MODERN THEORY PRINCIPLES

Thermodynamics of Corrosion
Thermodynamics of Corrosion
The change in free energy (
The change in free energy (

G) is a direc
G) is a direc
!eas"re #f he $#r% ca&aciy #r !a'i!"!
!eas"re #f he $#r% ca&aciy #r !a'i!"!
e(ecric energy a)ai(a*(e fr#! a syse!+
e(ecric energy a)ai(a*(e fr#! a syse!+

G , - n.E
G , - n.E
$here/
$here/
n
n
, n"!*er #f e
, n"!*er #f e
- -
in)#()ed
in)#()ed
.
.
, .araday c#nsan
, .araday c#nsan
, 01233 C#"(#!*s4!#( e
, 01233 C#"(#!*s4!#( e
- -
E
E
, ce(( &#enia(
, ce(( &#enia(

If
If

G is - (negai)e)5 (#ss #f energy5 he

G is - (negai)e)5 (#ss #f energy5 he
&r#cess is s&#nane#"s+
&r#cess is s&#nane#"s+

If
If

G is 6 (&#sii)e)5 increase #f energy

G is 6 (&#sii)e)5 increase #f energy
(he &r#cess re7"ires addii#na( energy)5
(he &r#cess re7"ires addii#na( energy)5
he &r#cess is
he &r#cess is
n#
n#
s&#nane#"s
s&#nane#"s

The change in free energy is a state function

The change in free energy is a state function
and is independent of the reaction path.
and is independent of the reaction path.

It is not possible to accurately predict the

It is not possible to accurately predict the
velocity of a reaction from the change in its
velocity of a reaction from the change in its
free energy.
free energy.

It reflects only the direction of reaction by

It reflects only the direction of reaction by
its sign.
its sign.

Standard Redox Potential
Standard Redox Potential
(25 (25
o o
C C, 1M) , 1M)



Cell Potentials and the EMF Series
Cell Potentials and the EMF Series

Consider the reaction between inc and

Consider the reaction between inc and
copper!
copper!
Cu " #n
Cu " #n
$"
% Cu
% Cu
$"
" #n
" #n
&e'uilibrium reaction(
&e'uilibrium reaction(
#n and Cu electrodes in e'uilibrium with their ions
#n and Cu electrodes in e'uilibrium with their ions

Cu % Cu
Cu % Cu
$"
" $ e
" $ e
) )
&"*.++,(
&"*.++,(


#n
#n
$"
" $e
" $e
) )
% #n &"*.,-+(
% #n &"*.,-+(
Electrodes must be
Electrodes must be
at e'uilibrium
at e'uilibrium
&.eversible electrodes(
&.eversible electrodes(

/alf cell
/alf cell

Consider the replacement reaction between

Consider the replacement reaction between
Copper and silver!
Copper and silver!
Cu " $0g
Cu " $0g
"
% Cu
% Cu
$"
" $0g
" $0g
&e'uilibrium reaction(
&e'uilibrium reaction(
In this cell Cu is negative
In this cell Cu is negative
with respect to 0g
with respect to 0g

/alf Cell Potential
/alf Cell Potential
/ydrogen)/ydrogen Ion
/ydrogen)/ydrogen Ion

$ /
$ /
" "
" $ e
" $ e
) )
% /
% /
$ $
#n
#n
$"
" $e
" $e
) )
% #n &)*.,-+(
% #n &)*.,-+(

Nerns
Nerns
E7"ai#n
E7"ai#n

E , E
E , E
# #
6 8+9 ( ) (#g ( )
6 8+9 ( ) (#g ( )

E
E
# #
he sandard ce(( &#enia(
he sandard ce(( &#enia(

T
T
a*s#("e e!&era"re
a*s#("e e!&era"re

n
n
n"!*er #f e(ecr#ns ransferred
n"!*er #f e(ecr#ns ransferred

.
.
.araday c#nsan (01233 c#"(4!#( e
.araday c#nsan (01233 c#"(4!#( e
- -
)
)

a
a
#'id #'id
aci)iy #f #'idi:ed s&ecies
aci)iy #f #'idi:ed s&ecies

a
a
red red
aci)iy #f red"ced s&ecies
aci)iy #f red"ced s&ecies

RT
nF
oxide
red
a
a

0pplication of Thermodynamics to
0pplication of Thermodynamics to
Corrosion
Corrosion

.ree energy &redics he s&#nane#"s direci#n #f .ree energy &redics he s&#nane#"s direci#n #f
any e(ecr#che!ica( reaci#n+ any e(ecr#che!ica( reaci#n+

In any e(ecr#che!ica( reaci#n he !#s negai)e #r In any e(ecr#che!ica( reaci#n he !#s negai)e #r
aci)e ha(f ce(( ends # *e #'idi:ed5 and he !#s aci)e ha(f ce(( ends # *e #'idi:ed5 and he !#s
&#sii)e #r n#*(e ha(f ce(( ends # *e red"ced+ &#sii)e #r n#*(e ha(f ce(( ends # *e red"ced+

;(h#"gh c#&&er and si()er are n# c#rr#ded *y acid ;(h#"gh c#&&er and si()er are n# c#rr#ded *y acid
s#("i#ns5 if diss#()ed #'ygen is &resen here is a s#("i#ns5 if diss#()ed #'ygen is &resen here is a
&#ssi*i(iy #f #'ygen red"ci#n+ &#ssi*i(iy #f #'ygen red"ci#n+

