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Electrochimica Acta 103 (2013) 266274
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Discussion
A kinetic model to describe the nickel electro-recovery from
industrial plating efuents under variable electrolyte conductivity
J.R. Hernndez-Tapia, J. Vazquez-Arenas

, I. Gonzlez
Departamento de Qumica, Universidad Autnoma Metropolitana, San Rafael Atlixco 186, C.P. 09340, Mxico, D.F., Mexico
a r t i c l e i n f o
Article history:
Received 27 March 2013
Received in revised form23 April 2013
Accepted 23 April 2013
Available online 3 May 2013
Keywords:
Nickel electrodeposition
Recovery
Modeling
Kinetics
Mass-transport
Electrolyte conductivity
a b s t r a c t
A comprehensive model is developed to account for the kinetics of nickel electro-recovery from industrial
plating efuents, typically containing low sulfate (1.2518.73 mol m
3
), chloride (0.497.41 mol m
3
)
and borates concentrations (9.96150 mol m
3
) at pH 4. The model is developed for linear sweep vol-
tammetry considering the mass-transport of six species in solution under stagnant conditions: Ni
2+
,
NiSO
4(aq)
, H
+
, Na
+
, SO
4
2
and Cl

, and accounting for the kinetic discharges of Ni

2+
, NiSO
4(aq)
, H
+
and H
2
O
on the substrate. Additionally, the challenges imposed for the analysis of different baths with variable
electrolyte conductivities (3974202 S cm
1
), migration effects and diffusion coefcients depending on
ionic strength (NernstHartley equation), are incorporated into the model to simulate the real conditions
of the plating efuents. When only one nickel species (Ni
2+
) is considered in the model, large deviations
are observed between the model and the experimental data at intermediate and high overpotentials
of the voltammograms. On the other hand, very good ts are obtained when two nickel species (Ni
2+
,
NiSO
4(aq)
) are introduced in the model for the experiments conducted at variable electrolyte conductiv-
ity. The prediction capabilities of the model are clearly proven by simulating different experimental data
generated at constant conductivities, using a single set of kinetic parameters calculated from the tting
stage. The model is developed in a general form such that it can be extended for the robust analysis of
other systems or experimental conditions.
2013 Elsevier Ltd. All rights reserved.
1. Introduction
In the last decades, the implementation of metal recovery pro-
grams has grown considerably for the treatment of industrial
efuents. These programs are the result of stricter environmental
policies, whichattempt tomitigatetheair andwater pollutions. The
electroplating industry has not been exempted to these changes,
whereby it has been stimulated to develop newand more efcient
technologies for the treatment of its discharges. Latest efforts have
been oriented to improve the recovery efciency of a large amount
of heavymetals (e.g. nickel) at low-cost. These metals are generated
fromrinsing solutions, whichuse a large volume of water. Although
these efuents can be processed with conventional methods such
as coagulation [1] and electrocoagulation [2], high costs of opera-
tion due to the generation of large amounts of sludge detract their
protability. Thus, alternative methods need to be implemented in
order to fulll these demands.
Electro-recovery methods offer attractive and efcient
alternatives in contrast with chemical methods (e.g. continuous

Corresponding author. Tel.: +55 58044600x2686; fax: +52 5558044611.

E-mail addresses: jgva@xanum.uam.mx, jorge gva@hotmail.com
(J. Vazquez-Arenas).
high volume treatment). Electro-recovery has been successful
in the treatment of efuents containing copper, since sludge
is not generated and the metal can be recovered with high
purity [3]. These characteristics are of great economic benet
since they augment the protability of the process. Additionally,
sewage discharges containing nickel represent a high economic
interest on account of its prize. However, its electro-recovery
is a challenge because nickel ions are typically found in low
concentration in the efuents [4]. This enhances the occurrence
of parasitic reactions (e.g. proton reduction), which leads to the
contamination of the recovered metal [5,6], and increases the
energy consumption of the process since the electrolyte con-
ductivity is low [7]. These factors affect the current efciency
of the process and generate the formation of nickel hydroxides
which passivate the cathode [8,9]. Consequently, these parasitic
reactions not only consume more energy for the process, but
also diminish the purity of nickel. Hence, the optimum opera-
tion conditions for the nickel electro-recovery result complex
to nd. In general, they are evaluated empirically whereby
can be time-consuming and do not necessary entails the best
results.
Comprehensive kinetic modeling of the electrochemical reac-
tions involved in this process offers a tractable and ideal alternative
in order to tackle the design, development and optimization of
0013-4686/$ see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.electacta.2013.04.122
Author's personal copy
J.R. Hernndez-Tapia et al. / Electrochimica Acta 103 (2013) 266274 267
Table 1
Typical synthetic solutions with variable electrolyte conductivity, simulating rinsing discharges generated from the plating industry (e.g. Watts-type bath for nickel
deposition).
Bath no. NiSO
4
(mol m
3
) NiCl
2
(mol m
3
) H
3
BO
3
(mol m
3
) pH Conductivity
a
(S cm
1
)
1 1.25 0.49 9.96 4.0 397
2 3.12 1.23 25.0 4.0 909
3 6.24 2.47 50.0 4.0 1515
4 9.37 3.70 75.0 4.0 2041
5 12.49 4.94 100.0 4.0 2488
6 15.61 6.17 125.0 4.0 2994
a
Experimental value.
Table 2
Typical synthetic solutions with relatively constant electrolyte conductivity, simulating rinsing discharges generated from the plating industry (e.g. Watts-type bath for
nickel deposition).
Bath no. NiSO
4
(mol m
3
) NiCl
2
(mol m
3
) Na
2
SO
4
(mol m
3
) NaCl (mol m
3
) H
3
BO
3
(mol m
3
) pH Conductivity
a
(S cm
1
)
7 3.12 1.23 15.61 12.34 150.0 4.0 4717
8 6.24 2.47 12.49 9.87 150.0 4.0 4425
9 12.49 4.94 6.24 4.94 150.0 4.0 3953
10 15.61 6.17 3.12 2.47 150.0 4.0 3817
11 18.73 7.41 0 0 150.0 4.0 4202
a
Experimental value.
electro-recovery processes. Although research in electrolysis of
nickel has been conducted primarily for the analysis of the macro-
scopic properties of the deposits [10], different efforts have been
carried out to propose and quantify the reaction mechanism of
the nickel electrodeposition in high nickel concentration and acid
media. To this concern, several studies have been carried out with
the intention to improve future developments through model-
ing [6,11,12]. Vazquez-Arenas and Pritzker have comprehensively
evaluated the Ni(II) reaction mechanism under different experi-
mental conditions using electrochemical impedance spectroscopy,
linear sweep voltammetry and steady-state polarization curves
[1214]. Experimental evidence and modeling indicated that H
+
reduction was the rst reaction occurring at more positive poten-
tials, followed by Ni(II) and water reduction. Ni(II) reduction was
assumed to involve an adsorbed intermediate species Ni(I)
ads
in
the rst mono-electronic step, which was then consumed to pro-
duce metallic nickel in a consecutive mono-electronic transfer
[12,13]. The second transfer step (i.e. metal deposition) of Ni(II)
reduction was much faster compared to the rst mono-electronic
step, whereby the nickel reaction mechanism could be simpli-
ed into one bi-electronic charge transfer step, particularly when
implemented in macroscopic scale such as an electrochemical
reactor:
Ni
2+
+2e Ni
0
(1)
Such implications could additional arise from the fact that is dif-
cult to account for the balance of sites where Ni(I)
ads
species are
adsorbed, due to the heterogeneities presented on large electrodes.
H
+
and water reduction (HER) have been also considered to reduce
in mono-electronic steps [12,13]. However, there are also ques-
tionable premises whether the HER affects or not the reduction of
iron-group metals [1517], as well as its occurrence on large elec-
trodes. Additionally, it is not simple to determine experimentally
if the consumption of H
ads
proceeds by chemical combination of
adjacent H
ads
adatoms (Tafel) or electrochemical reduction (Hey-
rovsky). Accordingly, in view of these possibilities and the lack of
experimental evidence, H
+
and water reduction have been consid-
ered to occur in a 2-electron transfer step [15]:
2H
+
+2e

