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1 Dec 1935

Volume 3, Issue 12, pp. 755-834


Ultraviolet Absorption of Mixtures of NO, NO2 and H2O

Eugene H. Melvin and Oliver R. Wulf

J. Chem. Phys. 3, 755 (1935); http://dx.doi.org/10.1063/1.1749588 (5 pages) | Cited 16 times

Online Publication Date: 3 November 2004

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In considerable amounts of NO containing small amounts of NO2 a continuous absorption occurs in the ultraviolet, obscuring both the absorption of NO and that portion of the absorption of NO2 which lies below 2500A. The behavior of this absorption with respect to temperature and the partial pressures of the constituents is rather convincing evidence that it is due to N2O3. When very small amounts of water are also present a group of bands occurs in the near ultraviolet, lying in the same region but not resembling the longer wave‐length NO2 absorption. These bands appear diffuse under low dispersion but possess an ordered arrangement. With increase of temperature the intensity of the bands decreases rapidly. They begin in the vicinity of 3850A, extending to shorter wavelengths. The first members are broader and more diffuse than those that follow, indicating a predissociation process in the carrier, which is probably HONO.

The Raman Spectra of the Isotopic Molecules H2, HD, and D2

Gordon K. Teal and George E. MacWood

J. Chem. Phys. 3, 760 (1935); http://dx.doi.org/10.1063/1.1749589 (5 pages) | Cited 20 times

Online Publication Date: 3 November 2004

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The Raman spectra of H2, HD and D2 gases, at 3 atmospheres pressure, were excited by Hg 2537 and photographed with a high dispersion quartz prism spectrograph. A total of 42 lines were analyzed. The positions of the pure rotation lines for H2 agree with the measurements of Rasetti but the lines in the Q vibration band do not. New vibrational constants calculated from the Raman and emission spectrum data of H2 and HD give calculated values of the positions of the rotational‐vibration Raman lines in good agreement with the values observed for the three isotopic molecules. Contrary to the theoretical predictions, the 0,0 line of the Q vibrational band of HD was observed. A source of error in Raman measurements, namely, the movement of the spectrum due to variations of the barometric pressure during the exposure of a plate, was detected and eliminated.

On the Possibility of a Metallic Modification of Hydrogen

E. Wigner and H. B. Huntington

J. Chem. Phys. 3, 764 (1935); http://dx.doi.org/10.1063/1.1749590 (7 pages) | Cited 327 times

Online Publication Date: 3 November 2004

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Any lattice in which the hydrogen atoms would be translationally identical (Bravais lattice) would have metallic properties. In the present paper the energy of a body‐centered lattice of hydrogen is calculated as a function of the lattice constant. This energy is shown to assume its minimum value for a lattice constant which corresponds to a density many times higher than that of the ordinary, molecular lattice of solid hydrogen. This minimum—though negative—is much higher than that of the molecular form. The body‐centered modification of hydrogen cannot be obtained with the present pressures, nor can the other simple metallic lattices. The chances are better, perhaps, for intermediate, layer‐like lattices.

The Electron Affinity of Iodine from Space‐Charge Effects

George Glockler and Melvin Calvin

J. Chem. Phys. 3, 771 (1935); http://dx.doi.org/10.1063/1.1749591 (7 pages) | Cited 5 times

Online Publication Date: 3 November 2004

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The electron affinity of iodine atoms has been determined by a direct method in which only iodine atoms and electrons were involved. The value so obtained is 74.6 k‐calories, which is in good agreement with values obtained by other methods. The concentration of the several ions of different masses (I— and E—) have been calculated from their effect on space charge. It has been established that iodine has no effect on the thermionic emission of tungsten.

Nonadiabatic Reactions. The Decomposition of N2O

Allen E. Stearn and Henry Eyring

J. Chem. Phys. 3, 778 (1935); http://dx.doi.org/10.1063/1.1749592 (8 pages) | Cited 29 times

Online Publication Date: 3 November 2004

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The experimental and theoretical absolute rates for the nonadiabatic decomposition of N2O are shown to be in good agreement. The amount of chemical inertia present in other reactions involving the singlet‐triplet transition of oxygen is considered. A convenient method of constructing potential functions for polyatomic molecules which fit the spectroscopic data, and which reduce in the proper way for the various dissociation processes, is indicated, and is carried through for the N2O molecule.

