Journal of Hazardous Materials 280 (2014) 315321

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Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

Promotion effect of KMnO4 on the oxidation of As(III) by air

in alkaline solution
Yuhu Li , Zhihong Liu, Fupeng Liu, Qihou Li, Zhiyong Liu, Li Zeng
Metallurgical Science and Engineering School, Central South University, Changsha 410083, China

h i g h l i g h t s

g r a p h i c a l

KMnO4 shows superstoichiometric

The mechanism of the oxidation of arsenic by air in the presence of KMnO4 : (a) Oxidation of Mn2+ and
formation of MnO2 ; (b) Catalytic oxidation of arsenic; (c) Oxidation of arsenic by dissolved oxygen; (d)
Dissolution and precipitation of Mn2+ .

oxidation for arsenic in solution.

Adding KMnO4 to alkaline solution
could improve the kinetics of arsenic
oxidation.
MnO2 acts as a catalyst to prompt
reaction between As(III) and dissolved oxygen.
The mole ratio of As/Mn and pH has
signicant effects on As(III) oxidation.
The adsorption and desorption of
MnO2 with As(III) and oxygen occurs.

a r t i c l e

i n f o

Article history:
Received 21 May 2014
Received in revised form 6 August 2014
Accepted 7 August 2014
Available online 17 August 2014
Keywords:
Arsenic oxidation
Air oxidation
Promotion effect
Potassium permanganate
Catalytic oxidation

a b s t r a c t
The mechanism of oxidation of As(III) in alkaline solution by air with promotion effect of KMnO4 was
studied. The experimental results indicated that the superstoichiometric oxidation of As(III) by KMnO4
could be attributed to the catalytic effect of reductive product of KMnO4 . The XRD and XPS results demonstrated that the catalyst was nascent MnO2 rich in potassium. The results also showed that the mole ratio
of Mn/As and the initial pH had signicant effects on the oxidation of As(III). The time for the oxidation by
air was less than 2 h with the mole ratio of Mn/As less than 1/10.5 and the initial pH higher than 13. The
kinetics of the catalytic oxidation of arsenic was interpreted using the pseudo rst order reaction, and
the apparent active energy was about 15.01 kJ/mol. The study suggested that the initial oxidation was
rstly dominated by the direct oxidation of KMnO4 followed by the catalytic oxidation with the nascent
MnO2 .
2014 Elsevier B.V. All rights reserved.

1. Introduction
Arsenic is a toxic element for human and animals, and the longterm intake of small doses of arsenic has led to the increased
occurrence of many cancers particularly those of the skin and bladder [1]. The behavior of arsenic in aqueous solution is strongly

Corresponding author. Tel.: +86 731 8883 0478.

E-mail addresses: lyh csu@163.com, hu115 2hu@hotmail.com (Y. Li).
http://dx.doi.org/10.1016/j.jhazmat.2014.08.008
0304-3894/ 2014 Elsevier B.V. All rights reserved.

a b s t r a c t

affected by the valency of arsenic [2,3]. Since As(III) is much more

toxic and more transportable than As(V), it is necessary to oxidize
As(III) to As(V) in the treatment of arsenic bearing solution [4,5].
The current methods on oxidation of arsenic include direct chemical oxidation [68], which is characterized with high efciency
(>99%) but costly, photocatalytic oxidation [912] and biological
oxidation [13,14]. For the photocatalytic oxidation using visible
radiation, there is still a large gap when compared to the case of
using high-energy radiations, such as ultraviolet radiation [9]. The
research of biological oxidation has been employed to oxide As(III)

