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

Article abstract of DOI:10.1134/S1070427210100198

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.

Full text of DOI:10.1134/S1070427210100198

ISSN 1070-4272, 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.
DOI: 10.1134/S1070427210100198
Metal alcoholates and phenolates are widely used,
in particular, for preparing high-purity oxides and
oxide compounds, catalysts and adsorbents with highly
developed surface [1], 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].
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.
EXPERIMENTAL
It is known [7] that only metals of Groups I and
II vigorously react with alcohols and phenols. Under
definite 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 film on the metal surface. It is
believed that metals of other groups of the periodic table
cannot react with alcohols and phenols.
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 significant. 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 deficiency, and also of
manganese (in some cases). For this purpose, it was
necessary to find such procedures of metal pretreatment
At the same time, under conditions of activation
in a high-performance bead mill, it appeared possible
to efficiently 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 film initially present on the
1837

1838
POZHIDAEVA et al.
Step-by-step scheme of the process
Liquid phase solvent
Separation and
identification of
product
(including alcohol ROH)
Process
Metal
Process start
termination
Stirring the reaction
mixture (RM), performing
the process, cooling
Separation
of RM from
beads
Separation
of product
solid phase
Glass beads
Sampling for current
monitoring
Filtrate analysis,
reprocessing, and utilization
Stimulating additive
in repeated process
Carboxylic acid and/or alcohol,
and/or phenol, and/or water; any
combinations of the above
compounds in various ratios
before analysis with which the metal particles would be
cleaned (at least partially) from surface deposits of the
product. First and foremost, it was necessary to estimate
the solubility of the products obtained in various media
(Table 1).
The parameters of the reactor used are as follows.
The casing is a cylindrical glass vessel with the inside
diameter of 43, height of 121, and wall thickness of
2.5 mm. The vessel is covered with a thick plastic lid
with a deep circular groove with a gasket on its bottom.
The groove diameter corresponds to the vessel diameter.
The stuffing box of the power-driven stirrer is arranged
in the center of the lid, and on its side there are a pipe for
connection with a reflux condenser and holes to arrange
a sampler and a housing for measuring the reaction
As can be seen, in most cases the reaction products
are poorly soluble in organic solvents. This fact explains
why in the course of the reaction they are mainly
accumulated in the solid suspended state, as reflected in
the scheme.
Table 1. Estimation of the solubility of manganese oxalate, phenolate, and 2-methylpropan-1-olate in various solvents
Solubility, mol kg–1
2-methylpropan-1-olate
oxalate (38.4% Mn)
26
phenolate (22.8% Mn)
(27.3% Mn)
Solvent
at indicated temperature, °C, ±1
15
55
15
26
67
10
26
65
Ethyl acetate
Butyl acetate
DMF
2-Ethoxyethanol
1-Propanol
2-Propanol
0.020
0.017
0.017
0.018
0.024
0.022
0.030
0.009
0.024
0.021
0.017
0.031
0.036
0.017
0.064
0.024
0.021
0.020
0.018
0.039
0.015
0.009
0.009
0.007
0.005
0.009
0.022
0.10
0.022
0.036
0.029
0.027
0.026
0.078
0.023
0.028
0.039
0.015
0.004
0.007
0.010
0.010
0.009
0.009
0.009
0.009
0.008
0.010
0.007
0.011
0.018
0.017
0.017
0.012
0.016
0.012
0.007
0.016
0.016
0.016
0.028
0.017
0.016
0.015
0.024
0.027
0.020
0.014
0.018
0.032
0.035
0.021
0.016
0.022
0.035
0.035
0.026
0.018
0.020
0.020
0.052
0.013
0.020
0.021
0.082
0.063
0.018
0.018
1-Butanol
2-Methylpropan-1-ol
3-Methylbutan-1-ol
o-Xylene
0.009
0.008
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 83 No. 10 2010

CHARACTERISTICS OF THE REACTION OF MANGANESE METAL
1839
mixture temperature. These holes are intermittently used
for adding the required chemicals in the course of the
process. The stirrer blade size is 41.5 × 40 × 3.7 mm. It
is fixed in the slit of a textolite shaft of diameter 11 mm
with two plastic pins. The stirrer shaft is connected to
the driver shaft with a flexible connection. The driver
power is 0.37 kW. The rotor rotation rate was 1560 rpm
in most cases.
