Physical Chemistry Volume 6-1

Table of Contents
AN INTRODUCTION TO PHYSICAL CHEMISTRY ............................................................................................. 3

TOPIC ONE: MATTER ..................................................................................................................................... 4
RELATIVE MOLECULAR OF GASES ........................................................................................................... 22
TOPIC TWO; THE ATOMIC STRUCTURE ..................................................................................................... 30
Discovery of some particles of an atom.................................................................................................. 31
Isotopes ................................................................................................................................................... 35
RADIOACTIVITY ....................................................................................................................................... 38
Electronic structure of an atom .............................................................................................................. 50
TOPIC THREE: Bonding and structure ......................................................................................................... 55
3.0 interatomic bonds ............................................................................................................................. 55
3.2 Types of bonds .................................................................................................................................. 55
POLARISATION AND ITS EFFECTS ON IONIC AND COVALENT BONDS..................................................... 58
INTERMOLECULAR FORCES OF ATTRACTION.......................................................................................... 62
The shapes of molecules and ions .......................................................................................................... 67
TOPIC 4 : THERMOCHEMISTRY ................................................................................................................... 72
Laws of thermo chemistry ...................................................................................................................... 81
STANDARD ENTHALPY OF NEUTRALIZATION .......................................................................................... 87
Lattice energy.......................................................................................................................................... 94
Enthalpy changes when ionic compounds dissolve in water................................................................ 102
BOND ENTHALPY or BOND ENERGY ...................................................................................................... 105
Topic 5: Physical equilibrium .................................................................................................................... 112
System, phase and component ................................................................................................... 112
One component system ........................................................................................................................ 113
TWO COMPONENT SYSTEM ............................................................................................................. 120
Mixtures of two liquids ..................................................................................................................... 120
COMPLETELY MISCIBLE LIQUIDS ............................................................................................... 120
IMMISCIBLE LIQUIDS ............................................................................................................................. 139
Steam distillation .......................................................................................................................... 141
THREE COMPONENT SYSTEMS. ............................................................................................................ 148
HOLISTIC APPROACH TO PHYSICAL CHEMISTRY Page 1

a)THE SOLVENT EXTRACTION .................................................................................................... 154
SOLID-LIQUID EQUILIBRIUM .......................................................................................................... 166
SUB-TOPIC3 :COLLIGATIVE PROPERTIES OF SOLUTION ........................................................................ 180
TOPIC6: CHEMICAL EQUILIBRIUM: ........................................................................................................... 201
CHAPTER SEVEN; IONIC EQUILIBRIA ......................................................................................................... 219
Terms used in ionic equilibria ....................................................................................................... 219
Acid-Base theory ............................................................................................................................... 219
IONIZATION OF WATER ................................................................................................................... 229
THE HYDROGEN ION INDEX pH ...................................................................................................... 230
BUFFER SOLUTIONS .......................................................................................................................... 234
SALT HYDROLYSIS............................................................................................................................. 244
ACID- BASE INDICATORS.................................................................................................................. 249
SOLUBILITY AND SOLUBILITY PRODUCTS ................................................................................... 260
T0PIC 8:CHEMICAL KINETICS ..................................................................................................................... 271
Measuring reaction rate ....................................................................................................................... 274
RATE EQUATION OR RATE LAW ............................................................................................................ 275
TYPES OF ORDER OF REACTION ............................................................................................................ 277
REACTION MECHANISMS ...................................................................................................................... 288
THEORIES RESPONSIBLE FOR OCCURANCE OF CHEMICAL REACTIONS ................................................ 289
Factors which influence rates of reaction............................................................................................. 291
EXPERIMENTAL DETERMINATION OF ORDER OF REACTION ................................................................ 297
TOPIC 9: ELECTRO CHEMISTRY.................................................................................................................. 301
SUB-TOPIC1 :ELECTROLYSIS .................................................................................................................. 301
SUB-TOPIC 2: ELECTROLYTIC CONDUCTION ......................................................................................... 308
SUB-TOPIC 3 ELECTROLCHEMICAL CELLS .............................................................................................. 322

AN INTRODUCTION TO PHYSICAL CHEMISTRY
Chemistry is the study of the elements and the compound formed when they bond with each other.
There are three main objectives in studying chemistry, these are:
 To discover as much as we can about the behaviour of different kinds of matter.

 To find out the reasons for this behaviour and so obtain a deeper understanding of nature
 To put the knowledge gained to practical use
The subject is subdivided into three main branches: physical chemistry, inorganic chemistry and organic
chemistry.
Inorganic chemistry is concerned with describing the properties and reactions of all elements and
compound other than those of carbon
Organic chemistry is concerned with chemistry of carbon compounds
Physical chemistry is concerned with how the chemical structure of a substance affects its properties
It attempts to discover general patterns in the behaviour of matter, summarizes these patterns in the
form of laws, and then tries to explain them by means of theories.
Laws. A law is a statement which summarizes some general features of substances or their behaviour.
Theories. A scientific theory is a well-substantiated explanation of some aspect of the natural world
based on a body of facts that have been repeatedly confirmed through observations and experiments.

TOPIC ONE: MATTER
1.O Particulate nature of matter
The entire universe is made up of two things matter and energy.
Matter can be simply described as anything which has mass and occupies space.
Space is that which is occupied by matter

All matter is particulate in nature this basically means that between separate bits of matter
there are spaces which contains no matter. This suggests that matter is not continuous and
indivisible in space.
Matter is made up of tiny particles held together by bonds that can be seen and felt around
us.
Common substances such as clothing buildings, pieces of furniture, food our bodies, metals
and non-metals plants animals, air, water are all made up of tinny particles
Matter can be classified into elements, compounds and mixtures each class exists in three
states namely solid, liquid and gas .in all these classes and states matter is made up of three
basic particles atoms, molecules and ions which are the building blocks or units of matter.
1.1 Atoms, molecules and ions
The three basic particles which make matter are atoms, molecules and ions these are the
building block or units of matter.
An atom is the smallest invisible electrically neutral particle of an element that can take
part in a chemical reaction.
A molecule is a group of two or more atoms chemically combined. Its the smallest, stable
particle of an element or compound that exists by its self.
A n ion is an electrically charged particle formed from an atom or group of chemically
combined atoms, by loss or gain of one or more electrons.
1.2 evidence of particle in matter
1.21 Brownian motion
Brownian motion provides a strong evidence for presence of moving particles. The motion of
liquid molecules was studied by Robert Brown who examined a suspension of pollen grain in
water under a microscope. The grains were observed to move in a random pattern over small
distances. this random movement called Brownian motion was found to occur in many other
liquids besides water and is evidence that molecules of pollen grains were constantly
bombarded by the mobile liquid molecules.

Brownian motion in gases can be demonstrated by viewing a suspension of smoke particles in
small glass cell through a microscope while the cell is illuminated by a beam of light. The smoke
particles of a gas are constantly in motion in all directions with different speed. This is because
they are constantly bombarded by air molecules which are mobile
1.22 Diffusion
is the random movement of particles to fill the available space and spread evenly.
Is the movement of fluid molecules from a region where they are highly concentrated to a
region where their concentration is low.
For gaseous molecules diffusion is spreading of gases from a region of high pressure to a region
of low pressure.
For gasses, diffusion takes place in all directions. The lighter the gas the faster the rate of
diffusion eg ammonia diffuses faster than hydrogen chloride because ammonia is lighter.
The diffusion of gasses is demonstrated by grahams law of diffusion
1.80 The kinetic theory of matter

The theory explains the behavior of matter and their physical properties in terms of movement
of its constituent particles.
The main points of the theory are:
 All matter is made up of tiny moving particles invisible to the naked eye.
 Different substances have different types of particles ( atoms, molecules or ions )
which have different sizes.
 The particles move all the time, the higher the temperature the faster they move on
average.
 Heavier particles move slowly than lighter ones at a given temperature.
Physical state of matter
State of matter: solid, liquid and gas
The conditions of temperature and pressure determine the state of matter. Matter can be
thought of as made of particles which are affected by heat and pressure.

Properties of the states of matter
solid
 At a given temperature solids has a definite volume and shape which may be affected by
changes temperature
 Consist of particles that are found to be stationary but vibrating about a fixed position
 Have very high density and are practically incompressible
 In a solid the particles attract one another there are bonds between the particles which
hold them close together.
 the particles have little freedom of movement and are only able to vibrate about a fixed
position they are arranged in regular manner, which explains why many solids form
crystals.
liquid
 At a given temperature liquids has a fixed volume and will take up the shape of any
container into which it is poured its volume is slightly affected by changes in
temperature
 The particles of a liquid are far apart and free to move throughout the entire system the
movement in a liquid is ordered
 Liquids are slightly compressible
 The forces of attraction between the particles in a liquid are very weak
Gas
 At a given temperature has neither a definite shape nor volume it will take up the shape
of any container into which it is placed
 Particles of the gas are free to move randomly as they have negligible force of
attraction; Particles in a gas are far apart from each other
 Gases are easily compressible
Changes of state
 Interco version of the physical states
The kinetic theory can be used to explain how a substance changes from one state to another

On heating solid the particles gain kinetic energy and this increases their vibration about a fixed
position
on application of sufficient heat, the particle breakdown and melt to form a liquid and the
process is termed as melting.
Melting is the process by which a solid changes to a liquid at constant temperature.
Melting point is a fixed temperature at which a solid changes to a liquid
On heating the liquid particles gain kinetic energy and they move with greater velocity on
applying sufficient heat energy particles break and form a gas and the process is called
evaporation.
Evaporation is a process by which liquid changes to a gas .eventually a temperature is reached

at which the particles escape from the liquid so quickly to form a gas.
The constant temperature at which a liquid changes to vapour on boiling is called boiling point
Boiling point is a constant temperature at which a vapour pressure of a liquid is equal to

atmospheric pressure
Boiling point is affected by
i) Atmospheric pressure the higher the atmospheric pressure, the higher the boiling point
ii) Altitude the higher the altitude, the lower the boiling point because atmospheric pressure
decrease with altitude.
iii) presence of impurities. Impurities decrease the escaping tendency of liquid molecules to
escape into vapour form. Since liquid boils when its vapour pressure is equal to atmospheric
pressure more heat is required and thus increase the boiling point.
During this process of melting and boiling the temperature remains constant because the
energy is used to break the bonds between the particles.
When a gas is cooled the average energy of the particles decreases, and the particles move
closer together. The forces of attraction between the particles now become significant and
cause the gas to condense into a liquid. When a liquid is cooled its particles will move closer
and slower until the forces of attraction are stronger enough to hold them tight together
forming a solid ie it freezes to form a solid. In each of these changes energy is given out
During this process of condensing and freezing the temperature remains constant because the
energy is given out when bond form between the particles

The graphs of temperature against time for the changes from solid to a gas and gas to solid
 Comparison of physical properties between solids, liquids and gases

Molecular structure solid liquid gas
Particle Very closely packed Closely packed Very far apart
arrangement
Intermolecular Extremely strong weak Very weak
forces
Movement of Vibrating in fixed Slowly slide over Moving randomly
particles position each other
compressibility Cannot be Can be hardly Very compressible
compressed compressed
diffusion Cannot diffuse Diffuse slowly Diffuse quickly
1.93 Gaseous state of matter
1.94 kinetic theory of gasses
Kinetic theory makes many assumptions in order to explain the reasons gases act the way they
do.
According to kinetic theory:
i) Gasses consists of small particles called molecules
ii) Molecules are in the state of rapid random motion colliding with one another and with the
walls of the container hence constituting pressure
iii) The average kinetic energy of the molecules is directly proportional to the average Kelvin
temperature.

iv) The collisions of the molecules are perfectly elastic there is no loss in kinetic energy.
v) Particles are point masses with no volume. The particles are so small compared to the space
between them, that we do not consider their sizes in ideal gases.
vi)No molecular forces at work. This means that there is attraction or repulsion between the
particles.
vii) All gases at a given temperature have the same kinetic energy.
viii) lighter gas molecules move faster than heavy molecules.
1.94 Basic gas laws
After experimental observations of the behavior of gases the following laws were formulated
Boyles law:
States that the volume of a given mass of a gas is inversely proportional to its pressure provided
that the temperature remains constant.
This law can be stated in mathematical terms as
P or PV=K or P= or V =
Where V is the volume at pressure P and K is a mathematical constant
If the pressure of the gas is increased from to then the volume decreases from to
and
Graphical representation of Boyles law
V
V P
P
V 𝑃
1
𝑉
Kinetic theory and Boyles law
Decreasing the volume of a fixed mass of gas at constant temperature increases the number of
collisions per unit time between the molecules and the walls of the container which results in
an increase of pressure of the gas since pressure is caused by gas colliding with the walls of the
vessel. On the other hand increase in volume of the gas decreases the rate of collision per unit
time this results in reduction of the pressure of the gas. So the volume is inversely proportional
to the pressure at a constant temperature.
Worked example
375cm3 of a gas M has a pressure of 87000Pa. what will be its volume if pressure is reduced to
85000Pa?
Solution
From Boyles law:
From data: 87000Pa
= 85000Pa
= 375cm3
= = = 384cm3
Charles law
Its states that the volume of a fixed mass of a gas at constant pressure is directly proportional
to its absolute temperature
This law can be stated in mathematical terms as
V T or =K
Where V is the volume at temperature T and K is a mathematical constant.
If a gas has a volume V1 at a temperature T1 and the temperature is changed to T2 the new
volume V2 at constant pressure is given by the equation.

Graphical representation of Charles law
-2730C (K) 0 T
NOTE
The temperature at which all gases would have zero volume is called the absolute zero and is -
2730C or 0K . at this temperature the molecules would come to rest and have no kinetic energy
and the gas would have zero pressure.
-2730C or 0K is theoretically the lowest temperature possible.
In practice however, the temperature of a gas can’t be reduced to absolute zero because all
gases liquefy above this temperature.
Kinetic theory of gases and Charles law
When a fixed mass of a gas is heated, the molecules acquire more kinetic energy and so they
move faster. Hence the number of collisions they make increases. For a constant pressure to be
maintained, more space must be provided for the molecules so that they are further apart than
before. The volume is therefore directly proportional to the temperature at constant pressure.
Worked example
At 340C a sample of a given gas occupies 250cm3. Find the new volume at 1000C if the pressure
remains constant.
Solution
According to Charles law =
From data = 250cm3

= (34 + 273) K = 307K
= (100 + 273) = 373K
= = = 304 cm3
The general gas laws
This is sometimes called the combined gas equation or gas equation. It is an equation
representing both the equation that express Boyles and Charles laws. This combined equation
allows the volume of a gas to be calculated at a given temperature and pressure provided the
volume of the gas is known at another temperature and pressure.
Boyle’s law: V
Charles law: V T
This implies that V or PV T and PV = KT or = K where K is a constant.
The general gas equation is stated as:
= or = Constant
Where V1 is the initial volume at initial pressure and temperature of P1 and T1, respectively;V2 is
the final volume at final pressure of P2 and T2 respectively. The value of the constant depends
on the mass of the gas.
Worked example
A fixed mass of a certain gas has a volume of 76cm3 at 370C and 85kpa. Find the volume the gas
would occupy at stp.
Solution
According to the general gas law: =
From the data = 76 cm3 , = 85000Pa , = (37 + 273) = 310K
= 100000Pa , = 273 K

= = = 73.4 cm3
Avogadro’s law
states that equal volumes of all gases at the same temperature and pressure contains the same
number of molecules.
Also the volume of a gas at constant temperature and pressure is directly proportional to the
amount of gas or the number of molecules of the gas ie V n and V =cn
( where c is a constant and n is amount of a gas in moles)
The volume occupied by one mole of a gaseous molecules at standard temperature and
pressure is always close to 22400cm3 or 22.4dm3. this quantity is often referred to as the molar
volume of the gas.
The ideal gas equation
This an equation that relates the pressure, temperature and volume of a perfect or ideal gas.
An ideal gas or a perfect gas is hypothetical gas that obeys the gas laws at all conditions with its
molecules occupying negligible space and forces of attraction between its molecules are
nonexistent.
Real gases such as helium, hydrogen and nitrogen (very low molecular masses) obey the
equation closely only at high temperatures and low pressures ie when their particles are very
far apart.
The equation may be considered as a combination of Boyles law, Charles law and Avogadro’s
law.
Boyles law: V ( n,T constant)
Charles law: V T (n, P constant )
Avogadro’s law: V n ( P,T constant )
So that the ideal gas equation is:
V and V = or PV = nRT
PV = n RT is the ideal gas equation because it holds only when gases are behaving ideal or
perfect.

R is molar gas constant its value depends on the units adopted for quantities in the equation.
For one mole of a gas at standard temperature and pressure (stp)
P= 101325Nm-2 =101325Pa = 1.0 atm = 760 mmHg
V = 22.4dm3 = 2.24 x 10-2 m3
T = 273K
From R = = = 8.314Jk-1mol-1
From R = = = 0.0821 atm dm3mol-1k-1
Conditions under which gases behave as ideal gases
Low pressure
High temperature
GRAHAMS LAW OF DIFFUSSION
Its states that at constant temperature and pressure the rate of diffusion of gasses is inversely
proportional to the square root of its density
Rate of diffusion of a gas

√
For two gases A and B
And
√ √
√ √
Dividing I by ii
√
= but density if volume is constant then density is direct proportional to mass
√
=√ and are relative mass of gas A and gas B respectively

√
Also rate = , for gas A rate = and gas B rate =

√
= and =√
√ √
Worked example one
A certain volume of oxygen diffused through a porous membrane in 120seconds under the
same conditions the same volume of a gas X diffuse in 112 seconds determine the relative
molecular mass of X (O = 16)
Solution
√
=
√
=√
= 28
Worked example two
A given volume of a gas Z diffuse through a hole is 14.1 seconds while the same volume of
carbon dioxide diffuses through the same hole in 10 seconds. Calculate the relative molecular
mass of a gas Z .
√
=
√
R.M.M of carbon dioxide = 12+ 2x16 = 32
MZ = 87.5
Worked example three
EXAMPLE FOUR
EXERCISES

1.95 Application of diffusion
a) separation of isotopes
diffusion is applied in separation of isotopes eg isotopes of uranium 235 from uranium 238
b)extraction of Helium from natural gas
c)determination of molar mass of gasses
d) determining the density of a gas
e) absorption of nutrients by cells in living organism
1.96 Effusion
Effusion is similar process. Effusion is the process where gas molecules escape from an
evacuated container through a small hole. It is assumed that while a molecule is exiting, there
are no collisions on that molecule.
1.97 Daltons law of partial pressure
It states that for gases that do not chemically react, the total pressure of the mixture of gases is
the sum of their partial pressures .
Ptotal = PA + PB +PC +……………….+ PZ Where PA , PB ,PC ……………and PZ are partial pressures of

individual gases
Partial pressure of a gas
Is the pressure the gas alone would exert if it occupied the volume that was initially occupied
by the mixture of the gases of which it was part.
Consider gases A and B in a given vessel
Using Daltons law, PTOTAL = PA + PB
Applying the ideal gas equation PV = n RT, PTV = nTRT
For gases A and B
PAV = nART , ………..(I) P BV = nBRT ………(II)
Dividing equation I and ii
= = this implies = Similarly =

Where are the mole fraction of the gases A and B
Mole fraction is the ratio of the number of moles of a component of a gas to the total number
of moles of the component of the gases in the mixture.
Partial pressure of a gas depends on the number of moles of that gas present and is related to
the total pressure by the equation.
Partial pressure = mole fraction x total pressure of the system
Worked example
12g of nitrogen 0.4g of hydrogen and 9.0g of oxygen are put in a one litre vessel at pressure of
22.4 atmosphere calculate the partial pressure of the respective gases.( N=14,H=1.0,O=16 )
SOLUTION
Relative molecular mass of nitrogen =2 x 14 = 28 ,moles of nitrogen = =0.43
Relative molecular mass of oxygen =2 x 16 = 32 , moles of oxygen = = 0.38
Relative molecular mass of hydrogen =2 x 1 = 2, moles of hydrogen = =0.2
Total number of moles 0.43 + 0.38 + 0.2 =0.91
Partial pressure of nitrogen x 22.4 =10.58 atmosphere
Partial pressure of hydrogen x 22.4 =4.92 atmosphere
Partial pressure of oxygen x 22.4 =6.89 atmosphere
1.98 Real gases or non-ideal gases
Kinetic theory assumes that all gases behave ideally, however we know that this is not the case.
Obviously real gas particles do occupy space and attract each other. These properties become
apparent at low temperature or at high pressure.
There are two factors that are responsible for the non- ideal gases
i) intermolecular forces of attraction

An ideal gas is assumed to have negligible intermolecular forces of attraction. However at
low temperature the vander-waals forces of attraction become more pronounced because

the molecules have insufficient energy to overcome the forces of attraction. The molecules
become closer together hence resulting into deviation from ideal gas behavior.
ii) Molecular volume

An ideal gas is assumed to occupy negligible volume. However at high pressure the
molecules of a gas become so tightly packed that their volume is significant
compared to the overall volume.
1.98 modification of the ideal gas equation vander- Waal equation
Vander- waal proposed that we correct for the fact that the volume of areal gas is two large at
high pressure by subtracting a term from the volume of a real gas before we substitute it into
the ideal gas equation.
If the total volume is V, and the volume occupied by gas molecules is nb the compressible part
of the total volume will be (V-nb) then P(V-nb) = a constant.
If molecules of a gas attract each other, then a molecule in the interior is attracted equally in all
sides by other molecules but this isn’t true for a molecule outside. And also the velocity of a
molecule just about to make an impact with the walls of the container will be reduced by the
attraction of the molecules towards the interior of the gas, hence pressure will be reduced.
Note pressure of a gas is due to molecular impacts on the walls of the container.
To correct for the fact that pressure of a gas is smaller than expected from ideal gas equation
vander-waal added a term to the pressure in this equation.
(P+ )(V-nb) = nRT where a and b are constants n number of molecules.
The ideal gas equation predicts that a plot of PV verses P for gas would be a horizontal line
because PV should be a constant.
NOTE
i) The effect of molecular attraction increases pressure and consequently the volume
is less than expected and the value of PV will be less than that of ideal gas.
The gas will be more compressible than the ideal case.
ii) At low pressure the volume occupied by gas molecules is not significant but at high
pressure the molecules are compacted to a degree such that they tend to behave
like liquids, which are almost incompressible as a result, at higher pressure the
volume of a gas remains larger than the ideal case and consequently the value of PV
increases

Experimental data for PV verses V for H2, N2 and CO2 are given in the figure below.
PV N2
H2
CO2
Ideal gas
For nitrogen and carbon dioxide, the values of PV decrease at first as pressure increases
because the effect of molecular attraction outweighs the deviation due to molecular volume at
low pressure.
Molecular attractions arise from vander-waal forces.
But at high pressure PV increases because the deviation due to molecular volume is greater
than that of molecular attraction.
The decrease in PV with increase in pressure shows that initially nitrogen and carbon dioxide
are at first more compressible than expected.
For hydrogen, PV increases from the beginning because deviation due to molecular volume is
greater than deviation due to molecular attraction at all pressure.
The increase in PV from the start for hydrogen shows that it’s less compressible than expected.

liquefaction of gases
By sufficiently cooling the gas at atmospheric pressure it can be condensed and turned into a
liquid. Many gases not all can be liquefied by increasing the pressure at ordinary
temperature(compression) or decreasing the temperature. These conditions of temperature
and pressure under which gases liquefy were investigated by Andrew.
Andrew plotted graphs of P against V for a fixed mass of carbon dioxide
321
C B 304
A 286
VOLUME
Isothermals of carbon dioxide
Each isothermal refers to the same mass of carbon dioxide and shows the variation of volume
of carbon dioxide with pressure for a particular temperature.
Isothermal 321K almost represents the behavior of an ideal gas.
The isothermal of 286K,ABCD is markedly different. Its course is interpreted in the following
way.
The portion AB represents the usual contraction of the volume of a gas as pressure increases
and approximates to a hyperbola

The portion BC represents a large contraction in volume for almost no pressure change at B the
pressure has become large enough to start the liquefaction of carbon dioxide at 286 K, and
from B to C this liquefaction continues and completes itself with only slight increase of
pressure at C liquefaction is completed and liquids being almost incompressible, further
increase of pressure produces no appreciable volume change.
Portion CD represents almost no volume changes for a very large pressure change.
At higher temperatures such as 295K a similar path EFGH is followed however above304K its
impossible to liquefy a gas however much pressure exerted. This temperature is called critical
temperature for carbon dioxide. The pressure required to liquefy the gas at critical temperature
is called the critical pressure and the volume of one mole of a gas at the critical temperature
and pressure is the critical volume.
Critical temperature: is the temperature above which a gas cannot be liquefied by increasing
pressure.
Every gas has its critical temperature above which it cannot be liquefied by increasing pressure
for example
H2 =-2300C ,N2 =-1470C,O2 =-1190C,SO2 = +1570C, NH3 = +1310C ,Cl2=+1410C
Above the critical temperature a gas may be regarded as a permanent gas since it cannot be
liquefied by increasing pressure
Note
Two factors are involved in liquefaction of a gas these are intermolecular attraction which tend
to bring the molecules together and thermal energy of molecules which tend to keep them a
part’
Liquefaction of gases occurs when the intermolecular attraction are greater than thermal
energy this is achieved below critical temperature.
Any gas which has critical temperature above room temperature can be liquefied by pressure
alone for example NH3,Cl2,SO2 CO2.

RELATIVE MOLECULAR OF GASES
Relative molecular mass: this is a mass of one molecule of an element or compound divided by
the mass of one-twelvelfth of the mass of an atom of carbon -12 isotopes.
Relative molecular mass of a gas can be obtained by measuring the relative density or vapour
density of the gas
Relative density of a gas is defined as the ratio of the weight of equal volume of the gas and
hydrogen measured at the same conditions of temperature and pressure.
Relative density =
Relative density of a gas can be obtained by direct weighing or by measuring the rate of
diffusion of a gas and comparing it to that of another gas of known relative density.
Relative density is equal to the mass of 11.2dm3 of vapour.
Relative molecular mass = 2 x relative density of a gas or = 2 x vapour density of a gas
This method can be applied to vapours of substances which are liquids or solids at ordinary
temperature provided they can be vapourised.
Experimental determination of relative molecular mass of gases
a) Direct weighing
A large container of volume V is weighed when full of a gas at a pressure P and temperature T.
the same container is then weighed after evacuation in order to obtain the mass of the gas .
Sample results
Mass of container full of gas = a g
Mass of empty container =bg
Mass of gas = a-b g
From the ideal gas equation PV = nRT
PV = RT
M= =

The following precautions should be taken
i)the gas must be pure
ii)the container should be completely evacuated
iii)all weighing should be done at the same temperature and pressure
note
Pressure must be converted to Nm-2, volume must be converted to m3, temperature to Kelvin.
Worked example
0.228g of ethoxyethane vapour occupies 94.08 cm3 at 1000C and100.8kNm-2 pressure.
Calculate the relative molecular mass of ethoxyethane.
Solution
Using PV = RT and M =
M= = 74.158
OR using =
= = = 68.52 cm3
One mole of a gas at stp occupies 22400cm3
68.52cm3 of the gas weighs 0.228g
22400cm3 of the gas will weigh = 74.558g

b)Using a graduated syringe(for volatile liquids and gases)
apparatus
A known quantity of a liquid is injected into a gas syringe, where it vaporizes and the volume
occupied by the vapour is measured. The temperature around the syringe and atmospheric
pressure are recorded.
The relative molecular mass is then calculated.
Worked example
0.160g of a volatile liquid X was injected into a gas syringe at 12 0 C and 745mmHg
pressure.55.5cm3 of the liquid vapour was produced. Calculate the formula mass of liquid X.
Solution
Using PV = RT
M= =
OR using =
= = = cm3
One mole of a gas at s.t.p occupies 22400cm3
68.52cm3 of the gas weighs 0.228g
22400cm3 of the gas will weigh = g

Empirical and molecular formula
The empirical formula of a compound is the simplest formula which expresses the ratio of the
number of atoms of the element present in the compound.
The molecular formula is one which shows the actual number of atoms of the elements present
in a molecule or compound.
Knowing the molecular mass of the compound then the molecular formula can also be
obtained.
The empirical formula can be obtained by using data from combustion analysis.
Formular of hydrocarbon on explosion
A gaseous hydrocarbon CxHy explodes in excess oxygen according to the equation
CxHy(g) + (x + )O2(g) XCO2(g) + H2O(l)
The initial volume of the hydrocarbon and oxygen are noted
After the explosion the water formed occupies negligible volume at room temperature and
pressure.
And the residual gases are carbon dioxide and oxygen.
Carbon dioxide is absorbed in concentrated potassium hydroxide solution.
The remaining residual gas will be the unused oxygen gas.
Worked example
15cm3 of gaseous hydrocarbon Z was exploded with 105cm3 of excess oxygen. The residual gas
occupied 75cm3, on addition of concentrated potassium hydroxide solution there was a
reduction in volume of 45cm3.determine the molecular formula of Z.
Solution:
Let the molecular formula of Z be CxHy
CxHy(g) + (x + )O2(g) XCO2(g) + H2O(l)
Volume of CxHy = 15cm3
Volume of CO2 = 45cm3

Volume of O2 that reacted = (105-30)cm3 = 75cm3
1cm3 of CxHy react with(x + ) cm3 of O2 to form Xcm3 of CO2
15cm3 of CxHy react with 15(x + ) cm3 of O2 to form 15Xcm3 of CO2
15X = 45
X=3
15(x + ) = 75
(3 + ) = 5
Y=8
the molecular formula of Z be C3H8
Formula of hydrocarbon by oxidation
The hydrocarbon is oxidized by oxygen, hydrogen is oxidised to water and weighed after
absorption in concentrated sulphuric acid. Carbon is oxidised to carbon dioxide and weighed
after absorption in concentrated potassium hydroxide.
Relative molecular mass of carbon dioxide = 12 +2x16 = 44
Relative molecular mass of water = 1 x2 + 16 = 18
If ag of compound produce Cg of CO2 and W g of H2O then
Mass of carbon in carbon dioxide = xC
Percentage of carbon in the compound = x100
Mass of hydrogen in water = xw
Percentage of hydrogen in the compound = x100

Worked example
On complete combustion of 120g of a hydrocarbon Z of molecular mass70g, 377.1g of carbon

dioxide and 154.4g of water was evolved.
a) Calculate the empirical formula Z.

b) Determine the molecular formula of Z.
solution
a)Percentage of carbon in the compound = x100 = 85.7%
Percentage of hydrogen in the compound = 1 =14.3%
Elements C H
% composition 85.7 14.3
Number of moles
7.14 14.3
Mole ratio
1 2
The simplest formula of Z CH2
b) Molecular formula of Z (CH2)n = 70
( (12x1) + (1x2))n = 70
14n = 70
n = =5
molecular formula = C5H10

Worked example
0.5g of organic compound Y containing carbon, hydrogen and oxygen gave on combustion
0.6875g of carbon dioxide and0.5625g of water if the vapour density of the compound is 16.
Suggest the structural formula of the compound.
organic compound containing nitrogen
a) compound is burnt so that nitrogen is evolved and measured as a gas.
CXHYNZ(g) +(x + )O2(g) x CO2(g) + H2O(l) + N2(g)
If ag of the compound produce n cm3 of nitrogen at stp
22400cm3 of nitrogen weigh 28g
ncm3 of nitrogen weighs )g
percentage of nitrogen in the sample 1 )
worked example
0.72gof a compound gave on combustion 1.615g of carbon dioxide and 0.99g of water. 0.42g of
the same compound gave 84cm3 of nitrogen at 150C and 760mmHg. Vapour density of a
compound is 29.5 find the formula of the compound.
solution

b)Nitrogen can be converted to ammonia sulphate by heating the compound with concentrated
sulphuric acid and potassium hydrogen sulphate. The ammonia sulphate is then diluted and
heated with excess alkali to expel ammonia gas. The ammonia gas is estimated by absorption in
a standard acid.
Worked example
0.708g of compound R gave on combustion 1.056g g carbon dioxide 0.54g of water. 1.23gof the
same compound yielded ammonia which required 20.4cm3 of 2.0M hydrochloric acid for
neutralization. Vapour density of compound is 29.5 calculate the formula of the compound
Chlorine, Bromine or iodine
The halogens are converted to corresponding silver compound by heating with silver nitrate
and fuming nitric acid. The silver halide is weighed after purification.
If ag of the compound produce b g of Ag Cl
Mass of chlorine in compound =( )g
Percentage of chlorine in the compound =( 1 )
sulphur
sulphur is converted to sulphuric acid by heating with fuming nitric acid and then precipitated
as barium sulphate,
if a g of a compound produce w g of barium sulphate
mass of sulphur =
% of sulphur =
Oxygen
This element is estimated as the difference from 100% after accounting for all other elements.
Note:
The calculation may not give actual integers at this stage it may give ratios such as
1.5:1,1.33:1,1.67:1 these are written in the lowest integral equivalents as

1.5:1 becomes 3:2 after multiplying by 2
TOPIC TWO; THE ATOMIC STRUCTURE

The Dalton’s atomic theory
The first modern atomic theory was proposed by John Dalton,who proposed that;
 Matter is made up of atoms (small invisible particles)

 Atoms cannot be created or destroyed
 Atoms of the same element are exactly alike even in mass but differ from atoms of
other elements.
 A chemical reaction involves rearrangement of atoms or combination of atoms. During
reactions, the individual atoms remain intact.
 When atoms combine, they do so in small whole numbers to form compounds or
molecules.
However, in the last hundred years or so it has been proved by great scientists, such as
Bohr,Eisten,Moseley,Thomson,Rutherford and chadwick,that ;
 Atoms can be split into simpler particles i.e neutrons, protons and electrons.
 New atoms can be created and destroyed i.e during radioactivity
 Atoms of the same element can differ in masses e.g in the case of isotopes.
 Not all reactions involve combination of atoms to form molecules or compounds; some
actually involve formation and combination of ions.

Discovery of some particles of an atom
a)Discovery of electrons
Electrons were discovered as streams of cathode rays by J.J. Thompson. In his experiment, he
applied a high voltage to a gas at low pressure in a discharge tube. A beam of rays that caused a
green glow on the screen were observed to be moving from the cathode in a straight line
These rays had the following properties:
 They were deflected by magnetic and electric fields in directions which indicated that
they were negatively charged.
 When an object was placed between the cathode and the screen, a shadow was formed
on the screen indicating that the rays travel in a straight line.
 The rays had the same properties regardless of the nature of cathode and gas used in
the tube.
From the above, the particles were negatively charged and present in all matter and were
therefore named electrons.
Only further analysis, it was found out that each of these particles had a mass of times the
mass of hydrogen atom.
c)Discovery of protons
When Thompson’s experiment was repeated by putting a cathode in the center of the
discharge tube, a red glow was observed in the opposite side of the green glow.
When a high voltage is applied to the discharge tube containing a gas at low pressure, the gas
molecules are converted to atoms and atoms are ionised by bombardment with fast moving
electrons from the cathode.
For example , when hydrogen gas is used;

The electron ejected from the atom is attracted towards the anode and detected by the screen
causing a green glow .The positively charged ions are repelled by the anode and attracted
towards the cathode and detected on a screen in the opposite direction as a red glow.
 The particles that caused the red glow had the following properties:
 They were deflected by magnetic and electric fields in directions that showed they were
positively charged.
 They required much stronger magnetic or electric fields to be deflected unlike cathode
rays indicating that they are heavier particles compared to cathode rays.
 Their mass depends on the mass of the gas in the discharge tube .i.e. when hydrogen
gas is used , the mass of the particle is equal to the mass of hydrogen atom.
 Masses of the particles from other gases are heavier than those from hydrogen gas.
These were positive rays that were later named protons. symbol
C)Neutrons
An atom consists of positive and negative particles (protons and electrons), and since an atom
is neutral, the number of protons must be equal to the number of electrons. The atomic mass
of an atom is found to be greater than the mass of protons in it. This therefore implied that
there must be other particles that makeup for the extra mass. These particles were called
neutrons and had almost the same mass as protons but were neutral (had no charge).
2.1.3 NUCLEAR MODEL OF THE ATOM
Rutherford’s experiment
Rutherford directed beam of alpha particles towards a very thin gold foil as shown below
Gold foil
Alpha particles +
A
+
+
+ B
+ +

The following observations were made:
i) Most of the alpha particles went through undeflected
ii) A few alpha particles suffered a slight deflection of less than 90 0
iii) very few of the alpha particles bounced
conclusion
the atoms consists of a very small positively charged nucleus surrounded by a large space.
The large space contains light negatively charged electrons
When the alpha particles pass through the large space no deflection occurs because its
electrons are negatively charged and the alpha particles are positively charged the rebounded
particles had collided with the core of the atom the nucleus which is positively charged.
2.2.3 structure of an atom
The atom is made up of three subatomic particles Electrons ,protons and neutrons
The three sub-atomic particles are found in distinct and separate regions. The protons and
neutrons are found in the Centre of the atom, which is called the nucleus.
The neutrons have no charge and protons are positively charged.
The nucleus occupies only a very small volume of the atom but is very dense.
The rest of the atom surrounding the nucleus is where electrons are most likely to be found.
The electrons are negatively charged and move around very quickly in electron energy levels.
The electrons are held within the atom by an electro-static force of attraction between
themselves and the positive charge of the protons in the nucleus
Characteristic of a proton, a neutron and an electron
particle symbol Relative mass(amu) Relative charge

proton P 1 +1
neutron n 1 0
electron e -1

Although atoms contain electrically charged particle, the atoms themselves are electrically
neutral.
This is because atoms contain equal numbers of electrons and protons.
2.1.4 Atomic number and mass number
Elements are made up of atoms. Atoms are in turn made up of subatomic particles- electrons,
protons and neutrons. The Symbols of the elements are used in showing the number of
different subatomic particles each atom has.
2.1.5 Atomic number Z
The atomic number is the number of protons in the nucleus of an atom.
In the neutral atom it is equal to the number of electrons around the nucleus.
The atomic number is also referred to as proton number.
All atoms of the same element have the same atomic number it has the symbol Z.
2.1.6 The neutrons number
The nucleus contains protons and neutrons. The protons and neutrons are called nucleons. The
number of neutrons in each atom differs. The number of neutrons in an atom is given the
symbol N
2.1.7 The mass number
The mass number is the sum of the number of protons and neutrons in an atom it can also be
called nucleon number.
It is possible for atoms of the same element to have different mass numbers.
This due to different numbers of neutrons. The mass number has the symbol A.
2.1.8 representation of the atom
To indicate the mass number and atomic number of an atom of symbol X:
i) The mass number, A is placed as a left superscript

ii) The atomic number, Z is placed as a left subscript
The element lithium (Li) has a mass number of 7 and atomic number of 3 it is shown as

Isotopes
Isotopes are atoms of the same element which have the same atomic number but different
mass numbers. It is the difference in the number of neutrons which brings about the different
mass numbers.
Each isotope has a different number of neutrons in the nucleus.
The three naturally occurring isotopes of carbon are represented as and orcarbon-
12,carbon-13 and carbon-14 respectively.
Note the isotopes of an element react in the same way. This is because chemical reactions
involve electrons, neutrons make no difference.
2.1.9Nuclides
The word nuclide is used to describe any atomic species of which the proton number and
nucleon number are specified. Nuclides are written as . The species is
a nuclide.
2.1. 9.1Isotopic abundance
Most elements consists of mixtures of isotopes the fraction or percentage of each isotope in
the mixture is called the isotopic abundance
Example silicon occurs naturally in naturally occurring compounds as silcon
isotope
Percentage abundance 92.28 4.67 3.05
Note percentage abundance add up to 100 whereas fractional abundance add up to 1.00
2.1.9.2 Atomic mass
The mass of an atom is too small to be measured on even the most sensitive balance.
Chemists use relative masses to compare the atomic masses of different elements
An atom of the carbon-12 isotope is chosen as the international standard for the measurement
of atomic mass.
Relative isotopic mass is the mass of an atom of an isotope compared with one-twelfth the
mass of an atom of carbon-12.
If a natural sample of any isotopic element is collected, each isotope would occur in different
amounts.

The different amount of each isotope in the naturally occurring element is called its abundance
When the proportion of the isotope in a sample of the naturally occurring element is expressed
as percentage, it is called percentage abundance. It is called fractional abundance when
expressed as a fraction.
2.1.9.3 calculating the relative atomic mass of an element having more than one isotope
Relative atomic mass Ar is the average mass of an atom of the element compared with one-
twelfth of the mass of an atom of carbon-12
Ar =
Worked example
Calculate the relative atomic mass of chlorine given that chlorine has two naturally occurring
isotopes
Consists of 75% and

∑
Relative atomic mass =
. = = 35.5
Worked example
Copper has two isotopes and of relative isotopic mass of 62.9 and64.9 respectively
the relative atomic mass of the naturally occurring copper is 63.55. calculate the percentage
abundance of each isotope.
Solution
Let the percentage abundance of isotope be y and that of be 100-y

∑
Relative atomic mass =
. = = 63.55
Y= 67.5
% =67.5 and%

2.1.9.3 Measuring relative atomic mass
Relative atomic mass is measured using a mass spectrometer. The mass spectrometer
separates species of different masses and measures their masses by electrical methods
2.1.9.4 structure of the mass spectrometer
2.1.9.5 action of a mass spectrometer
 The apparatus is first evacuated to avoid collision between air and ions of element.
 The sample of the substance is vapourised by heating.
 A stream of vapourised sample of the element is passed through a pin sized hole into
the ionization chamber were they are subjected to an electron gun emitted by a heated
element
 High energy electrons from the cathode are attracted to the opposite anode
 In the process they collide with vapourise sample and knock off electrons from atoms or
molecules to form positive ions.
 The positive ions are attracted and accelerated by a stronger electric field so that ions
which enter the magnetic field are of the same velocity.
 In the magnetic field the ions are deflected and focused onto the detector According to
their mass to charge ratio .
 Changing magnetic field brings species of different mass onto the detector, heavier
species are deflected less and nee a stronger magnetic field to focus them onto the
detector ligher species needs weaker magnetic fields.
o The detector collects the species of different masses separately and the
collected charges constitute an electric current.
o The separate amounts of electric currents are proportional to the percentage
abundance of each species of different mass.
The instrument amplifies the percentage abundance and mass and records it as amass
spectrum.

2.1.9.5 relative atomic mass from a mass spectrum.
A mass spectrum shows percentage abundance verses the mass of each species in mass
spectrometer.
The mass spectrum is calibrated(based) on the carbon-12 scale and therefore the relative
atomic or molecular mass of all species can be read directly
Isotopes present in the sample are shown as peaks.
The area under each trace at any mass point is proportional to the abundance of that
mass.
Each peak indicates one isotope with its percentage abundance and relative atomic
mass or mass number.
 The number of peaks is equal to the number of isotopes.

Relative atomic mass
RADIOACTIVITY
Radioactivity is the spontaneous disintegration of the nuclei of certain isotopes with emission of
beta particles, alpha particles or gamma rays.

Certain elements have an unstable isotope. The nuclei of these atoms break up spontaneously
with the emission of certain type of radiation. The atoms of these isotopes with unstable nuclei
are radioactive and they are called radioisotopes.
Radioisotopes : are atoms with unstable nucleus which disintegrate spontaneously to give off
one or more type of radiation.
Examples of radioactive isotopes are
There are two types of radioisotopes naturally occurring isotopes and artificially radioisotopes
Elements such as Uranium which spontaneously emit energy without absorption of energy are
said to be naturally radioactive.
Artificially radioactive isotopes may be produced by adding energy to stable nuclei.
When these unstable atoms spontaneously break up they are said to distergrate or decay.
The result of this process is that energy is released in the form of heat and radiation is emitted
from the nucleus.
Radioactive elements can emit one or more of the three types of radiation the types of
radiation are alpha, beta and gamma
Properties of radioactive elements
They are very unstable and disintegrate to stable nuclides.
They emit particles alpha and beta or rays gamma upon disintegration.
They affect photographic materials due to emission of particles and rays.
When they disintegrate they release a lot of energy.
They also ionize gases and produce phosphorescence.

Nature and properties of radiations
+ -
Type of Nature Electrica Effect of Effect of Relative Relative

radiatio l charge electric field magnetic field penetrating ionizing
n power power
Alpha(α) 2 protons and +2 Deflected to the Deflected by Very low Very high,
2 neutrons negatively magnetic field penetrating particles
written charged plate power. produce large
as Particles do numbers of
not pass ions as they
through penetrate
paper and gases
have a range
of only a few
cm in air
Beta(β) Β- particle in -1 Deflected to the Deflected by a Very good Low ionizing
the form of positively magnetic field penetrating power,
electrons charged plate in the power, particles
) deflection is opposite particles can produce weak
greater than direction to α- pass through ionization in
that of α- particle. They a few cm gases
particle due to can be thickness of

much smaller deflected by a aluminium
mass of the much weaker foil.
beta particle magnetic field
due to their
much smaller
mass
gamma Electromagneti No Unaffected by Unaffected Very high Very low

c wave contains charge electric field hence no penetrating ionizing
no particle thus 0 hence no deflection power power
atomic number deflection
and atomic
mass is
unchanged
when an atom
emits gamma
rays nucleus
only loses
energy
Detection of radiations
Use of photographic film the radiations destroy the film if exposed for some time
They cause surface of some substances to glow
They cause ionization of air molecules
Results of radioactive decay
Radioactive changes involve the nucleus and are called nuclear reactions
During nuclear reactions one element may be converted to another either by radioactive decay
or by atomic fission or atomic fusion.
Alpha particle emission.
Many of the heavy elements (atomic number 83 and above) undergo α-decay, eg radon-220,
polonium-218 andplutonium-238.

An alpha particle is a helium nucleus so that its loss causes a decrease of 2 in the atomic
number and 4 in the mass number.
Beta particle emission
β-decay occurs in both heavy elements and light elements(atomic number less than 83 ) in β-
decay, a neutron changes into a proton plu an electron the electron is lost while the proton
remains in the nucleus:
The daughter nucleus therefore contains one less neutron and one more proton than the
parent nucleus.The mass number is unchanged,but the atomic number is increased by one. For
example,
Gamma radiations
When gamma radiation is emitted, there is no change in the atomic number or mass number of
the isotope. For example,
Notice Ὡ
That the totals of mass number and proton number are the same on both sides of the equation
Gamma radiation is emitted during α-decay and β-decay, and is due to change within the
nucleus.
Differences between nuclear and chemical reactions
Nuclear reactions Chemical reactions
occurrence Takes place inside the nucleus Takes place in the outer

or with the nucleus. Protons, electronic shell. Valence
neutrons and electrons electrons involved
involved
Energy involved Large amount of energy Much less energy released
released.
products New nuclide is formed New compound but not
nuclide is formed.
conditions Not governed by Governed by environmental
environmental factors factors such as temperature.
Decay series
When the product of a radioactive disintegration is itself unstable, then a further radioactive
disintegration will occur. This goes on until eventually a stable isotope is formed each step
involving the loss of either an alpha or beta or occasionally both.
Consider the thorium decay series
Half-life
Half-life t1/2 of a radioactive nuclide is the time taken for the radioactivity of that nuclide to
decay to half of its original value.
Its independent of the amount of substance taken.
It’s the same whatever the initial amount of substance.

Its possible to characterize radioactive isotopes by quoting their half lives
The half-life period for polonium-214 is 1.6x 10-4seconds.This means that after 1.6 x 10-4
seconds the activity of a sample of this isotope of polonium will have been reduced by half.
After another1.6 x 10-4 seconds the activity will only be of the original level.
The half-life of a pure radioactive nuclide can be conveniently found using a graphical method.
Half life is used as a measure of the relative stability of an isotope
The shorter the half-life, the faster is the decay of the nuclide.
The longer the half-life, the slower the decay of the nuclide.
Half-lives of different isotopes of the same element are not the same.
The rate at which atoms of a radioactive nuclide decay, is directly proportional to the number
of atoms of the nuclide in the sample.
Rate = KN
= KN
Where N is the number of atoms and
K is the constant of proportionality, called the decay constant
∫ =∫
lnN = Kt + c
N =N0
ln =-Kt or ln = Kt converting to base ten 2.303log = Kt

at half-life period, t ,N= ,therefore
2.303log ( )=K
2.303log 2 = K
Worked example
Nuclear fission or atomic fission
Nuclear fission is the splitting of atomic nucleus into two approximately equal fragments, about
half the size of the original nucleus, together with a number of smaller particles
(neutrons, protons and α-particles).
A large amount of heat energy is released.
Spontaneous fission is the natural fission whereas induced fission is the fission of a nucleus
brought about by bombarding a nucleus with neutrons.
+ Energy
During fission there is loss in mass and this mass is converted into energy according to
Einstein’s equation E= MC2 Where E is energy is mass and C is speed of light.
Each of the fission neutrons (two or three) that are released can initiate the fission of another
nucleus. This result in a nuclear chain reaction such a nuclear chain reaction when unchecked
produces a huge explosion. This is the basis of an atomic bomb.

Nuclear fusion
Is the process whereby two light nuclei join to form a heavier one. A large amount of energy is
released during this reaction. It occurs at extremely high temperatures this is because large
energies have to be given to the positively charged nuclei to overcome strong repulsive forces
between them and unite them.
This is the basis of the hydrogen bomb. Thermo nuclear reaction take place on the stars and the
sun producing a very high temperature of approximately15x106 0C
Uses of radioactive isotopes
1. In carbon dating- carbon-14 can be used to calculate the age of plant and animal
remains. Living plants and animals take in carbon which includes the radioactive isotope
carbon-14. When a plant or animal dies it takes in no more carbon-14 and that which is
already present decays. The rate of decay decreases over years and the activity that
remains can be used to calculate the age of plant or animal.
2. Radioactivity is used to destroy cancer cells colbalt-60 is used to provide gamma rays to
destroy cancer cells without harming patients’ health tissues.
3. Used in surgery. Surgical instruments are more effectively sterilized by radioactivity than
boiling.
4. Used for detection of leakage in underground water and fuel pipes. By introducing a
short lived radioisotope into the pipe the level of radioactivity on the surface can be
monitored. A sudden increase of surface radioactivity shows where water or fuel is
leaking.
5. Tracer studies, tracer techniques use radioactive isotopes to track the path of an
element through the body. Radioactive iodine is administered to patients with defective
thyroids to enable doctors to follow the path of iodine through the body in the
treatment of goitre.
6. In industry as tracers in detection of wear in machinery eg bearings, pistons.

