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1 Dec 1933

Volume 1, Issue 12, pp. 817-887


The Derivation of Equations for Regular Solutions

J. H. Hildebrand and S. E. Wood

J. Chem. Phys. 1, 817 (1933); http://dx.doi.org/10.1063/1.1749250 (6 pages) | Cited 35 times

Online Publication Date: 3 November 2004

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The probability function of Menke has been used as a basis for a statistical treatment of the intermolecular potentials in solutions of symmetrical molecules for which the entropy of mixing is the same as for an ideal solution of the same composition. The resulting expressions enable calculations to be made of the departure of iodine solutions from the ideal solution laws which agree satisfactorily with the observed departures.

Technique for the Electrolytic Production of H2H2O

Hugh S. Taylor, Henry Eyring, and Arthur A. Frost

J. Chem. Phys. 1, 823 (1933); http://dx.doi.org/10.1063/1.1749251 (2 pages) | Cited 12 times

Online Publication Date: 3 November 2004

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A detailed description of a method of preparing heavy water in quantity is given and yields obtained over a period of months reported.

The Ground State of the Hydrogen Molecule

Hubert M. James and Albert Sprague Coolidge

J. Chem. Phys. 1, 825 (1933); http://dx.doi.org/10.1063/1.1749252 (11 pages) | Cited 354 times

Online Publication Date: 3 November 2004

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The method used by Hylleraas in treating the He atom has been extended to the H2 molecule. The method consists of setting up a wave function as a series in the five variables required, electronic separation being introduced explicitly as one of the variables. The coefficients are then determined so as to produce the lowest energy. The energy found is within 0.03 v.e. of the most probable experimental value, while the form and location of the potential energy curve for various internuclear distances agree with those deduced from spectra to within similar limits. The value of the function is computed for several configurations of the electrons, and compared with other approximations. Application of the method to other problems is discussed. A method is given for the numerical solution of secular equations of high degree.

Dielectric Constant Studies. I. An Improved Voltage Tuning Resonance Method and Its Application to Aqueous Potassium Chloride Solutions

J. Gilbert Malone, A. L. Ferguson, and L. O. Case

J. Chem. Phys. 1, 836 (1933); http://dx.doi.org/10.1063/1.1749253 (6 pages) | Cited 4 times

Online Publication Date: 3 November 2004

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An experimental study of the behavior of various types of apparatus used in the measurement of dielectric constants of aqueous solutions of electrolytes. Although simple theory indicates that the voltage tuning method of detection should give results which are uninfluenced by the conductivity of the solutions and should, hence, be particularly adapted to measurements on electrolytic solutions, it appears, however, that other disturbing factors are present. This is shown by the divergent results obtained when different types of detection are employed and leads to the conclusion that the change in dielectric constant of such solutions as observed by this method depends more or less upon the characteristics of the particular generating and receiving circuits used.

Dielectric Constant Studies. II. The Drude Method Applied to Aqueous Solutions of Potassium Chloride

J. Gilbert Malone, L. O. Case, and A. L. Ferguson

J. Chem. Phys. 1, 842 (1933); http://dx.doi.org/10.1063/1.1749254 (5 pages) | Cited 2 times

Online Publication Date: 3 November 2004

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This paper is an experimental comparison of several adaptations of the Drude method as applied to conducting solutions. With three distinct types of detecting device, results for the dielectric constant of water and of water‐alcohol mixtures agreed within experimental error. When, however, the same apparatus was applied to measurements with KCl solutions, different results were obtained with each. This indicates that any apparent change in the dielectric constant of electrolytic solutions, as observed by the Drude method, must depend in whole or in part upon the characteristics of the apparatus.

The Heat of Formation of Binary Liquid Solutions from Their Liquid Components

J. J. Coleman and Frank E. E. Germann

J. Chem. Phys. 1, 847 (1933); http://dx.doi.org/10.1063/1.1749255 (5 pages) | Cited 3 times

Online Publication Date: 3 November 2004

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It is pointed out that an equation giving the relation of the heat of formation per mol of liquid solutions from their liquid components, to temperature and composition can be used as the foundation equation for their thermodynamical theory. The empirical equation
math
in which ΔH is the heat of formation per mol of the solution, N1 is the mol fraction of one of the components of the binary solution, and α, β and γ are constants or functions of temperature, is presented. There are two degenerate forms of this equation. (Eqs. (7) and (8).) There are listed values of α, β and γ (or the values of the corresponding quantities in Eqs. (7) and (8)) for 59 solutions for one temperature and sometimes for several temperatures. It is noted that according to the data assembled in the International Critical Tables, some solutions composed of ``unassociated'' liquids present a behavior more irregular than those composed of ``associated'' liquids. It is suggested that this unexpected behavior may mean that some of these data are not as precise as they are indicated to be.

