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Electrochimica Acta 55 (2010) 57095718

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

On the modeling of electrochemical systems with simultaneous gas evolution.


Case study: The zinc deposition mechanism
H. Van Parys a,,1,2 , G. Telias b , V. Nedashkivskyi b , B. Mollay b,c , I. Vandendael a,1 ,
S. Van Damme a , J. Deconinck a,1 , A. Hubin a,1
a
Vrije Universiteit Brussel, Research Group Electrochemical and Surface Engineering (SURF), Pleinlaan 2, 1050 Brussels, Belgium
b
CEST, Centre of Competence in Electrochemical Surface Technology, Viktor-Kaplan-Strae 2, 2700 Wiener Neustadt, Austria
c
University of Vienna, Institute for Physical Chemistry, Whringerstrae 42, 1090 Wien, Austria

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

Article history: Electrodeposition of zinc with simultaneous hydrogen evolution in an aqueous acidic sulphate solution is
Received 18 December 2009 investigated in an Inverted Rotating Disk Electrode (IRDE) reactor. A simulation tool, based on the MITReM
Received in revised form 2 May 2010 (Multi-Ion Transport and Reaction Model) model is used to describe the electrochemical behavior. This
Accepted 3 May 2010
model can account for mass transport by convection, diffusion and migration and for the presence of
Available online 12 May 2010
homogeneous reactions. The electron transfer at the electrode is described by a ButlerVolmer relation.
A reaction mechanism is proposed from surface analysis of the deposited zinc layer. Field Emission Auger
Keywords:
Electron Spectroscopy (FE-AES) in combination with Factor Analysis (FA) is used to determine the com-
Electrode kinetics
Zinc electrodeposition
positional structure of the formed zinc layer. The model parameters such as diffusion coefcients, rate
AES analysis constants and transfer coefcients are determined by comparison of experimental and simulated polar-
Reaction mechanism ization curves and current efciency proles for different rotation speeds of the IRDE and concentrations
Hydrogen gas bubbles of supporting electrolyte. The importance of the homogeneous reactions is shown. The inuence of gas
bubble evolution (induced micro-stirring effects, reduced electrolyte conductivity and surface blockage)
on the electrodeposition process is elucidated.
2010 Elsevier Ltd. All rights reserved.

1. Introduction always in the case where no or almost no hydrogen evolution occurs


[58].
The elucidation of a reaction mechanism and quantication of When the hydrogen reduction reaction takes place, the pH in
the reaction rates of the electrode reactions have been the sub- the immediate vicinity of the electrode changes. This has a pro-
ject of many studies. However, when hydrogen evolution takes found effect on the chemical equilibria of the species present in
place simultaneously with metal deposition, the reaction mech- the solution. In literature few works can be found that consider the
anism becomes much more complex and is still poorly understood. effect of the chemical reactions taking place in the bulk and the
The hydrogen bubble formation changes the ow eld and, as a immediate vicinity of the electrode surface [911]. Nylen [9] for-
result affects the mass transport of the electro-active species. Also mulated a model to investigate the interplay between the acidifying
the conductivity of the electrolyte is affected by the presence of gas electrode reactions and the water dissociation reaction in the chlo-
bubbles [14]. rate production process. Zouari [11] studied the zinc deposition in a
In this paper the zinc deposition mechanism is chosen as a rep- diluted zinc sulfate medium. He studied two reaction mechanisms
resentative system for the study of this type of reactions. Over the (i) the simple two electron transfer and (ii) a simplied version
years, zinc deposition has been extensively investigated, but nearly of the model proposed by Wiart [5]. The latter model relies upon
the intermediate formation of Zn+ at the electrode surface and an
autocatalytic process involving Znads + . He concluded that the zinc
electrodeposition in a diluted zinc medium can be grossly tted by
Corresponding author. Fax: +32 2 629 32 00 the simple two electron transfer. He also emphasizes that, to come
E-mail addresses: hvparys@vub.ac.be (H. Van Parys), anhubin@vub.ac.be to a more complete model, the physical phenomena involved in
(A. Hubin). the overall electrodeposition of zinc carried in a sulfate medium
1
ISE member.
2
cannot be ignored. Mandin et al. [12] studied the electrochemical
Heidi Van Parys thanks the Flemish Institute for support of Scientic-
Technological Research in Industry (IWT SBO contract number 040092, project formation of ZnO thin lms in a ZnCl2 electrolyte at pH 6.5. He
acronym: Mutech). concluded that the coupling of the homogeneous reactions and the

