摘要:

General and Physical Chemistry Influence of Temperature on the Optical Properties of Dissolved Substances. C. CHENEYEAU (Compt. rend. 1907 146 1332-1334. Compare Abstr. 1907 ii 920).-The index of refraction of a dissolved substance varies slightly with the temperature ; the variation of the optical constant K r.K=A/c where A = n - l or (n,2 - l)/(ns2 + 2) and c is the concentration in grams per litre] with the temperature is due t o the change of volume of the solution and the relation is expressed by the equation Kt’ = Kt [I + m(t’ - t)] where m is the mean coefficient of expansion of the solution. The calculated and observed values of the optical constant in the cases of solutions of sodium chloride potassium chloride (Bender Sbstr. 1900 ii 461 ; 1902 ii 437) potassium nitrate and chloral hydrate are tabulated i n the original.31. A. w. Rotatory Power in Solutions. THOMAS S. PATTERSON (Ber. 1908 41 113-12O).-Polemical. A reply to Walden’s criticisms (Abstr. 190’7 ii 519) of Patterson and Thomas (Abstr. 1907 ii 332). S:e also Walden (Abstr. 1906 ii 209). E. F. A. Origins of Stereochemistry. EXANUALE PAT ERN^ ( A t t i it. Accud. Lincei 1907 [v] 16 ii 717-719).-A question ol priority. T. H. P. Optical Properties and Electron Theory. H. ERFLE (&4nn. Physik 1907 [iv] 24 672-70S++).-The dispersion of benzene a-bromonaphthalene and methyl iodide has been measured for wave- lengths in the visible spectrum. The results are discussed in reference to Drude’s theory of dispersion according to which i t is possible to calculate a limiting value ( p ) for the number of freely vibrating electrons in the molecule this value depending on the composition and constitution of t h e molecule in t h e same way that the refraction equivalent does.The values of p are calculated for a large number of compounds the dispersion of which was measured by Landolt Briihl and others and from these molecular vaIues constants fire deduced which represent the values of p for various atoms arid radicles and also for double and triple linkings and for the benzetje and naphthalene rings. I n aliphatic compounds the various atoms have the same value of p as they have in aromatic compounds when directly attached t o the benzene ring. When prcsent in aromatic compounds arid not directly attached to one of the six carbon atoms of the ring the values of p are different.I n nitrogen compounds the values of p for carbon hydrogen and oxygen are different from the values found in compounds not coutaining nitrogen. Between 10’ and 30° the numbers are independent of the temperature. H. M. D. * h i d Zcitbd. yh~sikii 1. CIIC?iZ. 1607 61 369-421. VOL. YCIV ii. G7'8 ABSTRACTS OF CHEMICAL PAPERS. Spectra of the Alkali [Metals]. CARL RUKGE (Physikal. Zeitsch. 1908 9 1-2).-It is pointed out that the new series of lines observed by A. Bergmann (Diss. Jena 1907) in the ultra-red region of the emission spectra of potassium rubidium and czsium nre similarly related to the lines in the first subsidiary series as the lines in the principal series are to those in the second subsidiary series.H. 31. D. The Variations of the Absorption Bands of Didymium and Erbium Salts in a Magnetic Field. JEAN BECQUEREL (Con~pt. rend. 1907 145 1412-1415. Compare Abstr. 1906 ii 317 421 ; 190'7 ii 147).-The author has extended his investigation on the variations of the absorption bands of rare earth salts in a magnetic field at low temperat,ures (this vol. ii 3) and in the present paper the results obtained with didymium chloride and nitrate and mixtures of the two didymium sulphilte oxalate and fluoride and erbium chloride are recorded. The soluble salts were dissolved in ~Icohol and the insoluble salts suspended in alcohol and solidified by means of liquid air. With the exception of the oxalate and fluoride of didymium the absorption band3 of all these salts suffered displace- ment when placed in a magnetic field and the author draws the conclusion that the influence of the magnetic field on the change of period of the corpuscles producing a band is independent of tho temperature and also of other conditions which tend to modify the band; the amount of displacement of a band in a magnetic fiold of known strength appears to be a characteristic property of the oscillating system. The author is of opinion that i t is premature to put forward any hypothesis in explanation of the curious result that rays which are .circularly polarised in the same direction are not all displaced in the same sense by a magnetic field. M. A. W. Influence of Temperature Changes on the Absorption in Solid Substances. JEAN BECQUEREL (Physikal. Zeitsch.1907 8 929-942).-The author ha3 investigated the changes which take place in the absorption bands of certain crystals containing rare earths (xenotime tysonite) when these are subjected to diff ererit temperatures. The bands were examined in mo t cases a t + 25" and a t - lSSo. I n general the absorption bands are shifted towards the smaller wave-lengths when the temperature is lowered although certain bands move in the opposite direction. The width of the bands diminishes with fall of temperature and in moat cases the intensity of the absorption increases. If the widths of the bands are measured by the distances between the two points which correspond with maximum disturbance on the curve of dispersion it is found that these are proportional to the square root of the absolute temperature.Some observations on the emission spectra of phosphorescing sub- stances a t the temperature of liquid air indicate that similar temperature effects are t o be met with in this case. H. M. D,GENERAL AND PHYSICAL CHEMISTRY. 79 Cause of the Emission of the Principal Series Lines of the Alkali Metals and the Doppler Effect in Canal- and Anode- Rays. CARL FREDENIIAGEN (I’hysiknl. Zeitsch. 1907 8 927-929).- Another explanation is given of the experimental observations which have led Gehrcke and Reichenheim (Verhczrzdl. Php Ges. 1906 8 559 and 1907 9 76) to the view that the L)-lines are emitted by positively charged sodium atoms The facts also agree with the view that collisions between sodium and oxygen atoms are the cause of the D-line emission.This theory derives strong support from the experi- mental observation that whiIst the intensity of the anode-rap emission from anodes containing sodium compounds increases as the exhaustion becomes more complete the D-line emission decreases in intensity. It is also consistent with Lenard’s observation that the D-lines are due to electrically neutral particles. H. 31. D. Reactions in Ultra-violet Light. HERXANN TIIIELE (Bey. 1907 40 4914-491 6)-In the experiments described the source of light mas a mercury lamp constructed of quartz ; t,he vessels were likewise composed of quartz. Hydrogen peroxide is formed in small quantities when water is exposed to the ultra-violet rays but a 0.3% solution of hydrogen peroxide is decomposed quickly. Formic acid is decomposed into carbon dioxide carbon monoxide and an inflammable gas.The formation of water from hydrogen and oxygen of carbon dioxide from carbon monoxide and oxygen of chlorine from hydrogen chloride and air (Deacon’s process) and of nitrite from N/lO potassium nitrate are accelerated when exposed t o ultra-violet rays. W. R Phosphorescence at Low Temperatures. JOSEPH DE KOWALSKI (Compt. rend. 1907 145 1270-1272).-The phosphorescence excited by ultra-violet light in alcoholic solutions of the nitrates of the rare earths and of phenanthrene anthracene and anthraquinone when cooled in liquid air and its persistence after extinction of the exciting light has been studied. When the solutions (which have solidified) of the nitrates of the rare earths are exposed to the light from a mercury arc lamp (taking a current of 4 amperes a t 25 volts) they become phosphorescent and the phosphorescence has a relatively long duration (five minutes) after extinction of the lamp. The phosphorescence of the erbium solution is green of the samarium greenish-yellow and of the neodymium violet but except in the case of samarium the intensity is too small to permit measurement of the emission spectra.The latter for samarium is cornposed of a series of fine lines The solidified solution of phenanthrene has a greenish-yellow of anthracene a blue and of anthraquinone a bright green phosphorescence. The phos- phorescence of these solutions is sufficiently intense for spectroscopic examination and their spectra are found to consist of thin bands and fine rays.Apparently clearness and fineness of the bands are characteristic of phosphorescence emission spectra at low tempera- t u r es. The intensity of the phosphorescence varies with the concentration of the solution ; saturated solutions exhibit very little phosphorescence probably owing to crystallisation of tbe solute Then the solution 6-280 ABSTRACTS OF CHEMICAL PAPERS. solidifies. The intensity of the phosphorescence of solutions of anthraquinone and anthracene diminishes gradually with their con- centration but t h a t of phenanthrene solution reaches a maximum at a concentration of about 0.2%. The non-observance of a ma,ximum intensity in the first two cases is perhaps due to the slight solubility of anthracene and anthraquinono in alcohol.E. H. Measurement of the Absorption Cloefflcients of Radium Emanation in Solutions and Mixtures. MARTIN KOFLER (Physikul. Zeitsch. 1908 9 6-S).-The influence of foreign substances on the solubility of radium emanation in water at 18" has been examined. Metallic salts and sucrose diminish the solu- bility the diminution being greater the greater the concentration of the dissolved substance. When the absorption coefficients for solutions of different metallic salts of the same density are compared i t is found t h a t the coefficient increases a s the molecular weight of the diGsolved substance increases. The solubility of the emanation in ethyl alcohol- water mixtures increases rapidly with the proportion of ethyl alcohol in the mixture. H. M. D. Radioactivity of Air Over the Open Sea.CARL RUNGE (Chem. Zentr. 1907 ii 1353 ; from Il'uchr. K. Ges. IViss. Gottingen 1907 211-229).-A wire IS metres long charged to a very high negative potential was fixed t o the mast of a vessel on the open sea. After thirty hours i t was wound on a small frame and its activity measured by the electroscope. The cause of the activity cannot be due only t o radium emanation because a noticeable activity remained after t h a t induced by radium must have disappeared. The values obtained do not agree with the rate of decay of activity induced by thorium. Comparative experiments with radium emanation performed in t h e laboratory indicate t h a t over the open sea some other source of radio- activity must exist ; the curve of decay logarithmically plotted resembles somewhat that of the activity induced by radium but is a t first steeper and finally flatter.The presence of radium and thorium emanations alone serves t o account for the activity induced in a wire on the Hainberge near Go ttingen. c. s. Specific Radioactivity of Uranium. HERBERT N. IllcCo~ and W. H. Ross ( J . Ar,zes*. Chem. Xoc. 1907 29,1698-1709).-'l'he values of the specific activity of uranium in pure uranium compounds and in minerals which have been obtained previously have been determined from measurements with a distance of 3.5-4-5 cm. between the active film and the charged electrode. Since it has been shown by Bragg and Kleeman (Phil. ilfag. 1905 [vi] 10 318) t h a t the ranges of rsdium-,4 and ritdium-C both exceed 4.5 cm.it follows that the value given for the specific radioactivity of uranium i n minerals is too low. Measurements have now been made with a now form of gold-leaf electroscope which allows a distance of S.5 cm between the active film and the electrode. With this instrument the activity of a pure uranium compound was the same at 4.5 cin. as at 8.5 cm. from theGEXERAI AND PHYSICAL CHERIISTRY. 81 electerode but the film of a uranium mineral was about 4% more active a t 8.5 em. than a t 4.5 cm. For these determinations the fllms were deposited on perfectly flat surfaces and the observed activity was corrected For deficiency due t o loss of emanation. The specific activity of uranium in minerals is 3616 and in pure uranium compounds 796. Hence for equal uranium content minerals free from thorium are 4.54 times as active as pure compounds.The relative activity of equilibrium amounts of uranium and radium in a mineral is 1.87. The range of uranium is about 3.4 cm. and it is considered probable that there is a uranium product which emits a-rays with a range of 3.25 cm. It is suggested that the supposed genetic relationship of actinium to uranium is due to the disintegration of uranium-X in two ways one giving P-rays and the inactive product which finally produces radium and the other a much slower change giving a-rays and actinium.. E. G. Speciflc Radioactivity of Thorium and the Variation of the Activity with Chemical Treatment and with Time. HERBERT N. NCCOY and W H. Ross ( J . Amer. Chem. SOC. 1907 29 1709-1718).-1n an earlier paper (Abstr.1906 ii 415) on the radioactivity of thorium minerals it was shown that after deducting the activity due to uranium from the total activity the residual activity was proportional t o the percentage of thorium present. The same conclusion has been arrived at by Boltwood and by Dadourian (Abstr. 1906 ii 415). Determinations OF the specific activity of thorium have been made with films deposited on flat plates and under such conditions that all the a-rays reach their maximum ranges *in air (compare preceding abstrart) and the value 1009 has been obtained. Experiments have been carried out with the object of finding a method of separating radiothorium from thorium by chemical means but without success. The reduction i n the activity of thorium which is effect-d by cert:tin chemical processes is due t o the removal of mesothorium and the consequent gradual decay of the radiothorium.If all the mesothorium is removed in the preparntion of pure thorium dioxide the activity of the latter will fall to a definite minimum. From the activity of a specimen suppobed to have reached this minimum it has been calculated that the period of mesothorium is 5.5 years; the quantitative changes of activity with time of a number of samples of the oxide have been found to agree with the values calculated on this assumption. Wehnelt Cathode in High Vacua. FREDERICK SODDY (Plzysikal. Zeitsch. 1908 9 8-lo).-Wehnelt has shown that currents of considerable intensity can be passed through a highly exhausted tube containing a platinum cathode coated with a layer of calcium oxide heated to a temperature of 1300-1400°.Experiments have been made to ascertain whether this phenomenon is as generally assumed independent of the degree of exhaustion of the apparatus. A tube containing a Wehnelt cathode and a calcium anode was filled withoxygen in order to remove argon and then by connecting the E. G.82 ABSTRACTS OF CHEMICAL PRPEltS. tube with an apparatus containing strongly heated calcium a high degree of exhaustion was produced. The electrodes were then con- nected with a battery of 250 volts and a current of 1.2 amperes was passed intermittently in order to allow the gases evolved by tho heated cathode and the tube to be absorbed by the heated calcium anode The current was finally allowed to pass continuously whereby the calcium anode was heated t o its vaporisation temperature.At this point the current ceased to pass through tho tube and although a feeble intermittent glow was subsequently evident the discharge was insufficient to affect the amperemetor. By means of an induction coil it was found possible to pass a current between the heated cathode and a second anode arid when this became hot by the continued passage of the current from the coil a sufficiont quantity of gas was evolved within the tube to enable the large current of 1.2 amperes to pass again from the cathode to the first anode. These facts indicate that the phenomenon associated with the Wehnelt cathode canoot be observed in very high vacua. I n contrast to the view that the large currents obtainable with this electrode are carried entirely by the emitted electrons the author maintains that the observed facts indicate that these currents are to be referred almost exclusively t,o the residual gas a very small fraction only being carried by the electrons as such. H.31. D. Electrochemical Equivalent and Temperature. FRIBDRTCH KOHLRAUSCH and RIJDOLF H. WEBER (Ber. deut. physikall. Ges. 1907 5 681-696).-Experiments are recorded the object of which was to ascertain if temperature has any measurable influence on the value of the electrochemical equivalent. The method of experiment consisted in passing a current through a solution contained in a U-tube the lower part of which was kept cool by immersion in ice-cold water whilst the solution in the upper portions of the two limbs was heated by the current passing through it.If the electrochemical equivalent varies with the temperature then a t the surface of separation of the hot and cold solutions ions should be set free and these may be recognised if suitable indicators are present in the solution. To prevent the disturbances resulting from convection currents a t the surface of separation it was found necessary t o gelatinise the solutions by the addition of arrowroot. The solutions examined were 40% sodium nitrate 40% sodium chlorate 30% potassium bromide and 2 6% pot'assium iodide litmus being added to the first three solutions t o indicate the liberation of alkali metal or acid ions a t the surface of temperature change. The starch in the gelatinised solution furnishes the indicator for any liberated iodine ions in the potassium iodide solution.The results obtained are in all cases negative and indicate that if the electrochemical equivalent varies with the temperature a t all the variation must be less than one-millionth per 1' in the case of sodium nitrate sodium chlorato and potassium bromide and less than one ten-millionth per 1' in the case of potassium iodide. If there should be a temperature-coetficient common to all electrolyt,es then this is presumably smaller than the lowest observed maxirniuin valueGENEltAL AND PHYSICAL CHEMISTRY. 83 (< 1 *lo-7). To this extent the electrochemical equivalent may be regarded as independent of the temperature. Emission of Negative Ions by Heated Metals and by Heated Calcium Oxide.FRITZ DEININGER (Be?*. deut. physikal. Ges. 1907 5 674-680 *).-The emission of negative ions by heated platinum carbon tantalum and nickel and by the same elements when covered by a layer of calcium oxide has been investigated by measuring the saturation currents a t a series of temperatures. I n all cases Richardson's formula expresses the relationship between the saturation current and the temperature of the heated material. The number of ions emitted by the uncovered elements increaces in the order nickel platinum tantalum carbon. When the heated wires are coated with a thin layer of calcium oxide the differences disappear the number of ions emitted although very much greater being in all cases the same. The author concludes that the emission of negative ions by heated metals depends very much on the nature of the metallic surface and the frequently observed irregularities are to be attributed to variation in the nature of the surface layers.Measurement of the Variatioq of Specific Heat with Temperature. ERNST LECHER (Be?.. deut. physikal. Ges. 1907 5 647-656).-A new method of measuring specific heats of metals a t high temperatures is described. The metal in the form of a wire 3-4 mm. in diameter is contained in an evacuated porcelain tube heated in an e!ectric furnace. A measured alternating electric current is passed f o r a known interval of time through the wire and the rise of temperature thereby produced is measured by means of a thernio- element in contact with the metal under examination. Although the method only yields relative specific heat values it is particularly suitable for the determination of the variation of the specific heat with the temperature for it gives relative specific heats a t definite tempera- tures whereas ordinary calorimetric methods give only mean specific heat values over considerable ranges of temperature.The results obtained for nickel and iron are recorded in the form of curves. From these it appears that the specific heat of nickel rises with the temperature and attains a maximum a t 320'. A similar maximum is found for iron a t about 740". I n a footnote the author alludes to the possibility that the observed maxima may be connected with molecular changes in the metals and prefers to regard the measured quantities as tho total quantities of heat required for the change in state (Erwarmungsenergien). Apparatus for Distillation in High Vacua.H. BUELER DE FLORIN (Chem. Zeit. 1908 32 66).-In the apparatus which is described and figured the side tube of the distilling bulb is fused into the receiver thus doing away with cork or rubber connexions and is surrounded by an extension of the air-bath in which the bulb is heated. The receiver is jacketed and may be heated with water or steam to assist in the removal of solidified distillates. A Water Thermostat for the Normal Temperature of 15". PODA (Zeitsch. angew. Chem. 1907 20 2245-2247).-The * And An??. Physik 1908 [iv]; 25 285-308. H. M. D. H. M. D. H. M. D. G. Y.84 ABSTRACTS OF CHEMICAL PAPERS. Ruthor has devised an arrangement for maintaining a water-bath at 1 5 O the variations in temperature amounting to less than 0.1 of a degree.For details t'he description and diagram in the original must be consulted. G. k- EMIL BOSE (Pl~ysikaZ. ZeitsclL. 1907 8 944-95 l).-The relationship between vapour pressure and temperature is accurately represented by the equation logp = A + B.1/1'+ C.1/T2 + D . l / P if low valuesof the absolute temperature T are excluded. The experimentally determined vapour pressure values for eight substances (ethyl alcohol water fluorobenzene methyl acetate ethyl formate n-pentane chlorine and ethyl ether) a t temperatures from - 20' to + 140' are compared with the requirements of this formula and also with those of the Nernst formula logp = A + BT + Clogl'+ D.1 /T. The mean relative deviations of the experimental vapour pressure values for these eight substances from those calculated are smaller in the case of the exponential formula than in that of Nernst's formula if ethyl ether is excepted. If curves representing the deviations as a function of the temperature are plotted the closer agreement of the experimental values with those calculated from the new formula is strikingly evident. This is particularly the case for water fluorobenzene methyl acetate and ethyl furmate the deviations being not only small but quite irregular and attributable to small errors in the determination of the vapour pressures. The exponential formula is more accurate for extrapolation to higher temperatures but for extrapolation to low temperatures the values calculated from Nernst's formula are more accurate.H. M. D. Thermodynamics of Non-homogeneous Mixtures. 11. EMIL BOSE [with 1\frss B. MAY CLARK] (Physikcd. Zeitsch. 1907 8 951 -957).-A furlher theoretical consideration of the relationship between the vapour pressures of partially miscible liquid mixtures and the heat change which takes place on mixing the two liquids. Measurements of t h e heat change on mixing isobutyl alcohol and water have been made a t three different temperatures. At 20.76" the two liquid phases contain respectively 10% and 83% of isobutyl alcohol ; at 50*74O 8% and SZ% and at 60*72O 6.5% and S 1%. The heat change which accompanies the formation of 1 gram of satmated solution of iso- butyl alcohol in water is at the three temperatures + 2.85 + 0.44 and - 0.13 cals.respectively. The heat change accompanying the formation of 1 gram of saturated solutiotl of water in isobutyl alcohol a t the same thtee temperatures is - 1.97 - 3.61 and - 4.36 cals. respectively. The partial pressures of the two components are calculated from the thermal measurements and it is found that the sums of the partial pressures are in close agreement with the total vapour pressures determined experimentally by Konow aloff . Molecular Attraction. VII. Examination of Seven Esters. JAMES E. MILLS (J. Physical Chern. 1907 11 594-622. Compare A bfitr. 1907 ii 226).-The validity of the equation ( L - E)/( Vc.3 - YE) = constant is further tested by reference to experimental data available for propyl formate ethyl acetate methyl propionate propyl New Vapour Pressure Interpolation Formula.H. M. D.G EX E It A I AS D PH Y SI C A L C H I3 11 I STRT . 8 5 acetate ethyl propionate methyl butyrate and methyl isobutyrate. The results are very favourable and therefore furnish additional support to the view that the attraction between the molecules of a liquid varies inversely as the square of their distance. Crompton’s formula for the heat of vaporisation has been further examined ; the values given by this formula are uniformly too high at low vapour pressures but at high vapour pressures in the vicinity of the cpitical temperature the formula is accurate. Some relations a t the critical temperature already discussed in earlier papers are confirmed for the seven esters which have been examined.J. C. P. Thermochemical Data relating to the Chlorinated Com- pounds derived from Millon’s Base. H . GAUDECHON (Compt. rend. 1907 145 1431-1425. Compare Abstr. 1907 ii 621 667).-The monohydrate of dimercurinmmonium chloride (NHg,Cl),,H,O (compare Andri. Abhtr. 1899 837) prepared either by neutralising the base (NHg,),0,4H20 with AT/2 HCl or by dehydrating the dihydrate (NHg,C1),,2H20 or by the limited action of boiling water on tho compound NHg,CI,NH,Cl or KHg2C1,3r\’H,C1 is a yellow amorphous substance. The dibydrate (NHg2C1),,2H,0 prepared by the action of ammonia on mercuric chloride or on the compound 3HgO,HgCl is also amorphous. From the determination of the heat of neutralisation of the base (NHg,),0,4H20 with iV/2 HC1 and the heat of solution of the salt BNHg,CI,H,O or 2NIIg2C1,BH,0 in potassium cyanide the heat of formation of tbe salt 2NHg2C1 (solid) from the base (NHg,),O (solid) and hydrochloric acid (dissolved) ifi 50.9 Gal.; the corresponding values in the case of potassium hydroxide barium oxide and silver- oxide are 27.4 Cal. 27.7 Csl. and 41.2 Cal. respectively and this explains why Millon’s base can displace potassium sodium and barium from solutions of their chlorides. The beat of formation of the compound NHg2C1,NH,C1 or NHg2CI,3NH,C1 (solid) from the salt NHg2Cl (solid) is 15.6 Cal. or 18.4 Cal. respectively and is comparable to the heat of formation of such complex salts as the platinichlorides plakinibromide or mercuri- cyanides. M. A. W. Density of Liquids below Zero.J. TIMSIERNANS (Bull SOC. chinla. Belg. 1907 21 395-402).-The author has studied the variation of density (compared with t h a t of water at 4’) with change in temperature of the liquids methyl and ethyl alcoholy ethyl ether acetotie isobutyric acid ethyl acetate acetonitrile ethyl bromide chloroform isopentane toluene chlorobenzene and pyridine below 0’. The liquids were repeatedly distilled using a Young column until their boiling points were constant to O.0lo and were finally distilled from a powerful dehydrating agent. The variation in density was determined by a dilatometer method temperatures being measured by a Callendar p!atinum resistance thermometer. The results obtained are subject to a maximum error of +_0.0005. For the liquids studied the density below 0” varies directly with the temperature (below zero).A table is given showing the temperature interval studied the density of the liquid at 0’ (Di) the coefficient86 ABSTRACTS OF CHEMICAL PAPERS. of increase in density per degree lowering of the temperature and tho densities (1) found experimentally (2) calculated by the author's formula and (3) calculated by Young's formula a t a definite temper- 'ature arbitrarily chosen for each liquid. I n no case was a maximum density observed. E. H. Vapour Density Determinations at very High Tempera- tures. H. VON WARTENBERG (Zeitsch. anorg. Chern. 1907 56 320-336. Compare Abstr. 1906 ii 161 ; Nernst Abstr. 1903 ii 636).-The vapour densities of a number of elements mainly metals have been determined in the neighbourhood of 2000' by Nernst's method (Zoc.c i f . ) . Some slight modifications of the earlier arrangements are described ; in particular the iridium bulb was coated inside and outsids repeatedly with a paste of magnesia and magnesium chloride and heated strongly after each addition. This coating proved much more satisfactory than that used previously. Argon or nitrogen was used for filling the bulb. In addition to the measurements in the neighbourhood of 2000° some experiments were made at lower temperatures the temperatures up to 1600O being determined by means of a thermocouple in the bottom of the bulb. The apparent average molecular weights a t the temperatures indicated are as follows bismuth 224 a t 2070"; antimony 128 at 2070" ; selenium 200 a t 1850° 120 a t 2100O ; tellurium 160 a t 2100" ; lead 225 at 1600-1S7O0; thallium 220 a t 1320-1690'; zinc 72 a t 1200-2070'; sulphur 50 a t 2070".The agreement of separate observations with the same substance is only moderate. The results show that all the metals so far investigated are monatomic in the state of vapour at the highest temperatures. From the temperatures a t which rapid volatilisation of the metals takes place the following boiling points have been estimated approximately thallium 1280" ; lead 1580O ; silver 2050-2100". Tin gold copper magnesium and aluminium boil above 2200". The results obtained by the author and by previous observers for the dissociation of the elements of the sulphur and phosphorus groups are tabulated. By means of Nernst's equation connecting equilibrium and temperature the energy required for the dissociation of a diatomic into a monatomic molecule is estimated a t 90,000 Gal.for the elements of the sulphur group and 80,000 Citl. for those of the phosphorus group. Incidentally it is shown that contrary to the btatement of Cook0 (Abstr. 1906 ii 539) the density of zinc is the same in argon as in nitrogen so t.hat the suggestion of this observer that zinc may form a compound with argon is incorrect. Attempts to obtain argon in combination with aluminiiim or magnesium were unsuccessful neither did argon combine with iridium under the conditions of the experiments. G. S. Application of the Method of Limiting Densities to Organic Vapours. PIIILIPPE A. GUYE (Compt. i-end. 1907 145 1330-1331).-Using the experimental values obtained by Namsny and Steele (Abstr. 1903 ii 635) for the densities and cvmpresbibilities of the vapours of the organic compounds ethyl ether hexane methylOESERLIL AND PHYSICAL CHEJIISTEY. 87 alcohol diisobutylbenzene n-octane and toluene the authors have calculated the corresponding values of the gas constant R from the relation R=M/L(1 - A:) The results show that the values of R are not constant but decrease as the critical temperatures of the vapours under consideration increase ; and the author concludes provisionally that the extrapolation methods which give the coefficient A are insufficient (compare Berthelot Abstr. l89S ii 502 ; 1907 ii 154). 31. A. W. Viscosity of Solutions. I. CLERK RANKEN and WILLIAM W. TAYLOR (Trans.Roy. Soc. Edin. 1906 45 397-406).-The viscosity of aqueous solutions of potassium chloride chlorate ferrocyanide and ferricyanide of ammonium iodide mercuric chloride and cyanide and of carbamide has been determined for a series of concentrations and temperatures. I n regard to the dependence of the relative viscosity on the concentration the results indicate that the relative viscosity of all solutions passes through a t least one minimum the position of this being determined by the nature of the dissolved substance and the temperature. For all the solutions examined with the exception of mercuric cyanide the relative viscosity increases with rice of temperature. For electrolytes the rate of increase is very much greater than €or non-electrolytes ; in this respect mercuric chloride which is but slightly ionised ranges itself with the non-electrolytes.A t low temperatures aqueous solutions of carbamide exhibit ‘‘ negative viscosity,” and thus furnish an exception to the general rule that this is only exhibited by aqueous solutions of electro- 1 y t,e s . The effect of the addition of an electrolyte or non-electrolyte t o pure water and on the other hand to a solution which has the same viscosity as pure water is found to be the same if the quantities added are small. H. 31. D. Viscosity and Conductivity. KURT A RNDT (Zeitsch. Elektrochenz. 1907 13 809-812).-The ruIe which says that the product of maximum equivalent electrolytic conductivity and viscosity is inde- pendent of the temperature and of the nature of the solvent is tested for fused sodium metaphosphate and mixtures of i t with boron trioxide.Between the melting point and about 900° the viscosity diminishes very rapidly whilst the conductivity is a linear function of the temperature ; the rule is therefore not even approximately true ; above about 900° however the viscosity diminishes more slowly and the rule holds good. It is also shown that above 900’ the product of viscosity and equivalent conductivity is constant for mixtures con- taining from 100% to 0.5% of sodium metaphosphate. If the dissocia- tion of the metaphosphate increases with dilution the more dilute solutions should be relatively better conductors than the more concentrated ones; since this is not the case the author draws the conclusion that the salt is completely dissociated even in the pure state at 900°.T. E.88 ARS'I'RBCTS OF CHEMICAL PAPERS. Spectrophotometry Viscosimetry and Electric Signs of Solutions. CHARLES HENRY (Cornpt. rend. 1907 145 1415-1417). -The results obtained by &layer Schaeffer and Terroine (this vol. ii 24) on the effect of traces of acids and alkalis on the size of colloidal granules are i n agreement with those observed by the author on the effect of t'races of chlorine water on solutions or colloidal suspensions of dyes (auramine crys tal-ponceau or methylene-blue). In the case of the solutions the molecular aggre- gates are increased in size and the viscosity of the solution is diminished and in the case of the colloidal suspensions the granules are diminished in volume and the viscosity of the solution is increased by the addition of chlorine water.Permeabilities of Collodion Gold-beaters' Skin Parchment Paper and Porcelain Membranes. 8. LAWRENCE BIGELOW (J. A me^. Che?n. Soc. 1907 29 1675 -1 692).-In an earlier paper (Bigelow and Gemberling Abstr. 1907 ii 933) the results of experiments on the permeability of collodion membranes under pressures varying from 50 mm. t o 250 mm. and at temperatures between 1' and 35" were recorded. Apparatus is now described by means of which determinat'ions have been made through a much greater range of pressr~re and temperature on the rate of the passage of water through collodion gold-beaters' skin parchment paper and pvcelain. The permeabilities of the different membranes are corn- pired.The results show that the rate of passage of water through the molecular interstices of these membranes conforms to the laws &I. A. W. regulating the rate of passage of liquids through capillary tubes. E. G . Diffusion of Electrolytes in Aqueous Solution. B. LTNO VANZETTI ( A t t i R. Accad. Lincei 1907 [v] 16 ii 696-702. Com- pare this vol. ii 20).-Into aqueous solutions of alkali haloid and silver nitrate the author dips the two vertical ends of a horizontal capillary tube filled with water. The length of the tube beneath the surface must be the same for the two solutions which must stand at the sime level and have the sRme sp. gr. The position a t which the silver haloid is deposited in the capillary is then noted. It is found that in the same time potassium chloride bromide and iodide traverse almost equal paths in the capillary tube.The positions of the layers of precipitate formed can be calculated approximately by assuming that the molecules of both the silver and alkali salts move with velocities equal to the means of the velocities of migration of their respective ions. Crystal-Systems a n d Optical Interference-Figures of Liquid Crystals. DANIEL VoRt,;imER (Zeitsch. physikal. Cheut. 1907 61 166-1 7O).-Liqiiid crystals of ethyl azoxyhromocinnamate were obyerved to have the form of tetragonal bjpyramids with straight edges. Iuterference figures in convergent polarised light were seen with liquid crybtals of several substances and are best shown by ethyl anisylideneaminocinnamate. All liquid crystals are optically uni- axial.L. J. S. T. H. P.GENERAL AND PHYSICAL CHEMISTRY. 89 Velocity of Crystallisation of Isomorphous Mixtures. MAURICE PADOA (Atti R. Accad. Lirzcei 1907 [v] 16 ii 695-696).-Bogojaw- lenski and Swharoff’s investigations on the velocities of crystalllsation of mixtures of isomorphous substances (Abstr. 1907 ii 751) although extending over a greater range of concentrations than the author’s experiments (Abstr. 1904 ii 390) are in accord with the latter and hence lead to the conclusions drawn by the author (Zoc. cit.). With some of the substances examined by the author the maximum velocity of crystallisation way only maintained over a very small temperature interval whilst in other cases this maximum could not be attained practically. I n these instances the velocities of crystallisation of the pure substances and of their mixtures were compared at equal degrees of supercooling.This procedure the author defends as his results were only qualitative. T. H. P. Solution in a Dissolved Solid. CHARLES L. PARSONS (J Physical Clbem. 1907 11 659-680).-The explanation suggested (this vol. ii 105) for the solubility of glucinum hydroxide in glucinum sulphate is capable of a wider application. The assumption of a complex in cases where the freezing point of a solution of two solutes is abnormally high is not always necessary for a dissolved solid may itself act as a solvent. Camphor dissolved in aqueous acetic acid raises the freezing point of the latter and lowers i t s conductivity and yet no assump- tion of complexes is made here. So also i t is possible that iodine dissolves readily in potassium iodide solution not because a complex is formed as is generally assumed but because iodine is soluble in potassium iodide just as iodine is more soluble in aqueous alcohol than it is in water.The author’s view is supported by the observation that the iodine and potassium iodide can be partially separated by dialysis whereas in cases of undoubted complex formation for example in potassium silver cyanide solutions no such separation by dialysis takes place. The dialysis experiments with potassium silver cyanide solutions show t h a t the Formation of any other complex than KAg(CN) is highly improbable. Further dialysis experiments with boric acid dissolved in borax solutions shorn that the boric acid is to be regarded as mixed with the borax rather than combined with it as a polyborate; there is no need in this case to assume the existence of complex molecules J.C. P. Adsorption and the Behaviour of Casein in Acid S o l u t i o n s . T. BRAILSFO~~D ROBERTSON (J. Biol Chent. 1908 4 35-44).--It is questioned whether adsorption or mechanical affinit’y exists a t all and the theory that proleins form adsorption compounds is considered t o be premature and unproved. W. D. H. Influence of Acids and Bases on the Absorption of Acidic and Basic Dyes by Wool. LOUIS PELET-JOLIVET and N. ANDERSEN (Compt. ?.end. 1907 145 1340-1341).-The authors have deter- ruined the amount of crystal-ponceau and rnethylene-blue absorbed by wool in the presence of varying amounts of hydrochloric sulphuric or phosphoric acids or of sodium hydroxide.The amountDO ABSTRACTS OF CHEMICAL PAPERS. of crystal-ponceau absorbed increases with the increasing acidity of the bath the greatest absorption taking place with hydrochloric acid and the least with phosphoric acid whilst the amount of mptliylene-blue absorbed diminishes under the same conditions. I n a n alkaline bath almost no crystal-ponceau is absorbed but methylene- blue shows a maximum absorption. These results are in accordance with the colloidal theory of dyeing (compare this vol. ii 18). Physico-chemical Researches on Lecithin and Cholesterol. OTTO PORGES and E. NEUBAUER (Uiochem. Zeitsch. 1907 7 152-177 Compare Abstr. 1903 i 301).-An investigation of the properties of emulsions prepired by adding a n ethereal solution of lecithin or a n acetone solution of cholesterol to distilled water and subsequently removing the organic solvent.The suspension of lecithin is horno- geneous and stable ; i t can be filtered and resembles a colloidal solution ; the cholesterol suspension is not very stable by itself but becomes so in the presence of albumin or of lecithin. The general conclusion arrived at is that lecithin is a '' hydrophilous " colloid and cholesterol a " suspension " colloid (these terms are from Hober's " Physikalische Chernie der Zelle und Gewebe." Hydrophilous colloids increase the viscosity of the solvent and suspension colloids do not. Solutions of the former approximate more closely t o true solutions). J n comparing the efficiency of various salts of the alkali metals as lecithin precipitants the anions and cations are found to be i n the same order as that observed by Pituli for the precipitation of albumin (Abstr.1903 i 299; 1904 i 356). Lecithin solutions are peculiar in not being precipitated by concentrated (nor by very dilute) solutions of salts of t h e alkali metals but only by solutions the concentration of which lies between certain limits. The precipitation of lecithin by salts of other metals is also for the most part closely analogous to the precipitation of albumin (Pauli). With several salts of the heavy metals the phenomenon is complicated by the occurrence of two precipitation zones separated by a region of intermediate concentra- tions in which no precipitation occurs.The precipitation reactions of cholesterol are much more uniform than those of lecithin and show great similarity to those found by Buxton and Shaffer for mastic suspensions (Abstr. 1906 ii 839). Lecithin and cholesterol suspensions are precipitated by acids and dissolved by alkalis indicating anodic convection. Accordingly both are precipitated by cathodic colloids at a certain optimal concentration. Cholesterol can for instance be precipitated by albumin (at a certain relative concentration and in neutral solution) but not by mastic which like cholesterol is electro-negative. Lesithin and cholesterol form a colloidal compound with each other since the former protects the latter against precipitation by salts. M. A. W. The biological application of the results is also discussed.Colloidal Amorphous and Crystalline States. P. P. YON WEIRIARN (Chem. Zentr. 1907 ii 1293-1294; from Zeit. chem. Ind. li'olloide 1 907 2 76-83).-The o5aervation t h a t the appearance and G. B.GENERAL AND PHYSICAL CHEMISTltP. 91 structure of the precipitate of barium sulphate obtained by t h e reaction between manganese sulphate and barium thiocyanate in aqueous solution depend essentially on the concentrations of both of the participating salts led the author to extend his researches with the following results. Equal volumes of normal solutions of different salts which yield very sparingly soluble precipitates are mixed at various dilutions and the precipitates examined macro- scopically microscopically and ultramicroscopically.Gelatinous precipitates are formed at concentrations so much the smaller the less soluble the precipitate the more viscous the solutions and the more complex the reacting substances. Precipitates such as the hydrated oxides of aluminium or silicon are obtained gelatinous on account of their slight solubility ; they can be obtained in crystals by a very slow reaction in very dilute solution. Moreover numerous crystalline sub3tances have been obtained in a gelatinous or quasi- gelatinous state by the addition of substances which lower the solubility (for exsmple alcohol in the case of the sulphates of calcium strontium barium and lead) or by increasing the concentration (easily applicable with very viscous sslt solutions or with substances the solubility of which does not exceed 10-2 per 100 grams of water).When a proportionality exists between the solubility and the con- centration at which a precipitate separates in the gelatinous state conclusions can be drawn as to the order of magnitude of the solu- bility of the precipitate that of aluminium hydroxide being lo-* t o per 100 grams of water at the boiling point and those of the hydroxides of iron and silicon i n water and of barium sulphate in alcohol being still smaller. By continuously increasing the concentrations of the reacting solutions the average size of the resulting crystals increases from the invisibly minute through those of ultramicroscopic dimensions (crystalline suspensions sols) to those of microscopic magnitude ; the last reach a maximum (microcrystalline precipitates) and then the size of the crystals still wit'h solutions of increasing concentration begins to diminish until finally invisibly minute crystals are again obtained (undifferentiated transparent jellies).The crystalline nature of precipitates formed at very small or a t very great concentrations cannot be proved optically ; nevertheless the characteristic properties of flocculent and gelatinous precipitated (such as increased solubility and vapour tension lower melting point and increased absorptive capacity) as well as their conversion into distinctly microcrystalline precipitates c m be attributed t o the properties of crystalline substances in a n exceedingly minute state of division. The author states the following conclusions (1) the so-called colloidal amorphous and crystalline states are general properties of matter ; (2) colloidal and amorphous states are modifications of the crystalline. Irreversible sols represent suspensions of very finely- divided crystalline substances which have lost the power of cohering t o form larger aggregates in consequence of the too slight mobility of the crxstslline particles and the too great viscosity of the medium.Sols of complex reversible colloids such as gluten are limit cases of92 ABSTRACTS OF CHEMICAL PAPERS. true solutions; their coagulation by cooling is identical with the ordinary phenomenon of crystallisation but the cryhtals do not attain visible magnitudes because they have lost the power of coherence i n consequence of the complexity of the molecule. A gelatinous sub- stance consists of a crystalline sponge-like framework which i s impregnated with the solution of the substance existing before o r produced by a reaction.The size of the crystals varies according t o the conditions of formation from the ultramicroscopically invisible t o the microscopically visible ; so-called amorphous precipitates are crystalline particles of distinctly greater dimensions than those of typical gelatinous substancev ; (3) the fundamental and possibly the sole cause of the formation of amorphous and gelatinous precipitates as opposed t o crystalline is found in the different conditions of their formation which is influenced by or is dependent on the relative velocity of formation of the subbtance in the solution the complexity of the substance and the viscosity of the medium ; (4) in markedly gelatinous media the velocity of diffusion and of reaction is small and often practically nil ; (5) crystalline structure is conditioned by the internal symmetry of the elementary crystalline particles of sub- stances ; this symmetry is not destroyed by the passage into the liquid and gaseous phases.The increase in mobility causes the particles to deviate from directions parallel t o their elements of symmetry. The viscosity of very concentrated solutions or of molten substances near the solidifying point is caused by the striving of the particles to move parallel to one another a striving which cannot be fulfilled under the given conditions of tomperature and pressut e. Identical conditions must hold for the transformation from the liquid c.s. Possibility of Determining the Mass of Suitable Precipitates by Obmrvation of their Rates of Settling. S. KOHN (Chem. Zed 1907,31 1287).-An attempt to determine the mass of a precipi- tate by comparing its rate of settling when suspended in a liquid with the rates observed for known masses of the same substance. The method emplojed is t o shake the washed precipitate with a liquid in which it is insoluble in a measuring cylinder and t o observe the times in which the upper surface of the precipitate falls throiigh equal intervals ; the results are compared with the rates of settling of two precipitates of known mass one of greater the other of less mass than t h a t t o be determined. Details quoted of experiments with barium carbonate and ferric hydroxide show that t h e rate of settling of a precipitate is only approximately proportional to its mass ; lience the error of the method diminishes with the differences between the masses of the three precipitates The observations for the first two or even three intervals must be discarded as abnormal in consequence of the persistence of the movemeut of the liquid after the mixing.The rates of settling of different precipitates are comparable of course only when all the conditions ok their precipitation and Equilibrium Relations of Chromatea in Solution. MILM s. ~iilzitnIr,r (J A7mr.. Chen,. &c. 1907 29 1614-16i5).-The con- t o the solid and from the gaseous to the liquid states. subsequent treatment are tho sitme.G. Y.GENERAL AND PHYSICAL CHEMISTRY. 93 ductivity determinations of solutions of chromates dichromates and chromic acid carried out by Walden (Abstr. 1888 1008) indicate that chromic acid exists in solution as H,CrO dissociating into H* + HCrO,' or as Ostwald (Abstr. 1888 1009) has suggested as H2Cr207 dis- sociating into 2H'+Cr20,". The latter view has been generally accepted whilst the possible existence of the HCrO ion has been overlooked. It is pointed out that both of these reactions must be taken into account in studying the constitution of chromic acid solutions. The relative amounts of the HCrO and Cr20 ionspresent depend on the concentration and the equilibrium constant of the reaction 2HCrO,'= H,O + CrgO/. [W; th F. ~IALCOLM EATON.]-cryOCCOpiC determinations have been made with dilute solutions of chromic acid and potassium dichromate.The depression of the f . p. in the most dilute solutions mas greater than that which would correspond with complete ionisation into Cr20 and H or K ions and the presence of an appreciable quantity of HCrO ions was indicated. The values of the equilibrium constant for the second reaction that is of the hydration constant K,= Cr,0~'/(IiICr0,')2 were calculated and found t o be 61 from the potassium dichromate and 27 from the chromic acid experiments. [With ALDEN M ~ ~ ~ ~ ~ ~ ] - D e t e r r n i n a t i o n s of the hydrolysis of ammonium chromate in dilute solutions were made by measuring the increase of conductivity produced by the addition of suacient ammonia to di ive back the hydrolysis completely ; the value of the ionisation constant K A =H' x CrO,'/HCrO; a t 1 8 O was found to be [With DONALD E.Kuss.]-By means of distribution experiments the concentration of the ammonia in chloroform was determined which is in equilibrium with the ammonia produced by hydrolysis in dilute ammonium chromate solutions. From the results the ionisation constant KA = H' x CrO,'/HCrO,' was found to be 6.2 x at 18" and 7.4 x 10-7 a t 25" and is thus about 1/30 of that of acetic acid. Determinations were made of the solubility r>f silver chromate in dilute ammonia at 2 5 O and the value of the solubility product wascalculatedand found to be 9 x 10-12 the corresponding silver-ion con- centration in the saturated aqueous solution being 2-5 x 1 0 - 4 mols.per litre. Experiments on the solubility of silver chromate in dilute nitric acid showed that in acid solutions of greater strength than O.O75N silver chromate is decomposed with separation of silver dichromate as a solid phase. Silver dichromate is decomposed by water or nitric acid solutions of lower concentration than 0.06N with separation of silver chromate. From these results and the solubility product of silver chromate the hydration constant KA the ionisation constant K and the solubility product K = (Ag')e x Cr207/1 for silver dichrornate were found to be 75 8.4 x 10-7 and 2 x 10-7 reqpectively. This value of the solubility product is equivalent to a concentratiou of 7.3 x mols. A g par litre. Tfie results of this work indicate that in a solution of potassium VOL.XCIV. ii. 7 5.7 10-7. x Cr04",94 ABSTRACTS OF CHEMICAL PAPERS. dichromate containing 0.1 mol. per litre about 15% of the salt exists as KHCrO and 85% as K2Cr207 whilst in a solution of concentration 0.01 mol. per litre approximately 45% is present as KHCrO,. It is shown that the results obtained are in accord with those of Whetham (Abstr. 1903 ii 405) on the conductivity of potassium dichromate solutions and of Spitalsky (Abstr. 1907 ii 695) on the catalytic decomposition of ethyl diazoacetate by chromate solutions but indicate that Spitalsky’s conclusion that dilute solutions of chromic acid and potassium dichromate do not contain any considerable quantity-of HCrO ions is incorrect. E. G. Equilibria in Ternary Systems. LUIGI MASCARELLI ( A t t i 22.Accud. Lincei 1907 [v] 16 ii 691-694).-Tn the case when the freezing-point curve of a binary system does not exhibit a maximum it may give indications of the formation of an additive product although no conclusion can be drawn with regard to the proportions in which the two components combine. I n general i t is theoretically possible t o find a third substance capable of bringing the maximum temperature corresponding with the additive compound below that a t which this compound decomposes. This substance should have no action on and should not be isomorphous with either of the two com- ponents or the additive compound. It is best to employ a third sub- stance of such a nature that the freezing points of the two Components are lowered considerably whilst the eutectic points of the three binary systems formed by the third substance with the two com- ponents and the additive compound respectively lie near to the freezing point of the third substance itself.These theoretical con- siderations are to be tested experimentally. IF. H. Y. Hydrolytic Fission of Acetylated Hydroxycarboxylic Acids. JULIUS RATH (Annnlen 1907 358 98-1 25).-Anschutz and Bertram found that the action of water on the acetyl derivatives of lactic and glycollic acids leads to the formation of acetic acid and the hydroxy-acid the hydrolysis taking place slowly a t the ordinary more quickly at the higher temperature (Abstr. 1906 i 966,990). I n continuation of this work the present author has studied the influence of concentration and temperature on the velocity of the hydrolysis of a number of acetoxy-acids.I n each case the velocity constant does not vary with the time only when calculated according to the equation for unimolecular reactions. This reaction between acetoxy- caxboxylic acids and water must therefore be intermediate between Ostmald’s autocatalysis and true catalysis ; although both the origina substance and the reaction products act catalytically the amount of the catalyst that is of the hydrogen ions which accelerate the hydrolysis miist remain approximately unchanged throughout the re- action. The influence of the concentration on the rate OF hydrolysis varies with the acid ; in most cases the velocity increases with the concentration but in some the rate of hydrolysis is almost unaltered by changes in the concentration whilst the constant for acetylcitric acid diminishes with increasing Concentration.Of the followingGENERAL AND PQYSICAL CHEMISTRY. 95 values for k obtained for the acids named the first is with v = 9 the second with v = 54 a t loo" or for acetylcitric acid a t 50'. Acetyl-lactic acid 0.0501 1 0,02548 ; acetylglycollic acid 0.06483 0*04001 ; diacetyltartaric acid 0.16149 0.11 128 ; acetylmalic acid 0.10467 0.09209 ; acetylsalicylic acid 0.17842 0.16976 ; acetyl- mandelic acidj 0.04423 0,02548 ; acetylcitric acid 0.12414 0.27512. The relation of the velocity constant to the temperature is re- presented by the expression logK= a + bt ; the value b = 0,02713 is obtained for d iace t ylt a r taric acid ; the t emperature-coefficient for intervals of 10' has the normal ~ a l u e 1.87.Whilst the abnormal behaviour of acetylcitric acid points t o R relation between the velocity constant and the constitution of the acetoxy-acid the data are as yet insufficient to allow of any definite conclusion. G. Y. Velocities of Catalytic Reactions in Heterogeneous Systems. Decomposition of Hydrogen Peroxide by Means of Platinum Foil Compared with Catalysis by Colloidal Platinum. I. S TELETOFF (J. Russ. Yhys. Chew,. Xoc. 1907 39 Chem. 1358-1379).-1n order to determine whether Nernst's hypothesis regarding the velocity of reaction in a heterogeneous system is also applicable to catalytic processes (compare Nernst Abstr. 1904 ii 315) it is necessary that both the surface of the catalyst and the rate of stirring ol the reacting substance should be determined readily.These conditions are fulfilled by the decomposition of hydrogen peroxide by platinised platinum foil. Ordinary platinum foil does not produce decomposition. The thickness of the layer of platinum-black has no influence on the reaction but in the presence of platinum poisons such as hydrogen sulphide carbon disulphide &c. its activity is destroyed; the activity can be restored by treating the plate with concentrated sulphuric acid a t 150-200°. The reaction is unimolecular and the thickness of the layer surrounding the plate in this case probably pure water through which the hydrogen peroxide diffuses can be calculated from the formula 8 = D. 0°'4343/(0*4343K).v (where 8 = thickness of layer D = the diffusion of hydrogen peroxide in C.C.per minute 0 = surface of plate and = volume of the solution). For v=900 C.C. and 0 = 2 0 c.c. 0*43431C=0-004 at 25' and 250 revolutions per minute and thus 8 = 0.014 mm. which agrees closely with Brunner's results (Abstr. 1904 ii 315). Contrary to Henri's statement (Abstr. 1906 ii 13) calculating 8 from Bredig's results it is found to be 0.065 mm. Towards the end of the reaction especially in concentrated solutions K diminishes owing to the growing passivity of the plate the activity of which cannot be restored by sulphuric acid ; it is probable that an intermediate oxidation product of platinum is formed analogous to the one already isolated for mercury. In acetic acid solution the reaction is slower but it is still unimolecular.I n sodium hydroxides it is also unimolecular and K rises to a maximum in solutions containing 50- 100% of the alkali. I n this as in many other respects the behaviour of the platinum is analogous to that of ferments. Both in the case of the platinum plate and in that of colloidal platinum K rises 2S% for every 10" rise in temperature. I n 7-296 ABSTRACTS OF CHEMICAL PAPERS. the latter a n ultramicroscopic examination has shown that the velocity of the platinum particles varies in the same degree. I n both cases (but especially for colloidal platinum) the velocity of the reaction is largely diminished when the viscosity of the reacting solution is increased by addition of sugar. The following relations for reactions in the presence of a platinum plate are also deduced K1/K2= O,v,/O,v = CJC and K2 = A”l(n2/ln,)3 (where C,,C = the concentra- tion of the catalyst and n = number of revolutions of the stirrer in the given time).Z. K. Evolution and Devolution of the Elements. A. C. and A. E. JESSUP (Phil Mug. 1907 Evil 15 21-55).-A theory of evolution of the elements based on astro-physical observations is put forward. According to spectroscopic evidence matter in the nebulous stage con- sists of only four elements two of which are unknown the third being hydrogen and the fourth helium. These original elements are termed protons and are supposed to be formed from primary corpuscles (which a t one time represented the only form of matter) by an aggre- gation into stable integral systems.By a process of condensation of corpuscles round the proton groups other atoms are supposed to be formed the various elements representing groupings of maximum stability in a gradual and continuous process. The authors consider that evolution takes place both along the vertical groups of the periodic table and along the horizontal series. The improbability of the existence of more t h a n four original elements considered in con junction with the apparent existence of considerably more groups leads t o the hypothesis that a t least one of the protons has given rise to more than one product of evolution The alkali met’al group the alkaline earth-metal group and the group of inert elements are supposed to have been evolved respectively from the first (hydrogen) the second (proto-glucinum) and t h e fourth (helium) protons.From the third proton (proto-boron) the tervalen t elements boron aluminium scandium yttrium lanthanum and ytterbium have been produced by “direct” evolution and in this case “indirect evolution” has also taken place with the production of quadrivalent carbon. Carbon gives rise directly to silicon and indirectly to nitrogen oxygen and fluorine. Silicon by similar indirect processes in which hereditary influence plays an important part is supposed to have given rise t o all the elements lying between titanium (atomic weight 48.1) and arsenic (75). With the exception of manganese these in turn appear to have given rise to direct evolution products of the same valency. A new form of the periodic table in which these ideas find expression is put forward; this table contains the elements arranged in seven- teen vertical groups.For details respecting the relationships expressed by the evolutionary grouping of the elements the original must be consulted Mention may here be made of the fact that the incom- plete table of elements given by Cuthbertson and Metcalfe (Phil. Tvam. 1907 A 207 135) from observations on the refractivities of the elements agrees closely with that of the authors With regard to th‘e processes of condensation which result in the formation of assemblages of corpuscles or ‘‘ rings ” around the originalGENERAL AND PHYSICAL CHEMISTRY. 97 proton aggregates it is supposed that all the principal chemical proper- ties of each element are determined by the structure of the ring that 4 4 direct ” evolution along vertical groups corresponds with the addition of similar rings and (‘ indirect ” evolution along horizontal series with the addition of dissimilar or “distorted” rings.Each (‘ ring ” is supposed to consist of assemblages OF corpuscles in sets of eight but a certain number of corpuscles (for distinction termed “electrons”) are attached in a different manner to the ring system. The number of such differentiated corpuscles determines the valency of an element and chemical combination is due t o the tendency of the electrons to yield sets of eight electrons which in some way constitute electrically neut,ral systems. The last two sections of the paper deal with the existence of quanti- tative relationships between t’he atomic weights and the possibility of explaining the degradation of the radioactive elements by devolution processes governed by influences similar to those which regulate the evolution of the elements.An outcome of this idea is the view that the a-particles emitted by the various radioactive substances are identical with one or other of the four protons. The values obtained for the masses of the a-particles are not inconsistent with this view. H. M. D. Significance of the Atomic Hypothesis. W. A. KURBATOFF (J. Buss. Yhys. Chem. SOC. 1907 39 1181-1216 1216-1218).-A theoretical discussion of the validity of atomic hypotheses. The relation between the atomicity of the elements and their electrical and heat conductivities and other properties are discussed a t length.It is most probable that the metals are all monatomic whilst most of the other elements are diatomic and with the exception of sulphur are never more than tetra-atomic ; highly complex association only occur- ring by the union of unlike individuals Tables are given showing that K/Kl is a constant approximately for the metals of each group in the periodic system (where K= atomic electrical conductivity a t m. p. i n absolute temperature and XI =electrical conductivity a t 1/2 1/3 1/4 this temperature. Thus for Zn at 692O K= 50.0 a t 692/2-273 = 73” Kl = 125 K/K = 2050). These constants as well as similar con- st,ants for t’hermal conductivity and other properties of the metals also shorn the usual periodicity in reviewing them from right to left of the periodic table.For the metals the temperature playing an analogous but not identical part with that played by the critical temperature for liquids will probably be the m. p. of the metal at zero pressure but for practical purposes the m. p. at the ordinary pressure can be taken. A table is given showing that at the temperature 1/3 m. p. (calculated as above) the atomic heat of the elements with but very few exceptions = 6 +_ 0.5. Z . K. Certain Relations between the Atomic Weights of the Elements. DELAUNEY (Cornpt. rend. 1907 145 1279-1280).-The atomic weights of the elements can be represented with considerable accuracy by ratios of the type A2/n where A and n are whole numbers ; $bus helium Z2/1 ; potassium 142/5 ; bromine 3g2/19 &c. Moreover,98 ABSTRACTS OF CHEMICAL PAPERS.for closely related elements the divisors (n) are in some instances approximately the same or in regular progression. Thus cadmium mercury and zinc have the values 152/2 202/2 and 142/3 whilst lithium rubidium and caesium have 132/24 4’i2/26 and 612/28 respectively. I n other cases however related elements have widely different divisors whilst unrelated elements have similar onefi. These anomalies can however be eliminated if the more general ratio (Aa)2/na2 where a is a whole number be employed. Thus the value for potassium (142/5) can be made comparable with that of sodium (222//31) by taking a = 2 when the former value becomes 2S2//20. The divisors for a family of elements often fall into a regular series ; thus €or boron scandium yttrium lanthanum and aluminium the atomic weights are represented by 1 12/11 232/12 342/13 502/18 and 252/23.E. H. The so-called Physico-chemical Atomic Weights and the Calculation of the Weight of a Normal Litre of Gases. GUSTAV D. HINBICHS (Chem. Zentr. 1907 ii 1290 ; from Man. sci. 1907 [iv] 21 11 581-583. Compare Abstr. 1893 ii 316 317 ; 1906 ii 197).-The author denies the possibility of obtaining accurate atomic weights by weighing gases because the so-called physico- chemical methods only confirm the gravimetric methods which he has shown to be false and depend on gas theories in particular that of van der Wads. The weight of a normal litre can be calculated by multiplying the absolute atomic weight by 44.655 mg. The discrepancy in the cases of hydrogen and carbon dioxide between the calculated values and those found experimentally by Leduc and by Rayleigh indicates that the molecular volumes of these gases are only 0.9936 of those of oxygen nitrogen and carbon monoxide.c. s. Are the Stoichiornetric Laws Intelligible without the Atomic Hypothesis? OTTO KUHN (Chern. Zeit. 1908 32 55-56. Compare Abstr. 1907 ii 678).-A further adverse criticism of Wald’s attempt to establish the stoichiometric laws without the aid of the atomic hypothesis (Chem. Zeit. 1906 30 963 975 ; Abstr. 1907 ii 755). G. Y. The Metallic Form of Metalloids. EDUARD JORDIS (Zeitsch. aizgeto. Chern. 1907 20 2241-2245.)-In the periodic system the rnetsls lie t o the left and foot the metalloids to the right and top of the table. Between these are certain intermediate elements such RS arsenic and antimony which may be obtained in both the metallic autl the non-metallic states. Others besides the typical intermediato elements might be expected under favourable conditions to change their state.Of the nine non-metals nitrogen and phosphorus occur as metals in alloys whilst oxygen sulphur and probably iodine exhibit metallic properties in certain oxides sulphides and iodides especially in regard to their optical thermal and electrical behaviour ; hydrogen unites directly with metals and forms the cation Ha. The metallic state is therefore a more common property of theGENERAL AND PHYSICAL CHEMISTRY. 99 elements than is generally supposed and it may be expected tbat under suitable conditions this state will be assumed by the remaining nm-metals chlorine bromine and fluorine with greatest difficulty probably in the case of the last.The converse change that of the metals into the metalloid state is considered to take place less frequently or in other manners. The passivity of the metals the cathodic and anodic phenomena and the properties of minerals and compounds of metals with metalloids are discussed from this point of view. G. Y. Modiflcation of Hundt’s Method of Producing Dust- Figures by Stationary Waves and a New Determination of C?/C for Helium. ULRICH BERN and H. GEIGER (Ber. deut. physzkccl. Ges. 1907 5 657-666).-The time of vibration of a closed tube can be altered very simply by loading the ends of the tube; this is effected by cementing discs of metal symmetrically on t o the two ends by means of sealing-wax. By taking the requisite number of such discs the pitch of the vibrating tube may be made to correspond with an exact multiple of half wave-lengths in the enclosed gas and stationary waves are then set up giving r k e to corresponding dust-figures. The wave-lengths in helium and air have been compared by this method and from the results the value of C,/C for helium is found to be 1.63 indicating that the gas is monatomic. H. M. D. A New Vacuum Regulator. K. W. HOLTERMAN (Chew. Zed. 1908 32 8).-The author describes and figures a vacuum regulator consisting of nine glass manometer tubes connected in series between the vacuum distillation apparatus and a bottle communicating with the outer air by a tube drawn to a fine point. The manometer tubes are charged with an amount of water such that air is drawn through the regulator when the pressure in the distillation apparatus falls below that desired. Variations in the atmospheric pressure are compensated by means of a tenth manometer tube arranged to rotate on its horizontal axis. G. Y. Porous Materials as Substitutes for Stopcocks in the Manipulation of Gases. ALFRED STOCK (Bey. 1907 40 4956-4959. Compare Prytz Arm. Physik 1905 [iv] 18 617).- Prytz’s porous material is replaced by a material made by burning a mixture of earthenware water glass and gum. Plates of considerable homogeneity are thus produced they are not affected by dilute acids or boiling water and can readily bs fused into glass vessels. Their porosity is indicated by the following numbers a plate of 8 mm. diameter and 2-3 mm. thickness allows 600-800 C.C. of air to pass per minute with a difference in pressure of 60 cm. of mercury. The plates do not admit of the passage of mercury even with a difference in pressure of 1 atmosphere. The plates can be fused into the ends or middle of tubes and used in much the same manner as suggested by Prytz. A more compIex apparatus is described containing two porotts plates and an ordinary cock surrounded by mercury. J. J. S.

