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Effect of pressure on the decomposition of 2-tert-butyl peroxide in solution

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Bulletin of the Academy of Sciences of the USSR, Division of chemical science Aims and scope

Abstract

A study was carried out on the effect of pressure up to 1400 MPa on the homolytic decomposition of di-tert-butyl peroxide (DTBP) at 403 K in 2-methoxy- (I) and 2-ethoxytetrahydropyran (II) as well as in a mixture of 30 mole % (I) and 70 mole % benzene. Spline approximation of the experimental pressure dependence of the logarithm of the decomposition rate constant (ka) gave the continuous dependence of the volumetric activation effect (ΔV≠) on pressure. The value of ΔV≠ at atmospheric pressure (ΔV≠ 0) and the nature of the change of AV≠ with increasing pressure were found to depend on the nature of the solvent. This dependence is difficult to explain in the framework of the accepted transition state theory.

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Authors and Affiliations

  1. N. D. Zelinskii Institute of Organic Chemistry, Academy of Sciences of the USSR, Moscow

    V. M. Zhulin, I. Khuéidzha, E. B. Kabotyanskaya & Yu. D. Koreshkov

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  1. V. M. Zhulin
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  2. I. Khuéidzha
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  3. E. B. Kabotyanskaya
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  4. Yu. D. Koreshkov
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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1911–1914, August, 1990.

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Zhulin, V.M., Khuéidzha, I., Kabotyanskaya, E.B. et al. Effect of pressure on the decomposition of 2-tert-butyl peroxide in solution. Russ Chem Bull 39, 1739–1742 (1990). https://doi.org/10.1007/BF00961517

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  • DOI: https://doi.org/10.1007/BF00961517

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