0013-4686/$ see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2010.05.006
5710 H. Van Parys et al. / Electrochimica Acta 55 (2010) 57095718

electrochemical processes in the immediate vicinity of the elec- All measurements were thermostatically controlled at 25 0.1
trode surface is strong and needs to be taken into account in the C by means of a water jacket around the cell, the temperature was
modeling of the entire reaction process. controlled by a thermostat (Lauda RE304).
In literature, several analytic procedures are developed to The conductivity of the electrolyte, , was measured with a
extract information concerning the mechanism and kinetics of Tacussel CD6N apparatus.
the electrochemical system under study. However, their validity The current efciency, representing the ratio of the current
becomes limited when more than one electrochemical reaction used for the zinc deposition reaction versus the total current, was
occurs or when also chemical reactions are involved in the pro- determined by charge integration. A zinc layer was deposited on a
cess [13,14]. In order to dene a reaction mechanism of such platinum substrate at a xed cathodic potential during 100 s. Sub-
complex processes and to quantify the model parameters a numer- sequently, the deposited zinc layer was anodically redissolved by
ical approach is required. A simulation tool, namely the MITReM applying an anodic potential in 0.5 M Na2 SO4 . The anodic poten-
(Multi-Ion Transport and Reaction Model) software, developed in tial (+0.4 V vs SHE) was chosen such that no other reaction besides
our group [1517], is used. This model can account for mass trans- the oxidation of zinc takes place. The current efciency is the ratio
port by convection, diffusion and migration and the presence of of the anodic and the cathodic charges. The error bars are calcu-
homogeneous reactions. The electron transfer at the electrode is lated from the standard deviation obtained from 4 measurements
described by a ButlerVolmer relation. at 1.3 V vs SHE for the different rotation speeds.
The aim of the present paper is to investigate the zinc electrode- For Auger analysis zinc layers were deposited on a platinum sub-
position mechanism with simultaneous hydrogen evolution and to strate at xed cathodic potentials. The Auger electron spectra were
propose a simple but reliable reaction mechanism that explains the taken in a JEOL JAMP-9500 F spectroscope, equipped with a Schot-
inuence of the hydrogen evolution reaction on the kinetics of the tky eld emission gun and a high energy resolution hemispherical
metal deposition. In order to clearly see the effect of the hydrogen analyzer that was operated at an energy resolution E/E of 0.06%. A
evolution reaction, a low zinc concentration is selected. A reaction primary electron beam of 10 keV and 10 nA at an angle of incidence
model will be proposed from a combination of surface analysis of of 30 with respect to the sample surface normal was used. The
the deposited zinc layer and analysis of polarization data. vacuum in the main chamber was about 5 107 Pa. Depth proles
were obtained by intermittently sputtering the surface atoms away
with Ar+ ions of 3 keV during 120 s and subsequently measuring the
elements present at the surface after each sputter cycle. A sputter
2. Experimental rate of 20 nm per minute, calibrated on SiO2 deposited on a Si sub-
strate, was used. The spectra recorded during the depth proling
Electrochemical experiments were done in an Inverted Rotat- were obtained using a step of 0.1 eV. To remove surface impuri-
ing Disk Electrode (IRDE) reactor. In this conguration the Rotating ties, the metal surface was cleaned before each measurement by
Disk Electrode (RDE) is placed at the bottom of the electrochemi- sputtering the surface layer for 120 s with 3 keV Ar+ ions. Chemi-
cal cell in contrast to the more conventional RDE set-up in which cal state analysis of the deposited zinc layer was obtained through
the electrode is positioned in the upper part of the cell. In the factor analysis, using a procedure written in Matlab. A 99.99% pure
conventional RDE set-up, gas bubbles tend to shield the electrode zinc standard (Alfa Aesar) and a ZnO sputter target (Goodfellow)
surface by sticking on the downward-facing electrode. By posi- were used as reference material.
tioning the electrode upward-facing at the bottom of the cell, the
formed gas bubbles can freely rise and are no longer shielding the 3. The MITReM model
electrode surface [18,19]. The IRDE reactor consists of a cylindrical
vessel of diameter 74 mm and height 200 mm, with a square water The MITReM model is used to calculate the electrochemical
jacket around it to control the temperature of the electrolyte. A behavior at the electrode and to obtain information about the con-
sketch of the IRDE is reported in [18,19]. Electrochemical measure- centration proles of all considered species in the electrolytes. The
ments were performed with a three electrode conguration using a numerical approach used to solve the complex multi-ion transport
PGSTAT100 potentiostat (Autolab Instruments) of Ecochemie, con- model is mainly based on nite element techniques. This is in detail
trolled by the GPES 4.8 software. The counter electrode was a large explained in the publications of J. Deconinck et al. [1517].
platinum grid (diameter 5 cm) and the reference electrode was a In this model the electrolyte is assumed to be innitely dilute.
Ag/AgCl electrode, saturated with KCl (Schott-Gerte). In the text all The mass transport in solution is described by the molar ux equa-
potentials are referred to the Standard Hydrogen Electrode (SHE). tion:
The working electrode was a zinc rod of diameter 6.7 mm (Alfa
i = zi ui Fci
N U Di
ci + ci v (1)
Aesar, 99.99% purity) embedded in an insulating poly-vinylidene
uoride cylinder of 18 mm diameter. The zinc IRDE electrode was where N i denotes the molar ux of species i, ci the concentration
mechanically polished with SiC 4000 grade paper and thoroughly of species i, zi the charge carried by the species i, F the constant
rinsed with demineralized water before each measurement. The of Faraday, U the solution potential, ui the mobility of species i, Di
rotation speed of the working electrode was set to 100, 500, 1000 the diffusion coefcient of species i and v the uid velocity eld.
and 1500 rpm. Polarization curves were measured from open cir- The three terms on the right-hand side of Eq. (1) represent from
cuit potential (=1.01 V vs SHE) to 1.8 V vs SHE, at a scan rate of left to right mass transport due to migration, diffusion and convec-
1 mV s1 to reach quasi steady-state conditions at each point of the tion. The velocity eld v for a non-conned innite RDE is solved
polarization curve. The step potential was xed at 0.15 mV in order analytically by von Karman and Cochran [20,21].
to measure the maximal amount of data points the software allows. The mobility constant ui expressed in the molar ux equa-
For the preparation of the solutions once-distilled and deminer- tion Eq. (1) is related to the diffusion coefcient through the
alized water and analytical reagents (all Merck p.a.) were used. NernstEinstein relation:
The experimental solutions contain 0.015 M ZnSO4 and 0.1 M or
1 M Na2 O4 as supporting electrolyte. The pH of the electrolyte was Di
ui = (2)
adjusted to pH 2.5 by adding concentrated H2 SO4 . Prior to each RT
experiment, the solution was bubbled with N2 gas for 5 minutes in The current density in an electrolytic solution is carried by the
order to de-oxygenate the electrolyte. motion of all charged species in the electrolyte and is expressed by
H. Van Parys et al. / Electrochimica Acta 55 (2010) 57095718 5711

