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CH.3.

E LECTROCHEMICAL K INETICS OF C ORROSION

Image Source: Corrosion Doctors, www.corrosion-doctors.org

Introduction

Corrosion is thermodynamically possible for most environments. Thus, it is of primary important to know how fast corrosion occurs. Methods

Weight loss measurements. A laboratory study and measurements What should be measured??

Objective

An understanding of the fundamental laws of electrochemical reaction


kinetics.

Thermodynamics and Kinetics of Corrosion Reaction


Thermodynamics provides a means of predicting the equilibrium state of a system of specified components, but provides no information on the detailed course of the reaction nor of the rate of reaction at which the system proceeds to equilibrium.

1 H2 (g) + O2 (g) = H2O( g ) 2

G0 (298K) = -237 kJ/mol

The rate of reaction is so slow that the reaction may be regarded as not occurring at all; however, in the presence of a catalyst, e.g., platinum black, the reaction proceeds instantaneously with explosive violence.

Thermodynamics and Kinetics of Corrosion Reaction

A steel pipe protected by an organic coating

An unprotected steel pipe buried in a corrosive soil

Kinetics of Aqueous q Corrosion


Anodic and cathodic reactions are coupled at a corroding metal surface.

Schematics of two distinct corrosion processes. processes n+ (a) The corrosion process M + O M + R showing the separation of anodic and cathodic sites. (b) The corrosion process involving two cathodic reactions.
5

Electroneutrality

There may be more than one cathodic reaction, i.e., more than one I Ic, , and more than one anodic reaction (i.e., more than one I Ia, , e.g., for alloy).

Icorr = Ia = Ic

Because of anodic regions, Aa, are generally different from areas of cathodic regions regions, Ac, CURRENT DENSITIES are generally not equal equal. Ia = - Ic Aa Ac iaAa = - icAc

Faradays Law

Charge (or corrosion current) is related to mass of material reacted (corroded) in an electrochemical reaction.

Qa Ita m= = nF nF

Where Q = charge (C) I = current (amperes, A) (1 A = 1 C/s) F = Faradays constant (96500 C/eq) n = number of equivalents (moles of electrons) transferred per mol of metal m = mass of metal corroded (g) a = molecular (atomic) weight of metal (g/mole) Corrosion rate, Or

kg ( A s ) mol [kg] = eq C mol eq

r=

m Ita It / nF F i ia = = nF tA tA

(mg/dm2/day; mdd)

Where A = surface area i = current density, I/A (icorr)

r' =

m Ita / nF ia = = tA tA nF

(mm/y)
7

Electrical Double Layer y ( (EDL) (EDL )


A. Helmholtz Model B. Gouy-Chapman Model C. Stern Model

Charge transfer reactions occur across the compact double layer and the influence of the diffuse layer is usually neglected.
8

Electrical Analog g of EDL


The electrical double layer is characterized by two layers of opposite charge facing each other, as in a capacitor. The electrical current can, however, pass across the metal-solution interface although there is some resistance to it. The electrode can then be represented by an electrical analogue composed of a capacitor parallel to a resistance RF called Faradaic resistance. The RF is called also the polarization resistance or charge-transfer resistance.
Cdl

eeeee-

M+z
z M+z

RF

Electrical double layer

Equivalent Circuit

When an electrical current is impressed on the electrode, the RF must be overcome. This generates additional voltage and causes a shift in the electrode potential. At rest (open circuit), the electrode has a charged layer; in the absence of an electric current, the capacitor Cdl is charged. The current impressed on the electrode, it, is divided into two parts. it = iF + inF
9

Electrical Analog g of EDL


Where U Usually ll iF : Faradaic current inF : current of charge accumulated in the capacitor (Non-faradaic current) iF inF .

The electrode potential is proportional to the charge Q of the double layer. Thus, the electrode potential changes under an electric current across the double layer ; E = Eeq + (i)

(i)= the additional voltage due to the current flow (overpotential; ).


inF it iF
RF Cdl

Electrode-Electric Analogue
10

General Scheme of a Faradaic Process

11

Activation Free Energy gy for Chemical Reaction


Chemical reaction: AB + C A + BC

kT G 0 / RT vc = ci e = kc ci h

12

Activation Control

Activation control is when the corrosion is controlled by charge transfer reactions.