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Y. Li et al. / Journal of Hazardous Materials 280 (2014) 315321

in drinking water plants, but this method was only suitable for low
levels of arsenic due to the lack of bacterial strain of high inhibitory
concentration for As(III) [15]. More recently, the advanced oxidation processes, using reactive oxygen species (O2 , H2 O2 , OH, or
other oxidizing intermediates) as the oxidants, have been successfully developed to treat arsenic bearing groundwater or drinking
water, but most of them use UV radiation instead of sunlight to promote the oxidation of arsenic, resulting in large cost of treatment
[1,16,17]. Therefore, strong oxidants such as H2 O2 [6], Cl2 [18],
NaClO [19], O3 [20] and KMnO4 [7] are normally used, especially
for the solution containing high concentration of arsenic. Although
the efciency of oxidation by these strong oxidants is satisfactory,
for example, it has been reported that a 1.0 mg/L free chlorine dose
was able to oxidize 100 g/L As(III) in less than 5 s [21], the high cost
limits their industrial application. It is urgent to explore a method
with low cost on the oxidation of arsenic.
Undoubtedly, the oxidation of arsenic by air is a promising
method, however, the slow kinetics/oxidation rate limit its application [19,22]. For example, some researchers found that only 57%
and 54% As(III) is oxidized at pH of 7.68.5 with oxygen and air
after 5 days, respectively [20]. Scott and Morgan even concluded
that dissolved oxygen had no effect on the oxidation of the As(III)
[21,23].
Although it was feasible for the oxidation of As(III) with dissolved O2 thermodynamically (GAsO 3 /AsO = 457.79 kJ/mol),
4

the reaction was kinetically controlled by the high activation

energy. The key to solve this barrier is to reduce the activation
energy to improve reaction kinetics of the oxidation of As(III) by
air. The introduction of a catalyst in the reaction system is a way.
Actually, some metal ions have been found to exist a certain promotion for the oxidation of As(III), such as Fe(III), Fe(II) and Cu(II)
[2426]. Kim et al. [20] reported that As(III) cannot be oxidized at
pH 3.57.5 by dissolved O2 but in the presence of Fe(II). Emett and
Khoe [10] conrmed that dissolved Fe(III) would act as a catalyst
for the reaction between arsenic and oxygen by emitting near-UV
light. In addition, it is reported that the rate of oxidation of As(III)
with dissolved oxygen could be improved in the presence of peroxydisulfate by using sonochemical methods [27]. The latest study
indicated FeMn binary oxide was positively correlated with As(III)
oxidation in the aeration-direct ltration (AF) process [28,29].
These results triggered researchers that it is feasible to employ
some catalysts to promote the oxidation of As(III) by air. Most of
the studies involving the interactions of arsenic and Mn oxides
only focused on the removal of arsenic in groundwater, while little
attention was given to the mechanism, especially for the treatment
of high concentrations of arsenic. In our tentative experiments, it is
found that the addition of KMnO4 greatly improved the oxidation
efciency of As(III) with air, but the mechanism was unknown. In
this paper, a new process for catalytic oxidation of As(III) in which
air is used as an oxidant with the addition of KMnO4 is further
investigated at laboratory scale. The study is expected to motivate
the researchers interest on the catalytic oxidation of arsenic and
to develop a new method for the oxidation of arsenic with low cost
and high efciency.

2. Experimental
2.1. Materials
All chemicals were of analytical grade and used without
further purication. All solutions were prepared using deionized water (resistivity 18.2 M cm; TOC < 10 g/L). A stock of
0.334 mol/L As(III) solution was made by dissolving 43.35 g of
NaAsO2 (>99%, Sinopharm) in 1000 mL of deionized water. 2 M
stock solutions of NaOH (>96%, Xilong) and HNO3 (>65%, Xilong)

