Unit

3
Objectives
Aft er s tu d yin g th is Un it , you will b e
a b le to
d e s c r ib e a n e le c t r oc h e m ic a l c e ll
a n d d iffer en t ia t e b et ween ga lva n ic
a n d elect r olyt ic cells ;
a p p ly Ne r n s t
e q u a t io n
fo r
ca lcu la tin g th e em f of ga lva n ic cell
a n d d e fin e s t a n d a r d p ot e n t ia l of
t h e cell;
d er ive r ela t ion b et ween s t a n d a r d
p ot en t ia l of t h e cell, Gib b s en er gy
of cell r ea ction a n d its equ ilib r iu m
c on s t a n t ;
d efin e r es is t ivit y (), con d u ct ivit y
() a n d m ola r con d u ct ivit y (m ) of
ion ic s olu t ion s ;
d iffe r e n t ia t e
b et ween
io n ic
(e le c t r o ly t ic ) a n d
e le c t r o n ic
c on d u c t ivit y;
d e s c r ib e
th e
m et h od
fo r
m e a s u r e m e n t o f c o n d u c t ivit y o f
e le c t r o ly t ic
s o lu t io n s
and
c a lc u la t io n
o f t h e ir
m o la r
c on d u c t ivit y;
ju s t ify
th e
va r ia t io n
of
c o n d u c t ivit y
and
m o la r
c o n d u c t ivit y o f s o lu t io n s w it h
ch a n ge in th eir con cen tr a tion a n d

d efin e m (m ola r con d u ct ivit y a t

z e r o c o n c e n t r a t io n o r in fin it e
d ilu t ion );
e n u n c ia t e Ko h lr a u s c h la w a n d
lea r n it s a p p lica t ion s ;
u n d e r s t a n d q u a n t it a t ive a s p e c t s
of elect r olys is ;
d es cr ib e t h e con s t r u ct ion of s om e
p r im a r y a n d s e c on d a r y b a t t e r ie s
a n d fu el cells ;
e x p la in
c o r r o s io n
as
an
e le c t r oc h e m ic a l p r oc e s s .

Electr
ochemistr
y
Electrochemistr
ochemistry
Ch e m ica l re a ction s ca n b e u s e d to p rod u ce e le ctrica l e n e rgy ,
con vers ely , electrica l en ergy ca n b e u s ed to ca rry ou t ch em ica l
rea ction s th a t d o n ot p roceed s p on ta n eou s ly .

E le c t r o c h e m is t r y is t h e s t u d y o f p r o d u c t io n o f
elect r icit y fr om en er gy r elea s ed d u r in g s p on t a n eou s
ch em ica l r ea ct ion s a n d t h e u s e of elect r ica l en er gy t o
b r in g
a b ou t
n on -s p on ta n eou s
c h e m ic a l
t r a n s for m a t ion s . Th e s u b ject is of im p or t a n ce b ot h
for t h eor et ica l a n d p r a ct ica l con s id er a t ion s . A la r ge
n u m b e r o f m e t a ls , s o d iu m h yd r o x id e , c h lo r in e ,
flu or in e a n d m a n y ot h er ch em ica ls a r e p r od u ced b y
e le c t r oc h e m ic a l m e t h od s . Ba t t e r ie s a n d fu e l c e lls
con ver t ch em ica l en er gy in t o elect r ica l en er gy a n d a r e
u s ed on a la r ge s ca le in va r iou s in s t r u m en t s a n d
d evices . Th e r ea ct ion s ca r r ied ou t elect r och em ica lly
ca n b e en er gy efficien t a n d les s p ollu t in g. Th er efor e,
s tu d y of electr och em is tr y is im p or ta n t for cr ea tin g n ew
t ech n ologies t h a t a r e ecofr ien d ly. Th e t r a n s m is s ion of
s en s or y s ign a ls t h r ou gh cells t o b r a in a n d vice ver s a
a n d com m u n ica t ion b et ween t h e cells a r e k n own t o
h a ve e le c t r oc h e m ic a l or igin . E le c t r oc h e m is t r y, is
t h er efor e, a ver y va s t a n d in t er d is cip lin a r y s u b ject . In
t h is Un it , we will cover on ly s om e of it s im p or t a n t
elem en t a r y a s p ect s .

In Cla s s XI, Un it 8 , we h a d s tu d ied th e con s tr u ction a n d fu n ction in g

of Dan ie ll c e ll (Fig. 3 .1 ). Th is cell con verts th e ch em ica l en ergy lib era ted
d u rin g th e red ox rea ction
(3 .1 )
Zn (s ) + Cu 2 +(a q) Zn 2 +(a q) + Cu (s )
t o e le c t r ic a l e n e r gy a n d h a s a n
electr ica l p oten tia l equ a l to 1 .1 V wh en
con cen tra tion of Zn 2 + a n d Cu 2 + ion s is
u n ity ( 1 m ol d m 3 )*. Su ch a d evice is
ca lled a galvan ic or a vo lt aic cell.
If a n extern a l op p os ite p oten tia l is
a pplied [Fig. 3 .2 (a )] a n d in crea s ed s lowly,
we fin d th a t th e rea ction con tin u es to ta ke
pla ce till th e oppos in g volta ge rea ch es th e
va lu e 1.1 V [Fig. 3.2 (b)] wh en , th e rea ction
s top s a ltogeth er a n d n o cu rren t flows
th rou gh th e cell. An y fu rth er in crea s e in
th e extern a l p oten tia l a ga in s ta rts th e
rea ction bu t in th e oppos ite direction [Fig.
3.2 (c)]. It n ow fu n ction s a s a n electrolytic
c e ll, a d evice for u s in g electrica l en ergy
t o c a r r y n on - s p on t a n e ou s c h e m ic a l
rea ction s . Both typ es of cells a re qu ite
im p orta n t a n d we s h a ll s tu d y s om e of
th eir s a lien t fea tu r es in th e followin g
Fig . 3 .1 : Da n iell cell h a vin g electrod es of z in c a n d
pa ges .
cop p e r d ip p in g in th e s olu tion s of th e ir

3.1 Electrochemical
Cells

res p ective s a lts .

*S trictly s p ea k in g a ctivity s h ou ld b e u s ed in s tea d of con cen tra tion . It is d irectly p rop ortion a l to con cen tra tion . In d ilu te
s olu tion s , it is equ a l to con cen tra tion . You w ill s tu d y m ore a bou t it in h igh er cla s s es .

C h e m is t r y

64

Fig . 3 .2 : Fu n ction in g of Da n ie ll ce ll w h e n e x te rn a l v olta ge E ext op p os in g th e

cell poten tia l is a pplied .

As m e n t ion e d e a r lie r (C la s s XI, Un it 8 ) a ga lva n ic c e ll is a n

electroch em ica l cell th a t con verts th e ch em ica l en ergy of a s p on ta n eou s
r ed ox r ea ction in to electr ica l en er gy. In th is d evice th e Gib b s en er gy of
th e s p on ta n eou s r ed ox r ea ction is con ver ted in to electr ica l wor k wh ich
m a y b e u s ed for ru n n in g a m otor or oth er electrica l ga d gets lik e h ea ter,
fa n , geys er, etc.
Da n iell cell d is cu s s ed ea r lier is on e s u ch cell in wh ich th e followin g
red ox rea ction occu rs .
Zn (s ) + Cu 2+(a q) Zn 2 + (a q) + Cu (s )
Th is rea ction is a com b in a tion of two h a lf rea ction s wh os e a d d ition
gives th e over a ll cell r ea ction :
Cu (s ) (r ed u ction h a lf r ea ction )
(3 .2 )
(i) Cu 2+ + 2 e
(oxid a tion h a lf r ea ction )
(3 .3 )
(ii) Zn (s ) Zn 2 + + 2 e
Th es e r ea ction s occu r in two d iffer en t p or tion s of th e Da n iell cell.
Th e r ed u ction h a lf r ea ction occu r s on th e cop p er electr od e wh ile th e
oxid a tion h a lf rea ction occu rs on th e zin c electrod e. Th es e two p ortion s
of th e cell a r e a ls o ca lled h alf-c e lls or re do x c o uple s . Th e cop p er
electr od e m a y b e ca lled th e r ed u ction h a lf cell a n d th e zin c electr od e,
th e oxid a tion h a lf-cell.
We ca n con s tru ct in n u m era ble n u m ber of ga lva n ic cells on th e pa tter n
of Da n iell cell b y ta k in g com b in a tion s of d iffer en t h a lf-cells . E a ch h a lfcell con s is ts of a m eta llic electr od e d ip p ed in to a n electr olyte. Th e two
h a lf-cells a r e con n ected b y a m eta llic wir e th r ou gh a voltm eter a n d a
s witch exter n a lly. Th e electr olytes of th e two h a lf-cells a r e con n ected
in tern a lly th rou gh a s a lt b r id ge a s s h own in Fig. 3 .1 . Som etim es , b oth
th e electrod es d ip in th e s a m e electrolyte s olu tion a n d in s u ch ca s es we
d on t r equ ir e a s a lt b r id ge.

3.2 Galvanic Cells

65

E le c t r oc h e m is t r y

At ea ch electr od e-electr olyte in ter fa ce th er e is a ten d en cy of m eta l

ion s fr om th e s olu tion to d ep os it on th e m eta l electr od e tr yin g to m a k e
it p os itively ch a r ged . At th e s a m e tim e, m eta l a tom s of th e electr od e
h a ve a ten d en cy to go in to th e s olu tion a s ion s a n d lea ve b eh in d th e
electr on s a t th e electr od e tr yin g to m a k e it n ega tively ch a r ged . At
equ ilib riu m , th ere is a s ep a ra tion of ch a rges a n d d ep en d in g on th e
ten d en cies of th e two op p os in g rea ction s , th e electrod e m a y b e p os itively
or n ega tively ch a rged with res p ect to th e s olu tion . A p oten tia l d ifferen ce
d evelop s b etween th e electr od e a n d th e electr olyte wh ich is ca lled
e le c t ro de po t e n t ial. Wh en th e con cen tra tion s of a ll th e s p ecies in volved
in a h a lf-cell is u n ity th en th e electrod e p oten tia l is k n own a s s t an dard
e le c t ro d e p o t e n t i a l. Ac c or d in g t o IUPAC c on ve n t ion , s t a n d a r d
r ed u ction p oten tia ls a r e n ow ca lled s ta n d a r d electr od e p oten tia ls . In a
ga lva n ic cell, th e h a lf-cell in wh ich oxid a tion ta k es p la ce is ca lled an o de
a n d it h a s a n ega tive p oten tia l with r es p ect to th e s olu tion . Th e oth er
h a lf-cell in wh ich r ed u ction ta k es p la ce is ca lled c at h o de a n d it h a s a
positive poten tia l with respect to th e solu tion . Th u s, th ere exists a poten tial
d ifferen ce b etween th e two electrodes a n d a s s oon a s th e s witch is in th e
on pos ition th e electron s flow from n ega tive electrode to pos itive electrode.
Th e d ir ection of cu rren t flow is op p os ite to th a t of electron flow.
Th e p oten tia l d ifferen ce b etween th e two electrod es of a ga lva n ic cell
is ca lled th e cell poten tia l a n d is m ea s u r ed in volts . Th e cell poten tia l
is th e d iffer en ce b etween th e electr od e p oten tia ls (r ed u ction p oten tia ls )
of th e ca th od e a n d a n od e. It is ca lled th e cell electrom otive force (em f)
of th e cell wh en n o cu r r en t is d r a wn th r ou gh th e cell. It is n ow a n
a ccep ted con ven tion th a t we k eep th e a n od e on th e left a n d th e ca th od e
on th e r igh t wh ile r ep r es en tin g th e ga lva n ic cell. A ga lva n ic cell is
gen er a lly r ep r es en ted b y p u ttin g a ver tica l lin e b etween m eta l a n d
electr olyte s olu tion a n d p u ttin g a d ou b le ver tica l lin e b etween th e two
electr olytes con n ected b y a s a lt b r id ge. Un d er th is con ven tion th e em f
of th e cell is p os itive a n d is given b y th e p oten tia l of th e h a lf-cell on th e
r igh t h a n d s id e m in u s th e p oten tia l of th e h a lf-cell on th e left h a n d s id e
i.e.
E cell = E r igh t E left
Th is is illu s tr a ted b y th e followin g exa m p le:
Cell rea ction :
(3 .4 )
Cu (s ) + 2 Ag +(a q) Cu 2 +(a q) + 2 Ag(s )
Ha lf-cell rea ction s :
(3 .5 )
Ca th od e (red u ction ):
2 Ag +(a q) + 2 e 2 Ag(s )
(3 .6 )
An od e (oxid a tion ):
Cu (s ) Cu 2 +(a q) + 2 e
It ca n b e s een th a t th e s u m of (3 .5 ) a n d (3 .6 ) lea ds to overa ll rea ction
(3 .4 ) in th e cell a n d th a t s ilver electrod e a cts a s a ca th od e a n d cop p er
electrod e a cts a s a n a n od e. Th e cell ca n b e rep res en ted a s :
Cu (s )| Cu 2 +(a q)|| Ag +(a q)| Ag(s )
(3 .7 )
a n d we h a ve E cell = E righ t E left = E Ag Ag E Cu Cu
+

3 .2 .1 Me as ure m e n t
o f Ele c t ro de
Po t e n t ial
C h e m is t r y

66

2+

Th e poten tia l of in dividu a l h a lf-cell ca n n ot b e m ea s u red. We ca n m ea s u r e

on ly th e d ifferen ce b etween th e two h a lf-cell p oten tia ls th a t gives th e em f
of th e cell. If we a r b itr a r ily ch oos e th e p oten tia l of on e electr od e (h a lf-

cell) th en th a t of th e oth er ca n b e d eter m in ed with r es p ect to th is .

