Electrochimica Acta 52 (2007) 5696–5703

Influence of anode material on electrochemical

decomposition of urea
Wojciech Simka ∗ , Jerzy Piotrowski, Ginter Nawrat
Department of Chemistry and Inorganic Technology, Faculty of Chemistry, Silesian University of Technology,
B. Krzywoustego 6, 44-100 Gliwice, Poland
Received 5 October 2006; received in revised form 13 November 2006; accepted 4 December 2006
Available online 17 December 2006

Abstract
Voltammetric investigations into the process of anodic decomposition of urea using Ti/Pt, Ti/(Pt–Ir)70:30 , Ti/RuO2 , Ti/(RuO2 –TiO2 )40:60 ,
Ti/(RuO2 –TiO2 –IrO2 )20:60:20 , Ti/(Ta2 O5 –IrO2 )70:30 electrodes have been carried out. Two anodes namely (Ti/(Pt–Ir)70:30 and Ti/(Ta2 O5 –IrO2 )70:30 )
were found to be stable enough and indicated the required activity to produce non-toxic N2 and CO2 in place of nitrites and nitrates, the commonly
reported electrochemical urea oxidation products. The kinetics of the process in question using the above two electrodes was further examined in a
periodic electrolyzer. The effect of the anodic current density (j = 2–10 A/dm2 ), initial urea concentration (c0M = 1–10 g/dm3 ) and the concentration
of sodium chloride (cNaCl = 1–10 g/dm3 ) on basic process indices (average rate of urea decomposition, a; current efficiency, Wp , and unit DC power
consumption, Zj ) was discussed.
© 2006 Elsevier Ltd. All rights reserved.

Keywords: Urea; Anode material; Electrochemical oxidation; Wastewater treatment

1. Introduction
The industrial synthesis of urea involves the reac-
tion of ammonia and carbon dioxide under high pressure
(p = 10–25 MPa) and temperature (T = 420–480 K). The process
can be divided into the following steps: synthesis, decomposi-
tion of byproducts, concentration of urea solution, crystallization
and granulation. The above process results in large quantities
of wastewaters of varying urea concentration, usually purified
by hydrolysis [1,2], however, other methods for urea removal
from aqueous solutions are also described [3–7]. The latter are
considered to be either costly, because of the requirement of
sophisticated apparatus, and thus are not suitable for the indus-
trial scale or are still being tested.
Anodic oxidation is an alternative method for treating the
wastewater produced during urea manufacture and may results
in not-toxic products (CO2 , N2 , H2 ). Most of the investigations
into the anodic decomposition of urea described in the litera-
ture were aimed at determining the mechanism and products of
∗ Corresponding author. Tel.: +48 32 237 26 05; fax: +48 32 237 22 77.
E-mail address: wojciech.simka@polsl.pl (W. Simka).
urea oxidation as well as the possibility for applying the urea
electrochemical decomposition process for the regeneration of
dialyzate in artificial kidney design. They were carried out using
potentiostatic techniques and were limited only to platinum elec-
trodes of small surface area. It has been there found that anodic
oxidation of urea depends on anode potential, kind and com-
position of the basic electrolyte, urea concentration, pH and
temperature of the solution. Different conditions of the treatment
result in different products of urea decomposition (CO2 , N2 , H2 ,
CNO− , NO3 − , NO2 − , [N2 O2 ]− , N2 O, NO2 , NH2 CONH2 •+ ).
At high potentials (over 1.7 V versus SCE) in the acidic envi-
ronment, urea is decomposed by a direct oxidation at electrode
surface primarily to CO2 and N2 [8,9], while at lower poten-
tials (below 1.6 V versus SCE), urea reacts with an OH• radical
and the decomposition products remain in the solution [10]. In a
phosphate buffer solution, the limiting factor at high potentials is
the urea decomposition to CO2 and N2 , and the process rate does
not depend on pH of the solution [11]. The authors of paper [12]
have found that urea decomposition to nitrate(III) and (V) ions is
the predominant process at high potentials in neutral solutions.
The lowest potentials result in a radical cation—NH2 CONH2 •+ ,
which may polymerize [15]. An increase in temperature as well
as the increase in acidity increase the rate and efficiency of urea

