JOURNAL OF APPLIED ELECTROCHEMISTRY 26 (1996) 379-384

Selective electrodeposition of metals from simulated

waste solutions
R. D. ARMS T RONG* , M. T ODD
Chemistry Department, Bedson Building, Newcastle University, Newcastle upon Tyne, NE1 7RU, Great Britain
J. W. AT KI NS ON, K. SCOTT
Chemical & Process Engineering Department, Merz Court, Newcastle University,
Newcastle upon Tyne NE1 7RU, Great Britain
Received 27 June 1995; revised 13 September 1995
Mo s t i ndust r i al was t e st r eams cont ai n a numbe r of di fferent heavy met al s. The feasi bi l i t y of selective
el ect r odepos i t i on of cadmi um, cobal t and ni ckel as t hei r pur e met al s ( ~9 9 %) f r om bi nar y mi xt ur es
has been i nvest i gat ed. Single cat i on l i near sweep vol t a mogr a ms and nucl eat i on pot ent i al measur e-
ment s have been ma de and used t o pr edi ct t he opt i mum pot ent i al s and condi t i ons f or selective el ect ro-
deposi t i on f r om t he mi xed- cat i on sol ut i ons. The ani ons us ed in this wor k are SO42-, CI - and BF 4 . The
opt i mum pot ent i al f or r emoval by el ect r odepos i t i on of Cd f r om a sol ut i on cont ai ni ng C d ( I I ) and
Co(II) or Ni ( n) wi t hout codeposi t i ng Co or Ni has been eval uat ed f r om a si mpl e di agr am cons t r uct ed
f r om nucl eat i on pot ent i al measur ement s. It is s hown t hat t he [Cd(H)] r emai ni ng in t he sol ut i on aft er
exhaust i ve el ect rol ysi s at a fixed pot ent i al is det er mi ned by t he Ner ns t equat i on, and not by t he elec-
t rol ysi s t i me pr ovi ded t hat a critical mi ni mum t i me has been exceeded.
1. Introduction
Electrodeposition of metals, particularly from
aqueous solutions, is an attractive met hod for the
recovery and recycling of metal ions in many indus-
tries such as plating, metal finishing and electronics.
Over thirty metals can be electrodeposited from
aqueous solutions including many precious metals
and heavy metals. Many of these metals pose environ-
mental hazards and legislation generally imposes
minimum discharge levels regarding quantity and
concentration. A standard approach to satisfy these
requirements is to precipitate the metal ions as
oxide/hydroxide and process the subsequent sludge
prior to disposal or further treatment. In many cases
the solution to be treated will contain more than one
metal ion, for example that produced in the dissolu-
tion of spent Ni / Cd batteries [1]. In this example there
is a requirement to recover the individual metals sepa-
rately to enable efficient economic recovery. It is,
therefore, unattractive to adopt precipitation to
recover the metal from solution, rather a met hod
such as electrodeposition has attractions if selective
deposition of individual metals can be achieved. The
area of metal recovery by electrodeposition has been
a subject of recent reviews [2]. There have been several
studies of electrodeposition from mixed metal ion
solutions, for example Cu/ Ni [3], Pb/ Cu [4] and Zn/
Cu [3]. In many cases, especially those involving Cu,
the difference in standard electrode potential indicates
that selective electrodeposition is effective and
research has demonstrated this to be true. In other
cases, such as Ni / Co the closeness of the standard
potentials indicates that selective electrodeposition
will be more difficult.
In the work reported here the extent, bot h theoreti-
cally and experimentally, to which mixtures of metal
cations in waste waters can be separated as metals
using successive electrodeposition has been explored.
For example, if we consider water containing Cd(n)
and Ni(n) it is important to establish the concentra-
tion to which Cd(I0 can be reduced in the solution
by electrodeposition without depositing Ni and the
purity of the electrodeposited Cd. Previous work of
this sort has been carried out by Walsh and Gabe
[5]. The theoretical basis of their work depended on
the use of the Nernst equation for the metals involved.
