Kinetics of phenol oxidation with iron-manganese concretions

Article abstract of DOI:10.1134/S1070363212040147

Kinetics of oxidation of phenols on the iron-manganese concretions in the temperature range 293-353 K at pH 5.5±0.5 was studied. Reaction of oxidation on the iron-manganese concretions has the second order by phenol. It is characterized by low activation energy, 17.5 kJ mol^-1, due to the catalytic action of iron(III) oxide. Lower rate of oxidation of phenols on the iron-manganese concretions is observed as compared to oxidation on the pyrolusite surface. It occurs because of the decrease in MnO₂ concentration in the iron-manganese concretions.

Full text of DOI:10.1134/S1070363212040147

ISSN 1070-3632, Russian Journal of General Chemistry, 2012, Vol. 82, No. 4, pp. 685–692. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © O.V. Cheremisina, D.E. Chirkst, M.A. Sulimova, 2012, published in Zhurnal Obshchei Khimii, 2012, Vol. 82, No. 4, pp. 599–606.
Kinetics of Phenol Oxidation
with Iron–Manganese Concretions
O. V. Cheremisina, D. E. Chirkst, and M. A. Sulimova
St. Petersburg State Mining University, 21 liniya 2, Vasil’evskii Ostrov, St. Petersburg, 199106 Russia
e-mail: ovcheremisina@yandex.ru
Received April 28, 2011
Abstract—Kinetics of oxidation of phenols on the iron-manganese concretions in the temperature range 293–
3
53 K at pH 5.5±0.5 was studied. Reaction of oxidation on the iron-manganese concretions has the second
–1
order by phenol. It is characterized by low activation energy, 17.5 kJ mol , due to the catalytic action of
iron(III) oxide. Lower rate of oxidation of phenols on the iron-manganese concretions is observed as compared
to oxidation on the pyrolusite surface. It occurs because of the decrease in MnO
manganese concretions.
2
concentration in the iron-
DOI: 10.1134/S1070363212040147
The problem of decontamination of industrial waste
waters from the dissolved organic compounds, in
particular, of phenols, is one of the most important and
at the same time of most complicated goals. Firstly, the
diversity of chemical compositions of systems, of their
formation and existence requires performing special
studies for each case, which is not always possible.
Secondly, the technology of the sufficiently complete
decontamination of water requires as a rule the
maintenance of special conditions, which as a rule can
be hardly fulfilled in practice. And finally, many
effective methods of deep decontamination need large
economical and resource investments, using rare
reagents with their subsequent regeneration, utilization
or disposal of waste. That is why the search for new
effective methods of decontamination of industrial
waste waters is still actual.
the VIII group metals as well as copper, manganese,
and their compounds are used as catalysts.
The liquid phase oxidation of phenol in water
catalyzed with copper oxide applied on the active
aluminum oxide at 130–145°C, 1.0–1.3 MPa pressure,
and the contact time 45–90 min permitted to achieve
its complete destruction [1].
Manganese dioxide is also used as the phenol
oxidant [2-4]. At pH 9–10 it plays the role of catalyst,
2
+
and Mn cations formed in the course of oxidation
precipitate as the poorly soluble Mn(OH) hydroxide
2
on the surface of the mineral. Performing the oxidation
process in the acidic medium at pH < 4 is not desirable
due to the dissolution of manganese dioxide and the
2
+
transfer of Mn ions in the solution. Their maximum
–
1
permissible concentration is 0.1 mg l [5]. In [6] the
oxidation of phenol with manganese dioxide at pH 5–6
was studied in the temperature range 323–393 K
leading to formation of hydroquinone and p-benzo-
quinone. Their maximum permissible concentration is
Methods of decontamination of the phenol-
containing waters may be classified as the regenerative
and destructive. Destructive methods are used when
isolation of phenols from waste waters is impossible or
expensive. Main destructive methods of decontamina-
tion from the dissolved phenol are thermal oxidation,
oxidation, electrochemical oxidation, and hydrolysis.
–
1
0
.2 mg l which is 200 times higher than that of
–
1
phenol (0.001 mg l ). This oxidation is the second
order reaction in the temperature range 393–323 K and
proceeds in the kinetic regime with the activation
energy 42.0 kJ mol . In the temperature range 333–
353 K the reaction proceeds according to the first order
equation in the external diffusion regime with the
Using catalytic systems permits the decom-position
of practically all organic substances which can be
found in waste waters. Such treatment may cause deep
oxidation of organic substances up to CO and H O.
