J. Ind. Eng. Chem., Vol. 13, No.

2, (2007) 231-236

Silver-Mediated Electrochemical Oxidation: Production of Silver (II)

in Nitric Acid Medium and in situ Destruction of Phenol in Semi-batch
Process
†
Manickam Matheswaran, Subramanian Balaji, Sang Joon Chung, and Il Shik Moon

Department of Chemical Engineering, Sunchon National University, Chonnam 540-742, Korea

Received August 14, 2006; Accepted November 30, 2006

Abstract: The mediated electrochemical oxidation was studied with Ag (II) as the mediator ion in nitric acid
medium. The oxidation of Ag (I) was performed in an electrochemical cell under various conditions, including
varying the temperature and the concentrations of nitric acid and mediator ions in a batch-type electrochemical
reactor in recirculation mode. The formation of Ag (II) increased upon increasing the concentration of nitric
acid, but it decreased at higher temperatures. The percentage of conversion decreased upon increaseing the
concentration of Ag (I). The destruction of phenol was performed in batch and continuous organic feeding
modes. A maximum destruction efficiency of 88.8 % (based on CO2) was achieved in the batch process. The
destruction efficiency during the continuous organic feeding increased upon increasing the temperature and in-
itial concentration of Ag (I) up to 0.5 M. The destruction was also tested in the long run for 2 h; the steady
state destruction efficiency was 75 %, based on CO2 production.

Keywords: mediated electrochemical oxidation, silver (I), destruction efficiency, phenol, organic destruction,
carbon dioxide