Although this approach is appropriate for the separa-
tion of for example A g ( I I ) and CU(II) where the cations
deposit close to their thermodynamic reversible
potentials and where they are present in some solu-
tions as uncomplexed species, a more realistic scheme
has to take account of complexation of the cations
and of the irreversible nature of the electrodeposition
of cations such a s N i ( I i ) . The anions used in this work
are SO]-, CI- and BF4. Appropriate conditions have
been identified where selective electrodeposition is
possible in the cases of Cd/ Co and Cd/ Ni mixtures.
2. Experimental details
2.1. Electrodeposition f rom single cation solutions
The electrodepositions of Cd, Co and Ni from
0021-891X 1996 Chapman & Hall 379
380 R. D. ARMSTRONG E T A L .
aqueous sul phat e solutions were investigated using
stainless steel and Cd rot at i ng disc electrodes (RDE)
of area 0. 16cm 2, shrouded in Teflon. The r ot at i on
rate was 500r. p. m. t hr oughout . The RDE surfaces
were prepared by polishing wi t h 0. 05#m al umi na
and washed wi t h 1 mol dm 3 ( - 1 M) sulphuric acid
fol l owed by deionized water. The Cd RDE was pre-
t reat ed by Cd electrodeposition using a cat hodi c
linear sweep f r om the solutions rest pot ent i al (Er)
for 100mV at 0. 5mVs 1. Cd(II) solutions were
made up from 3CdSO4.8H20 (Fluka, >99%) or
CdC12.2H20 (Fluka, >96%) or Cd(BF4)2 (Strem,
50% aqueous solution). Co(n) solutions were made
up using COSO4.7H20 (Fl uka, >99%) . Ni(II) solu-
tions were made up using Ni SOg. 6H20 (Fl uka,
> 99%). A base electrolyte was added in each case:
for sul phat e solutions, Na2SO4 (Fluka, > 99%), for
chloride solutions, NaC1 (Aldrich, > 99%), and for
fl uoroborat e solutions, NaBF4 (Fl uka, > 98%). Boric
acid was present in some solutions (Fluka, > 99.5%).
The pH of the solutions was adj ust ed in some cases by
the addi t i on of: for sul phat e solutions, H2SO 4
(Aldrich, 99.999%), for chloride solutions, HC1
(Fl uka, >99%) , and for fl uoroborat e solutions,
HBF4 (Strem, 48% aqueous solution).
Measurement s were made in a 3 electrode glass cell
of vol ume 200 cm 3 surrounded by a wat er jacket. A
sat urat ed calomel electrode (SCE) was connect ed to
the cell via a pot assi um ni t rat e salt bridge and a
Luggi n capillary. All pot ent i al measurement s listed
are recorded against the SCE. The count er electrode
was a pl at i num spade (1.9cm2). The solution was
purged wi t h ni t rogen for 5 mi n prior to runs in order
to deaerat e the system. The pot ent i al of the electrode
was cont rol l ed using an EG&G Versast at system con-
trolled by a Vtech 486SX25 comput er via an IEEE-
488 GPI B card. Cur r ent - pot ent i al measurement s
were ma d e b y linear sweep from anodi c to cat hodi c
pot ent i al s at 1 mV s -~.
