UNIVERSITY OF NUEVA CACERES COLLEGE OF ENGINEERING AND ARCHITECTURE

Week 5 - 6 : Electrochemistry

I. Introduction
[1] Electrochemistry is the study of the interconversion of electrical and chemical energy.
This conversion takes place in an electrochemical cell that may be a voltaic (galvanic ) cell, in which
spontaneous reaction generates electrical energy or an electrolytic cell, in which electrical energy is used
to bring about a nonspontaneous reaction. Electrolysis involves chemical reactions that take place when
electrical energy is put into the system. In these cells, oxidation takes place in the anode and reduction at
the cathode. The anode reactions may involve oxidation of an anion to a free element, oxidation of an
anion or cation to an ion of higher oxidation state, oxidation of a metal to a cation, or oxidation of water
to give O2 gas and H+ ion. The cathode reactions may involve reduction of a cation to the free metal,
reduction of an ion to a lower oxidation state, reduction of a non metal to an anion, or reduction of water
to give H2 gas and OH- ion.

II. Objectives
At the end of the week, you should be able to:

1. Balance redox half reactions in acid or base medium, and balance over-all reactions.

III. Oxidation-Reduction Reactions

The chemical equations in which there are changes in oxidation number ( or oxidation
state) of the reactants are called oxidation-reduction or redox equations. Redox reactions may
be balanced using the oxidation number method or ion-electron method.
Oxidation number is the charge assigned to an atom in a compound or a complex ion. If
there is change in oxidation state, then electrons must be transferred. If electrons are lost by an
atom, the oxidation state increases since an electron has a negative charge; the atom then has
more protons than electrons, and thus a higher charge or oxidation number. If electrons are
gained, the oxidation state decreases.
Oxidation is any chemical change in which a substance loses electrons and thus increases
in oxidation state. For example, when a Zinc atom loses two electrons to become Zn +2 ion, the
zinc has increased in oxidation state ( from 0 to +2):
Zn → Zn+2 + 2e-
Reduction is a chemical change in which a substance gains electrons and thus decreases
in oxidation state. For example, when a sulfur atom gains two electrons to become a sulfide (S 2-)
ion, it decreases in oxidation state ( from 0 to -2 ):
S + 2e- → S2-
In a given reaction, whenever one substance is oxidized, it loses electrons to another
substance, which is reduced. Oxidation is always accompanied by reduction, and these equations
are called oxidation-reduction equations. In these equations, the substance that is oxidized is the
reducing agent, and the substance being reduced is called the oxidizing agent.

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In summary, oxidation can be defined either as increase in oxidation number or loss of

electrons, and that reduction is a decrease in oxidation number or gain of electrons. For example
in the combination of zinc and sulfur:
0 0 +2 -2
Zn + S → ZnS

The oxidation state of Zinc changes from 0 to +2, increase in oxidation number, losing 2 electrons
( 0 – 2 = -2 ). Zinc undergoes oxidation, and is therefore the reducing agent. Sulfur on the other
hand changes its oxidation state from 0 to -2, decrease in oxidation number, gaining 2 electrons
[ 0 – (-2) = +2]. Sulfur undergoes reduction, and is therefore the oxidizing agent.
[3] Rules on how to determine Oxidation Numbers:
1. The oxidation number of an element in the free or uncombined state is zero.
2. The algebraic sum of oxidation numbers of all atoms in the formula for a compound
is zero.
3. The oxidation number of an ion is the same as the charge of the ion.
4. The algebraic sum of oxidation numbers of all atoms in a complex (polyatomic) ion is
equal to the charge of the ion.
(Note: Diatomic molecules ( H2, O2, N2, Cl2, Br2, I2, F2) has zero as their oxidation state.
Hydrogen when combined with other elements has (+1) as the oxidation state, and
Oxygen with (-2). Total number of atoms of an element in a compound/complex ion is
equal to the product of the subscript of the element and its charge.)

