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tA)b~
 CONCENTRATNON Po LARISATION (1.).
n t in souHon a canoda
Considet a
cduction 6 N a

M"ne M
nensh eqNaon,
potenHal, acLodin to
The electoda

E Eo o 0512 og()
n

n aiuhy Niong
So a sto a u s l e a k tha
Cen-1s
moda to tHo,
Iaa
n n enteina
tu ConnhaHorn M" ions in h
euutoh ae, qadually,
elecoda decrcae.
Deathe
SouHorn
naua iony h a n p e t o
OmunkaHon
cnn e
At hhe
nt

Ms londiHon 1 2ivers by
eleoda pottnhad a u
. Ne

E Eo +
0051 2 Vog )-
is knoun
A pokenhal E-E,
The dHfuena
oi conunhaHo oveaerHa
Con Dtredion PolausaHon

camoda e ) .

E- E2 00512 Loa aH
n

at pelauud elechmoe E2z is

NS ,tha Potenha
unpalauzd electreda e . Ih i entara cunt
he
ey han
be reauhud bend
inoreamd uthe, a r a t sil
imik
is ion
reduion cannd be Inortaud uuny. All h
whh
 the eleshode being rduud. Thu valuA uL
Teaching a

is knouwo a mHng uwanhr dunuh (L)

ee3RT23RT o

ppld u a danuh

3
L DFC lb Ac
SE
n no e
D d on coeidens reauH ie
Fauaday commtan

C conanbakon u lonmol lun3)

S thucknan ó t douslu laye

Pre - trem
pot numoe

Nobe
c)
imi

AcH
AL
yoq
CnLrcud o bolau 2ahon
kduhon boca
 Conunaiom l a u zaHon p r orid aHa reauHon a anwda is

3R.T. oq 1+ Aa 7
F
anodde u s n e
a miHn

Canpauin .
whun ta
applied cusin denuhi approa mHny cLRRn
tonLankaHors poallzaHon a t -ta cathode (Mce) inurcay
dansi
anodh is
whetaay COnnadors pdauzaHor atha
apidy
ley Smal

ie' 3R1- oq
Alo
k onianhaHors polau zaion ama
l (), tot
it cppean

cpproauhu co ha ppled e u u n danukdanuk appoauhy

appiauhey
eahode 1.. n e s e veadhý
pvath a polau 2ako
t maHny
muHne un denaiIn ,

eaHon eatabush insely a t a somausha

instead a n o t h e
int
-ue potenhal

* lemp, DIuion veloshy . Mhody td-

edua
L
* . , SHi hick 4 dafpuuan lau Conunhalhon
poouseHon
, Salt conunaHonT

poau2aHon is diuulon cono|led,

tuhaa, oa enunaHe
Sloug 3 Seyea Seand atu the
disappeau
it disappeau Veuy
 folaroaphy
d
elechochamical muhod anauss
folaigvAphisan

o rw ing tr
radhng
o he mealmant 4 wnt
micreleedi a
soluHn a a poausab
eleehesis s
elecbsysis o
a

applied valtage
a unchHor }

Tricip
poaeqaph is baed upam t pvineipl leat qrrdels irerain

voltse applle behw

is ,
eap
elechre, e r s s i h is
Polausablk [ D.N E) Dtee is noD- poausabe t uur
bew ean t 2 electroda is nokd (eord-d
louwng
C L n - vo ltage Cwweis cind e
ASigmoid haped
whih half waue potenhiad
a wel a duim cussnr is

Cal udard
c n is wedpy h deumiraion d erunain
* Distuuim
Sulestanu
Half aua potenhal fs chautusHe e euey elmant

Applie voltue
 CycLIC lbITAMETRY

x T s u t to
Shudy , ComoSio rate
Ina cycue voltumahy epemanky Simullaneuy oudaion and
medu cHon reouhon .a
inuaHqard dhanqiq t poenu
of he woviung elechode uneay ett Hme neau
inea
Sweap voltummat.
*CN tuksthe enipetmanl a step tuthy tan nea
inea uweap
Suleap
oltammy Whuch one udhon ik reahu a S e t pokenHal
wheeas , in C wwn ik eahe a Seh petesHal, the

wortcng elecrods potesha vamp s inuatd Thu

nueyio cas happen mudlipl H m i duung a nala

epeunane

Tha c a n îs ptotted agalnsr the applle voltage togve

Vollammoq vam
au
yeuuy
In C:1, tha elechroda poteshal is Inweqadoeou

is applled behoean h elecdrod q

wortung electras
The polenia
dectads andH C s e n t is m e a u ed
Tenu oute eecroda.
eeatod y
behpean, L wort
hun tplotted euun (ID
Yeu potenHal CE).
T h i daa is

