3.

T'I,ECTITOCHEMIS TRY
3.1 Introduction
lilectrociremistry deals r.vith the interaction of metals in contact with electrolytes, An electrollrte
is a solution of metal *'ith water. However. the electlolyte can contain other salts or metals
which can compete in deposition processes. Our focus wiil be on the follow.ing:
*+ Electrode potential
-+ Galvanic cells
-+ Effect of temperature and concentration on cell potentials

-> The effect of an externally applied voltage on electrolytes and the application of this
effect (electrolysis) in extractive metallurgy or metal recovery and purification processes.
3.2 Electrode Potentials
A metal ionizes when it is in contact with water or its solution in water (electrolye) (see figure
8A). For example if oopper is in contact with a CuSo+ solution it will ionize, dissociate or go
into solution to different extents depending on the concentration of the electrolyte. The ionization
is a reaction of the- form,

Metal
= cation t electrons

Or M= M"= + ne

e.g Cu Cuzn t'2e

=

Note that the solution of CuSoq is already ionizecl in the form CuSOq*> CIi2*i SOo2-
If the concentration of CuSo+ solution is too high then the dissolution of copper into the solution
reaches equilibrium too early

or Cu S Cu2* +2e

Befbre and after equilibrium is established lbr the copper eiectrode in contact r.r,ith its solution
(EI-ECTRODE) the distribution of positive and negative charges in the region close to the
electrode will be as shown in figure 3A. Such an arrangement or distribution is called a
DOUBLE LAYER. Three rnodels have been proposed, the HELMHOLTZ rnodel, the GOIIY-
CHAPMAN MODEL AND Tf{E STERN MODELS. The Stern models are n.}ore diffuse. f'lie
Steun model is trore realistic because it cloes indicale that the rnetal or.. electrode rvill har,'e mr:re
negative charge left rvhen catious go into solution. .,\nd thc solution or electlolyte rvi1l have
rnore positive charges. The major eff-ect of a double la1'er is that it 1'epresents SEPARz{I'ION iCI
CHAI{GE. creating an eiectric I'relcl betu-een the eiectrode and its solution. fhe presence ol an

electronic ficlc1 means that clrarges (positive or negative) can erpcrienue a force. That is. a

voltage exists betlveen the electrode and its electlolvte. This r.oitage dcpends on the extcnt to
rvhich a metal ionises. Sornc rnetal ionize more than others beibre equilibrium is established.
I{ence, eaoh rnetal develops its ou,n potential rvith its electrol_-rte. this potential is called the
ELEC'|RODE POTtrN'IiAL. lv'letals that r:eadil-v ionizes e.g. sodirim anci potassium are called
REACTIVE N4E1-ALS. fhe less active metals are callecl NOBLI NIETALS. e.g gold. Reactive
metals are characterized b_t, lor.v (more negative electrocie poterrtials). Noblc metals are

characterized by high (rnolc positive) electrode potentials. The stanclard electlocle potentials.
that is, l,aiues. obtained at 1 atmosphere. 25uC ancl a concentration of I molar ale placed in a

selies ca11ed the RIIDUC'|ION POTENTIALS. all leI'erenced to a Stanclarci Ei,vdrogen fJlectrode
lvithadesignated.potentialofzeror.olts. Astandardhydrogen"halfcell'"consistsofaplatinr,ul
electrode rlipping into a one rnolat sohttion of'hl,drochlonc acid into q,hich hy'drogen gar; is
ptrurped at a fixed pressure (see figure 8B). T'he rcactions in the half cel1s are as l'oliorvs:
i) H'+e*>H at the electrocle
ii) I{2---+ff 1= irr the solution
Note that tire reaction (oxidation)
H2 -+2Hr
.
is similar to the reaction
N4-+lvl''*
Standard reduction potentials aLe shorvn in figure 8R

3.3 Galvanic Cells

Wl-rcrr h,r,o metals of dissimilar electrocle potentials are placed in the same electroiyte or:

(see Fig BC) or separately in tireir respective electrolltes an electrochernicerl cell is Set upr in
u'hich the more actir,'e rnetal becomes an ANODE and the less actir.e rnetal becontes a

CA-|I-IODE. That is. thc flou,of'electrons will be frorn the Anodc to the Cathode.
Note that when an external voltage is applied in an arrangement shown in figure 9Il and l l Il
flow of electrons is fi'om the CATHODE to the ANODE. That is in the galvanic cell rthe
ANODE is negative. In the electlolytic cell the ANODE is positive.

Galvanic cells are imporlant because batteries are cleveioped and operatecl on the plinciple of a

galvanic cell. Horvever in the metallurgical industry galvanic couples iead to the corrosion of ,the

more active metal when it is coupled to a noble metal. Corrosion attacks can lead to failure of
metallic cornponents or stluctr-res.

