FEDERAL UNIVERSITY, LAFIA

FACULTY OF SCIENCES
DEPARTMENT OF CHEMISTRY
CHM 111- INTRODUCTORY PHYSICAL CHEMISTRY
BY: A.U AUGUSTINE and J.C ONWUKA
Physical quantities and unit: The physical quantities understood as consisting of numerical magnitude and unit.
International system of unit. Base unit ,mass, length ,time, current, amount of substance. The mole concepts
and the Avogadro constant. Determination of relative masses .Chemical reaction stoichiometry. Electrolysis:
The factors affecting the mass of a substance librated during electrolysis.
Equilibria: Chemical equilibrium , Factors affecting equilibrium , Le’ Chaterlier’s principle. Ionic
equilibria ;Bronsted -Lowry theory of acid and bases. Strong and weak acid in terms of conductivity. Strong
and weak electrolyte. Ionic production of water (Kw). pH. and calculation. pH indicators. Choice of
indicators. Buffer solution. Phase equilibria. Chemical kinetics: Simple rate equation ; order of reaction ; rate
constant. Half life. State and kinetic theory of matter. Thermochemistry and chemical energetic. Standard
enthalpy changes of reaction. Hess law.

DEFINITION OF PHYSICAL CHEMISTRY

Physical chemistry is defined as a branch of chemistry concerned with the application

of the techniques and theories of physics to the study of chemical systems. It can also be
defined as the study of macroscopic, atomic, subatomic and particulate phenomena in
chemical systems in terms of laws and concepts of physics such as motion, energy, force,
time, thermodynamics, quantum chemistry, statistical mechanics and dynamics. Again, it is
a branch of chemistry that deals with physical properties and structures of matter, and the
laws governing their chemical interaction.

Some of the relationships that physical chemistry strives to resolve include the effects
of:

(i) Intermolecular forces that act upon the physical properties of materials (plasticity)
tensile strength, surface tension in liquids
(ii) Reaction kinetics on the rate of reaction
(iii) The identity of ions on the electrical conductivity of materials.
(iv) Surface chemistry and electrochemistry of membrane

1
PHYSICAL QUANTITIES AND UNITS

Physical quantity Value Units

Avogadro’s constant 6.02 x 1023 mol-1

Electron charge 1.602 x 10-19 C

Electron mass 9.109 x 10-31 Kg

Faraday’s constant 96500 C

Gas constant 82.053 cm3 atmk-1mol-1

8.314 JK-1 mol-1

Ionic product of water at 298K 1.00 x 10 -14 mol2 dm-6

Neutron mass 1.675 x 10-27 Kg

Planck’s constant 6.626 x 10-34 Js

Proton mass 1.673 x 10-27 Kg

Specific heat capacity of water 4.18 Jg-1K-1

Speed of light (in vacuum) 3 X 108 ms-1

SOME PHYSICAL QUANTITIES AND THEIR INTERNATIONAL SYSTEM OF UNIT (S.I

UNITS)

THE S.I BASE UNITS

QUANTITY S.I UNIT SYMBOL

Mass Kilogram (kg) M

2
 Length Metre (m) L

Time Seconds T

Current Ampere, (A) I

Temperature Kelvin (k) T

Amount of substance Mole (mol) N

Luminous intensity Candela (cd) I

A SELECTION OF DERIVED UNITS

Physical quantity Derived unit Name of derived unit

Force 1kg ms-2 Newton, N

Pressure 1kgm-1 s-2 Pascal, pa

Energy 1kgm2 s-2 Joule, J

1Nm

1pam3

Power Kgm2 s-3 Watt, w

1Js-1

COMMON SI PREFIXES

PREFIX: Z a f p n

NAME: Zepto atto femto pico nano

FACTOR: 10-21 10-18 10-15 10-12 10-9

3
PREFIX: µ m c d k m G T

NAME: micro milli centi deci kilo mega giga tera

FACTOR: 10-6 10-3 10-2 10-1 103 106 109 1012

Conversion relating length, mass and volume

4
Example 1: convert 1.47mi to inches
Soln
? inches= 1.47miles
You have to do the following conversions: miles-feet-inches
5280 ft 12∈ ¿ ¿
? = 1.47mi X X 1 ft = 9.31X 10 in
4
1 mi

Example 2: a sample of aluminium has a mass of 0.234mg, what is the mass in kg?
1000mg= 1g
0.234mg=? 0.234/1000 = 2.34 X 10-4g
1000g=1kg

2.34 X 10−4
2.34 X 10-4g = ?kg => kg
1000
= 2.34X10-7kg
Example 3: How many cubic inches are there in 1000cm 3

Soln

1 inch= 2.54cm

1 3
? inches3 = 1000cm3 = ( ¿ X 1000 = 61.0 in3
2.54

Example 4: Express 1.0 gallon in milliliters

Soln

5
Gallons---quartz----litres----millilitres

Energy conversion

Example 5

Percentage conversion

Example 6

DENSITY AND SPECIFIC GRAVITY

6
They are often expressed as g/mL or g/cm3 units

Example7:

Example 8

Express the density of mercury in lb/ft3 (the density of mercury is 13.59g/cm3)

SPECIFIC GRAVITY

7
Example 9

HEAT AND TEMPERATURE

The temperature is measured by mercury in-glass thermometer. mercury is used as the

liquid because it expands more than the other liquids as the temperature rises. In scientific
work, temperature is often expressed in Kelvin scale. Other units of temperature are the
Celsius and Fahrenheit scales. The relationship among the three units could be expressed
as follows:

K= oC+273.15

8
Example 11.

Exercises

'

THE MOLE CONCEPT AND AVOGADRO’S CONSTANT.

Chemists use a unit called mole for counting the number of particles (including
atoms, molecules, ions and electrons) in substances.

The mole is defined as the amount of substance containing the same number of
particles as the number of carbon atoms in exactly 12g of carbon -12. The particles may be
atoms, molecules, ions or electrons.

One mole = 6.02 x 1023 particles

1 mole of carbon atoms = 6.02 x 1023 C atoms

2 moles of Na+ ion = 2 x 6.02 x 1023 Na+ ion

9
1 mole of NaCl formula unit = 6.02 x 1023 NaCl formula unit

3 moles of CO2 molecules = 3 x 6.02 x 1023 CO2 molecules

AVOGADRO’S CONSTANT: The number 6.02 x 10 23 is called the Avogadro’s constant as

this was experimentally determined by Amadeo Avogadro.

Number of moles = Number of particles

Avogadro’s constant

CONVERSION FACTORS
MASS [S.I Unit: kilogram (kg)] TEMPERATURE [S.I Unit: Kelvin (K)]

1kg =103 g = 2.205 lb 0 K = -273 0C

1 lb = 16 oz = 453.59 g K = 0C + 273
0
1 ton = 2000 lb =907.185 kg C = 5/9( 0F -32)
1 a.m.u = 1.660540 x 10-27 0
F = 9/5(0C) + 32
VOLUME [S.I Unit: cubic metre (m3)] ENERGY [S.I Unit: Joule (J) ]

1 L = 10-3 m3 = 1 dm3 = 1.057 qt 1 J = 1 kg m2 s-2

1 mL = cm3 1 cal = 4.184 J

1 gal = 4qt = 3.758 L 1 eV/molecule = 96.485 kJ mol-1

PRESSURE [S.I Unit: Pascal (Pa)] 1 MeV = 1.60218 x 10-13 J

1 Pa = 1 Nm-2 = 1 kg m-1 s-2

1 atm = 760 mmHg (torr)

= 101325 Pa

10
 = 14.70 lb in-2

LENGTH [S.I Unit: metre (m)]

1 m = 102 cm = 1.094 yd

1 km = 0.621 mi

1 mi 5280 ft= 1760 yd =1.609 km

1 in = 2.54 cm

1 pm = 10-12 = 10-10 cm = 10-3

THE MOLE AND THE MOLAR MASS

The molar mass is the mass of one mole of a substance. The molar mass of a
substance has the same numerical value as the relative atomic mass or the formula mass of
the substance but it is expressed in gram per mole. Relative atomic mass and formula mass
have no units.

Number of moles = mass of substance

Molar mass of the substance
As one mole of any substance contains 6.02 x 10 23 structural units, the number of particles
in a known mass of substance can be found by:

Number of particles = mass x Avogadro’s constant

molar mass
Examples
1. What is the mass of 0.2 mole of calcium carbonate (R.A.M:C = 12, O = 16, Ca = 40.1)
Solution:
Molar mass of CaCO3 = 40.1+ 12 + 3 x 16 = 100.1gmol-1
Mass of calcium carbonate = Number of moles x molar mass
= 0.2 x 100.1 = 20.02g

11
2. Calculate the number of gold atoms in a 20g gold coin.
(Au = 197.0)
Solution:
Number of moles = number of particles
Avogadro’s constant
:. Number of gold atoms in a 20g gold coin
= mass x Avogadro’s constant
Molar mass
= 20 x 6.02 x 1023
197 = 6.11 x 1022

3. A magnesium chloride solution contains 10g of magnesium chloride.

(a) Calculate the number of moles of magnesium chloride ions in the solution.
(b) Calculate the number of magnesium ions in the solution
(c) Calculate the number of chloride ions in the solution
(d) Calculate the total number of ions in the solution. (Mg = 24.3, Cl = 35.5)

Solution:

(a) Molar mass of MgCl2 = 24.3 + 35.5 x 2 = 95.3gmol-1

Number of moles of magnesium chloride = 10 = 0.105mol.

95.3

(b) 1 mole of MgCl2 1 mol Mg2+ and 2mol Cl -

.: 0.105 mol MgCl2 0.105 mol Mg2+

Number of Mg2+ ions = Number of moles of Mg2+ x 6.02 x 1023

= 0.105 x 6.02 x 1023 = 6.321 x 1022

12
 (c) 0.105mol MgCl2 contains 0.21 mole of Cl-
Number of Cl– ions = Number of moles of Cl- x 6.02 x 1023

= 1.264 x 1023

(d) Total number of ions = 6.321 x 1022 + 1.264 x 1023

= 1.896 x 1023

4. What is the mass of a carbondioxide molecule? (C = 12, O = 16)

Solution:

Molar mass of CO2 = 12 + 16 x 2 = 44.0gmol-1

Number of moles = mass = Number of molecule

Molar mass Avogadro’s constant

.: Mass of molecule = 1

44 6.02 x 1023

Mass of CO2 molecule = 44 = 7.31 x 10-23g

6.02 x 1023

MOLAR VOLUME OF GASES

When one mole of hydrogen is introduced into a container by a frictionless piston at 25 0C

and 1 atmospheric pressure ( room temperature and pressure, RTP), the gas occupies a
volume of 24 dm3. As the volume occupied by one mole of a gas is called the molar volume
of the gas, the molar volume of hydrogen at RTP is 24 dm 3 mol-1. The molar volume of any
gas, at RTP is 24 dm3 mol-1.

volume of the gas

Number of moles of a gas =
molar volume

Also

13
 No . of formulaunits
Number of moles of a gas = '
Avogadr o s constant

Examples

1. Find the volume occupied by 3.55 g of chlorine gas at RTP (molar volume of gas at RTP
= 24 dm3 mol-1, Cl = 35.5).

2. Find the number of molecules in 4.48 cm 3 of carbon dioxide gas at S.T.P (molar volume
of gas at STP = 22.4 dm3 mol-1, Avogadro’s constant = 6.02 x 1023)

Soln

22.4 dm3 = 22400 cm3

4.48
No. of moles of CO2 = = 2 x 10-4 mol
22400

No. of molecules = 2 x 10-4 x 6.02 x 1023 = 1.204 x 1020

3. The molar volume of nitrogen gas is 24 dm 3 mol-1 at RTP. Find the density of nitrogen
gas (N = 14). Ans; g/dm3.

4. 1.6 g of a gas occupies 1.2 dm3 at RTP. What is the relative atomic mass of the gas?
(molar volume of gas at RTP = 24 dm3 mol-1). Ans. Molar mass without unit.

