摘要:

ii. 72 ABSTRACTS OF CHEMICAL PAPERS. Analytical Chemistry. Rational Approximated Atomic Weights for Use in Chemical Analysis. N. SCEIOORL (Cham. Weekblad 19 1 8 1 5 547-562 ; Zeitsch. anal. Chem. 1918 57 209-225).-In ordinary analytical work it is customary to use for the atomic weights values given to the nearest decimal figure corresponding with the degree of accuracy possible for each determination. In 1904 Erdmann proposed to use atomic weights calculated from hydrogen as unity since most of the values were. very close t~ whole numbers. Since however the atomic weights of oce or two of the commonest elements cannot be rounded off to whoh numbers without intro- duction of considerable error the proposal has found little favour.A NALTTICAL C€€:E&TTTSTR3?. ii. $3 The author puts forward the consideration chat much inore satisfactory values are obtained for analytical purposes by taking account of the fact that whereas in all acciwate atomic weight determinations the weighings are reduced to the proper values for weighing in a vacuum in analytical work the correction for the weight of air displaced is seldom made.He proposes to use a set of ‘. air atomic weights ’’ obtained from the accepted atomic weights by introducing values based 011 the air correction. The acceptled atomic weight o€ iodine is for example 126.92. Allowing for the difference in specific gravity of iodine and the brass weights gener- ally used in chemical airaiysis the volume atom of iodine namely 126.92 grams weighed in a vacuum would weigh i n air.126.906 grams. Though the value of this air correction is so small as gener- ally to aifect only the third decimal place it becomes much Treater in the cases of carbon hydrogen and oxygen the elements chiefly concerned j i i organic analysis. The atomic weight of hydrogen is given by the International Committee for 1916 as 1.008. Assuming the atomic volume of hydrogen in combiliation to be 6 the “ a i r atomic weight ” becomes 1 *0005 which can without any inaccuracy be given as 1-00 for ordinary purposes. The correction for oxygen assuming an atomic volume of 6 does not’ alter the accepted value 16.00 whilst carbon with the accepted atomic weight of 12*00T> becomes 11.999 that is for ordinary purposes 12.00. Similarly the “ a i r molecular weight” of water becomes 15.00 instead of 18.02 011 the basis of the true atomic weights.The values given in the Interiiatioiial table of atomic weights for 1916 have been rnociified to give the air atomic weights for. atldytical purposes on the basis o€ the atomic volumes OC the cleiiients. The author devotes many page;; t o a selection of suit- able aC,ornic volunies for each element basing his calculatioiis 0;) Koppk law that the atomic volumes are additive. I n the case of most of the e,lements the values adopted f o r the atomic volumes are averages of very different figures; the values for cobalt for example deduced from the oxide chloride bromide sulphitle anti sulphate respectively are 7 9 2 1 and 4 the average value 5 being adopted. As the basis for the calculations for obtaining the atopic volumes of the elemepts from the specific gravities of their compounds the following atomic volumes are assumed 0 = 6 S=16 C1=15 Br=22 I=31.The atomic volumes of the halogens and of the alkali and alkaline earth metals are taken as approximately half of the values deduced from the atomic weights and the specific gravities. In order to obtain trustworthy figures f o r molecular and equi- valent weights for ordinary analysis it is suggested that use may be made of the true molecular volumes of the commoner reagents. The molecular weight of oxalic acid for example is 126.058 calcu- lated from the accepted atomic weights. The specific gravit.y being 1.64 the value to be subtracted t o arrive at the “air molecular weight” is 0.076 giving the value for use in volumetric analysis as 135.983.By addition of the air atoniic weights given in the 2” 3ii. 74 ABSTRACTS OF CHEMICAL PAPERS. {)able the value 125.976 is obtained which agrees with the figure of 125.982 obtained from the molecular volume better than does the figure 126.058 obtained by addition of the accepted atomic weights. This argument is repeated for the various reagents used in iodine determinations. It is shown also that in analysis of organic compounds for the elements use of the “ a i r atomic weights” would reduce the hydrogen content by nearly 1% ol its value and since in analysis the hydrogen content as a rule is somewhat too high i t is contended that the iiw ot’ the “air atomic weights ” will give more accnrnte re~iili~s. 8. I-.I . The Importance of Electrical Conductivity in Analytical Chemistry. I. M. KOLTHOBF (C‘hem. Weekbind 1918 15 889-896) .-The determination of conductivity can be employed in a great number of cases as an aid in quantitative analysis and is very simply and easily carried out. ‘l’hs author has indicated a Sew cases of the application leaving to later papers the detailed account and the theoretical discussion. The general cases that arise in volumetric work can be divided into two classes (1) reac- tions iu which all the ions remain i n solution; in this case the conductivity will generally increase ; (2) reactions in which ions disappear. I n t”lie second class the conductivity may ( a ) diminish ( b ) remain unaltered (c) increase. Suppose a material CD to be added in solution to a solut,ion of ALI and suppose AD to be precipitated as a result of the reactioii; the nett result is that ill the original solution the B ions remain whilst the A ions are replaced by C‘.I f the specific conductivity of A is greater than that. of C the conductivity will rise; this occurs for example in he neutralisation od a strong acid by a base the H ion being replaced by the ion of the metal of the base. I n the titration of hydrochloric acid by means of sodium hydroxide €or example the cviiductivity falls rapidly until all the acid is neutralised; if more alkali be added the conductivity begins sharply to increase. By plotting the conductivity of the solution against the quantity of alkali is added the conductivity begins sharply to increase.By iieutral point of minimum conductipity The application woulci 110 of great use for example with a strongly coloured solution for which no colour indicator could be used. I f in the above cases the conductivity of A is equal to that of C which may happen when a‘precipitate is formed the conductivity will change very little until the reaction is complete after which further addition of the second solution causes a rapid increase. Here also the measurementl can be of importance for analysis especially where the precipitate forms slowly or is microcrystalline. In the case of neutralisation of weak acids or bases the conductivity generally increases during the titration since the slightly dis- sociated acid is replaced by a highly dissociated salt. Further addition of the base causes a sharp rise in the conductivity by reason of the presence of the hydroxyl ion.If the values are plotted the neutral point can easily be determined and the methodANALYTIUAL CHEMISTRY. ii. 75 is of wide application iii this case since colour indicators are not' available with weak acids and bases. Further applicatioiis are for example titration of a weak acid in the presence of a stroiig acid determination of the combined alkali in a salt of a weak acid determiiiatioii of basic or acidic properties of a substance as for example the acid character of hydrogen peroxide etc. Siinilarly the concentration of an electro- lyte can be determined from the conductivity with the help of tables and determinations of conductivity combined with specific gravities or other physical constants can be used for analysis of a rnisture of two electrolytes.I n food analysis also the deter- The Effect of Dilution in Electro-titrimetric Analyses. mination may be of great use. s. I. I,. GILBERT ARTHUR FREAK (T 1919 115 55-61) The Quiaone Phenolate Theory of Indicators. Spectro- photometric Study of the End Points and Fading of Phenolsulphophthalein Indicators. CHARLES I;. BRIGHTNSN ,T. J. HOPFIELD M. R. MEACHAM and S. F. ACREE ( J . Bmw. Ch e m . Soc. 1918 40 1940-1944) .-The present communication deals with phendsulphophthdein and its tetrabromo- and tetrs- riitrorderivatives. It is found that these indicators have a number of properties which make them the best series yet developed. They are twice as deeplv coloured as phenolphthalein in alkaline solution and show sharper colour changes. The excess of alkali necessary t o produce the end-point of the neutralisatioii of the indicator does not caixse any appreciable fading in either short- or long-time periods in the case of phenolsulphophthalein and its tetrabromo- derivatire.The colour of phenolsulphophthalein in phosphate buffer solutions does not fade appreciably even in considerable periods of time. Staudsrdised stock solutions of phenolsulphophthalein can he kept. in an ice-box without appreciable change or even at. ordinarv teni peratureq if care is taken to prevent contamination and will then show the same absorption index when treated with an excess o f alkali a t different tiriie neriods. Different samples of the saiiie lot of solid pheiiolsulr~hcphthalein will give the same ahsorption iiidex when treated with an excess of alkali.An excess of alkali in solutions of te.tranitrophenolsL~rlpho- 1)IiLhaleiri causes a fading of the iiitcrise I-ed colonr to a light vellow I l i c t i m e OF Farliny dependiii,i; on the amount of alkali and other c ii 17 e r iin e 11 Gal co 11 di ti 017 s . Details of the es~)er.imerital niethod: are promised in a sub- q i r e i r t paper H. w. The Elimination of the Volume of a Precipitate. H. 13. STEENBERGEN (Chem. TVeeTzbZnd 1918 15 1268--1269).-1t is somethes convenient in order to avoid the washing of a pre- cipitate to make the estimation of a soluble constituent of a solu-ii T7ci ABSTRACTS OF CHEMICAL PAPERS. tioii in presence of the precipitate. This may be done by diluting trhe mixture to two known volumes and estimating the coiiceiilratiou of the solution in each case.A simple formula involving the con- centrations thus fourid is given for the correction required fur the volume occupied by the precipitate. Mi. S. M. The Significance of the Electrical Conductivity in the Analysis of Potable Water. I. M. KOLTEIOYF (ChP772. Week- blad 1918 15 1160- 1183).--The determination of the eleckical conductivity has been used by Reichert Kohlrausch and Holborn and others as a rapid method for estimating the total solid con- stituents in ordinary potable waters. For this purpose a mean equivalent weight and a mean equivalent collductivity are assumed. The author shows how untrustworthy are the results obtained by this method with different types of water.A series of measure- ments on the conductivity of dilute aqueous solutions of those salts which are ordinarily present in drinking-water such as sodium hydrogen carbonate chloride and sulphate potassium nitrate calcium ch1oride and sulphate magnesium chloride etc. and oE binary mixtures of t'hese establishes the rule! that the degree of dissociation of each salt' in the mixed solution is that which corre- sponds with the total coiicentration of electrolyte even in the case where the salts have no common ion. By means of this rule the author has prepared tables which permit the calculation of the equivalent conductivity of a mixture when the chemical composi- tion of the solution is known. The comparison of the calculatet1 and the measured conductivities of a water affords a check on the chemical analysis. w.s. M. Chlorometry. OCTAVE LECOMTE (Bull. Sci. Phurmacol 1918 25 217-218 ; from Chem. Zentr. 1918 ii 762-763).-The author estimates the active chlorine in bleaching powder or in hypochlorites by titrating a known quantity of sta,nnous chloride with ,I 10-potassium permanganate first with and then without the addition of the hypochlorite solution. 33. W. B. Detection of Hydrogen Chloride in Chloroform. D Neutral chloroform when shaken with a very small quantity of tliiiiethylaminoazobenzene gives a yellow-coloured solution ; if the chloroform contains a trace of free hydrochloric acid the yellow coloration changes t o violet-red. Carbon dioxide and anhydrous formic and acetic acids in chloroform solution do not gioe a red coloration with tlimethylaminoazobeiizene. [See further ,7.S o r Volumetric Estimation of the Sulphion. 13. HOWDEN ((:hem. Neuw 1918 117 383).-A rapid approximate method for the estimation of soluble sulphates of the alkali metals in solution is based on their decomposition by barium carbonate. The sola- Lion is shaken with pure precipitated barium carbonate in ~Tol?,LA~NDER (Bet'. d C / l t . ThGrm. {;CS. 1918 28 385-388).-- CILc.?lt. h 7 . 1919 tirin.] w. P. s.ANALYTICAL CHEMISTRY. ii. 77 yreseiice of phenolphthalein and standard hydrochloric acid is then run in until the red colour is discharged. The solution is filtered and the titration completed on the filtrate using methyl-orange as indicator.The addition of acid before filtration appears to be necessary t o complete the decomposition of the soluble sulphat,e by the barium carbonate. [See also J . Soc. Chew,. Z r i d . 1919 578.1 E. H. R. F o b ' s Direct Nesslerisation Method for the Estimation of Nitrogen. LOVELLANGSTROTH (J. Bid Chenz. 1918 36 377--38O) .-Accurate resu1t.s are obtained even when impure sulphuric acid is employed for the digestion provided the necessary corrections are made the latter beine ascertained bv control blank experiments (compare' Folin and De& A. 1916 ;i 573). H. W. B. Estimation of Phosphorus by the Nephelometric Method. Accurate estimations of phosphorus by rneaiis of the strycliiiine inolybdate reagent (compare Kober and Egerer A. 1915 ii 794) can only be obtained by adhering strictly to the prescribed pro- cedure.H. W. B. EDWARD B. J~EIGS ( J . UiOZ. C'?Le'l)L. 1918 36 335-346).- - Action of Iodine on Hypophosphorous Acid and Phos phorous Acid. Application to the Estimation of Hypo- phosphites and Phosphites. BOYER and BAUZII ( J . Pharm. Chiin. 1918 [vii] 18 321-334) .-In sulphuric acid solution iodine oxidises hypophosphorous acid to' phosphorous acid accolrding t o Lhe equation H,PO + I + H,O = H,PO + 2HI. This reaction requires about ten hours for completion. The oxidation proceeds a stage further if the solution is treated with an excess of sodiuiw hydrogen carbonate the phosphorous acid being then converted into phosphoric acid €X,PO + I + H,O == H,PO + 3HI. I n this case two hours' contact is required and the mixture must be acidified with acetic acid before the excess of iodine added is titmted.[See further 7. SOC. Chem. Ind. 1919 Febrnary. 1 IV. P. s. A Modified Scheibler Apparatus for the Estimation of Carbon Dioxide. M. J. VAN'T K R U Y S ( C ~ ~ ~ . Weekblad 1918 15 870--872).-1n order to meet the need for a Scheibler. apparatus a t the Agricultural Testing Station at Maastricht and i n view of the shortage of rubber in Holland a modification of the original apparatns has been made. The rubber bag and the three- flecked bottle in which this is contained between the reaction flask and the gas-measuring apparatus have been removed. The error which would have been caused had the carbon dioxide evolved been allowed to come into contact with the water in the measuring vessel is obviated by usingl water saturated with carbon dioxide.ii.78 ABSTRACTS OF CHEMICAL PAPERS. In its modified form the apparatus is found to give more accurate results than in the original form. s. I. L. Estimation of Carbon Dioxide in Carbonates. DONALD D. VAN SLYKE ( J . Bid. Chem. 1918 36 351-354).-The carbonate either pulverised or in solution is placed a t the bottom of a test-tube 30 to 25 mni. in diameter which is placed in a 250 C.C. suction flask containing an excess of N/lO-barium hydr- oxide solution. A rubber stopper carrying a small dropping funnel is inserted into the flask so that the bottom ol" the funnel dips into the test-tube. The flask is then exhausted t o a presstxre of 50 mm. or less and the outlet closed with a screw clamp.An excess of N-hydrochloric acid usually about 5 c.c. is admitted slowly from tKe funnel. When the rapid evolution of carbon dioxide has ceased the solutions are both agitated by a rotary motion for three minutes. I n the case of most substances this period is sufficient for the complete transfer of carbwi dioside from the inner tube to the bariizm hydroxide solution I n the analysis of unaslied animal tissues a longer time is necessary and in the case of bones a t least two hours should be allowed the solutions being stirred by rotation occasionally during this period and coil- tinuously for three minutes a t the end of it. When the reaction is completed the vacuum is released the barium carbonate filtered off. and the filtrate titrated with N / 1 0 - hydrochloric acid using phenolphthalein as indicator.The method appears t o be applicable to all carbonates soluble or iizsoluble in the absence of acids such as hydrogen suhhide. which are highly volatile from aqueous solution. H. W. B. A Physico-chemical Method of Estimating Alkali Carbonates in the Presence of Alkali Hydroxides. Ap- plication to the Analysis of Flue Gases. R E N ~ DUBRISAP TRIPIER. and TOQUET (Compt. ?-end. 1919 168 56-59).-Tf 50 C.C. of various solutions having the same alkalinity but con- taining varying proportions of sodium hydroxide and sodium carbonate. are mixed with 50 grams of phenol heated until solu- tion is complete and then allowed to cool it is found that) the temperature a t which the solution first becomes turbid is higher as the proportion of sodium carbonate to sodium hydroxide increases.The aut-hors have plotted curves for solut.ions having respectively a total allralinity of gLV. *V AT/? and N / 4 showing the relationship of temperature to sodium carbonate present. By weans of thece the amount of sodium carbonate in a qiven solir- tion containinq both carbonate and hydroxide may readily be deter- mined by bringing the total alkalinity up t o one of the four strengths given above by addition of sodium hydroxide then pro- ceeding as described above and reading off the amount of sodium carbonate present from the curve. For the determination of the amount of car-bou dioxide ptwent; in flue gases 1 litre of the gas is bubbled through 71-5 C.C. cfANA.LY TICAL CHEMISTRY. ii. $1) S i 4-sodium hydroxide and then the above estiiiiation is carried out on the resulting liquid the amount of carbon dioxide presejlt in the flue gases being readily cakulated from the amount of sodium carbonate found in the solution.w. G . Estimation of Alkali Hydroxide and Alkali Carbonate in Alkali Hypochlorite Solution. M. PHIL~BERT ( J . Pharrit Clztim. 1918 [vii] 18 260-272).-The total alkalinity is found by treating a portion of the sample with a meastired excess of J/ 10-hydrochloric acid and -potassium iodiLie solution titrating the liberated iodine with thiosulphate solution then adding polassiuiti iodide-iodate solution and again titrating the iodj ue with iliici- sixlphate solution ; the latter titration is a measure of the quantity of the added acid which remains uncombined and the difference corresponds with the alkalinity of the sample.To estimate t h e free alkali hydroxide another portion of the solution is treatetl with a measured quantity of N / 10-barium hydroxide solution barium chloride solution is also added the mixture diluted t o :t. definite volume filtered andl the alkalinity of the filtrate titmterl as described above. The difference between the quantities of free and total alkali gives the amount of alkali carbonate. [See further ,7. SOC. Chenz. Tnd. 1919 February.] IV. P. s. Carnot's Method €or the Estimation of Potassium Salts. CAROLINA ETILE SPEGAZZIXI (,4nal. SOC. Quim. Argentinn 1918. 6 196-209) .-Analyses according t o the original prescription of Cariiot (this Journal 1877 ii 921) gave results in every case much too high.The same method as modified by Grandeau and by Fresenius also gave high results. It is essential in the preparation of the bismuth chloride solntion from the subnitrate to give particular attention t o the acidity and temperature of the resulting solution the optirnuni acidity being determined by precipitatioii of a known quai.rtit-j7 of potassiuui froin AT/ 10-solution. Good results were obtained oiilv with pure dilute solutioiis of Tdassiuin chloride (,!!I 20-,7c'/ 1). Nitrate solutions also gave good iwults but with sulphate solutions the results were mnch too low. With mixtures of potassium chloride and calcium chloride mag- t!esiuni chloride or sodium chloride. the method is satisfactory only \ v h e ~ ~ the pot,nssiiim salt is in excess.w. x. nl-. Method for the Estimation of Potassium in Blood. S. W. CLAUSEN {,7. RioZ. Clzem. 1918 36 479--484).-Two C.C. of plasma or 1 C.C. of blood are oxidised by boilirig with 5 C.C. of a niixture of sulphuric and nitric acids (I 20) f o r half an hour. T ~ P excess of nitric acid is quickly evaporated and tJhe residual liquid washed into a beaker rendered alkaline and then evaporated t o dryness. The residue is taken up in glacial acetic acid and t h o potassium precipitated by sodium cobaltinitrite. The precipitatn is collected and then heated with dilute sodium hydroxide whichii. SO ABSTRACTS OF CHEMICAL PAPERS. changes all the nitrite groups to sodium and potassium nitrite whilst the cobalt is precipitated as the insoluble hydroxide. The nitrites are then estimated by acidifying with sulphuric acid and titrating with permanganate a t TOo.The method appears to give accurate results. Gravimetric Analysis. VIII. Separation of Calcium from 1Magnesiuz-n. L. W. WINKLER (ZeitscTz ciizgezo. Cheiiz. 1918 31 214-216).-The following niethod was found to be the most trustworthy for the separation of calcium aiid mag- nesiimi. The neutral solution nieasuring 100 C.C. and contain- ing not more thaii 0.1 gram of calcium and 0.05 gram of magnesium is treated with 3 grams of aniinonium chloride and 10 C.O. of A17/l-aceiic acid then boiled and 20 C.C. of 3-506 a~nmoniuin oxalate soliitioii are added slowly. The pre- cipitated calcium oxalate is collected after twenty-four hours dried at( looo and weighed. The magnesium in the filtrate is precipi- tated and weighed as ammoniiim magnesium phosphate (compare THOS.STEEL (A?znZyst 1919 44 29).--In the method proposed by Waddell (A. 1918 ii 4W) the use of water saturated with barium chromate is recom- inelided for washing the precipitate of barium chromate. [See Estimation of Copper by Means of Potassium Thio- cyanate Potassium Iodide and Thiosulphate. I. M. KOLTHOFF (C'lzem. Zeit. 1918 42 609-610).-The process ae described by Bruhns is criticised arid niodificatioiis are suggested ; trustworthy results are obtained if the copper solution is acidified with sulphuric acid after the potassium iodide has been added. The method may be used for estimatirig the excess of copper in sugar estimations and for estimating copper in the presence of iron provided that sodium pyrophosphate is added to inhibit the action of ferric salts.[See further ,7. Soe. C'?ieui. Zd 1919 February. Estimation of Copper and Sugar. G. BRUHNS (Zeitsc3z. cri/<gciu. GJwm. 1918 31 246).-A reply to Sclioorl and Kolthofl's iriorlification of the method dexribed originally by the author. (A A Very Exact and Rapid Method for the Estimation of Mercury in the Majority of its Compounds. S. PINR DE RUBIES (il?Lal. Pis. Quim. 1918 16 661- -689).-The method pro- posed is a combiuatioii of the niethocl of Rose-Finkener and t"hat of Eschka combining the accuracy of the former with the rapidity of the latter. A critical discussioii of both methods with tphe niodi- ?cations introduced by Comining and Macleod and Biewend ant1 Holloway is given together with a bibliography of recent litera- ture 011 the subject since 1914.The new method as applied to the analysis of mercury minerals H. W. B. A 1918 ii 455). w. P. s. Volumetric Estimation o€ Barium. further J . SOC. Cheiir. Tiid. 1919 February.] w. P. S. TV. P. S. 1918 ii 2'76). \v. 9. s.AXALYTICAL CNEI\IISTRY. ii. 81 is as follows. The mineral is mixed intimately with fine iron powder and is carefully heated in a porcelain crucible into which is closely fitted as a cover a small crucible of gold or silver for the condensation of the volatilised mercury. The cooling of the upper crucible is effected by means of a Finall bladder of iiidiarubber which when distended by a steam of cold water is in close con- tact with the whole interior surface.After cooling the inner crucible is washed with alcohol aiid the weight of the condensed mercury film deterniined. The results obtained by this procedure showed a maximum error of 0.077L. In the case cf more volatile compounds of mercury organic and inorganic anhydrous potassium carbonate and barium peroxide either separately or mixed. are substituted for the iron powder. Wheii the substance to be ssialysed contains much moisture for example a solution a weighed quantity is evaporated to dryness if1 the porcelain crucible after the addition of sodium sulphide and the mercury is determined as before. The methoa is applicable without special modification t o the aiialysis oE mercury fulminate aiid fulminate mixtures. W. S. M. Analysis of Aluminium Alloys.A. TRAVEKS (Cbiitu. ct Iud. 1918 1 708-711).-The alloy is heated with sodium hyctr- oxide solution containing a small quantity of sodium carbonate and the mixture is filtered. The filtrate contains the zinc and aluminium ; the zinc is precipitated as sulphide and estimated acidimetrically after precipitatioii as arniiionium zinc phosphate whilst the aluminium is estimated by Stock's method. The in- Foluble portion of the alloy k then rlivsolved in nitric acid the solution boiled with the addition OF animonium persulphate the iron and niangau ese precipitated with ammonia the precipitate then dissolved in hydrochloric acid and the iron titrated with titanium trichloride solution ; manganese is estimated in a separate portion of the alloy by the persulphate method.I f cobalt and nickel are present they mu4 be separated as sulphides before the iiiaiiganese is estimated ; cobalt is precipitated by meaiis of B-nit'l-o~oi7aplith 01. The magne5iuiii is estimated in the filtrate from the iron and mnngc?nese precipitates and copper is estimated iodometrically in a separate portion of the sample. [See further 147. P. s. Analysis of Aluminium Alloys and Metallic Aluminium. J . 5. Fox E. 117. SBELTON and F. R. ENSOS (,7. Soc. CJrem. Ind. 1918 37 328-333~).- -A cletxiled description is given of methods suitable f o r the separation of lead manganese silicon copper tin iroii zinc nragnesiam and nickel in aluminium and in aluminium aIIays containing a low or high proportion of zinc. Estimation of Molybdenum in Ferromolybdenum. W. I~OEPFNER and 0.BINDER (Ghenr. Zeit. 1918 42 564).-A weighed quantity of about; 0.5 gram of the sample is heated with .7. ,COC. CAeiti. J n d . 1919 February.] W. P. S.l i . 82 ABSTRACTS OF CHEMICAL PAPERS. nitric acid (D 1*2) sulphuric acid is then added and the heating continued until sulphuric acid fumes are evolved; the solution is diluted t o 250 c.c. heated with the addition of a few drops of nitric acid and the iron precipitated with ammonia. The pre- cipitate is dissolved in sulphuric acid and reprecipitated. The two filtrates which now contain all the molybdenum 2re mixed. treated with 50 C . C . of ammonium sulphide then acidified with sulphuric acid and heated. The precipitated molybdenum sulphide is ~olfect~ed and weighed or it may be converted into molybdic acid by ignition.Traces of impurities may be separated by dis- solving the molybdic acid in ammonia. Copper,..if present may be separated as described previously (A. 1918 11 372). w. P. s. The Precipitation of Zirconium Phosphate. GEORGE SL~ISIGER ( J . It’ashington A cad. Sci. 1918 8 63T-639).--1~1 estimating zircsuiam in minerals by precipitation as phosphate the coniposi- tjori of the precipitate approximates more closely to that of normal xircoriinni phosphate as the acidity of the solution increases. The presence of as much free sulphuric acid as possible is advisable to prevent simultaneous precipitation of iron and titanium phos- 1111 ates whilst thorough oxidation with hydrogen peroxide is also necessary to prevent titanium precipitating. At leastA 3% an tl Iiossibly as much as 5% of free sulphuric acid may be present without interfering with the accuracy of the results.Other phos- phates with the exception of those of the rare earth metals are readily soluble in the acid solution and may be separated from the filtrate. [See also J . SOC. Cheqz. Ind. 1919 February.] C. A. M. Analysis of Commercial t 4 Pure ” Benzols. F. BUTLER JONES ( J . SOC. Chem. Znd. 1918 37 324-327~).-h a mixtui*e containinj benzene thiophen toluene carbon disulphide aiid ‘ I paraffin,’ the quantity of carbon disulphide is proportional to thlze diff welice between the freezing points of the misture before atid after its removal; similarly the subsequent rotnoval of the fhiophen (by means of basic mercuric sulphate) also results in a clifferelice in the freezing point which is proportional to the ainount o f substance removed. The residual liquid is a mixtme of benzene.1 oluene and “ paraffin ” the difference between i t s freezing point and that of pure benzene gives the sum of the amounts of tolueiic illld ‘fparaffin” present; tho specific gravity of the liquid in cow iuiictioii with the freeziuq point affords R means of estimating these two constituents. A graph is given for solving the forit- quations involved. w. P. s. Modification of Webster’s Test for Trinitrotoluene in Urine. F. TUTIN (Lartcet 1918 ii 554; from Physiol. Abstr. 1918 3 452).-The urine is extracted with ether acidified with mineral acid and agaiii extracted with ether ; in the second extract,ANALYTIOAL CHBMISTRP.ii. 53 ail azoxy-compound from trinitrotoluene gives a violet coloration with alcoholic potassium hydroxide. The modifications now pro- posed are in part minor ones such as the number of times estrac- tion is performed but art important change consists in extracting the final ether extract with dilute sodium carbonate solution; this removes substances which mask the characteristic colour of the Webster reaction. H. W. B. Estimation of Small Quantities of Ethyl Ether in Ethyl Alcohol. H. J;. Cox (Analyst 1919 44 26-2T).-The method depends on the fact that alcohol of 99% and upwards distils iinrhanged; any ethyl ether present passe.; over in the first frat- 1 ioiis and a mixture of constant boiling point is [lot formed. 'The amount of ethyl ether may therefore be estimated from the specific. gravity before and after distillation the specific gravity of the alcohol being taken as that obtained after removal of the ethyl ether..[See further ,7. SOC. C'henz. Ind. 1919 February.] w. P. s. The Use of Diastatic Reagents. (11) The Detection of Pyramidone and the Differentiation of the Naphthols. LUCIANO P. J. PALET (Arzal. Soc. Quim. Argentina 1918 6 250-257).-To the solution of pyramidone are added some small pieces of the root of lucerne which contains oxydases and per- oxydases. A violet-bltie colour is protliiced o n the root fibres oil keeping. The addition of hydrogen peroxide accelerates the :tppertrance of but docs not intensify the colonr. The fiirthet- :ttfdition of a-naphthol immediately produces an intense wine-red (wIour characteristically cliff ereiit from that ~~roducecl by P-naphthol.This constitutes a delicate kest for the greseuc'e of Assay and Estimation of Nitroso-P-naphthol. YAUI NXCOLARDOT and LUCIEN VALLI-DOUAU (Bull. Soc. ckirn. 1918 iiv] 28 455-459).-For the assay 2 grams of the material dried a t 3 5 O are dissolved in 120 C.C. of acetone in the cold diluted to 200 C.C. with water and 100 C.C. of this solution is titrated with i L 1.5% solution of iron alum previously standardised against piire iiitroso-P-naphthol the end-point being shown by means of ammonium thiocyanate as an external indicator. For an exact estimation an excess of iron alum is added t o the solution prepared as above and the precipitate formed is left over- night collected washed free from iron salts with water dried at ?Oo and weighed. sinnll quantities of a-naphthol in &naphthol.w. s. N. It contains 90*776 of nitroso-&naphthol. W. G . Volumetric Estimation of Reducing Sugars. A Simpli- fication of Scales's Method for Titrating the Reduced Copper without Removing it from the Residual Copper Solution. W. BLAIR CLARK (J. Amer. Chem. Soc 1918 40 1759-1772. Compare A. 1916 ii ll'l).-The principle of theii. 84 -4BSTRACTS OF CHEMICAL PAPERS. method here described is as follows. The sugar solution t o be analysed is boiled under standard conditions with a copper citrate- carbonate solution and the cuprous oxide dissolved by means of hydrochloric acid. Standard iodine eolutioii is then added t o osidise the cuprous salt a i d the excess of iodine titrated by 3neans of sodium thiosulphate. To obtain corisistent results it is ueces- sary to carry out the whole operation under exactly standard con- ditions.These conditions and the strengths of solutions to be used are indicated for quantities of reducing sugar up t o 0.075 gram. It is essential however for the worker t o standardise his own conditions. The sugar. factor of the sodium tliiosulphate must be deterinined on a known sample of reducing sugar usinr a,pproxiin- ately the same quantity as t h a t to be determined and the same conditions of reduction. The ratio of copper t o reducing sngar is approximately constant. the greatest variation occtirring with small quantities of sugar. It was found that sucrose in quantities not exceeding 100 q.per 10 C.C. and 50% ethyl alcohol do not reduce copper ciirate- carbonate solution but 10y6 formaldehyde effects a sinall reduction. [See also +7. SOC. Chem. Irtt?. 1919 Febriiary.1 E. 1%'. R. Source of Error in the Use of Picric Acid in Colori- metric Estimations in Biological Fluids. .fitICE ROHDE and shown t h a t picric acid which has been preserved in a moist eondi- lion for several months loses Forno of its power of precipitating cliroinogenic substances in the blood. The use of such picric acid far the estimat3ion of destroc;e in the blood by the Benedict.Lewis colorimetric method would yield too high values. The Colorimetric Estimation of Sugar in the Blood by the Reduction of Picric Acid. C. SALOMON (Eioclzenz. Zm'tsch. 1915 90 39-52).-As a result of the critical examination of the method of Lewis and Benedict and its modifications the author arrives a t the conclusion t h a t it has considerablo value as regards accuracy and speed f o r clinical investigations.Estimation of Dextrose in the Blood. F. HAMEL (BzdZ. Rci. Phurmacol. 1918 25 223-224 ; from Chcm. Z e ~ r t r . 1918 ii 769).-Ten C.C. of venous blood are treated with 10 C.C. of a 10% solution of trichlorcacetic acid and after removal of the precipitated protein the dextrose is estimated by Fehling's solu- tion in the usual way. Estimation of Sugar in Milk and Urine. B. SJOLLEMA (Chem. IVeekhZnd 1918 15 1483-1485).-The method of Folin and Denis (A. 1918 ii 208) for estimating sugar i n milk and urine is recommended. A. J. W. nxARION SWEENEY ( J . Bid.Cht'n7 . 1918. 36 475-477).-1t i S H. W Iz. S. B. S. H. W. B. Estimation of Lactose. E. Hmwr (Compt. q-eizd. 1918 167 756-759).-For the determination OF lactose ill milk in whichthe sugar has undergone more or less hydrolysis the author recom- mends completing the hydrolysis by means of sulphonic acids such as those of benzene or phenol or those described by Twitchell (A. 1900 ii 396) and determining the cupric reducing power. One 36 solutions of these acids hydrolyse 0*5:! solutioiis of pure lactose in four hours a t looo but milk serum requires longer heating. No destructio8n of galactose occurs as when mineral acids are employed. I n the determination of rerluciiig power usirig 10 C.C. of boiling alkaline copper solution 0.0506 oram of hydrolysed lactose is equivalent in reducing power to O.i'i08 grain of lactose hydrate 01' 0.0495 gram of invert-sugar.Considerable destruction ol sugar takes place when the solids o€ milk which has become uiisound are dried at looo ; this is attributed to the formation of nielanoidins (see Maillard h.. 1919 i 169) by interaction of sugar and proteolytic prodncts. [See further Micro-estimation of Lipoids by Titration. IVAR BANG (Biocliem. Zeitsch . 1918 91 86-103j.-The fats are osidised by 110-potassium chromate solution a t the ordinary temperature in presence of excess of sulphuric acid. Excess of chromate solution is then estimated by the addition of potassivm iodide and the titration of the liberated iodine by thiosulphate solution. The fat {from blood etc.) is taken up i n benzene solution a little alkali is added (to emulsify the fat) and then the solvent is distilled off.C?iolest-eiol can be estimated in the same manner (and the same factor is used in making the calculations; this factor is determiued empirically as under the conditions of experiment employed thc oxitlation is not complete). When cholesterol is present with fats. the determination of both constitnents can be made by precipitx- tioii of the cholesterol as digitonide which is insoluble in benzene. When cholesterol esters are present with fats the determination of the amounts of the constituents can be made in two ways. Either a strength of alkali can be einployed which will hydrolyse the fats but not the cholesterol ester which can then be separated from the soaps by benzene o r sufkient 'alkali can be added to sapoaify both fgts and cholesterol esters and the cholesterol can then be extracted by benzene and estimated separately.In another portion fats and esters can be estimated together by oxida- tion. A series of experiments on the oxidation of the lecithides is also described. S. B. S. The Micro-estimation of the Lipoids of the Blood. IVAR BANG ( B i o c h ~ n ~ . Zeitsch. 1918 91 235-25G).-An amplifica- tion of the author's micro method (preceding abstract) is given. Cholesterol and neutral fats are extracted first by a fraction of light pet'roleum of low boiling point! containing chiefly pentane. TheFe can be separated by the method already given using the digitonin compound of cholesterol. After extraction with petroleum t>he blood is extracted with 92"/ alcohol in the cold.This fraction contains the phosphatide and the cholesterol esters. 07. ICOC. Che?E. Illd. 1919 5 1 A . I J . H. TA. S. B. S.ii. $6 ABSTSA4CTS OF CHEMTCATA PAPERS. Gravhznetric Estimation of Glycyrrhizin. A. ASTRUC and (MmE.) Gr. PICHARD ( J . fjhurrn. Chinz. 1918 [vii] 18 389-290).-Three grams of dry liquorice extract are dissolved i-u 30 C.P. of water containing five drops of ammonia the solution is liltered and 20 C.C. of the filtrate are treated with 2.6 C.C. of stllphuric acid ; the precipitated glycyrrhizic acid is coIlected after twenty-four hours washed with 30 C . C . of water then dissolved i n itnimoriia arid t)hci solution evaporated. The residue is dried at IihF and weighed; to the weight ohtaineti is added 0.04 gram as ;L correction for the soliubility of the glycyrrhizic acid in the wash- wntw.[See fiirl-hci* .T. ,SOV. ( ' ~ V U ) . r'nfl. 1919 February.] w. P. s. A New and Delicate Reaction of Pyramidone and its Differentiation from htipyrine. LUCIANO P. 3'. PALET (AnaZ SOC. Qwirn. ilygentina 1918 6 151-155).-The author finds that an acid solution of pyramidone when treated with a few drops of an acid solution of pot3assium ferricyanide and ferric chloride gives an intense blue coloration and precipitate of Russian-blue. The test is very delicate. WitEh antipyrine a blood-red colour is obtained with the same reagent. This colour is converted into a pale yellow by the addition of a few drops of hydrochloric acid. The test is therefore carried out in hydrochloric solution which perinits the blue due to the presence of pyramidone in a mixture t 0 emerge. In this way I / l o 0 part.of pyramirlone may be detecbed i i r o m part of antipyrine. Phenacetin acetani'tide. aq~iriu esalgin ant1 caffeine give no w. s. &I-. The Reaction of the ' Ferri-ferric 'I ' Reagent with Alkaloids Glucosides and other Vegetable Principles. LUCIANO P J . PALET (Anal. SOC. Quim. Argentilza 1918 6 156-158).-An exteusion of the application of a mixed solution of potnassium ferri- cyanide and ferric chloride as a reagent (see preceding abstract) t o the characterisation of alkaloids glucosides and other substances of vegetable origin. Of 103 substances of this kind tested 42 gave a positive reaction t t i t t t is a more or less intense blue coloration.r*cw"tio;n with t h e reagent. W. S. M. Estimation of Phenacetin and other p-Aminophenol Derivatives by Means of Hypochlorous Acid. *4. D. POWELL (Analyst 1919 44 23-25).-For the estimation of paminophenol rpphenetidine etc. the substance is treated with hydrochloric acid and sodium hypochlorite solution the excess of chlorine is removed by a current of air potassium iodide is then added and the liberatied iodine titrated with thiosulphate solution. I n the first phase of the reaction p-benzoquinonechlorimine is formed ; this after the removal of the excess of chlorine reacts with hydriodic acid liberating four atoms of iodine p-aminophenol being re-formed. In the case of phenacetin a preliminary boiling for two hours with hyclrochloric acid is necessary.Each C.C. of N / 10-thiostxlphateANALYTICAL CYHENIYTRY ii. S’i solution is equivalent to 0.00273 gram of y-aniiiiophmol 0.00343 grain of p-pheiietidine or 0.00448 gram of pheiiacetiii. [See Arsenotungstic and Arsenotungstomolybdic Complexes as Reagents for Phenolic Amines. LUIS GUGL~ALMELLI ( A mil. ,Vor. ( ) u i t t i . - 1 t * y ( ~ t i t i ~ t ~ ~ 1918 6. 185- -195).-Redgents prepared l ~ y Imiliug solutions of sodium triiigstat e bvith arbenic acid and a mix- ture of wxliuni tuiigstate ant1 inolybdate with ar-enic acid ulitil (*oncelitrated hydrochloric acid 110. loiiger produces a precipitatc have beeii showii to give delicate colour 1-eactions with phenols aiid so1iie purioe derivatives The same reactioii that is an intense blue coloiir is given by phenolic aniines.The author. has investi- gated a large iiumbei. of substances of this class aiicl also nitro-. sulphoriic and hydrosy-derivatives of these. Positive results were given with the fii t reagent with the substances NH;OFT compouncls c*ontaiiiiiig the same groiips separated from each other b u t united directly t o a benzene naphthalene ptiriiie or pyrazoloiie iiucleus. The second reagent reacts with substances containing the same groups and iu addition \ d h substances contaiiiiiig one Estimation of the Carbamide Fraction in Blood. HrmrucII SCHUK and FRANZ URBAN (l17icti. A l i r i . Il-oc’J1~iisc~ir. 1918 31 892-896 ; from C‘hvnt. X ( / i / t r . 1918 ii G73).-The blood serimi is freed from albuiriiti by t reatnientu with sulphosalicylic acid solit- tioti (20?/,) ; nitrogen is estiniatecl by means of bromine and socliirni hydroxide in accordance with the method of Knop and Iiiifiier.H. ?V. further .I. S O P . ( f h t ) t t t . J t t t l . 1919 February.] w. Y. s. N€€,-NH NIIR-N ? NI-TR-X€IR NHR-OH and also with amino-group. for example aniline. w. s. ?rl. Detection of Quinine. Kizus S a ~ o ~ o s ( U ~ T . t l c r i t . I J ~ ( ~ I . W L . Gcs. 1918 28 :>73--275) .-The green coloration obtained wheii a qiiiniiie solution is treated with chloriiie and theti with m i i i i o i i i ; ~ will detect 1 part of quinine in 10,000. The fluorescence olwsved when a quinine solution is treated with dilute sulphiiric acid will cletect 1 part of the alkaloid in 300,000 parts. It is advantageoils to use bromine-water in place of chlorine in the above test siiice it is easier t o add just t h e requisite quantity; the bromiiie is acldecl until the solution is coloured sliqhtly yellow.Another sensitive reagent for quiniiie consists of potarsiuni iodide (10 granis). niercuric chloride ( 2 - i grams) water (200 grams) and glacial acetic acid (2-3 grains). [See flirther. .I. ,i’or. Pltcrit. Iiid. 1919. W. KANSJ)ES I. J . LTPKIN arid E. WZIITLRE’ (,4 n i i . Trop. .Mtv7. Pm-isitoT. 1918. 12 233-358).- See thih vol. i 106. Estimation of Morphine in Complex Products. I. Revision of the Analytical Reactions Involved. AmRm TINGLE (-4 m p r . .7. Phcirm. 1918 90 689-7O6).- -A disciissioii of .5 4 A . 1 w. P. s. Estimation of Quinine in Animal Tissues.various methods and reactions used in the estimation of’ inorl’hiiie ; the acidimetric method arid iodometric method (clepeiidiiig on t he formation of the periodide) are trustworthy but the iodoacidi- metric method cannot be used.In methods where the rtiorphine is precipitated by aiiimonia the presence of alcohol should be avoided. Barium hydroxide solution docs not dissolve morphiiw completely in the presence of lead acetate. The statwnciit i n the British Pharmacopwia thatp morphine tartrate gives the reactions of morphine and of tartrates is substantially correct. [.See further ,7. (‘he???. 17nd.. 1919 ~?A.I v. P. s. Estimation of Morphine in Complex Products. IX. Mixtures containing Morphine as a Simple Salt. ,~LE’REI) TINGLE (dmer.. ,7. Pliar17~. 1918. 90 7E8-795).--The following met.hod is described for the estiinatioii of morphine in powders pills etc.provided that the alkaloid is iiot present in the form of opirmi. Six grams of the sample are wariiied with 2 grams of calcium carbonate and 20 C.C. of water iintil disintegrated 60 C.C. of cold saturated bariuni hydroxide solution are then added the mixture is shaken diluted to 100 c.c. and filtered. Fifty C.C. of the filtrate are treated with dilute sulphiiric acid in quantity just- sufficient t o precipitate the barium the mixture then diluted to 56 c.c. and filtered. Fifty C.C. of this filtrate are neutralised with sodinni hxdroxide solution then rendered Plightly acid with hydro- chloric acid evaporated t o 5 c.c. and extracted five times with a mixture of chloroform and alcohol ( 2 l ) after the solution has been rendered alkaliiie by the addition of a slight excess of saturated sodium hydrogen carbonate solution; 25 C.C. of the solvent are used each time. The residue obtained on evaporating the solvent from the extract is titrated with N/10-sulphuric acid. using cochineal or lacmoicl as indicator. [See furf;her .7. SOC. f‘J:r?ti. ?nd.. 1919 5 4 A . 1 w. P. s. Estimation of Tyrosine in Proteins. Csnr 0. JOHNS z t r d 1). RREESE JONES ( J . Bin7. Clren?.. 1918 36 519--32~).--Tyr~iti~ can be estimated in a protein after hydrolysis with hydrochloric acid by means of the colorinietric method of Folin and Denis ( A 1913 ii 101 2). Tryptophan and hydroxytryptophan are destroyed during the hydrolysis and their decomposition products. as well a< oxyprolhe do iiot give any coloiir with the Folin-Denis reagent. H. W. B. New Contact Test €or Albumin in Urine. IT. Y. STEWAR’I* (,7. A vier. &fed. -4ssoc. 1918 71 1050; from Physid. A h s f ~ . . 1918 3 45l).-The reagent is an aqueous soliltion of picric acid. magncsium sulphate and citric acid. H. w. n,