0013-4686/$ – see front matter © 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2006.12.017
 W. Simka et al. / Electrochimica Acta 52 (2007) 5696–5703 5697

decomposition [10,13]. The authors of paper [14] have found

that the use of phosphate buffer solutions at varying potential
from 0.75 to 1.4 V versus SHE results mainly in carbon diox-
ide and nitrogen, which is different from the reported elsewhere
[8,10]. The decomposition of urea can also take place through a
reaction with sodium hypochlorite produced during the electrol-
ysis of solutions containing chlorides [15–17]. The application
of a titanium electrode coated with titanium(IV) and ruthe-
nium(IV) oxides to urea decomposition produces carbon dioxide
and nitrogen [18]. The above process results in the formation of
intermediate products: monochlorourea and dichlorourea. Our
previous research showed that the electrooxidation technique is
applicable and may be very useful for solving the urea contain-
ing wastewaters utilization problem [19,20]. Although there has Fig. 1. Schematic of periodic laboratory electrolyzer (1—electrolyzer,
been a lot of research done, the process of anodic oxidation of 2—anode, 3—cathodes, 4—direct current supply, 5—voltmeter, 6—ammeter).
urea has not been fully recognized and explained up to date.
Electrochemical decomposition of urea is a complex process
and depends on many factors. The available literature on the appropriate salts on titanium support [25–27]. All the elec-
mechanism of urea electrooxidation is not explicit enough and trodes were examined in the form of thin rod, 5 cm × 0.3 cm
generally does not focus on the solutions whose composition (length × diameter).
is similar to that of industrial urea-containing wastewater, and The measurements were carried out at 25 ◦ C, at a poten-
thus cannot be directly used to develop an effective treatment tial range of 0–2.8 V versus SCE and potential change rate
technique. of 100 mV/s. The electrolyte solutions of constant NaCl con-
This study aims to select an anode material for electrochem- tent (of 5 g/dm3 ) and varying urea concentration of 0.01, 1 and
ical decomposition of urea, examine the kinetics of anodic urea 10 g/dm3 were applied. All the above solutions were prepared
oxidation in a periodic electrolyzer using the selected anode using analytical grade reagents manufactured by POCh Gliwice,
materials and finally determine the effect of process parameters Poland and deionized water produced with the Millipore Milli-Q
on its course. system.

2. Methods
2.2. Investigations into kinetics of anodic decomposition of
urea
2.1. Voltammetric examination of anodic decomposition of
urea
The electrolysis was carried out in a 1.5-dm3 electrolyzer
made of polymethyl methacrylate (Fig. 1). Two cathodes made
The voltammetric cell consisted of two compartments with
of a platinum coated titanium grid were placed inside and sep-
the tested electrode (titanium modified with active coatings),
arated with an anode. The gap between the anode and cathodes
auxiliary platinum electrode and Haber–Lugin capillary with
was 6 mm thick. The anode materials used were: Ti/(Pt–Ir)70:30 ,
a saturated calomel electrode (SCE) reference electrode placed
with surface area of s = 1.87 dm2 and Ti/(Ta2 O5 –IrO2 )70:30 (of
inside. The cell was powered through a potentiostat (AUTOLAB
s = 1.61 dm2 ).
PGSTAT 30), operated by General Purpose Electrochemical
The electrochemical decomposition of urea was conducted
System (GPES) software.
at a constant current intensity for 3 h. During the measurements,
The voltammetric examination of the following anode mate-
samples of the liquid phase were collected from the electrolyzer
rials was conducted:
at fixed intervals to determine pH, urea concentration and
hypochlorite. Urea was analysed spectrophotometrically [28]
- titanium coated with platinum, Ti/Pt;
while hypochlorite iodometrically [29]. Constant measurements
- titanium coated with Pt–Ir at a molar ration of 70:30,
of the voltage drop, current intensity and temperature of elec-
Ti/(Pt–Ir)70:30 ;
trolyte with accuracy of ± 0.1 V, ± 0.1 A, ± 0.1 ◦ C, respectively,
- titanium coated with ruthenium oxide, Ti/RuO2 ;
were carried out.
- titanium coated with RuO2 –TiO2 at a molar ratio of 40:60,
The results of the above measurements were used to calculate
Ti/(RuO2 –TiO2 )40:60 ;
the following process indices for electrochemical decomposition
- titanium coated with RuO2 –TiO2 –IrO2 at a molar ratio of
of urea:
20:60:20,Ti/(RuO2 –TiO2 –IrO2 )20:60:20 ;
- titanium coated with Ta2 O5 –IrO2 at a molar ratio of
70:30,Ti/(Ta2 O5 –IrO2 )70:30 . – average rate of urea decomposition:

Ti/Pt electrode was made by Pt electrodeposition [21–24]. mri
a [g/(h dm2 )] = (1)
The others were prepared by thermal decomposition of τs
5698 W. Simka et al. / Electrochimica Acta 52 (2007) 5696–5703

Table 1
The influence of urea content on electric current density at 2.0 V
Electrode material j [A/cm2 ]

cU = 0 g/dm3 cU = 0.01 g/dm3 cU = 1.0 g/dm3 cU = 10 g/dm3

Ti/Pt 0.085 0.045 0.041 0.038

Ti/(Pt–Ir)70:30 0.068 0.060 0.059 0.046
Ti/RuO2 0.096 0.084 0.079 0.075
Ti/(RuO2 –TiO2 )40:60 0.112 0.144 0.124 0.115
Ti/(RuO2 –TiO2 –IrO2 )20:60:20 0.093 0.083 0.081 0.072
Ti/(Ta2 O5 –IrO2 )70:30 0.070 0.084 0.131 0.092


where mri is the weight of urea decomposed in time τ (g); 3. Results and discussion
mri the weight of urea decomposed in time τ (g)
3.1. Voltammetric investigations into anodic decomposition
mri (g) = Vr (CUi−1 − CUi ) (2) of urea

τ is the electrolysis time in h; s the electrode surface area in
dm2 ; (cUi−1 − cUi ) the change in urea concentration over time
τ in g/dm3 ; Vr is the current volume of urea solution.
The average urea decomposition rate was defined as the
decrease in urea mass during unit time per unit electrode sur-
face area. The average rate defined in the above manner is
formally based on the system mass balance and for adiabatic
electrolyzer, no correction for temperature was required.
– current efficiency related to the total urea decomposition reac-
tion:
NH2 CONH2 + H2 O → N2 + 3H2 + CO2
Σmri
Wp = × 100%
mt
M
mt (g) = mh Iτ = Iτ
nF
where mt the theoretical weight of decomposed urea in g; mh
the electrochemical equivalent in g/Ah; M the molar mass
of urea (M = 60.06 g/mol); I the current intensity in A; n the
number of electrons exchanged during reaction (3), n = 6; F
is the Faraday constant (Ah/mol);
– unit DC power consumption:
3.1.1. Ti/Pt electrode
At a constant concentration of sodium chloride, an increase
in urea concentration caused a considerable decrease in current
density (Table 1), the largest one being found for urea concentra-
tion of 10 g/dm3 . This is suspected to be the result of adsorption
of urea on the electrode surface and its resulting blockage of
electrode active sides for chloride oxidation [30]. However, an
addition of urea does not affect the potential at which sodium
chloride decomposition takes part (approximately 1.1 V versus
SCE).
3.1.2. Ti/(Pt–Ir)70:30 electrode
(3) Similarily to Ti/Pt electrode, an increase in urea concentra-
tion at constant NaCl content caused the Ti/(Pt–Ir)70:30 electrode
active sides blockage which leads to the decrease in chlorine
(4)
release and consequent decrease in current density (Table 1).
This is consistent with the data presented in [30].
(5)
3.1.3. Ti/RuO2 electrode
As for the previous electrodes, in the case of Ti/RuO2 the urea
supplement in the range of 0.1–10.0 g/dm3 caused the blockage
of the electrode active sites and resulted in a decrease in cur-
rent density and chlorine release (Fig. 2, Table 1). The peak of
adsorbed chlorine reduction observed during the decomposition