the following equation: 4. Results and discussion



j = F i
zi N (3) 4.1. Proposition of a reaction mechanism
i
In this section, the compositional structure of deposited zinc
where j denotes the current density eld, F Faradays constant, zi layers is investigated in order to derive information about the
i the ux of species i.
the charge carried by species i and N (electro)chemical reactions taking place during zinc deposition. To
Mass conservation of each species is written as: this purpose, FE-AES measurements are performed on zinc layers
deposited at 500 rpm in the 0.015 M ZnS04 + 0.1 M Na2 SO4 elec-
ci trolyte. Fig. 1 shows the depth proles recorded on the respective
=
N
i + Ri (4)
t zinc layers deposited at 4 selected cathodic potentials, namely at
1.2, 1.3, 1.4 and 1.7 V. In Fig. 1a, which represents the zinc
where N
i denotes the divergence of the ux vector and Ri the
layer deposited at 1.2 V, it can be seen that oxygen is only mea-
production or consumption rate of the ion i due to homogeneous
sured in the rst measuring point, i.e. at the outermost surface of
reactions in the solution.
the zinc deposition layer. Into the layer only zinc and platinum
Electroneutrality in the electrolyte is expressed as:
are measured, the latter coming from the platinum substrate. At
 the surface of the zinc layer shown in Fig. 1b and (c), represent-
zi ci = 0 (5)
ing the zinc layers deposited at respectively 1.3 V and 1.4 V, Zn
and O are detected, while after roughly 20 minutes of sputtering
Eqs. (1), (4) and (5) result in a set of M + 1 equations in the M + 1
no oxygen is measured anymore. In the zinc layer deposited at -
unknowns, ci and U, with M being the total number of ions. So, a
1.7 V oxygen as well as zinc are measured until the interface with
complex set of coupled partial differential equations, with appro-
the platinum substrate is reached (see Fig. 1d). From these depth
priate boundary conditions, have to be solved.
proles the question arises what the chemical composition of the
The electrode reactions, i.e. the boundary conditions at the
zinc is, namely whether the zinc is deposited as pure zinc; as a zinc
respective electrodes, are described by the ButlerVolmer equa-
oxide or even as a combination of both. In literature [2225], it is
tion:
shown that factor analysis is a powerful tool to obtain information
ox,r nr F red,r nr F
about the chemical state of atoms.
jr = nF(kox,r e( RT
(EU))
cred,r kred,r e( RT
(EU))
cox,r ) (6)
In Fig. 2, the results of factor analysis are shown. In these graphs,
where kox,r (kred,r ) denotes the rate constant for the anodic reac- the background component corresponds to the inelastic scatter-
tion r (cathodic reaction r), ox,r (red,r ) the transfer coefcient for ing of the platinum substrate. The results show that the zinc layer
the anodic reaction r (cathodic reaction r), nr the number of elec- deposited at 1.2 V consists of metallic zinc, while Fig. 2b and c
trons exchanged during reaction r, R the universal gas constant, T indicate that the outer part of the deposition layer consists of a
the temperature, E the electrode potential, U the solution potential mixture of pure Zn and ZnO. Deeper into the layer only pure zinc is
and cred,r (cox,r ) the concentration of reductans oxidized (oxidans present. Due to the atomic mixing effect induced by the sputter pro-
reduced) in reaction r. cess, alloying interactions between Zn and Pt or roughness effects,

Fig. 1. Depth proles recorded on zinc layers deposited in 0.015 M ZnSO4 + 0.1 M Na2 SO4 at pH 2.5, 500 rpm, at resp. (a) 1.2 V, (b) 1.3 V, (c) 1.4 V and (d) 1.7 V.
5712 H. Van Parys et al. / Electrochimica Acta 55 (2010) 57095718