ISSN:0368-1769    

DOI:10.1039/CA9191605072

出版商:RSC    

年代:1919

数据来源: RSC

摘要:

ii. 89 General and Physical Chemistry. Quantitative Spectra of Lithium Rubidium Cesium and Gold. A. G. G. LEONARD and P. WHELAN (Sci. Proc. Roy. DztbE. SOC. 1918 15 274-278).-The spark spectra of dilute solutions of the chlorides of lithium rubidium msium and gold have been photographed with the object of ascertaining the per- sistency and intensity of the lines with dilution. The measure- ments were made with a single prism quartz spectrograph (Hilger). I n the case of lithium chloride the most persistent lines are hh6708.2 and 4602.5; these lines persist to a dilution O*OOl% whilst the line X6103.8 only persists to 0.01%. The lines of rubidium chloride do not exhibit any remarkable persistency only one h 4571.8 appearing with a 0.1% solution. Solutions of msium chloride exhibit a fair number of lines the most persistent being Ah4593-5 4555.5 4540.2 and 2525-8 these all being visible in a 0.001% solution.The solution lines of gold chloride are not very persistent; no lines are visible in a 0.01% solution; the lines obtained from a 0.1% solution are hh 4792.8 4310.7 3927.8 3133.2 3122.9 2918.5 2676-1 2641.6 and 2201.4. Gamma Ray Activity of Thorium-D. HERBERT N. McCoy and G. H. CARTLEDGE ( J . Amer. Chern. SOC. 1919 $1 50-53. See this vol. ii 120).-Two methods are described for the deter- mination of the y-ray activity of thorium-D. The first consists in measuring the activity of the sulphide in terms of a standard (0-355 rng. radium) and making emanation determinations by the method previously described (Zoc. cit.). The second method con- sists in sealing radiothorium precipitate in a crystallising dish and comparing with radium in a similar dish.As a mean value of the experiments i t is shown that Th-D Th =0.956 x Using the value found by McCoy and Henderson (A. 1918 ii 422) that 1 gram of radium is equivalent t o 8.85 x 106 grams of thorium it is shown that 1-46 x 10-7 grams of radium has the same y-activity as L gram of thorium. Combining the Ms:Th ratio 0.52 x lo-' with the present Th-D:Th ratio tqhe value 1 . 4 8 ~ lo-' is the radium equivalent of the y-products of thorium determined separately. Thorium-D therefore furnishes 1.81 times as much y-activity as the mesothorium in equilibrium with the same amount of thorium. Taking account of the fact that only 35% of the thorium disintegrates into thorium-11 this means that atom for atom thorium-D contributes 5.17 times as much y-activity as meso- thorium.J. F. S. J. F. S. Absorption of .X-Rays. TYCHO E SON AUREN (Phil. .Mtq. 1919 [vi] 37 165-207).-Making use of the method previously described (A. 1917 ii 350) the author has determined the relative VOL. CXVI. ii. 4ii. 90 ABSTRACTS OF CHEMICAL PAPERS. absorption coefficients of a number of elements including aluminium iron nickel copper and tin and of a very large number of inorganic and olrganic compounds. I n the case of the compounds the additive law has been found valid throughout. With the possible exception of carbon the state of aggregation appears to have no influence on the amount of adsorption. In examining chemical compounds in which the same element appears but with differing valencies it is shown that there is no difference in the quantity of absorption in any case.The relation between the atomic absorption coefficients f o r most elements has been determined a t the medium wave-lengths h=0.38 0-36 0.34 and 0 . 3 0 ~ 10-8 cm. Assuming that absorption for hydrogen is ex- clusively due to scattering produced by the electron combined with the atomic nucleus it has been found likely that scattering for other elements is solely due t o the electrons constituting the outer layer of the respective atoms that is fo the “ outer electrons,” and by aid of the relative atomic absorption coefficient for hydrogen the number of the outer electrons has been estimated for the lighter elements.The atomic absorption coefficient increases for different elements by groups nearly proportionally to the atomic number. If it is accepted that the atomic number gives the number of electrons combined with the atomic nucleus i t is possible from the increase of absorption with increasing atomic number to deter- mine the distribution of electrons between the outer and inner regions. From Barkla and White’s determinations of the ratio p / p for copper and water a formula of the mass scattering coefficient for different elements has been deduced. The values calculated for the relative absorption coefficients for y-rays agree fairly with the observed absorption coefficients. The value of the mass scattering coefficient of aluminium for ?-radiation calculated by means of the above-mentioned formula agrees very nearly with the value directly observed by Ishino.The number of the outer electrons in the lighter elements seems to be the same for the elements placed in the same group of the periodic system and the distribution of electrons thus appears to be in close connexion with the periodicity of the chemical qualities of the elements as expressed by this system. J. F. S. Investigation of Wontgen Spectra. 31-Series . W. STENSTR~M (Ann. Physik 1918 riv] 57 347-375) .-The author has investigated the iM-sekies of Rijntgen spectra for the elements uranium thorium bismuth lead thallium gold platinum iridium osmium tangsten tantalum lixtecium ytterbium erbium holmium and dysprosium. It is shown that the older method of measuring Rontgen spectra is not suiteble for the soft radiations of the M-series but that better results are obtained if a glowing cathode and high-frequency transformed alternating current are used.As cat.hode a Wehnelt cathode was a t first employed but this was later replaced by a tungsten spiral. To find a grating of suitable constant many crystals were examined and the constantGENERAL AND PHYSICAL CHEMISTRY. ii. 01 determined. These included rock salt d=2.814 x 10-8 cin.; potassium chloride d- 3.136 x lo-* cm. ; calcite 3.028 x 10-8 em. ; gypsum 7-621 x lo-* cm. ; potassium ferrocyanide 8.454 x 10-Scm. ; mica 10.1 x 10-8 an. ; quartz 4.23 x 10-8 cm. ; beryl 4.61 x 10-8 cm. (on plane 0.0.0.1) and 8 . 0 6 ~ lo-* cm. (on plane 1.0.1.0); sodium ammonium tartrate 7.30 x 10-8 cm.; sucrose 10-56 x 10-8 cm. ; and the co'mpound AgNaC,,€I,0,S,,NazC,H804S21 10H,O It= 19 x 10-8 cm. From a discussion of the sources of error it is shown that' the probable error of the measurements does not exceed 0.2-0*3%. The present measurements were made with a gypsum crystal and i t is shown that in addition to the a- and @-lines a y-line also exists in the 1M-series and this conforms t o the Moseley relationship. Other lines appear in some cases. but these are in all probabilit>y due to impurities. Each of the main lines is diffuse and wide aiid the blackening decreases with decreasing wave-length. They consist of several single lines which were not sufficiently separated for characterisation. J. F. S. Conductivity. PV. Conductivity of Alkaline Earth Formates in Anhydrous Formic Acid.€3. 1. SCEILESINGER and R. D. MULLINIX (.I. A m e r . C'hcm. Sue. 1919 41 72-75. Compare A. 1912 ii 26; 1914 ii 703; 1916 ii 210).-The electrical conductivity of solutions of calcium f ormate and strontium formate has been determined in anhydrous formic acid solutions a t 2 5 O . The conductivity conceii tration curves are com- posed of three parts-of two straight lines which intersect a t about iV/lO and a portion which curves upward in a manner similar to that observed for sodium formate (Zoc. c i t . ) . It is likely that these salts ionise into a metal formate ion which in more dilute solutions is decomposed into a simple metal ion and that this secoiid ionisation becomes sufficiently great a t the concentxations where ths two curves meet to affect the conductivity appreciably. J.F. S. Depolarisers of the Becquerel Effect . ALEXANDER VON SAMSONOW (Zeitseh. wia. YlLotocherrz. 1918 18 141-176).- Working with oxidised copper electrodes the autho'r has st.udied the action of certain depolarisers on the electrode when immersed in solutions of sodium sulphate bromate iodate and chlorate. The potential rises much higher in iodate and bromate solutions hhan in sulphate and chlorate solutiops. As depolarisers ferrous sulphate glycine developer sodium sulphit e iron oxalate pamino- phenol sodium arsenite and sodium phosphite were used. Work- ing hypotheses of the Becquerel effectl and the action of the depolarisers are discussed. J. F. S. Phenomenon of Electrical Supertension. A.SMITS (Proc. I<. Akad. ?Vetemch. Smsterdani 1919 21 375-381. Compare this vol. ii 8).-A theoretical paper in which an unattackable electrode is considered as a hydrogen electrode froin the point of 4*ii. 92 ABSTRACTS OE’ CHEMICAL PAP.GEBS. view of the phase rule. The superteiisioli of electrodes is con- sidered from the same point of view and a A-x diagram is drawn to illustrate the process. It is shown that there is no essential difference between the phenomena of supertension and polarisation. The former is only a little more complicated in so far that here an unattackable electrode has been inserted into the system. When however the phenomenon of supertension is considered at attackable electrodes the process becomes identical with that of polarisation. J.F. S. Periodic Passivity of Iron. 11. A. SMITS and C . A. LOBRY DE BRUYN (Yroc. I<. ,-Ik~cl. Wetensch. A nisterdcim 1919 2l 382-38<5. Compare A. 1917 ii 262).-A continuation of previous work in which it was shown that anodically polarised iron could be activated by the introduction of halogen ions. Hence by the electrolysis of a sclution of ferrous sulphate and ferrous chloride the phenomenon of passivity can be made periodic. This periodic property has now been photographically recorded together with the time duration of each stage of the process. The potential difference varies between - 0.3 volt and + 1.4 volts with respect to the normal calomel electrode and the current density changed from 33 milliamperes to 28 milliamperes per sq cm. With a sealed-in electrode 1.5 a.long the iron was active for a short period and passive for a comparatively long period. With a smaller current density the active and passive periods become nearly equal. The effects on the curves produced by changing the relative depth of the electrodes have been studied. Using a larger iron electrode the potential difference showed irregular oscilla- tions whilst the current strength was regularly periodic. The irregularity was such that even the most active state did not recur regularly and the whole curve shows periodicity under the influence of great distnrbances. Hence it follows that the electrode was never act’ive throughout the whole area a t the same time. This confirms tho previous view that the difficulty of rendering iron passive increases with increasing size.J. F. S. The Sign of the Electrical Phenomenon and the Influence of Lyotropic Series observed in this Phenomenon. H. ZWAARDEMAHER and H. ZEEWU~SEN (I’roc. R. A k d . Weterzsch. dIInzste&m 1919 21 417-427. Compare A . 1918 ii 351).- The nebula produced when an unsaturated solution of salicylic acid is sprayed always possesses a negative electric charge. This charge is weakened by both anions and cations in the order Li*<Na*,K*<Rb’<Cs*<K H,’ for cations and CB’S’,NO,’<I’,OI’,Br’ <C,H,O;< tartrate ion <PO;’’< citrate ion <SC j4” for anions. Acetic acid weakeiis or completely destroys the negative charge of salicylic acid. I n higher concentrations with a positive electrical phase it prevails as an acid over salicylic acid sprayed in weak solutions which gives a negative charge.Acetates also have a weakening effect on the charge of salicylic acid whereas of them-GENERAL A 3 JI PHYSICAL ClIEMISTftY. ii. $ 3 selves they produce no charge. Mixtures of salicylic and acetic acids showed the electrical property of acetic acid so long as the latter acid is present in the larger quantity. If the concentration of acetic acid in the mixture falls so low that such a solution of acetic acid alone would give scarcely any effect then the charge of the mixture sinks to zero; in still lower concentrations of acetic acid the charge reappears but this time negative. J. F. S. Dependence of the Magnetic Properties the Specific Resistance and the Density of Iron Alloys on their Thermal Treatment. E.GUMLICH (Zeztsck Elektrochem. 1918 24 372-377) .-The density specific resistance temperature coefficient of the resistance the first and second transition points and the magnetic propertjes (coercive force retentiveness permeability and hysteresis ioss) have been determined beiore and after anneal- ing processes carried cut under varims conditions on pure electro- lytic iron commercial iron (seven specimens) iron alloys with carbon (O-l-S%) with silicon (0--8*5%) with aluminium (0-10-5%) and manganese (0-16'?&). I n the case of pure iron the following values were obtained D 7.8176 ; specific resistance per sq. mm. 0.0994; temperature coefficient of the resistance between 20') and 100° 0.5 /%; saturation value 47rJ =21,620 where J is the intensity of magnetisation. These values were very little changed by annealing and stand in contrast t o the magnetic properties.It is shown that< the improvement in the magnetic properties brought about by annealing is not due as generally believed to a molecular change but rather t o the removal of adsorbed gases. In rich carbon alloys the first and second transi- tion points lie in the same position as those given in the diagram of condition. In the curves between the carbon content and the density coercivity and saturation value respectively there is a sharp break a t the point where normally cementite separates from perlite or martensite. The carbon content has a marked effect on the coercive force. This quantity increases approximately 7 gauss per 1% increase in the carbon content in tlia case of perlite and 70 gauss in the case of martensite.With smaller carbon content the influence is much greater; thus with 0.1% carbon impurity the coercive force rises 0.7 gauss. The presence of silicon diminishes the magnetic properties ; this substance behaves like non-rnag- netic impurities which diminish the magnetic properties of the iron. The presence of aluminium affects the iron in much the same way as silicon; the specific resistance increases nearly pro- portionally to the aluminium content. The second transition point is lowered 100O by 10% of aluminiuni. The manganese alloys show similarities to the carbon alloys. The coercive force is extra- ordinarily high after annealing and with 10% manganese has a value of 60 gauss whereas the retentiveness disappears with 14-1 6% manganese.With nianganese coiiceiitrations S-9?; the density specific resistance and the magnetic properties shou7 great irregularity. The txantiition points show a marked tempera- 4"-.2ture hysteresis and from this it is deduced that alloys coiitainiiig 10-1 2% manganese cannot be magnetised. J. F. S. Diamagnetism in Weak [MagneticJ Fields. 0. E. FRWOLD ( A m . Physik 1918 [iv] 57 471-488).-The magnetic suscepti- bility of tellurium water sulphur antimony zinc gold and silver has been investigated in magnetic fields of varying strength With the exception of zinc all the elements investigated show a depend- ence with respect to their susceptibility on the strength of the field for weak fields.I n the case of higher field strengths the susceptibility is constant except in the case of silver. The suscepti- bility is constant for field strengths down t o 100 gauss in the case of zinc to 600 gauss f o r gold tor 250 gauss for antimony to 200 gauss for tellurium and above 600 gauss for sulphur. Silver is paramagnetic i n weak fields but becomes diamagnetic in fields above 800 gauss. I n the case of antimony tellurium and sulphur a very strong dependence on the field strength for weak fields is displayed. The susceptibility of gold shows a dependence on the field strength which is in keeping with the theory of Gauss and on the basis of this theory the number of inagnetons per cu. cni. has been calculated and the value 1.7 x 101-1 obtained. Con- sequently a magnet,on of gold contains 3-65 x 109 atoms.J. F. S. The So-called First Quantum Theory of Planck. The Quantum Theory of Paramagnetism. ADOLF SMEKAL ( A m . Physilt 1918 [iv] 57 376-4OO).-A theoretical paper in which three f ormulz are deduced to represent susceptibility. These formulae are tested on measurements for ierric sulphate manganese sulphate and the tetrahydrate of manganese sulphate and a com- parison is made with the quanten theories of Planck. J. F. S. Thermal Conductivity of Neon. S. WEBER (Proc. K. dkad. Jl’etensclt. A?nsterdtzm 1919 21 342-356).-The thermal con- ductivity of neon has been determined under various pressures by Goldschmidt’s method which consists in electrically heating a wire in the gas and from resistance measurements calculating the rate of conduction.A correction is introduced for loss of heat a t thho ends of the wire. The thermal conductivity of neon a t the follow- ing temperatures is shown to be 1 0 5 9 lr2’=0.0001344; Oo 0*0001087 ; - 74*37O 0*0000879 ; and - 181*43O 0*0000499. These values are compared with the values calculated by means of the formula of Sutherland and a general formula of Maxwell. It is shown that whilst there is good agreement in the second case Sutherland’s formula appears to be inapplicable a t low tempera- tures. Prom a comparison of the thermal conductivities of argon helium and neon it appears that the reduced thermal conductivity of neon changes in a different manner with the reduced tempera- ture than the similar values for argon and helium. J. F.8.GENERAL AND PHYSICAL CHEMISTRY ii. 95 Empirical Formula for Calculating the Specific Heat of Water. J. N A R B u m (Physikal. Zeitsch. 1918 19 513-514).- The author has deduced an empirical formula for calculating the specific heat of water over the temperature range 0-looo. This formula is based on the experimental results of Ludin Dieterici BousfieId (A. 1911 ii 5SO) Callendar (A. 1912 ii 428) and Barnes and Cooke and has the form ct= 1,00733 - 0.00074166 -i- 0-000016S45t? - 0.00000009552t3 where c15= 1. The agreement between the values calculated by this formula and the best experi- mental values are extremely good. J. F. S. Calculation of the Ratio of the Principal Specific Heats of Benzene and cycZoHexane by Leduc's Cyclic Method. G. DEJARDIN (C'onzpf. TeftcF.1919 168 161-164) .-Using Leduc's formula (compare ,1 72n. Pliy.ciprie 1915 [viii] 23 577) the author finds that the value of y the ratio of the principal specific heats for benzene a t 2 0 O is y=l*lO6 and a t looo y=1*116 and for rqydohexane between 2 0 O and 90° is y=1.077. Using the forniula y = l + 2 / ( p - t - h ) where is the number of degrees of liberty relative to the kinetic energy of the molecule and h is the intramolecular potential energy the author finds f o r benzene y = l * l l l and for cyclohexaiie y=1.083 or 1.074 according as the degrees of liberty are taken as 24 or 37. vST. G . Thermochemical Studies Simplified Formula €or Calcu- lating the Molecular Latent Heat of Evaporation. DANIEL I,AGERL~F ( J . pr. CJieui. 1918 [ii] 98 136-142).-Since all the author's calculated values and also Thornsen's experimental values for the heats of combustion of the hydrocarbons refer to the gaseous state whilst most of the experimental values obtained by other authors refer to liquid or solid compounds comparison of these different values requires a knowledge of the molecular latent heat of evaporation.The latter has been determined in but few cases and can be derived only from Deprez and Trouton's law qiY=constant. For the value of this constant van't Hoff deduced the mean value 20.55 cal. whilst? for non-associated liquids Kurbatov obtained the mean value 20.7 cal. the variation from the mean being a t most 3-4%. (or 20*7Y) the author derives the expressions q = 0.02t + 5.6 + 0.00055t and q =0*03t + 5.65 + 0*000St which refer to kilogram calories ; t = T - 273.In order to arrive a t an expression which may be easily remembered he combines these two equations with t-he result q = w,,,~. = 0.02t + 5.6 + 0.0007f. The third variable member of the right-hand side may be neglected for values of f numerically less than 1 5 O . The available experimental data show however that? for uninuclear aromatic hydrocarbons a fourth negative member must be introduced the equation then becoming 2 0 % ~ ~ ~ . = 0.026 + 5.6 + 0.00076 - ( t - 80.) / 300. It is not known if COP From the equation 2Ura*,. = q = 20-55Tii. 96 ABSTRACTS OF CHEMICAL PAPERS. rection is needed for multinuclear aromat-ic hydrocarbons since no experimental numbers exist. The values for the different terms of the above equations and the calculated and experimental values of ? P ~ ~ ~ .are given in tabular form for a large number of hydrocarbons of different kinds. The differences between the calculated and experimental values are sometimes marked but in most cases the agreement between them is extremely good. T. H. P. Thermochemical Value of the Linkings Uniting the Atoms in Crystals. M. PADOA (Atta ZZ. Bccad. Lincei 1918 [v] 27 ii 327-331).-If the union of the atoms in crystalline networks is affected by means of valency (compare this VOI. ii 51) a relationship should exist between the thermochemical data and the values of such linkings. Since the heat of combustion of diamond is 94.32 Cal. per gram-atom and CO + 0 + CO + 68.22 Cal. and since the thermochemical equivalence of the Four valencies of carbon has been demonstrated the difference 94.32 - 68-23 = 26-10 Cal.may be taken as the heat of formation of carbon mon- oxide from an atom of carbon combined in diamond and the differelice 68.22 - 26-10=42*12 as the heat of disintegration of the carbon atom that is the heat-equivalent of the energy required to dissolve the linking holding it. in the crystal. From the struc- ture of the diarriond it follows that. with each carbon atom there correspond four half-valencies or two whole ones so that each valency has the value 42.12 :2-31*06 Cal. h similar value is obtained in the case of graphite. Each free atom of carbon gives then on complete combustion 94.32 -t 42.12 = 136.44 Cal. and four free hydrogen atoins yield similarly four times the heat of combustion oE a gram-atom of molecular hydrogen plus twice the heat of dissociation of the hvdrogeii inolecule.that is. 4 x 34.35 i 2 x 95 = 327.40 Cal. Hence the sum 136.44 + 327-40=463*84 Cal. diminished by the observed heat of cornbustion OE methane namely 312.70 Cal. gives 251.14 Cal. which constitutes the heat of formation of the methane mole- cule from its constituent free atoms cmwequentlv each C-H link- ing corresponds with 251.14 4 = 62.78 Pal. Similar calculation of the value of the C-Cl linkinqs in normal saturated open-chain hydrocarbons gives nnnibers varvjnq from ahout 16 Gal. for the lower to about 18 Cal. f o r the higher members of the series. I n the case of benzene which according t o Thornsen (“Thermo- chemistry,” 1908.393. 449) behaves thermochemicallv as if i t con- tained nine simDle linkings and thus corresponds with the centric formula. each of these nine linkings represents a value of 16.6 Cal. With other cvclic hydrocarbons increase in the niimber of nuclei is accompanied by increase in the mean number of linkincs competinq for each carbon atom. this number tending. t o the limiting value 2 ; rit the same time the inem value for each C-C linkinq increases towards the value 21.0 f o r granhite. IJ7it-h hvdrogenated hvdro- carbons such as cydohexane decahydronaphthalene and 7) -octane,GENEPAL AND PHYSICAL CHEMISTRY. ii. 97 the C-C values are somewhat higher than with the1 corresponding non-hydrogenated ones. T. H. P. The Heat of Dissociation of Diatomic Gases in Relation to the Increase in the Value of JZ of the Dissociated Atoms.J. J. VAN LAAR (Chenz. TVeeEblad 1918 15 1124-1137). -The theoretical considerations of this paper are based on the regularities observed by the author which are found t o exist when the values of b and d\lcG of the van der Waals’s equation of state are brought into relation to the groups of the periodic system (A. 1916 ii 386-387 610; 1917 ii 67). The values of b and d c for a compound are shown to be additive properties of the substance calculable from the values of the corresponding constants of the constituentl elements. The value1 of b for any element is found to be independent of its state of combination whether the element occurs free or combined in a molecule. On the other hand J&T which is dependent on the mutual attraction o’f the molecules is subject to variation according as the atom to which it relates is more or less shielded by other atoms in the molecule.For example the values of J n f o r the carboir atom in CH silicon in SiH nitrogen in 3J€Li are in each case fouiid tjo be zero that is the central atom exerts 110 external att’raction. T n the case of hydrogen nitrogen oxygen and the halogens all of which dis- sociate into single atoms in suitahle coitditioiis of temperature i t has been iounct t h a t dn is greatly increased iii the monatomic state of the gas. y‘n thus becomes a measure of the “valeiicy attraction” of the two atoms (%/.I ) whilst the value of J-i ordinarily to be attributed to the same atom in compounds repre- sents the ‘( residual attraction.” For carbon the ratio of the two valties is 32 3.1.Between the two eoiw-tants JA;- and at the critical temperature the following relation is established where Qo is the energy liberated a t 1’=0 in the formation of one gram-molecule of gas from the free atoms I’,i is the critical tempera- ture and @ a constant approximating to unity. The values of 2/if for various gases (hydrogen nitrogen oxygen the halogens) calcu- lated from this equation are in satisfactory agreement with the values which correspond with the position of these elements in the periodic arrangement. W. S. M. The Effect of some Simple Electrolytes on the Temperature of Maximum Density of Water. ROBERT WRIGHT (T. 1919 115 119-126). Compressibility of Aqueous Solutions especially of Urethane and the Polyrnesiaation of Water.THEODORE W. RIGBARDS and SVEN PALITZSCH ( J . ,4mer. Chem. SOL‘. 1919 41 59-69).-The compressibility of water and of aqueous solu- J’,<= J a x J(l+ ~ ~ ~ & o / ’ / i ) ,ii. 98 ABSTEACTS OF CHEMICAL PAPERS. tions of urethane has been carried out hy the method previously described (A. 1912 ii 896). The concentration was varied from 0-56*01% and the compressibility determined for pressures between 100-300 megabars. All experiments were conducted a t 20°. I n addition to these determinations the solution volume the surface tension and the viscosity 01 urethane solutions were also determined. It is shown &hat with rising concentration the com- pressibility decreases rapidly from 43.25 x 10-6 (the compressibility of pure water) to 38.91 x 10-6 the compressibility of a solutimi of 34 grams of urethane in 100 grams of water.From this point the compressibi1it.y increases at' first slowly and then more rapidly ; a t the highest measured concentration 127.35 grams of urethane in 100 grams of water the compressibility is 40.S6 x The surface tension specific volume and viscosity showed no such mini- mum and i t is shown t-hat none is to be expected. The results emphasise the theory of Whiting which ascribes polymerisation to water. J. F. S. Determination of the Compressibility of Solids at High Pressures. LEASON H. ADAXS ERSKINE D. WILLIAMSON and JOHN JOHNSTON ( J . .lwer. Ghm?. C o p . 1919 41 12-42).-The compressibility of quartz calcite aluminium sodium chloride lead brass cadmium zinc tin silver copper gold bismuth a tin- bismuth alloy tool steel and silica glass has been determined for pressures up t o 12,000 megabars.The principle of the method employed is to compare the change of volume under pressure of a cylinder of the material with that of a similar cylinder of soft steel the compressibility of which was considered to be 0.60 x cin ."megadyne. I n carrying out the determination the solid surrounded by a liquid such as kerosene was enclosed in a thick- walled steel bomb fitted with a movable non-leaking piston and pairs of simultaneous readings were made of (1) the displacement of the piston that is the volume change and (2) the pressure. The piston displacement was measured t o 0.01 mm. by means of a dial micrometer. I n measuring the pressure advantage was taken of the change of resistance under pressure of a "therlo" wire and in order to determine the pressure to within 1 megabar the resistance was measured with a type of Wheatstone bridge having no movable conttact,s.The P - A v graph for gold copper brass silver aluminium and calcite like that of steel is linear but the graph for zinc tliiin. cadmium lead the tin-bismuth alloy quartz bismuth and sodium chloride shows an appreciable curvature thus indicating €or those substances a measurable decrease of compressibility with increasing pressure. A compari- son was m d e of the Compressibility of two alloys with that of t-heir components. I n the case of a simple mixture. such as the tin-bismuth alloy the measurements indicate that the compressi- bility of mixtures the other properties of which such as specific volume electrical conductivity and spec:& heat are approxim- ately linear functions of the composition is related in the sameGENERAL AND PHYSICAL CHEMISTRY.ii. 99 simple way to the compressibility of the separate components. On the other hand the compressibility of alloys of the class to which brass belongs is much lower than the sum of the individual com- pressibilities . J. F. S. Thermal Dissociation of Sulphur Dioxide. J. B. FERGUSON ( J . Amer. Chern. Soc. 1919 41 69-72. Compare this vol. ii 15) .-Starting from the equilibrium constant of the reaction C0-1-@0 Zr C0,t-4S2 the author has calculated the degree of dissociation and the equilibrium constants of sulphur dioxide over the temperature range 1000-1500° and at pressures from 1 a h .to 0-001 atm. The degree of dissociation at 1500O and 1 atm. is found to be 5.9 whilst at 0.001 atm. it is 59. Consequently it is obvious that' the dissociation of sulphur dioxide is less than the dissociation of either carbon dioxide or water vapour. J. F. S. Capillarity Constants of Pure Mercury and of Liquid Potassium Amalgam in Contact with Potassium Iodide Solutions. V. POLARA (Atti €2. Accccd. Liwei 1918 [v] 27 ii 322-327).-Gouy (A. 1892 760) showed t?hat the capillarity constant of mercury i n contact with aqueous potassium iodide solutions assumes a maximum value somewhat less than that+ of the same metal in contact with dilute sulphuric acid (1 6 by vol.).This behaviour is in contradiction to Lippmann's law according to which the capillarity constant should be a function solely of the potential difference a t the contact and its maximum hence independent of the nature of the substances in contact. By means of Quincke's apparatus the author has investigated the influence of the concentration of the potassium iodide or1 the maximum value of the capillarity constant of the mercury in contact with it and on the polarisation determining such maximum. Gradual increase of the concentration is found to be accompanied by progressive lowering in t h s maximum value of the capillarity constant the difference f o r the two extreme cases (X/lO and 10iT) amounting to a variation of about' 1 mm. in the difference of level between the two limbs of the apparatus; within f*he limits of sensitiveness of the method the polarisation requisite for obtaining the maxi- mum depression does not appear to be influenced by t'he concen- tration.Depression of the surface tension of the solution by addition of ethyl alcohol in various proportions produces marked lowering of the maximum of the capillarity const'ant especially for percentages of the alcohol not exceeding 40; for higher propor- tions of alcohol the effect is less pronounceld. Also potassium amalgams (2-0.1 part of potassium per 1000 of mercury) in con- tact with normal potassium iodide solution exhibit a capillarity constant which is somewhat lower than the maximum capillarity constant of pure mercury in contact with sulphuric acid solution and diminishes sensibly with increase of the proportion of potassium dissolved in the mercury the diminution being slower for the more concentrated than for the more dilute amalgams.4-ii. 100 ABSTRACTS OF CHEMICAL PAPERS. Study of the variations in the density of the electlric double layer a t the contact with the polarisation by an apparatus detect- ing a change of 0.1 volt in the pollarisation confirms the relation X = - d A / d p where X is the density of the double layer ,4 the capillarity constant and p the polarisation. This relation may be brought into accord with the circumstance that the capillarity constant does not depend solely on the potential difference a t the contach by assuming thati the function A has the form A = S - T ( V - p ) where S the ordinary surface tension is in- dependent’ of the potential difference a t the contact but depends in agreement with the results obtained on the particular condi- tions of the contact; T ( V - p ) is the symbol of a function only of the potential difference (V-17) existing a t the contact for each value of the polarisation employed ( I’ =potential difference due to the contact and p the polarisation employed) and satisfying also the conditions GFTIdp= ,IT and ( d T / d p ) p = = 0.T. H. P. Velocity of Diffusion. PHILIPP FRANK (Physiknl. Zeitsclz. 1918 19 516-520).-A mathematical paper in which formulz are deduced for the velocity of diffusion of gaseous molecules. The calculations are based on considerations of the Brownian move- ment and are made in coriiiexion with single particles and with the rate of advance of the “head” of a particle swarm.J. F. 8. Crystal Assemblage in Relation to the Atomic Field of the Crystal. R. GROSS (Jahrb. Radiouktiv. Elektroizik. 1916 15 270-292) .-The author uses the term ‘‘ Sammelkrystallisation ” (crystal assemblage) to signify the transformation of a substance from an amorphous or sub-crystalline to a distinctly crystalline state. A number of examples of the phenomenon are discussed. One of the most striking examples is a process weld for making tungsten filaments. The finely divided metal obtained by reduc- tion of the oxide is pressed into the form of wire and drawn slowly through a small heated coil a t a temperature of 2000-2200°. When the rate of passage of the wire through the heated coil is properly regulated it becomes converted into a single homogeneous elongated crystal the rate of growth of the crystal being equal to the rate a t which the wire is travelling.The particles of tlungstmen of which the wire is originally composed have a mean diameter of about lop5 cm. and it has been shown by Debye (A. 1917 ii 574) by the X-ray method that this powder consists of cubic crystalline particles. Other examples of crystal assemblage are afforded by the increase in size of the crystals of many metals by annealing by the formation of silver crystals from a silver sol and by the formation of calcite crystals when powdered calcium carbonate is heated under pressure. Some substances for example calcium sulphate have a greater solubility than the normal when the particles in equilibrium with the solution are very small in size but in course of time t.he solu-GENERAL AND PHYSICAL CHEMISTRY.ii. 101 bility falls to the normal owing to increase in the size of the particles. It is shown themodynarnically t.hat the solubility should increase when the particIes become very small and it is concluded that the theory of minimum surface energy does not adequately explain ,crystal growth since for very small particles the surface energy is not independent of the size. E. H. R. Liquid Crystals. HI. Melting and Congelation Phenomena with p-Azoxyanisole. W. J. H. MOLL and L. 8. ORNSTEIN (Proc. K . A kud. ltl’etensch. Anzsterdurn 1919 21 264-258).-1n a previous paper on the extinction of liquid crystals it was sug- gested that two varieties of liquid crystals of p-azoxyanisole exist ex-solid (produced by melting the solid) and ex-liquid (produced by cooling the isotropic liquid).To confirm this point the authors have determined the fusion and congelation curves of pazoxy- anisole and show from the results that there is no evidence from this source of the existence of two forms of liquid crystals of p-azoxyanisole. On the other hand these curves show the exist- ence of three solid forms of this substance p-amxyanisole I (m. p. 1 1 8 O ) p-azoxyanisole I1 (m. p. 104*5O) and ’p-azoxyanisole 111 (m. p. 116O). A fourth form which melts a t 1 0 8 O was shown to exist in the previous paper but this form did not appear in the present work and it is now shown oiily to be capable of existence in capillary layers (between glass).J. F. S. Molecular Mechanism of Colloidal Behaviour. I. The Swelling of Fibrin in Acids. RICHARD C. TOLMAN and ALLEN E. STEARN ( J . Amer. Chem. SOC. 1918 40 264-272).-The amount of swelling of blood fibrin in solutions of hydrochloric nitric sulphuric acetic and formic acids of various concent‘ratJons has been determined as well as the amount of acid adsorbed by the fibrin from the solution. Similar experiments have been carried out with solutions of sodium chloride and with solutions of the above-named acids to which sodium chloride has been added. The data obtained are in accordance with the authors’ theory of the molecular mechanism of protein swelling. This theory embraces the following points. On account of the arnphoteric nature of protein colloids they possess a marked tendency to adsorb hydrogen ions from acid solutions and liydroxyl ions froin alkaline solutions. In an acid solution tho adsorbed hydrogen ions t’ogether with an equivalent number of anions form a “double layer” on the walls of the pockets or pores in the interior of the gel and this leads to swelling and the imbibition of water by electrostatic repulsion.The addition of a strong electrolyte to such a swoIIen colloid either a neutraI salt or excess of the strong acid which caused the original swelling will furnish ions in the interior of the pockets which will tend to arrange themselves so as to neutralise the electrical fields of the adsorbed layers and thus bring about a reduction of the swelling.The addition of a neutral salt to an acid solution tends to neutralise the electrical field af 4**-2ii. 102 ABSTRACTS OP CIXEMICAL PAPERS. the adsorbed acid and heuce makes it easier for more acid to reach the surface of the pockets thus leading to increased adsorp- tion. Salts with multivalent ions should be more effective in reducing swelling than salts with univalent ions since for example a bivalent ion will take up no inore room than a univalent ion and will be twice as effective in neutralising an existing electric field. No assumptions are made as to the. molecular nature of the adsorption of the hydrogen or hydroxyl ions; the theory would be equally tenable if the adsorption process should lead t o a fairly uniform coating of ions over the whole of the exposed surface or on the other hand if the hydrogen ion should only tend to go on to the proteiii molecule a t special points where there is a particu- larly strong stray field for example where the amino- and acid groups of the amino-acids approach one another.J. F. S. Colours of Colloids. WILDER D. BANCROFT (J. physicd Chewz. 1918 22 601-630).-A theoretical paper in which the author discusses the nature of the colour of natural objects. The subject is treated historically and the various types of colouring individu- ally treated. Colours are divided into two groups (1) structural colours and (2) pigmentary colours. The former group of colours owes its existence to the refraction absorption and interference of light. J. F. S. Degtee of Dispersion of Coloicls and its Determination. GEORGE KING ( J .SOC. Chen~. Iqzd. 1919 38 4-7~).-A short account is given of the slit ultra-microscope and its capabilities. In counting the number of colloidal particles in a definite volume of colloidal solution it is necessary owing to the rapid Brownian movement to take the mean of the numbers of particles observed a t ten momentary observations and the solutions should be diluted with colloid-free medium until there are never more than four particles in the field a t the same time. The periodic illumination may be effected by allowing a pendulum screen to swing in front of the micrometer slit the impression of the number of particles seen being then very definite. The solution in the observation cell should be changed at least ten times and the mean of the one hundred separate counts taken; further one or more controls with fresh dilution should always be made.The paraboloid Leitz and Cotton and Mouton devices for dark- ground illuminations serve well for qualitative observation but are useful only for coarse hydrosols; they are moreover unsuitable for the rapid examination of colloidal solutions as the adjustment of the instrument must be disturbed for each small quantity observed and a fresh volume of solution introduced into the special microscope slide. With the cardioid ultra-microscope it' is possible to distinguish particles beyond the range of the old slit! ultra- microscope owing to the fact that the hydrosol can be more intensely illuminated. The slite ultra-microscope has now been enhanced in sensitiveness by using objectives of high numericalGENERAL AND PHYSICAL CHEMISTRY a ii.103 aperture (1*05) one a t right angles to the other the front lenses made of quartz being both immersed in the hydrosol. By this means the size of the particles which can be counted is diminished froin 5pp to 3pp whilst even smaller particles can be seen in con- centrated solution but not accurately counted in dilute solution. With the new immersion ultra-microscope qualitative examina- tions were made of solutions of peptone starch gelatin agar-agar and dextrin in the concentrations used by Findlay and King (T. 1913 1170; 1914 lZ97) but these were found to be optically clear under the best conditions for illumination etc. ; the refractive indices of the medium and colloid are doubtless nearly equal.Merck’s ferric hydroxide is however countable. Of physiological inkeyest is t3he condition of casein in cow’s milk and human milk. The particles in the latter are uncountable in the slit ultra-microscope but they can be counted in the new instrument whilst casein in cow’s milk is easily seen in the slit ultra-microscope. Thus it would seem that when it is to be used for feeding infants cow’s milk should be so treated as to cause an increase in the degree of dispersion of the casein particles; this is not effected by mere diIution of the milk. When it is necessary to determine the size of microscopic particles in a suspension use may be made of Stokes’s formula V =F/G?ryr where Tr =velocity of fall F = force acting 7 = viscosity and r=radius of particle.Other methods which have been used are discussed by Henri (Truns. Faradap Soc. 1918 47) but are not convenient for technical application. The System Iron-Oxygen. A. SMITB and J. M. BIJVOET fProc. K. Akad. Wetemch. Amsterdam 191 9 2 1 386-400),-A theoretical paper in which the three-phase systems FeO,Fe,gas and Fe,O,,FeO,gas are considered. The gas in question is either of the reducing mixtures CO,,CO or H,O,H. On the basis of tjhe deductions drawn from the above-mentioned considerations the processes operative in the blast f urnace are theoretically investi- gated. The P.T. diagram of the system oxygen-iron is derived from the equilibria of the iron oxides in reducing and oxidising gases respectively. Calculations are made of the oxygen dissocia- tion tension and these values as was to be expected are very small.J. F. S. T. E. P. Influence of Temperature on Homogeneous Gas Reactions. GEORGE ?TT. TODD and S. P. OWEN (Phil. Mag. 1919 [vi] 37 224-230) .-A mathematical paper in which from Maxwell’s dis- tribution theorem an expression has been deduced by which the number of molecules having a velociby greater than a parkicnlar value may be calculated. 72 = 2Ne-x “/ d7F(x1 -+ &xl> in which .n is the number of molecules per C.C. which have a velocity greater than c and z=cy’m/2RO; all the other factors have their usual significance. Assuming that only molecules with kinetic This expression has the form -_____ii. 104 ABSTRACTS OF CHEMICAL PAPERS. energies greater than a definite minimum have the power to react wibh other molecules it is shown how the velocit3y constant of a gaseow reaction varies with temperature. This is represented for the general case by the equation in which TJ’ is a constant. The general relationship for the depend- ence of the equilibrium constant on the temperature is also deduced. J. F. S. The Evolution and Magnetic Properties of Chromic Hydroxide in Alkaline Solution. F. BOURION and A. SENECHAL (Compt. rend. 1919 168 89-91 Compare this vol. ii 66).- The velocity constants f o r the rate of oxidation of chromic hydr- oxide in alkaline solution by hydrogen peroxide a t 1 7 O and 30° during the first eight hours correspond fairly well with those for a quadrimolecular reaction. The paramagnetism of an alkaline solution of chromic hydroxide diminishes slowly wit-h time but the diminut.ion is small and never exceeds 210%. w. G . Polar and NOn-pOh’ VahlCy. RAJENDRALAL DE (T. 1919 115 127-134). Automatic Variation of Gas Pressure and its Application to a Vacuum PUIW~R Circulation of Gases and] Magnetic apparatus is described which when attached t o a Toepler mercury pump may be used for the periodic variation of gas pressure. By suitable adjust’ments which are described in the paper the apparatus may be eniployed for the circiilation of gases and f o r Stirrer. 0. MAASS ( J . Arner.. Chem. SOC. 1919 4 1 53-59),-An working a magnetic stirrer. J. F. S.