Either the anodic charge transfer or the cathodic charge can control.

The anodic reactions and the cathodic reactions in a system can be studied INDIVIDUALLY by electrochemical methods.

e.g., the changes in potential of an electrode caused by changes in the

current flowing through it (or vice versa) can be measured, i.e., we can measure the POLARIZATION.

13

Charge (Electron) Transfer Reaction at Interface:


At equilibrium
The metal atoms on the electrode surface are in energy wells associated with the lattice structure, and in order to pass into the solution they have to overcome the activation energy (G*). G*)
a
Gch Ga* Gc*

G = Gchem + Gechem
G

M Metal IHP Gechem

Electrolyte 10

M+ OHP + + + + M + + + + IHP OHP

G*
M+

S
+

M
Helmholtz Double Layer

Gouy-Chapman Layer

E = M - s
14

Charge g Transfer (Activation) ( ) Overpotential p


G* can be changed in electrochemical reactions by externally applied potential (Eapp). The change in electrode potential from the equilibrium value to acquire a net current (i.e., externally measurable value) is called polarization (; ). iepp = f(Eapp-Eeq) = f() (1) Anodic polarization M
ia ic
ie,a

Mn+ + ne- at Eapp > Eeq


M

e
-

iapp = ia ic = f(a) where Eeq q = reversible potential or equil. potential a = Eapp-Eeq (>0): ( ) anodic d overpotential l or anodic overvoltage (2) Cathodic polarization M
ic ia

M+z

: Eapp > Eeq

Mn+ + ne- ............. at Eapp < Eeq

e
-

ie,c

iapp = ic ia = f(c) c = Eapp-E Eeq (<0): (<0) cathodic overpotential o e potential or o cathodic overvoltage.

M+z

: Eapp < Eeq

15

Charge g Transfer (Activation) ( ) Overpotential p


If anodic polarization is applied to the metal electrode, what happens to the energy well curve? The energy of M(metal) increases by (nF) and the metal ions become more unstable t bl (high (hi h energy state). t t )
G At Equilibrium, Equilibrium ia = i c = i o G Ga* M nF 0 1- 1 OHP Solution Metal IHP M 0 1- 1 OHP G* M+ Solution (1-) ( )nF After anodic polarization ie,a = ia - ic > 0 Gc*

G* M 1- M+

nF nF (1-)nF 0 Metal 0 IHP

Anodic Polarization a >0

16

For anodic reaction, G*a= G* +(1( ) )nF - nF = G* - nF For cathodic reaction, G*c = G* + (1-)nF ia = Ka exp (- G*a/RT) = Ka exp -( (G*- nF)/RT = Ka exp -(G*/RT) exp (nF/RT) =io exp (nF/RT) (K: reaction rate constant; )

(at equilibrium (=0), ia = -ic = i0)

ic = Kc exp (( G*c/RT) / ) = Kc exp (- G* /RT) exp [-((1-)nF)/RT] = io exp [-(1-)nF/RT] iapp = ia- ic = io{exp (nF/RT) - exp [-(1-)nF/RT]} ............ Butler-Volmer equation
* Gf rf = K f exp RT

at equilibrium equilibrium,
* Gf i0 = K f ' exp p RT

rf = rr =

i0 a nF
17

G rr = K r exp RT

* r

Gr* = K r ' exp p RT

Activation Polarization
A plot of the Butler-Volmer equation for the metal dissolution/deposition gives the polarization curve:

If the symmetric coefficient is 0.5, the curve is symmetrical and has a sinh form.
18

Approximation pp of Activation Polarization


(1) At large enough , the reaction is essentially all in one direction (high field approx.) for > ~0.03 V ...........high field approximation. iapp ia = io exp (nF/RT) or

act ,a = a log g

ia i0

(where a = (where,

2.303 RT ): Tafel coefficient nF

for < ~ -0.03 V .......cathodic polarization iapp ic = io exp [-(1-)nF/RT] or

act ,c = c log

ic i0

(where, c =

2.303 RT ) (1 )nF

At sufficiently large overpotential, the [ i] relationship becomes exponential. (Tafel behavior)

