Introduction to Electrochemistry

Chapter18 p
18C-2 The Standard Hydrogen Reference Electrode

an electrode must be easy to construct, reversible, and

highly reproducible in its behavior. The standard hydrogen
electrode (SHE) meets these specifications and has been
used throughout the world for many years as a universal
reference electrode. It is a typical gas electrode.

The half-reaction responsible for the potential that

develops at this electrode is

Chapter18 p 504
Figure 18-2
Chapter18 p 495
(a)A galvanic cell at open circuit;
(b) a galvanic cell doing work;
Chapter18 p 495
18B-3 Representing Cells Schematically

Chemists frequently use a shorthand notation to describe

electrochemical cells. The cell in Figure 18-2a, for example, is
described by

single vertical line indicates a phase boundary, or

interface, at which a potential develops.
The double vertical line represents two phase
boundaries, one at each end of the salt bridge. A liquid-
junction potential develops at each of these interfaces.
Chapter18 p 498
 (cathode)

(anode) Chapter18 p
Figure 18-3
Movement of
charge in a
galvanic cell.

Chapter18 p 500
18C Electrode Potentials

Chapter18 p 499
If the reactants and products are in their standard
states, the resulting cell potential is called the standard
cell potential.

Chapter18 p 500
(a)

Chapter18 p 501
(b)

Chapter18 p 501
(c)

Chapter18 p 501
If we always follow this convention, the value of Ecell is
a measure of the tendency of the cell reaction to occur
spontaneously in the direction written from left to right.

the spontaneous cell reaction will occur.

we may write the cell potential Ecell as

Chapter18 p
 Galvanic Cell

anode cathode
oxidation reduction

spontaneous
redox reaction

Chapter18 p
19.2
Figure 18-6
The hydrogen gas electrode.

By convention, the
potential of the
standard hydrogen
electrode is assigned a
value of 0.000 V at all
temperatures.

Chapter18 p 505
 Standard Electrode Potentials

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

Anode (oxidation): Zn (s) Zn2+ (1 M) + 2e-
Cathode (reduction): 2e- + 2H+ (1 M) H2 (1 atm)
Zn (s) + 2H+ (1 M) Zn2+ + H2 (1 atm) Chapter18 p
19.3
18C-3 Electrode Potential and
Standard Electrode Potential

An electrode potential is defined as the potential of a cell

in which the electrode in question is the right-hand electrode
and the standard hydrogen electrode is the left-hand
electrode.
The cell potential is

EAg is the potential of the silver electrode.

Chapter18 p
p.505
The standard electrode potential, E0, of a half-
reaction is defined as its electrode potential when the
activities of the reactants and products are all unity.
the E0 value for the half-reaction

the cell shown in Figure 18-7 can be represented

schematically as

Chapter18 p 506
Figure 18-7
Measurement of the
electrode potential
for an Ag electrode.
If the silver ion
activity in the right-
hand compartment is
1.00, the cell
potential is the
standard electrode
potential of the
Ag+/Ag half-
reaction.

Chapter18 p 506
This galvanic cell develops a potential of 0.799 V with
the silver electrode

the standard electrode potential is given a positive

sign, and we write

Chapter18 p 506
18C-2 The Standard Hydrogen Reference Electrode

an electrode must be easy to construct, reversible, and

highly reproducible in its behavior. The standard hydrogen
electrode (SHE) meets these specifications and has been
used throughout the world for many years as a universal
reference electrode. It is a typical gas electrode.

The half-reaction responsible for the potential that

develops at this electrode is

Chapter18 p 504
 18C-6 The Standard Electrode Potential, E0

1. The standard electrode potential is a relative quantity in the

sense that it is the potential of an electrochemical cell in which
the reference electrode is the standard hydrogen electrode,
whose potential has been assigned a value of 0.000 V.
2. The standard electrode potential for a half-reaction refers
exclusively to a reduction reaction;
3. The standard electrode potential measures the relative force
tending to drive the half-reaction from the reactants and
products are at their equilibrium activities
4. The standard electrode potential is independent of the number
of moles of reactant and product shown in the balanced half-
reaction.
Chapter18 p 511
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 5. A positive electrode potential indicates that the half-
reaction in question is spontaneous with respect to the
standard hydrogen electrode half-reaction.