All parts of the installation are rigidly fixed on
a special framework and have strictly fixed positions in
all the steps of the work. The dismountable parts after
the experiment completion were the cooling water bath
in which the reactor casing was immersed to 0.5–0.8 of
its height and the bead mill casing with the beads and
reaction mixture. The bead size was 1.8–2.5 mm, and its
weight ratio to the charge was (1.0–1.5) : 1.
τ, min
Fig. 1. Kinetic curves of manganese consumption in reaction
with (1) oxalic acid, (2) 2-ethoxyethanol, (3) phenol, and (4)
water. Reactor: vertical bead mill with textolite blade stirrer,
gap between the blade and reactor casing 1.5 mm, beads to
charge weight ratio 1.5 : 1, beads weight 120 g, temperature
33 ± 1°С. (ХMn) Manganese content and (τ) time. Reactant
ratio: (1, 3) stoichiometric and (2, 4) excess alcohol and water.
Solvent: (1, 2) 2-ethoxyethanol, (3) butyl acetate, and (4)
water.
Figure 1 shows the kinetic curves of the manganese
consumption in its reactions with the acid, alcohol,
phenol, and water taken separately. As can be seen,
under the chosen conditions all these reactions start
immediately and proceed to high conversions, with
comparable reaction rates and times. It is important that
the manganese conversion was practically quantitative
Table 2. Influence of the nature of alcohol as reagent and liquid phase solvent on the characteristics of its reaction with manganese
metal in bead mill. Initial Mn content XMn = 1.4 mol kg–1
Time, min, of attainment of
indicated Mn conversion α
Alcohol
Reaction ordera
0.98 and
above
200
0.25
0.50
0.75
Methanol
1-Propanol
2-Propanol
1-Butanol
50
42
27
87
80
45
19
67
9
100
84
150
145
173
280
235
156
98
Zero in the entire range of conversions
300
253
418
337
292
179
388
150
79
Initially zero
96
Initially close to zero, zero in the range α = 0.45–0.83
175
156
90
Zero up to α = 0.85
2-Methyl-1-propanol
1-Pentanol
Initially close to zero
Zero up to α=0.55
3-Methyl-1-butanol
Cyclohexanol
40
Initially close to zero
138
18
237
63
"
1,2-Ethanediol
Zero
1,2-Ethanediol : butyl acetate =
1 : 1 (v/v)
14
27
43
"
2-Ethoxyethanol
40
80
100
120
Zero in the range α = 0.5–0.99
a
The reaction order was determined as follows: by the coordinate transfer, we cut out a portion of the kinetic curve of the initial reagent
consumption or product accumulation. Using known (in particular, integral) methods, this portion was checked for correspondence to one
or another order; simultaneously, the boundaries of the cut-out portion were determined in the entire range of conversions of the reagent
taken in deficiency.
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POZHIDAEVA et al.
Table 3. Influence of the nature of phenols on characteristics of their reaction with manganese metal in bead mill. Initial content,
mol kg–1: Х
= 1.4, Х
= 0.7; solvent butyl acetate, Т = 30 ± 1°С
0
0
Mn
phenol
Time, min, of attainment of indicated Mn
conversion α 0.98 and above
Characteristic of reaction mixture at high
conversions
Phenol
0.98 and
0.25
0.50
0.75
above
305
148
150
320
215
340
Phenol
o-Nitrophenol
m-Hydroxybenzaldehyde
Moderately viscous suspension
Reaction mixture poorly separable from beads
Strong thickening at high conversions
Suspension, green filtrate
80
31
170
63
223
94
10
35
80
p-Hydroxybenzaldehyde
p-Cresol
63
160
100
220
260
150
280
Poorly separable suspension
50
Moderately viscous suspension
2-Naphthol
100
in its reaction with all the chosen alcohols and phenols
(Tables 2, 3). Of course, the nature of the acid reagent
plays an important role, determining the macrokinetic
and time characteristics of the process and also the
phase state of the reaction mixture and the dynamics of
its variation in the course of the process. For different
reagents, these characteristics are naturally different.
Whereas alcohol was taken in a fairly large excess,
because it simultaneously acted as a reagent and
asolventfortheliquidphase, phenolwasaddedinstrictly
stoichiometric amounts. These differences are partially
associated with the fact that alcohols are weaker acids
than phenols. However, nonchemical factors can also be
important in the process. This indirectly follows from
the presence of a certain optimum in the manganese
content in the reaction mixture, at which the reaction
rate is maximal and the process time is correspondingly
minimal (Figs. 2, 3). With 2-propanol, which was
τ, min
τ, min
XMn, mol kg–1
XMn, mol kg–1
Fig. 2. Time τα of attainment of given conversion of manganese
α in reaction with 2-propanol as a function of the initial Mn
content ХMn. Temperature 33 ± 1°С, no additional solvent,
charge to beads weight ratio 1 : 1.4. Mn conversion α: (1) 0.25,
(2) 0.50, (3) 0.75, and (4) 0.98 and above; the same for Fig. 3.
