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ELECTRODE POTENTIALS
Electrochemistry
Cathodic reaction: Cu
2+
+ 2 e
-
Cu(s) E
o
=
0.34 V
Overall reaction: Zn
(s)
+Cu
2+
(aq)
Cu
(s)
+Zn
2+
(aq)
E
o
= 1.1 V
A galvanic
cell is a device
that converts
electron
transfer into
useful electrical
work
The Salt Bridge
Maintains electroneutrality
At standard conditions,
E
cell
= E
o
cell
= E
o
cathode
E
o
anode
Example: E
o
cell for Zn
(s)
+ Cu
2+
(aq)
Cu
(s)
+ Zn
2+
(aq)
Zn(s) Zn
2+
+ 2 e
-
E
o
= -0.76 V
Cu
2+
+ 2 e
-
Cu(s) E
o
= 0.34 V
E
o
cell
= E
o
cathode
E
o
anode
= 0.34 V (-0.76 V) = 1.10 V
The Nernst Equation
At 25
o
C (298 K):
Q log
nF
RT 303 . 2
E E
cell
o
cell
where R = 8.314 J/mol
K, F = 96485 C/mol e
-
,
n = no. of e
-
transferred, T = temp.
in K
Q log
n
0592 . 0
E E
cell
o
cell
For Cu
2+
+ 2 e
-
Cu(s),
] Cu [
1
log
n
0592 . 0
E E
2
cell
o
cell
+
Equilibrium constants from the
nernst equation
At equilibrium, G = 0, E
cell
= 0, and Q =
K
eq
thus,
becomes
Solving for K
eq
, we get:
Note that Keq can be K
sp
, K
a
, K
b
, K
f
, etc.
Q log
n
0592 . 0
E E
cell
o
cell
eq
cell
o
K log
n
0592 . 0
E
1
1
]
1
0592 . 0
) E )( n (
log anti K
cell
o
eq
G and E
cell
,
_
,
_
Note: 1 J = 1
CV
Equilibrium constant?
Let us now calculate for the K
eq
of the
previous example
Recall: E
o
cell
= (+0.15 V) (-0.74 V) = + 0.89
V
Thus,
=> the very large value of K
eq
reinforces our
previous conclusion that the reaction is
product-favored
90
eq
10 x 59 . 1
0592 . 0
) 89 . 0 )( 6 (
log anti K
1
]
1
EXPERIMENT
PROPER
Part A
Cell Notation Anode Cathode
Cu
(s)
|Cu
2+
(aq)
(0.01 M)|| Cu
2+
(aq)
(0.1M)|Cu
(s)
Cu
(s)
|Cu
2+
(aq)
(0.01M) Cu
2+
(aq)
(0.1M)|Cu
(s)
Zn
(s)
|Zn
2+
(aq)
(0.1M)|| Cu
2+
(aq)
(0.1M)|
Cu
(s)
Zn
(s)
|Zn
2+
(aq)
(0.1M) Cu
2+
(aq)
(0.1M)|Cu
(s)
C
(graphite)
|Fe
2+
(aq)
(0.5M), Fe
3+
(aq)
(1M)|| Cu
2+
(aq)
(0.5M)|Cu
(s)
C
(graphite)
|Fe
2+
(aq)
(0.5M),
Fe
3+
(aq)
(0.5M)
Cu
2+
(aq)
(0.5M)|Cu
(s)
Theoretical E
cell
= E
o
cell
= E
o
cathode
- E
o
anode
since the
cells have standard concentrations (all 1 M)
Concentration cell
Cu
2+
(aq) + 2e
-
Cu(s)
Current X
Time
no. of
Coulombs
Useful
Conversions
:
1 J = 1 CV
1 A = 1 C/s
Mass of
substance
Mol. of e
-
passed
( ) Cu g 47 . 2
e mol 2
Cu g 5 . 63
C 485 , 96
e mol 1
s
C 50 . 2
min 1
s 60
min 0 . 50 Cu g
,
_
,
_
,
_
,
_