CHM 101 General Chemistry I - LN - Part 1

CHM 101: General Chemistry I
Lecture Notes
For
Level 100 Students
Prepared by
Dr. Shehu Habibu
s.habibu@fud.edu.ng
Department of Chemistry
Faculty of Science
Federal University Dutse
2020/2021 Session
CHM 101 General Chemistry I, Federal University Dutse, 2020/2021 Session)First Semester(, Dr. Shehu Habibu
Course Outline
Part 1: Physical Chemistry
 Properties of gases
 Kinetic Molecular Theory of gases
 Thermochemistry
 Chemical Kinetics
 Equilibria and thermodynamics
 Concept of pH
 Redox Reactions
 Introduction to Electrochemistry
Part 2: Inorganic Chemistry

 Atoms, molecules and chemical reactions
 Modern electronic theory of atoms
 Electronic Configuration
 Periodicity and building up of the periodic table
 Chemical equations and stoichiometry
 Chemical bonding and intermolecular forces
 Radioactivity
 Hybridization of simple molecules.
Relevant Textbooks
1. M. S. Dagari (2006). Basic Physical Chemistry (with over 200 solved problems)
2. D. W. Oxtoby, H. P. Gillis and A. Campion (2008). Principles of Modern Chemistry (seventh
Edition), Brooks/Cole, Cengage Learning, Canada.
3. R. Chang (2008). General Chemistry (Fifth Edition), McGrawHill Higher Education
Course Lecturers
Group Students Lecturers
A Microbiology, Botany and Zoology Dr. S. Nasir and Dr. Sa’adatu M. Eri
B Biology and Biochemistry Dr. Y. A. Adamu and Mal. T. Abdulrahman
C Chemistry and Biotechnology Dr. M. B. Idris and Dr. S. Suleiman
D Physics and EMT Dr. Abdul A. Olaleye and Mal. S. L. Enesi
E Maths and Computing Dr. S. M. Yakasai and Mal. A. Shehu
F Faculty of Agric. (Group A) Dr. Hajara Momoh and Dr. N. I. Durumin-Iya
G Faculty of Agric. (Group B) Dr. I. S. Shina and Mlm. Hadiza U. Abdullahi
H College of Medicine Dr. S. Habibu and Mal. M. Ahmadu
Course Coordinator: Dr S. Habibu (s.habibu@fud.edu.ng)
2
CHM 101 General Chemistry I, Federal University Dutse, 2020/2021 Session)First Semester(, Dr. Shehu Habibu
PART 1: PHYSICAL CHEMISTRY
PROPERTIES OF GASES
Matter exists in three states these are: solid, liquid and gaseous.
Gaseous State
A gas consists of molecules separated wide apart in empty space. The molecules are free to move
about throughout the container.
Characteristics of a gas
 Expansibility
 Compressibility
 Diffusibility
 Ability to exert Pressure
Parameters of a Gas
A gas sample can be described in terms of four parameters (measurable properties)
i. The volume (V) of the gas,
ii. Its pressure (P),
iii. Its temperature (T) and
iv. The number of moles (n) of the in a container.
GAS LAWS
Boyle’s Law
Boyle’s Law states that; at constant temperature, the volume of a fixed mass of gas is inversely
proportional to its pressure. If the pressure is doubled, the volume is halved.
Mathematically,
V α or V = k x (k is proportionality constant)
Therefore, PV = k or P1V1 = k1 and P2V2 = k2
Where P1 = initial pressure
P2 = final pressure
V1 = initial volume
V2 = final volume
Charles’s Law
Charles’s law states that at constant pressure, the volume of a fixed mass of gas is directly proportional
to its absolute temperature. If the temperature is doubled, the volume is doubled.
Mathematically,
𝑽
V α T or V = KT or = K (k is constant of proportionality)
𝑻
Therefore,
= k1 and, = k2
3
CHM 101 General Chemistry I, Federal University Dutse, 2020/2021 Session, Dr. Shehu Habibu
Ideal Gas
An Ideal Gas is any gas that obeys the equation of state PV = nRT.
Where P is the pressure of the gas, V is the volume, n is the number of moles, R is the molar gas
constant and T is the temperature.
Where n = number of moles
R = molar gas constant with a value of 0.0821atmLmol-1K-1 or 8.314 Jmol-1K-1
Derivation of an Ideal Gas Equation
The ideal gas equation is derived by combining Boyle’s and Charles’s laws and Avogadro’s hypothesis.
From Boyle’s law
P1V1 = k1 and P2V2 = k2 ……………………………………………………………………………………..(1)
From Charles’s law,
= k1 and = k2 …………………………………………………………………………………….…….….(2)
Combining (1) and (2) gives;
= k1 and = k2 or = k ………………………………………...……………...............(3)
For a fixed mass of gas, the constant is proportional to the number of moles, n.
= (constant) x n …………………………….………………………….…………………...(4)
The new constant is called R, the molar gas constant.
So, = nR or PV = nRT …………………...............................................………………….(5)
PV= nRT (5) is known as the IDEAL GAS EQUATION.
The ideal - gas equation is called an equation of state for a gas because it contains all the variables
(T,P,V and n) which describe completely the condition or state of any gas sample. If we know the three
of these variables, it is enough to specify the system completely because the fourth variable can be
calculated from the ideal-gas equation.
The Numerical value of R
From the ideal-gas equation, we can write
R=
We know that one mole of any gas at STP occupies a volume of 22.4litres. Substituting the values in
the above expression, we have
× .
R= = 0.0821atmLmol-1K-1
×
R has various equivalent values depending on the units of P and V used in the ideal-gas equation.
R can also be expressed in Jmol-1K-1 as follows.
1atm = 1.0132𝚡105Nm-2 and 1dm3 = 10-3m3.
R= 0.0821 atmLmol-1K-1 = 0.0821 atmLmol-1K-1x 1.0132𝚡105Nm-2x10-3m3xatm-1xdm-3 = 8.314J mol-1K-1
where 1J= 1Nm.
Therefore R= 8.314J mol-1K-1
Calculating the number of Moles, n
Number of moles (n) =
4
Example:
Calculate the number of moles of the following gases;
a). 5.6g of Nitrogen gas, N2(g) b) 1.32g of CO2(g)
Solution:
.
a). nN2(g) = = 0.20mol
/
.
b). nCO2(g) = = 0.03mol
/
The usefulness of the ideal gas equation is that it relates the four variables, P, V, n and T, that describe
a sample of gas at one set of conditions.
Example:
What pressure, in atmosphere is exerted by 54.0g of Xe in a litre flask at 293K?
Solution:
V= 1.0L, n= 0.411mol, T = 293K and P=?
using PV= nRT
gives: P =
0.411𝑚𝑜𝑙 𝑥 0.0821𝐿 𝑎𝑡𝑚 𝑚𝑜𝑙 𝐾 𝑥 293𝐾

𝑃=
1.0𝐿
P = 9.89 atm
Dalton’s Law of Partial Pressure
This law states that the total pressure (P) of a mixture of gases is equal to the sum of the partial
pressures of all the gases present.
Mathematically;
Total Pressure, PT = P1 + P2 + …......................…… Pn
Where P1 , P2 and Pn are partial pressures of the gases 1, 2, .... n.
PT = (n1+ n2+ nn) RT/V or ntRT/V
Example
What pressure is exerted by a mixture of 2.00g of H2 and 8.00g N2 at 273K in 10L vessel?
Solution
Using P =
Moles of H2 = 2.0/2.02 = 0.99 moles
Moles of N2 = 8/28 = 0.286 moles

. .
PH2 = = 2.22 atm
.
. .
PN2 = = 0.64 atm
.
5
Thus, PT = PH2 + PN2 = 2.86 atm.
Hence, the pressure exerted by the mixture of Hydrogen and Nitrogen is 2.86 atm.
Exercise: What pressure is exerted by a mixture of 3.0 g of H 2 and 1.5g of O2 at 105 0C in a 10 litre
container?
Mole Fractions
By definition, nA + nB = ntotal …………………………….................................................….(1)

Divide eqn.1 through by ntotal
+ = =1
XA + XB = 1, where XA = , the mole fraction of A and XB = the mole fraction of B.

The sum of the mole fractions of the components of a mixture is equal to 1.
Relationship between Partial Pressure, Mole Fraction and Total Pressure

Consider an ideal gas mixture (binary) of A and B. From the ideal gas equation PV= nRT;
PA = ………………………………………...............................................……………….…….(i)
Ptotal = …………..........................................………………………………………………(ii)
Dividing equation (i) by equation (ii), we have:
= = XA ……………...........................................…………………………..…………(iii)
:. PA = XA Ptotal …………….................................…………………………………………….……...(iv)
The partial pressure of a particular component is equal to its mole fraction multiplied by the total
pressure.
Kinetic Molecular Theory (KMT) of Gases

Maxwell and Boltzmann (1859) developed a mathematical theory to explain the behaviour of gases
and the gas laws. It is based on the fundamental concept that a gas is made of a large number of
molecules in perpetual motion. This theory is called the Kinetic Molecular Theory or the Kinetic Theory
of Gases.
Assumptions of the KMT

i. A gas consists of extremely small discrete particles called molecules dispersed throughout
the container. It means that the actual volume of the molecules is negligible compared to
the total volume of the gas. The molecules of a given gas are identical and have the same
mass (m).
6
ii. Gas molecules are in constant random motion with high velocities. They move in straight
lines with uniform velocity and change direction on collision with other molecules or the
walls of the container.
iii. The distance between the molecules is very large and it is assumed that van der Waals
attractive forces between them do not exist. Thus, the gas molecules can move freely,
independent of each other.
iv. All collisions are perfectly elastic. Hence, there is no loss of the kinetic energy of a molecule
during collision.
v. The pressure of a gas is caused by the hits recorded by molecules on the walls of the
container.
vi. The average kinetic energy ( mv2) of the gas molecules is directly proportional to absolute
temperature. This implies that the average kinetic energy of molecules is the same at a
given temperature.
𝟏
Fundamental Equation for the Pressure of a Gas (PV= mNu2)
𝟑
This is the fundamental equation of the kinetic molecular theory of gases. It is called the Kinetic Gas
Equation. This equation although derived for a cubical vessel, is equally valid for a vessel of any shape.
The available volume in the vessel could well be considered as made up of a large number of
infinitesimally small cubes for each of which the equation holds.
u2 is the mean of the squares of the individual velocities of all the N molecules of the gas.
Kinetic Gas Equation in terms of Kinetic Energy
Let N be the number of molecules in a given mass of gas,

PV= mNu2 ………………………………....................…...............…(1)
But kinetic energy is equal to mu2 (where u = velocity of a molecule)
Therefore,
PV = × mNu2 ………………………………...........……............…(2)
= N x e……………………………………................….....................(3)
Where, e is the average kinetic energy of a single molecule.
Therefore, PV= Ne = E ………………….............…….................................................…(4)
Where, E is the total kinetic energy of all the N molecules.
Equation (4) is called the kinetic gas equation in terms of kinetic energy.
We know that the general ideal gas equation is PV= nRT…....................................(5)
From (4) and (5) above
E = nRT……………………………………………............................…(6)
For one mole of a gas, the kinetic energy of N molecules is,
E= ……………………………………………..........................….(7)
7
Example:
Calculate the kinetic energy of two moles of N 2 at 27oC. Take R = 8.314JK-1mol-1
Solution:
We know E = nRT,
Where, n = 2.0mol, T = (27 + 273) K = 300K and R = 8.314JK-1mol-1
On substitution we have, E = X 2.0mol X 8.314JK-1mol-1 X 300K =7482.6J
Therefore, the kinetic energy of two moles of N2 is 7482.6J.
Deduction of Gas Laws from the Kinetic Gas Equation

a). Boyle’s Law
According to the Kinetic Theory, there is a relationship between the average kinetic energy of the
molecules and absolute temperature (i.e. kinetic energy is directly proportional to the temperature),
Therefore,
mNu2 𝛼 T or mNu2 = kT ………………………..............................(1)
(Where, k = constant of proportionality).
Equation (1) can be written as;
× mNu2 = kT ...................................................................(2)
Multiplying equation (2) by , we have:
mNu2 = kT ………………..................................................…(3)
But the kinetic gas equation is, PV = mNu2 Therefore,
PV = kT ……………………………............................……(4)
The product PV, therefore, will have a constant value at a constant temperature. This is Boyle’s Law.
b). Charles’ Law
Also, according to the Kinetic Theory, there is a relationship between the average kinetic energy of
the molecules and absolute temperature (i.e. kinetic energy is directly proportional to the
temperature), Therefore,
mNu2 𝛼 T or mNu2 = kT ………………………...........................(1)
(Where, k = constant of proportionality).
Equation (1) can be written as;
× mNu2 = kT .................................................................(2)
Multiplying equation (2) by , we have:
mNu2 = kT ………………................................................…(3)
But the kinetic gas equation is, PV = mNu2 Therefore,
PV = kT …………………………….............................…(4)
Dividing both sides of equation (4) by P, we have:
V = kT x or V = T ……………….....………..….….. (5)
8
Therefore, V = (constant)T or V = k’T ……………………………….. (6)

