m. p. 94-95". With mercuric oxide it gives a-p-phenetyl-b-allylmrbamide crystallising from alcohol acetic acid or ethyl acetate in fine needles from chloroform in rectangular plabs m. p. 167". Similarly a - p -p henet y l - b - met h y It hiocarbamid e cryst allises from alcohol in truncated prisms m.p 128-128.5" and a-p-phenetyl-b- methylcarbamide forms fine long quadrilateral platelets m. p. 159". N-Methyl-p-phenetidine and methylthiocarbimide give a-p-phenetyl- ab-dimethylthiocurbamide truncated prisms m. p. 99-loo" and a-p-phenetyl-ab-dimethyhrbamide prisms m. p. 94-95" Simi- larly a-p-phenetyl-a-methyl- b-allylthiocarbamide forms long needles m. p. 68-69' and a-p-phenetyl-a-methyl-b-allylcarbamide thin needles m. p. 57-58'. P. M. Hydrogenated Polycylic Ring Systems. I. The Hydro- genation of Phenol and the By-products which are formed thereby. WALTHER SCHRAUTH WILHELM WEQE and FRITZ DANNER (Ber. 1923 56 [B] 260-268).-The hydrogenation of phenol in the gaseous state and under pressure has been studied in the presence of a nickel-copper catalyst.The arrangement of the apparatus for the first series of experiments is essentially that of Sabatier (Die Kutalyse 1914). Phenol is converted into a mixture of cyclohexanol (80-83%) cyclohexanone (6-9y0) and smaller quantities of products of lower boiling point which have not been investigated fully; about 10% of the phenol remains unchanged. The results are closely similar to those obtained inORGANIC CHEMISTRY. i. 205 the presence of reduced nickel by Sabatier and Senderens (A. 1904 i 156) and by Skita and Ritter (A. 1911 i 272). Hydrogenation under pressure in the presence of the nickel- copper catalyst is effected according to Schroeter's method (A. 1922 i 122). It leads essentially to a mixture of cyclohexanol and cyclohexanone containing about 9-14% of the latter. The volatile products formed during the hydrogenation in the vaporous phase are not observed their place being taken by dark oils of high boiling point the amount of which may rise to loo/ when the action is unusually prolonged.A condensation appears there- fore to occur in which cyclohexanol or more probably cyclohexanone takes part. Since the relative amounts of these substances is thereby undisturbed it follows that the equilibrium between them is rapidly restored in the presence of the catalyst which can also induce dehydrogenation (cf. Sabatier and Senderens A 1903 i 393). The liquids of high boiling point consist of di- and tri-cyclic condensation products consisting partly of saturated and partly of unsaturated ketones and aldehydes which are readily converted by further hydrogenation into homogeneous saturated compounds of alcoholic character. 1 3 -Dic y clohexy Zc y clohexan e -2 -one C 6H ,*C 6H ,O *C sH ,.long colourless prisms m. p. 131-132" is obtained by the adhtion of alcohol to the least volatile fractions of the condensation products obtained by the hydrogenation of phenol under pressure. As in analogous cases the presence of the ketonic group cannot be established by the help of semicarbazide hydrochloride or amino- guanidine hydrochloride but the constitution of the product is placed beyond doubt by its production by the hydrogenation of 1 3-dicydohexenylcyclohexane-2-one (cf. Mannich A. 1907 i 205). A solution of the ketone in methylcyclohexane is catalytically hydrogenated a t 180-190" to a mixture of isomeric 1 3-dicyclo- hexylcyclohexane-2-ols colourless needles m.p. 117" and a very viscous colourless liquid b. p. 220-221"/17 mm.; the latter is slowly converted into the solid variety when preserved. Either alcohol appears to be transformed into a mixture of the cis- and trans-acetctte when acetylated. The liquid alcohol is dehydrated by zinc chloride a t 200-210" with the formation of 1 3-dicyclo- hexyE-Al-cyclohexene b. p. 20P-207"/15 mm. d 0.9525 ; the hydro- carbon is also preparable from the solid alcohol but it is uncertain whether a uniform product is obtained in this manner. It is transformed by hydrogenation in the presence of methylcyclo- hexane to it mixture of 1 3-dicyclokexylcyclohexanes long colour- less needles m.p. 66-67' and a liquid b. p. 192-196"/12 mm. d 0.9335. H. W. The Synthesis of Phosphoric Acid Esters. I. SHIGERU KOMATSU and SHINICHIRO KUMAMOTO (Mem. Colt. Xci. Kyoto 1922 6 45-48).-cydoHexanol when left in contact with phos- phoric acid in presence of phosphoric oxide forms a mono-ester (C61iQl)~P04 colaurless crystals m. p. 77-78". The soluble VOL. CXXIV. i. ii. 206 ABSTRACTS OF CHEMICAL PAPERS. barium salt C6HI1BaPO is a white crystalhe substance ; the silver salt is insoluble in water. When heated the free ester and the barium salt are both decomposed into cyclohexene and phos- phoric acid or phosphate. The di- and tri-cyclohexyl phosphates could not be obtained. E. H. R. The Action of Iodine on Alkaline Solutions of Phenol. G.VORTMANN (Ber. 1923 56 [B] 234-246).-In a previous communication it has been shown that iodine reacts with an alkaline solution of phenol to give “ di-iodophenol iodide,” 0:C <cIicH>C<I (Messinger and Vortmann A. 1890 1473). The existence of this compound has been denied by Bougault (A. 1908 ii 738) by Wilkie (A. 1911 ii 546; 1912 i 346) and by Hunter and Woollett (A. 1921 i 238). Its isolation is now described. The action of iodine on an alkaline solution of phenol takes place by the initial substitution of the halogen for the sodium atom of the phenoxide and its subsequent migration into the nucleus Ph.0-I + C,H,I*OH. The process is then repeated until t i - iodophenol is produced. Even in the presence of a large excess of iodine the nature of the product depends essentially on the quantity of alkali.Iodination therefore is effected by the alkali hypoiodite. Even in the presence of more than three molecular proportions of sodium hydroxide a compound more highly iodinated than tri-iodophenol is not produced; if the solution is acidified after not more than five minutes this compound is quantitatively precipitated and is not further affected by the presence of much free iodine in the acid medium. If the phenol solution is not too dilute tri-iodophenol separates previously to acidification ; if it is shaken from time to time in the alkaline suspension it gradually darkens in colour and passes into a mixture of “di-iodophenol iodide ” and tetraiododiphenylenequinone (cf. Lautemann Annalen 1861 120 309). Iodination of phenol in the presence of a large excess of alkali yields only di-iodophenol.Di-iodophenol iodide is most conveniently prepared by thc prolonged action of cold sodium hypoiodite solution on phenol. The brown mixture of the product with Lautemann’s red is treated with acetone in which the former only is soluble to a yellowish-brown solution from which it is reprecipitated by the addition of much water and sodium chloride in the form of irregular dark violet-brown leaflets or scales m. p. 122”. It slowly loses iodine when exposed to air and gives a violet coloration when its dilute solution in acetone is treated with a little sodium thiosulphate solution. The mechanism of the formation of Lautemann’s red is dis- cussed in detail and appears t o be represented by the fdlowing equations C,H,I,*OH+NaIO=C,H,I,.OI+NaOH ; C,H,I,*OI -+ C6H212(:0):12 C,H212(:O):I,+NaOH=;c6H212(:O):IH+~a01; Oxidation of tri-iodophenol by the requisite amount of potassium CI’CH H %,H,I,( :o):HI =2HI + O:C,H,I,:C,H,I,:O.ORGANIC CHEMISTRY.i. 207 persulphate in the presence of sodium carbonate gives a mixture of di-iodophenol iodide and Lautemann's red. Reduction of the latter in glacial acetic acid solution by stannous chloride and hydrochloric acid gives a colourless compound which appears to be a hydrogenated derivative (cf. Hunter and Woollett Zoc. cit.). Phenol may be estimated by treating its solution which must contain at least four molecular proportions of sodium hydroxide with an excess of iodine solution; after five minutes the solution is acidified with dilute sulphuric acid whereby tri-iodophenol is precipitated.The excess of iodine is estimated in an aliquot portion of the supernatant liquor. If the time of action is prolonged beyond five minutes the precipitate is more or less discoloured but the consumption of iodine is not thereby changed. PAUL SCHORIGM (Ber. 1923 56 [B] 176-186; cf. A. 1910 i 547).- Diphenyl ether reacts exothermally with sodium wire a t 180- 20O0 giving phenol (60-75%) benzene (30%) a small quantity of diphenyl phenol-like products of high boiling point and car- bonised substances. The reaction also occurs in the presence of neutral solvents of suitable boiling point. The reaction is con- sidered to involve the primary addition of sodium to yield the product Ph,ONa and immediate scission of the latter into sodium phenoxide and sodium phenyl.The latter is decomposed by water (evolved during the production of the complex pitch-like products) with the formation of benzene and sodium hydroxide. The formation of diphenyl may be ascribed to the direct removal of oxygen from the ether by sodium or to the interaction of sodium phenoxide and sodium phenyl PhNa+PhONa=Ph*Ph+Na,O. The intermediate formation of organo-metallic sodium derivatives is rendered probable by the observation that an extremely vigorous action takes place when dry air is bubbled through the mixture but on the other hand salicylic acid is produced when carbon dioxide is introduced into it whereas sodium phenyl would be expected to yield benzoic acid.a-Naphthyl ethyl ether reacts vigorously with sodium a t 230- 270° yielding naphthalene a-naphthol carbonised and pitch-like products ethylene ethane and hydrogen. The volume of ethylene formed exceeds that of ethane ; the production of butane or butylene could not be established. P-Naphthyl ethyl ether reacts more energetically than the a-isonieride with sodium but yields similar products naphthalene @-naphthol ethylene ethane and hydrogen Phenetole does not react to an appreciable extent with sodium at any temperature below its boiling point. At 200-260" it becomes decomposed into phenol ethane ethylene hydrogen products of high boiling point carbonised material and small quantities of ethyl alcohol. The intermediate formation of organo- metallic substances is established by the observations that the product of reaction becomes heated sometimes to the point of ignition when exposed to air and that propionic acid is produced when it is treated with carbon dioxide. H.W. The Decomposition of Ethers by Metallic Sodium. i 2i. 208 ABSTRACTS OF CHEMICa PAPERS. Benzyl ethyl ether reacts with sodium a t lM' this temperature being much below its boiling point; benzyl alcohol appears to be produced but owing to an accident the products could not be fully investigated. isoAmyl ether yields small amounts of isoamyl alcohol when heated with sodium at 200-220' and subsequently at 235-2275" The experiments show that the desiccation of simple ethers by distillation over sodium is open to suspicion and that the process is quite unsuitable for fatty-aromatic and aromatic ethers of high boiling point.If the use of sodium is desired milder conditions should be adopted and the metal should be removed previously to the distillation of the ether. H. W. Simplified Methods of Preparing certain Organic Sub- stances. I. Nitrophenetoles and Nitroanisoles. H. VAN ERP (Ber. 1923 56 [B] 217-221).-The substances are prepared by the action of potassiuni alkyl sulphates on potassium nitro- phenoxides in the presence of a small quantity of glycerol. The latter after being purified and dehydrated by distillation under diminished pressure is placed in a +-litre flask provided with a reflux condenser filled with cold water but with both tubes closed; an intimate mixture of the potassium compounds previously desiccated a t 140' and loo' respectively is added; and the mixture is heated in an oil-bath usually at about 180" to 210° until the change appears to be complete.The yields obtained are as follows o-nitrophenetole above 90% ; 2 4-dinitrophenetole 56% ; 6-chloro-2 4-dinitrophenetole 0% ; p-nitroanisole 87%. Contrary to the statements in the literature pure methyl sulphate has b. p. 76'/15 mm. d15 1.3348. Contrary to statements in Beilstein's Handbuch crystalline potassium methyl sulphate is anhydrous and not deliquescent. H. W. Certain Bromine Derivatives of Thymol. HANS JOST and FRIEDRICH RICHTER (Ber. 1923 56 [B] 119-123).-The action of bromine on thymol dissolved in glacial acetic acid has been examined by Dannenberg (A. 1903 i 338) who has thereby isolated a product which he considers to be the keto-bromide The remarkable constitution of the com- pound has led the authors to re-examine the reaction; they draw the conclusion that the substance described by Dannenberg does not exist.The action of broniine on thymol under the conditions adopted by Dannenberg proceeds beyond the formation of a dibromo- compound and gives also a true keto-bromide CloH,,OBr (see later) which renders the product of the reaction incompletely soluble in solutions of alkali hydroxide; if a smaller proportion of bromine is used its production is avoided and the dibromo- fhymol is completely soluble; it crystallises in long colourless prisms m. p. +3*54' b. p. 160-161"/16 mm. 175'125 mm. CMegCBr-CO> CHBr.CH/ CPrS.ORQANIC CHEMISTRY. i.209 di! 1.6631 dij"; 1.6618 d$f 1.6588; the corresponding benzoate forms small colourless needles m. p. 89-90" whereas Dannenberg gives m. p. 80-81". v Thymoi is converted by a solution of calcium bromohypobromite into tribromo-p-menthccdienone CMegBr?-CIi>CPrp Br 420 or (see above) large dark yellow plGtes m. p. 59-60' after softening at 55". The substance decomposes somewhat readily when pre- served. It liberates two atomic proportions of iodine from neutral potassium iodide solution and is reduced by stannous chloride in the presence of hydrogen chloride and acetic acid to dibromo- thymol. It is converted by cold concentrated sulphuric acid into 2 4 6-tribromo-m-cresol its behaviour in this respect being similar to that of trichloro-p-menthadienone (Crowther and McCombie T.1913 103 539 545). The keto-bromide is also obtained by the action of sodium hypobromitc or of an excess of bromine on thymol. When dissolved in carbon tetrachloride and shaken with aqueous potassium hydroxide solution (a%) it is transformed into a brown amorphous powder m. p. 220-230" (decomp.) after darkening at 200". H. W. Amino-alcohols of Tetrdin [Tetrahydronaphthalene]. A. GONZLLEZ and M. CAMPOY (Anal. Pis. Quim. 1922 20 534- 538).-By the action of hypobromous acid on 1 4-dihydro- naphthalene 3 - bromo- 2 - h yd rox ytetrah ydronaphthulene is obtained . It is crystalline and has m. p. 107". By acting on it with anhydrous dimethylamine in benzene solution in a sealed tube at 120" 3-dimethylamino-2-hydroxytetrahydronaphthulene is obtained b.p. 165-1 70" / 14 mm. 2- Dimeth ylumino- 1 - hydroxytetrahydronaphthul- ene has b. p. 157-158"/13 mm. The following compounds were also prepared 2- benzoyl-3-dimethyZumirwtetrahydromphthulene hydrochloride m. p. 228" ; 2-valeryl-3-dimethylminotetrahydro- naphthalene hydrochloride m. p. 173" ; 2-cinnamoyl-3-dimethyl- aminotetrahydmnaphthalene hydrochloride m. p. 178" ; 2-pyro- mucyl-3 -dimethyluminotetrahydromphthcclene hydrochloride ; 1 - benxoyt 2-dimethylaminotetrahydromphthulene hydrochloride m. p. 176" ; 1 -valeryl-2-dimethylaminotetrahydronuphthulene hydrochloride m. p. 165" ; 1-cinnamoyl-2-dimethyluminotetrahydronuphthlene hydrochlor- ide m. p. 176.5" ; 1 -pyromucyl-2-dimethyluminotetrahydromphthulene hydrochloride m. p. 172". Hydrochlorides of the 1 2-series are more soluble and have a lower melting point than those of the 2 3-series.G. W. R. A New Class of Derivatives of @-Naphthol the l-AryL amino-@-naphthols. A. WAHL and ROBERT LANTZ (Bull. Soc. chim. 1923 [iv] 33 93-1 lo).-Certain atoms and groups which in the benzene nucleus are only displaced at high temperatures or not at all are extremely reactive when substituted in the a-position in p-naphthol. Thus the sulphonic group of p-naphthol-a-sulphonic acid is eliminated when the substance is treated in aqueous solutioni. 210 ABSTRACTS OF CHEMICAL PAPERS. with p-nitrobenzenediazonium chloride. I n alkaline solution the reaction occurs in two stages with the intermediate formation of an extremely unstable compound which is thought to be a diazo5 oxide of the formula S03Na*C,oH600*N:N*C,H,*N0,. In presence of the least trace of acid this yellow water-soluble substance is instantly converted into p-nitraniline-red OH*C1,H6*N:N*C6 H,*NO with liberation of sulphuric acid.With a-chloro- @-naphthol the intermediate product cannot be isolated the dye being produced at once with the elimination of the chlorine atom. The mobility of the halogen atom in the a-position is further illustrated by the action of sodium sulphite in weak alcoholic solution p-naphthol being formed and the halogen eliminated. a-Chloro- or a-bromo-8- naphthol also reacts vigorously with primary aromatic amines and moderating the reaction by using a large excess of the amine quantitative yields of 1-arylamino-2-hydroxynaphthalenes are obtained.1-Anilino-p-nuphthol forms white needles m. p. 155- 156" which darken on exposure to air. The hydrochloride forms a white crystalline powder and the methyl ether colourless needles m. p. 82-83". 1-p-Toluidino- p-naphthol forms white prisms in. p. 138-139" and its methyl ether white needles m. p. 94". 1 -0-Toluidino- @-nuphthol crystallised from acetic acid melts at 11A115". 1-o-Anisidino-@-nuphthol crystallises in small needles m. p. 110". 1-o-Methoxy-m-toluidino-@-naphthol forms white needles m. p. 118". 1-a-Naphthylamino-p-naphthol forms grey needles m. p. 171" aiid the corresponding p-derivative a grey powder m. p. 166-167". G. F. M. The Influence of Boric Acid on some Polyhydroxy-deriv- atives of Naphthalene and Anthraquinone. J. BOESEKEN [with (MILE) K.C. ANEMA and (MLLE) AT. A. J. BREVET] (Rec. trav. chim. 1922 41 778-783; cf. A. 1915 ii 667).-Two o-dihydroxynaphthalenes similarly to dihydroxyphenols (cf . Boeseken and Van Rossem A. 1912 ii 147) considerably increase the electrical conductivity of solutions of boric acid but the increase due to the 2 3-dihydroxy-compound is much greater than that conferred by its 1 2-isomeride. This difference is attributed to greater freedom of the hydroxyl groups in the former compound. The hydroxy-derivatives of anthraquinone were found to be insufficiently soluble in water for similar measurements of conductivity to be made but a coloration was observed in each case on the addition of boric acid to a solution of the substance.in dilute alcohol. The suggestion is made that the coloration depends on the presence of two hydroxyl groups in the ortho-position with respect to each other or alternatively that it is correlated with the presence of a hydroxyl group next to a carbonyl group.H. J. E. Preparation of Benzyl Esters of some Acids of High Boiling Point. T. J. THOMPSON and GERALD J. LEUCK ( J . Amer. Chern. Xoc. 1922 44 289&2896).-Benzyl esters of certainORGANIC CHEMISTRY. i. 211 acids which boil at above 100" without decomposition have been prepared by heating together the alcohol and acid in the requisite proportions in a flask fitted with an air condenser of such a length that the benzyl alcohol vapour condenses just below its upper end whilst it is not long enough to cause the condensation of the water vapour arising from the interaction of the alcohol and acid.Pure benzyl alcohol free from traces of benzaldehyde must be used. Good yields were obtained in the case of eight esters but in two cases it was necessary to vary the pressure in the flask. Other high boiling point alcohols were tried instead of benzyl alcohol but they did not give satisfactory results. JV. G. Triphenylmethyl. -11. p-Benzyloxy- and p-Methoxy- triphenylmethyl. M. GOMBERG and C. C . BUCHLER ( J . Amer. Chem. Soc. 1923 45 207-222).-p-Benxyloxytriphenylmrbinol m. p. 94" was prepared from the corresponding hydroxy-compound by the Schotten-Baumann reaction. When reduced with zinc and acetic acid it yielded p-benzyloxytriphenylmethune m. p. 116.5" and with hydrogen chloride gave p-betzzyloxytriphenylmethyl chloride m.p. 77" from which by the action of sodium ethoxide p-benzyloxytriphenylmethyl ethyl ether m. p. 89" was obtained. p-Benzyloxytriphenylmethyl bromide had m. p. 90". When the chloride was shaken with molecular silver in dry benzene p-benzyloxytri- phenylmethyl m. p. 142-145" was obtained ; it rapidly absorbed oxygen from the air giving a peroxide m. p. 171" and absorbed iodine from its solution giving an unstable iodide In benzene solution the free radicle reacts with hydrogen chloride to give a mixture of the carbinyl chloride and the triarylmethane and these interact only to a very slight extent to give a dialkyloxy-p-benz- hydryltetraphenylmethane. A benzene solution of the free radicle exposed in a quartz tube to sunlight undergoes auto-oxidation and reduction to form a biphenylene free radicle and p-benzyl- oxytriphenylmethane. The free radicle was crystallised from a number of different types of solvents but only in one case namely with ether was an additive compound formed.The degree of dissociation of di-p-benzyloxyhexaphenylethane in six different solvents over a temperature range from -17" to +53" and in concentrations from 1 to 6% was found to vary from 26 to 56% with the concentration the temperature and the nature of the solvent. p-Methoxytriphenylcarbinol gave a chloride and a bromide m. p. 143" and from the chloride the free radicle p-rnethoxytriphenyl- methyl m. p. 145-150" was obtained. It absorbs oxygen giving a peroxide m. p. 157" and iodine giving an iodide. Like the benzyloxy-compound the main reaction with hydrogen chloride in benzene solution is to yield the carbinyl chloride,and the tri- arylmethane.When exposed to sunlight in the same solvent a mixture of p-methoxytriphenylmethane and a biphenylenetriaryl- methyl result and from this solution on exposure to air 9-phSenyl-3- methoxyfEuury1 peroxide m. p. 200" (decomp.) was obtained. This peroxide was synthesised by a different method as follows :i. 212 ABSTRACTS OF CHEMICAL PAPERS. 3-methoxy-9-fluorenone was converted by the action of magneaium phenyl bromide into the carbinol (annexed Ph OH formula) m. p. S4" giving a chloride m. p. 119". From this by shaking ppith molecular silver the C /\/\/\ free radicle was obtained and this on exposure I 1 I to air gave the required peroxide. p-Methoxy- \,r-\/OMe triphenylmethyl did not give any additive com- pounds with the various solvents tried.The degree of dissociation of di-p-methoxyhexaphenylethane determined as in the case of the benzyloxy-compound varied from 22 to 42%. \/ W. G. Triphenylmethyl. XXXI. Tautomerism of o-Hydroxy- triphenylcarbinol ; o-Hydroxy- and Alkyloxy-triphenyl- methyl. M. GOMBERG and D. NISHIDA (J. Amer. Chem. Soc. 1923 45 190-207) .-When o-hydroxytriphenylcarbinol in solu- tion in glacial acetic acid carbon tetrachloride benzene toluene or xylene is warmed the solution becomes brown the coloration beginning a t 50-S0° according to the nature of the solvent and increasing in intensity with rise in temperature or concentration of the solution. This coloration is due to tautomerisation of the carbinyl to the quinonoid form and the change is reversible if the temperature does not exceed 110".Above 110" the carbinol in solution slowly loses water and yields not the expected o-fuchsone but a rearrangement product namely 9-phenylxanthane. The carbinyl chloride undergoes similar changes but a t much lower temperatures and loses hydrogen chloride instead of water. o-Benzyloxytriphenylcarbinyl chloride is considerably more stable than the o-hydroxy-compound but even a t ordinary temperatures it undergoes a gradual spontaneous decomposition. o-Hydroxy- o-benzyloxy- and o-methoxy-triphenylcarbinyl chlorides are all decomposed by molecular silver giving the free radicle but in the cases of the first two the free triarylmethyls could not be isolated owing to secondary changes but o-methoxytriphenylmethyl was isolated and its physical and chemical properties were determined.It exists in solution in the unimolecular state to the extent of 26-49y0 depending on the temperature. At ordinary tem- peratures only about one-third of the total amount of the uni- molecular triarylmethyl is in the quinonoid state the remaining two-thirds being benzenoid. o-Hydroxytriphenylchlorornethune was obtained by dissolving the carbinol in ether adding calcium chloride and saturating the solution with hydrogen chloride. Colourless crystals were obtained which rapidly became brown even in a desiccator. When shaken in benzene solution with molecular silver in the presence of air the polymeriaed o-hydroxytriphenylmethyl m. p.237" wa8 obtained together with a peroxide HO*C6H,*CPh,*O.O*CPh~*c6H~*0H m. p. 131". o-Benxyloxytriphenylmrbinol m. p. 172" was prepared from the hydroxy-compound and gave the carbinyl chloride m. p. 146" which with molecular silver gave the polymeride m. p. 207" of the triarylmethyl and also a peroxide m. p. 153".ORGANIC CHEMISTRY. i. 213 o-Methoxytriphenylcarbinol gave a stable chloride and bromide m. p. 127-128". The chloride when decomposed by molecular silver gave a mixture of di-o-methoxyhexaphenyletbne m. p. 117- 121" and o-methoxytriphenylmethyZ. The free radicle when exposed to air rapidly absorbs oxygen and gives its peroxide m. p. 160- 161" (decomp.) and similarly it absorbs iodine to give its iodide. Both the free radicle and its chloride and bromide show decided electrical conductivity in liquid sulphur dioxide.W. G. Pinacolic and Semi-pinacolic Transpositions. Compar- ative Migratory Aptitudes of Different Radicles. M. TIT- FENEAU and (MILE) J. LEVY (Cornpi. rend. 1923,176 312-314).- From examples of pinacolic and semi-pinacolic transpositions of substituted glycols and iodohydrins quoted i t is shown that ethyl and benzyl groups have a much more marked aptitude for migration than has the methyl group and in many cases the migration of the former groups is exclusive. W. G . Compounds containing the Trimethylene [cycZoPropane f Ring. P. BRTJYLANTS and A. STASSENS (Bull. Acud. roy. BeZg. 1921 702-7 19) .-cycZoPropanecarboxylonitrile when prepared from y-chlorobutyronitrile by distilling with dry potassium hydr- oxide contains crotono- or isocrotono-nitrile.The pure cyclo-nitrile boils at 134-134*2"/7626 mm. Pure cyclopropanecarboxylic acid has m. p. 18.1" and b. p. 181.8-182*0"/766 mm. The corresponding chloride on chlorination at the b. p. gives (a) 1-chlorocyclopopne- carboxyl chloride b. p. 141-143" dy 1.336 ng 14759 and (b) a small amount of what is apparently my-dichlmobutyryl chloride b. p. 212-214". The former (a) was converted by water into 1 -chlorocyclopro~necarboxylic acid colourless needles m. p. 70- 71" b. p. 206"; sodium salt colourless hygroscopic needles; methyl ester b. p. 152-153"/761 mm. 8F 1-179; ethyZ ester b. p. 65-66'115 mm. or 162-163"/762-5 mm. @ 1.126 ng 1.4447; amide white crystals m. p. 131-132". Ethyl 1 -chlorocyclopropanecarboxylate by treatment with mag- nesium methyl bromide is converted info a chlarohydrin C3H,C1*CMe,*OH.The latter has b. p. 1566-157"/756 mm. d," 1.065 forms an acetyl derivative dp 1.086 and is almost unaffected by hot aqueous potassium hydroxide. The chlorine atom in 1 -chlorocyclopropanecarboxylic acid is not reactive enough to permit of the preparation of derivatives by its replacement. The constitution of the acid was decided from conductivity measurements with the acid and its sodium salt whence the dissociation constant (100 k) was found to be between 0.05 and 0.06 a value only to be explained if the chloro-group is in the a-position. By treating the higher boiling fractions of the above chlorination with methyl alcohol in presence of a little sulphuric acid methyl a-chlorocyclopropanecarboxylate and methyl ay-dichlwobutyrate b.p. 212-214" were obtained. The molecular heats of combustion of cyclopropanecarboxylic i*i. 214 ABSTRACTS OF CHEMICAL PAPERS. acid at constant volume and at constant pressure were found to be 486.1 and 486.4 cal. respectively whereas for crotonic acid the value is 478.0 cal. The heat of formation of the acid in the liquid state is 97.8 cal. (crotonic acid 102.3 cal.). Determinations of the viscosities and melting points of mixtures of cyclopropanecarboxylic acid with water are described and point to the existence of a hydrate C,H602,H20. E. E. T. 4-Fluoro-3-nitrobenzoic Acid. H. ROUCHE (Bull. Acad. roy. Re&. 1921 534-547).4-Fluorobei1zoic acid on treatment with nitric acid (d 1*495) is converted to the extent of 80% into 4-$UOrO- 3-nitrobenzoic acid white needles m.p. 121.5" 4-fluoronitrobenzene also being formed as the result of the displacement of the carboxyl group by the nitro-group. The new acid forms soluble and highly coloured salts (alkali metals red alkaline-earth metals yellow or orange). The ethyl ester yellow crystals melts a t 45.3". The chloride 1). p. 210"/130 mm. on treatment with aqueous ammonia gives 3-nitro-4-aminobenzamide dry ammonia in ethereal solution however giving 4-Jluoro-3-nitro- benzamide a waxy mass m. p. 153". The solubilities of 4-fluoro- 4-chloro- and 4-bromo-3-nitro- benzoic acids have been compared. The dissociation constants (100 it) of 4-fluoro- and 4-chloro- 3-nitrobenzoic acids were found to be respectively 0.0433 and 0.048 (cf.A. 1890 1209) the corresponding 4-bromo-acid being stronger than these two acids. p-Fluorohenzoic acid used in comparison gave 100 k 0*00735. Owing to the labile nature of the fluoro-group in fluoronitrobenzoic acid conductivity determin- ations with the latter mere carried out in presence of hydrochloric acid. A study of the velocities of reaction with sodium methoxide of sodium fluoronitrobenzoate and o-fluoronitrobenzene showed that The silver salt is unstable. the carboxyl group renders a para-fluoro-group more labile. E. E. T. a-Nitrophenylacetamide and some of its Derivatives. A. J. VAN PESKI (Rec. trav. chim. 1922 41 687-700; cf. A. 1909 i 647) .-On treatment of m-isonitrophenylacetamide with concentrated sodium hydroxide solution the sodium derivative of the amide which is first formed gradually disappears and sodium nitrophenylacetainide is formed.This reacts with bromine to give a-bromo-Ix-nitrophenylacetamide which is easily obtained pure. The action of dilute sulphuric acid on the aqueous solution of the sodium derivative gives a white precipitate which becomes viscid and then solidifies. This consists of a-nitrophenylacet- amide which on crystallisation from benzene or chloroform is obtained in the form of white needles m. p. 82-5-83". These remain unchanged for a considerable time ; decomposition may be detected by a lowering of the melting point and after some months the substance is transformed into a thick brown syrup. Complete decomposition may be effected in less than two hours by heatingORGANIC CHEMISTRY.i. 215 on the water-bath among the decomposition products are nitro- gen nitrous oxide plienylglyoxylic acid phenylglyoxylamide benzonitrile water and two unidentified derivatives of phenyl- glyoxylamide. On boiling in contact with water the products are phenylglyoxylic acid and its amide benzoic acid and the oxime of phenylglyoxylamide. The chloro-derivative of a-nitrophenyl- acetaniide is prepared in a similar manner to the bromo-derivative but the corresponding iodine compound is obtained in ethereal solution of iodine by reaction with the silver salt of the amide. All three halogen derivatives liberate nitric oxide and the halogen on being heated; the decomposition may take place explosively. The following descriptions are given a-chloro-a-nitrophenylacet- amide white prisms m.p. 107-1 15" ; a-bromo-a-nitro~henylicet- amide crystals m. p. 108-1 16" ; a-iodo-a-nitrophenylucetamide yellow rod-shaped crystals ni. p. 97-100" ; o-bromo-a-nitrop~enyl- acetamide white rod-shaped crystals m. p. 125" ; p-bromo-a-nitro- phenylucetamide white rod-shaped crystals m. p. 101.5" ; ethyl imkbphenylperucetate CH,Ph*C(NH)*O*OEt small rod-shaped crystals m. p. 180". H. J. E. Asymmetrical Synthesis. EMIL ERLENMEYER and HANS ERLENMEYER (Biochem. Z. 1922 133 52-62).-1f bromine be added to a. solution containing cinnamic acid a sugar and a zinc salt the dibromophenylpropionic acid formed is optically active except in the case of lactose where the resulting acid is inactive. Presumably a complex salt of zinc with cinnamic acid on the one hand and with the sugar on the other is formed and this optically active compound adds on bromine asymmetrically.With dextrose laevulose and sucrose excess of the I- ap-dibromo - p-phenylpropionic acid is formed and with I-arabinose excess of the d-acid. Laevulose is particularly effective and it is likewise active if a-methylcinnamic acid is used instead of cinnamic acid. W. 0. K. The Iodination of ma-Hydroxybenzoic Acid. P. H. BEIJER (Rec. truv. chim. 1922 41 701-702).-Monoiodohydroxybenzoic acid was prepared by Wieselsky's method (Annulen 1874 174 105). An identical acid was obtained from 4-nitro-3-hydroxy- benzoic acid by reduction of the nitro-group diazotisation and treatment with potassium iodide. The acid is thus 4-iodo-3- hydroxybenzoic acid so that the action of iodine yields a derivative substituted similarly to that obtained on bromination.This was confirmed by the preparation of 6-iodo-3-hydroxybenzoic acid (cf. Limpricht A. 1891 1036) which is not identical with the acid obtained by Wieselsky. The Configuration of Mandelic Acid and other a-Hydroxy- acids. KARL FREUDENBERG FRITZ BRAUNS and HEINRICH SIEGEL (Ber. 1923 56 [B] 193-200).-The hypothesis that the optical activity of similarly constituted substances of the same configuration is influenced in a uniform manner by change of temperature dilution or addition of neutral salts has led Clough H. J. E. i" 2i. 216 ABSTRACTS OF CHEMICAL PAPERS. (T. 1918 113 526) to assign I-mandelic acid to the d-series (con- figuration I) whereas Hudson (A 1918 i yo$ 292) on the consideration that all hydroxy- H-V-OH H0.Y.H acids which yield dextrorotatory amides C,H and hydrazides belong to the d-series has (11.) assigned to i t the configuration I1 (l-mandel- amide is laevorotatory). Z-Hexahydromandel- amide has now been prepared and shown to be strongly dextro- rotatory.Since therefore I-mandelic and I-hexahydromandelic acids are configurationally related Hudson's rule appears to be broken. A consideration of the optical act,ivities of cr-hydroxy- acids of known configuration and of their amides confirms the validity of Clough's deductions. Hudson's rule appears merely to require a slight modification in the sense that a-hydroxy-acids are considered to belong to the d-series when their specific rotation is displaced in the dextro-direction on conversion into the amide.An actual transition from laevo to dextro is only observed with substances of low rotatory power such as the monocarboxylic acids of the sugar group from a study of which the rule was first developed. dl-cycloHexylglycollic acid m. p. 134-135" [Godchot (A. 1910 i 480) gives 130-131'1 is prepared by the catalytic hydrogenation of &I-mandelic acid in aqueous solution in the presence of plat,inum with gum arabic or gelatin as protective colloid. It is smoothly esterified to methyl dl-cyclohexylglycollate b. p. 122-123"/18 mm. from which the corresponding amide m. p. 156" (Godchot gives m. p. 155") is prepared. dl-cycloHexylglycollophen ylhydrazide has m. p. 213". d(-)cycloHexylglycollic mid prepared by hydrogenation of I-mandelic acid has m.p. 128-129" [ a x g yellow -26.6" [cxgg -25.8" in glacial acetic acid solution. The corresponding methyl ester has b. p. 123"/19 mm. [ Q ] & ~ ~ ~ ~ ~ -4.7" ; the phenylhydraxide m. p. about 216" (decomp.) [ o ~ ] ~ I O ~ ~ ~ ~ ~ ~ ~ +55.25" in glacial acetic acid and the amide m. p. 158" [a~geellow +47.4" in alcohol [E]& +41.16" in aqueous (20%) alcohol are described. d(-)-Lactic acid prepared by the resolution of the r-acid with morphine (cf. Irvine T. 1906 89 934 is converted into the methyl ester b. p. 50-60"/25 mm. [cx]~g'gyellow +7.3" and thence into the amide m. p. 49-41" [a]&8gydlow +22.2"; it is remarkable that the active amide is very deliquescent and that this property is not shared by the r-amide.yo&- C6H5 (1.1 H. W. The Theory of Reduction. The Reduction of the Carbonyl Group by Zinc Amalgam. WILHELM STEINKOPP and ARTHUR WOLFRAM (Annulen 1023 430 113-161).-A careful study of the action of zinc amalgam and aqueous or alcoholic hydrochloric acid on a variety of carbonyl compounds has shown that products of several distinct types may be obt,ained and that the formation of these may be accounted for by ascribing to the process the following general mechanism. In the first place hydrogen be- comes attached to the oxygen of the carbonyl group giving a radicle (containing tervalent carbon) which may react either withORGANIC CHEMISTRY. i. 217 itself yielding a pinacone or with more hydrogen forming an alcohol 1 ,+ 7 C(OH)*C(OH) < - >CH*OH >c=o + >C-oH Secondly if the alcohol contains a CH residue next to the carbinol group water may be eliminated giving first a compound containing two tervalent carbon atoms and ultimately either a saturated or unsaturated substance Stress is laid on the view that the formation of the saturated and unsaturated substances is simultaneous and not successive a t least in the main.The constitution of the original carbonyl com- pound and the conditions of the reduction may determine which of the above four side reactions takes place preferentially but the above mechanism is considered to be generally applicable. Benzophenone on reduction with zinc amalgam and aqueous hydrochloric acid yields benzpinacone and traces of diphenyl- methane ; by reduction in alcoholic solution tetraphenylethylene a- and p-benzpinacolin and diphenylmethane may be obtained.Benzhydrol on reduction in alcoholic solution gives diphenylmethane and the benzpinacolins give tetraphenylethylene. Ethyl acetoacetate on reduction in alcohol gives ethyl crotonate and ethyl butyrate. Ethyl crotonate is not reduced to ethyl butyrate under similar conditions. Ethyl laevulate yields ethyl valcrate and an unsaturated ester probably p-ethylidenepropionic ester. Ethyl benzoylacetate on reduction in alcohol with amalgamated zinc yields py-diphenylpentadilactone (A. 1912 i 889) ethyl B-phenylpropionate and an oil b. p. 210-212”/< 1 mm. Using unamalgamated zinc the products are the dilactone ethyl cinnamate e thy1 p -phenylpropionate Q y dphen yl-ha -crotono- lactone- y-acetic acid and probably m~so-PP’-dihydroxy-Fp’-diphenyl- adipic acid.Ethyl cinnamate on reduction with amalgamated zinc in alcoholic hydrogen chloride gives ethyl P-phenylpropionate Ethyl phenylglyoxylate gives ethyl mandelate and ethyl diphenyl- tartrate and phenylglyoxylic acid yields mandelic acid. Reduction of acetophenone in aqueous solution leads to ethyl benzene acetophenonepinacolin and styrene and its polymelfisation products along with small amounts of acetophenonepinacone and ay-diphenylbutane ( a). In alcoholic solution the products are styrene and its polymerides acetophenonepinacone and a-chloro- ethylbenzene. The products of reduction of benzaldehyde in aqueous solution are toluene benzyl alcohol stilbene and hydrobenzoin. The action of zinc chloride on benzyl alcohol gives rise fo stilbene hydrochloride.C . K. I.i. 218 ABSTRACTS OF CHEMICAL PAPERS. The Isomeric Esters of Benzoylacrylic Acid. GRACE POTTER RICE (J. Amer. Chem. SOC. 1923 45 222-238).-The yellow methyl benzoylacrylate obtained by Kozniewski and Marchlewski (cf. A. 1906 i 759) can be converted into a colourless stereo- isomeride m. p. 67" by exposure to sunlight. The reverse change occurs if the colourless isomeride is exposed to sunlight in a solution containing a trace of iodine or bromine. Both the esters behave alike on oxidation by potassium permanganate in cold acetone solution and they give the same product on treatment with nitro- methane. Their behaviour towards alkaline reagents is not how- ever the same.On boiling the yellow ester with dilute sodium carbonate solution almost complete decomposition takes place and it is not possible to isolate any benzoylacrylic acid. The colourless ester under similar conditions gives a 60% yield of benzoylacrylic acid. With concentrated hydrochloric acid both the esters give a mixture of benzoylacrylic and a-hydroxybenzoyl- propionic acids. The benzoylacrylic acid obtained in either of these cases corresponds in configuration with the yellow ester. The colourless ester reacts with two molecules of semicarbazide hydrochloride to give the semicarbaxone of rneihyl a-semicarbazido- benxoylpropionate m. p. 177-178". If however only one molecule of semicarbazide is used then the product is methyl u-semicarbaxido- benxoylpropionate m. p.150-150*5" which when treated in cold acid solution with sodium nitrite gives methyl nitroso-a-semicarbaxido- benzoylpropionate m. p. 125". With one molecule of semicarbazide the yellow ester gives the same product as the colourless ester but with two molecules it yields methyl a- semicarbaxido-3-phenyl- pyraxolone-4-acelate m. p. 172" which when decomposed by hydrochloric acid gives the methyl semicarbazidobenzoylpropionate described above. Ethyl benxoylacr!yZate was obtained in a yellow form b. p. 1 8 6 185"/25 mm. and in a colourless form m. p. 54". As in the case of the methyl esters the following products were prepared the semi- carbaxone of ethyl a-semicurbaxidobenxoyZpropionate m. p. 187" ; ethyl a-semicurbaxidobenxoylpropionnte m. p. 151-152" ; ethyl nitroso-a-semicarbazidobenxoylpropionute m.p. 127 " ; ethyl a-semi- carbazido-3-phenylpyraxobne-4-acetate m. p. 171". Benzoylacrylic acid reacts with semicarbazide and gives the same products whether one or two molecules of the latter are used namely two isomeric semicurbaxones m. p. 205" and 225" re- spectively and a hydrate of the former m. p. 190". All three compounds react with bromine as unsaturated compounds and two atoms of bromine are added on to the molecule and a Dyes derived from Diphenic Anhydride. SIKHIBHUSHAN DUTT (T. 1923 123 225-228). The Action of Bromine on Methylcoumaric and Methyl- coumarinic Acids. EINAR BIILMANN and HAKON LUND (Ann. Chim. 1922 [ix] 18 263-282).-The addition of bromine in anhydrous solution to methylcouniaric and methylcoumarinic compound m.p. 171" is obtained. w. Q.ORGANIC CIXEMISTRY. i. 219 acids apparently results in the formation of a single product (cf. Fittig and Ebert A. 1883 474; Werner A. 1906 i 180) but Perkin (T. 1881 39 420) and Stoermer and Friemel (A. 1911 i 633) have obtained indications of two acids resulting. The last-named workers isolated an acid m. p. 170"; the authors' work confirms the formation of this single compound but they were unable to determine its constitution with certainty although the substance is presumed to be ap-dibromo-p-methoxyphenyl- propionic acid. This acid on treatment with powdered zinc was converted into methylcoumaric acid whilst water readily effected its hydrolysis into a-homo- p-hydroxy- P-methoxyphenylpropionic acid crystals m.p. 134" which yields on dehydration a-bromo-p-meth- oxyphenylacrylic acid obtained directly from a p -dibromo - 8-meth- oxyphenylpropionic acid by Perkin (Zoc. cit.). The hydrolysis by which the acid was obtained must not be effected at a high temperature otherwise carbon dioxide is evolved with formation of methoxybrornostyrene a light yellow oil b. p. 142-143"/14- 16 mm. whilst hydrobromic acid in acetic acid solution reverses the hydrolysis. Treatment of the acid with zinc powder results in the formation of methylcoumaric acid. The last-named sub- stance yields on bromination by means of solution of bromine in aqueous potassium bromide ap-5-tribromo-p-methoxy-5-phenyl- propionic acid which was also obtained from ap-dihromo-p-methoxy- phenylpropionic acid and bromine water and also by the action of hydrobromic acid on a-5-dibromo- p-hydroxy- p-methoxyphenyl- propionic acid.The latter was prepared by the action of bromine water on a-bromo- p-hydroxy- p-methoxyphenylpropionic acid and forms crystals m. p. 137" isomeric with and transformed by heating into an acid of m. p. 155" identical with that prepared by Read and Andrews (T. 1921,119 1782). This acid may also be obtained by hydrolysis of a $ - 5 - tribrom o - @-met hox yp henylpropionic acid the reaction being reversed by hydrobromic acid. Mercuric acetate and methylcoumarinic acid combine to form a mercuric compound (cf. A. 1900 i 431). This was not isolated but was used as an intermediate in the preparation of p-hydroxy-p-methoxyphenyl- propionic acid which resulted from the elimination of the mercury by means of hydrogen sulphide.This acid has m. p. 88.5" and is quantitatively converted into methylcoumaric acid when boiled with dilute sulphuric acid whilst bromine water yields a ring- substituted derivative 5-bromo-p-hydroxy-$-me~hoxyphenylpropionic mid m. p. 108". All the ring-substituted bromo-compounds dealt with are converted on oxidation with permanganate into 2-methoxy- 5-bromobenzoic acid and the same substance was obtained by oxidation of methylcoumaric acid with permanganate and sub- sequent treatment of the methoxybenzoic acid so formed with bromine water. H. J. E. The Chemistry of the Glutaconic Acids. XIV. Three- carbon Tautomerism in the cycloPropane Series. FRANK ROBERT Goss CHRISTOPHER KELK INGOLD and JOCELYN FIELD THORPE (T 1923 123 327-361).i. 220 ABSTRACTS OF CHEMICAL PAPERS.The Thermal Decomposition of certain Hydroaromatic Dicarboxylic Acids. A. WINDAUS W. HUCKEL and G. REVEREY (Ber. 1923 56 [BJ 91-98).-Blanc's rule (A. 1907 i 710) according to which pimelic and adipic acids are converted into cyclic ketones when heated a t about 300" (in the presence of acetic anhydride if necessary) whereas glutaric and succinic acids give internal anhydrides under similar conditions appears to be generally applicable in the aliphatic series. An experimental examination of the possibility of applying it in the hydroaromatic series has been undertaken and the behaviour of certain hydroaromatic o-dicarboxylic acids is now described. cis-cyclo-Hexane-1 2-dicarboxylic anhydride is decomposed a t 380" into carbon dioxide water anthraquinone and various hydrogenated derivatives of anthracene ; its behaviour is thus similar to that of calcium succinate.Homophthalic [o-carboxyphenylacetic] acid is smoothly hydro- genated in glacial acetic acid solution in the presence of platinum black to a mixture of cis- and trans-o-carboxycyclohexaneacetic acids from which the pure cis-acid is isolated by fractional cryst,al- lisation; it forms aggregates of prisms m. p. 146" and is converted by acetic anhydride into the corresponding anhydride rectangular plates m. p. 57". The cis-acid is isomerised by hydrochloric acid at 200" to the trans-acid colourless crystals m. p. 157" (anhydride short needles m. p. SO-81"). When either anhydride is heated for a considerable time a t 220" an equilibrium mixture con- taining about 25% of the cis- and 75% of the trans-variety is produced. o-Carboxyphenylpropionic acid is catalytically hydrogenated to cis-o-carboxycyclokxanepropionic acid prisms m.p. 103" ; the calcium salt and the di-anilide lustrous leaflets m. p. 159" are described. The acid is isomerised by concentrated hydrochloric acid at 180" to trans-o-mrboxycyclohexanepropionic acid prisms m. p. 143'. The corresponding di-anilide m. p. 212" is prepared from the acid and aniline or by heating the cis-di-anilide a t 250"; it can be distilled unchanged in a high vacuum. The cis- or the trans-acid is not converted into an alicyclic ketone containing one less atom of carbon when heated alone but either acid is trans- formed by distillation with acetic anhydride into hexahydro-a-hydr- indone C H 1 < ~ ~ ~ C H a colourless liquid b.p. 216"/758 mm. d? 0.9982 n 1.47915 n 1.48117 ng 1.48827 n 1.49342. The corresponding semicarbaxone crystallises in needles m. p. 2 1 6 215" (decomp.) when rapidly heated ; the oxime lustrous needles m. p. 79-80' is described. H. W. Total Hydrogenation of Naphthalic [Naphthalene-1 8- dicarboxylic] Acid. J. CASARES and J. RANEDO (Anal. Pis. Quim. 1922 20 519-526).-Naphthalene-l 8-dicarboxylic acid was hydrogenated to the tetrahydro- and decahydro-acids by the action of hydrogen in the presence of platinum. Spccially purified reagents were used and repeated activations were necessary.ORGANIC CHEMISTRY. i. 221 The decahydronaphthalene-1 8-dicarboxylic acid thus obtained has no definite melting point and is probably a mixture of cis- and tram-isomerides.Hydrogenation was effected more easily and without activations by use of the methyl and ethyl esters of naphthalic acid. Methyl tetrahydromphthulene-1 8-dicarboxylate thus obtained from methyl naphthalate forms crystals m. p. 74O. Ethyl tetrahydronaphthalene-1 8-dicarboxylute forms crystals m. p. 52" and has b. p. 193'117 mm. Methyl decahydromphthulene- 1 8-dicarboxylute forms crystals m. p. 103-105". G. W. R. The Preparation of Benzenepentacarboxylic Acid. KARL REISCHER and EWALD RETZE (Ber. 1923 56 [B] 228-234).-A new method of preparing benzenepentacarboxylic acid (cf . Fleischer and Siefert A. 1920 i 621) which starts from tetrahydro- naphthalene is described.2-Ethyl-5 6 7 8-tetrahydronaphthalene condenses with diethyl- malonyl chloride in the presence of alu- minium chloride and carbon disulphide /6\//5\ to yield 2 2 4-triethyltetrahydro~~~h-up- indane-1 3-dione (annexed formula) colour- C H 2 ~ / ~ / \ ~ o less crystals m. p. 39". The substance is oxidised by nitric acid a t 125-150" to 2 2- diethylindune-1 3-dione-4 5 7-tricarboxylic acid colourless crystals m. p. 249" (decornp.) after slight previous softening; when more drastically treated with nitric acid it gives benzenepentacarboxylic acid m. p. 232-233'. 2 2 4-Triethyltetrahydronaphth-up-hydrindene a colourless liquid b. p. 203-205"/19 mm. di0 0.9673 n$ 1.5352 is isolated from the products of t,he action of amalgamated zinc and hydrochloric acid on 2 2 4-triethyltetrahydronaphth-@-indane-l 3-&one. It con- denses with acetyl chloride in the presence of aluminium chloride and carbon disulphide to yield 5-acetyl-2 2 4-triethyltetrahydro- naphth-ap-hydrindene colourless needles m.p. 66" after soften- ing a t 63' which with p-nitrobenzaldehyde and potassium hydroxide solution gives the corresponding p-nitrobenxylidene derivative C,8H330,M canary-yellow needles m. p. 161.5". The acetyl compound is reduced by zinc and hydrochloric acid to 3 2 4 1 5-tetraethyltetrahydronaphth-ap-hydrindene a pale yellow very viscous liquid b. p. 220-222"/20 mm. dj7 0.9647 nz 1.5365. H. W. CH2 CH,,; I 4 p t 'HZ 11 2 I Dicyclic and Polycyclic Compounds with Bridged Linking. di~y~~o-[1,3,3]-Nonane and its Derivatives.HANS MEER- WEIN [with FRANZ KIEL GUSTAV KLOSGEN and EDWTN SCHOCH] ( J . pr. Chem. 1922 [ii] 104 161-206; cf. A. 1913 i 869).- dzcyclo-[l,3,3]-Nonan-2 6-dione the preparation of which has now been slightly improved has been further characterised by the formation of the unsaturated diucetyl derivative of the dienol form colourless needles m. p. 78-79". When the disemicurbam a white crystalline powder m. p. 226" is heated for six hours at 220" with 10% ethyl-alcoholic sodium ethoxide solution (cf. Wolff,i. 222 ABSTRACTS OF CHEMICAL PAPERS. A. 1912 i 988) dicyclononane (annexed formula) snow-white feathery plastic crystals m. p. 145-146" FH,-:H-~ b. p. 168-5-170" may be isolated from the product in 40% yield by distillation in steam.vH2 '(iH2 'iH2 Reduction of the dicyclononandione with CH2-7H-CH2 * sodium amalgam gives a mixture of a tri- cydononandiol (see below) and trans-dicyclo- [1,3,3]-nonan-2 6-diol m. p. 219" which gives a reddish-violet coloration with alcohol and sulphuric acid and a sapphire-blue coloration with acetic anhydride and sulphuric acid. The di- acetate m. p. 35" b. p. 173-174'117 mm. and the dibenxoate. glistening white leaflets m. p. 96-97' are described. On oxid- ation with chromic acid the dicyclo-glycol is reconverted into the diketone. When dehydrated with sulphuric acid it gives dicyclo- [1,3,3]-A6-nonen-2-ol m. p. 133" b. p. 224-226" which has an intense camphor-like odour is plastic gives the same colour reac- tions as the dicycZo-glycol and forms a liquid acetate b.p. 111- ll2"/12 mm. having an intense odour resembling that of pine needles. This unsaturated alcohol when reduced by means of hydrogen and platinum black gives an 88% yield of dicyclo- [1,3,3]-nonan-2-ol colourless crystals m. p. 185" which forms a liquid acetate b. p. 12S0/20 mm. and is oxidised by chromic acid mixture to dicyclo-[l,3,3]-nonan-2-one plastic colourless crystals m. p. 150'; the ketone is characterised by the semicurbaxone colourless needle-shaped crystals m. p. 180-181 ' the benzylidene derivative m. p. 127-128" which dissolves in concentrated sulphuric acid with a lemon-yellow coloration and the cinnamylidene deriv- ative yellow needles m. p. 116-117" which similarly gives an orange-red coloration. Attempts to eliminate two molecules of water from the dicyclo-glycol have led only to resinous products probably because the second double bond appears in the 5 6 and not the 6 7 position the resulting hydrocarbon then isomeris- ing to cyclooctatetrene which is well known to polymerise easily.As mentioned above the reduction of the dicyclo-diketone leads also t o tricyclo-[l,32,36,0]-nonan-2 6-diol (annexed formula) which yH2-yH-F.0H may most readily be obtained by using the crude reduction product for the preparation yHz,/&2 c;H2 of the dicyclononenol it being then isolated unsaturated alcohol has been removed in a current of steam. It forms glistening needles m. p. 141" is appreciably volatile in steam dissolves without any coloration in concentrated sulphuric acid and is oxidised by chromic acid in glacial acetic acid solution to the original dicyclo-diketone.The diacetate tabular crystals m. p. 121" the dibeiaxoate needles m. p. 153-154" and the diphenylurethane fine needles m. p. 201" are described. iwethyl dicyclo-[l,3,3]-nonan-2 6-dione-1 3 5 7-tetracarboxylate forms with sodium methoxide (1 mol.) a white crystalline mono- sodium derivative which is decomposed by water into the free ester (1 mol.) and the disodium derivative (1 mol.); the latter which OH.C '/ CH-bH I from the sulphuric acid residue after theORGANIC CHEMISTRY. i. 223 is directly produced from the ester and sodium methoxide (2 mols.) is a colourless crystalline hygroscopic powder dissolving in water with opalescence. The action of bromine (2 atoms) on the mono- sodium derivative gives methyl 3-bromodicyclo-[ 1,3,3]-mmn-2 6- dione-1 3 5 7-tetracarboxylate rhombohedra m.p. 154" which is soluble in dilute alkalis and gives a reddish-violet coloration with ferric chloride. Methyl 3 7-dibromodicyclo-[l,3,3]-nonan- 2 6-dione-l 3 5 7-tetracarboxylate7 colourless prisms which is formed from the above-mentioned disodium derivative and bromine (5 atoms) is insoluble in alkalis does not give a coloration with ferric chloride and melts a t 142" with elimination of bromine giving methyl tricycl0-[1,3~,3~,0]-nonan-2 6-&one-l 3 5 7-tetra- carboxylate (annexed formula) colourless prisms from xylene and glacial acetic acid leaflets from amyl- alcohol m. p. 247-248". The same compound is produced by the action CO2Me*C'--]--$XO,Me of sodium and zinc dust in xylene solution on the dibromo-ester by the action of bromine on the disodium derivative or by the thermal decom- position of the copper compound of the dicyclo-tetracarboxylic ester (A.1913 i 869) but is most readily prepared by treating the monobromo-ester with sodium methoxide (1 mol.) care being taken to avoid excess of alkali during the reaction. The tricyclic ester undergoes fission with methyl-alco- holic sodium methoxide two molecules of methyl alcohol being taken up with formation of a methyl cycloheptanehexacarboxyhte white needles from amyl alcohol large prisms from methyl or ethyl alcohol m. p. 128" which must have one of the formuh (I) (11) or (111) according as fission occurs in the positions 2 3 and 6 7 1 2 70,Me 7H2-v-y0 I $332 I CO-v-CH C0,Me y02MeC;0,Me ( 5 O,Me),( 5 Q2Me )2 5 H- CH*CH2>C(C0,Me) CH2--C- CH2 CH -qH*CH y-- C-CH2\ CHC0,Me C0,Me (111.) and 5 6 or 1 2 and 6 7 respectively.The corresponding cyclo- heptanehexacarboxylic acid obtained by hydrolysing the ester with aqueous barium hydroxide separates from glacial acetic acid or anhydrous formic acid as a microcrystalline powder m. p. 177" (decomp.) and loses carbon dioxide when heated with water and a trace of hydrochloric acid giving cycloheptane-1 3 5 6-tetra- carboxylic acid m. p. 233" which is probably a mixture of several of the five possible stereoisomeric forms and may be derived equally well from any of the three possible hexacarbomethoxy- esters. Alternate formuh are suggested for the dianhydride m.p.i. 224 ABSTRACTS OF CITEMICAL PAPERS. 197-198". When the tricyclo-ester is heated with aqueous barium hydroxide hydrolytic fission of the bond 702H 2 3( 2) occurs with formation of dicyclo- CO2H*CH-CTH [ 1,2,3 1-octan- 8-one-pentacarbox ylic acid $0 y(CO,H) (probable formula annexed) beautiful transparent prisms which melt a t 18" 185" with evolution of carbon dioxide but not of water. C02H Oxidation of the dicyclononenol (above) with chromic anhydride in glacial acetic acid solution gives dicyclo-[1 ,3,3]-A6-nonen-2-one a white plastic mass of camphor-like odour m. p. 82" b. p. 213- 217" ; it forms a semicarbaxone star-shaped clusters of needles m. p. 190-5-191" and a cinnamylidene derivative yellow needles m. p. 117" which dissolves in concentrated sulphuric acid with an orange-red coloration.By the reduction of the dioxime of the dicyclononandione (A. 1913 i 869) by means of sodium and alcohol trans-2 6-diaminodicyclo-[l,3,3]-nonane is produced as a transparent crystalline hygroscopic mass b. p. 125-130/14 mm. which has a strong odour characteristic of bases and rapidly liquefies in contact with the air. The dihydrochloride colourless non- hygroscopic crystalline powder the diacetyl derivative glistening clusters of needles m. p. 214" and the dibenxoyl derivative indefinite crystals m. p. 351" are described. Distillation of the dihydro- chloride gives 2-aminodicyclo- [ 1 ,3,3]-A6-nonene a colourless trans- lucent crystalline mass m. p. 37.5" b. p. 104"/17 mm. which rapidly liquefies on exposure to the air possesses a strong odour reminiscent of both conine and nicotine and is immediately oxidised by potassium permanganate in sulphuric acid solution.Space formuh are used to indicate the absence of strain not only in dicyclo-[l,3,3]-nonane itself but also in the tricyclopinacone the 2 6 bridge-bond of which is opened and closed with extra- ordinary ease and in the tricyclo-tetracarboxylic ester the pro- duction of which by the thermal elimination of free bromine provides an entirely new type of ring formation. Since the tricyclononan- dionetetracarboxylic ester is nearly " spannungslos," the ready formation by the action of sodium methoxide of a cycloheptane ring is taken to indicate that the latter is also free from strain and therefore probably lies in more than one plane.The stability of the dicyclononandionetetracarboxylic ester and the ready fission of the tricyclo-ester with alkaline reagents are ascribed to the presence in the former but not in the latter of hydrogen attached to the ring-atoms 3 and 7 (cf. Dieckmann A. 1901 i 539). A similarity is indicated between the physical properties of the dicyclononane derivatives and compounds of the camphor series ; this does not however extend to the physiological properties examples of which contributed by Schuller are quoted. I CH2*y-CH W. S. N. Cryoscopic Investigations on the Capacity to form Schiff's Bases. BERNARDO ODDO and FRANCESCO TOGNACCHINI (Gazzettct 1922 52 ii 347-361).