–
1
2
2
–
1
Metals of varied valence, their oxides and salts, mainly
activation energy 6.65 kJ mol .
6
85

6
86
CHEREMISINA et al.
Table 1. Chemical composition of concretions of the Finnish
bay [7]
double silicates with aluminum of ferrihydrite type
Fe Al (Al Si O )(OH) and manganese(IV). But the
a
5
2
2
6
22
5
kinetics of oxidation on natural minerals at high con-
centrations of phenols remains practically unstudied
Average content, wt Limits of changes in
Component
%
content, wt %
9.91–26.43
0.21–0.36
[8, 9].
SiO
TiO
Total Mn calculated
on MnO
2
17.87
0.28
Kinetics of oxidation of phenol in waste water with
2
natural minerals of manganese(IV) oxide containing
soft manganese mineral, rodochrosite, and hematite
[10] was studied. The oxidation of phenol with starting
33.80 (35.87)
15.51–53.43
2
–
1
concentrations 100–1000 mg l at different pH in the
temperature range 293–333 K proceeds in the diffusion
regime.
Al
Fe
2
O
3
4.49
1.63–6.39
10.31–33.98
0.94–2.14
0.93–2.21
2
O
3
20.19 (36.23)
1.59
MgO
CaO
The catalytic activity of iron-manganese concre-
tions would differ from the properties of pure MnO2
1.41
and the minerals with its high content due to the
Na
2
O
1.43
1.92
1.11–1.77
1.29–3.13
presence of a significant amount of iron(III). It is
presumable that Fe O also exhibits the catalytic
2
K O
2
3
activity. The catalytic system described in [10] in-
cludes the activated carbon modified with the iron
additives.
P
2
O
5
2.70
1.42–4.88
Ba
Sr
0.328
0.1–1.0
0.0027 (0.263)
0.0076
0.0005–0.0050
0.0030–0.0120
0.0030–0.0120
0.0012–0.0025
0.0010–0.0500
0.0005–0.0025
0.0020–0.0150
0.0020–0.0080
0.0001–0.0200
0.0005–0.0150
In the course of liquid phase oxidation in the
boiling layer on this catalyst about 98% conversion of
phenol was observed. Song et al. ascribe the observed
results to the action of iron as the agent stabilizing the
transition state of oxidized phenol molecules on the
surface. Besides, it was reported lately [11] that the
synthesis of heavy organic substances can take place in
the course of oxidation of phenols in the presence of
iron. That is why the establishment of the role of
iron(III) in the course of oxidation of phenol is
necessary.
V
Co
Cr
Ni
Y
0.0067
0.0016
0.0134
0.0015
Mo
Cu
Pb
Zn
0.0070
0.0034 (0.339)
0.0034 (0.449)
0.0057 (0.074)
We have studied kinetics of oxidation of phenol on
iron-manganese concretions in the temperature range
2
93–353 K at the pH of water phase 5.5±0.5. The
a
Mass content of the elements defined in [12] by X-ray analysis
is given in parentheses.
composition of the catalyst evaluated by means of X-
ray luminescent method [14] is presented in Table 1.
Mass content of elements evaluated in [14] by
means of the X-ray fluorescent methods is given in
parentheses.
Analysis of reported data shows that natural
minerals containing manganese dioxide have good
adsorption properties and high catalytic ability while
demonstrating the oxidative properties [2–4]. For the
effective purification of the phenol-containing waste
waters of chemical-metallurgical plants it is promising
to use iron-manganese concretions. Mineral composi-
tion of iron-manganese concretions consists of todo-
rokite, vernardite, pyrolusite, psilomelane, and
ransierite [7]. Main mass of the ore part contains iron
hydroxides in a form of hydrogetite FeO(OH) and
It was shown in [6] that at pH 5.5±0.5 the main
product of oxidation of phenol with manganese
dioxide is hydroquinone. p-Benzoquinone is formed in
2+
the yield less than 10 mol %. The absence of Mn
cations in solutions is confirmed by the X-ray
fluorescent data.