2.2. El ect rodeposi t i on f r o m mi x e d cation sol ut i ons
A t hree el ect rode glass cell was used whi ch had t wo
compar t ment s each of 100 cm 3 vol ume, separat ed by
a Nat i on cat i on exchange membr ane. The wor ki ng
el ect rode compar t ment was sur r ounded by a wat er
j acket . The sol ut i on in this compar t ment was de-
aer at ed and st i rred by a st ream of wat er sat urat ed
ni t rogen. The wor ki ng el ect rode was a stainless steel
pl at e of area 4 cm 2 bl anked off on one side using a
st oppi ng of f l acquer (Lacomi t , Canni ng). The wor k-
ing el ect rode was held at a const ant pot ent i al using
a pot ent i ost at i c coul omet er and t he cur r ent being
passed was measur ed using a BBC SE120 char t recor-
der. All experi ment s were carri ed out at 20 C. The pH
of t he sol ut i ons were cont r ol l ed by t he addi t i on of
H3BO3 (Fl uka, >99. 5%) . The count er electrode,
present in t he ot her compar t ment , was a 2. 0cm 2
pl at i num spade el ect rode.
The el ect r odeposi t ed met al s were anal ysed using
EDAX measurement s. The sol ut i on concent r at i on
5
4 (a)
)
t (b)
(c)
o
-0.70 -0.75 -0.80 -0.85 -0.90
E / V
Fig. 1. Steady state i/E relationship for Cd deposition onto a Cd
RDE (500r.p.m.) at 20 C from (a) 0.01M Cd(BF4) 2 + 1U NaBF4,
(b) 0.01M CdSO4 -- 1M Na2SO4, (c) 0.01M CdC12 + 1M NaC1.
of Cd(II), Co(II) and Ni(II), after electrolysis, was
det ermi ned by pol arography.
3 . R e s u l t s
3.1. El ect rodeposi t i on f r o m single cat i on sol ut i ons
Fi gure 1 shows the st eady state i / E relationship for
Cd deposi t i on ont o a Cd RDE. The shapes of the
initial region of the sweeps are consistent wi t h the
quasi-reversible deposi t i on of Cd since deposi t i on
starts i mmedi at el y negative to the measured reversible
pot ent i al for the Cd(II)/Cd couple and plots of E
against log [id/(ia -- i)l give slopes between 0.040 and
0.050 V decade -1 which is close to the theoretical
value of 0.030 V decade -1 (Fig. 2). As the pot ent i al
becomes more negative a diffusion limited current
becomes evident. The current density increases furt her
due to powder format i on. Due to compl exat i on the
1.4
1 2 / /
o D
1.0
0.8
0.6

.a
047
0.2 ; 7
0.0 . . . .
-0.72 - 0. 74 - 0. 76 - 0. 78 - 0 . 8 0 -0.82
E / V
Fig. 2. Plots of 1og(ia//d -- i) against E for steady state Cd deposi-
tion onto a Cd RDE (500r.p.m.) at 20C from (a) 0.01M
Cd(BF4)2+ 1M NaBF4, (b) 0.01M CdSO 4-b 1M Na2SO4, (c)
0.01M CdC12 + 1 M NaCl.
DEPOSITION OF METALS FROM SIMULATED WASTE SOLUTIONS 381
Table 1. Comparison of experimental and theoretical E r values for 0.01 ~ Cd(H) + 2 M Na(O for different anions using a Cd RDE (500 r.p.m.) at
20 C
A n i o n Experimental Er Theoretical, Er Majority Cd(H) species % Cd(II) as Cd 2+ (aq)
/ v / v
BF 4 -0.701 -0.704 Cd 2+ (aq) 100
SOl- -0.748 -0.732 CdSO 4 (aq) 24
CI- -0.767 -0.777 CdCI 2 (aq) 2
di fferent ani ons cause differences in the act i vi t y and
concent r at i on of t he Cd 2+ species and this leads t o
di fferent val ues f or t he reversi bl e pot ent i al s (Er) f or
the Cd/ Cd(i i ) coupl e (Tabl e 1). The l i mi t i ng cur r ent
densities are al so di fferent because the maj or i t y
Cd( I I ) species is di fferent in each case due t o compl exa-
tion. Powder f or mat i on occurs at a mor e negat i ve
pot ent i al f r om f l uor obor at e sol ut i ons t han f r om sul-
phat e or chl ori de sol ut i ons.