;s he re)ersi*(e &#enia( #f a !ea( *ec#!es !#re ;s he re)ersi*(e &#enia( #f a !ea( *ec#!es !#re
n#*(e5 is endency # c#rr#de in he &resence #f n#*(e5 is endency # c#rr#de in he &resence #f
#'idi:ing agens decreases+ #'idi:ing agens decreases+

Pourbai1 2iagrams
Pourbai1 2iagrams
&Potential)p/ Plots(
&Potential)p/ Plots(

The !ain "ses #f hese diagra!s are/
The !ain "ses #f hese diagra!s are/

<+
<+
&redicing he s&#nane#"s
&redicing he s&#nane#"s
direci#n #f reaci#ns+
direci#n #f reaci#ns+

8+
8+
Esi!aing he c#!&#sii#n #f
Esi!aing he c#!&#sii#n #f
c#rr#si#n &r#d"cs5
c#rr#si#n &r#d"cs5

9+
9+
&redicing en)ir#n!ena( changes
&redicing en)ir#n!ena( changes
ha $i(( &re)en #r red"ce c#rr#si#n
ha $i(( &re)en #r red"ce c#rr#si#n
aac%+
aac%+


Electrode
Electrode
Kinetics
Kinetics

In Fig. 3.3 the inc electrode rapidly dissolves in the

solution and rapid evolution of hydrogen is observed on
the platinum electrode.
This is e1actly the same process when inc is immersed
in a hydrogen saturated acid solution containing inc
ions.

4hen a cell is short circuited and a net o1idation and

reduction processes occur at the electrode interfaces5 the
potential of these electrodes will no longer be at their
e'uilibrium potential.

The deviation from e'uilibrium potential is called

polarization.

Polarization
Polarization

Polarization
Polarization
is he dis&(ace!en #f e(ecr#de
is he dis&(ace!en #f e(ecr#de
&#enia( res"(ing fr#! a ne c"rren+ The
&#enia( res"(ing fr#! a ne c"rren+ The
!agni"de #f &#(ari:ai#n is !eas"red in
!agni"de #f &#(ari:ai#n is !eas"red in
er!s #f #)er)#(age (
er!s #f #)er)#(age (

)+
)+

O)er)#(age is a !eas"re #f &#(ari:ai#n

O)er)#(age is a !eas"re #f &#(ari:ai#n
$ih res&ec # he e7"i(i*ri"! &#enia( #f
$ih res&ec # he e7"i(i*ri"! &#enia( #f
an e(ecr#de5 $hich is c#nsidered as
an e(ecr#de5 $hich is c#nsidered as
:er#
:er#
+
+

O)er)#(age can *e i)e #r 6i)e $r his :er#

O)er)#(age can *e i)e #r 6i)e $r his :er#
reference+
reference+

Example of overvoltage
Example of overvoltage

Consider that the inc electrode which is

Consider that the inc electrode which is
coupled to the platinum electrode has a
coupled to the platinum electrode has a
potential after coupling of 6)*.--)&)*.,-(7 %"*.8
potential after coupling of 6)*.--)&)*.,-(7 %"*.8
volt.
volt.
The overvoltage is " *.8* volt % 8** m9
The overvoltage is " *.8* volt % 8** m9

Exchange Current Density
Exchange Current Density
(
(
i
i
# #
)
)

I is he rae #f #'idai#n and red"ci#n

I is he rae #f #'idai#n and red"ci#n
reaci#ns a an e7"i(i*ri"! e'&ressed
reaci#ns a an e7"i(i*ri"! e'&ressed
in er!s #f c"rren densiy+
in er!s #f c"rren densiy+

The e'change c"rren densiy )aries

The e'change c"rren densiy )aries
de&ending #n he !ea( e(ecr#de5 and
de&ending #n he !ea( e(ecr#de5 and
#n he s"rface r#"ghness+
#n he s"rface r#"ghness+

E'uilibrium conditions dictate that the rate of
E'uilibrium conditions dictate that the rate of
o1idation and reduction5 r
o1idation and reduction5 r
8 8
and r
and r
$ $
respectively5
respectively5
must be e'ual.
must be e'ual.

0t e'uilibrium hydrogen electrode there is a finite

0t e'uilibrium hydrogen electrode there is a finite
rate of interchange between hydrogen molecules
rate of interchange between hydrogen molecules
and hydrogen ions in solution.
and hydrogen ions in solution.

The e1change reaction rate is e1pressed in terms of

The e1change reaction rate is e1pressed in terms of
current density.
current density.
r
r
#'id #'id
, r
, r
red red
,
,
0t e'uilibrium
0t e'uilibrium

Plotting electrode potential versus reaction rate

Plotting electrode potential versus reaction rate
&following Fig( e1pressed in terms of moles reacting
&following Fig( e1pressed in terms of moles reacting
per cm
per cm
$ $
per s.
per s.
o
i
n F

E1change current density varies depending

E1change current density varies depending
on the metal electrode
on the metal electrode

There is no theoretical way of precisely

There is no theoretical way of precisely
determining the e1change current density for any
determining the e1change current density for any
given system! it must be determined
given system! it must be determined
e1perimentally.
e1perimentally.