The Absolute Rate of Homogeneous Atomic Reactions

Henry Eyring, Harold Gershinowitz, and Cheng E. Sun

J. Chem. Phys. 3, 786 (1935); http://dx.doi.org/10.1063/1.1749593 (11 pages) | Cited 33 times

Online Publication Date: 3 November 2004

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The absolute rate of the recombination of three hydrogen atoms is calculated entirely theoretically. The manner in which rotation determines the dimensions of the activated complex in cases having little or no activation energy is discussed. The theoretical data are in good agreement with the experimental rates of Steiner and of Amdur. An immediate consequence of the theory is that energy transfer occurs most effectively among particles which can react with each other, free atoms being more efficient than molecules. A qualitative application of potential surfaces to the problem of energy transfer as met in velocity of sound experiments and in experiments on maintenance of high pressure rates of unimolecular reactions is made.

A Summary of Experimental Activation Energies of Elementary Reactions Between Hydrogen and the Halogens

J. Carrell Morris and Robert N. Pease

J. Chem. Phys. 3, 796 (1935); http://dx.doi.org/10.1063/1.1749594 (7 pages) | Cited 14 times

Online Publication Date: 3 November 2004

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Existing experimental data on reactions between hydrogen and the halogens have been analyzed to give values of the activation energies of the intermediate reactions involved. These are compared with calculated values due to Eyring and Wheeler.

The Group Relation Between the Mulliken and Slater‐Pauling Theories of Valence

J. H. Van Vleck

J. Chem. Phys. 3, 803 (1935); http://dx.doi.org/10.1063/1.1749595 (4 pages) | Cited 55 times

Online Publication Date: 3 November 2004

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By means of the group theory of characters, it is shown that there is an intimate relation between Mulliken's molecular orbitals and the Slater‐Pauling directed wave functions. One can pass from the former to the latter by making a simple transformation from an irreducible to a reducible representation. Consequently the same formal valence rules are usually given by either method, and one can understand generally why wave functions of the central atom which are nonbonding in Mulliken's procedure are likewise never employed in constructing Pauling's ``hybridized'' linear combinations.

Valence Strength and the Magnetism of Complex Salts

J. H. Van Vleck

J. Chem. Phys. 3, 807 (1935); http://dx.doi.org/10.1063/1.1749596 (7 pages) | Cited 72 times

Online Publication Date: 3 November 2004

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Certain complex salts, notably ferro‐ and ferricyanides, have susceptibilities much lower than those predicted by the Bose‐Stoner ``spin only'' formula. The first interpretation was that given by Pauling on the basis of (I) directed wave functions. In the present paper it is shown that alternative explanations are possible with (II) the crystalline potential model of Schlapp and Penney, or with (III) Mulliken's method of molecular orbitals. In any of the theories, the interatomic forces, if sufficiently large, will disrupt the Russell‐Saunders coupling, and make the deepest state have a smaller spin, and hence smaller susceptibility, than that given by the Hund rule. This situation is not to be confused with that in normal paramagnetic salts, such as sulphates or fluorides, where only the spin‐orbit coupling is destroyed. The similarity of the predictions with all three theories is comforting, since any one method in valence usually involves rather questionable approximations. Because of this similarity, a preference between the theories cannot be established merely from ability to interpret the anomalously low magnetism of the cyanides. Covalent bonds, as in cyanides, seem to be more effective in suppressing magnetism than are ionic ones, as in fluorides, but so far the evidence to this effect is empirical rather than theoretical.

The Principal Magnetic Susceptibilities of K3Fe(CN)6

J. B. Howard

J. Chem. Phys. 3, 813 (1935); http://dx.doi.org/10.1063/1.1749597 (5 pages) | Cited 22 times

Online Publication Date: 3 November 2004

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The magnitudes, anisotropy and temperature dependence of the principal magnetic susceptibilities of K3Fe(CN)6 are calculated by the method of crystalline potentials, and prove to be in good agreement with experiment. The assumption is made that the interatomic forces in the Fe(CN)6‐‐‐ complex destroy Russell‐Saunders coupling. This results in a susceptibility corresponding to one free electron spin with a contribution, except at very low temperatures, from the unquenched orbital angular momentum. The effect of the latter is sufficient to make the susceptibility at room temperature almost twice as large as the value which would be obtained if the spin alone were considered. The superposition of a small rhombic crystalline field suffices to produce the large observed magnetic anisotropy. The behavior of the susceptibility of K3Fe(CN)6 is in sharp contrast to the higher effective magneton numbers and magnetic isotropy of many ferric compounds, such as the sulphates. In these the ground state of Fe+++ is the normal state of the free ion, namely a 6S state, so that five spins contribute to the susceptibility. Although the calculations ostensibly use the method of crystalline potentials, they are really based on general group properties and so apply even if the bonds in the cyanide are covalent, as they probably are, rather than ionic.