Tha rwaud San produs C n peak tov an

can be redund o1 0idized thoug
a
Cunady te
Scanned
ufF potenH ad
th raung e C
e th orersHal readhes 4 h
will inc
*Th wn

potenhad anayk, bu iE decrea a

VedeHon
1e reduued a t n e
couunrahon t h onalyte
t
eleatods Sutaua
hen tha applied polenkad is rcuajed i u i l l vdusus 4
fovmd In
Potenad a will Ye-odise tra produt
trst Yeduchon eauHon , and pvoduu cuan u

euese pelul tro t h owcud Scan

¥ Thù owdaHon peak olll uuiuálly wil hawe ea Simila

Snope totha reduuhon bea As a reul lndomaH0

cubout tha tedo poteshal e e o cham eo coHoy

a e u t h cempoiund co be obtaunad.

*The uHu ok Cu is highy dapendun

redon auHe
belng Stud edThL analye ha to be
ol m mpeu
ampeu mantol, windouo. i s adso nq
delrala Aor t h analyte to dieplau a revesibi waue

5+ mV
Epe-Fpa= nhell eaaHon

Cpe Asa veduuhior poleshal

Peale
OvidaHoe poBenkad
Cpa .

Lpe C nr paued at reduHon

ar ou dahon
Taa
Tpe CHee Volkmo qvun
Cohue voltamy
polenka waue m

t
OS
Opotent( V vs Ag| Aga)
 p i e d Clyau toy Cy clse voltamihy Setup

(A

V
Rttcuu
elecrals

Couur
lebodA elewd

3:5
CoRRO SloN REVENTION

) CovvOSloN In hi b Hon

covo ssom inhloitos an the Suostuny o upounou orqani

inho tha
l wdl ca Inovgoanuc) hidh a u ad ded dlubaaley
s e to mlm2e Coros lon.
SatuaHon f u amoshee by hai
th a u elhu b
reauHe
Sutab Vapou Prey ob adson on
tn
mut &ukau t h tomn a proledhve laye o

amospie g a .

Adsovph on inbitor mdlauud mo be tmoyh a y hkuo

3
ele chors danaiH p i amas ndn o
aom os
ony
atuhad ddrehy to t suau
auhate han n
Jona
noumcll evy t moleda a a thi y no enatein9
to he bulk sq m itsel
 AcHon wssiom InhiblHm.
Oj
elihe decveau t e \cuk cunuue Ct
E may
cahoC becki ai
matl

ii) t mau aut by inerain -he rstenHal

ion
weea
weie'a
ftat fhe madzul entei poudvaHo

natulaN oxida |aile bauui l em ov

mtal

clatcaHon dFteun type of covvosion inhiblbs om

the bars of heiv mwde oP AcHo

Adsorphon e
Anel RNW2

lourea
nJW2 CSNM2

Anhmony dichlond SLd

Hs Coo, Rtoo
Be2oe
4ilm bvet kuau
urahr tpe tovming pauive

Nih, alkt ltua, Al dibnte,

-
No2 CMNo
, RNOA

chyomoe CY Oy

Lead onid (rrad 2od Po34

C um punba Ca PO4
 Sutae Laue-omnu9 lyp
T5P, SPP
tekre pely phosphatey H2 PO,
phosphak, d, cq
M2Si O
Gba

Ay do ude
HCD3
Bicauo a n a t

Hema makuphos phae

aj Soduy N CPO3)
Henamutaphss phak (SHNP)
comsoro inhlbo-
cooiios n hlby
tonmsio inhbitos-Vepou pha
Amlne pe (SowHmy)
Corvosicinhbiby
VolaH
uq Vapou premu
rotenHol mty -fo
inhbibv shH
n clay COrosloo

Nimk thumbeuy pusak -

PnivaH
o a e
he
tradiHend Plaran d in pans
P b 1 )PLNO
a

The puumleale lon

Zine chmamate
MLri
Me in uqha OS
TEuntuy eord in th
cat
au a i q Oldi zing ag undl matzd
Meta
he .