Ez × 100
Zj [kWh/kg] = (6)
Wp mh

where EZ is the average voltage drop in V.

The experiments were designed to determine the effect of

anodic electric current density (j = 2–10 A/dm2 ), initial con-
centration of urea (c0U = 1–10 g/dm3 ) and concentration of
sodium chloride (cNaCl = 1–10 g/dm3 ) on basic process indica-
tors (a, Wp , Zj ). In addition, a set of experiments was conducted
to assess the reproducibility of the measurements.
Fig. 2. Exemplary Ti/RuO2 electrode voltammetric curves for NaCl solutions
of 5 g/dm3 content containing varying urea amounts; (1) cU = 0 g/dm3 ; (2)
cU = 0.1 g/dm3 ; (3) cU = 1.0 g/dm3 ; (4) cU = 10.0 g/dm3 .
 W. Simka et al. / Electrochimica Acta 52 (2007) 5696–5703
Table 2
Process indices for anodic decomposition of urea, c0U = 10 g/dm3 , cNaCl = 5 g/dm3 , τ = 180 min using the examined electrodes
j [A/dm2 ] Ti/(Pt-Ir)70:30
a [g/h dm2 ] Wp [%]
2 0.94 118
4 1.50 99
6 1.64 75
8 1.67 56
10 2.04 54
of pure NaCl at a potential close to 1.0 V disappears at urea
concentrations higher than 0.1 g/dm3 .
3.1.4. Ti/(RuO2 –TiO2 )40:60
For RuO2 –TiO2 mixture layered Ti electrode the supplement
of urea at constant sodium chloride concentration caused an
increase in current density which indicates a direct urea oxida-
tion on the electrode surface (Table 1). However, the destructive
action of urea on electric current density was noted since the
increase in urea content caused the decrease in electric current.
3.1.5. Ti/(RuO2 –TiO2 –IrO2 )20:60:20
An increase in urea concentration from 0.1 to 10.0 g/dm3
caused a decrease in current density (Table 2). Again, this was
found to be the results of the adsorption of urea on the electrode
surface.
3.1.6. Ti/(Ta2 O5 –IrO2 )70:30 electrode
An increase in urea concentration from 0.1 to 1.0 g/dm3
caused an increase in current density (Table 2). At higher urea
content, of 10.0 g/dm3 , current density exhibits a decreasing ten-
dency, yet it is still higher than the current density observed for
the decomposition of the base electrolyte (NaCl). This indicates
a direct oxidation of urea on the electrode surface.
In the presence of sodium chloride, urea becomes directly
decomposed on Ti/(RuO2 –TiO2 )40:60 and Ti/(Ta2 O5 –IrO2 )70:30
electrodes. The rate of electrochemical decomposition of urea
increases with increasing anode potential. For other electrode
materials, in the presence of NaCl, the adsorption of urea on
the electrode was observed, causing the blockage of its surface
and decrease in current density. The results for Ti/Pt elec-
trode are consistent with the results given in paper [30] which
shows that urea adsorbs on the surface of platinum and hinders
the adsorption of chloride ions. On the other hand, the results
obtained for Ti/(RuO2 –TiO2 )40:60 electrode are consistent with
