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On the Mass Spectra of Propanes and Butanes Containing C13
1.Beeck, Otvos, Stevenson, and Wagner, J. Chem. Phys. 16, 255 (1948).
2.Otvos, Stevenson, Wagner, and Beeck, 16, 745 (1948).
3.Stevenson, Wagner, Beeck, and Otvos, J. Chem. Phys. 16, 993 (1948).
4.See also Evans, Bauer, and Beach, J. Chem. Phys. 14, 701 (1946) on the analysis of mixed deuteromethanes.
5.See references 1 and 2 and C. D. Wagner, J. Am. Chem. Soc. (to be published).
6.D. P. Stevenson and C. D. Wagner, J. Chem. Phys. 18, 11 (1950).
7.See references 1 and 5 for reaction sequence.
8.It has been shown that for certain monodeuteroparaffins this is not true; see reference 6.
9.Although it is present, the concentration of is negligibly small in all cases of interest herein.
10.Phillips certified propane n‐butane and isobutane were used as reference compounds in this investigation.
11.For the Phillips hydrocarbons as well as Eastman Kodak Company White Label and n‐ ρ as measured with our mass spectrometer This value of ρ was obtained from measurements of the 45/44 ratio of carbon dioxide (corrected for natural ) prepared by the complete combustion of the various substances.
12.The possible effects of isotopic substitution on the parent ion sensitivity of substances is discussed elsewhere, reference 6.
13.See reference 5 for the evidence that these samples to represent intramolecular equilibration. The equilibrium constants of the various intramolecular rearrangement reactions were assumed to be , i.e., possible isotope effects on the relative free energy of isotopic isomers were neglected.
14.We refer to those portions of the mass spectrum of the labeled species which have not been assumed, i.e., to the relative intensities of the ion fragments formed through the breaking of one or more carbon‐carbon bonds as well as carbon‐hydrogen bonds.
15.D. P. Stevenson, J. Chem. Phys. 10, 291 (1942).
16.For proof that these are the correct representations of these processes, see Phys. Rev. 56, 256 (1939)
16.and J. Am. Chem. Soc. 64, 2769 (1942) for propane,
16.and J. Am. Chem. Soc. 64, 1588 (1942) for the butanes.
17.That these isotope effects here reported are not due to dependent variations of the efficiency of collection of ions by the Westinghouse mass spectrometer has been experimentally demonstrated. A detailed report on studies of the efficiency of ion collection [i.e., discrimination—N. D. Coggeshall, J. Chem. Phys. 12, 19 (1944)] in the Westinghouse mass spectrometer will be submitted for publication.
18.R. E. Honig, Phys. Rev. 75, 1319 (1949).
19.See J. A. Hipple, Phys. Rev. 71, 594 (1947) for the method of measuring the half‐lives of metastable ions formed by electron impact.
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