chemical engineering research and design 1 0 0 ( 2 0 1 5 ) 422–433

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Chemical Engineering Research and Design

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

Modeling the effect of non-ideal flow pattern on

tertiary current distribution in a filter-press-type
electrochemical reactor for copper recovery

Eligio P. Rivero a,∗ , Martín R. Cruz-Díaz a , Francisco J. Almazán-Ruiz b ,

Ignacio González b
a Departamento de Ingeniería y Tecnología, Universidad Nacional Autónoma de México, Facultad de Estudios
Superiores Cuautitlán, Av. 1o de Mayo, Cuautitlán Izcalli 54740, Estado de México, Mexico
b Departamento de Química, Universidad Autónoma Metropolitana-Iztapalapa, San Rafael Atlixco 186, México D.F.

09340, Mexico

a r t i c l e i n f o a b s t r a c t

Article history:
Received 28 September 2014
Received in revised form 29 April
2015
Accepted 30 April 2015
Available online 11 May 2015
Keywords:
Electrochemical reactors
Tertiary current distribution
Turbulent mass transfer
Copper recovery
Butler–Volmer kinetics
This work presents the numerical modeling of the effect of hydrodynamics on mass trans-
port and tertiary current and potential distribution in a filter press type electrochemical
reactor used to study the copper recovery process. The operating conditions of the reactor
were in turbulent regime and under charge and mass transfer mixed control.
For hydrodynamics, the Reynolds averaged Navier–Stokes equations and the stan-
dard k–ε turbulence model were used. The mass transfer model was a combination of
the convection–diffusion equation and a wall function adapted for mass transfer. The
Butler–Volmer kinetics for copper reduction, simplified Tafel equations for water oxidation
and ohmic potential drop through the electrolyte were also incorporated into the model.
The strategic part of the proposed numerical modeling is the concentration wall function
that allows linking the transport equations with Cu2+ concentration at the interface in order
to obtain, along with interfacial potential, the electrode kinetics. Using this approach it was
possible to model a very complex interrelation between physical phenomena and the elec-
trochemical reaction taking place in a reactor under a turbulent flow regime using moderate
computer resources. The numerical results obtained are in agreement with experimental
data of mass transfer coefficient and current–potential behavior.
© 2015 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction FM01-LC, like other kinds of flat plate electrochemical reactor,

The filter press type FM01-LC electrochemical reactor is a
common example of flat plate laboratory scale reactor used
to study electrochemical processes, such as synthesis, metal
recovery, recycling of industrial effluents, and water treat-
ment. To analyse experimental data from this kind of study
it is important to understand the effect of flow pattern on
the mass transfer from or toward the electrodes and then
on the electrode reaction kinetics and electric potential. The
exhibits a non-homogeneous flow pattern inside the reactor
channel caused by the reactor design, especially the inlet and
outlet liquid distributors (Frías-Ferrer et al., 2008; Wragg and
Leontaritis, 1997). Stagnant zones, channelling, bypass, recir-
culation and other observed flow phenomena (Bengoa et al.,
2000) give rise to variations in the mass transfer coefficient
along the electrodes.
In the FM01-LC reactor for Cu recovery, as in other types
of electrochemical reactor, these mass transfer coefficient

∗
Corresponding author. Tel.: +52 55 56232071.
E-mail address: priveromtz@msn.com (E.P. Rivero).
http://dx.doi.org/10.1016/j.cherd.2015.04.036
0263-8762/© 2015 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
 chemical engineering research and design 1 0 0 ( 2 0 1 5 ) 422–433 423