ISSN:0368-1769    

DOI:10.1039/CA9089405077

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

100 ABSTRACTS OF CHEMICAL PAPERS. Inorganic Chemistry Atomic Weight of Hydrogen. WILLIAM A. NOYES (J. Amer. Chem. SOC. 1907 29 1718-1 739).-In earlier papers (Abstr. 1889 672 ; 1890 1370) determinations of the composition of water have been recorded which indicated that the atomic weight of oxygen is probably slightly less than 15.S96. A t the close of each of these experiments a small amount of gas was obtained which was assumed to be nitrogen; the weight of this gas calculated as nitrogen was subtracted from the weight of hydrogen giving a correction of about 1 part per 1000. Later after the appearance of Morley's papers (Abstr. 1895 ii 261 ; 1896 ii 640) it wasconsidered likely that this gas came from the copper oxide and that its weight should be deducted from the weight of the oxygen instead of from that of the hydrogen.On applying this correction the value 15.879 (or H= 1.00765) was obtained which coincides with MoKley's result. F u i ther experiments are now described which have been carried out with the object of testing this explanation of the earlier results. The apparatus eniployed was similar to that used in the previous work and special precautions were taken to ensure the purity of the hydrogen and to avoid leakage. The weight of the hydrogen was determined by the increase in weight of a piece of apparatus con- taining copper oxide and in which the water formed by the oxidation of the hydrogen was coudensed. The first experiments mere vitiated by the retention of water by the copper oxide and mere therefore rejected.In subsequent experi- ments efforts were made to reduce this source of error as far as possible. I n the second series the hydrogen was obtained by the electrolysis of dilute sulphuric acid and was weighed first in palladium and again after being transferred to the copper oxide tube The mean result of seven determinations gave H = 1.00788 it 0*00002. I n the third series the hydrogen obtained by the electrolysis of dilute sulphuric acid was led directly into the copper oxide tube and converted into water. The mean of five experiments gave H '=-- 1.00771 +_ 0*00004. I n the fourth series the use of copper oxide was avoided by absorbing the hydrogen in palladium and converting it into water by means of oxygen both gases being obtained by thu electrolysis of dilute sulphuric acid.The mean of eight determinations gave I n the fifth series hydrogen and oxygen obtained by the electro- lysis of barium hydroxide solution were combined by means of palladium. The mean of five experiments gave H = 1.00787 & 0.00002. The most probable value for the atomic weight of hydrogen which can be calculated from t'hese results is 1.00787. For certain reasons however i t is considered that a more trustworthy value is a mean between this and Moriey's value (1.00762 + 0*00002) namely 1.00775 H = 1.008 12 +_ 0*00003.INORUANIC CHEMISTRY. 101 During the course of the work evidence was sought with regard to the qliestion as to whether change of weight occurs in a chemical reaction in which a large amount of energy is dissipated. Conclusive evidence was not obtained but it was found that if any change of weight takes place it must be very small.E. G. Formation of Ozone by the Action of the Electric Dis- charge at Low Temperatures. E. BRINER and E. DURAND (Conapt. rend. 1907 145 1272-1274. Compare Abstr. 1907 ii 759 ; Hautefeuille and Chappuis Abstr. 1880 847 ; Olszewski Abstr. 1887 634; Beill Abstr. 1893 ii 317; Troost Abstr. 1898 ii 569; Ladenburg Abstr. 1899 ii 18; Goldstein Abstr. 1903 ii 723)- By means of the apparatus described previously (Abstr. 1907 ii 342) in which the sparking-bulb is replaced by the ordinary double-walled ozoniser the authors have studied the action of the silent discharge on oxygen a t low temperatures. When the ozoniser is cooled in a mixture of solid carbon dioxide and ether ( - 78') a limiting concentration of 11% of ozone is obtained which is the Name as that observed by Beill and is characteristic of this temperature.A t - 7 8 O 12 grams of ozone are formed per kilowatt-hour. By immersing the ozoniser in liquid air ( - 194') the vapour tension of ozone is reduced nearly to zero and it becomes possible to change oxygen almost completely (99%) into ozone. As the mean pressure is reduced from 203 mm to 27 mm. the yield of ozone por kilowatt-hour rises to a maximum of 55 grams a t 98 mm. and then falls. The ozone as i t is formed con- denees to a deep blue viscous liquid. The optimum pressure of about 100 mm. is the same an that observed in sparking mixtures of nitrogen with oxygen and hydrogen and in the formation of oxides of nitrogen by the electric arc (Hrtber and Koenig this vol.ii 34). The action of the electric spark on oxygen cooled to - 194' produces ozone to the extent of only 0*79% and this is probably due to the silent discharge accompanying the spark. E. H. Acid Properties of Ozone. WILHELM MANCHOT and W. KAYP- SCHULTE (Ber 1907 40 4984-4990).-When ozone is passed into liquid ammonia which is strongly cooled a deep orange-red colour is obtained; this vanishes whilst the ammonia is still liquid when the temperature is raised. When the coloured liquid is introduced into cooled titanium sulphuric acid hydrogen peroxide can be detected and this is also the case with the colourless liquid. Ozone forms a thick fog with ammonia at the ordinary temperature whereby nitrite is not formed.A sirriilar fog is given by other organic bases and is the more illtense the stronger the ba.0. The ozone componnds of the alkali metals described by Baeyer and Villiger (Abstr. 1902 ii 650) obtained by the action of ozone on their hydroxides when orange-brown or yellow substances are formed $ve intense colorations when introduced into strongly cooled titanium sulphuric acid except in the case of sodium hydroxide. Cesium gives the most lithium the least stable ozone compound. When heated in a stream of 8-9% ozone the sodium compound is decolorised a t about 90°,102 ABSTRACTS OF CHEMICAL PAPERS. the potassium a t about llO',and the rubidium at about 140' ; the colour given by cmiurn hydroxide remains to above 160'. Lithium hydroxide gives no coloration with ozone and must decompose below the ordinary temperature.The hydroxides of magnesium calcium strontium and barium decompose ozone very rapidly a t the ordinary temperature ; a t lower temperatures barium oxide shows a distinct coloration that of calcium oxide is less marked and magnesium oxide gives no colour. These metals behave therefore analogously to the alkali metals. The oxygen-carrying power of the alkaline earths previously observed in the case of the action of ozone on metallic silver (Abstr. 1907 ii 616) may in view of the above be explained as due to calcium hydroxide combining with ozone and giving up oxygen to the silver. The formation of these compounds is attended by a considerable development of heat. They are decomposed by water and ozone may be passed through 50% sodium hydroxide almost without decom- position until a temperature of 70" is reached.Additional proof of the acid properties of ozone is afforded by the following observa- tions. Strong ozone above 6% fumes in moist air ; blue litmus paper is rendered faintly red and other indicators show an unmistakable acid reaction. Ozone passed into water increases the conductivity ; this appears to be due in part to a decomposition product since the water remains a conductor when ozone is no longer to be detected. E. F. A. Persulphides of Hydrogen. GIUSEPPE BRUNI and ALESSANDRO BORGO ( A t t i 22. Accad. Lincei 1907 [v] 16 ii 745-754).-The authors have prepared a number of persulphides of hydrogen and find that the proportion of sulphur added to the alkali sulphide or the composition of the alkali polysulphide employed has no influence on the composition of the hydrogen persulphide obtained.Cryoscopic examination of the various products dissolved i n bromoform indicates the probable existence in solution of compounds varying from H,S t o H2SY T. H. P. Acid Energy of Thiosulphuric Acid and the Decomposition of this Acid. JOSEPH A. MULLER (Bull. 8oc. chim. 1907 [iv] 1 1155-1 158. Compare Berthelot Abstr. 1889 824),-RIeasurements of the amounts of heat absorbed when (a) 1 gram-molecule of hydro- chloric acid and ( b ) 2 gram-molecules of hydrochloric acid are added to 1 gram-molecule of sodium thiosulphate show that the absorptiou of heat due to the formation of NaHS,O in the first reaction approximates t o that due to the formation of Na2S203 from NaHS,O first formed in the second when the reactions are conducted at such dilutions that the changes due t o secondary reactions become negligible.Consequently the "acid energies " of the t w o hydrogen atoms in thiosulphuric acid are approximately equal. As illustrating the instability of thiosulphuric acid it is mentioned that on the addition a t 1 2 O of a gram-molecule of hydrochloric acid dissolved in 16 litres of water to a gram-molecule of sodium thio- sulphate dissolved in a similar quantity of water sulphur begins toINORGANIC CHEMISTRY. 103 be deposited after 1.5 minutes and the reaction continues until one atom of the sulphur is liberated. When 2 gram-molecules of hydrochloric acid are employed in the place of 1 gram-molecule in such an experiment the precipitation of the sulphur is never complete indicating that whilst the sodium hydrogen thiosulphate formed in the firht case decomposes completely into sodium hydrogen sulphite and sulphnr the thiosulphuric acid liberated in the second case is only partially decomposed yielding sulphurous acid and sulphur.T. A. H. Effect of Heating Yellow Phosphorus in Ammonia Gas. \VrLr,IAM G. LLEWELLYN (Chem. News 1907 96 296-297).-Neither yellow nor red phosphorus reacts with ammonia gas between 10" and looo; white phosphorus is obtained by distilling yellow phosphorus in an atmosphere of ammonia. W. H. G. Carbon Suboxide. 111. OTTO DIELS and PAUL BLUMBERG (Bey. 1908 41 82-86. Compare Abstr. 1906 ii 227; 1907 ii 180).- An attempt t o solve the problem of the constitution of carbon suboxide has been made by an examination of its molecular refraction and dispersion.The actual values obtained mol. ref. 16,6 and mol. dis. 0.736 0.739 and 0.862 are more in harmony with Diel's formula CO:C:CO calculated values &I = 15.49 and y - a = 0.749 than with Michael's (Abstr. 1906 ii 442) for which the values M,= 13.57 and y - a 0.435 have been calculated. The fact that the values actually obtained are somewhat higher than those calculated for Diel's formula points to an " exaltation " due t o the numerous double bonds in the system 0:C:O:C:O. According t o Briihl (Trans. 1907,91,115) contiguous double bonds produce a measurable exaltation of the molecular refraction and dispersion whereas compounds with '' cumulative " double bonds are optically normal.J. J. S. Silicates. VII. EDUARD JORDIS (Zeitsch. anorg. Chem. 1907 56 296-319. Compare Abstr. 1903 ii 475 542 595; 1905 ii 88 248). -The preparation of crystalline sodium metasilicate is described and some of the properties of aqueous solutions of alkali silicates are discussed. I n aqueous solution sodium hydroxide retains silica in the proportion 2.5-2.7Si0 1Na,O. Fused sodium hydroxide dissolves more silicic acid than does the aqueous solution so that the fused mass is partially decomposed by water. Concentrated solutions of sodium silicate gelatinise on cooling and become liquid again on warming. Crystaliised sodium metasilicate Na,SiO with 6 and 10 H,O has been obtained by crystallisntion from a solution containing 3 mols.of sodium hydroxide to 1 mol. of silica. It is purified by recrystallisatioa from N-sodium hydroxide and mashing with 50:A alcohol. The meta- silicate dissolves in water forming a solution of definite and repro- d uci bl e pro pert i es . Attempts t o prepare s-odiuru orthosilicate sodium hydrogen meta-104 ABSTItACTS OF CHEMICAL PAPERS silicate or potassium metasilicate in crystalline form in the wet way have so far proved unsuccessfnl. Solutions of pure sodium silicate are not precipitated by a,mmonia or by electrolytes but solutions of ‘‘ water glass ” yield precipitates under these conditions. The precipit,ate which separates from solutions of alkali silicates a.fter a time consists mainly of impurities (aluminium and iron).G. S. Rubidium Calcium Sulphates. JOH. D’ANs and W. ZEH (Bey. 1907 40 4912-4914. Compare Abstr. 1907 ii 168).-A study of the double sulphates of rubidium and calcium has resulted in the isolation of two new salts although Ditte’s double salt could not be prepared (Abstr. 1877 i 440). Kubidiurn syngenite CaRb,(SO,),,H,O prepared by leaving finely- divided gypsum in contact with a 30% solution of rubidium sulphate crystallises in strongly refracting needles probably isomorphous with the potassium and ammonium syngenites. On boiling calcium sulphate with 30% aqueous rubidium sulphate rubidium dicalcium sulphate Ca,Rb2(S0& is formed ; its crystalline form is similar to that of the corresponding ammonium salt. The rubidium syngenite is converted into the dicalcium salt in contact with aqueous rubidium sdphate a t 40’.Attempts to prepare the pentasulphate have so far been unsuccessful. I n the series potassium ammonium rubidium the stability of the dicalcium salt increases whilst that of the pentasulphate decreases. Ca&qSO,)s 3H,O w. K. Action of Ammonium P e r s u l p h a t e on Metals. J. W. TURRENTINE (J. Physical Chem. 1907 11 623-631).-When a strip of copper is immersed in ammonium persulphate solution it loses in weight and the loss i n weight is very nearly the equivalent of the reduced persulphate Copper immersed in ammonium per~ulphate behaves therefore like a copper anode in the electrolysis of sulphates. This analogy between chemical corrosion in ammonium persulphate and electrolytic corrosion in ammonium sulphate is borne out also by the behaviour of nickel cadmium and aluminium.I n the ca=e of nickel the loss of weight is about 1376 less than the equivalent of the reduced persul phate. Cadmium dissolves readily in ammonium per- sulphate without evolution of gas but there is considerable discrepancy between the observed and calculated values for the loss of weight. Only slight corrosion of aluminium occurs in ammonium persulphate solution. Ammonium persulphate dissolves iron forming ferrous sulph- ate some of which is oxidised by the excess of the persulphate. It appears that the free acid formed by the hydrolysis of ferric sulpbate acts as a catalytic agent in the reaction between iron and water. J. C. P. Action of Silver N i t r a t e and of Mercuric N i t r a t e on Borne Inorganic Hydroxides.WILRELM BrLTz and FRIEDRICH ZIMMER- ~ I A N N (Ber. 190’7 40 4979-4984).-When freshly-precipitated magnesium hydroxide is moistened with a solution of silver nitrate,INORGANIC CHEMISTRY. 105 the hydrogel is coloured yellowish-brown owing to the separation of silver oxide. The authors have studied the behaviour of other inorganic hydroxides towards both silver nitrate and mercuric nitrate. The various hydroxides were precipitated by ammonia from the hot solutions of their salts washed until free from ammonia and then saturated with N/10 silver nitrate Glucinum aluminium indium zirconium stannic antimony and bismuth hydroxides respectively gave no reaction zinc hydroxide was coloured faintly brown cadmium hydroxide strongly brownish-yellow and lead hydroxide somewhat violet-brown.With mercuric nitrate the hydroxides of indium zirconium antimony and bismu th gave no reaction glucinum hydr- oxide was coloured yellowish-red magnesium hydroxide strongly yellowish-red zinc hydroxide faintly yellow cadmium hydroxide strongly yellowish-red aluminium hydroxide faintly yellow lend hydroxide yellowish-red and bismuth hydroxide brightly yellow. The behaviour of a number of hydroxides of rare elements was studied fiom the same standpoint. A. RICK. Solubility of Calcium Carbonate in Aqueous Solutions Of Potassium Chloride and Potassium Sulphate at 25'. FRANK K. CANERON and WILLIAM 0. ROBINSON (J. PhysicaZ Chenz. 1907 11 577-580. Compare Abstr. 1902 ii 320).-Calcium carbonate is much more soluble in aqueous solutions of potassium sulphate than in aqueous solutions of potassium chloride.The solubility curve for calcium carbonate in the chloride solutions passes through a maximum. When calcium carbonate is kept in contact with potassium sulphate solutions containing more than 2.98% K,SO spgenite is formed J. C. P. Soluble Basic Sulphates of Glucinurn. CHARLES L. PARSONS WILLIAM 0. ROBINSON and C. T. FULLER (S. Physical Clhem. 1907 11 651-658).-A solution of glucinum sulphate dissolves fairly large quantities of glucinum hydroxide and the solutions obtained in this way have been examined by the authors. It is shown that the addition of glucinum hydroxide to a solution of glucinum sulphate raises the freezing point of the latter and lowers its conductivity.The solutions obtained are not true colloids as shown by dialysis experiments nor does the glucinum enter into a complex anion. It is suggested that the dissolved glucinum salt acts as a solvent for the hydroxide just as acetic acid dissolved in water will dissolve camphor which is itself insoluble in water. J. C. P. Alloys of Zinc and Nickel. VICTOR TAFEL (Metallurgie 1907 4 781-785).-Alloys containing up to 50yh of nickel were prepared by adding nickel to molten zinc covered with a layer of borax. The freezing-point curve has a eutectic point very close t o the zinc end the eutectic temperature being only 0.5' below the melting point of zinc. Eight different crystalline constituents mere observed. I is pure zinc; the series of mixed crystals X I contain from 12.2% t o 23% of nickel ; I11 is the compound NiZn indicated by a maximum on the106 ABSTRACTS OF CHEMICAL PAPERS.freezing-point curve j the mixed crystals I V contain from 39.7% t'o 45.8% of nickel and break up on cooling to 640" into the crystals V and VI. Crystals VII separate from the molten mass but then react with i t at 1025-1037" to form IV. The mixed crystals VIII are formed when alloys containing more than 45.8% of nickel are cooled to 780". The exact nature of the crystals with the exception of the compound NiZn could not be determined. The brittleness of zinc is greatly increased by the addition of nickel ; NiZn is extremely brittle and gives a characteristic blue coloration with dilute nitric acid. Photomicrographs of the alloys are given. C.H. D. New Kind of Dioxides I. LUIGI MARINO (Zeitsch. anorg. Chem. 1907 56 233-245),-1t is shown that the dioxides of manganese lead and barium react quite differently towards sulphur dioxide and it is therefore suggested that the constitution of the three dioxides mnst be different. Pure manganese dioxide was suspended in water and sulphur dioxide passed in at 10-12O until a clear solution was obtained. Analysis showed that the solution thus obtained contained manganese dithionate and a little sulphate; the main reaction is therefore represented by the equation MnO + 250 = MnS20,. At the same time the '' induced " reaction R'lnS,O + MnO = 2MnS04 takes place to a slight extent. By the action of sulphur dioxide on lead peroxide on the other hand a heavy white powder consisting of a mixture of lead sulphate and sulphite was obtained and not a trace of dithionate was formed.Evidence is adduced t o show that the successive stages of the reaction are as follows PbO + SO = PbSO + 0 ; SO + 0 + H,O = H,SO ; PbSO + H,SO = PbSO + H,SO,. When barium peroxide is used the first stago of the reaction is represented by the equation BaO + H,SO = BaSO + H,O the hydrogen peroxide then oxidising the sulphur dioxide and barium sulphite to sul phuric acid and barium sulphate respectively. Selenious acid also behaves differently towards the peroxides of lead and manganese ; the results of the investigation mill be communicated later. The difference in behaviour of the dioxides in question is ascribed to a difference of constitution which for those of manganese and lead may be represented by the constitutional formulile M n g 0 and 0 0 P b e b .As the sesquioxides of iron and cobalt give like manganese dioxide additive compounds with sulphur dioxide (Seubert and Elten Abstr. 1893 ii 278) they may also contain a group of the type M g o ; 0 the formula for ferric oxide would thorefore be 0 Be:Feg0. 0 The constitutional formula of dithionic acid is also discussed. G. S.IN 0 RG A N I C C H E M I ST H Y . 107 Action of Oxygen 011 Copper Tin Zinc and the Alloys of Tin and Zinc with Copper. EDUARD JORDIS [with w. ROSENHAUPT] (Chem. Zed. 1908 32 19-21. Compare Jordis this vol. ii 98). -The rate of absorption of dry and of moist oxygen by copper tin zinc and alloys of tin and zinc with copper has been determined a t various temperatures and the results expressed in curves.The reaction commences with copper at about SOo with tin above loo' and with zinc a t IW" ; at temperatures below ZOO' the dry oxygen is absorbed slightly the more rapidly by copper and tin the moist oxygen by zinc but above 200° whilst the relation between the rates of absorption by tin remains approximately unchanged the moist oxygen is absorbed much more rapidly than the dry gas by copper and zinc. An alloy containing 70% of copper and 30% of tin acts as a mixture of the compound Cu,Sn with an excess of copper and the alloys of copper and zinc as mixtures of CuzZn with an excess of copper or of zinc. The absorption curves of the alloys resemble to some extent those of the metal present in excess.The discussion of the results leads to the conclusion that the oxidation of these metals and alloys is not a simple process but consists of several simultaneous reactions one of which must be a diffusion of the oxygen in the metallic state through the metal or alloy. G. Y. Action of Lime in Excess on Copper Sulphate Solutions. JAMES M. BELL and WALTER C. TABER (J. Physical C'hem. 1907 11 632-636).-The authors have determined the composition of the solution and of the precipitates obtained when lime and copper sulphate solutions are mixed in different proportions and concentra- tions. The results are summarised in the following table Gram per litre. CaO. 1.206 1.780 1.90s 1 m s 1.358 1.120 0.880 so, 0.0 0.872 1.060 1.052 1,112 1.144 1 -2 80 Solid phases.Cn(OH) blue copper hydroxide. Ca(OH) blue copper hydroxide. Ca(OH),,CaS0,,2H20 blue copper hydroxide. CaS0,,2H,O blue copper hydroxide. CaS0,,2H,O blue copper hydroxide. CaS04,2H,0 green copper hydroxide. CaSO 2H,O green copper hydroxide. I n the preparation of Bordeaux mixture a very large excess of lime is added and the precipitate mill consist of the three solids lime gypsum and the blue copper hydroxide. J. C. P. Solubility of Gypsum in Copper Sulphate Solutions. JAMES M. BELL and WALTER C. TABER (J. Physical Chern. 1907 11 637-638).-The solubility of gypsum at first diminishes as the con- centration of copper sulphate increases until at a copper sulphate concentration of 30 grams per litre the solubility of gypsum reaches a minimum of 1.7 grams CaSO per litre.Further increase in the copper sulphate concentratiou causes a rise in the solubility108 ABSTRACTS OF CHEMICAL PAPERS. (at first rapid and then slow) and a solution which is saturated with copper sulphate dissolves gypsum t o the extent of 2.08 grams per litre. J. C. P. The Nature of the Phosphorescent Elements and Meta- elements of Sir W. Crookes. GEORGES URBAIN (Conzpt. rend. 1907 145 1335-1337).-The phosphoresceut spectra afforded by mixtures in varying proportions of the anhydrous sulphates of pure gadolinium and terbium contain the bands which were attributed by Sir W. Crookes to the elernent,s or meta-elements G Gc Gg ionium and incognitum (Abstr. 1887 334; 1906 ii 62). The intensity of the bands varies with th‘e composition of the mixture and the mixtures containing less than 0.5% or more than 10% of terbium are very slight,ly phosphorescent.The author concludes that i n these mixtures the terbium which is the active phosphorescent substance is not a mixture of several elements. M. A. W. Bayer’s Bauxium. G. GRINER and GEORGES URBAIN (Bull. SOC. c l h z . 1907 [iv] 1 1158-1163).-1n manufacturing alumina from the red bauxite of Var the sodium aluminate obtained by roasting the mineral with sodium carbonate is decomposed by a current of carbon dioxide and the sodium carbonate is recovered from the filtrate by evaporation. The mother liquors from the last process contain chromic vanadic molybdic tungstic phosphoric arsenic and silicic acids with small quantities of alumina magnesia lime &c. and after the removal of these various constituents Bayer obtained (Abstr.1895 ii 313) a violet-coloured solution which on exposure to air became yellow and gave other reactions which led him to suppose that it contained a new element ‘‘ bauxium.” This material has now been examined spectrographically by the authors and they find that it consists essentially of a mixture of vanadium and tungsten containing it trace of molybdenum and minute traces of copper bismuth lead calcium and sodium and that a dilute solution of ammonium vanadate containing a small quantity of ammonium tungstate gives all the reactions which Bayer thought to be characteristic of bauxiurn. Bayer’s misapprehension of the nature of the solution he obtained appe:irs to have been due to his supposition that vanadium can be completely removed from solution as ammonium vanadate and tungsten as tungstic acid which it appears now is not the case. A detailed description of the spectrographic method employed by the authors is given in the original.Gases Occluded in Steels G. RELLOC (Compt. Tend. 1907 145 1280-1283. Compare Abstr. 1903 ii 484).-The work described refers to (1) the nature of the gases ; (2) the form of the curves in t and duldt relatively to the total volume and t o the volume of each gas ; (3) the relative proportions of each gas a t different temperatures ; (4) the relations of these curves to the critical points ; (5) variation of the gases according to the thickness of the section of metal from which they are derived and (6) their alteration with different steels.Two bars of a very soft steel containing 0.12% of carbon 0.03% of silicon 0.02% of T. A. H.INORGANIC CHEMISTRY. 109 sulphur 0.018% of phosphorus and 0.35% of molybdenum chosen so that Its critical points are well separated were examiued. Their critical points were caref lilly determined by Roberts- Austen's differential method. The evolution of gases is in intitreate relation with the critical points of the iron and may be divided irlto three stages. ( 1 ) The evolution begins a t a variable and ill-defined temperature ( 150°-4000) ; the dv/dt curve has a small minimum a t 200' and a small maximum a t 300° but the evolution is small below the point A,. (2) Between 500' and 600' the dv/dt curve exhibits a large maximum at the point A and then falls rapidly to a minimum (approaching zero) a t the end of A .The point A has no well-defined influence in the steel considered. (3) The evolution increases again a t the beginning of A then diminiybes slowly and seems to increase afresh with the tempera- ture. Adopting Osmond's definition of the point A these stages can be interpreted thus (1) I n the region of the a-iron the evolution of gas is very small and apart from small irrrgularities tends to increase with the temperature. (2) The commencement. of the conversion of a-iron into p-iron is characterrsed by an abundant evolution which diminishes as the conversion progresses. The transformation of the cementation carbon iuto '' temper " carbon to the extent of 0.12% has no marked influence. (3) Tho evolution recommences with the trans- formation of the /3-iron into y-iron and after passing through a maximum seems to increase with the temperature in the region of the y-iron.The gases evolved consist of carbon monoxide and dioxide hydrogen and nitrogen. The first produced is carbon dioxide which a t the beginning forms almost the total volume. It disappears at about 550' (Ao). Nitrogen begins to appear a t about 550' and persists a t all higher temperatures but the amount is small not rising above a mean val-le of 10%. Above 40(b0 hydrogen and carbon monoxide alone are evolved but their proportions are subject to sudden alteration with the temperature. A larger volume of gas was evolved and the evolution commencd sooner from the first bar than from the second probably owing to initial loss of gas from the latter by its fiuer sub- division.'l'he gases are very irregularly distributed in the steel the proportion in the intermediate layers being mucb greater t h cn in the superficial and central portiorts. As regards the state of the gas in the metal observations made are not in favour of the existence of a dissociation-tension. E. H. Extraction of Gases Contained in Metals. OCTAVE BOUDOUARD (Compt. rend. 1907 145 1283-1284).-The author has heabed in a vacuum commercial iron in the form of bars 1 square cm. in cross- section sheet 1 mrn. thick wire 2 mm. 1 mm. and 0.5 mm. in diameter and of filings. Wire 1 mm. thick when heated a t the temperature of boiling sulphur (445') does not evolve gas but under the same conditions 3 1-5 grams of filings evolve 6.45 C.C.of gas chiefly carbon monoxide and hydrogen. The results of heating the iron in its various form* a t l l O O o in a vacuum three times allowing fifteen days' exposure t o the air between the consecutive ignitions are given in tabular form. They show that it is extremely difficult t o extract the VOL. xclv. ii. 8110 ABSTRACTS OF CHEMICAL PAPERS. gases contained in iron and steel. The metal after a third ignition a t 1100' retains aa appreciable volume of gas varying according to its state of division (from 0.5% of total volume extracted in the case of filings to 20% with sheet- or bar-iron). A table is given containing the total percentage volumes and weights of carbon monoxide hydrogen carbon dioxide and nitrogen expelled by three ignitions a t 1100" of wire 0.5 and 1 mm.thick sheet 1 mm. thick and filings The total percentage weights of gas evolved are 0*0957% 0*1029% 0*09'3% and 0.2207% respectively these quantities being of the same order as the amounts of sulphur and phosphorus ordinarily present. The valuesobtainedfor nitrogen are of the sameorder as thoseobserved by Braune (Abstr. 1905 ii 638 ; Rev. de M&taZZurg& 1907 2 834). I n a vacuum iron begins t o volatilise at 900° and does so very appreciably a t 1 100". GEORGES CHARPY (Compt. re7zd. 1907 145 1277-1279. Compare Abstr. 1902 ii 209).-The determination of the solubility of graphite in iron is rendered very difficult by the exceeding slowness of the dissolution of graphite or the conversion of the combined carbon into graphite which necessitates prolonged beating involving either carburation or decarburation of the surface according to the conditions.An ingot of grey cast-iron Containing 3.75% total carbon (3.34% graphite) about 0.1% silicon and manganese and traces of sulphur and phosphorns was obtained by melting i n a crucible some Swedish iron cemented with excess of wood-charcoal and allowing it to cool slowly. Cubes of this iron (4 cm. edge) were heated f o r three to seven hours a t temperatures varying from 750-1 150° quenched in water and then annealed a t 500'. After planing off a thickness of 2 mm. from the faces the combined carbon was determined in the remaining cubes. It is found t o increase from 0.31% at 750" t o 2.47% at 1150". A white cast-iron containing 2.82% total carbon (all combined) obtained by running the fused metal into a metallic mould when heated a t 1150° cooled slowly t o lOOO' and then quenched in cold water gives z n ingot of which the central portion contains 2.74% total carbon 1.82% graphite and 0.92% combined carbon.When the crucible prepared as above containing the liquid iron is placed in a furnace maintained a t 1000' for three hours and then plunged in cold water an ingot is formed containing 3.10% total carbon 2-1 5% graphite and 0995% dissolved carbon. By the cementation of iron a t 1000° (compare Abstr. 1903 ii 430) with wood-charcoal two irons were obtained containing (1) 2.50% carbon of which 1040% was graphite and 1.10% dissolved carbon ; (2) 3.10% carbon 2.21% graphite and 0.89% dissolved carbon.The conclusion is drawn that the solubility of graphite in iron diminishes with the temperature and amounts to about 1% a t 1000°. E. H. Solubility of Graphite in Iron. E. H. Chemical Behaviour of High Percentage Ferro-silicon. JOHANKES HAAS (Chem. Zeit. 1908 32 8).-A 50% ferro-silicon dissolves in a concentrated solution of copper ammonium fluoride,INORGANIC CHEMISTRY. 111 metallic copper separating as a flocculent spongy precipitate. The reaction which takes place spontaneously is accompanied by a violent evolution of gas hydrogen silicofluoride probably being formed. Silicic acid is not formed and the evolution of hydrocarbons has not been observed. The copper ammonium fluoride solution is almost without action on 80% ferro-manganese.G. Y. Decomposition of Iron Sulphides by Aluminium and the Probable Existence of a Double Sulphide of Iron and Aluminium. HUGO DITZ (Metallurgie 1907 4 786-792).- Sulphides are less energetically reduced by ignition with aluminium powder than oxides. A mixture of iron pyrites and aluminium in the proportion 3PeS2:4Al yields less than one-half of its iron in the metallic form. In presence of a n excess of aluminium one-half of the iron is obtained. The copper present in the pyrites is only reduced when an excess of aluminium is employed The slag appears to contain a double sulphide A1,S3,FeS which has also been obtained by Houdard (Abstr. 1907 ii 468) from ferrous sulphide and aluminium. The reduction thus proceeds according to the equation 2FeS2 + 2A1= Al,S,,FeS + Fe.When ferrous sulphide is reduced the same double sulphide is formed according to the equation 4FeS + 2 A1 = Al,S,,FeS + 3Fe. C. H. D. Roussin’s Salts. V. ITALO BELLUCCI and P. DE CESARIS (Atti R. Accad. Lincei 1907 [v] 16 ii 740-745. Compare Abstr. 1907 ii 29 472) .-On oxidation of potassium ferronitrosulphide with permanganate each molecule of the former absorbs 26 atoms of oxygen this being the amount necessary theoretically for the oxidation of all the elements to the highest grade. This result excludes all possibility of the presence of hydrogen in the molecule of Roussin’s salts. Further taken along with the complete resistance of these salts to the action of the most energetic reducing agents this oxidisability indicates that most if not all of the iron atoms in the molecule are present in the ferrous condition. Comparison of the behaviour towards hydrochloric acid of potassium ferronitrosulphide with that of the complex sulphides Fe,S,,K,S and 2FeS,K2S shows that the three sulphur atoms in the molecule of Roussin’s salts exist in the form of sulphide and are probably combined with the iron.T. H. P. Hydrolyais of Ferric Chloride. 11. Action of Hydrochloric Acid. G. MALFITANO and LEOPOLD MICHEL (Compt. rend. 1907 145 1275-1277. Compare Abstr. 1907 ii 692).-The authors have compared the rates of change of the conductivity of ferric chloride solutions with that of the conductivity of solutions containing the same quantities of ferric chloride and varying quantities of hydrogen chloride. The results obtained are illustrated by curves.The latter show that the duration of the period of constant conductivity increases with the amount of hydrogen chloride added and other things being equal the quantity of hydrogen chloride required to render the solution 8-2112 ABSTRACTS OF CHEMICAL PAPERS stable increases considerably with the temperature and varies slightly with the concentration of the ferric chloride. The remarkable pheno- menon i s observed that during the hydrolysis of a ferric chloride solution a considerably larger quantity of hydrogen chloride can be formed than would have rendered the solution stable if added at first the conductivity of hydrolysed solutions rising t o values greater than those of so1ui;ions initially treated with hydrochloric acid. Moreover small additions of acid only retard hydrolysis a t the beginning after- wards appearing to accelerate it.Measurements of the conductivities of M/30 solutions of ferric chloride alone and with varying quantities of hydrogen chloride (M/30 to M/10) (1) immediately after dissolution (2) after thirty minutes’ heating a t looo and then (3) forty-six hours later show that the increase in conductivity on heating and its decrease subsequently diminish as the quantity of acid added increases. The conclusion is drawn that the products of hydrolysis are not constant in composition only those first formed being easily reconverted into FeCl by the hydrochloric acid present the action of the acid becoming more and more difficult as the hydrolysis progresses and further that the products of hydrolysis are rendered more resistant by the presence of hydrogen chloride.To justify these conclusions curves are given showing that the amount of hydrochloric acid which added at the beginning renders the solution stable when added during hydrolysis not only does not restore the solution to its original condition but does not stop the hydrolysis. These phenomena appear to be best explained by the hypothesis that the colloid formed from the products of hydrolysis is composed of complex ions. E. H. Ferric Chlorides. FRANK K. CAMERON and WILLIAM 0. ROBINSON (J. Physicul Chena. 1907 11 690-694).-The investigation deals with the cases in which there is relatively more ferric oxide than acid. It appears that at 2 5 O no definite basic chloride is formed the st,able solid phase being one of a series of solid solutions containing ferric oxide hydrochloric acid and water.J. C.P. Ferric Sulphates. FRANK K. CAMERON and WILLIAM 0. ROBINSON (J. PhysicaE Chem. 1907 11 641-650).-Ferric sulphate solutions of varying concentration were shaken with freshly-precipitated ferric hydroxide at 2 5 O for four months. At the end of this time the clear solutions were separated and analysed. It is shown that no definite basic ferric sulphates are formed. I n contact with solutions containing less than 25% SO the stable solid is one of a series of solid solutions containing ferric oxide sulphuric acid and probably water. I n contact with solutions containing from 25% to 28% SO the stable solid is a hydrated normal sulphate of the composition Fe20,,3S0,,1 OH,O.I n contact with solutions containing more than 28% SO the stable solid is a hydrated acid sulphate of t h i composition Ee,0,,&303 10H20. J. C. P. A New Chromium Sulphate. PAUL NICOLARDOT (Compt. r e d . 1907 145 1338-1 340).-When the green solution obtained byINORGANIC CHEMISTRY. 113 boiling a solution of violet chromium sulphate is heated with barium carbonate part of the sulphuric acid is precipitated and on complete spontaneous evaporation of the filtrate a new chromium suZphate Cr20,,2.5S03,7*5H20 is obtained as a non-crystalline solid readily soluble in water to form a green solution but insoluble in alcohol or acetone and precipitated from aqueous solution by these liquids. Solutions of the salt do not yield precipitates with barium chloride or with sodium phosphate ; it differs in this respect from the sulphate of sulphochromyl hydroxide described but not isolated by Recoura (Abstr.1896 ii 27) and resembles the sulphate (Cr,0,(S0,)3,8H,0 obtained by Recoura by dehydrating the solid violet chromium sulphate. &I. A. W. Chromates. SAMUEL H. C. BRIGCIS (Zeitsch. anorg. Chem. 1907 56 246-260. Compare Trans. 1903 83 391; 1904 85 677),- The preparation and properties of certain chromates dichromates and double chromates are described. Nickel dichromate 2NiCr,07,3H,0 obtained by heating together nickel carbonate and chromic acid in aqueous solution at a high temperature occurs in reddish-brown transparent prisms which are deliquescent. The corresponding cobalt salt CoCr207,H,0 prepared by an analogous method forms black lustrous deliquescent crystals.Ammonium cobalt chromate (NH,),CO(C~O,)~ 6H20 obtained by interaction of ammonium chromate and cobalt acetate in aqueous solution below - 5 O occurs in well-formed brownish-yellow prisms. The corresponding coesium compound prepared by an analogous method was not obtained quite free from basic salt ; it forms small lustrous crystals. The normal chromates of copper zinc and cadmium have already been isolated from aqueous solution and described by Schulze (Abstr. 1896 ii 24); exact methods for #preparing them are now given. Attempts to obtain normal chromates of these metals analogous in behaviour to the corresponding sulphates by interaction in non- aqueous solvents were unsuccessful.A large number of compounds of pyridine with dichromates have been prepared; in most cases by interaction in aqueous pyridine solution of chromic acid or potassium dichromate and a salt of the particular metal. The compounds in question are fairly stable nearly insoluble in water and insoluble in the ordinary organic solvents. The copper compound CuCr20,,4Py occurs in small light green crystals or in well-formed dark green prisms ; the sinc compound in lustrous orange prisms; the cadcmium compound i n orange crystals and the cobalt compound as a dark brown powder. Corresponding nickel and manganese compounds were also prepared. A silver compound Ag,Cr,O,,GPy was obtained in lustrous orange crystals. On dissolving this compound in water containing a little pyridine and cooling a second silver compound Ag2Cr,0,,4Py separated in orange prisms.Two mercury salts of the same composition HgCr,07,2Pg are described. One obtained from solutions containing little pyridine. The majority of them are of the type M"Cr,07,4Py.114 ABSTRACTS OF CHEMICAL PAPERS. forms orange crystals the other which crystallises from excess of pyridine occurs in lustrous golden-yellow leaflets. A uranium compound 2U0,,3Cr08,2Py also forms lustrous orange- coloured crystals. The pyridine double salts of zinc cadmium and mercury darken on exposure to light. G. S. Potassium Ammoniostannate. F. F. FITZGERALD (J. Amer. Chem. Xoc. 1907 29 1693-1698).-1n an earlier paper (Abstr. 1907 ii 545) an account was given of the preparation of potassium ammonio-zincate by the action of zinc on a solution of potassamide in liquid ammonia.Attempts have been made to prepare other salts of this class. When excess of a solution of potassamide in liquid ammonia is added t o a solution of stannic iodide in the same solvent a crystalline precipitate of potassium amrnoniostannute Sn(NK),,4NH3 is produced which when heated at 1 4 5 O loses 3 mols. of ammonia. On further heating in a vacuum a t 316O a brick-red powder is obtained which still contains some ammonia and is decomposed violently by water with evolution of gas and deposition of tin. Columbium Sulphide. I. HEINRICH BILTZ and LUDWIG GONDER (Be.. 1907 40 4963-4972).-For the preparation of columbium pentoxide a by-product from the manufacture of tantalum compounds was used containing 46 per cent.of columbium pentoxide 36 per cent. of sodium oxide 10 per cent. of iron oxide traces of tungstic acid a little tantalum oxide and several per cent. of water. I n order to remove iron sodium and tungsten the product was fused with potassium hydrogen sulphate water added the columbic acid filtered off and then boiled with a little concentrated hydrochloric acid and washed with dilute hydrochloric acid; the fusion was then repeated in order to remove the last traces of iron. The columbic acid was then separated from traces of tantalum according to Marignac’s method; it was dissolved in pure hydrogen fluoride potassium carbonate added diluted with water and allowed to crystallise when a little potassium tantalum fluoride separated ; on further concentration potassium columbium hydroxyfluoride separated. The latter was then heated with concentrated sulphuric acid fused with potassium hydrogen sulphate boiled with water and washed by decantation with dilute hydrochloric acid. The columbic acid obtained in this manner was still contaminated with a little sulphuric acid retained by adsorption. The product was accordingly heated for several hours in a combustion tube first in a current of ammonia and finally in a current of oxygen. The pure columbium oxide was then heated to redness for several hours in a current of a mixture of hydrogen sulphide and carbon disulphide the product extracted with carbon disulphide and finally dried over sulphuric acid. It is likely that columbium sulphide has not yet been obtained pure The authors conclude that their prepara- tions are mixtures of a columbium sulphide CbS or Cb,S either with columbium or with a lower sulphide. E. G. A. McK.