ISSN:0368-1769    

DOI:10.1039/CA9191605089

出版商:RSC    

年代:1919

数据来源: RSC

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PI~YSIOLOGICAL CHEMISTRY. Physiological Chemistry. i. 103 Quantitative Evaporation of Blood Serum. GEORGE H. BURROWS and EDTYIN J. COHN ( J . Biol. Chern. 1918 36 557-590). -The apparatus consists of an ordinary distilling flask of a t leash 1 litre capacity supplied with 100 grams of rather large glass pearls. The stopper carries a dropping funnel the lower end of which cxteiids into the bulb of tlie flask. The side-tube of the flask is coil- 1:scted with a vertical condenser ~ l l i c h empties into a previously weighed bottle of size suitable for trapping the evaporated and condensed water. Following this in succession is a weiglisd calcium cliloricle tower a iiiaiiometer arid a vacuum pimp. The trap bottle and calcium chloride tower are immersed in ice-cold water and ice- water should flow tlirougli the condenser jacket.The flask and appendages having been weighed the apparatiis is exhausted to a pressure of 1 em. of mercury or less. The flask is imniersed in a water-bath a t 50° and the liquid serum is then allowed to enter slowly through the funnel as nearly as possible a t the rate a t which evaporation proceeds. So treated the serum foams largely and leaves a friable product which adheres loosely to the walls of the flask. When the desired ainoiint of liquid has been evaporatecl the colt1 wiitcr of tlie coiitleiiser jacket is rcl’lacetl 1)yi. 104 ABSTRACTS OF CHEMICAL PAPERS. warm water and air slowly admitted through the funnel. This is followed by re-exhaustion with slight raising of the temperature of the bath.When the serum is dry the apparatus is dismounted and the parts weighed. Serum contains about 9% of solids which as thus obtained dissolve readily in water yielding a slightly tm%id solution. H. W. B. The Action of Ferric Thiocyanate on Normal Human Serum. ARTHUR VERNES and ROGER DOURIS (Compt. rend. 1918 '167 972-974).-The reagent prepared by the action of ammonium thiocyanate or ferric chloride is added to a series of tubes contain- ing 0.4 C.C. of diluted serum in diminishing dilutions. The first tubes show no precipitation then follow a series of tubes in which precipitation takes place and these are followed by another serie.; with no precipitation. KINGO GOTO (J. Biol. Chem. 1918 36 355-376).-The daily administra- tion of hydrochloric acid to a rabbit during a period of from one t o four weeks was accompanied by an increase in the urinary excretion of phosphoric acid.Subsequent investigation showed that tlw muscles were deficient in phosphorus soldium and potassium and the bones in calcium carbonate. The fat content of the skeleton was also1 greatly reduced. These results indicate that in acid intoxication after the carbonates in the body fluids have been ileutralised the alkali phosphates of the muscles and the calcium carbonate of the bones are drawn on in the attempt t o maintain tht hydrogen-ion concentration of the body tissues a t the normal level. S. B. S. Mineral Metabolism in Experimental Acidosis. R. W. B. Comparative Metabolism of certain Aromatic Acids. 11. Fate of p-Hydroxybenzoic Acid and p-Hydroxy- phenylacetic Acid in the Organism of the Monkey.CARL P. SHERWIN ( J . Biol. Chem. 1918 36 309-318. Compare A 1917 i 603).-Feeding experiments on a monkey (iwacacus rhesus) indicate that in relation to the process of the metabolism of the aromatic amino-acids the monkey stands in the same position as other lower animals and thus differs from man. The mcnkey excretes the p-hydroxybenzoic acid in the urine in an iincombined state whilst a partial combination with glycine take. place in the human organism. On the other hand p-hydrosy- phenylacetic acid is partly excreted as phydrcmyplienylaceturic acid ill the case of the monkey and lower animals but is excreted i n an uncombined form in man. Metabolic Changes induced by the Administration of Guanidine Bases. V. Change of Phosphate and Calcium Content in Serum in Guanidine Tetany and the Relation between the Calcium Content and Dextrose in the Blood.C. K. WATANABE ( J . Bz'ol. Chem. 1918,36 531-546. Compare A. 1 91 8 i 327).-The administration of guanidine to rabbits produces a. cudition of severe acidosis with the retention of phosphates R H. W. B.decrease of calcium ill the blood and a hypoglymmia. After the extirpation of the parathyroids in the rabbit phenomena and syrnp- toms are observed which are similar to those occurring after the administration of guanidine. Since there is a large increase in the guanidine bases in the blood in parathyroid and in idiopathic tetany it is possible that the fundamental cause of tetany is tlie i itcreased formation of guanidine brought about by tlie disturbance of the function of tlie parathyroids.H. W. B. Influence of Protein Feeding on the Concentration of Amino-acids and their Nitrogenous Metabolites in the Tissues. H. H. M1TcnEr.I; ( J . Biol. Chm. 1918 36 501-520).- The concentration of amino-acids ammonia and ureA in the tissues oi' rats is comparable to that in the tissues of other mammals. 111 the; young growing animal the concentration of the amino-acids in the tissues is considerably higher than in the adult animal due pos- sibly to the greater Eetabolic activity of the young as compared t o the adult tissues. The effect of feeding with protein depends also on the age of the animal; in young rats the concentration of the amino-acids and urea in the tissues is increased whilsh in the adult niiimal no or only a slight increase can be detected.M. W. €3. Animal Calorimetry. XV. Further Experiments Relative l o the Cause of the Specific Dynamic Action of Protein. H. v. ATKINSON and GRAHAM LUSK [with G. F. SODERSTROM] ( J . Mdol. C'hem. 1918 36 415-427. Compare Lusk A. 1915 i 614). -The administration of hydrochloric acid to a dog causes a slight increase in the basal metabolism but a further increase is not observed when asparkic acid is simultaneously given. Aspartic acid like glutamic acid does not therefore exert any specific dynamic action. Asparagine and glycine behave veiy differently in meta- bolism the former being without specific dynamic action whilst the latter exerts the most powerful specific dynamic action of any of the amino-acids in protein which have been thus far tested.There- fore the hypothesis of Grafe (Deictsch. Arch. Kh'n. Med. 1915 ,118 1) that the specific dynamic action of protein is due to tho amino-radicles of the amino-acids is shown t o be incorrect. Neither succinic acid nor acetamide is found to increase the heat produc- tion of the animal. The authors draw the conclusion that the pro- cesses of deaminisation and urea formation have nothing to do with the specific dynamic action of protein. H. w. B. Penetration of Neutral Salts into [Animal] Cells. WILHELM VON MOELLENDORFF (3olZoid Zeitsch. 1918 23 158-163).-A number of experiments on the penetration of solutions of sodium chloride manganese sulphate uranium nitrate and potassium sul- phate into liver and kidney cells of animals are described.The experiments show that sufficient of the salts penetrate to produce an intracellular precipitation of the acid d o u r substiaaces contained in the cells. This precipitation is identical with the action of neutrali. IOG ABSTRACTS OF CJIEMTCAL PAPERS. salts on semi-colloids and is cliaracterised as a diminution of’ the dispersion. The process indicates that the cell walls are permeable to neutral salts. The process is in keeping with the theory of a sponge-like structnre for protoplasm. Synthetic Capacity of the Mammary Gland. I. Can this Gland Synthesise Lysine ? E. B. HART V. E. NELSON mid \V. P ~ T Z (J. Uzol. C’kem. 1918,36,291-307).-Rats fed on a lysine- free diet of zein and tryptopliarr with non-nitrogenous substances are able to give birth t o their young but appear to be unable to rear them.It is considered that these results are due to the failure o i the mammary glands of the rats to produce sufficient milk owing to the absence of the lysine necessary for tlie formation of tlie protein normally present in rat’s milk. Vitamine Studies 11. Does Water-soluble Vitamine Function as a Catalase Activator? R. ADASIS DUTCHER and FERDINAND A. COLLATZ ( J . Biol. Chiem. 1918 36 547-550. Com- pars A. 1918 i 561).-Vitamine extracts do not increase the cata- lytic activity of extracts of liver. The vitamine in the body does not act as a direct activator of catalase but seems t o stimulate tlie organism to greater production of the enzyme. Vitamine Studies. 111. Curative Properties of Honey Nectar and Maize-pollen in Avian folyneuritk .1%. A D A m DUTCHE~ [with L. v. J ~ A N c E ] ( J . Bid. Chern. 1918 36 551-555. Compare preceding abstract).-Honey contains a small amount of the water-soluble vitamine but the amount is so small that its cura- tive effect can only be observed after concentration of the vitamino by adsorption with siliceous earth. Nectar appears to be almost free fr9m vitamines but maize-pollen is relatively rich in this respect small amounts of pollen extract being sufficient to cause the recovery of pigeons in the last stages of plyneuritis. It is possible that i t is the presence of pollen grains in ordinary honey which confers on it its small curative power over pdyneuritis. H. W. B. Quinine h Animal Tissues and Liquids with Methods for its Estimation.W. RAMSDEN I. J. LIPKIN and E. WHITLEY (Ann. Trop. Ned. Purcisitol 1918 12 223-258. Compare Rams- den and Lipkin A 1918 ii 251; Hartmann and Zila A. 1918 i 328).-The method previously described by Ramsden and Lipkin is applicable to the estimation of quinine in most tissues b u t not in liver and brain. Given in large doses the alkaloid accumulates in most tissues (particularly the suprarenals and kidneys) much more than in the blood where three-fourths is in the serum but scarcely any in the red corpuscles; 900L of an intravenous dose leaves the blood in tE,e first minute after injection. Quinine reisists putre- faction in urine and fzeces but is rapidly attacked post mortem by the liver presumably in a manner identical with the normal femen- tative process of quinine metabolism during life.In a succession of large doses by the mouth more than 9OoL may be so metabolised. I n J. 2’. S. H. W. B. H. W. B.VEGETABL33 PHYSIOLOGY AND AGRICULTURE. i. 10 man there is considerable iciiosyncracy bot,h as regards the rate of excretioii and the concentration in tlie blood ; high concentration in the blood is associated with the symptoms of quinine intoxica- tion. Quinotoxine is attacked by the liver like quinine but some at lsast is excreted unchanged by the urine. Creatinuria . I. Exogenous Origin of Urinary Creatine. 11. STEENBOCK and E. G. G~toss ( J . Bid. Clhenh. 1918 36 ~G5-~89).-Experimeiits on pigs are described the results of whicli indicate that creatine is formed from a precursor o r precursors iii the protein molecule.Urinary creatine has an exogenous origin only when the protein in the food happens to contain a large pro- portion of tlia creatine precursor. Feeding with excess of a protein containing a relatively small proportion of t'he creatiiie precursor may result in an inhibition of the production of creatine on account of the accompanying diminution in protein katabolism eff scted by the agency of the non-nitrogenous portion of the protein of the food. I n the discussion of the results attempts are made to reconcile tlie numerous apparently contradictory conclusions arrived a t by other workers on this subject. G. B. EL W. B. Method for the Identification of certain Carbaddo-acids in the Presence of Amino- acids and of Urea. ALICE ROEIDE ( J . Uiol. C'ltem. 1918 36 467-474).-The method consists in decomposing the urea by urease and then extracting the carbamido- acids after acidifying with phosphoric acid by means of etliyl acetate. The extract is then distilled with steam. and the aqueous residue clarified with charcoal and then concentrated to small bulk. The crystals of carbamido-acid which separate are identified by tlie melting point etc. A method for .the quantitative estimation of these acids by the Van Slyke process is based on the fact that the anhydrides foriiied from them are not decomposed by nitrous acid. The difference in the volumes of gas evolved before and after boiling the carb- amido-acid solution with hydrochloric acid is a measure t,herefore of the amount of carbamido-acid present. Applying these methods it is found that after the injection of amino-acids into cats carbaniido-acids cannot be detected in the urine whilst injected carbamido-acids are excreted in an unaltered form. Conjugation of amino-acids with urea preparatory t o excre- tion does not seem therefore to occur in the animal organism. H. W. B.

ISSN:0368-1769    

DOI:10.1039/CA9191600103

出版商:RSC    

年代:1919

数据来源: RSC

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ii. 104 ABSTRACTS OF CHEMICAL PAPERS. Inorganic Chemistry. Determination of the Rate of Solution of Atmospheric Nitrogen and Oxygen by Water. I. W. E. ADENEY and H. G. BECKER ( 8 c i . Proc. Roy. DzcbZ. Soc. 1918 15 385-404). -The rate of solution of nitrogen and oxygen in distilled water tap-water and sea-water has been determined a t temperatures between 1 1 . 3 O and 1 2 ' 3 O by allowing a bubble of the air to pass up a narrow glass tube containing the water. This affects the mixing of the solution and constantly exposes the air to a fresh surface of water. The object of the experiments was t o substantiate the authors' views on the mechanism of solution of a gas in the liquid. Contrary to the generally accepted view i t is held that the gas isINORGANIC CHEMISTRY. ii.105 absorbed by the surface layer but the gases do not remain con- centrated here; they are gravitationally drawn downwards through the lower layers of water with comparat,ive rapidity (compare ibid. 1914). J. F. S. Flame Reactions Selenium and Tellurium in the Hydrogen-Air Flame. JACOB PAPISH (J. physicul Clzem. 1918 22 640-646).-The elements selenium and tellurium as well as their dioxides and hydrides have been introduced into the hydrogen air flame and the colour changes observed. Atl the same time experiments were made to ascertain the nature of the deposit if any on a cold object introduced into the flame. Selenium di- oxide produces a deep blue luminescence in the inner zone pale blue in the middle zone and green in the outer zone. There was a deposition of selenium in the inner and middle zones butl no deposition in the outer zone. Hydrogen selenide produces a very faint blue luminescence in the inner zone deep blue in the middle zone and green in the outer zone.There was a deposition of selenium in the inner zone but no deposition elsewhere. Selenium produces a luminescence coloared blue xriclet and green in the inner middle and outer zones respectively; in this case and in all following casm %he element was deposited in the inner and middle zones but there was rio depo'sition in the outer zone. Tellurium dioxide hydrogen telluride and tellurium all produce a lilac luminescence in the middle zone and a green luminescence in the outer zone whilst) tellurium dioxide and the free element produce a green luminescence in the inner zone whereas the hydrogen telluride produces a blue luminescence in this region.Possible explanations f o r the differences in the various cases are suggested. J . F. 8. The Constitution of Nitrous Vapours. P. JOLIBOIS and A. SANFOURCHE (Conzyt. rend. 1919 168 235-237) .-When nitric oxide and oxygen are mixed at. the ordinary temperature in the proportion of 4 1 by volume combination is instantaneous and nitrogen trioxide is formed and remains unchanged. If the gases are mixed in the proportion of 2 1 or if an excess of osygen is used the combination rapidly reaches the stage of the trioxide but after twenty seconds 34% of the peroxide is formed after thirty-seven seconds 6876 and after 100 seconds 92%. I f nitrous vapours are heated a t 400° the equilibrium tends towards the formation of the trioxide with partial destruction of the nitrous vapours.W. G. The Synthesis of Ammonia at High Temperatures. 111. EDWARD BRADFORD MAXTED (T. 1919 115 113-119). Production of Ammonia from f 1 Nitrolime," and the Time Yield under Various Conditions. WERNER GRAHMARN (Zeitseh. Elektrochem. 1918 24 385-391) .-The rate sf produc-ii. 106 ABSTRACTS OF CHEMICAL PAPEBS. t,ion of ammonia from boiling mixtares of “ nitrolime” and water ‘‘ nitrolime ” and sodium hydroxide or sodium carbonate of various concenhrations and “ nitrolime ’’ and potassium hydroxide or carbonate of various concentrations has been determined. I n the case of “nitrolime” and water i t is shown that the rate of decom- position of calcium cyanamide is extremely slow in all concentra- tions a t the boiling point and atmospheric pressure.Thus a 1% solu- tion is decomposed to the extent of 98% by seventy-two hours’ boil- ing. In the presence of sodium carbonate the decomposition really amounts to the decomposition of sodium cyanamide (a) under a con- stant sodium hydroxide concentration and ( b ) under a concentration of sodium hydroxide which increases during the reaction. In the case of an addition of sodium hydroxide the decomposition takes place under a regularly increasing concentration of the hydroxide. The same remarks apply t o t.he decompositions in the presence of potassium carbonate and hydroxide. The presence of alkali hydr- oxide o r alkali carbonate has an accelerating influence on the reaction ; the velocity increases with increasing concentration of the added salt to a maximum after which it remains more or less constant.The maximum in the case of alkali hydroxides occurs with much lower initial concentration of alkali than in the case of the alkali carbonat-es folr in these experiments the alkali concentration increases continuously from beginning to end of the decomposition. The experiments with potassium hydroxide and carbonate do not show the same maximum as the. sodium com- pounds under siniilar conditions so that since sodium hydroxide and potassium hydroxide are ionised to practically t.he same extent it must be taken that the acceleration of the decomposition velocity is not dependent ent’irely on the hydroxyl-ion concentration but that the cation and the undissociated molecules also exert a specific action.A number of orientating experiments were carried out under 30 atmospheres pressure at 150O. Under these conditions it is shown that even without the addit’ion of alkali the decomposi- tion takes place very rapidly until 75% of the calcium cyanamide is decomposed after which t8he velocity becomes much less thus in an aqueous solution 75% is decomposed in forty-five minutes but only 90% is deco’mposed in 120 minutes. In the presence’ of 10% alkali hydroxide 75% decomposition is reached in thirty minutes and 90% in seventy-five minutes. The “nitrolime” used in the experiments contained 16.85% of cyanamide nitrogen 0.65% of dicyanodiamide nitrogen 22.30% free lime and 0.31% sulphur. J. F.S. Effect of Phosphine and Hydrogen Sulphide on the Oxidation of Ammonia to Nitric Acid. GUY B. TAYLOR and JULIAN H. CAPPS ( J . Znd. Emg. Chem. 1919 11 27-28).-Pure acetylene has no effect on the catalytic oxidation of ammonia to nitric acid in presence of platinum (compare A. 1918 ii 265) the opposite results obtained earlier being due to the fact that the acetylene used contained small proportions of phosphine.INORGANIC CHEMISTRY. ii. 107 Hydrogen sulphide in low coacentrations has no immediate toxic effect on the catalytic oxidation. [See J . Soc. Chem,. Znd. March.] T. H. P. Oxidation of Coal. J. R. PARTINGTON (Chenz. News 1919 118 50-51) .-The experimental results obtained by Wheeler (T.? 1918 113 945) are discussed and an alternative ex- planation offered.The assumption that air is absorbed by freshly won coal with formation of an additive compound such as a complex oxide is an improbable one. The facts agree better with the hypothesis that the process is one of adsorption followed by direct formation of carbon monoxide. Carbon dioxide may be produced by oxidation of the carbon monoxide by moisture or even by interactlion of carbon and water hydrogen being formed a t the same time. The adsorption hypothesis explains the differ- ences observed when moist or dry air is used. I n absence of moisture the proportion of carbon dioxide formed would be ex- pected to be lower than when moisture is present. The fall of the ratio CO,/CO with rise of temperature also follows from the adsorption hypothesis. E. H. R. The Interaction of Stannous and Arsenious Chlorides.REGINALD GRAHAM DURRANT (T.,. 1919 115 134-143). Stable Solution of Silver Nitrate. F. LIEBERT (Chem. tPeekbZuc2 1919 16 74).-The solution of the saltl is exposed to the light until the organic matter present is exhausted and is then filtered through asbestos. The resulting solution may be kept in light without further alteration. w. s. ill. Atomic Weight of Lead from Samarskite. ARTHUR L. DAVIS ( J . PhysicaE Cltem. 1918 22 631-639).-Using a speci- men of lead obtained from samarskite which conhained U,O 12.21% and Tho 1*03% the author has determined the atotmic weight of this element. The method adopt-ed was that of Baxter and Grover (A. 1915 ii 456) and consisted in converting lead chloride into silver chloride.I n three experiments results varying from 206.246 to 206.363 were obtained for the atomic weight of lead. Calculations made from the content of samarskite on thorium and uranium lead to a value of 206.06 for the le'ad contained in this mineral whereas the experimental value is 206.30. This corre sponds with a mixture of 3 parts of radio-lead and 1 part of ordinary lead. I f it is assumed that 8% of the uranium is trans- formed along the actinium seriee t o form a stable isotope of atomic weight 210 the value 206.38 is calculated for the atomic weight of samarskite lead. The experimental value however is in better agreement with the supposition that either or both of the isotopes of lead in the thorium series are relativeIy short-lived and that the lead in samarskite represents a mixture of radio-lead of the uranium series atomic weight 206 and radiolead of the actiniumii.108 ABSTRACTS OF CHEMICAL PAPERS. series atomic weight 210. This conclusion is not in agreement with the value 206.04 found by Honigschmidt for the atomic weight of lead from crystallised uraninite (A 1914 ii 653). J. F. S. The Sub-acetate and Sub-sulphate of Lead. HENRY GEORGE DENHAM (T. 1919 115 109-113). The Rusting of Iron on Contact with other Metals and Alloys. 0. BAUER and 0. VOGEL (Mitt. k. Jlnterialspriv 1918 36 114-208) .-A discussion of previous work and new experiments on the influence of other metals on the corrosion of iron in con- ductivity water distilled water and chiefly 1% sodium chloride solution. Much ahtention is paid to the potential difference between the metals and electrolyte which was measured as follows the cell together with a millivoltmeter and a resistlance of 100,000 ohms is placed in parallel with a standard resistance W .A small current i is passed which is adjusted until no deflection of the galvanometer is obtained when the potential difference =ill7. A large number of results are given for the potential difference of pure metals and graphite against the normal calomel electrode. The contact of two metals in the 1% salt solution results in a large increase in the corrosion of the more electro-negative metal that of the more electro-positive one being reduced. In the water this effect is much less marked. Rusting of iron is entirely prevented when a current was passed which counterbalanced the solution pressure in the electrolyte so rendering the passage of the ions into solution impossible.For electrolytic iron in 1% sodium chloride solution at 1 8 O a minimum currentl density of 0-0000106 amps. per sq. cm. is. required calculated from the formula ( a . F)/(Fe/Z. q s ) where a is tlhs loss of weight of the iron in grams F 96,540 coulombs Fe/2 half the atomic weight of iron q surface of iron in sq. cm. exposed to attack and s duration of corrosion in seconds. [See further ,7. SOC. Clzem. Ind. March.] F. C. TH. Investigation of the Crystal Structure of White and Grey Tin by means of X-Rays. A. J . BIJL and N. H. KOLKMEIJER (Proc. R. Akad. Wetensch. Amsterdam 1919 21 405-408).- The structure of the two allotropic modifications of kin has been investigated by means uf X-rays. The method adopted was that due to Debye and Schemer and the interference photographs obtained indicate that both forms of the metal are crystalline. J. F. S. Reduction of Osmium Tetroxide by Hydrogen Chloride. OTTO RUFF and SUSANNE MUGDAN ( J . pr. Chem. 1918 [ii] 98 143-144).-The conclusion drawn by Milbauer (A. 1918 ii 202) that- osmium tetroxide is reduced to osmium monoxide by hydro- chloric acid is opposed to the results obtained by Ruff and Borne- mann (A. 1910 ii 305) and by Ruff and Rathshnrg (A. 1917,MINERALOGICAL CHEMISTRY. ii. 109 ii 323) and repetition of Milbauer's experiments by the authors shows that the tetroxide undergoes reduction t o a slight extent to the dioxide but not to the monoxide; the bulk of the tetroxide remains unchanged in t"he hydrochloric acid solution. Milbauer's erroneous results appear t o be due to the presence in the tetroxide of impurities although the commonest of these namely ruthenium tetroxide behaves similarly t o osmium tetroxide. T. H. P.

