Lecture 15: The Nernst Equation: - 49, 50, 52 (Show You Can Do This), 53 (How Much Does Entropy Contribute), 55, 57d

1
Lecture 15: The Nernst Equation

Reading: Zumdahl 11.4
Outline:
Why would concentration matter in
electrochemistry?
The Nernst equation (contains Concentration
effects on Battery Voltage)
Applications
An entropically-driven battery
Problems (Ch 11 Zumdahl 5
th
Ed.)
49, 50, 52 (Show you can do this), 53 (how much does
entropy contribute), 55, 57d.
2
Concentration and E
cell
Consider the following redoxreaction:
Zn(s) + 2H
+
(aq) Zn
2+
(aq) + H
2
(g)
(spontaneous)
What if [H
+
] = 2 M?
Expect driving force for product formation to increase.
LeChatelier Prinicple
Therefore G
rxn
decreases, and E
cell
increases
How does E
cell
depend on concentration?
0
cell rxn
nFE G = >
0.76
o
cell
V = + E
3
E
cell
depends on Concentration
Recall, in general:
Putting this with our recent result:
The Nernst Equation
0
0
0
10
0
10
ln
ln
0.059
log
5.7log
rxn
rxn
cell rxn
cell cell
cell cell
rxn
nF G G RT Q
RT
Q
nF
Q V
n
G G Q kJ
= =
=
=
= +
E
E E
E E
0
ln
rxn
rxn
G G RT Q = +
4
E
cell
: The Nernst Equation
With the Nernst Eq., we can determine the effect
of concentration on cell potentials.
Example. Calculate the cell potential for the
following:
When [Cu
2+
] = 0.3 M and [Fe
2+
] = 0.1 M
Do you expect the potential to be greater/less than the
Standard potential?
0
10
60
log
cell cell
Q mV
n
= E E
2 2
( ) ( ) ( ) ( ) Fe s Cu aq Fe aq Cu s
+ +
+ +
When [Cu
2+
] = 1 M and [Fe
2+
] = 1 M
5
E
cell
example
First, need to identify the 1/2 cells (table, 11.1).
Get the voltage under standard conditions
2 2
( ) ( ) ( ) ( ) Fe s Cu aq Fe aq Cu s
+ +
+ +
Turn the iron half cell around and add. Note n=2
2 0
2 0
2 0
2 2
( ) 2 ( ) 0.34
( ) 2 ( ) 0.44
( ) ( ) 2 0.44
_______________________________________________
( ) ( ) ( ) ( )
cell
cell
cell
Cu aq e Cu s E V
Fe aq e Fe s V
Fe s Fe aq e V
Fe s Cu aq Fe aq Cu s
+
+
+
+ +
+ = +
+ =
+ = +
+ +
E
E
E
0
0.78
cell
V = + E
6
E
cell
example
Now, calculate Q and then E
cell
.
Notice, the concentrations are in separate containers.
0 0
0 0
2 2
2 2
10
10
(0.1)
0.33
(0.3)
2
0.06
log
0.06
0.78 log 0.33 0.78 0.014 0.80
2
Cu Cu
Fe Fe
An Cat
o
Cell Cell
Cell
Fe Fe
a a
Q
a a
Cu Cu
n
QV
n
V
+ +
+ +

= = = =

=
=
= = + =
E E
E
2 2 0
( ) ( ) ( ) ( ) 0.78
cell
Fe s Cu aq Fe aq Cu s V
+ +
+ + = + E
7
E
cell
another example
If [Cu
2+
] = 0.3 M, what [Fe
2+
] is needed so that
E
cell
= 0.76 V?
2 2 0
( ) ( ) ( ) ( ) 0.78
cell
Fe s Cu aq Fe aq Cu s E V
+ +
+ + = +
0
10
10
10
2 2
2
2
0.059
log
0.059
0.76 0.78 log
2
2 0.02 2
log
0.059 3
4.7
0.3
4.7 0.3 1.4
cell cell
E E Q
n
Q
Q
Fe Fe
Q
Cu
Fe M
+ +
+
+
=
=
= =

