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Study the kinetics of electrochemical removal of copper from dilute solutions

using packed bed electrode

Article  in  Egyptian Journal of Petroleum · March 2014

DOI: 10.1016/j.ejpe.2014.02.013

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Egyptian Journal of Petroleum (2014) 23, 93–103

Egyptian Petroleum Research Institute

Egyptian Journal of Petroleum

www.elsevier.com/locate/egyjp
www.sciencedirect.com

FULL LENGTH ARTICLE

Study the kinetics of electrochemical removal of

copper from dilute solutions using packed bed electrode
I.A. Khattab a, M.F. Shaffei a, N.A. Shaaban a, H.S. Hussein a,*
,
S.S. Abd El-Rehim b

a
National Research Centre, Chem. Eng. and Pilot Plant Dept., El-Tahrir Street, Dokki, Cairo, Egypt
b
Ein Shams University, Faculty of Science Chemistry Department, Cairo, Egypt

Received 28 July 2013; accepted 30 October 2013

Available online 18 March 2014

KEYWORDS Abstract A kinetic investigation of the electrochemical removal of copper ions from solutions of
Kinetics; different initial metal concentrations using fixed packed-bed electrode in circulated batch system
Copper removal; was made. The electro-deposition of copper was found to be electron transfer controlled and fol-
Packed bed electrode lows first-order kinetics. The rate was found to be dependant on initial copper concentration,
applied current density and supporting electrolyte concentration. The change of copper concentra-
tion with time could be described by the equation:

C ¼ C0 ekt
where

k ¼ k0 eaðCDÞ
The value of k0 seemed to be independent of the initial concentration of copper in the treated
solution. However, the value of a depends on the initial concentration of copper and equals:

– a = 0.0073 for C0 6 100 mg/l

– a = 0.0058 for 100 < C0 6 200 mg/l
– a = 0.0041 for C0 P 250 mg/l
ª 2014 Production and hosting by Elsevier B.V. on behalf of Egyptian Petroleum Research Institute.

* Corresponding author.
E-mail address: halasaid1@yahoo.com (H.S. Hussein). 1. Introduction
Peer review under responsibility of Egyptian Petroleum Research
Institute.
Researchers with various electrochemical-cell designs have
attempted to remove copper from solutions with varying
degrees of achievements and improvements. No doubt that,
Production and hosting by Elsevier generally, a good electrolytic cell should be easy to set-up, easy

1110-0621 ª 2014 Production and hosting by Elsevier B.V. on behalf of Egyptian Petroleum Research Institute.
http://dx.doi.org/10.1016/j.ejpe.2014.02.013
94 I.A. Khattab et al.

to maintain, and has good solution flow. Moreover, for the 120
100 A/m2
electrochemical deposition of a metal from electrolytes, a large 200 A/m2
Ci = 150 m g/l

