volmeter
Fe2+
Fe2+
solution 1M
Cu
Cu2+
solution 1M
Porous partition
0.323V
volmeter
Zn2+
Zn2+
solution 1M
Fe
Fe2+
solution 1M
Porous partition
2H+ + 2e = H2
Eo = 0.0 V
Acid Solution 1M
Reference Electrode
SHE
Equation
2H++2e=H2
Eo-0,059pH
AgCl+e=Ag+Cl-
Eo-0,059lg(aCl-)
Condition
pH=0
0,000
aCl-=1
0,1M KCl
1,0M KCl
Saturated KCl
Sea water
Hg2Cl2+2e=2Hg+2ClSaturated Calomel Electrode
(HgCl) = SCE
Eo-0,059lg(aCl-)
E(V) vs SHE
aCl-=1
SHE = SCE+0,268
0,1M KCl
1,0M KCl
Saturated KCl
Cu2++2e=CuSO4
aCu2+=1
Eo+0,0295lg(aCu2+)
Saturated CuSO4
Nernst equation
RT a OX
RT
eq
.
o
EE
ln
E E Me
ln CM n
e
nF a Red
nF
o
Table 1.1.
Eo
H++ e H
cathode
M+
M++
anode
2. Polarization
The displacement of each electrode potential from its equilibrium value is
termed polarization.
The magnitude of this displacement is the overvoltage
polarization curve
Ee
= E-Ee <0
cathodic polarization
lg i
In solution:
Ion distribute homogeneous activation polarization
Ion distribute non homogeneous concentration polarization
E, V
E, V
E, V
iL
Ee
EeH
iL
Ee
Activation
polarization
2H+ + 2e H2
Concentration
polarization
(a)
lgi
lgi
lgi
(b)
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
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
o
1
If E > 0 so
M2
e
E1e < E2 then M1 is corroded.
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
EM< EC M corroded
CCd 2
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)
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
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