I ncr easi ng t he t emper at ur e i ncreases t he cur r ent
densi t y at all pot ent i al s by decreasi ng t he ki nemat i c
vi scosi t y of the sol ut i on and i ncreasi ng t he di ffusi on
coefficient of t he el ect roact i ve species t hus enhanci ng
t he mass t r ans por t rat es of t he syst em. Er becomes
less negat i ve as t he t emper at ur e i ncreases as t he act i v-
ity of t he Cd 2+ increases. The l i mi t i ng cur r ent densi t y
i ncreases due t o a decrease in t he sol ut i on vi scosi t y
and the r esul t ant i ncrease in t he di ffusi on coefficient.
The p H of t he sol ut i on has no effect on t he i / E curves
over t he r ange of 2 to 5.5.
Fi gur e 3 shows t he st eady st at e i / E r el at i onshi p f or
Cd, Co and Ni deposi t i on ont o a stainless steel RDE
f r om sul phat e sol ut i ons. The E1/2 val ues f or t he differ-
ent sol ut i ons differ by a bout 100 mV f r om each ot her.
Cd is deposi t ed at t he least negat i ve pot ent i al fol l owed
by Co and t hen Ni. Di st i nct l i mi t i ng current s are
obser ved fol l owed by t he evol ut i on of hydr ogen nega-
tive t o - 1.2 V in the case of Co and negat i ve t o - 1.3 V
in t he case of Cd. For Ni, no di st i nct l i mi t i ng cur r ent
is obser ved bef or e hydr ogen evol ut i on. The i / E curves
f or Co and Ni are consi st ent wi t h i rreversi bl e deposi -
t i on since deposi t i on st art s well negat i ve t o the calcu-
l at ed reversi bl e pot ent i al s f or t he met al / met al i on
coupl es. Powder f or mat i on is onl y obser ved in t he
case of c a dmi um deposi t i on.
Fi gur e 4 shows t he st eady st at e i / E r el at i onshi p
f or Cd, Co and Ni deposi t i on ont o a Cd RDE. Cd
deposi t s at a pot ent i al whi ch is 0.040 V mor e negat i ve
and Co deposi t s at a pot ent i al whi ch is 0.120 V mor e
negat i ve ont o a stainless steel RDE c ompa r e d wi t h
deposi t i on ont o a pr edeposi t ed Cd RDE. Ni deposi t s
at a si mi l ar pot ent i al ont o bot h RDEs . Di st i nct limit-
ing current s are obser ved fol l owed by t he evol ut i on of
hydr ogen at pot ent i al s negat i ve to - 1 . 2 V in all t hree
cases. Powder f or mat i on is onl y obser ved in the case
of c a dmi um deposi t i on.
To est abl i sh t he mi ni mum el ect rode pot ent i al at
whi ch el ect r odeposi t i on of Co and Ni coul d be
achi eved ont o a stainless steel pl at e l i near sweep mea-
sur ement s were carri ed out at rel at i vel y l ow sweep r at e
of 0.05 mV s -1. Typi cal results f or Co are shown in
Fig. 5. The mi ni mum el ect r odeposi t i on pot ent i al s
were cal cul at ed by ext r apol at i on of t he rising curve
to t he base line.
3.2. El ect rodeposi t i on f r o m Co / Cd sol ut i ons
I t can be seen f r om Fig. 3 t hat f or a 0.01 M : 0.01 M Co/
12
10
8
4
2
0 I
-0.7 - 0. 8 - 0. 9 - 1. 0 - 1. 1 - 1 . 2 - 1. 3 -1. 4
E/ V
Fig. 3. Steady-state i / E relationship for deposition onto a stainless
steel RDE (500r.p.m.) at 20C from (a) 0.01M CdSO4 +0.04M
H3BO 3 + 1 M Na2SO4, (b) 0.01M CoSO 4 +0.04M H3BO 3 + 1M
Na2SO4, (c) 0.01 M NiSO4 + 0.04M H3BO3 + 1 M NazSO 4.