Where k’ = k/P,
Hence, V T ………………………………………........................… (7)
This implies that, at constant Pressure, volume of a gas is proportional to Kelvin temperature and this
is Charles Law.
c). Avogadro’s Law

If equal volume of two gases be considered at the same pressure, we have:
PV = m1N1u12 ………………………………..(i) (kinetic equation applied to one gas)
PV = m2N2u22 ………………………………..(ii) (kinetic equation applied to the 2nd gas)
Therefore, m1N1u12 = m2N2u22 ……………(iii)
At the same temperature, the mean kinetic energy per molecule will also be the same.
∴ m1u12 = m2u22 …………………………..(iv)
Dividing (iii) by (iv), we have:
N1 = N 2
Hence, at the same Temperature and Pressure, equal volumes of the 2 gases contain the same number
of molecules. This is Avogadro’s Law.
d). Graham’s Law of Diffusion:

If m1 and m2 are the masses and u1 and u2 the velocities of the molecules of gases 1 and 2, then
from PV= mNu2 , at the same pressure and volume,
m1N1u12 = m2N2u22 …………………………….……….(1)
By Avogadro’s Law, N1 = N2 ……………………………....................……..….…(2)
m1u12 = m2u22 ……………………………….....................(3)
If M1 and M2 represent the molecular masses of gases 1 and 2, then,
( )2 = ………………………..............................……(4)
=√( ) ………………………….............................…(5)
The rate of diffusion (r) is proportional to the velocity of molecules (u), therefore,
= = √( ) ……………….(6)
This is Graham’s law of diffusion.
Real Gas
Differences between Ideal and Real gases
1. An ideal gas is infinitely compressible; a real gas will condense to a liquid at some pressure.
2. The particles of an ideal gas lose no energy to its container. A real gas conducts and radiates
heat, thereby losing energy.
9
3. There is no attraction between the molecules of an ideal gas. A real gas has particle
attractions.
4. An ideal gas can follow the formula 𝑃𝑉 = 𝑛𝑅𝑇. A real gas does not follow this formula.
Deviations from Ideal Behaviour
An ideal gas obeys the equation 𝑃𝑉 = 𝑛𝑅𝑇 at all pressures and temperatures. However, no gas is
ideal, almost all gases show significant deviations from the ideal behaviour. Thus, the gases H 2, N2
and CO2 that fail to obey the ideal gas equation are termed non-ideal or real gases.
Compressibility Factor
This explains the extent to which a real gas departs from ideal behaviours. It is defined by the
equation;
𝑃𝑉
𝑧=
𝑅𝑇
Where, Z = compresibility factor Vm = molar volume of the gas
 For an ideal gas, Z = 1 at all conditions (independent of T & P).

 For a real gas, Z can either be < 1 or > 1
 The difference between 1 and the value of Z determines the extent of deviation of a gas from
ideality.
 For real gases, a deviation depends on P and T. At a very low pressure, for all gases, Z ≈ 1
therefore, real gases exhibit nearly ideal behavior at a very low P.
 At a lower T, Z < 1 and at fairly high PZ ≈ 1.
CONCLUSIONS
From the above discussions, it can be concluded that:
1. At low pressures and fairly high temperatures, real gases show nearly ideal behavior and the
ideal gas equation is obeyed.
2. At low temperatures and sufficiently high pressures, a real gas deviate significantly from
ideality and the ideal gas equation is no longer valid.
3. The closer the gas is to the liquefaction point, the larger will be the deviation from the ideal
behavior.
EXPLANATION OF DEVIATION – VANDER WAALS EQUATION

Van der Waals (1873) attributed the deviations of real gases from ideal behavior to two erroneous
postulates of kinetic molecular theory. These are:
i. The molecules in a gas are point masses and occupies zero volume.
ii. There are no intermolecular forces of attractions in a gas.
10
Therefore, the ideal gas equation 𝑃𝑉 = 𝑛𝑅𝑇 derived from kinetic theory could not hold for real gases.
Van der Waals pointed out that both the pressure (P) and volume (V) factors in the ideal gas equation
need to be corrected in order to make it applicable to real gases.
Volume Correction
The volume of a gas is the free space in the container in which molecules move about. Volume V of an
ideal gas is the same as the volume of the container. The dot molecules of ideal gas have zero-volume
and the entire space in the container is available for their movement. However, Vander Waals assumed
that molecules of a real gas are rigid spherical particles that possess a definite volume.
The volume of a real gas is, therefore, ideal volume minus the volume occupied by gas molecules. If b
is the effective volume of molecules per mole of the gas, the volume in the ideal gas equation is
corrected as: (V-b)
For n moles of the gas, the corrected volume is (V-nb)
Where, b is termed the excluded volume, which is constant, and characteristics for each gas.
Excluded volume is four times the actual volume of molecules. Therefore, excluded volume is not
equal to the actual volume of the gas molecules.
Pressure Correction
A molecule in the interior of a gas is attracted by other molecules on all sides. The attractive forces
cancel out. But a molecule about to strike the wall of the vessel is attracted by molecules on one side
only. Hence it experiences an inward pull, therefore, it strikes the wall with reduced velocity and the
actual pressure of the gas, P, will be less than the ideal pressure. If the actual pressure P, is less than
Pideal by a quantity x, we have P = Pideal – x or Pideal = P + x. x is determined by the force of attraction
between molecules (A) striking the wall of container and the molecule (B) pulling them inward. The
net force of attraction is, therefore, proportional to the concentration of (A) type molecules and also,
of (B) type molecules. That is,
𝑥 𝛼 𝐶 𝐶 or x 𝛼 . or x =
Where a is the proportionality constant and n is the total number of gas molecules in volume, V and.
Thus, the pressure P in the ideal gas equation is corrected as
(P+ ) for n moles of gas.
Substituting the values of corrected pressure and volume in the ideal gas equation,
𝑃𝑉 = 𝑛𝑅𝑇, we have
𝒂𝒏𝟐
(P+ )(𝑽 − 𝒏𝒃) = 𝒏𝑹𝑻
𝑽𝟐
This is known as Vander Waals equation for n moles of a gas. For 1 mole of a gas (n=1), Vander
Waals equation becomes ( P + )(𝑉 − 𝑏) = 𝑅𝑇
Constants a and b in Vander Waals equation are called Vander Waals constants. These constants are
characteristic of each gas.
11
Determination of a and b
From the expression P = , a is given as,
( )( )
a= = (atmlitre2mol-2 ). Thus a is expressed in atmlitre2mol-2 units.
( )
Since nb is excluded volume for n moles of gas, b = = = litre mol-1 units.
SI Units of a and b
( )( ) ( )
𝑎= =
( ) ( )
= Nm4mol-2
b = Volume mol-1 = m3mol-1
Example:
Calculate the pressure exerted by 1.00mole of methane (CH4) in a 250mL container at 300K using Van
der Waals equation. What pressure will be predicted by ideal gas equation? Take a= 2.253atmL 2mol-
2, b= 0.0428Lmol-1 and R= 0.0821atmLmol-1K-1.
Solution
(P + )(𝑉 − 𝑛𝑏) = 𝑛𝑅𝑇
P = 82.8atm.
The ideal gas equation predicts that
P= = 98.5atm.
Limitation of Van Der Waals Equation

Van der Waals equation explains satisfactorily the general behaviour of real gases. It is valid over a
wide range of pressures and temperatures. However, it fails to give exact agreement with
experimental data at very high pressures and low temperatures.
Exercises
1) One mole of CO2(g) occupies 0.382x103m3 at 40oC. Calculate the pressure that the gas would
exert assuming ideal behavior. Take R = 8.314Jmol-1K-1.
2) Convert the following Physical quantities to the required units: 365cm to m, 22400cm 3 to dm3
then to m3 and 760torr to Nm-2.
3) The hottest place on record in North America is Death Valley in California. It reached a
temperature of 134oF in 1913. What is this temperature reading in degrees Celsius? In
Kelvins?
4) The total pressure exerted by a mixture of 2 gases A & B is 76.2cmHg. The number of moles of
the 2 gases is 0.0075 and 0.0040 respectively. Calculate the partial pressures of the 2 gases.
5) Nitric acid, a very important industrial chemical, is made by dissolving the gas NO 2(g) in water.
Calculate the density of NO2 gas, in g/L, at 1.24atm and 50oC.
12
6) A sample of hydrogen gas (H2) has a volume of 8.56L at a temperature of OoC and a pressure
of 1.5atm. Calculate the moles of H2 molecules present in this gas sample.
7) What is the volume of a gas balloon filled with 4.00moles of He when the atmospheric
pressure is 748torr and the temperature is 30oC?
8) Calculate the root mean square speed of O2 molecules in a cylinder at 21oC and 15.7atm.
9) The density of a gas was measured at 1.50atm and 27oC and found to be 1.95g/L. Calculate
the molar mass of the gas.
10) Calculate the pressure exerted by 1.0mole of methane, in a 500mL vessel at 25 oC assuming a)
Ideal behavior and b) Non-Ideal behavior.
11) Define the compressibility factor of a gas. The compressibility factors of 2 gases are Z A =
0.65 and ZB = 1.23 (i) state the nature of deviation of each gas from ideality. (ii) How does the
ease of compression of each gas compare with that of an ideal gas?
13
THERMOCHEMISTRY
Thermochemistry is the study of energy changes that accompany chemical reaction
Heat Change in Chemical Reaction
Chemical reactions are usually accompanied by heat changes, either evolution or absorption of heat
energy. This heat change is called enthalpy change. Enthalpy is defined as the heat content of a
substance. Enthalpy is denoted by the symbol H, and the enthalpy change by ∆H. ∆H = H (products) –
H(reactants)
Endothermic Process
A chemical reaction or a physical change in which heat is absorbed in to the system is called an
endothermic process.
Surroundings
heat heat
system
An endothermic process
∆H = +ve
Exothermic Process
A chemical reaction or a physical change in which heat is evolved (goes out) from the system is called
an exothermic process.
Surroundings
heat heat
system
An exothermic process
∆H = -ve
14
Energy level diagrams for endothermic and exothermic processes:
Energy
H = HP - H R = +ve
Endothermic process
Reaction path
R
Energy
H
H = HP - H R = -ve
P
Exothermic process
Reaction path
Standard Enthalpy Change of Formation (∆Høf)
This is the enthalpy change that accompanies the formation of one mole of a substance from its
elements at standard state. Consider the following:
H2(g) + O2(g) H2O(l) ∆Hø1 = -286kJ………………………………… (1)
HCl(aq) + NaOH(aq) H2O(l) + NaCl(aq) ∆Hø2 = -57.9kJ….… (2)
2H2(g) + O2(g) 2H2O(l) ∆Hø3 = -572 kJ……………………………… (1)
Equation (1) is the only equation representing the standard enthalpy change of formation of water
because, hydrogen and oxygen at their standard states (gases) react to form one mole of liquid
water. In equation (2), the constituent element (hydrogen and oxygen) are not at their standard
states. In equation (3), even though, the constituent elements are at their standard states, two
moles of water is formed instead of one mole.
Note: Elements in an un-combined state have ∆H øf = 0
15
Standard Enthalpy Change of Combustion (∆Høc)
This is the enthalpy released when one mole of a substance is completely burnt in oxygen. For
example,
C(s) + O2(g) CO2(g) ∆Hø = 393kJmol-1
The equation below is not ∆Høc
C(s) + O2(g) CO(g) (because it is incomplete combustion that is, O2(g) )
Standard Enthalpy Change of Atomization (∆Høatm Or ∆Hødiss)
The enthalpy change required to convert one mole of gaseous molecule to atoms at standard state.
Example: Cl2(g) 2Cl(g) ∆Hødiss = …….kJmol-1
Standard Enthalpy Change of Sublimation (∆Høsub)
This is the enthalpy change required to convert one mole of solid to gas at standard state. That is,
A(s) A(g) ∆Høsub = …….kJmol-1
Ionization Potential (IP)
The energy required to remove an electron completely from an atom. That is,
A(g) A+(g) + e-
e.g. Na(g) Na+(g) + e-
Electron Affinity (EA)
The energy released when one mole of gaseous anion is formed from gaseous atom. That is,
B(g) + e- B-(g)
e.g. Cl(g) + e- Cl-(g)
Lattice Energy (∆Hlattice)
The energy required to separate one mole of ionic compound in to its gaseous ions. That is,
AB(s) A+(g) + B-(g)
e.g. NaCl(s) Na+(g) + Cl-(g)
Bond Enthalpy
This refers to the enthalpy required to break one mole of a gaseous covalent bond to form products
in the gaseous state at constant temperature and pressure. e.g. H-Cl (g) H(g) + Cl(g)
16
Standard Enthalpy Change of Solution (∆Hsolution)
This is the enthalpy accompanying dissolving a solid in a large excess of water. For example,
NaOH(s) + Water NaOH(aq) ∆Høsolution = -42.7kJmol-1
Standard Enthalpy Change of Neutralization (∆H neut)
This is the enthalpy change when one mole of OH- neutralizes H+. That is,
H+(aq) + OH-(aq) H2O(l)
Thermochemical Equation (TCE)
Thermochemical equation is a balanced chemical equation showing the physical states of all
reactants and products, and the enthalpy change of the reaction.
Example: H2(g) + O2(g) H2O(l) ∆Hø1 = -286kJmol-1
 When a thermochemical equation is reversed, the sign of ∆H is also reversed. e.g.
H2O(l) H2(g) + O2(g) - ∆Hø1 = +286kJmol-1
 When a thermochemical equation is multiplied by a factor n, the ∆H is also multiplied by

