REVIEWS The object of this department o j ~ t h e j o u r n ais~to issue, as pvomptly as posszble, critical digests of alllournal articles that bear upon any phase ojPhysicaI Chemislry.
General On the determination of specific heats, especially a t low temperatures. f1. E . Schmitz. Proc. Roy. Soc. 72, 177 (2903).-The author has deterniined the mean specific heat between - 182' and ordinary temperature for copper, thallium, lead, aluminum, cast iron, nickel, cobalt, zinc, silver, and tin. In each case the specific heat is lower thau that at ordinary temperatures, lhe atomic heats for the mean temperature of - 8 5 O coming out Cu 5.08, T1 6.12, Pb 6.06, W. D.B. A1 4.66, Mi 4.93, Co 4.96, Zn 5.47, Ag 5.53, and S n 5.91.
On the temperature of flames. C. Fkry. Comptes rendus, 137,909 (1903). The author adds a sodium salt to the flame to be studied and determines the temperature at which the spectrum from a standardized incandescent lamp reverses the D lines. The temperature of a Bunsen burner at full blast is 1871' ; of an acetylene burner 2548O ; of hydrogen in air 1g0oO ; of the oxyhydrogen blowpipe 2420'. The temperatures given are mean values and are believed to be accurate to k 10'. W. D . B. --
Calculation of the heats of combustion of the organic acids, their anhydrides and esters. P.Lemoult. Comples rendus, 137, 656 (1903).- For the monobasic acids the author writes Q = 157n-- 106 and for the dibasic acids Q = 157n - 212, where n is the number of carbons in the formula. Por the esters the formula is Q = 157n - go. D.B.
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A new method of calculating heats of combustion. P. i e m o u l t . Covnptes rendus, 137, 979 (1903).-The compounds in the formula
author's results can be summed up for non-cyclic
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Q = 157% A,. Suitable changes have been made for cyclic cornpouiids.
W. D.B.
One-Component Systenzs
Some physical properties of nickel carbonyl. J Dewar and H. 0. Jones. BOG. Roy. SOC.7 1 , 427
(2903).-By using atmospheres of inert gases it is possible to make vapor density determinations of nickel carbonyl even up to 2 1 6 ~ . It was found that the rate at which the liquid evaporated had an effect on the extent of the dissociation. I n an atmosphere of carbon monoxide at IOOO a determination was obtained, showing less than one percent dissociation, The critical temperature is probably about zooo, the value of 1 g 5 O actually found being probably lowered by the presence of carbon monoxide. The critical pressure is probably about thirty atmospheres. The vapor pressure curve has been
determined from -IO' to the boiling-point at 4 3 . ~ ~The . latent heat of vaporization is 38.1 calories per gram and the Trouton COhStallt is 20.6.
W. D.B. The vapor pressures of liquid oxygen on the scale of the constant-volume oxygen thermometer filled a t different initial pressures. M . W. Travers and C. J. Fox. PYOC. Roy. SOL.72,386 (Zg03). -The mean valuesof thedifference of the temperatures corresponding to the vapor pressnres of liquid oxygen on the scales of the oxygen and the helium thermometers, when plotted against the initial pressures at which the oxygen thermometer was filled are found to be nearly on a straight line. The differences are 1.18' at 731 mm and 0.77' at 336 mm if we take the experimental values. If we take the smooth values the differences are 0.72' at 336 mni and 0.4' by extrapolation to zero pressure.
w.D.B.