Nomenclature
ε turbulent energy dissipation rate
A empirical constant a electrolyte potential at the anode interface
a,b kinetic constants for water oxidation  electrolyte potential
B reactor channel width c electrolyte potential at the cathode interface
C constant of the turbulence model  Karman constant
Cε1 constant of the k–ε model  viscosity
Cε2 constant of the k–ε model T turbulent viscosity
C+ dimensionless concentration  density
Ci concentration of the electroactive species electrolyte conductivity
Ci,0 inlet concentration of the electroactive species k constant of k–ε model
Ci,w wall concentration of the electroactive species ε constant of k–ε model
de equivalent diameter = 2BS/(B + S)  shear stress
Di diffusion coefficient w wall shear stress
DiT turbulent diffusion coefficient
E potential
Ea anodic potential variations are very important, not only because of the amount
Ec cathodic potential of electroactive species which can reach the electrode sur-
Eeq equilibrium potential of copper reduction face, but also because of their effect on the overpotential in
Eeq,ox equilibrium potential of water oxidation each zone of the reactor. Mass transfer rate and overpoten-
E0 equilibrium cell potential difference tial are factors involved in the type of metallic copper deposit
E˝ ohmic drop formed (compactness, grain size, dendrite and powder pro-
F Faraday constant duction) as well as the flow characteristics are involved in
F external force the shear stress over the electrode surface for carrying the
J current density metallic copper out in the liquid stream. Rough deposit is
JL limiting current density formed at local laminar hydrodynamic conditions (current
Ja current density at the anode electrodeposition lower than the limiting current density con-
Jc current density at the cathode ditions), whereas a turbulent local regime provokes dendritric
J current density vector deposits (Bazan and Bisang, 2004; Robinson and Walsh, 1991a,
J0 exchange current density 1991b). In addition, high overpotentials may lead to unde-
k turbulence kinetic energy sired side reactions that may diminish the charge efficiency of
km mass transfer coefficient the reactor and lead to uncontrollable changes (pH, conduc-
L length of the reactor channel tivity, excessive gas formation, mass transfer rate, formation
n vector normal to the wall of solid byproducts, etc.). Therefore, coupling hydrodynam-
Ni mass transfer flux ics, mass transport, electrochemical kinetics and potential
Ni,w mass transfer flux at the wall and current distribution is necessary to obtain a comprehen-
P pressure sive understanding of the electrochemical reactor behavior.
Pc factor of integration of resistances in near-wall The importance of the fluid dynamics on mass transport and
layers electrochemical kinetics has been shown by modeling elec-
R gas constant trodeposition process on rotating electrodes (Mandin et al.,
Re Reynolds number = de v/ 2007a, 2007b, 2006a, 2006b). Also, in processes with inten-
S electrode spacing sive gas evolution reactions, as in water electrolysis, there is
Sc Schmidt number = /(Di ) a strong coupling of these phenomena since the bubble for-
ScT turbulent Schmidt number = T /(Di,T ) mation diminishes the electrolyte conductivity and modifies
ScT∞ constant of the Kays–Crawford model the hydrodynamic behavior affecting the current distribution
Sh Sherwood number = de km /Di over the electrode (Mandin et al., 2014, 2005). However, model-
t time ing tertiary current distribution in an electrochemical process
T temperature may be very complex, especially for reactors operating under
u velocity vector turbulent flow. Thus, several authors have studied the prob-
u velocity lem using some simplifications: the 2D current distribution
U cell potential = Ea − Ec over flat plate electrodes and other simple geometries where
u+ dimensionless velocity = u/( w /)1/2 electrolyte flows in the laminar regimen have been reported
Vin inlet velocity (Georgiadou, 2003; Boovaragavan and Basha, 2006). Also, the
x,y,z Cartesian coordinates relationships among mass transfer, ohmic drop and overpo-
y+ dimensionless distance to the tential have been studied for copper electrodeposition in a cell
wall = y( w /)1/2 / without any type of convection (Pohjoranta et al., 2010). How-
zi number of electrons exchanged in electro- ever, very few works have studied electrochemical reactions in
chemical reaction reactors under turbulent flow, which is a very important case
from a practical point of view. Even though the characteristic
Greek letters lengths of the laboratory scale FM01-LC electrochemical reac-
˛ transfer coefficient tor are small, the design of the inlet distributor produces high
ı+ dimensionless thickness selected for wall velocity streams or jets not parallel to reactor walls, which
function = ı( w /)1/2 / are discharged inside the reactor channel causing 3D flow
424 chemical engineering research and design 1 0 0 ( 2 0 1 5 ) 422–433
instabilities and eddy formation. The mixing of these jets with
the liquid inside the reactor and the changes of velocity direc-
tion generate additional turbulences avoiding the formation
of laminar zones (Rivero et al., 2012). The solution of Navier
Stokes equations for developed turbulent flow in a flat plate
electrochemical reactor was attained by Direct Numeric Sim-
ulation (DNS) coupled with mass transport equations and
electrochemical reaction kinetics through a first order Taylor
series approach of the Butler–Volmer equation (Doche et al.,
2013, 2012). However, in the simulation performed by these
authors a Schmidt number Sc = 1 was assumed owing to the
unrealistic computational requirements under typical Sc val-
ues.
Alternatively, turbulence has been often simulated by solv-
ing the Reynolds Averaged Navier Stokes (RANS) equations
using a closure condition known as a turbulence model. The
concentration and current density over the electrode have
been calculated by 2D RANS equations, the Low Reynolds (LR)
k–w turbulence model and Butler–Volmer kinetics in a flat
plate electrochemical reactor used for Cu electrodeposition
(Nelissen et al., 2004, 2003); also, it was applied for solving 2D
RANS equations on a wire (Vande Vyver et al., 2008) and for
studying the effect of anode position (Nelissen et al., 2007). The
low Reynolds turbulence models use damping functions for
simulation of the near-wall regions, but requires an extremely
fine mesh size for describing the fluid movement. Moreover,
considering typical Sc values the mass transport in such near-
wall region involves concentration changes in a thinner layer
of fluid that an even finer mesh is needed. In addition, it is very
often necessary to perform simulations in 3D to capture the
effect of non-ideal flow pattern on the local mass transport
rate toward or from the electrode in real reactor, making the
calculations of RANS equations and LR models highly com-
puter demanding (Santos et al., 2010).
On the other hand, it is well known that the combination
of RANS equations and analytical wall functions is a very effi-
cient way to find a velocity field description. Furthermore, we
have shown (Rivero et al., 2012) that a Launder–Spalding wall
function adapted for mass transfer, using a parameter that
takes into account the change of mass transfer resistance from
the viscous sublayer to the turbulent layer, can predict the
mass transfer coefficient in the reduction of ferricyanide ion
in the FM01-LC electrochemical reactor. Hence, the present
work propose to use this kind of mass transfer wall function
to solve the interfacial electrode kinetics and the tertiary cur-
rent distribution. The goal is to examine by simulation the
effect of non-ideal flow pattern on the local mass transfer
Fig. 1 – Exploded view of the FM01-LC reactor and details of
the spacer.
Fig. 2 – Hydraulic and electrical setup of FM01-LC
electrochemical reactor.
and electrode overpotential in the copper recovery in a typi-
cal flat plate electrochemical reactor working under mass and
charge transfer mixed control. To our knowledge there are not
reported works dealing with the use of mass transfer wall
functions to obtain a complete 3D tertiary current distribu-
tion in electrochemical reactors. Thus the present work aims
to fulfill a gap that is relevant in electrochemical engineering
and can be useful for evaluating reactor performance.
2. Experimental
2.1. Equipment and setup
The configuration of the FM01-LC cell has been described else-
where (Bengoa et al., 2000; Griffiths et al., 2005). An exploded
view of the cell is represented in Fig. 1 along with spacer
geometry showing the inlet/outlet manifolds. The channel is
0.16 m long, 0.04 m wide and 0.011 m thick (gaskets included).
The electrodes consisted of a 316 stainless steel plate and
a Pb–Ag plate as cathode and anode, respectively. The reac-
tor was installed in a recirculation system (Fig. 2) formed by
a 4 L reservoir made of polycarbonate, a 0.25 HP centrifu-
gal pump and rotameter-type flow meters. The electrodes
were connected to a Bio-logic Science Instruments VMP3TM
potentiostat–galvanostat coupled with a 20A–20 V VMP3B
booster. The Cu(II) concentrations were determined employ-
ing a VarianTM Atomic Absorption Spectrophotometer Model
220FS.
2.2. Experimental procedure
Experiments were performed in an undivided continuous-
flow FM01-LC cell by using the Cu2+ reduction reaction on
the flat plate electrode. Aqueous solutions of 1 M H2 SO4 , con-
taining 18.8 mM CuSO4 , were prepared with Milli-Q deionized
water and analytical reagents. Recently prepared solutions
were loaded into the electrolyte recirculation system reser-
voir and were bubbled with nitrogen for 10 min and nitrogen
atmosphere was preserved during the experiments. All elec-
trolyses were conducted in potentiostatic mode at T = 298 K. A
saturated sulfate reference electrode (SSE) was connected to
a Luggin capillary, which was in contact with the electrolytic
solution by means of a supporting device placed in the middle
 chemical engineering research and design 1 0 0 ( 2 0 1 5 ) 422–433 425