surface area of cathode is a must. Packed-bed electrodes of 300 A/m2

100 400 A/m2

Calculated concentrations, mg/l

granulate particles can offer large surface area per unit cell 500 A/m2
volume and are usually used to counteract the limitations of
the low space–time yield and low normalized space velocity 80
obtained in electrochemical processes with two-dimensional
electrodes [1]. More importantly, these electrodes are simple 60
to prepare, use, repack and regenerate in situ.
Generally, two extreme cases may be distinguished in the
electrochemical deposition process: electron transport control 40
and mass-transport control. In case of electron transport
control, the percent removal of copper rises linearly with time 20
[2]. On the other hand, in the second case, i.e. mass-transport
control, the current efficiency fell with time and the concen-
tration decay of the deposited species was exponential with 0
0 20 40 60 80 100 120
time [3].
Chu et al. [4] deduced a correlation, considering that the Observed concentrations, mg/l
electro-deposition process is mass-transfer controlled, correlat-
Figure 2 Comparison between observed and calculated copper
ing the concentration decay of the deposited species with time
concentrations (initial copper ion concentration = 150 mg/l).
in a packed-bed electrode system. The correlation presented by
Chu et al. [4] was:
CðtÞ ¼ C0 exp ½aut=V  ð1  expðL=kÞÞ ð1Þ Babatope et al. [6] utilized optimization techniques to theo-
where C(t): concentration of Cu at time t, second, C0: initial retically and practically optimize the fabrication and operation
concentration of Cu, mg/l, a: cross-sectional area of bed, of suitable electrochemical cells with the possibility of totally
cm2, u: superficial velocity (=volumetric flow rate/a), cm/s, removing copper from a CuSO4–Na2SO4 wastewater at almost
V: volume of electrolyte, cm3, L: bed height, cm, k: character- 100% current efficiency. No sufficient description of the cell is
istic length has a value of 7.3, defined by the authors. reported in their manuscript. They stated that the electrochem-
Ruotolo and Gubulin [5] studied the kinetic and hydrody- ical removal of copper ions follows first order kinetics and the
namic behaviors of a fixed-bed electrochemical reactor. The concentration at a particular time is given as:
porous cathode consisted of 1.0 mm equilateral cylindrical  
SC
copper particles. They reported that the curves describing ln CF ¼ ln C0  kt ð2Þ
VS
the kinetics of the decrease in copper concentration in the elec-
trolyte are linear up to the moment when they become expo- Where, CF: final concentration of copper ion after any given
nential in time. In spite they did not introduce any rate electrolysis time t, C0: the initial copper concentration, SC:
expression; the presented data indicate that the slope of the the total active cathode surface area, VS: volume of the electro-
linear portion, i.e. the rate of the deposition process, depends lyte solution being treated and k: the apparent first order reac-
on the range of initial concentration of copper. Moreover, the tion rate constant for copper electro-deposition at the cathode.
effect of current density on the deposition rate was not Eq. (2) indicates that the value of k is constant and indepen-
considered. dent of the applied current density. Additionally, the value of

120
100A/m2
200A/m2
Ci = 100 m g/l 100 A /m2 Ci = 300 m g/l
300A/m2
280 200 A/m2
100 400A/m2 300 A/m2
Calculated concetrations, mg/l

Calculated concentrations, mg/l

500A/m2 400 A/m2

240 500 A/m2

80
200

60 160

120
40
80

20
40

0 0
0 20 40 60 80 100 120 0 40 80 120 160 200 240 280
Observed concentrations, mg/l Observed concentrations, mg/l

Figure 1 Comparison between observed and calculated copper Figure 3 Comparison between observed and calculated copper
concentrations (initial copper ion concentration = 100 mg/l). concentrations (initial copper ion concentration = 300 mg/l).
Kinetic investigation of electrochemical removal of copper from dilute solutions 95

Time , min. Time , min.

0 10 20 30 40 0 10 20 30 40
0 0
100A/m 2
-0.05 (a) -0.1 (b) 200A/m 2

-0.2

ln c/co
ln c/c o
-0.1
-0.3
-0.15
-0.4
-0.2 y = -0.0066x y = -0.0174x
-0.5 R2 = 0.9552
R2 = 0.8772
-0.25 -0.6

Time , min. Time , min.

0 10 20 30 40 0 10 20 30 40
0 2
0
-0.2 (c) 300A/m -0.5 (d)
400 A/m 2

ln c/c o
-0.4 -1
ln c/c o

-0.6 -1.5
-0.8 y = -0.0336x
-2
y = -0.0725x
-1 R2 = 0.9928 -2.5 R2 = 0.9086
-1.2 -3

Time , min.
0 10 20 30 40
0
500 A/m 2
-1
(e)
ln c/co

-2

-3
y = -0.1272x
-4 R2 = 0.7835

-5

Figure 4 ln C/C0 versus time of electrolysis at 100 mg/l.

