Surface Technology, 12 (1981) 25 - 37 25

CONTROLLED-POTENTIAL ELECTRODEPOSITION OF METALS AT

A ROTATING CYLINDER ELECTRODE (THE ECO-CELL)*

F. C. WALSH and D. R. GABE

Department of Materials Engineering and Design, University of Technology, Loughborough,
Leics. LE11 3TU (Gt. Britain)
(Received September 15, 1980)

Summary

An i n v e s t i g a t i o n of e l e c t r o d e p o s i t i o n at a r o t a t i n g c y l i n d e r e l e c t r o d e
was c a r r i e d out using p o t e n t i o s t a t i c c o n t r o l for m u l t i m e t a l solutions. U n d e r
limiting c u r r e n t c o n d i t i o n s u n e x p e c t e d l y fast deposition o c c u r s by v i r t u e of
the p o w d e r y high surface a r e a deposits formed. Seldctive deposition of the
most noble metals was a c h i e v e d for a r a n g e of acid and c y a n i d e - c o m p l e x e d
solutions i n v o l v i n g c o m b i n a t i o n s of silver, gold, copper, nickel, cadmium
and zinc.

1. I n t r o d u c t i o n

The Eco-Cell [1 - 5] is an e l e c t r o c h e m i c a l r e a c t o r which m a k e s use of

the r o t a t i n g c y l i n d e r e l e c t r o d e (RCE) in a membrane-divided cell. It (a)
produces m e t a l in p o w d e r form on the e l e c t r o d e from dilute solutions, (b)
facilitates c o n t i n u o u s r e m o v a l of t h a t powder, (c) is capable of a u t o m a t i c
o p e r a t i o n and c o n t r o l and (d) has high mass t r a n s f e r capabilities.
The process has been applied to the selective r e c o v e r y of metals from a
v a r i e t y of i n d u s t r i a l waste solutions i n c l u d i n g those from the metal-finishing
o p e r a t i o n s of pickling and electroplating, o t h e r t r a d e effluents and hy-
d r o m e t a l l u r g i c a l process streams w h e r e b o t h e c o n o m i c a n d / o r c o m m e r c i a l
and ecological c o n s i d e r a t i o n s apply. Often such m e t a l - c o n t a i n i n g solutions
are v e r y dilute and a h i g h mass t r a n s f e r r e a c t o r is vital to p r o d u c e realistic
rates of m e t a l recovery. M a s s - t r a n s f e r - c o n t r o l l e d o p e r a t i o n of the Eco-Cell
gives rise to m a x i m u m r e a c t o r d u t y for a given r e a c t o r size, while uniform
mass t r a n s f e r and p o t e n t i a l give rise to a u n i f o r m p o w d e r e d deposit of good
p u r i t y with high c a t h o d e c u r r e n t efficiency. E l e c t r o d e p o s i t i o n is a clean,

* Paper presented at the Conference on Fundamentals of Electroplating and Metal

Finishing, Loughborough, September 22 - 24, 1980.

0376-4883/81/0000-0000/$02.50 © Elsevier Sequoia/Printed in The Netherlands

26

reliable and convenient technique capable of being automated and giving

rise to a relatively pure metal product in contrast with the competitive
processes of cementation or alkaline precipitation and sludging. Thus by
using the Eco-Cell further purification steps and plant size can be minimized
and the powdered metal can be fluidized out of the cell to be separated from
the liquid phase by centrifuging, gravity settlement, filtration or hy-
drocycloning.
While controlled-potential deposition of metals is a well-established
electroanalytical technique for estimation and separation by gravimetry and
coulometry [6 - 8], there are few examples of the technique being used to
recover metal selectively from industrial process solutions such as those
already enumerated. High current potentiostats are not readily available,
but as the response time required is not a critical factor sophisticated
circuitry is not essential. To apply the technique the reactor itself must give
rise to a uniform cathode potential, a requirement for which the RCE is
particularly advantageous [9].
Controlled-potential deposition has two practical implications. Firstly,
for a single metal in solution the current efficiency can be maintained at
approaching 100% efficiency by controlling the potential at or near the
limiting current density and below that for hydrogen evolution (Fig. l(a)).
Secondly, preferential deposition of a noble metal from a multimetal
solution can be achieved (Fig. l(b)), ideally with complete separation and at
high current efficiency, i.e. polarography with a solid cylindrical electrode.
Thus selective deposition is the converse of alloy plating where codeposition
must be achieved. The ease and success of separation depend upon (a) the
separation of the thermodynamic potentials, (b) the relative activity of the
metal ions as determined by the degree of complexing and (c) the degree of
polarization of each cathodic reaction. Other factors such as pH and
temperature may have relatively minor effects. The presence of complexants

E /
E E
._EE .....