ISSN:0368-1769    

DOI:10.1039/CA9089405100

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY Miner a 1 o gical C he mi s t ry. 115 Oil from the Roof of the Cockshead Goal Seam North Staffordshire. ARCHIBALD A. HALL (J. Xoc. C'hem. Ind. 1907 26 12S3-1234).-The dark brown oil which deposits crystals a t 1 8 O and is solid a t 1 5 O was found on investigation t o be a mixture of the higher paraffins with some olefines and possibly some naphthenes and phenolic substances. W. H. G. Optical Investigation of the Bibieibat Naphtha. M. A. RAKUSIN (J. Russ. Phys. Chem Soc. 1907 39 13113-1358. Compare Abstr. 1907 ii 883).-Of forty-seven naphthas examined those from the uppermost layers are of maximum transparency and with but a few ex- ceptions of lowest sp. gr. The curve expressing the relation between the depth a t which the naphtha is obtained and the corresponding coefficients of optical opacity approximates to a straight line; there is thus a genetic connexion between the various naphthas and they are a21 filtration products of one original naphtha but since this process could not have occurred everywhere a t the same speed the naphthas obtained from various parts of the globe are not identical in properties.The relation between the pressure within the earth and that of the outer layers as well as of the duration of filtration and the nature of the naphtha produced is discussed. When the outer pressure exceeds the inner no filtration can occur but the naphtha becomes compressed form- ing condensed products such as asphalt (compare Marcusson Abstr. 1907 i 466). All the Bibieibat naphthas are normal are not decom- posed and do not undergo racemisation when distilled at 850°/20 mm.Z . K. Paraffin W a x from the Ladysmith Pit Whitehaven Collieries. PETER P. BEDSON (J. SOC. CI~ern. Ind. 1907 26 1224-1 225).-An investigation of a substance which was discovered as an exudation in a drift of the Ladysmith Pit of the Whitehaven Collieries. It is a dark brown material having the consistency of vaseline and consists of a mixture of paraffin hydrocarbons contain- ing a considerable proportion of the solid members of this series with some olefines. American Pyrites Crystals. EDWARD H. KRAUS and I. D. SCOTT (Zeitsch. Kryst. itlin. 1907 44 144-153).-The following analyses are given of pyrites crystals from I Central City Mine Gilpin Co. Colorado; 11 a limestone quarry at Franklin Furnace New Jersey ; 111 an unknown locality in Colorado W.H. G. S. Fe. co. Ca. Insol. Total. I.* 53.26 46.51 - - 0 '59 100-37 11. 53'30 45.20 1-25 trace 0-03 99 -78 - 0.53 99.96 Ni Co As Sb aiid Au are absent. Detailed crystallographic descriptions are given. 111. 53-08 46'35 - L. J. S.116 ABSTRACTS OF CHEMICAL PAPERS. Artiflcial Haematite Crystals. CHARLES E. MUNROE (Arne?. J. Sci. 1907 [iv] 24 485-486).-Brilliant crystals of hmnatite were found attached to the inside surfaces of iron pipes which for seven years bad conducted alternately hydrogen chloride and air in a plant for the manufacture of chlorine by the Deacon process. The well-developed crystals are grouped in rosettes like the '' iron-roses " of the Alps. I n a six-inch pipe the crystals measured 1 cm. across and in a twenty-inch pipe they were 3 cm.across. Olivine in Serpentine from Chester Massachusetts. CHARLES PALACHE (Arne?.. J. Sci. 1907 [iv] 24 491-495).- A narrow vein two incbes or less in width of olivine occurs in serpentine a t Chester in Massachusetts. The olivine has the form of grains or of rough crystals and is associated with picrolite chrysotile brucite and magnetite. The following analysis by W. T. Schaller shows that the material although apparently pure must be inter- mixed with magnesite brucite and serpentine L. J. S . H20 H,O SiO,. FeO. MgO. NnO. CaO. F a t 100". >loo". GO,. Total. 39-43 7'83 49'26 0.12 1-20 1.49 0.77 100'10 The vein of olivine is very sharply defined from the surrounding serpentine and is evidently a younger formation representing a regeneration of olivine in the rock-mass.The serpentine pseudomorphs after olivine from this locality have been called " hampshirite," and recently the opinion has been expressed but without sufficient grounds that the original mineral was humite. Albite from Greenland. C. DREYER and VICTOR GOLDSCHMIDT (Meddelelser om Gronland 1907 34 1-60).-Measurements of well- developed wnter-clear crystals of albite from South Greenland give the following crystallographic constants a b c = 0.6373 1 0.5599 ; a= 94'18' ; j3= 116'41' ; y=87'37'. As shown by the following analyses by C. Winther the material is pure albite I of material from Kangerdluarsuk ; 11 from Narsarsuk L. J. S. SiO,. A120s. CaO. K20. Na,O. Total. I. 68-80 19-43 nil nil 11-86 100 '09 11. 68-80 19-40 0.20 11'68 100.08 L. J. S. Tourmaline from Asinara (Sardinia). AURELIO SERRA ( A t t i R. Accad. Lirzcei 1907 [v] 16 ii 102-704).-Large uniformly tinted black crystals of tourmaline D 3.08 found in pegmatitic rock at Asinara gave on analysis SiO,. E,O,. A1,0,. FcO. TiO,. P2OP MnO. CaO. MgO. 35.43 9.72 37'29 5.65 0'56 trace 0.89 1-10 4-60 Na,O. K20. H20 a t 100". H20 at red heat. F. Total. 2 -27 0 '64 - 1-50 0'12 99.77 The numbers are expressed by the formula T. H. P.

ISSN:0368-1769    

DOI:10.1039/CA9089405115

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. Physiological C h emistrg. 117 Effect of Hirudin on Blood-Gases. JOSEPH BARCROFT and G. R. MINES (J. Physiol. 1907 36 275-282).-1n work on blood- gases the principle of leech extract called hirudin is a valuable preparation. It may eitber be injected or the blood may be received into a suitable syringe containing a small quantity of hirudin solution. If the injection is made slowly no untoward results follow and no disturbance of the normal bluod-gases is produced. PETER RONA and LEONOR MICHAELIS (Biochem. Zeitsch. 1908 7 329-337).-The removal of protein by the adsorp- tive action of kaolin renders the estimation of sugar in the filtrate quite accurate in artificial mixtures containing serum to which a known amount of sugar is added. Colloidal iron hydroxide although in distinction from kaolin an electropositive colloid acts similarly.The free sugar of the blood-serum or plasma can therefore be estimated and the figures obtained by the kaolin method from plasma show the presence of from 92 to 172 mg. of sugar per 100 C.C. Glycogen is also adsorbed and removed by kaolin. I n fresh plasma the yield of sugar after treatment with iron hydroxide is always less than after treat- ment with kaolin; it is therefore suggested that some of the sugar in the blood is combined with an electroriegative colloid. W. D. H. Sugar in Blood. W. D. H. Proteoses in Blood. ERNST FREUND (Biochem. Zeitsch. 1908 7 36 1-368).-Abderhalden has stated that even during the height of digestion the blood is free from proteoses. The present paper is largely polernical and re-affirms the author’s previous position on the presence of these substances in the blood.Abderhalden’s method is criticised. W. D. H. Proteins of Horse-Serum. JOHN MELLANBY. (J. Physiol. 1907 36 288-333. Compare Abstr. 1907 ii 63 I).-Tbe usual methods of salt precipitation are not regarded as trustworthy for the separation of classes of proteins in serum. Alcohol shows a definite critical temperature for the precipitation of these proteins. The main conclusion drawn is that there are three main proteins present globulin about 3% of the total albumin-a about 85% and albumin-P about 12%; the last named is the crystallisable albumin. W. D. H. Leucoprotease and Anti-Leucoprotease of Mammals and Birds. (J. Exper. Bed. 1907 9 207-221).-The inhibiting action of the blood-serum on the enzyme of the polynuclear leucocytes (leucoprotease) is exerted by the albumin fraction of the serum ; the albumin fraction contains no proteolytic enzymes.The globulin fraction contains no anti-enzyme for leucoprotease ; i t contains on the contrary an enzyme which digests EUGENE L. OPIE and BERTHA L. BARKER118 ABSTRACTS OF CHEMICAL PAPERS. proteins in a neutral or alkaline medium. This which resembles leucoprotease is held in check by its anti-enzyme which is present in great excess. The anti-enzymotic activity of the serum of different animals varies considerably that of the rabbit for instance being stronger than dog’s serum when tested either with dog’s or with rabbit’s leucoprotease. The serum of birds (pigeon .and hen) almost completely fails to inhibit mammalian leucoprotease.The absence of the anti-enzyme is associated with an absence of leucoprotease in poly- nuclear leucocytes bone-marrow and spleen. W. D. H. Electrical Charge of Native Proteins and Agglutinins CYRUS W. FIELD and OSCAR TEAGUE (J. Exper. Xed. 1907 9 222-225).-Tetanolysin and anti-tetanolysin travel towards the cathode under the influence of an electric current ; the specific agglu- tinins are also electropositive; the protein matter of serum is not amphoteric but travels towards the cathode whether the reaction is acid neutral or alkaline. Hardy’s contrary results are attributed to the fact that he worked with “ denaturalised ” protein. The bacteria- agglutinin combination may be dissociated by means of the electric current.W. D. H. Oxygen Supply arid Saliva. ANTON J. CARLSOK and F. C. MCLEAN (Amer. J. Physiol. 1908 20 457-469. Compare Abstr. 1907 ii 891).-Further experiments confirming previous results are given. Stimulation of the cervical sympathetic does not increase the percentage of organic solids in the subsequent saliva obtained by stimulation of cranial secretory nerves or by the injection of pilo- carpine. Heidenhain’s statement to the contrary was due to itri perfect technique. This is considered to dispose finally of Heidenhain’s theory of trophic secretory nerves. Causes of Rise in Electrical Conductivity under the Influence of Trypsin. WILLIAM M. BAYLLIS (J. Phpsiol. 1907 36 221-252). -Fall of viscosity and liberation of adsorbed electrolytes from proteins will explain only a small fraction of the increase of electrical conductivity produced by tryptic action.The main cause is the production of peptones ” and amino-acids and especially of di- carboxylic acids and hexone basss. Amino-acids are more soluble in solutions of other amino-acids than in water but no evidence of salt formation was obtained. The hrmation of free carbaminoglycine and carbaminoalanine (Siegfried) is confirmed ; carbaminoleucine is also present. W. D. H. The Relationship of Dysoxidisable Carbon and Nitrogen on Different Diets. KARL SPIRO (Beitr. &em. Physiol. Path. 1908 11 144-145),-0n a protein diet the carbon nitrogen (C N) ratio of the urine falls because of the increase of urea in which the C N ratio is the lowest among urinary constituents. The carbon and nitrogen of the urine which are not in the form of urea or ammonia are spoken of as dysoxidisable ; the relationship of this form of carbon and nitrogen is on a flesh diet 1 5 ; on a carbohydrate diet 1 2.4 ; on a fat diet 1 3 ; and in inanition 1 2.38.W. D. H W. D. H.PHYSIOLOGICAL CHEMISTRY. 119 The Importance of So-called Plant-amides in Animal Metam bolism. VALDEMAR HENRIQUES and C. HANSEN (Zeitsch. physiol. Chem. 1907 54 169-187).-Experiments on rats show that if asparagine is the only nitrogenous substance in the diet it is unable to maintain equilibrium or to act as a protein-sparer. The same is true for amides separated from eight-day old germinating seedlings (F%ia fuba Phaseolus vuZgaris) or from potatoes and other vegetables.W. D. H. Nuclein Metabolism in a Dog with an Ecks Fistula. J. E. SWEET and PHCEBUS A. LEVENE (J. fi’xper. Ned. 1907,9 229-239).- I n a dog with an Eck’s fistula and on a purine-free diet the output of uric acid was much higher than in normal animals. Feeding with nucleo-protein only slightly raised the amount. Feeding with adenine had a similar effect but the experiment mas only done once ; indeed the whole series of observations are admittedly too scanty. Nucleic acid caused diuresis and a marked rise in the uric acid output some of which is attributed t o the diuresis. If thymin is injected part of it is eliminated by the kidneys but how much is absorbed and how much is decomposed in the intestinal tract was not ascertained.On a low protein diet the uric acid elimination suffered a marked fall. W. D. H. The Importance of Allantoin in Uric Acid Metabolism. WIL- HELM WIECHOWSKI (Beits.. them. Physi02. Pa& 1908 11 109-1 3 1). -On administration of uric acid to animals (dogs and rabbits) it is in part excreted as such but is mainly eliminated as allantoin which is therefore regarded as an end product of uric acid metabolism. W. D. H. Secretory Activity of the Pancreas Under the Influence of Hydrochloric Acid and Intestinal Extract. L. POPIELSKE (PJiiger’8 As.chiv 1907 120 451-491).-The work of Bayliss and Starling on secretin is criticised and the opinion advanced (and supported by experiments) that the injection of hydrochloric acid into the duodenum produces pancreatic secretion as the result of a nervous reflex.It is stated that extracts of all parts of the gastro-intestinal tract produce the same effect as the so-called secretin. W. D. H. The Nucleic Acid of the Pancreas. OTTO VON FURTH and ERNST JERUSALEM (Beitr. chem. Physiol. Path. 1908 11 146-150. Compare Abstr. 1907 i 993).-The pancreas contains as its principal nucleo-protein one which yields a nucleic acid differing in no essential points from that prepared from the thymus. The pancreas yields also another acid which is distinguished by its solubility in hot water (Hammarsten’s nucleo- protein Bang’s /3-guanylic acid) arid is of simpler structure its cleavage products being only guanine phosphoric acid and pentose. It is to this substance that the name guanylic acid should be restricted.W. D. H.120 ABSTRACTS OF CHEMICAL PAPERS. The SuperMal Layer of Cells and ite Relation to their Permeability and to the Staining of Tissues by Dyee. T. BEAILSFORD ROBERTSON (J. Biol. Chsm. 1908 4 1-34).-From experiments on the solubility of dyes in the presence of lipoids (ethyl acetate butyrate triacetin &c.) the conclusion is drawn that the theory of an oily layer on the surface of ceRs is untenable and that cell membranes are probably protein in nature ; proteins combine chemically with certain dyes. In many cases however a discontinuous lipoid layer may underlie the protein membrane. The Biological Importaiice of Lecithin. W. D. H. W. GLIKIN (Biochern. Zeitsch. 1907 7 286-298. Compare Abstr. 1907 ii 566).-A high percentage of lecithin in the bone-marrow is associated in newly-born animals with those species (both in birds and mammals) in which there is a helpless immature condition a t the time of birth.W. D. H. Action of Certain Metallic Ions on the Frog’s Heart. JEAN CAUTRELET (Compt. rend. 1907 146 1308-1309).-The following metals were dissociated electrically from their chlorides while introduced into the organism of the frog potassium copper and mercury were fouud to be toxic to the muscular tissue of the heart; magnesium poisons the heart by acting on its nerves. In the case of iron dissociated from ferric chloride both tissues are affected. Iron dissociated from ferrous chloride and calcium act tonically on the myocardium ; sodium and silver are inert. Consumption of Dextrose by Mammalian Cardiac Muscle.FRANK S. LOCKE and OTTO ROSENREIM (J. Physiol. 1907 36 205-220).-A new perfusion method is described by which a solution of dextrose in oxygenated Ringer’s solution can be repeatedly circulated through an excised rabbit’s heart. Five t o ten centigrams of the sugar disappear in eight to nine hours. This is not due to a minor metabolic or fermentative by-process but is associated with the main chemical change which underlies cardiac activity. If the activity of the heart is reduced by the omission of calcium (or better of both calcium and potassium) from the fluid the amount of sugar used up is lessened. No evidence was found of the formation of disaccharide in the h i d or of the storage of glycogen in the heart. The amount of carbon dioxide formed runs parallel with the disappearance of sugar.Lactic acid is absent and nitrogenous waste is very small. Contraction of Muscle and Receptive Substances. I. JOHN N. LANGLEY (J. Physiol. 1907 36 347-384).-The influence of uicotine on frog’s muscles varies in degrees in different muscles. The local application of the drug produces two main kinds of results namely local twitchings and prolonged tonic contractions. The former are rarely if ever produced except in the region of the nerve endings. The general bearing of the results recorded is deferred until a future paper but the theory is suggested that the normal tone of W. D. H. W. D. H.PHYSIOLOGICAL CHEMISTRY 121 muscles is maintained by an action on the special receptive substance which causes prolonged contraction when stimulated by nicotine that in some cases this may be restricted t o the neural region of the muscle fibre and that the tone is produced by a constant and not by an interrupted electric current (or -stimulus) passiiig down the nerves. W.D. H. Physical Chemistry of Excitation (of Muscle) and of Narcosis. RUDOLF HOBER (PJiiger’s Archiv 1907 120 492-5 16). -Isotonic solutions of normal salts of the alkali metals produce currents of rest of varying intensity and direction when applied locally to the non-injured sartorius muscle of the frog. When arranged according to their power of producing this current the various anions and cations form two series which coincide with those which have been deduced from their action on the solubility of egg- white and of lecithin (Compare Hober this VOI.ii 28; aIso as regards lecithin Porges and Neubauer this vol. ii 90). This coincidence is one of the reasons for the author’s conclusion that excitation and the electrical reaction accompanying it are closely connected with the consistency of the muscle colloids. Narcotics inhibit the change in the colloids (of the axis cylinder) which change accompanies the normal currant of action and in accordance with the current theory of narcosis due to Hans Meyer and Overton this colloidal change is supposed to occur in the lecithin. Narcosis would therefore consist firstly in the accumulation of the lipoid-soluble narcotic in the lipoid substance (lecithin) and secondly in the inhibition of the colloidal changes which excitation normally produces i n this substance. Influence of Inorganic Colloids on Autolysis.Part 111. Action of Poisons. M. ASCOLI and G. IZAR (Biochem. Zeitsch. 1907 7 142-151. Compare Abstr. 1907 ii 897).-The effects of various “ poisons ” on the catalytic acceleration of the autolysis of liver substance have been studied. They agree qualitatively and to some extent quantitatively wihh the effects on the decomposition of hydrogen peroxide by colloidal platinum (Bredig) and by blood catalase (Senter) which effects consist in a retardation of the action of the (inorganic or cirganic) ferment. A further analogy is especidly seen in the case of hydrocyanic acid namely that the ei€ect of traces of the poison on colloidal silver is not permanent. After forty-eight hours the silver recovers its activity so that it once more accelerates the autolysis.G. B. Behaviour of Human Milk to Rennet and Acids. BIANCA BIENENFELD (Biochem. Zeitsch. 1907 7 262-28 l).-Rennet does not curdle human milk ; after slight acidification and warming caseinogen is precipitated by rennet but this is the effect of the acid not of the rennet. Lactic acid also precipitates caseinogen and the precipitate contains only 16.2% of the total nitrogen. The remaining portions are precipitated by three-quarters saturation with ammonium sulphate. Human caseinogen appears to contain a carbohydrate complex. G. B. W. D. H.122 ABSTRACTS OF CHEMICAL PAPERS. Gases Produced in the Alimentary Canal of Goats. ARTHUR E. BOYCOTT and (3. C. C. DAMANT (J. Phylsiol. 1907 36 283-287).- Goats produce a large quantity of carbon dioxide (about 9 litres per day in a goat weighing 20 kilos).The amount of combustible gas (hydrogen and methane) varies from 3.5% to 6.6% of this; the pro- portion between the two gases averaging 1 2. Ten % of the total carbon dioxide a t least is not the result of tissue metabolism but leaves the alimentary canal and is produced there by fermentation. W. D. H. The Action of Various Chemical Substances on Sugar Excretion and Acidosis. 11. JULIUS BAER and L ~ O N BLUM (Beitr. chem. Physiol. Path. 1908 11 101-108. Compare Abstr. 1907 ii 640).-A previous research has dealt with the action of glutaric acid in lessening the sugar excretion and acidosis in phloridzinised dogs. Several other acids of the same series were investigated ; adipic acid (C=6) and pimelic acid (C=7) act in the same way but less powerfully ; suberic acid (C = 8) is still less powerful and azelaic acid (C =9) and sebacic acid (C = 10) have no action at all.The higher acids are less easily burnt in the body more passing unchanged into the urine but this appears to be only one factor concerned. Benzoic acid does not act like glutaric acid. W. D. H. Detection of Glyoxylic Acid and its Occurrence in Human Urine. F. GRANSTROM (Beitr. chem. Physiol. Path. 1908 11 132-142).-The different colour reactions which indole scatole and tryptophan give with glyoxylic acid formaldehyde and other aldehydes are described. Eppinger's test for glyoxylic acid in urine is criticised. Although it is sometimes possible to detect indole and scatole it is very doubtful whether glyoxylic acid ever occurs in human urine normal or pathological.W. D. H. Uric Acid of the Urine. DETERMEYER and WAGNER (BiocAem. Zeitsch. 1908 7 369-395).-Various factors playing a part in the condition of solution or precipitation of uric acid in the urine are considered. The most important are (1) solution owing to salt formation with inorganic bases ; (2) precipitation of free uric acid by organic acids and (3) inhibition of this precipitation by certain organic substances such as urochrome. W. D. H. Doubly-Refracting Substances from Pathological Organs. THEODOR PANZER (Zeitsch. physiol. Chem. 1907 54 239-254).-The crystalline doubly-refracting substance separated from diseased kidneys and previously called protagon is really an oleic acid ester of cholesterol.Further details of its preparation and properties as obtained from kidneys and other diseased structures are given and the question of the meaning of cholesterol in the body discussed. W. D. H. Lactic Acid in Eclampsia. A. TEN DOESSCHATE (Zeihh. physiol. Chem. 1907 54 153-168).-Sarco-lactic acid is undoubtedly presentVEGETABLE PHYSIOLOGY AND AGRICULTURE. 123 in the blood and the urine of the mother and in the umbilical blood of the fetus in cases of eclampsia. This substance however is not the cause of the convulsions as has been supposed but the result either of the convulsions or of the kidney disorder which underlies them. Hopkin’s new test for lactic acid was used and quantitative results in numerous cases given. Protein Metabolism in Poisoning by Bromobenzene. W. McK~M MAHRIOTT and CHARLES G. L. WOLF (Biochem. ZeitschmJ 1907 7 2 13-26 l).-In animals bromobenzeno increases the output of nitrogen; the relation between the different forms of excreted nitrogen is not markedly altered. The sulphur excretion runs parallel to this the ‘‘ neutral sulphur ” and ethereal sulphates being especially increased. During inanition these effects are still more marked but there is no acidosis. The drug produces no change in the excretion of amino-acids or i n the respiratory quotient. After death the liver and kidney cells are found to have undergone necrotic changes. W. D. H. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9089405117

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGRICULTURE. 123 Chemistry of Vegetable Physiology and Agriculture. Actionof Chlorine in the Tubercle Bacillus. Moussu and GOUPIL (Compt. rend. 1907,145,1231-1 232).-The resistance t o acids of the various constituents of the tubercle bacillus is one of its charac- teristic properties and this is not destroyed by various reagents which destroy the bacilli (alcohol ether chloroform light petroleum potass- ium hydroxide &c.). Exposure to chlorine however breaks up the bacilli and they lose then their acid-resisting property. W D. H. Phosphorus in the Fat of Micro-Organisms. E. ALILAIRE (Conzpt. rend. 1907 145 1215-1317).-The fatty matter of numerous micro-organisms contains phosphorus. The only exception found was Chlorelh vulgaris in which the total amount of f a t is small and chlorophyll is abundant.On the supposition that lecithin is present the iodine test for choline after saponification mas tried but with negative results. W. D. H. Influence of Organic Matter on Nitrification in Impure Cultures. ADA% KARPI~SKI and BR. NIKLEWSKI (Rul. Acad. Xci. Cracow 1907 596-615).-The presence of small amounts of some organic substances is favourable to nitrification in mixed cultures ; soil extracts humates and acetates were found to be favourable and even peptone and sugar in small quantities quickened nitrification in the first generations. The strength of solutions does not seem t o be of much importance favourable eff ecta being produced especially in the case of humates by extremely small amounts. N. H.J. M.124 ABSTRACTS OF CHEMICAL PAPERS. Microbiochemical Formation of Ammonia in Soil. RENATO PEROTTI ( A t t i R. Accad. Lincei 19U7 [v] 16 ii 704 -709. Compare Abstr. 1906 ii 304). -Calcium cyanamide undergoes a biochemical change in soil its nitrogen being converted into ammonia whilst dicyanodiamide does not undergo this chaoge but is utilised directly by various organisms. The explanation of this difference in bebaviour seems to lie in the fact that calcium cyannmide is poisonous i n nature whilst dicyanodiamide in moderate concentrations is not. When the dicyanodiamide is increased in concentration to such a n extent as to render it poisonous the soil bacteria attack it converting its nitrogen into ammonia. Favourable Influence of Small Quantities of Zinc in the Growth of Sterigmatocystis nigra.MAURICE JAVILLIER (Compt. Tend. 1907 145 1212-1215).-Raulin in 1870 described the favouring influence of small quantities of zinc on the mould mentioned above known also as AsyergilEus niyer. Coupin attributed this to the antiseptic action of t h e zinc preventing the growth of other micro- organisms. The present research coufirms Raulin's view that zinc is of real nutritive importance. The Organic Compounds of Nitrogen Phosphorus and Sulphur in Vegetables. ALBEET STUTZEH (Biochem. Zeituch. 190 7 471-487).-A method for the estimation of phosphorus and sulphur in orgatric union (as lecithin &c.) in vegetable tissues is described. Schulze's observatioiis on the value of orgauic phosphorus compounds in plants and especialIy in seeds are confirmed.After gastric digestion of vegetables the in*olu ble residue contains nitrogen phosphorus and sulphur in organic combination but the proportion of the three elements varies. The same is true for the fawes of sheep fed on various vegetables. The nature of the organic sulphur compounds is not known. EDMUND 0. VON LIPPMANN (Ber. 1907 40 4936-4937).-An appreciable amount of crystallihed quercitol was found between the woud and the bark of a recently felled oak. T. H. P. W. D. H. W. D. H. Occurrence of Quercitol. J. J. S. Occurrence of Salts of Anhydroxymethylenediphosphoric Acid or Phytin in Planta UMETARO ~ U Z U K I and K. YOSHIMURA (Bull. CoEl. Ayri. T6ky6 1907 7 493-502).-The amount of organic phosphorus soluble in 0.2% hydrochloric acid represents approximately the amount of phytin present in plants.The following results (per cent. in dry matter) were obtained Phosphorus Total. Rice bran ........................ 2.27 Wheat bran .................... 1'114 Seeds of Sesamum indieum ... 0.772 Seeds of IZicinus communis .. 0'261 011 cake (Brassica n a p s ) ...... 1.195 Barley bran ........................ 0.541 Bran from Paniczcm frzcment. 0.765 as lecithin. 0.02 0.010 0.030 0.013 0.034 0'010 0.026 Soluble in 0'2% HCll Organic. 1.68 0.579 0.1 25 0.109 0.532 0.344 o 238 Inorganic. 0 9 3 0-050 trace trace trace 0.089 traceVEGETABLE PHTSIOLOGY AND AGRICULTURE. 125 Preparations from rice bran which amounted to 743% of the dry matter gave the following results loss on ignition 27.31 ; P 23.48 &lg 17.48 and Ca 5.18%. Pectins from the Fruits of Lonicera Xylosteum Symphori- carpus Racemosa and Tamus Communis.MARC BRIDEL (J. Phaiwz. Chim. 1907 [vi] 26 536-543).-The pectins obtairied from Lonicercc Symphoricurpus and Tarnus by Bourquelot and HBrissey's method (ibid. 1898 [vi] 7 473) gave aD +183*36" +190.9" and + 111.42O (200 mm.) respectively. All three yield muck acid when treated with nitric acid are coagulated by barium and calcium hydroxides rtnd by pectase and are rendered incoagulable by malt pectase. The pectin from Lonicera Xplosteum yielded arabinose when hydrolysed with sulphuric acid N. H. 5. M. N. H. J. M. Composition of Tea Leaves at Various Stages of Develop- ment. SHIN SAWAMURA (BuZ2. Imp. Centr. Agric. Exper. Stat. Japan 1907 1 145-146.Compare Kellner Abstr. 1887 73).-The relative weights of the first second third and fourth leaves and the twigs were 100 203 412 577 and 717 and they contained respectively 72-48 71.98 73.28 74.54 and 83.91% of water. The composition of the dry matter mas as follows Ether 37-free Crude Pure extract. extract. fibre. Theine. Tannin. N. ash. 1. 6.91 18'40 10-87 3.578 13.97 7'545 4.969 2. 7.90 13'65 10'90 3-559 16'96 6.727 4988 3. 11.35 18.50 12'25 3.232 15-78 6-294 4'867 4. 11-43 20'73 14'75 2.570 15.44 5'504 4.935 5. 8.03 26.96 17.08 2-146 11'14 5'112 6'249 N. H. J. 15. Carbohydrate Metabolism of the Sugar Beet (Beta vulgaris). SIEGFRIED STRAKOSCH (Zeitscl.. Ver. deut . Zuckerind. 1907 623 1057-1068).-The author's results are briefly as follows. Dextrose is formed in the mesophyll of the whole surface of the leaves of Beta vulgaris and is the only sugar found in the mesophyll.The migration of dextrose into the leaf veins is followed by the appearance of lzvulose therein and later by the formation of sucrose. The formation of starch in the chlorophyll granules occurs subsequently to the production of sucrose from its components and only after the carbohydrates have accumulated to some extent in the mesophyll. Evidence is obtained in support of the view that the sucrose in the leaves of the beet must be regarded as the final product and that it migrates to the root as such. The conversion of the monosaccharides of the leaf into sucrose is connected with the action of light and ceases when the leaf is placed in the dark.The amount of the mono- saccharides in the leaf is not appreciably altered by the migration of the sucrose into the root. This amount is not perceptibly diminished when the leaves remain in the dark for a long time neither does pro- longed exposure of the leaves to the action of light cause it to increase beyond a certain maximum attained in a short time. T. H. P. VOL. XCIV. ii. 9126 ABSTRACTS OF CHEMICAL PAPERS Darkening of Beet Juice. MAX GONNERMANN (Zeitsch. r e i s . deut. Zuckerind. 1907 623 1068-1 087. Compare Abstr. 1899 ii 790).-Sugnr beet juice contains organic ferrous salts tyrosinase and catechol the last named being probably formed by the action of tyrosinase on tyrosine. These substances produce no colouring matter in absence of air but access of the latter to the liquid causes rapid darkening especially if a trace of ammonia is present.The author has isolated catechol from the juice. T. H. P. The Most Favourable Ratio of Lime to Magnesia for the Mulberry Tree. M. NAKAMURA (BUZZ. Imp. Centr. Agric. Exper. Stat. Japan 1907 1 129-133).-The best ratio for mulberry trees was found in accordance with previous observations by As. to be CaO/MgO = 3/1 N. H. J. BE. Influence of Stimulating Compounds on Cropa under Different Conditions. S. UCHIYAMA (Bull. Imp. Centr. Agm'c. Exper. Stat. Japan 1907 1 37-79).-A large number of plot experiments are described in which various plants were grown with- out and with manganese sulphate. The soil was a diluvial loam rich in organic matter and contained 0.076% Mn,O soluble in 1% citric acid and 0.413% soluble in hot 10% hydrogen chloride. In the caseof wheat and barley very little effect mas produced by manganese sulphate whilst grasses buckwheat radishes carrots Bvassica campegtyis and tea plants were considerably benefited.Ferrous sulphate was also found to be beneficial in some cases but less so than manganese. I n some cases a mixture of the two sulphates gave the best results. The amounts of manganese sulphate varied from 10 to 37.5 kilos. per hectare (reckoned as Mn,?,). Better results were obtained when it was applied as a top dressing than with the other manures. Further experiments in which plants grown in bottomless cylinders received varying amounts of manganese sulphate showed in each case a more or less stimulating action.In the case of barley the grain and total yield were increased 18% and 24% respectively by 25 kilos. of &ln,04 per hectare both smaller and larger applications producing less effect. The effect of manganese depends to some extent on the nature of the soil being greater on loam than on sandy soil; the effect is diminished by a1 kaline manures. Potassium iodide increased the yield of Panicum miliuceum (28%) and of barley (34%) the most suitable amounts being 376 and 500 grams per hectare respectively. Sodium fluoride has a powerfully stimulating action on Panicum and also increased the yield of barley ; the amounts of fluoride applied were 940 and 5000 grams per hectare N. H. J. M. Distribution of Solute Between Water and Soil. PRANK K. CAMERON and HARRISON E.PATTEN (J. Physicacl Chent. 1907 11 681-593).-The authors have studied the distribution of various solutes (gentian-violet sodium eosin manure extract) between water and various soils. The distribution of solute between solvent and absorbent presents the same general characteristics with soils as wlthVEGETABLE Pm’sIoLocP ASD AGRICULTURE. I 2 7 other absorbents.- For any series of soils or other absorbents the order of the absorptive capacities for one solute may be quite different from the order for another solute The distribution of a solute between solvent and absorbent may generally be represented by the formula C?z/C = K where n may be less than equal to or greater than unity. When soils however are the absorbents the flocculation introduces a modifying factor and the form of the distribution equation may become more complex. SHIGEHIRO SUZUKI (BUZZ.COX Agric. Tokio 1907,7,513-529. Compare ibid. 419 and Abstr. 1906 ii 889).-Tiie nitrogen of humus is mainly in the form of a kind of protein only traces of amino-acids being present. Udrhszky’s artificial nitrogenous humic acid obtained by boiling dextrose and urea with hydrochloric acid (Zeitsch. physiol. Chein. 1888 12 42) cannot therefore resemble natural humus. The following substances were obtained by treating humic acid (500 grams) with hot concentrated hydrochloric acid alanine 2.39 ; leucine 2.16 ; aminovaleric acid 0.57 ; impure aspartic acid 2.16 ; copper salts of active and inactive proline 0.67 and 0.50; copper salts of unknown acids 30.30 and ammonia 1.90 grams.Qlutamic acid tyrosine and histidine were also present. N. H. J. RI. J. C. P. Humus Formation. Sodium Nitrate Compared with Ammonium Sulphate. PAUL B~SSLER (Bied. Zentv. 1907 36,857 ; from .7arlLresber. Agrik-chem. Versuchs. u. Samenkontrollstat. Koslin 1905-1906 14).-The greatest effect with potatoes was produced when the manures were applied in two portions before planting and before the second hoeing. The two manures gave practically the same result. The warst results were obtained by applying the whole amount of the manures before planting ; ammonium sulphate produced considerably less effect than sodium nitrate. N. H. J. M. Behaviour of Nitrate in Paddy Soils. G. DAIKUHARA and T. IMASEKI (Bull. Imp Centr. Agric. Exper. Stat. Jccpan 1907 1 7-36.Compare Nagaoka Abstr. 1905 ii 837).-Results of determina- tions of dextrose and sucrose in paddy rice and in dry land rice at three or four periods ofLgrowth showed that the amount of sugar is practically the same and further that manuring with ammonium sulphate and sodium nitrate respectively has no effect on the sugar content. The low yields of rice obtained when nitrate is employed cannot therefore be due as suggested by Nitgaoka t o deficiency of sugar in paddy plants. The unsuitability of nitrate for paddy soils is due to loss of nitrogen by denitrification to the greater production of poisonous nitrites on paddy soils as compared with dry land and to loss of nitrates by the system of irrigation. Even in the case of dry land there may be some loss by denitrification in the subsoil; in rainy seasons when organic manures have been applied along with nitrate denitrification may be energetic in the subsoil and may also take place in the surface soil.9-2125 ABSTRACTS OF CHEMICAL PAPERS. When nitrates are applied t o paddy soils it is best t o avoid the use of organic manures unless in a well-rotted condition. N. H. J. M. Manurial Effect of Calcium Cyanamide under Different Conditions. s. UcHrYma (Bull. Imp. Centr. Agric. Exper. Stat. Jcipan 1907 1 93-103).-Pot experiments with barley and Brassicn canzpeslris in loamy and sandy soils. Calcium cyanaivide acts best under conditions approaching neutrality. Under favourable conditions it is equal t o ammonium sulphate ; the results were less favanable on sandy soil than on loam.Ammonium sulphate gave better results in conjunction with sodium phosphate than with superphospkate. Manuring with Bone Dust. S. UCHIYAMA (Bull. Imp. Ceittr. Agric. Exper. Stat. Japan 1907 1 105-120).-The results of sand- cuiture experiments with barley showed t h a t the availability of bone dust is diminished by magnesite and that it is less in conjunction with sodium nitrate than with ammonium sulphate. I n the case of sandy soil it was found that potassium sulphate and carbonate in presence of bone dust and sodium nitrate gave similar results. Wood ash and bone dust may therefore be used together. Bone dust (25 grams) kept in contact with water (2.5 litres) for four and a-half months showed an increase of 70% soluble P,O over the amount dissolved in the same time in presence of chloroform. The presence of potassium carbonate had a far greater effect than bacteria. N.H. J. M. N. H. J. M. Behaviour of Bone and Mineral Phosphates in Soil. CARLO MONTANART (Bied. Zenlr. 1907 36 797-801 ; from Stax. sper. agrcw. itat. 1906 39 323).-The absorptive power of soils for soluble phosphates depends on the amounts of alkaline earth carbon- ates of iron and aluminium oxides and especially of humus substances. The continued employment of phosphates diminishes the amount of alkaline earth carbonates in the soil di- and tri-phosphates being produced. There is also a diminution of alumina and iron oxide a withdrawal of the alkali of clay producing substances and consequently a diminution of the absorptive power of the soil and productiou of free silicic acid.N. H. J. M. Are Soils containing Iesa than 0.02% SO Benefited by Special Manuring with Sulphates 3 G. DAIKUHARA (BUZZ. Imp. Ceprtr. Agyic. Exper. Stat. Japan 1907 1 135-143).-Results of pot experiments in which barley was grown in three soils containing respectively 0.016 0.013 and 0*010% of sulyhuric acid (as SO,) showed that these amounts sufficed to meet the needs of barley. N. H. J. M. Influence of Solubility on Availability. G. DAIKUHARA (Bull. Imp. Centr. Ay~ic. Exper. Stat. Japan 1907 1 87-91. Compare Abstr. 1906 ii 388).-When calcium is present asANALYTICAL CHEMISTRI'. 129 carbonate the necessary amount of magnesium (as crystallised sulphate) for barley in sand culture is very small the best ratio of lime to magnesia being 60 1. I n water cultures containing calcium and magnesium nitrates the best ratio is between 1 1 and 2 1. This holds good for sandy soils whilst in clay soils the ratio CaCO MgSO mill vary (compare Nakamura Abstr. 1906 ii 389). I n the case of barley the agronomic equivalents of crystallised magnesium sulphate and msgnesite are as 4.9 100 ; with rice the equivalent is 9.8. G. DAIKUHARA (Bull. Imp. Centr. Agric. Ercpsr. Stat. Jchpan 1907 1 81-86).-Magnesium sulphate is the moqt effective magnesium compound to employ for regulating the lime factor and it is best to apply it annually as a top dressing in small quantities. On R loamy humus soil 10 parts of the salt (MgSO4,'7H,O) are agronomically equivalent to 100 parts of the finest-ground magnesite. N. H. J. M. Manuring with Magnesium Sulphate. N. H. J. M.

