ATOMS, MOLECULES AND

INTERMOLECULAR FORCES

CHE I56
 THE ATOMIC NATURE OF MATTER
• At about 400 B.C., Demotricus, a Greek
philosopher proposed the atomic nature of
matter-HYPOTHESIS

• If one piece of matter is divided into smaller and

smaller pieces, one would reach an invisibly
smallest particle with all the properties of the
parent matter
• This smallest particle cannot be further sub-
divided, it is therefore named atomos which
means ‘indivisble’ in Greek
 DALTON’S ATOMIC THEORY
• All matter is made up of tiny, indivisible particles
called atoms
• Atoms can neither be created nor destroyed (law
of conservation of mass)
• Atoms of the same elements are identical and
have the same mass and chemical properties (law
of constant composition)
• Atoms of elements combine to form compounds
in a small whole number ratio (law of multiple
proportion)
 DALTON’S ATOMIC MODERN ATOMIC
THEORY (1806-1896) THEORY

All matter are made An atom can be

up of tiny indivisible further sub-divided
particles called into sub-atomic
atoms particles e.g.
electrons, protons,
neutrons, positrons,
mesons, etc.
 DALTON’S ATOMIC MODERN ATOMIC
THEORY (1806-1896) THEORY

Atoms can neither be Radioactivity-

created nor destroyed spontaneous emission
from the nuclei of
some elements
resulting in new atoms
 DALTON’S ATOMIC MODERN ATOMIC
THEORY (1806-1896) THEORY
Atoms of the same Isotopes exist. These
element are identical are atoms of the same
and have the same element having the
mass & chemical same atomic numbers
properties and are but different mass
different from atoms numbers (16O, 17O and
of another element 18O)
 DALTON’S ATOMIC MODERN ATOMIC
THEORY (1806-1896) THEORY
Atoms combine Giant molecules
together in simple which contain
(& small) whole thousands of atoms
do exist. This is
number ratio (CO2,
referred to as
H2O, NH3,etc). CATENATION
(e.g. sucrose-
C12O22H11)
 EXPERIMENTAL EVIDENCE OF ATOMIC
STRUCTURE: SUB-ATOMIC PARTICLES
THE ELECTRONS
• William Crooke (1870’s) passed high-voltage electrical
discharge through various gases at low pressure inside
a sealed tube.

• He discovered a beam of rays came out from the

negative electrode (cathode) and hit the positive
electrode (anode)

• The beam was called cathode rays

The cathode ray tube
A schematic diagram of the gas discharge
tube
CharaterisTICS OF THE CATHODE
RAYS

• Cathode rays travel in straight line (they

produced shadows of objects placed in the
way)
• Cathode rays possess momentum and energy
(can rotate a light paddle placed in its path)
• Cathode rays are deflected by both
magnetic and electric fields
• (They are deflected towards the
positive terminal in an electric field)
 Other xTICS OF THE CATHODE RAYS
• They are independent of the material of the
electrode or nature of gas in the tube

• They penetrate small thickness of matter (e.g.

aluminium or gold foil)
Sir J. J. Thomson’s experiments (1897)

Bev
 a negatively charged electron is deflected in an
electric field and repelled from the negative plate and
attracted towards the positive plate

Sir JJ Thomson’s experiments (1897)

in a magnetic field, electrons are deflected in a
circular arc opposite in direction to that in an
electric field
Sir JJ Thomson’s experiments (1897)
when both fields are present, the forces cancel
out
Sir JJ Thomson’s experiments (1897)
modified cathode ray tube by JJ Thomson
• J.J Thomson had balanced the cathode rays
between electric and magnetic forces
• The force (F) on a charged object in an
electric field depends on the strength of the
electric field (E), multiplied by the charge (e)
on the object:
• The force (F) on a charged object in a
magnetic field depends on the strength of
the magnetic field (B), multiplied by the
charge (e) and velocity (v) on the object:
• Since the forces were balanced;

• The velocity was equal to the electric field strength

divided by the magnetic field strength.

• Since the two field strengths could be measured,

then velocity, v, of the cathode ray could then be
determined and be used in further calculations
• In a magnetic field, an electron moves
along the arc of circle of radius, r
• If the centrifugal force (F) on the electron
which has a mass, m, in a magnetic field
is given by

• Recall that in a magnetic field,

• If we equate the two forces, we have

• The charge to mass ratio (e:m) will be

given by:
•

Millikan’s oil can including an atomizer to create a mist
of oildroplets and a telescope to observe them
A cross-sectional view of Millikan’s oil drop apparatus
 Millikan’s oil droplet experiMents
• The oil drop apparatus had two chambers.
• The upper chamber had an atomizer that
dispersed a fine mist of micron-sized oil droplets.
• Individual droplets would fall through a pinhole
into the lower chamber, which consisted of two
horizontal plates, held 16 mm above each other.
• A small window on the side allowed the scientists
to observe the droplets through a telescope.
 Millikan’s oil droplet experiMents
• The air in this chamber was ionized so that ions or
free electrons could be captured on the falling
droplets

• High voltage was applied across the plates, till

electric field force balance the force of gravity making
the drop to hang suspended in the mid-air

• Using horizontal lines in the telescope, the speed,

size and mass of each droplet could be estimated
• When a drop is suspended, its weight (mg) is equal
to the electric field force mg=Eq
where; m = mass of an oil droplet,
g = acceleration due to gravity,
E = electric field strength,
q= total charge on the oil droplet (q= ne)
n= number of electrons
e= actual charge on the electron
• Thus the total charge q could be estimated:
• From the values of q obtained, the value of the
actual charge, e, was estimated to be : 1.602 x 10-19
Coulombs
• Recall,
• if e=1.602 x 10-19 C,
• Then,

• This is ≈ 2000 times lighter in weight than H,

the first known lightest element
• This explains the reason behind Crooke’s
observation about the penetrating abilities of
the electron
• PRACTICE QUESTION (pg 37)
• An experiment to determine the charge-to-
mass ratio of the electron was performed twice
with the same CRT. In the second experiment,
the magnetic field strength was double that
used for the first experiment. By what factor
must the electric field strength be changed ?
• Solution
Recall that the charge-to-mass ratio is given by:
In 1st expt, Let magnetic field strength =B and
electric field strength=E;
e =E 2 ........................(i)
m
nd
rB
In 2 expt, Let magnetic field strength =2B; and electric field
strength= x )

e = x 2 =x 2 ...........(ii )
m r (2 B ) r 4B
Equating (i) and (ii):
E 2 =x 2
rB r 4B
E=x
4 x = 4 E
(If B is doubled, E must be quadrupled
i.e. multiplied by a factor of 4)
 DISCOVERY OF THE PROTON
❖ Goldstein was used a modified cathode ray tube (CRT), in which
the cathode was perforated
❖ He observed a new type of rays that were attracted towards a
negatively charged plate, hence they have +ve charge
❖ He called these rays canal rays / anode rays (and later protons)
❖ The e/m ratio were much lower than those of electrons
❖ The e/m ratio also changes when the gas in the CRT was changed
❖ The magnitude of the charge (e) for the canal rays were found to
be equal to that of electrons but opposite in charge
❖ The mass of the proton was determined to be
1.672×10-27 kg
A modified cathode ray tube
 ATOMIC MODELS
• JJ Thomson had proposed a plum pudding model
for the atom
• negatively charged electrons floating in a sea of
positive charge
 rutherford’s experiMents
• To test this model, Ernest Rutherford performed
the gold foil scattering experiments
• A thin sheet of gold foil was bombarded with a
beam of α-particles (fast, positive charges)
• Three different observations
❑ Most of the rays passed through without deflection
❑ Very few were deflected through large angles
❑ Some rebounded
Rutherford gold-foil experiment
result of Rutherford’s experiment
Conclusions from Rutherford’s expt
• The fact that some of the alpha particles were
deflected or reflected meant that the atom had a
centre concentrated with positive charges

• These alpha particles had either hit the positive

centre directly or passed by it close enough to be
affected by its positive charge.

• Since many other particles passed through the

gold foil, the positive centre would have to be a
relatively small size compared to the rest of the
atom - meaning that the atom is mostly open
space.
 Conclusion from Rutherford’s expts
• Plum pudding model was incorrect
• The (gold) atom had a concentrated centre of positive charge
and relatively large mass
• The positive centre has to be relatively small size compared to
the rest of the atom
• The atom is mostly open space
• The concentrated centre is called the nucleus (containing the
positive charge and most of the mass of the atom)
• He proposed the name protons for the positive charge
 DISCOVERY OF THE NEUTRON
• For an atom to be electrically neutral, the number of
positive charges must equal the number of negative
charges no. of protons = no. of electrons

• But the mass of the atom is generally found to be twice

that of protons (1proton ≡ 1 amu)

• Rutherford was the first to propose an electrically

neutral entity to make up for the residual mass in the
nucleus
 SIGNIFICANCE OF THE NEUTRON
• They strongly bind protons (protons are unable
to bind with each other due to electromagnetic
repulsion

• Neutrons keep the atomic nucleus from flying

apart due to its heaviness
 The sub-atomic Particles
Sub- Location Charge Relative Mass (kg) Relative
atomic charge atomic
particle mass

Proton nucleus +1.6 × 10-19 +1 1.672 1

(p+) ×10-27 (1.0073)

Neutron nucleus 0 0 1.674 1

(n) ×10-27 (1.0087)

Electron Surround -1.6 × 10-19 -1 9.11× 10-31 0

(e-) -ing the (0.00055)
nucleus
 Number of protons in the nucleus
• The number of protons present in the nucleus of an atom was
determined by Henry Moseley using X-rays
• X-radiation (ray) was discovered by Konrad Rőntgen in 1896
• When fast-moving electrons (cathode ray) impinge on an object (anode),
they loose their kinetic energy. X-rays are the result of excess energy
which fast-moving electrons lose when they impinge on objects.

• He observed a penetrating radiation emitted from the anode

of a CRT
❖ It turned wrapped photographic film black
❖ It allows gas to conduct electricity by ionizing them
❖ It makes some substances fluoresce e.g. ZnS
❖ It is not deflected by magnetic or electric field
 Henry Moseley’s experiments
• He used different metals as anode (target for the
cathode rays) and analyzed the diffracted radiation
of the x-rays produced
• From his calculations, he observed an integer Z
(from the German word zahl -meaning number) for
each metal he used was ≈ half the relative atomic
mass of the metal
• He also found out that this no. was equal to the
+ve charges (protons) calculated for each metal
• The atomic number (Z) increases by one from one
element to the other as one progress in the
periodic table
 Atomic and Mass number
• The atomic number (Z) is equal to the number
of protons in the nucleus of an atom
• Because atoms are electrically neutral, the
atomic number must equal the number of
electrons surrounding the atom
Atomic number (Z ) = no. of protons = no. of electrons
• The relative atomic mass/weight of an atom
(also known as the mass number, A, is equal to
number of nucleons (protons and neutrons)
Mass number ( A) = no. of protons + no. of neutrons
 Atomic notations
The atom an element is usually denoted as:

The atomic number (Z) increases progressively from

one element to the other along the periodic table
 Relative atomic masses
• It is more convenient to quote the mass of atom on
a relative scale than the tiny masses of atoms in
grams or kilograms
• On the relative atomic mass scale, carbon-12 (12C)
has a mass of exactly 12
• That some elements like, chlorine and copper, have
non-whole number (fraction) relative atomic masses
is due to ISOTOPY
• The relative abundance of each isotope of an
element contributes to its atomic mass
Isotopes and relative atomic masses
• Isotopes are atoms of the same element having
different atomic masses

• For example, there are three isotopes of

hydrogen atom namely hydrogen, deuterium
and tritium

• All have the same atomic number but their mass

numbers differ
Isotopes and relative atomic masses
• Isotopes are atoms of the same element having
different atomic masses

• For example, there are three isotopes of

hydrogen atom namely hydrogen, deuterium
and tritium

• All have the same atomic number but their mass

numbers differ
 The isotopes of hydrogen
Isotopes of H No. of No. of No. of
electrons protons neutrons
1
1 H hydrogen 1 1 0
2
1 H deuterium 1 1 1
3
1 H tritium 1 1 2
three different isotopes of hydrogen
 Characteristics of isotopes
• Isotopes of the same element have the
same number of protons (and therefore
same number of electrons)

• Isotopes of the same element have

different number of neutrons

• Isotopes of the same element have similar

chemical properties because this is
determined by the electronic structure of
the atom
 The mass spectrometer
• The mass spec (or MS) is used to
determine relative atomic/molecular
masses of atomic/molecular species

• It can differentiate between isotopes of

the same element and give their relative
abundances

• It measures mass/charge (m/e or m/z)

ratio of ionized particles
Mass Spectrometry
 The operation of a MS
There are six important parts in a MS
1. The vaporization chamber
➢ The material to be analyzed (element or
compound) is injected into the chamber and
heated until it vaporizes and changes into the
gaseous form
2. Ionization chamber
➢ The vaporized sample is bombarded with
electrons from a heated filament. Electrons are
knocked off from neutral atoms or molecules.
Positive ions are formed
3. Accelerating electric field
➢ The positive ions formed are accelerated (moves
with a very high speed) by an electric field
towards the magnetic field

4. Deflecting magnetic field

➢ The +ve ions are deflected along a circular path.
➢ The lighter the +ve ion, the greater is the
deflection and the smaller the radius of the
circular path ⇨ mass (m)
➢ The higher the charge of the +ve ions, the
greater the deflection ⇨ charge (e)
➢ Ions with low m/e ratio are deflected more than
those with high m/e
5. Ion detector
➢ The detector converts the m/e ratio into
electric current
➢ The magnitude of the current is proportional
to the number of ions present
6. Recorder
➢ The ions detected are traced out by a recorder
which shows the m/e ratio and corresponding
intensity of the ions.
➢ The position of the peak gives the m/e ratio of
an ion
➢ The height of the peak gives the relative
abundance of the ion (usually in %)
➢ The chart is called a mass spectrum
Typical mass spectra
A typical mass spectrum of chlorine
Interpretation of the MS of Cl
m/e ratio Ions
35 35Cl+

37 37Cl+

70 35Cl- 35Cl+

72 35Cl-37Cl+

74 37Cl-37Cl+
A typical mass spectrum of chlorine
for example,
• Chlorine has two isotopes: 35Cl & 37Cl
• If in a sample of chlorine, 75% is 35Cl, while the
remaining 25% is 37Cl
• The relative atomic mass will be
(75 × 35) + (25 × 37) = 3550
100
3550 = 35.5
100
• The relative atomic mass of chlorine is 35.5
Calculating relative atomic masses
PRACTICE QUESTIONS
1. `A sample of neon is found to consist of
20Ne, 21Ne, 22Ne in the following percentages

20Ne 90.92%
21Ne 0.26%
22Ne 8.82%
Calculate the relative atomic mass of neon.
Solution
The rel. mass of neon=
(20  90.92) + (21 0.26) + (22  8.82) 2017.9
= = 20.18
90.92 + 0.26 + 8.82 100
Question 2
The relative atomic mass of potassium is
39.1. Calculate the relative abundances of
its two isotopes, 39K and 41K in a sample of
potassium
 Σ ( mass of each isotope × its rel. abundance )
R.a.m =
Σ ( relative abundances of all isotopes )
Let the rel. abundance of 39K be x and 41K be y
.
39 x + 41y .
x=
1.9 y
= 19 y
39.1 =
x+ y 0.1
39.1( x + y ) = 39 x + 41y but x + y = 100
39.1x + 39.1y = 39 x + 41y 19 y + y = 100
20 y = 100
39.1x − 39 x = 41y − 39.1y y =5
0.1x = 1.9 y If y = 5, then x = 95
 Mass defect

• It has been observed that the mass of a nucleus of

an atom is always less than the sum of the masses
of the protons and neutrons it contains

• The difference between the actual mass and the

observed mass is referred to as mass defect (∆m)

• This is due to the effect of the binding energy that

the nucleons exert towards one another
 Mass defect and Nuclear Binding
energy

∆m = {(mass of p ×no. of p)+(mass of n ×no. of n)} – {actual

mass of the nucleus}
 Example
• Find the mass defect of a nucleus if the
actual mass of 63Cu is 62.91367 amu.
Solution:
• The atomic number of Cu is 29,
• therefore the number of protons (p) is 29
• number of neutrons (n) in 63Cu is 63 – 29 = 34
(Recall that the mass of proton is 1.00728 amu
and mass of neutron is 1.00867 amu)
m = (1.00728  29 ) + (1.00867  34 )  amu − 62.91367  amu
= 0.59223amu
 NUCLEAR BINDING ENERGY (EB)
• This is the energy required to breakdown a
nucleus into its components (nucleons)
• It is expressed in Joules per nucleus
• It is given by the formula: EB= ∆mc2
• where ∆m is the mass defect in kg
(1 amu = 1.6606×10-27 kg)
c is the velocity of light =3.0×108 m/s
• For 63Cu with ∆m=0.59223, EB is equal to:

( 0.592231.6606 10 −27

) kg ( 3.0 10 )
8 2
m2 s −2
−11 2 −2
= 8.839 10 J (kgm s  J )
 Exercise
• Calculate the mass defect and the nuclear
binding energies of the following nuclides:
NUCLIDE ATOMIC NO ACTUAL
ATOMIC
MASS
(amu)
U-238 92 238.050784
Ni-58 28 57.935346
O-16 8 15.994915
 The electronic structure of the atom
• The electronic structure is a description of the
arrangement and distribution of the electrons around
the nucleus of an atom
• Different models were postulated to account for the
actual position of the electrons around the nucleus
of an atom
❖ Stationary model: electrons cannot be stationary ⇨ they would
be pulled into the positively charged nucleus

❖Continuous motion model: If they were to continue moving in a

circular orbit, they would radiate energy and slow down
continuously until they spiral into the nucleus
 Electrons & light: Spectral analysis
• When an electrical discharge is passed
through a gas at low pressure in a CRT, an
electromagnetic radiation is produced
• An electromagnetic radiation is Energy that
travels as a wave through space
• It is observed as a spectrum consisting of
narrow lines of bright colours. This is
referred to as a ‘Line spectrum’ (Can be seen
when passed through a prism)
• Each line corresponds to light of a specific
wavelength
➢ Each element (gas) gives its own (characteristic) line
spectrum i.e. every element has a unique pattern
(colours)
➢ WHEN AN ELECTRON ABSORBS ENERGY, IT
GIVES OFF LIGHT
 Electromagnetic radiations
• They consist of waves which have
electrical and magnetic properties
• A wave conveys energy from a vibrating
object (source) to a distant place
• Waves are characterized by wavelength
( λ) and frequency (ν)
• λ is measured in (Å)angstrom or
nanometers
1 Å = 0.1nm (1nm = 1x10-9m)
• ν is measured in Hertz (Hz)
 Why did electrons emit energy as light
of only certain wavelength?
• Atoms of a particular element could only
radiate energy within certain definite values
because
1. Electron moves in a certain allowed orbit around the
central nucleus
2. A definite amount of energy (quantum) is associated
with the electron in each allowed orbit (i.e. the
electronic energy is quantized)
3. The electron does not radiate (lose) energy when it
is in these orbits
4. These orbits are arranged around the nucleus in
increasing order of energy
5. The electron only radiates energy when it undergoes
transition from one orbit to another of a lower
energy
 Bohr’s theory & Planck’s hypothesis
• Max Planck was the one who suggested the theory of
quantization of energy ⇨ Quantum Chemistry
• This theory suggests that electromagnetic
radiation consists of minute packets of energy
called photons (or quanta)
• Niel Bohr’s theory states that in the atom, electrons exist
in quantum energy levels (n levels)
• Electrons have the lowest energy when closest to the
nucleus
• Under resting conditions, the electrons are in the lowest
possible energy level called ground state
• The allowed energy states associated with
individual electrons in an atom can be described
by a set of quantum numbers
 Bohr’s Model

Nucleus

Electron

Orbit

Energy Levels
• When an electron moves from one energy level
to the other, it absorbs or emits energy
• The difference in energy between the two
energy level is given by:
ΔE = hν
(where ΔE = Efinal state- Einitial state )
h is the Planck’s constant 6.626 x10 -34 Js
ν is the frequency of the emitted radiation