The magnitude of e1change current density is a

The magnitude of e1change current density is a
function of several variables:
function of several variables:

It is a specific function of the redo1 reaction.

It is a specific function of the redo1 reaction.

It is related to electrode composition.

It is related to electrode composition.

It is influenced by the ratio of o1idied and

It is influenced by the ratio of o1idied and
reduced species and the temperature of the
reduced species and the temperature of the
system.
system.


POL;RI=;TION
POL;RI=;TION
Electrochemical polariation is divided into two main types : Electrochemical polariation is divided into two main types :

0ctivation polariation. 0ctivation polariation.
and and
Concentration polariation. Concentration polariation.


0CTI90TI;< P;=0.I#0TI;<
0CTI90TI;< P;=0.I#0TI;<
(de&ends #n he e(ecr#de ise(f) (de&ends #n he e(ecr#de ise(f)
It is represented by Tafel e'uation:
It is represented by Tafel e'uation:


>
>
a a
% ?
% ?
@
@
log &iAi
log &iAi
o o
(
(
4here
4here
:
:

>
>
a a
is overvoltage5
is overvoltage5

@
@
is the Tafel constant.
is the Tafel constant.
It ranges between *.*B and .8B volts
It ranges between *.*B and .8B volts
5 in general it
5 in general it
% *.8 9olt.
% *.8 9olt.
and
and
i
i
is the rate of o1idation or reduction in
is the rate of o1idation or reduction in
terms of current density.
terms of current density.

0t all potentials more noble than the

0t all potentials more noble than the
reversible potential a net o1idation process
reversible potential a net o1idation process
occurs.
occurs.

0t all potentials more active or more

0t all potentials more active or more
negative than the reversible potential a net
negative than the reversible potential a net
reduction occurs.
reduction occurs.

0t the reversible potential5 or at ero

0t the reversible potential5 or at ero
overvoltage5 there is no net rate of o1idation
overvoltage5 there is no net rate of o1idation
or reduction since both rates are e'ual at
or reduction since both rates are e'ual at
this intersection point.
this intersection point.

C;<CE<T.0TI;< P;=0.I#0TI;<
C;<CE<T.0TI;< P;=0.I#0TI;<
(de&ends #n he i#ns c#ncenrai#n in he
(de&ends #n he i#ns c#ncenrai#n in he
s#("i#n)
s#("i#n)

0t low reduction rates the distribution

0t low reduction rates the distribution
of hydrogen ions in the solution
of hydrogen ions in the solution
adCacent to the electrode surface is
adCacent to the electrode surface is
relatively uniform.
relatively uniform.

0t very high reduction rates the region

0t very high reduction rates the region
adCacent to the electrode surface will
adCacent to the electrode surface will
become depleted of hydrogen ions.
become depleted of hydrogen ions.

If the reduction rate is increased further5 a

If the reduction rate is increased further5 a
limiting rate will be reached that
limiting rate will be reached that
determined by the diffusion rate of
determined by the diffusion rate of
hydrogen ions to the electrode surface.
hydrogen ions to the electrode surface.

This limiting rate is the limiting diffusion

This limiting rate is the limiting diffusion
current density i
current density i
= =
. It represents the
. It represents the
ma1imum rate of reduction possible for a
ma1imum rate of reduction possible for a
given system:
given system:

i
i
L L
,
,
i
i
= =
is the limiting diffusion current density
is the limiting diffusion current density
D
D
is the diffusion coefficient of the reacting ions
is the diffusion coefficient of the reacting ions
.
.
C
C
D D
is the concentration of the reacting ions in the bulE
is the concentration of the reacting ions in the bulE
solution
solution
1
1
is the thicEness of the diffusion layer.
is the thicEness of the diffusion layer.

=imiting diffusion current density is a function of
=imiting diffusion current density is a function of
diffusion coefficient5
diffusion coefficient5
concentration of reacting ion in solution5 and
concentration of reacting ion in solution5 and
thicEness of the diffusion layer.
thicEness of the diffusion layer.
B
n F C
!

There is a linear relationship between

There is a linear relationship between
concentration and the limiting diffusion
concentration and the limiting diffusion
current density.
current density.

The diffusion layer thicEness is influenced

The diffusion layer thicEness is influenced
by the shape of the electrode5 the geometry
by the shape of the electrode5 the geometry
of the system and by agitation.
of the system and by agitation.

0gitation tends to decrease the diffusion

0gitation tends to decrease the diffusion
layer thicEness because of convection
layer thicEness because of convection
currents and conse'uently increases the
currents and conse'uently increases the
limiting diffusion current density.
limiting diffusion current density.

=imiting diffusion current density is usually

=imiting diffusion current density is usually
only significant during reduction processes
only significant during reduction processes
and is usually negligible during metal)
and is usually negligible during metal)
dissolution reaction.
dissolution reaction.

=imiting diffusion current density can be

=imiting diffusion current density can be
ignored during most metal)dissolution
ignored during most metal)dissolution
reactions. The reason for this is5 simply5 that
reactions. The reason for this is5 simply5 that
there is an almost unlimited supply of metal
there is an almost unlimited supply of metal
atoms for dissolution.
atoms for dissolution.

