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ELECTROCHEMISTRY
ELECTROCHEMISTRY
ELECTROCHEMISTRY
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
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
(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.
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
-+ Temperature
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)
Figure t 0
Standard
reduction
potentials
I
I
Melal Metal
rod rod
it
+ l- -1+ -== * - l+ +l- -
j_.
- + l-
tt
-1+
-
A
;=*-=Solution;::=
Dlgiiai
voltrneier
FIGURE 8
:-l
DEVELOPMENT OF ELCTRODE POTTNTIAL
AND ITS MEASUREMENT
_.-,] *_._:
:_ -: i;()1. :- --
t___ ':-;---:-55--:-
*--- ::_-_.rxJ,_ ---.
_ _ _i.
\ il t
-:
---_:-_":---:-_^___:1_:
="-- *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
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
-
--