H
IL

(a) ~ I (b) I
Fig. 1. C a t h o d i c p o l a r i z a t i o n c u r v e s for (a) single-metal deposition w i t h h y d r o g e n
e v o l u t i o n a n d (b) d e p o s i t i o n of two m e t a l s w i t h h y d r o g e n e v o l u t i o n : E', c o n t r o l p o t e n t i a l
for m e t a l I; E", c o n t r o l p o t e n t i a l for m e t a l II; IL', l i m i t i n g c u r r e n t for m e t a l I; IL",
l i m i t i n g c u r r e n t for m e t a l s I a n d II.
 27

may complicate process steps because, for example, cyanide may be de-
stroyed by oxidation at an insoluble anode which may necessitate the use of
a membrane-divided cell.
Among recent attempts to achieve cathodic separation those using the
Swiss Roll cell [10] and the Akzo fluidized bed electrode [11] for the selective
deposition of copper and an electroanalytical application of both rot at i ng
cylinder and r o tat i ng disc electrodes in a flow-trough coulometric cell [12]
should be noted. Purification of nickel electroplating solutions has been
reported by Vaaler [13] who has deposited silver, copper and zinc.
In the investigations reported here the Eco-Cell was used as a batch
r e acto r operating under controlled well-stirred conditions in which the
selected metal will deposit such that the metal concent rat i on C~ in solution
falls exponentially with time t:
Ct = Co e x p ( - k t )
where k = K A / V is the apparent rate constant, K = iL/ZFC is the mass
transfer coefficient, A is the active electrode surface area, V is the r e a c t o r
volume, iL is the limiting c u r r e n t density, Z F is the faradaic equivalence and
C o is the initial concentration. Therefore, if IL is the limiting current,
log Ct = log Co -ILt/2.303ZFC
The progress of metal removal can be recorded graphically by means of a
plot of log Ct against t, and since the value of I L can be obtained from a
subsidiary polarization curve a theoretical slope can be calculated as a norm
for r e a c t o r performance. A study was made of several industrially important
mixed-metal effluents in both laboratory and commercial-sized cells.

2. Experimental

Experimental studies were carried out in a laboratory cell specifically

constructed to be a versatile miniature version of commercial Eco-Cells and
which is described in detail elsewhere [14]. Briefly, the cell consisted of a
polished stainless steel cylindrical r ot or approximately 6 cm in diameter and
6 cm high with an active electrode surface area of approximately 80 cm 2
capable of being rotated at precise speeds up to 1200 rev m i n - 1. The cell was
an approximately cubic sealed Perspex chamber with four cation exchange
membranes positioned in the four vertical walls to separate the catholyte
from the external anolyte and lead dioxide anodes. This divided cell served
to prevent the anode reaction affecting the cathode, and in particular
enabled cyanide catholytes to be used with the sulphuric acid anolyte. By
carefully selecting the a n o d e - a n o l y t e couple any possible anode reaction
control could be completely eliminated.
Cathode reactions were investigated by potentiodynamic polarization
curves using a sweep rate of 300 mV m i n - 1 and either a calomel
(Hg/Hg2C12) reference electrode with a 0.1 M KNO 3 bridge ( E = +0.244 V
28

on the h y d r o g e n scale) or an Hg/Hg2SO 4 r e f e r e n c e e l e c t r o d e with a 1 M