SC might be difficult if not impossible to estimate for a packed- In order to describe the performance of such a system or to
bed electrode made of graphite particles. The equation, as well, get data beyond the observed data, a mathematical expression
does not reflect the effect of the initial concentration of copper or correlation is needed. This correlation should establish the
on the electro-deposition rate. relationships between the variables controlling the system
In a previous study by Khattab et al. [7,8] it was found that behavior. In the literature there is no correlation correlating
the electrochemical removal of copper in a packed-bed batch- the six operational variables listed above. To find or to deduce
circulated system is a function of: such a correlation is a difficult task.
In this manuscript, the kinetics of the electro-deposition of
1. Applied current density. copper at the surface of a packed-bed cathode is dealt with
2. Initial copper concentration. when holding constant electrolyte flow rate, shape of current
3. Time of electrolysis. collector, concentration and type of supporting electrolyte
4. The flow rate of copper solution. and mass of graphite bed. Other variables, i.e. initial concen-
5. Type and concentration of supporting electrolyte. tration of copper, current density and time of deposition were
6. Shape of current collector. varied.

2. Experimental work
Table 1 Values of rate constant at different
current densities, 100 mg/l. The experimental set up and procedure were described
2
elsewhere (7).
Current density A/m k (rate constant)
100 0.0066 3. Results and discussion
200 0.0174
300 0.0336
400 0.0725 Generally, two extreme cases may be distinguished in the elec-
500 0.1272 trochemical deposition process: electron transport control and
mass-transport control. In case of electron transport control,
96 I.A. Khattab et al.

0.16
(a) y = 0.0036e 0.0073x
Table 2 Values of rate constant at different
0.14
R2 = 0.9919 current densities, 150 mg/l.

Rate constant (K)

0.12
0.1 Current density A/m2 k (rate constant)
0.08 100 0.0063
0.06 200 0.0147
0.04 300 0.0228
400 0.0369
0.02
500 0.0661
0
0 100 200 300 400 500 600
C.D A/m2
the fractional conversion (=% removal divided by 100) rises
6
linearly with time [2]. On the other hand, in the second case,
(b) i.e. mass-transport control, the current efficiency fell with time
5 and the concentration decay of the deposited species was expo-
4 nential with time [3].
Inspection of the results obtained in this work reveal that,
ln K

3
the fractional conversion rises in an exponential mode with
2 time and the current efficiency falls with time. Hence, it can
y = -0.0073x + 5.6336
1 R2 = 0.9919
be simply deduced that the system adopted in the present work
was operated under mass-transport control mode of operation.
0
0 100 200 300 400 500 600
C.D A/m2
3.1. Correlation for predicting percent removal

Figure 5 The effect of current density on the rate of reaction at Chu et al. [4] deduced a correlation, considering that the elec-
100 mg/l. trodeposition reaction is mass-transfer controlled, correlating

Time , min.
0 10 20 30 40
0
(a) 100A/m 2
-0.05
ln c/co

-0.1

-0.15 y = -0.0063x
R2 = 0.9913
-0.2

Time , min.
Time , min.
0 10 20 30 40
0 10 20 30 40
0 0
200 A/m 2
-0.1
(b) (c) 300 A/m 2
-0.2
-0.2
ln c/ co

in c/co

-0.4
-0.3
y = -0.0147x -0.6 y = -0.0228x
-0.4 R2 = 0.9987 R2 = 0.9409
-0.5 -0.8

Time , min. Time , min.

0 10 20 30 40 0 10 20 30 40
0 0
400 A/m 2 500 A/m 2
-0.2 (d) -0.5 (e)
-0.4
ln c/co

-1
ln c/co

-0.6
-1.5
-0.8
y = -0.0369x y = -0.0661x
-1 -2
R2 = 0.91 R2 = 0.95
-1.2 -2.5

Figure 6 ln C/C0 versus time of electrolysis at 150 mg/l.

Kinetic investigation of electrochemical removal of copper from dilute solutions 97

0.08 6
0.07 (a) (b)

Rate constant ( K )
5
0.06 y = 0.0041e 0.0056x
R2 = 0.9859 4
0.05

ln K
0.04 3
0.03 2
0.02 y = -0.0056x + 5.5033
1
0.01 R2 = 0.9859
0 0
0 100 200 300 400 500 600 0 100 200 300 400 500 600
C.D A/m2 C.D A/m2

Figure 7 The effect of current density on the rate of reaction for 150 mg/l (initial copper ion concentration).

Time, min. Time, min.

