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1 Dec 1948

Volume 16, Issue 12, pp. 1091-1176

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Cation Arrangement in Spinels

E. J. W. Verwey, F. de Boer, and J. H. van Santen

J. Chem. Phys. 16, 1091 (1948); http://dx.doi.org/10.1063/1.1746736 (2 pages) | Cited 48 times

Online Publication Date: 22 December 2004

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The Scattering of Light and the Radial Distribution Function of High Polymer Solutions

Bruno H. Zimm

J. Chem. Phys. 16, 1093 (1948); http://dx.doi.org/10.1063/1.1746738 (7 pages) | Cited 464 times

Online Publication Date: 22 December 2004

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A radial distribution function of polymer segments in a solution of a high polymer may be defined as a quantity proportional to the density of segments at a given distance from some given segment. An approximate expression is derived for this function for dilute solutions of chain molecules of moderate degrees of polymerization. By Fourier inversion a simple expression for the intensity of light scattering, as a function of angle and concentration, may be obtained.

Apparatus and Methods for Measurement and Interpretation of the Angular Variation of Light Scattering; Preliminary Results on Polystyrene Solutions

Bruno H. Zimm

J. Chem. Phys. 16, 1099 (1948); http://dx.doi.org/10.1063/1.1746740 (18 pages) | Cited 450 times

Online Publication Date: 22 December 2004

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A photoelectric apparatus for the measurement of the angular dependence of light scattering from solutions is described in detail and its performance is discussed. Methods of calculation for the determination of the average extension of the scattering molecules from the data are described. Data are presented for two fractions of polystyrene in various solvents, showing the effect of changing solvent power and temperature, and also confirming a theoretically derived formula for the concentration dependence of the scattering.

Entropy, Enthalpy, and Free Energy of the Electrical Double Layer at an Ideal Polarized Electrode. Part I. Thermodynamic Theory

David C. Grahame

J. Chem. Phys. 16, 1117 (1948); http://dx.doi.org/10.1063/1.1746742 (7 pages) | Cited 4 times

Online Publication Date: 22 December 2004

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There are several kinds of entropy, enthalpy, and free energy changes associated with the electrical double layer. Definitions of the thermodynamically significant quantities are given, together with equations for their evaluation. It is shown that the ideal polarized electrode may be regarded as one electrode in a galvanic cell and that the usual thermodynamic treatment of cells may be applied. The electrochemical process occurring in such a cell is identified, and a method of evaluating a new property, the transference number of the ions of the double layer, is given. The relationship between electrocapillary properties of metals and the thermodynamic properties of colloids is indicated. The thermodynamics of gas adsorption on solids is presented as an aid to the interpretation of the above.

Electronic States of Organic Molecules

William T. Simpson

J. Chem. Phys. 16, 1124 (1948); http://dx.doi.org/10.1063/1.1746743 (13 pages) | Cited 53 times

Online Publication Date: 22 December 2004

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The spectra of three simple dye‐like molecules, and of benzene and naphthalene, are treated in a semiquantitative fashion. The methods employed are the bond orbital, the molecular orbital (somewhat modified), the antisymmetrized molecular orbital, and two models, one related to the bond orbital, the other to the molecular orbital. The positions of main and second‐order bands, and intensities, are calculated. Extension of the calculations to complex cases is indicated.

Does Ultraviolet Absorption Intensity Increase in Solution?

Lois E. Jacobs and John R. Platt

J. Chem. Phys. 16, 1137 (1948); http://dx.doi.org/10.1063/1.1746745 (9 pages) | Cited 31 times

Online Publication Date: 22 December 2004

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Absolute absorption intensities and oscillator strengths were determined for isoprene and cis‐ and trans‐piperylenes in the region 1750–2400A, in vapor and in n‐heptane solution, using a vacuum fluorite spectrograph. More accurate oscillator strengths are obtained if our measurements at short wave‐lengths are combined with the Beckman data of Shell Development Company at longer wave‐lengths.
For the three compounds the best values of the experimental Lorentz‐Lorenz correction, or ratio of integrated intensities under the molar absorption curves for solution and vapor, were close to unity, a result obtained previously by Pickett and co‐workers for cyclopentadiene and cyclohexadiene absorption in this same region. A value of 0.98±0.04 for this correction represents the mean of all five of these determinations. Although the values obtained from our data alone without using the Shell curves showed a much larger spread, every determination was substantially below the correction factor of 1.30 predicted by Chako's classical oscillator theory for this wave‐length region and these solvents.