Accord in g to con ven tion , a h a lf-cell ca lled s ta n d a rd h yd rogen electrod e
(Fig.3 .3 ) r ep r es en ted b y Pt(s ) H 2 (g) H +(a q), is a s s ign ed a zer o p oten tia l
a t a ll tem p er a tu r es cor r es p on d in g to th e r ea ction
1
H (g)
H + (a q) + e
2 2
Th e s ta n d a r d h yd r ogen electr od e con s is ts of a p la tin u m electr od e
coa ted with p la tin u m b la ck . Th e electr od e is d ip p ed in a n a cid ic
s olu t ion a n d p u r e h yd r oge n ga s is b u b b le d t h r ou gh it . Th e
con cen tr a tion of b oth th e r ed u ced a n d oxid is ed for m s of h yd r ogen is
m a in ta in ed a t u n ity (Fig. 3 .3 ). Th is im p lies
th a t th e p r es s u r e of h yd r ogen ga s is on e
b a r a n d th e con cen tr a tion of h yd r ogen ion
in th e s olu tion is on e m ola r.
At 2 9 8 K th e em f of th e cell, s ta n d a r d
h y d r o g e n e le c t r o d e s e c o n d h a lf- c e ll
con s tr u cted b y ta k in g s ta n d a r d h yd r ogen
electr od e a s a n od e (r efer en ce h a lf-cell) a n d
th e oth er h a lf-cell a s ca th od e, gives th e
r ed u ction p oten tia l of th e oth er h a lf-cell. If
th e con cen tr a tion s of th e oxid is ed a n d th e
r ed u ced for m s of th e s p ecies in th e r igh t
h a n d h a lf-c e ll a r e u n it y, t h e n t h e c e ll
p ot en t ia l is equ a l t o s t a n d a r d elect r od e
p oten tia l,E !R of th e given h a lf-cell.
E ! = E !R - E !L
As E!L for s ta n d a r d h yd r ogen electr od e
is zer o.
Fig . 3 .3 : S ta n d a rd Hy d rogen Electrod e (S HE).
E ! = E !R 0 = E !R
Th e m ea s u r ed em f of th e cell :
Pt(s ) H 2 (g, 1 b a r ) H + (a q, 1 M) Cu 2 + (a q, 1 M) Cu
is 0 .3 4 V a n d it is a ls o th e va lu e for th e s ta n d a rd electrod e p oten tia l
of th e h a lf-cell cor r es p on d in g to th e r ea ction :
Cu 2+ (a q, 1 M) + 2 e Cu (s )
S im ila r ly, th e m ea s u r ed em f of th e cell :
Pt(s ) H 2 (g, 1 b a r ) H + (a q, 1 M) Zn 2 + (a q, 1 M) Zn
is -0 .7 6 V cor r es p on d in g to th e s ta n d a r d electr od e p oten tia l of th e
h a lf-cell r ea ction :
Zn 2+ (a q, 1 M) + 2 e Zn (s )
Th e p os itive va lu e of th e s ta n d a r d electr od e p oten tia l in th e fir s t
ca s e in d ica tes th a t Cu 2 + ion s get r ed u ced m or e ea s ily th a n H + ion s .
Th e r evers e p r oces s ca n n ot occu r, th a t is , h yd rogen ion s ca n n ot oxid is e
Cu (or a lter n a tively we ca n s a y th a t h yd r ogen ga s ca n r ed u ce cop p er
ion ) u n d er th e s ta n d a r d con d ition s d es cr ib ed a b ove. Th u s , Cu d oes
n ot d is s olve in HCl. In n itr ic a cid it is oxid is ed b y n itr a te ion a n d n ot
b y h yd rogen ion . Th e n ega tive va lu e of th e s ta n d a rd electrod e p oten tia l
in th e s econ d ca s e in d ica tes th a t h yd r ogen ion s ca n oxid is e zin c (or
zin c ca n r ed u ce h yd r ogen ion s ).
67

E le c t r oc h e m is t r y

In view of t h is con ven t ion , t h e h a lf r ea ct ion for t h e Da n iell cell in

Fig. 3 .1 ca n b e wr it t en a s :
Left electr od e : Zn (s ) Zn 2 + (a q, 1 M) + 2 e
Righ t electr od e: Cu 2 + (a q, 1 M) + 2 e Cu (s )
Th e over a ll r ea ction of th e cell is th e s u m of a b ove two r ea ction s
a n d we ob ta in th e equ a tion :
Zn (s ) + Cu 2 + (a q) Zn 2 + (a q) + Cu (s )
0
E m f of th e cell = E cell
= E0R - E0L

= 0 .3 4 V ( 0 .7 6 )V = 1 .1 0 V
Som etim es m eta ls lik e p la tin u m or gold a re u s ed a s in ert electrod es .
Th ey d o n ot p a r ticip a te in th e r ea ction b u t p r ovid e th eir s u r fa ce for
oxid a tion or r ed u ction r ea ction s a n d for th e con d u ction of electr on s .
For exa m p le, Pt is u s ed in th e followin g h a lf-cells :
Hyd rogen electrod e: Pt(s )| H 2 (g)| H +(a q)
With h a lf-cell r ea ction : H + (a q)+ e H 2 (g)
Br om in e electr od e: Pt(s )| Br 2 (a q)| Br (a q)
With h a lf-cell r ea ction : Br 2 (a q) + e Br (a q)
Th e s t a n d a r d elect r od e p ot en t ia ls a r e ver y im p or t a n t a n d we ca n
ext r a ct a lot of u s efu l in for m a t ion fr om t h em . Th e va lu es of s t a n d a r d
elect r od e p ot en t ia ls for s om e s elect ed h a lf-cell r ed u ct ion r ea ct ion s a r e
given in Ta b le 3 .1 . If t h e s t a n d a r d elect r od e p ot en t ia l of a n electr od e
is gr ea t er t h a n zer o t h en it s r ed u ced for m is m or e s t a b le com p a r ed t o
h yd r ogen ga s . S im ila r ly, if th e s ta n d a r d electr od e p oten tia l is n ega tive
th en h yd r ogen ga s is m or e s ta b le th a n th e r ed u ced for m of th e s p ecies .
It ca n b e s een t h a t t h e s t a n d a r d elect r od e p ot en t ia l for flu or in e is t h e
h igh es t in th e Ta b le in d ica t in g t h a t flu orin e ga s (F 2 ) h a s th e m a xim u m
ten d en cy to get r ed u ced to flu or id e ion s (F ) a n d th er efor e flu or in e ga s
is th e s tron ges t oxid is in g a gen t a n d flu orid e ion is th e wea k es t red u cin g
a gen t. Lith iu m h a s th e lowes t electrod e p oten tia l in d ica tin g th a t lith iu m
ion is th e wea k es t oxid is in g a gen t wh ile lit h iu m m et a l is th e m os t
p ower fu l r ed u cin g a gen t in a n a qu eou s s olu tion . It m a y b e s een t h a t
a s we go fr om t op t o b ot t om in Ta b le 3 .1 t h e s t a n d a r d elect r od e
p ot en t ia l d ecr ea s es a n d wit h t h is , d ecr ea s es t h e oxid is in g p ower of
t h e s p ecies on t h e left a n d in cr ea s es t h e r ed u cin g p ower of t h e s p ecies
on t h e r igh t h a n d s id e of t h e r ea ct ion . E lect r och em ica l cells a r e
ext en s ively u s ed for d et er m in in g t h e p H of s olu t ion s , s olu b ilit y
p r od u ct , equ ilib r iu m con s ta n t a n d oth er th er m od yn a m ic p r op er ties
a n d for p ot en t iom et r ic t it r a t ion s .

Intext Questions
3 .1 How wou ld you d eterm in e th e s ta n d a rd electrod e p oten tia l of th e s ys tem Mg2+| Mg?
3 .2 Ca n you s tor e cop p er s u lp h a te s olu tion s in a zin c p ot?
3 .3 Con s u lt th e ta b le of s ta n d a r d electr od e p oten tia ls a n d s u gges t th r ee s u b s ta n ces
th a t ca n oxid is e fer r ou s ion s u n d er s u ita b le con d ition s .
C h e m is t r y

68

Table 3 .1 Th e s t an dard e le c t ro de po t e n t ials at 2 9 8 K

Ion s a re p res en t a s a qu eou s s p ecies a n d H 2 O a s liqu id ; ga s es a n d s olid s a re s h own b y g a n d s .

F 2 (g) + 2 e
Co

3+

+ e

H2O2 + 2 H + 2 e

Mn O 4 + 8 H + 5 e
3+

Au

+ 3e

Cl2 (g) + 2 e
Cr 2 O 7

+ 14H + 6e

O 2 (g) + 4 H + + 4 e
+

Mn O 2 (s ) + 4 H + 2 e
Br 2 + 2 e

In cr ea s in g s t r en gt h of oxid is in g a gen t

NO 3 + 4 H + 3 e
2 Hg

2+

+ 2e

Ag + e
Fe

3+

+e

O 2 (g) + 2 H + + 2 e
I2 + 2 e

Cu + e
Cu

2+

+ 2e

AgCl(s ) + e

AgBr(s ) + e
2 H+ + 2 e
Pb 2 + + 2 e
2+

Sn
Ni

2+

Fe

2+

Cr

3+

Zn

2+

+ 2e

+ 2e

+ 2e

+ 3e

+ 2e

2 H2O + 2 e

Al3 + + 3 e
Mg

2+

+ 2e

Na + + e
Ca
+

2+

+ 2e

K +e
+

Li + e

Re du c e d fo rm )

2F
Co 2 +
2 H2O
Mn 2 + + 4 H 2 O
Au (s )
2 Cl
2 Cr 3 + + 7 H 2 O
2 H2O
Mn 2 + + 2 H 2 O
2 Br
NO(g) + 2 H 2 O
Hg 2 2 +
Ag(s )
Fe 2 +
H 2O2
2 I
Cu (s )
Cu (s )
Ag(s ) + Cl
Ag(s ) + Br
H2 (g)
Pb (s )
S n (s )
Ni(s )
Fe(s )
Cr (s )
Zn (s )

E / V
2 .8 7
1 .8 1
1 .7 8
1 .5 1
1 .4 0
1 .3 6
1 .3 3
1 .2 3
1 .2 3
1 .0 9
0 .9 7
0 .9 2

In cr ea s in g s t r en gt h of r ed u cin g a gen t

Re ac t io n (Oxidis e d fo rm + n e

0 .8 0
0 .7 7
0 .6 8
0 .5 4
0 .5 2
0 .3 4
0 .2 2
0 .1 0
0 .0 0
0 .1 3
0 .1 4
0 .2 5
0 .4 4
0 .7 4
0 .7 6

H 2 (g) + 2 OH (a q)

0 .8 3

Al(s )

1 .6 6

Mg(s )

2 .3 6

Na (s )

2 .7 1

Ca (s )

2 .8 7

K(s )

2 .9 3

Li(s )

3 .0 5

1 . A n ega tive E m ea n s th a t th e red ox cou p le is a s tron ger red u cin g a gen t th a n th e H +/ H 2 cou p le.
2 . A p os itive E m ea n s th a t th e red ox cou p le is a wea k er red u cin g a gen t th a n th e H +/ H 2 cou p le.
69

E le c t r oc h e m is t r y

3 . 3 Nernst
Equation

We h a ve a s s u m ed in th e p r eviou s s ection th a t th e con cen tr a tion of a ll

th e s p ecies in volved in th e electr od e r ea ction is u n ity. Th is n eed n ot b e
a lwa ys tr u e. Ner n s t s h owed th a t for th e electr od e r ea ction :
Mn +(a q) + n e M(s )
th e electrode p oten tia l a t a n y con cen tra tion m ea s u red with res pect to
s ta n d a rd h yd rogen electrod e ca n b e rep res en ted b y:
E(

= E(

Mn + / M)

Mn + / M)

RT
ln [M]
nF
[M n + ]

b u t con cen tra tion of s olid M is ta k en a s u n ity a n d we h a ve

E(

E(

Mn + / M )

RT

= E( n+ )
ln
M)
M
/ M
nF
[M n + ]
V

n+

(3 .8 )

h a s a lr ea d y b een d efin ed , R is ga s con s t a n t (8 .3 1 4

J K m ol ), F is Fa ra d a y con s ta n t (9 6 4 8 7 C m ol1 ), T is tem p er a tu r e in

k elvin a n d [M n +] is th e con cen tr a tion of th e s p ecies , M n +.
In Da n iell cell, th e electrode poten tia l for a n y given con cen tra tion of
Cu 2+ a n d Zn 2+ ion s , we write
For Ca th od e:
1
V
RT
E( 2+
E
2+
=

ln
(3 .9 )
2
+
)
(
)
Cu
/ Cu
Cu ( a q )
Cu
/ Cu
2F
For An od e:
E(

Zn

2+

1
V
RT
E
2
+
=

ln
( Zn 2 + / Zn )
/ Zn )
Zn ( a q )
2F

(3 .1 0 )

Th e cell p oten tia l, E (cell) = E ( Cu 2 + / Cu ) E ( Zn 2 + / Zn )

1
1
V
V
RT
RT
= E ( Cu 2 + / Cu )
ln Cu 2 + (a q) - E ( Zn 2 + / Zn ) +
ln Zn 2 + (a q)
2F
2F

= E ( Cu 2 + / Cu ) E ( Zn 2 + / Zn )

E (cell) = E

V
( cell )

RT
2F

RT
2F

ln

[Zn 2 + ]
ln
[Cu 2 + ]

1
Cu

2+

( a q )

ln

1
Zn

2+

( a q )
(3 .1 1 )

It ca n b e s een th a t E (cell) d ep en d s on th e con cen tr a tion of b oth Cu 2 +

a n d Zn 2 + ion s . It in cr ea s es with in cr ea s e in th e con cen tr a tion of Cu 2 +
ion s a n d d ecr ea s e in th e con cen tr a tion of Zn 2 + ion s .
By con vertin g th e n a tu ra l loga rith m in Eq. (3 .1 1 ) to th e b a s e 1 0 a n d
s u b s titu tin g th e va lu es of R, F a n d T = 2 9 8 K, it red u ces to
E (cell) = E ( cell )
V

0 .0 5 9
[Zn 2 + ]
log
2
[Cu 2 + ]

(3 .1 2 )

We s h ou ld u s e th e s a m e n u m b er of electr on s (n ) for b oth th e

electr od es a n d th u s for th e followin g cell
C h e m is t r y

70

Ni(s ) Ni2+(a q) Ag +(a q) Ag

Th e cell r ea ction is Ni(s ) + 2 Ag +(a q) Ni2 +(a q) + 2 Ag(s )
Th e Nern s t equ a tion ca n b e written a s
[Ni 2 + ]
[Ag + ]2

RT

E (cell) = E ( cell )
ln
2F
V

a n d for a gen er a l electr och em ica l r ea ction of th e typ e:

ne
a A + b B cC + d D
Ner n s t equ a tion ca n b e wr itten a s :

RT

E (cell)= E ( cell ) nF 1n Q
V

[C]c [D]d

RT

= E ( cell ) nF ln [A]a [B]b

V

(3 .1 3 )

Rep r es en t th e cell in wh ich th e followin g r ea ction ta k es p la ce

Mg(s ) + 2 Ag +(0 .0 0 0 1 M) Mg2 +(0 .1 3 0 M) + 2 Ag(s )

Example 3.1

Ca lcu la te its E (cell) if E ( cell ) = 3 .1 7 V.