• The lowest electronic energy state is called the

ground state
• Any state with greater energy than the ground
state is called the excited state
 Energy Levels in an atom
• The allowed energy levels within which an electron has
definite energy values are designated by four quantum
numbers
1. Principal quantum number (n) and also by letters K to
P
quantum no (n) = 1 2 3 4 5 6
shell =K L M N O P
• The maximum number of electrons in a particular shell,
is equal to 2n2
• For example, within the L-shell (n=2), the maximum no
of e- = 2 (2)2 =8 electrons
2. Angular momentum/azimuthal quantum number (l )
divides the shells into subshell which are further
divided into orbitals
• It describes the shape of the orbitals in which
electrons are found
• The minimum value of l is 0, while the maximum
value is n-1(l = 0,1,2,…., n-1)
• Each value of l corresponds to a particular subshell
s, p, d, f,___, respectively.
• The maximum number of electron that is allowed
in a subshell is given by 2(2l + 1)
• The s subshell (with l =0 )can therefore contain
2(2×0+1) electrons = 2 electrons
• The f shell (with l =3 ) will have a maximum of
2(2×3+1) electrons=14 electrons
3. Magnetic quantum number (ml or m)
• This quantum number arises to differentiate the
orbitals that are available in a subshell
• When these orbitals are exposed to strong magnetic
field, orbitals which are degenerate i.e. have the same
energy level become non-degenerate i.e have different
energies
• ml ranges from –l , ___, 0, ___, +l
• The ml of the s subshell (l =0) is 0 (it has only one
orbital)
• For p subshell (l =1), ml is -1, 0, or +1 (has three
orbitals)
• For d subshell (l =2) has five orbitals,
ml = -2, -1, 0, +1 or +2
4. Spin quantum number (ms or s )
• Describes the orbital angular momentum of an
electron.
• An electron spins around an axis and has both
angular momentum and orbital angular
momentum
• Because angular momentum is a vector, the Spin
quantum number (s) has both a magnitude (½)
and direction (+ or -)

 Each atomic orbital can admit only two identical

electrons with opposite spin
Pauli exclusion principle
• The numbers of electrons that can occupy each
shell and each sub-shell arise from equations of
quantum mechanics

• One of such is Pauli exclusion principle

• It states that no two electrons in the same atom

can have the same values for the four quantum
numbers
pg 18
 How many subshells, orbitals and electrons are
contained within the principal shell with n=4?
Solution
A. Given n=4, l can have values from 0 to n-1
l=0,1,2 and 3 (four subshells ≡ s, p, d, f)
B. l =0, ml =0: 1 orbital
l =1, ml = -1, 0, +1: 3 orbitals
l =2, ml = -2, -1, 0, +1, +2: 5 orbitals
l =3, ml = -3, -2, -1, 0,+1,+2,+3: 7 orbitals
• Total = 16 orbitals
• Total number of electrons = 2n2 =2(4)2
=2x16=32 electrons
 Filling electrons into subshells and
orbitals
• According to Aufbau principle, (German
word meaning construction or building
up), electrons orbiting an atom fill
subshell/orbitals in order of increasing
orbital energy
• The lowest energy subshell are filled before
electrons are placed in higher energy subshell:
s<p<d<f
• A maximum of two electrons can occupy a
given orbital
• Where the available orbitals are
Energies of orbitals
Fitting electrons into orbitals
 CHE 156

ACIDS, BASES AND SALTS

NATHANAEL DAMILARE OJO

COURSE CONTENT
BROAD DIVISION

• ACIDS
• BASES
• pH
• SALT
• BUFFER SOLUTION

2
COURSE CONTENT
• Unit 1: Acid and bases in our environment
• Unit 2: Properties of acids and bases
• Unit 3: Concepts of Acids and Bases: Arrhenius, Lowry-Bronsted
and Lewis concept

3
Objectives of the Section
• At the end of the section, you should be able to

➢Define acids and bases

➢List at least two properties each of acids and bases

4
Expected Learning Outcome
• By the end of this section, you should be able to

• Identify and list common acidic and basic substances in

the environment
• Differentiate between an acid and a base using their
definitions and properties

5
Unit 1: Acid and bases in our environment

ACIDS: WE LIVE WITH THEM

6
ACIDS: A DANGER OR A DARLING
Unit 1: Acid and bases in our environment

• Acids in our environment:

✓Unripe fruits
✓Sour milk
✓Aspirin
✓Car batteries
✓Human stomach acid
✓Acid rain: SO2, CO2, NO2 in rain

This Photo by Unknown Author is licensed under CC BY-SA-NC

8
https://creativecommons.org/licenses/by-nc-sa/3.0/
• Bases in our environment:
• Milk of magnesia
• Ammonia in cleaning agents
• Bleach
• Lye (NaOH)

11
 Unit 2
Properties of acids and bases: neutralization;
acid salts; monoprotic, diprotic and
polyprotic acids

12
Properties of an Acid
• Physical properties:
➢Sour taste
➢Concentrated acids are corrosive
➢Turn moist blue litmus red
➢pH < 7
➢Soluble in water
➢Aqueous acidic solutions are electric conductors

13
Properties of an Acid
• CHEMICAL properties:
➢Releases hydrogen gas when reacted with highly electropositive
(active) metals
➢Forms salt with alkali (neutralization)

14
Properties of a Base
• Physical properties:
➢Bitter taste
➢Slippery to touch
➢Concentrated bases are corrosive
➢Turn moist red litmus blue
➢Good conductor of electricity
➢pH > 7
➢Bases that are very soluble in water are called ALKALI e.g., NaOH,
KOH

15
Properties of a Base/Alkali
• CHEMICAL properties:
➢Neutralization Reaction: base + acid form salt and water
• Alkali reacts with ammonium salt to release ammonia gas e.g.
Ca(OH)2(s) + (NH4)2SO4(s) Heat CaSO4 + 2NH3(g) + 2H2O(l)

• Alkali solution precipitates insoluble metal hydroxides from solution

of its salt:
2NaOH(aq) + CuSO4(aq) Cu(OH)2(s) + Na2SO4(aq)

16
Properties of a Base/Alkali
• Reaction with metal: Strong alkalis (NaOH) reacts with aluminium to
liberate hydrogen gas (not a general reaction)
• 2Al(s) + NaOH(aq) +6H2O(l) 2Na3Al(OH)4(s) + 3H2(g)

17
UNIT 3
DEFINITIONS OF ACIDS AND BASES
• Learning Outcomes: at this end of this unit, you should
be able to
✓Define an acid and a base according to Arrhenius, Bronsted-
Lowry and Lewis theories
✓Classify acids based on the presence of oxygen and
replaceable hydrogen atoms, and strength

18
WHAT IS AN ACID?

19
 UNIT 3
DEFINITIONS OF ACIDS AND BASES
▪ Only hydrogen atoms involved in polar bonds are ionizable
• Arrhenius theory of acids
▪ Acids produce H+ (H3O+)ions in aqueous solution
▪ HA +H O
2
H3O+(aq) + A-(aq)

20
DEFINITIONS OF ACIDS AND BASES
• Arrhenius acids can be grouped into:
➢Non-oxygen acids and oxyacids
➢Monoprotic, diprotic and triprotic acids
➢Strong and weak acids

21
DEFINITIONS OF ACIDS AND BASES
• Non-oxygen acids: HCN(aq), HI(aq) and HCl(aq)
• Oxyacids e.g. H2SO4(aq), HClO4(aq) and H3PO4(aq)

22
DEFINITIONS OF ACIDS AND BASES
• Monoprotic acids: HClO4(aq), HNO3(aq), HCl(aq), CH3COOH(aq)
• Diprotic acids: H2SO4(aq), H2SO3(aq), H2CO3(aq)
• Triprotic acids: H3PO4(aq), citric acid and arsenic acid

• NOTE: (aq) means the acid is dissolved in water to form an aqueous

solution

23
DEFINITIONS OF ACIDS AND BASES
• Strong acids: HClO4(aq), HNO3(aq), HCl(aq), HI(aq) and H2SO4(aq)
• Weak acids: HF(aq), H2S(aq), H3PO4(aq) and HCN(aq)

24
Arrhenius theory of bases
• An Arrhenius base releases its OH- ions in water

25
Arrhenius theory of bases
• Strong Arrhenius base completely ionizes in water e.g. NaOH
• NaOH(aq) Na+(aq) + OH-(aq)
• Weak Arrhenius base partially ionizes in water e.g. Al(OH)3(s)

• Arrhenius definition of acids and bases is limited to aqueous solution

26
BRÖNSTED-LOWRY ACIDS AND BASES
• An acid is a proton donor
• A base is a proton acceptor
• The B-L acid-base definition is broader than Arrhenius definition
• All Arrhenius acids and bases are Bronsted-Lowry’s acids and bases
• For example:
NH3(g) +HCl(g) NH4Cl(s)
Base Acid Salt

27
BRÖNSTED-LOWRY ACIDS AND BASES
• Every B-L acid has a conjugate base, and vice versa
• HCl(aq) + H2O(aq) H3O(aq)+ + Cl-(aq)
• Acid1 + Base2 Acid2 + Base1
• Strong acid forms a weak conjugate base; weak base forms a strong
conjugate acid
• B-L theory restricts the definition of acids and bases to proton transfer

28
Lewis Theory of Acids and Bases
• Lewis acid is an electron pair acceptor
• Lewis base is an electron pair donor

29
Lewis Theory of Acids and Bases
• Every B-L base is a Lewis base
• Every B-L acid is a Lewis acid
• Electron pair can be donated to other electron deficient species other
than H+
• Examples of Lewis acid are AlCl3, metal ions, BCl3
• Examples of Lewis base are NH3, ethylene diamine, OH-
• For instance, Na2O(s) + SO3(g) Na2SO4(s)

✓No proton transferred, no hydrogen ion transferred, yet a neutralization

reaction: Lewis acid-base reaction
30
Class Quiz
• Group the following into Arrhenius acids, Bronsted-Lowry and Lewis
acids:
1. H2SO4(aq)
2. HCl(g)
3. H2O(l)
4. NH4+(aq)
5. HCl(aq)
6. AlCl3(s)

31
 UNIT 4
The Strength of Acids and Bases
• This can be compared using
➢Degrees of dissociation, α
➢Dissociation constant: Ka and Kb
➢pH and pOH
• Ka and Kb are temperature dependent; concentration independent
• The degree of dissociation is based on Ostwald’s dilution law

30
Ostwald’s dilution law
• This law relates to weak electrolyte; employs the degree of
dissociation
• The degree of dissociation of a weak electrolyte is inversely
proportional to the square root of molar concentration
• Consider a weak binary electrolyte MA
• MA(aq) M+(aq) + A-(aq)
c: molar concentration
• c(1-α) cα cα α: degree of dissociation

31
• Dissociation constant, (1)

• K = cα2 ; α = 𝐾Τ𝑐 1/2 if α <<1 (2)

• NOTE: α depends on concentration (a major set back)

32
Dissociation constants
• Consider the ionization of water:
+ −
• H2O(l) 𝐻(𝑎𝑞) + 𝑂𝐻(𝑎𝑞)
• The dissociation constant at equilibrium, K = 3
• [H2O] >> [H+], [OH-] for pure water;
• Kw = [H+][OH-];
• [H+] = [OH-] = 1.00 x 10-7 moldm-3 during full ionization at 25 oC
• Kw : ionic product of water is temperature dependent

33
Dissociation of an acid
• HA(aq) H+ + A-
+ −
𝑎𝐻 𝑎𝐴
• 𝐾𝑎 = 𝑎𝐻𝐴
4
• aH+, aA- and aHA are the activities of hydrogen ions, anion and
the weak acid
• Activity ≈ concentration for a dilute solution
• Ka = 5

34
Dissociation of a base (A-)
• A-(aq) + H2O HA(aq) + OH-
[𝐻𝐴][𝑂𝐻 −]
• Kb = 6
[𝐴−]
• Equations 5 x 6 become
• Kw = Ka x Kb = [H+][OH-] 7
• pKa = -Log10Ka 8
• pKb = -Log10Kb 9

• NOTE: 1. Large Ka ≡ small pKa ≡ strong acid

• 2. Large Kb ≡ small pKb ≡ strong base

35
Table 1: Dissociation constants of acids (Ka) and weak bases (Kb)

Adapted from Fundamental Physical Chemistry (Iweibo et al.) 2007 Revised Edition 36
 Unit 5
Acid-Base equilibria in aqueous solutions: The pH
concept; calculations of pH of strong/weak acid
solution, strong/weak base solution

37
Expected Outcomes for Unit 5
• At the end of the unit, you should be able to:
➢define pH of a solution
➢calculate the pH of an aqueous solution of a strong acid
➢calculate the pH of an aqueous solution of a weak acid
➢calculate the pH of an aqueous solution of a strong base
➢calculate the pH of an aqueous solution of a weak base

38
The pH concept
• pH expresses the acidity or basicity of a solution
• pH = -Log10[H+] 10
• [H+]: molar concentration of the hydrogen ion (or H3O+) in solution
• p : potenz (German word which means power to which 10 is raised)

39
The pH concept
• When pH < 7: an acidic solution; [H+] > [OH-]
• When pH >7: a basic/alkaline solution [H+] < [OH-]
• When pH = 7: a neutral solution [H+] = [OH-]

40
The pH of an aqueous solution of a strong acid

• A strong acid fully dissociates in solution

• The pH of a strong acid solution follows equation 10:
• pH = -Log10[H+] 10

41
Example 1: The pH of an aqueous solution of a strong acid
• Determine the pH of a 0.20 M HNO3 solution.
• Solution
HNO3(aq) H+(aq) + NO3-(aq)
1 mole 1 mole 1 mole
0.20 moldm-3 0.20 moldm-3 0.20 moldm-3
[H+] = 0.20 moldm-3
pH = -Log10[H+]
pH = - Log10(0.20) = 0.70

42
Example 2: The pH of an aqueous solution of a strong acid
• Determine the pH of a 0.20 M H2SO4 solution.
• Solution
H2SO4(aq) 2H+(aq) + SO42- (aq)
1 mole 2 mole 1 mole
0.20 moldm-3 (2 x 0.20) moldm-3 0.20 moldm-3
[H+] = 0.40 moldm-3
pH = -Log10[H+]
pH = - Log10(0.40) = 0.40

43
The pH of an aqueous solution of a weak acid

• Weak acids dissociate partially in solution

• The degree of dissociation is less than 1
• The concentration is better expressed as activity of the solution

44
The pH of an aqueous solution of a weak acid

• The pH of a weak acid solution in expressed as:

1 1
• 𝑝𝐻 = 𝑝𝐾𝑎 − 𝐿𝑜𝑔 𝑐 11
2 2
• Where 𝑝𝐾𝑎 = −𝑙𝑜𝑔𝐾𝑎 12
• [H+] = 𝐾𝑎 𝑐 13
• c = molar concentration of the acid (not the hydrogen ion concentration)
• Ka = acid dissociation constant

45
Example: The pH of an aqueous solution of a weak acid

• Calculate the pH of a 0.001 M solution of methanoic acid.

Ka =1.8 × 10−4
Solution
1 1
𝑝𝐻 = 𝑝𝐾𝑎 − 𝐿𝑜𝑔 𝑐 11
2 2
1 1
pH = − 𝑙𝑜𝑔 1.8 × 10−4 − 𝑙𝑜𝑔 1.0 × 10−3
2 2
pH = 1.87 + 1.50
pH = 3.37

46
The pH of an aqueous solution of a strong
base
• A strong base dissociates completely in water to give OH- ions
• A strong base produces a weak conjugate acid

47
The pH of an aqueous solution of a strong
base
• For example:
• Calculate the pH of 0.05 M NaOH solution.
• Solution:
• NaOH(aq) Na+(aq) + OH-(aq)
• 0.05 M 0.05 M 0.05 M

• 𝑝𝐻 = − log 2 × 10−13 = 12.70

48
The pH of an aqueous solution of a weak base
• For a weak base, the pH is
1 1
• 𝑝𝐻 = 𝑝𝐾𝑤 − 𝑝𝐾𝑏 + 𝐿𝑜𝑔 𝑐 12
2 2
• 𝑝𝐾𝑤 = 14
• 𝑝𝐾𝑏 = −𝐿𝑜𝑔10 𝐾𝑏

49
Example: The pH of an aqueous solution of a weak base

• Determine the pH of a 0.05 M aqueous hydroxylamine solution. Kb =

1.1 x 10-8 at 298 K.
• Solution
• HONH2(aq) + H2O(l) HONH3+(aq) + OH-(aq)
1 1
• 𝑝𝐻 = 𝑝𝐾𝑤 − 𝑝𝐾𝑏 + 𝐿𝑜𝑔 𝑐 12
2 2
1 −8 1
• 𝑝𝐻 = 14 − (−log(1.1 × 10 ) + 𝐿𝑜𝑔 0.05
2 2
• 𝑝𝐻 = 14 − 3.98 − 0.65 = 9.37

50
 Unit 6
Hydrolysis: Definition and description of salt of
strong/weak acid and strong/weak base

51
Expected Outcome
• At the end of this unit, you should be able to
✓Define salt
✓Describe hydrolysis of salt

52
Salt
• Ionic compound in which H+/OH- ion is totally/partially replaced by a
metal ion or positive radical
• Types: normal, acid, basic, complex and double salt
• Normal salt: Strong acid + Strong base e.g. NaCl
➢Acid salt: Strong acid + weak base e.g. NaHSO4 , NH4Cl
➢Basic salt: Weak acid + Strong base e.g. CH3COONa
➢Complex salt e.g. Cu(NH3)42+
➢Double salt e.g. KAl(SO4)2.12H2O, (NH4)2[Fe(H2O)6](SO4)2

53
Salt of strong acid and strong base
• Does not hydrolyze in solution
• It is neutral: pH = 7
• MA M+ + A-
• Examples: NaCl, NaNO3, K2SO4

54
Salt of strong acid and weak base
• Hydrolyzes to produce acidic solution
• pH on hydrolysis < 7
• Examples: NH4NO3, CuSO4, NH4Cl

55
Salt of weak acid and strong base
• Hydrolyzes to produce basic solution
• pH on hydrolysis > 7
• Examples: CH3COOK, HCOONa
• HCOONa HCOO- + Na+(aq)

56
Salt of weak acid and weak base
• Hydrolyzes to produce acidic, basic or neutral solution
• Examples: CH3COONH4, HCOONH4, (NH4)2CO3

57
 UNITS 7 AND 8

Buffer Solution: Definition and buffer action: Preparation and uses of

buffer solution; Calculation of the pH of buffer solutions

58
Expected Outcome
• At the end of the units, you should be able to
❖Define a buffer
❖Explain the preparation of a buffer solution
❖Determine the pH of a buffer solution

59
Buffer solution
• Resists sharp change in pH
• Buffer: helps living organisms to resist drastic change in pH
✓For instance: Human blood (pH = 7.4), enzyme operate at specific pH
✓Blood plasma contains carbonic acid, carbonate and sodium salts of
phosphoric acid
✓Citric acid is used to stabilize milk of magnesia
✓Tears possess high buffer capacity

60
Buffer action
• Buffer contains
• Weak acid and its salt e.g. ethanoic acid and sodium ethanoate
• Weak base and its salt e.g. aqueous ammonia and ammonium chloride
• Salt of a weak acid and a weak base e.g. ammonium ethanoate

61
Buffer action
• Weak acid and its highly ionizable salt:
➢added hydrogen ions will combine with excess anion e.g. ethanoate
ion;
➢Added base (OH-) will react with be removed by the acid part (e.g.
ethanoic acid) of the buffer

62
Buffer action
• Weak base and its salt e.g. aqueous ammonia and ammonium
chloride
✓Added hydrogen ions will be removed by aqueous ammonia
✓Added hydroxide ions (base) will be removed by ammonium ions

63
Buffer action
• Salt of a weak acid and a weak base e.g. ammonium ethanoate
✓Added hydrogen ions will be removed by ethanoate ions
✓Added hydroxide ions (base) will be removed by ammonium ions

64
pH of a buffer solution
• Buffering capacity and pH of a buffer are very important
• Buffering capacity: amount of acid/base the buffer can neutralize before
pH change becomes appreciable
𝑛𝑜.𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑎𝑑𝑑𝑒𝑑 𝑎𝑐𝑖𝑑/𝑏𝑎𝑠𝑒 𝑝𝑒𝑟 𝑙𝑖𝑡𝑟𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑏𝑢𝑓𝑓𝑒𝑟
• Buffer capacity β = 𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑝𝐻
13