7. Nuclear power stations harness the tremendous amounts of energy released when
uranium-235 undergoes nuclear fission. The energy released, by this controlled chain
reaction is then used to produce electricity.
8. Food preservation, the preservation of food using gamma rays is quite widespread
worldwide. Treating food with gamma rays can: slow down the ripening of some fruits
and sprounting of potatoes, kill highly dangerous micro-organisms such as salmonella,
kill micro-organisms that spoil food.
Effects of radioisotopes
A radioactive material, despite its importance and numerous uses can be dangerous.
Large dosages of ionizing radiations can kill living cells and whole organisms or can cause
illness.
Low dosages over long periods can cause foetal deformities, leukemia, and bone cancer
and other forms of cancer.
Stability of the nucleus and binding energy

A stable nucleus is one which does not undergo radioactive disintegration. A relatively
stable nucleus possesses a very long half life. Light nuclei atomic numbers less than 20
are stable if their neutron to proton ratio is one, nuclides with even number of protons
or neutrons or both are more stable than those with odd number of protons or
neutrons.
Unstable nuclides are atoms having number of neutrons much greater than the number
of neutrons and therefore undergo radioactive disintegration or decay emitting alpha or
beta particles
Nuclides with atomic number greater than 83 are heavy and unstable hence undergo
radioactive decay.

A graph of number of neutrons against number of protons
neutron
proton
The graph shows a stable belt shaded area running diagonally starts to curve upwards at atomic
number 20 and stops abruptly at atomic number 83.
All the known stable nuclei lie within the shaded area. A long the dotted line the nuclides have
equal number of neutrons and protons.
Factors that determine stability of a nucleus
Atomic number/ atomic mass
Stability reduces as atomic mass increases. Atoms with atomic number greater than 83 are too
heavy to be stable.
Half- life
The longer the half-life, the more stable the nucleus.
Binding energy
The greater the binding energy, the more stable the nucleus.
Binding energy is the energy given out when a nucleus is formed from the individual neutrons
and protons or it is the energy required to separate the nucleus into the individual nucleons.
Neutron to proton ratio
Very light nuclei atomic number less than 20 are stable if their neutron to proton ratio is
1.relative light nuclei atomic number between 19 and 83 are stable if their neutron to proton
ratio is slightly greater than 1

Nuclei with high neutron to proton ratio lying above the belt of stability gain stability by beta
decay during beta ,a neutron splits up forming a proton and an electron
The proton remains in the nucleus but the electron is ejected. This results in the decrease in the
number of neutrons in the isotope by one and the protons increases by one
Nuclei with low neutron to proton ratio lying below the belt of stability gain stability by
positron decay or electron capture. The unstable nucleus captures an electron from its inner-
most shell and the electron combines with a proton in the nucleus to form a neutron
The isotopes which undergo electron capture have fewer neutrons than stable isotopes.
Nuclei with atomic number greater or equal to 84 are heavy and lie beyond the upper right
edge of the stable belt. These gain stability by emission of alpha particles which decreases both
the number of neutrons and protons by two.
Very heavy nuclei cannot achieve stability with single emission such unstable nuclei undergo a
series of emission.

Electronic structure of an atom
ATOMIC SPECTRUM
When an element or compound is heated in a flame, or by means electric discharge, they emit
energy in form light. Analysis of this light with a spectroscope shows that a discontinuous
spectrum appears in form of light, and this is known as atomic/line spectrum. And is a typical
characteristic of an atom.
An atomic spectrum consists of patterns of lines which are found at various wave lengths and
the actual pattern is different for each element.
The lines might be so closely grouped that they appear in bands. This is called band
spectrum and is characteristic of a molecule.
NB: When energy is supplied to an atom, the outermost electrons are the first most likely to
absorb energy .The energy gained by the electron causes it to move an added distance from the
nucleus.
An electron which has been removed from a given level, but still within the influence of the
nucleus may still fall back to the initial energy level with the emission of light energy .The
energy given out is of definite amount for each unit is known as Quantum.
Quantum theory therefore states that matter cannot absorb or emit energy in continuous
amounts but in small continuous units called quanta.
If energy supplied is enough to move an electron from an energy level, it will emit light of
only one kind of wavelength on returning.
When the energy is enough to move an electron many energy levels away from the ground
state, it returns in series of moves emitting different wavelengths of light for each transition
level .
If energy is not enough to move an electron, no spectrum is emitted, and the energy
absorbed by an atom just increases its potential energy.
Emitted energy=K.E=hf –hfo
But f=
Energy =h -h
E =hc( )

where
h is plank’s constant
f is new frequency
fo is thresh hold frequency
c is velocity of light
energy at a given energy level =
HYDROGEN SPECTRUM
When electric discharge is passed through hydrogen gas at low pressure in a test tube, it glows
reddish pink .Many molecules break into single molecules.
If the light emitted is passed through a prism, the atomic spectrum of hydrogen which
consists of series of sharp lines are recorded on a photographic plate .The atom emits both
visible and invisible radiation.
FORMATION OF HYDROGEN SPECTRUM
When electricity is passed through a discharge tube containing hydrogen gas at low pressure
the molecules break up into single hydrogen atoms.
The single electron of the hydrogen atom absorbs energy and is promoted from ground state
(energy level n= 1) to higher energy levels where it becomes unstable.
When the electron falls back to the ground state, energy is given out in the form of radiations of
particular wavelength.
On passing this light through a prism a discontinues line spectrum consisting of several sharp
lines is obtained
This gives rise to the emission spectrum of hydrogen recorded on a photographic plate.
Four strong coloured lines were observed in the visible region of this spectrum by balmer, in
the ultraviolet region by layman, in the infrared region by Paschen, bracket and pfund these
series of lines were named after these scientists who discovered them. NB:In a hydrogen
spectrum , there are four most prominent lines labeled hα, hβ and hθ and they are called balmer
series. They are caused by electrons moving from higher energy to second level. They appear in
Red, Green, Blue, and Violet.

The electron may fall back directly to ground state or it may fall in steps through different
energy level
( n=2,n=3, etc). to each energy level the electron falls, a different series of lines is found for
example the balmer series are formed when the electron falls back to energy level n=2.
The wavelength of the lines and series to which they belong are related by the equation.
= ( - )
Where v = wave length of a particular line
Rydbergs constant (109678cm-1)
n = energy level to which the electron has fallen
m= energy level from which the electron has fallen.
Emission line series and their regions
series n m Region of the series

Layman 1 2,3,4,5 Ultraviolet
Balmer 2 3,4,5, Visible
Paschen 3 4,5,6 Infrared
Bracket 4 5,6,7 Infrared
pfund 5 6,7,8 infrared
OR:
When light is passed through hydrogen atom electrons jump from ground state to excited
state after absorbing energy of definite amount, thus forming absorption spectrum which is
needed on a photographic plate.
THE EMISSION SPECTRUM OF HYDROGEN
The hydrogen spectrum is a series of lines, some in the visible region and others in the invisible
region. In each series, the spacing between the adjacent lines decreases as frequency of the
waves giving the lines increases or as wavelength decreases. The decrease in the spacing is

caused by decreased nuclear attraction on the electrons resulting into continuum in each
series,
Evidence of existence of energy levels in atom
The hydrogen spectrum provides an evidence for existence of energy levels within an atom .
This is because;
Hydrogen has one electron yet it produces a spectrum containing many lines separated from
each other.
There are several series of lines e.g. balmer series, layman series etc. each series representing a
particular energy level to which an electron returns.
The spacing between adjacent lines in each series differs
There is a continuum in each series of lines
The light giving each line is of definite energy or frequency.
Give out light of different colours.
Each of the big line comprises of two small lines.
Bohr,s explanation of the hydrogen spectrum
An atom consists of a small, heavily positively charged nucleus around which electrons revolve
in definite circular paths called orbits.
These orbits are associated with definite energies called energy levels.
They are designated as K, L, M, N,…..etc shells or numbered as 1,2,3,4 ……..etc from the
nucleus.
No energy is radiated by the electron while it is rotating in a permissible orbit.
The one electron of hydrogen being closet to the nucleus is in its lowest energy shell (n=1) or
normal ground state it can absorb a definite amount of energy and jump to a higher energy
state. This excited state being unstable, the electron comes back to a lower level.
The sample of hydrogen gas contains a large number of atoms and when energy is supplied, the
electrons in the different hydrogen atoms absorbs different amounts of energies these are
raised to different energy states for example, the electrons in some atoms may jump to second
energy level while in others it may be to the third M fourth N and so on. These electrons come

back from higher energy levels to the ground state in one or more jumps emitting different
amount of energies. Different line depends upon the difference in energies of the levels
The difference in energy levels become smaller with increasing distances of the energy levels
from the nucleus
The convergence limit is reached when n= when an electron jumps from n=1 to n= , the
electron is said to be completely removed from the atom. The atom is said to be ionized and
the energy required for this change is called ionization energy.
Electron distribution in atoms

TOPIC THREE: Bonding and structure
3.0 interatomic bonds

A chemical bond is inter-atomic or intermolecular or inter-ionic attraction which holds the
constituents together.
A chemical bond can be formed when electrons are transfer from one atom to another or
shared between two atoms.
During the transfer of electrons, one atom loses electron(s) which is or are simultaneously
gained by another atom.
Electrons that are available and therefore can be involved in the bonding are the outermost
electrons.
Atoms lose, gain or share outermost electrons in order to complete their octet and obtain a
stable configuration.
3.2 Types of bonds

The chemical bond may be ionic, covalent, metallic or molecular (hydrogen bonding)
3.2.1 The ionic or electrovalent bond
When an atom loses one or more electrons it becomes a cation, which is positively charged ion.
Atoms of metals form ions by loss of electrons. When an atom gains one or more electrons it
becomes an anion, which is a negatively charged ion. Cations and anions attract each other to
form electrovalent bond. in a reaction involving a metal and a non-metal, metal atoms lose
electrons to attain the electron configuration of the nearest noble gas while non-metal atoms
gain electrons also to attain the electron configuration of the nearest noble gas.
Therefore the ionic bond is an electrostatic attraction between the positively charged ions and
the negatively charged ion.
Metals form positively charged ions because they have low ionization energies; non-metals
form negatively charged ions because they have high values of electro negativities and electron
affinities.
The following are some of the characteristics of electrovalent compounds
 They are usually solids at room temperature, with high melting points. This is due to the
strong electrostatic forces holding the crystal lattice together. A lot of energy is
therefore needed to separate the ions and melt the substance.
 They are usually hard substances

 They usually cannot conduct electricity when solid, because the ions are not free to
move.
 They mainly dissolve in water. This is because water molecules are able to bond with
both the positive and negative ions, which breaks up the lattice and keeps ions apart.
 They usually conduct electricity when in the molten state or in aqueous solution. The
forces of attraction between the ions are broken and the ions are free to move.
 Ionic compounds are generally non -volatile and crystalline.
3.2.2 The covalent bond
This is a bond formed by sharing of electrons between two atoms in which each atom
contributes an electron(s) in the formation of the bond e.g X-Y
The covalent bond is formed when the two atoms achieve the noble gas stability by sharing a
pair of electrons, where each of the bonding atoms contributes one electron to the pair.
It is generally the tendency of non-metals to form covalent bonds.
If two atoms have both high electro negativities and the difference between their electro
negativities is small or none, they are most likely to form a covalent bond.
There are three types of covalent bonds
a)simple covalent bond
This is a covalent bond formed between two similar atoms or two different atoms with the
same electro negativity for example carbon to carbon, carbon to hydrogen. Compounds with
such a covalent bonds are purely non-polar and are insoluble in water soluble in organic
solvents and are made up of discrete molecules.
b)polar covalent bond
this is a bond formed between two atoms in which one atom is more electo negative than the
other
the more electro negative atom attracts the shared electrons towards itself gaining partial
negative charge and inducing partial positive charge on the less electronegative atom e g in
HCl chloride atom is more electro negative than hydrogen
H+ Cl- the result brings about a dipole.
A dipole is a separation of 2 positive charges by a small distance
such compounds are soluble in non- polar solvents but also readily soluble in water.

c)the co-ordinate covalent or dative bond
This is a bond formed between two atoms in which the shared electron pair is contributed by
one atom.
The atom contributing the electron pair must be having a lone pair of electrons and the atom
which is accepting the lone pair must be having an empty orbital
A coordinate bond once formed becomes similar in properties to a normal covalent bond.
However it is weaker than normal covalent bond
When the difference between coordinate and normal covalent bond need not be shown, both
bonds may be represented by a single line. When it is necessary to show the difference, the
coordinate bond is shown by an arrow pointing to the acceptor atom. The following are typical
molecules involving dative bonding.
i)ammonium ion H
H3N: H+ NH4+ N
ii) hydroxonium ion
H2O: H+ H3O+
iii ) dative bonds can be formed between molecules eg ammonia combines with boron chloride
through a dative bond
H3N: + BCl3 H3N : BCl3
some chloride dime rise in vapour form through dative bond e.g AlCl3 or FeCl3
Cl Cl Cl
Al Al
Cl Cl Cl

The covalent bond may be shown by dots, crosses or a line (-) or dash to represent the
bonding electrons.
For example
H2
HCl
CH4
In these examples each hydrogen atom acquires the helium structure (doublet) each carbon
atom achieves the neon configuration, and each chlorine atom acquires the argon
configuration.
It is possible to form multiple bonds between two non-metal atoms. When two electrons are
shared between two atoms on from each atom we represent them by single line eg Cl-Cl.
When four electrons are shared such that each atom contributes two electrons we may
represent the double bond formed by two lines e.g .O=O like- wise when six electrons are
shared such that each atom contributes three electrons we may represent the triple bond by
three lines N= N.
The following are some characteristics of covalent compounds

 Low molecular weight covalent compound are volatile gases; others are liquids at room
temperature. They exist as solids when their molecular weights are high.
 Their melting and boiling points are relatively low compared to ionic compounds
 They are generally insoluble in water but soluble in organic solvents
 They do not conduct electricity both in the molten state and in solution
 Generally they do not form ions in solution.
POLARISATION AND ITS EFFECTS ON IONIC AND COVALENT BONDS

The bonding in most compounds is intermediate between purely ionic and purely covalent.
Purely ionic bonds cannot exist, as the proximity of the ions involved in the bond allows some
degree of sharing electron density between them.
The electrons tend to be more less shared hence purely ionic bond gains some degree of
covalency.
If the positive ion is small and/or highly charged, it will attract the electrons in the anion and
repel its nucleus bringing about distortion

This distortion of the electron cloud of the negative ion is called polarization.
Therefore, all ionic bonds have some covalent character. Thus, an ionic bond is considered a
bond where the ionic character is greater than the covalent character. The larger the difference
in electro negativity between the two atoms involved in the bond, the more ionic (polar) the
bond is
Electro negativity is the tendency of an atom to attract bonding electrons towards its self so as
to become negatively charged in a covalent bond.
The ability of a cation to polarize an anion is called its polarizing power and it depends on the
strength of the electric field used to pull electrons away from the anion. The stronger the
electric field the greater the polarization of the anion and the more covalent character
introduced.
The electric field strength is based on the charge density of the cation. The charge density is
proportional to the charge to radius ratio of the cation. It means the greater the charge to
radius ratio value, the greater the polarizing power of the cation for an ion which is polarizable.
The ability of an anion to get polarized is called its polarisability it depends on the product of
anionic radius and magnitude of charge. The higher the product the greater the covalent
character or polarisability.
Polarization in ionic bonds is increased by the following factors which introduces covalent
character into ionic bonds
i)small cation radius with high charge.
ii)large anion radius with high charge.
Some of the covalent properties polarization can induce are low melting or low boiling point
and solubility in organic solvents
Polarizing power of a cation =
For a cation to have high polarizing power, it must be having high charge and small ionic radius
for example Lithium, beryllium, boron and aluminium ions. The charges on the above ions are
higher compared to their radius therefore most of their compounds have higher degree of
covalence
Larger negative ions are more easily polarized, but the effect is usually important when
positive ions with charges of 3+ (e.g, Al3+ )are involved. However ,2+ ions (e.g Be2+ ) or even 1+
(e.g,Li+ )show some polarizing power because their ionic radii are so small.

Decrease in ionic character in period 3
chlorides charge Radius(nm) Charge Melting Solubilityin

density point(0C) non polar
solvents
NaCl +1 0.102 9.8 801 Insoluble
MgCl2 +2 0.072 27.8 714 Soluble
AlCl3 +3 0.053 56.6 190 soluble
Effects of polarisability of anions
compound Anionic Anionic Radius x character Melting point

radius charge charge
MgF2 0.136 -1 0.136 ionic 1361
MgI2 0.216 -1 0.216 Covalent 637
COMPOUND melting point(k)

Al2O3 2290
AlCl3 451
CaO 2850
CaCl2 1051
We note that the melting point of aluminium chloride is lower than that of aluminium oxide.
This is explained by the fact that the chloride ion has a bigger ionic radius than the oxide ion.
Aluminium chloride is thus more covalent than aluminium oxide. It can also be argued that
aluminium chloride is more covalent than calcium chloride due to very high charge density of
the aluminium ion compared to that of the calcium ion.
POLAR COVALENT COMPOUNDS
when a covalent bond is formed between two atoms of different electro negativity, the
bonding electrons are not equally shared. This brings about electrical dipoles within the bond
.The molecule is said to be polar
e.g H-F
Other examples of polar molecules include water, hydrogen chloride, sulphur dioxide,
phosphorous trichloride and ammonia among others.
When the resultant dipole moment is not equal to zero then the molecule is polar and the bond
is polar
Because of the dipoles, polar molecules possess some ionic character
Example
Water O
H H
Since the dipole moment is not zero water molecules are polar
Ammonia N
H H H
Nitrogen-hydrogen bond is polar, since the dipole moment is not zero ammonia molecule is
polar
However, some molecules have polar bonds but they are not polar themselves.
An example of such molecules are
carbon tetrachloride (CCl4).
Cl
Cl C Cl
Rel
Cl
chlorine is more electro negative than carbon therefore attracts bonding pair of shared
electrons towards its self . gaining partial negative charge inducing partial positive charge on
carbon the carbon-chloride bond therefore is polar but due to symmetrical arrangement of
chloride atoms about carbon the dipole moment in all direction are equal and opposite and
therefore cancel out the dipole moment and the resultant dipole moment is equal to zero
such that the CCl4 molecule is non -polar .

carbon dioxide
O== C==O
Oxygen is more electro negative than carbon therefore attracts bonding pair of shared
electrons towards its self gaining partial negative charge inducing partial positive charge on
carbon the carbon-oxygen double bond therefore is polar but due to symmetrical arrangement
of oxygen atoms about carbon the dipole moment in all direction are equal and opposite and
therefore cancel out the dipole moment and the resultant dipole moment is equal to zero
such that the CO2 molecule is non polar .
The metallic bond
In metallic bonding, each metal loses its valency electrons forming metal cations. The metal
cations are attracted together by the cloud of lost electrons resulting into strong metallic
bonds.
Thus a metallic bond can be defined as an electrostatic force of attraction between positively
charged metal ions and a cloud of negatively charged electrons lost by metal atoms. The lost
electrons are delocalized and free to move throughout the entire metal lattice thus metals
conduct electricity and heat.
The strength of the metallic bonds depends on the atomic radius and the number of valence
electrons delocalized. Generally the smaller the atomic radius and the greater the number of
valence electrons the stronger the metallic bond.
The alkali metals, which form large cations, have only one electron per atom which is available
to enter the delocalized system. The strength of the metallic bond is therefore low, and these
metals have low melting points and are soft, malleable and ductile.
Transition metals form small cations and can release quite a number of electrons into the
metallic bond. These metals are hard with high tensile strength and have high melting points,
corresponding to a strong metallic bonding system.
INTERMOLECULAR FORCES OF ATTRACTION

In any liquid or solid there are forces between molecules these are called inter molecular forces
A dipole is a molecule (or part of a molecule) with a positive end and a negative end for
example
H—Br.
When a molecule has a dipole we say it is polarized.

Molecules with permanent dipole are polar.
1)Dipole-dipole forces of attraction
These occur between polar molecules, the dipole is formed by un equal sharing of electrons.
The dipole- dipole forces is caused by attraction of a partially positive end of a dipole to an
oppositely charged end of another nearly dipole.
H- Cl …..H- Cl
The intermolecular dipole-dipole forces are weak and in their solid state these substances form
softer solids with melting points generally much lower than those of ionic and metallic solids.
Many of those dipole molecules are soluble in water using hydrogen bonding and dipole-dipole
attraction release of energy makes them dissolution favorable.
2. Vander waal,s forces of attraction
Inert gases and other non-polar and polar molecules are bonded by vander-waals forces
Vander- waal forces are weak electrostatic forces binding all polar and non-polar molecules
together.
They are much weaker than covalent, ionic or metallic. They are forces responsible for non-
metallic behavior of gases and for the lattice energy for molecular crystals. The dipoles involved
can be either permanent or temporary. These intermolecular forces are weaker than the
interatomic forces less energy is needed to overcome inter molecular forces.
The more polar the molecule the stronger the vander Waal forces.
There are three factors that cause such forces;
Dipole-dipole interaction
I.e the electrostatic attraction between two molecules with permanent dipole moment
Induced dipole- induced dipole
These are dipole of one molecule polarizes the neighboring molecule
The electron distribution in a non polar molecule or atom of an inert gas is not always
symmetrical at a given time such that one side has more electrons than the other, it becomes a
dipole. This dipole will induce another dipole on a neighboring atom. There will exist a weak

force of attraction between the two existing molecules or atoms. It depends on the number of
electrons and therefore size of the molecules.
Dispersion forces caused by small instantaneous dipole in atoms
3.The hydrogen bonds
Hydrogen bonding it is the electrostatic attraction between a strongly partially positive

hydrogen atom attached covalently to the highly electro negative elements fluorine, nitrogen
or oxygen and a strongly partially negative fluorine, nitrogen or oxygen atom on another
molecule.
Hydrogen bonding can form between molecules or within molecule.
Hydrogen bonding are usually shown as broken lines and are longer than covalent bonds.
Hydrogen bonding has considerable effects on the properties of substances which have it.
Effects of hydrogen bonding
The boiling point of hydrogen fluoride is abnormally higher than that of other hydrides of group
(vii)
i.e HCl,HBr and HI.
HCl,HBr and HI molecules are held by weak Vander-waals. Boiling point increases with increase
in magnitude of the vander waal forces.
The magnitude of vander-waals forces increase with increasing formula mass.
Molecular mass of the hydrides increase in the order HCl<HBr<HI. Hydrogen fluoride has an
abnormally high boiling point because its molecules associate through hydrogen bonds due to
the high electro negativity of fluorine.
-Ammonia has a higher melting point and boiling point than other hydrides of group (v)i.e PH 3
and ASH
-Water is a liquid and has higher boiling point than hydrides of group(VI), which are gases
i.e.H2S and H2Se.
-Ice floats on water due to having a lower density than water.

In ice, the water molecules are held by hydrogen bonds. Each oxygen atom is covalently bonded
to two hydrogen atoms and then also to two other hydrogen atoms through hydrogen bonds.
This gives ice an extremely open tetrahedral structure with low density.
In liquid water, the hydrogen bonds are constantly broken and reformed due to thermal
movement of water molecules. This leads to close packing of water molecules thus a higher
density than ice.
-The formula mass of ethanoic acid as determined by freezing point depression method in
benzene is twice the theoretical formula mass. This is because ethanoic acid associates in
benzene through hydrogen bonding to form dimmers.
-Alcohol molecules are held by strong hydrogen bonds while Alkane molecules are held by
weaker vander Waals forces. Intermolecular forces in alcohols are therefore stronger than
those in Alkanes thus alcohols require more energy for these forces to be broken.
EVIDENCE FOR EXISTANCE OF HYDROGEN BONDS
We are surrounded by substances that exhibit presences of hydrogen bonds.
Notable among these includes the following facts;
-Ice has a lower density than water.
-Boiling points of carboxylic acids and alcohols are higher than those of other hydrocarbons of
comparable formula mass.
-Amines have higher boiling points than Alkanes of approximately the same molecular mass.
Also since primary amines form more hydrogen bonds than secondary amines , primary amines
have higher boiling points than secondary amines.
-Molecular masses of carboxylic acids determined by cryoscopic method in organic solvents are
observed to be twice the theoretical ones. This is because carboxylic acids dimerise in organic
solvents through hydrogen bonding.
-Ammonia ,water and hydrogen fluoride have higher boiling points than hydrides of group
v,vi,vii respectively.

Types of hydrogen bonding
1.intermolecular hydrogen bonds
This is the type of hydrogen bonds that exist between the same or different molecules.
O………H
2.intra hydrogen bonding
this is the type of hydrogen bonding formed between atoms of the same molecule e.g 2-
nitrophenol
intra hydrogen bonding reduces the molecular attraction between molecules and consequently
reduces the melting and boiling points of a compound
- 2-hydroxybenzoic acid has a lower boiling point than 4-hydroxybenzoic acid. This can be
explained by first considering their structures below;
In 2-hydroxybenzoic acid , the functional groups are very close to each other hence molecules
form more intra-molecular hydrogen bonds than inter-molecular hydrogen bonds. Therefore
very few intermolecular hydrogen bonds need to be broken thus low boiling point.
In 4-hydroxybenzoic acid ,the functional groups are very far apart thus 4-hydroxybenzoic acid
forms more inter-molecular hydrogen bonds than intra-molecular hydrogen bonds. Therefore
very many inter-molecular hydrogen bonds have to be broken for 4-hydroxybenzoic acid to boil.
This requires a lot of energy hence a high boiling point.
Representation of covalent bonds
A pair of electrons shared between two atoms is represented in electron dot/cross diagrams or
by a dash (-). One, two or three dashes indicate single, double or triple bonds respectively. The
bonds are formed starting from the single atoms to achieve the stable configuration. Only outer
electrons involved in the bonding are shown. Valence electrons which are actually donated and
shared to form covalent bonds are called bonding electrons. Those which are not shared but
help in giving the atoms their octet of configuration are called non-bonding electrons.
A pair of electrons on an atom which is not shared is called a lone pair. Lone pairs of electrons
can be used for bonding

The shapes of molecules and ions
Shapes of molecules and ions can be predicted using the valency shell electron pair repulsion
theory (VSEPR)
The VSEPR theory is based on the following principles:
1. All electrons have electrostatic repulsions for one another

2. Electron pairs around a central atom are distributed so as to minimize repulsion between them
3. The shape of any molecule is determined by the number of electron pairs around a central atom
4. Repulsion decreases in the sequence :lone pair-lone pair>lone pair- bonding pair>bond pair-
bond pair
5. Repulsion between orbital’s is increased by increased electro negativity of the central atoms the
more electronegative the central atom is the greater the electron displacement.
The most stable structure is one where there is maximum distance between electron pairs
(i.e least repulsion)
The total number of electron pairs in a molecule is given by VSEPR formula: AXmEn
Where;
A=central atom,
X=bond pairs
E=Lone pairs of electrons
M&n= integers
Note:Total electron pairs=bond pairs+lone pairs
Geometry adopted by molecules

Case 1:AX2(2 bond pairs and 0 lone pairs)
 Such molecules will adopt a linear structure
X-E-X minimum repulsion when <XAX=1800)e.g BeCl2,CO2,C2H2,HCN e.t.c
Case 2:AX3(3 bond pairs and 0 lone pairs)
 Such molecules will adopt a triagonal planar structure with a bond angle of 1200
e.g.SO3, BF3
Case 3:AX4(4bonding pairs and 0 lone pairs)
 Such molecules will adopt a tetrahedral structure with a bond angle of 109.50
e.g.CH4CCl4,SO42-,PO43-

Case 4:AX5(5bonding pairs and 0lone pairs)
 Such molecules will adopt a triagonal bi-pyramidal structure.e.g.PCl5
Case 5:AX6
 Such molecules will adopt a structure bi-pyramidal or octahedral structure .e.g. SCL6
Case 6:AX7
 Such molecules will adopt a pentagonal bi-pyramidal structure .e.g. IF7
EFFECT OF LONE PAIR ON THE GEOMETRY ADOPTED
NOTE: the lone pair is not considered in naming the geometry adopted
Consider a molecule with 4 electron pairs:
 AX4E0(e.g. BF4-,CH4,CCl4,NH4+)
Geometry adopted =tetrahedral structure
 AX3E1(e.g.NH3,PH3,PCl3,H30+)
Geometry is triagonal pyramidal
 AX2E2(e.g. H2o,H2S,H2Te,NH2-)
Such molecules will adopt a V- shaped structure
Consider a molecule with 5 electron pairs :
 AX5E0
Such molecules will adopt a triagonal bi-pyramidal structure e.g.PCl5
 AX4E1
Such molecules normally adopt a distorted tetrahedral structure or square
planar e.g.SF4
 AX3E2
Such molecules will adopt a T-shaped structure e.g. CIF3
 AX2E3
Such molecules will adopt a linear structure e.g. XeF2,ICI2-
HOW TO DETERMINE THE NUMBER OF LONE PAIRS AND BOND PAIRS IN A MOLECULE .
NOTE: lone pairs considered are those on the central atom: all valence electrons of central atom
considered & only electron(s) contributed to bonding is/are considered for a non-central atom
a)Working out the shapes of molecules with single bonding pairs
The number of electron pairs in molecules containing only single bonds is found by the
following steps
1. Identify which atom is at the Centre of the molecule.

(usually the atom of which there is only one).

2. Determine the number of the outer electrons or valence electrons it has, this is equal to its
group number within the periodic table.
3. Add one electron for each atom joined to the central atom to the number of the outer
electrons
4. Divide the sum by two to get the number of electron pairs.
5. Determine the number of lone pairs (non-bonding pair)
(Number of lone pairs=number of electron pairs – number of bonding atoms)
6. For the structure and name of the shape refer to the last table
Examples of working out of shapes of molecules
molecule BeCl2 BF3 CH4 PCl5 NH3 H2O

Bonding 2 3 4 5 3 2
atoms
1 Be B C P N O
2 2 3 4 5 5 6
3 2+2=4 3+3=6 4+4=8 5+5=10 5 +3=8 6+2=8
4 =2 =3 =4 =5 =4 =4
5 2-2=0 3-3=0 4-4=0 5-5=0 4-3=1 4-2=2
Triagonal Triagonal Triagonal

linear planar tetrahedral bipyramidal pyramidal bent
Working out the shapes of charged molecules with single bonding pairs
The number of electron pairs in molecules containing only single bonds is found by the following steps

2. Determine the number of the outer electrons or valence electrons it has, this is equal to its
group number within the periodic table.

3. Add one electron for each atom joined to the central atom to the number of the outer
electrons ,then .Add an electron if the particle is negatively charged; subtract an electron if the particle
is positively charged
4. Divide the sum by two to get the number of electron pairs.
5. Determine the number of lone pairs (non-bonding pair)
(Number of lone pairs=number of electron pairs – number of bonding atoms)
6. For the structure and name of the shape refer to the last table
molecule NH4+ H3O+ NH2- PCl4+ C̅ l2
Bonding 4 3 2 4 2
atoms
1 N O N P I
2 5 6 5 5 7
3 5+4-1=8 6+3-1=8 5+2+1=8 5+4-1=8 7+2+1
4 =4 =4 =4 =4 =5 =4
5 4-4=0 4-3=1 4-2=2 4-4=0 5-2=3
VSEPR SHAPES OF COMPOUNDS WITH MULTIPLE BONDS
Many molecules and ions contain oxygen. This oxygen is; sometimes double bonded and sometimes
single bonded, in which case the oxygen atom carries a minus charge.
The shape of these particles can be worked out by the following these steps:


2. Determine the number of the outer electrons or valence electrons it is using in bonds to the
oxygens , this is equal to its group number within the periodic table.
3. Determine the number of single bonded oxygen atoms

(For each minus charge on the particle there is one single bonded oxygen atom with a minus charge)
4. Determine the number of double bonded oxygen atoms.
5. Draw the two types of oxygen around the central atom and
6. Check if there are any unused pair of electrons, these will be the lone pairs put them in
6. Choose the shape of the number of electron charge clouds around the central atom.
molecule CO32- SO32- SO42- SO3 NO3- ClO3-

1 C S S S N Cl
2 4 6 6 6 5 7
3 2 2 2 0 1 1
4 1 1 2 3 2 2
5
6 4-4=0 6-4=2(1lp) 6-6=0 6-6=0 5-5=0 7-5=2(1lp)
Effect of electro negativity of atoms on the bond angles
Consider the bond angles group(v) hydrides
compound NH3 PH3 ASH3 SbH3

Bond angle 107 94 92 91
Bond angles within a molecule decreases with decreases in electro negativity of the central
atom. This is because the highly electro negative central atom with drawls electrons towards its

self this increases repulsion between the bonds as the attraction of the central atom for
electrons falls the bonding pairs are less closely held consesequently,bond angles of group(v)
hydrides reduce in that order
However, bond angles within a molecule reduces with increase in electo negativity of the
ligands ie
Compound PF3 PCl3 PBr3

Bond angle 96.3 100 101
TOPIC 4 : THERMOCHEMISTRY
Thermochemistry is the study of energy changes that accompany chemical reactions.

It deals with the measurements or calculations of heat absorbed or heat given out in a chemical
reaction.
In the course of chemical reactions, bonds between atoms are broken and new bonds are made as
atoms regroup to form new substances.
Energy is needed to break bonds in reactants and energy is released when new bonds are made in
products. It’s very ,very unlikely that these two process will be exactly in balance, and so some energy
will either be released to the surroundings or absorbed from the surroundings.
Thermochemical terminology
The System is the part under study for example hot water in the beaker
The surroundings the outside of the system
Energy is a measure of systems capacity to do work.
Work an energy transfer that is the result of a force moving a body through a distance.
Heat an energy transfer that is the result of temperature difference between a system and its
surroundings.
Temperature is the property of a system that determines the direction of heat flow between the system
and its surroundings. Heat flows from a hotter region to the colder.
Enthalpy(symbol H) is a term that describes the heat content of the system. its actual value cannot be
measured.
Enthalpy change (symbol ΔH read delta H) is the difference between heat content of the products and
reactants measured at constant temperature and pressure during a chemical reaction.
H is measured in kilo joules per mole and at constant pressure.
H is written at the end of a chemical equation.
Enthalpy change is called heat of reaction and is denoted as ΔHrxn
Where ΔH = ∑ -∑
HEAT OF REACTION

Is the amount of heat evolved or absorbed when the reaction occurs between molar quantities of the
substance as represented by the equation
H2(g) + O2(g) H2O(l) H = -286kjmol-1
This means that when one mole of hydrogen in gaseous state reacts with half mole of oxygen in gaseous
state to forms one mole of water with evolution of 286 kj mol-1 of energy.
Per mole relates to the whole equation expressed in mole quantities
TYPES OF HEAT OF REACTION
Exothermic reactions; this is a chemical reaction accompanied by evolution of heat to the surroundings
It’s characterized by rise in temperature
In such reactions the heat content of products is less than that of the reactants
The enthalpy of reaction is therefore negative.
The negative sign of the enthalpy changes shows that the reacting system has lost heat energy to the
surroundings.
These changes can be represented on an energy level diagram.
reactants
ΔH(-ve)
products
Examples of exothermic reactions include;
All combustion reactions
Most neutralization reactions
Endothermic reactions; this a chemical reaction accompanied by absorption of heat from the
surroundings

It’s characterized by a fall in temperature
In such reactions the heat content of products is more than that of the reactants enthalpy of reaction is
positive.
The positive sign of the enthalpy changes shows that the reacting system has gained heat energy from
the surroundings.
These changes can be represented on an energy level diagram.
Products
ΔH(+ve)
Reactants
Examples of endothermic reactions include
Dissolution of ammonium nitrate
Formation of carbon disulphur from sulphur and carbon
THE QUANTITY OF HEAT DEPENDS ON
i) amount of substances involved
ii) physical state of reactants and products
iii) temperature at which the experiment is carried out
iv) pressure at which the experiment is carried
V) Allotropic form of the element
STANDARD CONDITIONS OF HEAT CHANGES

In order to make comparisons, the energy changes of reactions are determined under standard
conditions. Any heat change measured under standard conditions is described as a standard heat of
reaction or standard enthalpy change denoted by Hᶿ (which refers to an enthalpy(H)change(Δ) under
standard conditions(θ) )
Standard conditions are
 The gases at a pressure of one atmosphere
 Temperature of 250c (298k)
 Solutions of unit concentrations
 Substances in their standard states (s, l, g).
The standard state of a substance is the physical state of substance under standard conditions. (s, l, and
g) at 1 atmosphere pressure and at 298 k.
STANDARD ENTHALPY CHANGE
Is the amount of heat given out or taken in when molar quantities of reactants as stated in the equation
react together under standard conditions.
TYPES OF STANDARD ENTHALPY CHANGES
STANDARD ENTHALPY OF FORMATION
is the enthalpy change when one mole of the compound is formed from its constituent elements in
their standard states at 298k and 1 atmosphere. e.g.
+ O2g H2Ol Hᶿ l = -286kjmol-1
Hᶿ l = +90.2kjmol-1
Hᶿ l = -74.8kjmol-1
Hᶿ l = -46.1kjmol-1
Note
 In all cases the equation must be written so that one mole of a compound is formed
 Start from element the only compound is the equation is the one being formed
 Everything must be present in its standard state
 The enthalpy of formation an element like oxygen in its standard state is zero

The formation of H2 (g) from H2 (g) does not involve a chemical change so there is no enthalpy
change.
Importance of enthalpy of formation
1. It gives a guide to the stability and reactivity of a compound formed. Compounds with negative
values of heat of formation are more stable with respect to their elements and less reactive.
Whereas compounds with positive values of enthalpy of formation are more reactive and
unstable with respect to their elements.
2. It is used for comparing electro negativity values of elements ie the greater the electro
negativity in a binary compound the more exothermic is the heat of formation and the more
stable is the compound.
Enthalpies of formation are not measured experimentally but determined indirectly.
Problem
Write equations representing the enthalpy change of formation of
a)sodium iodide ,NaIS
…………………………………………………………………………………………………………………………………………………………..
b)ethanol, CH3CH2OH(l)
………………………………………………………………………………………………………………………………………………………….
c)aluminium oxide,Al2O3(S)
………………………………………………………………………………………………………………………………………………………….
d)sodium chlorate,NaClO3(s)
……………………………………………………………………………………………………………………………………………………….
e)ethane,C2H6 (g)
………………………………………………………………………………………………………………………………………………………
STANDARD ENTHALPY OF COMBUSTION ( Hc)

This is the heat evolved when one mole of a substance in its standard state is completely burnt in excess
oxygen under standard conditions.eg
C graphite s + O2 g CO2 g Hᶿ l = -393.5kjmol-1
CH4g + 2O2 g CO2 g + 2H2Ol Hᶿ l = -890.3kjmol-1
CH3CH2OHl + 3O2 g 2CO2 g + 3H2O l Hᶿ l = -1367.3kjmol-1
Note
You must be burning only one mole of the substance
Importance of enthalpy of combustion
1. Since the values can be determined experimentally, the method is used on large scale to
determine the heating values of fuel.
2. It helps in nutrition so that suitable food stuff is recommended to an individual depending on its
energy requirement.
3. They are used to calculate the enthalpy of formation of substance.
4. The values can be used to estimate the difference in the energy content of allotropies (
allotropies are different forms of the same element
5. It is used to establish structure of organic compounds since compounds with the same number
of atoms and similar bonds have almost the same value of enthalpy of combustion.
Experimental determination of enthalpy of combustion of a substance,

(i) Using a bomb calorimeter.
Apparatus setup
Procedure
 A known mass of a substance (say a g) to be ignited is placed in a crucible suspended in a bomb

calorimeter.
 The bomb is filled with oxygen and immersed in a calorimeter containing a known volume of
water (say Vcm3)
 The temperature of water is recoded every minute for five consecutive minutes.
 The substance is then ignited by passing electric current through the fuse wire.
 The substance burns and the heat generated raise the temperature of water.
 The temperature of water is recorded for a period of time after a certain known interval until
the temperature has shown a fall for five consecutive minutes.
 A graph of temperature against time is plotted and the maximum rise in temperature is
determined
Graph

temp (oc)
Time (minutes)
Neglecting heat gained by a thermometer and calorimeter.
Heat evolved by burning the compound is equal to the heat gained by water.
Heat gained by water =( mass of water)x(s.h.c)x(temp change
= (density of water x volume of water)x(s.h.c)x(temp change)
= ( v x × ρ c× T ) joules
Heat evolved by burning ag of substance = (v x × ρ c× T ) joules
Heat evolved by burning one mole of substance = kjmol-1
=( ) kjmol-1
Where i ρ s the density of water
C is the heat capacity of water;
M is the molar mass of a substance
Problems

1-Write equations representing the enthalpy change of combustion of
a)hydrogen ……………………………………………………………………………………………………………………………………….
b)carbon …………………………………………………………………………………………………………………………………………
c)methane,CH4 (g) ……………………………………………………………………………………………………………………………
d)ethanol,C2H5OH(l) ………………………………………………………………………………………………………………………..
e)ethane,C2H4 (g)………………………………………………………………………………………………………………………………
2-describe laboratory experiment to determine the enthalpy of combustion of ethanol by spirit lamp
Laws of thermo chemistry

There two laws of thermo chemistry and are based on the principle of conservation of energy
This states that;
Energy cannot be created nor destroyed but may be converted from one form into another.
The first law was given by Lavoisier and Laplace’s in 1780
It states that
The heat change in a reaction is equal to and opposite to heat change in a reverse reaction
Which means that if the reverse of a chemical reaction is written, the sign of enthalpy change is
changed, but its magnitude remain same
H2(g) + O2(g) H2O(l) H = -286kjmol-1
H2O(g) H2(g) + O2(g H = +286kjmol-1
Hess’s law of constant heat summation
It states that enthalpy change for a given reaction is independent of the route by which the reaction is
achieved, provided that the, pressure and physical states of the reactants and products are the same
in each case.
This means that if you convert reactant A into product E in one step or in many steps, the overall
enthalpy change is always the same.
For example
ΔH2
HOLISTIC APPROACH TO PHYSICAL CHEMISTRY
Intermediate B Intermediate C Page 81
ΔH1 ΔH3
Reactant A ΔH
Product E
ΔH4
ΔH5
Intermediate D
ΔH = ΔH1 + ΔH2 + ΔH3
= ΔH4 + ΔH5
Significance of Hess’s law
It can be used in the determination of enthalpies of reactions which cannot be experimentally

determined e.g. enthalpies of formation.
Using Hess’s law to calculate enthalpy changes
Step 1
Write down a balanced equation for the enthalpy you are asked to find.
Step 2
Use the information you are given to complete a cycle that you can apply Hess’s law to. The direction of
arrows depends entirely on the information given.
Step 3
Find two routes within the diagram which do not go against the flow of any arrow
Example 1

Calculate the standard enthalpy of formation of methane given that the standard enthalpies of
combustion of carbon, hydrogen and methane are -394,-286 and -890 kjmol-1
Solution
𝛥𝐻
C(s) + 2H2 (g) CH4 (g)
𝛥-
8 )
9 89
CO2 (g) +2H2O(l)
ΔH – 890 = -390 + 2(-286)
ΔH =+ 890 - 390 + 2(-286)
ΔH = -76kjmol-1
Note for enthalpy of combustion data only
Hf = ∑ (reactant) - ∑ (products)
Example 2
Calculate the enthalpy change of combustion of ethene,C2H4, given that the standard enthalpies change
of formation of ethene,water and carbon dioxide are +52,-286 and -394kjmol-1 respectively
𝛥𝐻
C 𝑂 CO g
Ol
𝑔 𝑔
(0) 2(-394)
+52 2(-286)
2C(g) + 2H2(g) +3O2(g)
ΔH =2(-394) +2(-286) –(+52)-(0) =-1412Kjmol-1
If enthalpy of formation data is provided
Hc =∑ (products) - ∑ (reactants).
OR by rearranging the equations

Step 1
write the equation whose enthalpy is required
2CO2(g) + 2H2O(l)
Step 2
Write equations of reactions from the given data
2C(s) +2H2(g) C2H4(g) ΔH=+52Kjmol-1 ………………..(i)
H2 g + H2O(g) H. = -286 kjmol-1 …………..(ii)
C S + O2 g CO2 g H. =-394 kjmol-1 …………..(iii)
Step 3
Re arrange the equation above to obtain the required equation
Equation (ii)x2 + equation (iii)x2 + equation (i) reversed
2H2 g + O2(g) 2 H2O(g) H. = 2(-286) kjmol-1 …………..(ii)
2C S +2 O2 g 2 CO2 g H. =2(-394) kjmol-1 …………..(iii)
C2H4(g) 2C(s) +2H2(g) ΔH= -52Kjmol-1 ………………..(i)
C 2CO2(g) + 2H2O(l) ΔH= -1412Kjmol-1 overall equation
Example three

Calculate the enthalpy change for the reaction
4NH3(g) + 5O2 (g) 4NO (g) + 6H2O
Given that the standard enthalpies of formation of ammonia, nitrogen monoxide and water are
-46.2,+90.4 and -242 kjmol-1 respectively
4NH3(g) + 5O2(g) 4NO(g) + 6H2O(g)
4(+90.4)
4(-46.2)
ΔH 6(-242)
2N2(g) + 6H2(g) + 5O2 (g)
ΔH = (4×90.4 +6×-242) – (4×-46.2 + 5×0) = -906kjmol-1
Or rearranginging Equations
N2 (g) + H2 NH3(g) H = -46.2 kjmol-1 …………….(i)
H2+ O2(g) H2O(g) H = -242 kjmol-1 ………………(ii)
N2 + O2 NO(g) H= 90.4 kjmol-1 …………..(iii)
Equation of interest
4NH3(g)+ 5 O2(g) 4NO(g)+6 H2O(g)
Multiply equation (i) by 4 and reverse it + equation (ii) Multiply by 6 + equation(iii) Multiply by 4
4NH3(g 2N2 (g) + 6H2 g H = 4x -46.2 kjmol-1
6H2+ O2(g) 6 H2O(g) H = 6x -242 kjmol-1
2N2 + 2 O2(g) 4 NO(g) H = 4 x 90.4 kjmol-1
4NH3(g)+ 5 O2(g) 4NO(g)+6 H2O(g) H = - 906 kjmol-1 overall equation

Exercise
1) Calculate the enthalpy change for the reaction
C2H6(g)+ O2(g) 2CO2(g) + 3H2O(l) given
substance C2H6(g) CO2(g) H2O(l)
Hf. (kjmol-l -85 -394 -286
2. Calculate the heat of formation of propane C3H8 given that heat of combustion in the table below.
substance C( s) H2(g) C3H8 g
Heat of combustion(Kjmol-1) -394 -286 -2220
3. Calculate the standard enthalpy change for the reaction
C2H4(g) + H2(g) C2H6(g)
Given that the standard enthalpies of combustion of ethene, hydrogen and ethane are -1411,-286 and
-1560 kjmol-1
4. Calculate the enthalpy change for the reaction
CaCO3(s) CaO(s) + CO2(g)
given that the standard enthalpies change of formation of calcium carbonate, (C CO ) calcium oxide
and carbon dioxide are -1207,-635 and -394kjmol-1 respectively
5. Calculate the standard enthalpy of formation of propan-1-ol (CH3CH2CH2OH ) given that the standard
enthalpies of combustion of carbon, hydrogen and propan-1-ol are -394,-286 and -2010 kjmol-1
6 Calculate the standard enthalpy change of formation of solid ammonium chloride, NH4Cl, using the
following data:
ΔHf (NH3 (g)) = -46.1kjmol-1
ΔHf (HCl (g)) = -92.3kjmol-1
NH3 (g) + HCl(g) NH4Cl(S) ΔH = -176.0kjmol-1

STANDARD ENTHALPY OF NEUTRALIZATION
This is the heat given out when an acid and alkali react together under standard conditions to give one
mole of water
HNO3 + NaOH NaNO3 + H2O l H = -57.32 kjmol-1
HNO3 aq + aq aq + H2O l H = -57.36 kjmol-1
CH3COOH (g)+NaOH CH3COONa(g) +H2O H = -56.1KJmol-1
CH3COOH+NH3 CH3COONH4 +H2O H = -50.4 kjmol-1
HCN(aq) + NaOH(aq) NaCN (aq) + H2O(l) H = -12.0 kjmol-1
Notice
i) From each equation that one mole of H+ ions from an acid, reacts with one mole ŌH ions from
an alkali to produce one mole of water.
H+ (aq) + -OH(aq) H2O(l) H neutralization
ii) For strong acids and strong bases the heat of neutralization is almost constant at -57.3 kjmol-l .
this because they are fully ionized in their aqueous solutions when the solutions are mixed there
is no bond breaking
iii) For weak bases and acids the enthalpy of neutralization is below -57.3 Kjmol-1
The low values are due to the fact that the weak acids and bases are not fully ionized in aqueous
solutions. So some energy is used to break the bonds within their molecules before they are fully
ionized.
iv) Enthalpy of neutralization Varies with the degree of weakness of acids or the bases.
IMPORTANCE OF ENTHALPY OF NEUTRALIZATION
 Provides the relative molecular mass of an acid is known, its basicity can be determined from
measurements of the enthalpy of neutralization of the acids.
 The enthalpy of dissociation or ionization of weak acid or weak base can be determined
provided the neutralization data is given.