3.4 Computation of standard potential

Reference is raade to reduction potentials indicated (see figure 9A.)

Zn---22n2-+ 2e :0.76Y
Cu2f -l-2e-+ Cu 0.34V

The standard cell iotential is obtained by adding the two half cell potentials.
That is,
Cell potential:0. 76+0. 3 4V
: 1. 1 volts
As an exercise ver;r the standard cell potential in figure 98, BETWEEN COPPER AND SILVIIR

3.5 Concentration and Ternperatures effects

Electlode potentials depend on sever-al flactors, such as,

-+ Concentration of the electrolyte

-+ Surtbce area of electrodes

-+ Temperature

-) Presence or absence ofpolarization

Helmholiz 6oijy - Chopmon Slern
fiod€l frodei mocels

il:I-
+
+
+ ++
-l -;-; +
+.I=
+-i
+ I+ I + t- -i-r I
il_ +
i l- :+- t- a *+-
+ l- -+
+ il-:-4 + t- *-++
rl_
i Il- -;_ l++
t_. -
-i. t_
+l-
+
il r; . t-
+ t-
,-
+++:
Fixed .Moorr€ Filed Mobile l:i;;ed Moi:ile
tulodsls for elocriJcai double layers.

S'r,{NDA]RD
Renucrrox
REl:ucrroN F[ar.r' B-nacrrou FoTENTI.AI,
(vor-rs)

-Ll ', t e ..-- Li(s)

+ K(s) -3-t).f
--2.S3
K+ -F e*
Bae- -t 2 e- -. Ba(s) -2.90
Ca?+ * 2 e- r\^ /^\
'va\o/
* Na(s) -2-87
Na+ e*
-J-
l,fg?+. * 2 e- N4g(s)
AI3+ -1- 3 e- ----+
-2.3i
Mnz+ -l- 2 e-
- Al(s)
--+ Mn(s)
-1.66
ZrP+ * 2 e- _* Zn(s)
-*o.76
1.18

Cr8+ -F 3 e- + Cr(s) -a.74

Fe2+ -1- 2 e- - IF^/^\
Et!,'
-0.44
Cr3+ -l- e- Q1z+
Cdz+ -l 2 e-
- -o.41
*0.40
-.> cd(s)
PbSO+(s) * 2 e' * Pb(s) l- Sor2-
T.l+ + e- *- Tl(s)
-0.36
-0.34
Cot+ -i- 2 e- * Co(s) -0.28
Ni2+ -F 2 e- -*
*
Ni(s) -o.25
AgI(s) + e- Ag(s) + I- --0.15
Sn'+ *i- 2 e- ,* Sn(s) -4.t4
Pb2+ -f- 2 e- Pb(s) --0.13
2II+-F2e* -* Ag(s) + Br-
------+ Hs(g) o.00
AgBr(s) + e- 0.10
S(s)-r-211++2e- _.+ HeS o.14
Sna- -l- I e- ---+ Sn2+ c}.15
* e*
Cu2'F * Cu+ 0.15
SO42-+4Ht+2e' 0.20
Cu2+ -F 2 e- ---.-.* Cu(s)
Cu+ -l- e-
-sor(g)+2H2o
* Cu(s)
o.34
0.52
I:(s) -F 2 e- +tT- 0.53
Fe8+ -l- e- + Fe2+ 0.77
Ifg2e" + 2 e- 2 He(]) 0.79
Ag* -l- e- - Ag(s) 0.80
2Hgz+*2e, F{o.z+ +
- 0.92
NOs*-{-4H++3e- -=+NO(e)+2H,O 0.96
AuCla- t 3 e- --'--+Au(s) +4Cl- 1.00
Br:(i) -l 2 e- +2Br- r.07
Or(e)+4IJ^+*4e-
-.+ 2 HsO
MnOz(s)+4tT+*2e- +fiuf11zt*?tI*O
1.23
L.23
CrrOrr- -r 14 H* * 6 e- ___-_> Z Crts+ * 7 Hr{) 1,33
CI,(g) + z e- +2Cl* 1.36
ClOs-+6H+t-5e- ---->*CIr(e)+3FI,O L.47
Aua+"-i- 3 e-' Au(s) r.50
MnO+-+8H+*5e- -
-----+ IvJnz+ +4HrO L.52
HeOzl-2H+*2e- +2HnO L. I I
Co3+ -l- e- ? Co"* 1.82
Fg(e) + 2 e- -----+ 2 F- 2.87.