Example 2.1
Determine the oxidation numbers of following elements in the given compounds/ions:
a. Mn in HMnO4
b. S in Na2SO4
c. Cr in CrO42-
d. Mn in MnBr2
e. Br in Ca(BrO3)2
f. P in P2O74-
Solution:

a. Mn in HMnO4

we let x = ON of Mn

+1 x -2
HMnO4 writing the ON on top of symbols,
H with +1, O with -2
(+1)(1) + x (1) + (-2)(4) = 0 taking the sum of atoms of each element
and equating to zero, HMnO4 a compound
1 + x - 8 = 0 simplifying the equation
x = 8 -1 solving for x, transposing -8 and 1 to the
right side of equation
x = +7 sign should be indicated

Answer: +7

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b. S in Na2SO4

we let x = ON of S
+1 x -2
Na2SO4 writing the ON on top of symbols,
Na with +1(using its charge)
O with -2
(+1)(2) + (x)(1) + (-2)(4) = 0 taking the sum of atoms of each element and
equating to zero, Na2SO4 a compound
2 + x - 8 = 0 simplifying the equation
x = 8 - 2 solving for x, transposing -8 and 2 to the
right side of equation
x = +6 + sign should be indicated

Answer: +6

c. Cr in CrO42-

we let x = ON of Cr
x -2
CrO4 2- writing the ON on top of symbols
O with -2
(x)(1) + (-2)(4) = -2 taking the sum of atoms of each element and
equating to -2, charge of ion CrO4-2
x - 8= -2 simplifying the equation
x = 8 - 2 solving for x, transposing -8 to the right side of
equation
x = +6 + sign should be indicated

Answer: +6

d. Mn in MnBr2

we let x = ON of Mn
x -1
MnBr2 writing the ON on top of symbols
Br with -1 (using its charge)
(x)(1) + (-1)(2) = 0 taking the sum of atoms of each element and
equating to 0, MnBr2 a compound
x - 2= 0 simplifying the equation
x = 2 solving for x, transposing -2 to the right side of
equation
x = +2 + sign should be indicated

Answer: +2

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e. Br in Ca(BrO3)2

we let x = ON of Br
+2 x -2
Ca(BrO3)2 writing the ON on top of symbols,
Na with +2(using its charge)
O with -2
(+2)(1) + (x)(2) + (-2)(6) = 0 taking the sum of atoms of each element and
equating to zero, Ca(BrO3)2 a compound
2 + 2x - 12 = 0 simplifying the equation
2x = 12 - 2 solving for x, transposing -8 and 2 to the
right side of equation
2x = 10
x = +5 + sign should be indicated

Answer: +5

f. P in P2O74-

we let x = ON of P
x -2
P2O7 4- writing the ON on top of symbols
O with -2
(x)(2) + (-2)(7) = -4 taking the sum of atoms of each element and
equating to -4, charge of ion P2 O74-
2x - 14 = - 4 simplifying the equation
2x = 14 - 4 solving for x, transposing -8 to the right side of
Equation
2x = 10
x = +5 + sign should be indicated

Answer: +5

IV. Learning Activity 2.1

1. Find the oxidation state of the underlined element in each of the following:
a. H2SO3
b. Mn2O7
c. H3PO4
d. K2Cr2O7
e. AsO43-
f. ClO4-

2. Name some general types of reactions that are typically redox reactions
a.________________
b.________________

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c.________________
d.________________

3. Identify the element oxidized, the element reduced, oxidizing agent and reducing agent in the
following redox equations:
a. MnO2 + HCl → MnCl2 + Cl2 + H2O
b. P + HNO3 + H2O → NO + H3PO4

V. Balancing Redox Equations by Ion-Electron Method

A second method used to balance redox equations is the ion-electron method or the
method of half-reactions. We shall first balance half-reactions and then apply these to the ion-
electron method of balancing equations. Half-reactions will be very useful in electrochemistry. In
this method of balancing redox equations, two partial equations are written, representing half-
reactions. One equation describes oxidation reaction(electron loss), and the other one,
reduction(electron gain). To balance each half-reaction, it is necessary to find the same number
of each atom on each side of the equation, using H2O and the H+ where needed, and OH- in basic
solution, and then balance the charge by putting electrons in where needed on either side of the
equation.