H
2
(2)
2H
2
O+2e

H
2
+2OH

(3)
Reaction (2) is thermodynamically more noble than reaction (1),
whereas water reduction arises at more negative potentials when
reactions (1) and (2) become mass-transport limited.
However, the previous models developed by these authors
[6,1113] are not applicable to the electro-recovery of nickel from
electroplating efuents, since they were developed for high con-
centrated solutions. The present case involves mimic solutions
of different rinsing efuents where low supporting electrolyte
(3974202S cm
1
) andNi(II) concentrations rangingunder dilute
conditions 2001000ppm are considered. Accordingly, migration
effects become important andpresumably the variationof the elec-
trolyte conductivity affects considerably the reduction rate of the
metal. Additionally, variations in the electrolyte composition (e.g.
Cl

, SO
4
2
) of the efuent could modify the predominance of the
nickel species and, thus the kinetic rate to discharge the metal.
The present study is intended to analyze and quantify the reaction
mechanismof nickel electro-recovery fromtypical industrial efu-
ents generated fromplating operations. Linear sweep voltammetry
(LSV) techniques under stagnant conditions are utilized in combi-
nation with modeling to develop a model capable to account for
different experimental conditions observed in these efuents. Pre-
vious ndings, assumptions and models reported by other authors
are considered[6,11,12]. Tothe authors knowledge, this study con-
stitutes the rst effort to analyze the nickel electro-recovery from
industrial plating euents, considering the challenges imposed by
these solutions. This work comprises the rst stage of the design
and optimization of an electrochemical reactor for nickel electro-
recovery fromindustrial plating efuents (e.g. rinsing solutions).
2. Experimental
The experiments were conducted at room temperature in typ-
ical synthetic solutions simulating rinsing discharges generated
from the plating industry (e.g. Watts-type bath for nickel deposi-
tion). Different NiSO
4
(99.9%, J.T. Baker), NiCl
2
(98%, J.T. Baker) and
B(OH)
3
(99.8%, Merck) concentrations were considered according
to the electrolyte conductivity () of the solution. Table 1 considers
baths with variable conductivity (without supporting electrolyte),
and Table 2 reports electrolytes of relatively constant (addi-
tion of Na
2
SO
4
and NaCl as supporting electrolyte). The pH of
the electrolytes was always adjusted to 4. Thermodynamic stud-
ies, micro and macro electrolysis conducted by our research group
Author's personal copy
268 J.R. Hernndez-Tapia et al. / Electrochimica Acta 103 (2013) 266274
have shown that this pH value is optimum to mitigate the proton
and water reduction, as well as suppressing the formation of nickel
hydroxides [18]. All solutions were freshly prepared with deion-
ized water and deoxygenated with N
2
(Praxair, grade 4.8) prior to
experiments.
The electrochemical experiments were conducted in a
conventional 3-electrode cell with volumetric capacity of
100mL. A long pure graphite rod (99.999%, Alfa AESAR) and a
Hg/HgSO
4(s)
/K
2
SO
4(sat)
electrode were, respectively, used as the
counter and reference electrodes. All the potential values are
reported in this scale (0.641V vs. SHE). The working electrodes
were nickel (99.999%, Alfa AESAR) rods embedded in Teon, with
0.196cm
2
of exposed area. The three electrodes were connected
to a Princeton Applied Research
TM
potentiostat/galvanostatmodel
VMP3, controlled by the EC-Lab
TM
software version V10.18. Prior
to each experiment, the working electrode was polished using
SiC-type abrasive paper (1200 grade) and then Buehler alumina
powder (nal grain size 0.05m) to a mirror nish. The electrode
was then sonicated and rinsed with deionized water to remove
remaining particles on its surface. The conductivity was measured
using a multi-parameter meter model MP551pH/mV/ISE/Cond/DO
Meter Shanghai San-Xin Instrumentation, Inc.
3. Modeling
3.1. Kinetics reaction mechanism
This section details the derivation of a model proposed in this
study to analyze the nickel electrorecovery in typical synthetic
solutions simulating rinsing discharges generated fromthe plating
industry (i.e. lowsupporting electrolyte). Assumptions considered
in the model as well as other aspects to implement it are also
provided. The model is developed in a general form such that it
can be extended to the analysis of other systems or experimental
conditions. The model is subsequently utilized to t the experi-
mental data reported in Section 4. The nickel electro-recovery is
carried out onto nickel substrates and parasitic reactions (i.e. HER)
occur simultaneously on these surfaces. The model describes the
electrode response during a LSV under stagnant conditions.
The current density expressions for the Ni(II), H
+
and water
reduction(reactions (1)(3)) proceed, respectively, throughthe fol-
lowing expressions without considering the backward steps (e.g.
reactor implementation):
j
Ni
2F
= k
Ni
exp
_