were used as pH adjuster. The reagents used for spectroscopic

determination, including (NH4 )6 Mo7 O24 4H2 O (>99%, Sinopharm),
K(SbO)C4 H4 O6 0.5H2 O (>99%, Sinopharm) and ascorbic acid (>99%,
Sinopharm), were those quoted by the ISO norm [30].
2.2. Methods
For each test, 500 mL of 0.06670.334 mol/L As(III) solution was
made by diluting the stock solution with predetermined volumes
of deionized water, and the initial pH measured with a combined
glass electrode was adjusted using NaOH or HNO3 solution for
the experiments at pH 1214. The resultant solution was stirred
at 300 rpm and heated by a thermostat circulating water bath. A
designated quantity of KMnO4 (0.13, 0.25, 0.50, 0.75, 1.05 g) was
then added into the solution after it reached the setting temperature (15, 40, 60, 80, 90 C) while the air was conducted into the
ask at a certain ow rate (0, 0.1, 0.2, 0.3, 0.4, 0.5 m3 /h). Each of
10 mL slurry was sampled and ltered immediately through a cellulose acetate membrane of 0.45 m pore size every 30 min, and
the liquor ltered from the sample was acidied with 20% HCl for
the determination of As(III) and the total As. The precipitates were
collected, washed with deionized water and dried at 50 C for 48 h
in a vacuum drying oven before sampled for X-ray diffraction (XRD)
and X-ray photoelectron spectroscopy (XPS) analysis.
2.3. Characterization
As(V) was determined by molybdate-bule method [31], which
was an optimization of the colorimetric method of Johnson and
Pilson [32] to accurately measure arsenic concentrations in the
2400 g/L range in water. Total As was measured by inductively
coupled plasma atomic emission spectroscopy (ICP-AES). All samples and standards were treated according the standard methods
[33]. The concentration of As(III) was obtained from the difference
between total As and As(V). The residue was identied by X-ray
and scans from
diffraction (Siemens D5000, Cu K,  = 1.541874 A),
10 to 70 2 were made at rates of 5 2/min. The valence state
of Mn element in the solid was performed by X-ray photoelectron
spectroscopy (PHI5300, PERKIN-ELMER) using a monochromated
Al K X-ray source (hv = 1486.6 eV) at a spot size of 500 m in
diameter.
3. Results and discussion
3.1. Factors affecting the oxidation of As(III)
The performance of KMnO4 in catalytic oxidizing As(III) with air
under different conditions, including the mole ratio of Mn/As, pH,
temperature, and air ow rate, was investigated.
3.1.1. Effect of the mole ratio of Mn/As
The results shown in Fig. 1 revealed that the oxidation of arsenic
increased with the increase of the molar ratio of Mn/As. More than
5 h were needed to completely oxidize As(III) with the molar ratio
of Mn/As of 1/21 in comparison to that of 2 h with the molar ratio of
Mn/As of 1/10.5. According to Eqs. (1) and (2), the theoretical mole
ratio of Mn/As for complete oxidation of As(III) with KMnO4 was
about 1/2.5. Lee et al. also conrmed that the stoichiometry ratio
of Mn(VII)/As(III) was 1/(2.49 0.09), when As(III) was in excess of
permanganate [34]. However, the experimental results indicates
that the amount of KMnO4 for complete oxidation of As(III) was
much less than the theoretical value under the condition of aeration. Given that only air could be involved in the oxidation reaction
except for KMnO4 , it can be inferred that oxygen was involved in the
reaction as an oxidant. However, the previous study demonstrated
that oxygen was not an effective oxidant for As(III) oxidation in

Y. Li et al. / Journal of Hazardous Materials 280 (2014) 315321

Fig. 1. Effect of the mole ratio of Mn/As on the oxidation of arsenic. Air ow
rate = 0.2 m3 /h; initial pH = 13; temperature = 80 C; initial [As(III)] = 0.0667 mol/L.

aqueous solution, since only 54% As(III) was oxidized to As(V) in ve

days when air was used as the only oxidant [20,21,23]. Thus, it can
be supposed that there must be a promotion effect with the addition of KMnO4 in the reaction system. The total oxidative reaction
of arsenic included two consecutive reactions: the initial oxidation
was rstly dominated by the direct oxidation of KMnO4 followed by
the catalytic oxidation with the nascent MnO2 by air. The oxidative
reaction of As(III) can be expressed as follows:
5AsO2 + 2MnO4 + 3OH + 3H2 O = 2Mn(OH)2 + 5HAsO4 2 (1)
5AsO2 + 2MnO4 + 8OH = 2Mn(OH)2 + 5AsO4 3 + 2H2 O

2AsO2 + O2 + 2H2 O = 2HAsO4

(2)

+ 2H

(3)

2AsO2 + O2 + 2H2 O = 2AsO4 3 + 4H+

(4)

