Electrochemical Thermodynamics and Concepts

Sensitivity of electrochemical measurements

Measurements of electrochemical processes are made by measuring electrical currents and voltages.
The currents results from the flow of charged ions (positive or negative) and or electrons. Current
measurement can be extremely sensitive as small as 10-15 amps (coulombs per second). Let’s get
“feeling” for the sensitivity of such a measurement.

monolayer: ≈1.5 x1015 atoms/cm2 . Suppose each atom on the

surface dissolves as a single charged positive ion (i.e., a cation).

A M Þ M + + e-
+1
corresponding to 1.6 x 10-19 C/atom of charge. Today we can
easily measure at the nanoamp scale. Suppose we measure a
current density of 10-6 A cm-2 for 1 s or 10-6 C. A full monolayer of
1 cm metal dissolving as a +1 cation results in a charge of 1.6 x 10-19
1 cm C/atom x 1.5 x 1015 atoms/cm2 or ≈ 2.4 x 10-4 C cm-2. Then 10-6 C
corresponds to only of order 0.01 ML.
An electrochemical reaction is a chemical reaction involving electron
transfer.

An ordinary chemical reaction does not involve electron transfer

Chemical reactions: Note the mass balance

N2 +3H2 = 2NH3 synthesis of ammonia

Electrochemical Reactions: Note the mass and charge balance

2H+ +2e- = H2 Hydrogen ion reduction

Zn = Zn2+ + 2e- Zn oxidation

Since electrochemical reactions involve electron transfer we can measure
the rate of these processes by designing an appropriate electrical circuit and
measuring the flow of an electric current.

Faraday’s Law relates the flow of electric current to the mass of metal
reacting.

Ita
m
nF
m= mass of metal reacting (gm)
t = time (s, min, hours, years)
I = current (Amps)
a = atomic weight of metal
n = number of electrons transferred in the reaction
F = 96,500 C; Faraday’s constant which is equal to the
charge associated with 1 mole of electrons.
If , for example, we divide Faraday’s law by the time and area of
A dissolving surface, we obtain a relation describing the rate of this process.

m ia
r 
tA nF

A = surface area of corroding metal (cm2)

i = I/A: the current density (A/cm2)
r= Rate measured as a weight per unit area per
unit time (gm/cm2-s).
 Examples

Consider the case for steel or iron corrosion. Suppose we make a measurement
of the current associated with the corrosion of 100 cm2 of a steel surface and
find a current of 0.1A. Then dividing through by the area of the sample,

0.1 A/100 cm2 = 0.001 A/cm2 = 1 mA/cm2 current density.

m ia
r  Fe  Fe2  2e
tA nF

i = 1 mA/cm2
0.001A / cm 2  55.85 g
a = 55.85 g  2.89 107 gm / cm 2 s
F = 96,500 C 2  96,500C
n = 2
We can convert this to a penetration rate (cm/s) by dividing by the density of Fe.

 Fe  7.88 g / cm3

0.001A / cm 2  55.85 g
r  2.89 107 gm / cm 2 s
2  96,500C

r 2.89 107 gm / cm 2 s 8
p   3.67  10 cm / s
 Fe 7.88 gm / cm 3
Next consider:
 Electrochemical Cells
V

{Zn2+} =1 {H+} =1 We measure a potential

difference of - 0.762 V
Zn Pt

H2 at 1Atm

porous barrier
Pt is inert and acts as a catalyst: 2H+ + 2e- = H2
Zn is oxidized: Zn = Zn2+ +2e-
Total reaction: Zn + 2H+ = Zn2+ + H2

2H+ + 2e- = H2 E0 = 0.000 V (defined as zero by convention)

Zn2+ +2e- = Zn E0 = - 0.762 V (NHE) sign taken to be negative

since Zn is oxidized.
 Electrochemical Cells

{Cu2+} =1 {H+} =1 We measure a potential

difference of 0.342 V
Cu Pt

H2 at 1Atm

porous barrier

Pt is inert and acts as a catalyst: H2 = 2H+ + 2e- : hydrogen is oxidized

Cu plates; Cu2+ +2e- = Cu
Total reaction Cu2+ + H2 = Cu + 2H+

2H+ + 2e- = H2 E0 = 0.000 V (defined as zero by convention)