Na2SO 4 salt bridge ( E = +0.646 V on the h y d r o g e n scale). P r o l o n g e d
electrolysis, typically o v e r a period of 3 h, was c a r r i e d out by c h a r g i n g the
cell with fresh s o l u t i o n and o p e r a t i n g the RCE at a preselected potential,
t e m p e r a t u r e and r o t a t i o n rate, t y p i c a l l y 22 C and 360 or 500 rev rain-1.
C o n c e n t r a t i o n changes were m o n i t o r e d by w i t h d r a w i n g negligibly small
samples from the cell at 10 min i n t e r v a l s for analysis by atomic a b s o r p t i o n
spectroscopy.
S o l u t i o n s were selected for study e i t h e r by v o l u m e t r i c p r e p a r a t i o n or
by the sampling of i n d u s t r i a l effluent streams. A m o n g those e x a m i n e d were
the following: (a) acid n i t r a t e A g - C u s o l u t i o n (0.014 M Ag and 0.014 M Cu
in 0.15 M H N O 3) typical of t h a t e n c o u n t e r e d d u r i n g the r e c o v e r y of elec-
t r o n i c scrap; (b) acid sulphate C u - Z n s o l u t i o n (0.014 M Cu and 0.014 M Zn
in 1.5 M H2SO4) typical of t h a t e n c o u n t e r e d as a brass pickle liquor; (c) acid
s u l p h a t e C u - N i solution (0.014 M Cu and 0.014 M Ni in 1.5 M H2SO4)
arising as a c u p r o n i c k e l pickle liquor; (d) c y a n i d e Au Ag Cu effluent
arising from precious metal plating rinse and d r a g o u t t a n k s and h a v i n g the
c h a r a c t e r i s t i c s given in Table 1.
TABLE 1

Metal Concentration (ppm)

Solution I Solution I I

Au 14.3 830
Ag 20.4 O.08
Cu 23.0 2.2
Fe 2.6 25
Ni 25.6 O.04
Sn 18.0

pH 11.7 4.8

P a r a l l e l i n v e s t i g a t i o n s were c a r r i e d out on a commercial-type Eco-Cell

w h o s e c h a r a c t e r i s t i c s included a k n u r l e d t i t a n i u m RCE 8.8 cm in d i a m e t e r
and 18.1 cm long, an active e l e c t r o d e a r e a of a p p r o x i m a t e l y 500 cm 2 and a
r o t a t i o n speed of t y p i c a l l y 980 rev rain 1. F u r t h e r m o r e , the 70 1 of liquor it
c o n t a i n e d could be r e c i r c u l a t e d t h r o u g h the cell at a p p r o x i m a t e l y 4 1 min 1
at 20 ~'C. Two a d d i t i o n a l solutions were i n v e s t i g a t e d . i n this cell: (e) acid
s u l p h a t e C d - Z n l i q u o r (825 ppm Cd and 437 ppm Zn in 0.3 M H2SO 4) arising
from a chemical p i g m e n t a t i o n process; (f) acid s u l p h a t e Cd-Zn liquor (128
ppm Cd and 127 g 1-1 Zn, pH 3.2) arising from an o r e - e x t r a c t i o n c a l c i n a t i o n
process.

3. R e s u l t s

E a c h s o l u t i o n e x a m i n e d was initially subjected to p o t e n t i o d y n a m i c

 29

p o l a r i z a t i o n to e s t a b l i s h the o p t i m u m p o t e n t i a l s for s e l e c t i v e deposition. The

s y n t h e t i c s o l u t i o n s were also studied as i n d i v i d u a l s i n g l e - m e t a l solutions,
p a r t i c u l a r l y s o l u t i o n (a) w h i c h g a v e good p o t e n t i a l s e p a r a t i o n (Fig. 2). By
s e l e c t i n g a n o v e r p o t e n t i a l of 180 m V (i.e. +0.222 V on the s t a n d a r d c a l o m e l
e l e c t r o d e (SCE) scale) p r e f e r e n t i a l d e p o s i t i o n of silver o c c u r r e d w i t h the
deposit c o n t a i n i n g 0.25 w t . % Cu on a n a l y s i s . The fall of c o n c e n t r a t i o n with
t i m e is s h o w n in Fig. 3 w h e r e it c a n be s e e n t h a t it follows the p r e d i c t e d line
for 20 - 30 min but t h e n as the e l e c t r o d e b e c o m e s r o u g h e n e d t h r o u g h p o w d e r
f o r m a t i o n the c o n c e n t r a t i o n falls m u c h m o r e r a p i d l y until a f t e r 180 min i t
h a s fallen to a p p r o x i m a t e l y 19 ppm.