the results from paper [18–20] which reveal that urea is decom-
posed directly on the anode to non-toxic products (N2 , CO2 ,
H2 ).
Since the rate of electrochemical decomposition of urea
increases with increasing electrode potential, the process of
anodic decomposition should be conducted at the highest anodic
potential possible. This excludes the electrodes whose coating
contains RuO2 since it is oxidized to volatile RuO4 when its
potential exceed 1.45–1.50 V versus SHE that result the elec-
trode deactivation. No such limitation is observed for highly
corrosion resistant Ti/(Pt–Ir)70:30 electrode, which is commonly
5699
Ti/(Ta2 O5 –IrO2 )70:30
Zj [kWh/kg] a [g/h dm2 ] Wp [%] Zj [kWh/kg]
8.2 0.47 63 15.9
11.1 0.86 57 20.9
18.6 1.20 54 24.7
24.4 1.41 49 29.7
35.4 1.66 44 34.5
applied to for sodium hypochlorite obtaining from dilute NaCl
solutions. Another material without the above shortcoming is a
titanium electrode coated with tantalum and iridium oxides, the
electrode that oxidizes urea directly.
When considering the above, and the available literature, the
following electrodes were selected for further kinetic investiga-
tions: Ti/(Pt–Ir)70:30 , Ti/(Ta2 O5 –IrO2 )70:30 .
3.2. Investigations into kinetics of anodic decomposition of
urea
3.2.1. The influence of anodic current density on the urea
decomposition rate
The rate of anodic decomposition of urea was found to depen-
dent strongly on current density (Fig. 3) when Ti/(Pt–Ir)70:30
electrode is applied. An increase in density from 2 to 10 A/dm2
caused an increase in the average rate of urea decomposition
from 0.94 to 2.04 g/h dm2 and unit power consumption from 8.2
to 35.4 kWh/kg (Table 2). At the same time current efficiency
decreased more than two times. At current density of 2 A/dm2 ,
NO2 − and NO3 − ions were found, which indicates an excessive
oxidation of urea and prevents its industrial application since
these ions are serious and toxic contaminants of water. The
electric current efficiency at 2 A/dm2 current density exceeded
100%, when Eq. (3) was applied for Wp determination, since
the number electrons exchanged to oxidize urea to nitrogen
is much smaller than the value for nitrite or nitrate obtaining
(see Table 2). In this case urea may be oxidized by eventually
formed hydroxyl radicals and nitrites or nitrates may be
produced.
The process is accompanied by a drastic increase in temper-
ature of the solution—from 20 to approximately 90 ◦ C, being
approximately constant after 20 min. At the end of the process,
when urea concentration reached the lowest values, the con-
Fig. 3. Kinetic curves of anodic decomposition of urea at varying electric
current densities for Ti/(Pt–Ir)70:30 electrode; c0U = 10 g/dm3 , cNaCl = 5 g/dm3 ,
τ = 180 min.
5700 W. Simka et al. / Electrochimica Acta 52 (2007) 5696–5703