V

Th e cell ca n b e written a s MgMg 2 +(0 .1 3 0 M)Ag +(0 .0 0 0 1 M)Ag

E ( cell ) = E ( cell )
V

= 3 .1 7 V

Solution

2+
RT Mg
ln
2
2F
Ag +

0 .0 5 9V
0 .1 3 0
log
= 3 .1 7 V 0 .2 1 V = 2 .9 6 V.
2
(0 . 0 0 0 1 )2

If th e cir cu it in Da n iell cell (Fig. 3 .1 ) is clos ed th en we n ote th a t th e 3 .3 .1

rea ction
(3 .1 )
Zn (s ) + Cu 2+(a q) Zn 2 +(a q) + Cu (s )
t a k es p la ce a n d a s t im e p a s s es , t h e con cen t r a t ion of Zn 2 + k eep s
on in cr ea s in g wh ile t h e con cen t r a t ion of Cu 2 + k eep s on d ecr ea s in g.
At t h e s a m e t im e volt a ge of t h e cell a s r ea d on t h e volt m et er k eep s
on d ecr ea s in g. Aft er s om e t im e, we s h a ll n ot e t h a t t h er e is n o ch a n ge
in t h e con cen t r a t ion of Cu 2 + a n d Zn 2 + ion s a n d a t t h e s a m e t im e,
volt m et er gives zer o r ea d in g. Th is in d ica t es t h a t equ ilib r iu m h a s b een
a t t a in ed . In t h is s it u a t ion t h e Ner n s t equ a t ion m a y b e wr it t en a s :
E (cell) = 0 = E ( cell )
V

or E ( cell ) =
V

Equilibrium
Co n s t an t
fro m Ne rn s t
Equ at io n

2 .3 0 3 RT
[Zn 2 + ]
log
2F
[Cu 2 + ]

2 .3 0 3 R T
[Zn 2 + ]
log
2F
[C u 2 + ]

Bu t a t equ ilib riu m ,

71

E le c t r oc h e m is t r y

[Zn 2 + ]
[Cu 2 + ]

= K c for th e rea ction 3 .1

a n d a t T = 2 9 8 K th e a b ove equ a tion ca n b e written a s

E ( cell ) =
V

0 .0 5 9 V
log K C = 1 .1 V
2

log K C =

( E ( cell ) = 1 .1 V)
V

(1 .1 V 2 )
= 3 7 .2 8 8
0 .0 5 9 V

K C = 2 1 0 3 7 a t 2 9 8 K.
In gen era l,
E ( cell ) =
V

2 .3 0 3 RT
log K C
nF

(3 .1 4 )

Th u s , E q. (3 .1 4 ) gives a r ela tion s h ip b etween equ ilib r iu m con s ta n t

of th e r ea ction a n d s ta n d a r d p oten tia l of th e cell in wh ich th a t r ea ction
ta k es p la ce. Th u s , equ ilib r iu m con s ta n ts of th e r ea ction , d ifficu lt to
m ea s u r e oth er wis e, ca n b e ca lcu la ted fr om th e cor r es p on d in g E va lu e
of th e cell.

Example 3.2 Ca lcu la te th e equ ilib riu m con s ta n t of th e rea ction :

Cu (s ) + 2 Ag +(a q) Cu 2 +(a q) + 2 Ag(s )
E ( cell ) = 0 .4 6 V
V

Solution E (Vcell ) =
log K C =

0 .0 5 9 V
log K C = 0 .4 6 V or
2

0 .4 6 V 2
0 .0 5 9 V = 1 5 .6

K C = 3 .9 2 1 0 15

3 .3 .2 Ele c t ro c h e m ic al
Ce ll an d
Gibbs
En e rgy o f
t h e Re ac t io n

C h e m is t r y

72

E lectr ica l wor k d on e in on e s econ d is equ a l to electr ica l p oten tia l

m u ltip lied b y tota l ch a r ge p a s s ed . If we wa n t to ob ta in m a xim u m
wor k fr om a ga lva n ic cell th en ch a r ge h a s to b e p a s s ed r ever s ib ly. Th e
revers ib le work d on e b y a ga lva n ic cell is equ a l to d ecrea s e in its Gib b s
en er gy a n d th er efor e, if th e em f of th e cell is E a n d n F is th e a m ou n t
of ch a r ge p a s s ed a n d r G is th e Gib b s en er gy of th e r ea ction , th en
(3 .1 5 )
rG = n FE (cell)
It m a y b e rem em b ered th a t E (cell) is a n in ten s ive p a r a m eter b u t
r G is a n exten s ive th er m od yn a m ic p r op er ty a n d th e va lu e d ep en d s on
n . Th u s , if we wr ite th e r ea ction
(3 .1 )
Zn (s ) + Cu 2 +(a q) Zn 2 +(a q) + Cu (s )
r G = -2 FE (cell)
b u t wh en we write th e rea ction
2 Zn (s) + 2 Cu 2+(aq) 2 Zn 2 +(a q)+2 Cu (s )

r G = 4 FE (cell)
If th e con cen tr a tion of a ll th e r ea ctin g s p ecies is u n ity, th en E (cell)
= E ( cell ) a n d we h a ve
V

r G = n F E (cell)
V

(3 .1 6 )

Th u s , from th e m ea s u rem en t of E ( cell ) we ca n ob ta in a n im p orta n t

V

th erm od yn a m ic qu a n tity, r G , s ta n d a r d Gib b s en er gy of th e r ea ction .

From th e la tter we ca n ca lcu la te equ ilib riu m con s ta n t b y th e equ a tion :
r G = R T ln K.

Example 3.3 Th e s ta n d a r d electr od e p oten tia l for Da n iell cell

is 1 .1 V. Ca lcu la te th e s ta n d a r d Gib b s en er gy for th e r ea ction :
Zn (s ) + Cu 2 +(a q) Zn 2 +(a q) + Cu (s )
V
Solution r G = n F E (cell)

n in th e a b ove equ a tion is 2 , F = 9 6 4 8 7 C m ol 1 a n d

E ( cell ) = 1 .1 V
V

Th erefore, r G = 2 1.1V 9648 7 C m ol 1

= 2 1 2 2 7 J m ol1
= 2 1 .2 2 7 k J m ol1

Intext Questions
3 .4 Ca lcu la te th e p oten tia l of h yd r ogen electr od e in con ta ct with a s olu tion wh os e
p H is 1 0 .
3 .5 Ca lcu la te th e em f of th e cell in wh ich th e followin g r ea ction ta k es p la ce
Ni(s ) + 2 Ag + (0 .0 0 2 M) Ni 2 + (0 .1 6 0 M) + 2 Ag(s )
Given th a t

E V(cell) = 1 .0 5 V

3 .6 Th e cell in wh ich th e followin g r ea ction occu r s :

0
2 Fe 3 + ( a q ) + 2 I ( a q ) 2 Fe 2 + ( a q ) + I2 ( s ) h a s E cell
= 0.236 V a t 298 K. Ca lcu la te
th e s ta n d a r d Gib b s en er gy a n d th e equ ilib r iu m con s ta n t of th e cell r ea ction .

3 . 4 Conductance
of Electrolytic
Solutions

It is n eces s a ry to defin e a few term s before we con s ider th e s u bject of

con du cta n ce of electricity th rou gh electrolytic s olu tion s . Th e electrica l
res is ta n ce is repres en ted by th e s ym bol R a n d it is m ea s u red in oh m ()
wh ich in term s of SI ba s e u n its is equ a l to (kg m 2 )/ (s 3 A 2 ). It ca n be
m easu red with th e h elp of a Wh eatston e bridge with wh ich you are fam iliar
73

E le c t r oc h e m is t r y

from you r stu dy of ph ysics. Th e electrica l resista n ce of a n y object is directly

proportion a l to its len gth , l, a n d in vers ely proportion a l to its a rea of cros s
s ection , A. Th a t is ,
R

l
A

or R =

(3 .1 7 )

Th e con s ta n t of p rop ortion a lity, (Greek , rh o), is ca lled re s is t ivit y

(s p ecific r es is ta n ce). Its SI u n its a r e oh m m etr e ( m ) a n d qu ite often
its s u b m u ltip le, oh m cen tim etre ( cm ) is a ls o u s ed . IUPAC recom m en d s
th e u s e of th e ter m r es is tivity over s p ecific r es is ta n ce a n d h en ce in th e
res t of th e book we s h a ll u s e th e term res is tivity. Ph ys ica lly, th e res is tivity
for a s u b s ta n ce is its r es is ta n ce wh en it is on e m etr e lon g a n d its a r ea
of cr os s s ection is on e m 2 . It ca n b e s een th a t:
1 m = 1 0 0 cm or 1 cm = 0 .0 1 m
Th e in ver s e of r es is ta n ce, R, is ca lled c o n duc t an c e , G, a n d we
h a ve th e r ela tion :
G =

1
R

A
l

(3 .1 8 )

Th e SI u n it of con d u cta n ce is s iem en s , rep res en ted b y th e s ym b ol

S a n d is equ a l to oh m 1 (a ls o k n own a s m h o) or 1 . Th e in ver s e of
res is tivity, ca lled c o n duc t ivit y (s p ecific con d u cta n ce) is rep res en ted b y
th e s ym b ol, (Greek , k a p p a ). IUPAC h a s recom m en d ed th e u s e of term
con d u ctivity over s p ecific con d u cta n ce a n d h en ce we s h a ll u s e th e term
con d u ctivity in th e r es t of th e b ook . Th e SI u n its of con d u ctivity a r e S
m 1 b u t qu ite often , is exp res s ed in S cm 1 . Con d u ctivity of a m a ter ia l
in S m 1 is its con d u cta n ce wh en it is 1 m lon g a n d its a rea of cros s
s ection is 1 m 2 . It m a y b e n oted th a t 1 S cm 1 = 1 0 0 S m 1 .
Table 3 .2 Th e
value s o f
Co n duc t ivit y o f
s o m e Se le c t e d
Mat e rials at
2 9 8 .1 5 K

Ma t e ri a l
Co n d u c t o r s
S od iu m
Cop p e r
S ilve r
Gold
Ir on
G r a p h it e
In s u l a t o r s
G la s s
Teflon

Co n d u c t i v i t y /
S m 1
3

2 .1 1 0
5 .9 1 0 3
6 .2 1 0 3
4 .5 1 0 3
1 .0 1 0 3
1 .2 1 0
1 .0 1 0 1 6
1 .0 1 0 1 8

Ma t e ri a l
Aq u e o u s S o l u t i o n s
Pu r e wa t er
0 .1 M HCl
0 .0 1 M KCl
0 .0 1 M Na Cl
0 .1 M HAc
0 .0 1 M HAc
S em icond uct ors
Cu O
Si
Ge

Co n d u c t i v i t y /
S m 1
3 .5 1 0 5
3 .9 1
0 .1 4
0 .1 2
0 .0 4 7
0 .0 1 6
1 1 0 7
1 .5 1 0 2
2 .0

It ca n b e s een fr om Ta b le 3 .2 th a t th e m a gn itu d e of con d u ctivity

va r ies a gr ea t d ea l a n d d ep en d s on th e n a tu r e of th e m a ter ia l. It a ls o
d ep en d s on th e tem p era tu re a n d p res s u re a t wh ich th e m ea s u rem en ts
C h e m is t r y

