Lecture 2

Electrode potential - Nernst equation

Walther NERNST (1864-1941)

Electrochemical thermodynamics and electrode potential

Electrode potential
0.78V

volmeter

Fe2+
Fe2+
solution 1M

Cu

Cu2+
solution 1M

Porous partition

An electrochemical cell consisting

of iron and copper electrodes, each
of which is immersed in a 1M
solution of its ion. Iron corrodes
while copper electrodeposits.

0.323V
volmeter

Zn2+
Zn2+
solution 1M

Fe

Fe2+
solution 1M

Porous partition

An electrochemical cell consisting

of zinc and iron electrodes, each of
which is immersed in a 1M
solution of its ion. Zinc corrodes
while iron electrodeposits.

Standard Hydrogen Reference Electrode

2H+ + 2e = H2
Eo = 0.0 V

Acid Solution 1M

Standard Hydrogen Electrode = SHE

Reference Electrode
SHE

Equation
2H++2e=H2
Eo-0,059pH
AgCl+e=Ag+Cl-

Silver / silver chloride

(Ag/AgCl)

Eo-0,059lg(aCl-)

Condition
pH=0

0,000

aCl-=1

SHE = (Ag/AgCl) + 0,222

0,1M KCl

SHE = (Ag/AgCl) + 0,288

1,0M KCl

SHE = (Ag/AgCl) + 0,235

Saturated KCl

SHE = (Ag/AgCl) + 0,199

Sea water
Hg2Cl2+2e=2Hg+2ClSaturated Calomel Electrode
(HgCl) = SCE

Copper/ Copper Sulphat

(Cu/CuSO4)

Eo-0,059lg(aCl-)

E(V) vs SHE

SHE = (Ag/AgCl) - 0.25

aCl-=1

SHE = SCE+0,268

0,1M KCl

SHE = SCE + 0,336

1,0M KCl

SHE = SCE + 0,280

Saturated KCl

SHE = SCE + 0,244

Cu2++2e=CuSO4

aCu2+=1

SHE = (Cu/CuSO4) + 0,340

Eo+0,0295lg(aCu2+)

Saturated CuSO4

SHE = (Cu/CuSO4) + 0,318

Nernst equation

RT a OX
RT
eq
.
o
EE
ln
E E Me
ln CM n
e
nF a Red
nF
o

E : Half cell potential

E0: Standard half cell potential,
n: number of electrons transferred,
F Faraday constant (~96500)
R : Gas constant
T : Temperature
aOx and aRed: Activity of oxidized or reduced species COX and Cred

Table 1.1.

Eo

Measurement of electrode potential with SHE

volmeter

H++ e H

cathode

M+

M++

anode

Electrochemical cell consisting of standard

zinc and hydrogen electrodes that has been
short-circuited.

This is called a galvanic coupletwo metals electrically connected in a liquid

electrolyte wherein one metal becomes an anode and being corroded, while
the other acts as a cathode polarization

2. Polarization
The displacement of each electrode potential from its equilibrium value is
termed polarization.
The magnitude of this displacement is the overvoltage

Overvoltage is normally represented by the symbol . Overvoltage is expressed in

terms of plus or minus volts (or millivolts) relative to the equilibrium potential.
When:
anodic polarization
> 0 anodic polarization
, V
= E-Ee >0
< 0 cathodic polarization

polarization curve

Ee
= E-Ee <0
cathodic polarization

lg i

Distribution in the vicinity of the cathode for two types

(a) Activation polarization
(b) Concentration polarization.

In solution:
Ion distribute homogeneous activation polarization
Ion distribute non homogeneous concentration polarization

Activation polarization overvoltage versus

logarithm of current density for both oxidat
ion and reduction reactions.

E, V

E, V

E, V

iL

Ee
EeH

iL

Ee

Activation
polarization

2H+ + 2e H2

Concentration
polarization

(a)

Activation polarization potential

versus logarithm of current density for
both oxidation and reduction
reactions.

lgi

lgi

lgi

(b)

For reduction reactions, schematic plots of potential

versus logarithm of current density for (a) concentration
polarization, and (b) combined activation-concentration
polarization.

Activation polarization refers to the condition wherein the reaction rate is controlled
by the activation energy barrier
i
i
(1.12)
o

a log

io

E E log

io

where and io are constants for the particular half-cell. The parameter io is termed the
exchange current density
Concentration Polarization only pour cathodic polarization
exists when the reaction rate is limited by diffusion in the solution
The mathematical expression relating concentration polarization overvoltage c and
current density i is:

RT
i

C
Ln1
nF iL

(1.13)
where R and T are the gas constant and absolute temperature, respectively, n and F
have the same meanings as above, and iL is the limiting diffusion current density.