14
12
~, 10
8
4 (b)
2
0 ~ L
-0.7 -0.8 -0.9 -1.0 -1.1 -1.2 -1.3
~ / V
Fig. 4. Steady state i / E relationship for deposition onto a Cd RDE
(500r.p.m.) at 20 C from (a) 0.01 M CdSO 4 + 0.04M H3BO 3 1 M
NazSO4, (b) 0.01M COSO4+0.04M H3BO3+IM Na2SO4,
(c) 0.01 M NiSO4 + 0.04M H3BO3 + 1 M Na2SO 4.
382 R. D. ARMSTRONG ET AL.
2.0
1.5
r-q
i
< 1.0
0.5
0.0 i J
-0.78 -0.80 -0.82 -0.84 -0.86 -0.88 -0.90 -0.92
E/ V
Fig. 5. i/E relationship for Co deposition onto a stainless steel sheet
at 20C from 0.04M H3BO3 + IM Na2SO4 + (a) 0.5M, (b) 0.1M,
(c) 0.05 M, (d) 0.025 M, (e) 0.01 M COSO4. Stirring by water saturated
nitrogen.
Cd mi xed sol ut i on t here is a regi on of pot ent i al of
6 0 mV wher e t he el ect r odeposi t ed met al woul d be
expect ed t o be pr edomi nant l y Cd. I n t he electrolysis
of 1 M Na2SO 4 + 0.2M CoSO 4 + 0.002M CdSO 4
0.04M H3BO 3 t he Co : Cd r at i o in t he sol ut i on is
1 0 0 : 1 and t he pot ent i al r ange in whi ch Cd is expect ed
t o be deposi t ed wi t hout t he codeposi t i on of Co is
decreased. El ect r odeposi t i on was carri ed out on this
sol ut i on at a var i et y of pot ent i al s. Fig. 6 shows t he i
agai nst t t r ansi ent s f or t he electrolysis of this sol ut i on
at t wo of t hese pot ent i al s. The cur r ent shar pl y rises
over t he initial per i od as t he Co nucl eat es ont o t he
RDE, becomes di ffusi on cont r ol l ed at l onger t i mes
and t hen sl owl y decreases as t he Cd(ii) species is
r emoved f r om t he sol ut i on. El ect rol ysi s was st opped
when ei t her t he cur r ent dr oppe d bel ow 0.01 mA cm -2
or 40 C (the char ge avai l abl e f r om compl et e r emoval
of Cd(iI) f r om t he wor ki ng el ect rode compar t ment )
had been passed. Tabl e 2 summar i zes these el ect ro-
deposi t i on experi ment s. The cur r ent efficiency was
close t o 100% at - 0. 79 V. At mor e cat hodi c pot ent i al s
it fell due t o si mul t aneous hydr ogen evol ut i on. At
- 0 . 7 8 V t he fall is due t o t he l onger t i me avai l abl e
f or st r ay r eact i ons t o occur. The basis f or t he t heo-
ret i cal val ues is descri bed in Sect i on 4. The
0.4
^ (b)
0.3
eq
~ 0 . 2
0.1
0.0 , , ,
0 20 40 60 80
Time ! ks
Fig. 6. Current-time for the electrolysis of 0.002 M CdSO 4 -- 0.2 M
COSO4+0.04M H3BO3+I M Na2SO 4 at (a) -0.79V and
(b) -0.80 V onto a stainless steel plate at 20 C. Stirring by water
saturated nitrogen.
el ect r odeposi t ed met al pr oduced at pot ent i al s
bet ween - 0. 78 and - 0 . 8 1 V was 95 + 3% Cd. The
concent r at i on of Cd0I ) r emai ni ng in the sol ut i on fell
syst emat i cal l y as t he pot ent i al was made mor e cat ho-
dic. At a pot ent i al of - 0 . 8 2 V Co nucl eat i on occurs
bef or e t he pr edi ct ed [Cd(II)]mi n is reached.
