BCHES102-202

MODULE 3 : Corrosion and Electrode System

Corrosion chemistry:Introduction,
electro chemical theory of corrosion,
typesofcorrosion differential metal and differential aeration.
Corrosioncontrol-galvanization,anodization and Sacrificial
anode method. Corrosion Penetration Rate (CPR) –
Introduction and numerical problem.

Electrode System : Introduction, types of electrodes. Ion

selective electrode –Definition,construction, working and
applications of glass electrode. Determination of pH using
Glasselectrode. Reference electrode- Introduction, calomel
electrode– construction,
Working and applications of calomel electrode.
Concentration cell–Definition,
construction and Numerical problems.

Analytical Techniques: Introduction, principle and

instrumentation of Conductometry; Its application in the
estimation of weak acid. Potentiometry; its application in the
Estimation of iron.
Def
ini
ti
onofcor
rosi
on:
“
Theprocessofsl
owconversi
onofmet al
si nt
othei
rundesi
rabl
ecompoundsbyr
eact
ionwi
th
moist
ureandot
hergasespr
esenti
ntheenvi
ronment”

Metal Cor
rosi
on(Oxi
dati
on) Metal + Ener
gy
(
Higherenergyor Met
all
urgy(
Reducti
on) (Lowerener
gyor
Thermody namical
l
y Thermody
nami
cal
l
y
Unstabl
e) st
able)

Exampl
es:
(i
) Rusti
ngofiron:Wheni r
onrodi
sexposedt otheenv i
ronmentf oralongtime,al ay
erof
reddi
shbrownpowderofFe2O3 (
fi
naloxi
dati
onpr oduct)isfor
medont hesurfaceofi r
on
rod.
(i
i) Formati
onofgr eenlayeroncoppermet al
:A gr eencol orofcoppercar bonat elayer
consi
sti
ngof[ CuCO3 +Cu(
OH)2]isfor
medont hesur faceofcopperwhenex posedt o
moist.

El
ect
rochemi
cal
theor
yofcor
rosi
on:
Accordingtothistheory ,
 Whent wodi ssimilarmet alsar ei
ncont actwitheachotherinasol ut
ionalar
genumberof
galvani
ccel l
sar eformedwi t
ht heexist
enceofanodicandcathodicareaonthemetal
.
 I nthiscorrosion,Oxidati
onoft hemet alandreducti
onofspeciespresentint
hesolut
iontakes
place.
 Anodi cpar toft hemet alundergoesoxidati
onandsuf f
ersfrom corr
osionwhil
ethecathodic
partofthemet alundergoesr educti
onandpr ot
ectedfr
om corrosi
on.
 El ectr
onsar etransferredthroughthemet alfr
om anodetocathode.
Dur
ingt
hiscor
rosi
onthef
oll
owingreact
iont
akespl
ace,
 AtAnode(Oxidat
ionr
eacti
on)
M Mn++ne

I
ntheabsenceofdi
ssol
vedox
ygen I
nthepr
esenceofdi
ssol
vedox
ygen

I
naci
dicmedi
um t
her
eact
ioni
s I
naci
dicmedi
um,
ther
eact
ioni
s
+ +
2H +2e H2 2H +1/
2O2+2e H2O
I
nneut
ral
oral
kal
i
nemedi
um,
ther
eact
ioni
s I
nneut
ral
oral
kal
i
nemedi
um,
ther
eact
ioni
s

2H2O+2e 2OH +H2 H2O+1/

2O2+2e 2OH

EXAMPLE:
Rust
ingofani
roni
nthepr
esenceofmoi
stai
r.

React
ionatanodi
cr egi
on
Asmentionedabove,oxi
dat
ionofmet
alt
akespl
aceatanode.

e.
g.Fe Fe2++2e
React
ionsatcat
hodi
cregi
on
H2O+1/2O2+2e 2OH

Ov
erall
react
ion
Themet alions(Fe2+)li
berat
edatanodeandsomeani ons(OH-
)formedatcathodedif
fuse
towardseachotherthroughtheconduct
ingmedi
um andfor
m acorr
osi
onproductsomewhere
betweentheanodeandcat hodeas
2Fe2++4OH- 2Fe(
OH)
2

I
nanox
idi
zi
ngenv
ironment
,thei
nsol
ubl
eFe(
OH)
2oxi
diz
edt
ofer
ri
coxi
deasf
oll
owi
ngr
eact
ion.
4Fe(
OH)
2+O2+2H2O 4Fe(OH)
3 2Fe2O3.
6H2O
(
Brownrust
)
I
ftheconcent
rat
ionofoxy
geni
sli
mit
edt henFe(
OH)2isconver
tedi
ntomagnet
icox
ideofFeandi
s
knownasblackrust
.
3Fe(
OH)
2+½O2 Fe3O4.
3H2O

Ty
pesofcor
rosi
on:
1.Dif
f er
enti
almet alcorrosi
on:Di f
ferentialmet alcorrosionariseswhent wodissimilarmet al
s
suchasi ronandcopperar eincont actwi theachot heri nacor r
osivemedi um.Thepot ent i
al
dif
fer
encebet weent womet al
si sthecauseordr iv
ingf orceforcor r
osion.Themet alwithlower
el
ectrodepot enti
alormor eact ivemet al( topi nelect r
ochemi calseries)actsasanodeand
undergoescor r
osionquickly
.Ot hermet al(cathode)isunaf fect
edf rom thecor r
osion.Exampl e:I
n
Fe-Cugalvani
ccel l,i
ron(E°=- 0.44V)wi thlowerr eductionpotent i
althancopper( E°=+0. 34V) ,
hencez i
ncactsasanodeandt heel ectronsflowf rom anodi cmetal t
ocat hodic(Cu)Fig.
2.3.