19

Approximation pp of Activation Polarization


(2) when is very small, ..... ||<0.01~0.02 V.....low field approximation Because: ex = 1 + x + x2/2 1 + x , when x 1, iapp = io{ exp (nF/RT) - exp [-((1-)nF)/RT]} io(nF/RT) ............a a linear relationship between and iapp

20

Polarization Diagram g (Evans ( Diagram) g )


(1) For anodic polarization

act,a

i = a log a i0
E

Anodic current

a
a Eeq c

(2) For cathodic polarization

act ,c = c log g

ic i0

c
Cathodic current log io log |i|

a =

2.303 RT nF
2.303 RT (1 )nF

c =

Normally, -0.05V < |a, c| < 0.15V For =0.5, a or c is 0.12 V.

where, io = exchange current density Eeq = equil. potential, or rest potential a, c : Tafel T f l constant t t
21

Activation Polarization - Summary y


An electrode reaction is described by i0 and . How one can determine i0? From charge transfer resistance i0 = RT/nFR RT/ FRct (Rct = /i at <<RT/ RT/nF) F) From Tafel plot by linear extrapolation to =0 How one can determine ? From the slope of the Tafel plot From i0
1 i0 = nFAk0 Cox Cred

22

Concentration Polarization
One of the assumptions in the derivation of the B-V equation is the uniformity of concentration near the electrode. This assumption fails at high current densities because migration of ions towards the electrode from the bulk is slow and may y become rate determining. g A larger g overpotential is then needed to produce a given current because the supply of reducible or oxidizable species has been depleted. This effect is called concentration polarization.

Activation control

Mass Transfer control


23

Concentration Polarization
For reduction reaction: Mn+ + ne- M eeq = e + RT/nF ln CB .................(1) (1) When a passage of external current is made through the cell, the interfacial conc. changes to a value of CS, resulting in change of electrode potential. ep = e+ RT/nF ln CS ..................(2) Concentration overvoltage, conc conc = ep - eeq = RT/nF ln Cs/CB ...(3)

24

Concentration Polarization
From the Ficks 1st law, a flux of cathodic reactant to surface, J, is: J= -D C/x = -D (CS - CB)/ = i/nF where D = diffusivity of Mn+ = Nernst layer, ~0.1mm. So, i = DnF(CB CS)/ In the limit, CS 0, i iL: limiting current density, Thus, iL = DnFCB/ CS/CB = (1 - i/iL) i = iL(1 - CS/CB), Finally, conc =

c = Ep - Eeq =RT/nF ln Cs/CB

2.303 RT i log 1 i nF L
25

Concentration Polarization
Polarization curve for the cathodic process

Point 1: Small shift from equilibrium. No limitation on reactant supply activation control. Point 2: Mixed control: Activation + Concentration total = act + conc Point 3: Large shift from equilibrium reaction rate maximum, conc infinite.
26

Concentration Polarization
During corrosion, concentration polarization for anodic dissolution can be ignored because an unlimited supply of metal atoms is available at the interface. But, at high corrosion i rates, t the th concentration t ti of f Mn+ ion i in i the th anolyte l t is i significantly i ifi tl increased i d and d exert a back emf which results in anodic conc. polarization.

+
A
iL M

+ +
Tafel (Linear Kinetics)

Tafel Region

+ ++ + ++ ++ + ++ ++
Conc. polarization
27

log ia

Concentration Polarization
iL is increased by

iL = DnFCB/

Higher solution concentration, CB. Higher temperature which increases diffusivity, D. Hi h solution Higher l i agitation, i i which hi h decreases d .

28

Combined Polarization
Total cathodic polarization
c = act ,c + conc,c = c log
ic ic 2.303 RT + log 1 i0 nF iL

Total anodic polarization


a = act ,a = a log
ia i0

29

Summary: y Tafels Law

Po otential

b=2.303 Slope b

E0a

i0,a 0a

log |i|

30

Summary y
[O2] Cathodic reaction Rate with constant rate increases withsurface Rate with surface concentration decreasing potential concentration of of oxygen oxygen varying

[O2]

Eeq,c Poten ntial

[O2]

i0,c

ln || log i| i|

iL

Parameters (or a, c), i0, iL can be used to describe virtually all electrochemical corrosion systems.
31

Resistance Overvoltage g

Resistance Overvoltage (R) arises from the passage of electric current through an electrolyte solution (with low conductivity) surrounding the electrode. Significant when surface oxide films forms on the electrode surface as a result esu t o of e electrochemical ect oc e ca reaction. eact o

