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 5th Ed.)
49, 50, 52 (Show you can do this), 53 (how much does
entropy contribute), 55, 57d.
1

Concentration and Ecell

Consider the following redox reaction:
Zn(s) + 2H+ (aq)

Zn2+(aq) + H2(g) Ecello = +0.76V

nFEcell = Grxn > 0

(spontaneous)

What if [H+] = 2 M?
Expect driving force for product formation to increase.
LeChatelier Prinicple
Therefore Grxn decreases, and Ecell increases
How does Ecell depend on concentration?

Ecell depends on Concentration

The Nernst Equation

Grxn = Grxn + RT ln Q
0

Recall, in general:

Putting this with our recent result:

nFEcell = Grxn = Grxn RT ln Q

0

Ecell =E

0
cell

Ecell =E

0
cell

RT

ln Q
nF

0.059
log10 Q V

0
Grxn = Grxn
+ 5.7 log10 Q kJ

Ecell: The Nernst Equation

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

0
cell

60
log10 Q mV
n

Example. Calculate the cell potential for the

following:
2+
2+

Fe( s ) + Cu (aq ) Fe (aq) + Cu ( s )

When [Cu2+] = 1 M and [Fe2+] = 1 M

When [Cu2+] = 0.3 M and [Fe2+] = 0.1 M
Do you expect the potential to be greater/less than the
Standard potential?
4

Ecell example
Fe( s ) + Cu 2+ (aq ) Fe 2+ (aq) + Cu ( s )

First, need to identify the 1/2 cells (table, 11.1).

Get the voltage under standard conditions
Cu 2+ (aq) + 2e Cu ( s )

EEcell0 = +0.34V

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

Ecell0 = 0.44V

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

Ecell0 = +0.44V

_______________________________________________
Fe( s ) + Cu 2+ (aq ) Fe 2+ (aq) + Cu ( s )

Ecell0 = +0.78V

Turn the iron half cell around and add. Note n=2
5

Ecell example
Fe( s ) + Cu 2+ (aq ) Fe 2+ (aq ) + Cu ( s )

Ecell0 = +0.78V

Now, calculate Q and then Ecell.

Notice, the concentrations are in separate containers.
Fe 2+ a 0 Fe 2+ a 0
(0.1)
Cu
Cu
Q=

=
=
= 0.33

2+
2+
(0.3)
Cu aFe0 aFe0 Cu

An
Cat
n=2
0.06
o
ECell =ECell
log10 Q V
n
0.06
ECell = 0.78
log10 0.33 = 0.78 + 0.014 = 0.80 V
2
6

Ecell another example

If [Cu2+] = 0.3 M, what [Fe2+] is needed so that
Ecell = 0.76 V?
Fe( s) + Cu 2+ (aq ) Fe 2+ (aq ) + Cu ( s )

0
Ecell
= +0.78V

0.059
log10 Q
Ecell = E
n
0.059
0.76 = 0.78
log10 Q
2
2 0.02 2
log10 Q =
=
0.059 3
Fe 2+ Fe 2+
Q = 4.7 =
=
2+
0.3
Cu
0
cell

Fe 2+ = 4.7 0.3 = 1.4 M

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?

Concentration Cells: Concentration Effects Only

Ag+ + e-

Ag

E1/2 = 0.80 V

E1/2 is measured when all

species are in standard state, so
this means both sides have 1 M
concentrations of Ag+.
Therefore , Ecell = 0.

Silver Concentration Cell

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)
Anode: Ag
Cathode: Ag+ + e-

Ag+ + e- E1/2 = -0.80 V

Ag

E01/2 =+ 0.80 V

Ag +
(0.1)
Anode
Q=
=
= 0.1
+
(1.0)
Ag
Cathode

n =1
0.059
log10 Q
n
0.059
= 0.0
log10 0.1 = 0. + 0.059 = 0.06V
1

0
Ecell = ECell

Ecell

10

Concentration Cells (2nd example)

Another Example:
The number of electrons per rxn is different

What is Ecell?
11

Iron Concentration Cells

Fe2+ + 2e- Fe
2 e- transferredn = 2

e-

Fe 2+
(0.01)
Anode
Q=
=
= 0.1
2+
(0.1)
Fe
Cathode

n=2
0.059
log10 Q
n
0.059
= 0.0
log10 0.1 = 0. + 0.03 = 0.03V
2

Ecell = ECell

Ecell

anode

cathode

Ecell = 30mV Same Result for Cu/Cu2+ battery

12

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:
Hg2Cl2(s) + 2eH2(g)
Hg2Cl2(s) + H2(g)

2Hg(l) + 2Cl-(aq) E1/2 = 0.27 V

2H+(aq) + 2e-

E1/2 = 0.0 V

2Hg(l) + 2H+(aq) + 2Cl-(aq)

Ecell = 0.27 V

13

Measurement of pH
2Hg(l) + 2H+(aq) + 2Cl-(aq)

Hg2Cl2(s) + H2(g)

What if we let [H+] vary?