ValH
m t
t4 Stoue ir
ik pYUmoe past
tal b in cud nahulal Oni Hlm
- IE prote

¥ ||I1 clan Coros slon nhdo toy- tomy Sutauoy

osphoakl, dhmm at th

Cahwdi e
Anodi c
poy phos phaty Amina
phospnay Sdeni dy.
CoCt co3)a
*Silca lompoundy *Maylardo-phuspha
 CATHODIC PROTECTIO

matig mutalse
The rrduchon o Preuento cowosium
ll is calud
SuwL canod i n me elechoyke
anudic aua
the wilnt be an
cahwdie prokcHa uu au 2
ccu
doeindt
maad, Comasiom
e
mehwds p l y n cahe die pokc Hm

Suaua
Ci baciteid arodic pokeaie 9alvanue uteah oy)
cahodie prutrio
Cu) ipreu ed eu

bacniia Anadie Prothom

is madu a camode
meballic Stnuue t b e wtehed

wi more
auHe mu Anodic mud)
s tonnected
th Comosim oil eanhrt
eny cn anade
Hena al
mer

Stnuhuu is h y protetted
Paen
Henu anvdse maa or auive mtd i s colled SacMHdal
anode. ( t is epland a t tull comsion

muta
q'- or anodse
C adlogs
M, Zn, A
pvov I e hiqhe
ha mos
Ve pokenHa cC Can

19
wn oupu ay hon is iely wedun h ushhy
c
uke Soil.
eleoyk
 yound Laved

wie
Ins ulahd p p

Bk l
Så c r l ano d

Cng,zn,
P'pelin to be
Prohe

Applcata

pyotrH n aj buuted Pipeli n , unduq vound caLleu tom Sodl

)
) pokeHon drov Naur comosiom coabu, shp halls,Pieu, -

3 I n setH on Mapnu uno shects Ino-t clonmelhe Wote olley

InseaHon
tpwe t omaHon vu
t l m z e he e i n
H)Calun muzd is employad
ComisAD

Aduan
eos
qUpeciy
), Louo itedlao ukuny
SMLhuny
to poteak smplu
2) copeuuy eye
-)Atplr-el tu wid "Nam ee

Limuion
Skauhy. Cuwenr fs nuadso

canno e protekd
2)ncocched pa
PotenHa. lenne no ppicalsh tovv
mh4 dvivi
Roe ojeus
 Malhoc
Mpreued uwen Cathodic proteHo
In
I n th,mehed Impreue c u u n rs applied
an ppesi
dreehHonto nuluty h e covDssior euint y Conuek
rid bo anod to cahods .

Convocd
nd

Insubrd isppa whr

Sot

Aracle

Pipeb fo b
Potet

uuuu
Peuh te dure unk Souuu ur impuud

Anvde Inesh, insoubie eg.- qrephuk, Soep I n , Srud

Sh plakinu o hh Siuca im ).

A&Hden D.c ls pplred to a n iner ande buurd m t

t th matdlr s muuhu fo be protcukd,
Se Cnaurd
ande is waly, a balk ll pokd 4 coka brea
Th
YPSu, So UnUrtauL
m eeco c o n u wth

tme &uuoundn[otl.

mehod
ud n epen udate om coole cooles,
war ton u
buwed oil ot wata pipe Londunuos
tvammissitm.. ntowes, Navna pu,
p y Lasd wp
lasd zi
p 5np a

i s pauudaly ud for lasny Stuhue Son

tuno eauHon
 s vaion of Meteds

matual so it beuwrmu p a u i u e , h o is ley

k am coaHny a

covodud by h enuivovmnt
Neadly atfruted a

becauue thy adhee to.

h oudel a4e inat. inuhcally
an penehabla ove å tady
utal &utue dounin
thu kinue pvoteuHon is calld o4 p o vadono.
wlde vuyt,

N..t

Descutwd dealleA tn Fuan dia ran

3h
Diagyam
Pouybain Diaqvam Euans Diagvarn
Anodic q canodie au a ypes of elechiods casHan ur
on t h med Sutau o daMon takas plau at anod

n in prena Comvsive ernulron manh pmduu Fi

Olnode

+ae O
At highau PH, t owdakon reauHon acnode poduu a

Suau m a u e oxd

aFe t 3H,o t¬202t 6 t be

Strmlayy a cahodie
imla nreaion is e alechdhumical rdustn
oF diss elue d ayqen sl uak ou e

Ot an,o th Ho

cahedse reduHon oygen at an eechods lads to

inorcaue in p of ha mediu and y by produuh on ydy-

O da m
ac oS S
diffen E is qeneard chtseen t a elechted
T Polenkial
tntea
bw muted i s Seludion wi cdh inereou t ra