The value of the diffusion layer thickness

The value of the diffusion layer thickness
must be determined experimentally.
must be determined experimentally.

If $e c#nsider an e(ecr#de in $hich

If $e c#nsider an e(ecr#de in $hich
here is n# aci)ai#n &#(ari:ai#n5 hen
here is n# aci)ai#n &#(ari:ai#n5 hen
he e7"ai#n f#r c#ncenrai#n
he e7"ai#n f#r c#ncenrai#n
&#(ari:ai#n is/
&#(ari:ai#n is/


>
>
c c
, 8+9 (R T4n .) (#g (< i4i
, 8+9 (R T4n .) (#g (< i4i
L L
)
)

0s the solution velocity5 concentration5 or

0s the solution velocity5 concentration5 or
temperature are increased5 limiting diffusion
temperature are increased5 limiting diffusion
current increases.
current increases.

C;MDI<E2 P;=0.I#0TI;<
C;MDI<E2 P;=0.I#0TI;<

Doth activation and concentration

Doth activation and concentration
polariation usually occur at an electrode.
polariation usually occur at an electrode.

0t low reaction rates5 activation

0t low reaction rates5 activation
polariation usually controls5 whereas at
polariation usually controls5 whereas at
higher reaction rates concentration
higher reaction rates concentration
polariation becomes controlling.
polariation becomes controlling.

The total polarization of an electrode is the sum

The total polarization of an electrode is the sum
of the contribution of activation and
of the contribution of activation and
concentration polarizations.
concentration polarizations.

,
,

a a
6
6

c c

,
,
-
-

(#g (
(#g (
i
i
4
4
i
i
# #
)
)
6 8+9 (RT4n.) (#g (<-
6 8+9 (RT4n.) (#g (<-
i
i
4
4
i
i
L L
)
)

2uring 0nodic dissolution5 Concentration

2uring 0nodic dissolution5 Concentration
polariation is not a factor.
polariation is not a factor.


>
>
diss diss
% ?
% ?
@
@
log &iAi
log &iAi
o o
(.
(.
This e'uation applies to almost all anodic
This e'uation applies to almost all anodic
dissolution reactions e1cept for metals which
dissolution reactions e1cept for metals which
demonstrate active)passive behavior.
demonstrate active)passive behavior.

During reduction processes 9such as hydrogen

During reduction processes 9such as hydrogen
evolution or oxygen reduction), concentration
evolution or oxygen reduction), concentration
polarization is important as the reduction rate
polarization is important as the reduction rate
approaches the limiting diffusion current density.
approaches the limiting diffusion current density.
Then the overall reduction e'uation is:
Then the overall reduction e'uation is:
>
>
red red
% )
% )
@
@
log &iAi
log &iAi
o o
( "
( "
$.+ &. TAn F( log &8 F iAi
$.+ &. TAn F( log &8 F iAi
= =
(.
(.

This e'uation applies to any reduction reaction.

This e'uation applies to any reduction reaction.


MIGE2)P;TE<TI0= T/E;.H
MIGE2)P;TE<TI0= T/E;.H
The mi1ed)potential theory consists of two simple
The mi1ed)potential theory consists of two simple
hypotheses
hypotheses
:
:
8. 0ny electrochemical reaction can be
8. 0ny electrochemical reaction can be
divided into two or more partial
divided into two or more partial
o1idation and reduction reactions.
o1idation and reduction reactions.
$. There can be no net accumulation of
$. There can be no net accumulation of
electric charge during an electrochemical
electric charge during an electrochemical
reaction &the law of conservation of
reaction &the law of conservation of
charge(.
charge(.
This means that the total rate of o1idation
This means that the total rate of o1idation
must e'ual the total rate of reduction.
must e'ual the total rate of reduction.

MIGE2 E=ECT.;2E
MIGE2 E=ECT.;2E

0 mi1ed electrode is an electrode or

0 mi1ed electrode is an electrode or
metal sample that is in contact with
metal sample that is in contact with
two or more o1idation)reduction
two or more o1idation)reduction
systems.
systems.

<+
<+
;ac% #n :inc *y hydr#ch(#ric
;ac% #n :inc *y hydr#ch(#ric
acid (air-free HC()
acid (air-free HC()
If a &iece #f :inc is insered in HC(
If a &iece #f :inc is insered in HC(
c#naining s#!e :inc i#ns5 he
c#naining s#!e :inc i#ns5 he
e(ecr#de cann# re!ain a eiher #f
e(ecr#de cann# re!ain a eiher #f
hese $# re)ersi*(e &#enia(s *"
hese $# re)ersi*(e &#enia(s *"
!"s (ie a s#!e #her &#enia( $here
!"s (ie a s#!e #her &#enia( $here
he #a( rae #f #'idai#n e7"a(s he
he #a( rae #f #'idai#n e7"a(s he
#a( rae #f red"ci#n (E
#a( rae #f red"ci#n (E
c#rr c#rr
)+
)+
E1amples:

;nly at this point &E

;nly at this point &Ecorr corr
( is charge
( is charge
conservation maintained.
conservation maintained.

The current density corresponding to this

The current density corresponding to this
point is usually called corrosion current
point is usually called corrosion current
density5 i
density5 i
corr corr
5 since it represents the rate of
5 since it represents the rate of
inc dissolution.
inc dissolution.