2

H Cl
+ 2
2
Q=
= H Cl
PH 2
+

n=2
ECell = E

0
Cell

0
ECell = ECell
0
ECell = ECell

0.059

log10 Q
n
0.059
+ 2
2

log10 H Cl
2
0.059 log10 H + 0.059 log10 Cl

Saturate the Chloride ion so that it is constant.

14

Application of pH Measurement
0
Ecell = { Ecell
+ Eoffset } (0.0591) log10 [ H + ]

Ecell = Eref + 59.1 pH

mV

Ecell is directly proportional to pH or log [H+]

electrode

15

Summary
electricl
wrev
= G = Grxn X
0
Grxn = Grxn
+ RT ln Q
0
Grxn = Grxn
+ 2.48ln Q kJ

Grxn = nF ECell

ECell =E

0
Cell

0.0591

log Q V
n

None of these ideas is separate. They are all connected,

and are all derived directly from thermodynamics.
16

Nernst Equation and half reactions (Z11.52)

Show that the Nernst Equation can be applied to half
reactions as well:
0.06
log Q V
n
=E 1 E 2
Q = Q1Q21

0
ECell =ECell

ECell

E 1 =E1 0

0.06
log Q1
n

E 2 =E2 0

0.06
log Q2
n

However each half reaction has to be multiplied by some factor so that the
number of electrons is the same for both half reactions.

n = n1m1 = n2 m2
0.06
0.06
0.06
m1
0
0
m1 log Q1 =E1
log ( Q1 ) =E1
log ( Q1m1 )
E =E1
n1 m1
n1 m1
n
1

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.
17

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
E o = 0.34V

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

n = 2 Cu 2+ ( aq ) = 0.1M

Q=

= 10

Cu ( aq )
0.06
0.06
E 1 =E1 0
log Q1 = 0.34
log10 = 0.34 .07 = 0.27V
n1
2
2+

18

Sample Problems (Z11.49, 52)

Analyze the galvanic cell for the reaction:
Au 3+ + 3e Au
Tl + + e Tl

E o = 1.5V
E o = 0.34V

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:
Au 3+ + 3Tl Au + 3Tl +
E o = 1.84V
cell

Get Gibbs energy and K:

o
o
Grxn
= nF ECell
= RT ln K

So a 2V battery is VERY

o
Grxn
= 550kJ

Spontaneous.

o
ECell
1.84
=3
= 220
ln K = n
0.025
0.025
19

Sample (Z11.49, 52)

How much change in EMF if product and reactant
concentrations are low? There is a trade off.
Au 3+ + 3Tl Au + 3Tl +
Ecello = 1.84V

Au 3+ = 1102

Tl + = 1104 M

ECell E

0.0591
=
log Q
n

ECell E

0.6
=
log10 = 0.46
3

0
Cell

0
Cell

Tl
1012
10
Q=
10
=
=
Au 3+ 102
+

ECell = 1.8 + 0.46 = 2.3V

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.
20

Lead Acid Car Battery (Z11.53)

For the car battery, calculate the standard EMF at -20C.

Pb ( s ) + PbO2 ( s ) + 4 H + 2 Pb 2+ ( aq ) + 2 H 2O
Pb 2+ ( aq ) + SO4 2 ( aq ) PbSO4 ( aq )

K sp = 1.3 108

Pb ( s ) Pb 2+ PbO2 ( s ) Shorthand/no salt bridge

Ecello = 2.04V

The EMF is the total for both reactions; does the

second reaction increase the EMF or decrease it?

o
o
o
o
GRxn
= nF ECell
= H Rxn
T S Rxn

The reaction is exothermic and the entropy is positive. So both parts contribute
to the battery functioning. Because the entropy is positive the EMF of the cell
will be smaller at lower temperatures. It is not surprising that a battery works
worse at low temperatures.

An extra question: What percentage of the battery is driven

entropically under standard conditions?
o
T S Rxn
0.298 263
78
=
=
= 0.2 = 20%
o
GRxn 316 + 0.298 263 395

21

The Concentration Battery (Z11.55)

NiA ( s ) Ni 2+ A ( aq ) Ni 2+ B ( aq ) NiB ( s )

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?
0.0591
0
ECell =ECell

log Q = .03log10 10 = 0.03V = 30mV

n
Not spontaneous in
2+

Ni
direction written. E 0 = 0 Q =
A
= 10
n=2
Cell
2+
Ni
B
It is a totally Entropic
22

battery!!!!!