The Mercury Photosensitized Reactions of Isobutene

G. A. Allen and H. E. Gunning

J. Chem. Phys. 16, 1146 (1948); http://dx.doi.org/10.1063/1.1746747 (7 pages) | Cited 6 times

Online Publication Date: 22 December 2004

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An investigation has been made of the reaction of isobutene with mercury (3P1) atoms at 30°C. Acetylene and propylene have been shown not to be among the main products of the reaction. The over‐all rate of consumption of isobutene and the rate of pressure decrease both decrease with increasing initial pressure in the complete quenching region. These rates approach constant values for initial pressures of 180 mm and higher The results of this investigation show that isobutene behaves similarly to the other olefins in reacting with mercury (3P1) atoms at 30°C, in that the reactions can be explained by the following initial steps for the mechanism:
math
accompanied by the decomposition of the activated isobutene molecule into reaction‐initiating fragments.
The discrepancies between the results of this investigation and those of the earlier work of Gunning and Steacie may be due to the effect of impurities in the original isobutene, since it is shown that small amounts of added propylene or acetylene change the rate of reaction markedly.

The Effect of Electric Fields on the Decomposition of Nitrous Oxide by Alpha‐Rays

Nelson T. Williams and Harry Essex

J. Chem. Phys. 16, 1153 (1948); http://dx.doi.org/10.1063/1.1746749 (5 pages) | Cited 5 times

Online Publication Date: 22 December 2004

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Combination of oppositely charged ions plays no part in initiating the decomposition of nitrous oxide by alpha‐rays at 10 cm and at 20 cm pressure. The decomposition in the absence of a field is evidently largely initiated by the splitting of molecules on electron collision. The application of electric fields above those required to attain half‐saturation increases the ion yield because of the acceleration of free electrons by the fields. At higher field strengths the ion yield attains a value which remains unchanged on further increase in field strength. When the ion yield has this final constant value all electrons are attached to form negative atomic or molecular ions before reaching the electrode. Assuming the same reactions occur on electron collision as in the photo‐chemical reaction the increase in ion yield as a result of the effect of the field involves a minimum of 1.2 molecules of nitrous oxide split without attachment of the electron for each molecule split with attachment.

Infra‐Red Christiansen Filter Effect in Slurries of Organic Crystals

W. C. Price and K. S. Tetlow

J. Chem. Phys. 16, 1157 (1948); http://dx.doi.org/10.1063/1.1746751 (6 pages) | Cited 25 times

Online Publication Date: 22 December 2004

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The Christiansen filter effect in slurries of organic crystals is reported for the first time, in the infra‐red. The main difference between the effect in molecular and in ionic crystals is that the Christiansen (transmission) peak and the ``Reststrahlen'' (reflection) peaks are much closer together for organic crystals since they are produced by a single frequency instead of a wide band of lattice frequencies. The Christiansen effect is much more selective in organic crystals since it occurs for some bands but not for others. This is thought to be due to the nature of the coupling between the particular vibration and the atoms or groups in the molecule which make major contributions to the polarizability.
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Raman Spectra of Certain Phosphoric Acids and Their Salts

P. Hoffman and T. J. Hanwick

J. Chem. Phys. 16, 1163 (1948); http://dx.doi.org/10.1063/1.1746752 (1 page) | Cited 2 times

Online Publication Date: 22 December 2004

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Abstract Unavailable

Effect of Temperature on the Absorption Spectrum of Ozone: Chappuis Bands

A. Vassy and E. Vassy

J. Chem. Phys. 16, 1163 (1948); http://dx.doi.org/10.1063/1.1746754 (2 pages) | Cited 3 times

Online Publication Date: 22 December 2004

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Nuclear Magnetism in Studies of Molecular Structure and Rotation in Solids: Ammonium Salts

