Kinetics of the Thermal Decomposition of Dimethylmercury. II. Carbon‐13 Isotope Effect
1.M. E. Russell and R. B. Bernstein, J. Chem. Phys. 30, 607 (1959), preceding paper.
2.See A. Maccoll and P. J. Thomas, J. Chem. Phys. 23, 1722 (1955)
2.and Friedman, Bernstein, and Gunning, J. Chem. Phys. 23, 109, 1722 (1955), for a somewhat similar situation in the ethyl bromide pyrolysis.
3.M. Dole, Chem. Revs. 51, 266 (1952);
3.C. R. McKinney et al., Rev. Sci. Instr. 21, 724 (1950).
4.See Friedman et al., 2.
5.It was shown [Ph.D. dissertation of M. E. Russell, University of Michigan (1958) available from University Microfilms, Ann Arbor, Michigan] by the tracer technique that essentially none of the carbon in the methane product originated from the cyclopentane, with >98% derived from the DMM decomposed.
6.Not shown on the graph are a number of points at higher values of Q (with correspondingly smaller values of ) for which the total pressure was not comparable with the rest of the series.
7.It should be noted that the increase in the isotope effect upon addition of cyclopentane does not occur by virtue of the pressure effect alone; from Table II, the addition of a great excess of to DMM caused no significant change in the (low) isotope effect of 1.1%.
8.The symbols C and represent and respectively. In order to simplify (without loss of rigor), the original Steps 2 and 1 have been combined as the new Step 1; similarly for the original Steps 3 and 7, giving the new Step 3.
9.The observed positive curvature of the vs Q curve (Fig. 1) is satisfactorily explained by the hyperbolic form of Eq. (6);
9.however, no attempt at quantitative treatment of data at high Q is warranted in view of the oversimplified reaction mechanism assumed in the present treatment.
10.R. B. Bernstein, J. Phys. Chem. 56, 893 (1952);
10.R. E. Weston, Jr., J. Chem. Phys. 26, 975 (1957).
11.(a) J. Bigeleisen, J. Phys. Chem. 56, 823 (1952);
11.(b) J. Bigeleisen, J. Chem. Phys. 17, 675 (1949);
11.(c) N. B. Slater, Proc. Roy. Soc. (London) A194, 112 (1948).
12.R. B. Bernstein, J. Chem. Phys. 22, 710 (1954).
13.H. S. Gutowsky, J. Chem. Phys. 17, 128 (1949).
14.J. Bigeleisen and M. Wolfsberg, J. Chem. Phys. 21, 1972 (1953);
14.J. Bigeleisen and M. Wolfsberg, 22, 1264 (1954)., J. Chem. Phys.
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