ISSN:0368-1769    

DOI:10.1039/CA9089405123

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRI‘. 129 Analytical Chemistry. ass-generating Apparatus for Analytical Purposes. EUCIEN M~~LLER (Chem. Zeit. 1907 31 1257).-A modification of J. M. Sanders’s appargtus (ibid. 1184). As now constructed i t consists of n U-tube with two or only one ground stoppers and a gas-delivery tube. The advantages gained are saving of material obtainment of a pure (washed or dried) gas and proper regulation of the gFs- current. L. DE K. Estimation of Organically-combined Iodine and Chlorine in (‘ Erythrosine.” FERDINAND JEAN (Ann. Chim. anccl. 1908 13 12-14 *).-Two portions of 0.6 gram each are burnt to ash one with addition of 0.5 gram of sodium carbonate 0.5 gram of potassium carbonate and 5 grams of ma.gneFium oxide. The ashes are treated with water the solutions are carefully neutralised with acetic acid made up to 100 c.c.and the iodine and chlorine are estimated. The difference between the results of the two ashes is then due t o organically-combined iodine or chlorine. The estimation of the halogen is carried out as follows 50 C.C. of each solution are titrated for iodine only by Pisani’s method (#/I0 silver in presence of iodide of starch). The other 50 C.C. are then titra.ted with N,lO silver for joint iodine and chlorine using potassium chromate as indicator. L. DE K. Estimation of Total Sulphur in Urine. RUGO SCHULZ (Pfiiger’s Archiv 1907 121 114-116).-Ten C.C. of urine are heated in a round-bottomed flask with 10 C.C. of fuming nitric acid; the * And Bztll. Xoc. CII&IL Belg 1908 22 45-46.130 ABSTRACTS OF CHEMICAL PAPERS.heating is continued for about fifteen minutes that is until all violent action has ceased and the contents of the flask are then cooled. Water and hydrochIoric acid are now added the solution is trans- ferred to a beaker and the sulphuric acid is precipitated in the usual way as barium sulphate. w. P. s. Assay of Highly Concentrated Sulphuric Acid. ERNST BUCHWALD (Chein. Zeit. 1907 31 1256).-About 5 grams of the sample are weighed accurately in a small weighing bottle and then made np t o a litre. The solution is placed in a burette and run into a flask containing 50 C.C. of accurately prepared N/lO sodium hydr- oxide free from carbon dioxide and coloured with phenolphthalein until the liquid is decolorised. Good results are also obtained by K jeldahl’s iodometric process (liberation of iodine from a mixture of potassium iodide and iodate).L. DE K. Titration of Sodium Thiosulphate. THADDEUS MILOBENDSKI (J. Russ. Phys. Chem. Soc. 1907’30 Chem. 1404-1411).-The three methods of titrating sodium thiosulphate namely those of Zulkowsky and of Volhard and direct titration with iodine have been found to be equally good ; but in cases where the iodine is only very slowly liberated the thiosulphate should be titrated by Zulkowsky’s method without however allowing as usual half an hour for the completion of the reaction. Z. K. Modification of Kj eldahl’s Process for Estimating Nitrogen in Foods. REMO CORRADI (Boll. d i m . farm. 1907 46 861-864). -2.5 Grams or if the amount of the nitrogen is less than 3% 5 grams of the food are weighed dried in a steam-oven and heated for five t o six hours in a Kjeldahl flask with 30 C.C.of fuming sulphuric acid. The colourless or pale yellow liquid is intro- duced into a 250 C.C. flask containing about 40 C.C. of water the cooled solution being then rendered faintly acid by means of 20% sodium hydroxide solution and finally made up t o volume. Twenty- five C.C. of the liquid are then treated with 25 C.C. of sodium hypo- bromite solution prepared by mixing 25 C.C. of bromine 350 C.C. of 30% sodium hydroxide solution and 275 C.C. of water. The nitrogen evolved is measured in a slightly modified DuprB’s azotometer (compare Abstr. 1906 ii 505) the volume being increased by 1.7%. This method gives numbers differing insensibly from those obtained by the ordinary Kjeldahl proceEs.Employment of Nitron- for Determining Nitrates in Soils and Plants. JAKOB LITZENDORFF (Zeitsch. angew. Chem. 1907 11 2209-223 I).-Correct results are obtained with soils containing 20-30 parts per million of nitric nitrogen. When however smaller amounts are present the extracts have to be evaporated down and in this process substances are produced which hinder the separation of the nitrate. This difficulty can be overcowe by repeatedly adding hydrogen peroxide to the extract during evaporation and by heating T. H. P.ANALYTICAL CHEMISTRY. 131 the sufficiently concentrated extract with hydrogen peroxide in a flask in boiling water for several hours until decolorised. N. H. J. M. Estimation of Phosphorus in Calcium Carbides F.WILLY HINRICHSEN (Chem. Zentr. 1907 ii 1356-1357; from Mitt. K. MateriaZpriiyg.-Amt. Gyoss. Lichterfeelde Vest 25,110-1 12)-On pass- ing impure acetylene through a solution of sodium hypochlorite ex- plosions occur now and then and the phosphorus is not completely absorbed as it occurs in part as an organic phosphorus compound. The process recommended by Lidholm (Ahstr. 1904 ii 776) gives satisfactory results. L. DE K. A New Modiflcation of Petermann’s Method for Estimating Citrate-Soluble Phosphoric Acid in Precipitated Calcium Phosphate (Futterkalk). GUSTAV FINaERLTNG and ADOLF GROM- BACH (Zeitsch. anal. Chm. 1907 46 756-761).-0ne gram of the sample is put into a 2OOc.c. flask and moistened with 5 C.C. of alcohol 100 C.C. of Petermann’s alkaline citrate solution are added and the whole is rotated for half an hour.The liquid is then heated a t 40° for another hour with constant shaking and when cold diluted with water to 200 C.C. and filtered. One hundred C.C. of the filtrate are mixed with 20 C.C. of strong nitric acid evaporated t o half the bulk and when cold neutralised with ammonia and mixed with 50 C.C. of Hallenser’s solution. To the cold solution are then added drop by drop 20 C.C. of magnesium mixture and after shaking for half an hour the precipitate may be collected. L. DE K. Detection of Arsenic by Means of the Marsh Apparatus. HEINRICH STRUVE (Zeitsch. and. Chem. 1907 46 761-764).-The author recommends the use of sheet zinc which almost invariably he finds to be free from arsenic. Addition of activating agents are Estimation of Commercial Silicon ; Separation of Silica and Silicon.FRITZ LIMMER (Chem. Zeit. 1908 32,42).-0-25-0.50 Gram of the finely-powdered sample is heated in a slow current of dry chlorine care being taken not to apply heat until every trace of air has been expelled from the apparatus. The silicon (also aluminium iron &c.) is volatilised whilst the silica remains in the residue which is then tested in the usual way by fusion with alkali carbonate &c. The silica is deducted from the amount of total silica obtained from a separate portion of the sample and the difference calculated into superfluous. L. DE K. silicon. L. DE K. Estimation of Carbon in Pig-Iron and Steel MAX ORTHEY (Chem. Zeit. 1908 33 31-33).-A criticism of some of the methods used for the estimation of carbon in iron or steel.Sarnstrom’s modified chromic acid process and the copper ammonium chloride method are quite satisfactory for the ordinary kinds of iron. The method of burning in a current of oxygen in presence of bismuth oxide gives good results with all kinds of iron. I n the case of samplcs132 ABSTRACTS OF CHEMICAT PAPERS. oxidised with great difficulty the chlorine process may be used as a check. Some other recognised methods were tried but with less satisfactory results L. DE K. The Use of Silver in the Combustion of Nitrogenous Substances. F. EPSTEIN and RICHARD DOHT (Zeitsch. anal. Chew. 1907 46 771-773).-A silver spiral 10 cm. long heated to intense redness is again recommended instead of metallic copper in order to decompose the nitrogen oxides formed i n the combustion of nitrogenous organic substances (C and H estimation).Silver also effectually retains halogens. L. DE K. Dennstedt's Method of Elementary Analysis Applied t o the Hzemoglobin Derivatives. JEAN ZALESKI (Bull. Acad. Sci. Cracow 1907 ii 646-651).-The elementary analysis of substances such as acetonehaemin or iodohaemin (Merunowicz and Zateski ibid. 633) is attended with great difficulty when ordinary methods are employed but is rendered simple by the use of Dennstedt's method (compare Abstr. 1906 ii 51). G. B. Estimation of Carbon Dioxide in Electrolytic Chlorine. PETER PHILOSOPHOFF (Chent. Zeit. 1907 31 1256-1257).-The author (Abstr. 1907 ii 908) now dispenses with the use of brine in order to facilitate the readings and reads off the volume of the gas before and after absorption by means of a graduated levelling tube attached to the Bunte burette and filled with mercury.L. DE K. Quantitative Estimation" of Metals in Organic Substances. J. ROTRE (Chem. Zentr. 1907 ii 1362-1364; from Mitt. K. &fate&Iprufs.-Amt. Gross. Lichterfdde West 25 105-1 06) .-The dried substance is heated in a round-bottomed flask with 15 C.C. of fuming nitric acid and 2 C.C. of sulphuric acid for every gram taken at first gently afterwards,more strongly on a sand-bath. Substances which are readily inflammable are first moistened with four times the weight of nitric acid D 1.4. When sulphuric fumes begin to appear the contents are allowed to cool and another portion of nitric acid is added and t h i s operation may be repeated if necessary. Finally the bulk of the sulphuric acid is driven off and any metal will be found in the residual mass.L. DE K. Analysis of Sodium Peroxide. R. NIEMEYER (Chem. Zeit. 1907 31 1257)-With care the permanganate method gives trustworthy results. 0.15-0.2 Gram of the peroxide is weighed out in a little dish placed in a weighing tube. This is then seized with a pair of tongs and quickly immersed in a beaker containing 500 C.C. of water; care should be taken that none of the peroxide floats on the surface as otherwise the experiment fails. A sufficiency of dilute sulphuric acid is now added and the liquid titrated at once with iV/ 10 permanganate. L. D E K ,ANALYTICAL CHEMISTRY. 133 Quantitative Separation of Barium from Strontium.ZELDA KAHAN (Analyst 1908 33 12-14).-The method proposed depends on the precipitation of the barium as chromate in ammonium acetate solution. The solution containing the barium and strontium salts is treated with ammonium dichromate solution until precipitation is ne;trly complete ; the dichromate solution is added drop by drop with constant stirring. Ammonium acetate solution is then added until the solution becomes colourless a few more drops of the dichromate solution are added so that the solution remains pale yellow and next a little more ammonium acetate solution. After the lapse of about three hours the precipitate of barium chromate is collected in a Gooch crucible washed with ammonium acetate solution until the filtrate gives only a slight coloration with silver nitrate solution and is then w.P. x. dried at a temperature of 180’ and weighed. Estimation of Mercuric Chloride in Pastilles. UMBERTO SAPORETTI (Boll. chinz. farm. 1907 46 S65-867).-The amount of mercuric chloride contained in pastilles used for antiseptic purposes may be readily estimated as follows. Five of the pastilles are dissolved in water in a porcelain basin or crystallising dish with tall sides and t o the solution decolorised with chlorine water or dilute hydrochloric acid sodium hypophosphite is added gradually as long as any action takes place. The finely-divided mercury is then caused t o collect into a globule by gently boiling the solution and is washed with dilute hydrochloric acid. The amount of mercury is estimated by weighing or measuring.For the latter estimation the author has devised a narrow burette or (‘ hydrargyrometer,” by means of which the weight of mercuric chloride per five pastilles can be read off directly. T. H. P. Estimation of Manganese in Potable Water. EDMUND ERNYEI (C‘iiem Zeit. 1908 32 41-42).-The sample is acidified with sulphuric acid and any iron removed by shaking with a slight excess of zinc oxide. One hundred C.C. of the filtrate are mixed with 5 C.C. of 3076 sulphuric acid the chlorine is removed with slight excess of silver sulphate and the whole is boiled for twenty minutes after adding 1-2 grams of potassium persulphate. When cold the liquid is made up t o the original volume; the permanganate formed is evtimated by adding potassium iodide and titrating with N/100 thiosulphate with starch as indicator.The process may be used also for the estimation Detection of Nickel as Double Nickel Ammonium Molybdate. 31. EMMANUEL POZZI-ESCOT (Ann. Chim. and. 1908 13 16. Compare Abstr. 1907 ii 818).-A modification of the author’s previous test for nickel. The neutral or slightly acid solution is mixed with a small quantity of saturated solution of ammonium molybdate and then with a large excess of saturated solution of ammonium chloride. The mixture is heated gently when should nickel be present it becomes turbid-in a few minutes. of manganese in ferruginous water deposits. L. DE K. L. DL K.134 ABSTRACTS OF CITEMICAL PAPERS. Volumetric Estimation of Tin by Means of Potassium Dichromate.H. REYNOLDS (Chem. News 1908 97 13-1 5). - The process is based on the fact that sulphonated azobenzene is bleached by stannous chloride,rand that the red colour is restored by potassium dichromate. The metal is dissolved in hydrochloric acid inacurrent of carbon dioxide free from oxygen a definite amount of potassium dichromate (1 C.C. -0.01 gram of tin) very nearly sufficient to complete the oxidation is added and then sufficient of the indicator to fully mask the green colour of the reduced chromate. More dichromate is now added until the colour changes t o red. The process may be used for the assay of ferro-tin and Britannia metal L. DE K. New Method for Separating Titanium and Zirconium. MAX DITTRICH and 5. FREUND (Zeit.sch. anorg. Cl~m. 1907 56 344-345).-The method depends on the fact that a neutral solution of titanium nitrate gives in the cold with ammonium salicylate a precipitate (titanium salicylate) easily soluble in hot water whilst the corresponding precipitate with zirconium nitrate is insoluble in exces of the reagent.A solution of the mixed nitrates neutralised with sodium carbonate is added drop by drop to a boiling concentrated solution of ammonium salicylate (1 salt to 5 water). The solution is then boiled for some time concentrated filtered the precipitate ,washed with a boiling solution of ammonium salicylate until free from titanium and the zirconium then estimated as dioxide. The titanium is precipitated from the boiling filtrate with excess of ammonia and also estimated as the dioxide. G. 5.Separation of Titanium and Thorium by Means of Ammonium Salicylate. MAX DITTRICH and S. FREUND (Zeitsch. unorg. Chem. 1907 56 346-347).-The separation is effected exactly as described in the preceding abstract; thorium like zirconium being completely precipitated from a neutralised solution of the nitrate when the latter is slowly added t o a boiling concentrated solution of ammonium salicylate. G. 8. Simultaneous Precipitation of Titanium and Zirconium in the Presence of Iron. MAX DITTRICH and 8. FREUND (Zeitsch. anorg. Chen?. 1907 56 337-343. Compare Abstr. 1905 ii 287).- Four methods for the simultaneous precipitation of titanium and zirconium salts from a mixture also containing iron are given. A complete separation in t'he presence of sodium acetate is possible when the iron is in the ferrous st,ate.The mass obtained by fusing a mix- ture of the three salts with acid potassium sulphate is dissolved in water saturated with hydrogen sulphide filtered nearly neutralised with sodium carbonate and the hydrogen sulphide removed by passing a stream of carbon dioxide through the hot solution. Then whilst the solution is protected from oxidation by means of carbon dioxide excessANALYTICAL CHEMISTRY. 135 of sodium acetate is added the solution heated for one hour and the mixed precipitate of titanium and zirconium removed by filtration. According to another method which has some advantages ammonium sulphate is used inetead of acetate otherwise the procedure is the same as above. The titanium and zirconium are obtained as oxides.The separation in question may also be effected by means of sulphurous acid or sodium thiosulphat'e; full details are given in the paper. The titanium in the mixed precipitate is estimated colorimetrically with sulphuric acid and hydrogen peroxide and the zirconium by difference. G. S. Separation of Thorium Titanium and Zirconium from Iron. MAX DITTRICH and S. FREUND (Zeihch. anorg. Chem. 1907 56 348-352. Compare preceding abstracts).-It is shown that the com- plete separation from iron of (a) titanium and thorium ( b ) thorium and zirconium (c) titanium zirconium and thorium can be effected by the sodium acetate method described in the preceding abstract. I n order to separate the individual oxides from the mixture of the three oxides obtained in ( c ) they are converted into nitrates the zirconium and thorium are precipitated with ammonium salicylate as described above and are then separated by the ammonium oxalate method due to Jannasch.G. S. The Action of Methyl Sulphate on Oils of the Aromatic and Aliphatic Series. THOMAS WEATHERILL HARRISON and F. MOLLWO PERKIN (AnaZyst 1908 33 2-9).-The authors find t h a t Valenta's method (Abstr. 1906 ii 310) is untrustworthy for the estiinationiof tar oils in mixtures of the same with mineral oils. Whilst t a r oils are soluble in all proportions in methyl sulphate mineral oils are not insoluble. The method is however of use qualitatively; methyl sulphate removes most of the tar oil together with only a small quantity of mineral oil when shaken with mixtures of these oils.If the methyl sulphate layer is then saponified with potassium hydroxide and the solution diluted and extracted with ether the tar oil mixed with only a small portion of mineral oil is recovered. It can then be tested to prove that it is a tar or aromatic oil. The fact that methyl sulphate dissolves a portion of an oil is no proof that the dissolved portion is an aromatic hydrocarbon. w. P. s. Estimation of Naphthalene in Coal Gas and in Spent Oxide of Iron. C. J. DICKENSON GAIR (J. Xoc. Chem. Ind. 1907 26 1263-1264).-The method described previously (Abstr. 1906 ii 201) has been modified as follows so as to be available either gravi- metrically or volumetrically. The naphthalene picrate obtained is collected on a filter and washed with about 400 C.C. of dilute picric acid solution to remove the acetic acid and is then washed into a beaker with a little cold water; 180 C.C.of water are added together with 25 C.C. of N/10 sodium hydroxide solution and the mixture is boiled for ten minutes with the result that the naphth-136 ABSTRACTS OF CHEMICAL PAPERS. alene is liberated. If on testing with lacmoid indicator the solution does not give a green coloration a further quantity of sodium hydroxide is added and the boiling continued. N/20 picric acid solution is now added in excess as is shown by the indicator becoming yellowish-brown and the solution is titrated with N/10 sodium hydroxide solution until the green coloration is per- manent. The quantity of sodium hydroxide solution required t o decompose the naphthalene picrate is thus found ; 1 C.C.of A710 sodium hydroxide solution corresponds with 0.01 28 gram or 0.197 grain of naphthalene. For the estimation of naphthalene in spent oxide of iron 10 grams of the undried oxide are placed in a closed flask and extracted with 100 C.C. of 80% alcohol. At the end of three hours the solution is poured through a filter the residue is washed with dilute alcohol and to the filtrate are added 300 C.C. of concentrated picric acid solution. After a short time the naphthalene picrate is collected on a filter and the naphthalene is then estimated volumetrically as described above except that there is no necessity to wash the picrate before decompos- Estimation of Alcohol in Wine. MARCEL DUBOUX and PAUL PUTOIT (Ann. Chim. a n d 1908 13,4-9).-Five volumes of redistilled aniline are mixed with 3 volumes of alcohol (95' French). A mixture of 1 volume of nitrobenzene and 9 volumes of alcohol may be used also. Fifteen C.C.of the mixture are placed in a test-tube 3.5 cm. in width and 15 cm. long fitted with a doubly-perforated cork through which pass a delicate thermometer and a glass stirrer bent upwards at the lower end. Ten C.C. of the alcoholic solution (wine- distillate) are added and t h e whole is heated with constant stirring until a clear solution is obtained The temperature at which this occurs is noted and referencemade to a table constructed from similar experiments made with alcoholic mixtures of known composition. ing i t with sodium hydroxide solution. w. P. s. L. DE K. Formation of Methylacetol (Acetylmethylcarbinol) in the Acid Fermentation of Wines. J. PASTUEREAU (J. Pharrn. Chcm. 1908 [vil 27 10- 12).-The author states that acetylmethylcarbinol is a normal constituent of wine-vinegars and that it is formed during the acetic fermentation of the wine. Its presence may be ascertained and its amount determined by subjecting the neutrdised vinegar t o distillation under reduced pressure or by passing a current of steam. The ketone is then estimated in the distillate either by Fehling's solution or by means of ammoniacal silver nitrate containing sodium hydroxide. 2.85 Grams of copper reduced = 1 gram of methylacetol ; 4 atoms of silver = 1 mol. of methylacefol. Methylacetol is also characterised by yielding with phenylhydrazine acetate an osazone melting a t 2 4 3 O of which the corresponding osotetrazone melts gt 151'. With semicarbazide a semicarbazone is obtained melting at 200'. L. DE E.

