Chapter18 p

Introduction to Electrochemistry
CHAPTER
Chapter18 p
Oxidation
Reduction
Reducing agent :

Oxidizing agent

Example 18-1
The following reactions are spontaneous and thus
proceed to the right, as written
What can we deduce regarding the strengths of H
+
,
Ag
+
, Cd
2+
, Zn
2+
as electron acceptors? (or oxidizing
agents)
493
2H
+
+ Cd(s) H
2
+ Cd
2+
2Ag
+
+ H
2
(g) 2Ag(s) + 2H
+
Cd
2+
+ Zn(s) Cd(s) + Zn
2+
Ag
+
> H
+
> Cd
2+
> Zn
2
+
Chapter18 p
493
Figure 18-1
Photograph of a silver tree.
Ag
+
+ e Ag(s)

Chapter18 p
Galvanic Cell
19.2
spontaneous
redox reaction
anode
oxidation
cathode
reduction
Chapter18 p
495
Figure 18-2
(a)A galvanic cell at open circuit;
Chapter18 p
495
(b) a galvanic cell doing work;
Chapter18 p
495
(c) an electronlytic cell.
Chapter18 p

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.
498
Chapter18 p
(anode)
(cathode)
Chapter18 p
500
Figure 18-3
Movement of
charge in a
galvanic cell.
Chapter18 p
18C Electrode Potentials

The cell potential E
cell
is related to the free energy of
the reaction G by
499
Chapter18 p
If the reactants and products are in their standard states,
the resulting cell potential is called the standard cell
potential.
where R is the gas constant and T is the absolute
temperature.
500
Chapter18 p
501
(a)
Chapter18 p
501
(b)
Chapter18 p
501
(c)
Chapter18 p
503
Figure 18-5
Cell potential in the galvanic cell of Figure 18-4b as a function of
time. The cell current, which is directly related to the cell potential,
also decreases with the same time behavior.
Chapter18 p
If we always follow this convention, the value of E
cell
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 E
cell
as
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
504
Chapter18 p
Figure 18-6
The hydrogen gas electrode.
505
By convention, the
potential of the
standard hydrogen
electrode is assigned a
value of 0.000 V at all
temperatures.
Chapter18 p
Standard Electrode Potentials
19.3
Zn (s) | Zn
2+
(1 M) || H
+
(1 M) | H
2
(1 atm) | Pt (s)
2e
-
+ 2H
+
(1 M) H
2
(1 atm)
Zn (s) Zn
2+
(1 M) + 2e
-
Anode (oxidation):
Cathode (reduction):
Zn (s) + 2H
+
(1 M) Zn
2+
+ H
2
(1 atm)
Chapter18 p
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
E
Ag
is the potential of the silver electrode.
p.505
Chapter18 p
The standard electrode potential, E
0
, of a half-
reaction is defined as its electrode potential when the
activities of the reactants and products are all unity.
the E
0
value for the half-reaction
the cell shown in Figure 18-7 can be represented
schematically as
506
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
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
506
Chapter18 p
18C-5 Effect of Concentration on Electrode Potentials:
The Nernst Equation
Consider the reversible half-reaction
508
Chapter18 p
E
0
= the standard electrode potential, which is
characteristic for each half-reaction
R = the ideal gas constant, 8.314 J K
1
mol
1
T = temperature, K
n = number of moles of electrons that appears in the
half-reaction for the electrode process as written
F = the faraday 96,485 C (coulombs) per mole of
electrons
If we substitute numerical values for the constants,
convert to base 10 logarithms, and specify 25C for the
temperature, we get
509
Chapter18 p
Nernst equation
p.509
If we substitute numerical values for the constants,
convert to base 10 logarithms, and specify 25C for the
temperature, we get
Chapter18 p
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
p.511
18C-6 The Standard Electrode Potential, E
0
511
4. The standard electrode potential is independent of the number
of moles of reactant and product shown in the balanced half-
reaction.
Chapter18 p
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
512
Chapter18 p
System involving precipitates or complex ions
Chapter18 p
Ch 19 Applications of Standard
Electrode Potentials
EXAMPLE 19-1
Calculate the thermodynamic potential of the following
cell and the free energy change associated with the cell
reaction.



395

2e
-
+ Fe
2+
Fe
2Ag 2Ag
+
+ 2e
-
Oxidation:
Reduction:
What is the equilibrium constant for the following reaction
at 25
0
C? Fe
2+
(aq) + 2Ag (s) Fe (s) + 2Ag
+
(aq)
=
0.0257 V
n
ln K E
cell

0
19.4
n = 2
EXAMPLE 19-2
Calculate the potential of the cell


Ag Ag
+

( 0.0200 M) (0.0200M) Cu
2+
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).


p 525
EXAMPLE 19-4
Calculate the cell potential for

Note that this cell does not require two
compartments (nor a salt bridge) because
molecular H
2
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).

p.526

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


where x = 5.00x10
-4
, 2.00x10
-3
, 1.00x10
-2
, and 5.00x10
-2


Zn ZnSO
4
( xM), PbSO
4
(sat'd) Pb

PbSO
4
(s) + 2e Pb(s) + SO
4
2-
E
0
= - 0.350 V
PbSO
4
/Pb
(a) concentration
EXAMPLE 19-5
Calculate the potential for the following cell using (a)
concentration (b) activity


where x = 5.00x10
-4
, 2.00x10
-3
, 1.00x10
-2
, and 5.00x10
-2


Zn ZnSO
4
( xM), PbSO
4
(sat'd) Pb

(b) activity
EXAMPLE 19-6
Calculate the potential required to initiate
deposition of copper from a solution that is 0.010 M
in CuSO
4
and contains sufficient H
2
SO
4
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, O
2
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)
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.

p.534
Cu(s) + 2Ag
+
2Ag(s) + Cu
2+
EXAMPLE 19-8
Calculate the equilibrium constant for the
reaction shown in Equation 19-4 at 25C.
p.535
EXAMPLE 19-9
Calculate the equilibrium constant for the
reaction
2Fe
3+
+ 3I
-
2Fe
2+
+ I
3
-
2 Fe
3+
+ 2e 2 Fe
2+
E
0
= 0.771V
I
3
-
+ 2e 3 I
-
E
0
= 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.
p.538