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BlIlletin of ELectrochelllistrv 16 (I) January 2000, pp 5-9 0256-1654/2000/$ 3-50

© 2000CECRI

CYCLIC VOLTAMMETRIC STUDIES ON SPHALERITE ELECTRODES

G N SRINIVASAN AND S VENKATAKRISHNA IYER

Central Electrochemical Research Institute, Karaikudi 630 006. INDIA

Cyclic voItammetric studies on sphlarite compact electrodes containing 30% Graphite and 10% pitch and
carbon paste electrodes have been carried out in sulphuric acid of concentration 0.5N, l.ON and 2.0N at
different scan rates. The open circuit voltage varies from 200 to 300 mV. It has been observed that the
dissolution current increases with acid concentration and scan rate. The peak current also increases slightly
if the initial potential is changed from 0 to -0.4 V. The cyclicvoItammogram shows the oxidation of ZnS,
the product, sulphur in the forward cycle and the reduction of the oxidation product in the reverse
(cathodic) cycle. The peak potential shifts anodically, as the scan rate is increased; but shifts to less anodic
potential with the rise in the concentration of the acid. '

Keywords: Sphalerite, cyclicvoltammogram, anodic polarisation, electroleaching, anodic dissolution

INTRODUCTION to the platinum wire. The exposed wire portion and one face
of the electrode are masked with an epoxy resin, These
compacts posess sufficient strength with a resistivity less than
Zinc is an important metal, which finds extensive application
2 ohm cm. Electrodes used for the study have an area of
in various fields including agriculture and rubber making. 2
0.7854 cm .
The demand for the metal is day by day increasing. Zinc
For the cyclic voltammetric studies a Potentioscan (Wenkmg
occurs in nature as sulphide ore and is produced both by
pyrometallurgical and electrohydrometallurgical processes. model POS73) which is a Combined version of Potentiostat
and Scan generator is used. The study comprises anodic
Direct recovery of the metal from zinc concentrate were'
sweep followed by a cathodic sweep between two potentials,
attempted as in the case other base metal sulphides [I]. The
The current out put is recorded as a function of input
present investigation was undertaken to study the
potential using a Rikadenki X-Y recorder model Rw 2017,
electrochemical oxidation 'of sphalerite using cyclic
Each time the electrodes are polished with emery sheets, I/O
voltammetric technique.
to 4/0 and washed well with distilled water. Cyclic
voltammograms are taken only after the electrodes are
EXPERIMENTAL
allowed to attain the equilibrium potential. All potentials
In the direct electrolysis of sulphides the major problem is refen'ed to in the text are with reference to saturated calomel
the tabricative of a stable electrode. In the case other base electrode.
metal sulphide the electrodes can either be massive mineral
itself or cast type. But in the case of sphalerite it can not be RESULTS AND DISCUSSION
casted and the electrodes are fabricated using compaction
Cyclic voltammetric studies on sphalerite compacts have
technique. As sphalerite in pure form is regarded as an
been carried out in sulphuric acid of concentrations 0,5 N.
insulator with a resistivity of 10-10 ohm cm [2,3], it has to
be mixed with a conducting inert material like graphite. The T ABLE I: Partial chemical composition of sphalerite
composition of sphalerite concentrate used in this
investigation is given is Table I Element Percentage
For the present study sphalerite concentrate is mixed with Zn 50.50
300/, natural beneficiated graphite and 10% pitch and the 31.61
2 S
mixture is compacted in a die at a pressure of 46.4 KN cm-
Fe 8.08
and heat treated at 423K. The detailed preparation has been
Si02 4.06
described elsewhere [4J, The electrical connection to the
Pb 1.74
pellet is effected through a platinum wire embedded during
Cd 0.81
compaction process. A thin insulated Copper wire is soldered