74

a r e m a d e. Ma ter ia ls a r e cla s s ified in to con d u ctor s , in s u la tor s a n d

s em icon d u ctor s d ep en d in g on th e m a gn itu d e of th eir con d u ctivity.
Meta ls a n d th eir a lloys h a ve ver y la r ge con d u ctivity a n d a r e k n own a s
con d u ctors . Certa in n on -m eta ls lik e ca rb on -b la ck , gra p h ite a n d s om e
orga n ic p olym ers * a re a ls o electron ica lly con d u ctin g. Su b s ta n ces lik e
gla s s , cer a m ics , et c., h a vin g ver y low con d u ct ivit y a r e k n own a s
in s u la tor s . Su b s ta n ces lik e s ilicon , d op ed s ilicon a n d ga lliu m a r s en id e
h a vin g con d u ct ivit y b et ween con d u ct or s a n d in s u la t or s a r e ca lled
s em icon du ctors a n d a re im porta n t electron ic m a teria ls . Certa in m a teria ls
ca lled s u p er con d u ctor s b y d efin ition h a ve zer o r es is tivity or in fin ite
c on d u c t ivit y. E a r lie r, on ly m e t a ls a n d t h e ir a lloys a t ve r y low
tem p era tu res (0 to 1 5 K) were k n own to b eh a ve a s s u p ercon d u ctors ,
b u t n owa d a ys a n u m b er of cera m ic m a teria ls a n d m ixed oxid es a re
a ls o k n own to s h ow s u p er con d u ctivity a t tem p era tu res a s h igh a s
1 5 0 K.
Electrica l con d u cta n ce th rou gh m eta ls is ca lled m eta llic or electron ic
con d u cta n ce a n d is d u e to th e m ovem en t of electron s . Th e electron ic
con d u cta n ce d ep en d s on
(i) th e n a tu r e a n d s tr u ctu r e of th e m eta l
(ii) th e n u m b er of va len ce electr on s p er a tom
(iii) tem p er a tu r e (it d ecr ea s es with in cr ea s e of tem p er a tu r e).
As th e electron s en ter a t on e en d a n d go ou t th rou gh th e oth er en d ,
th e com p os ition of th e m eta llic con d u ctor r em a in s u n ch a n ged . Th e
m ech a n is m of con d u cta n ce th rou gh s em icon d u ctors is m ore com p lex.
We a lr ea d y k n ow (Cla s s XI, Un it 7 ) th a t even very p u r e wa ter h a s
s m a ll a m ou n ts of h yd rogen a n d h yd roxyl ion s (~1 0 7 M) wh ich len d it
very low con d u ctivity (3 .5 1 0 5 S m 1 ). Wh en electrolytes a re d is s olved
in wa ter, th ey fu r n is h th eir own ion s in th e s olu tion h en ce its con du ctivity
a ls o in cr ea s es . Th e con d u cta n ce of electr icity b y ion s p r es en t in th e
s olu tion s is ca lled electrolytic or ion ic con d u cta n ce. Th e con d u ctivity of
electr olytic (ion ic) s olu tion s d ep en d s on :
(i) th e n a tu r e of th e electr olyte a d d ed
(ii) s ize of th e ion s p r od u ced a n d th eir s olva tion
(iii) th e n a tu r e of th e s olven t a n d its vis cos ity
(iv) con cen tr a tion of th e electr olyte
(v) tem p er a tu r e (it in cr ea s es with th e in cr ea s e of tem p er a tu r e).
Pa s s a ge of d irect cu rren t th rou gh ion ic s olu tion over a p rolon ged
p eriod ca n lea d to ch a n ge in its com p os ition d u e to electroch em ica l
rea ction s (Section 3 .4 .1 ).
*

Electron ica lly con d u ctin g p oly m ers In 1 9 7 7 Ma cDia rm id , Heeger a n d S h ira k a w a d is covered th a t a cety len e ga s ca n
b e p oly m eris ed to p rod u ce a p oly m er, p oly a cety len e w h en exp os ed to va p ou rs of iod in e a cqu ires m eta llic lu s tre a n d
con d u ctiv ity . S in ce th e n s e v e ra l orga n ic con d u ctin g p oly m e rs h a v e b e e n m a d e s u ch a s p oly a n ilin e , p oly p y rrole a n d
p oly th iop h e n e . Th e s e orga n ic m e ta ls , b e in g com p os e d w h olly of e le m e n ts lik e ca rb on , h y d roge n a n d occa s ion a lly
n itrogen , oxy gen or s u lp h u r, a re m u ch ligh ter th a n n orm a l m eta ls a n d ca n b e u s ed for m a k in g ligh t-w eigh t b a tteries .
B es id es , th ey h a ve th e m ech a n ica l p rop erties of p oly m ers s u ch a s flexib ility s o th a t on e ca n m a k e electron ic d evices
s u ch a s tra n s is tors th a t ca n b e n d lik e a s h e e t of p la s tic. For th e d is cov e ry of con d u ctin g p oly m e rs , Ma cDia rm id ,
Heeger a n d S h ira k a w a w ere a w a rd ed th e Nob el Priz e in Ch em is try for th e y ea r 2 0 0 0 .

75

E le c t r oc h e m is t r y

3 .4 .1
Me a s u re m e n t o f
t h e Co n d u c t i v i t y
o f Io n ic So lut io n s

We k n ow th a t a ccu ra te m ea s u r em en t of a n u n k n own res is ta n ce ca n b e

per for m ed on a Wh ea ts ton e bridge. However, for m ea s u rin g th e res is ta n ce
of a n ion ic s olu tion we fa ce two p rob lem s . Firs tly, p a s s in g d irect cu rren t
(DC) ch a n ges th e com pos ition of th e s olu tion . Secon dly, a s olu tion ca n n ot
b e con n ected to th e b rid ge lik e a m eta llic wir e or oth er s olid con d u ctor.
Th e firs t d ifficu lty is res olved b y u s in g a n a ltern a tin g cu rren t (AC) s ou rce
of p ower. Th e s econ d p r ob lem is s olved b y u s in g a s p ecia lly d es ign ed
ves s el ca lled c o n duc t ivit y c e ll. It is a va ila b le in s evera l d es ign s a n d two
s im p le on es a re s h own in Fig. 3 .4 .

Fig . 3 .4 : Tw o d ifferen t ty pes of con d u ctivity cells .

Ba s ica lly it con s is ts of two p la tin u m electrod es coa ted with p la tin u m
b la ck (fin ely d ivid ed m et a llic Pt is d ep os it ed on t h e elect r od es
electroch em ica lly). Th es e h a ve a rea of cros s s ection equ a l to A a n d a re
s ep a ra ted b y d is ta n ce l. Th er efor e, s olu tion con fin ed b etween th es e
electr od es is a colu m n of len gth l a n d a r ea of cr os s s ection A. Th e
r es is ta n ce of s u ch a colu m n of s olu tion is th en given b y th e equ a tion :
R =

l
l
=
A
A

(3 .1 7 )

Th e qu a n tity l/ A is ca lled cell con s ta n t d en oted b y th e s ym b ol, G*.

It d ep en d s on th e d is ta n ce b etween th e electrod es a n d th eir a rea of
cros s -s ection a n d h a s th e d im en s ion of len gth 1 a n d ca n b e ca lcu la ted
if we k n ow l a n d A. Mea s u r em en t of l a n d A is n ot on ly in con ven ien t
bu t a ls o u n relia ble. Th e cell con s ta n t is u s u a lly determ in ed by m ea s u rin g
th e res is ta n ce of th e cell con ta in in g a s olu tion wh os e con d u ctivity is
a lrea d y k n own . For th is p u rp os e, we gen era lly u s e KCl s olu tion s wh os e
con d u ctivity is k n own a ccu ra tely a t va riou s con cen tra tion s (Ta b le 3 .3 )
a n d a t d ifferen t tem p era tu res . Th e cell con s ta n t, G*, is th en given b y th e
equ a tion :
G* =

C h e m is t r y

76

l
= R
A

(3 .1 8 )

Mo larit y

Con c e n t rat ion Con duc t ivit y

Mo lar Conductivity

m ol L1

m ol m 3

S cm 1

S m 1

S cm 2 m ol 1

S m 2 m ol1

1 .0 0 0

1000

0 .1 1 1 3

1 1 .1 3

1 1 1 .3

1 1 1 . 3 1 0 4

0 .1 0 0

1 0 0 .0

0 .0 1 2 9

1 .2 9

1 2 9 .0

1 2 9 . 0 1 0 4

0 .0 1 0

1 0 .0 0

0 .0 0 1 4 1

0 .1 4 1

1 4 1 .0

1 4 1 . 0 1 0 4

O n c e t h e c e ll c o n s t a n t is
d e t e r m in e d , we c a n u s e it for
m e a s u r in g t h e r e s is t a n c e o r
con d u ctivity of a n y s olu tion . Th e
s et u p for th e m ea s u rem en t of th e
res is ta n ce is s h own in Fig. 3 .5 .
It con s is ts of two res is ta n ces R 3
a n d R 4 , a va ria ble res is ta n ce R 1 a n d
t h e con d u ct ivit y cell h a vin g t h e
u n k n o w n r e s is t a n c e R 2 . Th e
Wh ea t s t on e b r id ge is fed b y a n
os cilla tor O (a s ou r ce of a .c. p ower
in th e a u d io frequ en cy ra n ge 5 5 0
to 5 0 0 0 cycles p er s econ d ). P is a
s u ita b le d etector (a h ea d p h on e or
ot h er elect r on ic d evice) a n d t h e
b rid ge is b a la n ced wh en n o cu rr en t p a s s es th r ou gh th e d etector. Un d er
th es e con d ition s :
Un k n own res is ta n ce R 2 =

R1 R 4
R3

Table 3 .3
Co n d u c t i v i t y a n d
Mo lar c o n duc t ivit y
o f KCl s o lut io n s at
2 9 8 .1 5 K

Fig . 3 .5 : Arra n gem en t

f or m e a s u re m e n t of
re s is t a n c e
of
a
s o lu t io n
of
an
e le ctroly te .

(3 .1 9 )

Th es e d a ys , in exp en s ive con d u ctivity m eter s a r e a va ila b le wh ich

ca n d ir ectly r ea d th e con d u cta n ce or r es is ta n ce of th e s olu tion in th e
con du ctivity cell. On ce th e cell con s ta n t a n d th e res is ta n ce of th e s olu tion
in th e cell is d eterm in ed , th e con d u ctivity of th e s olu tion is given b y th e
equ a tion :

cell constant G*
=
R
R

(3 .2 0 )

Th e con d u ctivity of s olu tion s of d iffer en t electr olytes in th e s a m e

s olven t a n d a t a given tem p er a tu r e d iffer s d u e to ch a r ge a n d s ize of th e
ion s in wh ich th ey d is s ocia te, th e con cen tr a tion of ion s or ea s e with
wh ich th e ion s m ove u n d er a p oten tia l gr a d ien t. It, th er efor e, b ecom es
n eces s a ry to d efin e a p h ys ica lly m ore m ea n in gfu l qu a n tity ca lled m o lar
c o n duc t ivit y d en oted b y th e s ym b ol m (Gr eek , la m b d a ). It is r ela ted
to th e con d u ctivity of th e s olu tion b y th e equ a tion :
Mola r con d u ctivity = m =

(3 .2 1 )

In th e a bove equ a tion , if is expres s ed in S m 1 a n d th e con cen tra tion ,

77

E le c t r oc h e m is t r y

c in m ol m 3 th en th e u n its of m a re in S m 2 m ol1 . It m a y b e n oted

th a t:
1 m ol m 3 = 1 0 0 0 (L/ m 3 ) m ola r ity (m ol/ L), a n d h en ce

m (S m m ol ) =
2

(S m 1 )
1 0 0 0 L m 3 m ola r it y (m ol L1 )

If we u s e S cm 1 a s th e u n its for a n d m ol cm 3 , th e u n its of

con cen tra tion , th en th e u n its for m a re S cm 2 m ol1 . It ca n b e ca lcu la ted
b y u s in g th e equ a tion :
Lm (S cm 2 m ol 1 ) =

(S cm 1 ) 1 0 0 0 (cm 3 / L)
m ola r ity (m ol/ L)

Both typ e of u n its a r e u s ed in liter a tu r e a n d a r e r ela ted to ea ch

oth er b y th e equ a tion s :
1 S m 2 m ol1 = 1 0 4 S cm 2 m ol1 or
1 S cm 2 m ol1 =1 0 4 S m 2 m ol1 .

Example 3.4 Res is ta n ce of a con d u ctivity cell filled with 0 .1 m ol L1 KCl s olu tion

is 1 0 0 . If th e r es is ta n ce of th e s a m e cell wh en filled with 0 .0 2 m ol L1 KCl

s olu tion is 5 2 0 , ca lcu la te th e con d u ctivity a n d m ola r con d u ctivity of 0 .0 2 m ol
L1 KCl s olu tion . Th e con d u ctivity of 0 .1 m ol L1 KCl s olu tion is 1 .2 9 S/ m .

Solution Th e cell con s ta n t is given b y th e equ a tion :

Cell con s ta n t = G* = con d u ctivity r es is ta n ce
= 1 .2 9 S/ m 1 0 0 = 1 2 9 m 1 = 1 .2 9 cm 1
Con d u ctivity of 0 .0 2 m ol L1 KCl s olu tion = cell con s ta n t / r es is ta n ce
=

G*
1 2 9 m 1
=
= 0 .2 4 8 S m 1
R
520

Con cen tra tion = 0 .0 2 m ol L1

= 1 0 0 0 0 .0 2 m ol m 3
= 2 0 m ol m 3
Mola r con d u ctivity = m =

2 4 8 1 0 3 S m 1
2 0 m ol m 3

= 1 2 4 1 0 4 S m 2 m ol1
Alter n a tively, =
a n d m

C h e m is t r y

78

1 .2 9 cm 1
520

= 0 .2 4 8 1 0 2 S cm 1
= 1 0 0 0 cm 3 L1 m ola r ity1

0 .2 4 8 1 0 2 S cm 1 1 0 0 0 cm 3 L1
0 .0 2 m ol L1

= 1 2 4 S cm 2 m ol1
Th e electrica l r es is ta n ce of a colu m n of 0 .0 5 m ol L1 Na OH s olu tion Example 3.5
of d ia m eter 1 cm a n d len gth 5 0 cm is 5 .5 5 1 0 3 oh m . Ca lcu la te its r es is tivity,
con d u ctivity a n d m ola r con d u ctivity.

