Chapter 18: Electrochemistry

Key topics:
Galvanic cells
Nernst equation
Batteries; electrolysis

Balancing Redox Reactions

A redox reaction involves a transfer of electrons from one

species to another. This results in a change in oxidation
number.

Oxidation (reducing agent): loss of

electrons Reduction (oxidizing agent):
gain of
electrons
these reactions must occur together

example: thermal decomposition of potassium chlorate

2 K O3 (s) ⌦ 2 Kz} |C{zl}| (g)
|{ z} | |{
C l {z (s) + 3 O2
| {z } } {z
+1 +5 —2x3 +1 —1 0x2

example: combustion of methane

H4 (g) +2 O2 (g) ⌦ O2 (g) +2 H2 Oz}
| | | | | | |{
(l)
{C {z {z {C {z {z —2
} } } }
z} +1x4 0x2 z} —2x2 +1x2
—4 +4

Balancing Simple Redox Reactions

In a redox reaction both the mass and the charge must be
balanced
example: (net ionic equation)
Al(s) + Ni2+(aq)  Al3+(aq) +
Ni(s) balanced by mass, but not by
charge
What do we do?

1. Divide reaction into two half-reactions and add e–

to each half-reaction to balance the charge.
The two half-reactions correspond to reduction and
oxidation
Al(s)  Al3+(aq) + 3e–
Ni2+(aq) + 2e–  Ni(s)
2. Multiply to get same number of e– in each reaction:
(number of e– lost must equal number of e– gained)
2 [Al(s)  Al3+(aq) + 3e– ]
3 [Ni2+(aq) + 2e–  Ni(s) ]

3. Cancel e– to get the balanced net ionic reaction:

2 Al(s)  2 Al3+(aq) + 6 e
3 Ni2+(aq) + 6 e  3 Ni(s)

2 Al(s) + 3 Ni2+(aq)  2 Al3+(aq) + 3 Ni(s)

Balancing Redox Reactions involving H and O

o you will be told if the reaction occurs under acidic or
basic conditions
o use H2O to balance oxygen
o use H+ to balance hydrogen
o use OH– to make basic (under basic conditions)

example: balance the following reaction (acidic

conditions) Cr2O72– + Fe2+  Cr3+ +
Fe3+
1. Half
reactions 3+
7 ! Cr
Cr2O2—

Fe2+ ! Fe3+
2. Balance by mass for elements other than H and O
Cr2O2—
7 ! 2Cr
3+

Fe2+ ! Fe3+
3. Balance O using H2O
Cr2O2—
7 ! 2Cr3+ + 7H2O

Fe2+ ! Fe3+
4. Balance H using H+
14H+ + Cr2O72— ! 2Cr3+ + 7H2O

Fe2+ ! Fe3+
5. Balance change using e–
6e— + 14H+ + Cr2O
7
2—
! 2Cr3+ + 7H2O

Fe2+ ! Fe3+ + e—

6. Balance e– in two half reactions to add them together

6e— + 14H+ + Cr2O72— ! 2Cr3+ + 7H2O
6⇥ ⇤
2+ 3+
Fe ! Fe + e —
7. Add half reactions and cancel species common to both
sides
14H+ + Cr2O2—
7 + 6Fe
2+
! 2Cr3+ + 6Fe3+ + 7H2O

8. Check your answer for mass and charge balance

Under basic conditions:

o balance as if under acidic conditions
o for each H+ in the final equation, add OH– to both
sides
o combine H+ and OH– to produce H2O
o cancel H2O from both sides if needed

example: balance the following reaction (basic

conditions) 4 4
3 + MnO
SO2—
—
! SO2 + MnO2
—

Balancing under acidic conditions gives

2H+ + 3SO32— + 2MnO
4
—
! 3SO42 + 2MnO2 + H2O
—

Then we add 2OH– to both sides to obtain

H2O + 3SO2—
3 + 2MnO —
4 ! 3SO4
2—
+ 2MnO 2 + 2OH —

Galvanic Cells

If we put a piece of copper metal into a AgNO 3

solution, a redox reaction occurs:2Ag+(aq) + Cu(s) 
2Ag(s) + Cu2+(aq)
The reaction will stop when the copper metal gets
covered with silver.
If we want to use this spontaneous reaction to extract
energy and do work we need to separate the two half
reactions by building a galvanic cell (also called a
voltaic cell):
Electrodes
o anode, oxidation
o cathode, reduction