Cu2+ +2e- = Cu E0 = 0.342 V (NHE) This sign is positive since

Cu is reduced.
 Electrochemical Cells
+1.104 V

1 M CuSO4
1 M ZnSO4

If we construct this “cell” we observe the following:

Zn dissolves; Zn = Zn2+ +2e-; oxidation occurs at the anode
Cu plates; Cu2+ +2e- =Cu reduction occurs at the cathode

If we connect a voltmeter as shown we measure a voltage of 1.104 V.

 Daniell Cell
+1.104 V

Zn dissolves; Zn = Zn2+ +2e-; oxidation occurs at the anode

Cu plates; Cu2+ +2e- =Cu reduction occurs at the cathode

For the Cu-Zn cell we measured a voltage difference of 1.104 V.

Zn2+ +2e- = Zn E0 = - 0.762 V (NHE)

Cu2+ +2e- = Cu E0 = +0.342 V (NHE)

This difference is 1.104 V

 Standard Reduction Potentials: EMF Series
Volts (NHE): E0
Au 3+ +3e- =Au +1.498 Noble
O 2 +4H + +4e- =2H 2 0 (pH = 0) +1.229
Ag + +1e- =Ag +0.798
Fe3+ +1e- =Fe 2+ +0.771 Cathode

Cu 2+ +2e- =Cu +0.342

2H + +2e- =H 2 +0.000
Pb 2+ +2e- =Pb -0.126
Sn 2+ +2e- =Sn -0.138
Ni 2+ +2e- =Ni -0.250 Anode

Co 2+ +2e- =Co -0.277

Cd 2+ +2e- =Cd -0.403
Fe 2+ +2e- =Fe -0.447
Zn 2+ +2e- =Zn -0.762
Active
Al3+ +3e- =Al -1.662
 Standard conditions
Standard states:

• For a solid; a =1: pure metal, metal oxide, etc.

• For a gas, 1 Atm pressure is taken as unit activity.

• For dilute solutes typically found in most instances of corrosion,

activity is reasonably approximated by the concentration in M. The
standard state is 1 M.

• Temperature is taken as 25ºC = 298 K

definition: pH = -log [H+]

 Thermodynamics of Chemical Equations

aA + bB xX + yY

A, B … reactants
X, Y … products
a, b, …., x, y,…. Stoichiometric Coefficients defining how
many moles of A and B produce moles of X and Y

The chemical reaction can proceed as indicated if the energy change is

negative. That is if the energy of the products is less then that of the
reactants. Mathematically we say

Gproducts  Greact  0 OR G  0

Gi  Gi0  RT ln ai Activity or concentration “correction”

-non standard state
Energy of the standard state
 Chemical Equilibrium
aA + bB + … ® xX + yY + …

A, B … reactants
X, Y … products

a, b, …., x, y,…. Stoichiometric Coefficients

Equilibrium is defined by the condition

(
DG = xGx + yGy + ) - ( aG A + bGB + )=0
Since G ≣ standard free energy change /mole
Gi  G  RT ln ai
i
0

(
DG = xGx0 + yG y0 + ) - ( aG 0
A
+ bG B0 + )
+RT (x ln ax + y ln a y + ) - RT (aln aA + bln aB + ) = 0
 Chemical Equilibrium
Solving for G
x y
a a
DG = -RT ln
0 X Y
a b
= -RT ln K
aa
A B
K is the equilibrium constant for the reaction.

The equilibrium constant is defined by

G 
K  exp( )
RT
When components are not in standard state:

a Xx aYy
DG = DG 0 + RT ln
aAaaBb
 Electrochemical Equilibrium
a Xx aYy
DG = DG 0 + RT ln
aAaaBb
Free energy is measured in units of kcal or kJ.