/ere5 i
/ere5 i
corr corr
also corresponds to the rate at
also corresponds to the rate at
which hydrogen gas is evolved.
which hydrogen gas is evolved.

$. Corrosion behavior of iron in dilute
$. Corrosion behavior of iron in dilute
hydrochloric acid solution.
hydrochloric acid solution.

The steady state of this particular system

The steady state of this particular system
occurs at the intersection between the
occurs at the intersection between the
polariation curves for iron dissolution
polariation curves for iron dissolution
and hydrogen evolution.
and hydrogen evolution.

0lthough the free energy for the dissolution

0lthough the free energy for the dissolution
of iron is lower than that of inc &the cell
of iron is lower than that of inc &the cell
potential for iron and hydrogen electrode
potential for iron and hydrogen electrode
under standard conditions is *.II volt as
under standard conditions is *.II volt as
contrasted to *.,- volt for inc(5 the
contrasted to *.,- volt for inc(5 the
corrosion rate of iron is greater than that of
corrosion rate of iron is greater than that of
pure inc when e1posed to identical
pure inc when e1posed to identical
concentrations of hydrochloric acid.
concentrations of hydrochloric acid.

This is due to the very low e1change current

This is due to the very low e1change current
density for hydrogen)evolution reaction on
density for hydrogen)evolution reaction on
inc surfaces.
inc surfaces.

Thus5 although the free)energy change for the

Thus5 although the free)energy change for the
corrosion of inc is negative and greater than
corrosion of inc is negative and greater than
that for iron5 the corrosion rate of inc is less
that for iron5 the corrosion rate of inc is less
than that of iron.
than that of iron.
This illustrates the error that may be introduced
This illustrates the error that may be introduced
by assuming that free)energy change and
by assuming that free)energy change and
corrosion rate are proportional.
corrosion rate are proportional.

9
9
. 0 fre'uent impurity in commercial /Cl is
. 0 fre'uent impurity in commercial /Cl is
ferric ion5 present as FeCl
ferric ion5 present as FeCl
+ +
!
!

The point at which the total rate of

The point at which the total rate of
o1idation e'uals the total rate of reduction
o1idation e'uals the total rate of reduction
&at steady state( is the mi1ed or corrosion
&at steady state( is the mi1ed or corrosion
potential of this system.
potential of this system.

0 horiontal line is drawn in E

0 horiontal line is drawn in E
corr corr
since the
since the
metal is e'uipotential.
metal is e'uipotential.

The rate of metal dissolution or the corrosion

The rate of metal dissolution or the corrosion
current is given by i
current is given by i
corr corr
.
.

The rate of ferric)ion reduction is e'ual to

The rate of ferric)ion reduction is e'ual to
i
i &Fe &Fe
+" +"
J J Fe Fe
$" $"
(. (.

The rate of hydrogen evolution is given by

The rate of hydrogen evolution is given by
i
i &/ &/
" "
J J / /
$ $
(. (.

In the absence of o1idiers5 the corrosion rate of

In the absence of o1idiers5 the corrosion rate of
metal M is given by the intersection of the
metal M is given by the intersection of the
hydrogen)reduction and metal dissolution
hydrogen)reduction and metal dissolution
polariation curves.
polariation curves.

The addition of an o1idier5 such as ferric ions5

The addition of an o1idier5 such as ferric ions5
shifts the corrosion potential to E
shifts the corrosion potential to E
corr corr
and
and
conse'uently increases corrosion rate from iK
conse'uently increases corrosion rate from iK
corr corr

to i
to i
corr corr
and decreases hydrogen evolution from
and decreases hydrogen evolution from
iK
iK
corr corr
to i
to i &/ &/
" "
J J / /
$ $
(.
(.

In o1idier)free acids i
In o1idier)free acids i
corr corr
% rate of /
% rate of /
$ $
evolution.
evolution.



I. Corrosion of metal M under reduction)
I. Corrosion of metal M under reduction)
diffusion control
diffusion control

0 corrosion of a metal M in a weaE acid

0 corrosion of a metal M in a weaE acid
solution where the reduction process is
solution where the reduction process is
under diffusion control.
under diffusion control.

In this e1ample5 the metal M follows the

In this e1ample5 the metal M follows the
typical anodic dissolution reaction under
typical anodic dissolution reaction under
activation control.
activation control.

Initially5 the reduction rate of hydrogen ions

Initially5 the reduction rate of hydrogen ions
under activation control! at higher
under activation control! at higher
reduction currents it is controlled by
reduction currents it is controlled by
concentration polariation.
concentration polariation.

The corrosion rate of this system is e'ual to

The corrosion rate of this system is e'ual to
i
i
corr corr
or i
or i
= =
and5 as before5 is determined by the
and5 as before5 is determined by the
intersection between the total reduction rate
intersection between the total reduction rate
and total o1idation rate.
and total o1idation rate.

P0SSI9ITH
P0SSI9ITH

It is defined as a loss of chemical reactivity

It is defined as a loss of chemical reactivity
under certain environment conditions.
under certain environment conditions.