Fig. 3. Time τα of attainment of given conversion of manganese
α in reaction with phenol as a function of the initial Mn content
ХMn. Stoichiometric ratio of metal and phenol, liquid phase
solvent butyl acetate, temperature 33 ± 1°С, charge to beads
weight ratio 1 : 1.25, stirrer rotation rate 1440 rpm.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 83 No. 10 2010

CHARACTERISTICS OF THE REACTION OF MANGANESE METAL
1841
chosen for systematic studies because with this alcohol,
acting as both reagent and solvent, the reaction order
changes from 1 to 0 (Table 2), such manganese content
is 3.6–3.9 mol kg–1 (Fig. 2), and with phenol (the
simplest representative of this class of acid reagents)
it is somewhat greater than 1 mol kg–1. Whereas with
the alcohol the minimal time of attainment of any given
degree of conversion is observed at the same initial
content of the metal in the reaction mixture, with phenol
the pattern is different: The lower the conversion, the
more is the time minimum shifted toward higher initial
manganese amounts.
rate law. Then accumulation of Mn(II) compounds
sharply ceases again, and after a certain period
accumulation of manganese compounds in a higher
oxidation state ceases also.
It cannot be excluded that this self-inhibiting process
can resume again. In some cases this was indeed the
case. However, this required, as a rule, longer time,
and the resumed process ceased again. Presumably,
surface deposits of products formed in the reaction of
manganese with water are stronger and, hence, exert
stronger hindering effect on the process than surface
deposits of manganese carboxylates, alkoxides, and
phenolates.
It is impossible to attribute these phenomena to
chemical interactions only. Most probably, they are
associated with such factors as an increase in the
content of abrasion products (fine metal particles), on
the one hand, and thickening of the suspension by metal
particles coated with surface deposits and by the product
suspended in the liquid phase, on the other hand. As
a result, the time required to attain any given degree
of metal conversion as a function of the initial metal
content passes through a minimum.
It was shown above that, under the chosen
experimental conditions, manganese can react at
comparable rates with acids, phenols, alcohols, and
water, i.e., with reagents whose рKа is in the range 2–18
and above. Clearly, рKа is not a decisive factor in such
processes. Itwasinterestingtodeterminehowtheprocess
characteristics would change on replacing a reagent by
its mixture with another reagent so that the total amount
of the reagents in the mixture would correspond to the
stoichiometric ratio to the metal loaded. The results are
given in Fig. 5 and in Tables 4–6.
With water as reagent, the manganese conversion is
quantitative very seldom, and usually it ranges from 40
to 85%. Then the process spontaneously decelerates, and
it cannot be brought to completion within reasonable
time. The process is additionally complicated by
partial oxidation of Mn(OH)2 with atmospheric oxygen
(Fig. 4) whose contact with the reaction mixture was
not specially limited. Probably, the presence of oxygen
favors to certain extent more complete conversion of the
metal.
As seen from Table 4, relatively small amounts of
water in the charge, even if it is present in a certain
stoichiometric excess, exert a moderate effect on the
conversion and on the time in which the chosen degrees
of metal conversion are attained. On the whole, the
presence of water somewhat inhibits the combined redox
As seen from Fig. 4, initially the major reaction
product is manganese(II) hydroxide. With time, its
accumulation stops. In the beginning of this period,
compounds of manganese in a higher oxidation state
are absent. The process cessation can be accounted for
by full blocking of the metal surface with Mn(OH)2
deposits. After accumulation of a definite amount of
blocking deposits, oxidation of manganese(II) hydroxide
with atmospheric oxygen occurred concurrently, and
starting from a certain moment it led to partial opening
of the metal surface and resumption of the formation
of manganese(II) hydroxide, but at a considerably
lower rate than in the initial moment, because the
surface was opened only partially. Then, for a certain
period, accumulation of Mn(II) and, apparently, Mn(IV)
compounds occurs concurrently, following zero-order
τ, min
Fig. 4. Kinetic curves of accumulation of (1) manganese(II)
hydroxide and (2) manganese(IV) hydroxide X
in
Mn(OH)
n
the reaction of manganese with water under the conditions of
curve 4 in Fig. 1. (τ) Reaction time.