-The method previously used (A. 1913 i,ORGANIC CHEMISTRY. i. 225 1233; 1915 ii 414 415 and this vol.i 255) has now been applied to the investigation of the course of the reaction between aniline and a number of aliphatic and aromatic aldehydes and ketones. The molecular weight calculated from the depression of the freezing point of the aniline is expressed as a percentage of the theoretical value for the aldehyde or ketone taken and the result plotted as a function of the time. Like all aromatic aldehydes p-tolualdehyde reacts promptly with aniline whereas phenylacetaldehyde reacts decidedly more slowly ; with cinnamaldehyde the reaction takes place more easily. As in the reaction with phenylhydrazine anisaldehyde reacts with aniline far more rapidly than does vanillin the hydroxyl group apparently exerting a retarding effect ; a similar effect is exercised by a nitro-group in the meta-position to the aldehyde group.Anis- aldehyde cuminaldehyde p-nitrobenzaldehyde and p-tolualdehyde all of which are substituted in the para-position exhibit similar molecular weight-time curves. The reaction is relatively slow with aromatic and more rapid with aliphatic ketones mixed ketones showing intermediate behaviour. The results given by benzil acetylacetone and acetonylacetone show that the reactivity increases with the degree of separation of the two carbonyl groups; with benzil however it is doubtful if the reaction proceeds in the direction of the formation of the Schiff’s base. Further it seems that only one carbonyl group reacts in the case of P-diketones whereas both carbonyl groups of the 7-diketones react.With acetylacetone and acetonyl- acetone the experimental conditions and with the former also the results obtained preclude the formation of heterocyclic nuclei. Camphor reacts not a t all with aniline and menthone and carvone only slowly. As regards the cyclohexane ketones the reaction is slowest with the ortho- and most rapid with the para- substituted compounds cycbhexanone occupying an intermediate position. Phenanthraquinone and santonin react slowly and phenolphthalein instantaneously the stage reached in ten minutes persisting unchanged for twenty-one hours. Preparation of a-Homopiperondl from Safrole by the Action of Ozone and Synthesis of its Derived Perfumes. I. SH~ICHIRG NAGAI ( J . Chem. Ind. Japan 1922 25 1409-1421; cf. S. Nagai ibid.1922 25 631).-By passing about 36 litres per hour of air containing 2-3% of ozone into a glacial acetic acid (10-15 parts) solution of safrole (1 part) at the ordinary tem- perature safrole ozonide is produced readily. The ozonide is however liable to decompose spontaneously even a t the ordinary temperature when freed from the solvent or when heated and is also readily polymerised into resinous matter by the effect of heat air alkali etc. If the ozonide is decomposed by adding gradually water and zinc powder to the acetic acid solution a yield of about 60-65% of a-homopiperonal is obtained which is further purified by conversion into the additive product with sodium hydrogen sulphite. a-Homopiperonal is a light yellow oil b. p. T. H. P.i. 226 ABSTRACTS OF CHEMICAL PAPERS.131-133"/8 mm. di6 1-2654 n1,5 1.5547 and gives an oxime white needles m. p. 119" semicurbaxone white crystals m. p. 176-177" and phenylhydraxone light yellow crystals m. p. 176". Gallaldehyde. KARL W. ROSENMUND (Ber. 1923 56 [ B ] 136).-In reply to the recent observations of Nierenstein (this vol. i 91) the author maintains that the acidity of gallaldehyde is sufficiently great to prevent its isolation from sodium carbonate solution in the manner described by Nierenstein. KARL CEDER- QUIST and BROR HOLMBERG (Ber. 1923 56 [B] 298-300).-The formation of a solid product CI2Hl60 was observed in the con- densers during the purification of wood spirit distilled without previous neutralisation from pyroligneous acid derived from a mixture of pine wood (80%) and spruce wood (20%).It forms colourless prisms m. p. 69-70' and is optically inactive. It appears to be either an aldehyde or a ketone since it is convertible into a semicarbazone flattened needles or thin prisms m. p. 198- 199" and two oximes long flattened prisms m. p. 110-113" and hairs or needles m. p. 85-86'. Action of Organomagnesiwn Compounds on Nitriles. Action of Magnesium Phenyl Bromine. LOUIS BUY (Bull. Xoc. chim. Belg. 1922 31 397-410).-The action of magnesium phenyl bromide on nitriles has been studied to compare i t with that of magnesium methyl and ethyl bromides (cf. Bruylants Bull. A d . roy. Belg. 1922 [v] 8 7 ; Baerts A. 1922 i 817). In general far higher yields of ketone are obtained than is the case with the magnesium methyl and ethyl bromides none at all for example being formed when these react with acetonitrile whereas mag- nesium phenyl bromide gives a yield of about 45% of ketone.In the case of the aliphatic nitriles the yield of ketone increases with increase of the length of the carbon chain. In the case of benzonitrile the intermediate product diphenyl- ketimine CPh,:NH was isolated in 75% yield and is characterised by exceptional stability compared with those ketimines in which an alkyl group is united to the ketonic carbon. This is attributed to the fact that in diphenylketimine there is no possibility of tautomeric change of the type NH:CR*CH,Me NH,*CR:CHMe. The nitrile of cycbpropanecarboxylic acid also gave a good yield of phenyZcyclopropyZketimine a liquid of pungent disagreeable odour b.p. 135-136'/25 mm. d:" 1.0663 n$ 156201. It is rapidly converted by dilute acid into phenyl cycbpropyl ketone (Perkin T. 1885 47 840)) a liquid of pleasant odour b. p. 239" di0 1.0566 n; 1.5565. Phenylacetonitrile acetonitrile propionitrile and n-butyronitrile yielded the ketone and condensation products but the ketimine was not obtained. P. M. The Formation of Ketazines Phenylhydrazones and Semicarbazones of Ring-substituted Acetophenones. W. J. BRUINING (Rec. trav. chim. 1922 41 [ii] 655-686).-1n order to K. K. H. W. A New Compound from Conifer Distillates. H. W. The semicurbaxone has m. p. 189".ORGANIC CHEMISTRY. i. 227 ascertain whether acetophenone derivatives react with hydrazine phenylhydrazine and semicarbazide in an analogous manner to those of benzaldehyde the author has studied the formation of ketazines phenylhydrazones and semicarbazones of ring-sub- stituted acetophenones.The general conclusions drawn are ( 1 ) that glacial acetic acid is a suitable solvent for the preparation of such phenylhydrazones (2) that the ketazines are only formed in acid solution their preparation presenting no difficulty when hydrazine sulphate is used whilst a boiling solution of hydrazine brings about no reaction (3) that the nature of the ketone used is related to the speed of formation of the ketazine and conditions the state of equilibrium when formation and decomposition of ketazine are taking place at equal rates (4) that the formation of the semicarbazones occurs more rapidly in acid than in alkaline or neutral solution but excess of acid decomposes the semi- carbazones into their constituents and (5) that in some cases the nitro-group in the ortho-position with respect to carbonyl con- siderably diminishes the reactivity of the carbonyl group.The following substances are described p-acetamidoacetophemeket- axine yellow crystals m. p. 31 1" ; p-acetamidoacetophemphenyl- hydrazone m. p. 196-200" ; p-acetumidoacetophenonesemica;rbaxon,e white crystals decomp. 220" ; 3 6-dibrm-p-aminoacetophenone- ketaxine yellow crystals decomp. 297" ; 3 5-dibromo-p-amino- acetophenonesemicurbazone white crystals m. p. 255" (decomp.) ; 3 5-dibromo-p-acetamidoacetophenone m. p. 188-189" yielding a ketuxine yellow m. p. 344" (decomp.) a phenylhydraxone pale yellow crystals m.p. 244-246" and a semicarbazone white crystals decomp. 325" ; 3 5-dibromo-p-diacetamidoacetophenone obtained in two modifications (a) unstable m. p. 67" which passes after some days into ( b ) stable m. p. 88"; 3 5-dibromoacetophenone- ketaxine m. p. 231 " ; 3 5-dibromoacetophenonephenylhydraxone light yellow needles m. p. 109-110" ; 3 5-dibromoacetophenone- semicurbaxone white crystals m. p. 268" (decomp.); 3 4 5-tri- bromoacetophenone white crystals m. p. 134-135" yielding a ketaxine small yellow crystals m. p. 300" a phenylhydraxone yellow crystals m. p. 129-134" and a semicarbaxone white crystals decomp. 265" ; 3" 5-dibromo-2-nitroacetophenone pale yellow crystals m. p . 133-144" yielding a Eetaxine m. p. 210" a phenylhydraxone m. p. 165-166" and a semicurbaxone m.p. 234" (decomp.); 3 4 5-tribromo-2-nitroacetophenone white needles m. p. 188- 189*5" yielding a ketazine yellow needles m. p. 244" a phenyl- hydrazone red crystals m. p. 173-174" and a semicurbaxone decomp. 249". H. J. E. The Action of an Alcoholic Solution of Potassium Hydr- oxide on Ketones. VII. The Action of an Alcoholic Solution of Potassium Hydroxide on p-Hydroxy- and p-Ethoxy- benzophenone and their m-Bromo-derivatives. P. J. MONTAGNE (Rec. trav. chim. 1922 41 703-721; cf. A. 1920 i 394).-The action of alcoholic potassium hydroxide on benzo- phenones effects the reduction of the carbonyl group to an alcoholici. 228 ABSTRdCTS OF CHEMICAL PAPERS. group and also in the case of halogen-substituted benzophenones the partial replacement of halogen atoms in the ring by hydrogen.A retarding action is exerted by the ethoxyl group in the para- position ; this is considerably diminished by the presence of a bromine atom in a similar position in the other ring. In the case of benzo- phenone itself heating at 100" for two days completes the reduc- tion whilst on heating 4-ethoxybenzophenone for six days under similar conditions so little change occurs that it is found impossible to isolate the reduction product. On introducing a bromine atom into the meta-position in the ring to which the ethoxyl group is attached the greater part of the substance is reduced after two days ; a second bromine atom in the meta-position in the same ring entirely masks the retarding effect of the ethoxyl group and the substance behaves similarly to benzophenone. The author points out that the action of bromine is similar in the case of 4 4'-di- bromo-3 3'-diaminobenzophenone (A.1917 i 143). None of the corresponding hydroxybromobenzophenones is reduced even after prolonged heating so that the effect of the hydroxyl group in inhibiting reduction is not diminished to any appreciable extent by bromine. The products resulting from the action of alcoholic potassium hydroxide on 3 5-dibromo-4-ethoxybenzophenone are 3 5-dibromo-4-ethoxybenzhydro1 3-bromo-4-ethoxybenzhydrol and 3 5-dibromo-4-hydroxybenzophenone the two last-named being formed in small quantity. Hydrolysis of the ethoxyl group thus takes place to a limited extent. The introduction of a second ethoxy-group into the other ring increases the influence of the first and reduction is then incomplete after heating for six days.The following substances were prepared 3'- bromo-4-hydroxy- benzophenone crystals m. p. 171" ; 3-bromo-4-ethoxybenmpherwne rhombic bipyramidal crystals (a b c=0*7935 1 0.2691) m. p. 102*25" ; 3-brom0-4-ethoxybenxhydro.J colourless crystals m. p. 85" ; 3 5-dibrm-4-ethoxybenzophenone colourless monoclinic crystals (a b c=1.0901 1 0.8591 ; p=59" 41') m. p. 83.5" b. p. 244"/11 mm. ; 3 5-dibromo-4-ethoxybenxhydroZ small needles m. p. 81.75" ; 3'-brorno-4-etbxgbenzophenone colourless crystals m. p. 79.5" b. p. 232"/11 mm. ; 3'-bromo-4-ethoxybenxhydroZ needles m. p. 43"; 3 5-dibromobenmphenone m. p. 75" b. p. 232'118 mm. ; 4 4'-diethoxybenzophenone small colourless plates m.p. 132" b. p. Z5S0/15 mm.; 4 4'-diethoxybenxhydrol crystals m. p. 59". 4-Ethoxybenzophenone crystallises in the monoclinic system (a b ~=0*7427 1 1.6049; p=87" 58'). H. J. E. Formation and Transformation of the Naphthyl Ketoximes. ERNST BECKMANN OTTO LIESCHE and ERICH CORRENS (Ber. 1923 56 [B] 341-354).-The isomerism of ketoximes has been explained by Hantzsch and Werner in accordance with the principles of ethylenic isomerism and the arbitrary but plausible assump- tion that the vicinal groups in these compounds exchange places during the course of the Beckmann transformation has been generally accepted until recently. Bucherer however (Lehrhch der Farbenchemie 1914) has put forward a scheme in which theORGANIC CHEMISTRY. i. 229 R1*C*R2 R2*C*OH R2*C:0 subsidiary valencies (I) are + 1 1 -+ I considered to become con- R,*N R1.NH verted under the conditions (11.) (111.) of the change into principal valencies with consequent conversion of the form I into form 11 from which the stable modification (111) of the transformation product is readily derived.The transformation thus consists in a change of position between the hydroxyl group and the oppositely situated radicle. Similar views have been expressed more recently by Biltz and Rob1 (A. 1921 i 891) and by Meisenheimer (A. 1922 i 152 176). The conception has the advantage that the chemical unity of the molecule is regarded as being in a measure preserved throughout the change whereas the direct exchange of position of two neigh- bowing groups is scarcely possible without intermediate rupture of the molecule. Confirmation of this view of the transformation is deduced in a somewhat different manner.In accordance with Abegg’s electro- chemical view of the stability of oximes the disposition of the relatively positive and negative radicles in the alkali-stable and “ acid-stable ” oximes must be that shown in the annexed formulae (IV) and (V). It is found that in the “alkali-stable” form the more strongly negative radicle R1 wanders RI.c.& whereas in the ‘‘ acid-stable ” variety the less strongly negative radicle R2 migrates The evidence (v.) is based on the behaviour of the phenyl naphthyl ketoximes (Betti and Becciolini A. 1916 i 49; Poccianti A. 1915 i 822) and the dinaphthyl ketoximes in which in accordance with the dissociation constants of the corresponding carboxylic acids the phenyl and p-naphthyl groups are considered to be about equally negative and consider- ably inferior in this respect to the cc-naphthyl radicle.Difficulties appear to be encountered when these views are applied to aldoxjmes. The varieties which readily yield nitriles are in general favoured by the action of acids R.c.6 6.c.k and to them the constitution VI must be ascribed whereas the isomerides which can HO* + 1 NOH be successively esterified and hydrolysed ( ~ 1 . 1 ( ~ 1 1 . ) without undergoing decomposition must have the configuration VII. This however is contrary to the accepted view that the water-forming groups must be obtained from vicinal positions in the compound. The change is possibly explicable in accord- ance with the annexed scheme. In any case it appears to be established that in the acid-stable variety of aldoximes (syn-oxime) the hydrogen as positive radicle wanders when the change resulfs in the formation of a nitrile or when a normal Beckmann rearrange- ment occurs.’.? . !&:OH (1.1 R 1 . ~ . & 2 #.OH HO.N -+ II during the Beckmann change. (W.1 R*L+ a*c i4 iHO*NI I - 7 HO* Ni. 230 ABSTRACTS OF CHEMICAL PAPERS. Di-p-naphthylketoxime needles m. p. 180-181" is convertsd by phosphorus pentachloride in the presence of anhydrous ethyl ether into p-naphtho- p-naphthyhmide colourless lustrous needles m. p. 239" the constitution of which is established by its synthesis from p-naphthoyl chloride and p-naphthylamine. Di-a-naphthyl- ketoxime small colourless needles m.p. 200" is transformed similarly into a-naphtho-a-naphthylamide m. p. 241". a-Naphthyl P-naphthyl ketone m. p. 135" is prepared by the action of mag- nesium u-naphthyl bromide on p-naphthonitrile (the intermediate compound ap-(C10H,)2C:N*MgBr yellow crystals m. p. 255" was isolated); it is converted quantitatively in acid solution at 135- 140" into u-naphthyl (3-naphthyl ketoxime m. p. 171" which is transformed into u-naphtho- p-naphthylamide colourless needles m. p. 200" identical with the product obtained by the action of a-naphthoyl chloride on p-naphthylamine. H. W. Studies in the Anthracene Series. IV. EDWARD DE BARRY BARNETT and MARCUS AURELIUS MATTHEWS (T. 1923 123 380-394). Benzaurin. RICHARD MEYER and WILLY GERLOFF (Ber.1923 56 [B] 98-104).-1n a previous communication (Meyer and Fischer A. 1913 ii 167) it has been shown that the absorption spectrum of benzaurin is so similar to that of fuchsone that it must almost necessarily be regarded as a p-hydroxyfuchsone OH4?,H4*CPh:C6H4:0. Analysis of the dye however gives results which are in harmony with the formula OH*CPh(C,H,-OB),. It is found however that a molecular proportion of water is readily lost when the dye is heated and that the residue has the composition of p-hydroxyfuchsone. Benzaurin is therefore re- garded as a hydrate of p-hydroxyfuchsone. This conception explains the behaviour of the substance when dissolved in alcohol or acetic acid (Meyer and Fischer Zoc. cit.) the deepening in colour observed when the alcoholic solution is warmed and the form- ation of an orange-coloured solution in the cold acid being attribut- able to the withdrawal of water and the production of the more intensely coloured p-hydroxyfuchsone.Since benzaurin obtained by Doebner's method from benzo- trichlorido and phenol (p-hydroxybenzophenone is formed as by- product) is not crystalline and has not a definite melting point various attempts have been made to secure a more definitely homogeneous product. The oxidation of 4 4'-dihydroxytriphenyl- methane m. p. 161" (acetate m. p. 115") or the hydrolysis of benzaurin diacetate m. p. 119" or benzaurin dibenzoate colourless needles m. p. 183-184" did not lead to the desired result. More success is obtained by decomposing benzaurin perchlorate (cf.Pfeiffer A. 1917 i 210) with the requisite quantity of sodium hydroxide and subsequently adding dilute sulphuric acid; whereby benzaurin is caused to separate as a brilliant red precipitate. It loses one molecular proportion of water a t 110-120". Benmurin hydrochloride dark red needles is obtained by theORGANIC CHEMISTRY. i. 231 addition of an excess of fuming hydrochloric acid to a solution of benzaurin in glacial acetic acid. Di- and Tri-hydroxydeoxybenzoins. ERNEST CHAPMAN and HENRY STEPHEN (T. 1923 123 404409). The Reactivity of Doubly-conjugated Unsaturated Ketones. IV. The Effect of Substitution on the Reactivity of 4'-Di- methylamino-2-hydroxydistyryl Ketone. ISIDOR MORRIS HEILBRON and ABRAHAM BRUCE WHITWORTH (T 1923 123 The Benzilic Acid Transformation.I. G. SCHEUING (Beri 1923 56 [B] 252-259).-1t is shown that the bluish-violet dye which is produced during the preparation of benzilic acid from benzil and ethyl-alcoholic potash has no direct effect on the trans- formation. The attempts which have been made previously to explain the course of the benzilic acid transformation assume the rupture of one or both double bonds between the carbon and oxygen atoms of benzil by the addition of water or potassium hydroxide. Such compounds have now been isolated. B e n d potassium hydroxide C14Hlo02,KOH small indistinct pale yellow crystals is obtained when an intimate mixture of benzil and dry potassium hydroxide is triturated beneath a Little pyridine or benzene or by the addition of a concentrated alcoholic solution of potassium hydroxide to a cold solution of benzil in ether.It is decomposed into its components by water and into potassium hydrogen carbonate and benzil by dry carbon dioxide. It is con- verted slowly at 0" in a few hours at the atmospheric temperature and almost instantaneously at 80" into potassium benzilate so that it appears to be a definite intermediate product of the con- version of benzil into benzilic acid. In a similar manner the addition of a solution of potassium in methyl alcohol and ether to an ethereal solution of benzil leads to the separation of the compound C14H,o02,MeOK,MeOH small almost colourless crystals which is decomposed by water alcohol or carbon dioxide in the same manner as the product from potassium hydroxide.On the other hand it does not undergo a similar smooth transformation which only occurs to the extent of 15% when it is preserved beneath ether during two days a t the atmospheric temperature. The product of the change is benzilic acid whereas methyl benzilate or methoxydiphenylacetic acid would be expected. Transformation does not take place to any considerable extent when it is heated in the presence of benzene; the main products are unchanged benzil and benzoin the latter being formed owing to the reducing action of potassium methoxide. Bend sodium ethoxide C14H,o02,EtONa a pale yellow distinctly crystalline substance is prepared by the addition of sodium ethoxide dissolved in a mixture of ethyl alcohol and xylene to a solution of benzil in the latter solvent.The formation of benzil potassium ethoxide can only be observed at a low temperature; it becomes altered in an unexplained manner a t 0". H. W. 238-245). H. W.i. 232 ABSTRACTS OF CHEMICAL PAPERS. The Beckmann Transformation in the Cases of 0- and p-Quinoneoximes. ERNST BECKMANN and OTTO LIESCHE (Ber. 1923 56 [BJ 1-23).-The experiments described do not establish beyond all doubt the normal course of the Beckmann trans- formation in the cases of p - and o-quinones. The expected enlarge- ment of the ring appears to be proved most conclusively in the instance of anthraquinonemonoxime. The direct action of the transforming agents on dioximes does not appear to lead to the production of an eight-membered ring containing two nitrogen atoms but this seems possible in the case of anthraquinone if the monoxime is first transformed and the product converted into its oxime and again transformed.I. Phenanthraquinone- and naphthaquinone-oxime [with HERBERT DIETRICH].-T~~ action of phosphorus pentachloride on (3-naphtha- quinoneoxime [2-nitroso-cr-naphthol] has been studied by Borsche and Sander (A. 1915 i 299) who have isolated a product to which they ascribe 'the constitution COC1*C6H,*CH:CHC~ but for which the cyclic structure C6H4<gg.iz>C0 appears to the authors to be equally possible. The same chloride colourless matted needles m. p. 80° is obtained by the action of phosphorus pentachloride on the oxime in the presence of light petroleum. It is converted by ammonia in the presence of anhydrous ether into the substance C,,H,0N2 m.p. 207" and by boiling water into the monobasic acad C10H,02N m. p. 179" the silver sodium potassium and barium salts of which are described. It is hydrolysed by boiling aqueous sodium hydroxide solution to o-carboxycinnamic acid m. p. 184" (the silver salt is described). The action of a saturated solution of hydrogen chloride in a mixture of glacial acetic acid and acetic anhydride or of benzenesulphonyl chloride in the presence of pyridine on p-naphthaquinoneoxime gives the acid C,,H,O,N m. p. 179" the properties of which appear to the authors to be compatible with either the cyclic or open structure. p-Naphthaquinonedioxime is converted by phosphorus penta- chloride in the presence of light petroleum by the Beckmann mixture and by benzenesulphonyl chloride and pyridine into the anhydride C1,H60N m.p. Sl" the ready formation of which causes a stabilisation which inhibits the Beckmann transformation. a-Naphthaquinonemonoxime [4-nitroso-a-naphthol] does not undergo a smooth transformation with any of the reagents investi- gated. With Beckmann's mixture it yields a cornpound Cl2H,O3NC1 long needles m. p. 165" after previous softening. With benzenesulphonyl chloride and pyridine the ester c('o'so2ph) :YH colourless matted needles m. p. 183- c6H4<C(NO)=CH' 184" is produced. a-Naphthaquinonemonoxime is not affected by boiling acetyl chloride but is converted by the cold reagent into ill-defined compounds containing halogen. The acetyl derivative C H <C(*oAc):?H lustrous brown needles m. p. 132~5"~ is obtained readily by the action of acetic acid and acetic anhydride; C( NO)= CH' 6 4ORGIANXC CHEMISTRY.i. 233 it does not yield homogeneous products when treated with the transforming agents. a-Naphthaquinonedioxime is converted by the Beckmann mixture into the corresponding diacetate m. p. 164" which is transformed by the reagent at a higher temperature into ill-defined chIorinated compounds. 11. Benxoquinone- and Anthraquinone-oximes [with A. PHILIPPO- VICH VON PHILIP~~~~~~].-p-Benzoquinonemonoxime is converted by benzenesvlphonyl chloride in the presence of pyridine into the corresponding ester m p. 131" which (without being isolated) is transformed by being further heated and subsequently treated with sulphuric acid into the compound CO\ brown needles m. p.224". The substance dissolves in solutions of alkali hydroxides and carbonates yielding soiutions from which the cobalt silver molybdenum mangawse tin zinc l d and iron salts are prepared; it gives a benzoyl derivative leaflets m. p. 189- 190". Many attempts are described to effect the transformation of p-benzoquinonedioxime but these have not been successful. Apparently the conversion only occurs if a certain minimum temperature is exceeded (below which only salt formation takes place). With the compound in question this temperature is so high that when augmented by the local and unavoidable heat of the reaction i t causes the extensive decomposition of the products of the change. Anthraquinonemonoxime is converted by a mixture of phosphorus pentachloride and acetyl chloride into the compound short colourless needles m.p. 245" which is transformed by BUC- cessive treatment with boiling sodium hydroxide solution and acid into 2 -0 -aminobenzoyl benmic acid NH,*C 6H,*C 0-C ,H4*C0,H m. p. 199" (decornp.) the silver lea& and wpper salts of which are described. It yields a methyZ ester m. p. (indefinite) 168-173". The presence of the amino-group is established by its ability to yield a diazo-compound. Anthraquinonemonoxime is converted by it mixture of phosphorus pentachloride and phosphoryl chloride into the phosphoric acid derivative which is isolated as the silver C H salt CO< 6 4>C:N*O*PO( OAg) whereas benzenesulphonyl chlor- ide and pyridine transform it into the corresponding ester C,,H,,O,NS slender colourlew needles m.p. 154". The trans- formation product Cl4H,O,N is converted by further freatment with hydroxylamine hydrochloride in boiling alcoholic solution (96%) into the corresponding oxime C6H4<gg%y>C& colourless needles M. p. 243" (decomp.) [benzoyl derivative m. p. 209"] which is converted by the Beckmann mixture at 170" into phthalyl-o-phenylenediamine 6 H <co*NH co,NH>C&4 m. p. 275- /CH:CH*yO yellohh- CH:CH*NH' c,H,<;:;p,I c,H,i. 234 ABSTR-4CTS OF CHEMICAL PAPERS. 278" identical with the product synthesiaed by Anderlini and Meyer (A. 1906 i 765) for which however an alternative con- stitution has been suggested by Thiele and Falk (A. 1906 i 750). H. W. Arylamine Salts of the Anthraquinonesulphonic Acids. A. G. PERKIN and W. G.SEWELL ( J . SOC. Chem. Id. 1923 42 27-3 1 ~ ) .-The arylamine salts of the anthraquinonesulphonic acids are well-defined crystalline substances sparingly soluble in water or alcohol. They are readily obtained by adding an acic solution of the arylamine hydrochloride to a solution of the sodium salt of the sulphonic acid. The salts are useful for the purification of t'he alkali salts of the sulphonic acids and they can also be used for transforming one alkali or alkaline-earth salt into another as they are easily reconverted into a metallic salt by boiling with the requisite quantity of either aqueous or alcoholic slkali or alkaline-earth hydroxide. Certain of these salts notably the aniline salts can be employed with fair exactitude for the analysis of anthraquinone-mono- and -di-sulphonates by titrating a sus- pension of the aniline salt in boiling water with standard alkali hydroxide in presence of phenolphthalein.Advantage can be taken of the sparing solubility of the methylaniline compared with the dimethylaniline P-sulphonates to effect a fairly complete separation of methylaniline from a mixture of the two bases provided it is present in considerable amount. The following are among the salts described Aniline anthraquinone-2-sulphonute colourless needles m . p. 309" ; p-toluidine anthraquinone-2-sulphon- ate colourless needles m. p. 308" ; a-mphthylamine 2-sulphomte m. p. 253" ; aniline anthraquinone-1-sulphonate m. p. 284" ; methyl- aniline anthraquimne-2-sulphonute m. p. 202-203" ; dimethylanil- ine 2-sulphonate m.p. 192-194" ; 1-sulphomte m. p. 215" ; diethyl- aniline anthraquinone-2-sulphonute m. p. 174-175" ; the aniline salts of the following anthrayuinonedisulphonic acids 1 5- orange- yellow crystals; 1 8- needles; 2 6- plates; and 2 7- plates; none of these salts exhibited a melting point. The methyl- aniline salts of the 1 5-disulphonic acid m. p. 251" orange plates; 1 8-disulphonic acid 2 6-disulphonic acid needles m. p. 205- 210" and 2 7-disulphonic acid m. p. 230" are described as also are the corresponding dimethylaniline salts. Quinoline anthraquinone- 1-sulphnate melts at 195" and the 2-sulphonate a t 225". Pyridine a?tthraqziinone- 1 -sulphonate forms needles m. p. 158". G. F. nt. The Camphor Series. 11. SHICERU KOMATSU (Mem. Coll. Sci. Kyoto 1922 6 5&72).-[With KITARO Fu~~~.]-Applying Reformatzky's synthesis to d-camphor using ethyl 2-menthyl and d-bornyl esters of iodoacetic acid esters of boraylacetic acid were obtained all of which gave the same 1-isobornylacetic acid on hydrolysis.Ethyl isobornylacetute C,H,,:C(OH)*CH,*CO,Xt is a viscous liquid b. p. 108-112°/3 mm. [a12 -24.97". I-Menthy2 isobornylacetate was obtained as a syrup. d-Bornyl isobornyl- acetate m. p. 196-197" has [a] +17*44". I-Bornylacetic acid,ORGANIC CHEMISTRY. i. 235 prepared from the ethyl ester had [a]" -20*32" from the d-menthyl ester - 19-85" and from the d-bornyl ester -25.62" all in alcohol. For the barium salt in water values of [a]:" from 9.53" to 12.91" were observed. [With S ~ o z o YAMAGUCHI.]-when d-camphoroxime was reduced by Forster's method in amyl alcohol with sodium &-bornylamine and I-iaobornylamine were formed in the proportions of 65.9% of the former to 34.1% of the latter.The high proportion of laevo compound formed compared with the proportion of I - borneol formed by the reduction of d-camphor 19% may be attributed to the influence of the more positive amino-group on the a s p - metric transformation of the carbonyl carbon atom in the camphor molecule. When d-bornylamine was passed over thoria at 400° it was decomposed into camphene and ammonia. [With RISABURO N~K~1.1-when d-borneol was passed over thoria at 400" with ammonia gas no bornylamine was formed but d-camphene was obtained; in the same way I-borneol gave I-camphene. It is probable that camphene was not formed directly from borneol by the Wagner rearrangement but through the intermediate formation of bornylamine which as shown above decomposes into camphene and ammonia.Both d- and I-camphene gave the same I-isocamphane when reduced with hydrogen in pres- ence of nickel. Some specimens of d-camphene were found to solidify on keeping; the crystals had m. p. 50" [a] 3.17-61". The question of the existence of solid and liquid forms of camphene is being further investigated. Pinene of Spanish Turpentine. A. MADINAVEITIA (Anal. Pis. Quim. 1922 20 531-533).-By fractional distillation of different samples of Spanish turpentine collecting the fraction 154%-157' yields of pinene varying from 35 to 90% are obtained. Except in the case of turpentine from Pinus hlepensis the pinene obtained is dextrorotatory.The differences in yield of pinene by fractional distillation are attributed to the presence of varying amounts of nopinene. Castelamarin-A Bitter Principle from Castela Nicholsoni. LOUIS PIERRE BOSMAN (T. 1923 123 207-210). Chinese Tannin. J. HERZIG (Ber. 1923 56 [BJ 221-228).- The methylation of Chinese tannin by means of diazomethane has been reinvestigated and methylotannin (cf. Herzig and Tscherne -4. 1905 i 254) has been prepared in excellent yield. As judged by the specific rotation and methoxyl content the product must be regarded as homogeneous; if this is the case the yields show that the parent substance of methylotannin must be present to the extent of at least about 90% in Chinese tannin. Additional evidence of the chemical individuality of Chinese tannin i s thus adduced (cf.Iljin A. 1914 i 567; Freudenberg A. 1922 i 1170). The main reason for the poor yields of methylotannin which have been encountered frequently is to be found in ester trans- formation which leads to the production of methyl trimethoxy- E. H. R. G. W. R.i. 236 ABSTRACTS OF CHEMICAL PAPERS. benzoate. In two instances methyl pentamethyl-m-digallate was isolated and this appears to be the first instance in which this compound has been prepared from Chinese tannin directly. The improvement in the methylation of the tannin is brought about by the preliminary repeated distillation of the ethereal solution of diazomethane a t as low a temperature as possible and with the help of a dephlegmator.The residue after removal of the excess of the reagent and desiccation in a vacuum is solid and can be powdered ; occasionally it is obtained directly in pulverulent form. It is almost completely insoluble in cold methyl alcohol after treatment with which it has a methoxyl content almost identical with that of methylotannin obtained previously. After further purification from warm methyl alcohol it has [ayi +12*44" [a]"; +12*75" [a]'; + 12.22" in benzene solution (2y!.) whereas Herzig and Renner (A. 1909 i 713) found +9" to +11". H. W. [Tannins and Similar Substances. 11. Chinese Tannin.] KARL FREUDENBERG and WILHELM SZILASI (Ber. 1933 56 [B] 406).-The preparation of highly active Chinese tannin (A. 1922 i 1169) only succeeds when the crude tannin [a],+90" has remained for a protracted period in aqueous solution in contact with aluniinium hydroxide. H.W. Reduction of an Indanthrene Dye by Means of Sodium Hyposulphite. JOHN H. YOE and GRAHAM EDGAR (J. Physical Chem. 1923,27,6&73).-The reaction between an oxyindanthrene dye (Ponsol-yellow-G) and sodium hyposulphite has been investi- gated and it is shown that the reduction and solution of the dye involve (a) the comparatively rapid reaction of the dye with the hyposulphite to form an insoluble crystalline reduced dye and ( b ) peptisation of the latter by hydroxyl-ions with the formation of a colloidal solution. The rate of solution and the amount of dye peptised by a given solution depend on the state of subdivision of the dye. Positive ions tend to coagulate the solution and to retard the peptisation of the reduced dye.Oxygenase of the Bach-Chodat System. OBDULIO FERN~NDEZ and ANTONIO PIZARROSO (Awl. Fis. Quim. 1922 20 589-594; cf. Fernandez A. 1921 i 485).-The ability of a number of alkaloids and other compounds containing the group -CO*NH- to form oxides in the presence of hydrogen peroxide is investigated. The conclusions drawn are indefinite. Aristolochic Acid. ARMAND CASTILLE (3. Pharm. Belg. 1922,4,569-571; from Chem. Zentr. 1922 iii 1301).-Aristolochic acid from Aristolochia clementis A . longa and A. rotundifolia is identical with Pohl's aristolochine (A. 1892 874). It has mole- cular weight 343 and corresponds with the formula C,,H,,O,N. It gives on reduction a substance C1,H,,04N which is characterised by its fluorescence in solution and probably contains an anthra- quinone nucleus.G. W. R. J. S. G. T. Ability of Alkaloids to Form Oxides. G. W. R.ORGANIC CHEMISTRY. i. 237 Aldehydes derived from Cinchonine Quinine and their Acyl Compounds. L. SEEELES (Rec. truw. chim. 1923 42 69-104).-When quinine cinchonine or their acetyl or benzoyl derivatives are subjected to the action of ozone in cold chloroform solution addition occurs at the double linking of the vinyl group with formation of an ozonide which when treated with water decomposes into formaldehyde and a new aldehyde. The terms quininal and cinchoninal are suggested for the new aldehydes from quinine and cinchonine respectively. These and a large number of their derivatives are described. m-Chloropicric acid (3-chloro- 2 4 6-trinitrophenol) was found useful for obtaining derivatives of the new aldehydes since it readily precipitat'ed them in a crystal- line form and an estimation of chlorine provided a ready method of analysis.Quinine+2X (X=rn-chloropicric acid) yellow m. p. 217' (decomp.) ; cinchonine+X yellow crystalline clusters m. p. 198" ; +2X greenish-yellow crystals m. p. 209" ; acetylcinchonine +X greenish-yellow m. p. 188"; +2X yellow m. p. 143-144"; benzoylcinchonine+X yellow m. p. 140-141" ; +2X yellow m. p. 156" ; acetyZquinine+2X m. p. 139" ; benxoylpuinine+X greenish-yellow m. p. 129-130"; +2X yellow crystals m. p. 150". Acetylcinchonine when pure has [a] +139*5" in water con- taining 3 mols. HC1; it could not be crystallised. Acetyl- quinine under the same conditions has [0!]'4;''~ -120.8" m.p. 116". It crystallises in the bisphenoidal class of the rhornbic system u b ~=1.1142 1 0.6119. Acetylcinchonine oxonide forms a white voluminous mass soften- ing a t 75" decomposing a t 95-100". Acetylcinchoninul was ob- tained as a white amorphous substance having a marked tendency to polymerise m. p. 106-109"; [a]:'" +28*2". Attempts to hydrolyse the acetyl group were unsuccessful. It forms it mono- m-chloropicrute m. p. 155" and a di-m-chloropicrute m. p. 156- 165". The phenylhydruzone of acetylcinchoninal is an amorphous powder m. p. 135-142" ucetute amorphous m. p. 106"; p4womo- phenylhydruzone yellow powder m. p. 126" acetate yellow m. p. 105" ; p-nitrophenylhydruxone yellow powder sintering from 125" m.p. 134" decomp. 141"; acetate yellow m. p. 90". When the last was recrystallised from alcohol small yellow crystals m. p. 226" were obtained but were not identified. The phenylhydrazone forms a m-chZoropicrute m. p. 154-165" (decomp.). L4cetylcin- choninal also forms a compound with ammonia and one with sodium hydrogen sulphite. Benzoylcinchonine oxonide forms a white voluminous mass decomposing at about 100". Benzoylcinchoninul is a white sub- stance m. p. 130" (decomp.); -72.4". Its mono-m-chloro- picrute forms greenish-yellow crystals m. p. 165" and the di- m-chloropicrute yellow crystals m. p. 165". The phenylhydrazone is amorphous yellow m. p. 117-118" acetate m. p. 127"; p-bromo- phenylhydruzone orange ainorphous m. p. 120-122" acetate m. p. 112-114" ; p-nitrophenylhydrazone yellow m.p. 126- The following new salts of this acid were prepared. VOL. CXXTV. i. Ici. 238 ABSTRACTS OF CHBIMICAL PAPERS. 127" (decomp.) izcetute m. p. 130-131". An aldehyde-ammonia compound is indicated Acetylpuinine ozonide forms a very voluminous white mms softening at 75" decomposing at 90-105" with evolution of gas. Acetylpuininal is a white substance m. p. about 120" (decomp.) [a] " -63.5". It forms a mono-m-chloropicrate greenish-yellow m. p. 166" (decomp.) and a di-m-chloropicrate yellow softening and decomposing from 138". The phenylhydraxone is a yellow substance m. p. about 125" acetate very hygroscopic yellow m. p. 65"; p-bromophenylhydrazone yellow m. p. 120"; p-nitro- phenylhydrazone yellow m. p. 125". Acetylquininnlammonia is a white powder m.p. 82-85'. Benzoylquinine oxonide is a voluminous white mass m. p. 95- 100". Benzoylquiniml is a white substance m. p. 126"; [aE'4 +79.4" ; mono-m-chloropicrute greenish-yellow m. p. 142" (decomp.) ; di-m-chloropicrate yellow blackening at 155". The phenylhydraxone is a yellow powder softening from 116" m. p. 128" acetate m. p. 118"; p-bromophenylhydrazone yellow m. p. about 125" acetate softens a t 118-119" (decomp.) ; p-nitro- phenylhydrazone yellow m. p. 122-133" acetate m. p. 112- 115" (decomp.). Benzoylquininal-ammonia. is a white substance m. I>. 131-132" containing 1 mol. of ether. When prepared in benzene solution it separates with 1 mol. of benzene m. p. 136-139". Cinchonine oxonide is a white amorphous substance not very voluminous decomposing at 105".Cinchoniml C,,H,,0,N2 is a white amorphous substance m. p. 143-146" [a]$'8 +l00*5" ; it readily reduces Fehling's solution and silver nitrate. It forms a mono-m-chloropicrale greenish-yellow crystals decomposing slowly at 151" and a di-m-chloropicrate decomp. at 155". The phenylhydrazone is amorphous m. p. 130-135" and decomposes violently at 140" ; p-bromophenylhydrazone yellow m. p. 120" ; p-nitrophenylhydraxone m. p. 130-132" (decomp.). These three hydrazones do not form acetates. Quinine oxonide is a white amorphous substance decomposing at 109". Quininal C19H2,08N2 forms small colourless crystals m. p. 160" having strong reducing properties [a] -30". The mono-m-chloqicrate forms yellow crystals m. p. 130" ; di-m-chloro- picrate a yellow vitreous substance m.p. 126" (decomp.). The phenylhydraxone has m. p. 145-147" ; p-bromophenylhydrazone yellow m. p. 125-130" (decomp.). Quininal does not form a compound with ammonia but forms an additive compound with sodium hydrogen sulphite in alcohol decomposed by water. E. H. R. The Synthesis of Ephedrine. E. FOURNEAU and J. PUYAL (Anal. Fh. Quim. 1922 20 394-399; cf. SpBth A 1921 i 45; Fourneau A. 1905 i 57; Eberhard A. 1915 i 834).-Ephedrine is obtained from phenylethylcarbinol by the following reactions. Dehydration of phenylethylcarbinol gives propenylbenzene ; by the action of bromine water the corresponding bmmohydrin 1sommrc CHEMISTBY. i. 239 obtained b. p. 145-155"/25 mm. By heating the bromohydrin with a 10% methylamine solution in a sealed tube at 120" for three hours phenyl-a-methylaminoethylcarbinol (ephedrine) is obtained and separated by appropriate methods.After recrystal- lisation colourless prisms are obtained m. p. 60". The hydro- chloride gives m. p. MOO subsequently rising to 190". The stereo- isomeric +-ephedrine is obtained from ephedrine hydrochloride by way of acetylation of the latter compound whereby acetyl +-ephe- drine is obtained as colourless crystals m. p. 176". Acetyl +-ephe- drine by treatment with hydrochloric acid gives a +ephedrine hydrochloride m. p. 175" from which the base m. p. 117" is obtained. G. W. R. The Influence of Papaverine on the Optical Activity of Narcotine in Acid Solution. HAROLD EDWARD ANNETT (T. 1923 123 376-379). [Scopoline. VI. The Constitutions of Scopolamine and Scopoline.The Hofmann Degradation of Scopoline. 1 J. GADAMER (Ber. 1923 56 [B] 130-131).-A criticism of the recent communication of Hess and Wahl (A. 1922 i 854). H. W. Furylethylamine. YASUHIKO ASAHINA and ATSUSHI FUJITA ( J . Phrm. SOC. Japan 1922 1084-1090).-According to the method of Claisen (A. 1905 i 286) furfuraldehyde (12 g.) and ethyl chloroacetate (15 g.) were condensed in cold absolute ethereal solution by the aid of metallic sodium (3.5 g.) yielding ethyl furyl- glycidate C40H,*CH<? b. p. 114-117"/5 mm. The ester was saponified with alcoholic potash; the resulting potassium salt was dissolved in water to which the calculated quantity of hydroxylamine hydrochloride was added when the resulting oxime separated as an oil (Rosenmund and Dornsaft A.1920 i 56). Furylacetaldoxime C,OH,*CH,*CH:N*OH b. p. 90-92"/4 mm. i s a light yellow viscid liquid having a strongly sweet taste (about fifty times that of sucrose). When kept the oily oxime (anti- form) gradually changes into the crystalline stable form (syn- form) m. p. 64" the sweetness being reduced by half. By reduc- tion with 3% sodium amalgam and 50% acetic acid in methyl- alcoholic solution the oxime is converted into furylethyhmine C,OH,*CH,*CH,*NH a colourless liquid b. p. 155"/762 mm. d 1*0080 nz 1.47994; it has a strongly amine-like odour and absorbs carbon dioxide from the air the carbarnate C6H ,0*NH*CO*O*NH3*C6H,0 m. p. 87" being formed. Methylisopyromucic Acid and a Method of Characterising Acids of the Sugar Group. L. J. SIMON and A.J. A. Gum- LAUUIN (Compt. rend. 1922 175 1208-1211; cf. Chavanne A. 1905 i 77).-As isopyromucic acid may be prepared by dehydr- ation of a dibasic acid derived from a hexose or of a monobasic acid k 2 C H*CO,E t ' The benzoate has m. p. kl0. K. K.i. 240 ABSTRACTS OF CHEMICAL PAPERS. derived from a pentose dehydration of a methyl pentose was effected the lactone of rhamnose being used. The homologue of isopyromucic acid thus obtained methylisopyrmucic acid C,H,O is of yellow colour m. p. 133". Oxidation by the sulpho-chromic mixture shows the presence of a methyl group directly linked to carbon. The acid has a strong reducing action on silver salts and on permanganate. Its benzoyl derivative m. p. 121" may be prepared by the action of benzoyl chloride either directly or in alkaline solution. It is not a true acid but rather a phenol CH<CH=CMe>O C( OH)*CO (cf.Chavanne A. 1902 i 637 690); the coloration with ferric chloride is bluish-green. A method of characterising the acids derived from sugars details of which are given depends on the fact that dibasic acids derived from hexoses and monobasic acids derived from pentoses and methyl pentoses give colours with ferric chloride whilst monobasic acids derived from hexoses do not do so. The latter give a positive result after careful oxidation. H. J. E. Selenium Organic Compounds. 11. Synthesis of Diaryl- thiophens and Diarylselenophens. MARSTON TAYLOR BOGERT and PILAR PEREZ HERRERA ( J . Amer. Chem. SOC. 1923 45 238- 243).-When acetophenoneanil is fused with sulphur at 220- 240" a 28% yield of pure 2 4-diphenylthiophen is obtained.The tolils may be used with equal success and if substituted aceto- phenones are used the corresponding diarylthiophens are obtained. If selenium is used instead of sulphur the products are diaryl- selenophens. The following new compounds are described aceto- phenone-o-tolil b. p. 210-220"/57 mm. ; p-methylucetophenoneanil b. p. 220-240"/53 niin. ; 2 4-diphenylthiophen-5-rnercurichloride m. p. 223" (corr.); 2 4-diphenylseZemphen m. p. 112.3" (corr.) and its 5-mercurichloride in. p. 224" (corr.) ; 2 4-di-p-tolylselenophen m. p. 136-3" (corr.). Acetophenonedimethylacetal was prepared by heating together a t 40" for several hours methyl orthoformate acetophenone anhydrous methyl alcohol and a trace of concentrated hydro- chloric acid. After the mixture had stood for sixteen hours it was made just alkaline with sodium methoxide and the methyl alcohol distilled off.W. G . Derivatives of Hydroxypyrrole. ERICH BENARY and RUDOLF KONRAD (Ber. 1923 56 [B] 44-52).-Previous attempts to obtain simple hydroxypyrrole derivatives from the hydroxy-esters (Benary and Silbermann A. 1913 i 651) by hydrolysis and sub- sequent removal of carbon dioxide have been unsuccessful on account of the small stability of the pyrrole ring towards albali hydroxide. Attempts have therefore been made to increase the stability by the introduction of the phenyl group in position 1. The hydrolysis of the esters to the corresponding acids is thus rendered possible but the subsequent removal of carbon dioxide can only be effected without extensive decomposition if the hydroxyl group is protected by methylation.ORGANIC CHEMISTRY.i. 241 Ethyl 8-anilinoacrylate is transformed by chloroacetyl chloride in the presence of anhydrous ether and pyridine into a mixture of ethyl. (3-anilino- u-chloroacetylacrylate NHPh*CH:C(CO*CH,Cl) CO,Et needles m. p. 83" and ethyl N-Chloroacetyl-B-anilinoacrylate CH,Cl*CO*NPh*CH:CH*CO,Et colourless prisms m. p. 136-137". The former ester is transformed by a cold alcoholic solution of potassium hydroxide into et h y 1 41h ydroxy - 1 -phen y lp yrrole - 3 -curb - oxylate NPh "CH:?*co2Et colourless matted needles m. p. 83- ' CH:C.OH 84". The corresponding acid crystallises in small rods m. p. 172- 174" (decomp.) and becomes resinified when heated above its melting point in a vacuum.The hydroxy-ester is converted by amyl nitrate into ethyl 5-oximino-4-keto- 1-phenylpyrroline-3-carb- oxylate lemon-yellow hexagonal prisms decomp. about 185" after softening and gradually melting above 175'; if an excess of sodium nitrite is gradually added to a solution of the ester in glacial acetic acid an isomeric product C,,H,,O,N almost colourless coarse needles m. p. 157-158" is formed the constitution of which has not been elucidated. 4-Acetoxy-l-phenylpyrroZe-3-carbox~lic acid colourless needles m. p. 145-147" is produced from the hydroxy- acid acetic anhydride and anhydrous sodium acetate ; when heated a t the atmospheric pressure or in a vacuum it loses carbon dioxide and acetic acid and leaves a black resinous residue.Ethyl 4- h ydrox y - 5 - benxeneaxo- 1 -phen ylp yrrole-3 -carbox y late orange- yellow needles rn. p. 170-172" after previous softening could not be L I CH=v*CO,H C(N:NPh):C*OH ' hydrolysed to the corresponding acid NPh< which however is prepared by the action of benzenediazonium chloride on an alkaline solution of the hydroxy-acid; it crystallises in orange-coloured needles m. p. about 185-187" after softening at 175". It is decomposed witih loss of aniline when heated in a vacuum. 4-Methoxy-1 -phenylpyrrole-3-carboxylic acid is prepared by the action of methyl sulphate on the hydroxy-acid and sub- sequent hydrolysis of the methyl ester; it forms leaflets m. p. 166-167" (decomp.) [the potassium salt long colourless needles is described].The acid loses carbon dioxide when heated in a vacuum at- 180-200" and yields 3-methoxy-1 -phenyZpyrrole colourless needles m. p. 33-34' which when Nph < CHI YH CH:C *OMe ' molten or dissolved rapiclJy become brown on exposure to air. Attempts to hydrolyse the methoxyl to the hydroxyl group by aluminium chloride hydrogen chloride or hydrogen bromide were unsuccessful owing to the instability of the free hydroxypyrrole. Methyl P-anilino-a-chloroacetylcrotonate is converted by potass- ium hydroxide in methyl alcoholic solution into methyl 4-hydroxy- l-phenyl-2-methyZpyrrole-3-carboxylate NPh<CMe:Y*co2Me small needles m. p. 123-124"; the corresponding acid crystallises in colourless needles m. p. 145". The hydroxy-ester is converted by amyl nitrite into methyl 5-oximino-4-keto-2-methyl-l-phenyl- CH =C*OHi.242 ABSTRACTS OF CHEMICAL PAPERS. pyrroZine-3-carboaylate C,,H,,O,N pale yellow needles m. p. 185-187" (decomp.) from which the corresponding acid C12H,,04Nz small pale yellow needles m. p. 171-172" (decomp.) is obtamed. Sodium nitrite converts the hydroxy-ester dissolved in glacial acetic acid into methyl 5-nitroimino-4-keto-1-phenyl- 2-methylpyrroZine-3-carboxylate orange-coloured needles m. p. 192- 193" (decomp.) after previous softening. The Action of Diazomethane on Dyes and certain Nitro- pyrroles. WILLIAM KUSTER and WILHELM MAAG (Ber. 1923 56 [B] 55-69).-1t has been shown previously (Kuster A. 1923 i 885) that the action of diazomethane on bilirubin leads to the introduction of two methyl groups into the molecule and in addition a molecule of diazomethane is combined forming a com- pound C3,H4,06N,.A further investigation of this compound and comparison of its properties with those of substances obtained by the action of diazomethane on pyrrole derivatives led the authors to the conclusion that a portion of the bilirubin molecule must contain the pyrrolenylmethanepyrrol group. The product C36H4206"$ of the addition of diazomethane to esterified bilirubin is a red amorphous powder which contains three methyl groups eliminable by hydriodic acid. It can be prepared in a crystalline form resembling bilirubin by the action of diazomethane on pure bilirubin and bilirubinammonia suspended in anhydrous ether; it however passes readily into the resinous variety. Indigoid ethyl bis-2-methylpyrroline-3-carboxylate (Benary and Silbermann A. 1913 i 652) contains two carbethoxy-groups which are readily hydrolysed by hydriodic acid a t 140" whereas a further evolution of alkyl iodide is not observed below 300"; it is converted bv diazomethane in the presence of ether into a red resin.H. W. Meth y 1 5 -$'-acety lt etronylidene-4 -&et o -2 -methylpjrrole- 3 -curb ox ylat e yellow needles m. p. 190" CO,Et*fl- CO; C:C<CH,-- ? Me*C*NH C( :CMe*OH)*CO' (decomp.) is prepared by the action of alcoholic potassium hydroxide solution on a mixture of acetyltetronamide and ethyl chloroacetylaminocrotonate ; it is converted by diazomethane into a reddish-brown resin C16H,,06N m. p. 75" (decomp.). Ethyl 5 5'-bis-4-keto-2-methylpyrroline-3-carboxylate hydrate C16H,,0,N,,H,0 (cf.Benary and Silbermann loc. cit.) loses two ethyl groups under the action of hydriodic acid at 140" and does not suffer further loss of allwl iodide below 340" it is converted by diazomethane into a yellow brittle resin CIiHHO5N2 m. p. 73-74" (decomn.). 3 - Hydroxy - &- darbethoxy - 5 - methylpyrrolenyl - 2 - furylmethane C13H1304N (Kuster A. 1922 i 858) combines with hydrogen chloride in the presence of acetone to form a hydrochlorzde C,3H140,NCl rust-brown needles which readily lose hydrogen chloride on exposure to air. The substance is converted by diazo- methane into a dark brown resin. 3-Hydroxy-4-carbethoxy-5- methyl-2-o-pjrrolenylhydroxyphenylmethne brownish-yellow needles,ORGANIC OREMISTRY.i. 243 m. p. 207" (decornp.) is readily prepared from Benary's pyrrole and salicylaldehyde and is transformed by diazomethane into a yellow resin m. p. about 40" after previous darkening. Ethyl 2 5-dimethylpyrrole-3-carboxylate is oxidised by chromic acid to carbethoqmleinimide C,H,O,N colourless needles m. p. 115". Benary's indigoid pyrrole (loc. czt.) is oxidised by nitric acid (d 1.4) at 0" to ethyl 5-nitro-2 4-dihydroxy~rrole-3-carboxylate colourless needles decomp. 100". The potassium salt C,H,O,N,K decomp. 167" barium salt decornp. 165" lead and copper salts are described. Hydrogen sulphide reduces the nitro-compound to a colourless substance m. p. 121". The ester is readily hydro- lysed to 5-nitro-2 4-dihydroxypyrrole-3-carboxylic acid colourless needles decornp.124" the ammonium and silver salts of which are described ; the methyl ester crystallises in colourless needles decomp. 112". Ethyl 5-nitro-2-hydroxy-4-methoxypyrrole-3-carb- oxylate a pale yellow liquid b. p. 146" which solidifies to needle- shaped crystals when cooled with ice is readily prepared by the action of diazomethane on the corresponding dihydroxy-ester. 5-Nitro-2-hydroxy-4-methoxypyrrole-3-carboxyZic acid crystallises in colourless needles ; the ammonium salt silver salt and the methyl ester a colourless liquid b. p. 145" are described. Ethyl 5-nitro-4-hydroxy-2-methylpyrrole-3-carboxylate colourless needles m. p. 100.5" (decomp.) is readily hydrolysed to 5-nitro-4- hydroxy -2 -met hylpyrrole- 3 -carboxylic acid colourless needles decomp.124". It is converted by diazomethane into ethyl 5-nitro-4-methoxy- 2-methylpyrrole-3-carboxylate. H. W. The Tetrachlorodipyridinoiridiates. Configurations of the Two Series of Iridiumdipyridinotetrachloro-compounds. MARCEL D~~L~CPINE (Compt. rend. 1922 175 1211-1213; cf. this vol. i 135).-These are neutral un-ionisdl substances. cis- and trans-Isomerides exist which are derived from the orange and red salts respectively. They are not of equal stability towards oxidis- ing agents and are themselves of unequal oxidising power. Both decompose iodides according to the equation Ir(C,H,N),Cl,+ MI -+ Ir(C,H,N),Cl,M+I but only the cis-compound decomposes bromides. This is consistent with the fact that bromine can be used only in preparing the orange salts. The author concludes that the cis-isomeride behaves as a halogen intermediate between chlorine and bromine and the trans as intermediate between bromine and iodine.The constitution was determined by reason of the dichroism of the chloride derived from the orange salt which is isomorphous with and confers the property of dichroism on platinum tetrachlorodipyridine PtCl,(C,H,N), It has been shown (Werner and Fassbender A. 1897 i 631; Jorgensen A. 1901 i 163) that the latter substance has the cis-configuration hence the same configuration is inferred for the orange salts. The red salts have therefore the trans-configuration. H. J. E. &Ketonic Nitriles and their Relation to Cyclic Compounds. E. P. KOHLER and B. L. SOUTHER ( J . Amer. Chem. Xoc. 1922 44 2903-2914 ; cf. this vol.i 54).-Cyanoacetamide and cyano-i. 244 ABSTRACTS OF CHEMICAL PAPERS. acetonitrile like methyl cyanoacetate condense with phenyl styryl ketone but the three products although closely related behave differently towards most reagents. All three form cyclic compounds under the influence of halogen acids in indifferent media. The product from methyl cyanoacetate forms a tetrahydropyridine derivative in the production of which the cyano-group is involved and molecular rearrangement occurs. The product from cyano- acetamide also forms a tetrahydropyridine derivative but in its production the amide group is involved. Under the same con- ditions the product from the dinitrile forms only a trace of a tetrahydropyridine derivative the main product being a mixture composed of a pyridine and a hexahydropyridine derivative. This mixture is doubtless due to a series of reactions starting with the addition of halogen acid to one of the cyano-groups and ending with the spontaneous oxidation and reduction of an intermediate dihydropyridine derivative.The results confirm the view that such oxidation-reduction reactions are associated with the extra- ordinary activity of hydrogen which is in combination with atoms that are flanked on both sides by unsaturated groups; but they do not support the conclusion of Knoevenagel and his co-workers (cf. A. 1903 i 785) that hydropyridine derivatives are incapable of reacting in all possible desmotropic modifications. Cyanoacetamide condenses with phenyl styryl ketone under the conditions previously described (loc.cit.) to give a-cyano-y- benzoyl-p-pheri ylbutyramide m. p. 161-163" and similarly cyano- acetonitrile yields u-cyano-y-benxoyl-p-phenylbutyronitrile m. p. 125-126". When dry hydrogen chloride or bromide is passed into a chloroform solution of the above amide 2-keto-3-cyano- 4 6-diphenyltetrahydropyridine m. p. 220" is obtained and this on hydrolysis with concentrated sulphuric acid yields 2-keto-3- carbamyl-4 6-diphenyltelrahydropyridine m. p. 181-182" and when treated with nitrous acid gives 1-hyclroxy-3-cyano-4 6- diphenylpyridine m. p. 313-315". With alcoholic ammonia the dihydropyridine derivative undergoes spontaneous oxidation-reduc- tion and the products are a hydroxypyridine and 2-keto-3-cyano- 4 6-diphenylpiperidine m. p.188-189". a-Cyano-7-benzoyl-p- phenylbutyronitrile also reacts with halogen acids in dry chloroform solution. With hydrogen chloride one of the products is 2-chlmo- 3-cyano-4 6-diphenylpyridine m. p. 154.5" and with hydrogen bromide 2-bromo-3-cyano-4 6-diphenylpyridine m. p. 169-170" is obtained. In the latter reaction a red oil was also formed from which after pouring it into a solution of sodium hydrogen carbonate 2-keto-3-carbamyl-4 6-diphenylpiperidine m. p. 170" was isolated and this on treatment with hydrogen chloride in methyl alcohol gave methyl 2-keio-4 6-diphenylpiperidine-3-carboxylate m. p. 177". With alkalis the cyanoamide additive product m. p. 161-163" described above is transformed into its cyclic isomeride the only other product being zz trimolecular compound.With alcoholic alkalis the dinitrile additive product gives pyridyl ethers of which 2-methoxy-3-cyano-4 6-diphen ylpyridine m. p. 1 lo" and 2-ethoxy- 3-cyazo-4 6-diphenylpyridine m. p. 112" wt'rc yrcpred.ORGANIC CHEMISTRY i. 245 The rearrangement of the cyanoacetamide additive product to cyclic compounds takes place so easily that only cyclic bromo- compounds were obtained from it even when the bromination was carried out in the presence of potassium acetate. From the dinitrile however it was possible to obtain one open-chain bromo- compound by brominating it in the presence of potassium acetate. The behaviour of this substance towards halogen acids confirms the view previously expressed (loc. cit.) regarding the mechanism by which bromopyridine derivatives are formed when bromine acts on open-chain ketonic nitriles since when dry hydrogen chloride is passed into a chloroform solution of the bromo-corn- pound the product is a chloropyridine derivative.The compounds described are cc-bromodi-cc-cya?ao-y-benxoyl-p-phenylbutyronitrile m. p. 126-127 " 5- brorno-2 - keto- 3-cyano-4 6-diphenyltetrahydropyridine m. p. 165" 5-chloro-2-keto-3-cyano-4 6-diphenyltetrahydropyridine m. p. 178-181" 3 5-dibromo-2-keto-3-cyano-4 6-diphenyltetrahydro- pyridine m. p. 195" (decomp.) 