I
ncor
rosi
vemedi
um,

Atanode: Fe Fe2+ +2e-

- -
Atcathode:O2+2H2O+2e 4OH
Fact
orsaf
fect
ingrateofgal
vani
ccor
rosion:
• Hi gherthepotent
ialdiff
erencebet weent heanodicandcathodicmetal
s,hi
gheri
s
ther ateofcor
rosi
on.
• Smal leranodicar ea and largercathodicar ea i
ncreasesthe r
ate ofgal
vani
c
cor r
osion.Thi
stypeofcor rosioncanbeobser vedinthefoll
owingexampl
es:
(
i)Steel screw’
sinabr assmar i
nehar dware.
(
ii
)Steelpi peconnectedt ocopperpl umbi ng.
(i
ii)Zinccoatedmildsteelstructur
es.

2.Di
ff
erent
ial
Aer
ati
oncor
rosi
on(
Concent
rat
ioncel
lcor
rosi
on)

Thistypeofcor rosionoccur swhent wodi f

ferentpartsofthe
samemet alareexposedt odifferentox ygenconcent rati
ons.
(e.
g.Ani ronr odpar ti
all
ydi ppedi nwat er.
) Thepar tof
themet alwhichisex posedt olessox ygenconcent r
ation
actsasanodeasshowni nFi g:3.5. Thepar twhichi s
exposedt omor eoxy genconcent r
at i
onact sascat hode.
Thus,anox ygenconcent r
ationcel lisformed.
Metal/
Lessoxy gen//moreoxy gen/ Metal
Theanodi cregionunder goescor r
osi onandt hecathodic
regi
oni sunaffected.

Ther
eact
ionsmayber
epresent
edasfoll
ows:
n+ -
Atanode:(l
essO2concent
rat
ion)
:M M +ne

Atcat
hode:
(mor
eO2concent
rat
i :O2+2H2O+4e-
on) 4(
OH)
-

Exampl
esofdi
ff
erent
ial
aer
ati
oncor
rosi
onar
ethewat
erl
i
necor
rosi
onandpi
tt
ingcor
rosi
on.
2.Wat
erl
i
necor
rosi
on:
Thi
sisanexampl
eofdi
ff
erent
ial
aer
ati
oncor
rosi
on.

Whenast eeltanki spar ti

all
yf i
ll
edwithwater
foralongt i
me,t hei nnerpor ti
onoft hetank
below t
hewat erl i
nei sexposedonl ytoDO,
whereas,thepor ti
onabov et hewaterlineis
exposedtomor eox ygen.Thust hepor t
ion
below the waterl ine act s as anode and
undergoescorrosion.Theupperpor t
ionacts
as cathode and i s unaf fected.A disti
nct
brownl i
neisf ormedj ustbel ow t
hewat er
l
ineduet ot he deposi ti
onofr ustasshowni n
Fig3.6.

Ther
eact
ionsmayber
epr
esent
edasf
oll
ows:
n+
Atanode:M M +ne (
Oxi
dat
ionofmet
al,
M)
Atcat
hode:2H2O+O2+4e 4OH (
Reduct
ionofox
ygen)

Otherexample:Shi
pswhi
chr
emai
npar
ti
all
yimmer
sedi
nseawat
erf
oral
ongt
imeunder
gowat
er
l
inecorrosi
on.

 Galvanizi
ng
Gal
vani
zingisthepr
ocessofcoat
ingametalsurf
acesuchasir
onwi t
hzi
ncmetal
.Gal
vani
zi
ngof
i
ronisanexampleofanodi
cmetalcoat
ingonthesur
faceofacathodi
cmetal
.
Process:Galvani
zat
ioni
scar
ri
edoutbyhotdi
ppi
ngmet
hodasshowni
nFi
g.2.
6.I
tinv
olv
est
he
fol
lowingsteps
1. SolventCl eaning:Themet alsur faceiswashedwi t
hor ganicsol
ventst oremov eor gani
c
i
mpur i
ti
esont hesur
face.
2. AlkaliCleaning:Residualorganici mpur i
tiesareremov edbyt r
eati
ngtheobjectwithalkal
isuch
asNaOH.
3. Picking: RustandScal eisremov edbywashi ngt heobj ectwit
hdil
utesulphuri
cacidH2SO4
4. Finall
y,thear ticl
eiswashedwi thwat erandai r-
dried.
5. Thear ticleist hendi
ppedi nabat hofmol tenzincat430˚ Ct o470˚
C( Moltenzinciscov er
ed
withaf luxofammoni um chl or
idet oprev enttheox idati
onofmol t
enz i
nc.)
6. Theexcesszi nconthesurfacei sremov edbypassi ngthroughapairofhotroll
ers.
Appli
cation
Gal
vanizationofi roniscarri
edoutt opr oducer oofingsheet s,fenci
ngwire,buckets,bolt
s,nuts,
pi
peset c.
 Anodi zi
ng
(Anodizingofal
uminum):I
tisatypeofi
nor
gani
ccoati
ng.Aprocessinwhicht
oplayerofametal
i
sconv ert
edtoitsoxi
de,whichact
sasapr ot
ect
ivebar
ri
erandr educescor
rosi
oniscall
edas
anodizing.
Process:Thearti
cleissubject
edt odegreasingandpoli
shingandt henmadeasanode, r
eferfi
g16.
Chromicacidelectrol
yteismaintainedatabout350Candsui t
ablev ol
tageisappl
iedt
ogetdesired
thi
cknessoft heoxi defil
m.Anodi sedart
icleisseal
edbyt reati
ngwi thboil
ingwaterorsteam
contai
ningsaltsofNi ckelorCobal t
.TheAl 2O3.
nH2O l
ayeront hesur f
aceactsasapr otect
ive
coati
ng,hencecorrosionisprevented.