Solution

A = r2 = 3 .1 4 0 .5 2 cm 2 = 0 .7 8 5 cm 2 = 0 .7 8 5 1 0 4 m 2
l = 5 0 cm = 0 .5 m
R =

l
A

or

RA
5 .5 5 1 0 3 0 .7 8 5 cm 2
=
l
5 0 cm

= 8 7 .1 3 5 cm

1
1
Con d u ctivity = = = (
) S cm 1
8 7 .1 3 5
= 0 .0 1 1 4 8 S cm 1
Mola r con d u ctivit y , m =

1000
cm 3 L1
c

0 .0 1 1 4 8 S cm 1 1 0 0 0 cm 3 L1
0 .0 5 m ol L1

= 2 2 9 .6 S cm 2 m ol1
If we wa n t to ca lcu la te th e va lu es of d iffer en t qu a n tities in ter m s of m in s tea d of
cm ,

RA
l

5 .5 5 1 0 3 0 .7 8 5 1 0 4 m 2
=
0 .5 m
= 8 7 .1 3 5 1 0 2 m

100

m = 1 .1 4 8 S m 1
= 8 7 .1 3 5

and

m =

1 .1 4 8 S m 1
5 0 m ol m 3
= 2 2 9 .6 1 0 4 S m 2 m ol1 .

B o t h c o n d u c t ivit y a n d m o la r c o n d u c t ivit y c h a n g e w it h t h e
con cen t r a t ion of t h e elect r olyt e. Con d u ct ivit y a lwa ys d ecr ea s es wit h
d ecr ea s e in con cen t r a t ion b ot h , for wea k a n d s t r on g elect r olyt es .
Th is ca n b e exp la in ed b y t h e fa ct t h a t t h e n u m b er of ion s p er u n it
volu m e t h a t ca r r y t h e cu r r en t in a s olu t ion d ecr ea s es on d ilu t ion .
Th e con d u ct ivit y of a s olu t ion a t a n y given con cen t r a t ion is t h e
c on d u c t a n c e of on e u n it volu m e of s olu t ion k e p t b e t we e n t wo

3 .4 .2 Variat io n o f
Co n duc t ivit y
an d Mo lar
Co n duc t ivit y
wit h
Concentration
79

E le c t r oc h e m is t r y

p la t in u m elect r od es wit h u n it a r ea of cr os s s ect ion a n d a t a d is t a n ce

of u n it len gt h . Th is is clea r fr om t h e equ a t ion :
G =

A
l

= (b oth A a n d l a r e u n ity in th eir a p p r op r ia te u n its in

m or cm )
Mola r con d u ctivity of a s olu tion a t a given con cen tr a tion is th e
con d u ct a n ce of t h e volu m e V of s olu t ion con t a in in g on e m ole of
electrolyte k ep t b etween two electrod es with a rea of cros s s ection A a n d
d is ta n ce of u n it len gth . Th er efor e,
A
m =
=
l
Sin ce l = 1 a n d A = V ( volu m e con t a in in g 1 m ole of elect r olyt e)
m = V
(3 .2 2 )
Mola r con d u ct ivit y in cr ea s es wit h d ecr ea s e in con cen t r a t ion . Th is
is b eca u s e t h e t ot a l volu m e, V, of s olu t ion con t a in in g on e m ole of
elect r olyt e a ls o in cr ea s es . It h a s b een fou n d t h a t d ecr ea s e in on
d ilu t ion of a s olu t ion is m or e t h a n com p en s a t ed b y in cr ea s e in it s
volu m e. Ph ys ica lly, it m ea n s t h a t a t a given con cen t r a t ion , m ca n b e
d efin ed a s t h e con d u ct a n ce of t h e electr olytic s olu tion k ep t b et ween
t h e elect r od es of a con d u ct ivit y cell a t u n it d is t a n ce b u t h a vin g a r ea
of cr os s s ect ion la r ge en ou gh t o a ccom m od a t e s u fficien t volu m e of
s olu tion th a t con ta in s on e m ole of th e electr olyte. Wh en con cen tr a tion
a p p r oa ch es zer o, t h e m ola r con d u ct ivit y is k n own a s lim it in g m o lar
c o n du c t iv it y a n d is r ep r es en t ed b y t h e s ym b ol m. Th e va r ia t ion in
m wit h con cen t r a t ion is d iffer en t (Fig. 3 .6 ) for s t r on g a n d wea k
electr olytes .
For s tr on g electr olytes , in crea s es s lowly with d ilu tion a n d ca n b e
rep res en ted b y th e equ a tion :
m = m A c
(3 .2 3 )
It ca n b e s een
th a t if we p lot (Fig.
3 . 1 2 ) m a ga in s t
c 1 / 2 , we ob t a in a
s t r a igh t lin e wit h
in ter cep t equ a l to
m a n d s lop e equ a l
to A. Th e va lu e of
th e con s ta n t A for
a given s olven t a n d
t em p er a t u r e
d ep en d s on t h e
t yp e of elect r olyt e
i.e., th e ch a rges on
t h e c a t io n a n d
a n ion p rod u ced on
th e d is s ocia tion of
t h e elect r olyt e in
C h e m is t r y

80

St ron g Ele c t rolyt e s

Fig . 3 .6 : Mola r
con d u ctivity vers u s
c for a cetic a cid
(w e a k e le ctroly te )
a n d pota s s iu m
ch lorid e (s tron g
electroly te) in
a qu e ou s s olu tion s .

th e s olu tion . Th u s , Na Cl, Ca Cl2 , MgSO 4 a re k n own a s 1 -1 , 2 -1 a n d 2 2 electr olytes r es p ectively. All electr olytes of a p a r ticu la r typ e h a ve th e
s a m e va lu e for A.

Th e m ola r con d u ctivity of KCl s olu tion s a t d iffer en t con cen tr a tion s a t Example 3.6
2 9 8 K a re given b elow:
m / S c m 2 m o l 1
c / m o l L1
0 .0 0 0 1 9 8
1 4 8 .6 1
0 .0 0 0 3 0 9
1 4 8 .2 9
0 .0 0 0 5 2 1
1 4 7 .8 1
0 .0 0 0 9 8 9
1 4 7 .0 9
Sh ow th a t a p lot b etween m a n d c1 / 2 is a s tr a igh t lin e. Deter m in e th e va lu es
of m a n d A for KCl.
Ta k in g th e s qu a r e r oot of con cen tr a tion we ob ta in :
Solution
m / S c m 2 m o l 1
c 1 / 2 / (m o l L1 )1 / 2
0 .0 1 4 0 7
1 4 8 .6 1
0 .0 1 7 5 8
1 4 8 .2 9
0 .0 2 2 8 3
1 4 7 .8 1
0 .0 3 1 4 5
1 4 7 .0 9
A p lot of m ( y-a xis ) a n d c 1 / 2 (x-a xis ) is s h own in (Fig. 3 .7 ).
It ca n b e s een th a t it is n ea r ly a s tr a igh t lin e. Fr om th e in ter cep t (c1 / 2 = 0 ),
we fin d th a t m= 1 5 0 .0 S cm 2 m ol1 a n d
A = s lop e = 8 7 .4 6 S cm 2 m ol1 / (m ol/ L1 )1 / 2 .

Fig . 3 .7 : Va ria tion

of m a ga in s t c .

81

E le c t r oc h e m is t r y

Koh lra u s ch exa m in ed m va lu es for a n u m b er of s tr on g electr olytes

a n d ob s er ved cer ta in r egu la r ities . He n oted th a t th e d iffer en ce in m of
th e electr olytes Na X a n d KX for a n y X is n ea r ly con s ta n t. For exa m p le
a t 2 9 8 K:
m (KCl) m (Na Cl)= m (KBr) m (Na Br)
= m (KI) m (Na I) 2 3 .4 S cm 2 m ol1
a n d s im ila rly it wa s fou n d th a t
m (Na Br) m (Na Cl)= m (KBr) m (KCl) 1 .8 S cm 2 m ol 1
On th e b a s is of th e a b ove ob s erva tion s h e en u n cia ted Ko h lraus c h
law o f in de pe n de n t m igrat io n o f io n s . Th e la w s ta tes th a t lim itin g
m ola r con d u ctivity of a n electroly te ca n be repres en ted a s th e s u m of
th e in d ivid u a l con tribu tion s of th e a n ion a n d ca tion of th e electroly te.
Th u s , if Na + and Cl a re lim itin g m ola r con d u ctivity of th e s od iu m a n d
ch loride ion s res pectively, th en th e lim itin g m ola r con du ctivity for s odiu m
ch lorid e is given b y th e equ a tion :
(3 .2 4 )
m (Na Cl) = 0 Na + + 0 Cl
In gen er a l, if a n electr olyte on d is s ocia tion gives v + ca tion s a n d v
a n ion s th en its lim itin g m ola r con d u ctivity is given b y:
(3 .2 5 )
m = + 0 + + 0
Here, 0+ a n d 0 a r e th e lim itin g m ola r con d u ctivities of th e ca tion
a n d a n ion r es p ectively. Th e va lu es of 0 for s om e ca tion s a n d a n ion s a t
2 9 8 K a re given in Ta b le 3 .4 .
Io n

0 / (S c m 2 m o l 1 )

Io n

0 / (S c m 2 m o l 1 )

H+

3 4 9 .6

OH

1 9 9 .1

Na

K+

5 0 .1

Cl

7 6 .3

7 3 .5

Br

7 8 .1
4 0 .9

Ca 2+

1 1 9 .0

CH 3 COO

Mg 2 +

1 0 6 .0

SO 4

1 6 0 .0

Wea k electr olytes lik e a cetic a cid h a ve lower d egr ee of d is s ocia tion a t
h igh er con cen tra tion s a n d h en ce for s u ch electrolytes , th e ch a n ge in m
with d ilu tion is d u e to in cr ea s e in th e d egr ee of d is s ocia tion a n d
con s equ en tly th e n u m ber of ion s in tota l volu m e of s olu tion th a t con ta in s
1 m ol of electr olyte. In s u ch ca s es m in cr ea s es s teep ly (Fig. 3 .1 2 ) on
d ilu tion , es p ecia lly n ea r lower con cen tr a tion s . Th er efor e, m ca n n ot b e
ob ta in ed b y extra p ola tion of m to zero con cen tra tion . At in fin ite d ilu tion
(i.e., con cen tr a tion c zer o) electr olyte d is s ocia tes com p letely ( =1 ),
b u t a t s u ch low con cen tr a tion th e con d u ctivity of th e s olu tion is s o low
th a t it ca n n ot be m ea s u red a ccu ra tely. Th erefore, m for wea k electrolytes
is ob ta in ed b y u s in g Koh lr a u s ch la w of in d ep en d en t m igra tion of ion s
(E xa m p le 3 .8 ). At a n y con cen tr a tion c, if is th e d egr ee of d is s ocia tion
th en it ca n b e a p p r oxim a ted to th e r a tio of m ola r con d u ctivity m a t th e
con cen tr a tion c to lim itin g m ola r con d u ctivity, m. Th u s we h a ve:
C h e m is t r y

82

Table 3 .4
Li m i t i n g m o l a r
c o n d u c t i v i t y fo r
s om e ions in
wat e r at 2 9 8 K

We ak e le c t ro ly t e s

m
m

(3 .2 6 )

Bu t we k n ow th a t for a wea k electr olyte lik e a cetic a cid (Cla s s XI,

Un it 7 ),
K

c 2
=
(1 )

m 2

c m2
c m2
=

m m ( m m
1
m

(3 .2 7 )
Applic at io n s o f
Ko h lraus c h law

Us in g Koh lra u s ch la w of in d ep en d en t m igra tion of ion s , it is p os s ib le to

ca lcu la te m for a n y electr olyte fr om th e o of in d ivid u a l ion s . Mor eover,
for wea k electrolytes lik e a cetic a cid it is p os s ib le to d eterm in e th e va lu e
of its d is s ocia tion con s ta n t on ce we k n ow th e m a n d m a t a given
con cen tra tion c.

Ca lcu la te m for Ca Cl2 a n d MgSO 4 fr om th e d a ta given in Ta b le 3 .4 .

Example 3.7
Solution

We k n ow fr om Koh lra u s ch la w th a t

m (Ca Cl ) = Ca + 2 Cl = 1 1 9 .0 S cm 2 m ol1 + 2 (7 6 .3 ) S cm 2 m ol1

2+

= (1 1 9 .0 + 1 5 2 .6 ) S cm 2 m ol1
= 2 7 1 .6 S cm 2 m ol1

m ( MgSO ) = Mg + S O
2+

2
4

= 1 0 6 .0 S cm 2 m ol1 + 1 6 0 .0 S cm 2 m ol1

= 2 6 6 S cm 2 m ol1 .
m for Na Cl, HCl a n d Na Ac a re 1 2 6 .4 , 4 2 5 .9 a n d 9 1 .0 S cm 2 m ol1
r es p ectively. Ca lcu la te o for HAc.

m ( HAc ) = H + Ac = H + Cl + Ac + Na Cl Na
+

Example 3.8
Solution

= m ( HCl ) + m ( Na Ac ) m ( Na Cl )
= (4 2 5 .9 + 9 1 .0 1 2 6 .4 ) S cm 2 mol 1
= 3 9 0 .5 S cm 2 m ol1 .