Symmetry Considerations Concerning the Splitting of Vibration‐Rotation Levels in Polyatomic Molecules

E. Bright Wilson

J. Chem. Phys. 3, 818 (1935); http://dx.doi.org/10.1063/1.1749598 (4 pages) | Cited 7 times

Online Publication Date: 3 November 2004

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The interaction of rotation and vibration and perhaps other effects may split degenerate vibration‐rotation energy levels of symmetrical polyatomic molecules into a number of components. The permutation symmetry of molecules containing several identical atoms provides certain restrictions on this splitting. This paper discusses the maximum number of fine‐structure components, their quantum weights when nuclear spins are taken into account, and the selection rule for transitions. All arguments are based solely on symmetry considerations so that no estimate of the magnitude of the splitting is given.

The Molecular Structures of Sulfur Dioxide, Carbon Disulfide, and Carbonyl Sulfide

Paul C. Cross and L. O. Brockway

J. Chem. Phys. 3, 821 (1935); http://dx.doi.org/10.1063/1.1749599 (4 pages) | Cited 8 times

Online Publication Date: 3 November 2004

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The structures of the molecules SO2, CS2, and COS have been investigated by the electron diffraction method with the following results; SO2, S ☒ O = 1.46±0.02A; CS2, C ☒ S = 1.54±0.03A; COS, C ☒ O = 1.16±0.02A, C ☒ S = 1.56±0.03A. The types of bond arrangement compatible with these interatomic distances are discussed. In SO2 the molecule resonates between the structures having single‐double and double‐single bonds between the sulfur and the two oxygen atoms, with a bond angle of 122°±5°. CS2 is a linear molecule with the structure having the two double bonds predominating over those having a single and a triple bond. In COS the double‐double bond arrangement and the structure having the triple carbon‐oxygen bond predominate.

Thermodynamic Properties of Sulfur Compounds II. Sulfur Dioxide, Carbon Disulfide, and Carbonyl Sulfide

Paul C. Cross

J. Chem. Phys. 3, 825 (1935); http://dx.doi.org/10.1063/1.1749600 (3 pages) | Cited 5 times

Online Publication Date: 3 November 2004

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The thermodynamic properties of sulfur dioxide, carbon disulfide, and carbonyl sulfide are calculated from the molecular constants obtained by electron diffraction and Raman and infrared spectra. — (F0 — E00) / T298.1 = 50.95, 48.28, 47.39; S0298.1 = 59.40, 56.84, 55.34 for SO2, CS2(g), and COS, respectively. The results are applied to several reactions involving these compounds. The free energies of formation of CS2(l) and COS at 298.1°K are +15.24 and —40.48 kg.cal.

The Molecular Structure of Nickel Carbonyl

L. O. Brockway and Paul C. Cross

J. Chem. Phys. 3, 828 (1935); http://dx.doi.org/10.1063/1.1749601 (6 pages) | Cited 26 times

Online Publication Date: 3 November 2004

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Electron diffraction by the vapor of Ni(CO)4 leads to a molecular model in which the four carbonyl groups have a tetrahedral arrangement about the nickel atom with the distances Ni ☒ C = 1.82±0.03A and C ☒ O = 1.15A. These distances are compatible with resonance between two electronic structures in which the C ☒ O bond resonates between triple and double electron pair bonds and the Ni ☒ C bond between single and double electron pair bonds. Nickel carbonyl is the first quadricovalent compound of neutral nickel whose structure has been determined, and its tetrahedral configuration is contrasted with the square arrangement of bonds in the quadricovalent compounds of divalent nickel ion.
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The Conductance of Salt Crystals

W. H. Rodebush and T. G. Cooke

J. Chem. Phys. 3, 834 (1935); http://dx.doi.org/10.1063/1.1749602 (1 page) | Cited 2 times

Online Publication Date: 3 November 2004

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Vibrations of Benzene and Raman Spectra of Benzene‐d and Benzene‐d2

O. Redlich and W. Stricks

J. Chem. Phys. 3, 834 (1935); http://dx.doi.org/10.1063/1.1749603 (1 page) | Cited 3 times

Online Publication Date: 3 November 2004

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