ISSN:0368-1769    

DOI:10.1039/CA9089405129

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

137 General and Physical Chemistry. Chemistry in Space. GIACOMO L. CIanrIcIaN (Atti I?. Accad. Lincei 1908 [v] 17 i 3-4).-A reply to Paterni (this vol. ii 77). T. H. P. Stereoisomerism and the Law of Entropy. ARTHUR MICHAEL (Amer. Chem. J. 1908 39 1-16).-A theoretical paper in which attention is drawn to the intimate connexion between the energy relations of stereoisomeric compounds and their chemical behaviour. E. G. State in Solution of the Camphorcarbosylates of Aliphatic and Aromatic Amines a8 revealed by the Rotatory Power. JULES MINGUIN (Compt. Tend. 1908 146 287-290. Compare Abstr. 1905 ii 130).-The author has measured the rotatory power of M/100 solutions of camphorcarboxylic acid (1 ) alone ; (2) containing equivalent quantities of propy 1- but y 1- diet h y 1- and trie t h yl-am i n e and (3) containing excess of the same amines and finds that the deviations of the rotatory power of solutions (3) from that of solutions (1) are practically the same as those of t>e rotatory power of solutions (2) from that of solutions (l) showing that the aliphatic amine campborcarboxylates are undissociated or only very slightly dis- sociated in solution. Moreover the results verify the law (Haller and Minguin Abstr.1903 i 267) that in the same optically active homologous. series the same fraction of the molecular weight under the same conditions produces the same deviation. The aliphatic amines in their capacity as solvents have no influence on the rotatory power. Pmppkamine cnmphorcarboxykate forms crystals m. p. 1 10' (decomp.) ; the diethylamine salt has m.p. 124O and the 6utyZanzine salt m. p. 155'. Measurement of the rotatory power of N/300 solutions of camphor- carboxylic acid in alcohol ether benzene toluene xylene and acetone and of the same solutions containing an equal molecular quantity of aniline shows that the optical activity of the acid is largely influenced by the solvent and that the addition of aniline has practically no effect. The conclusion is drawn that aniline camnp~orcarboxylccte (solid m. p. 65' decomp.) is completely dissociated in solution. Excess of aniline lowers the rotatory power from = 3' (in 2-dcm. tube) with an equivalent amount of aniline to aJ2= 1 O 2 6 ' with all. aniline. This change is probably due both t o the formation of an aniline salt of a lower rotatory power than that of the acid (since-a reaches a constant value with the concentration 70M/300 of aniline) and t o the influence of the aniline as a solvent.Addition of a large excess of aniline to a H/100 solution of csmphorcarbovylic acid and triethylamine very considerably reduces its rotatory power and that this is not due t o the displacement of the amine from triethylarnine camphorcarboxylate by aniline is shown by VOL. xclv ii. 1 0138 ABS’I’RSCTS OF CHEMICAL PAPERS. the fact that n similar although smaller reduction is produced when equivalent quantities of both amines (both largely in excess of the acid) are added to R M/100 solution of the acid. A similar phenomenon is observed with butylamine camphorcarboxylate. The camphorcarhoxylates of methylnniline dimethylaniline cthyl- aniline 0- and nt-tolnidine and a- and P-nnphthylamine are likewise completely dissociated in solution and these &mines act similarly to aniline towards the aliphatic amine salts.E. H. Resolution of the Spectral Lines of Barium Yttrium Zirconium and Osmium in a Magnetic Field. BURTON E. MOORE (Ann. Physik 1908 [iv] 25 309-345).-An attempt has been made to discover series in the spectral lines of certain metals by grouping together those lines which show a similar behaviour in the magnetic field. I n the spectra of the metals examined the types discovei ed are very complicated and very few regularities applicable to more than a small number of lines could be observed. Yttrium and zirconium are particularly rich in new types of resolution.Runge’s rule that the distances of the components from the middle are aliquot parts of the ‘‘ normal distance,” is confirmed. C. H. D. Spectrum of Strontium in the Orange and Red. PETER JECHEL (Chenz. Zenty. 1907 ii 1588-1589 ; from Zeitscli. wiss. Photocliernie 1907 5 322-339).-The spectrum of strontium has been photographed with the aid of a large Rowland concave grating the source of light being an electric arc between carbon poles ; the positive carbon is drilled and filled from time to time with strontium chloride. The strontium spectrum in the orange and red consists of five groups of lines and bands which are described in detail. The reeults agree satisfactorily with Deslandres’s formula. G. Y. Energetics and Chemistry of Banded Spectra.JOHANNES STARK (Physikul. Zeitsch. 1908 9 85-94).-A theoretical paper dealing with the structure of the atom considered as an aggregation of electrons. Two types of electrons are distinguished the one type arranged in the form of a ring represents the positive electricity of the atom and the second type consists of negative electrons which neutralise the positive charge of the ring and are separated from the atom when ionisation takes place these being termed valency electrons. Banded spectra are supposed to be determined by the valency electrons the energy radiated when the valency electrons enter into combination with the positively charged atomic groups representing the potential energy corresponding with the separation of the valency electrons from the atomic aggregates.Three kinds of valency electrons are also distinguished and the characteristics of banded spectra are discussed in terms of these three types. Anomalous Modifications of the Band Spectra of Different Compounds in the Magnetic Field. A . DUFOUR (Compt. rezm?. 1908 146 229-231).-The band spectra of strontium and barium H. M. D.GENERAL AND PHYSICAL CHEMISTRY. 139 fluoride and of calcium strontium and barium chlorides obtained by volatilising the salts in a flame placed in the centre of a Weiss electro- magnet exhibit similar anomalous modifications to those observed in HENRI BECQUEREL (Conapt. rend. 1908 146 257-259. Compare ibid. 163).-Poleinical against Dufour (preceding abstract) (compare also Jean Pecquerel Abstr. 1906 ii 317 ; this vol. ii 3 ; Wood this vol.ii 150 ; Henri Becquerel Abstr. 1889 553). Spectrum of the Ruby. A . & I r E T m (Bet-. Deut. physiknl. G'es. 1907. 5 715-717) -In addition to the absorption band noticed by Vogel the spectrum of the ruby is characterised also by a number of absorption lines particularly two very close together in the red These two lines which with a pocket spectroscope are seen as one line appear to be due to chromium. The author shows that there is a simple connexion between the position of the absorption lines and the fluorescence lines of the rnby. Absorption of Light in Solutions of Aniline Coloure from the Standpoint of Optical Resonance. STANISLAW KALANDEK (Plqsikal. ZeitscTt. 1908 9 128 -134).-8ccording to Kossonogoff's theory (Physikal. Zeitsch. 1903 4 208 258) the absorption bands of a given coloured substance should be displaced towards the red end of the spectrum when the substance is dissolved in solvents with increasing refractive powers.The absorption bands of four colouring matters dissolved in aniline and ethyl alcohol and of two others in aniline and water have been compared The requirements of the theory are satisfied qualitatively in five cases but with cornllin in aniline and ethyl alcohol the displacement of the bauds is in the opposite direction from that indicated by the theory. An attempt is made to explain the quantitative deviations which are met with in all the cases examined. The changes in the absorption spectra which take place when the concentration and thickness of the absorbing column are varied are also recorded for a number of substances dissolved in water and ethyl alcohol .H. &I. D. the case of calcium fluoride ( i b i d 1 IS). 11. A. w. Spectra of Non-dissociated Compounds. E. H J. C. P. Detection of Ultra-violet Rays. CARL SCHALL (Chew. Zenti.. 1907 ii 1442 ; from Phot. Woch. 1907 33 321-322).-Paper soaked in a solution of 1 gram of p-phenylenediamine in 4 C.C. of dilute nitric acid (2 C.C. acid D 1.2 and 3 C.C. water) and dried rapidly over a bunsen flame is recommended as test paper for ultra-violet rays. On exposure to ultra-violet light the paper becomes blue less so on exposure to white light. The paper remains unchanged in daylight in a room but becomes grey or greyish-blue in the open. The blue colour is produced instantaneously by the rays from a quartz lamp more slowly by those from a uviol lamp.The rays from gas Auer electrical glow and Nernst lamps do not affect the paper. The spectrum of the Heraeus lamp has a blue band extending int,o the ultra-violet. G. Y. 10 -2140 ABSTRACTS OF CHEMICAL PAPERS. Changee in the Colour of Calcium Sulphide under the Influence of Light. Josh R. MOURELO (As*ch. Sci. phys. nat. 1908 [iv] 26 16-25).-When calcium sulphide is prepared by heating calcium oxide obtained from different forms of the carbonate with sulphur or in n current of dry hydrogen sulphide the white or greyish- white colour of the sulphide is found in many cases to change into a reddish-violet when the substance is exposed to light. Sulphides prepared from calcium sulphite thiosulphate or sulphate do not exhibit this colour change.The exact conditions for the production of the colour-sensitive sulphide could not be ascertained for pure and impure calcium carbonates natural and artificial sometimes yield a colour-sensitive sulphide and a t other times under the same con- conditions a sulphide is obtained which is quite inert towards light. The colour-sensitiveness seems to be independent of the phosphor- escent power some samples with strongly and others with very feebly developed phosphorescent properties exhi biting the same sensitiveness towards light in regard to the colour change. Experiments are described which indicate that the change in colour is confined to the surface of the sulphide exposed to light. The observed effects are not attributable to oxidation and are referred to chemical changes directly induced by light.H. M. D. Pseudo-reversible Photochemical Processes. Photochemical Cyclic Action. ROBERT LUTHER and JOH. PLOTNIKOFF (Zeitsch. physikal. Chem. 1908 61 513-544).-An example of pseudo- reversible photochemical action is furnished by the oxidation of oxaiic acid by atmospheric oxygen in presence of light and iron salts. A solution of ferrous oxalate when kept in the dark in contact with air changes colour and is oxidised to ferric oxalate. I f this solution containing ferric oxalate is exposed to bright light reduction takes place ferrous oxalate is regenerated and carbon dioxide is liberated. This reaction is not a perfectly reversible one because there is involved an irreversible change namely the oxidation of oxalic acid by atmospheric oxygen.It is a case of cyclic action (" Uebertragungs- katalyse "). Another case of photochemical catalysis studied quantitatively by the authors is the oxidation of phosphorous acid by atmospheric oxygen in presence of light and iodine. The reactions here involved are (1) 2HI + 0 =I + HqO a change which is slow in the dark butl rapid in light (see Plotnikoff Abstr. 1907 ii 212) ; (2) H,PO + H,O + I = H,PO + 2H1 ft reaction which takes place rapidly and on which light has no influence (see Pederlia Abstr. 1903 ii 14). The authors show that in the absence of iodine the velocity of the irreversible change H,PO + 0 = H,PO is negligibly small either in the dark or in light. The kinetics of the separate reactions and of the total reaction are considered from the theoretical point of view and formuls are deduced for the cburse of the photochemical change.The results of the experimental work which the authors have carried out are in harmony with their formula?. Thus the equilibrium concentration of the iodine is proportional to the intensity of the light proportional to theGENERAL AND PHYSICAL CHEMISTRY. 141 velocity of the photochemical reaction and inversely proportional to the velocity of the opposing reaction (2). It is found also in harmony with theory that rise of temperature favours the opposing reaction. From the authors' work the general conclusion may be drawn that the laws governing pseudo-reversi ble photochemical reactions resemble very closely those to which perfectly reversible reactions are subject.The paper contains a description of a n apparatus which provides for the constant saturation of a liquid with oxygen and at the same time permits a determination (from the diminution in volume) of the rate a t which the oxygen is reacting with the liquid. The Atomic Weight 'of Radium. HENRY WILDE (Mem. Manchester Phil. Xoc. 1907 52 :No. 1 1-3).-The author has previously expressed the view that the atomic weight of radium is 184 (Abstr. 1907 ii 149); this view is now confirmed by a calcula- tion of its equivalent which proves to be 92 from the ratio Ag RaCl,. J. C. P. P. H. Decay of Radium-B and -0 at High Temperatures. HEINRICH W. SCHMIDT (Plr~ysikcd. Zeitsclz. 1908,9 11 3-1 17. Compare Makower and RUSS Abstr.1907 ii 421 ; Bronson Abstr. 1905 ii 567).-The question as to whether radioactive change is influenced by high tempera- tures has been again examined experimentally. The method was similar to that adopted by Bronson (Zoc. cit.). The conclusion is drawn that the rate of decay of radium4 is independent of the temperature up to 1300'. This result does not agree with the observations of Makower and lcuss (Zoc. cit.) who found that the rate of decay of radium4 was smaller a t high temperatures than at room temperature. H. M. D. Radio-Lead. BELL SZILARD (Compt. rend. 1908 146 11 6-1 18). -The object of this work is to determine how the radiums D E and F are separated from the substance known as radio-lead by certain chemical reactions. Recrystallisation of the nitrate from a neutral solution gradually removes the radium-F (polonium) which remains i n the mother liquor but does not appreciably influence the amounts of radiums I) and E in the crystals. The same separation can be effected in a strongly acid solution.Addition of sodium ethyl sulphate to a solution of a salt of the active lead gives after a time a slight precipitate containing the greater part of the radiums E and F but only a trace of radium-D. Dissolution of radioactive lead carbonate in concentrated sul phuric acid and evaporation of the filtrate to dryness leaves a residue only slightly enriched in radium-D. Commercial carbamide but not the pure substance gives a rosy precipitate in active lead solutions which contains a greatr part of the radiums E and F but very little of radium-D.Ammonium carbonate gives a similar but less active precipitate. The latter seems to be a true chemical reaction and the precipitate has almost the same activity immediately after formation as after several days. Hofmann and Zerban showed (Abstr. 1902 ii 311 ; 1903 ii 732) that the double thiosulphate of sodiarn arid active lead decomposes143 ABSTRACTS OF CHEMICAT PAPERS. spontaneously giving a precipitate of which the first f mctions are more active than those following. The author finds that this reaction is influenced both by light and by filtration the formation of the precipitate being hastened by these agencies whilst its composition is changed its colour becoming red if produced in a strong light. The first fraction is the most active and contains five to seven times more radium-l) than the later fractions.The latter have all about the same activity but contain very little radium-D of which the greatest part remains in solution. If the first fraction is reconverted into nitrate a second precipitation gives a better yield. In some cases the separation of the active substances is influenced advantage- ously by light. Removal of radium-l) has not been effected radium-$’ (polonium) can be removed by many chemical reactions and radium-E also with a little more dificulty. Radiums B and P in some cases can be removed simply by addition of a substance in suspension. The time constant of radium-& corresponds in certain cases with that of radium-El and in others with that of radium-X2.E. H. Penetrating Radiation. W. W. STRONG (Physikccl. Zeitsch. 1908 Q 117-119).-Three lines OF evidence are brought forward to show that the greater part of the ionisation observed in closed vessels is due t o a penetrating form of radiation emitted by radioactive substances present in the atmosphere. I n the first place the radium content of the earth’s surface is too small to account for the observed ionisation effects. Secondly the ionisation is found to vary with changes in the atmospheric conditions ; with normal atmospheric conditions diurnal variation similar to that exhibited by temperature can be traced. Thirdly constant ionisation values are observed in caves there being no evidence of diurnal variation H. ill. D. Have X-Rays an Action on Radioactive Substances 3 CHABLES E.GUYE A. SCHIDLOF and M. KERNBAUN ( A w h . Xci. phys. nat. 1908 [iv] 25 26-35).-ExpeIiments have been made t o ascertain whether the rate of decay of the activity of radioactive substances is altered when they are subjected t o the action of X-rays. The substances examined were polonium the induced activity from radium an impure radium compouud and radium emanation; the rate of decay of these when acted on by X-rays being directly compared with the rate when not subjected to this influence. I n no case was any definite di-flference observable. H. &I. D. So-called Moser-Rays. XLISABETH L~GRBDY (Zeitsch. Photochem. 1908 6 60-67).-The photochemical action exhibited by certain metals in the dark has been investigated. By means of a small gas- tight chamber provided with inlet and outlet tubes the influence of different gases and of moisture on the activity of the metals could be examined.In the absence of metals the photographic plates were not acted on when dry air nitrogen or hydrogen was passed through the chamber A negative result was also obtained with dry air and nitrogen in thepresence of freshly-polished aluminium cadmium magnesium and zinc but the plates were acted OD when the gases were not dried. Hydrogen was found to be active in the presence of the above nietals whether dried or moist. From these observations the author draws the conclusion that the metals per se have no photochemical properties and that the observed photochemical effects are dependent on the presence of hydrogen (or hydrogen compounds).The directly active agent is supposed to be ionised hydrogen which is produced from molecular hydrogen (or from water) by the action of the metals. Experiments are also described which show that the action cannot be attributed to the emission of active rays by the metals or by the ionised hydrogen. Certain metals appear t o exhibit two kinds of photochemical activity but the second type which gives rise to light pictures has not been examined in detail. H. M. D. Radioactivity of the Kisaingen Mineral Springs. FELIS JENTZSCH (Physikccl. Zeitsch. 1908 9 120. Compare this vol. ii 9). -The author withdraws his criticism of the formula used by H. W. Schmidt (Physikcd. Zeitsch. 1906 7 209) for calculating the radio- activity of mineral waters from ionisation experiments.The difference between this formula and that employed by the author is due to a slight modification in the experimental method. The numbers previously given for the water of the Rakoczy spring are recalculated on the assumption that the natural radiation in a closed electroscope is t o bereferred to causes other than the emanation present in the air. Data are given for the activity of samples of Rakoczy water which have been kept for periods reaching to three years. The activity decreases for about fifteen months and then increases and i t is suggested that this may be due to the gradual formation of an emanation-emitting substance. H. 311. D. Radioactivity of the Waters of Lavey-les-Bains. ED. SAKASIN CHARLES E. GUYE and JULES MICHELI (Arch. 8ci.phys. rznt. 1908 [iv] 25 36-44).-The radioactivity of the Lavey springs has been measured by the method of Elster and Geitel and found to be 11 in terms of Mach's unit. With the exception of the Dissentis springs this represents a radioactivity of much greater magnitude than that of any Swiss waters which have been examined. The activity is probably due to radium emanation since it falls to the half value i n four days. H. 3%. D. Radioactivity of the Waters of Plombieres. ANDR~ BROCHET (Compt. rend. 1908 146 175-1 77).-The author has determined the radioactivity of minerals and other solids of gases and of wAters collected i n Plombikres. That of the solids is either zero or approaches the limit of sensitiveness of the apparatus (a Curie electroscope having an aluminium leaf and micrometer' adapted to a condenser).Three hours after collection the gas from the Yauquelin spring had a radioactivity of 14.9; from the Thaltveg gallery 13.6 arid that from the Savonneuses gallery 6 -1 expressed in milligramme-mi nutes1-4 4 ABSTRACTS OF CHEMICAL PAPERS per 10 lityes of gas. For the former two gases Curie and Laborde found 5.7 and 3.3 respectively but their experiments mere made four days after collection. The radioactivity 01 the gas extract-ed from the water from Vanquelin (temperature 69') is 0.84 (Curie and Laborde found 0.22) ; of Roman Robinet (temperature 70°) 0.43 ; from the Capucins (temperature 4 6 O ) 3-03 (Curie and Lsborde found 0*46) and from the Snvonneuses gallery No. 1 (temperature 22O) 0.75 No.2 (temperature 2S0) 1.29. The emanation extracted from the water from the Capucins loses half its activity i n four days. The results establish the fact that there is no relation between the radioactivity of the waters and their temperature. IE. H. Anomalous Behaviour in the Radioactivity of Certain Uranium Compounds. HERMAN SCHLUNDT and RICJ-IARD B. MOORE (Physikal. Zeitsch. 1908 9 81-85).-When excess of a hot 4-normal ammonium carbonate solution is added to a nearly saturated solution of uranyl nitrate the uranium and uranium-X both dissolve completely. On cooling crystals of the double carbonate separate but the whole of the uraninni-X remains dissolved. The radioactivity of the double carbonate increases after a time a maximum being attained a t the end of about twelve days.A similar increase takes place when the substance is gently heated. I n both cases the increase in activity is accompiznied by a slight deepening of the yellow colour of the crystals. The phenomenon appears to be due to the decomposition which the substance undergoes the removal of ammonia carbon dioxide and water resulting in a diminution of the retardation of the particles which are emitted by the active element contained in the compound. The increase in the activity is pro- port,ional to the loss of weight a similar effect being observed when thin layers of uranyl acetate and nitrate are gently heated. The experimental results are compared with the calculated increases in activity assuming that the retarding power of the volatile products of decomposition is inversely proportional to the square root of the atomic weights of the elements contained in these products.Association of Helium and Thorium in Minerals. U0p,,2(NH4),C0 H. AX. D. ROBERT J. STRUTT (Proc. Roy. Soc. 1907 80 A 56-57).-Boltwood (Abstr. 1907 ii 220) has recently suggested that the helium in radioactive minerals always originates from the uranium-radium series of transformations. The author has now examined a mineral from Greenland yielding helium which contains only traces of radium much too small to account for the helium present but yields abundant thorium emanation ; he therefore considers that the helium in this case is a product of thorium radioactivity. WILLY MARCKWALD and B. KEETMAN (Rela. 1908 41 49-50).-The authors' investigations confirm the results obtained by Boltwood (Abstr.1907 ii 836) and Hahn (ibid. 921). Attempts to separate ionium and thorium have as yet been unsuccessful. G. S. Ioniurn.GENERAL AYD PIIYSTCBL CIIEMISTRT. 145 i h investigation of autunite shows that 10 grams of this mineral does not contain so much as 0.1 mg. of lead; this is remarkable since lead is generally supposed to be the final product of the transformation of uranium. Amalgam Concentration Cells Chemical Cells and Daniel1 Cells Constructed with Solid Electrolytes. 31. KATAYAMA (Zeitsch. physikd. Chem. 1908 61 566-587).-The i7.H.F. of the cells referred to was measured by the usual compensation method except that a quadrant electrometer was employed as zero instrument. The first type of cell studied mas P b amalgam c1 I solid PbBr I Pb amalgam cg and it is shown that the E.J!f,F.of such a cell may be calculated by the formula E=RT/21?logc,/cl where c and c1 are the concentrations of the lead in the two amalgams. The chemical cells mere of the type Metal [ Metallic haloid I Halogen and many precautions detailed in the paper must be observed if trust- worthy values for the l7.iW.P. of such a cell are to be obtained. The cells actually examined were as follows Ag 1 solid AgCl 1 C1 for which E = 1.130 + 0.0006 (20 - t ) between 15' and 159O ; Pb I solid PbCl I C1 for which E= 1.581 + 0.00065 (60 - t ) between 60' and 1 5 5 O ; Pb I solid PbBr 1 Br for which E= 1.338 + 0.00065 (GO - t ) between 60° and 162O. Three cells of the type of the Daniel1 element mere also constructed and studied with the following results P b I solid PbCl I solid AgUl I Ag E=0.480 +0*0001 (60 - t ) between 23' and 151'; Pb 1 solid PbBr I solid AgBr I Ag E= 0.342 + 0.00025 (20 - t ) between 20" and 145' ; Ag 1 solid AgCl 1 solid AgBr I Ag E = 0 except for slight differences due to experimental errors.Concentration Calls. I. Cadmium Chloride Cells. EUGEN VON BIRON (J. Izuss. Phys. Chenz. SOC. 1907 39 1506-152l).- Three kinds of concentration cells mere investigated in various cadmium chloride solutions (1) those in which there is no transport of an ion ; (2) those in which the anion is transported; (3) those in which the cation is transported. Curves are drawn showing the relation between the logs. of con- centration of the solution and the corresponding ,9.M.B'.for the three cases. The following concentration cells were studied Cd I mCdC1,aq I nCdC1,aq I Cd; Cd 1 CdCl,aq.KCl I HgC1.Hg; Hg.HgC1 1 mCdClsaq 1 mCdClsaq [ HgC1.Hg ; Ag.AgC1 I mCdC1,aq 1 nCdC1,aq 1 AgC1l.Ag ; Cd 1 .nzCdCl,aq ! AgCl.Ag.AgC1 I nCdC1 I Cd (where m and n are the concentration ot the solutions and m>n. It is impossible t o apply Moser's method here for the calculation of the transport numbers but another method for effecting this is deduced. When however the numbers so obtained for chlorine in cadmium chloride are compared with those obtained by the customary Hittorf's method they agree well for dilute but not for concentrated solutions ; the conclusion is therefore drawn that whereas Nernst's theory of diffusion for electrolytes is completely justified for dilute solutions it is not applicable to Concentrated solutions and in all probability the l a s s governing the latter art of :ti1 esserltially different character.2. K. W. H. G. J. C. P.146 ABSTRACTS OF CHEMICAL PAPERS. Alkali Electrode. PAUL T. MULLEK and H. ALLEMANDET (J Chim. Phys. 1907 5 533-556).-The authors have prepared :in alkali electrode consisting of mercury slid yellow mercuric oxide in contact with solutions of dif‘ferent bases. The purification of the reagents and the arrangements employed for preventing contamination with carbon dioxide during the measurements are fully described. I n order t o increase the condilctivity the solution in the alkali compartment also contained potassium nitrate. The electrode was connected with a calomel electrode thus con- stituting a cell Hg I HgCl + KCl / KNO + KOH + HgO I Hg and the potential measurements carried out by the cornpensation method at 25’.Results are given for iV/lO to AT/lOOO solutions of the hydroxides of potassium sodium lithium thallium barium strontium and calcium and it is shown that with proper precautions the E.F.M.’s are repro- ducible to about a millivolt. In L ~ r / l O O solution the so-called ‘‘ absolute ” value of the single potential difference (calculated by means of Ostwald’s value for the calomel electrode) varies only from 0.5042,to 0 5078 for the different bases the mercury being positive in satisfactory agreement with the view that the O H ion concentration alone determines the potential. At higher concentrations the alkaline earth bases give a slightly greater E.Af.8’. than the alkali bases indicating a less complete electrolytic dissociation in the former case but the difference in the degree of dissociation in corresponding solutions could not be calculated from the results owing to the nncertainty introduced by the diffusion potential at the liquid junction.Even in the most dilute solutions there is a slight difference of potential not much greater than the experimental error between the &.iU.P. of the potassium and sodium electrodes ; this is ascribed t o the fact that in the former case the potassium nitrate added t o increase t h e conductivity has an ion in common with tho alkali surrounding the electrode. G. S. Nickel Peroxide Electrodes.FRITZ FOERSTER (Zeitsch. Elektro- clmn. 1907 13 414-434).-Bellucci and Ciavari (Abstr. 1905 ii 823) have shown that in the oxidation of nickelous hydroxide the primary product is always Ki02. The author finds that the active mass of a nickel peroxide accumulator plate after complete discharge consists of Ni(OH) when it is dried over snlphuric acid. The active oxygen in a fully-charged electrode was estimated by treating a portion of it with acid hydrogen peroxide and measuring the oxygen evolved or by boiling with hydrochloric acid and estimating the chlorine produced; in this way it was found that the oxidised mass contains from 0.53 t o 0.56 atom of active oxygen to 1 atom of nickel. After mashing and drying as quickly as possible over sul- phuric acid the substance liad the composition Ni,O,,l*l-l~3H,O.This is quite stable when dry but decomposes slowly at the ordinary temperature when wet. Ths equilibrium potential of a charged electrode in 2 *8AT-potassium hydroxide solution diminishes! quickly at first more slowly afterwards to a constant value which is identical with that obtained with Ki203. Oxygen gas is evolved during this change. The decreased concentratioii of the potassium hydroxide inGENERAT AND PRTStCAT CHEMISTRY. 147 the pores of the electrode due to the charging would account for a higher potential a t first but it is found that a siiidar increase of potential a t the iron electrode disappears in less than one hour whereas twenty to thirty days are required for the peroxide electrode.The author therefore regards i t as more probable that the fully-charged electrode consists OF a solid solution of NiO in Ni,O,. The evolution of oxygen which takes place from a freshly-charged electrode is due to the decomposition of the NiO,. The author does not agree with Zedner (Abstr. 1906 ii 595) as to the meaning of the different portions of the discharge curve. The comparatively rapid fall of I3,M.F. a t the beginning of the discharge is regarded as due to the disappearance of the NiO existing in solid solution in Ni,O,. The first period of approximately constant E.M.F. corresponds with thereductionof Ni,O to Ni(OH) and the second period of constant E.M.F. (about 0.55 volt below the first) is due to an oxide lying between Ni20 and NiO. In charging the electrode a higher E.ALF.is required than that observed during discharge owing to the fact that NO is the primary product of oxidation Ni,O being formed by its reaction with Ni(OH)? the change is therefore not strictly reversible. T. E. FRITZ FOERSTER (Zeitsch. Eleklro- chem. 1908 14 17-19).-A reply t o Zedner's criticism (this vol. ii 12) ; the author maintains that the behaviour of a freshly-charged nickel oxide electrode is quite inexplicable on Zedner's assumption that it contains occluded oxygen b u t is in complete harmony with the view that it contains NiO,. The actual degree of hydration of the oxides contained in the electrode in contact with the concentrated solution of potassium hydroxide cannot be determined by analysis of mashed and dried samples.Wehnelt Cathode in High Vacua. A. WEHNELT (Physikal. Eeitsch. 1908 9 134-135).-The author replies to Soddy (this vol ii 81) and maintains that he has never held the view attributed to him that the large currents attainable in spectrum tubes provided with a Wehnelt cathode arc entirely due t o electrons emitted by the strongly heated cathode. It is however claimed that currents may pass through highly exhausted tubes in which the only carriers are the electrons emitted by the cathode but the intensity of such currents is of a much smtller order of magnitude (10-2 amperes). The fact that maximum saturation currents are obtainable which are indepen- dent of the pressure provided this is less that 0.1 mm. is evidence of such electron currents. The part played by the electrons emitted by the hot cathode in the case of the larger ionisation currents consists in the removal of the large fall of potential at the cathode which results from the tleficiehcy of electrons i n consequence of the very different velocities of the positive ions and the electrons. Electrical Resistance and Expansion of the Metals.WITOLD BRONIEWSKI (J. China. Phys. 1907 5 609-635. Cornpar e Abstr. 1906 ii 646 ; J . Chim. P h p 1907 5 57).-In previous [Nickel Oxide Electrode.] T. E. H. 31. lJ.148 ABSTRACTS OF CHEMICAL PAPERS. papers the relation botwcun the variation Qf the electrical resistance and the expansion of monatomic metals and of some polyatomic metals has been dealt with; in the present paper the consideration of polyatomic metals is coinpleted and a r6sum8 of the results is given.The polyatomic metals are divided into two groups ( a ) the iron group ‘‘ for which the space between the atoms is constant ” ; ( b ) the antimony selenium and gallium groups ‘( for which the space between the atoms is variable.’’ The behaviour of the first group has already been considered (Zoc. cit.). Unlike monatomic metals the quotient of the atomic latent heat of fusion by the absolute temperature of fusion is not constant for polyatomic metals ; it is 4-86 for bismuth and 1-80 for thallium. For t h e second group of metals mentioned it is shown from available data that the variation of the electric resistance with temperature is repre- sented satisfactorily by the formula yt = const. x T(2P+ T) where yt is the resistance at a definite temperature 1’ is the absolute temperature and P is the absolute temperature of fusion a formula which also holds for monatomic metals.Matthieseon has shown (1863) that for a pure and impure form of the same metal the relation yR = y’R’ holds where y and y’ and R and R’ are the temperature-coefficients and the specific resistances of the pure and impure metal respectively. The limiting specific resistances R for a number of pure metals are calculated from the known values of y,y’ and A’ and the results are compared with the experimental values. It is considered probable that the observed diminution of the tempera- ture-coefficient of the resistance of palladium and platinum with temperature is due t o traces of impurities and that the pure metals like nearly all other metals have a positive temperature-coefficient of conductivity.G. S. Ionisation of Liquid Dielectric Media by Radium Rays. GEORGE JAFFE (Ann. PILysik 1908 [iv] 26 257-284).-The electrical conductivity of light petroleum carbon tetrachloride carbon d i - sulphide and benzene is increased by exposure to radium rays. The relation between the current (i) thus produced and the E.M.F. (e) applied to the electrodes is i =f(e) + c.e where c is a constant. When the field strength is greater than a certain value between 500 volt/cm. and 1000 volt/cm. the terrnjle) is a constant and the relation between current and potential is then a linear one. There is thus considerable analogy between the behaviour of liquid dielectric media exposed to the action of radium rays and t,he behaviour of ionised gases.J. C. P. A Relation Between Ionic Mobility and Temperature- coefficient. EWALD RASCH and F. WILLY HINBICHSEN (Zeitsch. E’lektrochem. 1908 14 46-47).-Using the values calculated by Kohlrausch and Drucker i t is shown that the product als.logZls is a constant I and a18 being the mobility of an ion and its temperature- coefficient at 18’. The values of the constant calculated lie between 0.0367 and 0.0404 f o r t8he nrrit-dent ions and hetween 0.0407 and 0.0434 for the bivalent ions T. E.GENERAL AND PHYSICAL CHEMISTRY. 149 Abnormal Mobility of the Ions of some Rare Earths. JULES Roux (Conzpt. rend. 100S 146 174-176).-The mobility of the univalent ions except hydrogen (3 18) and hydroxyl (1 74) ap- proximates to the value 67 (Cl 65 ; Rb 68) that of the bivalent ions to 48 (Zn 46; Ca 51) and that of the negative tervalent ions t o 85 ($t[Fe(CN),] 82 ; $[Cr(CN),] 90). Hitherto the mobilities of the positive tervafent ions have not been determined owing to the hydrolysis of their salts.Some of the metals of the rare earths however form perfectly neutral solutions and by measurement of the conductivity of solutions of lanthanum nitrate and of the bromides (prepared by Bourion's method Abstr. 1907 ii 773) of lanthanum yttrium cerium gadolinium and samarium a t concentrations I/ 100th 1/200th and 1/10,00Oth normal the author has determined the mobility of the ions of these metals. The following values were obtained a t 18' with respect to mercury a t 0". Lanthanum (in nitrate) 111 a t N/lOO 112 at iV/200; (in bromide) 111 a t h7/100 112-5 at N / Z O O 116 at N/lO,OOO; yttrium 115 a t N/100 116.5 a t N/200; cerium gadolinium and samarium 112 91 and 66 re- spectively a t iV/lOO.Thus these ions (except that of samarium) have a greater mobility than either univalent bivalent or negative tervalent ions. The low value for samarium suggests the possibility of separating t h i s metal from the others by diffusion or by electrolysis. With a rise of temperature the mobility of the lanthanum ion in N/100 solutions of the nitrate increases from 111 at 18' €0 131 at 2 5 O . E. H. A Relation Between Electrical Conductivity and Tempera- ture. EWALD RASCH and F. WILLY HINRICHSEN (Zeitsch. EZektroc?bem. 1908 14 41-46).-An equation of the same form as van't Hoff's equation (dlogK/dT= - q / B P ) expresses the connexion between the conductivity of an electrolyte and the tempera,ture.Putting x the conductivity in place of K and assuming that q is a thermal constant the exact physical meaning of which is undefined there is obtained after integration l o p = - y / T + C where y and C are constants. This equation is shown to hold good for antimony trichloride (100-2 loo) three kinds of glass (200-350°) porcelain (50-210°) linseed oil (24-135') water and ice ( - 17-50') a mixture of zirconia and yttria (432-987*) and fused sodium chloride (800-950'). The numbers i n brackets are the temperatures between which the relationship is tested. T. E. Electrolytic Conductivity of Bromine and Iodine in Nitro- benzene Solution.LUDWIK BRUNER (Bull. Acnd. Sci. Cracow 1907 731-738. Compare Briiner and Dluska this vol. i 146).-The results obtained in the investigation of the action of bromine on toluene in nitrobenzene solution having suggested that halogens are electrolytically dissociated in this solvent the author has commenced the study of the conductivity of bromine and iodine in organic solvents. The present paper contains an account of the preliminary experiments. It is found that bromine and iodine in nitrobenzene solution have a marked conductivity which varies with the time.The cause of this variation remains unknown but cannot be substitiition in the nucleus of the solvent since in that case the variation would increase with the concentration whereas i t is found to be greatest in dilute solution. The value of A increases rapidly in concentrated solutions the resistance being almost independent of the concentration Bromine does not conduct in carbon tetrachloride nor does iodine in toluene solution.G. Y. Conductivity of Picric Acid Solutions and the Ionic Conductivity of Hydrogen. HERBERT GORKF (Zeitsch. phpikccl. Chew,. 1908 61 495-508).-The conductivity of dilute solutions of picric acid has been determined with special precautions. Extra- polation of the observed values gives A = 346.4 at 18" and A = 384.3 a t 25". From these figures it may be shown that picric acid does not obey Ostwald's dilution law (compare Rothmund and Drucker Rbstr. 1904 ii 231). The conductivity of solutions of sodium picrate has also been rneasured,and the conductivity of the picrate ion is found to be 26.0 and 30.7 a t lSo and 25" respectively.Hence the ionic con- diictivity of hydrogen is 320 at 18' and 353 a t 2 5 O and the temperature- coefficient is 0,0148 (compare Kohlrausch's value 0.0153). These values for the ionic conductivity of hydrogen are higher than those given by Kohlrausch and by Ostwald and Luther. The author himself regards them RS possibly 1% too low; even allowing for this they would still be lower than the values which are deduced from Noyes and Sammet's work (Abstr. 1903 ii 126). J. c. P. The Existence of Positive Electrons in the Sodium Atom. ROBERT W. WOOD (Phil. Mag. 1908 [vi] 15 274-279; Physikccl. Zeitsch. 1908 9 124).-Plane polarised white light is passed through sodium vapour unmixed with any other gas and placed in a strong magnetic field parallel to the direction of the light.Before exciting the magnet a Nicol prism is placed so as to extinguish the light which has passed the sodium vapour. When the magnet is excited a large number of bright lines become visible when the light which now passes the second Nicol is examined spectroscopically. The author has succeeded in showing that in some of these lines the plane of polarisation has been rotated to the right and in others to the left. Since the direction in which the plane of polarisation is rotated by the D lines indicates that they are due to the vibration of negative electrons the opposite rotation observed in some of the lines would ipdicate the existence of positive electrons in the sodium atom.T. E. Difference of Potential in the Arc Produced by a Continuous Current between Metallic Electrodes. CHARLES E. GUYE and L. ZEBRIROFF (Arch. JSci. phys. 9 2 u t . 1907 [iv] 24 549-,574).-Tho formula clcduced by hrrs. Ayrton for the relation between the length of the arc the difference of potential and the intensity of the current was verified by her when carbon poles were used. The authors findGENERAL AND PHYSlCBI CHEi\IISTRY. 151 that this formula is applicable also when the poles consist of gold platinum silver palladium copper cobalt nickel or iron. J. C. 1'. Electric Discharge in Monatomic Gases. VRE:UEMC'K SODDY and THOMAS D. 31ACKENZrE (]'roc. hh~/. sbc. 1908 80 A 9%-109).- The high resistance ofYered to the electric discharge in spectrum tubes containing monatomic gases has been studied.For this purpose tho conditions of the discliarge through helium argon neon mercury hydrogen nitrogen and carbon dioxide have been compared. Non- conductance equivalent to that represented by an inch gap in s i r a t atiiiospheric pressure was attained at the following pressures helium 0.35 mm. argon 0.04 nizn. neon 0.07 mm. hydrogen 0.03 to 0.04 mm. nitrogen 0.035 mm. carbon dioxide 0.02 IUYTI. of mercury. With a spark gap of 10 mm. mercury vapour was found to conduct with difficulty a t a pressure of 0.1 mni. and thus resembles helium in regard to the high pressure a t which it ceases t o bo conducting. The results obtained indicate that the difference between helium and other gases is one of degree only and that the monatomic gases are relatively inert electrically as well as chemically.To explain the observed facts it is only necessary to assunie that the helium molecule is at all pressures only about one-fifth to one-tenth as effective electrically as a molecule of hydrogen. This view has been confirmed by determining the relation of the potential to the pressure in helium argon and hydrogen a t high pressures. Some observat'ions relating to the Campbell Swinton efEect indicate that the bubbles formed when the glass of a discharge tube is fused are clue to chemical decomposition of the glass under t h e influence of the local heating which takes place in the course of the bombardment of the glass by the enclosed gas particles. I€. M. D Certain Phenomena Exhibited by Small Particles on a Nernat Glower.C. E. MEEDENHALL and L. R. INGERSOLL (Phil. Mag. 1908 [vi] 15 205-214).-Small globules (0.2 to 0.2 m a . diameter) of molten metals may be supercooled as much as 370' (rhodium and platinum). Gold palladium silicon and iridium behave similarly A flash due t o liberation of the latent heat occurs at the moment of solidification. A reversible change in radiating power occurs in rhodium at 1050'. Small globules of molten metals slide or roll along a Nernst glower and solid particles roll end over end. Boron rhodium palladium silver barium oxide coluiubiuni oxide iridium platinum and gold move with the current and magnesium oxide silicon titanium chromium manaanese iron oxide cobalt nickel copper and ruthenium against it.?!he rate of motion varies widely with the nature of the particle cobalt and copper giving the fastest motion ; i t also increases with the current Bowing and to a less extent vith the temperatnre. Carbon dioxide oxygen or n vacuum do not affect the motion. No satisfactory explanation of the motion has been found. It does not occur on metallic conductors. T. E.1 .ti2 ABSTRACTS OF CHEBIICAL PAPERS. Magnetic Behaviour of Air Argon and Helium in Relation t o Oxygen. PAUL TANZLER (Ann. Physik 1907 [iv] 24 931-938). -Whilst air and oxygen are paramagnetic argon and helium are dia- magnetic. J. C. P. Decomposition of Complex Chemical Compounds in a Variable Magnetic Field. J. ROSENTHAL (Sitxu92gsber. k. Akad. Jt’iss. Berlin 1908 20-26).-Evidence has been obtained that complex organic compounds are decomposed when subjected to the action of varying electromagnetic forces.The substances examined dissolved or suspended in water were brought into a solenoid through the coils of which intermittent or alternating currents were passed. For the success of the experiment the frequency of intermittence or alternation must have a definite value which depends on the nature of the substance examined. With the requisite frequency the heat developed in the liquid is very much smaller than when other frequencies are employed and the author supposes that in the first case the energy is chiefly used up in bringing about the decomposition of the complex molecules whilst with unfavourable frequencies rise of temperature is the only result.For starch the effective frequencies lie between 440 and 480 oscillations per second and for proteins the number is 320-360 whilst other substances examined (glucoside9 disaccharoses) require very much higher frequencies. The decomposi- tion of starch takes place in stages the succession of products being the same as those found in the action of diastatic enzymes. Proteins give rise to albumoses and peptones. The analogy between the action of the electromagnetic forces and that of enzymes is regarded as important from tge standpoint of the general theory of enzyme action. H. M. D. Zeeman Phenomenon. W. LOHMANN (Zeiisch. Photochem. 1908 6 1-24 41-6O).-By means of a n echelon diffraction grating the Zeemnn phenomenon has been investigated for the chief spectral lines of sodium mercury helium neon and krypton.Observations were made parallel and at right angles t o the magnetic lines of force and the gradual resolution of the spectral lines with increasing intensity of the magnetic field was traced by observations in fields varying from about 2000 t o 15,000 Gauss. Here it may be noted that the extent to which the component lines are separated is proportional t o the strength of the magnetic field The differences in the Zeeman effect which are observable with the different spectral lines indicate that these are to be ascribed to atoms of unlike structur.e. H. M. D. Expansion of Commercial Pentane and the Scale of the Pentane Thermometer. FRIEDRICH H o F F n r A N N and RUDOLF ROTHE (Chem. Zen.fr. 1907 ii 1369-1 370 ; from Zeitsch.~nstrumentee?zkunde 1907 27 265-351).-The expansion of commercial peiitane has been calculated previously from observations a t three fixed points with the aid of a quadratic interpolation formula. The authors’ determinations show that the error of pentane thermometers standardised in thisGENERAL AND PHYSICAL CHEMISTRY. 153 manner may amount to 2 O . It is necessary to determine the expansion a t least at four points. I n the method employed t v o dilatometers filled with pentane are compared with a platinum resistance thermometer. A thermostat cooled by liquid air and electrically heated for use at temperatures between - 190’ and - 130’ is described. The expansion at to is represented by the expression A t = lo+%( 1506.97 + 3.453,t + 0*0097,t2 - O*OOOOlt3).The corrections t o be applied to the old pentane thermometer at different temperatures are given in a table. The b. p. of oxygen as observed by Grunmach (Abstr. 1906 ii 655) when corrected for the error of the pentane thermometer for the pressure and for the presence of 2% of nitrogen is - 182 66O/760 mrn. which is in agreement with the observations of other investigators. G. Y. Measurement of the Velocity of Sound in Liquids and of the Ratio of the Two Speciflc Heats of Ether with the Help of Kundt’s Dust Figures. KARL DORSING (Ann. Physik 1908 [iv] 25 227-251).-The liquids examined were water alcohol ether strong ammonia solution concentrated hydrochloric acid sodium chloride solutions chloroform carbon disulphide turpentine and “benzin.” With rising temperature the velocity of sound in water increases whilst the velocity in other liquids diminishes.In liquids which contain either dissolved gases or salts the velocity of sound increases with the amount of the dissolved gas or salt. The ratio of the two specific heats for ether at 15’ is 1.376. It should be noted that in order t o obtain dust figures in liquids the vibration of the liquid column must be in harmony with that of the containing tube. The dust employed by the author was powdered pumice stone. J. C. P. A New Method of Determining the Melting Point of Metals. IWAN I. SHUKOFF and W. J. KURBATOFF (J. Buss. Phys. Chim. SOC. 1907 30 1546-1548).-A similar apparatus has been described by Loebe (Abstr. 1907 ii 735) but the authors claim priority.Internal Friction and Density of the Bunsen Flame. AUGUST BECKER (Ann. Physik 1907 [iv] 24 823-862).-Measure- rnents have been made of the extent to which small solid spheres are buoyed up a t various points in the interior of a bunsen flame and in currents of different gases moving with known velocity. From these observations it appears that the variation of the interns1 friction from point to point of bhe bunsen flame is similar t o that detected by Bunsen for the thermal and chemical action and by Lenard for the emissivity. From the variation of the internal friction it is possible t o make an estimate of the composition of the gaseous mixture at different points in the flame. Curves of Instantaneous Heat Power determined from Chemical Reactions. ALDO MIELI (Gazxettu 1907 37 ii 636-647).