Electrochemical apparatus:

chemical electric:
primary cell (Galvanic
cell)

electric
chemical:
cell

electrolytic

Electrode: anode, cathode

positive electrode; negative
electrode

Galvanic Cells (cont.)

GalvanicCell:Electrochemicalcellinwhichchemical
reactionsareusedtocreatespontaneouscurrent(electron)
flow

The Nernst Equation

The potential between
a metal and its ions
can be calculated from
the equation
formulated by Nernst
in 1889 as follows:

E t the oxidation potential of the redox electrode at T

o
E a constant value, characteristic for every redox system

called "standard electrode potential"

gas
constant

8.314

o
T absolute temperature of the system which at 25 C
25 273 298o C

F Farady 96500 coulombs

log natural logarithm, that is to the base 2.718, and is
e

convertable to common logarithms, that is to the

base 10, by multiplying by 2.303

n valency of the ions.

A nM

E t Eo

activity of the metal ions in solution.

A activity of the metal.

M

RT
nF

log

AM
A nM

Reduction Half-Reaction

E (V)

F2(g) + 2e- 2F-(aq)

2.87

Au3+(aq) + 3e- Au(s)

1.50

Cl2(g) + 2 e- 2Cl-(aq)

1.36

Cr2O72-(aq) + 14H+(aq) + 6e- 2Cr3+(aq) + 7H2O

1.33

O2(g) + 4H+ + 4e- 2H2O(l)

1.23

Ag+(aq) + e- Ag(s)

0.80

Fe3+(aq) + e- Fe2+(aq)

0.77

Cu2+(aq) + 2e- Cu(s)

0.34

Sn4+(aq) + 2e- Sn2+(aq)

0.15

2H+(aq) + 2e- H2(g)

0.00

Sn2+(aq) + 2e- Sn(s)

-0.14

Ni2+(aq) + 2e- Ni(s)

-0.23

Fe2+(aq) + 2e- Fe(s)

-0.44

Zn2+(aq) + 2e- Zn(s)

-0.76

Al3+(aq) + 3e- Al(s)

-1.66

Mg2+(aq) + 2e- Mg(s)

-2.37

Li+(aq) + e- Li(s)

-3.04

Red. agent strength increases

Ox. agent strength increases

Standard Reduction Potentials

Cell Potential
Ecell = Ecathode - Eanode = Eredn - Eox
Ecell = Ecathode - Eanode = Eredn - Eox
.(Ecathode and Eanode are reduction potentials by definition)

Standard Hydrogen Electrode

E = 0 V (by
definition;
arbitrarily
selected)
2H+ + 2e- H2

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?

Concentration and Ecell

With the Nernst Eq., we can determine the effect of concentration on cell potentials.

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

Concentration and Ecell (cont.)

First,needtoidentifythe1/2cells
Fe(s)+Cu2+(aq)

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

Concentration and Ecell (cont.)

Now,calculateEcell
Fe(s)+Cu2+(aq)

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

Concentration and Ecell (cont.)

If[Cu2+]=0.3M,what[Fe2+]isneededsothatEcell
=0.76V?
Fe(s)+Cu2+(aq)

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

Concentration and Ecell (cont.)

Fe(s)+Cu2+(aq)

Fe2+(aq)+Cu(s)

4.7=Q
Q

2
Fe

4.7

Cu
Fe

Q
4.7
2

0.3

[Fe2+]=1.4M