On the compressibilities of oxygen, hydrogen, nitrogen and carbonic oxide between one atmosphere and half an atmosphere of pressure, and on the atomic weights of the elements concerned. Lord Rayleigh. Proc. Roy. SOC.73, z53 ( ~ 9 0 4 ). The ratio of pv for fi = 0.5 atm to p v for$ = 1.0 atm is found to be 1.00040 for oxygen, 0.99976 for hydrogen, 1.00017 for hydrogen, and 1.00028 for carbon monoxide. The author points out that, if Avogadro's law is applicable at low pressures, the atomic weight of nitrogen must be less than 14.01 instead of the 14.05 found by Stas. The ratios of the vapor densities of hydrogen and carbon monoxide to the vapor density of oxygen are so close to the ratios of the atomic weights that it evidently seems very improbable to the author that there should be any such discrepancy with nitrogen as is implied in W. D.B. Stas's value. On the measurement of the pressure coefficient of oxygen a t constant volume and different initial pressures. W. Makower a n d H . R. Noble. Proc. Roy. SOC. 72,379 (1903). -By extrapolation, the value of the pressure coefficient for oxygen at zero initial pressure is found to lie between 0.003664 and o 003665. This is higher than the value of 0.0036625 found by Travers and Jaquerod for hydrogen by the same method. Using the Callendar method and the pressure coefficient just found, the difference between 8, the temperature on the thermodynamic scale, and T, the temperature by the gas thermometer, is W. D. B. found to be 0.913~. This makes 0, = 273.09. The density of chlorine. H. Moissan and Binet du Jassoneix. Comptes rendzrs, 137, r198 (1903). -The determination of the density of chlorine by the Dumas method gave values at first which varied between 2.424 and 2.506. The chief sources of error were : air in the bulb ; moisture ; and the solubility of other gases in liquid chlorine. When these errors were eliminated as completel; as possible, the density of chlorine at oo was found to be 2.490. W. D.B. The state of vaporized carbon. JZ. Berthelot. Comptes rendus, 137,589 (1903). - A study of the filaments of incandescent lamps and of the black deposit on the inside of old lamps, shows that both are amorphous carbon and that the carbon does not precipitate from the vapor as graphite, It is main-
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tained that carbon is not always the same, as the degree of polymerization varies with the temperature. W. D.B. Some remarks on molecular transformation. J . D.van der Waals. Arch. nkerl. ( 2 ) 8, 104 (r903).-1n the case of acetic acid and nitrogen peroxide, the molecular complexity decreases with rising temperature. With acetaldehyde and paraldehyde, the effect of pressure is so great that the percentage of paraldehyde iii the vapor appears to pass through a minimum with rising temperature. The author discusses the way in which this appears in the gas equation for two components in reversible equilibrium. I n the case under consideration, the pressures are so high that it is unsafe to deduce the composition of the vapor from the density. W. D.8. Equilibria in the system acetaldehyde and paraldehyde with and without molecular changes. H. W. Rakhuis Roozeboom. Arch. nkerl. ( 2 ) 8, 97 (‘903). This is essentially an abstract of Hollemann’s paper (7, 476).
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W. D.B. Two-Component System A representation in space of the fields for the components of a binary system and their complexes when only the components occur as solids. H. W. Bakhuis Roozeboom. Arch. nkerl. ( 2 )8, 92 (1903).- A very complete discussion of the pressure-temperature-concentration diagram for the simplest type of two-component systems, in which there is only one liquid phase and the two components form no solid compounds and no solid solutions. Two phoW. D.B. tographs of a solid model help to make the text clearer.
On the nature of the inactive diformalic derivative of racemic acid. W. E . Ringer. Recueil Trav. Pays-Bas, 21,374 (z902). -The freezing-point curve for the dextro-rotary and the inactive diformalic derivatives of tartaric acid shows that the inactive form is a compound and not a mixture of the two optiW. D.B. cally active forms. The properties of the aluminum-tin alloys. W. C. Anderson and G . Lean. Proc. Roy. SOC. 72, 277 (1903).- The authors give data for the liquidus and for the solidus curve for aluminum and tin. The latter curve is certainly wrong and the flat in the freezing-point curve has since been shown not to exist (8, 233). With this pair of metals it is practically impossible to obtain results W. D.B. which mean anything unless the melt is stirred while cooling,
On certain properties of the alloys of the gold-silver series. W. C. RobertsAusten and T. K. Rose. Proc. Roy. SOC. 71, z6r (1903).- The freezing-point curve for gold and silver has been re-determined. The two metals form a con tinuous series of solid solutions and consequently any mixture must be homogeneous after annealing. I t is shown that this is the case for the alloy containing 9f.66 percent gold. The English law requires that the trial plates for testing the standard of the coinage shall contain 916.6 parts of gold and 83.3 parts of some other metal, the nature of this latter not being specified. Since 1873 the other metal has been copper, but a change was made in 1902 to silver on account of the importance of obtaining homogeneous trial-plates.