0 10 20 30 40 0 10 20 30 40
0 0
300A/m 2
(a) 100 A/m 2 -0.1 (b)
-0.05 -0.2
-0.3

ln C/CO
ln C/CO

-0.1 -0.4
-0.5
y = -0.0061x -0.6 y = -0.0231x
-0.15
R2 = 0.9164 R2 = 0.9756
-0.7
-0.2 -0.8

Time, min.
0 10 20 30 40
0
500A/m 2
(c)
-0.5
ln C/CO

-1

-1.5

-2 y = -0.0678x
R2 = 0.9786
-2.5

Figure 8 ln C/C0 versus time of electrolysis at 200 mg/l.

Table 3 Values of rate constant at different Moreover these authors reported values of removal or
current densities, 200 mg/l. extraction efficiencies for operational conditions very near to
those in the present work.
Current density A/m2 k (rate constant)
100 0.0061 3.1.1. Comparison between observed and calculated copper
300 0.0231 concentrations
500 0.0678
Fig. 1 shows a comparison between the observed and calcu-
lated Cu concentrations using the correlation (1) presented
by Chu et al. [4], the initial copper concentration had a nomi-
the concentration decay of the deposited species with time in a nal value of 100 mg/l at different current densities and
system similar to the experimental set-up adopted in this work. sampling time ranged from 10 to 30 min. The diagonal line
This correlation was chosen to predict the values of the ob- represents the coincidence between the observed and calcu-
served copper concentrations obtained in the current work. lated concentration.
Reasons for selecting this correlation are: As shown in the above figure it is interesting to note that, at
current densities less than 400 A/m2 the applied correlation
1. The deposited species is copper. underestimates the residual Cu in the treated solution. At
2. The system and mode of operation are similar. 400 A/m2 the observed and calculated concentrations get clo-
3. The bed material and the average particle size are the same. ser; the three concentrations of residual Cu corresponding to
4. The electrolyte flow rate is almost similar. sampling times 10, 15 and 20 min still underestimated by the
98 I.A. Khattab et al.

6
(a) 0.08 (b)
0.07 y = 0.0035e 0.006x 5

Rate of reaction (K)

0.06 R2 = 0.9963
4
0.05

ln K
0.04 3
0.03 2
0.02 y = -0.006x + 5.6591
1 R2 = 0.9963
0.01
0 0
0 100 200 300 400 500 600 0 100 200 300 400 500 600
C.D A/m2 C.D A/m2

Figure 9 The effect of current density on the rate of reaction at 200 mg/l.

Time , min. Time , min.

0 10 20 30 40 0 10 20 30 40
0 0
200 A/m 2
(a) 100 A/m 2
-0.05 (b)
-0.05

ln c/co
-0.1
ln c/co

-0.1
-0.15
-0.15 y = -0.0058x y = -0.0066x
-0.2 R2 = 0.5929
R2 = 0.9666
-0.2 -0.25

Time , min. Time , min.

0 10 20 30 40 0 10 20 30 40
0 0
300 A/m 2 400A/m 2
-0.1
(c) -0.1 (d)
-0.2
-0.2
ln c/co

ln c/co

-0.3
y = -0.0131x -0.4
-0.3 R2 = 0.9325 y = -0.0192x
-0.5 R2 = 0.9209
-0.4 -0.6
-0.5 -0.7

Time , min.
0 10 20 30 40
0
(e) 500 A/m 2
-0.2
ln c/ co

-0.4

-0.6
y = -0.0281x
-0.8 R2 = 0.935

-1

Figure 10 ln C/C0 versus time of electrolysis at 250 mg/l.