3.1.2. Effect of the initial pH

As it is shown in Fig. 2, the oxidation of As(III) increases sharply
with the increase of initial pH of the feed from 12 to 14 and reached
nearly 100% in 3 h. The oxidation of As(III) was not complete when
the initial pH was less than 12.5. Since the reductive product of
KMnO4 existed as ionic species at low pH values, such as Mn2+ ,
or solid at high pH values, such as Mn(OH)2 or Mnx Oy , the phenomenon above indicated that the promotion effect was caused by
manganese oxide or manganese hydroxide rather than manganese

Fig. 3. The XRD pattern of the precipitates obtained from the solution.

ions. Some researchers found that manganese existed as several

solid forms in alkaline solution, such as Mn(OH)2 , MnO2 nH2 O,
MnOOH, MnO(OH) [5,35]. To identify the cause of promotion effect,
the precipitate in the solution was sampled and characterized by
XRD, and the results are shown in Fig. 3. As seen, the precipitate was probably the nascent MnO2 rich in potassium, maybe as
K0.27 MnO2 (H2 O)0.54 . Scott and Morgan reported that the amount
of dissolved oxygen could not affect the oxidation of arsenic when
MnO2 is employed, and MnO2 only acts as an oxidant but a catalyst
[23]. This viewpoint was not supported by some researchers, who
argued that MnO2 would not exhibit the catalytic effect with the
absence of reductants in the solution [36], such as Mn2+ or Fe2+ .
However, the results from this paper indicated that this was not
the case; it was found that the magnication of catalytic effect of
MnO2 did not depend on the presence of reluctant, but pH value
of the solution. This is why the reductive product of KMnO4 , probably K0.27 MnO2 (H2 O)0.54 , which is a potassium manganese oxide
hydrate with a rhombohedral structure, had a signicant promotion effect for the oxidation of arsenic with air when the initial pH
was higher than 12.5.
3.1.3. Effect of the initial concentration of As(III)
As it is shown in Fig. 4, the oxidation of As(III) gradually
decreased with the increase of the initial concentration of As(III).
Only 92% of As(III) was oxidized to As(V) even in 19 h when the
initial concentration of As(III) was 0.334 mol/L, while the oxidation
of As(III) is completed after 2 h when the initial concentration of
As(III) was 0.0667 mol/L. It was also observed that the pH value of

pH=14
pH=13
pH=12.5
pH=12

80

100
The oxidation of As(III) (%)

The oxidation of As(III) (%)

100

317

60

40

20

80
60
Intial As(III) concentration
0.0667 mol/L
0.1335 mol/L
0.2002 mol/L
0.2670 mol/L
0.3337 mol/L

40
20

0
0

10

Time (h)

10

12

14

16

18

20

Time (h)
Fig. 2. Effect of the initial pH on the oxidation of As(III). Initial[As(III)] = 0.0667 mol/L; mole ratio of Mn/As = 1/10.5; air ow rate = 0.2 m3 /h;
temperature = 40 C.

Fig. 4. Effect of the initial concentration of As(III) on the oxidation of As(III). Mole
ratio of Mn/As = 1/10.5; air ow rate = 0.2 m3 /h; initial pH = 13; temperature = 80 C.

318

Y. Li et al. / Journal of Hazardous Materials 280 (2014) 315321

The oxidation of As(III) (%)

100
80
60
40
20
0

Fig. 5. The XRD patterns of the solid obtained at different initial concentrations of
As(III).
(a) 0.0667 mol/L; (b) 0.1335 mol/L; (c) 0.2002 mol/L.

