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1 Dec 1937

Volume 5, Issue 12, pp. 927-994


The Raman Spectra of the Methyl Alcohols, CH3OH, CH3OD, and CH2DOD

J. O. Halford, Leigh C. Anderson, and G. H. Kissin

J. Chem. Phys. 5, 927 (1937); http://dx.doi.org/10.1063/1.1749965 (6 pages) | Cited 14 times

Online Publication Date: 22 December 2004

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Measurements of the Raman spectra of CH3OH, CH3OD, and CH2DOD, produced by the mercury lines at 2536 and 4358A units, are analyzed to yield a provisional assignment of the fundamental frequencies. The significance of the character of the OH and OD bands to the problem of internal rotation is discussed. A new approximation to a potential constant for the C☒O bond is presented.

The Structure of H3, H3+, and of H3—. IV

David Stevenson and Joseph Hirschfelder

J. Chem. Phys. 5, 933 (1937); http://dx.doi.org/10.1063/1.1749966 (8 pages) | Cited 29 times

Online Publication Date: 22 December 2004

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In this paper, a direct calculation is made of the force constant for bending the nuclei in the triatomic hydrogen molecule, H3, and in the ion, H3+, from a straight line. The neutral molecule has lower energy when the atoms are in a line rather than in neighboring triangular configurations. The opposite is true for the positive ion. The quantum‐mechanical variational method is used together with the most general eigenfunctions which can be compounded from 1s hydrogen‐like orbitals. The polar‐homopolar composition of these eigenfunctions and the effective nuclear charge are varied simultaneously to give the lowest energy. For H3, we obtain the force constant for bending, 15.88 kcal./radian2, and the corresponding vibration frequency for bending, 3.26×1013 sec.—1. These values agree well with those obtained by the semi‐empirical scheme. The force constant for bending H3+ from a straight line is — 15.41 kcal./radian2. This negative value for the force constant indicates that the positive ion has lowest energy for triangular configurations, as predicted by Coulson. The energy of H3— is calculated for a linear symmetrical configuration. It is found that for reasonably small separations, H3— is unstable with respect to H2+H—. At large separations H— is attracted to H2 to form a loose cluster but a rough calculation of the equilibrium constant indicates that Concentration H3—/Concentration H—=0.2×pressure H2 in atmospheres. Thus at the low pressures which are used in the mass spectrograph, H3— could not be detected.

A Mechanical Analyzer for the Solution of Secular Equations and the Calculation of Molecular Vibration Frequencies

D. P. MacDougall and E. Bright Wilson

J. Chem. Phys. 5, 940 (1937); http://dx.doi.org/10.1063/1.1749967 (5 pages) | Cited 7 times

Online Publication Date: 22 December 2004

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A set of coupled harmonic oscillators has been constructed, so designed that it can be used to solve the numerical secular equations occurring in the theory of the vibration of polyatomic molecules and in other problems. Each oscillator consists of a shaft with cross arms carrying weights to increase the moment of inertia and springs to provide restoring force. The unit is free to rotate about the axis of the shaft, except for the restoring force of the springs. The various units are connected to one another by additional springs. In operation the springs and weights are adjusted to values which represent the coefficients of the secular equation to be solved, the whole device is driven by an eccentric of variable speed, and the frequencies of resonance, representing the roots of the equation, are measured.

Phosphorus at High Temperatures and Pressures

Robert B. Jacobs

J. Chem. Phys. 5, 945 (1937); http://dx.doi.org/10.1063/1.1749968 (9 pages) | Cited 12 times

Online Publication Date: 22 December 2004

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A detailed study of the transformations of the element phosphorus has been carried out at high hydrostatic pressures and at elevated temperatures. This has resulted in the discovery of a new modification of phosphorus, which is noncrystalline in structure and black in color. Its properties have been investigated to a certain extent. Some new calorimetric data are described which shed light on the question of the relative thermodynamic stabilities of this and the other forms of phosphorus.

An Electron Diffraction Study of the Grain Boundaries in Iron

Raymond Morgan, Sylvia Steckler, and Bernard L. Miller

J. Chem. Phys. 5, 953 (1937); http://dx.doi.org/10.1063/1.1749969 (7 pages) | Cited 1 time

Online Publication Date: 22 December 2004

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Grain boundary membranes, left after the dissolution of iron in ammonium persulphate solution, were studied by means of electron diffraction to determine whether crystalline materials are present in the membranes, and if present to identify the crystals. Samples of untreated and heat‐treated transformer iron, and heat‐treated electrodeposited iron were used. It was found that heat‐treated electrodeposited iron left residues which were suitable for study by electron diffraction when supported by Resoglaz backing films. From the electron diffraction patterns obtained, identification was made of the presence of Fe3C and of αFeOOH. It is suggested that the αFeOOH did not exist originally in the grain boundaries, but may have been formed by some chemical reaction either between iron and ammonium persulphate, or between some grain boundary constituent such as an iron oxide and the persulphate solution. The method of studying grain boundary materials does not afford a complete analysis, but it is believed that it makes possible important contributions since the presence of crystalline materials in the residues may be detected.

