KINETIC FEATURES OF DECOMPOSITION OF BENZOYL PEROXIDE
763
result confirms the suggested twostep mechanism of
decomposition of peroxide I in superbasic media.
2. Dutka, V.S., Pankevich, R.V., and Koval’skii, Ya.P.,
Ukr. Khim. Zh., 1988, vol. 54, no. 4, p. 429.
3. Dutka, V.S., Tsvetko, N.S., and Markovskaya, R.F.,
EXPERIMENTAL
Kinet. Katal., 1982, vol. 23, no. 5, p. 1071.
4. Bylina, N.S., Matveentseva, M.S., and Ol’de-
kop, Yu.A., Zh. Org. Khim., 1975, vol. 11, no. 11,
p. 2237.
The experiments were carried out in a temperature-
controlled cell equipped with a magnetic stirrer over
the temperature range 298 328 K. NaOH and KOH
were preliminarily crushed in a mortar in the Ar
atmosphere. The solvents were dried over CaO,
5. Walling, C., Waits, H.P., Milovanovic, J., and Pap-
piaonnou, C.G., J. Am. Chem. Soc., 1970, vol. 92,
no. 16, p. 4927.
vacuum-distilled, and stored over 4
molecular
6. Tsvetkov, N.S., Zhukovskii, V.Ya., and Markov-
skaya, R.F., Ukr. Khim. Zh., 1976, vol. 42, no. 12,
p. 1294.
sieves [19]. Benzoyl peroxide was synthesized as in
[20] and then was recrystallized three times from
ethanol. The purity of the product was 99.5
99.8 wt%.
7. Dutka, V.S., Ukr. Khim. Zh., 1987, vol. 53, no. 9,
p. 973.
Decomposition of benzoyl peroxide (I). A
weighed portion of the base was placed into the cell,
a fixed volume of the solvent was added, the system
was allowed to stand for 30 min at the desired tem-
perature, and, finally, the peroxide was added. The
process kinetics was monitored iodometrically. As a
kinetic parameter we used the initial decomposition
rate v0. Liquid reaction products were determined by
gas chromatography on a Chrom-5 instrument (flame-
ionization detector; 3000 3 mm glass column;
stationary phase SE-30; carrier gas argon; temperature-
programmed mode, 323 523 K; heating rate
8. Dutka, V.S., Ukr. Khim. Zh., 1988, vol. 54, no. 16,
p. 1091.
9. Dutka, V.S. and Pankevich, R.V., Ukr. Khim. Zh.,
1991, vol. 57, no. 5, p. 462.
10. Tsvetkov, N.S., Markovskaya, R.F., and Ostapo-
vich, B.B., Ukr. Khim. Zh., 1986, vol. 52, no. 4,
p. 434.
11. Tsvetkov, N.S., Zhukovskii, V.Ya., Pirig, Ya.N., and
Makitra, R.G., Kinet. Katal., 1979, vol. 20, no. 6,
p. 1418.
1
12. Lyavinets, A.S., Zh. Fiz. Khim., 1999, vol. 73, no. 3,
8 deg min ). The resulting chromatograms were
processed using an internal reference.
p. 466.
13. Pobedimskii, D.G., Usp. Khim., 1971, vol. 40, no. 3,
The electrolytic conductivity of the reaction mix-
tures was measured by the compensation method
using an R-577 ac bridge and an F-582 null indicator.
p. 254.
14. Shashin, S.S., Emanuel’, O.N., and Skibida, I.P., Izv.
Akad. Nauk SSSR, Ser. Khim., 1983, no. 10, p. 2223.
Alkylation of intermediate sodium perbenzoate
was carried out at 290 K using the same procedure as
in studying the decomposition kinetics. The alkylating
agent was introduced 15 min after addition of the
peroxide. The process was monitored by the consump-
tion of available oxygen using the iodometric method
and also by the accumulation of butyl benzoate using
GC. Since peroxy compounds are unstable under GC
conditions, they were reduced with triphenylphos-
phine prior to analysis. In so doing, butyl perbenzoate
was reduced to butyl benzoate.
15. Lyavinets, A.S., Choban, A.F., and Chervinskii, K.A.,
Zh. Fiz. Khim., 1993, vol. 67, no. 7, p. 1364.
16. Lyavinets, A.S., Choban, A.F., Slipchenko, E.K., and
Chervinskii, K.A., Neftekhimiya, 1993, vol. 33, no. 5,
p. 445.
17. Lyavinets, A.S., Choban, A.F., and Chervinskii, K.A.,
Neftekhimiya, 1995, vol. 35, no. 5, p. 448.
18. Lyavinets, A.S., Ukr. Khim. Zh., 1998, vol. 64, no. 2,
p. 77.
19. Gordon, A.J. and Ford, R.A., The Chemist’s Com-
panion: A Handbook of Practical Data, Techniques,
and References, New York: Wiley, 1972.
REFERENCES
1. Rakhimov, A.I., Khimiya i tekhnologiya organiches-
kikh perekisnykh soedinenii (Chemistry and Tech-
nology of Organic Peroxides), Moscow: Khimiya,
1979.
20. Karnojitzki, V., Les peroxydes organiques, Paris:
Herman, 1958. Translated under the title Organiches-
kie perekisi, Moscow: Inostrannaya Literatura, 1961,
p. 61.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 5 2005