Redox Reactions and

Electrochemistry
Lecture 4
Lecturer: PhD Tamriko Supatashvili
(invited specialist)

2020

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The chemical changes that occur when electrons are
transferred between reactants are called oxidation –
reduction reactions

- -principal source of energy on earth

- -combustion of gasoline
- -burning of wood
-burning food in your body

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Oxidation reactions are always
accompanied by a reduction reaction
Oxidation
- originally meant combining with oxygen
- iron rusting (iron + oxygen)

Reduction
- originally meant the loss of oxygen from
a compound
removing iron from iron ore ( iron II oxide)
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20.2 Electron Transfer in Redox Reactions

Today
OXIDATION means:
- a complete or partial LOSS of ELECTRONS

REDUCTION means:
- a complete or partial GAIN of ELECTRONS

Memory Device :
LEO the lion says GER or OIL RIG
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The substance that donates electrons in a redox
reaction is the REDUCING AGENT

The substance that takes electrons in a redox

reaction is the OXIDIZING AGENT

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Oxidation is… Reduction is…

–the loss of electrons –the gain of electrons

–an increase in oxidation –a decrease in oxidation

state state

–the addition of oxygen –the loss of oxygen

–the loss of hydrogen –the addition of hydrogen

MgO + H2  Mg + H2O
2 Mg + O2  2 MgO

notice the Mg2+ in MgO is gaining

notice the magnesium is losing electrons
electrons

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 20.3 Assigning Oxidation Numbers (ON)
Oxidation States

Oxidation states are numbers assigned to atoms that

reflect the net charge an atom would have if the electrons
in the chemical bonds involving that atom were assigned to
the more electronegative atoms.

Oxidation states can be thought of as “imaginary” charges.

They are assigned according to the following set of rules:

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#1
The ON of a simple ion is equal to its
ionic charge
+1 +2 -3
Na + Cu 2+ N3-

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#2
The ON of hydrogen is always +1,
except in metal hydrides like NaH
where it is –1

+1 -1
HCl NaH

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#3
The ON of oxygen is always –2 except in
peroxides like X2O2 where it is –1

-2 -1
+2 H2O H2O2
OF2

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#4
The ON of an uncombined element is
always zero

0 0 0
Na Cu N2

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#5
For any neutral(zero charge) compound,
the sum of the ON’s is always zero

+4-2
CO2

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#6
For a complex ion, the sum of the ON’s
equals the charge of the complex ion

+7 -2
MnO41-

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 Examples - assigning oxidation numbers

Assign oxidation states to all elements:

H2 SO3 SO42-
+ -
K NH3 MnO4

Cr2O72- CH3OH PO43-

- -
ClO3 HSO3 Cu

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20.4 Oxidation # Changes

an increase in oxidation number of an atom

signifies oxidation
+2 to +4
a decrease in oxidation number of an atom
signifies reduction
0 to -1

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 Oxidation Numbers

• The oxidation number of an atom in an

element is zero.
E.g. Mg in Mg, O in O2.
 Oxidation Numbers
• The oxidation F -1
numbers of atoms in
a compound add up to
zero. O -2
Oxidation state of C in
CO2? H +1
?–4=0
Put the +! Cl -1
? = +4
 Oxidation Numbers
• The oxidation F -1
numbers of atoms in
a compound add up to
zero. O -2
Oxidation state of Mg
in MgCl2? H +1

Cl -1
+2
 Oxidation Numbers
• The oxidation F -1
numbers of atoms in
a compound add up to
zero. O -2
Oxidation state of N
in NH3? H +1

Cl -1
-3
 Oxidation Numbers
• The oxidation numbers
of atoms in an ion add F -1
up to the charge on the
ion.
O -2
Oxidation state of S in
SO42-? H +1
? – 8 = -2
Cl -1
? = +6
 Identifying Redox Reactions

Oxidation and reduction always occur

together in a chemical reaction. For this
reason, these reactions are called “redox”
reactions.