AtAnod
3+
2Al +3H2O Al2O3+6H+
AtCat
hode:6H++6e 3H2
2Al+3H2O Al2O3+3H2

Ot
hermet
alssuchasMg,
Tiet
c.canal
sobeanodi
zed.
Appl
i
cat
ions:
Met
alssuchasAl
,Mg,
Tiet
c.ar
eanodi
zedt
ocont
rol
cor
rosi
on.
3.
7Cor
rosi
onPenet
rat
ionRat
e(CPR)
Defi
nit
ion:
TheCorrosi
onpenetr
ati
onrat
eisthespeedatwhichanymetal
orall
oydet
eri
orat
esi
na
speci
fi
ccorrosi
veenvi
ronmentt
hroughchemical
orelect
rochemi
cal
react
ions.
I
tisalsodefinedastheamountofweightl
ossperyeari
nthethicknessofmet
aloral
l
oyduet
o
cor
rosion.TheCorr
osionpenet
rat
ionr
ateal
soref
err
edascorr
osionrate.
Cor
rosi
onpenet
rat
ionr
atedependsonf
oll
owi
ngf
act
ors;
1. Natureofmetal
.
2. Natureofcor
rosi
v eenvironment/
medi um.
3. Natureofcor
rosi
onpr oduct.
4. Speedatwhichcor r
osionspreadsintheinnerpor
ti
onofmet
al.
TheCorrosi
onpenetrati
onr atei
scalcul
atedusingthefol
l
owi
ngfor
mul
a;

kxW
CPR
D()
xAxT
Wher
e,
W-
iswei
ghtl
ossaf
terex
posur
eti
meT
-
isexposur
eti
mei
ncor
rosi
vemedi
um.
D-i
sthedensi
tyofmet
aloral
l
oy.
A-
issur
facear
eaofex
posedspeci
men.
K-
isconst
ant
.
TheCPRisconv
eni
ent
lyexpr
essedi
nter
msofei
thermi
l
s(0.
001i
nch)pery
ear(
mpy
)ormi
l
li
meter
spery
ear(
mmpy).
CPRi
nmpy CPRmmpy
K 534 87.
6
W Mg Mg
3
(
D)ρ g/
cm cm3
g/
A nch2
i cm2
Hr
s Hr
s Hr
s
NumericalPr
obl
emsonCPR
1.Asheetofcarbonst eelonemeterwidebyt hr
eemeterslonghaslost40gt ocor
rosi
onover
thepastsixmonths.Conv er
tthatmasslosstoapenetr
ati
onr at
eoft hesteeli
nmm unitsand
mpyuni t
s.Whatwoul dbet hecorrosi
onrate?(Car
bonsteeldensi
ty=7.8g/cm3)Tocalcul
ate
CPRinmmpy

Sol
uti
on:
Tocalcul
ateCPRi
nmmpy
Given CPRinmmpy
K 87.
6
W 40g 40x1000mg
3 3
(
D)ρ 7.
8g/
cm 7.
8g/cm
 2 2
A 1mx3m=3m 3x100x100cm
T 6months 6x30x24hr s

kxW
CPR Tocal
cul
ateCPRi
nmpy
D xAx
T
Gi
ven CPRinmpy
K 534
W(
wtl
oss) 40g 40x1000mg
Ρ 7.
8g/cm3 7. cm3
8g/
2 2
A 1m x
3m =3m 3x1550inch
T 6months 6x30x24hr
s
1sqmt=1550 sq i
nch
kxW
CPR
D xAx T
534x40x1000CPR

7.
8x3x100x
100x
6x30x24
CPR0.
0503mpy

2.Cal
cul
atet
heCPRi
nbot
hmpyandmmpyf
orat
hickst
eel
sheetofar nch2whi
ea100i ch
exper
iencesawei
ghtl
ossof485gaf
teroney
ear
.(Densi
tyofst
eel
=7. cm3)
9g/ .Sol
uti
on:

Tocalcul
ateCPRi
nmmpy
Given CPRi nmmpy
K 87.6
W 485g 485x1000mg
3
ρ 7.9g/
cm 7.
9g/cm3
A 100inch2 100x6. 45cm2
t 1year 365x 24hrs
2 2
1inch=6.
45cm