Contact Potentials and the Effects of Unimolecular Films on Surface Potentials. I. Films of Acids and Alcohols

William D. Harkins and E. K. Fischer

J. Chem. Phys. 1, 852 (1933); http://dx.doi.org/10.1063/1.1749256 (11 pages) | Cited 17 times

Online Publication Date: 3 November 2004

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Simultaneous measurements of film pressure and surface potential have been carried out by the use of an apparatus designed in such a way that the potential may be determined for any location on the surface of the film. At film pressures above that of the gaseous films, organic substances with homo‐heteropolar molecules give a single smooth curve for the relation between surface potential and molecular area. At areas sufficiently great to reduce the pressure to that of the gaseous film the surface potential becomes variable and remains variable until the area becomes so great that the continents and islands of condensed film evaporate in the two‐dimensional system to give a gaseous film alone. For example with films of myristic acid at 17° the surface potential is represented by a single curve below a molecular area of about 50 sq. Å, and by any value below 170 mv at higher areas, at which islands in the film persist. The areas above which the surface potentials become variable, due to the effects of islands or continents of film, are found to be about as follows: stearic acid, 28; palmitic acid, 28; pentadecylic acid, 41; lauric acid (on NaCl‐HCl solution), 36; oleic acid, 52; cetyl alcohol, 23.7; myristyl alcohol, 27. The surface potential rises rapidly with the number of carbon atoms in the hydrocarbon chain, and is about 400 mv for condensed films of stearic acid. It is higher for alcohols than for acids with the same number of carbon atoms. The increment is about that given by the addition of two carbon atoms to the acid. The change of one of the single bonds of stearic acid to the double bond of oleic acid as the film forming substance lowers the surface potential by from 37 to 65 percent, and makes this potential much more greatly affected by the molecular area. The following numbers give the number of carbon atoms in several normal acids and the corresponding potentials at 20 sq. Å at 17°: (12), 276; (14), 336; (15), 375; (16) 383; and (18), 410. The surface potential increases with decrease of temperature, with an increase of concentration in the film, and for the substances investigated, by a replacement of a basic by an acid solution. A collapse of the film lowers the surface potential since it changes the molecular orientation in the film. The films exhibit in the condensed state considerable hysteresis, both with respect to film pressure and surface potential. This feature has not been sufficiently noted in other work. The relation between surface potential and the molecular moments of the molecules which constitute the film is discussed. The dipole moment as calculated from surface potentials by the equation of Helmholtz are only about one‐sixth as large as those found by ordinary methods for independent molecules in nonpolar solvents. The discrepancy is attributed partly to a lowering of potential by an orientation of the dipoles with respect to each other, and partly to the too great simplicity of the equation. The apparatus used for this work has been found to give good determinations of the contact potentials of metals. In its design use was made of ideas suggested principally by Lord Kelvin, and by Guyot and by Frumkin.

Acoustical Studies. II. The Behavior of a Gas with Several Independent Internal Energy States

William T. Richards

J. Chem. Phys. 1, 863 (1933); http://dx.doi.org/10.1063/1.1749257 (17 pages) | Cited 6 times

Online Publication Date: 3 November 2004

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The method founded by Einstein for the description of the acoustical behavior of a dissociating gas has been extended to cover a nondissociating gas in which five groups of internal energy states have different relaxation times. Since the resulting expressions are unwieldly, approximations based on them, which permit the rough description of experiment, have been given. The study of the variation of the velocity of sound with frequency demonstrates differences in the relaxation times of the various states. The variation of the velocity of sound with pressure shows in addition effects due to three‐body collisions or to radiation from optically active states. It has been suggested to treat the temperature coefficient of the kinetic relaxation time by the introduction of an expirical quantity which may be called ``the activation energy of collision.'' By this means a rough kinetic analysis of the transition probability is possible. In gaseous mixtures, the relative spatial and energetic effectiveness of various types of collisions in exciting internal energy may be compared.

Thermodynamic Considerations on a New Kind of Transition Points

Otto Halpern

J. Chem. Phys. 1, 880 (1933); http://dx.doi.org/10.1063/1.1749258 (2 pages) | Cited 2 times

Online Publication Date: 3 November 2004

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According to previous experiments liquid helium shows a ``transition point'' with discontinuity in the values of its specific heat and expansion coefficient. It has not been possible, however, to observe the coexistence of the two ``phases.'' This fact is here explained on a thermodynamic basis. Coexistence of two phases at a transition point can only be anticipated if the two phases exhibit a discontinuity in energy. An analogy is made with similar cases like that of the ``transition point of superconductivity.''

On Electrophoretic Mobilities and the Isoelectric Point of Protein‐Coated Particles

Otto Halpern

J. Chem. Phys. 1, 882 (1933); http://dx.doi.org/10.1063/1.1749259 (1 page)

Online Publication Date: 3 November 2004

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It is a fact known by experiment that quartz or glass particles of microscopic size suspended in a liquid and coated with a superficial layer of protein exhibit in almost every instance the same mobility in response to the application of an electric field. This indicates that their electrophoretic potential is independent of the size and shape of the particles. Furthermore, the isoelectric point of these particles coincides with the isoelectric point of the proteinic ions in the solution. Some very general thermodynamic arguments are given in this paper indicating that we should expect a similar behavior as a consequence of simple model properties.

The Thermal Dissociation of Cyanogen into Cyanide Radicals. A Correction

G. B. Kistiakowsky and H. Gershinowitz

J. Chem. Phys. 1, 885 (1933); http://dx.doi.org/10.1063/1.1749260 (1 page)

Online Publication Date: 3 November 2004

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The Formation of Formaldehyde by the Action of Ultraviolet Light on Carbon Dioxide and Water: An Application of the Allison Magneto‐Optic Apparatus

John H. Yoe and R. E. Wingard

J. Chem. Phys. 1, 886 (1933); http://dx.doi.org/10.1063/1.1749261 (1 page) | Cited 4 times

Online Publication Date: 3 November 2004

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Helium Hydride Ion

George Glockler and D. L. Fuller

J. Chem. Phys. 1, 886 (1933); http://dx.doi.org/10.1063/1.1749262 (2 pages) | Cited 3 times

Online Publication Date: 3 November 2004

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