Although there are different ways of

identifying a redox reaction, the best is to
look for a change in oxidation state:

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 Oxidation numbers (states) can be
assigned to atoms and ions. Changes
in oxidation numbers indicate that
oxidation and reduction have
occurred.
0 2+ 5+ 2- 2+ 5+ 2- 0
Zn + Cu(NO3)2 Zn(NO3)2 + Cu
Find the oxidation numbers and see which ones change.
Nitrate NO3 is -1

Zn0 Zn2+ + 2e- Oxidation

Cu2+ + 2e- Cu0 Reduction 23
 In a redox reaction the number of
electrons lost is equal to the number
of electrons gained.
The number of electrons must be
balanced!
0 0 3+ 2-
Al + O2 Al2O3
Al0 Al3+ + 3e- oxidation - 3 electrons lost
O20 + 4e- 2O2- reduction - 4 electrons
gained
4(Al0 Al3+ + 3e-) multiply by 4
3(O20 + 4e- 2O2-( multiply by 3
12 electrons are transferred in this reaction 24
 +2 = LEO

OA
+2 -1 +4 -1 +4 -1 +2 -1

SnCl2 + PbCl4 SnCl4 + PbCl2

RA

-2 = GER

-3 = GER
RA
+2 -2 +1 +5 -2 +2 0 +2 -2 +1 -2
CuS + H+ + NO3- Cu+2 + S + NO + H 2O
OA

+2 = LEO

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 Examples - labeling redox reactions
In each reaction, look for changes in oxidation state.
Ifchanges occur, identify the substance being reduced, and the
substance being oxidized.
Identify the oxidizing agent and the reducing agent.

= +1 (H is oxidized) (reducing agent)

0 +2 -2 0 +1 -2

H2 + CuO  Cu + H2O

= -2 (Cu is reduced) (oxidizing agent)

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 Try These!!

+1 = Fe 2+ is oxidized (reducing agent)

5 Fe2+ + MnO4- + 8 H+  5 Fe3+ + Mn2+ + 4 H2O

- 5 = Mn 7+ is reduced (oxidizing agent)

+2 = Zn 0 is oxidized (reducing agent)

Zn + 2 HCl  ZnCl2 + H2

- 1 = H 1+ is reduced (oxidizing agent)

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20.5 Balancing Redox Equations

There are two methods used to balance redox

reactions

1)the oxidation number change

method

2)the half reaction method

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These methods are based on the fact that the
total number of electrons gained in reduction
must equal the total number of electrons lost in
oxidation

Redox reactions are often quite complicated and

difficult to balance. For this reason, you’ll learn a
step-by-step method for balancing these types of
reactions, when they occur in acidic or in basic
solutions.
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 Oxidation Number Change Method
Balance the following: Fe2O3 + CO Fe + CO2

1)Assign ON to all atoms

+3 -2 +2 -2 0 +4 -2
Fe2O3 + CO Fe + CO2

2)Identify which atoms are oxidized and which are reduced

-3 (Fe reduced)

+3 -2 +2 -2 0 +4 -2
Fe2O3 + CO Fe + CO2

+2 (C oxidized)
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3) Make the total increase in oxidation number equal the total
decrease in oxidation number by using appropriate coefficients
on the reactant side only.
-3 (x 2 atoms) = 6 electrons gained

+3 -2 +2 -2 0 +4 -2
Fe2O3 + 3CO Fe + CO2

+2 (X 3 atoms) = 6 electrons lost

4) Finally check to be sure that the equation is balanced both for

atoms and charge.

Fe2O3 + 3CO Fe
2 + CO
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 Balancing Equations with the Half-Reaction Method

1) First split the original equation into two half-reactions, one “reduction” and the other
“oxidation”.