Fig. 4. Kinetic curves of anodic decomposition of urea at varying electric current Fig. 6. Kinetic curves of anodic decomposition of urea at varying initial urea
densities for Ti/(Ta2 O5 -IrO2 )70:30 electrode; c0U = 10 g/dm3 , cNaCl = 5 g/dm3 , concentration for Ti/(Ta2 O5 –IrO2 )70:30 electrode; j = 8 A/dm2 , cNaCl = 5 g/dm3 ,
τ = 180 min. τ = 180 min.

The increase in the initial concentration of urea favourably

Fig. 5. Kinetic curves of anodic decomposition of urea at varying initial urea
concentration for Ti/(Pt–Ir)70:30 electrode; j = 8 A/dm2 , cNaCl = 5 g/dm3 .
centration of hypochlorite in the solution increased. This may
indicate that the decomposition of urea takes place with con-
comitant hypochlorite in the bulk of the electrolyte and explain
the absence of the minor amounts of hypochlorite during urea
oxidation.
For Ti/(Ta2 O5 –IrO2 )70:30 electrode an increase in anodic cur-
rent density leads to a considerable increase in the rate of the
process (Fig. 4). The average rate of urea decomposition rised
from 0.47 to 1.66 g/h dm2 while current efficiency decreased
from 63 to 44% (Table 2). At the same time the unit power con-
sumption increases twofold (from 15.9 to 34.5 kWh/kg). The
average rates of urea decomposition and current efficiencies
determined are lower than determined for Ti/(Pt–Ir)70:30 elec-
trode. The concentration of chloride ions during the process does
not practically change, that suggest no hypochlorite formation
and direct urea oxidation on the electrode surface.
affected the unit power consumption which decreased from 39.9
to 24.4 kWh/kg. Irrespective of the initial urea concentration,
the concentration of chloride ions decreased and the quantity of
hypochlorite increased during the process when the concentra-
tion of urea reached the lowest values.
For Ti/(Ta2 O5 –IrO2 )70:30 the rate of anodic decomposition
of urea increased with an increase in urea concentration (Fig. 6,
Table 3). Current efficiency rises from 16 to 49% with a con-
comitant substantial decrease in the unit power consumption
from 72.5 to 29.7 kWh/kg. The decrease in urea concentration
during the process to approximately 0.3 g/dm3 did not cause any
change in the concentration of hypochlorite which remained
constant. Lower concentrations of urea lead to an increase in
hypochlorite content. This indicates that urea is decomposed on
the surface of the electrode by adsorbed chlorine and conforms
the voltammetric tests results.
3.2.3. The influence of sodium chloride concentration on
the rate of urea decomposition
The concentration of sodium chloride negligibly affects the
rate of the process (Fig. 7) when applying Ti/(Pt–Ir)70:30 . elec-

3.2.2. The influence of initial urea concentration on the

rate of its decomposition
An increase in the initial concentration of urea from 1 to
10 g/dm3 caused a twofold increase in the process rate (Fig. 5,
Table 3) when applying Ti/(Pt–Ir)70:30 electrode. The current Fig. 7. Kinetic curves of anodic decomposition of urea at varying NaCl concen-
efficiency of the process increased as well (from 28 to 56%). tration for Ti/(Pt–Ir)70:30 electrode; c0U = 10 g/dm3 , j = 8 A/dm2 , τ = 180 min.

Table 3
Process indices for anodic decomposition of urea, j = 8 A/dm2 , cNaCl = 5 g/dm3 , τ = 180 min. using the examined electrodes
c0U [g/dm3 ] Ti/(Pt–Ir)70:30 Ti/(Ta2 O5 –IrO2 )70:30

a [g/h dm2 ] Wp [%] Zj [kWh/kg] a [g/h dm2 ] Wp [%] Zj [kWh/kg]

1 0.83 28 39.9 0.49 16 72.5

3 1.05 35 36.4 0.60 20 71.3
5 1.28 43 32.9 1.01 34 41.4
7 1.45 48 29.5 1.39 47 30.0
10 1.67 56 24.4 1.41 49 29.7
 W. Simka et al. / Electrochimica Acta 52 (2007) 5696–5703 5701

Table 4
Process indices for anodic decomposition of urea, c0U = 5 g/dm3 , j = 8 A/dm2 , τ = 180 min. using the examined electrodes
cNaCl [g/dm3 ] Ti/(Pt–Ir)70:30 Ti/(Ta2 O5 –IrO2 )70:30
a [g/h dm2 ] Wp [%] Zj [kWh/kg] a [g/h dm2 ] Wp [%] Zj [kWh/kg]