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Constant-standard silver trial-plates. E . Matthey. PYOC. R o y . SOC. 73, 124 (1904). - By using a thin cold mould and filling it from the bottom, the autiior casts standard silver trial-plates weighing as much as 8 to I O kilograms, which are practically homogeneous. The author states that this method of casting contradicts the belief that a uniformity of standard was best obtained by slow and uniform cooling." He overlooks the fact that what is best for a gold-silver alloy is not the best for a silver-copper alloy. The first pair of metals forms a continuous series of solid solutions ; the second pair forms two series of solid solutions with very limited solubility. This must be kept in mind in consideriiig the conditions for getting a homogeneous plate. D.B.
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Dissociation of the alkali carbonates. P. Lebeau. Comptes rendus, 137, 1255 (1903). -Determinations were made of the' dissociation pressures of sodium, potassium, rubidium and caesium carbonates at temperatures between 700' and IZOOO. Potassium carbonate is the most stable, the order being potassium, sodium, rubidium and caesium. D.B.
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The fusibility of mixtures of sulphur and bismuth. H . Pklabon. Conzpks rendus, 137, 648 (1903).-The bismuth used by the author is said i n one paragraph to have melted at 255' and in another at 260'. Addition of sulphur is said to have caused a rise of freezing-point. At 435O aiid a composition of sixteen atoms of bismuth to one of sulphur there is a quadruple point. No attempt is made to determine the phases at this point. There is another quadruple poitit at 685O and a cornposition of one of bismuth to one of sulphur. From this the author deduces the existence of the compound BiS, apparently believing that the solution at a quadruple point always has the composition of a compound. I t is more than probable that the variable melting-point of bismuth masked B eutectic. Altogether this is an inexcusably inaccurate and careless W. D.B. piece of work.
On the fusibility of the mixtures of bismuth and silver sulphides and of the sulphides of bismuth and antimony. H. Pklubon. Compte: rendus, 137, 920 (1903).-This is another bit of inaccurate work. The freezing-point curve for bismuth sulphide and silver sulphide is said to show two eutectics, an angular niaximuni and a quadruple point which is not a maximum. The angular maximum represents experime:ital error ; the assuniptioii that the co-ordinates of the quadruple point give the composition of the solid phase is a theoretical error. The freezing-point curve for bismuth sulphide and antimony sulphide is said to consist of three parts with neither maximuui nor minimum. There is nothing in the experiments to show whether these breaks are real or imaginary, I n any case they cannot have the significance attributed to them by the author.
W. D.B. On mixtures of antimony and antimony trisulphide. H. Pklabon. Compfees
rendus, 138, 277 (1904).- Antimony sulphide and antimony form two liquid layers with a quadruple point at 615'. The author takes the melting-point of pure antimony as 632' and that of the sulphide as 555O. The eutectic temperW. D.B . ature is 515'. Crystallization and dissociation in solid solution. C. A. Lobry de Bruyn
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Reviews and C. L . J u n g i u s .
Recueil Trav. Pays-Bas, 22, 298 (1903). -Under the influence of light, solid o-nitrobenzaldehyde changes into o-nitrosobenzoic acid. Up to a certain extent the acid remains dissolved in the aldehyde, giving a green color. When the concentration of the acid exceeds 2.6 molecular percents, the excess crystallizes as a white solid. W. D.B. Critical phenomena with partially miscible liquids. J . D . van der Waals. Arch. nkevl. ( 2 ) 8 , 109 (‘903). -Mixtures of ethane and ethyl alcohol give two separated curves of folding. The author had previously joined these two theoretically by means of a continuous curve. The experiments of Kuenen lead him n o w to consider these two lines as joined by a third, making sharp angles with the other two. The matter is discussed a t length and i t is shown that this new point of view excludes the possibility of a maximum temperature. W. D. B. Experimental investigations on distillation. E. Charabot and]. Rocherolles. Comfites rmdus, 138,497 (1904). -The authors consider the case in which the vapor of one liquid is bubbled through a second non-miscible liquid kept at a temperature higher than the boilingpoints of the mixed liquids. Under these circumstances, the first liquid cannot condense and there will be a definite relation between the composition of the distillate and the vapor pressures of the two liquids provided equilibriuin is reached. I n any actual case i t is difficult to reach equilibrium, but’the experinleiits of the authors do not show this. W. D.B. The extraction of oxygen by partial liquefaction of air and a reverse flow. C. Claude. Comples rendus, 137, 783 (1903). -The author condenses a part of the air under moderate pressure and makes the liquid flow in the opposite direction to the condensing gas. In this way he gets a liquid containing 55 percent oxygen and a gas containing 97 percent nitrogen without having to liquefy all the air. This result was made possible by a study of the phase rule. u. B.