In each half-reaction, follow these steps:

2) Balance all elements except “H” and “O”.
3) Balance the “O’s” by adding water, H2O.
4) Balance the “H’s” by adding hydrogen ions, H+.
If your rxn is taking place in an acidic solution, skip to step 8
If your rxn is taking place in a basic solution proceed to step 5
5) Adjust for basic conditions by adding to both sides the same # of OH- ions as the
number of H+ ions already present
6) Simplify the equation by combining H + and OH- that appear on the same side of the
equation into water molecules.
7) Cancel any water molecules present on both sides of the equation
8) Balance the charges by adding electrons
9) Recombine the ½ reactions into a complete balanced equation. 33
Example:

Fe2+ + Cr2O72-  Fe3+ + Cr3+ acidic solution

6( Fe2+ Fe3+ + 1e- )

1( 6 e- + 14 H+ + Cr2O7
2-  2 Cr3+ + 7 H2O )

Cr2O72- + 6 Fe2+ + 14 H+  2 Cr3+ + 6 Fe3+ + 7 H2O

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 What if the solution was basic?
Notice that the method has assumed the solution was acidic - we added
H+ to balance the equation. The [H+] in a basic solution is very small.
The [OH-] is much greater.

For this reason, we will add enough OH- ions to both sides of the
equation to neutralize the H+ added in the reaction.

The hydrogen and hydroxide ions will combine to make water, and you
may have to do some canceling before you’re done.

Cr2O72- + Fe2+ + H2O  Cr3+ + Fe3+

Try this in a basic solution!!!

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 Cr2O72- + Fe2+ + H2O  Cr3+ + Fe3+ Basic Solution

6 ( Fe2+ Fe3+ +)1e-

1 (6 e- + 14OH
14
- +H O
2 14H
+ + Cr2O72- 2 Cr3+ + 7 H2O + )14OH-

Cr2O72- + 6 Fe2+ + 7 H2O  2 Cr3+ + 6 Fe3+ + 14 OH-

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Balancing Redox Equations Practice
Balance in acidic solution:

H2C2O4 + MnO4-  Mn2+ + CO2

5 H2C2O4 + 2 MnO4- + 6 H+  2 Mn2+ + 10 CO2 + 8 H2O

Balance in basic solution:

CN- + MnO4-  CNO- + MnO2

3 CN- + 2 MnO4- + H2O  3 CNO- + 2 MnO2 + 2 OH-

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 Redox Reactions - What’s Happening?

Zinc is added to a
blue solution of
copper(II) sulfate Zn (s) + CuSO4 (aq)  ZnSO4 (aq) + Cu (s)

The blue colour

disappears…the zinc
metal “dissolves”, and
solid copper metal
precipitates on the
zinc strip

The zinc is oxidized

(loses electrons)
The copper ions are
Zn (s) + Cu2+ (aq)  Zn2+ (aq) + Cu (s)
reduced (gain
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electrons)
Copper ions (Cu2+)
collide with the zinc
metal surface
A zinc atom (Zn)
gives up two of its
electrons to the
copper ion
The result is a
neutral atom of Cu
deposited on the
zinc strip, and a
Zn2+ ion released
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into the solution
A more active metal
will replace a less
active metal from its
compound.

• Zn + CuSO4 Cu + ZnSO4
Zinc replaces copper because zinc is
more active than copper.
• Cu + ZnSO4 No Reaction
Copper cannot replace zinc

Oxidation is on top
Reduction is on bottom 40
Oxidation and Reduction

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 Zn and Cu2+

Zn(s) Zn2+(aq) + 2e- oxidation

Silvery metal

Cu2+(aq) + 2e- Cu(s) reduction

Blue orange

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Electron Transfer from Zn to Cu2+

Oxidation: electron loss

Reduction: electron gain

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 Learning Check
Identify each of the following as
1) oxidation or 2) reduction.

__A. Sn(s) Sn4+(aq) + 4e−

__B. Fe3+(aq) + 1e− Fe2+(aq)
__C. Cl2(g) + 2e− 2Cl-(aq)

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 Solution
Identify each of the following as
1) oxidation or 2) reduction.