1 1.62 54 36.1 0.93 31 86.6

3 1.66 54 27.4 1.27 42 40.1
5 1.67 56 24.4 1.41 49 29.7
7 1.68 56 21.8 1.63 55 23.1
10 1.69 56 19.5 1.85 62 18.6

ride concentration in the solution may cause an increase in the

Fig. 8. Kinetic curves of anodic decomposition of urea at varying NaCl
concentration for Ti/(Ta2 O5 –IrO2 )70:30 electrode; c0U = 10 g/dm3 , j = 8 A/dm2 ,
τ = 180 min.
trode. The average rate of urea decomposition increased from
1.62 to 1.69 g/h dm2 (Table 4). Current efficiency of the process
practically didn’t change with the increase in the concentration
of sodium chloride. A significant decrease is observed for unit
power consumption (from 36.1 to 19.5 kWh/kg), which relates
to the increase in the conductivity of the solution, hence a
decrease in the voltage drop. When urea concentration is lower
than approximately 0.3 g/dm3 , an increase in the hypochlorite
content is observed. Moreover, it was observed that the higher
the concentration of sodium chloride, the bigger the increase in
the concentration of hypochlorite.
When Ti/(Ta2 O5 –IrO2 )70:30 electrode is applied, an increase
in sodium chloride concentration leads to a rise in the rate
of urea decomposition (Fig. 8). The average rate increases
twofold from 0.93 to 1.85 g/h dm2 and the current efficiency
rises twofold as well (Table 4). The increase in sodium chloride
improves the conductivity of the solution which consequently
substantially decreases the voltage drop and the unit power con-
sumption. During the process, the concentration of chloride ions
and hypochlorite remains constant. An increase in sodium chlo-
amount of chlorine adsorbed at the electrode which might react
with urea resulting in its decomposition. This is confirmed by the
increase in the rate of anodic urea decomposition with increasing
concentration of sodium chloride.
The anodic oxidation of urea in the solutions containing chlo-
ride ions may be the result of:direct electrode reaction, oxidation
by chlorine produced during an anodic process, oxidation by
chlorine adsorbed at the electrode or simultaneously in all of
the above [18]. The predominance of one of the mechanisms of
electrochemical decomposition of urea and its products depend
on factors such as: anode material, type and concentration of an
electrolyte which affects conductivity and process parameters.
When Ti/(Pt–Ir)70:30 electrode is applied for the urea removal
from aqueous solutions, it is decomposed in the entire volume
of the solution primarily to non-toxic products (N2 , CO2 , H2 ) by
hypochlorite produced during the process, but not directly on the
anode surface [19,20]. The results obtained conforms the find-
ings of previous voltammetric research on anodic decomposition
of urea carried out on that anode material and proves that urea
does not undergo a direct electrode decomposition. The course
of urea decomposition by hypochlorite in the entire volume of
the solution is also described by non-linear correlations cM = f(τ)
obtained for different initial concentrations of urea (Fig. 5).
When Ti/(Ta2 O5 –IrO2 )70:30 electrode is applied to the
removal of urea from aqueous solutions, its reaction with chlo-
rine adsorbed at the electrode resulting in non-toxic products
(N2 , CO2 , H2 ) predominates [19,20]. This is proved by the
voltammetric tests which showed that urea is directly decom-
posed at the electrode. The rate of urea decomposition is not
significantly dependent on its current concentration in the solu-
tion which is confirmed by the straight line correlation cM = f(τ)

Table 5
The analysis of the reproducibillity of the examined process, c0U = 5 g/dm3 , cNaCl = 5 g/dm3 , j = 8 A/dm2 , τ = 180 min.
No measurement Ti/(Pt–Ir)70:30 Ti/(Ta2 O5 –IrO2 )70:30

a [g/h dm2 ] Wp [%] Zj [kWh/kg] a [g/h dm2 ] Wp [%] Zj [kWh/kg]

