We have established that tert-butyl hydroperoxide decomposes into radicals under the effect of hydrogen ions of perchloric acid. At sufficiently low concentrations of acid (< 0.01 mole) and hydroperoxide (< 0.03 mole) the rate of initiation wi=ki[ROOH]2− [HClO4], ki=4.0×1015 exp (−28,000/RT) mole−2 · sec−1.
Only 20% of the hydroperoxide decomposes into radicals. Heterolytic decomposition of the hydroperoxide into molecular products is more intense.
It is postulated that radical formation takes place as follows: ROOH2 ++ROOH → RO+H3O++ROO.
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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1391–1393, June, 1968.
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Solyanikov, V.M., Denisov, E.T. Decomposition of tertiary butyl hydroperoxide into radicals under the effect of hydrogen ions. Russ Chem Bull 17, 1315–1316 (1968). https://doi.org/10.1007/BF01106298
- Perchloric Acid
- Radical Formation