In Table 2 and in Fig. 1 the experimental
dependences of concentration of phenol on the time of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 4 2012

KINETICS OF PHENOL OXIDATION
Table 2. Dependence of concentration of phenol on time
687
с, M
323 K
t, min
2
93 K
303 K
313 K
333 K
343 K
0.0128
0.0127
0.0120
0.0112
0.0105
0.0109
0.0094
0.0098
0.0094
0.0081
–
353 K
0
2
5
0.0137
0.0152
0.0146
0.0129
0.0130
0.0115
0.0117
0.0099
0.0107
0.0104
0.0094
–
0.0126
0.0171
–
0.0149
–
–
0.0152
0.0131
0.0147
–
–
0.0140
1
1
2
2
3
3
4
5
6
7
9
0
5
0
5
0
5
5
0
0
0
0
0.0128
0.0141
0.0141
0.0119
0.0130
0.0129
0.0135
–
–
0.0108
–
–
0.0134
0.0114
0.0113
0.0114
0.0132
–
0.0105
0.0109
–
–
–
–
0.0098
0.0114
0.0128
0.0130
0.0104
0.0105
–
–
–
–
0.0094
0.0090
0.0107
–
–
–
–
–
0.0118
–
0.0080
0.0090
0.0081
–
0.0086
–
–
0.0104
–
–
–
–
0.0105
–
–
0.0088
–
0.0070
1
1
1
1
1
1
1
1
2
2
2
2
3
3
10
20
30
40
50
60
70
80
00
10
30
40
00
20
0.0097
–
0.0095
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
0.0096
–
0.0070
–
0.0063
–
0.0093
–
–
–
–
–
–
–
0.0065
–
–
0.0094
–
0.0080
–
–
–
–
–
–
0.0055
–
–
0.0082
–
–
–
–
–
–
0.0078
–
0.0083
0.0071
–
0.0053
0.0058
–
–
–
0.0063
–
–
–
–
–
–
–
0.0070
–
–
0.0070
–
–
–
–
–
–
0.0054
–
0.0071
–
–
–
–
0.0063
–
–
–
0.0036
0.0033
oxidation on iron-manganese concretions at pH
of the value of reverse concentration on time is
presented in Fig. 2. Linear trend equations and values
of rate constants, evaluated from the slopes are listed
in Table 3.
–
1
5
3
.5±0.5, V/m ratio 20 ml g and 293, 303, 313, 323,
33, 343, 353 K are presented.
Treating the results of measurements in the tem-
perature range 293–353 K showed that the de-
pendences obtained are described by the kinetic equa-
tions of the second order reactions. Linear dependence
The value of activation energy calculated from the
slope of linear trend E = R|tan α| (y = –2102.59x +
a
2
–1
5.75; R = 0.99) presented in Fig. 3 was 17.48 kJ mol .
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 4 2012

6
88
CHEREMISINA et al.
Table 3. Kinetic characteristics of oxidation of phenol
c
M
Rate constant k,
Т, K
Trend equation
–
1
–1
mol l–1 min
2
293
303
313
323
333
343
353
y = 0.271x + 75.43; R = 0.97
0.271
0.301
0.378
0.465
0.583
0.652
0.864
2
y = 0.301x + 67.35; R = 0.99
2
y = 0.378x + 66.93; R = 0.99
2
y = 0.465x + 86.03; R = 0.94
2
y = 0.583x + 77.26; R = 0.96
2
y = 0.652x + 81.91; R = 0.98
t, min
2
Fig. 1. Dependence of concentration of phenol on time at
the temperature, K: (1) 292, (2) 303, (3) 313, (4) 323,
y = 0.864x + 68.55; R = 0.95
(5) 333, (6) 343, and (7) 353.