A Study of Melting of the Mononitrophenols at High Pressure

R. B. Dow and H. B. Hibshman

J. Chem. Phys. 5, 960 (1937); http://dx.doi.org/10.1063/1.1749970 (5 pages) | Cited 2 times

Online Publication Date: 22 December 2004

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The melting of the mononitrophenols has been studied over a pressure range of 4,000 kg/cm2 by separate application of a piston displacement and a new dynamic method. By the dynamic method, the procedure was to observe the sudden change of temperature difference as the nitrophenol underwent melting with change of pressure. Comparison of results obtained by the two methods indicate close agreement for the pressure‐melting temperature data of ortho‐ and metanitrophenol which have not been studied previously over the present pressure range. Application of the dynamic method is compared briefly with that of the piston displacement method in respect to melting and polymorphic transitions of solids at high pressure.

The Phase Diagram of Water to 45,000 kg/cm2

P. W. Bridgman

J. Chem. Phys. 5, 964 (1937); http://dx.doi.org/10.1063/1.1749971 (3 pages) | Cited 78 times

Online Publication Date: 22 December 2004

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On the Correlation of Fluidity Curves with Freezing Point Curves in Binary Systems

Raymond H. Ewell

J. Chem. Phys. 5, 967 (1937); http://dx.doi.org/10.1063/1.1749972 (7 pages) | Cited 3 times

Online Publication Date: 22 December 2004

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Binary systems which form crystalline compounds nearly always exhibit negative deviations from the ideal laws for liquid solutions of the type G = N1G10+N2G20 , where N is mole fraction and G may be volume, heat content, vapor pressure or fluidity. The deviations from ideality are often approximately parabolic functions of the molecular composition with the maximum deviation at or near 50 mole percent. In the case of fluidity this type of deviation is observed whatever the composition of the crystalline compound or compounds which occur in the system, leading to the conclusion that there is no correlation between the position of the maximum fluidity deviation and the composition of the crystalline compounds indicated by the freezing point curve. The bearing of this conclusion on the question of compound formation in the liquid is discussed.

An Experimental Determination of Ultrasonic Velocity in Several Gases at Pressures Between One and One Hundred Atmospheres

Alfred H. Hodge

J. Chem. Phys. 5, 974 (1937); http://dx.doi.org/10.1063/1.1749973 (4 pages) | Cited 8 times

Online Publication Date: 22 December 2004

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An acoustic interferometer of the resonator or driven type has been developed for the study of the behavior of ultrasonic waves in gases under pressures ranging from vacuum to several hundred atmospheres; measurements of acoustic velocity at several frequencies and in several gases at pressures ranging from one to 100 atmospheres have been made. Increase of velocity with pressure was found for air, N2, He, and H2, a decrease for CO2, the approximate pressure and velocity ranges being respectively as follows: air, 1–101 atmos., 347–371 m/sec.; N2, 1–102 atmos., 353–380 m/sec.; CO2, 1–63 atmos., 270–198 m/sec. The He and H2 were known to be impure. For them an increase in velocity nearly linear with pressure was found. Using frequencies from 88 to 499 kc dispersion was found for CO2 at atmospheric pressure, but almost entirely disappeared above 8 atmospheres. The availability of this method for the indirect determination of specific heats is shown.

Ratio of Specific Heats of Air, N2, and CO2 as a Function of Pressure by the Ultrasonic Method

J. C. Hubbard and Alfred H. Hodge

J. Chem. Phys. 5, 978 (1937); http://dx.doi.org/10.1063/1.1749974 (2 pages) | Cited 7 times

Online Publication Date: 22 December 2004

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Measurements have been made by Hodge of ultrasonic velocities at 27°C at pressures from 1 to 100 atmos. in air and N2 and at 1 to 60 atmos. in CO2. The results for air and N2 combined with the respective compressibility data of Holborn and Otto give at 27°C for air, values of γ between 1.406 at 1 atmos. and 1.580 at 100 atmos., and for N2, 1.403 at 1 atmos. to 1.564 at 100 atmos. The acoustic velocities in CO2 combined with the compressibility data of Amagat, give for γ at 27°C values from 1.304 at 1 atmos. to 3.524 at 60 atmos. These and the other results between these limits are in excellent general agreement with the few results in this temperature and pressure region available for comparison.