of the hydraulic channel. Such a configuration ensures a (5) only Cu2+ reduction at the cathode and water oxidation at
more uniform flow and electric potential distribution so the anode are considered.
that mass transport measurements are only associated with
the flow pattern in the hydraulic channel. For experimental 3.1. Fluid flow
determination of the limiting current, polarization curves
were constructed using sampled current density vs. poten- For the purposes of the present work, the bulk-flow dynamics
tial. It is important to mention that the authors decided to can be approximated by the Reynolds averaged Navier Stokes
construct the polarization curves in this way instead of by equation (Eq. (3)) using turbulence models as closure condition
using the linear sweep voltammetry technique, because a since it is still an effective and practical tool to approach this
voltammetric study always involves competition between the kind of problem (Bernard and Wallace, 2002; Eςa and Hoekstra,
rate of electrochemical reaction at the interface and the rate 2010; Lacasse et al., 2004; Trujillo et al., 2009). The standard
of potential change. This competition is eliminated in the k–ε turbulence model and the balances of k and ε given by
potential pulse technique. Eqs. (4)–(6) are used in this work. Since this approach is not
The polarization curves have been constructed as follows: applicable in the proximity of solid surfaces, log-law based
a series of potential double pulses was applied to the elec- wall functions are commonly used as boundary conditions
trochemical reactor. The direct pulse was started from open (Bernard and Wallace, 2002; Eςa and Hoekstra, 2010; Lacasse
circuit potential OCP (−0.34 versus SSE) in the potential range et al., 2004), i.e. Eq. (3) is solved only in the fluid bulk sepa-
of −1.0 ≤ E ≤ −0.4 V versus SSE during 30 s, with increments of rated by a distance ı from walls where the velocity is linked
0.05 V. The inverse pulse was 0.58 V to ensure the oxidation to the wall function (Eq. (7)). This wall function based on the
of the previously deposited copper. The corresponding cur- universal velocity distribution in the viscous, buffer and turbu-
rent time curves were obtained at different volumetric flows lent layers defines the parallel-to-wall velocity in the turbulent
between 2 and 7 LPM (1384 ≤ Re ≤ 4845). From these current layer as a function of its distance to the wall, where molecu-
time curves obtained for direct pulses at the applied poten- lar viscosity is considered negligible compared to turbulent
tial, the current density was sampled at 15 s and polarization viscosity.
curves were constructed (J–E) for a specific flow rate. The
T
 
sampled time ensures both a negligible contribution of the (u · ∇) u = −∇P + ∇ · ( + T ) ∇u + (∇u) + F (3)
capacitive current to the measured current and a pseudo-
steady state (the current is time-independent). k2
T = C (4)
ε
3. Mathematical model and simulation  T
  1  2
u · ∇k − ∇ · + ∇k = T ∇u + (∇u)T − ε (5)
k 2
Copper recovery in a continuous bench scale electrochemical
reactor may be carried out under either potentiostatic or gal-
 T
 
vanostatic conditions where copper reduction (Eq. (1)) takes
u · ∇ε − ∇ · + ∇ε
place with a minimum effect of side cathodic reactions (hydro- ε

gen evolution reaction, HER). Pb–Ag (95.5–05 mol%) alloy plate 1 ε  2 ε2

previously anodized in sulfuric medium (to form a PbO2 film)
was used as anode in the FM01LC reactor. In this way, the reac-
tion taking place at the anode concerns only water oxidation
that forms oxygen gas bubbles (Eq. (2)).
Cu2+ + 2e− → Cu (1)
H2 O → 1/2O2 + 2H+ + 2e− (2)
The electrolyte flows into the reactor in the turbulent
regime from the inlet manifold, spreading across the entire
volume of the reactor channel and finally leaving through
the outlet. Once the electrolysis starts, cupric ions are trans-
ported from the bulk to the electrode surface at a local
hydrodynamics-dependant rate. Thus, non-homogenous
interfacial cupric ion concentration and overpotential over
the electrode surface are expected leading to a different
electrochemical reaction rate or even different electrochem-
ical reactions. To keep the model as simple as possible, the
following assumptions are made: (1) the reaction extent of
metallic Cu deposition is small enough that changes on reac-
tor channel dimensions and bulk velocity field are negligible,
(2) hydrodynamic and conductivity changes caused by gas
evolution reaction at the anode are not considered (a reason-
able approximation when low current density and high flow
rates are used), (3) the process is in a pseudo-steady state, (4)
there are no spatial variations of electrolyte properties, and
= Cε1 T ∇u + (∇u)T − Cε2 (6)
2 k k
1
u+ = 5.5 + ln y+ (7)

where u is the average velocity, P is the pressure,  is the
viscosity, T is the turbulent viscosity, F is any external force, 
is the fluid density, C is a turbulence model constant (C = 0.09
to guarantee consistency with the log-law of the wall (Bernard
and Wallace, 2002)), k is the eddy kinetic energy, ε is the tur-
bulent energy dissipation rate, Cε1 , Cε2 , k and ε are empirical
constants, u+ is a dimensionless velocity (=u/( w /)1/2 ), u is the
velocity,  w is the wall shear stress and y+ is a dimensionless
distance to the wall (=y( w /)1/2 /) and  is the wall-law pro-
portionality constant known as Karman constant. Constants
of the model are shown in Table 1.
The boundary conditions used in Eq. (3) are as follows:
• u = −Vin n, at the reactor inlet, where n is the normal vector
at the boundary.
 