nal solution gradually decreased from 12.92 to 12.23 increasing

the initial concentration of As(III) from 0.0667 to 0.334 mol/L.
According to Eqs. (3) and (4), the release of the hydrogen ion
during the oxidation of As(III) determines the decrease of the pH
value of the solution, resulting the dissolution of MnO2 served as
catalyst. The results showed in Fig. 5 also conrmed it. The characteristic peak of K0.27 MnO2 (H2 O)0.54 weakened and disappeared
with the increase of the initial concentration of As(III). The dissolution of MnO2 resulted in poor crystallinity of MnO2 and the
decrease of MnO2 precipitate, therefore, the oxidation of arsenic
would inevitably be affected.
3.1.4. Effect of air ow rate
As it is shown in Fig. 6, the oxidation of arsenic is completed
after 2 h by blowing air with a ow rate of 0.1 m3 /h, while it is
completed after 14 h without blowing air. This result is in contrast
with other studies that show that the reaction between air or oxygen and As(III) is hardly proceed [19,20,23]. As described above, the
reason for the oxidation of As(III) by air in this experiment could
be attributed to the catalytic effect of MnO2 , but there is no doubt
that dissolved oxygen was the oxidant for As(III), and the concentration of dissolved oxygen directly affected the reaction kinetics.
The results shown in Fig. 6 also indicated that increasing the air
ow rate had little effect on the oxidation of arsenic when it was
higher than 0.1 m3 /h. Blowing air to the reactor would increase
the dissolution rate of oxygen to maintain the concentration of

2
Time (h)

Fig. 7. Effect of temperature on the oxidation of As(III). Initial

[As(III)] = 0.0667 mol/L; mole ratio of Mn/As = 1/10.5; air ow rate = 0.2 m3 /h;
initial pH = 13.

dissolved oxygen and also improve the reaction kinetics by accelerating transfer of dissolved oxygen and As(III) into the particles of
the catalyst since the heterogeneous catalytic reaction was always
dominated by diffusion and adsorption.

3.1.5. Effect of temperature

As seen from Fig. 7, the time for complete oxidation sharply
shortened with the increase of temperature. The oxidation of As(III)
rapidly increased when temperature increased from 40 C to 80 C,
and only a slight increase was observed when temperature further
increased. It can be explained that it was favorable to accelerate
the oxidation reaction rate between As(III) and dissolved oxygen
since the amount of activated molecules and the chance of the
reaction molecule collision rapidly increased with the increase of
temperature. In addition, another reason for the increase of arsenic
oxidation was the difference in the structure of the reductive products of KMnO4 at different temperature, which greatly affected the
catalytic property. As it is shown in Fig. 8, K0.27 MnO2 (H2 O)0.54 ,
which may act as a catalyst, was produced only when temperature
exceeded 40 C, or an amorphous product was obtained. However,
the solubility of oxygen in solution decreased rapidly as the temperature increased, which restrained the oxidation of As(III) at certain
degree. For example, the solubility of oxygen is 3.08 103 g/100 g
H2 O at 40 C and 1.38 103 g/100 g H2 O at 80 C [34].

The oxidation of As(III) (%)

100
80
Air flow rate
3
0 m /h
3
0.1 m /h
3
0.2 m /h
3
0.3 m /h
3
0.4 m /h
3
0.5 m /h

60
40
20
0

6
8
Time (h)

10

12

14

Fig. 6. Effect of air ow rate on the oxidation of aqueous As(III). Initial

[As(III)] = 0.0667 mol/L; mole ratio of Mn/As = 1/10.5; initial pH = 13; temperature = 80 C.

Fig. 8. The XRD patterns of the solid obtained at different temperature.

(a) 90 C; (b) 80 C; (c) 60 C; (d) 40 C; (e) 15 C.

Y. Li et al. / Journal of Hazardous Materials 280 (2014) 315321

-7.5

319

0
-50

ln K= -2.43/T-1840.68

-7.8

-100

-8.1

ln K

Gr /kJ

-150

-8.4

-200
-250

-8.7

-300

-350
0

-9.0
0.0028

0.0030

0.0032

0.0034

1/T
Fig. 9. The pseudo rst order rate constants at different temperatures. Initial
[As(III)] = 0.0667; mole ratio of As/Mn = 10.5; air ow rate = 0.2 m3 /h; pH = 13.

20

40

60

80

100

C
Fig. 10. The change of the Gibbs free energy for the oxidation reaction of arsenic
and manganese by dissolved oxygen.

