REVIEW OF AMERlCAN CHEMICAL RESEARCH. VOL. IX. No. 3.
M. T. Bogert, E. M. Chamot, B. S. Cushman, Benton Dales, I,. M. Dennis. A. H. Gill,
WILLIAMA. NOYES,Editor. REVIEWERS : H. M. Goodwin, W. F. Hillebrand, I,. P. Kinnicutt, H. W. Lawson, G . N. Lewis, H. N. McCoy,
A. A . Noyes, J. W. Richards, S . P.Sadtler, J. 0. Schlotterbeck, W. H. Seaman, F. P. Underhill.
GENERAL AND PHYSICAL CHEMISTRY. The Optical Rotatory Power of Cane-Sugar when Dissolved in Amines. BY G. M. WILCOX. 1. P h p . Chem., 6 , 339-342.T h e author finds that cane-sugar has a much higher rotatory power in isopropylamine, allylamine and amylamine solutions than in aqueous solution. G. N. LEWIS. The Expansion of a Gas into a Vacuum and the Kinetic Theory of Gases. BY PETERFIREMAN. J . Phys. Chem., 6, 463-466. --The author discusses the changes in temperature of a gas escaping into a vacuum and concludes that the lack of uniformity in the molecular velocities is alone responsible for the temperature changes in question, the Joule-Thomson effect being negligible. Whether or not this conclusion is justifiable, the paper serves to call attention to a problem whose solution has been too frequently taken for granted in the development of the kinetic theory. G. N. LEWIS. Deduction of the Ilagnitude of the Osmotic Pressure in Dilute Solutions According to the Kinetic Theory. BY PETER FIREMAN.3. Phys. Chem., 6 , 636-638.-An unsatisfactory attempt to explain osmotic pressure. T h e hypotheses are not clearly defined, nor are the processes of reasoning made apparent to the reader. G. N. LEWIS. Limitations of the nass Law. BY WILDERD. BANCROFT. J . Phys. Chem., 6 , ~gc-~gz.-The author points out that if, in equilibrium, the concentrations of the factors and products of a chemical reaction are known for the gaseous phase, it is not possible to calculate the extent of the reaction in a solution, even if each of the molecular species alone obeys Henry’s law, for Henry’s law may not apply to one of the species in the presence of the other. G. N. LEWIS.
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A Derivation of the Phase Rule. BY J . E. TKEVOR. /. Phys. Chenz., 6, 18j-l92.-This is a formal derivation of the phase rule, first for a system in which ail the substances in t h e system are independent components, then for the general case. T h e proof is brief and appears to be rigorous. I t introduces no new principle and differs from its nciinero~i~ predecessors chiefly in form and tiomenclature. G . X. LEWIS.
Alloys of Tin, Lead and Bismuth. BY F. S. SHEPHERD. J. Phys. Chent., 6, 519-j53.-When a molten alloy of lead, tin and bismuth is cooled there are three singular points in the temperature curve. This is the simplest case, indicating the separation of three solid phases and giving no evidence of metallic compouiicls. By t h e aid of a new analytical method, the three phases were proved to be pure tin and solid solutions of lead in bismuth and of bismuth in lead. T h e existence of these solutions is confirmed by the aid of the microscope and by etching. Bismuth is able to dissoive 5 per cent. of lead ; lead to dissolve 4 per cent. of bismuth. T h e phenomenon of recalescence was studied and the author conjectures that it is due to the formation of a denser unstable modification of tin. This. however, would seem inconsistent with the author’s statement that recalesceiice takes place at no fixed temperature, for the two phases of tin with the other two phases should make a non-variant system. The paper contains a discussion of earlier work and a bibliography. G. N. LEWIS. Crystallization from a Current-Bearing Electrolyte. BY PAULR. HEYL.P h p . Rev., 15,335-344. -Careful nieasurements were made and discussed statistically to determine whether crystals have any different properties when separating from a solution during electrolysis. Copper sulphate and mercuric iodide were G.pu’. LEWIS. used. T h e results were negative. The Spectra of Gases at High Temperatures. BYJoHx TROWProc. A m . Phil. Soc., 41, 138-14o.-The author summarizes his recent work on electric discharges through gases, carried on by means of his enornious storage battery, which is capable of giving a spark of two meters, at over six million volts. With varying conditions, striking variations i n the spectra are obtained, Thus it is possible to show distinctly the two spectra of argon, even in tubes filled with purest hydrogen. T h e spectrum of water vapor is present in all cases and the author comes to the remarkable conclusion that a perfectly dry gas would be a perfect electrical insulator. “ Just as a certain degree of moisture is necessary for chemical reactions, so is water vapor essential for the discharge of electricity through gases. ” The paper coiicludes with the mention of the occurrence of bright lines in the photographic negative of the spectra, a phenomenon apparently analBRIDGE.