Example 3.9
Th e con d u ctivity of 0 .0 0 1 0 2 8 m ol L1 a cetic a cid is 4 .9 5 1 0 5 S
1

cm . Ca lcu la te its d is s ocia tion con s ta n t if m for a cetic a cid is 3 9 0 .5 S cm 2 m ol1 .

m

Solution

4 .9 5 1 0 5 S cm 1 1 0 0 0 cm 3

= 4 8 .1 5 S cm 2 m ol 1
0 .0 0 1 0 2 8 m ol L1
L

m 48 .15 S cm 2 m ol 1
=
= 0 .123 3
m 3 9 0 .5 S cm 2 m ol 1

K=

0 .001028 molL1 (0.1233)2

c2
1
=
= 1.78 10 5 m ol L
1

1 0.1233
( )

83

E le c t r oc h e m is t r y

Intext Questions
3 .7 Wh y d oes th e con d u ctivity of a s olu tion d ecr ea s e with d ilu tion ?
3 .8 S u gges t a wa y to d eter m in e th e va lu e of wa ter.
m

3 .9 Th e m ola r con d u ctivity of 0 .0 2 5 m ol L1 m eth a n oic a cid is 4 6 .1 S cm 2 m ol1 .

Ca lcu la te its d egr ee of d is s ocia tion a n d d is s ocia tion con s ta n t. Given 0(H +)
= 3 4 9 .6 S cm 2 m ol 1 a n d 0(HCOO ) = 5 4 .6 S cm 2 m ol1

3 . 5 Electrolytic
Cells and
Electrolysis

In a n e le c t ro ly t ic c e ll extern a l s ou rce of volta ge is u s ed to b rin g a b ou t

a ch em ica l rea ction . Th e electroch em ica l processes a re of grea t im porta n ce
in th e laboratory an d th e ch em ical in du stry. On e of th e sim plest electrolytic
cell con s is ts of two cop p er s trip s d ip p in g in a n a qu eou s s olu tion of
cop p er s u lp h a te. If a DC volta ge is a p p lied to th e two electrod es , th en
Cu 2+ ion s dis ch a rge a t th e ca th ode (n ega tively ch a rged) a n d th e followin g
rea ction ta k es p la ce:
(3 .2 8 )
Cu 2 +(a q) + 2 e Cu (s )
Cop p er m eta l is d ep os ited on th e ca th od e. At th e a n od e, cop p er is
con ver ted in to Cu 2 + ion s b y th e r ea ction :
(3 .2 9 )
Cu (s ) Cu 2 +(s ) + 2 e
Th u s c op p e r is d is s olve d (oxid is e d ) a t a n od e a n d d e p os it e d
(r ed u ced ) a t ca t h od e. Th is is t h e b a s is for a n in d u s t r ia l p r oces s in
wh ich im p u r e cop p er is con ver t ed in t o cop p er of h igh p u r it y. Th e
im p u r e cop p er is m a d e a n a n od e t h a t d is s olves on p a s s in g cu r r en t
a n d p u r e cop p er is d ep os ited a t th e ca th od e. Ma n y m eta ls lik e Na , Mg,
Al, et c. a r e p r od u ced on la r ge s ca le b y elect r och em ica l r ed u ct ion of
t h eir r es p ect ive ca t ion s wh er e n o s u it a b le ch em ica l r ed u cin g a gen t s
a r e a va ila b le for t h is p u r p os e.
Sod iu m a n d m a gn es iu m m eta ls a re p rod u ced b y th e electrolys is of
th eir fu s ed ch lorid es a n d a lu m in iu m is p rod u ced (Cla s s XII, Un it 6 ) b y
electr olys is of a lu m in iu m oxid e in p r es en ce of cr yolite.

Quan t it at ive
As pe c t s o f
Ele c t ro ly s is

Mic h ae l Faraday wa s th e fir s t s cien tis t wh o d es cr ib ed th e qu a n tita tive

a s p ects of electrolys is . Now Fa ra d a ys la ws a ls o flow from wh a t h a s
b een d is cu s s ed ea r lier.

Faraday s Laws
o f Ele c t ro ly s is

After h is exten s ive in ves tiga tion s on electr olys is of s olu tion s a n d m elts
of electr olytes , Fa ra d a y p u b lis h ed h is res u lts d u rin g 1 8 3 3 -3 4 in th e
form of th e followin g well k n own Fa ra d a ys two la ws of electrolys is :

1 . Fir s t La w

Th e a m ou n t of ch em ica l r ea ction wh ich occu r s a t a n y electr od e d u r in g

electr olys is b y a cu r r en t is p r op or tion a l to th e qu a n tity of electr icity
p a s s ed th r ou gh th e electr olyte (s olu tion or m elt).

2 . S e c on d La w

Th e a m ou n ts of d iffer en t s u b s ta n ces lib er a ted b y th e s a m e qu a n tity of

electr icity p a s s in g th r ou gh th e electr olytic s olu tion a r e p r op or tion a l to
th eir ch em ica l equ iva len t weigh ts (Atom ic Ma s s of Meta l Nu m b er of
electr on s r equ ir ed to r ed u ce th e ca tion ).

C h e m is t r y

84

Th ere were n o con s ta n t cu rren t s ou rces a va ila b le d u rin g Fa ra d a ys

tim es . Th e gen er a l p r a ctice wa s to p u t a cou lom eter (a s ta n d a r d
electrolytic cell) for d eterm in in g th e qu a n tity of electricity p a s s ed from
th e a m ou n t of m eta l (gen era lly s ilver or cop p er) d ep os ited or con s u m ed .
However, cou lom eters a r e n ow ob s olete a n d we n ow h a ve con s ta n t
cu r r en t (I) s ou r ces a va ila b le a n d th e qu a n tity of electr icity Q, p a s s ed
is given b y
Q = It
Q is in colou m b s wh en I is in a m p ere a n d t is in s econ d .
Th e a m ou n t of electr icity (or ch a r ge) r equ ir ed for oxid a tion or
r ed u ction d ep en d s on th e s toich iom etr y of th e electr od e r ea ction . For
exa m p le, in th e r ea ction :
Ag +(a q) + e Ag(s )
(3 .3 0 )
On e m ole of th e electr on is r equ ir ed for th e r ed u ction of on e m ole
of s ilver ion s . We k n ow th a t ch a r ge on on e electr on is equ a l to 1 .6 0 2 1
1 0 1 9 C. Th er efor e, th e ch a r ge on on e m ole of electr on s is equ a l to:
C = 6 .0 2 1 0 2 3 m ol 1 1 .6 0 2 1 1 0 1 9
N A 1 .6 0 2 1 1 0 1 9
C = 9 6 4 8 7 C m ol1
Th is qu a n tity of electr icity is ca lled Faraday a n d is rep res en ted b y
th e s ym b ol F.
For a p p roxim a te ca lcu la tion s we u s e 1 F 9 6 5 0 0 C m ol1 .
For th e electr od e r ea ction s :
(3 .3 1 )
Mg 2+(l) + 2 e Mg(s )
3+

(3 .3 2 )
Al (l) + 3 e Al(s )
It is ob viou s th a t on e m ole of Mg 2 + a n d Al3 + r equ ir e 2 m ol of
electr on s (2 F) a n d 3 m ol of electr on s (3 F) r es p ectively. Th e ch a r ge
p a s s ed th r ou gh th e electr olytic cell d u r in g electr olys is is equ a l to th e
p r od u ct of cu r r en t in a m p er es a n d tim e in s econ d s . In com m er cia l
p rod u ction of m eta ls , cu rren t a s h igh a s 5 0 ,0 0 0 a m p eres a re u s ed
th a t a m ou n ts to a b ou t 0 .5 1 8 F p er s econ d .

Example 3.10

A s olu tion of Cu SO 4 is electr olys ed for 1 0 m in u tes with a cu r r en t of

1 .5 a m p eres . Wh a t is th e m a s s of cop p er d ep os ited a t th e ca th od e?

t = 6 0 0 s ch a rge = cu rren t tim e = 1 .5 A 6 0 0 s = 9 0 0 C

Solution
Accor d in g to th e r ea ction :
Cu 2+(a q) + 2 e = Cu (s )
We r equ ir e 2 F or 2 9 6 4 8 7 C to d ep os it 1 m ol or 6 3 g of Cu .
For 9 0 0 C, th e m a s s of Cu d ep os ited = (6 3 g m ol1 9 0 0 C)/ (2 9 6 4 8 7 C m ol1 )
= 0 .2 9 3 8 g.
Pr od u ct s of elect r olys is d ep en d on t h e n a t u r e of m a t er ia l b ein g
electr olys ed a n d th e typ e of electr od es b ein g u s ed . If th e electr od e is
in er t (e.g., p la tin u m or gold ), it d oes n ot p a r ticip a te in th e ch em ica l
r ea ction a n d a cts on ly a s s ou r ce or s in k for electr on s . On th e oth er
h a n d , if th e electrod e is rea ctive, it p a rticip a tes in th e electrod e rea ction .
Th u s , th e p rod u cts of electrolys is m a y b e d ifferen t for rea ctive a n d in ert

3 .5 .1 Pro duc t s o f
Ele c t ro ly s is

85

E le c t r oc h e m is t r y

electrod es .Th e p rod u cts of electrolys is d ep en d on th e d ifferen t oxid is in g

a n d r ed u cin g s p ecies p r es en t in th e electr olytic cell a n d th eir s ta n d a r d
electr od e p oten tia ls . Mor eover, s om e of th e electr och em ica l p r oces s es
a lth ou gh fea s ib le, a r e s o s low k in etica lly th a t a t lower volta ges th es e
d on t s eem to ta k e p la ce a n d extr a p oten tia l (ca lled overpoten tia l) h a s
to b e a p p lied , wh ich m a k es s u ch p r oces s m or e d ifficu lt to occu r.
For exa m p le, if we u s e m olten Na Cl, th e p r od u cts of electr olys is a r e
s od iu m m eta l a n d Cl2 ga s . Her e we h a ve on ly on e ca tion (Na +) wh ich is
red u ced a t th e ca th od e (Na + + e Na ) a n d on e a n ion (Cl) wh ich is
oxidis ed at th e an ode (Cl Cl2 +e ) . Du r in g th e electr olys is of a qu eou s
s od iu m ch lorid e s olu tion , th e p rod u cts a re Na OH, Cl2 a n d H 2 . In th is
ca s e b es id es Na + a n d Cl ion s we a ls o h a ve H + a n d OH ion s a lon g with
th e s olven t m olecu les , H 2 O.
At th e ca th od e th er e is com p etition b etween th e followin g r ed u ction
rea ction s :
Na + (a q) + e Na (s )

E ( cell ) = 2 .7 1 V

H + (a q) + e H 2 (g)

E ( cell ) = 0 .0 0 V

Th e r ea ction with h igh er va lu e of E is p referred a n d , th erefore, th e

r ea ction a t th e ca th od e d u r in g electr olys is is :
(3 .3 3 )
H + (a q) + e H 2 (g)
+
b u t H (a q) is p rod u ced b y th e d is s ocia tion of H 2 O, i.e.,
(3 .3 4 )
H 2 O (l ) H + (a q) + OH (a q)
Th erefore, th e n et rea ction a t th e ca th od e m a y b e written a s th e s u m
of (3 .3 3 ) a n d (3 .3 4 ) a n d we h a ve
(3 .3 5 )
H 2 O (l ) + e H 2 (g) + OH
At th e a n od e th e followin g oxid a tion r ea ction s a r e p os s ib le:
Cl (aq) Cl2 (g) + e
2H 2 O (l ) O 2 (g) + 4 H +(a q) + 4 e

E ( cell ) = 1.36 V
V

E ( cell ) = 1 .2 3 V
V

(3 .3 6 )
(3 .3 7 )

Th e rea ction a t a n od e with lower va lu e of E is p referred a n d

th er efor e, wa ter s h ou ld get oxid is ed in p r efer en ce to Cl (a q). However,
on a ccou n t of overp oten tia l of oxygen , rea ction (3 .3 6 ) is p referred . Th u s ,
th e n et r ea ction s m a y b e s u m m a r is ed a s :
H O

2
Na + (a q) + Cl (a q)
Na Cl (a q)
Ca th od e:
H 2 O(l ) + e H 2 (g) + OH (a q)
An od e:
Cl (a q) Cl2 (g) + e
Net rea ction :
Na Cl(a q) + H 2 O(l ) Na +(a q) + OH (a q) + H 2 (g) + Cl2 (g)
Th e s ta n d a rd electrod e p oten tia ls a re rep la ced b y electrod e p oten tia ls
given b y Nern s t equ a tion (Eq. 3 .8 ) to ta k e in to a ccou n t th e con cen tra tion
effects . Du rin g th e electrolys is of s u lp h u ric a cid , th e followin g p roces s es
a r e p os s ib le a t th e a n od e:

2H 2 O(l ) O 2 (g) + 4 H +(a q) + 4 e

C h e m is t r y

86

E ( cell ) = +1 .2 3 V,
V

(3 .3 8 )

2 SO 4 2 (a q) S 2 O 8 2 (a q) + 2 e

E ( cell ) = 1 .9 6 V
V

(3 .3 9 )

For d ilu te s u lp h u r ic a cid , r ea ction (3 .3 8 ) is p r efer r ed b u t a t h igh er

con cen tr a tion s of H 2 SO 4 p roces s , rea ction (3 .3 9 ) is p referred .

Intext Questions
3 .1 0 If a cu r r en t of 0 .5 a m p er e flows th r ou gh a m eta llic wir e for 2 h ou r s , th en h ow
m a n y electr on s wou ld flow th r ou gh th e wir e?
3 .1 1 S u gges t a lis t of m eta ls th a t a r e extr a cted electr olytica lly.
3 .1 2 Con s id er th e r ea ction :
Cr 2 O 7 2 + 1 4 H + + 6 e 2 Cr 3 + + 8 H 2 O
Wh a t is th e qu a n tity of electr icity in cou lom b s n eed ed to r ed u ce 1 m ol of
Cr 2 O 7 2 ?
An y b a tter y (a ctu a lly it m a y h a ve on e or m or e th a n on e cell con n ected
in s er ies ) or cell th a t we u s e a s a s ou r ce of electr ica l en er gy is b a s ica lly
a ga lva n ic cell wh er e th e ch em ica l en er gy of th e r ed ox r ea ction is
con verted in to electrica l en er gy. However, for a b a ttery to b e of p ra ctica l
u s e it s h ou ld b e r ea s on a b ly ligh t, com p a ct a n d its volta ge s h ou ld n ot
va ry a p p recia b ly d u rin g its u s e. Th ere a re m a in ly two typ es of b a tteries .