Ni
F(E

s
)
RT
_
C
s
Ni(II)
(4)
j
H
F
= k
H
exp
_

H
F(E

s
)
RT
_
C
s
H
(5)
j
W
F
= k
W
exp
_

W
F(E

s
)
RT
_
(6)
C
s
Ni(II)
and C
s
H
represent the surface concentrations of Ni(II) and H
+
,
respectively, while k
Ni
, k
H
and k
W
are rate constants and
Ni
,
H
and
W
are charge transfer coefcients for the Ni(II), H
+
and water
reduction, respectively. E

is the electrode potential corrected for

the ohmic resistance R
s
(E

=Ej
T
R
s
) and
s
the electric potential
in the electrolyte. The Tafel for a half-cell reaction can be written
in one of two alternative forms one in terms of rate constants
and the electrode potential E

(present case) and the other in terms

of the exchange current density and the overpotential [19]. When
usingthepresent formthat involves theelectrodepotential E

, there
is no need to deal with the formal or reversible potentials in the
formulation of the model.
The model is used to describe the electrode response when the
potential is perturbed during LSV. In this technique, the potential
is varied linearly with time as follows:
E = E
OCP
s
rate
t (7)
where E
OCP
is the open-circuit potential (V) and s
rate
is the scan rate
in Vs
1
.
The total current density measured during the potential scan is
composed of faradaic (j
f
) and capacitive (j
c
) components:
j
T
= j
f
+j
c
= j
Ni
+j
H
+j
W
+C
dl
dE

dt
(8)
where C
dl
is the double layer capacity.
3.2. Transport equations
The following assumptions are considered to develop a 1-
dimensional model:
(a) The current distribution is uniformover the working electrode;
onlytransport inthe y-directionnormal tothe electrode surface
is considered.
(b) The uid is incompressible Newtonian, constants (e.g. diffu-
sion coefcient, density) and kinetic parameters are uniform
throughout the system.
(c) The solution is isothermal at 298K.
(d) Ideally dilute behavior is assumed in the solution (i.e. activity
coefcients are equal to 1.0).
(e) H
3
BO
3
species does not dissociate, whereby has a negligible
contribitution to the electrolyte conductivity.
(f) Homogeneous reactions are considered to be faster than the
electrode reactions and the rate of mass transport.
(g) The electrode is under stagnant conditions, thus, the transient
diffusion layer region grows at a rate equals to (t) = 2
_
D
i
t
[19], whence the boundary situated at the bulk must be treated
as a moving boundary.
The transient mass balance for the different soluble species in
the systemis:
C
i
t
= N
i
(9)
where the migrational-diffusional ux N
i
(y,t) of the dissolved
species i (Ni(II), H
+
, Na
+
, Cl

and SO
4
2
) can be expressed as:
N
i
= D
i
C
i
y

z
i
D
i
F
RT
C
i

s
y
(10)
D
i
is the diffusion coefcient of any species involved in diffusive
transport, and whose concentration dependence is given by the
NernstHartley equation [20].
D
i
= D
0
i
_
1 +C
i
ln
i

C
i
_
(11)
where D
0
i
is the limiting value of the diffusion coefcient (refer to
Table 3) and
i

is the activity coefcient of the dissolved species i.

In order to solve coherently for
s
, the electroneutrality condition
is added to the transport equations. This condition establishes that
the net charge is zero everywhere in the solution:

z
i
C
i
= 0 (12)
In order to isolate and identify the electrolyte conductivity term
in the model, it is necessary to sumthe ux of all dissolved species
subjected to chemical and electric gradients. Thus, the mass bal-
ances expressed by Eq. (9) for the dissolved species i (Ni(II), H
+
, Na
+
,
Author's personal copy
J.R. Hernndez-Tapia et al. / Electrochimica Acta 103 (2013) 266274 269
Table 3
Parameters obtained fromtting the model to the experimental LSV data shown in
Table 1, and utilized to compute the simulations of the LSV data shown in Table 2.
Parameter Value
D
0
Ni
2+
= D
0
NiSO
4
5.510
10
m
2
s
1
D
0
H
+
9.7810
9
m
2
s
1
D
0
Na
+
1.3310
9
m
2
s
1
D
0
SO
2
4
6.610
10
m
2
s
1
D
0
Cl

1.3210
9
m
2
s
1
2
Ni
2+ 0.19
2
NiSO
4
0.32
H 0.5
W 0.5
k
Ni
2+ 6.610
14
ms
1
k
NiSO
4
2.2610
12
ms
1
kH 2.510
12
ms
1
kW 1.2210
18
mol m
2
s
1
C
dl
0.46F m
2
Cl

and SO
4
2
) can be added and multiplied by Fz
i
in the following
form:
F
5

i=1
z
i
C
i
t
=
_
F
5

i=1
z
i
N
i
_
=
_
F
5

i=1
z
i
_
D
i
C
i
y

z
i
D
i
F
RT
C
i

s
y
_
_
(13)
where the term on the right-hand side is zero as a result of
the electroneutrality condition (Eq. (13)). This generates one of
the equations forming the system of partial differential equations
(PDEs), when the electrolyte conductivity is variable () as a func-
tion of the chemical gradients:

_
5

i=1
_
Fz
i
D
i
C
i
y
+
F
2
z
2
i
D
i
RT
C
i

s
y
_
_
=
_
5

i=1
_
Fz
i
D
i
C
i
y
_
+

s
y
_
= 0 (14)
Typical rinsing solutions originated from the electroplating
industry present two main characteristics, as observed in the con-
centrations shown in Tables 1 and 2: the supporting electrolyte is
relatively lower (or virtually zero) compared to the metallic species
whereby migration effects become important, and the concentra-
tion of the species in solution is variable whence the electrolyte
conductivity changes fromthe bulk solution as it approaches to the
surface of the electrode:
=
F
2
RT

i
z
2
i
u
i
C
i
(15)
where F is Faradays constant (96,487Cequivalent
1
), R is the gas
constant, T is the temperature on the Kelvin scale, z
i
is the charge
of the i specie, u
i
is the mobility i specie, and C
i
is the concen-
tration of the i specie. Eq. (15) could be replaced by a constant
value (e.g. bulk measurement) when the chemical gradients cre-
ated by the electrochemical reaction do not affect its value, or by
an empirical tted value calculated at different electrolyte compo-
sitions [21]. The other three equations for H
+
, Na
+
, Cl

and SO
4
2
,
complementing this systemof PDEs are:
C
i
t
=
_
D
i
C
i
y
+
z
i
D
i
F
RT
C
i

s
y
_
(16)
The concentration of each species i at y =(t) is at its bulk level
C
b
i
at any stage of the experiment, i.e.
C
i
_
, t
_
= C
b
i
(17)
Since migration also holds at the electrode surface y =0, the rst
boundary condition results from simplifying the addition of the
ux of all dissolved species and multiplying by Fz
i
:
5

i=1
_
D
i
C
i
y
+
z
i
D
i
F
RT
C
i

s
y
_

y=0
=
j
Ni
2F
+
j
H
F
(18)
Additional boundary conditions required to solve the model are:
D
H
+
C
H
+
y
+
z
H
+D
H
+F
RT
C
H
+

s
y

y=0
=
j
H
F
(19)
D
Na
+
C
Na
+
y
+
z
Na
+D
Na
+F
RT
C
Na
+

s
y

y=0
= 0 (20)
D
Cl

C
Cl

y
+
z
Cl
D
Cl
F
RT
C
Cl

s
y

y=0
= 0 (21)
D
SO
2
4
C
SO
2
4
y
+
z
SO
2
4
D
SO
2
4
F
RT
C
SO
2
4

s
y

y=0
= 0 (22)
The concentration of each species is initially uniform everywhere
at its bulk level C
b
j
,
C
i
(y, 0) = C
b
i
(23)
The systemof PDEs, algebraic expressions, boundary conditions
and initial conditions given by Eqs. (4)(23) are solved using the
nite element method in the COMSOL Multiphysics
TM
4.2a soft-
ware package. The model parameters are estimated by tting the
model totheLSVdatarecordedunder different experimental condi-
tions (e.g. Ni(II) concentration, electrolyte composition, scan rate),
using a simplex search algorithmprovided by the MATLAB R2010b
toolbox.
4. Model tting and discussion
Two different scenarios were considered to assess the capa-
bilities of the model to describe and predict the Ni(II) reduction
process from industrial platting efuents (i.e. dilute conditions).
The rst one considers the tting of linear sweep voltammograms
under variable electrolyte conductivity subjected to changes in the
supporting electrolyte (Table 1), in order to determine the kinetic
parameters of the system. Note that this scenario does not con-
sider the mass-transport of Na
+
species. The second case is used
to predict the voltammetric response using the kinetic parameters
determined in the rst scenario. This second case contemplates the
use of solutions with a relative constant conductivity (e.g. xed
supporting electrolyte). This scheme has been considered since it
provides sufcient information to identify the different relaxation
phenomena arising when the solution conductivity is varied, and
the supporting electrolyte is not added.
The effects of the Ni(II) concentration during the potential
scan at 50 and 70mV s
1
are, respectively, shown in Fig. 1a
and b, under variable electrolyte conductivity. These voltam-
mograms were obtained at three different Ni(II) concentrations
and supporting electrolyte presented in Table 1, baths 13. In
these voltammograms, the scan was started fromthe open circuit
potential (OCP) in the negative direction. As observed in Fig. 1,
Author's personal copy
270 J.R. Hernndez-Tapia et al. / Electrochimica Acta 103 (2013) 266274
0
10
20
30
40
a
b
-2 -1.5 -1 -0.5 0
-
j
T
/

A

m
-
2
E - j
T
R
s
vs SSE/ V
bath 2
bath 1
bath 3
symbols - experiment
continous line - model
0
10
20
30
40
50
-2 -1.5 -1 -0.5 0
-
j
T
/

A

m
-
2
E - j
T
R
s
vs SSE/ V
bath 2
bath 1
bath 3
symbols - experiment
continous line - model
Fig. 1. Experimental (symbols) and model-tted (continous line) linear sweep
voltammograms obtained at variable electrolyte conductivity (baths 13,
3971515S cm
1
): (a) 50mV s
1
and (b) 70mV s
1
, simulating rinsing discharges
generated fromthe plating industry. A model describing the discharge of single Ni
2+
species was utilized.
a higher current density is in general obtained for the voltam-
mograms recorded at higher Ni(II) concentrations (bath 3) due to
the enhancement of the reaction rate, as a result of a larger surface
concentration of these species. The current density obtained from
the experiments conducted in baths 1 and 2 becomes lower, as a
function of the Ni(II) concentration. Note the different waves pre-
sentedduringthecourseof theseexperiments, whichcanberelated
to the occurrence of multiple electrochemical reactions contribut-
ing tothe total current. These processes present different activation
energies and become coupled at intermediate potentials, whence it
is difcult to identify experimentally their onset in the system, and
the magnitudes of their contributions. As a rst approach, visual
inspection of Fig. 1a and b indicates that the rst wave located at
the least negative potentials arises approximately at 0.6V, while
two more waves start at potentials around 1.1 and 1.5V. Pre-
vious studies carried out at higher electrolyte concentrations have
combined experimental work and modeling to propose that nickel
deposition is accompanied with H
+
and water reduction [8,13]. In
this direction, H
+
reduction is suggested to occur at less negative
potentials than nickel deposition, since they are thermodynami-
cally more noble than Ni(II) species [8], whereas more negative
potentials are characterized by the onset of water reduction. This
former reaction is enhanced since the H
+
and Ni(II) concentrations
deplete close to the surface of the electrode, as a result of their con-
sumption during the early stages of scan. However, as mentioned
above, these studies [8,13] were experimentally conducted at very
0
10
20
30
a
b
-2 -1.5 -1 -0.5 0
-
j
T
/

