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Infrared and Raman Spectra of Tetramethylmethane‐d 12
1.Rank, Saksena, and Shull, Discussions Faraday Soc. No. 9, 187 (1950);
1.D. H. Rank, ibid. No. 9, 219 (1950).
2.Sheppard, Simpson, and Sutherland, Discussions Faraday Soc. No. 9, 216 (1950).
3.G. H. Fleming, Ph.D. dissertation, The Pennsylvania State College, June, 1933;
3.F. C. Whitmore and G. H. Fleming, J. Am. Chem. Soc. 55, 3803 (1933).
4.Halford, Anderson, Bates, and Swisher, J. Am. Chem. Soc. 57, 1663 (1935).
5.J. O. Halford and L. C. Anderson, J. Am. Chem. Soc. 58, 736 (1936).
6.For the benefit of other investigators, it might be in order to write out the elementary general theory for the quantitative progress of such an exchange reaction when the process is stepwise and statistical distribution is assumed. Let A and B be the number of moles of and respectively present in the material to be exchanged with heavy water. C and D represent the number of moles of and contributed to the mixture by the heavy water component of the mixture. If statistical distribution of H and D in the mixture is achieved, the fractional deuteration is obviously . It can easily be seen that repetitive operation of such a stepwise process to achieve large values of is a powerful method of testing the assumption of statistical distribution of H and D in the process. Our results have shown very conclusively that such statistical distribution is achieved in the acetone and malonic exchange processes. Furthermore, after the completion of the synthesis of tetramethylmethane‐ a very sensitive test of the completeness of deuteration in the absence of further exchange of reagents is available. The statistical distribution of isotopic molecules of the various species present will be proportional to the terms of the expansion of where n is the number of hydrogen atoms present in the molecule. In all probability the expression just given is strictly valid only for equal in the acetone and the methyl bromide reagents. The relative abundance of the species containing one hydrogen can easily be estimated from the spectrum with considerable certainty.
7.W. Bockemuller and F. W. Hoffman, Ann. d Chem. 519, 165 (1935).
8.D. H. Rank and J. S. McCartney, J. Opt. Soc. Am. 38, 279 (1948);
8.Rank, Sheppard, and Szasz, J. Chem. Phys. 16, 698 (1948).
9.Rank, Scott, and Fenske, Ind. Eng. Chem. Anal. Ed. 14, 816 (1942).
10.A. E. Douglas and D. H. Rank, J. Opt. Soc. Am. 38, 281 (1948).
11.D. H. Rank, J. Opt. Soc. Am. 40, 462 (1950).
12.A. Walsh, J. Opt. Soc. Am. 42, 96 (1952).
13.D. H. Rank and E. R. Bordner, J. Chem. Phys. 3, 248 (1934).
14.See G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules (D. Van Nostrand Company, Inc., New York, 1947), p. 231.
15.E. D. Fitz, M.S. thesis, The Pennsylvania State College, August, 1951.
16.F. Lechner, Wien Anz. (1933), No. 14; quoted by Herzberg (reference 14) p. 182.
17.J. E. Rosenthal, Phys. Rev. 45, 538 (1934).
18.J. E. Rosenthal, Phys. Rev. 46, 730 (1934).
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