ISSN:0368-1769    

DOI:10.1039/CA9191605104

出版商:RSC    

年代:1919

数据来源: RSC

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VEGETABL33 PHYSIOLOGY AND AGRICULTURE. i. 10 Chemistry of Vegetable Physiology and Agriculture.. Autolysis of Starch. W. BIEDERMANN (Fermentforsch. 19 18 2 200; from C'hem. Zentr. 1918 ii 735. Compare A. 1917 i 62). -Boiled starch solutions aftper some weeks become infected with a bacterium which forms a sulphur-yellow pigment and hydrolysesi. 108 ABSTRACTS OF CHEMICU PAPERS. the starch to dextxose. The bacterium is possibly identical with or a t least closely relatled to Schardinger's BaciElus macerum. The previously recorded autolysis of starch was probably due to infection with this micro-organism. J. E. GREAVES (Soil Sci. 1918 6 163-217).-A r6sum6 of the literature on the subject of nitrogen fixation by Azoto- bacter and Clostridizinz psteum'nnunz. A full bibliography is appended.W. G. Influence of certain Conditions on the Comparative Con- sumption of Dextrose and Lavulose by Sterigmatocystis nigra starting from Sucrose. MARIN MOLLIARD (Conzpt. rend. 1918 167 1043-1046).-Using a culture liquid in which the nitrogen is entirely supplied by one ammonium salt and the ratio nitrogen carboa is 1 IG it is found that the ratio of dextrose to tzvulose consumed is considerably increased by the presence of acid. Similarly the ratio dextrose to lzevulose consumed is in- creased if the ratio nitrogen carbon is diminished to 1 160. In each of these cases the weight of mycelium obtained in a given Lime is also diminished. It is considered that lzvulose plays the principal part in the building up of the tissues. Capacity of Alcohols and Acids to Sustain the Growth of Yeasts and other Common Fungi.TH. BOKORNY (Allg. Brau iEopj. Zeit. 1917 747; from Bied. Zentr. 1918 47 191).-The. author has collected information regarding the behaviour of fungi yeasts and bacteria when cultivated in media containing various alcohols and acids. All acids exert an inhibiting action on fermentatioii when the concentration is increased to a certain limit which differs for each substance. Formic and oxalic acids are specially toxic. Bases are more poisonous than acids towards yeast. H. W. B. Quantitative Estimations of the Enzymic Activity of Living Cells. I. H. Eurmt 0. SVANBERG and S. HEINTZE (Fermentforsciz. 1918 2 194-199 ; from Ohem. Zentr. 1918 ii 746).-At 1 6 O an increase in px from tihe optimum for yeast invertase (5.07 t o 4.67) to 7.7 reduces the activity of the invertase from 0.067 to 0.007.Influence of certain Substances Extracted from Yeast by Alcohol on the Activity of the Yeast Enzymes. EMIL ABDERRALDEN and R. SCHAUMANN (Fementforsch. 1918 2 120-151; from Chem. Zentr. 1918 ii 737-738).-An extract of yeast prepared by boiling with 10% sulphuric acid and subse- quently treating with alcohol exerts an accelerating action on the enzymic cleavage of sucrose knd maltose and on the fermentation of dextrose I~vulose and parbicularly galactose by yeash The fermentation of lactose is not affected. The activity of carb- oxylase is increased. The accelerative action of the extract is observed not only with living yeast but in the cases of dried yeast and pressed yeast juice.Various fractions can be prepared from H. W. B. Azofication. W. G. -. H. W. B.VEGETABLE PHYSIOLOC;Y AXD AGRICULTURE. i. 109 the esti.sct poseasill; tliverse degrees of activating power one of the more powerful beiiig termed +. eutouin." This latter substaiice is prepared by precipitation of the alcoholic extrmt with acetone and is completely free from phosphorus. The author suggests that vitamines may resemble these extracted substances in exert- ing an activating influence on certain enzymic processes in the body. H. W. B. Behaviour of Yeast towards various Carbohydrates in various Concentrations and the Effect of the Addition of Amino-acids on tne Fermentation. ENIL ABDERHALDEN (Fei.iirei?tfol.sc?i. 1916 229; irolu Bied. Zentr. 1918 47 190).- "be extent of alcoholic'fermentation is not affected when the con- centration of the sucrose iii the solution is increased from 10 grams to SO grams per 250 C.C.The loss in weight is greater when alaniiie is added to the sucrose solution. When dextrose is sub- stituted for sucrose the extent of fermentation is found to vary with the concentration of the carbohydrate. When dried yeast is employed a distiiici latent period precedes the onset of ferment- atioii. H. W. B. Phytoehemical Reductions. XIV. Hydrogenation of a Ketone by Yeast. Change of Methylheptenone into the Corresponding Heptenol. C. NEUBERG and A. LEWITE (Biochem. Zeitscb. 1918 91 257--26G).-The change C~~e2:CIE.CH,*CH,*COMe into @~e,:CI-I.C~~,*@H,*GHMe*OH takes place t o the extent of about 10%.The product is sometimes lmorotatory and a t other times dextrorotatory. There is produced a t the same time an equimolecular proportion of acetaldehyde. The ketone appears to compete with this product fornied as an ordinary intermediary product of alcoholic ferrhentation for the available hydrogen. s. €3. s. Excitation oE Ferment Action. I\-OLE'C:ANG M+EICXIARDT and HERMANN APITZSCH (Biochenz. Zeitsch. 1918 90 337-347).-A criticism of certain statements in literature with regard to excita- tion of ferment action with some demonstrations of sources of error in methods of manipulation in experiments on which certain state- ments are founded. These refer more especially to the measurement of catalase action volumetrically to the difficulties of measuring the same amounts of catalase (or blood) and to the errors in the estima- tion of the action of urease due tto t h e neglect of hydrolysis of carbarnide while distilling off the ammouin.s. B. s. The Influence of Aluminium on the Germination of Seeds and the Development of Plants. JULIUS XTOKLASA with J. ~ E B O R W. ZDOBNICKY F. TYMICH 0. HORAK A. N ~ E c and 5. CWAGH (Biochem. Zeitsch. 1918 91 137-223).-This com- munication contains a very det,ailed account of the acbion of aluminium manganese and iron on the germination of seeds and the development of the plants. It indicat'es generally that very VOL. CXVL i fsmall amounts of aluminium salts exert a f avourable infiuence on the geriiiiiiation ol seeds whereas larger amo’unts exer-c a toxlc action. Similar remarks apply t o saim o i rnanganabe.\%‘hen large amounts oi manganese salts exert a toxic action an antagonistic effect can be produced by aluminium salts when the concelitiation of the latker is not too high and the toxic effect of both ions comes into play. h study of the action of these variow salts ,iilell 7,IJed in the nutrient solutio’ns for growing plants indicated thah aluminium is very toxic to xerophytes whereas the hydrolytes and hygrophils show a considerable resistance. As regards the meso- phytes a toxic action could be determined iu the case of iron ions which could be antagonised by aluiiiinium. Aluminium and man- ganese ions iii sufficiently !ow coiicentrations both together or alone produce a iavourable efTect on growth ; higher coneentra- tiom act tosically.There is no antagonistic action as regards toxicity of iron and manganese. The authors deduce from their results a mathematical expression for the growth curves and develop a general theory of the acticn of chemical reagents 011 growth. Measurements were made of the electrical conductivities of the salts employed and comparisons instituted between the intensity oE action of the various ions and the dissociation grade of the salts; a considerable parallelism was found to exist between this physiological in tensity of action and the conductivities of the salt solutions. s. €3. s. Catalase and Oxydase Content of Seeds in Relation to their Dormancy Age vitality and Respiration. WILLIAM CROCKER and GEORGE T. HARRINGTON ( J . ,-2gric. Res. 1918 15 137-1 74).-The concentration or’ solutions of hydrogen peroxide may readily be measured by.determining the volume of oxygen liberated on the addition of an excess of powdered seeds contain- ing plant catalase. Similarly the catalase activity of seeds may be measured by using an excess of hydrogen peroxide but in this case the latter solution must first] be made neutral to phenol- phthalein by the addition of N/lO-sodium hydroxide. The authors have carried out a general investigation as to the coadi- tions affecting catalase and oxydase activity of seeds and find t h a t in certain seeds there is a close correlation between catalase activity and respiratory inteneity but no correlation between these twol factors and the vitality of the seeds or the vigour of the resulting seedlings.They find t h a t general conclusions cannot be drawn as t o the cataIase behaviorir in a11 seeds. but it seems probable that seeds can be separated into several physiological types for each of which more or less general conclusions can be drawn. Catalase activity of seeds seems to agree more closely and generally with phyFiologiea1 behaviour than does oxydase activity. [See further J. SOC Chem. Ind. 1919 February.] Distribution of. the Mineral Elements and Nitrogen in the Etiolated Plant. G ANDRB (Comnpt. rend. 1918 167 1004-1006) .-The author has investigated the proportions of W. G .VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 1 11 mineral matter and nitrogen which pass during etiolation from the cotyledons into the plantule in seeds germinated in t'he dark in an inert medium.The seeds used were white haricot germinated in sand previously extracted with dcid and calcined. After twenty-five days the stenis being 30-35 cm. in lengt6h the plants were removed and their roots washed. Their cotyledons were separated from the ?tern and roots and weighed separately. and then analysed. The major portion of the calcium remained in !he cotyledons whilst the niagnesiiirn and t o a still greater esterit the potassium had migrated t o the roots and stem. Nearly 75% of the phosphoric acid and nitrogen were transported from the cotvledons to the plantule and the migration of the sulphur was v e ~ similar w. G. Mechanism of Assimilation Processes. K. RCHAUW (Bey. 1918 51 1372-1375).-The conclusions recorded by Willstatter and Stoll (A.1918 i 207) had been drawn previously by the author (Sitzungsber. Ges. Befiid. gesnmt. Natzcrwiss. Mnrhury 1907 158). c. s. Colloidal Properties of Protoplasm. Imbibition in Rela- tion to Growth. FRANCIS E. LLOYD (Tram. Roy. Sue. Canada 191'7-18 11 133-139).-Living protoplasm as such behaves towards acids and alkalis in a manner sufficiently like t h a t of gelatin t o warrant the view t h a t imbibition is a factor in growth. The results in growth are called forth by much lower concentrations of the reagents; this is probably due t o the different nature of the emulsoids involved. J. F. S. Conductivity as a Measure of Permeability. W. J V. OSTERHOUT (1. Biol. Chenz. 1918 36 485-487).-Experiments are described which are designed t o elircidate whether when an electric current passes through a tissue any of the current passes through the protloplasm or all through the intercellular substance.Employ- ing a green marine alga ( U h n ) and a marine flowering plant (Zostern) 'both with cellulose walls it is found t h a t after killing by methods which do not produce irreversible changes in the properties of cellldose the condnctivity rises t o a constant value and is not thereafter affected bv exposure t o reagents which moduce great alterations in the conductivity of living tissues. Noreaver the tem- perature-coefficient of the electric.11 conductivity of livinq tissue differs from that of dead tissue and the effect of placing a tissue in cont'act with a strong calcium chloride solut.ion is not an increase in the conductivity b u t a decrease on account of the diminished conductivity of the protoplasm killed by tke salt more than counter- balancing the increased conductivitv of the intercellalar tissues.The alterations of conductivity observed in livinq tissue are due therefore to chanqes in the protoplasm and not t o chanqes in the non-livinq intercellular snbstar-lce. and as the results obtained by the electrical method are in complete aqreement with those obtained by other methods for measuring permeability such as exosmosis.i. 112 ABSTRACTS OF CBEMICAL PAPERS. diffusion through membranes of living tissue etc. the author draws the conclusion that tho electrical conductivity is a measure of the permeability of the protoplasm of the cell. H. W. B. Effect of Diffusion on the Conductivity of Living Tissue.W. J. V. OSTERHOUT (J. Bid. Chem. 1918 36 489-490).-Elec- trolytes with univalent cations usually produce an increase in the electrical conductivity of living tissues whilst those with bi- or ter- valent cations first diminish and then increase the conductivity. Certain apparent exceptions t o this rule have been noted and theso are now shown to1 be due to' the effect of diffusion. Thus on trans- ferring tissue of .Laminark from sodium chloride to rubidium chloride solution of the same conductivity the molecules of sodium chloride diffuse o a t of the tissue more rapidly than the larger mole cules of rubidium chloride can diffuse inward. Hence there is a temporary deficiency of salt in the tissue and the conductivity accordingly falls.Reverse effects are prociuced on transference into lithium chloride solutions. E. W. B. Method of Measuring the Electrical Conductivity of Living Tissues. W. J. V. OSTERHOUT ( J . Bid. Chem. 1918 36 557-568).-Various types of apparatus are figured and described which permit of the measurement of the electrical conduc- tivity of pieces of living tissue or of intact organisms. Successive measurements do not vary more than 1% from the mean value. H. W. B. The Absorption Curve of the Green Colouring Matter in Living Leaves. A. URSPRUNG (Ber. Dezct. bot. Gcs. 1918 36 73-85).-The absorption curve has been determined by the thermoelectric method for the green pigments in a living leaf of Trudescantiu". A very slight absorption occurs in the green part of the spectrum which increases towards the red and the violet ends reaching a maximum in the violet which is greater than that occurring in the red.Towards the red end of the spectrum the absorption cwve reaches a maximum point between B and C and then falls rapidly towards the ultra-red. H. W. B. Significance "of the Wave-length for StarcMormation fin the Green Leaf]. A. URSPRUNG (Ber. Deut. bot. Ges. 1918 36 86-100. Compare preceding abstract) .-A comparison of the absorption curve with one indicating the extent o€ formation of starch in the green leaf reveals a close parallelism extending from the ulttra-red to the green part; of the spectrum. From this point towards the violet marked divergence is observed ; the absorption increases to a maximum whilst the starch-formation greatly dimin- ishes.It ia probable that the latter phenomenon is occasioned by the action of the ultra-violet light on the stomata which results in the reduction of the supply of carbpn dioxide for photo-synthetic purposes. In a few experiments with leaves containing no stomata,VECIETABLE PHYSIOLOGY AND AGRICULTURE. i. 11 3 the par allelism between absorption and starch-formation could be established as far as the bluish-violet part of the spectrum. H. W. B. Microchemistry of Plants. X. Siliceous Bodies in the Epidermis of Campelia Zanonia I Rich. XI. Crystalline Carotin in the Cup of Narcissus poeticus. HANS MOLISCII (Ber. deut. bot. Ges. 1918 36 277-281 281-282).-Siliceous bodies similar t o those discovered by Mobius ( Wiesner-Festschrif t Vienna 1908 p.81) in the leaves of Cnllisin repens are pre- sent in the epidermis of Campelin Zrr7207zia. They occur in small cells in the leaves and stalks and are insoluble in acids except hydrcrffuoric acid. When the leaf is immersed in phenol solution o r in Millon's reagent the bodies assume a peculiar red hue which renders them very apparent. These two Cornmelime therefore are related not only botanically but also in a pronounced chemical manner. The xed colour in the rim of the cup of Narcissus po2ticU-s is found to be due to the presence of accumulations of carotin crystals in the cells. H. W. B. The Phenol of the Leaves of Coleus amboinicus Lour (C. Carnosus Hassk.). F. WEEHUIZEN (Rec. trail. chin&. 1918 37 355-356 ; Pharm. Weekblad 1918 55 1470-1472).-The essential oil of Coleus amboiiiic~cs contains a phenol which the author has identified as carvacrol.W. G. Presence of Hydrogen Cyanide in a Fern Cystopteris alpina. MARCEL MLRANDE (COP@. rend. 1918 167 695-696).- The fern Cystopteris alpinn Desv. contains in its leaves a cyano- genetic glucoside which under the influence of an enzyme also contained in the plant is hydrolysed and yields hydrogen cyanide and benzaldehyde. The proportion of hydrogen cyanide given by the leaves is lowest in the early part of SBptember (for example OoO1lo/o). C. A. M. Production of Glycine by Isaria densa. MARIN MOLLIARD (Compt. rend. 1918 167 786-788) .-The fungus Isaria densa when cultivated on gelatin decomposes it giving glycine the yield of this amino-acid being equivalent to 33% of the gelatin decorn- posed whereas by acid hydrolysis gelatin only yields 1605% of glycine.Similarly this fungus decomposes fibrin giving 38% of gIycine and also ovalbumin serum-albumin and casein giving on an average 33*6% of glycine. L. REUTTER DE ROSEMONT (Schweiz. Apoth. Zeit. 1918 56 55-56; from Chem. Zentr. 1918 ii 89 736-737) .-The results indicate that certain alkaloids exist pre- formed in poppy juice and are not the products of subsequent fermentation processes. On distillation in a vacuum poppy juice W. G. Sterilised Poppy Juice.gives off fomiic and acetic acids aud after subsequent treatment; with sodium hydroxide ammonia pyrrolicline. and methylpgrrol- idine. By extraction of the tarry residue several bssic mbstances including codeine but nob morphine are obtained.Light petroleum extracts pyrrolidine benzene a yellow ZiquZcZ (C8H3Q4N) awi- cIdo?.ide m. p. 231° chloroform a yellsmish-brown powder (C$&O,N) arid amyl alcohol a solid trlknloid (C2H305N),. The residue is soluble in dilute hydrochloric acid and from the solut.ion sodimii hydroxide precipitates a colourless sirb.rtatice (CHO,N),. Lactic meconic and oxalic acids together with dextrose were also detected in the original juice. El. TV. B. Vegetable and Animal Fats and Waxes. HI. ALBERT 33. WEINHAGEN (Zeitsch. physio7. Ghenz. 1918 103 84-86. Com- pare A. 1918 i 56).-The solid fat isolated from rice bran dces n o t contain any glycerol whilst? the liquid oil contains olnly about 1.7%. H. W. B. Oxydases with Special Reference to their Presence and Function in the Sugar-cane.RAXJI NARAIN (Aqric. J. India 1918 47-64).-Laccases and aldehydsse are found t o Fr? present in the cane but tyrosinase is absent". The author finds t,h;it. the direct guaiacum reaction depends niore on the presence of a peroxide than on t h a t of catechol. As a preservative for oxydases chloroform is far more satisfactory than either ether or toluene. In the cane the lower portions show a greater oxydase activity than the xpper portions and thus tke oxydases are stronzer in that part of the plant where the sugar is stored. Similarlv tke leaf and the adjoining green portion of the c m e are ricliex- in oxydasec than thc stem. The oxydases are not destroyed by boiliiq the extract con- taining them f o r fifteen miniites. nfthouqb they take some time t~ recover their a,ctivity after coolitig.Similwlv a reducing agen b such as hydrogen sulphide only temmrarity inhibits their activitv but does not dest.rog it. perrnanent.ly. The a.ut?hor considers tli-t oxydases are not enzymes in the true s e ~ s c of the word. W. G. Gaseous Products of the Putrid Fermentation and the Odour of Trumes. I. GUARESCHI (Gaxxetta 1915 48 ii 98-106).-The gaseous or highly volatile px-oducts emitted during the putrefaction of truffles are mostly absorbable by soda lime (com- pare! A. 1916 ii 324 562). Those not so absorbed have the odcur of the fresh trufie such odonr being- due t o one o r mol-e gases or volatile compounds which are formed by the putrefactive alteratir,?. of the proteins lout are n o t yet identified. T.R. P. Action of Coal Gas on Plants. IV. Action of Coal Gas on the Root Systems of Trees. Cause of the Action of the Gap,. C. WEX-IMER (Be?.. Bezit. hot. G'es. 1918 36 140-150. Compare 4. 191'7 i 618).-The experiments on the effects produced by pass- ing gas through soil contaix;:: the roots of plants have beenVEGETABLE PHYSIOLOGY AND AGRICULTUEE. i . P 15 esteiided to small trees in pots. It is found that the effect produced is ciependelnt on the seasou of the year in which the experiment is performed; it completely kills the tree in the spring; in autumn the leaves fall off b u t the tree remains alive whilst in winter no pernicious effect is observable. When the soil is replaced by a solution of salts similar toxic efiects are observed.The toxicity appears t o be due t o one or more constit?uents of the gas and not to mere absence of oxygerr. Any treatment of the gas which removes its peculiar odour also abolishes its toxicity a result which seems t o sliow that the toxic agent is that. constituent of the gas which confers on it its characteristic adour. Soil Acidity as Affected by Moisture Conditions of the Soil. S. I). CONNER ( J . Agi-zc. l i e s 1918 15 321-329).-The acidity of acid soils kept under different& conditions of moisture in pots for a year varied with the differellit coiiditions of moisture for a given soil. Soils rich in organic matter showed the greatest acidity alter being kept Tully saturated whilst soils poor in organic matter showed ihe greatest acidity after being kept half-saturated.The potassium nitrate extract from the fully saturated soils contained more soluble ferrous ircii and manganese but less aluminium than the other soils. Thus the measurable acidity of acid soils varies to a large degree under different conditions of moisture and aeration but this variation is due to chemical rather than to physical cfiarrges in the soil. ?V. G . 33. W. B. Determining the Absolute Salt Content of Soils by Means of the Freezing-point Method. GEORGE J. Bou~oucos and M. AT. McCoo~ ( J . Agrzc. Res. 1918 15; 331-336).-The authors find that at a comparatively high content of moisture the iufiuence of the unfree water on the concentration of the soil solu- tion is practically negligible. The f reezing-point method can there fore be used to determine the absolute salt content of soils by bring- ing them to a suitable content of moisture before determining the depression of the freezing point.[For details see J . SOC. Cizem. 1 n d. 191 9 February.] Hydrogen-ion Concentration--Soil Typcs--Common Potato Scab. LOUIS J. GILLESPIE and LmvIs A. HURST (Sod. h'ci. 1918 6 219-235).-The authors find that the electrometric method (compare Giilespie A. 1916 i 303) and the colorimetric method of Clark and Lubs (compare J. U a e f . 1917 2 1 109 191) for determining hydrogen-ion concentration of soiIs give results wliich are in agreement within the limits of experimental error. It is necessary t o add 1 or 2 C.C. of water to each gram of air-dry soil. but this addition of water does n o t seem to be a serious limitation.From an examination of a large number of soils the authors find a close correlation between the hydrogen-ion exponent and the occur- rence of common potato scab. With an exponent below 5.2 scab seldoim appears but with exponents much above this figure the potatoes are generally scabbed. W. G . W. G .i. 116 ABSTRACTS OF CHEMICAL PAPERS. Chlorine index as a Comparative Measure of the Bichness of Soils in Humus. 1,. LAPICQUE and E. BARB^ (Compt. rend. 1919 168 118-121).-The authors find that the amount of an aqueous solution of sodium hypochlorite decomposed in a given time by a given volume of soil varies considerably with the soil taken and that this estimation forms a rough method of placing the soils in the order of their probable richness in humus the volume of chlorine liberated varying directly with the humus content of the soil.W. G . Importance of kIcduici Action in the Soil. SELNAN A. WAKSMAN (Sod SCZ. 1918 6,137-155).-&1oulds have been isolated in large numbers from cultivated and unculbivated soil. By t110 growth of their mycelia changes in the organic and inorganic con- stituents of the soil are brought about but no nitrification or fixa- tion of nitrogen is eff'ected. Not1 much ammonia is produced i n the presence of available carbohydrate as a source of energy as it is absorbed in the formation of mould protein but in the absence of carbuhydrate considerable amounts of ammonia are left in the soil. Carbohydrates are decomposed with the formation of carbon dioxide. Moulds exercise an unfavourable effect on soil fertility in that they compete with green plants for available nitrogen compounds.On the other hand they exercise also a beneficial effect on account of their large production of enzymes and acids which produce further changes in soil constituents favourable to the growth of green plants. [See J. Soc. Clzenz Ind. 1919 February.] Nitrogen Compounds in Rain and Snow. FRANK T. SHUTT and R. L. DORRANCE (Trans. Boy. SOC. Carrzada 1917-1918 [iii] 11 63-72).-A series of analyses of snow and rain which have fallen in o r near Ottawa during the years 1908-1917 is recorded. The analyses deal with the nitrogen compoundfi and are expressed as parts of nitrogen per million as (i) free ammonia (ii) albuminoid ammonia (iii) nitrates and nitrites. The average of these for the ten years is 0.461 nitrogen as free ammonia 0.138 as albuminoid ammonia 0.277 as nitrite and nitrate. This corre- sponds with 6.583 lb. of nitrogen per acre. A further analysis of the results for the various months is also given from which it is shown that snow is decidedly poorer in all forms of nitrogen compounds than rain (compare A. 1915 i 636). Composition of the Waters of the *Inter-Mountain Region. J. E. GREAVES and C. T. HIRST ( J . I d . Eng. Chem. 1918 10 1001-1004).-Analyses of a large number of river waters are recorded the majority of which are used for irrigation purposes. Whilst some of the waters are free from objectionable constituents others although good a t their source were found to contain large quantities of alkali sulphates etc. after flowiiig through a dis- trict rich in soluble salts. The effect of these saline waters on J. H. J. J. F. S. vegetation is discussed. w. P. s. - _.

ISSN:0368-1769    

DOI:10.1039/CA9191600107

出版商:RSC    

年代:1919

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY. Mineralogical Chemistry. ii. 109 Fibrous Quartz from Rhode Island. ALFRED C. HAWKINS (Amer. Min. 1918 3 149-151).-Fibrous quartz resembling asbestos in appearance and consisting of long delicate flexible fibres fills narrow veins in metamorphic slates a t several localities in Rhode Island. It ranges in colour from pure whibe to green. The green colour is due to the presence of admixed actinolite as shown by microscopical examination and by the following analyses I green from Feuner’s Ledge Crsnston; 11 white from the same locality; 111 green from Portsmouth. SiO,. A1,OR. Fe,O,. CaO. MgO. H,O. CO,. S. Totd. I. 77.15 8.72 7.68 0.70 3.96 1.40 - 0.52 100.13 11. 9442 4-68 trace &race 0.16 - - 99.64 111. 91.83 1-61 3.81 0.80 1.37 0.70 0.60 0.12 100.74 v L.J. S. Hambergite from Kashmir. R. C. BURTON (Rec. Geol. S.zcrvey Zndia 1913 43 168--172).-C?rystals of harnbergite together with cookeite prehnite tourmaline beryl euclase ( ?) and amblygonite have been found in the granitic dkbris in the Kashmir sapphire mines. They were probably derived from the iieighbouring pegmatites. A description is given of a twinned crystal Analysis gave G10. B,OP H,O. Total. Sp. gr. 52.40 [37.39] 10.21 1 oo*oo 2.36 L. J. S. Phosphorite from the Island of Juan de Nova Madagascar. J. ORCEL (Bull. Soc. fmm. Mim. 1918 41 104-108).-The phosphate deposits on the small island of Juan de Nova or St. mristophe aboutl eighty miles off the west coast of Madagascar have been formed by the action of soluble phosphates derived from guano on the underlying caral-rock.Analysis I is of brown con- cretionary phosphorite and I1 of brourn earthy material of prac-ii. 110 ARSTRA4CTS OF CHEMICAL PAPERS. tically the same composition. The latter is worked under the name “leached guano.” The analysis (I) shows an excess of 8.45% CaO indicating t,he voedckerite formula 3Ca,(P04)2,Ca0 (A. 1912 ii 565). CaO. 8r0. MgO. Al,03. P,Os. C1. so,. I. 48.63 0.17 1-75 0.15 35-56 0.29 0.56 11. 46.85 n.d. 0.38 35.19 0.14 0.58 - Organic Loss CO,. matter. H,O. at 110’. Insol. Total. I. 0.14 1.27 7-97’ 4.00 0-05 100.54 11. 10.08 5-35? 0.03 98.57 \ 2 L. J. S. The Colour Change in Vivianite. THOMAS L. WATSON (Ainer. &€in. 1918 3 159-161).-The large pale green crystals of vivianite from Plant City Florida (A* 1918 ii 119) are non- pleochroic and yield a colourless powder.This powder rapidly changes especially in sunlight t o deep blue and becomes strongly pleochroic. An unground sample of the crystals showed FeO 42*88% whilst the finely ground material gave FeO 38.43%. Tho change i n d o u r and pleochroism is thus due to the partial oxida- tion of the iron and not to inversion as was ah first suggested by the microscopical aspect of &he material. A tabulation of the refractive indices of pale green and of dark blue vivianite from various localities indicates that the oxidation has been accom- panied by an increase in the values of j3 and y. L. J. S. Copiapite in Coal. WILLIAM J. MCCAUGHEY (Amer. Mzn. i918 3 162-163).-A specimen of pale green fibrous melanterite from the Congo coal mine in Perry County Ohio changed in ths course of a year to dull white and the fibres became brittle.Yellow spots also developed especially a t the points of contact between the melanterite and the associated shale. This yellow material consists of minute tabular crystals and is proved by the following analysis and refractive indices to be copiapite Fee03 5 SO 18H20. SO,. Fe,O,. H,O. Insol. Total. a. B. Y* 39.68 29-98 30.45 0.31 100.42 1.525 1.545 1.595 L. J S . Nasonite from Langban Sweden. G. AMINOFF (Geol. Fiir. Forh. 1916 38 473).-This mineral hitherto known only from Franklin New Jersey (A. 1900 ii 89) has been observed a t Lingban in the veins of ‘‘ secondary calcite,” where i t is associated with schefferite native lead apophyllite etc. It forms white to pearl-grey lamellar masses or less often hexagonal prisms with&TI?TERALOGZ('hL CHEMISTRY. ii.111 rounded faces. Refractive indices (Na) o = 1.9453 e = 1.9710. Analysis by R. MAUZELIUS agrees with the usual formula Pb,( PbCYI),Ca,( Si20,)3. SiO,. PbO. FeO. JInO. CaO. MgO. C1. H,O. Total. 18.23 67.67 0.04 0.14 11.29 0.20 2.90 0.34 100.71 L. J. S. Anorthite from Japan. 8. KOzu (Sci. h ' e p Y'dhokic Imp. Unav 1914 Geol. Ser. 2 7-33).-The results are given of elaborate determinations of the optical constants (refractive indices optic axial angle and dispersion of the optic axes) for different wave- lengths of anorthite from three Japanese localities. As these show certain differences amongst themselves the following analyses by H. s. \ \ 7 ~ ~ ~ ~ ~ ~ ~ ~ ~ were made of I aiiorthite crystals from Miyake-jima one of the Seven Izu Islands south of Tokyo and 11 crystals from the Tarumas volcano in Holrkaid6.SiO,. Alto,. Fe,O,. CaO. MgO. K,O. Na,O. Total. Sp. gr. I. 44-49 36.00 0.08 19.49 0.04 0.03 0.59 100.72 2.758 11. 44.03 35.93 0.10 18.66 trace 0.07 1-00 100.24 2.757 Barium aiid strontium are absent and the slight differences in composition cannot be co'rrelated with the differences in the optical constants. I corresponds with Ab3.,An,5.,Cg,.7 and I1 with Ab,.7An,,.,,C"g:!.,0t-,.6. The melting points are 1538O and 1536O k 2O respectively. L. 5. s. Racewinite a New Mineral from Utah. A. N. \YINCHELL (ECOPZ. Geol. 1918 13 611-615).-The mineral occurs as veins and irregular masses in limestone and also replacing the carbonate portion of calcareous sandstones near the contact with porphyry in the Highland Boy mine a t Bingham Utah where it is often intergrown with pyrites and other ore minerals. It is brownish-black with a dull to bright lustre and somewhat resembles coal in appearance.When freshly taken from the mine it is bluish-green ; the change in colour t o brownish-black takes place slowly throughout the whole mass and after six months the largest pieces were altered to the centre. The mineral undergoes other remarkable changes in colour. I n boiling xiitric acid it is insoluble but gradually changes to yellowish-brown and translucent. I n hydrochIoric acid it7 is slowly soluble and shows the same change in colour. Thin splinters and particles under the microscope are pale to brownish-yellow.I n clove-oil this colour changes first to grass-green aiid then to black but the same change does not take place in cedar-oil and some other oils. The finely powdered mineral is nearly white with a yellow tinge. The material is coarsely crystalline with no cleavage or crystal-faces; it is friable and the fracture coiichoidal. Sp. 9:. 1.94-1-98 H 24 ; optically biaxial with large angle and negative IZ. about 1-51. It adheres to the tongue and slakes in water breaking up with a sharp audibleii. 112 ABSTRACTS OF CHEMICAL PAPERS. sound. respectively Analyses I and I1 by 5. P. HICKEY and C. L. AUSTIN SiO,. A1.03. Fe203. CaO. MgO. H,O. Total. 11. 43.24 23.69 8.05 2.42 0.78 21.80 99.98 r. 43-92 23.68 7.37 2.52 0-50 22.04 100.0: A sample of the green unaltered mineral showed 0.60% FeO.Over sulphuric acid 7-8% H,Q is lost in one day and 14% after forty-nine days ; this is re-absorbed from a moist atmospf-ex. Other determinations gave the loss a t 70° as 8% and a t ZOOo as 12.1%. Heated to dull redness the crystal structure is not destroyed and the optical characters are not materially altered. L. J. S. New Swedish Minerals = GUST. FLINK (Geo 1. For. Fo~h. 1917 39 426-452).-Ektropite forms crusts of small brown rect- angular plates on garnet with calcite and barytes in magnetite ore from the Norrbotten mine at L;Pngban. The crystals are mono- clinic (a b c = 0.74 1 0.84 p= 61%’) with a tabular habit parallel to the orthopinacoid and elongated in the direction of the axis of symmetry.They are opaque with a vitreous to silky lustre but i n thin splinters under the microscope the material is translucent and yellow. Analysis I by N. SAML- BOM gives the formula 12R8,8Xi0,,7H2O. The mineral is related to caryopilite and neotocite. D 2.46 H 4 n 1*62-1*63. sio,. Sb,05. PbO. A1,0,. Fe,O,<. FeO. - 0.75 - 5.80 11. 7-75 20.76 - 9.50 3.58 2.44 I. 35.02 _. - - - 111. 34.72 - 41-74 MnO. CaO. MgO. H,O. Total. I. 37-20 3-59 7-20 8.89 99.89” 11. 52-61 0.58 3.06 0.11 100.39 I11 2.17 20-28 0.20 0.10 99.90-f * Including K,O 1-13 Na20 0.12 metallic sulphides 0.19. i- Including BaO 0-69. li’-atoptrite occurs as tabular crystals and irregular lumps with magnetite in granular limestone in the Brattfors mine at Nordmark. The crystals are nionoclinic (a h c == 0.79223 1 0.48985 f l = 78O57’) and have a highly perfect cleavage parallel to the orthopinacoid n(100).This cleavage resembles that of mica but the cleavage flakes are very brittle and not flexible. D 4.5 H 54. The mineral is black and opaque with a bright metallic lustre. Thin flakes am red by transmitted light and strongly pleochroic. Analysis 11 by R. MAUZELIUS gives the ratios 14R0,Z (A1,Fe),03 Sb,O 2Si0,. The mineral resembles manganostibite in appearance and itl may perhaps be identical with the incompletely described helinatostibite. Margarosanite (A.. 1916 ii 532).--This new mineral has been found in some quantity in the “Lukas Ort ” and Bjelkes shaft a t LBngban where it is associated with nasonite schefferite apo-MINERALOGICAL CHEMISTRY. ii.113 phyllite calcite etc. The masses weighing up to 1 kilo. are snow- white with pearly lustre and columnar structure. Crystpals are rare; these are triclinic (a b c = 0.74998 1 1.2849 u= 74O37’ j3 = 50°28’ y = 78O53’) with three cleavages that in one direction being highly perfect. D 4.39 €€ 24. Analysis 111 by R. MAUZELIUS gives the formula PbCa,(Si0,)3. The mineral is readily and completely soluble in dilute nitric acid. It is perhaps a member of the pyroxene group. Thaumasite from Langban is described as loose aggregates of small but distinct crystals. These are hexagonal with prismatic habit a c = 1 0.9479. L. J. s. Minerals in the Crystalline Limestone of Crestmore California. ARTHUR S. EAKLE (Bull. Dep. Geol. Unav. C‘ulifornia 1917 10 327-360).-At Crestmore in Riverside County two hills of crystalline limestone resting on a boss of granodiorite and intruded by veins of quartz-monzonite-porphyry and pegmatite are extensively quarried for the manufacture of Portland cement the partly decomposed granodiorite (anal.I ) being used as a sub- stitute for clay. In one hill the limestone is a white marble (anal. I I ) whilst in the other it is composed largely of blue calcite. In the latter the metamorphic processes have been more intense there having also been hydrothermal action by phosphatic siliceous and carbonated solutions and zones composed of a great variety of metamorphic minerals have been developed at the contacts with the intrusive veins. The blue calcite which forms bands and patches intermixed with the metamorphic minerals is sonietimes of a deep colour fading on exposure to sky-blue.It is decolorised a t a low heat and the colour is thus perhaps due t o organic matter. Detailed descriptions are given of about fifty mineral species from this locality and analyses of the following. Wilkeite (A. 1914 ii 283) and xanthophyllite (A. 1916 ii 443) have been previously described. Brucite (anal. 111) forms grey yellow or red granules eiribedded in the white liniest*oiie. It consists of an aggregate of twisted plates aiid threads much compressed aiid strained and has no doubt been derived from periclase (&!go) with an accompanying considerable (2; times) increase in volume. Wollastonite is of abundant occurrenco as columnar and fibrous masses ; as snow-white finely granular and loosely coherent aggregates (anal.IV); axid as crystals of various types (anal. V of clear crystals). The distribii- tion of the faces 011 these crystals indicates that the symmetry is non no clinic-hemimorphic or perhaps triclinic. Several new crystal- forms are noted. The mineral is strongly triboluminescent. Refractive indices a= 1.614 p == 1.629 y = 1-631. Idocrase as yellow or brown crystals and masses is also abundant; anal. VI by J. B. WRIGHT of green idocrase. Garnet crystals and massive of a cinnamon colour occurs with the ittocrass; anal. V I I by J. B. WRIGHT of massive grossularite. A new analysis (VIII byii. 114 RBSTRAC'PS OE' CHEMICAL I'AYNlLY. G . SURR) is given of the monticellite which occurs iii intimate association with the xanthophyllite Two new species crestmoreite and riversideite hydrated calciuin silicates are described. Crestmoreit e is an alteration product of wilkeite and in the description of this mineral it; was provisionally referred t o as okenit'e (A.1914 ii 283). It occurs as small patches of earthy t o compact snow-whit>e and opaque material in the blue calcite. Under the microscope it shows straight extinction with positive elongation low birefringence and fi = 1.590. Hardness 3. It is readily soluble in acid with separatlion of some flocculent silica although most of the silica goes into solution. Boiling water extracts some calcium. Water is expelled mostly a t a high temperature; a t 200° the loss is 3'27% and a t 300° 10.27%. From the analyses IXa-c a complex formula is deduced but the phosphate sulphate and carbonate no doubt represent admixed unaltered wilkeite. Simpler formulae are CaSiO,,H,O' and 4H,CaSi0,,2H20 preference being apparently given to the former.Riuersideite occurs as narrow seams of white fibrous material in massive idocrase. H = 3 ; refractive indices a= 1.595 y = 1.603 ; the fibres give straight extinction with positive elongation. A complex formula is deduced from anal. X; neglecting phosphate and sulphate simpler f umulz are 2CaSiO,,H,O and 6H2Ca Si,07 H,O preference being given to the formelr. These two new minerals may be regarded as hydro-wollastonites. Orthoclase pure white material from the pegmatite anal. XI. Okenite (anal. XII by W. FOSHAG) occurs as tufts of long slender needles and fibres on apophyllite which is found in cavities in wollastonite between the pegmatites and the limestone.The crystals are probably orthorhombic ni= 1.55. Prehnite occurs in cavities in the felspar of the pegniatites; in addition to tbe usual green drusy type there is also a pale brown to colourless type which forms crystals or more often compact granular masses. Anal. XI11 of the brown prehnite. TAaumontite (anal. XIV) as columnar and fibrous masses occurs on the green prehaite. SiOz. Alsoit. Fe&+ I. 60'60 16'61 5'03 11. 4'15 1'20 III. - - 0'55 IV. 51'77 - 2'12 V. 50'42 - 0'51 VI. 36'88 17'61 3'11 VII. 35'53 21'11 3'95 VIII. 37'46 - - IXa. 36'12 - - IXb. 38'30 - - IXC. 34'42 - - X. 41'26 - - -+ XI. 64-54 20'86 trace xrr. 56-17 - - XIII. 44'10 24.20 - XIV.53'49 22'01 - FeO. - - - 0'46 0' 60 2'94 - CaO. 7'93 50'78 44'83 48.29 35-27 36'06 35'14 42'71 41'20 43'54 44'58 1 8 6 26'10 25'20 10'80 - MgO. 2'08 2' 50 67'48 0'60 4'73 0'7s 25'32 - - - trace trace - - PyOj. I I - - - 2'38 3'50 3'50 3'84 - SO3. - 40'60 - 31'73 - 1-02 - 0'07 - 0'61 - 1'23 - - 2'42 1'16 14'98 1'25 - 15'17 224 - 16'24 1'84 - 8'11 I 0'52 - 16'88 - 5'86 I 13'39 TotaI. Sp. gr. 97'08* - 99'58 - 99'76 2 3 9 99'76 - 99'89 - 99'57t 3'36 100'15f 3'39 100'86 3'078 99'77 - 99'42 - 98'42 - 99'63 - 100'81 2'54 99'10 2'206 99'36 - 99'69 - * Alkalis not determined t Incl. MnO 1'50 CuO 1'06 Na2O 0'61. Incl. CuO 0'70 Na2O 0.20. fi Incl. K20 11'85 Na20 1'18. L. J. S.ANALYTIUAL CHEMISTRY. ii. 115 Two New Zircon Minerals-Orvillite and Oliveiraite . T. H. LEE (Amer.J . Sci. 1919 [iv] 47 126-132; Revista da Sociedde Bmsileira de Scierzcins Ria de Janeiro 1917 No. 1 31-38).-The zirconia-bearing rock or ore (" caldasite ") of the Caldas region in Minas Geraes Brazil consists a t times mainly of baddeleyite containing ZrO 92%. One variety in which the cavities are lined with small crystals of zircon consists of a mix- ture of zircon and a new zirconium silicate the latter being soluble in a mixture of hydrofluoric and hydrochloric acids. Analyses I and I1 are of the mixture and I11 of material picked out nnder the microscope. 8Zr0 6Si0,,5H2O. and for this the name owiE7ite is proposed. The last. corresponds with the formula ZrO,. SiO,. S O 2 . A1&. Fe,O,. FeO. H,O. Total I. 71.88 35.31 0.62 0.15 - 0.43 1.56 99.95 11. 85.01 9.63 1.52 - 5-57 - - 99.7 3 TII. 68.04 25.46 - - - - 6.35 99.72 The second mineral-oli t~ciirnif 6-occurs with euxenite (anal. IV) a t Pomba Minas Geraes. %lost4 of the euxenite crystals are coated with a yellow crust (anal. V). An analysis (VI) is also given of another euxenite froin Espirito Sailto which was supposed to contain a new element. The oliveiraite is greenish-yellow with a radially fibrous structlure ; analysis V I I corresponds with 3Zr0,,2TiO,,2H,Of Cb,O,. ZrO,. TiO,. uo,. v TR20.5. IV. 1-46 36.39 25.00 10.06 . V. Iii-51 I 25.00 4.93* VI. 3.20 28.70 4.2 3 23-70 7.50 VII. - - 63-36 29-92 - Ce,O,. Y203 PbO. H,O. Total. IV. 0.46 23.08 0.14 2.41 99-00 V. 7.40 - 11-14 100.98 VT. - 23.12 0-14 6.41 100.12.1. VII. - I I 6.48 99-76 v * UOs. t Including iron oxide 3.12 SnO trace. L. J . S.