R = i(Relectrolyte + Rfilm)

32

Mixed Potential Theory y ()


Presented by Wagner and Traud in 1938. Based on the following hypotheses

All free corrosion reactions involve at least one anodic and one cathodic
process process. During the corrosion of an electrically isolated metal, the total partial anodic current must equal to the total partial cathodic current : Aaia = Acic

at E = Ecorr (mixed equilibrium)

33

We plot the cathodic reaction on the same diagram as the anodic reaction (Butler-Volmer expression)

Current-potential relationships for a metal dissolution/deposition and an accompanying redox reaction showing how the two reactions couple together at the corrosion potential, Ecorr

Mixed Potential Theory y


Note: ia = -ic (=icorr) at one spot on the diagram the corrosion potential Ecorr Ecorr is the mixed potential eeq,a < Ecorr < eeq,c Metal dissolution is driven by the anodic activation overpotential: act,a = Ecorr - eeq,a And the cathodic reaction is driven by the cathodic activation overpotential: act,c = eeq,c - Ecorr Note: the thermodynamic driving force for corrosion, Etherm Etherm = eeq,c eeq,a Usually, Etherm is large enough to put Ecorr in the Tafel regions for both reactions (i.e., the reverse reactions are negligible) unless oxide films interfere.

35

Evans Diagram
The coupled portions of the curves for the anodic and cathodic reactions (i.e., ia +ve, ic ve) are usually plotted as potential vs. logarithm of the current, with the negative sign of the cathodic curve neglected

Both curves appear in the positive quadrant. This is the Evans Diagram.

Evans diagram for the corrosion process M + O Mn+ + R

36

Mixed Potential Theory


- Corrosion Potential and Current Density

Eo and io for the cathodic reaction Electrod de Potenti ial Mixed equilibrium occurs when sum of all currents Tafel fTafel slope p expressed pis is zero as mV Anodic reaction, reaction slope Ecorr and icorr per decade of current positive for the corrosion reaction
mV Cathodic reaction, Tafel slope is negative

log (-i2) - log (-i1)

log |current|
Eo and io for the anodic reaction
37

Mixed Potential Theory: y


Anodic reaction: Zn2+ + 2eZn eeq,Zn = e0Zn /Zn + 0.059/2 log aZn = - 0.763 + 0.059/2 log 10-6 = - 0.763 0 763 - 0.177 0 177 = - 0.94 0 94 V. V
2+ 2+

Corrosion of Zn in Acid

Consider Zn undergoing active corrosion in a deaerated HCl solution at 25oC.

Zn2+

2H+ 2e-

H2

H+ Cl-

Cathodic reaction : 2H+ + 2eH2 0 eeq,H 0 059/2 log PH /aH H = e H /H + 0.059/2 = - 0.059 V (at PH = 1 atm and pH =1)
2 2+ 2 + 2

Zn

For hydrogen reduction reaction, eeq,H = 0.059 V, io,H /H (on Zn) = 10-11 A/cm2, c = 0.12 V/decade
2 + 2

For Zn oxidation reaction, 7 A/cm eeq,Zn = 0.94 0 94 V, V io,Zn /Zn= 10-7 A/ 2, a =0.06 0 06 V/decade V/d d
2+

38

Reduction Reactions Involving g O 2 and H 2O


With or Without O2 Acidic Neutral Basic (Alkaline)

With O2

O2 + 4H+ + 4e- = 2H2O

O2 + 2H2O + 4e- = 4OH-

O2 + 2H2O + 4e- = 4OH-

Without O2

2H+ + 2e- = H2

2H2O + 2e- = H2 + 2OH-

2H2O + 2e- = H2 + 2OH-

39

Mixed Potential Theory: y


+0.2
eeq,H = 0.059
2

Corrosion of Zn in Acid

0 -0.2 -0.4 io,H /H


+

E( (SHE) V

(Zn)

2H+ +2e- H2

c
2 +2e Z Zn Zn Z 2+ 2 -

-0.6 E corr -0.8 -1.0 1.0


10-10 10-8

eeq,Zn = 0.94

a icorr
io,Zn /Zn
2+

10-6

10-4

10-2

10-0

log |i| A/cm2

Corrosion potential (Ecorr) and corrosion current density (icorr) are determined at the point where the total rates of oxidation and reduction are equal.
icorr (the rate of Zn dissolution) = iH at Ecorr (the rate of hydrogen evolution at Zn surface)
2