–1
On the basis of the value n = 2 of the reaction order
t
1/c , M
–
1
and the activation energy 17.48 kJ mol it may be
suggested that in the temperature range 293–353 K the
rate of oxidation is limited by the chemical reaction
taking place on the surface. For the confirmation of
nature of the limiting stage the experiment at the V/m
–1
ratio 50 l kg was carried out. Obtained values of rate
–
1
–1
constants equal 0.269 mol l min at 293 K and
–
1
–1
0
.577 mol l min at 333 K and within the limits of
experimental error they agree with the values of
–
1
constants evaluated at V/m 20 l kg . The independence
of the reaction rate constant from the phase ratio at 293 and
3
33 K contradicts the diffusive regime of oxidation.
Lower values of the rate of oxidation of phenol on
the iron-manganese concretions as compared to
pyrolusite [6] is due to the 3–4 times decrease in the
MnO2 content in iron-manganese concretions as
compared to pyrolusite. From the data in [6] it follows
that in the temperature range 293–333 K the values of
rate constants of oxidation of phenol on pyrolusite vary
t, min
Fig. 2. Linear form of kinetic dependencies at the tempera-
ture, K: (1) 292, (2) 303, (3) 313, (4) 323, (5) 333, (6) 343,
and (7) 353.
1
/T
–
1
–1
from 0.314 to 1.556 mol l min , and at 333 K the
reaction goes over to the diffusive regime. Due to the
low content of MnO (35.87 wt %) in iron-manganese
2
concretions the decrease in the rate of the chemical
reaction occurs which limits the process of oxidation at
the increase in temperature from 333 to 353 K in
contrast to the oxidation on pyrolusite.
The decrease in the activation energy from 42.0 to
–
1
1
7.5 kJ mol at the transfer from pyrolusite to iron-
manganese concretions can be attributed to the
catalytic action of iron(III) oxide whose content is
ln k
-1
comparable with the content of MnO (Table 1). For
2
Fig. 3. Dependence of ln k = f(T ) in the temperature range
03–303 K.
2
the confirmation or rejection of this assumption we
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 4 2012

KINETICS OF PHENOL OXIDATION
689
carried out the oxidation of phenol on the surface of
pure Fe O and on a mixture of Fe O and MnO in 1:2
Table 4. Dependence of concentration of phenol on the time
of oxidation on the surface of Fe and a mixture of Fe
and MnO at 323 K
2
O
3
2 3
O
2
3
2
3
2
2
molar ratio characteristic of iron-manganese concre-
tions and at the ratio of volume of the liquid phase to
c, M
–1
the mass of solid V/m 20 l kg and 323 K.
t, min
Fe
2
O
3
2 3 2
Fe O + MnO
Results of this experiment are presented in Table 4
and Fig. 4.
333 K
0.0157
0.0155
0.0155
0.0149
0.0144
0.0137
0.0136
0.0131
0.0131
0.0123
0.0120
0.0115
0.0112
0.0109
0.0105
0.0101
0.0101
333 K
0.0155
0.0151
0.0149
0.0137
0.0126
0.0099
0.0111
0.0094
0.0094
0.0086
0.0090
0.0064
0.0066
0.0070
0.0062
0.0040
0.0034
0
2
5
Dependences of concentration of phenol on the
time of oxidation on the surfaces of Fe O and of the
2
3
mixture of Fe O and MnO are described by the
2
3
2
kinetic equations of the second order reaction. In Fig. 5
linear dependences of the reverse concentration on
time are presented. In Table 5 equations of linear
trends and the rate constants evaluated from the slopes
for Fe O3 and Fe O –MnO mixture are listed.
1
0
15
2
2
3
3
0
5
0
5
2
2
3
2
Analogous values for pure MnO were taken from [6].
2
In the kinetics of the liquid phase heterogenic
catalysis a significant role is played by the surface
concentration of catalyst because the liquid phase
oxidation of phenol takes place on the surface of solid
catalyst. That is why for evaluation of the real rate
constants of the process the values of specific surfaces
of iron-manganese concretions, of pyrolusite, and of
Fe O were measured. Results of these evaluations are
45
6
9
0
0
120
2
3
1
2
80
40
as follows.
Iron-manganese
concretions
Mineral
MnO
2
Fe
2
O
3
300
15
3
Specific surface,
35.39
40.34
9.67
2
–1
–
1
–1
m g
0
.997 mol l min . Within the limits of experimental
error it coincides with the value calculated from the
separate experimental rate constants of the reaction on
the surface of MnO and Fe O considering the molar
As the rate of heterogenic catalytic and heterogenic
reactions are referred to the unit of surface of catalyst
or the solid phase, the real rate constant of oxidation kr
can be calculated from the experimental value kexp
according to Eq. (3).