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The evaporation of water in a current of air. E. P. Perman. Pvoc. R o y . SOC.72, 72 (1903). - The author draws the following conclusions : I . When air is aspirated through water, it becomes saturated with aqueous vapor with grcat rapidity. 2 . I n the saturated air so obtained, the pressure of the aqueous vapor is the saine as the vapor pressure of water when n o other gas is present. 3 . T h e density of the aqueous vapor in the mixture is norntal. 4. The density of saturated aqueous vapor (without admixture) is probably only very slightly (if at all) above normal at temperatures up to goo. W. D .B. Some addition products of different acids. S. H o o g e w e r f a n d W. A . van Recueik Trav. Pays-Bas, 21,349 (1902).-The authors give a list of thirty-four organic substances, m hich have been obtained with sulphuric acid of crystallization. I n each case the coinpound is decomposed by the action of solvents The authors, however, discuss the question whether one is to assume the presence of quadrivalent oxygen 111 these substances or not. W. D. B. Dovp.
366
Reviews
The density and the expansion with heat of magnesium chloride solutions. 21, 59 (z902).-The author has determined the densities of solutions containing from six to twenty grams of magnesium chloride per hundred cubic centimeters of solution a t temperatures from 1 5 O to rooo. With the more dilute solutions, density determinations were At low temperatures the expansion per degree is greatest made down to - 6 O . for the most concentrated solutions, but the reverse is true for the higher temperatures. Starting with the same volnnies a t oc, the solutions have the same volumes at about 5 6 O 3. 16.' D.B.
G.J.W. Bremer. Recueil Trav. Pays-Bas,
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Multi-Component Systems The sulphates of potassium. W. Stortenbeker. Recueil Trav. Pays-Bas, 21,399 (1902). -Solubility curves have been determined for some mixtures of potassium sulphate, sulphuric acid and water. The stable solid phases were As instable solid phases we have K,SO,, K,SOI.KHSOI and KHSO,. K,S0,.3KHS04 and K,S046KHS04. W. D.B. The hydrates of nickel sulphate and methyl alcohol. C. A. Lobry de Bruyn. Recueil Trav. Pays-Bas, 22, 407 (1903). -The author has determined the solubility of various hydrates of nickel sulphate in methyl alcohol solutions of different strengths. The values are only approximate ones because these hydrates are not stable. The stable solid phase has the composition NiSO,. 3CH8OH.3H,O. D. B.
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On the state in which the hydrated nickel sulphates occur in methyl alcohol solutions. C. A . Lobry de Bruyn and C. L . Jungius. Recireil P a n . Pays-Bas, 2 2 , 421 (1903). - Boiling-point measurements appear to show that NiS0,7H,O loses 6H,O when dissolving in methyl alcohol. If the sulphate retains one of water i n methyl alcohol, the authors feel certain that i t must retain a t least as much in aqueous solutions. W. D. B. The application of physical chemistry to the study of toxines and antitoxines. s. Arrhenius and T. Madsen. Zeit. phys. Chew. 44, 7 (zgo3).This is an investigation of the effect of antitoxines (salts, proteids, normal serum, antitetanolysin, etc.) on the power of toxines (ammonia, alkalies, tetanolysin) to produce haemolysis of blood corpuscles, and an attempt to explain the results on the basis of the mass law. The method of investigation consisted in allowing the toxic solution to react a t 37O with a suspension of the blood corpuscles, and, after removal of the undestroyed corpuscles, estimating the extent of haemolysis colorimetrically. The results and their interpretation are hardly definite enough to give in abstract, hut the following striking cases may be mentioned. The decrease in the toxicity of tetanolysin caused by increasing quantities of antitetanolysin is exactly proportional to the free toxine calculated from the mass law equation : free toxine X free antitoxine = K(toxine-aiititoxine-compound)L. An analogous case in which ammonia was the toxine and boric acid the antitoxine was investigated and the results were found to be in accord with the mass law. F. B. K.