the same factor. e.g.
3H2O(l) 3H2(g) + O2(g) - 3∆Hø1 = +855kJmol-1
 Physical states of all reactants and products must be indicated.
Examples:
1. Reverse the following thermochemical equations:

a. 2C(s) + H2(g) C2H2(g) ∆H1 = +22.6 kJmol-1
b. C(s) C(g ) ∆H2 = +716 kJmol-1
c. CaCl2(s) Ca(s) + Cl2(g) ∆H3 = +794 kJmol-1
Answer
a. C2H2(g) 2C(s) + H2(g) - ∆H1 = -22.6 kJmol-1

b. C(g) C(s ) - ∆H2 = -716 kJmol-1
c. Ca(s) + Cl2(g) CaCl2(s) - ∆H3 -794 kJmol-1
2. When 2moles H2(g), 1mole O2(g) react to give liquid water, 572kJ of heat evolves.
2H2(g) + O2(g) 2H2O(l) ∆H = -572 kJ.
Write this equation for 1mole of liquid water. Give the reverse equation in which 1mole of
liquid water dissociates in to hydrogen and oxygen.
17
Solution
Multiply the coefficients and ∆H by
H2(g) + O2(g) H2O(l) ∆H = -286 kJmol-1
Reversing the equation, we get
H2O(l) H2(s) + O2(g) ∆H = +286 kJmol-1
Exercises
1. Given that C2H2(g) + 3O2(g) 2CO2(g) + 2H2O(l) ∆H = -1393 kJmol-1
If the equation is reversed and multiplied by , write down the thermochemical equation for the
changes.
2. The standard enthalpy changes of formation of carbon dioxide, benzene and ethanol are -393,
+49, and – 278kJmol-1 respectively. Write down the thermochemical equations for the
changes.
3. A propellant for rockets is obtained by mixing the liquids hydrazine, N2H4, and dinitrogen
tetroxide, N2O4. These compounds react to give gaseous nitrogen, N2, and water vapour,
evolving 1049kJ of heat at constant pressure when 1mole N 2O4 reacts. Write the
thermochemical equation for this reaction.
4. Aqueous sodium hydrogen carbonate (baking soda) reacts with hydrochloric acid to produce
aqueous sodium chloride, water and carbon dioxide gas. The reaction absorbs 12.7kJ of heat
at constant pressure for each mole of sodium hydrogen carbonate. Write the thermochemical
equation for this reaction.
5. Write a thermochemical equation to represent the exothermic reaction that occurs when two
moles of butane burn in excess oxygen gas. The molar enthalpy of combustion of butane is –
2871kJmol-1.
Using energy symbol to write Thermochemical Equation
Examples
Write thermochemical equations for the following changes:
a. ∆Høf (C6H6(l)) = +49kJmol-1

b. ∆Høf (H2O(l)) = - 286kJmol-1
c. ∆Høc (C(s)) = +393kJmol-1
18
Answer
a. 6C(s) +3H2(g) C6H6(l) ∆Høf = +49kJmol-1

b. H2(g) + O2(g) H2O(l) ∆Høf = - 286kJmol-1
c. C(s) + O2(g) CO2(g) ∆Høc = +393kJmol-1
Exercises
Use energy symbols to represent the following TCEs
a. C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(l) ∆Høc = -2222kJmol-1

b. 3C(s) + 4H2(g) C3H8(g) ∆H = -104 kJmol-1
c. Rb(s) + Cl2(g) RbCl(s) ∆H = -430.5kJmol-1
Calculating Standard Enthalpy Change of Reaction (∆Hørxn) From (∆Høf)
For a hypothetical reaction aA + bB cC + dD
Where a, b, c and d are stoichiometric coefficients,
∆Hørxn = [c ∆Høf (C) + d ∆Høf (D) ] - [a ∆Høf (A) + b ∆Høf (B) ]
That is, ∆Hørxn = [n ∑ Hf (products) ]- [n ∑ Hf (reactants) ]
Example
Calculate the enthalpy change for the reaction;
C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(l) given that,
∆Høf (C3H8(g)) = - 104kJmol-1 ∆Høf (H2O(l)) = - 286kJmol-1 ∆Høf (CO2(g)) = - 394kJmol-1
Answer: - 2222kJmol-1
Exercises
1. Calculate the standard enthalpy change for the reaction;
CaO(s) + H2O(l) Ca(OH)2(s) given that, the standard enthalpy changes of formation of
calcium oxide, water, and calcium hydroxide are - 635, - 286 and -987 kJmol -1 respectively.
Hess’s Law of Constant Heat Summation
A Switzerland-born Russian Chemist (Germain Hess) developed this law, which is a thermochemical
version of the law of conservation of energy, in 1840.
19
The law states that, ‘’ the enthalpy change for a reaction is the same whether it occurs by one-step or
by a series of steps.
Consider the following:

A+B P
H1 P (one step) or
If A + B
H2 C+D H3 P (two step)
A+B
By Hess’s law, ∆H1 = ∆H2 + ∆H3
Below is a schematic representation of Hess’s law:
reactants
H2
direct
route
indirect
H1
route
H3
H1 = H2 + H3
products
Example
Calculate ∆H for the reaction;

2C(s) + H2(g) C2H2(g) given the following thermochemical equations:
C2H2(g) + O2(g) 2CO2(g) + H2O(l) ∆H1 = -1299.6 kJmol-1 ………………...(1)
C(s) + O2(g) CO2(g) ∆H2 = -393.5 kJmol-1………………………………(2)
H2(g) + O2(g) H2O(l) ∆H3 = -285.8 kJmol-1 …………………….……….(3)
Answer
The target equation is 2C(s) + H2(g) C2H2(g)
Since the target equation contains C2H2(g) , we reverse equation (1). That is,
2CO2(g) + H2O(l) C2H2(g) + O2(g) - ∆H1 = +1299.6 kJmol-1 ……….....(4)
The target equation has 2C(s) as a reactant; therefore, we multiply equation (2) by 2. That is,
2C(s) + 2O2(g) 2CO2(g) 2∆H2 = 2(-393.5) = - 787.0 kJmol-1…………(5)
The target equation has H2(g) as a reactant thefore, we leave equation (3) as it is.
By adding equation (3), (4) and (5), we obtain the desired equation. That is,
20
H2(g) + O2(g) H2O(l) ∆H = -285.8 kJmol-1

2CO2(g) + H2O(l) C2H2(g) + O2(g) - ∆H1 = +1299.6 kJmol-1
2C(s) + 2O2(g) 2CO2(g) 2∆H2 = 2(-393.5) = - 787.0 kJmol-1
2C(s) + H2(g) C2H4(g) ∆Hrxn = + 227.1 kJmol-1
Exercises
1. Calculate the standard enthalpy change of formation of CO given that the standard enthalpy
changes of combustion of graphite and carbon monoxide are -393.5, and – 283.0 kJmol-1
respectively.
2. Given the thermochemical equations below;
H2(g) + O2(g) H2O(l) ∆H1 = -285.5 kJmol-1 …………………………………….(1)
C(s) + O2(g) CO2(g) ∆H2 = -393.5 kJmol-1……….…………..……….………(2)
CH4(g) + 2O2(g) CO2(g) + 2H2O ∆H3 = - 890.3 kJmol-1….………………..………………(3)
Determine the ∆Hrxn for the following: C(s) + 2H2(g) CH4(g) ∆Hrxn = ?
3. Carbon occurs in two forms, graphite and diamond. The ∆Hc (C(graphite)) = - 393.5 kJmol-1 and
∆Hc (C(diamond)) = - 395.4 kJmol-1 calculate the ∆H for the conversion of graphite to diamond.
Answer: +1.9kJmol-1
4. Given the following thermochemical equations;
2W(S) + 3O2(g) 2WO3(s) ∆H1 = 1685.8 kJ
C(s) + O2(g) CO2(g) ∆H2 = -393.5 kJ
2WC(S) + 5O2(g) 2WO3(s) + 2CO2(g) ∆H3 = -2391.8 kJ
Calculate the enthalpy change for the formation of tungsten carbide WC.
5. Manganese metal can be obtained by reaction of manganese dioxide with aluminium.

4Al(s) + 3MnO2(s) 2Al2O3(s) + 3 Mn(s)
What is the ∆H for this reaction? Use the following data;
2Al(s) + O2(g) Al2O3(s) ∆H1 = -1676kJ
Mn(s) + O2(g) MnO2(s) ∆H2 = -520 kJ [Answ: - 1792kJ]
21
Born-Haber Cycle
It was developed by Max Born and Fritz Haber and therefore named after them. It is useful in
calculating the enthalpy changes such as of formation, combustion, lattice energy, bond energy, and
so on.
Generally, the following diagram can represent combustion and formation reactions:
aA + bB AaBb
combustion
combustion
ion
ust
omb
c
Combustion products
Example: The heat of formation of water is –286 kJmol-1, the heat of combustion of C(s) is –393
kJmol-1 . The heat of formation of benzene is +84.1 kJmol-1
a. Write the thermochemical equation for the energy changes.

b. Construct a Born-Haber cycle and use it to calculate the standard enthalpy change of
combustion of benzene.
Answer
a. The thermochemical equations are;

H2(g) + O2(g) H2O(l) ∆H1 = -286 kJmol-1 …………………………………….(1)
C(s) + O2(g) CO2(g) ∆H2 = -393 kJmol-1 …………………………………….(2)
6C(s) + 3H2(g) C6H6(l) ∆H3 = + 84.1 kJmol-1………………………….……….(3)
C6H6(l) + O2(g) 6CO2(g) + 3H2O(l) ∆H4 = ?………….……………………………….(4)
b. Since there are 6H atoms and 6C atoms in C6H6(l), we multiply equation (1) by 3 and equation (2) by
6. That is,
3H2(g) + O2(g) 3H2O(l) 3∆H1 = 3(-286) = - 858 kJmol-1 …………….……(5)
6C(s) + 6O2(g) 6CO2(g) 6∆H2 = 6(-393) = -2358 kJmol-1………………….(6)
We use equation (3), (4), (5) and (6) for the construction of the cycle.
22
H3
6C(s) + 3H2(g) C6H6(l)
3H1
6H2
3/2O2(g)
H4
6O2(g)
g)
O 2(
1 5 /2
6CO2(g) + 3H2O(l)
By Hess’s law, ∆H3 = 6∆H2 + 3∆H1 - ∆H4 ⇒ ∆H4 = -3300.1 kJ
Exercise: The standard enthalpy changes of combustion (in kJmol-1) are as follows:
C(s) = - 393.5 H2(g) = -285.5 CH3NO2(l) = - 709.2 ∆Høf (CH3NO2(l)) = ?
Formation of Ionic Solids
Example
Which ions are present in MgO(s)? Given the following information, calculate the standard enthalpy
change of formation of MgO(s); Mg(g) + O2(g) MgO(s) ∆Hf = ?
∆Hatm (O) = +249kJmol-1 ∆Hsub (Mg) = +148kJmol-1 1st IE (Mg) = +738kJmol-1
2nd IE (Mg) = + 1451kJmol-1 1st EA (O) = - 141kJmol-1 2nd EA (O) = + 798kJmol-1
∆Hlattice (MgO(s)) = - 3791kJmol-1
Answer
The ions present are: Mg2+ and O2-
Hf = ?
Mg(s) + 1/2O2(g) MgO(s)
Hsub Hatm
Mg(g) O(g)
Hlattice
1nd IE
2nd EA 1st EA
Mg+(g) O-(g)
2nd IE
Mg2+(g) + O2-(g)
 Hf = - 548kJmol-1
23
CHEMICAL KINETICS
Chemical kinetics is the study of the rates of chemical reactions, the factors on which the rates depend
and the mechanism of reactions.
Measuring the rate of reaction
The rate of a reaction is the rate of decrease in concentration of a reactant or the rate of increase in
concentration of a product.
𝑑𝑒𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 [𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡] −𝑑[𝑅]