ISSN:0368-1769    

DOI:10.1039/CA9191605109

出版商:RSC    

年代:1919

数据来源: RSC

摘要:

ANALYTIUAL CHEMISTRY. Analytical Chemistry. ii. 115 Approximation in the Calculation of Chemical Analyses. G. PANEBIANCO (Gnzretta 1918 48 ii 189-206) .-Independently of experimental errors the accuracy of analytical results is limited to two or three figures by the fact that the atomic weights of the6. 116 ABSTRACTS OF CHEMICAL PAPERS. elements are exact to a t most four and more usually only three figures. Various examples are considered the values taken for the atomic weights and their absolute errors being those of the international table for 1911. Since Sb == 120.2 and S = 32.07 the percentages of these two elements in antimonite are 71.417 arid 28.582 respectively. If however the values 120.2 +O-3 and 32*07?0.01 are employed in the calculation the limiting per- centages for the antimony are 71.730 arid 71.106 the absolute error being 0.5 (71.7'30-71*106) ; similarly for the sulphur the absolute error is 0*06?(,. Hence the percentage of antimony is accurate to only two figures namely 71 and that.of sulphur t o three figures namely 28.5. The relative error B o€ an atomic or molecular weight may be expressed in the form of a fraction with 1 as numerator and some multiple of a power of 10 as denominator that is l / h . I o n . If then the value of this fraction is known relat-ively t o ail approxiniate number of which the first significant. number to the left is p this number will have I? figures exact if h is equal to or less than p o r ( / z + l ) figures exact if h is greater than 77. Thus for antimony with the atomic weight 120.2 and an absolute error P equal to 0.3 E<1/4.102; f o r antimony trisulphide B<(2 x 0.3 + 3 x 0*1)/(2Sb 1- 3s) =0.63/333*61<1/5 . 'LO?. Further for 100 2Sb/(2Sb + 3S) E,<E + E = 1,'4.102 + 1/5. lo2 = 9/20. 1/102<1/2.102 rrnd since 100 2Sb/(38b+35)= 71.41'7 and 2 is less than 7 only two digits namely 71 are accurate ; similarly for the percentage of sulphur three digits are accurate. A table is given showing for the atomic weights of the elements the absolute and relative errors. None o€ the latter is greater than 1/10? and since for a coinpound the relative error must be less than the greatest' of the relative errors of its constitluent elements such relative ei-l'or of the molecular weight may be less than 1 / 1 0 2 . The number of accurate digits in the percentages of the con- stituent elements of a compound may be rapidly established with- out calculation by application of the rule stating that the number of accurate digits of a quotient or product is one less than that of the term with the least number of accurate digits.Since no atoniic weight has mm-0 than four d-igits exact the percentage of any element o r group of elements in a compound cannot have more than three digits accurate ; further such percentage cannot have less than two digits accurate (see above). These considerahions are extended by taking into account the weight of substance taken f o r analysis and the sensitiveness of the balance the calculation of the error being employed to determine the minimum quantity of substance necessary to give the maximum accuracy in the digits of the percentage composition.T. 13. P.ANALYTICAL CHEMISTRY ii. 117 The Estimation of Solutions of Hydrochloric Acid and of Ammonia by WeigKing Ammonium Chloride and the Volatilisation of this Salt at Different Temperatures. VICTOR AUGER (Ui(71. SOC. chiin. 1918 [iv] 23 467-472).-A reply to Villiers (compare A. 1918 ii 332). W. G. Estimation of Phosphorns and Silicon in Cast Iron. ALPREDO CAVAZZI (Aiznali Cbzim. A p p l . 1918 10 137-149).- The method of estiniating phosphorus in cast iron (A. 1917 ii 540) has been simplified in many of its details. The mixture of ferric sulphate with silica and carbon separated as described is boiled for about thirty minutes with dilute nitric acid (1 5) in a beaker over which is placed a retort containing cold x.vater to act as a reflux condenser.The solution of ferric sulphate is filtered the residue washed with water acidified with nitric acid and the orthophosphoric acid in the filtrate precipitated by means of ammonium molybdats. The precipitate is washed dissolved re- precipitated and dissolved in ammonia solution as described in the original method and the solution is boiled with 3 gram of sodium chloride in order to precipitate any remaining iron as ferric phosphate. The precipit'ate is washed with boiling sodium chloride solution and fused with alkali carbomtes the mass treated with boiling water and filtered and the filtrate acidified with nitric acid trested with ammonia in slight excess and added to the iiiaiir solution.The phosphoric acid is then precipitated with magnesia mixture. The silica is estimated in an aliquot portion of the residue of carbon and silica by ignition over a blowpipe flame in a platiirum crucible. [See also J . Sor. Phrut. 7m7. 1919 March. J C. A. M. Estimation of Arsenic in Ferro-molybdenum and other Alloys. 0. BINDER (Clzem. Zeit. 19 18 42 6 19)-The estiination of arsenic in feno-molybdenum and similar alloys may be accelerated by carrying out all the operations in a long-necked Kjeldahl flask. The alloy is dissolved in nitric acid the solution heated with sulphuric acid until acid fumes 110 longer appear and then diluted axid the arsenic distilled from the same flask in the form of arsenious chloride. C. A. &I. Accurate Estimation of Carbon Monoxide in Gas Mix- tures.J. IVOR GRAHAM (J. SOC. Chem. I~zd. 1919 38 10-14~1.- The author's experimr,ents show that methods of estimation of carbon monoxide based on tha reaction 5C0 + XzO = 5C0 + I are capable of yielding exceedingly accurate resultss if certain precau- tions are observed. Two modes of procedure are adopted for the routine estimation of this gas according as ( ( I ) the carbon mon- oxide content exceeds 0*2(j/ and an accuracy of 0.02% is sufficient. o r ( 6 ) the carbon monoxide content' is about or less than 0.2% and a greater degree of accuracy than 0.02% is required. For theii. 118 ABSTRACTS OF CHEMICAL PAPERS. analysis of samples as under (a) the apparatus described by the author and Winmill (T. 1914 105 1996) is modified mainly by replacing the beaker of water used for heating purposes by a small steam-bath all burette readings being taken with the U-tube a t the constant temperature of the steam-bath.Descriptions and sketches are given of the apparatus and of a portable form capable of estimating very much smaller quantities of carbon monoxide accurately to within less than O*OlyL. The latter apparatus is varied slightly according as i t is t o be used in safetay pits or in " naked-light " pits or other places. T. 13'. P. Rapid Organic Combustions of Substances containing Nitrogen. HARRY I;. FISHER and A. H. WRIGHT ( J . Anzer. Chem. ,COP. 1918 40 868-869).-Reimer (A. 1915 ii 578) has used cerium dioxide as a catalyst in the combustion of organic sub- stances; cupric oxide is also employed and by the addition of lead peroxide and minium carbon and hydrogen can be estimated in substances containing nitrogen.To prevent formation of eupric nitrate the layer of cupric oxide must be maintained atl a dull red heat ; the lead peroxide-minium mixture is placed in the coinbus- tion tube about 5 cm. beyond the cnpric oside and is heated at> 300-320O. Several successive combustions mav then be made in the same tube without changing trhe cupric oxide. W. P. 8 . Methods of Water Analysis. Armo A. BADO TTrcToR J. BERNAOLA AURELIO F. NIAzzA and TAOPOLDO D ~ s s o (0btw.s ,Smifarins cla 7n S n r i d i i Rireno.c. A i m 1918 98 pp.).-A mono- graph giving a detailed account of the chemical and micrcbio- logical analytical methods in use in the Laboratorio de Andisis de Aguas y Eiisayos de Materiales de las Obras Sanitarias de la Nacioii of Buenos Aires for the examiiiatcion of potable waters. T;5r.S. M. Rapid Method of Reduction of Potassium Platinichloride. EORSCH (Compf. fzmd. 1919 168 167-169).-1ii the estimation of potassium the precipitate of potassium platinichloride after being well washed with 80% alcohol is dissolved in boiling water and the solution transferred to a weighed platinum crucible. Two to three C.C. of alcohol are added and the whole heated on a rapidly boiling water-bath for twenty-five minutes after which a few more drops of alcohol are added and the heating continued f o r five minutes. In this way the platinum is deposited gradually and uni- formly on the interior surface of the crucible and is quite adherent.The liquid is poured out the deposit washed with water and the crucible is dried ignited and weighed. During the ignition the deposit turns from black t o a shiny metallic appearance and remains adherent. For the process it- is essential to use a platinum crucible as the reduction only takes place in the presence of platinum and the concentration of the potassium platiiiichloride sohitlion must not exceed 0.25- -0.30%. W. G.ANALYTICAL CHEMISTRY. ii. 119 Gravimetric Analysis. IX .-XI. Estimation of Calcium in the Presence of Phosphoric Arsenic and Boric Acids. L. W. WINKLER (Zeitsch-. angew. C'hem. 1919 32 i 24).- Calcium is precipitated quantitatively as oxalate in solutions con- taining phosphoric arsenic and boric acids provided the solution is hot and that acetic acid and ammonium chloride are present.The following procedure is recommended. About 50 C.C. of solu- tion containing not more than 0.1 gram of calcium are made slightly alkaline by the addition of ammonia drop by drop. The solution is diluted to 100 c.c. and 3 grams of ammonium chloride added and allowed to dissolve; the solution is bhen acidified with 10 C.C. of iT-acetic acid and the calcium is precipitated as oxalate as prescribed for the pure solution. The last traces of precipitate may be removed from thel beaker by means of a little pure methyl or ethyl alcohol which is then poured on to the edges of the filter so as t o wash them. The result may be corrected by a blank using a pure calcium salt. If a considerable portion of arsenic or phosphoric acid is present a double precipitation is desirable the first precipitate being allowed to remain overnight collected washed with ammonium oxalate solution ignited the residue dissolved in hydrochloric acid and the calcium oxalate re- precipitated as before.A. B. S. Rapid Estimation of Lead in Brass and Alloys. G. H. HODGSON (Chem. News 1919 118 37--38).-A gravinietric and a volumet'ric method for the rapid estimation of lead in brass and similar alloys are described. The gravimetric method consists in precipitation of the lead as chromate from an acetic acid solution conversion into sulphate and finally weighing as molybdate. Five grams of the alloy are dissolved in 25 C.C. of nitric acid (D 1.4) the solution diluted with 200 C.C. of water and sufficient aqueous ammonia (20 c.c.D O*SSO) added t o precipitate all the copper. Sufficient 80% acetic acid is then added t o produce a clear slightly acid solution and 10 C.C. of 3% potassium dichromate are added the mixture shaken and kept fvr one hour. The precipitated lead chromate is filtered on a paper pulp pad and washed to remove the copper; hot douches of 307L sulphuric acid are poured on to the pad until the precipitate is entirely white. The sulphate is then washed with water. The lead sulphate[ is now dissolved by pouring about 40 c,c. of hot ammonium acetate solut>ion contain- in6 acetic acid through the filter. The solution is raised to the boiling point and treated with ammonium molybdate. The pre- cipitate is allowed to settle filtered through an ashless paper pad washed with water containing a little ammonium acetate ignited and weighed as lead molybdate.The whole process may be corn- pleted in four hours. The volumetric process consists in p r h p i t a - tdon of the lead as chromate as described above; the chromate pre- cipitate is washed with water and warm dilute acetic acid (5%) until free from copper and the excess of potassium chromate. The chromate is dissolved by pouring 1 4 hydrochloric acid on to theprecipitate and t h s pad finally washed with water t o wash all chromic acid through The free chromic acid may be estimated by titration with iV/ 10-ferrous ammonium sulphate solution or by adding 10 C.C. of 10% potassium iodide solution and titrating the liberated iodine with AV 10-sodium thiosulphate solution.The whole process may be carried out in two hours. Both methods have been compared with the gravimetric sulphate method and found to give results in excellent agreement with those obtainecf by the better known method. Unification of Methods for the Analysis of Cast Iron and Steel. A. MARINOT ( A m . C I t k anal. 1929 [ii] 1 5-lO).-The following methods are suggested as being trustworthy. Total carbon niay be estimated by Wiborg's method (combustion with sulphuric acid aiid chromic acid) by the ordinary method of com- bustion or by hhe method described by Mahler and Goutal (A. 1912 ii 807). Manganese is estimated by Traver's method (A. 1917 ii 511) and phosphorus by the molybdate method. Sulphur is liberated as hydrogen sulphide in an atmosphere of carbon dioxide collected in zinc acetate solution and estimated iodo- metrically.Arsenic is also estima%ed iodmnetrically after distilla- tian. J. F. S. [See further J . SOC. C'Aein. Z i i d . March.] W. P. S. Direct Estimation of combined Ferric Oxide in Silicates Tnsoluble in Acids. 0. HACKL (Chem. Zeit. 1919 43 9).- Knecht's volumetric metho'd of estimating ferric salts by titration with titanous chloride using potassium thiocyanate as indicator is not directly applicable to silicates which have been decomposed with hydrofluoric acid. The influence of a small amount of this acid in preventing the appearance of the colour reaction with thio- cyanate may be obviated by dissolving- boric acid in the solution. This also restores the colour of ferric thiocyanate which has been destroyed by hydrofluoric acid ; or methylerre-blue the colour of which is not affected by traces of hydrofluoric acid may be used as indicator in place of potassium thiocyanate.C. A. &I. Estimation of Molybdenum. Kun-o WOLF (ZeitscA. cuzgc?~. ('hem. 1918 31 i 140).-When molybdenum is separated as its sulphide and the latter then converted by ignition into molyb- denum trioxide and weighed the temperature during the ignition should not exceed 425O. The conversion of the sulphide into tri- oxide is complete at' 400c; no further change takes place between 40O0 and 450° but above 450° the trioxide sublimes. The correct temperature (400--425°) is most readily attained by using an electric furnace. w. P. s. Emanation Method of Estimating Thorium.G. EL CARTLEDGE ( J . -titter. Chetu. Xoc. 1919 41 42-50).- l t is showi~ by circulating it current$ UP air through a thorium solutioii and ail ionisitioii chauilxr until t-he activit.y bas become constantANALYTICAIJ CHEMISTRY. ii. 121 that the thorium content of any substance which can be dis- solved completely may be estimated with an error which is not greater than 1.5%. In making the determination it is advisable to draw air through the solution for some minutes before connect- ing to the ionisation chamber €or the purpose of removing any radium ernanation which may be present. It is also essential that the dimensions of the apparatus used should be the same in all experiments aild that the temperature should be as nearly as possible the same.The method has been tested with a specimen of mbnazite sand and it is found by this method that 8.61% of thorium oxide is present' whereas the g-ravirnetric analysis indicates 8.57%. Details are given of a method of preparing a solution of monazite for this analysis. Two notes on the gravimetric analysis of monazite are appended tol the paper. Carney and Campbell (A 1914 ii 583) use ammonium perchlorate and sulphuric acid for the destruction of the filter paper and the conversion of thorium pyrophosphate into thorium sulphate. This process may be carried out in one-half the time by using sulphuric acid and fuming nitric acid (D 1-53) instead. It is shown that the practice of using a slightly turbid unfiltered solution of monazite in the analysis leads to high thorium results since the titanium oxide is weighed along with the thorium.J. F. S. Estimation of Gold especially in Animal Tissues. SIDNEY M. CADWELL and GLADYS LEAVELL ( J . A n i c r . C ' l i ~ m . Soc. 1919 41 l-l2).-With the object of finding a method cap- able of estimating the amount of gold present in tissues the authors have investigated the methods available for the estimation of gold and have devised a method which tvit'h a maximum error of 0.05 mg. is capable oE estimating amounts of gold of 3.0 mg. and less. This method was required in connexiori with the gold salt treatment of tuberculosis aucl consists in placing 10 grams of fresh tissue in a 300 C . C . Kjellc-tahl llask ac?&ng 10 C.C. each of concen- trated sulphuric and niiric acids aild digesting over a free ilaiiic until the cooled solution is culourless.Air is then blolwn into the flask and the mixture again heated until the volume of solution is reduced to 2 c.c.; this procedure removes most of the sulphuric acid. One C . C . each of hydrochloric and nitric acids is then added and the mixture boiled f u r a few minute? and then a further C.C. of hydrochloric acid added. The solution is cooled diluted with 5 C.C. of water and concentrated ammonium hydroxide added until ths colour is discharged and then an excess of 2 C.C. The mixture is boiled and the white precipitate which forms a t this point dis- solved by adding 5 c . ~ . of concentrated hydrochloric acid and boil- ing for three minutes. The solution is filtered through asbestos on an aluiidum plate and the filtrate treated with ammonium hydroxide uiitil it.smells distinctly of ainrnonia. The volume of the solution should be uow about 40 C.C. ; 1.1 C.C. of SSqL phosphoric acid and 0*75 p a i n of disodium hydrogen phosphate are added and the solutioii electrolysed. A rotatiug anode aiid a cathode ofii. 122 ABSTRACTS 03’ CHEMICAL PAPERS. platinum sheet are used. The difference of electrode potential should be 0.9-1.2 volts and the mostl efficient temperature is 60”. The method has been slightly modified to allow of its use for larger quantities of gold. By the addition of 6 grams of ammonium chloride to prevent precipitation 30 t o 40 mg. of gold can be electrdysed a t 60° with a voltage of less than 0.6 volt for the first thirty to forty-five minutes aiid below 1.3 volts for the remainder of the time complete deposition usually requiring one and a-half hours.Under the conditions stated gold can be completely separated from equivalent amounts of copper and iron but the time required for electrolysis is greater than when these substances are not presentl. It makes very little difference whether the electro- lysed solution is neutral or much more acid than stated above. The average time required for carrying out a complete analysis of gold by this methold is less than tqwo hours. Quantitative Estimation of Sugar. A New Apparatus for the Estimation of Sugar in Urine. H. CITRON (Niinch. med. ll~oeh. 1918 65 1053; from Chem. Zemtr. 1918 ii 869).-The author describes a simple apparatus for t$e estimation of sugar in urine according to Bang’s method.Quantitative Colorimetric Estimation of Pentosans in Meal. G. TESTONI (Stax. sper. agr. Itnl. 1917 50 97-108 ; front Chenz. Zentr. 1918 ii 865-866).-The method of Tollens and Krueger gives high results because the starch is slowly but con- tinuously converted into furf uraldehyde. Sucrose maltose and dextrose when heated with hydrochloric acid of the prescribed con- centration also yield distillates from which phloroglucides are obtained. The hexoses starch and cellulose cause incorrect results in the estimation of methylpentosans since when treated with dilute mineral acid they give as intermediate product o-hydroxy- methylf urf uraldehyde which yields a phloroglucide m. p. 95* soluble in alcohol. The author has therefore endeavoured to find a process by which the pentosans can be converted into pentoses easily identified by colour reactions whilst the other constituent8 of the meal are not attacked in a vitiating manner.The most suitable reagent is a mixture of acetic acid (90 c.c.) and concentrated hydrochloric acid (D 1.19 10 c.c.) at 45-50°. On addition of 0.2576 phloro- glucinol to this mixture a red solution is obtained which remains clear even when diluted with one hundred times its volume of water and has well-marked absorption bands in the red yellow and blue. Different varieties of starch dextrins and different sugars have no influence on the reaction whilst. pentoses alone and in artificial mixtures are quantitatively found. The pentosans even those contained in clover are completely hydrolysed when heated for forty-five minutes with the reagent.Action of Potassium Cyanide on Ammoniacal Copper Sulphate and its Application to the Estimation of Hydro- cyanic Acid and Copper. L. JENNESSEAUX ( A m . Chirrt. a~tut. 1919 [ii] 1 15-20).-IJassaigne’s test for hydrocyanic acid (form- J. F. S. H. W. H. W.ANALYTICAL CHEMISTRY. ii. 128 ation of a white precipitate when a cyanide solution is treated with a drop of copper sulphab solution then with sodium hydr- oxide solution and the mixture acidified with sulphuric acid) may be rendered more sensitive if the copper sulphate solution is first treated with sodium hydrogen sulphite in quantity sufficient to change the colour from blue t.0 green. When potassium cyanide solution is added t-o ammoniacal copper sulphate solution a crystal- line precipitate forms having the composition ~CU~(CN),,CU(CN)~,~NH~.Further addition of cyanide then causes the solution to become colourless and the precipitate dissolves. This point is reached when a definite proportion of cyanide has been added and the reaction may be used f o r the estimation of hydrocyanic acid and conversely of copper. The copper sulphate solution used should contain 4.99 grams of the crysta1lise)d salt per 100 c.c. and this solution is mixed with 80 C.C. of K/l-ammonia and 20 C.C. of water; 10 C.C. of the mixture is a convenient quantity t o take for an estimation. [See further J . SOC. Chem. Id. 1919 March.] w. P. s. Opium Analysis. D. B. Do~~(Pha9-m. J. 1918 101 318)- The author deals with certain criticisms by Annett and Singh (A.1918 ii 279) on the British Pharmacopeia method for the assay of opium by the lime-water process. Whatever may be the solvent influence of codeine on morphine in aqueous solution the condi- tions of the assay process are entirely different; in that sufficient ether is added to hold in solution all the codeine possibly present. Moreover the author has checked the alternative method proposed (toc. cit.) consisting in shaking the limewater solution of the alkaloids with toluene to remove the codeine before precipitating. the morphine by the official process. This alternative method (using benzene instead of toluene) gave a morphine precipitate heavier in weight and showing a higher titration value but obviously less pure than the morphine prepared by the standard method.When the impurities were removed by washing with 80% alcohol saturated wit.h morphine the morphine prepared by the new process was- no more than that prepared by the Pharma- copceia process and there is no reason f o r altering the latter in the direction indicated by Annett and Singh. Separation and Estimation of Uric Acid and other Purines in Urine. F. TEbLE (Bull. S c i . Phnrmacol. 1918 25 208-211 ; from Crhem,. Zentr. 1918 ii 770).-The uric acid is pre- cipitated by the addition of solid ammonium chloride and ammonia to the acid urine and after collecting on a small filter estimatd by titration with pemanganate in the presence of sulphuric acid. The purines in the filtrate are estimated by Denigks’s method.J. F. B. H. W. B. Quick Estimation of Albumin (in Urine). A. SIMON and C. PAGEL (Bull. Sci. Pharmacol. 1918 25 204-208; from Chem,. Z e n t r . 1918 ii 767).-The urine is treated with saturated sodiumii. 124 ABSTRACTS OF CHEMICAL PAPERS. sulphate solution and two o r three drops of acetic acid and is then heated until the albumin separates in flocks. By means of the diaphanometer described in the original paper the height of the liquid is determined a t which a line drawn on the bottom of the vessel is no longer discernible. The amount of albumin in t’he urine can then be read off from the accompanying table. H. W. B. Estimation of Urobilin in Urine. S. MARCUSSEN and SVEND HANSEN ( J . Bid. Citem. 1918 36 381-389).-The presence of urobilin i n urine may be readily detected by the following modifi- cation of Schlesinger’s test.One gram of zinc acetate is weighed into a test-tube and 10 C.C. of absolute alcohol are then added; 10 O.C. of the urine are placed in another test-tube to which are added three drops of a 5% alcoholic solution of iodine. The con- tents of the two tesbtubes are then mixed by repeated decantations until all the zinc acetate has dissolved. After filtering off the precipitate the filtrate is found to be fluorescent if urobilin or urobilinogen was originally present in the urine. By diluting the urine until fluorescence is no longer obtainable a rough idea is furnished of t3he quantitative relationship of t-he urobilin. H. W. B. The Estima€ion of the Nuclein Content of Yeast.C. A. LUBSEN (Phtam. Weekblad 1918 55 (50) 1625-1628).- The hydrolysis of nucleoproteins by hydrochloric acid-pepsin solu- tions yields soluble albumins and an insoluble residue of nucleins; the latter contain 4-7% of phosphoric acid representing the whole of the phosphorus present in t,he nucleoprotein. Further hydro- lysis for example by trypsin yields another albumin group together with a nucleic acid. I n analysing foodstuffs for nuclein content Jebbink employs the pepsin-hydrochloric acid hydrolysis using a solution containing 0.24% HC1 and determines the phos- phorus in the insoluble residue of nuclein using this as a measure of the nuclein content. Grijns criticises this method on the ground that so strong a solution of hydrochloric acid would cause further hydrolysis of the nuclein t o the soluble nucleic acid thus leading to low results. m e author has examined the question by carrying out experi- ments with yeast using pepsin-hydrochloric acid solutions con- taining various proportions of hydrogen chloride. He finds that the weak solution (0.1% HC1) recommended by Grijns gives low results owing to the slowness of the hydrolysis whereas Jebbink’s solution (0.24% HCI) and even stronger solutions (0.35% HCl) gives accurate results. It is therefore clear that the nucleins are not further hydrolysed by acid solutions of this strength and Grijns’s contention appears to have been wrongly based on the assumption that hydrolysis proceeded to the soluble nucleic acids. S. T. 1,.

ISSN:0368-1769    

DOI:10.1039/CA9191605115

出版商:RSC    

年代:1919

数据来源: RSC

摘要:

Organic Chemistry. Products of the Action of the Silent Electric Discharge on Acetylene. H. P. KAUFMANN (Annalen 1918 417 34-59)- After giving a r & u d of previous work on this subject the author describes in detail his own apparatus photographs of which are given. The essential part consists of two concentric glass tubes about 75 cm. long having a space of 5 mm. between their walls. The interior of the inner tube is silvered and through it a rapid stream of cold water is passed. The outer cube is immersed in dilute sulphuric acid in which is a cooling coil. Electrical con- nexion is made between the silvered surface and the sulphuric acid with the poles of an induction coil operated by a high-frequency machine (230-250 volts 2.5-3 amperes). A stream of acetylene is passed between the tubes and all air in the apparatus must be completely displaced by the acetylene before t$e silent dis- charge is passed.When the reaction vessel is allowed to get warm the product is a mixture of a solid and a liquid but if the vessel is kept cold a liquid product only is obtained which collects a t the bottom of the vessel a t the rate of about 30-50 grams per hour. The liquid is a brown viscous oil having an un- pleasant odour. It has the composition (C,H,) and is very unstable changing by warming by keeping in solution or by the attack of almost any chemical agent into the solid which appears to be identical with t-hat described by de Wilde (Be,.. 1814 7 357). The liquid decomposes and carbonises above looo but a small quantity distils a t 70°/10 mm.which is a mixture of several substances; the residue in the flask changes to a plastic mass which ultimately becomes brittle. The solid product obtained in the warm reaction vessel is more conveniently obtained by warming a solution of the liquid product in ether a t about 60°. It is a pale yellow odourless powder which is insoluble in all solvents. Both the liquid and the solid rapidly absorb oxygen and it is only during such absorption that t'hcy produce any action on a photographic plate. The solid does not react with,a dilute solution of bromine under ordinary conditions but is attacked by more concentrated solu- tions hydrogen bromide being evolved. The liquid readily absorbs bromine best in solution in carbon tetrachloride a pale yellow powder being obtained the composition of which appears to be (C2H2Br)28 assuming it to be an individual substance.A 98% alcoholic solution of silver nitrate produces with a solution of the liquid product in carbon tetrachloride a pale yellow floccu- lent precipitate of a silver derivative which explodes on heat'ing; $he presence of a iCH group in the liquid product is thus indicated. By boiling with 47% nitric acid the solid product yields nitro- YCL. cxvr. i 9i 118 ABSTRACTS 0s CHENIICAL PAPERS. compounds of high molecular weight together with a little benzoic acid By oxidation with alkaline permanganate the liquid pro- duct yields beiizoic isophthalic and terepht,halic acids. The same three acids are obtained although with much greater difficulty by oxidising the solid product with alkaline permanganate.C. S. Ally1 Alcohol. M. J. STRITAR (2l/lonats7z. 1918 39 617-626).- Bromine is quantitatively absolrbed by allyl alcohol whether the former is in excess or not; the reaction is suitable for the exact quantitative estimation of allyl alcohol which may be effected either by directl titration with bromine water until a permanent yellow coloration is obtained or by treating the acidified aqueous solution of the alcohol with an excess of bromide-bromate solution followed by addition of potassium iodide and titration of tlhe liberated iodine with sodium thiosulphate (compare Stritar and Zeidler A 1904 ii 686). When bromination is effected in dilute aqueous solution about 47.5% of the added bromine is immediately and spontaneously eliminated as hydrogen bromide.Elimination of the second bromine atom (exchange for hydroxyl) occurs slowly and incom- pletely in acid solution small amounts ol acraldehyde being formed. Practically the whole of the bromine is removed when the product is heated under pressure a t looo with the calculated quantity of potassium hydroxide (or with a 10% excess); the yield of glycerol is about 97% of that theoretically possible. The small deficiency is caused by the formation of a volatile saturated bromide which is fairly resistant t o alkali. H. W. The System Ethyl Ether-Chloroform. A. SMITS and V. S. F. BERCKMANS (YTOC. K . Akad. Wetensch. Amsterdam 1919 21 401-404) .-A melting-point curve for various mixtures of ethyl ether and chloroform has been determined.The curve shows that an equimolecular compound is formed (m. p. -94*4") as was stated by Dollezalek and Schulze (A. 1913 ii lOS) but in addition two other compounds (i) a compound made up of two molecules of chloroform and one molecule of ethyl ether (ni p. - 9 3 . 3 9 and (ii) one made up of two molecules of ethyl ether and one of chloro- form. The latter compound does not melt but dissociates a t - 113*8* into the equimolecular compound and ethyl ether. J. F. S. Physical Constants of Mustard Gas " [PP'-Dichloroethyl Sulphide]. LEASON H. ADAMS and ERSKINE D. WILLIAMSON (J. Tl'nshtingtom Acad. Sci. 1919 9 30-35) .-The compressibility of PP'-dichloroethyl sulphide has been determined over the pressure range 392-1713 megabars a t 31.5O by the method previously described (this vol.ii 98). The compressibility is represented by the equations Au/vo=4*24 x 10-5(P-P0) - 6 . 3 x 10-6(P-Po)2 and - A v / g U g = O*ll8(1 - e-0'364x~O-y(P- Po)). Differentiating this the relationship - du/dP = 49*5e-0'36*X10-:'PI The Compressibility a tORGANIC CEEMISTRY. i. 119 1'=0 is 49.5 x 10-6 per niegabar and at 1000 megabars it is 34.4 x 10-6 per niegabar. The freezing pressure and volume change were also determined at a few temperatures and the following results obtained Freezing pressure. Temp. Megabars. ( V2 - V e x ) dP/dT. 13.9 1 0.054 68 21.9 670 0.080 71 2'3.6 1110 - - 31.4 1210 0*04s 74 38.9 1800 0.042 77 The latent' heat of fusion per grain is found t o be 25 cal. J. F. $3. The Liquid Crystals of Agaricic Acid. PAUL GAUBERT (CompPt.Tend. 1919 168 277-279).-Agaricic acid gives two types of liquid crystals one belonging to the cubic syst,ern and the other being optically uniaxial and positive. The crystals are but slightly birefringent and consequently the polychroism is feeble. w. G. Phytochemical Reductions. XV. The Conversion of Acetaldol into Optically Active P-Butylens Glycol by Yeast. CARL NEUBERG and (MME.) ELISABETH KERB (Biochem. Zeitscli. 1918 92 96-110).-The reaction OH*CHMe-CH,-CHO -+ OH*CHMe*CH,*CH2~OH t-akes place in the presence of yeast both when actively fermenting sugar and when also sugar is not added. A. dextrorotatory productl was obtained. The P-butylene glycol was amongst other methods characterised by preparing the di-a- naphthylurethane derivative m. p. 154O by its treatment with a-naphthylcarbimide.A method is given for preparing in goo*d yield acetaldol by the action of disodium sulphite on aldehyde in the cold (at - 15.). From the aldol were prepared the P-brornophe?zylhydzo~e C,,H,,ON,Br white seemingly hexagonal leaflets m. p. 127-1 28O and also the L-Eip?henylrnethnnedinzeth:yldihy~raaone CH (C,H,-N Me* N C H C H,. C H &/re* OH) o colourless plates m. p. 1 1 7 O . S. B. S . Phytochemical Reductions XVI. The Conversion of Citral into Geraniol by Yeast. CARL NEUBERG and (MME.) ELISABETH KERB (Biochem. Zeitseh. 1918 92 111-123).-This reaction takes place both in the presence and absence of added sugar. The geraniol which is produced is accompanied by some optically active substance which has not yet been identified.The autho'rrs describe the two following derivatives of cyclocitral the thiosemicarbazo.ne C,,Hl9N,S white leaflets m. p. 200-201° and the p-nitrophenylhy~razone C,,H2,0,N orange crystals m. p. 1 2 5 O . S. B. S.5. 120 ABSTRACTS OP CHXMICAL PAPERS. Preparation of Soluble Starch. A. LEULIER ( J . Plzamz. Chirn. 1918 [vii! 18 291).-Trventy-five grams of starch are boiled f o r fifteen minutes under iz reflux apparatus with a mixture of 100 grams of 950/ alcohol and 5 grains of sulphuric acid; the starch is then collected on a filter and washed with water o r alcohol until free from acidity. Starch thus treated is insoluble in cold water but very soluble in hot water. [See further J . Soc. Chenz. The Preparation of Methylamine from Chloropicrin . PERCY FARADAY FRANKLAND FREDERICK CHALLENGER and NOEL ALBERT NICHOLLS (T.1919 115 159-162). Ind. 1919 8 6 ~ . ] w. P. s. The Present Condition of the Benzene Problem HERMANN PAULY ( J . pr. Cherii. 1918 [ii] 98 106-135),-The various representations suggested for the benzene molecule are discussed. From a consideration of the relationships between the physical constants of benmne derivatives the corresponding hydrogenated compounds etc. t,he following coiiclusions are drawn (1) The atoms of the benzene molecule lie in one plane. (2) The benzene ring must be symmetrically arranged and the linkings uniform. (3) Neither centric nor oleiinic linkings are present the degree of saturation of the linkings being approximately midway between those of simple a i d double linkings.Thiele's formula the valence- e!ectronic representabion of benzene the tetrahedral model and the problem of orientation are also considered. T. H. P. 11-10-Bromophenanthrene-3- or -6-sulphonic Acid. HAKAN SANDQVIST (AnnaZel-L. 1918 417 1-16).-A hot aqueous solution of potassium phenanthrene-3-sulphonate is cosoled t o about 50° uiitil crystals begin t o separate and a solution of bromine in water satarated a t the ordinary temperat.ure (about 3 mols. of bromine) is added gradually whereby is obtained in addition to oxidation products potassium 11-10-bromophenanthrene-3- or -6-sulphonate. t h e crude salt is converted through the chloride into I I - l O - b ~ ~ o ~ ~ ~ o - phenanth~ene-3- or -6-siiZphonic acid C,,H,Br*S03H,4H,0 an almost white am-crystalline mass rn.p. 152-153° or anhydrous 223O (in a closed capillary m. p. 160-170°) which has an astringent but. unlike the I-isomeride (A. 1917 i 552) no sweet taste forms yellow flocculent solutions and shows some tendency t o form liquid crystals. The pota&um urn?rmnizL?1z sodi~tm caZcZum barium and copper salta are described. The methyl ester flattened needles has m. p. 158O the ethyl ester needles has m p. usually 143*5O but sometimes 134O (to a turbid liquid); the former yields methyl phenanthraquinone-3-sulphonate by oxidation with chromic and acetic acids. 11-1 0-Bromophenml threii e-3- o r -6-suLpho~j1l chlo~ide prepared f rorn t-he potassium salt forms faintly yellow prisms m. p. 199-199*5O from which are prepared the arnide C,,H,,O,NBrS needles m. p. 266*5O and the anilide needles or leaflets m.p. 2 1 1 O . c. s.ORGANIC CHEMISTRY. i. 121 I- 10-Chlorophenanthrene-3- or -6-sulphonic Acid and 1 0-Chlorophenanthrene . H ~ K A N SANDQVIST (Annalelz 191 8 417 17-33).-1t has been shown (A. 1917 i 552) that the abnormal viscosity and anisotropy of solutions of I-lO-bromophen- anthrene-3- or -6-sulphonic acid disappear when the bromine is replaced by the -SO,H or *C,,H,Br*SO,Me group. It is now found t.hat they are increased when the bromine is replaced by a chlorine atom. I-lO-Chlorolrhenanth1.e,ie-3- or -6-szilphoiiic acid prepared by fusing together I-10-bromophenanthrene-3- or -6-sulphonyl chloride and phosphorus pentachloride and heating the resulting chloride with water at abolut 145O forms a white microcrystalline powder possessing an acid sweet astringent taste.A 0*04S-solution has a viscosity 1.03 a t 1 8 O (water a t lS0=1); this is increased to about 140 by the addition of one-sixth volume of 3S-hydrochloric acid the value f o r I-10-bromophenanthrene-3- or -6-sulphonic acid being increased only to about? 6 by similar treatment. The air-dried acid m. p. 160-161° contains 3H,O (decomp.); the anhydrous acid has m. p. 206-207O. The ammonium sodium potassium calcifcm bnri?cm and copper salts are described. The methyl ester leaflets o r prisms has m. p. 172-172*5O and the ethyl estLer colourless crystals m. p. 182*5-183°. The chloride C,,H,Cl=SO,Cl pre- pared as above forms prisms m. p. 196-197O and from it hare been obtained the amide needles m. p. 281-282O and aniline crystals m.p. 197-198O. lO-ChTaropkennnth7.ene C,,H,Cl m. p. 35-55O (purest specimen 52.5-53.5O) b. p. 343-346O is obtained together with other pro- ducts (of which 9 10-dichloroanthracene and 9 10-phenanthrene dichloride have beea identified) by adding a cold solution of chlorine (26 grams) in carbon disulphide to phenanthrene (50 grams) dissolved in the same solvent. It yields phenanthraquinone by oxidation forms a picmtp C ,H,Cl,C,H,(NO,),*OH. yellowish- red needles m. p. 111-112° and is converted by sulphonation a t 1G5-17Oo into a sulphonic acid. from which the preceding I-10-chlorophenanthrene-3- or -6-sulphonyl chloride m. p. 196--197O can be prepared. c. s. The Mobility of the Methylnitroamino-group in the Derivatives of Tetranitrophenylmethylnitroamine and in Trinitrodi(methy1nitroamino)benzene. C.F. VAN DUIN (Rec. trav. ckirrz. 1919 38 89-lOO).-A study of the action of ammonia aniline and m-nitroaniline on certain derivatives of 2 3 4 6-tetranitrophenylmethylnitroamine obtained by substi- tuting the nitro-group in position 3 by an hydroxyl an anilino- a methylnitroamino+- an amino- and a dimethylaminegroup. The results show that a negative substituent in this position hinders the substitution of the methylnitroamino-poiin whilst a positive substituent increases its mobility. As opposed t o this however. is the fact that in 3 4 6 - t r i i i i t r ~ - 3 - d i m e t h y l a n ~ i ~ ~ o ~ ~ h ~i. 122 ABSTRACTS OF CHEMICAL PAPERS. methylnitroarnine the methylnitroamino-group is not replaced by rn-nitroaniline.I n the action of ammonia on 2 4 6-trinitro-1 3-di(methylnitro- amino)benzene two compounds one having m. p. 195-196O (corr.) and the other having m. p. 1 4 4 O (corr.) were obtained but could not be characterised. W. G. The Formation of Phenol in the Action of Sodium Methoxide on the Higher Chlorobenzenes. P. W. DE LANGE (Rec trav. chim. 1919 38 101-105. Compare Xolleman and Mooy A. 1916 i 22).-The author finds that p-chIoroanisole and p-dichlorobenzene when heated in sealed tubes a t 176-177O with sodium methoxide in methyl alcohol each yielded pchlorophenol and methyl ether the reaction being far more complete with the p-chloroanisole than with the dichlorobenaene. He considers that the reaction wikh dichlorobenzene takes place in two stages as follows (1) C,H,CTI,+ NaOMe=C,H,Cl-OMe+ MaCl.(2) C,H,Cl*OMe + NaOMe= C,H4Cl*ONa + Ne,O. w. 0. Velocity of Nitration of Phenols in Ethereal Solution. 11. ALFONS KLEMENC and ELISABETR EKL (Monatsh. 2918 39 641-696. Compare A 1914 i 272).-The velocity constants of the nitration of phenol guaiacd 0- and pcresol and resorcinol methyl ether have been determined. NiLration is in general found to be a positive autocatalytic process and the rate of nitra- tion is dependent on the proportion of nitrogen peroxide or nitrous acid in the nitric acid. From this point of view a mathematical expression for the velocity of nitration of a benzene derivative has been developed which when applied to the particular case of phenols takes into account the fact that the nitrous acid formed during the course of nitration (the cause of the autocatalytic nature of the process) is itself absorbed by t'he phenol. Pure nitric acid free from nitrogen peroxide and nitrous acid does not cause nitration.Nitrogen peroxide induces both the nitrating and oxidising action of n h i c acid towards derivatives of benzene. I n the case of nitration in ethereal solution action either does not occur a t all or rapidly comes to an end if the number of mole- cules of nitric acid is greater than that of the phenol or guaiacol this behaviour being apparently opposed to the law of mass action. The necessary solutions are obtained by dissolving anhydrous nitric acid in dry ether a t a temperature of -80° (solutions pre- pared in this manner remain colourless a t Oo for weeks) and by dissolving nitrogen peroxide in the same solvent in a special form of apparatus which is figured in the text and allows the necessary adjustment.of concent<ration and removal of known amounts of sollution. The course of the reaction is followed byORCANIG CHEMISTRY. i. 123 determining the decrease in the titre of the nitric acid a t given intervals. I n the case of phenol this can be done directly with standard barium hydroxide solution (the nitrophenol behaving as indicator) during the early stages of the reaction; during the later stages the end-point is obscured by coloured bye-products and it is then preferable to shake the ethereal solution with saturated potassium chloride solution and t o add potassium hydroxide or barium hydroxide until the nitric acid is neutralised when the next drop extracts a portion of the nitrophenol from the ether and colours the aqueous solution deep red.I n the cases of guaiacol and other phenols this method cannot be used and recourse must bs had to the iodometric process previously described (Zoc. cit.). I n addition to the phenols already mentioned experiments with catechol resorcinol and quinol are also described. I n the first two cases satisfactory results could not be obtained; with quinol the initial reaction consisted in the evolution of nitric oxide and formation of quinhydrone which gradually underwent nitration * It i g noteworthy that the presence of nitrogen peroxide is here found to be essential to the oxidising action of the nitric acid. R.w. Oxidation of Quinol and its Sulphonic Acids by means of Fehling’s Solution. JOH. PINNOW (J. pr. Chem. 1918 [ii] 98 81-95 Compare A. 1911 i 339).-Further experiments show that when oxidised by Fehling’s solution in absence of air quinol and its sulphonic acids require almost exactly 3 atoms of oxygen per molecule and give dihydroxyquinol or its sulphonic acids. The less amount of Fehling’s solution earlier found sufficient with low coxentrations of quinol (compare Bourquelot and Fichtenholz A. 1910 i 273) is explained by concurrent oxidation a t the expens3 of atmospheric oxygen. I n presence of sulphite quinol and its sulphonic acids are oxidised by means of Fehling’s solution principlly to dihydroxyquinoldisulphonic acid 5 or 4 atoms respectively of oxygen being used; this oxidation proceeds by way of qumone quinolsulphonic acid quinonesuIphonic acid and quinolcisulphonic acid and not by way of dihydroxyquinone and its sulphonic acids.Unlike quinone and its sulphonic acids dihydrexyquinone and its sulphonic acids do not unite with sulphit3. Part of the quinol which is not oxidised by Fehling’s solutioa to the readily separable dihydroxyquinonedisulphonate yields a readily soluble pale-coloured isomeride but the most important side reaction is the action of the alkali on the quinone- suJphoiate which should lead through hydroxyquinolsulphonate to the final product of oxidation hydroxyquinonesulphonate. T. H. P. Some Derivatives of Resorcinol. H. VERMEULEN (Rec. trav. chim. 1919 38 106-lll).-2-Nitroresorcinol when added to nitric rcid (D 1-5) in the cold yields 2:4-dinitroresorcino17 m.p. 146* mhich when converted into its potassium salt. and heated with an excess of methyl sulphate gives 2 4-dinitro-l 3-dimethoxy-i. 12-1. ABSTRACTS OF CHEMICAL PBPERS. benzene; this when reduced with tin and hydrochloric acid 111 alcoholic solution and the product treated with acetic anhydride gives 2-ni t m-4 -uce t y lam i n 0-1 3-di1?2 e t 12 D c y b en z e il e m . p . 1 6 1-1 6 2 O. This compound on nitration yields 2 6-dinifro-4-acet!/Znmino-I 3- dimethoxybenzene in. p. 129O which when hydrolysed gives 2 6-dinitro-4-amino-1 3-~~2nsethoxyBeiize1ae in. p. 141'. 4-Acztyl- amino-1 3-dimethoxybenzene m. p. 1 1 7 O when nitrated in acetic acid solution yields 6 - n i t r o - 4 - c c c e t ~ ~ ~ ~ ? ~ ~ ~ ? z 0-1 3-di7nethoxybencene m.p. 173* which is also obtained by the acetylation of 6-72itro-4- amim-l 3-dimethoxybenzet~e m. p. 136-137@ obtained by the reduction of 4 6-dinitro-1 3-dimethoxybenzene. Acetylsalicylic [a-Acetoxybenzoic] Acid. HENRY L. DAJXM ( J . Z H ~ . Eny. Chern. 1919 11 29-3O).-The melting point J€ aspirin is determined by immersion of the capillary tube in a stirred paraffin oil bath heated a t the rate of 1' per minute the thermometer being immersed during the whole time of heating but the melting-point tube inserted only when the temperature reaches 1 3 0 O . The free salicylic acid present may be determined by comparison of the colour given with dilute ferric chloride with a series of cobalt chloride solutions of various concentrations. [See J .Sac. Chem. Ind 1919.1 The Elimination of the Carbethoxyl Group from Tautomeric Systems. I. Derivatives of Indene. CHRISTOPHER KELK INGOLD and JOCELYN FIELD TRORPE (T. 1919 115 Preparation of Mercury Derivatives of Phthaleins and Analogous Compounds. SACCHARINFABRIK AKT.-GES. VORSI. FAHLBERG LIST & Co. (D.R.-P. 308335; from Chen2. Zentr. 1918 ii 881-882) .-NeutraI solutions of tzhe alkali salts of phthaleins succineins and " sacchareins " are boiled with large excess of a mercuric salt particularly mercuric chloride whereby uniform products are formed in an easily isolable condition. Thus fluorescein and mercuric chloride yield a reddish-brown l_lrodzict insoluble or sparingly soluble in the usual organic media soluble in sodium carbonate sodium hydroxide o r amrnoiiia to dcep red solutions which show a strong greenish-yellow fluorescenc when diluted.The ammoniacal solution is blackened by amnoniuiii sulphide a t its boiling point. The sodium salt of met.hylflucrescein gives a pale brown derivative with mercuric chloride which dfes silk orange-yellow . Mercuriated compounds from dibromofluo-escein tetrabromofluorescein tetraiodofluorescein phenolphthalein tetra- iodophenolpht halein q uindph thalein ? hydrox yq uin olphihalein resorcinsuccinein cresorcinsuccinein and resorcinsaccharein zre also described. H TI7. W. I). COHET (Rec. trau. chim. 1919 38 72-88).-1n acid solution bemophaone is reduced with the formation of benzopinacone benzhydrol nct being formed. If the actioii is energetic a little diphenylmethane is? W.G . T. H. 1'. 14 3-1 59). The Reduction of Aromatic Ketones.ORGANIC CHEMISTRY. i. 125 formed. I n an alkaline medium on the other hand benzhydrol is almost exclusively obtained unless the alkali is very weak in which case a little benzopinacone is formed. An energetic reduc- tion produces some diphenylmethane. I n neutral medium as when reduced by aluminium amalgam in alcohol benzophenone yields 68% of benzhydrol and 32% of benzopinacone. FARBWERKE VORM. MEISTER LUCIUS & BRUNING (D.R.-Y. 308666; from Chenk. Zentr. 1918 ii 852).-The products of the action of ammonia on P-diazoanthra- quinones are heated in solvents of high boiling point with or with- out a condensing agentl. Thus anthraquinone-P-diazonium sulphate is made into a paste with alcohol and treated with well- cooled Concentrated alcoholic ammonia ; the product is heated with nitrobenzene under reflux when fiP'-dianthrimide separates as a dark brownish-red substance which becomes yellowish-brown when dried or acidified; it forms a scarlet solution in concentrated sulphuric acid which gradually becomes olive and then green.The product from 1 3-dibromoanthraquinone-fi-diazonium sulphate and alcoholic ammonia gives tetrabrol?to-P-d~a?2thru'mide (partly as the benzoyl derivative which is hydrolysed with concentrated sulphuric acid) when heated to gentle boiling with nitrobenzene and benzsyl chloride. The substance is yellow and yields a bluish-green solution in concentrated sulphuric acid; it dyes cotton yelIow from a reddish-brown bath.II ichloro b iadiaz oa n t hraq itin oneamide (from diazotised 1-chloro-2-aminoanthraquinone and ammonia in excess) is pale yellow and is converted by treatment with boiling nit;ro- benzene and benzoyl chloride into 1 l/-dichloro-2 2!-dianthrirnide orange-yellow matted needles soluble in concentrated sulphuric acid to a pure blue solution; it dyes cotton orange-yellow from a reddish-brown bath. H. W. sec.-P-Methylcamphor and sec.-P-Phenylcarnphor a New Series of Synthetic Camphors and tert .-Naphthylborneol and Naphthylcarnphene. J. BREDT ( J . p-. Chern. 19 18 [ii] 98 96-105).-1n consequence of the publication of Ruzicka's paper (A. 1918 i 398) the author gives a short account of work carried out in 1914-1918. [With MARIA SAVEL SBERG.]-The action of magnesium mebhyl iodide on camphor or on fenchone yields the tertiary alcohols methylborneol and methylfenchol which under the action of dehydrating agents yield one and the same hydrocurbon CllH18 b p.172-17507 m. p. 71-73O which shows great stability towards permanganate and is regarded as a homocyclene of the 3b ?Hay- yields an acetyl compound C,,H,,O b. p. zb CH*CMe,--CMe 106-107°/13 mm. and this on hydrolysis I '' gives a secondary dcohol CllHmO m. p. b' CH,- 193O which forms a phenylurethane m. p. 1 0 2 O ; oxidation of the alcohol yields a W. G . Preparation of p-Anthrimides . cc annexed structure. When treated with acetic and sulphuric acids the hydrocarbon 3 at a*i. 126 ABSTRACTS OF CHEMICAL PAPERS. ketone (P-methylcamphor) C,,H,,O m.p. 167-168O giving an oxinze m. p. 125-127O and a senaicarbazone m. p. 255O (decomp.) and yielding 2-metkylcamphoric acid C?IlH1S04 m. p. 191O; the anhydm'de of the acid has m. p. 205*5-207°. The properties of t'hese products indicate that they belong to the camphor series so that in the splitting of the trimethylene ring of the hydrocarbon (see formula above) the linking 3a-3~' is ruptured. This indica- tion is confirmed by the molecular refraction of the ethyl ester of the acid; this ester has D\*"" 1.0289 which differs but little from the vaIue l.);O 1.0298 for ethyl camphorate whereas ethyl isofencho- camphorate has DF 1.0054. The specific exaltation of the mole- cular refraction of the ester olf the new acid EX,= -0.229 is similar t o that -0.18 for ethyl camphorate and is con- ditioned by the annexed grouping whilst in ethyl isofencho- camphorate the grouping CH-CH2-b-Me pro- (IH-C-G-Me derivatives of the 2-methylcamphoric acid were I I prepared the diclaboride b.p. 155O/15 mm. the chlorimted chloride the chlororamh.ydrk?e m. p. 204-20607 the sec.-tert.-amino-acid m. p. 162-163O and its calcium saltl and the acid imide m. p. 256O. [With A. C. HEINEMANN and F. aomm.]--The interaction of magnesium phenyl bromide and camphor followed by treatment of the product with water and dilute hydrochloric acid yields the tert.-phenylborneol m. p. 41° b. p. 119*5.-120*5°/2-2.5 mm. [a]; - 5 0 ~ 3 3 ~ (in benzene) already prepared by Haller. Treat- ment of this tertiary alcohol with acetic anhydride gives a liquid JL?/drocarbon C16H20 b.p. 99O'/2 mm. Di4 0.9920 [u]? + 3 ' 2 7 O which is converted into the acetyl derivative of a tertiary alcohol b. p. 136O/2 mm. m. p. 8 7 O . This hydrocarbon partly undergoes rearrangement t o an isomeride b. p. 86O/2 mm. DjP7 1.0034 [a] -3.75O whilst a third isomeride b. p. 106O/2 mm. m. p. 33-34*5O Dlg6 0.9742 is formed in good yield on repeated dry distillation of the above acetyl compound. The hydrocarbon b. p. 99O/2 mm. does not combine with hydrogen chloride in light petroleum solution but the isomeride b. p'. 86O forms the hydro- chloride C,,H,,Cl m. p. 76'5O which with milk of lime gives a tertiary alcohol C,,H,O b. p. 106*5O [u]go + 23*06O isomeric with the tert.-phenylborneol. Hydrolysis of the above acetyl derivative yields a secondary alcohol C,,H,O m.p. 115-116° which like the products derived from it is optically inactive. Oxidation of this alcohol by means of chromic acid gives a phenylcacmphor C,,H,,O m. p. 68O the formation of which takes place as shown on p. i 127. The new phenylcamphor forms a semicarbaaone xi. p. 189-190° and an oxime m. p. 141-142*5° and when reduced with sodium and alcohol gives a mixture of phenylborneol and phenylisoborneol which were not separated. With sodiopotassamide and amyl uitrite phenylcamphor yields the isonitroso-derivative which forms I I I I duces no exaltation. The following further Me I I heORGANIC CHEMISTRY. i. 127 greenish-white crystals m. p. 1 8 9 O and this with sodium hydrogen sulphite gives phenylcamphwquinone a golden-yellow substance m. p.145O. The latter is also obtained by the action of perman- ganate on phenylcamphorcarboxylic acid m. p. 149-1 50° (evolu- CH,-CH-CH CH,-CH-CH I I CMe I I -+ 1 +32 1 c' H,-CMe-CO CH,-CMe-CPh OH g' CH,-CH-CH I bMe 1 CH-i--CPh \ I CMe,-OH-CH / I I YH2 I CH,:C-CPh-L'H I CMe,-CH-CH I CB,:C-CH-t'HPh v CH,-CH-CH CH,-OH-CH I 1 + I CMe I . I CIHPh-bMe-UH*OH C'HPh-UMe-CO tion of CO,) which is formed from phenylcamphor with the help of sodiopotassamide and carbon dioxide. Phenylcumphom'c acid C16H2004 m. p. 123*5O is formed by t.he protracted action of per- manganate solution on the quinone; its amhydride C,,H,,O m. p. 1 7 3 * 5 O was prepared. [With H. D u s s ~ ~ ~ . ] - T h e action of magnesium a-naphthyl bromide on camphor yields tert.-n~crphtl~?/ZFo~neoZ m. p. 122-124* I C&b,-CH-CH CH,-CH-CH I I YH2 I -+ C€€,:C--CH-CH*C,,H7 (111.) / Y I YH2 CMe,-CH-- I 1 bH!a I CH, C-C( CIoH7)-CH,i.128 ABSTRACTS OF CHEMICAL PAPERS. [a]$ -41.96O in benzene. When subjected to dry distillation this alcohol yields the napht hylcam ph ene C,,H which crystallises in felted needles m. p. 92-93O b. p. 210°/16 mm. and gives no hydrochloride with dry hydrogen chloride in ethereal solution. Treatment of the hydrocarbon with acetic and sulphuric acids yields only an isomeride m. p. 116-117O. From results obtained with methylcyclene and phenylcamphene i t may be assumed that the naphthylcamphene m. p. 92-93O has structure I or 11 and that treatment with acetic and sulphuric acids under the influence of the naphthyl residue leads to rearrangement t o the compound 111 which cannot be acetylated.Condensation of Unsaturated Compounds in Relation to Terpenes Resins and Caoutchouc. H. J. PRINS (Chem. Weekblad 1919 16 64-74) .-The type of condensation discussed is that between molecules of the same subst’ance containing the gr?up :C=C:. The reaction is brought about by catalysts such as acids acid anhydrides halogens and halogen compounds with active halogen sulphur and sulphur colmpounds (persulphides) oxygen and peroxides metallic oxides and metals. The catalyst and sub- strate are (( reciprocally activated .” Three reactions are possible polymerisation of the unsaturated substance combination of catalyst with the substance a t the double bond and combination of catalyst with the pollymerised substance formed.The theory of reciprocal activation is discussed in relation t o the simultaneous polymerisation and oxidation of unsaturated hydrocarbons such as terpenes the formation of resins and the vulcanisation of caoutchouc. Ths following theory for the lastimentioned process is suggested. The caoutchouc molecule is rendered active by means of the catalyst sulphur whilst the sulphur undergoes a change analogous t,o the formation of ozone from oxygen in presence of unsaturated substances There results (1) a simple polymerisation of the caoutchouc molecule with formation of cy clobutane deriv- atives ; (2) polymerisation of the caoutchouc molecule with inclusion of sulphur in the ring giving compounds of the type T. H. 9. :C;-C :C?-C S s i L (3) direct addition of sulphur a t the double bond to form :C-C C-0 \/ 0 1- \ /.S s n w. s. M. Constituents of Resins. 111. Further Investigation of Siaresinol from Siamese G u m Benzoin. ALOIS ZINKE and HANS LIEB (Mortatsh. 1918 39 627-639).-1t has been pre- viously shown that the benzoresinol obtained by Ludy fromORQABNIC CHEMISTRY. i. 129 Sumatra gum benzoin (A. 1893 i 480-666) is probably a mix- ture of d-sumaresinol and I-benzoresinol (A. 1918 i 502); further examination of the substance prepared according to Ludy's direc- tions only led to the isolation of siaresinol (A. 1918 i 398). Ludy's benzoresinol should theref ore be deleted from the literature. Further examination of d-sumaresinol and siaresinol has shown that these substances are acidic in character and that the acidic hydrogen is contained in the carboxyl and not in the hydroxyl group as assumed by Ludy (loc.c i t . ) ; the former is therefore to be regarded as d-szinzaresinolic acid and the latter as d-siuresinolic mid. Oxidation of d-siaresinolic acid leads to ths formation of a monobasic acid C2,H4004 and the loss of three atoms of carbon and eight atoms of hydrogen appears to denote the elimination of a propyl or an isopropyl group; the formula for the parent substance may be written C,H,*C2,H,o0,*C0,H. [With LUDWIG z~c~~~n.]-r%kver siaresinokute forms a white powder which darkens in colour when preserved and decomposes when warmed with water acetone or alcohol. It is converted by methyl iodide into ?nethyZ siaresinolat e which crystallises in pris- matic crystals with 1*5H,O from aqueous alcohol m.p. about 150° in needles with $H,O from benzene and in anhydrous prismattic crystals m. p. 169-170° from light petroleum. The ethyl ester separates from light petroleum in needles or prismatic platelets m. p. 1 0 8 O ; from aqueous alcohol in nodular masses which melt indefinitely a t 102O and contain water of crystallisation. The mixed althyd&'de of acetic and siaresinolic acids melts at 125-127° after softening a t 104O. Chromic acid oxidises the double compound of acetic and d-siaresinolic acid to an acid C27H4004 short prisms m. p. 317O [ulg - 193'8O in chloroform solution < the potassium salt long white needles with 3$H,O and the methyl ester colourless leaflets m. p. 186-187O are described. R. w. Hydroxymethylfurfuraldehyde .J. A. MIDDENDORP (Rec. trau. clzim. 1919 38 1-7l).-The author finds that o-hydroxy- methylfurfuraldehyde obtained by the action of acids on the hexoses can be distilled unchanged in an absolute vacuum giving a distillate b. p. 114-116°/1 mm. which will crystallise and has m. p. 31*5* Dig 1,268 DY 1.2629 n$ 1,556 ~ 2 ~ 1.552 rtr 10563 and its heat of combustion is 664.8 cal. per gram-mol. Contrary to the general statements the author finds that this aldehyde is miscible with water in all proportions and t,hat there is no indica- tion of the formation of a hydrate. It gives a phenyZmthJ- kydrazotne m. p. 161* and an ddazi?ze m. p. 168O (deeomp.) and its hydroxyl group may readily be replaced by halogen by the action of the hydrogen halide in dry ether.o-Chloromethylfur- f uraldehyde is readily converted int.0 ~-metkoxtymetlztylf~~~fu~- aIdeh?/de an oil b. p. 68-70°/2 mm. D17.9 1.146 rig's 1.5088 giving a phen,ylhyclrazone m. p. 56-57O a p-nitrophenylhydr-i. 130 ABSTRACTS OF CHEMICAL PAPEBS. aaone m. p. 140-141° an oxime an aldcczine m. p . 86O a semi- carbazofie m. p. 170° and a semioxamazone m. p . 209-210°. Similarly o-ethoxymethylf urf uraldehyde gives a p-nitrophemyl- hydrazone m. p. 140-141° an oxime an aldazime m. p. 70° and a semioxamazone m. p. 212-213O. Benzoyloxymethylfurfur- aldehyde gives a phenylhyhazone m. p. 112O a p-nitrophenyl- hydrazone m. p. 142O an oxime m. p. 85-86-5O an aldaaine m. p. 163* a semicarbazone m. p. 198O and a semioxamazone rn. p. 204O (decomp.). When distilled a t a pressure of 10-20 mm.hydroxpethylfur- f uraldehyde is partly decomposed giving its anhydride dif urfuryl- methyl etEer which yields a semicarbaame m. p. 255O and when oxidised by moist silver oxide gives di(2-methyl-5-carboxylfuryl) ether m. p. 165O. Sodium hydroxide readily decomposes hydroxymethylf urf ur- aldehyde giving 2 5-dihydroxyrnethylfuran m. p. 80° and 5-hydr- oxymethylpyromucic acid. Under similar conditions methoxy- methylfurf uraldehyde gives 2-hydroxymefhyl-5-metho~xymethyl- furam b. p. 132-134O123 mm. m. p. 37O ng‘51*4860 and 5-meth- oxymethtylpyromzLcic acid m. p. 66-66.5O ; the ethoxy-aldehyde similarly gives 2-hydr~symethyl-5-etkozymethylficram~ b. p. 152-157O/ 20 mm. lz 1.4865 and 5-ethoxymethylpyromucic acid m. p. 62O. Hydroxymethylf urfuraldehyde condenses with ethyl malonate giving ethyl hydroxymethylfurfurylicFenemalonc;cte m.p. 48*5O b. p. 221°/11 mm. Di* 1.1648 rz; 1,539 lzt9 1.536 and with malonic acid giving JLydroxymethylfurf~rylidcnemalonic acid decomposing a t 130O. Ammonia or potassium cyanide react readily in alcoholic solution with hydroxy- methoxy- or ethoxy-methylf urfuraldehyde but the products in every case resinify. From a study of the absorption spectra of the coloured products obtained from f urfuraldehyde and its methyl and hydroxymethyl derivatives respectively with the following reagents resorcinol Sesami oil &naphthol acetone diphenylamine egg-albumin aniline acetate narcotine and orcinol it is shown that the coloured products formed by warming sucrose with hydrochloric acid and the respective reagents resemble those obtained from hydroxy- methylfurfuraldehyde but differ from those obtained from furfur- aldehyde itself.It is shown that diphenylamine is the most satis- factory reagent for distinguishing between pentoses and hexes- and that the reaction with acetone is the most satisfactory for dis- tinguishing methylpentoses f rom penbses and hexoses. FRANK LEE W. G. The Alkaloids of Molarrhena congolensis. PYMAN (T. 1919 115 163-166). Nicotine Content of the Smoke of Heavy Light and ‘1 Nicotine-free ” Cigars. W. STORM VAN LEEUWEN (Arch. expt. Rath. Pharm. 1918 84 282-316),-This content was measuredORGANIC CHEMISTRY. i. 131 physiologically by the effect on the blood-pressure of an acid extract of the smoke and bears no relationship to the trade description or even to the nicotine content of the cigars themselves.The smoke of so-called nicotine-free cigars (Wendt) contains as much as that of average normal ones. A full account of earlier work is given. G . B. Cyclic Acetone Bases. C. HARRIES (Annulem 1918 417 107-191. Compare A. 1896 i 317).-The author has shown that vinyldiacetonamineoxime (4-oximino-2 2 6-trimethylpiperidine) yields a-4-amino-2 2 6-trimethylpiperidine by reduction with zinc dust and cold alcoholic hydrochloric acid and j3-4-amino-2 2 6- trimethylpiperidine by reduction with sodium and boiling amyl alcohol (Zoc. cit. and A. 1897 i 293). These two bas= behave differently towards carbon disulphide. Whilst the j3-base yields only one dithiocarbamate which cannot be converted into a thio- carbimide by mercuric chloride the a-base yields an easily soluble dithiocarbamate which is changed by boiling water into a sparingly soluble dithiocarbamate ; from t)he last hot aqueous mercuric chloride solution produces a substance which has the composition of the expected thiocarbimide but n o t its properties and is there- fore probably an internal thiocarbamide.By treatment with iodine the two a-dithiocarbarnates (2 mols.) lose carbon disulphide (1 mol.) and hydrogen sulphide (1 mol.) and yield two isomeric thiocarbamides probably having the constitution C So N H ( C5H7Me3N)% ; these are probably syn- and anti-stereoisomerides and so also are the two a-dithiocarbamates. The question why the &base does not yield an analogous series of isomerides cannot be answered a t present.[With A. BAUDREXEL H. HOHENEMSER and R. HAARMANN.J- Bet'ween 1896 and 1908 the reduction of 4-oximino-2 2 6-tri- methylpiperidine to a-4-amino-2 2 6-trimethylpiperidine by cold alcoholic hydrogen chloride and zinc dust has frequently been effected. It is all the more remarkable therefore that the authors using present-day zinc dustl (since 1913) have obtained not the above a-base but 2 2 6-trimethyl-4-piperidone. I n order to prepare the a-base therefore 4-oximino-2 2 6-trirnethylpiperidine has been reduced by 3% sodium amalgam in 80% alcoholic solution a t 10-20° 25% hydrochloric acid being constantly added to maintain an acid reaction. This method produces about equal weights of a- and j34-amino-2 2 6-trimethylpiperidine ; the hydrochloride of the latter is insoluble in absolute alcohol.[With BERNHARD S c ~ ~ ~ ~ ~ o n r a . ] - w h e t ~ h e r reduced by cold alcoholic hydrochloric acid and zinc dust or by boiling amyl alcohol and sodium 4-oximino-2 2 6 6-teet~ramethylpiperidine yields only one 4-amirto-2 2 6 6 - t e t r a m e t ~ y l ~ ~ e r i d i n e lea%ets m. p. 16-18O b. p. 79O/7 mm. which is converted by acetic anhydride into the acetnte of the a~et~yylamino-derivative m . p. 2 0 5 O ; the acetylamino-i. 132 ABSTRACTS OP CHEMICAL PAPERS. derivative itself C,,H,ON forms pyramidal crystals m. p. 120° b. p. 161-163°/6-8 mm. I n cold ethereal solution 4-amincr2 2 6 6-tetramethylpiperidine (2 mols.) and carbon disulphide (1 mol.) yield 4-amino-2 2 6 6- tetramethyl@peridine 2 2 6 6-tetranzethylpiperidykdithiocarb- amate CgH,,N-NH*CS*SH,CgH,,N*NH2 crystals m.p. 154O but in the ratio of 1 1 yield tetramethyllnl?eridyldith~ocarbam~c acid C,H,,N*NH*CS*SH m. p. 1 8 0 O ; this and also the preceding salt are converted into a substame m. p. 205O (decornp.) by recrystal- lisation from boiling water. The dithiocarbamic acid in boiling aqueous-alcoholic solution is converted by alcoholic iodine into the hydriodide (two crystalline forms) of the thiocarbamide triangular plates m. p. 170O. Corresponding with the production of two alkamines by the reduction of 2 2 6-trimethyl-4-piperidone (Harries A. 1897 i 293) it is found that 2 2-dimethyl-6-isobutyl-4-piperidone reduced by sodium amalgam in faintly acid solution yields B mixture of labile cis -valerdiac e t onalkamine [4-hydroxy -2 2-dim e t h yl-6-iso b u tyll^/aper- CH(CHzPr~~*CB,>CH*OH m.p. 91-92O (hydro- chloride m. p. 215O) and the stable trans-isomeride m. p. 65O; trhe former is converted into the latter by heating with a solution of sodium amyl oxide. 2 2-Dimethyl-6-isobutyl-4-piperidone forms an oxime C,,H,,ON needles m. p. 121O (monohydrochloride m. p. 238O; &hydro- chloride needles m. p. 222O) which is reduced by sodium and boil- ing amyl alcohol to 4-amino-2 2 - c E i r n e t h y C G - i s o b u t y l ~ ~ ~ ~ ~ ~ n e CllH2*N2 b. p. 147O/65 mm. (hydrochlwide C,,H2,N,,2HC1 ; acetate of the acetyl derivative m. p. 143-144O). The base yields a carbamate by absorption of carbon dioxide and is converted by nitrous acid into the preceding cis-alkamine m.p. 91-92O. By warming with acetic anhydride 2 2 6-trirnethyl-4-piperidone is converted into its acetyZ derivative prisms m. p. 92" which yields ncetylvinyl~~acetonu~ineoxime (1-acetyl - 4 - olmmino-2 2 6-tri- methyllriperidine) m. p. 130° by t-reatment with aqueous hydroxyl- amine. [With A. Z~~~.]-Benzylidenediacetonamineoxime yields only products of fissive decomposition when reduced by zinc dust and aIcoholic hydrochloric acid but is converted by reduction with sodium and boiling amyl alcohol into /3-4-mino-2-phen?/Z-6 6- dimethylpiperidine six-sided plates softening at 60° no definite m. p. b. p. 183O/36 mm. which is isolated as the hydrobromidf C,,H,,N,,ZHBr prisms with 3H20 m. p. 75O decomp.looo; the hydrochloride ~ k f f t ~ T ~ i c h l o r ~ ~ ~ ~ hydriidide and picrate art3 mentioned. [With AUGUST BAUDREXEL.]-U-~-A~~~~-~ 2 6-trimethyl- piperidine and ethyl chloroformate react in cold ether to form the hpdrochloride C,,H,,02N,,HC1 crystals m p. 244-245O of C S( NH CgH,&) idinel NH <CMe,-- CH,ORGANIC CHEMISTRY. i. 133 a-ethyl t r i m e t h y l l n ' ~ e r i d y ~ c a ~ ~ a ~ ~ t e b. p. I 48-150°/ 12 rnm. (picrate m. p. 208-209°). Attempts to eliminate ethyl alcohol from the carbarnate with the object of creating a bridge linking in the 1 4-position were unsuccessfully made with zinc chloride fused sodium acetate phosphoric anhydride phosphoryl chloride and concentrated hydrochloric acid. The a-aminotrimethylpiperidine reacts in ethereal solution with carbon dioxide to form the ca,rbamate C,H7Me3N*NH*CO2H,NH2*C5H,Me3N m.p. 112O. The following compounds of the &series were prepared by similar metbods &ethyl 2 2 6-trimethylpiperidyl-4-carbamate b. p. 151-152O/12 mm. m. p. 6B0 and its hydrochloride m. p.. 253-254O (decomp.) and picrate m. p. 164-165O ; B-arninotrf- me thylp-peridine tm'met hylp'peridylcarbamat e m. p. 92O. [With A. ZART. ]-a- and B-4-Amino-2 2 6-trimethylpiperidine yield dibenzoyl derivatives C,H,O,N m. p. 192-193O and 210-21 lo respectively on benzoylation. The a-base reacts with phenylcarbimide in cold benzene to form the phertyltrimethyl- piperidylcarbamide NHPh*CO*NH*C,B,Me,N needles rn. p. 21 1-212° and with phenylthiocarbimide in ethereal solution to form the corresponding thiocarbumide C,,H,,N,S crystals m.p. l l O o whilst the hydrochloride of the a-base reacts with potassium cyanate in concentrated aqueous solution to form a-trimethyl- piperidylcurbmide C,H,Me,N*NH*CO*NH2 leaflets m. p. 55O (not sharp) decomp. below looo. The corresponding substances in the @-series are p~enyltrimethylpiperidylcar~a~i~e rn. p. 130- 138O the thioctzrbamide C,,H2,N3S m. p. 160-161° and fl-tri- m e thy 1 p@t! ridylcar b amid e m. p . 1 7 0-1 7 1 O . [With HERBERT THOERL.]-E~U~~ mdecular quantities of 2 2 6- trimet8hyl-4-piperidone and ethyl chloroformate in ethereal solution heated on the water-bath with a saturated solution of potassium carbonate yield ethyl 4-keto-2 2 6-trimethylpiperidine-1-carb- oxylate m. p. 34-35O b. p.141-142°/12 mm. (osime leaflets m. p. 136O). The o x h e is reduced by sodium amalgam and a mixture of alcohol water and acetic acid on the water-bath to ethyl 4-amino-2 2 6-trimethylpiperidine-l-carbosylate7 b. p. 160°/ 12 mm. from which an internal 1 :4-carbamide could not be pro- duced. The direct methylation of 2 2 6-trimethyl-4-piperidone a t the imincl-group is very difficultly effected. The result. is attained indirectly however by oxidising a- and 8-N-methylvinyldiaceton- alkamines (see below) by chromic and acetic acids. Although the a-isomeride is very resistant to oxidation both yield the same N-meth~luin~ytdaacetorsumine (1 2 2 6-t~tranaethyl-4-piperidor~e) b. p. 96-97O/f4 mm. which is purified through the hydro- bromide. It forms an oxime prisms m.p. 93O (picrate needles m. p. 216O [decomp.]). [With AUGUST BAUDREXEL .]-The following derivatives have been prepared with the object o€ obtaining substances suitable fori. 134 ABSTRACTS OF CHEMICAL PAPERS. the easy identification of the more important cyclic acetone bases but none of them compares with the oxime f o r this purpose. 2 2 6-Trimethyl-4-piperidone f orms a semicarbasonle CgHI8ON crystals m. p. 196-197O (oxalate m. p. 182O) the triacetonamine forms a semicadazone C,,H,,0N4 crystals m. p. 219-220° whilst benzylidenediacetonamine forms a p-nztrophenylhydrazone CI9H,O,N,? 111. p. 105-106°. [With ARTHUR Z~~~.]-+Hydroxy-a- and -p-1 2 2 6-tetra- methylpiperidines are readily obtained by heating the 4-hydroxy- 2 2 6-trimethylpiperidines with 40% formaldehyde on the water- bath.The hydrochloride of the a-compound reacts with benzoyl chloride at 120° to form a-4-beneoyl-l 2 2 6-tetramethylpiper- idine b. p. 194-195O/16 mm. (hydrochloride m. p. 192O platinlzi- chloride m. p. 208O [decomp.] nitrate and picrate m. p. 180-181*). The corresponding B-benzoyl derivative has b. p. 195O/15 mm. and forms a hydrochloride m. p. 58O (not sharp) pZatinichZoride m. p. 2 1 8 O (decomp.) nitra.te m. p. 163O (decomp.) and picrate m. p. 213O. [With ERICH GROSCHUFF.]-T~~ behaviour of cyclic acetone bases towards nitrous acid has been already published (A. 1901 i 745). c. s. New Mode of Formation of Pyrrole-black. A. ANGELI and A. PIERONI (Atti R. Accad. Lincei 1918 [v] 27 ii 300-304. Compare A. 1918 i 547).-Treatment ob pyrrole with the calcu- lated quantity of magnesium ethyl iodide in very dilute ethereal solution and passage through the liquid of a gentle curTent of air for about twenty-four hours yields a voluminous very black powder which may be obtained almost free from ash by treatment with dilute sulphuric acid.This substance is far more intensely black than the pyrrole-blacks obtained by metlhods previously described and like these and the natural melanins it does not melt but furnishes vapours which turn a pine splinter moistened with hydrochloric acid an intense red; it is insoluble in all ordinary solvents and also in alkali solutions. It is slowly oxidised by hydrogen peroxide in acetic acid or dilute aqueous permanganate or dichromate and dilute sulphuric acid.The compositions of the different pyrrole-blacks obtained in various ways are given. The yellowish-white product formed together with pyrrole-black by tbe action of peracetic acid is probably a derivative of tripyrrole and its composition is in agreement with the formula CI,Hl70,N,. Like aniline-blacks pyrrole-blacks react readily with phenylhydrazine. T. H. P. Action of Cyanogen Haloids on Phenylhydrazine. IV. Passage to Derivatives of o-Phenylenediamine . G. PELLIZZARI and AUGUSTO GAITER (Gazaetta 1918 48 ii 151-182.)-FurtherORGANIC CHEMISTRY. i. 135 investigations (compare A. 1892 1323; 1907 i 873 and 1911 i 338) show that i t is possible to eflect the following series of changes NHPh-NH + CN*NPh*NH + CBH4(- N>C*NH*CN -+ C6H4<G:>C*NHeCN + C,E3,<~~>C*NH*CO-~H2 + W N ) (c,H,<~:>c*NEIco) 2 NH c,H,<;~>c*NH~co-NH -+ C ~ ~ < ~ ~ > C ~ N H ~ 9 N ,-? c 6 B 4 < ~ ( ~ ~ ) ~ c (NH2) \ * C,H,<;>C*NH NH:d.OEt C,H,( NH,) -+ G6H4<~~>c*NH,.--N> ' C*NH.CN C6H&I (CN) aP -Die y ano-o- ph eniy 1 e n egua nidine obtained by the action of cyanogen bromide on A-cyanophenyl- hydrazine in presence of water and pieces of marble forms white crystals and turns yellow and then brown when heated but does not melt a t 300O; it reach acid towards litmus and emits ammonia when heated with alkali hydroxide. The sodium salt forms a crystalline magma and the potassium salt a gelatinous mass. P - C y a n o - o - ~ h e ~ y ~ e ~ e g u u ~ ~ d i n e C,H,s;>C*NH*CN prepared by the action of potassium hydroxide on the preceding compound forms long thin elastic shining needles and turns yellow a t 240' and softens and decomposes a t 250-260O; it has slightly acid properties and exhibits normal ebullioscopic behaviour in alcohol.It is highly resistant t o the action of potassium hydroxide and only in a sealed tube a t 140° is it possible to detach the B-cyanogen group. C,H~G;>C=NH-CO *NH obtained as hydrochloride by the action of hot dilute or cold con- centrated hydrochloric acid forms shining colourless needles and becomes opaque b u t does not melt a t 300O. Its hydrochloride C,H,ON,,HCl decomposing a t 255-260° platinichtoride and picrude were prepared and analysed. niphenyleneguanylbiuret (C,H4Gg>C*NH*CO) NH ob- tained by heating the preceding compound a t 180-200° crystal- lises in slender needles.o-Phenyleneguanidine prepared by the action of hydrochloric acid on o - p hen y len egu a n y 1 c arbamid e or as - d icy ano- 0-p h en y lene - Its silver salt was prepared and analysed. o - ~ h enytene -P-g uanyt car b amide 2i. 136 ABSTRACTS OB CHEMICAL PAPERS. guanidine is identical with the compound obtained from cyanogen bromide and o-phenylenediamine (compare Pierron A . 1908 i 926). The following salts were prepared and analysed carbonate ; nitrate exploding without melting a t 225O; acetate m. p. 2 1 8 O ; p k u t e m. p. 270° (decomp.); and $atimichtoride +$H,O which softens a t 225O and then melts and decomposes. The free base may be recognised by the alkaline reaction of its aqueous solution towards litmus and by the inteme blue coloration changing to green and then to brownish-yellow obtained by the action of hypobromites or hypochlorit es.A cetyl-o-phenaylemeguanidine C6H4<N -N\ H>C*NHAc forms slender white needles m. p. 314-315O (decamp.). The action of nitrous acid on the corresponding benzoyl derivative (compare Pierron loc. cit .) yields phenylenecaybarnide C,H,<GE>C*OH or c,H,<~~>co. NH rn-Nit rob e nz ylidene phe nyle mequnnidime prepared from o-phenyleneguanidine and m-nitrobenzaldehyde in presence of a drop of piperidine forms minute yellow needles m. p. 1 7 0 O . from o-phenyleneguanidine and cyanogen bromide forms long colourless needles and decomposes a t 173-175O rapidly in a moist atmosphere and slowly in a desiccator.Its plutimichlom'de turns brown a t looo and undergoes change when boiled with water. a-Cyamo-a-phenylemeguanidine C,H*<N(CN)> -N C*NH obtained m-Nitrob en2 ylidene-a- cyano-o-phen yleneg uanidine prepared by the interaction of a-cyano-o-phenyleneguanidine and m-nitrobenzaldehyde in alcoholic solution in presence of a drop of piperidine forms microscopic yellow crystlals and decomposes at a-Ethoxy-oyhenylenecarbirnimoguanidine C6H4<z>C*NH obtained together with the preceding compound f o m s colourless needles m p. 1 5 5 O . Its ~ Z u t ~ n ~ c h l ~ ~ d e forms pale yellow rhombs m. p. 222-224O (decomp.). With m-nitrobenzaldehyde in presence of a drop of piperidine the base yields m-nitro benzy2idene-a- ethox~-o-pheny~enecarbi~~?~ogu~nidine 6'17H1503N5 which crystal- lises in pale yellow needles m. p. 205-206O (deco'mp.). According to Pierron (Zoc. cit.) the action of cyanogen bromide (3 molls.) and sodium hydrogen carbonate (3 mols.) on o-phenylme- 285-290O. N H :C*OEtPHYSIOLOGICAL CHEMISTRY. i. 137 diamine (1 rnol.) yields a little phenyleneguanidine and a large proportion (1 2 0 4 4 0 % of the phenylenediamine used) of iminodi- carboaylphenyleneguanidine C H /NH\C=ZN This 4\N-/ 'co ' \ c! 0. N d compound may be obtained also from phenyleneguanidirie (I mol.) cyanogen bromide (2 mols.) and sodium hydrogen carbonate (2 mols.) or from phenyleiieguanidine and biuret. The mechanism of its formation is under investigation. T. H. P. Simultaneous Biochemical Syntheses of Gentiobiose and of the two P-Glucosides of Glycol by Emulsin. EM. BOUIXQLTELOT and M. BRIDEL (C'ompt. mTLd. 1919 168 253-256). -From the products of the action of emulsin from almonds on a mixture of dextrose and ethylene glycol in the molecular propor- tion of 2:1 in aqueous solution the authors have isolated and charscterised gentiobiose glycyl fl-glucoside and glycyl fl-di- glucoside. w. G.

