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Thermodynamics of Iodine Addition to Ethylene, Propylene, and Cyclopropane
1.R. B. Mooney and E. B. Ludlam, Proc. Roy. Soc. (Edinburgh) 49, 160 (1929).
2.G. R. Cuthbertson and G. B. Kistiakowsky, J. Chem. Phys. 3, 631 (1935).
3.A. Abrams and T. W. Davis, J. Am. Chem. Soc. 76, 5993 (1954).
4.R. A. Ogg, Jr., and W. J. Priest, J. Chem. Phys. 7, 736 (1939).
5.S. W. Benson, J. Chem. Phys. 34, 521 (1961).
6.The additivity rule in this paper specifically refers to S. W. Benson and J. H. Buss, J. Chem. Phys. 29, 546 (1958).
7.Correction is made to the value of which was originally and erroneously reported as 19.4 kcal/mole. Several numerical figures in reference 5 should accordingly be corrected to the values that will appear in this paper. Superscript zeros always refer to standard states at 1 atm and 25 °C.
8.See for example, S. W. Benson and E. O’Neal, J. Chem. Phys. 34, 541 (1961).
9.The volume of the ‐containing side arm was so small relative to the reaction flask that diffusive mixing was always fast compared to experimental times.
10.L. B. Arnold and G. B. Kistiakowsky, J. Chem. Phys. 1, 166 (1933).
11.The change in the heat capacity, the entropy and the enthalpy refers to the direction of the dissociation reaction.
12.Ta‐You Wu, J. Chem. Phys. 7, 965 (1939);
12.L. Kahovec and K. W. F. Kohlrausch, Ber. 73, 159 (1940). The unknown frequencies are estimated by the normal coordinate analysis and also by the extrapolation, dichloride‐dibromide‐di‐iodide. The entropy value so obtained may be in error by about
13.W. D. Gwinn and K. S. Pitzer, J. Chem. Phys. 16, 303 (1948).
14.It is to be noted that this form of barrier puts the gauche configuration at much less than 120° away from the more stable trans form. For dichloride and dibromide, respectively, these become about 116° and 108°.
15. for the 1, reaction based on our estimates of the maximum curvature possible in the experimental logK vs 1/T plots.
16.The uncertainty here is in The values quoted are all based on additivity rules, not experiments.
17.In setting up this equation, the following rate laws are assumed: and Cf. references 4 and 8.
18.The isomerization is assumed to follow the following mechanism: (rate‐determining), , . The rate‐determining step in this sequence is compared with the reaction , which is also the rate‐determining step for the I‐atom catalyzed decomposition of n‐propyl iodide and to which the value of used here was assigned by
18.J. L. Jones and R. A. Ogg, Jr., J. Am. Chem. Soc. 59, 1931 (1937). In equating these two rates, the effects of the terminal iodine, on the steric probability of the attack on the central H atom and also on the C (central)–H bond energy, are ignored, (cf. reference 5).
19.The following values are assumed: van der Waals radii
20.D. N. Rank, N. Sheppard, and G. J. Szasz, J. Chem. Phys. 17, 86 (1950).
21.K. S. Pitzer, J. Chem. Phys. 23, 1753 (1955);
21.L. S. Bartell, J. Chem. Phys. 32, 827 (1960). The assumption is justifiable if only 1,3‐repulsions are considered for longer chain molecules.
22.J. O. Hirscnfelder, C. F. Curtiss, and R. B. Bird, Molecular Theory of Gases and Liquids (John Wiley & Sons, Inc., New York, 1954), pp. 167, 563 and 966.
23.S. Mizushima, Structure of Molecules (Academic Press Inc., New York, 1954), p. 10.
24.Reference 22, p. 850. F denotes dipole‐dipole interaction energy.
25.E. T. Butler and M. Polanyi, Trans. Faraday Soc. 39, 19 (1943).
26.R. A. Ogg, Jr., J. Am. Chem. Soc. 56, 526 (1934).
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