Fig. 2. Results of factor analysis applied to the depth proles obtained on the zinc layers deposited in 0.015 M ZnSO4 + 0.1 M Na2 SO4 , pH 2.5, 500 rpm, at resp. (a) 1.2 V, (b)
1.3 V, (c) 1.4 V and (d) 1.7 V.

no sharp interfaces between zinc and platinum are observed. How- k3


2H2 O + 2e H2 + 2OH (9)
ever, the obtained results clearly show that in the rst stages of
the deposition process only zinc is deposited and after a certain k4
Zn(OH)3 + 2e Zn + 3OH (10)
period of time besides the deposition of Zn also ZnO is formed. In
contrast, in the layer deposited at 1.7 V according to the factor The electrochemical reactions are assumed to occur as one step
analysis only ZnO is formed. It needs to be emphasized that the two-electron transfer reactions and only the reduction half reac-
ZnO compound found with factor analysis is located at the same tions are taken into account.
depth as the oxygen peak in the depth proles, which illustrates The electrochemical reactions (7) and (8) take place under acidic
that the factor analysis results are very reliable. conditions, while reactions (9) and (10), resp. hydrogen evolution
Summarized, the results of the factor analysis show that Zn and zinc deposition occur under alkaline conditions.
metallic, ZnO or a mixture of both is formed under different exper- Since ZnO is formed due to a signicant pH shift near the elec-
imental conditions. The presence of ZnO can be explained by a trode surface, it is clear that the electrode reactions are coupled by
pH shift during zinc deposition. Due to the hydrogen gas evolu- the presence of homogeneous reactions taking place in the elec-
tion reaction, H+ ions are consumed. Subsequently, according to trolyte. In Table 1 the considered homogeneous reactions and their
Le Chateliers principle, fresh H+ ions are provided by the disso- equilibrium constants are listed. It is assumed that complete dis-
ciation reaction of HSO4 . However, also these H+ ions rapidly sociation of H2 SO4 and Na2 SO4 occurs by the rst step dissociation
become depleted. As a result, the pH in the immediate vicinity of reaction [26]. For all other reactions equilibrium is assumed. There-
the electrode shifts from an acidic to an alkaline environment. pH for, all reactions are determined by an equilibrium constant, being
measurements near the electrode surface (not shown) have con- the ratio of a forward and backward rate constant. The forward and
rmed that a strong pH increase exist near the electrode surface, backward rate constants for the water dissociation are given in lit-
while the bulk pH remains constant. In alkaline conditions the Zn2+
ions in solution react with OH ions, present in abundance, and
Table 1
can precipitate as Zn(OH)2 . From literature [39,10], it is known that
Homogeneous reactions and their equilibrium constants.
Zn(OH)2 can react further to ZnO in aqueous circumstances. In addi-
tion, under alkaline conditions zinc deposition occurs from the zinc K Ref

hydroxy complex Zn(OH)3 , which is the hydrated form of the zin- H2 O  H+ + OH 1.80E13 mol m3 [27]
cate ion, ZnHO2 . Also, the H2 gas evolution reaction takes place Na2 SO4  Na+ + NaSO4 [26]
H2 SO4  H+ + HSO [26]
from H2 O molecules in alkaline conditions. 4
HSO4  H+ + SO4 2 0.38E+02 mol m3 (in 0.1 M Na2 SO4 ) Exp.
So when all this information is translated into electrochemical 1.01E+02 mol m3 (in 1 M Na2 SO4 ) Exp.
reactions, the proposed reaction mechanism is the following: ZnSO4  Zn2+ + SO4 2 4.90E+00 mol m3 [28]
NaSO4  Na+ + SO4 2 1.48E+02 mol m3 [29]
k1
2H+ + 2e H2 (7) Zn2+ + OH  Zn(OH)
+
2.04E+03 mol1 m3 [39]
+
Zn(OH) + OH  Zn(OH)2 1.55E+08 mol1 m3 [39]

k2 Zn(OH)2 + OH  Zn(OH)3 2.04E+11 mol1 m3 [39]
Zn2+ + 2e Zn (8)
H. Van Parys et al. / Electrochimica Acta 55 (2010) 57095718 5713

