KINETICS AND MECHANISM OF THE PUDOVIK REACTION IN THE AZOMETHINE SERIES: III. 429
Kinetic studies were carried out by spectroscopy
on SF-46 and SF-26 spectrophotometers in tempera-
ture-controlled cells in the temperature range 293
358 K. Reaction progress was controlled by the de-
crease of absorbance (or increase of transmittance) of
the reaction mixture in the range 280 350 nm at a
wavelength corresponding to the maximum change of
the optical density of imine and the minimum absorp-
tion of reaction products in the course of the reaction.
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The kinetic experiments were carried out under
pseudofirst-order conditions in azomethines. The
5
4
concentrations of azomethines were 10 10 M at
1
large excesses of dialkyl hydrogen phosphite (10
1 M) and water (10 1 M).
1
Solutions were prepared directly in the working
cell by two procedures. According to the first proce-
dure, solutions of purified amines and necessary ad-
ditives of known concentrations in corresponding
solvents were placed in the cell, after which 0.1 ml of
individual dialkyl hydrogen phosphite was added
(procedure A). According to the second procedure, a
necessary amount of a solution of a freshly purified
dialkyl hydrogen phosphite in the same solvent
(method B) was added last. The resulting solution was
stirred and placed in the cell. From this moment time
reading and photometry were begun.
The pseudofirst-order rate constants were calcu-
lated from the linear dependence of ln[1/(D D )]
on t, where D is the current optical density, D is the
optical density measured after the spectral picture no
longer changed (usually after a day), and t is the
current time (s).
The activation parameters were calculated from the
rate constants measured at no less than four different
temperatures [21]. The calculated activation param-
eters are listed in Table 3.
ACKNOWLEDGMENTS
The work was financially supported by the Russian
Foundation for Basic Research (project no. 04-03-
32906), Universities of Russia Basic Research
Program of the Ministry of Education and Science of
the Russian Federation, and Basic Research and
Higher Education Bilateral Program of CRDF and the
Ministry of Education and Science of the Russian
Federation (project no. REC-007).
REFERENCES
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21. Weissberger, A. and Proskauer, E.S., Organic Sol-
vents: Physical Properties and Methods of Purifica-
tion, Riddick, J.A. and Toops, E.E., Jr., Eds., New
York: Interscience, 1955.
2. Cherkasov, R.A. and Galkin, V.I., Usp. Khim., 1998,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 76 No. 3 2006