5-bromo-2-hydroxy-3-cyano-4 6- diphen ylpyridine m. p. 303-306" (decomp.) 2-chloro-5-bromo-3- cyano-4 6-diphenylpyridi~e m. p. 181-182" and 2 5-dibromo- 3-cyano-4 6-diphenylpyridine m. p. 189-190". W. T. K. BRAUNHOLTZ ( J .Amer. Chem. Soc. 1922 44 2967; cf. T. 1922 121 169).-In reference to a paper by Gutekunst and Gray (A. 1922 i 950) the author directs attention to the preparation and description of the 5- 6- and 7-ethoxyquinaldines by himself (loc. cit .). The Constitution of Dianhydrodiacetylanthranilic Acid. GUSTAV HELLER and HERBERT GRUNDMANN (Ber. 1923 56 [B] 200-205).-The action of phosphoryl chloride on acetylanthranilic acid or its esters or on acetylanthranil has yielded a compound which Anschiitz and Schmidt (A 1903 i 56) designat'e dianhydrodiacetyl- anthranilic acid. and to which thev assign the constitution W. G. The Ethoxyquinaldines. W. G. . I This compound has now been obtained incidentall? 'by the action of acetic anhydride on benzene- or p-toluene-sulphonylanthranilic acid and is shown to be the o-carboxyanilide of 4-hydroxy-2- met h ylq uinoline - 3 - carboxylic acid p-Toluenesulphonylanthranilic acid is converted by boiling acetic anhydride into the mixed anhydride of toluene-p-sulphonic acid and the o-carboxyanilide of 4- hydroxy -2 -methylquinoline-3-carb- OXyh acid c6H4< C( OH)'~*CO*NH*C,H,*CO-O*S02*C6H4M~ ' pale yellow crystals m.p. 214-215" (decomp.). The substance is decomposed by dilute sodium hydroxide solution into the o-carb- oxyanilide of 4-hyclroxy-2-methylquinoline-3-carboxylic acid m. p. 249-250" (decomp.) identical with the product obtained by Anschutz and Schmidt (Zoc. cit.). It is converted by glacial acetic N-CMe k*i. 246 ABSTRACTS OF CHEMICAL PAPERS. and concentrated hydrochloric acids at 130-140" info 4-hydroxy- 2-methylquinoline. A substance C3,H,,0,,N,S slender needles m.p. 133.5" is obtained as by-product of the action of acetic anhydride on p-toluenesulphonylanthranilic acid. It appears to contain acetic anhydride and solvent of crystallisation ; when deprived of this it has m. p. 159-160" (decomp.) but the amount of it available was insufficient for an extended examination. Benzenesulphonylanthranilic acid is transformed by boiling acetic anhydride into the mixed anhydride c1$&5Ns slender needles m. p. 157-158". p-Toluenesulphonylanthranilic acid is transformed by glacial acetic and concentrated hydrochloric acids a t 140" into anthranilic acid toluene-p-sulphonate C,,H,,O,NS slender needles m. p. 218" (decomp.). The corresponding benzenesulphonate has m.p. 230" (decomp.). H. W. The Constitution of Naphtholisatin and its Derivatives C. C ~ D E A (Bull. Acad. Sci. Roumaine 1922 8 31-39).-Colour- less condensation products of isatin with a-naphthol were pre- pared. These differ from similar compounds obtained from phenols in that they are almost insoluble in alkaline solutions are not oxidised to coloured substances and do not form acetyl deriv- atives. The condensation probably occurs at the 3-position of the indole nucleus (cf. DLnLilL and Ckndea A. 1916 i 417). The derivatives obtained were Di-or-naphtholisatin C2,H1903N p r i s m - atic needles m. p. above 300". Di-a-nccphtholmonobrommsatzn C28H,,0,NBr prismatic needles m. p. above 300". Di-a-nccphthol- dibromisatin C28H1,03NBr2 prismatic needles m.p. above 300". ni- u-naphtholmonochlorisat in C,,H 1803NC1 crystals m . p . above 300". I)i-u-naphtholdichlmoisatin C2,H,,03NC1 prismatic needles m. p. above 300". Stereochemical Studies. VII. 2-Thion-4-methylthiazol- ine-3-acetic Acid. BERTIL GROTH and BROR HOLMBERG (Ber. H. J. E. 1923 56 [B] 289-298).-2-Thion-4-methylthiaxoline-3-metic 'acid; S<"-Y *CH~*co2H pale honey-yellow thick plates or short CH:CMe prisms m. p. 198-199" (decomp.) is prepared in 87% yield by the action of chloroacetone on an aqueous solution of glycine hydro- chloride and pptassium hydroxide which has been agitated with carbon disulphide until the latter is completely dissolved; it dis- solves in wat,er to the extent of 2.06 g. per litre at the atmospheric temperature. The sodium salt rectangular plates ( +5H20) ba,rium salt rosettes of needles ( +2H20) methyl ester almost colourless needles m.p. 96-97" and ethyl ester long almost colourless needles m. p. 97-98" are described. The acid could not be resolved into its optical antipodes by treatment with I- or d-phenylethylamine in aqueous or alcoholic solution ; the salts of the r-acid with the optically active bases were isolated (m. p. 161-162" and 160-162"). The acid is unusually stable towards hydrolysis by acid or alkali. It is oxidised by nitric acid (or lessORGANIC CHEMISTRY. i. 247 conveniently by bromine water) to the inner anhydride of 2-keto-4- rnethylt hiaxoline- 3 -acetic acid CO <:?I$ gEi>CH which is isolated as the hydrogen sulphte C,H,0,SN,H2S04 a colourless crystalline somewhat hygroscopic substance m.. p. 114-115" to a turbid liquid. The corresponding hydrochlorzde (anhydrous and monohydrate) is described; it has m. p. above 230" (decomp.) after darkening at 200" and becoming black at 230". The free base is a colourless crystalline powder (+2-5H20) m. p. 110-115" (decomp.) after softening and becoming discoloured at 95" m. p. (anhydrous) 165" (decomp.). It is stable in hot aqueous acidic solution but is readily decomposed in neutml or alkaline solution with the formation of ill-defined products. It was not found possible to isolate the corresponding acid since the tendency towards dehydration is so marked that the anhydride can exist even in faintly alkaline solution. H. W. Stereochemical Investigations of the Diketothiazolidines.I. STEN KALLENBERO (Ber. 1923,56 [B] 316-331).-In contrast to the $-thiohydantoins and the rhodanines the diketothiazolidines which have a mobile hydrogen atom attached to the asymmetric P-carbon atom exhibit normal stereochemical relationships. They can readily be prepared in optically active forms which easily undergo racemisafion in consequence of the possibility of desmo- tropic change. Potassium ethylthiocarbamate NHEt*CO*SK is prepared con- veniently by the action of carbon oxysulphide on a solution of potassium hydroxide and ethylamine hydrochloride in absolute alcohol. Under certain conditions particularly with regard t o concentration i t reacts with a solution of sodium 1-bromosuccinate in cold water to give d-ethylcarbamidothiolsuccinic acid CO,H*CH (S*CO*NHEt)*CH,*CO,H small plates +103.5" in absolute alcoholic solution.The acid is readily decomposed by concentrated ammonia with the production of d-thiomalic acid by warm acids to d-thiomalic acid carbon dioxide. and ethvlamine. on the one hand. and to r-diketo. " ethylthiazolidineacetic acid ~Et*co>CH*CH2*C0,H on the co-s other by alkalis into d-thiomalic acid carbon dioxide and amine. r-Ethylcarbamidothiolsuccinic acid crystallises in colourless thin prisms or short needles m. p. 141-142" (decomp.). The action of cold concentrated hydrochloric acid on d-ethyl- carbamidothiolsuccinic acid gives a mixture of r-diketoethylthiazol- idineacetic acid colourless prisms m. p. 113-115" and the corre- sponding d-mid which however could not be caused to crystallise.The racemic acid can be resolved with the aid of active phenyl- ethylamine but the active acids are again obtained only in the form of non-crystalline syrups. d-~~ethylcarbarnidothiolsuccinic acid prepared from potassium methylthiocarbamate and sodium 1-bromosuccinate has m. p. 114-116" (decomp.) [a] +99.2" in absolute alcoholic solution. ln* 9i. 248 ABSTRACTS OF CHEMICAL PAPERS. The corresponding r-acid crystallises in colourless spherical aggre- gates m. p. 135-136" (decomp.). The active acid is converted by concentrated hydrochloric acid into d-diketomethylthiazolidineacetic acid transparent prisms m. p. 101-102" [aID +ZOS.O" in absolute alcoholic solution (the success of the reaction greatly depends on the conditions of the experiment which are described in detail in the original).It is converted in alkaline solution into r-methyl- carbamidothiolsuccinic acid. Since d-methylcarbamidothiolsuccinic acid is not racemised under similar conditions it follows that d-diketomethylthiazolidineacetic acid must be converted into the corresponding r-compound previously to fission of the thiazole ring. Preliminary measurements show that the velocity of racemisation is diminished with increasing concentration of hydrogen-ions and increased by increasing concentration of hydroxyl-ions. r-Diketo- methylthiaxolidineactic acid crystallises in small colourless plates m. p. 98-99". d-Dimethylcarbamidothiols21ccinic acid forms colourless prisms m. p. 138-139" (decomp.) [a]= +81-7" in absolute alcoholic solu- tion.It is decomposed by hot N-sodium hydroxide solution to a small extent into thiomalic acid carbon dioxide and dimethyl- amine but the greater portion is constitutionally unchanged and only slightly racemised. Similar treatment with N-sulphuric acid causes an almost complete fission into partly racemised thio- malic acid ; concentrated hydrochloric acid at the atmospheric temperature gives the same result except that fission is less extensive and racemisation of the products more pronounced. H. W. The Tautomerism of Amidines. I. 2:4- and 2 :5-Di- RICHARD BURTLES and FRANK LEE PYATAN The Tautomerism of Arnidines. 11. The Alkylation of Open-chain Amidines. FRANK LEE PYMAN (T. 1923 123 H. A. SHONLE and A. MOMENT ( J . Amer. Chem. Xoc. 1923 45 243- 249) .-Various dialkyl- and alkylaryl- barbituric acids were pre- pared and tested for hypnotic action.The monoalkyl- and aryl- derivatives were found to be inactive in doses of 0.5 to 1 g. per kg. of body weight when injected subcutaneously in rabbits. Dimethylbarbituric acid was without any apparent action on rabbits in a dose of 0-75 g. per kg. of body weight. Then as the molecular weight increased the activity increased until a maximum was reached after which i t declined until the hypnotic activity was lost and the animal showed only muscular inco-ordination or no effect at all as was the case with dibenzylbarbituric acid. How- ever the length and type of the carbon atom chains of the entering groups play an important part in modifying the activity. Branched chains are more active and less toxic than are the straight chains.Of the aliphatic compounds investigated ethylisoamylbarbituric phenylglyoxalines. (T. 1923 123 361-367). 367-370). Some New Hypnotics of the Barbituric Acid Series.ORQANTC! CHEMISTRY. i. 249 acid was found to be the most active as well as to possess the lowest toxicity. The relative activities of the barbituric acid derivatives tested are tabulated. New malonic esters prepared are as follows ethyl-sec.-butylmalonic ester b. p. 155-160"/60 mm. d$ 0-9858 n5 1.4264; ethylisobutylmalonic ester b. p. 119-120"/8 mm. dz 0.9682 n'?j 1.4228 ; ethylisoamylmalonic ester b. p. 150"/20 mm. d$ 0.9540 nm 1.4255; propylisopropylmalonic ester b. p. 143"/42 mm. d! 0.9803 n25 1.4239 ; isopropyl-n-butylm,lonic ester b. p. 136"/14 mm.djz 0.9742 n25 1.4291. New derivatives of barbituric acid are ethylisobutylbarbituric acid m. p. 174-1'76" ethylisoamylbarbituric acid m. p. 1&156" isoprop yZ-n-butylbarbituric acid m. p . 209-2 lo" n-prop ylisopropyl- barbituric acid m. p. 161-162" isopropylisoamylbarbituric acid m. p. 173-175" propylisoamylbarbituric acid m. p. 129-132" ethyl-sec .-but ylbarbituric acid m. p. 155-157 '. BRUXO EMMERT and JULIUS STAWITZ (Ber. 1923 56 [B] 83-91).-An extensive series of 4 4'-dipyridylium di- and mono-alkyl halides has been examined. The various colours which they exhibit in substance and when dissolved and the failure of their solutions to observe Beer's law are explained by the application of Hantzsch's views on the constitution of ammonium salts.C H N(R)I [(;~H~N(R)]I (1.) (11.) (111.) UV.1 (V.) z5E4z(:)1 [C5H4NR The constitution I is ascribed to the red dipyridylium di-iodides and the corresponding pseudo-form IV to the yellow monoiodides. The yellow hydrates of the di-iodides have the constitution 11 whereby the difference between their colour and that of the anhydrous compounds and their similarity with the monoiodides is explained. In the aqueous and alcoholic solutions of the di- iodides the three forms I 11 and 111 are present in equilibrium the two latter being electrolytically dissociated. In a similar manner the failure of the monoiodides to obey Beer's law in solution is explained by the equilibrium between the yellow mole- cules (IV) and the colourless molecules (V). 4 4'-Di- pyridyl dihydriodide red piisms and the corresponding mom- hydriodide (golden-yellow prisms $- 1H,O and anhydrous).The corresponding dihydrobromide long pale yellow needles mono- hydrobromide colourless prismatic needles ( + H,O) and mm- hydrochloride (+H,O). 4 4'-Dipyridyl monomethaodide a pale yellow crystalline powder and the corresponding hydriodide. 4 4'-Dipyridyl dimethobromide yellow prisms. 4 4'-Dipyridyl diethiodide orange-coloured prisms and the corresponding mono- ethiodide lustrous yellow leaflets. 4 4'-Dipyridyl dipropiodide red crystals which yields a pentahydrute on exposure to moist air the monopropiodide yellow crystals the dipropobromide greenish- yellow crystals and the dipropochloride colourless lustrous leaflets W. G . T h e Colowr of the 2 2'-Dipyridyliurn Halogenides.6 4* ( >I (,"5H4N(R)I I v5H4NR 1 [I ,H4NRIr2 C5H4N The following individual compounds are described :i. 250 ABSTRACTS OF CREMICAL PAPERS. which deliquesce on exposure to air. 4 4'-DipyridyE metkiodide propiodide red oblique prisms. 4 4'-Dipyridyl moisobutiodide which closely resembles the monopropiodide. 4 4'-DipyridyZ anonoisoamyliodide. 4 4'-Dipyridyl di-sec.-hexyliodide a brownish- red substance di-hydrate yellow needles. 4 4'-Dipyridyl di- benzyziodide a red substance which gives an unstable yellow hydrate dibenzylbromide and the corresponding pale yellow tetrahydrate. H. W. Some Derivatives of Methylenediquinaldine and their FRANCES MARY HAMER The Colour of Di- and Tri-Zquinolyhethanes and their Derivatives. GUNTER SCHEIBE (Ber.1923 56 [ B ] 137-148 ; cf. A. 1921 i 62 451; 1922 i 1190).-Di- and tri-2-quinolyl- methanes exist in colourless and coloured forms which yield an equilibrium mixture in solution or in the molten condition. The former varieties can be represented satisfactorily by formulae of the type CH,(C,H,N) but the coloured compounds do not possess the quinonoid structure C,H,N*CH:C,H,:NH since their absorp- tion spectra differ entirely from those of the l-alkyl derivatives. The hydrogen atom is not attached directly to the central carbon atom or to either nitrogen atom but as it is shown by the chemical reactions of the compounds to be related to all three it must be ascribed a position within their sphere of influence. The optical effect of this mode of union of the hydrogen appears to be similar to that of the union of the anion in the dye salts although i t is not ionisable.In this case ionisation does not appear to have an immediate relationship to optical properties. [With R. PFLOCK K. SCHOLL and E. FRIEDEL.]-Di-2-quinoly~- methane is prepared without particular difficulty by the process described recently (A. 1922 i 1190); the success of the operation depends on the presence of small quantities of hydrogen chloride such as are usually retained by 2-chloroquinoline. Konig's failure to prepare the compound (A. 1922 i 1188) is due to the use of too carefully purified materials. A cold solution of di-2-quinolylmethane in alcohol is converted by four molecular proportions of nitric acid into the dinitrate Cl,Hl,N2,2HN0 colourless lustrous leaflets.The salt is con- verted when heated by itself or in alcoholic solution into nitro- di-2-quirwlylmethane mononitrate NO,*CH(C,H,N),,HNO yellow plates decomp. 145"; this is converted by sodmm hydroxide into a colourless crystalline substance which after desiccation in a toluene bath gives the sodium salt of the mononitro-compound C19H,,0~,Na yellow crystals m. p. 282". Nitrodi-2-quinoZyE methane crystallises in yellow needles m. p. 200". It appears to yield only monoacid salts even with an excess of mineral acid. It is converted by nitric acid in warm glacial acetic acid solution into dinitrodi-2-quinoZyZmet~neY C(C,H,N),(NO,) almost colour- less prisms m. p. 140". Tri-2-quinolylcarbinol is converted by acetic anhydride and Relationship to the Carbocyanines. (T.1923 123 246-259).ORGANIC CHEMISTRY. i. 251 sodium acetate into the corresponding acetate C3,-,H210,N3 colour- less prisms m. p. 190". Bromine and tri-2-quinolylmethane yield tri-2-quinoZylbronw- methane CZ8Hl8N3Br colourless crystals m. p. 169". It gives a di-picrafe and is converted by alcoholic potassium hydroxide solution into tri-2-quinolyZmthyl ethyl ether colourless crystals m. p. 179" and a compound of high melting point which appears to be the ether derived from two molecules of the carbinol. It is smoothly reduced by phenylhydrazine in the presence of benzene to tri -2-quinolylmet hane . p-Dimethylaminobenxylidenepicoline forms pale yellow crystals m. p. 139" and like the corresponding quinaldine derivative gives coloured salts with acids which are immediately decomposed by alkali.Nitrous acid appears to transform the compounds into nitroso- amines but the investigation of these substances is not complete. When molecular proportions of acetylacetoneanil aniline and zinc chloride are warmed with a little alcohol the additive com- pound of the dianil with zinc chloride C1,H18N2,ZnC12 colourless prisms decornp. 256" is obtained. This suffers decomposition into the monoanil when treated with ammonia. The dianil mono- hydrochloride yellow prisms m. p. 218" is prepared from the mono- anil and aniline hydrochloride but it was not found possible to obtain the crystalline base from the salt. Acetylacetonecarbamide (cf. Stark A. 1909 i 260) which has been prepared in the light and is therefore yellow melts at 95" to a colourless liquid which re-solidifies at about loo" becomes yellow when further heated and has m.p. 198". Dibenzylideneacetyl- acetonecarbamide yields a monohydrochloride C,,H ,0N2C1. H. W. Contraction of the Ring in the Cases of Quinoxaline Deriv- atives and a New Method of Formation of Benziminazoles. I. K. BRAND and E. WILD (Ber. 1923 56 [B] 105-119).-The condensation of the hydrochlorides of N-mono-substituted aromatic o-diamines with 1 2-dicarbonyl compounds leads in general to the production of quinoxaline derivatives. It is therefore remarkable that benzil and 4-nitro-2-aminophenyl-p-tolylamine in the presence of hydrochloric acid yield 5-nitro-2-phenyl-1 -p-tolylbenziminazole hydrochloride in place of the expected stilbazonium chloride the 5-membered iminazole ring being formed in place of the expected 6-membered diazine ring.A number of possibly similar instances have also been examined. 5-Nitro-2-phenyl- l-p-tolylbenziminazole hydrochloride colourless slender needles m. p. 235" readily separates when a solution of benzil and 4-nitro-2-amino-4'-methyldiphenylamine in alcohol is boiled with hydrochloric acid. Benzi1-5-nitro-2-anilinoani1 COPh*CPh:N*C,H,(NO,)*NHPh pale yellow needles m. p. 205" is slowly converted by sulphuric acid into the $-base of 6-nitro-1 2 3-triphenylstilbazonium NO .C H <N-- 'ph NiTk?h*OH'i. 252 ABSTRACTS OF CHEMICAL PAPERS. m. p. 161" which is more conveniently prepared by the action of hydrochloric acid on the anil under conditions which are described in detail in the original communication. The anil is transformed by treatment with concentrated hydrochloric acid in boiling alcoholic solution into 5-nitro- 1 2-&phenylbenziminazole m.p. 181" (cf. Walther and Kessler A. 1906 i 898); the latter sub- stance is also prepared by the action of hydrochloric acid and alcohol on 6-nitro-1 2 3-triphenylstilbazonium base and from benzil and 4-nitro-2-aminodiphenylamine under somewhat similar conditions. The 6-chloro-1 2 3-triphenylstilbazonium $-base yellow needles m. p. 164" prepared by the condensation of benzil and 4-chloro- 2 -aminodiphenylarnine in boiling alcoholic solution could not be converted inOo 5-chloro- 1 2-diphenylbenziminazole by treatment with alcohol and hydrochloric acid even after addition of nitro- benzene to the mixture.6-Nitro-2 3-diphenylquinoxaline is unchanged when heated a t 150-170" with alcohol and hydrochloric acid. According to the conditions particularly with respect to the amount of acid used the acticn of 4-nitro-2-amino-N-methylaniline on benzil in the presence of alcohol and hydrochloric acid leads to the formation of benxil-S-~~.itro-2-methylaminomo,20cc72il yellow leaf- lets m. p. 195" 6-nitro-2 3-diphenylquinoxaline 6-nitro-2 34%- phenyl- 1 -methylstilbaxoniunz chloride dark yellow needles m. p. 168" (decomp.) and a substance m. p. about 280" which has not been completely investigated. More favourable conditions for the conversion of the anil into 6-nitro-2 3-diphenylquinoxaline and 6-nitro-2 3-diphenyl- 1-methylstilbazonium chloride are described in detail.The $-base corresponding with the substance last mentioned crystallises in yellow needles m. p. 170" (from alcohol) 176" (from benzene) ; repeated crystallisation from hot alcohol effects its re-conversion into the anil. H. W. The Indigotin Group. 11. A New Vat Dye Prepared from Indigotin and Ethyl Malonate. THEODOR POSNER and GOTTFRIED PYL (Ber. 1923 56 [B] 31-44; cf. Posner and Aschermann A. 1920 i 8SO).-A vat dye derived from indigotin and ethyl malonate has been patented by Posner (D.R.-P. 281998). The full investigation of the product is now described the sub- stance being of particular interest since it gives violet-red shades which are quite distinct from the usual indigo colours. Ethyl indigotinrnalonate (annexed formula) reddish-violet crystals m.p. 296-297" is prepared con- -N/ \c2 veniently by heating a solution of / \c=c/ \c6H indigotin in nitrobenzene with ethyl 4\c()/ \NH/ malonate and a little solid sodium hydroxide. It may also be obtained in poor yield by the protracted ebullition of a solution of indigotin in a large excess of ethyl malonate; as by-product of the latter action a curboxylic acid C16H,,010 m. p. 129" is formed which has not been investigated completely. It is converted by aqueous alcoholic co~c-co EtORGANIC CHEMISTRY. i. 253 potassium hydroxide solution into the corresponding potassium salt C2,H1404N2,KOH an emerald-green powder. Hydrolysis of the carbethoxyl group could not be effected by means of acid or alkali; the protracted action of the latter appears to cause the slow loss of the whole malonyl group without however giving a homogeneous product.The introduction of a second malonyl complex into ethyl indigotinmalonate could not be effected but the compound reacts with phenylacetyl chloride in the presence of boiling xylene to yield ethyl arihydrophenylacetylirLdigotin- malonate (annexed formula) m. p. above 310". Ethyl benxoyldi- CO-C-O,&t hy~roindigotinmalonate C,,H,,O,N colourless leaflets which become c/ \c,H4 red at about 192" and decompose without melting a t a higher tem- perature is prepared by reduction of ethyl indigotinmalonate with sodium hyposulphite in the presence of sodium hydroxide and addition of benzoyl chloride to the solution. The presence of the imino-group in ethyl indigotinmalonate is established by the preparation of ethyl benxoytindigotinmalonate C,,H1,0,N2 orange-coloured leaflets m.p. 240" which is obtained in small yield by boiling the ester and benzoyl chloride or more con- veniently from these substances in the presence of pyridine. Acetyl chloride and pyridine convert ethyl indigotinmalonate into ethyl acetylindigotin~nalonate red crystals m. p. 182". Ethyl nitroso- indiyotinmulonate C2,H130,N3 tile-red crystals decomp. 267- 270" is prepared by the action of nitrous fumes on a boiling alcoholic suspension of ethyl indigotinmalonate into which it is re-converted by successive treatment with zinc dust and air. It is not affected by a boiling mixture of acetic anhydride and acetyl chloride but is converted by benzoyl chloride in the presence of boiling pyridine into ethyl benzoylnitrosodi- h ydroindigotiizrnal onat e (an- C H /-N/ \c.cJc- \c nexed formula) orarige- \N(NO),/ 6 4 yellow crystals which com- mence to sublime a t 236" and decompose a t 245-250" ; it is hydrolysed by aqueous-alcoholic potassium hydroxide solution. to ethyl nitrosoindigotinmalonate.A compound C&1707& small almost colourless needles which become red a t ZlO" is formed during the preparation of ethyl indigotinmalonate. H. W. peri-Naphthindigotin. SIKHIBHUSHAN DUTT (T. 1923 123 2 5-Iminodihydro-1 2 3-triazole. I. Constitution of PAVITRA KUMAR DUTT (T. 1923 Purines. IV. The Action of Hydrogen Peroxide on certain Phenyl-substituted Uric Acids. F. J. MOORE and ZLIZABETH S. GATEWOOD ( J . Amer. Chem.Soc. 1923 45 13&145).-1t has % N' w4(c)c= \N/ \CPh*CO' CO-C-C0,Et 4\Co(eZ)// 224-225). Dimroth's 5-Anilinotriazole. 123 265-274).i. 254 ABSTRACTS OF CHEMICAL PAPERS. previously been shown (A. 1918 i 104 409 410) that the action of hydrogen peroxide on uric acid may lead to two distinct series of products according to experimental conditions but the results indicated no intermediate product between uric acid and the final products obtained. With a view to obtain information as to the relationship which may exist between the mechanism of this reaction and that of the permanganate oxidation certain sub- stituted uric acids have been prepared and their behaviour on oxidation by hydrogen peroxide has been studied. 9-Phenyluric acid on oxidation in alkaline solution with hydrogen peroxide gives as-phenylbiuret and a new phenylbiuret m.p. 196-1976" (cf. following abstract) together with ammonia oxalic acid and phenylcarbamide. 7-Methyluramil when treated in alkaline solution with phenylcarbimide yields 9-phenyl-7-methyl- +-uric acid m. p. 245-250" na 1.636; ny 1*714+ from which by boiling with hydrochloric acid 9-phenyl-7-methyluric acid na 1.887 ny 1.674 is obtained. On oxidation with hydrogen peroxide in the presence of potassium hydroxide this uric acid gives oxalic acid ammonia and b-phenyl-a-methylcarbamide. By a similar series of reactions starting with 1 3-dimethyluramil 9-phenyl- 1 S-dimethyl-+-uric acid m. p. 189-190" na 1.525 ny 1.647 giving a monohydrate and 9-phenyl-1 3-dimethyluric acid na 1*155+ ny 1.684 are obtained. The latter compound on oxidation as above also yields ammonia oxalic acid and b-phenyl-a-methyl- carbamide .9-AlZyl-$-uric acid m. p. 227-228" (decomp.) nu 1.591 ny 1.69 is also obtained from the uramil and was converted into 9-allyluric acid nu 1.75 ny 1.775. The optical properties of a number of familiar compounds allied to the above were determined during the work and the results are tabulated. From the above results on the oxidation of substituted uric acids it is considered that the first step in the reaction is the breaking of the bonds between the carbon atoms 2 and 3 4 and 5 and 5 and 7 forming in the case of 9-phenyluric acid s-phenylbiuret and in the cases of the other two the same phenylmethylbiuret. The phenylmethylbiuret then decomposes giving ammonia and phenylmethylcarbamide while the s-phenylbiuret partly undergoes a similar decomposition forming phenylcarbamide and another portion is rearranged by the ammonia to form as-phenylbiuret.W. G. Purines. V. A Third Phenylbiuret. ELIZABETH S. GATE- WOOD ( J . Amer. Chem. Xoc. 1923 45 146-150; cf. preceding abstract).-The new phenylbiuret m. p. 196-198" (decomp.) nu 1.559; % 1.73 obtained during the oxidation of 9-phenyluric acid by hydrogen peroxide (bc. cit.) is clearly distinguished by its properties from the two isomerides already known. It can be converted into as-phenylbiuret by the action of ammonia and a great variety of organic bases but not by alkalis. No method of reversing this change has been discovered. From certain theoretical considerations the author is inclined to the view thatORGANIC CREMlSTRY.i. 255 the structure of this new biuret is that of N-phenylbiuret a struc- fure at present assigned by Schif€ (A. 1907 i 206) to the phenyl- biuret prepared by Weith (A. 1878 141). The Upper Limit of Diazdisability in the Benzene Series. Diazo-derivatives of Mesitylene. GILBERT T. MORGAN and GLYN REES DAVIES (T. 1923 123 228-237). Azopicric Acid [2 4 6 2' 4' 6'-Hexanitro-5 5'-di- hydroxyazobenzene]. K. Ems and FR. SCHLIEPHAKE (J. pr. Chem. [ii] 1922 104 282-284).-The nitration of m-azophenol (cf. A. 1903 i 539) by the prolonged mtion of an ice-cold mixture of concentrated sulphuric acid and potassium nitrate subsequent treatment with water and extraction with benzene leads to the compound of 1 mol.of azopicric acid with 2 mols. of benzene flat deep blood-red prisms ; this loses benzene gradually more quickly on warming a t go" giving a 60% yield of pure nxopicric acid as a yellowish-red powder m. p. 238-239" (decomp.) which explodes violently when quickly heated. Azopicric acid dissolves readily in benzene (giving the above-mentioned compound) and also in water alcohol ether or acetone but is insoluble in carbon disulphide or concentrated hydrochloric acid. In aqueous solution it is a fast dye to wool and has an astringent (not bitter) taste. The potassium and barium salts are described. Capacity to Form Phenylhydrazones. VI. BERNARDO ODDO and LUIGI PIATTI (Gaxxetta 1922 52 ii 333-346).-Cryoscopic investigations in anhydrous phenylhydrazine similar to those already described (A. 1913 i 1233; 1915 ii 414 415) have now been made on a number of compounds containing in the molecule either two carbonyl groups or one carbonyl together with other radicles.Diacetyl reacts immediately with the phenylhydrazine giving a precipitate which does not dissolve readily. After a time how- ever the liquid becomes almost clear and the depression of the freezing point gradually attains a value which is 50% of the theoretical value for the diacetyl taken the formation of the monophenylhydrazone being thus indicated. Later the phenyl- osazone is precipitated in increasing amount. Similar difficulties as regards solubility are presented by anthraquinone with which a clear solution cannot be obtained. With acetylacetone the apparent molecular weight rapidly reaches a value equal to 40% of the theoretical value and subsequently slowly falls to become constant at about one-third the calculated value the diphenylhydrazone or more probably the pyr- azole compound being formed OH*CMe:CHAc +NH,*NHPh= OH*CMe:CH*CMe:N*NHPhfH,O=T ='cMe>CH+2H20.Similar results are obtained with benzil except that the initial velocity of the reaction is somewhat less. With dipyrroyl although the phenylosazone is known no reaction with phenylhydrazone occurs under the experimental conditions of the present investigation. As regards terpenic ketones camphor bromocamphor and W. G. W. S. N. NPh-CMei . 256 ABSTRACTS OF CHE"AL PAPERS. fenchone which are bicyclic are' h0rt towards phenylhydrazine. The monocyclic pulegone however reacts completely the mole- cular weight falling at approximately constant velocity to about 60% and then at gradually diminishing velocity to 52% of the theoretical value.Menthone behaves similarly to pulegone with which rather than with the other terpenic ketones examined it presents structural analogies. Carvone is inactive towards phenyl- hydrazine the double linking in the nucleus possibly favouring an enolic configuration. The results obtained wit! aldehydes emphasise the promptitude with which the aldehydic function is exercised in presence of phenylhydrazine. The aldehydes investigated were dextrose cuminaldehyde (isopropylbenzaldehyde) 0- m- and p-nitrobenz- aldehydes phenylacetaldehyde cinnamaldehyde m-nitrocinnam- aldehyde vanillin p-dimethylaniinobenzaldehyde f urfuraldehyde and phthalaldehyde. None of these remains inert towards phenyl- hydrazone and most of them quickly precipitate the phenyl- hydrazones.Furfuraldehyde reacts instantly but gives no pre- cipitate. With phenylacetaldehyde which also yields no pre- cipitate the reaction is somewhat slow in its final phase this aldehyde thus resembling the aliphatic aldehydes. Cinnam- aldehyde and its m-nitro-derivative on the other hand exhibit towards phenylhydrazine the behaviour of an aromatic aldehyde in spite of the fact that the aldehyde group lies in the side chain. Dextrose furnishes no precipitate with phenylhydrazine but the reaction proceeds with the regularity. shown in the case of the aliphatic aldehydes although t'he retarding influence of the alcoholic groups is manifest.Phthalaldehyde behaves abnormally the value of the molecular weight in phenylhydrazine solution being only 23% of the value calculated from the amount of the aldehyde taken. T. H. P. Santonin also is inactive. The Opening of the Lactone Ring of Phthalide Derivatives by Hydrazine. J. TEPPEMA (Rec. trav. chim. 1923 42 30- 68).-The object of this work was to study the influence on the stability of the lactone ring in phthalide of substituents both in the benzene ring and in the methylene group of the lactone ring. The stability of the ring is gauged by the ability or otherwise of hydrazine to open the ring with formation of a benzhydrazide and further by the stability of aldehydo- and keto-derivat'ives of the benzhydrazide.The action of hydrazine on phthalide was studied by Wedel who concluded that the product formed was the hydrazide of o-hydroxyrnethylbenzoic acid (A. 1900 i 363) but Blaise and Luttringer concluded that the additive compound was formed at the keto-group without rupture of the lactone ring (A. 1905 i 329). The results of the present work do not support the latter view. A number of derivatives of o-hydroxymethyl- benzhydrazide with aldehydes and ketones were prepared. p - Methox y benx ylidene - o - h y drox ymeth y 1 benzh yd razide OH~CH,*C,H,*CO*NH*N:CH*C,H,*OMe forms colourless needles m. p. 165". isoPro~yZidene-o-hydroxy-ORGANIC CHEMISTRY. i. 257 methylbenzhydruzide forms colourless spangles m. p. 148". A deriv- ative could not be obtained with acetophenone.d-Mannose-o- hydroxymethylbenzhydruzide crystallises in colourless needles m. p. 106-109"; in boiling aqueous solution it is decomposed by benzaldehyde with formation of benzylidene-o-hydroxymethyl- benz h ydrazide . d- Galactose - o - h yd rox ymeth y Zbenzh ydrazide was o b - tained in crystals m. p. 70-75" but could not be recrystallised unchanged. The corresponding dextrose derivative was obtained only as a syrup; it is decomposed by benzaldehyde in hot aqueous solution. An acetyl derivative of o-hydroxymethylbenzhydrazide can be obtained by the action of acetic anhydride in the cold. Its decomposition in the hot with formation of phthalide accounts for Wedel's failure to prepare it. The acetyl compound does not react with benzaldehyde and must therefore be a N-acetyl derivative.N- A cet yl-o-h ydrox ymeth y Zbenzh ydrazide OH*CH,*C,H,*C OONH-NHAc forms colourless spangles m. p. 146". No benzoyl derivative of o-hydroxymethylbenzhydrazide could be obtained with benzoyl chloride. The mono-nitro-derivative obtained by nitrating phthalide either with pure nitric acid or with a nitrate and sulphuric acid is 5-nitro- phthalide m. p. 143" not 4-nitrophthalide as stated by Hoenig (A. 1886 242). In the literature different methods of notation are adopted by different authors; the present author adopts the method shown in the annexed formula. 5-iVitro-2-hydroxymethyl- benzhydruzide forms yellow needles m. p. 167- N02c\lC0 ->o 168". The isopropylidene derivative of this forms colourless needles m. p. 165"; the benzylidene derivative forms colourless spangles m.p. 167O. The aldehyde and ketone derivatives of nitro-o-hydroxymethyl- benzhydrazide are not hydrolysed so readily as those of o-hydroxy- methylbenzhydrazide with re-formation of the phthalide and conversely the presence of the nitro-group facilitates the rupture of the lactone ring. N-Acetyl-5-nitro-2-hydroxymethylbenzhydrazide forms colourless spangles m. p. 171"; when boiled with acetic anhydride it is decomposed forming 5-nitrophthalide. 5-Aminophthalide is best prepared by reducing 5-nitrophthalide with hydrogen sulphide in ammoniacal alcoholic solution. When reduced with phosphorus and hydrogen iodide it gives an amino-o- tduic acid m. p. 196" not 153" as stated by Hoenig. This was identified as 4-amino-o-toluic acid which establishes the constitu- tion of the above 5-nitrophthalide.4-Amino-o-toluic acid was synthesised by a new method through the steps 4-nitro-o-toluidine -+ 4-nitro-2-cyanotoluene -+ 4-amino-2 -cyanofoluene -+ 4-amino- o-toluic acid. The lactone ring of 5-aminophthalide is opened by hydrazine with formation of 5 -amino -2 - hyd rox ymethylbenzhydrazide colourless needles m. p. 147"; benzylidene derivative m. p. 161"; isopropyl- idene derivative m. p. 170". 5-Acetamihphthulide forms colourless needles m . p. 222-4223'. When 5-amino -2-hydroxymethylbenz- hydrazide is treated with cold acetic anhydride it forms the diacetyl derivative 5-acet~mido-2- h ydrox ymeth ylucet yl benzhydrazide y3/CH,i. 258 ABSTRACTS OF CHEMICAL PAPERS. small colourless needles m.p. 195" ; but with hot acetic anhydride 5-acetamidophthalide is formed. Contrary to the statement of Hoenig 5-aminophthalide can be readily diazotised and transformed almost quantitatively into a halogen derivative by Sandmeyer's method. 5-Chwhthalide forms colourless needles m. p. 110" ; 5-brmophhaZide forms similar crystals m p . 98". 5- Chloro-2 - h ydrox ymeth ylbenxh ydraxide forms colourless needles m. p. 139"; benzylidene derivative m. p. 165-166" ; isopropylidene derivative m. p. 153" ; acetyl derivative m. p. 160". 5-Brmo-2-hydroxymethylbenxhydrazide forms colourless needles m. p. 152" ; benxylidene derivative m. p. 171" ; isopropyl- idene derivative m. p. 157"; acetyl derivative m. p. 153". The introduction of a single methyl ethyl or phenyl group into phthalide in the a-position stabilises the lactone ring to such an extent that hydrazine cannot effect the rupture.A chloro- bromo- or nitro-group in the 5-position of a-methylphthalide weakens the lactone ring sufficiently to permit rupture by hydrazine but this is not the case with a-ethylphthalide or a-phenylphthalide. 5-Amino-a-ethyl- and 5-amino-a-methyl-phthalide do not react with hydrazine. The dialkyl and diphenylphthalides are extremely stable and their inactivity towards hydrazine is not affected by substituents in the 5-position. 5-Nitro- a-methylphthalide the principal nitration product of a-methyl- phthalide is accompanied by a small quantity of an isomeride probably the 3-nitro-compound. With hydrazine 5-nitro-a- methylphthalide gives 5-nitro-2-a-hydroxyethylbenxhydraxide CH3*CH( OH)*C,H,(NO,)*CO*NH~NH forming colourless needles m.p. 120". The isopropylidene derivative has m. p. 127" but when recrystallised from alcohol partly decomposes with regeneration of the lactone. A benzylidene derivative could not be obtained on account of the formation of lactone. The lactone ring in 5-nitro-a- methylphthalide is therefore more stable than that in 5-nitro- phthalide . 5 - Nitro-2 - a- h ydroxy et h yl -acet ylbenzhydraxide m . p . 1 26" has similar properties to the other acetyl derivatives described. 5-Amino-a-methylphthalide does not react with hydrazine. From i t were prepared 5-chloro-a-methylphthaZide colourless needles m. p. 45" and 5-bromo-a-methylphthcclide m. p. 59". 5-Chloro- 2-a-hydroxyethylbenxhydraxide forms colourkss needles m.p. 108" ; its isopropylidene derivative has m. p. 119". The 5-bromo-2-a- hydroxyethylbenzhydraxide has m. p. 119" and its isopropylideize derivative 135". 5-Amino-a-ethylphthalide was obtained by reduc- tion of the corresponding nitro-compound ; it forms small yellow needles m. p. 140". From this were obtained fj-chloro-a-ethyl- phthalide colourless needles in. p. 54" and 5-bromo-a-ethylphtha;lideY similar crystals m. p. 63". By the action of hydrazine on a-amino- or a-bromo-phthalide 1-keto-1 2-dihydrophthalazine (annexed formula) is obtained and the same substance is /\*C":T formed from hydrazine and diphthalide ether ICO-NH which thus behaves as the anhydride of phthal- \ / * aldehydic acid. 5-Amino-a-dimethylphthalide crys- a-Methylphthalide has n14 1.5450 d'j 1.1601 m.p. 7".ORGANIC CHEMISTRY. i. 259 tallises in colourless needles m. p. 115". With bromine it gives 4 6-dibromo-5-amino-a-di~~hyl/phthalide colourless needles m. p. 138". 4 6-Dibr~no-5-amino-~-diethylp~~lid~ crystallises in spangles m. p. 93". Not one of these derivatives of a dialkyl- phthalide is acted on by hydrazine. The work serves to confirm and extend Hjelt's rule regarding the stability of lactone rings (A. 1891 822). The Configuration of the Doubly-linked Tervalent Nitrogen Atom. The Resolution of the Pyridylhydrazone of cyclo- Hexylene Dithiocarbonate. WILLIAM HOBSO N MILLS and HANS SCHINDLER (T. 1923 123 312-323). DAVID I. HITCHCOCK ( J . Gen. PhysioE. 1923 5 383-394).-By the use of the silver- silver chloride electrode and the hydrogen electrode electrometric determinations have been made of the chloride and hydrogen-ion concentrations in solutions of proteins (gelatin egg-albumin casein edestin and serum-globulin) to which varying quantities of hydrochloric acid have been added. It is concluded that the hydrochlorides of these proteins are strongly ionised and that there is no marked repression of the ionisation by excess of hydro- chloric acid.W. 0. K. Density of Albumin Solutions. M. A. RAKUSIN and G. D. FLIEHER (Chem. Ztg. 1923 47 66).-A table is given of the density of albumin solutions a t 17" up to a concentration of 15*35% a t which the solution is saturated. White of egg is a saturated solution of albumin. When freed from fat and clarified by treat- ment with lead acetate albumin has a considerably lower density than the crude substance the value for a 5% solution being df5 1.01288 for the pure substance and d15 1.01341 for the crude.E. H. R. The Ionisation of Protein Chlorides. The specific rotatory power is unchanged by the purifying process. H. C. R. The Nature of Nucleins. S. NAKAGAWA (2. physiol. Chm. 1923 124 274-277).-Hydrolysis of nucleoprotein by pepsin yields no nuclein. The idea of Steudel is confirmed that nucleo- proteins are loose compounds of nucleic acid and a protein base. W. 0. K. The Hydrolysis of Proteins by Strong Sulphuric Acid. E. SALKOWSKI (Biochem. Z. 1922,133,1-2O).-Horn on complete hydrolysis by three times its weight of 73.6% sulphuric acid gives practically no humin material.The hydrolysate reduces Fehling 's solution to an extent which indicates the presence of 13% of apparent sugar.. Pyruvic acid aldehydes of the aliphatic series and furfuraldehyde are also present. E. ZUNZ and P. GYORGY (Bull. A d . roy. Be&. 1914 359-380).-An investigation of Pick's heteroalbumose (A. 1900 i 68) by two methods (1) Fractionation by Siegfried's method (A. 1906 i 144) and (2) ultra-filtration using collodion and acetic acid of three different concentrations. The authors W. 0. K. Heteroalbumose.i. 260 ABSTRACTS OF CHEMICAL PAPERS. conclude that Pick's hetero-albumose is really a mixture. The chief constituent (insoluble in twice its bulk of 95% alcohol) is a heteroalbumose with [ x ] -72*5" but associated with it are several protoalbumoses of low rotatory power and soluble in twice their bulk of alcohol.One of these is apparently responsible for the Adamkiewicz reaction given by some preparations of Pick's heteroalbumose. Altogether fifteen different fractions of the latter are examined and compared with the original substance by means of elementary analysis rotatory power gold numbers refractive indices etc. Bioluminescence. XV. Electro-reduction of Oxyluci- ferin. E. NEWTON HARVEY ( J . Gen. Physiol. 1923 5 275- 284) .-If a solution containing luciferin and luciferase and some sodium chloride is electrolysed the oxyluciferin is reduced a t the cathode by the nascent hydrogen and as it is oxidised back again in the presence of the luciferase by the oxygen dissolved in the water with the production of light there is immediately luminescence.Similar reduction by nascent hydrogen also takes place at the surface of metals (aluminium manganese zinc and cadmium) when these are immersed in water containing oxy- luciferin although there is no actual production of molecular hydrogen. Other systems are described where electrochemical reduction of luciferin occurs. I n general the production of light by the combination oxyluciferin-luciferase is a very good test for nascent hydrogen. Molecular hydrogen does not produce lumines- cence. If however a palladiumised surface be introduced i t becomes strongly luminescent as it activates the hydrogen. E. E. T. W. 0. K. The Mechanism of the Effect of Acids and Alkalis on the Digestion of Proteins by Pepsin or Trypsin.A Correction. JOHN H. NORTEELOP ( J . Gen. Physiol. 1923 5 415; cf. this vol. i 69)-A statement made in the previous paper (loc. cit.) to the effect that the amount of acid required to bring protein solution to a given PSI is independent of the nature and valency of the aaion is true only of strong acids. Influence of Reaction on the Activity of Trypsin. 11. W. E. RINGER (2. phpiol. Chem. 1923 124 171-193; cf. A. 1922 i 282).-The solution of fibrin by trypsin is inhibited by sulphates thiocyanates and ferrocyanides but more strongly by multivalent kations such as calcium which also strongly inhibit the swelling of fibrin in water. The effects however are not quite analogous ; bile salts for example completely inhibit the solution of fibrin at concentrations a t which the effect on the swelling is quite inappreciable.Salts with multivalent kations affect the viscosity of alkaline protein solutions (dialysed serum). The effect of these salts on the tryptic hydrolysis of such solutions is at first one of inhibition but this very soon disappears. Experi- mentls confirm the fact that alkaline protein solutions show a gradual increase in internal friction and that after a long time W. 0. K. the internal friction again becomes less. w. 0. I<.ORQANIC CHEMISTRY. i. 261 Equilibrium between the so-called " Antitrypsin '' of the Blood and Trypsin. RAYMOND G. HUSSEY and JOHN H. NORTHROP ( J . Gen. Physiol. 1923 5 335-351).-From a study of the inhibition of trypsin by blood plasma it is concluded that the effect is not one of adsorption but that it is more probably chemical in nature.It is shown that if the assumption is made that an easily dissociated compound of the trypsin and the inhibiting substance is formed the law of mass action is obeyed according to the equation [Trypsin] [inhibiting substance]/[Com- pound of Trypsin and inhibiting substance]=K. Equilibrium is attained very quickly and is reversible and this fact opposes the view that there is an adsorption. Quantitative experiments have been carried out by the authors' method on (1) the effect of adding varying amounts of plasma to a constant amount of trypsin (2) the effect of adding varying amounts of trypsin to a constant amount of plasma and (3) the effect of dilution on a plasma- trypsin mixture and the results accord with the theory that a reversible equilibrium is attained.These conclusions are in harmony with the results that have been obtained with other enzymes. W. 0. K. Invertase. A. FODOR (2. physiol. Chem. 1923 124 278- 281).-Criticism of the results of Willstatter Graser and Kuhn (A. 1922 i l200) pointing out the difficulty of being certain of the purity of the preparations obtained. Kinetic Researches on Saccharase. H. VON EULER and K. MYRBACK (2. physiol. Chern. 1923 124 159-170).-The unimolecular reaction constant k is determined for the inversion of sucrose by saccharase (invertase) from the expression Ic= 1 It. log u/(u-x) where x is the amount of sucrose inverted in a time t out of the initial amount a. With increasing values of c the initial concentration of the sucrose the value of the product kc increases until c is about 4 g.per 100 c.c. after which it is constant until c is about 20 g. per 100 c.c. and then it decreases. If on the assumption that a reversible equilibrium is reached between enzyme and substrate the constant K= [Enzyme][Sub- strate]/[Enzyme Substrate] is calculated which is possible if i t be also assumed that all the enzyme is combined with the substrate when E is maximal it is found to vary from 0.027 to 0.0175. W. 0. K. W. 0. K. Influence of Amino-acid in Protecting Amylase from Inactivation by Mercury. H. C. SHERMAN and MARY L. CALD- WELL ( J . Amer. Chem. Soc. 1922 44 2923-2926).-Glycine and phenylalanine and presumably other amino-acids protect against small concentrations of mercuric chloride added when testing the activity of purified pancreatic amylase and allow the latter to act almost as efficiently as if no mercury were present.The minute amounts of mercury which might conceivably have been present in the histidine and tryptophan preparations used could not therefore account for their entire lack of activating influence oni. 262 ABSTRACTS OF CHEMICAL PAPERS. the amyloclastic action of the enzyme as previously recorded (A. 1922 i 283). Influence of Lysine on the Hydrolysis of Starch by Purified Pancreatic Amylase. H. C. SHERMAN and MaRy L. CALDWELL ( J . Amer. Chem. Xoc. 1922 44 2926-2930).-Lysine has no effect on the amyloclastic action of pancreatic amylase but exerts a favourable influence on its saccharogenic action.Accepting the view that the enzyme (pancreatic amylase) is essentially a protein substance which gradually becomes inactivated through hydrolysis in the aqueous medium in which it acts and that the apparent activating influence of amino-acids is due to retardation of this hydrolysis of the enzyme it is suggested that the lysine in the enzyme molecule is not split off until after the stage of amylo- clastic action has passed but is only concerned in the later stages represented by saccharogenic activity. These observations con- firm and extend the theory advanced to explain the effect of histidine and tryptophan on the same enzyme (A. 1922 i 283). W. G. W. G. Influence of some Organic Compounds upon the Hydrolysis of Starch by Salivary and Pancreatic Amylases. H.C. SHERMAN and NELLIE M. NAYLOR ( J . Amer. Chem. Xoc. 1922 44 2957-2966) .-The authors consider that the favourable effect reported by Rockwood (A. 1917 i 358; 1918 i 86 274) to be exerted by several types of organic compounds on the activity of amylolytic enzymes was due in most if not in all cases other than those of natural amino-acids to hydrogen-ion or salt effects rather than to the organic structure of the compounds. In the presence of favourable concentrations of chloride- phosphate- and hydrogen-ions no favourable effect on the activity of the enzyme was shown by methyl- and ethyl-amine hydrochlorides aniline sulphate benzoic acid benzamide anthranilic acid or hippuric acid. Previous results as to the favourable influence of several amino-acids resulting from protein hydrolysis have been confirmed and extended.This influence may be attributed either to a direct activating effect dependent on the structural nature of these substances as a-amino-acids or to conservation of the enzyme by retarding its hydrolysis but the results with hippuric acid fail to confirm the activation hypothesis. Some Actions of Thorium-X on Diastases and Micro- organisms. J. P. AVERSENQ L. JALOUSTRE and E. MAURIN (Compt. rend. 1923 176 193-195).-Thorium-X a t the concen- trations used activates in a marked manner the hydrolysing and oxidising enzymes studied the increased action in a given time being of the order of 30%. Similarly relatively small amounts of thorium-X were capable of increasing the vitality of certain pathogenic organisms and of certain living cells.Peroxydase. 111. RICHARD WILLSTATTER and ADOLF POL- LINGER (Annulen 1923 430 269-319).-In continuation of previous work (A. 1918 i 555) on the purification of peroxydase W. G. W. G.ORGANIC CHEMISTRY. i. 263 preparations the authors have made a detailed study of the influence of adsorption on and subsequent elution from alumina and kaolin and of precipitation by tannic acid on the activity of peroxydase solutions. On the basis of these experiments two methods of purification are worked out in detail the results of each operation being followed by determinations of the " purpuro- gallin number " (loc. cit.). According to one method the per- oxydase in a solution having a purpurogallin number 302 is first adsorbed on alumina suspended in 50% alcohol removed in carbonic acid solution and then again adsorbed on alumina in dilute alcohol.One further adsorption on kaolin in 50% alcohol and three.sub- sequent adsorptions on alumina raise the purpurogallin number to 4900 the highest value as yet observed. According to the second method the peroxydase is subjected to four adsorptions on alumina in 50% alcohol and three on kaolin in 0-O2N-acetic acid and a precipitation by tannin the final purpurogallin number being 3070. The question as to whether iron enters into the constitution of peroxydase cannot be conclusively settled on the analytical data because although for a given natural source and method of purification the iron content runs roughly parallel with the purpuro- gallin number a change either in the source or the process affects the proportion of iron in a way which cannot at present be simply accounted for.C. K. I. Reductases. 11. Comparison of the InfIuence of Alkalis on Potato Reductase. I. A. SMORODINCEV (2. physiol. Chem. 1923 124 202-210; cf. A. 1922 i 1201).-The effect of alkali on the reductase in potatoes (nitrase) is to inhibit the activity an effect apparently independent of the kation and due to the hydroxyl-ion concentration. W. 0. K. Mode of Action of Vitamins. AKTONIO DE GREGORIO ROCASOLANO (Anal. Fis. Quim. 1922 20 433436).-Theoretical. The vitamins are held to act as colloidal catalysts. Vitamins-B and -D. CASIMIR FUNK and JULIA B. PATON ( J . Metabolic Research 1922 1 737-775).-Vitamin-B is destroyed by alkali and also by heating in an autoclave under pressure for three hours; the effect of such treatment on vitamin-D is much smaller.When grown in a solution containing both vitamins yeast or other fungi removes the latter which is retained tenaciously by the yeast-cells. CHEMICAL ABSTRACTS. An Attempt to Resolve Quaternary Phosphonium Com- pounds. L. G. RADCLIFFE and W. H. BRINDLEY (Chemistry and Industry 1922 42 64-66).-1n the hope of effecting a resolu- tion of a quaternary phosphonium compound phenyl-p-toZyEmethyZ- allylphosphonium d-bromocamphorsulphonate was prepared but attempts to crystallise it failed; it was only obtained as a jelly- like mass finally becoming resinous. The synthesis of the com- pound was accomplished from p-tolyldichlorophosphine through phenyl-p-tolylchlorophosphine to phenyl-p-tolylmethylphosphine G. W. R.i. 264 ABSTRACTS OF CHEMICAL PAPERS. which was then combined with ally1 iodide. The ha1 yield was very small. Attempts t o prepare phenyl-p-tolylethyl-n-butyl- phosphonium iodide from phenyl-p-tolylethylphosphine and n-butyl iodide led only to the formation of an uncrystallisable oil. E. H. R. Additive Reactions of Phosphorus Halides. VI. The 1 2- and 1 4-Addition of Diphenylchlorophosphine. J. B. CONANT J. B. S. BRAVERMAN and R. E. HUSSEY ( J . Amer. Chem. Xoc. 1923 45 165-171; cf. A. 1921 i 69).-Diphenylchloro- phosphine reacts with benzaldehyde and phenyl styryl ketone in the presence of glacial acetic acid giving respectively an hydroxy- and a keto-phosphine oxide. By using acetic anhydride in place of the acid the mechanism of the reaction with the unsaturated ketone has been established. Under these conditions an un- saturated intermediate compound O ( P P h < ~ ~ ~ ~ > C H ) is formed but could not be isolated in a crystalline state. On tieat- ment with water it gives the ketophosphine oxide and it readily combines with two equivalents of bromine to yield a dibromide without the evolution of hydrogen bromide. This dibromide not isolated as such on treatment with water gives a mixture of two isomeric monobromoketophosphine oxides one of which can be obtained by direct bromination of the ketophosphine oxide itself. These two monobromo-derivatives behave differently towards alcoholic sodium hydroxide. The one with the high m. p. loses hydrogen bromide to give an unsaturated ketophosphine oxide whilst the other is reduced to the ketophosphine oxide. On the other hand by boiling it with potassium acetate in methyl alcohol the bromo-compound with the high m. p. is reduced to the keto- phosphine oxide. The following compounds are described. Diphenyl-a-hydroxy- benxylphosphine oxide m. p. 230" obtained from benzaldehyde and diphenylchlorophosphine. Ciphen yl- p - benxoyl- a-phen ylethylphos - phine oxide m. p. 227" similarly obtained from phenyl styryl ketone. oxide m. p. 225-226". Diphenyl- p-bromo- p-benzoyl- a-phenylethylphos- phine oxide in two isomeric forms m. p. 187" and 158" respectively. Diphenyl-p-bromo-p-p-chlorobenxoyl-a-phenylethylphosphine oxide in two isomeric forms m. p. 196" and 187" respectively. Biphenyl- @-benzoyE-a-phenylvinylphosphine oxide m. p. 143" ; and diphenyl- P-p-chlorobenzoyl-a-phenylvilzylphosphine oxide m. p. 151 ". W. G. Diphen y 1 - p - p - c hl orobe nzoy 1 - a - phen y let h y 1 phos phin e Tetraphenyldiarsine. PARRY BORGSTROM and MARGARET M. DEWAR ( J . Amer. Chem. Xoc. 1922 44 2915-2923).-An exten- sion of previous work (A. 1920 i 196). When tetraphenyl- diarsine is prepared in a pure state out of contact with air its m. p. is 130-130.5" (corr.) (cf. Michaelis and Schulte A. 1883 187). Quantitative data are given for its oxidation in moist air and for its absorption of iodine which latter decreases with theORQANIC CHEMISTRY. i. 265 age of the solution. This decrease in iodine absorption corresponds with an increase in molecular weight as determined cryoscopically in naphthalene as solvent. The specific conductivity in liquid sulphur dioxide increases with the age of the solution changing from 1 3 . 3 ~ 1 0 ~ to 100x10-6 mhos in nineteen days. The con- ductivity also increases with rise in temperature. The data indicate that the bond between the arsenic atoms of the tetraphenyldi- arsine is easily broken. Bivalent arsenic of the type Ph,As' may be present transitorily in solution but it is doubtful if it is the stable form. The valency or configuration of the stable form is not known. Tetraphenyldiarsine reacts with methyl iodide forming dimethyl- diphenylarsonium iodide (cf. Steinkopf and Schwen A. 1921 i 694). W. G. Some Determinations of Molecular Weight in the Arsinic Acid Series. RICHARD LORENZ and ELISABETH BREHMER (Ber. 1923 56 [B] 174-176; cf. Lorenz and Schmidt A. 1920 i 777 897 ; ii 465).-The molecular weights of arsanilic o-toluidino- resorcino- 3-nitro -4-aminophenyl- 3 -nitro-4-hydroxyphenyl- 3-nitrophenyl- p-phenylenedi- and o-phenylenediamine-arsinic acids have been estimated in aqueous solution by the ebullioscopic method. They appear generally to have the simple non-poly- merised structure of the type [ P ~ . A s O < ~ ] ~ . .O H o-Phenylenedi- aminearsinic acid however is polymerised to such an extent that it may exhibit double the normal molecular weight but different preparations give different values. Arsanilic acid (NH,*C,H,-AsO,)H is strictly monobasic and is preferably represented as an internal salt [C6H,( NH,)*O*AsO*O]H. Similar observations are recorded with o-toluidinoarsinic acid p - dime t h y lamino p hen ylarsinic and 0- p hen ylenediamin e - arsinic acid. Resorcino- 3-nitro-4-aminophenyl- dichlorophenyl- dibromophenol- 3-nitro-4hydroxyphenyl- p-iodophenyl-arsinic acids and 4-amino-3-carboxyphenyl-arsine oxide behave normally with regard to electrical conductivity and exhibit normal molecular weights . H. W. acid Preparation of Mercury Dibenzyl. A. GARCIA B A N ~ S (Anal. Pis. Quim. 1922 20 667-668).-Mercury dibenzyl is prepared by treating benzyl chloride with excess of magnesium dust and adding mercuric chloride to the liquid after decanting from excess of magnesium. The mixture is heated with frequent shaking under a reflux apparatus. Dilute acetic acid is added and mercury dibenzyl is obtained by crystallisation from the ethereal solution. It has m. p. 110-111". G. W. R.