1 calorie = 4.186 Joules

1Joule = 6.24 x 1018 eV

Since 1 Volt = Joule/Coulomb

G  QE where Q is the total charge. The total charge transferred

in an electrochemical reaction will be equal to the number
of moles of electrons participating in the reaction times the
charge/mole, Q = nF

DG = -nFE By convention a minus sign relates ΔG and E.

 Electrochemical Equilibrium

If we flip the numerator and denominator in the argument of the ln function,

 Electrochemical Equilibrium

Nernst Equation

Formal Potential
 Electrochemical Equilibrium: pH effects

We can write a general metal dissolution reaction in the following way:

aA  mH   ne   bB  dH 2 0
Here A could correspond to some oxidized species such as Fe2+ and B
would be its reduced form, metallic Fe. Alternatively A could be an oxide such as
FeO and B its reduced form, also metallic Fe.

The Nernst equation for this general reaction is

a m
RT é
ë A ù
û éH ù +

E = E0 + ln ë û
nF é B ùb é H O ù d
ë û ë 2 û
 Electrochemical Equilibrium and Corrosion
a m
RT é
ë A ù
û éH ù +

E = E0 + ln ë û
nF é B ùb é H O ù d
ë û ë 2 û
It’s convenient at this stage to convert the natural log (Ln) to base 10.
In general:

Ln (x) = 2.303 Log (x)

Also

RT 2.303  8.31J / moleK  298K

  0.059 V
F 96,500C / mole
 Electrochemical Equilibrium and Corrosion

The Nernst Equation above can now be rewritten as:

a
0.059 éë Aùû m
E=E + 0
log + 0.059log é H +
ù
n b
n ë û
éë B ùû

a
0.059 éë Aùû m
E=E + 0
log b
- 0.059 pH
n éë B ùû n
 Electrochemical Equilibrium and Corrosion
a
0.059 éë Aùû m
E=E +
0
log b
- 0.059 pH
n éë B ùû n

Examples:
2
(1) Consider the reaction Fe  Fe  2e

This type of reaction is favored at low values of pH.

First note that for this and all simple metal dissolution reactions there is no
H+ in the reaction and no dependence of the reaction on pH, m = 0

The Fe2+ is equivalent to A. Also a =1. The quantity [Fe2+ ] is the

concentration of Fe2+ in the electrolyte.

Fe is equivalent to B. Since Fe is a pure metal [Fe ] = 1

Then: E = E 0 + 0.0295log[Fe 2+ ] = -0.447 + 0.0295log[Fe 2+ ]; (V)

Electrochemical Equilibrium and Corrosion
ΔE [Fe2+]
(V) M
E = -0.447 + 0.0295log[Fe 2+ ]; (V)
-0.477 1

-0.506 0.1

-0.534 0.01 For every decade change in ferrous cations

there is ~ 30 mV decrease in the equilibrium
potential.
-0.565 0.001
What is the difference between an open
-0.595 10-4 circuit potential (corrosion potential) and an
Equilibrium Potential????? – Lab.
-0.624 10-5

-0.654 10-6
Electrochemical Equilibrium and Corrosion
a
0.059 éë Aùû m
E=E + 0
log b
- 0.059 pH
n éë B ùû n
Examples:
 
(2) Consider Al2 O3  6 H  6e  2 Al  3H 2 O

This type of reaction occurs at some intermediate value of pH.

Both Al and Al2O3 are solids with unit activity, A=1, B=1.
On a complete EMF series one could find that E Al o
/ Al2 O3  1.55 V.
Also note that m = 6, n = 6 so,

E Al/ Al O = -1.55 - 0.059 pH

2 3

The equilibrium potential decreases by ~ 60 mV per pH unit.

 Electrochemical Equilibrium and Corrosion
a
0.059 éë Aùû m
E=E + log0
b
- 0.059 pH
n éë B ùû n
Examples:
(3) One other type of corrosion reaction that can occur involves the formation
of a soluble metal oxide anion at some high pH,

AlO2  4 H   3e   Al  2 H 2O

0.059 4
E Al/ AlO - = E Al/
o
AlO -
+ log éë AlO2- ùû - 0.059 pH
2 2 3 3

E Al/ AlO- = -1.262 + 0.020log éë AlO2- ùû - 0.079 pH

2

The ΔE for this reaction is a function of both the dissolved ion content
and the pH of the electrolyte.
 Cathode reactions Supporting Corrosion
Hydrogen reduction

+ -
2H + 2e = H2 EH 
/ H2
 EH0 
/ H2
 0.059 pH

The above reaction occurs in an acid solution.

