The Limiting High Temperature Rotational Partition Function of Nonrigid Molecules VI. The Methanol Equilibrium (English)

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In: The Journal of Chemical Physics   ;  4 ,  8  ;  493-496  ;  1936

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The entropy of methanol and the equilibrium constant for methanol synthesis are calculated for two molecular models, one of which rotates freely about the CO bond, while the other possesses a torsional oscillation of frequency 700 cm—1 about that bond. The latter model is indicated by spectroscopic evidence and gives an entropy in close agreement with the third law value and an equilibrium constant close to the mean of the widely scattered experimental results. The former model is supported strongly by valence theory; it can be made to agree with the third law entropy by assuming a zero‐point entropy of R log 3, and its rather poor agreement with experimental equilibrium data is not conclusive evidence against it. The true equilibrium constant probably lies between these two calculated values, or at worst slightly beyond one of them.

Table of contents – Volume 4, Issue 8

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461
The Reactions of Deuterium Atoms with Methane and Ethane
Steacie, E. W. R. / Phillips, N. W. F. | 1936
469
The Absorption Spectrum of Methyl Alcohol Vapor in the Photographic Infrared
Badger, Richard M. / Bauer, Simon H. | 1936
474
The Continuous Absorption Spectrum of Bromine: A New Interpretation
Acton, A. P. / Aickin, R. G. / Bayliss, N. S. | 1936
479
The Theoretical Treatment of Chemical Reactions Produced by Ionization Processes Part I. The Ortho‐Para Hydrogen Conversion by Alpha‐Particles
Eyring, Henry / Hirschfelder, J. O. / Taylor, Hugh S. | 1936
492
The Electron Affinity of Bromine Atoms from Space‐Charge Effects
Glockler, Geo. / Calvin, Melvin | 1936
493
The Limiting High Temperature Rotational Partition Function of Nonrigid Molecules VI. The Methanol Equilibrium
Kassel, Louis S. | 1936
497
Kinetics of Recombination of Iodine Atoms
Rabinowitch, E. / Wood, W. C. | 1936
504
The Homogeneous Unimolecular Decomposition of Gaseous Alkyl Nitrites VI. The Decomposition of n‐Butyl Nitrite
Steacie, E. W. R. / Smith, W. McF. | 1936
508
The Normal Vibrations and the Isotope Effect of Molecules of the Type X2YN with an N‐Fold Axis of Symmetry
Schimmel, Herbert | 1936
513
Transfer of Rotational Energy in Molecular Collisions I. Elementary Processes Which Lead to Abnormal Rotation of the HgH Molecule
Rieke, F. F. | 1936
526
The Effect of Rotational Distortion on the Thermodynamic Properties of Water and Other Polyatomic Molecules
Wilson, E. Bright | 1936
529
Thermodynamic Properties of Phosphorus Compounds
Anderson, Thomas F. / Yost, Don M. | 1936
530
Atomic Dimensions from the Coefficients of Compressibility and Thermal Expansion
Djang, G. F. | 1936
532
The Structure of Rubrene and Some Remarks on the ``Ortho‐Effect''
Bergmann, E. / Herlinger, E. | 1936
535
The Raman Spectra of Deutero‐acetones and Methyl Alcohol‐d
Bates, J. R. / Anderson, Leigh C. / Halford, J. O. | 1936
536
Raman Spectrum of Deutero‐Acetaldehyde
Wood, R. W. | 1936
537
Preliminary Note on the Phase Relationships in the Nickel‐Tin System
Fetz, Erich / Jette, Eric R. | 1936