H. S. Gutowsky and G. E. Pake

J. Chem. Phys. 16, 1164 (1948); http://dx.doi.org/10.1063/1.1746756 (2 pages) | Cited 29 times

Online Publication Date: 22 December 2004

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An Equation of State for Gases at High Pressures and Temperatures from the Hydrodynamic Theory of Detonation

Melvin A. Cook

J. Chem. Phys. 16, 1165 (1948); http://dx.doi.org/10.1063/1.1746757 (1 page) | Cited 1 time

Online Publication Date: 22 December 2004

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The Vapor Pressure and Melting Point of Graphite

Leo Brewer

J. Chem. Phys. 16, 1165 (1948); http://dx.doi.org/10.1063/1.1746759 (2 pages) | Cited 5 times

Online Publication Date: 22 December 2004

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Notes on the Properties of Synthetic Rutile Single Crystals

S. Zerfoss, R. G. Stokes, and C. H. Moore

J. Chem. Phys. 16, 1166 (1948); http://dx.doi.org/10.1063/1.1746761 (1 page) | Cited 6 times

Online Publication Date: 22 December 2004

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Viscosity‐Composition‐Temperature Relations in the System Na2O☒SiO2

Stephen W. Barber

J. Chem. Phys. 16, 1167 (1948); http://dx.doi.org/10.1063/1.1746763 (1 page) | Cited 1 time

Online Publication Date: 22 December 2004

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The Hydrogen Fluoride Dipole Moment and the Structure of the Dimer

R. A. Oriani and C. P. Smyth

J. Chem. Phys. 16, 1167 (1948); http://dx.doi.org/10.1063/1.1746764 (2 pages) | Cited 2 times

Online Publication Date: 22 December 2004

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The Ultimate Liquid Transmission Limit?

H. B. Klevens and J. R. Platt

J. Chem. Phys. 16, 1168 (1948); http://dx.doi.org/10.1063/1.1746766 (2 pages) | Cited 2 times

Online Publication Date: 22 December 2004

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The Average Boundaries of Statistical Chains

C. A. Hollingsworth

J. Chem. Phys. 16, 1169 (1948); http://dx.doi.org/10.1063/1.1746768 (1 page)

Online Publication Date: 22 December 2004

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On the Classification of Symmetry Coordinates

William J. Taylor

J. Chem. Phys. 16, 1169 (1948); http://dx.doi.org/10.1063/1.1746770 (2 pages)

Online Publication Date: 22 December 2004

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Note on the Energy of a Rotating Molecule

Robert Karplus

J. Chem. Phys. 16, 1170 (1948); http://dx.doi.org/10.1063/1.1746772 (2 pages)

Online Publication Date: 22 December 2004

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Chemical Kinetics of Bromine Following Neutron Capture

William H. Hamill and Russell R. Williams

J. Chem. Phys. 16, 1171 (1948); http://dx.doi.org/10.1063/1.1746773 (2 pages) | Cited 3 times

Online Publication Date: 22 December 2004

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Linear Atomic Chain and the Metallic State

T. A. Hoffmann and A. Kónya

J. Chem. Phys. 16, 1172 (1948); http://dx.doi.org/10.1063/1.1746775 (2 pages) | Cited 11 times

Online Publication Date: 22 December 2004

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Structure and Conductivity in the VIB Group of the Periodic System

F. de Boer

J. Chem. Phys. 16, 1173 (1948); http://dx.doi.org/10.1063/1.1746777 (2 pages)

Online Publication Date: 22 December 2004

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The Calculation of Interaction Potentials from Collision Cross‐Section Measurements

M. C. Kells

J. Chem. Phys. 16, 1174 (1948); http://dx.doi.org/10.1063/1.1746779 (2 pages) | Cited 12 times

Online Publication Date: 22 December 2004

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Abstract Unavailable
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