Table 2 Because the simulations are one-dimensional and the computa-


Equilibrium concentration of every species present in the bulk of the electrolytes
tion domain is limited to 5.0E04 m, the ohmic drop between the
0.015 M ZnSO4 + 0.1 M Na2 SO4 and 0.015 M ZnSO4 + 1 M Na2 SO4 .
edge of the computation domain and the reference electrode has to
Species 0.015 M 0.015 M be taken into account. In case of a rotating disk, the largest poten-
ZnSO4 + 0.1 M Na2 SO4 ZnSO4 + 1 M
tial variation is found in the region close to the working electrode.
[mol m3 ] Na2 SO4 [mol m3 ]
Therefore, the resistance depends essentially on the radius of the
H2 O 5.56 E+04 5.56E+04 working electrode and much less on the conguration of the cell
H+ 3.16 E+00 3.16E+00
[31]. Hence, it is assumed that the equation of the ohmic drop for
OH 3.14E09 3.14E09
SO4 2 5.02E+01 1.17E+02 the RDE conguration is also valid for the IRDE conguration. As
HSO4 4.17E+00 3.66E+00 a result, the far eld ohmic drop can be included in the numerical
Na+ 1.49E+02 1.12E+03 simulations by using following formula [31]:
NaSO4 5.07E+01 8.83E+02
ZnSO4 1.37E+01 1.44 E+01 1
Zn2+ 1.33E+00 6.02E01
Rohmic = (12)
4r0
Zn(OH)+ 8.55E06 1.88E06
Zn(OH)2 4.16E06 1.88E06 where r0 represents the radius of the Rotating Disk Electrode and
Zn(OH)3 2.67E03 1.20E03  the electrolyte conductivity.

4.2. Reaction kinetics


erature, i.e. kf = 2.5E05 s1 and kb = 1.4E+08 m3 mol1 s1 [27].
For the other reactions, arbitrary values for kf and kb are chosen The results in this study are divided into two parts. First, the
such that they are fast compared to the electrochemical reactions. results of the experimental study are discussed. The kinetics of the
The obtained equilibrium concentration of every species is calcu- zinc electrodeposition process are investigated by means of linear
lated and listed in Table 2. voltammetry and current efciency measurements. The modeling
Next, the diffusion coefcient of every ion present in the elec- of the reaction mechanism and quantication of the model param-
trolyte must be determined. In literature most often only values for eters (rate constants and transfer coefcients) are explained in a
an innitely dilute solution are found. Since the electrolyte used in next part.
this work is not innitely dilute, the diffusion coefcients have to be
scaled such that the computed and measured electrolyte conduc- 4.2.1. Experimental results
tivities agree. The conductivity of the electrolyte can be computed The experimental polarization curves obtained in 0.015 M
by the following equation: ZnSO4 + 0.1 M Na2 SO4 (pH 2.5) are presented in Fig. 3a for different
F2  2 rotation speeds. In the potential region [0.8 V; 1.15 V] the polar-
= zi Di ci (11) ization curves coincide for all rotation speeds. At potentials more
RT
i negative than 1.15 V the inuence of mass transport becomes visi-
ble; especially at 100 rpm. At 100 rpm, the polarization curve shows
where F denotes Faradays constant, R the universal gas constant,
a limiting current plateau between -1.1 V and 1.6 V. This limiting
T the temperature, xj the charge carried by ion i, Di the diffusion
current plateau is not observed at higher rotation speeds.
coefcient of ion i and ci the concentration of ion i.
In Fig. 3b, the polarization curves obtained in 0.015 M
In some cases the diffusion coefcients are not known, also not
ZnSO4 + 1 M Na2 SO4 (pH 2.5) are shown for different rotation
for an innite diluted solution. This is the case for the following
speeds. As for the polarization curves in Fig. 3a all curves overlap
ions: NaSO4 , Zn(OH)+ , Zn(OH)2 and Zn(OH)3 . In this paper the
until 1.15 V. It can be seen that the obtained current densities are
diffusion coefcient of NaSO4 is assumed to have the same numer-
higher in this more concentrated electrolyte, which is due to the
ical value as the diffusion coefcient of the HSO4 ion. The diffusion
fact that the conductivity of this electrolyte is higher. The polar-
coefcients of Zn(OH)3 , Zn(OH)2 and Zn(OH)+ are assumed to have
ization curves show a limiting current plateau between 1.2 V and
the same numerical value as the diffusion coefcient of Zn2+ . In
-1.8 V for 100 rpm and between ca 1.4 V and 1.6 V for 500, 1000
Table 3, the diffusion coefcients of every ion are listed for the 0.1 M
and 1500 rpm.
Na2 SO4 and 1 M Na2 SO4 supporting electrolytes. The diffusion coef-
If we compare Fig. 3a and (b), the graphs show that although the
cient of the ion pair ZnSO4 is adjusted to obtain the best match
same amount of ZnSO4 is added to the solution, the polarization
with the experimental data.
curves obtained in the 1 M Na2 SO4 supporting electrolyte are more
mass transport controlled than the polarization curves obtained
Table 3 in the 0.1 M Na2 SO4 electrolyte. This is attributed to the fact that
Diffusion coefcients after scaling of every species present in the electrolytes
the dissociation reaction of the large amount of NaSO4 ions in
0.015 M ZnSO4 + 0.1 M Na2 SO4 and 0.015 M ZnSO4 + 1 M Na2 SO4 .
the 1 M Na2 SO4 electrolyte shifts the ZnSO4 equilibrium to the left,
Species Diffusion coefcient Diffusion Reference according to Le Chateliers principle, so less Zn2+ ions are available
0.1 M Na2 SO4 coefcient 1 M for the zinc reduction. This shows again the importance of including
[109 m2 s1 ] Na2 SO4
[109 m2 s1 ]
the proper homogeneous reactions in the reaction mechanism.
The experimentally determined current efciency in 0.015 M
H2 O 2.3 2.3 [30]
ZnS04 + 0.1 M Na2 SO4 (see Fig. 4) shows that zinc deposition takes
H+ 8.8 8.0 [31]
OH 4.9 4.2 [31] place between the cathodic potentials 1.1 V and 1.6 V for 500
SO4 2 1.0 0.9 [31] and 1000 rpm and between -1.1 V and 1.8 V for 1500 rpm. For 500
HSO4 1.3 1.1 [31] and 1000 rpm, the largest current efciency (50%), is found for a
Na+ 1.3 1.1 [31] deposition potential of respectively 1.2 V and 1.3 V. A maximal
NaSO4 1.3 1.1
ZnSO4 0.5 0.1 [32]
current efciency of 60% is found for a rotation speed of 1500 rpm
Zn2+ 0.5 0.2 [11] at 1.4 V. So, at least 40% of the total current is used for the hydro-
Zn(OH)+ 0.5 0.2 gen forming reactions. At potentials more cathodic than 1.6 V for
Zn(OH)2 0.5 0.2 500 and 1000 rpm, and more cathodic than 1.8 V for 1500 rpm no
Zn(OH)3 0.5 0.2
electrodeposited zinc is detected. It is possible that, although the
5714 H. Van Parys et al. / Electrochimica Acta 55 (2010) 57095718