65
pH of a buffer solution
[𝐴−]
• pH = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 14
[𝐻𝐴]
OR
[𝑆𝐴𝐿𝑇]
• pH = 𝑝𝐾𝑎 + 𝑙𝑜𝑔
[𝐴𝐶𝐼𝐷]
• [𝐴− ] = concentration of the salt
• [𝐻𝐴] = concentration of the acid
• Equation 14 is Henderson-Hasselbalch equation

66
EXERCISE (pH of buffer solution)
• 0.065 M sodium ethanoate is added to 0.02 M ethanoic acid to prepare
a buffer solution. Calculate:
1. the pH of the buffer (assume no change in volume)
2. The change in pH if 1 cm3 of 1 M NaOH is added to the buffer

Ans: 1. pH = 5.25
2. change in pH = 0.03

67
 0.065 M sodium ethanoate is added to 0.02 M ethanoic acid to prepare a buffer
solution. Calculate:
the pH of the buffer (assume no change in volume)
The change in pH if 1 cm3 of 1 M NaOH is added to the buffer

• Determine the new concentration of NaOH, CH3COOH and salt

• [NaOH]: C1=1M, V1= 1cm3 (10-3 dm3); V2= 1001 cm3, C2= ? (Ans:
0.000999 M)
• Since a base was added, [acid] reduces; [salt] increases
• [Acid] = 0.02 – 0.000999 M = 0.019001 M
• [Salt] = 0.065 + 0.000999 M = 0.065999 M
[𝑆𝐴𝐿𝑇]
• pH = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 = 5.28
[𝐴𝐶𝐼𝐷]
• ΔpH = 0.03
• NOTE: The buffer experiences a slight change in pH
68
Unit 9: Acid-Base Indicators: Acid/base
strength and chemical structure
• Expected outcome
• By the end of the unit, you should be able to
✓describe an indicator
✓state appropriate indicator for specific acid-base reactions

69
Indicator

• Substance to determine the endpoint of an acid-base reaction

✓Each indicator has pH range where it gives a notable colour
✓Phenolphthalein: 8.3 – 10.5 (pink); < 8.3 (colourless)
✓Methyl orange: 3.2 – 4.5 (red); >4.5 (yellow)

70
Acid-base indicator
• It can be a weak acid or a weak base; partially ionizable
• Change in concentration of indicator can alter the degree of ionization
• HIn + H2O H3O+ + In-
• Indicator Conjugate base
• The unionized indicator and its conjugate base display different colour
• The equilibrium constant, KIn = 15

71
Acid-base indicator
• Useful relationship between pH and pKIn :
• pH = 𝑝𝐾𝐼𝑛 ± 1 16
• That is, the useful pH range at which the colour of the indicator is
perceptible
• A universal indicator may contain 4-5 different indicators with pH
range 4-11

72
Acid-base indicator
Table 2: Acid-base indicators and their pH range

Adapted from PHYSICAL CHEMISTRY textbook by K.K. Sharma and L.K. Sharma 73
Acid-base indicator in titration
• Strong acid - Strong base Titration: Methyl orange and
phenolphthalein are suitable.
• Strong acid - Weak base Titration: Methyl orange is suitable
• Weak acid - Strong base Titration: Phenolphthalein is suitable
• Weak acid - Weak base Titration: No suitable indicator. No accurate
endpoint

74
Practice Questions
1. AlCl3 is an example of ___
(a). Arrhenius base
(b). Lewis base
(c). Lewis acid
(d). Bronsted-Lowry acid

75
2. The pH of 0.01 M H2SO4 is ___
(a). 0.02
(b). 2.0
(c). 1.7
(d). 0.8

76
3. The pH of 0.00023 M citric acid is _______ (Ka = 3.5 x 10-4)
(a). 3.55
(b). 1.82
(c). 3.46
(d). 1.73

1 1
𝑝𝐻 = 𝑝𝐾𝑎 − 𝐿𝑜𝑔 𝑐 11
2 2
1 −4 1
pH = − 𝑙𝑜𝑔 3.5 × 10 − 𝑙𝑜𝑔 2.3 × 10−4
2 2
pH = 1.73 + 1.82
pH = 3.55

77
4. The Kb of 0.010 M NH3 solution with 0.0424 degree of ionization is _
(a). 1.8 x 10-4
(b). 1.8 x 10-5
(c). 1.8 x 10-8
(d). 1.8 x 10-10

C = 0.010 M, α = 0.042, Kb = ?
Kb = cα2
Kb = 0.010 × (0.0424)2 = 1.8 x 10-5

78
5. The pH of a buffer containing 0.100 M lactic acid and 0.100 M
sodium lactate is _______ (Ka = 1.4 x 10-4)
(a). 1.93
(b). 4.85
(c). 3.85
(d). 3.55

[𝑆𝐴𝐿𝑇]
pH = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 14
[𝐴𝐶𝐼𝐷]
−4
pH = −𝑙𝑜𝑔 1.4 × 10 + 𝑙𝑜𝑔 1
pH = 3.85 + 0
pH = 3.85

79
6. The pH of a buffer containing 0.100 M lactic acid and 0.100 M
sodium lactate when (a) 0.01 M NaOH (b) 0.01 M HCl is added is
_______. Assuming no volume change. (Ka = 1.4 x 10-4)
(a). 3.85 and 3.76
(b). 3.94 and 3.76
(c). 3.85 and 3.94
(d). 3.94 and 3.00
Add
[𝑆𝐴𝐿𝑇]
pH = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 14
[𝐴𝐶𝐼𝐷]
−4
pH = −𝑙𝑜𝑔 1.4 × 10 + 𝑙𝑜𝑔 ? ?
pH = 3.85 + ??
pH = ??

80
6. The pH of a buffer containing 0.100 M lactic acid and 0.100 M
sodium lactate when (a) 0.01 M NaOH (b) 0.01 M HCl is added is
_______. Assuming no volume change. (Ka = 1.4 x 10-4)
• Note: When base is added, the concentration of the acid decreases; the conc of the
salt increases
• When acid is added, the concentration of the salt decreases; the concentration of
the acid increases
[𝑆𝐴𝐿𝑇]
(a) pH = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 14
[𝐴𝐶𝐼𝐷]
−4 0.1+0.01
pH = −𝑙𝑜𝑔 1.4 × 10 + 𝑙𝑜𝑔
0.1 −0.01
pH = 3.94

81
 [𝑆𝐴𝐿𝑇]
(b) pH = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 14
[𝐴𝐶𝐼𝐷]
0.1 − 0.01
pH = −𝑙𝑜𝑔 1.4 × 10−4 + 𝑙𝑜𝑔
0.1+ 0.01
pH = 3.76

82
83
Henderson-Hasselbalch Equation
• HA H+ + A-
• Acid + −
Conjugate base or Salt
𝐻 [𝐴 ]
• Ka=
[𝐻𝐴] + −
𝐻 [𝐴 ]
• −𝑙𝑜𝑔𝐾𝑎 = −𝑙𝑜𝑔
[𝐻𝐴]
+ −
• −𝑙𝑜𝑔𝐾𝑎 = −𝑙𝑜𝑔 𝐻 − − log 𝐴 + log 𝐻𝐴
[𝐴 ]
• 𝑝𝐾𝑎 = 𝑝𝐻 − 𝑙𝑜𝑔
[𝐻𝐴]
−
[𝐴 ] [𝑠𝑎𝑙𝑡]
• 𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔 ; 𝑝𝐻 = 𝑝𝐾𝑎 + 𝑙𝑜𝑔
[𝐻𝐴] [𝑎𝑐𝑖𝑑]

84
Henderson-Hasselbalch Equation

•For a base, B + H+ BH+

• Base Acid

85
References
• Fundamental Physical Chemistry, Revised edition, Edited by Iweibo I.,
Okonjo K. & Obi-Egbedi N.
• https://www.pdfdrive.com/physical-chemistry-books.html

• https://www.pdfdrive.com/download.pdf?id=39587383&h=b2d7b6e2e
394267f626af702fbaff3d0&u=cache&ext=pdf
• https://www.pdfdrive.com/download.pdf?id=26523760&h=8a81af9a1
729968e5ba2e3d72eb2e984&u=cache&ext=pdf

86
 WEEK ONE

CHE 156
Thermochemistry
 Matter and Energy

⚪ The universe is composed of matter

and energy.
⚪ Matter includes all tangible things,
and has mass and volume which can
be measured.
⚪ The concept of energy is more difficult
to grasp because energy is intangible,
Energy, unlike matter, cannot be held
in your hand.
 Energy

⚪ Energy can be defined as the

capacity to do work (move matter)
or produce heat. A wound clock
acquires "something" with which it
can do work. This "something" that
enables the clock to do work is
energy. An object can exhibit energy
in two fundamental ways, kinetic
energy (Ek) and potential energy (Ep).
 Kinetic Energy

⚪
 Potential Energy

⚪
 Matter and Energy
⚪
 WEEK TWO

CHE 156
Thermodynamics
 Basic Concepts
(Thermodynamics terms)
⚪ System: Part of the universe under
study = object of study
⚪ Boundary: The real or imaginary
surface separating the system from
the surroundings.
⚪ Universe: System + Surroundings =
an isolated system.
⚪ Surroundings: Remaining part of the
universe around the system, which is
not under study. It is where
observation is made.
 The Law of Conservation of
Energy

⚪ States that in physical or chemical

change energy may be exchanged
between a system and its
surroundings but energy cannot be
created or destroyed. Energy may be
converted from one form to another,
but the total quantity of energy
remains constant. The energy of the
universe remains unchanged and is
therefore constant.
 The Law of Conservation of
Energy

⚪ ∆E universe = O
⚪ The total energy of the universe
is constant, it is not created or
destroyed, however it can be
transferred from one substance
to another.
⚪ ∆E universe = ∆E system + ∆E surroundings
Types of System
Open-system
⚪ both matter and
energy can freely
cross from the
system to the
surroundings and
back.
⚪ Ex: an open test
tube
Closed-System
⚪ energy can cross
the boundary, but
matter cannot.
⚪ Ex: a sealed test
tube, a bottle of
water, etc.
Isolated-System
⚪ neither matter
nor energy can
cross between the
system and the
surroundings.
⚪ Ex: The universe
● there are no
surroundings to
exchange matter
or energy with (as
far as we know!)
A State:
⚪
 Homogeneous and
Heterogeneous System
⚪ Homogeneous system: A system is
homogeneous if it is uniform throughout.
It consists of only one phase e.g. a
system contain only pure solid or a pure
liquid or a pure gas or completely
immiscible liquids or gases etc.
⚪ Heterogeneous system: not uniform
throughout contains more than one
phase i.e. polyphaser e.g. a mixture of
two (2) immiscible liquids, or gases, or
solids etc.
 Thermodynamic Properties
Systems properties are:
1. Intensive Properties: do not depend on
the amount or quantity of matter or
material present in the system i.e.
depends on the nature of the material in
the system e.g. viscosity, surface tension,
thermal conductivity, boiling points,
freezing points, refractive index, vapour
pressure, temperature, density, specific
heat capacity, etc.
 Thermodynamic Properties
2. Extensive Properties: depends on the
amount of matter in the system e.g. mass,
internal energy, volume, pressure, heat
capacity, free energy, heat content,
entropy, etc.
 Thermodynamic Processes
⚪
 Thermodynamic Processes
⚪
 Thermodynamic Processes
⚪
 Thermodynamic Processes
⚪
 Thermodynamic Processes
⚪
 Thermodynamic Processes
⚪ Reversible Process:- A process is said to
be reversible if it is carried out
infinitesimally slowly so that the driving
force in only infinitesimally greater than
the opposing force. Such types of
processes are ideal and cannot be
realized in practice. This is because
reversible process requires infinite time
for its completion.
⚪ Irreversible Process:- It is a process
that cannot return both the system and
the surrounding to their original
 WEEK THREE

CHE 156
Matter and Energy
 Matter and Energy

⚪
⚪ Chemists define work as directed
energy change resulting from a
process. Chemical processes
(reactions) are almost always
accompanied by the absorption or
release of one form of energy, heat
(thermal energy). The study of the
energy (heat) change associated
with chemical reactions is known as
thermochemistry.
⚪
 Thermal energy, Heat, and
Temperature

⚪ Thermal energy is the energy of

motion (kinetic energy) of the unit
particles of a substance. The unit
particles of any substance not at
zero K (absolute zero) have thermal
energy. The unit particles of a solid
are in close contact and movement
of such particles is limited to
rotational and vibrational.
 Thermal energy, Heat, and
Temperature

⚪ Particles in a liquid exhibit all three

types of molecular motion
(translational, rotational, and
vibrational) even though they are in
constant contact with each other.
⚪ The particles of a gas have the
greatest freedom of the three states
of matter and move freely about in
space. The higher the temperature,
the faster the particles move.
 Temperature

⚪ A relative measure of how hot or

how cold an object is. It is a
measure of the average random
motion (kinetic energy) of the unit
particles of an object.
⚪ It is the property of an object that
determines the direction in which
thermal energy will be transferred
when it is in contact with another
object at a different temperature.
 Temperature

⚪ When two objects are

in contact with one
another, and at the
same temperature,
the average kinetic
energy of the unit
particles of the two
objects is equal.
⚪ Measured with a
thermometer
 Temperature
⚪ A temperature change is explained
as a change in kinetic energy
⚪ Temperature depends on the
quantity of heat (q) flowing out or in
of the substance.
 Heat

⚪ Heat (q) is the thermal energy that

"flows" into or out of a substance
due to a temperature difference.
Heat flows spontaneously from the
warmer object to the colder object.
 Internal Energy

⚪
 The kinetic energy
(thermal energy)

⚪ Is associated with random molecular

motion. There are three types.
1. Translational
2. Rotational
3. Vibrational
 The potential energy
(chemical energy)

⚪ Is associated with electrostatic

attractions within and between
molecules. There are two types
1. Intramolecular forces (bonds)
2. Intermolecular forces
⚪
 WEEK FOUR

CHE 156
Thermodynamics
&
Equilibrium system
 FIRST LAW OF
THERMODYNAMICS
⚪
⚪
⚪
 Expansion Work or Pressure-
Volume Work
⚪
⚪
 b.) Free Expansion:
⚪
 Solution:
⚪
 Reversible and Irreversible
Process
⚪
⚪
⚪
 Expression for Reversible
Expansion
⚪
⚪
⚪
 WEEK FIVE

CHE 156
Heat Capacity
 Isothermal irreversible
Expansion Work of an ideal Gas
⚪
Example 2:
⚪
 Example 3:
⚪
Example 4:
⚪
 Example 5:
⚪
 HEAT CAPACITY
⚪
Table of Specific Heats
⚪
⚪
⚪
⚪
⚪
 A change of state or phase transition is a change of
a substance from one state to another.

⚪ Melting (fusion) is the change of a solid to the liquid

state. H2O(S) ---> H2O (1)
⚪ Freezing is the change of a liquid to the solid state,
H2O (l) ---> H2O(s)
⚪ Vaporization is the change of a liquid to the vapor.
H2O (l) ---> H2O (g)
⚪ Condensation is the change of a gas to a liquid. H2O
(g) ---> H 2O (1)

⚪ Sublimation is the change of a solid directly to the

vapor. H2O (S) ---> H2O (g)
⚪ Deposition is the change of a vapor directly to the
solid. H2O (g) ---> H2O (s)
⚪ In any phase transition, heat (q) will be transferred as
the substance undergoes the transition.
⚪
 WEEK SIX

CHE 156
Enthalpy
⚪
⚪
⚪
⚪
⚪
 Stoichiometric Calculations
involving Thermochemical
Equations
⚪
 EXAMPLE 3
⚪
 EXAMPLE 4
⚪
 EXAMPLE 5
⚪
 CALORIMETRY
Calorimetry is the
measurement of heat changes.
A calorimeter is an apparatus
used to measure the quantity
of thermal energy gained or
lost during physical or
chemical changes.
Bomb Calorimetry: Reactions at
Constant Volume
⚪ The amount of heat given off by the
combustion of a fuel can be
determined very accurately in the so-
called bomb calorimeter, which
consists of a combustion chamber
(the "bomb") set in another chamber
filled with water. Heat generated by
combustion of the fuel is transmitted
to the water, raising its temperature.
The calorie content of food is tested
this way.
⚪
⚪
⚪
 EXAMPLE 11
⚪
⚪
 EXAMPLE 12
⚪
 WEEK SEVEN

CHE 156
HESS LAW
 HESS'S LAW
For a chemical equation that can be written
as the sum of two or more steps, the
enthalpy change for the overall equation
equals the sum of the enthalpy changes for
the individual steps. In other words, no
matter how you go from given reactants to
products (whether in one step or several),
the enthalpy change for the overall
chemical change is the same.
Hess's law states that the heat transferred
in a given change is the same whether the
change takes place in a single step or in
⚪
 EXAMPLE 12
⚪
 In order to use Hess's Law:

⚪
 EXAMPLE 13
⚪
 EXAMPLE 14
⚪
 Solution:
⚪
⚪
⚪
 The standard enthalpies of formation of
the elements in their standard states are
zero
⚪
 EXAMPLE 15
⚪
 EXAMPLE 16
⚪
 EXAMPLE 13
⚪
 PREMIER
DEPARTMENT OF CHEMISTRY
 Course Outline
Atoms and Molecules- Olatunde
Acids, Bases and Salts - Ojo
Thermochemistry - Adejoro
Oxidation and Reductions/
Electrochemistry- Babalola
Rates of Reactions- Obi-Egbedi
Kinetic Theory of Gases- Odozi
Oxidation and Reductions/
Electrochemistry-

J. O. Babalola
 OXIDATION AND REDUCTION
There are many definitions that can be
given to oxidation and reduction

A) Definition in term of oxygen

B) Definition in term of hydrogen

C) Definition of oxidation and reduction

in term of oxidation number
 Definition in term of oxygen
Oxidation can be defined as the addition of
oxygen to a substance (that is, an element
or a compound).

For example, iron nail exposed to oxygen

from the atmosphere rusts because of
the addition of oxygen.