-05

W
103
~ " ~ - " ~ ~ ~ Theory

:>

~
o
"4
J
i 102
"~ : 01BY i
c~

05 l L 10 I L I
05 ~0 0 50 iO0 ]50
Current ( A } /Jme Imln)
Fig. 2. Cathodic polarization curves for 0.014 M Ag and 0.014 M Cu in 0.15 M HNO3 : 150
mV min 1 sweep rate at 22 C; electrode area, 85.1 cm2; speed of rotation, 340 rev min 1.
Fig. 3. Selective removal of silver from Ag-Cu at 180 mV overpotential (+0.222 V, SCE).
The other conditions are as given for Fig. 2.

S i m i l a r c o n s i d e r a t i o n was g i v e n to s o l u t i o n s (b) and (c) for the

p r e f e r e n t i a l d e p o s i t i o n of copper. T w o d e p o s i t i o n p o t e n t i a l s were selected for
s o l u t i o n (b) (Fig. 4), firstly 0.85 V ( H g / H g 2 S O 4 (MMS) scale) w h e r e the
c o n c e n t r a t i o n fell a c c o r d i n g to t h e o r e t i c a l p r e d i c t i o n and the deposit
c o n t a i n e d 0.2 w t . % Zn, and s e c o n d l y - 1 . 0 V (MMS) w h e r e the c o n c e n t r a t i o n
fell m o r e r a p i d l y as p o w d e r deposits developed, a l t h o u g h the deposit con-
t a i n e d 0.4 w t . % Zn, a n d e v e n t u a l l y a t t a i n e d a low level of 11 p p m a f t e r 180
min. S o l u t i o n (c) was also t r e a t e d at the s a m e p o t e n t i a l s (Fig. 5), b u t the
s e p a r a t i o n was n o t quite so effective a l t h o u g h c e r t a i n l y a c c e p t a b l e .
P o t e n t i o d y n a m i c p o l a r i z a t i o n of the c y a n i d e - b a s e d liquors (d) i n d i c a t e d
30

~0 ~

O 8S '~

"1~.\
10, ¸ i,
\\

!
,i
",~\

- - ~ __ t - - - ~ I0 [ I J J
0 bO 100 150, 0 5C 19(i IB0

Time ; r~,n ,

Fig. 4. S e l e c t i v e r e m o v a l of copper from Cu Zn at 0.85 a n d 1.0 V (MMS).

Fig. 5. S e l e c t i v e r e m o v a l of copper from Cu Ni at - 0 . 8 5 a n d - 1 . 0 V (MMS).

t h a t effective selective deposition could not be achieved at strongly alkaline

pH, and t h e r e f o r e gradual acidification of solution (d I) with nitric acid was
used as a p r e t r e a t m e n t in which H C N e v o l u t i o n o c c u r r e d at pH 3.5. Analyti-
cal m o n i t o r i n g of the acidification (see Table 2) indicated t h a t both silver
and copper were appreciably removed by p r e c i p i t a t i o n at pH 4, the pre-
cipitate a p p a r e n t l y being mainly silver chloride. The p o l a r i z a t i o n curves
o b t a i n e d at several pH values are shown in Fig. 6. An a t t e m p t was made to
r e c o v e r gold selectively at pH 4.0 in divided and undivided cells. Two
possible c o n t r o l p o t e n t i a l s can be d i s c e r n e d at pH 4.0 and selective de-
position was attempted. Firstly, at a c o n t r o l p o t e n t i a l of - 0 . 5 5 V (MMS)
silver was selectively deposited and its c o n c e n t r a t i o n dropped from 20 to 1
ppm in 120 rain in a divided cell (Fig. 7) and to 3 ppm in 90 min in an
u n d i v i d e d cell (Fig. 8). Gold r e m a i n e d u n a f f e c t e d but some copper was
r e m o v e d at the early stages. Secondly, at a c o n t r o l p o t e n t i a l of - 0 . 9 V the
gold r e m a i n e d u n a f f e c t e d whereas both copper and silver were progressively
TABLE 2
A c i d i f i c a t i o n of a l k a l i n e c y a n i d e - b a s e d liquor