5. What mass of oxygen has the same number of moles as in 3.2. g of sulphur dioxide (O =
16, S = 32.1).

6. The molar volume of oxygen gas is 22.4 dm 3 mol-1 at STP. Find the density of oxygen in g
cm-3 at STP (O = 16).

Exercises

1. Find the mass in grams of 0.01mole of zinc sulphide (S = 32.1, Zn = 65.4)

2. Find the number of ions in 5.61g of calcium oxide. (O = 16, Ca = 40.1)
3. Given that the molar mass of water is 18gmol-1

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 (a) What is the mass of 4 moles of water molecule
(b) How many molecules are there?
(c) How many atoms are there? (H = 1, O = 16)
4. Given 4.80g of ammonium carbonate, find:
(i) Number of moles of the compound
(ii) Number of moles of ammonium ions
(iii) Number of moles of carbonate ions
(iv) Number of moles of hydrogen atoms
(v) Number of hydrogen atoms
5. How many grams of CO2 is formed when 73.9g of propane is burnt?
C3H8 + 5O2 →3CO2 + 4H2O
6. What is the mass in grams of 10.0million SO2 molecules?

(H = 1, C = 12, N = 14, 0 = 16, S= 32)

Determination of relative atomic masses

Atomic mass of element appear as fraction because most naturally occurring elements have
more than one isotope

63 65
The atomic masses of two stable copper isotopes Cu (69.09%) and Cu(30.91%) are
62.93amu and 64.93amu respectively. Calculate the average atomic mass of copper.

Solution

69.09 30.91
The average atomic mass = X 62.93 + X 64.93 = 63.55amu
100 100

CHEMICAL EQUATION AND STOICHIOMETRY OF CHEMICAL REACTION

A chemical equation is a statement, in formulae and symbols, which shows the

relative number of particles involved in a chemical reaction. e.g.

Mg (s) + 2HCl (aq) MgCl2 (aq) + H2 (g)

15
 In this case, the equation tells us that 1 atom of Mg reacts with 2 molecules of HCl to
give 1MgCl2 formula unit and 1H2 molecule. The numbers appearing before the chemical
formulae in the equation are called STOICHIOMETRIC COEFFICIENT.
STIOCHIOMETRY OF CHEMICAL REACTION refers to the relative number of moles
of substances involved in a chemical reaction. It is also the art of measuring chemical
elements in terms of quantitative relationship in chemical reactions.

Stoichometry is based on

i. Conservation of mass
ii. Relative masses of atoms
iii. The concept of mole

And it involves

i. Predicting the quantities of reacting materials required to give products

ii. Interpreting the results of chemical analysis
iii. Choosing the most economical way of carrying out reaction on large scale
iv. Preparing solutions containing specific concentrations of dissolved substances.

Experiments can be designed to study the stoichiometry of reactions. The types of

reactions that are commonly studied include:

(a) Precipitation reactions

(b) Displacement of hydrogen from acids
(c) Displacement of metallic oxides
(d) Reduction of metallic oxides

CALCULATIONS BASED ON CHEMICAL EQUATIONS

We can use chemical equations to calculate the relative amounts of substances involved in chemical reactions.
Let us consider the combustion of methane in excess oxygen. The balanced chemical equation for that reaction
is

On a quantitative basis, at the molecular level, the equation says

16
EXAMPLE 1. Number of Molecules
How many O2 molecules react with 47 CH4 molecules according to the following equation?

Plan
The balanced equation tells us that one CH4 molecule reacts with two O2 molecules. We can construct two unit
factors from this fact:

These expressions are unit factors for this reaction because the numerator and denominator are chemically
equivalent. In other words, the numerator and the denominator represent the same amount of reaction. To
convert CH4 molecules to O2 molecules, we multiply by the second of the two factors.
Solution

EXAMPLE 2. Number of Moles Formed

How many moles of water could be produced by the reaction of 3.5 mol of methane with excess oxygen ( i.e.,
more than a sufficient amount of oxygen is present)?

Plan
The equation for the combustion of methane

shows that 1 mol of methane reacts with 2 mol of oxygen to produce 2 mol of water. From this information we
construct two unit factors:

We use the second factor in this calculation.

Solution

EXAMPLE 3. Mass of a Reactant Required

What mass of oxygen is required to react completely with 1.20 mol of CH 4?
Plan
The balanced equation

17
EXAMPLE 4 Mass of a Reactant Required

What mass of oxygen is required to react completely with 24.0 g of CH 4?

Plan: Recall the balanced equation in Example 3.

This shows that 1 mol of CH4 reacts with 2 mol of O2. These two quantities are chemically equivalent, so we
can construct unit factors.
Solution

Steps:

18
EXAMPLE 5 Mass of a Reactant Required
What mass of CH4, in grams, is required to react with 96.0 grams of O2?
Plan
We recall that one mole of CH4 reacts with two moles of O2.

EXAMPLE 6 Mass of a Product Formed

Most combustion reactions occur in excess O 2, that is, more than enough O2 to burn the substance completely.
Calculate the mass of CO2, in grams, that can be produced by burning 6.00 mol of CH4 in excess O2.

Plan
The balanced equation tells us that one mole of CH 4 produces one mole of CO2.

EXAMPLE 7 Mass of a Reactant Required

Phosphorus, P4, burns with excess oxygen to form tetraphosphorus decoxide, P 4O10. In this reaction, what mass
of P4 reacts with 1.50 moles of O2?
Plan

19
The balanced equation tells us that one mole of P4 reacts with five moles of O2.

THE LIMITING REACTANT CONCEPT

In the problems we have worked thus far, the presence of an excess of one reactant was stated or implied. The
calculations were based on the substance that was used up first, called the limiting reactant. Before we study
the concept of the limiting reactant in stoichiometry, let’s develop the basic idea by considering a simple but
analogous nonchemical example.

Suppose you have four slices of ham and six slices of bread and you wish to make as many ham sandwiches as
possible using only one slice of ham and two slices of bread per sandwich. Obviously, you can make only three
sandwiches, at which point you run out of bread. (In a chemical reaction this would correspond to one of the
reactants being used up—so the reaction would stop.) The bread is therefore the “limiting reactant,” and the
extra slice of ham is the “excess reactant.” The amount of product, ham sandwiches, is determined by the
amount of the limiting reactant, bread in this case. The limiting reactant is not necessarily the reactant present
in the smallest amount. We have four slices of ham, the smallest amount, and six slices of bread, but the
“reaction ratio” is two slices of bread to one piece of ham, and so bread is the limiting reactant.

EXAMPLE 8 Limiting Reactant

What mass of CO2 could be formed by the reaction of 16.0 g of CH4 with 48.0 g of O2?
Plan
The balanced equation tells us that one mole of CH 4 reacts with two moles of O2.

We are given masses of both CH4 and O2, so we calculate the number of moles of each reactant, and then
determine the number of moles of each reactant required to react with the other.
From these calculations we identify the limiting reactant. Then we base the calculation on it.
Solution

Now we return to the balanced equation. First we calculate the number of moles of O 2 that would be required
to react with 1.00 mole of CH4.

20
We see that 2.00 moles of O 2 is required, but we have 1.50 moles of O 2, so O2 is the limiting reactant.
Alternatively, we can calculate the number of moles of CH 4 that would react with 1.50 moles of O2.

This tells us that only 0.750 mole of CH4 would be required to react with 1.50 moles of O2.
But we have 1.00 mole of CH 4, so we see again that O 2 is the limiting reactant. The reaction must stop when
the limiting reactant, O2, is used up, so we base the calculation on O2.

Thus, 33.0 grams of CO2 is the most CO2 that can be produced from 16.0 grams of CH 4 and 48.0 grams of O 2.
If we had based our calculation on CH 4 rather than O2, our answer would be too big (44.0 grams) and wrong
because more O2 than we have would be required.

Limiting Reactant
What is the maximum mass of Ni(OH) 2 that could be prepared by mixing two solutions that contain 25.9 g of
NiCl2 and 10.0 g of NaOH, respectively?

Plan
Interpreting the balanced equation as usual, we have

We determine the number of moles of NiCl 2 and NaOH present. Then we find the number of moles of each
reactant required to react with the other reactant. These calculations identify the limiting reactant. We base the
calculation on it.
Solution

21
PERCENT YIELDS FROM CHEMICAL REACTIONS
The theoretical yield from a chemical reaction is the yield calculated by assuming that the reaction goes to
completion. In practice we often do not obtain as much product from a reaction mixture as is theoretically
possible. This is true for several reasons. (1) Many reactions do not go to completion; that is, the reactants are
not completely converted to products. (2) In some cases, a particular set of reactants undergoes two or more
reactions simultaneously, forming undesired products as well as desired products. Reactions other than the
desired one are called “side reactions.” (3) In some cases, separation of the desired product from the reaction
mixture is so difficult that not the entire product formed is successfully isolated. The actual yield is the
amount of a specified pure product actually obtained from a given reaction.

The term percent yield is used to indicate how much of a desired product is obtained from a reaction.
Consider the preparation of nitrobenzene, C6H5NO2, by the reaction of a limited amount of benzene, C 6H6, with
excess nitric acid, HNO3. The balanced equation for the reaction may be written as

EXAMPLE 10 Percent Yield

A 15.6-gram sample of C6H6 is mixed with excess HNO3. We isolate 18.0 grams of C6H5NO2.
What is the percent yield of C6H5NO2 in this reaction?
Plan
First we interpret the balanced chemical equation to calculate the theoretical yield of C 6H5NO2.
Then we use the actual (isolated) yield and the previous definition to calculate the percent yield.

22
Solution
We calculate the theoretical yield of C 6H5NO2.

The amount of nitrobenzene obtained in this experiment is 73.2% of the amount that would be expected if the
reaction had gone to completion, if there were no side reactions, and if we could have recovered all of the
product as pure substance.

Stoichiometry in solution

Solution= solute + solvent

The composition of a solution is often described in terms of the amount of solute in a given
amount of solvent or in a given amount of solution. One way of describing solution
concentration is mass percent

mass of solute
Mass percent = X 100%
mas s of solution

Suppose a solution is prepared by dissolving 2.0g of NaCl in 50.0g of water. The solution
has a mass of 52.0g and there is 2.0g of solute present.

2.0 g solute
Mass percent of the solute = X 100 = 3.85%
52.0 g solution

Exercises

1. A solution is prepared by mixing 5.00g ethanol with 150.0g of water; calculate the mass
percent of ethanol in this solution
2. What mass of water must be added to 450g of formaldehyde to prepare to a 45.0% of
(by mass) solution of formaldehyde?

Alternatively, a solution could be described in terms of concentration.

23
Concentration of a solution is the amount of solute in a given volume of solution. Molarity is
the most common expression of concentration.

moles of solute
Molarity(M) = = mol/l
litres of solution

Example

Calculate the molarity of a solution prepared by dissolving 10.5g of solid NaOH in enough
water to make 1.50L of solution.

Solution

Amount of solute= 10.5g NaOH

Amount of solution = 1.50L

M= moles of solute/ litres of solution

1 mol of NaOH →40.0g

? → 10.5g = 10.5/40.0 = 0.2625mol

Molarity = 0.2625mol/1.50L = 0.175M

What mass of HNO3 is contained in 200ml of 0.200M HNO3 solution?