3.3. Reaction mechanism of the oxidation of As(III)

3.2. Catalytic kinetics of the oxidation of As(III)
The reaction between dissolved oxygen and As(III) could be
expressed as:
MnO

a As(III) + b ODIS 2 c As(V)

where ODIS is dissolved oxygen. The overall rate equation for the
reaction may be expressed by

d[As(III)]
= k[As(III)]a [ODIS ]b
dt

where a and b are the order of the reaction with respect to the concentrations of As(III) and dissolved oxygen. Since air ow was great
enough, the concentration of dissolved oxygen can be assumed to
be constant over the course of the reaction. Thus, the rate function
can be written as follows

d[As(III)]
= k [As(III)]a
dt

where [As(III)] and [ODIS ] are the concentrations of As(III) and

dissolved oxygen at any time. Since the initial oxidation was dominated by the direct oxidation of KMnO4 , and the oxidation was very
fast with reaction time less than 1 min [8,34], thus the experimental
data in the rst half hour was removed to avoid the direct oxidation
of KMnO4 before establishing reliable kinetics model for catalytic
oxidation. Preliminary kinetic experiments were carried out with
400 mL solution of 0.0667 mol/L As(III) with the mole ratio of Mn/As
of 2/21 by blowing air with a ow rate of 0.2 m3 /h at 40 C and various pH. Under these conditions, values of ln [As(III)] were linear
as a function of time, and similar slopes (k ) were obtained when
different initial concentrations of As(III) were used at constant pH,
temperature, air ow and the mole ratio of Mn/As. This is indicative
of the independence of the pseudo rst order rate constant of the
initial As(III) concentration in each reaction. The pseudo rst order
rate constants, k at different temperature are shown in Fig. 9; the
apparent energy of activation is about 15.0053 kJ/mol with initial
solution of 0.0667 mol/L As(III) and the mole ratio of Mn/As of 2/21
by blowing air with ow rate of 0.2 m3 /h at pH of 13, indicating
that the oxidation of arsenic was dominated by a diffusion process,
which was consistent with experiment phenomena.

It is well known that there are four major solid species for manganese in alkaline system: Mn(OH)2 , Mn3 O4 , MnOOH and MnO2 .
As it is shown in Fig. 10 and Table 1, the oxidation of other
manganese species except MnO2 by dissolved oxygen could all
occur since the changes of Gibbs free energy of these reactions
are negative [37,38]. The species of Mn3 O4 and MnOOH can be
easily oxidized by dissolved oxygen other than being reduced by
arsenic. Therefore, according to the results of thermodynamic calculation, the promotion effect of arsenic oxidation by oxygen could
be attributed to MnO2 , and the reaction path can be described as
follows: Mn(OH)2 Mn3 O4 MnOOH MnO2 , which could be
demonstrated by the XRD and XPS results of the solid product
obtained in the reaction systems. The main species presented in
the XRD pattern was most probably MnO2 or K0.27 MnO2 (H2 O)0.54 .
The XPS analysis results in Fig. 11 further illustrated that the location of Mn2P3/2 peak was similar to that of Mn with a four valence
state, which locates in 642.55 eV. Thus, it can be inferred that the
promotion effect of arsenic oxidation by air was attributed to the
nascent MnO2 with potassium-rich, which was produced as the
reductive product of KMnO4 .

Fig. 11. XPS analysis result of the reductive product of KMnO4 at pH of 12.5 and
80 C.

320

Y. Li et al. / Journal of Hazardous Materials 280 (2014) 315321

Table 1
Possible oxidation reaction among As(III), Mn species and dissolved oxygen.
No.

Oxidation reaction

r Gm

1
2
3
4

The oxidation of Mn
species

6Mn(OH)2 + O2 (a) = 2Mn3 O4 + 6H2 O

4Mn3 O4 + O2 (a) + 6H2 O = 12MnOOH
4MnOOH + O2 (a) = 4MnO2 + 2H2 O
2MnO2 + 1.5O2 (a) + 2OH = 2MnO4 + H2 O

<0
<0
<0
>0

5
6
7

The oxidation of arsenic

Mn3 O4 + AsO2 + 3H2 O + OH = 3Mn(OH)2 + HAsO4 2

2MnOOH + AsO2 + OH + H2 O = 2Mn(OH)2 + HAsO4 2
MnO2 + AsO2 + OH + H2 O = Mn(OH)2 + HAsO4 2

<0
<0
<0

r Gm
is the difference in the chemical potential between the reactants and the reaction products at standard state.