40

Mixed Potential Theory y


Ecorr

Corrosion potential Rest potential Open circuit potential Mixed potential. potential

41

Mixed Potential Theory


eeq,c

eeq,c Ecorr act,a act,a Ecorr eeq,a

Generally, Etherm [= (eeq,c - eeq,a)] < Etherm [= (eeq,c - eeq,a)] So, icorr < icorr Also anodic activation overpotential for reaction (act,a) < (act,a) Also, ) Thermodynamics are controlling
42

Mixed Potential Theory


eeq,c

eeq,c act,c

eeq,c Ecorr act,a Ecorr eeq,a

eeq,c act,c

act,a

icorr < icorr

icorr > icorr

For both cases, , Etherm [ [= (e ( eq,c [= (e ( eq,c eq c - eeq,a eq a)] < Etherm [ eq c - eeq,a eq a)] Kinetics are controlling
43

Effect of Exchange g Current Density y


i0,H /H (on Zn) = ~10-11 A/cm2
+ 2

i0,H /H (on Fe) = ~10-6 A/cm2


+ 2

P Potential

io,H2 (on Zn)

io,H2 (on Fe)

Ecorr (Fe)

io,Fe
Ecorr (Zn) (Z )

io,Zn log |i|


icorr (Zn) icorr (Fe)
44

Effect of Exchange g Current Density y


Er,Zn = 0.94V < Er,Fe = 0.62 V icorr,Fe corr Fe > icorr,Zn corr Zn This is due to the lower exchange current density for hydrogen evolution on Zn compared to that on Fe. i,e io,H /H (Zn) < io,H /H (Fe)
+ 2 + 2

The exchange current density ( io,H /H ) for hydrogen evolution reaction is highly sensitive to the nature of the metal substrate on which the reaction occurs, and are markedly reduced by the presence of trace impurities such as Sb, Sb S, S Hg and As compounds, compounds etc etc.
+ 2

45

Effect of Oxidizer
The driving force for corrosion is increased by the addition of a stronger oxidizer, idi th that ti is, a redox d system t with ith a half cell electrode potential much more noble than that of any others present. Consider the corrosion of metal M in an acid containing Fe2+-Fe3+.

Fe3+ Fe3+

2 Fe2+ F

H 2O H2 2e2H+ H+

Fe2+

46

Effect of Oxidizer
Ecorr is determined by the point at which the total rate of oxidation equals the total rate of reduction. icorr = iMM+ = iFe3+Fe2+ + iH+H2 (1) shifts corrosion potential in the noble direction, (2) increases the corrosion rate from i'corr to icorr, (3) decreases hydrogen evolution from i'corr to iH+H2. The effect of an oxidizer on the corrosion rate is dependent on its redox potential and its exchange current density.

47

Effect of Dissolved Ion Concentration


Drawing appropriate polarization diagrams, determine the effect of increasing increasing the concentration of dissolved H+ on E Ecorr and i icorr of a metal M corroding to dissolved M+ in a deaerated acid solution under activation control with all other parameters constant.

48

Example p Problems
The corrosion potential of mild steel in a deaerated solution of pH = 2 is -0.324V vs. SHE. Determine the corrosion rate in mm/y taking the exchange current density for hydrogen evolution on the steel, i0 = 10-7 A/cm2, the Tafel constant for the hydrogen evolution reaction c = -0.1 V and the molecular weight of steel mwFe=55.85 and density of the steel Fe = 7.89 g/cm3.