correlation. However, the two concentrations corresponding

Table 4 The effect of current density on rate
to 25 and 30 min coincide with the diagonal; this is a very good
constant at 250 mg/l.
prediction. The successfulness of Eq. (1) in predicting the two
Current density A/m2 k (rate constant) points may be explained by the situation that after processing
100 0.0058 the treated solution for 20 min, the residual Cu concentration –
200 0.0066 which will be the initial concentration of the next processing
300 0.0131 time – is very near to the initial concentration of the solution
400 0.0192 treated by Chu et al. [4]. At 500 A/m2, however, the correlation
500 0.0281 overestimates the residual copper concentration in spite of the
Kinetic investigation of electrochemical removal of copper from dilute solutions 99

closeness of the concentration corresponding to 30 min sam-
pling time.
Fig. 2 illustrates the situation where the initial Cu concen-
tration was 150 mg/l. Correlation (1) underestimates the ob-
served results. Nonetheless, concentrations after 25 and
30 min, at 500 A/m2, are very close to the diagonal; the reason
for this closeness may be due to the operating regime but at
this situation it was the mixed regime, as was previously
pointed out [3,9].
On the other hand, Fig. 3 indicates that, when the initial
concentration was 300 mg/l, all residual concentrations lie very
far from the diagonal to the right. It might be observed, how-
ever, that increasing current density shifts the points to the left
i.e. get closer to the diagonal.

0.03 6
(a) (b)
0.025 5
Rate constant (K )

0.02 4
y = 0.0034e 0.0042x
0.015 3

ln K
R2 = 0.971
0.01 2

0.005 1 y = -0.0042x + 5.6726

R2 = 0.9709
0 0
0 100 200 300 400 500 600 0 100 200 300 400 500 600
C.D A/m2 C.D A/m2

Figure 11 The effect of current density on the rate of reaction at 250 mg/l.

Time , min. Time , min.

0 10 20 30 40 0 10 20 30 40
0 0
(a) 100A/m 2 (b) 200 A/m 2

-0.05 -0.05
ln c/co
ln c/co

-0.1 -0.1

y = -0.0057x y = -0.0063x
-0.15
-0.15 R2 = 0.917 R2 = 0.6756

-0.2
-0.2

Time , min. Time, min.

0 10 20 30 40 0 10 20 30 40
0 0
-0.05 (c) 300A/m 2
-0.1
(d) 400A/m 2

-0.1
-0.15 -0.2
ln c/co
ln c/co

-0.2 -0.3
-0.25 -0.4
-0.3 y = -0.0123x y = -0.0185x
-0.35 -0.5 R2 = 0.8693
R2 = 0.9789
-0.4 -0.6