It is reported that the particle surface of the nascent MnO2 carries a negative charge, and has a great deal of hydroxyl groups
[23,39]. As known, both As(III) and As(V) exist in the form of negative ions in alkaline solutions. Thus, the adsorption between the
nascent MnO2 and arsenic was not certainly caused by the Coulomb
interaction, and it referred to the adsorption and desorption of
hydroxyl groups of the nascent MnO2 particles with As(III) ions and
dissolved oxygen. Therefore, the mechanism of arsenic oxidation in
solution by air with the addition of KMnO4 at alkaline pH could be
described as follows: the reaction was initially dominated by the
direct oxidation of KMnO4 followed by the catalytic oxidation of the
nascent MnO2 . The adsorption and desorption of the As(III) ions and
dissolved oxygen and the desorption of As(V) occurred at the surface of MnO2 particles. The relevant reactions can be expressed as
follows:

is shown the mechanism of catalytic oxidation can be represented

by ve steps:

(6)

(1) An inner-sphere complex is formed by the adsorption between

As(III) and MnO2 ;
(2) Electron transfer; two electrons move from As(III)to Mn(IV);
(3) Mn O bond breaks, and As(III) is oxidized to As(V) while Mn(IV)
is reduced to Mn(II) in the form of Mn(OH)2 ;
(4) Another inner-sphere complex is formed by the adsorption
between oxygen adsorbed and Mn(OH)2 ;
(5) Mn(II) is re-oxidized with the Mn O bonds reconstructed.
Actually, the oxidation of Mn(II) is not one step reaction, and
it is widely believed that Mn(II) is rstly oxidized in the form
of MnO(OH), then MnO2 , which may involve with the heterogeneous or homogenous autocatalytic oxidation of Mn(II) [40].
In other words, the oxidation reaction between the dissolved
oxygen and Mn(II) or Mn(III) takes place prior to the oxidation of As(III) in alkaline solution, which was different from the
previous view [41].

Fig. 12 shows a schematic diagram of the redox reactions

between As(III) and dissolved oxygen in the presence of MnO2 . As it

Thus it can be easily concluded that MnO2 acts as a catalyst in

the oxidation of As(III) to As(V).

2MnO4 + 3AsO2 + 4OH = 2MnO2 + 3AsO4 3 + 2H2 O

MnO

2AsO2 + [O2 ]aq + 4OH 2 2AsO4 3 + 2H2 O

(5)

Fig. 12. Schematic diagram of the redox reactions between As(III) and dissolved oxygen in the presence of MnO2 .

Y. Li et al. / Journal of Hazardous Materials 280 (2014) 315321

4. Conclusions
Laboratory scale tests were carried out to investigate the oxidation of arsenic by air in the presence of KMnO4 and its mechanism
and kinetics from synthetic alkaline As(III) solutions. It was found
that the promotion effect of KMnO4 on the oxidation of arsenic by
air could be attributed to the catalytic effect of Mn species, probably the nascent MnO2 . The oxidation of As(III) sharply increased
with the increase of initial pH of feed from 12 to 14, and there were
no catalytic effect when the initial pH was less than 12, which may
be due to the dissolution of MnO2 at low pH. Furthermore, the oxidation reaction was an heterogeneous catalytic oxidation process,
which referred to the adsorption and desorption of the As(III) ions
and dissolved oxygen and the desorption of As(V) occurred at the
surface of MnO2 particles. The kinetics of the catalytic oxidation of
arsenic was interpreted using the pseudo rst order reaction, and
the apparent active energy was about 15.01 kJ/mol.
Acknowledgments
This research was funded by General Financial Grant from the
China Postdoctoral Science Foundation (2012M521544).
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