Experiments to determine enthalpy of neutralization
a) Experimental determination of the enthalpy of neutralization of sodium hydroxide and

sulphuric acid by simple calorimetry
Procedure
 A known volume of sodium hydroxide ( Vb )of known concentration( Mb) is placed in a plastic
cup and its temperature (T10C) accurately measured and recorded.
 A known volume of sulphuric (Va) of known concentration (Ma) required to neutralize sodium
hydroxide is placed in a plastic cup and its temperature (T20C) accurately measured and
recorded.
 The sodium hydroxide is transferred into the acid and the mixture stirred gently with the
thermometer.
 The maximum temperature (T30C) reached is measured and recorded.
NOTE; the thermometer should be thoroughly washed between the two readings as a precaution.
TREATMENT OF RESULTS
Temperature change T =( - T3 ) 0C
Total volume is V = (Va +Vb) cm3
Density of solution (ρ) = 1.0gcm3
Mass of the mixture M = (V x ρ)g
Specific heat capacity of solution C =4.2j g-1 k-1
Heat absorbed by solution = ( mass of solution x specific heat capacity of solution

x ) J
Equation of reaction
2NaOHaq + H2SO aq Na2SO4 aq + 2H2O(l
1 mole of H2SO4 aq produces 2 moles of water
mole H2SO4 aq produces 2× moles of water
2x of water is produced by ( m x 4.2 x T )j

1 mole of water is produced by ( kjmol-1
The enthalpy of neutralization is – kjmol-1
EXAMPLE
When 50cm3 of 1.0M sulphuric acid was added to 50cm3 of 2.0M sodium hydroxide solution the
temperature rose by 13.60C. Calculate the enthalpy of neutralization.(specific heat capacity of solution
4.2jg-1k-1 and density of solution 1.0gcm-3
Temperature change T =13.6 0C
Total volume is V = (50 +50) cm3
Density of solution = 1.0gcm3
Mass of the mixture = (100 x 1)g
Specific heat capacity of solution =4.2jk-1
Heat absorbed by solution = ( mass of solution x specific heat capacity of solution

x ) J
2NaOHaq + H2SO aq Na2SO4 aq + 2H2O(l
1 mole of H2SO4 aq produces 2 moles of water
mole H2SO4 aq produces 2× moles of water
2x of water is produced by ( 100 x 4.2 x 1 )j
1 mole of water is produced by ( kjmol-1

Alternative method for determining the enthalpy of neutralization
Procedure:
A known volume of alkali Vb is pipette into a plastic cup and its initial temperature T10C measured and
recorded.
A known volume of acid is then added to the alkali at intervals of 5cm3 using a burette while taking note
of the temperature rise at each interval.
A graph of temperature against volume of acid added is then plotted
The graph has the shape below
Initial temp
Volume of acid required for complete neutralization
Volume of acid added

3
(cm )
From the graph, the maximum temperature and volume of acid for complete neutralization are
determined hence the enthalpy of neutralization can be calculated.
Exercise
In an experiment to determine enthalpy of neutralization of the reaction between sodium hydroxide

and sulphuric acid, 2.0M sulphuric acid was added at intervals to 40cm3 of 2.0M sodium hydroxide and
the following results were obtained.
Volume of sulphuric acid added (cm3) 4 8 12 16 20 24 28 32 36
Temperature (0C) 29.0 32.0 35.0 36.0 37.0 37.0 36.0 34.0 32.0

a) Plot a graph of temperature against volume of sulphuric acid added
b) Use the graph to determine the volume of sulphuric acid required to neutralize sodium
hydroxide
c) Determine the molar enthalpy of neutralization
Enthalpy of precipitation
On mixing some two or more aqueous solution a precipitate is formed for example when sodium
chloride solution is added to solution of silver nitrate a white precipitate is formed and the enthalpy
accompanying this reaction is called enthalpy of precipitation.
Enthalpy of precipitation is the enthalpy change when one mole of an ionic compound is precipitated
from solution.
Example
25.0cm3 of 0.3 M silver nitrate was added to 25cm3 of sodium chloride solution. The temperature of
mixture rose by 3.00C .calculate the enthalpy of precipitation of silver chloride.
Assuming heat capacity of solution is 4.2jg-1K-1 and density of solution is 1.0gcm-3.
Total volume of solution = 25 +25 = 50cm-3
Mass of solution = 100 x 1.0 = 100g
Heat produced = 50x 4.2 x3 =0.63Kj
Moles Ag+ in 25 cm3 =
From the equation Ag+(aq) + Cl-(aq) AgCl(s)
Moles of Ag Cl precipitated = 0.0125
When 0.0125 moles of AgCl is formed it gives out 5.46 Kj
When 1 mole of AgCl is formed it gives out = 50.4kjmol-1
Enthalpy of displacement
This is the enthalpy change when one mole of an element is displaced from its solution by another
element higher in the reactivity series
Metals higher in reactivity series displace those from solution containing their ions for example
Zn(s) + Cu2+ (aq) Zn2+ (aq) + Cu(s)

Also more electronegative elements will displace less electronegative elements from solution containing
its ions.
Cl2(g) + 2 Br-(aq) 2Cl- (aq) + Br2(aq)
Exercise
Excess zinc powder was added to 25cm3 of 1.0M copper(ii) sulphate solution in a plastic beaker and the
temperature of solution recorded at some time intervals the data obtained is shown in the table below
Copper (ii) ions react with zinc powder according to the equation
Zn(s) + Cu2+ (aq) Zn2+ (aq) + Cu(s)
Time (min) 0 2.5 3.0 3.5 5.0 6.0 7.0
Temperature( 0C) 27.2 66.0 69.5 68.5 65.0 62.0 59.5
a) Plot a graph of temperature against time
b) use the graph to determine the molar enthalpy of solution.
Defining some more terms
Standard enthalpy change of vaporization ΔHθV)
This is the heat needed to convert one mole of a substance at its boiling point from a liquid state to
gaseous state at one atmosphere.
For example to convert one mole of water at 1000C to steam requires 41Kj
H2O(l) H2O(g) ΔHθV = +41kJmol-1
Standard enthalpy change of atomization, (ΔHθa)
This is the heat required to produce one mole of gaseous atoms from the element in its standard state.
The following changes represent enthalpy changes of atomization
H2(g) H(g) ΔHθa =+218kjmol-1
K(s) K(g) ΔHθa = +89kJmol-1
P4(s) P(g) ΔHθa = +315kJmol-1
When the element is in the solid state the enthalpy of atomization is known as enthalpy of sublimation.

Ionization energy
Refers to the minimum energy required to remove completely one mole of electron from a gaseous
atom or gaseous ion against the attractive forces of the nucleus to form a positively charged ion
First ionization energy
Is the minimum amount of energy required to remove completely one mole of electron from one mole
of gaseous atoms to produce one mole of uni-positively charged gaseous ions.
Example, Al(g) Al+(g) ΔH = 1st ionization energy of aluminium
Second ionization energy
Is the minimum amount of energy required to remove completely one mole of electron from one mole
of gaseous ion to produce one mole of di-positively charged gaseous ions.
Example, Al+(g) Al2+(g) ΔH = 2nd ionization energy of aluminium.
You can then have as many successive ionization energies as there are electrons in the original atom.
The process of removing an electron from an atom requires energy since the electron is being removed
against the attractive forces of the nucleus. Therefore the process is endothermic.
Electron affinity
Is the energy change that occurs when one mole of electron is being added to one mole of gaseous
atom or ion
First electron affinity
This is the energy given out when one mole of an electron is being added to one mole of gaseous atoms
to form one mole of uni-negatively charged gaseous ion.
The more exothermic the value of electron affinity the more stable the ion formed
Example, O(g) + e O-(g)ΔH = -142Kj mol-1 1st electron affinity of oxygen.
First electron affinity is always an exothermic process because the electron being added is attracted by
the nucleus thus heat is given out.
Second electron affinity
This refer to the energy absorbed when one mole of electron is being added to one mole of uni-
negatively charged gaseous ions to form one mole of a di-negatively charged gaseous ion
Example, , O-(g) + e O2-(g)ΔH = +844Kj mol-1 2nd electron affinity of oxygen.

Second electron affinities are always positive because energy is needed to force an electron into an
already negative ion.
Lattice energy
This term is applied to crystals which are essentially ionic in character
The lattice energy of a crystal is defined as the amount of energy given out when one mole of an ionic
crystal lattice is formed from its constituent gaseous ions.
Na+(g) + Cl-(g) Na Cl (s) ∆H = - 760kjmol-1
Or is the minimum amount of energy required to break one mole of ionic crystal lattice into its
constituent gaseous ions.
Other examples
K+(g) + Cl- (g) KCl (s) ∆H = -707kjmol-1
Mg2+(g) + O2-(g) MgO (s) ∆H = -3791 kjmol-1
Ba2+(g) + O2- (g) BaO (s) ∆H = -3050 kjmol-1
When ionic crystal is formed from its gaseous ions
Lattice energy values are will be negative because lattice energy involves attraction of oppositely
charged particles into a fixed crystal lattice.
The more negative the lattice energy the more stable the crystal structure.
Lattice energy also indicates how strongly the cat ion and anion are held together in the crystal
structure.
Factors affecting the magnitude of lattice energy.
a)The charge on each ion ( ionic charge )
Lattice energy is proportional to the product of charges of ions. The larger the product of ionic charge,
the bigger the lattice energy. This is because of the strong electrostatic forces of attraction between
oppositely charged ions.
Na+(g) + Cl-(g) Na Cl (s) ∆H = - 760kjmol-1
Mg2+ (g) + 2Cl-(g) MgCl2 ∆H = -2493 kjmol-1
e.g. MgCl2 has bigger lattice energy than NaCl because magnesium has a high charge of positive whereas
sodium has a charge of positive one.

b)Ionic radius
Lattice energy is inversely proportional to the sum of the radii.
The smaller the sum of ionic radii, the bigger the lattice energy.
This is because the higher the charge density = the higher the electrostatic forces of attraction
between oppositely charged ions.
This explains why NaF has bigger lattice energy than CsF because the ionic radius of Na+ is smaller than
that of Cs+ ,Na+ has higher charge density.
Na(g)+ + F-(g) NaF(s) ∆H = -918 kjmol-1
Cs+(g) + F-(g) CsF(s) ∆H = -747 kjmol-1
Importance of lattice energy
 Substances with high lattice energy will have high melting points
 The solubility of ionic compounds, will depend upon the relative values of lattice energy and
hydration energy the smaller the lattice energy and the greater the hydration energy the larger
is the solubility in water.
 Lattice energy can be used to explain the existence of some compound
o Example why magnesium chloride is MgCl2 but not MgCl)

o The main factor which favours the formation of MgCl2 is the very high lattice energy.
This more than compensates for the additional energy that has to be supplied for the
second ionization of magnesium to form Mg2+ from Mg+.
 Comparison of the calculated and experimental values for lattice energy gives indication of the
degree of covalent bonding in a compound if the theoretical value is less than the calculated
value then the solid is not purely ionic there is appreciable covalent character

Born – Haber cycles
The Born – Haber cycle is a technique for applying Hess’s law to the standard enthalpy changes which
occurs when ionic compound is formed.
It relates the enthalpy of formation of ionic compounds and to the enthalpy of atomization of elements
concerned, the ionization energies for the formation of gaseous cat ions, the electron affinity for the
formation of gaseous anions and the lattice energy of ionic substances.
This can either be drawn as a Hess’s law cycle or as an enthalpy level diagram.
In enthalpy level diagram
Each horizontal line represents the energy level the species existing on this level are written on the line
together with their states.
The gaps represent the enthalpy changes accompanying the changes in the species shown.
For convenience we will look at the changes affecting cation first and the anion after wards
Positive enthalpy changes and shown going up the diagram, while negative values are shown going
down the diagram
Consider the Born- Haber cycle for formation of sodium chloride
Some thermo-chemical data of sodium and chlorine are given below
Heat of formation of sodium chloride = -602 Kjmol-1
Heat of atomization of sodium = +109 Kjmol-1
First ionization energy of sodium = +494 Kjmol-1
Atomization energy of chlorine = +121 Kjmol-1
First electron affinity of chlorine = -364 Kjmol-1
i)draw an energy level diagram for the formation of sodium chloride
ii)calculate the lattice energy of sodium chloride
solution

From the thermo-chemical data given the following equations can be written
Na (s) + Cl2 (g) NaCl (S) ∆H = -411 Kjmol-1
Na(s) Na(g) ∆H = +109 Kjmol-1
Na(g) Na+(g) + e ∆H = +494 Kjmol-1
Cl2 (g) Cl (g) ∆H = +121 Kjmol-1
Cl(g) + e Cl-(g) ∆H = -364 Kjmol-1
Enthalpy level diagram
Na+(g) + e + Cl (g)
+121kjmol-1 -364kjmol-1
Na +(g) + e+ Cl2 (g)
Na+(g)+ Cl- (g)

-1
+494kjmol
enthalpy
Na(g)+ Cl2 (g)
+109kjmol-1
Na(s) + Cl2(g) Lattice energy
-411kjmol-1
NaCl2 (s)
Enthalpy diagram showing Born-Haber cycle for formation of sodium chloride
From Hesss law -411+(+109)+ (+494)+ (+121)+ (-364)+ lattice energy =-411
Lattice energy=-771kjmol-1

Example two
Consider the Born- Haber cycle for formation of magnesium oxide
Some thermo-chemical data of magnesium and oxygen are given below
Heat of formation of magnesium oxide = -602 Kjmol-1
Heat of atomization of magnesium = +150 Kjmol-1
First ionization energy of magnesium = +736 Kjmol-1
Second ionization energy of magnesium = +1450 Kjmol-1
Atomization energy of oxygen = +248 Kjmol-1
First electron affinity of oxygen = -142 Kjmol-1
Second electron affinity of oxygen = +844 Kjmol-1
i)draw an energy level diagram for the formation of magnesium oxide
ii)calculate the lattice energy of magnesium oxide
Mg (s) + O2 (g) MgO (S) ∆H = -602 Kjmol-1
Mg(s) Mg(g) ∆H = +150 Kjmol-1
Mg(g) Mg+(g) + e ∆H = +736 Kjmol-1
Mg+(g) Mg2+(g) + e ∆H = +1450 Kjmol-1
O2 (g) O (g) ∆H = +248 Kjmol-1
O(g) + e O-(g) ∆H = -142 Kjmol-1
O-(g) + e O2-(g) ∆H = +844 Kjmol-1

Enthalpy level diagram
Mg2+ (g) + O2- (g)
Mg2+ (g) + O (g)

Mg2+ (g) + O- (g)
Mg2+ (g) + O2 (g)
Mg+ (g) + O2 (g)
Mg (g) + O2 (g)
Mg (s) + O2 (g)
MgO (S)
By Hess’s law
+150 + 736+1450+248 -142 +844 +LE =-602
LE =-3888kJmol
Born-Haber cycle
∆H1
Mg(s) + O2 (g) MgO(s)
∆H2 ∆H5
Mg(g) O(g)
Mg+∆H
(g) 3 O-(g) ∆H6
∆H7 ∆H8
∆H4
Mg2+ (g) + O2- (g)

Consider the Born- Haber cycle for formation of aluminium oxide
Some thermo-chemical data of aluminium and oxygen are given below
Heat of formation of aluminium oxide = -1675.7 Kjmol-1
Heat of atomization of aluminium = +324.3 Kjmol-1
First ionization energy of aluminium = +578.0 Kjmol-1
Second ionization energy of aluminium = +1817.0 Kjmol-1
Third ionization energy of aluminium = +2745.0 Kj mol-1
Atomization energy of oxygen = +248 Kjmol-1
First electron affinity of oxygen = -142 Kjmol-1
Second electron affinity of oxygen = +844 Kjmol-1
i)draw an energy level diagram for the formation of aluminium oxide
ii)calculate the lattice energy of aluminium oxide
2Al (s) + O2 (g) Al2 O3 (S) ∆H = -1675.7 Kjmol-1
Al(s) Al(g) ∆H = +342.3 Kjmol-1
Al (g) Al+(g) + e ∆H = +578.0 Kjmol-1
Al+(g) Al2+(g) + e ∆H = +1817.0 Kjmol-1
Al2+(g) Al3+(g) + e ∆H = +2745 Kjmol-1
O2 (g) O (g) ∆H = +248 Kjmol-1
O(g) + e O-(g) ∆H = -142 Kjmol-1
O-(g) + e O2-(g) ∆H = +844 Kjmol-

Energy level diagram

Enthalpy changes when ionic compounds dissolve in water
Enthalpy change of solution
This is the enthalpy change when one mole of ionic compound completely dissolves in a specific amount
of water to form infinitely dilute solution.
‘’Infinitely dilute’’ means that you have used enough water so that adding some more doesn’t result in
any more heat change.
The equation for such reactions would be written as, for example:
NaCl(s) + (aq) NaCl (aq) ∆Hsol = +5kjmol-1
CuSO4 (S) + (aq) CuSO4 (aq) ∆H = - 66kjmol-1
CuSO4 5H2O(s) + (aq) CuSO4(aq) + 5H2O(l) ∆H = +11kjmol-1
The process of dissolving ionic compound in water involves two energy stages.
Stage one
Separating of ionic compounds into oppositely charged gaseous ions and the energy involved is called
lattice energy. The process is endothermic.
Stage two
Wrapping them in water molecules and the energy involved is called hydration energy. The process is
exothermic
Enthalpy change of hydration
This is the energy given out when one mole of gaseous ions is surrounded by water molecules to form
an infinitely dilute solution. It applies equally to positive and negative ions.
Mg2+ (g) + (aq) Mg2+ (aq) ∆HHn = -1920 kJmol-1
Cl-(g) + ( aq ) Cl- (aq) ∆HHn = -364 kJmol-1
Hydration enthalpies are always exothermic because of the formation of attractive forces between the
ions and water molecules.
For a cat ion it is the results of the force of attraction between the ion and the
ẟ- oxygen in water.
For the anion it is the result of the force attraction between the ion and the
ẟ+ hydrogen in water.

The value of the enthalpy of hydration will depend upon the value of the charge on the ion and its ionic
radius.
The larger the charge, the more exothermic the enthalpy of hydration
Na+ (g) + (aq) Na+ (aq) ∆HHn = -406 kJmol-1
Magnesium ion has a charge of +2 whereas sodium ion has a charge of +1
The larger the ionic radius the less exothermic the enthalpy of hydration
Ba2+ (g) + (aq) Ba2+ (aq) ∆HHn = -1360 kJmol-1
The ionic radius of magnesium ion is less than that of barium ion
Calculating enthalpy change of solution
Consider the dissolution of barium chloride in water.
Using Hess’s law cycle
BaCl2(s) + (aq ) Heat of solution Ba2+(aq) + 2Cl- (aq)
Lattice energy
-1360 hydration energy

2x -364
+2018 aq aq
Ba2+ (g) + 2 Cl- (g)
by applying Hess’s law
Heat of solution = lattice energy + hydration energy
NOTICE
 When the lattice energy is greater than the hydration energy the enthalpy change of solution
will be positive (endothermic)
 Whereas when the hydration energy is greater than the lattice energy the enthalpy change of
solution will be negative (exothermic)
 For an ionic compound to dissolve in water easily, the lattice energy should be overcome by the
hydration energy such that overall enthalpy change of solution is negative.

 Compounds which dissolve exothermically are more stable than those which dissolve
endothermically.
 the dissolution of sodium chloride is endothermic yet sodium chloride readily dissolves in water
. the reaction occurs spontaneously because of the increase in the entropy of the system
 Hydrated copper (ii) sulphate crystals dissolves endothermically whereas anhydrous copper(ii)
sulphate dissolves exothermically.
CuSO4(s) + aq Cu2+(aq) + SO42-(aq)
CuSO4.5H2O(s) + aq
For hydrated copper (ii) sulphate, the ions are partly hydrated thus hydration energy is partly lost. When
the crystals are dissolved in water, further hydration occurs and this energy is not enough to outweigh
lattice energy therefore heat of solution is endothermic. For anhydrous copper (ii) sulphate, the
hydration energy is readily available and is able to outweigh lattice energy therefore heat of solution is
exothermic.
Experiment to determine the enthalpy of solution of an ionic salt eg sodium chloride
Procedure
 -a known volume of water( vcm3) is put in a plastic beaker(or insulated calorimeter)
 -the initial temperature of water(t10c) is measured and recorded
 -a known mass of the sodium chloride( ag) is added to the water and stirred
 -the final temperature of solution(t20c) is measured and recorded
Treatment of results
Temperature change =( t1 –t2)
Mass of solution = (a + Vx1)g
Heat change = mass of solution x C x = (a + V) x 4.2 x
ag of the salt evolves =((a + V) x 4.2 x )joules
One mole of the salt will evolve = kjmol-1
Where W is the molar mass of the salt.

BOND ENTHALPY or BOND ENERGY
During chemical reactions between covalent compounds, a number of bonds in reactants are broken
and new bonds are formed in products.
Forming bonds liberates energy and breaking bonds requires energy
Bond energy is the energy required to break one mole of covalent bond into its constituent gaseous
atoms.
or This is the energy released when one mole of a particular covalent bond is formed from its
constituent gaseous atoms.
Bond dissociation energy (or enthalpy) and average bond energy
For simple diatomic molecules (one containing only two atoms) like hydrogen,H2 or hydrogen
bromide,HBr,the energy needed to break one mole of the bond is referred to as bond dissociation
energy(or bond dissociation enthalpy):
ᶿ
H2(g) H(g) +H(g) =+ 436kjmol-1
HBr(g) H(g) + Br(g) ΔH = +366 kjmol-1
For poly atom molecule (one containing more than two atoms) like methane, the energy required to
break a given bond will depend upon the nature of the other atoms or groups joined to it and will vary
from compound to compound for instance the energy required to break the O-H bond in an alcohol is
not the same as the energy needed to break the same bond in an organic acid.
Therefore this energy required to break a particular bond in poly atomic molecule is called average
bond energy or just bond energy
Average bond enthalpy may be taken as
the average calculated from the sum of the bond dissociation enthalpies of all similar bonds in a
molecule
The average of the four C – H bond enthalpy for methane = = 1 kjmol-1
Or Average bond enthalpy may be taken as
As the average of the average bond energy of all compounds containing that particular bond
Where the average bond energy of all compounds containing C – H bond is 413 kjmol-1
In a poly atomic molecules, the energy required to break a given bond will depend to some extent on
the nature of the remainder of the molecule and will vary from compound to compound

Below are some of the bond enthalpies at 25o
BOND H/kjmol-1
H-H 436
C-C 348
C=C 612
C≡C 838
C-H 413
C-O 358
C=O 805
N-N 158
N=N 410
N≡N 945.4
C-F 484
C-Cl 338
C-Br 275
C-I 238
Br-Br 192
Cl-Cl 243.3
F-F 158
I-I 151
Factors affecting bond energies
Number of bonding electrons
The more electrons that are contributed in the formation of the bond, the greater the strength of that
bond eg triple bonds between carbon atoms are stronger than the double bonds which are in turn
stronger than the single bonds
Single bonds ˂ double bond ˂ triple bonds
Bond polarity
As the difference in electro-negativity between bonded atoms increase the bond becomes more polar
and this increases the ionic character of the bond thus increasing the bond strength
The bond strength of the hydrides of nitrogen, oxygen and fluorine is in the order
F H O H H explain
Bond length
The larger the atoms joined by a particular bond the longer the bond length. This is because, in lager
atoms there are more electrons than in smaller ones this will result in an increase in screening effect of

the nucleus and hence an increase in electron repulsion in the bonded atoms these two effects weaken
the bond hence giving a low bond energy
Uses of bond energy
Strength of bonds can be compared
To understand the mechanism of a chemical reaction
To understand the structure and bonding of covalent compounds
Can be used to explain a number of facts from inorganic and organic chemistry
for example the increased reactivity of phosphorous compared to nitrogen,
the increased rate of substitution reactions for lodo- Alkanes compared with other hydrogen Alkanes.
The enthalpy change for the atomization can be estimated using bond enthalpies
ᶿ
H2(g) 2H(g) =+ 436kjmol-1
ᶿ
H2(g) H(g) =+ 218kjmol-1
Atomization energy =
Bond enthalpies can be used to estimate likely enthalpy changes of reaction
Calculations involving bond energies
For example 1
Estimate enthalpy change for the reaction
CH4(g) + Cl2(g) CH3Cl(g) + HCl(g)
Given the following bond enthalpies;
C-H =+413Kjmol-1 C-Cl =+346kJmol-1
Cl-Cl=+243kJmol-1 H-Cl=+432kJmol-1
The method does require some knowledge of the bonding present in the particular molecules.
Start by writing the balance equation,
Show the structure of all the molecules to make counting bonds easier.
Draw arrows from compounds to gaseous atoms in the bottom corner.

Now find two routes around the diagram without going against the flow of an arrow and equate them
according to Hess’s law.
Enthalpy of reaction
H-C-H g + Cl - Cl g H -C-Clg + H-Clg
C(g) +4 H(g) +2 Cl(g)
H= (the sum of the average bond enthalpies of reactants) – (the sum of the average bond enthalpies of
the products)
H0=( 412 + 242) – ( 3×412) + 338 + 431 = -115kjmol-1
Example 2
Estimate the enthalpy change for the reaction
3H2(g) + N2(g) 2NH3(g)
Given the following bond enthalpies;
N-H =+381Kjmol-1
H-H=+436kJmol-1
N-N=+946kJmol-1
3(H-H)(g) + (N N)(g) 2(N - H ) (g)
3 𝐻 𝐻 1 𝑁 𝑁
6 𝑁 𝐻
6H + 2N
H= (8 ×435) + (945.4) + (6 × 381) = 93.3kjmol-1

Example 3
Given that the standard enthalpy of formation of methane is -74.8kjmol-1 and the enthalpies of
atomization of graphite and hydrogen are +751 and +218kjmol-1 in the gas phase.
Calculate the bond energy of C-H.
C(s) + 2H2 (g) H1= -74.8kjmol-1 CH4(g)
H3=2x218kjmol-1
H2=751kjmol-1
H4 =4(C-H)kjmol-1
C(g) + 4Hg
H1 = H2 + H3 + H
Example 4
The enthalpy of formation of phosphorous tri-chloride is -306kjmol-1 and the enthalpy of atomization of
phosphorous and chlorine are + 314 and + 242 kjmol-1 respectively. Calculate
The average the bond energy of P –Cl bond

-306
P4(s) + Cl2(g) PCl3(g)
+314 +3 x 242
3(P-Cl)
P(g) + 3Cl(g)
-306 = 314 + 3x 242 + 3BE (P-Cl)
BE (P-Cl) = = -448.67 kjmol-1

ENTHALPY OF HYDROGENATION
This is the enthalpy change when one mole of unsaturated compound is completely converted into the
corresponding saturated compound by reaction with gaseous hydrogen
The hydrogenation of cyclohexene and ethene can be represented respectively by
+ H2(g)
ΔH = -120kjmol-1
CH2=CH2 + H2(g) CH3CH3 ΔH = -120kjmol-1
It’s possible to predict a value for standard enthalpy of hydrogenation of benzene if its structure is
assumed to consist of alternate double and single carbon-carbon bonds. The reaction may be
represented by the equation
+ 3(H-H)
The enthalpy change of hydrogenation should be 3x(-120)=-360kjmol-1.
The experimental value for the enthalpy change of hydrogenation of benzene is -208kjmol-1
The difference between these two values indicates that the actual structure of benzene is more stable
than the alternate double and single bond structure by a factor .equivalent to 360 – 208 =152kjmol-1
This extra stability is attributed to the delocalization of the bonding electrons over all six carbon atoms

Delocalization of energy
The sharing of elections over more than two atoms is referred to as delocalization and the energy
associated with the resulting extra stabilization is known as the delocalization energy.
+ 3H2(g)
152kjmol-1
+ 3H2
-360kjmol-1
-208kjmol-1

Topic 5: Physical equilibrium
This involves the study of behaviour of substances as they change phase
General objectives
By the end of this topic, the learner should be able to comprehend the concept of inter
conversion of phases due to changes in the physical conditions and its application
System, phase and component

System
A system is the part of universe being studied, for example hot water or cold water in a beaker.
A system may be homogeneous or heterogeneous. A homogeneous system shows uniform
composition or structure for example salt solution where as a heterogeneous system is one
with a mixture of state such as liquid-solid or liquid-solid-gas. There three types of system
Open system which is a system that freely exchanges energy and matter with its surroundings
for example liquid in a vessel from which vapour can escape.
Closed system is a system that exchanges only energy with its surroundings for example liquid
and vapour in a sealed container.
And an isolated system is one which does not exchange energy or matter with its surrounds for
example cold or hot water in a sealed thermos flask.
Phase
Each of the three homogeneous physical states (solid, liquid and gas) in which a substance can
exist is called a phase.
A Phase is a homogeneous part of system which is physically distinct from other parts of system
and can be separated from other parts by a definite boundary surface.
Examples; mixture of gases is one phase, Aqueous solution is one phase, Two immiscible
liquids is a two phase system

Phase equilibria; involves the study of the conditions (temperature, pressure and
concentration) under which different phases are in equilibrium.
Equilibrium can only be achieved in closed system when the rate of movement of molecules
from one phase to the other is exactly balanced by the rate of movement of molecules to the
other.
The conditions of temperature and pressure under which different phases are stable can be
shown on the phase diagram
In a phase diagram a phase is represented by a region that is separated from other regions by
lines or curves. The lines or curves represent the conditions under which two phases can exist
in equilibrium and a triple point describes the conditions under which three phases can coexist.
Component
This is the number of chemical species needed to define a phase system. It can be one
component system for example water system, sulphur system, two components for example
solution of sodium hydroxide or three component system for example iodine in two immiscible
liquids in contact.
One component system

Example of one component system include; water, carbon dioxide and sulphur
Water system
Water can exist in three possible forms; ice (solid), water (liquid) and water vapour. These three
forms can exist in two phase equilibria i.e solid-liquid, solid-vapour and liquid-vapour or in
three phase equilibria as solid-liquid-vapour
The various equilibria which can exist when water is held at various pressures and
temperatures are summarized in the pressure-temperature diagram below

C
B 218atm
LIQUID
Vapour pressure(atm)
1 atm
ICE WATER
VAPOUR
A O
100 374
0 Temperature(0c)
Point O is called the triple point of water i.e. the temp and pressure at which all the three
phases solid, liquid and vapour can co-exist in equilibrium with each other.
Point B is called the critical point of water; it corresponds to the critical temperature. critical
temperature is the temperature beyond which the vapour cannot liquefied no matter the
applied pressure, the vapour and liquid become indistinguishable
Curve AO is the sublimation curve for ice. Shows the combination of temperature and pressure
at which ice and its vapour are in equilibrium
Curve OB is the vapour pressure curve of liquid water or the vaporization curve of liquid water
shows the combination of temperature and pressure at which liquid water and its vapour can
exist in equilibrium the curves show effect of pressure on the boiling point of water
An increase in pressure causes an increase in boiling point .any temperature along this curve
boiling occurs and any particular temperature along this curve gives the boiling point of liquid
water at that pressure.
Boiling point is the constant temperature and pressure at which the liquid turns into a vapour.

Curve OC is the melting point curve of ice or the freezing point curve of liquid water. Shows the
combination of temperature and pressure at which a solid and its liquid can exist at equilibrium
The line shows the effect of pressure on the melting point of ice or the freezing point of liquid
water. The curve slopes towards the pressure axis (towards the left) indicating that the melting
point of ice is lowered by an increase in pressure.
Effect of change of temperature or pressure or both on the system
(i) suppose water at point M was cooled at constant pressure of 1 atmosphere up to

point N
The liquid continues to cool but without changes in phase until curve OC is reached at which
temperature freezing starts. The temperature remains constant at the freezing point and a
liquid solid equilibrium is established at the freezing point further decrease in temperature
beyond curve OC, all the liquid molecules freeze forming a solid at phase N.
(ii) Suppose water vapour at point R is subjected to an increase in pressure at

constant temperature up to point S
When the pressure at point R is increased at constant temperature, the vapour is compressed
causing a decrease in its volume but it remains a vapour. i.e. No change in phase occurs until
the pressure on curve OB is reached at which pressure the vapour starts to change into a
liquid (condensation) and the two (liquid and vapour remain in equilibrium at this pressure)
further increase in pressure beyond curve OB compress the remaining vapour causing a further
decrease in volume until all is a liquid at phase S
(iii) Suppose ice at point M is converted to vapour at point T

ii) Carbon dioxide system
An example of a substance which melt with increases in volume
B C
SOLID CO2 Liquid CO2

Pressure (mmHg)
M N
O Gaseous CO2
A
Temperature(k)
This diagram is similar to that of water though it has two important differences
(i)The line OB slopes away from the vapour pressure axis indicating that the melting point of
solid carbon dioxide is increased with increase in pressure because molecules of carbon dioxide
in the solid phase are parked more closely than in the liquid phase unlike in water..
(ii)the triple point of carbon dioxide occurs at a higher vapour pressure than that of water.
Describe what happens when a substance at point m is subjected to increase in temperature

at constant pressure to point n
If the solid phase is heated at constant pressure, the solid expand causing an increase in its
volume without a change in phase. However, further heating of the solid makes it liquefy at its
melting point which occurs along curve AB. At this point the solid remains in equilibrium with
liquid.
Further heating of the solid turns everything into a liquid. When the liquid is heated
continuously, it begins to vaporize until curve AC at what the vapour remain equilibrium with
the liquid at the boiling point.

Describe what happens when a substance at point P is subjected to decrease in pressure at
constant temperature to point q
The solid expands on decreasing its pressure causing an increase in its volume and it changes
into a vapour i.e. it sublimes if the pressure of the liquid is decreased, the liquid changes to a
vapour.
The sulphur system
Sulphur exists in two allotropic forms i.e the α-sulphur which has rhombic crystalline form and
β-sulphur which has monoclinic crystalline form which are stable over different temperatures.
The temperature at which the two forms are in equilibrium is called transition temperature and
it is960C monoclinic sulphur is stable above 960C until a temperature of 1190C when it melt
while rhombic sulphur is stable below 960C
D
LIQUID SULPHUR
C
PRESSURE
B
VAPOUR
TEMPERATURE
(0C)
Curve AB; is called sublimation curve of rhombic sulphur, it shows the variation of vapour
pressure of rhombic sulphur in equilibrium with its vapour with temperature.

Curve BC; is called the sublimation curve of mono clinic sulphur, it shows the variation of
vapour pressure of monoclinic sulphur in equilibrium with its vapour with temperature
Curve CD; it is called vaporization curve of liquid sulphur and stable up to point D,it shows
the variation of vapour pressure of liquid sulphur with temperature
Curve BF; it is called a transition curve Shows the effect of pressure on the transition point
between rhombic sulphur and monoclinic sulphur along this line monoclinic sulphur is in
equilibrium with rhombic sulphur.
Curve CF; is called the fusion curve of monoclinic sulphur, it shows the effect of pressure on the
melting point of monoclinic sulphur
Curve EF; is called the fusion curve of rhombic sulphur, it shows the effect of pressure on the
melting point of rhombic sulphur
Point B is called the triple point for rhombic sulphur, monoclinic sulphur and sulphur vapour
Point C is called the triple point for monoclinic sulphur, liquid sulphur and sulphur vapour
Point E is called the triple point for rhombic sulphur, monoclinic sulphur and liquid sulphur
Point D is called a critical point
When any of the phases is subjected to a change in temperature or pressure .it will
disappear and another dominates.
When rhombic sulphur is heated, no change in phase occurs but it expands causing an
increase in volume. This continues until curve EF, is reached when rhombic sulphur starts
liquefying at its melting point. The solid remains in equilibrium with the liquid at the melting
point.
Further heating beyond curve EF, it completely liquefies giving a liquid phase at point Y
decreasing the pressure of phase Y causes no change but an increase in volume until when it
vaporizes along curve CD where the liquid remains in equilibrium with the vapour.

Further decreases in pressure beyond curve CD all the liquid turns into a vapour.
When the vapour at phase Z is heated, there is no change in phase up to point W instead the
vapour expands due to increase in temperature.
Decreasing the pressure of rhombic sulphur at X, there is no change in phase but an increase in
volume due to a reduced pressure until curve AB is reached at which point rhombic sulphur
begins to sublime. The vapour remains in equilibrium with the solid at the sublimation
temperature.
Further decrease in pressure beyond curve AB all rhombic sulphur sublimes into sulphur
vapour.

TWO COMPONENT SYSTEM
LIQUID-VAPOUR EQUILIBRIUM
Mixtures of two liquids

When two liquids which do not react chemically are brought together they give rise to three
possibilities completely miscible, completely immiscible and partially miscible.
COMPLETELY MISCIBLE LIQUIDS

These are liquids which completely dissolve in each other in all proportions to give a
homogeneous solution and have no saturation limit. Water and ethanol are completely
miscible and so are methyl benzene and benzene, hexane and Heptane.
Generally it has been observed that those liquids which have similar chemical structure are
completely miscible in each other while liquids which have different chemical structure are
completely immiscible.
Thus water is completely miscible with alcohol because the two are chemically similar.
There are two types of solution; ideal solution and non-ideal solution
Ideal or perfect solution

This is a mixture of compatible liquids with intermolecular forces between molecules of the
pure components and those intermolecular forces between the molecules of the unlike
components similar and equal in strength. The solution obeys Raoult’s and no heat changes or
changes in volume occur when the mixture is made.
Characteristics of ideal solutions
They obey Raoults law under all conditions
The cohesive forces between like molecules are equal to adhesive forces between unlike
molecules
There is no heat change that occurs when the components of the solution are mixed.The total
volume of the solution is equal to the sum of the volume of the individual components.

Pairs of liquids which act in this way are those with little or no polarity in their valency bonds or
with similar degree of polarity. They include benzene and methyl benzene methanol and water
and propan-1-ol and propan-2-ol.
RAOULT’S LAW
There is, in a solution, as in a pure liquid a nature tendency for some molecules to overcome
the intermolecular forces of attraction and escape from solution and pass into the vapour
phase.
When the solution is in equilibrium with vapour, the total vapour pressure of the solution
above the mixture will depends on the partial vapour pressure of the components and on the
composition of the mixture. The partial vapour pressure of each component in the mixture can
be calculated using Raoults law
Raoults law which states that;
The partial vapour pressure of a component of an ideal solution, is equal to the vapour
pressure exerted by the pure component at that temperature multiplied by the mole fraction
of that component.
The assumption made here is that vapour behave as ideal gases
Mole fraction is a convenient way of expressing the composition of each component in a

mixture.
The mole fraction of A in a mixture of A and B is XA =
The mole fraction of B in a mixture of A and B is XB =
The sum of the mole fraction of the components in the mixture equals to one + =1
Raoult’s can be expressed mathematically as

and are the partial vapour pressures of the components A and B over the liquid
In any mixture of gases each gas exerts its own pressure independently of the other gases in the
mixture
is the vapour pressure of A over pure A at that temperature
and are the vapour pressure of B over pure B and B at that temperature
the total vapour pressure of the mixture (at a given temperature) over the liquid is equal to
the sum of the partial pressures of the two components this is according to Dalton’s law
= +
+ + 1
In the mixture of ideal solution partial vapour pressure of a component is proportional to its
mole fraction. This is expressed in the figure below
VAPOUR PRESSURE- COMPOSITION DIAGRAM FOR BINARY IDEAL SOLUTION
F P0A
PT
P0B D
PA
PB
E C
0.8A
0 Mole fraction of A .8 1
Fig 4.4 the vapour pressure composition diagram of an ideal solution

P0A is the vapour pressure of pure A
P0B is the vapour pressure of pure B
< This shows that liquid A is more volatile than liquid B
Line CD shows the variation of vapour pressure of component B with composition
Line EF shows the variation of vapour pressure of component A with composition.
Line DF shows the variation of total vapour pressure with composition
The a vertical dotted line represents a solution of composition 80%A
Beginning with pure A(100%A and 0%B) the partial vapour pressure of A decreases as B is
added and it tends to zero when B is 100%. This is because the molecule of B gradually replaces
the molecules of A above liquid mixture
Worked examples
Example one
At 880C, the vapour pressure of benzene and toluene are 935 and 378 mmHg respectively.
Calculate the vapour pressure of the benzene –toluene mixture containing two moles of
benzene per mole of toluene assuming ideal behavior.
Moles of benzene =2
Moles of toluene =1
PBenzene = x935
PToluene = x378
PTotal = x935 + x378 =749.333mmHg
Example 2

Calculate the vapour pressure of a solution containing 50g of Heptane and 38g of Octane at
200C.the vapour pressure of Heptane and Octane are 473.2pa and 139.8pa respectively.
RFM of Heptane C7H16 =12x7 + 1x16 =100
RFM of Octane C8H18 =12x8 + 1x18 =114
Moles of Heptane = =
Moles of Octane = =
PHeptane = x473.2
POctane = 1 98
PTotal =283.92 + 55.92 =339.84pa
NON-IDEAL SOLUTIONS OR REAL SOLUTIONS

A real solution is one which shows deviation from Raoult’s law
These are deviations brought about by the difference in the intermolecular forces between the
molecules of pure component and molecules of different components.
The vapour pressure of such solutions are either higher or less than that expected from Raoults
law these deviations are generally observed for systems in which the two components of liquid
mixture have different molecular structure. Majority of liquid mixtures do not obey Raoults law
and exhibit either a positive or negative deviation from Raoults law.
NEGATIVE DEVIATION FROM RAOULTS LAW
If the intermolecular forces of attraction between the different particles from the two liquids
are stronger than the attractive forces in the pure liquids then the particles will be held in the
liquid more strongly. There is less tendency for molecules to escape from the solution than

from the pure liquids the total vapour pressure above the liquid will be lower than that
predicted by Raoults law.in some cases the deviations are small but in others they are much
greater giving a minimum value for the vapour pressure lower than that of either pure
component.
Vapour pressure diagram for negative deviation from Raoults law
Composition X ,corresponding to the lowest vapour pressure, at this composition the inter
molecular forces of attraction between the two liquids are strongest
Explaining the deviations
The stronger forces could be due to extra inter molecular forces which exist in the mixture but
do not exist in pure liquids, which may be due to association of one or both of the component
in solution via weak inter-molecular hydrogen bonding or to some degree of compound
formation between the components of solution.it is recognized by the contraction in volume
and evolution of heat in making the solution (heat is given out when new bonds are made)
Examples of solutions which show negative deviation from Raoults law include;
i) Chloroform and Propanone
ii) Phenol and ethyl amine
iii) Ethanol and ethyl ethanoate

This is due to hydrogen bonding formed between the two molecules; hydrogen bonds are
stronger than the cohesive forces in the pure liquids
iv) Hydrochloric acid and water
v) Nitric acid and water
This is due to ionization of covalent molecules of acid in water forming the hydroxonium ions
and nitrate ions or chloride ions which have a stronger ionic attraction causing low escaping
tendency of the molecules into the vapour phase.
H2O (l) +HNO3(l) H3O+(aq) + NO3-(aq)
Properties of mixture that deviate negatively from Raoults law
i) The total volume decreases when the liquids are mixed
ii) Heat energy is evolved
iii) The adhesive forces between the components are stronger than the cohesive forces
in the individual components
POSTIVE DEVIATION FROM RAOULTS LAW
If the intermolecular forces of attraction between the different particles from the two liquids
are weaker than the attractive forces in the pure liquid then the particles will be held in the
liquid less well. The molecules in the solution will have a greater tendency to escape from the
solution than from pure liquids. The vapour pressure will be higher than that predicted by
Raoults law. in some cases the deviations are small but in others they are much greater giving a
maximum value for the vapour pressure higher than that of either pure component

Vapour pressure composition diagram for positive deviation from Raoults law
Composition X, corresponding to the highest vapour pressure, at this composition the inter
molecular forces of attraction between the two liquids are weakest
Explaining the deviations
The weaker forces in the solution is commonly brought about by the breakdown of the
hydrogen bonds in the pure liquids and replacing them with weaker intermolecular forces
which make it easier for the molecules of liquid to escape from the solution into the vapour. It
can also be caused by mixing a highly polar compound with a non- polar or a much less polar.
This is recognized by increase in volume and absorption of heat on mixing(less heat is evolved
when the new attractions are set up than was absorbed when to break the original ones).
Examples of solutions which show positive deviation from Raoults law include;
Ethanol and water
Ethanol and water molecules associate through stronger inter molecular hydrogen bonding but
when the two are mixed the hydrogen bonds break down. This causes less attraction between
molecules in water –ethanol mixture than the average attraction between the molecules in the
pure components of ethanol-ethanol molecules and water-water molecules hence increasing
escaping tendency into the vapour phase.

Benzene and ethanol
Benzene has a non- polar structure while ethanol is polar and associate via hydrogen bonding
these two forces of attraction are different in nature and when the component are put
together there will be greater repulsion between molecules of benzene and ethanol hence a
higher vapour pressure than that expected from Raoults law other examples include
cyclohexane and methanol, carbon di-sulphide and ethanol carbon tetra chloride and methanol
Properties of mixture that deviate positively from Raoults law
i) The total volume increases when the liquids are mixed
ii) Heat energy is absorbed
iii) The adhesive forces between the components are weaker than the cohesive forces
in the individual components.
The relationship between boiling point and vapour pressure
A liquid boils when its vapour pressure equals the atmospheric pressure.
The atmospheric pressure is frequently 1 atmosphere.
Boiling point is the temperature at which the vapour pressure becomes equal to atmospheric
pressure
Thus solution of two components A and B will boil when the total pressure i.e. PA + PB becomes
equal to 1 atmosphere.
The higher the vapour pressure of a liquid the more volatile is the liquid.
A liquid with higher vapour pressure will boil at a lower temperature than a liquid with lower
vapour pressure.

Thus a solution whose components have higher vapour pressure will boil at a lower
temperature than the solution in which the components have lower vapour pressure, this is
because solutions of higher vapour pressure can reach the external pressure at relatively lower
temperature and start boiling than the solution of lower vapour pressures.
Since according to Raoults law different compositions of solutions have different vapour
pressures it follows that solutions of different composition will boil at different temperatures
Increasing temperature increases the vapour pressure of both liquids in the mixture but the
vapour pressure of a more volatile component increases more rapidly
such that the graph of the temperature at which the mixture boils when plotted against
composition gives a curve. For a liquid mixture of any one composition the vapour with which it
is in equilibrium will be richer in the more volatile component so the composition of the vapour
lies on the other side of the straight line joining the boiling point.
BOILING POINT COMPOSITION DIAGRAMS OF BINARY MISCIBLE LIQUID MIXTURES
Boiling point composition diagrams are constructed from vapour pressure composition diagram
There are three important types of boiling point-composition diagram:
One where there is no maximum or minimum boiling point-this corresponds to the vapour
pressure composition diagram for ideal and nearly ideal solution.
One where there is a maximum boiling point-this corresponds to the vapour pressure
composition diagram with a minimum vapour pressure ie negative deviation.
One where there is a minimum boiling point-this corresponds to the vapour pressure
composition diagram with a maximum vapour pressure ie positive deviation.

Boiling point-composition with no maximum or minimum
Consider the vapour composition diagram of an ideal solution of A and B below
V.P of pure B
Vapour pressure
V.P of pure A
Mole fraction
 Component B has a higher vapour pressure than component A this means component B
will boil at lower temperature than component A.
 Different compositions of solution have different vapour pressure this implies that the
solutions of different composition will boil at different temperature. Therefore the
boiling point of the mixture will be between the boiling points of pure components.
 Increases in temperature, increases the vapour pressure of both liquids in the mixture,
but the vapour pressure of a more volatile component increases more rapidly such that
the graph of temperature at which the mixture boils when plotted against composition
gives a curve.
 For a liquid mixture of any composition the vapour with which it is in equilibrium will be
richer in the more volatile component, so the composition of the vapour lies on the
other side of the straight line joining the boiling points
vapour
Temperature(0C)
boiling point of pure A
liquid
mole fraction
vapour

Separating components in an ideal solution by distillation
Components in ideal solution can be separated by fractional distillation
Distillation is the process of vaporization of one component of the mixture and then condensing
the vapour back to the pure liquid. The process separates and purifies components with
significantly different boiling points
Whereas fractional distillation is the process of separating of completely miscible liquids with
boiling point close to each other .
In this technique, the mixture to be separated is placed in the distillation flask and a
fractionating column (long tube packed with glass beads to give the maximum possible surface
area for vapour to condense on) fitted with a thermometer as shown in the diagram below.
Then liquid mixture is heated and the rising vapour passes up the fractionating column, the
vapour of the less volatile component condenses on the beads as temperature fall up the
column and trickles back in the distillation flask where it will meet new hot vapour rising that
will cause the already condensed vapour to reboil. The vapour condenses on the beads and
vaporizes again many times as it passes up the column At each condensation and vaporization
the composition of the vapour changes as it becomes richer in the more volatile component
.the vapour of the more volatile component continues to rise up to the top of the column
where it is cooled in the condenser and collected as the distillate the less volatile component
tend to condense and fall back down the column. The first fraction to be collected is the most
volatile of the mixed liquids then the next most volatile comes through and so on
All the vapour due to the more volatile component is therefore obtained at its boiling point and
on cooling all the components are isolated in case of ideal solutions.

