MS617 Solid State Electrochemistry

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Chap. 2 Electrochemical Reaction Kinetics

2-2. Mixed Potential Theory

2020. 4. 27.

EunAe Cho

Department of Materials Science and Engineering

Korea Advanced Institute of Science and Technology (KAIST)

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Contents
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2-1. Polarization

1. Overpotential
2. Activation Polarization
3. Concentration Polarization
4. Ohmic Polarization

2-2. Mixed Potential Theory

2-3. Experimental Polarization Curve

1. Reference Electrode Charge

2. Three-electrode System Discharge
3. Experimental Polarization Curve

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Review: Electrode Potential
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• At equilibrium, electrode potential

E=E°-(RT/zF) ln [Paproduct/Pareactant] : Nernst Equation. Zn

• With an external current i, E = Eeq + h(i)

htot = hact + hconc. + hohm Zn2+

water
ie,a = ia- ic = io{exp (βzFηa/RT) - exp [-((1- β)zFηa)/RT]} : Volmer- Butler equation.
1) high field approximation.: hact = Ba log ie,a/io : Tafel equation
2) low field approximation: hact = RT/zF (ie,a/ io ) = ie,a∙Rp e-
Zn
hconc. = RT/zF ln (1 - i/iL) = 0.059/z log (1 - i/iL)
hohm = i(Rionic + Relectrical) Zn2+
Noble
Zn2+
Corrosion
water
Zn2+
e-
EZn2+/Zn
-0.76 V Zn Zn

Electroplating Zn2+ Zn

Active Zn2+ Zn

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Introduction to Mixed Potential Theory
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- presented by Wagner and Traud in 1938.

- based on the following hypotheses; Zn

H+
1) All free corrosion reactions involve at least one anodic and one cathodic process.
2) During the corrosion of an electrically isolated metal, Zn2+

the total partial anodic current must equal to the total partial cathodic current. water

SAa ia = SAc ic at E = Ecorr

3) For metals, the electrical (Galvani) potential of the metal at the anodic site is equal to that at the cathodic site due to their very
low resistivities. This may not be valid for semiconductors, particularly if the anodic and cathodic sites are widely separated.

H2O Zn++
H+ H2

Zn e-

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Mixed Potential Theory
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Consider Zn undergoing active corrosion in a deaerated HCl solution at 25°C,

[Zn2+] = 10-6 M, pH = 1

Zn2+ 2H+ H2 H+
Anodic reaction : Zn2+ +2e- Zn
Er,Zn = EZn2+/Zn + 0.059/2 log aZn2+
= – 0.763 + 0.059/2 log 10-6 2e- Cl-
Zn
= – 0.763 – 0.177 = – 0.94 V.

Cathodic reaction : 2H+ + 2e- H2

Er,H2 = EH2+/H + 0.059/2 log PH2/aH+
= – 0.059 V at PH2= 1 atm and pH =1

For hydrogen reduction reaction,

Er,H2 = – 0.059V, io,H+/H2(on Zn) = 10-11A/cm2, Bc = 0.12 V/decade

For Zn oxidation,
Er,Zn = – 0.94V, io,Zn2+/Zn= 10-7A/cm2, Ba =0.06 V/decade

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Mixed Potential Theory
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+0.2

0
Er,H2 = – 0.059

E (SHE) V
-0.2
hC
io,H+/H2 (Zn) 2H+ +2e- ®H2
-0.4
Zn®Zn2+ +2e-
-0.6
Ecorr
-0.8 hA

-1.0 Er,Zn = – 0.94 icorr

io,Zn2+/Zn
10-10 10-8 10-6 10-4 10-2 10-0
log |i| A/cm2

• A mixed electrode is an electrode or metal that is in contact with two or more oxidation-reduction systems.
• 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 = iH2 (Zn) at Ecorr

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Mixed Potential Theory
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Consider the corrosion of iron in deaerated acid solution.

1) For Fe oxidation :
Fe2+ + 2e- ¬ Fe ............E°Fe2+/Fe = – 0.44 V Fe2+
Er,Fe = E°Fe2+/Fe + 0.059/2 log aFe2+
H2
= – 0.44 + 0.059/2 log10-6 H2O
= – 0.62 V 2H+ H+
io,Fe2+/Fe = 10-6 A/cm2
Ba =0.08 V/decade

2) For hydrogen reduction :

2H+ + 2e- ® H2
Er,H2 = – 0.059 pH = – 0.059 V at pH=1
io,H+/H2(on Fe) = 10-6 A/cm2
Bc = – 0.15 V/decade

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Mixed Potential Theory
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+0.2
H2®2H+ +2e-
0 Er,H2 Fe®Fe2+ +2e-