-The heat power of a constant source of heat is defined as the quantity of heat either positive or negative developed per unit Z .K. J. C. P. VOL. XCIV. ii 11154 -4BS'l'RACTG OF CHEMICAL PAPERS of time. With a variable heat source the notion of an instantaneous heat power must be employed. The author deduces theoretically the time curves of instantaneous heat power for different chemical reactions. For a simple isothermal reaction this curve is homologous with that expressing the velocity of the reaction. The same is the case with reversible or lateral reactions but with polygrade reactions the two curves are not homologous. Similar relations hold for these various types of reactions when the latter take place adiabatically.The general case in which a reacting system is exchanging heat with its surroundings but is not a t constant temperature is also considered. T. H P. Calorimetric Method Applied t o the Study of Slow Reactions. JACQUES DUCLAUX (C'on~pt. re76d.) 1908 146 120-1 23). -The corrections which must be applied to the numbers observed in the calorimetric study of a reaction and become large and uncertain when the reaction is a slow one can be reduced to very small quantities by using as a calorimeter a Demar tube provided with a cork and immersed completely in the water of a ttermostat and by ensuring that initially the tube and liquids studied have the same temperature as the thermostat. For a tube cont,aining 35 C.C. of liquid and having an excess temperature of 1" after one minute duration the correction is only 0*003" and the method has the very great advantage that this correction can be determined once for all with an approximation of at Ieast 1 iu 20.The volume of air above the liquid being small no correction is necessary for evaporation and the rise of temperature being slow the lag of the thermometer causes an inappreciable error. The only difficulty arising when it is required t o measure absolute quantities of heat consists of the determination of the water-equivalent of the calorimetric tube which may amount t o 20% of the whole heat value. It can be determined either from the dimensions of the tube or by comparative experiments with sub- stances developing a known quantity of heat. Besides being used for thermochemical measurements the method has a very important application in the study of diastatic reactions of all kinds.By its means the course of a reaction can be followed since in the absence of any complication due to a secondary reaction the quantity of matter transformed in dilute solutions is proportional t o the rise of temperature continued observations of which will there- fore lead to the determination of the law of the transformation. The method has been successfully applied to the catalysis of hydrogen peroxide solutions by ferric hydroxide the inversion of sucrose and the saponification of ethyl and amyl acetates. The degree of accuracy obtained when using a thermometer reading to 0.02' is two to four times less than the ordinary titrimetric or polarinietric methods but it could be increased a t the expense of simplicity by using a n electrical thermometer.The method has the advantage of being applicable t o any liquid whatever at any temperature below loo" the only cou- clition essential being that ail appreaiablo yusntiCy of heat is developed. E. H.1 Y * GENERAL AND PHYSICAL CH EMIS‘l’ltY. 11 5 Determination of the Heat of Combustion of Organic Com- pounds by Use of the Platinum Resistance Thermometer. EMIL FISCHER and FRANZ WREDE (Sitxzcngsbcr. k. Akccd. TViss. BerZirL 1908 129 -1 46)-By substituting a platinum resistance thermometer for the mercury thermometer commonly used the accuracy with which the heat capacity of the bomb stirrer $c. can be determined is considerably increased. The estimated maximum possible error in the calibration of the apparatus used by the authors is 0.05%.For the purpose of obtaining standard values which may be used in the calibration of other calorimetric bombs the heats of combustion of sucrose and benzoic acid have been carefully determined. The calculated heats of combustion for 1 gram of substance (weighed in vacuum) are for sucrose 16.545 for benzoic acid 26.475 kilowatt seconds. Assuming that 1 kilowatt second=0*2390 Cal. the numbers are respectively 3.954 and 6.328 Cal. H. 11 D. Heat of Formation of Anhydrous Barium and Strontium Oxides. ROBERT DE FORCRAND (Compt. rend. 1908 146 2 17-220). -Pure anhydrous barium and strontium oxides can be obtained in the form of colourless powders by heating the corresponding hydroxide in a current of dry hydrogen a t SOO-S50° (Abstr.1907 ii 683 928). The heats of solution of these oxides calculated from their heats of solution in dilute hydrochloric acid ar0 for 1 gram-molecule of’ SrO in 20 litzes and 1 gram-molecule of BaO in 12 litres of water a t 1 5 O 30.8 Cal. and 55.640 Cal. respectively. The dis- crepancies between these values and those obtained by Thomsen (29.34 Cal. and 34.52 Cal.) are probably due to the impurities which are always present in alkali-earth oxides obtained by ignition of the nitrates. The heat of formation of the oxide of calcium lithium strontium or barium calculated from the heat of Fohtion of the oxide (Abstr. 1907 ii 683 928) aDJ of the metsl (Guntz Abstr. 1903 ii 410; 1905 ii 300; 1906 ii 229) is 151.90 143.32 137.60 or 125.86 Cal.respectively and the corresponding values for the peroxides of the metals are 157.33 162.65 152.10 and 145.71 Cal. respectively. The author draws attention to the close approximation between the thermochemical constants of strontium and lit,hium (comparelvyrouboff Abstr. 1897 ii 173). M. A. W+ Heats of Dissolution of the Alkali Metals and the Heats of Formation of their Protoxides. ~ T I E N N E RERGADE (Conzpt. rend. 1908 146 129-131. Compare Abstr. 1907 ii 737).-Owing to the explosive violence with which rubidium and czesium react with water Joannis’ apparatus (Abstr. 1888 1238) cannot be used to determine their heats of solution. The author has employed instead a modifi- cation of Mahler’s calorimetric bomb of which a diagram and descrip- tion are given.By niems of this apparatus the heats of dissolution of sodium potzssiiini 1-nbidium cresium arid their protoxides were mexsurecl. The sodium used contained less than 0.1% of potassium the potassium was re-distilled in a vacuum from the commercial metal and the rubidium and cssiuru were prepared from the pure chlorides 11-2156 ABSTRACTS OF CHEMICAL PAPERS. The following are the mean values obtained from a concordant series of experiments (1) (Na,Aq) = 44.1 Citl. (K,Aq) = 46:4 Cal. (Rb,Aq) = 47.25 Cal. (Cs’Aq) = 48.45 Cal.; (2) (Na,O,Ay) = 56.5 Cal. (K,O,Aq) = 75.0 Cal. (Rb,O,Aq) = 80.0 Cal. (C.s,@,Aq) = 83.2 Cal. The heats of dissolution of rubidium and czsium are lower than the values 48-2 and 51.6 given by Beketoff whilst the values f o r sodium and potassium are slightly higher than those of Joannis.The numbers obtained for the heats of dissolution of rubidium and ccesium oxides differ from those previously found by the author. The dis- crepancy in the case of the former oxide may be due to the fact that rubidium oxide gradually decomposes on exposure t o light with libera- tion of the metal. Froin the series (1) and (2) the following values are calculated (Na,,O) = 100.7 Gal. (K2,0) = 86.8 Cal. (Itb,,O) = 83.5 Cal. (CS,,~) = 82-7 Cal. for the heats of formation of the oxides. Both series of numbers indicate a perfectly regular variation in the thernial properties of the alkali metals with increasing atomic weight. The anomalous value for cmium obtained by using Beketoff’s value for the heat of dissolution of the metal is no longer observed and the alkali metals are now shown t o follow the general rule of decreasing affinity for oxygen with increasing atomic weight.E. IT. Densities of Some Fused Salts and their Mixtures at Various Temperatures. RICHARD LORENZ H. FRET and A. JABS (Zeitsch. physikcd. Chew. 1908 61 468-474).-The method employed was essentially that described by Brunner (Abstr. 1904 ii 244). The results obtained for the densities of the pure fused salts may in all cases be represented by a formula of the type y = a + bt where y is the weight of 1 c.c. t is the temperature on the centigrade scale and a and b are constants. The formu12 for the various salts are as follows ; potassium nitrate (m. p. 3 2 9 O ) y = 2.044 - 0.0006t ; sodium nitrate ( i n p.310°) y = 2.12 - 0.0007t; lead chloride (m. p. 5 1 2 O ) y = 5.627 - 0.00144t ; lead bromide y = 6.175 - 0.00145t ; cadmium chloride y = 3.731 - 0.000685t ; potassium bromide y = 2.626 - 0~000Slt. I n the case of sodium chloride potassium chloride and sodium bromide the authors’ results are represented satisfactorily by Brunner’a formulze (Zoc. cit.). Densities at various temperatures and various concentrations have also heen determined for the following pairs of salts lead and potassium chlorides ; lead and barium chlorides ; lead and potassium bromides ; cadmium and potassium chlorides. The variation of density with temperature and concentration may be represented by the iormula y = a - b.t + c.Nt + d.N where N is the molecular proportion of one constituent 1 - N the molecular proportion of the other and a 6 c and d are constants J.c. P. A Simple Form of Release for Victor Meyer’s Vapour-Density Apparatus. THOMAS S. PATTERSON (Chem. News 1908 98 73).- A device which enables the little tube containing the weighed quantity of substance to be introduced into the apparatus in n. vertical position.h cork diaphragm with an eccentrically-bored hole is fitted at the base of the wide- part of the neck. The cork closing the apparatus has a hole bored in a slanting direction through which a glass t u b e passes The tube of substance is dropped into this and by rotating the cork i t is allowed to fall through the hole in the diaphragm. 1'. H. New Method Suggested for Determining Vapour Densi- ties. 11. PHILIP BLACKMAN (Chenz.News 1908 97 27. Compare Abstr. 1907 ii 931).-The apparatus previously described has been simplified. I n the new form the manometer consists of a capillary U-tube one end of which is sealed and the other closed by a short thread of mercury. The U-tube is placed in the glass cylinder the stopper a t the lower end being made tight by pouring in a little mercury. H. M. D. An Apparent Exception to the Theory of Heterogeneous Dissociation Equilibria. RICHARD ABEQG (Zeitsch. physikal. Chem. 1908 61 455-456).-Attention is directed to Baker's observations (Trans. 1894,65 611 ; 1898,73 422) according t o which perfectly dry ammonium chloride vaporises without dissociat,ion. From these and other experiments it appears in fact that ammonium chloride when vaporised exerts about 1 atmosphere pressure at 360° whether it is dis- sociated or undissociated.I n the first case the partial pressure of the undissociated molecules is very small; in the second case it is about 1 atmosphere. This result is inconsistent with the theory of hetero- geneous equilibria according to which the concentration of the undissociated vapour should a t a given temperature be independent of the presence of other gases including the dissociation products. With the view of finding whether this inconsistency is real or apparent the subject has been treated experimentally by Johnson (see following abstract). J. c. P. Vapour Pressure of Dry Sal Ammoniac. FREDERICK 31. G. JOHNSON (Zeitsch. physiklcl. Chcm. 1908 61 457-463. Compare A begg preceding abstract).-An apparatus is described made entirely of glass in which ammonium chloride could be dried perfectly and examined (1) as regards vapour pressure and (2) as regards vapour density.The pressure was measured with the help of a flat spiral glass tube which acted as a manometer (see Laclenhrg and Lehmann Verh. physikal. Ges. 1906 8 20). The author confirms Baker's results and finds that the density of perfectly dry ammonium chloride a t 345' is that of the undissociated compound. The vapour pressures a t various temperatures of this specially dried ammonium chloride and also of the ordinary ammonium chloride have been determined and it is found that the vapour pressui e of the undissociated salt in the one case is equal to tho sum of the vapour pressures of the dissociation products in the other case.The result is not in harmony with the theory of heterogeneous dissociation equilibria but no simple explanation of this can be suggested. J. C. P.158 ARSTRACTS OF CHEMICAT PAPERS. Relationships between Compressibility Surface Tension and other Properties of Substances. ?'i~eouorm W. I~IC'HARDS and J. HOWARD MATHEWS (Zeitsch. pltgsikid. C'hm. 1908 61 449-454. Compare Ritzel Abstr. 1907 ii 740).-111 this pre- liminary comrnunicatioii the a11 thors record valucs for the coin- pressibility boiling point density surface tension vapour tension a t ZOO and molecular latent heat of vnporisation for thirty-seven organic liquids. The compressibility (p) and the surface tension (7) are found to be connected by the following equation pf = coast. = 2.5 x low3 which is valid for all the liquids examined exccpt four halogen compounds.The fact that substances with a high surface tension are only slightly compressible is discussed from the point of view of the theory that the atoms are compressible. It is pointed out that conipressibility must depend not only on the volume changes resulting from the alteration of the molecular distances but also on the internal changes of the molecules. Surface Tension of Liquids Investigated by the Method of Jet Vibration. P. 0. PEDERSEN (Proc. h'oy. Xoc. 1907 80 A 26-27).-Lord Rayleigh showed many years ago (ibid. 1879 29 71) that the surface tension of a liquid could be calculated from observa- tions on a vibrating jet when the length of the standing waves the velocity and cross-section of the jet and the density of the liquid are known.The author has worked out methods for determining these magnitudes and has obtained very consistent results for the surface tension. The surface tension of water toluene and aniline are 74.30 28.76 and 43.00 dynes/cm. at 15". Some measurements have also been made with aqueous solutions. G. S. LEOPOLD ROSENTHALER (Arch. Pharm. 1907 245 686-689).-A reply t o certain criticisms made by Glassner and Suida (Abstr. 1907 ii 932) on a paper by Rosenthaler and Tiirk (Abstr. 1907 ii 12). The former authors did not observe that charcoal adsorbs relatively much more strongly from dilute than from concentrated solutions because they used dyes. I n the case of dyes various chemical complications disturb the purely physical phenomena of adsorption Rosenthaler and Turk on the other hantl worked with caffeine and with dextrose and were thus able t o observe the great effect of the concentratim of the solution.Velocity of Absorption of Gaseous by Solid Substances. ARTHUR HANTZSCH and G. WIEGNEH (Zeitsch. physiknl. Chein. 1908,61 475-490).-Re-examination of the experimental basis of a previous paper (Abstr. 1904 ii 541) shows that the conclusions then reached must be modified. The absorption of ammonia by solid acids and of hydrogen cliloride by solid bases does under certain conditions take place in approximate accord with the formula for a unimolecular reaction but it is not possible to draw any trustworthy conclusions as to the magnitude of the affinity constant of tho acid or base from the magnitude of the absorption constant.The absorption of ammonia or hydrogen chloride in a diluted condition takes place nccording to the J. C. P. Decolorising Action of Charcoal. G. B.C,I3NERAT AND PHYSICAT CHEMISTRY. 159 formula for R bimolecular reactioii only in a limited number of cases. Difference in the rate of absorption cannot be employed RS a means of distinguishing true acids from pseudo-acids or true bases from pseudo- bases. J. C. P. Absorption of Gases by Rubber Tubing. RUDOLF DITMAR (Chena. ZerLtr. 1907 ii 1578-1579 ; from The I-HL&~ Eubber JournnE 34 85-86 197-198).-An arrangement is described for measuring the pressure of a gas in a rubber tube jacketed with the same or with another gas I n experiments with a tube of red rubber of unknown composition air is found t o exert pressure when the tube is surrounded by air.Carbon dioxide on the other hand is absorbed by the rubber tube when the jacket is air or t o a smaller extent when the jacket is hydrogen whilst hydrogen is absorbed although to a smaller extent than carbon dioxide when the tube is surrounded by air or carbon dioxide but exerts pressure when the tube is jacketed with hydrogen. The absorp.ion of carbon dioxide by a tube of Para rubber is found to be the same whet.her the atmosphere surrounding the t u l e is ctrbon dioxide or air. G. Y. [Diffusion of Metals in Mercury.] G. ~ICPIFAIL S m n t (Ann. Physik 1908 [iv] 25 252-256).-The author criticises CVogaii’s view (Abstr. 19tr7 ii 606) that certain metals when dissolved in mercury are in the monatomic condition and suggests that in many cases at least compounds of mercury and the dissolved metal are formed (compare Haber Abstr.1902 ii 638; Smith Abstr. 1906 ii 673; 1907 ii 463). It is pointed out that when Wogau’s values for the diffusion constants of the metals are divided by the correspond- ing atomic weights and the figures so obtained are plotted against tho atomic weight two curves reLult; on one of these lie the figures for Li Ka K Ca Rb Sr Cs Ba and T1 the metals which form com- pounds with mercury ; on the other lie the figures for Zn Cd Sn and Po the met& which dJ not combine with mercury. J. C. P. Organic Solvent and Ionising Media. X Solvent Power and Dielectric Constant. PAUL \VALDEK (Zeitsch.physikctE. Chem. 1908 61 633-639. Compare Abstr. 1904 ii 227 ; 1906 ii 149 335 336 527 ; 1907 ii 231 437 519 734).-The variation in the solubility of tetraethylammonium iodide in water and a number of organic liquids is recorded. For the purpose of this paper the solubility (s) is expressed as molecular percentage of the salt in the saturated solution that is if the saturated solution contains n molecules of tetraethylammonium iodide for every LV molecules of solvent then s = 100rz/(n + N). It is found that the solvent power for tetraethylammonium iodide falls off as the dielectric constant of the solvent diminishes; in fact’ s:f is very nearly proportional t o the dielectric constant. An analogous result is obtained with tetrapropylanirrionium iodide as solute.J. C P.160 ABSTRACTS OF CJIKMICAL PAPERS. Solutions in Mixtures of Alcohol and Water. ERNST CUNO (Ber. Deut. physikul. Ges. 1907 5 735-738; Ann. Physik 1908 [iv] 25 346-376).-The author has determined the composition of the two layers which are formed when varying quantities of potassium carbonate or manganese sulphate are dissolved in mixtures of alcohol and water. I n the case of both salts alteration of temperature has only a very slight effect on the composition of the two layers. The expressions suggested by Bodkinder (Abstr. 1891 ii 794) and by Herz and Knoch (Abstr. 1905 ii 709) are fairly constant for medium alcohol concentrations. The conductivity of potassium carbonate and manganese sulphate in mixtures of alcohol and water has also been studied.For a given quantity of salt the conductivity rapidly diminishes as the concentra- tion of the alcohol increases. Increase in the proportion of alcohol lends also to a displacement of the maximum conductivity in the direction of solut,ions containing less salt J. C. P. Crystallisation from Aqueous Solutions. ROBERT MARC (Zeitsch. physikul. Chem. 1908 61 385-398).-1t is suggested that there is a rate of crystallisation from a supersaturated solution quite distinct from a diffusion velocity This view is supported by experi- ments on the rate of crystallisation of potassium sulphate from super- Fatimated solutions a t 0’. A quantity of fine crystals was introduced into n supersaturated solution the solution was vigorously stirred and the process of crystallisation was followed by taking out samples of the solution from time t o time and analysing.The quantity of crystals introduced a t the beginning of the experiment was three to five times the quantitywhich separated during the crystallisation. Thesurface of the ctmystals may be taken as proportional to (W)3 where W is the weight of crystals present and the rate of crystallisation is approxi- mately proportional t o the surface of the crystals calculated in this way. It appears that the crystallisation proceeds according to the formula for a bimolecular reaction and that the temperature-coefficient is about 1.6 for an interval of 10’. The theoretical interpretation of these results is postponed until more experimental material is available. J. C. P. Action of Some Electrolytes on Colloidal Silver Solutions.The Process of Coagulation. H. W. WOUDSTRA (Zeitsch. physikal. Chem. 1908 61 607-632).-The various solutions of colloidal silver employed by the author were prepared by the methods of Muthmann Carey Lea and Bredig. The colloidal silver prepared by Muthmann’s method resembles that prepared by the other methods in being electro- negative and in promoting the decomposition of hydrogen peroxide. The procedure adopted in studying the coagulative power of different salts was to find in each case which of a number of solutions of gradually diminishing concentration was just unable to produce turbidity on addition of a given quantity of colloidal silver solution. The concentration of this particular salt solution is described as the ‘‘ limiting concentration ” for that salt.C E N E HA T AN 1) P M Y 8 I C A L C H EM I STRI’.161 The coagulation is accompanied by peculiar colour effects the nature of the colour depending apparently on the anion of the salt. Chlorides (except lead chloride) give a bluish-white opalescence resembling silver chloride. Coagulation by lead chloride and by sulphates is accompanied by a red coloration. The power of salts to coagulate colloidal silver solutions depends almost entirely on the cation and increases with the valency of the cation (compare Whetham Abstr. 1900 ii G2). For a given salt the ‘‘limiting concentration” diminishes (1) with the age of the colloidal solution on which it is allowed to act and (2) with increasing concentration of the colloidal solution. The author discusses the various theories of coagulation which have recently been brought forward and concludes that the formation of large aggregates from the fine colloidal particles is t o be attributed to the electrical action of the ions.His experiments are in general harmony with Whetham’s views (loc. cit.). J. C. P. The Process of Gelatinisation. 111. S. A. LEVITES (Zeilsch. Chem. I n d . Iiolloide 1908 2 208-215. Compare Abstr. 1902 ii 312 ; 1903 ii 641).-The transition from the colloidal to the gelatin- ised condition can be conveniently follo~ved by measurement of the viscosity. With this object in view the influence of concentration of temperature and of foreign substances on the viscosity of colloidal solutions has been examined.For concentrated colloidal solutions the viscosity T,I is approximately represented by the exponential formula v=A% where A is a constant and x the concentration of the dissolved colloid. For dilute solutions closer agreement with the experimental data is obtained by means of the linear expression T,I = 1 + CLX in which CL is a constant. Lowering of temperature increases the viscosity but for a given solution there exists a certain temperature minimum below which the viscosity gradually increases with time according to a linear equation. Foreign substances (crystalloids) which increase the viscosity of water increase the viscosity of colloidal solutions and a similar relationship holds for crystalloids which diminish the viscosity of water. This does not hold if two or more crystalloids are added to the colloidal solution or if the crystalloid reacts chemically with the dissolved colloid.H. 3%. D. Non-miscibility and the Mass Law. WILDER D. BANCROFT (J. Physical Chem. 1908 12 30-35).-h theoretical discussion of the deviation of a reversible change A + B S A B from the simple equilibrium equation y x = K x which may be expected when the two components A and B are not completely miscible in the piire condition. Such a system is exemplified in chloral + water chloral hydrate. The author argues that the non-miscible components A and B will render each other less soluble in the compound AB and hence increase one another’s chemical potential (compare McIntosh Abstr. 1898 ii 65). The result will be a forcing back of the actual percentage dissociation of AB.The degree to which the chemical potentialsI62 ABSTRACTS OF CHEMICAT PAPERS. of A and B would be affected is not known but the author considers the effect 011 the equilibrium in several hypothetical cases. R. J. c'. Equilibria in Ternary Systems ; Additive Products of Aromatic Nitro-derivatives and Mercuric Chloride. LIJIGI MASCARELLI (Atti 12. Acctcd. Lincei 1908 [v] 1'7 i 29-39. Com- pare Abstr. 1907 i 25).-The author has investigated the equilibria in tbe systems p-nitrotoluene and merctiric chloride p-nitroanisole and mercuric chloride and a-nitronaphthalene and mercuric chloride using ethylurethane as third substance (compare this vol. ii 94). The results are in complete accord with the theoretical deductions concerning equilibria i n ternary systems (Zoc.cit.). The double salts which these aromatic nitro-derivatives form with mercuric chloride have the same composition as the corresponding double salts formed by iodoxy-derivatives with mercuric chloride and it is probable t h a t similar relations exist bet ween the corresponding mercuric bromide double compounds. T. H. P. Attempt to Measure the Rate of Neutralisation at Low Temperatures. RICHARD ABEW and J. NEUSTADT (Zeitscli EZektro- cfienz. 1908 14 2 - 3)-Alcoholic solutions of hydrochloric acid and lithium hydroxide were mixed a t - 80° but neutralisation was completed in the time required to mix the solutions. At - looo the reaction did not appear to be quite complete thirty and forty seconds after mixing but one minute later i t was complete.The conductivity of the solutions was used to follow the progress of the change. Alcoholic solutions are too viscous at temperatures below - 100' to permit of rapid mixing. Reaction Velocity in Gases which are in a State of Motion. MAX BODENSTEIN and KARL WOLGAST (Zeitscli. physikal. Chem. 1908 61 422-436).-It is incorrect to assume always t'hat when a mixture of reactive gases passes through a vessel kept at a constant tempers- ture their concentratioii diminishes uniformly from the entrance to t h e exit of the tube. If the temperature is such t h a t the p s e s react slowly if the vessel is not very narrow in proportion to its width and if the rate of passage of the gases is not too great then thorough mixing will occur the composition of the gaseous mixture will be the same throughout the tube and the same as that of the issuing mixture.F o ~ i i i ~ ~ l ~ . applicable to these conditions are developed and they differ from the f o r m u l ~ usually employed. Thus for a uni- inolecular reaclion X the absolute amount of the product formed will be proportional t o the duration 1' of the experiment t o the volume v of the reaction vessel and to the concentration ___ of the substance which is undergoing change hence X = l / 1'. V/v.X',l(A - LY). The formula which is similarly deduced for a bimolecular reaction is The validity of the latter formula was tested by experiments on the 3lixtnres of hydrogen T. E. A - X V k = 117'. V2/v. X / ( A - X ) ( B - S). rate of Combination of hydrogen and iodine.and iudiiie with hydrogen i n largo excess were passed through tuhes heated to constant temperutureu (406” 430” 440 ’) and the issuing niistures n-erc analysed.At thmc tempemtureh the reaction between Iiydrogeu an~l iodine is slow SO hlixt if the gnws are not passed too rapidly the conditions are fulfilled on wvhicli the foregoing formulae are based. The results :we in satisfactory accord with the formulae and values itre obtained for the velocity constant of the reaction H + I = 2H1 which agree well with those deduced from the experi- ments made in closed vessels (Abstr. 1899 ii 637). Jellinek’s experiinents (Abstr. 1906 ii 437) are considered from the authors’ point of view and the velocity coefficients calculated by their formha vary less than those calculated in the usual way.J. C P. Urazoles. XII. Velocity Constants and Mechanism of the Reactions of Alkyl Halides with Urazoles and Urazole Salts. SALOMON F. ACREE and G. H. SHADINGER (Amer. Cheirz. J. 1908 39 226-227. Compare this vol. i 224).-An investiga- tion is being carried out with the object of elucidating the mechanism of the reactions which take place between alkyl salts and other substances such as hydroxides carbonates nitrates and urazoles. The present paper deals with the velocity of the reactions of alkyl halides with 3-thio-1-plienylurazole and its metallic salts sodium thioacetdte and potassium hydroxide. The rate of change of the urazole into its disulphide and the rate of hydrolysis of methyl iodide in 50% alcohol have also been determined.The reaction between sodium 3-thio-1-phenylurazole and ethyl iodide was followed by con- dnctivity measurements and evidence was obtained that ethyl iodide does not unite t o an appreciable extent with the sodium or urazole ions I n the reactions of alkyl halides with urazoles hydroxides carbonates and thioacetates the alkyl halide reacts with the anion of the other compound thus The results of the work lead t o the following conclusions. - - C,H,I -I- OH -+ C,H,*OH +I or dxldt = Ktl.rc,la x C ‘ ~ t r x COW. 7’he hypothesis of Bruyn and Steger (Abstr. 1899 i 849) that alkyl hslides react with other substances by dissociation into alkyl and halogen ions and subsequent union of the alkyl ion with the anion Nef’s view that the reaction is due to the dissociation of the alkyl halide into the corresponding halogen acid and an unsaturated methylene complex which reacts with other substances and Euler’s hypothesis (Abstr.1906 i 789) that the reaction is due to the forma- tion of a complex cation and its subsequent reaction with the anion are discussed and shown not to be in harmony with the evidence now obtained. The alkyl halide molecules react with the anion of the substance which is b&ng alkylated probably forming an intermediate unstable - complex anion C,H’,I*X which immediately yields lislogen ions and C,H,X. -Afkyl iodides react more readily with the urazoles than do nlkyl164 AHSTR kCTS OF CHERIICAL PAPERS bromides and the bromides more readily than the chlorides. Priuary alkyl halides are more reactive than secondary alkyl halides towards urazoles and the latter more so than the tertiary compouuds.This may be partly dne to the so-called space interference. E. (2. Hydrolysis of Salts. AUGUSTE ROSENSTIEHL (BUZZ. SOC. chim. 2908 [ivl 3 86-89).-The author has shown in a former paper (Abstr. 1907 ii 610) that all salts of which the aqueous solutions obey Berthollet's laws are completely hydrolysed in solution and the present paper isconfined t o a discussion of the cases in which both the bases and acid formed on hydrolysis are soluble in water and do not readily reveal themselves. The experimental evidence is that supplied by H. ltose (AWL Php. CJiena. 1853 86 101) in his work on the action of water on various salts and includes such observations as t,he following (1) a dilute aqueous solution of an alkali carbonate on ebullition loses some carbon dioxide; (2) a concentrated solution of sodium carbonate precipitates from a solution of lead nitrate the substance 6(Pb0,C02),Pb(H,02) whilst a dilute solution furnishes the product 3(Pb0,C02),Pb(H,0,) ; (3) a concentrated solution of borax gives a reddish-violet colour with reddened litmus paper whereas a dilute solution of borax gives a blue colour; (4) alkaline osmates are inodorous when dry but on solution in water develop the odour of osniic acid and similarly a dilute aqueous solution of an alkali salt of a fatty acid has always a slight odour of the fatty acid although the dry salt may be inodorous.The action of water in these cases is (a) chemical (in effecting hydrolysis) and ( b ) physical (in maintaining by its mass the new condition set up by the hydrolysis).T. A. H. Hydrolysis of the Salts of Weak Acids and Weak Bases and its Variation with the Temperature. HARALD LUND~N (J. Chim. Phps. 1907 5 574-608).-The dissociation constants k and kb of certain weak acids and bases of which the values of k and KO respectively lie between 10-7 and 10-10 have been determined by cobductivity measurements as previously described (Abstr. 1907 ii 443) at intervals of temperature between 10' and 50' (in the case of boric acid only between 15' and 40"). H' + H2B03' is 5.48 6.62 and 8.49 x 10-10 a t 15" 25" and 40' respectively ; when the acid is neutralised with ammonia only the salt NH,H2B0 is formed in appreciable amount. at lO" 40° and 60' respectively ; for p-nitrophenol ka is 4.5 7.0 and 12.7 x loe8 at loo 25" and 50' respectively and for 2 4 6-trimethyl- pyridine kb is 1-22 2-05 and 3.75 x 10-7 at loo 25O and 50' respectively.In connexion with the results for p-nitrophenol i t is poiuted out that the colorimetric method for determining the dissocia- tion constants of indicators employed by Friedenthal and Salm (Abstr. 1906 ii 218) does not give trustworthy results. The dissociation constant for water has been calculated from the constants for p-nitrophenol and 2 4 6-trimethylpyridine and the degtee of hydrolysis of the salt formed by these two compounds; the For boric acid ha for the dissociation H,BO For pyridine kb is 1.06 4.25 and 8.6 xGEXERBL AKD PHYSICAL CHEMISTRY 16.5 values are 0.31 1-05 and 5.17 x a t lo" %* and 50" respectively in excellent agreement with Kohlrausch's values froin the conductivity of pure water.From the variation of the dissociation (ionisation) and of the degree of hydrolysis of the salts with temperature the heats of dissociation and of neutralisation respectively have been calculated for the compounds ment'ioned nbove. The values obtained agree satisfactorily with those obtained cnlorimetrically as far as coinparison is possible. The heat of neutralisation of boric acid is 11,440 - 37.St cal. and that of pyridine 6037- 14-5t cal.; the heat of dissociation of ammonia is - 2608 + 58-05t cal. The heat of dissociation increases with the temperature for all the electrolytes examined but the temperature-coefficient for the heat of neutralisation may be positive or negative. G.S. RUDOLF WEGSCHEIDER (Xonatsh 190S 29 83-133).-A discussion of the results of various authors who have studied the hydrolysis of the glycerides. The view that the hydrolysis takes place in three stages is supported by observations made in determining the velocity constants of the hydrolysis of other esters. The arguments are shown t o apply to all the seven reactions which may occur within the three stages. The conditions are laid down under which the velocity coefficients of similar reactions with substances differing in the number of t'heir reactive groups are proportional to the numbers of such groups. The theory of the progressive hydrolysis of the glycerides is developed on the assumption that all the possible isomerides are formed.New conditions are discovered under which the whole reaction may be birnolecular or in presence of an excess of the hydrolysing agent' unimolecular and a basis is provided for the theoretical treatment of observed deviations. The following general conclusions are arrived at the hydrolysis of the glycerides takes place in stages in the course of which all the possible isomerides are formed. If the whole reaction as measured by the amount of acid liberated takes place wit'h tri- or di-glycerides approximately according to the law of unimolecular reactions and if the unimolecular constants for the hydrolysis of mono- di- and tri- glycerides are almost equal the velocity constants for the various reactions must be related as follows ( I ) the hydrolysis constants of the two monoglycerides must be equal.(2) The hydrolysis constant of the s-diglyceride must be double that of a monoglyceride and equal to the sum of the two hydrolysis constants of the as-diglyceride. (3) The sum of the two hydrolysis constants of the triglyceride is three times the constant for a monoglyceride. This is the case in the hydrolysis in acid solution but has not yet been shown to apply to the a1 kaline hydrolysis. If the hydrolysis of the briglyceride is unimolecular but not that of the diglyceride the various hydrolysis constants must be represented by the expressions k = 3KB,/C k = - 3K/C k = H k + k,,z2K k = [K(2a - k21) - ag]/B - kal k = K in which K is the constant for the whole apparently unirnolecul;tr reaction a = k + kz2 Theory of the Saponification of the Glycerides.166 ABSTRACTS O F ClIERIlCAL PAPERS.I! = 2 K - cc and C= I<- ( I or by the expressions k + k = 311 k = [ 12 Kk + k,,(3 K - k1)2]/3k1(3K+ k ) k2( = K. The non-appearance of mono- and di-glycerides in recognisable amounts amongst the products of the hydrolysis of insoluble tri- glycerides in heterogeneous systems by means of aqueous solutions cannot be urged as an argument :tgainst tlie view that the hydrolysis takes place i n stages as in geneid if the transfo~mation of an almost insolnble substance is accompanied by a process of solution the appearance of an intermediate product in quantity is possible only if its velocity of transformation or its solubility is markedly smaller than that of the original substance.The various points are treated mathematically in an appendix which fornis the second arid larger part of t'he paper. JEAN R. SENDERENS (Compt. rewt. 1908 146 125.-127. Compare Abstr. 1907 i 577)- The silim precipitated from sodium silicate washed free from acid dried and completely dehydrated by moderate calcination is a catalyst of alcohols giving et hylenic hydrocarbons exclusively. Thus it dehydrates ethyl alcohol a t 280") giving 99.5% of ethylene. But the same silica after being calcined in a platiniim crucible a t a bright red heat for an hour does not act on ethyl alcohol beIow 340° and then gives 5.3% of hydrogen and 94.7% of ethylene whilst if it is calcined for six hours at a white heat tlie decomposition of ethyl alcohol requires a temperature of 390' and then gives 17.1% of hydrogen Hyaline quartz when finely powdered does not begin to catalyse atcohol below 460° giving ethylene and 52% of hydrogen and if this quartz is previously calcined for six hours a t a white heat the decomposition temperature of alcohol rises to 480' and the yield of hydrogen to 95.2%.The latter prepared by precipitation from a salt washed dried and slightly calcined is exclusively a dehydrating catalyst towards alcohols giving with ethyl alcohol 99.5% of ethylene at 2 7 5 O whilst after calcination for six hours at a white heat it does not decompose alcohol below 420' and then gives 12% of hydrogen. The conclusion is drawn that silica and alumina when gently calcined are dehydrating catalysts whilst prolonged calcination besides diminishing their catalytic power tends to make i t iriore dehydrogenating in character.The author considers that this will explain the disagreement amongst chemists as t o the action of silica and alumina on alcohols. k =[lZIi-k + k 1 ( 3 1 ~ ~ 1 ) 2 ] / k ( 3 1 + k ) k21;K k,,= [6l;r((K-k2,)]j3K+k G. Y. Catalytic Power of Silica and Alumina. Similar behaviour is observed with alumina. E. H. Action of Alternating Currents of High Frequency on tha Decomposition of Hydrogen Peroxide by Colloidal Platinum. A. LEBEDIWB (Hw71. ~So'oc. c h i m 1908 1 iv] 3 56-75).-For these oxperirtitmt,s a roil giving n s p r k 40 c m . long was employed with a primary current varying froiii 2.5 t o 4.5 amperes. The platin~ini electrodes were each 2 sy. em. in area and each was enclosed ill a small glass tube having a constricted aperture covered with yarchmeiitGENERAL AND PHYSICAL CHEMISTRY.167 paper and dipping in the reaction liquid contained in a voltameter which is figured in the original. The water employed as a solvent had a conductivity 2 x and the colloidal platinurn was prepared by Bredig and von Berneck's method (Abstr. 1900 ii 213). The whole apparatus was immersed in a thermostat at 25". I n the several series of experiments made it was found that the normal rate of decomposition of the peroxide by the coIloidal platinum (Bredig and von Berneck Zoc. cit.) was diminished under the influence of alternating currents of high frequency and the irregularity of the diminution is attributed to irregularity in the primary current employed. On the contrary the rate of decomposition increased under the influence of the current when a small quantity of sodium hydroxide wa* added to the reaction liquid thereby increasing its conductivity.When a direct current from a 70 volt battery was employed no effect on the rate of decomposition of the peroxide was noticed and this was also the case when a direct discontinuous current was taken from the coil with an air-break of 0.75 cm. length. The greater part of the paper is taken up with a discussion of tho bearing of these preliminary results on theories of catalytic action and it is shown that the results are readily explicable on the assumption that catalytic action is due to a change in state of the surface of the catalyst and in this connexion attention is directed to Helmholtz's idea that between the two phases solid and liquid there exists a thin double layer carrying an electric charge which tends to diminisli surface tension.The influence of an electric current on catalytic action can then be explained as due to the change in potential difference and consequently in surface tension that i t induces and the further effect due to the addition of an electrolyte such as sodium hydroxide to the reaction liquid would be explained as due to change in potential difference induced by t h e electrical charges on the ions As t= the mechanism of the reaction the author dissents from Haber's view (Abstr. 1900 ii 720) that the platinum is alternately oxidised and reduced and suggests instead that the oxygen is merely stored temporarily in the colloidal platinum in the form of a solid solution T.A. H. Catalysis. I. Catalysis of Esters and of Imino-esters by Acids. JULIUS STIEGLITZ (An2ei*. Chern. J. 1908 39 29-63).-This paper is based on the results of experiments which have not yet been described. Methyl iminobenzoate is slowly decomposed by water with formation of methyl alcohol and benzonitrile very small quantities of methyl benzoate and ammonia being also produced (1) NH:CPh*OMe -+ C,H,.CN + MeOH ; (2) NH:CPh*OMe + H,O-+Ph*CO,Me +NH,. Both reactions are practically non-reversible under the conditions of the experiment. I n presence of hydrochloric acid however the velocity of the second reaction is greatly increased whilst the first reaction may be entirely suppressed.The acid unites will) the iniino- ester tho hythochloride is partially hydrolysed and ;L condilion of equilibrium is established thus NH,Cl:CPh-OMe t- H,O S OH*NH,:CPh*ORle + HC1.168 ABSTRACTS OF CHEMICAL PAPERS. It has been proved that the reacting substance which gives ammonia and a benzoate is the hydrochloride or rather its positiveion and that the accelerating action of the acid is simply due to the formation of larger reacting masses of the active ion from the scarcely ionised weak base. Non-electrolytes do not affect the velocity of the reaction between imino-ester salts and water but electrolytes have a decided ‘‘ salt effect ” (Euler Abstr. 1900 ii 269). The decomposition into nitrile and alcohol according to reaction (l) is greatly accelerated by the addition of alkali hydroxides owing to an increase in the con- centration of the negative ions.In the decomposition of an imino- ester in aqueous solution the non-ionised molecules of the ester also break down into nitrile and alcohol but the velocity constant is very small in comparison with that of the negative ions. An imino-ester decomposes therefore in accordance with three simultaneous reactions each proceeding with an established velocity constant (1) NH,:CPh*OMe + Ph*CO,Me + NH (2) kCPh*OMe -+ -t + PhCN + &Me and (3) NH:CPh*OMe -+ PhCN + MeOH. A mathematical treatment of these reactions is given and their theoretical significance and application to the catalysis of ordinary esters are discussed. The results of the work lead to the conclusion that none of the usual assumptions regarding catalytic action (compare Euler Abstr.1900 ii 532 ; 1901 ii 5 ; 1904 ii 318) is absolutely true under any conditions and that the only fundamental fact common to all catalytic actions is that of acceleration due to an increase in the active mass or concentration of a reacting component. E. G. Catalysis. 11. Catalysis of Imino-esters. JULIUS STIEGLITZ (Amer. Chem. J. 1908 39 166-183. Compare this vol. ii 29 and preceding abstract).-It was stated in the earlier paper that the catalysis of an imino-ester may take place in either of two ways (1) ROC( :N H)*OR’ + H,O -+ R*CO,R’ + NH and (2) R*C( :NH)*OR’ --+ R-CiN -+ R’*OH. The former reaction is enormously accelerated by acids and the latter by alkali hydroxides.Evidence was adduced to show that the reacting component in (1) is the positive imino-ester ion R*C(:NH,)*OR’ -+ R*CO,R‘+ NH and in (2) the negative ion R*C(:N)*OR’ -+ R*CiN+&R’. A third reaction takes place in the absence of acid or alkali involving the decomposition of the imino-ester according to (2) and in this case the reacting component is the non-ionised imino-ester itself. Each of these reactions proceeds with its characteristic velocity constant. A further study of the subject has led to the following conclusions. Imino-esters resemble acid esters in being decomposed much more rapidly by alkali hydroxides than by acids. The decomposition in aqueous solution cannot be accounted for by the decomposition of the negative ion by a process of autocatalysis or by assuming that it is produced by ionisation due to its amphoteric character ; the reacting mass is the non-ionised ester.The acceleration of tho decomposition according to (1) being greatly -t 4-GE’PUERAL AND PHYSICAL CHEMISTRY. 1G9 accelerated by acids it was tho-ught possible that the reacting component was not all the imino-ester salt but only its positive ion. It has been found however that a second accelerating force is involved and that the imino-ester salt itself as an electrolyte exerts a ‘ I sa.lt effect ” in its own catalysis. This effect is probably concerned with an increase in the ionisation of water. The salts of those imino-esters whish are the weakest bases have the greatest velocity of decomposition. A series of analogies between imino-esters and acid esters is given and it is shown that the chief point of difference between the two classes of substances lies in the more pronounced basic properties of the former and the formation of salts which are comparatively little hydrolysed.E. G. Catalysis. SALOMON F. ACREE (Arnes.. Chenz. J. 1908 39 145-156).-Polemical. A reply to Stieglitz (this vol. ii 29). E. G. Catalysis. VII. Reaction of Carbonyl Compounds with Hydroxylamine and Hydroxylamine Rydrochloride. SALONON F. ACREE (Amer. Chem. J. 1908 39 300-309. Compare Acree and Johnson Abstr. 1907 ii S56).-This paper has been written in view of the recent work of Abel (this vol. ii 26) Lapmorth (Trans 1907 91? 1133) Landrien (Abstr. 1905 ii 445) and Euler (Abstr. 1907 ii 1098). The data obtained by Acree and Johnson indicate that acetone and hy droxylamine in aqueous solutions combine readily and nearly completely thus (CH,),CO + NH,*OH z= (CH,),C:N*OH + H,O and that the velocity of the reaction is accelerated by acids owing to the formation of cations which are more reactive than the free bases (CH,),CO + NH,*OH (CH,),C*OH+ NH,*OH Z (CH,),C:NH*OH + H,O.The quantitative results seem to show that the free bases hydroxyl- amine and acetoxime as well as their cations enter into the reaction. I n this and in other cases the question as to whether the free base dissociated salt or non-dissociated salt undergoes transformation depends simply on the relative activity of each in the particular reaction. If it qnantity of acid is added which is not sufficient to use up all the base the non-catalysed and catalysed reactions take place side by side each with measurable rapidity and in this case the velocity of the reaction cannot be proportional to the concentration of the catalysing agent.In the presence of alkali hydroxide the reaction is greatly accelerated and proceeds nearly to completion. The alkali probably forms small amounts of XH,O ions which react much more rapidly with acetone thnn hydroxylamine does COMe + NH,OH + K + OH + + (CH,),:NH*OH + H,O or + + + - - + - + ClOMe + NH,O + I< + H,O CMe,:NO + K + 2H,O. VOL. XCIV. ii. 12170 ABSTRACTS OF CHEMICA Ti PAPERS. The acetone may however form a salt the anions of which react with the hydroxylamine COMe + K + OH + XH,OH + - + - f OH*CMe,O + NH,*OH + K -+ CMe,:NO + K + 2H,O.The equilibrium point for the non-catalysed reversible reaction between acetone and hydroxylamine in concentrations of 1 gram-mol. per litre is different from that of the catalysed reversible reaction in which the concentrations of the acetone hydroxylamine and hydrochloric acid are also each 1 gram-mol. per litre and the equi- librium in the latter case varies greatly with the variation in the amount of hydrogen ions of the catalyst. A catalysing agent may influence the velocity of a reaction physically by condensing the reacting substances on the surfaces of solids thus increasing the effective concentration or by imparting energy to or withdrawing i t from the solution A catalyst may also change the velocity chemically by altering the concentrfition of some substance taking part in the reaction or by forming some new substance which yields the same end-produots.I n some cases side- reactions may be developed or suppressed by the addition or removal of the catalysing agent. E. G. Landolt’s Experiments on Change of Weight in Chemical Transformation. T. H. LABY (Chem. News 1908 97 1-3).-A summary and discussion of Landolt’s results (Abstr. 1906 ii 528). G. S. Observations and Deductions-obtained from a Consideration of the Numbers given for the Atomic Weights of the Elements by the International Committee ( 1905) which lead to a Rational Determination of the Constitution and Structure of each Element. HAWKWORTH COLLINS (Chem. News 1907 96 176-1 77).-Certain relationships between the approximate numbers which represent the atomic weights of the twenty-eight elements with atomic weights below 60 as exact multiples of that of hydrogen are noted Deductions involving the assumption that the elements contain protyle are made.Reciprocal Displacement of the Constituents of Molecular Compounds and their Relative Stability. BORIS N. MENSCBUTKIN (J Rus8. Phys. Chem. soc. 1907 39 1548-1565. Compare Abstr. 1907 ii 751).-To determine the ability of one substance to replace another in a molecular compound the latter is dissolved in a small quantity of the desired organic compound and the mixture left in a desiccator. The resulting crystals are then decomposed by water and the products analysed. The following is the order of relatire stability of the molecular compounds formed by magnesium bromide and iodide with organic substances.Carbamide ; water ; aniline acetamide cthyl carbamate formic ncid ; methyl alcohol ; ot hyl ctlcohol ; acetonitrile acetic anhydride ; acetic acid ; propionic acid ; ethyl acetate acetone ; et,byl orthoforantp benzaldohyde ; methyl acetate ; H M.D.GENERAL AND PIIYSICAL CHEMISTRY. 171 acetal acetyl chloride ; methylal ; ethyl ether ; anisole ; anethole (which does not yield a conipound). The substances separated only by commas f orm molecuiar compounds of very nearly equal' stability and do not replace one another. The Eubstances at the close of the list yield t'he most unstable compounds and are readily replaced by those before them. I n general substances with a high dielectric constant and also those with a high coefficient of association form the most stable compounds with the magnesium halides but there seems t o be no direct quantitative relation between the stability and the physical properties of the organic constituent. Of the substances containing oxygen the most stable compounds are formed by those containing the hydroxyl group next come those with a carbonyl group and finally substances of the type R*O*R. Compounds containing an amino- group are as stable as those containing an hydroxyl group and contrary to Werner's statement it is highly probable that t,he constituents of a molecular compound containing both an NH and a C:O group are connected to one another by means of the nitrogen atom. Qualitat,ive experiments show that whilst little heat is developed in the formation of the unstable molecular compounds considerable quantities are developed in the case of the more stable compounds. Z. K. Lecture Experiments with Ozone. CARL D. HARRIES (Be?*. 19OS 41 42-43).-(1) A stoppered cylinder about 30 cm. long is filled with ozonised oxygen ; the presence of ozone in the cylinder is shown by introducing a piece of potassium iodide starch-paper. About 50 C.C. of turpentine oil are poured quickly into the cylinder which is then well shaken ; if a piece of potassirim iodide starch-paper is now placed in the cylinder it will not turn blue but does so when dipped in the ozonised turpentine oil. (2) A strip of absorbent paper is satwated with turpentine oil the excess removed by pressing between drying paper and the strip then placed in a long wide cylinder full of ozonised oxygen; in a few seconds the turpentine oil ignites and burns with a luminous smoky dull red flame. W. H. G. Balances with Non-metallic Pans. ERNST BORNEMANN (Chna. Zeit. 1908 32 125-126).-Attention is called to the trouble occasionally experienced in accurate weighings of glass utensils when using a balance with glass pans. The author finds this is caused by electric disturbances and advises covering the pans with a disc of sheet copper. L. DE E(.

