The limitations of the simple collision theory for reactions are discussed. The Menschutkin and related reactions are shown to involve the formation of an activated complex with an electric moment of a magnitude which is calculated for the various cases. The free energy of activation for proton transfer is found from the experiments on conductance in water and the dispersion effects on polarization in ice. A partition function for liquid H2O and D2O based upon experimental quantities is given. The abnormal rapidity of the denaturation of proteins in spite of an enormous activation energy is typical of reactions, involving the simultaneous breaking of many bonds.
REFERENCES
1.
2.
3.
4.
Tolman, Statistical Mechanics. (The Chemical Catalog Co., New York, 1927), p. 261.
LaMer has used this equation to develop an expression for the temperature coefficient of the entropy of activation and related quantities;
J. Chem. Phys.
1
, 289
(1933
).5.
6.
7.
8.
9.
10.
11.
Hildebrand, Solubility (Reinhold Publishing Co., New York, 1936).
12.
13.
Wynne‐Jones
and Eyring
(J. Chem. Phys.
3
, 492
(1935
)) give too large a value for because of an incorrect interpretation of the equilibrium results of Essex and Gelormini.14.
W. M.
Latimer
and W. H.
Rodebush
, J. Am. Chem. Soc.
42
, 1419
(1920
).15.
16.
17.
18.
19.
20.
Smyth
and Hitchcock
, J. Am. Chem. Soc.
54
, 4631
(1932
). We also want to express our appreciation for the opportunity of discussion with Professor Smyth.21.
22.
Debye, Polar Molecules (Chemical Catalog Co., 1929).
23.
24.
25.
Lewis and Randall, Thermodynamics (McGraw‐Hill, New York, 1923), p. 80.
26.
Brown
, Barnes
, and Maass
, 13B
, 167
(1935
).27.
28.
Newton and Eyring, Trans. Faraday Soc. In press.
29.
30.
Anson, The Chemistry of Proteins, Chap. IX, edited by C. L. A. Schmidt.
31.
32.
Chick and Martin, Kolloid chemische Beihefte V, 49 (1913).
33.
This content is only available via PDF.
© 1937 American Institute of Physics.
1937
American Institute of Physics
You do not currently have access to this content.