ISSN:0368-1769    

DOI:10.1039/CA9191600117

出版商:RSC    

年代:1919

数据来源: RSC

摘要:

ii. 125 General and Physical Chemistry. Reversal of Spectrum Lines Produced by a Spark under Water. TOSHIKAZU MASHIMO (jfeem. toll. scz. Kyoto. Imp. ulziv. 1918 3 73-79).-The spectra of aluminium zinc cadmium and iriercury produced by sparking between poles of these metals under water have been examined down to A = 1850 pp. It is shown that certain of the lines are reversed by this process; in the case of aluminium the lines hh1930 1935 2205 2210 2263 2268 2367 2378 2567 2575 2653 2661 3082 3093 and 3944,up are reversed. With zinc the lines hX2026 2062 2087 2097 2102 2105 2139 2288 and 2832 ( 2) suffer reversal. Cadmium gives the lines hh 2144 2288 3069 and 3095p.p reversed whilst in the case of mercury the lines hh 2482 and 2537 pp are reversed. Effect of an Electric Field on the Spectrum Lines of Helium.11. TOSHIO TAKAMINE and NOBORU KOKUBU (Mem. Coll. 8 c i . Kyoto. Imp. Univ. 1918 3 81-92. Compare A. 1917,ii 401). -Making use of Lo Surdo’s method the effect of electric fields (3000-70,000 volt per em.) on the helium lines hh 4169 4144 4026 4009 3966 3868 3830 3820 3614 3448 and 2945 has been examined and the results compared with those ob Stark Brunetti and Koch. It is shown that helium lines are dected in three ways by an electric field (1) symmetrical resolution (A 4686) (ii) non- symmetrical resolution (diffuse seriries of lines of helium and par- helium) (iii) one-sided displacement (principal series lines and sharp series lines of helium and parhelium). In the last-named case only the lines belonging t o the principal series of parhelium are displaced toward the violet whilst the other three series lines are displaced toward the red.Diffuse series lines are usually accom- panied by an isolated component on the violet side the starting point of which approaches mure nearly to the initial line as the tern1 number increases. The liize X 3830 the position of which was cal- culated by Koch but not observed by him appears in the photo- graphs of some of the present experiments. Two lines A2804 and 2482 A.U. which are1 probably due to mercury were also found to be displaced slightly .towards the red in an electric field. J. F. S. Investigation of Extreme Ultra-violet Spectra with a Vacuum-grating Spectrograph. J. C. MCLENNAN and R. J. LANG (Proc. Roy. Soc. 1919 [ A ] 95 258-273).-A preliminary paper in which a full description of a vacuum-grating spectrograph designed and made by the Adam Hilger Colmpany is given.The theory of the concave grating is developed and the experimental details f o r deterrnifiing wave-lengths by means of this instrument are described. A short summary of the previous work in €he extreme ultra-violet region precedes a description of the various J. F. S. VOL CXVI. ii. 6ii. 126 ABSTRACTS OF CHEMICAL PAPERS. types of arcs used in the present examination of the extreme ultra- violet spectra of mercury copper iron and carbon. The spectra were photographed on Schumann plates made by Hilger and the wave-lengths are measured to within one Angstrom unit. I n the case of mercury nine lines appear in the photograph lying between A=2054 A.U. and h = 1435 A.U.; with copper thirteen lines appear between A=2243 A.U. and A=1925 A.U.; in the case of iron tu-enty-seven lines are found between h=2027 A.U. and h=1427 A.U. ; carbon shows twenty-eight lines between A = 2023 A.U. and 584 B.U. Photographs of all the spectra are reproduced in the paper. J. F. S. Emission and Absorption in the Infra-red Spectra of Mercury Zinc and Cadmium. RAYMOND C. DEARLE (Proc. Roy. SOC. 1919 [,4] 95 280-299).-The absorption spectra of mercury zinc and cadmium have been measured in the infra-red region; for the region up t o 8500 A. the spectrum was photo- graphed whilst above this wave-length a linear thermopile and galvanometer were) used. The light was obtained from a mercury amalgam lamp of the Heraeus type; the amalgam consisted of 60% mercury 20% lead 20% bismuth 3% zinc and 4% cadmium.In some cases an arc of the metal in a vacuum was employed. For the energy measurements a 100 volt Nernst glower was used. I n the case of mercury absorption bands A = 1.014 p 1.038 p 1-065 p 1.089 p 1-129 p 1.160 p 1.207 p and 1.359 p were observed. Energy measurements were made in the region 1.2-1-5 p the only absorp- tion band observed lying a t A = 1.359 p. No absorption was shown in the case of the energy measurements of zinc until the tempera- ture had been raised t o 275O. A t this temperature absorption was observed a t A = 1.105 ; in the longer wave-lengths evidence was more difficult to obtain but indications of absorption were obtained at Ah 1,379 p 1.41 p 1-57 p and 1.65 p.Witb cadmium vapour absorption was found a t A = 1.040 p) which is the first line of the series v = (2.58) - (n7,P) ; a second strong absorption band occurs at A = 1.503 p whilst less marked absorption occurs a t Ah = 1.129 v 1.395 p 1.4475 p 1.522 p ) and 1.563 p. By the photographic method a line was observed a t 6977.4 A. in one series of experi- ments but this line could not be reproduced. Some absorption expriments were carried out with a quartz cell containing cadmium iodide; it was found that there was no absorption in the visible and ultra-violet regions at comparatively low temperatures but with increased temperature a broad band was observed which extended from the limit of the ultra-violet end of the spectrum u p to a wave- length of about ~ = 4 0 0 0 A.Attemph to resolve this band failed. In the longer wavelengths no absorption was visible a t wave-lengths characteristic of the cadmium spectrum. Energy measurements made in the long wavelength region above h=1*0 p showed the presence of an absorption band a t h=1*040 when the temperature of the cell was above that necessary for dissociation. The emission anad absorptio'n curves obtained by bombarding mercury vapourGENERAL AND PRYRlCAL CHEMISTRY. ii. 129 with electrons with the object of producing the single line spectra are given. J. F. S. Characteristic Ultra-red Vibrations of Diatomic Crystals. M. BORN (Physikal. Zeitsch. 1918 19 539-548).-A mathemati- cal paper in which the relationship between the constants of a diatomic regular crystal grating is considered.The influence of electrons on the index of refraction in the ultra-red is also con- sidered mathematically. The results obtained are applied to crystals of rock salt sylvine potassium bromide potassium iodide pyrites fluorspar and sodium chlorate. Absorption Spectra and the Ionisation Potentials of Calcium Strontium and Barium. J . C. MCLENNAN and J. F. T. YOUNG (Proc. Roy. SOC. 1919 [,4] 95 273-279).-The absorption spectra of calcium strontium and bariwn have been determined and from the values of the wavelengths the ionisation potential of these elements calculated. I n the case of calcium a hollow carbon filled with metallic calcium was used and it was observed that the reversals were confined entirely t o those wave- lengths which were members of the series v = (1-5,s) - (m,P) ; as given by Lorenser (Inaug.Diss.) these are J. F. S. m = 2. 3. 4. 5. 6. 7. A = 4326.91 2721-77 3298.66 2275.60 2200.8 2151.00 7% = 8. 9. 10. 11. A = 2118.99 2097.8 2083.2 2072.8 In the case of strontium the sulphide was ernpJoyed instead of the metal and the wavelengths for v = (1.5,s) - (mJ') also accord with those of Lorenser. The following were found nt = 2. 3. 4. 5. 6. A = 4607.52 2931.98 2569.60 2428.16 2354.40 m = 7. 8. 9. 10. 11. h = 2307.5 2275.5 2253.5 2237-4 2226.0 In the case of barium the oxide was used and by noting the reversals nine members of the series Y = (1.58) - (m,P) were ob- tained ; these are m= 2. 3. 4. 5. 6. A = 5535 3275 2 845 2697 2542 v = 10864.6 30534.4 35 149.4 38502.1 39339.1 m = 7. 8.9. 10. A = 2498 2470 2455 244 1 Y = 40032 40486 40733.2 40966.8 From the limiting frequencies of the single series of the spectra the following ionisation potentials of the vapours have been calculated mercury 10.45 volts; zinc 9.4 volts; cadmium 9.0 volts ; magnesium 7.65 volts ; calcium 6.12 volts ; strontium 5.7 volts; and barium 5.21 volts. J. F. S. 6-2ii. 128 ABSTRACTS OF CHEMICAL PAPERS. Changes in Spectrum Intensity and Weakening of the Iodine Fluorescence by means of a Magnetic Field. W. STEUBING (Amz. Physik 1919 [iv] 58 55-104).-1n a previous note (Verh. deut. physih-al. Ges. 1913 1181) it was shown that when fluorescent iodine vapour is brought between the poles of a powerful electric magnet the intensity of the fluorescent light is greatly diminished.The preseiit paper deals with the investiga- tion of this phenomenon. The light changes have been investigated spectrophotometrically and spectrographically and a series of energy measurements have also been made. It is shown that it has been impossible to attribute the weakening of the iodine fluorescence to any definite cause but that i t depends on the action of a magnetic field on the electron vibrations which give rise to the emission of a band spectrum. The effect is greater with the higher frequencies than with the lower and further the magnetic field has a more pronounced action the greater the vibration amplitude during the emission. The present phenomenon theref ore bas nothing in common with other processes which diminish o r destroy fluorescence. The magnetic action has little to do with the actual fluorescence and the same effect is to be expected if the same band spectrum is produced in some other way; it is to be expected that t’he magnetic weakening will take place more easily the greater the energy per molecule with which the emission occurs and conse- quently an electrically produced spectrum will be correspondingly more strongly weakened by weaker magnetic fields.J. F. S. The Magnetic Field and the High Frequency Spectrum of the Elements. RITA BRUNETTI (NUOZIO Cim. 1918 [vi] 16 ii 5-18).-Assuming that the action of a magnetic field results in decomposition of high frequency radiations the results of the author’s experiments show bhat the ordinary means of spectral analysis would be insufficient t o reveal directly such decomposition if the latter were of the type and order of magnitude of the Zeeman phenomenon.None of the theories on the emission o f high fre- quency radiations excludes the possibility of a decomposition pro- duced in this manner. The lines of the K spectrum f o r iron nickel and copper are found by the curved crystal method to be double the mean difference between the two components being 81 1000 and 11/1000 Angstrom units for the a and fl lines respectively. No qualitative modification of any kind is exhibited in the character- istic spectra of these elements under the influence of magnetic fields of moderate magnitude and degree of variation. T. H. P. Light Positive and Light Negative Photophoresis [in Connexion with) Sulphur and Selenium.IRENE PARANKIEWICZ (Ann. Physik 1918 fivl? 57 489-518).-1t has been shown by Ehren’haft (ibid. 1918 56 81) that particles of matter fall under the action of gravity but rise in an electric field; some particles when subjected t o a strong beam of light are deflected in the hori- zontal direction from their original path. Thus sulphur particlesGENERAL ANT) PHYSICAL CHEMISTRY. ii. 129 move in the direction opposite to that of the beam of light (light negative) ; selenium particles under some conditions move in the direction of the beam of light (light positive). The present paper is a continuation of this work and deals with the dependence of the phctophoresis on the chemical nature of the particles the intensity of the light pressure of the surrounding medium and the size of the particles.The work has been carried out with sulphur and selenium particles of radius 8-60x10-6 m. The methods adopted in the investigation were similar tot those employed b'y Ehrenhaft. It is shown that sulphur particles are always light negative whereas selenium par ticles are either light negative or light positive depending on the duration of heating in the production of the particles. The light negative photophoric force! on selenium particles is approximately six times as great as the force of the same light beam on sulphur particles of the same mobility. The intensity with which particles of a given material react on the light is dependent on the size of the particles. The negative photo- phoresis shows its maximum action on sulphur particles of radius 27 x 10-6 cm.and on selenium particles of radius 15 x 10-6 cm. The photophoric force on sulphur and negative selenium is independent of the time whilst with positive selenium it is a function of the time. The power of reaction on the light of positive selenium decreases with time. The photophoric force is independent of the surrounding gas and also of the pressure. The independence of the photophoric force on the pressure the chemical nature of the sur- rounding gas the decrease of the positive reaction of selenium par- ticles which is due t o an internal change of the selenium and further the fact that particles of different materials but of the same mobility are very differently acted on by light all tend to confirm the conclusion of Ehrenhaft that t,he action is a direct one of the light on the material.X-Ray Spectra and the Constitution of the Atom. 11. L. VEGARD (Phil. Mag. 1919 [vi] 37 237-280. Compare A. 1918 ii 144).-A theoretical paper in which the process of recom- bination of the primaries is discussed together with some of the consequences which follow from them. Calculations are made of the quant-number and the number of electrons of the ring systems from the observed frequencies. The possibility of there being two L and two M rings is considered. It is shown that whether recom- bination is assumed from a normal or deformed primary system or recombination from a secondary one it must be assumed that the angular momentum of the electrons left behind in the atom remains unchanged; and further i t must be assumed that the changes of energy of the systems situated between the broken ring and the ring of departure enter into the energy quantum of radiation which is emitted as the result of recombination.On the basis of the theory of the production of X-rays developed by the author it must follow that recombination takes place from secondary systems and that always the angular momentum of the electrons left behind J. F. S.ii. 130 ABSTRACTS OF CTIEMTCAL PAPERS. in the atom is kept constant during expulsion and recombination. A number of relationships of the atomic constitution and proper- ties of the atoms are given. All elements belonging to the same period of the periodic classification have the same quanbnumber and this number increases by onel unit on passing from one period t o the next.Radioactivity and the Coloration of Minerals EDGAR NEWBERY and HABTLEY LUPTON (Mern. Munchester Phil. SOC. 1918 62 No. 10 1-15).-The colours obtained on exposing various substances to the action of the @- and y-rays of radium and some- times to the a- @- and y-rays osf the radium emanation are recorded. Various differently coloured fluorspars owing to their wonderful range of colours and remarkable thermoclumine8scence proved the most interest>ing the changes produced by radium being so varied as t o be bewildering. A colourless Matlock fluorspar after twenty-four hours’ exposure to 50 mg. of radium became blue deeper than a copper sulphate crystal the colour being permanent in the dark but destroyed by direct sunlight or more slowly by daylight and by gentle heating but the fluorspar may be recoloured by radium indefinitely.Under cathode rays only a faint purple surface colour was produced. The blue colour is probably due to the y-rays as it penetrates right through the crystal. Tha thermo- luminescence was green and feeble but a Pyrenean fluorspar not coloured by radium gave a remarkable and lasting green light on heating even though only exposed 150 mm. away from the radium. The thermocluminescence of Cornish chlorophane is to be ascribed to y-rays from radioactive materials. On crystal quartz there was no sign of the ‘ I rotting ” produced by radium rays in fused quartz. The natural colours are discharged by heating but may be restored by radium. Clear selenite cryst’als were coloured brown in regular figures the remaining parts being colourless a phenomenon which Miers explains by certain faces of the crystal during growth attracting impurities to which the colour is to be ascribed.Among other sub- stances examined were diamond native sulphur cryolite rock-salt sylvine ruby anhydrit e celestine barytes anglesite apatite phos- phorite topaz zircon beryl kunzite calcite glass and bakelite an artificial amber-like material used for electric insulation. The view that the colours are due t o dissociation of minute traces of impurities and the luminescence to the recombination of the pro- ducts of dissociation is favoured. F. s. Dependence on Temperature of the Dielectric Constant of some Gases and Vapours. MARIO JONA (PhysikaZ Zeifsch.1919 20 14-21) .-The dielectric constant of air carbon dioxide ammonia sulphur dioxide methyl alcohol vapour and steam has been measured a t a series of temperatures from 17.8O to 178*1°. Curves of the variation of the constant with temperature are given and the significance of the curves i s discussed mathematically. J. F. S. J. F. S,GENERAL AND PHYSICAL CHEMISTRY. ii. 131 Significance of the Volta Effect in Measurements of Electromotive Equilibria. A. SMITS and J. M. BIJVOET (Proc. K . Akad. Wetensch. Amsterdam 1919 21 562-569) .-Applica- tion of the more recent views of edectromotive equilibria to the Volta effect leads to the result that on polarisation and passiva- tion the change in this effect must be great and that in these phenomena the Volta effect would constitute even the greatest part of the total change in the electromotive force.It is found further that if the Volta effect between metals in which the state of internal equilibrium prevails are really very small as is rendered probable by recent experimental work this must be regarded as a characteristic property for metals in internal equilibrium. The values found on measurement of potentdal differences for metal-electrolyte termed experimental electrical potentials always contain an unknown Volta effect and it is this which renders impossible calculation from the said potentials of the saturation concentrations of the metal ions. Relations have been derived which contain t'he solubility pro- duct of %'he metal the solubility quotient af the non-metal or the electron concentration in the electrolyte but not the Volta effect and these pertnit of the preparation of a solubility product series of metals and a solubility quotient series of non-metals from which conclusions may be drawn as to the chemical and electrochemical behaviour of the metals.T. H. P. Hydrogen Overvoltage. DIJNCAN A. MACINNBS and LEON ADLER ( J . Amer. Clzem. Soc. 1919 41 194-207).-None of the theories advanced to account €or overvoltage with the exception of that of Moller (A. 1909 ii 114) a t t m p h to explain the great influence exerted by the physical condition of the electrode on the overvoltage a polished platfinurn t3lectrode for instance showing an overvoltage as high as 0.1 volt whereas that for platinised platinum is nearly zero.The authors have made a number of measurements of hydrogen overvoltage with platinised platinum electrodes use being made of an apparatus resembling but differ- ing in detail from that of Thiel and Breuning (Zeitsch. anorg. Chem. 1913 83 329). With such low currents tthat one bubble od hydrogen appears in one or mcrre minutes fluctuations in the overvoltage are observed the curve connecting overvoltage with time being sinuous with a sharp break invariably following the highest voltage. At low current densities the bubbles come off a t one point and continue to do so no matter how long the observa- tions are continued so that each bubble probably leaves a nucleus behind it when it becomes detached. I n explanation of these results it is assumed that molecular hydrogen when formed from hydrogen ions by the reaction 2H+ + 2~ = H goes directly into solution in the electrolyte immediately surrounding the eleckrode so that the hydrogen a t that point will tend to rise in concentration and produce a supersaturated solu- tion unless carried away by diffusion stirring or other means.If.ii. 132 ABSTRACTS OF CHEMICAL PAPERS. however a nucleus of gaseous hydrogen is present in the electrode a portion of the hydrogen will enter this gaseous phase either directly from the electrode or by absorption from the electrolyte the gaseous nucleus thus playing a part similar to that of a small crystal in a supersaturated salt solution. Hydrogen gas in the form of small bubbles must have a higher energy content per mol.of gas than the same volume of undispefrsed gas as energy must be expended in overcoming the surface tension in the formation of small bubbles. Such bubbles will be more soluble t.hat is will remain in equilibrium with more concentrated dissolved hydrogen than the undispersed gas this phenomenon being analogous t o the increase in solubility produced by the fine grinding of solids. Since other factors being constant the potential a t a hydrogen electrode depends primarily on the concentration of the dissolved hydrogen an electrode in equilibrium with the m a l l bubbles will reach a higher potential than a similar electrode in equilibri-clm with the undispersed gas. As electrolysis proceeds and the nucleus of gaseous hydrogen grows the energy necessary to produce further growth must decrease since the value of the ratio increase in surface increase in volume is continually decreasing; if the bubble grows slowly the hydrogen-bearing solution surrounding the elec- t r d e will tend to get into equilibrium with the bubble. This accounts for the decrease in overvoltage from a maximum point of the sinuous curve to a minimum point where the buoyant effect of the solution is sufficient to overcome the attraction of the elec- trode for the bubble which breaks away leaving a nucleus behind.On the rising part of the curve the concentration of the dissolved hydrogen is increasing to a value such t.hat the nucleus can again grow and so on. As the bubbles are not always evolved a t the minimum points of the curve it seems probable that since the nuclei tend to form in depressions in the electrode the bubbles that separate from the nuclei remain in these depressions until forced out by the growth of succeeding bubbles. I f the electrode can adsorb large hydrogen gas nuclei to start' bubble formation the supersaturation cannot rise to high values and the electrode will have1 a low overvoltage metals with small adsorptive powers however hold small nuclei and have high over- voltages.Supporf of the above explanation is furnished by microscopic examination wf various electrodes when evolving hydrogen this indicating experimental agreement with a theoretical quantitative relation between t-he size of the bubbles from and the overvolt.age of platinised platinum electrodes. Further theory indicates that the overvoltage should increase as the pressure decreases and this is shorn to be the case by the authors' results and also by un- published work of R.M. Gmdwin and L. A. Wilson. T. H. P. The Modalit'y of Reactions and Chemical Dynamics ; Application to the Phenomena of Electrolysis and Spectro- scopy. J. MEUNIER (Bull. SOC. chim. 1919 [iv] 25 49-68).-TheGENERAL AXD PHYSIUAL OHEMISTRY. ii. 133 chemical dynamics are the same in principle in the different forms of electric cells which only differ amongst themselves in their com- plex and variable secondary reactions. There is the same analogy in the production of spectral rays. The appearance od rays in the spectsum does not characterise as is usually stated an element but rather a reaction of this element and consequently indicates the presence of another element reacting with it.W. G. Theory of Specific Heat. 11. WALTER JANKOWSKY (Zeitsch. Elektrochem. 1919 25 1-3. Compare A. 1918 ii 59).-The author answers the criticism of Drucker (A. 1918 ii 216) made in connexion with the earlier paper and a further development of the theory of specific heat is contributed. It is shown that the statement that the change of the specific heat with temperature disproves the law of Dulong Petit and Joule is incorrect for in every case regular relationships exist beitween the specific heat the number of atoms and the molecular weight. J. F. S. Specific Heat Determinations at Higher Temperatures. WALTER P. WHITE (Amer. J . S C ~ . 1919 [iv] 47 44-59).-1n determining the specific heats of various substances a t temperatures up to 14OOu by the method of mixtures the errors in the final result frequently approach one part per thousand even with precise work.The chief sources of error are (1) the determination of tempera- ture in the furnace (2) tlhe loss of heat during the dropping of the charge (3) the exposure of the calorimeter to the atmosphere during the drop (4) the effect of external conditions on the calori- meter and (5) internal effects such as auxiliary changes in the interior of the calorimeter after the drop. Of these errors the variability of the heat losses attending t4he dropping of the hot substance into the water is surprisingly great and should be prevented. Modifications in furnaces and in methods of transference to the calorimeter are described in detail.[See further J . SOC. Chem. Ind. 1919 158~.1 A. B. S. Specific Heats of Silicates 11. WALTER P. WHITE (Amer. J Sci. 1919 [iv] 47 1-43. Compare A. 1909 ii 966).-The specific heats of various silicates a t various tempelrature intervals frolm 0-1400° were determined using the met'hod of mixtures with greater precision than hitherto. For quartz and silica glass the values of the interval specific heats satisfy the expressions Quartz .... .. . . . ... Silica glass.. . . . . . . 0.1685 + 0.0001948 - 0~000000116z 0-1670 I- 0.0001896 - 0~00000012582 The " iiistantaneous," or true atomic heats rise regularly from about 3.5 a t Oo to about 5.96 (with anorthite to 6.6) a t 1300° the value given by the classical kinetic theory.The variations of the atomic heat from the theoretical constant 6*ii. 134 ABSTRACTS OF CHEMICAL PAPERS are due partly ta secondary thermal effecb connected with ex- pansion change of s t a b or chemical action and partly to the universal tendency towards a maximum value a t a high tempera- ture. The location of the development curve agrees approximately with the values of the atomic vibration frequency calculated from the known properties of the atoms. The difference in the value of the elemenh and compounds shows that it is not a property of the atom but appears to be related to the combined oxygen. The calculated specific heat of silica glass a t constant volume and that a t constant pressure are equal but the actual heat- temperature curve of silica glass above 600° is above the theoretical value; that of the cristobalite is identical with the theoretical curve a t 900° but then rises above it.With albite and microcline the specific heat a t constant pressure is considerably above the specific heat at constant volume and this confirms the evidence that the theoretical value of the dimension constant R in the expression C - C = [ A (3a)2 0 I/ Kd is exceeded a t high tempera- tures. On comparing the specific heats of various silicates in the crystal- line and glassy form respectively it was found that the specific heat of the glass is seldom greater than that of the cryst>al. A. Smits’ attempt6 to correlate inversion with equilibriun- temperature changes in liquids or liquid and solid systems have been examined with negative results and it is suggested that pre- mature fusion due to impurities and sluggishness of transformation account for the observed phenomena.The conclusion is drawn from the expansion and specific heats of solids being much less anomalous and irregular than those of liquids that the molecular changes in solids are of a different order of magnitude. The author partly agrees with Bridgman that t4here is no relation between the volume specific heat and cohesion of pre-inverted and inverted substances but considers that the change of properties during inversion although rapidly accelerated a t times is nowhere sudden and discontinuous. The observed difference in the atomic heat of different crystal- line forms of the same substance is so irregular that similar differences with substances of unlike composition must be inter- preted cautiously. [See further J .Soc. Chern. Znd. 1919 14OA.l A. B. S. Specific Heat of Aqueous Solutions with Special Reference to Sodium and Potassium Chlorides. W. R. BOUSFIELD and C. ELSPETR BOUSFIELD (Phil. Trams. 1919 [ A ] 218 119-156). -The specific heat of aqueous solutions of sodium chloride and potassium chloride of various concentrations has been determined by the same method and using the apparatus previously described (A. 1911 ii 580). I n each case the mean specific heat over $he temperature ranges 0--13O 13-26O and 26-39O was determined. The results of the present work indicate that the specific heat andCENXRAL AND PHYSICAL CHEMISTBY. ii. 135 specific volume of the combined water may be treated as approxirn- ately constant and the lowering of the specific heat and specific volume of the free water on the introduction of a solute are each proportional to the percentage concentration of the solute.121 dilute solutions the specific heat curve approximates t'oi that of water which has a minimum a t about 2 5 O . In concentrated solu- tions the variation of the specific heat with temperature appears to follow an almost straight line law. This behaviour is attributed to the simplification of the water by a considerable destruction of ice and steam molecules and is analogous to the corresponding phenomenon noted previously (Bousfield and Lowry A. 1905 ii 135). The relationship (d&/dO) = L(dx/dH) is found between the heat of dilution and the contractmion. The following constants have been derived (i) for potassium chloride the specific heat of the liquid solute 1.655; the molecular heat of the liquid solute 123.4; (ii) f o r sodium chloride specific heat of the liquid solute 2.433 and the molecular heat of the liquid solute 142-1.The number of molecules of water combined with a molecule of solute is calculated for various dilutions. J. F. S. Neumann-Kopp's Law. FRIEDRICH B i f ~ l ~ i (Helv. Cfzinz. Actc; 1919 2 27-38).-For a number of the elements the difference C'p-C'v between the atomic heats a t constant pressure and a t constant volume has beeii calculated by means of the formula 6fp-Cv=Ta2V/41*89x cal. where V is the atomic volume a the coefficient of cubical expansion and x the coefficient of compressi- biliby; foil- chemically related elements the differences are its a first approximation the same.In the case of the haloids of the elements of the first group of the periodic table the Neumaiin-Kopp law is more exactly fulfilled for molecular heats a t constant pressure than for molecular heats a t constant volume. c. s. Determination of Melting Points by means of Electric Heating. SIEGFRIED LAURENS MALOWAN (Zeztsch aizgew. Cl~em. 1919 32 i 16).-Two test-tubes are fastened concentrically one inside the other leaving a small air-space a t the sides and 15 mm. between the bottoms of the tubes. The inner tube is provided with a two-holed rubber stopper one hole for the thermometer the other for slipping in the melting-point tube. For making a melt- ing-point determination the apparatus is fixed with the bottom of the outer tube 5 mm.inside the mouth of a small electrically heated Heraeus crucible furnace. It is claimed that t'he tempera- ture control is better and the relsults more accurate than with the usual forms of melting-point apparatus and in addition the whole apparatus can be very quickly cooled. Boundaries of Existence of the Liquid State. G. BRUNI ( R t t i R. A c c d . Lincei 1918; [v] 27 ii 394-397).-The author criticises the conclusions drawn by Herz (A.? 1918 ii 150) who. like Meyer (A 1918 ii 292) has overlooked the fact that the true E. H. R. 5*-2E. 136 ABSTRAOTS OF CHEMICAL PAPERS. melting point (triple point solid-liquid-vapour) does not delimit the liquid state a t its lower boundary the melting point varying with the pressure.Herz considered only twenty-two out of eight,y- eight dements and his deductions have neither theoretical bearing nor empirical confirmation. T. H. P. Application to Eight Different Substances of the Formula which Expresses the Heat of Vaporisation of a Liquid. E. ARISS (Cornpt. rend. l919,168,444-447).-Using the formula previously given (compare ibid. 204) the author has calculated the heat of vaporisation for carbon dioxide ammonia stannic chloride methyl formate pentane hexane heptane and octane and finds that the calculated results agree very well with those obtained by different workers. Limits of Separation by Fractional Distillation A New Still-head. S. F. DUFTON ( J . SOC. Chem. Iyzd. 1919 38 45-46~).-The still-head described consists of an open tube inside which is another closed one with a wire wound spirally round it so that it just fits the outer tube. The latter may be mads of parts of different sections increasing in diameter downwards this gradation of the annulus serving to carry away the increasing volume of condensed liquid; a form more easily constructed consists of one length of tubing of approximately uniform bore the spirals being wound on cores of decreasing diameter. For any particular set of conditions there is a certain minimal value for the working volume of the still-head; if this is exceeded there is no consequenlt increase in the amount of inseparable mixture in the still-head the extra length a t the bottom becoming filled with vapour and liquid of one of the pure constituents.Such still-heads are far more efficient than the Young pear-bulb column in common use and have the greatl practical advantage that the distillation having been started a t the proper rate slows down and sitops when the limit of each pure constituent is reached rise in the temperature being then necessary to drive olff the next constituent. From a dx%ure of 5 C.C. of benzene with 10 C.C. of toluene 4.6 C.C. of benzene and 9.4 C.C. of toluene were recovered by direct distilla- tion; the loss was 0.3 C.C. and the unseparated intermediate por- tion 0.7 c.c. which is not far removed from the actual working volume the total volume found in the flask a t the end of tlhe opera- tion being just twice this amount. A similar arrangement provides a very efficient means of wash- ing a gas with a small quantity of liquid.I n this ease the annulus is made of the same size throughout and the pitch of the wire spiral is kept as small as practicable so as to reduce the speed of descent of the liquid. Such a washer gives more intimate average contact betwe~en gas and liquid and introduces no hydrostatic pressure. T. H. P. Ultramicroscopic Examination of very thin Deposits of Metals and Salts obtained by Evaporation in High Vacua. 11. HAMBURGER (Kolloid Zeitsch. 1918 23 177-199) .