ISSN:0368-1769    

DOI:10.1039/CA9089405137

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

ABS'I'RAC'J'S OF CHEMICAL PAPERS. Inorganic Chemistry. Slow Combination of Chlorine and Hydrogen under the Influence of H e a t . HEINRICEI SIRK (Zeitsch. physikal. Chenl;. 1908 61 545-565).-h!tixtures of hydrogen and chlorine in different pro- portions occasionally with hydrogen chloride in addition were heated in glass vessels in a thermostat a t 242.5'. After different intervals the contents of the glass vessels were analysed. The reacting gases were protected from light throughout. The combination of hydrogen and chlorine under the influence of heat is a very complicated problem and for some of the author's observations no explanation can be suggested. The initial rate of combination is proportional to the chlorine concentration ( c ) and is independent over a wide range of the concentrations of hydrogen and hydrogen chloride.A t the same time the reaction is not a uni- molecular one throughout for the value of k = l/t.log.c/(c - x) diminishes as the reaction proceeds. If the chlorine or the mixture of chlorine and hydrogen has been heated previously tho combination of the two gases is accelerated (compare Burgess and Chapman Trans. 1906 89 1399) ; a similar effect is produced by previous exposure of the chlorine t o light. The activity of a mixture of hydrogen and chlorine is diminished by contact with concentrated sulphuric acid but this apparently has nothing to do with the removal of traces of moisture. One experiment made a t 25S0 indicates that the tempera- ture-coefficient of the rate of combination of hydrogen and chlorine is 1.6 for a rise of 10'.J. C. P. MAX BODEN- STEIN (Zeitsch. physikal. Chern. 1908 61 447-44S).-The author found previously (Abstr. 1897 ii 252) that the decomposition of hydrogen iodide in the dark at high temperatures was a bimolecular reaction whereas the decomposition in light was a unimolecular reac- tion. The suggestion that this difference is only an apparent one and that. the lowering of the order of the reaction might be due to t h e absorption of the active rays by the surface layer of the hydrogen iodide has been tested by experiment The glass tubes containing the hydrogen iodide were surrounded by wider tubes containing in some cases air in other cases hydrogen iodide and were then exposed to sunlight. The decomposition in the inner tubes was practically equal under the two sets of conditions; hence the suggested explanation is disproved. J.C. P. Action of Oxygen on Metals. EDUARD JORDIS and W. ROSENHAUPT (Zeitsch. angew. Chenz. 1908 21 50-66).-A coniplete account of work already partly published (this vol. ii 98 107). It is now found that above 1 4 5 O air attacks copper more energetically than does oxygen. The greater oxiclising power of s i r and of moist oxygen n s compared with that of dry oxygen is asciibetl t o the participation in the reaction of oxidation proclucts of nitrogen and water. The course of the oxidation depends on the behaviour of the surface layer Decomposition of Hydrogen Iodide in Light.INORGANIC CHEMISTRY. 173 of the imtal ; progressive oxidation is possible only if the oxide first formed does not act as a protective coating.An oxidisable surface may be the result of (a) the solution of the oxygen in the metal as such or as an alloy of copper and oxygen ; ( b ) the diffusion of the oxygen through the layer of oxide which may dissolve the oxygen or be merely porous to i t ; (c) the alternate formation of lower and higher oxides or ( d ) the layer of oxide scaling off from the metal. Examples of each case are given. During the oxidstion metallic filings shrink together and form LZ mass. With suitable apparatus i t would be possible to judge from the surface colours as t o the ratio M 0 in the outermost layer of the metal. [Formation of Ozone Nitrogen Peroxide and Hydrogen Peroxide in Reactions in Air which Develop High Tempera- tures &c.].EDWARD H. KEISER and LEROY MCBIASTER (A912er. Chenz. J. 1908 39 101-104).-See this vol. ii 223. Presence of Sulphur in some of the Hotter Stars. SIR NORMAN LOCKYER (Proc. Rog. Soc. 1907 80 A 50-57).-Certain lines in the spectrum of a star (Rigel) have been found to coincide in wave-length with prominent lines in the spark-spectrum and vacuum-tube spectrum of sulphur. There are however in that part of the spectrum in which comparison is possible a t least two well- defined lines (A = 4253.8 4285.1 and possibly 4295.0) in the spark- stsectrum of sulphur which are not present in the spectrum of Rigel but these two lines are present in certain stars hotter than Rigel. The evidence for the presence of sulphur in stars is therefore regarded as conclusive.G. S. G. Y. Behaviour of Thiosulphuric Acid and its Use in Volumetric Analysis. ANGELO CASOLARI (Gaxxetta 1907 37 ii GO1 -608).- The decomposition of thiosulphuric acid begins immediately the acid is liberated froin its salts but titration of acidified solutions of sodium thiosulphate with iodine shows that the decomposition occurs slowly in dilute solutions. Sodium thiosulphate is hence capable of giving exact results when titrated with acid solutions (compare this vol. ii 22 2). The opalescence appearing in solutions of sodium thiosulphate in presence of acid is due to the presence of a small proportion of free sulphur which probably owing t o a change of state has assumed the molecular form. Such opalescent liquids become clear when sulphite ions are added to them or hydrogen ions are removed thiosulphuric acid being regenerated.When solutions of thiosulphuric acid are rendered alkaline and then faintly acidified they yield an appreciable odour of hydrogen sulphide; the same is the case with the thionic acids which liberate sulphur. Action of Carbonates on Tetrathionates. V. AUGUST GUTMANN (Bey. 1908 41 300-307. Compare Abstr. 1905 ii 384 813 ; 1906 i 149 ; 1907 ii 862).-The action of alkali carbonates on sodium tetrathionate is different from that of alkali hydroxides ; in addition to sodium thiosulphate sulphnte is formed instead of the sulpbite obtained in the latter case. The experiments were carried T. H. P.174 ABSTRACTS OF CHl3MIChL PAPERS out with sodium potassium and lithium carbon:iteu as well as arrirnonia the solutions being boiled for half an hour.Quantitative experiments carried out either by the author's method (Abstr. 1907 ii 812) or by direct titration of the excess of carbonate show that the reaction takes place in accordance with the equation 4Na,S,06 + 5Na2C0 = 7Na2S20 + 2Na2S0 + 5CO or 45,0 = 7S,O + 280,. When however the carbonates of barium strontium and calcium were examined it was found that the thiosulphate could not be determined by the cyanide and silver nitrate msthod as silver sulphide was precipitated notwithstanding the fact that there was no sulphide in the solution before treatment with cyanide. This accords with Drechsel's suggestion that thiosulphate may have the isomeric forms " > S < ~ ~ ~ 0 and ~ > S < ~ ~ ~ . An aqueous solution of sodium tetrathionate on boiling fdrms sodium sulphate sulphur dioxide and sulphur not trithionate and sulphur as stated by Kessler (Ann.Yhys. Chem. 1848 [ii] 74 253). w. R. Synthesis of Ammonia. HERRIANN C. WOLTERECK (Cov2pt. rend. 1908 148 124-125. Compare Abstr. 1904 ii 115 ; Brunel and Woog t,his vol. ii 34).-When a mixture of nitrogen (1 vol.) and hydrogen is passed over reduced iron spread in thin layers on asbestos fibre and heated at 550° small quantities of ammonia are formed. The yield is increased slightly by substituting the oxide for the metal but in both cases the reaction stops after a time. Similar results are obtained with the oxides of nickel cobalt copper cadmium silver lead bismuth chromium and iron the last three giving the best yields.The reaction is made continuous by replacing the nitrogen by air and the results are improved by introduction of water vapour whilst the hydrogen can be replaced by coal gas freed from nitrogenous products. Passage of 100 litres of a mixture of hydrogen (I vol.) and air (78 vols.) t'hrough water kept at SO' and then over iron ovidised and reduced by carbon monoxide before the experiment gave a t different temperatures the following amounts of ammonia 260-300° 0.0803 gram 300-350' 0.204 gram 350-400' 0.1 19 gram 400-450° 0.0134 gram 450-550' 0.041 1 gram 550-650' 0.0236 gram all the experiments occupying 4-5 hours. These results show that 300-350° is the most favourable temperature. Diminishing the velocity of the gas that is pFolonging its contact with the iron diminishes the yield.Other oxidisable materials which can be substi- tuted for the reduced iron are coke and wood-charcoal but better results are obtained with peat. A series of comparative experiments using sugar-charcoal and varying the temperature and the volume and velocity of the mixed gases shorn that the best results are obtained at 450' with 40 litres oE gas passing in six hours in which case 0.9 gram of ammonia is formed per 100 grams of charcoal burned. E. H. Electrolytic Reduction of Hydroxylamine at Copper Cathodes. JULIUS TAPEL and HANS HAm (Zeitsch. ccnos*g. CILe?)z. 1908 56 375-384).-111 R previous paper (Abstr. 1909 ii 550) itINORGANIC CHEMISTRY 175 tvas shown that hydroxylamiue sulphate dissolved in water containiiig u large proportion (20-50%) of sulphuric acid is not reduced at a copper cathode whilst Flaschner (Abstr.1907 ii 454) has observed a certain amount of reduction in dilute sulphuric acid solution. It is now shown that reduction always takes place when the sulphuric acid concentration in the layer of electrolyte in contact with the cathode is reduced beyond a certain point ; and when there is no excess of acid ; in other words when hydroxylamine sulphate itself is electrolysed the reduction is quantitative. These results are most readily accounted for on the view that only free hydroxylamine (produced in this case by partial hydrolysis of the sulphate) but not the hydroxylamnionium ion NH,OH* is reduced a t a copper cathode. Analysis of the Oxides of Nitrogen by means of their Ultra-red Absorption Spectra.XMIL WARBURU and CX. LEITHAUSER (Sitsuwgsber. k. Akccd. TVi'iss. Berlin 1908 148-153).- The absorption spectra of the oxides of nitrogen and of ozone for ultra- red radiation between the wave-lengths 2 . 7 ~ and 7p have been determined. The apparatus consisted of a Nernst lamp as the radi- ating source a mirror spectrometer provided with a fluorspar prism and a vacuum-bolometer as the receiving instrument. The maxima of absorption are very different for the various oxides of nitrogen; the wave-length values and the angles of minimum deviation corresponding with these absorption maxima are tabulated for N,O N,O NO NO N,O and 0,. The wave-lengths characteristic of the N,O and NO molecules were determined by observations on nitrogen peroxide a t different temperatures.The data are applied to the examination of the products formed when electric discharge takes place in air. It is found that theaction of the silent discharge in the Siemens' ozoniser not only yields ozone but also nitrous oxide and nitrogen pentoxide. Spark discharge through air bet ween platinum electrodes yields nitrogen peroxide and nitrous oxide. Alternating arc discharge at high potential in dry air yields only nitrogen peroxide. Preparation of Pure Nitrites from Nitrous Fumes. BADISCHE ANILIN- & SODA-FABRIK (D.R.-P. 188188).-Inasmuch as the oxidation of nitric oxide to nitrogen trioxide is known to occur very rapidly whilst the further oxidation to nitrogen peroxide proceeds relatively slowly it has been recently suggested by Raschig that if the oxides from atmospheric nitrogen could be absorbed in about one second after their production in the electric arc it would be possible to prepare in this way pure nitrous acid or nitrites.It has now been found that this inconveniently rapid absorption of the gas is un- necessary if only the gaseous mixture containing chemically combined nitrogen and oxygen in the proportion N 0 is heated a t 300" until absorption occurs. I n these .circumstances the further oxidation to nitrogen peroxide is almost entirely inhibited and pure nitrites can be prepared on a technical scale by absorbing with alkali hydroxides or carbonates or even with the hydroxides of the alkaline earths. As the absorption of the heated gas leads to the geuerntion of steam solutions of low vapour pressure are employed in order that the action G.8. H. M. D.176 ABSTRACTS OF CHEMICAL PAPERS may not be retarded owing t o dilution of the gases with steam. With this end in view strong solutions of nitrites are employed as absorbents. Heteromorphic (Allotropic) Modiflcations of the [Elements of the] Phosphorus-Arsenic Group. GOTTLOB E. LINCK (Zeitsch. anorg. C'hem. 1908 56 393-400).-The paper contains a summary of the progress of knowledge as to the allotropic modifications of the elements of the phosphorus group since the author's former publication on the subject (Abstr. 1899 ii 415). The work of Reppert (Digs. HaZZe) on the modifications of arsenic is adversely criticised in some respects. The crystals of red phosphorus (Hittorf's phosphorus) are biaxial and probably monoclinic.G. S. H i t t o r f ' s Phosphorus. ALFRED STOCK (Bey. 1908,41,250-251. Compare Linck preceding abstract) .-Largely polemical. Stock and Johannsen (Diss. RerEin 1904) found that Hittorf's crystalline red phosphorus described as crystallising in the hexagonal hemihedric system in reality forms reddish-brown transparent plates which appear violet-red in reflected light; these are biaxial and probably belong to the monoclinic system. Transformation of Solutions of White Phosphorus into Red Phosphorus. ALBERT COLSON (Compt. rend. 1908 146 71-73. Compare this vol. ii 35).-The velocity of the change of white into red phosphorus depends on the temperature and on the pressure of the vapour and in the present paper the author shows that similar factor8 regulate the transformation of white phosphorus in solution into red phosphorus ; the velocity of the change varies with the temperature and with the concentration of the solution.The experiments were con- ducted on solutions of phosphorus in oil of turpentine or carbon disulphide placed in sealed tubes and in order to avoid inequalities of temperature these were placed in solutions of phosphorus in turpentine and heated to the required temperature. A solution of phosphorus in oil of turpentine containing 23 grams per litre remained clear after heating for fifty-two hours at 230-235" but gave a thick deposit of red phosphorus after heating for eight to ten hours at 285-290'. A solution containing 30 grams of phopphorus in a litre of oil of turpentine deposited red phosphorus after heating for fifty-five hours at 260-265' whilst a solution of phosphorus in carbon diaulphide containing 90 grams per litre deposited red phosphorus after heating for fifteen hours at the same temperature.Three tubes containing respectively 150 125 and 10 grams of phosphorus in 100 grams of carbon disulphide were heated a t 225-230'; a t the end of four hours the first tube contained a large qiiantity of red phosphorus the second tube contained traces of the red phosphorus whilst the contents of the third tube were unaltered. Action of Arsenic Hydride on Solutions of Halogens Halogen Acids and other Oxidising Agents. HANS RECIZLEBEN and GEORG LOCKENANN (Zeitsch. c m d . Chem. 1908 47 105-125).- A rsenic hydride is oxidised quantitatively to arsenic acid by iodine G.T. M. E. I?. A. M. A. W.INORGANIC CHEMISTRY. 177 bromine and chlorine in presence of water ; hypochlorites and hypo- bromites act in a lees satisfactory manner. I n presence of a catalyst the oxidation may be carried out by iodic acid and iodates also by bromic acid and bromates. Chloric acid oxidises it to arsenious acid but chlorates are quite inactive. Perchlorates in acid solution and in presence of a catalyst (a trace of iodine for instance) act but very slowly. Periodates act like iodates but much more slowly. Per- manganates in neutral or acid solution also alkaline ferricyanide (very slowly) and potassium dichrornate in sulphuric acid solution absorb the arsenic hydride completely.Nitric acid sulphuric acid solutions of persulphate chromate dichromate aud neutral ferricyanide absorb arsenic hydride very slowly and incompletely whilst solutions of metallic nitrites nitrates hydrogen sulphates and arsenious and arsenic acids are still less active. Hydrogen peroxide acts very slowly; a t first arsenic is deposited which is then gradually oxidised to arsenious or arsenic acid. In contact with potassium or sodium hydroxide and air a separation of arsenic is noticed. L. DE K. Constitution of the Carbon Molecule from the Standpoint of Thermo-chemistry. H. STANLEY REDGROVE (Chem. News 1908 97 37).-An attempt t o elucidate the constitution of the carbon molecule from a consideration of the heat values of the different types of carbon linkings (compare Abstr.1907 ii 446 604 929). The formula recently suggested by Dewar (Chem. iVews 1908 97 19) is not in agreement with thermochemical data. H. M. D. Density of Graphite. HENRY LE CHATELIER and S. WOLOGDINE (Corn@. rend. 19OS 146 49-53).-The belief in the existence of the numerous polymerides of carbon is based on their difference in density ; thus the density of amorphous carbon varies from 1 to 2.6 of graphite from 1.8 to 2.6 whilst that of the diamond is practically constant at 3.50 to 3-51 The authors have redetermined the density of graphite from eight different sources natural or artificial using a mixture of tetrabromoethane and ethyl ether in which the graphite floated a t any height. Preliminary experiments showed that the discrepancies in the densities of the different specimens mere due to the presence of traces of impurities not removed by treatment with nitric acid or to air in the pores of the graphite which was not completely eliminated in a vacuum.When however the graphite was fused with potassium hydroxide after preliminary treatment with warm fuming nitric acid washed and then boiled with hydrochloric acid D 1.12 dried a t a dull red heat and finally subjected to a pressure of 5000 kilos. per square centimetre each specimen of graphite had DY 2.255. M.A. W Relation Between the Composition of Goal and the Amounts of Carbon Monoxide and Dioxide contained in Gas Distilled from it. LEO VIGNON (BuEI. SOC. china. 1908 [iv] 3 109-1 14).-The object of the investigation was to determine what178 ABSTRACTS OF CHEMICAL PAPERS.relationship existed between the amount of oxygen in the coal and that in the oxygenated gases produced on its distillation Five samples of coal were used and in these the amounts of calcium carbonate carbon hydrogen nitrogen sulphur and oxygen (by difference) were determined and finally the washed gases produced by their destructive distillation at 900" were analysed. The results which are given in detail in the original show that the more oxygen the coal contains the larger are the amounts of carbon monoxide and dioxide producsd on its distillation and that the quotient of the total oxygen in these two gases produced on distillation by the oxygen originally present in the coal ranges from 0.292 to 0.314 that is rather less than one-third is evolved in these two forms.The relative proportions of the two gtses vary with the conditions and at temperatiires above 900' there is a tendency for carbon dioxide to be replaced by the monoxide Dissociation of Carbonyl Chloride. MAX BODENSTEIN and GEORGE DUNANT (Zeitsch. physikal. Chem. 1908 61 437-446).- Carbonyl chloride or a mixture of carbon monoxide and chlorine in equivalent proportions was passed through a heated tube and the issuing gas mas analgsed. A t 800° carbonyl chloride is completely decomposed ; a t 603" it is dissociated to about 91% ; at 5534 to about 80% and at 503O to about 67%. From the corresponding equilibrium constants the heat effect of the reaction CO + CI = COCI is calculated to be about 23,000 cal. a figure in rough agreement with the calorimetric determinations of Thomsen and Berthelot and with Nernst's theory (see Nernst Abstr.1906 ii 727; Brill Abstr. 1907 ii 233). Some experiments on the rate of formation and decomposition of carbonyl chloride have been made a t 503O and the results obtained are best represented by the formulz which Bodenstein and Wolgast have suggested (see this vol. ii 162). T. A. H J. C. P. Dissociation of Fused Silicates. CORNELIO DOELTER (Monntsl.. 1307 28 1313-1379. Compare Abstr. 1906 ii 665)-An investi- gation of the extent to which silicates in the fused state are electrolytically dissociated if at all has been undertaken as a know- ledge of this subject is necessary for the elucidation of the results obtained from the general study of fused silicates. I n view of the experimental difficulties met with in the course of the work the results now published must be regarded only as provisional.It is found that the conductivity of the silicates depends chiefly on the temperature; silicates which in the solid state are almost non- conductors have a conductivity approaching that of dilute salt solutions when r'tised to a sufficiently high temperature. As a t high but varying temperatures the different silicates examined have approximately the same conductivity comparisons must be made only at a given temperature interval above or below the melting points which are represented on the temperature-resistance curve by a break or by a gradual bend. I f the conductivity is measured during cooling a shayp break occurs in the curve for silicates which crystallise butINORGANIC CI-IEMISTRP.179 Chere is no break in the curve for those which solidify to a glass. The increase in the conductivity with riso of temperature may depend on increasing dissociation or on an increase in the mobility of the ions. It is concluded that a gradual change in the conductivity in the neighbourhood of the temperature of solidification must depend a t least partly on a diminution of the dissociation but that a sharp break resuIts chiefly from the marked loss of mobility of the ions which must occur on crystallisation since such wandering of the ions as may be possible in an amorphous solid cannot take place in a crystalline substance. I n connexion with this the author discusses the relation between the coefficient of internal friction and the con- ductivity of fused salts From the comparison of the results obtained with the different silicates examined it is concluded that.a t high temperatures all silicates are electrolytically dissociated ; at medium temperatures orthoclase is dissociated to a greater labradorite to a smaller extent than augite or hornblende Of two silicates that which melts a t the higher temperature is dissociated to the less extent at a given medium temperature. In agreement with this are the results of experiments which show that whilst siinplo silicates such as olivine enstatite augite and also labradorite always separate after fusion other silicates are not reformed. G. Y. Colloidal Sodium Chloride. CART YAAL and GUSTAV KUIIN (Bey. 1908 41 51-57).-Relatively stable organosols of sodium chloride similar to those described previously (Abstr.1906 ii 749) are obtained by the action of ethyl chloroacetate chloroacetone and phenacyl chloride on ethyl sodioethylmalonate in benzene or ether. The colloidal solution obtained by acting on ethyl sodioethylmalonate with ethyl chloroacetate in benzene when heated for some time becomes more viscid remainiag however quite liquid and apparently homogeneous. This product when poured into a glass vessel deposits x gel on the sides of the vessel and when filtered through a filter paper separates into a gel which remains on the filter and into a benzene solution of the organic compounds formed in the reacttion which passes through the filter and is almost free from sodium chloride.The action of sulphuryl chloride on ethyl sodioethylmalonate in benzene results in the formation of a sodium chloride sol which rapidly changes into the liquid gel. The authors propose t o name such products tiquid gels. W H. G. Colloidal Sodium Bromide and Iodide. CARL PAAL and GUSTAV KUHN (Bey. 1908 41 5s-61. Compare preceding abstract).- Organosols and gels of sodium bromide areobtained by using ethyl sodioethylmalonate instead of ethyl sodiomalonate (Abstr. 1906 ii 749) and are similar to those previously described (Zoc. cit.). Wheu ether is employed as the solvent the organosol of sodium bromide changes into a. gel which is not gelatinous but consists oE largo aggregates of small transparent amorphous globules.180 AESTRACTS OF CIIEMlCAL PAPERS.It has also been found possible by acting on ethyl sodioethylmalonstts with ethyl P-iodopropionate in benzene or ether to obtain an oi*gcmosol of sodium iodide which is however exceedingly unstable and rapidly changes into a gel. The sodium iodide previously inaccurately described as crystalline (Eoc. cit.) when examined under a microscope is found to consist of aggregates of amorphous transparent globules. Percarbonates. XICHARD WOLFFENSTEIN and ERICH PELTNER (Bey. 1908 41 2SO-397. Compare this vol. ii 153; Constnm and von Hansen Abstr. 1597 ii 550; von Hamen 1898 ii 23; Tanatar 1899 ii 482; 1903 ii 208; Willstiitter 1903 ii 537 ; Kasanezky 1903 ii 366 ; Bauer D.R.-P. 145746).-The investigation of the action of carbon dioxide on peroxide of sodium has led to the preparation of sodium percarbonates containing in general water of crystallisation but not hydrogen peroxide of crystallisation. This is shown by a study of the analytical results and by the mode of prepara- tion the first product being the normal salt and the second the hydrogen salt or its anhydride.Sodium dioxide carbonate Na,CO,,l&H,O is best prepared by first hydrating 4 gram-mol. of sodium peroxide with 50 grams of ice and then slowly passing a current of carbon dioxide over the mass. The temperature is kept below Oo and as soon as the mass becomes pasty another 4 gram-mol. of sodium peroxide is added in portions. The action is finished when 1 gram-mol. of carbon dioxide has been absorbed. The unstable salt is washed with alcohol and ether and dried in a vacuum.SocEizcm dioxide dicarbonate Na,C,O is obtained when the gas can no longer be absorbed. It is more stable than the normal carbonate. When a similar series of experiments were carried out with Tafel'a sodyl hydroxide (Abstr. 1394 ii 448) it was found that t-he dry substance was not acted on by carbon dioxide but in the presence of a trace of moisture action occurs the mass becoming warm and decomposing. Sodyl hydroxide containing 26-30% water is kept below Oo and treated carefully with carbon dioxide solid or gm when sodium trioxide dicarbonate NnHCO or Na,C,O results. It is very unstable. The preparation of a sodium trioxide hydrate Na*O*O*H isomeric with Tafel's sodyl hydroxide O:Na*OH is accomplished by treating sodium ethoxide with a mixture of 30% hydrogen peroxide (1 mol.) and absolute alcohol when it is precipitated. From this material an isomeric sodium trioxids dicarbonate Na HCO or Na,C,07 is obtained in the above way.Washing the product with alcohol and ether removes hg drogen peroxide but analysis of the washed material agrees with the formula. It is shown that the sodium trioxide hydrate as above prepared contains hydrogen peroxide of crystallisation. The dicarbonate is much easier to prepare than its isomeride is much more stable and behaves differently towards heat. Sod,ium trioxide carbonate Na,C05 is formed on treating sodium trioxide hydrate with the calculated quantity of carbon dioxide; i t is less stable than the dicarbonate. W. R. EMANUEL MERCK (D.R.-P. 188569).-At low temperatures hydrated sodium ?V.H. G. Preparation of Sodium Hydrogen Percarbonates.INORGANIC ClIEBlISTRY. 181 peroxide furnishes sodium percarbonate Na2C0 on treatment with solid liquid or gaseous carbon dioxide. A substance containing a greater proportion of CO is obtained by adding 20 parts of ice to 39 parts of sodium peroxide and then treating the sodium peroxide hydrate thus produced with 33 parts of carbon dioxide the mixture being stirred until the reaction is complete. Xodiunz hydrogen pewarbonate 4Na,C103,H,C03 finds employment as a dis- infectant-and in the preparation of hydrogen peroxide. G. T. 31. Constitution of Sodium Hyposulphita. E. I. ORLOFF (J. Russ. Phps. Chem. Soc. 1907 39 1588-1617).-See this vol. i. 132. Rubidium Dichromate. GREGOIRE WYROUBOFF (Bull. A'oc.chinz. 1908 [iv] 3 7-10. Compare Bull. Xoc. chirn. 1901 [iii] 25 105 ; Abstr.. 1901 ii 149 and Stortenbeker Abstr. 1907 ii 764)-The author reiterates his opinion that the monoclinic and triclinic forms of this salt have practically the same solubility and attributes the greater solubility observed by Stortenbeker for the monoclinic form to the fact that this investigator did not render his preparation of the monoclinic form anhydrous by melting it t o eliminate occluded water. Further he cannot confirm S tortenbeker's observation that the mono- clinic forin disintegrates slowly in contact with a solution containing excess of the salt and still more slowly when dry. Crystals of the two forms in his experience can be kept for months in contact with a saturated solution of the salt without showing any tendency to transformation mhilst crystals have been kept in a dry state f o r eighteen years without showing any change in form.T. A. H. Ammonium Nitrite. JuLrus MEYER and EMIL TI~UTZER (Zeitscii. Elektrochem. 1908 14 69-76).-The decomposition of ammonium nitrite in aqueous solution has been studied. The discrepancies in the results of previous observers appear to be due to the use of impure water and impure ammonium nitrite. A trace of carbon dioxide in the water was found to increase the rate of decomposition by about 30%. The ammonium nitrite was purified by fractional precipitation of an alcoholic solution with ether. The :dry salt decomposes when kept ammonia and oxides of nitrogen being formed ; these are absorbed by the salt which becomes yellow.The rate of decomposition of the solutions increases nearly in proportion to the age of the salt. A sample of the salt three months old decomposes almost explosively a t 60". The rates of decomposition of solutions of salt up to eight weeks old were measured and velocity constants calculated. The results are well represented by the equation of the unimolecular reaction but the velocity constant instead of being independent of the initial con- centration of the solution is proportional to it. This is regarded as indicating that the change is clue to the catalytic action of the acid decomposition products contained in the dry salt and t h i s view is also in accordance with the inweme of the constants with the age of the salt.Colloidal platinum appears to accelerate the rcac tion. T. E.Ammonium Syngenite. JOII. D'RNs (Be?.. l!lOS 41 lS7-189). -Replying to Bell and Taber (Abstr. 1907 ii 867) the author shows that the double sulphate of calcium and niniiioniurn which has not been treated with 50% alcohol but freed from mother liquor by the use of a hydraulic press or by washing first with absolute alcohol and then with ether has the coniposition represented by the formula CrtSiO,,(NI~,),SO,,I-I,O (compare Abstr. 1906 ii 751). W. H. G . The Reduction of Silver Oxide by Hydrogen Colloidal Bilver. VOLKMAR KOIILSCII~TTBR (Zeitsch. EZektrochem. 19OS 14 49-63).-Tn order to throw light on the apparent volatilis' [L t ion of irietnls in vacuum tubes the forniation of silver films in the reduction of silver oxide by hydrogen bas been studied.The perfectly dry substances do not react; in presence of a trace of moisture the reaction takes place even a t the ordinary temperature. The presence of larger quantities of water retards the change which always begins at the points of contact of silver oxide and glass. If a little silver oxide dust is distributed over the walls of a flask which is then filled with hydrogen nearly saturated with aqneous vnponr minute drops of water can be caused to condense roiincl the silver oxide particles by cooling one side of the flask. The reduction takes place in these drops much more rapidly than in the dryparticles and when the drops are evaporated ,z film of silver is left on the glass. The film coiisists of colloidal silver ; it does not conduct electricity at first but soon passes into the ordinary forin of the metal.When a suspension of silver oxide in pure water is reduced by hydrogen the reaction takes place almost exclusively in the contact surface of glass and solution the solid oxide being unattsckecl ; the reduced silver is obtained partly as a mirror and partly as a hydrosol. The rate of reduction of the silver oxide increases with the ratio (glass surface)/(volnnie of solution) whilst the ratio hydrosol/mirror diminishes. The nature of the hydrosol obtained depends on the kind of vessel used. Ordinary glass and quartz glass give yellowish-brown solutions Jena glass yields red blue o r violet solutions whereas platinum gives no hydrosol all the silver separating as a crystalline deposit on the platinum.The solutions contain dissolved silver hydroxide in addition to the colloidal silver. The latter is estimated by precipitation with potassium nitrate solution. The conductivity of a solution is only slightly larger than that of a solution of silver hydroxide of the same strength. By-passing R current of hydrogen through a solution of hydrosol and silver hydroxide contained in a plxtinised platinum basin the silver hydroxide is reduced leaving a solution of the pure hydrosol. The conductivity of the purified solution is about one-tenth of the original conductivity and about three times that of the pure water used so that the removal of electrolytes is very complete. The quantity of colloidal silver in the purified solutions is always less than that in the original solution; calling thc difference A 2nd the qiinntiky in thc purified solution Ag the rntio Ag/A is usually not very f a r from unity for all the yellowish- brown solutions whilst i t varies from 3 to 20 for the blue or violetINORGANIC CHE?lfISTltY.133 solutions. This is the only difference found between the two kinds of solution ; the quantity and quality of dissolved glass does not affect the result; a solution of ordinary glass in a Jena flask gave a blue hydrosol a,nd not a brown one. The author thinks that the original hydrosol molecule is a compound of silver and silver hydroxide; the treatment with hydrogen in a platinum vessel removes both the combined and the dissolved silver hydroxide ; the brown solutions would therefore contain molecules having Ag AgOH = 1 whilst in the violet solutions this ratio is much larger.If a trace of silver is brought into a borax bead a brown or violet coloration is obtained as the bead cools which is probably due to the separation of colloidal silver. The reduction of silver oxide by carbon monoxide also yields silver hydrosols. T. E. Some Effects of Sunlight on Colourlests Glass. Ross AIKEN QORTNEE (Amer. Chenz. J. 1908 39 157-162).-1t has been shown by Crookes (Chenz. News 1905 91 73) Avery (Abstr. 1905 ii 589) Simpson (Chem. News 1905 91 236) and Rueger (Abstr. 1905 ii 709) that certain specimens of glass assume a violet colour on exposure to sunlight for a considerable time. Fischer (Abstr. 1905 ii 320) has found that the same change can be effected in glass containing manganese by exposing it to the ultra-violet rays from a quartz- mercury lamp.I n only one case ( Alway and Gortner ili?zer. Chem. J 1907 37 1) has the time necessary to produce the coloration been recorded. Several specimens of glass from various sources have been exposed to the direct action of the sun and the following observations have been made. Glass which is relatively rich in manganese (about 0*2-0*3%) becomes coloured in less than a month the degree of coloration being proportional to the manganese present. Most specimens of glass containing only a small quantity of manganese become coloured in less than a year and the colour becomes deeper if the time of exposure is increased. The production of this violet coloration is a proof of the presence of manganese but some specimens of glass although containing this element do not become coloured.Rueger’s suggestion (Zoc. cit,) that glass may become coloured by lying in the proximity of manganese or its ores is untenable. A violet background is more favourable to the action of the ultra-violet rays than one of any other colour. White yellow blue and red act alike and seem to have no effect on the rate of coloration whilst brown and black appear to have a retarding action. E. G. Barium Percarbonate [Barium Dioxide Carbonate]. RICHARD WOLFFENSTESN and ERICH PELTNER (Be?.. 1908 41 275-280).-According to Duprey (Compt. Tend. 1862 55 736) and Balard (ibid. 738) the action of carbon dioxide on barium dioxide in water is to form barium carbonate and hydrogen peroxide.A re- investigation of the reaction according to Duprey’s conditions shows that a t the beginning the hyclrogen peroxide forinecl corresponds with the barium peroxido used but after some time the action ceases. If instead of using carbon clioxide in excess barium dioxide is employed184 AESTK BC'IS OF CHEMICAL PAPERS. in considerable excess then no separation of hydrogen peroxide occurs although the carbon dioxide is absorbed. Continued saturation of this solution with the gas leads however to the formation of hydrogen peroxide and in a short time all the active oxygen exists :as hydrogen peroxide. The reaction therefore occurs in two stages and in order to separate the intermediate compound barium dioxide carbon- ate BaC04 particular care must be taken to avoid the presence of too much water on the one hand otherwise hydrogen peroxide is liberated or of too little water on the other as that leads t o the development of heat and decomposition of the compound. It is best prepared by cool- ing 30% barium dioxide solution to Oo and slowly saturating the solution with carbon dioxide.The compound is light yellow and does not lose hydrogen peroxide quickly in cold water or on washing with ether o r alcohol so that although the compound has not been obtained free from water it does not contain hydrogen peroxide of crystallisa- tion. w. R. False Equilibria. ERNST H. B~~CIINER (Zeitsch. Elektrochem. 1 908 14 63-64).-The reaction MgCO3,3H,O + KHCO + mH,O MgC0,,KHC0,,4H20 + (n - l)H,O has been stated by Engel t o yield solutions of different composition when the double salt is digested with water on the one hand and when magnesium carbonate is digested with a solution of potassium hydrogen carbonate on the other.The experiments have been repeated at 20' and 30° allowing the reaction to go on for twenty-four to thirty-two days instead of for a few hours. It appears that the same solution is obtained but that from four 50 eight days elapse before equi-librium is reached. T. E. Magnesium Silicide. PAUL LEBEAU and ROBERT BOSSUET (Compt. rend. 1908 146 282-284. Compare Gattermann Abstr 1889 342 ; Winckler Abstr. 1890 1372 ; Vigouroux Abstr. 1899 ii 211).-Alloys of magnesium and silicon have been prepared those containing 0-45% of silicon by heating fragments of magnesium with a mixture of magnesium filings and potassium silicofluoride and those containing more than 45% by fusing magnesium filings with crystal- lised silicon and a small quantity of potassium silicofluoride.Metallo- graphic examination of the polished surfaces of these shows (1) in the alloy containing 0.38% of silicon grains of magnesium surrounded by a eutectic but no crystals of the silicide; (2) in alloys containing 6-S% of silicon well-defined crystals of the ailicide in the midst of a eutectic very rich in magnesium ; (3) that an alloy containing 40% of silicon is composed mainly of crystals of the silicide and a eutectic differing from the former and containing free silicon and (4) crystals of free silicon in alloys containing more than 50% of that element.The pure silicide cannot bc isolated by treating the alloys with any aqueous reagent owing to the ,decomposing action of water but the magnesium is dissolved avi%y from an alloy containing 25% of silicon by means of ethyl iodide and ether leaving brilliant slate-blue octahedral crystals of magnesiiiin silicide the analysis of which correiponds nccnrat,ely with the formula Mg2Si. Magnesium silicide slowly decomposes water a t the ordinary temperature giving hydrogen,INORGANIC CHEMISTRY. IS5 but no silicon hydride ; i t is vigorously attacked by cold hydrochloric acid evolving ljydrogen aiicl spontaneously inflammable silicon hydrides and is completely dissociated when heated i n a vacuum or in a current of hydrogen at 1100-1 200O.Analyses of alloys containing free silicon show that in every case the ratio of the magnesium t o the combined silicon is that required by the formula lsIg,lsi. The conclusion is drawn that by the direct action of magiiesiuni on silicon only the single definite compound Rlg,Si is produced. E. H. The System Zinc Oxide-Carbon Dioxide-Water. HANS MIICUSCI-I (Zeitsch. ccnorg. C/'1,371~ 1908 56 365-374).-As there is much nncertainty with regard t o the number of basic carbonates of zinc the question has been investigated on the basis of the phase rule. Neutral zinc carbonate was hydrolysed progressively with water at 25' 50° and looo and the composition of the liquid phase and of the residue detehmioed from time t o time; conversely zinc carbonate was formed by the progressive action of carbon dioxide on the hydroxide and the solid and liquid phases analysecl from time to time.I n both caces sodium acetate was added to the liquid pliasc (compare Hauley Abst'r. 1906 ii 854) to dissolve sufficient of the carbonate and hydroxide to allow of analysis. The results indicate that only the conipound 5 % n O 2 ~ o 2 4 ~ 0 exists; the other basic salts described in the literature arc solid solutions of zinc oxide and carbonate. c. s. Direct Production of Dry Zinc Hyposulphite. C i i ~ m s c ~ i ~ FABRIK GRGNBU LANDSHOFF and XEYKR (U.lt.-P. 154564).-Witherto zinc hyposulphite has ouly been obt:iined in the foriii of the sodium double salt but by iiieans of suitnhle concentrations employed at definite temperatures i t has been found possible to isolate the siniple salt ZnS,O in a dry state. One hundred parts of zinc dust mixed w i t h 150 to 200 parts of water were treated at 45-50" with a rapid stream of sulphur dioxide until the metal had entirely dissolved.The viscid greyish-yellow mass thus produced when cooled to the ordinary summer temperature set to a stiff paste which was collected and drained in an inert atmosphere. A large excess of sulphur dioxide iuust be avoided ax this oxide reacts with the zinc hyposulphite giving rise t o polytliionic acids. G. T. 111. Specific Gravity of Aqileous Solutions of Cadmium Chloride. EUGEN VON BIRON (J. IZuss. Yhys. Chew,. Soc. 1907 39 1503-1506). -The specific gravity of cadmium chloride solutions of various con- centrations has been redetermined and on the basis of the three most accurate determinations the followiag formula has been deduced 104-D30 = 9983 + 8 7 .1 4 4 ~ + 0.474~2 + O*O0991ps (where p = percentage concentration of the solution i n question) The results calculated by means of this formula agree well with the experimental values and also with those obtained by other investigators. z K. VOL. S C ~ V . ii. 131.86 ABSTRACTS OF CHEMICAL PAPERS. Alloys of Copper and Magnesium. G. G. URAZOFF (J. Russ. Phys. Chem. Xoc. 1907 39 1566-1581).-The curve expressing tho relation between the composition of the copper magnesium alloys and their freezing points consists of six branches and is characterised by two maxima at 570" and 799" corresponding with the compounds Mg,Cu and AlgCu and by three eutectic points a t 480" and 16 at.% Cu 555" and 41.5 at. % Cu and 725" and 78 at. % Cu. Neither the metals nor the compounds form solid solutions. The eutectic and melting points observed by Boudouard (Abstr. 1903 ii 78 480) differ from those given here i t is also improbable that there is such a com- pound as MgCu (compare Guillet hbstr. 1905 ii 712). Photographs of the microstructure of various alloys are given and agree completely with the results deduced from the freezing-point curve Z . K. Heat Treatment of Copper-Zinc Alloys. GUY D. BENGOUGH and 0. F. HUDSON (J. Soc. Clzem. Ind. 1908 27 43-52).-An alloy containing 60.43% of copper and 39.21% of zinc (Muntz metal) was cast and hard-rolled and the effect of annealing on the structure and properties was studied. The relations of the a and P solid solutions mere found to be in agreement with Shepherd's diagram (Abstr.1904 ii 662). By coating fractured surfaces with electrolytic copper and cutting sections it was found that the fracture passes by preference through the /3 areas but the mineralogical hardness of the two const'ituents is about the same. C. H. D. Alloys of Copper with Cobalt Iron Manganese and Mag- nesium. R. SAHMEN (Zeilsch. anoyg. Clmn. 1908 57 1-33).-The investigation was carried out by Tammann's method of thermal analysis controlled by microscopic observations. All the pairs of metals are completely miscible in the fused state. Only magnesium and copper enter into chernical combination forming the compounds Cu,Mg m. p. 797O and CuBlg m. p. 570". Copper-Cobalt Alloys.-These metals form two series of mixed crystals from O-lO% and 95.5-100% by weight of copper respectively.There is a break in the cooling curve at 1100" from 10-95% copper below which the alloy completely solidifies to a conglomerate of the two series of mixed crystals. On cooling P-cobalt which is non-magnetic changes t o magnetic a-cobalt. The transition temperature is lowered from 1115" (for pure cobalt) to 1050" by the addition of 10% of copper remains constant at 1050' up to 90% of copper and then falls with further addition of copper. Alloys containing 99% of copper are still magnetic. Copper-Iron AEZoys (compare Pfeiff er hbstr. 1906 ii 35S).-The cast-iron employed contained less than 0.3% of impurities. The equi- librium diagram is very similar to that for copper-cobalt alloys.There are two series of mixed crystals from 0-3*5% and 97.3-100% by weight of copper respectively. There is a break in the cooling curve from 3-97% of copper below which the alloy is completely solidified t o a conglomerate of mixed crystals. By the gradual addition of copper up to 4% (saturated mixed crystals) it The transition from y- to p-iron has been followed thermally.INORGANIC CHEMISTRY. 187 is lowered from 878O to 715' and remains constant on further addition of copper. If however the solidified alloy is heated for some time a t 900" to 1000" and again cooled the transition take? place a t 790". The change from p- t o a-iron has been followed by magnetic observa- tions. It occurs about 790° and is not influenced by the presence of copper so that the latter is not miscible in the solid state with a-iron. The colour of the polished surface of the alloys varies gradually from red to grey as the proportion of iron increases.The tensile strength of the alloys was not determined. Copper-Mangunese Alloys (compare Schemtschuschny Urasoff and Rykowski (Abstr. 1307 ii 777).-The freezing-point curve of these alloys falls from the melting points of both metals and has a minimum a t 866' and 65% by weight of copper. The deduction from the form of the curve that the metals form a continuous series of mixed crystals is confirmed by microscopic observations but the alloys only become completely homogeneous when heated for some time below their melting point. The alloy containing 2% of copper is about as hard as manganese.with further increase of the former metal they become softer and between 10% and 100% of copper are not much harder than that metal. Copper-Magnesium Alloys (compare Boudouard Abstr. 1903 ii 78 480).-The freezing-point curve shows two maxima at 797" and 33.3 atom. % and 570' and 66.7 atom. % of magnesium respectively corresponding with the compounds Cu,Mg and CuMg and three eutectic points at 730' and 21.5 atom. % 555" and 56 atom. % and 465' and 85 atom. % of magnesium respectively. On the etched surface of the alloys the compound Cu,Mg appears as polygonal crystals and CuMg in long rod-shaped crystals. Both compounds are very brittle and of the same colour as magnesium. The author's results differ in several respects from those of Boudouard (Zoc.cit.). The paper is illustrated by 17 photomicrographs. Ammonio-cuprous Sulphate. ALBERT BOUZAT (Compt. ?.end. 1908 146 75 -77). -Ammonia-cuprous sulphate Cu,S0,,4NH3 (compare Joannis Abstr.. 1898 ii 221 ; 1903 ii 371 ; 1904 i 844 ; PBchard Abstr. 1903 ii 293 ; Foerster and Blankenberg Abstr. 1907 ii 89) is precipitated as a white crystalline powder on the addition of alcohol to a solution of cuprous oxide and ammonium sulphate in aqueous ammonia at 50" in an atmqsphere of hydrogen. Ammoniacal cuprous oxide like the corresponding cupric compound (Abstr. 1902 ii 490 550) is therefore a sufficiently strong base t o displace ammonium from its salts. JOHN W. UALLET (Proc. Roy. Xoc. 1908 80 A 83-S7).-The action of mercnry on certain alloys at the ordinary temperature has been examined.An alloy of tin and platinum corresponding with the formula Sn,Pt is not acted on by mercury but if a very small quantity of sodium is added to the mercury amalgamation takes place a t once. The soft amalgam was strained by squeezing it through chamois leather All the alloys up to SO% of copper are grey in colour. G. S. M. A. W. Interaction of Mercury with Alloys of other Metals. 13-2188 ABSTRBCTS OF CHEMICAL PAPERS. and the fluid portion found to contaiii very sinall quantities of both platinum and tin. A silver platinum alloy corresponding with the formula Ag,Pt anialgmuates witli mewury. The fluid obtained by squeezing through chnmois leather contains both silver and platinum but the proportion of silver is greater than in tlie solid alloy.A copper-tin alloy corresponding approximately with the formula Cu,Sn amalgamates very slowly with mercury and the strained fluid contains only very smdl quantities of the two metals. The experiments show that platinuiii prevents the amalgamation of tin that silver CilUSes platinum to pass into solution and that by alloying copper aud tin the reacliriuss ..tiid extent with which they unite with mercury when separately exposed to its action is greatly diminished. H. M. D. Dissociation by Water of the Double Chlorides of Ammonium and Diniercuriammonium. I€. GAUDECHON (C0712pt. ?*end. 190S 146 1~7-180).-The decomposition of the double chlorides Hg2NC1:N H,C1 (Rxminelsbei*g and Pesci) and Hg,N C1,3N H,Cl ('( white precipitate ") by water at the ordinary temperature is limited by tlie concentration of the ammonium chloyide.Hg,NCl,NH,Cl (solid) + H20 Hg,NCl,H,O (solid) + NH,Cl (dissolved) (1) comprising three components in four phwes constitutes a univariant system. A t 1 5 O the concentration of the liquid phase in equilibrium is 0.011 molecule of NH4C1 per 100 molecules of water whilst at 27" the concentration is 0*20. This increase in the decoinposition is in accordance with the law of the displacement of equilibrium with variatioiis in temperature and it is sl~o\rn that sinmonium chloride colubines with Hg,NCl,H,O with a notable development of heat. The decomposition of Hg2E C1,3NH4C1 by water also constitutes an univariant system NHg2C1,3N13,Ci (solid) '-r Hg,NC1,NH4C1 (solid) + NH,C1 (dissolved) (2).A t 14O the concentration of tjhe liquid phase in equilibrium is 0.65 molecule per 100 molecules of waber and a t 27" the concentration has increased to 0.S 4 molecule which again agrees with the law of displaceixierit of equilibrium aiid the constant coil- centration at a given temperature establishes the non-existence of the compound Ilg2NC1,9NH,C1 In the system (1) there is only a trace of mercury in solution but i n the system (2) the liquid contains a small quantity of the metal as Hg,NCI or its compounds with NH,C1. At 15" the compound Hg2NC1,3NH,C1 does not combine further with ammonium chloride. At 1 OOO the decomposition of the two chlorides proceeds according to reactions which are the converse of those representing their forma- tion thus The equation Hg,NCl+ 3NH,C1= BHgCl + 4NH * (3) 2Hg2NCI,H,0 + 2H,O = 2NH + HgCI + 3HgO .(4) The reactions are really more complicated it beiiig necessary to dissolve the chlorides in arnmoriium chloride solution but the quantities of amnionia inercui ic chloride aud mercuric oxide here represented are act i d l y procl wed.1 NO RG A N IC C H E 311 ST R Y . 189 The conclusions w e drawn that a t the ordinary temperature in the presence of water the two chlorides behnve as true double salts although combination of NH,Ul mitfh Hg,NCl to forni Hg,NCl,NH,*Cl develops a n unusnally large amount of heat and that i n presence of boiling water the radicle Hg,N tends to re-form i t s generators cmmonia mercuric chloride and mercwic oxide. KARL A. HOFMANN and 0.BURGER (Ber. 1908 41 308-3 12).-Yeo-erbium oxide prepared by Wilson and Cleve’s method contains thulium holmium and dysprosium as impuyities. Fractional precipitation with aniline hydrochloride (Kruss Abstr. 1903 i 376) is of no value for purification as the holmium cannot be reniovecl by this process. The methods adopted were (1) treatment of the salts with concentrated potassium sulphate solution (2) evaporatictn to dryness with excess of sodium nitrite and extraction with water when most of the erbium hydroxide is insoluble (3) crystallisation of the for mates (4) grattlual fractional precipitation with dilute ammonia ( 5 ) Urbain’s method of crystallising the ethyl sulphate (dbstr. 1900 ii 346 ; 1906 ii 360). Welsbach’s method of crystallising the double oxalate (this vol.i 26) is very effective for separating holmium and erbium. The purifird material appeared to be homogeneous and repeated purification did not alter it. The atomic weight determined by the sulphate method using Brauner’s precautions (Trans. 1902 8 1 12-13) mas found to be 167.43 (four determinations O = 16 S=32*06). The absorption spectrum of a 1G$/ nitrate solution has bands X 653 55.1 487 450 442. GEORGES URRAIN and Q. JANTSCH (Co~npt. rend. 1908 148 127-129).- Terbium peroxide has a composition corresponding exactly with the formuh Tb 0 so long as too high R temperature has been avoided i n its preparatwn by calcination of a terbium salt. The peroxide loses oxygen at a white heat and consequently the composition of the product of calcining the sulphate at 1600’ contains a variable quantity of oxygen as estimated by dissolving in a sulphuric acid solution of ammonium ferrous snlphate and determining the excess of the latter by permanganate.Terbium peroxide di*solves in nitric acid diluted with a small quantity of water (c“ l) giving colourless monoclinic needles of t e d i u m nitlaate Tb(NOY)3,6H20 which give an aqueous solution neutral to litmus and when heated in a sealed tube melt in their water of crystalliaat8ion a t 89.3”. Th,(SO,) SH,O (Urbain Abstr. 1905 ii 711) is also obtained as a crystalline powder of micaceous lamells by precipitation of a solution of terbium containing sulphuric acid by alcohol. 2’e~biz6?n chloride TbCI,,GH,O formed by dissolution of the peroxide in hydrochloric acid forms colourless transparent prismatic crystals which are extremely h y p o - scopic and give a n aqueous solution neutral to litmus.Dysprosium does not form a peroxide the oxide Dy,O rernains unchanged when heated in either an oxidising or a reducing atmos- phere. Under the conditions in which the hexahydrated terbium E. €I. Neo-Erbium. J. J. S. Some Compounds of Terbium and of Dysprosium. 4. 7 Terbium sulpliate,190 ATHTRACTS OF CHEMICAL PAPERS. nitrate is formed dysprosium gives the pentahydrated dysprosium nitrate Dy(N0,),5H20 resembling bismuth nitrate. This loses water in a dry atmosphere gives a neutral aqueous solution and has m. p. 88.6' (in water of crystallisation). Dysprosium sulphate Dy2(S0,),,8H20 (Urbain and Demenitroux Abstr. 1906 ii 855) closely resembles the terbium salt.Dysprosium chloride DyCl,,GH,O is prepared similarly to the terbium chloride to which it is analogous but is less deliquescent. E. H. Bromates of the Rare Earths. I. New Method for the Separation of the Yttrium Earths. CHARLES JAMES (Chem. News 1908 97 61-62. Compare Abstr. 1907 ii 467).-The author briefly points out the disadvantages of the methods for the separation of the yttriuin earths employed by Urbain (Abstr. 1898 ii 518; 1899 ii 28 ; 1901 ii 160) Demarqay (Abstr. 1896 ii 475 ; 1900 ii 347) von Welsbach (Abstr. 1907 ii 26) Muthmann and Rolig (Abstr. 1898 ii 518) and Muthmann and Bohm (Abstr. 1900 ii 209) and after examining the solubilities of the salts of a large number of inorganic and organic acids recommends the fractional crystallisation of the bromates. The rare earth material generally in the form of the oxalates is made into a paste with concentrated sulphuric acid and heated until fumes cease to be evolved.The residue is powdered dissolved in water at Oo and the solution poured over an excess of barium bromate the operation being performed on the water-bath with efficient stirring. When the double decomposition is completed tho filtered liquid is evaporated to such a concentration that about half the substance in solution crystallises out on cooling. After six series of crystallisations the spectroscope shows that a separation is being effected. After twenty operations the least soluble fraction is colourless and consists mainly of yttrium bromate the absorption spectrum showing however that some dysprosium and in a smaller degree samarium and holmium are present.The brown colour of the oxide also indicates that terbium collects in this fraction. The more soluble fractions become yellower those exhibiting the strongest colour showing very intense bands of dysprosium and holminm. Succeeding fractions attain a rose pink colour and show only erbium bands. Then thulium begins to appear and finally the most soluble fraction is reached consisting largely of ytterbium. The bromates of the rare earths arrange themselves in the following order of increasing solubility samaririm (europium 1 gadolinium P) terbium yttrium dysprosium holmium erbium thulium and ytter- bium. This order is not quite the same as that of the ethyl sulphates; the bromate method in conjunction with Urbain's should prove very valuable for the separation of yttrium from dysprosium and holmium Action of Finely-divided Metals on Water.WILLEM VAN RYN (Chew&. Feekblad 1908 5 1-5. Compare Birnie Abstr. 1907 ii 469) -The author has investigated the action of finely-divided aluminium zinc magnesium nickel copper and lead on pure distilled and possibly of thulium from ytterbium. c. s.INORGANIC CHEMISTRY. 191 water at the ordinary temperature and a t 100'. The lead and nickel were obtained by reduction of the oxalates in a current of hydrogen and the copper by reduction of cuprous oxide. The oxalates of the other metals could not be reduced so that finely-powdered commercial samples were employed. Aluminium has no action on cold or boiling water but addition of a small quantity of mercury produces an evolution of hydrogen which is increased by heat. Zinc decomposes cold water slowly boiling water rapidly the presence of mercury producing no effect.Magnesium resembles zinc but addition of mercury causes a greater evolution of hydrogen than with aluminium. Nickel copper and lead with or without mercury do not liberate hydrogen at temperatures up to 100'. Formation of Certain Precious Stones of the Family of the Aluminides. FRED. BORDAS (Conzpt. rend. 1908 146 21-24. Compare Abstr. 1907 ii 956 ; this vol. ii 8).-When a yellow corundum artificially coloured hy the action of radium bromide is heated on a bath of a lead-tin alloy maintained constant a t 300' by means of a Schlesing regulator the colour becomes paler at the end of three hours and after four hours the stone regains its original colour and transparency.A similar result is obtained with an oriental topaz the yellow colour disappearing. If a sapphire is exposed to the action of radium i t gradually becomes green usually a disagreeable cabbage-green colour but by careful heating as above it can be converted to the beautiful green of the oriental emerald. The conclusion is drawn that oriental topazes were not coloured at the time of their formation but became yellow subsequently by the radio- activity of t h e sun and that an oriental emerald is simply a sapphire in which the blue colour has been exactly neutralised by the yellow resulting from the same radioactive influence. By means of a modification of the alpparatus described by d'Arsonva1 and Bordas (Compt.rend. 1906 143 5673 in which precautions are observed to prevent a rise in temperature of the stone treated the author has submitted corundums to the cathodic rays and finds that the colourless stones do not become yellow whilst the yellow corun- dum retains its colour. Thus the cathodic rays like the P-rays from radium and unlike the X-rays have no action on corundum. A. J. W. E. H. Dissociation Temperatures of Manganese Dioxide (MnO,) and Dimanganese Trioxide (Mn,03) in Air and Oxygen. RICHARD J. MEYER and KURT ROTGERS ,(Zeitsch. umo~g. Chem. 1908 57 104-1 12).-Pure manganese dioxide was prepared by prolonged heating of the nitrate at 500". The experiments were made in an electric furnace the chemical changes being followed by weighing and also by estimating the products iodometrically.The change MnOz -+- Mn,O begins in air a t 530° and is complete (under the conditions of the experiment) in eighty-six hours; the change Mn20 + Mn30 begins about 940° and is complete in twelve hours The oxide R1n304 is stable in air up t o 1300° and does not re-absorb oxygen from the air on cooling. I n dry oxygen a t192 ABSTRACTS OF CHEMICAL PAPERS. atmospheric pressure the reaction MnO -+ nfn,O begins a t 565* and the reaction Mn,03 -3 nh,O a t 1090'. I n oxygen at 650-900° the tetroxide is reconverted into the oxide ISiCn,O,. Spontaneous Combustion of Manganese Sulphide. 0 . BINDER (-3eitsch. nrznl. Chein. 1908 47 144)-A precipitate of hydrated manganese sulphide placed in a tvatch-glass and covered over with a larger one was found t o have become ignited in two 01- threo places.G. S. 'The space between the glasses was filled with fumes. L . D E K Constitution of Cast-irons containing Manganese. LBON GUILTAT (Corryt. rend. 190S 146 74-75).-The chemical and micro- graphical examination of a n extensive series of white cast-irons containing increasing quantities of manganese (0.86% to 42.22%) shows that contrary to the conclusion drawn from earlier experiments (Abstr. 190'7 ii &75) 7-iron is present in cast-irons containing high per- centages of manganese and these also contain a carbide. The cast- iron containing 3.6% of carbon and 15% of manganese when cooled sufficiently slowly consists of tho pure eutectic mixture carbide-y-iron.The addition of manganese t o a grey cast-iron causes the production of y-iron before the graphite has disappeared. HAR'S MALFATTI (Zeilsch. anal. Chew. 190S 47 133-1 40) -Experiment$ showing th:tt the precipitate formed in ferric iron solutions by aminonin and ammonium sulphide is a ferric compound. So long as the supernatant liquid contains not less than 0.5% of NH the precipitate consists of the compound FeS,NI3,. On adding ammonium chloride or by prolongecl washing with water the ammonia is removed and Fe,S is left behind. The same substance is forwed by the action of hydrogen snlphide on ferric hydroxide. A%. A. W. Iron Sulphide. L. DE I<. The Reducing and Oxidising Power of Salts of Iron. ERICR RIULLER and FRIEDRICH KAPELLER (Zeitsch.E'Eektyochem. 1908 14 76-82).-The reducing power of a solution containing ferrous and ferric ions increases with the ratio Fe"/Fe*". Three examples of this are studied (1) Atmospheric oxygen does not oxidise a n acid solution of ferrous sulphate but is quickly absorbed if a n alkali is added. In the former the ratio cannot much exceed lo3 whereas in presence of normal alkali it is 1.5 x lo" owing t o the greater solubility of ferrous hydroxide. (2) Solutions of ferrous and cupric sulphates do not react but cuprous oxide is precipitntetl if potassium fluoride is added to t h e neutral mixture and metallic copper if it is added to the acid solution. I n this case the ratio is increased by the conversion of ferric ions into complex ions containing iron and flnorine.In neutral solution the cuprous ions produced by the reduction separate as hyclroxide whilst in acid solution owing t o the higher concentration reached they yield metallic copper and cupric ions. (3) The oxidation of hydriodic acid to iodine by ferric ions 21' + 2Fe"' =I + ZFe" is reversed by the addition OF potassium fluoride the explanation being the same as that giveii above T. E.1 NORGANIC CHEMISTRY. 193 Some Complex Iron Salts in which the Iron is Masked. P. PASCAL (Conzpt. rend. 1908 146 231-233).-The solubility of ferric pyrophosphate in the corresponding sodium salt is due t o the formation of a new complex salt Fe4(P207)3 3Ka,P207 o r analogous t o the ferricyanicles for which i t is suggested that the name f erri~?,?/ro~~hosphccte be re served.Sodium ferrir,?lropl~os;r?l~ccte Na,Fe,(P,07),,9H,0 is slowly deposited as a pale violet microcrystalline precipitate at 30" from a 15% solution of sodium pyrophosphate saturated with ferric pyrophosphate and yields by double decomposition the silver salt Ag,Fe,( P,07) 4H20 which is greenish-yellow or the copper salt Cu,Fe,( P207) Z2€1,0 which is greenish-blue. The complex acid HGFe2(P,0,),,7H,0 is obtained as a white solid when ferric pyrophosphate is heated fov twelve hours at 50° with two-thirds of its weight of syrupy pyrophos- phoric acid dissolved in acetone. By similar methods the author has prepared sodium fewopyrophos- phccte Na SFeB( P207)$ the corresponding ferro- and j'es.~~i-metn~hosp~c~~es Na,Fe(P0,)6 and Na,Fe(PO,),,and also the corresponding salts in which the iron is replaced by cobalt chromiuni or nickel.N@e,(P,O7),7 31 A. W. A New Series of Ammonio-ferric Salts in which the Iron is Masked. P. PASCAL (C'ompt. rend. 1908 146 279-2S2).-Acldition of ammonia to a ferripyrophosphate solution (preceding abstract) does not precipitate ferric hydroxide but colours the solution reddish- yellow. When ammonia (29' Baumh) is added to the solution at loo obtained by mixing 15.4 solutions of sodium pyrophosphate and ferric chloride the Iiquid is colonred red and there are produced (1) a crystalline precipitate equal to one-third of the sodium pyrophosphate used ; (2) a t tho junction of the two liquids initially separate a layer of red clots surmounted by one of yellow and (3) in the upper layer of the liquld a niass of long felted silky needles. All three com- pounds are nmmonio-ferric salts in which the iron is masked. The compound ( 1) contains sodium pyrophosph:tte which has carried down with it varying proportions of ammonia and iron the ratio between the quantities of the two latter having one of two values.When much ammonia is present the precipitate consists of short thick orange-coloured needles containing iron and ammonia in the ratio Fe NH = 1 1.5. It can be represented as a combination of sodium pyrophosphate and aninioniacal ferripyrophosphate thus rL(Na4P2O7 1 0H,O),Na,Fe,(P,O7) 3NH,,pH20. Values are obtained for n 4 2.5 and 18 and for 22 8 15 and 25. On the other hand i n the presence of but little ammonia the pre- cipitate is composed of small rectangular yellow plates of ten having broken corners.In t,hese the ratio Fe NH equals unity and their constitution is represented by n(Na,P207,1 OH,0),Na,Fe,(P,0,),,~~H~,;r?H20 the values foiind for rz being 18 and 9 and for p 50 and 60. When removed from the liquid and exposed t o the air the red clots (2) liquefy becoming deep violet-red in colour and losing water ancl ammonia. If dried in an atmosphere of dilute ammonia which194 ABSTRACTS OF CHEMICAL PAPERS. prevents dissociation they have a composition corresponding with Fe,(P20p)3,2Na4P207,4NH3,68H20. The substance dissolves in water t o a red solution which is alkaline towards phenolphthalein gives a rusty precipitate with silver salts but does not exhibit the character- istics of ferric salts except towards ammonium hydrosulphide.On prolonged contnct witb dry air the salt loses water and ammonia and is transformed into a brick-red powder of the formula 5 [ Fe,( p207)3,2Na4P207] 4N H 1 6 0 H,O the iron still being masked. When the red liquid obtained by adding ammonia to the ferripyro- phosphate solution is slowly evaporated a precipitate is formed i n two layers the upper one being red and the lower yellow. The latter is a very easily dissociated ammoniacal derivative the former however is a stable compound of the composition Fe,(P207),,SNH,,32H,0 which dissolves in water to a neutral solution giving a pale yellow pre- cipitate with silver salts. All the constituent radicles of this salt seem to be masked. These new derivatives may be members of series having the general [Fe4(NH3),,-~~(P,0,)3+*1R~~ formula I [Fe4( NHJ - 4p(P207)~](P207)3 - p and comparable to the cobaltammines.Perriphosphstes have been prepared having the formula II in which q = 3 whilst the red clots correspond with the same formula when q = 2. E. H. Alloys of Nickel with Tin Lead Thallium Bismuth Chromium Magnesium Zinc and Cadmium. G. Toss (Zeitsch. anorg. Chem. 1908 57 34-71).-The thermal and microscopic examination of the alloys mentioned in the title show that the follow- ing compounds exist Ni8Sn2 Ni3Sn Ni4Sn ; NiBi NiBi ; Ni,Mg NiMg ; NiZn ; NiCd,. Nickel does not enter into chemical combina- tion with lead thallium or chromium. The magnetic properties of the alloys have also been investigated. NickeE-Tifi Alloys (compare Gautier Bull.SOC. Encour. 1896 i 1293 ; Heycock and Neville Trans. 1890 57 376).-The behaviour of these metals is remarkable inasmuch as they separate into two layers in the fused state from 3.5-18% and 26-45% of nickel. There are no distinct maxima on the freezing-point curve but there are three breaks and two eutectic points at 1135" and 68.5% and 229' and 1.3% of nickel respectively. Between 30% and 45% nickel the two liquid layers react at 1262' to form the compound Ni,Sn,. A break in the cooling curve at 1162' corresponds with the forma- tion of the compound Ni3Sn (long needles) from the compound Ni,Sn and a fused mass containing 65% of nickel. Between 60% and 85% nickel there is a break in the cooling curve a t S55O due to the formation of the compound Ni,Sn by interaction of Ni,Sn and the mixed crystals.From 42*5-60% of nickel a slight thermal effect at 837' (sometimes lower owing t o supercooling) appears to indicate the breaking down of the compound Ni,Sn into Ni,So2 and Ni4Sn. There is one series of mixed crystals from 0-15% of tin. Only alloys up to 60% of nickel are magnetic. The temperature atINORGANIC CHEMISTRY. 195 which the magnetic property disappears on heating falls from 350' for pure nickel to 145" for 62% of that metal. From 67-65% of nickel the fall is 60" (I 90'-1 30°) corresponding with the disappearance of the mixed crystals. Nickel-Lead AEloys.-These alloys are not miscible in the fused state between 16% and 72% of nickel. There is a series of mixed crystals which when saturated contain 4% of lead ; a t 1338O these are in equilibrium with the two liquid layers.The solubility of the mixed crystals in lead decreases very rapidly with fall of temperature and a t its melting point pure lead separates. The transition temperature of non- magnetic to magnetic nickel is raised about 5" by the addition of 4% of lead and remains constant a t 350' on further addition of lead. Nickel- Thccllium Alloys.-These metals are not miscible in the fused state from 0-90% of nickel. Nickel retains in solid solution up to about 3% of thallium; these mixed crystals are in equilibrium a t 1386O with the two liquid layers The transition temperature of non- magnetic to magnetic nickel is lowered 15" by the addition of suficienf thallium to form the saturated mixed crystals and remains constant on further addition.Nickel-Bismuth Alloys.-These metals are completely miscible in the fused state. The freezing-point curve consists of three branches without maxima or minima. There is one series of mixed crystals containing up to 0.5% of bismuth. At 638O the saturated mixed crystals react with a fused mass containing 32% of nickel to form the compound NiBi; the latter reacts at 472" with the fused mass con- taining 11% of nickel to form a second compound NiBi,. These com- pounds could not be obtained pure even on prolonged heating in the neighbourhood of their temperatures of formation. The transition temperature of magnetic to non-magnetic nickel is lowered 20' by the addition of sufficient bismuth to form the saturated mixed crystals and then remains constant a t 325" up to a composi- tion of 32% of nickel beyond which point the alloys are no longer magnetic.Nickel-Chromium Alloys.-The freezing-point curve of these alloys consists of practically two branches; from 0-42% of nickel mixed crystals rich in chromium separate and from 42*5-100% of nickel mixed crystals rich in the latter metal. There is a very short break in the miscibility from about 42.0% to 42.5% of nickel. The transition temperature is lowered 100" by the addition of 2% of chromium. NickeZ-Magnesium AZEoys.-These metals are completely miscible in the fused state. The freezing-point curve shows a flattened part (not a true maximum) a t 1145" from 75-83% nickel which from other indications corresponds with the compound Ni,Mg (thin leaflets) two eutectic points at 1082' and 89% nickel (nickel and Ni,Rfg) and 512' and 34% nickel (NiMg and magnesium) respectively and a break at 768'.At the latter temperature Ni,Mg and the fused mass containing about 45% of nickel react to form the second compound NiMg2. All the alloys are magnetic. Alloys containing less than 90% of nickel are non-magnetic.196 ABSTRACTS OF CHEMICAL PAPERS. The magnetic transition temperature of nickel a t 350’ is not altered by the addition oE 17% of magnesium. Prom S3-55(;/ of nickel the transition takes place a t 235’ and alloys containing less than 55% are not inagnetic. .\7icickeZ-Ziizc A Zlop (compare Heycock and Neville Trans. 1897 71. 383).-0nly alloys up to 23%) of nickel were investigated. From 14.5-23°/ of nickel mixed crystals of a compound NiZn3 and zinc sepnrate kntb between 0:A and 14.506 of nickel these niisecl crystals are insoluble in zinc.These results ngreo well with those of Tafel (this vol. ij lOS) except that the latter ~ ‘ O U R C ~ the saturation point of the nlixecl crystals at 12.5% of nickel. A t room temperature these alloys were non-magnetic. ~liickr Z-Cadnxizcn~ AZlo?ys.-Owing t o the volatility of cadmium these alloys could only be investigated 1113 to 15% of nickel. A t Ml” n compound of nnknovn composition reacts with the fused mass to form a compound KiCd,. Nickel is insoluble in solid cadmium at the melting point of the latter. The alloys with zinc and caclniium are not magnetic. The paper is illust,rated by thiyty-four photomicrographs. Sulphide Compounds of Nickel and Cobalt.G. S. ITALO RELLUCCI and LILIO EELLUCCI ( A t t i R. Acead. Lincei 1908 [v] 17 i 18-29j.- By fusing at n high temperature n mixture of a nickel salt with sulphur and a n alkali the crystalline double sulphides 3NiS K,S and 4NiS,BaS may be obtained. Under similar conditions cobalt salts yield only the sesquisnlphide Co,S,; in one case in which the mixture was kept at a white-red heat for n long period a crystalline p d u c t l approximating in composition t o Co3S1 was obtained. Thus nickel behaves analogously to its homolognes palladium and platinum whilst the sulphiur compounds of cobalt in vhich theitervalent type predominates are in accord with those of rhodium and iridium. Theso tncts confirm the position of nickel in the periodic system after cobalt and before copper.Chromic Acid as an Oxidising Agent. 11. KARL SEUBERT and J. CARSTENS (Zeitsch. nn0s.g. Chem. 19OS 58 357-364. Compare Abstr. 1906 ii 6 17).-1n dilnte hydrochloric acid solution hydrazine is oxidised quantitatively by chromic acid to nitrogen and water. The chemical dynamics of the reaction have been investigated at 20° its progress being followed by withdrawing a portion of tahe mixture from time t o time mixing with acidified potassium iodide solution aud titrating the iodine liberated with thiosulphate. The reaction is extremely rapid; in a solution 1/8000 and 1/16000 molar with regard to hydrazine and chromic acid respectively and lj200 molar with regard t o hydrochloric acid it is complete in about a n hour. The rate is proportional t o the concentrations of chromic acid and hydrazine respectively in the presence of excess of hydrochloric acid and is also proportional to the concentration of the latter.The mechanism of the reaction cannot be fully elucidated owing t o the want of knowledge of the constitution of cbromate solutions but the ionic equation Cr20” + N,H; = 2Cr0 + N + 2H,O + OH’ is in agree- rnent with the kinetic measurements. T. H. P G S,ISORGAKIC CHEMISTRY 19'9 The Hydrolysis of Ammonium Molybdate in the Presence of Iodides and Iodates. SETH E. bloom ( A m e ~ . J. Sci. 1'308 [iv] 25 76-78. Compare Glasinann Abstr. 1905 ii 209).-hriirnonium molpbclate is completely hydrolysed in presence of potassinin iodide and potassinin icdate iodine being liberated according to the equations 3(NH4),,M~~O,,,4€I2O = 18NH -I- 2lH,M00 ; 2 1 H,R~OO,~ + 351iI + 7KI0 = 2 I lil,lI09 + 2 1 I + '3 1 €€,(On distilling the free ammonia acts 011 three-sevenths of the iodine unless prevented by acidifying.The detwrnposition of ammonium molybdate is not a partial one as supposed by Glazsm:tnn. R. J. U. Preparation of Silicotungstic Acids. HrPi>oJAwI?" C'o~avs (Bull. Soc. c h i m 1908 [iv] 3 101-109).-Marign,zc descriLed tlii ee acidsof this type namely,silicotungstic acid 12W03,Si0,,2H,0 + 31H,O in quadratic crystals ; tungstosilicic acid 12W03,Si0,,2H20 + 2 2 H,O in triclinic crystals and silicodecitungstic acid 10 WO,,Si0,,4H2O + 3H,O amorphous and unstable. The present paper deals matnJy with methods of preparing these substances. Three methods are available for the preparation of silicotungstic acid and the simplest arid most expeditious Consists it1 treating sodium tungstate with sodium silicate in presence of acetic acid.Tiingstosilicic acid may be most easily made by adding sodium silicate to a faintly acid solution of sodium tungstate making the mixture slightly acid with sulphuric acid and heating a t 100' until 011 adding sulphuric acid and ether oiiy drops separate. I n addition t o tungstosilicic acid some silicotungstic acid is formed and the two mtiy be separated by fractional crystallisation of the potassium salts the silicotungstate separating first. Both salts are isomorphous similarly hydrated liare the same eleztrical conductivity and may be equally well used as alkaloidal reagents.Con tmry to RIarignac's statement! potassium tungstosilicate dowly passes into the silicotungstate when heated with water in a closed vessel at 150'. A slight improvement i n Marignaa's method of preparing silicodeci- turigstic acid may be effected by adding aiiimonia in great excess to a solution of silicotun~stic acid and boiling the mixture the latter being shaken constantly. bThe aniniouium salt so obtained crystallises in orthorhombic prisms aud on solution in water and evaporation yields the required acid. The methods employed for the analysis of these substances have been described alreaJy (compare Copaux Abstr. 1906 ii 170 Friedheim Henderson and Yinagel Abstr. 1905 ii 614). T. A. H Heterogeneous Colloidal Hydroxides of Uranyl Thorium Zirconium Lead Yttrium Iron and Copper.B ~ L A SZILAED ( J . Ciiinz. phys. 1907 5 636-646).-Colloidal solutions we often prepared by dissolving an insoluble hydroxide in a solution of a salt with a common ion. The author has modified the method by ern- ploying hydroxides and electrolytes without a coiilrnon ion and terms the products heterogeneous colloids Such colloids containing thorium lead zirconium and uranyl have198 ABSTRACTS OF CHEMICAL PAPERS been prepared and their properties are described. Isomeric colloids of different behaviour prepared for example from thorium hydroxide and uranyl nitrate on the one hand and from thorium nitrate and uranyl hydroxide on the other are of particular interest. In these colloids it is not in general possible t o displace one component by another directly.They do not give the ordinary chemical reactions for the elements present but a colloid containing lead was found not to be typical in this respect as it gives the reactions for the metal. G. S. Stannic Acids. Huao KUHL (Phurm. Zeit. 1908 53 49).-The stannic acid obtained by treating a hot solution of sodium stannate with sulphuric acid when freshly prepared is completely soluble in 5% hydrochloric acid and concentrated sulphuric acid ; the solution in the latter deposits prismatic crystals whon heated. The stannic acid kept as a paste for ten days is soluble in 5% hydrochloric acid only on boiling and is only partly soluble in concentrated sulphuric acid; the insoluble gelatinous portion is not completely soluble in strong hydrochloric acid neither is the gelatinous stannic acid precipi- tated on heating the sulphuric acid solution.The stanuic acid obtained by carefully adding dilute sulphuric acid to a cold solution of sodium stannate when freshly prepared is readily soluble in 2% hydrochloric acid and strong sulphuric acid ; the solution in sulphuric acid gives no deposit when heated. The acid loses its solubility in sulphuric acid but not in hydrochloric acid when kept for some time in a pasty condition. The staunic acid obtained from a freshly propared solution of sodium stannate is readily soluble in 2% hydrochloric acid and 2% potassium hydroxide whereas that obtained from the same solution after being kept for twelve days is not soluble in solutions containing less than 6% of potassium hydroxide and 5% of hydrogen chloride.W. H. G. So-called Amorphous Antimony. ERNST COHEN and J. OLIE (Zeitsch. phyaikal. Chem. 1908 61 588-595. Compare Abstr. 1904 ii 345 ; 1905 ii 170 532).-H&rard’s experiments (Abstr. 1888 1256) on which is based the existence of amorphous antimony are subjected t o a critical examination. It is shown that when pure antimony and pure nitrogen are used the phenomena described by HQrard are not to be observed. If on the other hand the nitrogen is insufficiently purified these phenomena are reproduced. What HQrard described as ‘‘ amorphous antimony ” appears t o be nothing else than the ordinary stable antimony contaminated with more or less trioxide. J. C. P. Compounds of Antimony Sulphur and Chlorine. HERMAN J. TAVERNE (Chem.Weekblud 1908,5,19-28. Compare Ruff Abstr. 1905 ii 22 ; Bertrand and Finot Abstr. 1881 239 ; Ouvrard Abstr. 1893 ii 533; Hensgen Abstr. 1891 1160; and Walden Abstr. 1901 ii ll).-A review of previous work on compounds of antimony with sulphur and chlorine and an account of two derivatives prepared by the author are given. When dry hydrogen sulphide is passed into aINORGANIC CHEMISTRY. 199 solution of antimony trichloride in dry carbon disulphide or tetra- chloride or in n mixture of these solvents there is formed a white precipitate which is converted by a little water into antimony trisiilphide. On continued passage of hydrogen sulphide the colour of the white compound changes to yellow yellowish-red orange and finally dark red. The end-product is crystalline and has the formula Sb,S,C12. It is identical with that obtained by Ouvrard.The author gives reasons supporting the view that it results from replace- ment of one S-atom in two molecules of antimony trisulphide by two C1 atoms. A light orange crystalline intermediate product Sb,S,Cl has also been isolated. A. J. W. So-called Amorphous Bismuth. ERNST COHEN and J. OLIE (Zeitsch. physikal. Chem. 1908 61 596-598).-The results described by Hbrard (Abstr. 1889 572) can be obtained only wiBh imperfectly purified nitrogen. What HBrard refers to as amorphous bismuth is the ordinary form of the metal contaminated with more or less trioxide. J. C. P. Bismuthous Compounds. 11. WALTER HERZ and ARTHUR GUTTMANN (Zeitsch. unory. Chem. 1908,56,422-428. Compare Abstr. 1907 ii 274).-The freezing-point curve of the system bismuth trichloride-bismuth shows a maximum corresponding with the composi- tion of bismuthous chloride BiCl and the formation of this compound is confirmed by the fact that its density 4.85-4.88 is lower than that of a mixture of bismuth trichloride and bismuth of corresponding composition.It occurs in thick lustrous black needles m. p. 163'; the black colour may be due to a trace of impurity Bisrnuthous bromide and the corresponding iodide are formed by heating the bismuthic compounds with the calculated amount of bismuth ; the former occurs in greyish-black crystalline leaflets D 5.9 m. p. 1 9 8 O the latter in crystals with metallic lustre D 6.5 which decompose below their melting point. An unsuccessful attempt was made to prepare the chloride and bromide by leading the corresponding halogen acid over heated bismuthous oxide.The authors now admit that contrary to their previous statement and in agreement with Aten (Abstr. 1906 ii ll) there is no evidence of the existence of bismuthous sulphide BiB. G. S. Ghemical Decomposition of Platinum by means of an Alternating Current. THEODOR GROSS (Chern. Zentr. 1907 ii 1729 ; from Elektrochern. Zeitsch. 1907 14 146-147).-When potassium carbonate containing a little potassium nitrate is treated in a platinum crucible at a yellow heat with an alternating current (50 alternations per second 120 volts 35 amperes) the platinum is attacked and needles resembling graphite are formed on and in the fused mass. The brown residue obtained on extracting the fusion with water is attacked by hydrogen only with difficulty is soluble in hot hydrochloric acid or after ignition in aqua regia and gives a dark brown precipitate with hydrogen sulphide. The filtrate from this on evaporation yields200 ABSTRACTS OF CHEMICAL PAPERS. a red powder which does not contain platinum dissolves in hydrochloric acid is precipitated by potassium hjtlroxicle and after ignition is soluble only when first disintegrated by means of a n alkali.The needles forined during the electrolysis behave in the same manner as the brown residue after solution in aqua regia. It is considered that the red powder is the hydrate of a new substance. After ignition the hydrogen sulphide precipitate fram the whole of the product's weighs 157;. less than the loss of platinum from the crucible and electrodes. Ordinary plat'inum cannot be detected in tlie electrolysed fused mass. The electrolysis of potassium hydroxide and of a mixture of nitric and sulphuric acids in platinum gives similar results. G. Y. Rhodium. ALEXANDER GUTBIER and A. H~TTLINGER (Bey. 1908 41 2 10-21 6).-The double halogen salts of rhodium described were prepared with the object of finding a material suitable for atomic weight determinations. When heated in a stream of hydrogen they all give up the halogen attached to rhodium as halogen hydride and can therefore be aiialgsed by the method described by Gutbier 'I'renkner and Ransohoff (ZeitscJl. unorg. Chena. 1905 45 166 243). Potassium rhodi~eiatncJ~lo?.ide K,LthCl,,H,O prepared either by heating potassium chloride and rhodium i n a sti-earn of chlorine or by con- centrating a solution of the components in niolecular proportions forms small glistening dark red plates. Sodium 1.Aodil~elL.acJ~Eoride Na,€LhCl 1 %H,O forms a rose-coloured powder. A~rimoniuin rhodi- Iiexachlorzde (NHJ3RhC16 1 &H,O forms dark red crystals whilst the y ~ ~ o d i ~ ~ e ~ z t a c l ~ ~ o 1 . i d e (NH,),RhCl,,H,O separates in glistening dark red Ccesiuwb and rubidium ./'~o~il;eentac?~Eo.r~ides corild not be prepared by heating ctesium or rubidium chlorides with rhodium in a stream of chlorine but were obtained (with 1 H,O) as sparingly soluble brilliant rose-coloured products by the aliernative method. The corresponding rhodibromides were obtained from the potassium salt (the only one accessible) by heating a iuixture of finely-divided rhodium and the alkali bromide in a stream of bromine. Potnssiurn rhodipe?ztabi.ontide K,KhBi* forms brilliant dark green irregular plates ; ammo?~ium yliodz;ue?atccbro,12ide (NH,),IthBr is black with a green shade ; the m s i u m mid rubidium coinpouiids which are sparingly soluble have a Lrilliant green colour. cry s t a1 s . E. F. A.