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1842
POZHIDAEVA et al.
process but does not alter many of its characteristics
such as the presence of a minimum in the dependence of
the time of practically complete metal conversion on the
initial metal content (Fig. 5). Here it should be noted that
such metal conversion often follows the rate equation
for an irreversible zero-order reaction and that going to
water as a solvent for the liquid phase and removal of
glass beads from the reactor drastically deteriorate the
process characteristics.
Considerably more complex pattern is observed
with the phenol–2-propanol and phenol–water systems
(Table 6). With the components of these systems present
in comparable amounts, the time in which the given
degree of metal conversion is attained passes through
a maximum. The time in this maximum considerably
(sometimes by a factor of 5 and more) exceeds the
process duration in the presence of only one component
(but not water). It should be noted that, with water as
the major component, small additions of phenol favor
practically complete metal conversion at the highest
rates for this system and within the shortest time.
Similar pattern is observed with the phenol–2-propanol
system, with the only difference that with the alcohol
taken alone the process goes to completion without self-
inhibition observed with water.
In the oxalic acid–2-ethoxyethanol reagent system,
the times in which the given manganese conversions
are attained as functions of the relative acid content
pass through a minimum (Table 5). In other words, the
addition of alcohol favors the reaction of the acid with
the metal. This fact apparently explains why alcohols are
among the most widely used solvents for liquid-phase
processes for preparing carboxylates of manganese [12–
14] and other metals [15–21].
Presumably, these systems are characterized by
the occurrence of a number of parallel heterogeneous
Table 4. Effect of the solvent and additive on the reaction of manganese with oxalic acid and water in bead mill at 30 ± 1°С.
Weight ratio of charge to beads 1 : 1.25; initial content, mol kg–1: XMn = 0.8, Xox.ac =0.6, X
= 1.2
Н О
2
Time, min, of attainment of
indicated Mn conversion α
Liquid phase
solvent
Additive, mol
kg–1
Process characteristics
0.98
and
0.25
0.50
0.75
above
140a
10
10
28
12
15
24
12
7
No additive
Self-cessation on the 360th minute at α = 0.39
Water
23
20
41
24
39
56
37
16
20
24
24
44
38
65
43
80
88
61
40
45
70
71
78 k = 0.026 min–1, α
=0.73
k = const
60 k = 0.020 l mol–1 min–1, α
= 0.53
Water
k = const
110 Pronounced self-acceleration period at the beginning
p-Xylene
White spirit b
White spirit
Butyl acetate
1-Propanol
1-Butanol
71 Order close to zero up to α = 0.5
No additive
128 k = 0.020 min–1, α
= 0.48
k = const
120 Order close to zero in the range α = 0.15–0.95
132 No range with clear reaction order
80 Order close to zero from α = 0.61
80 No range with clear reaction order
150 Order close to zero after α = 0.61
6
2-Ethoxyethanol
1-Butanol
Water, 1.53
NaCl, 0.06
8
10
121 Intermediate self-inhibition followed by self-
acceleration at α = 0.75
KI, 0.06
NH4Cl, 0.06
I2, 0.06
20
13
9
78
35
18
143
110
46
220 Zero order after α = 0.30
180 Zero order after α = 0.50
84 Zero order up to α = 0.50, k = 0.022 l mol–1 min–1
a Without glass beads.
b Fraction boiling out up to 180°C.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 83 No. 10 2010

CHARACTERISTICS OF THE REACTION OF MANGANESE METAL
Table 5. Influence of the stoichiometric deficiency of oxalic
1843
acid on its reaction with manganese in 2-ethoxyethanol in
a bead mill at 25 ± 1°С
Time, min, of attainment of indicated
Mn conversion α
Oxalic acid dosage,
% of stoichiometric
amount значения
0.98
and
above
0.10 0.25 0.50 0.75
100
95
90
85
80
70
60
50
40
30
20
15
10
5
3
2
8
5
18
15
13
15
19
37
38
36
35
33
31
31
31
37
65
37
31
25
30
40
68
68
62
55
49
46
48
50
70
125
113
87
1
3
75
2
5
83
3
8
119
130
145
161
158
152
150
150
155
163
238
XMn, mol kg–1
4
12
13
14
13
13
14
14
14
15
40
Fig. 5. Time of attainment of practically quantitative
conversion of Mn metal to Mn(II) compounds in the reaction
of manganese with oxalic acid (71.4% of stoichiometric
amount) and water introduced with the acid (water of
crystallization), τα = 0.98, as a function of the initial Mn content
Mn. Liquid phase solvent 2-ethoxyethanol, temperature 29 ±
1°С. (1) Without additives and (2) in the presence of 0.4 mol
kg–1 MnO2 and 0.05 mol kg–1 iodine.