= = =

= =

8
Concentration Cells
Consider the cell
presented on the left.
The 1/2 cell reactions
are the same, it is just
the concentrations that
differ.
Will there be electron
flow? Why?
9
Concentration Cells: Concentration Effects Only
Ag
+
+ e
-
Ag E
1/2
= 0.80 V
E
1/2
is measured when all
species are in standard state, so
this means both sides have 1 M
concentrations of Ag
+
.
Therefore , E
cell
= 0.
10
Silver Concentration Cell
Anode: Ag Ag
+
+ e
-
E
1/2
= -0.80 V
Ag
+
+ e
-
Ag E
0
1/2
=+ 0.80 V Cathode:
Driving force for the reaction: Get the concentration up on the
left, so produce more ions there. Will stop when concentrations
in both beakers are equal (Q=1 but not Std State)
0
10
10
(0.1)
0.1
(1.0)
1
0.059
log
0.059
0.0 log 0.1 0. 0.059 0.06
1
Anode
Cathode
cell Cell
cell
Ag
Q
Ag
n
E E Q
n
E V
+
+

= = =

=
=
= = + =
11
Concentration Cells (2
nd
example)
Another Example:
The number of electrons per rxnis different
What is E
cell
?
12
Iron Concentration Cells
Fe
2+
+ 2e
-
Fe
2 e
-
transferredn = 2
E
cell
= 30mV Same Result for Cu/Cu
2+
battery
anode cathode
e
-
2
2
0
10
10
(0.01)
0.1
(0.1)
2
0.059
log
0.059
0.0 log 0.1 0. 0.03 0.03
2
Anode
Cathode
cell Cell
cell
Fe
Q
Fe
n
E E Q
n
E V
+
+

= = =

=
=
= = + =
13
Measurement of pH
pH meters use electrochemical reactions.
Ion selective probes: respond to the presence of a
specific ion. pH probes are sensitive to H
+
.
Specific reactions:
Hg
2
Cl
2
(s) + 2e
-
2Hg(l) + 2Cl
-
(aq) E
1/2
= 0.27 V
Hg
2
Cl
2
(s) + H
2
(g) 2Hg(l) + 2H
+
(aq) + 2Cl
-
(aq)
H
2
(g) 2H
+
(aq) + 2e
-
E
1/2
= 0.0 V
E
cell
= 0.27 V
14
Measurement of pH
Hg
2
Cl
2
(s) + H
2
(g) 2Hg(l) + 2H
+
(aq) + 2Cl
-
(aq)
What if we let [H
+
] vary?
{ }
2
2 2
2 2
0
10
2 2
0
10
0
10 10
2
0.059
log
0.059
log
2
0.059log 0.059log
H
Cell Cell
Cell Cell
Cell Cell
H Cl
Q H Cl
P
n
E E Q
n
E E H Cl
E E H Cl
+
+
+
+

= =

=
=

=

=

Saturate the Chloride ion so that it is constant.
15
Application of pH Measurement
E
cell
is directly proportional to pH or log [H
+
]
electrode
{ }
0
10
(0.0591)log [ ]
59.1
cell cell offset
cell ref
E E E H
E E pH mV
+
= +
= +
16
Summary
None of these ideas is separate. They are all connected,
and are all derived directly from thermodynamics.
0
0
ln
2.48ln
rxn
rxn
electricl
rev rxn
rxn
rxn
w G G X
G G RT Q
G G Q kJ
= =
= +
= +
rxn Cell
G nF = E
0
0.0591
log
Cell Cell
Q V
n
= E E
17
Nernst Equation and half reactions (Z11.52)
Show that the Nernst Equation can be applied to half
reactions as well:
0
1 2 1
1 2
1 0 2 0
1 1 2 2
0.06
log
0.06 0.06
log log
Cell Cell
Cell
Q V
n
Q QQ
Q Q
n n
=
= =
= =
E E
E E E
E E E E
However each half reaction has to be multiplied by some factor so that the
number of electrons is the same for both half reactions.
( ) ( )
1 1
1 1 2 2
1 0 0 0
1 1 1 1 1 1 1
1 1 1 1
0.06 0.06 0.06
log log log
m m
n n m n m
m Q Q Q
n m n m n
= =
= = =

