Russian Journal of Applied Chemistry, 2010, Vol. 83, No. 10, pp. 1837−1845.
Pleiades Publishing, Ltd., 2010.
Original Russian Text
S.D. Pozhidaeva, A.M. Ivanov, T.A. Mayakova, 2010, published in Zhurnal Prikladnoi Khimii, 2010, Vol. 83, No. 10, pp. 1698−1706.
PROCESSES AND EQUIPMENT
OF CHEMICAL INDUSTRY
Characteristics of the Reaction of Manganese Metal
with Phenols, Alcohols, Water, and Their Mixtures
with Each Other and with Carboxylic Acids
in a Bead Mill
S. D. Pozhidaeva, A. M. Ivanov, and T. A. Mayakova
Kursk State Technical University, Kursk, Russia
Received December 29, 2008
Abstract—The macrokinetic relationships of the mechanochemical reaction of manganese with phenols,
alcohols, water, and their mixtures with each other and with carboxylic acids taken in various molar ratios but,
in some cases, in total stoichiometric amount were examined.
Metal alcoholates and phenolates are widely used,
in particular, for preparing high-purity oxides and
oxide compounds, catalysts and adsorbents with highly
developed surface , high-purity elements and oxide
coatings [2, 3], for doping semiconductor compounds,
for preparing specialty ceramics and thin and ultrathin
coatings, and in nanotechnologies [4–6].
It is known  that only metals of Groups I and
II vigorously react with alcohols and phenols. Under
deﬁ nite conditions, such reactions are also possible
with metals of Group III. However, such reactions
require catalysts and initiators whose role consists
in overcoming the barrier caused by the presence of
an impermeable oxide ﬁ lm on the metal surface. It is
believed that metals of other groups of the periodic table
cannot react with alcohols and phenols.
At the same time, under conditions of activation
in a high-performance bead mill, it appeared possible
to efﬁ ciently perform reactions of a number of heavy
transition metals with many carboxylic acids [8–11]
at technologically acceptable rates [12–20]. It was
emphasized that the main problem in such processes
is breakdown and removal of strong surface deposits
of salts that are formed in the reaction and prevent
the access of the acid to the reaction site, rather than
breakdown of the oxide ﬁ lm initially present on the
metal. Similar process seems to be feasible with alcohols
and phenols. To check this assumption, we examined in
this study the reactions of alcohols, phenols, and water
with manganese in comparison with the reaction of
manganese with oxalic acid.
The experiment was performed in a vertical bead mill
in accordance with the step-by-step scheme in which
the horizontal line is the time axis (without consistent
scale), arrows directed toward it denote feed streams,
arrows denoted from the axis denote takeoff streams,
and legends above and under the axis denote the main
operations performed at the given instant of time.
In the above scheme, certain time can be provided
for preparing reagent solutions in the chosen liquid
phase solvent, and the moments of introducing the metal
and stimulating additive can be varied. In some cases,
this factor appeared to be signiﬁ cant. In current process
monitoring, we primarily determined the content of
Mn(II) compounds in the samples taken. In addition,
we analyzed the residual amounts of the reagents taken
in stoichiometric amounts or in deﬁ ciency, and also of
manganese (in some cases). For this purpose, it was
necessary to ﬁ nd such procedures of metal pretreatment