A

m
-
2
E - j
T
R
s
vs SSE/ V
bath 7
bath 8
symbols - experiment
continous line - model
0
10
20
30
40
50
-2 -1.5 -1 -0.5 0
-
j
T
/

A

m
-
2
E - j
T
R
s
vs SSE/ V
bath 7
bath 8
symbols - experiment
continous line - model
Fig. 2. Experimental (symbols) and model-simulated (continous line) linear sweep
voltammograms obtained under constant electrolyte conductivity (baths 78,
47174425S cm
1
): (a) 50mVs
1
and(b) 70mV s
1
, simulating rinsing discharges
generated fromthe plating industry. A model describing the discharge of single Ni
2+
species was utilized. The kinetic parameters (not shown) utilized in the simulations
were obtained fromthe tting to the experimental data presented in Fig. 1.
high concentrations (supporting electrolyte and Ni(II)) and under a
constant electrolyte conductivity, whereby the reaction rates and
the contribution of each reaction are different. In addition, previ-
ous modeling was computed neglecting the migration inputs and
without considering the electrolyte conductivity. Thus, in order to
analyze the reaction mechanismof Ni(II) reduction under the con-
ditions of this study, the model proposed in section 3 was t to the
experimental data presented in Fig. 1 (only the results presented
in Fig. 1a and b are included for a better appreciation), the tted-
model results areshownas continous lines. Ingeneral, thequalityof
the ts is good at lowoverpotentials, but there are important devi-
ations at intermediate and more negative potentials, particularly at
70mV s
1
. As observed fromthese gures, the currents calculated
withthe model overestimate the currents obtainedfromthe exper-
iments. Note that the LSVs computedwiththe model showa peakat
more negative potentials, which is typically associated with mass
transfer limitations. In addition, the current density values esti-
mated using the model do not match with the experimental ones
in this region. If the kinetic parameters obtained fromthe t to the
previous experimental data (Table 1, variable electrolyte conduc-
tivity) are used to simulate the experiments collected at constant
electrolyte conductivity (e.g. baths 7 and 8, Table 2), plots as shown
in Fig. 2a and b are obtained. These simulations reveal similar fea-
tures to those obtained in the tting stage (Fig. 1a and b), low
overpotentials are well-described, while intermediate and more
negative potentials present somehow deviations that suggest the
lack of mechanistic information accounting for the electrochemi-
cal response inthese potential regions.These differences couldarise
fromthe formation of different nickel species in solution resulting
Author's personal copy
J.R. Hernndez-Tapia et al. / Electrochimica Acta 103 (2013) 266274 271
0
0.2
0.4
0.6
0.8
1
1.2
0 2 4 6 8 10 12 14
F
r
a
c
t
i
o
n

N
i
(
I
I
)
pH
NiSO
4
Ni
2+
Ni(OH)
2 (s)
[Cl
-
]
tot
= 0.49
[Ni
2+
]
tot
= 1.74 mol m
-3
[SO
4
2-
]
tot
= 1.25
a)
0
0.2
0.4
0.6
0.8
1
1.2
0 2 4 6 8 10 12 14
F
r
a
c
t
i
o
n

N
i
(
I
I
)
pH
NiSO
4
Ni
2+
Ni(OH)
2 (s)
[Cl
-
]
tot
= 6.17
[Ni
2+
]
tot
= 21.78 mol m
-3
[SO
4
2-
]
tot
= 15.61
b)
0
0.2
0.4
0.6
0.8
1
1.2
0 2 4 6 8 10 12 14
F
r
a
c
t
i
o
n

N
i
(
I
I
)
pH
NiSO
4
Ni
2+
Ni(OH)
2 (s)
[Cl
-
]
tot
= 7.41
[Ni
2+
]
tot
= 4.36 mol m
-3
[SO
4
2-
]
tot
= 18.73
c)
0
0.2
0.4
0.6
0.8
1
1.2
0 2 4 6 8 10 12 14
F
r
a
c
t
i
o
n

N
i
(
I
I
)
pH
NiSO
4
Ni
2+
Ni(OH)
2 (s)
[Cl
-
]
tot
= 7.41
[Ni
2+
]
tot
= 26.14 mol m
-3
[SO
4
2-
]
tot
= 18.73
d)
Fig. 3. Fraction-pH diagrams of Ni(II) species calculated at the experimental conditions established by: (a) bath 1, (b) bath 6, (c) bath 7 and (d) bath 11.
fromthe equilibria formed with sulfates and chlorides. This would
account for the presence of different waves along the linear voltam-
mograms. In order to analyze the co-existence of different nickel
species, thermodynamic diagrams were constructed for these sys-
tems.
The solution chemistry of the different baths analyzed in this
work is crucial since it reveals thermodynamic information of the
stability of the aqueous species co-existing in solution. This infor-
mation is overriding since it could yield a prediction of the species
susceptible to react on the electrode surface. Species distribution
diagrams were built with the purpose of evaluating the solution
chemistry of the Ni(II) system. They represent the fraction of Ni(II)
used to forma determined species as a functionof the pHand inter-
actions with SO
4
2
and Cl

ions. The equilibrium constants used

to construct these distribution diagrams were collected from the
HYDRA program database [22]. The methodology to build these
diagrams was based on the free energy minimization algorithms
reported by Eriksson [23] and implemented by the Chemical Equi-
libriumSoftware MEDUSA