CovvoSiun YoCauy.

ise
h a P.D
As cawed ayes of
ehaure at
Sutau t a eleumody Inta
eleatmd s oma elecony pruent atha Suuu
on

aye mated oha eleectods s domu esu

a n j o acaHary u H on d a eleboy e
 fue hG

ht
Cle blybht
solov
callud
chauye avoss -te ineaue is
SepaiaHm
eleczod doubl laye or delmhel Nayey.
a d unde n o n - egulibu
T h e maqnihud f P DE is not
an
c a n be tuhe u chayed by eime uw
ComcuH un, but
chode YcauHoy.
vcauioy.
emk a
cuua o1 chaning spcad
conaneldon oyqen, e rak cahode
e u Louidau the
emore euu o to Hha
whidh will
caion IncNtou ey
matal datden J eleary
muty utua, han makl -h
intmanes it
make ik poslHvely ehaueod th
ohi ch
Polenieil E
elechuds potenhal E ahe
in
Tha ettet chani doua Laye n-th produ
eleeted inteue , ie, at
e undasood tron ouvblx duaYam.
vcauMony can
COYosi o
mukal uc tYbm 1s in
*AF neqahe petHals, 1eynulde Slake
coyYoSIOn is possisu cy is ter
ho
Btabl ovm
D
heut
m t etakgnPehsaste-e
mmuni hy Covdu Hon

i isin the
Ph uauo, nnakelld e.
von
alde
A hiqhe pokeniedy e

om more mo Peavy iony au o r dKoadu no

cuuhe

ion is pvoduus d, ie at a
potenial vedw,-Feuuie
Ata a SHIl hrhe
Pokenti Valuu qreoate ha O V Pn vOYe 9 - 12
s
 t n alkane Sd, h n 4in so Sau e

+e304 will e fmd

Pa i aua

feCm)
fe203

da
feCt)

Non oYYodiaa
J
PuL iVon

pH Scalk
Poubau diaaam

Te e mapnaH a l a k ive ide )is 4ovad at loue

ele ds potenaly
The iro onide torms a s u e of t metw which block
Yeukas 4 nanna comosiom Va a Lowed

Thu j nown aPaul A poterral Coepond to pauink

is knou noy Paucivain poBershcd o i d s plmtomudan
the Suts s Cnouwn o4 poude tlm

Electochomica polausahiar Cuwe also knouwn as Evan diaqvay

electoda reautio ouh teut ploua an th mury

sutal
T h a ollouo in e yans DIAGRAMS showsha anodc <y

cahodse pelau2ahom cuuy o i r o in an audie d u i a

penauu
wo m
a
 oMy
Fe203

Paulye

.olrdicq

Avwdie poluizaHay

ecoYY
c a o d i c Palau2aHy
Cydogtn erduia)

coYY
CL Ct(MA)
EVans diaqveun

xuu ut H clectw de au dependenn

v a k OtoHon
T
the Vou q E
aH in au dUe SduH , Ha i s erolved y
nn a a cadhudse on

rduuion ydegen ion

th
the elew de potenha Eta qak
T moe - te
Sutus
connhaHm <lechony a Suau4 mu
nmu y

be t u
rak o evoluuHor tydvosun qaj.
f a u u oill

Ht +Re
pktion iu):
u x e e s l e a l y to
As we Encue enk T
haus t vaiaHon q cLi
cduaranm
e n u e eva
unlon ctevhal E
rak anodic veaH on Car be Inoreaud b
&mila
n we ddrechoo
ntread potena E
Rare e covvo slon 1 in vaue potenmtal I e divedion

ple a coa r n emtent.

 rraio In wnch
In thu
o lons 'aue prudund
colll tuca plaur
A a sH| hiqn raue l potepkalu, -the r e a i o paM int

T pAuly aHom raion, ha Ycte comosi s r datta

Cythan be . admosr Lou tan y paul raHm d mJ
elehwda In aw dre Seuuion taea pau

PallraHon o mtad electrods Is obseved cu to a

Vey &vnalI yalua t un s towin In t d reaion

h matal In paniye rzion is Pro d by-the preu

of paunie of fwe oude ove tne Sua mat

CoYYrosio reuhe OX
v Mayitud t
COYVosí m cuw

Jcovv dsnnik
can
beeund uat te poi inkuei
unodic ytahodse Tatel polauzaHon cui n
evanu aqamb

Atthi polnt condi kom

equll biun pvevouls,MA
raks cadhods rcardons beuam eaualto Ran
andue
oh aysem s behavia a a cloeed cruuut wi
all eletons pvoduund in he anvda reauhon bel ng
Conunad In calhodie reaHay.