pH Metal concentration

Cu Ag Au

11 - 7 23.0 20.4 14.3

5.0 22.6 20.4 14.3
4.0 22.4 19.0 14.2
3.5 21.2 12.3 14.2
3.0 5.7 4.4 14.2
2.0 3.8 2.1 14.2
 31

removed, the former at an a p p r e c i a b l y h i g h e r rate t h a n before, with final

c o n c e n t r a t i o n s of 3.0 ppm and 1.4 ppm r e s p e c t i v e l y after 140 min (Fig. 9).

-1 4 t~? 115

_ - 1 /////50
" 0- ~ 30
>
~-I

-08

~_ o6

I - - I I ~
I ~ I0 100
Current ( m A )

Fig. 6. Polarization curves for eyanide-eomplexed liquor (d [) at various pH values.

- Cu
2O 20

g 2
u

Ag
N X N

20, z,O
, ;0 80 100
. 120
. . 140 . . . . . 20 . 40. 60 80 I00 120 140
Time (m,nJ Time (m,n)

Fig. 7. Concentration time curve for cyanide-based effluent at pH 4 and -0.55 V (MMS)
in a divided cell.
Fig. 8. As for Fig. 7 but in an undivided cell.

The p o l a r i z a t i o n c u r v e for s o l u t i o n (d II) in an undivided cell i n d i c a t e d

t h r e e possible c o n t r o l p o t e n t i a l s (Fig. 10) at - 1.0, - 1.3 and - 1.75 V (MMS).
P r o l o n g e d electrolysis at these p o t e n t i a l s r e m o v e d gold (Fig. 11) and at the
h i g h e s t p o t e n t i a l a faster r a t e was a c h i e v e d (830 ppm r e d u c i n g to 54 ppm in
420 min). However, the absence of a n y p o w d e r e d deposit suggested t h a t the
true limiting c u r r e n t lay outside this r a n g e of p o t e n t i a l a l t h o u g h the
r e a c t i o n was clearly mass t r a n s f e r c o n t r o l l e d as s h o w n by the effect of the
electrode r o t a t i o n rate in i n c r e a s i n g the d e p o s i t i o n rate.
S o l u t i o n s (e) and (f) were t r e a t e d in a larger-scale p l a n t with effective
selective removal. F o r s o l u t i o n (e) a c o n t r o l p o t e n t i a l of - 1.8 V (SCE) was
32

l 1 i T 1 | i

20
Au

~ IO

I l l I i i l
20 40 60 80 100 120 ,140

Time (rain)

Fig. 9. As for Fig. 7 but in an undivided cell at - 0 . 9 V (MMS).

-16 , 1

--
:>
-;4

/
-- I0

O6

I I L
0 I I I0 I00

Current (mA)

Fig. 10. P o l a r i z a t i o n curve for s o l u t i o n (d II).

1000

AO0

~,~ -10 V
o_

C_o 200

g
u

50

L i i L

IO0 200 300 400

Line (mln)

Fig. 11. C o n c e n t r a t i o n - t i m e curves for s o l u t i o n (d II) at t h r e e control potentials.

 33

1 I I

500 ~ Entry

200

L>

5O

20 l ) I
0 I0~ 2OO 3OO
Time {rain)

Fig. 12. Concentration time curves for the removal of cadmium from solution (e) :
electrode area, 500 cm 2; RCE at 980 rev min 1; flow rate of 4 1 m i n - 1 at 20 :C.

i I i

20 ~ F n t r y
a.