4Fe(s) + 3O2(g) 2Fe2O3(s)

Iron rust
 Definition in term of oxygen
Reduction is the removal of oxygen
from a compound.
For example, most metal ores are in oxide forms,
the production of these metals are done by
reducing the metal ores (metal oxides) to the
metal. In the production of iron from iron ore
 Definition in term of hydrogen
•Oxidation is the removal of hydrogen
from a compound.
 Definition in term of hydrogen
Reduction is the addition of
hydrogen to an element or a
compound.
Examples: CuO(s) + H2(g) Cu(s) + H2O(l)

Cl2(g) + H2(g) HCl(g)

Definition in term of hydrogen
Definition of oxidation and reduction
in term of oxidation number
An example of such is the addition of metallic zinc
to an aqueous CuSO4, which is blue, to give a
colourless aqueous solution of ZnSO4 and a red-
brownish deposit of Cu metal. This reaction can
be divided into two halves, called half-reactions,
the oxidation reaction and the reduction reaction.
Definition of oxidation and reduction
in term of oxidation number
•Oxidation is increase in the oxidation number
( that is, loss of electrons)
•Reduction is decrease in the oxidation
number (that is, gaining of electrons).
The oxidation and reduction half-reactions
must always occur together and the total
number of electron loss in the oxidation
reaction(s) must be the total number of
electron gained in the reduction reaction(s).
Definition of oxidation and reduction
in term of oxidation number

Oxidation reaction Zn(s) Zn2+(aq) + 2e-

Reduction reaction Cu2+(aq) + 2e- Cu(s)
Net reaction Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

The oxidation number of zinc increases from 0 to +2

(that is, loss of two electons).
The oxidation number of copper decreases from +2 to 0
(that is , it gained two electrons).
 General Rules for Calculating
Oxidation Number
1. The oxidation number of an atom
(uncombined) is zero.
2. The sum of oxidation number of all atoms in a
molecule is equal to zero. For an ionic formular
unit, this is equal to the charge on the
formular unit both in magnitude and sign.
3. The alkali metals (group IA) (Li, Na, K, Rb, Cs and
Fr) have the oxidation number of +1 while the
alkaline earth metals (group IIA) have the
oxidation number of +2.
 General Rules for Calculating
Oxidation Number
4. The oxidation number of hydrogen is +1 in its
compounds while that of fluorine is –1.
5. Oxygen has an oxidation number of –2 in its
compound.
6. In their binary compounds with metals, the
elements of group 7A have oxidation number
of –1, group 6A, -2 and group 5A, -3.
7. The application of the rules are in order of 1, 2,
3……6, that is, rule 1 supercedes rule 2 and rule
2 surpercedes rule 3 and so on.
 General Rules for Calculating
Oxidation Number
1. The oxidation number of an atom
(uncombined) is zero.
2. The sum of oxidation number of all atoms in a
molecule is equal to zero. For an ionic formular
unit, this is equal to the charge on the
formular unit both in magnitude and sign.
3. The alkali metals (group IA) (Li, Na, K, Rb, Cs and
Fr) have the oxidation number of +1 while the
alkaline earth metals (group IIA) have the
oxidation number of +2.
 General Rules for Calculating
Oxidation Number
4. The oxidation number of hydrogen is +1 in its
compounds while that of fluorine is –1.
5. Oxygen has an oxidation number of –2 in its
compound.
6. In their binary compounds with metals, the
elements of group 7A have oxidation number
of –1, group 6A, -2 and group 5A, -3.
7. The application of the rules are in order of 1, 2,
3……6, that is, rule 1 supercedes rule 2 and rule
2 surpercedes rule 3 and so on.
 Example: Calculate the oxidation number of sulphur in the
Following compounds a) S8 b) ZnS
c) H2S d) Na2SO3 e) Na2SO4 f) Na2S2O3

Solution: a) Oxidation number of S atom is equal to 0 (Rule 1)

8 (S) = 0.
Therefore S = 0/8 = 0

b) ZnS
Rule 6, S is in group 6 A. Hence in its binary compound
with metals. Its oxidation number is –2.
S = -2
c) H2S Rule 4, H = +1
Therefore 2(+1) + S = 0
2+ S=0 S = -2
 e) Na2S2O3
d) Na2SO3
Rule 3, Na = +1
Rule 3, Na = +1
Rule 5, O = -2
Rule 5, O = -2
2(Na) + 2(S) + 3(O) = 0
2(Na) + S + 3(O) = 0
2(+1) + 2(S) + 3(-2) = 0
2(+1) + S + 3(-2) = 0
2 + 2S – 6 = 0
2+S–6=0
2S – 4 = 0
S–4=0
S = +2
S = +4
Example: What is the oxidation number of hydrogen in
the following compounds?
a) NaH b) H2O c) H2O2
a) NaH
Rule 3, Na = +1
Na + H = 0
1+H=0
H = -1

b&c) the determination of hydrogen’s

oxidation number comes before that of
oxygen. That is, Rule 4 should be applied
before Rule 5. Hence H = +1 in both cases.
Example: Calculate the oxidation number of oxygen
in the following compounds
a) H2O b) H2O2 c) K2O d) KO2
Solution: a) H2O b) H2O2
2H + O = 0 2H + 2(O) = 0
Rule 4, H = +1 Rule 4, H = +1
2(+1) + O = 0 2(+1) + 2(O) = 0
2+O=0 2 + 2(O) = 0
O = -2 2(O) = -2
O = -1.
c) K2O d) KO2
2K + O = 0 K + 2(O) = 0
Rule 3, K = +1 Rule 3, K = +1
2(+1) + O = 0 1 + 2(O) = 0
2+O=0 2(O) = -1
O = -2 O=-½
 Example: Calculate the oxidation number of the
metal atom in each of the following ionic formular
units a) Re2Cl82- b) Al(H2O)63+ c) Fe(CN)63-
Solution: a) Re2Cl82-
Rule 2, 2(Re) + 8(Cl) = -2
Rule 6, Cl = -1
2(Re) + 8(-1) = -2
2(Re) – 8 = -2
2(Re) = +6
c) Fe(CN) 3-
Re = +3 6

b) Al(H2O)63+ Rule 2, Fe + 6(CN) = -3

Rule 2, Al + 6(H2O) = +3 , N is a formular unit on its
H2O = 0 own. Its charge is –1
Al + 6(0) = +3 (carbon is +4 and N = -5)
Al + 0 = +3 Fe + 6(-1) = -3
Al = +3 Fe - 6 = -3
Fe = +3
Identifying Redox Reactions

Redox reactions are identified by checking the

oxidation numbers of the elements present in
the reaction at both the reactant side and the
product side, whether they change or not.
If the oxidation number of some of the
elements change, then it is a redox reaction.
If there are no changes in oxidation number of
the elements, then the reaction is not a redox
reaction.
Example: State whether the following reactions
are redox reactions or not.

1. Fe2O3 (s) + 3CO(g) 2Fe(s) + 3CO2(g)

Fe has changed from Fe3+ to Fe (oxidation state 0)
C has changed from C2+ to C4+
Therefore it is a redox reaction.

2. Ca3P2(s) + 6H2O(l) 3Ca(OH)2(aq) + 2PH3(g)

No element in this reaction has a change in
oxidation number.
P is –3 in Ca3P2(s) and PH3(g)
Ca is +2 in Ca3P2(s) and Ca(OH)2(aq) .
This is not a redox reaction
3. P4(s) + 5O2(g) P4O10(s)
P has changed from 0 in P4 to +5 in P4O10
O has changed from 0 in O2 to –2 in P4O10
This is therefore a redox reaction.

Note that in any redox

equation, there is at least one
oxidation half-reaction and at
least one reduction half-
reaction.
 Balancing of Redox Equations
Step 1:- Identify the species involved in oxidation
number changes and write out their
half-reactions.
Step 2:- Balance each of the half-reactions atomically
in this order.
i) atoms other than oxygen and hydrogen
ii) oxygen atoms by adding H2O
iii) hydrogen atoms by adding H+

Step 3:- Balance each half-reaction electrically by

adding necessary number of electrons.
 Balancing of Redox Equations
Step 4:- Obtain the net redox reaction by combining
the two half-reactions after the number of
electrons must have been made equal in
the two half-reactions.

Step 5:- Simplify the net equation by bringing the

same species together.

Step 6:- Verify the final equation to be sure that it is

balanced atomically and electrically.
For example: Balance the following redox reactions
in acidic medium.
i) MnO4- + Fe2+ Mn2+ + Fe3+
ii) SO32- + MnO4- + H+ SO42- + Mn2+ + H2O
i) Step 1: MnO4- Mn2+
Fe2+ Fe3+
Step 2: Balancing each half-reaction atomically
MnO4- Mn2+ + 4H2O (4H2O added for 4
oxygen atoms)
Since we now have 8 hydrogen atoms on the right, we need to add 8H + to the left.
MnO4- + 8H+ Mn2+ + 4H2O
Fe2+ Fe3+
Step 3: Balancing each half-reaction electrically
MnO4- + 8H+ Mn2+ + 4H2O
-1 + 8(+1) +2 + 0
+7 +2
The required number of electron(s) is(are) added to the side with higher oxidation
number to make them equal. Hence 5 electrons are added to the left side.
MnO4- + 8H+ + 5e- Mn2+ + 4H2O ……………(1)
For Fe2+ Fe3+ + e- ………………..……….(2)
(an electron is added to the right-hand side)
Step 4: There are 5e- in equation (1) and one in equation (2).
Therefore, equation (2) has to be multiplied by 5 so that it will
have the same number of electrons as equation (1).

MnO4- + 8H+ + 5e- Mn2+ + 4H2O ………(1)

5Fe2+ 5Fe3+ + 5e- ………………..…………….(3)
MnO4- + 5Fe2+ + 8H+ + 5e- Mn2+ + 4H2O + 5Fe3+ + 5e-

The balanced redox reaction is therefore

MnO4- + 5Fe2+ + 8H+ Mn2+ + 4H2O + 5Fe3+
ii) SO32- + MnO4- + H+ SO42- + Mn2+ + H2O
Step 1: SO32- SO42-
MnO4- Mn2+
Step 2: SO32- SO42- (left-hand side is one oxygen less, hence
H2O is added)
SO32- + H2O SO42- (add 2H+ to make up for hydrogen on
the right-hand side)
SO32- + H2O SO42- + 2H+
MnO4- Mn2+ is balanced as in example (i) to give
MnO4- + 8H+ Mn2+ + 4H2O
Step 3: Balancing the reaction electrically
SO32- + H2O SO42- + 2H+
-2 0 (2 electrons are to be added to the
left-hand side)
SO32- + H2O SO42- + 2H+ + 2e- ……………(1)
MnO4- + 8H+ Mn2+ + 4H2O becomes
MnO4- + 8H+ + 5e- Mn2+ + 4H2O……………(2)
Step 4: Equation (1) has 2 electrons while equation (2) has 5 electrons, therefore
eq. 1 should be multiplied by 5 and eq. 2 multiplied by 2.
(1) x 5 5SO32- + 5H2O 5SO42- + 10H+ + 10e-
(2) x 2 2MnO4- + 16H+ + 10e- 2Mn2+ + 8H2O
5SO32- + 5H2O + 2MnO4- + 16H+ + 10e- 5SO42- + 10H+ + 2Mn2+ + 8H2O + 10e-
Step 5: Simplifying the reaction, collecting like terms to the same side we have
5SO32- + 2MnO4- + 6H+ 5SO42- + 2Mn2+ + 3H2O
Reaction in Basic medium
It is easier to use a similar method as those in acidic medium; the only difference is that
after obtaining the net reaction, hydroxyl ion equivalent to the number of hydrogen ions
in the equation is added to both sides of the equation. This can then be simplified. This
method is simpler than other methods.
For example, balance the equation below in a basic medium.
Cr3+ + IO3- I - + CrO42-
Step 1: Cr3+ CrO42-
IO3- I-
Step 2: Balancing each half-reaction atomically
Cr3+ + 4H2O CrO42- (4H2O added to balance 4
oxygen atoms)
Cr3+ + 4H2O CrO42- + 8H+ (8H+ added to balance for
8 hydrogen atoms introduced by 4H 2O)
IO3- I- + 3H2O (3H2O added to balance 3 oxygen
atoms)
IO3- + 6H+ I- + 3H2O (6H+ added to balance the 6 hydrogen
atoms introduced by 3H 2O)
Step 3: Balancing each half reaction electrically
Cr3+ + 4H2O CrO42- + 8H+
+3 +6 this implies that 3 electrons should be
added to the right-hand side
Cr3+ + 4H2O CrO42- + 8H+ + 3e-………………..(1)
For IO3- + 6H+ I- + 3H2O
+5 -1 this implies that 6 electrons should be
added to the left-hand side
IO3- + 6H+ + 6e- I- + 3H2O…………………………(2)
Step 4: Combining the two half-equations
(1) x 2 2Cr3+ + 8H2O 2CrO42- + 16H+ + 6e-……………..(3)
(2) IO3- + 6H+ + 6e- I- + 3H2O…………………………(2)
(3) + (2) 2Cr3+ + 8H2O + IO3- + 6H+ 2CrO42- + 16H+ + I- + 3H2O
simplifying we have
2Cr3+ + 5H2O + IO3- 2CrO42- + 10H+ + I-
Step 5: To balance the reaction in a basic medium add 10 OH- to both sides
2Cr3+ + 5H2O + IO3- + 10 OH- 2CrO42- + I- + 10H+ + 10 OH-
2Cr3+ + 5H2O + IO3- + 10 OH- 2CrO42- + I- + 10H2O
Step 6: Simplying step 5 by collecting like terms, we have
2Cr3+ + IO3- + 10 OH- 2CrO42- + I- + 5H2O
Balancing a disproportionation reaction
A disproportionation reaction is a reaction in which the same substance (on the reactant side)
that is being oxidized is also being reduced.
An example is P4(s) + OH-(aq) H2PO2-(aq) + PH3(g) +
H2O
Step 1: P4 H2PO2-
P4 PH3
Step 2: (a) balancing P
P4 4H2PO2-
P4 4PH3
(b) balancing O
P4 + 8H2O 4H2PO2-
P4 4PH3
(c) balancing H
P4 + 8H2O 4H2PO2- + 8H+
P4 + 12H+ 4PH3
Step 3: Balancing the half-equations electrically
P4 + 8H2O 4H2PO2- + 8H+ + 4e-……………….(1)
P4 + 12H+ + 12e- 4PH3………………………….(2)
Balancing a disproportionation reaction

Step 4: Combining the half-reactions

(1) x 3 3P4 + 24H2O 12H2PO2- + 24H+ + 12e-……………….(3)
(2) P4 + 12H+ + 12e- 4PH3…………………………...….(2)
(3) + (2) 4P4 + 24H2O 12H2PO2- + 4PH3 + 12H+
Step 5: For the reaction to be in a basic medium, add 12 OH- to both sides
4P4 + 24H2O + 12 OH- 12H2PO2- + 4PH3 + 12H+ + 12 OH-
4P4 + 24H2O + 12 OH- 12H2PO2- + 4PH3 + 12H2O
Step 6: Simplifying the net equation by collecting like terms we have
4P4 + 12H2O + 12 OH- 12H2PO2- + 4PH3
dividing through by 4 we have
P4 + 3H2O + 3 OH- 3H2PO2- + PH3
In disproportionation reaction, a particular substance splits into two different oxidation
states in the products. One is the oxidized form while the other is the reduced form.
 Balancing a conproportionation reaction
In this case, we may have the same element in two different
compounds in the reactants coming together to form the only
product or one of the products. In this process, one is
oxidized to the product, while the other is reduced to the
product. This example is known as conproportionation
reaction. Such equations can be balanced in the same way as
the disproportionation reaction. An example is

HIO3 + HI + H+ I2 + H2O

There are a number of practical problems that involves redox

reactions, in such problems the redox equations must be
balanced first and then apply the mole ratio obtained from it
for calculations.
 Oxidizing and Reducing agents
The substance that is oxidized is the reducing agent because it is the
one that made it possible for the other substance to be reduced. The
substance that is reduced is therefore the oxidizing agent.
A compound that is an oxidizing agent in a reaction can be a reducing
agent in another reaction. This is essentially due to whether it is
reduced or oxidized in the reaction.
For example, hydrogen peroxide can behave as both an oxidizing agent and a reducing agent
depending on the substance it is reacting with as in the following reactions

i) H2O2(aq) + 2Fe2+(aq) + 2H+(aq) 2H2O + 2Fe3+(aq)

ii) 5H2O2(aq) + 2MnO4-(aq) + 6H+(aq) 8H2O + 2Mn2+(aq) + 5O2(g)
iii) H2O2(aq) + Cl2(g) + 2 OH-(aq) 2H2O + 2Cl-(aq) + O2(g)

In (i) H2O2 oxidized Fe2+ to Fe3+, therefore it is an oxidizing agent in this reaction.
(ii) H2O2 reduced MnO4- to Mn2+, it is therefore a reducing agent in this reaction.
(iii) H2O2 reduced Cl2 to Cl-, it is therefore a reducing agent in this reaction.
Some common strong oxidizing agents are
Permanganate ion (MnO4-)
Ozone (O3)
Hypochloride ion (OCl-)
Some common strong reducing agents are
Carbon (C)
Thiosulphate ion (S2O32-)
Iodide ion (I-)
 Exercise 1
Calculate the oxidation number of carbon in the following compounds
a) CO b) CO2 c) COCl2 d) CaCO3
e) CCl4 f) CH4 g) H2CO h) HCO2H

What is the oxidation number of manganese in each of the following compunds?

a) KMnO4 b) Mn2O7 c) MgMnO3 d) MnO e) MnO2

Assign oxidation number to each of the elements in the following compounds

a) OF2 b) HOF c) O2F2 d) PH3
e) CaH2 f) PH4+ g) ClF3 h) MnO42-
 Exercise 2
State whether the following reactions are redox reactions or not. If they are, identify
the oxidizing agents and the reducing agents.
a) PH3(g) + HCl(g) PH4Cl(s)
b) SiO2(aq) + 3C(s) SiC(s) + 2CO(g)
c) Cu(s) + 2H2SO4(aq) CuSO4(aq) + SO2(g) + 2H2O(l)
d) NaI(aq) + 3HOCl(aq) NaIO3(aq) + 3HCl(aq)
e) I2(g) + 10HNO3(aq) 2HIO3(aq) + 10NO2(g) + 4H2O(l)
f) 2HBr(aq) + H2SO4(aq) SO2(g) + Br2(g) + 2H2O(l)

Write a balanced equation for each of these half-reactions in an acidic medium

a) Cl2 ClO3-
b) H4IO6- I
c) Fe Fe(OH)2
d) BiO3- Bi3+
e) NO3- NH4+
 Exercise 3
Balance the following redox reactions, which occur in an acid medium.
a) UO2+ + NO3- + H+ UO22+ + NO + H2O
b) S2O32- + MnO4- SO42- + Mn2+
c) H2S + CrO42- S8 + Cr3+
d) Br2 + SO2 H2SO4 + HBr
e) BrO3- + Cr3+ Br2 + HCrO4-

Write a balanced equation for the following reactions, which occur in a basic medium
a) As2S3 + H2O2 AsO43- + H2O + SO42-
b) NO + MnO4- NO3- + MnO2
c) Fe(OH)2 + O2 Fe(OH)3 + H2O
d) CN- + MnO4- MnO2 + CNO- + H2O
e) NH3 + MnO4- N2 + MnO2
 ELECTROCHEMISTRY
•is the study of how chemical reactions
can be used to produce electricity

•how electricity can be used to produce

chemical reactions.
• Electricity involves a flow of
electrons.
 APPLICATIONS OF
ELECTROCHEMISTRY
• include batteries and fuel cells as
electric power sources
• manufacturing of chemicals
• refining of metals
• Electroplating
• methods of controlling corrosion
 ELECTRODE POTENTIAL
• When a Cu metal is put in each of the following
solutions; AgNO3(aq) and Zn(NO3)2(aq)
• a redox reaction occurs between Cu(s) and Ag+
in the solution containing AgNO3(aq) but not
between Cu(s) and Zn2+ in the solution
containing Zn(NO3)2 (aq).
• The difference in behaviour of the two solutions
is due to their metal ion electrode potential.
• Ag+ is easily reduced than Zn2+.
 ELECTROCHEMISTRY
• When a strip of metal, M, is put in a solution
containing metal ion Mn+, the metal, M, is called
an electrode because it allows the passage of
electrons.
• The combination of the metal, M, and the
solution containing Mn+ is called a half-cell or a
half-equation (electrode and solution).
• There are three types of possible interactions
between the electrode and the solution
(electrolyte).
 POSSIBLE INTERACTIONS BETWEEN
THE ELECTRODE AND ELECTROLYTE
• A metal ion Mn+ may collide with the electrode
and undergo no change
• A metal ion Mn+ may collide with the electrode
and gain ‘n’ electrons to be converted to metal
M, the ion is said to be reduced.
Mn+(aq) + ne- → M(s)
• A metal atom may lose ‘n’ electrons and enter
into the solution. The metal atom is said to be
oxidized M(s) → Mn+(aq) + ne-
 POSSIBLE INTERACTIONS BETWEEN
THE ELECTRODE AND ELECTROLYTE
• These possibilities can be represented as:
M(s)  Mn+(aq) + ne-.
• If we have two different metals, M
(electrodes), electrons will flow from
electrode of higher negative charge density
(electrode potential) to electrode of lower
potential. A small difference in electrode
potentials is enough to set up electric current.
 MEASUREMENT OF DIFFERENCE IN
POTENTIAL BETWEEN TWO ELECTRODES
• This difference can only be measured when the
two half-cells are connected.
• The electrodes are normally connected by a wire
to permit the flow of electrons while the
solutions are normally connected through a
porous plug or a membrane or another solution
usually in a U- tube. This connection is called a
salt bridge.
• The salt bridge allows the passage of electric
current in form of migration of ions.
This set-up is called electrochemical cell and an
example is shown below;
 The Electrochemical Cell
Zn atom from the electrode will lose
electrons and become Zn2+ in solution.
The electrons lost by the Zn atom will pass
through the wire and the potentiometer to
the Cu(s) electrode.
These electrons will be gained by Cu2+ ion
solution to become Cu(s) and subsequently
Cu(s) will be deposited at the Cu electrode.
 The Electrochemical Cell
Without a salt bridge,
there will be excess Zn2+, that is, a net
positive charge at the Zn half-cell.
A deficiency of Cu2+, that is, a negative
charge will be observed at the Cu half-cell,
therefore electric current would not
continue to flow.
 The Electrochemical Cell
Salt bridge solves this problem.
The anions (SO42-) from the salt bridge
migrate to the Zn half cell to neutralize the
net positive charge
while the cations (Na+) from the salt bridge
migrate to the Cu half-cell to neutralize the
net negative charge.
Current now flows through the solutions.
The equation of the reaction is:

Oxidation Zn(s) → Zn2+(aq) + 2e-

Reduction Cu2+(s) + 2e- → Cu(s)
Net Zn(s) +Cu2+(aq) → Zn2+(aq) + Cu(s).
The reading of potentiometer is 1.10V.