𝑅𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = =
𝑡𝑖𝑚𝑒 𝑡𝑎𝑘𝑒𝑛 𝑑𝑡
𝑖𝑛𝑐𝑟𝑒𝑎𝑠𝑒 𝑖𝑛 [𝑝𝑟𝑜𝑑𝑢𝑐𝑡] 𝑑[𝑃]
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = =
𝑡𝑖𝑚𝑒 𝑡𝑎𝑘𝑒𝑛 𝑑𝑡
Factors affecting rates of reactions
(1) Concentration: The rate of reaction increases as the concentration of reactants is increased
since the reactant particles become more crowded and closer, thus increasing the number of effective
collisions.
(2) Temperature: The rate of a reaction increases as the temperature of reactants makes more
energy to be available to break bonds to form products as well as increasing the speed of the collision
of the particles.
(3) Catalysts: A Catalyst is any substances which alter the rate of a chemical reaction and remain
chemically unchanged at the end of the reaction. It acts by lowering the activation energy so that more
reactant particles have sufficient energy to react.
(4) Surface area of contact: The larger the surface area exposed for the reaction, the faster the
reaction. Thus, the reactions on powdery surfaces of solids are faster than those on the surfaces of
lumpy solids.
(5) Pressure: Pressure has a similar effect as concentration. An increase in pressure will bring about
the crowding of the particles in a small space. This will increase the number of effective collisions and
hence the rate of reaction.
(6) Light: Presence of light causes some reactions to take pale and increasing the number of
effective collisions and hence rate of reaction.
Collision Theory of Reactions
According to the collision theory, for a chemical reaction to occur, the reactant particles must collide,
and their energy after collision must at least be equal to a minimum value called the activation energy.
However not all collisions are effective, only few fraction results in a chemical reaction. Hence, the rate
of chemical reaction depends on the frequency of effective collision.
24
Activation energy
Activation energy is the minimum energy required for an effective collision. It results in bond re-
organisation to form products. The higher the energy the slower the reaction, positive catalysts lower
the activation energy.
The Rate Law
The rate law is a mathematical expression, which relates the rate of reaction to the concentrations of
the reactants raised to some powers. The rate law expresses the relationship the rate of reaction and
concentration.
For a reaction 𝐴 + 𝐵 → 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠
The rate law, 𝑅𝑎𝑡𝑒 = 𝑘 [𝐴 ] [𝐵] where K is called rate constant of the reaction, x is the order of the
reaction with respect to A and y as the order of reaction with respect to B. The overall order of the
reaction is𝑥 + 𝑦.
Example
Reactions Rate Law

2N2O5 4NO2 + O2 Rate = k[N2O5]
H2 + I2 2HI Rate = k[H2] [I2]
2NO2 2NO + O2 Rate = k[NO2]2
2NO + 2H2 N2 + 2H2O Rate = k[H2] [NO] 2
Order of Reaction
The sum of the powers of concentrations in the rate law is known as the order of reaction.
25
For example, 𝑅𝑎𝑡𝑒 = 𝑘 [𝐴 ] [𝐵] the order of reaction is (x + y).
The order of reaction can also be defined with respect to a single reactant. Thus, the reaction order
with respect to A is x and with respect to B is y. The overall order of reaction may range from 1 to 3
and can be fraction. Example,
Rate Law Reaction order

Rate = k[N2O5] 1
Rate = k[H2] [I2] 1 +1 = 2
Rate = k[NO2]2 2
Rate = k[CHCl3][Cl2]1/2 1 + ½ = 1½
Classification of order of reaction
If in the rate law, x + y = 1, the reaction is first order
x + y = 2, the reaction is second order
x + y = 3, the reaction is third order
NB: for an elementary reaction, the order of reaction and the molecularity are equal.
Molecularity of a reaction
Chemical reactions may be classified in to two types:
a). Elementary reactions and b). Complex reactions
An elementary reaction is a simple reaction that occurs in a single step. A complex reaction is that
which occurs in two or more steps.
Molecularity of an elementary reaction
The molecularity of an elementary reaction is defined as: the number of reactant molecules involved
in a reaction.
a). Unimolecular: (molecularity = 1)
A → products
e.g Br2 → 2 Br
b). Bimolecular: (molecularity = 2)
A + B → products
A+ A → products
26
e.g CH3COOC2H5 + H2O → CH3COOH + C2H5OH

2HI → H2 + I2
c). Termolecular: (molecularity = 3)
A + B + C → products
e.g 2NO + O2 → 2NO2

2NO + Cl2 → 2NOCl
First order reactions
A reaction is first order if the exponent of the reactant concentration in the rate law is 1. The rate of
the first order reaction is proportional to the concentration of the reactant.
Consider a first order reaction 𝐴 → 𝑃roducts

𝑅𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 𝛼 [𝐴]
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = 𝑘 [𝐴] … … … … … … … … … … … … … … . . 𝑖
[ ]
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = − . … … … … … … … … … … . . … . . . . 𝑖𝑖
𝑑[𝐴]
∴ − = 𝑘 [𝐴] = 𝑅𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛
𝑑𝑡
Take all terms in one variable, [A] to one side and all terms to other side.
𝑑[𝐴] 𝑑[𝐴]
− = 𝑘𝑑𝑡 𝑜𝑟 = 𝑘𝑑𝑡 … … … … . . … 𝑖𝑖𝑖
[𝐴] [𝐴]
Take integral of both side since k is constant
𝑑[𝐴]
= −𝑘 𝑑𝑡 … … … … … . . … 𝑖𝑣
[𝐴]
In kinetics, the change in concentration with time is followed from the start of the reaction, [𝐴] at
𝑡 = 0 to [𝐴] at 𝑡 = 𝑡𝑖𝑚𝑒. These are the limits between which the integral is taken.
Let [𝐴] = 𝑥 and [𝐴] = 𝑥

[ ]
𝑑[𝐴]
∴ = −𝑘 𝑑𝑡 … … … … . … . 𝑣
[ ] [𝐴]
𝑑𝑥
= ln 𝑥 − ln 𝑥 , −𝑘 𝑑𝑥 = 𝑥 − 0 = 𝑥 𝑎𝑛𝑑 𝑥 = 𝑡
𝑥
𝑆𝑖𝑛𝑐𝑒 𝑥 = [𝐴] 𝑎𝑛𝑑 𝑥 = [𝐴]
ln[ 𝐴] – ln[𝐴] = −𝑘𝑡 … … … … … … … . . . . . 𝑣𝑖
Or ln[ 𝐴] = ln[𝐴] − 𝑘𝑡 … … … … … … … … … … … . … . 𝑣𝑖𝑖
The half-life for a first order reaction
The half-life of a reaction is defined as the time required for the concentration of a reactant to decrease
to half its original value. In other words, half-life is the time required for one-half of the reaction to be
completed.
1
[𝐴] = [𝐴] = 𝑘𝑡
2
27
Substituting [𝐴] = [𝐴] 𝑖𝑛 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 𝑣𝑖 𝑜𝑟 𝑣𝑖𝑖 , 𝑤𝑒 ℎ𝑎𝑣𝑒;

𝑘𝑡 = ln[𝐴] − ln 1 2[𝐴] ,
∴ 𝑘𝑡 = ln[𝐴] − ln[𝐴] + ln 1 2
𝑘𝑡 = − ln 0.5 ,
0.693
𝑡 =
𝑘
Examples
1. Compound A decomposes to form B and C the reaction is first order. At 25 0C the rate constant
for the reaction is 0.450 s-1. What is the half-life of A at250C?
Solution
We know that for a first order reaction, half-life t1/2, is given by the expression
0.693
𝑡 =
𝑘
Where k = rate constant
Substituting the value k = 0.450s-1, we have
.
𝑡 = = 1.54s
.
2. The half-life of a substance in a first order reaction is 15 minutes. Calculate the rate constant.
Solution
. . .
Using 𝑡 = , we have k = = = 4.62 x 10-2min-1
28
CHEMICAL EQUILIBRIUM
Reversible Reactions
Not all chemical reactions proceed to completion. In most cases, two or more substances react to form
products which themselves react to give back the original substances. Thus A and B may react to form
C and D which react together to reform A and B. That is,
C + D (forward reaction)
A + B
C + D (backward reaction)
A + B
A reaction which can go in the forward and backward direction simultaneously is called reversible
reaction. That is,
A + B C + D
Examples of reversible reactions
2NO2(g) N2O4(g)
H2(g) + I2(g) 2HI(g)
PCl5(s) PCl3(s) + Cl2(g)
Chemical Equilibrium
A state of a reversible reaction when the two opposing reactions occur at the same rate and the
concentrations of reactants and products do not change with time is called chemical equilibrium.
That is,
Rate of forward reaction = Rate of backward reaction
Chemical equilibrium is dynamic and concentrations at equilibrium are called equilibrium

concentrations.
Law of Mass Action

Law of mass action states that: the rate of a chemical reaction is proportional to the active masses of
the reactants. Active mass implies molar concentration (number of moles divided by volume).
Mathematically,
Rate of reaction α [A][B]
= K[A][B]
29
Equilibrium Law (Equilibrium Constant)
Let us consider
A + B C + D
Where [A], [B], [C], [D] represent molar concentrations at equilibrium,
According to the law of mass action
Rate of forward reaction α [A][B]

= K1[A][B]
Rate of reverse reaction α [C][D]
= K2[C][D]
Where K1 and K2 are rate constants for the forward and reverse reactions respectively
At equilibrium,
Rate of forward reaction = Rate of reverse reaction
Therefore,
K1[A][B] = K2[C][D]
Or
𝐾 [𝐶][𝐷]
=
𝐾 [𝐴][𝐵]
At any given temperature, is constant. Therefore, 𝑖𝑠 𝑐𝑎𝑙𝑙𝑒𝑑 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡(Kc) or

[ ][ ]
simply K. Hence, K= [ ][ ]
this is called equilibrium constant expression or equilibrium law.
Generally, for a reaction

𝑎𝐴 + 𝑏𝐵 𝑐𝐶 + 𝑑𝐷
[𝐶] [𝐷]
𝐾 =
[𝐴] [𝐵]
Where a, b, c and d are numerical coefficients of A, B, C and D respectively.
Example
Give the equilibrium constant expression for the following reactions:
i. N2(g) + 3H2(g) 2NH3(g)
ii. N2O5(g) NO2(g) + O2(g)
iii. N2(g) + O2(g) 2NO(g)
iv. CH4(g) + H2O(g) CO(g) 3H2(g)
30
Solution
[ ] [ ]
i. Kc = =
[ ] [ ][ ]
ii. N2O5(g) NO2(g) + O2(g)
The above equation is not balanced and the balanced equation is as follows:
ii. 2N2O5(g) 4NO2(g) + O2(g) and K = [ ]

=
[ ] [ ]
c
[ ] [ ]
[ ]
iii. Kc = =
[ ][ ]
[ ][ ]
iv. Kc =
[ ][ ]
Calculation of Kc from experimental information
Examples
1. Consider the following reaction at equilibrium:
2SO2(g) + O2(g) 2SO3(g)
The concentrations of reactants and products at 7270C were found to be: SO2 = 0.27molL-1; O2 =
0.40molL-1; and SO3 = 0.33molL-1. What is the value of the equilibrium constant Kc at this temperature?
Solution
[ ] [ ]
Kc = =
[ ] [ ] [ ]
We know that ;
[SO3] = 0.33molL-1, [SO2] = 027molL-1, [O2] =0.40molL-1
[ . ]
Therefore, Kc = = 3.7
[ . ] [ . ]
2. Some nitrogen and hydrogen are placed in an empty 5.0 litre container at 500 0C. When equilibrium
is established, 3.01mol of N2, 2.10mol of H2 and 0.565mol of NH3 are present. Evaluate Kc for the
following reaction at 5000C 𝑁 ( ) + 3𝐻 ( ) 2𝑁𝐻 ( )
Solution
The equilibrium concentrations are :
[N2] = 3.01mol/5.00L = 0.602M, [H2] = 2.10mol/5.00L = 0.420M, [NH3] = 0.565mol/5.00L = 0.113M
[𝑁𝐻 ] (0.113)
𝐾 = = = 0.286
[𝑁 ][𝐻 ] (0.602)(0.420)
31
Partial Pressures and the Equilibrium Constant

It is often more convenient to measure pressures rather than concentration of gases.
In general for reaction involving gases
( ) ( )
𝑎𝐴( ) + 𝑏𝐵( ) ↔ 𝑐𝐶( ) + 𝑑𝐷( ) 𝐾 =
( ) ( )
( )
𝑁 ( ) + 3𝐻 ( ) ↔ 2𝑁𝐻 ( ) 𝐾 =
( )( )
Example
In an equilibrium mixture at 5000C we find
𝑃 0
= 0.147 𝑎𝑡𝑚, 𝑃 = 6.00 𝑎𝑡𝑚 and 𝑃 = 3.70 𝑎𝑡𝑚. Evaluate Kp at 500 C for the following
reaction
𝑁 ( ) + 3𝐻 ( ) ↔ 2𝑁𝐻 ( )
Solution
(𝑃 ) (0.147)
𝐾 = = = 7.11 𝑥 10
(𝑃 )(𝑃 ) (6.00)(3.70)
Relationship Between Kp and Kc