Introduction In the electrochemical cell,

1)
The mediated electrochemical oxidation (MEO) process
is an emerging new technology for the destruction of or-
ganic waste materials. In this process, the hazardous or
mixed organic waste streams can be destructed at am-
bient temperatures (less than 100 oC) and atmospheric
pressure. In the MEO process, the mediator oxidant is re-
generated continuously by an electrochemical cell to
minimize the production of secondary wastes [1-3]. Steel
and coworkers [4] reported that mediated electro-
chemical oxidation might provide a new alternative for
the safe disposal of chemical wastes. Mediated electro-
chemical oxidation is a cyclic process involving the elec-
trochemical regeneration of mediator ions in the electro-
chemical cell and subsequent destruction of organic ma-
terials by the produced metal ion oxidant. The general re-
actions in the cell and in the reactor for organic destruc-
tion can be represented as follows:
† silver [5-13]. Sulfuric acid possesses low solubility to-
To whom all correspondence should be addressed.
(e-mail: ismoon@sunchon.ac.kr)
Red ⇔ Ox + ne
In the reactor during the organic destruction,
Ox + S ⇔ P + Red
where ‘Red’ represents the mediator in the reduced state,
‘Ox’ represents the mediators in the oxidized state, ‘S’
represents the reactants, and ‘P’ is the product of the re-
action [4].
Commonly used mediator redox pairs in MEO proc-
esses are Ag2+/Ag+, Mn3+/Mn2+, Co3+/Co2+, and Ce4+/
Ce3+. Among these systems, silver is the most powerful
oxidizing agent in acid media owing to its high redox po-
tential (1.98 V). It may react directly with the organic
material to be destroyed or it may first react with water to
form hydroxyl radicals that in turn oxidize the organic
compounds.
Sulfuric acid, nitric acid, or perchloric acid is generally
employed as the electrolyte for the electrogeneration of
ward metal ions, perchloric acid is explosive, and hydro-
232 Manickam Matheswaran, Subramanian Balaji, Sang Joon Chung, and Il Shik Moon
Figure 1. Schematic diagram of the MEO system.
-
chloric acid is unstable due to the oxidation of Cl to Cl2
[14]. Considering these working difficulties, nitric acid
can be considered as the best choice in terms of its high
solubilizing capacity, stability, and low viscosity. The
potential of the Ag (II)/Ag (I) couple in a nitric acid me-
dium lies between 1.91 and 1.98 V versus a standard hy-
drogen electrode. Some researchers have studied the ki-
netics of the oxidation of Ag (I) in nitric acid media.
Fleishmann and coworkers [15] reported the oxidation
kinetics of Ag (I) in 3 M nitric acid with a platinum
electrode. However, a systematic study of the kinetics of
Ag (I) oxidation at various nitric acid concentrations and
its instantaneous usage towards phenol destruction has
not been reported so far.
The objectives of the present study were to investigate
the generation of Ag (II) in a batch-type electrochemical
reactor in recirculation mode with various operating pa-
rameters, including the temperature and the concen-
trations of the mediator and nitric acid, under the con-
stant potential mode, and to destruct phenol in batch and
continuous feeding modes under the optimum conditions
of Ag (II) production.
Experimental Section
Figure 1 shows a schematic diagram of the mediated
electrochemical oxidation process. The electrochemical
reactor of flow type consisted of two compartments sepa-
rated by a Nafion 324 membrane. The membrane is capa-
ble of allowing protons to move from the anodic to
cathodic compartment to maintain the current flow. IrO2-
Coated titanium and titanium mesh-type DSA electrodes,
having an area of 4 cm2 (2 cm × 2 cm × 0.5 cm), were
used as the anode and cathode, respectively. A 50-mL
solution of Ag (I) in nitric acid (0.5 M in 8 M) and nitric
acid (12 M) were placed in the anolyte and catholyte res-
ervoirs, respectively. The electrolyte solution was con-
tinuously circulated through the anolyte and catholyte
compartments of the reactor at a constant flow rate. A
constant potential was applied between the electrodes
during the oxidation reaction. In both the anolyte and
catholyte reservoirs, the temperature was maintained
constant throughout the reaction using thermostated
mantles. During the experiment, Ag (I) was oxidized to
Ag (II) at the anode and nitric acid was reduced into ni-
trous acid at the cathode. In the catholyte reservoir, NO
produced during the reduction of nitric acid was reoxi-
dized with continuous passage of atmospheric oxygen in-
to NO2, and dissolved in water to reform nitric acid.
During the electrochemical oxidation, the concentration
of Ag (II) in solution was determined rapidly and con-
veniently using a method reported previously [16]. The
procedure involved the quantitative oxidation of cerium
(III) to cerium (IV) by Ag (II), followed by the photo-
metric determination of the cerium (IV) concentration at
a fixed nitric acid concentration. The anodic and cathodic
reactions can be represented as follows [6]:
At anode:
+ 2+ -
Ag → Ag + e
2+ - +
Ag + NO3 → AgNO3
At cathode:
- + -
NO3 + 3H + 2e → HNO2 + H2O
After oxidation, Ag (II) is present as a dark-brown nitrate
+
complex, AgNO3 , in the solution.
After finding suitable and optimal operating conditions
for silver oxidation, the destruction of phenol was