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Ternary systems. J . D.van der Waals. Arch. nberl. ( 2 ) 7,343 (r902).This is an elaborate study of the t function as applied to ternary systems.
w.D.B . On the conditions for the existence of a minimum critical temperature in a ternary system. 1.D.van der Waals. Arch. nierl. ( 2 ) 8 , 69 (1903). -The
general conclusion reached is that the conditions for a niininium critical temperature in a ternary system are given if we know the behavior of the three binary systems. W . D.B. Vapor pressures in the system: water, acetone and phenol. F. A. H. Schreinemakers. A r c h . nberl. ( 2 ) 8 , I (2903).-Reviewed ( 7 , 2 2 9 ) from Zeit. phys. Chem. 39, 485 ; 40, 440 ; 41,331 (1902). Vapor pressures of ternary mixtures. F. A. H. Schreinemakers. A r c h . nbrl. ,(z)8, 99 ('902). -Reviewed ( 7 , 228) from Zeit. phys. Chem. 36, 257, 412, 7 1 1 ; 37, 1 2 9 ; 38, 2 2 7 (1901). Some remarks on the vapor pressures of ternary mixtures. F. A. H. Schreinemakers. A r c h . nCerl. ( a ) 8, 395 (1903). -Reviewed (7, 545) from Zeit. phys. Cheni. 43, 6 7 1 (1903). Direct preparation of cyclohexanol and of cyclohexanone from phenol. f. Sabatier a n d J . B. Senderens. Comptes rendus, 137, 1025 (1903). - When a mixture of phenol vapor and hydrogen is passed over nickel powder at 1 4 0 ~ 1 5 0 O there is formed cyclohexanol, C,H,,OH. By passing the same mixture first over nickel at and then over copper at 330°, there is obtained cyclohexanone, C,H,,O. W. D.B. Direct hydrogenization of aniline. P. Sabatier and J . B. Senderens. Comptes rendus, 138, 457 (1904). -When hydrogen and aniline are passed over pulverulent nickel heated to go', there is a condensation, and also an evolution of ammonia. The product consists chiefly of C,H,,NH, boiling at 134O, (CGH,,),NH boiling at 2 5 0 ° , and C,H5NHC,Hl, boiling a t 275'. The last W. D. B. two substances are new. Direct reduction of aromatic halogen compounds by pulverulent nickel and hydrogen. P.Sabatier and A . Mailhe. Comptes rendus, 138, 245 (1904). When hydrogen and chlorbenzene are passed over pulverulent nickel at 2 7 0 ° , nickel chloride and benzene are formed, with traces of diphenyl. At the same temperature 30 percent of m-dichlorbenzene was converted into benzene ; 60 percent into chlsrbenzene, while about IO percent was unchanged. At 200° 0- and m-chloranilines are reduced to aniline. Brombenzene is also readily reduced, but the iodine compounds are more refractory, apparently because hydriodic acid reacts less readily with nickel. u. B.
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Synthesis of hydrogenized aromatic alcohols. L. Brunel. Cornpies rendus, 137, zz69 (1903).- The method was that of Sabatier and Senderens. By passing hydrogen and phenol over nickel a t I ~ c J O - I ~ ~ O a, practically quantitative yield of cyclohexanol, C,H,,OH, was obtained. I n this experiment about 2 5 0 cc of hydrogen passed through the tube per minute and about 1 2 g of phenol per hour.