49

Effect of Concentration Polarization


At low cathodic polarization the reduction process is activation controlled, but at high polarization it is diffusion or concentration controlled. a = a log i/io c = c log i/io + 2.3RT/nF log(1 - i/iL) [3.14] A common example of corrosion controlled by concentration polarization is iron (or steel) in dilute aerated seawater. The cathodic process is reduction of dissolved oxygen (DO). The maximum solubility of dissolved oxygen in water is relatively low, about 8 ppm at ambient temperature. O2 + 2H2O + 4e- 4OH iL = 100A/cm2

50

Concentration Polarization

Oxygen reduction is often affected by concentration polarization


Rate of cathodic oxygen reduction without concentration polarization

Electrode Po otential

Rate of cathodic oxygen reduction with concentration polarization Limiting current density rate of reaction limited by availability of oxygen at the metal surface log og |current u density| d y|

51

ioH /H2(M)
+

Ecorr,C Ecorr,B Ecorr,A

ioC /C
+

ioB /B
+

ioA /A
+

iL

log|i|

In this system, icorr=iL, depending on conc., temperature and velocity velocity.

For different metals; A, B and C, icorr is equal to iL.

52

Resistance Polarization

If there is a resistance between the anode and the cathode in a cell, then the current flowing through that resistance will cause a potential drop given by Ohms Law: V = IR

This is important for paint films and for high resistance solutions (e g soils) (e.g.,

53

Resistance Polarization
Resistance Polarization causes potential of anode and cathode to differ due to p potential drop p across solution, hence corrosion current is reduced

Electrode P Potential

log |current density|

54

Experimental Polarization Curve


Cathodic Polarization

Corrosion rate (icorr) and exchange current density (i0) can be measured from polarization data (Ch.5). Fig. 3.15. - The Tafel behavior is limited to only about one decade of current density. y Fig. 3.16. Effect of pH (concentration polarization)
55

Experimental Polarization Curve


Cathodic Polarization

Polarization of cathodic reaction by shift of potential to a more negative value Increase cathodic polarization by c (from c = Ecorr ec to c = E*-ec) and plot applied current, iapp vs. potential, E. ia + iapp = ic Same principle is applied in cathodic protection which is to be covered later.
56

Experimental p Polarization Curve

57

Experimental p Polarization Curve


Iron in hydrochloric acid

Elec ctrode Pot tential

Anodic iron dissolution Cathodic hydrogen evolution

log |current density|


58

Experimental p Polarization Curve


Iron in sulfuric acid

Elec ctrode Pot tential

Oxygen evolution (with on passive film (or Anodic iron dissolution activetranspassive corrosion as metal is passive transition) oxidised idi d t to a hi higher h oxidation id ti state) t t ) Cathodic hydrogen evolution

log |current density|


59

Experimental p Polarization Curve


Iron in aerated neutral NaCl Solution
Anodic iron dissolution

Electrode Potential l

Cathodic oxygen reduction

Cathodic hydrogen evolution

log |current density|

60

Experimental p Polarization Curve

61

NonNon - ideal Experimental Polarization Curves


Use of cathodic polarization data to form the anodic polarization curve in the case of non-linear anodic data (distorted probably by accumulated corrosion products at high currents)

62

Instrumentation

63

Instrumentation

64

Measurement Methods

Potential control

Connect electrodes to corresponding terminals on potentiostat Reference Electrode Luggin Probe - allows potential reference connection for AE to be detected close to metal potential measurement surface RE WE

Potentiostat

Counter Electrode (or Auxilliary Electrode or Working Electrode - metal Secondary Electrode) Potentiostat controls being studied provides current path into potential solution
65

Measurement Methods

Current control
Current path Potentiostat

AE RE WE Counter Electrode R

Reference Electrode Current controlled by control of only Luggin used to monitor potential Probe stillpotential, needed tonot voltage across resistor (I=V/R) Working Electrode connected to potentiostat limit IR error
66

Working g Electrode

Requirements

reproducible representative free of crevices free of edge effects free of galvanic effects free of water-line effects

67

Working g Electrode

Epoxy-embedded electrode:

Apply thin layer of epoxy to minimise stress and risk of crevice formation

Pretreat specimen for good adhesion g

Weld or solder connecting wire to specimen

Apply thick layer of epoxy to seal connecting tube and for strength

Carefully grind surface to expose metal

Clean surface - dont use acetone


68

Working g Electrode ( (Cylindrical) y )


Metal rod Retaining nut Washers

Heavy-walled glass tube

Lip seal between PTFE case and electrode

PTFE Washer Electrode

69

Working g Electrode
Avesta cell:

Pure H2O feed

NaCl Solution

Filter paper

Specimen

70

Reference Electrode

Commonly use Saturated Calomel Electrode (SCE) Properties may degrade with time (and misuse)