• ( + T ) ∇u + ∇uT n = 0, P = 100 kPa, at the reactor outlet.
• Logarithmic function (Eq. (7)) for y+ = ı+ at all walls.
This last boundary condition means that the thin layer next
to all walls in the reactor is not included in the simulation
domain where Eq. (3) will be solved. The dimensionless thick-
ness of this thin layer ı+ should be greater than 30 in order
426 chemical engineering research and design 1 0 0 ( 2 0 1 5 ) 422–433

Table 1 – Electrolyte properties and parameters used in the model.

Parameter Value References
−3
Density () 1059 kg m Hotlos and Jaskula (1988)
Viscosity () 0.001 kg m−1 s−1 Hotlos and Jaskula (1988)
Diffusion coefficient of Cu2+ (Di ) 7.2 × 10−10 m2 s−1 Newman (1991)
Conductivity ( ) (this work) 39 S m−1 This work
Constants of k–ε turbulence model
C 0.09 Bernard and Wallace (2002)
Cε1 1.44 Bernard and Wallace (2002)
Cε2 1.92 Bernard and Wallace (2002)
k 1 Bernard and Wallace (2002)
ε 1.3 Bernard and Wallace (2002)
Karman constant () 0.41 Bernard and Wallace (2002)
Constant for turbulent Schmidt (ScT∞ ) 0.85 Weigand et al. (1997)
Equilibrium potential of copper reduction (Eeq ) 0.288 V This work
Exchange current density (J0 ) 1 A m−2 Nelissen et al. (2003)
Kinetic constant of water oxidation (a) 0.17 A m−2 Zeng and Zhang (2010)
Kinetic constant of water oxidation (b) 12.03 V−1 Zeng and Zhang (2010)
Transfer coefficient (˛) 0.25 Nelissen et al. (2003)

to locate the boundary in the turbulent layer and the logarith-
mic velocity distribution given by Eq. (7) could be applied. Fig. 3
illustrates this wall function along with the location of viscous
(y+ ≤ 5), buffer (5 ≤ y+ ≤ 30) and turbulent (y+ ≥ 30) layers, the
mass transport wall conditions and other model conditions
for the cathode surface.
where u is the averaged velocity vector, Ci the averaged con-
centration field, Di the diffusion coefficient and Di,T the eddy
diffusivity or turbulent diffusivity. This last term can be deter-
mined from the turbulent Schmidt number (ScT = T /(Di,T ))
given by the following Kays Crawford model as described pre-
viously (Rivero et al., 2012).

   −1
1 0.3 T
T
2 −Di
ScT = +√ − 0.3 1 − exp  √  (9)
2ScT∞ ScT∞ Di Di 0.3T ScT∞

where ScT∞ = 0.85 (Weigand et al., 1997).

3.2. Mass transport
The mass transport model is derived considering the migra-
tion term of the Nernst–Planck equation to be negligible
because of the high concentration of supporting electrolyte.
In addition, under turbulent flow conditions, the concentra-
tion and velocity fluctuation terms can be grouped into a
so-called turbulent diffusion term (·Di,T Ci ) of an averaged
diffusion–convection equation analogous to the RANS equa-
tion, as follows:
−u · ∇Ci + ∇ · (Di + Di,T ) ∇Ci = 0
The model proposed by Eq. (8) has to be solved in the
same fluid region where RANS equations are solved, i.e. sepa-
rated y+ = ı+ dimensionless distance from the wall (see Fig. 3)
(Lacasse et al., 2004), because turbulent viscosity and average
velocity field need to be known. In the unsolved near-wall
region of the electrode, a distribution of dimensionless con-
centration C+ can be considered.
The following Launder–Spalding distribution was adapted
to the mass transfer case (Trujillo et al., 2009) and is used in the
present work, where Eq. (10) corresponds to the distribution
in the viscous sublayer and Eq. (11) to the distribution in the
turbulent layer.
(8)

Ci + = Sc y+ (10)

1 
Ci + = ScT ln y+ + 5.5 + Pc (11)


where Ci + is defined by:

(Ci,w − Ci ) C 1/4 k1/2

Ci + = (12)
Ni,w

where Ci,w is the fluid concentration at the electrode surface,

Ci is the concentration at a distance y+ = ı+ from the wall, Ni,w
is the diffusion flux in the near-wall region and the term Pc
is given by the following empirical equation, which takes into
account the change of resistance to mass transfer from the
viscous sublayer to the turbulent layer:

Fig. 3 – Schematic of near-cathode region showing the  Sc 3/4

variables at the interphase and their relationship with Pc = A −1 (13)
velocity and copper ion concentration at y+ = ı+ . ScT
 chemical engineering research and design 1 0 0 ( 2 0 1 5 ) 422–433
where A is a constant whose value (A = 9.24) has been deter-
mined from heat transfer experimental data in smooth tubes
(Jayatillake, 1969).
Considering the transport of Cu2+ ion toward the cathode
(i.e. subscript i is equal to Cu2+ ) where a reduction reaction
takes place, the boundary conditions of the mass transport
model are:
• Ci = Ci,0 , at the reactor inlet.
• n·(−Di Ci ) = 0, at the reactor outlet (convective flux)
• Wall function (Eqs. (11) and (12)) at the electrode, with
Ni,w = Jc /zi F.
• n·(−Di Ci + uCi ) = 0, in all other (impermeable) walls.
where Jc is the local current density at the cathode, zi the num-
ber of electrons in the reduction reaction (two electrons in this
case) and F the Faraday constant.
3.3. Electrode kinetics
The most accepted mechanism for Cu2+ reduction involves
two successive monoelectronic transfer reactions, adsorp-
tion processes and ion migration over the electrode surface.
Even though other mechanisms have been reported and there
has not been a clear discrimination among several reaction
sequences to elucidate the real mechanism, the experimental
electrodeposition rate data might be fitted to Butler–Volmer
kinetics, according to:
zi (1 − ˛)F (Ec − c − Eeq )
Jc = J0 exp
RT
CCu2+ ,w −zi ˛F (Ec − c − Eeq )
− exp
CCu2+ RT
where J0 is the exchange current density, Ec the cathodic
potential, c the electrolyte potential at the cathode inter-
face, Eeq the equilibrium potential, CCu2+ ,w the interface Cu2+
concentration, CCu2+ the bulk concentration, R the gas con-
stant and T the temperature (parameters are given in Table 1).
Eq. (14) corresponds to a mixed control (kinetics and diffu-
sion). The potential range for the copper electrodeposition in a
mixed control was previously determined in a microeletrolysis
study. In this potential range, HER is negligible.
Assuming that oxidation of the medium (water) follows a
Tafel expression:
Ja = a exp (b (Ea − a − Eeq,ox ))
where Ea is the anodic potential, a the electrolyte potential
at the anode interphase, Eeq,ox the equilibrium potential of
the water oxidation, a and b are empirical constants shown in
Table 1.
3.4. Electric continuity
The cell potential defined by the voltage difference (Ea –Ec ) is
given by the sum of absolute values of overpotentials at both
electrodes plus the ohmic drop E˝ and the equilibrium cell
potential difference E0 , as follows:
U = (Ea − a − Eeq,ox ) + E˝ − (Ec − ϕc − Eeq ) + E0
427
The ohmic potential drop can be obtained from the con-
tinuity equation for the electrolyte between the electrodes,
according to
∇ · J = −∇ · ( ∇) = 0 (17)
where J is the current density vector and the electrolyte
conductivity.
As the overpotentials are given by the Butler–Volmer equa-
tion for copper reduction (Eq. (14)) and Tafel equation for water
oxidation (Eq. (15)), Eq. (17) applies for the potential between
c and a . Assuming constant cathodic and anodic potentials,
Ec and Ea respectively, the interface electrolyte potentials, c
and a , vary over the electrode and are unknown. Therefore,
Dirichlet type boundary conditions of Eq. (17) for the electrode
interface are not possible, instead Neumann type conditions
are to be used as follows.
• −n · J = Jc , at the cathode.
• −n · J = Ja , at the anode.
• n · J = 0, at all other boundaries.
where Jc and Ja are the local current density given by the kinetic
equations (Eqs. (14) and (15)), which depend on overpotential.
With these equations the mathematical development to
obtain the tertiary current distribution in an electrochemical
reactor for copper recovery under turbulent flow is complete.
3.5. Simulation
The equations for hydrodynamic, mass transport, electrical
continuity, electrode kinetics and concentration wall func-
tion form a coupled set of partial differential equations and
algebraic equations. However, since hydrodynamic changes
(14)
caused by anodic and cathodic reactions are not considered
(assumptions 1 and 2), the hydrodynamic model was solved
first. It was made by use of finite elements using commercial
software (COMSOL Multiphysics® ) as follows.
The hydrodynamic model was solved with the option of the
k–ε turbulence model, momentum transport, using calculation
options by default: stationary segregated solver with BICGStab
iterative methods for u and P, and GMRES for logarithms
of the turbulence model variables, log(k) and log(ε). Galerkin
Least Squares (GLS) was used as a stabilization method; tol-
erance was fixed at 10−3 . Upon verifying numerical solutions
reached at different values of ı+ and mesh size, the ı+ value
was fixed at 100 (typical value used within the validity of
the logarithmic velocity distribution law, assuming no effects
(15) of roughness caused by copper deposits) and the maximum
mesh size in the reactor channel at 2 × 10−3 m. Fig. 4 shows
the mesh in the reactor inlet used in simulation (37,042 total
mesh points and 185,250 tetrahedral elements). The results
obtained were stored through the option available in the pro-
gram, in order to be used in the mass transfer model. The
diffusion–convection equation (Eq. (8)) along with mass trans-
port wall functions given by Eqs. (11)–(13) were then added to
the model, linking the results of the hydrodynamic calcula-
tion: (i) the time-averaged velocity to evaluate the convection
term in Eq. (8), (ii) the turbulent viscosity to obtain turbulent
diffusivity through the turbulent Schmidt number, ScT , and (iii)
the eddy kinetic energy necessary for the concentration wall
functions (Eqs. (11) and (12)).
The mass transport model requires the current density Jc
(16) at the boundary conditions, which is set by Cu2+ reduction
428 chemical engineering research and design 1 0 0 ( 2 0 1 5 ) 422–433
Fig. 4 – Mesh configuration of the simulation domain in the
FM01-LC reactor.
kinetics given by the Butler–Volmer equation. But, this last
equation is a function of interfacial variables: Cu2+ concentra-
tion, Ci,w , and potential, c . The first variable, Ci,w , is related
to the concentration at the boundary of the mass-transport
model domain Ci (y+ = ı+ ) by the concentration wall function
(see Fig. 3 and Eqs. (11) and (12)). The second variable, c , is
related to the interfacial potential at the anode, a , by the
ohmic potential drop through the electrolyte given by the elec-
trical continuity equation (Eq. (17)). However, as the potential
drop is a function of the current density it is necessary to eval-
uate the boundary conditions of Eq. (17), Jc and Ja , from the
kinetic equations, Eqs. (14) and (15), respectively. The kinet-
ics of anodic reaction given by Eq. (15) are only related to one
interfacial variable: a , and must satisfy the current continuity
criterion i.e. anodic and cathodic currents are equal, although
the current density distribution over the anode, Ja , could be
different from that of the cathode Jc . Taking into account all
these relationships the complete model can be solved for given
electrode potentials, Ea , Ec and inlet Cu2+ concentration. The
mass transport and electrical continuity models were solved
simultaneously by finite elements along with kinetics equa-
tions for Jc and Ja and the concentration wall function, using
COMSOL Multiphysics® . The solver employed was iterative,
FGMRES, and a relative tolerance of 1 × 10−6 was established.
The values of ı+ and mesh size were as those of the hydro-
dynamic model. Simulations were done using a 4-core Intel i7
920 processor at 2.67 GHz, 12 GB RAM. The values of electrolyte
properties and model parameters used to solve the model are
shown in Table 1.
4. Results and discussion
4.1. Hydrodynamics
There has been a number of works dealing with hydrody-
namics inside flat plate electrochemical reactors; some of
them have specifically treated the FM01-LC reactor (Rivero
et al., 2012; Vázquez et al., 2010). As they commonly used
CFD to describe the reactor behavior we only show the
