Reactions Involving Hydrogen and the Hydrocarbons
The activation energies of the reactions H+CH4=CH3+H2 (1) and D+CH4=CH3D+H (2) have been calculated by using the semi-empirical method in combination with the treatment of directed valence used by Van...
The activation energies of the reactions H+CH4=CH3+H2 (1) and D+CH4=CH3D+H (2) have been calculated by using the semi-empirical method in combination with the treatment of directed valence used by Van...
On Intramolecular Diffusion, Quantum Theory, and the Calculation of Unimolecular Velocity-Constants
The internal rearrangement of molecules can be considered as the diffusion from one part of a potential energy surface to another. It is suggested that the ordinary diffusion equations might be applie...
The internal rearrangement of molecules can be considered as the diffusion from one part of a potential energy surface to another. It is suggested that the ordinary diffusion equations might be applie...
Some Remarks on the Theory of Reaction Rates
J. Chem. Phys. 7, 646 (1939); doi:10.1063/1.1750508
Issue Date: August 1939
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Effects connected with a more complicated nature of the energy surfaces of relatively simple reactions are discussed. The theory of elementary association reactions is examined and it is shown that better results are obtained in the rate of association of atoms when three additional attraction states are taken into consideration. The rates of association of iodine, bromine and chlorine atoms are calculated and compared with the experimental rates. The improvement to be expected from consideration of the angular momentum of the associating pair of atoms is discussed.
The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
| History: | Received April 21, 1939 |
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http://link.aip.org/link/?JCPSA6/7/646/1 |
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REFERENCES (17)
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- Cf. various papers in the Trans. Faraday Soc. (1937) in the general discussion on reaction kinetics.
- Cf. also J. O. Hirschfelder and E. Wigner, J. Chem. Phys. (in publication).
- Hirschfelder, Eyring, and Topley, J. Chem. Phys. 4, 170 (1936).
- J. L. Magee, unpublished.
- J. Knipp, Phys. Rev. 53, 734 (1938).
- H. Beutler and M. Polanyi, Zeits. f. Physik 47, 379 (1928);
- C. F. Goodeve,
Trans. Faraday Soc. 30, 60 (1934) . - F. London, Sommerfeld Festschrift (Leipzig, 1928), p. 104.
- F. London, Zeits. f. Physik 74, 143 (1932).
- E. Wigner, J. Chem. Phys. 5, 720 (1937).
- E. Rabinowitch and W. C. Wood, J. Chem. Phys. 4, 497 (1936).
- Cf. Landolt-Börnstein's Tables, Vol. I, p. 69.
- E. Rabinowitch and W. C. Wood,
Trans. Faraday Soc. 32, 907 (1936) .
(a) Zeits. f. Physik. Chemie B30, 399 (1935). - E. Rabinowitch,
Trans. Faraday Soc. 33, 283 (1937) . - Cf. R. S. Mulliken,
Phys. Rev. 46, 549 (1934) ;
W. G. Brown, - Cf. G. Herzberg, Erg. exact. Naturw. 10, 207 (1931).
- M. G. Evans and M. Polanyi,
Trans. Faraday Soc. 35, 178 (1939) .
St. v. Bogdandy and M. Polanyi, ibid. 1B, 21 (1928);
M. Polanyi and G. Schay, ibid. 1B, 30 (1938).
H. Cordes, Zeits. f. Physik 97, 603 (1935). Note added in proof.—Professor Mulliken has kindly informed me that he does not consider the evidence leading to the second lowest curve (1
u) of Cordes to be satisfactory. In fact, theoretical considerations lead him to expect this state to be repulsive. In this case, the theoretical values of Table II should be reduced by about 30 percent.