Fig. 3. Polarization curves obtained in (a) 0.015 M ZnS04 + 0.1 M Na2 SO4 , pH 2.5 and (b) 0.015 M ZnS04 + 1M Na2 SO4 , pH 2.5, at T = 25 C and 100, 500, 1000 and 1500 rpm.

current efciency measurements indicate otherwise, a zinc layer speeds. The parameters of the electrode reactions, i.e. electrochem-
is formed at high cathodic potentials, but the formed zinc layer is ical rate constants and transfer coefcients, are adjusted such to
badly adhering. Because of the strong hydrogen bubble formation achieve a good correlation between the experimental and simu-
and the precipitation of Zn(OH)2 a badly adhering zinc deposition lated polarization curves. This is done separately for each rotation
layer is formed that can not be detected anymore by the current ef- speed. The obtained kinetic parameters must be independent of
ciency measurements. The 100 rpm case is a special case since low the rotation speed. The kinetic model parameters are presented in
current efciencies are observed. This is attributed to the surface Table 4.
blockage of gas bubbles that remain attached to the electrode sur- Not only a best match between the polarization curves is aimed
face. Because of the low rotation speed the bubbles are not swept at, the model must also hold for complementary measurements.
away by the rotational movement of the IRDE, but reside on the In this case, the measured and computed current efciencies are
surface. At higher rotation speed, gas bubbles are swept away more compared.
easily. On the simulated polarization curves of Fig. 5 different regions
can be distinguished. It can be seen that at small overpotentials
4.2.2. Simulation results only hydrogen evolution takes place in an acidic environment. This
In Fig. 5, the simulated polarization curves obtained in the reaction shows a limiting current plateau between 1.0 V and -1.4 V
0.015M ZnSO4 + 0.1 M Na2 SO4 electrolyte are plotted and compared for 100 rpm. At higher rotation speeds this plateau is not observed.
to the experimental polarization curves at the respective rotation At 1.0 V the zinc deposition from Zn2+ starts. Then, around 1.4 V

Fig. 4. Experimental and computed current efciency at (a) 100 rpm, (b) 500 rpm, (c) 1000 rpm and (d) 1500 rpm obtained in 0.015 M ZnSO4 , 0.1 M Na2 SO4 , pH 2.5 and
T = 25 C.
H. Van Parys et al. / Electrochimica Acta 55 (2010) 57095718 5715

Fig. 5. Experimental and computed polarization curves at (a) 100 rpm, (b) 500 rpm, (c) 1000 rpm and (d) 1500 rpm in 0.015 M ZnSO4 + 0.1 M Na2 SO4 at pH 2.5. The partial
current densities attributed to the reduction of H2 O, H+ , Zn2+ and Zn(OH)3 are shown at each rotation speed.

the partial current of the H+ reduction reaction decreases. The Zn2+ In the second region, between 1.2 V and 1.6 V, a zone of
reduction reaction decreases between 1.5 V and 1.6 V for 100 mixed reaction kinetics is observed, both mass and charge trans-
and 500 rpm and between 1.6 V and 1.8 V for 1000 and 1500 rpm. fer play a role. This means that the current is also determined by
Since no experimental proof concerning the Zn(OH)3 reduction the ow eld. In this region, zone II, it is visually observed that gas
reaction is at hand at this point, this reaction is not taking into bubbles are formed. When gas bubbles are formed at supersatu-
account. The H2 O reduction takes over from a potential of 1.4 V, rated nucleation sites, such as for example scratches or pits at the
this is from the moment the pH in the immediate vicinity of the electrode surface, the formed gas bubbles induce a micro-stirring
electrode surface rises. effect near the electrode surface. This results in an enhanced mass
So, if we have a closer look at the simulated polarization curves, transport [1] and as a result an increased experimental current
three different regions can be distinguished. In the rst region, density is observed. This effect is most clearly seen for 100 rpm,
between 0.8 V and 1.2 V, the H+ and Zn2+ reduction are charge where the current is totally mass transport controlled in region
transfer controlled. It is known [3436] that gas bubbles are not II. Since the model does not take this micro-stirring effect into
immediately formed; the bubble formation mechanism requires account, the computed current density underestimates the exper-
rst a zone supersaturated with dissolved H2 gas. In that region, imental one. However, for 500, 1000 and 1500 rpm, in the second
the formed hydrogen gas is transported away as dissolved gas from zone, both mass and charge transfer are playing a role for different
the electrode by convection and diffusion. Therefor, since no gas electrochemical reactions. So, yet another effect plays a role. The
bubbles are formed in that region, the computed and experimental gas bubbles also reduce the electrolyte conductivity [2,3]. Due to
polarization curves match well. the large distance between the reference and working electrodes