.
FractionNi(II) vs. pHdiagrams areshowninFig. 3under theelec-
trolyte concentrations established in Tables 1 and 2: (a) bath 1, (b)
bath6, (c) bath7and(d) bath11. As observedinthese diagrams, the
variationof the total Ni(II), Cl

andSO
4
2
concentrations contained
in the baths are signicant to determine the fraction of Ni(II) occu-
pied for each species and as a result, the predominant species as a
functionof the pH. Note that chloro-complex are not formedwithin
the range of concentrations reported for Tables 1 and 2, probably
due tothe lowchloride contents insolutioncomparedtothe sulfate
ions. Alkaline conditions are characterized for the appearance of
Ni(OH)
2(s)
as a result of the high OH

concentration, which cannot

be counteracted for any other ligand. When the supporting elec-
trolyte concentration and conductivity are variable, more drastic
changes are observed between the fractions of Ni
2+
and NiSO
4(aq)
species (Fig. 3a and b). This nding emphasizes the importance of
the supporting electrolyte on the electrolyte conductivity and the
change of fraction of Ni(II) species with concentration, which could
have a deep impact in the reaction mechanismof nickel electrore-
covery. Likewise, when the supporting electrolyte is xed in the
electrolyte (e.g. constant conductivity), Fig. 3c and d shows that the
NiSO
4(aq)
fraction decreases as the Ni(II) concentration is increased,
most likely since the sulfate ions cannot bond with Ni(II) as occurs
in lower concentrations (Ni
2+
). Indeed, these changes related to the
existence of two nickel species could be reected in the kinetic
behavior analyzedwiththe linear sweepvoltammograms, andcon-
sequentlygeneratingthedeviations observedinFigs. 1and2, where
the Ni(II) reduction was considered to occur froma single species.
Hessami andTobias wereoneof therst researchers toacknowl-
edge this type of concomitant reduction mechanisms for transition
metals, where the simultaneous discharge of metallic and metallic-
hydroxide ions occurred on the electrode surface [24]. They also
developed a kinetic model where these reactions were incorpo-
rated into the mechanism by modifying the Tafel equation. Since
the nickel electrorecoveryfromindustrial platingefuents involves
the simultaneous reductionof two possible nickel species as shown
in Fig. 3, we have adopted the same approach considered by
these authors and implemented a new model appropriate for our
experimental conditions (e.g. variable electrical conductivity, low
supporting electrolyte composition). This imply that a newspecies
(e.g. NiSO
4(aq)
) needs to be introduced in Eq. (14) and the former
reactive ux of nickel species (Eq. (18)) at the electrode surface
Author's personal copy
272 J.R. Hernndez-Tapia et al. / Electrochimica Acta 103 (2013) 266274
0
10
20
30
40
a
b
-2 -1.5 -1 -0.5 0
-
j
T
/

A

m
-
2
E - j
T
R
s
vs SSE/ V
bath 2
bath 1
bath 3
symbols - experiment
continous line - model
0
10
20
30
40
50
-2 -1.5 -1 -0.5 0
-
j
T
/

A

m
-
2
E - j
T
R
s
vs SSE/ V
bath 2
bath 1
bath 3
symbols - experiment
continous line - model
Fig. 4. Experimental and tted linear sweep voltammograms obtained under vari-
able electrolyte conductivity (baths 13, 3971515S cm
1
): (a) 50mV s
1
, (b)
70mV s
1
, simulating rinsing discharges generated from the plating industry. A
model describing the discharge of Ni
2+
andNiSO
4(aq)
species was utilized. The kinetic
parameters and constants obtained fromthe tting are reported in Table 3.
needs to be modied to account for the reduction of Ni
2+
and
NiSO
4(aq)
species:
6

i=1
_
D
i
C
i
y
+
z
i
D
i
F
RT
C
i

s
y
_

y=0
=
j
Ni
2+ +j
NiSO
4
2F
+
j
H
F
= k
Ni
2+

_
2
Ni
2+
F(E

s
)
RT
_
C
s
Ni
2+
+k
NiSO
4
_
2
NiSO
4
F(E

s
)
RT
_
C
s
NiSO
4
+k
H
exp
_

H
F(E

s
)
RT
_
C
s
H
(24)
Additional boundary conditions (H
+
, Na
+
, Cl

and SO
4
2
)
required to solve the model can be expressed by Eqs. (19)(22).
The following homogeneous reactionalsoneeds tobe consideredin
order to establish the equilibriumconditions for Ni
2+
and NiSO
4(aq)
species,
K
NiSO
4
=
C
Ni
2+C
SO
2
4
C
NiSO
4
(25)
The bi-sulfate equilibriumis not considered in the systemsince the
bulk pH is 4 (e.g. HSO
4

is dominant at pH<4), and H

+
reduction
increases evenmorethis valueinlater stages of thenickel electrore-
covery. Mass-balances are then developed for the newequilibrium,
incorporating the reactive ux expressed by Eqs. (24) and (25).
Fig. 4a and b shows the experimental data recorded in the baths
13 using two different scan rates (50 and 70mV s
1
), and the ts
obtained with the variations to the model proposed with Eqs. (24)
and (25). It is evident from the gures that the presence of the
equilibrium:
NiSO
4
Ni
2+
+SO
2
4
(26)
provides the appropriate uxes for mass-transfer of the Ni(II) and
NiSO
4(aq)
species producing the deposit on the electrode surface,
and thus, adequate ts are obtained in all the potential regions of
the scans. Also, note that the peak presented in the model pre-
viously used is gone (Figs. 1 and 2), and instead a smooth line
is obtained at more negative potentials. Calculations of the Ni
2+
and NiSO
4(aq)
surface concentrations (not shown) reveal that both
species decay as they approximate to the electrode surface. This
conrms that the concomitant transport of these species to the
substrate is what results into higher current density values, as
described by the experimental data. However, NiSO
4(aq)
mostly
makes up the partial current density of nickel deposition since the
equilibriumdescribed in Eq. (26) proceeds faster than the electro-
chemical reactions [17,24]. Therefore, the consumptionof NiSO
4(aq)
is hastily replenished by Ni
2+
and SO
4
2
ions close to the elec-
trode surface. Additionally, Ni
2+
reduction is slower compared to
NiSO
4(aq)
reduction, a similar behavior has been obtained by Hes-
sami and Tobias for Ni
2+
and NiOH
+
[24]. Further evidence of the
rates of these reactions can be observed from the kinetic parame-
ters and constants reported in Table 3. It is worth mentioning that
all the kinetic parameters and constants including diffusion coef-
cient were allowed to vary during the tting stage, and a single set
of kinetic parameters can describe the whole set of experimental
data (experimental conditions reported in Tables 1 and 2). None of
these parameters is foundout of the typical range reportedby other
authors, evenunder different experimental conditions. As observed
from this table, the rate constant associated with the NiSO
4(aq)
reduction is two orders of magnitude faster than the one for the
Ni
2+
reduction process. Additionally, the charge transfer coef-
cient is larger for NiSO
4(aq)
. Similar differences have been obtained
by Hessami and Tobias for the rate constants and charge transfer
coefcients of the NiOH
+
and Ni
2+
reductions [24]. Likewise, the
diffusion coefcients for all the species are pretty close to those
reported in other studies [1113,15,24].
Any theoretical model is useless if it is not capable to predict
accurately the output variables under different conditions to what
it was designed or developed. Thus, in order to examinate the pre-
diction capabilities of our model, the voltammograms recorded
under the experimental conditions shown in Table 2 were simu-
lated using the kinetic parameters (Table 3) obtained fromthe ts
to the data collected at variable electrolyte conductivity. Fig. 5a and
b shows these simulations where it can be observed that the model
is capable to simulate satisfactorily the experiments obtained at
constant electrolyte conductivity. Simulations for baths 911 are
not included for a better appreciation of the conditions shown in
Fig. 5a and b, but similar quality was obtained.
As discussed above, different waves arise in the experiments
during the potential scans presented in Figs. 4 and 5. These pro-
cesses can be related to the electrochemical reactions occurring
on the cathode, as a result of the presence of several electroactive
species in the electrolyte. Although the nature of these electro-
chemical reactions occurring is difcult to analyze since they
depend on several factors, this can be achieved calculating the
partial current densities as a function of the applied potential.
Fig. 6 shows these calculations for the scan conducted in bath 8
using a scan rate of 50mV s
1
. It is evident from this gure that
H
+
reduction occurs at the less negative potentials, followed by
nickel deposition, and then water reduction at the most negative
potentials. The onset of water reduction depends on H
+
and Ni(II)
concentrations, however, an approximate value of 1.5V vs. SSE
can be proposed for this reaction. The occurrence of these reactions
coincides with the potential where qualitatively the waves show
Author's personal copy
J.R. Hernndez-Tapia et al. / Electrochimica Acta 103 (2013) 266274 273
0
10
20
30 a
b
-2 -1.5 -1 -0.5 0
-
j
T
/