6. The standard electrode potential for a half-reaction is

temperature dependent.

Chapter18 p
Chapter18 p 512
System involving precipitates or complex ions

Chapter18 p
Ch 19 Applications of Standard
Electrode Potentials

Chapter18 p
EXAMPLE 19-1
Calculate the thermodynamic potential of the following
cell and the free energy change associated with the cell
reaction.

395
 What is the equilibrium constant for the following reaction
at 250C? Fe2+ (aq) + 2Ag (s) Fe (s) + 2Ag+ (aq)
0 0.0257 V
Ecell = ln K
n

Oxidation: 2Ag 2Ag+ + 2e-

n=2
Reduction: 2e + Fe
- 2+
Fe
EXAMPLE 19-2
Calculate the potential of the cell

Ag Ag+ ( 0.0200 M) (0.0200M) Cu2+ Cu

EXAMPLE 19-3
Calculate the potential of the following cell and indicate
the reaction that would occur spontaneously if the cell
were short circuited (Figure 19-1).

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EXAMPLE 19-4
Calculate the cell potential for

Note that this cell does not require two

compartments (nor a salt bridge) because
molecular H2 has little tendency to react
directly with the low concentration of Ag in
the electrolyte solution. This is an example of
a cell without liquid junction (Figure 19-2).

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 EXAMPLE 19-5
Calculate the potential for the following cell using (a)
concentration (b) activity

Zn ZnSO4 ( xM), PbSO4 (sat'd) Pb

where x = 5.00x10-4, 2.00x10-3, 1.00x10-2, and 5.00x10-2
(a) concentration
PbSO4(s) + 2e Pb(s) + SO42- E0PbSO /Pb = - 0.350 V
4
 EXAMPLE 19-5
Calculate the potential for the following cell using (a)
concentration (b) activity

Zn ZnSO4 ( xM), PbSO4 (sat'd) Pb

where x = 5.00x10-4, 2.00x10-3, 1.00x10-2, and 5.00x10-2
(b) activity
EXAMPLE 19-6
Calculate the potential required to initiate
deposition of copper from a solution that is 0.010 M
in CuSO4 and contains sufficient H2SO4 to give a pH
of 4.00.
The deposition of copper necessarily occurs at the
cathode.
Since there is no more easily oxidizable species than
water in the system, O2 will evolve at the anode.
EXAMPLE 19-7
D. A. MacInnes found that a cell similar to that
shown in Figure 19-2 had a potential of 0.52053 V.
The cell is described by the following notation.

Calculate the standard electrode potential for the

half-reaction (by activities)
 Cu(s) + 2Ag+ 2Ag(s) + Cu2+
19C CALCULATING REDOX EQUILIBRIUM
CONSTANTS
Thus, at chemical equilibrium, we may write

or

We can generalize Equation 19-6 by stating that at

equilibrium, the electrode potentials for all half-
reactions in an oxidation/reduction system are equal.

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EXAMPLE 19-8
Calculate the equilibrium constant for the
reaction shown in Equation 19-4 at 25C.

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EXAMPLE 19-9
Calculate the equilibrium constant for the
reaction
3+ - 2+ -
2Fe + 3I 2Fe + I3
2 Fe3+ + 2e 2 Fe2+ E0 = 0.771V
I3 -
+ 2e 3I- E0 = 0.536V
EXAMPLE 19-10
Calculate the equilibrium constant for the
reaction

Again we have multiplied both equations by

integers so that the numbers of electrons are
equal. When this system is at equilibrium.

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