1 1.67 56 24.4 1.40 49 29.9

2 1.69 56 24.3 1.39 48 29.7
3 1.70 57 23.8 1.41 50 29.5
4 1.68 56 24.2 1.41 47 29.8
5 1.66 56 24.5 1.42 49 30.1
x̄ 1.68 56.2 24.2 1.41 48.6 29.8
Sx̄2 0.0002 0.20 0.07 0.0001 1.30 0.05
Sx 0.02 0.45 0.27 0.011 1.14 0.22
5702 W. Simka et al. / Electrochimica Acta 52 (2007) 5696–5703
determined for different initial concentrations of urea (Fig. 6).
They also prove that the reaction of urea decomposition takes
place directly at the anode.
3.2.4. The reproducibility of anodic urea decomposition
The reproducibility of anodic urea decomposition utilizing
Ti/(Pt–Ir)70:30 i Ti/(Ta2 O5 –IrO2 )70:30 electrodes was examined.
In order to attain that, the experiments were multiplied (Table 5)
[31]. The low values of variance (Sx̄2 ) and standard deviation (Sx )
indicate that the experiments are fully reproducible.
4. Conclusions
The process of anodic decomposition of urea in the presence
of chloride ions may be the result of direct electrode reaction,
reaction with hypochlorite produced during the process or a
reaction with chlorine adsorbed on the surface of the electrode.
Usually, all these reactions occur simultaneously, however, often
one of them being predominant depending on the conditions.
Although numerous investigations into anodic oxidation of urea
have been carried, its mechanism has not been explained fully
yet. Nor have the optimum process parameters for anodic decom-
position of urea to non-toxic and volatile products (N2 , CO2 ,
H2 ), which might help develop a technology for removing urea
from aqueous solutions by the electrochemical oxidation. Due
to a lot of discrepancies in the literature, there was a need for
a thorough examination of anodic decomposition of urea over
a wide range of parameters. Thus, voltammetric tests on anodic
decomposition of urea on different anode materials and exami-
nation of the kinetics of the process on selected electrodes have
been carried out.
The voltammetric tests have revealed the following findings:
- urea adsorbs on the surface of the following anode materials:
Ti/Pt, Ti/(Pt–Ir)70:30 , Ti/RuO2 , Ti/(RuO2 –TiO2 –IrO2 )20:60:20
in the presence of sodium chloride (electrolyte aiding solution
conductivity);
- urea undergoes a direct electrode reaction on the following
anode materials Ti/(RuO2 –TiO2 )40:60 , Ti/(Ta2 O5 –IrO2 )70:30
in the presence of sodium chloride (electrolyte aiding solution
conductivity);
- the following anode materials are suitable for anodic decom-
position of urea: Ti/(Pt–Ir)70:30 , Ti/(Ta2 O5 –IrO2 )70:30 .
The investigations into the kinetics of anodic decomposition
of urea in a periodic electrolyzer on Ti/(Pt–Ir)70:30 electrode
have yielded the following results:
- urea is oxidized to nitrate(III) and (V) ions at current density
lower than 4 A/dm2 which prevents from the application of
low current densities in anodic decomposition of urea;
- the reaction of urea and chlorine produced during the process
predominates the anodic decomposition of urea. It takes place
in the entire volume of the solution;
- non-toxic N2 , CO2 , H2 , are major products of anodic decom-
position of urea;
- Ti/(Pt–Ir)70:30 anode may be applied to the removal of urea
from aqueous solutions by electrochemical method on an
industrial scale;
- current density of 8 A/dm2 and sodium chloride concentration
of 5 g/dm3 are optimum process parameters.
The investigations into the kinetics of anodic decomposi-
tion of urea in a periodic electrolyzer on Ti/(Ta2 O5 –IrO2 )70:30
electrode have yielded the following results:
- urea reaction with chlorine adsorbed on the surface of the
electrode predominated the anodic decomposition of urea;
- non-toxic N2 , CO2 , H2 , are major products of anodic decom-
position of urea;
- Ti/(Ta2 O5 –IrO2 )70:30 anode may be applied to the removal of
urea from aqueous solutions by electrochemical method;
- current density of 8 A/dm2 and sodium chloride concentration
of 5 g/dm3 are optimum process parameters.
The comparison of the basic indicators of anodic decom-
position of urea for Ti/(Pt–Ir)70:30 and Ti/(Ta2 O5 –IrO2 )70:30
electrodes in the periodic electrolyzer at optimum process
parameters has revealed that the former electrode is more favor-
able.
Acknowledgement
The research was financed by the state within the 2005–2006
budget for research projects.
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