ISSN:0368-1769    

DOI:10.1039/CA9232400173

出版商:RSC    

年代:1923

数据来源: RSC

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ii. 174 ABSTRACTS OF CIIEMICAL PAPERS. Mineralogical Ch e mist r y. Parsonsite a New Radioactive Mineral. ALFRED SCHOEP (Compt. rend. 1923 176 171-173).-The green colour of some specimens of torbernite from Kasolo Katanga Belgian Congo (A. 1922 ii 155) is obscured by a brown powder. This is readily separated by washing in water and consists of minute crystals (monoclinic or triclinic) with d17 6-23 n> 1.99. When heated it turns yellow and fuses to a black bead; it is readily soluble in acids. Analysis gave PbO. CuO. 5-0,. P,O,. TeO,. MOO,. CaO. 44-71 0.25 29.6; 15.08 3.01 0.43 0.63 A1203. co,. Inqol. H,O. Total. 1.23 1.19 1.51 1.56 99.47 Deducting impurities (copper due to admixed torbernite) the formula is 2Pb0,U0,,P20,,H,0. Tellurium and molybdenum were de- tected also in the torbernite; and the pitchblende from Kasolo contains selenium and molybdenum.Presence of the Element No. 72 (Hafnium) in Malacon and Alvite. V. M. GOLDSCHMIDT and L. THOMASSEN (Norsk Geologisk Tidsskrift 1923 7 61-68) .-The relation of element 72 to zirconium suggested the examination of some anomalous zircon-like minerals by the method of X-ray spectrum analysis (A. Hadding A. 1922 ii 780 855) using a rock-salt crystal turned by clockwork. Malacon from Hittero Norway showed the lines of zirconium element 72 iron manganese yttrium and trace of tungsten. Alvite from Kragero Norway showed the lines of zirconium strong 72 iron manganese aldebaranium yttrium weak thorium and perhaps traces of cerium and tungsten. The formula of alvite is written as (Zr,72,Th)0,,Si02. Meteoric Iron from Glasgow Kentucky.GEORGE P. MERRILL (Amer. J . Sci. 1923 [v] 5 63-64; Chem. News 1923 126 63-64).-Two much-oxidised masses weighing about 25 and 20 lb. were recently ploughed up. The structure is that of a coarse octahedrite. L. J. S. L. J. S. Analysis by J. E. WHITFIELD gave Fe. Ni. co. S. P. C. c1. 70.63 7.27 0.62 0.11 0.13 0.06 0.36 Fe,Ni oxides. SiO,. Ign. Total. 19.22 trace 1.65 100.04ANALYTICAL CHEMISTRY. ii. 175 The percentage of chlorine corresponds with 0.62 yo of lawrencite (FeClJ. This is high and accomts for the ready disintegration of the material which is difficult to arrest. Meteoric Iron from Somerset County Pennsylvania. GEORGE P. MERRILL (Amer. J . Sci. 1923 [v] 5 175-176).-An oxidised mass of about 18 kg. was ploughed up in 1922 on Allegheny Mountain and is called the New Baltimore iron. It is an irregularly granular mass readily breaking into fragments; and it therefore probably belongs to the same fall as the Mt. Joy iron found 90 miles away. Analysis by J. E. WHITFIELD gave Fe . Ni. co. P. Si. C. Total. 93.256 6.420 0.325 0.037 0.010 0.015 100.063 L. J. S. Copper manganese and sulphur are absent. L. J. S.

ISSN:0368-1769    

DOI:10.1039/CA9232405174

出版商:RSC    

年代:1923

数据来源: RSC

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ANALYTICAL CHEMISTRY. An a1 y t ieal Chemistry. ii. 175 New Vessel for Electrometric Titration. W. T. Born ( J . Amer. Chem. Soc. 1922 44 2892-2893).-A new form of glass vessel for use in electrometric titrations is described. The vessel has a capacity of about 150 C.C. ; it is oviform in shape and at its wider end is fitted with four tubulures one in the exact centre being for the burette jet and the other three situated a t equi- distant points on a circle being for the hydrogen electrode calomel electrode and hydrogen inlet respectively. The vessel is attached to a stout glass rod a t its lowest point which slips into a hole in a heavy support. J. F. S. Some Applications of Oxygen Electrode Air Electrode and Oxidation Potential Measurements to Acidimetry and Alkalimetry. N.HOWELL FURMAN ( J . Arner. Chem. Soc. 1922 4-4 2685-2697).-An oxygen or air electrode constructed in the manner generally adopted for a hydrogen electrode may be used for the titration of the acid or alkali in the presence of oxidising agents such as potassium dichromate or potassium permanganate. The method yields accurate results and by using an empirical scale the E.M.F. readings of the cells are built up as indicated. Platinised platinum I oxygen/ lacid or alkaline solution of an oxidising agent I calomel-electrode ; will serve to give a quantitative indication of the hydrogen-ion concentration. Mixtures of Tartrates and Phosphates as Buffers. An- tagonistic Action of Calcium Chloride. L. J. SINON and L. ZIVY (Compt. rend. 1923,176 136-138; cf. A 1922 ii 880).- The addition of calcium chloride exerts inverse effects in the neutral- isation of tartaric acid and phosphoric acid.In the case of tartaric acid the neutral zone as between helianthin and phenolphthalein J. F. S. 7*-2ii. 176 ABSTRACTS OF CHEMICAL PAPERS as indicators tends to disappear whilst in the case of phosphoric acid it is doubled. This phenomenon is additive and if the two acids are mixed in equimolecular proportions the neutral zone and the correlative buffer effect are invariable. Method €or the Micro-estimation of Chlorine in Blood. PAUL IVERSEN and M. J. SCHIERBECK (Ugeskr. Zueger 84 454- 456; from Chem. Zentr. 1922 iv 1076).-0.1 C.C. of blood is added to 0.8 C.C. of 0-1N-sodium hydroxide and 4 C.C. of 0.45% zinc sulphate solution. After heating for three minutes the liquid is filtered and treated with 0.2 C.C.of 29% nitric acid and 1 C.C. of 0-O1N-silver nitrate solution. When the precipitate has settled the clear supernafant liquid is titrated with 0-OO5N-ammonium thiocyanate in the presence of one drop of saturated iron ammonium alum solution. G. W. R. Bang’s Method for the Micro-estimation of Chlorine. PAUL IVERSEN (Ugeskr. Zueger 84 4 5 6 4 5 8 ; from Chem. Zentr. 1922 iv 1076) .-Discordant results in the micro-estimation of chlorine are attributed to variations in the amount of ethyl alcohol used for the extraction of blood and in the method of extraction. G. W. R. W. G. The Reaction between Hypochlorite and Potassium Iodide. I. M. KOLTHOFF (Rec. truv. chim. 1922,41 615-626; cf. following abstract).-Hypochlorous acid to which a solution of sodium hydrogen carbonate has been added reacts with potassium iodide according to the equation 3HCIO+I’ -+ 10‘,+3H0+3C1’ the form- ation of hypoiodite being a preliminary stage in the oxidation of the iodine.When the quantities of each substance are equivalent the hypoiodite reacts with iodide liberating iodine. The rate of transformation of hypoiodite into iodate depends on the hydrogen- ion concentration of the solution. In the presence of mineral acids the end-point cannot be ascertained by means of starch as no iodine-ions remain in the solution; moreover iodate may be transformed into chloro-compounds of iodine in solutions con- taining sulphuric or hydrochloric acid. It is stated that Klimenko’s method of estimation of hypochlorite and chlorine in presence of each other (A.1904 ii 205) is untrustworthy. Chlorine in sodium hydrogen carbonate solution may be titrated in a similar manner to iodine. H. J. E. I. M. KOLTHOFF (Rec. trav. chim. 1922 41 740-750) .-Solutions of hypocklorites on being kept are transformed into chloride chlorate and also into chlorite. I n estimating hypochlorite in bleaching powder by means of potassium iodide in sulphuric acid solution the presence of chlorite introduces an error as it reacts according to the equation ClO,’+ 4I’+4H’ -+ 2I2+C1’+H,O although chlorates have no such influence. Chlorite reacts very slowly if a t all with arsenious acid or with potassium iodide in sodium hydrogen carbonate solution so that the titration of hypochlorite may be carried out accurately with either of these reagents according to Treadwell’s The Titration of Hypochlorite.ANALYTICAL CHEMISTRY.ii. 177 method. I n effecting the titration by Pontius's method the operation must be carried out slowly in presence of a large excess of sodium bicarbonate (cf. J.S.C.I. 1923 1 8 1 ~ ) . Detection of Hypochlorites and Chloroamines in Milk and Cream. PHILIP RUPP (U.S. Dept. Agr. Bull. 1922 1114 1-5).-Five C.C. of the milk or cream 1.5 C.C. of a 7% solution of potassium iodide and 4 C.C. of hydrochloric acid (1 2) are heated in a water-bath a t 85" for ten minutes cooled and 0.5 to 1 C.C. of starch solution is added. The presence of available chlorine in amounts as low as 1 in 50,000 is indicated by the pale yellow colour of the milk below the curd changing to a light reddish-purple passing through reddish-purple to a deep bluish- purple as the amount of chlorine is increased.Milk pasteurised after the addition of hypochlorites at 63" for thirty minutes reacts in the same way as raw milk. P. POCH (Anal. F k Quim. 1922 20 662-666).-The reactions for chlorates are discussed. Potassium chlorate and ammonium thiocyanate heated together a t 140-150" produce an orange-red mass with deflagration. The mass contains carbon nitrogen and sulphur and when heated on platinum foil burns with a violet flame leaving a small residue of carbon. The orange-red colour may be used as a test for chlorates by adding 1 C.C. of O.5N-ammonium thiocyanate to 1 C.C. of a solution of a chlorate and evaporating to dryness.The orange- red coloration is given even with 0.00025 g. of potassium chlorate. G. W. R. A Method for the Simultaneous Estimation of Sulphur and Halogen in Organic Compounds. CLIFFORD S. LEONARD ( J . Amer. Chem. SOC. 1923 45 255-257).-A detailed account of Klason's method for the combined estimation of sulphur and halogens in an organic substance (A. 1886 918). The material to be analysed is placed in a porcelain boat a t one end of a com- bustion tube which contains in sequence a platinum spiral a boat filled with fuming nitric acid and a second platinum spiral. The first end of the tube has attached to it a bubbling flask of fuming nitric acid and the other end is drawn out so as to dip into water or silver nitrate solution. The combustion is thus carried out in an atmosphere of nitrous fumes and air or oxygen may be slowly passed through the tube.At the end of the combustion the tube and its contents are rinsed with distilled water the rinsings being added to the liquid in the receiving flask. I n this liquid the halogens and sulphur may then be estimated as is done after a Carius combustion. W. G. Micro-estimation of Sulphuric Acid and Sulphur in Organic Substances by the Benzidine Method. G. ZIMMER- LUND and 0. SVANBERG (Svensk. Kem. Tidslcr. 1922 34 139- 146 ; from Chem. Zentr. 1922 iv 1094).-The solution containing sulphuric acid is exactly neutralised and precipitated with a solution of beilzidine hydrochloride. The precipitate is centrifuged H. J. E. CHEMICAL ABSTRACTS. Analytical Investigation of Chlorates.ii.178 ABSTiUCTS OF CHEMICAL PAPERS. and the total filtrate titrated with O.05N-sodium hydroxide and phenolphthalein according to Bang's method (lililcrobestimmung von Blutbestandteilen 1922). The sulphuric acid content is derived from the difference between the titre thus obtained and the titre of the acid benzidine solution. Directions are given for the pre- paration of the benzidine hydrochloride solution. Josk GIRAL PEREIRA (Ancrl. Fis. Quim. 1922 20 577-585).-The method consists in boiling the solution containing an alkali sulphate with excess of a solution of barium chromate in 0.1N-hydrochloric acid. Excess of calcium carbonate is added and after filtering 5 C.C. of fuming hydrochloric acid are added for each 100 C.C. of filtrate followed by excesci of solid potassium iodide.By the action on the alkali chromate (equivalent to the original sulphate) iodine is liberated and may be titrated in the usual way with thiosulphate. G. W. R. Volumetric Estimaticjn of Sulphates in Sea-water. G. W. R. Refractive Indices of Selenic and Selenious Acid. HOSMER W. STONE ( J . Amer. Chem. Xoc. 1923 45 29-36).-The refractive indices of solutions of selenic and selenious acid in water have been determined for concentrations varying between 0.00 yo and 98.98 yo for selenic acid and 0.00% and 79.14% for selenious acid using an Abb6 refractometer and sodium light at 20". Tables have been constructed giving the refractive indices of solutions of the two acids for every percentage value over the whole range measured.Using this method the two acids may be rapidly and accurately estimated in solution. Selenic acid may be estimated gravi- metrically as follows. The sample 0.2-0.5 g . is treated with 50 C.C. of concentrated hydrochloric acid and diluted to 75-100 C.C. with water. The solution is heated to boiling and 30 C.C. of saturated aqueous sulphur dioxide solution are added. The solution is maintained a t 98" until the red precipitate first formed turns black and further additions of sulphur dioxide gave no red pre- cipitate. After the reaction mixture had been kept four to five hours a t 80-go" the precipitate was collected on a Gooch crucible Estimation of Nitric Oxide. A. KOEHLER and M. M u - QUEYROL (Me'm. PoudTes 1922 19 359-361).-Escess of oxygen is added to the gaseous mixture in the presence of a liquid secondary amine such as ethylaniline which absorbs the nitrous anhydride formed.The excess of oxygen is removed with alkaline pyrogallol and the contraction of volume gives the volume of nitric oxide. Under atmospheric pressure ethylaniline dissolves its own volume of carbon dioxide so that if this gas is present considerable excess of oxygen should be added so as to keep the partial pressure of the carbon dioxide low. A high degree of accuracy is attainable. RODILLON ( J . Pharm. Chim. 1923 [vii] 27 64-65).-The author concedes priority to Denighs and dried a t 105-110". J. F. S. H. C. R. Detection of Nitrites in Water.ANALYTIC.& CHEMISTRY. ii. 179 (Bull. Sci. Pharmawl 1914) for the use of resorcinol in sulphuric acid solution as a reagent for nitrites.G. F. M. The Detection of Nitric Acid by Ferrous Sulphate. CARL FAURHOLT (Ber. 1923 56 [B] 337-341).-The customary brown- ring test for nitric acid occasionally gives very erratic results. These are traced to insufficient rapidity in the reduction of nitric acid. The defect can be most readily remedied by the addition of hydrochloric acid a drop of which (4N) is introduced previously to the addition of sulphuric acid. The brown coloration is produced immediately. The presence of 0.5 mg. of potassium nitrate in 2 C.C. of solution can be detected with certainty. The limit of applicability of the method lies a t about 0.2 mg. if control solutions are used to obviate the disturbance caused by the formation of yellow solutions of ferric chloride.The oxidation of ferrous sulphate in solutions containing nitric and hydrochloric acids appears to proceed in such a manner that the acids first react with one another and that the chlorine and nitrosyl chloride thus produced convert the ferrous into the ferric salt. The oxidation of ferrous sulphate by nitric acid which occurs at high concentrations of nitric and sulphuric acids or at elevated temperature in the absence of hydrochloric acid does not occur to an appreciable extent under the experimental conditions. H. W. Estimation of Nitrogen in Nitrates Cellulose Nitrates and Glyceryl Nitrates by Devarda's Method. A. KOEHLER M. MARQUEYROL and P. JOVINET ( M h . des Poudres 1922 19 348-350 ; 351-355 ; 356-358).-1f any ammonia is present it is estimated by distilling into acid in the usual way.The contents of the flask are then cooled and a volume of water is added equal to that which has been distilled over. Twenty-five g. of finelypul- verised Devarda's alloy (A1=45% Cu=50% Zn=5%) are added and the flask is connected to a Kjeldahl distillation apparatus and hydrogen allowed to come off for fifteen to twenty minutes after which i t is gently boiled for ten minutes and the ammonia formed is distilled into acid and estimated in the usual way methyl-red being used as indicator. A blank determination must be carried out with the reagents used. In the case of cellulose nitrate the ester is first hydrolysed with aqueous potassium hydroxide and hydrogen peroxide. The temperature must not exceed 60" until all the cellulose nitrate is dissolved but the liquid is afterwards boiled until oxygen ceases to be given off and then cooled to the ordinary temperature.The nitrate is then reduced with Devarda's alloy as described above. The method can be applied to glyceryl nitrate but t o obtain accurate results the hydrolysis must be carried out below 40". This is only possible with the aid of violent agitation. A form of glass agitator suitable for use in a conical flask for this purpose is illustrated. It is provided with two bulbs blown on the stem so as nearly to close up the mouth of the flask and so prevent loss of the contsnts through splashing. Afterii. 180 ABSTRACTS OF CHEMICAL PAPERS. forty minutes' treatment the glyceryl nitrate is completely dis- solved and the temperature increased to 70" for a few moments.The estimation is then carried out as described above. This method gives more accurate results than the nitron method. H. C. R. N. TARUGI (Gaxxetta 1922 52 ii 323-332).-The quantitative separation of arsenic from antimony tin copper lead mercury and iron may be effected as follows the arsenate solution is heated for thirty minutes with hydrazine sulphate and sufficient sodium hydroxide to correspond with about one-half of the hydrazine. The liquid is then cooled and distilled for one and a half hours with concen- trated hydrochloric acid the distillate which is found to contain the whole of the arsenic being collected in a flask connected with a Pkligot tube. The arsenic may then be estimated either gravi- metrically as sulphide or after the distillate has been rendered alkaline to methyl-orange by means of sodium hydroxide and then treated with excess of solid sodium hydrogen carbonate by titration with iodine solution.R. GUERIN (Ann. Chim. Analyt. 1923 5 &S).-The official French method for estimating iron silicon and aluminium oxide in metallic aluminium is described and the composition and nature of silicon-aluminium alloys are discussed. A method is also given for the estimation of combined silicon (as aluminium silicide) and of graphitoidal silicon in the alloys depending on the insolubility of the latter form in aqua regia and its solubility in a mixture of hydrofluoric and nitric acids (cf. J.S.C.I. 1923 186A). Use of Malic Maleic and Fumaric Acids in Volumetric Analysis.N. A. LANGE and HBRY KLINE ( J . Amer. Chem. SOC. 1922 44 2709-2711).-The suitability of malic maleic and fumaric acids for use as standards in the titration of alkalis and potassium permanganate has been investigated. It is shown that the three acids suitably purified give accurate and trustworthy resulk9 when used to standardise sodium hydroxide or potassium hydroxide. The commercial products must however always be purified before use for the above-named purpose. In the case of maleic acid the purification is effected by a single crystallisation from water containing four drops of nitric acid for every 200 C.C. of solution; after air drying the crystals are dried to constant weight over sulphuric acid or in an oven a t 90". Phenolphthalein is the best indicator for this acid.Pumaric acid is purified and used in the same way as maleic acid but in this case owing to the smaller solubility of the acid the titration must be effected a t a higher temperature. Malic acid is purified by dissolving in hot acetone filtering adding carbon tetrachloride to the hot solution and allowing to crystallise. The crystals are air-dried for twenty-four hours then for an equal time over sulphuric acid or for two hours a t 90-120°. Although maleic and fumaric acids Separation of Arsenic from other Elements. T. H. P. [Estimation of] Silicon in Aluminium. A. R. P.ANALYTICAL CHEMISTRY. ii. 181 may be used as standards for potassium permanganate solutions they are neither as accurate nor as convenient as sodium oxalate for this purpose.Succinic malic maleic and fumaric acids cannot be used as standards for ammonium hydroxide solutions and the two last-named acids cannot be used for iodine titrations. J. F. S. The Estimation of Potassium as Alum. (IMLLE) DE LE PAULLE (Compt. rend. 1923 176 105-107).-The method is for use in estimating small quantities of potassium in rocks. It is based on the comparative insolubility of potash alum in 30% (by volume) aqueous ethyl alcohol. In alcohol of such a strength aluminium sulphate is readily soluble. The mineral is digested with sulphuric and hydrofluoric acids ; the solution is evaporated to dryness and the residue ignited a t a dull red heat. A weighed portion of the residual sulphates is dissolved in water and the solution cooled and sufficient alcohol is added to bring it to 30%.After the whole of the potash alum has separated it is collected washed with the dilute alcohol dried and weighed. Estimation of Potassium Salts with Sodium Cobaltinitrite. E. CLERFEPT (Bull. SOC. chirn. Belg. 1922 31 417420).-The perchlorate method of estimating potassium salts is said to be unsatisfactory but it is claimed that accurate results are obtained by the use of sodium cobaltinitrite numerous analyses showing an agreement within 0.1 to 0.2% of the results obtained by pre- cipitation with platinic chloride. The reagent is made up in two solutions I. 28.6 g. of cobalt nitrate and 50 C.C. of glacial acetic acid are made up to 500 C.C. with water. 11. A solution of 180 g. of sodium nitrite in 500 C.C.of water. The two solutions should be kept separately and for use I is slowly added to I1 twenty-four hours before the estimation to permit of the precipitation within that period of any potassium in the technical sodium nitrite in which case the solution must be filtered before use. An excess of the reagent is added gradually with mechanical stirring to as concentrated as possible a solution of the potassium salt slightly acidified with acetic acid. Forty C.C. are required for 0.25 g. of potassium chloride in 25 C.C. of solution and in any case not less than 10 C.C. of reagent are used. Stirring is continued for half an hour and the beaker set aside until next day when its contents are filtered on a tared filter the precipitate washed with 10% acetic acid until the washings are colourless and then once with 95% alcohol and dried at 120". The dried precipitate has the formula K,NaCo(N0,),,H20 and contains 20.74% K,O. Estimation of Potassium by Przibylla's Sodium Hydrogen Tartrate Method and its Application to the Analysis of Potassium Salts of the Alsatian Basin.PAUL HUBERT (Ann. Chim. Analyt. 1923 5 9-14).-The method of Przibylla (Kali 1908 No. 18) as modified by Bokemuller (ibid. 1918 No. 15) has been further modified and adapted to the estimation of potassium in Alsatian sylvinites of very varying richness. The method W. G. P. M.ii. 182 ABSTRACTS OF CHEMICAL PAPERS. consists essentially in adding a slight excess of sodium hydrogen tartrate to the solution containing a definite weight of the sample filtering an aliquot part of 'the liquid and titrating with sodium hydroxide free from carbonate. According to the richness of the sample the quantities of reagents used are altered so that the percentage of potassium can be calculated directly from the amount of sodium hydroxide used (cf.J.S.C.I. 1923 1818). A. R. P. Separation and Estimation of Sodium and Lithium by Precipitation from Alcoholic Perchlorate Solution. H. H. WILLARD and G. FREDERICK SMITH (J. Amer. Chem. Soc. 1922 44 2816-2824).-A method for the quantitative separation of sodium and lithium is described. The method depends on the precipitation of sodium chloride from a mixture of the perchlorates by means of a butyl alcohol solution of hydrogen chloride and is carried out as follows. The mixture of sodium and lithium salts must be converted into chlorides by any suitable method and must contain no trace of sulphate.The mixed chlorides are evaporated to dryness with an excess of perchloric acid. If potassium is present it is f i s t separated by the usual perchlorate separation and the filtrate after the addition of water is evaporated to dryness. The mixed perchlorates of sodium and lithium free from perchloric acid are dissolved in n-butyl alcohol using a t least 18.5 C.C. for each 0.1 g. of sodium chloride likely to be formed later. The mixture dissolves readily if the alcohol is boiled. Then 0.1 C.C. of 70% perchloric acid is added and the solution cooled to -No and 1.0-1-5 C.C. of 20% hydrogen chloride in n-butyl alcohol are added slowly from a burette with continuous stirring after which sufficient of the hydrogen chloride solution is rapidly added t o form a 6% solution.The solution is then heated to boiling for a few minutes allowed to cool and the sodium chloride filtered on a Gooch crucible washed eight to ten times with a 6-7% solution of hydrogen chloride in n-butyl alcohol dried for one hour at 250° and ignited a t 600" for five to eight minutes in a muffle furnace cooled and weighed. A correction of 0.6 mg. must be made for the sodium chloride remaining in each hundred C.C. of filtrate. The filtrate and washings diluted with one-third of their volume of water are evaporated to dryness. If the residue is brown it must be heated on a gauze until fumes of perchloric acid are evolved and if insufficient of this acid is present to effect the complete oxidation of the organic matter a little should be added.The colourless residue is treated with 0.5 C.C. of concentrated sulphuric acid and heated until the whole of the acid has been expelled. The beaker is cooled 5-10 C.C. of water are added and the lithium sulphate is transferred to a platinum crucible evaporated to dry- ness ignited to drive off all free acid and finally heated at 600" in a muffle furnace for five to ten minutes. A correction of 0.7 mg. per 100 C.C. of filtrate and washings should be subtracted from the weight of lithium sulphate. The results given by the pro- cedure are uniformly good. The solubilities of sodium perchlorate lithium perchlorate sodium chloride and lithium chloride inANALYTICAL CHEMISTRY.ii. 183 n-butyl alcohol at 25" have been determined along with the densities of the saturated solutions and the following values are recorded lithium perchlorate 44.23 ; &5= 1.1341 ; sodium perchlorate 1.83 ; di5=0*8167 ; lithium chloride 11.49 ; df=0.8713 ; sodium chloride 0.014; e'=0*8060. The solubilities are given in g . per 100 g. of solution. The densities dy of solutions of hydrogen chloride in n-butyl alcohol have also been determingd and the following recorded Oyo 0.8060; lyi 0.8130; 2y0 0.8195; 3% 0.8255; 4% 0.8315; 5% 0.8370; 6% 0.8425; 7% 0.8485; 8yo 0.8540; 9% 0.8590; lo% 0.8635; 11% 0.8685; 120/ 0.8730; 13% 0.8770; 14% 0*8810; 15% 0.8850; 16% 0*8S&; 17% 0.8935; IS% 0.8960; 19% 0.9010 and 20% 0.9050. J. F. S. Oxidimetric Estimation Qf Calcium and its Employment in Technical Work. J.GROSSFELD (Chem. Weekbhd 1923 20 3941).-In the method of estimating calcium by adding excess of ammonium oxala$e filtering and titrating an aliquot part of the filtrate with permanganate the solution should con- tain a considerable quantity of a weak acid; phosphoric acid is most suitable but the amount used must be carefully regulated. The procedure of Vurtheim and van Bers (A. 1922 ii 869) is tedious requiring two hours' heating on the water-bath. A simplified method which may be carried out in a beaker consists in dissolving the substance (containing not more than 0.140 g. CaO) in the cold in 20 C.C. 4N-phosphoric acid adding with stir- ring exactly 20 C.C. of the oxalate solution (20 g. per litre) and finally 30 C.C.of 2-5N-sodium hydroxide; the solution is filtered through a fine-pored filter and 50 C.C. are titrated with N/10- permanganate. The method can be employed for fertilisers foodstuffs waters and for estimating very small quantities of calcium. If reducing substances are present the material may be ignited. S. I. L. The Approximate Estimation of Magnesium in a Single Drop of Sea-water. G. DENIG~S (Compt. rend. 1922 175 1206-1208) .-The author describes the conditions under which the brown precipitate produced by the action of potassium hypo- iodite on a solution containing magnesium-ions may be employed as a method for the colorimetric estimation of magnesium. Full experimental details are given (cf. J.S.C.I. 1923 2 0 7 ~ ) . It is claimed that the method is rapid and sufficiently accurate for most purposes; moreover a single drop only of the solution to be analysed for magnesium is required. The Acidirnetric Titration of Magnesium in its Salts.I. M. KOLTHOFF (Rec. truv. chim. 1922 41 787-794).-The potentiometric titration of solutions of magnesium salts by means of alkalis is tedious and can only be carried out in solutions of a concentration greater than 0.5N ; even under the most favourable conditions the error lies between 1 yo and 2 yo. No greater accuracy is attained by titrating a magnesium solution of concentration 0-6N or greater with normal sodium hydroxide using nitramine H. J. E.ii. 184 ABSTRACTS OB CHEMICAL PAPERS. aa indicator. The method recommended is based on the addition of excess of alkali to the solution containing magnesium which is then made up to a definite volume shaken and allowed to remain.An aliquot portion of the clear solution is then titrated for excess of alkali which should not be present to a greater extent than 0-01N. The presence of calcium is not disadvantageous. H. J. E. A New Method of Estimating Cadmium. R. CERWATESCO (Bull. Acud. Sci. Roumaine 1922 8 43-46).-The cadmium is precipitated as sulphide by means of hydrogen sulphide and excess of the gas boiled off. A known volume of silver nitrate is added to the solution together with the precipitate and the latter is blackened immediately owing to the formation of silver sulphide. The whole is heated so as to complete the transformation and the excess of silver nitrate determined by titration (cf.Mann A. 1879 1054). If chlorine is present the precipitated cadmium sulphide must be separated by filtration through asbestos before the silver nitrate is added. The Titration of the Mercuric-ion with the Chlorine-ion and its Application to the Analysis of Cinnabar axid Organic Derivatives of Mercury. MILE VOTO~EK and LADISLAV KA~P~REK (Bull. SOC. chim. 1923 [iv] 33 110-122).-The method previously described for the mercurimetric estimation of chlorides may conversely be used for the estimation of mercury (cf. A 1918 ii 238 272). The metal in the form of a mercuric salt of an oxygenated mineral acid is titrated in the cold with standard sodium chloride solution in presence of 0.06 g. of sodium nitroprusside per 200 C.C. volume of liquid. The titration is con- tinued until the cloudiness due to mercuric nitroprusside just disappears and under these conditions 1 C.C.of N/lO-sodium chloride is equivalent to 0.010124 g. of mercury. For the estim- ation of mercury in mercuric sulphide or in cinnabar about 0.3 g. of substance is digested with 50 C.C. of an oxidising mixture of 1 vol. of nitric acid with 2 vols. of sulphuric acid and diluted to 1000 C.C. after complete decolorisation 200 C.C. of the diluted solution being used for a titration. For the estimation of mercury in organic derivatives the same treatment was successful in the aliphatic series but in the aromatic and heterocyclic series nitric acid and powdered potassium permanganate were required to effect the destruction of the organic matter.Oxides of manganese in the reaction product were dissolved by the addition of sodium nitrite solution excess of nitrous acid was eliminated by per- manganate and sulphuric acid followed by a few drops of oxalic acid to produce a colourless solution which was then titrated with sodium chloride as above. When halogens are present i t is of course necessary to precipitate the mercury as sulphide and redissolve the precipitate in the ni tric-sulphuric acid mixture before proceeding to the titration. The direct titration is not disturbed by the presence of metals of which the nitroprussides are soluble in water and mercury can accordingly be estimated H. J. E.by this method in presence of alkali or alkaline-earth metals of lead zinc aluminium chromium ferric iron or manganese. G.3'. M. Estimation of Iron in Ores and Silicate Rocks. F. R. ENNOS and R. SUTCLIFFE (Summary of Progress Qeol. Survey 1921 174-176).-1n the case of samples containing iron aluminium titanium and phosphate the weighed oxides of the aluminium group are fused with pyrosulphate and the titanium is estimated colorimetrically in the solution resulting from this fusion. The solution is then evaporated to a volume of about 100 c.c. the excess of hydrogen peroxide is destroyed by treating the hot solution with the required quantity of sulphurous acid and the solution a t 90" is saturated with hydrogen sulphide. The precipitate of sulphur and platinum sulphide (the platinum is derived from the crucible in which the fusion was made) is separated by filtration and washed with very dilute sulphuric acid.The filtrate is cooled oxidised with dilute potassium permanganate solution 10 C.C. of concentrated hydrochloric acid and 5 C.C. of 20% ammonium thiocyanate solution are added and the iron is titrated with standardised titanium trichloride solution. w. P. s. The Separation of Iron and Zinc by Means of Bases. K. SCHERINGA (PiZarm. Weekblad 1923 60 39-43).-Addition of sodium hydroxide to a solution containing both zinc and ferric salts precipitates the two metals together the weight of zinc oxide carried down varying with the amount of iron present although not directly. Even if the zinc salt be added after the sodium hydroxide the resalts are the same nor could complete separation be effected in any way with this base.Precipitation with cold concentrated ammonia (25 %) effects complete separation if ammonia of the same strength be used to wash the precipitate. s. I. L. Successive Electrometric Titration of Iron Uranium and Vanadium. R. G. GUSTAVSON and C. M. KNUDSON (J. Amer. Chem. Xoc. 1932 44 2756-2761).-Analysss of salts of iron vanadium and uranium have been investigated by the electro- metric method individually and in all possible combinations and it number of curves plotted indicating the results. Iron vanadium and uranium may each be titrated electrometrically after reduction with zinc and sulphuric acid but in the case of vanadium the titration must be carried out in an indifferent atmosphere such as carbon dioxide. A high concentration of acid favours sharp inflection points a t all three end-points in the vanadium titration.Mixtures of salts of iron and uranium may be titrated with per- manganate solution after reduction with zinc and sulphuric acid by the electrometric method provided the acidity is kept low the optimum concentration being about 5 C.C. of concentrated sulphuric acid to 250 C.C. of solution. Iron and vanadium in mixtures may be estimated by a similar method using 10 C.C. of acid to 250 C.C. of solution but in this case the titration must be made in an atmosphere of carbon dioxide to obtain trustworthyii. 186 ABSTRACTS OF CHEMTCAL PAPERS. results. The volume representing the vanadium is obtained directly from the final step in the curve whilst that representing iron can be obtained by subtracting this value from the fimt step in the same curve. The estimation of vanadium and uranium in mixtures when 5-10 C.C.of sulphuric acid are present may be made by titrating the mixture in a non-oxidising atmosphere. The vanadium is obtained directly as before and the uranium by difference. When all three elements iron vanadium and uranium are present the estimation may be made similarly. It is best to use 4 C.C. of sulphuric acid to 250 C.C. of solution for the first part of the titration and then after the second inflection is obtained a like quantity of acid is added and the titration con- tinued. The vanadium and iron are represented by the last and the next to the last steps respectively whilst the uranium is again found by subtracting the value found for vanadium from the value indicated in the portion of the curve between the first and second inflections.J. F. S. Gravimetric and Volumetric Methods for the Estimation of Tin in Alloys. ANTON~N J ~ E K (Chem. Listy 1923,17 7-ll).- Two methods for the estimation of tin in alloys are examined namely the gravimetric method of Czerwek (2. anal. Chem. 1876 15 505) and an iodometric method. Czerwek’s method and its modifications for the analysis of bearing metals are closely studied. The following observations are made. The atanniphosphate precipitate should be washed with a mixture of acids similar to that used to dissolve the alloy but with the addition of phosphoric acid and not with nitric acid alone as Czerwek recommends otherwise antimonic acid which is insoluble in nitric acid would remain adsorbed on the precipitate.The solution of this precipitate in alkali sulphide should not be boiled very long as a gelatinous precipitate containing stannic oxide and phosphoric oxide tends to separate with increase in hydroxyl-ion concentration. In the conversion of the stannous sulphide into stannic oxide the sulphide should be moistened before the addition of nitric acid as otherwise the violence of the reaction would lead to spattering of the contents of the crucible. A series of analyses of pure tin was carried out reducing progressively the quantity of tin but keeping the quantities of the reagents constant. As a result it was found that with the quantities of the latter used [6 g . of acetic acid 15 C.C. of nitric acid (d 1*4) 30 drops of 45% phosphoric acid and 15 C.C.of water followed by dilution with 300 C.C. of boiling water] the best results are obtained using 0.1 g. of tin Should more be used the results are high whilst with less precipitation of tin is slow and incom- plete so that using 0-0022 g. of tin only 43% was found by this method. The stanniphosphate precipitate was examined and its composition found to be roughly 2Sn0 P,O,. This varies with the quantity of phosphoric acid used and can contain adsorbed lead copper and antimony salts. For this reason the tin cannot be estimated by weighing the stanniphosphate precipitate. R. T.ANALYTICAL CHEMISTRY. ii. 187 New Method for the Electrometric Titration of Vanadium in the Presence of Iron and Chromium. H. H. FVILLARD and FLORENCE FENWICK ( J .Amer. Chem. Soc. 1923 45 84- 92).-The electrometric titration of vanadium by means of ferrous sulphate solution and potassium permanganate solution has been investigated. It is shown that a polarised bimetallic electrode system affords a more sensitive means of determining the end-point in the reduction of vanadic acid by ferrous sulphate than the usual monometallic electrode. I n acetic acid solution the reduction of chromic acid by hydrogen peroxide in the presence of vanadic acid may be made selective and gives an excellent means of estimating the latter element in all alloy steels. Results may be obtained which agree to 0.005% when 5 g. samples are used; one advantage over the method involving selective oxidation of vanadium with nitric acid lies in the reduced period of boiling required.Traces of vanadium may be titrated directly in the presence of large quantities of phosphotungstate and phospho- molybdate. For the analysis of vanadium steels the following procedure is recommended. Chromium and chromium vanadium steeE. A sample requiring about 10 C.C. of 0.02N-ferrous sulphate is placed in a 600 C.C. beaker 20-30 C.C. of water are added and the calculated quantity of concentrated sulphuric acid is added from a burette. Each gram of steel requires 1.0 C.C. of this acid and a 4.0 C.C. excess to effect rapid solution. The beaker is heated gently until the sample is dissolved and salts commence to separate. The solution is then diluted with 20 C.C. of hot water and warmed until clear when 4-5 C.C.of concentrated nitric acid are added cautiously and the solution is boiled. The oxidation of the iron and vanadium is completed with a slight excess of a solution of potass- ium permanganate. Sufficient sodium acetate is added to combine with the sulphuric acid in excess over that required for solution of the steel (1 C.C. concentrated sulphuric acidE4.8 g. of sodium acetate trihydrate) and 40-50 C.C. of glacial acetic acid. Then 0.5 g. of neutral sodium perborate is added the solution diluted to 200 c.c. and boiled for twenty minutes. The solution is cooled to the ordinary temperature 25-30 C.C. of concentrated hydro- chloric acid are added and titrated with 0-OBN-ferrous sulphate solution using a bimetallic system to ascertain the end-point (this vol. ii 33).Chromium vanadium molybdenum steels are treated in exactly the same way. Chromium vanadium tungsten steels. The sample is treated with 40 C.C. of hydrochloric acid (3 l) and heated until action ceases. Then 8-10 C.C. of con- centrated nitric acid are added drop-wise and when the f i s t violent action has ceased the solution is evaporated to 20 C.C. It is then diluted with hot water and boiled to dissolve soluble salts filtered and the residue washed with 2y0 hydrochloric acid. The filtrate is oxidised with potassium permanganate and the free acid neutralised by a sufficient excess of sodium acetate (1 g . of hydrochloric aciE3.73 g. of sodium acetate trihydrate). From this point the analysis is as described above. A small quantity of vanadium is occluded by the tungstic acid; to estimate this,ii.188 ABSTRACTS OF CHEMICAL PAPERS. the tungstic acid is dissolved in sodium carbonate solution and boiled for ten minutes with about 0.5 g. of perborate. It is then acidified with 3-5 C.C. of phosphoric acid and 25-40 C.C. of sulphuric acid (3 1) and titrated electrometrically to the permanent drop in potential. Detection of Antimony and Tin in Qualitative Analysis. E. RUPP (Ber. Deut. pharm. Ges. 1922 34 334-335).-A modific- ation of the usual test for antimony in presence of tin (by means of platinum foil and granulated zinc) is described in which the platinum foil is replaced by a very small piece of platinum wire. Details are also given of a method in which the platinum is entirely dispensed with being replaced by a piece of iron wire by which it is claimed that 0.08 mg.of antimony can be detected with certainty. P. M. J. F. S. Interferometric Analysis of Liquid Mixtures of Organic Substances. ERNST COHEN and H. R. BRUINS (2. physikal. Chem. 1923 103 337-348).-The authors have investigated the difficulties which arise when the Rayleigh-Lowe water inter- ferometer is used for the analysis of solutions of organic liquids. It is shown that when using this instrument with organic liquids the upper interference band undergoes a lateral displacement and becomes diffuse whilst the bands are oblique and bent and continuously change their form. These changes are due to the influence of temperature on the refractive index of the solvent the vaporisation of the liquid and condensation on the cover glass the absorption of water from the air during the placing of the liquid in the observation vessels and the index of refraction of the bath liquid.Each point has been subjected to careful experiment and precautions for eliminating the disturbance in each case are in- dicated. When all these precautions are taken the water inter- ferometer gives results which are as sharp and as exact as those obtained with aqueous solutions. HUGO MASTBAUM (Anal. Fis. Quim. 1922 20 501-504).-Phenols are extracted from thyme oil by repeated shaking with sodium hydroxide solution. On addition of strong hydrochloric acid to an aliquot portion of the extract the phenols separate. The thymol is obtained by crystallisation and weighed after collection and drying. J. F.S. Estimation of Thymol in Thyme Oil. G. W. R. Colorimetric Estimation of Pyrogdol Gallotannin and Gallic Acid. C. AINSWORTH MITCHELL (Bnalyst 1923 48 2-15).-The method is based on the fact that it solution con- taining 0.1% of ferrous sulphate and 0.5% of sodium potassium tartrate reacts immediately with gallotannin to form a soluble compound which unlike the ink formed with ferrous sulphate alone is fairly stable. The coloration ranges from reddish- to bluish-violet it is a,pparently specific for the pyrogallol grouping,ANALYTICAL CHEMISTRY. ii. 189 and its intensity is proportional to the amount of this tinctogenic group in gallic acid and the various tannins. Thus the colour factor for gallic acid referred to pyrogallol is identical with the ratio of their molecular weights namely 1 1.5 for crystalline gallic acid and 1 1.36 for the anhydrous acid.Owing to its greater stability it is preferable to use solutions of gallic acid rather than of pyrogallol as the standard for comparison and in the estimation of the natural gallotannins the gallic acid equivalent is determined colorimetrically and this must then be multiplied by a suitable factor to obtain the absolute amount of gallotannin. Owing to the uncertainty of the constitution of these substances this factor can only be obtained empirically and it varies with different varieties; for Aleppo galls for example the factor 1.85 was found suitable whilst for the tannin in Chinese galls the factor 2.1 is appropriate. Por the estimation of the tinctorial value of a tannin i t is however unnecessary to use these factors a t all the pyrogallol equivalent expressing all that is required.Based on the hypothesis that the colour intensity is always a measure of the pyrogallol groups present it is suggested that the average " pure " gallotannin is a mixture o€ different glucosides but mainly of di-digalloyl glucose with a digallic anhydride of the type described by Nierenstein (J. SOC. Chem. Ind. 1922 2 9 ~ ) . Such a mixture would yield the required proportion of dextrose and contain the necessary pyrogallol groups to give the observed coloration with the ferrous tartrate reagent. Most natural gallo- tannins contain a proportion of gallic acid and each can be colorirnetrically estimated by estimating the two substances together first in terms of gallic acid then precipitating the gallo- tannin by means of quinine hydrochloride and finally estimating the gallic acid in the filtrate the difference between the two results multiplied by the appropriate factor giving the amount of gallo- tannin.The results of the estimation of gallic acid and gallo- tannin in numerous commercial varieties of nut galls including white and roasted galls and also in myrobalans and various other materials containing tannin such as tea are given. G. F. M. Estimation of the Admixed Arachidic and Lignoceric Acids in Peanut Oil by means of Magnesium Soaps. ARTHUR W. THOMAS and CHAI-LAN Yu (J. Amer. Chem. SOC. 1923 45 113-128).-The authors have made a systematic and quantitative study of the behaviour of a number of pure soaps in various solvents and in particular the solubilities of the magnesium soaps of various fatty acids in 90% (by volume) ethyl alcohol have been measured.At 25" 100 g. of the alcohol dissolve 0.007 g. of mag- nesium stearate or 0.006 g. of magnesium lignocerate but 8-60 g. of magnesium oleate. The results indicate that an excellent separation of magnesium stearate arachidate and lignocerate from magnesium oleate linolate and linolenate is possible by means of this solvent. Under the same conditions 100 g. of 94.3% (by volume) alcohol dissolve 0.633 g. of potassium stearate 0.153 g. of potassium lignocerate or 41.1 g. of potassium oleate. Theii. 190 ABSTRACTS OE" CHEMICAL PAPERS. solubilities of stearic and lignoceric acids in three strengths of alcohol have been determined and the results show that a quanti- tative separation of arachidic and lignoceric acids from other saturated acids can best be accomplished with 90% (by volume) alcohol after remaining for one night at 20" or 25".A new method for the estimation of peanut oil based on the above separation of the magnesium soaps of saturated and un- saturated acids is outlined as follows 10 g. of the oil are saponified by boiling with a mixture of 50 C.C. of 5% alcoholic potassium hydroxide and 50 C.C. of 95% alcohol for half an hour. The soap solution while still warm is neutralised with 20% alcoholic acetic acid and then made just alkaline with the alcoholic potassium hydroxide using phenolphthalein as indicator. To this solution 25 C.C. of alcoholic magnesium acetate (50 g.of magnesium acetate dissolved in 100 C.C. of water heated to boiling and filtered and the filtrate diluted with three volumes of 95% alcohol) are added and the mixture is heated to boiling and left over-night at 10". The insoluble soaps are collected and washed with 30 C.C. of 90% alcohol. These insoluble soaps are then hydrolysed by boiling with 100 C.C. of 5N-hydrochloric acid for five minutes. Cold water is added to precipitate the solid acids which are collected and washed free from magnesium and chlorine. The solid acids are extracted with three successive portions of 20 C.C. of warm 90% alcohol and the solution left over-night a t 20" or 25". The crystals which form are separated and washed twice with 10 C.C. of goo/ alcohol and then with 70% alcohol until the washings give no turbidity with water.The filtrate and washings are collected and measured. The solids are washed with alcohol into a weighed beaker; the solvent is evaporated and the residue dried at 80" and weighed. This weight is corrected for the weight of lignoceric and arachidic acids which remain dissolved in the filtrate and washings of 90% alcohol. I n estimations of known mixtures of peanut oil with olive oil or cotton-seed oil the error did not exceed 5% of the value found for the peanut oil. The percentage of arachidic and lignoceric acids in peanut oil are taken as 5% on an average. Time and work may be saved by using the solution left after the ordinary determination of the saponification number for the above procedure if a high order of accuracy is not required.The proposed method is not intended for the separation of saturated acids from all unsaturated acids in all fatty oils as magnesium erucate and an unsaturated magnesium soap from tung oil (probably eleomargarate) were found to be insoluble in 90% alcohol (cf. following abstract). W. G. New Qualitative Tests for Rape and T u g Oils. AF~THUR W. THOMAS and CHAI-LAN Yu ( J . Amer. Chern. Xoc. 1923 45 129-130).-Rapeseed oil is subjected to the method of analysis outlined for peanut oil (cf. preceding abstract) and the acid cake left after hydrolysis of the magnesium soaps is dissolved in 60 C.C. of 90% alcohol and the solution is left over-night a t 20" or 15".ANALYTICAL CHEMISTRY. ii. 191 Any crystals which may have formed are filtered off and discarded and the filtrate and washings evaporated to dryness and the m.p. or acid number or preferably the iodine number of the residue is determined. Two samples of genuine rapeseed oil thus treated yielded about 25% of the final acid product having m. p. 35" (erucic acid has m. p. 32") iodine number 70-72 (erucic acid has 74.99). I n the case of tung oil the insoluble magnesium soaps are collected while hot washed with 90% alcohol and decomposed with dilute hydrochloric acid in the absence of air. The liberated acid has a strong odour characteristic of tung oil. It is soluble in cold 90% alcohol and melts a t about 44". After one or two days' contact with air it absorbs oxygen and gradually changes to a dark brown resinous mass.The yield of this acid (eleomargaric) obtained from one sample of tung oil tested was about 20%. W. G. The Estimation of Chloral Hydrate. I. M. KOLTHOFF (Plmrm. Weekbhd 1923 60 2-8).-In the ordinary method in which the chloral is converted by excess of sodium hydroxide into chloro- form and sodium formate and the excess of alkali titrated with standard acid the results are always high ; this has been attributed to action of the excess of alkali on the chloroform produced. The error is in fact due to absorption of carbon dioxide from the air by the alkali during the time required for the reaction and if decinormal sodium hydroxide is used the mixture may be allowed to remain at 40" for twenty minutes without decomposition of the chloroform. Accurate results are obtained by allowing 30 C.C.of N/lO-sodium hydroxide to act on 25 C.C. of 0.1 molar chloral hydrate solution for fifteen minutes in a closed flask and then titrating the excess using phenolphthalein ; the alkali must be standardised by carrying out the same procedure. The iodine method of Rupp (A. 1903 ii 699) in which the aldehyde is oxidised to trichloroacetic acid by excess of iodine the latter being titrated back in the usual way gives poor results if sodium hydroxide is used as proposed by Rupp. Good results are obtained by adding 2 C.C. of N-sodium carbonate and 10 C.C. of 0.1 molar chloral hydrate to 25 C.C. of N/lO-iodine solution leaving one hour in a closed vessel adding hydrochloric acid and titrating with thiosulphate. The chloral hydrate for the work was standardised by Wallis's method (A.1906 ii 255) as modified by van Rossum (A. 1908 i 501) i.e. complete hydrolysis to sodium chloride and sodium formate by heating with sodium hydroxide in a sealed tube and gravimetric estimation of the chloride. Bromine in acid solution will not oxidise chloral which therefore must have a much greater reducing power in alkaline than in acid solutions. s. I. L. A New Test for Acrddehyde and Its Bearing on Rancidity in Fats. WILMER C. POWICK ( J . Id. Eng. Chem. 1923 15 66).-To a few drops of dilute acraldehyde solution in a test-tube a drop of 3% hydrogen peroxide is added and after about oneii. 192 ABSTEACTS OF CHEMICAL PAPERS. minute 5 C.C. of concentrated hydrochloric acid are added and the test-tube is shaken.On shaking with 5 C.C. of a 1% ethereal solution of phloroglucinol a deep red colour is imparted to the aqueous layer showing a fairly narrow absorption band in the yellow-green. The red colour is not obtained in the absence of hydrogen peroxide whilst if there be an excess of acraldehyde a purple precipitate is obtained. This test differs from the Kreis test for rancidity in fats by the addition of the hydrogen peroxide and under these conditions no coloration is given by the saturated aldehydes or by crotonaldehyde. The spectrum given by the substance formed in the Kreis test is identical with that obtained as above and it therefore seems that the substance responsible for this test in rancid fats is identical with that produced by the action of hydrogen peroxide on acraldehyde.P. 31. Use of Schiff’s Reagent for the Estimation of Acraldehyde. CHARLES MOUREU and ETIENNE BOISMENU ( J . Pharm. Chim. 1923 [vii] 27 49-54 89-97).-Acraldehyde can be accurately estimated colorimetrically by means of Schiff ’s reagent by adopting the following procedure a standard solution of acraldehyde con- taining 0.5 g. per litre is prepared from the freshly distilled sub- stance by collecting in an ampoule sealing and weighing and then breaking in the requisite quantity of water to give a solution of the required strength. One arm of each of two inverted Y-tubes is filled respectively with 10 C.C. of this standard solution and 10 C . C . of the unknown acraldehyde solution diluted to contain slightly less than 0*05y0 of acraldehyde. The other arms are then filled with 5 C.C.of Schiff’s reagent the tubes are closed with glass stoppers and simultaneously inverted thereby mixing the reagent with the two solutions a t the same moment. For the attainment of the maximum intensity of coloration twenty-five minutes are allowed before examining the tints in the colorirneter. The height of the standard solution having the same intensity of coloration as 25 mm. of the solution under test is measured and the acralde- hyde content of the latter may be read off directly from the curve provided which may be reconstructed from the following figures where I is the height of standard solution in mm. and I1 the concen- tration of acraldehyde in mg. per litre in unknown solution. I. 25 22 20 0 18.5 15.6 12.8 10.3 11.500.0 476-2 454.5 434.8 4004 370.4 333.3 It will be seen from these figures that on diluting EL solution of acraldehyde the intensity of coloration is lowered more rapidly than the acraldehyde content. The whole of the above procedure must be carried out with cold solutions as a t higher temperatures the colours obtained are never comparable but consist of a mixture of colours tending towards green with varying velocities with solutions of varying concentrations. The presence of stabilisers such as pyrogallol pyrocatechol quinol or gallic acid does not interfere with the colorimetric estimation. G. F. M.ANBLYT1cA.L CHEMISTRY. ii. 193 The Estimation of Acetone in Methyl Alcohol and the Purification of Methyl Alcohol by Sodium Hypoiodite. HENRY HUTCHIKSON BATES JOHN MYLNE MULLBLY and HAROLD HARTLEY (T.1923 123 401-44). Estimation of Acetone in Methyl Alcohol. ELLA SODER- LUND (Svensk. Kern. Tidslcr. 34 152-157; from Chem. Zenfr. 1922 iv 1074-1075).-A modification of the method of Messinger (A. 1889 313). Ten C.C. of methyl alcohol are diluted to 100 c.c.; 10 C.C. of this solution are treated in a stoppered flask with 25 C.C. of sodium hydroxide solution. A large excess of 01-N-iodine solution is added and after keeping in darkness for ten minutes 26 C.C. of A’-sulphuric acid are added. The excess of iodine is estimated by titration with thiosulphate. Rapid Volumetric Method of Estimating Acetone. M. MARQUEYROL and P. LORIETTE (Mim. des Yozdres 1922 19 362-367).-The method depends on the action of sodium hypo- iodite on acetone in alkaline solution whereby iodoform and sodium acetate are produced.The hypoiodite is formed by the interaction of potassium iodide and sodium hypochlorite. Commercial eau de Javel is used and is standardised against pure acetone 10 C.C. of which are dissolved in water and made up to 1 litre. Ten C.C. of this solution are diluted with 90 C.C. of water and 10 g. of potassium iodide and 20 C.C. of sodium hydroxide (d 1.325) added. The hypochlorite is run in from a burette with constant agitation and the solution tested with an outside indicator consisting of 1 g. of starch 10 g. of sodium hydrogen carbonate and 100 C.C. of water. The end-point is very sharp and is heralded by the precipitation of flocks of iodoform. In estimations of acetone the acetone is distilled into a 500 C.C.measuring flask and 100 C.C. are taken for tlhe estimation which is carried out as described above. The presence of alcohol aldehyde diphenylamine or ammonia does not affect the titration. Substituted carbamides however give traces of iodoform which can usually be neglected. Estimation of Reducing Sugars by Means of Fehling’s Solution with Methylene-blue as Internal Indicator. J. HENRY LANE and LEWIS EYNON ( J . Xoc. Chem. Id. 1923 42 32-37~).-In the volumetric estimation of sugars by means of Fehling’s solution the disadvantages attending the use of an external indicator can be altogether avoided by using a lyJ solution of methylene-blue as internal indicator. So long as any copper remains unreduced the indicator retains its colour but it is immedi- ately decolorised by the sugar the moment all the copper is reduced.The action is reversible. To attain the maximum of accuracy consistent procedure is necessary in combination with conversion tables based on the same method of operation. The following standard method of titration is recommended 10 C.C. or 25 C.C. of Soxhlet’s modification of B’ehling’s solution are meaiiured into a 300 C.C. flask and treated cold with almost the whole of the sugar solution (determined by a preliminary trial) required to effect G. W. R. H. C. R.ii. 194 ABSTRACTS OF CHEMICAL PAPERS. reduction of all the copper. The liquid is then heated to boiling kept in moderate ebullition for two minutes and then without removing the flame 3-5 drops of the indicator are added and the titration is completed in one minute further so that the liquid is boiled in all three minutes.The end-point can be determined generally to within 1 drop of the sugar solution. Based on this method of procedure tables have been drawn up giving the weight in mg. of sugar required to reduce the volume of Fehling’s solution employed. This factor varies appreciably with the concentration of the sugar solution and values are given for volumes of 15-50 C.C. Tables are given for invert-sugar both in presence and absence of sucrose for dextrose laevulose maltose and lactose. J. LANZA (Anal. Pis. Quim. 1922 20 400402).-The method is based on the reaction whereby picric acid and dextrose in alkaline solution give picramic acid Oh*C,H,(N0,),*NH2 which is distinguished by its red colour. To 2 or 3 C.C.of the cerebrospinal fluid picric acid in the proportion of 0.05 g . for each C.C. of liquid used is added. After warming the liquid is rapidly cooled and centrifuged. Dex- trose is then estimated colorimetrically by comparison with a standard dextrose solution in A Duboscq colorimeter. G. F. M. Estimation of Dextrose in Cerebrospinal Fluid. G. W. R. The Tryptophan-Aldehyde Reaction. ERNST KOMM and EBERHARD OHR RINGER (2. physiol. Chem. 1923 124 287-294).- A new modification of the aldehyde test for tryptophan is described One C.C. of the solution of tryptophan is added to a 15% solution of hydrochloric acid containing in 500 c.c. 6 C.C. of a 0.1% solution of formaldehyde. To the mixture are added 10 C.C. of concentrated sulphuric acid.The whole is shaken and allowed to cool. The colour produced is stable and proportional to the tryptophan present for the colorimetric estimation of which the reaction may be applied. It is sensitive to a solution of tryptophan containing 1 part in 175,000 parts. Modification of the Moreigne Ureometer. J. LANZA (Anal. Pis. Quim. 1922 20 403405).-A modification of Moreigne’s apparatus for the estimation of urea by the hypobromite method is described. G. W. R. The Hydrocyanic Acid Question. XI. The Detection of Hydrocyanic Acid in Plants. L. ROSENTHALER (Schweiz. Apoth. Ztg. 1922 60 477481; from Chem. Zentr. 1922 iv 1124-1125; cf. A. 1922 i 614-616).-Hydrocyanic acid in plants may be detected by its decolorisation of blue starch-iodide solution.In the presence of essential oils which contribute iodine the plant material should first be extracted with ether. Where only traces of hydrocyanic acid are to be expected it may be removed from the material by long passage of a stream of air and collected in mercuric chloride solution. By addition of potassium iodide to the mercuric chloride solution with subsequent passage of carbon dioxide or warming with sodium hydrogen carbonate W. 0. K.ANALYTICAL CHEMISTRY. ii. 195 the hydrocyanic acid is again liberated. For the detection of hydrocyanic acid in plant sections the starch-iodide method is suitable. G. W. R. Analysis of the Products of Hydrolysis of Cyanamide by Acids. A. GRAMMONT (Bull. Soc. chim. 1923 [iv] 33 123- 128) .-A satisfactory evaluation of fertilisers derived from cyanamide requires not only an estimation of organic and ammoniacal nitrogen but also that the former should be differentiated into carbamide nitrogen dicyanodiamide nitrogen and dicyanodiamidine nitrogen as these substances have widely different values as fertilisers and some are even toxic.Such discrimination between the forms of combination of the nitrogen present is obtained by the following method of assay Total nitrogen is estimated by Kjeldahl's method; ammonia by converting the ammonium salts present in solution of the material neutralised to phenolphthalein with dilute sodium hydroxide into hexamethylenetetramine by the addition of formaldehyde and titrating the liberated acid with standard alkali hydroxide ; carbamide by precipitation by the Posse method with xanthydrol as dixanthylcarbamide and weighing as such ; dicyanodiamidine by precipitation as its nickel compound Ni(C,H,ON,),,H,O by the method of Dafert and W o m b washing the precipitate with 2% ammonia drying at 100" and weighing; and finally arriving at the amount of dicyanodiamide by difference as cyanamide itself is always absent. If the fertiliser contains phosphoric acid or soluble phosphates they must first be removed by adding sodium hydroxide solution to the material after digesting for one hour in water until neutral to phenolphthalein whereby soluble phosphates are precipitated as calcium phosphate.The above estimations are then carried out on the filtrate. The Interconvertibility of Creatine and Creatinine. 111.The Estimation of Creatinine and Creatine in Blood-serum. AMANDUS HAHN and GEORG MEYER (2. Eiol. 1922 76 247- 256; cf. A. 1921 i 517).-In the estimation of creatine in blood- serum trichloroacetic acid is very suitable for precipitating the proteins Fifty C.C. of serum are diluted with 25 C.C. of water and 50 C.C. of a freshly prepared 10% solution of trichloroacetic acid are added. The creatine in the filtrate is then estimated by conversion into creatinine by treatment a t 60-65" with hydro- chloric acid and estimated along with the preformed creatinine as previously described (Eoc. cit.). In the estimation of the preformed creatinine colloidal ferric hydroxide may be conveniently used as a protein precipitant. W. 0. K. Purification of Picric Acid for Creatinine Estimations.STANLEY R. BENEDICT ( J . Biol. Chem. 1922 54 239-241).- Recrystallisation from benzene is recommended. Folin and Doisy's method (A 1917 ii 159) is unsuitable. JOSEPH M. LOONEY ( J . Biol. Chem. 1922 54 171-175).-Foh and Looney's method (A. 1922 ii 539) for the estimation of cystine is applied G. F. M. E. S. Colorimetric Estimation of Cystine in Urine.ii. 196 ABSTRACTS OF CIEEIYLfCdL PAPERS. directly to urine. The coloration due to the presence of uric acid and other reducing substances is corrected for by making an estim- ation without the addition of sodium sulphite to the urine and subtracting the resulting value from that obtained in the presence of sodium sulphite. The readings must be made not later than eight minutes after the addition of the phosphotungstic acid reagent.E. S. Colorimetric Method €or the Estimation of Cystine. EUGEN HERZFELD (Schweix. med. Woch. 52 411412; from Chem. Zentr. 1922 iv 1076).-The method consists in precipitating the sulphur from an alkaline solution of cystine by addition of copper sulphate solution. After freeing the precipitated copper sulphide from copper oxide by treatment with dilute sulphuric acid it is dissolved in nitric acid and by addition of ammonia converted into solution suitable for colorimetric estimation. For comparison a solution is prepared from a known weight of pure cystine. Experimental details of the method are given. G. W. R. Estimation of Morphine. JOHN RALPH NICHOLLS (AnaZyst 1922 47 506-510).-A general method for the extraction of morphine is described. One volume of the morphine solution is mixed with 1 volume of alcohol the mixture is rendered anirnoniacal and shaken with 1 17olurne of chloroform. The chloroform layer is drawn off and the mixture is again shaken with the addition of 0.5 volume of alcohol and 1 volume of chloroform. This process of extraction is made three or four times the combined extracts are then evaporated the residue is dissolved in a definite volume of standardised acid the solution diluted to a known volume and the morphine is then estimated volumetrically colorirnetrically or A cystine standard is used in each case. polarimetrically . w. P. s. System of Blood Analysis. Supt. IV. Revision of the Method for Estimating Uric Acid. OTTO FOLIN (J. Biol. Chem. 1922 54 153-170).-The various recent methods for the estimation of uric acid in blood are reviewed and the author’s method (A. 1919 ii 308) is modified. The procedure now adopted is in its essentials similar to that of Benedict (A 1922 ii 403) except that the uric acid reagent of Folin and Denis is retained. The original precipitation method is retained in a modified form as a check on the direct method. Contrary to Pucher’s statement (A. 1922 ii 66S) 90-100% of added uric acid can be recovered from the tungstic acid filtrate; the heat process recommended by this author gives irregular results and should be avoided. E. S. STANLEY R. BENEDICT ( J . Biol. Chem. 1922 54 233-238).-Mainly a reply to Folin (cf. preceding abstract). E. S. Estimation of Uric Acid.