main characteristics investigated in this work. The manifold
effects, mainly those of the inlet manifold, on the velocity
field are shown in Fig. 5, where jets of different velocity are
clearly formed causing preferred flow paths, recirculation
and low velocity regions. Two high velocity streams, one
higher than the other, close to lateral walls and a low veloc-
ity region in between can be identified. The axial velocity
Fig. 5 – Simulation of the velocity field inside the FM01-LC
reactor channel at Re = 4845 showing the effect of inlet
distributor on the flow pattern and jet formation.
1.4
1.2
1.0 z1
Velocity/m s-1
0.8
0.6
z2
0.4
0.2
0.0
z3
-0.2
0 0.01 0.02 0.03 0.04
Cell width, y/m
Fig. 6 – Axial velocity profile as a function of channel width
at 0.005 m (continuous line) and 0.01 m (broken line) from
the channel inlet and different distances from the cathode,
z1 = 0.005 m, z2 = 0.008 m and z3 = 0.01 m; Re = 4835.
profiles at different distance from the cathode, z1 = 0.005 m,
z2 = 0.008 m and z3 = 0.01 m, and from the inlet, 0.005 m (solid
line) and 0.01 m (broken line) are shown in Fig. 6, where
negative velocity indicates a recirculation pattern. These flow
instabilities caused by the inlet distribution and the absence
of calming zone make it impossible for the flow to be laminar
even at low Re. Also, it is clear that a fully developed flow
is not reached in the short axial length of the FM01-LC. All
these characteristics of the Reynolds averaged velocity field
reveal complex velocity variations in all directions making
impossible to find symmetries for performing 2D simulations
so that simulations in 3D are necessary.
4.2. Mass transfer assessment
Before the model for tertiary current distribution can be used
for simulating Cu reduction in a FM01-LC reactor, the mass
transfer rate should be adjusted by experimental results. The
mass transport model given by Eqs. (8)–(13) uses an empirical
parameter (A) for correcting the concentration wall function.
The A-parameter value has been reported for heat transfer
over smooth surfaces (A = 9.24). This value has allowed the
 chemical engineering research and design 1 0 0 ( 2 0 1 5 ) 422–433
2.4
2.3
log(Sh/Sc0.33)
2.2
2.1
2 possible variations of roughness caused by different rates of
1.9
3 3.2 3.4 3.6 3.8
log(Re)
Fig. 7 – Mass transfer correlation in copper reduction at the
FM01-LC reactor determined by simulation (continuous
line) and comparison with experimental results.
description of experimental mass transfer coefficients for fer-
ricyanide ion reduction over smooth electrodes (Rivero et al.,
2012). In the case of copper reduction, a rough surface is
formed over the electrode owing to the appearance of the cop-
per metallic phase, so a different A-value is expected which
has yet to be determined experimentally.
Under mass-transfer controlled conditions, the current
density value is related to the maximum copper ion flux
toward the cathode surface. This limiting current density is
not dependent on applied potential at each Re, and the mass
transfer coefficient can be determined from its value by the
following equation:
JL
km =
zi FCi
where JL is the limiting current density at the cathode, zi the
number of electrons involved in the electrochemical reaction,
F is the Faraday constant and Ci the bulk copper ion concen-
tration.
Simulations were performed under the same experimental
conditions searching for the A parameter value of the mass
transport model. At the limiting current conditions the cop-
per ion concentration at the interface approaches zero, thus
the mass transfer model might be solved independently of the
electrode kinetics and current continuity model. Therefore,
the simulations were performed using only hydrodynamic
and mass transport models to obtain the mass transfer flux
distribution over the electrode and the global mass transfer
coefficient according to a previously reported methodology
(Rivero et al., 2012). Using a trial and error procedure, the A
parameter value was determined at 2.3 by matching experi-
mental and calculated mass transfer coefficients.
Fig. 7 shows the experimentally determined mass transfer
coefficient values along with the simulation results (contin-
uous line) in dimensionless form. The empirical correlation
found is
Sh = 0.304Re0.785 Sc0.33
The A parameter value found (A = 2.3), lower than those
reported for heat transfer in smooth pipes (Jayatillake, 1969)
and mass transfer in a smooth flat plate electrode (Rivero et al.,
2012) (A = 9.24 in both cases), accounts for the enhancement
429
of mass transfer rate caused by roughness of the copper elec-
trodeposits. This is in agreement with our previous results
for copper electrodeposition at the surface of a rotating cylin-
der electrode (Rivero et al., 2010). Although, there is a slight
difference in the A value from this last case (A = 2.9), this
is explained on the basis of different geometry and rela-
tive movement of fluid and solid surface making different
proportionality between the dimensionless concentration dis-
tribution Ci + and the mass transport resistances of the viscous,
buffer and turbulent layers. It is important to note that the
copper electrodeposition have no appreciable effect on the
values of parameters A and those of Eq. (19) (coefficient and
exponent of the Re). This is in agreement with the typical cor-
relations for mass transfer reported in the literature where no
variation of parameters of these correlations in copper elec-
trodeposition is obtained upon varying the electrodeposition
rate.
The exponent of the Re in the empirical correlation (Eq.
(19)) for the mass transfer coefficient is expected to be 0.8 for
fully developed turbulent flow on flat plates (Bird et al., 2007).
The lower value found in this study (0.785) can be related to
the fact that in the small axial distance of the FM01-LC reac-
tor (0.16 m), fully developed flow is not reached as shown in
Fig. 5. On the other hand, this exponent of Re is slightly higher
than those reported by Griffiths et al. (2005) (0.73), Brown et al.
(1993) (0.71) and Hammond et al. (1991) (0.68) for the FM01-
LC reactor using the ferrocyanide/ferricyanide system. This
difference can be associated with the higher Re used in the
present study that prevents the formation of laminar zones in
the reactor, and the presence of micro-turbulences in the near-
electrode region induced by the copper deposits; both factors
promote turbulences and, consequently, higher values of the
Reynolds exponent.
(18)
4.3. Potential and current distribution
Using the results of hydrodynamics, Section 4.1, and the value
of A-parameter determined from experimental mass trans-
fer coefficient, Section 4.2, the copper reduction process was
simulated under mass and charge transfer mixed control by
simultaneous solution of the mass transport, electrical con-
tinuity and anode and cathode kinetic equations. The results
obtained are illustrated in Figs. 8–11 for FM01-LC operation
under the same experimental conditions: Re = 4845, 18.8 mM
inlet copper ion concentration and potential (−0.3 V vs. SHE in
Figs. 10 and 11) between the cathode and the reference elec-
trode placed in the middle of the reactor channel as described
in Section 2.
The concentration Ci,w at the cathode interface (Fig. 8),
given by the concentration wall function, reveals the zones
where the limiting current is reached (Ci,w approaches zero)
as the potential becomes more negative. The effect of the flow
pattern produced by the inlet distributor on the interface con-
centrations is clearly observed.
The ohmic potential drop across the electrolyte
(E˝ = a − c ) calculated from Eq. (17) along the x-axis
(reactor flow direction) at different cathodic potentials (−0.06,
(19) −0.13, −0.21 and −0.3 V vs. SHE) is shown in Fig. 9. This nor-
mal to the electrode surface potential drop shows variations
through the reactor: it is large at the entrance, but diminishes
in the flow direction until reaching a minimum and, finally,
increase slightly near the channel exit. This potential drop
distribution is in agreement with hydrodynamic behavior in
430 chemical engineering research and design 1 0 0 ( 2 0 1 5 ) 422–433