3.3. Electrodeposition f r om Ni / Cd solutions
I t can be seen f r om Fig. 3 t hat for a 0.01 : 0.01 Ni / Cd
mi xed sol ut i on t here is a regi on of pot ent i al of 160 mV
where t he el ect r odeposi t ed met al woul d be expect ed to
be pr edomi nant l y Cd. I n t he electrolysis of 1 M
Na2SOa + 0.2 M NiSO4 + 0.002 M C d S O 4 + 0.04 M
HBBO 3 t he Ni : Cd r at i o in t he sol ut i on is 100 : 1 and
t he pot ent i al r ange in whi ch Cd is expect ed t o be
deposi t ed wi t hout t he codeposi t i on of Ni is decreased.
El ect r odeposi t i on was carri ed out on this sol ut i on at a
var i et y of pot ent i al s. Fi gur e 7 shows t he i agai nst t
t ransi ent s f or the electrolysis of this sol ut i on at t wo
pot ent i al s in this pot ent i al region. El ect rol ysi s was
st opped when ei t her t he cur r ent dr opped bel ow
0.01 mAc m 2 or 40C had been passed. Tabl e 3 sum-
mar i zes these el ect r odeposi t i on experi ment s. The cur-
r ent efficiency was close t o 100% at - 0 . 8 0 V. At mor e
Table 2. Results of selective electrodeposition of Cd onto a stainless steel plate at 20 C f rom a Cd/Co mixture with O.O02 M CdSO 4 + 0.2 M
CoSO 4 -}- O.04 M H3BO 3 + 1 M NazSO 4
Stirring by water saturated nitrogen.
Potential Charge passed Predicted [ Cd(II) ]rain Final [ Cd(II) ] Current efficiency
/V /C /p.p.m. /p.p.m. /%
-0.770 1.1 190 220 -
-0.780 24.0 89 100 89
-0.790 30.7 41 48 99
-0.800 38.5 19 27 88
-0.810 39.8 8.9 19 89
-0.820 39.9 4.1 65 67
0. 8 - 0. 6
0. 6
0. 2
~
0. 4
0. 0 i t
10 20 30 40 50
T i m e / ks
DEPOSITION OF METALS FROM SIMULATED WASTE SOLUTIONS 383
Fi g. 7. C u r r e n t - t i m e f o r t h e e l e c t r o l y s i s o f 0. 002M CdSO 4 + 0. 2M
Ni SO4 - - 0 . 0 4 M H3 B O3 + I N Na2SO 4 a t (a) - 0 . 8 1 V a nd (b)
- 0 . 8 2 V ont o a s t a i n l e s s s t e e l p l a t e a t 20 C. S t i r r i n g b y w a t e r s a t u -
r a t e d n i t r o g e n .
>
"-- -0. 7

o -0. 8
-0. 9
- 1. 0
/ . 4
/
/
/
/ I Y
/
2 1 o / -
I ) m / , ,
/
- ~ [ . m
f [
m / j / m
[
m / 3 / / I
( - / I
/ I
I / I
z
( . . . . I
- 6 -5 - 4 -3 -2 -1 0
l o g [M]
Fi g. 8. V a r i a t i o n o f m e t a l d e p o s i t i o n p o t e n t i a l w i t h d i f f e r e n t c o n -
c e n t r a t i o n s o f C d S O 4 a n d C O S O 4 w i t h 0. 04 M H3BO 3 + 1 M Na2SO 4
o n t o a s t a i n l e s s s t e e l p l a t e a t 20 C. S t i r r i n g b y w a t e r s a t u r a t e d
n i t r o g e n . K e y : ( 0 ) Cd a n d ( l l ) Co.
cat hodi c pot ent i al s it fell due t o s i mul t aneous hydro-
gen evol ut i on. At - 0 . 7 9 V the fall t o 60% i s due t o
-0.6
the l onger t i me avai l abl e f or stray react i ons t o occur.