Using boiling point diagram
The boiling point composition diagram can be used to describe the changes that take place
when miscible liquids are fractionally distilled
Temperature(0C)
boiling point of pure A
V1 T1
V2
T2
L2 L1
L3
vapour
Percentage by composition by mass
Suppose you heat a liquid mixture of composition L1, until it begins to boils at temperature T1
then the vapour over the top of boiling liquid will have the composition V 2 . If the vapour is
condensed by meeting the cold surface of the distillation column, it condenses to form a liquid
of composition L2 .this liquid starts to trickle down the column towards the distillation flask. If it
is heated by upcoming vapour,it begins to boil at T2,to form a vapour of composition V2 ,if this
vapour is condensed, it forms a liquid of composition L3.by repeated vaporization and
condensation, the composition of the vapour is made to follow the curve V 1V2V3,becoming

richer in the more volatile component. The liquid is becoming richer in the less volatile
component, and the composition follows the curve from L1 towards the less volatile.
The longer the column, the more vaporization followed by condensation steps will be achieved,
and the closer to pure A and pure B will the distillate and residue become.
Therefore successive boiling and cooling results in isolation of the more volatile component at
its boiling point which is collected as the distillate leaving the residue in the flask as pure less
volatile component
By fractional distillation it is possible to separate two components which are ideal solution
Composition of the vapour
If you boil a liquid mixture, you can find out the temperature it boils and the composition of the
vapour over the boiling liquid.
Composition of the vapour ; is the fraction contributed by each component in the vapour
phase
The composition of any ideal solution is governed by Raoults law and the composition of the
vapour above solution by Dalton‘s law of partial pressure
For example if you boil a liquid mixture of composition XB it will boil at a temperature T1 and
the vapour over the top of the boiling liquid will have the composition Y B
Temperature(0C)
YB boiling point of pure A
XB
molevapour
fraction

According to Daltons law
PB = YB PT
YB = ==
Worked examples
The saturated vapour pressure of benzene and Toluene are 957mmHg and 378mmHg
respectively
i) Calculate the composition of benzene –toluene mixture at 760mmHg
PTotal =PB +PT
760 =957XB +378XT
760 =957(1-XT) + 378XT
XT =0.34
XB =0.66
ii)Calculate the composition of the vapour obtained when a liquid mixture boils
YB =
= = 0.83
YToluene =1-0.83 = 0.17
iii) Which of the two liquids is more volatile
Benzene, because it has a higher vapour c

Boiling point composition diagrams for non- ideal liquid mixture
Minimum boiling point –composition diagram
A diagram of this type is given by non- ideal solution that deviates positively from Raoults law.
A large positive deviation from Raoults law produces a vapour pressure curve with a maximum
value at some composition other than that of pure components, this implies that the boiling
point composition curve will have a minimum value lower than the boiling points of either pure
components
In cases of a mixture of ethanol and water which deviates positively from Raoults law; this
minimum occurs with 95.6% by mass of ethanol in the mixture. The boiling point of this mixture
is 78.20C, compared with the boiling point of pure ethanol at 78.5 0C and water at 1000C
vapour
100(0C)
Temperature(0C)
78.5(0C)
78.2(0C)
0(0C) 95.6% 100(0C)

% by mass ethanol
Fractional distillation of a non- ideal liquid mixture
Distilling a mixture of ethanol and water containing less than 95.6% by mass of ethanol
Suppose you heat a liquid mixture of composition C1 as shown in the diagram above, it will boil
at a temperature given by the liquid curve and produce a vapour with composition C 2,when the
vapour condenses it will of course still have the same compositionC2.if you reboil that it will

produce a new vapour with composition C3 much richer in the more volatile
component(ethanol).repeating this process of boiling-condensing reboiling sequence you would
eventually end up with a vapour with composition 95.6% by mass ethanol. If you condense that
you obviously get a liquid with composition 95.6% by mass ethanol. If this liquid is reboiled it
will give a vapour of the same composition and condensing it still gives a liquid of the same
composition 95.6% by mass of ethanol.
Distilling a mixture of ethanol less than 95.6% by mass ethanol lets you collect a distillate
containing 95.6% by mass ethanol in the collecting flask and pure water in the boiling flask.
It is impossible to get pure ethanol by distilling any mixture of ethanol and water containing less
than 95.6% by mass of ethanol.
This particular mixture of ethanol and water boils as if it were a pure liquid.it has a constant
boiling point and the composition of liquid and vapour have fixed and exactly the same
composition. It is known as a constant boiling mixture or azeotropic mixture or an azeotrope.
An azeotropic mixture is a liquid mixture which at constant pressure boils at constant

temperature to give a vapour of the same composition.
Azeotropes are not classified as compounds because; their compositions vary with pressure,
they can be separated by physical means and cannot be represented by a general formula.
Distilling a mixture of ethanol and water containing more than 95.6% of ethanol
component(water).repeating this process of boiling-condensing reboiling sequence you would
eventually end up with a vapour with composition 95.6% by mass ethanol. If you condense that
you obviously get a liquid with composition 95.6% by mass ethanol. If this liquid is reboiled it

will give a vapour of the same composition and condensing it still gives a liquid of the same
composition95.6% by mass of ethanol
Distilling a mixture of ethanol more than 95.6% by mass ethanol lets you collect a distillate
containing 95.6% by mass ethanol in the collecting flask and pure ethanol in the boiling flask.
It is possible to get pure ethanol by distilling any mixture of ethanol and water containing more
than 95.6% by mass of ethanol
A maximum boiling point-composition diagram
A diagram of this type is given by non-ideal mixtures that deviate negatively from Raoults law
A large negative deviation from Raoults law produces a vapour pressure curve with a minimum
value at some composition other than that of pure components, this implies that the boiling
point composition curve will have a maximum value higher than the boiling points of either
pure components
In cases of a mixture of nitric acid and water which deviates negatively from Raoults law; this
maximum occurs with 68% by mass of nitric acid in the mixture. The boiling point of this
mixture is 120.50C, compared with the boiling point of pure nitric acid at 86 0C and water at
1000C
Azeotropic point
120.50C
L V
Temperature (0C)
1000C
860C
% by mass nitric acid 68%

Fractional distillation of a non- ideal liquid mixture
Distilling a mixture of nitric acid and water containing less than 68% by mass of nitric acid
component(water).repeating this process of boiling-condensing reboiling sequence you would
eventually end up collecting pure water. As the acid loses water it becomes more concentrated
its concentration gradually increases until it gets to 68% by mass nitric acid.at that point the
vapour produced has exactly the same concentration as the liquid. The distillate will be the
constant boiling mixture or azeotropic mixture this means you can’t produce pure nitric acid
from dilute nitric acid by distilling it.
Distilling a mixture of nitric acid and water containing more than 68% by mass of nitric acid
at a temperature given by the liquid curve and produce a vapour with composition C5,when the
produce a new vapour with composition C5 much richer in the more volatile component(nitric
acid).repeating this process of boiling-condensing reboiling sequence you would eventually end
up with eventually end up collecting pure nitric acid.
Distilling a nitric acid-water mixtures containing more than 68% by mass nitric acid gives you
pure nitric acid as the distillate and the constant boiling mixture as the residue.
Separating azeotropic mixture
Liquid mixture that deviates positively or negatively from Raoults law cannot be separated
completely by fractional distillation however such mixtures can be separated by means like
a)Azeotropic distillation(distillation by use of a third component)

An azeotrope mixture of ethanol and water can be separated by addition of benzene (the third
component to be added must be readily dissolves in the components to form an ideal solution
and must be immiscible with the other component such that the other two are separated using
a separating funnel the third component is separated from the dissolved components by
fractional distillation)
b) Solvent extraction one of the components can be extracted by use of a solvent
c)by chemical method
i)by adding another component that has a strong affinity for one of the component in the
mixture
for example water and ethanol azeotrope, the liquid can be shaken with calcium oxide which
reacts strongly with water to form calcium hydroxide which can be separated by filtration and
the filtrate redistilled to obtain 100% pure ethanol.
ii)by addition of a compound which absorbs one of the components(adsorption)
IMMISCIBLE LIQUIDS
These are liquid which do not dissolve in each other when mixed together; they form two
separate layers depending on their densities for example water and paraffin water and mercury
water and carbon tetrachloride.
Generally liquids which have different chemical structure are completely immiscible. since
mercury is very different chemically from water, the two are completely immiscible.
Vapour pressure of two immiscible liquids
The lack of any sort of interaction (absence of adhesive) between two immiscible liquids means
that each liquid behaves almost independently of the other. If two immiscible liquids are kept
agitated, the vapour pressure above the mixture is the total of the two separate vapour
pressures.

Agitation of the mixture is necessary to enable each liquid to establish its vapour pressure.
Moreover, the vapour pressure above the mixture will be independent of the amount of each
liquid present, so long as there is enough to give a saturated vapour
For example octane and water are immiscible, at 250C the vapour pressure of octane and
water are approximately 3.0kpa and 2.3kpa respectively the vapour pressure above the
agitated mixture of them will be nearly 5.3kpa
Boiling point of the immiscible mixture
When the mixture ie of octane and water is heated the vapour pressure of both liquids will
increase as shown in the figure below. the vapour pressure above the mixture is the sum of the
individual vapour pressure. When the total vapour pressure equals the atmospheric pressure
the mixture will boil. However this happens at a temperature lower than the boiling point of
either component in the mixture
Variation of the vapour pressures of water, organic and the mixture of the two with
temperature
Atmospheric pressure
Vapour pressure(kpa)
890C 1000C 125.8

0
C
Temperature(0C)

Distilling immiscible liquids
Steam distillation
Steam distillation is a method used to separate a volatile component, which is immiscible with
water, from other non- volatile impurities at a temperature less than 1000C using steam.
The processes of distillation of immiscible liquids is generally utililised in the laboratory and in
the industry for the purification of those liquids which boil at too high a temperature or which
decompose when heated to their normal boiling points.
It is mainly used in purification of organic substances that are immiscible with water
Principle of steam distillation
When a mixture of two practically immiscible liquids is heated, while being agitated to expose
the surface of each liquid to the vapour phase. Each component contributes its own vapour
pressure at a particular temperature to the total vapour pressure independent of
other.consequently,the vapour pressure of the whole system increases. Boiling begins when
the sum of the vapour pressure of the two immiscible liquids just exceeds the atmospheric
pressure at a temperature lower than the boiling point of either components.
Properties of a substance to be purified by steam distilled
For the substance to be purified by steam distillation, it must;
i) Be immiscible with water so that at a given temperature, each one of them in

the mixture would produce vapour pressure independent of their proportions in
the mixture as a result the mixture would have higher vapour pressure and will
boil at lower temperature than that of the volatile component . The substance
can easily be separated from water when it collects as a distillate using a
separating funnel.
ii) Be more volatile than the impurities so that it exerts a higher vapour pressure
near the boiling point of water so that the mixture boils at a temperature below
1000C and also so that much of it is obtained with the distillate

iii) have a high molecular mass, so that a reasonable mass of the substance is
obtained in the distillate
iv) Not react with water
v) Exert a high vapour pressure. Near the boiling point of water. This enables a
reasonable mass of the substance to be obtained in the distillate
Apparatus for steam distillation
procedure
Steam is passed through the heated mixture containing the components to be purified. The
distillate collected in the receiver consists of water and the organic component (most

volatile).the organic liquid can be isolated by using a separating funnel and drying with a drying
agent or by extraction with a solvent The non- volatile impurity remains in the distillation flask.
THE COMPOSITION OF THE DISTILLATE
From Dalton law the partial pressure, the partial pressure of an individual gas is equal to the
total pressure multiplied by the mole fraction of that gas at constant temperature =
for water, PW =PTOT( ) …………………………………..(i)
for organic, PO =PTOT( ) …………………………………..(ii)
Dividing equation( i)by(ii)
= = =
On rearranging the above equation
The mass of the substance can be expressed in gram or as a percentage.
The above expression can be used to determine mass of the organic compound in the distillate
or the molecular mass of the organic compound isolated
Example one
2-Aminohydroxyl benzene was steam distilled at 96oC at 760mmHg pressure. Calculate the
percentage composition of the distillate.
(The saturated vapour pressure. of water was 654mmHg at 960C. )
solution

Rmm of water ( H2O) = (1 x 2) + (16 x 1) = 18
Rmm of 2-amino hydroxyl benzene
NH2 = (12 x 6) +(1x7) + (14 x 1) + (16 x 1) = 109
OH
OH
= =
Total mass =0.981 + 1=1.981
% of organic substance = = 49.9%
% of water 100-49.9=51.1
Examples two
An organic compound X was steam distilled at 80oC at 760mmHg pressure. if distillate

contained 90% by mass of X. Calculate the relative formula mass of X
(the saturated vapour pressure of water at 800c is 240mmHg)
Solution
Molar mass of X is 74.8g

Example three
The following data was obtained for the steam distillation of Bromo- benzene at pressure of
760 mmHg
Temp (oc) 90 92 94 96 98 100
v.p mmHg Water 526 567 640 658 707 760
Bromo- benzene 98 106 114 123 132 141
i) Plot a suitable graph of vapour pressure against temperature.
ii) Use the graph to calculate the percentage by mass of Bromo- benzene that can be
steam distilled.
iii) state the temperature of steam distillation
iv) Explain how Bromo- benzene can be isolated from the distillate.
Copy the above table and indicate on the column for total
Temp (oc) 90 92 94 96 98 100
v.p mmHg Water 526 567 640 658 707 760
Bromo- benzene 98 106 114 123 132 141
Total 624 673 725 701 839 901

ii) From the graph,
Total v.p = 760
v.p of water= 600
v.p of bromo- benzene = 108
molar mass of Bromo- benzene = C6 H5 Br = 157
Let mass of bromo- benzene in the distillate be = X %
Mass of water in the distillate will be =(100-X)%
1 8 1
1 18
X=

iii)Temp of steam distillation 93 0C
iv)Distillate is separated by using a separating funnel. The bromo- benzene is dried using a
suitable drying agent e.g. anhydrous Calcium chloride
Advantages of using steam distillation.
1. Distillation takes place at lower temperature than the boiling point of the components of the
distillate
2. It enables purification of substances that decompose at a temperature close to their boiling

points
Application of steam distillation
 It is used in purification of organic compound which decomposes near their boiling

points
 It is used in extraction of some natural products for example to extract eucalyptus oil
from eucalyptus, citrus oils from lemons or orange peels and to extract oils used in
perfumes from various plant materials
 It is used in determining relative molar mass of some compounds
exercises

THREE COMPONENT SYSTEMS.
DISTRIBUTION OF A SOLUTE BETWEEN TWO IMMISCIBLE SOLVENTS
If a solute (solid or liquid) is shaken with two immiscible solvents or liquids in both of which it is
soluble at a given temperature, then the solute distributes or partitions itself between the two
solvents until equilibrium is established.
At equilibrium, the ratio of the concentration of the solute in one solvent to the concentration
of solute in the second solvent is always constant.
THE PARTITION LAW
states that “When a solute is taken up with two immiscible liquids in both of which the solute is
soluble, the solute distributes itself between the two liquids in such a way that the ratio of its
concentration in two liquids phases is constant at a given temperature provided the molecular
state of the distributed solute is the same in both phases.”
The constant ratio is known as the partition coefficient or distribution coefficient KD.
THE PARTITION OR DISTRIBUTION COEFFICIENT KD
This is the constant ratio of the concentrations of the solute in one solvent to the
concentration of the same solute in another solvent, when the two solvents are immiscible and
in contact with each other at constant temperature.
Ie if a solute X is shaken between two immiscible liquids A and B in contact with each other at
constant temperature then at equilibrium
= a constant = KD
The value of KD is independent of volume of the solvents used and the mass of the solute
Limitations of partition law
 Temperature must be kept constant
 The solute must be miscible in both solvents

 The solute must not dissociate or associate in either solvent i.e. it should remain
the same molecular state.
 The solute must not react with either solvent.
 The solvents must be immiscible.
 Solutions used must be fairly dilute i.e. the solute should not saturate either
solvent.
DETERMINATION OF KD BETWEEN SOLVENTS
a) Experiment to determine of KD of ammonia between water and trichloromethane
A given volume of a standard solution of ammonia is shaken with a given volume of a mixture
of water and trichloromethane in a given temperature for about 5 minutes. This ensures that
equilibrium is attained.
The mixture is allowed to stand to let the layers separate out. Equal volumes of either layer are
pipette and separately titrated with standard solution of HCl using phenolphthalein indicator.
Ammonia reacts with HCl according to the equation.
NH3 (g) + HCl (aq) NH4Cl
The volume HCl required to reach end point is noted and the concentration of ammonia in
either layer can be calculated. The value of KD is obtained from the expression.
[ ]
KD = [ ] l
Ammonia is much more soluble in water that in trichloromethane and the partition coefficient
of ammonia between the two solvents at a given temperature gives the number of times
ammonia is more soluble in water than trichloromethane.
Experiment to Determine of KD of ethanoic acid between tetra chloromethane and water.

A known volume of tetra chloromethane and a known volume of water are introduced in a
separating funnel.
A known volume of standard solution of ethanoic acid added to the mixture. The funnel is
stoppered and shaken for the equilibrium to be attained at a given temperature, the mixture is
then allowed to stand to let the two layers separate out and equal volumes of either, layer are
pipetted and titrated separately with a standard solution of NaOH using phenolphthalein as
indicator.
Ethanoic acid reacts with sodium hydroxide according to the equation.
CH3COOH(aq) + NaOH(aq) CH3COONa(aq) + H2O(l)
The volume of sodium hydroxide required to reach endpoint for separate layers is noted and
the concentration of ethanoic acid in either layer is the determined from which the partition
coefficient of ethanoic acid can be calculated.
[ ] l ]
KD = [ ]
Ethanoic acid is much more soluble in tetra chloromethane than in water and the K D value
obtained is an indicator of the number of times ethanoic acid is more soluble in the organic
layer than in water.
Determination of KD of iodine between tetra chloromethane and water.
A given mass of iodine is shaken with a given volume of a mixture of tetra chloromethane and
water in a stoppered separating funnel at a given temperature until the equilibrium of iodine
between the two layers is attained.
The mixture is allowed to stand to let the two layers separate out.
Equal volumes of each layer are pipette in separate conical flasks and separately titrated with a
standard sodium thiosulphate using starch indicator.
The volume of standard sodium thiosulphate required to reach endpoint is noted for each layer.

Sodium thiosulphate reacts with iodine according to the equation.
I2(aq) + 2S2O32(-aq) 2I-(aq) + S4O62-(aq)
The concentration of iodine in either layer is then determined from which the partition
coeffient of iodine can be calculated
[ ]
KD= [ ]
Worked questions and answers
1) 100cm3 of an aqueous solution of ammonia was shaken with100cm3 of chloroform at 198k,

when equilibrium was established; 25cm3 samples of each layer were titrated against 0.1M HCl.
If 25cm3 of the aqueous layer required 127.5cm3 of the acid while 25cm3 of the chloroform
layer required 5cm3 of the same acid.
Calculate the value of KD for the distribution of ammonia between chloroform and water.
Solution
Organic layer
1000cm3 of solution contain 0.1mole of HCl
5cm3 of solution contains moles of HCl
moles of HCl reacts with moles of ammonia
25cm3 of solution contain moles of NH3
1000cm3 of solution contain =2.0X 10-2 M
Aqueous layer
1000cm3 of solution contain 0.1 moles of HCl

127.5cm3 of solution contain x 127.5 moles of HCl
x 127.5 moles of HCl reacts with x 127.5 moles of ammonia
1000cm3 of solution contain ==5.1x 10-1M
KD = == =0.04
2) 50cm3 of 1.5M ammonia solution were shaken with 50cm3 of trichloromethane in a

separating funnel. After the layer had settled, 20cm3 of the chloroform layer were pipette and
titrated with 0.05M HCl .If 23cm3 of the acid were required for neutralization,
Calculate the value of KD of ammonia between water and chloroform at that temperature.
SOLUTION
Organic layer
1000cm3 of solution contain 0.05moles of HCl
23.0cm3 of solution contain ( )moles of HCl
( )moles of HCl reacts with( )moles of ammonia
1000cm3of solution contain =0.0575M
Concentration of NH3 remaining in aqueous layer (1.5- 0.0575) =1.4425M
[ ]
KD = [ = = = =25.1
]

3) 50cm3 of an aqueous solution of iodine was shaken with an equal volume of carbon
tetrachloride in a separating funnel at 290k.when equilibrium was established, the two layers
were left to separate out. 25cm3 of each layer were pipetted and titrated separately against a
0.05M sodium thiosulphate solution using starch indicator. The organic layer required 47.50cm 3
while the aqueous layer required 7.5cm3 of the same solutions of sodium thiosulphate.
Calculate the value of KD of iodine between the organic layer and the aqueous layer.
Solution
I2(aq) + 2S2O32- (aq) 2I- (aq) + S4O62-(aq)
Organic layer
1000cm3 of solution contain 0.05moles S2O32-(aq)
47.5cm3 of solution contain( )moles of S2O32-(aq)
2 moles of S2O32-(aq) react with 1 mole of I2
( ) moles of S2O32-(aq)will react with ½ ( ) of I2
25cm3 of solution contain ½ ( ) moles of I2
1000cm3 of solution contain ½ ( )
=0.0475M
Aqueous layer
1000cm3 of the solution contain 0.05 moles of S2O32-(aq)
7.5cm3 of solution contain ( ) moles of S2O32-(aq)
2moles of S2O32-(aq) react with 1 mole of I2 (aq)

( ) Moles of S2O32-(aq) will react with ½ ( ) moles of I2
1000cm3of solution will contain ½ ( ) moles of I2 = 7.5X10-3
[ ]
KD = [ = = 6.3
]
APPLICATION OF DISTRIBUTION LAW
 Solvent extraction
 Investigation of complex ions
 Distinguishing bromides from iodides
 De-silverisation of lead
 Ions exchange
 Partition chromatography
a)THE SOLVENT EXTRACTION

This involves separating one component from a mixture using a solvent in which the
component is more soluble than any of the other components in the mixture.
For example, iodine is more soluble in many organic solvent than water therefore carbon
tetrachloride can be used to extract iodine from aqueous solution
Solvent extraction is a process of separating a compound (mainly organic) from aqueous

solution in which it is slight soluble by adding a suitable organic solvent in which a solute is
more soluble.
Solvent extraction is normally used to remove solutes from their aqueous solutions by shaking
with extracting solvent in which the solute is more soluble at a given temperature.
Each layer is then collected and the solute can be obtained by distilling off the extracting
solvent.

Organic compounds and nonpolar substances are extracted using organic solvents such as
carbon tetra chloride ethoxy ethane benzene etc
Ether is particularly used as an extracting solvent because its very volatile and therefore easily
distilled off.
During solvent extraction, the process can be performed at once using all the available solvent
to extract or in several small portions
Using separate portions is more economical and preferred during solvent extraction since much
amount of the solute is extracted.
Worked example
Calculate the mass of Z that can be extracted from 100cm3 of aqueous solution containing
30g of Z by shaking the aqueous solution with
a)100cm3 of ether
b) Two successive portions of 50cm3 of ether (KD of Z between ether and water is 5)
Solution
KD =
5=
5= =
150-5a=a
a=25g
The mass of Z extracted by 100cm3 of ether is 25g.
c) Using first portion of 50cm3

Let b g be the mass of Z extracted by the first portion of 5o cm3, then mass of Z remaining in
aqueous layer is (30-b)g.
KD =
5=
150-5b=2b
b= = 21.43g
Mass remaining in aqueous layer
= (30-21.43) =8.57g
For the 2nd portion of 50cm3
Let c g be the mass of Z extracted by the second portion of 50cm 3
Mass of Z remaining in the aqueous layer is (8.57-c) g
KD =
⁄
5.0=
⁄
5.0=
7c=42.85
C=6.12g

Total mass extracted using portions
= 21+3+6.12 =27.55g
b)Determination of formula of complex ions
the partition law can be used to determine the number of a ligands bonded to the central
metal cation
for example to determine the value of n in the following complexes
Zn(OH)n 2- , Al(OH)n - ,Cu(NH3)n 2+ , Fe(H2O)n 2+ , Ni(NH3)n 2+
Experiment to determine the formula of the complex formed between copper (ii) ions and
ammonia;
procedure
A known volume of standard excess ammonia is added to standard solution of Cu2+ ions in a
separating funnel .
The mixture is then shaken with a known volume of trichloro methane for some time, and then
allowed to stand at constant temperature for the two layers to separate.
A fixed volume of each layer is pipetted in a separate conical flask and each is titrated against
standard solution of hydrochloric acid using phenolphthalein indicator.
From the volume of acid that reacted with each layer, the concentration of ammonia in each
layer can be determined using the equation.
HCl aq + NH3aq NH4Cl aq
Part of ammonia in aqueous layer reacted with copper (ii) ions to form a deep blue solution
Cu2+(aq) + nNH3(aq) [Cu (NH3)2 ]2+(aq) (deep blue solution)

The remaining part of ammonia the ‘free ammonia’ distributes itself between the aqueous
layer and organic layer
From the known partition coefficient of ammonia between water and trichloromethane, the
concentration of free ammonia in the aqueous layer can be obtained.
[ ]
KD= [ ]
[NH3] free in aqueous layer = KD [NH3] organic
[NH3] (aq) complexed =[NH3]total in aqueous - [NH3](aq)free
[NH3] (aq) complexed = [NH3]total - KD [NH3]organic
By comparing the concentration of Cu2+ and complexed ammonia in the aqueous layer the
[ ]
value n in the complex formed between the Cu2+ and NH3 is obtained as n= [ ]
Worked example
Excess ammonia was shaken with an aqueous solution of 0.025M Cu2+ and trichloromethane in
a stoppered separating funnel. The separating funnel was allowed to stand for the two layers to
separate out. Some ammonia reacted with the Cu2+ in the aqueous layer to form a complex.
At equilibrium the concentrations of ammonia in trichloromethane and the aqueous layers

were 0.025 and 0.725 respectively.
(The partition coefficient KD of ammonia between water and CHCl3 is 25)
Calculate
i)The concentration of free NH3 in the aqueous layer
ii)The concentration of NH3 that formed the complex with Cu2+
iii)The value of n in the complex and write the formula of the complex.
solution

[ ]
KD= [ ]
25= [NH3](aq) free
[NH3](aq) free =0.021 x 2
[ NH3]complexed = [ NH3] (aq) total - [ NH3] (aq) free
=0.725 – 0.625= 0.1
[Cu2+] (aq) : [ NH3 ](aq) fixed
n =4.0
Formula of the complex is [Cu (NH3)4 ]2+
Alternatively the value of n in the formula of the complex [Cu (NH3)n ]2+ can be obtained
graphically.
A known volume of standard solution of copper( ii )ions is put in a separating funnel and excess
of standard solution of ammonia is added to it the solution is then vigorously shaken with
known volume of trichloro methane for some time and left to stand at constant temperature
for the layers to separate out.
The concentration of ammonia in each layer is determined by titrating with standard

hydrochloric acid using phenolphthalein indicator
The above procedure is repeated with different volumes of copper (ii) ions and trichlomethane
and the concentration of ammonia determined for different volumes.
The results are tabulated in the table below
[ ]
[ ]

A graph of concentration of ammonia in 0.1M CuSO4 against concentration of ammonia in
trichloro methane is plotted and a typical example is shown below.
[NH3]in 0.1MCuSO4
[𝑁𝐻 ]𝑖𝑛𝐶𝐻𝐶𝑙
The concentration of fixed ammonia is obtained as the intercept on the y-axis from which the
value of n can be obtained using the ratio,
Cu2+: [NH3] fixed = 1: n
The slope of straight line gives the partition coefficient of ammonia between water and
trichloro methane
Example
The table below shows the results of partition of amino methane ( CH3NH2)
between trichloromethane and 0.1m copper (ii) sulphate solution
[CH3NH2] in 0.1M CuSO4 0.87 1.10 1.33 1.57 1.80
[CH3NH2] in CHCl3 0.02 0.03 0.04 0.05 0.06

Represent the above data graphically and use the graph to determine the number of moles of
amino methane that formed the complex with Cu2+
Worked example
To a solution of 25cm3 of 0.1M CuSO4was added 25cm3 of NH3 and the resultant solution was
shaken with CHCl3 and the mixture allowed to settle. 20cm3 of the chloroform layer needed
10.2cm3 of 0.05m HCl and 10cm3 of the aqueous was titrated with 0.5m HCl and needed
16.5cm3 of the acid to reach and point.
the KD of ammonia between water and trichloromethane at that temperature is 25.
Calculate the value of n in the complex Cu (NH3]n2+
Solution
Organic layer
10.20cm3 of solution contain ( 1 )moles of HCl
NH3(aq) +HCl (aq) NH4Cl (aq)
( 1 )moles of HCl reacted with( 1 )moles of ammonia
20cm3 of solution contains 5.1 X 10-4 moles
1000cm3 of solution contain 1 = 0.0255 Moles
Aqueous layer (this contains complexed and free ammonia)
16.5cm3 of solution contain moles of HCl

NH3(aq) +HCl (aq) NH 4Cl(aq)
moles of HCl reacted with moles of ammonia
1000cm3 of solution contain 0.825
[ ]
But from KD= [ ]
[NH3] (aq) (free) = KD [NH3] organic
= (25 x 0.0255) = 0.6375 M
[NH3] (aq) complexed = [NH3] (aq) total – [NH3] (aq) free
= 0.825 – 0.6375 = 0.1875 M
From the equation leading to the formation of the complex
Cu2+ (aq) +nNH4 Cu (NH3)n2+
1000cm3 of solution contain 0.1 mole of Cu2+
25cm3 of solution contain =2.5 X 10-3moles of Cu2+
50cm3 of solution contain 2.5 X 10-3 moles
1000cm3 of solution contain = 0.05Moles
[Cu2+]: [NH3] complex
1: 4
n=4
Hence formula = Cu (NH3)42+

Determination of the equilibrium constant Kc
Partition can be used to determine the equilibrium constant between a covalent species and an
ionic species in the equilibrium
For example to determine the equilibrium constant Kc for the reaction
I2 (aq) + I-(aq) I3 (aq)
Procedure;
A known volume of aqueous solution of iodine in potassium iodide is shaken with carbon
tetrachloride in a separating funnel and allowed to stand at constant temperature for the two
layers to separate
A fixed volume of each layer is pipetted in separate conical flask and each is titrated against
standard solution of sodium thiosulphate using starch indicator.
From the volume of sodium thiosulphate that reacted with each layer the concentration of
iodine in each layer is determined using the equation
2 S2O32-(aq) +I2(aq) 2I-(aq) + S4O62- (aq)
Part of iodine in aqueous layer react with iodide ions to form a complex tri-iodide ion the
remaining part will distribute itself between the aqueous layer and the organic layer. Only the
covalent iodine molecules I2 will dissolve in the organic solvent
From the known partition coeffient of iodine between the organic and aqueous layer the
concentration of free iodine in the aqueous is determined using the expression
[ ]
KD = [ ]
[ ]
[ ] =

From the concentration of iodine in the aqueous layer which includes the free iodine and
complexed iodine. The concentration of complexed iodine is obtained by subtracting the free
iodine from the total iodine in aqueous
[I3-] = [I2] (aq) total – [I2](aq) free
The concentration of iodide ions is obtained by subtracting, [I3-] from the original iodide ions.
The equilibrium constant is calculated using the expression
[ ]
KC = [ ][ ]
Worked example
A known mass of Iodine is dissolved in water containing 0.16moldm-3 potassium iodide and the
solution is shaken with known volume of tetra chloromethane. The concentration of iodine in
the aqueous layer was found to be 0.08M and that in organic layer 0.1M.
(The partition coefficient for iodine between tetra chloromethane and water is 85.)
Calculate the equilibrium constant for the reaction.
Solution
[ ] =0.1 M
[ ]
= [ ]
[ ]
[ ] = = =1.176X1 moldm-3
[I2- ] (aq) total =0.08M
[ I3-] (aq) =[I2] (aq) total – [I2](aq) free
= 0.08 – 1.176 x 10-3 = 0.0788M
Initial [I-] = 0.16M

[I-] reacted = 0.0788
[I- ] at equilibrium = 0.0812 M
[ ]
KC = [ ][ ]
= = 825.21 mol-1 dm3
d)Distinguishing bromides and iodine
To the test solution add dilute nitric acid followed by bleaching powder then shake with tetra
chloro methane and allow to stand.
Observation: brown or orange colouration in the carbon tetrachloride layer signifies bromide
ion in solution and Purple colouration in carbon tetrachloride layer signifies iodide ions in
solution.
e)Partition chromatography
Chromatography is the process of separating a solution containing many solutes, which are
often present in very small amounts, by placing the solution on the some absorbent medium
and passing yet another solvent across the medium.
Each solute in the original mixture will distribute itself between the solution on the absorbent,
stationary medium and the second moving solvent in a unique way. The result is that some
solute will travel across the absorbent medium faster than others leaving the individual solutes
separated and spread.
solvent
Each component in the original sample can be recognized by measuring the distance it has
travelled compared to the distance the solvent has travelled, this is known as retention factor
Rf. Rf =

Rf value is constant for a particular compound
Types of chromatography
Paper chromatography
The partition is between the stationary phase(water) on the paper and the mobile
phase(solvent)
Column chromatography
A column of an inert material has the sample placed on top and the solvent (the eluent) washes
the various components down the column at different rates
Ion exchange chromatography
The column is packed with an ion exchange resin this is made of beads of polymer that have
charged groups on their surface.in anionic exchange resin the groups are negatively charged
and trap positive ions in cationic exchange resin negatively charged ions will be trapped.
Application of chromatography
Separate compound in dyes
Identification of amino acids
TWO-COMPONENT SYSTEMS
SOLID-LIQUID EQUILIBRIUM
Cooling curves for pure substances
When a molten compound is cooled, its temperature decreases but remains in the same phase until it
begins to freeze then the temperature remains constant as it freezes and solid compound will be in
equilibrium with its liquid. When the whole compound has frozen, the temperature of the solid then
drops to the minimum. The constant temperature is referred to as the melting point.
The melting point is the temperature at which solid and liquid can exist in equilibrium with
each other. Above the melting point, the solid will change completely into liquid. Below the
melting point liquid will change completely into solid.
The diagram below shows the cooling curve of molten lead

A
328 B C
At first the temperature decreases steadily, then it remains constant, before finally decreases
again,
Point A is the freezing point of pure substance
AB represents the cooling curve of the hot liquid
BC is a plateau where crystals of pure solid begins to crystallize out
CD is the cooling curve of the solid
Super cooling is the cooling below the freezing point without formation of crystal
Cooling curve for mixtures
Addition of a solute to a solvent lowers the melting point of the solvent.

The decrease in melting point or freezing point is approximately proportional to the relative
amount of solute added. The cooling curve is obtained by varying the amount of each
component in the mixture and then determine the temperature at which the mixture begins to
freeze at each composition.
At each time the mixture freezes it’s one of the components that act as the solvent that
crystallizes out first until a certain composition when both components freezes out together.
Consider Tin-lead mixture
Addition of little tin to molten lead lowers the melting point of lead. On cooling pure lead
separates out first. The freezing point continues to be lowered as more and more lead
crystallizes out, until a certain composition (62%tin and38%lead) when both tin and lead
crystallizes out

Similarly Addition of little lead to molten tin lowers the melting point of tin. On cooling pure tin
separates out first. The freezing point continues to be lowered as more tin crystallizes out until
a certain composition (62%tin and38%lead) when both tin and lead crystallizes out.
This particular mixture of lead and tin has a cooling curve which looks like exactly that of a pure
compound rather than a mixture, this particular mixture is known as eutectic mixture
Liquid mixture of tin and

lead cooling
Crystals of lead separates Liquid mixture of tin and
Temperature(0C)
Liquid mixture and crystals of lead lead cooling
Temperature(0C)
separating
Eutectic mixture crystallizes Solid eutectic mixture

separating
Solid eutectic plus lead crystals

cooling
Solid eutectic mixture
cooling
Time (min) Time (min)
Cooling curve for a mixture of 25% tin and 75% lead Cooling curve for a mixture of 62% tin and 38% lead
by mass by mass
Eutectic mixture is defined as a liquid mixture which at constant pressure solidifies at constant
temperature to give a heterogeneous solid of the same composition
An eutectic mixture freezes at a fixed temperature (i.e. 1830C for liquid mixture of tin and lead)
called eutectic temperature
Eutectic temperature is defined as the constant temperature at which a liquid mixture solidifies
at constant pressure to give heterogeneous solid of the same composition.
Properties of eutectics
They have sharp melting points like a pure substance
They have a cooling curve like a pure substance
They are not compounds
Eutectic mixtures behaves as compounds but they are not because

a)they can be separated into their components by physical means whereas compounds are
separated by chemical means.
b) Microscopic examination shows the presence of two kinds of crystals ie they are
heterogeneous whereas a pure compound is homogeneous.
c) Their composition and melting points change with pressure whereas those of compound are
independent of pressure changes
d)their properties are simply the sum of the properties of its components whereas the
properties of a compound are completely different from those of the components in it.
Similarity between Eutectic mixture and a compound
I. Both have similar cooling curves
II. Both have sharp melting point
Solid-liquid phase diagrams:
a) tin and lead mixture
Plotting temperature at which freezing starts against the proportion of tin and lead in the
mixture
Temperature(0C)
Temperature(0C)
Melting point of lead
Molten tin and lead
Melting point of tin
Solid lead and molten mixture Solid tin and

molten mixture
Solid lead + solid tin
62%Sn
Percentage by mass of tin
Point W is the eutectic mixture (36% lead and 64% tin) melts at 1830C
XY represents the solubility of tin in molten lead between 1830C and 2320C
YZ represents the solubility of lead in molten tin between 1830C and 3270C
At all points above XYZ the system is entirely liquid
In area XYR solid tin is in equilibrium with molten mixture.
In area YZS solid lead is in equilibrium with molten mixture
Below RYS the system is entirely solid
Cooling a molten mixture of tin and lead containing less than 38% of lead, no visible change
occurs until a point on the curve XY is reached when pure tin begins to solidify, further decrease
in temperature more tin is formed and the composition of solution follows curve XY when point
Y is reached both tin and lead solidifies as eutectic mixture
Cooling a molten mixture of tin and lead containing more than 38% of lead, no visible change
occurs until a point on the curve ZY is reached when pure lead begins to solidify, further
decrease in temperature more lead is formed and the composition of solution follows curve ZY
when point Y is reached both tin and lead solidifies as eutectic mixture
Cooling a molten mixture of tin and lead containing 38% of lead, no separation of solid occurs
at all until the temperature reaches 183oC, then the temperature remains constant while a
eutectic mixture crystallize out.
b) SALT SOLUTION:
solution of sodium nitrate
if a dilute solution of sodium nitrate is cooled below 0 o C, pure ice will form when the freezing
point of the solution is reached. This freezing point will be less than 0o C, because the added
solute lowers the freezing point of water.
As ice is formed, the solution become more concentrated so that its freezing point becomes
lower still, but further cooling will deposit more ice.Eventually, at -17.5oC, the solution
remaining will become saturated, and any further cooling will deposit a mixture of ice and solid
sodium nitrate, the temperature remaining constant at -17.5oC until whole system solidifies.
If a concentrated solution of sodium nitrate is cooled, crystals of pure sodium nitrate will be
deposited until at a temperature of -17.5oC,a mixture of ice and sodium nitrate will a again
crystallize out at constant temperature

Crystallization will occur at lower temperature for more dilute solutions and at higher
temperature for more concentrated solutions
This is summarized in the temperature-composition diagram below

B
Solution of sodium nitrate in water
A
TEMPERATURE (oC)
Saturated solution +
Ice +
solid sodium nitrate
solution
-17.5
E
Solid sodium nitrate and ice
C
% BY MASS OF NaNO3
The line BE describes the solubility curve of sodium nitrate in water.
The line AE describes the way in which the freezing point of water is lowered as more and more
sodium nitrate is added to it. Along this curve equilibrium is established between the liquid
mixture and ice.
Point E is known as the eutectic point; it corresponds to the lowest temperature which must be
reached before the whole system solidifies.
At this point the crystals deposited from solution have the same composition as the solution.
This composition is given by C i.e. 38.6% by mass of sodium nitrate and the mixture of this
composition is known as the eutectic mixture
It is also the only point at which the three phase’s ice, solid sodium nitrate and saturated
solution of sodium nitrate in water are in equilibrium.

Application of eutectic mixtures
1-are used in the formation of alloys eg solder , brass
2-are used in industries where it is desirable to lower the melting point of a substance e.g in
extraction of aluminium from bauxite; cryolite is added to bauxite to lower its melting point.
3-are used in safety appliances as plugs
Examples of mixtures which form eutectics include;
Zinc and cadmium
Bromo- benzene and benzene
Silver chloride and potassium iodide.
Benzene and naphthalene

Qn. The phase diagram for a certain substance is shown below.
a) Label the following on the diagram
(i) The axes.
(ii) The phase present.
(iii) The critical temperature.
(iv) The triple point.
b) Define the terms;
(i) Critical point.
(ii) Triple point.
c) Explain what would happen when the substance in point X changes to point B.
Solution .
b) (i) Critical point is the temperature and pressure beyond which the vapour cannot be
liquefied no matter the applied pressure.
(ii) Triple point is the temperature and pressure where all the three phases co-exist in
equilibrium with each other.
c) When the phase at point X has its pressure reduced with a slight increase in temperature,
no change in phase occurs but there is an increase in volume due to expansion of rhombic

sulphur when the curve EF is reached, rhombic sulphur turns into monoclinic sulphur and
the two remain in equilibrium at the transition temperature.
d) Further decrease in pressure with slight increase in pressure with slight increase in
temperature all the rhombic sulphur turns into monoclinic sulphur. when the pressure of
monoclinic sulphur is reduced , it continues to expand with no change due to an increase in
volume until when curve ED is reached at which point monoclinic sulphur turns into a
vapour and the two remain in equilibrium with the vapour at a given temp and pressure.
Further decrease in pressure with slight increase in temperature all solid monoclinic turns into
sulphur vapour
Question
The sketch below shows the phase-diagram of mixtures of metals X and Y
A
R
TEMPERATURE (0C)
Q
C
% BY MASS OF X
100
a)State how above curve was obtained.

By cooling molten metals X and Y.
b) Identify the regions P, Q, R and S.
i) P Liquid mixture of x and y
ii) Q Solid Y and is liquid mixture of x and y
iii) R Solid x and solid y
iv) S Solid x and liquid mixture of x and y
c) State what the following points represent
B It represents the eutectic point.
A melting point of pure X
C melting point of pure Y
Describe what would happen if a mixture containing 50% by mass of X and Y is cooled from
410oC to 270oC.
Using points L and v as shown on the graph:
The mixture would remain in liquid state during the cooling, until point v on the curve AB where
compound y begins to solidify out. It would continue to solidify along curve VB until point B, the
eutectic point where both compounds x and y solidify out together. Solidification would
continue until all is solid.

Draw a cooling curve to represent the above changes in part( d)
A A
390
C D
290
E
25
Time (minutes)
AB represent cooling of the hot liquid mixture
BC represents cooling of the liquid mixture as Y crystallize out
CD show the constant temperature when both components solidifies
DE shows the cooling curve of the eutectic mixture
Question two
a) Explain what is meant by the term eutectic mixture.
Eutectic mixture is a liquid mixture which at constant pressure solidifies at constant

temperature to give a heterogeneous solid of the same composition.
b) Two components A and B form eutectic mixture of composition 0.75A. The melting points
of pure A, B and eutectic are 320, 260 and 140oc respectively. Using the above information
sketch a fully labeled phase diagram for the mixture A and B.

(b)
Liquid mixture
Melting point
Melting
2600c o
point ( c)
3200C
Solid A + liquid
mixture
E
140
Solid A + Solid B
o
Composition of A in mole fraction
c) Explain what happens if a liquid mixture of 40% B at 400oc cooled to room temperature.
If the mixture at 400oc is cooled, no visible change along xc, at point c freezing of B starts and
solid B remains in equilibrium with the liquid mixture. Further cooling along CE more solid B is
formed leaving the mixture richer in A, At point E, solid B and A solidify out together as an
eutectic and they do so at a constant temperature until when all is converted into a solid
which is left to cool to room temperature.

Question three
The melting point of pure Cadmium and pure bismuth are 321 oc and271oc respectively. The
table below shows the melting point of the various compositions of the two metals.
Percentage of cadmium 21 35 50 65 80 95
Melting point in( oc) 216 190 156 184 242 300
a) Draw a fully labeled phase diagram for the mixture and explain the shape of the graph.
The graph is V-shaped. Pure bismuth has a high freezing point of 271 oc but the freezing point
lowers along AE due to the increase in the amount of cadmium which acts a solute responsible
for lowering the freezing. Pure cadmium has a high freezing point which similarly decreases
along BE due to the increase in the amount of bismuth which acts as a solute. Point E is the
Eutectic mixture which freezes at a constant temperature and cooling beyond the eutectic
mixture both solids solidify out.
b) Using the graph, explain what would happen if a liquid mixture containing 25% Cd at350 oc
was gradually cooled.

No change in state is observed when the mixture is cooled from 350oc until a temp lower than
271oc at point x along curve AE, At this point pure bismuth starts solidifying out and remains in
equilibrium with the liquid mixture. It continues solidifying out as temp is lowered until the
eutectic temp is reached at point E when both Cadmium and bismuth start solidifying out
together as eutectic and they do so at a constant temperature until when all is converted into a
solid.
worked questions and answers
1. At 100.3 KNm-2, the steam distillation of Nitro benzene takes place at 98%. If the vapour
pressure of water at the same temperature is 93.6knm-2, Calculate the Composition of
the distillate as a percentage by mass of 67.16%
2. At 1732mmHg, the steam distillation of compound x takes place at 98oc.
The ratio of the mass of the Compound to the mass of water in the distillate is 0.188. If the
vapour pressure. of water at the same temp is 712mmHg, calculate the relative formula mass of
X.
During steam distillation, the distillate obtained consists of the substance being isolated and
water
separation of miscible liquids which have boiling points that differ greatly from each other for
example
A mixture of 2- nitro phenol and 4-nitrophenol can be separated by steam distillation because
2-nitrophenol and 4- nitro phenol are miscible, but 2-nitrophenol is immiscible with water
while 4-nitrophenol is miscible with water when steam is passed through a heated mixture of
2-nitro phenol and 4-nitro-phenol the mixture will boil at a temperature lower than that of
water such that 4-nitrophenol with a much higher boiling point will remain in the flask and the
distillate will be a mixture of 2-nitrophenol and water the vapour is condensed to give a
distillate which contains 2-nitrophenol

A mixture of phenyl amine (b.p.=1840C) and water (b.p.=1000C),for example will boil at 98oC
under a pressure of 760mmHg
Reason:
Water and phenyl amine are immiscible liquids and each of the liquids exerts its own vapour
pressure independent of the vapour pressure of other liquid at a given temperature. Each liquid
evaporates independently of the other such that the total vapour pressure above the mixture is
equal to atmospheric pressure at a temperature below the boiling point of the pure liquid.
The above principle of immiscible liquids is the basis of steam distillation (distillation under
reduced pressure
SUB-TOPIC3 :COLLIGATIVE PROPERTIES OF SOLUTION

When a non- volatile solute is added to a solvent to form a solution, this solution will exhibit
four properties namely
Vapour pressure lowering of solvent
Freezing point depression of solution
Boiling point elevation of solution
Osmosis and osmotic pressure of solution
These four properties are collectively known as the colligative properties of solution.
A colligative property is a physical property of dilute solution which depends on the number of
nonvolatile solute particles dissolved in a fixed amount of solvent but is independent of their
chemical nature.
The solute present should not undergo any association or dissociation
If there is association of solute particles the number of particles actually added will become
small. And correspondingly the properties mentioned above will be lowered similarly if the
solute particles are dissociated as in case of electrolytes the numbers of particles become larger
than the original number and the value of the colligative property becomes higher.
The solutions are assumed to be very dilute and the solute should not react with the solvent.

The study of these properties has proved very help- ful in the determination of molecular mass
of the dissolved substances which are non-volatile.
LOWERING OF VAPOUR PRESSURE
Vapour pressure of a liquid at a given temperature is the pressure exerted by the vapour when
it is in equilibrium with its liquid.
Whenever some non-volatile solute is added to a liquid solvent vapour pressure of the solvent
is lowered.
This because the molecules of solute on the surface of the solution tend to hinder the escape of
the molecules into the vapour phase leading to a lower vapour pressure.
This can be shown by drawing a graphs of vapour pressure of solvent and solution against
temperature
solvent
solution
temperature
The vapour pressure of the solvent or solution increases with increase in temperature however
the vapour pressure of pure solvent is always greater than that of solvent
Po is the vapour pressure of the pure solvent
P is the vapour pressure of the solution at the same temperature.

Raoults law of vapour pressure
It state that; the relative lowering of vapour pressure of a solvent is equal to the mole fraction
of non-volatile solute dissolved in the solvent
Where n is the number of moles of the solute
N is the number of moles of the solvent.
If the solution is very dilute n is negligibly small compare to N such that n + N ~ N
And the Raoults law in approximate form is =
Note the relative lowering of vapour pressure
i) is independent of temperature
ii) proportional to concentration of solute
iii) Constant if the same numbers of moles of different solutes are dissolved in the same
mass of the same solvent.