ISSN:0368-1769    

DOI:10.1039/CA9232405175

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

ii. 197 General and Physical Chemistry. Variation of the Refractive Index of Oxygen with Pressure and the Absorption of Light by Oxygen at High Pressures. (MISS) H. I. EADIE and JOHN SATTBRLY (Tram. Roy. 8m. Can& 1922 16 111 63-73).-Gladstone and Dale's law for the relation of refractive index to density has been confirmed in the case of oxygen for pressures ranging from 2.1 to 140 kg. per sq. cm. Evidence for the existence of absorption in oxygen at pressures up to 100 atmospheres in the regions hh 6285 5800 and 5350 8. was not conclusive. Variation of the Index of Refraction of Water Ethyl Alcohol and Carbon Disulphide with the Temperature. ELMER E. HALL and ARTHUR R. PAYNE (Physical Rev. 1922 20 249-258).-Measurements were made with a precision spectro- meter the construction and use of which are described.The two prisms used were of gold-plated brass and optical glass sides and had an angle of 60" and 75" respectively; the temperature of the bath could be maintained indefinitely within 0.1" of any desired point. From tables showing the index of refraction of water relative to air and the absolute index of refraction of water (both for sodium light) respectively the following values are abstracted 15" 1.33341 1,33377 ; 20" 1.33299 1.33327 ; loo" 1.31783 1.31819 (all &0.00002). When reduced to a vacuum the experimental values for pure water are well represented by the empirical formula n = 1-33401 -lo-'( 66t+26.2t2 -0.1817t3+0*0~755t4). The temper- ature coefficient dnldt at the temperatures mentioned has the values -0@0008 -0.00009 and -0.00030.Corresponding values of the index of refraction relative to air and of the temperature coefficient dn/dt of ethyl alcohol (Kahl- baum's 9908% absolute) are abstracted as follows la" 1.36290,- (75") -0.00046. For carbon disulphide 15" 1062935 -040077 ; the absolute values obtained differ somewhat from those given by others for pure samples the temperature coefficients are probably not affected by the slight amount of impurity present. For ethyl alcohol between 15" and 70" the results correspond with the empirical equations dn ldt = - lo*[& +0*44 (t - 15) + 0 4075 (t - 1 5)2 J ; for carbon disulphide between 15" and 45" dn/dt= - 10+[766+ 5~12(t-i5)-0~105(t - 15)2]. E. GEHRCKE and E. LAU (Sitzungber. Preuss. Akd. Wiss. Berlin 1922 32 453- 458).-The secondary spectrum of hydrogen has been obtained almost free from the Balmer series by using a discharge tube silvered on the inside.The bands in the red-yellow and the yellow- green portion of the spectrum consist of a number of lines arranged J. S. G. T. (16") -040040 ; 24" 1.35885 (25") -0.00041 ; 76" 1.33626 20" 1.62546 (25") -0.00081 ; 45" 1.60499 -040083. Although A. A. E. The Secondary Spectrum of Hydrogen. VOL. CXXIV. ii. 8ii. 198 ABSTRACTS OF mEXICAL PAPERS. symmetrically about a middle point but the middle line about which the other lines are grouped is missing. The distances between the principal line and its a- and @-companions stand in the relation- ship 1 2 ; the 8 line divides up the distance between the principal line and 0 in the proportion 2 3.The distance between the principal lines of the successive bands shows that the series approximates to a system of Ah-bands and in this respect they are similar to the resonance spectrum of sodium. In the bands in the blue-green region the companions of the principal lines show a 3 2 relationship in their distances. The lines lying in the regions between the bands form symmetrical groups and repetition of similar groups frequently occurs. By the introduction of a spark gqp into %he discharge tube the relative intensities of the hydrogen lines are very much altered. The change is in many respects similar to that observed by Merton when helium is mixed with hydrogen. The lines in the secondary spectrum are much sharper than the H line in the Balmer series.Prom the thickness of the lines it is deduced that the secondary spectrum owes its origin to molecular hydrogen (€I& H and H,,). The thickness of the lines increases with increase in the diameter of the tube owing to the higher temperature in the narrower tubes. From the absence of the secondary spectrum in the light from the stars it is concluded that the hydrogen giving rise to the Balmer series is always contaminated with other gases and it is possible that it exists in the state of dissociated water vapour. W. E. G. Band Spectrum in the Arc Spectrum of Silicon. C. PORLEZZA (Atti R. Amad. Lkncei 1922 [v] 31 ii 513-517).- The author’s examination of the arc spectrum of silicon gives results differing little from those of Gramont and Watteville (A.1908 ii 909) but showing a band spectrum not previously observed. Relative Intensities of the Stark Effect Components in the Helium Spectrum. JOHN STUART FOSTER (Phpicd Rev. 1922 20 21&-22O).-By the use of a discharge tube of the type first employed by Lo Surdo the relative intensities of Stark effect components have been measured by means of a neutral wedge. Spectrograms were taken of the p and s components in turn using a five-prism spectrograph ; energy distribution curves were then calculated from the contour of the images and the corresponding wedge densities and the relative intensities obtained by integration. The results for the main p components are ii 4388 8.2 (isolated) 4.1 19-2 28.0 ; A 4472 168 694 ; A 4922 9*7,31-6. Corresponding results for the s components are A 4388 1.0 (isolated) 3.0 11.3 9.5 ; 14472 76 464; A 4922 6.2 21.4.A. A. E. The Band Spectrum Associated with Helium. Y ~ K A TWASHX (Prroc. Php. Math. Sac. Japan 1922 4 187-193).- The band spectrum of helium consists of two double-headed bands the lines of which form series for which Fowler has derived formuls T. H. P.(31ENBUSAL AND PHYSICAL CHEMISTRY. ii. 199 of the Hicks type. Band spectra are usually attributed to mole- cules and not to atom It is possible however to assume that under certain conditions unstable helium molecules may exist from which the observed band spectrum may originate. A mathe- matical analysis shows that the form of a helium molecule is such that two nuclei each accompanied by one electron about it are connected by means of an electron and form something like a nucleus around which the remaining electron describes its orbit. CHEMICAL ABSTRACTS.Arc Spark and Absorption Spectra of Argon. W. W. SHAVER (Trans. Roy. SOC. Canada 1922 16 111 135-144).- The radiation produced in argon by electronic bombardment with an accelerating potential of 10-1 volts has been detected photo- graphically and shown to consist of wave-lengths 4335.4 4300.2 4259.8 4198.4 4158.7 and 4055.9 A. With accelerating fields ranging from 16 to 30 volts the lines in the arc spectrum corre- sponded with those of the red argon spark spectrum. At 31 volts the blue or enhanced spectrum began to appear and at 54 volts all the enhanced lines predicted by Bohr’s theory were found. No new lines appeared when the potential was increased to 240 volts. No evidence of absorption was detected in the spectrum of ionised argon at pressures of 155 5 and 2 mm.of mercury between wave- lengths 7000 & and 2150 8. or in the spectrum of argon at 102.4 atmospheres pressure in the same region. The Arc Spectra of Metals in Different Media and in a Vacuum. ST. PROCOPIO (Compt. rend. 1923 176 385-388).- In continuation of the work on mercury (A. 1922 ii 600) the author has studied the arc spectra of copper gold zinc cadmium magnesium calcium aluminium and carbon in air hydrogen coal gas nitrogen under water and in a vacuum. As in the case of mercury in the arc spectra of the metals under water in coal gas and in hydrogen the rays of the am series become much broadened and those of the higher order are weakened or dis- appear.In addition spark rays appear. In nitrogen the arc is stable with all the metals and the rays appear to be greater in number than in air. Certain rays previously only found in a vacuum appear. The radiated energy is displaced towards the last terms of the arc- series. Numerous rays axe inverted. The spark rays are weakened. In a vmum the arc is stable in all cases. The last terms are more intense than in the other media. The energy radiated is displaced towards the ultra-violet. Numerous rays particularly the cathodic rays are inverted and the rays are broadened. The arc in a vacuum shows enhanced rays and for the most part they are spontaneously inverted. Series Regularities in the Arc Spectrum of Chromium.C. C. KIESS and H~RRIET KNUDSEN m s s (Science 1922,56,666).- The arc spectrum of chromium contains at least three sets of seriee of which the members are triplets two sets being composed of wide triplets and one of narrow triplets. A constant difference J. S. G. T. W. G. G-2ii. 200 ABSTRACTS OF CYHEMICAL PAPERS. exists between the wave-numbers of homologous members of the wide-triplet series. Each component of the first member of the diffuse series is itself a narrow triplet. The principal sharp and diffuse series of the two parallel systems give values for Av of 11244 81-38 ; 112.45 81.35 ; 112.78 81-29 ; and 115*10 91-42 ; 115.2 91.3 ; 115.16 91.54 respectively whilst the narrow triplets are characterised by the frequency differences Av,=8.80 and Av = 5 *65.H. M. HANSEN and S. WERNER (Nature 1923 111 322; cf. A. 1922 ii 463!.-The optical spectrum of a large number of preparations containing hafnium has been examined and compared with that of a specimen of very pure zirconium prepared by Coster and Hevesy from com- mercial zirconium by removing the hafnium content. A table gives the wave-lengths and intensities of a number of lines some of which have been observed by earlier investigators and ascribed to zirconium. There was however not the slightest trace of any of the lines ascribed by Urbain to an element celtium belonging to the family of rare earths although this element has recently been assumed to possess the atomic number 72. The K Absorption Spectrum of the Element 72 (Celtium). M. DE BROGLIE and J.CABRERA (Cmpt. rend. 1923 176 433- 434).-Dauvillier has described in a preparation of celtium the presence in the spectrum of several feeble lines undoubtedly belong- ing to the element of atomic number 72 the presence of which has recently been recorded in several zirconium minerals by Coster and Hevesy. The absorption spectra of X-rays is an excellent means of revealing an element by its discontinuity K and this method when applied to some minerals has shown the presence of the new element of atomic number 72. A. DAUVILLIER (Compt. rend. 1923 176 676-679).-A reply to a s t e r and von Hevesy’s criticism (this vol. ii 80 171) of the author’s attribution to celtium of the lines 1319.4 and 1561% 9 observed in a pre- paration of ytterbium oxides (A. 1922 ii 463). It is contended that the difference between the observed wave-lengths and the theoretically calculated values is not outside the limits of possible error that the lines cannot belong to higher orders of other elements and that the line PI of celtium lying between the two intense lines 1366.7 of lutecium and 1377.7 of copper would not be expected to be visible on the photographic plate.L-Series of Tungsten and Platinum. J. S . ROGERS (PYOC. Camb. Phil. SOC. 1923 21 430433).-The values of the wave- lengths obtained for the L-series of tungsten and platinum are in good agreement with those given by Dauvillier and Coster although there are discrepancies for some of the fainter lines. A number of new lines have been discovered and ascribed to definite electron passages within the atom. I n the tungsten spectrum the line 14503 has been called x3 and the line 1.2489 p i and the former A.A. E. The Optical Spectrum of Hafnium. A. A. E. W. G. The High Frequency Spectrum of Celtium. G. F. M.QENERAL AND PHYSICAL CHEMISTRY. ii. 201 is ascribed to the passage M L and the latter to N3 L,. Other faint new lines have been observed. In the platinum spectrum line 1.0660 has been called PI,- the line 1.0803 appears to be due to the passage from an 0 to a L orbit and the line 1.0375 may be due to the passage Ml L,. Calculations have been made of the energies of these lines and good agreement is found with the calculated values. The lines fall on the Moseley graphs. W. E. G. Ultra-violet Absorption Spectra of the Cresols. F. W. KLINGSTEDT (Cmpt.rend. 1923,176 674-67G).-o-Cresol and m- cresol have almost the same absorption spectra having two broad bands occupying approximately the same position as those of phenol a t X=2780 and 2716 for the former and at X=2796 and 2720 for the latter. The coefficients of molecular absorption r=1810 and 1770. Compared with toluene the bands are con- siderably displaced towards the red and their intensity is about nine times as great. p-Cresol has seven bands between X=2858 and 2644. Compared with the 0- and m-cresols the spectrum of p-cresol is displaced 70 8. towards the red the intensity of absorp- tion is greater and like other para-derivatives there are numerous narrow bands instead of two wide bands this distinction being so characteristic as definitely to identify a para-compound.The seven bands of p-cresol can be distributed into three groups the difference in the frequencies of each group being constant whilst the intensity of absorption decreases. The mean fundamental period A =1217 8. The Ethylene Chromophor. H. LEY and F. RINKE (Bey. 1923 56 [B] 771-776; cf. Ley A 1917 i 261; 1919 ii N).- A continuation of previous work. The introduction of a methyl group into stilbene in the a-position causes a diminution of the selective absorption and a displacement of the continuous absorption towards the region of shorter wave- lengths. The presence of a second methyl group increases the effect to such an extent that only a trace of selective absorption is observed with 7 7’-dimethylstilbene. A methyl radicle attached to the nucleus in the para-position has a normal influence.The spectroscopic analogy between stilbene and cinnamic acid is pre- served in the methyl and dimethyl derivatives which contain the substituents in the aliphatic portion of the molecule. The presence of a chlorine atom in the a-position of styrene has a weak hyposochromic influence whereas in the @-position it displaces the absorption towards greater wave-lengths. The absorption curve of 7-chlorostilbene is similar to that of the parent substance with the exception that the band is sharper and some- what displaced towards the ultra-violet ; nuclear chlorine has a distinct bathochromic effect. Comparison of the absorption curves of stilbene 7-phenylstilbene and 7 ‘7‘-diphenylstilbene shows that in the region of greater thickqesses or higher concentrations the absorption is progressively G.3’. M.ii. 202 ABSTRACTS OF CHEMICAL PAPERS. displaced towards the red end in the region of least transparency the absorption is diminished ; with increase in the number of phenyl groups the extinction coefficients become smaller and the head of the bands is displaced slightly towards greater wave-lengths. The additive compound of 7 7'-dimethylstilbene and 1 3 5-tri- nitrobenzene is markedly less coloured than the corresponding compound from 7-methylstilbene ; similarly in the phenylstilbene group the colour diminishes with increasing number of substituents. By-Diphenyl-n-butane m. p. 123-124" is prepared by the action of magnesium on an ethereal solution of ct-bromoethyl- benzene; an isomeride b.p. 162-164"/25 mm. appears to be produced simultaneously. Tetraphenyletliylene m. p. 221 O obtained from benzophenone chloride and sodium iodide in the presence of acetone is reduced by sodium and boiling amyl alcohol to tetraphenylethane m. p. 209". a-Chlorostyrene has b. p. 83"/23 mm. 85-85*5"/22.5 inm. 73-74'115 mm. di0 1.0975 and 1.0916 for two different specimens. Determination of Constitution by Spectrochemical Methods. The so-called Triphenylvinyl Alcohol. Enolic Salts. H. LEY and W ~M~NECIIE (Ber. 1923 56 [B] 777- 783).-As a result of purely chemical investigation Meyer and Gottlieb-Billroth (A. 1921 i 422) have been drawn to the con- clusion that the so-called triphenylvinyl alcohol CPhJFh-OH is actually a ketone cHPh,*COPh.Spectrochemical investigation leads the authors to the same conclusion. The optical behaviour of " triphenylvinyl alcohol " is completely different from that of triphenylvinyl acetate CPh,:CPh*OAc in which the enolic form is fixed. According to previous observations i t is to be expected that the optical properties of triphenylvinyl alcohol would not differ greatly from those of the parent hydro- carbon 7-phenylstilbene ; it is observed however that the absorp- tion spectra of the hydrocarbon and triphenylvinyl acetate are closely similar and differ entirely from that of triphenylvinyl alcohol. The enolic constitution of the latter compound is therefore regarded as impossible. Its ketonic nature is demonstrated by a comparison of its optical properties with those of acetophenone deosybenzoin and p- benzpinacolin COPh*CPh,. Further the colour of the additive product of " triphenylvinyl alcohol " and 1 3 5-trinitrobenzene shows that it is not a derivative of stilbene.The optical behaviour of 9- benzoylfluorene YBH4>CHBz has been examined in connexion with that of triphenylethanone. The parent hydrocarbon 9- benzylidenefluorene is closely analogous to 7-phenylstilbene but the analogy between triphenylethanone and 9-benzoylfluorene is not a t first sight so marked probably by reason of the increased absorption attributable to the fluorenone ring. The absorption of the sodio-derivative of the enolic form of 9-benzoylfluorene has also been measured as well as that of the free enol (the apparatus required for the latter purpose is described in detail).H. W. c6p4GENERAL AND PHYSICAL CHEMISTRY. ii. 203 The enols which have been generally investigated spectro- scopically contain a carbonyl group and it hanS been assumed that in their salts the metal is also united to this group by a subsidiary valency whereby an internal complex salt is produced. The authors consider this hypothesis untenable and prefer to attribute the behaviour of the salts to the presence in them of readily altered conjugated systems. H. W. Mode of Absorption of Triphenylmethane Colauring Matters. E. ADINOLFI (Atti R. Accad. Lincei 1922 [v] 31 ii 551-554) .-Consideration of the various theories advanced to establish chemico-physical connexions between constitution and absorption together with the results previously obtained (A.1922 ii Wl) shows that triphenylmethane colouring matters in solution in water or in methyl ethyl isobutyl or amyl alcohol give rise to absorption spectra of similar type and with maxima which undergo increasing displacement as the molecular weight of the solvent increases. To this rule rhodamine-B and uranine form exceptions probably owing to re-emission resulting from fluorescence. The two characteristic absorption bands of these colouring matters are due to two distinct vibrators which in some cases diffuse with unequal velocities and in others disappear alternately in acid or alkaline solutions and undergo displacements to different extents in different solvents. T. H. P. ma-red Spectroscopy. V. P. LUBOVICH and (MISS) E. M. PEAREN (Trans.Roy. Soc. Canada 1922 16 111 195-212).-The absorption of infra-red radiation by dilute alcoholic solutions of dicyanin dicyanin- A pinacyanol nigrosin-SS alizarin-blue-S and Eastman red sensitiser No. 700 has been investigated. The results indicate that photography of the infra-red spectrum can be readily extended to X 20,000 8. Nigrosin and alizarin-blue are more suitable for the photography of certain regions of the spectrum than dicyanin or dicyanin-A. The infra-red spectra of tin lea! bismuth zinc and antimony have been investigated from X 8000 A. to h 11,000 8. Particulars are given of the application of the ( ( thalofide cell ” to determine wave-lengths in infra-red spectra. J. S. G. T. A Simple Appliance €or Detecting Traces of Fluorescent Substances.ED. MOREAU ( J . Pharrn. Chim. 1923 [vii] 27 184-187).-A box lined with black paper measuring about 8 cm. cube has a narrow observation slit in the middle of one side and a hole in the top opposite to the slit just large enough to take the test-tube containing the solution fo be examined. This is illumin- ated from above by an electric lamp which is shaded from the observer by means of a cylinder fixed to the top of the box. By means of this appliance the least traces of fluorescence can mth certainty be detected and minute quantities of urobilin in bio- logical work fluorescein for detecting infiltrations in sanitary investigations etc. can with certainty be found G . F. iN.ii. 204 ABSTRACTS OF CHEMICAL PAPERS. Destruction of the Fluorescence of Dilute Solutions by Ultra-violet Light.(MISS) F. M. CALE (Trans. Roy. 8oc. Canada 1922 16 111 267-263) .-Determinations have been made of the decrease of fluorescence of a dilute aqueous solution of aesculin by exposure to ultra-violet light. After the solution was once exposed its fluorescence continued to decay even when the solution was kept in absolute darkness. On subsequent exposure of the solution to ultra-violet light the rate of decay decreased very rapidly a t first then steadily. On further exposure after an interval of several hours the rate of decay was greater than before the interval Ozone bubbled through the solution caused a very rapid decay of the fluorescence the solution finally possessing the same colour and absorption spectrum as that transformed by ultra-violet light.Tesla-luminescence Spectra. I. The Form of Apparatus and the Spectrum of Benzene. WILLIAM HAMILTON MCVICKER JOSEPH KENNETH &SH and ALFRED WALTER STEWART (T. Luminescence of Compounds formed by the Action of Magnesium on p-Dibromobenzene and Related Compounds. W. V. EVANS and R. T. DUFFORD ( J . Amer. Chem. Soc. 1923 45 278-285) .-Solutions of magnesium p-bromophenyl bromide in ether are strongly chemi-luminescent so much so that if it is dropped from a rod through air the luminescence is visible in daylight; stirring the solution in air gives a strong luminescence and when poured from a tube it glows with a greenish-blue light which sug- gests molten metal. The luminescence of this substance has been compared with that of other aromatic halogen compounds when the substances are exposed to air or oxygen.No luminescence results from the action of other gases such as carbon dioxide hydrogen sulphide sulphur dioxide and nitrogen on Grignard compounds. The spectrum of the chemi-luminescence of magnesium p-bromophenyl bromide has been investigated by the use of light filters and its lower and upper limits have been found to lie within the region X5200-h3500. This spectrum is found to be distinct from that of the associated fluorescence spectrum Photographs of two kinds of fluorescence have been obtained from the oxidation products one giving a single-banded spectrum the other an entirely different multiple-banded spectrum. J. I?. S. Spectral Study of the Triboluminescence of certain Sub- stances. HENRI LONGCHAMBON (Compt.rend. 1923 176 691- 693; cf. A 1922 ii 603).-A spectral study was made of the tri boluminescence of tartaric acid cadmium sulphate uranium nitrate and calcium fluoride. I n spite of their widely different chemical constitution and crystalline form the spectrum of the triboluminescence was in all cases the line spectrum of nitrogen. In the case of the uranium salt however and i t would probably be so with other fluorescent substances such as the platinocyanides etc. the triboluminescence was masked by the secondary pheno- J. S. G. T. 1923 123 642-654).GENERAL AND PHJ?SlCAL CHEMISTRY. ii. 205 menon of fluorescence. Nevertheless by the spectrographic method after an exposure of six hours the presence of four other lines coincident with the four most intense nitrogen lines was revealed. Investigations on the Dependence of Rotatory Power on Chemical Constitution. XIX.The Rotatory and Refractive Dispersions and the Absorption Spectrum of d-y-Nonyl Nitrite. ROBERT HOWSON PICKARD and HAROLD HUNTER (T. 1923 123 434-444). Rotatory Dispersion of the Esters of Lactic Acid. I. Normal Esters. CHARLES EDMUND WOOD JOHN EDWARD SUCH and FRANK SCAEF (T 1923,123 600-616). T. H. HAVELOCK (Phil. Mag. 1923 [vi] 45 560-576).-A comparison is made between the ordinary dispersion of certain gases and the dispersion of magnetic rotation in regions free from absorption. The formulae derived from a simple static molecule with one type of vibrator are sufficient for both dispersions in the visible spectrum for gasea like hydrogen and nitrogen.In the case of oxygen i t is necessary to include the magnetic properties of the molecule before a complete theory can be formed. Omitting paramagnetic effects expressions for the rotatory dispersion are obtained for the anisotropic static molecule such as have been used for the ordinary dispersion of hydrogen. The Bohr molecule of hydrogen is studied numerically. In order that the adjustable constants of the ordinary dispersion formuls may be known more accurately it is desirable that parallel sets of observations on ordinary rotatory dispersion be made on the same gas under similar conditions The Mechanism of Photochemical Processes. 11. The Behaviour of a Dry Mixture of Oxygen and Hydrogen. ALFRED COEHN and HEINRICH TRAMM (Ber. 1923 56 [B] 455- 458).-A repetition of Baker's work (T.1902 81 4000) has con- firmed the observation that mixtures of hydrogen and oxygen which have been desiccated by prolonged contact with phosphoric oxide can be heated to redness in Jena glass tubes without the occurrence of an explosion. On the other hand the presence of moisture does not appear to exert an appreciable influence on the rate of combination of hydrogen and oxygen when exposed to the ultra-violet light of the Heraeus lamp. Similar observations have been made previously (A. 1921 ii 476) with mixtures of carbon monoxide and oxygen. H. W. The Mechainism of Photochemical Processes. 111. The Effect of Desiccation on the Combination of Hydrogen and Chlorine. ALFRED COEHN and HEINRICH TRAMM (Ber. 1923 56 [B] 458462).-The chlorine is dried and purified by fractional distillation a t the temperature of liquid air.The hydrogen is prepared electrolytically passed over heated palladised asbestos and thence at increasing pressure through a series of U-tubes in 8" G. F. M. Magnetic Rotatory Dispersion in Gases. W. E. G.each of which it is subjected to protracted cooling by liquid air. The moist and dry mixtures are exposed in quartz tubes to the light of a 100 candle-power Qsram lamp; the gases are subse- quently treated with neutral potassium iodide solution and the liberated iodine and the hydrogen chloride estimated. Under identical conditions the union of hydrogen with chlorine in the presence of moisture occurs quantitatively within twelve minutes whereas in the dry mixture there is no sign of combination after two hours.It has been shown previously (Coehn and Wassiljewa A. 1909 ii 846 ; Coeha and Stackardt A. 1917 ii 5) that hydrogen chloride bromide and iodide are decomposed to some extent by exposure to ultra-violet light. The presence of moisture is found to be without influence on the rate of decomposition of hydrogen bromide or iodide whereas in the case of hydrogen chloride decomposition of the completely dry gas is not observed. The velocity of combination of carbon monoxide with chlorine can be greatly reduced by thorough desiccation of the gases but the process invariably takes place a t an appreciable rate. Reaction in the case of sulphur dioxide and chlorine is completely inhibited by protracted drying of the gases. H.W. The Mechanism of Photochemical Processes. IV. The Behaviour of Dry Mixtures of Hydrogen and Chlorine in Ultra-violet Light. ALFRED COEHN and GERHARD JUNG (Ber. 1923 56 [B] 696-698).-It has been shown recently (preceding abstract) that dry hydrogen and chlorine do not combine with one another when exposed to visible light Under similar conditions union is quantitative within twelve minutes under the influence of ultra-violet light; the wave-length of the active rays is less than 254 pp. H. W. Spectrophoto-electrical Sensitivity of Bournonite and Pyrargyrite. W. W. COBLENTZ and J. F. ECKFORD (U.S. Bureau of Standards Xci. Paper No. 451 1922).-A study of the effect of chemical constitution on spectrophoto-electrical sensitivity. The minerals were tested in the spectral region from 0.3 p in the ultra-violet to 2 p in the infra-red.Bournonite 3(Cu2Pb)S,Sb2S has a high spectrophoto-electrical sensitivity from the extreme violet to 1 p in the ultra-red with two wide ill-defined maxima in the region of 0.55 p and 0.95 p its reaction being entirely different from that of the constituent sulphides. The intrinsic intensity is greatly increased with fall of temperature the maxima shifting towards the short wave-lengths. The spectrophoto-electrical re- action of pyrargyrite Ag,SbS consists at 22" of a wide unsym- metrical maximum in the ultra-violet with a weak ill-defined maximum in the region of 0.63 p. It also differs from that of the constituent sulphides but resembles that of proustite (silver arsenic sulphide). At -165" pyrargyrite reacts electrically to all wave- lengths from the extreme ultra-violet to 1 . 5 ~ ~ but the greatest reaction is localised in the band a t 0 .6 3 ~ ~ On increasing the intensity of the radiation stimulus there is a more rapid increaseQENERAZ AND PHYSICAL CHEMISTRY. ii. 207 of the response of bournonite and pyrargyrite in the long wave- lengths than the short. In a general way the properties of photo- electrical reaction spectra and absorption spectra are affected analogously by chemical constitution indicating that the two phenomena may have a common source within the molecule. T. H. B. The Distribution of the Length of a-Rays. (RILLE) I R ~ E CURIE (Compt. rend. 1923 176 434-437).-A study of the distri- bution of the length of rays by photographing the trajectories obtained in an apparatus similar to that described by Wilson (A.1913 ii 92). On account of the difficulty of knowing in a precise manner the density of the gas in the chamber a t the moment when the rays are emitted the measurements are essentially a comparison of the length of the rays emitted at the same instant in an exposure. The rays used were those of polonium. For each exposure two curves are traced namely the number n of rays the lengths of which are comprised between x-Ax and x+Ax and the number N of rays of length superior to x in function of x. The first curve shows the existence of the most probable trajectory I of the rays. The second curve the fall of which resembles that of Bragg's curve shows that it is possible to define an extrapolated trajectory p in the same manner as Henderson defines it for the ionisation curve (A.1921 ii 617). Several hundred rays were photographed and curves are given for the results of 142 rays. The ratio of p' p for the rays of polonium and radium-C is exactly equal to that given by Geiger from the ionisation curve namely 6.971 3.925=1*775 (2 Physik 1922 45). Except for the very short rays the results as plotted correspond exactly with a law of probability of the form Ke-E*zz. About 90% of the rays have a length between I-1 and Z+1 mm. The second curve shows that p=Z+0.7 mm. and taking for p the value 3.92 mm. as given by Geiger (Zoc. cit.) the most probable length of the trajectory will be 3.85 a m . in air a t 15" and 760 mm. As a corollary it is necessary to admit that the ionising power of an a-ray along its trajectory commences by increasing passes a maximum 4-3 mm.from its end and then decreases rapidly during the last millimetres. W. G. Extension of the X-Ray into the Ultra-violet Spectrum. OTTO STUHLMAN jun. (Science 1922 56 344).-When thermions liberated from a tungsten filament are accelerated and allowed to impinge on a metal grid maintained a t a variable positive potential secondary electrons are emitted from the grid the number being measured by means of a galvanometer in series with the grid and a plate maintained at a constant positive saturation potential. When the secondary current is plotted as a function of the acceler- ating voltage a sudden change in the slope of the curve occurs at critical potentials the equivalent wave-lengths being calculated from the energy-quantum relation V(volts)L(d.)= 12320.Pre- liminary measurements are given in the case of tungsten and iron. A. A. E. s*-2ii. 208 ABSTRACTS OF CHEMICAL PAPERS. The Increase of the Dispersion in the Photo-electric Spectra of X-Rays. RENL LEDRIJS (Compt. rend. 1923 176 383- 385).-The dispersion is best increased by exciting the electronic emission by means of an X-radiation the frequency of which is slightly superior to the frequencies of the layers to be studied and by adjusting the magnetic field so as to bring the regions studied towards the edge of the photographic plate which corresponds with high values of the radius of trajectory of the electron. These conditions have been fulfilled in a study of the spectrum of velocities of electrons emitted by a radiation of gold excited by the radiation from a molybdenum anti-cathode.Seven rays were observed and the results obtained agree closely with those calculated. The Colson-Russell Effect Photechie Radiation from Metals Photoactivity and Other Similar Radiation Pheno- mena. E. RUMPF (Jahrb. Radioaktiv. Elektronik 1923 19 214-222).-A historical survey is given of the literature on this subject. The activity of a zinc surface has been investigated with a view to testing if the darkening of a photographic film is due to radiation or to the emission of corpuscles. Contrary to the observations of Blaas and Czermak (Physikal. Z. 1904 5 363) the colour of the gelatin film is without effect.The action on the photographic film is not stopped by 16 sheets of aluminium foil. Since the foil is pierced by numbers of small holes the possibility of diffusion of gases from the zinc plate to the film has not been eliminated. A powerful stream of air over the surface of the zinc was effective however in preventing any darkening of the film and by maintaining a potential difference of 150 volts between the film and the zinc plate it was shown that the effect cannot be due to electrically charged corpuscles. The only explanation of the phenomenon would thus appear to lie in some chemical influelice such as that suggested by Russell who ascribed the action to hydrogen peroxide formed during the oxidation of the zinc plate in the presence of water vapour. Positive Rays in Simple Gases.J. J. MCHEXRY (Phil. fiIag. 1923 [vi] 45 433-443).-A study of the proportion of atomic and molecular positive rays of the simple gases under varying conditions of pressure in the discharge tube. The prescncc of mercury vapour in oxygen gas causes most of the positive rays to become atomic and its removal always brings into prominence the molecular positive rays. Mercury seems to exert no effect on the nitrogen positive rays. The slower positive rays are mostly atomic whilst those of greater energy are mostly molecular. Since the energy of a positive ray depends on the potential difference through which it falls to the cathode those of small energy must be produced near the cathode. In this region ionisation by the cathode rays is a t a minimum and ionisation by positive rays at a maximum so it would appear that the positive rays tend to give atomic ions and cathode rays molecular ions. This view is in agreement with experiments made on the action of a magnetic field a t varying distances from the cathode in which it is shown W.G. W. E. G .GENERAL AND PHYSICAL CHEMISTRY. ii. 209 that the molecular positive rays are reduced in increasing measure as the distance from the cathode increases. The ratio of molecular to atomic positive rays is the greater the lower the pressure and the higher the voltage of the tube. In mixtures of one volume of hydrogen and two volumes of oxygen the hydrogen positive rays are smaller in number than the atomic positive rays but the ratios OJO and HJH are practically the same in the two cases.This regularity does not persist with other mixtures of hydrogen and oxygen. Carbon monoxide is more easily broken down into its atoms than oxygen and the proportion of atomic positive rays is much greater in the former gas than in pure oxygen. W. E. G. The Radiation and Ionisation Potentials of the Rare Gases and the Singlet and Enhanced Series of Argon. W. M. HICKS (Phil. Mug. 1923 [vi] 45 480-496).-The true radiation and ionisation potentials are defined as the potentials required to produce radiation or ionisation of the atom when this is in its radiating configuration. The observed ionisation potential should be the sum of the dissociation potential and the true ionisation potential. In hydrogen both radiation and ionisation potentials are observed on account of the long life of the hydrogen atom.In the rare gases the observed potentials are too large to represent the true values although these gases are already in the atomic state. It is suggested that the ordinary atom in these gases is not capable of ionisation but requires preliminary work to change it into a configuration capable of emission. The nature of these prepared atoms is discussed and the true radiation and ionis- ation potentials deduced from the spectral lines of these gases. Evidence is adduced from the work of Kammenstine (Astrophys. J . 1922 55 343) as to the existence of prepared atoms of the rare gases with long life periods. The life of a prepared helium atom must be of the order 1/200 of a second since a frequency of 220 cycles per second is just sufficient to enable an arc to strike in helium at 4 volts. Helium gives two types of prepared atoms the first requiring about 1 volt less than the second for their prepar- ation and possessing the longer life.The two forms are represented b y - 0-• 0 and 0 - e where a large dot represents an electron a small dot a potential level and a dash the nucleus. The true radiation and ionisation potentials of helium are given as follows radiation potentials He= 1.14 ; He+=7*4 ; ionisation potentials He=4*75 ; He+=13.5 volts. The ionisation and radiation poten- tials of neon may be explained if there are three kinds of prepared atoms for this gas. The work required to change the fist prepared state to the second is 6.1 volts and to change the latter into the third is 11.8 volts.A similar analysis is made for argon from the work of Horton and Davies on radiation and ionisation potentials of argon and from its spectrum. Luminous Discharge in Iodine. Determination of the Ionisation Potential of Iodine. W. ALBERT NOYES jun. ( J . Amer. Chem. Xoc. 1923,45,337-342).-The theory of the luminous W. E. G.ii. 210 ABSTRACTS OF Cl€EMICAL PAPERS. discharge put forward by Gibson and Noyes (A. 1921 ii 610; 1922 ii 812) has been discussed with reference to its applicability to the luminous discharge in an electro-negative gas or vapour such as iodine vapour. The discharge potential in iodine vapour a t various temperatures between -3" and 29" has been determined. Prom the experimental values the most probable value of the ionisation potential of iodine is found to be lO.Olf0-2 volts.This leads to the value 8.4 volts as the ionisation potential of the iodine atom which would corresTsond with a wave-length of 1472 A. It is im- possible to verify t6is from the spectrogriphic data now available. J. F. S. Liquid Chlorine as an Ionising Solvent. J. MENNIE and D. MCINTOSH (Trans. Roy. SOC. Canada 1922 16 111 301- 305).-In agreement with the observations of Johnson and I\/IcIntosh (A 1909 ii 881) the authors find no evidence of ionis- ation when inorganic substances or ordinary organic compounds are dissolved in liquid chlorine. Ethyl ether ethyl alcohol acetone and ethyl acetate dissolved in liquid chlorine yield conducting solutions when hydrochloric acid is added and determinations are detailed of the variations of the conductivities of these solutions as the amount of acid is increased up to 2.5 molecular proportions.In the case of alcohol the conduction is due to the ionisation of an oxonium acid compound by the acid. The results obtained with a solution of acetone in toluene to which hydrochloric acid was added resembled those for the corresponding liquid chlorine solution but the actual conductivities were much smaller in the former case. J. S. G. T. Condition of Bismuth Salts in Aqueous Solutions and the Molecular Electrode Potential of Bismuth. DAVID P. SMITH ( J . Arner. Chem. SOC. 1923 45 360-370).-The electrical con- ductivity and solubility of bismuth nitrate have been determined in solutions of nitric acid containing various quantities of acid a t 25".The results indicate that bismuth nitrate exists in solutions containing a considerable excess of nitric acid mainly in the form of partly ionised normal salt. Conductivity measurements of solutions of bismuth perchlorate show that the very soluble basic salt Bi(OH),ClO has the conductivity of a non-hydrolysed uni- univalent salt like potassium nitrate and that it is converted into less basic salts such as Bi(OH)(ClO,) and Bi(C10,) only slowly on the addition of an excess of acid. Even when the ratio of per- chlorate to bismuth is as much as 4 1 not more than 40-50% of the bismuth oxyperchlorate is converted into the hydroxy- salt Bi(OH)(ClO,),. E.M.F. measurements of cells of the type H,~HC10,~~HC10,+Bi0C104~ Bi have been made at 25" for various concentrations of perchloric acid and the bismuth salt.The results fully confirm the conclusions drawn from the conductivity values. The measurements lead to the following values for the molecular electrode potential of bismuth which were calculated on the two assumptions that the bismuth in solution exists entirely as the ion BiO+ and the ion Bi(OH)++ respectively BilBiOT+H+ :GENERAL AND PHYSICAL CHEMISTRY. ii. 211 -0.314 volt Si]Bi(OH)+ + +3+ -0.298 volt. For comparative purposes the electrical conductivity of solutions of nitric and perchloric acid have also been measured a t 25O. Electrode Potential of Bismuth determined by Equilibrium Measurements. ERNEST H. S m ( J . Amer. Chem. Soc. 1923 45 371-377 ; cf. preceding abstract).-The position of the equi- librium between bismuth and copper perchlorates and metallic copper and bismuth has been determined at 25" by shaking together the metal and the perchlorate of the other metal and analysing the equilibrium mixture.The reaction is represented by the equation 3Cu+ 2Bi(C10,) zz 2Bi+3Cu(C104) and from the composition of the equilibrium solution the value of the molecular electrode potential of bismuth has been calculated on the assumption that the bismuth exists in such solutions entirely as the ion BiO' and on the assump- tion that it exists solely as the ion Bi(0H)" and that the free perchloric acid present is completely ionised. The following values referred to the molecular hydrogen electrode were obtained BilBiO*+HII = -0.318 volt Bi]Bi(OH)"+H'II = -0.310 volt.If the copper salt is regarded as completely ionised whereby the errors in the ionisation assumptions are partly compensated there result values which differ by about 5 m.-volt from the above namely -0.323 and -0.314 volt respectively. These results are in fair agreement with the values -0.314 and -0,298 volt obtained by Smith (loc. cit.) from E.M.F. measurements. J. F. S. Hydrogen-Chlorine Cell. F. FOERSTER [with A. NOBIS and H. ST~TZER] (2. Elektruchem. 1923 29 64-79).-With the object of finding'a method by which chlorine and hydrogen can be com- bined on the large scale to form hydrochloric acid the authors have investigated the element Pt,H,J HC1]C12,Pt. The cell was built up in a U-tube which was divided a t the bend by a porous diaphragm platinised electrodes were inserted and chlorine was led into one side hydrogen into the other.It is shown that with such an arrangement current is furnished without any great amount of polarisation up to amperes lcm.2 of platinum surface in the solution. The action consists in the combination of hydrogen and chlorine to form hydrogen chloride and since the transport number of the hydrogen-ion is greater than that of the chloride-ion the concentration of the hydrochloric acid in the chlorine side of the cell increases much more rapidly than in the hydrogen side. By increasing the temperature the terminal voltage of the cell increases up to a definite maximum temperature which is higher the larger the current drawn from the cell. At 80° however the voltage falls when large currents are drawn from the cell because the reduction in the gas concentration retards the electromotive action more than it would normally have been increased by the increase in temperature.The velocity of the electromotive action of the chlorine is very great and independent of the nature of the electrode platinum or various forms of carbon being equally good. Hydro- gen however requires the catalytic action of platinum black to give it a somewhat larger activity and even when this is used the J. F. S.ii. 212 ABSTRACTS OF CHEMICAL PAPERS. reaction velocity of the hydrogen is not very large so that a marked polarisation appears when considerable quantities of current are withdrawn. The electromotive activity of %he hydrogen is restricted to the thin layer of the electrolyte covering the surface of the electrode which protrudes into the gas atmosphere.To increase the surface layer and to keep the concentration of hydrogen in it sufficiently high to furnish the necessary amount of current it is essential that a very rapid stream of hydrogen should be passed into the solution. Platinised carbon will serve as electrode just as well as platinised platinum. The action is very slow if a bright platinum electrode is used and it does not take place at all with carbon electrodes. In apparent connexion with this is the fact that the overvoltage of hydrogen on carbon electrodes is consider- able. On paraflhed carbon electrodes the overvoltage of hydrogen shows unexpectedly large variations with time.Combinations such as H21carbonlHC11carbonlC1 or H21 bright PtlHCllcarbonjCl give E.M.F. values which arise from concentration cells of the form Cl,(of small partial pressure)lHClICl,(p= 1 atm.). If on a platinised electrode the process H - 2H’+2@ is no longer sufficient to furnish the current the electrode becomes polarised to +0*8-+0*9 volt and the current furnishing process is then Pt-Pt*’o*+4@ which continues as long as the platinum deposit lasts. The potential of the element Pt[0*01MH2PtC1 in 2NHClJI has been measured and found to have the value +0*74 volt. Oxygen is capable if but slowly of displaying an electromotive activity on carbon electrodes which appears to be brought about by a small quantity of a carbon oxide present on the electrode. By using comb-shaped electrodes of which the one in the hydrogen part of the cell is platinised cells of about 600 C.C.capacity can be constructed which will furnish a continuous current of 0 . 5 - 0.63 ampere at 0.75 volt for many hours. To achieve this result the hydrogen must be led in a t 10-30 litres per hour. I n the chlorine part of the cell 10N-hydrochloric acid is produced with a 90% yield calculated on the chlorine led in and a material yield on the hydrogen of 1-2%. I n view of the necessity of using highly platinised electrodes and a very high rate of flow of hydrogen it is shown that the process considered is impossible for the com- mercial manufacture of hydrochloric acid. The burning of hydro- gen in chlorine is a more suitable and a t the same time a simpler process for this purpose.J. F. S. New Form of Electrical Resistance of Electrolytes. M~URICE PHILIPPSON (Bull. &ad. roy. Belg. 1922 [v] 8 76- 80) .-Since an electrolytic ion possesses inertia the magnitude of an alternating current passing through an electrolyte should decrease as the frequency of the current increases the effect being analogous to that of electromagnetic self-induction. An electro- lyte should in fact possess two kinds of resistance frictional and kinetic. The author obtained evidence of the existence of the latter kind of resistance and succeeded in measuring the “self- inductance ’’ and “ kinetic reactance ” of an electrolytic cell,GENERAL AND PHYSICAL CHEMISTRY. ii. 213 using a resonance method "tuning" a circuit containing the cell to one in which induced alternating currents of known fre- quency were produced.For a cell of 20 ohms resistance containing a normal solution of potassium chloride the kinetic reactances corresponding with frequencies of 4 x lo5 1.5 x lo6 and 3 x lo6 were found to be respectively 0.60 13-09 and 7-35 ohms a maxi- mum figure also being obtained at frequency 1.5 x lo6 when a cell of 100 ohms resistance was used or when sodium lactate or acetate was substituted for potassium chloride. For frequencies of 1 x lo6 to 3 x lo6 the kinetic reactance of a cell is roughly proportional to the volume of solution between the electrodes. Anodic Behaviour of Metals in Non-aqueous Solutions. 111. Iron Nickel Cobalt and Chromium in Ethyl-alcoholic Solutions of Nitrates. UMBERTO SBORGI and Gmo CAPPON (Nuouo Cim.1922 [vi] 23 303-331).-The authors have in- vestigated the anodic behaviour of various metals in ethyl-alcoholic solutions of calcium and ammonium nitrates the apparatus employed being similar to that previously used (A. 1921 ii 572) but modified to render it applicable at higher temperatures and to allow of the separate collection of the anodic and cathodic gases. Cobalt exhibits complete activity dissolving as a bivalent metal at all current densities from 0.03 to 3 amps. per sq. dcm. and a t all temperatures (from -10" to 60"). The other three metals show passivity phenomena. Nickel is passive at all temperatures from -10" to 25". At 60° it is partly active if the current- density is high (0-3-3 amps. per sq. dcm.); in the ammonium nitrate solution at low current density (0.03) not only is there complete electrochemical activity but superposed on this is chemical activity nickel being attacked by alcoholic ammonium nitrate particularly at high temperatures.With iron there is complete passivity a t all temperatures and current densities employed. Chromium shows in the alcoholic solutions passivity phenomena similar to those observed in aqueous solutions the attack being approximately (but somewhat less than) sexavalent ; chromic and not chromate ions appear. In the alcoholic calcium nitrate solutions there is formed at the cathode a badly conducting layer composed partly a t least of calcium ethoxide. I n all cases in which partial or total passivity is observed a t 25" oxygen is liberated a t the anode in amount corresponding with 7.5% of the total current the remainder allowing for the current expended in dissolving the metal giving rise to acetaldehyde ; the latter is formed almost quantitatively only a trace of acetic acid being obtained.Application of the Theory of Magnetism to the Calculation of Atomic Diameters. J. F. T. YOUNG (Trans. Roy. SOC. Canada 1922,111,16,49-61).-Aftention is directed to the periodic distribution of paramagnetic and diamagnetic properties among the elements arranged in the customary periodic table. A mathe- matical theory applicable either to the dynamic or static atomic model permitting atomic dimensions of an element to be calculated E. E. T. T. H. P.ii. 214 ABSTRBCTS OF CHEMICAL PAPERS. from the value of the magnetic permeability is detailed and the results me applied to calculate the atomic radii of 26 elements.The values obtained are of the correct order in all cases. J. S. G. T. The Specific Heat of Saturated Benzene Vapour and the Adiabatic Curve of the Liquid-Vapour Mixture. G. BRUHAT and A. DELAYGUE ( J . Phys. Radium 1923 4 1-lo).-From the experimental critical constants of benzene its specific heat a t low pressure and its heat of evaporation deductions have been made of the specific heat of the saturated vapour over a range of tem- peratures. At low temperatures and in the neighbourhood of the critical temperature this specific heat is negative but a t inter- mediate temperatures becomes positive. The values deduced for the two inversion points 121' and 254O are in good agreement with the experimental values 122" and 258" (cf.A. 1922 ii 348). From the specific heats of the saturated vapour the entropies of the vapour the liquid and mixtures of both have been deduced for temperatures ranging from ordinary temperatures up to the critical temperature. On a diagram in which values of the entropy are plotted against temperature the paths of the points for which an adiabatic expansion does not change the relative amounts of the two phases is indicated. By employing Young's tables the usual volume-temperature and pressure-temperature diagrams may be constructed. W. E. G. The Specific Heats of Nitrous and Nitric Oxides. J. R. PARTINGTON and W. G. SHILLING (Phil. Mag. 1923 [vi] 45 416-430).-The specific heats of nitrous and nitric oxides are of special interest from the point of view of the Lewis-Langmuir theory because of the similarity of the electronic configurations of nitrous oxide and carbon dioxide and of nitric oxide carbon monoxide and nitrogen.Nearly all the previous work on nitrous oxide was vitiated by the use of impure gas and results varying from Cp/Cw=1*25-1*32 are recorded in the literature. For nitric oxide previous values range from 1*38-1*415. The nitrous oxide in the present experiments was freed from oxygen and nitrogen by passing it through a tube immersed in liquid air. The ratio of the specific heats of the two gases was determined by measurement of the relative velocities of sound in these gases and in pure dry air. The effect of the tube on the velocity of sound was eliminated.It was shown that Wohl's equation of state has no advantage over that of Berthelot for the reduction of the results and that of the latter is employed as the basis of the calculation of the specific heats. The values obtained were for nitrous oxide CP/cu=1*302 CP=8*799 cal. CV=6*75S cal. ; for nitric oxide Cp/Cu=1*400 C,=6.990 cal. and Cw=4.993 cal. ANGUS F. CORE (Phil. Mag. 1923 45 [vi] 622-624).-1n the general d i a l equation p=RT+B/v the term B/v does not naturally f d l into two parts one of which is proportional to the temperature W. E. G . The Meaning of a and b in the Equation of State.GENERAL AND PHYSICAL CHEMISTRY. ii. 215 RTblv and the other independent of the temperature aJv. It is necessary to define either a or b.Thus a/v may be defined rn half the work necessary to.abstract N molecules chosen at random from the interior of the gas to infinity outside the gas the other molecules remaining fixed in position. Thus defined a/v corre- sponds most closely with the equation of van der Waals. The term RTb/v cannot be called the collision virial for when the molecules contain a hard kernel it does not in general reduce to the collision virial of Reinganum. The effect of making RTb/v equal to the collision virial is critically discussed and shown to lead to a/v=O if the molecule is regarded as a hard sphere without external field. W. E. G. Freezing Points of Organic Substances. VII. JEAN TIMMERMANS (Bull. SOC. chirn. Belg. 1922 31 389-397; cf. A 1921 ii 622).-The freezing points of a further 68 organic liquids are given in tabular form.The results confirm the author's previous conclusion that the alternation of melting points between the odd and even members of a homologous series is a general phenomenon and allow this generalisation to be extended to include substances possessing two hydrocarbon chains linked by a central characteristic group (secondary amines ethers alkyl sulphides etc.). Inverse alternation in which the odd members of a series melt a t a higher temperature than the adjacent even members is shown to be frequent even in series of symmetrical compounds. The melting points of the higher terms of all the homologous series considered tend towards a common value of 117" and further for the paraffins and most of their monosubstitution derivatives i t is found that the C,O member melts at about 65" the C member a t about 20° and the C member at about -45".Compounds containing an amino- or a hydroxyl-group do not conform to this rule their melting points being always higher than those quoted above. Amongst the lower members of a series there is often considerable and irregular variation in the melting points of successive members but a minimum is usually observed at about the C term. Outer Jacket for Beckmann's Boiling-point Apparatus. JAMES FREDERICK SPENCER ( J . SOC. Chem. Id. 1923 42 126).- An outer jacket for the Beckmann boiling-point apparatus is described. The jacket is made on the same plan as the usual porcelain jackets but is of copper. The mica windows are carried by light copper castings brazed to the inner and outer walls of the jacket.Only one side tube is attached to the jacket and this serves for putting the solvent and beads into the jacket and also for carrying the condenser. The boiling tube is supported by a ring of cork placed a t the top of inside wall of the jacket. The jacket is superior to porcelain and glass jackets since it reduces the breakage and danger of fire with inflammable liquids to a minimum and since it is less sensitive to draughts the equilibrium temperature is reached more rapidly and becomes steady much more quickly. J. F. S. H. H.ii. SIG ABSWCTS OF CHEMICAL PAPERS. Comparison of the Normal Boiling Temperatures of Un- desiccated Sulphur as Measured by the Dynamic and Static Methods. ALAN W. C.MENZIES ( J . Amer. Chem. Soc. 1923 45 327-331).