The basi s f or the predi ct ed val ues is descri bed i n the
di s cus s i on sect i on. The fi nal [Cd(n)] is si gni fi cantl y
hi gher t han t hat predi ct ed usi ng the Ne r ns t equat i on. > -0.7
Thi s may be because there is a si gni fi cantl y hi gher
concent rat i on o f sul phat e i ons i n the s ol ut i on cont ai n- ~
i n g Cd(II) a n d N i ( I I ) than i n that wi t h Cd 0 0 al one ~ -0.8
l eadi ng t o a greater ext ent o f Cd(II) c ompl e xat i on. . =
The el ect rodepos i t ed met al produced at pot ent i al s :~
be t we e n - 0 . 7 9 and - 0 . 8 3 V was 95 + 3% purity. ~, - 0. 9
The concent rat i on o f Cd(i i ) remai ni ng i n the s ol ut i on ~z
fell syst emat i cal l y as the pot ent i al was made mor e
cat hodi c. At a pot ent i al o f - 0 . 8 4 V Ni nucl eat i on N -1.0
occurs bef ore the predi cted [Cd(II)]mi n is reached,
4. Di scussi on
The above results s ho w that i t is pos s i bl e usi ng
el ect rodepos i t i on t o remove c admi um f rom s ol ut i ons
cont ai ni ng mi xt ures o f Cd/ Co and Cd/ Ni . The l owe s t
l evel o f Cd remai ni ng i n the s ol ut i on is det ermi ned by
the pot ent i al whi c h is used f or the Cd el ectro-
depos i t i on. The opt i mum pot ent i al f or the removal
o f Cd( I0 f r om s ol ut i on wi t hout the s i mul t aneous
-1.1 v , , / , , ,E
-6 -5 -4 -3 -2 -1 0
r log [ M ]
Fi g. 9. V a r i a t i o n o f m e t a l d e p o s i t i o n p o t e n t i a l w i t h d i f f e r e n t c o n -
c e n t r a t i o n s o f C d S O 4 a n d N i S O 4 w i t h 0. 04M H3BO3 + 1 M Na z SO 4
o n t o a s t a i n l e s s s t e e l p l a t e a t 20 C. S t i r r i n g b y w a t e r s a t u r a t e d
n i t r o g e n . K e y : ( 0 ) Cd a n d ( l l ) Ni .
Table 3. Resul t s o f selective eleetrodeposition o f Cd ont o a stainless st eel pl at e at 20 C f r o m a Cd/ Ni mi xt ur e wi t h O.O02 M CdSO 4 + 0. 2 M
Ni S O 4 + O.04 M H3BO 3 -t- ] M Na z S O 4
S t i r r i n g b y w a t e r s a t u r a t e d n i t r o g e n .
Potential Charge pas s ed Predi ct ed [ Cd(II) ]mi n Fi nal [ Cd(xl) ] Current efficiency
/ V / C / p. p. m. / p. p. m. / %
- 0 . 7 9 0 26.8 4i 131 60
- 0 . 8 0 0 31.6 19 39 101
- 0 . 8 1 0 36.5 8.9 27 93
- 0 . 8 2 0 39.6 4.1 17 90
- 0 . 8 3 0 39.8 1.9 6 94
- 0 . 8 4 0 39.8 0.9 35 82
384 R. D. ARMSTRONG ET AL.
Table 4. The metal deposition potentials (Era) for Cd, Co and Ni over
a range of concentrations onto a stainless steel plate at 20 C
St i r r i n g b y wa t e r s a t u r a t e d n i t r o g e n .