10

i I I I
100 200 300
Time(ram)
Fig. 13. Concentration-time curves for the solution obtained at the end of Fig. 12 with the
pH adjusted to 3.

u s e d s u c h t h a t t h e c a d m i u m c o n c e n t r a t i o n fell f r o m 487 to 30 p p m i n 300

m i n w i t h o u t a n a p p r e c i a b l e c h a n g e i n t h e z i n c c o n c e n t r a t i o n (Fig. 12). T h i s
r e s i d u a l s o l u t i o n w a s a d j u s t e d w i t h c a u s t i c s o d a to p H 3, w h e r e u p o n t h e
potentiostatic deposition continued with the cadmium concentration falling
f r o m 33.5 to 1.5 p p m (Fig. 13) b u t w i t h c o d e p o s i t i o n of z i n c w h i c h fell f r o m
437 to 112 ppm.
S o l u t i o n (f) w a s s u b j e c t e d to c o n t i n u o u s t r e a t m e n t a t 1.3 V ( M M S ) , 540
r e v m i n - 1 a n d a flow r a t e of 16.2 1 m i n - 1 a t 60 °C. A f t e r One p a s s t h e
34

c o n c e n t r a t i o n was lowered f r o m 128 to 84 p p m yielding c a d m i u m p o w d e r of

99.2% purity.

4. D i s c u s s i o n

The ability to deposit the m o s t n o b l e m e t a l s e l e c t i v e l y depends pri-

m a r i l y on the r e d u c t i o n p o t e n t i a l at the p r e v a i l i n g conditions. If simple
u n c o m p l e x e d ions a n d ideal s o l u t i o n s are a s s u m e d an a p p r o p r i a t e n e r n s t i a n
plot of p o t e n t i a l a g a i n s t c o n c e n t r a t i o n for the ions of i n t e r e s t h e r e is as
g i v e n in Fig. 14. This c a n be a useful guide to the u n d e r s t a n d i n g of some of
t h e b e h a v i o u r r e p o r t e d here. C l e a r l y in s o l u t i o n s of these types s e p a r a t i o n is
effective in m o s t i n s t a n c e s d o w n to c o n c e n t r a t i o n s of 10 -~ M a n d in m a n y
cases e v e n lower. B e c a u s e t h e s e c o n d i t i o n s are m o s t g e n e r a l l y realized in
acid s o l u t i o n s s u c h s o l u t i o n s are u s u a l l y preferred.

Au/Au"

A u / A u )"

l0

Ag/Ag"

CulCu'

Cu/Cu 2"

NUN, 2"
/
Cd/Cd 2.

ZnlZn Z"
/
-10

i i L ~ J ~ L

10-10 I0 5

Concentration (M }

Fig. 14. Nernstian plot of the reduction potential against the concentration assuming
uncomplexed ions and ideal solutions.

A d e q u a t e s e p a r a t i o n of the Ag ÷ - C u 2 ÷ and Cu 2 ÷ - N i 2 ÷ s o l u t i o n s is
i n d i c a t e d by Fig. 14 a n d this was realized e x p e r i m e n t a l l y once the o p t i m u m
 35

c o n t r o l p o t e n t i a l was deduced. The d e g r e e of p o t e n t i a l difference for