If a small piece of iron or steel is immersed

If a small piece of iron or steel is immersed
in nitric acid of appro1imately ,*L
in nitric acid of appro1imately ,*L
concentration at room temperature5 no
concentration at room temperature5 no
reaction is observed.
reaction is observed.

If water is now added5 diluting the nitric

If water is now added5 diluting the nitric
acid appro1imately 8 to 85 no change
acid appro1imately 8 to 85 no change
occurs.
occurs.

If the iron is scratched with a glass rod or if

If the iron is scratched with a glass rod or if
the beaEer is shaEen violently so that the
the beaEer is shaEen violently so that the
sample striEes the sides5 a violent reaction
sample striEes the sides5 a violent reaction
occurs. The iron rapidly goes into solution5
occurs. The iron rapidly goes into solution5
and large volumes of nitrogen o1ide gases
and large volumes of nitrogen o1ide gases
are released.
are released.

0 similar effect occurs if the iron is directly

0 similar effect occurs if the iron is directly
introduced into diluted nitric acid.
introduced into diluted nitric acid.

Iron5 chromium5 nicEel5 titanium and alloys

Iron5 chromium5 nicEel5 titanium and alloys
containing maCor amounts of these elements
containing maCor amounts of these elements
demonstrate active)passive transitions.
demonstrate active)passive transitions.

The behavior of the active)passive metal

The behavior of the active)passive metal
initially demonstrates behavior similar to
initially demonstrates behavior similar to
non)passivating metals &follows Tafel
non)passivating metals &follows Tafel
behavior(. This is the active region.
behavior(. This is the active region.

0t more noble potentials5 dissolution rate

0t more noble potentials5 dissolution rate
decreases to a very small value and remains
decreases to a very small value and remains
essentially independent of potential over a
essentially independent of potential over a
considerable potential region. This is
considerable potential region. This is
termed the passive region.
termed the passive region.

Finally5 at very noble potentials5 dissolution

Finally5 at very noble potentials5 dissolution
rate again increases with increasing
rate again increases with increasing
potential in the transpassive region.
potential in the transpassive region.

The transpassive region where dissolution

The transpassive region where dissolution
rate again increases with increasing
rate again increases with increasing
potential is apparently due to the
potential is apparently due to the
destruction of the passive film at very
destruction of the passive film at very
positive potentials.
positive potentials.

I
Ic c
% critical anodic current density for
% critical anodic current density for
passivity5 and E
passivity5 and Epp pp
% primary passive
% primary passive
potential.
potential.

Effec #f increasing e!&era"re and
Effec #f increasing e!&era"re and
acid c#ncenrai#n #n *eha)i#r #f an
acid c#ncenrai#n #n *eha)i#r #f an
aci)e-&assi)e !ea(+
aci)e-&assi)e !ea(+

Doth temperature and hydrogen)ion

Doth temperature and hydrogen)ion
concentration tend to increase the critical
concentration tend to increase the critical
anodic current density and usually have
anodic current density and usually have
relatively little effect on the primary passive
relatively little effect on the primary passive
potential and passive dissolution rate.
potential and passive dissolution rate.

0 similar effect is noticed upon increasing

0 similar effect is noticed upon increasing
chloride additions in the case of stainless
chloride additions in the case of stainless
steels and other ferrous)base alloys.
steels and other ferrous)base alloys.

0 single reduction process such as hydrogen

0 single reduction process such as hydrogen
evolution with three different possible
evolution with three different possible
e1change current densities.
e1change current densities.

Case 8:
Case 8:
Titanium in dilute5 air)free sulfuric
Titanium in dilute5 air)free sulfuric
or hydrochloric acid.
or hydrochloric acid.

Mnder these conditions5 titanium corrodes

Mnder these conditions5 titanium corrodes
rapidly and cannot passivate.
rapidly and cannot passivate.

Case $:
Case $:
Chromium in air)free sulfuric acid
Chromium in air)free sulfuric acid
and iron in dilute nitric acid.
and iron in dilute nitric acid.

Case +:
Case +:
Stainless steels and titanium in acid
Stainless steels and titanium in acid
solution containing o1idiers such as ferric
solution containing o1idiers such as ferric
salts or dissolved o1ygen and also iron in
salts or dissolved o1ygen and also iron in
concentrated nitric acid.
concentrated nitric acid.
Spontaneous passivation only occurs if the
Spontaneous passivation only occurs if the
cathodic reduction process clears the tip of
cathodic reduction process clears the tip of
the nose of the anodic dissolution curve.
the nose of the anodic dissolution curve.


MODERN THEORY;PPLIC;TIONS

Mi1ed potential
Mi1ed potential
theory is useful in
theory is useful in
corrosion studies because5
corrosion studies because5
8.
8.
It permits prediction of comple1
It permits prediction of comple1
corrosion behavior.
corrosion behavior.
$.
$.
It has been used to develop new
It has been used to develop new
prevention methods.
prevention methods.
+.
+.
It has been used as a basis for new
It has been used as a basis for new
rapid corrosion rate measurement
rapid corrosion rate measurement
techni'ues.
techni'ues.

