1

Chem215/P.Li/electrochem & redox/P 1

Electrochemical measurements (Ch 14-5 to 6)
Potentiometric redox titration (Ch 16-1)
1. To state the relation between E
o
and K.
(Do Ex 14-24b, 14-27)
2. From galvanic cell voltage measurement
(a) K
sp
(Do Exercise 14-18, 14-34)
(b) K
sp
and (Do Exercise 14-39)
(c) K
a
(Do Exercise 14-G, 14-36)
(d) K
f
(Do Exercise 14-H, 14-I)
(e) K
f
and 2 K
a
(Do Exercise 14-37)
To perform calculations for potentiometric redox
titration (Do Exercise 16-4)
Chem215/P.Li/electrochem & redox/P 2
E
o
and the equilibrium constant, K
1
]
1

+ d
D
b
B
a
A
c
C
A
A
n
E
A
A
n
E log
05916 . 0
log
05916 . 0
0 0
+
E E E
b
B
a
A
d
D
c
C o
A A
A A
n
E E log
05916 . 0
) (
0

+
Q
n
E
o
log
05916 . 0

When the cell is at equilibrium, Q = K and E = 0 with no current flow.
K
n
E
o
log
05916 . 0
0
05916 . 0 /
10 log
05916 . 0 o
nE o
K or K
n
E
V E E E
o o o
201 . 1 ) 402 . 0 ( 799 . 0
+
40 60 . 40 05916 . 0 / ) 201 . 1 ( 2
10 0 . 4 10 10 K
0
+

+ E cC ne aA
Cathodic reaction:
o
E bB ne dD

+
Anodic reaction:
Potentiometric measurements allow us to
find K that are too large or too small.
V E s Ag e Ag
o
799 . 0 ) ( 2 2 2 +
+
+
V E s Cd e Cd
o
402 . 0 ) ( 2
2
+

+
Example:
2
Chem215/P.Li/electrochem & redox/P 3
Electrochemical cells as chemical probes
1. Equilibrium between 2 half-cells and the net reactions are not redox reactions
11 05916 . 0 / ) 31 . 0 ( 2
10 10
6


sp
K K
E
o
is just another way of expressing the free energy change
or equilibrium constant of a reaction
K RT G and nFE G
o o o
ln
V E CO s Fe e s FeCO
o
756 . 0 ) ( 2 ) (
2
3 3
+ +
+

V E s Fe e Fe
o
44 . 0 ) ( 2
2
+

+
V E CO Fe s FeCO
o
6
2
3
2
3
31 . 0 ) 44 . 0 ( 756 . 0 ) ( +
+
Solubility product determination
Chem215/P.Li/electrochem & redox/P 4
Electrochemical cells as chemical probes
2. Equilibrium within each half-cell
If a galvanic cell has a non-zero voltage, then the net cell reaction is not at equilibrium. However, we
do allow the half-cells to stand long enough to come to equilibrium within each half-cell.
(A) Acid-base equilibrium constant determination
) ( ) ( ) 10 . 0 ( ) 0050 . 0 ( ), 050 . 0 ( ), ( ) 00 . 1 ( ) (
2 3 2 3 2
s Ag s AgCl M Cl M Na CO CH M H CO CH xM H atm H s Pt
+
E = 0.503V
The net cell reaction is not at equilibrium because the measured voltage is 0.503V, not 0V.
1
]
1

1
]
1

+ 2
] [
log
2
05916 . 0
0 ] [ log
1
05916 . 0
222 . 0
2
H
P
Cl E E E
H
2
] [
00 . 1
log
2
05916 . 0
) 10 . 0 log( 05916 . 0 222 . 0 503 . 0
+
+
H
M H
4 7 . 3
10 8 . 1 10 ] [
5
+

This allows us to evaluate the equilibrium constant for the acetic acid dissociation
5
7 4
4 4
2 3
2 3
10 8 . 1
) 10 8 . 1 050 . 0 (
) 10 8 . 1 ( ) 10 8 . 1 0050 . 0 (
] [
] ][ [

+


+

H CO CH
H CO CH
K
a
The anodic half-cell (the left one) may be
thought of as a probe to measure the unknown
[H
+
], leading to the evaluation of K
a
.
V E atm g H e M aq H
V E M aq Cl s Ag e s AgCl
o
o
0 ) 1 , ( 2 ) , ( 2
222 . 0 ) 10 . 0 , ( ) ( ) (
2
+
+ +

+
+

3
Chem215/P.Li/electrochem & redox/P 5
Electrochemical cells as chemical probes
V E Hg M aq EDTA M aq HgY E H S 331 . 0 ) ( ) 0150 . 0 , ( ), 00500 . 0 , ( . . .
2

l
(B) Complex formation constant determination
+
E E E
0
] [
1
log
2
05916 . 0
852 . 0 331 . 0
2

1
]
1

+
Hg
M Hg
18
4
6 . 17 2
10 . 2 10 ] [
1
+

This value allows us to evaluate K
f
[HgY
2-
].
[ ]
[ ] [ ]
21
5 18
4
2
2
10 6
) 0150 . 0 )( 10 3 . 2 )( 10 . 2 (
00500 . 0
4