Worked examples
Example one
A solution of 100g of a solute in 1000g of water has a vapour pressure of 2.27 x 10-3Nm-2 at
200C if the saturated vapour pressure of water is 2.34 x 10-3 Nm-2 calculate the molecular mass
of a solute.
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Example two
The vapour pressure of benzene is 9970Nm-2 at 200C calculate the vapour pressure of solution if
1.8g of naphthalene ( C10H8) are dissolved in 100g of benzene (C6H6)
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Example three
The vapour pressure of water at 1000C is 94200pa the vapour pressure of 1% solution of
sucrose is 94150pa calculate the molecular mass of a solute.
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ELEVATION OF BOILING POINT
Boiling point of a liquid is the temperature at which the vapour pressure above the liquid is
equal to that of external atmospheric pressure.
Dissolving a non-volatile solute in a solvent increases or elevates the boiling point of a solvent
this is because:
When anon volatile solute is added to the solvent to form a solution the solute particles
introduced in the solvent tend to hinder or prevent the molecules of the solvent from escaping
into the vapour phase hence there will be a few solvent molecules in the vapour exerting a low
vapour pressure on the surface of the solution. .consequently, this solution, has to be heated to
much higher temperature in order for the vapour pressure to be equal to atmospheric pressure
for boiling to occur.
The vapour pressure curve for the solution and the solvent are shown below
Atmospheric pressure

The vapour pressure of solution is less than the vapour pressure of the pure solvent at all
temperatures.
Where T2 is boiling point of solution
T1 is the boiling point of solvent
For dilute solutions, the elevation of boiling point (T2-T1) is proportional to the lowering of
vapour pressure
ΔTα
Δ T =k( ) ………………..(i)
From Raoults law =
Substituting in equation (i)
ΔT =
The vapour pressure of a solvent is constant at particular temperature therefore KP 0 is

constant let it be equal to K1
ΔT=
If one mole of solute is dissolved in 1000g of solvent ie
1 and m=1000g
ΔT= = Kb
= 1000Kb
Δ Tb =
Where w is the mass of solute
M is the mass of solvent

W is the molecular mass of the solute
Kb is the elevation in boiling point constant or ebullioscopic constant
Definition
EBULLIOSCOPIC constant is the elevation in boiling point caused when one mole of a solute is
dissolved in 1000g of the pure solvent.
For example the Kb for water is 0.52Kmol-1Kg-1 which means that when one mole of non-
volatile solute is dissolved in 1000g of water the boiling point is raised by 0.52K
NOTE
The elevation in boiling point is directly proportion to the mass of solute dissolved and inversely
proportional to the molecular mass of the non-volatile solute
EXPERIMENT TO DETERMINE THE RELATIVE MOLECULAR MASS OF A SOLUTE USING THE

BOILING POINT ELEVATION METHOD
Using cottrells apparatus
Procedure
 A know mass of of pure solvent (ag) is put in the tube and heated until it starts to boil.
 The temperature of boiling pure solvent (T0) is recorded.
 A known mass of the solute (bg) is introduced into the solvent through the side arm
 The solution is heated until it starts to boil and the boiling point of solution T 1 is
recorded when temp remains constant.

Let the boiling point constant of the solvent be Kb 0cmol-1kg-1
Elevation of boiling point be ΔTb = ( T1-T0)0C
If ( a)g of solvent is dissolves ( b)g of solute
1000g of solvent will dissolve ( g of a solute
Δ Tb is the elevation in b.p caused by )g of a solute in 1000g of solvent
Kb is the elevation in b.p caused by dissolving( g of a solute in 1000g of solvent
Hence the molar mass of a solute is
Worked examples
Example one
A solution of 5.0g of compound X in 100g of water boiled at 100.420C calculate the relative
molecular mass of X. (Kb for water is 0.520C mol-1Kg-1)
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Example two
The boiling point of ethanol is 780C. Calculate the boiling point of a solution containing 2.7g of
ethanamide CH3CONH2 in 75 g of ethanol (Kb for ethanol is 1.15Kmol-1 Kg -1 )
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Example three
The addition of 2.01g of glucose C6H12O6 to 25g of benzene caused the boiling point elevation of
1.2040C while the boiling point elevation caused by 2.04g of X in 20g of benzene was 2.413 0C
calculate the
i) Kb for benzene (ii) Molecular mass of X
DEPRESSION IN FREEZING POINT
The freezing point of a substance is defined as constant temperature at which the solid solvent
is in equilibrium with the liquid solvent at constant pressure.
Dissolving a non-volatile solute in a solvent lowers the vapour pressure of the pure solvent
leading to a decrease of the freezing point of a solution. This is because
For a solvent to solidify the intermolecular forces should be strong enough to hold solvent
molecules in a fixed position, a non- volatile solute added lowers the freezing point of pure
solvent because the solute molecules weaken the intermolecular forces of attraction between
the solvent molecules therefore much lower temperature is required for freezing to occur.

Variation of vapour pressure of a solvent or solution with temperature
A D H
B E
G F
M
L
C
CURVE BC is the sublimation curve for the solid solvent along which the solid solvent is in
equilibrium with its vapour.
Curve BA is the vapour pressure curve for the liquid solvent along which the liquid solvent is in
equilibrium with its vapour.
Curve GD is the vapour pressure curve of solution A ,Along which the solution is in equilibrium
with its vapour
Curve MH is the vapour pressure curve of solution B, Along which the solution is in equilibrium
with its vapour.
To is the freezing point of the solvent because
T1 is the freezing point of solution A
T2 is the freezing point of solution B

Solution A more dilute than solution B
For dilute solution the depression in freezing point (T0-T1 )is proportional to the lowering of
vapour pressure
ΔT α(
ΔT =k( )
From Raoults law =
ΔT =
The vapour pressure of a solvent is constant at particular temperature therefore KP 0 is

constant let equal to K1
ΔT=
If one mole of solute is dissolved in 1000g of solvent ie
1 and m=1000g
ΔT = = Kf
= 1000Kf
Δ Tf =
Where w is the mass of solute
M is the mass of solvent
W is the molecular mass of the solute
Kf is the depression in freezing point constant or cryoscopic constant
Definition
CRYOSCOPIC constant is the depression in freezing point caused when one mole of a solute is
dissolved in 1000g of the pure solvent.

For example the Kf for water is 1.86Kmol-1Kg-1 which means that when one mole of non-volatile
solute is dissolved in 1000g of water the freezing point is lowered by 1.86K
NOTE
The depression in freezing point is directly proportion to the mass of solute dissolved and
inversely proportional to the molecular mass of the non-volatile solute.
One advantage of freezing point depression over boiling point elevation is that it is not affected
much by pressure changes unlike boiling point elevation method which depends on
atmospheric pressure.
Its unsuitability is due to the polymers having very large relative molecular masses. In dilute
solutions there are fewer particles of the polymer and causes very small depression of freezing
point which are difficult to measure
EXPERIMENT TO DETERMINE THE RELATIVE MOLECULAR MASS OF A SOLUTE
BY DEPRESSION IN FREEZING POINT METHOD.
Apparatus set up
a) Using Beckmann’s method

Procedure
 A known mass of a pure solvent is put in the freezing tube fitted with a stirrer and
Beckmann’s thermometer.
 The freezing tube is then put in the air jacket to prevent rapid cooling of the content
below its freezing point and to ensure uniform cooling.
 The whole assembly is placed in a larger outer vessel which contains the freezing
mixture.
 The solvent is stirrered until when freezing just starts and the freezing temperature of
the pure solvent is recorded at a steady state.
 The freezing tube is then removed and warmed on the Bunsen burner to melt the
crystals.
 Its then re inserted in the air jacket and freezing mixture
 A known mass of the solute under investigation is then introduced through the side arm
stirred completely to form a uniform solution.
 The temperature of solution is noted until when freezing just starts and the freezing
point of solution is recorded at steady state.
Let the mass of solvent be ag
Mass of solute be bg
Freezing Temperature of solvent be T 10C
Freezing temperature of solution be T 20C
Freezing depression (T 1 –T2) 0C
Cryoscopic constant of solvent be Kf0Cmol-1 Kg-1
a g solvent dissolves b g of solute
1000 g of solvent will dissolve g of solute
(T1-T2)0C is the depression caused by g of solute
Kf 0C is the depression caused by g of solute
The molecular mass of solute is g
Alternatively
The depression in freezing point can be determined from the cooling curves of the solvent and
solution.
 In this case a known mass of the solvent is placed in the tube and is then placed in the
freezing mixture.
 The solvent is then stirred continuously and its temperature recorded after a known
interval of time until solidification occurs


Its then removed and melted and a known mass of the solute introduced in the solvent
stirred to dissolve the placed back in the freezing mixture.
 The temperature of solution is recorded for the same interval of time as for the solvent
until solidification occurs
Graphs of temperature against time are plotted
The graphs have the shapes below
Vopour
pressure
Temperature
b)by Rasts method
this method is based on the use of melted camphor as the solvent
Experiment to determine the molecular mass of naphthalene using camphor as the solvent
Procedure
 A known mass of pure camphor is put in a boiling tube and a thermometer inserted.
 The boiling tube and its contents are transferred into a beaker containing water and the
water heated on the burner.
 Camphor is continuously stirred as boiling occurs until when all the crystals have melted.
 The flame is removed and camphor is allowed to cool in the water bath.
 The freezing temperature of pure camphor is noted when crystals begin to form.

 The flame is put back to melt the crystals and a known mass of naphthalene is
introduced into the boiling tube and stirred to form a solution, the heating is continued
until the whole mixture is a solution.
 The flame is removed and the solution is allowed to cool in a water bath the
temperature at which the crystals begin to form is noted.
Let the mass of camphor be ag
Mass of naphthalene be bg
Freezing Temperature of camphor be T 10C
Freezing temperature of solution be T 20C

Freezing depression (T 1 –T2) 0C
Cryoscopic constant of solvent be K f0Cmol-1 Kg-1

a g camphor dissolves b g of naphthalene
1000 g of camphor will dissolve g of naphthalene
(T1-T2)0C is the depression caused by g of naphthalene
Kf 0C is the depression caused by g of naphthalene
The molecular mass of is naphthalene g
Worked examples
Example one
0.55g of nitro benzene in 22 g of ethanoic acid depressed the freezing point of ethanoic acid by
0.780C. Calculate the relative formula mass of nitrobenzene
(Kf of ethanoic acid is 3.9Kmol-1 Kg-1)
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Example two
Calculate the freezing point of a solution of 28 g of ethanamide( CH3CONH2) in 500 g of water

given that the cryoscopic constant of 100 g of wateris18.60C
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Example three
1.5 g of compound Q of molecular mass 90 g on dissolving in 30 g of water produced a freezing

point of -1.04 calculate the freezing point constant of water
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OSMOSIS AND OSMOTIC PRESSURE
OSMOSIS is the movement of solvent molecules move from a region where they are highly
concentrated to region where their concentration is low across a semi-permeable membrane.
OSMOTIC PRESSURE of solution is the pressure that must be applied to the solution side to
balance the tendency of the solvent molecules to flow from the solvent side to the solution
side across a semi-permeable membrane.
Note the semi-permeable membrane allows only solvent molecules and not the solute
molecules to pass through it freely. This membrane can be obtained from pig’s bladder,
cellulose membrane or a film of cupric ferrocynanide.

EXPERIMENT TO DEMONSTRATE OSMOTIC PRESSURE
If a cell is set up so that the liquid level is initially the same in both compartment you will soon
notice that the liquid rises in the left compartment and falls in the right side
Indicating that solvent molecules from the right compartment are migrating through the
Semi-permeable membrane into the left compartment. This migration of solvent molecules is
known as osmosis
When the level in the tube no longer rises, the pressure of this column of solution is equal to
the osmotic pressure.
EXPERIMENT TO MEASURE OSMOTIC PRESSURE
(Berkeley and Hartley method)

Procedure
A known mass of solute is dissolved in a known volume of a solvent and the solution formed is
placed in the outer tube connected to the pressure gauge.
A pure solvent is placed in the inner tube containing a porous pot to act as a semi-permeable
membrane.
Osmosis is allowed to take place at a given temperature ToC and the level of the solvent in the
capillary tube is seen to drop below mark x
Pressure is applied on the solution to force back the solvent molecules to the solvent side.
The pressure is adjusted until the liquid level in the capillary tube is maintained at point x
This is the osmotic pressure of the solution at ToC which can be registered by the pressure
gauge.
FACTORS THAT AFFECTS OSMOTIC PRESSURE
1. Concentration
Osmotic pressure increases with concentration this is because more solvent molecules will
move into the solution to reduce on the concentration gradient a higher osmotic pressure is
required to force back the many solvent molecules.
2 temperatures
Osmotic pressure increase with increase in temperature this because more solvent molecules will
gain more kinetic energy and move faster and can easily diffuse through the semi-permeable
LAWS OF OSMOTIC PRESSURE
These two laws apply to un ionized solutes only
First law
It states that at a given temperature, the osmotic pressure of a dilute solution is directly
proportional to concentration C.
= Constant

Since concentration is inversely proportional to the volume of the of the solution, this law
can also be written as
…………………………..(i)
This is analogous to Boyle’s law for gases, expressed in the form PV =constant
Second law
Its state that at a given concentration, the osmotic pressure of a dilute solution, is directly
proportional to its absolute temperature
= (Constant) ………………………………..(ii)
This is analogous to Charles law for gases =K (if V is constant)
OSMOTIC PRESSURE AND THE IDEAL GAS EQUATION
Combining law 1 and law 2
For n moles of the solute T
Vant Hoff said that if the pressure is in standard units ,solutions are dilute , temperature is
absolute and volume is in dm3 the value of K is universal for all solutions and is approximately
equal to the ideal gas constant R
Therefore the expression T can be written as
This expression is similar to the expression PV= nRT for ideal gases
Vant Hoff came up with a gaseous theory which state that the pressure a dilute solution exerts
is the same pressure it would have exerted if it were a gas under identical conditions of
temperature and pressure.
For
n=

Where C is concentration in g per dm3
R = 8.314jmol-1 K-1 or 0.082dm3atmK-1 mol-1 is gas constant
LIMITATION OF OSMOTIC PRESSURE LAWS
i) The solution must be very dilute

ii) The solute must particles must not react with solvent molecules
iii) The solute particles must not dissociate or associate in solvent
iv) The solute must be non-volatile
SIGNIFICANCE OF OSMOSIS
1 it is used in determining of relative molecular mass of polymers
2. it is used in process of excretion e.g filtration in kidney gaseous exchange in lungs
3. up take of water by plants through the roots
WORKED EXAMPLES
Example one
20g of cane sugar in 2dm3 of solution at 283K produced an osmotic pressure of 0.68
atmospheres. Calculate the relative molecular mass of cane sugar
Using =
= M = 341
OR 2dm3 of solution contains 20 g of a solute
22.4dm3 of solution will contain of a solute
At 283K the osmotic pressure of solution was 0.68 atm
At 273K the osmotic pressure of solution will be atm

atm is caused by g of cane sugar
1 atm is caused by g of cane sugar = 341g
OR
Direct application of the gas equation(SI units must be used in this case)
The volume of solution containing 1 mole is given by V = = = 3.414x10-2M 3
2x10-3 M 3 Contains 20g of cane sugar
3.414x10-2 M 3 will contain = 341g
EXAMPLE TWO
The osmotic pressure of solution containing 1.24% of a polymer is 3.1x 10 -3 atmosphere, at

250C.. Determine the relative molecular mass of the polymer.(R=0.0821dm3atm K-1mol-1)
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note
Advantage of osmotic pressure over the elevation in boiling point and depression in freezing
point method is that it can be used to determine molecular mass of polymers
Since molecular mass of polymers are very high they produce very small depression in freezing
point or elevation in boiling point which cannot be red on the thermometer.
Exercises

TOPIC6: CHEMICAL EQUILIBRIUM:
CHEMICAL EQUILIBRIUM:
Deals with the study of reversible reactions
Reversible reactions
A reversible reaction is one in which the reaction can go either forwards or backwards depending on the
conditions of the reaction.
Reversible reactions make products which themselves react to give back the products. These reactions
never stop because once some products is made it can regenerate the reactants from which it came.
In equation the symbol (double headed arrow) is used to show that the reaction is reversible.
For example; When steam is passed over heated iron, hydrogen and tri- iron tetra oxide are produced
3Fe(s) + 4H2O(g) Fe3O4(s) + 4H2 (g)
During this reaction, the concentration of reactants decrease and this is the forward reaction.
Also when dry hydrogen gas is passed over heated tri- iron tetra oxide, the reverse reaction takes place
and tri- iron tetra oxide is reduced to iron
Fe3O4(s) + 4H2 (g) 3Fe(s) + 4H2O(g)
If the four chemicals are sealed in the container, the iron would react with steam to form hydrogen and
tri- iron tetra oxide, but at the same time hydrogen would be reacting with tri- iron tetra oxide to
produce iron and steam. The forward and reverse reaction together form a reversible reaction
3Fe(s) + 4H2O (g) Fe3O4(s) + 4H2 (g)
Both forward and reverse reaction proceeds indefinitely in a reversible reaction up to the point when
there is no further observable change. At this point the rate of the forward reaction equals the rate of
the backward reaction and thus a reaction never goes to completion, and the reaction is said to have
reached a chemical equilibrium a state at which the concentration of reactants and products get fixed
and the reaction appears to come to standstill thus chemical equilibrium is dynamic in nature.
A dynamic equilibrium occurs when
 You have a reversible reaction in a closed system(A closed system is one in which no substances
are either added to the system or lost from it)
 The concentration of all reactants and products remain constant although the reaction is still
continuing.
 The rate of the forward reaction is equal to the rate of the back ward reaction

In chemical reaction ,Chemical equilibrium is the state in which both reactants and products are
present in concentrations which have no further tendency to change with time.
Equilibria are of two types:
Homogeneous equilibria
Is a type of equilibrium in which all the products and reactants are in the same physical state e.g
N2 (g) + 3H2(g) 2NH3(g)
2SO2(g) + O2(g) 2SO3(g)
CH3COOCH2CH3(aq) + H2O(l) CH3COOH(aq) + CH3CH2OH(aq)
Heterogeneous equilibria
Is the type of equilibrium in which all the products and reactants have different physical states e.g
CaCO3(s) CaO + CO2(g)
3Fe(s) + 4H2O (g) Fe3O4(s) + 4H2 (g)
The equilibrium law
Equilibrium law states that; for any system at equilibrium, there is a numerical relationship between the
concentration of products, raised to the power of their stoichiometric numbers and the concentration of
the reactants raised to the powers of their stoichiometric numbers. The numerical relationship is called
the equilibrium constant.
The equilibrium constant
This is the ratio of the product of the concentration of products to the product of the concentration of
reactants when each is raised to an appropriate power according to the balanced chemical equation at a
given temperature. The equilibrium constant is normally expressed as Kc or Kp
The equilibrium constant Kc for homogeneous systems
Homogeneous system is a type of equilibrium in which all the products and reactants are in the same
physical state. Here Kc is the equilibrium constant when concentration is measured in moldm-3
Consider a homogeneous equation below
aA+Bb cC+ Dd
[ ] [ ]
Kc = [ ] [ ]

[ ] [ ]
i)Kc is only equal to [ ] [ ]
when the system is at equilibrium
ii) the square brackets [ ] means concentration in moldm-3 of whatever is inside them.
iii)it’s the product of products raised to their Stoichiometric numbers divided by products of reactants
raised to their Stoichiometric number
The table below contains the expressions for Kc for some common equilibrium reactions
reactions Equilibrium constant Kc units

PCl5(g) PCl3(g) + Cl2(g) [ ][ ] Moldm-3
[ ]
H2(g) + I2(g) 2HI(g) [ ] No units
[ ][ ]
2SO2(g) + O2(g) 2SO3(g) ][ Moldm-3
[ ] [ ]
N2(g) + 3H2(g) 2NH3(g) [ ] Mol-2dm6
[ ][ ]
CH3CH2OH(aq) + CH3COOH(aq) CH3COOCH2CH3(aq)H2O(l) [ ] [ ] No units
[ ] [ ]
Cu2+(aq) + 4Cl-(aq) CuCl42-(aq) [ ] Mol-3dm9

[ ][ ]
The equilibrium constant kc for heterogeneous systems
Many systems contain more than one phase and so are heterogeneous. If one of the phases is pure solid
or liquid, then although the amount of the solid or liquid may change, its concentration will not. In these
cases it is usual to write an equilibrium law expression that does not contain the pure solid or liquid
phase’s concentration (which is actually included in the modified equilibrium constant).
reactions Equilibrium constant Kc units

CaCO3(s) CaO(s) + CO2(g) KC =[ ] Moldm-3
Fe2O3(s) +3CO(g) 2Fe(s) + 3CO2(g) [ ] No units

Kc = [ ]

Equilibrium constant KP for gaseous systems
Kp is the equilibrium constant when concentration is expressed in terms of partial pressure and this
applies only in gaseous systems. For gases it is usually more convenient to measure the pressure of the
gas than its concentration.
The partial pressure of a gas A, PA in a mixture is the pressure that a gas would exert if it alone filled the
container.
It is calculated from the expression partial pressure =mole fraction x total pressure
Where mole fraction =
Total pressure P is equal to the sum of the partial pressure of each gas in the mixture.
Consider a homogeneous gaseous equation below
aA+Bb cC+ Dd
Kp =
Where is the partial pressure of gas A
Where is the partial pressure of gas B
Where is the partial pressure of gas C
Where is the partial pressure of gas D
The table below contains expression for Kp for some common equilibrium reactions
Reactions Expression of equilibrium units

constant Kp
PCl5(g) PCl3(g) + Cl2(g) ( )( )
( )
H2(g) + I2(g) 2HI(g)
( ) ( )
2SO2(g) + O2(g) 2SO3(g) ( )
( ) ( )
N2(g) + 3H2(g) 2NH3(g) ( )
( ) ( )
CaCO3(s) CaO(s) + CO2(g) ( )
C(s) + H2O(g) CO(g) + H2(g)

3Fe(s) + 4H2O (g) Fe3O4(s) + 4H2
(g)
Experimental determination of equilibrium constant Kc
a)experiment to determine the equilibrium constant Kc for the reaction between ethanol and ethanoic
acid to form ethylethanoate
Procedure
 A known amount of ethanoic acid, a moles is mixed with a known amount of ethanol, b moles
 The mixture is heated under reflux in a thermostatically controlled bath at say 600C for several
hours in order to achieve equilibrium.
 The mixture is rapidly cooled by placing it in large bath of cold water containing ice.
 The amount of ethanoic acid remaining can then be determined by titrating with standard
solution of sodium hydroxide using phenolphthalein indicator.
 The concentration of other substances in the equilibrium mixture need not be experimentally
determined since they can be deduced from the stoichiometry of the reaction.
Let the x be the moles of ethanoic acid remaining at equilibrium
Vdm3 be the Volume of the container
CH3CH2OH(aq CH3COOH(aq) CH3COOCH2CH3(aq) H2O

Moles at start b a 0 0
change -(a-x) -(a-x) +(a-x) +(a-x)
Moles at equilibrium b-(a-x)=(b-a+x) a-(a-x) =x (a-x) (a-x)
Concentration at
equilibrium (moldm-3)
CH3CH2OH(aq) + CH3COOH(aq) CH3COOCH2CH3(aq) + H2O(l)
From the equation
[ ][ ] ( )( )
Kc = [ ][ ]
= =
( )( )

b) Experiment to Determine the equilibrium constant Kc for the reaction between iodine and
hydrogen to form hydrogen iodide.
Procedure
 A known amount of hydrogen, a mole is mixed with a known amount of iodine b moles in a bulb
of known volume V dm3.
 The mixture is heated under reflux in a thermostatically controlled bath at say 4500C for several
hours in order to achieve equilibrium.
 The bulb is rapidly cooled to room temperature and broken under potassium iodide solution to
dissolve the iodine.
 The aqueous potassium iodide solution containing the dissolved iodine is titrated against
standard sodium thiosulphate solution using starch indicator
 The concentration of iodine can be calculated from the equation
I2(aq) + 2S2O32- (aq) 2I-(aq) + S4O62- (aq)
Treatment of results:
Moles of iodine at equilibrium = x
Moles of iodine at equilibrium = b-x
H2(g) I2(g) 2HI(g)

Moles at start a b 0
change -(b-x) -(b-x) +2(b-x)
Moles at equilibrium a-(b-x)=(a-b+x) b-(b-x)=x 2(b-x)
Equilibrium concentration
-3
in moldm
From the equation H2(g) + I2(g) 2HI(g)
[ ] ( )
Kc = [ ][ ]
= =
( )( )

Calculations involving equilibrium constant
Example one
A mixture containing 0.25moles of nitrogen and 0.40moles of hydrogen was allowed to reach
equilibrium at a temperature T0C in a vessel of volume 0.5dm3.At equilibrium; it was found that 0.075
moles of ammonia had been produced. Calculate the value of the equilibrium constant Kc
N2(g) + 3H2(g) 2NH3(g)
N2(g) 3H2(g) 2NH3(g)

Moles at start 0.25 0.400 0.0
change - =-0.0375 - x0.075= -0.1125 +0.075
Moles at equilibrium 0.25-0.0375=0.2125 0.400-0.1125=0.2875 0.075
Concentration in moldm3 =0.425 =0.575 =0.1500
[ ]
Kc =[ ][ ]
= = 0.278 mol-2 dm6
Example two
3.4 moles of sulphur trioxide were decomposed at 600C in 5.0dm3 container in the reaction
2SO3(g) 2SO2(g) + O2(g) when equilibrium was established the amount
Of sulphur dioxide formed was 0.060moles.calculate the equilibrium constant at 600C.
2SO3(g) 2SO2(g) O2(g)

Moles at start 3.4 0 0
change -0.06 +0.06 + = +0.03
Moles at equilibrium 3.4-0.06 =3.34 0.06 0.03
Concentration in moldm3 = 0.668 =0.012 = 0.006
[ ] [ ]
Kc = [ ]
= = 1.936 X 1 moldm-3

Example three
In an experiment 10g of methane CH4 and 54g of water H2O were heated in a container of volume
4.0dm3.at equilibrium 2.0moles of hydrogen,H2 had formed. Calculate the value of Kc from the equation
of reaction. CH4(g) + 2H2O(g) CO2(g) + 4H2(g)
CH4(g) 2H2O(g) CO2(g) 4H2(g)

Moles at start =0.625 =3.0 0 0
change - x2.00 =-0.50 - x2.00= -1.00 + x2.00= +0.5 +2.00
Moles at 0.625-0.50=0.125 3.0-1.00= 2.00 0.5 2.00
equilibrium
Concentration in =0.03125 =0.5 =0.125 =0.5
moldm3
[ ] [ ]
Kc=[ ][ ]
= = 1.0 mol2dm-6
Example four
When 1.0moles of carbon dioxide was heated with excess carbon to a temperature of 700C in a vessel
of volume 20dm3,95% of carbon dioxide reacted to form carbon monoxide. Calculate Kc for the reaction
C(s) + CO2 (g) 2CO (g)
CO2 (g) 2CO (g)

Initial moles 1.0 0
change -0.95 +0.95x2 = 1.9
Moles at equilibrium 1.0-0.95=0.05 1.9
Concentration at equilibrium in =0.0025 =0.095
moldm3
[ ]
Kc= [ ]
= = 3.6moldm-3
Note C(s) does not appear in the Kc expression because it it a solid.

Example five
0.080 molesPCl5 was placed in a vessel and heated to 1750C when equilibrium had been reached. It was
found that the total pressure was 2.0 atmospheres and that 40% of PCl5 had dissociated. Calculate Kp for
the reaction. PCl5(g) PCl3(g) + Cl2(g)
PCl5(g) PCl3(g) Cl2(g) total

Initial moles 0.080 0 0
change - x0.08=-0.032 +0.032 +0.032
Moles at 0.08-0.032=0.048 0.032 0.032 0.112
equilibrium
Mole fraction =0.429 =0.286 =0.286
Partial pressure in 0.429x2=0.857 0.286x2=0.571 0.286x2=0.571
atmospheres
( )( )
KP = = =0.38 atm
( )
Example six
Nitrosylbromide decomposes according to the following equation.
2NOBr (g) 2NO(g) + Br2(g)
In closed vessel at 250C, it is 24% dissociated resulting in a total pressure of 4.0 atm calculate the value
of Kp
(Assume that there was 1.0moles of Nitrosylbromide.)
2NOBr(g) 2NO(g) Br2(g) total

Initial moles 1.0 0 0
change +0.24 1
x1.0 =-0.24 + xo.24=0.12
Moles at equilibrium 1.0-0.24 =0.76 0.24 0.12 1.12
Mole fraction 1
=0.679 =0.214 =0.107
11 11 11
Partial pressure 0.679x4=2.72 0.214x4=0.856 0.107x4=0.428
( )
Kp= = =0.0424 atm

Example seven
Thionyl chloride decomposes according to the equation SO2Cl2(g) SO2(g) + Cl2(g)
At a pressure of 1.0atm and temperature of 1000C a sample of SO2Cl2 in the gas phase was found to
contain 34% of chlorine calculate the value of Kp
Let a be the moles of chlorine at equilibrium
SO2Cl2(g) SO2(g) Cl2(g) total

Moles at start 1.00 0 0
change -a +a +a
Moles at equilibrium 1-a a a 1+a
Mole fraction 1
=0.32 =0.34 =0.34
1 1 1
Partial pressure 0.32x1=0.32 0.34x 1=0.34 0.34x1=0.34
34% of chlorine means = ,a=0.515
( )( )
Kp = = = 0.36 atm
( )
Exercises
RELATIONSHIP BETWEEN KP AND KC
KP and KC for a given reaction are not same numerically. It is possible to obtain a relationship between
these two constants at any temperature provided the gases in the reaction obey the ideal gas laws
Consider the reactions
a)N2O4(g) 2NO2(g)
( )
KP =
( )
But PV=nRT where V is the volume occupied by n moles of a gas at temperature T
P= RT but is equal to the molar concentration C therefore P= CRT,substituting this value of P
=[ ]
=[ ]
[ ]
KP = [ ]
[ ]
KC = [ ]

KP = KCRT This implies that KP>KC
b)H2(g) + I2(g) 2HI(g)
=[ ]
=[ ]
=[ ]
[ ] [ ]
KP = [ ] [ ]
=[ ][ ]
=KC
KP =KC
c ) N2(g) + 3H2(g) 2NH3(g)
=[ ]
=[ ]
=[ ]
[ ] [ ]
KP = [ ] [ ]
= [ ][ ]
KP =KC
Generally for any reaction KP =KC
Where Δn= total number of moles of product – total number of moles of reactant
Example
Calculate the value of equilibrium constant Kp for the reaction
2SO3(g) 2SO2(g) + O2(g)
Given that Kc at 600C is 1.936x10-6 moldm-3
Factors affecting equilibrium reactions include;
i)concentration
ii)Temperature
iii)Pressure of gaseous equilibrium
iv)Catalyst
v)Presence of an inert gas (argon or helium)

A change in the conditions of the above factors may affect the following
a) Position of equilibrium
Position of equilibrium: this refers to proportion of products to reactants at equilibrium.

Consider a general equation
aA+bB cC + dD
If the conversion of A and B into C and D is small or slow then the equilibrium position is said to shift
from right to left and if the conversion of A and B is large or fast the equilibrium position is said to shift
from left and right.
The equilibrium position of the system may be altered by the following changes
i)Changing Concentration of products and reactants.
ii)Changing the equilibrium Temperature
iii)Changing Pressure of gaseous equilibrium
iv)Adding an inert gas.
The likely effect on the position of equilibrium can be predicted by le’chatelier’s principle;
The principle states that: When a system is in equilibrium and one of the factors holding the system in
equilibrium is altered, the system will adjust itself in order to nullify the effect of change.
b)Rate of attainment of equilibrium
This refers to how fast equilibrium concentrations are attained
the rate of attainment of equilibrium may be altered by
i)Changing Concentration of products and reactants.
ii)Changing the equilibrium Temperature
iii)Changing Pressure of gaseous equilibrium
c)The equilibrium constant
This refers to the ratio of concentration of products raised to appropriate powers to products of
concentration of reactants raised to appropriate powers
This is affected by changes in temperature only

1)Effect of concentration on
a) the position of equilibrium
For a system at equilibrium, when the concentration of the reactants is increased, the reaction will
proceed in the direction that will reduce the concentration of the reactants.
Consider the equation aA+bB cC + dD
When the concentration of A is increased the equilibrium position shifts to the right more A or B react
to produce C and D similarly when the concentration of C or D is increased the equilibrium position
shifts from left to right ie more C or D react to produce A and B.
b)on the rate of attainment of equilibrium
increase in concentration increases the number of particles and hence the number of collision which
increases the rate of reaction.
c) on the equilibrium constant (KC or KP)
A change in the concentration of one of the substance in the equilibrium mixture will not alter the value
of equilibrium constant, but it will alter the value of the quotient. Therefore the reaction will no longer
be at equilibrium. It will react until the value of the quotient once again equals KC or KP
For example
Sodium chromate reacts with dilute acids to produce sodium dichromate according to the equation.
2CrO42- (aq) + 2H+(aq) Cr2O72- (aq) + H2O(l)
State what is observed and explain your observation when
i)dilute sulphuric acid is added to the equilibrium mixture
ii) dilute is added to the equilibrium mixture
iii) water is added to the equilibrium mixture
2)effect of temperature on
The effect of temperature on the equilibrium position depends on whether the forward reaction is
exothermic or endothermic.
For exothermic reactions increase in temperature favours the backward reaction ie the position of
equilibrium shifts in the direction which absorbs heat from right to left
2HI(g) H2(g) + I2(g) ΔH=+ve

For endothermic reactions increase in temperature favours the forward reaction ie the position of
equilibrium shifts in the direction which absorbs heat from left to right
2SO2 (g) + O2(g) 2SO3(g) ΔH=-ve
b)on the rate of attainment of equilibrium
Increase in temperature leads to an increase in the rate of attainment of equilibrium because of the
increase in the frequency of collision of the reacting particles. However, a decrease in temperature
lowers the rate of attainment of equilibrium.
c)On the equilibrium constant
This is the only factor that alters the value of equilibrium constant
If a reaction is exothermic left to right, an increase in temperature will lower the value of equilibrium
constant. This means that the position of equilibrium will shift to the left (the endothermic direction).
If a reaction is endothermic left to right, an increase in temperature will increase the value of
equilibrium constant. This means that the position of equilibrium will shift to the right (the exothermic
direction).
3) Effect of pressure on reactions
Pressure has generally little or no effect on equilibrium reactions involving solids and liquids.
a) on the position of equilibrium
The effect of pressure on a reversible reaction depends on whether a reaction occurs with volume
change ( change in number of molecules)
for a gaseous reaction that proceeded with an increase in volume or number of molecules such as
PCl5(g) PCl3(g) + Cl2(g)
Increase in pressure favours the backward reaction ie when pressure increases the equilibrium position
shifts to the left.
For a gaseous reactions that proceeds with a decrease in volume or number of molecules such as
N2(g) + 3H2(g) 2NH3(g)
Increase in pressure shifts the equilibrium position to the right ie as pressure increases nitrogen and
hydrogen molecules collide more often to produce more ammonia.
For a gaseous reactions that proceeds with no change in volume or number of molecules such as
2HI(g) H2(g) + I2(g)
Change in pressure does not affect the equilibrium position.

b) On the rate of attainment of equilibrium. if there is more gas molecules on one side than the other,
the value of the quotient will be altered by a change
Increase in pressure increases the rate of attainment of equilibrium because of decrease in volume the
particle will be closer and collide more often.
c) On the equilibrium constant.
A change in pressure does not change equilibrium constant
4)Effect of a catalyst on reactions
a)On the rate of attainment of equilibrium
This neither alters the value of K nor the position of equilibrium. It speeds up the forward and reverse
reactions equally by providing a new route for the reaction, of lower activation energy.
Thus it causes equilibrium to be reached more quickly.
5)Effect of adding an inert gas or noble gas on
the effect adding an inert gas to a system in equilibrium depends on the type of reaction.
i)for reaction which proceed with no change in volume for example
2HI(g) H2(g) + I2(g)
Addition of inert gas will simply increase the total pressure of the system without changing the partial
pressure of reactants and products, hence no effect on the position of equilibrium since they are not
affected by pressure changes.
ii)For reactions which proceed with change in volume for example
N2(g) + 3H2(g) 2NH3(g)
PCl5(g) PCl3(g) + Cl2(g)
addition of an inert gas is at constant volume,
The various equilibrium concentration terms involved are not changed. Since the concentration of an
inert gas is not involved in the equilibrium expressions. Therefore the equilibrium remains unchanged.
Addition of inert gas is at constant pressure,
Introduction of an inert gas causes an increase in volume leading to a dilution or reduction in the partial
pressure of the system therefore the system will adjust itself to the direction that leads to the increase
in the number of molecules in order to maintain the partial pressure constant

APPLICATION OF LE CHATELIERS PRINCIPLE
This principle is widely applied in the manufacturing industry to choose conditions necessary to give a
high yield of a given product at a reasonable rate
The principle is used in;
a) Manufacture of ammonia by Haber process
b) Manufacture of sulphuric acid by contact process.
Manufacture of ammonia (Haber process)
Ammonia is synthesized from nitrogen obtained from the atmosphere by fractional distillation of liquid
air and hydrogen obtained from natural gas according to the equation
N2(g) + 3H2(g) 2NH3(g) ΔH=-92.4kjmol-1
Because this reaction, left to right is exothermic and the number of gas molecules decrease the yield
and kinetic are affected. The following conditions are found to be the most economical for the high yield
of ammonia
 Low temperature of about 4000C since the forward reaction is exothermic, high temperature
reduces the yield of ammonia
 High pressure of about 200atmospheres because the reaction proceeds with a decrease in
volume
 iron catalyst to speed up the rate of attainment of equilibrium. Because at low temperature the
reaction rate would be very slow and hence the reaction would take long to attain equilibrium
and the process become economically unviable,
 Constantly removing ammonia as soon as it had been produced
 Increasing the concentration of either hydrogen or nitrogen but excess nitrogen is preferred
since its cheaply obtained from atmosphere
Uses of ammonia
 Manufacture of fertilizers eg ammonium sulphate
 Manufacture of explosives
 Manufacture of nitric acid ammonia solution is used in laundry
 Liquid ammonia is used in refrigeration
Manufacture of nitric acid
The process involves the following stages
i) catalytic oxidation of ammonia to nitrogen monoxide.

The catalyst used is platinum at about 7000C and a pressure of 9 atmospheres
4NH3(g) +5O2(g) 4NO(g) + 6H2O(l) ΔH=-ve
ii)oxidation of nitrogen monoxide to nitrogen dioxide.
2NO(g) + O2(g) 2NO2(g) ΔH=-ve
iii)nitrogen dioxide obtained is reacted with water to form nitric acid.
2NO2(g) + H2O(l) + O2(g) 2 HNO3(aq)
In presence of oxygen the nitrous acid formed is oxidised to nitric acid
4NO2 (g) + 2H2O(l) + O2(g) 4HNO3(aq)
Uses of nitric acid
 Manufacture of fertilizers especially ammonium nitrate
 Manufacture of explosives eg trinitrotoluene (TNT)
 Manufacture of dyes
Manufacture of sulphuric acid (contact process)
Three stages are involved
i) Formation of sulphur dioxide
Sulphur dioxide can be obtained by burning sulphur in air or roasting metallic sulphides in air
S(s) + O2(g) SO2(g)
4FeS(s) + 7O2(g) 2Fe2O3(s) + 4SO2(g)
The sulphur dioxide formed is purified and dried to remove any impurities like arsenic (iii) oxide that
would otherwise poison the catalyst as sulphur dioxide reacts in air to form sulphur trioxide
ii) Conversion of sulphur dioxide to sulphur trioxide.
Sulphur dioxide and excess oxygen are passed over finely divided vanadium (v) oxide at a temperature
of 400-5000C and a pressure of less than 10 atmospheres.
2SO2 (g) + O2(g) 2SO3(g) ΔH=-98kjmol-1
iii) Conversion of sulphur trioxide to sulphuric acid
Concentrated sulphuric acid is fast used to absorb sulphur trioxide to form oleum

H2SO4(l) + SO3(g) H2S2O7(l)
Oleum is then converted into ordinary sulphuric acid by adding a calculated amount of water.
H2S2O7(l) + H2O(l) 2 H2SO4(l)
The amount of sulphuric acid produced depends on the amount of sulphur trioxide formed from the
reaction.
2SO2 (g) + O2(g) 2SO3(g) ΔH=-ve
A high yield of sulphur trioxide is favored by
 Use of low temperature since the forward reaction is exothermic

 Use of high pressure of about 150-250atmospheres since the forward reaction occurs with a
decrease in volume.
 Vanadium (v) oxide catalyst to speed up the rate of attainment of equilibrium. Because at low
temperature the reaction rate would be very slow and hence the reaction would take long to
attain equilibrium and the process become economically unviable,
 Constantly removing sulphur trioxide as soon as it had been produced
 Use of excess oxygen since it is cheaply obtained from air.
Uses of sulphuric acid
i) Manufacture of fertilizers e.g calcium dihydrogen phosphate
ii) Manufacture of pigments,detergents,plastics fibres,dyes etc
worked examples
example one
Sodium chromate reacts with dilute acids to produce sodium dichromate according to the equation.
2CrO42- (aq) + 2H+(aq) Cr2O72- (aq) + H2O(l)
State what is observed and explain your observation when
i)dilute sulphuric acid is added to the equilibrium mixture
ii) dilute is added to the equilibrium mixture
iii) water is added to the equilibrium mixture

CHAPTER SEVEN; IONIC EQUILIBRIA
OBJECTIVE; by the end of this topic, the learner should be able to describe the behavior of acids, bases
and salts in aqueous solutions.
The equilibrium established between the unionized molecules of the electrolyte and the ions produced
by the electrolyte in the solution is called ionic equilibrium.
Terms used in ionic equilibria

Electrolyte: is a chemical substance which can conduct electricity in aqueous state or in molten state
There two types of electrolytes, strong electrolyte and weak electrolyte.
Strong electrolyte: This is the electrolyte which dissociate almost completely into its constituent ions in
aqueous solution.
Weak electrolyte: This is the electrolyte which dissociate to lesser extent into its constituent ions in
aqueous solution.
Dissociation; is a physical process in which ions of an ionic compound are separated by dissolving the
compound in water e.g NaCl(s) + aq Na+(aq) + Cl-(aq)
Ionization is a reaction between a covalent compound and water to form ions eg
NH3(aq) + H2O(l) NH4+(aq) + ̅ (aq)
Degree of dissociation or ionization α; It is a fraction of the total number of molecules which ionise ( or
dissociate) into constituent ions. Or is a fraction of each mole of an electrolyte that exist as free ions
For strong electrolytes α=1 for weak electrolyte α<1 values of degree of dissociation depends upon the
following facts: nature of solvent, concentration and temperature.
Acid-Base theory
Acids and bases were first defined in several ways depending upon easily recognizable chemical and
physical properties e.g taste, change in colour of litmus etc.
According to Arrhenius theory (1887);
An acid is defined as a substance which when dissolved in water dissociates to form hydrogen ions (H+)
or hydroxonium ions (H3O+).
A base is defined as a substance which when dissolved in water dissociate to form hydroxyl ions ( ̅ H)
Arrhenius theory fails to explain the acidic and basic behavior in non-aqueous solution.

According to Bronsted-Lowry theory(1923)
An acid is a chemical substance that can donate a proton (H+) to some other substance.
A base is a chemical substance that can accept a proton from other substance.
Thus an acid is a proton donor where as a base is a proton acceptor
It applies to both aqueous and non-aqueous systems and bases which do not contain the hydroxyl
group.
All neutralization reactions may be regarded as equilibria involving proton transfer. For example the
reaction between ammonia and hydrochloric acid in aqueous solution can be described by the reaction.
NH3(aq) + H3O+(aq) NH4+(aq) + H2O (l)
In the forward reaction, the base NH3 accepts a proton from the acid H3O+.in the reverse reaction, the
base H2O accepts a proton from the acidNH4+.
The acid NH4+ and the base NH3 are conjugate acid-base pair because they are related by transfer of a
proton. Similarly, the acid H3O+ and the base H2O are conjugate acid-base pair.
The conjugate acid is the species that results when a base accepts a proton,e.g. the ammonium ion
NH4+(aq) is the conjugate acid of the base ammonia NH3(aq)
The conjugate base is the species that results when an acid donates a proton,e.g. water H2O(l) is the
conjugate base of the oxonium ion H3O+.
Thus the equilibrium mixture consists of two acids and two bases and this must always be the case.
Short comings of Bronsted definition
-For an acid to behave as a proton donor, a base must be present to accept a protons from it.this is why
a solution of hydrogen chloride in water is acidic because water act as a base to accept a proton but a
solution of the same gas in benzene is not acidic this because there are no molecules present that can
accept a protons.
-For a base to behave as a proton acceptor, an acid must be present to donate protons to it
-some substances, which are considered to be acidic such as SO3 or BCl3 are excluded due to lack of
hydrogen.
According to Lewis theory
An acid is a chemical substance which can accept a lone pair of electrons from another substance
A base is a chemical substance which can donate a lone pair of electrons so as to form a covalent bond
with another substance

The definition applies to aqueous, non-aqueous species and species with or without protons.
In this system, an acid does not exchange atoms with a base, but combines with it. for example consider
the reaction between hydrochloric acid and sodium hydroxide:
HCl (aq) + NaOH(aq) NaCl (aq)+ H2O(l)
The definition regards the acid to be the H+ itself and the base to be OH- ion, which has un shared
electron pair. The donation of electron pair from OH- to the H+ ions results in formation of a covalent
bond between H+ and OH- thus producing water molecule H2O
H+ + : O:H H O—H
Lewis acid
Lewis acid
- Also The reaction between
i) Boron trifluoride,BF3 and ammonia, NH3 F:B + :N:H F:B:N:H

Lewis acid Lewis base
ii) Copper (ii) ions and water Cu2+ + 4H2O Cu(H2O)42+

iii) Aluminium trichloride and dimethyl ether, AlCl3 + CH3OCH3 Cl: Al:O
Lewis acids and bases take part in many reactions including redox reactions the formation of complex
ions by transition element ions and as electrophiles and nucleophiles in organic chemistry
Strengths of acids and bases
Strong and weak acids
The strength of an acid is a term used to indicate the amount of ionization which occurs when the acid is
dissolved in water.
A strong acid is one that fully ionises in aqueous solution producing its constituent ions.
All mineral acids are strong acids
HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq)
Or
HCl(aq) H+(aq) + Cl-(aq)

A weak acid is one that partially ionises in solution producing very few of its constituent ions
eg organic acids.
C (aq) + H2O(l) C ̅ (aq) + H3O+(aq)
C (aq) C ̅ (aq) + H+(aq)
Strong and weak of bases
The strength of a base is a term used to indicate the amount of ionization which occurs when the base is
dissolved in water.
A strong base is one which is fully ionizes in its aqueous solution producing hydroxyl ions as part of its
constituent ions for example sodium hydroxide
NaOH(aq) Na+(aq) + ̅ )(aq)
A weak base is one which partially ionises in its aqueous solution producing hydroxyl ions as part of its
constituent ions for example ammonia solution
NH3(aq) + H2O(l) NH4+(aq) + ̅ (aq)
Methyl amine
C + C + ̅
comparing the strength of acids and bases under similar conditions
The strength of acids or bases can be compared by
a)degree of ionization or dissociation α
It shows the extent to which an acid is dissociated or ionized
The higher, the degree of ionization or dissociation, the more hydrogen ions concentration or hydroxyl
ion concentration in solution.
The degree of dissociation α is determined by measuring the molar conductivity of solution at a given
concentration ( and the molar conductivity of solution at infinity dilution
α =
b) Dissociation constant or ionization constants of acids and bases
The equilibrium law cannot be applied to the ionization of strong acids and bases in a solvent like water
because they are completely ionized. But ionization equilibria of weak electrolytes can be easily studied
in water as they are feebly dissociated.

i)Weak acids
the equilibrium set up when a weak monobasic acid HA dissolves in water is
HA(aq) + H2O(l) H3O+(aq) + A - (aq)
Applying the equilibrium law
[ ][ ]
Kc = [ ][ ]
the concentration of water is essentially constant because it is so large compared to the concentration
of other species present . Concentration of water can be incorporated into the value of Kc so that it
becomes a new constant KC[ ] which is given the symbol Ka
[ ][ ]
Ka = [ ]
Ka is the acid dissociation constant
Its is temperature dependant and its value depends on the position of equilibrium
The greater the value of , Ka value, the stronger the acid HA
Thus a quantitative comparison of the strengths of acids when dissolved in water can be made.
A weak acid strength can also be measured using its pKa value
pKa = -logKa
the lower the pKa value, the stronger the weak acid
some values of Ka for some common acids are given in table 7.1
Table 7.1 Ka and pKa values for some weak acids
Acid formula Ka PKa

Ethanoic acid CH3COOH 1.7 x 10-5 4.77
Chloro ethanoic acid ClCH2COOH 1.38 x 10-3 2.86
Dichloro ethanoic acid Cl2CHCOOH 5.13 x 10-2 1.29
Benzoic acid C6H5COOH 6.30 x 10-5 4.20
Nitrous acid HNO3 5.00 x 10-4 3.30
The acid strength is in the order C6H5COOH CH3COOH ClCH2COOH Cl2CHCOOH explain
In dichloroethanoic acid, the chlorine atom is more electronegative than the carbon atom it therefore
withdraws electrons from the carbon. i.e the chlorine atoms have a negative inductive effect; they
therefore pull electrons towards themselves increasing the partial positive charge on the hydrogen

atom. This weakens the hydrogen-oxygen bond making the proton more easily lost. The more the
chlorine atoms bonded to the carbon atom adjacent to the carbonyl carbon of the carboxylic acid the
higher the negative inductive effect, so dichloroethanoic acid is stronger acid than chloro ethanoic acid.
In ethanoic acid, the methyl group which is bonded to the carbonyl group has a positive inductive effect.
The methyl group therefore pushes electrons towards the oxygen-hydrogen bond which reduces the
partial positive charge on the hydrogen atom. This strengthens the oxygen hydrogen bond making the
proton less readily to released, so ethanoic acid is weaker acid than chloro ethanoic acid.
In benzoic acid
For weak polypro tic acids(these are acids which contains two or more ionizable hydrogen ions)
They do not ionise in a single step but in successive stages depending on the number of protons
For example
Carbonic acid which is dibasic has two dissociation constants
H2CO3(aq) + H2O(l) H3O+(aq) + HCO-3(aq) k1 =3.0 x 10-7
HCO3- (aq) + H2O(l) H3O+(aq) + CO32-(aq) k2 =6.0 x 10-11
Over all equation
H2CO3 (aq) +2 H2O(l) 2H3O+(aq) + CO32-(aq)
[ ] [ ]
Ka = [ ]
= K1 x K 2
Relationship between degree of dissociation and acid dissociation constant Ka
Consider the ionization of a weak mono basic acid HA whose original concentration is C moldm-3
HA(aq) + H2O(l) H3O+(aq) + A- (aq)
Initially C 0 0
At equilibrium C-Cα Cα Cα
[ ][ ]
Ka = [ ]
= =
For a dilute solution of a weak acid α is much smaller than 1 such that 1-α 1 therefore Ka=Cα2
Worked example

The dissociation constant Ka of 1.0x10-4 moldm-3 ethanoic acid is 1.8x 10-5 moldm-3.find
i)the degree of dissociation
ii)the concentration of hydrogen ions and ethanoic molecules at equilibrium.
Solution
i) CH3COOH(aq) + H2O(l) CH3CO ̅ (aq) +H3O+(aq)
Initially c - -
Conc at equilibrium C-Cα Cα Cα
From Ka=Cα2 α=√ =√ = 0.42
ii)[ ] = Cα = 1.0x10-4 X 0.42 = 4.2x10-5 moldm-3
[ ] = C-Cα =1.00x10-2(1-0.424) =5.76x 10-5moldm-3
Question
A solution containing 0.001moldm-3 of methanoic acid is 1% ionised calculate
i)the acid dissociation constant Ka of the acid
…………………………………………………………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………………………………………………………
ii)determine the hydrogen ion concentration.
…………………………………………………………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………………………………………………………
……………………………………………………………………………………………………………………………………………………………….