This is what is called the potential

difference between the two half-cells.

It is also called electromotive force

(emf) because it is a driving force and
sometimes called cell potential or cell
voltage.
 POTENTIOMETER
• is an electrical device that produces voltage of
known values.
• measures the potential difference in the cell
precisely by generating enough voltage that
opposes the current in the cell.
• The value of voltage it generates to do this, is
equal to the value of voltage from the cell.
• Special voltmeters that draw only a very little
current can also be used to measure the
voltage generated from the cell directly.
 POTENTIOMETER
• Anions from the salt bridge migrates to the Zn
half-cell, the electrode in this cell is called an
anode.
• always on the left side of the diagram.
• Cations from the salt bridge migrates to the
Cu half-cell, this electrode is called a cathode.
It is a negative electrode where reduction
takes place and is always on the right side of
the diagram.
 POTENTIOMETER
• Instead of describing an electrochemical cell
or drawing a cell diagram, cell notation can be
used.
• Boundaries (interface) between electrodes
and solutions - a single vertical line (│).
• Boundaries between solutions - a double
vertical line (║), if it is a salt bridge and a
series of vertical dots is use (  ), if it is a
porous plug or a membrane.
 POTENTIOMETER
• For example the cell diagram above can be
written as;

Zn(s)│Zn2+(aq) ║ Cu2+(aq)│Cu(s)
Oxidation salt bridge Reduction
(Anode) (Cathode)
 ELECTROCHEMISTRY
•Is the study of the relationship between chemical
reactions and electrical energy
•Is the study of how chemical reactions can be used to
produce electricity and how electricity can be used to
produce chemical reactions.
Chemical reaction Electrical Energy
• Electricity involves the flow of electrons.

• Applications of electrochemistry include: as electric

power sources in batteries and fuel cells , manufacturing
of chemicals, refining of metals, Electroplating, methods
of controlling corrosion 1
 ELECTROCHEMISTRY
Electricity passes through a circuit under the
influence of a potential or voltage, (the driving force
of the movement of charge)
The potential difference is the work done per unit
charge to move a unit charge from one point to
another in an electric field
The tendency of a metal to loss or gain electron
oxidation potential -tendency to lose electrons
reduction potential - tendency to gain electrons
Electrode- a conductor which allows the passage
of electric current 2
 ELECTRODE POTENTIAL

Zn(s) in Cu(NO3)2(aq) Cu(s) in Zn(NO3)2(aq) Cu(s) in AgNO3(aq)

Deposit of Cu(s) NO METAL DEPOSIT Deposit of Ag(s)
The difference is due to their metal ion electrode potential.
A metal cannot displace another metal with a higher
negative electrode potential. Hence, Cu (E0 = +0.34V)
cannot displace Zn (Eo = -0.76V) from Zn2+ solution, but
can displace Ag (Eo = +0.80 V) from Ag+ solution 3
 ELECTROCHEMISTRY
• When a strip of metal, M, is put in a solution
containing metal ion Mn+, the metal, M, is called
an electrode
• The combination of the metal, M, and the
solution containing Mn+ is called a half-cell or a
half-equation (electrode and solution).
• There are three types of possible interactions
between the electrode and the solution
(electrolyte).
4
 POSSIBLE INTERACTIONS BETWEEN
THE ELECTRODE AND ELECTROLYTE
• Mn+(aq) collide with M(s)  no change
• Mn+ may gain ‘n’ electrons and be converted to
M(s), (Mn+ is reduced) .
Mn+(aq) + ne-  M(s)
• M(s) may lose ‘n’ electrons and enter into the
solution. (M(s) is oxidized)
M(s)  Mn+(aq) + ne-
These possibilities can be represented as:
M(s)  Mn+(aq) + ne-. 5
 POSSIBLE INTERACTIONS BETWEEN
THE ELECTRODE AND ELECTROLYTE
• If we have two different metals, M
(electrodes), electrons will flow from
electrode of higher negative charge density
(electrode potential) to electrode of lower
negative potential.
• A small difference in electrode potentials is
enough to set up electric current.
• This difference can only be measured when
the two half-cells are connected. 6
This set-up is called electrochemical cell
• The electrodes
are connected by
a wire to permit
the flow of
electrons
• the solutions are
connected
through a salt
bridge. It allows
the passage of
(anode, negative (cathode, positive
electric current in
electrode, oxidation electrode, reduction
reaction; always on the reaction, always on form of migration
LHS). the RHS). of ions. 7
 The Electrochemical Cell
Oxidation: Zn(s)  Zn2+(aq) + 2e-
Reduction: Cu2+(s) + 2e-  Cu(s)
Net Equation: Zn(s) + Cu2+(aq)  Zn2+(aq) + Cu(s)
The reading of
potentiometer is 1.10V
This is what is called the
potential difference
between the two half-
cells.
AKA cell potential or cell
voltage or electromotive
force (emf) because it is
a driving force 8
Without a salt bridge… • there will be excess
Zn2+ (since Zn2+ is
produced), i.e a net
positive charge at the
Zn half-cell
• A deficiency of Cu2+
(since Cu2+ is
converted to Cu), , ie a
net negative charge at
With a salt bridge… the Cu half-cell
Anions from the salt bridge (SO42-)
migrates to the Zn half-cell • electric current would
Cations (Na+) migrates to the Cu not continue to flow.
9
half-cell. CURRENT FLOWS
 POTENTIOMETER
• measures the potential difference in the cell
precisely by generating enough voltage that
opposes the current in the cell.
• It produces voltage of known values equal to
the value of voltage from the cell.
• Special voltmeters that draw only a very little
current can also be used to measure the
voltage generated from the cell directly.

10
 CELL NOTATION
• cell notation -to describe electrochemical cell.
• Boundaries (interface) between electrodes and
solutions - a single vertical line (│).
• Boundaries between solutions - a double
vertical line (║), for salt bridge and a series of
vertical dots (  ) for porous plug or membrane.

Zn(s) │ Zn2+(aq) ║ Cu2+(aq) │ Cu(s)

Oxidation salt bridge Reduction
(Anode) (Cathode)
LHS RHS 11
 TYPES OF ELECTROCHEMICAL CELLS
Electrochemical Cells

Voltaic/galvanic cells Electrolytic cells

• Spontaneous reactions. • non-spontaneous
• The chemical changes • Applied electricity
produce electricity. produces chemical change
• They have positive • They have negative
voltage (Eocell > 0) voltage (Eocell < 0)
• Cathode is the negative and
• Cathode is +ive and anode is the positive
anode is negative electrode 12
Example: In the Daniel’s cell, Zn(s) displaces copper(II) in
aqueous solution. (a) write the half-cells and the net
equation (b) write a cell notation for the spontaneous
reaction.
Solution: (a) Zn(s) displaces Cu(II) ion , Zn goes into
solution to become Zn2+(aq) and Cu2+(aq) gets out of the
solution to become Cu(s).

Oxidation : Zn(s) → Zn2+(aq) + 2e-

Reduction : Cu2+(aq) + 2e- → Cu(s)
Net equation : Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s).

(b) The notation for reaction will be

Zn│Zn2+(aq)║Cu2+(aq)│Cu(s)
13
 STANDARD ELECTRODE POTENTIAL
• It would be very advantageous to be able to measure
the potential of a single electrode
• For instance :
Cu2+(aq) │ Cu(s).

• The potential would be a measure of the tendency of

the reduction process to occur:

Cu2+ + 2e- → Cu(s)

A standard reference electrode is needed for this.

This reference electrode is called standard hydrogen
electrode (SHE). Its electrode potential is taken as zero.
14
 STANDARD HYDROGEN ELECTRODE
Pt
SHE is made by
e- passing H2(g) at
1 atm pressure
H2 (g, 1 atm)
Salt bridge
over an inert
Pt metal
surface in a
solution of H+
+
whose activity
H (a= 1 M)
is 1 at 250C

15
The standard electrode (reduction) potential of
Cu2+/Cu electrode in the diagram below is 0.337V.
V=+0.337V
The emf
- + obtained is
e-
the standard
electrode
H2 (g, 1 atm) Cu
Salt bridge potential or
the standard
reduction
2+
Cu (a = 1 M)
potential of
+
H (a= 1 M)
the other cell
(Eo).

Oxidation occur in the H2 cell

Reduction takes place in the other cell (Cu cell). 16
Pt,H2(g,1atm) │H+(1M) ║ Cu2+(1M)│Cu(s) (Eo =0.337 V)
Oxidation: H2 (g, 1 atm) → 2H+(1M) + 2e-
Reduction: Cu2+(aq)(1M) + 2e- → Cu(s)
Net: H2(g,1atm) + Cu2+(1M) → 2H+(1M) +Cu(s)
Eocell = +0.337 V.
The positive value of EoCell = +0.337 V implies that Cu2+ is
more easily reduced than H+(1M).
In the case of Zn2+(1M)│Zn(s)
Pt, H2 (g,1 atm) │H+(1M) ║ Zn2+(1M)│Zn(s)
Eocell = -0.763V
The negative value of EoCell = -0.763 V implies that Zn2+ is
less easily reduced than H+(1M). (Oxidation, Current will
flow in the opposite direction, from Zn electrode to the
SHE) 17
 STANDARD ELECRODE (REDUCTION)
POTENTIALS.
Half-reactions in Acidic solution. Eo/V
• F2 + 2e- → 2F-(aq) 2.866
• O3 + 2H+(aq) + 2e- → O2(g) + H2O 2.07
• S2O82-(aq) + 2e- → 2SO42-(aq) 2.01
• H2O2(aq) +2H+(aq) → 2H2O 1.77
• Ce4+(aq) + e- → Ce3+(aq) 1.72
• Au+(aq) + e- → Au(s) 1.692
• MnO4-(aq) + 8H+ +5e- → Mn2+ + 4H2O 1.52
• PbO2(s) + 4H+(aq) + 2e- → Pb2+ + 2H2O 1.455
• Cl2 + 2e- → 2Cl-(aq) 1.360
• Cr2O72-(aq) + 14H+(aq) + 6e- → 2Cr3+(aq) + 7H2O 1.332
• O2(g) + 4H+(aq) + 4e- → 2H2O 1.229 18
 STANDARD ELECRODE (REDUCTION)
POTENTIALS.
Half-reactions in Acidic solution. Eo/V
• MnO2(s) + 4H+(aq) + 2e- → Mn2+(aq) + 2H2O 1.224
• 2IO3-(aq) + 12H+(aq) + 10e- → I2 + 6H2O 1.195
• Pt2+ + 2e- → Pt 1.18
• Br2(l) + 2e- → 2Br-(aq) 1.065
• NO3-(aq) + 4H+(aq) + 3e- → NO(g) + 2H2O 0.96
• Hg2+(aq) + 2e- → Hg(s) 0.851
• Ag+(aq) + e- → Ag(s) 0.800
• Fe3+(aq) + e- → Fe2+(aq) 0.771
• O2(g) + 2H+(aq) + 2e- → H2O2(aq) 0.682
• I2(s) + 2e- → 2I-(aq) 0.535
19
 STANDARD ELECRODE (REDUCTION)
POTENTIALS.
Half-reactions in Acidic solution. Eo/V
• Cu+(aq) + e- → Cu(s) 0.52
• H2SO3(aq) + 4H+(aq) + 4e- → S(s) +3H2O 0.45
• Cu2+(aq) + 2e- → Cu(s) 0.337
• Sn4+(aq) + 2e- → Sn2+(aq) 0.154
• S(s) + 2H+(aq) +2e- → H2S(g) 0.141
• 2H+(aq) + 2e- → H2(g) 0.0000
• Pb2+(aq) + 2e- → Pb(s) -0.126
• Sn2+(aq) + 2e- → Sn(s) -0.136
• Cr3+(aq) + e- → Cr2+(aq) -0.407
• Fe2+(aq) + 2e- → Fe(s) -0.440
20
STANDARD ELECRODE (REDUCTION)
POTENTIALS.
Half-reactions in Acidic solution. Eo/V
• Zn2+(aq) + 2e- → Zn(s) -0.763
• Al3+(aq) + 3e- → Al(s) -0.1.66
• Mg2+(aq) + 2e- → Mg(s) -2.375
• Na+(aq) + e-→ Na(s) -2.714
• Ca2+(aq) + 2e- → Ca(s) -2.76
• K+(aq) + e- → K(s) -2.925
• Li+(aq) + e- → Li(s) -3.045

21
 STANDARD ELECRODE (REDUCTION)
POTENTIALS.
BASIC SOLUTION Eo/V
• O3(g) + H2O +2e- → O2(g) + 2OH- +1.24
• OCl-(aq) + H2O + 2e- → Cl- + 2OH- +0.89
• O2(g) + 2H2O + 4e- → 4OH-(aq) +0.401
• CrO42-(aq) + 4H2O + 3e- → Cr(OH)3(s) + 5OH- -0.13
• S(s) + 2e- → S2-(aq) -0.48
• 2H2O + 2e- → H2(g) + 2OH-(aq) -0.828
• SO42-(aq) + H2O + 2e- → SO32-(aq) + 2OH-(aq)-0.93

22
 CALCULATION OF STANDARD ELECTRODE
(REDUCTION) POTENTIAL OF A CELL
• Eo is calculated by combining the standard electrode
potential of the half-cell reactions. The steps are:
• Step 1: Write out the reduction equations for the half-
cells and their standard reduction potential.
• Step 2: For oxidation half-cell reactions, reverse the
reduction equation. Hence Eo will become -Eo.
• Step 3: Balance the number of electrons in the 2 half-
equations. Note however that potential is an intensive
property and therefore Eo values are not affected by
the multiplying factors of the half-cell reactions.
• Step 4: Add the oxidation and reduction equations and
do the same for their Eo. 23
Example: Calculate the Eo cell of a Daniel cell, the
half-cells equation is
Zn│Zn2+(aq) (1M)║Cu2+(aq) (1M)│Cu(s)

Solution: The reduction half equations involved are

Cu2+(aq) + 2e- → Cu(s) = 0.337 V (or EoCu2+/Cu = 0.337 V)
Zn2+(aq) + 2e- → Zn(s) = -0.763 V (or EoZn2+/ Zn =-0.763V)

The oxidation equation is Zn(s) → Zn2+(aq) + 2e- Eo = 0.763V

(sign changed from negative to positive)

The Eo cell for the cells will be EoZn/Zn2+ + EoCu2+/Cu = Eo cell.

Oxidation: Zn(s) → Zn2+(aq) + 2e- Eo = 0.763V
Reduction: Cu2+(aq) + 2e- → Cu(s) Eo = 0.337V
Net: Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) Eo = 1.100V
24
Example: A new battery under test for commercial uses is
the Zinc-Chlorine battery, its Eocell is 2.123 V. Given that the
standard reduction potential of Zn is -0.763V, calculate the
standard reduction potential of Chlorine.

Solution:
The net reaction of this cell is Zn(s) + Cl2(g) → ZnCl2(aq)
Therefore, the half-equations are
Oxidation: Zn(s) → Zn2+ + 2e- Eo = -(-0.763)
Reduction: Cl2(g) + 2e- → 2Cl-(aq) Eo = x V
Zn (s) + Cl2(g) → Zn2+ + 2Cl- (aq) Eocell =2.123V.

EoZn/Zn2+ + EoCl2/2Cl- = Eo cell.

0.763V + Eo Cl2/2Cl- = 2.123V.
Eo Cl2/2Cl- = 2.123 - 0.763V.
25
= 1.360V.
It should be noted that, the oxidation and reduction standard
potentials couldn’t just be added up or subtracted if there
are electrons left in the net reaction.
For example, calculating the Eo of
Cu+ + e- → Cu
From the following half-equations cannot just be treated like
it was done in the previous example
Cu2+ + e- → Cu+ Eo = 0.153 V
Cu2+ + 2e- → Cu Eo = 0.337 V.
giving Cu+ → Cu2+ + e- Eo = -0.153 V
Cu2+ + 2e- → Cu Eo = 0.337 V.
Cu+ + e- → Cu Eo  0.184 V.
This is wrong!
NOTE that once there are electrons in the net equation, Eo
should be calculated through the Go procedure. 26
The correct solution in this case, where an electron is left in
the net equation, has to be calculated through the Go of the
two half reactions.
Cu2+ + e- → Cu+ G1o = -nE1oF = -1 x 0.153 x 96485 J mol-1
Cu2+ + 2e- → Cu G2o = -nE2oF = - 2 x 0.337 x 96485 J mol-1.
The Gxo for the reaction of Cu+ + e- → Cu
is Gxo = G2o - G1o
= {(- 2 x 0.337 x 96485) - (-1 x 0.153 x 96485)} J mol-1
= (0.153 –0.674) 96485 J mol-1
= -0.521 x 96485 J mol-1
Since Gxo for the reaction of Cu+ + e- → Cu
= -nxExoF and nx = 1, F = 96485 C mol-1
-Exo x 96485 = -0.521 x 96485
Therefore Exo = 0.521 V
For any of the previous examples, going through the Go will
27
still give the same answer as the direct additions
For example, calculating the Eocell for the reaction
Zn + Cu2+ → Zn2+ + Cu giving that
Zn2+ + 2e- → Zn E1o = -0.763 V
Cu2+ + 2e- → Cu E2o = 0.337 V.
Gxo = G2o - G1o
-nxExoF = (-n2E2oF) – (-n1E1oF)
-2ExoF = {-2 x 0.337F} – {-2 x (-0.763)F}
-2ExoF = -2F (0.337 + 763)
Exo = 0.337 + 0.763 V = 1.100 V

It is important to note that once there are

electrons in the net equation, Eo should be
calculated through the G procedure.
o 28
 FEASIBILITY OF REDOX REACTIONS AND
GIBB’S ENERGY CHANGE IN A CELL.
• Feasibility of redox reactions simply implies the
spontaneity of the reaction.
• If a reaction is spontaneous, it shows that the reaction
occurs without any external input.
• The maximum useful work done by a system at
constant pressure is equal to the change in Gibb’s free
energy of the system. ∆G = Wmax(useful). Since work
done by a system is negative, therefore the ∆G of a
spontaneous reaction is negative, that is, ∆G < 0.
• For a non-spontaneous reaction ∆G > 0.
• Wmax(useful). = Welec (Welec is Welectrochemical cell) because it’s
the only non pressure-volume work in this process. 29
FEASIBILITY OF REDOX REACTIONS AND GIBB’S
ENERGY CHANGE IN A CELL.
Welec = - nFEcell where
‘n’ is the number of moles of electrons
F is Faraday’s constant, that is the electric charge per mole of
electrons and is approximately 96485 Coulumbs per mole of
electrons (C/mol.e-).
Ecell is the emf (potential difference of the cell in volts).
∆G= -nFEcell and in the standard states ∆Go = -nFEo cell
• From the equation above, ∆G can only be negative (∆G< O)
when Ecell is positive (Ecell>0). Therefore when Ecell is positive
the reaction occurs spontaneously (REACTION IS POSSIBLE)
and when Ecell is negative, the reaction is non-spontaneous
in the forward direction. When Ecell is equal to zero, then the
reaction is in equilibrium. 30
Example: Calculate the standard free energy change, ∆Go of
Daniel cell from the reduction potential of Zn and Cu.
Comment on the process spontaneity (Eo Zn2+/Zn = -0.763 V
and EoCu 2+/Cu = 0.337 V)
Solution :
Zn(s) → Zn2+ + 2e- Eo = 0.763V
Cu2+ + 2e- → Cu Eo = 0.337V
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s) Eo = 1.100V

∆Go = -nFEo cell.

n = 2 , F = 96485 C/mole of e-
= -2 mole of e- x 96485C x 1.1V
mole of e-
= -212265CV = -212265J
= -212.3 kJ.
31
Reaction is Spontaneous since ∆Go is negative
Example: Will magnesium displace Al3+ ion from its
solution? Given that,
Mg2+(aq) + 2e- → Mg(s) Eo = -2.375V
Al3+(aq) + 3e- → Al(s) Eo = -1.660V