If the ideal gas equation is rearranged, the molar concentration of a gas is n/V = P/RT or M = P/RT.
Substituting P/RT for n/V in the Kc expression for the N2-H2-NH3 in ammonia production reaction,
equilibrium gives the relationship between Kc and Kp for the reaction.
[𝑁𝐻 ] (𝑃 /𝑅𝑇) (𝑃 ) (1⁄𝑅𝑇 )
𝐾 = = = 𝑥
[𝑁 ][𝐻 ] (𝑃 /𝑅𝑇)(𝑃 /𝑅𝑇) (𝑃 )(𝑃 ) (1⁄𝑅𝑇 )
Kc = Kp(RT)2 and Kp = Kc(RT)-2
In general, the relationship between Kc and Kp is Kp = Kc(RT)∆n or Kc = Kp(RT)- ∆n
Where ∆n = (ngas product(s)) – (ngas reactant(s))
For reactions in which equal numbers of moles of gases appear on both sides of the equation, ∆n = 0
and Kp = Kc.
Example
If Kc for ammonia reaction at 5000C (or 773K) is 0.286, calculate the Kp for such reaction
𝑁 ( ) + 3𝐻 ( ) ↔ 2𝑁𝐻 ( ) ∆n = 2 - 4 = -2
Kp = Kc(RT) ∆n
= (0.286)[(0.0821)(773)]-2 = 7.10 x 10-5
32
Heterogeneous Equilibria
Heterogeneous equilibria involves species in more than one phase. Consider the following reversible
reaction at 25 0C
2𝐻𝑔𝑂( ) ↔ 2𝐻 ( ) + 𝑂( )
For any pure solid of pure liquid, the activity is taken as 1, so terms for pure liquids or pure solids do
not appear in the K expressions for heterogeneous equilibria, ie for above reaction
Kc = [O2] or Kp = PO2
Example
Write both Kc and Kp for the following reactions
a) 2𝑆𝑂 ( ) + 𝑂( ) ↔ 2𝑆𝑂 ( )
b) 2𝑁𝐻 ( ) + 𝐻 𝑆𝑂 ( ) ↔ (𝑁𝐻 ) 𝑆𝑂 ( )
c) 𝑆( ) + 𝐻 𝑆𝑂 ( ) ↔ 𝐻 𝑆 𝑂( )
Solution
a) 𝐾 = = [𝑁𝐻 ] 𝐾 = = (𝑃 )
[ ] ( )
[ ] ( )
b) 𝐾 = 𝐾 =
[ ][ ] ( )( )
[ ]
c) 𝐾 = Kp is undefined because no gases are involved.
[ ]
Example
The value of Kp is 27 for the thermal decomposition of potassium chlorate at a given high temperature.
What is the partial pressure of oxygen in a closed container in which the following system is at
equilibrium at the given temperature?
∆
2𝐾𝐶𝑙𝑂 ( ) → 2𝐾𝐶𝑙( ) + 3𝑂 ( )
Solution
Kp = (PO2)3 = 27
Let x atmosphere = PO2 at equilibrium
Then (PO2)3 = 27 =x3; x = 3.0 atmospheres
Relationship Between ∆G0rxn and K

The relationship between the free energies both at standard and nonstandard conditions is given as
∆Grxn = ∆G0rxn + RTlnQ

Where R is the universal gas constant, T is the absolute temperature and Q is the reaction quotient
When a system is at equilibrium ∆G0rxn = 0 and Q = K
Upon substitution 0 = ∆G0rxn + RTlnK; ∆G0rxn = -RTlnK
When the relationship ∆G0rxn = -RTlnK is used with
i) all gaseous reactants and products, K represents Kp
33
ii) All solution reactants and products, K represents Kc

iii) A mixture of solution and gaseous reactants, K represents the thermodynamic equilibrium constant
and there is distinction between Kp and Kc.
The thermodynamic equilibrium constant is defined in terms of activities of the species involved
𝑎𝐴 + 𝑏𝐵 ↔ 𝑐𝐶 + 𝑑𝐷
(𝑎 ) (𝑎 )
𝐾 =
(𝑎 ) (𝑎 )
Where a is the activity of the substances.
∆G0rxn K Product formation
∆G0rxn < 0 K > 1 Products favoured over reactants at equilibrium
∆G0rxn = 0 K = 1 At equilibrium where [C]c[D]d…….= [A]a[B]b
∆G0rxn > 0 K < 1 Reactants favoured over products at equilibrium
Example
Calculate Kp for the following reaction at 250C
2𝑁 𝑂( ) ↔ 2𝑁 ( ) + 𝑂 ( ) 𝑤ℎ𝑒𝑟𝑒 ∆𝐺 (𝑁 𝑂) = 104.2𝐾𝐽/𝑚𝑜𝑙
Solution
For all gaseous reaction, K = Kp and ∆G0rxn = -RTlnKp
∆𝐺 = [2∆𝐺 (𝑁 ( ) ) + ∆𝐺 (𝑂 ( ) )] − [2∆𝐺 (𝑁 𝑂)( ) ]
= [ 2(0) + 0 ] - [ 2(104.2)] = -208.4KJ/mol or -2.084 x 105J/mol
But ∆G0rxn = -RTlnKp
lnKp = ∆G0rxn/-RT = -2.084 x 105/-(8.314 x 298) = 84.1
Kp = e84.1 = 3.3 x 1036
Evaluation of Equilibrium Constants at Different Temperatures
This is achieved by the use of van’t Hoff equation
𝐾 ∆𝐻 1 1
ln = ( − )
𝐾 𝑅 𝑇 𝑇
Where 𝐾 is the equilibrium constant at T1
𝐾 is the equilibrium constant at T2
Thus knowing the value of ∆H0 for a reaction and R at a given temperature, van’t Hoff equation can
be used to calculate the value of K at any other temperature.
Example
𝑁( ) + 𝑂( ) ↔ 2𝑁𝑂( )
If Kp for the above reaction is 4.4 x 10-31 at 250C(298K) and ∆H0 is 180.5KJ/mol. Evaluate Kp at 2400K.
34
Solution
𝐾 ∆𝐻 1 1
ln = ( − )
𝐾 𝑅 𝑇 𝑇
.
ln = ( − ) = 63.8
.
= e63.8 = 5.1 x 1027

𝐾 = 5.1 x 1027 x 4.4 x 10-3 = 2.2 x 10-3
Displacement of Equilibrium: Factors Affecting Chemical Equilibrium

The establishment of a chemical equilibrium is the result of a balance between the forward and reverse
reactions of a reversible reaction. Therefore, the equilibrium position is altered by the factors, which
affect the rates of the forward and reverse reactions unequally, and H. Le Chatelier summarized their
effects in 1885. Le Chatelier’s principle states that if one of the external factors which affect a system
in equilibrium is altered, then the system tends to react in such away as to minimize any changes
resulting from the alteration of the external factors.
1. Effect of concentration change

 Addition of inert gas – Inert gas has no effect on the position of equilibrium but increases
the total pressure of the system and the partial pressure remains constant.
 Effect of concentration
Let consider a reaction
𝐴 + 𝐵 𝐶
When a reactant say A is added at equilibrium, its concentration is increased. According to Lé
Chatelier’s principle, a new equilibrium will be established so as to reduce the concentration of A. Thus
the addition of A causes the equilibrium to shift to the right thereby increasing the concentration of
the product C. Similarly, decrease in concentration of A, shift the equilibrium position to the left.
2. Effect of pressure change

Pressure affects only those equilibria, which show a change in volume between the reactants and
products. The effect of pressure changes on reactions in which gases are involved are particularly
important for the following reasons
i) in any gaseous reaction, an increase in pressure brings the reaction molecules closer together and
the reaction speeds up, that affects both forward and reverse reactions.
ii) the composition of the equilibrium mixture (but not the Kc) is altered in those cases where there is
a volume change
Example
In the reaction
2𝑆𝑂 ( ) + 𝑂( ) ↔ 2𝑆𝑂 ( )
∆n = nproduct – nreactant = 2 – 3 = -1
35
Increase in pressure favours smaller volume ie more SO3 will be formed, while decrease in pressure
favours higher volume ie more SO2 and O2 will be formed.
3. Effect of temperature Change

Effect of temperature change depends upon whether the reaction is endothermic or exothermic. The
following diagram summarises the effect of temperature change on the equilibrium position:
Exothermic Reaction Endothermic Reaction
A+B C A+B C
Equilibrium shift Equilibrium shift
Increase in Temperature Increase in Temperature

Example
𝑁 ( ) + 3𝐻 ( ) 2𝑁𝐻 ( ) ∆𝐻 = −92𝐾𝐽
The forward reaction is favoured by a decrease in temperature the reaction being exothermic, while
the reverse reaction is favoured by an increase in temperature.
NOTE: Effect of catalyst

A catalyst speeds up the rate of a chemical reaction. In equilibrium reactions, both forward and reverse
reactions are equally affected so that the position of equilibrium is not changed, although the
equilibrium state is arrived at more rapidly.
36
CONCEPTS OF ACIDS AND BASES

There are three concepts these are:
 Arrhenius concept
 Brønsted – Lowry concept
 Lewis acid – base concept
Arrhenius Concept
Acid: Substance which gives H+ in water. E.g
HCl(aq) 𝐻( ) + 𝐶𝑙( )
H2SO4, HCl, HNO3 etc., when dissolved in water dissociate completely and are therefore, strong acids.
CH3COOH, HCN, H3PO4, H2CO3 etc., dissociate to a lesser extent and are therefore called weak acids.
Base: Gives OH- in water. e.g., NaOH, KOH. i.e., NaOH(aq) 𝑁𝑎( ) + 𝑂𝐻( )
Brønsted – Lowry Concept

Acids: Donates proton (H+)
Base: Accept proton (H+)
An acid after losing H+, the residual part becomes a conjugate base. Similarly a base after accepting a
proton H+ becomes a conjugate acid.
NH4+ + Cl-
HCl + NH3
Base Conjugate acid
Acid Conjugate base

If an acid is strong, then its conjugate base will be weak and vice versa. Water can act both as acid as
well as base. Hence they are amphiprotic.
e.g HC𝑂 + H 2O C𝑂 + H3O+
HC𝑂 + H2O H2CO3 + OH-
Lewis’s concept
Acid; A Lewis acid is any molecule that accept lone/ nonbonding pairs of electrons to form coordinate
or dative covalent bond. E.g AlCl3, BF3
Base: A Lewis base on the other hand is any molecule which donates pairs of nonbonding electrons in
order to form a coordinate or dative covalent bond. e.g. NH 3, H2O etc
H3N + BF3 H3N BF3

Lewis base Lewis acid coordinate bond
37
Concept of pH
By definition, “pH is the negative log to base ten of the molar hydrogen ion concentration”
Mathematically, pH = -log [H+] or pH = -log [H3O+]
For basic solution
We know that, [H3O+][OH-] = 1.0 x 10-14
Log of both sides gives log[H3O+] + log[OH-] = -14 or,
(-log[H3O+]) + (-log[OH-]) = 14
pH pOH
Hence, pH + pOH = 14.
Summary
PH = -log [H3O+] or PH = -log [H+] (for strong acid)
POH = -log [OH-] (for strong base)
PKw = -log Kw PKb = -log Kb

PKa = -log Ka
Ka x Kb = Kw
Example:
Calculate the pH of (a) 0.05 moldm-3 KOH (b) 0.1moldm-3 HCl
Answer
(a)
KOH + H2O K+(aq) + OH-(aq)
Since KOH ionises completely in water
[OH-] = [KOH] = 0.05 mol/dm3
For a strong base pOH = -log[OH-]
or pOH = -log (0.05) = 1.3
But pH + pOH = 14
 pH = 14-pOH = (14-1.3) = 12.7
(b)
HCl + H2O H3O+(aq) + Cl-(aq)
Since HCl ionises completely in water
[HCl] = [H3O+] = 0.05 mol/dm3
For a strong base pH = -log[H3O+] or pH = -log (0.1) = 1.0
38
Buffer Solutions
It is often necessary to maintain a certain pH of a solution in laboratory and industrial process. This is
achieved with the help of buffers. A buffer solution is one which maintains its pH fairly constant even
upon the addition of small amount of acid or base. A buffer solution contains a mixture of a weak acid
and its conjugate base (acidic buffer) or a weak base and its conjugate acid (basic buffer). Examples
are: CH3COOH + CH3COONa (acidic buffer), and NH4OH + NH4Cl (basic buffer).
To illustrate the the mechanism for buffer action, consider the following:
+
CH COOH CH3COO- + H
3
+
CH3COONa CH3COO- + Na
Common ion in excess

