Chapter 21

Electrochemistry:

Chemical Change and Electrical Work

Silberberg & Amateis (S&A) : Section 21.1 – 21.3, 21.5 – 21.7

Silberberg (S) : Section 21.1 – 21.3, 21.5 – 21.7

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Electrochemistry: Chemical Change and
Electrical Work
21.1 Redox Reactions and Electrochemical Cells

21.2 Voltaic Cells: Using Spontaneous Reactions to Generate

Electrical Energy
21.3 Cell Potential: Output of a Voltaic Cell

21.5 Electrochemical Processes in Batteries

21.6 Corrosion: An Environmental Voltaic Cell

21.7 Electrolytic Cells: Using Electrical Energy to Drive

Nonspontaneous Reactions
 Sec. 21.1

HALF-REACTION METHOD FOR BALANCING REDOX REACTIONS

STEPS (p. 689 in 3rd Edition textbook):

1) Divide the skeleton reaction into two half-reactions (oxidation half-reaction and reduction half-
reaction)
2) Balance the atoms and charges in each half-reaction
• First balance atoms (a) other than O and H, (b) then O, (c) then H.
o Balancing in an acidic solution: use H2O molecules and H+ ions
o Balancing in a basic solution: balance as if in acidic solution and then add OH- to both
sides of the equation for every H+ ion present (OH- and H+ combine to form H2O)
• (d) Charge is balanced by adding e-
3) If necessary, multiply one or both half-reactions by an integer so that: no. of e- gained in reduction =
no. of e- lost in oxidation.
4) Add the balanced half-reactions, cancelling substances that appear on both sides, and include states
of matter.
5) Check that the atoms and charges are balanced.
Balancing Redox Reactions in Acidic Solution

BrO3-(aq) + N2H4(aq) Br2(l) + N2(g)

1. Divide the reaction into half-reactions -
Determine the O.N.s for the species undergoing redox.
+5 -2 0 0
BrO3-(aq) + N2H4(aq) Br2(l) + N2(g)
BrO3- Br2 Br is going from +5 to 0

N2H4 N2 N is going from -2 to 0

2. Balance atoms and charges in each half-reaction -

12H+(aq) + 2BrO3- Br2 + 6H2O(l)
Add 10e- to
net: +10 net: 0 reactants.
10e- + 12H+(aq) + 2BrO3-(aq) Br2(l) + 6H2O(l)
Balancing Redox Reactions in Acidic Solution
continued
10e- + 12H+(aq) + 2BrO3-(aq) Br2(l) + 6H2O(l)
N2H4(aq) N2(g) + 4H+(aq)+ 4e-
BrO3- is the oxidizing agent and N2H4 is the reducing agent.
3. Multiply each half-reaction by an integer, if necessary -
[10e- + 12H+(aq) + 2BrO3-(aq) Br2(l) + 6H2O(l) ] X2

[N2H4(aq) N2(g) + 4H+(aq)+ 4e- ] X5

4. Add the half-reactions together -
20e- + 24H+(aq) + 4BrO3-(aq) 2Br2(l) + 12H2O(l)
5N2H4(aq) 5N2(g) + 20H+(aq) + 20e-

4H+(aq) + 4BrO3-(aq) +5N2H4(aq) + 12H2O(l) + 5N2(g)

2Br2(l)
5. Do a final check on atoms and charges.
 Balancing Redox Reactions in Basic Solution

Balance the reaction in acid and then add OH- so as to

neutralize the H+ ions.
4H+(aq) + 4BrO3-(aq) +5N2H4(aq) 2Br2(l) + 12H2O(l) + 5N2(g)

+ 4OH-(aq) + 4OH-(aq)
4H2O(l) + 4BrO3-(aq) +5N2H4(aq) 2Br2(l) + 12H2O(l) + 5N2(g) + 4OH-(aq)

Reconcile the number of water molecules.