Time, min.
0 10 20 30 40
0
500A/m 2
(e)
-0.2
ln c/co

-0.4

-0.6
y = -0.0278x
-0.8
R2 = 0.9299
-1

Figure 12 ln C/C0 versus time of electrolysis for 300 mg/l copper ion concentration.
100
Table 5 Values of rate constant at different
current densities, 300 mg/l.
Current density A/m2 k (rate constant)
100 0.0057
200 0.0063
300 0.0123
400 0.0185
500 0.0278
In the present work, to model this system black box
approach was considered. The black box approach provides
a simpler and more appealing description of the cell and hence
its behavior toward the major process variables [3].
So far, the data presented in Figs. 1–3 without any doubt,
reveal that the controlling regime of copper deposition in this
work was mostly the electron-transfer regime.
Hence, for determining the order of copper deposition, a
plot of ln C/C0 against electrolysis time was constructed.
Fig. 4 describes this relation at 100 mg/l initial copper ion con-
centration. It is clear from this set of figures that the relation is
almost linear. Therefore, the deposition of copper follows a
first order reaction kinetics.
In this figure, the applied current density varied from
100 A/m2 to 500 A/m2 and the slope of line gave the value of
rate constant. The values of rate constant at different current
densities are listed in Table 1.
From the inspection of the results in Table 1, it is obvious
that the rate constant increased as the applied current density
increased. Then, by plotting the rate constant (k) versus cur-
rent density, it appeared that the rate constant changes with
current density in an exponential trend. Consequently, the rate
constant for copper electrodeposition process can be described
by the following equation:
k ¼ k0 eaðCDÞ ð3Þ
or in a linear form as:
ln k ¼ ln k0  aðC  DÞ ð4Þ
where; k is the rate constant value, k0 is the rate constant at
zero current density, a is the slope of line, and (CÆD) is the ap-
plied current density in A/m2.
Eq. (3) indicates that the dependence of the rate constant
on CÆD fits into an equation of the Arrhenius type.
Fig. 5 shows this relation at a copper ion concentration of
100 mg/l. The slope of the line gave the value of a = 0.0073
and k0, which may be defined as the rate constant at zero
current, equal to 0.0036.
Figure 13 The effect of current density on the rate of reaction at 300 mg/l.
I.A. Khattab et al.
Similar relationship is represented in Fig. 6 when the initial
copper concentration of the solution was 150 mg/l.
The effect of current density on the rate constant value at
150 mg/l is also shown in Table 2. We can notice that, the in-
crease of current density increased the rate constant value.
Also, Fig. 7 represents an exponential relationship of the
rate constant and the applied current density for 150 mg/l
initial copper ion concentration.
The slope of line, shown in Fig. 7b, gave a value of a
equal to 0.0056 and k0 equal to 0.0041.
Also, similar relationship is shown in Fig. 8 for a solution
of an initial copper ion concentration of 200 mg/l. The applied
current density had the values 100, 300 and 500 A/m2. Values
of the rate constant are shown in Table 3.
From plotting rate constant versus current density, an
exponential relationship was obtained as well. The lineariza-
tion of the exponential relationship, Fig. 9b, gave the value
of a equal to 0.006 and k0 equal to 0.0035.
Moreover, Fig. 10 shows ln C/C0 versus time of electrolysis
for the treatment of a solution having 250 mg/l of copper ions.
Table 4 includes the values of rate constant at different cur-
rent densities when the initial copper ion concentration was
250 mg/l.
When the rate constant was plotted versus the applied cur-
rent density, an exponential relationship was also obtained as
shown in Fig. 11 for 250 mg/l initial copper ion concentration.
The values of a and k0 were 0.0042 and 0.0034, respectively.
Also, Fig. 12 indicates almost similar results when the initial
copper ion concentration was 300 mg/l. The slope of the pro-
duced lines gave the values of rate constant listed in Table 5.
Fig. 13 shows also the rate constant versus applied current
density for the solution containing 300 mg/l of copper. The
values of a and k0 were 0.004 and 0.003, respectively.
Moreover, Fig. 14 illustrates the relation of ln C/C0 and time
of electrolysis for a solution of copper having 350 mg/l initial
concentration. The slope of each line gave the value of rate con-
stant at the corresponding current density. These values are listed
in Table 6 and plotted in Fig. 15a. Inspection of Fig. 15b shows a
semi-logarithmic presentation of the rate constant versus the
applied current density for 350 mg/l of copper ions; a straight line
correlates ln k and CÆD. The slope and intercept of this line give
the values of a and k0 as 0.004 and 0.004, respectively.
The effect of initial copper concentration on the rate con-
stant of the deposition process was investigated; the values
of a and k0 are listed in Table 7. These values reveal that
k0 can be assumed constant without introducing significant er-
ror. The value of a, however, is remarkably affected by initial
copper concentration.
Kinetic investigation of electrochemical removal of copper from dilute solutions 101

Figure 14 ln C/C0 versus time of electrolysis at 350 mg/l.

For C0  100 mg=l;k ¼ k0 eð0:0073CDÞ ð5Þ

Table 6 Values of rate constant at different current densities,
ð0:0058CDÞ
350 mg/l. For 100 < C0  200 mg=l;k ¼ k0 e ð6Þ
ð0:0041CDÞ
Current density A/m2
k (rate constant) For C0  250 mg=l;k ¼ k0 e ð7Þ
100 0.0052 The average value of k0 is 0.0037.
200 0.0096 In performing the electrodeposition of copper using 0.5 M
300 0.0149
NaCl solution as supporting electrolyte, the value of retained
400 0.0192
500 0.0296
copper concentration at any time is given as:
C ¼ C0 ekt ð8Þ
The electrochemical deposition of copper is a heteroge-
where
neous process. Therefore, the expression for the rate of an
electrode reaction includes both activation controlled and k ¼ 0:0037eðaCDÞ ð9Þ
diffusion controlled reactions. Actually, the reaction rate ex-
In a previous study, Chen et al. [2] mentioned that the elec-
pressions at such electrodes are of a very complex form, but
trodeposition of copper follows a first order kinetics; however,
can be approximated by considering the black-box approach.
the value of k was different.
It seems that the rate of such a reaction will in general depend
Then, a comparison between the observed and calculated
not only on the concentration of the principal reactants, but
copper concentrations was carried out by applying Eqs. (8 and
also on the concentration of every ion in the solution.
9). Figs. 10–15 show the effect of current density on the rate of
From Table 7, it is clear that, there are three rate expres-
removal of copper at 100, 150, 200, 250, 300 and 350 mg/l,
sions depending on the initial concentration, i.e.:
102 I.A. Khattab et al.