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Revzews
With thymol and hydrogen at rSoo-18j0 hexahydrothymol, CloH,,OH, is obtained, while hexahydrocarvacrol can be prepared by passing carvacrol and hydrogen over nickel heated to 1g5~--200~. W. D.B. Alcoholic fermentation. f. H. Aberson. Recupil Tmv. Pays-Bas, 22, 78 (1903). -The alcoholic fermentation of sugar is a monomolecular reaction modified by action due to the glucose and alcohol. The temperature coefficient is normal. The reaction does not run to an end, and adding the reaction products causes eqnilibrium to be reached sooner. On the other hand i t was not possible to effect a reversal of the reaction. w. D.B. A rigorous separation in the rare earth series. G. Urbain and H. Lacombe. Cotnptes rendus, 137, 792 (1903).-The authow make the erroneous statentent that it is not possible to separate by fractional crystallization two salts which are not isomorphous. [This is true only in case one insists on crystallizing always at the same temperature ( 2 , 4 j ) ] . With isomorphous mixtures fractional separation can be effected a t constant temperature, but the process is a slow one. By adding a third component isomorphous with the two rare earth elements, having an intermediate solubility and easily separable by chemical means, the separation can be niade more quickly. The authors have added to the double magnesium nitrates of the earths rich in samarium a large amount of the double nitrate of magnesium and bismuth. The neodymium came out in the first fractions and then the samarium, while the last fractions were almost exclusively bismuth. When the double nitrate of magnesium and bismuth is added to the double magnesium nitrates of the rare earths rich in gadolinium, the first fractions contained the bismuth and the last the rare earths. From this the authors conclude that i t would be easy to separate samarium from gailoliniuni by means of bismuth, but they did ndt actually W. D.B. do it. Action of quick-lime on carbon at the fusing temperature of platinum. H. Moissan. Comptes rendus, 138, 243 (f904j.- Quick-lime and sugarcarbon were heated in a quartz tube to a temperature a t which platinum fuses. No reaction took place and a piece of calcium carbide does not soften a t that temperature. It was noticed that silica sublimes slowly from the quartz tubeseven D.R. a t 1200°, forming needles of a calcium silicate.
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Chemical nature of COllOidal SOlUtiOnS. J . DUClaUX. Comptes rendus, 138, 144 (1904). -It is pointed out that the colloidal substance obtained by mixing potassium ferrocyanide and copper sulphate solutions always contains potassium, the amount decreasing with increasing excess of copper sulphate solution. From this and other experiments, the author draws the very proper conclusion that the composition of the colloid is fixed only when that of the solution is fixed. As he does not consider the possibility of the colloid being a second solution phase, h e is very much puzzled by the results. W. D.E. An attempt t o estimate the relative amounts of krypton and of xenon in at(7, Ramsay. B O c . Roy. SOC. 71, 4.21 (rg03!.-Reyiewed mospheric air. 597) from Zeit. phys. Chem. 44, 74 ( 1 9 0 3 ) . New preparation of argon. H . Moissan and A . R i g a u t . Compfes yen-
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Reviews
dus, 137,773 (1903). -Metallic calcium combines with nitrogen at a red heat, forming Ca,N,, and with hydrogen at the same temperature, forming CaH,. This property has been made use of in the precipitation of argon. There are four steps in the process. In the first oxygen is removed by copper ; in the second some of the nitrogen is removed by niagnesium and linie ; in the third the bulk of the nitrogen is taken out also by magnesium and lime ; in the fourth step the last five percent of nitrogen is removed with metallic calcium. After the apparatus is set up and tested, two people can make a liter of argon in twelve hours. W. D.B.
Examination of the gases occluded or set free by radium bromide. J . Dewar and P.Curie. Comptes rendus, 138,190 (1904). - A small sample of radium bromide was placed in a vacuum for three months. Some gas was given off which appeared to be hydrogen, and which probably came from traces of moisture. The radium bromide was then placed in a quartz tube, a vacuum established, and the tube heated until the radium bromide fused. More gas was given off and was condensed in another tube by means of liquid air. The quartz tube containing the radium was then sealed in the oxyhydrogen blowpipe. The condensed gases were self-luminous and showed nitrogen bands. When the tube containing the radium bromide was excited by an induction coil, the complete spectrum of helium was obtained. W. D.B. Action of oxygen and hydrochloric acid on some metals. C. Matignon. Comples rendus, 137,1051 (rpo3).- I n presence of oxygen, hydrochloric acid attacks the platinum metals at temperatures below that at which hydrochloric acid is oxidized. Palladium reacts cold ; ruthenium readily at 1 2 5 O ; iridium, rhodium and osmium at 1.50'. W. D.B. New method of determining critical points of irons and steels. 0. Roudouard. Comptes relzdus, 137, 1054 (1903). - A bar of metal, IO cm in length, is taken and the thermo-electric force between the two ends is measured as a function of the temperature. This is said to give a very satisfactory method of determining transition points. W. D.B. Allotropic changes of nickel steels. 0. Boudounrd. Comples rendus, 138, 370 (1904). -The author has determined the so-called transition points for nickel steels containing 0 . 1 2 and 0.8 percents carbon and percentages of nickel varying from two to thirty. The results are very irregular, so much so as to make one wonder what their real accuracy is. I t may be desirable to determine apparent temperatures of change ; but it certainly would be well to determine equilibrium temperatures also. D.B.