3.6 Batteries

In t h e p r im a r y b a t t er ies , t h e r ea ct ion occu r s on ly on ce a n d a ft er u s e 3 .6 .1 Prim ary

over a p er iod of t im e b a t t er y b ecom es d ea d a n d ca n n ot b e r eu s ed
Bat t e rie s
a ga in . Th e m os t fa m ilia r exa m p le of t h is t yp e is t h e d r y cell (k n own a s
Lecla n ch e cell a fter its d is coverer) wh ich is u s ed com m on ly
in ou r t r a n s is t or s a n d clock s . Th e cell con s is t s of a zin c
con t a in er t h a t a ls o a ct s a s a n od e a n d t h e ca t h od e is a
ca r b on (gr a p h ite) r od s u r r ou n d ed b y p owd er ed m a n ga n es e
d ioxid e a n d ca r b on (Fig.3 .8 ). Th e s p a ce b et ween t h e
elect r od es is filled b y a m ois t p a s t e of a m m on iu m ch lorid e
(NH 4 Cl) a n d zin c ch lor id e (Zn Cl 2 ). Th e elect r od e r ea ct ion s
a r e com p lex, b u t t h ey ca n b e wr it t en a p p r oxim a t ely a s
follows :
An od e:
Zn (s ) Zn 2 + + 2 e
Ca th od e:
Mn O 2 + NH 4 ++ e Mn O(OH) + NH 3
In th e r ea ction a t ca th od e, m a n ga n es e is r ed u ced fr om
th e + 4 oxid a tion s ta te to th e +3 s ta te. Am m on ia p r od u ced
in th e rea ction form s a com p lex with Zn 2 + to give [Zn
(NH 3 )4 ]2+. Th e cell h a s a p oten tia l of n ea r ly 1 .5 V.
Mer cu r y cell, (Fig. 3 .9 ) s u ita b le for low cu r r en t d evices
lik e h ea r in g a id s , wa tch es , etc. con s is ts of zin c m er cu r y
a m a lga m a s a n od e a n d a p a s te of HgO a n d ca rb on a s th e
ca th od e. Th e electr olyte is a p a s te of KOH a n d Zn O. Th e
Fig . 3 .8 : A co m m e rcia l d ry ce ll
electr od e r ea ction s for th e cell a r e given b elow:
c o n s is t s o f a g ra p h it e (c a rb o n )

An ode:
Zn (Hg) + 2OH Zn O(s) + H 2 O + 2e
ca t h od e in a z in c con t a in e r; t h e
Ca th od e:
HgO + H 2 O + 2 e Hg(l ) + 2 OH
la tter a cts a s th e a n od e.
87

E le c t r oc h e m is t r y

Th e over a ll r ea ction is r ep r es en ted b y

Zn (Hg) + HgO(s ) Zn O(s ) + Hg(l )
Th e cell p oten tia l is a p p roxim a tely 1 .3 5 V
a n d rem a in s con s ta n t du rin g its life a s th e overa ll
r ea ction d oes n ot in volve a n y ion in s olu tion
wh os e con cen tr a tion ca n ch a n ge d u r in g its life
tim e.
3 .6 .2 Se c o n dary Bat t e rie s
A s econ d a r y cell a fter u s e ca n b e r ech a r ged b y
p a s s in g cu r r en t t h r ou gh it in t h e op p os it e
d ir ection s o th a t it ca n b e u s ed a ga in . A good
s econ d a ry cell ca n u n d ergo a la rge n u m b er of
Fig . 3 .9 : Com m on ly u s ed m ercu ry cell.
d is ch a r gin g a n d ch a r gin g cycles . Th e m os t
Th e re d u cin g a g e n t is z in c a n d t h e
im p or ta n t s econ d a r y cell is th e lea d s tor a ge
oxid is in g a gen t is m ercu ry (II) oxid e.
b a t t e r y (F ig . 3 . 1 0 ) c o m m o n ly u s e d in
a u tom ob iles a n d in ver tor s . It con s is ts of a lea d a n od e a n d a gr id of
lea d p a ck ed with lea d d ioxid e (Pb O 2 ) a s ca th od e. A 3 8 % s olu tion of
s u lp h u r ic a cid is u s ed a s a n electr olyte.
Th e cell r ea ction s wh en th e b a tter y is in u s e a r e given b elow:
An od e: Pb (s ) + SO 4 2(a q) Pb SO 4 (s ) + 2 e
Ca th od e: Pb O 2 (s ) + SO 4 2(a q) + 4 H +(a q) + 2 e Pb SO 4 (s ) + 2 H 2 O (l )
i.e., over a ll cell r ea ction con s is tin g of ca th od e a n d a n od e r ea ction s
is:
Pb (s )+Pb O 2 (s )+2 H 2 SO 4 (a q) 2 Pb SO 4 (s ) + 2 H 2 O(l)
On ch a r gin g th e b a tter y th e r ea ction is r ever s ed a n d Pb SO 4 (s ) on
a n od e a n d ca th od e is con verted in to Pb a n d Pb O 2 , r es p ectively.

Fig . 3 .1 0 : Th e Lea d s tora ge ba ttery .

C h e m is t r y

88

A n o t h e r
im p or ta n t s econ d a r y
c e ll is t h e n ic k e lc a d m iu m c e ll (F ig.
3 . 1 1 ) w h ic h h a s
lon ger life t h a n t h e
lea d s tor a ge cell b u t
m o r e e x p e n s ive t o
m a n u fa c t u r e .
We
s h a ll n o t g o in t o
d eta ils of work in g of
t h e c e ll a n d t h e
e le c t r o d e r e a c t io n s
d u rin g ch a rgin g a n d
d is c h a r g in g .
Th e
o ve r a ll
r e a c t io n
d u rin g d is ch a rge is :
Cd (s )+2 Ni(OH)3 (s ) Cd O (s ) +2 Ni(OH)2 (s ) +H 2 O(l )

Fi g . 3 .1 1 : A rech a rgea ble

n ick e l-ca d m iu m ce ll in a
je lly roll a rra n ge m e n t a n d
s e p a ra t e d b y a la y e r
s oa k ed in m ois t s od iu m or
p ota s s iu m h y d roxid e.

Prod u ction of electricity b y th erm a l p la n ts is n ot a very efficien t m eth od 3.7 Fuel

a n d is a m a jor s ou r ce of p ollu tion . In s u ch p la n ts , th e ch em ica l en er gy
(h ea t of com b u s tion ) of fos s il fu els (coa l,
ga s or oil) is fir s t u s ed for con ver tin g
wa ter in to h igh p r es s u r e s tea m . Th is is
th en u s ed to ru n a tu rb in e to p rod u ce
electr icity. We k n ow th a t a ga lva n ic cell
d ir ectly con ver ts ch em ica l en er gy in to
electricity a n d is h igh ly efficien t. It is n ow
p os s ib le to m a k e s u ch cells in wh ich
r ea cta n ts a r e fed con tin u ou s ly to th e
elect r od es a n d p r od u ct s a r e r em oved
c o n t in u o u s ly fr o m t h e e le c t r o ly t e
com p a r t m en t . Ga lva n ic cells t h a t a r e
d e s ign e d t o c o n ve r t t h e e n e r gy o f
c om b u s t ion of fu e ls lik e h yd r oge n ,
m et h a n e, m et h a n ol, et c. d ir ect ly in t o
electr ica l en er gy a r e ca lled fue l c e lls .
Fig . 3 .1 2 : Fu el cell u s in g H 2 a n d
On e of th e m os t s u cces s fu l fu el cells
O 2 prod u ces electricity .
u s es th e rea ction of h ydrogen with oxygen
to form water (Fig. 3.12 ). Th e cell was u sed
for providin g electrica l power in th e Apollo s pa ce progra m m e. Th e wa ter
va pou rs produ ced du rin g th e rea ction were con den s ed a n d a dded to th e
drin kin g wa ter s u pply for th e a s tron a u ts . In th e cell, h ydrogen a n d oxygen
a re bu bbled th rou gh porou s ca rbon electrodes in to con cen tra ted a qu eou s
s odiu m h ydroxide s olu tion . Ca ta lys ts like fin ely divided pla tin u m or
pa lla diu m m eta l a re in corpora ted in to th e electrodes for in crea sin g th e ra te
of electrode rea ction s . Th e electrode rea ction s a re given below:
Ca th od e:
O 2 (g) + 2 H 2 O(l ) + 4 e 4 OH (a q)
An od e: 2H 2 (g) + 4 OH (a q) 4 H 2 O(l) + 4 e
89

Cells

E le c t r oc h e m is t r y

Overa ll rea ction b ein g:

2H 2 (g) + O 2 (g) 2 H 2 O(l )
Th e cell r u n s con tin u ou s ly a s lon g a s th e r ea cta n ts a r e s u p p lied .
Fu el cells p rod u ce electricity with a n efficien cy of a b ou t 7 0 % com p a red
to th erm a l p la n ts wh os e efficien cy is a b ou t 4 0 %. Th ere h a s b een
tr em en d ou s p r ogr es s in th e d evelop m en t of n ew electr od e m a ter ia ls ,
b etter ca ta lys ts a n d electrolytes for in crea s in g th e efficien cy of fu el cells .
Th es e h a ve b een u s ed in a u tom ob iles on a n exp erim en ta l b a s is . Fu el
cells a r e p ollu tion fr ee a n d in view of th eir fu tu r e im p or ta n ce, a va r iety
of fu el cells h a ve b een fa b r ica ted a n d tr ied .

3.8 Corrosion

Cor r os ion s lowly coa ts th e s u r fa ces of m eta llic ob jects with oxid es or
oth er s a lts of th e m eta l. Th e r u s tin g of ir on , ta r n is h in g of s ilver,
d evelop m en t of green coa tin g on cop p er a n d b ron ze a re s om e of th e
exa m ples of corros ion . It ca u s es en orm ou s da m a ge to bu ildin gs , bridges ,
s h ip s a n d to a ll ob jects m a d e of m eta ls es p ecia lly th a t of ir on . We los e
cr or es of r u p ees ever y yea r on a ccou n t of cor r os ion .
In cor r os ion , a m eta l is oxid is ed b y los s of electr on s to oxygen a n d
form a tion of oxid es . Corros ion of iron (com m on ly k n own a s ru s tin g)
occu rs in p r es en ce of wa ter a n d a ir. Th e ch em is try of corr os ion is qu ite
com p lex b u t it m a y b e con s id er ed es s en tia lly a s a n electr och em ica l
p h en om en on . At a p a rticu la r s p ot (Fig. 3 .1 3 ) of a n ob ject m a d e of iron ,
oxid a tion ta k es p la ce a n d th a t s p ot b eh a ves a s a n od e a n d we ca n write
th e r ea ction
An od e: 2 Fe (s ) 2 Fe 2 + + 4 e

E V(Fe 2 +/ Fe) = 0 .4 4 V

Electron s relea s ed
a t a n od ic s p ot m ove
t h r o u gh t h e m e t a l
a n d go t o a n o t h e r
s pot on th e m eta l a n d
r e d u c e o x y g e n in
p res en ce of H + (wh ich
is b e lie ve d t o b e
a va ila b le from H 2 CO 3
2+

fo r m e d
du e
to
Oxid a tion : Fe (s ) Fe (a q) +2 e
+

d is s olu tion of ca rb on
Red u ction : O 2 (g) + 4 H (a q) +4 e 2 H 2 O(l)
At om os p h er ic
d ioxid e from a ir in to
oxid a tion : 2 Fe 2+(a q) + 2 H 2 O(l) + O 2 (g) Fe 2 O 3 (s ) + 4 H +(a q)
wa ter. Hyd r ogen ion
in wa ter m a y a ls o b e
Fig . 3 .1 3 : Corros ion of iron in a tm os ph ere.
a va ila b le d u e t o
d is s olu t ion of ot h er
a cid ic oxid es from th e a tm os p h ere). Th is s p ot b eh a ves a s ca th od e with
th e r ea ction
Ca th od e: O 2 (g) + 4 H +(a q) + 4 e 2 H 2 O (l ) E H + | O 2
V

| H2 O

= 1 .2 3 V

Th e over a ll rea ction b ein g:

2 Fe(s )+O 2 (g) + 4 H +(a q) 2 Fe 2 +(a q)+ 2 H 2 O (l )
C h e m is t r y

90

E V(cell) =1 .6 7 V

Th e fer r ou s ion s a r e fu r th er oxid is ed b y a tm os p h er ic oxygen to

fer r ic ion s wh ich com e ou t a s r u s t in th e for m of h yd r a ted fer r ic oxid e
(Fe 2 O 3 . x H 2 O) a n d with fu rth er p rod u ction of h yd rogen ion s .
Pr even tion of cor r os ion is of p r im e im p or ta n ce. It n ot on ly s a ves
m on ey b u t a ls o h elp s in p r even tin g a ccid en ts s u ch a s a b r id ge colla p s e
or fa ilu r e of a k ey com p on en t d u e to cor r os ion . On e of th e s im p les t
m eth od s of p reven tin g corros ion is to p reven t th e s u rfa ce of th e m eta llic
ob ject to com e in con ta ct with a tm os p h ere. Th is ca n b e d on e b y coverin g
th e s u r fa ce with p a in t or b y s om e ch em ica ls (e.g. b is p h en ol). An oth er
s im p le m eth od is to cover th e s u rfa ce b y oth er m eta ls (Sn , Zn , etc.) th a t
a r e in er t or r ea ct to s a ve th e ob ject. An electr och em ica l m eth od is to
p r ovid e a s a cr ificia l electr od e of a n oth er m eta l (lik e Mg, Zn , etc.) wh ich
cor r od es its elf b u t s a ves th e ob ject.