-0.2
io,H+/H2
Ecorr
-0.4
icorr
-0.6 Er,Fe

-0.8 2H+ +2e- ®H2

io,Fe2+/Fe Fe2+ +2e-®Fe

10-10 10-8 10-6 10-4 10-2 10-0

Ecorr = corrosion potential, rest potential, open circuit potential, mixed potential
Hydrogen overvoltage = Ecorr – Er,H2 = Ecorr – ( – 0.059pH)

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Effects of Exchange Current Density on Corrosion Rate: Zn vs. Fe
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+0.2

0
Er,H2 = – 0.059
-0.2
hC
io,H+/H2 (Zn) 2H+ +2e- ®H2
-0.4
Zn®Zn2+ +2e-
„ Comparison of corrosion behavior between Zn and Fe -0.6
Ecorr
-0.8 hA
1) Er,Zn = – 0.94V < Er,Fe = – 0.62 V
-1.0 Er,Zn = – 0.94 icorr
2) icorr,Fe > icorr,Zn
This is due to the lower exchange current density for 10-10 10-8
io,Zn2+/Zn
10-6 10-4 10-2 10-0
hydrogen evolution on Zn compared to that on Fe. i,e
io,H+/H2(Zn) < io,H+/H2(Fe) +0.2
H2®2H+ +2e-
0 Er,H2 Fe®Fe2+ +2e-

-0.2
io,H+/H2
Ecorr
-0.4
icorr
-0.6 Er,Fe

-0.8 2H+ +2e- ®H2

io,Fe2+/Fe Fe2+ +2e-®Fe

10-10 10-8 10-6 10-4 10-2 10-0

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Effects of Exchange Current Density on Corrosion Rate
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„ The exchange current density ( io,H+/H2) 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 arsenic, sulfur, and antimony compounds.

„ For corrosion of metals in acid.

h = B log i/io
hH2 = Ecorr – ErH+/H2 = Ecorr + 0.059pH
hH2 (Zn) < hH2 (Pt) at i = i1
In the electrical analogue of double layer
RF (Zn) > RF (Pt)

„ Exchange current density, io (A/cm2) depends on :

• electrode composition
• redox reaction
• temperature
• surface roughness

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Effects of Exchange Current Density on Corrosion Rate
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E
i0, (M) - • 2H+ + 2e- → H2 (on M)
e
E (Oxd)/(Red) +z +z
(O M
xd → io
)+ M (Zn)
ze -
Ecorr →
(R
ed
)
E Mz+//M
i0, M/M+z
icorr log i

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Effects of Oxidizer on Corrosion Rate
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Oxidizer + ze- → Reducer

E = Eo + (RT/zF) ln([Oxd]/[Red])

E ↑[Oxd]
(Oxd ↑ [Oxd] Þ ↑ icorr
ER, (Oxd)/(Red) )+z -
e →
(Red
) ex) To remove oxygen in
Ecorr -

+z
e water, add hydrazine
+z
M (N2H4) into water :
ER, M/M+z →
M
i0, M/M+z N2H4 + O2 → N2 + 2H2O
i0, (Oxd)/(Red) icorr log i

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Effects of Oxidizer on Corrosion Rate
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The driving for corrosion is increased

by the addition of a stronger oxidizer
that is a redox system with a half cell
electrode potential much more noble
than that of any others present.
Consider the corrosion of metal M in
an acid containing Fe3+.

Fe3+ Fe2+
Fe3+ H2O

H2 H+
Fe2+
2e-
2H+

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Effects of Oxidizer on Corrosion Rate
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• Ecorr is determined by the point at which the total rate of oxidation equals the total rate of
reduction.

icorr = iM®M+ = iFe3+®Fe2+ + iH+®H2

The addition of an oxidizer to an acid solution :

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.

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Effects of Concentration Polarization on Corrosion Rate
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At low cathodic polarization the reduction process is activation controlled, but at high polarization it is diffusion or
concentration controlled.
hdiss. = Ba log i/io
hred. = Bc log i/io + 2.3RT/zF log(1 - i/iL)

A common example of corrosion controlled by concentration polarization is iron or steel in dilute aerated sea water.
The cathodic process is reduction of dissolved oxygen. The maximum solubility of dissolved oxygen in water is
relatively low, about 8ppm at ambient temperature.
O2 + 2H2O + 4e- ® 4OH-
Æ iL = 100µA/cm2

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Summary
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• A mixed electrode is an electrode or metal that is in contact with two or more oxidation-reduction systems.

• The total partial anodic current must equal to the total partial cathodic current.

SAa ia = SAc ic at E = Ecorr

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