+

EDTA Hg
HgY
K
Y
f

6 10 3 . 2 Re
5
4
pH at call
Y

V E Hg e Hg
o
852 . 0 ) ( 2
2
+
+
+
l
V E g H e H
o
0 ) ( 2 2
2
+

+
Chem215/P.Li/electrochem & redox/P 6
Potentiometric redox titration
Titration of 100.0 mL of 0.0500M Fe
2+
with 0.100M Ce
4+
.
) 1 16 (
:
3 3 2 4
+ +
+ + + +
Fe Ce Fe Ce
reaction Titration
K 10
17
in 1M HClO
4
This is a rapid and quantitative reaction. Now, we need to perform some potentiometric
calculations in monitoring [Fe
2+
]/[Fe
3+
] for the establishment of a titration curve.
4
Chem215/P.Li/electrochem & redox/P 7
Potentiometric redox titration
At the Pt indicator electrode:
There are 3 regions in the titration curve.
At the S.C.E.:
Hg
2
Cl
2
(s) + e
-
Hg(l) + Cl
-
(aq) E
-
= 0.241V
) ( ) ( ), ( ) ( ) ( ) ( ) 1 (
2 3
2 2 2
1
s Pt aq Fe aq Fe aq Cl s Cl Hg l Hg
+ +
The line notation of either cell (1) or (2):
At the Pt electrode, reactions 16-2 and 16-3 are both in equilibrium.
) ( ) ( ), ( ) ( ) ( ) ( ) 2 (
3 4
2 2 2
1
s Pt aq Ce aq Ce aq Cl s Cl Hg l Hg
+ +
) 9 16 (
] [
] [
log
1
05916 . 0
767 . 0
3
2

+
+
+
Fe
Fe
E
) 10 16 (
] [
] [
log
1
05916 . 0
70 . 1
4
3

+
+
+
Ce
Ce
E
Note that there is only one value of E
+
.
) 2 16 ( 767 . 0
2 3
+
+ +
V E Fe e Fe
o
) 3 16 ( 70 . 1
3 4
+
+ +
V E Ce e Ce
o
Chem215/P.Li/electrochem & redox/P 8
Potentiometric redox titration
1) Before EP (e.g. v = 36.0 mL)
Since there is excess Fe
2+
, and both [Fe
2+
] and [Fe
3+
] are known, it
is convenient to use equation 16-9 to calculate E
+
.
241 . 0
] [
] [
log 05916 . 0 767 . 0 .) . . (
3
2

+
+
+
Fe
Fe
E C S E E E

,
_

L M
L M L M
0360 . 0 100 . 0
0360 . 0 100 . 0 1000 . 0 0500 . 0
log 05916 . 0 526 . 0
V 550 . 0
0 . 36
0 . 14
log 05916 . 0 526 . 0
,
_

5
Chem215/P.Li/electrochem & redox/P 9
Potentiometric redox titration
2) At EP (e.g. v
e
= 50.0 mL)

,
_

+ +
+
+
+
+
+
] [
] [
log
] [
] [
log 05916 . 0 70 . 1 767 . 0 2
4
3
3
2
Ce
Ce
Fe
Fe
E
7 7
46 . 2 1 log 05916 . 0 46 . 2
) 7 16 ( ] [ ] [
3 3

+ +
Ce Fe
) 8 16 ( ] [ ] [
4 2

+ +
Ce Fe
There will be tiny amount of Ce
4+
and Fe
2+
present because of the following equilibrium.
Since [Fe
2+
], [Fe
3+
], [Ce
3+
] and [Ce
4+
] are not known, we must use both
equations 16-9 and 16-10 to calculate E
+
. We add the two equations,

,
_

+
+
+
+
] [
] [
] [
] [
log 05916 . 0 46 . 2
4
3
3
2
7
Ce
Ce
Fe
Fe
V E 23 . 1
+
Note that E
+
is just the average of E of equations 16-2 & 16-3.
V V E C S E E E 99 . 0 ) 241 . 0 23 . 1 ( .) . . (
+
M mL M v
e
0500 . 0 0 . 100 100 . 0
After the complete reaction of Ce
4+
and Fe
2+
, equal amount of Ce
3+
and Fe
3+
should be produced.
+ + + +
+ +
2 4 3 3
Fe Ce Fe Ce
Chem215/P.Li/electrochem & redox/P 10
Potentiometric redox titration
3) After EP (e.g. v = 63.0 mL)
Since there is excess Ce
4+
, and both [Ce
4+
] and [Ce
3+
] are known, it
is convenient to use equation 16-10 to calculate E
+
.
241 . 0
] [
] [
log 05916 . 0 70 . 1 .) . . (
4
3

,
_

+
+
+
Ce
Ce
E C S E E E

,
_

L M L M
L M
1000 . 0 0500 . 0 0630 . 0 100 . 0
1000 . 0 0500 . 0
log 05916 . 0 459 . 1
V 424 . 1
0 . 13
0 . 50
log 05916 . 0 459 . 1
,
_

See Fig. 16-2 for a potentiometric redox titration curve for Fe
2+
with Ce
4+
.
Note the cell voltage at any point depends only on the ratio, but not absolute values,
of the concentrations of the reactants. We should expect to see the same curve if
both reactants (e.g. Fe
2+
and Ce
4+
) are diluted by a factor of 10.