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Original Articles

Isotopic and Optical Studies of the Decomposition of Crystalline Dibenzoyl Peroxide

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Pages 121-132 | Received 21 Aug 1978, Published online: 12 Oct 2011

References

  • Vary , M. W. and McBride , J. M. 1979 . Molec. Cryst. Liq. Cryst. , 52 : 133 [Following paper in this issue]
  • Karch , N. J. , Koh , E. T. , Whitsel , B. L. and McBride , J. M. 1975 . J. Am. Chem. Soc. , 97 : 6729
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  • Morsi , S. E. , Thomas , J. M. and Williams , J. O. 1975 . J. Chem. Soc., Faraday I , 71 : 857
  • Barchuk , V. I. , Dubinsky , A. A. , Ginberg , O. Ya. and Lebedev , S. Ya. 1975 . Chem. Phys. Lett. , 34 : 476
  • Sagdeev , R. Z. , Obynochny , A. A. , Peruvkin , V. V. , Molin , N. Yu. and Moralyov , V. M. 1977 . Chem. Phys. Lett. , 47 : 292 In collaboration with Professor D. Rye of Yale's Department of Geology and Geophysics we have measured the isotope effect at 1.8 K. We find an increase in the 13C/12C ratio of 0.5% in going from BPO to CO2, where Sagdeev et al. reported a decrease of 30% at 4.2 K.
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  • Bowes , P. C. Fire Research Note No. 571 (Department of Scientific and Industrial Research and Fire Offices' Committee Joint Fire Research Organization, Oct. 1964).
  • Measured on the Brucker spectrometer of the Southern New England High Field NMR Facility (NIH No. 1-PO7-PR00798).
  • This pressure, higher than that reported in Reference 8, was kindly communicated to the authors by Professor Thomas.
  • Walling , C. and Savas , E. S. 1967 . J. Am. Chem. Soc. , 82 : 1738
  • Cadogan , J. I. G. , Hey , D. H. and Hibbert , P. G. 1965 . J. Chem. Soc. , : 3939 have proposed induced decomposition mechanisms for BPO which involve radical attack at the para position. A mechanism for the 1,4-hydrogen shift and decarboxylation, which would be required in the present case is not obvious.
  • DeTar , D. F. 1967 . J. Am. Chem. Soc. , 89 : 4058
  • Miller , W. H. 1863 . Proc. Roy. Soc., London , 12 : 394
  • The benzene-grown crystal illustrated in Figure la of Reference 8 is indexed incorrectly. This raises additional questions about the subsequent interpretation in that paper.
  • Although Barchuk et al. did not claim this fine a distinction, it is almost surely attainable.
  • Barchuk et al. proposed that the transition is polarized along the C–O(peroxy) bond, which makes an angle of 70° with [010]. If this be so, it must be completely different from the transition we have characterized above.
  • This description is approximate because the {110} planes make angles of 32.1° rather than 45° with [010].

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