-The thin W. G.GENERAL AND PHYSICAL CEEMTSTRY. ii. 137 deposits produced on the walls of a vessel in which metals and other substances have been strongly heated have been examined by means of an ultramicrosco'pe. The metals were mounted in the form of thin wires and heated electrically in a vacuum; salts such as sodium chloride and calcium fluoride were heated on a tungsteii wire.It was found that on admitting air t o the cooled vessel changes in the nature of the film occurred and in consequence the film was protected by a thin layer of Canada balsam before air was admitted and the ultramicroscopic examination made. The experiments were carried out with the metals silver gold tungsten molybdenum platinum iron copper nickel magnesium zinc and cadmium and also with carbon sodium chloride and calcium fluoride. It is shown that the metals with high melting points molybdenum platinum nickel and iron and also carbon produce sublimates which are either compleltely unresolvable or mainly un- resolvable into particles.The lower melting elements with a higher vapour tension gold silver copper magnesium zinc and cadmium show a greater tendency t o a less disperse condensation and produce a complete network of ultramicrons. Generally it can be stated that the higher the temperature necessary for slow sublimation the finer is the structure of the sublimate. The elec- trical conductivity of films of gold silver platinum and tungsten of measured thickness has also been determined and itl is shown that st covering of calcium fluoride or Canada balsam is a very efficient protection for these metals. Films condensed a t the temperature of liquid air on warming t o the ordinarv temperature undergo a non-reversible change of resistance which is very great in the case of gold and silver.This is probably due to a change in the structure of the deposit for ultrnmicroscopicallv the deposits are seen t o lm different at the two temperatures. Many deposits undergo a change of resistance when there is not temperature change. I n particular silver deposits produced and kept. a t the ordinary temperature f o r l o n ~ neriods increase in their resistance to an infinitely large value. This must be dixe t o changes in the optically unresolvable part of the deposit which lies between the network. These changes are probalolp of such a nature that small mx)s occur and consequently the direct metallic c o n t a t t is broken. The influence of tnhe temperature of the walls on which the deposit is formed has been investimted.and it is shown th%t the hieher the vanour tension of the metal is at. tthe temperatiire of the walls the Jess disnerse i s the structure of the deuosit. Manv of the metals produce films of definite eolours which are eharaeteristic of the metal and are determined by the selective absorption of liqht' by the atoms. J. F. S. Evaporation and Condensation Velocities and the Calcula- tion of Chemical Constants from the Density of the Condensate. MAX TRAUTZ (Zeitsch. anorg. Chew,. 1919 105 9 7 - 4 1 l).-A mathematical discussion of the equilibrium between vapour and liquid treated as a simple chemical reaction. From theii. 138 ABSTRACT3 OF CHEMICAL PAPERS. gas theory an4 the thermodynamic laws formulz are developed expressing evaporation and condensation velocities in terns of lieat of evaporation molecular heat molecular weight molecular dia- meter density of the condensate and closeness of packing.The chemical constant of the “reaction” is the logarithm of the ratio of the maximum evapolration and condensation velocities. It in creases with increasing molecular diameter with decreasing mole- cular volume and with decreasing densitv of packing of the mole- cules. With increasing molecular weight the constant first rises and subsequently falls continuously. It is shown that all the factors involved in the calculation of the evaporation and condensation veiocities can be given 8 purely mechanical interpretation with the exception of the heat of evaporation. For the first time a purely mechanical interpretation of the chemical constant is given its calculation requiring only the molecular diameter molecular weight and density.The method of investigation here used involving a mathematical amlysis of the processes occurring a t the surface between two phases is spplicitble t’o other problems such as the solution of gases in liquids and ciihsion problems. The Extension of the Gas Laws to Liquids and Solids. JOHN SCOTT HALDANE (Biochem. J. 1918 12 464-498).-The three gas laws may be combined and more correctly stated and a t the same time extended to liquids in the fomn The intermolecular volume of a given volume of gas or liquid varies inversely as its mean intermolecular pressure and directly as the absodute tempera- ture the concentration of gram-molecules and a constant which is the ssme for all gases and liquids.This may be embodied in the equation P( T; - v) = 22*4nT/273 or P( V - v) = 0.082nI’ where P= mean intermolecular pressure in atmospheres V =volume in litres v =volume virtually occupied by the molecules themselves ~b=relative number of molecules so thak when P and n=l and T = 273O ahsol. P( P - v) = 22.4. This casts new light on the physi- cal properties of solutions and on varioas phenomena connected with gases and liquids. Thus it can be shown that ( a ) Diffusion pres- sure of any one substancel between one liquid or gas and another is proportional t o the values of its partial pressures p in the one liquid or gas and 1 - v in the other. ( 6 ) The intermolecular pres- sure is the1 same f o r all solutions in the same solvent up to high concentrations and with wide variations of temperature.( c ) Os- motic pressure is simply the increased intermolecular pressure required to neutralise the excess of diffusion pressure of a pure solvent inwards over that of a diluted solvent outwards through 3 membrane permeable t o the solvent but not to the solute which dilutes it. po = 0*082NT(n/N1 - n) where p(,= osmotic pressure and n N N =gram-mols. of solute pure solvent and solution per litre. (d) Diminution of vapour pressure of the solvent and rise of vapour pressure of the solute are propor- E. H. R. This excess is given by the equationCIENERAL AND PHYSTCATJ CTTRMTSTRY. ii. 139 tional to n / N . ( e ) Elevatioii of b. p. and depression of m. p. o'f the solvent are proportional to nf ( N -n) and can be calculated respectively if the latent heats of boiling or melting of solvent are known.(f) When the ratio n/N1 is the same in different solutions with the same solvent the substances of which denotes gram- mols. per litre (including the solvent) are in diffusion equilibrium and their mutual diffusion pressure is 0*O82iliT(72 /AT,). This diffu- sion pressure which has hitherto often been confused with osmotic pressure is of fundhmental importance in physical chemistry and p h ysiolsgy . The Dissociation Pressures of some Nitrides EOLAND EDGAR SLADE and GEOFFREY ISHERWOOD HIGSON (T. 1919 115 W. G. 2 15-2 1 6 ) . Structure of Crystals in very thin Lamina. NewExperi- mental Determination of Molecular Dimensions. R E N ~ MARCELIN (Anm.Physique 1918 [ix] 10 189-194).-The method employed in the investigation consists in examining a thin sheet of the substance between crossed nicols side by side with a thin wedge of quartz which is moved until the same colour is obtained with both and from the indices of refraction of the quartz and the thickness of the wedge a t the measured point calculating the thickness of the lamina of substance under investigation. By this method lamina of mica and p-toluidine have been examined and it is shown that with mica laminze may be obtained of thickness equal tot the diameter of the molecules. With p-toluidine lamins have been obtained which are certainly not thicker than twice the molecular diameter and probably not thicker than a single molecular diameter. J. F.S. The Theory of Gels. SAMUEL CLEMENT BRADFORD (Biochem. J. 1918 12 351-381. Compare A. 1917 ii 366).-The low diffusion constant of the natural emulsoids by retarding the crystallisation of the hot sols allows the accumulation of a large excess concentra- tion which together with their large value of IT in von Weimam's formula causes gelation on cooling. The small crystallisation velocity is also responsible f o r the permanency of the gels and the hysteresis of the sols. The viscosity changes in the) sols of the natural emulsoids by heating are seen to be in conformity with Einstein's formula since thermal changes cause alterations in the numbers as well as the size of the crystallisation centres. Applying von Weimam's theory to the reversible sol-gel transformation the conclusion is drawn that gds should comprise two1 phases namely an ultramicroscopic solid phase bathed in a liquid dispersion medium from which i t has crystallised and which i t retains partly by molecular and partly by capillary forces.Complex organic substances and such as are highly aggregated in solution tend to crystallise as spherites and this leads t o the sup- p i t i o n that the ultimate solid particles of gels az"8 spherites. Thisii. 140 ABSTRACTS OF CHEMICAL PAPERS. is supported by the! fact that by suitable precipitation with alcohol gelatin can be made to assume the folrm of microscopic spheres. The liquid adsorbed a t the liquid-so'lid boundary surfaces of gels is under an internal pressure intermediate between those of the soslid and of the liquid.This intermediate value of the internal pressure is much greater than that of the free liquid and conditions certain peculiarities in the properties of gels. W. G. IT. R. KRUYT and A. E. VAN ARKEL (Chem. Weekbhd 1919 16 220-225).-A preliminary note on the measurement of the velocity of coagulation of colloidal solutions. The hydrosol studied is that of selenium prepared by the reduction of selenious acid by means of hvdrazine. The concentration of the hydrosol was determined by direct enumeration of the particles under the ultramicroscope the progress of the coagulation being exhibited by the fall in concentration observed from time to time over a period of thirteen days after the addition of the electrolyte. In presence of potassium chloride solutions of concentration 10 and 20 mg.mol. per litre coagulation of the st]andard sol was scarcely perceptible; with 40 and 50 mg. per litre coagulation was extremely rapid. The concentration 30 mg. per litre brought about coagula- tion a t a convenient measurable rate. Velocity of Coagulation. W. S. M. Forms assumed by Drops and Vortices of a Gelatinising Liquid in Various Coagulating Solutions Ebm HATSCHEK (Proc Roy. Soc. 1919 [ A l 95 303-316).-The effect of a1lo;wing a 14% geiatin sol to fall drop by drop into a solu0ion of aluminium sulphate or ferrous sulphate is described and illustrations of the forms; assumed by the gelatin drops are given in the paper. Tem- peratuse and the density of the coagulating medium determine to a large extent the form assumed.By dropping a solution containing 10 grams of gelatin and 8 grams of crystallised poltassium ferro- cyanide into a solution of copper sulphate of suit-able density discs were produced which bear a remarkable resemblance to highly magnified blood cospuscles. The effect of the addition of a large number of substances to the gelatin solution is also described. J. F. S. Investigations dealing with the State of Aggregation. IV. The Flocculation of Colloids with Salts containing Univalent Organic Ions. S. B. SCHRYVER and NITA E. SPEER (Proc. Roy. SOC. 1919 [B] 90,400-414).-1f adsorption of the dis- charging ion plays the chief part in the! flocculation of colloids it might be expected that thm0 salts the normal solutions of which have the lowe& surface tension would exhibit the greatest flocculat- ing capacity.This capacity was investigated for a series of sodium salts of organio acids and of hydrochlorides of organic bas= of which the normal solutions show wide variations in the surface tensions. As a general rule no relationship was shown to exist between surfam texision of the1 solutions and flocculation capacity.GENERAL AND PHYSICAL CHEMISTRY. ii. 141 I n only one case that of the mastic sol did such a relationship exist--the hydrochlorides of those bases the solution of which had lower surface tensions precipitating the mastic in lower con- centrations. It is suggested by the authors that tIwo classes of suspensoid should exist namely those which olwe their charge t o an ion derived from a salt from which they are obtained by hydrolysis as for example the chlorine ion in the ferric hydroxide sol obtained by dialysis of ferric chloride solutions and those which owe their charge to an ion derived by dissociation in a colloid act- ing as an electrolyte in which the active rapidly moving ion is held electrostatically in an outer layer to the other more slowly moving colloidal ion.The former class are designated exionic and the latter endionic colloids. Nastic belongs probably to the latter class. s. B. s. ROLAND EDGAR SLADE and GEOFFREY ISHERWOOD HIGSON (T. 1919 115 Relations between Distribution Ratio Temperature and Concentration in System Water Ethyl Ether Succinic Acid. GEORGE SHANNON FORBES and ALBERT SPRAGUE COOLIDGE ( J . Amer. Chem. Soc. 1919 41 150-167).-The published data on the solubilities and distribution rabios for this system being insufficiently numerous and concordant a complete set of new determinations has been made.The ethyl ether used was care- fully purified especially frolm alcohol a trace of which may be detected by means of the green coloration given with strong sodium hydroxide solution containing a little permanganate ; the presence of. 1% of ethyl alcohol is found to increase the solubility of ether in water by about 2% and that of succinic acid in ether by about 20% the effect on t’he solubility of the acid in water being much less. The method of analysis used consisted in shaking a mixture of the desired composition in a “Pyrex ” vessel shapeld like a sub- marine with periscope; as the stopper is in contact with neither the contents of the vessel nor the water of the thermostat it need n o t be greased danger of contamination being thus obviated.The vessel was rocked a t such a speed that the air bubble travelled the whole length to and fro the rocking being stopped for ten minutes and the two layers extracted separately by inclining the vessel first one way and then the other. Special pipettes were used which did not require greased stoppers and which allowed of the evapora- tion of the solutions without transference to other vessels. The compositions of solutions unsaturated with one of t2he con- stituents were determined a t 15* 20° and 25O and a series of measurements of the distribution ratio was made a t each of the three temperatures and a t various concentrations of acid.If s is the mol. fraction of succinic acid (undissociated) in the water layer and e w CT w and E those of ether in the water layer water in the waker layer succinic acid in the ether layer water in the ether layer and ether in the ether layer respectively the corn- Equilibria in the Reductionof Oxides by Carbon. 2 0 5 -2 I 4).ii. 142 ABSTRACTS OF OHRMICAL PAPERS. plete differential of the distribution ratio (I?=.$/ a) with respect to temperature is shown to have the form dR / dt = ( b + am) cr( 1 - am) - s ( p +av)/u2(1 -up> where a=[8Cr/8wIt J3="fju/dt] p= [8o/8u]t and v = [ 8 w / 6 t ] . The reasoning involved is followed out by means of a solid diagram. Further an expression is derived for the value of dR / d t between solutions having constant composition of solvent (compare Herz and Kurzw A 1910 ii 399 1045) the value thus obtained for dR / d t being 0.0257 whereas the expression given above yields the result dR / d t = 0.0258. Succinic acid is not distributed in constant ratio between water and ether; the ratio of activit.y to concentration in aqueous solu- tion falls with increasing concentration or more strictly this deviation is greater in water than in ether solution solvation being undoubtedly largely responsible for this phenomenon. Application of Rothmund and Wilsmoire's mutual solubility equation (A.1902 ii 447; compare Nernst A. 1901 ii 647) t o the solubility data a t ZOO shows that 60 mols. of H,O furnish 33 molecules of wateir which therefore consist almost entirely of (H,0)2; this result is only an approximate one but i t agrees well with estimates made by other workers using different methods (compare Richards and Palitzsch t-his vol.ii 97). T. H. P. Influence of Substitution in the Components on the Equilibrium in Binary Solutions. XIV. Binary Solution Equilibria between Pyrogallol and the Aromatic Amines or Acid Amides. ROBERT KREMANN and LUDWIG ZECHNER (Monatsh. 1918 39 777-805. Compare A. 1918 ii 69; this vol. ii 54). -Previous results have led the authors to the conclusion that pyrogallol as a trihydroxyphenol should be capable of uniting with three molecules of a primary amine unless the close proximity of the hydroxy-groups leads to steric hindrance. The latter is found to be the case since pyrogallol unites with only two mole- cubs of aniline.ptoluidine or B-naphthylamine and with but one molecule of a-naphthylamine ; with the isomeric phenylene- diarnines compounds of the type 2 molecules pyrogallol + 2 mole- cules diamine are obtained whilst with the para-isomeride there is also formed a compound of two molecules of the phenol with one of the diamine. As is to be expecbed an equimolecular compound of pyroqallol and benzamide is found to exist and a similar corn- pound is in all probability formed from acetamide. H. W. Influence of Substitution in the Components on the Equilibrium in Binary Solutions. XV. The Binary Systems of Benzophenone with Phenols and their Deriv- atives. ROBERT KREMANN and LUDWIG ZECHNER (Monatsh. 1918 39 807-832).-The affinity of diff eretnt classes of substances towards phenols generally appears to be weakened by the replace- ment of the methyl by the phenyl group in the former; the work now described was undertaken with the object of obtaining a direct comparison of acetone and benzophenone in this respect.GENERAL AND PRYSTUAL CHEMTSTRT.ii. 143 Renzophenone forms equimolecdar compounds with phenol and a-naphthol thus resembling acetone ; with &naphthol the three mononitrophenols the three dihydroxybenzenes and pyrogallol on the other hand it gives simple eutectics. It therefore appears that Lhe ability of a phenol to form compounds with benzophenone is lessened by the introduct’ion into i t of groups which strengthen its electronegative character. H. W. Influence of Substitution in the Components on the Equilibrium in Binary Solutions.XVI. The Binary Sys tems of Benzophenone and certain Amines . ROBERT KREMANN and RUDOLF SCHADINGER (Monatsh. 1918 39 833-2338). -The inability of benzophenone to yield Compounds with nega- tively substituted phenols (preceding abstract) might be due merely to steric hindrance or to insufficient. difference in the heteropolarity of the components such that whilst the electronegative carbonyl group can react with amphoteric phenol i t is unable to do so with its electronegative derivatives. I n the latter case it appeared probable that benzophenone would react with amines. Experi- ment however shows that it yields simple eutectics with ptolu- idine and u7it.h a- or /3-naphthylamine. The difference in behaviour of benzophenone towards phenol on the one hand and towards negatively substituted phenols on the other must be ascribed to steric hindrance.H. W. Velocity of Reaction in the System 2NO + 0,. MAX TRAUTZ (Zeitsch. Elektrochem. 1919 25 4-9).-Polemical between t,he author and Bodenstein on the method adopted in calculating from the experimental results in connexion with the above-named system (see Bodenstein A. 1918 ii 302; Trautz and Dalal A. 1918 ii 162). J. F. S. Relationship of the Constants of Formation and Hydro- lysis of Esters of Symmetrical Dicarboxylic Acids. ANTON SKRABAL ( M m t s h . 1918 39 741-763) .-A theoretical considera- tion of the subject and partial review of the literature The author is led to the following conclusions. The esterification of a symmetrical dicarboxylic acid and the hydrolysis of its normal ester in the presence of acid lead ta an “ acid-ester ” equilibrium (2 acid ester normal ester + dicarb- oxylic acid) the constant If of which is related to the constant rat& of consecutive hydrolysis and esterification in accordance with the equation nnf = K .I f therefore the acid-ester equilibrium is not appreciably altered by change in temperature and other experi- mental conditions nnf must be constant. This is most readily the case when both w and n’ are of the order unity and when further n=nf. Actually R is found t o be practically independent of the temperature and its numerical value is frequently 4 hence the simplified constant ratio n =n’ = 2. The acid-ester equilibrium is displaced with decreasing acidity and in consequence the relation-5.144 ABSTRACTS OF CHEMICAL PAPERS. ship of the constants for alkaline hydrolysis differs from that for acidio hydrolysis. The esterification of a symmetrical dihydric alcohol and the hydrolysis of its normal ester leads to an ‘ I ester-alcohol ” equil- ibrium (2 ester alcohol Z normal ester + alcohol) the constant K of which is related to the constant ratiois of the consecutive actions according to the equation nn’ = K . The “ ester-alcohol ” equilibrium is not influenced by the acidity and the relationship of the constants is consequently the same for acid and alkaline hydrolysis. Replacement of the alkyl group is analogous to esterification and hydrolysis. Consecutive replacement in a symmetrical mixed ester leads to the establishment of a ‘ I mixed-ester ” equilibrium the constants of which are similarly related to the ratios of the constants for consecutive replacement.The ratios of the constants of the hydrolysis and formation of mixed esters are governed by their relationships to the constants of the two acid-ester equilibria (or ester-alcohol equilibria) and of the mixed ester equilibrium. The dynamic conception of the ester equilibrium imposes neces- sary but not complete conditions with respect to1 the relationship of the constants of formation and hydrolysis of spmetrical di- esters and its variation with the experimental conditions. The pmsible variations are limited by the simultaneous application of the parameter rule (A. 1916 ii 607). Tbe lattler leads to assump- tions which can be experimentally testeld and are therefore valu- able working hypotheses.H. W. Consecutive Reactions. V. Dynamics of the Oxalic Ester Equilibrium. ANTON SHRABAL and DANICA MRAZEK (Monatsh. 1918 39 697-739. Compare A. 1916 ii 477; 1917 ii 250; 1918 ii 12).-The hydrolysis of normal Methyl oxalate the esterification of oxalic acid and the reaction of the acid ester in aqueous-alcoholic solution have been kinetically investigated a t 25O. The acid titre and the amount of normal ester have been analytically det-ermined at* given intervals of time. All three pro- cesses show uniformly that the relationship of the constants is 2 l both for the consecutive hydrolysis of the normal ester and for the consecutive esterification of oxalic acid. The esterification equilibrium of oxalic acid has beerr determined for both stages of the process.H. W. ANTON SKRABAL and ANTON MATIEVIG (Monatsh. 1918 39 765-773).-To gain insight into the influence of the nature of the alkyl group on the velocity of hydrolysis of esters the authors have examined the behaviour of ethyl oaalate under conditions similar t o those. used with the methyl ester (A 1917 ii 250). Comparison of the con- stants obtained with those found for the met-hyl ester shows the latter to undergo the first stage sf hydrolysis three times as rapidly and the second stage two and a-half times as rapidly as t h e ethyl ester. H. w. Hydrolysis of Ethyl Oxalate with Alkali.QENERAL AND PHYSICAL CHEMISTRY. ii. 145 Studies in Catalysis. X. The Applicability of the Radia- tion Hypothesis to Heterogeneous Reactions.WILLIAM CUDMORE MCCULLAGR LEWIS (T. 1919 115 182-193). Chemical Structure of Atoms. I. FRANZ WENZEL ( J . pr. Chem. 1918 [ii] 98 155-203) .-A theoretical paper containing the following sections I. Typical Elements.-The author's method of building structural forms of atoms is based on two hypotheses. The first is that the tervalent nitrogen atom is composed of two nuclei united by a double linking (compare A. 1918 ii 17); in addition to the three valencies four others are involved in the double linking thus -@=a<. The second hypothesis is that the mass 14.01 of the nitrogen atom is distributed uniformly over these seven valencies so that with each valency correspotnnds a mass of approximately two units designated valency mass 2.It is assumed therefore that to each valency is related a definite mass magnitude. This is usually 2 but in connexion with the atoms of lithium glucinum and boron a valency mass 3 must be assumed. Starting therefore from the helium atom (composed of two singly linked nuclei) the elements of the first small period can be built u p by the systematic addition t o both niiclei of the 'helium atom of valency masses 2 and 3 in num- bers increasing from 1 to 7 ; thus He. Li . (21 €3. ( 0 = valency mass 2 ; o = valericy mass 3.) carbon nitrogen oxygen and fluorine are represented by similar structures containing 6 7 8 and 9 valency masses respectively. Analogous structures can be formed f o r the elements of the second period starting from the neon atom.The author claims that these structures which are not a t variance with the physical properties of atoms are fitted to express the most important chemical proper- ties of the elements and render possible the treatment of general questions such as variability of valency and the cause of the metallic and metalloid characteristics of elements. 11. Valewy Masses nnd their Node of LirLking.-Assuming that the forces which hold together the valency masses in the atomic nucleus can be treated as valency forces the maximal value of the valency masses 2 and 3 (and also of valency mass 1 from which valency masses 2 and 3 must be assumed to be derived) can be ascertained. By introducing these maximal values of the valency masses into the structural pictures above structural formulze are obtained which allow the deduction of many interesting phenomena such as (a) the existence of a metallic form of the quinquevalent nitrogen atom on which arel founded the ammonium compounds ( 6 ) the variations of the atomic weights from whole numbers ( c ) aii.146 ABSTRACTS OE CHEMICAL PAPEBS. structural formula of the hydrogen atom which appears to account for its metallic properties and for the variation of its atomic weight from exactly 1. 111. St ereoissrnerism of Ammonium Compomds.-The preceding theory of atomic structure leads to the evolution of a model of the nitrogen atom which is in agreement with crystallographic require- ments concerning the spatial psitions of the atoms in ammonium iodide and in tetramethylammonium iodide.By the help of this model the possibilities of isomerism t o be anticipated in ammonium compounds can be derived. These are exceedingly complicated and of all the nitrogen models hitherto proposed only the pyramidal formula of Bischoff is applicable for the graphic representation of the isomerism of ammonium compounds and then only if it is amplified by the insertion of a diagonal in the square base. For the explanation of such isomerism chemistry must call in the help of crystallography in a much greater degree than has hitherto been the case. The isomerism off the optically active ammonium com- pounds requires for its establishment the conception of a binuclear nitrogen atsm. IV. The Metallic Carbon Atom.-It is known that one of the valencies of the carbon atom occasionally functions with basic pro- perties (Baeyer's carbonium valency) .This necessitates a " metallic " carbon atom the structure of which includes the group- ing characteristic of the atoms of the metals. Such a structure can be derived from that of the metalloid carbon atom. I n the latter the valencies are directed tetrahedrally whilst in the metallic carboln atom the three metalloid valencies lie in a plane to which the metallic valency lies a t right angles a spacial disposition of the valencies of the metallic carbon atom which the author c1aims.k confirmed by the position of the atoms in the crystal lattice of graphite. c. s. New Reaux Condenser. JAMES J. BAJDA ( J . I d . Eng. Chent. 1919 11 52).-A side-tube leading from the stem of the con- denser just above the flask containing the volatile liquid conducts the vapours into the top of the condenser jacket where they enter the condensing coil. The lower part of the latter is formed into a siphon-trap which delivers the condensed liquid into the flask through a tube entending down the stem of the condenser. A branch tube on the coil just above the trap extends through the top of the condenser jacket. w. P. s. An Efficient Laboratory Funnel for Filtering Neutral Liquids especially the Volatile Organic Solvents. T. B. ALDRICH ( J . Ind. Eng. Chem. 1919 11 139-140).-1n this funnel the filter paper is clamped securely between two1 plates so' that it cann0.t lift even when the suction is interrupted; the formation of channels and passages for the liquid and precipitate beneath is thus avoided. The funnel is of aluminium and consists of four parts (1) a cast hollow cylinder with a small flange a t the top and aINORQANIC CHEMISTRY. ii. I47 heavier one a t the bottom both outside the lower one being screwed; (2) a plate 1-5 mm. thick perforated with 0.75 mm. holes (3 mm. centre to centre); (3) a ring threaded on the inside and milled on the outside; (4) a conical lower portion provided with a stem and having a flange a t the top threaded on the outside to mesh with the threads on the inside of the ring. After the filter- paper has been introduced the ring is screwed up and holds the other three parts together rubber rings being inserted to render the joints tight. T. H. P.

ISSN:0368-1769    

DOI:10.1039/CA9191605125

出版商:RSC    

年代:1919

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. Physiological Chemistry. i. 137 The Blood Sugar. GUSTAV KROK (Biochem. Zeitsch. 1918 92 84-89).-An analysis of the sugar in blood was made by Bang’s micro-method both before and after hydrolysis by acids in the case of rabbits after ingestion of starch and of maltose (at varying intervals) and after administration of adrenaline and a few similar analyses were made on the blood of t’he human subject. There was no appreciable difference in the reduciiig power before and after hydrolysis in any case and the results give no support to LBpine’s conception of the ‘‘ sucre virtue1 ” of blood. S . B. S . The Theory of Clotting. ALFRED PERUTZ and MAX ROSEMANN (Biochem. Zeitsch. 1918 92 90--95).-The amount of fibrin which is obtained by mixing serum and plasma stands in some proportional relationship to the amounts of these two components used when they are employed in great.dilutions. I f diminishing amounts of serum are added t o the same amount of plasma the amount of fibrin formed diminishes. I n the same way diminish- ing amounts of plasma added to the same amount of serum also produce diminishing amounts of fibrin. If very great dilutions are employed of plasma and serum so as to be near the limits of a reaction. in order that the reaction should take place atl all t’he serum concentration must be greater t,han the plasma con- centration. s. B. S.i. 138 ABSTRACTS OF CHEMICAL PAPERS. The Presence of Phosphates in Human Blood-serum. VII. JOH. FEIGL (Biochem. Zeitsch. 1918 92 1-83).-The author gives a very extensive and detailed review of the methods of separating the constituents which contain phosphorus in the blood especially the lipoid phosphorus and inorganic (acid soluble) phos- phorus giving in particular a detailed criticism of the recent methods of Bloor Greenwald and their collaborators.He also gives a critical account of the micro-methods for estimating the phosphorus after ashing including the various nephelometric and colorimetric methods. R e gives finally a series of tables of analyses of the phosphorus of the blood (chiefly lecithin phos- phorus) in pathological cases obtained by himself by the employ- ment of various methods. S. B. s. Shark and Ray Liver Oils. M. TSU~JIMOTO (J. Chem. Ind. Tokyo 1918 21 1015-1042).-The analytical values of the liver oils of thirteen species of Japanese sharks and five species of Japanese rays are given. The olil derived from the shark Pristittriis pilosus had an exceptionally high iodine value (309.0) and a very low sp.gr. (D:" 0.8664). It was found that all the shark liver oils of low sp. gr. (below 0.9) contained the hydrocarbon squalene which was also present in the egg oils of two! species of shark but i t was not a constituent of any of the ray liver oils. [See also J . Soc. Chem. I d . 1919 109a.l C. A. M. Genesis of Thiocyanic Acid in Animals. V. SERAFINO DEZANI (Arch. Farm. sper. sci. aff. 1918 25 278-288; from Chem. Zentr. 1918 ii 836-837).-The quantity of thiocyanic acid formed in the dog depends on the albumin content of the foo'd; this result is in striking contrast with the experience of Bruylants and Grober with the human subject.After administration of acetsonitrife thiocyanic acid could be detelcted in the blood serum and saliva of the dog as soon as in the urine; its formation cannot therefore in any case be an exclusive function of the kidneys. H. W. Calcium-Form of Reserve in the Female of the Phasmides ; its Forms of Elimination in the two Sexes. J. PANTEL (Compt. r e d . 1919 168 242-244).-Calcium exists as a reserve in the form of its carbonate in the lower malpighian tubes of the females of the Phasmides. I n both sexes the prin- cipal form in which it is eliminated is as its phosphate accessory forms being the oxalate and probably the urate. Catalytic Action of Serpent Venoms on the Nucleic Acids @. DELEZENNE and H.MOREL (Compt. r e d . 1919 168 244-246) .-Both plant and animal nucleic acids are hydrolysed by venoms from members of the Colubrides and Viperides groups. The curves showing the velocity of the reaction indicate that the reaction is catalytic and it has been shown that the amount of W. G .VEGETABLE PHYSIOLOGY AND AGRICULTURE. i. 139 hydrolysis is independent of the amount of venom used. The optimum temperature is 50-5Z0 and the venom loses its hydro- lytic powers if heated for a few minutes a t looo or if to the medium is added specific antivenom serum. The different venoms vary in the intensity of their catalytic action this variation being The Guttam2ter and its Application to the Study of Drugs and Poisons. FRIEDRICH ESCHBAUM (Bey. Dezct.pharm. Ges. 19 18 28 397-416).-The guttameter is a capillary pipette with a wide delivery orifice from which ten drops are collected in a weighing bottle and the weight recorded. The instrument is standarclised with water a t 20° ten drops of which should weigh 1-20 grams. The weight of ten drops of the liquid corrected by the factor of st.andardisation of the instrument is proportional to the surf ace tension; thus the results are inversely proportional t a those obtained with the stalagmometer. The author has extended certain observations of Traube and others on the use of this instru- ment from which it was deduced that the toxicity of solutions of alkaloids is in direct relation to the lowering of the surface tension of water produced by the alkaloid a t standard concentration.Thus a number of derivatives of the quinine alkaloids hape been studied and ranged in the order of decrease in surface tension pro- duced in 0.1% solutions of their salts mixed with increasing small proportions of sodium carbonate. The order of classification so obtained colincides with that of increasing toxicity. Quinine and quinidine approximately equal had the least effect on surface tension ; stronger depressions were recorded in the following order hydroquinine ethylhydrocupreine ethylapohydroquinidine iso- amylhydrocupreine and isooctylhgdrocupreine. The depreqsion of the surface tension increases with the amount of alkali added. Morphine and apomorphine occupy a peculiar position among the alkaloids in that solutions of their salts when treated with sodium carbonate do not show a depression of the surface tension as com- pared with water. It is shown however that morphine salts when treated with certain small proportions of ammonia liberate the alkaloid in a disperse form and a depression of the surface tension is then observed. in the same direction as is that of their toxicity. w. G. J. F. B.

ISSN:0368-1769    

DOI:10.1039/CA9191600137

出版商:RSC    

年代:1919

数据来源: RSC