The common ion suppresses the ionization of CH3COOH and therefore, reduces the concentration of
H+ and caused an increase in pH. For example, addition of HCl increases H+ and this is counteracted by
association with excess CH3COO-. Thus, the added H+ are neutralised and the pH remains virtually
unchanged.
Addition of OH- H2 O
+
CH3COOH CH3COO- + H
Acidic Buffer
+
CH3COONa CH3COO- + Na
Addition of H+ CH3COOH
Addition of H+ H2O
-
NH4OH NH4+ + OH
Basic Buffer
-
NH4Cl NH4+ + Cl
Addition of H+ NH4OH
The empirical equation that computes the pH of buffer is the Henderson-Hasselbalch equation.
[Acid]
pH = pK a  log (Henderson-Hasselbalch equation)
[Salt]
Similarly, for weak base and its salt:
[Acid]
pOH = pK b  log
[Salt]
Exercise: Calculate the pH of an aqueous buffer solution which contains 0.1 mol/dm 3 NH3 and 0.2
mol/dm3 NH4Cl. (pKa (NH4+) = 9.3). Answer: pH = 9.0
39
OXIDATION-REDUCTION REACTIONS (REDOX REACTIONS)
Redox reactions refers to all reactions in which electrons are transferred from one reactant to another.
The term ‘redox’ is a contraction of the words REDuction and Oxidation. Oxidation and reduction take
place simultaneously.
Examples
1. Combustion: Basically, every combustion is a redox reaction (e.g. car combustion engine)
2H2 + O2 2H2O
CH4 + 2O2 2H2O + CO2
2. Oxidation of metals e.g.
2Mg + O2 2MgO
3. Cellular respiration i.e.
C6H6O12 + 6O2 6CO2 + 6H2O + Energy
(glucose)
Oxidation Number (Oxidation State)
Oxidation number of an element is the number of electrons that needs to be added to the element to
make a neutral atom. For example, Fe2+ requires the addition of 2 electrons to make a neutral atom
O2- requires the addition of -2 electrons to make a neutral atom.
Rules for assigning an Oxidation Number
1. The oxidation number of uncombined element is equal to zero. For example, Na, Cu, Cl2, P4,
H2, He, Zn, Ca, O2, Mg, etc. have oxidation number equal to 0.
2. The oxidation number of every monatomic ion is equal to its charge e.g. (H+ = +1), (Ca2+ = +2),
(S2- = -2) (O2- = -2) (Zn2+ = +2) e.t.c.
3. In its compound, the oxidation number of every alkali metal and alkaline earth metal is equal
to its group number.
4. Summation zero rule: The sum of oxidation numbers of all atoms in a neutral compound is
zero. e.g. H2SO4 = 0.
5. Summation charge rule: The sum of oxidation numbers in a polyatomic ion equals to the charge
on the ion. E.g. SO42- = -2, (H3O+ = +1).
6. The oxidation number of hydrogen when combined with non-metals is +1, when combined
with metals is -1.
7. The oxidation number of oxygen in its compounds is -2 except in peroxides (-1) and in
𝟏
superoxides (- ), and in OF2 and O2F2 (+ve). Examples of peroxides include; hydrogen peroxide
𝟐
(H2O2), barium peroxide (BaO2), and sodium peroxide (Na2O2). Superoxides include; potassium
superoxide (KO2), tin(iv)oxide (SnO2).
8. The oxidation number of every halogen atom in its compound is -1, except for a Cl, Br, or I
atoms combined with oxygen or halogen atom higher in the periodic table. For example, in
40
SnCl2, SiCl4, KCl PCl3 and HCl, the oxidation state of Cl is -1. But in Cl2O3 and ClO2-, the oxidation
𝟏
number of Cl is - , and in ClF3, F has oxidation number of -1.
𝟐
Examples
1. Determine the oxidation number of each element in the following: a.

Al3+ b. MgCl c. O3 d. Cr2O72- e. H2SO4 f. CO2 g. NaNO3
Answer
a. Al3+ is a monatomic ion so, the oxidation number = +1.

b. MgCl: Mg is a group II element therefore, its oxidation number = +2
Let the oxidation number of Cl be x
2 + (2x) = 0
2 + 2x = 0
2 = -2x, ⇒ x = -1. Therefore, the oxidation number of Cl in MgCl = -1.
c. The oxidation number of O3 is 0 because it is in an uncombined state.
2. Calculate the oxidation number of Se in
Answer
HSeO3-
(+1) + x + (-2 x 3) = -1
1 + x – 6 = -1 and x = +4
Therefore, the oxidation number of Se in HSeO3- is +4.
3. Determine the oxidation state of each element in the following:

a. CH3OH b. CS2 c. LiAlH4 d. Cl2O7 e. Fe(ClO4)
Answer
a. The oxidation number of H is +1 and the oxidation number of O is -2.
Let the oxidation number of C be x
x + (1 x 3) + (-2) + 1 = 0
x+3–2+1=0
x + 4 – 2 = 0 ⇒ x + 2 = 0 and x = -2. Therefore, the oxidation number of C in CH3OH is -2
4. Calculate the oxidation number of fluorine and iodine in IF4
Answer
F has oxidation number of -1 and I have oxidation number of +7
Reason: Both F and I are in group seven (halogens) but F is higher in the group.
41
Exercises
1. Determine the oxidation number of S in each of the following: a. H2S b. S8 c. SCl2 d.

Na2SO3 e. SO4 2-
2. What is the oxidation number of the underlined element in the following: a. P2O5 b. NaH
c. Cr2O72- d. SnBr4
3. Determine the oxidation number of the indicated element in each of the following substances.
a. Br in HBrO b. S in SO2 c. C in COCl2 d. As in As4 e. C in C2O42- f. O in K2O2.
4. What is the sum of the oxidation numbers of all the atoms in the following compounds or ions?
a. PO43- b. VO2+ c. ClO2- d. Cr2O72- e. SiCl4 f. NaCl
5. What is the oxidation number of chlorine in each of the following: a. Cl2O3 b. ClO4- c. ClF5
Definitions of Oxidation and Reduction
In terms of Hydrogen / Oxygen transfer
Oxidation: Oxidation can be defined as the removal of hydrogen from a substance or addition of
oxygen to a substance.
Reduction: Reduction can be defined as the removal of oxygen from a substance or addition of
hydrogen to a substance.
Examples
2C(s) + H2(g) C2H2(g)
C2H4(g) + 3O2(g) 2CO2(g) + 2H2O(l)
2Mg + O2 2MgO
a. In terms of electron-transfer
Oxidation Reduction
OIL RIG
Oxidation is ‘losing’ electrons ‘Reduction is ‘gaining‘ electrons
For example,
2H2(g) + O2(g) 2H2O(l) + heat
-2
+1 O
+1
H H + O O H H
0 0
Here, the oxygen atom gains 2 electrons and each hydrogen atom losses 1 electron. Therefore,
Hydrogen is said to be oxidized by oxygen and oxygen is said to be reduced by hydrogen.
42
b. In terms of oxidation number

Oxidation: refers to an increase in oxidation number while Reduction: refers to a decrease in oxidation
number.
For example,
0 +1 -2 +1 -1 0
Cl2 + H2S 2HCl + S
In the above reaction, S is oxidized by Cl and Cl is reduced by S
Reason: Oxidation number of S increased from -2 to 0. That of Cl decreased from 0 to -1.
Note:
 Reducing agent causes specie to be reduced
 Oxidizing agent causes another specie to oxidized
Exercise: Which species is oxidized and which is reduced in the following reactions?
Zn(s) + 2H+(aq) H2(g) + Zn2+ (aq)

a.
b. MnO4-(aq) + 5Fe2+(aq) + 8H+(aq) Mn2+(aq) + 5Fe3+(aq) + 4H2O(l)
c. CrCl2 + Cl2 2CrCl3
d. N2(g) + 3H2(g) 2NH3(g)
BALANCING REDOX EQUATIONS
At first glance, the following equation might appear to be balanced i.e.
Zn(s) + Ag+(aq) Zn2+(aq) + Ag(s)
However, because a balanced chemical equation must have a charge balance as well as mass balance,
this equation is not balanced. The total charge for the reactant is (+1) and the total charge for the
product is (+2).
The Half- Reaction Method
This method consists of first separating the equation in to two half-reaction, one for oxidation, the
other for reduction. Balance each half reaction, and then combine them to obtain a balanced
oxidation-reduction reaction.
Steps:
1. Identify the species oxidized and the species reduced by assigning appropriate oxidation state.
2. Form separate oxidation and reduction half equations.
3. Add electrons to the more positive side of each equation to balance charges.
4. Adjust the amount of electrons.
5. Add the two equations and cancel down.
43
Example: Balance the following redox reaction using half-reaction method:
Zn(s) + Ag+(aq) Zn2+(aq) + Ag(s)
Solution
0 +1 +2 0
Zn(s) + Ag+(aq) Zn2+(aq) + Ag(s) .........................................................(1)
Zn Zn2+ .............................................................................................(2)
Ag+ Ag ..............................................................................................(3)
-
Zn Zn2+ + 2e ........................................................................................(4)
Ag+ + e- Ag ........................................................................................(5)
Multiply equation (4) by 1 and equation (5) by 2 to equalize the number of electrons. That is,
-
1 x (Zn
-
Zn2+ + 2e ) = Zn Zn2+ + 2e .................... (6)
+ -
2 x (Ag+ + e- Ag) = 2Ag + 2e 2Ag .......................(7)
Add equation (6) and (7);
-
Zn Zn2+ + 2e
2Ag+ + 2e- 2Ag
Zn + 2Ag+ + 2e- Zn2+ + 2Ag + 2e-
The 2e- on both sides can cancel out to give the balanced oxidation-reduction equation as follows:
Zn + 2Ag+ Zn2+ + 2Ag
Example 2
A useful analytical procedure involves the oxidation of iodide ions to free iodine. The free iodine is
then titrated with a standard solution of sodium thiosulfate, Na2S2O3. Iodine oxidizes S2O32- ions to
tetrathionate ions, S4O62-, and is reduced to I- ions. The unbalanced equation for this recation is:
I2 + S2O32- I- + S4O62-
Write the balanced net ionic equation for this reaction.
Answer
I2 + S2O32- I- + S4O62-
I2 I (reduction half equation)
-
I2 2I-
I2 + 2e- 2I- (balanced reduction half equation)
…………………………………………………………………………………………….......................
44
S2O32- S4O62- (oxidation half equation)

2S2O32- S4O62-
2S2O32- S4O62- +2e- (balanced oxidation half equation)
Since each balanced half equation involves a transfer of 2e - we add them up and cancel the
electrons;
I2 + 2e- 2I-
2S2O32- S4O62- + 2e-
I2(s)+2S2O32-(aq) 2I-(aq) + S4O62-(aq)
Exercise: Consider the reaction: Mg(s) + N2(g) Mg3N2(s) Apply the half-reaction
method to balance this equation.
Balancing Redox Equations in Acidic Medium
Steps:
1. Balance atoms other than H and O (using inspection)

2. Balance O atoms (using H2O)
3. Balance H atoms (using H+)
4. Balance charge using electrons (e-)
Examples:
1. Balance the following half reaction which occurs in acidic medium

ClO3- Cl-
Solution
ClO3- Cl-
ClO3- Cl- + 3H2O (balance O)
ClO3- + 6H+ Cl- + 3H2O (balance H)
ClO3- + 6H+ + 6e- Cl- + 3H2O (balanced)
2. Permanganate ions oxidize iron(II) to iron(III) in sulfuric acid solution. Permanganate ions are
reduced to manganese(II) ions. That is,
Fe2+ + MnO4- Fe3+ + Mn2+ write the balanced net ionic equation for this
reaction.
Answer
45
Fe2+ + MnO4- Fe3+ + Mn2+
Fe2+ Fe3+ (oxidation half reaction)
Fe2+ Fe3+ + e- (balanced oxidation half reaction)
MnO4- Mn2+ (reduction half reaction)
MnO4- Mn2+ + 4H2O
MnO4- + 8H+ Mn2+ + 4H2O
MnO4- + 8H+ + 5e- Mn2+ + 4H2O (balanced reduction half reaction)
Now, we balance the electrons and add the two half equations. That is,
5(Fe2+ Fe3+ + e-)
1 (MnO4- + 8H+ + 5e- Mn2+ + 4H2O)
5Fe2+(aq) + MnO4-(aq) + 8H+(aq) 5Fe3+(aq) + Mn2+(aq) + 4H2O(l)
Exercise
Balance the following equations (in acidic medium)
a. C2O42- + Cr2O72- CO + Cr3+
b. As2S3 H2AsO4- + SO42-
Balancing Redox Reactions in Basic Medium
Steps: start with the same four steps as in acidic medium.
5. Add OH- to balance (neutralize H+).