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ogous to solarization, but which the author considers due to the unreactiveness of the sensitive plate towards light of certain G. N. LEWIS. wave-lengths.
Studies in Vapor Composition, 11. BY H. R. CARVETH. J . Phys. Chem., 6 , 237-256 ; 321-338.-The paper discusses the experimental attainment of equilibrium in heterogeneous systems containing a vapor phase, and contains a method of obtaining the boiling-point curve and the vapor composition of binary mixtures, a method for the practical separation of two volatile liquids, and a method of obtaining the boiling-point of a liquid in contact with a solid phase. G. N. LEWIS. Ilolecular Attraction. BY J. E. MILLS. J . Phys. Chem., 6 , 209-236. -On the assumption that molecules attract each other with a force inversely proportional to the square of their distance apart and independent of the temperature, the author obtains several equations which express a proportionality between the change of internal energy on evaporation and the quantity, -#‘d-lVD, where d and. D are the densities respectively of liquid and vapor. T h e author shows that his equations hold within certain limits and he concludes that his assumptions are correct. Unfortunately this conclusion is rendered very doubtful by the occasional deviations from the formulas and by the fact that the author introduces other assumptions of doubtful validity besides those stated, such for example as the assumption that the internal latent heat is a true measure of the work done against molecular attractions. The author does not point out the simple relation between the densities of vapor and liquid, and the difference in their specific heats which would be the direct consequence of his equations. G. N. LEWIS. Synthetic Analysis in Ternary Systems. BY A. W. BROWN. J . Phys. Chem., 6 , 287-312.-The indirect methods previously suggested by Bancroft (this Rev., 8, 440) of determining ,the coniposition of a solid phase separating from a ternary system have been tested experimentally. Several cases in which the solid phases are compounds or solid solutions were studied. T h e method of plotting results on the triangular diagram is shown together with a method of indicating 011 the diagram the probable experimental error. T h e author concludes that with similar care the new methods give better results than direct analysis. G. N. LEWIS.
On the Stability of the Equilibrium of Univariant Systems. BY PAULSAUREL./. Phys. Chem., 6 , 257-26o.-The author gives another proof of the two theorems of Roozeboom establishing criteria of stability of univariant systems. G. N. LEWIS.
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On the Fundamental Equations of the multiple Point. BY PAUL SAUREL.J . Phys. Chent., 6, 261-~64.-The author gives a simple mathematical form to Riecke’s equations of a mul(;. N. LEWIS. tiple point.
On the Triple Point. BY PAULSAUREL.J . Phys. Chem., 6, 3gg-40g.-Two new methods of obtaining the classification of triple points given by Roozebooni are described. G. S . LEWIS. On a Theorem of Tammann. BY PAULSAUREL.J. P/lys. Chem., 6 , 410-416.--A generalization of a curious geometrical theorem of Tammann regarding the triple point. G. N. LEWIS.
On Indifferent Points. BY PAVLSAUREL.1. Phys. Chem., 6, 313-32o.-This is a mathematical discussion of such points as those at which a liquid mixture and its vapor have the G . S . LEWIS. same composition. On the Displacement of Equilibrium. BY PAULSAUREL.J. Phys. Chenz., 6, 467-473.-The author derives eight equations which embody, in his opinion, a more general statement of Le Chatelier’s theorem. G. N. LEWIS. On the Critical State of a One-Component System. BY development and aniplification of a number of familiar theorems by the aid of the Gibbs energy surface are presented. G. N. LEWIS.
PAULSAUREL.J . Phys. Chenz., 6 , 474-491 .--A
BY PAUL from the fundamental assumptions of Gibbs of theorems already given by G. X. LEWIS. van der Waals and Duhem.
On the Critical States of a Binary System.