-Since the boiling point of sulphur is used as a standard in thermometry the author has redetermined this value by both the static and dynamic methods with the object of ascer- taining whether or no the equilibrium between liquid sulphur freshly condensed from recently generated sulphur vapour and sulphur vapour occurs at the same temperature as that between liquid sulphur and vapour of a greater age a t the same pressure near to 760 mm. The results show that the boiling point of undesiccated sulphur is the same whether the dynamic or the static method be used. The actual values are not given in the paper but it is stated that the two values do not differ by more than 0.02" an amount which is not outside the estimated error of the experiment.It is suggested that this similarity might not be found if the sulphur were accidentally or intentionally intensively desiccated. The statement that delay may occur before a new phase freshly formed reaches its equilibrium constitution and properties has been examined for certain cases of liquids and vapours. J. I?. S. A New Process of Microsublimation. RICHARD KEMPF (2. anal. Chem. 1923 62 284-291).-The substance to be sub- limed is placed on a square brass plate 12 cm. square and 1 cm. thick heated by means of two resistors of nickel-chromium wire connected with an external resistance and regulator. The resistors are so arranged that they may be used separately or together either in series or in parallel. The layer of substance is made as thin as possible and is covered a t a distance of 0.1 to 0.01 mm.with the microscope slide. In this arrangement the temperature of the plate can be kept constant over long periods and by suitable cooling of the slide sublimates of most substances in characteristic forms may be obtained at comparatively low temperatures e.g. for mercuric chloride 17" arsenic and sulphur 50° stearic acid 3S0 vanillin 53" indigotin 95" cocaine 36" strychnine 103". These temperatures are considerably lower than those at which the substances sublime in a vacuum. By this process characteristic crystalline deposits from evaporated human urine and blood may be obtained even if present as stains on fabrics so that the method may find application in forensic analyses. Heat of Oxidation of Glucinum.H. COPAUX and CH. PHILIPS (Compt. rend. 1923 176 579-580).-A redetermination of the heat of oxidation of glucinum by measuring separately the heat of dissolution of the metal and its oxide in acids and taking into account this time the variation from unity of the specific heat of the acid solutions used gave a value of 131-3 Cal. The heat of oxidation of calcium determined in a similar way as a check on the correctness of the principles employed was 150 Cal. a value in close agreement with that obtained by Guntz by other methods. G. F. M. A. R. P.GENERAL AND PHYSICAL CHEMISTRY. ii. 217 Heats of Combustion and Energy of Dissociation. 111. A. VON WEINBERG (Ber. 1923 56 [B] 4 6 3 4 6 6 ; cf. A. 1920 ii 668-669).-A reply to Fajans (A. 1922 ii 818) and to Hiickel (A.1922 ii 818). Calorimetric Researches. 111. Some Remarks on an Attempt of Swientoslawski to Calculate the Heat of Com- bustion of Benzoic Acid by a Semi-theoretical Method. P. E. VERKADE (Rec. traw. chim. 1923,42 105-111; cf. A. 1922 ii 474 740).-A critical survey of the conclusions drawn by Swientoslawski and Popov (A. 1915 ii 315) and of the method of calculation adopted. The author stresses his criticism on the ground that benzoic acid is accepted as the calorimetric standard substance with a heat of Combustion of 6324 cal.,,..per g.(air) which is about 2% greater than the value given by Swientoslawskl from a consideration of various experimental results (A 1918 ii 32; 1921 ii 679). H. J. E. D. P. KONO- VBLOV (J. Buss. Phys. Chem. Soc.1918 50 81-105).-The heats of combustion of many naturally occurring fuels and of many organic substances are compared. These heats are calculated not on unit weight of substance burned but as calories per unit quantity of oxygen used in the combustion. A new factor r the oxygen potential of carbon compounds is introduced. This is calculated from the equation ?r = T/K where T the calorific power is the heat of combustion & minus the heat of vaporisation of the water produced and K the oxygen coefficient is the ratio of the weight of oxygen used to the sum of the weight of substance and of the water produced. r is calculated for a number of different coals for petrol for animal fat and for various types of saturated aliphatic compounds including paraffis alcohols amines ketones aldehydes and acids and found to vary very little for these sub- stances the mean value being 3.05 Cal.and hence T for normal carbon compounds is very little different from that for pure carbon. In the case of compounds containing oxygen it is incorrect to calculate the heat of formation or combustion on the basis that one oxygen atom may be balanced against two hydrogen atoms in the compound ; the correct method is to balance one carbon against two oxygen atoms. A formula for the calculation of the heat of formation of oxygen- containing saturated aliphatic substances is given and the results obtained from it are found to agree satisfactorily with those found experimentally for a number of substances. In the case of nitro- compounds however in which the oxygen is united to nitrogen and not to carbon this formula cannot be applied and in these cases the heat of formation may be calculated by assuming that the oxygen is present in the free state.In the case of homologous hydrocarbons it is found that ?r gradually increases as the pro- portion of hydrogen falls. Formu18 for the calculation of T for unsaturated hydrocarbons are deduced and found to agree satis- factorily with results obtained experimentally for ethylene acetylene and allylene r in these cases increming with the degree )I. W. The Calorific Value of Organic Substances.ii. 218 ABSTRBCTS OF UHEMICAL PAPERS. of unsaturation. The same formula is applied to the calculation of T for carbon as Cz which is found to 4-704. From this result the heat of vaporisation of C is calculated to be 103-6 Cal.r for saturated cyclic compounds differs little from that for straight chains whilst for aromatic compounds i t increases with increasing unsaturation varying between 3.1 for benzene and 3.138 for diphenylacetylene. For terpenes this value is of the same order as for aromatic substances. For rings containing oxygen how- ever a great increase is observable T for ethylene oxide being 3.585 for furfuraldehyde 3-364 and for trioxymethylene 3.509. Esters such as ethyl nitrite glyceryl trinitrate and mannitol hexanitrate behave differently from ordinary nitro-compounds liberating more energy on combustion. A formula is deduced for the calculation of the heat of combustion of such substances and it is shown that results calculated from it agree well with experi- mental figures.For cyanogen T is only slightly less than for Cz i.e. 4.097 whilst for hydrocyanic acid it is 3.847 both being very close to calculated values. Nitriles also give values for T above the normal and a small increase is apparent for compounds in which every carbon atom has a hydroxyl group attached such as glycerol. Acid amides and carbamide on the other hand have a value below normal e.g. for carbamide R = 2.914 and for oxamide 2.739. Many organic acids such as acetic propionic malonic and succinic acids have also low values. Carbohydrates have all values con- siderably above normal the heat effect being on the average 7.5% greater than that of their carbon content alone. Lignite and peat have slightly higher values than the normal 3.05 although lower than that of cellulose 3.262 indicating that they are transition stages to coal.R. T. The Heats of Combustion and of Formation ot certain Explosive Nitro-compounds from their Elements. P. P. RUBCOV and L. A. SEVERJANOV (J. Buss. Phzp. Chem. Soc. 1918 50,140-144) .-The heats of combustion of various nitro-compounds are measured and their heats of formation hence calculated. These are for 1 3 5-trinitrobenzene 3178 cal. and + 8.5 Cal. respec- tively for 2 4 6-trinitro-1-methylnitroaminobenzene 3016.5 cal. and - 14.2 Cal. for 2 4 6-trinitrotoluene 3691 cal. and + 13.6 Cal. for 2 3 4 6-tetranitro-1-methyhitrcaminobenzene 2551 cal. and - 29.9 Cal. for ammonium picrate 2890 cal. and + 78 Cal. for the ammonium salt of hexanitrodiphenylamine 3128 cal.and + 14 Cal. and for trinitroethane 1777 cal. and + 4.3 Cal. R. T. Nernst’s Theorem. TH. DE DONDER (Bull. A d . TOY. Belg. 1922 [v] 8 461465).-The author obtains various expressions for the heat of reaction a t constant pressure making use of Nernst’s theorem. E. E. T. Heat of Coagulation of Ferric Oxide Hydrosol with Sodium Sulphate. FREDERICK L. BROWNE ( J . Amer. Chem. am. 1923 45 311-321).-The heat of coagulation of ferric oxide hydrosol,GENERAL AND PHYSICAL CHEMISTRY. ii. 219 of widely varying purity by means of 0-2N-solution of sodium sulphate has been investigated using sols prepared by three dissimilar mekhods. The sols employed were prepared by the oxidation of a solution of ferrous chloride with hydrogen peroxide followed by dialysis by the peptisation of precipitated ferric hydroxide in ferric chloride solution and by the addition of various amounts of hydrochloric acid to a sol of a high degree of purity prepared by the first-named method.The same value for the heat of coagulation a t a given purity and total iron concentration is obtained with sols prepared by all three methods indicating that ferric oxide hydrosols represent an equilibrium which is defined by the tempera- ture pressure concentration and purity. The change in the degree of dispersion of ferric oxide during coagulation does not involve a measurable heat effect. The heat effects observed during the coagulation of sols of low purity are due to the dilution of the ferric chloride and hydrochloric acid contained in the sols to the mixing of these electrolytes with the added coagulating electrolyte and to changes in the adsorption equilibria.Interfacial Tension. JAMES ROBERT POUND (T. 1923 123 Viscosity Neutralisation and Isomorphism. L. J. SLVON (Compt. rend. 1923 176 437-4-40).-A study of the variation in viscosity of solutions of phosphoric acid and arsenic acid during their neutralisation by sodium hydroxide shows that the curves obtained for the two acids are superposable. The results indicate that in aqueous solution of the same molecular concentration isomorphous substances modify the viscosity of water a t a given temperature in the same manner. By isomorphous substances is meant those having similar chemical formula the same crystal- line form and showing syn-crystallisation.A study of the chlorides of sodium potassium rubidium and ammonium shows that this holds good for the last three named but that for sodium chloride there is a marked difference at all temperatures and all concentrations. Dissociation Pressures of certain Salt Hydrates by the Gas Current Saturation Method. WALTER C. SCHUMB ( J . Amer. Chem. Soc. 1923 45 342-354).-Measurements of the dissociation pressures of nine pairs of salt hydrates have been made by the gas current saturation method a t 25" and the results compared with those obtained by other investigators using the same or other methods. The pairs of hydrates examined were the mono- and di-hydrates of barium chloride di- and hexa- hydrates of strontium chloride tri- and penta-hydrates of copper sulphate anhydrous sodium sulphate and the decahydrate hexa- and hepta-hydrates of magnesium zinc ferrous cobalt and nickel sulphates.It is found contrary to the experience of several who have previously used the method in particular Menzies (A. 1920 ii 738) and Baxter and Lansing (A. 1920 ii 286) that when suitable precautions are takcn perfectly trustworthy results are obtained. J. B. S. 578-599). W. G.ii. 220 ABSTRACTS OF CHEMICAL PAPERS. The necessary precautions concern the size of the saturator con- taining the mixture of salt hydrates the method of measuring the total internal pressure the intimate mixing of the two solid phases the rate of flow of the current of air passing through the apparatus and the weighing of the water taken up by the air.It is shown that the objection raised to this method namely that insufficient time is given for the attainment of an equilibrium is without foundation since the equilibrium may be reached from both sides. No certain relationship has been found to hold between the com- position of analogous salt hydrates and their dissociation pressures measured at a given temperature although the influence of such factors as atomic volume and valency is admitted. Exception is taken to the generalisations of Clark and Buckner (A. 1922 ii 300) connecting the composition of ammines and hydrates with their stability in view of the numerous exceptions found in the literature. It is pointed out that much further work is necessary both in the formation and examination of new molecular compounds and in showing that numerous assumed compounds have no real existence before any definite relationships can be established.Abnormal Osmosis through Collodion Membranes. G. ~ E U N E R [with 0. RODER] (2. Elektrochem. 1923,29 54-64).-A number of osmosis experiments with dilute solutions of various potassium salts are described together with measurements of the potential difference at the collodion walls used to separate the dilute from the more concentrated solutions. The osmosis is shown to reach a maximum value a t concentrations between N/256 and N/512. It is shown that when a concentrated solution is separated from a dilute solution by a collodion membrane a fall of potential is brought about by the diffusion and this drives the solvent from the dilute solution to the concentrated solution and so brings about the abnormal osmosis.Since the diffusion potential between the walls of the membrane depends on the fall of concentration inside the walls of the membrane it follows that the abnormal osmosis is different with rotating membranes than with fixed membranes. With fixed membranes and stationary solutions the concentration on the surface of the membrane contiguous with the dilute solution is much greater than that in other portions of this solution. The ratio of the concentration on the two walls of the membrane approaches a maximum with increasing concentration of the concentrated solution. The maximum is reached a t a concentration such that with the same concentration on both sides of the collodion wall the electro-endosmosis and the electro-adsorp- tion potential 5 also have their maximum value.This is explained if it be assumed that a t this concentration the coefficient of diffusion is a t its minimum. Such an assumption is in keeping with the fact that the diffusion potential difference is much greater with membranes than without. The electrolyte behaves in the membrane aa though the migration velocity of the anion v is reduced and the more reduced the greater the value of [. Since in the equation for the diffusion potential difference the value of (u - V ) / ( Z L + u) J. F. S.QENERAL AND PHYSICAL CHEMISTRY. ii. 221 and the ratio of the concentrations for concentrations in the region where the more concentrated solution shows a maximum osmotic pressure decrease in the same way as [ the maxima of the diffusion potential difference of the abnormal osmosis and the electro-endosomosis must lie close together. With rotating membranes the concentrations on the surface of the membrane differ only slightly from the concentration in the interior of the solution since there is only a fall of concentration over the very thin adhering layer of the solution on the outside of the membrane.The diffusion potential difference increases with increasing concen- tration of the concentrated solution up to a very high value of this concentration. For these reasons and because of the increased pure osmotic action no maximum of the transport of liquid occurs. The maximum of the abnormal osmosis with collodion membranes is due to a further cause if as is stated by Loeb it is caused by the increase in the diffusion potential d8erence and the decrease in the charge on the membrane with increasing concentration of the more concentrated solution.Potential Difference occurring in a Doman Equilibrium and the Theory of Colloidal Behaviour. A. V. HILL (Proc. Roy. Soc. 1923 [ A ] 102 705-710).-A theoretical paper in which the contention of Loeb (Proteins and the Theory of Colloidal Behaviour) that the Donnan membrane equilibrium (A 1911 ii 848) involving the presence of an ion which does not diffuse is the basis of the colloidal properties of a protein solution is discussed. Whilst the possibility of Loeb’s conclusion is admitted it is pointed out that one of the main arguments used in its favour by Loeb is incorrect. Loeb shows that the potential difference observed experimentally between a protein and a non-protein solution separated by a membrane agrees very exactly with that calculated from the difference in hydrogen-ion concentrations also observed experimentally and concludes that this supports his hypothesis. As it matter of fact this equality is a necessary and inevitable consequence of the manner in which the observations were made and of general thermodynamic principles and its proof is independent of any hypothesis of the mechanism by which the potential difference is produced.J. F. S. Anomalous Osmosis of Solutions of Electrolytes with Colloidal Membranes. I. The Electrical Properties of the Membrane System. F. E. BARTELL and DWIGHT C.CARPENTER ( J . Physical Chem. 1923 27 101-116).-1t is shown that in the measurement of osmosis in collodion bags as prepared by Loeb (A. 1919 ii 399 497) an increase in volume of 15% is brought about by small heads of solution which causes a considerable error in the pressure values obtained. To avoid this source of error the authors have used collodion membranes prepared by Bigelow and Gemberling’s method (A 1907 ii 933) which they find are uniform in thickness and permeability and by regulating the conditions under which they are formed the permeability can be adjusted to any particular value. The membranes were mounted in a non- J. F. S.ii. 222 ABSTRACYL'S OF CHEMICAL P-4PERS. leaking osmotio cell made of two 9'-shaped glass compartments of equal volume held together by a brass coupling which holds the membrane firmly between the two compartments.The osmosis values of 1.0 0.1 0.01 and 0.001M solutions of hydrochloric acid and potassium hydroxide chloride sulphate ferrocyanide ferri- cyanide carbonate phosphate acetate oxalate and tartrate sodium chloride calcium magnesium and aluminium chlorides have been determined and the maximum potential of each osmotic system has been measured at 25". The sign of the membrane charge has been determined by cataphoresis experiments using finely ground suspended membrane material. The data show that the initial rate of osmosis bears a definite relationship to the electrical properties of the membrane system for practically all the salts examined. The anomalous effects obtained with collodion are very similar to those obtained with membranes of porcelain gold beater's skin calf's bladder and parchment paper.The maximal and minimal values obtained with these different membranes do not come at exactly the same concentrations but when the results are considered in the light of the exact condition of the electrical orientations of the different membrane systems they are found to be closely comparable. It is also shown that the anomalous effects are somewhat related to a time factor. For example the data for the osmosis of potassium carbonate a t the end of a two-hour period when plotted against the logarithm of the concentration did not give an N-shaped curve whilst the A'-shape is pronounced in the curve obtained a t the end of a twelve-hour osmosis period.This makes it appear probable that the process of diffusion is in some way responsible for the repressing effects noted at the intermediate concentrations. J. 3'. S. Four Laws of the Mutual Influence of Salts on the Solubility. P. P. VON WEIMARN (ICoZZoid Z. 1923 32 145-149).-The author discusses four laws of mutual influence of salts on solubility and shows the importance of these to the behaviour of colloidal solutions. The four laws are (1) Nernst's law. The solubility of a salt is decreased by the presence of a second salt which has a common ion with the first. The solubility of a salt increases in the presence of a second salt which has no ion in common with the first salt. (3) The solubility of a salt in the presence of a second salt with a common ion commences to increase from a definite concentration of the second salt.The definite concen- tration is determined by the nature of the two salts and the solvent and is lower the smaller the power of the solvent to break up the complexes formed. (4) When two or more salts are dissolved in a given solvent a competition for the solvent between the salts takes place so that a decrease in the solubility of the salt which takes up least of the solvent follows. The existence of the third law demands a new statement of Nernst's law which is therefore now written The solubility of a salt in the presence of a second salt with a common ion decreases when the concentration of the second salt does not exceed a definite value. (2) Noyes's law. J I?.S.BENERAL AND PHYSICAL CHEMISTRY. ii. 223 Relation between Molecular and Crystal Symmetry as shown by X-Ray Crystal Analysis. G. SHEARER (Proc. Physical Xoc. 1923 35 81-100).-A theoretical paper in which the methods of X-ray analysis the nature of the elementary crystal lattice and the meaning of axes and planes of symmetry in the lattice are discussed. It is shown that the methods of X-ray analysis enable the number of molecules associated with the unit cell to be determined. With the aid of this information an attempt is made to connect the symmetry properties of the crystal with this number and with the symmetry properties of the molecules from which the crystal is formed. The symmetry number for each of the thirty-two crystal classes is given and is shown to mean the mini- mum number of asymmetric molecules necessary in the unit cell to satisfy the symmetry conditions.The relative orientations and positions of these molecules in the cell are discussed. It is suggested that this symmetry number is the actual number of molecules in the cell when the molecule is asymmetric ; further that if the mole- cule possesses symmetry this symmetry appears also in the crystal and the number of molecules in the unit cell is obtained by dividing the symmetry number of the crystal by the symmetry number of the molecule. Evidence is produced in support of these hypotheses arid examples are given of their application to inorganic and organic crystals. J. F. S. Structure of Metal Crystals. Modification of the Powder Method of Determining the Structure of Metal Crystals.E. A. OWEN and G. D. PRESTON (Proc. Physical Soc. 1923 35 101-108).-Plates of aluminium iron copper lead and magnesium have been examined by means of a Bragg X-ray spectrometer employing radiation from a molybdenum anti-cathode. The maxima observed in the spectra are sufficiently intense to measure with accuracy and the crystalline structure of the materials examined is readily determined. The following data have been obtained aluminium has a face-centred cubic lattice the length of the side of the unit cube of which is a = 4.041 A and the number of atoms associated with each elementary cube is n = 3.98; iron has a centred cubic lattice n = 2.015 and a = 2.869 8.; copper has a face-centred cubic lattice a = 3.628 d. and n = 4.06 ; lead also has a face-centred cubic lattice a = 4.983 A.and n = 4.11 and magnesium has a hexagonal lattice the side of the hexagon having a mean value a = 3.17 A. and n = 0.98. The Mesomorphic State of Matter. G. FRIEDEL (Ann. Physique 1922 [ix] 18 273-474).-A new classification of liquid crystals according to their structure. Matter is capable of existing in two forms neither crystalline nor liquid for which the new designation the mesomorphic state is proposed. The first form is called the smectic phase after the soaps which occur in this class and the second the nematic phase on account of the linear discontinuities which are its principal feature. A short historical account of liquid crystals and a summary of the substances giving rise to either or both of the two types are given.J. F. S.ii. 224 ABSTRACTS OF CHEMICAL PAPERS. The smectic and nematic phases when they occur together are always separated by a discontinuity and the former is the phase which is stable at the lower temperature. The smectic form is always optically positive but the latter may be divided into two classes nematic proper and cholesteric according to the sign of the rotation. The smectic phase possesses high viscosity and is rigid except in the direction of the optical axis and displacement is accom- panied by a change of structure. On the other hand the nematic type is fluid often more fluid than the liquid and accommodates itself to movements within the film brownian or otherwise. When the smectic phase is not homogeneous as when the temperature is raised there appears a new structure showing groups of lines which are always in the form of focal conics.The conics form groups of two an ellipse and a hyperbola and the focal groups are often systematically arranged inside a polygonal structure. This structure is discussed in detail. On cooling from the liquid or nematic state the smectic phase makes its appearance in short rods ornamented by focal groups; the nematic type gives droplets in similar circumstances. A magnetic or electric field is without action on the smectic phase whereas the structural lines in the nematic phase are oriented so that the optical axis becomes parallel and normal respectively to the lines of force. Another point of difference between the two forms is the behaviour on transition from the crystalline to the mesomorphic state.In both types the new structure is based on the old but whereas the old surfaces of separation of the crystals show focal conics in the smectic phase the division in the nematic type is always absolute. The two kinds of complex structure possessed by the latter type are based on threads with no characteristic geometric form and on centres which give rise to a spherolytic structure. The cholesteric type which is optically negative is only a special form of the optically positive variety for there is a gradual change from the optically negative class to the normal nematic type. The Cholesteric Type of. Compounds. GEORGES FRIEDEL (Compt. rend. 1923 176 475478).-The addition of very small amounts of a cholesteric substance to a substance such as azoxy- anisole or azoxyphenetole having a nematic phase impresses on the latter the characteristic properties of the cholesteric type.If it is admitted that the rotatory power of the cholesteric phase is due to a very high torsion round the normal to the positive optical axis then the rotatory power measured in the normal region of the spectrum should be greater the smaller the torsion. This is shown to be the case for mixtures of azoxyanisole and cholesteryl acetate. From a consideration of the behaviour of mixtures of azoxy- anisole or azoxyphenetole or of methylbenzylidenebenidine with colophony it is shown that the addition to a nematic substance of any substance having molecular rotatory power gives rise to a cholesteric substance in which the two typical structures of this form of matter are seen.If the amount of the asymmetric sub- W. E. G.GENERAL AJFD PHYSICAL CHEMISTRY. ii. 225 stance exceeds a certain generally very small amount the structure with planes shows a very shong rotatory power of the type of ordinary cholesterol compounds but if the amount of the asym- metric substance tends towards zero there is a gradual passage from the cholesteric to the nematic characteristics. Dielectric Constants of Colloidal Solutions. 11. J. ERRERA (Kolloid Z. 1923,32,157-163).-A continuation of work previously published (A 1922 ii 694). The dielectric constant of a number of vanadium pentoxide sols has been determined under a variety of conditions. It is shown that the constant is increased by passing an alternating current through the solution due to electric coagul- ation.Dilution of a sol causes an immediate decrease in the value of the dielectric constant but on keeping the value increases with time; this is due to the partial solution of the disperse phase. Increasing temperature decreases the dielectric constant to an amount corresponding with the increase in the molecular motion and the degree of dispersion. The dielectric constant increases with increasing current strength and increasing wave-length in accordance with the increased directing force. Measurements of the electrical conductivity of the solutions show that the changes observed in the dielectric constant are real and not due to changes in the conductivity factor.The importance of the above results for the theory of electrical double refraction and anomalous dispersion is pointed out. The Study of Soap Solutions. J. W. MCBAIN (Rep. Brit. ASSOC. l922,360-361).-A review of the evidence for the existence of the ionic micelle and the theories arising therefrom. Lyotropic Action in Processes of Solution of Colloids. N. P. PESKOV (Kolloid Z. 1923 32 163-166).-The action of the kations ammonium lithium sodium potassium rubidium and cmium on the rate solution of arsenic sulphide gold and cupric sulphide sols in alkaline media has been investigated. It is shown in all cases that the lyotropic action of these kations is in the order NH,'IH,OILi' Na' K' Rb. Cs'. The ammonium ion decreases the rate of solution very strongly whilst the other ions increase it more the greater the atomic weight of the element.The effect of adding the chlorides of the alkali metals on the time required for the pro- duction of the blue colour in mixtures of sodium sulphife sulphuric acid and iodic acid has also been investigated and found to have in all cases an accelerating action the order of increasing acceler- ation being Li' Na' K' NH; Rb' Cs'. With the exception of ammonium the order is the same as that noted above. Similar experiments with coagulated arsenic sulphide and gold gave exactly the same order as was obtained with the uncoagulated sols showing that the lyotropic action extends to macro-heterogeneous systems. A still coarser system gold obtained by the reduction of gold chloride with hydrogen peroxide furnished identical results and finally gold powder dissolved more rapidly in the presence of rubidium chloride than in pure water.Hence it is shown that the W. G. J. F. S. E. H. R.ii. 226 ABSTEBCTS OF CHEMICIAL PAPERS. lyotropic action refers only to the solvent and is manifested with a& degrees of dispersion of the system. Adsorption only plays a parti in so far as it may displace the action. The Effect of Dissolved Substances on the Deposition of Colloidal Particles from a Solution by means of an Electric Current. RICHARD D. KLEEMAN (Physicid Rev. 1922 20 272-279).-The addition of 0.1-0*3~0 of sodium hydroxide silicate sulphate phosphate hydrogen phosphate or tartrate potassium hydroxide or tartaric acid to porcelain slip (a colloidal solution of clay flint and felspar in water) results in the formation of a solid instead of a semi-liquid deposit when it is subjected to an electric current.The increase in compactness of the deposit obtained on the addition to the slip of one of the substances men- tioned was found to be intimately connected with the increase in fluidity of the slip produced by them. In explanation it is assumed that the addition of a small amount of a substance to the slip decreases the radii of the spheres of action of the particles or the spheres associated with the particles which do not penetrate into each other during their motion of translation. The fact that continued addition of the substance first precipitates some of the particles mainly the flint and felspar and then causes redissolution is explained in the same way.The equations of distribution of colloidal particles under the action of gravity are obtained. The experimental results indicate that the volume of the spheres of action of a particle in porcelain slip is about twice the actual volume of the particle. Ultramicroscopic Method for the Measurement of the Velocity of Kataphoresis. H. R. KRUYT and A. E. VAN ARKEL (Rolloid Z. 1923 32 B1-95).-An apparatus is described whereby the velocity of kataphoresis of ultramicroscopic partieles may be measured. From the measurements it is shown that the potential a t the interface colloid-dispersion medium may be calculated. Using this apparatus the velocity of kataphoresis of selenium sols has been determined a t distances 0-900 mm.from the walls of the containing vessel. The potential a t the interface is found to be 43 m.-volts. Heterogeneous Equilibria between the Chlorides of Cal- cium Magnesium Potassium and their Aqueous Solutions. I. WILLLAM BELL LEE and ALFRED CHARLES EGERTON (T. 1923 123 706-716). Equilibria between the Acido- and Aquo-iridiwnpent- ammines. ARTRTJR B. LAMB and LAWRENCE T. FAIRHALL ( J . Amer. Chm. Soc. 1923 45 378-395).-Slight modifications have been made in Palmaer's method of preparing iridiumpentam- mine salts; these modifications give purer products and are more convenient (A 1896 ii 179). Chloropentammineiridium chloride has been shown to undergo no appreciable decomposition in aqueous solution a t 100". The velocity of transformation of chloro- bromo- iodo- and nitrato-pentammines iato the corresponding aquammines and vice versa has been measured at 95" and in the case of the J.F. S. A. A. E. J. F. S.bromo-ammines a t 80". All these transformations have been found to follow the course of a unimolecular reaction and their velocity constants have been found to have the same relative magnitudes as the corresponding constants of the cobaltammines. The equilibria reached in these transformations have been in- vestigated analy-tacally. For this purpose the method of McLean and Van Slyke (A. 1915 ii 479) has been carefully studied and still further refined. The values for the equilibrium concentrations thus found are shown to be substantially in agreement with those calculated from the velocity measurements and similar to those of corresponding equilibria among cobaltammines.They are ali however markedly displaced from the aquo-side of the reaction as compared with the corresponding cobaltammines. The values for the concentrations found in the bromo-bromide equilibrium have been shown to agree reasonably well with the requirements of an empirical equation similar to that found for the cobaltammines. This equation has the form [C,-Cc,,,]0.46/Cp=K2 where CB and Cp represent the total concentration of q u o - and acido-salts respectively. The conclusion has therefore been drawn that whilst the exchange of the central cobalt atom for an iridium atom in the ammines considered has produced a general displacement in the velocity and equilibria constants it has produced no relative displacements.J. F. S. Dynamics of the Formation of Nitriles from Acid M y - drides and Amides. lV. Investigation of the Reaction between Acetamide and BenzQic anhydride by Phase Rule Methods. ROBERT KREMANN ALOm AUER VIKTOB OSWBLD and ALFRED ZOFF (Xonatsh. 1923 43 345-358).-The inter- action of equimolecular quantities of acetamide and benzoic an- hydride proceeds according t o the simple equation CH3*CO*Nq+ (C,H5*CO),0 =+= CH,*CN+BC,H,*CO,H no side-reaction (to pro- duce acetylbenzoylimide) occurring (cf. A. 1922 ii 748). The reaction was followed by the method previously employed by the author. The formation of an equimolecular compound (cf. this vol. i 336) between acetamide and benzoic anhydride melting a t a temperature (84') at which these two substances inferacti rapidly caused difficulty in obfaining accurately the firat few points on the temperature-freezing point curve.Other difimlties arose from the volatility of metonitrile. The reaction studied is reversible equilibrium (at 98') being reached a t 69% conversion from left to right of the above equalion. The formation of the compound between acetaslide md benzoic anhydride is thought to explain the fact fiat; from the r d t s of the present investig- ation benzoic anhydride appeazs to be a less effective dehydrating agent than acetic anhydride w h r w other results point to the contrary conclusion (cf . following abstract). Dynamics of the Formation of Nitriles from Acid Amides and Mydrides. V. The Study of the Reaction 1 3BetpeOi;C Anhydride + 2 Acetic Acid 2 Benzoic Acid + 1 Acetic Anhydride.&;BERT &EM~NN and WILHELM B i b E R (ikfoZuZkh. 1923 43 359-365).-The reaction studied proceeds from left to E. E. T.ii. 228 ABSTRACTS OF C m C A L PAPERS. right (at 77-45") to the extent of about 65% giving a reaction con- stant K=6*4. The reaction was studied by the usual method (freezing-point determinations a t intervals with subsequent refer- ence to a freezing-point curve obtained from known mixtures etc.) and it is shown that although undoubtedly two side reactions producing the mixed anhydride occur these do not affect to any extent the figures given above for the main reaction. E. E. T. The Conditions of Reaction of Hydrogen with Sulphur. I. Direct Union. RONALD GEORGE WREYFORD NORRISH and ERIC KEIQHTLEY RIDEAL (T.1923 123 696-705). The Propagation of Flame in Complex Gaseous Mixtures. V. The Interpretation of the Law of Speeds. WILLIAM PAYMAN (T. 1923 123 412-420). The Rate of Detonation in Complex Gaseous Mixtures. WII;LI~LM PAYMAN and NOEL STANLEY WALLS (T. 1923 123 420-426). The Effect of Pressure on the Limits of Inflammability of Mixtures of the Paraffin Hydrocarbons with Air. WILLIAM PAYMAN and RICHARD VERNON WHEELER (T. 1923 123 426- A Simple Form of Apparatus for Observing the Rate of Reaction between Gases and Liquids and its Use for Deterplining the Rate of Solution of Oxygen by Water under Different Conditions of Mixing. H. G. BECKEB (Phil. Mag. 1923 [vi] 45 581-592).-The principle on which the apparatus is based depends on the changes in pressure which occur when a liquid is placed in contact with a closed volume of gas.The measurements of the absorption of oxygen were made with a suspension of ferrous hydroxide in water. Five different rates of stirring of the water were employed ranging from zero to 1000 revolutions per minute. The process of adsorption followed a linear law showing that the deoxygenation of the water was com- plete in a few seconds. The rate of solution per unit area increases rapidly with increase in the rate of stirring and tends to a maximum a8 the higher rates are reached. Gentle stirring of the under layers of the water increases the rate of solution as much as twenty-fold compared with stationary water. When in the quiescent state the rate of solution of a gas by a liquid is liable to sudden unaccount- able changes.The maximum rate of solution attained in these experiments was 0.0016 C.C. per min. which was about half that 434). obhined by another method previously reported (cf. A. 1919 ii 510). W. E. G. The Velocity of the Absorption of Carbon Dioxide by Ammoniacal Solutions. PAUL RIOU (Cmpt. rend. 1923 176 581-583).-The influence of varying amounts of sodium and ammonium chlorides and sodium hydrogen carbonate on theGENERAL AND PHYSICAL CIFEMISTRY. ii. 229 absorption of carbon dioxide by ammonium carbonate solutions was studied and the results obtained are expressed by curves showing the C.C. of gas absorbed per second per,sq. cm. of surface by ammonium carbonate solutions containing 0.04 g. mol. per 100 C.C. in presence of varying concentrations of the other salts.Sodium and ammonium hydrogen carbonates have the greatest retarding influence on the absorption and ammonium chloride the least a t 20". The influence of temperature on the absorption in presence of ammonium and sodium chloride at different concen- trations is also shown. With decreasing concentrations the maximum absorption velocity is displaced slightly on the temperature axis being a t about 20" with 0.5 g. mol. NH4C1 per 100 C.C. and 35" with 0.1 g. mol. per 100 C.C. The maximum with sodium chloride solutions lies a t about 50". G. F. M. The Antagonistic Action of Ions. H. WASTL (Biochern. Z. 1922 134 131-138).-The influence of the anions of various potassium salts on the time which elapses before the blue colour of starch iodide appears in the reaction between iodic acid and sulphurous acid (Landolt's reaction) has been studied.The results c o n h Berczeller's observations that the reaction is accelerated by the anions in the order I7Br> Cl>NO,> SO,. Sulphate is antagonistic to chloride bromide or iodide the latter accelerating the reaction the former retarding it. H. K. The Velocity with which Carbon Monoxide Displaces Oxygen from Combination with Haemoglobin. I. H. 18Sa~- RIDUE and F. J. W. ROUGHTON (Proc. Roy. Soc. 1923 [B] 94 ([B] 662) 336-367).-The reaction CO+02gb G+ O,+CO% is a reversible one and the equilibrium constant has a value in light differ- ent from that in darkness. On this circumstance are based two methods for measuring the velocity constant of the reaction a determination difficult to carry out directly as equilibrium is attained very quickly.In the first method hzemoglobin solution con- taining oxygen and carbon monoxide flows through two glass tubes in series one illuminated and the other in darkness. Measure- ments are made of the percentage of oxyhaemoglobin and carboxy- haxnoglobin at various points in the illuminated tube by means of the reversion spectroscope (Hartridge this vol. ii 105). If the rate of flow is known the time taken to reach the various points at which measurements have been made can be calculated and hence the velocity constant of the reaction found. The second method consists in interrupting the illumination of the haemoglobin contained in a trough and measuring accurately the time taken for the change towards the new equilibrium to proceed a certain distance as indicated by analysis by the reversion spectroscope.The values of k the equilibrium constant obtained by the two methods at 16" are 0.55 and 0.42 respectively the difference being within the experimental error. The mean temperature coeffic6wt as obtained by the two methods is 2.5 and log k is approximatdy inversely proportional to the temperature. W. 0. K. VOL. CXXIV. ii. I)ii. 230 ABISTELBCTS OP aREMICAL PAPERS. The Decomposition of Formic Acid by Sulphuric Acid. ERNEST R. &?HIE= ( J . Amer. Ohem. soc. 1923 45 47465).- A study of the velpity of decomposition of formic acid by sulphuric mid of different concentrations a t temperature intervals of 10" from 15" to 45".The reaction is unimolecular and probably one of dehydration The addition of small amounts of water t o the reaction mixture markedly decreases the velocity of the reaction whioh however increases rapidly with rise in temperature. There is a marked irregularity in the temperature coefficients of the reaction for 91*8~0 sulphuric acid. The presence of copper silver potassium sodium or mercurous sulphates causes only a slight retardation of the reaction. Acetone and acetic acid act M inert diluents but hydrochloric acid increases the velocity of the reaction considerably. w. G. Hydrolysis of Methyl o-Nitrobenzoate in Acid Solution. GERALD E. I(. BRANCH and DON- S. MCKITTRICK ( J . Arner. Chem. Soc. 1923,45 321-327).-The rate of hydrolysis of methyl benzoate and methyl o-nitrobenzoate the rate of eaterificetion of o-nitrobenzoic acid and the position of the equilibrium in each case has been determined under the same conditions.The reaction mixtures contained 60% of methyl alcohol 40% of water O*2€" sulphuric acid and 0.1104 g.-mols. per litre of organic acid or ester. It is found that the equilibrium for the unsubstituted and the substituted compound lies a t practically the same point. The esterification is found to be of a higher order than the corresponding hydrolysis. The rate of hydrolysis of methyl benzoate is found to be twenty times as great as that of methyl o-nitrobenzoate. This result is a t variance with the results obtained by K e h (A 1898 i 96) for alkaline solutions. The discrepancy is explained by wum- ing the reactions to be preceded by complex formation between the ester and the hydrogen- or hydroxyl-ion.As is to be expected tho -nitro-group favours the formation of the complex with the hydroxyl- ion and the dissociation of that with the hydrogen-ion and conse- uently accelerates the reactions in alkaline solution but retards t B ose in acid solution. J. IF. S. Enzymatic Hydrolysis of Alkyl Glucosides. Detemnin- ation of some Molecular Weights. H. COI;" and (MILE) A. CHAUDUN (Corn#. rend. 1923 176 440-442).-When to a given weight .of a glucoside increasing amounts of a preparation of emulsin are added the weight of dextrose liberated in hwenty- four hours gradually increases to a maximum beyond which any further addition of the enzyme does not cause any increase in the amount of dextrose liberated.In the cam3 of methyl pmpyl kopropyt butyl and isobutyl glucosides it is shown that the volume of the given enzyme preparation required to give the m h u m hydrolysis in twenty-four hours is within the limits of error of the experiment inversely proportional to the molecular weight of the grucoside. W. G.GENERAL ABND PHYSICAL CHIMfsTBp. 3. 231 Dependence of the Velocity of Coagulation of Suspensoids on the Temperature. W. W. LEPESCHKIN (Kolloid Z. 1923 32 166-167).-The temperature coefficient of the rate of coagul- ation of denatured albumin arsenic trisulphide and lecithin in the presence -of alkali salts has been determined. The value of the coefficient in the case of arsenic sulphide is the smallest and is the same as that of the salt diffusion.Lecithin has a somewhat greater coefficient whilst that of albumin is greatest and has a value approximating to that of a chemical reaction. Mechanism of the Catalysis of Hydrogenation by Nickel. ~ ~ T L A N D c. BOSWELL (Trans. Roy. Xoc. Canada; 1922 16 111 1-26) -By a quantitative study of the reduction of nickel oxide by hydrogen and of the catalysis of the hydrogenation of ethylene by partially reduced nickel oxide it is shown that oxygen necessarily present in a normal nickel catalyst exists partly in the form of nickel oxide in the interior of the catalyst particles and partly as negatively charged hydroxyl groups together with positively charged hydrogen on the surface nickel of the particles. Hydrogen absorbed during the reduction of nickel oxide exists on the nickel surfaces with both positive and negative charges.The structure of the catalyst is represented by (NiO),,Ni(HOHHOH . . . .) and the catalysis of the hydrogenation of ethylene by the following (1) (NiO),,Ni(HOHHOH . . . .)+C2H4(F) - + + - (NiO)z,Ni(&X%3) + C a S H20. (2) (NiO),,Ni(HOHHOH) + &H) -+ (NiO),,Ni(HOHHH) + H20. (3) (NiO),,Ni(HOHHH) -+ (NiO),,,Ni(HOH) + H,O. A fourth reaction representing the mechanism of hydrogen absorption also occurs and involves the addition of positive and negative hydrogen-ions derived from neutral hydrogen molecules to the complex on the right-hand side of reaction (1) to form the complex on the left-hand side of reaction (3). of these reactions (1) is very fast and (2) and (3) are very slow.The latter pair also represents the reactions occurring on continued reduction of nickel oxide by hydrogen. Finally by such reduction all hydroxyl groups on the surface are removed and only absorbed hydrogen with positive and negative charges remains. J. F. S. + - + - - I - - + - - -I- + - + - + - J. S. G. T. The Catalytic Decomposition of Formic Acid in Acetic Anhydride. ERNEST R. SCHIERZ ( J . Amer. Chern. Xoc. 1923 45 455468).-Sulphuric nitric hydrochloric hydrofluoric phos- phoric and oxalic acids act as catalysts in 6he decomposition of formic acid in acetic anhydride but owing to side reactions it is no6 possible to obtain quantitative data. Tertiary baaes <cause a siinilar catalytic decomposition and the velocity of decomposi lion corresponds rdughly with the basicity of the base.A weak base like cafleine does not cause decomposition. Velocity constanla have bcen determined for a number of bases at 50". The reactibs 9-25. 232 ABSTRACTS OF CHEMICAL PAPERS. is one of the h t order and the velocity increases with the con- centmtion of the catalyst. The decomposition by pyridine proceeds with different velocities in different solvents such as benzene toluene acetone carbon tetrachloride nitrobenzene ethyl amyl and isobutyl alcohols amyl acetate and benzaldehyde. Acetic acid has an inhibitory effect on the catalysis by brucine strychnine and morphine but not on the catalysis by pyridine. This inhibitory effect may be used as a quantitative method for estimating acetic acid in its anhydride.In two cases the joint effect of two bases was the sum of their separate effects. The author suggests a possible mechanism for the reaction by the formation of an inter- mediate compound. W. G. The Constitution of ’the Atom. A. REYCHLER (Bull. SOC. chim. Belg. 1922,31,411-417 ; cf. A. 1922 ii 279).-The author’s previous formula for the calculation of atomic weights from atomic numbers A=2N+ bN2 is now derived from theoretical consider- ations and it is showwthat the atomic radii of the elements of the helium group deduced by extrapolation from Bragg’s crystal measurements are proportional to the cube roots of their atomic numbers. From a consideration of the energy changes involved when an electron is transferred from one shell to another the author is able to derive Moseley’s frequency formula v =const.( l/m2- l/?$)(N-b)? H.H. The Structure of the Atomic Nucleus. W. VAN DER BERG (Chem. WeekbEad 1923 20 54-58) .-A critical discussion of the results of Harkins (A. 1922 ii 172). The packing effect of four protons in the helium nucleus corresponds with a loss of mass of 0.032 on the mass 4.032 or about 0.8%; a loss of mms is to be expected from the theory of relativity. The deduc- tions of Lunn are criticised as being based on the assumption that Coulomb’s law is valid within the nucleus and as ignoring differences in m a s due to the velocity of the nucleus. The velocity required in an a-particle to disintegrate a helium nucleus is calculated as more than one-eighth the velocity of light ; the fastest a-particle that projected by radium C has a velocity one-fifteenth that of light.The P-particle has a velocity approach- ing that of light but its mass is insufficient ; neither has any known electro-magnetic radiation a frequency high enough to effect the disintegration. Since there is no measurable loss of weight in the formation of carbon oxygen and heavier atoms from &particles i t should be possible to disintegrate these by bombardment. From a consideration of the atoms of low atomic weight up to calcium it appears that where elements of uneven atomic number contain in addition to a-particles both external and internal (binding) electrons the stable configuration is na-particles with three protons and two external electrons. No stable configuration can be formed from two helium nuclei.It is clear that for the lighter elements those having an even atomic number are much qore stable than those having an odd atomic number whilst the heavier elements are much less stable than the lighter. S. I. L,GENERAL AND PHYSICAL CHEMISTRY. ii. 233 The Number of Radiating Atoms of Various Dimensions within Gaseous Hydrogen from the Point of View of Bohr’s Atom Model. P. LASAREV (Phil. Mag. 1923 [vi] 45 430- 432).-On the Rutherford-Bohr theory the radius of an electronic orbit moving round a hydrogen atom is given by a=h%/&2rne2. On account of the mutual influence of the electric fields of t’he atoms 7 cannot exceed 15 and thus the dimensions of the orbits will range between 2 a = 1 * 1 ~ 1 0 - ~ cm. ( ~ = 1 ) to 247*5~10-~ cm. (~=15).In star spectra however the existence of atoms with an electronic orbit of the order 33 is indicated. Calculations are made from the energy of definite spectral lines of the relative number of atoms of hydrogen gas possessing electron orbits of the different orders. Most of the electrons causing the radiation spring over from the third orbit to the second and the quantity springing over from the fourth orbit to the second equals only 25% of the first quantity. Those from the fifth to the second orbit are only 17% of the number from the third to the second. Thus the quantity of springing electrons decreases with the distance of the electrons from the centre. Compressibility Internal Pressure and Atomic Mag- nitudes. THEODORE W. RICHARDS ( J . Arner. Chem. Soc. 1923 45 422-437).-A theoretical paper in which the respective bulks of the elements in combination have been evaluated from consider- ations of the compressibilities of the individual elements and t’he contraction which occurs during combination.With the help of Bridgman’s accurately determined pressure volume curves for potassium and sodium (Proc. Nat. Acad. Xci. 1922 8 361) and the author’s own earlier results of the compressibilities of bromine and chlorine (A. 1922 ii 42) extrapolated by careful study of the nature of the curves [for which surprisingly concordant equations of the type (p+P)(v-B)=R are derived] the values of the internal pressures existing in these salts as well as the relative volumes of the components and the atomic diameters in combination were calculated.J. F. S. The Influence of the Atomic Nucleus on Valency Orientation and the Induced Polarity of Atoms. HERBERT HENSTOCK (Chem. News 1923 126 129-135).-A theoretical paper in which the alternate polarity of a chain of atoms is ascribed to a rotation of the nuclei and the inner electrons of the atoms. The nucleus of an atom is assumed to be a dipolar sphere with the inner electrons situated a t or near the poles and according to the direction of the dipole within the atom the valency bond will be either positive or negative. A strong outside influence may rotate the nucleus of a key atom thus determining its polarity and inducing an opposite arrangement in a neighbouring atom. This in turn will determine the orientation of the next atom and so give rise to alternate polarity. The relationship between electrovalence and covalence is discussed. Method of Representing Co-ordinated Compounds. T . 3 . LOWRY (Chemistry and Industry 1923 42 22&225).-The &- W. E. G. W. E. G.ii. 234 ABSTRACTS OF CWEMICAL PAPERS. advantages of the conventional representation of the stereoiso- merism of co-ordinated compomds e.g. potassium cobaltinitrite or cobalthexammine chloride by a square pieroed by an axis of fourfold symmetry as suggested by Werner or by the crystallo- graphic projection of an octahedron are briefly referred to. Altern- atively the author suggests that such stereoisomerism should be graphically represented by the plane diagram of an octahedron obtained by drawing the customary hexagonal representation of the benzene ring and joining the 2 4 6 positions by full straight lines and if desired joining the 1 3 5 positions by dotted straight ation is illustrated by diagrams showing the enantiomorphism of the different types of compounds to which Werner attributed asymmetry. More especially it is pointed out that enantiomorphs exhibiting optical activity and in which three identical bivalent radicles are associated with a single atom of metal can be readily depicted by using the two variants of KekulB's formula for benzene. Change of Water of Hydration into Adsorbed Water during the Mechanical Subdivision of Crystal Hydrates. T. HAQI- WARA (KoZZoid Z. 1923 32 154-156).-Weimarn has previously stated that the affinity of a substance for its water of crystallisation decreases aa the size of the particles diminish. With the object of testing this statement the author has determined the amount of water which the hydrate A12Q3,3H20 will retain at various temper- atures in ordinary circumstances and how this amount is affected by grinding the alumina with four times its weight of quartz. The experimental results show that Weimam's hypothesis is in keeping with the facts for example after heating a specimen of A1,0,,3H20 n t 180" for five hours the material still retained 2-82 molecules of water whilst heating the finely ground material a t the same temperature for four hours removed all the water but 0.99 mol. per mol. J. I?. S. Lecture Experiment Demonstrating Adsorption. H. G. TANNER ( J . Amer. Chem. Soc. 1923 45 437438).-A quantity of a solution of malachite green oxalate is poured into a clean beaker and immediately poured away. The beaker is then washed with large volumes of water. Then a few C.C. of water are poured into it shaken round the walls and poured into a test-tube. The solution is quite colourless. A few C.C. of glacial acetic acid are next added to the beaker shaken round the walls and poured into a test-tube. The solution in this case is distinctlygreen due to malachite-green which has been adsorbed on the walls of the beaker and dissolved in the acetic acid. J. 3'. 8. J. S. G. T.