investigated. The destruction was studied either in batch
or in continuous feeding mode. In the case of continuous
 Silver-Mediated Electrochemical Oxidation: Production of Silver (II) in Nitric Acid Medium and in situ Destruction of Phenol in Semi-batch Process 233
Figure 2. Effect of temperature on the formation of Ag (II).
(Experimental conditions: [AgNO3], 0.1 M; [HNO3], 8 M;
o o
Temp., 25 C; Cell Voltage, 2.5 V; q, 100 mL/min).
organic feeding, phenol was added into the anolyte after
the concentration of Ag (II) attained its steady state. The
phenol solution (10,000 ppm) was constantly fed at a rate
of 0.05 mL/min up to 30 or 120 min using a syringe
pump. The phenol was oxidized into carbon dioxide and
water and the mediator ion was reduced.
+
C6H5OH + 28Ag(II) + 11H2O → 6CO2 + 28Ag(I) + 28H
The reduced mediator ions were continuously oxidized
in the cell. The CO2 formed during the organic destruc-
tion reaction was removed by passing a carrier gas
stream (500 mL/min of N2) into the reservoir. The con-
centrations of CO2 and CO produced were measured con-
tinuously (ppm) by using an Infrared CO2 analyzer
(Anagas CD 98, Environmental Instruments) and con-
o
verted into volume at 25 C. From the accumulated CO2
and CO volumes, the destruction efficiency was cal-
culated.
Destruction Efficiency (% of CO2)
= (Expt. volume/Theo. Volume) × 100
Results and Discussion
Silver Oxidation
Effect of Temperature
The effect of temperature on the electrochemical oxida-
tion of Ag (I) was studied in the temperature range 25∼
o
60 C at fixed Ag (I) and nitric acid concentrations.
Figure 2 shows the concentration of Ag (II) generated
with respect to the reaction time at different tem-
Figure 3. Effect of nitric acid concentration on Ag (II)
generation. (Experimental conditions: [AgNO3], 0.1 M; Temp.,
25 C; Cell Voltage, 2.5 V; q, 100 mL/min).
peratures. As the temperature increased, the formation of
Ag (II) decreased due to the increased reactivity of Ag
(II) with water and corresponding decrease in the stabil-
ity of Ag (II). Upon increasing the temperature, the ni-
trous acid production increased in the anolyte and, as a
result, the acid concentration decreased in the anolyte.
This reduced nitric acid concentration lowered the stabil-
ity of the silver (II) complex and, hence, the silver (II)
concentration also decreased. A similar trend was also
observed by Sequeira and coworkers [1]. The reduction
of Ag (II) by water is represented by
+ +
4AgNO3 + 2H2O → Ag + O2 + 4HNO3
Effect of Nitric Acid
The oxidation of Ag (I) was studied under different ni-
tric acid concentrations at a fixed concentration of Ag (I)
(0.1 M) at 25 oC. Figure 3 shows the concentration of Ag
(II) produced with respect to the reaction time at different
nitric acid concentrations. From the figure, we observe
that the formation of Ag (II) increased upon increasing
the nitric acid concentration, due to the higher stability of
the [Ag(NO3)]+ complex at higher acid concentrations
[17]. The highest conversion, 45 % Ag (II), was obtained
at 8 M nitric acid. From Figure 3 we also observe that the
concentration of Ag (II) increased initially and attained a
steady state near 30 min for a lower acid concentration (6
M); the same effect was observed at ca. 60 min at a high
acid concentration (10 M nitric acid).
Effect of Initial Ag (I) Concentration
The oxidation of silver was studied under different ini-
tial concentrations of Ag (I) at a fixed concentration of
o
nitric acid of 8 M at 25 C. Figure 4 shows the increase
234 Manickam Matheswaran, Subramanian Balaji, Sang Joon Chung, and Il Shik Moon
Figure 4. Effect of initial Ag (I) concentration on the formation
of Ag (II). (Experimental conditions: [HNO3], 8 M; Temp., 25
o o
C; Cell Voltage, 2.5 V; q, 100 mL/min).
Figure 5. Effect of temperature on the destruction efficiency of
phenol in the continuous feeding mode (Experimental con-
ditions: [AgNO3], 0.1 M; [HNO3], 8 M; Cell Voltage, 2.5 V;
feed time, 30 min).
in the Ag (II) concentration with time at different initial
concentrations of Ag (I). The percentage conversion of
Ag (II) formation decreased upon increasing the concen-
tration of Ag (I). At 0.1 M Ag (I), 45 % of Ag (II) was
obtained at the steady state. In this case, the steady state
concentration of Ag (II) was attained at ca. 30 min for al-
most all concentrations of silver (I), except for 1 M Ag
(I).
Figure 6. Effect of concentration of Ag (I) on the destruction
efficiency of phenol in the continuous mode (Exper-imental
conditions: Temp., 60 C; [HNO3], 8 M; Cell Voltage, 2.5 V;
feed time, 30 min).
Destruction of Phenol during Continuous Organic
Feeding
Short-term Feeding
Effect of Temperature
The destruction of phenol was undertaken at different
temperatures with fixed concentrations of 0.1 M Ag (I)
and 8 M nitric acid. The Ag (I) was oxidized into Ag (II).
Initially, the Ag (II) concentration increased with in-
creasing time and reached a steady state after 30 min.
The steady state Ag (II) concentration was established
when the rates of Ag (II) generation and loss were
equivalent. At this point, the only loss of Ag (II) was due
to the reduction by water. After the steady state was
reached, the organic solution was continuously fed into
the anolyte for 30 min. The organic fed to the anolyte