Solution

Molarity = 0.200M, Volume = 200ml=0.2L, Molar mass of HNO 3 = 63.0g

Molarity = number of moles of solute/volume of the solution

0.200M = no of moles of HNO3/ 0.2L

No of moles of HNO3 = 0.2M x 0.2L= 0.04mol

1 mol of HNO3 = 63.0g

0.04mol = ? 0.04 X 63.0 = 2.52g

Exercises

1. Give the concentration of all the ions in each of the following

(a) 0.75M Na2CO3 (b) 2M KCl
2. How many moles of Na+ ions are present in 20cm 3 of a 0.45M NaCl

24
 solution?

Molality

This is the number of moles of solute per kilogram of the solvent. A 4.5 molal salt solution
contains salt and water in a ratio such that there are 4.5mol of salt for every 1000g of water.

What is the molality of a solution prepared by dissolving 25.0g of I 2 in 150g of CCl4( molar
mass of I2 = 254gmol-1)

Solution

No of moles of I2 = 25/254 = 0.098mol

This 0.098mol is for 150g

1000
For 1000g we have ? = X 0.098 = 0.653m
150

Exercise

What is the molality of a 1.50M H2SO4 solution that has a density of 1.20g/ml?

Mole fraction

The mole fraction of a component of a solution is defined as the ratio of the number of moles
of that component to the total number of moles of all the constituents of the solution.

Thus in a solution of M dissolved in N

mol es of M
Mole fraction of M (Xm) =
moles of M +moles of N

What is the mole fraction of glucose (C6H12O6) in 20 wt % solution of glucose in water?

Solution

There is 20g of glucose in every 80g of water

(C6H12O6) = 180 g/mol

180g glucose = 1 mole

20g = ? = 20/180 = 0.11mol C6H12O6

H2O = 18 g/mol

25
18g water = 1 mole

80g = ? 80/18 = 4.44mol

0.11
Mole fraction of glucose = = 0.02
0.11+4.44

Normality(N) This is defined as the number of equivalent weights of solute per litre of
solution.

The equivalent weight is the formula weight divided by the number of reacting units

number of equivalents
N=
1 litre of solution

For acids and bases the number of reacting units is based on the number of protons an acid
will furnish or a base will react with; for redox reactions, it is based on the number of
electrons an oxidizing or reducing agent will take on or supply.

Examples

 The equivalent weight of H2SO4 is ?

H2SO4 has 2 equivalents of protons, molar mass = 98.08g/mol

98.08 g /mol
This means Equiv. weight =
2≡¿ mol

= 49.04g/equiv

This means that the normality of H2SO4 is twice its molarity.

 The equivalent weight of KMnO4 is ?

Mn changes from +7 to +2 oxidation state, the molar mass of KMnO 4 = 158.04

This means that the equiv. weight = 158.04/5 = 31.6g/eq

A solution of HCl contains 86g of HCl per litre of solution. calculate the normality of this
solution?

Solution

Equivalenght weight = 36.5/1 = 36.5g

26
 We have 86g of HCl

1 eq wt = 36.5g

? = 86g

86/36.5 = 2.36 equiv

N= 2.36/1.0L = 2.36N HCl

DERIVATION OF FORMULAE FROM ELEMENTAL COMPOSITION

The simplest or empirical formula for a compound is the smallest whole-number ratio of atoms
present. For molecular compounds the molecular formula indicates the actual numbers of atoms
present in a molecule of the compound. It may be the same as the simplest formula or else some
whole-number multiple of it. For example, the simplest and molecular formulae for water are both
H2O; however, for hydrogen peroxide, they are HO and H2O2, respectively.

Each year thousands of new compounds are made in laboratories or discovered in nature. One of the
first steps in characterizing a new compound is the determination of its percent composition. A
qualitative analysis is performed to determine which elements are present in the compound. Then a
quantitative analysis is performed to determine the amount of each element.

Once the percent composition of a compound (or its elemental composition by mass) is known, the
simplest formula can be determined.

EXAMPLE 1 (Simplest Formulae)

Compounds containing sulfur and oxygen are serious air pollutants; they represent the major cause of
acid rain. Analysis of a sample of a pure compound reveals that it contains 50.1% sulfur and 49.9%
oxygen by mass. What is the simplest formula of the compound?

Plan
One mole of atoms of any element is 6.02 x 1023 atoms, so the ratio of moles of atoms in any sample
of a compound is the same as the ratio of atoms in that compound. This calculation is carried out in
two steps.
Step 1: Let’s consider 100.0 g of compound, which contains 50.1 g of S and 49.9 g of O. We
calculate the number of moles of atoms of each.
Step 2: We then obtain a whole-number ratio between these numbers that gives the ratio of atoms in
the sample and hence in the simplest formula for the compound.
Solution

27
Step 2: Now we know that 100.0 g of the compound contains 1.56 mol of S atoms and 3.12 mol of O
atoms. We obtain a whole-number ratio between these numbers that gives the ratio of atoms in the
simplest formula.

A simple and useful way to obtain whole-number ratios among several numbers follows: (a) Divide
each number by the smallest, and then,
(b) if necessary, multiply all of the resulting numbers by the smallest whole number that will
eliminate fractions.

The solution for the above Example can be set up in tabular form.

EXAMPLE 2
A 20.882-gram sample of an ionic compound is found to contain 6.072 grams of Na, 8.474 grams of
S, and 6.336 grams of O. What is its simplest formula?
Plan
We reason as in Example 1, calculating the number of moles of each element and the ratio among
them. Here we use the tabular format that was introduced earlier.
Solution

The ratio of atoms in the simplest formula must be a whole-number ratio (by definition). To convert
the ratio 1:1:1.5 to a whole-number ratio, each number in the ratio was multiplied by 2, which gave
the simplest formula Na2S2O3.

DETERMINATION OF EMPIRICAL FORMULA FROM COMBUSTION DATA

28
Example 3. A compound X is known to contain carbon, hydrogen and oxygen only. When it is burnt
completely in excess oxygen, carbon dioxide and water are given out as the only products. It is found
that 0.46 g of X gives 0.88 g carbon dioxide and 0.5 g of water. Find the empirical formula of
compound X.
Solution: Mass of X = 0.46 g
Mass of carbon in X = 0.88 x 12/44 = 0.24 g
Mass of hydrogen in X = 0.54 x 2/18 = 0.06 g
Mass of oxygen in X = 0.46 – (0.24 + 0.06) = 0.16 g
Let the empirical formula of X = CxHyOz
Carbon hydrogen Oxygen
Mass 0.22 0.06 0.16
No. of moles 0.24/12 = 0.02 0.06/1 = 0.06 0.16/16 = 0.01
Relative No. of moles 0.02/0.01 = 2 0.06/0.01 = 6 0.01/0.01 = 1
Simplest mole ratio 2 6 1

∴ Empirical formula of X = C2H6O

EXAMPLE 4 (Percent Composition)
A 0.1014-g sample of purified glucose was burned in a C-H combustion train to produce 0.1486 g of
CO2 and 0.0609 g of H2O. An elemental analysis showed that glucose contains only carbon,
hydrogen, and oxygen. Determine the masses of C, H, and O in the sample and the percentages of
these elements in glucose.
Plan
Steps 1 and 2: We first calculate the masses of carbon and hydrogen as we did in Example 2
Step 3: The rest of the sample must be oxygen because glucose has been shown to contain only C, H,
and O. So we subtract the masses of C and H from the total mass of sample.
Step 4: Then we calculate the percentage by mass for each element.

29
5.Calculate the mass percent of each component of a solution which contains 40.2 g of sodium
chloride, 20.2 g of methyl alcohol and 100.2 g of water.

Total mass of solution components = 40.2 + 20.2 + 100.2 = 160.6 g

Mass % of NaCl = 40.2/160.6 x100/1 = 25.03 %
Mass % of CH3OH = 20.2/160.6 x 100/1 = 12.58 %
Mass % of H2O = 100.2/160.6 x 100/1 = 62.39 %

DETERMINATION OF MOLECULAR FORMULAE

Percent composition data yield only simplest formulas. To determine the molecular formula for a
molecular compound, both its simplest formula and its molecular weight must be known.

For many compounds the molecular formula is a multiple of the simplest formula.
Consider butane, C4H10. The simplest formula for butane is C2H5, but the molecular formula contains
twice as many atoms; that is, 2 X (C2H5) = C4H10. Benzene, C6H6, is another example. The simplest
formula for benzene is CH, but the molecular formula contains six times as many atoms; that is, 6 X
(CH) = C6H6.
The molecular formula for a compound is either the same as, or an integer multiple of, the simplest
formula.

Molecular formula = n X simplest formula

So we can write
Molecular weight = n X simplest formula weight

30
The molecular formula is then obtained by multiplying the simplest formula by the integer, n.
EXAMPLE 6(Molecular Formula)
In Example 4, we found the elemental composition of glucose. Other experiments show that its
molecular weight is approximately 180 amu. Determine the simplest formula and the molecular
formula of glucose.
Plan
Step 1: We first use the masses of C, H, and O found in Example 3 to determine the simplest formula.
Step 2: We can use the simplest formula to calculate the simplest formula weight. Because the
molecular weight of glucose is known (approximately 180 amu), we can determine the molecular
formula by dividing the molecular weight by the simplest formula weight.

The molecular weight is n times the simplest formula weight, so the molecular formula of glucose is
n times the simplest formula.
Solution
Step 1:

Step 2: The simplest formula is CH2O, which has a formula weight of 30.03 amu. Because the
molecular weight of glucose is approximately 180 amu, we can determine the molecular formula by
dividing the molecular weight by the simplest formula weight.

The molecular weight is six times the simplest formula weight, 6 X (CH2O) = C6H12O6, so the
molecular formula of glucose is C6H12O6.

EXERCISES
1. Each 325 mg tablet of aspirin consists of 195.0 mg carbon, 14.6 mg hydrogen and 115.4
mg oxygen. Determine its empirical formula.
2. Compound Z is the major component of a healthy drink. The composition of compound Z
is 40 % carbon, 6.67 % hydrogen and 53.33 % oxygen. If the molecular mass of compound
Z is 180, find its molecular formula.
3. Calculate the percentages by mass of potassium, chromium and oxygen in potassium
dichromate, K2Cr2O7.(K = 39, Cr = 52, O = 16).

31
4. 5 g of sulphur gives 10 g of sulphur oxide on burning. What is the empirical formula of the
oxide?
5. A hydrocarbon is burnt completely in excess oxygen. It is found that 1 g of the
hydrocarbon gives 2.92 g carbon dioxide and 1.8 g water. Find the empirical formula of the
hydrocarbon. ( H = 1, C = 12, O = 16).

CHEMICAL EQUILIBRUM.

In a reaction which is enclosed in a vessel, a stage is reached when the products formed
react back to form the reactants again. This stage which is characterized by a continual
exchange but no change is referred to equilibrium.

Chemical Equilibrium therefore can be defined as the condition in which two opposing
reactions occur at equal rates ie the rate of forward reaction is equal to the rate of backward
reaction.

Consider this reaction: xX + yY ⥫ wW + zZ … … … … … …(1)

The rate at which X and Y reacts to form W and Z is equal to the rate at which W and Z
react to form X and Y.

A system is said to be in dynamic equilibrium when there are no net changes in the
concentrations of the reactants and the products with time.

In reaction 1 above: The rate of forward reaction R 1 =K1 [X]x[Y]y

The rate of backward reaction R -1 =K-1 [W]w[Z]z

At equilibrium R1 = R-1 which means that K1 [X]x[Y]y = K-1 [W]w[Z]z

K1/K-1 = [W]w[Z]z/[X]x[Y]y = Kc…………………….(2)

Kc is the equilibrium constant.

This is a law of chemical equilibrium which states that when x and y moles of reactants (X
and Y) react to form w and z moles of products(W and Z), in equilibrium, that the
concentration of the products divided by that of the reactants is constant, provided they are
expressed to the powers of their stoichiometric moles.

