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Electrochemical

System
Part 2

Cell Nomenclature
A shorthand way of expressing what takes place
electrochemical cell.

in an

Cell written with oxidation reaction on the left & reduction on


the right

s
t
P
g
2
H

( )

Cathode, reduction

()

q
a
4
O
S
n
Z

s
n
Z

Anode, oxidation

( )

()

Overall reaction in this cell,

g
2
H

q
a

( )

2
n
Z

q
a
4
O
S
n
Z

s
n
Z

( )+

( )+ ( )

Example
A mixture consisting of pieces of solid zinc and solid chromium
in contact with a solution containing 1 M Zn2+ and 1 M Cr3+.
Write the cell equation for this reaction and calculate the value
of the Ecell.
Cr3+(aq) + 3e Cr(s)

E = 0.74 V

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

E = 0.76 V

Example
Calculate the following standard cell potential, label the
anode and the cathode and write the net (redox)
reaction for the following cell.
Zn(s)|Zn2+(aq)||Ni2+(aq)|Ni(s)
Calculate the standard cell potential for this
electrochemical cell

Example
The spontaneous reaction under standard conditions:
Cu2+(aq) + Sn(s) Cu(s) + Sn2+(aq)
Cu2+(aq) + 2e Cu(s)

+0.34 V

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

0.14 V

a) What is the potential under the conditions [Cu2+] = 0.1M and


[Sn2+] = 0.5M and 298K?
b) Calculate the equilibrium constant for this reaction.

Example (from text book)


Calculate the potential of the H+/H2 half-cell when aH+ = 0.770
and fH2 = 1.13

Example
Assuming that the electrolyte solutions are dilute,
calculate the EMF of the cell
Co | Co2+ || Ni2+ | Ni
if the concentrations are
a. [Ni2+] = 1.0 m and [Co2+] = 0.10 m
b. [Ni2+] = 0.010 m and [Co2+] = 1.0 m

Example (from text book)

( )

( )+

g
2
O
C
0
1
l
O
2
H
8

( )+

q
a

2
n
M
2

( )+

q
a
H
O
O
H
C
C
O
O
H
5

q
a
H
6

q
a
n4
M
2

Consider

( )+

( )

The reduction & oxidation half-reactions


=+

=+

V
9
4
.
0

V
1
5
.
1

( )+ + ( )+
()
( ) + ( )+
( )+

E E

l e
O 2
2
H
4 g2
O
q C
a 2

( )+

n q
M a
H
2
e
5
q
q a
a H
H O
8 O
H
q C
a C
O
n4 O
M H

V
9
4
.
0

V
1
5
.
1

8
.
7
7

K
5
1
1 .
8
l 9
o
m 2
J 1
k
2
0
1
3
9
.
1

l
o
m
1
K
J
4
1
3
.
8

3
0
1
5
.
6

K
o

T
G R

K
n
l
o

l
o
m
J
k
2
0
1
3
9
.
1

l
o
m
C
5
8
4
6
9
0
1

E
F
n

The equilibrium corresponds to essentially complete


conversion of reactants to products.

Determination of E &
Measurement of the cell potential at low concentration
(dilute solution).
Consider an electrochemical cell consisting of the Ag+/Ag &
S.H.E half-cells at 298 K.

q
a
H

( )

s
g
A

( )+

g
2
H
2
1

q
a
g
A
+

( )+ + ( )

Assume Ag+ arises from the dissociation of AgNO3.

d
e
R

d
e
R
x
O

d
e
R
x
O

x
O

a a
n
l
T F
R n

m
m

1
1
0
3
0
.
0

)+

g
A

)=

g
A

m
m

g1
o
l
6
1
9
5
0
.
0
E

n
l
T
R F

g
A

g
A

m
m
n
l
T
R F

Extrapolation: best fits the


data on m = 0 gives E as
intercept
Electrochemical cells provide a powerful method of
determining activity coefficient.

Example
The cell potential E for the cell
Pt(s)|H2(g, aH2=1)|H+(aq, aH+=1)
||NaCl(aq,m=0.300)|AgCl(s)|Ag(s)
is +0.260 V. Determine Cl assuming that = Na+= Cl

Example
The data in the following table have been obtained for the potential of the cell
Pt(s) | H2(g, f = 1 atm) | HCl(aq, m) | AgCl(s) | Ag(s)
as function of m at 25C

m (mol kg1)

E (V)

m (mol kg1)

E (V)

m (mol kg1)

E (V)

0.00100

0.59715

0.0200

0.43024

0.500

0.27231

0.00200

0.54425

0.0500

0.38588

1.000

0.23328

0.00500

0.49846

0.100

0.35241

1.500

0.20719

0.0100

0.46417

0.200

0.31874

2.000

0.18631

a) Determine E using a graphical method.


b) Calculate for HCl at m = 0.00100, 0.0100, and 0.100.