6. Simplify H2Os where necessary.
Example
Balance the half reaction: N2 NH2OH taking place in basic medium
Answer
N2 NH2OH
N2 2NH2OH (balance N)
46
N2 + 2H2O 2NH2OH (balance O)
N2 + 2H2O +2H+ 2NH2OH (balance H)
N2 + 2H2O +2H+ +2e- 2NH2OH (balance charge)
Now, we add 2OH- to both sides (to neutralize H+)
N2 + 2H2O +2H+ +2e- + 2OH- 2NH2OH + 2OH-
N2 + 2H2O +2H2O +2e- 2NH2OH + 2OH-
N2 + 4H2O +2e- 2NH2OH + 2OH- Balanced!
2. In basic solution, hypochlorite ions ClO-, oxidize chromite ions, Cr2-, to chromate ions, CrO42- and are
reduced to chloride ions. Write the balanced net ionic equation for this reaction.
Solution
CrO2- + ClO- CrO42- + Cl-
CrO2- CrO42- oxidation half equation
CrO2- + 4OH- CrO42- + 2H2O
CrO2- + 4OH- CrO42- + 2H2O + 3e-(balanced oxidation half reaction)
ClO- Cl- reduction half equation
ClO- + H2O Cl- + 2OH-
ClO- + H2O + 2e- Cl- + 2OH-(balanced reduction half reaction)
The oxidation half reaction involves 3e- and the reduction half equation involves 2e- therefore, we
balance the electrons and add the half reactions.
2 x (CrO2- + 4OH- CrO42- + 2H2O + 3e- )
3 x (ClO- + H2O + 2e- Cl- + 2OH-)
2CrO2- + 8OH- + 3ClO- + 3H2O 2CrO42- + 4H2O + 3Cl- + 6OH-
We can eliminate 6OH- and 3H2O from both sides to give the balanced net ionic equation as follows:
2CrO2- + 2OH- + 3ClO- 2CrO42- + H2O + 3Cl-

47
Exercises: Balance the following redox reactions which occur in basic medium
a. Br2 BrO3-
b. I- IO4-
c. NH3 N2
d. CH3OH + MnO4- MnO2 + HCOOH
e. Bi(OH)3 + SnO22- SnO32- + Bi
48
ELECTROCHEMISTRY
Electrochemistry: A branch of physical chemistry concerned with the behaviour of ions in solutions,
their interaction with one another and with a metallic conductor (Electrode) and the subsequent
relation between chemical energy and electrical energy.
Uses of Electrochemistry
Power source (i. Batteries ii. Fuel cells (Space craft), Corrosion prevention, Pollution analysis,
biomedical research, preparation of certain compounds like sodium hydroxide, chlorine etc.
ELECTROLYSIS
Electrolysis is the chemical decomposition of a compound brought about when electric current is
passed through either a solution or molten form of a compound
Electrolytic and electrochemical cells
Electrolytic cell: Any device in which electrical energy is converted into chemical energy, e.g. any set-
up used in electrolysis; which comprises of:
Electrolytes; These are substances in solution or molten form that allow the passage of electricity
through them. They are electrolytic conductors and mostly ionic compounds. Example Acid solutions,
molten salts.
Electrodes; These are conductors in the form of wires, rods or plates through which an electric current
enters or leaves the electrolyte. The electrodes could be anode or cathode;
Anode is the positive electrode by which the conventional current enters the electrolyte or by which
electrons leave the electrolyte.
Cathode is the negative electrode by which the conventional current leaves the electrolyte or by which
electrons enters the electrolyte.
Both the electrolyte and the electrode are contained in the same container; with the two electrodes
connected externally by an electric circuit serving as a source of direct current (DC).
Electrochemical cell
This is a device that converts chemical energy into electrical energy e.g. batteries. In this type of cell
Anode is the negative electrode while Cathode is the positive electrode. Each electrode is dipped
separately into its electrolyte or a paste containing ions. The two separate electrolytes are connected
(joined) by a salt bridge; which is a paste of KNO3 or KCl.
Mechanism of electrolysis
The figure below illustrates how the electrolysis actually take place.
49
e battery
e Cathode
Anode
Electrolyte / . . cation . .
' anion .
.
Neutral atom
Figure: The Mechanism of Electrolysis
The cations migrate to the cathode and form a neutral atom by accepting electrons from it. The anions
migrate to the anode and yield a neutral particle by transfer of electrons to it. As a result of the loss of
electrons by anions and gains of electrons by cations at their respective electrodes chemical reaction
takes place. Let us consider the electrolysis of HCl as an example. In solution, HCl is ionized,
HCl H+ + Cl-
In the electrolytic cell Cl- ions will move toward the anode and H+ ions will move toward the cathode.
At the electrodes, the following reaction will take place.
At the cathode
H+ + e H (reduction)
-
Each hydrogen ion picks up an e from the cathode to become a hydrogen atom. Pairs of hydrogen
atom then unite to form molecule of hydrogen gas H2.
H + H H2
At the anode
Cl Cl + e (oxidation)
After the chloride ion loses its electron to the anode, pair of chlorine atoms unite to form chlorine gas,
Cl2.
Cl + Cl Cl2
The net effect of the process is the decomposition of HCl in to hydrogen and chlorine gases. The overall
reaction is:
2HCl H2 + Cl2 (decomposition)
50
Preferential discharge of ions in electrolysis
The discharge of ions during electrolysis is governed by three factors;
1. Position of the ions in the electrochemical series; electrochemical series is the arrangement of ions
in order of their ability to accept electron(s) (Oxidizing agent strength) under the influence of an
applied external potential. If all other factors are constant, the lower the position of a cation in the
electrochemical series (less electropositive) the greater is tendency of the ion to be discharged in
preference to other cation high in the series (more electropositive) present. This is because the former
gains electrons more readily and therefore reduced. While for anion, the one higher in the series (less
electronegative) is discharged in preference to another lower down in the series (more
electronegative) as the former loses electrons more readily.
Cations: K+ Na+ Mg2+ Al3+ Zn2+ Fe2+ Sn2+ Pb2+ H+ Cu2+ Hg2+ Ag+ Au+
Increasing Preference for discharge
Anions: OH- I- Br- Cl- NO3- SO42- F-

Decreasing Preference for discharge
2. Concentration of the ions in the electrolyte; if other conditions are equal, increasing the
concentration of a given ions tends to promote its discharge from solution. For example, in the
electrolysis of dilute NaCl, Oxygen is produced at the anode. If the solution is concentrated, chlorine
will be evolved instead.
3. Nature of the electrode; the preference for ionic discharge also depends on the nature of electrodes
used. Inert electrodes are those that do not participate in the electrolytic reaction. Examples are
platinum and carbon (graphite). However, platinum is attacked by liberated chlorine and carbon by
oxygen. An electrode which has a strong affinity for a certain ion will promote the discharge of the ion.
For example in the electrolysis of aqueous sodium chloride using platinum electrodes, H 2(g) is produced
at the cathode.
Electrolysis of molten or fused electrolytes
In the electrolysis of molten or fused electrolytes, the only ions present at the electrodes come from
the electrolyte. Hence, there is no competitive discharge.
Electrolysis of molten sodium chloride using carbon electrodes
The ions present are: 𝑁𝑎 𝑎𝑛𝑑 𝐶𝑙 .
At the cathode: 𝑁𝑎 𝑖𝑠 𝑟𝑒𝑑𝑢𝑐𝑒𝑑, 𝑁𝑎( ) + 𝑒 𝑁𝑎( )
At the anode: 𝐶𝑙 𝑖𝑠 𝑜𝑥𝑖𝑑𝑖𝑧𝑒𝑑 , 2𝐶𝑙( ) 𝐶𝑙 ( ) + 2𝑒
Note: Platinum anode cannot be used because it is attacked by 𝐶𝑙 ( )

51
Electrolysis of aqueous electrolyte solutions
In aqueous solutions, competitive discharge occurs due to the oxidation and reduction of both water
and the solute.
Electrolysis of acidified water(𝒅𝒊𝒍𝒖𝒕𝒆 𝑯𝟐 𝑺𝑶𝟒 ) , the species present are 𝐻 𝑂 , 𝐻 𝑎𝑛𝑑 𝑆𝑂
At the anode:
𝐻 𝑂 𝑖𝑠 𝑜𝑥𝑖𝑑𝑖𝑧𝑒𝑑 𝑖𝑛 𝑝𝑟𝑒𝑓𝑒𝑟𝑒𝑛𝑐𝑒 𝑡𝑜 𝑆𝑂 , 2𝐻 𝑂( ) 𝑂 ( ) + 4𝐻( ) + 4𝑒
At the cathode:
𝐻 𝑖𝑠 𝑟𝑒𝑑𝑢𝑐𝑒𝑑 𝑖𝑛 𝑝𝑟𝑒𝑓𝑒𝑟𝑒𝑛𝑐𝑒 𝑡𝑜 𝐻 𝑂, ( 2𝐻 + 2𝑒 𝐻 ( )) ×2
The overall equation is;
2𝐻 𝑂( ) 𝑂 ( ) + 4𝐻( ) + 4𝑒 + 4𝐻 + 4𝑒 → 2𝐻 ( )
= 2𝐻 𝑂 → 𝑂 ( ) + 2𝐻 ( )
Note: The overall process is equivalent to removal of water from the solution and the solution will
become more concentrated.
Electrolysis of copper (ii) sulphate solution using copper cathode and platinum anode
The species present are 𝐻 𝑂, 𝐶𝑢 𝑎𝑛𝑑 𝑆𝑂
At the anode:
𝐻 𝑂 𝑖𝑠 𝑜𝑥𝑖𝑑𝑖𝑧𝑒𝑑 𝑖𝑛 𝑝𝑟𝑒𝑓𝑒𝑟𝑒𝑛𝑐𝑒 𝑡𝑜 𝑆𝑂 , 2𝐻 𝑂( ) 𝑂 ( ) + 4𝐻 4𝑒 … . . … 𝑖
At the cathode:
𝐶𝑢 𝑖𝑠 𝑟𝑒𝑑𝑢𝑐𝑒𝑑 𝑖𝑛 𝑝𝑟𝑒𝑓𝑒𝑟𝑒𝑛𝑐𝑒 𝑡𝑜 𝐻 𝑂, 𝐶𝑢 + 2𝑒 𝐶𝑢( ) … … … . 𝑖𝑖
𝑀𝑢𝑙𝑡𝑖𝑝𝑙𝑦𝑖𝑛𝑔 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 (𝑖𝑖 ) 𝑏𝑦 2 = 2𝐶𝑢 + 4𝑒 2𝐶𝑢( )
𝐵𝑦 𝑎𝑑𝑑𝑖𝑛𝑔 𝑡ℎ𝑒 𝑡𝑤𝑜 𝑒𝑞𝑛𝑠 𝑡𝑜𝑔𝑒𝑡ℎ𝑒𝑟 𝑤𝑒 ℎ𝑎𝑣𝑒
2𝐻 𝑂( ) + 2𝐶𝑢( ) 𝑂 ( ) + 4𝐻 + 2𝐶𝑢( )
Electrolysis of copper (ii) sulphate solution using copper electrodes
𝑇ℎ𝑒 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑝𝑟𝑒𝑠𝑒𝑛𝑡 𝑎𝑟𝑒 𝐻 𝑂, 𝐶𝑢 𝑎𝑛𝑑 𝑆𝑂
52
At the anode:
𝑡ℎ𝑒 𝑐𝑜𝑝𝑝𝑒𝑟 𝑎𝑛𝑜𝑑𝑒 𝑑𝑖𝑠𝑠𝑜𝑙𝑣𝑒𝑠 𝑖𝑛 𝑝𝑟𝑒𝑓𝑒𝑟𝑒𝑛𝑐𝑒 𝑡𝑜 𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐻 𝑂 𝑎𝑛𝑑 𝑆𝑂
𝐶𝑢( ) 𝐶𝑢( ) + 2𝑒
At the cathode:
𝐶𝑢 𝑖𝑠 𝑟𝑒𝑑𝑢𝑐𝑒𝑑 𝑖𝑛 𝑝𝑟𝑒𝑓𝑒𝑟𝑒𝑛𝑐𝑒 𝑡𝑜 𝐻 𝑂, ∴
𝐶𝑢( ) + 2𝑒 𝐶𝑢( )
During the electrolysis, copper is merely transferred from the anode to the cathode. Hence, there is
no change in the composition of the electrolyte.
QUANTITATIVE ASPECTS OF ELECTROLYSIS
Faraday’s first law of electrolysis: It states that the mass (m) of a substance liberated or deposited at
an electrode during electrolysis is directly proportional to the quantity of electricity (Q) that has passed
through electrolyte. Mathematically,
𝑚 ∝ 𝑄 … . . … … … … … … … … … … … … … … … … … … … … … … … … … … . . … (𝑖)
We know that Q = It
Where, I = current (in ampere), t = time (s)
Therefore, 𝑚 ∝ 𝐼𝑡 and 𝑚 = 𝑍𝐼𝑡
Where Z = electrochemical equivalent of the substance (electrolyte)
If I = 1ampere, and t = 1s then m = Z.
Thus, the electrochemical equivalent is defined as the mass of a substance deposited by one ampere
current passing for one second (one coulomb). It has been found experimentally that the quantity of
electricity required to liberate one gram-equivalent of a substance is 96,500 coulumbs. This quantity
is known as Faraday (F). The quantity of electricity needed to deposit one mole of a substance is given
by the expression.
Quantity of electricity = n x F (where n = valency of its ion)
Thus, the quantity of electricy required to discharge:
One mole of Ag+ = 1 x F = 1F
One mole of Cu2+ = 2F
Al3+ = 3F
53
Reactions at the cathode are represented as;
Ag+ + e = Ag
Cu2+ + 2e = Cu
Al3+ + 3e = Al
It is clear that the moles of electrons required to discharge one mole of ions Ag+ Cu2+ and Al3+ are 1, 2
and 3 respectively. Therefore it means that the quantity of electricity in one Faraday is one mole of
electrons.
Now we can say that, 1Faraday = 96,500coulumbs = 1 mole electrons
The quantity of charge carried by 1 mole of electrons is calculated as follows;
𝐶ℎ𝑎𝑟𝑔𝑒 𝑐𝑎𝑟𝑟𝑖𝑒𝑑 𝑏𝑦 1𝑚𝑜𝑙𝑒 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠

= 𝑁𝑜. 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 𝑖𝑛 1𝑚𝑜𝑙𝑒 × 𝑐ℎ𝑎𝑟𝑔𝑒 𝑐𝑎𝑟𝑟𝑖𝑒𝑑 𝑏𝑦 𝑎 𝑠𝑖𝑛𝑔𝑙𝑒 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛
𝐶ℎ𝑎𝑟𝑔𝑒 𝑐𝑎𝑟𝑟𝑖𝑒𝑑 𝑏𝑦 1𝑚𝑜𝑙𝑒 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 = (6.0225 × 10 ) × (1.60219 × 10 𝐶 ), = 96492 𝐶
The charge carried by 1 mole of electrons is called the Faraday constant F and is rounded off to 96500C
in most of the calculations.
Q is related to the number of electrons (n) by the expression 𝑄 = 𝑛𝐹 … … … . (𝑖𝑖𝑖)
Problem 1. Calculate the amount of charge required to liberate 23 𝑔 𝑜𝑓 𝑁𝑎 𝑎𝑛𝑑 71 𝑔 𝐶𝑙 in the

electrolysis of molten 𝑁𝑎𝐶𝑙.
Solution: 23 𝑔 𝑜𝑓 𝑁𝑎 𝑖𝑠 𝑑𝑒𝑝𝑜𝑠𝑖𝑡𝑒𝑑 𝑏𝑦 1𝑚𝑜𝑙𝑒 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠.