T h e c u n af equilb bviur ie at t pon inteyeHo

is now a eeul: biu .emihange cunnt dauy o)
he pohenha
The pohenil cortapun tothu eaill bfuo Vadu q uun
i lcpwn
S Cnown a eauwllibiu potnha open duit potenHa
(ocP).
T h e elan dlagra MLtd eleehocds dipped In audie
SouHons can be h p l In predicdn s rak t corasl
in mils pes ueumPy wiy Sten exy aH o

303 cow (F 1Pe)

AE slope hich 1s neas poolauizah on eNsrneKr)

anoduc e Cahodie slope epeiely

PaPe
Co YYDc\ m eaun danuk iD MA Co

COvcSion rae = Ola88 x Tesvy X ta wE

Denul
5.2 MIXED-ELECTRODE POTENTIAL
Electrochemical comosion systems can be characterized using the kinetic para-
meters previously described as Tafel slopes, exchange and limiting current den
sities. However, the mixed potential theory requires a mixed electrode systemn.
This is shown in Figure 5.l for the classical pure zinc (2n) electrode immersed
in hydrochloric (HC)acid solution [18-9. This type of graphical representa-
tion of electrode potential and current density is known as Evans Diagram for
representing the electrode kinetics of pure zinc.

S6 CHAPTER5. MIXED POTENTIAL THEORY

0.2 H- 2H+2e Simple Electrode

0.0 E
E
(VStE) 0.2 lo.H
P2H +2e -H
HCkag
0.4
Polarization on the
EconEE Electrode Surface
-0.6 oZn
Zn-Zn+2e
Eozn on ie |B 0.10 v
Pe-0.10V

10 10 10 10
i (AVcm)
Figure 5.1 Evans Diagram for Zinc in HC acid solution.

The Evans diagram requires anodic and cathodic straight lines and the cor
rosion potential (Beorr) and the corosion curent density (ioorr) point located
where hydrogen reduction (H*/Ha) line and zinc oxidation (Zn/Zn*) line
converge. Furthermore, the exchange current densities (o) and the open-circuit
potentials for hydrogen and zinc are necessary for completing the diagram asS
shown in Figure 5.1 for a simple Zn/electrolyte electrochemical system.
In fact, this type of potential-curent density diagram can be developed
for any solid material in contact with an electrolyte containing one or more
oxidizing agents such as H*, Fet", etc..As a result, the corrosion potential
and the corrosion current density can be determined from the diagram (Figure
S.1.n addition, connecting the to and fcorr provides the shown straight lines
which are accompany by their respective overpotential equation. With regard
to the Boorrcorr point in Figure 5.1, the potentials and current densities are
equal since this point represents electrochemical cquilibrium.
On the other hand, Stem [10] used eq. (3.38) to draw anodic and cathodic
nonlinear polarization curves, which provide a more realistic representation of
the electrode kinetics of an electrochemical system. Evans (straight lines) and
Stern (solicd curves) graphical methods are illustrated in Figure 5.2 for a cor
roding hypothetical metal M immersed in an comosive medium containing H*
and Ft oxidizers [6,I3).
5.2. MIXED-ELECTRODE POTENTIAL
157

Evans Diagram
EFe Stem Diagram

E i-i

Ecom -Corrosion Point

EoM ---
lcor

i=i-i
Log (iL)
Figure 5.2 Comparison af polarization diagrams.

The addition of ferrous F* oxidizer to the electrolyte increases the cor

siveness of the electrolyte and
requires an additional Evans
corrosion point of the metal M. In this diagram
in order
to determine the
particular case, the
exchange curent density, open-circuit potential and the Tafel slopes for each
oxidizing agent and the metal is
question must be known prior to construct the
Evans diagram. This, then, is
disadvantage of this technique for determining
a
Eeorr and icorr for the metal M.
Furthermore, using the potentiostatic or
useful in potentiodynamic technique is very
determining the polanization curve near the corosion point. However,
the latter
technique is a faster approach for obtaining even an entire
curve from a low polarization
potential at the limiting current density to a high potential for
oxygen evolution. This dynamic approach
is quite advantageous in
obtaining a
complete polarization curve in a few minutes.