Fig. 10 – Total overpotential over cathode surface of the

FM01-LC in Cu2+ reduction. Inlet Cu2+
concentration = 18.8 mM, Re = 4845, potential between the
cathode and reference electrode = −0.3 V vs. SHE (see Fig. 2).

The contour lines of the total cathodic overpotential (con-

centration and activation overpotential), calculated as the
difference between the potential of the electrode Ec and the
potential of the electrolyte at the interface c , are depicted in
Fig. 10. Such overpotential distribution shows the strong effect
of hydrodynamics on the mass transport of copper ions toward
the cathode coupled to the electrochemical reaction rate and
the electrical potential. The higher overpotential lines corre-
spond to lower turbulence regions and vice versa, following
the flow pattern caused by the geometry of the reactor, mainly
the inlet and outlet distributor.
Fig. 11 shows the current density distribution at both
Fig. 8 – Simulation of Cu2+ concentration at the cathode
electrodes. The cathodic current distribution exhibits a strong
interface when different potentials between the cathode
influence of the inlet and outlet distributor; the five jets
and reference electrode placed in the middle of the reactor
formed (see Figs. 5 and 6) produce regions of low mass trans-
channel (see Fig. 2) are applied (potential values indicated
fer resistance decreasing the concentration polarization, and
in the figure vs. SHE). Inlet Cu2+ concentration = 18.8 mM,
allowing for an increase in current density, but at the same
Re = 4845.

the reactor where higher turbulence regions produce higher

mass transfer rate and higher current density. Moreover, the
change of potential drop with cathodic potential depicted
in Fig. 9 is consistent with results of concentration at the
interface shown in Fig. 8, i.e. in zones where concentration
at the interface approaches zero a minor change of potential
drop with cathodic potential is observed. It is clear that a
simple primary distribution is insufficient to describe the
behavior of the potential drop in the reactor.