5
 Srinivasan et al- Cyclic voltammetric studies on sphalerite electrodes

1.0 Nand 2.0 N at different scan rates. The open circuit (2)
potential varies from 200-300 mY. A typical
cyclicvoltammogram of sphalerite compact in l.0 N H 2S0 4
Hence it is expected that oxygen has a significant effect on
at potentials ranging from 0 to 1.5 V at 20 mVs- 1 is given
the rate of dissolution. But Narasagoudar et al. [8] observed
in Fig.l. It is seen that the current increases rapidly, with
no change in the rate of dissolution when either oxygen or
increasc in potential forming a well-defined peak' AI' at 560
nitrogen sparging is used. This suggests that during
mV and then decreases till a potential of 800 mV is reached.
polarization, most of the Zn ++ is produced electrochemically.
Thereafter again it increases continuously till the final
potential is reached. A small broad kink' A2' is observed at Peak A2
a potential of 1.1 V. On reversing the sweep at 1.5 V the This peak can be attributed to the oxidation of the product
current drops slowly and is anodic upto a potential of 600 formed during the anodic dissolution of ZnS.
mV Indicating the dissolution of sphalerite and thereafter
The product, S, is thermodynamically oxidisablc at much
the current decreases rapidly. A peak 'C' is observed at 180
lower potential. Since there is no oxidation of sulphur upto
mY, which is not sharp. Considering the potentials at which
a potential of 800 mY, the oxidation may occur with
peaks are observed the following electrochemical reactions
overpotential [9] at this value. The reaction. which occurs,
are envisaged.
can be described by the following reaction:
Peak Al
The main reaction at this peak is the oxidation of ZnS, as (3)
shown by the equation given below:
A similar behavior has also been observed by Choi et al.
ZnS = Zn 2+ + SO + 2e EO = 0.02V (1)
[10]. Another .evidence which may be got for the formation
of sulphate is that when electrode is held at 1.5 V for
Price and Warren [5] have also obtained similar results when sometimes (10 sees), the Current during the reverse sweep is
ZnS is anodically polarized in IN H~S04 (maximum current much more anodic than the one when the sweep is reversed
at 0.61 V) Kunieda et al. [6] and Oki et al. [7] have suggested
that graphite or a noble metal sulphide can act as galvanic
couple and oxygen reduction takes place at the cathode by
immediately after reaching 1.5V.
This is described in Fig.2. The possible reason may be that
during the anodic sweep all the sulphur formed on the
~

the following reaction: . electrode surface might not have been oxidized within the 1
short span of time. Hence the current starts decreasing I lj
I
ISITIA

1
.i
o

00 0·4 0·8 1·2

0'0 0·4 0·8 1·2

Potential. V vs SCE
Potential. V vs S C E

Fig.I:Cvclic voltammogram of sphalerite comp~ct electrode ill Fig.2:Cyciic voltammogram of sphalerite compact electrode 111
-\
I N H 2S0 4, Sweep rate 20 mVs IN H2S0 4 held at 1.5 V for 10 secollds. Sweep rate 20 mVs

6
 Srinivasan et al - Cyclic voltammetric studies on sphalerite electrodes

immediately after the reversal of the sweep due to the confirmity with the observed result. Other researchers r11.12]
blockage by sulphur on the surface of the electrode. Once have also noticed similar behaviour.
the sulphur is oxidised to soluble sulphate by the prolonged
Peak C
polarisation of the electrode at 1.5Y the surface area of the
electrode exposed is much larger than the previous case and During reverse scan a cathodic peak is formed at 0.l8Y This
hence the increase in the anodic current in the reverse sweep. may be the reverse reaction of equation (3). which may be
It has been observed by Narasagoudar et al. [8] that when represented as:
ZnS is potentiostatically polarised at 0.61 Y, the Zn++IS ratio
was found to be greater than one suggesting either sulfur
S042- + 8H+ + 6e = SO + 4Hp EO = 0.18 Y (6)
removal by the reaction (3) or by the production of excess
Zn ++ ion by the following reaction: or by the reduction of S

ZnS + 2H+ = Zn++ + H 2S (4) S(5) + 2H+ + 2e = H 2S(nq) EO = -0.10 Y

The H2S. which is unstable at this potential, may be oxidized If the reaction mentioned in equation (6) is the only reaction,
by the reaction (5) the electrode surface is expected to be covered either fully
or partially by sulphur and the area of the electrode exposed
(5) in the subsequent cycle is expected to be less. Even in the
case of chemical oxidative dissolution of zinc sulphide and
But when the electrode is polarized at 0.26 Y. the Zn++IS other metal sulphides the sulphur formed on the mineral
ratio was found to be 1.04 [1] suggesting the absence of particle surface controls further dissolution. Hence the peak
sulphur oxidation or the formation of Zn++ through equation current should be less than that in the Ist cycle. In actual
(4). Hence in all probability above 0.8Y the main reaction practice it can be seen from Fig.3 that the current Increases
that removes sulphur is its oxidation to sulphate. which is in

IsmA

IX) 0·4 0.. l-2 M

Potential, V VI SeE
-0·4 0-0 0·4 0·8 '-2
Pot~ntial , V vs seE
Fig.3:Effect of cyclillg 011 the voltammogram of

sphalerite compact electrode ill 1 N H2 S0 4

Fig.4:Cyclic voltammogram of sphalerite compacr electrode In
-1 -1
Sweep rate 20 mVs (a)lst cycle (b) 2nd cycle (c) 3rd cycle
2 N H2 S0 4, Sweep rate 5 III Vs