Equation 2 is a general case but we can use the pressure parameter to deduce the
equilibrium constant (Kp)

Consider this reaction N2 + 3H2 ⥫2NH3

32
 [ NH 3 ] 2 2
P NH 3
Kc= ∧Kp=
[ N2] [ H2]3 ¿¿¿

THE RELATIONSHIP BETWEEN TWO REVERSE REACTIONS

Consider these reverse reactions

H2 + I2⥫2HI

2HI ⥫ H2 + I2
2
[ HI ]
K1 = and K2 =¿ ¿ ¿
H 2¿ ¿¿

Comparing the two expressions, K 1 = 1/K2. This means that equilibrium constants for a
reaction and its reverse are reciprocals.

The relationship between Kc and Kp

In reactions involving gases , Kc ≠ Kp

If we consider our general equation 1 above

w z
PW PZ
Kp = x y ------------------------------(3)
P X PY

Assuming an ideal gas behavior PV =nRT and concentration C=n/V (moldm -3). This means
that P/RT = Concentration.

Px = [X]x(RT)x-------------------------------------(4)

Substituting this relationship into Kp in equation 3, we have

w
Kp = [ W ] ¿ ¿

Kp = [ W ] w ¿ ¿(RT)(w+z)-(x+y)

Kp = Kc(RT)∆n-----------------------( 5) where ∆n is the number of moles of products – the

number of moles of the reactants.

Example 1. In this reaction 2SO 2(g) + O2(g) ⥫ 2SO3(g). Kc = 2.8 X 102 moldm-3 at 1000K.
Calculate the Kp?

solution

33
Kp = Kc(RT)∆n

2SO2(g) + O2(g) ⥫ 2SO3(g). , ∆n = 2-(1+2) = -1, R = 8.314KPamol-1K-1, T = 1000K

Kp= 2.8 X 102 moldm-3 X (8.314KPamol-1K-1X 1000K)-1

Kp= 3.37 X 10-2(KPa)-1

Combining equilibrium constant expressions

N2(g) + O2(g) ⥫ 2NO(g) K1 = 4.1 X 10-31

N2(g) +1/2 O2(g) ⥫ N2O(g) K2 = 4.2 X 10-18

N2O(g) + 1/2O2(g) ⥫ 2NO(g) K3 = ?

Solution

To obtain K3, we can see that when we combine 1 and 2 we get 3. ie

N2(g) + O2(g) ⥫ 2NO(g) K1 = 4.1 X 10-31

1
N2O(g) ⥫ N2 + 1/2O2(g) K2 = −18
4.2 X 10

N2(g) + O2(g) + N2O(g) ⥫ 2NO(g)+ N2 + 1/2O2(g)

Therefore N2O(g) + 1/2O2(g) ⥫ 2NO(g)------------K3

2
K3 = [ NO ] = K 1 X K2
¿¿
1
K3 = 4.1 x 10-31 x
4.2 X 10−18

K3 = 9.8 x 10-14

This means that the equilibrium constant for a net reaction is the product of the equilibrium
for the individual reaction added.

Factors affecting equilibrium

The different factors affecting equilibrium could be attributed to the Le Chatelier’s principle
which states that if a system at equilibrium is disturbed, the system or reaction will adjust in
order to relieve the disturbing influence.

The system can be disturbed by

34
 1. Adding or removing reactant or products (concentration change)
2. Changing the temperature
3. Changing the pressure or volume

Concentration change
If the concentration of the reactants or products of a system in equilibrium is altered, the
system will adjust to maintain equilibrium. For example: In this reaction, N 2 +3H2⥫2NH3 . If
more H2(g) is introduced into the system, the reaction proceeds from left to right to relieve
the disturbance (or stress). This results to an increase in the amount of NH 3 but decrease in
the amount of N2(g)

Change in volume

In this case there is no change in the amount of reaction mixture but the volume of reaction
is reduced by increasing the pressure of the mixture. Assuming the reaction volume is
reduced by one tenth, there will be readjustment of equilibrium amounts and K c may become

Kc =[So3]2 /[SO2]2[O2] = ¿ ¿ ¿
2
nSO 3
= 2
.V
nSO 2 n02
2
nSO 3
This means that if V is reduced by a factor of ten, then the ratio 2 must increase by a
nSO 2 n02
factor of ten.

The equilibrium amounts of SO 3 must increase and the amounts of SO 2 and O2 must
decrease. In the reaction 2SO 2 + O2 ⥫2SO3, 3 moles of gases (2+1) in the left give rise to 2
moles of SO3 on the right. This means that SO 3 occupies a smaller volume than the gases
that formed it. Thus forcing the equilibrium into a smaller volume produces more SO 3. In
other words, decrease in volume favors the production of SO 3 and increase in volume favors
the backward reaction(proceeds to the left).

Effect of catalyst

The presence of a catalyst has the effect of speeding up both the forward and backward
reactions but the equilibrium amount of the species are unaffected.

Change of pressure

A change in pressure will alter the equilibrium condition only if this pressure change
produces changes in concentrations. However, increasing the pressure by adding an inert
gas into a system would not affect the equilibrium conditions.

35
Change in temperature

Changing the temperature of a system in equilibrium is the same as adding or removing

heat from the system. When we add heat, the temperature is increased and the equilibrium
shifts to the direction of the endothermic reaction but when we remove heat or lower the
temperature, the equilibrium shifts to the direction of the exothermic reaction

In this reaction, N2 + 3H2 ⥫2NH3 -92.0KJ when we raise the temperature, the reverse
reaction (endothermic) is favored but when we reduce the temperature the forward reaction
is favoured (more NH3 is produced from N2 and H2)

Relating the equilibrium constant with temperature

−∆ H 0 1
Log K = . + constant
2.303 R T

For exothermic reactions, K decreases with an increase in temperature but for endothermic,
K increases with an increase in temperature.

K 2 −∆ H 0
At different temperatures, log = ¿) This is called Van’t Hoff equation
K 1 2.303 R

When ∆H ˃ 0, the equilibrium constant increases.

Heterogeneous equilibrium( Gas-solid or Gas-liquid reactions)

This is equilibrium that involves heterogeneous reactions (liquids and solids).In this type of
equilibrium; the concentrations of solids and liquids do not appear because their
concentrations do not change in the course of the reaction.

Example, In this reaction CaCO3(s)⥫CaO(s) + CO2(g)

Because CaO and CaCO3 are solids, their concentrations do not take part in the equlibruim
constant.

Kc =[CO2(g)]

Following similarly Kp = PCO2 where P = nRT/V

Kp = Kc(RT)

This means that the pressure of CO2 does not depend on the quantities of CaO and CaCO 3
present.

Predicting the direction of reaction

36
In predicting the direction of a reaction, we should be conversant with the reaction
quotient Q which is the ratio of the concentration of the products to that of the
reactants.

From our earlier general reaction, we can say that Q= [ W ] w ¿ ¿

When the reaction is at equilibrium, K = Q. If Q ¿K, then the reaction proceeds from
left to the right(forward reaction).when Q˃K, the reaction proceeds from right to
left(backward reaction). When the reaction quotient is zero, it means we have pure
reactants only but if it is infinity, it means pure products.

Facts about Equilibrium constant, Kc

1. Only species that are gases or solution appear in the equilibrium expression, pure
solids and liquids do not.
2. The larger the equilibrium constant, the more the equilibrium favor the product; the
smaller the equilibrium constant , the more the equilibrium favour the reactants.
3. The equilibrium constant (Kc) has a constant value at a given temperature
independent of original concentration ,volume of container or pressure
4. The Kc depends on the way the equation is written.

An 0.0240mol sample of N2O4(g) is allowed to dissociate and come to equilibrium with

NO2(g) in an 0.372L flask at 25 OC. What is the percent dissociation of the N 2O4?
N2O4(g) ⥫2NO2(g) Kc = 4.61X 10-3 at 25oC.

Solution

Let x be the number of moles of N2O4(g) that dissociated

The reaction N2O4(g) ⥫ 2NO2(g)
Initial amount 0.024mol 0.00mol
Change -xmol +2xmol
Equil. Amount (0.024-x)mol 2x
Equil. Conc (0.024-x)mol/0.372L 2xmol/0.372L

K = ¿ ¿ = ( 2x/0.372)2/(0.024-x)/0.372

-3 4 x2
4.61X 10 =
0.372(0.024−x)
4x2 = 4.12 X 10-5 – (1.71 X 10-3)x

X = 3.00 X 10-3 mol N2O4

37
 % dissociation = 3.00 X 10-3 mol N2O4/0.024mol X 100
= 12.5%

Equilibrium calculations Exercises.

1. For the reaction 2NH3 ⥫1/2N2 + 3/2H2, Kc = 5.2X10-5 at 298K. what is the
value of Kc at 298K for the reaction N2 + 3H2 ⥫2NH3
2. Write an equilibrium constant expression, K c, for each of the following
reactions :
a) CO(g) + H2O(g) ⥫ CO2(g) + H2(g)
b) NO(g) + O2(g) ⥫ 2NO2(g)
3. What effect would decreasing the volume of the reaction mixture have on the
equlibruim condition in each of the following reactions:
a) C(s) + H2O(g) ⥫ CO(g) + H2(g)
b) CO(g) + H2O(g) ⥫ CO2(g) + H2(g)
c) 4HCl(g) + O2(g) ⥫ Cl2(g) + 2H2O(g)
4 If 0.39mol SO 2, 0.156mol O2 and 0.657mol SO3 are introduced
simultaneously into a 1.90mol reaction vessel at 1000K,
(a) Is this reaction mixture at equilibrium?
(b) If not, in what direction must a reaction proceed to establish equilibrium?
2SO2(g) + O2(g) ⥫ 2SO3(g) + H2(g) Kc = 2.8 X 102 at 1000K

c) Calculate the actual equilibrium amounts of SO2, O2 and SO3

5. A 0.02mol sample SO3 is introduced into an evacuated 1.52L vessel
and heated to 900K, where equilibrium is established. The amount
of SO3 present at equilibrium is found to be 0.0142mol. what are the
values of Kc and Kp at 900K for the reaction 2SO3(g) ⥫ 2SO2(g) +
O2(g)

Ionic Equilibrium

Bronsted- Lowry Theory: This theory simply put acid as a proton donor and base a proton
acceptor.

NH4Cl + NaNH2→NaCl +2NH3

Or in ionic from : NH4+ + NH2- ⥫ NH3+ NH3

Acid(1) Base(2) Acid(2) Base(1)

38
 Conjugate base

If the acid is a strong one, the conjugate base is weak and when the acid is weak, the
conjugate base is strong. The same thing happens in the case of base.

Example: In these reactions, identify the acid and bases.

(a) HClO2 + H2O ⥫ H3O+ + ClO2

(b) NH3 + H2PO4 ⥫ NH4+ + HPO42-
(c) HCl + H2PO4- ⥫ H3PO4 + Cl-

The Bronsted-Lowry is a development on Arrhenius theory which states that an acid is a

substance that dissociates to produce H + and a base is a substance that dissociates to
produce OH- ions. Lewis also developed his own theory and said that an acid is an electron
pair acceptor and a base, an electron pair donor. The Lewis theory is more advantageous in
the sense that it permits the acid-base classification to be used for some reactions in which
neither H+ nor OH- is present. It also allows reactions to be considered of the acid-base type
even when there is no solvent at all, such as certain reactions in the gaseous phase.

Eg

Zn2+(aq) + 4NH3 (aq) → Zn(NH 3)42+. This NH3 donates electrons to Zn2+ to form the
complex. This is the type of reaction seen in coordination chemistry.