?ha effec $i(( increasing e!&era"re

?ha effec $i(( increasing e!&era"re
ha)e #n he (ife #f e7"i&!en@
ha)e #n he (ife #f e7"i&!en@

?i(( increasing )e(#ciy ca"se an

?i(( increasing )e(#ciy ca"se an
increase #r decrease in c#rr#si#n rae@
increase #r decrease in c#rr#si#n rae@

If dissi!i(ar !ea(s are "sed5 $i(( his

If dissi!i(ar !ea(s are "sed5 $i(( his
affec c#rr#si#n rae@
affec c#rr#si#n rae@

Effec #f O'idi:ers
Effec #f O'idi:ers
:
:
Genera((y
Genera((y
/
/

?hen an #'idi:ing agen is added # a

?hen an #'idi:ing agen is added # a
c#rr#ding syse! c#naining a n#n-
c#rr#ding syse! c#naining a n#n-
&assi)aing !ea(5 c#rr#si#n rae is
&assi)aing !ea(5 c#rr#si#n rae is
increased+
increased+

; y&ica( aci)e-&assi)e !ea( M
; y&ica( aci)e-&assi)e !ea( M
i!!ersed in an e(ecr#(ye c#naining a
i!!ersed in an e(ecr#(ye c#naining a
red#' agen s"ch as ferric5 c"&ric5 #r
red#' agen s"ch as ferric5 c"&ric5 #r
chr#!ae i#ns+
chr#!ae i#ns+

;ddii#n/
;ddii#n/
;5 A5 C5 D5 G5 H5 I5 B
;5 A5 C5 D5 G5 H5 I5 B
Red"ci#n/ B5 I5 H5 G5 .5 E5 A5 ;
Red"ci#n/ B5 I5 H5 G5 .5 E5 A5 ;

;n #'idi:er c#ncenrai#n #f C is
;n #'idi:er c#ncenrai#n #f C is
re7"ired # &r#d"ce &assi)iy5 $hereas a
re7"ired # &r#d"ce &assi)iy5 $hereas a
c#ncenrai#n #f #'idi:er as (#$ as 8 can
c#ncenrai#n #f #'idi:er as (#$ as 8 can
!ainain &assi)iy+
!ainain &assi)iy+
Ir#n in c#ncenraed HNO
Ir#n in c#ncenraed HNO
9 9
, &#in H(2)D
, &#in H(2)D
If di("ed # 8-C5 hen scraching is
If di("ed # 8-C5 hen scraching is
danger#"s+
danger#"s+
To safely maintain passivity, oxidizer concentration
To safely maintain passivity, oxidizer concentration
should be equal to or greater than the minimum
should be equal to or greater than the minimum
amount necessary to produce spontaneous
amount necessary to produce spontaneous
passivation.
passivation.


Effec #f Ee(#ciy
Effec #f Ee(#ciy

; !ea( M i!!ersed in a c#rr#si)e

; !ea( M i!!ersed in a c#rr#si)e
syse! in $hich he red"ci#n &r#cess
syse! in $hich he red"ci#n &r#cess
is "nder diff"si#n c#nr#(+
is "nder diff"si#n c#nr#(+

S#("i#n )e(#ciy affecs he c#rr#si#n

S#("i#n )e(#ciy affecs he c#rr#si#n
rae #f a diff"si#n c#nr#((ed syse!+
rae #f a diff"si#n c#nr#((ed syse!+
Ee(#ciy has n# effec #n ai)ai#n
Ee(#ciy has n# effec #n ai)ai#n
c#nr#((ed syse!s+
c#nr#((ed syse!s+

;s a c#nse7"ence5 he c#rr#si#n rae

;s a c#nse7"ence5 he c#rr#si#n rae
*ec#!es inde&enden #f )e(#ciy a
*ec#!es inde&enden #f )e(#ciy a
)ery high )e(#ciy+
)ery high )e(#ciy+

The effec #f )e(#ciy #n an aci)e-

The effec #f )e(#ciy #n an aci)e-
&assi)e !ea( is i(("sraed *e(#$/
&assi)e !ea( is i(("sraed *e(#$/

The smaller the critical anodic current
The smaller the critical anodic current
density5 the easier a metal will be
density5 the easier a metal will be
passivated by an increase in velocity
passivated by an increase in velocity

Ga()anic C#"&(ing
Ga()anic C#"&(ing

Since hydr#gen-hydr#gen i#n

Since hydr#gen-hydr#gen i#n
e'change c"rren densiy is )ery high
e'change c"rren densiy is )ery high
#n &(ain"! and )ery (#$ #n :inc5 he
#n &(ain"! and )ery (#$ #n :inc5 he
#a( rae #f hydr#gen e)#("i#n is
#a( rae #f hydr#gen e)#("i#n is
effeci)e(y e7"a( # ha #n he
effeci)e(y e7"a( # ha #n he
&(ain"! s"rface+
&(ain"! s"rface+

The increase in c#rr#si#n rae #f :inc

The increase in c#rr#si#n rae #f :inc
#*ser)ed $hen his !ea( is c#"&(ed #
#*ser)ed $hen his !ea( is c#"&(ed #
&(ain"! is he res"( #f he higher
&(ain"! is he res"( #f he higher
e'change c"rren densiy f#r hydr#gen
e'change c"rren densiy f#r hydr#gen
e)#("i#n #n &(ain"! s"rface and n#
e)#("i#n #n &(ain"! s"rface and n#
d"e # he n#*(e re)ersi*(e &#enia( #f
d"e # he n#*(e re)ersi*(e &#enia( #f
&(ain"!-&(ain"!-i#n e(ecr#de+
&(ain"!-&(ain"!-i#n e(ecr#de+