Half-cell
o one container, electrode, and solution

Salt bridge
o conducting medium through which ions can move
from one half-cell to the other half-cell
o this is electrolytic conduction (the movement of
ions carrying electrical charge)
o contrast with metallic conduction (electrons through
wire)

Ion migration
o anions migrate towards the anode
o cations migrate towards the cathode

Conduction of charge
o Cu2+ enters anode solution (+ charge builds up)
o anions from the salt bridge counter this buildup
o Ag+ leaves cathode solution (– charge builds up)
o cations from the salt bridge counter this buildup
o salt bridge maintains electrical
neutrality (otherwise the reaction will
quickly stop)

Charge on the electrodes

o anode: negative (electrons left by Cu oxidation)
o cathode: positive (Ag+ becomes part of electrode)
Cell Notation (shorthand for describing a galvanic cell):

Standard Reduction Potentials

Electrical current flows from the anode to the cathode

due to a difference in electrical potential energy
between the electrodes

This current is measured, in volts (V), by a voltmeter.

Measured current
o called the overall cell potential (Ecell)
o is the difference between the electrical potentials
at the two electrodes (the two half-cell potentials)
o varies with concentration, temperature, metals/ions
used.

Standard cell potential : The cell potential under standard

state conditions, [ions] = 1 M, T = 25C, 1 atm gas
pressure.
 Zn(s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu(s)

Each half-reaction can be considered to have a

reduction potential associated with it. This measures
the natural tendency of the half-reaction to proceed
as a reduction.

Standard reduction potential (E or Ered): Reduction

potential for a half-reaction under standard state
conditions.

When two half-reactions are connected

o the one with the larger (more positive) Ered goes as
a reduction
o the other one (less positive Ered) goes as an
oxidation with Eox = -(Ered)
○ = E ○
+ E ○
Ecell
| |{ozx}
{rzed anode
}
cathode

We can only measure Ecell so how do we get Ered and

Eox ? We select a specific half-cell as our reference
(defined as zero) and then use this one to get Ered for
all other half-cells.
Reference half-cell : standard hydrogen electrode (SHE)
o standard state conditions
o assigned a value of 0 V
o reaction is 2H+ (1 M) + 2e–  H2 (1 atm)
E○ + /H = 0 V
2
H

How to measure the Cu2+ standard reduction potential:

Measure the
charge on the
electrodes: Cu
(+)  cathode H2
(–)  anode

Measure the
current: 0.34 V
Cu2+ + 2e— → Cu(s) E○ = ○ + ox,
○
cell red, Cu2+ /Cu H+ /H2
H2(g) → 2H+ + 2e— 0.34 VE= red, Cu
2+
E
/Cu +0
E○
——— ————— ————
Cu2+ + H2(g) → 2H+ + Cu(s) Ered,
○
Cu 2+ /Cu = +0.34 V

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

How to measure the Zn2+ standard reduction potential:

Measure the
charge on the
electrodes: H2
(+)  cathode Zn
(–)  anode

Measure the
current: 0.76 V

2H+ + 2e— → H2(g) E○ = ○ + ○

cell red, H+ /H2 ox, Zn2+ /Zn
Zn(s) → Zn2+ + 2e— E= 0 +
0.76 V E
2+
ox, Zn /Zn
E○
——— ————— ————
2H+ + Zn(s) → Zn2+ + H2(g) Eox,
○
Zn
2+
/Zn = +0.76 V
○
Ered, Zn2+ /Zn = —0.76 V
Zn(s) | Zn2+ (1 M) || H+ (1 M) | H2 (1 atm) | Pt(s)

Once the half-cell potentials are determined, we can calculate

Ecell
○ ○ ○
Ecell = red + ox ○
○
=
E E ○
E 2+ + E 2+
Ecell red, Cu /Cu ox, Zn /Zn
= 0.34 V + 0.76 V = 1.10 V
Table 18.1: E values for several half reactions

more (+) : more

likely to be
reduced, better
oxidizing agent

more (–) : more

likely to be
oxidized, better
reducing agent