Ionization of water
Water is a poor conductor of electricity but for the fact that it conducts feebly means
that it has some ions in it H+ and OH-.
H20 ⥫ H+ + OH-
This self ionization of water is a case of acid-base reaction according to Bronsted-
Lowry theory.

H20 +H2O H3O+ + OH-

Acid base conj acid conj. Base

39
In this case the conjugate acid and base produced are stronger than thee acid and
base, therefore the reaction proceed more to the left(equilibrium is shifted more to the
left) or the reverse reaction is more significant.

Expressing the reaction in terms of equilibrium constant

K = [OH-][H3O+]/[H2O]2 or (a H3O+)(a OH-)/(a H2O)2

Water is a pure liquid and has its activity as 1.
This means that K= [OH-][H3O+] . Also the quantity of water is very large here, so the
concentration is regarded as unity.
Molar concentrations are used here because the ion concentrations are very small, if
not, activities should be used.
Kw= [OH-][H3O+]
At 25OC, the concentrations of [H3O+] =[OH-] in pure water
Ie [H3O+] =[OH-] = 1.0 X 10-7M
The equilibrium constant for autoionsation of water is Kw and it is preferably called
ion-product of water.
Kw =(1.0 X 10-7) X (1.0 X 10-7)= 1.0 X 10-14
This value is only valid at 25Oc temperature
A solution in which the [H+] equals [OH-] is said to be neutral. If the H + is larger than
the OH-, the solution is said to be acidic and when OH - is larger than the H+, it is a
basic solution.
Strong acids and strong bases
When an acid is added to water, two acid-base reactions occur concomitantly as
follows:

a) H20 +H2O H3O+ + OH-

b) HCl + H2O → H3O+ + Cl-

In (a) the forward reaction occurs to a slight extent(no complete ionization) but in (b) it
is assumed that the sole producer of H 3O+ is HCl. The ionization of the HCl goes to a
completion and this is a strong acid.

Example
Calculate H3O+, OH- and Cl- in 0.02M HCl(aq)
Solution
[H3O+] = 0.02M
[Cl- ] = 0.02M ( if we assume that HCl is completely ionsed and the sole source of
H3O+)

40
 Kw = [H3O+][OH-] = 1.00x 10-14
[OH-] = 1.00x 10-14/ 0.02
[OH-] = 5.00x 10-13

The concept of pH and pOH (potential of H and OH)

If a solution has [H3O+] = 10-x, the pH =x

pH =-log[ H3O+]
In 0.01M HCl; [ H3O+] = 10-2
pH = -log(10-2) = - -2log210 = 2

For 0.03M HCl, [ H3O+] = 3X 10-2

Ph = -log(3 X 10-2) = -(log 3.0 + log10-2)
= (0.48-2) = 1.5

To determine [H3O+] from a known pH eg 1.5

pH =-log[ H3O+] = 1.5

log[ H3O+] = -1.5
log[ H3O+] = 0.5-2
[H3O+] = log-1 (0.5) X log-1 (-2)

In the same way,

pOH = -log [OH-]
-log [H3O+][OH-] = -log (1.00x 10-14)
-log [H3O+] X -log[OH-] = - - 14
pH + pOH = 14
Example
What is the Ph of Mg(OH)2 in water. Mg(OH)2
Mg(OH)2 ⥫ Mg2+ + 2OH- Ksp = 2 X 10-11

Solution
Assume that Mg(OH)2 is the sole source of OH-
Let x be the number of moles of Mg(OH) 2 in 1L of saturated solution; x = [Mg 2+] and
2x = [OH-]

[Mg2+][OH-]2 =( x)(2x)2 = 4x3

4x3 = 2 X 10-11
X3 = 2 X 10-11/4
X = 2 X 10-4

41
 [OH] = 2x = 2 X 2 X 10-4 =4 X 10-4 M
pOH = -(log4 + log10-4)
= -(0.6 – 4) = 3.4
pH = 14 -3.4 = 10.6

Exercises
1. Calculate the pH of a solution of 0.02M H+
(b) The pH of a solution 2.5 X 10-3 in OH-
(c) Given that the pH of sea water is 8.5, calculate the H + in sea water.
2. Calculate the molarity of ammonia solution if the pH is 11.50, K b= 1.8 X 10-5

Weak acids and weak bases

In weak acids and bases, their ionisation in water is more complex and could be
represented as follows:
H20 +H2O H3O+ + OH-

HClO +H2O ⥫ H3O+ + ClO-

In this case the ionsation of HClO is a true reversible reaction but in the case of
strong acid and strong base, it is a one-way reaction.

Ionization constant Ka = [H3O+][ClO-] / [HCLO] = 2.95 x 10 -8 . The value of K a is

determined by experiment.

pKa = -logKa = -log( 2.95 X 10-8).

The weaker the acid, the smaller its dissociation or ionization constant.

Example

What is the [H3O+] in 0.0025M HNO2(aq) solution.

Solution

HNO2 + H 2O ⥫ H3O+ + NO2- Ka = 5.13 X 10-4

0.025 - -

-x +x +x

0.025-x +x +x

42
 xX x
Ka = [H3O+][NO2-]/[HNO2] = = 5.13 X 10-4
(0.025−x)

x2 = (0.025-x)(5.13 X 10-4)

x2 + 5.13 X 10-4x - 1.28 X 10-6 = 0

solving quadratically, x = 9.04 X 10-4 M =[ H3O+]

2 A saturated aqeous solution of NH 3 contains 6.0g NH3/L. What is the pH of this solution?
NH3 + H2O ⥫ NH4+ +OH- Kb = 1.74 X 10-5

Solution

[NH3] = 6.0g NH3/L x 1mol NH3/15.0g NH3 = 0.4M

NH3 + H2O ⥫ NH4+ + OH-

initial 0.4M - -

change -x +x +x

at equil 0.4-x +x +x

Kb = [NH4+][OH-]/[NH3] = x.x/0.4-x = 1.74 X 10-5

Assuming the value of x << 0.4, we now have

x2/0.4 = 1.74 X 10-5

x2 = 0.4 X 1.74 X 10-5

x = 2.64 X 10-3 ( this is small compared to 0.4, so assumption is accepted)

[OH-] = 2.64 X 10-3 M

pOH = -log[OH-] = -log(2.64 X 10-3) =

pH = 14- pOH =

Amphiprotic substances

These are substances that can act both as a base and an acid. Examples include H 2O,
HCO3-,HSO4- etc

43
 H2CO3- + H2O ⥫ H3O+ + HCO3- (primary ionization)
Acid base acid base

HCO3- + H2O ⥫ H3O+ + CO32- (secondary ionization)

Acid base

Some acids have more than one proton and they are called polyprotic acids e.g. H 2SO4 –
(has two protons diprotic)etc. because it has two protons, two stages are involved in its
dissociations.

1. H2SO3 (aq) ⥫ H+ + HSO3-(aq)

2. HSO3-(aq)⥫ H+(aq) + SO32-aq)
Or as Bronsted-Lowry definition:

H2SO3 (aq) + H2O ⥫ H3O+ + HSO3-(aq)

HSO3-(aq) + H2O⥫ H+(aq) + SO32-aq)

The K1 and K2 are evaluated as before and it should be noted that K 2 is always
smaller than K1 for any acid. This is because it takes more energy to separate a
proton from a dinegative ion than from a corresponding mononegative ion.

Buffer solution

Pure water has a pH of 7 but it cannot maintain this pH for a long time due to some
chemical and biochemical reactions. As a result of this it is now pertinent to have
solutions that maintain constant pH even when little acid or base is added. Solutions
that are resistant to pH changes when little acid or base is added are called buffer
solutions. Such solutions include a mixture of weak acid and its salt or weak base
and its salt. Eg. Acetic acid + sodium acetate; ammonium hydroxide + ammonium
chloride etc.
If a strong acid is added to the buffer (acetic acid + sodium acetate), the H 3O+ from
the acid reacts with the buffer as follows: C2H3O2- + H3O+ → HC2H3O2 + H2O.
If a base is added, the OH -from the base reacts thus: HC 2H3O2 + OH → C2H3O2- +
H2O.
Buffer capacity is the amount of acid or base that may be added to a buffer solution
before its pH changes appreciably. At pH= pK a, buffer has its maximum capacity but
when the ratio of salt to weak electrolyte concentration is either less than 0.1 or
greater than 10, the buffer loses its capacity.

44
Calculating pH from Buffer Solution

Considering CH3COOH ⥫CH3COO- + H+

Ka = ¿ ¿

H+ = Ka [ C H 3 COO H ]
¿¿
Since acetic acid is a weak acid, its dissociation is to a small extent. In the presence
of sodium acetate which completely dissociates, acetic acid does not dissociate at all.
[acid ]
[H+] = Ka
[ salt ]

[salt ]
-log[H+]= -logKa + log
[ acid]

[salt ]
pH = pKa + log -----------This is Henderson-Hasselbalch equation.
[acid]

1. Calculate the pH of a buffer solution that is 0.15M HC 2H3O2 – 0.50M NaC2H3O2

Solution
HC2H3O2 + H2O ⥫ H3O+ + C2H3O2- Ka = 1.7 X 10-5
Initial 0.15M 0.50M
Changes x x x
Equi. Cond 0.15-x x 0.50 + x

pH = -logKa + log ¿ ¿
(0.5+ x)
pH = -log(1.7 X 10-5) + log
(0.15−x)
Assuming x is far less than 0.15 and 0.5, this means that pH = -log(1.7 X 10-5) +
0.5
log
0.15
pH = 5.8

2. What mass of NaC2H3O2 must be dissolved in 0.3L of 0.25M HC 2H3O2 to produce

a solution with pH of 5.10( assume that the solution volume remains constant and K
= 1.7 X 10-5)

Solution

45
 ph= pka + log ¿ ¿

5.10 = -log(1.7 X 10-5) + log ¿ ¿

5.10 = 4.76 + log ¿ ¿

¿ ¿ = log-1 0.34

[C2H3O2-] = 0.25 X 2.19 = 0.55M

1mol of C2H3O2Na = 82g

0.55mol → 1L
? → 0.3L = 0.3 x .55 = 0.16mol

1mol = 82g
0.16mol = 0.16 X 82g = 13.5g NaC2H3O2

Exercise.
What is the effect of pH on a 0.1M C 2H3O2H-0.1M C2H3O2Na buffer solution
produced by adding 0.001mol H3O+ to 1.0L of solution?

Acid-base indicators

The pH of a substance can be measured using indicators. Acid-base indicators are

substances which undergo a definite colour change within a fairly narrow range of pH.

Litmus paper is sometimes used to determine whether a solution is acidic or alkaline. It is

not very sensitive to slight changes in pH.

The most common indicators are

1) Phenolphthalein- this indicator is colourless at pH below 8 but turns to pink at pH

close to 10.
2) Bromothymol blue- this a weak organic acid indicator which is yellow at pH 6 and
below; and blue at pH 8 and above. Its direction in dilute aqeous
HIn + H2O⥫H3O+ + In-
Yellow blue
Adding an acid favour the reverse reaction (moves to the left) and gives more HIn.
Alternatively the ionization is suppressed (common ion effect), this explains why the
colour turns to yellow when the solution becomes acidic.

46
3) Methyl red is red at pH.4-6 and yellow at pH 7 and above. Methyl orange shows red
at a very low pH(3.1-4.4) while methyl red at (4.2-6.2)

The equivalence point in an acid-base titration is determined by the use of neutralization

or acid-base indicators which exhibit different colours according to the pH of the solution.