E E E E
So this shows that yes one can do each half reaction separately and get the same
result as doing both half reactions together as a single reaction.
18
Nernst Equation half reactions (Z11.52a)
Apply the Nernst Equation to the Half reaction Cu/Cu2+
So you need to write and balance the half reaction in the
same direction as the half cell EMF is specified, which is
written as a reduction potential in table 11.1
( ) ( )
( )
( )
2
2
2
1 0
1 1
1
0.34 2
1
2 0.1 10
0.06 0.06
log 0.34 log10 0.34 .07 0.27
2
o
V Cu aq e Cu s
n Cu aq M Q
Cu aq
Q V
n
+
+
+
= +

= = = =

= = = =
E
E E
19
Sample Problems (Z11.49, 52)
Analyze the galvanic cell for the reaction:
3
3 1.5
0.34
o
o
Au e Au V
Tl e Tl V
+
+
+ =
+ =
E
E
As you can see it really doesnt matter what the metals are: The overall
cell is just the sum of the half cell potentials
For later we need to know that n=3 and have the balance reaction for the
cell:
3
3 3 1.84
o
cell
Au Tl Au Tl V
+ +
+ + = E
Get Gibbs energy and K:
So a 2V battery is VERY
Spontaneous.
ln
550
1.84
ln 3 220
0.025 0.025
o o
rxn Cell
o
rxn
o
Cell
G nF RT K
G kJ
K n
= =
=
= = =
E
E
20
Sample (Z11.49, 52)
How much change in EMF if product and reactant
concentrations are low? There is a trade off.
3
3 2 4
3 3 1.84
110 110
o
cell
Au Tl Au Tl V
Au Tl M
+ +
+ +
+ + =

= =

E
3
12
0 10
2
3
0
0.0591 10
log 10
10
0.6
log10 0.46 1.8 0.46 2.3
3
Cell Cell
Cell Cell Cell
Tl
Q Q
n
Au
V
+

+

= = = =

= = = + =
E E
E E E
The voltage will stay up until the Gold ion concentration goes way down.
Thats the way batteries are: When they start to go out, they go quickly.
21
Lead Acid Car Battery (Z11.53)
For the car battery, calculate the standard EMF at -20C.
( ) ( ) ( )
( ) ( ) ( )
( ) ( )
2
2 2
2 2 8
4 4
2
2
4 2 2
1.3 10
Shorthand/no salt bridge
sp
Pb s PbO s H Pb aq H O
Pb aq SO aq PbSO aq K
Pb s Pb PbO s
+ +
+
+
+ + +
+ =
The EMF is the total for both reactions; does the
second reaction increase the EMF or decrease it?
2.04
o
cell
V = E
o o o o
Rxn Cell Rxn Rxn
G nF H T S = = E
An extra question: What percentage of the battery is driven
entropicallyunder standard conditions?
0.298 263 78
0.2 20%
316 0.298 263 395
o
Rxn
o
Rxn
T S
G

= = = =
+
The reaction is exothermic and the entropy is positive. So bothparts contribute
to the battery functioning. Because the entropy is positive theEMF of the cell
will be smaller at lower temperatures. It is not surprising that a battery works
worse at low temperatures.
22
The Concentration Battery (Z11.55)
Two cells, each contains Ni metal and Ni
2+
ions.
Why would there be any potential at all?
The concentration in the different Beakers is different.
Eg(c) 1 M Ni
2+
in beaker A and 0.1M Ni
2+
in beaker B.
What is the standard EMF ?
What is the EMF?
Which way do the electrons go?
What is the concentration of Ni
2+
in A/B at equilibrium?
What is EMF at equilibrium?
( ) ( ) ( ) ( )
2 2
A A B B
Ni s Ni aq Ni aq Ni s
+ +
0
10
2
0
2
0.0591
log .03log 10 0.03 30
0 10 2
Cell Cell
A
Cell
B
Q V mV
n
Ni
Q n
Ni
+
+
= = = =

= = = =

E E
E
Not spontaneous in
direction written.
It is a totally Entropic
battery!!!!!

Lecture 15: The Nernst Equation: - 49, 50, 52 (Show You Can Do This), 53 (How Much Does Entropy Contribute), 55, 57d

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Lecture 15: The Nernst Equation

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