A

m
-
2
E - j
T
R
s
vs SSE/ V
bath 7
bath 8
symbols - experiment
continous line - model
0
10
20
30
40
50
-2 -1.5 -1 -0.5 0
-
j
T
/

A

m
-
2
E - j
T
R
s
vs SSE/ V
bath 7
bath 8
symbols - experiment
continous line - model
Fig. 5. Experimental (symbols) and model-simulated (continous line) linear sweep
voltammograms obtained under constant electrolyte conductivity (baths 78,
47174425S cm
1
): (a) 50mV s
1
and(b) 70mV s
1
, simulating rinsing discharges
generated from the plating industry. A model describing the discharge of Ni
2+
and
NiSO
4(aq)
species was utilized. The kinetic parameters utilized in the simulations are
shown in Table 3.
up, whereby they support the experimental evidence presented
before and observed by other authors [8,13]. Other observation is
the decay of the partial current density for Ni(II) reductionat poten-
tials around 1.62V, which denotes the mass-transport control of
this reaction. However, unlike the calculations obtained with the
rst model considering a single nickel species, the current densities
of the second model are in general higher, whence the experi-
mental current is not underestimated. Indeed, a mass-transport
0
10
20
30
40
50
-2 -1.5 -1 -0.5 0
-
j
T
/

A

m
-
2
E - j
T
R
s
vs SSE/ V
0
2
4
6
8
10
-1.7 -1.5 -1.3 -1.1 -0.9 -0.7
-
j
/

A

m
-
E vs SSE/ V
j
exp
j
mod
j
H+
j
Ni
j
H2O
Fig. 6. Experimental (circles) and model-tted (continous line) linear sweep
voltammogram obtained in bath 5 (Table 1) at 50mV s
1
. The computed partial
current densities are also shown: j
Ni
, j
H
+ and j
H
2
O
. Computed curves were generated
using parameters and constants listed in Table 3.
control is observed since the electrode is not rotated, whereby
(t) grows as function of t
1/2
and the current drops unlike the cur-
rent plateau depicted under rotating conditions [13]. Note that this
situation does not apply for the case of H
+
perhaps because its con-
centration can be rapidly replenished (e.g. highest diffusivity and
ionic conductivity), whence its reduction at this pHvalue proceeds
at pseudo-steady-state conditions. While H
+
reduction is coupled
with nickel deposition at lees negative, water reduction accompan-
ies the deposition process at more negative. This latter reaction is
characterized by a steep rise in current once its activation has been
overcome since it does not depend on mass transfer. Similar trends
were found for other experimental conditions of these systems.
5. Conclusions
Nickel electro-recovery is a promising alternative to purify
industrial plating efuents (e.g. rinising solutions) and recover
high purity nickel. However, in order to overcome the challenges
imposed for this technology and efuents (e.g. low concentration,
parasitic reactions, low electrolyte conductivity), it is necessary to
nd the optimum operating conditions which capitalize the pro-
tability of the process. This study proposes the derivation of a
comprehensive model to account for the kinetics of nickel electro-
recovery from industrial plating efuents, typically containing
low sulfate (1.2518.73mol m
3
), chloride (0.497.41mol m
3
)
and borates concentrations (9.96150mol m
3
) at pH 4. The tran-
sient model is developed for a microelectrolysis scale (i.e. linear
sweep voltammetry) considering the mass-transport (diffusion
and migration) of six species in solution under stagnant condi-
tions: Ni
2+
, NiSO
4(aq)
, H
+
, Na
+
, SO
4
2
and Cl

