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chemical electric:
primary cell (Galvanic
cell)
electric
chemical:
cell
electrolytic
GalvanicCell:Electrochemicalcellinwhichchemical
reactionsareusedtocreatespontaneouscurrent(electron)
flow
o
E a constant value, characteristic for every redox system
gas
constant
8.314
o
T absolute temperature of the system which at 25 C
25 273 298o C
A nM
E t Eo
RT
nF
log
AM
A nM
Reduction Half-Reaction
E (V)
2.87
1.50
Cl2(g) + 2 e- 2Cl-(aq)
1.36
1.33
1.23
Ag+(aq) + e- Ag(s)
0.80
Fe3+(aq) + e- Fe2+(aq)
0.77
0.34
0.15
0.00
-0.14
-0.23
-0.44
-0.76
-1.66
-2.37
Li+(aq) + e- Li(s)
-3.04
Cell Potential
Ecell = Ecathode - Eanode = Eredn - Eox
Ecell = Ecathode - Eanode = Eredn - Eox
.(Ecathode and Eanode are reduction potentials by definition)
eH2 (1 atm)
ePt
1 M H+
H2 2H+ + 2e-
Cu
1 M Cu2+
Cu2+ + 2e- Cu
Example 1
A voltaic cell is made by connecting a
standard Cu/Cu2+ electrode to a S.H.E. The
cell potential is 0.34 V. The Cu electrode is
the cathode. What is the standard reduction
potential of the Cu/Cu2+ electrode?
e-
e-
H2 (1 atm)
Pt
1 M H+
2H+ + 2e- H2
Zn
1 M Zn2+
Zn Zn2+ + 2e-
Example 2
A voltaic cell is made by connecting a
standard Zn/Zn2+ electrode to a S.H.E. The
cell potential is 0.76 V. The Zn electrode is
the anode of the cell. What is the standard
reduction potential of the Zn/Zn2+
electrode?
Ecell=Ecell(0.0591/n)log(Q)
Example. Calculate the cell potential for the following:
Fe(s)+Cu2+(aq)
Fe2+(aq)+Cu(s)
Where[Cu2+]=0.3Mand[Fe2+]=0.1M
Fe2+(aq)+Cu(s)
Cu2+(aq)+2e
Cu(s)
E1/2=0.34V
Fe2+(aq)+2e
Fe(s)
E1/2=0.44V
Fe(s)
Fe(s)+Cu2+(aq)
Fe2+(aq)+2e
E1/2=+0.44V
Fe2+(aq)+Cu(s)
Ecell=+0.78V
Fe2+(aq)+Cu(s)
Ecell=+0.78V
Ecell=Ecell(0.0591/n)log(Q)
2
Fe
(0.1)
Q
0.33
2
Cu (0.3)
Ecell=0.78V(0.0591/2)log(0.33)
Ecell=0.78V(0.014V)=0.794V
Fe2+(aq)+Cu(s)
Ecell=+0.78V
Ecell=Ecell(0.0591/n)log(Q)
0.76V=0.78V(0.0591/2)log(Q)
0.02V=(0.0591/2)log(Q)
0.676=log(Q)
4.7=Q
Fe2+(aq)+Cu(s)
4.7=Q
Q
2
Fe
4.7
Cu
Fe
Q
4.7
2
0.3
[Fe2+]=1.4M