Factors which determines the strength of acid
Strength of the bond holding ionizable hydrogen
The acidic strength of group(vii) hydrides is shown below
Halogen acid Bond length Bond strength(Kjmol-1) Acid strength

H F 562 5.62 x10-4
H Cl 431 1.0 x107
H Br 366 1.0 x109
H I 299 1.0 x1011
Acidic strength is in the order HI
Fluorine being the most electronegative and iodine being the least electronegative, the bond strength of
the hydrides is in the order H-F
In solution-F bond is not easily broken and hence, there will be low concentration of hydrogen ions in
solution while H-I bond, being the weakest is easily broken and thus will have a very high concentration
of hydrogen ions in solution. This makes HI the most acidic; hence the acidic strength of the hydrides is
in in the order HI
Nature of solvents
The more basic the solvent the stronger will be the acid in the solvent e g ethanoic acid is a stronger acid
in liquid ammonia than in water because ammonia is more basic than water.
Nature of the substituent group
Electron withdrawing groups attached to carbon atoms increases the acidic strength and electron
releasing groups’ decreases acidity by inductive effect
For example chloro ethanoic acid ClCH2COOH is 80 times stronger than ethanoic acid CH3COOH this is
because the chlorine nucleus in the anion ClCH2CO-2 attracts the electrons in the Cl-C bond, enabling the
charge to be spread through the anion more than it is in CH3CO-2
The reduction of the charge located on the oxygen atoms makes ClCH2CO-2 a weaker proton acceptor t
ii)Weak bases
the equilibrium set up when a weak base acid B dissolves in water is
B(aq) + H2O(l) BH+(aq) + ̅ (aq)
Applying the equilibrium law

[ ][ ̅ ]
Kc = [ ][ ]
the concentration of water is essentially constant because it is so large compared to the concentration
of other species present . Concentration of water can be incorporated into the value of Kc so that it
becomes a new constant KC[ ] which is given the symbol Kb
[ ][ ̅ ]
Kb = [ ]
Where Kb is the dissociation constant
The greater the value of Kb the stronger the weak base
The strength of the weak base can also be determined using its PKb value
PKb = - log Kb
The lower the PKb value the stronger the weak base
some values of Kb for some common bases are given in table 7.2
Table 7.2 Kb and pKb values for some weak bases
base formula Ka PKb

Ammonia NH3 1.81 x 10-5
Methyl amine CH3NH2 4.38 x 10-4
Dimethyl amine (CH3)2NH 5.12 x 10-4
Trimethyl amine (CH3)3N 5.12 x 10-5

Amino benzene C6H5NH2 3.83 x 10-10
The order of increasing basic strength is C6H5NH2 (CH3)3N NH3 C (CH3)2NH explain
Phenyl amine is less basic compared to trimethyl amine this is because the basic strength of an amine
depends on the availability of the lone pairs of electrons on the nitrogen atom.
In phenyl amine, the lone pair of electrons on the nitrogen atom interacts with the delocalized pie
electrons of the benzene ring. The lone pair is therefore not readily available
The hydrogen atoms bonded to nitrogen in ammonia have no effect on the availability of the lone pair of
electrons on nitrogen. They have neither positive nor negative inductive effect
In methyl amine the methyl group has a positive inductive effect releasing bonding electrons to the
nitrogen atom this increases the electron density on the nitrogen atom of methyl amine making the
molecules more basic

Factors which determines the strength of bases
The strength of a base depends on how readily it accepts a proton and this depends on the availability of
lone pairs
Relationship between degree of dissociation and base dissociation constant Kb
Consider the ionization of a weak base B whose original concentration is C moldm-3
B(aq) + H2O(l) BH+(aq) + ̅ (aq)
Initially C 0 0
At equilibrium C-Cα Cα Cα
[ ][ ̅ ]
Kb = [ ]
= =
For a dilute solution of a weak acid α is much smaller than 1 such that 1-α 1 therefore Kb=Cα2
Question
At 250C, 0.01moldm-3 ammonia NH3 is 4.5% ionised
a)write the
i)equation for the ionization of ammonia
…………………………………………………………………………………………………………………………………………………………………
ii)expression for ionization constant Kb for ammonia
………………………………………………………………………………………………………………………………………………………………….
b)calculate the
i) ionization constant Kb for ammonia
…………………………………………………………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………………………………………………………
………………………………………………………………………………………………………………………………………………………………..
ii)concentration of hydroxyl ions at equilibrium
…………………………………………………………………………………………………………………………………………………………………
………………………………………………………………………………………………………………………………………………………………..

IONIZATION OF WATER
Water, no matter how pure it is made, always ionises to a very small extent
H2O(l) + H2O(l) H3O+(aq) + ̅ (aq) or simply
H2O(l) H+(aq) + ̅ (aq)
And this is itself an acid-base equilibrium. Water produces its own conjugate acid and its own conjugate
base at the same time.
Application of the equilibrium law to this leads to the following expression for the equilibrium constant
Kc.
[ ][ ̅ ]
Kc = [ ]
However, since water is dissociated to a very small extent, its concentration in aqueous solution may be
regarded as constant. Including this constant in Kc
Kc[ ] [ ][ ̅ ]
KW =[ ][ ̅ ]
KW is called the ionic product of water and has units of mol2dm-6
Since KW is equilibrium constant it is temperature dependent its numerical value

at 00c is about 1x10-14 mol2dm-6 at 298k its value is 1x10-15 mol2dm-6
and at 1000C is about 5.4 x 10-13 mol2dm-6
This implies that KW increases with increase in temperature because the dissociation of water is
endothermic H2O(l) H+(aq) + ̅ (aq) ΔH=+ve
Increase in temperature increases the concentration of H+ ions and ̅ ions and therefore KW
In water the concentration of H+ ions must be the same as that of ̅ ions thus
[ ] [ ̅ ] = 1x10-7 moldm-3 at 298k
When acids or alkalis are dissolved in water there will be different concentration of H+ ions and ̅ ions
but the product of these two concentrations is always equal to the value of KW at that temperature
If the solution has [ ] [ ̅ ] it is said to be neutral

THE HYDROGEN ION INDEX pH
By definition PH is the negative logarithms to base ten of the concentration of hydrogen ions in moldm-3
i.e PH = -Log[ ] the relationship between the quantities is shown below.
PH 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
[ ]mold 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
Note that PH rises as [ ] falls
Calculating pH of water at 298k
The hydrogen ion concentration pure water, [ ] = 1x10-7 moldm-3 at 298k
pH = -Log(1x10-7) = 7
since pure water is the end product of neutralization of a strong acid and a strong base, a PH of 7 is
regarded as defining a neutral solution at 250C.solution with a PH of less than 7 are therefore acidic and
those with a PH greater than 7 are alkaline, but at 250C.neutral solution in general (i.e at any
temperature) are those where [ ] [ ]
Calculating pH of strong acids
For purpose of calculation, it is assumed that all strong acids are completely ionised hence the hydrogen
ion concentration is obtained directly from the molarity of the acid.
Example 1;
Calculate the PH of 0.1moldm-3 hydrochloric acid solution
The acid ionises completely as
HCl(aq) H+(aq) + Cl-(aq)
0.1 0.1 0.1
[ ] 1moldm-3
PH = -Log(0.1) =1.0
Example 2
Calculate the of 0.01moldm-3 sulphuric acid.
Each mole of sulphuric acid produces 2 moles of hydrogen ions in solution
H2SO4(aq) 2H+(aq) + SO42-(aq)

The concentration of the hydrogen ions is therefore twice the concentration of the acid
[ ] = 2x 0.01= 0.02 moldm-3
PH = - =1.70
Example 3
Calculate the concentration of sulphuric acid whose pH is 2.5
[ ] =1 =
Concentration of the acid is half the concentration of hydrogen ions= ……moldm-3
Calculating pH of strong bases
Strong bases are also assumed to be completely ionised. The hydroxide ion concentration is therefore
easily obtained from the molarity of the base
Example 4
Calculate the PH of a solution of 0.3 moldm-3 sodium hydroxide.
Sodium hydroxide ionises completely as
NaOH(aq) Na+(aq) + ̅ aq)
0.3 0.3 0.3
[ ]=
[̅ ]
= = 3.33X10-14 moldm-3
pH =-Log(3.33X10-14) =13.50
Or from KW =[ ][ ̅ ] = 1x10-14
-log(KW) =-Log([ ][ ̅ ]
14 = -log[ ] +-Log[ ̅ ]
= PH + POH
pH = 14-POH
pOH = -Log(0.3) =0.523
pH = 14-0.523=13.477

Calculating pH of weak acids
Weak acids are slightly ionised in aqueous solution and thus the degree of ionization and the
dissociation constant must be known
Example 5
Calculate the pH of 0.1 moldm-3 ethanoic acid at 298k given that its Ka value is 1.7 x 10-5 moldm-3 at this
temperature
CH3COOH(aq) CH3CO ̅ (aq) + H+(aq)

[ ̅ ][ ]
Ka = [ ]
Assumption; ethanoate ions and hydrogen ions must be produced in equal concentrations such that
[ ̅] [ ]
[ ] [ ]
Ka = [ ]
= =1.7 x 10-5
[ ] =1.3 X10-3 moldm-3
pH = -log (1.3 X10-3) =2.88
Example 6
Calculate the pH of 0.1moldm-3 solution of ethanoic acid for which the acid is 2.5% ionised
Initially c 0 0
At equilibrium c-αc αc αc
[ ]= αc = 1 =0.025moldm-3
pH = -Log(0.025) = 2.6
Example 7
The pH of 0.001M solution of benzoic acid is 3.59 calculate the
i) Dissociation constant of the acid
ii) Degree of dissociation of the acid
solution
C6H5COOH(aq) C6H5CO ̅ (aq) + H+(aq)
pH = -log[ ] =3.59

[ ]=1 =2.57 X 10-4 moldm-3
Assumption[ ̅] [ ]
[ ̅ ][ ] ( )
Ka = [ ]
= =6.6 x 10-5 moldm-3
[ ]= αc =2.57 X 10-4 moldm-3
α= = 0.257
calculating the pH of weak bases
Weak bases are slightly ionised in aqueous solution and thus the degree of ionization and the
dissociation constant must be known.
Example 8
Calculate the pH of 0.01 moldm-3 ammonia solution in which the degree of dissociation is 0.043
NH3(aq) + H2O(l) NH4+(aq) + ̅ (aq)
Initially c c c
At equilibrium c – αc αc αc
[ ̅ ]=αc = 0.043x 0.01 = 4.3 x 10-4 moldm-3
pOH = -log (4.3 x 10-4) =3.37
pH = 14- 3.37 = 10.63
Factors which affect pH of solution
1. concentration of H+ ions the higher the concentration of hydrogen ions the lower the pH
2. Addition of a common ion
Consider addition of sodium ethanoate to ethanoic acid
Sodium ethanoate is a strong electrolyte completely ionizes producing excess ethanoate ions
CH3COONa(aq) CH3CO ̅ (aq) + Na+(aq)
where as ethanoic acid is a weak electrolyte that partially ionizes
Excess ethanoate ions react with H+ ions to form undissociated ethanoic acidic molecules reducing
concentration of H+ ions, shifting the equilibrium to the left increasing pH of solution

BUFFER SOLUTIONS
When an acid is added to a neutral solution, the pH of the solution falls, and when an alkali is added to
such a solution, its pH rise.
Some solutions resist pH changes when small quantities of an acid or alkali are added to them such
solutions are known as buffer solutions.
A buffer solution is a solution that resists pH changes, when a small amount of acid or alkali is added to
it.
There are two types of buffer solutions
Acidic buffer (a buffer solution with pH less than seven)
This is a solution which contains a weak acid and its salt from a strong base. Eg
Ethanoic acid and sodium ethanoate
Benzoic acid and sodium benzoate
Phosphoric acid and sodium phosphate
Basic buffer ( a buffer solution with pH greater than seven)
This is solution which contains a weak base and its salt with a strong acid.eg
Ammonium hydroxide and ammonium chloride
Ammonium hydroxide and ammonium sulphate
Action of acid buffer solution
We will take ethanoic acid and sodium ethanoate as a typical example. The ethanoic acid is a weak acid,
and so it partially ionizes as
CH3COOH (aq) CH3CO ̅ (aq) + H+ (aq)
Sodium ethanoate is ionic salt, and in solution consists of free sodium and ethanoate ions.
CH3COONa (aq) CH3CO ̅ (aq) + Na + (aq)
This mixture therefore contains a relatively high concentration of undissociated acid molecules,
ethanoate ions and a small amount of hydrogen ions formed by the original ionization of ethanoic acid.
When small a amount of acid is added to such a solution, these will nearly all combine with the
ethanoate ions to form ethanoic acid molecules and so the pH will hardly change at all.
CH3CO ̅ (aq) + H+(aq) CH3COOH (aq)

When small amount hydroxyl ions are added to this solution, almost all of these will react with the un-
ionised ethanoic acid to make ethanoate ions and water. So the pH will hardly change at all.
CH3COOH (aq) + ̅ H (aq) CH3CO ̅ (aq) + H2O(l)
In other words, trying to alter the pH of the solution by increasing the concentration of H+ or ̅ largely
fails.
Action of basic buffer solution
We will take ammonia and ammonium chloride as a typical example. The ammonia is a weak base and
so it partially ionises as
NH3(aq) + H2O(l) NH4+(aq) + ̅ H(aq)
Ammonium chloride is an ionic salt, and so its solution consist of free ammonium and chloride ions:
NH4Cl (aq) NH4+ (aq) + Cl- (aq)
The mixture therefore contains a relatively high concentration of undissociated ammonia molecules and
ammonium ions and enough hydroxyl ions to make the solution alkaline.
When a small amount of hydrogen ions are added to such a solution, these will nearly all combine with
the ammonia present to make more ammonium ions, and so the pH hardly changes at all.
NH3(aq) + H+(aq) NH4+(aq)
When a small amount of hydroxyl ions are added to such a solution, most of them react with ammonia
ions to produce ammonia molecules and water.
NH4 +(aq + ̅ (aq) NH3(aq) + H2O(l)
Once again, trying to change the pH by increasing the concentration of H+ or ̅ largely fails.
CALCULATING pH OF A BUFFER SOLUTION
The pH of a buffer solution can be calculated using the dissociation constant of the weak acid or base
For an acidic buffer containing ethanoic acid and its salt with a strong base, the dissociation of ethanoic
acid is considered.
CH3COOH (aq) CH3CO ̅ (aq) + H + (aq)
[ ][ ]
Ka = [ ]
Assumption: ethanoate ions are produced by the dissociation of the salt, sodium ethanoate. Therefore
[ ]=[ ]

[ ]
[ ]=
[ ]
[ ]
pH = -Log[ ] = -Log
[ ]
For an alkaline buffer containing ammonia and ammonium chloride, the ionization of ammonia
molecules is consider.
NH3(aq) + H2O(l) NH4+(aq) + OH(aq)
[ ][ ̅ ]
Kb = [ ]
Assumption: ammonium ions are produced by the dissociation of the salt, ammonium chloride.
Therefore [ ]=[ ]
[ ]
[ ̅ ]=
[ ]
[ ]
pOH = -Log[ ̅ ] = -Log( [ ]
)
pH = 14- pOH
Worked examples
Example one
A buffer solution was made by dissolving 18.5g propanoic acid,CH3CH2COOH, and 12.0g of sodium
propanoate,CH3CH2COONa,in water and then making the volume up to 250cm3.
(pKa for propanoic acid=4.87,C=12,O=16,Na=23,H=1)
a)calculate the pH of a buffer solution
b)what will be the effect of adding
i)1.00cm3 of 10moldm-3 hydrochloric acid.
ii)1.00cm3 of10moldm-3 sodium hydroxide solution to 1000cm3 of the buffer solution.
Solution
Molar mass of CH3CH2COOH =12x3+6x1+16x2=74g
Moles of CH3CH2COOH in 250cm3 =
Moles of CH3CH2COOH in 1000cm3 = =1.00moldm-3
Molar mass of CH3CH2COONa =12x3+5x1+16x2+23x1=96g

Moles of CH3CH2COONa in 250cm3 =
Moles of CH3CH2COONa in 1000cm3= =0.50moldm-3
pKa = 4.87
Ka =1.35 x 10-5 moldm3
[ ][ ]
Ka = [ ]
assumption
Because virtually all the propanoate ions CH3CH2COO-,are coming from the sodium propanate,and
almost none from propanoic acid, the propanoate concentration is also equal to 0.50moldm-3 and that
so little of propanoic acid ionizes that its equilibrium concentration is 1.00moldm-3
[ ]
1.35x 10-5 =
[ ] =2.70 X10 -5 moldm-3
pH= 4.57
b i)the buffer solution works by combining the hydrogen ions from the added acid with propanoate ions
from the sodium propanoate, turning them into propanoic acid. This means that the concentration of
the propanoate ions will fall, while that of the propanoic acid will rise.
Number of moles of H+ ions added = =0.010mol
CH3CH2COO- aq + H+ aq CH3CH2COOH aq
New moles of CH3CH2COO- = 0.5-0.01 =0.49
New moles of CH3CH2COOH = 1.00+ 0.01 =1.01
[ ][ ]
Ka = [ ]
[ ]
1.35x 10-5 =
[ ] =2.78X10-5
pH =
the pH falls by

ii)the buffer solution works by reacting the hydroxide ions from the sodium hydroxide with propanoic
acid, producing more propanoate ions. This means that the concentration of the propanoate ions will
rise, while that of the propanoic acid will fall.
Number of moles of -OH ions added = =0.010mol
CH3CH2COOH aq + -OH aq CH3CH2COO- aq + H2O l
New moles of CH3CH2COO- = 0.5+0.01 =0.51
New moles of CH3CH2COOH = 1.00- 0.01 =0.99
[ ][ ]
Ka = [ ]
[ ]
1.35x 10-5 =
[ ] =2.62X10-5
pH =
the pH rise by
Example two
Calculate the pH of a buffer solution made by mixing 50cm3 of 0.300moldm-3 ethanoic acid with 100cm3
of 0.600 moldm-3 sodium ethanoate. (Ka for ethanoic acid = 1.75 x 10-5 moldm-3 )
Total volume 100 +50 =150cm3
Moles of ethanoic acid in the total volume of 150cm3 = = 0.015
Moles of ethanoic acid in 1000cm3 = =0.100moldm-3
Moles of sodium ethanoate in the total volume of 150cm3 = = 0.0600
Moles of sodium ethanoate in 1000cm3 = =0.400moldm-3
[ ̅ ][ ]
Ka = [ ]
[ ]
[ ]= ̅]
[
[ ]
[ ] =
[ ̅]
= = 4.375x10-6 mol
pH = -log(4.375x10-6)

=
Example three
A solution was made by mixing 30cm3 of a 0.1M ethanoic acid and 20cm3 of 0.1M sodium hydroxide
solution. Calculate the PH of the resultant solution
State any assumption made. ( Ka for ethanoic acid = 1.8 x 10-5 moldm-3)
Solution
1000cm3 of ethanoic acid solution contains 0.1 moles
30cm3 of ethanoic acid solution contains = 3 x10-3 moles
1000cm3 of sodium hydroxide solution contains 0.1 moles
20cm3 of sodium hydroxide solution contains = 2 x10-3 moles
CH3COOH(aq) + NaOH(aq) CH3COONa (aq) + H2O(l)
One mole of sodium hydroxide reacts with one mole of ethanoic acid
Therefore moles of ethanoic acid reacting = 2 x10-3 moles
Excess moles of ethanoic acid in solution = 3 x10-3 - 2 x10-3 =1 x10-3 moles
The resultant solution is a buffer containing excess ethanoic acid and the salt sodium ethanoate formed
Total volume of the mixture (30+20) = 50cm3
Concentration of ethanoate ions in the mixture = =0.04moldm-3
Concentration of ethanoic acid in the mixture = =0.02moldm-3
[ ][ ]
Ka = [ ]
[ ]=[ ].
[ ]
[ ]=
[ ]
[ ]
[ ] = = = 9.0 x 1 mol
[ ]
pH = -Log(9.0 x 1 ) = 5.0

Example four
Calculate the mass of sodium ethanoate that should be added to 1dm3 of 0.1 M ethanoic acid at 250 C to
give a solution whose pH is 5.5 State any assumption made
(Ka for ethanoic acid =1.8 x 10 -5 mol dm-3)
[ ][ ]
Ka = [ ]
[ ]=[ ]
[ ]
[ ]=
[ ]
[ ]
[ ] =
[ ]
pH = -Log[ ]
[ ] =1 = 3.16 X 10-6 moldm-3
[ ]
[ ̅] = = = 0.5696 moldm-3
[ ]
Molar mass of CH3COONa= (12x2) +(1x3) +(16x2) +(23x1) =82
0.5696 moles of CH3COONa weighs (0.5696 x 82) = 46.71g
Example five
A buffer solution was made by mixing 0.1 M ammonia solution and 0.025 ammonium chloride in 1.0dm 3
a)Calculate the pH of this solution.
b)calculate the pH of the above solution when
i)10cm3 of 0.1 M NaOH was added
ii)10cm3 of 0.1M HCl was added .(Kb for ammonia = 1.8 x 10-5 moldm-3 )
solution
⌈ ⌉⌈ ̅ ⌉
a)K = [ ]
⌈ ⌉
[ ̅ ]=
[ ]
Assumption: [ ] [ ]

[ ̅ ]= = 7.2 x 10-5 moldm-3
[ ]= = = 1.389 X 1
[̅ ]
pH = -log (1.389 X 1 = 9.857
b) moles of NaOH in 10cm3 = = 1 x 10-3
after the addition of sodium hydroxide concentration of NH3 increases by 0.001 while concentration of
NH4Cl decreases by 0.001 moles.
NH4+(aq) + ̅ (aq) NH3(aq) + H2O(l)
New concentration of NH3 = 0.1 + 0.001 = 0.101moles
New concentration of NH4+ = 0.025 – 0.001 = 0.024 moles
⌈ ⌉⌈ ̅ ⌉
a)Kb = [ ]
⌈ ⌉
[ ̅ ]=
[ ]
Assumption: [ ] [ ]
[ ̅ ]= = 7.515 x 10-5 moldm-3
[ ]= = = 1.320 X 1
[̅ ]
pH = -log (1.320 X 1 = 9.879
ii) b) moles of HCl in 10cm3 = = 1 x 10-3
after the addition of hydrochloric acid concentration of NH4Cl increases by 0.001 while concentration of
NH3 decreases by 0.001 moles.
NH3(aq) + HCl(aq) NH4Cl(aq)
New concentration of NH3 = 0.1 - 0.001 = 0.099moles
New concentration of NH4+ = 0.025 + 0.001 = 0.026 moles
⌈ ⌉⌈ ̅ ⌉
Kb = [ ]
⌈ ⌉
[ ̅ ]=
[ ]

Assumption: [ ] [ ]
[ ̅ ]= = 6.854 x 10-5 moldm-3
[ ]= = = 1.459 X 1
[̅ ]
PH = -log (1.459 X 1 = 9.834
Example six
Calculate the pH of a solution obtained when 25cm3 of 0.02 M HCl are added to 25cm3 of 0.04M
NH4OH.(pKb of ammonia is 4.76 at 250C).
Solution
1000cm3 of hydrochloric acid contains 0.02 moles
25cm3 of hydrochloric acid contains = 1 moles
1000cm3 of ammonia solution contains 0.04 moles
25cm3 of ammonia solution contains =1 1 moles
NH4OH(aq) + HCl(aq) NH4Cl(aq) + H2O(l)
One mole of HCl reacts with one mole of NH4OH
Therefore moles of ammonia reacting = 1
Excess moles of ammonia =1 1 1 1
The buffer formed is composed of excess NH4OH add the salt formed NH4Cl
Total volume of the mixture =(25 +25) = 50cm3
Concentration of ammonium ions in the mixture = =0.01moldm-3
Concentration of ammonia in the mixture = =0.01moldm-3
[ ][ ̅ ]
Kb = [ ]
Kb = 1 = 1.738 x 10-5 moldm-3

[ ]
[̅ ]= = = 1.738X1 moles
[ ]
KW = [ ][ ̅ ]
1X 1 [ ] X1.738 X1
[ ] 5.754 X 1 moldm-3
pH = -log(5.754 X 1 = 9.24
Example seven
In what proportions should ammonia and ammonium chloride be mixed in solution to give a buffer
solution of pH 10.0? pKa for NH4+ is 9.25
Solution
pH=10
[ ] =1.00X 10 -10 moldm-3
pKa =9.25
Ka =5.62 x10-10 moldm-3

[ ][ ]
Ka = =5.62X10-10
[ ]
[ ]
= =
[ ]
The concentration of ammonia to ammonium chloride should be 5.62to 1.0
Application of buffer solutions
 in medicine,injections into blood stream given for medical reasons should be buffered.the pH of
living cells and blood must be maintained at its value of pH7.4 any variation of about 0.5 in this
pH could prove fatal.
 In agriculture,specific plants grow in specific soil ph and therefore the ph of the soil has to be
maintained . Fertilizers applied must be well buffered
 In industial process,for example in fermatation process any change in ph would cause death of
the fermatation organisms fermatation process must be buffered.
 In Preservation of food
 In Preparation of standard solutions of definite pH
 In electroplating processes must be buffered

SALT HYDROLYSIS
SALTS
A salt; is an ionic compound formed when the hydrogen of an acid is partially or totally replaced by a
metal(or ammonium ion)
A salt is an ionic compound formed by the reaction of an acid and a base
Salts are strong electrolyte and are completely dissociated in water.
Types of salts
Normal salts; these are salts obtained by complete neutralization of an acid with a base eg NaCl and
K2SO4.
Acidic salts; these are salts formed by incomplete neutralization of polybasic acids eg NaHCO3 and
Na2SO4.
Basic salts; these are salts formed by incomplete neutralizations polybasic bases e.g Mg(OH)Cl
Double salts; these are salts containing more than one cation or anion and are formed by the
combination of two simple salts eg (NH4)2SO4 FeSO4.6H2O.
Hydrolysis: is a reaction involving the breaking of a bond in a molecule using water. The reaction mainly
occurs between an ion and water molecules and often changes the pH of solution.
There three types of hydrolysis; salt hydrolysis, acid hydrolysis and base hydrolysis
SALT HYDROLYSIS
When an acid reacts with a base in aqueous solution neutralization takes place.
This neutralization is complete only in case of a reaction between strong acid like hydrochloric acid and
a strong base like sodium hydroxide and the final solution will be neutral ie containing equal moles of
hydrogen ions and hydroxide ions.
In all other cases, the final solution will not be neutral and is either acidic or basic
The acidity or basicity of a final solution is due to the tendency of the salt formed by neutralization to
react with water thereby partially reversing the process of neutralization. Therefore
Salt hydrolysis is the partial reversal of neutralization due to reaction of the salt with water to form
either acidic or alkaline solution.
When the solvent is not water the phenomenon is generally referred to as solvolysis

When a salt is dissolved in water, water spontaneously ionizes into hydroxide anions and hydronium
cations. The salt also dissociate into its constituent anions and cations the cation or anion may react
with water
There are four types of salt to consider.
a)salt of strong acid and a weak base
Salts of strong acids and weak bases such as NH4Cl NH4NO3 (NH4)2SO4 C6H5NH3 undergo hydrolysis to
give acidic solution.
Consider for example the hydrolysis of NH4Cl
Ammonium chloride dissociate completely into ions in solution whereas water partially ionises
NH4Cl(aq) NH4+(aq) + Cl-(aq)
H2O (aq ̅ (aq) + (aq)
Chloride ions will not undergo hydrolysis because HCl is a strong acid so there is no formation of HCl
molecules, however the ammonium ions react with hydroxyl ions from water to form feebly ionised
NH4OH molecules and this increases the concentration of hydrogen ions in solution. The removal
of ̅ ions by ammonium ions causes water to ionise further to keep KW constant this lead to the
accumulation of hydrogen ions in solution, the PH of solution falls below 7 and it reacts acidic
Overall equation of hydrolysis NH4+(aq) + H2O (l) NH3(aq) +H3O+(aq)
Further examples include
CH3CH2NH3(aq) + H20(l) CH3CH2NH2(aq) + H30+ (l)
b)Salt of strong base and weak acid
salts of weak acids and strong bases such as sodium ethanoate, sodium carbonate,sodiumcyanide e.t.c.
undergo hydrolysis to give basic solutions.
Consider for example the hydrolysis of sodium ethanoate.
Sodium ethanoate dissociates completely into ions in solution whereas water partially ionises
CH3COONa(aq) CH3CO ̅ (aq) +Na+(aq)
H2O (aq ) (aq) ̅ (aq)
Sodium ions will not undergo hydrolysis because NaOH is a strong base so there is no formation of
NaOH molecules, however the ethanoate ions react with hydrogen ions from water to form feebly
ionised CH3COOH molecules and this increases the concentration of hydroxyl ions in solution. The

removal H+ of ions by ethanoate ions causes water to ionise further to keep KW constant this lead to the
accumulation of hydroxyl ions in solution, the PH of solution increases above 7 and it reacts alkaline
Overall equation of hydrolysis CH3CO ̅ (aq) + H2O (l) CH3COONa(aq) ̅ (aq)
c)a salt of weak acid and weak base
salt of weak acids and weak bases such as ammonium ethanoate undergo hydrolysis to give either acidic
or alkaline or neutral solution depending on
consider for example ammonium ethanoate in aqueous solution the equilibrium
CH3COONH4(aq) CH3CO ̅ (aq) +NH4+(aq)
H2O (aq ) (aq) ̅ (aq)
Since the acid and base are both weak unionized molecules of ethanoic acid and ammonium hydroxide
are formed by utilizing the hydrogen and hydroxyl ions derived from water the removal of these ions
disturbs the equilibrium of water, to restore KW water ionises further. in this particular case the acid and
base are about equally weak so that the concentration of hydrogen ions and hydroxyl ions remains
about equal in solution in spite of hydrolysis ammonium ethanoate is strongly hydrolysed in solution but
the solution remains almost neutral.
Equation of hydrolysis
CH3CO ̅ (aq) +NH4+(aq) + H2O (aq ) CH3COOH(aq) + NH4OH(aq)
In general a salt formed from a weak acid and a weak base will hydrolyse but the acidity or basicity
depends on the equilibrium constants Ka and Kb if Ka value is greater than Kb value the resultant solution
will be acidic or if Ka is less than Kb the resultant solution will be basic or if Ka is equal to Kb the resultant
solution will be neutral.
d)a salt of a strong acid and a strong base
a typical case of this kind is sodium chloride the situation in a solution of this salt is
NaCl(aq) Na+(aq) + Cl-(aq)
H2O(l) ̅ (aq) + H(aq)
The acid and base are both strong so that no formation of molecules, NaOH or HCl, occurs. The ionic
equilibrium of water remains undisturbed, there is no hydrolysis, and the solution remains neutral. The
salt of sodium and potassium hydroxide with any of the three mineral acids show this situation.

e) salts involving ions with a high charge density
Ionic compounds dissociate 100% into ions in solution. These ions become solvated by water molecules
(the water molecules bond to the ions- this is one of the driving forces behind dissolution)
the polar water molecules use the lone pairs on the oxygen of the water to coordinate to the positive
metal ion. The ions are then enclosed by a cage of water molecules usually in an octahedral
arrangement. Ie Al(H2O)63+ Fe(H2O)63+ Cr(H2O)63+
the high charge density of the ions polarizes the water molecules surrounding the ion in solution this
results in weakening of the O-H bonds within water molecules allowing the hydrogen ions to be released
into solution hence the solution is acidic.
Al(H2O)63+ (aq) Al(OH)(H2O)52+ (aq) + H+(aq)
or
Al(H2O)63+ (aq) + H2O(l) Al(OH)(H2O)52+ (aq) + H3O+(aq)
Quantitative treatment of hydrolysis
a)Consider hydrolysis of a salt of weak acid and a strong base e.g sodium ethanoate
CH3CO ̅ (aq) + H2O (l) CH3COOH(aq) ̅ (aq)
Iniatialy C 0 0
At equilibrium C-hC hC hC
Where C is the original concentration
h degree of hydrolysis (fraction of the total salt that under goes hydrolysis when equilibrium has
been established)
Kh is hydrolysis constant(this gives the extent to which the salt under goes hydrolysis)
[ ][ ̅ ]
Kh= [ ̅]
……………………………….(1)
= =
Assuming the concentration of water is virtually constant.
If h is very small compared to 1 then Kh =h2C
Relationship between Kh and KW
Consider the ionization of the conjugate acid CH3COOH formed from hydrolysis of sodium ethanoate

CH3COOH(aq) CH3CO ̅ (aq) +H+(aq)
[ ̅ ][ ]
Ka = [ ]
………………………………(2)
Multiplying expressions (1) and (2)
[ ][ ̅ ] [ ̅ ][ ]
Kh x Ka = [ ̅]
x [ ]
= [ ̅ ][ ]=KW
For a salt of a weak acid Kh =
b)consider the hydrolysis of a salt of weak base and a strong acid eg ammonium chloride
NH4+(aq) + H2O (l) NH3(aq) +H3O+(aq)
Iniatialy C 0 0
At equilibrium C-hC hC hC
[ ][ ]
Kh= ………………………………………………………(4)
[ ]
= =
Assuming the concentration of water is virtually constant.
If h is very small compared to 1 then Kh =h2C
Relationship between Kh and KW
Consider the ionization of the conjugate base NH4OH formed from hydrolysis of ammonium chloride
NH4OH(aq) NH4+(aq) + ̅ (aq)
[ ][ ̅ ]
Kb = [ ]
…………………………………..(4)
Multiplying expressions (3) and (4)
[ ][ ] [ ][ ̅ ]
KhxKb = x =[ ][ ̅ ] =Kw
[ ] [ ]
For a salt of a weak base and a strong acid , Kh =
It can also be shown that if the salt is derived from a weak base and a weak acid its hydrolysis constant
is given by Kh=

ACID- BASE INDICATORS
Theory of acid-base indicators
Indicators are used to detect the equivalence point or end point in titration of solutions of unknown
concentration with a standard solution.
An acid -base indicator is either a weak organic acid or weak organic base which change colour
according to the hydrogen ion concentration of the solution in which it is added.
It is a vital feature of an indicator that there should be a marked difference of colour between the
undissociated molecule and the dissociated form of an indicator.
Consider a weak organic acid indicator represented by HIn
In a solution, the indicator partially ionizes according to the equation
HIn(aq) H+(aq) + In- (aq)
Colour Y colour X
The undissociated form of phenolphthalein indicator is colourless while the dissociated form is pink.
The colour change is used to indicate the end point of the titration.
The equivalence point (the point at which stoichiometrically equivalent amount of acid and base have
been added together) can be determined accurately with an indicator when the end point coincides
with the equivalent point. At the equivalent point of an acid base titration, the pH changes rapidly
through several units of pH
HOW ACID-BASE INDICATOT WORK
i)addition of an acid(H+)
The extra hydrogen ions of the acid will combine with the ionised species In- to form the unionized
molecule HIn. The equilibrium will shift from the right to the left reducing the amount of In- species
while increasing the amount of HIn molecules. The predominant HIn molecule will then show its colour
in solution i.e. the solution becomes colourless for phenolphthalein
H+(aq) + In-(aq) HIn(aq)
Addition of a base ( ̅ )
The hydroxyl ions from the base combines with the hydrogen ions to form water molecules which
reduces the amount of hydrogen ions in the equilibrium therefore more HIn molecules will ionise to
produce more hydrogen ions which shifts the equilibrium from the left to right the amount of HIn
molecules reduces while that of the In- species increases consequently the predominant In- will show its
colour for the case of phenolphthalein it becomes pink.

THE INDICATOR DISSOCIATION CONSTANT; Kin
The strength of an indicator as an acid will depend on the Ka value for the indicator. This is called
indicator dissociation constant Kin
For acid indicator, HIn, this partially ionizes in aqueous solution.
HIn(aq) H+(aq) + In-(aq)
Colour A colour B
[ ][ ]
Kin = [ ]
The indicator will show an intermediate colour when colour A and colour B are present in equal
concentration ie when [HIn]=[In-]
And therefore Kin = [H+]
-log = -log [H+]
pKin= pH
The indicator will show its intermediate colour at a pH value which is determined by the Kin value for the
indicator.
Since indicators have different Kin values, they will change colour at different pH value.
For phenolphthalein Ki = 7x10-10
[ ]=7x10-10
pH =9.15
Phenolphthalein will show its intermediate colour at pH=9.15
The complete colour change from colour A to colour B,or vice, versa requires a change of about 1.5 to
2.0 units of pH. This range is the working range of the indicator.
The working range of an indicator
is the pH range over which an indicator changes colour effectively in a solution.
The pH of the intermediate colour is at the midpoint of this range.

The following table shows the pH range and colours shown by some commonly used indicators.
indicator pH range PKIn Colour in

Acid Alkali
Thymol blue 1.2-2.8 1.5 Red Yellow
Methyl orange 2.9-5.0 3.7 Pink Yellow
Congo orange 3.0-5.0 red yellow
Methyl red 4.8-6.3 5 Pink Yellow
Litmus 5.0-8.0 6.4 Red Blue
Bromothymolblue 6.0-7.6 yellow blue
Phenol red 6.8-8.4 yellow red
Thymolblue 8.0-9.0 yellow blue
phenolphthalein 8.3-10.0 9.15 Colourless Pink
Alizarin yellow 10.1-13.0 yellow orange
note
It will be seen that Thymol blue undergoes two colour change at different pH values this is true for
mixed indicators.
A mixture of carefully selected indicators which gives a gradual change in colour over a wide range of
pH is known as a universal indicator
Choice of indicator in titration
The indicator to be chosen for any titration should be one whose pH at neutral point is almost the same
as the pH of the neutralized mixture at the end point i.e. the pH of the mixture at the end point must fall
within the working range of the indicator to be chosen
The choice of indicators depends on the pH of the end point of the reaction and on the pH range over
which the indicator changes colour.

A suitable choice of indicators for different types of acids and bases is shown in the table below.
Reactants Suitable acid – base Reason

indicator
Strong acid Vs strong Methyl orange When a strong acid H+ is titrated against a strong base, the
base Phenolphthalein salt formed does not undergo hydrolysis the resultant
e.g NaOH and HCl litmus solution is neutral within pH =7.
There is a sharp pH change from
3 – 10 when the acid is in the flask.
The working range of phenolphthalein (8.2 – 10)
methyl orange (3.2 – 4.4)
litmus (5 – 8)
are within this sharp pH change and either can therefore
be used in locating the end point.
Strong acid Vs weak Methyl orange When a strong acid H+ is titrated against a weak base eg
base e.g HCl and NH3 NH3, the product cat ion NH4+ hydrolyses to give an acidic
solution
With pH less than seven
NH4+ + H2O NH3 + H3O+
The is sharp a pH change from approximately 3 to 7
This is within the working range of methyl orange 3.2 – 4.6
hence methyl orange can be used to locate end point.
Weak acid Vs strong Phenolphthalein When a weak acid H+ is titrated against a strong base eg
base eg CH3COOH and indicator NaOH the anion product CH3 COO- hydrolyses to give base
NaOH solution
CH3COO- + H2O CH3COOH + OH-
the resultant solution has a pH above 7.
There is remarkable pH change from approximately 7 – 10.
This is within the working range of phenolphthalein
(8.2 – 10) hence can be used to locate the end point.
Weak acid Vs weak base No indicator An acid base indicator cannot be used to locate the end
point of the titration between a weak acid and a weak
base because there is no sharp pH change at the end point
to cause a colour change.

TITRATION CURVES
These are graphs showing how the pH of acid or base changes as it is neutralized. The curves usually
obtained by placing a glass electrode into the titration flask and recording the pH as the alkali is run in.
Characteristics of titration curves
 At the end point, a small addition of the base or acid produces a sharp change in pH
 The end point corresponds to the vertical or nearly vertical portion.
 The pH of the mixture at the end point lies in the middle part of the vertical length of the curve.
 The strength of acid added to the base is shown by the pH value from where the curve starts on
the vertical axis
 The strength of the base is shown by the height of the vertical part of the curve above 7
the shape of the PH curve depends on the strength of the acid and alkali used.
a) Titration curve for a strong base added to a strong acid

This curve shows what happens when 1.0moldm-3 sodium hydroxide is added to 50cm3 of
1.0moldm-3 hydrochloric acid.
Explanation of the shape of the curve
 initially at A, before the addition of the base, pH of the acid is very low because of the high
concentration of H+ ions produced by the complete ionization of HCl which is a strong acid.
 Along AB,pH gradually rises as the base is added because the acid is still in excess and the
hydrogen ions are being neutralized by the hydroxyl ions from the base.

 At B, a small amount of sodium hydroxide added gives a sharp rise in PH indicating that the end
point has been reached or neutralization is complete
 pH at the endpoint is 7 because the strong salt formed can’t undergo hydrolysis.
 Along CD, Beyond endpoint, the PH rises gradually due to excess sodium hydroxide adde
b)Titration of a strong alkali against a weak acid
This curve shows what happens when 1.0moldm-3sodium hydroxide is added to 50cm3 of 1.0moldm-3
ethanoic acid
 Initially pH of the acid is a bit high because the acid is weak and thus partially ionises in solution
producing few hydrogen ions.
 The pH gradually rises as the base is added because the acid is still in excess which together with
the salt formed constitute a buffer solution that resist change in pH.
 At the end point, a very small amount of sodium hydroxide added gives a sharp rise in pH since
the alkali is strong
 The pH at the end point is greater than 7 because the salt formed undergoes hydrolysis
producing hydroxyl ions that make the solution alkaline.
CH3CO ̅ (aq) + H2O(l) CH3COOH(aq) + ̅ H(aq)

 Beyond the end point, the p H rises gradually due to excess sodium hydroxide added.
c)Titration curve for a weak base added to a strong acid
this curve shows what happens when 1.0moldm-3 ammonia solution is added to 50cm3 of 1.0moldm-3
hydrochloric acid
 Initially, the pH is very low because of the high concentration of H+ ions produced by the
complete ionization of HCl which is a strong acid.
 pH gradually rises as the base is added because the acid is still in excess and the hydrogen ions
are being neutralized by the hydroxyl ions from the base.
 At the end point, a small amount of ammonium hydroxide added gives a sharp rise in pH
 pH at the end point is less than 7 because the salt formed is hydrolyses to form a slightly acidic
solution.
NH4 + + H2O(l) NH3(aq) + H3O+(aq)
 Beyond endpoint, the pH increases gradually due to excess sodium hydroxide added.

d)Titration curve for a weak base added to a weak acid.
This curve shows what happens when 1.0moldm-3 ammonia is added to 50cm3of 1.0 moldm-3 ethanoic
acid.
The above curve does not show a significant change at the end point ie there is no sharp rise in PH at the
end point.
Therefore pH measurements are not suitable for such a titration.
Ammonia solution reacts with ethanoic acid to give ammonium ethanoate.
CH3COOH(aq) + NH3(aq) CH3COONH4(aq)
The salt hydrolyses in water
CH3COO-(aq) + H2O(l) CH3COOH(aq) + O H(aq)
NH4+(aq) + H2O(l) NH3(aq) + H3O+(aq)
The acid and acid formed from hydrolysis have the same strength
ie Ka of CH3COOH=1.8 x10-5 mol dm-3, and Kb for NH3 =1.8 X 10-5 moldm-3
Therefore, the pH of the resultant solution at the end point

Question
25cm3 of a weak acid HX of concentration 0.01moldm-3 was titrated with 0.10moldm-3 sodium hydroxide
solution, and the pH measured at intervals. the results are set out below
Volume of sodium hydroxide(cm3) 5 10 12 20 23 24 25 26 30

pH 4.5 4.8 4.9 5.5 6.5 7.0 9.0 12.0 12.5
a)Plot a graph of pH against volume of the base added
b)Determine the pH at the end point
…………………………………………………………………………………………………………………………………………………………………
c)Explain the shape of the graph
…………………………………………………………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………………………………………………………
…………………………………………………………………………………………………………………………………………………………………
………………………………………………………………………………………………………………………………………………………………..

Two-indicator titrations
Titration of alkali carbonate.
A cold solution of sodium carbonate can be titrated with a strong acid
if methyl orange is the indicator since the indicator is not affected by carbonic acid (pH = 6.3)
The solution appears to be alkaline and the indicator remains yellow as soon as all the carbonate has
reacted and a slight excess of HCl appears pH decreases rapidly covering the change point of methyl
orange which alters its colour to orange (or pink) to give the end point.
Na2CO3 + 2HCl 2NaCl + H2CO3
On the other hand litmus and phenolphthalein indicator are both sensitive to carbonic acid and can
only be used when the solution is kept boiling to decompose off the carbonic acid.
However if phenolphthalein indicator is used without boiling it changes colour from purple to colourless
when sodium carbonate is only half neutralized.
Na2CO3 + HCl NaCl + NaHCO3
But when methyl orange is used as the indicator, complete neutralization of the sodium carbonate takes
place via two stages.
Na2CO3 (aq) + HCl(aq) NaHCO3(aq) + NaCl(aq)
NaHCO3(aq) + HCl(aq) NaCl(aq) + CO2(g) + H2O(l)
Titration of 0.1 M Na2CO3 with 0.1M HCl
50cm3 of0.1M HCl added to 20cm3 of 0.1M Na2CO3
pH
20 40
Volume of hydrochloric acid added ( cm3)


There are two stages to this reaction, which correspond to two equivalence points at 20cm3 and
40cm3
 Initially pH is 11 corresponds to the pH of sodium carbonate solution
CO32- (aq) + 2H2O(l) H2CO3(aq) + ̅ (aq)
 pH decreases slowly as hydrochloric acid is added the H+ ions react with hydroxyl ions to form
water.
 There is a rapid change in pH when small amount of acid are added corresponding to the first
end point which is due to the reaction
Na2CO3 (aq) + HCl(aq) NaHCO3(aq) + NaCl(aq)
 The pH is 8.3 at the first end point so it can be detected by phenolphthalein indicator since its
within its range.
 The pH continues to decrease on addition of the acid.
 There is a rapid change in pH when small amount of acid is added corresponding to the second
endpoint which marks complete neutralization.
NaHCO3(aq) + HCl(aq) NaCl(aq) + CO2(g) + H2O(l)
 The pH is 3.7 at the second endpoint so it can be detected by methyl orange indicator since its
within its range.
 After the end point pH decreases because excess acid added.
APPLICATION
used in the estimating the amount of sodium hydroxide and sodium carbonate in the mixture or sodium
carbonate and sodium hydrogen carbonate in the mixture or sodium hydroxide and sodium hydrogen
carbonate
Such Mixtures are analyzed by titrating the mixture with standard mineral acid using both
phenolphthalein and the methyl orange indicators either by two step method or by a continuous
method

SOLUBILITY AND SOLUBILITY PRODUCTS
When a certain solute is continuously added to a given solvent at constant temperature a point is
reached when the solvent cannot dissolve any more solute. The solution obtained at this point is called a
saturated solution.
A saturated solution is one which cannot dissolve any more solute at a given temperature in presence of
undissolved solute.
The amount of solute in grams or in moles that dissolves in specific amount of solvent at a given
temperature to form a saturated solution is called solubility.
Some solutes do not easily dissolve in water. Such solutes are said to be sparingly soluble.
A sparingly soluble salt or solute is one which dissolves up to a certain extent beyond which it cannot
dissolve at that temperature.
When a sparingly soluble salt such as silver chloride or barium sulphate is added to water and vigorously
shaken, it is found that after some time a little of the salt dissolves in water to give a saturated solution
at this point an equilibrium is established between the undissolved salt and the ions produced. Ie
AgCl(s) + aq Ag+(aq) + Cl-(aq)
BaSO4(s) + aq Ba2+ (aq) + SO42- (aq)
In general for a sparingly soluble salt AxBy dissolved in water
AxBy (s) + aq xAy+ (aq) +yBx- (aq) ………………(i)
Applying the equilibrium law(law of mass action)
[ ] [ ]
K=
[ ]
K[ ]=[ ] [ ]
Since the concentration of solid remains constant at constant temperature we have
[ ] [ ] = a constant (KSP) or
KSP =[ ] [ ] ……………………………………………………(ii)
The constant KSP is the solubility product of the salt AxBy
Solubility product is the product of the molar concentration of the ions of a saturated solution of a
sparingly soluble salt or electrolyte raised to appropriate powers according to the stoichiometry of the
solubility equation.

