Modern Theory of Corrosion
Modern Theory of Corrosion
Modern Theory of Corrosion
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
If
If
$ /
$ /
" "
" $ 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
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 (
)+
)+
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
!
,
,
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
)
)
/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.
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
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(+
Case 8:
Case 8:
Titanium in dilute5 air)free sulfuric
Titanium in dilute5 air)free sulfuric
or hydrochloric acid.
or hydrochloric acid.
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.
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