ELECTROCHEMISTRY

By

Dr. rer. nat. H. Muharram, M.Si

 ELECTROCHEMISTRY
English chemists John Daniell (left) and
Michael Faraday (right), both credited as
founders of electrochemistry today
Electrochemistry is a branch of
chemistry that studies chemical
reactions which take place in a
solution at the interface of an
electron conductor (a metal or
a semiconductor) and an ionic
conductor (the electrolyte), and
which involve electron transfer
between the electrode and the
electrolyte or species in
solution
ELECTROCHEMISTRY
1. Concept of Redox reaction
2. Balancing Redox Reaction

Illustration of a redox reaction

 CONCEPT OF REDOX REACTION

Redox (shorthand for reduction-oxidation) reactions describe

all chemical reactions in which atoms have their oxidation number
(oxidation state) changed. This can be either a simple redox process,
such as the oxidation of carbon to yield carbon dioxide (CO 2) or the
reduction of carbon by hydrogen to yield methane (CH4), or a
complex process such as the oxidation of sugar (C6H12O6) in the
human body through a series of complex electron transfer processes.
The term comes from the two concepts of reduction and oxidation. It
can be explained in simple terms:
 Oxidation is the loss of electrons or an increase in oxidation state
by a molecule, atom, or ion.
 Reduction is the gain of electrons or a decrease in oxidation state
by a molecule, atom, or ion.
CONCEPT OF REDOX REACTION
 Oxidizers
Substances that have the ability to oxidize
other substances are said to be oxidative or
oxidizing and are known as oxidizing agents,
oxidants, or oxidizers
Oxidants are usually chemical elements or
substances with elements in high oxidation
numbers (e.g., H2O2, MnO4-, CrO3, Cr2O72-, OsO4)
or highly electronegative substances/elements that
can gain one or two extra electrons by oxidizing an
element or substance (O, F, Cl, Br).
CONCEPT OF REDOX REACTION
 Reducers
Substances that have the ability to
reduce other substances are said to be
reductive or reducing and are known as
reducing agents, reductants, or reducers.
Reductants in chemistry are very
diverse. Electropositive elemental metals,
such as lithium, sodium, magnesium, iron,
zinc, aluminium, carbon, are good reducing
agents
CONCEPT OF REDOX REACTION
 Examples of redox reactions
A good example is the reaction between hydrogen and
fluorine in which hydrogen is being oxidized and
fluorine is being reduced:
H2 + F2 → 2 HF
We can write this overall reaction as two half-
reactions:
the oxidation reaction:
H2 → 2 H+ + 2 e−
and the reduction reaction:
F2 + 2 e− → 2 F−
 BALANCING REDOX REACTION

Redox reaction can be balanced by ion-electron method

and oxidation number method.
Ion-Electron Method in Acid Solution
For this method, we consider the reaction of HCl with
KMnO4. In this reaction Cl- is oxidized to Cl2 and
MnO4- is reduced to Mn2+
Step 1. Divide the equation into half reactions.
Cl-  Cl2
MnO4-  Mn2+
 BALANCING REDOX REACTION
Step 2. Balance atoms other than H and O. In the first half-
reaction of 2 in front of Cl-. We don’t have to do
anything to the second half-reaction.
2Cl-  Cl2
MnO4-  Mn2+
Step 3. Balance oxygens by adding H2O that side that needs O.
In the second half-reaction, there are 4 oxygens on the
left and none on the right. We therefore have to add 4
H2O to the right side. Then the oxygens will balance.
2Cl-  Cl2
MnO4-  Mn2+ + H2O
 BALANCING REDOX REACTION
Step 4. Balance hydrogens by adding H+ to the side that needs H.
The right side of the second half-reaction has a total of 8
hydrogens; there is none on the left. Therefore, we add
8H+ to the left side.
2Cl-  Cl2
H+ + MnO4-  Mn2+ + H2O
Step 5. Balance the charge by adding electrons. In this step we
make the net charge the same on the both side. In the first half-
reaction we have to add 2 electrons to the right side. In the
second half-reaction we must add 5 electrons to the left side.
2Cl-  Cl2 + 2e-
5e-+ H+ + MnO4-  Mn2+ + H2O
 BALANCING REDOX REACTION
Step 6. Make the number of electrons gained equal the number lost. This can
be accomplished by multiplying the first half-reaction through by 5 and
the second through by 2. There will then be 10e- lost and gained.
5(2Cl-  Cl2 + 2e-)
2(5e-+ H+ + MnO4-  Mn2+ + H2O)
Step 7. Add the two half-reactions. When we do this, we will not bother
to bring down the electrons, because we know they will cancel. They
have to-we went to the trouble to make them the same in each half-
reaction.
5(2Cl-  Cl2 + 2e-)
2(5e-+ H+ + MnO4-  Mn2+ + H2O)