1 A. Sn(s) Sn4+(aq) + 4e−

2 B Fe3+(aq) + 1e− Fe2+(aq)
2 C. Cl2(g) + 2e− 2Cl-(aq)

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Writing Oxidation and Reduction Reactions
Write the separate oxidation and reduction reactions for
the following equation.

2Cs(s) + F2(g) 2CsF(s)

A cesium atom loses an electron to form cesium ion.

Cs(s) Cs+(s) + 1e− oxidation

Fluorine atoms gain electrons to form fluoride ions.

F2(s) + 2e- 2F−(s) reduction

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Chapter Outline

 Oxidation-Reduction Reactions
b. The Chemistry of Photography
1. For photographic film that contains AgBr, light causes loss of an
electron by bromide (Br-) and gain of that electron by silver ion
(Ag+).
2. Grains of reduced metallic silver (Ag) form the photographic
image.

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 Learning Check

Identify the substances that are oxidized and reduced in

each of the following reactions:

A. Mg(s) + 2H+(aq) Mg2+(aq) + H2(g)

B. 2Al(s) + 3Br2(g) 2AlBr3(s)

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 Solution

A. Mg is oxidized Mg(s) Mg2+(aq) + 2e−

H+ is reduced 2H+ + 2e− H2

B. Al is oxidized Al Al3+ + 3e−

Br is reduced Br + e− Br −

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Common uses of the terms oxidization and
reduction

Term Meaning
Oxidation To combine with oxygen
To lose hydrogen
To lose electrons
To increase in oxidation number
Reduction To lose oxygen
To combine with hydrogen
To gain electrons
To decrease in oxidation number

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Chapter Outline

 Oxidation-Reduction Reactions
c. The Chemistry of Batteries
1. Combining a readily oxidized substance with an easily reduced
substance can create a battery.
2. The oxidized material is the anode and the reduced material is the
cathode of the battery.

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Figure 10.4 Batteries

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Figure 10.5: An alkaline
"dry cell" in circuit with a lightbulb

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 An electrolytic cell requires
electrical energy to produce
chemical change. This process
is known as electrolysis.

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 Electrolysis
If you melt or dissolve an ionic compound (such as NaCl or CuCl2),
then the ions become free to move around – and carry electrical
current.

Molecule of solid
copper chloride
CuCl2 (s)

Molecule of solid copper

chloride after being
dissolved
chloride Copper CuCl2 (aq)
ion
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ion
 Electrolysis
Electrolysis is used to separate a metal from its compound.

When we electrolysed copper

chloride the _____ chloride ions
moved to the ______ electrode
and the ______ copper ions
moved to the ______ electrode
– OPPOSITES ATTRACT!!!

= chloride ion

= copper ion
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 Oxidation and Reduction in Electrolysis
At the positive At the negative
electrode the negative electrode the positive
ions LOSE electrons – ions GAIN electrons –
This is called Oxidation. this is called Reduction.
The half equation is: The half equation is:
2Cl- - 2e- Cl2 Cu2+ + 2e- Cu

Oxidation Is Loss, Reduction Is Gain

(of electrons)
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OILRIG
 Electrolysis of brine
Sodium chloride (salt) is made of an alkali metal and a
halogen. When it’s dissolved we call the solution “brine”, and
we can electrolyse it to produce 3 things…

Chlorine gas (Cl2) – used to kill Hydrogen gas (H2) – used to

bacteria and to make acids, manufacture ammonia and
bleach and plastics margarine

Sodium chloride
(brine)
NaCl(aq)

Sodium hydroxide
(NaOH(aq)). Used to make
Positive electrode Negative soap, paper and ceramics
23/04/2020 electrode
Chapter Outline

 Oxidation-Reduction Reactions
d. Role in Metabolism
1. Oxidation can also be considered to be gain of oxygen or loss of
hydrogen in a molecule.
2. Reduction can also be considered to be loss of oxygen or gain of
hydrogen in a molecule.
3. Respiration is a redox process whereby living organisms oxidize
food to release energy.

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