5
7
7
7
X
8
8
8
chemical schemes to account for the observed fact. It
seems more probable that the process is controlled by
the step of transport of the reagent Re occurring in the
liquid phase to the site of the chemical reaction via
adsorption. The process is described by the main mass
transfer equation
9
0
11
reactions involving the metal and consecutive-parallel
reactions involving primary transformation products,
e.g., basic salt. However, it is difficult and even hardly
possible to attribute the observed maxima to this factor.
Most probably, the cause is associated with different
strengths and structures of the blocking deposits formed
on the metal surface. The composition of these deposits
is naturally variable, so that in the course of the reaction
their strength can both increase and decrease. Numerous
examples can be found in the literature [9]. The use of
various stimulating additives is also associated with this
phenomenon.
W = KRFR([Rе] – [Rе]*),
(1)
where KR and FR are, respectively, the mass transfer
coefficient (adsorption coefficient of reagent Re) and
working (not occupied by product deposits) area of the
phase contact surface; [Rе] and [Rе]* are the running
and equilibrium (with the surface concentration on the
metal) concentrations of the reagent whose adsorption
on the metal surface is the limiting step of the process.
If the chemical reaction on the surface is fast, the
surface concentration of the reagent Re will tend to zero.
Hence, [Re]* → 0 and
It was already noted above that, in some cases, the
product accumulation occurred in accordance with the
rate equation for an irreversible zero- and/or first-order
reaction. Because the processes are heterogeneous
and diffusion-controlled and the reaction rate on
replacement of only a liquid phase solvent can change
by a factor of not only several units, but even several
tens and hundreds, there are no grounds to search for
W = KRFR[Rе].
(2)
Here the result will largely depend on the type of the
function FR = f(τ). If FR ≈ const, which is quite realistic
when the major part of the physical surface area is
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POZHIDAEVA et al.
Table 6. Influence of the molar ratio of phenol to 2-propanol or water in the initial solution on the reaction of these agents with
manganese at 22 ± 1°С in butyl acetate as liquid phase solvent in bead mill. Initial Mn content 1.0 mol kg–1
Reagent, mol kg–1
Time, min, of attainment of indicated Mn conversion α
phenol
2-propanol (water)
0.10
0.25
0.50
0.75
0.98 and above
Phenol–2-propanol
60
2.00
1.97
1.90
1.75
1.50
1.25
1.00
0.75
0.50
0.25
0.10
0
0
10
23
92
118
342
970
745
482
285
200
211
238
120
145
214
150
684
1560
1270
811
410
288
282
287
150
165
321
0.03
0.10
0.25
0.50
0.75
1.00
1.25
1.50
1.75
1.90
2.0
132
233
705
531
383
210
154
157
161
93
125
120
103
43
57
49
40
8
480
354
251
120
95
88
82
61
7
33
87
19
57
121
Phenol–water
60
1.95
1.80
1.65
1.50
1.25
1.00
0.75
0.50
0.25
0.15
0.05
0
0.05
0.20
0.35
0.50
0.75
1.00
1.25
1.50
1.75
1.85
1.95
2.00
25
75
55
38
33
25
21
13
16
57
41
33
113
138
215
275
253
192
173
158
65
163
158
320
480
407
350
307
263
94
219
175
480
570
550
540
458
337
125
150
479
108
108
105
112
118
106
63
36
80
92
113
243
115
127
197
572
Not attained in 1250 min
W = const.
(4)
blocked by product deposits (FB), i.e., when FR << FB,
then at KR ≈ const Eq. (2) will take the form of a rate
equation for an irreversible first-order reaction:
The correspondence to Eq. (3) or (4) is possible only
in certain (sometimes large with respect to conversion
intervals) steps of the process. There is always
a moment when Eqs. (3) and (4) cease to be observed.
Furthermore, there may be cases when the reaction
does not clearly follow Eq. (3) or (4) at all. At a large
excess of the reagent, the reaction instead of Eq. (4) can
follow Eq. (3) or a certain, more complex, equation.
W = keff[Rе].
