Lecture 2

Electrode potential - Nernst equation

Walther NERNST (1864-1941)

 Electrochemical thermodynamics and electrode potential
Electrode potential
0.78V 0.323V

volmeter
volmeter

Zn2+ Fe
Fe2+ Cu

Zn2+ Fe2+
Fe2+ Cu2+ solution 1M solution 1M
solution 1M solution 1M

Porous partition Porous partition

An electrochemical cell consisting An electrochemical cell consisting

of iron and copper electrodes, each of zinc and iron electrodes, each of
of which is immersed in a 1M which is immersed in a 1M
solution of its ion. Iron corrodes solution of its ion. Zinc corrodes
while copper electrodeposits. while iron electrodeposits.
 Standard Hydrogen Reference Electrode

2H+ + 2e = H2

Eo = 0.0 V Acid Solution 1M

Standard Hydrogen Electrode = SHE

 Reference Electrode Equation Condition E(V) vs SHE

2H++2e=H2
SHE pH=0 0,000
Eo-0,059pH
AgCl+e=Ag+Cl- aCl-=1 SHE = (Ag/AgCl) + 0,222
0,1M KCl SHE = (Ag/AgCl) + 0,288
Silver / silver chloride
1,0M KCl SHE = (Ag/AgCl) + 0,235
(Ag/AgCl)
Eo-0,059lg(aCl-)
Saturated KCl SHE = (Ag/AgCl) + 0,199

Sea water SHE = (Ag/AgCl) - 0.25

Hg2Cl2+2e=2Hg+2Cl- aCl-=1 SHE = SCE+0,268

Saturated Calomel Electrode 0,1M KCl SHE = SCE + 0,336

(HgCl) = SCE
Eo-0,059lg(aCl-) 1,0M KCl SHE = SCE + 0,280

Saturated KCl SHE = SCE + 0,244

Cu2++2e=CuSO4 aCu2+=1 SHE = (Cu/CuSO4) + 0,340

Copper/ Copper Sulphat
(Cu/CuSO4) Eo+0,0295lg(aCu2+) Saturated CuSO4 SHE = (Cu/CuSO4) + 0,318
 Nernst equation

RT a OX RT
E=E + lno
E = E Me +
eq. o
ln C M n+
nF a Red nF e

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 M+

cathode anode
M→ M++ e

Electrochemical cell consisting of standard

zinc and hydrogen electrodes that has been
short-circuited.

This is called a galvanic couple—two 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:
 > 0 anodic polarization , V anodic polarization
 < 0 cathodic polarization  = E-Ee >0

polarization curve Ee
 = E-Ee <0
cathodic polarization

lg i
Distribution in the vicinity of the cathode for two types Activation polarization overvoltage versus
(a) Activation polarization logarithm of current density for both oxidat
(b) Concentration polarization. ion and reduction reactions.

In solution:
Ion distribute homogeneous → activation polarization
Ion distribute non homogeneous → concentration polarization
E, V E, V E, V
iL iL
Ee Ee
Activation
polarization
EeH
2H+ + 2e → H2

Concentration
polarization

lgi lgi lgi

Activation polarization potential
versus logarithm of current density for
both oxidation and reduction
reactions.
(a) (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)
 a =  log E = E +  log
o

io 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 = Ln1 − 

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
volmeter
M1 − ne− → M1n + − E1 (1.8)

M 2n+ + ne− → M 2 + E2 (1.9)

M1 M2

M 1 + M 2n+ → M 1n+ + M 2 M1n+ M2n+

conc. C1 conc. C2
RT
E1e = − E1o − ln C M n +
nF 1
An electrochemical cell consisting
RT
E2 = E2 +
e o
ln C M n + of M1 and M2 electrodes, immersed
nF 2 in C1 & C2 solution of its ion. M1 or
M2 corrodes .
RT C M n2 +
E=E +E =E −E +
e
2 ln e
1
o
2 = E e2 − E1e
o
1
nF C M n +
1

e
If E > 0 so E1e < E2 then M1 is corroded.
Metal: E stable in Ecorr= EM determinating
by experience.
Be corroded ?
E cathode = EC =?
Aqueous solution
2H+ + 2e → H2
2,3RT PH
E eC = E o + lg 2 2 = −0,059 pH + 0,03 lg PH 2
nF CH +

O2 + 4H+ + 4e → 2H2O
2,3RT 1
E eC = E o + lg 4
= 1,23 − 0,059pH + 0,015 lg PO2
nF PO2 C H +
EM< EC → M corroded
O2 + 2H2O + 4e → 4OH-
4
2,3RT C OH −
E =E +
e
C
o
lg = 1,23 − 0,059 pH + 0,015 lg PO 2
nF PO 2

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