M 1 M 1n ne

What electrode can be oxidized or reduced ?

E1o

M1 ne M1n

E1

M 2n ne M 2

E2

volmeter

(1.8)
(1.9)

M1

M 1 M 2n M 1n M 2

M1n+
conc. C1

RT
E E
ln CM n
1
nF
RT
e
o
E2 E2
ln CM n
2
nF
e
1

o
1

RT CM n2
E E E E E
ln
E e2 E1e
nF CM n
e
2

e
1

o
2

M2n+
conc. C2

An electrochemical cell consisting

of M1 and M2 electrodes, immersed
in C1 & C2 solution of its ion. M1 or
M2 corrodes .

o
1

If E > 0 so

M2

e
E1e < E2 then M1 is corroded.

Metal: E stable in Ecorr= EM determinating

by experience.
E cathode = EC =?

Aqueous solution

2H+ + 2e H2
E eC E o

Be corroded ?

PH
2,3RT
lg 2 2 0,059pH 0,03 lg PH 2
nF
CH

O2 + 4H+ + 4e 2H2O
E eC E o

2,3RT
1
lg
1,23 0,059pH 0,015 lg PO 2
4
nF
PO 2 C H

O2 + 2H2O + 4e 4OH4

2,3RT COH
E E
lg
1,23 0,059pH 0,015 lg PO2
nF
PO2
e
C

( n = 4, Eo = 0,4 and lg COH- = pH-14)

EM< EC M corroded

CCd 2

Example problem 1.1

One half of an electrochemical cell consists of a pure nickel electrode in a solution of
Ni2+ ions; the other is a cadmium electrode immersed in a Cd2+ solution.
(a) If the cell is a standard one, write the spontaneous overall reaction and calculate
the voltage that is generated.
(b) Compute the cell potential at 25oC if the CCd2+ and CNi2+ concentrations are 0.5
and 10-6M, respectively. Is the spontaneous reaction direction still the same as for the
standard cell?

o
o
E ENi
ECd
0.250 (0.403) 0.153V

SOLUTION
(a) From Table 1.1, the half-cell potentials for cadmium and nickel are, respectively,
-0.403 and -0.250 V. The cadmium electrode will be oxidized and nickel reduced
because cadmium is lower in the standard Eemf series (tab. 1.1); thus, the spontaneous
reactions will be:
Cd Cd2+ + 2e(a)
Ni2+ + 2e- Ni
(b)
Ni2+ + Cd Ni + Cd2+
(c)

E EC EA EoNi EoCd 0.250 (0.403) 0.153V

b) Comparing electrode potential of Cd and Ni with CNi2+ =0,5M and CNi2+=10-6M

assume that in contrast to part a, nickel is oxidized and cadmium reduced according to
reaction (c) : Ni2+ + Cd Ni + Cd2+
(c)
RT CCd
8.314 x 298 106
o
o
E ENi ECd
ln
(0.25 (0.403)
ln
0.015V
nF CNi
2 x96500
0.5
2

Since E is negative, the spontaneous reaction direction is the opposite to that of Equation
(c), or opposite to that of the standard cell.
Ni + Cd2+ Ni2+ + Cd
Ni corrode
Other way

8.314 x298
ENi 0.25
ln(106 ) 0.427V
2 x96500
8.314 x298
ECd 0.403
ln(0.5) 0.412V
2 x96500

Example problem 1.2

Possibility to corrosion in seawater:
(Fe, Eo = -0.44V), (Cu, Eo = 0.34V), (Pt, Eo =1.118V)
CFe2+= CCu2+= CPt2+= 10-6 M, T=25oC (298K)

SOLUTION
Possibility to corrosion in seawater: Fe, Eo=-0.44V, Cu, Eo=0.34V, Pt, Eo=1.118V
CFe2+= CCu2+= CTi2+= 10-6 M
Metal

Eo, V

CMn+

EM, V

Fe

-0.44

1.00E-06

-0.617

Cu

0.34

1.00E-06

0.163

Pt

1.118

1.00E-06

0.941

EC 1.23 0.059 * pH 0.015* lg( PO2 )

1.23 0.059 * 7 0.015* lg(0.21) 0.807V

Fe and Cu can be corrode, Pt non