Analysis of Figure 52:

The hypothetical polarization curve shown in Figure 5.2 illustrates a near
realistic industrial condition since most
coroding solutions contain more than
one
oxidizing agent. Normally, ferric-ferrous salts and other ionic
are contained in acid solutions due impurities
and existing oxidizers
contamination from corrosion products
to
4). Nevertheless, the electrochemical situation shown
Figure 5.2 implies that in

The Ecorr icorr point is shifted

addition of Fet ions compared with Figure 5.l due to
as
to M/HT system. Consequently, both Beorr and
corr are inCreased.

The rate
of metal dissolution is increased as well as corosion rate.
 58 CHAPTER 5. MIXED POTENTIAL THEORY

Reduction of Fets/Fet and

H*/H oxidizers
causes a mixed
shift known as corosion potential Eeorr. This upward potential shift
potential
means that the metal becomes more noble (more positive).

Redox reactions occur simultaneously on the metal surface. The exchange

current densities (to) and their corresponding potentials open-circuit po
tentials (E,) are indicated in Figure 5.2 according to the following reduc-
tion reactions

2Fet+2e 2Fet2 BretaFeta =

0.438 VsHE
Ha 2H* +2e BH,/H=00
2Fet3+ Ha 2Fet2+2H* E 0.438 VsHE
Recall that the potential for the redox reaction is E° = Bpeta/Fet» t
BH/H+ and that the potentials for the anodic and cathodic reactions are
given in Table 2.1.

The principle of charge conservation at the point of intersection between

requires Fet"/Fetd reduction line and Ha/H* oxidation line requires an
addition of current density for reducing H*/H2. Then, H*/H2 follows
the dashed line above the Fet"/Fet line until it intersects the M/M**
line. The dashed line represents the total rate of reduction.

For one metal oxidation reaction, two reduction reactions are needed.
Therefore, the addition of Fet ions reduce the hydrogen evolution.

The possible reactions that can occur due to the electrochemical system
shown in Figure 5.2 are

2Fe+2e» 2Fe*2 (Cathodic) (5.1)

2Ht+2e - Ha (Cathodic) (5.2)
2M 2M*+4e" (Anodic) (5.3)
M+2H*+2Fe*3 = M*+2Fet3+2H* (Redom) (5.4)

Addition of an oxidizer to an electrolyte not necessarily increases the cor

rosion potential. It is the exchange current density that dictates such a sit
uation. Ror instance, if io,Feta/Feta << io,M/M*3, then Fet ions does not
have a strong eftects on Beorrand icorr. The opposite IS clearly understood Since
o,onidiser must be high enough to have an effect on Beor-and iearr Further
more, if the applied potential is E =0, then the current does not flow and metal
Oxidation and oxidizer reduction occur simultaneously at the metallelectrolyte
interface. Therefore, the oxidation and reduction curent densities are equal
and i= ioa-ired= 0. On the other hand, if E # 0, then polarization takes
place due to developed anodic and cathodic overpotentials

Ta ( E - Eeorr) >0 (5.5)

e (E- Ecor) < 0 (5.6)
5.3. INTERPRETATION OF POLARIZATION 159

5.3 INTERPRETATION OF POLARIZATION

Anodic reactions represent metal deterioration since a comoding metal osses
electrons. This is a surface electrochemical phenomenon that may cause drastic
effects on metallic structures. Therefore, the driving force for corosion is the
overpotential (7) defined by

7-B-E (5.7)
The subscript "a" and " stand for anodic and cathodic. With regard to
Figure 5.1, assume that current does not flow, then the local potentials become
the open-circuit potentials of the coroding system. Thus,

E
E = Ez»/zat" (5.8)
On the other hand, if current flows, irreversible efects occur at the electrode
surface due to electrochemical polarization effects. In this case, the corosion
and current density compared with the cathodic and
potential comosion
anodic terms. Thus,
are

E<Eoor,E (5.9)
icore ioa >ioe (5.10)
o, o,n/Znt (6.11)
io,e=io,H* /Ha (5.12)
Additionally, electrochemical polarization is a measure of the overpotential
and represents a deviation of the electrochemical state of half-cell electrodes
induced by an applied extermal potential. Therefore, the driving force for elec
trochemical polarization is the overpotential.
Consequently, the electrochenical polanzation is divided into two classifica
tions, such as anodic polarization and cathodic polarzation. The coresponding
Overpotentials are defined by eqs. (3.35a) and (3.356). Recall that the over-
potentials for the anodic and cathodic parts of a polarization curve represent
deviation from equilibrium anodically or cathodically. For convenience,