Solution:
Oxidation: Mg → Mg2+ + 2e- Eo = 2.375V
Reduction: Al3+ + 3e- → Al(s) Eo = -1.660V
To balance the number of electrons we have;
3Mg → 3Mg2+ + 6e- Eo = 2.375V
2Al3+ +6e- → 2Al(s) Eo = -1.660V
Net : 3Mg(s) + 2Al3+(aq) → 3Mg2+(aq) +2Al(s) Eo = 0.715V
Since Eocell is positive, the reaction will be spontaneous, hence
Mg will displace Al3+ ion from its solution.
32
Calculation of equilibrium constant, K, from Eocell
It is already stated that ∆G = -nFEocell.
From thermodynamics, ∆Go = -RT ln K or ∆Go = -2.303 RT logK
Where R is gas constant, (8.314 J mol-1K-1),
T is the absolute temperature and
K is the equilibrium constant.
-RT lnK = -nFEocell
Eocell = RT ln K
nF
- 2.303 RT log K = -nFEocell or Eocell = 2.303 RT log K
nF
At standard conditions T is equal to 250C =298K and
R = 8.314 J mol-1K-1, F = 96485 C/mol e-.
Eocell = 0.0592 log K
n 33
Example: Calculate the equilibrium constant at 250C
for the reaction occurring in Daniel cell.
Zn(s)/Zn2+(aq) (1M) ║ Cu2+(aq) (1M)/Cu.
Solution:
It has been shown from previous examples that the
standard emf of this cell is 1.100V, and n is equal to
two.
Eocell = 0.0592 log K
n
Log K = n x Eocell = 2 x 1.10
0.0592 0.0592

K = 1.5 X 1037 34
Example : Calculate the equilibrium constant for the
reaction H2(g) + 2Fe3+(aq) → 2H+(aq) + 2Fe2+(aq)
Given that 2H+(aq) + 2e- → H2 (g) Eo = 0 V
Fe3+(aq) +e- → Fe2+(aq) Eo = 0.771 V
Solution: The net equation is written as ;
H2(g) → 2H+(aq) + 2e- Eo = 0.0V
2Fe3+(aq) + 2e- → 2Fe2+(aq) Eo = 0.771V
H2(g) + 2Fe3+(aq) → 2H+(aq) + 2Fe2+(aq) Eocell = 0.771V
n = 2 and Eo = 0.771V
0.771 = 0.0592 log K K = 1.14 x 1026 mol2 dm-6
2
The unit of K is determined from the equation . The ionic
species in the aqueous medium are Fe3+, H+, Fe2+.
The unit of K = [Fe2+](mol dm-3)2 [H+] (mol dm-3)2
[Fe3+] (mol dm-3)2
35
= mol dm2 -6.
The equilibrium constant of the reaction;
½H2 + Fe3+ → H+ + Fe2+ given from that of
H2 + 2Fe3+ → 2H+ + 2Fe2+
but their Eo will be the same.
½H2 → H+ + e- Eo = 0V
Fe3+ + e- → Fe2+ Eo = 0.771V
but in this case n = 1.
Therefore, 0.771 = 0.0592 log K
1
K = 1.1 X 1013 mol dm-3
The value is actually the square root of 1.14 x1026 mol2 dm-6.
Various types of equilibrium constants can be calculated from
the standard cell potentials of reactions. Below are examples
of how solubility products and complex formation equilibrium
constants are calculated.
36
Example: Calculate the solubility products of AgCl(s) given
that Ag+(aq) + e- → Ag(s) Eo = 0.800 V
AgCl(s) + e- → Ag(s) + Cl -(aq) Eo = 0.220 V
Solution: The equation for finding the solubility product of
AgCl(s) is AgCl(s) → Ag+(aq) + Cl-(aq)
To obtain this equation, we reverse the first equation and
then add it to the second equation.
Oxidation: Ag(s) → Ag+(aq) + e- Eo = -0.800 V
Reduction: AgCl(s) + e- → Ag(s) + Cl-(aq) Eo = 0.220 V
Net: AgCl(s) → Ag+(aq) + Cl-(aq) Eocell = -0.580 V
Since Eocell = RT ln K
nF
ln Ksp = nFEo = 1 x 96485 (-0.58) = -22.587
RT 8.314 x 298
Ksp = e-22.587 = 1.55 x 10-10 37
Example: Given that
Zn(NH3)42+(aq) + 2e- → Zn(s) + 4NH3(g) Eo = -1.040 V
Zn2+(aq) + 2e- → Zn(s) Eo = -0.763 V , calculate
the complex formation equilibrium constant for Zn(NH3)42+.
Solution: The equation for the formation of Zn(NH3)42+
complex is Zn2+(aq) + 4NH3(g) → Zn(NH3)42+(aq)
To get this equation, we reverse the first equation and then
add it to the second one.
Oxidation: Zn(s) + 4NH3(g) → Zn(NH3)42+(aq) + 2e- Eo = 1.040 V
Reduction: Zn2+(aq) + 2e- → Zn(s) Eo = -0.763 V
Net: Zn2+(aq) + 4NH3(g) → Zn(NH3)42+(aq) Eocell = 0.277 V
At equilibrium Ecell = 0
ln Kf = nFEo = 2 x 96485 (0.277) = 21.575
RT 8.314 x 298
Ksp = e21.575 = 2.344 x 109
38
 NERNST EQUATION
• This equation shows the relationship between
electrode potential and concentration of the reactants.
It is named after Walter Nernst (1864-1941) who first
established the relationship at standard conditions.
Zn(s) + Cu2+(1M) → Zn2+(1M) + Cu(s) Eo = 1.100V

• At non-standard conditions like;

Zn(s) + Cu2+ (0.2M) → Zn2+(0.1M) + Cu Ecell = ?
• The value of electrode potential, Ecell, depends on the
ratio of the concentration of Zn2+ to Cu2+.
• The effect of concentration change of either the
reactant or the products is determined from Le
Chatelier’s principle. 39
 NERNST EQUATION
• If we have a reaction ; aA + bB  cC + dD.
• K = ( aC)c (aD)d (K is equilibrium constant)
• (aA)a (aB)b
• a = partial pressure for gases or a = molar
concentration for liquid components.
• where a = 1 for pure solids and liquids.

• Therefore, Ecell = Eocell - 2.303.RT log ( aC)c (aD)d

nF (aA)a (aB)b
• It is also possible to look at the effect of change in
temperature on Eocell. 40
 NERNST EQUATION
• If we have a reaction ; aA + bB  cC + dD.
• From thermodynamics; ∆G = ∆Go + RT ln K
that is,
• ∆G = ∆Go + 2.303 RT log K.
• since ∆G = -nFEcell and ∆Go = -nFEocell
• then we have; -nFEcell = -nFEocell + 2.303RTlogK
dividing through by -nF
• Ecell = Eocell - 2.303RTlogK
• nF
• K = ( aC)c (aD)d (where a = 1 for pure solids
• (aA)a (aB)b and liquids).
• a = partial pressure for gases and a = molarity
concentration for components. 41
Example: Calculate the emf of the cell
Co/ Co2+(0.1M) // Ni 2+(1M) / Ni at 25oC.
Given that Ni2+ + 2e- → Ni Eo = -0.257V
Co2+ + 2e- → Co Eo = -0.280V
Solution:
Oxidation: Co → Co2+ + 2e- Eo = 0.280V
Reduction: Ni2+ + 2e- → Ni Eo = -0.257V
Net: Co + Ni2+ → Co2+ + Ni Eo = 0.023V
n =2 Ecell = Eocell - 2.303RT log [Co2+]
nF [Ni2+]
= 0.023 - 2.303 x 8.314x298 log [0.1]
2 x 96485 [1]
= 0.023 - 0.0592 log {1/10}
2
= 0.023 + 0.0296
42
= 0.052V ≈ 0.053V
Example: Calculate the Ecell for
• Pt/Sn2+(0.1M), Sn4+(0.2M)//Ag+(1.0M)/ Ag(s) at 25oC.
• Given that Eo(Sn4+/Sn2+) = 0.154V and Eo(Ag+/Ag) = 0.800V
Solution: Oxidation: Sn2+(aq) → Sn4+(aq) + 2e- Eo = -0.154V
• Reduction: 2Ag+(aq) + e- → Ag(s) Eo = 0.800V
Net: Sn2+(aq) + 2Ag+(aq) → Sn4+(aq) + 2Ag(s) Eocell = 0.646V
From Nernst equation,
• Ecell =Eocell - 0.0592 log [Sn4+]
• n [Sn2+][Ag+]2
n = 2, Eocell = 0.646, [Sn4+] = 0. 2M, [Sn2+] = 0.1M, [Ag+] = 0.1M
• Ecell = 0.646 - 0.0592 log 0.2
• 2 0.1x12
• = 0.646 - 0.0592 log 2
• 2
• = 0.646 - (0.0296x0.301
• = 0.646 - 0.009
• = 0.637V 43
• Example: In the above equation, what is the minimum
[Ag+] at which the cell is able to function as voltaic cell with
Sn2+/Sn4+ as anode?
Solution: the minimum concentration of [Ag2+] will make Ecell
to be equals to zero.
• Ecell = Eocell - 0.0592 log [Sn4+]
• n [Sn2+][Ag+]2
•
• 0 = 0.646 - 0.0592 log 0.2
• 2 0.1x[Ag+]2
• log 2.00 = 0.646 = 21.824
• [Ag+]2 0.0296
• 2.00 = 1021.824
• [Ag+]2
[Ag+] = 1.731 x 10-11 M 44
The concentration of an ion in a redox reaction can also be calculated from
Nernst’s equation, if the other parameters are known
Example: Calculate the molar concentration of Fe3+ ion in the cell
• Ni/Ni2+(0.02 M)//Fe3+(x M), Fe2+(0.2 M)/Pt at 25oC.
Given that the Ecell is 1.053 V, EoFe3+/Fe2+ = 0.770 V and EoNi2+/Ni = -0.230 V
Oxidation Ni → Ni2+ + 2e- Eo = -(-0.230 V) = 0.230 V
Reduction 2Fe3+ + 2e- → 2Fe2+ Eo = 0.770 V
Net: Ni + 2Fe3+ → Ni2+ + 2Fe2+ Eocell = 1.000 V
Using Nernst equation Ecell = Eocell - RT ln K ;
nF
• 1.053 = 1 – 8.314 x 298 ln [Ni2+][Fe2+]2
• 2 x 96485 [Fe3+]2
• 0.053 = - 0.01284 ln (0.02)(0.2)2 ; - 4.1277 = ln 0.0008
• x2 x2
• 0.0008 = e-4.1277 ; x2 = 0.0008
• x2 0.0161
• x2 = 0.0496 ; x = 0.223 M. 45
 CONCENTRATION CELLS
• These are voltaic cells having the same species on
the two half-cells but with different concentrations.
The Eocell for these cells is normally zero {0}.

• pH: A popular example of a concentration cell

comes into being while measuring the pH of a
solution. One of the half-cells is the standard
hydrogen electrode (SHE) and the other is a
hydrogen electrode immersed in a solution of
unknown concentration of hydrogen ion.
46
 CONCENTRATION CELLS
• Pt, H2 (g, 1atm) / H+ (x M) // H+ (1M) / H2 (g, 1atm), Pt.
• Oxidation: H2 (g, 1atm) → 2H+ (xM) + 2e- Eo = 0.000V
• Reduction: 2H+(1M) + 2e- → H2 (g, 1atm) Eo = 0.000V
• Net: 2H+(1M) → 2H+(xM) Eocell = 0.000V
• At 25oC. Ecell = Eocell - 0.0592 x log x2
• 2 12
• Ecell = 0 - 0.592 x 2 log x
• 2
• = - 0.0592 log x.
• Since (x) is (H+) then, -log x = - log (H+) = pH.
• Therefore,
• Ecell =0.0592pH 47
SILVER ELECTRODE
The SHE is not the most convenient electrode because of the
necessity of bubbling hydrogen over the platinum electrode.
A common type of secondary standard electrodes is one, in
which silver electrode is in contact with solid silver chloride,
which is a highly insoluble salt. The whole is immersed in
potassium chloride solution in which the chloride ion
concentration is 1 molar.
Ag / AgCl(s) / Cl (1M).
A cell involving this electrode (silver chloride) and hydrogen
electrode gives a voltage of 0.022233V at 25oC.
Pt, H2 (1atm)/H+(1M)//Cl- (ion)/AgCl(s)/Ag
The half-equations are
• ½H2→H+ + e-
• e- +AgCl→Ag +Cl-
• ½H2 + AgCl → H+ +Cl- + Ag 48
CALOMEL ELECTRODE
Another type of secondary electrode is the calomel
electrode. Mercury is in contact with mercurous
chloride (calomel) immersed either in 0.1 M KCl or
in a saturated KCl solution.
• The emf of this cell at 25oC is 0.3337 V.

• Pt, H2 (g, 1atm)/H+ (1M)//Cl- (0.1M)/Hg2Cl2(s)/Hg

• ½H2 → H+ + e-
• e- + ½Hg2Cl2 → Hg + Cl-
______________________
• ½H2 + ½Hg2Cl2 → H+ + Cl- + H+ 49
 GLASS ELECTRODE
The most convenient secondary standard electrode
is the glass electrode.
It a hollow glass tube that has a thin glass
membrane of a carefully regulated chemical
composition at the bottom.
The tube is filled in part with a dilute solution of HCl
and dipping into this solution is a silver wire
coated with a layer of silver chloride.
A potential difference is normally established on the
outer surface of the membrane when the
electrode is dipped into a solution.
50
 GLASS ELECTRODE
Since the H+ concentration inside the electrode is
constant, the potential value depends on the type
and concentration of ions present in the solution
into which the electrode is dipped.
• A glass electrode is normally used with another
reference electrode whose potential is known and
constant. A combination of these two electrodes
gives a galvanic cell whose potential depends on
the pH of the solution into which the electrode is
immersed.
• These days, we often have a combined glass
electrode in which the reference electrode is
already inserted into the glass electrode.
51
 ION-SELECTIVE ELECTRODE
• There are special electrodes that are sensitive to
other ions.
• These are called ion-selective electrode, “pX meter”.
• They can measure the concentration of various ions,
X such as Na+, K+, Ca2+, Ag+ and NH4+, we also have
such electrodes for anions like F-, Cl-, Br-, CN- and S2-

• Ordinary pH meter electrode cannot be used to

measure the concentration of Na+ and K+ because
they will react with water to liberate hydrogen gas.
52
• The concept of concentration cell is normally used
to determine the solubilty product constants of a
compound electrochemically.
• For example the solubility product of AgI is
determined as shown below:
• Ag(s)/Ag+ (saturated) AgI(aq) )//Ag+ (0.2M)/Ag(s)
Ecell = 0.435 V
•
• The anode, a silver electrode, is placed in a
saturated solution of silver iodide while the
cathode, also a silver electrode, is placed in a
solution of silver iodide of known concentration.
The two half-reactions are connected by a salt-
bridge and the cell potential is measured. 53
• The standard potential of this concentration cell is zero
because
Oxidation: Ag(s)Ag+ (sat’d) + e- Eo = -0.800 V
Reduction: Ag+ (0.2M) + 2e-  Ag(s) Eo = 0.800 V
Net: Ag+ (0.2M)  Ag+ (sat’d) Eocell = 0.000 V
• Using Nernst equation
• Ecell = Eocell - 2.303RT log [Ag+ (sat’d)]
• nF [0.200]
• 0.435 V = 0 - 0.0592 log [Ag+ (sat’d)]
• [0.200]
• 7.348 = - log [Ag+ (sat’d)] + log 0.2
• log [Ag+ (sat’d)] = log 0.2 – 7.348 = -8.047
• [Ag+] = 10-8.047 = 8.975 x 10-9 M
• Since [Ag+] = [I-]
• Ksp = [Ag+][I-] = [8.975 x 10-9][8.975 x 10-9]
• = 8.055 x 10-17
54
 Potentiometric titration
• This titration makes use of the Ecell to determine the
pH or the equivalent point of such titration.
• The solution of unknown concentration is placed at
the anode and is titrated with a strong base.
• A plot of the Ecell (or pH) versus volume of the strong
base (titration curve) shows the equivalence point.

• Can be achieved by either of these methods:

1. the concentration of one of the reactants changes
rapidly at equivalence point OR
2. an electrode can be found whose potential depends
on the concentration of the reactions.
A good example of potentiometric titration is the
titration of Ag+ with I- to precipitate AgI. 55
 ELECTROLYSIS
There are chemical changes that are non-
spontaneous because the redox reaction has a
positive free energy (G > 0); that is, the Eocell is
negative (Eocell < 0).
The process of driving a reaction in a non-
spontaneous direction by passing electric current
through the reaction is called electrolysis.
The cell in this electrochemical process is called an
electrolytic cell.
In most cases, an electrolytic cell has a single
electrolyte and the two electrodes share the same
compartment (without a salt-bridge)
The conditions of electrolytic cells are usually far
from the standard condition. 56
 ELECTROLYSIS
• Differences between a galvanic (voltaic) cell and an
electrolytic cell are:
• The anode is the positive electrode in electrolytic cells
whereas it is the negative electrode in a galvanic cell.
• The cathode is the negative electrode in an electrolytic
cell whereas it is the positive electrode in a galvanic cell.
• The Redox reaction is spontaneous (G > 0; Eocell < 0) in
electrolytic cell but non-spontaneous (G < 0; Eocell < 0).
• The direction of the electron flow is reversed (opposite)

NOTE: In both electrolytic and galvanic cells, oxidation

takes place in the anode and reduction in the cathode
57
Galvanic cell: Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
Oxidation: Zn(s) → Zn2+(aq) + 2e- (anode, negative)
Reduction: Cu2+(aq) + 2e- → Cu(s) (cathode, positive)

Electrolytic cell: Cu(s) + Zn2+(aq) → Cu2+(aq) + Zn(s)

Oxidation: Cu(s) → Cu2+(aq) + 2e- (anode, positive)
Reduction: Zn2+(aq) + 2e- → Zn(s) (cathode, negative)

Galvanic cell: Cl2(g) + Mg(l) → 2Cl-(aq) + Mg2+(s)

Oxidation: Mg(l) → Mg2+(s) + 2e- (anode, negative)
Reduction: Cl2(g) + 2e- → 2Cl-(aq) (cathode, positive)

Electrolytic cell: 2Cl-(aq) + Mg2+(s) → Cl2(g) + Mg(l)

Oxidation: 2Cl-(aq) → Cl2(g) + 2e- (anode, positive)
Reduction: Mg2+(s) + 2e- → Mg(l) (cathode, negative)58
 THE POTENTIAL NEEDED FOR ELECTROLYSIS
The voltaic cell: Zn (s) + Cu2+(aq) Zn2+(aq) + Cu(s) Eocell = 1.100V
• To reverse this spontaneous cell reaction to
• Zn2+(aq) + Cu(s)  Zn (s) + Cu2+(aq)

• In practice, to obtain appreciable product, the applied potential

is often significantly greater than the cell potential (1.10 V).
• The excess voltage over the cell potential is called
Overpotential. The interactions (called polarization) that occur
between the electrode reactions is the responsible for this.

• Very common when gaseous species are involved.