1cm2=0. nch2
155i

kxW
CPR D ρ xAxT

7.
9x
0.
9518mmpy
 Tocal
culat
eCPRinmpy
Given CPRi nmpy
K 534
W 485g 485x1000mg
ρ 7.9g/cm3 7.
9g/cm3
A 100i nch2 100inch2
t 1year 365x24hr s

kxW
CPR D ρx
AxT

7.
9x
37.
42mpy
3.At
hicknessofbr
asssheetofar nch2i
ea400i sexposedt
oai
rneart
heocean.Af
tert
wo
yearsperi
oditwasf
oundtoexper
ienceawei
ghtl
ossof375gduetocor
rosi
on.I
fthedensi
tyof
Brassis8. cm3.
73g/ Cal
cul
atetheCPRinmm/yearmpy.Sol
uti
on:
Tocal
cul
ateCPRi
nmmpy
Given CPRinmmpy
K 87.6
W 375g 375x1000mg
ρ 8.73g/cm3 8.73g/cm3
A 400inch2 400x6.45cm2
t 2year 2x365x24hrs
2 2
1i nch=6.45cm

1cm2=0. nch2
155i

kxW
CPR D ρx
AxT

8.
73
0.
083mmpy
Tocal
cul
ateCPRinmpy
Gi ven CPRinmpy
K 534
W 375g 375x1000mg
Ρ 8.
73g/ cm3 8.73g/cm3
A 400i nch2 400inch2
T 2year 2x365x24hrs

kxW
 CPR D ρx
AxT

8.
73
3.
27mpy

TYPESOFELECTRODES:
METAL-METALION ELECTRODE:Thi
sty
peofel
ect
rodeconsi
stsofamet
ali
ncont
actwi
tha
sol
uti
onofit
sownions.
Eg:1.
Zinci
nasol
uti
onofzi
ncsulphate.
2.Copperi
nasol
uti
onofcoppersulphat
e.

METAL-METALSALTIONELECTRODE:Thi
st y
peofel
ect
rodeconsi
stsofamet
ali
ncont
actwi
th
oneofit
sspari
ngl
ysolubl
esal
tsandasol
uti
onofasol
ubl
esalthav
ingacommonani
onwit
hthe
spar
ingl
ysol
ubl
esalt
.
-
Eg:
1.Cal
omel
elect
rode Hg/Hg2Cl
2/Cl
-
2.Si
l
ver
-Si
l
verchl
ori
deel
ect
rodeAg/AgCl
(s)/Cl

GASELECTRODE:Agasel
ect
rodeconsistsofapar
ti
cul
argasfl
ushedaroundani
ner
tel
ect
rode
(Pt
),whi
chi
sdi
ppedi
nasolut
ioncont
ainingi
onstowhi
chiti
srev
ersi
ble.
Eg:
SHE Pt/H2( m)/H+(
1at 1M)

OXIDATI
ON-REDUCTI
ONELECTRODE:Thi stypeofel
ect
rodeconsi
stsofaninertel
ect
rode(
Ptor
Au)immersedi
nami xedsol
uti
oncont
ainingbot
htheoxidi
zedandreducedfor
msofamol ecul
e
ori
on.
Pt/Fe2+:
Eg: Fe3+
Pt/Sn2+:
Sn4+

IONSELECTIVEELECTRODE:I nionselecti
veelectrode, amembraneisincont
actwi t
hasolut
ion,
wit
hwhi chitcanexchangeions.(I
onselecti
veel ectrodeisonewhichselect
ivel
yrespondst
oa
speci
fi
ci oninami xtur
eandt hepot enti
aldev elopedatt heelect
rodeisaf uncti
onofthe
concent
rati
onofthationint
hesoluti
on)Exampl e-Glasselect
rode.

REFERENCEELECTRODE:
Referenceel
ect
rodesar
ethosewhosepot
ent
ial
sar
eknown.

 PRIMARYREFERENCEELECTRODE[ SHE]
:Hydrogengasatapressureofoneat
mospherei
n
equi
l
ibr
ium wi
thonemol
arhydrochl
ori
cacidinthepresenceofplat
inum i
scal
ledst
andar
d
 hy
drogenel
ect
rode.

Const
ruct
ionofnor
mal
hydr
ogenel
ect
rode[
nheorshe]
:

I
tconsistsofar ectangularpieceofplatinum foil
,whi chi scov er
edwi thfinal
lydivi
dedPt
bl
ack,whi chadsor bsl ar
gequant i
tyofhy drogenandsoact sashy drogenel ectr
ode.The
el
ectr
odei simmer sedi nasol uti
onofHClcont ai
ninghy dr ogenionsatuni tacti
vit
yFig:3.
12.
a
Purehydrogengasi sbubbl edatoneat mosphericpressur e.Thet emperatureismaintai
nedat
298K.Byconv enti
ont hepotentialofsuchel
ect r
odehasbeent akenasz ero.
Thi
selectr
odei srepresentedas
Pt,H2(1at
m) ;H+(1M)

Wor
king:
Atanode½H2 H++e-
+ -
Atcat hode H +e ½H2
Li
mi tati
onsofhy drogenelectrode:
1.Itisdiff
iculttomai ntainthepressureofhydrogengasuni formlyatoneat mosphere.
2.Itisdiff
iculttomai ntainthehy dr
ogenionconcentrati
on1M t hr
oughoutt heexperi
ment .
3.Pl ati
num foiliseasil
ypoi sonedbyt headsorpt
ionofimpur it
iespresentint hesol
ution.
4.Theadsor ptionsofi mpur it
iesont heplat
inum foildecreaset headsor ptionofhy dr
ogenand
henceequilibrium betweenhy drogengasandhy drogenionsget sdisturbed.
5.Hy dr
ogenel ectrodecannotbeusedi nthepresenceofoxi di
zingagent.
Thesel i
mitationsleadt otheconst r
ucti
onofsecondar yreferenceelectr
ode.