𝐹𝑟𝑜𝑚 𝑄 = 𝑛𝐹
∴ 𝑄 = (1𝑚̸𝑜𝑙) × (96500𝐶 𝑚𝑜̸𝑙 ) = 96500 𝐶
71 𝑔 𝑜𝑓 𝐶𝑙 𝑖𝑠 𝑑𝑒𝑝𝑜𝑠𝑖𝑡𝑒𝑑 𝑏𝑦 2 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠.
𝐹𝑟𝑜𝑚 𝑡ℎ𝑒 𝑒𝑞𝑛 𝑄 = 𝑛𝐹,
𝑄 = (2 𝑚𝑜𝑙) × (96500 𝐶 𝑚𝑜𝑙 ) = 193,000 𝐶
Problem 2. In the electrolysis of molten 𝑁𝑎𝐶𝑙, 𝑎 𝑐𝑢𝑟𝑟𝑒𝑛𝑡 𝑜𝑓 50 𝐴 𝑖𝑠 𝑝𝑎𝑠𝑠𝑒𝑑 𝑓𝑜𝑟 1 ℎ𝑟, calculate:
(a) The amount of charge passed (b) The number of electrons (c) The weight of 𝑁𝑎 𝑎𝑛𝑑 𝐶𝑙
liberated.
Solution: (a) 𝑄𝑢𝑛𝑎𝑡𝑖𝑡𝑦 𝑜𝑓 𝑐ℎ𝑎𝑟𝑔𝑒 = 𝐼𝑡, 𝑓𝑟𝑜𝑚 𝐶 = 𝐴 × 𝑠,

1𝐶 60 𝑚𝑖𝑛 60 𝑠
𝑄𝑢𝑎𝑛𝑡𝑖𝑡𝑦 𝑜𝑓 𝑐ℎ𝑎𝑟𝑔𝑒 = 50 𝐴 × × 1ℎ𝑟
1𝐴 𝑠 1 ℎ𝑟 1 𝑚𝑖𝑛
𝑄 = 50 × 1 𝐶 × 60 × 60 = 180,000 𝐶
(b) Number of electrons,
𝑄
𝐹𝑟𝑜𝑚 𝑄 = 𝑛𝐹, 𝑛=
𝐹
180,000 𝐶
𝑛= , 𝑛 = 1.87 𝑚𝑜𝑙𝑒𝑠 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠
96500𝐶 𝑚𝑜𝑙
(c) Weight of 𝑁𝑎 𝑎𝑛𝑑 𝐶𝑙 𝑙𝑖𝑏𝑒𝑟𝑎𝑡𝑒𝑑
54
𝑁𝑎 + 𝑒 → 𝑁𝑎( )
1𝑚𝑜𝑙 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 𝑑𝑒𝑝𝑜𝑠𝑖𝑡 23 𝑔 𝑁𝑎
1.87𝑚𝑜𝑙 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 𝑑𝑒𝑝𝑜𝑠𝑖𝑡 ? ? 𝑁𝑎
1.87 𝑚𝑜𝑙 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 × 23𝑔
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑁𝑎 = = 43 𝑔 𝑁𝑎
1 𝑚𝑜𝑙 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠
2𝐶𝑙 → 𝐶𝑙 ( ) + 2𝑒
2 𝑚𝑜𝑙 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 𝑑𝑒𝑝𝑜𝑠𝑖𝑡 71 𝑔 𝐶𝑙
1.87 𝑚𝑜𝑙 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 𝑑𝑒𝑝𝑜𝑠𝑖𝑡 ? ? 𝐶𝑙
1.87 𝑚𝑜𝑙 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 × 71𝑔
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐶𝑙 = = 66.4 𝑔 𝐶𝑙
2 𝑚𝑜𝑙 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠
Faraday’s second law of electrolysis
It states that when the same quantity of electricity is passed through different electrolytes, the number
of moles of elements discharged is inversely proportional to the charges on the ions. For example when
the same quantity of electricity is passed through a solution containing
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑠 𝑜𝑓 𝐴𝑙 𝑐ℎ𝑎𝑟𝑔𝑒 𝑜𝑛 𝐶𝑢 𝑖𝑜𝑛 2
𝐴𝑙 𝑎𝑛𝑑 𝐶𝑢 𝑖𝑜𝑛𝑠; = =
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶𝑢 𝑐ℎ𝑎𝑟𝑔𝑒 𝑜𝑛 𝐴𝑙 𝑖𝑜𝑛 3
Problem 3. A current is passed through three electrolytic cells connected in series containing solutions
of 𝐴𝑔𝑁𝑂 , 𝐶𝑢𝑆𝑂 𝑎𝑛𝑑 𝑁𝑎𝐶𝑙 respectively. If 12.7 g of copper are deposited in the second cell,
calculate;
(a) The mass of Ag deposited in the first cell

(b) The volume of chlorine liberated in the third cell
(Ag = 106, Cu = 63.5, molar volume of STP = 22.4 L)
Solution
(a) Consider first , the silver and copper cells and apply second law of electrolysis
𝑛 𝑐ℎ𝑎𝑟𝑔𝑒 𝑜𝑓 𝐶𝑢 𝑖𝑜𝑛
=
𝑛 𝑐ℎ𝑎𝑟𝑔𝑒 𝑜𝑓 𝐴𝑔 𝑖𝑜𝑛
𝑚𝑎𝑠𝑠 𝑜𝑓 𝐶𝑢 12.7 𝑔
𝑛 = = 0.2𝑚𝑜𝑙
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝐶𝑢 63.5𝑔 𝑚𝑜𝑙
𝑐ℎ𝑎𝑟𝑔𝑒 𝑜𝑛 𝐶𝑢 × 𝑛 2
𝐵𝑦 𝑐𝑟𝑜𝑠𝑠 𝑚𝑢𝑙𝑡𝑖𝑝𝑙𝑦𝑖𝑛𝑔 𝑛 = = × 0.2 𝑚𝑜𝑙 = 0.4 𝑚𝑜𝑙
𝑐ℎ𝑎𝑟𝑔𝑒 𝑜𝑛 𝐴𝑔 1
𝑚𝑎𝑠𝑠 𝑜𝑓 𝐴𝑔
∴ 𝐹𝑟𝑜𝑚 𝑡ℎ𝑒 𝑟𝑒𝑙𝑎𝑡𝑖𝑜𝑛 𝑛 = , 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑖𝑙𝑣𝑒𝑟 = 𝑛 × 𝑚. 𝑚
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝐴𝑔
= 0.4 𝑚𝑜𝑙 × 108 𝑔𝑚𝑜𝑙 , ∴ 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑠𝑖𝑙𝑣𝑒𝑟 = 43.2 𝑔
(b) Consider the copper and chloride cells and apply Faraday’s second law of electrolysis
𝑛 𝑐ℎ𝑎𝑟𝑔𝑒 𝑜𝑛 𝐶𝑢 𝑖𝑜𝑛 𝑐ℎ𝑎𝑟𝑔𝑒 𝑜𝑛 𝐶𝑢 𝑖𝑜𝑛 × 𝑛
= n =
𝑛 𝑐ℎ𝑎𝑟𝑔𝑒 𝑜𝑛 𝐶𝑙 𝑖𝑜𝑛 𝑐ℎ𝑎𝑟𝑔𝑒 𝑜𝑛 𝐶𝑙 𝑖𝑜𝑛
55
2 × 0.2 𝑚𝑜𝑙
𝑛 = = 0.4 𝑚𝑜𝑙
1
.
𝑆𝑖𝑛𝑐𝑒 1𝐶𝑙 𝑐𝑜𝑛𝑡𝑎𝑖𝑛𝑠 2𝐶𝑙 𝑎𝑡𝑜𝑚𝑠, 𝑡ℎ𝑒𝑛 𝑛 = = = 0.2𝑚𝑜𝑙
.
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝐶𝑙 = 𝑛 × 𝑚𝑜𝑙𝑎𝑟 𝑣𝑜𝑙𝑢𝑚𝑒 𝑎𝑡 𝑆𝑇𝑃, = 0.2 𝑚𝑜𝑙 × 4.48 𝐿 𝑎𝑡 𝑆𝑇𝑃
56
PART 2: INORGANIC CHEMISTRY
COMING SOON!
57

CHM 101 General Chemistry I - LN - Part 1

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

CHM 101 General Chemistry I - LN - Part 1

Uploaded by

Copyright:

Available Formats

CHM 101: General Chemistry I

Level 100 Students

Dr. Shehu Habibu

Part 1: Physical Chemistry

Part 2: Inorganic Chemistry

Course Coordinator: Dr S. Habibu (s.habibu@fud.edu.ng)

PART 1: PHYSICAL CHEMISTRY

0.411𝑚𝑜𝑙 𝑥 0.0821𝐿 𝑎𝑡𝑚 𝑚𝑜𝑙 𝐾 𝑥 293𝐾

Moles of H2 = 2.0/2.02 = 0.99 moles

Moles of N2 = 8/28 = 0.286 moles

Thus, PT = PH2 + PN2 = 2.86 atm.

By definition, nA + nB = ntotal …………………………….................................................….(1)

XA + XB = 1, where XA = , the mole fraction of A and XB = the mole fraction of B.

Relationship between Partial Pressure, Mole Fraction and Total Pressure

Kinetic Molecular Theory (KMT) of Gases

Assumptions of the KMT

Kinetic Gas Equation in terms of Kinetic Energy

Let N be the number of molecules in a given mass of gas,

Deduction of Gas Laws from the Kinetic Gas Equation

Therefore, V = (constant)T or V = k’T ……………………………….. (6)

c). Avogadro’s Law

d). Graham’s Law of Diffusion:

Deviations from Ideal Behaviour

 For an ideal gas, Z = 1 at all conditions (independent of T & P).

EXPLANATION OF DEVIATION – VANDER WAALS EQUATION

Since nb is excluded volume for n moles of gas, b = = = litre mol-1 units.

Limitation of Van Der Waals Equation

Thermochemistry is the study of energy changes that accompany chemical reaction

Heat Change in Chemical Reaction

Energy level diagrams for endothermic and exothermic processes:

Standard Enthalpy Change of Formation (∆Høf)

H2(g) + O2(g) H2O(l) ∆Hø1 = -286kJ………………………………… (1)

HCl(aq) + NaOH(aq) H2O(l) + NaCl(aq) ∆Hø2 = -57.9kJ….… (2)

2H2(g) + O2(g) 2H2O(l) ∆Hø3 = -572 kJ……………………………… (1)

Note: Elements in an un-combined state have ∆H øf = 0

Standard Enthalpy Change of Combustion (∆Høc)

C(s) + O2(g) CO2(g) ∆Hø = 393kJmol-1

The equation below is not ∆Høc

C(s) + O2(g) CO(g) (because it is incomplete combustion that is, O2(g) )

Standard Enthalpy Change of Atomization (∆Høatm Or ∆Hødiss)

Example: Cl2(g) 2Cl(g) ∆Hødiss = …….kJmol-1

Standard Enthalpy Change of Sublimation (∆Høsub)

A(s) A(g) ∆Høsub = …….kJmol-1

Ionization Potential (IP)

e.g. Na(g) Na+(g) + e-

Electron Affinity (EA)

e.g. Cl(g) + e- Cl-(g)

Lattice Energy (∆Hlattice)

AB(s) A+(g) + B-(g)

e.g. NaCl(s) Na+(g) + Cl-(g)

Standard Enthalpy Change of Solution (∆Hsolution)

NaOH(s) + Water NaOH(aq) ∆Høsolution = -42.7kJmol-1

Standard Enthalpy Change of Neutralization (∆H neut)

H+(aq) + OH-(aq) H2O(l)

Thermochemical Equation (TCE)

Example: H2(g) + O2(g) H2O(l) ∆Hø1 = -286kJmol-1

 When a thermochemical equation is reversed, the sign of ∆H is also reversed. e.g.

H2O(l) H2(g) + O2(g) - ∆Hø1 = +286kJmol-1

 When a thermochemical equation is multiplied by a factor n, the ∆H is also multiplied by

1. Reverse the following thermochemical equations:

a. C2H2(g) 2C(s) + H2(g) - ∆H1 = -22.6 kJmol-1

Multiply the coefficients and ∆H by

H2(g) + O2(g) H2O(l) ∆H = -286 kJmol-1