• Can be minimized choice of electrode.
• Competing reactions due to the presence of more than one
species can also determines the potential. 59
 THE POTENTIAL NEEDED FOR ELECTROLYSIS
Using the electrolysis of sodium chloride as an example.
In molten NaCl, there is only one oxidation and only one-reduction
reactions that are possible. (There will be no water)
Oxidation 2Cl-  Cl2(g) + 2e-
Reduction 2Na+ + 2e-  2Na(l)
In aqueous NaCl, because of the presence of water, we have two
oxidation and two reductions
Oxidation 2Cl-  Cl2(g) + 2e- Eo = -1.36 V
• 2H2O  O2(g) + 4H+(aq) + 4e- Eo = -1.23 V
• Reduction 2Na+ + 2e-  Na(l) Eo = -2.71 V
• 2H2O + 2e-  H2(g) + 2OH- Eo = -0.83 V
• The choice of the species to be discharged is often determined by Eo
of the half-reactions except if there are other constraining factors.
• The species that needs the least voltage (smaller amount of energy
ie the least negative or the highest positive emf) is discharged. 60
 THE POTENTIAL NEEDED FOR ELECTROLYSIS
• Oxidation:
• 2H2O  O2(g) + 4H+(aq) + 4e- Eo = -1.23 V
• Reduction:
• 2H2O + 2e-  H2(g) + 2OH- Eo = -0.83 V
• In reality chlorine is discharged at the anode because of
the high overpotential needed by oxygen to be
discharged. This normally will increase voltage needed to
discharge oxygen to about 1.73 V.
• An exception can also occur with mercury electrode as
cathode. H2(g) has a high overpotential on mercury (about
1.5 V) and therefore Na(s) will be discharged.
• sodium is soluble in mercury, it forms sodium amalgam. 61
 FARADAY’S LAWS OF ELECTROLYSIS
• Michael Faraday published the results of his series of
investigations (conducted in 1833 and 1834) on the
quantitative basis of electrolysis. His findings are
expressed as the Faraday’s laws of electrolysis.
• 1. The mass, m, of an element produced at the
electrode is proportional to the quantity of electricity,
Q, passing through the electrolytic cell.
• mQ
• the SI unit of Q is the coulomb (C).
• The quantity of electricity, Q, is defined as the current,
I, multiplied by time, t.
• Q = I.t
• SI unit of I = Ampere, A t = second, s.
62
 FARADAY’S LAWS OF ELECTROLYSIS
• 2. The mass of an element liberated at an electrode is
proportional to the equivalent weight of the element.
• m  Eq
• Eq = mr/n where mr is the relative
molecular/atomic mass of the substance and n is the number
of moles of electron the substance gains or loses.
• E.g, Cu loses two moles of electrons to become Cu2+. The
relative atomic mass of Cu is 63.5, therefore its equivalent
weight will be 63.5/2 =31.75.
• The relative atomic mass of Ag is 108. Its equivalent weight is
also 108 because it only needs to lose one mole of electron to
be completely discharged.
• The equivalent weight of an element is therefore defined as
the mass of the substance that is discharged by the passage
of one Faraday of electricity. 63
 FARADAY’S LAWS OF ELECTROLYSIS
• One Faraday of electricity will discharge one mole of electron. One
electron has a charge of 1.602 x 10-19 C and there are 6.022 x 1023
electrons in one mole of it.
Therefore one Faraday of electricity (Faraday constant, F) will be
1.602 x 10-19 C/e- x 6.022 x 1023 e/mol = 96,485 Cmol-1.
Example: What mass of sodium metal will be discharged at the
cathode when a current of 10 Amperes is passed through molten
sodium chloride for a period of 4 hours.
Solution: Quantity of electricity, Q Q = I.t I = 10 Amperes,

t = 4 x 60 x 60 seconds =14400 s Q = 10 x 14400 C = 144000 C

• A balanced equation at the cathode is Na+(l) + e- Na(l)
• 1 Faraday (96485 C) will deposit 1 mole of Na, that is, 23 g.
• 144000 C will deposit (23/96485) x 144000 g of Na= 34.3 g of Na.
64
 FARADAY’S LAWS OF ELECTROLYSIS
• Example: Calculate the oxidation number of chromium in
an unknown salt, if the electrolysis of this salt yields 9.71
g of chromium at the cathode after 10 Amperes of current
is passed through the cell for 1.5 hours. The relative
atomic mass of chromium is 52.
• Solution:
• Q = I.t I = 10 Amperes, t = 1.5 x 60 x 60 s = 5400 s
• Q = 10 x 5400 C = 54,000 C.

• 96485 C discharge 1 mole of electron

• 54000 C will discharge (54000/96485) moles of electrons
• = 0.56 mole of e-
65
 FARADAY’S LAWS OF ELECTROLYSIS
• The number of moles of chromium deposited is 9.71 g
(given in the question) of mass will be mass/Mw
(9.71/52) = 0.187 mole of chromium.
• The ratio of moles of chromium to moles of electrons
discharged is
• 0.187 : 0.560
• 1:3
• Therefore 1 mole of chromium requires 3 moles of
electrons to be discharged.
• The chromium therefore has an oxidation number of +3.
• Cr3+(aq) + 3e-  Cr(s)
66
 FARADAY’S LAWS OF ELECTROLYSIS
• Example: Calculate the mass of aluminum that can be
produced by the electrolysis of aluminium oxide, Al2O3,
dissolved in molten cryolite, Na3AlF6 in one day, if the
electrolytic cell is operated constantly at 1 x 105Amperes.
• Solution:
The reduction equation is Al3+ + 3e-  Al(l)
This means that one mole (27 g) of Al requires 3 Faradays
(3 x 96485 C) to be deposited.
• The quantity of electricity supplied, Q = I.t
• I = 1 x 105 Amperes, t = 24 x 60 x 60 s = 8.64 x 104 s
• Q = 1 x 105 x 8.64 x 104 C = 8.64 x 109 C
Al3+ + 3e-  Al(s)
• 3 Faraday (3 x 96485 C) will deposit 1 mole of Al, that is, 27 g.
8.64 x 109 C will discharge (8.64 x 109 x 27)/( 3 x 96485 ) of Al.
= 805.928 kg 67
 Electrorefining, Electrosynthesis and Electroplating
• These are electrolytic processes that are used
commercially in producing a number of substances.
• Electrorefining of metals involves the deposition of
pure metal at a cathode from a solution containing
the metal ion.
• The electrorefining of copper metal as electrical
conductor is probably the most important example.
• Silver and gold are impurities in copper; these
impurities are normally deposited at the anode.
Hence they are called anode mud.
• The value of the gold and silver deposited at the
anode is sufficient to defray the cost of electrolysis.
 Electrosynthesis
is a method of producing substances through non-
spontaneous reactions of electrolysis. For example,
manganese dioxide, MnO2, is obtained naturally as
pyrolusite but this MnO2 is not good enough for the
construction of alkaline batteries. A synthetic MnO2 is
prefered.
Electrosynthesis of MnO2 is carried out in a solution of
MnSO4(aq). MnO2 is produced at an inert anode by
oxidation of Mn2+.
Anode Mn2+ + 2H2O MnO2(s) + 4H+ + 2e-
Cathode 2H+(aq) + 2e-  H2(g)
Net Mn2+ + 2H2O  MnO2(s) + 2H+ + H2(g)
A very important commercial electrolysis process is the
chlor-alkali process for the manufacture of NaOH, H2
and Cl2.
 Electroplating
• The objective is to prevent corrosion and wear,
produce hardness and conductivity, and give
products an attractive appearance.
• The principle: thin metallic layers with specific
properties are deposited on base materials
including steel, brass, aluminium, plastic and die-
cast parts.
• Silver electroplating was the first large-scale use of
electrolysis for coating base metal objects with a
higher value decorative finish.
 BATTERIES
• A battery is a device (a voltaic cell) that stores
chemical energy, which is later released as
electricity. Some batteries have just a single voltaic
cell while some others have a number of voltaic
cells connected in series.
• There are three major types of batteries.
• Primary batteries (also called primary cells) are
galvanic cells that produce electricity from chemical
reaction that is not reversible. Once all the
reactants are converted to products, supply of
electricity stops and the battery is said to be dead.
 BATTERIES
• Secondary batteries (secondary cells) are galvanic
cells whose reactions can be reversed by passing
electricity through it from an external source. This
means that when the reactants are used up, more
reactants are produced from the products by
“charging” the cell. This type of cell can be
recharged several times before it is eventually
discarded.
• Flow batteries (fuel cells) are electrochemical cells
in which a combustion reaction is used to generate
electrical energy. They therefore require continuous
feed of the combustible material and oxygen.
 PRIMARY BATTERIES
Leclanche (Dry) Cell.
This is the first type of primary cell. It was introduced
in 1860 by a French Engineer George Leclanche.
The cell produces about 1.5 V initially. When this
voltage drops to about 0.8 V, the reaction products
inside it make it difficult to produce electricity.
This is because products are accumulated but if it is
left for about a day unused, the products disperse
and the voltage climbs up to about 1.3 V.
These cells are called dry cells because there is no
liquid in them.
Leclanche (Dry) Cell
 Leclanche (Dry) Cell
The container of the cell also acts as the anode, is a zinc metal.
Zn(s)  Zn2+(aq) + 2e-
• The cathode is a carbon rod at the centre but the cathode
reaction is a complicated reduction of manganese(IV)oxide to
manganese(III). For example
• 2MnO2(s) + H2O + 2e-  Mn2O3(s) + 2OH-(aq) or
• MnO2(s) + H2O + e-  MnO(OH) (s) + OH-(aq)
• The electrolyte is a moist paste of NH4Cl, ZnCl2 and MnO2. The
OH- ion from the cathode reaction will migrate towards the
anode and will react with NH4+ from NH4Cl to form NH3
NH4+ (aq) + OH-(aq)  H2O(l) + NH3(g)
• Cell reaction is irreversible
• Drop in voltage may occur due to NH3 gas buildup and slow
dissolution of the Zn(s) electrode in the acidic electrolyte.
 Leclanche (Dry) Cell
• To eliminate the last two problems, a better Leclanche cell is
made of alkaline electrolyte, KOH or NaOH instead of NH4Cl. It
is called alkaline cell. The anodic half-reaction involves the
formation of Zn(OH)2(s).
• It has a number of advantages;
1. This is a cheap cell.
2. It can be used over a wider range of temperatures because the
electrolyte is more stable.
3. It requires just a little electrolyte hence the size can be compact.
4. Because ions move easily through the electrolyte, it produces
more power and a steadier current.
• The major disadvantage of this battery is that it is more
expensive because extra sealing material is needed to prevent
hydroxide leakage.
Lead-Acid (Storage) Battery
 Lead-Acid (Storage) Battery
This is the most common secondary cell. It is often used
as automobile batteries. It contains a number of
galvanic cell which are connected in series, so that their
voltages are additive. Each cell contains several grids
that acts as electrodes. The total surface area of these
grids is large, hence the battery can generate a large
current.
The electrodes are initially plates of a lead-antimony alloy
covered with a paste of lead(II)sulphate.
The electrolyte is sulphuric acid. During the first charging,
the PbSO4 on one of the electrodes is reduced to lead,
this is the anode, while that on the cathode is oxidized
to PbO2.
 Lead-Acid (Storage) Battery
• discharging
• Pb + SO42-  PbSO4 + 2e- (anode plate (Pb) )
• Charging
• Its discharge standard potential is 0.386 V.

• discharging
• PbO2 + 4H+ + SO42- + 2e-  PbSO4 + 2H2O cathode (PbO2) plate
• Charging
• Its discharge standard potential charge is 1.682 V.
• A combination of the two half-cells gives
• discharging
• PbO2 + Pb + 4H+ + 2SO42-  2PbSO4 + 2H2O
• charging
• This gives an overall discharge voltage of 2.068 V.
 Lead-Acid (Storage) Battery
• As the battery discharges, the concentration of the
sulphuric acid decreases, that is, the density of the
sulphuric acid decreases. The sulphuric acid density of
a fully charged battery is between 1.25 to 1.3 g/mL,
once this falls below 1.20 g/mL, the battery must be
charged.
• The density of can be checked with hydrometer.
Hydrometer is a glass tube that can be used to draw the
acid, it has a float whose sinking depth is inversely
proportional to the concentration (density) of the acid.
The major disadvantages of this battery are
1. They are heavy
2. Sulphuric acid is corrosive, hence the spillage of the
acid corrodes every metal it comes in contact with.
 Nickel-Cadmium (NICAD) storage battery
This is a rechargeable (secondary) battery
It is used in portable electronic equipment and power
tools.
Its net potential is 1.4 V. the reactions of the battery
are shown below;
Anode (Ox): Cd(s) + 2OH-(aq) Cd(OH)2(s) + 2e-
Cathode(Red): NiO2(s) + 2H2O + 2e-  Ni(OH)2(s) + 2OH-
Net: Cd(s) + NiO2(s) + 2H2O  Cd(OH)2(s) + Ni(OH)2(s)

• Other potable specialized batteries used in

electronic calculator, cameras, wristwatches
 Mercury Battery
It generates 1.35 V and this voltage remains virtually
constant during the lifetime of the battery. The
reaction equations are shown below;
Anode (ox): Zn(s) + 2OH-(aq) ZnO(s) + H2O + 2e-
Cathode(red): HgO(s) + H2O + 2e-  Hg (l) + 2OH-
Net: Zn(s) + HgO(s)  ZnO(s) + Hg(l)

• Mercury could be poisonous and therefore disposal

of the dead the battery poses a danger. A better
alternative to this battery is the Silver-Zinc battery
 Silver-Zinc battery (Button Battery)
• It generates a net potential of 1.5 V. The anodic
(oxidation) reaction is similar to that of the mercury
battery but in the cathodic (reduction) reaction silver
oxide replaces mercury oxide.
•
Anode (ox): Zn(s) + 2OH-(aq)  ZnO(s) + H2O + 2e-
Cathode(red): Ag2O(s) + H2O + 2e-  2Ag (s) + 2OH-
Net: Zn(s) + Ag2O(s)  ZnO(s) + 2Ag(s)

• The advantage of this battery is that they are small in

size, the electrolyte quantity is very small. The storage
capacity of this battery is about six times that of lead-
acid battery of the same size.
 Flow Batteries (Fuel cells)
They convert chemical energy of the fuel (natural gas) directly
by combustion (oxidation) to electricity.
The simplest and most successful fuel cell is the reaction
between hydrogen gas and oxygen gas.
The fuel (hydrogen) is passed over one of the electrodes while
oxygen is passed over the other. The electrolyte for this fuel
cell is aqueous 25% KOH. The reactions of this cell are shown:
Anode (oxidation) 2H2(g) + 4OH-(aq)  4H2O + 4e-
Cathode (reduction) O2(g) + 2H2O + 4e-  4OH-
Net 2H2(g) + O2(s)  2H2O(l)
• As long as the fuel and oxygen are supplied the cell continues
to produce electricity. Fuel cells are used in space shuttles.
Motor cars powered by hydrogen fuel cells was introduced
into the American car market in 2002.
Flow Batteries (Fuel cells)
 Flow Batteries (Fuel cells)
• Methane gas can be used as fuel, the reaction becomes
Anode (oxidation): CH4(g) + 2H2O(l)  CO2 + 8H+ + 8e-
Cathode(reduction): 2O2(g) + 8H+ + 8e-  4H2O (l)
Net: CH4(g) + 2O2(s)  CO2 + 2H2O(l)
• This reaction is in acidic medium.
• The power supplied by fuel cells is often rated in terms of
efficiency value rather than voltage. Efficiency value  =
Go/Ho of the reaction.
• The electric potential generated by electric eels
(Electrophorus electricus) and catfish has been classified as
natural fuel cells. The cells are fuelled by food. In electric eels,
each cell produces about 0.15 V, an average potential
difference it produces along its 1-metre length is 350 V. The
eel’s head acts as the cathode while its tail acts as the anode.
REACTION KINETICS
• It is not enough to understand the
stoichiometry and thermodynamics of reaction,

• We must also understand the FACTORS that

govern/affect the rate of reaction.

• Chemical kinetics/Reaction kinetics is the

study of how reaction rates change under
varying conditions and what molecular events
occur during the OVERALL REACTION.
• The rate or velocity with which a
chemical reactant is converted under
varying conditions into a product and the
mechanism by which such a reaction
occurs constitute the field of study
known as Reaction Kinetics.
• The rate of such a chemical reaction is
determined by measuring the change in
the concentration of either the reactant
or the product with time.
• In practice, the observation of a change in a
physical property (spectroscopic, hydrogen ion
concentration, etc) of the reactant or product
is used to measure the extent of change as a
function of time.
• The mode by which a reactant is transformed
into a product is the mechanism of the
reaction.
• Collection of individual kinetic processes/
elementary steps involved in the
transformation of reactants into products.
• Explanation of how a reaction takes
place/occurs.
• The molecular EVENTS which occur during a
reaction.
• The SERIES of individual steps leading to the
overall observed reaction.
• Consider the thermal decomposition of
dinitrogen pentoxide. The STOICIOMETRIC
equation for the reaction is: 2 N 2 O 5  4 N O 2  O 2
• The reaction can take place in stages, probably
as follows:
N 2O5 
slow
 NO2  NO3

NO2  NO3 

fast
NO2  NO  O2 One Way
NO  NO3 
fast
2 NO2

2 N 2O5  4 NO2  O2
 WHY MEASURE REACTION RATES.
• How fast a chemical product will ‘work’
• How quickly, and economically, a product can
be made.
• A knowledge of the reaction mechanism helps
the industrial chemist to modify a product,
thereby increasing its effectiveness.
• Learn a great deal about how reactants
change into products.
 FACTORS THAT AFFECT REACTION RATES
• The chemical nature of the reactants;
• The ability of the reactants to come in contact
with each other;
• The concentrations of the reactants:
increasing the concs.;
• Temperature of the reaction system and
• The availability of agents called CATALYSTS.
 Rates of Chemical Reaction
• When a chemical reaction occurs, the molar
concentrations of the reactants decrease as the
reactants are used up, while those of the products
increase as they are formed. The average rate of
such a reaction is expressed as:

[ ]
• Average rate of reaction = - 1(a)

[ ]
• Average rate of reaction = + 1(b)
• =  [C o n c ] ,  = change in.
 [tim e ]
• The instantaneous rate or the reaction rate at
a particular time can be obtained by taking
the tangent to a plot of concentration of
reactant or product against time.

• Equation (1) indicates that the rate of a

reaction may be defined in two major ways,
either in terms of the disappearance of the
reactants or the appearance of the products,
depending upon whether the reactant or the
product is being observed or monitored.
• What one observes experimentally in
determining the rate of a reaction is the
change in conc . Ci, of one or more of the
reactants or product as a function of time, t.
• Consider a hypothetical homogeneous
reaction, which is unidirectional in the
direction of the arrow in Equation (2), with
reactant concentration as the only monitored
variable

• A(g) + B(g) C(g) + D(g) (undefined) (2)

• The rate of the chemical reaction can be
expressed thus:

[ ] [ ] [ ] [ ]
• Rate = = = = (3)
• The concs of A or B decreases during the time
interval, therefore the change in A or B is a
negative quantity.

• The rate of a reaction is a positive quantity, so

a minus sign is needed in the rate expression
to make the rate positive.
• In Equation (2), all the stoichiometric
coefficients of the reactants and the products
are the same. When they are not, the
stoichiometric factors have to be taken into
account in the definition of the rate of
reaction.

• Consider a general reaction

aA + bB →cC + dD (4)
• The rate of reaction is defined by Equation (5)
[ ] [ ] [ ] [ ]
• Rate =- = − = = (5)

• a, b, c, & d are stoichiometric coefficients.

• In Equation (5), the relative rates at which the

reactants are consumed and the products are
formed are related via the coefficients of the
balanced chemical equation for the reaction.
• Take an arbitrary reaction A B
d[ A]
[ A ] slope    cons tan t
dt
C o n c.

[ B] d[B]
slope   cons tan t
dt

Time / s

linear plot
• C D

Conc. [C ]

[ D]

• Non-linear plot. The rate depends on reaction

conc. and time.
 Quiz # 1
• In 5 minutes, the conc of A( g ) falls from
4.400 x 10-2 mol dm-3 to 4.352 x 10-2 mol dm-3
by the reaction A B + C, what is the rate
of reaction?
• The rate of reaction is a function of factors
such as the concentrations of the reactants,
the temperature of the reaction system, and
the catalyst used.
 Concentration and the Rate Law
• The rates of most reactions change when the
concentrations of the reactants change.
• In general, the rate is proportional to the
concentration of the reactants raised to
appropriate powers/indices/exponents.

• Consider the following chemical equation:

xA + yB Product(s) (6)
• In Equation (6), x and y are molar coefficients
of reactants A and B, respectively. A general
rate law involving the reactants A and B will be
of the following form:

[ ]
• - = [A]n [B]m (7a)
[ ]
• - = [A]n [B]m (7b)
• In Equation (7), k is the specific reaction rate
constant.
• The exponents n and m are called reaction
orders, and the sum (m + n) is the overall
reaction order.
• Equation (7) is known as the rate law.
• The rate law is an expression for the rate as a
function of concentration at a fixed
temperature.

• Equation (7) is determined experimentally.

 Experimental Determination of Rate Laws
• Most chemical changes consist of several steps
called elementary steps.

• Different reactants can affect the rate of a

particular reaction differently.