SAUREL.J. Phys. Chem., 6, 629-635.-Deduction
Absorption, Dispersion, and Surface Color of Selenium. BY R . XV.XTOOD. Phil. Mag. ( 6 ) , 3, 607-622.-The author points out that little attention has been paid to substances with absorption bands just beginning in the visible spectrum and extending Glassy ” selenium i i such a subinto extreme ultraviolet. stance. I t s refractive index and absorptive power were studied with red and yellow light by means of very acute prisms. For shorter wave-lengths it was necessary to use the interferometer method with films prepared by cathode discharge. T h e extinction curve is steep, the absorption for short waves being as great as that of metals. T h e refractive index has a niaxiniuiii at wavelength o.Oooj, where it is 3.13, the highest yet recorded for any substance. The author gives a preliminary notice of work 011 nitrosodimethyl aniline, a prism of which is transparent to red and yellow and gives a spectrum twelve times as long as a similar ( ‘
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quartz prism. T h e substance is, however, almost completely opaque to blue and violet. G. N. LEWIS. The Solubilities of Some Carbon Compounds and the Densities of their Solutions. BY CLARENCEL. SPEYERS.A m . J. Sn'., 14, 293-30z.-The experiments recorded were undertaken t o determine whether different molecular aggregations of solutes had any connection with their differences in solubility. T h e solubility of the following substances was determined at various temperatures : urea, urethane, chloral hydrate, succinimide, acetamide, resorcinol, acetanilide, naphthalene, acenaphthene, phenanthrene, benzamide and p toluidine ; the solvents used being water, methyl alcohol, ethyl alcohol, propyl alcohol, chloroform and toluene. Plots showing the variation in solubility in passing from one solvent to another are given, and it is also shown that the relative solubility of a solute in several solvents can change very much with changing temperature. There appears to be no regularity, however, in the change of solubility as the molecular weights of the alcoholic solvents increase, whether the molecular aggregation of the solutes be regarded or not, nor are the results in accord with Schroeder's formula (Ztschr. $&s. Chenz., 11, 449 (1893) ) . T h e densities of the solutions a t various temperatures were determined by the pycnometer. Only urea, acetanilide, naphthalene and acenaphthene were found to exist in the solutions as solutes with normal molecular weights, and from these particular solutions the solubility and density a t 27' was ascertained and the osmotic pressure of the solutes determined. T h e latter is not a t all constant for the same solute in various solvents, and the analogy of solution t o vaporization is, therefore, far from complete. Plots are given, showing the variation in the molecular volume as the solute passes from one solvent into another. T h e following observations are made : ( I ) T h e molecular volumes of the solutes are larger in water than in the other solvents and decrease in the order of methyl alcohol, ethyl alcohol, propyl alcohol, toluene and chloroform, the only exception being perhaps chloral hydrate in ethyl alcohol compared with its solution in chloroform; ( 2 ) the molecular volumes in chloroform show decided constancy for every temperature and concentration observed, and to a lesser extent in toluene ; (3) in general, the molecular volumes of the solutes decrease as the temperature rises and the concentration increases, the exceptions being urethane and chloral hydrate in M. T.BOGERT. chloroform.
The Forecast of Chemical Reactions from the Algebraic Signs of the Quantities of Heat Liberated. BY H. LE CHATELIER. Trans. A m . Inst. Min. Eng., 31, 471.-Starting with the science of energetics, we start with the impossibility of creating energy from nothing. Some chemical reactions absorb heat, others, more
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numerous than the first, evolve it. A t very low temperatures, all possible reactions directly liberate heat ; at high temperatures, the possible reactions which absorb heat become more and more numerous. Of all the reactions which can take place, that particular one tends to occur which will develop the greatest amount of exterior work, but it is usually impossible to find out which reaction satisfies these conditious, for want of data. Another way of stating it is that the reaction tending to occur is that in which the heat of reaction diminished by T times S is a maximum, where T is the absolute temperature and S is the variation of the entropy. I t is thus seen that the diminishing terni increases indefinitely with the temperature and, therefore, the tendency for a reaction to take place diminishes as the temperature increases ; in case S is negative, the tendericy for the reaction to take place increases as the temperature increases. J. W.RICHARDS. INORGANIC CHEMISTRY The New Gas From Radium. BY E. RUTHERFORD.Tram. Roy. SOL.Caizada, 7, 2 1-2 j.--The rates of diffusion of the emanation from radium was determined by means of the quadrant electrometer. T h e method of measuring the activity of the emanation was similar to that used by the author in studying the radioactivity of thoria (this R e v . , 25). T h e rate of diffusion indicated a gas of molecular weight between 40 and 100. This could not have been radium vapor as the molecular weight of radium is greater than that of barium. H. X. McCoy.
The Conversion of Amorphous Carbon to Graphite. BY FRANCIS J. FITZGERALD. J . FraizR. 1 1 2 5 t . 154, 321--34S.-Tlie paper is a review of the most important work on this subject. It ~
treats especially of the comniercial method of Acheson by which graphite is produced from anthracite, containing 5 to 6 per cent. of ash, by heating electrically. T h e resulting graphite is practically pure carbon, all other substances having volatilized at the H . N. MCCOY. high temperature employed.
The Conversion of Amorphous Carbon to Graphite. BY F. J. FITZGEKALD. J . Fra72tk 172st., November, 1902. --An exhaustire article of 28 pages giving the complete history of this subject, from the first experiments of Despretz to the last results obtained by Acheson. The discussion of the work of IJoissan, and of the various pateuts coveriug this field is temperate and fair, and the whole article is a substantial contribution to the J. \V. RICHAKDS. literature of this subject.