Choice of indicators

The pH of a salt solution formed during titration depends on the nature of the acids or
bases used

a) Consider strong acids and strong bases

KCl →K+ + Cl-
H2O ⥫ H+ + OH-
Adding the two equations KCl + H2O ⥫ K+ + Cl- + H+ + OH-
The electrolytes formed here are of strong acid and strong base. Any indicator can be
used to accurately detect the neutralization point.
b) Weak acid and strong base e.g CH3COONa

CH3COONa → CH3COO- + Na+

H2O ⥫ H+ + OH-

CH3COONa + H2O ⥫ CH3COOH + Na+ + OH-

There is an increase in OH- concentration, so the solution is alkaline and the appropriate
indicator that can give a color change in the alkaline solution is phenolphthalein.

c) Strong acids and weak bases eg NH4Cl

NH4Cl →NH4+ + Cl-

H2O ⥫ H+ + OH-

NH4Cl + H2O ⥫ H+ + NH4OH + Cl-

There is an increase in the H + ion concentration over that present in water. Therefore
the indicators with pH color change interval in the acid region is used for the titration
of strong acid and weak base.eg methyl orange
d) Weak acids and weak bases. Eg CH3COONH4
In this case, any indicator can serve. If ka = kb, the salt solution is neutral and any
indicator serves. If ka˃ kb, pH < 7, the solution is acidic and indicators with pH range
less than 7 is used. The reverse is the case for alkaline medium.

47
ELECTROLYSIS

Electrolysis is the chemical change brought about by the passage of an electric current
through an electrolyte. It is carried out in a cell containing two electrodes connected to a
source of direct current. Electrochemical processes require some method of introducing a
stream of electrons into a reacting chemical system and some means of withdrawing them.
The reacting system is contained in the cell and electric current enters or exists through the
electrodes. The electrodes are surfaces in which oxidation reduction half reaction occur. The
electrodes may or may not involve in reactions and in cases they do not involve they are
called inert electrodes.

Reduction reactions occur at the cathode (electrons are gained) and oxidation reactions
occur at the anode.

The REDOX reactions which involve loss of electrons(oxidation) and gain of

electrons(reduction) are the major reactions in electrolysis.

However for electrolysis to take place there must be a reacting system (electrolyte),
electrodes, source of direct current (for electrolytic cell)

There are two types of cells, the electrolytic cell and voltaic or galvanic cell.

VOLTAIC CELL.
If we put a Zn bar in a solution containing Cu 2+, we will find out that the blue colour of
Cu2+ fades and a brown black crust is formed on the Zn bar. This shows that the
reaction involves the reduction of Cu2+ to Cu metal and oxidation of Zn to Zn2+.
Cu2+ + 2e- →Cu(s)---------------reduction
Zn(s)→Zn2+ + 2e- -----------oxidation
Cu2+ + Zn → Cu + Zn2+
This is the basis of voltaic cell. There is no generation of electricity in this case
because the Zn/Cu2+ solution are in physical contact in the same beaker. When they
are separated and connected by an external circuit, the electrons would now travel
through the circuit and produce electric current.

48
The ends of the salt bridge are covered with porous glass disks that allow ions to
diffuse but minimizing mixing of the bridge inside and outside.
The electrons are generated in the anode and consumed in the cathode. The salt
bridge acts as a “liquid wire” allowing ions to flow and complete the circuit. It prevents
the build-up of charges in each half cell which may impede the functioning of the cell.
As the reactants and products serve as the electrodes in the reaction as explained
above, it is not always for many redox reactions. Voltaic cell is always denoted as
Zn(s)/ Zn2+(aq)//Cu2+(aq)/Cu(s)
The components of the anode(oxidation half cell) is on the left and that of the cathode
is on the right.
In a voltaic cell that has the electrodes different from the electrolytes, we write it in
this form: graphite/I-(aq)/I2// H+(aq),MnO4-(aq)/graphite. The electrodes are graphite. In the
cathode, there are H+ and MnO4- solutions and they are separated by comma.

Example
Write the cell notation for the voltaic cell that incorporates each of the following redox
reactions:
a) Al(s) + Cr3+(aq)→Cr(s) + Al3+(aq)
b) Cu2+(aq) + SO2(g) + 2H2O →Cu(s) + SO42-(aq) + 4H+

Solution
a) Al(s)/Al3+(aq)//Cr3+(aq)/Cr(s)

49
 b) Pt/SO2(g)/SO42-(aq),H+(aq)//Cu2+(aq)/Cu(s)

The voltage produced in a voltaic cell is refered to as cell potential or EMF and it is
measured in volts.
1 volt = 1joule/coulomb.
The EMF is affected by changes in concentration of the reactants by energy losses
due to heating of the cell and external circuit.
The standard cell potential(Eocell) is a measured at a specified temperature usually
298K. The standard electrode(half cell) potential(E ohalfcell) is the potential associated
with a given half reaction.
For this reaction:
Cu2+ + Zn → Cu + Zn2+
Eocell = Eocopper + -EoZn = EoCu- EoZn
The standard electrodes potential are
Zn2+ + 2e- → Zn (reduction)
Cu2+ + 2e- → Cu (reduction)
But in our cell we have, Zn → Zn 2++ 2e- ie the reverse, this implies that
Eocell = EoCu + (-EoZn). This is because a standard electrode potential always refers to a
half reaction written as reduction.
Eocell = Eocathode - Eoanode
Example
A voltaic cell incorporates the reaction between aqeous bromine and zinc metal
Br2(aq) + Zn(s) → Zn2+(aq) + 2 Br(aq) Eocell = 1.83V
Calculate Eo for the oxidation of 2Br- to Br2 if EoZn= -0.76V

Solution
Zn →Zn2+ + 2e- Eo Zn = +0.76V
Br2 + 2e- →Br- Eo Br = ?

Eocell = Eocathode - Eoanode = EoBr - EoZn

EoBr = EoCell + EoZn = 1.83V + (-0.76V) = 1.07V
Determining –EoBr, we reverse the reaction and change the sign
2Br-(aq)→Br2(aq) + 2e- EoBr = -1.07V
The more positive the Eo value, the more the reaction tends to occur.

Considering these reactions Cu2+ + 2e- →Cu Eo Cu = +0.34V

2H+ + 2e- →H2 Eo Cu = 0.00V
Zn2+ + 2e- →Zn Eo Cu = -0.76V

50
 The Eo of Cu is positive, so Cu gains more electrons than hydrogen ie oxidizing
strength is Cu2+ ˃H+˃Zn2+

ELECTROLYTIC CELL
Electrolytic cells are those cells in which electrical energy from an external source
causes non-spontaneous chemical reactions to occur. Voltaic cells are those in which
spontaneous reactions produces electricity and supply it to external circuit.

Electrolysis of molten sodium chloride (DOWNS CELL)

Solid sodium chloride does not conduct electricity. Its ions vibrate about fixed positions,
but they are not free to move throughout the crystal. Molten (melted) NaCl, however, is an
excellent conductor because its ions are freely mobile. Consider a cell in which a source of
direct current is connected by wires to two inert graphite electrodes. They are immersed in a
container of molten sodium chloride. When the current flows, we observe the following.
1. A pale green gas, which is chlorine, Cl2, is liberated at one electrode.
2. Molten, silvery white metallic sodium, Na, forms at the other electrode and floats on top of
the molten sodium chloride.

(a)The apparatus showing the electrolysis of molten NaCl and (b) is the DOWNS
CELL, the molten NaCl is commercially electrolysed producing Na metal and Cl 2 gas

From these observations we can deduce the processes of the cell. Chlorine must be
produced by oxidation of Cl- ions, and the electrode at which this happens must be the

51
anode. Metallic sodium is produced by reduction of Na + ions at the cathode, where electrons
are being forced into the cell.
2Cl- → Cl2(g) + 2e (oxidation, anode half-reaction)
2Na++ 2e→ 2Na (reduction, cathode half-reaction)
2Na+ + 2Cl-→ 2Na + Cl2(g) (overall cell reaction)

The formation of metallic Na and gaseous Cl2 from NaCl is nonspontaneous except at
temperatures very much higher than 801°C. The direct current (dc) source must supply
electrical energy to force this reaction to occur. Electrons are used in the cathode half
reaction (reduction) and produced in the anode half-reaction (oxidation). They therefore
travel through the wire from anode to cathode. The dc source forces electrons to flow
nonspontaneously from the positive electrode to the negative electrode. The anode is the
positive electrode and the cathode the negative electrode in all electrolytic cells. The figure
above is a simplified diagram of the cell.
Sodium and chlorine must not be allowed to come in contact with each other because they
react spontaneously, rapidly, and explosively to form sodium chloride. The figure (b) shows
the Downs cell that is used for the industrial electrolysis of sodium chloride. The Downs cell
is expensive to run, mainly because of the cost of construction, the cost of the electricity,
and the cost of heating the NaCl to melt it. Nevertheless, electrolysis of a
molten sodium salt is the most practical means by which metallic Na can be obtained, owing
to its extremely high reactivity. Once liberated by the electrolysis, the liquid Na metal is
drained off, cooled, and cast into blocks. These must be stored in an inert environment (e.g.,
in mineral oil) to prevent reaction with O2 or other components of the atmosphere.
Electrolysis of NaCl in the Downs cell is the main commercial method of producing metallic
sodium. The Cl2 gas produced in the Downs cell is cooled, compressed, and marketed. This
partially offsets the expense of producing metallic sodium, but most chlorine is produced by
the cheaper electrolysis of aqueous NaCl.

THE ELECTROLYSIS OF AQUEOUS SODIUM CHLORIDE

Consider the electrolysis of a moderately concentrated solution of NaCl in water, using inert
electrodes. The following experimental observations are made when a sufficiently high
voltage is applied across the electrodes of a suitable cell.
1. H2 gas is liberated at one electrode. The solution becomes basic in that vicinity.
2. Cl2 gas is liberated at the other electrode.
Chloride ions are obviously being oxidized to Cl 2 in this cell, as they were in the electrolysis
of molten NaCl. But Na+ ions are not reduced to metallic Na. Instead, gaseous H 2 and
aqueous OH- ions are produced by reduction of H2O molecules at the cathode.
Water is more easily reduced than Na ions. This is primarily because the reduction of Na +
would produce the very active metal Na, whereas the reduction of H 2O produces the more
stable products H2(g) and OH-(aq). The active metals Li, K, Ca, and Na displace H 2 from
aqueous solutions, so we do not expect these metals to be produced in aqueous solution.
This is explained in the diagram below.

52
FARADAY’S LAW OF ELECTROLYSIS.
Faraday states that the amount of substance that undergoes oxidation or reduction at each
electrode during electrolysis is directly proportional to the amount of electricity that passes
through the cell.
A quantitative unit of electricity is now called the Faraday.
One Faraday is the amount of electricity that corresponds to the gain or loss, and therefore
the passage, of 6.022 x 1023 electrons, or one mole of electrons.
A smaller electrical unit commonly used in chemistry, physics, and electronics is the
Coulomb (C). One coulomb is defined as the amount of charge that passes a given point
when 1 ampere (A) of electric current flows for 1 second. One faraday is equal to 96,485
coulombs of charge.

Second law of electrolysis

Faraday’s second law of electrolysis states that when the same amount of electricity is
passed through different electrolytes, the mass of substance liberated/deposited at the
electrodes is directly proportional to their equivalent weights.

Electric charge
Electric charge(q) is measured in coulombs(C). The magnitude of the charge of a single
electron is 1.62 X 10-19C. This means that 1 mole of electrons has a charge of 9.649 X 10 4 C
and this is called faraday constant.
q= n X F

53
Example
1.If 5.58g of Fe3+ was reduced to Fe 2+ and V2+ oxidized to V3+, how many coloumbs of
charge must be transferred from V2+ to Fe3+.
Solution
Fe3+ + e- → Fe2+
5.58g of Fe3+ = 0.1mol Fe3+
q = 0.1mol X 9.649 X 104 C/mol
= 9649C.