(5.13)

.14)

In general, the higher the current density the higher the overpotential and
the faster the electrochemical rate of reaction. Furthemore, other aspects of
the polarization must be considered as a beneficial phenomenon for electromet
allurgical operation, such as electrowinning, electrorefining, electroplating, and
 160 CHAPTER 5. MIXED POTENTIAL THEORY

cathodic protection against corosion or a detrimental process for material sur-

face deterioration known as corrosion. Therefore, continuous polarization causes
local potentials to change until a steady state is reached and the observed mixed
polentials is the comosion potential (Eeo) of the coroding electrochemical sys-
tem. it been assumed the and
Thus far has that
temperature pressure are
constant; otherwise, temperature and pressure gradients must included in the
remain
analysis of the electrochemical
system.
A polarization diagram predicts the type of half-cell controlling the elec-
trochemical sysiem. Figure 5.3 depicts two schematic case for determining the
controlling type of polarization.

Anodic Control Cathodic Control

E E Ba | p
ExoE EcoE

M= M+ ze

Log (loo) Log((loom)

Figure 5.3 Schematic Evans diagrams showing controlling polarization.

Consider the electrochemical cels illustrated in Figure 54. When the cir-
Cuit s disconnected current does not flow and the cell is at thermodynamics
equilibrium. However, when curent flows
the cell 1s polanzed and the forward
(cathodic) and reverse (anodic) currents and potential at the electrodes have
the following conditions

I>la for M*+ze Mat the cathode electrode

for M> M**+ zeat the anode electrode
. = (-16). atat the
EE<E the voltmeter
anode electrode
V

Subsequently, the rates of charge transter processes are not equal and
the
equilibrium state is disturbed. Therefore, the electrodes are polarized. The
5.4. PREDETERMINED CORROSION RATE 161

comesponding overpotentials for this polarized cell are given by egs. (5.13) and
(5.14).

ED.C. Supply
A

M
MXaq

Anode (a)
Cathode (c)|
Figure 5.4 Polarization call for metal M.

5.4 PREDETERMINED CORROsION RATE

Consider the cell shown in Figure 5.5 for measuring corosion rate of zinc (Zn)
at a predetenined rate through a resistor in the circuit [12].

R E

wH

Gas
ZnSO4 TIHC
Figure 5.5 Reveraible cell for measuring corrosion rate of zinc.

RESISTANCE-OFF. The reversible cell shown in Figure 5.5 can be rep-

resented by the following notation
 62 CHAPTER S. MIXED POTENTIAL THEORY

Zn Zn*,ZnSO||H*, Ha|Pt (5.15)

According to this cell with the resistance Ra being disconnected the following
reactions Occur

Zn Zn**+ 2e (Anode) (6.16)

2Ht+2e Ha (Cathode) (5.17)
Zn +2H* Zn* + Ha (Re dor) (5.18)
According to eq. (5.17), hydrogen evolution occurs on the Zn surface elec-
trode not on the Pt electrode [12]. This is far way from the real electrochemical
interaction and therefore, the current cannot be measured. This implies that
the potential of each electrode can be measured by connecting high-impedlance
voltmeters, V1 and V2, as shown in Figure 5S. At equilibrium, the currents and
potentials are Ie = a = 0 and E = E e - Ea. The free energy change (4G)
and the electric potential difference (E) of the cell for the redox reaction can
be determined using eqs. (2.31) and (2.32), respectively. For convenience, these
equations

E E- (K) (5.19)
AG =-zFE (5.20)

RESISTANCE-ON. Adjusting the resistance in the external circuit de-

velops an overpotential and corrosion of Zn proceeds at a finite rate. This sug-
gests that the cell is polarized. This polarization process implies that the anode
becomes more positive for the oxidation of zinc (Zn/2n**) and the cathode
becomes more negative for the reduction of hydrogen ions or hydrogen evolu-
tion (2H*/Ha). The measurable cell electric potential is defined in terms of
open-circuit electric potential, anodic and cathodic electric overpotentials and
Ohm's law
by law. Hence, E = B, (ate+IR,) and according to Ohm's
the potential is B = IRE. Therefore, E - ( 7 + e + I R ) / R , which suggests
that the current / is strongly dependent oh the external resistance R=, but the
comosion of zine can proceed at a finite rale when R 1S Constant. If R = 0,
of rate
then the cell becomes short-circuited and the current becomes
of charge transfer [12]. Thus,
a measure