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The styles of deformation and rupture of irons and soft steels. F. Osnzond, C. Frkmont and G. Cartaud. Comptes rendus, 137, 851 (1903). -The authors consider the polyhedral grains usually found in cast or wrought iron as cellular in nature, and they therefore speak of iron as occurring in the amorphous, cellular and crystalline states. Cellular iron is supposed to be very plastic, while crystalline iron is brittle. This duality is believed to explain many of the peculiarities of iron and steel. W. D. B. The constitution and properties of vanadium steels.
L . Guillet. Cowpies
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rendus, 138,367 (1904).- With a steel containing 0 . 2 percent carbon, vanadium could not be detected until its concentration exceeded 0.7 percent. With a steel containing 0.8 percent carbon, vanadium could be detected microscopically when its concentration exceeded 0.5 percent. I t is not known in what form the excess of vanadium separates. Vanadium steels are so brittle that they appear to be worthless except possibly for tools. u. B.
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The constitution and properties of silicon steel. L . Guillet. Comptes rendus, 137,1052 (1903).- With up to five percent silicon in iron, the silicon cannot be detected microscopically. With five to seven percent silicon part of the carbon is present as graphite, while the carbon is all changed to graphite when the silicon exceeds seven percent. The author hazards no guess at the form in which the silicon appears after its concentration exceeds five percent. A steel containing over five to seven percent of silicon cannot be worked.
w.D.B. Osmotic Pressure and Uiflusion On osmotic pressure. A. Smits. Recueil Trav. Pays-Bas, 22,153 (1903).-
I f we have two solutions of benzene and ether separated by a membrarie permeable to ether only, ether will pass from the place of higher concentration to the place of lower concentration. If the solutions are separated by a membrane permeable only to benzene, benzene will pass through the membrane in the opposite direction. From this the author deduces the conclusion that there is no theoretical difference between the solvent and the solute. The author makes the common mistake of trying to deduce quantitative conclusions from qualitative experiments. The question is whether there is a difference in the quantitative relations. Superficially there is. The change of the vapor presSure of the solvent is dependent chiefly on the concentration of the solute and is indepehdent of the nature of the solute for limiting cases. The vapor presSure of the solute varies much more with the nature of the solvent than with its molecular concentration. So far as the facts are concerned, there is a fundamental difference between solvent and solute. This difference can be made to disappear hy saying that in one case we are dealing with concentrated solutions and that any discrepancy is possible in a concentrated solution. This may, of course, be true ; but it has never been proved. D.B.
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On osmose. A. Guillemin. Comptes rendus, 138,38 (1904). - It is repugnant to the author to consider sugar dissolved in water as behaving like a gas. He prefers to assume that osmotic pressure is due to water vapor dissolved D.R. in liquid water.
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Relation between diffusion and viscosity. J. Thoverl. 138,481 (1904). - Experiments on the rate of diffusion of solvents have shown that the diffusion constant of phenol relative viscosity of the solvent is very nearly a constant for
Comptes rendus, phenol in twelve multiplied by the the whole twelve. W. D.B.
On the measurement of the diffusion of salts in solution. J. C. Graham. Roy. SOL.72, 212 (1903).- A description of an apparatus for ' floating ' pure water on a denser salt solution. Tables are also given for calculating the &oc.
371
Reviews diffusion coefficient. lar salt.