Rotatory Dispersion of Configurationally Related Unsaturated Secondary Carbinols and Their Corresponding Chlorides

P. A. Levene and Alexandre Rothen

J. Chem. Phys. 5, 980 (1937); http://dx.doi.org/10.1063/1.1749975 (5 pages) | Cited 2 times

Online Publication Date: 22 December 2004

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In several instances a periodic change in sign of the partial rotation of the chromophoric groups has been observed with the increase in the distance of these groups from the asymmetric carbon atom. In many unsaturated substances, the ethylenic bond is known to possess a partial rotation of significant value. It was desired to determine whether this partial rotation is subject to a periodic change in sign with the progressive increase in the distance of the double bond from the asymmetric center. The observations reported here seem to indicate that such a change exists although it is expressed less strikingly than in the case of the carbonyl group previously discussed.

Rotatory Dispersion of Configurationally Related Alkyl Azides

P. A. Levene and Alexandre Rothen

J. Chem. Phys. 5, 985 (1937); http://dx.doi.org/10.1063/1.1749976 (4 pages) | Cited 2 times

Online Publication Date: 22 December 2004

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From the viewpoint of chemical behavior, the —N3 group may be regarded as a pseudohalogen. Like iodides, azides possess an absorption band in the near ultraviolet region. For both practical and theoretical reasons it was important to obtain information on the rotatory properties of the azides as compared with those of the corresponding halides. The correlation of the configurations of primary and secondary azides is discussed in this communication. From the analysis of the rotatory dispersion of the primary azides and halides it became evident that the partial rotations of the azido group and of the halogen atom may be of opposite sign in configurationally related substances. An unexpected observation was made with regard to the members of a homologous series of secondary azides, namely, the rotation in the visible region as well as the partial rotation of the azido group, changes sign on passing from the second member of the series to the third. A tentative explanation of the phenomenon is given. It was found that in all alkyl azides the absorption band at λ2880 is not anisotropic or at best, insignificantly so.
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Plane Fundamental Modes of Vibration of Deuteroethylenes

C. Manneback

J. Chem. Phys. 5, 989 (1937); http://dx.doi.org/10.1063/1.1749977 (1 page) | Cited 2 times

Online Publication Date: 22 December 2004

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Abstract Unavailable

The Gaseous Equilibrium of 1,2‐Diiodobutane, Butene‐1 and Iodine

J. E. Cline and G. B. Kistiakowsky

J. Chem. Phys. 5, 990 (1937); http://dx.doi.org/10.1063/1.1749978 (1 page)

Online Publication Date: 22 December 2004

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Raman Spectrum of Solid H2S

S. C. Sirkar and J. Gupta

J. Chem. Phys. 5, 990 (1937); http://dx.doi.org/10.1063/1.1749979 (1 page)

Online Publication Date: 22 December 2004

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Revised Calculation of the Translational Fluctuation Effect in Gaseous Dielectrics

J. H. Van Vleck

J. Chem. Phys. 5, 991 (1937); http://dx.doi.org/10.1063/1.1749980 (1 page) | Cited 2 times

Online Publication Date: 22 December 2004

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The Infrared Association Band of a Heavy Alcohol

G. Bosschieter

J. Chem. Phys. 5, 992 (1937); http://dx.doi.org/10.1063/1.1749981 (1 page) | Cited 14 times

Online Publication Date: 22 December 2004

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The Raman Spectra of CH3CF3 and CCl2CF2

John B. Hatcher and Don M. Yost

J. Chem. Phys. 5, 992 (1937); http://dx.doi.org/10.1063/1.1749982 (2 pages) | Cited 7 times

Online Publication Date: 22 December 2004

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Abstract Unavailable

The Separation of Mixtures by Centrifuging

J. W. Beams and L. B. Snoddy

J. Chem. Phys. 5, 993 (1937); http://dx.doi.org/10.1063/1.1749983 (2 pages) | Cited 2 times

Online Publication Date: 22 December 2004

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Low and High Raman Frequencies for Water

James H. Hibben

J. Chem. Phys. 5, 994 (1937); http://dx.doi.org/10.1063/1.1749984 (1 page) | Cited 2 times

Online Publication Date: 22 December 2004

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Abstract Unavailable

Corrections to: A Method for Deriving Expressions for the First Partial Derivatives of Thermodynamic Functions

Frank Lerman

J. Chem. Phys. 5, 994 (1937); http://dx.doi.org/10.1063/1.1749985 (1 page)

Online Publication Date: 22 December 2004

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Abstract Unavailable
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