 Secondar
yref
erenceel
ect
rode:

1.
Calomelel
ect
rode
2.Ag-
AgClel
ect
rode

CALOMEL ELECTRODE:The cal omelel ectrode

consi
stsofagl assv esselcont
aini
ngal ayerof
Hgov erwhichisplacedapasteofanHg,Hg2Cl 2
andKCl .Abovet hi
st hereisasol ut
ionofKCl
satur
ated wit
ht heMer curoussalt
.A pl at
inum
wir
ei sf used i
nt he glass t
ube forelectrical
 connect
ionFi
g:3.
13.Asal
tbr
idgei
susedt
ocoupl
ewi
thot
herhal
f-
cel
l
.

Thehal
f-
cel
li
srepr
esent
edas

KCl
(sat
),Hg2Cl
2(sat
),Hg

Thehal
f-
cel
lreact
ioni
s

1/
2Hg2Cl
2(s)+e- -
Hg+Cl

Thepotentialofthecalomelel
ect
rodedependsontheconcent
rat
ionofKClused.Forsaturat
ed
KCl,the potenti
alis +0.
241V,FOR 1M and 0.1M KClthe val
ues ar
e 0.
280V and +0.334V
respect
ivel
y.

USES:Thecalomelelect
rodeissimpl
etoconstr
uct,t
hecellpotent
iali
sreproduci
bleandst
abl
e
overalongperi
odanddoesnotv ar
ywit
htemperat
ure.Henceiti
scommonl yusedasasecondar
y
ref
erenceel
ectr
odeforpotent
ial
measurement
s.

3.
10Ionselect
iveel
ectr
ode:
I
onselect
iveelect
rodeisonewhichsel
ect
ivelyr
espondstoaspecif
ici
oninamixtur
eandt he
pot
enti
aldevel
opedattheel
ect
rodeisaf
unctionoft
heconcent
rat
ionoft
hati
oni
nthesolut
ion”

GLASSELECTRODE:
A gl assel ectr
odeisani onsel ectiv
eel ectr
odewher epotenti
aldependsupont hepH oft he
medi um.
Const ructi
onofglassel ectrode:
A glassel ect
rodeisani onselectiveel ect r
odewher epotenti
aldependsupont hepH oft he
medi um.Thegl asselect rodeconsi stsofagl assbulbmadeupofspeci alt y
peofglasswhi ch
consi sti
ngof72% ofSi O2,22% Na2O and6% CaO,hasl ow mel ti
ngpoi ntandr el
ati
vel
yhi gh
electricalconducti
vi
ty.( Fig:
1.3)Thegl assbul bisf i
l
ledwi t
hasol utionofconst antpH (0.
1M
HCl )
andi nsertwithaAg- AgClelectrode, whichi stheInt
ernalref
erenceelectrodeandalsoserves
fortheext ernalel
ectr
ical contact.Theel ectrodedippedinasol ut
ioncontainingH+ions(Fi
g:)
Theel
ect
roder
epr
esent
ati
oni
s,Ag-
AgCl
|0.
1M HCl
|Gl
ass.

Pri
nciple:
I
fat hinwal l
edgl assbulbcont ai
ninganaci
disimmersedinanothersolut
ioncontai
ning
H+ ions,apot enti
ali sdeveloped acr
osstheglassmembr ane.Thisi sduet hei on
exchanger eactiont aki
ngpl aceatt hegellay
ersofglassmembr ane.Thisiscalled
boundar ypotenti
al Eb

Theboundarypot
ent
ialisduetot
hedif
fer
enceinpot
ent
ial(
E1-
E2)dev
elopedacr
osst
he
gell
ayeroft
hemembr anebet
weenthet
woliqui
ds.

WORKING
Consi
der,
C2>C1
Theboundar
ypotent
ial
isgi
venbyNer
nstequat
ionatmembr
aneEb=E2–E1

Theref
oreEb=0. 0591logC2 0. 0591logC1
Eb=K+0. 0591l ogC2wher eK= 0. 0591l
ogC1
Eb=K 0. 0591pH
Si
ncepH= l og[H+]
TheglasselectrodeEG has3t hreecomponent
s
1.Boundar yPot enti
alEb
2.Potent i
aloft hei
nternalrefer
enceel
ect
rodeEAg|AgCl
3.Asy mmet ri
cPotenti
alEasy

Ther
efor
e,EG=Eb+EAg|AgCl+Easy
EG=K–0. 0591pH+EAg|AgCl+Easy

EG E0G 0.
0591pH

Advantages
1. Thi
select r
odecanbeusedt odeterminepHi ntherange0 9, wit
hspecialty
peofglasseven
upto12canbecal cul
ated.
2. I
tcanbeusedev eninthecaseofst rongoxidizi
ngagents.
3. Theequi l
i
brium i
sreachedquickl
y.
4. I
tissimplet ooperat
e,henceextensi
v el
yusedi nvar
iouslaborat
ori
es.Limit
ati
ons
1. Thegl assmembr anethoughi tisv erythin,itoffer
shi ghresist
ance.Theref
oreordi
nary
pot
entiomet er
scannotbeused; henceitisnecessar
yt ouseelectr
onicpotent
iometer
s.
2. Thi
selectrodecannotbeusedt odeter mi
net hepHabov e12
Appl
icationsofGlassel ectrode:
• pHmeasur ement.
• FoodAnal ysi
s.
• Cosmet i
canal
y si
s.
• Environmentalregulations.
• Soilacidit
ydet
er mination.