• Consequently, Equation (7) cannot be written

from the balanced chemical equation but from
experimental data.
• To determine the order with respect to each
reactant in expression (7),

• it is necessary to study the mechanism by

which changes in the concentration of each
reactant affect the initial rate of the reaction.
• A + B → Product
• Let us conduct a hypothetical experiment for
the above-named reaction in order to
determine its rate law, using the initial rates
method.
• How the initial rate depends on the starting
concs is preferable. As the reaction proceeds,
the concs of the reactants decrease and it may
become difficult to measure the change
accurately.
• Mix the solutions of the reactants A and B
with initial concentrations [A]0 and [B]0,
respectively.

• The temperature of the mixture is fixed.

• At convenient time intervals, withdraw some
aliquots of this mixture, stop the reaction or
slow it down drastically, analyze the
withdrawn sample chemically to determine
the change in concentration of the reactant A
which occurs after reactants have been mixed.
• Instead of monitoring the change in
concentration of reactant A,
• the change in its physical property as a
function of time could be measured.
• For example, its optical absorbance,
fluorescence, optical activity or refractive
index.
• Perform other experiments with different
values of the initial concentration of A at the
same fixed temperature, keeping the initial
concentration of reactant B constant.

• Determine the initial rate, at (time = 0), for

each experiment from a plot of concentration
against time.
• Compare the initial rates obtained from these
experiments.

• If there is no change in rate, the order with

respect to A is zero.

• If the rate of reaction doubles when the initial

concentration of A is doubled, the order with
respect to A is one.
• If the rate quadruples when the initial
concentration of A is doubled, then the order
with respect to A is two.
• Similarly, varying the initial concentration of
reactant B and keeping the initial
concentration of reactant A and the
temperature of the reaction constant, the
effect of the concentration of reactant B on
the initial rate of the reaction can also be
investigated and
• the order with respect to B determined.
These experimentally determined orders with
respect to each reactant will enable us to
write Equation (7), the rate law.
• For example, consider the reaction:
A(g) + B(g) →C(g)

• The experimental rate law of the preceding

reaction is:
• Rate = k [A] [B]0

• What is the overall order of the reaction?

• Since the overall order is the sum of the
exponents, we obtain (1 + 0) = 1 as the
reaction order.
• For a hypothetical reaction in which B and C
react to form the product, D, the following
data were obtained from three experiments.
• B+C D
Experiments [B] [C] (Rate of formation of D)
1. 0.15M 0.075M 3.5 x 10-3mol dm-3min-1
2. 0.30M 0.15M 1.4 x 10-2mol dm-3 min-1
3. 0.15M 0.15M 7.0 x 10-3mol dm-3 min-1
• Suppose we have the reaction: oxidation of Bromide ions by
Bromate ions in acid solution.

BrO3 (aq)  5Br (aq)  6H  (aq)  3Br2 (aq)  3H2O(l)

Mixture [Bro3] [Br-] [H+] Relative

initial rate of
formation of
Br2
I 0.05 0.25 0.30 1
II 0.05 0.25 0.60 4
III 0.10 0.25 0.60 8
IV ? ? ? ?

R  k [ B rO 3 ] l [ B r  ] m [ H  ] n
•
• 1  k[0.05] [0.25] [0.30]
l m n

4  k[0.05] [0.25] [0.60]

l m n

• 1 [ 0 .3 0 ] n

4 [ 0 .6 0 ] n
1 1
• 2
 n
2 2
• n= 2
 Quiz #2

3A + B C
The rate of formation of C in the above
reaction is found experimentally to be
independent of the concentration of B
and to quadruple when the
concentration of A is doubled. Write
the rate law for the reaction.
• The exponents in the rate law appear to be
unrelated to the coefficients in the overall
chemical equation. See Equation 7

• There is, in fact, no way to know for sure what

the exponents in the rate law of an overall
reaction will be without doing expts to
determine them.
• Sometimes, however, the coefficients and the
expts are the same by COINCIDENCE, as in the
case of elementary reactions.

• In general, the order of a reaction must be

determined by expt; it cannot be deduced
from the overall balanced equation.
 Reaction Mechanisms and Rate Laws
• An overall balanced chemical equation does
not tell us much about how a reaction takes
place.
• 2H  O  2H O
2 2 2

• The chemical equation represents the sum of

a series of simple reactions called the
elementary steps/elementary reactions.
• They represent the progress of the overall
reaction at the molecular level.

• The sequence of elementary steps that leads

to product formation is called the reaction
mechanism.
 Molecularity, Mechanism and Predicted Rate
Law

• Most chemical reactions consist of elementary

reactions or steps.

• One of these steps, which is much slower than

the others, determines the rate of the
reaction and it is referred to as the rate-
determining or rate-limiting step.
• An elementary reaction can be characterized
by the number of reactant molecules involved
in it.

• This number of molecules or species on the

reactant(s) side / in an elementary reaction
/step is known as the molecularity of the
reaction.
• For the elementary process, the order(s) in its
rate law are the same as the stoichiometric
factors, or equal to the coefficients of the
reactants in the chemical equation for the
process.
• An elementary step in which only one reacting
molecule participates is UNIMOLECULAR

• Two molecules is BIMOLECULAR .

• TERMOLECULAR reaction involves the

participation of three molecules in one
elementary step.
• The rate of an elementary reaction is
proportional to the product of the
concentrations of the reactants that are in
that step.

• Therefore, the rate law for an elementary

process can be predicted from the chemical
equation for the process.
• Consider the reaction:

• PCl5 →PCl3 + Cl2

• The above reaction can be explained by a two-step
mechanism:
• Step (1) is the slow (rate limiting) step.
• PCl5 →PCl4 + Cl. slow
• Step 2 PCl4 →PCl3 + Cl. fast

Net: PCl5 →PCl3 + Cl2

• The experimentally determined rate law is:

• Rate = k [PCl5]
• and, from the rate-limiting step, the predicted rate law
is
• Rate k [PCl5]
• The elementary steps must satisfy two
requirements:

• The sum of the elementary steps must give

the overall balanced equation for the reaction.

• The rate-determining step, which is the

slowest step in the sequence of steps leading
to product formation, should predict the same
rate law as is determined experimentally.
• The order of multistep reaction must be
obtain experimentally.

• For example, the conversion of A + C D

• A B slow, RDS
• B+ C D very fast
• A+C D

• The rate at which D is formed depends on how

quickly A gives B, not how quickly B reacts
with C. The rate equation would be:

• Rate = k[A]x
 UNITS OF RATE CONSTANTS
• The units of the specific rate constant depend
on the overall order of the reaction.

• The units are worked out from the units of the

individual terms in the rate equation.

• Units of rate constants = Units of initial rate

(Units of initial concentration)x
(9)
• where x is the overall order. For example, a
reaction that is first order with respect to a
single reactant B, and first order overall, has a
rate law,

[ ]
• rate = = [ ] (10)
• The units of rate are mol dm-3 time-1 and the
units of [B] are mol dm-3

• Substituting these units into Equations (9)/

(10), and assuming that time is in seconds and
x = 1, gives the units of k as s-1 or time-1.

• [ ] = mol dm-3
• M = mol dm-3
• Use this
 ORDER OF REACTION
• Reaction can be classified by its order/ we can
classify reactions into:
• Zeroth/Zero order
• First order
• Second order
• Third order(rarely)
• Fractional order
• Negative order
 KINETICS EQUATIONS/CONCS-TIME
EQUATIONS

• The rate law tells us how the speed/rate of a

reaction varies with concentrations of the
reactants at a particular moments.

• The relationship between the concentration of

a reactant and TIME can be obtained from the
rate law of a reaction.
• This can be done by integration of the rate
expression/ transform a rate law into a
mathematical relationship between conc. and
time.
 [ ]
• rate = = [ ] (10)

• The differential rate law, or Equation (10), tells

us how the rate of a reaction depends on the
reactant concentrations.
• Equation (10) should be integrated to find out
how the concentrations of the reactants
depend on time.
• First-order Reactions
• Consider the decomposition of reactant, B,
which follows first-order kinetics
• B→C
• let b mol dm-3 stand/stand(s) for the initial
concentration of reactant, B, and x mol dm-3 of
B have disappeared after time t, the rate of
formation of the product can be expressed as:
• = − (11)
 [ ]
• rate = = [ − ] (12a)

• rate = = [ − ] (12b)
• rate = = [ − ] (12b
x x tt
dx
• 
x0
b x
 
t0
kdt (13)
• Separating the variables and integrating
Equation (13) between the limits x = 0 at t = 0
and x = x at some time t, we have

x x t t
• [ ln(b  x)]
x0  k[t ]
t 0 (14)

b
• ln  kt (15)
b  x
1
•  xdx  ln x  loge x
• Take a function y  ln ( b  x )
• If u=(b-x)
• y  ln u
• dy  1
du u

d u
  1
• d x
dy 1
• Therefore dx
 
u
• Equation (15) can be written as:
log = (14)
.
• or log10 (b – x) = log10 b - (15)
.

• Equations (14) and (15) are kinetic equations

for a first-order reaction.
• These equations can be used to determine the
concentration of reactant(s) or product(s) at
any time during the reaction.
• We can have the equation as:

b
• ln  kt
b  x
b
•  exp  kt 
b x
• (b  x)  b exp  kt 
• [B]t  [B]0 exp(kt )
• From Equation (15), a plot of log10 (b – x) as a
function of t gives a straight line with a slope
of − and an intercept of log10 b.
.

•
 Second-order Reactions
• let us consider a situation in which the
reactants are present with initial equimolar
concentrations.

• Consider a reaction

• C+D → Products
• [C] = [D] i.e., the initial conc. of [C]=[B]
• Since the reactants are of equal molar
concentrations, let the initial concentration of
each reactant be c mol dm-3 at t = 0 and (c – x)
mol dm-3 after time t when x mol dm3 of each
reactant must have decomposed .
• The rate of formation of the product will given
by:
• Rate of reaction = = ( − ) (16)
 d [C ]
  k [C ][ D ]
• OR dt
d[C] d[D] dx
   k2[c  x]2
• OR dt dt dt

x t
dx
• 
0
(c  x ) 2
 
0
k2dt (17)
 x
 1 
• k 2t   (18)
 b  x  0

1 1
• k2t   (19)
b x b
• Equation (19) is the second-order kinetic
equation. k2 can be evaluated graphically(Fig.
5.2)

• Or by substitution of the initial concentration

and the concentration of a reactant at time t
into Equation (19).
• A first-order reaction is 45 percent complete
after 400 seconds. How long will it take for
the reaction to be 90 percent complete?
• The kinetic equation for a first-order reaction
is
• log =
.
• b = 100%
• b–x = 55%
• time = 400s

• Substituting the values of b and b – x into the

first-order kinetic equation gives
• log = 400
.
• k = 1.495 x 10-3s-1
• But log = .
.
• Where k = 1.495 x 10-3s-1

• Substituting the numerical value of k gives

.
• log = .t
.

• ∴ = 1541 seconds
 METHODS FOR ORDER
• The order of a reaction can be determined by:
• Graphical method
• Substitution method- constant ks
• Half-life method.
 Half-Life Method
• The half-life of a reaction, t½, is the time required for
the concentration of a reactant to decrease to half of
its initial value.
• The time it takes for half the reactant to form
product.
• Consider the first-order kinetic equation
• log = t (19)
.
• The initial concentration of the reactant is b
mol dm-3 .
• x mol dm-3 is the concentration of the product
formed at time t.
• At the half-life, x = b/2.
• Substituting x = b/2 into equation (19), gives
.
• t½ = log (20)
/
• Example
• The rate constant for the first-order
decomposition of N2O5 at temperature t0C is
2.2 x 10-1s-1.
• If the initial concentration of N2O5 is 3.6 x 10-3
mol dm-3, what will the concentration be after
four half-lives?
• For a first-order reaction, the half-life is
independent of the initial concentration of the
reactant.
• After the first half-life, the initial
concentration would have decreased by half.

• Therefore, after the fourth half-life, the

concentration will be 2.25 x 10-4 mol dm-3.
 The Temperature Dependence of Reaction Rates:
The Arrhenius Equation

• The rate of reaction, or the rate constant,

increases if the temperature of the reacting
system rises.

• This arises from the increase in the collision

frequency and the fraction of molecules with
energy equal to or greater than Ea (the
activation energy).
• For fixed conc. of reactants, a reaction
proceeds at different rates at different
temperatures.
• The increase in the specific rate constant, k,
with rise in temperature varies according to
the following equation.

• k = A exp – (Ea/RT)
• where k = the specific rate constant;
• A = the pre-exponential factor/frequency
• factor;
• Ea = the activation energy in J;
• R = the gas constant (8.314J K-1mol-1)
• T = the absolute temperature in K (0C + 273);
• The effect of temperature on the reaction rate
can be seen in Equation (21).

• A reaction will always be faster at a higher

temperature because many more molecules
will possess the activation energy on collision.
• The higher the activation energy is, the slower
the reaction at any given temperature.
• k  A exp(
Ea
) (21)
RT

• Equation (21) is called the Arrhenius

Equation. It relates the rate constant k for a
reaction to the absolute temperature T.

• 1n k = 1n A - (22)

• Or log10 k = log10 A - (23)

.
• Let us write Equation (23) for k1 and k2 at
temperatures T1 and T2, respectively.
• log10k1 = log10 A - (24)
.

• log10k2 = log10 A - (25)

.
• Substract Equation (24) from Equation (25
• log10k2 - log10 k1 = . - .
. .

• or log10 = . (26)
.
• Equation (26) indicates that if T1, k1 and Ea are
known, k2 can be calculated for any choice of
T2
• Consequences of Arrhenius equation.

• The Ea of the reaction can be calculated.

• The k can be calculated.

• Knowing the activation energy , Ea ,the

exponential factor can be calculated.
 Test # 1
• (1) B + 2A A2 + D
has been established experimentally to be :
• Rate = k[A][B].

• What are the units of k if the concentrations

are expressed in mol dm-3 and the time in
seconds?
• [A] mol-1 dm3 s-1 [B] mol dm3 s
[C] mold m-3 s-1 [D] mol-1 dm-3 s-1
• (2). What is the rate law for the following
elementary reaction ?
O3 + NO O2 +NO2

• [A] rate = k[O2][NO2]; [B] rate = k[O3][NO] ;

[C] rate = k[O3][O2] ; [D] rate= k[NO][NO2]
• (3) B C

• In the above reaction, the rate of formation of

C increased four times when the
concentration of B was doubled. What is the
rate law for the reaction?
• (4) The rate determining step for a gaseous
reaction is as follows: A(g) + B(g) →C(g) . What is
the molecularity of the reaction?
• 1. A

• 2. B

• 3. Rate = k[A]2

• 4. 2
• Example
• A certain first-order reaction has a half-life, t½, of
2400s at 300C and 240s at 1500C. Calculate the
activation energy of this reaction.
• Since it is first-order reaction,
.
• t½ =
.
• At 300C, k1 = = 2.8875 10-4s-1
.
• At 1500C, k2 = = 2.8875 10-3s-1

• But log k 2  E a  T2  T1 
 
k1 2.303 R  T2T1 
• T1 = 30 + 273 = 303k
• T2 = 150 + 273 = 423k

• Substitution gives:

.
• log =
. . .
• Ea = 20.450 kJ mol-1
 THEORIES OF REACTION RATES
The collision Theory

• The rate constant, k, varies with temperature

and one of the theoretical models used to
explain the variation of k with temperature is
the collision theory.
• For a bimolecular gaseous reaction with
colliding molecules possessing the required
energy of impact and the molecules properly
oriented, the collision theory predicts that the
specific rate constant, k, at a temperature T0
Kelvin, is a product of the following
• the collision frequency (Z)

• the orientation factor P, and

• the activation state factor exp (-Ea/RT)

• From these three requirements, the rate

constant can be defined as
• k = ZP exp (- Ea/RT) (27)
• Equation (27) is in the same form as Equation
(21) if the pre-exponential factor is given by A
= ZP.

• Equation (27) indicates that the rate of a

reaction is proportional to the number of
collisions between reactant molecules per unit
time.
 The Transition-State Theory
• The transition-state theory explains that at
any given temperature the rate of a reaction
depends on the concentration of the activated
complex, which is in thermodynamic
equilibrium with the molecules of the
reactants,

• and on the rate of decomposition of the

activated complex to form product(s).
• Consider a bimolecular reaction between A and
B to form product(s).
• According to the theory, a reaction proceeds as
follows:
• The equilibrium constant, K , for the reaction


producing the activated complex can be

• written as A + B  [ −
K 
]± ( )

 [ ]±
K = (28)
[ ]
• The reaction rate, - d[A]/dt or –[B]/dt, is given
as
[ ]
• Rate = - = [ − ]± (rate of
crossover/passage) (29)
• = [A – B]± v

• Where [A – B]± v is the concentration of the

activated complex and v is the frequency of
vibration giving rise to bond rupture in the
activated complex.
• The minimum energy required to excite
vibrational motion is E = h v where h is
Planck’s constant.

• Therefore, v can be expressed by

• v=
• where kB is Boltzmann’s constant and T is the
absolute temperature.
• Form Equations (28), (29), and (31) one
obtains
• -d[A] /dt = K [A] [B] (32)
• For a bimolecular reaction (second-order).
Equation (32) can be written as
• k[A] [B] = K [A][B] (33)
• From the relationships ΔG± = -RT1n K , and
• ΔG± = ΔH± - TΔS±, if all substances are in their
standard states of unit activity, the rate
constant, k, in Equation (33) can be expressed
• as k = exp (ΔS±/R - ΔH±/RT ) (34)
• Now ΔH± = Ea + Δ(PV)±
• For reactions involving liquids and solids,
• Ea =ΔH± since Δ(PV)± is very small.
• Equation (34) can therefore be written as

• k= exp (ΔS±/R) exp (-Ea/RT) (35)

• On comparing Equation (35) with Equation

(21), k  A a
exp( 
E
RT
) ,one finds that

• A= exp (ΔS±/R)
• From equation (35), the expression for k can
be written as:

• k = A exp- (Ea/RT)

• The introduction of an entropy of activation,

ΔS±, in Equation (35), leads to a better
interpretation of reaction rates.
 Catalysis
• A catalyst is a substance that alters the speed
of a chemical reaction without itself
undergoing any net chemical change.

• A positive catalyst causes a reaction to

proceed more rapidly and a negative catalyst,
such as an inhibitor, retards the rate of a
reaction.
• A positive catalyst performs some or all of the
following functions:

• It increases the collision frequency (Z)

• It orientates the reactant molecules to obtain
the correct collision geometry,
• It provides an alternative pathway or a
mechanism with a lower activation energy.
• Consider, for example, a bimolecular reaction
catalyzed by a positive catalyst at 298K.

• A + B → Product(s),

• with a rate expression:

• Rate of reaction = k [A]x [B]y (37)

• In Equation (37), k is the specific rate constant,
x, and y are the orders with respect to A and
B, respectively.
• If the concentration of the reactants and the
temperature of the reaction medium are kept
constant, for uncatalyzed and catalyzed
reactions,
• Equations (21), (27) and (37) indicate that a
positive catalyst can speed up a reaction by a
combination of all or some of the enumerated
functions.
• k  A exp(
Ea
) (21)
RT

• k = ZP exp (- Ea/RT) (27)

•
• Rate of reaction = k [A]x [B]y (37)

• Equations (21), (27) and (37) indicate that a

positive catalyst can speed up a reaction by a
combination of all or some of the enumerated
functions.
• The effect produced by a positive or negative
catalyst is referred to as catalysis.

• The changes in the thermodynamic functions

of state, ΔG, ΔH and ΔS, that are characteristic
of the reaction are not affected by catalysis.

• There are two types of catalysis:

• Homogeneous catalysis, and

• Heterogeneous catalysis
 Homogeneous catalysis
• A reaction is said to be kinetically homogeneous
if it takes place in one phase only.
• That is, the catalyst is present in the same
physical state as the reactant(s).

• For example, the oxidation of sulphur dioxide to

sulphur trioxide in the presence of nitric oxide in
the lead-chamber process of sulphuric acid.
 Heterogeneous catalysis
• In heterogeneous catalysis or surface contact
catalysis, the reacting species and the catalyst are
in different physical states.
• In this type of catalysis, the catalyst is solid and
the reactants are gases or sometimes liquids.
• For example, the synthesis of ammonia from
hydrogen and nitrogen by the Haber process. In
this case, the catalyst, iron (in finely divided form)
in the presence of molybdenum is a solid and the
reactants are gaseous.