0.16 -0.3 V vs. SHE

-0.21
-0.13
Potential drop/V

0.12 -0.06

0.08

0.04

0 Fig. 11 – Current density distribution over the cathode

0 0.04 0.08 0.12 0.16 surface for copper reduction and its effect on the anodic
Distance, x/m current distribution for water oxidation given by coupling
the hydrodynamic-dependent mass transport, electrode
Fig. 9 – Axial variation of the ohmic potential drop along kinetics and electrical continuity (conditions given in
the reactor channel (conditions given in Fig. 8). Fig. 10).
 chemical engineering research and design 1 0 0 ( 2 0 1 5 ) 422–433
Fig. 12 – Patterns of copper electrodeposition over the
electrode of the FM01-LC reactor at (a) Re = 2769 and 5 min
electrolysis time, and (b) Re = 1384 and 10 min electrolysis
time.
time this high current density demands a higher overpo-
tential according to the Butler–Volmer equation. In addition,
high current density regions provoke high ohmic potential
drop diminishing the available overpotential in potentiostatic
experiments so that a dynamic balance is reached at the
steady state. The final results are a low overpotential and
high current density (absolute values) regions at the electrode
surface at the entrance of the reactor (Figs. 10 and 11). There
is then a calm region, where a high overpotential and low
current density are evident. It is worth noting that the mass
transfer resistance is due not only to the low local velocity
but also to the low turbulence intensity.
At the anode, the electrochemical reaction is not
dependent on mass transport of reactants, however, the non-
uniformity of current density at the cathode surface produces
an anodic current density distribution due to the electrical
continuity requirement. Nevertheless, the variations of cur-
rent density at the anode are smoother than those at the
cathode showing a steady decrease of current density from
the inlet in the axial direction that reaches a minimum at
13.8 cm from the inlet and then a slight increase close to the
outlet. Since the overpotential depends on the current density
distribution, an ovepotential distribution at the anode is also
evident. It is worthy of note that the oxygen evolution at the
anode was not taken into account in the model. Although gas
bubble production may lead to several changes like decreas-
ing the effective conductivity and modifying the flow pattern,
their effects were considered minor as the high flow used can
carry the bubbles away rapidly.
The general behavior obtained by simulation and depicted
in Figs. 8–11 for copper recovery in the FM01-LC reactor was
found to be qualitatively similar to the results of simulations
at different Re ranging from 1384 to 4845 at the same cathodic
potential (with respect to the reference electrode). The jet for-
mation and the flow pattern developed determine the mass
transport rate in each zone of the reactor leading to equivalent
effects on current density and overpotential on the electrode
surface but with faster rate as Re increases.
Experimentally, the type of copper deposits is different
depending on Re. At high Re, keeping the same cathodic poten-
tial, the high copper deposition rate leads to loosely adherent
copper deposits making the removal of copper deposits easier
because of the high shear stress of the fluid flowing at high
velocity.
431
0
-10
Current density, Jc/A m-2
-100
-25
-200
-40
-300
-55
-400 -70
-500 -85
-0.5 -0.25 0 0.25
Potential, Ec vs SHE/ V
Fig. 13 – Average current density obtained from copper
electrodeposition simulations at FM01-LC reactor under
different cathodic potentials (solid line) and experimental
sampled current (dots). Results of simulation (broken line)
of a reactor channel with homogenous inlet velocity and
constant sectional area are shown for comparison.
Conditions: 18.8 mM CuSO4 in 1 M H2 SO4 , Re = 4845.
Fig. 12 shows the patterns of the copper deposits on the
electrode surface obtained after 5 and 10 min of electrolysis.
The regions covered by copper follow the current density dis-
tribution pattern at the cathode shown in Fig. 11. At short
times the figure reveals the effect of jets on copper deposition.
Also, the effect of the two high velocity streams near the chan-
nel wall (Fig. 5) and the consequently high current density at
the cathode edges (parallel to the flow direction in Fig. 11), is
displayed in Fig. 12a. At longer electrolysis times (10 min), the
copper deposit shape follows the high and low current den-
sity zones (Fig. 12b) depicted by simulation in the cathode in
Fig. 11.
With regard to simulations at different cathodic potentials,
Fig. 13 shows the average current density obtained by surface
integration of the current density over the electrode divided
by the electrode area at each steady state simulation (solid
line) and the comparison with experimental data (dots).
Even though the current distributions are not uniform on the
electrode, the average current densities calculated are close to
the experimental data. This fact proves the capability of the
approach used in the model. On the other hand, the very wide
sigmoidal curve (solid line) depicted in Fig. 13 represents the
wide current density distribution on the electrode, i.e. at not
very negative cathode potential some areas of the electrode
surface reach the limiting current density while others (with
lower mass transfer resistance) close to the entrance of the
reactor are far from limiting current density; and the more
negative is the cathode potential, the larger is the area of
the electrode surface reached by the limiting current density.
For comparative purposes Fig. 13 shows the current potential
curve (broken line) predicted by the model when ideal inlet
and outlet reactor distributors are used. The simulations at
the same Re (Re = 4845) and inlet copper ion concentration
(18.8 mM) were performed only in the reactor channel (formed
by the space between the electrodes) with a homogenous
inlet velocity. Under these circumstances, the sigmoidal curve
is more sharply so that the mass-transfer-controlled plateau
is reached at less negative potential. In this case, as expected
the current density is lower than that obtained for the actual
432 chemical engineering research and design 1 0 0 ( 2 0 1 5 ) 422–433
FM01-LC reactor since the additional turbulence generated
by distributors in the last case leads to higher mass transfer
coefficients.
Furthermore, as the cathode potential in the FM01-LC
becomes more negative, the overpotential of higher mass
transfer resistance zones increases more (in absolute value)
than the average overpotential value, which increases the risk
of side reactions in these zones. The experimental points at
more negative potential in Fig. 13 show that the current begins
to increase (absolute value) due to the appearance of the
hydrogen evolution reaction (HER) which shows that higher
overpotential regions started to develop this side reaction. It
is important to note that at this potential (0.386 V vs. SHE) the
HER is not expected to take place based on micro electroly-
sis experiments on an RDE (Rivera and Nava, 2007). However,
in the FM01-LC reactor, higher overpotential regions might
be developing before the reference point can reach such high
overpotential owing to the non uniform overpotential distribu-
tion. Clearly, under these conditions the model deviates from
the experimental data as the side reactions are not taken into
account in the model, but the implications of the model calcu-
lations remain valid since regions of higher overpotential than
that where the potential is measured exhibit an overpoten-
tial high enough to drive the reduction of protons. Moreover,
the overpotential and current density distribution explain the
experimental results. The picture described for the overpo-
tential and current density distribution where the fraction of
surface area of the electrode reaches the limiting current con-
ditions and the overpotential is high enough to develop side
reactions as the cathode potential becomes more negative,
produces current–potential curves with ill-defined plateaux
which is in agreement with experimental results.
5. Conclusions
A comprehensive mathematical model was developed to sim-
ulate the complex relationship between hydrodynamics and
distribution of tertiary current and potential for copper recov-
ery in a continuous filter press type electrochemical reactor,
where non-ideal flow patterns, like backmixing, preferen-
tial flow, inlet effects, dead zones, etc., are present. The
model comprises the following equations: Reynolds averaged
Navier Stokes, convection–diffusion, Butler–Volmer kinetics
for copper reduction, Tafel for water oxidation and electri-
cal continuity. The model was able to provide information
on velocity, copper ion concentration and electrical potential
fields inside the reactor, from which important distributions
could be calculated: overpotential, mass transfer flux and cur-
rent density over the electrode surface. As part of the model
development the mass transfer coefficients were determined
experimentally and a fitting parameter (A) of the concentra-
tion wall function was tuned to the mass transfer model.
The A-value and mass transfer coefficients obtained account
for the enhancement of mass transfer due to the roughness
caused by copper deposition. Simulation results show the
importance of the reactor geometry, especially of the inlet and
outlet distributors in the FM01-LC reactor where some flow
characteristics such as back mixing, preferential flow and low
velocity zones cause strong variations of the mass transfer
rate in different parts of the electrode and, consequently, a
nonuniform overpotential distribution over the electrode sur-
face. These characteristics have profound implications on the
reactor performance that require assessment in order to ana-
lyze experimental data of copper recovery before process scale
up. The results obtained from the simulation are in agree-
ment with potential current experimental data before the HER
takes place. Moreover, they allow explanation of the difference
between the potential necessary to start the HER in the FM01-
LC and that expected from microelectrolysis experiments. It
is important to note the advantages in approach presented
here which allowed a complete description of the tertiary cur-
rent distribution in an electrochemical reactor under the most
practical type of flow regime (turbulent flow) requiring mod-
erate computer resources.
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