Table 4
Kinetic parameters of the electrode reactions leading to the best match between the simulated and the experimental results, in 0.015 M ZnS04 + 0.1 M Na2 SO4 and 0.015 M
ZnS04 + 1 M Na2 SO4 , at pH 2.5 and T = 25 C. kred is expressed in m/s and red is dimensionless.

Conc. supp. electr. and rotation speed

0.1 M/100 rpm 0.1 M/500 rpm 0.1 M/1000 rpm 0.1 M/1500 rpm 1 M/1500 rpm

Reaction (7) kred 5.7E13 5.7E13 5.7E13 5.7E13 5.7E13


red 0.25 0.25 0.25 0.24 0.26

Reaction (8) kred 2.9E23 2.9E23 8.2E24 8.2E24 1.9E22


red 0.55 0.55 0.57 0.57 0.52

Reaction (9) kred 3.1E17 3.0E20 4.5E21 4.5E21 8.6E18


red 0.18 0.29 0.32 0.32 0.20

Reaction (10) kred


red
5716 H. Van Parys et al. / Electrochimica Acta 55 (2010) 57095718


Fig. 6. Experimental and computed (a) polarization curves and (b) current efciency, in 0.015 M ZnS04 , 1 M Na2 SO4 , pH 2.5, at T = 25 C and 1500 rpm.

and the relatively low conductivity of the 0.1 M Na2 SO4 support- density values of the Zn2+ reduction can be found [11,37,38]. These
ing electrolyte, the ohmic drop between the reference and working values are recalculated to obtain the kred . The obtained values vary
electrodes cannot be ignored. Since the model does not take the between 5.67E21 m/s and 5.8E25 m/s. This agrees well with the
increased ohmic drop due to the presence of gas bubbles into con- value obtained in this work. The literature transfer coefcients vary
sideration, the computed current density now overestimates the between 0.46 and 0.49, which is in line with the value determined
experimental current density. So, here the effect of the reduced in this work (0.56).
electrolyte conductivity is more dominant than the enhanced mass In a next step, the zinc deposition mechanism proposed for the
transport caused by the micro-stirring. 0.015 M ZnSO4 + 0.1 M Na2 SO4 electrolyte is applied to simulate
In region III, 1.6 until 1.8 V, the current density is again solely the electrochemical behavior of the 0.015 M ZnSO4 + 1 M Na2 SO4
charge transfer controlled by the H2 O reduction reaction, so the electrolyte. If the proposed mechanism is appropriate, the kinetic
effect of reduced conductivity by the presence of gas bubbles plays parameters must be independent of the concentration of the sup-
the most important role. However, since we have no experimental porting electrolyte. The simulation results are only shown for
information about the void fraction at this point, i.e. the ratio of the 1500 rpm (see Fig. 6 ). In the potential regions between 0.8 V and
gas volume to the total volume, we cannot correct for this effect. As 1.1 V and between 1.6 V and 1.8 V, a good match between the
a result, the kinetic parameters adjusted to match the experimental computed and experimental polarization curves is found. In the
data inherently contain the effect of the gas bubbles. region of mixed electrode kinetics the experimental and the com-
In Fig. 4, the computed and experimental current efciencies puted curves dont correspond. Since in the 1 M Na2 SO4 electrolyte
obtained in the 0.1 M Na2 SO4 supporting electrolyte are com- the hydrogen evolution reaction is much more important (at least
pared for different rotation speeds. At 100 rpm the computed and 70% of the current is consumed by the hydrogen evolution reaction)
experimental current efciency do not correspond. This is due the match is less good than in the case of the 0.1 M Na2 SO4 sup-
to the surface blockage effect described previously. Although the porting electrolyte. Here, the experimental current density is larger
numerical values for the current efciencies obtained for 500, 1000 than the simulated current density, so, the micro-stirring effect is
and 1500 rpm are not perfectly corresponding with the exper- the most dominant effect. The kinetic parameters for the electro-
imental ones, the courses of the proles are comparable. For chemical reactions are shown in Table 4. The kinetic parameters
500 rpm, in the potential region between 1.2 V and 1.6 V, the agree well with the values for the respective parameters obtained
computed current efciencies are higher than the experimental in the 0.1 M Na2 SO4 supporting electrolyte.
values, which is attributed to the gas bubble coverage. This effect In Fig. 7 the simulated concentration proles as a function of the
becomes less important at higher rotation speeds. Moreover, the distance from the electrode surface (z) are shown for the ions H+ ,
current efciency measurements are performed on a platinum Zn2+ , Zn(OH)+ , Zn(OH)2 and Zn(OH)3 . Fig. 7a shows that the H+
surface. Although it is assumed that very quickly a thin layer of concentration at a potential of 1.4 V reaches zero at the electrode
zinc on platinum is formed, it is known that the overpotential surface. According to theory the limiting current of the H+ reduc-
for the H+ reduction is smaller on platinum than on zinc [33]. So tion is reached at that potential. At a potential of 1.7 V a depletion
the experimentally obtained current efciency will always be an zone of about 7 m from the electrode surface is observed for H+
underestimation of the true current efciency. This explains why ions. This is due to the fact that H+ ions recombine with the OH
at small overpotentials the computed current efciency is system- ions according to the water equilibrium. Because the concentration
atically larger than the experimental value. In Table 4, it can be seen of H+ ions decreases signicantly in the diffusion layer and because
that the kinetic parameters of the H+ reduction reactions are inde- the backward rate constant for the H2 O equilibrium is very high,
pendent of the rotation speed, while the kinetic parameters of the the water recombination takes place more easily than the reduction
Zn2+ and H2 O reduction are not. Those parameters show a trend; the reaction of H+ to H2 . Since the solution near the electrode surface is
value of the transfer coefcient is increasing with increasing rota- alkaline now, the reduction of H2 O to H2 becomes favorable. Due to
tion speed while the rate constant is decreasing. This is attributed the increased pH the Zn2+ ions react with the OH ions and form the
to the gas bubble formation. The numerical values of the kinetic Zn(OH)+ , Zn(OH)2 and Zn(OH)3 complexes. As a result, the Zn2+
parameters are determined by looking for the best correspondence ions near the electrode become depleted (see Fig. 7b) and the Zn2+
between the experimental and simulated data without using phys- reduction current decreases (see Fig. 5). This agrees well with the
ically unrealistic values. As a consequence of this trial and error observed experimental current efciencies (see Fig. 4). The Zn(OH)+
procedure, it is not possible to assign an uncertainty interval to and Zn(OH)2 complexes are mainly formed in the outer part of the
these parameters. In literature, Tafel slopes and exchange current Zn2+ diffusion layer, as can be seen in Fig. 7c and (d). In that region
H. Van Parys et al. / Electrochimica Acta 55 (2010) 57095718 5717