2
2
3
c
M
k
r
= kexp/c
s
.
(3)
Here c is the surface concentration of solid phase,
s
–
2
mol m calculated according to the formula (4).
= 1/(S M).
Here M is the molecular mass of MnO or Fe O .
c
s
s
(4)
2
2
3
Calculated k values for the oxidation at 323 K on
r
the surface of pure Fe O and MnO were 4.94×
2
3
2
5
–1
–1
6
–1
–1
1
0 m min and 5.6×10 m min respectively.
t, min
While studying the process on the surface of the
Fig. 4. Dependence of concentration of phenol on the time
of oxidation at 333 K. (1) on Fe surface and (2) on the
surface of a mixture of Fe and MnO
mixture of Fe O and MnO in 1:2 molar ratio the
value of the experimental rate constant was
2
3
2
2 3
O
2
O
3
2
.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 4 2012

6
90
CHEREMISINA et al.
the value of rate constant of the surface chemical reac-
–1
t
1/c , M
tion and significantly decreases the activation barrier.
Data [12] show that chemosorption of two-atomic
and more complex molecules proceeds mono-
molecularly or dissociatively. Molecular chemisorp-
tions proceeds with the preservation of bonds in the
adsorbed molecule. It is caused by the coordinational
interaction of adsorbate and adsorbent.
δ+
IV
–
δ–
>
6 5
Mn < (2О ) + 2 С Н ОН
δ+
IV
–
δ–
⇄
⇄
[> Mn < (2О )] ····· (2 С
6
Н
5
ОН),
(6)
δ+
III
–
δ–
>
Fe ―(О ) + С
6
δ–
Н
5
ОН
δ+
III
–
[> Fe ―(О )] ····· ( С Н ОН).
6 5
(7)
t, min
Fig. 5. Linear form of kinetic dependencies at 323 K.
1) Oxidation on Fe surface and (2) oxidation on a
surface of Fe –MnO mixture.
The specific feature of molecular chemisorptions is
also the low value of activation energy as was de-
monstrated in the process of oxidation of phenol on the
surface on iron-manganese concretions. The
interaction of the charged forms of oxygen in metal
oxides with the oxidized substance is accompanied by
the electron transfer to the catalyst.
(
2 3
O
2
2
O
3
parts of oxides ω in the mixture [Eq. (5)] which is
–
1
–1
equal to 1.160 mol l min
Fe
2 3
O
MnO
2
k
exp = kexp
ω
1
+ kexp
ω
2
.
(5)
δ+
IV
–
δ–
[
→
>
Mn < (2О )] ····· (2 С
6
Н
5
ОН)
ОН),
ОН)
ОН).
According to the data of Table 1 the molar part
δ+
II
–
+
>
Mn ····· (2О ) ····· (2 С
6
Н
5
(8)
(9)
values ω are 0.67 and 0.33 respectively. From the
δ+
III
–
δ–
1
[
>
>
6 5
Fe ―(О )] ····· ( С Н
calculated k values at 323 K on the surfaces of pure
δ+
II
–
+
r
→
6 5
Fe ····· (О ) ····· ( С Н
oxides Fe O and MnO considering the given molar
2
3
2
–
1
–1
The presence of electron transfers in the inter-
mediate interaction explains the exclusive role of the
transition metal compounds as the oxidation catalysts.
High catalytic activity of compounds of the transition
d-metals is caused by the comparatively low energy of
valence alterations of their ions, which facilitates the
electron transfer. A significant role belongs also to the
ability of formation of coordination compounds. The
electron transfer is the quick stage of oxidation. The
rate of the process would be limited by
chemimolecular adsorption [reactions (1), (2)] and the
ratio 1:2 kexp the value equal to 0.427 mol l min was
evaluated. It agrees with the experimental value
–
1
–1
0
.465 mol l min measured in the process of
oxidation on the surface of iron-manganese concretions.