Figure 15 The effect of current density on the rate of reaction at 350 mg/l.

Table 7 The effect of initial copper concentration on the rate 350

100 mg/l
constant value. 150 mg/l

Calculated concentrations, mg/l

300 200 mg/l
Initial copper conc. a k0 250 mg/l
100 0.0073 0.0036 250 300 mg/l
350 mg/l
150 0.0056 0.0041
200 0.006 0.0035 200
250 0.0042 0.0034
300 0.0042 0.0033 150
350 0.004 0.004
100

50
respectively. Also, Fig. 16 collects these results and gave good
agreement between the observed and calculated concentrations. 0
The effect of supporting electrolyte concentration on the 0 50 100 150 200 250 300 350
values of the rate constant of the deposition process was also Observed concentrations, mg/l
considered. Fig. 17 shows ln C/C0 versus electrolysis time at
different sodium chloride concentrations ranged from 0.5 M Figure 16 Comparison between the observed and calculated
to 1 M. It is clear from this mentioned figure that, sodium copper concentrations at different initial copper concentrations.

Time, min. Time, min.

0 10 20 30 40 0 10 20 30 40
0 0
-0.1 (a) 500A/m 2 0.5 M NaCl
-0.2 (b) 500 A/m 2 0.75 M NaCl
-0.2
-0.4
-0.3
lnC/Co
ln C/Co

-0.4 -0.6
-0.5 -0.8
-0.6
-1
-0.7 y = -0.0278x y = -0.0403x
R2 = 0.9299 -1.2 R2 = 0.9754
-0.8
-0.9 -1.4

Time, min.
0 10 20 30 40
0
-0.2 (c) 500 A/m 2 1M NaCl
-0.4
-0.6
lnC/Co

-0.8
-1
-1.2 y = -0.0445x
-1.4 R2 = 0.97
-1.6

Figure 17 ln C/C0 versus time of electrolysis at different sodium chloride concentrations.

Kinetic investigation of electrochemical removal of copper from dilute solutions 103

0.05 concentration. The value of a (is the slope of the line repre-
0.045
0.04
senting the relation between ln k versus applied current
Rate constant ( k)
0.035 density), however, depends on the initial concentration of
0.03 copper.
0.025
0.02
0.015 – a = 0.0073 when C0 6 100 mg/l
0.01
– a = 0.0058 for 100 < C0 6 200 mg/l
0.005
0 – a = 0.0041 for C0 P 250 mg/l
0 0.2 0.4 0.6 0.8 1 1.2
NaCl conc., M By introducing this simple model, good agreement could be
obtained between predicted and observed data. The reaction
Figure 18 The effect of sodium chloride concentrations on the
was found to be electron transfer controlled.
rate constant value.

chloride concentration has a positive effect, i.e. increasing so- References

dium chloride concentration increases the deposition process
as shown in Fig. 18.
4. Conclusion
The electrodeposition of copper was found to follow first-
order kinetics and dependant on initial copper concentration,
applied current density and supporting electrolyte concentra-
tion then it was described by the equation:
C ¼ C0 ekt
where
k ¼ k0 eaðCDÞ
The value of k0 (is the value of k when CÆD = 0) seemed
to be independent of the initial concentration of copper in
the waste solution. The rate constant increased as the applied
current density increased and with increasing sodium chloride
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