ISSN:0368-1769    

DOI:10.1039/CA9089405172

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

200 ABSTRACTS OF CHEMICAL PAPERS. Mineralogical Chemi strg. Sodium Fluoride in Nepheline-Syenite from Los Islands. ALFRED L A C ~ ~ O ~ X (C'orript. T e d . 1'308,146 3 13-2 16).-The Los Islands off tho West Coast of Afyics are composed entirely of nepheline-Yyenites which vary from fine-grained to pegnitttitic in texture aiid contain thoMINERAEOCICAL CHEMISTRY. 201 following minerals microcline albite nepheline bright blue sodalite aegirite arfvedsonite astrophyllite biotite Gvenite eudialyte fluorite and analcite. The analcite occurs as a n original constituent in limpid masses the size of the fist. A fine-grained grey rock from the island of Rnma is spotted with a crimson mineral which mas found to be essentially sodium fluoride (with traces of potassium calcium and possibly zirconium) ; D 2.79; H < 3.This new mineral cailed villiccumnite is tetragonal and pseudo-cubic with three perfect cleavages at right angles to one another. The refractive index (ns,t = 1.328) is lower than t h a t of any other mineral and less than t h a t of water; t h e birefringence is very feeble and no interference-figure is seen in convergent polarised light. A striking feature is the very strong pleochroism the colours being crimson and golden for vibrations respectively perpendicular acd parallel to the vertical axis. The colour and pleochroism were thought to be possibly due t o the presence of tt trace of manganese but this element could not be detected. At a red-heat. t'he colour is destroyed and the mineral fuses t o a colourless mobile liquid.The mineral is soluble in water and from the solution sodium fluoride crj stallises as cubes or octahedra with cubic cleavages and D 2.76 n,=1*327. Boiling water extracts from the rock 0*35% of soluble salts consisting mainly of sodium fluoride with some sodium chloride. The new mineral is present as a primary coustitueut of the nepheline-syenite. The minerals most closely related to i t are the alkali aluminium fluorides cryolite cryolithionite arid chiolite. L J. S. Magnesium-pectolite from the Diabase of Burg Hesse- Nassau. E. REUNING (Centr. illin. 1907 739-741).-Pectolite occurs in crevices of the diabase at Burg near Herborn as white masses with a radially fibrous structure. SiO,. Al,O,. CaO. BIgO. Na,O. K20. <110". >110". CO,. C1. Total.81). gr. 54-11 0'64 24-54 5.54 6.63 0 2 1 1.7s 5'32 0.82 trace 99'89 2.688 Analysis by M. Dittrich gave H,O. H,O. These results besides showing an abnormal amount of magnesia differ appreciably from other analyses of pectolite and no simple formula is deducible from them. The material is no doubt impure since it is not always completely decomposed by hydrochloric acid. The mineral is largely altered apparently t o prehnite,. L. J. S. Composition of Nepheline. J ~ Z E F A. MOROZEWICZ (Bull. Acud. Sci. Cracow 1907 958-1008).-Nepheline is completely soluble in a N/4 solution of hydrochloric acid and this gives a method of readily separating enclosed impurities (felspars mica hEmatite &c.) which in earlier analyses must have been weighed with the silica. I n the following new analyses each the mean of two determinations special precautions were observed ; the alkalis for example were not determined at the end of the analysis since their amount would be increased by the accumulation of impurities from the reagents. I is of grey porphyritic crystals from mnriupolite (Abstr.1902 ii 668) ; VOL. SCIV ii. 14D 2.631 (not allowing for 1276 of enclosed albite). 11 R large mass of eholite also from msriupolite with 9.8% insoluble material (albite sgirite beckelite &c,). 111 grains of red elzolite from mariupolite enclosing 50% of perthitc and lmmatite. IV elzolite from Alias Urals ; D 2.645 ; the powdered mineral gives an alkaline reaction in water and after digestion foy twelve hours 0.45% is dissolved V well-formed crystals of nepheline from Vesuvius ; D 2.64.TI small prismatic crystals from Vesuvius with 0.5 % insoluble enclosures SiO,. TiO,. A1,0,. Fe,Os. CaO. MgO. K,O. Na,O. H,O. Total. I. 43-65 0.10 33.12 0.48 0-49 - 5.69 15-91 0-74 100.18 16-12 0'89 99.97 11. 43'46 0.07 32.82 0.75 0.31 - 5.55 111. 43.55 0.03 32.96 0'66 0.25 - 6.09 16'00 0.33 99.86 IV. 42'71 0-04 33.83 0'40 0.32 trncc 5.SG 1G.46 0-18 99-86 V. 42-53 0.01 33.92 0.30 1.97 0.07 5.82 15.12 0'13 100'11 VJ. 43.34 trace 33.75 0'50 2.20 0'24 4.34 15.66 0.23 100.26 I n all these analyses the molecular ratio of (Al,Fe),O (Na,,K,,Ca)O = 1 1 ; but the ratio of (Si,Ti)O (AI,Fe),O varies from 2-11 1 to 2-21 :1 (being 2.21 1 in analyses 1-111). The ratio of K,O (Na,O+CaO) varies from 1 4-06 t o 1 6.6 being usually 1 4.4.These and previous analyses are discussed in detail and evidence is adduced to show that potassium (which is invariably present in nepheline) and sodium do not replace each other isoinorphously. Most analyses may be referred to the following series of normal nephelines These formuls represent double compounds of a potassiurn alumino- trisilicate (comparable with the silicate portion of sodalite &c.) with a sodium alumino-disilicate (analogous t o n atrolite minus water). A few analyses (amongst them 1 V nud V now given) represent 3 slightly more basic type with the formula K4Na18A12,Si230~lo = 2T(,Al,Si,!O!) + DNa,Al,Si,08. L. J. S. Mineralogy of Iron Mine Hill Rhode Island. B. L. JOHNSON and CHARLES HYDE WARREN (Amer. J. Xci. 1908 [iv] 25 1-38).- I n an account of the geology and petrography of Iron Mine Hill near Cumberland i n Rhode Island a detailed description is given of the ultra-basic igneous rock called cum berlandite which consists of olivine (46%) labradorite (9%) magnetite (go$%) and ilmenite (18%) with some spinel (34%) and metallic sulphitles (1%).Analysis I of the olivine shows it to be the iron-rich variety hyalosiderite. Analysis I1 is of the fresh unaltered cumberlandite. Chloritic (anal. 111) actinolitic and serpentine (anal. IV) types of alteration of the cumberlandite are distinguished. The altered rock is traversed by narrow veins of secondary minerals which are mainly actinolite (anal. V) clinochlore and hortonolite (VI) :MINERALOGICAL CHEMISTRY. 203 Si02. TiO2. A1203 Fez03.FeO. MnO. MgO. CaO. K2O. NazO. H20. Total. Sp. gr. I. 37.16 0'07 - 0.12 31 38 0'40 31'16 tracr - - - 100.63" 3.728 11. 22'35 10.00 5.26 14.05 28'84 0'43 16.10 1-17 0'10 0'44 0'42 99.2Gt 3'92-4'0 111. 20'89 9.57 6.93 17'81 26'04 - 15.65 0 9 6 nil trace 2'71 100.54 3'80-3'S5 IV. 19'98 9% 6.75 19% 21'42 0'40 16'53 11. d. trace trace 4.77 99-32 3.56-3'65 V. 66'00 trace 1'00 0.10 7'14 0.10 20'52 14.03 trace 0'50 0'80 l O O l 9 l 3'062 VI. 33'27 trace - 0'37 49.32 1.50 16'08 - - - 11. cl. 100'54 4.054 * Also insoluble felspar 0.347. + Also (not included in total),'V203 0.18 ; CI203 trace ; C02 0'02 ; P205 0'02 ; 8 0.38 ; Zn 0.71; Cu 0.08; Co+Ni 0'0s; Pb trace. f Also trace of fluorine(?). This analysis of actinolite gives ratios agreeing closely with those of Penfield (Abstr.1907 ii 102). The hortonolite is a dark resinoils mineral with distinct cleavages in two directions a t right angles ; in small fragments it is pale yellow by transmitted light. The occurrence of this rare member of the olivine group as a secondary vein mineral is of interest. L. J. S. The Volcano of Siroua in the Morocco Atlas. LOUIS GEXTIL (Compt. q*end. 1908 146 185-187).-A description is given of this extinct volcano the rocks of which belong to two series trachytic and phonolitic. Analyses are given of a biotite-trachyte and of a hauyne-aegirite-phonolite. L. J. S. Origin of Laterite. JEAN CHAUTARD and PAUL LEMOINE (Compt. rend. 1908 146 239-242).-The products of decomposition of rocks are diBerent in temperate and in tropical regions; in the former they consist of aluminium and iron hydroxides and i n the latter of aluminium silicates (clays).The products in tropical regions consist of bauxite and laterite which are analogous in constitution and are of importance as ores of aluminium and iron respectively. Twelve analyses by F. Pisani are given of rocks and their decomposition products from Guinea; the following are selected as examples. I and I1 are of fresh diabase and Icc and IIa of the laterite which has been derived from the same rocks Loss on SiO2. TiO% 81203. Fe203. FeO. CaO. MgO. K2O. NazO. PzO% ignition. Total. I. 51'50 1-56 13'83 - '?SO 11'21 7.85 0.68 2-27 0'06 0 5 0 99.56 Ia. 12'60 3'24 35.71 23-78 1.26 0 63 0'16 0'32 0'14 - 23.70 99.54 11. 48'51 2'96 14'18 2'40 10.35 8.00 6'05 0.67 4.51 0'13 3.12 100.75 IIa.5'52 9'05 34'10 27'13 1'26 - 0'65 0.26 0 25 - 22'50 100.72 Assuming the titanium dioxide to be the most stable and constant constituent it will be seen from these analyses that the decomposition has resulted in the removal of the calcium magnesium and alkalis a removal of about four-fifths of the silica and a slight removal of alumin- ium and iron; the percentage amounts of the latter being relatively increased. The aluminium is present as minutely crystallised hydrargil- lite (A120,,3H20) and the silica is free. The process of lateritisation therefore consists in the removal of certain constituents and in the oxidation and hydration of others. L. J. 5. The Williamstown Meteorite. EDWIN E. HOWELL (Amer. J. Xci. 19OS [iv] 25 49-50).-This meteoric iron was found on 25th April 1892 near Williamstown Grant Go.Kentucky. It weighed about 31 kilos. with D 8.1. The structure is that of a typical octa- 14-2PO$ rlBS'I'RtlCT8 OF CHEMICAL PAPERS. hedrite of medium coarseness. Exnds of kamncite tznite and plessite are visible on the etched surfaces with hero and there nodules of troilite some of which enclose carbonaceous matter and are sur- rounded by a skin of schreibersite. Fe. Xi. Co. Cn. Cr. P. 8. C. 8i. Total. 91-54 7'26 0.52 0.03 0.05 0.12 0.17 0'004 trace $9.694 Analysis by W. Tas>in gave L. J. S. The Ainsworth Meteorite. EDWIN €2. HOWELL (Anzer. J. Sci. 1908 [ iv] 25 105-107).-This meteoric iron which weighed 10.65 kilos was found in the winter of 1906-7 near Ainsworth in Brown Uo. Nebraska. The structure is octahedral with very wide bands on the surface of which a minute octahedral structure is also evident. Troilite and schreibersite are present. Fe Ni. Co. CIL 1'. S. Cr. Si. C. Sp. gr. Analysis by W. Tassin gave 92.22 6.40 0'42 0.01 0.28 0.07 0'01 0.05 0.09 7'SFi L. J. S.

ISSN:0368-1769    

DOI:10.1039/CA9089405200

出版商:RSC    

年代:1908

数据来源: RSC

摘要:

PO$ rlBS'I'RtlCT8 OF CHEMICAL PAPERS. Physiological Chemistry. Cheyne-StokeB Respiration. MARCUS S. PEMBREY (J. Pathol. Bacteiiol. 1908 12 258-265).-This type of breathing is not necessarily pathological but is a sign of decreased excitability of the nervous system. Carbon dioxide increases and oxygen diminishes until the depressed cells of the respiratory centre are stimulated to produce shallow and inefficient respiratory efforts so that the increase of carbon dioxide and decrease of oxygen in the blood still continue ; this in time increases the respiratory efforts and culminates i n dyspnceic breathing which sweeps out the carbon dioxide and increases the oxygen taken in ; the stimulation of the centre wanes and finally apnaa sets in until the same series of events is repeated.This view is supported by analyses and numerous tracings of the respiratory movements are given. W. D. H. Equilibrium between the Cell and its Environment with Special Reference to Red Blood Corpuscles. BENJAMIN MOORE and HERBERT E. ROAF (Bio-Chem. J. 1908 3 55-81).-The membrane theory fails to explain many phenomena such as the difference in composition of the electrolytes within and without the cell and the variations they undergo in different media. The view is advanced that adsorpates or chemical combinations are formed within the cell between the electrolytes and the proteins. These constituents undergo reversible changes of association and dissociation with altera- tions of osmotic pressure ; the range varies for each constituent and within it labile changes are alone possible.nrugs toxins and other agencies produce other adsorpates or compounds which upset cell- metabolism on account of their stability a t given osmotic pressures. W. D. H.PHYSIOLOGICAL CHEMISTRY. 205 Proteic Acids in Blood. J. BKOWI~~SKI (Zeitsch. phpsiol. Chem. 1908 54 548-549).-The proteic acids of Bondzydski and other? which are discoverable in human urine occur also in the urine of the horse They can also be detected in the blood-serum of the horse after proteins have been removed by acidification boiling and filtering. They are not identical with nrochrome. IT. I). H. Researches in Phagocytosis. HARTOC J. HAMBURGER and E. HEKMA (PTOC. k. Akad. Vetensch. Amstei-dam 1907 10 144-1 66).-The activity of the cells was determined by counting the percentage which took up carbon particles.The addition of water lessens this activity but replacement of the cells in their own serum restores i t either wholly or partly. A heightening of the concentration of the serum by salt similarly damages the cells and again restoration O C C I I ~ S when they are returned to their own serum. I n solutions of 0.9% sodium chloride the phagocytic power is about equal to that in sei-urn. I n some cases chemical action rather than osmotic changes alters phagocytic power; thus Ca ions and aLo OH ions increase it. Na ions are not harmful to Ieucocytes although Loeb found they were to larva? heart muscle &c. W. D. H. Variations in the Proteolytic Activity of Pancreatic Juice. LUCIEN CAMUS and EUG~NE GLEY (J.Physiol. et PuthoE. g h . 1907 967-998).-The juice secreted under the influence of secretin is not always without action on proteins When the secretion ceases after the first injection the firat portion of that secreted as a result of a second injection is slightly active digesting egg-white more or less completely in thirty-six to forty-eight hours. If the second injection is made before the effect of the first has passed off the juice is inactive. The juice which is secreted under the influence of an injection of Witte’s peptone or pilocarpine is always slightly active the secretion of active juice alternating with periods of the secretion of inactive juice. The addition of potassium oxalate to the juice sufficient in amount to precipitate all its calcium salts hinders but does not abolish its proteolytic activity.W. D. H. Calcium Metabolism. S. W. PATTERSON (Bio-Chem. J. ‘1908 3 39-54).-A diet of oatmeal and maize produces calcium starvation in rabbits but the blood undergoes no loss of calcium. The bones however lose calcium. I n experiments on rabbits and men the conclusion is drawn that; the bones are the seat of calcium storage. W. D. H. Fate of Carbon Acids in the Dog. I. Normal dl-a-Amino- acids. 11. Meth ylated dl-a-Amino (Normal)-acids. 111. Methylated dl-a-Amino-acids containing Side-Ghains. IV. Dime t hylated dl-a-Amin o( Normal)-ac ids. V. Synthesis of Acetoacetic Acid by Perfusion through the Liver. ERNST FRIEDMANN (Beitr. chm. Physiol. Path. 1908 11 161-157 158-176 177-193 194-201 202-213).-Dogs were fed by the mouth on the various acids and the urine examined for the substances given; the206 ABSTRACTS OF CHEMICAL PAPERS.C N ratio was also taken as a guide as to whether the materials administered had passed into the urine. 1. Glycine dl-alanine dl-amino-m-butyric acid dl-amino-m-valeric acid and dl-amino-n-hexoic acid were given. Thirteen % of the lest-named substance passed into the urine; the remaining acids were almost completely broken down in the body. 11. I n the second series sarcosine dl-a-methylamino-propionic -butyric -Valerie and -hexoic acids were given. The first two were found in the urine to about one-third of the amount given. The last three left the body almost unchanged. 111. I n the third series dl-a-aminoisobutyric acid dl-a-methylamino- isovaleric acid dl-a-methylamino-P-methylvaleric acid and dl-a-methyl- amino-y-methylvaleric acid were given.The presence of a second tertiary hydrogen atom increases the ability of the organism to decom- pose the acid given; this is still more the case when the tertiary hydrogen atom is in the P-position to the carboxyl group. IV. Dimethylaminoacetic dl-a-dimethylamino-n-propionic dl-a-di- methylamino-n-butyric dZ-a-dimethylamino-~~-valeric and dl-a-dimethyl- amino-n-hexoic acids were given. On the average about 50% of the sub- stance administered was excreted as such. The introductionof the second methyl group does not therefore increase the difficulty of the organism to deal with the acids. V. This research is on rather different lines to the four which precede it.The liver was perfused with a mixture of Ringer’s fluid and blood t o which various substances were added (alcohols aldehydes organic acid &c.); many of these lead to the appearance of acetone in the issuing fluid. Of those investigated only acetaldehyde and aldol led also to the appearance of acetoacetic acid. In the case of the first of these aldol is probably first formed as a condensation product. W. D. H. Production of Fat from Proteins. Estimation of Fat. ELLY A. BOGDANOFF (J. Landw. 1908 56 53-87).-The results of experiments with pigs indicated that mixed foods very rich in proteins had very slight fattening effect. It is however considered probable that a certain amount of fat can he formed from protein. I n eatimnting the amounts of fat the substance cut thin and dried at 97-100° is first kept in contact with ether for some hours.It is then cut into smaller pieces and again extracted. The residue is then finely ground extracted with ether for two days in a Soxhlet apparatus after which i t is treated with boiling alcohol for two days or longer. Ths residue obtained by distilling the alcoholic extract is extracted with ether and all the ether extracts united. The substance is practically free from fat after the above treatment. Traces of fat can however be obtaiued by Dormeyer’s artificial digestion method followed by extraction with ether. N. H. J. R I . Parenteral Nitrogenous Metabolism. I. LEONOR MICHAELIS and PETER RONA (Pfliigw’s Archiv 1908,121 163-168).-1n a dog in nitro- genous equilibrium half of the milk in the diet used during the first period of the research was withdrawn and a subcutaneous injection of the corresponding quantity of caseinogen substituted.There was aPHPSTOLOGICAL CHENISTKY. 207 great increase in nitrogenous excretion although no caseinogen as such passed into the urine. The injected protein is believed t o have been katabolised and a t the same time some of the nitrogenous break- down is attributed to a toxic action ; the animal gave indications of this by a rise of temperature and otJier symptoms. The most noteworthy effect which was sulmquently confirmed on other animals was a swelling of the mammary glands leading in some cases t o actual milk formation. This suggests t h a t the iiiammzt? do not actually form caseinogen but are merely the seat of i t s excretion.W. D. H. Protein Synthesis in Animals. VALDEMAR HENRIQUES (Zeitsch. physiol. Cheiu. lYOS 54 406-422).-If animals are fed with the abiuretic products of protein cleavage obtained by the action of trypsin and erepsin they remain in nitrogenous equilibrium or may even put on nitrogen. If these products are boiled for six hours with 30% sulphuric acid they retain this property ; but after seventeen hours’ boiling they lose it. What this means exactly it is impossible to say. It was however noticed thiit the trypt,ophan reaction remained unchanged in t,he products capable of utilisation. W. D. H. The Value of Amides in Carnivora. W. VOLTZ and G. YAKUWA (P’uyev’s A~chiv 19OS 121 117-149. C.ompare Abstr. 1907 ii log).-A mixture of ainmoniurn acetate acetamide and glycine increases tlie absorption of nitrogenous material ; asparagine does not influence niti,ogenous katabolism until after its adiuinistration ceases and then i t is lessened ; acetnmide increases nitrogenous katabolism and ammonium :acetate has a still more marked effect; glycine has no effect.W. D. H. Chemical Studies on Growth. IV. Transformation of Glycogen by Enzyme Action in Embryonic Tissues. LAFAYETTE B. MENDEL and TADASU S A m r . V. Autolysis of Embryonic Tissues. VI. Purines Pentose and Cholesterol of Eggs. VII. C a t a l a s e in Embryonic Tissues. VIII. Lipase in Embryonic Tissues. IX. Embryonic Muscular and Nervous Tissues. LAFAYETTE B. MENDEL and CHARLES S. LEAVEN WORTH (Amer. J. Phgsiol. 190S 21 64-68 69-76 77-84 85-94 95-98 99-104.Compaxe Abstr. 1907 ii 895).-Embryo pigs were used throughout. IT. The embryonic muscle contains glycogen at an earlier date than the liver and when digested with glj~cogen causes more of it t o disappear thau in the case of tlie liver. I n later embryonic life t h e liver acquires it’s characteristic capacities and overtakes the muscles in efficiency. These organs were not freed from blood but in all case8 the glycogen digesting power of the blood is relatively small. V. Experiments on aiito1:;sis were confined to the liver ; autolysis in tlie fetal liver is less rapid thixrl that in the adult ; this is not due to lack of autolytic ferments but t o the waut of development of acid which in its turn inay be attributable to scarcity of carbohydrate. If the acidity is artificially equalised in the two cases autolypis proceeds at an equal velocity in both.208 AESTRACTS OF CHEMICAL PAPERS.VI. The figures given adduce further evidence of the progressive synthesis of purines during embryonic growth and as in adult and embryo org;~ns already examined guanine and adenine predominate. The yield of pentose (absent in fresh eggs) increases as nucleo-proteins are elaborated. There is no evidence that a synthesis of cholesterol occurs in the development of the chick; that present in early stages appears like other lipoids of the yolk to disappear acting as sources of energy in growth. VIT. Any difference in the amount of oxygen liberated from hydrogen peroxide by embryonic as compared with adult organs appears to be due to ext,raiieous cnnses (for example the inhibiting influence of acid) mthw than to an absence of catalase in the embryonic tissues.VIII. Lipase is present at an early stage in the embryonic liver and intestine; but the action of extracts is lees pronounced than that of those ,obtained from full-grown animals. IX. Embryonic tissues are relatively rich in water. Clreatine is present in the embryonic muscle but in less amount than in the adult. Among the purine bases adenine and guanine preponderate as in other tissues. Hypoxanthine is free in the tissue as in the adult. W. D. H. Importance of Calcium Salts for the Growing Organism. HANS ARON and ROBERT SEBAUER (Biochem. Zeitsch. 1908 8 1-28).-The amount of lime required by a growing mammal is at least 1.2% of the increase in body weight.The same diet may a t one time contain enough lime when given in small quantity so as t o pxoduce but little growth and a t another time when given in large rations i t may not contain enough lime on account of tbe more rapid increasein body weight. The body as a whole is not affected by a shortage of lime; the effects are limited to the skeleton (possibly the brain is also affected to some extent). The bones do not weigh less but contain less organic substance and more water than normal ones. The dry substance of the skeleton of he-starved animals also contains a smaller percentage of ash than that of normal animals but the proportion of calcium in the ash is not appreciably decreased. These chemical changes agree with those observed in rachitic bones.G. B. Nitrates in Vegetable Foods Cured Meats and Elsewhere. 1757-1767).-The results of a large number of determinations of nitrates in different foods (fruits vegetables and cured meats) showed that with a diet consisting of fresh vegetables the equivalent of 1 to 2 grams of sodium nitrate could be consumed daily. Smaller amounts of nitrates could be consumed with a diet consisting partly of cured meats so that the quantities of nitrates in the latter must be considered harmless. N. H J. M. The Substitution of Bromine by Chlorine in the Animal Body. M. BONINGER (Chena. Zentr. 1907 ii 1530 ; from Zeitsch. exper. Puth. Z'heT. 1907 4 414-418).-1n absolute chlorine hunger in the WlLLIAM D. RICHARDSON (J. AmW. Chen2. XOC. 1907 29,P H 1’s 0 LOG1 C A L C H E hf I STRP .209 dog bromine can take its place; even in the blood serum chlorides are replaced by bromides. Cumulation of the halogen was not observed. W. D. €1. The Cell and its Medium. 111. Inorganic Salts of the Protozoan Cell and its Medium. h f o s W. PETERS (Amey. J. Pl~ysiol. 1908 21 105-1 25).-Yarcc7?2acin were placed in pure distilled water which mas frequently changed the organisms being a t each change separated by the centrifuge. 3Iel.e centrifugalising was found to produce no injury. I n spite of tliis the animals contaminated the water ; this WLS due to the diffusion outwards of the salts of the cells and this led to loss of movement and finally death. Noderate withdrawn1 of the salts is harmless. W. D. H. [Amount of] Arginine Lysine and Histidine in the Hydrolytic Products of Various Animal Tissues.ALFRED J. WAKENAN (J. Biol. Chem. 19OS 4 11 9-147).-Variations occur in the yield of these three substances froui different tissue proteins. The group (or groups) in the protein molecule which yield the bases is large in the case of muscle and small in that of the kidney; but in the same organ of different species of animal the variations are very small. I n pathological organs even when gross changes occur as in acute atrophy of the liver the composition of the liver protein is not essentially changed so far as the amount of and proportion between the bases is concerned and the amount of histidine is least influenced by degenerative changes. W. D. H. The Work of the Intestinal Muscle.OTTO COHNHEIM (Zeitsch. plqsiol. C’henz. 1908,54 461-480).-The production of carbon dioxide in the normal movements of the intestine is from 20 to 36 mg. per 100 grams of muscle per hour. This is about one-tenth of that found in striped muscle and from 1/20 to 1/70 of t h a t produced by glandular activity. The movements were made to occur by placing the intestine in oxygenated Ringer’s solution. W. D. H. Formation of Dextrorotatory Lactic Acid in Autolysis. 111. In Muscle KATSIJJI INOUYE and K. KONDO (Zeitsch. physiol. Chem. 1908 54 481-500).-During autolysis of rabbit’s and bird’s muscle there is as in rigor mortis ft formation of sarco-lactic acid even in the presence of chloroform water. Later (about the seventh day of autolysis) the amount diminishes.I n the muscles of cold- blooded animals (fish) the same occurs but the increase is not so marked. The same occurs in filtered extracts of khe muscles and therefore the acid cannot be a product of cellular activity. The action is regarded as due to a ferment and the source of the acid to be both carbohydrate and protein. W. D. H. Vagus Inhibition and the Output of Potassium from the Heart. WILLIAM H. HOWELL and vi’. W. DUKE (Amel.. J. Yhylsiol. 1908 21 51-63. Compare Abstr. 1907 ii llO),-If the isolated mammalian heart is perfused with Locke’s fluid and the vagus210 ABSTRACTS OF CHEMICAL PAPERS. stimulated the increase in potassium of the fluid may amount to as much as 29%. It is beliet-ed that the inhibiting influence of the vagus is due to the liberation of potassium in diffusible form and it is the potassium which inhibits the heart.The amount of calcium in the circulating fluid does not alter. Stimulation of the accelerator nerves causes no increase in the amount of potassium in the circulating fluid. W. 13. H. Carbon Dioxide in the Regulation of the Heart Rate. YANDELL HENDERSON (Amer. J. Physiol. 1908 21 126-156).-1n dogs under artificial respiration the development of shock is dependent not upon the extent of injury or the intensity of stimulation of afferent nerves but on the rate of pulmonary ventilation. Diminution in the amount of carbon dioxide in arterial blood increases the heart rate up to cardiac tetanus and by regulation of the rate of pulmonary ventilation the heart can be adjusted to any desired rate of beat.The hypothesis is presented that acapnia (this is diminution of carbon dioxide in the blood and tissues resulting from hyperpnea and from exhalation of carbon dioxide from exposed viscera) is the cause of surgical shock. The Iron of the Liver. V. SCAFFIDI (Zeitscfh. physiol. Chem. lOOS 54 448-460).-0oe hundrcd grams of rabbit's liver contains 9 mg. of iron; there are on the averago 19 mg. of iron para-nucleinates in the whole liver. The nucleo-protein contains from O.lS% to 0.4404 of iron. I n animals treated with iron para-nucleinate this rises to 1.1%. The quantity of iron in the nucleo-protein is however not proportional to the total iron of the liver. Alt'hough the amount of iron in the nucleo- W. D. H. protein is thus variable the percentage of phosphorus is constant.W. D. H. Nature of the Fat in Normal and Pathological Human Livers. PERCIVAL HARTLEY and A. MAVROGORDATO (J. Path. Bact. 1908 12 371-377).-The iodine value of the higher fatty acids from adipose tissue is 65 ; that from the normal liver 115-120. When the amount of fat in the liver is abnormally great the iodine value falls. Whether this is due to fat transported from the adipose tissue or t o excessive formation of fat from carbohydrate is discussed but left uncertain. Perfusion of Excised Kidneys. IX. Effects of Poisons. TORALD SOLLMANN and ROBERT A. HATCHER (Anzer. J. Ph,pioZ. 1908 21 37-50).-The ureter-flow in excised kidneys depends mainly on glomerular pressure and the various poisons investigated are regarded as having their effect rather on the vessels than on the renal epithelium.Cbloral Hydrastis b ydrocyanic acid and juniper cause vaso-dilation and increase of ureter flow ; adrenaline sodium arsenate digitalis mercuric chloride and picric acid have the reverse effect. Alcohol caffeine cantharidin carbon dioxide carbon monoxide ergot formaldehyde hydrastininc and sodium thiocyanate in the con- centrations used have no effect. The effect of the drugs on the intact kidney in vivo in cases where the comparison is capable of being made is stated to be the same as in the excised organ. W. D. H. W. I>. H.PHYSIOLOGICAL CHEMISTRY. 211 The Occurrence of Scatole in the Human Intestine. CHRISTIAN A. HERTER (J. Biol. C'hem. 1908 4 101-109).-Scatole is b7 no means always present in the lower gut in either children or adults.When intestinal putrefaction is excessive it is present and this is sometimes accompanied with increased formation of indole. When indole is absent in the fzces indican is present in the urine ; hence the scatole is probably produced later in the intestine. Its formation is due mainly to putrefact,ive anaerobic bacteria. Certain strains of the bacillus of malignant edema and of 3. putriJicus form scatole; but B. coli conamunis forms indole and usually little or no scatole. The conditions giving rise to the two products are thus different. The formation of indoleacetic acid is perhaps a necessary step in the production of scatole most bacteria attacking it with difliculty if a t all. W. D. H. Constituents of Ox Bile. I. KURT LANGHELD (Bey.1908 41 378-385).-A new method is described for treating the acids of ox bile which allows of the isolation of more than 80% of the crude pro- duct in the form of definite chemical compounds. The crude acids are treated directly with alcohol which leaves t h e cliolic acid undissolved and after separation of the fatty acids the remainder is esterified by Fischer's method. The substances isolated are obtained in the following percentages cholic acid 50.8 ; palmitic and stearic acids 5-4 ; deoxycholic acid from the esters soluble in light petroleum 1 ; deoxycholic acid from the insoluble esters 2o.7. The last is a mixture of deoxycholic acid m. p. 172-173° [a12 + 53*%3" and its isomeride Mylius's choleic acid m. p. 187-188° [a] + 47*97" the existence of which although denied by Latschinoff (Abstr.1887 682) and Lassar-Cohn (Abstr. 1893 ii 220) is now confirmed. Myristic acid was not found in the bile. G. Y. The Protein Hydrolysis of Cows' Milk. ALBERT J. J. VANDEVELDE (Bull. Soc. cliim. Belg. 1907 21 434-458).-The author finds that a 3% solution of iodoform in acetone is the most suitable reagent for use in studying the enzymes of milk. The addition of 3.3 C.C. of this solution to 25 C.C. of milk sterilises the latter complet,ely without interfering with the action of the enzyme. It is shown that the proteolytic enzyme present in cows' milk is capable of digesting about two-thirds of the proteins present i n the milk; the action is limited and does not appear t o be influenced by the age of the cow or by the quantity of milk yielded by the cow.The activity of the enzyme bears no relation to the period of lac tation. w. P. s. Parent Substance of the Hippuric Acid Produced in Animals. HARALAMB VASILIU ( B i d Zentr. 1908 37 29-32 ; from Mitt. Landw. Inst. Univ. Breslau 1906).-The chief source of bippuric acid seems to be phenylalanine. The fact that carnivorous animals notwithstanding the considerable amounts of phenylalanine present in meat eliminate only small amounts of hippuric acid in the212 ABSTRACTS OF CIIEMICAI PAPERS. urine is shown by an experiment iiiade by the author on himself to be probably due to the combustion of the benzene ring. N. H. J. M. The Relation of Nitrifying Bacteria to the Urorosein Reaction of Nencki and Sieber. CIIRISTIAN A. HERTER (J.BioZ. Chern. 1908 4 239-251).-The urorosein reaction sometimes (perhaps always) depends for its developnient when the reaction is induced by adding hydrochloric acid t o the iirine on the presence of bacteriit in that fluid. The bacteria can be isolated and a pure culture obt'ained; if this is added to sterile urine the typical urorosein reaction can then be obtained. These bacteria are capable of forming nitrites and the reaction depends on the liberation of nitrous acid. Doubtless the urorosein chromogeii would be more frequently detected if nitrites mere employed; the action is probably due to oxidation and not to the formation of a nitroso-componnd. Urorosein is distinct from scatole-red and its chromogeii occurs quite indepen- dently of the absorption of scatole from the intestine.The urorosein chromogen is indoleacetic acid but further evidence of this is postponed. W. D. H. A Therrnosoluble Protein said to be that of Bence-Jones. L. GRIMBERT (J. Pharnr. Chim.? 1908 [vi] 27 97-101).-The proteins from urine described by various authors as the albumose of Bence-Jones are not identical and chiefly resemble each other in being redissolved on heating. The solubilities of the protein in a case observed by the author are compared with those observed by other French investigators (compare Pstein Abstr. 1904 i 954). G. B. Excretion of Urochrome in Man. ST. DOJIBROWSKI (Zeitsch. p7ysioE. Chern. 1908 54 390-397).-Urochrorne is precipitated as a compound with cuprous oxide. The nitrogen in this was determined and from this mas subtracted the nitrogen due to the presence of purine substances in the precipitate.Normal urine cont,ains from 0.45 t o 0.47 gram in the twenty-four hours. I n pnetxmonia (1 case) the amount was 0.78 ; in typhoid fever (4 cases) i t rose to 0-76-.1.05. W. D. H. Changes in the Bile Occurring in some Infectious Diseases. HELEN BALDWIN (J. Biol. Chern. 1908 4 213-220).-Althoogh t9he method used (Ritter's) for the estimation of the cholesterol is not con- sidered absolutely accurate the following facts were noted the increase in the cholesterol of the bile is slight in cholecystitis if t'here is free drainage and but little disintegration of epithelium cells is present. The increase is marked when the bile flow is obstructed and the bile filled with masses of degenerating cells.Most of the increase is in suspension rather than solution. Cholecystitis is a common com- plication not only in typhoid fever as is well known bnt a.1~0 in pneumonia and suppuration in various parts. W. D. H.PH YSI OLO G I C A L C H EXi I STRP . 213 Prosecretin in Relation to Diabetes Mellitus. FRANCIS A. BAINBRIDGE (Bio-Chem. J. 1908 3 82-86).-The yield of secretin from the duodenal mucous membrane is almost or quite as great in diabetic as in non-diabetic people. It is doubtful if t’he absence of prosecretin has any causal relationship to diabetes. I n the cases where observers have failed to find it it is suggested that its dis- appearance is due to rapid post-mortem changes. Production of Glycosuria in Rabbits by Intravenous In- jection of Sea-water made Isotonic with the Blood.THEO. C. BURNETT (J. Biol. Chern. 1908 4 57-62).-The magnesium in sea-water is responsible for the glycosurin that follows its injection. W. D. €1. W. D. H. Metabolism Nitrogenous and Inorganic in Pancreatic Diabetes in Dogs. W. FALTON and JAMES LYMAN WIIITNEY (Beitr. chem. Phgsiol. Path. 1908 11 224-228).-After extirpation of the pancrecls there is an enormous increase in protein kataluolism which cannot. be ascribed to fever (as it partIy may in phloridzin diabetes) nor to accidental occurrence of infectious disease. This is accompanied by a relatively large increase in the mineral constituents of the urine and also a rise in endogenous uric acid formation. The tissue break- down appears t o be particularly great for the tissue proteins are richer in saline material than reserve proteins. It is possible that bone atrophy may contribute to the result Lactic Acid in Eclampsia.JULIUS DONATH (,Teilsch. physiol. Chem. 1908 54 550).-It is pointed out that A . ten Doesschate’s view (this vol. ii 122) that lactic acid is the result and not the cause of convulsions has been advanced previoudy by the author. The Purgative Inefflciency of Saline Cathartics when Injected Subcutaneously or Intravenously. JOHN AUER (J. Biol. Chenz. 1908 4 197-212).-~~acCallum (hbstr. 1903 ii 742 ; 1904 ii 63 191 755) stated that saline purgatives have the same action whether they are introduced into the alimentary canal or injected subcutaneously or intravenously. This was disputed by the present author (Abstr.1906 ii 876) but confirmed by Bancroft. The present paper is a reply to the latter and reaffirms the author’s previous contentions. W. D. H. The Behaviour of Calcium Formate and Acetate in the Organism. ATTILIO BONANNI (Chem. Zentr. 1907 ii 1803 ; from Arch. Farm. sper. 1907 6 419-443).-The urine of dogs and rabbits contains normally minute quantities of formic and acetic acids. After intravenous or subcutaneous administration of the calcium salts of these acids the amount increases but the quantity excreted is not so great as that given. The actual quantit.ies vary in the two animals. Numerical details are given. VIT. D. 11. Behaviour of Quinine in the Body. PAUL GROSSER (Biochenz. Zeitsch. 1908 8 98-1 17)-Great discrepancies as to what happens to quinine in the body occur in previous writings on the subject.W. D. H. W. D. H.214 ABSTKhCTS OF CHEMICAL PAPERS Phosphotungstic acid precipitates it quantitatively in the urine and in albuminous solutions such as extracts of organs the loss is almost 2% if protein material is removed by the kaolin method of Rona and Michaelis. The present observations were made on people suffering from malaria. The faxes contain at inost 1% of the amount of quinine administered. If given by the mouth or injected into the muscles a quantity varying from 8% to 46% is recoverable in the urine. The causes of this extreme variation is far from clear. The remainder does not accumulate in the tissues but is destroyed there. Perfusion of the liver by Brodie’s method with Ringer’s solution containing quinine shows that the issuing fluid contains less than that which enters and the liver has the power of decomposing quinine.Is Arsenious Anhydride Introduced into the Animal Organism Eliminated Unchanged or as Arsenic Acid 3 MARIO TONEGUTTI (BOX chim. fcwm. 1907 46 899-908. Compare Abstr. 1907 ii 908).-Arsenious acid when introduced into the organism either by ingestion or intravenously reappears unchanged in the urine and is transformed into arsenic acid when the urine is treated with magnesia mixture. W. D. H. T. H. P. The Influence of Potassium Cyanide on Protein Metabolism. ALFRED N. RICHARDS and GEORGE B. WALLACE (J. Biol. Chem. 1908 4 179-196).-There is a n increase in the excretion of total nitrogen which is due partly to the increased muscular work associated with the convulsions and partly to the dyspncea but mainly t o a specific influence of the poison on cell metabolism.The urea excretion runs parallel with that of total nitrogen in spite of interference with respiration. This affords evidence that urea formation is not oxidative. The ammonia output varies within normal limits. There is a distinct increase in preformed creatinine; creatine was also found in the urine. The undetermined nitrogen varies considerably but there is no evidence that any significant excretion of amino-acids occurs. Small doses of cyanide cause a greater increase in oxidised sulphur excretion than large doses and probably in the latter case the increase in “neutral sulphur” occurs at the expense of sulphur which would otherwise be oxidised.W. D. H. The Influence of Hydrazine on the Intermediary Metabolism of the Dog. FRANK P. UNDERHILL and ISRAEL S. KLEINER (J. B o l . Chenz. 1908 4 165-178).-1n inanition the dog excretes urine in which the ammonia-nitrogen is slightly increased in proportion to the urea-nitrogen. The excretion of creatiriine varies and there is a large output of creatine. Allantoin also is a constant constituent of such urine. I n hydrazine poisoning the partition of urinary nitrogen and sulphur is only slightly different from that which obtains during inanition. It has no specific action in causing a n elimination of allantoin. It causes fatty degeneration of the liver. Emphasis is laid on the protective adaptation of the liver duri~ig hydrazine poisoning. W. D. H.VEGEI’ABLE PHYSIOLOGY AND AGRICULTURE. 21.5 Comparison of the Hmnolytic and Toxic Action of Eel’s Serum on the Marmot. LUCIEN Cams and EUGBNE GLEY (Arch. internat. Phamzacodyn. ThZr. 1905 15 159 -1 69).-Eel’s serum is globulicidal and also toxic towards the rabbit and guinea-pig. The pigeon on the other hand is very resistant to both actions. There are however animals such as the marmot in which the hzemolytic action is slight and yet the serum is very toxic. Moreover a tempera- ture sufficiently high to destroy the hgmolytic power of eel’s serum only lessens its poisonous action. Not only are toxic actions elective but the same is true for immunity. W. D. H. Lecithid Formation. PRESTON KYES (Riochem. Zeitsch. 1908 8 42-46. Compare Abstr. 1907 ii 569).-Polemical. A reply to Michaelis and Rona (Abstr. 1907 i 667) ; and Morgenroth and Carpi (Abstr. 1907 ii 570).-The author adheres to the views he has expressed. G. B.

ISSN:0368-1769    

DOI:10.1039/CA9089405204

出版商:RSC    

年代:1908

数据来源: RSC