ISSN:0368-1769    

DOI:10.1039/CA9232405197

出版商:RSC    

年代:1923

数据来源: RSC

摘要:

INORGANICY CREMISTRY. Inorganie Chemistry. ii 236; Preparation of Active Hydrogen. Y. VENKATARMAIAH (J. Amer. Chem. &oc. 1923,45,261-288).-An active form of hydrogen which will react with cold sulphur to produce hydrogen sulphide may be produced by the continuous burning of oxygen in hydrogen by the surface combustion of hydrogen and oxygen on a platinum surface and by a high tension arc in hydrogen between silvcs electrodes. When gold or platinum electrodes were used in plme of silver electrodes in the last method no active hydrogen a,s tested by the non-formation of hydrogen sulphide wm obtained. The author considers that the failure in this case is due to the adsorption of the gas by the thin film of these metals which is deposited on the walls of the reaction vessel during the experiment.Success in all the experiments depends on the temperature being kept low. J. F. S . Ethyl Alcohol as a Stabiliser €or Hydrogen Peroxide. (hzME) LISIE~ICI-DRAGAN~S~ (Bul. SOC. China. R d n i a 1922 4 65-68).-Ethyl alcohol is a satisfactory stabiliser for hydrogen peroxide. Added in the proportion of 10% to hydrogen peroxide of 10 vols. strength a diminution of only about 0.3% was obsemed after four months with a sample stored in open glass bottles and exposed to sunlight and only 0.1% in closed coloured glass bottles. To effect the same stabilisation with “ perhydrol,” the addition of 30:/ of ethyl alcohol was necessary. The Magmeto-chemical Effect. IV. A. N. SCHTSCHUKAREV ( J . Buss. Phys. Chem. Soc. 1918,50,109-122).-Chlorine produced by the electrolysis of barium or cesium chlorides in a magnetic field disintegrates giving rise to positive particles having a mass of about 0.013 that of a hydrogen atom and to negative particles which are shown to be ordinary electrons. This decom sition is explained as being due to the effect of the magnetic field% the chlorine produced under conditions of changed valency.R. T. Reaction between Silver Perchlorate and Iodine Chlorine Tetra-oxide. M. GOMBERG ( J . Amer. Chem. Soc. 1923 45 398421).-An investigation of the action of iodine and bromine on dry silver perchlorate in anhydrous solvents has been carried out with the object of ascertaining whether a substance of the formula (ClO,) could be prepared. The reaction 2AgC1O4+I2= 2AgI+2(C104) --f (ClO,) is found to take place in ethereal solu- tion but in this case there is a very small amount of a labile iodine compound also formed which is assumed to be iodine tetra-oxide produced according to the equation C104+I -+ IO,+Cl.This iodine compound is very unatrtble and decomposes readily into iodine and oxygen so that it solution of pure chlorine tetra-oxide in ether is readily obtained. It was found adviwble in the pre. pamtion to use solutions not exceeding 0.1N. With solutions of this ooncentration the properties of tbe new oxide have been G. F. M.ii. 236 ABSTRACTS OF CHEMICAL PAPERS. investigated. The substance is colourless and is stable in ether solution. It does not volatilise in the ether vapour. It is probably bimolecular (C104)2. The chemical activity of the substance would indicate that there is a considerable dissociation into single mole- cules but this point has not been investigated.It is readily hydrolysed yielding ultimately perchloric acid as the only product but reasons are given for assuming that the primary course of the reaction with water is 2C10,+H20=HC10,+H0*C10,. It liberates iodine from iodides but not in equivalent amount. It reacts quantitatively with zinc and magnesium forming perchlorates ; with iron tin and copper forming salts of the metal of lower and higher valency. It acts slowly and incompletely on cadmium bismuth and silver. Ethereal solutions of anhydrous perchloric acid and ethyl perchlorate have been submitted to the tests which am chmacteristic of chlorine tetra-oxide and found to respond to them in a manner entirely different from chlorine tetra-oxide.J. F. S. Atomic Weight of Selenium. P. BRUYLANTS and J. DON- DEYNE (Bull. A c d . roy. Be@. 1922 [v] 8 387405).-A previous determination was made in 1912 (A. 1913 ii 500) and gave the figure 79.18. The weight of a normal litre of hydrogen selenide has been determined a t pressures of 1 0.6 and 0.3 atmosphere the three values being respectively 3.6721 3.65732 and 3.64407 g. The atomic weight of selenium is calculated making use in con- nexion with the compressibility values of the two methods recom- mended by Guye (A. 1919 ii 318) and taking the weight of a normal litre of oxygen as 1.4289 (Moles and Gonsalez A. 1921 ii 546). The difference between the new value of the atomic weight 79.37 and that previously obtained is due to three causes (a) The divergence of the compressibility between 0 and 1 atmo- sphere A,' is by Guye's method 0.01083 whilst the value of A,,' Calculated from direct measurements of pv at different pressures and using Berthelot's formula is 0.01302.Guye's method is pre- ferable owing to the high compressihility of hydrogen selenide. ( b ) The 1912 determinations of compressibility (from measurements of p ) give A,' 0*01191 the density figures giving A,' 0.01083. (c) In 1912 the local value of g was not known this difficulty being surmounted by actually determining the weight of a normal litre of oxygen. These three causes of difference all act in the same direction. The above figure (79.37) will therefore be subject to further correction when new data (for compressibility and weight of normal litre of hydrogen selenide) are available.The paper contains a very complete table of vapour pressure measurements from t-78*01" ( p 82.89 mm.) to t-20.77" ( p 1799-0 mm.). From these results the following constants are obtained b. p.-41*2"/760 mm. ; triple point at p 203.3 mm. t-65.9"; mole- cular latent heat of vaporisation at -41-2" L4.76. The boiling points of hydrogen selenide and carbon disulphide give a constant TJT2 ratio between pressures of 230 and 1550 mm. E. E. T.INORQAXIC CHEMISTRY. ii. 237 Catalysis in Homogeneous Gas Reactions (I) "be Catalysis of Formation of Nitrosyl Chloride by means of Bromine. A. KISS (Rec. trau. chirn. 1923 42 112-144).- The preparation of nitrosyl chloride by combination of nitrio oxide and chlorine in presence of bromine takes place with preliminary formation of nitrosyl bromide.Measurements of the velocity of reaction between nitrosyl bromide and chlorine were carried out at temperatures ranging from 0" to 100" and show the reaction to be a clean rapid gas reaction of the third order. It is accelerated by the presence of water vapour although water does not act as a catalyst in the reaction between nitric oxide and chlorine at 18". The formation of nitrosyl chloride either directly or through the intermediate stage of nitrosyl bromide is not affected by light ; the direct formation is stimulated by the catalytic effect of a rough surface. The reaction velocity is not affected by the presence of hydrogen chloride or carbon dioxide and if light is excluded both hydrogen and carbon monoxide are without effect.In the case of the reaction between nitrosyl bromide and chlorine no alteration is brought about by carbon dioxide. H. J. E. A Low Temperature Electrolyte. WORTH H. RODEBUSH and THEODORE 0. YNTEMA ( J . Amer. Chem. Soc. 1923 45 332- 337).-When nitric oxide and hydrogen chloride mixtures are submitted to the temperature of liquid air an intensely p-le coloured solid is produced. This solid melts to a purple liqmd which between the temperatures 120" K. and 130" K. has a specifk conductivity of more than ohms a value which is about the same as that of O.OlN-potassium chloride solution. Attempts to ascertain the composition of this substance were unsuccessful but it is shown that the vapour pressure of nitric oxide from the purple solid is not appreciably less than that of pure liquid nitric oxide. This indicates that the complex is an exceptionally unstable one.The range over which it exists is small being roughly between 120" K. and 130" K. It is suggested that the complex is of the form [NOH]+Cl- and that it is one of the type of compounds containing an odd number of electrons and therefore according to Lewis's hypothesis (A. 1916 ii 310) is highly coloured. Behaviour of Phosphoric Oxide towards Water. A Direct Method for the Preparation of Tetraphosphoric Acid. M. A. RAKUSIN and A. A. ARSEN~EV (Chem. Z@. 1923,47 195).- After the violent reaction resulting from the addition of phosphoric oxide to water and formation of orthophosphoric acid has subsided further quantities are gradually added until the amount reaches about 520% of the water present.After keeping for five days crystals of tetraphosphoric acid H6P4013 separate from the syrupy liquid. This acid has previously only been prepared in the farm of its salts. It melts at 34" and has d16 1.8886. The Solubility of Phosphoric Oxide in Ethyl and Methyl Alcohols. M. A. RAKUSIN and A. A. ARSEN~EV (Chem. Ztg. 1923 47 178). Phosphoric oxide dissolves readily to the extent J. F. S. G. F. M. 9'ii. 238 ABSTRACTS OF CHEMICAL PAPERS. Or 60% in ethyl and methyl alcohob with the dsvebpmeut af heat. Cansidembly greabr quantitiee of the oxide dissolve in the resulting li uids oxi Qontinbed stirring and heatin xip to 295 @I.in f&e w e &he cam of eth 1 alcohol giving a liquid of d15 1-6894. Them liquids with silver nitrate solution. Phosphurio oxide causes phenol menthol and similar sub&mces to dissolve in chloroform without apparently entefing into any reaction with them. If the solutions are left for several days and the chloroform is then removed by a current of dry air the phos- phoric oxide and the phenol are recovered unchanged. A. R. P. Studies in Hypophosphorous Acid. V. Its Reaction with Silver Nitrate. ALEC DUNCAN WTCHELL (T. 1923 123 629- Reducing Action of Arsenious Acid. MORITZ KGHN (bloncttsh. 1923 43 367-371).-Silver nitrate is complete1 reduced to metallic silver in ammoniacal solution by arsenious aci$ which is oxidised to arsenic acid. The reduction is.not affected by the addition of neutral salts such as sodium nitrate or sulphate but is hindered by ammonium sulphate which causes a decrease in the concentration of hydroxyl-ions.The reduction of cupric sulphate bye arsenious acid in presence of aqueous ammonia is not influenced by neutral salts such as potassium chloride or nitrate. o P methyl alclcahol giving a liquid of d15 854.37 and up fa 258 g. in mact acid aIt c9 du not boil on adding water or give B precipitate W). E. E. T. Phosphorescent Boric Acid. EKICH TIEDE and ALFRED RAGOSS (Ber. 1923 56 [B] 655-686 ; cf. Tiede A. 1921 ii 75 ; Tiede and Wulf€ A. 1922 ii 245).-It has been shown previously that intense hosphorescence is produced by the presence of certain otganic subLnces in partly dehydrated boric acid.It is how found that similar products can be derived from boric acid and fmm completely dehydrated boron trioxide. Products derived from boric acid are obtained by crystallising the acid from water or acetone containing a small amount of the desired organic substance e.g. terephthalic acid whereas those from boron trioxide are prepared by drying a mixture of hydrated boric acid and the required impurity over phosphoric oxide a t ZOO". Since boric acid readily becomes " infected " by the organic impurities present in the air it is necessary to work under particular conditions which are described in detail in the original. Phosphorescence is excited by exposure to the light of a mercury lamp or iron-carbon arc; it does not generally persist during more than two minutes the greatest diminution in intensity being observed during the h s t thirty seconds. The activating effect; of a large number of organic compoullds has been examined. Aliphatic compounds do not exert an appre- oiable effect unless they have become deoomposed to some extent.The preBence of an aromatic nucleus or condensed system appears to be necessary. The colour of the emitted light depends almostINORGANrC CI-IEMISTRY. if. 239 dntirely ou the nucleus which is present with increasing complexity of which it is displaced towards the red. The presence of substi- tuents greatly influences the intcnsity but not the colour of the emitted light. Two substituents present simultaneously have their maximum action when in the para-position to one another their minimum effect in the ortho-position.Saturated side chains hydroxyl and sulphonyl groups are feebly activating the amino- group is inactive by reatson of salt formation and carboxyl greatly increases. bhe brightness particularly in the presence of a second carboxyl or of oiie of the feebly activating groups. CoIoured sub- stances seldom excite emission. Chlorinated compound8 cause an extraordinary shortening of the period of phosphorescence. The presence of bromine iodine or the nitro-group inhibits phos- phorescence. Both physical and chemical examinations lead to the conclusion that the organic molecule is to be regarded as causative of the luminescence and that the boric acid provides the necessary physical conditions. The presence of compounds derived from boric acid and the organic component is in many cases possible and probable but these substances e.g.triphenyl borate and tri- P-naphthyl borate are not in themselves phosphorescent. The physical characteristics of boric acid phosphors have been described in detail by Tomasohek (A. 1922 ii 763). It is however pointed out that the absorption spectra of organic subetanoes in boric acid are similar to those in alcohol and that phosphorescence of the boric acid phosphors is excited by rays of the same length as those absorbed ; the emission spectra in boric acid and in alcohol are compared. H. W. The Hydrates of ICrypton and Argon. R. DE PORCRAND (Compt. rend. 1923 176 355-358).-The dissociation pressures of the hydrate of krypton as measured at various temperatures are 14.5 atmos.at 0" 23.5 atmos. a t 4-8" 38.7 atmos. at 10.3" and 47-5 atmos. a t 12.5". At 13" the hydrate could not be obtained even with a pressure of 100 atmos. The critical tem- perature of decomposition of the hydrate is thus between 12.5" and 13". From the above data the formula of the hydrate is calculated as being Kr,SH,O. A redetermination of Villard's value of the dissociation pressure of argon hydrate (A. 1897 ii 31) gives the value as 98.5 atmos. at 0-Z" Villard's value thus being too high. From this and the value 210 atmos. a t 8" the formula for this hydrate is calculated Perchlorates of the Alkali and Alkaline-earth Metals and Ammonium. Their Solubilities in Water and Other Solvents. H. H. WILLARD and G. FREDERICK SMITII (J. Amer. CAem. Soc.1933 45 286--297).-The perchlorates of calcium strontium barium magnesium lithium sodium potassium rubidium cesium and ammonium have been prepared and investigated. The method of preparation in all cases but that of ammonium consists in evaporating the chloride or nitrate to dryness with an excess as being Ar,5&H20. w. G. 9*-2ii. 240 ABSTRACTS OF CHEMICAL PAF'ERS. of perchloric acid. The ammonium salt was prepared by leading ammonia into a dilute solution of perchloric acid. The solubility of the salts has been determined a t 25" in water methyl alcohol ethyl alcohol n-propyl alcohol rt-butyl alcohol isobutyl alcohol acetone ethyl acetate and ethyl ether. The density of the solvents and saturated solutions at 25" and the solubility in each solvent in grams per 100 C.C.and per 100 g. of solvent and solution and in g.-mob. per 100 C.C. and per 100 g. of solvent and solution are recorded in a number of tables. J. F. S . Inorganic Luminescence Phenomena. V. Preparation and Properties of Phosphorescent Sulphides of Sodium and Rubidium. ERICH TIEDE and HERBERT REINICKE (Ber. 1923 56 [B] 666-674).-In continuation of previous work (Tiede and Richter A. 1922 ii 215) the sodium and rubidium sulphide phosphors have been examined. As in the case of the phosphors of the sulphides of the alkaline-earth metals the presence of a trace of a heavy metal appears necessary for the development of phosphorescence. Attempts to prepare sodium sulphide by the direct union of sulphur vapour with sodium by the use of carbon disulphide as in the caae of magnesium sulphide (Zoc.cit.) from the azide or by the reduction of sodium sulphate with hydrogen did not yield a sufficienli)y pure product. Success was however obtained by dissolving sodium hydroxide in absolute alcohol at the atmospheric temperature dividing the filtered solution into two nearly equal portions saturating the smaller portion with hydrogen sulphide uniting it with the second portion and crystallising sodium sulphide pentahydrate from the mixture as rapidly as possible. The product is dried in small portions over phosphoric oxide a t 55" and is subsequently heated a t 600-650" in a graphite boat in a current of pure dry nitrogen. The material prepared in this manner contains 95% of sodium sulphide the remainder being composed of sodium hydroxide and a little sodium oxide the presence of which is regarded as advantageous.When excited by the light of the mercury lamp it shows a faint ill-defined phosphorescence whereas specimens prepared from the technical sulphide are either non-phosphorescent or more frequently emit a relatively bright green light. The active agent in causing the sulphide to phos- phoresce is iron which exerts its maximal action when present in traces much smaller than those generally necessary to produce similar effects ; the introduction of suitable traces of the metal is effected by the addition of ferric chloride to the original sodium hydroxide solution. The induced phosphorescence is green whereas that due to copper is pale yellow. The emission spectrum of sodium sulphide iron phosphor exhibits a narrow green band a t 505- 560 pp whereas that of the corresponding copper phosphor has a broad band a t 510-650 pp with a maximum a t about 550 pp.It is remarkable that iron should be the excitant with sodium sulphide phosphors since it has been found to be inactive with the sulphides of the second group a t the concentrations examinedINORGANIC CHEMISTRY. ii. 241 previously. New experiments on the action of much smaller amounts of iron on highly purified zinc sulphide indicate that the metal is active under these conditions. Attempts to apply the method wed in the preparation of sodium sulphide to that of the sulphides of lithium potassium or rubidium did not meet with success. Phosphorescent mixtures of rubidium sulphide and sulphate are prepared by the reduction of rubidium sulphate in a graphite boat by hydrogen a t about 650".The emitted light is bluish-red. The preparations decompose very readily. The amount of material available was insufficient to permit the certain identification of the exciting agent which rtppeara to be effective a t very small concentrations. The Action of Alcohol on the Sulphates of Ammonium. HORACE BARRATT DUNNICLIFF (T. 1923 123 476-484). Reaction between Selenium and Silver Nitrate in Aqueous Solution. F. GARELLI and A. ANGELETTI (Atti R. A d . Lincei 1922 [v] 31 ii 440445).-The authors are unable to confirm Guyot's statement (this Journal 1871 660) that from neutral or acid solutions of salts of the metals selenium dissolved in carbon disulphide precipitates only silver as silver selenide.In aqueous solutions the silver may be precipitated completely if excess of selenium is used and the liquid is boiled the reaction corresponding with the equation 4AgN03+3Se+3H,0=2Ag,Se+H,Se0,+ 4HN03 (cf. Senderens A. 1887 331). F'rom a neutral solution containing silver lead and mercurous or mercuric nitrate the silver may be precipitated completely in this way the amount o€ selenium added being a t least twice that of the silver in solution and the liquid being boiled for fiffeen minutes and filtered when cold. The precipitate is heated with nitric acid and the silver estimated as chloride. Before precipitating selenium from a nitric-hydrochloric acid solution of selenious acid Treadwell recommends that the liquid be evaporated to dryness to expel excess of nitric acid.This p ~ - cedure however involves loss of selenium owing to the volatihty of selenious acid The addition of alkali chlorides as suggested by Fresenius does not entirely overcome this diEculty. If how- ever oxidation is effected by nitric acid alone this may be elimin- ated by evaporation and the residue then taken up in hydrochloric acid without appreciable loss of selenium. G. WEISSENBEROER (Kdloid Z. 1923 32 181-192).-The hydration of anhydrite has been investigated by following the hardening of the material in the presence of water. It is found that the rate of hydration is accelerated by the presence of ferrous sulphate and other catalysts. The rate of hydration also depends on the size of the particles.When the size of the particles is greater than a definite maximum value anhydrite is not hydrated but when the particles are very small water is taken up readily. The following substances are shown to be definite compounds involved in the process of the H. W. T. H. P. Hydration of Anhydrite.ii. 242 ABSTR-4CTS OF CHEMICAI PAPERS. hydration of anhydrife gypsum CaS0,,2HZ0 ; soluble ctnhydrite CaSO ; anhydrite (CeSO,) ; and the hemihydrate 2CaS0,,H20. J. F. S. Sus ensions of Particles of Barium Sulphate of Various Sizes %xamined by Transmitted and Reflected Light. A A ~ E W. OWE (Kolloid Z. 1923 32 73-77).-Suspensions of barium sulphate in glycerol mixtures of alcohol and glycerol and water and glycerol have been examined by both reflected and transmitted light.It is shown that the degree of turbidity as determined nephelo- metrically and also by transmitted light is dependent not only on the size of the particles but also on the composition of the dispersion medium. This dependence is due chiefly to changes of the index of refraction of the solvent and to the changes in the form of the combined particles. The degree of turbidity obtained nephelometrically in pure glycerol reaches a maximum value with particles somewhat less than 200pp. In aqueous glycerol the maximum is probably displaced toward larger particles. The degree of turbidity as obtained by means of transmitted light increases steadily with increasing size of particles a t least up to 1oOOpp. The maximum which must of necessity exist lies prob- ably in the region of particles having a size of several thousand pp.[A Simple Method for the Preparation of Highly Phos- phorescent Zinc Sulphide. ] ERICH TIEDE and ARTHUR SCHLEEDE (Ber. 1923 56 [BJ 6’74-675).-1n a recent com- mqnication (this vol. ii 75) Schmidt has described the preparation of highly phosphorescent zinc sulphide and has been drawn to the conclusion that its phosphorescence is inhibited by the presence of metals which yield black sulphides. ThiEl observation is directly opposed to the observations of Tomaschek (A 1921 ii 588). It is pointed out that Schmidt’s procedure does not give any guarantee that the necessary amounts of copper are not intro- duced with the many salts employed and that it iEl therefore quite possible that subsequent additions of the element may cause its concentration to exceed the narrow limits required for optimal effect.A gpecific action in Schmidt’s method caanot be attributed to the chlorides of the alkaline-earth metals and magnesium since they can be replaced by the alkali chloride; the chloride is the The Action of Water and Steam under Pressure on some Soda-Lime-Silicate Glasses. E”. W. HODEIN and W. E 8. TURNER (J. SOC. Glass Tech. 1922 6 291-308).-Four soda-lime- silicate glasses having the approximate compositions 6SiO2,0-3Ca0 1*7Na20 6Si0,,0-7Ca0,1*3Na,0 6Si0,,0~8Ca0,1*2Na,O and 6SiO,,CaO,Na,O were subjected to the action of water and steam a t presswes varying from 2 to 25 atmospheres above normal. The action af steam on these glasses is considerable being greater than that of water at the higher pressures in the case of the glass hatag the J.F. S. important component. R w.SNOWAN1[0 CHEMISTRY. ii. 243 low& lime content. Corrosion diminishes a8 the amount of b e is increased and the arnomt of sodium oxide deeretassd T4e glass with fhe highest h e content was unattacked. by steam or water in three hours at 2 fo 4 atmospheres. The incrwhtion formed 8s a reault of corrosion was harder the greater &he lime content; 8 gelatinous layer was formed beneath the incrustation on the glaces containing only 093Ca0 at 15 atm. preasure. Sirwe the loss in weight recorded was less than the tota.1 alkali found in the water it is clear that the glass absorbs a considerable quantity of water. The character of the corrosion which clearly brings out pouring and moulding lines is influenced markedly by the condition of the surfwe.The autoclave test is considered too severe for sodaAmesilicate glasses which are only required to resist the action of boiling water. The Crystal Structure of the Alums. RALPH W. G. WYUKOFF (Arne?. J . Sci. 1923 5 209-217).-Studies of the h u e and ~peu- trum photographs of potassium and ammonium aluminium duma were undertaken with a view to determine the space grouping of the alums. The hemihedral nature of the crystal structure is evident a t once from the photogmphs and from a study of the reflections fI!om planes with one index zero it is shown that the corresponding space group is The rather than Th2. mere me four molecules with the composition R'R"'(SO,) 12H20 in the unit cell and in this space group the four sulphate oqgen afoms cannot be exactly alike.Three of these atoms will be similarly placed but the fourth will be different from the other three. The twelve water molecules fall in two groups of six each. The positions of the K or N and the Al and S atoms are given but no attempt has been made to locate those atoms having variable parametem. The hydrogen atoms of the ammonium group cannot be arranged in a chemically plausible radicle which will possess a symmetry in keeping with the rest of the crystal. The spectrographic observ- ations show that unaided spectrometer measurements me in- sufficient for the determination of crystal structure. Some Properties of Manganese Dioxide. A. DE RIMP- 'IIWNE (BUZZ. A d . roy. BeEg.1922 [v] 8 71-75).-Mangassae dioxide is slowly reduced by hydrogen at room femperafww to give a product which slowly re-oxidises in the air. The dioxide rapidly absorbs hydrogen sulphide from a mixture of a with h drogen man anese sulphides being formed. The absorption in presence of moisture this gas is readily absorbed by manganese dioxide. E. E. T. Cementation by means of Boron. N. PARRAVANO and C. MAZZETTI (Atti 8. h m d . fincei 1922 [v] 31 ii 42-61.- When steel is heated at 900" in an atmosphere of boron chloride and hydrogen it becomes matad wi6h tb layer of very hesd alloy rich in boron and capble of cutting glass. Niekel also und om3 oemenbtion under them conditions. E. €I. R. W. E. G. is muc I more rapid f % an with dry hydrogen sulphide alone although T.H. T .ii. 244 ABSTRACl'S OF CHEMICAL PAPERS. The Constitutional Diagram of the Iron-Carbon-Tungsten System. SIUEAEI OZAWA (Sci. Rep. T6hOku Imp. Univ. 1922 11 333-36O).-There is only one compound in the iron-tungsten system' viz. Fe,W. In the iron-carbon-tungsten system this com- pound and iron carbide are mutually soluble a t certain concentrations and the resulting solution splits up with the simulhneous separation of tungsten carbide WC. A ternary eutectic containing 15% W 306% C and 81.4% Fe is formed and melts a t 1066" (cf. J.S.C.I. 1923 April). A. R. P. Constitution of Ferric Oxide Hydrosol from Measurements of the Chlorine and Hydrogen Activities. FREDERICK L. BROWNE ( J . Amer. Chem. Xoc. 1923 45 297-311).-Using a calomel electrode as comparison electrode the chloride-ion activity has been measured in solutions of ferric chloride and in ferric oxide sols of various concentrations and widely varying purity.A method is described for using the hydrogen electrode in the presence of dilute solutions of ferric chloride and this has been used for the measurement of the hydrogen-ion ativity in ferric oxide sols. Ferric oxide sols having a total iron concentration of about 0-5 g. equiv. per litre and a purity of less than 14 (purity=g. equiv. Fe/g. equiv. C1) contain ferric chloride and hydrochloric acid in the aqueous phase and the dispersed ferric oxide cazries considerable amounts of adsorbed ferric chloride and hydrochloric acid. The adsorption of ferric ion and hydrogen-ion is greater than that of chloride-ion thus giving the dispersed phase a positive charge.At higher purities the adsorption of ferric-ion and hydrogen-ion is complete and the aqueous phase contains only chloride-ion the " kations " for which are the dispersed particles. At lower concentration of total iron ferric-ion and hydrogen-ion disappear from the aqueous phase at somewhat lower purity and at higher concentrations a t high purity. The effect of dextrose on the freezing point of ferric oxide sol shows that practically all the water present in the sol acts as solvent for substances dissolved in the sol. Tables are given showing the concentrations of chloride-ion and its distribution between ferric chloride and hydrochloric acid in sols of widely varying purity and concentration as well as the total chloride compounds adsorbed by the ferric oxide.The Higher Oxide of Nickel. OWEN RHYS HOWELL (T. The System Chromium Trioxide-Nitric Acid-Water. STANLEY AUUUSTUS MUMPORD md LIONEL FELIX GILBERT (T 1923,123 471475). The Adsorption of Stannous Chloride by Stannic Acid. GEORGE ERNEST COLLINS and JOHN KERFOOT WOOD (T. 1923,123 462456). C. J. SMITHELLS and F. S. GOUCECER (Nature 1923 111 397; cf Scott T. 1923 123 311).-Careful chemical and X-ray analysis of the black sand from J. F. S. 1923,123 669-676). Constitution of Black Maketu Sand.INORGtLLNY.0 CHEMISTRY. 2. 245 Maketu N.Z. confirms Bohr's conclusion that no new element is present. A residue insoluble in sulphuric acid and fused sodium hydrogen sulphate was attacked by potassium hydrogen sulphate and was found to contain iron and aluminium in equal parts (cf.Scott T. 1923,123 881). Studies on Metal Hydrides. The Electrolytic Formation of Stibine in Sulphuric Acid and in Sodium Hydroxide Solution. HENRY JULIUS SALOMON SAND EDWARD JOSEPH WEEKS and STANLEY WESON WORRELL (T. 1923 123 456- 470). Perchlorates of Bismuth and Antimony. FR. RCHTER and ERNST JENNY (Helv. Chim. Acta 1923 6 225-231).-The method described by Muir (this Journal 1876 i 878) for the preparation of a perchlorate of bismuth which is reproduced in the text-books is attended with serious danger of explosion especially when bismuth powder is dissolved in 70% perchloric acid. By dissolving bismuth powder very carefully in 40% per- chloric acid a solution was obtained similar to that obtained by dissolving bismuth oxide in 70% acid.When this solution is evaporated in a vacuum desiccator bismuth perchlorate Bi( C1O4),,5H2O is obtained in small hexagonal tables which rapidly change in moist air into a bismuthyl salt. When an aqueous solution of the normal perchlorate is evaporated slowly bismuthyl p e r W & trihydrute Bi0*C10,,3H20 is obtained in aggregates of doubly refracting prismatic needles. It is very unstable and has a great tendency to change even in the mother-liquor into the momhphzte BiO*ClO,,H,O. This is the most stable salt and separates from all solutions not too concentrated with respect to perchloric acid. It forms very hygroscopic rhombohedra1 crystals. The anhydrous salt obtained by drying the monohydrate a t 80-100" is a white powder Wering from that described by Muir in being completely soluble in water.When concentrated perchloric acid is saturated with bismuth oxide a mass of crystals separates the composition of which approximates to OH*Bi(ClO,),,%O. A perchlorate of antimony is obtained by dissolving antimony oxide in ten times its weight of 70% hot perchloric acid. Too high a temperature causes oxidation to antimonic wid. On cooling antimony1 perchlorate separates in small needles having the composition Sb0*C104,2H20. Some preparations were anhydrous. E. H. R. Formation of Colloidal Gold Solutions by Means of Electrical Spark Discharges. W. NAUMOV (Rolbid Z. 1923 32 95-lOO).-During a repetition of Donau's experiments on the preparation of colloidal solutions of gold (A. 1915 ii 352) it was found that two types of discharge have to be differentiated. In the first type where the discharge occurs between two dry electrodes hydrosols are produced because new reducing gases are produced in the vapour above the solution ; these gases dissolve A. A. E.ii. 246 ABSTRACTS OF CHEMXJAL PAPERS. in the solution and reduce the gold chloride. In the second typesn the discharge occum between one dry electrode and the solution or between two moist electrodes whereby hydrogen peroxide is produced in the solution which reduces the gold chloride. In the portion of the solution which serves as negative pole coarse violet or blue sols or suspensions are produced whilst the positive portion of the solution contains more or less highly disperse red hydrosols. In both positive and negative parts of the solution acid hydrosols are produced. The polarity of the solution exercises a great infiuence on the amount of acid in these solutions which in its turn is determinative of the character of the sol and of its properties. The addition of a solution containing nuclei to the gold chloride solution causes the formation of the sol to take place more easily reduces the time required for reduction and produces bright red sols. J. I?. S.

ISSN:0368-1769    

DOI:10.1039/CA9232405235

出版商:RSC    

年代:1923

数据来源: RSC

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ii. 246 ABSTRACTS OF CHEMXJAL PAPERS. Mineralogic a1 Cbemis try. Some New Derivatives of Bituminous Coal. ARCHIBALD R. PEARSON ( J . 8oc. Chem. Id. 1923 42 68-72~).-The term “ ultrahumin ” is suggested for the constituents of coal derived from humified vegetable proteins and celluloses as distinct from resins waxes etc. The preparation of a-(pyridine insoluble) and g- and 7-(pyridine soluble) ultrahumins is described. Oxahumins produoed by oxidation of ultrahumins with fuming sulphuric acid contain more than 90% of the nitrogen content of the ultrahumins and when brominated take up about one-third of their weight of bromine forming a series of compounds of approximately con- stant composition. The brominated products form negative sols in water or alcohol. It is concluded that ultrahumins contain a very stable molecular nucleus including the nitrogen in heterocylic combination.The oxidised nucleus is retained a t least in part in oxahumins brominated to saturation. The Deposits of Potassium Chloride at Solikamsk. N. S. KWRNAKOV K. F BELOGLAZOV and M. K. SCHMATKO ( J . Raw. Phyt?. Chem. Soc. 1918 50 122-130).-Samples of rock salt and of aylvine from Solikamsk are described and analysed. The potassium chloride in the former is from 0.26% to 11.9% and in the latter up to 63*2%. The sylvine is very similar in content and appearance to that found at Stasfurt or Kalusz. Varying small percentages of potassium chloride are found to be present in the mother-liquors from salt works in different parts of Russia. R. T. BMxgaatellite from Monte Ramazzo (Liguria).ETTORE ARTINI (Atti R. A&. Lincei 1922 [v] 31 ii 491-496).-Analysis of brugnatellite from Monte Ramazzo gives the following results &O. CO,. Fe,O,. MnO. CaO. MgO. residue. Total J. S. G. T. *o’. 3243 8.W 16.12 1-17 1.19 39.13 0.99 99.62Wben cow6ed for the small proportion of elstiranmus- mlcium Garborrate pment them numbers are in good agreement with those obtained fsr brugnatellite from Val Malenco (A. 1909 ii 247) and with the formula proposed by the author the alight excw of ferric oxide probably existing in the free state aa a product of alteration. The resulfs also render evident the distinction between this mineral and pyroaurite this being borne out by physid differences (cf. Foshag A. 1920 ii 765). The brucite from which this brugnatellite is derived by epigenesis contains H,O 30.37; FeO 1-37 ; MnO 0.38 ; MgO 67.96 ; insoluble residue 0.10 ; total 100*18.If these numbers are corrected for the insoluble matter and the FeO and MnO are replaced by MgO they correspond closely with the composition of Mg( OH),. Chemical and Optical Study of the Axinite of Prali (Valle della Germanasca). E. GRILL (Atti R. Accad. L i w i 1922 [vJ 31 ii 621-524).-This axinite d 3.314 occurring as a pale violet- red vein in a mass of erratic gneiss has the composition SiOo. TiO,. Also1. Fe,Os. FeO. MnO. I&&. 41.26 nil %% 18.74 2.02 6.11 4.43 CaO. HSO (- 110'). Ha0 (+ 110'). I?. Total. 19.52 0-46 1.25 tram 100.24 T. H. P. These figures correspond with the formula H20,8( &,Fe,Mn,Mg)0,3( Al,Fe),0,,B20 lOSiO which contains 1 mol. of water less than that established by Whit- field (A. 1888 347) and is not reducible to that of an orthosSca@ (of. Ford A. 1903 ii 436). T. H P.

