556
MAKHIN et al.
CONCLUSIONS
REFERENCES
1. Carey, F.A. and Sundberg, R.J, Advanced organic chem-
As a result of the experimental study, we deter-
istry, New York: Kluwer Academic–Plenum, 2000.
mined the reaction kinetics of the liquid-phase hydro-
chlorination of ethanol. An analysis of the kinetics of
hydrochlorination of monohydric primary alcohols
and polyols showed that the negative effect of the con-
centration of water on the reaction rate is a common
feature of reactions of this kind. In accordance with
the SN2 mechanism, second-order equation (2),
which is used to describe the kinetics of these reac-
tions, can be valid only in a narrow range of reactant
concentrations. The approach that takes into account
the degree of hydration of hydrogen chloride makes it
possible to solve this problem by the introduction of
correction coefficient γ into the kinetic equation. The
rate equations obtained in this case are empirical ones,
and they are valid in the ranges of temperatures and
concentrations for which they were derived.
2. Hinshelwood, C.N., J. Chem. Soc., 1935, p. 599.
3. Vigdorovich, V.I. and Gorelkin, I.I., Zh. Prikl. Khim.,
1973, vol. 46, p. 1083
4. Grunwald, E. and Winstein, S., J. Am. Chem. Soc.,
1947, vol. 69, no. 8, p. 2051.
5. Kingsley, H.A. and Bliss, H., Ind. Eng. Chem., 1952,
vol. 44, no. 10, p. 2479.
6. Gerrard, W., Madden, R.W., and Tolcher, P., J. Appl.
Chem., 1955, vol. 5, issue 1, p. 28.
7. Daté, R.V., Butt, J.B., and Bliss, H., Ind. Eng. Chem.
Fundam., 1969, vol. 8, no. 4, p. 687.
8. Reichardt, C., Solvents and Solvent Effects in Organic
Chemistry, Weinheim: Wiley-VCH, 2003.
9. Fialkov, Yu.A., Rastvoritel’ kak sredstvo upravleniya
khimicheskim protsessom (Solvent as a Tool to Control
the Chemical Process), Leningrad: Khimiya, 1990.
10. Schmid, R. and Sapunov, V.N., Non‐Formal Kinetics,
Weinheim: Verlag Chemie, 1982.
A comparison between the rates of hydrochlorina-
tion of primary and polyhydric alcohols made it possi-
ble to determine the relative reactivity of an alcohol
depending on its structure. The results of this work can
be used for studying the reaction kinetics of hydro-
chlorination of other alcohols and for evaluating the
rate of reaction without conducting experiments.
11. Amis, E., Vliyanie rastvoritelya na skorost' i mekhanizm
khimicheskikh reaktsii (Effect of Solvent on the Rate
and Mechanism of Chemical Reactions), Moscow:
Mir, 1968.
12. Dmitriev, G. and Zanaveskin, L., Chem. Eng. Trans.,
2011, vol. 24, part 1, p. 43.
13. Makhin, M.N., Zanaveskin, L.N., and Dmitriev, G.S.,
Kinet. Catal., 2013, vol. 54, no. 6, p. 667.
14. Makhin, M.N., Zanaveskin, L.N., and Dmitriev, G.S.,
Kinet. Catal., 2014, vol. 55, no. 2, p. 163.
ACKNOWLEDGMENTS
15. Gordon, A.J., and Ford, R.A., The Chemist’s Compan-
ion: A Handbook of Practical Data, Techniques, and Ref-
erences, New York: Wiley, 1972.
This work was supported by the Federal Agency for
Scientific Organizations (FASO) of the Russian Fed-
eration and performed within the framework of a state
contract at the Topchiev Institute of Petrochemical
Synthesis, Russian Academy of Sciences.
16. Bennett, G.M. and Reynolds, F.M., J. Chem. Soc.,
1935, p. 131.
Translated by V. Makhlyarchuk
KINETICS AND CATALYSIS
Vol. 59
No. 5
2018