Note:
 Equation (i) is the solubility equation for the salt AxBy
 Equation (ii) is called the solubility product expression for the salt AxBy
 [ ] [ ] are the ionic concentration in moldm-3 in the saturated solution
 [ ] [ ] is called the ionic product of the salt AxBy
 A solution of AxBy is saturated if the solubility product is equal to the ionic product i.e.
KSP =[ ] [ ]
 A solution of AxBy is unsaturated if the solubility product is greater than ionic product i.e
KSP [ ] [ ]
 A solution of AxBy will be precipitated out of solution if the solubility product is much less than
the ionic product i.e KSP [ ] [ ]
Examples of sparingly soluble salts include Ag2CrO4,PbCl2,Ca(OH)2,Ca3(PO4)2
Write the i) equation of dissolution of each of the salts
ii) Expression for the solubility product of each of the salt.
Experimental determination of solubility products
The following methods are used to experimentally determine solubility products
 Volumetric analysis or titration method
 Precipitation method
 Conductivity measurements
 Ion exchange method

a) Experiment to determine the solubility product of silver oxalate by volumetric method
Procedure;
A saturated solution of silver oxalate is prepared by adding excess of oxalate to water and shaken
strongly for some time and left for a period of time so as to reach equilibrium at a fixed temperature.
A fixed/known volume of the saturated solution is pipetted, acidified with sulphuric acid, warmed and
titrated with standard solution of potassium permanganate to determine the concentration of oxalate
ions according to the equation.
2MnO4-(aq) + 16H+(aq) + 5C2O42- (aq) 2Mn2+(aq) + 8H2O(l) + 10CO2(g)
The results of the titration are used to determine the concentration of oxalate ions
If the concentration of oxalate ions is Xmoldm-3 that of silver ions is 2X moldm-3
From the equation, Ag2C2O4(s) + aq 2Ag+(aq) + C2O42- (aq)
KSP = [ ] [ ]
= =4 mol3 dm-9
b) Experiment to determine the solubility product of calcium iodate
Procedure;
A saturated solution of calcium iodate is prepared by adding excess of iodate to water and shaken
strongly for some time and left for a period of time so as to reach equilibrium at a fixed temperature.
After equilibrium has been established a fixed/known volume of the saturated solution is pipetted into a
conical flask containing excess potassium iodide and dilute sulphuric acid
The acidified iodate reacts with iodide ion according to the equation
IO3-(aq) + 5I-(aq) + 6H+(aq) 3I2(aq) + 3H2O(l)
The iodine liberated is titrated with standard solution of sodium thiosulphate using starch indicator.
I2(aq) + 2S2O32- (aq) 2I-(aq) + S4O62- (aq)
The titration is repeated and the average volume of sodium thiosulphate calculated
Knowing the volume of sodium thiosulphate that reacted and using the equations above the
concentration of iodate ions in the saturated solution can be calculated
If the concentration of iodate ion is 2xmoldm-3 from the solubility equation that of calcium will be
xmoldm-3
Ca(IO3)2(s) + (aq) Ag+(aq) + 2IO3-(aq)

KSP =[ ][ ]
= mol3dm-9
Precautions
 Pipette after equilibrium has been established
 Pipette only saturated solution
 Maintain a constant temperature
c) Determining of solubility product of calcium iodate by conductivity measurement
Procedure;
 to a known volume of distilled water in a clean beaker excess calcium iodate is added and the
mixture vigorously shaken to reach equilibrium and allowed to stand at constant temperature
 the mixture is filtered and the conductivity of the filtrate is measured using a conductivity
meter
 the molar conductivities of calcium and iodate ions are obtained
 the concentration of calcium iodate in a saturated solution

x=
 From the solubility equation
Ca(IO3)2(s) + (aq) Ca2+(aq) + 2IO3-(aq)
KSP =[ ][ ]
= mol3dm-9
Calculations involving solubility and solubility product
Example one
The solubility of silver oxalate Ag2C2O4, at 250C is 3.344x10-2 gdm-3 . calculate the solubility product at
this temperature . (Ag=108,C=12,O=16)
Solution
Molar mass of Ag2C2O4 =(108x2) +(12x2)+ (16x4) =304g
Solubility of Ag2C2O4 = =1.1 x 10-4 moldm-3

Each mole of siver oxalate that dissolves produces 2mole of Ag+ and 1mole of C2O42- ions in solution.
[ ]= 1.1 X 10-4 moldm-3
[ ] = 2x1.1 x 10-4moldm-3
KSP = [ ] [ ]
KSP = 1 11 1 =5.3x1 mol3dm-9
Example two
Calculate the solubility in gdm-3 of lead(ii) chloride,PbCl2 at25 0C if its solubility product is 1.6x10-5 mol
3
dm-9 (Pb=207, Cl=35.5 )
Solution
Let the solubility of lead(ii)chloride be S moldm-3
PbCl2(s) + (aq) Pb2+ (aq) + 2Cl-(aq)
S S 2S
KSP =[ ][ ] = =4 = 1.6x10-5
√
S= =1.587 x 10-2 moldm-3
Molar mass of lead (ii) chloride = 207+ (2x35.5) = 278g
Solubility of lead (ii) chloride = 1.587 x 10-2x 278 =4.412 gdm-3
Example three
The solubility product of iron (iii) hydroxide Fe (OH)3 at 250 C is 8x10-40 mol4dm-12
Calculate the solubility of iron (iii) hydroxide in moldm-3
Solution;
Let the solubility of iron (iii) hydroxide be S
Fe(OH)3(s) + (aq) Fe3+ (aq) + 3 ̅ H (aq)
S S 3S
KSP = [ ][ ̅ ]

KSP = =27 =8 x 10-40 mol4 dm-12
S= √ 8 1 = 0.74 x 10-10 moldm-3
Limitations of solubility products
 Solubility products only apply to saturated solution at equilibrium.
 Solubility products only apply to sparingly soluble ionic compounds
 Solubility products are only constant at a particular temperature
Significancy
It reveals the point at which the compound is to precipitate
Factors that affects the solubility of a sparingly soluble salt at constant temperature
a) Common ion effect
Adding a strong electrolyte or an ionic salt that contains a common ion to a sparingly soluble salt at
equilibrium reduces the solubility of the salt and this effect is called common ion effect.
Common ion effect is the precipitation of a sparingly soluble compound/salt/electrolyte from its
saturated solution by adding a soluble ionic compound containing one of the ions released by the
sparingly soluble salt.
Suppose you had a saturated solution of calciumsulphate:
CaSO4(s) + (aq) Ca2+ (aq) + SO42- (aq)
KSP =[ ][ ] =2.4X10-5 mol2dm-6 at 250 C
Now suppose you added sodium sulphate solution to this which contained an ion in common with it(
sulphate ions).
Increasing the concentration of sulphate ions will cause the position of equilibrium to move to the left
according to le Chateliers principle, and so more of the calcium sulphate will precipitate out. i.eThe
calcium sulphate becomes less soluble.the value of solubility product cannot be exceeded it must
remain at 2.4x10-5 mol2dm-6, because it is an equilibrium constant.increasing the concentration of the
sulphate ions by adding more of them must be compensated for by lowering the concentration of
calcium ions .the only way that can be done is to turn them into solid calcium sulphate.
Therefore;Addition of a common ion reduces the solubility of a sparingly soluble salt.

Worked examples
Example one
The solubility product of calcium iodate (v) is 1.69 x10-9 mol3dm-9 at 250C
a) calculate the solubility of calcium iodate (v) in moldm-3 in
i)water.
ii)sodium iodate solution of concentration 0.2moldm-3
b) Calculate the mass of calcium iodate(v) precipitated out due to addition of 0.1moldm-3 calcium nitrate
solution.(Ca=40,I=127,O=16 )
Solution
Ca(IO3)2(s) + (aq) Ca2+(aq) + 2IO3-(aq)
Let the solubility of Ca(IO3)2 in water be ymoldm-3
[ ] =ymoldm-3
[ ] =2y moldm-3
KSP =[ ][ ] = =4 =1.69x10-9
Y=7.50 x 10-4
ii)let the solubility of Ca(IO3)2 in 0.2 M sodium iodate be S
[ ] =S moldm-3
[ ] =(2S+ 0.2) moldm-3
But Solubility of Ca(IO3)2 is very small compared to solubility of 0.2 M NaIO3
Such that (2S+ 0.2) 0.2
KSP =[ ][ ] = =1.69x10-9
s=4.225 x 10-8 moldm-3
b) let the solubility of Ca(IO3)2 in 0.1 M calcium nitrate be w moldm-3
[ ] =(w+0.1) moldm-3
[ ] =2w moldm-3
But Solubility of Ca (IO3)2 is very small compared to solubility of 0.1 M Ca(NO3)2

Such that (W+ 0.1) 0.1
KSP =[ ][ ] = 1 =1.69x10-9
w=6.5 x 10-5
Moles of Ca (IO3)2 precipitated= solubility in water – solubility in calcium nitrate
=7.50 x 10-4 -6.5 x 10-5 =6.85x 10-4 moldm-3
Molar mass of Ca (IO3)2 =40+(127x2) +(16x6)=390g
Mass of Ca (IO3)2 precipitated= 390x6.85x 10-4=0.267g
Deciding whether or not precipitate will form when solutions are mixed.
Will a precipitate of calcium hydroxide form if
a) 5.0cm3 of 0.050moldm-3 sodium hydroxide solution, NaOH,is added to 5cm3 of 0.05moldm-3 calcium
chloride CaCl2.
b) 5.0cm3 of ammonia solution containing OH- ions with concentration 0.002 moldm-3 is added to 5.0cm3
of 0.05moldm-3 calcium chloride solution,CaCl2
Ksp(Ca(OH)2) = 5.5X10-6 mol3dm-9 at 298K
Solution
Moles of hydroxide ions in 1000cm3 = =0.025moldm-3
Moles of calcium ions in 1000cm3 = = 0.025moldm-3
[ ][ ] =0.025x(0.025)2=1.6X 10-5 mol3dm-9
This value is greater than the solubility product of calcium hydroxide 5.5X10-6 mol3dm-9 calcium ions and
hydroxide ions will precipitate out as calcium hydroxide until the ion concentrations are sufficiently
reduced.
b) Moles of hydroxide ions in 1000cm3 = =0.001moldm-3
Moles of calcium ions in 1000cm3 = = 0.025moldm-3
[ ][ ] =0.025x(0.001)2=2.5X 10-8 mol3dm-9
This value is less than the solubility product of calcium hydroxide 5.5X10-6 mol3dm-9
The solution is not saturated with calcium hydroxide so no precipitate will form

Application of common ion effect
i) Purification of common salt (sodium chloride)
Common salt or sodium chloride contains calcium chloride and magnesium chloride as impurity which
make it appear damp.
Pure common salt may be obtained by bubbling hydrogen chloride gas into saturated solution of impure
sodium chloride since the solution is saturated with sodium chloride.
Addition of hydrogen chloride gas provides chloride ions which precipitate only pure sodium chloride
and not magnesium chloride or calcium chloride i.e
Na+(aq) + Cl- (aq) NaCl(s)
ii salting out soap
Ordinary soap is a sodium salt stearic acid; a saturated solution of soap has equilibrium
NaSt(s) Na+(aq) + St-
In the manufacture of soap, a concentrated solution of sodium chloride added provides sodium ions
and this increases the concentration of sodium ions making the solubility product of soap to exceeded
ksp of soap.
Therefore the soap precipitates out in order to maintain the Ksp value.
iii) Determining the percentage of the chloride ion in solution by volumetric analysis
iv)In extraction of aluminium
b) Complex ion formation
A complex ion is a species formed between a central metal ion and one or more surrounding ligands,
molecules or ions that contains at least one lone pair of electron .
a sparingly soluble salt will dissolve in a solution if it has the ability to form a complex.
For example;
Silver chloride is sparingly soluble in water but readily dissolves in ammonia solution
In water silver chloride ionizes according to the equation.
AgCl(s) + (aq) Ag+(aq) + Cl-(aq)
The solubility product of silver chloride is very small and is easily reached when negligible amount of
silver chloride dissolves in water.

in ammonia solution,silver ions reacts with ammonia solution to form a soluble complex cation
diammonia silver(i)ion .
Ag+(aq) + 2NH3(aq) [ ] (aq)
The with draw of silver ion decreases their solubility at equilibrium and therefore more silver chloride
dissolves to restore the equilibrium constant no longer participates in the solubility product equilibrium
of silver chloride. This continues if sufficient ammonia is present until all the silver chloride precipitate
has dissolved and the concentration of Ag+ in the solution is so small that the solubility product of silver
chloride cannot be reached.
Similarly
Silver cyanide is almost insoluble in water but readily soluble in potassium cyanide solution.
The solubility product of silver cyanide in water is very small and is easily reached when negligible
amount of siver cyanide dissolves in water
AgCN(s) + (aq) Ag+(aq) + CN-(aq)
In potassium cynide,cynide ions react with poassiumcynide solution to form a soluble complex anion
Ag+(aq) + C ̅(aq) + C ̅(aq) Ag (aq)
Copper (ii) hydroxide, almost insoluble in water; readily soluble in excess aqueous ammonia solution
The solubility product of copper hydroxide is very small and is easily reached when negligible amount of
copper hydroxide dissolves in water.
Cu(OH)2(s) + (aq) Cu2+(aq) + 2 ̅ (aq)
in ammonia solution,copper(ii) ions reacts with ammonia solution to form a soluble complex cation
tetra amminecopper(ii) ion .
Cu2+ (aq) + 4NH3(aq) [ ] (aq)
Lead (ii) chloride is sparingly soluble in cold water but considerably soluble in concentrated hydrochloric
acid.
In water lead(ii) chloride ionizes according to the equation.
Pb(Cl)2(s) + (aq) Pb2+(aq) + 2 Cl-(aq)
The solubility product of lead(ii) chloride is very small and is easily reached when negligible amount of
lead(ii) chloride dissolves in water.
in concentrated hydrochloric acid solution,lead chloride reacts with concentrated hydrochloric acid
solution to form a soluble complex anion .

Pb2+(aq) + 2 Cl-(aq) + 2 Cl-(aq) [ ] (aq)
Iodine is sparingly soluble in water because it is covalent, but readily soluble in concentrated potassium
iodide due to formation of a soluble complex.
I2(aq) + 2I-(aq) I3-(aq)
Therefore formation of soluble complex ion results into increase in solubility of a sparingly soluble salt
Note adequate presentation of each of these cases requires a ful argument on the lines shown for the
case of silver chloride in ammonia solution.
c)addition of soluble salt that doesn’t contain the common ion but forms a precipitate with one of the
ions
Addition of a soluble salt, which does not contain a common ion but reacts with one of the ions in
solution increases solubility of sparingly soluble salt.
Example; barium sulphate is more soluble in calcium nitrate than in water
In water barium sulphate ionizes according to the equation.
BaSO4(s) + (aq) Ba2+(aq) + SO42-(aq)
The solubility product of barium sulphate is very small and is easily reached when negligible amount of
barium sulphate dissolves in water.
In calcium nitrate solution, calcium ions reacts with sulphate ions at equilibrium to form calcium
sulphate precipitate. Ca2+(aq) + SO42- (aq) CaSO4(s)
This disturbs the equilibrium of barium sulphate and therefore more barium sulphate dissolves to
restore the equilibrium thus increase in solubility of barium sulphate.
Application of the concept of solubility product
1.Solubility product is applied in qualitative analysis in
a)precipitation of sulphides in qualitative analysis
Sulphides with low solubility product eg copper sulphide and lead sulphide are precipitated in acidic
media while those with high solubility product eg nickel sulphide and manganese sulphides are
precipitated in alkaline media.
Hydrogen sulphide is a weak electrolyte and is used for precipitation of various sulphides in qualitative
analysis, it ionizes to a small extent as H2S(aq) 2H+(aq) + S2- (aq)

In acidic medium the ionization of hydrogen sulphide is suppressed due to common ion,the
concentration of S2- is so low that the ionic product of sulphide of group (ii) can exceed their solubility
product and get precipitated.
While in alkaline medium, NH4OH(aq) NH4+ (aq) + ̅ (aq)
the OH- ions furnished by NH4OH removes H+ ions from solution in form of water.more of the ionization
of H2S occurs and thus the concentration of S2- ions increases it becames so high that the ionic product
of the sulphides of group (iv) exceed their solubility product and get precipitate
b)Precipitation of metallic hydroxides in qualitative analysis
the hydroxides of Fe3+,Al3+ , and Cr3+ are precipitated by ammonia solution in presence of ammonium
chloride because they have low solubility product while Zn2+ ,Fe2+ and Co2+ are not precipitated by
ammonia solution in presence of ammonium chloride because they have a high solubility product.
Aqueous ammonia is a weak electrolyte producing few ̅ ions where as ammonium chloride is a strong
electrolyte ionizing completely.
NH4OH(aq) NH4+ (aq) + ̅ (aq)
NH4Cl(aq) NH4+ (aq) + Cl-(aq)
In presence of ammonium chloride the concentration of NH4+ ions is high and due to common ion effect
the equilibrium is displaced to the left ie the ionization of ammonia is suppressed. Therefore the low
concentration of ̅ ions exceeded the low KSP value of Fe(OH)3 Al(OH)3 hence precipitated while for
Zn(OH)2 Fe(OH)2 the low concentration of ̅ ions cannot be exceed the KSP of these hydroxides
T0PIC 8:CHEMICAL KINETICS

8.1 INTRODUCTION

Is the study of speed with which a chemical reaction occurs, the factors that affect this
speed ie temperature, concentration of reactants in solution, pressure of gaseous
reactants, particle size of solid reactants, presence of light ,addition of catalyst and the
mechanisms by which reactants are converted to products.
Speed of a reaction is the rate at which the concentration of reactants and products
change
Reaction rates
Rates of reactions can be determined by monitoring the change in concentration of

either reactants or products as a function of time
Reaction rate is the measure of change in the concentration of reactants or products

with time
Rate =
A plot of concentration of reactant or product against time yields a curve like this
conc
conc
time
time
The slope of a line tangent to the curve at any point is the instantaneous rate at that time
The reaction for the reactant slows down with time because the concentration of
[ ] [ ]
reactants decrease . Therefore rate can be written as rate = = -
The reaction for products increase with time because the concentration of products
increases

[ ] [ ]
Therefore rate can be written as rate= = +
The steeper the gradient, the faster the rate of the reaction.
The reaction is fastest at the start when the concentration of reactant is greatest.
When the reaction is complete,the gragh levels off and the gradient becomes zero.
Reaction rates and stoichiometry
For the reaction
H2(g) + I2(g) 2HI(g)
[ ]
The rate of disappearance of H2 =-
[ ]
The rate of disappearance of I2 =-
[ ]
The rate of formation of HI =+
Since one mole of hydrogen combines with one mole of iodine to form two moles of
hydrogen iodide the rate of decrease of concentration of hydrogen and concentration of
iodine must be equal and should be half the rate of increase of concentration of
hydrogen iodide so that we have.
[ ] [ ] [ ]
Rate = - =- =+
for the reaction,IO3-(aq) +5I-(aq) +6H+(aq) 3I2(aq) + 3H2O(l)
[ ] [ ] [ ]
Rate = - = - (reactants)
[ ] [ ]
=+ =+ (products)

Measuring reaction rate
The rate of reaction is found by measuring some property of reactant or product
proportional to concentration such as gas volume, gas pressure, colour change, electric
properties e t.c at various times after the start of reaction.
Then the property is plotted against time elapsed since the start of a reaction.
The rate of reaction is the gradient of the tangent to the curve at that point
Some of the methods of following the reaction include;
a)chemical methods
i) By recording the time for the reaction to reach a certain stage
Examples of this method are
-classic iodine-clock experiment, in which the time for the iodine-starch colour to
appear is recorded
-the acid-thiosulphate reaction in which the time for the sulphur precipitate to reach a
certain density is recorded.
ii) By following the progress of a reaction
Known volumes are withdrawn from the reaction mixture at regular intervals of time.
Each sample is quickly run into excess of a reagent which will arrest the reaction or the
reaction is stopped by rapid cooling the sample.
The sample is then analyzed usually by titration to determine the concentration of

either a reactant or a product present.
Example of these include
-Reaction between iodine and Propanone
-Catalyzed decomposition of hydrogen peroxide
b)physical methods
This is done by
i) Measuring the volume of a gas produced by using a graduated syringe in a given

time
eg 2H2O2(l) 2H2O(l) + O2(g)

ii) Measuring the loss in mass of a reaction mixture due to the loss of gaseous products
CaCO3(s) + 2HCl(aq) CaCl2(g) + H2O(l) + CO2(g)
iii) Measuring the change in conductivity of liquid due to the change in number of ions
e.g in the hydrolysis of halogen alkane
(CH3)3CBr + H2O (CH3)3COH +H+(aq) + Br-(aq)
LAW OF MASS ACTION
According to the law of mass action
The rate of any chemical reaction at constant temperature is directly proportional to the
concentration of the reacting species with each concentration term raised to a power
equal to the number of molecules of each reacting species.
For the reaction
aA +b B c C +d D
Rate α [A]m[B]n
Rate = K [A]m[B]n
Where: K is the rate constant
The above expression is called the rate equation for the reaction
RATE EQUATION OR RATE LAW

The rate equation or the rate law shows the relationship between the reaction rate and
the concentration of reactants involved in the rate determining step.
Rate determining step refers to the slowest stage in a chemical reaction through which a
reactant is converted into products.
The rate equation of any given chemical reaction must be experimentally determined; it
can’t be deduced from a given chemical equation
Rate constant K;
This is the ratio of the rate of a chemical reaction to the product of concentration of its
reactants raised to an appropriate power as in the experimentally determined rate
equation.

 K is unique for each reaction
 K is constant at constant temperature
 Its magnitude determines whether the reaction is slow or fast
 Its value depends on the activation energy (Ea) and temperature of reaction
(K= A )
 The units of K must always be worked out from the rate equation
Order of reaction
This is the sum of the powers to which the concentrations of the reactants in the
experimentally determined rate equation are raised.
For example from the rate equation Rate = K [A]m[B]n
The exponent’s m and n which are usually integers tell the order of reaction with
respect to each reactant.
m is the order of reaction with respect to A
It’s the power to which the concentration of A is raised in the rate equation
n is the order of reaction with respect to B
It’s the power to which the concentration of B is raised in the rate equation
m+n is the overall reaction order
its the sum of the powers to which the concentration terms of the reactants are raised in
the rate equation
NOTE
i) M and n bears no relationship to the coefficients a and b

ii) M and n are determined experimentally
iii) The exponents in the rate law are not equal to the Stoichiometric coefficients
unless the reaction actually occurs via a single step mechanism however the
coefficients are equal to the Stoichiometric coefficient of the rate determining
step

TYPES OF ORDER OF REACTION
Zero order
An order of 0 is called zero order. If a reaction is zero order with respect to a particular
reactant, it means that the concentration of that substance does not affect the rate of
reaction.it would be written in the rate equation as for example
Rate =k[ ] =K
First order
An order of 1 is called first order. If a reaction is first order with respect to a particular
reactant, it means that the concentration of that substance is proportional to the rate of
reaction. Doubling the concentration doubles the rate of reaction tripling the
concentration triples the rate and so on .it would be written into the rate equation as for
example
Rate =k[ ]
Examples of first order reaction
a)all radioactive decays
b) Decomposition of nitrogen pent oxide
2N2O5(g) 4NO2(g) + O2(g)
c) Hydrolysis of methyl acetate in aqueous solution
CH3COOCH3 (aq) + H2O(l) H+ CH3COOH (aq) + CH3OH(aq)
d)hydrolysis of sucrose (sugar)
C12H22O11 + H2O(l) C6H12O6 (aq) + C6H12O6 (aq)
e) Decomposition of hydrogen peroxide
2H2O2(aq) 2H2O(aq) + O2(g)
Second order
An order of 2 is called second order. If a reaction is second order with respect to a

particular reactant, it means that the square of the concentration of that substance is
proportional to the rate of reaction. Doubling the concentration the rate will increases

four times (22), tripling the concentration of the reactant the rate goes up nine times (32).
It would be written into the rate equation as, for example rate= [ ]
DETERMINING THE OVERALL ORDERS OF REACTION
a) From initial rate method

In this method, series of experiments with different initial concentrations are carried out
separately and their initial rate of reaction measured. the order with respect to a given
reactant is done by comparing the initial rate for two experiments in which the
concentration of only the reactant whose order is to be determined is changing while
the concentration of other reactants are kept constant. The initial rate is the gradient of
the tangent to the concentration vs time curve at t=0.
(This method requires more than one reactant.)
If doubling the concentration of A has no effect on the rate, the reaction is zero order
with respect to A: rate =k[ ] i.e rate=k
If doubling the concentration of A doubles the rate, the rate and the concentration are
directly proportional, and the reaction is first order with respect to A: rate =k[ ] i.e
rate=k[ ]
If doubling the concentration of A increases the rate by a factor of four, the reaction is
second order with respect to A: rate =[ ]
In general, if the concentration of a reactant A is increased or decreased by X and the

initial rate increases or decreases by Xn the order of reaction with respect to that reactant
A is n. and rate = [ ]
Example one
The table below shows some kinetic data for the following reaction
2A+B+ 3C products
experiment Initial Initial Initial Initial rate

concentration concentration concentration Moldm-3 s-1
of A (moldm-3) of B (moldm-3) of C (moldm-3)
1 0.1 0.1 0.1 2.0x10-4
2 0.2 0.1 0.1 4.0x10-4
3 0.2 0.2 0.1 1.6x10-3
4 0.1 0.1 0.2 2.0x10-4
(a) Determine the order of reaction with respect to A,B and C

i)By inspection
Look for two experiments where the concentration of everything else have remained
unchanged, but the concentration of A is different.in this case experiment 1 and 2
The concentration of A has doubled and so has the initial rate of reaction.
The reaction is therefore first order with respect to A
unchanged, but the concentration of B is different.in this case experiment 2 and 3
Doubling concentration of B has caused the rate to go up four times (22).
The reaction is second order with respect to B
unchanged, but the concentration of C is different.in this case experiment 1 and 4
Doubling concentration of C the initial rate remain the same (20).
the reaction is zero order with respect to C
ii)by calculation
let rate = [ ] [ ] [ ]
using experiment 1 and 2
rate1 =k(0.1)x(0.1)y(0.1)z =2.0x10-4 ………(i)
rate2 = k(0.2)x(0.1)y(0.1)z =4.0x10-4 ………(ii)
equation (ii) divide by equation (i)
2x = 21 x=1
Using experiment 2 and 3
Rate3 =k(0.2)x(0.2)y(0.1)z =1.6x10-3 ………(iii)
rate2 = k(0.2)x(0.1)y(0.1)z =4.0x10-4 ………(ii)
equation (iii) divide by equation (i)

2y = 22 y=1
using experiment 1 and 4
rate1 =k(0.1)x(0.1)y(0.1)z =2.0x10-4 ………(i)
rate4 = k(0.1)x(0.1)y(0.2)z =2.0x10-4 ………(iv)
equation (iv) divide by equation (i)
2z = 20 z=0
b) write the rate equation for the reaction
rate = k[ ][ ]
c)state the overall order of reaction
The overall order of reaction is 3 (because the sum of the individual orders 1+ 2+0,is3)
d)Calculate the rate constant and give its units
Rearranging the rate expression gives

K=[ ][ ]
Substituting in the numbers for the first experiment gives:
K= =0.2
Units for k
K= =mo d
Exercises
The table below shows the experimental data for the reaction between
Peroxodisulphate ion S2O82- and iodides ions according to the reaction:
2I-(aq) + S2O82- (aq) I2(aq) + 2SO42- (aq)
Experiment no Initial concentration(moldm-3) Initial rate of

[ ] [ ] reaction(moldm-3s-1)
1 0.038 0.030 7.0x 1
2 0.076 0.030 14.0x 1
3 0.076 0.060 28.0x 1
a)find the order of reaction with respect to I- and S2O82-

b)state the overall order of reaction
c)write the rate equation

d)calculate the value of the rate constant and state its units
FINDING ORDERS OF REACTION GRAPHICALLY

First order with respect to A
Consider the reaction A B
Rate concentration- graphs
Rate = K[A]1
If a reaction is first order a plot of rate against concentration
gives a straight line through the origin with positive gradient k
rate
slope=k(rate constant)
Concentration
Concentration-time graphs
[ ]
From First order differential form - = K[A]
-d[A] = k[A]dt
[ ]
= - Kdt (separating variables)
[ ]
[ ] [ ]
∫[ ] [ ]
=∫ (intergrating)
[ ]
ln[ = -kt or [A]t = [A]0
]
[ ]
log10[ =- (converting to base ten)
]

log[A]t = + log [A]0
where [A]0 is the initial concentration of A, at t=0,
[A]t is the concentration of A at some time, t during the course of the
If a reaction is first order a plot
i) log[A]t against time gives
a straight line graph with a negative gradient and intercept on the y -axis
log[𝐴]𝑡
time t
i) [A]t against time t gives a curve with constant half life
[A]t
Time t
For first order reaction (t1-0) = (t2-t1) = (t3-t2)

HALF LIFE ( )
Half life is defined as the time it takes for the concentration of a reactant to fall to half of
its initial value
HALF LIFE OF FIRST ORDER REACTION

[ ]
From the equation log10[ =-
]
[ ]
At, t = [A]t =
[ ]
Log10 [ ]
) =
This shows that first order reaction is independent of the initial concentration of the
Reactant
a) Second order reaction

Consider the reaction A products
Rate-concentration graphs
Rate = K[A]2
A plot of rate against the square of concentration gives a straight line graph
rate
[𝐴]⬚
Concentration-time graphs
[ ]
From second order differential form - = K[A]2

-d[A] = k[A]2dt
[ ]
= - Kdt (separating the variables)
[ ]
[ ] [ ]
∫[ ] [ ]
=∫
= kt + [
[ ] ]
A reaction is said to be second order if a plot of
against time Gives straight line with positive gradient and intercept on y-axis
[ ]
1
[𝐴]𝑡
time
ii) [A]t against time t gives a curve with non-constant half life(doubles)
[A]t
Half life of second order reaction

Time
from the equation = kt + [
[ ] ]
[ ]
At, t = ,[ ] =
=k +[ , =
[ ] ] [ ]

c)zero order reaction
Consider the reaction A B
rate- concentration graphs
Rate = k[A]0 = K
A reaction is said to be zero order reaction if the rate of reaction is independent of the
concentration of reactants
rate
Concentration
Concentration-time graph
[ ]
From zero order differential form - =K
-d[A] = kdt (separating the variables)

[ ]
∫[ ]
[ ] =∫ (integrating)
[A]t = -kt + [A]0
A reaction is said to be zero order if:
a plot of [A]t against time t gives a straight line with negative gradient and intercept on
the
y-axis
[A]t Slope = -k
Intercept = [A]0
Time
Half life of zero order reaction
From the equation [A]t = -kt + [A]0

[ ]
At, t = [A]t =
[ ]
=- k +[A]0
= [A]
d) Pseudo first order reactions
Some reactions which may appear to be second order overall may be first order, if one
of the reactants is in excess or a solvent
In hydrolysis of methyl ethanoate
CH3COOCH3 + H2O H+ CH3COOH + CH3OH
The reaction is very slow it is studied in presence of a small amount of mineral acid
which acts as a catalyst
The concentration of water is in large excess and its concentration is therefore almost
constant as the reaction proceeds the rate equation therefore reduces to
Rate = k[CH3COOCH3]
Exercises
A compound B decomposes according to the following equation
2B products
The table below shows the concentration of B at various times
Time (min) 2.0 4.0 7.0 10.0 14.0 20.0

[ ]moldm-3 0.820 0.670 0.490 0.372 0.240 0.141
(a)draw the graph of log10[ ] against time
(b) using the graph determine the
i)original concentration of B

ii)order of reaction
iii)rate constant for the reaction
iv)half life for the reaction
1 Given the data below, find the rate law for the following reaction at 300K.
A+B→C+D
exp initial[A] (Moldm-3) initial[B] (Moldm-3) Initial rate (Moldm-3 s-1
1 0.010 0.010 1.0x10-5
2 0.010 0.030 1.0x10-5
3 0.030 0.030 9.0 x 10-5
a) Find the orders of reaction with respect to A and B

b) Write the rate equation
c) Calculate the rate constant including its units
3.The rate equation for the reaction
2A +4B + 2X- X2 + 2Y + 2Z- is given by
Rate = k[A] [X-] [B]2
Where k is the rate constant
How would the rate of the reaction alter
If (i) [B] and [X-] were kept constant but [A] doubled
i) [X-] and[A] are kept constant but [B] halved
ii) [X-] and[A] were kept constant but [B] doubled
i)From the rate equation Rate = k[A] [X-] [B]2
Rate = k[2A] [X-] [B]2
Rate =2 k[A] [X-] [B]2
Therefore The rate would be doubled
ii)from the rate equation Rate = k[A] [X-] [B]2
Rate = k[A] [X-] [ ]2

Rate = k[A] [X-] [B]2
Hence the rate reduces by
iii) From the rate equation Rate = k[A] [X-] [B]2
Rate = k[A] [X-] [2B]2
Rate =4 k[A] [X-] [B]2
Hence the rate increases by 4
REACTION MECHANISMS
A reaction mechanism is a detailed step-by-step account of how an overall reaction
happens.it specifically states all intermediate stages and mentions all intermediate
species formed, even though some do not appear as products.
A suggested mechanism must be consistent with the order of reaction the partial order
of any species which occurs in the mechanism after the rate determining step will be
zero. A chemical reaction proceeds through several steps, but the slowest step is the rate
determining step
for example
NO2 (g) + CO(g) NO(g) + CO2(g)
Suggested mechanism
Step one NO2 (g) + NO2(g) slow NO3(g) + NO(g)
Step two NO3 (g) + CO(g) fast NO2(g) + CO2(g)
Rate = k[NO2]2[CO]0
MOLECULARITY OF A REACTION
This is the number of ions, molecules or atoms which take part in the rate determining
step of a reaction.
Molecularity is a theoretical postulate (believed to be true) and not an experimentally

measured quantity un like the order of reaction Molecularity must be a whole number.
Types of Molecularity
Unimolecular is a reaction where one molecule is involved in the reaction
for example; Hydrolysis of tertiary alkyl halide
(CH3)3CBr + NaOH (CH3)3C-OH + NaBr

Suggested mechanisms
CH3 CH3
CH3- C OH SLOW CH3-C+ + Br-
CH3 CH3
CH3 CH3
CH3- C+ fast CH3-C OH
CH3 - OH CH3
Bimolecular is a reaction where two molecules are involved in the reaction for example
Hydrolysis of primary alkyl halide
CH3CH2Br + NaOH CH3CH2OH + NaBr
Suggested mechanisms
H fast
CH3-C- Br CH3CH2OH + NaBr
THEORIES RESPONSIBLE FOR OCCURANCE OF CHEMICAL REACTIONS

There are two theories responsible for occurrence of chemical reactions
The collision theory and the transition state theory
The collision theory
This is based on kinetic theory of gasses that assumes that before particles can react
i) They must collide
(old bonds may break and new bonds form during collision.)
ii) they must have a certain minimum amount of energy often referred to as the
activation energy Ea for the bonds within the reactant molecules to break and
become sufficiently activated for products to be formed
ACTIVATION ENERGY: is the minimum energy which reactant molecules must

absorb before a reaction can take place.

Or this is the energy barrier which must be overcome before a reaction can take place
iii) reactant molecules must collide in the correct position
The transition state theory
this theory considers the details of the actual collision between two molecules
according to this theory reactants are not directly converted into products the molecules
first absorb energy to form highly unstable species in which bonds are partially broken
and others partially formed this un stable species is known as the transition state or
activated complex
ACTIVATED COMPLEX is an unstable intermediate state in which the bonds between

the molecules of reactants are partially broken and the bonds between products are
partially formed.
H2 (g) + I2(g) H H 2HI(g)
I I
During this process, the kinetic energy of the collision is converted into potential energy
which can be shown on an enthalpy diagram usually referred to as the reaction profile
and the energy gap between the reactants and this peak is known as the activation
energy for the reaction
When the activated complex decomposes into products energy is released
The difference in the energy ΔH is equal to the activation energy of forward reaction
minus the activation energy of the reverse process
The reaction profile for an exothermic reaction
P.E
Reaction coordinate

The reaction profile for an endothermic reaction
P.E
Reaction coordinate
Factors which influence rates of reaction

Any factor which increases frequency of collision lowers the activation energy for the
reaction.
Or any factor which increases the number of molecules with energy equal to or greater
than the activation energy of the reaction increases the rate of reaction. These factors
include;
Concentration
If concentration of a reactant in solution is increased, The ions will be closer together,

the closer together they are the more frequently do the ions collide ,the more they
collide the greater is their chance of reacting and this results in increased reaction rate
therefore rate of reaction is proportional to concentration of reactant except for zero
order reaction
Pressure of gaseous reactants

If the pressure of gaseous reactants is increased the molecules of gases are pushed
closer together as a result they collide more frequently and react more rapidly
Physical state of reactants or surface area
The rate of chemical reaction involving a solid reactant is increased by increasing the
surface area of the solid. in such reactions collisions occur between moving molecules
and the solid reactants it follows that the greater the surface area of reactants the greater
the surface area available for collisions and the greater the reaction rate
Increase in surface area increase the rate of reaction because the amount of contact or
surface area for contact between the reactant molecules or particles do increase and
hence the rate or frequency of collision increases
The effects of a Catalyst on the rate of reaction
A catalyst is a substance which alters the rate of chemical reaction without undergoing
any chemical change and can be recovered at the end of reaction.
it may be a positive or a negative catalyst
A positive catalyst increases the rate of chemical reaction by providing an alternate

path way with lower activation energy while a negative catalyst decreases the rate of
chemical reaction by providing an alternate path way with higher activation energy
Below are energy diagrams showing positive and negative catalyzed reactions

Types of catalyst.
There are generally two types of catalyst
i)homogeneous catalyst and
ii)heterogeneous catalys
Homogeneous catalyst
This is when the catalyst and reactants exist in the same phase during a reaction .
These can be gaseous or liquid phase
Examples of homogeneous catalyst
2SO2 g + O2 g NO 2SO3 g
CH3COOCH2CH3 + H2O l H+ CH3COOH aq + CH3CH2OH aq
Heterogeneous catalyst
This is when the catalyst and reactants are in different phases during reaction for
example vanadium (v) oxide is a solid catalyst that catalyses a reaction between sulphur
dioxide and oxygen to form sulphur trioxide which are gases
2SO2 g + O2 g V2O5 2SO3 g
Auto catalyst
In some reactions one of the products of the reaction acts as a catalyst for the reaction
for example in the reaction of ethane dioate with acidified potassium manganate (vii)
the reaction has to be heated to 600C to get the reaction to start but the reaction
manganese (ii) ions produced catalyses the reaction and reaction continues even if the
solution is cooled to room temperature.
2MnO4-(aq) + 5C2O42- (aq) + 16 H+(aq) 2Mn2+ (aq) + 10CO2(g) + 8H2O(l)

Essential properties of a catalyst
 It should remain chemically unchanged at the end of the reaction

 It alters the rate of reaction
 Only small amount of the catalyst is required to bring about a change
 Its specific in action ie it catalyses only particular reaction
 It has optimum temperature. (the temperature at which the catalyst is most
active)
 It catalyses both forward and back ward reaction to the same extent this explains
why a catalyst has no effect on the value of equilibrium constant but increase the
rate of attainment of equilibrium
 A catalyst provides an alternative route with lower activation energy barrier for
the reaction more molecules possess the lower activation energy and so the
reaction is speeded up
 The enthalpy values are the same for catalyzed and unanalyzed reaction
 A catalyst can be poisoned by presence of impurities(catalyst poison) they form
strong bonds with active sites of the catalyst to make the surface an available for
chemisorption’s for example platinum is poisoned by arsenic (iii) oxide in the
Haber process.
 Its activity can be enhanced by a catalyst promoter a material added to a catalyst
to increase its activity but not to catalyze the reaction for example iron in Haber
process is en hanced by aluminium(iii) oxide
Mechanism of a catalyst
THE EFFECTS OF TEMPERATURE ON THE RATE OF REACTION AND RATE
CONSTANT
Increase in temperature increases the average kinetic energy of the reacting particles
therefore
- the molecules move faster and have more kinetic energy

- there are more collision each second
- the increased kinetic energy produces more energetic collisions
- a greater proportion of molecules exceed the activation energy hence the rate of
reaction increases.
The increased energy means more particles now exceeds the energy of activation so
there are many more successful collisions this leads to a dramatic increase in the rate of
reaction
This can be shown on the Maxwell-Boltzmann distribution of molecular energies
Lower temperature
Higher temperature
Kinetic energy
Minimum energy needed for the reaction
As temperature increases the curve flattens and broaden thus at higher temperature a
larger population of molecules has higher energy and the number of molecules that can
overcome the activation energy barrier increases as a result the reaction rate increases
For some chemical reactions the reaction rate increases approximately two folds for
every 100C rise in temperature.
From the simple collision theory, the rate of reaction is proportional to the number of
molecules possessing energy greater than or equal to

The effect of temperature on reaction rate
An increase in temperature increases the rate of a reaction by increasing the rate

constant.
The variation of rate constant with temperature was studied by Arrhenius and found to
fit the equation k =A this equation is known as the Arrhenius equation.
K is the rate constant
Ea is the activation energy
T is the temperature(in kelvin)
R is the gas constant (8.31JK-1 mol-1 )
A is approximately constant and is taken as constant over small temperature ranges.

The constants can be found by using the equation in logarithmic form.
lnk= lnA - in log10,
logk=logA -
Aplot of logk against is a straight line of gradient and the intercept is logA.
The rate constant of a reaction was found to vary with temperature as follows
T(K) 290 310 330 350

k x10 -3 1.01 5.04 20.7 72.2
By plotting a suitable graph,find the activation energy of reaction.
(R=8.31JK-1mol-1)
EXERCISE
The following data was obtained from the reaction between hydrogen and iodine at
different temperature use the given data to determine the activation energy of the
reaction
TEMP(K) RATE CONSTANT k(mol-1 dm-3)

678 4.32 x 105
727 43.07x105
761 177.8x105
816 1432x105
855 5012x105

EXPERIMENTAL DETERMINATION OF ORDER OF REACTION
1)Experiment to determine the order of reaction with respect to hydrogen peroxide
FeCl3
2H2O2(aq) 2H2O(l) + O2(g)
Procedure
 A known volume of hydrogen peroxide is placed in a conical flask, small amount

of dilute sodium hydroxide added
 Iron (iii) chloride (a catalyst) added to the mixture and a stop clock
simultaneously started.
 After certain time ie two minutes a fixed volume is pipetted into a conical
containing a known volume of dilute sulphuric acid
( to stop the reaction and prevent further decomposition of hydrogen peroxide).
 The amount of hydrogen peroxide left undecomposed after two minutes is
determined by titrating with standard potassium permanganate solution
 2MnO4-(aq) + 5H2O2(aq) +6H+(aq) 2Mn2+(aq) +5O2(g) +8H2O(l)
 The volume of potassium permanganate is proportional to the concentration of
hydrogen peroxide present after time t.
 The procedure is repeated after a given interval for at least five intervals
 a graph of log(volume of potassium permanganate) against time is plotted
 if it gives a straight line with negative gradient and an intercept on the y-axis
the reaction is first order with respect to hydrogen peroxide.
2) iodination of Propanone
Iodine reacts with propanone in acidic medium according to the equation
CH3COCH3(aq) + I2(aq) CH3COCH2I (aq) + HI(aq)
Procedure
 A known volume of propanone and dilute sulphuric acid are measured into a conical flask.
 A known volume of iodine is added to the mixture above and the stop clock simultaneously
started.
 After a given time a fixed volume of the mixture is pipetted into a conical flask containing
aqueous sodium hydrogen carbonate( to stop the reaction and prevent further
decomposition of iodine).
 The amount of iodine left undecomposed after a given time is determined by
titrating with standard sodium thiosulphate solution

 2S2O32-(aq) +I2(aq) S4O6 2-(aq) +2I-(aq)
 The volume of sodium thiosulphate solution is proportional to the concentration
of iodine present after time t.
 The procedure is repeated after a given interval for at least five intervals
 a graph of (volume of sodium thiosulphate solution ) against time is plotted
 if it gives a straight line with negative gradient and an intercept on the y-axis
the reaction is zero order with respect to iodine.
3.Experiment to determine the order of reaction with respect to sodium
thiosulphate.
Sodium thiosulphate react with dilute hydrochloric acid slowly according to the
equation S2O32-(aq) +2 H+(aq) H2O(l) + SO2(g) + S(s)
Procedure
 A known volume of known concentration of sodium thiosulphate is placed in

a beaker and placed on a piece of paper marked with cross.
 A known volume of hydrochloric acid is added and a stop clock
simultaneously
 Started.
 The time taken for the cross to disappear when view from above the beaker
is noted.
 The procedure is repeated for different concentration of sodium thiosulphate
which is varied by adding a known volume of water
 A graph of reciprocal of time taken for the cross to disappear is plotted
against concentration of sodium thiosulphate.
 If a straight line graph passing through the origin with positive gradient is
obtained then its first order with respect to sodium thiosulphate.

Exercises
1)The table below shows variation in concentration of sodium thiosulphate with time when a fixed
volume of hydrochloric acid was added to sodium thiosulphate of various concentrations.
Concentration of sodium thiosulphate(mol dm-3) 0.2 0.16 0.12 0.08 0.04
Time, t(s) 24 29 39 60 138
a) Plot a graph of against concentration of sodium thiosulphate.

b) state the order of reaction and Give a reason for your answer.
c) Calculate the rate constant of the reaction and indicate its units.
d) Determine the time taken for the concentration of sodium thiosulphate to decrease from 0.2
mol dm-3
2.The table below shows the kinetic data obtained for hydrolysis of methyl ethanoate in acidic media.
[CH3COOCH3](mol dm-3) 0.241 0.161 0.109 0.073 0.046 0.034
Time(minutes) 0 60 120 180 240 320
a) Plot a graph of concentration of methyl ethanoate against time
b)Using the graph determine the:
i. Half-life of the reaction

ii. Order of the reaction with respect to CH3COOCH3.Give a reason for your answer.
iii. Calculate the rate constant and indicate its units.
2. (a)Distinguish between activation energy and rate constant.
( b) Briefly explain how activation energy and rate constant affect the rate of reaction
(c) Hydrogen reacts with iodine according to the following equation
H2(g) + I2(g) 2HI(g) ΔH = +25.9KJmol-1
The table below shows the rate constant for the reaction varying with temperature.
Temperature,T (K) 556 629 700 7.81
Rate constant, k(dm3mol-1s-1) 7.04x10-7 6.04x10-5 2.32x10-3 7.90x10-2

i. Plot a graph of log(k)against
ii. Use the graph to determine the activation energy of the reaction from Arrhenius equation
K=A e-Ea/RT(R=8.314JK-1mol-1)
(d)Draw an energy level diagram for the reaction in (c) above and use it to determine the activation
energy for the backward reaction.
e) Briefly explain how temperature affects the activation of the reaction.
3.(a)describe briefly how you determine the rate of reaction of the following reactions
i) Decomposition of hydrogen peroxide
ii) Iodination of propanone
iii) Reaction of sodium thiosulphate and dilute hydrochloric acid
END
3.(a) What is meant by the following terms?
i. Saturated solution
ii. Solubility of a salt
iii. Solubility product
(b)The solubility product of silver phosphate at 250C is 1.4*10-21 mol-4dm-12.
Calculate the
i. Solubility of silver phosphate in gdm-3 at 250C.

ii. Molar concentration of silver ions in the saturated solution of silver phosphate at 250C.
(c) Describe an experiment to determine the solubility product of strontium hydroxide in the laboratory
at 250C.
25cm3 of a saturated solution of strontium hydroxide at 250C were mixed with 50cm3 of 0.2M
hydrochloric acid . The resultant solution was diluted to 250cm3 .20cm3 of this solution required
12.55cm3 of 0.025M sodium hydroxide solution using phenolphthalein indicator. Calculate the solubility
product of strontium hydroxide at 250C

TOPIC 9: ELECTRO CHEMISTRY
This is the branch of chemistry which explains the inter conversation between chemical energy
and electrical energy in a chemical reaction.
ELECTROLYSIS
Definition:
This is the decomposition of a substance when in solution or molten state by passing an

electric current through it.
Terms used in electrolysis
ELECTROLYTE
This is an ionic compound which when in solution or molten state allows a current to go
through it and become decomposed.
Types of electrolytes
a)Strong electrolytes
these are electrolytes which completely dissociate or ionize in dilute solution and readily
conducts electricity . example include; all strong mineral acids ,all strong alkalis while in solution
and all aqueous solution of soluble ionic salts.
b)Weak electrolytes
These are electrolytes which partially ionize in aqueous solution producing few free mobile
ions. These allow small current to pass through them. Example include all weak acids and weak
alkalis ions.
Conductors
This is a solid substance which allows an electric current to go through it e,g all metals and
graphite. These conduct electricity because they have delocalized electrons which transmit the
electric current.