Fig. 7. Concentration proles of (a) H+ , (b) Zn2+ , (c) Zn(OH)+ , (d) Zn(OH)2 and (e) Zn(OH)3 ions obtained in 0.015 M ZnSO4 + 0.1 M Na2 SO4 at pH 2.5 and 500 rpm.

still a sufcient amount of Zn2+ is present to react with OH ions. presence of gas bubbles is elaborated. To this purpose, the zinc
Part of the Zn(OH)2 complex reacts further to Zn(OH)3 ions that deposition mechanism with simultaneous hydrogen evolution was
diffuse toward the electrode surface. So, although from theory it can investigated in the electrolyte 0.015 M ZnSO4 with two different
be expected that zinc deposition in alkaline conditions takes place concentrations of supporting electrolyte, i.e. 0.1 and 1 M Na2 SO4 .
from Zn(OH)3 ions and although according to the numerical sim- Surface analysis of the deposited zinc layer showed that depending
ulations a relatively high concentration of Zn(OH)3 ions is formed, on the experimental conditions either pure zinc, ZnO or a mixture
the reduction to Zn is not observed under the experimental condi- of both can be formed. From this information a reaction model
tions used in this work (see the experimentally determined current is put forward including both electrochemical and homogeneous
efciencies shown in Figs. 4 and 6b). It is possible that besides the reactions. At rst, the electrochemical reactions concern the H2
formation of a badly adhering zinc layer at high cathodic poten- evolution reaction from the H+ ions and the zinc deposition from
tials, the formed Zn(OH)2 precipitates before reacting further to Zn2+ ions. Then, due to the H+ consumption the pH rises in the
Zn(OH)3 . Precipitation reactions are not included in the MITReM immediate vicinity of the electrode surface making the H2 evo-
model. lution from the H2 O molecules favorable. The reduction reaction
from Zn(OH)3 ions is not (yet) taken into account. The proposed
5. Conclusions reaction model is able to qualitatively describe the zinc deposi-
tion mechanism for different process parameters, such as rotation
This work contributes to a better understanding of the model- speed of the IRDE and concentration of the supporting electrolyte.
ing of electrochemical systems with gas formation reactions. The From the comparison between the simulated and the experimental
complex interaction between (electro)chemical reactions and the data it is shown that the formed hydrogen bubbles affect the model
5718 H. Van Parys et al. / Electrochimica Acta 55 (2010) 57095718

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