Hence, the process of oxidation of phenols on the
iron-manganese concretions proceeds slower as
compared to pyrolusite which can be ascribed to the
decrease in concentration of MnO in iron-manganese
2
concretions. Nevertheless, the presence of iron(III)
oxide in the iron-manganese concretions contributes to
δ+
IV
–
stability of activation complexes [> Mn <(2O )]···
(
δ–
δ+
III
–
δ–
2 C H OH) and [> Fe <(O )]···( C H OH).
Table 5. Kinetic characteristics of oxidation of phenol on
6 5 6 5
the surface of minerals at 323 K
The activated complex with iron oxide is less
stable. This statement is based on the lower value of
energy of the iron-oxygen bond as compared to the
energy of manganese-oxygen bond [12]. The active-
tion energy of oxygen desorption is the sum of values
of the metal-oxygen bond energies and the activation
energies of oxygen adsorption. For the iron and
manganese oxides these values are comparable.
Rate constant k,
Oxidants
Trend equation
–
1
–1
mol l–1 min
2
Fe
Fe
2
2
O
3
3
y = 0.356x + 64.18; R = 0.97
0.356
0.997
1.556
2
O
+ MnO
2
y = 0.997x + 65.42; R = 0.95
2
а
MnO
2
y = 1.556x + 82.91; R = 0.98
The cleavage of activated complexes does not lead
to the formation of Mn and Fe cations in solution as
show the X-ray fluorescent analysis data. Evidently
a
2+
2+
Linear trend equation and value of the rate constant on MnO
surface at 323 K were evaluated in [6].
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 4 2012

KINETICS OF PHENOL OXIDATION
691
these ions remain on the surface of the solid phase and
then according to [8, 13] are oxidized with air oxygen
to form FeO and MnO.
aliquot was diluted in the measuring flask up to 10 ml
with 0.1 N hydrochloric acid and its optical density
was measured at the same wavelength against the
neutralized solution of sodium hydroxide.
Summary equations of the reactions may be
represented as follows:
Linear dependence of optical density on concentra-
–
1
tion is observed in the range up to 10 mg l ,
MnO
MnO(s) + 2 НО–С
2
(s) + 2 С
6
Н
5
ОН(sol) + Н
–ОН(sol) + 2 Нaq,
2
О(l)
–1
evaluation limit is 0.5 mg l . The evaluation of phenol
+
⇄
⇄
6
Н
5
is possible in the presence of nitrogen and sulfur
oxides, hydrogen sulfide, aldehydes, ketones, alcohols,
benzene and its homologs, but it is impeded by the
presence of amines exhibiting the same red shift [15, 16].
Fe (s) + 2 С
2FeO(s) + 2 НО–С
2
O
3
6
Н
5
ОН(sol) + Н О(l)
2
+
6
Н
5
–ОН(sol) + 2 Нaq.
Hence, the oxidation of phenol on iron-manganese
concretions in the temperature range 293–353 K has
the second order by phenol and is characterized by low
In alkaline medium at pH 13, the light absorption is
proportional to the content of phenol and its
derivatives, while at pH 7 it is caused only by the
presence of impurities. Absorption spectra of water
solutions of phenol, hydroquinone, pyrocatechol, and
–
1
value of activation energy (17.5 kJ mol ) due to the
catalytic action of iron(III) oxide. The lower rate of
oxidation of phenol on iron-manganese concretions as
compared to the rate on the surface of pyrolusite
–
1
resorcinol in the concentration 5 mg l at pH 7 showed
that no light absorption takes place only in the case of
phenol. Selectivity of evaluation is achieved due to the
red shift of the absorption bands in the alkaline
solutions of phenol and its derivatives as compared to
neutal ones (pH 7) caused by the formation of
phenolates. The content of phenol was found from the
difference of optical densities of solutions measured at
pH 13 and pH 7.
originates from the decrease in MnO concentration in
2
iron-manganese concretions.
The presence of iron(III) oxide in iron-manganese
concretions contributes to the value of the rate constant
of the surface-chemical reaction and significantly
decreases the activation barrier.
EXPERIMENTAL
In the course of our work specific surfaces of iron-
manganese concretions, of pyrolusite, and of pure
iron(III) oxide were measured. The specific surface
was evaluated by means of sorption of methylene blue
from water solution [17]. A batch of the air dry
sample, 5 g, was placed in a 100 ml Erlenmeyer flask
and 50 ml of 0.01 N methylene blue solution was
added by means of a pipette. The resulting mixture was
shaken and left for 12–14 h. The colored suspension
was twice filtered through the blue band filter. First
portions of filtrate (~10 ml) were thrown away because
of sorption of the methylene blue with filter. Aliquots
of filtrate and starting solution (1 ml) were diluted to
Experiments were carried out in the temperature-
controlled vessel loaded with 800 ml of aqueous
phenol solution with the concentration about 1 g l
–1
and 40 g of iron-manganese concretions of the granulo-
metric composition 1.0–2.0 mm. The vessel content
was stirred at a rate 400 rpm. After the definite time
intervals 15 ml aliquots were taken and the content of
phenol [15, 16] and manganese cations was analyzed
in them.