Check one against another (should not be more than 1 to 2 mV


difference) Do not pass current through the reference electrode (e.g. do not connect to working or counter electrode) Do not allow to dry out

Solution in SCE (or Ag/AgCl electrode) is saturated KCl

Beware of chloride contamination of test solution by Cl- leaking from


reference electrode Make sure solution remains saturated

71

Reactions on CE During Cathodic Polarization


For the working electrode as an anode, metal dissolution reactions of the type M Mn+ + neare of interest in corrosion. When the working electrode is polarized as cathode (auxiliary electrode as anode), M must be selected for the auxiliary electrode with a very noble eM/Mn+ to prevent anodic dissolution, which would contaminate the electrolyte. Either platinum or carbon/graphite is the usual choice. In the absence of anodic dissolution at the auxiliary electrode by reaction (1), other anodic oxidation reactions are possible to liberate electrons. These include oxidation in a redox reaction such as Fe2+ Fe3+ + eAnd oxygen evolution by 4OH- 2H2O + O2 + 4e(3) (2) ( ) (1)

Reactions (2) and (3) both must operate at potentials below eM/Mn+ (e.g. ePt/Pt3+) so that noble metal auxiliary electrode is not dissolved.
72

Solution

Requirements:

as high a conductivity as possible (add supporting electrolyte) remain the same (pH, composition) throughout the experiment - ensure
that volume is adequate oxygen yg concentration often critical - aerate by y bubbling g air or O2 or deaerate with N2 or Ar most reactions are temperature sensitive, so control, or at least record, temperature

73

Summary y
Eh 1.23 eeq(c) c Cu2+ CuO CuO2 0 Cu Cu2O
2-

C = C Cu Cu2++ 2e 2

Tafel

Ecorr a eeq(a) l g io(c) log l g io(a) log l icorr log l i log Tafel

1/2O2+ 2H+ +2e = H2O

15

pH

74

Summary y
Eh

total reduction current= ired(O2) + ired(H+) 1/2O2 + 2H+ + 2e = H2O

1 23 1.23

Zn2+

Z (OH)2 Zn(OH)

2H+ + 2e = H2

ZnO22-

Zn

Zn = Zn2+ + 2e
7 14

pH

Log icorr

75

Summary
Effect of Electrochemical Parameters on Corrosion Rates

(1) Equilibrium potential, eeq

(2) io

(3)

76

Summary y

77

References

Textbook (D.A. Jones) M G Fontana, M.G. Fontana Corrosion Engineering Engineering, 3rd ed., ed McGraw-Hill McGraw Hill, 1987 1987. Homepage for Prof. Kwons Laboratory, http://corrosion.kaist.ac.kr Lecture Notes by Dr. D.H. Lister, and Dr. W. Cook, Department of Chemical Engineering, Engineering University of New Brunswick. Brunswick H.H. Uhlig and R.W. Revie, Corrosion and Corrosion Control, John Wiley and Sons, 1985.

78

Homework Problems

Problems 1, 6, 7, 8, 10, 11 of Chapter 3 in textbook.

79

APPENDICES

Faradays y Constant

One mole of metal (MW g) contains Avogadros number (61023) of metal atoms Hence each mole of metal will produce n times that many number of electrons Charge on the electron is 1.6 1 610-19 C (Coulomb) Hence, one mole of metal will produce a charge of n96500 C 96,500 C/equivalent is known as Faradays constant C Conversions: i 1 A = 1 C/s, C/ 1 J = 1 CV CV

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Oxygen yg Solubility y

Cited from P.R. P R Roberge, Roberge Handbook of Corrosion Engineering, Engineering McGraw-Hill McGraw Hill, New York, York 2000. 2000

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Effect of Diffusion Rate of Oxidizer


O2 + 4H+ + 4e 2 H2O :
ic = 4Fv = 4FD(Cb-Ci)/ Limiting current density iL= 4FDCb/ Cb : :

' C B Ecorr A log icorr log i '

A: , B: A noble A . C: .

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Counter electrode

Counter electrode should allow current to pass with tolerable polarization Often claimed that counter electrode should have much larger area than working electrode, but this is not often necessary for corrosion stud es studies Usually use platinum or graphite, although stainless steel can be used in some situations (e.g. where only anodic polarization of specimen p is used) )

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