2. Suppose that electrons are forced into a platinum wire immersed in a solution
containing Sn4+ which is reduced to Sn2+ at a constant rate of 4.24mmol/h. how
much current flows into the solution.

solution
Sn4+ + 2e- → Sn2+
If Sn4+ reacts at a rate of 4.24mmol/h, electrons flow at a rate of 2 X 4.24 = 8.48mmol/h
8.48 mmol /h
= 2.36 X 10-3mmol/s
3600 s/h
= 2.36 X 10-6mol/s
To find the current, we convert the moles per second to coloumbs/s
Current = 2.36 X 10-6mol/s X 9.649 X104C/mol
=0.23C/s =0.23 amperes
Where a charge ,q, moves through a potential difference ,E, the work done is W = E . q

3. How much work is required to move 2.36mmol of electrons through a potential

difference of 1.05V.

Solution
q = nF = 2.36 X 10-3 mol X 9.649 X 104 C/mol
= 2.28 X 102 C
W = 1.05V x 2.28 x 102C
= 239J.

4. Calculate the mass of copper metal produced during the passage of 2.5 amperes of
current through a solution of CuSO4 for 50mins.

Solution
The half reaction that describes the reduction is :
Cu2+ + 2e- → Cu ( reduction, cathode)
1mol of Cu2+ + 2(6.02 x 1023)e- → 1 mol of Cu metal
63.5g 2 X 96500 C 63.5g

No of coloumbs passing through the cell Q =It

= 2.5 X 50 X 60 =7500C

54
63.5g Cu produces 2X 96500C

? gives 7500C

= 63.5 x 7500/193000 = 2.47g( This is the amount of copper deposited by the current in
50mins)

Examples

5. How many Faradays passes through a resistance in a circuit carrying of 5A for 1

hour?
(1F = 96500)

Solution: Q = It Q = 5 x (60 x 60)

= 18000c

Number of Faradays = 18000

96500 = 0.187F
6. What is the number of moles of silver formed when a current of 0.3A is passed
through a Silver nitrate for 30 minutes?
Solution: Ag+ + e- Ag(s)

To form 1 mole of Ag, 1 mole of electrons, i.e. 1F is required.

Q = It = 0.3 x 30 x 60
Number of moles of Ag formed = It = 0.3 x 30 x 60
nF 1 x 96500
= 5.6 x 10-3mol.
7. What is the mass of copper formed at the cathode when a current of 0.25A is passed
through a copper (II) Sulphate solution for 1 hour? (Cu = 63.5)
Solution: (Cu2+ (aq) = 2e- Cu (s)

To discharge 1 mole of Cu2+, 2 moles of e-, i.e. 2F are needed

Number of moles of Cu formed = 0.25 x 60 x 60

55
 2 x 96500

= 4.66 x 10-3mol

.: mass of Cu formed = 4.66 x 10-3 x 63.5 = 0.296g

8. Find the masses of the products formed when a dilute sulphuric acid solution is
electrolyzed with a current of 0.6A for 90 minutes. (H = 1.0, O = 16.0)
Solution: when a dilute sulphuric acid solution is electrolyzed, hydrogen is formed
at the cathode and oxygen is formed at the anode of the electrolytic cell.

At cathode: 2H+ (aq) + 2e- H2 (g)

To give 1 mole of hydrogen gas, 2 moles of electrons i.e 2F are required.

Number of moles of H2(g) formed = 0.6 x 90 x 60

2 x 96500

= 0.0168mol

.: mass of hydrogen formed = 0.0168 x (1.0 x 2)

= 0.0336g

At anode: 40H- (aq) O2 (g) + 2H2O (l) + 4e-

To give 1 mole of oxygen gas, 4 moles of electrons, i.e 4F are given out by the
hydrogen ions.

Number of moles of O2(g) formed = 0.6 x 90 x 60

4 x 96500

= 8.394 x 10-3mol

Mass of oxygen formed = 8.394 x 10 -3 x (16 x 2) = 0.2686g.

56
Exercises

1. What mass of copper would be deposited by the quantity of electricity that liberates
2.4dm3 of oxygen measured at room temperature and pressure? (molar volume of gas at
R.T.P = 24dm3mol-1, O = 16, Cu = 63.5)
2. A current of 0.37A flowing for 15 minutes liberates 0.20g of a metal X. What mass of X
would be liberated by a current of 0.30A for 30 minutes?

CHEMICAL KINECTICS

Chemical kinetics is the study of reaction rates, factors that affect rates and the
theory of reaction rate in terms of reaction mechanism.

RATE EQUATIONS:

A rate equation is a mathematical equation that shows the rate in terms of changes in
concentrations of substances.
For a chemical reaction, the change in concentration of a reaction or a product (Dc)
that occurs over a time interval (Δt) is the average rate:

Average rate = Δc
Δt
When the time interval (Δt) approaches zero, what we obtain is the reaction rate at that
particular time. Mathematically, it is given by:
Instantaneous rate = lim Dc = dc
Δt o Δt dt

In particular, when t = to, the instantaneous rate is known as initial rate.

The rate we consider is the reaction rate at that particular time. Using the following
reaction as an example: A + B 2C

57
 The rate of reaction can be expressed as the rate of decrease in concentration of A
or B, or increase in the concentration of product C. Since two moles of C are formed from
any one mole of A and B reacted, the rate of decrease in concentration of A or B is only half
of the rate of increase in concentration of C.
The rate equation of the reaction is:
Rate = -d[A]= -d[B] = ½ x d[C]
dt dt dt
where –d[A] and –d[B] represent the decrease in concentrations of reactants A and B
respectively,
d[C] represents the increase in concentration of product C,
dt represents a very short time interval, and the minus sign changes the negative
values of
d[A] and d[B] to positive ones
dt dt
In general, aA + bB cC + dD
Where A and B = reactants in the reaction

C and D = products in the reaction

a, b, c, and d = coefficients in a balanced chemical equation.

Rate = -1 x d[A] = -1 x d[B] = 1 x d[C] = 1 x d[D]

a dt b dt c dt d dt

Example: Haemoglobin (Hb) reacts with carbon monoxide according to the following
equation. Write its rate equation.

4Hb + 3CO Hb4 (CO)3

Solution: Rate = d [Hb4 (CO)3]

dt

= -¼ x d [Hb] = -1 x d [CO]

dt 3 dt

58
Exercise

(a) Write a rate equation for the following reaction:

N2 (g) + 3H2 (g) 2NH3(g)

ORDER OF REACTION

The order of reaction is defined as the sum of the power of the concentration terms in
the rate law.

In general, for the reaction:

aA + bB C

The reaction is expressed by the rate equation or rate law,

Rate = K[A]x [B]y

In the rate equation, K is the rate constant of the reaction. x and y are constant for
that particular reaction which can be determined experimentally. x is the order of reaction
with respect to A, while y is the order of reaction with respect to reactant B. The overall
order of the reaction is x + y.

OVERALL ORDER OF REACTION: This is the sum of powers of the concentration of

individual reactants. This is equal to x + y in the case above.

The orders of reaction are usually integers like 0, 1, 2, etc. If x = 1, the reaction is first
order with respect to reactant A. If y = 2, the reaction is second order with respect to
reactant B. The overall order of reaction is x + y = 3, i.e. third order. It should be noted that
orders of reaction x and y are not related to a and b in the balanced stoichiometric
equation.The order of reaction, i.e x + y is a value which can only be determined
experimentally.

ZEROTH ORDER REACTION:-For a zeroth order reaction,

59
A product: RATE = K [A]0 = K.

A zeroth (or zero) order reaction is the one that the rate of reaction is independent of the
concentration of the reactant. By plotting rate against [A], a horizontal straight line is
obtained.

Rate

Slope = 0

[A]

Zeroth order reaction

FIRST ORDER REACTION: For a first order reaction, the rate is directly proportional to the
concentration of the reactant. For a first order reaction,

A product: Rate = K[A], and a straight line is produced when a graph of rate is plotted
against [A].

Rate

Slope = K

[A]

FIRST ORDER REACTION

SECOND ORDER REACTION: There are two types second order reaction:

(1) For a second order reaction with its rate depending on one reactant only:

60
 A products, Rate = -d[A] = K [A]2

dt

In a second order reaction (second order with respect to reactant A), the rate is directly
proportional to the square of the concentration of reactant A. By plotting rate against [A] 2, a
straight line is produced.

Rate

Slope = K

[A]2

Second order reaction with respect to reactant A

(2) For a second order reaction with its rate depending on two reactants:
A + B Products

Rate = -d[A] (For constant [B])

dt

= -d[B] (for constant [A])

dt

= K [A] [B]

In this case, the rate is directly proportional to [A] when [B] is kept constant, and vice
versa. Hence, the reaction is actually of first order with respect to A and B respectively.

(a) Rate (b) Rate

Second
Slope = K
Order Slope = K
provided [A]
Reaction when [B] is
is constant
constant

61
 [A] [B]

The overall reaction is of the second order. It should be noted that only the effect of
concentration of one reactant can be studied at a time (the concentration of the other one
must be kept constant).

RATE CONSTANT: The rate constant K, is temperature dependent. At a fixed temperature,

it is a constant for a reaction.

For the reaction, aA + bB C

If [A] and [B] are both 1.0 moldm-3, then

Rate = K[1.0]x [1.0]y = K

Hence, K is numerically equal to the rate. It tells how fast the reaction is. In general,
the greater the rate constant K, the faster the reaction rate. The unit of K depends on the
overall order of the reaction.

Rate = K[A]x [B]y

K= Rate

[A]x [B]y

i.e unit of K = moldm-3S-1

(moldm-3)n

Unit of K = (moldm-3) 1-n S-1

NB: Assume the overall order of reaction is n, n = x + y

UNITS OF RATE CONSTANT K FOR DIFFERENT ORDERS OF REACTION

62
Order of reaction Units of K

Zeroth order moldm-3s-1

First order s-1
Second order mol-1 dm3 s-1
Third order mol-2 dm6 s-1

Example: In the kinetic study of the reaction, CO + NO 2 → CO2 + NO, the initial
concentration of the reactants and initial reaction rates were determined by a number of
experiments. The results were as follows:

Experiment Initial conc.of CO, Initial conc.of NO2, Initial Rate, mol dm-3
mol dm-3 mol dm-3 s-1

1 0.1 0.1 0.015

2 0.2 0.1 0.030
3 0.1 0.2 0.030
4 0.4 0.1 0.060

i. Establish the rate equation for the reaction.

ii. Find the initial rate of the reaction when the initial concentration of both CO and NO 2 are
0.3 mol dm-3.

Soln: Let Rate = k [CO]m [NO2]n

Then, 0.015 = k [0.1]m [0.1]n (1)

0.03 = k [0.2]m [0.1]n (2)

0.03 = k [0.1]m [0.2]n (3)

0.06 = k [0.4]m [0.1]n (4)

63
 n
0.015 [0.1]
1 ÷ 3: =
0.03 [0.2]n

0.5 = 0.5n ∴ n=1

0.03 [0.2]m
2 ÷ 4: =
0.06 [0.4 ]m

0.5 = 0.5m ∴ m=1

From (1): Rate = k [CO]m [NO2]n

0.015 = k [0.1] [0.1]

0.015 −1 3 −1
K= =1.5 mol dm s
0.01

∴ Rate equation: Rate = 1.5 [CO] [NO2]

(ii) Rate = 1.5 [CO] [NO2] = 1.5 [0.3] [0.3] = 0.135 mol dm-3 s-1

HALF-LIFE:- This is the time taken for half of the reactant to be converted to the product. It
is denoted by t½ . The half life is the time required for the concentration of A to decrease
from [A]o to ½ [A]o

For a first order reaction,

I.e. In [A]o = K1 t½
½ [A]o

ln 2 = K1 t½
t½ = ln2 = 0.693
K1 K1

Example: The half-life of a radioactive isotope A is 1997 years. How long does it take for a
sample of A to decay to 20% of its original radioactivity?