Example 2.2
Balance the following half-reactions:
a. Sn+2(aq) → Sn+4(aq)
b. Br2(g) → Br-(aq)

Solution:

a. Sn+2(aq) → Sn+4(aq) (ON Sn: +2 → +4 ); oxidation half-reaction

Mass and charge balance can be achieved by adding 2 electrons on the right side

Sn+2(aq) → Sn+4(aq) + 2e-

+2 = (+4) + (-2) balancing charges on both sides
total charge=(charge)(no.of atoms)
+2 = +2

Answer: Sn+2(aq) → Sn+4(aq) + 2e-

b. Br2(g) → Br-(aq) (ON Br: 0 → -1 ); reduction half-reaction

Mass balance is obtained by writing a coefficient of 2 for Br -

Charge is balanced by adding 2 electrons to the left side of equation
The balanced half-reaction is

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Br2(g) + 2e- → 2Br-(aq)

0 + (-2) = -2 balancing charges on both sides
total charge=(charge)(no.of atoms)
-2 = -2
Answer: Br2(g) + 2e- → 2Br-(aq)

There are some elements other than those being oxidized or reduced which also takes
part in the reaction. Most often, these elements are oxygen (ON = -2) and hydrogen (ON =
+1). Example for this will be the half-reaction for reduction of the permanganate ion (MnO 4-).

MnO4-(aq) → Mn+2(aq) (ON Mn: +7 → +2 )

Solution for ON of Mn in MnO4- : x -2

MnO4- x + (-2)(4) = -1
x - 8 = -1
x = 8 -1
x = +7
or the oxidation of chromium(III) hydroxide, Cr(OH) 3:

Cr(OH )3(s) → CrO4-2(aq) (ON Cr: +3 → +6 )

Solution for ON of Cr in Cr(OH)3 : x -2 +1

x - 6 + 3 =0
x = 6 -3
x = +3
Solution for ON of Cr in CrO4-3: x -2
CrO4-2 x + (-2)(4) = -2
x - 8 = -2
x = 8 -2
x = +6
[1] Rules in Balancing Half-reactions:

a. Assign oxidation numbers to each element.

b. Balance the atoms of each element being oxidized or reduced.
c. Multiply the oxidation number by the number of atoms that have that oxidation number. This
gives you the “total” oxidation number. The number of atoms is indicated either
by the coefficient that you used to balance the atoms or by the subscript of the atom.
d. Balance oxidation number by adding electrons. Electrons are added to the left for a reduction
half-reaction, and added to the right for an oxidation half-reaction.
e. Balance charge by adding H+ ions in acidic solution and OH- ions in basic solution.
f. Balance Hydrogen by adding H2O molecules.
g. Check to make sure that oxygen is balanced. If oxygen is balanced, the half-reaction is
almost certainly balanced correctly with respect to mass and charge.

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[1] Figure 2.1 Flowchart for balancing half-reactions in acid or base medium

BrO- → Br2
| assign oxidation numbers (ON)
Br = +1 → Br = 0
| atom balance
1 Br → 2 Br
X2 |
|
2BrO- → Br2
| total ON (atoms x ON)
2 (+1)= 2 → 2 (0) = 0
| ON decreases by 2
| reduction (2e- added on reactant side)
2e- + 2BrO- → Br2
|
________________________________________
↓ ↓
ACID BASE
2e- + 2BrO- → Br2 2e- + 2BrO- → Br2
| charge balance | charge balance
2(-1) + 2(-1) → 2(0) 2(-1) + 2(-1) → 2(0)
-4 | 0 -4 | 0
| Balance with H+ | Balance with OH-
↙↘ ↙↘
4H+ +2e- +2BrO- → Br2 2e- + 2BrO- → Br2 + 4OH-
4H atoms | 0 H atoms 0 H atoms | 4 H atoms
| Balance with H2O Balance with H2O |
4H+ +2e- +2BrO- → Br2 + 2H2O 2H2O + 2e- + 2BrO- → Br2 + 4OH-

Note: Charges are balanced by adding H+ for acid medium and adding OH- for base medium.
To balance H, add H2O molecules on the side where you have no H atoms(or opposite side on
where the H+ or OH- was added , and use the correct coefficient for H 2O.