There are no actual data on the diffusioii of any particu-
W. D.3. Velocities
The inversion of sugar. L . Lindet. Comptes rendus, 138,508 (1904). The author has studied the rate of inversion of sugar in distilled water a t moo. Presence of copper, lead, tin or bismuth increases the rate of inversion very much, aluminum or antimony but slightly. Nickel, chromium, arsenic, gold, platinum, silver and mercury have practically no effect, while cobalt, iron, zinc, cadmium and magnesium retard the inversion. Alumina increases the rate much more than does aluminum. W. D.B. Studies of dynamic isomerism, I. T.Lowry. j o u r . Chem. SOC.83, 1314 (1903). -The rate of change of rotation of a 5 percent glucose solution was measured in the presence of hydrochloric acid, potash and potassium chloride of various concentrations. From the fact that the mutarotation of aqueous solutions of glucose was not checked by the addition of small quantities of acid, the author concludes that the process cannot be due to the presence of traces of alkali in the solution. F. B. K. The rate of decomposition of diazo-compounds, 11. J . C. Cain and F. Nicoll. Jour. Chem. SOL.83, 206 (1903). - This is an extension of the former investigation (7,231) to the diazo-salts of the following amines : a-naphthyl:SOsH, 2 , 4, 5 , and 8) ; P-naphthylamine and its nionosulphonic acids (“,I amine and its nionosulphonic acids (NH,z : SO,H, 6 and 7 ) ; and disulphonic acids (NH,;? : SO,H, 3 : 6 and 6 : 8 ) ; ~-arnino-a-naphthol-~-sulphonic acid, and 8-amino-a-naphthol-3: 6-disulphoriic acid. With soluble diazo-compounds good first order constants were obtained “ u p to the point” where the hydroxy product began to couple with the undecomposed diazo-salt to form azo-compounds. From this point on, the solutions became colored and the constants fell off rapidly, Though it is not likely that the diazo-salt and naphthol can exist side by side u p to a certain point, as assumed by the authors, the decrease i n the constant certainly becomes very rapid a t a certain stage of the process. I n the case of insoluble diazo-compounds the rate of decomposition was found to be constant. Most of the experiments were carried out at 60°. F. 3.K. The rate of decomposition of diazo-compounds, 111. J . C. Cain and F. Nicoll. Jour. Chem. SOL.83, 470 (1904). -Calculation of temperature coefficients of the velocity constants from Parts I and I1 of the investigation. F. 3.K. The conditions of decomposition of ammonium nitrite. V. N. Veley. Jour. Chem.SOL.83, 734 (1903).-TThe decomposition of ammonium nitrite is a monomolecular reaction both in the presence and absence of an accelerator. The reaction is impeded or stopped by ammonia, and oxides which liberate ammonia ; also by amines, hydrazines and, to a lesser degree, by oximes. Amides of the paraffin series cause a temporary acceleration, while benzamide and urea have no influence. Benzoic sulphinide caused considerable acceleration. The experiments were carried out between 60° and 7 0 ° . F. B. K. The enzyme of blood which decomposes hydrogen peroxide, I.
G. Sen-
372
Reviews
ler. 2czt.jhys. C h e m 44, 257 (1903).-The author has definitely established the fact that the enzyme of blood which causes the decomposition of hydrogen peroxide is neither the stromata nor the hmnoglobin, but can beseparated from the latter by precipitation by 50 percent alcohol. The enzyme obtained by extracting the precipitate is called h a n a s e . I t differs from hmnoglobin in not giving a blue color with a mixture of hydrogen peroxide and guajak. The decomposition of hydrogen peroxide by hEmase was followed quantitatively, and in the case of dilute solutions was found to accord very closely with the formula for monomolecular reactions. The effect of acids, sodium hydrate, salts and the enzyme poisons, aniline and hydrocyanic acid, was investigated. Most of the experiments were carried out at oo, to avoid the oxidation of the enzyme by the peroxide, but the temperature coefficient between oa and IOO was also determined. A good account is given of previous work done on the blood enzyme. b F. B. K. The multirotation of milk sugar. C. S. Hudson. Zeit. phys. Chem. 44, 485 (1903).-Solutions of milk sugar hydrate and milk sugar lactone show multirotation, both finally giving the same value. The author shows that the phenomenon is due to the two solutions gradually approaching a common state of equilibrium between the two substances. The sum of the two velocity constants is determined by following the change of a solution of milk sugar hydrate, while a similar investigation of a solution in equilibrium with solid hydrate leads to a determination of the values of the individual constants. F.13'. K. The catalytic racemisation of amygdalin. J . W. Walker. Jour. Chew. SOL.8 3 , 472 (1903).- From a polarimetric investigation of the racemisation of amygdalin, the author shows that it is probable that the process is a catalytic one induced by the presence of alkalies. F.B.I