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 Solution: t½ = 0.693

.: K1 = 0.693 = 3.47 x 10-4 years-1

1997

Since ln [A]o = K1

[A]

ln 100% = 3.47 x 10-4t

20%

.: t = 4638 years

STATES OF MATTER

Matter is anything that has mass (or weight) and can occupy space. There are three
states of matter – solid, liquid and gas.

KINETIC THEORY OF MATTER

The kinetic theory of matter postulates that matter is composed of small particles
such as atoms, molecules and ions in constant motion and collisions between these
particles are perfectly elastic. An increase in temperature causes an increase in the average
kinetic energy of the particles.

Properties of solids, liquids and gases

S/N SOLID LIQUID GAS

1. Fixed mass Fixed mass Fixed mass

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2. Particles vibrate and rotate Particles vibrate, rotate Particles move about
about a fixed position and move about within a constantly at great
restricted space speed and at random

3. Fixed shape No fixed shape (assumes No fixed shape

the shape of a container)

4. Fixed volume Fixed volume No fixed volume

5. Incompressible Incompressible Compressible

6. Very dense Less dense Least dense

Random motion and kinetic energy of particles increases from solid to gas, i.e.

Solid < liquid < gas

Orderliness of particles increases from gas to solid i.e.

Gas < liquid < solid

CHANGE OF STATE: A substance can exist as a solid, a liquid or a gas. Change of state of
a given substance is brought about by a change in temperature (i.e. heating or cooling). By
heating a substance, its particles acquire more kinetic energy. When cooled they become
less energetic.

Gas

Evaporation Sublimation

Condensation

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Freezing

Melting
 Liquid Solid

A SUBSTANCE CAN EXIST AS A LIQUID, SOLID OR A GAS

Examples:

H2O (l) Freezing H2O (s)

H2O (g) Condensation H2O (l)

NH4Cl (s) Sublimation NH4Cl (g)

THERMOCHEMISTRY AND CHEMICAL ENERGETIC

THERMOCHEMISTRY: This is the study of energy transferred as heat during the course of
chemical reactions.

During a chemical reaction, there is an associated energy change which is due

to difference in the energy contents between the reactants and the products. This change is
as a result of transfer of energy between the reacting system and its surroundings. Such
energy change may be in form of electromagnetic radiation or electrical energy but most
commonly in the form of heat. The study of such energy change is known as ENERGETIC.

Energy transfer must satisfy the law of conservation of energy. The law of
conservation of energy states that energy can neither be created nor destroyed but can be
changed from one form to another. Thus the total amount of energy of the system remains
the same.

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 In thermochemistry, the total energy stored in a substance is called the HEAT
CONTENT OR ENTHALPY, with symbol, H. Actually, the enthalpy of a substance cannot be
measured, but the enthalpy change, ΔH can be measured experimentally as there is heat
absorbed or evolved during a reaction.

ΔH = Enthalpy of products – Enthalpy of reactants

ΔH = Hp – Hr

EXOTHERMIC AND ENDOTHERMIC REACTIONS

An exothermic reaction is a reaction that releases heat to the surroundings. ΔH of

exothermic reactions is negative.

An endothermic reaction is one that absorbs heat energy from the surroundings.
Here, ΔH is positive.

STANDARD ENTHALPY CHANGES

The enthalpy of a substance depends on its physical state, the temperature and
pressure. So in order to standardize the data on enthalpies of reactions, it is necessary to
define the standard states and conditions. They are defined as

(1) Elements or compound in their normal physical states

(2) A pressure of 1 atm (101325 Nm-2)
(3) A temperature of 250C (298K)

ΔHθ refers to enthalpy change specified at standard conditions or is simply called the
standard enthalpy change of reaction.

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STANDARD ENTHALPY CHANGE OF REACTION: This is defined as the heat absorbed
or evolved (enthalpy change) when molar quantities of reactants as stated in the balanced
equation react together under standard conditions.

ΔHθ = Standard Enthalpy of Products - Standard Enthalpy of Reactants

i.e ΔHθ = ΔHθp - ΔHθr

STANDARD ENTHALPY CHANGE OF NEUTRALIZATION – Is the enthalpy change when

one mole of water is formed from neutralization of an acid by an alkali under standard
conditions.

H+ (aq) + OH -(aq) H2O (l) ΔHθneut = - 57.3kjmol-1

1mole

ΔHθneut always negative (exothermic)

STANDARD ENTHALPY CHANGE OF SOLUTION: Is defined as the enthalpy change when

one mole of a solute is dissolved to form an infinitely dilute solution under standard
conditions.

NaCl(s) + (aq) Na+(aq) + Cl-(aq) ΔHθsoln = +3.9KJmo-1

1 mole

.: ΔHθsoln [NaCl(s)] is + 3.9KJmol -1

The standard enthalpy change of solution can be endothermic or exothermic.

STANDARD ENTHALPY CHANGE OF FORMATION: Is the enthalpy change of reaction

when one mole of the compound in its standard state is formed from its constituent elements
under standard conditions.

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 The process may be exothermic or endothermic. e.g.
Water: 2H2(g) + O2 (g) 2H2O(l) ΔHθ = - 572KJmol-1

H2 (g) + ½ O2 (g) H20(l) ΔH = -286KJmol-1

1mole

NITROGEN (IV) OXIDE

N2(g) + 2O2(g) 2NO2(g) ΔHθ = + 67.8Kjmol-1

½ N2(g) + O2(g) NO2(s) ΔHθf = + 33.9KJmol-1

1mole

STANDARD ENTHALPY CHANGE OF COMBUSTION: This is the enthalpy change when

one mole of substance is burnt completely in oxygen under standard conditions.
It is simply the standard enthalpy change for the reaction of the substance with
oxygen.
Standard enthalpy change of reaction is negative as combustion is exothermic.
C(s) + O2(g) CO2(g) ΔHθC = - 393.5KJmol-1
HESS’S LAW: Hess’s law of constant heat summation states that the total enthalpy change
accompanying a chemical reaction is independent of the route by which the chemical
reaction takes place.
Consider two routes for reactants A and B to form products C and D, the standard
enthalpy change of reaction by route 1 is the same as the standard enthalpy change of
reaction by route 2 as shown below.
A + B Route 1 C+D
Diagram showing
ΔH2
different routes of
ΔH2 ΔH3 chemical reaction.
E
Route 2
Enthalpy change by route 1 = enthalpy change by route 2 i.e, ΔH1=ΔH2 +ΔH3

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 E
Enthalpy

Route 2
A + B
Route 1 C + D

A simplified enthalpy level diagram showing the relative energetic stabilities

Hess’s law is actually a direct consequence of the conservation of energy. In order to obtain
reliable ΔH values for reactions, the reactions must go to completion. The importance of
Hess’s law lies in the fact that the enthalpy change can be calculated for reactions that
cannot be performed in the laboratory, or reactions that are too slow or involve the formation
of side products.
CALCULATIONS INVOLVING STANDARD ENTHALPY CHANGES OF REACTIONS
The standard enthalpy change of a reaction is equal to the standard enthalpy content of the
products minus the standard enthalpy content of reactants (ΔH θ = HθP - Hθr). There are two
simple methods to calculate the enthalpy change of a reaction:
(1) using enthalpy change of combustion
(2) Using enthalpy change of formation.
Examples:
1. Given the following information, find the enthalpy change for the reaction:
4CH3.NH.NH2(l) + 5N204 (l) 4CO2 (g) + 12H2O (l) + 9N2(g)

ΔHθf [CH3.NH.NH2 (l)] = + 53KJmol-1

ΔHθf [N2O4(l)] = - 20KJmol-1

ΔHθf [CO2(g)] = -392.5KJmol-1

ΔHθf [H2O(l)] = -285.8KJmol-1

Solution:

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 4CH3.NH.NH2 + 5N2O4 ΔHθ 4CO2 + 12H2O + 9N2

ΔH1 ΔH2

4C(graphite) + 12H2 + 9N2 + 10O2

ΔH1 = 4 x ΔHθf [CH3.NH.NH2] + 5 x ΔHθf [N2O4]

ΔH2 = 4 x ΔHθf [CO2 + 12 x ΔHf [H2O]

From Hess’s law: ΔHθ + ΔH1 = ΔH2

ΔHθ =ΔH2 - ΔH1

= (4 x ΔHθf [CO2] + 12 ΔHθf [H2O]

- (4 x ΔHθf [CH3.NH.NH2] + 5 x ΔHθf [N2O4(l)]

= [4 (-3.93.5) + 12 (-285.8)] – [4 (+53) + 5 (-20)] = - 5115.6 KJmol -1

.: Enthalpy change (ΔHθ) = - 5115.6 KJmol-1

2. Given the following information, find the enthalpy change of the formation for ethanol.
C(s) graphite + O2(g) CO2(g)

ΔHθC [C(s) graphite)] = - 393.5 KJmol-1

H2(g) + ½ O2(g) H2O (l). ΔHθc [H2(g)] = - 285.8 KJmol-1

C2H5OH(l) + 3O2(g) 2CO2(g) + 3H2O (l)

ΔHθc [C2H5OH(l)] = -1371 KJmol-1

Soln. 2C(g) (graphite) + 3H2(g) ΔHθf [C2H5OH] C2H5OH(l)

+
+ + ½ O2(g)
1 ½ O2(g) + 3O2(g)
2O2 ΔH2
ΔH3
(g) 2CO2 + 3H2O
ΔH1

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 ΔH1 = 2 x ΔHθc [C(s) (graphite)]

ΔH2 =3 x ΔHθc [H2(g)]

ΔH3 = ΔHθc [C2H5OH(g)]

Using Hess’s law: ΔHθf [C2H5OH] + ΔH3 = ΔH1 + ΔH2

ΔHθc [C2H5OH] = ΔH1 + ΔH2 – ΔH3

= 2 x ΔHθc [C (s) graphite] + 3 x ΔHθc [H2]

- ΔHθc [C2H5OH]

= 2( -393.5) + 3(-285.8) – (- 1371)

= - 273.4KJmol-1

.: The enthalpy change for the formation of ethanol is – 273.4KJmol-1

3. Given the following information, find the enthalpy change for the reaction.
6PbO(s) + O2 (g) 2Pb3O4(s)
ΔHθf [PbO(s)] = - 220.0KJmol-1

ΔHθf [Pb3O4 (s)] = - 737.5KJmol-1

6PbO(s) + O2(g) ΔHθ 2Pb3O4(S)

ΔH1 ΔH2

6Pb(s) + 4O2(g)

Solution:

ΔH1 = 6 x ΔHθf [PbO(s)]

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 ΔH2 = 2 x [Pb3O4(s)]

Using Hess’s law: ΔHθ + ΔH1 = ΔH2

ΔHθ = ΔH2 - ΔH1

= 2 x ΔHθf [Pb3O4] - 6 x ΔHθf [PbO]

= 2 x (-737.5) - 6 x (-220.0)

= - 155.0KJmol-1

Exercise:

1. Given the following information, find the enthalpy change for the reaction.
Fe2O3 + 3CO 2Fe + 3CO2

ΔHθf [Fe2O3] = -822.0KJmol -1

ΔHθf [CO] = -110.5KJmol-1

ΔHθf [CO2] = - 393.5KJmol-1

2. Find the enthalpy change of formation for butane [C 4H10(g)]

Given: ΔHθc [C(s) graphite] = - 393.5KJmol-1

ΔHθc [H2(g)] = - 285.8KJmol-1

ΔHθc [C4H10(g)] = 2877KJmol-1

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