Example 2.3
Balance the following half equations:
a. Fe3+ (aq) → Fe(s) in basic medium
b. CH3OH(aq) → CO2(g) in acidic medium

Solution:
a. Fe3+ (aq) → Fe(s) in basic medium

Fe3+ (aq) → Fe(s) ( ON Fe: +3 → 0 ) reduction; 3e- added to reactant side(L)

3+ -
Fe (aq) + 3e → Fe(s)
(+3)+ (-3) 0 Charge balance
0 0
Answer: Fe3+ (aq) + 3e- → Fe(s)

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b. CH3OH(aq) → CO2(g) in acidic medium

CH3OH(aq) → CO2(g) ON C: -2 → +4 ; oxidation (6e- lost added to right side)

ON C = -2 ON C = +4 assign Oxidation Numbers for C

x +1 -2 +1 x -2
ON for C in CH3OH ON for C in CO2
x + (+1)(3)+(-2)(1)+(+1)(1)= 0 x(1) + (-2)(2) = 0
x+3–2+1=0 x -4 =0
x+2 = 0 x = +4
x = -2

CH3OH(aq) → CO2(g) + 6e- ( in acidic medium)

0 0 + (-6)
0 → -6 charge balance

CH3OH(aq) → CO2(g) + 6e- + 6H+ balance with H+ (acidic medium)

4 H atoms 6 H atoms

CH3OH(aq) + H2O → CO2(g) + 6e- + 6H+ balance with H2O

Answer: CH3OH(aq) + H2O → CO2(g) + 6e- + 6H+

VI. Exercise 2.1

Balance the following half- equations:

1. O2(g) → O2-(aq) in basic medium

2. Cr2O7 2- (aq) → Cr3+ (aq) in acidic medium
3. Cl – (aq) → Cl2(g) in acidic medium
4. NO3- (aq) → NH4 + (aq) in acidic medium
5. V2+ (aq) → VO3- (aq) in basic medium

VII. Balancing Over-all Redox Reactions

[1] Rules in Balancing Over-all Redox Reactions
a. Split the reaction into two half-equations, one for reduction, the other one for oxidation.
b. Balance one of the half-equations with respect to both atoms and charge as described on the
rules in balancing half-equations ( steps a to e ).
c. Balance the other half-equation.
d. Combine the two half-equations in such a way as to eliminate electrons.
For example, the two half-equations are

G(s) → G2+(aq) + 2e- (1)

D3+ (aq) + 3e- → B(s) (2)

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Multiplying the the first half-equation (1) by 3, the second equation (2) by 2, and then adding
equations (1) and (2) gives the following net equation

3G(s) + 2D3+ (aq) → 3G2+ (aq) + 2D(s)

The six (6) electrons on both sides cancel.

Example 2.4
Write the balanced equation for the following reaction in acid solution:
Ni2+ (aq) + IO4- (aq) → Ni3+ (aq) + I- (aq)

Solution:

Split into two half-reactions:

(1) Ni2+(aq) → Ni3+ (aq) oxidation
(+2) – (+3) = -1 (1e- lost)
(2) IO4- (aq) → I- (aq) reduction
(+7) – (-1) = +8 (8e- gained)
Balancing the half-equations:

(1a) Ni2+(aq) → Ni3+ (aq) + e- 1e lost placed on the right side

Balanced charges
Left side: +2
Right Side: (+3) + (-1) = +2
(2) IO4- (aq) → I- (aq)
IO4- (aq)
+ 8e- → I- (aq) 8e gained added on the left side
H + IO4- (aq) + 8e- → I- (aq) + H2O
+
H2O added on the right side to
balance O atoms; H+ added on
left side to balance H atoms

(2a) 8H+ + IO4- (aq) + 8e- → I- (aq) + 4H2O Balancing H and O atoms
Balanced charges
Left side: (+8)+(-1)+(-8) = -1
Right Side: (-1) + 0 = -1

Adding the balanced half-equations (1a) and (2a):