ISSN:0368-1769    

DOI:10.1039/CA9232405246

出版商:RSC    

年代:1923

数据来源: RSC

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An a1 y t ie a 1 C h e mi s t r y. ii. 2-47 Spectroscopic Methods of Analflical Chemistry. C. AUER- WELSBACH (Monahh. 1923 43,387-403).-A survey of the actual experimental methods employed by the author in carrying out analyses with the aid of spark spectra. Photographs of the apparatus used and a chart showing the lines in the spark speatra of a large number of elements are appended. The effect of the presence of alkalis zinc oxide etc. on the spark spectrum of platinum is discussed. The Application of the Quinhydrone instead of the Hydro- gen Electrode in the Potentiometric Measurement of Aciaty I. M. KOLTHOFF (Rec. tmw chim. 1923,42 186-198; cf. Biilmann A. 1921 ii 372).-The quinhydrone electrode gives excellent results in the titration of acid solutions and may replace the hydrogen eleotrode for that purpose.It is however unsuitable for use in alkaline solution if air is not excluded owing to $49 oxidGtioa of @ portion Qf the quinhydrone to acid E. E. T. H. J. $,ii. 248 ABSTRACTS OF CHEMICAL PAPERS. -ation of Blood Alkalmz 'ts. HANS GOIXWITZER (Bio- chem. Z. 1923 134 590-60O).-The exact gas analysis method of Barcroft has been compared with the titration methods of Rohanyi (Munch. med. Woch. 1920 67 51) and of Van Slyke (A. 1919 ii 298). The Van Slyke method yields too high and the Rohanyi method too low results. The gas analysis method is much to be preferred to either of the other two. The Stability of an O*OlN-Sodium Oxalate Solution. EDWARD S . HOPIIINS (Ind. Eng. Chem. 1923 15 149).-The addition of 100 C.C. of 1 4-sulphuric acid per litre to sodium oxalate solution prevents its deterioration for a t least two months even when the solution is stored in clear glass bottles exposed to daylight.G. I?. M. The Colorimetric Estimation of Water in Absolute Alcohol. I. M. KOLTHOFF (Phurm. Weekblad 1923 60 227-231).-The sensitiveness of methyl-orange to acids is much less in alcohol solutions than in water solutions diminishing to a minimum for afcohol of about 90% volume strength and increasing again for alcohols between 90 and lOOyo. The sensitiveness is determined by the volume of alcoholic hydrogen chloride (N/10) required to produce a standard tint with 0.1 C.C. saturated methyl-orange solution in 25 C.C. of the alcohol under examination. A suitable standard is obtained by adding 0.4 C.G. of N/100-hydrochloric acid solution to 0.1 C.C.of saturated methyl-orange solution in 25 C.C. of water; a table is given showing for various alcohols between 95 and 99.7 yi by volume the sensitiveness expressed in quantities of acid required a t 15" to produce the standard tint compared with the quantity used in water the figure rising from 5.2 for 99.7% alcohol to 126 for 95% alcohol compared with 1 for water. The influence of temperature is important a rise causing the colour to change to the alkaline side in water but having the opposite effect in alcohol. W. 0. K. Figures for temperature correction are given. s. I. L. Detection of Chlorine Bromine Iodine and Silver in a Mixture of Silver Halides. H. SCHMALFUSS (2. anal. Chem. 1923 62 [6] 229-231).-Silver chloride is extracted from the mixture of silver halides by shaking with a 15% solution of am- monium hydrogen carbonate.The presence of the chloride is confirmed by reprecipitation as silver bromide with potassium bromide. The residue is shaken with hydrogen sulphide solution and the silver precipitated as sulphide collected dissolved in nitric acid and confirmed by precipitation as chloride with hydro- chloric acid. Half the filtrate after the removal of the silver sulphide is treated with carbon disulphide and sodium nitrite and concentrated nitric acid added drop by drop. A violet color- ation in the carbon disulphide indicates iodine. The remaining half of the filtrate is treated with carbon disulphide and chlorine water ; after the iodine has been oxidised to iodic acid any bromine liberated produces a brown coloration in the carbon disulphide.ANALYTICAL CHEMISTRY.ii. 249 Alternatively the liquor from the first half after the removal of the iodine may be decanted off more carbon disulphide added and the bromine liberated with chlorine water. Apparatus for the Estimation of Halogens in Organic Compounds. K. RUBKE (2. angew Chem. 1923 36 156- 158; cf. Voigt A. 1923 ii 34).-The halogen compound is dissolved in benzaldehyde or in the case of liquids of high b. p. and of solids in a mixture of benzaldehyde and alcohol and the solution burnt in a lamp of about 20 C.C. capacity provided with an asbestos thread as wick. The lamp is surrounded by a glms chimney and the products of combustion pass through two U-tubes containing glass beads. In each U-tube 25 C.C.of N/50-potassium hy.droxide are placed to absorb the halogen acid produced in the combustion; this is ultimately washed out through taps a t the bottom and titrated with standard silver nitrate. Halogen-free air for the combustion drawn from outside the laboratory by means of a water-pump passes through a sulphuric acid drier and enters the combustion chimney through a glass tube in which the lamp is loosely held. The current of air should be about 1 litre per minute. In the case of chlorine compounds the whole of the hydrogen chloride is absorbed in the first U-tube. Hydrogen bromide however is not so readily absorbed and part of it is found in the second U-tube. Whilst the method of Voigt (cf. above) is valuable for rapid routine analyses the present variation is to be preferred where the time involved is of secondary import- ance.Further oxy-hydrogen explosions which can occur if due precautions are not taken in Voigt’s method are impossible in the above. Full working details and a sketch of the apparatus are given. W. T. I(. B. The Titration of Bleaching Powder. I. M. KOLTHOFX (Phurm. Weekblad 1923 60 241-.248).-Bunsen’s iodine titration in acid solution gives higher results than other methods; this is not due to the presence of chlorate but to chlorite formed when the solution or the damp solid is kept. Suitable conditions for the titration are given. Penot’s direct titration with arsenite and Pontius’s iodide method give accurate results for the hypochlorite content; the best conditions are given.In the latter petrol is suggested as an indicator instead of starch the first trace of free iodine forming a violet solution in the organic liquid on shaking. s. I. L. J. B. F. The Detection of Fluorine in Inorganic Fluorides. H. TER MEULEN (Chem. Weefiblad 1923 20 59).-In presence of borates the etching test gives no result owing to the formation of boron fluoride. If the gas is passed into water a cloud is formed which is seen under a lens to consist of fine crystals. Limit of Sensitiveness of the Acidification Reaction for Thiosulphates. 0. HACKL (Chem. 2@. 1923 47 174).-The limit of sensitiveness of the reaction for the detection of thio- sulphates by the precipitation of sulphur on acidification lies s. I. L.ii.250 ABS'l!R,ACYJ!S OR' CHEMIUAL PAPERS. between ~b content of 0-1 and 0-05 mg. of S,O per C.C. With the latter concentration no cloudiness whatever appears even on boiling or on long keeping and even with the former concentration and up to 1 mg. of S,03 per C.C. no immediate separation of sulphur occm in the cold and only after some minutes a t the boiling temperature. G. F. M. The Reaction of Silver Nitrate with Thiosulphate and its Sensitiveness 0. HACKL (Chem. Ztg. 1923 47 210).-The production of a yellow to brown colour when very dilute solutions of a thiosulphate are treated with silver nitrate is a very delicate iwaution &s 0.1 mg. of S,03 can thereby be detected in 100 C.C. of water whereas the acid test (formation of a white sulphur cloud on aoidifimtion) will detect 0-1 mg.in 1 C.C. only. General Method for the Detection of Volatile Acids. G. KARAQQLBNOV (2. anal. Chem. 1923 '62 217-222).-The salt solution is mixed in a flask wi6h 2N-acetic acid and a current of an indifferent gas such as air or hydrogen drawn through the solution. The gas is then led through tubes containing reagents sensitive to the acids concerned. The method is applicable to the following volatile acids hydrogen cyanide hydrogen sulphide nitrous acid sulphurous acid hypochlorous acid and carbonic acid the detection reagents being silver nitrate lead acetate diphen ylamine dilute starch -iodide solution indigo - s olu tion and bazium hydroxide respectively. Thiosulphuric acid is decom- posed by concentrated acetic acid with the precipitation of sulphur but in dilute acid no decomposition takes place. Elerro- and ferri.cyanic acids only decompose on long keeping. The remaining acids under these conditions are non-volatile. To detect sulplritc in presence of thiosulphate acetic acid is added of such iz strength that no sulphur is precipitated and the issuing gas passed through starch-iodide solution. To test for thiosulphite To a portion of the clear solution from the flask sulphuric acid is added ; a precipitation of aulphur indicates thiosulphate. If sulphide is also present the sdphide is precipitated from neutral solution by zinc chloride the atrate tested as above and the precipitate tested separately. Nitrite in presence of nitrate and chlorate hypochlorite in mixtures of hypochlorite chlorate and perchlorate cyanide in presence of chloride bromide ferro- and ferri-cyanides can be readily detected s h e the remaining acids in each case are not volatile under thc conditiom of the experiment.To detect two or more volatile acidsin the same mixture the gas is passed through the reagents in series Thus (a) for cyanide and sulphite it is passed successively through (i) a nitric acid solution of silver nitrate (ii) starch-iodide solution. (b) For sulphide and cyanide through (i) an acetic acid solution of lead acetate (ii) nitric acid solution of silver nitrate. (c) For sulphite cyanide and carbonate through (i) a nitric acid solution of silver nitrate (ii) a weak solution of staroh-iodide to detect sulphite (iii) concentrated iodine solution to retain sulphite (iv) barium hydroxide solution.(d) For cyanide sulphite sulphide thiosulphate and carbonate zinc chloride is added to a neutral solu- A. R. P.ANdLyTlolLtr CHEMISTRY. ii. 261 tion and the sulphide cyanide and carbonate precipitated and filtered off. The filtrate end precipitate are then examined separately ag above. As a preliminary experiment in order to determine whether any of the volatile acids are present the gas is passed separately through reagent tubes containing (i) a nitric acid solution of silver nitrate (ii) barium hydroxide solution (iii) starch-iodide solution. A turbidity indicates in (i) cyanide sulphide or hypochlorite in (ii) sulphite or carbonate; a blue coloration in (iii) indicates hypochlorite or nitrite. The volatile acids included in this scheme form an analytical group.Detection of Nitrogen in Mineral and Organic Substances by Microchemical Methods. AL. IONESCU and C. HriRqov~scu (Bul. Sm. Chim. R d n i a 1922 4 61-65).-The formation of yellow crystals of ammonium picrate of characteristic appearance when even small traoes of ammonia vapour are allowed to impinge on e drop of picromslonic reagent (a saturated solution of picric acid in ethyl malonake) or of an alcoholic solution of picric acid containing 5% of glycerol on a microscope slide may be used as a delicate specific test for ammonia nitrogen. With the picromalonic reagent tiny quadratic crystals are formed whilst with the alcoholio picric acid larger crystals in the form of more or less elongated yellow prisms are obtained.The latter reagent is the more sensitive owing to the evaporation of the alcohol. The ammonia is generated by heating the substance to be tested with sodium hydroxide solution if inorganic or with soda-lime if organic. Volatile axnines do not give the reaction. G. E. F. LUNDEIL and J. I. HOFFMBN (Ind. Eng. Chern. 1923 15 171-173).-Deta& are given of the application of the methods described in the fist part of this paper (this vol. ii 85) to the estimation of phosphorus in metallurgical products such as iron plain carbon steel alloy steel and bronze. The reduction method is slightly more trustworthy with solutions which do not contain interfering elements than the alkali- metrio method but the advantage does not outweigh its hconveni- ence and probably vanishes with phosphomolybdate obtained in the presence of such reducible substances rn titanium amenic or vanadium.The alkalimetric method yields under severe aon- ditions values sufficiently acourate for technical purposes provided attention is paid to the temperature at which precipitation is effected. The direct precipitation of phosphorus as phospho- molybdate in bronze assays has not hitherto been recommended but by following the method here described provided a clear solu- tion can be obtained in the amount of mixed nitric and hydrochlorio acids specified better recovery of the phosphorus has actually been obtained than by the widely-used Oettel method. 1-3 G. of the bronze are dissolved in a mixture of 15 C.C. of nitric acid and 6 C.C. of hydrochloric acid 15 C.O.of water are added and after digesting at 80" for ten minutes and diluting to 50 c.c. 100 O.C. of the molybdate reagent are added and the mixture is kept for four to six how. The precipitate is then collected dissolved in 20 C.C. of ammonia J. B. F. G. I?. M. Estimation of Phosphorus.ii. 252 ABSTRACTS OF CREMICAL PAPERS. containing 2 g. of citric acid and the ammoniacal solution treated aa previously described (la. cit.). Tungsten steel must also .be dissolved in a nitro-hydrochloric acid mixture. Estimation of Phosphorus in Vanadium Ores. F. W. KRLESEL (Chem. Ztg. 1923 47 177-178).-Precipitation of phos- phoric acid in the presence of relatively large amounts of vanadic acid by means of ammonium molybdate yields an orange-brown precipitate containing much vanadic acid.Treadwell's modification involving reduction of the vanadium to vanadyl sulphate also gives high results. Satisfactory results may be obtained by removing the vanadium as vanadyl ferrocyanide after first effecting a concentration and partial separation of the phosphoric acid by boiling the solution with nitric acid and tin. The precipitate contains all the phosphorus and some vanadium; it is fused with potctssium cyanide to remove tin and arsenic and the solution of the fused mass is boiled with hydrochloric acid to expel hydro- cyanic acid then with potassium ferrocyanide to precipitate the remaining vanadium. The filtrate is treated with alum and ammonia to separate the phosphoric acid from chlorides and ferro- cyanides the precipitate is dissolved in nitric acid and the solution treated with molybdate mixture in the usual way (cf.J.S.C.I. 1923 April). A. R. P. Valuation of Insoluble Phosphates by means of a Mowed Citric Acid Test. G. S. ROBERTSON and E'. DICKINSON (J. Soc. Chem. Id. 1923 42 59-62~).-The authors contend that the respective values of phosphatic fertilisers may be determined by a modification of the solubility test proposed by Wagner. For this purpose they propose that the solubility be determined by shaking 1 g . of the phosphate (in place of 5 g. proposed by Wagner) with 500 C.C. of 2% citric acid solution for half an hour in a shaker making 30 revolutions per minute. Results of field tests are given in support of the contention. Electrolytic Apparatus for the Estimation of Arsenic.G. W. MONIER-WILLUMS (Analyst 1923 48 112-l14).-The apparatus is a modification of that described by Sand and Hack- ford (T. 1904 85 1018) lead electrodes being used. The wal4 of the porous pot are little more than 1 mm. thick. The anode is a strip of lead foil and the cathode a disk of the same material about 2% cm. in diameter. The central glass vessel and the tap funnel are blown in one piece and the calcium chloride tube is connected by a ground glass joint. The hard glass tube for the reception of the arsenic mirror is 2 mm. in diameter and is con- nected with the apparatus by a short piece of caoutchouc tubing. A piece of metal gauze is wrapped round the part of the tube exposed to the flame and a sharper arsenic mirror is obtained by wrapping a small piece of filter-paper round the tube with its end dipping into water.The current used is 5-6 amperes the potential difference between the electrodes being 7-9 volts. Foodstuffs of the most varied character can be tested without preliminary treat- G. I? M. J. S. G. T.ANALYTICAL CHEMISTRY. ii. 2.53 ment. Large amounts of phosphoric acid or phosphates appear to inhibit the formation of arsine. Iron also acts as an inhibiting agent when no organic matter is present. The small quantities of phosphates and iron present in many foodstuffs do not appear to have any effect. The electrolytic method is sensitive to 0.001 mg. of arsenious oxide and to a great extent eliminates the personal equation. H. C. R. Potentiometric Titration of Arsenic and Antimony. EDUARD ZINTL and HEW” WATTENBERG (Ber.1923 56 [BJ 472480).-Tervalent arsenic and antimony can be readily estim- ated by titration with standard potassium bromate in hydrochloric acid solution the end-point being determined potentiometrically (cf. Zintl and Wattenberg A. 1922 ii 871). I n the case of tervalent arsenic the end-point indicated potentio- metrically is identical with that given .by methyl-orange if the concentration of hydrochloric acid is below 10%. The potentio- metric method has however the advantage that the proximity to the end-point is much more distinctly indicated and the titration can therefore be more rapidly performed. Tervalent antimony may be estimated in cold solution in the same manner as arsenic. [Test analyses indicate that the value 120’2 usually adopted for the atomic weight of antimony is more than 1% low but are in harmony with the datum 121.77 of Willard and McAlpine (Ao 1921 ii 405).] The titration can be equally effected in hot solution if atmospheric oxidation is avoided by rapid manipulation.Reduction of quinquevalent antimony is effected by the action of titanium trichloride solution in the presence of a little copper sulphate on the nearly boiling antimony solution which must contain about 5% of hydrochloric acid. The end-point of the reduction is determined potentiometrically after which the titration with bromate is effected as usual. Alternatively the antimony solution containing at least 5% of free hydrochloric acid is heated nearly to boiling and treated with ten drops of phosphotungstic acid (10%).Titanium trichloride is added with constant shaking until a marked blue colour is developed which does not disappear after two minutes. Three drops of copper sulphate solution (1%) are added as catalyst and the solution is shaken and exposed to air as much as possible whereon the blue colour disappears within one to two minutes. The solution is immediately titrated with bromate in the presence of methyl-orange. The presence of stannic salts does not cause complications in this or the potentiometric estimation of antimony. The reduction of quinquevalent arsenic is effected with greclt difEculty by stannous chloride chromous chloride or titanium trichloride. It is therefore readily possible to estimate antimony by titration in the presence of quinquevalent arsenic; in this case the potentiometric method must be used since the presence of phosphotungstic acid causes the reduction of arsenic acid.If arsenic and antimony are present entirely in the tervalentii. 25p ABSTRA(PrS OF UHEMICIAL PAPERS. mndition they may be estimated in a single solution. Their sum is first estimated by titration with bromate solution and subse- quently the antimony is determined alone after reduction with titanium chloride under potentiometric control. Preliminary experiments show that thallium sulphurous acid potassium ferrocyanide and hydrazine can also be estimated The Estimation and Separation of Arsenic Antimony and Tin. K. K. JABVINEN (2. awl. Chem. 1923 62 18” 204).-Mter describing experiments in which the accuracy of the bromate method for the titration of arsenious and antimonious chlorides is proved it is shown that the completeiiess of the reduc- tion of stannic chloride by iron depends on the complete exclusion of air from the apparatus until the solution is quite cold and on the use of suflicient iron at least 6 g.of ferrum redactum per 100 C.C. of solution being required. The most satisfactory reducing and volatilising agents for use in the separation of arsenic from antimony and tin by distillation from a chloride solution were found to be potassium iodide and a mixture of potassium bromide and sodiuni sulphite. I n the latter case the distilling flask must be fitted with a 3-bulb Young’s stillhead in order to avoid any antimony passing over towards the end of the distillation.The complete separation of antimony from tin by precipitation with metallic iron is extremely difficult as the precipitate almost in- variably contains tin and if an attempt to remove this by pro- longed digestion of the precipitate in the solution is made a certain amount of antimony dissolves. However addition of a further small quantity of iron and filtration of the solution before all the iron is dissolved yields a precipitate free from tin but containing iron and not suitable for titration with bromate. It is rinsed back into the beaker the residue on the paper dissolved in hydrochloric acid with a few mg. .of potassium chlorate and the solution treated with twice its bulk of hydrogen sulphide water. The precipitate is collected washed and dissolved in nitric and sulphuric acids.The solution including the filter-paper is heated in a Kjeldahl flask until colourless 1 g . of soditini thiosulphate is added and the heating continued until all the sulphur has disappeared. The mass is dissolved in water and titrated with potassium bromate. The filtrate from the fist antimony precipitate is reduced with iron and titrated for tin as usual. Apparatus for Use in the Combustion Analysis of Volatile Hygrosoopic Liquids. JOHN BALDWIN SHOESMITH ( J . Xoc. C‘hem. Id. 1923 42 57-58~).-The apparatus consists of a capillary bulb tube which is connected by a capillary opening with a second and somewhat larger bulb; the latter serves as an air reservoir. After the sample has been introduced into the capillary bulb the capillary is sealed and the end inserted into a short piece of glass tubing which is constricted at its middle.The whole is placed in the combustion tube and the capillary is broken against the constriction in the glass tubing by applying pressure to the potentiornetrically . H. w. A. R. P.ANALYTICAL CHEMISTRY. ii. 265 latter. The sample is expelled from the capillary bulb by $he expansion of the air in the second bulb as this becomes heated. w. P. s Estimation of Carbon Dioxide in Carbonates. K. H. JI~RVINEN and 0. SUMELIUS (2. anal. Chern. 1923 62 222-2229]. -For carbonates associated with starch as in baking powders the substance containing 0*3-0*6 g. of carbon dioxide is intro- duced into a 200 C.C. gask fitted with a dropping funnel and connected to a ten-bulbed absorption tube containing 60 C.C. of N-sodium hydroxide and this in turn connected to a guard tube also containing sodium hydroxide.The rate of evolution should be one to two bubbles per second. Then air free from carbon dioxide is slowly passed through the contents of the flask a t the ordinary temperature for two hours to expel the last tracm of carbon dioxide. The solution from the bulbs is treated with 50 C.C. of barium chloride solution then titrated with N-hydrochloric acid with phenolphthalein as indicator. In cases in which the solution may be boiled the substance together with 100 C.C. of water is placed in a 300-400 C.C. Kjeldahl flask through the stopper of which passes a 40 cm. dropping funnel; the stem is filled with water and the funnel closed with a well-fitting stopper to prevent regurgitation by the back pressure due to boiling.By means of a 50 cm. tube drawn out for 2 cm. a t the lower end the flmk is connected to the bottom of an 80 cm. burette tube the two tubes being inclined at about 30". The top 01 tbe burette is fitted with a soda-lime tube. Fifty C.C. of N-sodium hydroxide are put into the burette lacmoid and pumice added to the flask and the con- tents boiled to expel all the air. Keeping a similar rate of boiling 25 C.C. of 2N-hydrochloric acid are added at a rate of one fo two drops per second and when all the acid has been added tho liquid is boiled for two to three minutes. The contents of the burette are then treated with barium chloride and titrated as already described. The operation takes half an hour and is very accurate.Rapid Estimation of Potassium in Acid-insoluble Silicates. M~NUEL M. GREEN ( I d . Eng. Chew. 1923 15 163).-The method depends on the assumption that all metals exce t potassium sample is weighed out into cz platinum crucible 1.5 C.C. of 2N-per- chloric acid and 3 4 C.C. of 48% hydrofluoric acid are added and evaporated until fumes of perchloric acid aye given off. The crucible is cooled and two-thirds filled with water heated to boiling filtered and thoroughly washed with hot water the filtrate and washings being run into a platinum dish. The liquid is evapor- ated until fumes of perchloric acid are evolved cooled and 25 C.C. of 97% alcohol are added. The residue is broken up and filtered on an untared Gooch crucible and thoroughly washed with the per- chloric acid-alcohol mixture. The asbestos mat and precipitate &re transferred fo a filter thoroughly washed with hot water and filtered isfo a platinum dish.04-1.0 C.C. of 2 N-perchlOric J. B. F. form perchlorates soluble in 97% alcohol; 0-15-0. B 5 g. of theii. 256 ABSTRACTS OF CHEMICAL PAPEW. acid is added and the liquid evaporated until fumes appear cooled 25 C.C. of 97% alcohol are added the precipitate is broken up and filtered on a tared Gooch crucible washed with alcohol containing perchloric acid and dried to constant weight a t 110". The method is accurate to &0-27( and the estimation requires two to three hours. H. C. R. The Alkali Content of Blood and Cerebrospinal Fluid. A New Method for the Estimation of Sodium.M. RICHTER- QUWNER (Biochern. Z. 1922 133 417432).-A method for the estimation of sodium in the blood is described based on ultra- fitration followed by precipitation of the sodium by potassium pyroantimonate. Venous stasis and likewise the removal of carbon dioxide has no influence on the sodium content. Under normal conditions the corpuscles contain no sodium. Isatin as a Microchemical Reagent. J. B. MENKE (Bee. trav. chim. 1923 42 199-203).-The silver and cuprous salts of isatoic acid have crystalline forms which are easily recognisable. They are precipitated on addition of a solution of the metallic salt to a 5% solution of ammonia in which isatin has been dissolved. The corresDondinp silver ammonium compound is also noted. W. 0. K. H. J. E. The Application of Conductometric Titrations to Pre- cipitation Analysis.VIII. Conductometric Titrations with Lithium Oxalate. I. M. KOLTHOFF (2. anal. Chem. 1923 62 161-177).-Silver lead and copper may be accurately titrated conductometrically with lithium oxalate the end-point in each m e being accompanied by a very abrupt change in the conductivity of the solution. Cadmium and zinc salts give much less trust- worthy results which become very erratic if alcohol is added. Nickel- cobalt- manganese- and ferrous-ions appear to form complexes on the addition of the oxalate so that two deflections neither of which is very definite occur in the conductivity curve the first corresponding with the addition of half the oxalate re- quired to form the normal salt. Magnesium gives low results owing to the appreciable solubility of magnesium oxalate and its tendency to form complexes and supersaturated solutions.Barium strontium and calcium in neutral solutions may be satisfactorily estimated by the process; calcium also gives good results in ammmacal solutions and a t extreme dilutions provided that 30% of alcohol is present. The presence of magnesium in the calcium solution gives very high results but if a great preponcler- rtnce of calcium ions is present the sum of the two metals is accur- ately estimated by titration conductometrically with lithium uxalate so that this process may be applied to the determination of the hwdness of potable water. Application of Conductometric Methods to Precipitation Analysis. X. Conductometric Titrations with Potassium Ferricyanide.I. M. KOLTHOFF (2. anal. Chem. 1923 62 214- 215).-On account of the great mobility of the potassiurn-ions the A. R. P.B;NALpTICAL CHEMISTRY. ii. 257 different points of inflection of the conductometric c\ifvss with potassium ferricyanide are not sharp and as an analytical ratgent the latter finds only a little application. Lithium ferricpnide would be more suitable. Silver forms a red-coloured salt Ag,E'e(CN),. The conductometric curve resembles that for potassium being almost horizontal up to the point of inflection. Copper and cadmium can be accurately estimated. Lead does not form a precipitate with potassium ferricyanide and the conductometric curve is a straight line. Cobalt forms a blue precipit,ate Co,[Fe(CN)&.A very dilute solution of cobalt containing 10 mg. of cobalt per litre gives a distinct red coloration Nickel gives a faintly orange- coloured precipitate with the reagent. Nickel and cobalt are accurately estimated by this method. Manganese gives irregular results. Zinc also is not accurately estimated. With the exception of those of zinc and manganese the salts are of normal composition. Application of Conductometric Methods to Precipitation Analysis. XI. Conductometric Titrations with Sodium Nitroprusside. I. M. KOLTHOFF (8. anal. Chern. 1923 62 216-217).-Various metals give with sodium nitroprusside a pre- cipitate of normal composition. Only silver is accurately estimated by conductometric titration. The Volumetric Estimation of Calcium. A. VURTEEIM and H.G. C . VAN BERS (Chem. Weekblad 1923 20 68).-An answer to the criticisms of Grossfeld (this vol. ii 183) on the method put forward by the authors (A. 1922 ii 869). Neutralisation with sodium hyaoxide in the cold is more likely to cause precipitation of phosphate than addition of ammonia drop by drop a t the boiling Method for the Quantitative Separation of Glucinum and Uranium. PAUL H. M.-P. BRINTON and REUBEN B. ELLESTAD (J. Amer. Chem. Soc. 1923 45 395-398).-The quantitative separation and estimation of uranium and glucinum in mixtures of compounds of the two elements has been investigated and the folloiving method evolved. To the hydrochloric acid solution about 5 g. of ammonium chloride and 5 g . of hydroxylamine hydro- chloride are added followed by a concentrated solution of ammonium carbonate which is added until the precipitate a t fist formed is entirely redissolved. The solution is heated to boiling and the boiling continued for one minute after the appearance of a heavy precipitate of basic carbonate.The precipitate is filtered immedi- ately and thoroughly washed with cold water. This basic carbonate precipitate is free from uranium. It is set aside to be ignited with the small amount of glucinum hydroxide which is to be sepamted from the atrate. The filtrate is acidified with hydrochloric acid and boiled to expel carbon dioxide then after the addition of 1 g. of hydroxylamine hydrochloride a slight excess of ammonia is added to the cold solution and the small precipitate of glucinum hydroxide is atered and washed with 2% ammonium nitrate solufion to which J.B. F. J. B. F. point. s. I. L.ii. 258 ABSTRACPS OF CfEEMICAL PAPERS. have b ~ a added a few crystals of hydroxylamine hydrochloride and sufiioient ammonia to make the solution faintly allraline. The combined glucinum preoipitates are ignited and weighed a1 oxide. The filtrate is acidified with hydrochloric acid and the hydroxyl- amine oxidised either by adding 75-100 C.C. of 3% hydrogen peroxide solution and boiling until the evolution of oxygen ceases or by adding solid sodium or potassium bromate with constant stirring until the solution assumes an intense colour of bromine. The oxidised solution is heated nearly to the boiling point and a slight excess of ammonia is added with constant stirring. After settling the ammonium uranate is filtered and washed with 2% ammonium nitrate solution which contains a little free ammonia. The precipitate is ignited and weighed as U,O,.The method is good and gives trustworthy and accurate results. A Rapid Volume€ric Method for the Estimation of Mag- nesia in Carbonate Rocks. H. XI. BEANDENBERG and A. H. AVAKIAX (Cmrete [Hill Section] 1922 2'9 78).-0me g. of thc sample is treated in an Erlenmeyer flask fitted with a reflux con- denser with 60 C.C. of O.4N-hydrochloric acid containing 2 C.C. of an alcoholic solution of phenolphthalein per litre. After boiling and cooling the excess of hydrochloric acid is titrated with 04.X- sodium hydroxide the first pale pink colour being taken as the end-point. The mixture is again boiled 1-5 g.of sodium oxalate and an excess of O4V-sodium hydroxide are added and boiling is continued for a few minutes. The liquid is then cooled diluted to 200 c.c. filtered and 100 C.C. of the filtrate are titrated with 0.4N- hydrochloric acid. It is assumed that the loss of acidity in dis- solving the substance is due entirely to the presence of calcium and magnesium carbonates and that the final precipitate consists of calcium oxalate and magnesium hydroxide. J. F. S. CHEMICAL A~STRAOTS. The Alkalimetric Estimation of Magnesium and Calcium Saltsl RICHARD WILLSTATTER and ERNST WALDSCHMIDT-LEITZ (Ber. 1923 56 [B] 488491).-The methods depead on the observation that the solubility of magnesium and calcium hydr- oxides can be so depressed by the use of suitable solvents that the subrJtances do not affect appropriate indicators. The aqueous solution of a magnesium salt is gradually treated with an excess of alkali hydroxide solution ( N / I O - N / l ) and so much ethyl alcohol is added that the concentration of the latter is 66-75%.After ten to fi€teen minutes the excess of alkali is titra;ted with hydrochloric acid in the presence of thymolphkbalein (about 10 drops of a 06;% alcoholic solution are used for each 100 O.C. of liquid); phenolphthalein cannot be employed. Ethyl alcohol may be replaced by methyl alcohol the suitable Concen- tration of which is also 66-75%; in this case the titration is complicmted by the adsorption of the indicator by the precipitated magnerrium hydroxide and the method is only suitable in certain circumshnces (see later).Aqueous alcoholic solutions are unsuitable for the estimation ofANALYTICAL CmEmTRY. ii. 259 calcium which is performed as follows. An excess of alkali hydr- oxide (N/10 to N/1) is added drop by drop to the aqueous solution of the calcium salt which is subsequently treated with neutral acetone until the concentration of the latter is 85-90%. After fifteen minutes the excess of alkali is titrated in the presence of thymolphthalein (10 drops in 200 C.C. of liquid) until the blue colour permanently disappews. Towards the end of the titration the colour is temporarily discharged but returns as the adsorbed alkali hydroxide again passes into solution. When magnesium and calcium hydroxides are simultaneously present the sum of the bases is estimated in 90% acetone.Mag- nesium alone is estimated in 66% methyl or ethyl alcohol. If calcium is present in relatively small amount ethyl alcohol is to be preferred on account of the sharper end-point. If however calcium is present in equal or excess quantity the method is in- accurate since the magnesium hydroxide carries down and retains small amounts of calcium hydroxide. In these circumstances methyl alcohol (66-70%) in which calcium hydroxide is more freely soluble must be used; the end-point of the titration is shorn by the first complete disappearance of the blue colour of the thymolphthalein; no attention is paid to the bluish-violet color- ation which gradually develops in the magnesium hydroxide. If iron is also present as in the analysis of dolomite it is either precipitated with the aluminium hydroxide and the ammonium salt is expelled or is completely converted into the ferrous state by means of sulphur dioxide.Ferrous hydroxide behaves like mag- nesium hydroxide in the presence of ethyl alcohol or acetone and is estimated simultaneously ; it is separately determined by titration with potassium permanganate. H. W. The Estimation of Zinc in Minerals. ET. OLIVIER (Mon. Sci. 1923 13 31-35).-About 1.5 g. of the mineral; ound to pass an 80-mesh sieve is dissolved in 20-25 O.C. of &drochloric acid with subsequent addition of 10 C.C. of nitric acid After evaporation to dryness and dehydration of silica the residue is taken up with 5 C.C. hgdrochloric acid and diluted with 30 C.C. of warm water. Saturated hydrogen sulphide solution is added until the volume amounts to about 125 C.C. The pre- cipitated lead copper antimony arsenic and cadmium sulphides are atered and washed with about 150 C.C.of warm water containing 5 C.C. of hydrochloric acid and a few C.C. of hydrogen sulphide solution. The filtrate is boiled to expel hydrogen sulphide and brought to a volume of about 200 C.C. Ten C.C. of nitric acid and after cooling 2-20 C.C. of hydrogen peroxide or 5-50 C.C. of bromine water (according to the amount of manganese present) are added Go the solution. Iron aluminium and manganese are precipitated by the addition of 60 C.C. of ammonia $he liquid being allowed t o remain over-night with free access to the air. The solution is atered and titrated with sodium sulphide solution using lead test-paper as an outside indicator.Titrations am compared with those of a standard zinc solution which is larepasedii. 260 ABSTRACTS OF OHEMICAL PAPERS. by a similar process to that to which the mineral has been subjected. The same tint of sulphide stain on the test-paper should be adopted as the end-point in each case and this should be further confirmed by the addition of (say) 0.2 and 0.5 C.C. of sulphide solution which should produce similar intensifications of the stain in both cases. A. G. P. Electrometric Estimation of Zinc by means of Silver Nitrate. ERICH MULLER and ALFRED ADAM (2. Elektrochern. 1923 29 49-53).-Using much the same method as was pre- viously employed for the estimation of nickel and cobalt (A. 1922 ii 875) the authors now show that zinc may be estimated electro- metrically.The determination is carried out by treating 10 C.C. of the zinc solution with an excess of potassium cyanide solution and titrating the excess of potassium cyanide with N/lO-silver nitrate solution using a silver wire as indicator electrode. It is also possible to determine simultaneously the amount of silver which may be present with the zinc by the same process. Cad- mium lead and copper cannot be estimated by this method. J. I?. S. Application of Conductometric Methods to Precipitation Analysis. IX. Conductometric Titrations with Potassium Ferrocyanide. I. M. KOLTHOFF (2. anal. Chem. 1923,62 209- 214).-Lead can be accurately estimated by conductometric titration with potassium ferrocyanide since it forms only the normal salt.Zinc may also be accurately estimated in weak ammoniacal solution ; stronger ammoniacal solutions require less reagent. A mixture made up of 20 c.c. 0.05 M of zinc sulphate 20 C.C. of water and 2.5 C.C. of a 10% solution of ammonia required 1-99 C.C. of 0.25 M reagent a t the point of inflection whereas with 18 C.C. of the ammonia solution this point was reached with 1-78 C.C. of the reagent 2-00 C.C. being the calculated value. In the absence of ammonia two points of inflection occur the first corresponding with the normal salt ZII~F~(CN)~ and the second with Silver copper cadmium manganese mckel and cobalt first give rise to a normal salt which combines with a further quantity of reagent to form double salts. Silver gives a second point of inflection corresponding approximately with KAg3Fe(CN)6 copper and cadmium a t K2Cu,[Fe(CN),] and &Cd [Fe(cN)6]2 respec- tively.Copper gives a third point a t K4CU,[Fe(h)&. Manganese nickel and cobalt behave similarly to copper but with the form- ation of a further point corresponding with a composition of the type [3K,Fe(CN),+4MnFe(CN),]. J. B. F. Electro-analytical Methods for the Estimation of Metals in Hydrochloric Acid Solution. ANNA J. ENGELENBURG (2. anal. Chern. 1923 62 257-284).-The methods proposed by Schoch and Brown (A. 1913 ii 794) for the electrodeposition of tin copper antimony bismuth lead and cadmium from chloride solutions in the presence of h ydroxylamine hydrochloride have &2Zn3[Fe(CN) 612.ANALYTICAL CHEMISTRY.ii. 261 been further studied and modifications in the temperature quantity of hydroxylamine hydrochloride added and the current used are suggested. Application of the reaults to the separation of certain of the above metals from one another are also suggested. Cadmium is deposited from a solution containing 10 C.C. of hydrochloric acid in 200 C.C. bulk by electrolysing for twenty minutes at 1 ampere then adding 20 g. of ammonium oxalate and 10-20 g. of oxalic acid and con- tinuing the electrolysis for a further forty minutes a t 1.2 amperes. Zinc is estimated by electrolysis of a solution containing 1.5 C.C. of hydrochloric acid and 2 g. of hydroxylamine hydrochloride in 200 c.c.; the temperature is maintained a t 18" and the current increased slowly from 4 to 8 amperes.In all the above processes hydrazine sulphate may be used instead of hydroxylamine hydro- chloride and in the case of copper 0.1-0.2 g . of ammonium per- sulphate in place of either of the other two reagents gives a more firmly adherent and smoother deposit. A mixture of 0.4 g. of ammonium persulphate and 0.5 g. of hydroxylamine hydrochloride in 150 C.C. of a tin solution containing 12 C.C. of hydrochloric acid improves the nature of the tin deposit. By measuring the cathode potentials of a solution containing the above metals the presence or absence of each in the solution may be ascertained by the potential changes as each metal is deposited. The following new processes are described. A. R. P. Lead. 11. Electrolytic Estimation of Lead in Biological Material.A. S. MINOT ( J . Biol. Chem. 1923 55 1-S).-The method described by Denis and Minot (A. 1919 ii 372) is inaccurate and is in fact untrustworthy even as a qualitative test for lead. This is due partly to the presence of manganese and partly to other factors. Fairhall's method (A. 1922 ii 659) however gives accurate results. E. S. The Carrying Down of Acids by Alumina Precipitates. ANDRB CHARRIOU (Cmpt. rend. 1923 176 679-682).-When alumina is precipitated by ammonia in presence of an alkali chrom- ate the precipitate remains yellow even after prolonged washing with boiling water. The alkali metal could not be detected in the precipitate and i t is therefore only the acid which is carried down by the alumina and it probably forms a layer of aluminium chromate on the alumina which may constitute anything from 1-7% of the total weight.A similar absorption of chromic acid oceurs when precipitated aluminium hydroxide is placed in contact with potassium chromate solutions. The precipitate cannot be freed from chromic acid by washing with ammonium nitrate chloride or acetate solutions but when the alumina is precipitated with ammonium hydrogen carbonate or precipitated with ammonia and washed subsequently with 5% ammonium hydrogen carbonate solution it is obtained perfectly colourless and free from chromate. A similar result is obtained with lithium or sodium carbonate or with ammonium phosphate the carbonic or phosphoric acid apparently displacing the chromic acid and taking its place. In VOL. CXXIV. ii. 10ii. 262 ABSTRACTS OF CHEMICAL PAPERS.analysis it is sufficient therefore to wash the alumina with 5% ammonium hydrogen carbonate solution in order to eliminate chromic acid the carbonic acid and ammonium salts remaining in the precipitate being subsequently removed during the calcin- ation. G. 3'. M. Qualitative Analysis of the Iron Group. RALPH W. HUFFERD ( J . Arner. Chem. Xoc. 1923 45 438439).-A modified method of treating the iron group precipitate in qualitative analysis is described. The precipitate is treated with a large excess of sodium hydroxide to remove the aluminium zinc and chromium. The precipitatle is treated directly with nitric acid and potassium chlorate to remove the manganese. Iron is removed by adding a large excess of ammonia. The filtrate from the iron precipitate is evaporated until it has only a faint odour of ammonia and one- fifth of the solution treated with dimethyl-glyoxime to test for nickel.The remainder of the solution is evaporated to a syrup treated with sufficient water to dissolve the salts and tested for cobalt by adding 3 C.C. of 10% potassium thiocyanate followed by 3 C.C. of a mixture of amyl alcohol and ether (1 3). I n the presence of cobalt the solution becomes bluish-green; if the colour is indistinct the careful addition of a few drops of 12N-hydro- chloric acid will develop the colour if cobalt is present. I n the absence of cobalt the colour of the ether layer will be straw- coloured or colourless. 5. F. s. Volumetric Estimation of Tervalent Iron and of Copper in the Presence of Iron.FRIEDRICH L. HAHN and HEINRICH WINDISCH (Ber. 1923 56 [B] 598-601).-The iodometric estim- ation of ferric salts involves a large expenditure of time and iodide since the reaction Fe***+I' =s= Pe"+I is reversible and dissociation only occurs slowly when the liberated iodine is removed. Since however cupric salts are instantaneously reduced by iodides to iodine and cuprous salts and the latter convert ferric salts into ferrous compounds it is possible to catalyse the action of ferric salts and iodides by the addition of a small amount of cuprous compounds to such an extent that the titration can be performed immediately and in the presence of only a small quantity of iodide. The use of isolated cuprous iodide is unnecessary. It is sufficient if the potassium iodide solution is treated with a little copper sulphate and starch and subsequently with sodium thiosulphate until the blue colour is just discharged; the suspension is added to the solution of the ferric salt and the liberated iodine is imme- diately titrated with thiosulphate.The method is considered to be the most convenient and trustworthy for the standardisation of thiosulphate solutions. It appears therefore that the sum of copper and iron can be immediately estimated by titration in mixtures of ferric and cupric salts. The action of the iron can be eliminated by the addition of a solution of sodium phosphate which has been treated with phosphoric acid until it decolorises p-nitrophenol to theANALYTICAL CHEMISTRY. ii. 263 neutral or faintly acid solution.If the ferric solution is strongly acidic it may be partly neutralised phosphate without phosphoric acid may be used or a larger proportion of the mixture may be employed It is sufficient if two molecular proportions of phos- phate are added for each molecule of ferric salt. It is immaterial whether ferric phosphate is precipitated or not. The estimation of copper is not influenced by the addition of phosphate. H. W. Estimation of Bismuth as Phosphate and Its Separation from Lead Copper and Cadmium. G. LUFF (Chem. Ztg. 1923 47 133-134) .-The precipitation of bismuth as phosphate from a slightly acid solution of the nitrate serves to separate it from copper lead and cadmium if the operation is conducted as follows. The nitric acid solution of the metals is exactly neutralised with ammonia using methyl-orange as indicator 4 C.C.of nitric acid are added and the bismuth is precipitated by the addition drop by drop to the boiling solution of a solution of 1 g. of ammonium phosphate in 40 C.C. of water and 2 C.C. of nitric acid. The dense crystalline precipitate of bismuth phosphate is collected washed with hot water ignited wet together with the filter-paper and weighed. If the filtrate contains only cadmium this is precipitated as sulphide after the addition of an excess of ammonium acetate and the sulphide is dissolved in hydrochloric acid. The solution is rendered neutral to methyl-orange by the addition of potassium carbonate and the cadmium precipitated by a large excess of diammonium hydrogen phosphate.The pre- cipitated cadmium ammonium phosphate is collected on a filter washed fust with dilute ammonium phosphate solution then with 60% alcohol ignited and weighed as pyrophosphate (cf. Schoeller and Waterhouse A. 1921 ii 195). A. R. P. New Compounds of Platinum Palladium Iridium and Rhodium and a New Method for their Estimation. W. N. IVANOV (Chem. Ztg. 1923 47 209-21O).-When 0*25% solutions of potassium chloroplatinite and sodium thiocyanate are mixed and left for five to six hours a t the ordinary temperature then shaken with 50 g. of ammonium nitrate or sulphate per litre a light brown flocculent precipitate of platinous thiocyanate is produced. The precipitate is soluble in aqua regia and in potassium cyanide solution but not in single acids or alkalis. I f the pre- cipitation is carried out in boiling solutions a black flocculent precipitate having the composition Ptd(OH),S(CS*NH,) is obtained.On ignition a residue of platinum is left so that the compound is suitable for use in the estimation of platinum. Under similar conditions palladium gives a precipitate of Pd,S,( CS-NH,) which on ignition leaves a very fusible residue of Pd,S whch is slowly transformed after prolonged heating into the metal. Rhodium also gives a black precipitate the composition of which however was not ascertained. On ignition it yields metallic rhodium. ~ d i u m is incompletdy precipitated as a flocculent yellow corn- pound. A. R. P. 10'ii. 264 ABSTRACTS OF CHEMICAL PAPERS. The Detection of Methyl Alcohol in Ethyl Alcohol. H. W. VAN URK (Phrm.Weelcbbd 1923 60 273-276) .-Distillation should be carried out as recommended in the German official method the first 10 C.C. from 100 C.C. of the sample being again distilled and the first 1 C.C. taken. Oxidation may be conveniently carried out by means of the copper spiral and formaldehyde detected by DenigAs’s method ; a positive result should be confirmed by the morphine-sulphuric acid test. s. I. L. Characterisation of the Alkylglycerols. RAYMOND DELABY (Compt. rend. 1923 176 396-399; cf. this vol. i 84 85).-Thc author has tested the reactions described by DenigAs (“ Prkcis de Chimie analytique,” 1920 151) for glycerol with methyl- ethyl- propyl- and butyl-glycerols to see how far they are specific. After oxidation with bromine of the colours obtained in the presence of sulphuric acid with certain alkaloids or phenols only that with codeine namely a blue colour is specific to glycerol Similarly if potassium bromide is added to the oxidation products before the sulphuric acid and then the colour tests described are applied only the colour blue with guaiacol serves to distinguish glycerol from its homologues. If the osazone test is applied to the oxid- ation products the osazone from methylglycerol is quite different from that obtained from glycerol and the other glycerols only give oily products.All the products of oxidation with bromine of the alkylglycerols reduce Nessler’s reagent Fehling’s solution and ammoniacal silver nitrate. None of the oxidation reactions with potassium permanganate is specific to glycerol and the same applies to the oxidation with lead peroxide.W. G . Modification of Windaus’s Method for the Estimation of Cholesterol. ROUER CANINADE (Bull. SOC. Chim. biol. 1922 4 601-613) .-Windaus’s method yields irregular results unless the precipitation of the digitonin cholesteride is made under definite conditions. More consistent results may however be obtained with much greater rapidity if the precipitate is formed in a solvent consisting of acetone (78 parts) water (18 parts) and alcohol (9 parts). A 5% solution of digitonin in the mixed solvent is added to the hot solution of cholesterol in the samc solvent. The precipitate forms immediately and after a few minutes is filtered and washed first with hot water then with the mixed solvent and finally with ether to remove lecithin.E. S. Molybdo-manganimetry and its Applications. G. PONT~S and L. TIIIVOLLE (Bull. XOC. Chim. biol. 1922 4 614-622).- The authors have shown that the volumetric micro-estimation of dextrose (A. 1921 ii 563) and of lactose (A 1922 ii 323) may be conveniently carried out by means of potassium permanganate when used in conjunction with a phosphomolybdic acid reagent. The method appears to be generally applicable t o the micro-ANALYTICAL CHEMISTRY. ii. 265 estimation of reducing substances and it is accordingly proposed to class such volumetric methods under the heading “molybdo- manganimetry.” The phosphomolybdic acid reagent is reduced by cuprous ferrous stannous and mercurous salts by sodium hyposulphite and even by metallic copper iron zinc and mag- nesium.The blue oxides of molybdenum so produced may be titrated with potassium permanganate by which they are re- oxidised to molybdic acid but the details of the method have not yet been worked out for each case It is shown however that the copper deposited on the cathode in Pregl’s apparatus for the micro- electrolysis of copper dissolves readily in the phosphomolybdic acid reagent and that titration of the blue solution so obtained gives results agreeing with those obtained gravimetrically. For purposes of calculation the reaction is regarded as a direct oxid- ation of the reducing substance by potassium permanganate ; hence in the estimation of dextrose the use of a standard may be dispensed with if desired. Micro-estimation of Blood-sugar with Ferricyanide.H. C. HAGEDORN and B. NORMAN JENSEN (Biochem. Z. 1933 135 46-58).-A new method which is claimed as superior to Bang’s micro-method for the estimation of sugar in 0.1 C.C. of blood has been worked out in detail and depends on the oxidation of the sugar by excess of potassium ferricyanide the excess being estimated by the iodine liberated in presence of zinc salts from potassium iodide. About eighteen analyses can be carried out in an hour. For details and tables the original should be consulted. Methods of Chemical Investigation on Blood. V. Estirn- ation of Sugar in Blood. ALMA ROSENTHAL (Biochem. Z. 1922 133 4 6 9 4 7 5 ) .-Details are given of a slightly modified Hagedorn method for the estimation of blood-sugar. After precipitation of the protein by metaphosphoric acid or sodium tungstate the filtrate is boiled with sodium ferricyanide and the excess which is not reduced to ferrocyanide is estimated by adding potassium iodide and titrating the iodine liberated with thiosulphate. From the result the content of the blood in dextrose can be obtained from a table.W. 0. K. The Detection and Identification of Maltose Galactose Sucrose and Inulin by a Mycological Method. ALDO CASTEL- LANI and F. E. TAYLOR ( J . Trop. Ned. 1922 25 4146).-An extension of the previously published method (Brit. Med. J. 1917 Dec. Rep.; Physiol. Abstr. 3 263). A table shows the reaction of a number of bacteria and fungi with a great variety of carbo- hydrates. Fermentation tests with two suitable micro-organisms is suEcient to establish the identity of any of the sugars named (cf.A. 1922 ii 879). Effects of the Method of Desiccation on the Carbohydrates of Plant-tissue. KARL PAUL LINK and W. E. TOTTIXGHAM ( J . Amer. Chenz. Soc. 1933 45 439447).-In preparing plant- E. S. H. K. CHEMICAL ABSTRACTS.ii. 266 ABSTRACTS OF CHEMICAL PAPERS. tissues for carbohydrate estimations a temperature of 98" should not be used for drying the fresh plant material when the sugar and starch contents are high. With tissue that can be dried rapidly a temperature of 65" in a current of air a t atmospheric pressure can be used safely if the tissue can be reduced to thin sections. When drying in a vacuum 80" is a better working temperature than 65" and in the case of coarse tissues improved results are obtained if the material is first heated in an autoclave to inhibit enzymatic and respiratory processes.The results obtained by this method in the case of beet leaves and corn ears were the same as when the alcohol method of preservation (cf. Davis and Daish A 1914 ii 152) was used. Drying a t low tem- peratures with a minimum error can be carried out only in a well- ventilated oven in which a large volume of air circulates con- tinuously over the material. Estimation of Incrustating Substances on Flax Fibres by Saccharification of the Cellulose. P. P. BUDNIKOV and P. W. SOLOTAREV (2. angew. Chem. 1923 36 138-139).-1n the purific- ation of flax waste by digesting it under pressure with liquors containing sodium hydroxide and sodium hydrogen sulphite the cellulose-content of the product was estimated by the method of Ost and Wilkening.In this method which gave satisfactory results 1 g . of the purified flax is dissolved in 7-43 C.C. of 72% sulphuric acid and the solution thereby obtained is afterwards diluted until its acid content is 3:4 and is then heated for two hours a t 120" in an autoclave. The reducing sugars present in the product are then estimated by means of Fehling's solutlion and the original cellulose-content calculatled. (See further J.X.C.I. 1923 April.) A. J. H. The Estimation of the Iodine Nwnber of Fats under Unfavourable Conditions. B. M. MARGOSCHES RICHARD BARU and LISBETH WOLF (2. anal. Chem. 1923 62 178-184).-The method of Aschman (Chem. Ztg. 1898 22 59 71) for the estim- ation of the iodine number of fats in which an aqueous solution of iodine monochloride is allowed to react on the fat gives accurate results even without the use of a solvent for the fat and without continual shaking provided that the solutions are left for a sufficient length of time (about twenty-four hours) before the excess of reagent is estimated.This period may be considerably reduced if the fat is dissolved in carbon tetrachloride or other suitable solvent and the mixture frequently agitated. A Simple Method for the Estimation of Lactic Acid in the Stomach-contents. RICH. Eaz (Biochem. Z. 1923 134 476488).-A method is described for the estimation of lactic acid in the stomach contents depending on the extraction of the lactic acid by ether and re-extraction by water before titration.The distribution of lactic acid between ether and water is allowed for. W. 0. K. W. G. A. R. P.ANALYTIC& CHEMISTRY. ii. 267 Cyanogenesis. A Reaction of Citric Acid. A. M. JORISSEN (Bull. A d . roy. Belg. 1919 731-737).-The author had pre- viously shown (A. 1914 i 813) that hydrocyanic acid was formed under the influence of light in solutions containing citric acid and traces of iron salts and nitrous acid. Hydrocyanic acid is not formed when citric acid is replaced by formaldehyde acetaldehyde formic lactic isobutyric or lzenilic acids sucrose dextrose gelatin vanillin or ethyl acetoacetate (cf. loc. cit.). A test is developed using ferric chloride acetic acid and potassium nitrite a8 reagents. A more sensitive test is as follows 100 C.C.of the solution to be tested are treated with 5 g. of manganese dioxide and 5 drops of acetic acid and the mixture is left for twenty-four hours. After filtration the liquid is treated with 5 to 10 drops of acetic acid and 5 C.C. of 1% potassium nitrite solution the mixture left over-night and then distilled in steam after adding calcium carbonate. The first 130 C.C. of distillate are tested for hydrocyanic acid (ferrous and ferric salt sodium hydroxide etc.). Glycerol lactose dextrin and the other substances detailed above do not give rise to hydrocyanic acid under these conditions. E. E. T. It fails in presence of tartaric acid. Comparison of the Pentabrornoacetone Method and Salant and Wise's Method €or the Estimation of Citric Acid in Urine. W. B. MCCLURE and L.W. SAUER (Amer. J . Physiol. 1922 62 140-144).-When known amounts of citric acid were added to normal urine the pentabromoacetone method (Amberg and McClure A. 1918 i 141) gave much better results than Salant and Wise's method (A. 1917 i 106) in three cases. In the fourth case there was close comparison between the results of the two methods. The pentabromoacetone method is preferred by the authors (cf. A. 1922 ii 791). CHEMICAL ABSTRACTS. Identzicatisn of Benzonaphthol [P-Naphthyl Benzoate I Salol [Pnenyl Salicylate] Betol [P-Naphthyl Salicylate 1 Cresalol b-Tolyl Salicylate] and Salophen b-Acetamido- phenyl Salicylate] by Microchemical Means. G. DE N I G ~ S (Bull. SOC. phrm. Bordeaux 1922 60 163-1 69) .-@-Naphthyl benzoate a fraction of 1 mg. of the material is dissolved on a glass slide in a drop of chloroform from a tapered rod of end diameter 2 4 mm.; evaporation leaves crystal groups forming more or less concentric zones. A drop of glacial acetic acid when placed a t the centre of the dry residue and allowed to evaporate yields arborisations often accompanied by isolated or crossed prisms. If the residue from chloroform or acetic acid is mixed with a drop of concentrated sulphuric acid and a glass rod which has been dipped into formaldehyde solution inserted a yellowish-brown colour develops and on gentle heating the mixture blackens. Phenyl salicylafe when similarly treated with chloroform yields an oily droplet which is not changed by treatment with acetic acid. The residue by dissolution in 'a drop of ethyl alcohol yields by evapomtion groups of rhombic plates similar crystalsii. 268 ABSTRACTS OF CHEMICAL PAPERS.being obtained also by seeding the oily droplet with the original material. Treatment as before with sulphuric acid and formalde- hyde gives a white cloudiness followed by a red coloration which is intensified by heating. p-Naphthyl salicylate is deposited from chloroform as an oily droplet; acetic acid then gives isolated rhombic plates mixed with clusters of prisms With sulphuric acid and formaldehyde the substance behaves in the same way as 9-naphthyl benzoate. p-Tolyl salicylate yields crystals (m. p. 36") by seeding the oily droplets obtained from chloroform acetic acid ethyl alcohol acetone or pyridine. With sulphuric acid and formaldehyde the substance behaves like phenyl salicylate.p-Acetamidophenyl salicylate is deposited from acetone as isolated or tangled rhombic plates. When treated with sulphuric acid and formaldehyde a rose colour develops in the cold; when heated the colour is intensified at first and then changes to brown. Demonstration of Salicylic Acid in Serum and Similar Fluids. H. HBRISSEY (Bull. Xoc. Chim. bid. 1922 4 64s- 651).-The serum is acidified with sulphuric acid extracted with ether and the presence of salicylic acid in the latter demonstrated by means of the ferric chloride reaction. Estimation of Formaldehyde and Acetaldehyde. E. W. BLAIR and T. s. WErEELER (Anulyst 1923,48,110-112).-Mixtures of formaldehyde hydrogen peroxide formic acid and a trace of ozone obtained in investigations on the action of oxygen and ozone on hydrocarbons were analysed as follows. Formic acid was estimated in an aliquot part by titrating with N/lOO-alkali methyl- red or phenolphthalein being used as indicator.Ozone was estimated in the neutralised solution by adding a 5% neutral solution of potassium iodide acidifying with 5% hydrochloric acid free from chlorine and immediately titrating $he iodine liberated with N/lOO-thiosulphate solutiolz. The hydrogen peroxide was estimated by Kingzctt's method (T. P880 3'7 SO2). To estimate the formaldehyde the ozone and hydrogen peroxide were destroyed by adding potassium iodide and sulphuric acid. The iodine set free was not titrated but the diluted solution was just neutralised with thorough cooling with sodium hydroxide solution. Twenty-five C.C.of N/lO-iodine solution were then added and the formaldehyde estimated by Romijn's iodometric method (A. 1897 ii 166) allowance being made for the iodine set free in previous reactions. If acetaldehyde was also present Ripper's method (A. 1901 ii 205) was used to obtain an iodine figure for both aldehydes and the cyanide figure (Sufton " Volumet'ric Analysis," 10th ed. p. 391) for formaldehyde applied t o it to estimate the acetaldehyde present. A Micro-method for the Estimation of Acetone and of p-Hydroxybutyric Acid in Urine and Blood. ALFRED LUBLIN (Biochem. Z. 1922 133 626-641).-A micro-metbod is described CHEMICAL ABSTRACTS. E. S. H. C. R.BNALY!PICAL CHEMISTRY. ii. 269 for the estimation of acetone and of p-hydroxybutyric acid in 0.2 C.C.of blood or in 0.5 C.C. of urine the estimation requiring thirty minutes in the first case and twenty minutes in the second. The acetone is distilled into an alkaline iodine solution and the iodine left is titrated with thiosulphate. w. 0. K. Reaction of Phenolphthdlein. G. DE BENAVENT (Anal. Fis. Quim. 1922 20 473-474).-An alkaline urine containing phenol- phthalein previously administered and eliminated by the kidneys was found to lose its red coloration on heating whilst on cooling the red coloration reappeared. The reaction is shown to be due to the presence of uric acid. A number of other organic acids were examined for this reaction which was however only given by salicylic acid and benzoic acid in addition to uric acid. G. W. R. Estimation of Amino-acids and Ammonia using an Apparatus to Control the Distillation.GIOVANNI REVOLT= (Biochem. Z. 1922,134,349-353).-The formal titration of amino- acids in pigmented urine is facilitated by using a colour match of the same urine instead of water as used by Sorensen. A n apparatus is also described which is designed to shorn when the evolution of ammonia is finished in a distillation. H. K. Estimation of Codeine. €€AROLD EDWARD ANNETT and RAM RICHHPAL SANGHI (Analyst 1923 48 16-18).-Eight g. of opium are triturated with 2 g. of freshly slaked lime and 80 C.C. of water for thirty minutes 50 C.C. of the filtrate are extracted three times with 50 C.C. portions of toluene the filtered extract is concentrated to 25 c.c. dry hydrogen chloride is passed through and the pre- cipitated codeine hydrochloride and colouring matter are dissolved in water and evaporated to dryness thereby rendering the colouring matter insoluble.The residue is treated with hot water the volume adjusted to 50 c.c. and the whole process is repeated from the beginning with 40 C.C. of the filtrate from the lime treatment (=4 g. of opium). In the h a 1 evaporation no further colour should develop and the addition of a little alcohol when nearly all the water has evaporated causes the separation of codeine hydrochloride in small colourless rosettes. The residue is dried to constant weight in a steam oven and taken as The method was tested mth pure codeine and on opium with and without added amounts of codeine and 95-96% of the codeine present was regularly recovered.C&,,P,”HC~,1&H,O* G. F. M. Estimation of Narcotine and Papaverhe in Opium. H. E. ANNETT and M. N. BOSE (Analyst 1923 48 53-58).- Opium (1.5 9.) is triturated to a smooth paste with 30 C.C. of 0.5% sulphuric acid and after thirty minutes 20 C.C. of the filtrate are boiled with 16 g. of sodium acetate until complete solution of the salt has been effected. After keeping over-night the liquid isii. 270 ABSTRACTS OF C%XEMIC& PAPERS. atered the precipitate completely transferred to the filter-paper washed and dried. It is then extracted with 20-25 C.C. of hot toluene the toluene extract is shaken with 20 C.C. of 10% sodium hydroxide to remove resins and colouring matters and the washed toluene solution is evaporated almost to dryness with the addition of 2-3 C.C.of alcohol to facilitate crystallisation of the narcotine and papaverine which after drying at 100" are weighed as such. The narcotine can then be estimated polarimetrically papaverine being optically inactive. The rotation is measured in toluene solution as in acid solution papaverine considerably depresses the optical activity of narcotine. The process was tested on opium with and without the addition of known amounts of the two alkaloids and satisfactory results were obtained without the use of any correction factor. A Rapid Process for the Exact Estimation of Small Quantities of Uric Acid in Urine and in Blood-serum. HEINRICH CHANTRAINE (Biochem. Z. 1922 133 605-612).-Uric acid in urine is separated as in Hopkin's method by the addition of ammonia and ammonium chloride after precipitating it as the copper salt and liberating it from that with hydrogen sulphide.Excess of potassium permanganate solution is added to the uric acid and the excess is estimated iodometrically. A similar method may be used for estimating uric acid in blood-serum. G. F. M. W. 0. K. Behaviour of Uric Acid in Protein Solutions. LUDWIG PINCUSSEN (Biochem. Z. 1923 134 447458).-Uric acid in serum is only partly free and results obtained on estimation are increased if the protein is first hydrolysed by it ferment or an acid as only the free uric ncid is determined by these methods. Other proteins and also fats lipoids etc. combine with uric acid. W. 0. K. The Iodometric Estimation of Antipyrine. I. M. KOLTHOFIT (Pharm.Weekbkud 1923 60 196199).-Very good results are obtained by the method of Bougault (A. 1917 ii 344) namely addition of excess of N/lO-iodine solution in presence of sodium hydrogen carbonate acidification after one hour and titration back with thiosulphate after addition of chloroform The reaction is C,,H,,ON + I = CllHl10N21 + HI. Sodium acetate may be used in place of the hydrogen carbonate and alcohol in place of chloroform. The results are not affected by the presence of sodium saJicylate caffeine acetanilide pheaacetin or aspirin. S. I. L. Measurement of the Colour of Brown Solutions with Special Reference to Tannin Extracts. HENRY R PROCTER (J. Sot. Chem. Inn?. 1923 42 73-79~).-The colours of brown solutions more especially of tannin extracts are determined by observing by means of a spectro-colorimeter the depth of solution required to reduce the light transmitted by the solution to a defkite fraction of its initial value e.g.one-half. Observations are madeANALYTICAL CHEMISTRY. ii. 271 with red yellow green and blue light of defkite wave-lengths. Alternatively colour screens of copper-ruby and copper-green glass and it screen containing a solution of copper sulphate made alkaline with ammonia may be employed to afford light of sufficiently definite composition. In this case the rotating neutral tint sector of the spectro-colorimeter is replaced by a 20% solution of iron alum and the colour of the tannin extract compared with the colour of this solution. J. S. G. T. The Estimation of Albumin by the so-called Nephelo- metric Processes.HENRI BBNARD and ALBERT LABORDE (Compt. rend. 1923 176 98-101).-A comparison of the results obtained by a diffusimeter of the type of Baudouin and Benard (Compt. rend. SOC. Biol. 1920 May) and by an opacimeter of the type of Cheneveau and Audubert ( A . 1920 ii 327) in the estim- ation of albumin in blood-serum using trichloroacetic acid as a precipitant. The final dilutions were of the order of 2-40 per 100,000. In the diffusion method a control curve is necessary at the higher concentrations. The opacimeter can be used if arranged vertically in cases where the precipitate settles rapidly as the thin sediment gives the same reading as the initial suspension. The diffusimeter is however more sensitive for very dilute emulsions. W.G. Estimation of Trypsin and Pepsin. JOHN H. NORTHROP and RAYMOND G. HTJSSEY ( J . Gen. Physiol. 1923 5 353-358).- Estimation of trypsin (or pepsin) may be effected by measuring the change in a definite time and at a given PH and temperature in the viscosity of purified gelatin to which a given amount of the trypsin solution has been added. It is found that the time taken to cause a given percentage change in the viscosity is approximately inversely proportional to the amount of trypsin added. W. 0. K. Arginase. VI. Modification of the Volumetric Method for Detecting Arginase. AKTONINO CLEMENTI (Atti R. Accad. Lincei 1922 [v] 31 ii 454-459).-1f the acid liquid obtained by the acid hydrolysis of edestin or the phosphotungstic precipitate of hexone bases obtained therefrom is treated in vitro in presence of toluene with the pulped liver of a mammifer (monkey man rat) which contains arginase a considerable increase is effected in the proportion of nitrogen titratable with formaldehyde.No such increase occurs however if the above liver is first boiled or if hen’s liver which is devoid of arginase is used. The conclusion is drawn that the increase in nitrogen titratable with f ormaldehyde corresponds with the ornithine formed by scission of the arginine by the arginase and that such increase furnishes an indication of the presence of A New Reaction of the Blood. GIUSEPPE EECCADELLI (Biochem. Z. 1922,134 180-182).-1f to 0.5 C.C. of serum or blood arginase in an organ or in an organic liquid. ‘r. H. P.ii. 272 ABSTRACTS OB CHEMICAL PAPERS. there be added equal volumes of formaldehyde (#yo) silver nitrate (0*75%) and ammonia (0*9%) after a few minutes the solution acquires a colour depending on the origin of the serum. Normal human serum gives an amber colour that of various animals a shade of yellow whilst that of syphilitics is decolorised. H. K. A Sensitive Reaction for Meo-salvarsan. K. SCHERINGA (Pharm. Weekblad 1923 68 248).-One drop of a solution of one part in a thousand gives a violet coloration to a concentrated solution of ammonimn persulphate. Colorations are given more or less quickly with other organic substances which form coloured oxidation products salvarsan also giving a violet colour but the reaction with neo-salvarsan is much more sensitive. s. I. r,. Estimation of the Grignard Reagent. H. GXLMAN I>. D. WILKINSON W. P. FISHEL and C. H. MEYERS ( J . Amr &'hem. Xoc. 1923 45 150-158).-Five methods for the es+iP ion of Grignard's reagent have been studied namely titration I dodine (cf. Jolibois A. 1912 i 675) gravimetric analysis by ti prepar- ation of some insoluble compound indirect analysis gas !alysis and titration with acid. Of these methods the first was rejected as giving resultsvyhich varied considerably with slight alterations in the condifiom the second was rejected as being unsuitable and giving low results. Of the three remaining methods the last two namely the method of gas analysis and that of titration with acid gave satisfactory results. They are based on the smooth decomposition of the Grig- nard compound with water the gas evolved being measured in one method and the basic magnesium halide titrated with standard acid in the other method. For the gas analysis method an apparatus somewhat of the type of Van Slyke's apparatus for the estimation of amino-acids is used. For the titration method the known volume of solution containing the Grignard reagent is warmed with a known excess of standard acid until all the basic magnesium halide is dissolved and then the excess of standard acid is titrated back with standard sodium hydroxide using methyl- orange as indicator. W. G. k

ISSN:0368-1769    

DOI:10.1039/CA9232405247

出版商:RSC    

年代:1923

数据来源: RSC