Chemistry, The Central Science, 10th edition

Theodore L. Brown; H. Eugene LeMay, Jr.; and Bruce E. Bursten

REDOX

Electrochemistry
Electrochemical Reactions

In electrochemical reactions, electrons

are transferred from one species to
another.
Metals tend to lose electrons and are
oxidized, non metals tend to gain
electrons and are reduced.

Electrochemistry
LEORA GEROA
Losing
Electrons is
Oxidation.
Reducing
Agent

Gaining
Electrons is
Reduction.
Oxidizing Electrochemistry
Agent
 OIL RIG

• Oxidation
• Is
• Loss.

• Reduction
• Is
Gain.
Electrochemistry
 REDOX REACTIONS
• Are reduction – • When an atom is
oxidation reactions. losing electrons its
• Electrons are O.N. increases. It is
transferred. being oxidized.

• When an atom gains

electrons its O.N.
decreases. It is being
reduced
Electrochemistry
Oxidation Numbers

In order to keep
track of what loses
electrons and what
gains them, we
assign oxidation
numbers.

Electrochemistry
 Assigning Oxidation Numbers
1. Elements in their elemental form have an ON= 0.
2. The oxidation number of a monatomic ion is its
charge.
3. Nonmetals tend to have negative oxidation
numbers, although some are positive in certain
compounds or ions.
 Oxygen has an oxidation number of −2,
except in the peroxide ion in which it has an
oxidation number of −1.
 Hydrogen is +1 except in metal hydrides when
is −1 .
 Fluorine always has an oxidation number of −1.
Electrochemistry
Assigning Oxidation Numbers
 The other halogens have an oxidation
number of −1 when they are negative;
they can have positive oxidation
numbers, however, most notably in
oxyanions
4. The sum of the oxidation numbers in a
polyatomic ion is the charge on the
ion.
5. The sum of the oxidation numbers in a
neutral compound is 0.

Electrochemistry
 Oxidation and Reduction

• A species is oxidized when it loses electrons.

 Here, zinc loses two electrons to go from neutral
zinc metal to the Zn2+ ion.

Electrochemistry
 Oxidation and Reduction

• A species is reduced when it gains electrons.

 Here, each of the H+ gains an electron and they
combine to form H2.

Electrochemistry
 Oxidation and Reduction

• What is reduced is the oxidizing agent.

 H+ oxidizes Zn by taking electrons from it.
• What is oxidized is the reducing agent.
 Zn reduces H+ by giving it electrons.
Electrochemistry
 Oxidation-Reduction
Reactions
• Zn added to HCl yields the spontaneous reaction
Zn(s) + 2H+(aq)  Zn2+(aq) + H2(g).
• The oxidation number of Zn has increased from 0 to 2+.
• The oxidation number of H has reduced from 1+ to 0.
• Zn is oxidized to Zn2+ while H+ is reduced to H2.
• H+ causes Zn to be oxidized and is the oxidizing agent.
• Zn causes H+ to be reduced and is the reducing agent.
• Note that the reducing agent is oxidized and the oxidizing
agent is reduced. Electrochemistry
 Balancing Oxidation-
Reduction Reactions
• Law of conservation of mass: the amount of each element
present at the beginning of the reaction must be present at
the end.
• Conservation of charge: electrons are not lost in a
chemical reaction.
Half Reactions
• Half-reactions are a convenient way of separating
oxidation and reduction reactions.
Electrochemistry
 Half Reactions
• The half-reactions for
Sn2+(aq) + 2Fe3+(aq)  Sn4+(aq) + 2Fe2+(aq)
are
Sn2+(aq)  Sn4+(aq) +2e-
2Fe3+(aq) + 2e-  2Fe2+(aq)
• Oxidation: electrons are products.
• Reduction: electrons are reactants.
Loss of Gain of
Electrons is Electrons is
Oxidation Reduction Electrochemistry
 Balancing Equations by the Method of
Half Reactions
• Consider the titration of an acidic solution of Na2C2O4
(sodium oxalate, colorless) with KMnO4 (deep purple).
• MnO4- is reduced to Mn2+ (pale pink) while the C2O42- is
oxidized to CO2.
• The equivalence point is given by the presence of a pale
pink color.
• If more KMnO4 is added, the solution turns purple due to
the excess KMnO4.

Electrochemistry
What is the balanced chemical equation?
1. Write down the two half reactions.
2. Balance each half reaction:
a. First with elements other than H and O.
b. Then balance O by adding water.
c. Then balance H by adding H+.
d. If it is in basic solution, remove H+ by adding OH-
e. Finish by balancing charge by adding electrons.
3. Multiply each half reaction to make the number of electrons
equal.
4. Add the reactions and simplify.
5. Check!

Electrochemistry
 Half-Reaction Method

Consider the reaction between MnO4− and C2O42− :

MnO4−(aq) + C2O42−(aq)  Mn2+(aq) + CO2(aq)

Electrochemistry
 Balancing Equations by the Method of
Half Reactions
• Consider the titration of an acidic solution of Na2C2O4
(sodium oxalate, colorless) with KMnO4 (deep purple).
• MnO4- is reduced to Mn2+ (pale pink) while the C2O42- is
oxidized to CO2.
• The equivalence point is given by the presence of a pale
pink color.
• If more KMnO4 is added, the solution turns purple due to
the excess KMnO4.

Electrochemistry
 Half-Reaction Method

First, we assign oxidation numbers.

+7 +3 +2 +4

MnO4− + C2O42-  Mn2+ + CO2

Since the manganese goes from +7 to +2, it is reduced.
Since the carbon goes from +3 to +4, it is oxidized.
Electrochemistry
For KMnO4 + Na2C2O4:

• The two incomplete half reactions are

MnO4-(aq)  Mn2+(aq)
C2O42-(aq)  2CO2(g)
2. Adding water and H+ yields
8H+ + MnO4-(aq)  Mn2+(aq) + 4H2O
• There is a charge of 7+ on the left and 2+ on the right.
Therefore, 5 electrons need to be added to the left:
5e- + 8H+ + MnO4-(aq)  Mn2+(aq) + 4H2O

Electrochemistry
• In the oxalate reaction, there is a 2- charge on the left
and a 0 charge on the right, so we need to add two
electrons:
C2O42-(aq)  2CO2(g) + 2e-
3. To balance the 5 electrons for permanganate and 2
electrons for oxalate, we need 10 electrons for both.
Multiplying gives:
10e- + 16H+ + 2MnO4-(aq)  2Mn2+(aq) + 8H2O
5C2O42-(aq)  10CO2(g) + 10e-

Electrochemistry
4. Adding gives:
16H+(aq) + 2MnO4-(aq) + 5C2O42-(aq)  2Mn2+(aq) +
8H2O(l) + 10CO2(g)
5. Which is balanced!

Electrochemistry
 Balancing in Basic Solution

• If a reaction occurs in basic solution, one

can balance it as if it occurred in acid.
• Once the equation is balanced, add OH−
to each side to “neutralize” the H+ in the
equation and create water in its place.
• If this produces water on both sides, you
might have to subtract water from each
side.
Electrochemistry
Examples – Balance the following oxidation-
reduction reactions:
1. Cr (s) + NO3- (aq)  Cr3+ (aq) + NO (g) (acidic)

2. Al (s) + MnO4- (aq)  Al3+ (aq) + Mn2+ (aq) (acidic)

3. PO33- (aq) + MnO4- (aq)  PO43- (aq) + MnO2 (s)

(basic)

Electrochemistry