10Cl- + 16H+ + 2MnO4-  5Cl2 + 2Mn2+ + 8H2O

 BALANCING REDOX
REACTION
Ion-Electron Method in Base Solution
In a basic solution the dominant species are H2O and OH-, so
these are the species that should be used to achieve material
balance. Consider for the oxidation of plumbite ion, Pb(OH)3-,
to lead dioxide by hypochlorite ion in basic solution.
Pb(OH)3- + OCl-  PbO2 + Cl-

Step 1. The equation is balanced as though it occurred in

acidic solution. We begin by dividing it into half-
reaction.
Pb(OH)3-  PbO2
OCl-  Cl-
 BALANCING REDOX
REACTION
Step 2. We balance them according to atoms.
Pb(OH)3-  PbO2 + H2O + H+
H+ + OCl-  Cl- + H2O
Step 3. Balance the charge by adding electrons.
Pb(OH)3-  PbO2 + H2O + H+ + 2 e-
2 e- + 2H+ + OCl-  Cl- + H2O
Step 4. Since number of electron lost in the first half-
reaction is already equal to the number gained in
the second, we can add them.
H+ + OCl- + Pb(OH)3-  PbO2 + 2H2O + Cl-
 BALANCING REDOX REACTION
Step 5. We perform three step conversion to basic
solution. First we add to each side the same
number of OH- as there are H+ in the equation. H+
+ OH- forms H2O.
H+ + OH- + OCl- + Pb(OH)3-  PbO2 + 2H2O + Cl-+ OH-
H2O + OCl- + Pb(OH)3-  PbO2 + 2H2O + Cl-+ OH-
Step 6. We cancel one H2O from each side to get the final
balanced equation.
OCl- + Pb(OH)3-  PbO2 + H2O + Cl-+ OH-
 BALANCING REDOX REACTION
Oxidation State Method
To see how these methods apply, let’s balance the
equation for the reaction KMnO4 with NaSO3 and sulphuric
acid as catalyst. The reaction was produced K2SO4, MnSO4,
Na2SO4 and H2O.
Step 1. Write down the equation of reaction.
KMnO4 + Na2SO3 + H2SO4  K2SO4+ MnSO4 + Na2SO4 + H2O

Step 2. Give the oxidation number each element.

+1+7(-2)4 (+1)2+4(-2)3 (+1)2+6(-2)6 (+1)2+6(-2)4 +2+6(-2)4 (+1)2+6(-2)4 (+1)2-2
KMnO4 + Na2SO3 + H2SO4  K2SO4 + MnSO4 + Na2SO4 + H2O
 BALANCING REDOX
REACTION
Step 3. Choose the elements that change the oxidation number. Write the oxidation
reaction and reduction reaction.
Oxidation : S4+  S6+ + 2e-
Reduction : Mn7+ + 5e-  Mn2+

Step 4. Make the number of electrons gained equal the number lost. This can be
accomplished by multiplying the first half-reaction through by 5 and the second
through by 2. There will then be 10e- lost and gained.
Oxidation : (S4+  S6+ + 2e-)5
Reduction : (Mn7+ + 5e-  Mn2+)2

Step 5. Add the two half-reactions. When we do this, we will not bother to bring down
the electrons, because we know they will cancel. They have to-we went to the
trouble to make them the same in each half-reaction.

S4+  S6+ + 2e-

Mn7+ + 5e-  Mn2+

5 S4+ + 2Mn7+  5S6+ + 2 Mn2+

 BALANCING REDOX
REACTION
Step 6. We write the equation with the coefficient.
2KMnO4 + 5Na2SO3 + ? H2SO4  K2SO4 + 2MnSO4 + 5Na2SO4 + ? H2O

Step 7. We determine the coefficient of H2SO4 by the number of

mole S on the both side. On the right side, there are 8
mole S, and the left side there 6 mole S. Therefore, we
add 2 mole S to the left side by multiplying H2SO4 by 3.

2KMnO4 + 5Na2SO3 + 3 H2SO4  K2SO4 + 2MnSO4 + 5Na2SO4 + ? H2O

Step 8. We determine the coefficient of H2O by the number of

mol H or O on the both side. On the left side, there are
6 mole H and 35 mole O, and the right side there are 2
mole H and 32 mole O. Therefore, we add 4 mole S and
3 mole O to the right side by multiplying H2O by 3.
2KMnO4 + 5Na2SO3 + 3 H2SO4  K2SO4 + 2MnSO4 + 5Na2SO4 + 3H2O