Electrodes
These are terminals through which current enters or leaves the electrolyte or terminal of
conductors through which electrons enter or leave the electrolyte. ,
electrodes are usually made of unreactive metals such as platinum or non- metal carbon which
do not take part in the chemical change occurring in electrolysis or active metals like copper
which take part in the chemical change occurring in electrolysis
Types of electrodes
Anode
This is the positive terminal through which current enters the electrolyte or the positive
terminal through which electrons leave the electrolyte.it is connected to the positive terminal
of the battery, negatively charged ions are attracted to this terminal.
Cathode,
This is the negative terminal through which current leaves the electrolyte or the negative
terminal through which electrons enters the electrolyte.it is connected to the negative terminal
of the battery, positively charged ions are attracted to this terminal.
Ion
This is a charged atom which has either gained or lost an electron.
Types of ions
Cations these are positively charged ions which migrate to the cathode
Anions these are negatively charged ions which migrate to the anode.
Discharge
Discharge is the process by which ions gain or lose electrons during electrolysis and become
atoms or molecules ie they lose their charge.

Cations are discharged at the cathode by gaining electrons and are deposited there for example
Cu2+(aq) + 2e Cu(s)
Anions are discharged at the at the anode by losing electrons and are liberated there for
example ; 2Cl-(aq) Cl2(g) +2e
ELECTROLYTIC CELL
This is the apparatus in which electrolysis is carried out
Current flows through the electrolyte from the positive terminal through the electrolyte then to
the negative terminal. Electrons flow from the negative terminal through the electrolyte then
to the positive terminal. When the circuit is complete the bulb light.
Process of electrolysis
It involves two stages
Stage one: Movement of ions to electrodes
During electrolysis the electrolyte is first dissociated into cations and anions, when current is
passed through an electrolyte, the anions move towards the anode and the cations move
towards the cathode.

Stage two: discharge of ions
At the anode anion loses electrons and form a neutral atom or molecule. Oxidation occurs at
the anode
Xn- X + ne
At the cathode, the cations gain electrons and form neutral atoms or molecules. Reduction
occurs at the cathode.
Mn+ + ne M
the electrons lost at the anode enter the external circuit and re-enter the electrolytic cell at the
cathode.
The migration of ions results in conduction of electricity
Selective or preferential discharge of ions at the electrode
When two or more ions of similar charge are present in solution under similar conditions for
example OH- and Cl- or H+ and Na+, one is preferentially selected for discharge depending on
the following factor
Position of the ion in the electro chemical series
An electro chemical series is an arrangement of ions in the order of decreasing reactivity
Cations anions
+
K
Ca2+
Na+
Mg2+
Zn2+ SO42-
2+ -
Fe NO3
2+ -
TO CATHODE Pb Cl TO ANODE
H+ Br-
Cu2+ I-
Ag+ OH-

If all factors below are constant, any ion will be discharged from the solution in preference to
those above it.lower cations are preferentially selected at the cathode and lower anions are
preferentially selected at the anode.
Concentration of the electrolyte
Irrespective of the position of the ion in the electrochemical series, there is a tendency to
promote the discharge of the most concentrated ion present in solution.
Nature of electrodes
Some electrodes are reactive while others are inert.
Inert electrodes: these are electrodes which do not react with electrolytes or products during
electrolysis example include platinum and graphite.
Active electrodes: theses are electrodes which react with product of electrolysis affecting the
course of electrolysis and the products of electrolysis e.g mercury and copper
Quantitative aspect of electrolysis
Faraday first law of electrolysis:
It states that the amount of any substance deposited, evolved or dissolved at the electrode is
directly proportional to the quantity of electricity passing through the electrolytic cell.
M C
Where C = quantity of electricity in coulomb
One coulomb = one ampere x one second = I x t
I = current strength in amperes
t = time in seconds

Experimentally, it has been found that one mole of electrons has a charge of 96500C.
Therefore, when one mole of a singly-charged ion is discharged at an electrode this happens:
M + + e- M
Or X- X + e-
This process requires the passage of 96500C (or the addition or removal of one mole of
electrons).
Similarly, in the discharge of one mole of a doubly charged ion at an electrode this happens:
M2+ +2 e- M
Or X 2- X + 2e-
This process requires the passage of 2 x 96500C (or the addition or removal of two moles of
electrons).
In general,then,to discharge one mole of an ion,Mn+ or Xn- ,at the electrode n x 96500C of
electricity must passed through the electrolyte.
Worked example one
What mass of magnesium is deposited at the cathode by the passage of 2.00 amperes through
molten magnesium chloride for 30 minutes?
solution
Quantity of electricity passed in coulombs = amperes x time in seconds
= 2 x 30 x 60 = 3600C
From the equation for the discharge of magnesium
Mg2+(aq) + 2e- Mg(s)
2 x96500C are required for the formation of one mole of magnesium (24g)

3600C will be required for formation of = 0.45g of magnesium.
Faraday second law of electrolysis
It states that the quantity of electricity required to liberate one mole of any element is
proportional to the charge number
Application of electrolysis
1. Extraction of sodium by electrolysis of molten sodium chloride in the downs process
2. Manufacture of sodium hydroxide by electrolysis of aqueous sodium chloride I a diaphragm

cell.
3. Manufacture of sodium chlorate (i) and sodium chlorate (v) by electrolysis of aqueous
sodium chloride.
4. Manufacture of hydrogen by the electrolysis of sodium chloride as in 1 and 2 above.
5. Manufacture of hydrogen by the electrolysis of brine (aqueous sodium chloride) as in 2

above.
6. Extraction of magnesium and calcium by electrolysis of the molten chlorides .
7. Extraction of aluminium by the electrolysis of molten aluminium oxide
8. Anodisation and dyeing of aluminium.
9. Purification of copper by electrolysis, using a lump of impure copper as the anode.
10. Electroplating, e.g chromium plating.

SUB-TOPIC 2: ELECTROLYTIC CONDUCTION
Electrolytes conduct electricity in molten or in liquid state by movement of ions
Conductivity (or specific conductance)of electrolytic solution is a measure of its ability to conduct
electricity
Conductivity measurements are used in many industry and environmental application in measuring the
ionic content in solution. for example drinking water must have a conductivity in the range 5-50msm-1
The electrical conductivity of a solution of an electrolyte is measured by determining the resistance of

solution between two flat electrodes separated by a fixed distance by electrical conductivity meter.
The resistance, R is proportional to the distance L between electrodes and inversely proportional to the
cross-sectional area, A of solution between the electrode
R= ρ
Where R=is the electric resistance measured in ohms( Ω )
L=is the distance between electrodes measured in meters or centimeters
Ρ(rho)= resistivity of the material
A =cross-section area of the electrode measured in metres squared or centimeter squared

When L =1cm and A=1cm2
R= ρ in this case ρ is known as the specific electrolytic resistance
By definition
Specific electrolytic resistance is the resistance of a given volume of electrolyte between two
electrodes of cross-sectional area 1cm2 placed between two electrodes 1cm apart at constant
temperature.
Causes of resistance in an electrolyte
 Presence of unionized water molecules which abstract conducting ions
 Collision between opposite charged ions as they migrate
 Viscosity of water due to the bonding and vander-waals forces of attraction
 Hydration which makes ions heavier
 Attraction between opposite charged ions.
In dealing with solutions of electrolytes it is more convenient to use the quantities conductance and
electrical conductivity than resistance and resistivity to minimize the contribution of each of the factors
above which can’t be easily quantified.
Conductance of solution is
The reciprocal of resistance of solution of an electrolyte is called conductance. (C = )
This implies high resistance means low conductance. units are per ohm Ω-1 or Siemens(s)
The electrical conductance of an electrolyte is due to the ions it contains, the greater the concentration
of ions the higher will be the conductance
Electrolytic conductivity ( k)
Is the reciprocal of the resistivity of an electrolyte.
K= = units of k are per ohm per meter or per ohm per centimeter

Experiment to determine electrolytic conductivity of an electrolyte
The electrical conductivity of a solution of an electrolyte is measured by determine the resistance of a

solution between two electrodes separated by a fixed distance.
 The apparatus is arranged as shown above.
 A solution of electrolyte is prepared using conductance water
 The electrolyte is placed in a conductivity cell
 The sliding contact is connected to a cathode ray oscilloscope and moved along resistance wire
AB until a point when no signals are registered.
 At the balance point = , =
 The procedure above is repeated using another electrolyte of known electrolytic k in order to
determine the cell constant
 The procedure the repeated using pure conductivity water to obtain its electrolytic
conductivity.
 The conductivity of the electrolyte is given by k electrolyte=k electrolyte in solution-k water
Note
an alternating voltage is used in order to avoid electrolysis.
Factors that affect the electrolytic conductivity of solution
in general conductance of an electrolyte depends upon the number of ions present in the solution,
therefore the greater the number of ions in the solution the greater is the conductance.
conductance depends upon the following factors
1)nature of electrolyte(type of electrolyte( weak or strong)
The number of ions produced by the electrolyte depends upon its nature
Strong electrolytes have high electrolytic conductivity because they undergo complete ionization
producing a very high concentration of ions in solution such that the resistance to conduction is low.

Weak electrolytes have low conductivity because they undergo partial ionization producing few ions in
solution making the resistance to conduction to increase
b) Temperature
For strong electrolyte, increase in temperature increases electrolytic conductivity because since they are
completely ionized in water increase in temperature decreases viscosity of water since heat weakens
the hydrogen bonds and the vander-waals forces of attraction.
For weak electrolytes which ionizes endothermically, increases in temperature increases the degree of
ionization of electrolytes. Hence, producing many conducting ions resulting in increased conductivity.
e) concentration of ions in solution
The higher, the concentration of ions in solution the higher the conductivity.
A graph of variation of electrical conductivity k with concentration
Explanation of the shape of the graph
Strong electrolytes have higher conductivity than weak electrolytes because they are considered to be
fully ionized in solution yet weak electrolytes are considered to be partially ionized in solution
For strong electrolyte:
Conductivity increases with increase in concentration at first because the number of conducting
particles per unit volume of solution increases with concentration and ions in electrolyte are still at

maximum distance apart. Beyond a certain concentration of electrolyte further increase in
concentration leads to a decreases in conductivity this because at higher concentration ions of opposite
charges are close to each other and exert a dragging effect (inter ionic interferences) which lowers the
mobility of the ions hence the decreases in conductivity
For weak electrolyte:
Conductivity increases with increase in concentration at first because the number of conducting
particles per unit volume of solution increases with concentration and the degree of dissociation is still
high beyond a certain concentration of electrolyte further increases in concentration leads to a decrease
in conductivity this is because at higher concentration the degree of dissociation decreases this leads to
a decrease in number of conducting ions per unit volume hence conductivity decreases
MOLAR CONDUCTIVITY( λ)
This is the conductance of one mole of an electrolyte in a given volume of a solution which is placed or
enclosed between two electrodes with unit cross-section area and unit length apart.
Mathematically; molar conductivity λ = or kV
where k is the electrolytic conductivity
C is concentration of the electrolyte
V = Dilution = is the volume of electrolyte containing one mole .
Units of molar conductivity
If concentration is expressed in molm-3 and electrolytic conductivity in Ω-1m-1 units of molar

conductivity λ will Ω-1 mol-1 m2
If concentration is expressed in molcm-3 and electrolytic conductivity in Ω-1cm-1 units of molar

conductivity λ will Ω-1 mol-1c m2
If concentration is expressed in moldm-3 and electrolytic conductivity in Ω-1cm-1 units of molar

conductivity λ will 1000Ω-1 mol-1c m2 ie molar conductivity will be expressed as λ =

A graph of variation of molar conductivity with dilution
For strong electrolyte
At low dilution or high concentration the molar conductivity is low this is because the ions of opposite
charge are close and exert a dragging effect on each other(inter-ionic interferences)with increase in
dilution the separation of ions increases and the dragging effect decreases. Molar conductivity therefore
increases up to a limiting value beyond which further dilution has no effect. At this point the ions can
move independently without exerting a drag on each other. The molar conductivity is the molar
conductivity at zero concentration or infinite dilution.
For weak electrolyte
At low dilution (or high concentration) the molar conductivity is low this is because the electrolyte is less
dissociated /ionized with increase in dilution degree of dissociation of electrolyte increases therefore
the number of ions per unit volume increases hence molar conductivity increases . it is not possible to
get molar conductivity at infinity dilution using this method because molar conductivity continues to
increase drastically at high dilution without reaching a limiting value.

A graph of variation of molar conductivity with concentration
For strong electrolytes
At low concentration there are few ions per unit volume and ionic interferences are low, therefore the
speed of the ions is high hence high molar conductivity at low concentration.
As concentration increases ions per unit volume increases ionic interferences increases and therefore
ionic mobility decreases hence the decrease in molar conductivity at high concentration.
By extra-polating this graph to the axis the intercept is the molar conductivity at infinity dilution
For weak electrolytes
At low concentration molar conductivity is high due to the high degree of dissociation which results into
increase in number of ions.
As concentration increases degree of dissociation decreases and the number of ions per degree
therefore molar conductivity decreases with increase in concentration.
Factors affecting molar conductivity
b)charge on the ion
the higher the charge on the ion the greater the conductivity.
e.g the electrical conductivity of magnesium chloride is greater than that of sodium chloride with both at
the same concentration because the magnesium Mg2+ gives a higher charge and higher number of ions
in solution than sodium ion Na+

c) Ionic radius
Increase in ionic radius decreases the ionic mobility and hence the decreases in conductivity.
For example in molten state the conductivity of lithium salts are greater than those of cesium salts since
the ionic radius of Li+ ion is smaller than that of Cs+
However in aqueous solution the extent of hydration affects the mobility of the ion, which in turn
affects the conductivity.
In aqueous solution Li+ ion with high charge density is heavily hydrated than Cs+ ion with low charge
density hence hydrated Li+ ion is bigger than hydrated Cs+. As a result lithium salts show lower
conductivities compared to those of cesium salts in water.
Explain each of the following observations
1. The electrical conductivity of a 0.01M solution of hydrochloric acid is greater than that of 0.001M
solution of hydrochloric acid. But the molar conductivity of 0.001M hydrochloric acid is greater than that
of a 0.01Mhydrochloric acid.
2. The molar conductivity of 0.5M ethanoic acid is less than that of 0.5Mhydrochloric acid.
KOHLRAUSCHS LAW OF INDEPENDENT MIGRATION OF IONS
It states that the molar conductivity of an electrolyte at infinity dilution is equal to the sum of the molar
ionic conductivities at infinity dilution of the ions produced by the electrolyte at a given temperature.
For example NaOH = + ̅
BaC = B +2
Note
This law can be used to determine the molar conductivities at infinite dilution for weak electrolytes
whose molar conductivities cannot be determined experimentally.
For example to determine the molar conductivity at infinity dilution of ethanoic acid which ionises as
follows CH3COOH(aq) CH3CO ̅ (aq) + H+(aq)
We require the value of the molar conductivity of sodium ethanoate, hydrochloric acid and sodium
chloride which are strong electrolyte.
Worked example
1.9.05g of anhydrous magnesium chloride was dissolved in water and the solution made up to one litre.
The electrolytic conductivity of the solution of the solution was found to be2.58x 10-4Ω-1cm-1 at
250C.calculate the molar ionic conductivity of the chloride ions at this temperature.
(RFM of MgCl2 =95, M =106Ω-1mol-1cm2)

2.calculate the molar conductivity of water at infinity dilution given that
1 Ω-1mol-1cm2 8 Ω-1mol-1cm2 and Ω-1mol-1cm2
3.Calculate the molar conductivity of ammonia solution at infinite dilution given
(λ0Ba(OH)2 =497.6 λoBaCl2=240.6 λoNH4Cl=129.8
APPLICATION OF CONDUCTIVITY
1.In determination of molar conductivity at infinity of strong electrolyte.

From the graph of molar conductivity against the square root of concentration after an experiment.
Worked example
The molar conductivity of sodium hydroxide solution at different concentration is shown below
Concentration(moldm-3) 0.01 0.04 0.09 0.16 0.25 0.36
Molar conductivity(Ω-1 mol-1 cm2) 238 230 224 217 210 202
i)draw a graph of molar conductivity against the square root of concentration
ii)explain the shape of the graph
iii)determine the value λ of sodium hydroxide
2.In determination of molar conductivity at infinity dilution for weak electrolyte using the kohlrauschs
law of independent migration of ions.
3.It can be used to determine the dissociation constant of a weak electrolyte HX
HX(aq) H+(aq) + X-(aq)
[ ][ ]
Ka = [ ]
=
α=
Worked example
Calculate the equilibrium constant Ka of 0.1M ethanoic acid given that the molar conductivity of 0.1 M
ethanoic acid is 5.2 x 10-4 Ω-1 mol-1 cm2 and is 3.9x10-2 Ω-1 mol-1 cm2 at infinity dilution.
α= = =
Ka =

4.In Determining the solubility of a sparingly soluble salt.
Worked example
A saturated solution of silver chloride has a conductivity of 1.89 x 10 -6 Ω-1 cm-1 at 298K the electrical
conductivity of water is 5.5 x 10-8 Ω-1 cm-1( AgNO3=133.4, KCl=149.9, KNO3=145 )
a)Calculate the solubility of silver chloride
KAgCl =Ksolution – Kwater
= 1.89 x 10 -6-5.5 x 10-8=1.835 x 10 -6 Ω-1 cm-1
AgCl = AgNO3 + KCl – K NO3
= 133.4+149.9-145 =138.3 Ω-1 mol-1 cm2
Since concentration of silver chloride is very small its concentration is taken as concentration at infinity
dilution
C = = =1.33 X 10 -8 molcm-3 = 1.33 X 10 -5moldm-3
b)hence determine the solubility product of silver chloride
KSP =[ ][ ] = 1 1 1 1 =1.77 x 10 -10 mol2 dm-6
In determining the ionic product of water
H20(l) H+ (aq) + ̅ (aq)
KW =[ ][ ̅ ] =CxC =C2
C= ̅
5.In Conductrimetric titration
This involves the determination of the end point during titration by measurement of conductivity other
than by use of an indicator
Experimental determination of end point by conductivity measurement

Apparatus set up
Procedure
a known volume of strong acid is placed in a conductivity cell the solution is stirred magnetically, small
volumes of strong base e.g1.0Msodiumhydroxide solution are added from the micro burette and the
resistance of the solution is measured after each addition. It important that the acid is much more
dilute than the alkali in order to minimize dilution effects which will tend to mask any conductivity. The
graph of1/R or conductivity K against volume of base added is plotted.
The end point of the titration is obtained from the intersection of the straight line portion of the graph.
Conductricmetric titration curves for acid-base reactions depends on the relative strength of the acids
and bases used.
a) Strong acid vs strong base e.g HCl and NaOH

Initially conductivity is high because HCl is a strong electrolyte which completely ionises into many
highly conducting H+ ions.
Along AB conductivity decreases with addition of the base because the highly conducting H+ ions are
being neutralized by hydroxide ions to form water and are being replaced by less conducting Na+ ions
due to the reaction
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)
At B It’s the end point indicated by a minimum conductivity due to the conductivity of Na+ and Cl- ions
only
Beyond the end point conductivity increases due to the addition of excess sodium ions and hydroxide
ions
Note the rise is not as steep as the fall in AB because the sodium ions and hydroxide ions added are less
conducting than the hydrogen ions.
b)strong acid vs a weak base e.g HCl and NH3
Initially conductivity is high because HCl is a strong electrolyte which completely ionises into many
highly conducting H+ ions.
Along AB conductivity decreases with addition of the base because the highly conducting H+ ions are
being neutralized by hydroxide ions to form water and are being replaced by less conducting NH+ ions
due to the reaction
HCl(aq) + NH4OH(aq) NH4Cl(aq) + H2O(l)
At the end point indicated by a minimum point conductivity due to the conductivity of NH4+ and Cl-
ions only.

After the end point the ionisation of a weak base added is suppressed by ammonium ions from the salt
NH4Cl formed.
NH4Cl(aq) NH4+(aq) + Cl-(aq)
NH4OH(aq) NH4+(aq) + ̅ (aq)
The equilibrium lies to the left consequently conductivity of the few ̅ is negligible leading to a
constant conductivity
c)weak acid vs strong base e.g CH3COOH and NaOH
Initially conductivity is low because ethanoic acid is a weak electrolyte that partially ionises into few H+
ions
Along AB conductivity falls slightly as the base is added because the few H+ ions from the ionisation of
ethanoic acid is/are being neutralized.
Along BC conductivity gradually increases due to increase in number of ions CH3CO ̅ and Na+ from the
completely ionised salt CH3COONa formed during neutralization
CH3COOH (aq) + NaOH(aq) CH3COONa(aq) + H2O(l)
At C conductivity is due to CH3CO ̅ and Na+ ions only
After the end point conductivity increases further hue to excess hydroxyl ions added from sodium
hydroxide.

d) weak acid vs a weak base e.g CH3COOH and NH4OH
Initially conductivity is low because ethanoic acid is a weak electrolyte that partially ionises into few H+
ions
Along AB conductivity falls slightly as the base is added because the few H+ ions from the ionisation of
ethanoic acid is/are being neutralized.
Along BC conductivity gradually increases due to increase in number of ions CH3CO ̅ and NH4+ from the
completely ionised salt CH3COONH4 formed du ring neutralization
CH3COOH (aq) + NH4OH(aq) CH3COONH4(aq) + H2O(l)
At C conductivity is due to CH3CO ̅ and NH4+ ions only after complete neutralization.
Along CD conductivity remains constant because the ammonia solution added is suppressed by the
ammonium ions from the salt formed.
QUESTIONS
The table below shows the variation of conductivity with volume of ammonia when inert electrodes
connected to a conductivity meter were immersed in 50cm3 of 0.025M zinc nitrate solution and 2cm3
portions of 0.5M ammonia added at intervals.
Volume of ammonia solution addedcm3 0 2 4 6 8 10 12 14
Conductivity of resultant solutionΩ-1cm-1 1.2 1.16 1.12 1.08 1.05 1.045 1.06 1.10
i)draw a graph of conductivity of solution against volume of ammonia
ii)determine the volume of ammonia solution that gave the lowest conductivity.
iii)determine the formula of the species present in the solution.

SUB-TOPIC 3 ELECTROLCHEMICAL CELLS
ELECTROLCHEMICAL CELLS
An electrochemical cell is a device capable of generating electrical energy from chemical

reactions.
An electrochemical cell can be created by placing metallic rod into an electrolyte where
a chemical reaction generates an electric current. Electrochemical cells which generates
an electric current are called voltaic cells or galvanic cell
When a metal rod is dipped in solution containing its ions an equilibrium is set up.
There is a tendency for metal ions from the metal lattice to pass into solution and form
hydrated metal cations leaving electrons on the metal strip, therefore the metal strip
becomes negatively charged.
M(s) Mn+(aq) + ne-
there is also a tendency for the hydrated metal ions in solution to gain electrons from
the metal and form metal atoms which are then deposited on a metal strip in this case
the metal will become positively charged.
Mn+(aq) + ne- M(s)
A dynamic equilibrium will be established when the rate at which ions are leaving the
surface is exactly equal to the rate at which they are joining it again.
Mn+(aq) + ne- M(s)
The difference is that for some metals the equilibrium lies to the left(these give extra
positive ions into the solution),while for others it lies to the right(these take positive
ions out of solution)
The metal, therefore acquire a negative or positive charge respectively depending upon
which process predominates.
The difference between the negativeness of the metal and the positiveness of the solution
around it, called potential difference could be recorded as voltage. The bigger the difference, the
bigger the voltage
The potential difference generated between the metal and solution of its ions when they are in
contact is called electrode potential ( E).
The value of the electrode potential for a particular metal depends on

 the concentration of the metal ions,
 temperature,
 charge on the ions and
 pressure of gas electrode.
The absolute value of the potential difference cannot be measured since the measurement
would mean inserting another electrode into the electrolyte and this leads to formation of
another potential difference.
A metal dipping into a metal salt solution is called a half cell /electrode
a metal strip or rod which is dipped into the electrolyte is called an electrode.
Types of Half cells/electrodes
a-metal-metal ion electrode
This is made up of a metal rod dipped into solution of its ions
For example zinc metal dipping into a solution of zinc sulphate Zinc
Half cell symbol Zn(s)/Zn2+ (aq)
Half cell equation Zn2+ (aq) + ̅ Zn(s)
b-Gas electrode
This consist of a gas under pressure on the surface of a catalyst
For example hydrogen in contact with platinum electrode in the hydrogen electrode
Half cell symbol Pt/H2(g),H+(aq)
Half cell equation 2H+ (aq) + ̅ H2(g)
c-Ion-ion electrode
This consists of an inert metal in contact with a solution containing ions in two different
oxidation states.
For example a platinum electrode dipped into a solution containing Fe2+ and Fe3+
Half symbol Pt/Fe2+ (aq) ,Fe3+(aq)
Half cell equation Fe3+(aq) + ̅ Fe2+ (aq)

d-Metal- metal sparingly soluble salt electrode
This is made up of a piece of metal coated with the desirable sparingly soluble salt then
the set up immersed into a solution with an anion common to that of the sparingly
soluble salt of the metal.eg
Silver metal coated with silver chloride immersed in a chloride solution.
Half- cell symbol Ag(s)/AgCl(s) ,Cl-(aq)
Half- cell equation AgCl(s) + ̅ Ag(s) + Cl-(aq)
Electrochemical cell/galvanic cell
For relative measurements of potentials of various metals in various solutions two half
cells are connected together to make galvanic cell
Typical galvanic cell consists of two metallic electrodes e.g zinc and copper immersed
into different solutions i.e zinc sulphate and copper sulphate respectively. The solutions
are electrically connected by a salt by a salt bridge. The metallic electrodes are
connected to high resistance voltmeter.as illustrated in the diagram below.
Electrons will flow along the wire from the electrode with higher concentration of
electrons to the one with lower electron concentration
By convention; the negative electrode is put on the left and the positive electrode on the
right of the diagram
In the daniell cell, the zinc is the negative electrode because it has the more negative
electrode potential; it constitutes the left hand electrode (the anode) and the electrons
travel from the zinc through the wire to the positive copper electrode. This means the
reaction in the zinc half-cell must be

LHS Zn(s) Zn2+ (aq) + ̅
The copper is the positive electrode because it is has a more positive electrode potential,
it constitutes the right hand electrode (cathode) and the reaction in copper half-cell is
the one that absorbs the electrons travelling round the circuit.
RHS Cu2+(aq) Cu(s) + ̅
The overall equation
Zn(s) + Cu2+(aq) Cu(s) + Zn2+ (aq)
If the value of the current is negligible (high resistance voltmeter is used) the measured
potential difference between the electrodes is equal to the electromotive force (EMF) of
the galvanic cell.
The measurements of electromotive force are usually made under standard conditions:
 Temperature of 250C or 298K

 Pressure of gasses at 1.0 atm
 Electrolyte solution of 1.0 moldm-3
Electromotive force measured under standard conditions has a notation Eθ
EMF of galvanic cell is a resulting sum of potential difference of the anode and cathode:
Eθ = Ecathode – Eanode
A cell diagram
The galvanic cell is schematically described by the cell notation or cell diagram
this is an agreed way of depicting cells on paper for example, in the galvanic cell above
Zn(s) Zn2+(aq) Cu2+(aq) Cu(s)
By convention:
 The two parallel lines represent the salt bridge.
 Each single line represents the change of phase between aqueous ions and solid metal
 Broken line represents a porous partition(for some cell)
 A comma represents separation between two elements in different oxidation state
 Pt represent platinum electrode

 The electrode through which electrons flow are placed at the start and the finish of the
cell diagram.
 The half-cell undergoining oxidation is written on the left of the diagram.
 The half-cell undergoing reduction is written on the right of the diagram.
 Oxidation will take place in the half-cell with the more negative standard electrode
potential
 Reduction will take place in the half-cell with the less negative(more positive) standard
electrode potential.
 The electrode where reduction takes place is called the cathode and where oxidation
takes place is the anode
 The e.m.f of a combination of two half-cells is the difference between the e.m.f of the half
cell on the right-hand side minus the e.m.f of the half-cell on the left-hand side, ie
Ecell = Eθright - Eθleft
Note
The salt bridge
The salt bridge is included to complete the electrical circuit but without introducing any more
bits of metal into the system it is just a glass tube filled with an electrolyte like potassium nitrate
solution. The ends are stoppered by bits of cotton wool. This stops too much mixing of the
contents of the salt bridge with contents of the two beakers. The electrolyte in the salt bridge is
chosen so that it does not react with the contents of either beaker.
The voltmeter
High resistance voltmeter is used to avoid any flow of current through the circuit such that
maximum possible voltage is measured. This is called the electromotive force e.m.f. the e.m.f
measured under standard conditions is given the symbol cell

STANDARD ELECTRODE POTENTIAL
Standard electrode potential is the electromotive force measured in the galvanic cell consisting
of the half cell with the electrode under standard conditions and half -cell with the standard
hydrogen electrode
THE STANDARD HYDROGEN ELECTRODE
Standard hydrogen electrode(SHE) consists of platinum foil coated by platinum black,

which is dipped into an acidic solution with concentration of hydrogen ions(H+)
1.0moldm-3 at 298k and which is in contact with gaseous hydrogen bubbling at
1.0 atmospheres around the electrode.
As the hydrogen gas flows over the platinized platinum, equilibrium is set up between
hydrogen molecules and hydrogen ions in solution. The reaction is catalyzed by platinum
2H+ (aq) + ̅ H2(g)
This is the equilibrium that we are going to compare all the others with.
Platinum does not take part in the reaction but it serves as a catalyst for oxidation-reduction
reaction of hydrogen
 It acts as an inert connection to the H2/H+ system because there is no tendency of

platinum to form ions
 It allows hydrogen gas to get adsorbed on its surface
 Being platinized, the surface area for the establishment of equilibrium between
hydrogen gas and hydrogen ions is increased.
Standard electrode potentials are measured relatively to the standard hydrogen electrode,
potential of which is defined as 0.0volts

Measuring the standard electrode potential of a metal in a solution of its ions.
The metal plate is dipped in a solution containing 1.0moldm-3solution of the metal ions. The
electrode is connected to the positive terminal of the voltmeter and the standard hydrogen
electrode is connected to the negative terminal of the voltmeter and the two solutions by
means of a suitable salt bridge, as shown below.
The maximum potential difference, known as the e.m.f of the cell is then measured by a high-
resistance voltmeter in volts (because it withdraws negligible current from the cell set up). Since
the standard hydrogen electrode has a potential of 0.00V, the reading on the voltmeter is the
standard electrode potential of the metal.
Standard electrode potential Eθ is the potential value measured with respect to a standard
hydrogen electrode at conditions of 1 atmosphere, 298K and 1.0moldm-3 concentration of ions in
the solution. or
The e.m.f measured when the metal is in solution of its ions coupled to a standard hydrogen
electrode is called the standard electrode potential for the metal/metal ion combination. The
hydrogen electrode must be the left-hand electrode, and everything must be under standard
conditions (all ion concentration 1.0moldm-3, temperature of 298K, and gas pressure of 1.0
atmosphere.
By convention, standard electrode potentials are recorded as standard reduction potentials.

this is because the second electrode on the right is being reduced by gaining electrons from the
standard hydrogen electrode As EθMn+/M = + xxV
The reaction is written with the reduced species on the right i.e
Oxidised species + ne reduced species
The sign of the standard electrode potential Eθ value
When the metal M is above hydrogen in the reactivity series e.g Zinc or Magnesium or
Aluminium, electrons will flow from the metal rod to the standard hydrogen electrode and

hence the metal electrode becomes negative with respect to the hydrogen electrode. The minus
(-) sign signifies that the electric potential on the electrode is more negative than the potential on
the standard hydrogen electrode.
When the metal M is below hydrogen in the reactivity series e.g copper or gold or silver
electrons will flow from the standard hydrogen electrode to the metal electrode and the
electrode potential will be registered as positive. The plus (+) sign signifies that the standard
hydrogen potential has the more negative potential
Electro-chemical series
Standard electrode potentials of metals are arranged in electrochemical(galvanic)series
The arrangement of elements according to their electrode potentials gives rise to the electro-
chemical series in which the most reactive metals has the most negative reduction potential and
it is the one the top.
The more negative a reduction potential is the easier it is for the oxidation process to take place
and the more difficult it is for the reduction process to take place.
The elements or species with the greatest negative electrode potentials have a greater tendency
to donate electrons and therefore exist as the anode. Therefore these metals are strong reducing
agents.
Consider the potential of the following electrodes
electrode EθV
Li+(aq)/Li(s) -3.04
K+(aq)/K(s) -2.92
Na+(aq)/Na(s) -2.82
Ca2+(aq)/Ca(s) -2.71
Mg2+(aq)/Mg(s) -2.31
Al3+(aq)/Al(s) -1.66
Zn2+(aq)/Zn(s) -0.76
Fe2+(aq)/Fe(s) -0.44
Pb2+(aq)/Pb(s) -0.13

H+(aq)/H2(s) 0.00
Cu2+(aq)/Cu(s) +0.34
Ag+(aq)/Ag(s) +0.80
Au2+(aq)/Au(s) +1.50
Measuring redox potentials for other systems
Since the electrochemical series is essentially about redox reactions, it would make sense to
include reducing agents and oxidizing agents other than metals and their ions-for example,
oxidizing agents like chlorine, acidified potassium dichromate(vi) or acidified potassium
manganate(vii).all of these have measurable Eθ often called redox potentials rather than
electrode potentials
a)Systems involving gases
For example to measure the electrode potential for the chlorine system,
Cl2(g) +2e 2Cl-(aq) an electrode similar to hydrogen is used.
Chlorine gas is bubbled over platinum electrode which is immersed in a solution containing
chloride ions with concentration 1.0moldm-3 and coupled this to standard hydrogen electrode.
b)Redox ions
The Fe2+/Fe3+ system
Iron(ii) ions are easily oxidised to iron(iii) ions and iron(iii) are fairly easily reduced to
iron(ii) ions.
Fe3+(aq) +e Fe2+(aq)
To measure the redox potential of this you would simply insert a platinum electrode into a
beaker containing a solution containing both iron(ii) and iron(iii) ions of concentration
1.0moldm-3 with respect to both and coupled this to a hydrogen standard electrode.
c)In acidified potassium manganate(vii)
MnO-4(aq)+8H+(aq)+ 5e Mn2+(aq)+4H2O(l)
To measure the redox potential of this you would simply insert a platinum electrode in
the a beaker containing all the ions MnO-4 ,H+(aq) and Mn2+ all at 1.0moldm-3

An updated electrochemical series looks like this
electrode EθV
Li+(aq)/Li(s) -3.04
K+(aq)/K(s) -2.92
Na+(aq)/Na(s) -2.82
Ca2+(aq)/Ca(s) -2.71
Mg2+(aq)/Mg(s) -2.31
Al3+(aq)/Al(s) -1.66
Zn2+(aq)/Zn(s) -0.76
Fe2+(aq)/Fe(s) -0.44
Pb2+(aq)/Pb(s) -0.13
H+(aq)/H2(s) 0.00
Cu2+(aq)/Cu(s) +0.34
Ag+(aq)/Ag(s) +0.80
Au2+(aq)/Au(s) +1.50
MnO-4(aq),H+(aq),Mn2+(aq) +1.52
F2(g)/2F-(aq) +2.87
Factors which affects the magnitude of standard electrode potential of a metal and hence the
overall e.m.f of a cell
The factors are generated from the process that occurs when a metal dipped into solution
containing its ions ionises to produce electrons hence generate electrode potential
M(s) Mn+ (aq) +n ̅
Sublimation hydration
M(g) ionisation Mn+ (g) +n ̅
The value of standard electrode potential depends on the overall enthalpy change which
depends on sublimation energy, ionization energy and hydration energy.
Sublimation energy
This is the energy required to convert one mole of a solid metal into one mole of gaseous atom
the process is endothermic the higher the sublimation energy, the more positive the electrode
potential

Ionization energy
This is the energy required to convert one mole of gaseous atom into one mole of gaseous ions
the process is endothermic, the higher the sublimation energy the more positive the electrode
potential.
Hydration energy
This the energy liberated when one mole of gaseous ions is complexly surrounded by water
molecules the process is exothermic the more negative the hydration energy the more negative
the electrode potential.
note
if ΔHsub + IE ΔHhydration then Eθ is positive
if ΔHsub + IE ΔHhydration then Eθ is negative
if Δsub + IE = ΔHhydration then Eθ is zero( only possible for standard hydrogen electrode.
Standard electrode potential and standard free energy change
There is a relationship between electro chemistry and thermo chemistry. In the electrode
reaction
Mn+ (aq) + n ̅ M(s)
If the standard electrode potential is Eθ then the value of the standard free energy change ΔGθ
At the same temperature is given by ΔGθ = -nFEθ
Where n is the number of electrons transferred in the electrode reaction
F is the faradays constant
Eθ overall emf of the cell
Example
The equation for some half-cell conventions are given below
SO42- (aq) +H2O(l) +2e SO32- (aq) + 2 ̅ H(aq) Eθ = -0.90v
Cu2+ (aq) + 2e Cu(s) Eθ = +0.337v
a)write the
i)convention for the combined cells

Pt(s)/ SO32- (aq) 2 ̅ H(aq) ,SO42- (aq) // Cu2+ (aq) / Cu(s)
ii) Overall cell equation
SO32- (aq) + 2 ̅ H(aq SO42- (aq) +H2O(l) +2e
Cu2+ (aq) + 2e Cu(s)
SO32- (aq) + 2 ̅ H(aq + Cu2+ (aq) SO42- (aq) +H2O(l) + Cu(s) overall
b)calculate the
i)emf of the cell
Ecell = ERHS -ELHS =0.337 - -0.90 =+1.237v
ii)the maximum work done by the cell
ΔGθ = -nFEθ
= -2 x96500x1.237 = -238.741kjmol-1
Application of standard redox potentials
1-Predicting an e.m.f value of a cell
example
Predict the cell reaction and calculate Ecell given that
Sn4+ (aq)/Sn2+ (aq) Eθ =+0.15V
Fe3+ (aq)/Fe2+ (aq) Eθ =+0.77V
From the size of the Eθ values for the half-cells it is apparent that Fe3+ has a greater attraction for
electrons than Sn4+,and so Fe3+ should be able to take electrons from Sn2+ to give Fe2+ and Sn4+
.this suggests that the half-reaction for tin should be reversed to obtain the actual equation for
the process, ie
Sn 2+ (aq) Sn4+ (aq) +2 ̅
Fe3+ (aq) +2 ̅ Fe2+ (aq)
Sn 2+ (aq) + Fe3+ (aq) Sn4+ (aq) + Fe2+ (aq)
The cell is therefore written as
Pt(s)/ Sn 2+ (aq) , Sn4+ (aq) // Fe3+ (aq) ,Fe2+ (aq)/ Pt(s)

Ecell = ERHS - ELHS =0.77-0.15 = +0.62V
When two electrodes combine to form a cell the value of Eθ for the cell must be positive if the
cell reaction is to happen spontaneously.
A redox reaction will go to almost to completion between two redox systems which differ by
0.3v or more in their electrode potentials.
Some reactions which are predicted to be feasible do not always occur this is because kinetic
factors may make the reactions so slow that no change can be observed
2-It shows the order of reactivity of elements. The metals decrease in reactivity as the series
descends, whilst the reverse is the case for non-metals.
3-It shows which elements can displace each other from solutions of their salts, e.g iron will
displace copper from copper (ii) sulphate solution since it is higher up the series similarly;
chlorine will displace bromide ions from their solutions:
Cl2(g) + 2Br-(aq 2Cl-(aq) + Br2(aq)
4-It shows why zinc and aluminium may be used to protect the surface of iron- they are higher
up in the series and so will dissolve first.
5-It can be used to predict the products discharged at the electrode during electrolysis but it
should be remembered that other factors, such as the nature of the electrodes etc also affects.
b) State whether the reaction is feasible or not give a reason for your answer
Its is feasible because overall emf is positive and standard free energy change is positive
Some standard electrode potentials for metal/metal ion half-cells
Types of emf /voltaic/galvanic cells
Primary cell
This is a voltaic cell in which the chemical reaction producing emf isn’t satisfactory reversible and
therefore cannot be recharged by application of a current e.g a Daniel cell, the lechlanche cell (dry cell, a
fuel cell.
Lechlanche cell
Is made up of zinc container encasing the cell(anode),a graphite rod surrounded by a layer of
manganese (iv) oxide(cathode) a mixture of pasted zinc chloride and ammonia chloride in
water(electrolyte).
At the anode

Zn(s) Zn2+ (aq) + 2 ̅
At the cathode
2NH4+(aq) + MnO2(s) + 2 ̅ Mn2O3 (s) + 2NH3(g) + H2O(l)
Overall
2NH4+(aq) + MnO2(s) + Zn(s) Zn2+ (aq) + Mn2O3 (s) + 2NH3(g) + H2O(l)
Advantage of a dry cell
 Maintains a stable voltage over a long period of time
 Convenient and portable since its components are pastes which are tightly sealed from the
environment.
 Its cheap
Disadvantage
 Cannot be recharged
Fuel cell
It’s a primary cell in which the reactants are continuously replaced as the products are continuously
removed the most common fuel cells generate electricity from hydrogen and oxygen using platinum
electrodes and a solution in alkali
At the anode
2H2(g) + 4 ̅ (aq) 4H2O(l) + 4 ̅
At the cathode
Overall
2H2 (g) + O2(g) 2H2O(l)
Secondary cells
This is a cell that can be recharged by passing electricity through it from the external source
Atypical secondary cell is a lead storage battery or lead accumulator its made up of lead metal as the
anode, a grid of lead packed with lead (iv) oxide (cathode) immersed in desirably dilute sulphuric acid as
the electrolyte.
At the anode

Pb(s) + SO42- (aq) PbSO4(s) + 2 ̅
At the cathode
PbO2(s) +4H+(aq) + SO42- (aq) + 2 ̅ PbSO4(s) + 2H2O(l)
Over all
PbO2(s) +4H+(aq) + 2SO42- (aq) + Pb(s) 2 PbSO4(s) + 2H2O(l)
From the overall equation for the cell reaction if the cell continuous produces current the sulphuric acid
gradually gets dilute as the H+ and SO42- ions are used up.
Recharging of the cell connected it to an external source of electricity triggers the reaction.
PbSO4(s) + 2 ̅ Pb(s) + SO42- (aq)
PbSO4(s) + 2H2O(l) PbO2(s) +4H+(aq) + SO42- (aq) + 2 ̅
This produces more hydrogen and sulphate ions which combine to form sulphuric acid.
WORKED OUT QUESTIONS.
1.The standard electrode potential for some standard half cells are shown below
Fe3+(aq)/ Fe2+(aq) Eθ =+0.76V
I2(g)/I- (aq) Eθ = +0.54V
a) write the (i) cell convention for the combined cell
Pt(s) / I-(aq)/I2 (aq) // Fe3+(aq)/ Fe2+(aq)/Pt(s)
(ii) the equation for the over all reaction
Half equation

2I- (aq) I2(aq) + 2e
2(Fe3+(aq) + e Fe2+(aq) )
Over all equation
2Fe3+(aq) + 2I- (aq) I2(aq) + 2Fe2+(aq)
b)Calculate the emf of the cell
Ecell = ERHS -ELHS =0.76-0.54 = +0.22v
c)State what is observed at each electrode
i)at the anode the colourless solution turns brown
ii)at the cathode the brown solution turns green
2. The standard electrode potential for some standard half cells are shown below
Half cell Eθ (V)
Fe2+(aq)/ Fe3+(aq)/Pt(s) -0.771
Cr3+(aq) ,Cr2O72- (aq) ,H+(aq)/Pt(s) -1.33
a)write the cell notation for the cell formed when the two half-cells are connected
by convention half cells are written as reduction and more negative as LHS
Pt(s)/Fe3+(aq)/ Fe2+(aq) Eθ = +0.771V
Pt(s)/ Cr2O72- (aq) ,H+(aq), Cr3+(aq) Eθ = +1.33V
Pt(s)/Fe2+(aq)/ Fe3+(aq)// Cr2O72- (aq) ,H+(aq), Cr3+(aq) / Pt(s)
b)write equation for the half reaction
at the anode Fe2+(aq) Fe3+(aq) + e
at the cathode Cr2O72- (aq) + 14H+(aq) + 6e 2Cr3+(aq) + 7H2O(l)
overall equation
Cr2O72- (aq) + 14H+(aq) + 6 Fe2+(aq) 2Cr3+(aq) + 6Fe3+(aq) + 7H2O(l)
c)Calculate the emf of the cell
Ecell = ERHS -ELHS =1.33-0.771 = +0.659v

3. The standard electrode potentials for the system Ag(s)/AgCl(s)/Cl-(aq) /CuCl2(aq)/Cu(s) are +0.223
and+0.340volts respectively.
a) write the equation for the half-cell reactions that take place at the
i)anode Ag(s) + Cl-(aq) AgCl(s) + e
ii) cathode Cu2+ (aq) + 2e Cu(s)
b)write the overall equation for the cell reaction
2Ag(s) + 2Cl-(aq) + Cu2+ (aq) Cu(s) + 2 AgCl(s)
c)Calculate
i)the emf of the cell
Ecell = ERHS -ELHS =0.34-0.223 = +0.117v
ii)the standard free energy of the cell
ΔGθ = -nFEθ
= -2 x96500x0.117 = -22.581kjmol-1
d) state whether the reaction is feasible or not give a reason for your answer
feasible because Ecell is positive or because ΔG is negative
4.The equation for some redox reactions are given below
3Zn(s) + 6 ̅ (aq) + BrO3-(aq) +3H2O(l) 3Zn(OH)42- (aq) + Br-(aq)
a)write the half cell reaction taking place at each electrode
i)at the anode Zn(s) + 4 ̅ (aq) Zn(OH)42- (aq) + 2e
ii)at the cathode BrO3-(aq) +3H2O(l) +6e Br-(aq) + 6 ̅ (aq)
b)write the cell notation of the cell made by combining the electrode
Zn(s) / ̅ (aq) , Zn(OH)42- (aq)// BrO3-(aq),Br-(aq) , ̅ (aq)/Pt(s)
The table below shows the electrode potentials for some group( i) metals
Electrode Li+/Li Na+/Na K+/K Rb+/Rb Cs+/Cs
Eθ volts -3.09 -2.71 -2.92 -2.99

State and explain the trend in variation of standard electrode potential of group (i)
Electrode pontetials generally inceases from sodium to rubidium
From sodium to rubidium ,atomization energy,ionization energy and hydration energy decreases as full
energy level is added from one element to the next and as ionic radius increases but both atomization
energy and ionization energy decreases more rapidly than hydration energy thus making the electrode
potential more negative.
However,the electrode pontential of lithium is abnomally high.lithium has higher sublimation and
ionization energy due to its small ionic radius,but due to its high charge density it attracts a pool of
water molecules and become heavily hydrated which results in abnomally high enthalpy of
hydration,this off sets the large enthalpy of sublimation and ionization giving lithium abnomally high
negative value of electrode potential.
end

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Table of Contents

AN INTRODUCTION TO PHYSICAL CHEMISTRY ............................................................................................. 3

HOLISTIC APPROACH TO PHYSICAL CHEMISTRY Page 1

HOLISTIC APPROACH TO PHYSICAL CHEMISTRY Page 2

There are three main objectives in studying chemistry, these are:

 To discover as much as we can about the behaviour of different kinds of matter.

Organic chemistry is concerned with chemistry of carbon compounds

HOLISTIC APPROACH TO PHYSICAL CHEMISTRY Page 3

The entire universe is made up of two things matter and energy.

Space is that which is occupied by matter

HOLISTIC APPROACH TO PHYSICAL CHEMISTRY Page 4

The diffusion of gasses is demonstrated by grahams law of diffusion

1.80 The kinetic theory of matter

The main points of the theory are:

State of matter: solid, liquid and gas

HOLISTIC APPROACH TO PHYSICAL CHEMISTRY Page 5

 Interco version of the physical states

HOLISTIC APPROACH TO PHYSICAL CHEMISTRY Page 6

Melting is the process by which a solid changes to a liquid at constant temperature.

Melting point is a fixed temperature at which a solid changes to a liquid

Evaporation is a process by which liquid changes to a gas .eventually a temperature is reached

Boiling point is a constant temperature at which a vapour pressure of a liquid is equal to

Boiling point is affected by

HOLISTIC APPROACH TO PHYSICAL CHEMISTRY Page 7

 Comparison of physical properties between solids, liquids and gases

1.93 Gaseous state of matter

1.94 kinetic theory of gasses

According to kinetic theory:

i) Gasses consists of small particles called molecules

HOLISTIC APPROACH TO PHYSICAL CHEMISTRY Page 8

viii) lighter gas molecules move faster than heavy molecules.

1.94 Basic gas laws

This law can be stated in mathematical terms as

Where V is the volume at pressure P and K is a mathematical constant

Graphical representation of Boyles law

From Boyles law:

From data: 87000Pa

This law can be stated in mathematical terms as

Where V is the volume at temperature T and K is a mathematical constant.

HOLISTIC APPROACH TO PHYSICAL CHEMISTRY Page 10

-2730C or 0K is theoretically the lowest temperature possible.

Kinetic theory of gases and Charles law

According to Charles law =

From data = 250cm3

HOLISTIC APPROACH TO PHYSICAL CHEMISTRY Page 11

= (100 + 273) = 373K

The general gas laws

This implies that V or PV T and PV = KT or = K where K is a constant.

The general gas equation is stated as:

According to the general gas law: =

From the data = 76 cm3 , = 85000Pa , = (37 + 273) = 310K

HOLISTIC APPROACH TO PHYSICAL CHEMISTRY Page 12

( where c is a constant and n is amount of a gas in moles)

The ideal gas equation

Boyles law: V ( n,T constant)

Charles law: V T (n, P constant )

Avogadro’s law: V n ( P,T constant )

So that the ideal gas equation is:

HOLISTIC APPROACH TO PHYSICAL CHEMISTRY Page 13

For one mole of a gas at standard temperature and pressure (stp)