4BrO3-(aq) +5N2H4(aq) 2Br2(l) + 8H2O(l) + 5N2(g) + 4OH-(aq)

Do a final check on atoms and charges.

Sample Problem 21.1 S&A

Permanganate ion reacts in basic solution with oxalate

ion to form carbonate ion and solid manganese
dioxide. Balance the skeleton ionic equation for the
reaction between NaMnO4 and Na2C2O4 in basic
solution:

MnO −4 (aq ) + C2 O 24− (aq ) → MnO 2 ( s ) + CO32− (aq ) [ basic solution ]

A summary of redox terminology.
(Recall Chapter 4)
Zn(s) + 2H+(aq)
OXIDATION
One reactant loses electrons.
Reducing agent is oxidized.
Oxidation number increases.
REDUCTION
Other reactant gains electrons.
Oxidizing agent is reduced.
Oxidation number decreases.
Zn2+(aq) + H2(g)
Zn loses electrons.
Zn is the reducing agent
and becomes oxidized.
The oxidation number of
Zn increases from 0 to +2.
Hydrogen ion gains
electrons.
Hydrogen ion is the oxidizing agent and
becomes reduced.
The oxidation number of H decreases
from +1 to 0.
The spontaneous reaction between zinc and copper(II) ion.
General characteristics of voltaic and electrolytic cells.

Spontaneous Reaction Nonspontaneous Reaction

A voltaic cell based on the zinc-copper reaction.
A voltaic cell using inactive electrodes.
Determining an unknown Eohalf-cell with the standard
reference (hydrogen) electrode.
Calculating Cell Potential
• Standard electrode potential is the difference between the standard
electrode potential of the cathode (reduction) half cell and the standard
electrode potential of the anode (oxidation) half cell

E0cell = E0cathode (reduction) – E0anode (oxidation)

Eocell = Eoreduction - Eooxidation
• Spontaneous Reaction E0 > 0

• Reduction half cell potentials are measured against H2 half cell

E0 = E0unkown – 0.00 V

N.B. the reference cell can be anode or cathode

16
Writing Spontaneous Redox Reactions
•By convention, electrode potentials are written as reductions.

•When pairing two half-cells, you must reverse one reduction half-cell
to produce an oxidation half-cell.

•The difference between the reduction half-cell potential and the

oxidation half-cell potential give the Eocell.

•When writing a spontaneous redox reaction, the left side (reactants)

must contain the stronger oxidizing and reducing agents.

Example: Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

stronger stronger weaker weaker
reducing oxidizing agent oxidizing reducing
agent agent agent
Sample Problem 21.4
A voltaic cell houses the reaction between aqueous
bromine and zinc metal:

Br2(aq) + Zn(s) → Zn2+(aq) + 2Br-(aq)

Eocell = 1.83 V

Calculate Eobromine, given Eozinc = - 0.76 V

Relative Reactivities (Activities) of Metals
(Recall Chapter 4)
1. Metals that can displace H2 from acid.

2. Metals that cannot displace H2 from acid.

3. Metals that can displace H2 from water.

4. Metals that can displace other metals from

solution.
Using standard cell potentials we can calculate which
metal/acid/water reactions produce hydrogen
i.e. when E0cell >0
Figure 21.9 The reaction of calcium in water.
 Spontaneous reaction
Find the Eocell for a tin-silver voltaic cell.

Sn2+ +2e- <-> Sn(s) Eotin = -0.14 V

Past Exam Question

Urea electrolysis is a potential process for disinfecting domestic wastewater.