7
 Srinivasan et al - Cyclic voltammetric studies on sphalerite electrodes

in subsequent cycles and hence it can be assumed that after and the anodic current is found to be less in the
this reaction, the sulphur thus produced also undergoes a subsequent cycle. Since there is no reduction in the anodic'
reduction process and gets reduced to H 2S. This reaction may peak current in the next cycle, it may be assumed that the
result in the removal of blocked surface, though the product peak 'C' is not due to the reaction mentioned in equation
H2S may also adsorb on the surface. This action should end (8); but probably due to reaction (6) which is supported by
up either with the maintenance of same level of anodic peak other workers [10] and also due to the reaction (equation 7),
current or increased amount of current due to the increase though it is claimed [10] that sulphate ion is stable at this
in porosity of the compact as some ZnS molecules have potential. Such a process may be expected to provide an
already reacted. anodic peak around -0.14 V. Kelsal and Page [13] observed
The other possibility is the reduction of Zn++ to ZnS i.e. the a reduction peak at -0.34 V and an oxidation peak at -0.19
reverse of the reaction mentioned in equation (I), which can V. It has been observed during polarisation in 2N H2S04
be writLen as follows: (Fig.4), a peak appears at 0.08V during anodic cycle and
this may correspond to the oxidation of H 2S. In other cases
Zn++ + S(s) + 2e = Z1!S Eo = 0.02 V (8) it can be assumed that the rising portion of the curve in the
forward or anodic cycle may be composed of ZnS and any
adsorbed H 2S undergoing oxidation.
ZnS formed in this way may be expected to I:>e an insulator,
A peak in cathodic cycle has also been observed by
as this film does not make a good contact with the graphite.
Narasagoudar et al. [8] and they have attributed the decrease
This has been proved [8] by passing H 2S through the
in current after 600 mV as observed in the present case to
solution, which precipitates Zn++ as ZnS on the electrode,
the reduction of Zn(OHh or ZnO
by the reaction.
Zn(OH)2 + 2H+ + S + 2e = ZnS + 2H 20 (10)
(9)

-0·4 0·0 0·4 0·8 1-2

-0,4 0-0 0" 0·8 1·2 16
Potential. V vs S C E
Potential, V vs SCE

Fig. 5: Cyclic voltammogram of!rhalerite compact electrode i/l Fig.6:Effect of scan rate on voltammogram of

IN H2S0 4, Sweep rate 5 mVs . Potential range -0.4 to 1.5V sphalerite compact electrode in 1 N H2S0 4 , a.5. b.10 mVs-

8
 Srinivasan et al - Cyclic voltammetric studies on sphalerite electrodes

As in the case of H2S sparging, ZnS produced by the reaction Effect of scan rate
(equation 10) also is expected to be less conducting. As the scan rate is increased from 5 mVs- J to higher values
Moreover it does not provide any reason for the increase in (maximum scan rate = 200 mVs- I ), peak currents increase
current in the subsequent cycle. The reduction of ZnO by and also the tenden~y of the current changing from cathodic
H+ ions takes place at a much more negative potential to anodic becomes less. Except for 5 mVs- 1 sweep rate, all
(-0.68 V). curves taken at higher scan rates remain cathodic after second
cathodic peak and their cathodic peak currents increase with
Effect of change of initial potential the scan rates. These are presented in Figs.6 and 7. The
It is seen from Fig.5 that a reduction appears near 0 V and reason may be due to less adsorption of H2S on the electrode
also below 0 V. In order to have a complete picture of surface because of faster scan rates. Also there is a slight
oxidation and reduction reaction below 0 V, the initial increase in the anodic peak current when the initial potential
potential is changed to slightly cathodic i.e. to -0.4 V and is changed from 0 V to -0.4 V (At 20 mVs- 1 scan rate the
the final potential is kept at the same level i.e. at 1.5 V. It ip = 33 rnA when initial potential is 0 V. It increases to 35
can be seen from the Fig.5 that two well defined peaks rnA when initial potential is changed to - 0.4 V).
appear in the reverse cycle around a potential of 0.15 V (C I)
and 0.06 V (C 2 ). As already explained the peak at 0.06 V CONCLUSION
may be due to the reduction of sulphur to H 2S. It can be
Cyclic voltammetric studies with compacted sphalerite
seen that after the second. peak the current becomes less
electrodes show that during anodic oxidation of ZnS the main
cathodic and crosses zero and becomes anodic. This may be
products are sulphur and sulphate which undergoes reduction
due to the adsorption of H 2 S formed on the electrode thereby to H2S during reverse cycle.
preventing the further reaction. After a potential of -0.1 V,
By changing initial potential to -0.4 V the study shows two
the current again becomes cathodic and it may be due to the
well defined peaks in the reverse scan due to the reduction
reduction of ZnO or Zn(OHh.
of sulphur to H2S.
The increase in the scan rate produces higher anodic CUITents
and the tendency to remain cathodic also decreases. The
cathodic peak currents also increase with scan rates.

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Fig.7:Effect of scan rate on voltammogram of
-I
sphalerite compact electrode in 1 N H 2S0 4 , a.ZO, b.50.mVs