Electrochemistry

Chapter 18

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Galvanic/Voltaic Cells: Generating

electricity from spontaneous chemical
reactionshttps://www.youtube.com/watch?v=0o
SqPDD2rMA
anode
oxidation

cathode
reduction

spontaneous
redox reaction

Galvanic Cells
The difference in electrical
potential between the anode
and cathode is called:
cell voltage
electromotive force (emf)
cell potential
Zn (s) + Cu2+ (aq)

Cu (s) + Zn2+ (aq)

[Cu2+] = 1 M and [Zn2+] = 1 M

Cell Diagram
phase boundary
Zn (s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu (s)
anode

salt bridge

cathode

Standard Reduction Potentials

Standard reduction potential (E0) is the voltage associated
with a reduction reaction at an electrode when all solutes
are 1 M and all gases are at 1 atm.

Reduction Reaction
2e- + 2H+ (1 M)

H2 (1 atm)

E0 = 0 V

Standard hydrogen electrode (SHE)

Standard Reduction Potentials

Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

Anode (oxidation):

Zn (s)

Cathode (reduction): 2e- + 2H+ (1 M)

Zn (s) + 2H+ (1 M)

Zn2+ (1 M) + 2eH2 (1 atm)

Zn2+ (1 M) + H2 (1 atm)
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Standard Reduction Potentials

0 = 0.76 V
Ecell

0 )
Standard emf (Ecell

0
0 = E0
Ecell
cathode - Eanode

Zn (s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt (s)

0 = E 0 + - E 0 2+
Ecell
H /H 2
Zn /Zn
0 2+
0.76 V = 0 - EZn
/Zn
0 2+
EZn
/Zn = -0.76 V

Zn2+ (1 M) + 2e-

Zn

E0 = -0.76 V

Standard Reduction Potentials

0 = 0.34 V
Ecell

0
0 = E0
Ecell
cathode - Eanode
0 = E 0 2+
0
Ecell
Cu /Cu EH +/H 2
0 2+
0.34 = ECu
/Cu - 0
0 2+
ECu
/Cu = 0.34 V

Pt (s) | H2 (1 atm) | H+ (1 M) || Cu2+ (1 M) | Cu (s)

Anode (oxidation):

H2 (1 atm)

Cathode (reduction): 2e- + Cu2+ (1 M)

H2 (1 atm) + Cu2+ (1 M)

2H+ (1 M) + 2eCu (s)

Cu (s) + 2H+ (1 M)

E0 is for the reaction as

written

The more positive E0 the

greater the tendency for the
substance to be reduced

The half-cell reactions are

reversible

The sign of E0 changes

when the reaction is
reversed

Changing the stoichiometric

coefficients of a half-cell
reaction does not change
the value of E0
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Example 18.2

Predict what will happen if molecular bromine (Br2) is added to

a solution containing NaCl and NaI at 25C. Assume all species
are in their standard states.

Example 18.2
Strategy To predict what redox reaction(s) will take place, we
need to compare the standard reduction potentials of Cl2, Br2,
and I2 and apply the diagonal rule.
Solution From Table 18.1, we write the standard reduction
potentials as follows:
Cl2(1 atm) + 2e-

2Cl-(1 M)

E = 1.36 V

Br2(l) + 2e-

2Br-(1 M)

E = 1.07 V

I2(s) + 2e-

2I-(1 M)

E = 0.53 V
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Example 18.2
Applying the diagonal rule we see that Br2 will oxidize I- but will
not oxidize Cl-. Therefore, the only redox reaction that will occur
appreciably under standard-state conditions is
Oxidation:
2I-(1 M)
I2(s) + 2eReduction:
Br2(l) + 2e2Br-(1 M)
______________________________________________
Overall:
2I-(1 M) + Br2(l)
I2(s) + 2Br-(1 M)

Check We can confirm our conclusion by calculating Ecell. Try

it. Note that the Na+ ions are inert and do not enter into the
redox reaction.
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Example 18.3

A galvanic cell consists of a Mg electrode in a 1.0 M Mg(NO3)2

solution and a Ag electrode in a 1.0 M AgNO3 solution.
Calculate the standard emf of this cell at 25C.

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Example 18.3
Strategy At first it may not be clear how to assign the
electrodes in the galvanic cell. From Table 18.1 we write the
standard reduction potentials of Ag and Mg and apply the
diagonal rule to determine which is the anode and which is the
cathode.
Solution The standard reduction potentials are
Ag+(1.0 M) + e-

Ag(s)

E = 0.80 V

Mg2+(1.0 M) + 2e-

Mg(s)

E = -2.37 V

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Example 18.3

Applying the diagonal rule, we see that Ag+ will oxidize Mg:
Anode (oxidation):
Mg(s)
Mg2+(1.0 M) + 2eCathode (reduction):
2Ag+(1.0 M) + 2e2Ag(s)
_________________________________________________
Overall:
Mg(s) + 2Ag+(1.0 M)
Mg2+(1.0 M) + 2Ag(s)

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Example 18.3
Note that in order to balance the overall equation we multiplied
the reduction of Ag+ by 2. We can do so because, as an
intensive property, E is not affected by this procedure. We find
the emf of the cell by using Equation (18.1) and Table 18.1:
Ecell = Ecathode - Eanode
= EAg+/Ag - EMg2+/Mg
= 0.80 V - (-2.37 V)
= 3.17 V
Check The positive value of E shows that the forward reaction
is favored.
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Example

Seatwork:

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Effect of Concentration on Electrode

Potentials: Nernst Equation
Nernst Equation
c
d
RT
[C]
[D]
...
E E
ln a b
nF [A] [B] ...

At 25 0C,
c
d
0.0592
[C]
[D]
...

EE
log a b
n
[A] [B] ...

where
R gas constant, 8.314
T temperature in Kelvin
n number of electrons that appear in the half-cell reaction

F Faradays Constant, 96487.38

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Spontaneity of Redox Reactions

0
G0 = -RT ln K = -nFEcell

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Example 18.6
Calculate (a) the standard-state potential, (b) the equilibrium
constant, and (c) the potential when [Ag+] = 0.020 M and [Cd2+]
= 0.050 M, for the following reaction taking place at 25 C.
Cd(s) + 2Ag+(aq) Cd2+(aq) + 2Ag(s)

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Example 18.7

Consider the galvanic cell shown in Figure 18.4(a). In a certain

experiment, the emf (E) of the cell is found to be 0.54 V at 25C.
Suppose that [Zn2+] = 1.0 M and PH2 = 1.0 atm. Calculate the
molar concentration of H+.

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Example 18.7
Strategy
The equation that relates standard emf and nonstandard emf is
the Nernst equation. The overall cell reaction is
Zn(s) + 2H+(? M)

Zn2+(1.0 M) + H2(1.0 atm)

Given the emf of the cell (E), we apply the Nernst equation to
solve for [H+]. Note that 2 moles of electrons are transferred per
mole of reaction; that is, n = 2.

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