2
+
The content of Mn cations in solution was
evaluated by means of the X-ray fluorescent analysis
using the Spectroscan-U crystal diffraction spectrometer.
1
00 ml with water and optical densities of these
The phenol content was evaluated by the absorption
in the UV spectrum at 235 nm. For this purpose the
solutions at 665 nm were measured. From the value of
calculated concentration of methylene blue in filtrate
the capacity was evaluared by means of formula (1)
with the accuracy 0.1 meq.
1
ml aliquots of analyzed solution with the phenol
–1
content 1–0.1 g l were placed in the 100 ml measure-
ing flask, and 0.1 M sodium hydroxide solution was
added to the completion of the flask volume. From the
solution thus obtained two 5 ml aliquots were taken.
The first one was diluted in the measuring flask to
–3
–1
Е = (ΔсV×10 )/m (eq g ).
(1)
Here Δc is the difference in concentrations of starting
–
1
and equilibrium solutions of methylene blue, eq l ; V
1
0 ml with NaOH solution and optical density of the
solution obtained was measured on the wavelength
35 nm against the 0.1 M NaoH solution. The second
3
is the volume of starting methylene blue solution, cm ;
m is the mass of mineral batch, g.
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 4 2012

6
92
CHEREMISINA et al.
From the value of exchange capacity and the
dimensions of the area, occupied by one methylene
snabzheniya. Kontrol’ kachestva (Drinking Water.
Sanitary Demands to the Quality of Water of the
Centralized Systems of Potable Water Supply. Quality
Control), SanPiN 2.1.4.1074-01.
. Chirkst, D.E., Cheremisina, O.V., Sulimova, M.A.,
Kuzhaeva, A.A., and Zgonnik, P.V., Zh. Obshch. Khim.,
–20
2
blue cation equal to 95.6×10 m according to X-ray
measurements specific surface was calculated. As the
maximum amount of the adsorbed methylene blue
corresponds to the monomolecular layer of dye,
specific surface value can be found by means of
formula (2).
6
7
2
011, vol. 84, p 612.
. Konk etsii i konk etsionnyi analiz (Concretions and
r
r
Concretion Analysis), Zaritskii, P.V., Ed., Moscow:
Nauka, 1977.
2
–1
S = EN
A
W
0
(m g ).
(2)
8
9
. Uk ainczyk, L. and McBride, M.B., Clays and Clay
Minerals, 1992, vol. 40, no. 2, p. 157.
. Zhang, L.Z., Chen, Z.L., Ma, J., and Yu, M.,
Environmental Sci., 2006, vol. 27, no. 5, p. 945.
Here E is the value of capacity of adsorbent with
r
–
1
respect to methylene blue, eq g ; N is the Avogadro
A
constant, W is the area occupied by one methylene blue
cation.
1
1
0. Song, Y.X., Qiao, X.G., and Chen, T.X., Bull. Mineral
Petrol and Geochem., 2006, no. 4. p. 324.
ACKNOWLEDGMENTS
1. Quintanilla, A., Fraile, A.F., and Casas, J.A., Abstract
of Papers, European Conf. on Environmental Applica-
tions of Advanced Oxidation Processes no. 1, Chania,
Gresse (07/09/2006), 2007, vol. 146, no. 3, p. 250.
The work was carried our within the frame of the
analytical departmental target program “Development
of scientific potential of higher school (2009–2011)”
and Federal target program “Scientific and scientific-
pedagogical staff of innovational Russia” (2009–
1
1
2. Boreskov, G.K., Geterogennyi kataliz (Heterogenic
Catalysis), Moscow: Nauka, 1986.
3. McBride, M.B., Clay and Clay Minerals, 1989, vol. 37,
2
013).
no. 4, p. 34.
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