(3)
At a large excess of reagent Re, e.g., when an alcohol
is used both as reagent and as liquid phase solvent, the
rate equation of the reaction will take the form of a zero-
order rate equation:
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 83 No. 10 2010

CHARACTERISTICS OF THE REACTION OF MANGANESE METAL
1845
Vestn. Nizhegor. Univ. im. N.I. Lobachevskogo, 2007,
no. 36, pp. 72–76.
This depends on the form of the function FR = f(τ),
determined by the parameters of the steps of breakdown
of surface deposits and fine disintegration of particles
changing their size owing to surface deposits. If there
were no surface deposition, the metal particle size
would not increase in the course of the process. Only
disintegration to the size determined by the performance
of the bead mill would be observed. On reaching this
moment, the process would sharply decelerate up to
practical cessation. Virtually 100% metal conversion
into the product would never be attained. In practice,
however, it is attained, and rather frequently. Here we
can see the positive role of the surface deposits.
2. RF Patent 2076106.
3. Luchinskii, G.P., Khimiya titana (Titanium Chemistry),
Moscow: Khimiya, 1971.
4. RF Patent 2223925.
5. RF Patent 2088319.
6. Matveev, Yu.S. and Kuchin, A.V., Khim. Rast. Syr’ya,
2001, no. 2, pp. 21–29.
7. Preparative Inorganic Reactions, Jolly, W.L., Ed., New
York: Interscience, 1965, vol. 2.
8. Ivanov, A.M. and Grechushnikov, E.A., Zh. Prikl. Khim.,
2008, vol. 81, no. 4, pp. 559–564.
CONCLUSIONS
9. Ivanov, A.M. and Pozhidaeva, S.D., Ispol’zovanie
bisernoi mel’nitsy dlya predotvrashcheniya
preodoleniya samoprekrashcheniya okislitel’no-
i
(1) In an efficiently operating bead mill, manganese
metal fairly readily, rapidly, and in many cases
quantitatively reacts not only with carboxylic acids, but
also with fatty alcohols, phenols, water, and mixtures
of these compounds in the form of their solutions in
organic solvents. Despite very large difference in рKа
values for acids, phenols, and alcohols, the rates of the
reaction of these compounds with manganese are not
only comparable but often even close.
vosstanovitel’nykh i inykh protsessov s uchastiem oksidov
perekhodnykh metallov i prakticheskie resheniya na
baze takogo podkhoda (Use of Bead Mill for Preventing
and Overcoming Self-Cessation of Redox and Other
Processes Involving Transition Metal Oxides and
Practical Solutions Based on Such Approach), Kursk:
Kursk. Gos. Tekh. Univ., 2008.
10. Pozhidaeva, S.D., Ivanov, A.M., Grechushnikov, E.A.,
and Mayakova, T.A., in Problemy prirodopol’zovaniya
i ekologicheskaya situatsiya v evropeiskoi Rossii i
sopredel’nykh stranakh (Problems of Nature Management
and Environmental Situation in European Russia and
Adjacent Countries), Moscow: Politerra, 2008, part 3,
pp. 61–64.
(2) Oxidation of manganese with water leads to the
formation of comparable amounts of Mn(II) compounds
and compounds of Mn in a higher oxidation state, formed
by heterogeneous oxidation of Mn(II) with atmospheric
oxygen.
(3) In reactions of manganese with mixtures of
acidic reagents, both significant acceleration and
strong deceleration of the overall redox process can be
observed, depending on the molar ratio of the acidic
reagents, their nature, and absolute amount of each
reagent in the reaction mixture.
11. Pozhidaeva, S.D., Ivanov, A.M., Grechushnikov, E.A.,
and Mayakova, T.A., Izv. Kursk. Gos. Tekh. Univ., 2008,
no. 1(22), pp. 30–39.
12. RF Patent 2294921.
13. RF Patent 2316536.
14. RF Patent 2331629.
15. RF Patent 2326861.
16. RF Patent 2326107.
17. RF Patent 2307118.
18. RF Patent 2304575.
19. RF Patent 2291856.
20. RF Patent 2291855.
(4) The observed correspondence of the kinetic
curves for separate components of the system to rate
equations for irreversible zero- and first-order reactions
is accounted for by the mechanism in which the limiting
step is adsorption of the reagent dissolved in the liquid
phase on the working surface of manganese as the site
of the redox reaction.
REFERENCES
21. Lux, H., Anorganisch-chemische Experimentierkunst,
Leipzig: Barth, 1959, 2nd ed.
1. Drobotenko, V.V., Balabanov, S.S., and Storozheva, T.I.,
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 83 No. 10 2010