Det
ermi
nat
ionofpHusi
nggl
assel
ect
rode:

Principl
e:When a t hin glass membr ane is
placedbet weent wosol ut
ionsofdi f
fer entpH
values,apot enti
aldiffer
encear i
sesacr osst he
membr ane.Thepot enti
aldifferencev ar i
esas
thepHoft hesesol uti
onsv ari
es.Inpract ice,pH
ofoneoft hesesol uti
onsi skeptconst antand
thereforetheel ectr
odepot entialdependsonpH
oft heothersol uti
oni.e.experi
ment alsolut i
on.

Procedure:gl
assel
ectr
odeisimmersedint
hesoluti
on;
thepHist
obedetermined.I
tiscombined
withar ef
erenceel
ect
rodesuchasacalomelel
ectr
odethr
oughasal
tbr
idge.Thecellassembl
yis
represent
edas,
-
Hg(l)|
Hg2Cl
2|
Cl||Sol
uti
onofunknownpH|
glass|
0.1M HCl
|
AgCl
|Ag(s)
Theemfoft
heabov
ecel
l
,Ecelli
smeasur
edusi
nganel
ect
roni
cvol
tmet
erwi
thapH
met
er.Theemfoft
hecel
li
sgi
venby

Ecell=Ecathode-
Eanode …………….
1 E
=EG-ESCE
cel
l …………….
2

EG E0G 0.
0591pH

Ecell=E0G–0.
0591pH ESCE

E0G ESCE EcellpH

0.0591

CONCENTRATIONCELLS
Aconcent
rati
oncelli
sanelect
rochemi
calcel
linwhi
cht heel
ect
rodemater
ialandthesol
uti
onin
bot
htheelect
rodesarecomposedofthesamesubstancesbutonl
ytheconcentr
ati
onofthetwo
sol
uti
onsi
sdiffer
ent”
At
ypi
cal
exampl
eofZi
ncconcent
rat
ioncel
li
sshownbel
ow
I
tconsists oftwo zi
nc electr
odes ar
ei mmersed int wo di
ff
erentconcent
rati
ons ofZnSO4
sol
uti
ons.Thesetwoelectrodesareext
ernal
lyconnectedbymetall
icwi
reandinternal
l
ybyasalt
bri
dgeasshowni nFi
g:7.Thecellcanberepr
esentedas,
Zn2+(
Zn| C1)|
|Zn2+(
C2)|
Zn
Byconv
ent
ionl
efthandel
ect
rodei
stheanodeandr
ighthandel
ect
rodei
scat
hode.
Zn Zn2++2e
Atanode:
2+
Atcat
hode:
Zn (
C2)+2e Zn
_
___
___
___
___
___
___
___
___
___
___
___
___
__

+
Netcel
lreact
ion: [ ]

Thenetcel
lreact
ioni
smer
elyt
hechangei
nconcent
rat
ionasar
esul
tofcur
rentf
low.
EMFofConcent
rat
ionCel
l
We know thatel
ect
rode potent
ialdepends upon t
he concent
rat
ion oft
he el
ect
rol
yte.By
conv
enti
on,
thepot
enti
alofthecel
l i
s

Ecel
l=E hode E
cat anode …(
1)
0.
0591 0.
0591
Ecell logC 2 l
ogC 1 …(
2)
n n

Ecell 0.
0591l
og C2 at298K …(
3)n C1

Fr
om equat
ion(
3)f
oll
owi
ngconcl
usi
onsmaybedr
awn.
1.Whent
het
wosol
uti
onsar
eoft
hesameconcent
rat
ion,t
henl
og C2 andnoel
ect
ri
ci
ty
fl
ows.
C1
2. Hence,
Ecell=0
3. WhenC2| C1>1i .
e.,
C2>C1,logC2|C1i
sposi
ti
ve&electrodepot
ent
ial
isposi
ti
ve.
4. Hi
gherther at
ioofC2|C1,
higheri
stheval
ueofcel
lpotenti
al.

Numer
ical
Probl
ems
1.Cal
cul
atetheemfofCopperconcent
rat
ioncel
lat25 C,wher
ethecopperi
onsr
ati
oint
hecel
l
is10.
Sol
uti
on

Gi
ven:
[Cu 22] hode C
cat 2 10
[
Cu]
anode C1

0.
0591 C2
w.
k.tEcell l
og ;
at298K
n C1

0.
0591
Ecell l
og(
10)
2
Ecell=0.
0296V
2. Aconcentrat
ioncel
lwasconstr
uctedbyimmersi
ngt wosil
verel
ect
rodei
n0.05M and1M
AgNO3soluti
on.Wri
tet
hecellr
epresent
ati
on,
cel
lreacti
onsandcal
cul
atet
heEMFofthecel
l
.
(Jul
y-
06)Soluti
on
Cel
lrepr
esent
ati
on:
Ag(
s) AgNO3(
0.05M) AgNO3(
1M) Ag(
s)
+
Atanode:
Ag(
0.05M) Ag (
0.05M)+e
Atcat Ag+(
hode: 1M)+e Ag(
1M)
_
___
___
___
___
___
___
___
___
___
___
___
___
__
Netcel
lreact
ion:
Ag(
0.05M)+Ag+ Ag+(
0.05M)+Ag