[M]/M Log [M] Cd Em Co E m Ni Em
/V /V /V
1 x 10 - 6 - 6 - 0 . 8 6 8 - -
1 x 10 - 5 - 5 - 0 . 8 3 8 -
1 x 10 - 4 - 4 - 0 . 8 0 8 - -
1 x 10 . 3 - 3 - 0 . 7 7 8 - -
1 x 10 . 2 - 2 - 0 . 7 4 8 - 0 . 8 7 9 - 0 . 9 7 1
2. 5 x 10 2 - 1 . 6 - - 0 . 8 5 8 - 0 . 9 2 2
5 10 . 2 - 1 . 3 - - 0 . 8 4 2 - 0 . 8 9 4
t x 10 -1 - 1 - 0 . 7 1 8 - 0 . 8 2 5 - 0 . 8 7 3
2. 5 x 10 -1 - 0 . 6 - - - 0 . 8 4 5
5 x 10 -1 - 0 . 3 - - 0 . 8 1 1 - 0 . 8 2 8
1 0 - 0 . 6 8 8 - -
deposi t i on of either Co or Ni is the pot ent i al which is
j ust anodi c to the pot ent i al (Em(Co) or Em(Ni)) at
which electrodeposition of Co or Ni commences. In
the case of Cd, Em( Cd ) = Er(Cd) for any given
[Cd(ii)] since it exhibits a quasi-reversible wave. These
values are summari zed in Table 4 t oget her wi t h the
related values for Co and Ni obt ai ned by slow linear
sweep as described earlier.
These values make it possible to predict the extent
to which Cd(II~ can be removed from any sol ut i on
cont ai ni ng Co and Ni. The opt i mum pot ent i al for
the removal of Cd(II) can be predicted from Figs 8
and 9. In order to evaluate this pot ent i al in the par-
ticular case of C d ( I I ) from Co(n) the following pro-
cedure is used:
(i) Select the value of log [ C o ( I I ) ] o n the x-axis and
draw a line perpendi cul ar from this poi nt until the
Ni line is reached.
(ii) Dr aw a line f r om the poi nt on the Co line perpen-
dicular to the y-axis. This poi nt is the nucl eat i on poi nt
for the Co when it is at this part i cul ar concent rat i on.
(iii) Dr aw a line f r om the poi nt where line 2 crosses
the Cd line down to the x-axis. The value reached
on the x-axis gives us the mi ni mum concent rat i on
which we can t ake the Cd down to at this concentra-
t i on of Co i f there is to be no codeposi t i on of the Co.
In the case of the electrolysis of a (a) Cd/ Co and (b)
Cd/ Ni mixture:
(a) (i) [COO0 ] = 0.200 M ~ log [Co(n)] = - 0. 699 V
(ii) Edep = - 0. 831V
(iii) mi ni mum [Cd(ii)] = 3.68 x 10 -5 M
= 4. 14p. p. m.
(b) (i) [Ni(n)] = 0.200M ~ log [Ni(II)] = - 0. 599V
(ii) Edep = - 0 . 8 5 3 V
(iii) mi ni mum [ C d ( I I ) ] - - 3.16 x 1 0 - 6 M
= 0.36 p. p. m.
These compare wi t h experimental values of (a)
19p. p. m. at - 0. 810V and (b) 6.3 p. p. m, at - 0. 830V.
5. Conclusions
(i) Cd(n) can be electrodeposited f r om a solution
c o n t a i n i n g C d ( I I ) and Co(n) or Ni(II) wi t hout
codepositing Co or Ni.
(ii) The [Cd(II)] remai ni ng in the sol ut i on after
exhaustive electrolysis at a fixed pot ent i al is
det ermi ned by the Nernst equation, and not by
the electrolysis time provi ded t hat a critical mini-
mum time has been exceeded.
(iii) The opt i mum pot ent i al for removal by electro-
deposi t i on of Cd from a solution cont ai ni ng
Cd(ii) and Co(n) or Ni(II) wi t hout codepositing
Co or Ni can be evaluated f r om a simple dia-
gram.
References
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