Increasing he area #f an e(ecr#de

Increasing he area #f an e(ecr#de
increases is e'change c"rren+
increases is e'change c"rren+

If re(ai)e area #f he an#de in a

If re(ai)e area #f he an#de in a
ga()anic c#"&(e is increased5 is
ga()anic c#"&(e is increased5 is
#)era(( c#rr#si#n rae is red"ced+
#)era(( c#rr#si#n rae is red"ced+
0.E0 EFFECT



From the above figures5 the following
From the above figures5 the following
discussion can be drawn:
discussion can be drawn:
8.
8.
If two corroding metals are galvanically
If two corroding metals are galvanically
coupled5 the corrosion rate of the most
coupled5 the corrosion rate of the most
active metal &anode( is accelerated and that
active metal &anode( is accelerated and that
of the other metal &cathode( is reduced.
of the other metal &cathode( is reduced.
$.
$.
The corrosion behavior of a galvanic couple
The corrosion behavior of a galvanic couple
is determined by reversible electrode
is determined by reversible electrode
potential of the actual processes involved5
potential of the actual processes involved5
their e1change current density and Tafel
their e1change current density and Tafel
slopes and the relative areas of the two
slopes and the relative areas of the two
metals. Its behavior cannot be predicted
metals. Its behavior cannot be predicted
accurately on the basis of emf potentials.
accurately on the basis of emf potentials.

Fn"s"a( *eha)i#r

This "n"s"a( *eha)i#r #n(y #cc"rs if

This "n"s"a( *eha)i#r #n(y #cc"rs if
he &assi)e regi#n #f he !ea( *egins
he &assi)e regi#n #f he !ea( *egins
a a &#enia( !#re aci)e han he
a a &#enia( !#re aci)e han he
re)ersi*(e &#enia( #f he red#'
re)ersi*(e &#enia( #f he red#'
syse!+
syse!+

On(y $# !ea(s5
On(y $# !ea(s5
iani"!
iani"!
and
and
chr#!i"!
chr#!i"!
5 if c#"&(ed $ih &(ain"!
5 if c#"&(ed $ih &(ain"!
&r#d"ce s&#nane#"s &assi)ai#n in
&r#d"ce s&#nane#"s &assi)ai#n in
he a*sence #f #'ygen #r #'idi:ers+
he a*sence #f #'ygen #r #'idi:ers+

;((#y E)a("ai#n
;((#y E)a("ai#n

O'ygen is he !#s c#!!#n #'idi:er+ I

O'ygen is he !#s c#!!#n #'idi:er+ I
is s(igh(y s#("*(e in $aer and
is s(igh(y s#("*(e in $aer and
a7"e#"s s#("i#ns+ Theref#re5 is
a7"e#"s s#("i#ns+ Theref#re5 is
red"ci#n is "s"a((y "nder diff"si#n
red"ci#n is "s"a((y "nder diff"si#n
c#nr#(+
c#nr#(+

In air-sa"raed n#n-agiaed s#("i#ns5

In air-sa"raed n#n-agiaed s#("i#ns5
he (i!iing diff"si#n c"rren densiy
he (i!iing diff"si#n c"rren densiy
f#r #'ygen red"ci#n is a&&r#'i!ae(y
f#r #'ygen red"ci#n is a&&r#'i!ae(y
<33
<33
G
G
;4c!
;4c!
8 8

If an aci)e-&assi)e !ea( is e'&#sed #

If an aci)e-&assi)e !ea( is e'&#sed #
an aeraed c#rr#si)e !edi"!5 i
an aeraed c#rr#si)e !edi"!5 i
s&#nane#"s(y &assi)aes if is criica(
s&#nane#"s(y &assi)aes if is criica(
an#dic c"rren densiy is e7"a( # #r
an#dic c"rren densiy is e7"a( # #r
(ess han a&&r#'i!ae(y <33
(ess han a&&r#'i!ae(y <33
G
G
;4c!8+
;4c!8+

Th"s5 if he an#dic diss#("i#n *eha)i#r

Th"s5 if he an#dic diss#("i#n *eha)i#r
#f a !ea( #r a((#y is %n#$n5 i is
#f a !ea( #r a((#y is %n#$n5 i is
&#ssi*(e # &redic $heher #r n# i $i((
&#ssi*(e # &redic $heher #r n# i $i((
&assi)ae in an aeraed s#("i#n+
&assi)ae in an aeraed s#("i#n+

;ddii#n #f Cr H Ni # ir#n increase he

;ddii#n #f Cr H Ni # ir#n increase he
ease #f &assi)ai#n+
ease #f &assi)ai#n+

The addii#n #f s!a(( a!#"ns #f 8I

The addii#n #f s!a(( a!#"ns #f 8I
M# # a"seniic sain(ess see(s
M# # a"seniic sain(ess see(s
&r#d"ces a f"rher decrease in i
&r#d"ces a f"rher decrease in i
c c
5 and
5 and
&assi)aed in n# c#!&(ee(y air-
&assi)aed in n# c#!&(ee(y air-
sa"raed s#("i#ns+
sa"raed s#("i#ns+