0.
0591 C2
Ecell l
og n
C1

0.
0591 1
Ecell log
n 0.
05
Ecell=0.
0768V
3. Thespont
aneousgal
vaniccel
lTi
n|Ti ni
on(0.
024M)|
|Ti
nion(
0.064M)|Ti
ndev
elopanemf
of
0.0126Vat25 C,Cal
culatet
heValencyofTi
n (Jan-
06)
Sol
uti
on

0.0591 C2
Ecell l
og n
C1
0591 C2 n l
0. og

Ecell C1

0.
0591 0.
064 n
l
og
0.
0126 0.
024

n=2(
Val
encyoft
in)
4.Calcul
atetheconcent
rat
ionoft
heunknown,gi
vent
heequat
ionbel
ow andacel
lpot
ent
ialof
0.
26Vandcel lAg|Ag+(xM)|
|Ag+(
1.0M)|Ag
Solut
ion

0.
0591 C2
Ecell l
og n
C1

0.
0591 1.0
0.
26 l
og
1 x
4.
362=−l
og(
1.0)+l
og(
x)
341 105M
x=4.

5.Theemfofacel lAg/
AgNO3(
0.02M)/
/AgNO3(
X)/
Agf
oundt
obe0.
084Vat298K.Wr
it
ethecel
l
reacti
onsandcal
cul
atet
heval
ueofX.
Sol ut
ion:

0591n C2
0.

Ecell og C1
l

0.
0591 X Ecell
l
og
1 0.
02
 = .

a.
Conduct
omet
ri
cTi
tr
ati
on
Theelect r
ochemi calmet hodofanal
ysi
susedf orthedeter
minati
onoft heel
ectri
calconduct
ance
ofanel ectrol
ytesolutionbymeansofaconduct ometer
.TheoryTheconductanceoft hesol
uti
on
i
sexpl ainedbyconsi deri
ngohm’ sl
aw.Accordingtoohm’ slaw thecurr
entfl
owingt hr
oughthe
conductorisdirectlyproport
ional
tovol
tageandi nv
ersel
yproport
ionalt
otheresi
stance.
E=IR
Theresist
anceoftheconductorisdi
rect
lypropor
ti
onalt
othel
engt
handi
nver
sel
ypr
opor
ti
onalt
o
theareaofcrosssect
ion.
Speci
ficconduct
anceisalsocal
ledconducti
vit
y.
 AR
Fur
ther
,
l
1l
1
AR
1
CA
OrSpeci
fi
cconduct
ance=Conduct
ance×cel
lconst
ant
Specifi
cconduct ancei sdefinedast heconduct anceofasol ut
ionenclosedinacel lhavingt wo
el
ect r
odesofuni tareasepar atedbyonecent imeterapar t
.Theconduct anceoft hesolutionis
dependsonmobi lityoft heionsandnumberoft heionspr esenti
nt hesoluti
on.
–1 –1
Unitofspecifi
cconduct ance:Ohm cm
Typesofconduct ance:Conduct ancei scl assifiedintot hreetypes,i
.e.,speci
fi
cconduct ance,
equivalenceconduct anceandmol arconduct ance.
Equivalenceconduct ance( λeq):istheconduct anceoft hesol ut
ionwhen1gequi val
entwei ghtof
2
soluti
oni spl
acedbet weent woel ectrodesofar ea1cm at1cm apar t
.
Mol arconductance( λ):istheconduct anceoft hesolutionwhen1gmol ecularweightofsoluteis
2
pl
acedbet weentwoel ectr
odesofar ea1cm at1cm apar t
.
λ=1000k/ c
K=specif
icconduct
ance(ohm-1cm-1)
3
C=molarconcent
rat
ion(moles/
cm )
-1 2 -
1
Theuni
tofmol
arconduct
ancei
sOhm cm mol

Pri
ncipl
e:Conductomerti
ct it
rati
onsarebasedont hemeasurementofconductanceofsolut
ion,
whichismainlydependsonnumberofi ons,chargeont hei
onsandmobi l
i
tyoftheions.Duri
ng
theti
trat
ionfastmov i
ngi onsarereplacedbysl ow movingi
onsandaltertheconduct
anceofa
solut
ion.Conductance valuesupon addi t
ion oftit
rantvsv ol
ume oftit
rantare pl
ott
ed and
equiv
alencepointi
sobtai
nedf r
om thegraph.

I
nst
rument
ati
on:
Applicationsofconduct
ometri
ctitration:Estimat i
onofweakaci d
Si
ncet heacidisweak,it
sconductiv i
tyisr el
ativelylow.Ont headditi
onofbase,thereisdecrease
i
n conduct ance notonlydue tot he r eplacementofH+ byNa+ butal so suppresses the
di
ssoci ationofaceti
cacidduetocommoni onacet at
e.Butv erysoon,t
heconductanceincreases
onaddi ngNaOHasNaOHneut ralizest heun- dissociatedCH3COOHt oCH3COONawhi chi sthe
strongel ectr
oly
te.Thi
sincr
easeinconduct ancecont inuesraiseupt otheequi
valencepoint.The
graphneart heequival
encepointi scur v edduet hehy drol
ysisofsaltCH3COONa.Bey ondt he
equivalencepoi nt
,conduct
ancei ncr easesmor er apidlywitht headdi
t i
onofNaOH duet ot he
hi
ghl yconduct i
ngOH−ions.