According to Shreir |12], a well-defined electrochemical cell containing an

electrolyte of high conductivity dictates that Ohm's law for the external circuit
and for the solution must give IR s0 and IR, 0 . Thus, the cell reversible
open-circuit potential becomes E = 7a tIe This expression clearly shows
that there is a mixed potential relationship. which implies that the measured
potential is a mixed-potential in nature. This mixed potential is shown in Figure
32 as the Stern diagram or the polanzation diagram.
5.5. POLARIZATION OFA GALVANIc CELL 65

Example 5.1 Determine the overpotential and free energ)y change profiles
as functions of the reaction constant at varying temperature. Explan the elec-
trochemical behavior.

Solution:

below show the required profiles for E f(K, T) and n=

The Jigures
F(K,T) in two dimensions Succincily, both overpotential and free energy change
are very sensitive to variations of bolh the reaction constant and temperature.

-(5.20)
Increasing
Temperatur

Increusing
Temperature

Eq. (5.19)

Example 5.1

5.5 POLARIZATION OF A GALVANIC CELLL

hypothetical
This is the case for galvanic coupling areParticular
polarizing a
shown in Figure 5.6.
curves for metals Mi
and Ma
galvanic polarization and electron
These curves imply that metals Mi and Ma
are
connected (coupled)
For
from M1 to since Ma since leorr,M1
< loorr,M2* convenience,
flow occurs
reactions that take
valence 3. The main
that the metals have the
same
assume
 164 CHAPTER 5. MIXED POTENTIAL THEORY

place in the coupling are

M *3E Mi (Anode) (5.21)

Ma M+ze". (Cathode) (5.20)
M+Ma Mi+M (Redax) (5.23)
Thus, the coupling corrosion cuTent density is depicted from Figure 5.6 at
the crossover (intersect) of the anodic and cathodic polarization curves. This
cOuple curent density has a value
metal Miand M2, respecuvely
between the comosion current density for

corr,M1couplecorr leorr,M2 (5.24)

When steady-state is reached the current densities and potentials become
equal; that is,

ooupie Equilibrium (5.25)

Ecouple Ecorr O Equilibrium (5.26)

Metal M,

EoMm

Ecor Ecouple
EoMa Metal M|

Log[loM lo,xa lcorlcouple

Figure 5.6 Schematic Galvanic couple polarization.

t should be pointed out that the cormosion potential in the galvanic series
(Table 2.3) and that in the emf series (Table 2.4) are not the same. The former
may be measured as a coupled potential at different temperatures and ionic
concentrations used in the latter senes. Therefore, the galvanic series must be
Used with caution since it is temperature and concentration dependent kinetie
parameter.
5.6. EFFECT OF SURFACE AREA 165

5.6 EFFECT OF sURFACE AREA

The surface area of the electrode in the corrosive medium is known as the
relative area, which influences the rate of galvanic corosion. For nstance,
the experimental data on
brass/steel couple in 20%NaCl at mom temperature
reported by Jones [19] can be used to determine that increasing the surface area
ratio increases the the galvanic iscomosion potential. Therefore, the corosion
on the cathode-to-anode
potential of galvanic couplings strongly dependent
surface area ratio.

5.7 SUMMARY

The mixed-potentialspecies
theory includes both anodic flowing
and cathodic
the polarization,
is related to the curent
in
electrolyte. The in
which
diffusion of
principles mixed-potential allows the characterization
of of electrochemical c o r
rosion systems by developing an Evan's diagram if the 1Tafel slopes and exchange
The
current densities and at least one
oxidizer agent are
known. kinetic para
meters that are determined from an Evan's diagran are the corrosion potential
also
and the
corosion current densities. Potentiodynamic polarnization curves
know as Stern diagrams are oblainable very easily and exhibit different features
that are useful in charactenzing the electrochemical behavior of electrodes.
In addition, a departure from electrochemical equilibrium leads to a polar-

1zation scheme due to a developed overpotential > 0

for anodic polarization
and 7 < 0 for cathodic polarization. lf cument flows and 7 0, iTeversible el-
fects occur on the electrodes surfaces during polarization, which in turn, causes

steady-state is reached.
changes in local potentials until a

Charactenzing galvanic thee

corosion in a particular environment simulating the
service atmosphere must be done with caution. AS previously mentioned,
concen
galvanic coTosion potential is sensity
to
changes in temperature, ionic
traion and cathode-toanode surface area ratio.