Figure t 0
Standard
reduction
potentials
I
I
 Melal Metal
rod rod

it
+ l- -1+ -== * - l+ +l- -
j_.
- + l-
tt
-1+
-
A
;=*-=Solution;::=

' The origln

-intoot Helmhaltz dauble layars araund
a
metal rad dipping a solution. (a) For this metal, the
equilibrium hf*(aqj+ne-=M(s) lies to ffie left Sams ol
the rneta, alorxs go irlo so/ution as positive ion*. Electmns
re$lain on the iod. (b) For fhis metal the.' aquilibrium
M"* (aq) + ne- M(s,} ftes to the right. Positive ions leave the
=
solulbn. thus giving tne $unailnding:solution an ovenll noga'
tive charge

Dlgiiai
voltrneier

FIGURE 8
:-l
DEVELOPMENT OF ELCTRODE POTTNTIAL
AND ITS MEASUREMENT

_.-,] *_._:
:_ -: i;()1. :- --
t___ ':-;---:-55--:-
*--- ::_-_.rxJ,_ ---.
_ _ _i.
\ il t
-:
---_:-_":---:-_^___:1_:

Hydrochloric PlatinJnl Zinc $u phaie

oleclrode sof ui.ion,
1 rnol rim '
1 moi d:t-] '

. An apparalus lo n?eas!re the standard electrcde

patential ol zinc. For accurate work the solution s|tould hate
an activity af 1, rather than a cancentratian of 1 nta,i dn-r. Trt*
temperaturc shculd he 25'C. li is not essenf/al to use a ciigital
valtmeter, bui ihe fieler fiust have a very high res,slance

="-- *ffi::::E
:-:---:-:Pft- - -=-=
:----, *ffi,--=-:-:*-
-:.:-=-:Efl:-:::-:
-& -B- -_ .* K{::_:_=:
:.:_.-.*-_- *:
Zinc sutphato
solulion.
1 mot om-i
Negativo half-celt
on the lett Positiv6 half-cell
on tho- "v"r
right
-7t cunent is allowed to t
?s.srr,yay.* m6\ja tr *.,-'Y-thyusn calt, a Daniell
!;,;;;i:;i.,*r:!::*::::::,fi!t:rqtr:Pla?;t:[;fl!;
""i,';;?,8'r"{;',i:""",:l:"i':::f
,!iiiiii:r";;31':,::,:!::,\':"'lX
Zi{:,{?::tt'lf ,Zf:!x*!i::{".itq?:':Z;iE:iX::',",i2i3!,
?,iir!i!i,?{,}11f
hatf-cel to tn" Xi:ri:::x;::iii;1W';#:;#:itr;
iii'iiinive hatf-cel
 Zinc
electrode
electroci€

{- --- PAi. -
-
t--,-r\^l.---IXr- - -_- --.

l=-=ffi--__-
E=-=E==a-
ffi E€*lt: Eo,iet" - E?tft
sulphate Copper(l!) sulphaie = Esc,r,*tc. - E%n"tzn
solution,
-
solution : *0.3,tV'- (*0-76V)
1 mol dm 1 mol dm-"
Negalive hall-cell Positive half-cell
: *l'l V
on lhe 1efl on the righl

", , A Daniell cell cafl be rnade by ioining a zinc in

zinc sulpl'tate half-cett with a copper in copper(tt) sulphate
halt-celt'. The cells are linked by a piece of filter papet'soaked
ln potassjum nitrcte solution. Ihrs acts as the .$a/t bricige.
ftlote: lf yau sef up thls cell in the laboratory, do not thjnk that it
will onty work if the zinc half'cellls on the left as you lqok at it!
The key thing is ihat the voltmeter will anty give a positive
reading if the zinc electrode is connected ta the negative
(black cotoured) cannection on the volimeter. Similarly' the
copper electrode has fc be connected to the (red) positive
terminal af the voitmeter
-
FIGURE 9
COMPUTATION OF CELL
STAN DARD ELECTRO DE POTENTIATS

Copper Siiver
electrode
alectrode

E%r,:E56shr-zl?"
_. EO E:e
-- L('ur+/Cu
-cAS./Ag
: +0.80 V - O-14 v
-E--r
--- --
3.
xt_.-.- -,.
\,4. --_ -. -----
: *0.46V
<)---
=-----[
t_ _-
-N
/j *- -
x,1.
--
-F -_ -- - -
L--
t_-_ S---:-:-:1:
t_
t---- -P--\ - ._--l
* .::::-:::=-82
-
--

Copper(il) sulphate Silver nitrate

solution. so1uti6n,
1 moldm " l mol dm "

., A cet! rnade from copper in copper(tt) sulphate

artu silver in sitver nitrate half'celts- Again, we have shcwn the
more rtegative hatf'oell on the lett of the diagftm