was completely oxidized into carbon dioxide and water.
Also, a minor quantity of carbon monoxide was detected
during the destruction reaction. Figure 5 shows the de-
struction efficiency for various temperatures in the con-
tinuous feeding mode. The destruction efficiency was
calculated based on the volume of CO2 produced up to
the end point of organic feeding (30 min). The destruc-
tion efficiency increased upon increasing the temperature
(Figure 5).
Effect of Silver (I) Concentration
The effect of the silver (I) concentration on phenol de-
o
struction was studied at a fixed temperature of 60 C with
a fixed nitric acid concentration of 8 M. After reaching
the steady state concentration of Ag (II), the destruction
of phenol was performed in continuous mode. Figure 6
 Silver-Mediated Electrochemical Oxidation: Production of Silver (II) in Nitric Acid Medium and in situ Destruction of Phenol in Semi-batch Process 235
Figure 7. (a) Phenol conversion to CO2 and moles of CO2. (b)
Phenol conversion to CO and moles of CO produced during
phenol destruction in continuous feeding mode (Experimental
conditions: [AgNO3], 0.1 M; Temp., 60 oC; [HNO3], 8 M, Cell
Voltage, 2.5 V; [Phenol], 10000 ppm).
shows the destruction efficiency plotted against the ini-
tial concentration of Ag (I). The destruction efficiency
increased upon increasing the concentration of Ag (I).
However, the increase in the destruction efficiency was
not significant over 0.5 M Ag (I). An increase in the Ag
(II) concentration beyond 0.5 M did not result in in-
creased destruction efficiencies. This finding coincides
with the results reported by many authors for silver MEO
systems [1,6,8,18], in which 0.5 M Ag (I) has been used
for organic destruction to obtain maximum destruction
efficiency.
Long-Term Feeding
Figure 7a shows the percentage conversion of CO2 and
moles of CO2 produced during continuous feeding of
phenol for 120 min at a constant flow rate of 0.05
o
mL/min at 60 C. The steady state of CO2 evolution was
reached after 20 min. The steady state destruction effi-
ciency of the process was 80 % based on CO2 formation.
The accumulated concentration of CO2 increased linearly
with respect to the reaction time. During the destruction
of phenol, a small amount of CO was also observed.
Figure 7b shows the percentage of CO produced and the
moles of CO produced over time during phenol
destruction.
Destruction of Phenol in Batch-Type Organic Feeding
In this case, both the phenol and silver solutions [with
fixed concentrations of silver (I) and nitric acid] were
mixed to obtain the desired concentrations of phenol
(10,000 ppm) and silver (I) (0.1 M); this solution was
then fed into the anolyte tank. A constant potential of 2.5
Figure 8. Phenol conversion to CO2 plotted against time in
terms of (a) percentage and concentration and (b) concentration
of CO in batch mode of organic addition (Experimental con-
ditions: [AgNO3], 0.1 M; Temp., 60 oC; [HNO3], 8 M; Cell
Voltage, 2.5 V; [Phenol], 10000 ppm).
V was applied between the electrodes throughout the ex-
o
periment at 60 C. Figure 8a shows the percentage con-
version of CO2 and the amount of CO2 formed during the
reaction time. The destruction efficiency of the process
was observed to be 88 % based on CO2 produced. Figure
8b shows the concentration of CO formed during the
reaction. A maximum destruction of 80 % was obtained
at ca. 30 min and then the extent of further destruction
slowed down. At 60 min, the CO2 production had almost
ceased, and the increase in the destruction efficiency af-
ter 30 min was observed to be only 8 %. This typical pat-
tern of an initial fast destruction and then slow kinetics is
the inherent nature of MEO systems featuring the for-
mation of slowly degrading intermediates [19,20]. It was
reported by Balazs and coworkers [19,20] that in the sil-
ver MEO process, the coulombic efficiency [21] was ca.
80 % to obtain 95 % organic destruction, whereas to ob-
tain 99 % destruction, the coulombic efficiency was ob-
served to be only 40 %, indicating the slow destruction
of remaining organics and the greater amount of energy
required to achieve complete destruction.
Conclusions
The electrochemical oxidation of Ag (I) was studied
with respect to various parameters, including the temper-
ature and the concentrations of nitric acid and mediator
in an electrochemical cell. The concentration of Ag (II)
increased upon increasing the concentration of nitric acid
and decreased upon increasing the temperature. The con-
version ratio also decreased upon increasing the initial
236 Manickam Matheswaran, Subramanian Balaji, Sang Joon Chung, and Il Shik Moon
concentration of Ag (I). The destruction of phenol was
studied in batch and continuous feeding modes under the
optimum oxidation conditons for Ag (II) production by
the cell. The destruction efficiency in the batch mode
was ca. 88 % (based on CO2 evolution) and in the con-
tinuous mode it was 80 %. Long-term organic feeding
experiments showed that the efficiency of the process,
with large amounts of organic destruction and consistent
Ag (II) production by the cell.
Acknowledgments
This study was supported by the Ministry of Commerce,
Industry, and Energy (MOCIE), Republic of Korea,
through the project of the Regional Invocation Center
(RIC).
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