I
ntheabov
egr
aph,
poi
nt(
B)r
epr
esent
stheequi
val
entpoi
ntort
heneut
ral
i
zat
ionpoi
nt.

Pot
b. ent
iomet
ri
cTi
tr
ati
on
Potenti
omet
ri
ct i
trat
ions i
nvolv
et he measur
ementoft he pot
enti
alofa suitableindi
cator
el
ectrodewi
threspecttoar ef
erenceel
ect
rodeasafunct
ionoftit
rantv
olume.Potenti
ometr
yi s
usuall
yempl
oyedtofindtheconcentr
ati
onofasol
utei
nsolut
ion.

Potenti
ometryisthef i
eldofelectr
oanalyt
icalchemist r
yinwhi chpotent
ialismeasuredundert he
conditi
onsofno cur r
entf l
ow.Themeasur edpot enti
almayt henbeusedt o det
erminet he
analyt
icalquanti
tyofi nter
est,gener
all
yt heconcent rati
onofsomecomponentoft heanal yti
c
sol
ution.Thepot ent
ialthatdev el
opsintheel ect
rochemi calcelli
sther esultofthefr
eeener gy
changet hatwoul d occurift hechemicalphenomenawer et o pr
oceed unt i
ltheequil
ibri
um
conditi
onhasbeensat isfi
ed.Thesemethodsr elyont hemeasur ementofEcellf
orquant
ifi
cati
on.
Pr
inci
ple:Redoxti
trat
ionscanbecarr
iedoutpotent
iomet
rical
l
yusi
ngpl
ati
num andcal
omel
el
ectr
odecombinat
ioninamannersi
mil
art
oacid-
baseti
tr
ati
ons.
Fort
her
eact
ion;
Reducedf
orm Oxi
disedf
orm nel
ect
rons
Thepot
ent
ial
isgi
venbyNer
nstequat
ion

E Eo 0.
0591log
[
Oxidi
sedf
orm]n
[
Reducedf
orm]

o
0.
0591 [ Fe3]
E E l
og
n [Fe2]
Where,E0 isthest andardel
ectr
odepot enti
aloft hesy st
em.Thepot entialofthesy stem is
contr
oll
edbyt her ati
oofconcent
rati
onoft heoxidizedtothatofthereducedspecies.Apl otof
changei npotentialagai
nstvol
umei schar act
eri
z edbyasuddenchangeofpot enti
alatt he
equiv
alentpoint.Attheendpoint,potentialisdeterminedbylargejumpi nthepot ent
ialval
ue.
Hencet her
eislargeincr
easei
npotenti
al attheendpoi nt.
I
nst
rument
ati
on:

Procedure:25.0cm3 ofFASwasPipett
edoutint
oacleanbeakerand5.0cm3 ofdil
utesulphuri
c
acidwasadded,andt heplati
num-
cal
omelelect
rodeassembl
ywasi mmersedintot hebeaker
containi
ngt het
estsolut
ion.Theel
ect
rodesar
econnectedtopotent
iometerandini
tialpotent
ial
wasr ecordedwit
houtthe

Platinum el ectrode: I tis an i ndicator

electrode,usedt omeasur ethepot entialof
theanal ytesolutioncompar i
ngwi t
ht hatof
referenceelectr
ode.
Calomel el
ectr
ode: I
tisar eferenceelectrode
and used f or t he det ermination of t he
anal yt
ebymai ntainingt hefixedpotential.
Bur ett
e:StandardK2Cr 2O7soluti
on.
Beaker :Testsolution( FAS)and5ml ofdi l
ute
Sulphur i
cacid(K2Cr O
2 7isa strongoxidizi
ng
agenti nacidi
cmedi um)

addi
ti
onofK2Cr2O7.K2Cr
2O7 wasaddedintheincr
ement
sof0.25mlfrom thesemimi
croburet
te
andcorr
espondingemfwasr ecor
ded.Thi
sprocesswascont
inuedt
il
lther
ewasasuddenrisein
t
hepot
ent
ialandaddi
ti
onalf
ivemor
ereadi
ngswer
erecor
dedaf
tersuddenr
isei
npot
ent
ial
.A
gr
aphwasplott
edbytaki
ng al
ongy-
axi
sandv
olumeofK2Cr
2O7al
ongX-
axi
s.AmountofFAS
wascal
cul
atedusi
ngequi
val
entpoint
.

Vol
.ofK2Cr
2O7 EmfE ∆V(
V2 V1) ∆E ∆E/
∆V
ml (
mv/ml
)
(
V)ml (
mv) (
E2-
E1)

(
NV)
KCrO227

NFAS
VFAS

AmountofFASper
li
ter NFAS Eq.
Wt.
ofFAS(
392)

.
..
..
..
..
..
..
..
..
.g(
say'
a')

392gofFAScont
ains55.
85gFe agofFAS
a
cont
ains 55.
85392 .
..
..
..
..
..
..
..
..
.gofI
ron

bAdvant
agesofPotenti
ometri
cti
trat
ioni)
Themethodisi
nexpensi
ve.
i
i) Thetechni
quecanbeusedf orcolor
ed,tur
bidorf
luor
escentsol
uti
on.
i
ii
) Thetechni
quecanbeusedi nthetit
rat
ionofmixt
ureofaci
dsormi xt
ureofbases.
i
v)Itprovi
desveryaccurat
eresul
ts.