, and accounting
for the kinetic discharges of Ni
2+
, NiSO
4(aq)
, H
+
and H
2
O on the
substrate. The model is capable to describe the electrochemical
response of different baths with variable electrolyte conductivi-
ties (3974202S cm
1
) using a single set of kinetic parameters.
It was found that when only one nickel species (Ni
2+
) is consid-
ered in the model, large deviations were observed between the
model and the experimental data at intermediate and more nega-
tive potentials. On the other hand, very good ts were obtained
when two nickel species were introduced in the model for the
experiments conducted at variable electrolyte conductivity, con-
rming the existence of Ni
2+
and NiSO
4(aq)
species in solution. The
model was developedina general formsuchthat it canbe extended
for the robust analysis of other systems or experimental conditions.
This work constitutes the rst stage of the design and optimiza-
tion of an electrochemical reactor for nickel electro-recovery from
industrial plating efuents (e.g. rinsing solutions). Future efforts
will be devoted to analyze the buffer effects arising from the dis-
sociation of H
3
BO
3
, which must entail the incorporation of water
hydrolysis into the model; and the selection of optimum experi-
mental conditions for nickel electro-recovery inanelectrochemical
reactor with a rotating cilinder electrode.
Acknowledgments
The authors are indebted to the CONACyT (Mexico) for their
nancial support to carry out this work, and for the fellowship
granted to JRHT to pursue Ph.D. studies.
References
[1] P. Papachristou, K.J. Haralambous, M. Loisidou, N.J. Spyrellis, Studies on the
nickel removal fromaqueous solutions, Journal of Environmental Science and
Health, Part A: Toxic/Hazardous Substances andEnvironmental Engineering 28
(1993) 135.
[2] C. Escobar, C. Soto-Salazar, M.I. Toral, Optimization of the electrocoagulation
process for the removal of copper, lead and cadmium in natural waters and
simulated wastewater, Journal of Environmental Management 81 (2006) 384.
Author's personal copy
274 J.R. Hernndez-Tapia et al. / Electrochimica Acta 103 (2013) 266274
[3] F.F. Rivera, I. Gonzlez, J.L. Nava, Copper removal froman efuent generated by
a plastics chromium-plating industry using a rotating cylinder electrode (RCE)
reactor, Environmental Technology 29 (2008) 817.
[4] J.W. Patterson, Industrial Wastewater Treatment Technology, 2nd ed., Butter-
worth Publisher, Stoneham, MA, 1985, pp. 512.
[5] J.O. Bockris, D. Drazic, A.R. Despic, The electrode kinetics of the deposition and
dissolution of iron, Electrochimica Acta 4 (1961) 325.
[6] I. Epelboin, M. Joussellin, R. Wiart, Impedance measurements for nickel deposi-
tion in sulfate and chloride electrolytes, Journal of Electroanalytical Chemistry
119 (1981) 61.
[7] J. Newman, K.E. Thomas-Alyea, Electrochemical Systems, 3rd ed., John Wiley &
Sons, NewJersey, 2004.
[8] J. Vazquez-Arenas, L. Altamirano-Garcia, T. Treeratanaphitak, M. Pritzker, R.
Luna-Snchez, R. Cabrera-Sierra, CoNi alloy electrodeposition under differ-
ent conditions of pH, current and composition, Electrochimica Acta 65 (2012)
234243.
[9] Y. Tsuru, M. Nomura, F.R. Foulkes, Effects of chloride, bromide and iodide ions
on internal stress in lms deposited during high speed nickel electroplating
from a nickel sulfamate bath, Journal of Applied Electrochemistry 30 (2000)
231.
[10] R. Orinakov, M. Streckov, R. Rozik, L. Glov, Comparison of chloride and
sulphate electrolytes in nickel electrodeposition on a parafn impregnated
graphite electrode, Journal of Electroanalytical Chemistry 594 (2006) 152.
[11] C.C. Cheng, A.C. West, Nickel depositioninthepresenceof coumarin: anelectro-
chemical impedancespectroscopystudy, Journal of theElectrochemical Society
144 (1997) 3050.
[12] J. Vazquez-Arenas, M. Pritzker, EIS study of nickel deposition in borate-sulfate
solutions, Journal of the Electrochemical Society 157 (2010) D283.
[13] J. Vazquez-Arenas, L. Altamirano-Garcia, M. Pritzker, R. Luna-Snchez, R.
Cabrera-Sierra, Experimental and modeling study of nickel electrodeposition
including H
+
and water reduction and homogeneous reactions, Journal of the
Electrochemical Society 158 (2011) D33D41.
[14] J. Vazquez-Arenas, M. Pritzker, Steady-state model for anomalous CoNi elec-
trodeposition in sulfate solutions, Electrochimica Acta 66 (2012) 139.
[15] N. Zech, E.J. Podlaha, D. Landolt, Anomalous codeposition of iron group metals
II. Mathematical model, Journal of the Electrochemical Society 146 (1999)
2892.
[16] J. Vazquez-Arenas, M.D. Pritzker, Transient and steady-state model of cobalt
deposition in borate-sulfate solutions, Electrochimica Acta 55 (2010) 8376.
[17] J. Vazquez-Arenas, M. Pritzker, Comprehensive impedance model of cobalt
deposition in sulfate solutions accounting for homogeneous reactions and
adsorptive effects, Electrochimica Acta 56 (2011) 8023.
[18] M. Tesillo, S. Alonso, F.F. Rivera, E.P. Rivero, I. Gonzalez, Nickel removal from
rinse waters generated by electroplating industry using a rotating cylinder
electrode (RCE) reactor, Proceedings of the ECS Transactions (2009).
[19] A.J. Bard, L.R. Faulkner, Electrochemical Methods: Fundamentals and Applica-
tions, 2nd ed., John Wiley & Sons, Inc., USA, 2001.
[20] R.A. Robinson, R.H. Stokes, Multicomponent Electrolyte Solutions, 1st ed., Per-
gamon Press Oxford, NewYork, 1968.
[21] J. Vazquez-Arenas, M. Fowler, X. Mao, S.-K. Chen, Modeling of combined capac-
ity fade with thermal effects for a cycled LixC
6
LiyMn
2
O
4
cell, Journal of Power
Sources 215 (2012) 28.
[22] I.I. Puigdomenech, SED, and PREDOM. Computer Programs, Drawing Equilib-
rium Diagrams, TRITA-OOK-3010, Royal Institute of Technology, September
1983, 1983, 12 pp.
[23] G. Eriksson, An algorithm for the computation of aqueous multi-component,
multiphase equilibria, Analytica Chimica Acta 112 (1979) 375.
[24] S. Hessami, C.W. Tobias, Mathematical model for anomalous codeposition of
nickeliron on a rotating disk electrode, Journal of the Electrochemical Society
136 (1989) 36113616.