An equivalent reaction in neutral or alkaline solutions is:

2H2O + 2e- = H2 + 2OH - EH 

/ H2
 EH0 
/ H2
 0.059 pH

EH  / H  0  0.059 pH
2
 Cathode reactions Supporting Corrosion
Oxygen reduction

O2 + 4H + + 4e- ® 2H2O EO 2 / H 2O  EO02 / H 2O  0.059 pH

The above reaction occurs in an acid solution.

An equivalent reaction in neutral or alkaline solutions is:

O2  2 H 2 O  4e   4OH  EO2 / H 2O  EO02 / H 2O  0.059 pH

EO2 / H 2O  1.229  0.059 pH

 Potential/pH (Pourbaix) Diagram

It turns out to be very convenient to represent the

results of all these anodic metal oxidation
processes and cathodic reduction process on a
Map-like “phase diagram”.

The map considers the parameters of voltage and

solution pH and shows the possible
electrochemical/corrosion reactions that can
occur for a particular metal such as Fe, Al, Cd,
Zn, … and water.
Potential/pH (Pourbaix) Diagram
Water

oxygen evolution
and acidification

EO2 / H2O  1.229  0.059 pH

EH  / H  0  0.059 pH
2

hydrogen evolution
and alkalization
 Potential/pH (Pourbaix) Diagram
Generic diagram for a metal

1.2 Corrosion-soluble ions of the

metal are stable
0.8
POTENTIAL, E(V)

0.4

0.0
Passivation- oxides are stable

-0.4 Corrosion
Immunity-reduced form of the
-0.8
metal is stable
-1.2 Passivation

-1.6 Corrosion

-2.0
Immunity

-2.4

-2 0 2 4 6 8 10 12 14

pH
 Potential/pH (Pourbaix) Diagram

Pourbaix diagram for Al

Reaction 1: Metal oxidizes to

aqueous cations
M = M n + + ne-
Al = Al 3+ + 3e-

 A
a

eAl / Al 3  e0 
0.059
log 
m
0.059 pH
Independent of pH since
 B n no H+ is involved.
b
n

log  Al 3 
0.059
eAl / Al 3  1.662 
3 Only depends on Al3+
activity
 Potential/pH (Pourbaix) Diagram

Pourbaix diagram for Al

Reaction 2: Metal reacts to metal
hydroxide or oxide
M + nH 2O = M (OH ) n + nH + + ne-
2Al + 3H 2O = Al2O3 + 6H + + 6e-

EAl / Al2O3  1.55  0.059 pH

At higher pH Al2O3 is formed. At lower pH Al2O3 chemically

dissolves to Al3+
Intersection depends depends on Al3+ activity (dashed lines are
portions of the reactions with no significance)
 Potential/pH (Pourbaix) Diagram

Pourbaix diagram for Al

The reaction rate constant for

2Al 3+ + 3H2O = Al2O3 + 6H +

is known
K=
( H ) + 6

= 10-11.4
( Al ) 3+ 2

For (Al3+)=10-6,

log K  6log  H    2log  Al 3   6 pH  2log  Al 3 

log  Al 3  106   0.5log(1011.4 )  3 pH
Independent of potential
6  5.7  3 pH
pH  3.9
 Potential/pH (Pourbaix) Diagram

Pourbaix diagram for Al

Reaction 3: Metal reacts to form
soluble aqueous anions
Al  2H 2 O  AlO2  4H   3e 

EAl / AlO  1.262  0.020log  AlO2   0.079 pH


2

At higher pH, Al2O3 dissolves to AlO2-

K   H    AlO2   1029.2
2 2
 
Al2O3  H 2O  2 AlO  2H2

pH  14.6  log[ AlO2 ]