Urea has a molecular formula of CO(NH2)2. During the electrolysis process,
urea is converted into nitrogen gas and carbon dioxide at one electrode whilst
hydrogen gas is evolved from water at the other electrode. Electrolytic
conditions are alkaline and the standard potential for urea is Eo = -0.46 V
relative to the standard hydrogen electrode.

a) Write down the two half reactions and the final balanced equation

b) Calculate the standard cell potential for the process

c) Two metals are available for use as electrode material for the anode: Al(s)
and Ni(s). Choose the appropriate electrode material and justify your choice.
 BATTERIES
PRIMARY SECONDARY
(Nonrechargeable) (Rechargeable)

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• Dry cells • Lead-acid battery
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• Alkaline battery • Ni-MH battery

• Mercury & silver • Lithium-Ion
(button) battery battery

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Electrochemical Electrochemical
reaction is not reaction is reversible
reversible
DISCHARGE: DISCHARGE:
Anode – oxidation Anode – oxidation
Cathode – reduction Cathode – reduction
RECHARGE:
Anode – reduction
Cathode – oxidation
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 BATTERIES
FUEL CELL
o Does not get ‘flat’
o Not necessary to recharge
o Provides electrical & heat energy as long as
fuel is supplied
o Comprises two electrodes surrounding
electrolyte
o H2 enters anode
o O2 enters cathode
o H2 separates into proton & electron
o H+ moves through electrolyte
o Electrons form external electrical circuit
•Anode (oxidation):
that can be utilized 2H2(g) 4H+(aq) + 4 e-
•Cathode (reduction):
o H+, O2 & electrons gather at the cathode to O2(g) + 4H+(aq) + 4 e- 2H20(g)
form H2O •Overall (cell) reaction:
2H2(g) + O2(g) 2H20(g)
 CORROSION & RUST
o CORROSION = A chemical or electrochemical reaction between a material
(usually metal) and the environment that leads to deterioration of the material.
o Most common form of corrosion is oxidation: rust (iron), verdigris (copper),
tarnish (silver) etc.

o Corrosion is a natural redox process that changes metals into oxides or sulphides,
and can be explained by the principles of electrochemistry.
o RUST = A red or brown oxide layer on e.g. iron or steel that results from a
reaction with the metal, oxygen and moisture.

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 CORROSION & RUST
GENERAL FACTS ON IRON CORROSION
• Iron does not rust in dry air; moisture must be present
• Iron does not rust in oxygen-free water; oxygen must be present
• Iron loss and rust deposit often occur at different places on the
same object (‘rust’ is not a direct product of Fe and O2)
• Iron corrodes more quickly at low pH (high [H+])
• Iron corrodes more quickly when in contact with ionic solutions
• Fe corrodes more quickly in contact with a less active metal (e.g.
Cu) and more slowly in contact with a more active metal (e.g.
Zn).
 CORROSION & RUST
There are reactions at the anode and the cathode which together make up the total
redox reaction for corrosion.

OXIDATION at ANODE: Fe(s)  Fe2+(aq) + 2e-

REDUCTION at CATHODE: O2(g) + 4H+(aq) + 4e-  2H2O(l)
TOTAL: 2Fe(s) + O2(g) + 4H+(aq)  2Fe2+(aq) + 2H2O(l)
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 CORROSION & RUST
Rust forms through a redox reaction where Fe2+ disperses through the water and
reacts with oxygen to form the Fe3+ in the rust.

RUST reaction: 2Fe2+(aq) + ½O2(g) + (2+n)H2O(l)  Fe2O3.nH20(s) + 4H+(aq)

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 CORROSION & RUST

If Fe makes contact with a less If Fe makes contact with a more

active metal e.g. Cu:
• Fe loses e- more easily
• Fe more anodic
• Fe corrodes more easily
active metal e.g. Zn:
• Zn acts as anode and loses e-
• Fe is cathodic and does not corrode
• Cathodic protection
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 CORROSION & RUST
Figure 21.23: The use of sacrificial anodes to prevent iron corrosion.

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TO PREVENT CORROSION:
◦ Connect a more active metal (e.g. Mg or Al) to Fe pipe
◦ The more active metal, not Fe, will corrode (cathodic protection)
◦ “SACRIFICIAL ANODE”
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The electrolysis of water.
Questions