Cu 2 + Zn 2 + s o l u t i o n s is e v e n g r e a t e r a n d a g a i n effective s e p a r a t i o n was
found. H o w e v e r , two c h a r a c t e r i s t i c s r e q u i r e s o m e c o n s i d e r a t i o n . Firstly,
d e v e l o p m e n t of a p o w d e r e d deposit leads to i n c r e a s e d s u r f a c e r o u g h n e s s a n d
t h e n c e to m o r e r a p i d d e p o s i t i o n t h a n w o u l d be a n t i c i p a t e d from e x t r a p o -
l a t i o n of the c o n c e n t r a t i o n - t i m e c u r v e at v e r y s h o r t times or from a
c a l c u l a t i o n b a s e d on the l i m i t i n g c u r r e n t d e n s i t y derived from the polariz-
a t i o n curve. This c a n be a t t r i b u t e d to an i n c r e a s e d a c t i v e s u r f a c e a r e a on
the c y l i n d r i c a l e l e c t r o d e but m o r e p a r t i c u l a r l y to an i n c r e a s e in s o l u t i o n
t u r b u l e n c e or e d d y i n g at the e l e c t r o d e interface. R o u g h n e s s is k n o w n to be
effective in this w a y and a n a l y s i s of the m a s s t r a n s f e r d a t a o b t a i n e d d u r i n g
p o w d e r d e p o s i t i o n h a s s h o w n this to be i m p o r t a n t in this i n s t a n c e [15].
Secondly, this i n c r e a s e in m a s s t r a n s f e r a s s o c i a t e d w i t h p o w d e r d e p o s i t i o n
gives a v e r y m u c h m o r e r a p i d d e p l e t i o n of the solution, t y p i c a l l y an im-
p r o v e m e n t of a f a c t o r of 15 (Figs. 3 or 4), b u t at the e x p e n s e of deposit
purity. T h u s the i n c r e a s e d d e p o s i t i o n r a t e b u t d e c r e a s e d p u r i t y m u s t be a
d e l i b e r a t e o p e r a t i n g policy choice d e p e n d i n g u p o n the use e n v i s a g e d for the
p o w d e r as the b o n u s in effluent t r e a t m e n t . In all these cases the c a t h o d e
c u r r e n t efficiency was h i g h ( a p p r o x i m a t e l y 100%) a n d not a c a u s e of a n y
real c o n c e r n .
The need to e x a m i n e c o m p l e x e d m e t a l s o l u t i o n s arises p r i m a r i l y from
m e t a l - f i n i s h i n g or e l e c t r o p l a t i n g effluents b e c a u s e a v a r i e t y of c o m p l e x a n t s
are d e l i b e r a t e l y used e i t h e r to i m p r o v e the q u a l i t y of finish a c h i e v e d or in
some cases to m a k e d e p o s i t i o n possible. Of the c o m p l e x a n t s used c y a n i d e is
by far the m o s t i m p o r t a n t , b e i n g used in m a n y gold, silver, copper, c a d m i u m
a n d zinc process solutions. C y a n i d e c r e a t e s the f u r t h e r c o m p l i c a t i o n t h a t if
d e l i b e r a t e l y m a d e acidic it m a y g e n e r a t e H C N gas or if d e s t r o y e d by an
o x i d a t i o n t r e a t m e n t the m e t a l m a y p r e c i p i t a t e as h y d r o x i d e t h e r e b y p r e v e n t -
ing r e c o v e r y as m e t a l by e l e c t r o w i n n i n g .
Tests in t h e t w o c y a n i d e - b a s e d p r e c i o u s m e t a l effluents s h o w e d t h a t a
d e g r e e of s e l e c t i v e d e p o s i t i o n was possible, but o w i n g to the r e l a t i v e
s t a b i l i t i e s of the gold a n d s i l v e r c o m p l e x e s silver a n d c o p p e r tended to be
p r e f e r e n t i a l l y r e m o v e d and gold was only r e m o v e d w h e n t h e i r concen-
t r a t i o n s were r e l a t i v e l y insignificant. T h e i m p o r t a n c e of u s i n g a divided cell
was a p p a r e n t b e c a u s e it p r e v e n t e d a n o d i c o x i d a t i o n of r e s i d u a l c y a n i d e
b e i n g a r e a c t i o n of u n d u e influence, a l t h o u g h the a d d i t i o n a l i n c o n v e n i e n c e
of o p e r a t i n g a divided cell c a n n o t be denied. It was also c l e a r t h a t o p e r a t i o n
at p H 4 is n e c e s s a r y to a c h i e v e r e a s o n a b l y s e l e c t i v e d e p o s i t i o n a n d this does
n e c e s s i t a t e c a r e f u l p r e l i m i n a r y c h e m i c a l t r e a t m e n t . T h u s s e p a r a t i o n is
possible b u t the c o n d i t i o n s m u s t be c a r e f u l l y defined before an o p t i m u m c a n
be declared.
In c o m m e r c i a l - s i z e d cells it h a s b e e n f o u n d best to o p e r a t e the cell as a
c o n t i n u o u s flow r e a c t o r e i t h e r in a s i n g l e - s t a g e closed c i r c u i t or as a
multiple-cell c a s c a d e s y s t e m [5]. T r e a t m e n t of this type was used for the
C d - Z n s o l u t i o n s a n d in Fig. 13 the c o n c e n t r a t i o n s at e n t r y and exit are
shown. A c o n v e r s i o n f a c t o r c a n be defined as
36

