REDUCTION OF 4-NITROSODIPHENYLAMINE
1791
we evaluated the angular coefficient of the depen-
Containing Reducing Agents), Moscow: Khimiya,
1994.
dence v = f(c ) by Eq. (11) and compared with the
ov
r
experimental data (Fig. 2b) (Table 4). Satisfactory
agreement of these results additionally confirms the
adequacy of the proposed kinetic model. From the
temperature dependences of the rate constants listed in
Table 3, we evaluated the activation energies for the
associative and dissociative pathways to be 106 10
2. Makarov, S.V., Reactivity of Sulfur- and Oxygen-
Containing Reducing Agents with C S Bond, Doctor-
al Dissertation, Ivanovo, 2000.
3. USSR Inventor’s Certificate no. 1158561.
4. Polenov, Yu.V. and Budanov, V.V., Izv. Vyssh.
Uchebn. Zaved., Khim. Khim. Tekhnol., 1988, vol. 31,
no. 4, pp. 40 43.
1
and 53 2 kJ mol , respectively.
5. Makarov, S.V., Budanov, V.V., and Shalimova, G.V.,
Zh. Prikl. Khim., 1985, vol. 58, no. 5, pp. 1098 1102.
6. Makarov, S.V., Sokolova, I.N., and Budanov, V.V.,
It should be noted in conclusion that the found rate
constants k (Table 2) characterize the ease of the
1
rupture of the C S bond in alkanesulfinate molecule.
From the above data, the reducing agents can be
ranked in the following order with respect to stability:
SHES < SAMS < SHMS.
Zh. Obshch. Khim., 1985, vol. 55, no. 4, pp. 724 730.
7. Budanov, V.V., Khimiya i tekhnologiya vosstanovite-
lei na osnove sul’foksilovoi kisloty (rongalit i ego
analogi) [Chemistry and Technology of Reducing
Agents Based on Sulfoxylic Acid (Rongalite and Its
Analogs)], Moscow: Khimiya, 1984.
CONCLUSION
8. Sputnik khimika (A Guide for Chemist), Blokh, M.A.,
Based on the kinetic data for reduction of 4-nitro-
sodiphenylamine with sodium hydroxymethanesulfi-
nate, sodium hydroxyethanesulfinate, and sodium
aminomethanesulfinate, the kinetic equations were
obtained. These equations suggest that the reaction
proceeds by two parallel pathways: direct reaction of
the substrate with reducing agent molecule (associa-
tive pathway) and reaction with the product of reduc-
ing agent decomposition, sulfoxylate anion (dissocia-
tive pathway).
Ed., Leningrad: ONTIKhimteor, 1935.
9. Sarsenbaeva, G.L., Avrutskaya, I.A., and Fio-
shin, M.D., Elektrokhimiya, 1977, vol. 13, no. 2,
pp. 290 293.
10. Sokolova, I.N., Budanov, V.V., Polenov, Yu.V., and
Polyakova, I.R., Izv. Vyssh. Uchebn. Zaved., Khim.
Khim. Tekhnol., 1983, vol. 26, no. 7, p. 822.
11. Budanov, V.V., Sokolova, I.N., Solov’eva, L.B., and
Mel’nikova, B.N., Izv. Vyssh. Uchebn. Zaved., Khim.
Khim. Tekhnol., 1974, vol. 17, no. 7, pp. 993 997.
12. Nesmeyanov, A.N. and Nesmeyanov, N.A., Nachala
organicheskoi khimii (Principles of Organic Chemis-
try), Moscow: Khimiya, 1974, vol. 1.
REFERENCES
1. Budanov, V.V. and Makarov, S.V., Khimiya seroso-
derzhashchikh vosstanovitelei (Chemistry of Sulfur-
13. The Chemistry of the Nitro and Nitroso Groups, Feu-
er, H., Ed., New York: Wiley, 1969, part 1.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 76 No. 11 2003