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C13 and Deuterium Isotope Effects in the Photolysis of Methyl and Ethyl Bromide
1.E. Warburg, Sitzber. Preuss. Akad. Wiss. Physik‐Math. Kl. 1916, 314.
2.Friedman, Bernstein, and Gunning, J. Chem. Phys. 26, 528 (1957).
2.More complete details are given in the Ph.D. thesis of H. L. Friedman, Illinois Institute of Technology, Chicago (1956).
3.As early as 1920, T. Merton and H. Hartley [Nature 105, 104 (1920)] suggested the possibility of a photolytic isotope separation based on a difference in the absorption spectra of isotopic chlorine molecules.
3.W. Kuhn and H. Martin [Naturwissenschaften 20, 772 (1932);
3.W. Kuhn and H. Martin, Z. Physik. Chem. B21, 93 (1933)] observed an enrichment of Cl35 in the photolysis of phosgene at 2816 A.
3.A. Farkas and L. Farkas [Trans. Faraday Soc. 34, 1120 (1938)] reported substantial hydrogen‐deuterium separation factors in photochemical reactions liberating hydrogen from aqueous solutions.
3.H. C. Urey [Manhattan District Declassified Document A–750 (July 10, 1943)] discussed aspects of the problem of the photochemical separation of uranium isotopes.
4.Bates, Halford, and Anderson, J. Chem. Phys. 3, 415, 531 (1935).
5.A. A. Gordus and R. B. Bernstein, J. Chem. Phys. 22, 790 (1954).
6.In preliminary experiments (results not reported herein) the isotopic methanes were transferred to a sample tube, the stopcock of which was coated with silicone high‐vacuum grease. Some of these samples showed abnormally high and erratic ratios of perhaps as a result of conversion to through some post‐irradiation exchange reaction. Attempts to determine quantitatively whether any excess was present were not wholly successful due to the variable residual water background at in the mass spectrometer. The origin of spuriously high ratios of to could have been via a radical exchange reaction [Lavrovskaia, Mardaleishvili, and Voevodskii, Voprosy Khim. Kinetiki, Kataliza, i Reaktsionnol Sposobnosti Akad. Nauk SSSR., Otdel, Khim. Nauk, 40–53 (1955).
6.(Technical Translation TT‐701, Natl. Research Council of Canada) Nuclear Sci. Abstr. 12, 4097(A (1958)] possibly occurring during the irradiation. Such a reaction, however, must have been of negligible importance in the present case, since the amount of molecular hydrogen in the products was generally less than 0.01% of the total amount of the reactants.
7.Mohler, Dibeler, and Quinn, J. Research Natl. Bur. Standards, 61, 171 (1958).
8.This assumes random distribution of carbon isotopes in the ethyl bromide. It can be shown that small (ca 2%) differences in the C13 content of the two carbon positions will not noticeably affect the correction factor of 2.0.
9.The correction was made as follows: Let ; ; . It was assumed that and Thus, using the previously quoted values of the mole fractions of each deuterated species: Thus,
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