entry concentration kA
exit c o n c e n t r a t i o n = 1 +

w h e r e A is the e l e c t r o d e area, L the v o l u m e t r i c solution flow r a t e and K the

mass t r a n s f e r coefficient; in this case K = 0.038 c m - 1, A = 500 cm 2 and
L = 66.7 cm 3 s - 1. Thus a c o n v e r s i o n f a c t o r of 1.28 has been achieved. A
calculatior~ of this type is primarily of v a l u e in c a l c u l a t i n g the cell c a p a c i t y
r e q u i r e d for a given drop in c o n c e n t r a t i o n for a p a r t i c u l a r solution flow r a t e
and presupposes an ability to deposit selectively, which in this case was
established at h i g h e r c o n c e n t r a t i o n s and acidities.
While the ability to deposit metals selectively with the RCE is an
i n v a l u a b l e asset, i t should briefly be p o i n t e d out t h a t it should only be
exploited in cases where mixed-metal solutions are unavoidable, e.g. with
alloy pickling liquors. If it is at all possible to keep all individual metal
waste streams s e p a r a t e it must always be preferable to do so. U n f o r t u n a t e l y ,
the t r a d i t i o n of effluent t r e a t m e n t by a l k a l i n e p r e c i p i t a t i o n and sludging is
well e n t r e n c h e d and is designed simply to dispose of r a t h e r t h a n to r e c o v e r
the waste, in this case metal, as an i m p o r t a n t directly reusable feedstock or
m a r k e t a b l e commodity.

5, Conclusions

The r o t a t i n g cylinder used as an active r e a c t i o n surface in the Eco-Cell

r e a c t o r is well established as a high mass t r a n s f e r electrode and has been
studied for its e q u i p o t e n t i a l surface c h a r a c t e r i s t i c . With p o t e n t i o s t a t i c
control, e l e c t r o d e p o s i t i o n can be m a i n t a i n e d u n d e r limiting c u r r e n t con-
ditions and yields a powdered metal deposit which, t h r o u g h the r o u g h e n e d
surface produced, enables e n h a n c e d r a t e s of deposition to be achieved. The
p o t e n t i o s t a t i c c o n t r o l also allows selective metal deposition to be main-
tained, t h e r e b y enabling r e c o v e r y and s e p a r a t i o n of metals in solution to be
a t t a i n e d simultaneously.

Acknowledgments

The provision of a CASE a w a r d (to F.C.W.) by the Science R e s e a r c h

Council and the s u p p o r t of E c o l o g i c a l E n g i n e e r i n g Ltd. made this in-
v e s t i g a t i o n possible. The a u t h o r s a c k n o w l e d g e v a l u a b l e discussions with Dr.
F. S. H o l l a n d and Mr. N. A.. G a r d n e r and the provision of l a b o r a t o r y
facilities by Professor I. A. Menzies.

References

1 F.S. Holland, Br. Patent 1,444,367 (1976).

 37

2 F.S. Holland, U.S. Patent 4,028,199 (1977); Br. Patent 1,505,736 (1978).
3 F.S. Holland, Chem. Ind. (London), (1978) 453.
4 F.S. Holland and H. Rolskov, Effluent Water Treatment Cony., Birmingham, 1978.
5 F.C. Walsh, N. A. Gardner and D. R. Gabe, J. Appl. Electrochem., to be published.
6 J . J . Lingane, Electroanalytical Chemistry, Wiley Interscience, New York, 1979.
7 A. I, Vogel, Textbook of Quantitative Inorganic Analysis, Longmans Green, Harlow,
Essex, 4th edn., 1978.
8 G.A. Rechnitz, Controlled-potential Analysis, Pergamon, Oxford, 1963.
9 D.R. Gabe, J. Appl. Electrochem., 4 (1974) 91.
10 P.M. Robertson and N. Ibl, J. Appl. Electrochem., 7 (1977) 323.
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12 G. Johansson, Talanta,12 (1965) 163.
13 L.E. Vaaler, J. Electrochem. Soc., 125 (1978) 204.
14 F.C. Walsh and D. R. Gabe, to be published.
15 R. Kappesser, I. Cornet and R. Greif, J. Electrochem. Soc., 118 (1971) 1957.