(1a)x 8: 8 Ni2+(aq) → 8 Ni3+ (aq) + 8 e- eqn1a multiplied by 8 to

balance e-with eqn2a
(2a): 8H+ + IO4- (aq) + 8e- → I- (aq) + 4H2O 8e- cancels out

8 Ni2+(aq)+ 8H+ + IO4-(aq) → 8 Ni3+(aq) + I-(aq) + 4H2O Balanced charges

Left Side: (+16)+(+8)+(-1)=+23
Right Side: (+24)+(-1) = +23

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Answer:

8 Ni2+(aq)+ 8H+ + IO4-(aq) → 8 Ni3+(aq) + I-(aq) + 4H2O

Example 2.4
Write the balanced equation for the following reaction in basic solution:
Ca(s) + VO4-3(aq) → Ca+2(aq) + V+2(aq)

Solution:

Split into two half-reactions:

(1) Ca(s) → Ca+2(aq) oxidation
0 – (+2) = -2 ( 2e- lost)
(2) VO4-3(aq) → V+2(aq) reduction
(+5) – (+2) = +3 (3e-gained)

Balancing the half-equations:

(1a) Ca(s) → Ca+2(aq) + 2e- 2e- lost placed on right side
Balanced charges
Left side: 0
Right Side: (+2) + (-2) = 0
(2 ) VO4-3(aq) → V+2(aq)
VO4-3(aq) + 3e- → V+2(aq) 3e- gained added on the left side
VO4-3(aq) + 3e- + 4H2O → V+2(aq) + 8OH- OH- added on the right side to
balance O atoms;H2O on the
left to balance H atoms
Balanced charges
Left side: (-3) +(-3) = -6
Right Side: (+2)+ (-8) = -6
(2a) VO4-3(aq) + 3e- + 4H2O → V+2(aq) + 8OH-

Before adding the two balanced half-equations, (1a) should be multiplied by 3, and (2a) should be
multiplied by 2 to balance the number of electrons for the two half-equations.

Adding the two half-equations:

(1a) x 3 : 3Ca(s) → 3Ca+2(aq) + 6e-

(2a) x 2 : 2 VO4 (aq) + 6e- + 8H2O → 2 V+2(aq) + 16OH-
-3
6e- cancels out

3Ca(s) +2VO4-3(aq)+ 8H2O →3Ca+2(aq)+ 2V+2(aq)+16OH- Balanced charges

Left Side: 0+(-6)+0 = -6
Right Side: (+6)+(+4)+(-16)=-6
Answer:

3Ca(s) +2VO4-3(aq)+ 8H2O → 3Ca+2(aq)+ 2V+2(aq)+16 OH-

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VIII. Exercise 2.2

Write balanced equations for the following Redox reactions:

1. P4(s) + Cl- (aq) → PH3(g) + Cl2(g) in acid solution

2. MnO4- (aq) + NO2- (aq) → Mn2+ (aq) + NO3- (aq) in acid solution

3. C2H4 (g) + BiO3- (aq) → CO2(g) + Bi3+ (aq) in basic solution

4. PbO2(s) + H2O → O2(g) + Pb2+ in basic solution

5. CrO42-(aq) + SO32-(aq) → Cr3+ (aq) SO42- (aq) in acid solution

IX. Quiz
Submit test booklets to the testing center before taking the examination. Schedule will be announced to
the class group. Coverage for Quiz 5 will be balancing Redox reactions in acid and basic solution.

X. Laboratory
Laboratory activity for the week will be posted by your instructor. Video demo and instructions will be
given. Submission of written reports will be announced to the class group.

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XI. Exercises

Exercise 1.1
Instructions: Instruct InstructInstructInstructInstructInstruct
1. Problem Statement with answers at the Appendix
2. Problem Statement with answers at the Appendix
3. Problem State of the ment with answers at the Appendix
4. Problem Statement with answers at the Appendix
5. Problem Statement with answers at the Appendix
6. Problem Statement with answers at the Appendix
7. Problem Statement with answers at the Appendix
8. Problem Statement with answers at the Appendix
9. Problem Statement with answers at the Appendix
10. Problem Statement with answers at the Appendix

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