Intext Questions
3 .1 3 Wr ite th e ch em is tr y of r ech a r gin g th e lea d s tor a ge b a tter y, h igh ligh tin g a ll th e
m a ter ia ls th a t a r e in volved d u r in g r ech a r gin g.
3 .1 4 S u gges t two m a ter ia ls oth er th a n h yd r ogen th a t ca n b e u s ed a s fu els in fu el
cells .
3 .1 5 E xp la in h ow r u s tin g of ir on is en vis a ged a s s ettin g u p of a n electr och em ica l cell.

The Hydrogen Economy

At p r es en t th e m a in s ou r ce of en er gy th a t is d r ivin g ou r econ om y is fos s il fu els s u ch
a s coa l, oil a n d ga s . As m or e p eop le on th e p la n et a s p ir e to im p r ove th eir s ta n d a r d
of livin g, t h eir en er gy r equ ir em en t will in cr ea s e. In fa ct , t h e p er ca p it a con s u m p t ion
of en er gy u s ed is a m ea s u r e of d evelop m en t. Of cou r s e, it is a s s u m ed th a t en er gy is
u s ed for p r od u ctive p u r p os e a n d n ot m er ely wa s ted . We a r e a lr ea d y a wa r e th a t ca r b on
d ioxid e p r od u ced b y t h e com b u s t ion of fos s il fu els is r es u lt in g in t h e Gr een h ou s e
E ffect . Th is is lea d in g t o a r is e in t h e t em p er a t u r e of t h e E a r t h s s u r fa ce, ca u s in g
p ola r ice t o m elt a n d ocea n levels t o r is e. Th is will flood low-lyin g a r ea s a lon g t h e coa s t
a n d s om e is la n d n a tion s s u ch a s Ma ld ives fa ce tota l s u b m er gen ce. In or d er to a void
s u ch a ca ta s tr op e, we n eed to lim it ou r u s e of ca r b on a ceou s fu els . Hyd r ogen p r ovid es
a n id ea l a lt er n a t ive a s it s com b u s t ion r es u lt s in wa t er on ly. Hyd r ogen p r od u ct ion
m u s t com e fr om s p littin g wa ter u s in g s ola r en er gy. Th er efor e, h yd r ogen ca n b e u s ed
a s a r en ewa b le a n d n on p ollu tin g s ou r ce of en er gy. Th is is th e vis ion of th e Hyd r ogen
E con om y. Bot h t h e p r od u ct ion of h yd r ogen b y elect r olys is of wa t er a n d h yd r ogen
com b u s tion in a fu el cell will b e im p or ta n t in th e fu tu r e. An d b oth th es e tech n ologies
a r e b a s ed on elect r och em ica l p r in cip les .

Summary
An e le c t ro c h e m i c a l c e ll c on s is t s of t wo m e t a llic e le c t r od e s d ip p in g in e le c t r olyt ic
s olu tion (s ). Th u s a n im p or ta n t com p on en t of th e electr och em ica l cell is th e ion ic con d u ctor
or elect r olyt e. E lect r och em ica l cells a r e of t wo t yp es . In galv an ic c e ll, t h e c h e m ic al
91

E le c t r oc h e m is t r y

e n e rgy of a s po n t an e o us re do x re ac t io n is con ver ted in to electr ica l wor k , wh er ea s in

a n elect r olyt ic cell, elect r ica l en er gy is u s ed t o ca r r y ou t a n o n -s po n t an e o u s re do x
re ac t io n . Th e s t an dard e le c t ro de po t e n t ial for a n y electr od e d ip p in g in a n a p p r op r ia te
s olu t ion is d efin ed wit h r es p ect t o s t a n d a r d elect r od e p ot en t ia l of h y dro ge n e le c t ro de
ta k en a s zer o. Th e s ta n d a r d p oten tia l of th e cell ca n b e ob ta in ed b y ta k in g th e d iffer en ce
V
V
V
of t h e s t a n d a r d p ot en t ia ls of ca t h od e a n d a n od e ( E ( cell ) = E ca t h od e E a n od e ). Th e
V

s ta n d a r d p oten tia l of th e cells Va r e r ela ted to s ta n d a r d Gib b s en er gy (rG = n F E ( cell ) )

a n d e quilibrium c o n s t an t (rG = R T ln K) of th e r ea ction ta k in g p la ce in th e cell.
Con cen tr a tion d ep en d en ce of th e p oten tia ls of th e electr od es a n d th e cells a r e given b y
Ne r n s t e q u a t ion .
Th e c o n duc t ivit y , , of a n electr olytic s olu tion d ep en d s on th e con cen tr a tion of th e
elect r olyt e, n a t u r e of s olven t a n d t em p er a t u r e. Mo lar c o n du c t iv it y , m , is d efin ed b y
= / c wh er e c is t h e con cen t r a t ion . Con d u ct ivit y d ecr ea s es b u t m ola r con d u ct ivit y
in c r e a s e s w it h d e c r e a s e in c o n c e n t r a t io n .
It in c r e a s e s s lo w ly w it h d e c r e a s e in
con cen tr a tion for s tr on g electr olytes wh ile th e in cr ea s e is ver y s teep for wea k electr olytes
in ver y d ilu t e s olu t ion s . Koh lr a u s ch fou n d t h a t m ola r con d u ct ivit y a t in fin it e d ilu t ion ,
for a n elect r olyt e is s u m of t h e con t r ib u t ion of t h e m ola r con d u ct ivit y of t h e ion s in
wh ich it d is s ocia t es . It is k n own a s law o f in de pe n de n t m igrat io n o f io n s a n d h a s
m a n y a p p lic a t ion s . Ion s c on d u c t e le c t r ic it y t h r ou gh t h e s olu t ion b u t oxid a t ion a n d
r ed u ction of th e ion s ta k e p la ce a t th e electr od es in a n electr och em ica l cell. Bat t e rie s
a n d fu e l c e lls a r e ver y u s efu l for m s of ga lva n ic cell. Co rro s io n of m eta ls is es s en tia lly
a n e l e c t ro c h e m i c a l p h e n o m e n o n . E le c t r o c h e m ic a l p r in c ip le s a r e r e le va n t t o t h e
Hy dro ge n Ec o n o m y .

Exercises
3 .1

Arra n ge th e followin g m eta ls in th e ord er in wh ich th ey d is p la ce ea ch oth er from th e

s olu tion of th eir s a lts .
Al, Cu , Fe, Mg a n d Zn .

3 .2

Given t h e s t a n d a r d elect r od e p ot en t ia ls ,
K+/ K = 2 .9 3 V, Ag +/ Ag = 0 .8 0 V,
Hg 2 +/ Hg = 0 .7 9 V
Mg 2 +/ Mg = 2 .3 7 V, Cr 3 +/ Cr = 0 .7 4 V
Ar r a n ge t h es e m et a ls in t h eir in cr ea s in g or d er of r ed u cin g p ower.

3 .3

Dep ict t h e ga lva n ic cell in wh ich t h e r ea ct ion Zn (s )+2 Ag +(a q) Zn 2 + (a q)+2 Ag(s )
t a k es p la ce. Fu r t h er s h ow:
(i) Wh ich of t h e elect r od e is n ega t ively ch a r ged ?
(ii) Th e ca r r ier s of th e cu r r en t in th e cell.
(iii) In d ivid u a l r ea ct ion a t ea ch elect r od e.

3 .4

Ca lcu la te th e s ta n d a rd cell p oten tia ls of ga lva n ic cell in wh ich th e followin g rea ction s
t a k e p la ce:
(i) 2 Cr (s ) + 3 Cd 2 + (a q)

2 Cr 3 +(a q) + 3 Cd

(ii) Fe 2 + (a q) + Ag +(a q) Fe 3 +(a q) + Ag(s )

Ca lcu la t e t h e r G a n d equ ilib r iu m con s t a n t of t h e r ea ct ion s .
3 .5

Write th e Ner n s t equ a tion a n d em f of th e followin g cells a t 2 9 8 K:

(i) Mg(s )| Mg 2 + (0 .0 0 1 M)|| Cu 2 + (0 .0 0 0 1 M)| Cu (s )

C h e m is t r y

92

(ii) Fe(s )| Fe 2 + (0 .0 0 1 M)|| H +(1 M)| H 2 (g)(1 b a r )|

Pt (s )

(iii) S n (s )| S n 2 + (0 .0 5 0 M)|| H +(0 .0 2 0 M)| H 2 (g) (1 b a r )| Pt (s )

(iv) Pt (s )| Br 2 (l )| Br (0 .0 1 0 M)|| H +(0 .0 3 0 M)|
3 .6

H 2 (g) (1 b a r )| Pt (s ).

In th e b u tton cells wid ely u s ed in wa tch es a n d oth er d evices th e followin g rea ction
t a k es p la ce:
Zn (s ) + Ag 2 O(s ) + H 2 O(l ) Zn 2 +(a q) + 2 Ag(s ) + 2 OH (a q)
Determ in e r G a n d E for th e r ea ction .

3 .7

Defin e con d u ct ivit y a n d m ola r con d u ct ivit y for t h e s olu t ion of a n elect r olyt e.
Dis cu s s t h eir va r ia t ion wit h con cen t r a t ion .

3 .8

Th e con d u ctivity of 0 .2 0 M s olu tion of KCl a t 2 9 8 K is 0 .0 2 4 8 S cm 1 . Ca lcu la te

it s m ola r con d u ct ivit y.

3 .9

Th e res is ta n ce of a con d u ctivity cell con ta in in g 0 .0 0 1 M KCl s olu tion a t 2 9 8 K is

1 5 0 0 . Wh a t is th e cell con s ta n t if con d u ctivity of 0 .0 0 1 M KCl s olu tion a t 2 9 8
K is 0 .1 4 6 1 0 3 S cm 1 .

3 .1 0

Th e con d u ctivity of s od iu m ch lorid e a t 2 9 8 K h a s b een d eterm in ed a t d ifferen t

con cen t r a t ion s a n d t h e r es u lt s a r e given b elow:
C on c e n t r a t ion / M 0 .0 0 1

0 .0 1 0

0 .0 2 0

0 .0 5 0

1 0 / S m

1 1 .8 5

2 3 .1 5

5 5 .5 3 1 0 6 .7 4

1 .2 3 7

0 .1 0 0

Ca lcu la te m for a ll con cen tra tion s a n d d ra w a p lot b etween m a n d c . Fin d th e

va lu e of m0 .
3 .1 1

Con d u ctivity of 0 .0 0 2 4 1 M a cetic a cid is 7 .8 9 6 1 0 5 S cm 1 . Ca lcu la te its m ola r

con d u ctivity a n d if m0 for a cetic a cid is 3 9 0 .5 S cm 2 m ol1 , wh a t is its d is s ocia tion
c on s t a n t ?

3 .1 2

How m u ch ch a r ge is r equ ir ed for th e followin g r ed u ction s :

(i) 1 m ol of Al3 + to Al.
(ii) 1 m ol of Cu 2 + to Cu .
(iii) 1 m ol of Mn O 4 to Mn 2 +.

3 .1 3

How m u ch electr icity in ter m s of Fa r a d a y is r equ ir ed to p r od u ce

(i) 2 0 .0 g of Ca from m olten Ca Cl2 .
(ii) 4 0 .0 g of Al from m olten Al2 O 3 .

3 .1 4

How m u ch electricity is requ ired in cou lom b for th e oxid a tion of

(i) 1 m ol of H 2 O to O 2 .
(ii) 1 m ol of FeO to Fe 2 O 3 .

3 .1 5

A s olu tion of Ni(NO 3 )2 is electrolys ed b etween p la tin u m electrod es u s in g a cu rren t

of 5 a m p eres for 2 0 m in u tes . Wh a t m a s s of Ni is d ep os ited a t th e ca th od e?

3 .1 6

Th r ee electr olytic cells A,B,C con ta in in g s olu tion s of Zn SO 4 , AgNO 3 a n d Cu SO 4 ,

res p ectively a re con n ected in s eries . A s tea d y cu rren t of 1 .5 a m p eres wa s p a s s ed
th rou gh th em u n til 1 .4 5 g of s ilver d ep os ited a t th e ca th od e of cell B. How lon g
d id th e cu rren t flow? Wh a t m a s s of cop p er a n d zin c were d ep os ited ?

3 .1 7

Us in g th e s ta n d a rd electrod e p oten tia ls given in Ta b le 3 .1 , p red ict if th e rea ction

b et ween t h e followin g is fea s ib le:
(i) Fe 3 + (a q) a n d I (a q)

93

E le c t r oc h e m is t r y

(ii) Ag + (a q) a n d Cu (s )
(iii) Fe 3 + (a q) a n d Br (a q)
(iv) Ag(s ) a n d Fe

3+

(v) Br 2 (a q) a n d Fe
3 .1 8

(a q)
2+

(a q ).

Pr ed ict th e p r od u cts of electr olys is in ea ch of th e followin g:

(i) An a qu eou s s olu tion of AgNO 3 with s ilver electr od es .
(ii) An a qu eou s s olu t ion of AgNO 3 wit h p la t in u m elect r od es .
(iii) A d ilu te s olu tion of H 2 SO 4 with p la tin u m electr od es .
(iv) An a qu eou s s olu t ion of Cu Cl2 wit h p la t in u m elect r od es .

An s we rs t o S o m e In t e xt Qu e s t io n s
3 . 5 E (cell) = 0 .9 1 V
3 . 6 r G V = 4 5 .5 4 k J m ol 1 , K c = 9 .6 2 1 0 7
3 . 9 0 .1 1 4 , 3 .6 7 1 0 4 m ol L1

C h e m is t r y

94