(CHAPTER#1)

INTRODUCTION TO THE FUNDAMENTAL CONCEPTS OF CHEMISTRY

CHEMISTRY
It is the branch of Science that deals with the study of composition, states and changes in Properties
of matter.
 Chemistry also deals with the energy associated with these changes.
 Chemistry is not concerned with forms in which materials are designed, e-g; The composition
and structure of rubber is significant for Chemistry but their designs like tires, sheets etc are
not concerned with Chemistry.
 The changes like rusting of iron, evaporation of spirit, digestion of food, synthesize of food
by plants by photosynthesis are studied under the heading of Chemistry.
SIGNIFICANT FIGURES
Definitions:
The reliable digits, known with certainty in a given number are significant figures.
Explanation:
Significant figures are those digits whose removals create an uncertainty in value.
The degree of precision and certainty of a measured quantity increases with the increasing number
of significant figures in it.
The number of significant figures in a measured quantity depends upon the following factors.
(a) Scale used for measurement
(b) Size of object
(c) Degree of approximation
Rules to determine significant figures:
1. All non zeros are significant. For example:
18 has two significant figures. 398 has three significant figures.
2. Zeros appearing between nonzero digits are significant. For example:
60.8 has three significant figures. 39008 has five significant figures.
3. Zeros appearing in front of nonzero digits are not significant. For example:
0.093827 has five significant figures. 0.0008 has one significant figure.
0.012 has two significant figures.
4. Zeros at the end of a number and to the right of a decimal are significant. For example:
35.00 has four significant figures. 8,000.000000 has ten significant figures.
5. Zeros at the end of a number without a decimal point are not significant. For example:
1,000 has one significant figures.

EXPONENTIAL NOTATIONS “OR” SCIENTIFIC NOTATIONS

Definition: The method of expressing a number as a factor of power of 10 is called exponential
notations.
Explanation:
 Exponential notations are used to express very large values like Avogadro’s number (carrying
twenty four digits) or very small values like Plank’s constant (carrying twenty seven / thirty
four digits) conveniently.
 Exponential notation is a scientific method of representing very large or very small values.
 Exponential notations consist of three parts, co-efficient, base and power. Base in Exponential
notations is always 10.

Examples:
Exponential Values Co-efficient Power of 10
6.02 x 1023 6.02 23
6.625 x 10-34 6.625 -34

Ways of writing a value in Exponential form: Rules for writing a value into exponential form:
The Exponential form should be given to Decimal is shifted after the first digit and the number of
a value in such a ways that decimal point must be digits shifted is expressed as exponent of 10.
1. When decimal is shifted towards left, the power of
after one digit from left. For example, 6.02 × 1023
10 will be positive.
is correct form of exponents whereas 60.2x1022 2. When decimal is shifted towards right, the power of
is not the standard way of writing exponents. 10 will be negative.

ROUNDING OFF DATA

Rules to round off a value:
Definition: Following rules are used for rounding-off the measured
The process of reducing the number of quantities in various mathematical functions.
significant figures in a measured quantity to the 1. If the last significant digit is greater than 5, then it
desired number is called as rounding of data. will be dropped by increasing preceding digit by one.
For example, 30.36 will become 30.4.
Explanation: 2. If the last significant digit is less than 5, then it will
 Rounding off data is used to avoid least be dropped without making any change in the preceding
significant digits. digit. For example, 15.74 will become 15.7.
 Third digit after decimal point and beyond 3. If the last significant digit is exact 5, then we will see
the preceding digit whether it is even or odd.
this becomes uncertain so rounding off data
(a) If the preceding number is odd (3, 5, 7, 9), then it
is recommended will be increased by one with the dropping of last digit.
 Rounding off data is applied to remove the For example, 24.75 will become 24.8.
digits after decimal point only. (b) If the preceding number is even (2, 4, 6, 8), then it
will not be increased by one with the dropping of last
digit. For example, 39.45 will become 39.4.
ERROR (c) If the preceding number is zero or one then we will
The deviation in measured value from the actual see the second preceding digit whether it is even or odd.
value is called error. For example, 48.615 will become 48.61 and 48.305 will
Types of error: There are two types of errors. become 48.31.
1. Systematic “or” Determinate errors
2. Random errors “or” In determinate errors
Systematic “or” Determinate errors:-
Definition: The error those can be determined, usually caused by the defect in analytical method
by improper functioning of instrument “or” improper handling of apparatus is called systematic
error. The systematic errors can be eliminated.

Random errors “or” Indeterminate errors:

Definition: The errors for which source cannot be determined are said to be random errors. For
example, if we take reading 13.7 ml from a burette, there will be the +/– 0.01 error. This is called
random error.
Random errors can be minimized by taking average of at least three readings.
LOGARITHM
It is a power to a positive number other than one.
Explanation:
If a number “Y” is expressed in exponential notation “ax” (i.e.: Y = ax), where “a” is any positive
number other than one. Than “x” is a logarithm of “Y” and “a” is the base. Mathematically we
can write as follows:
Y = ax OR X = loga Y
Uses of logarithm: Logarithm is very useful in complicated calculations of multiplications,
divisions, roots and powers.
Rules of logarithm:
There are following three rules applied for solving the numerical with the help of logarithm.
log a.b = log a + log b
a
log  log a  log b
b
log an = n log a

MOLE
Definitions:
 The amount of substance that contains as much number of particles (atoms, ions or molecules)
as there are in 12g of C12 is called mole.
 The gram atomic weight of an atom, gram molecular weight of a compound or gram formula
weight of a salt is called a mole.
Examples:
 16g of Oxygen atoms (O) contain 1 mol.
 16g of Oxygen molecules (O2) contain 0.5 mol.
 32g of Oxygen molecules (O2) contain 1 mol.
 18g of water (H2O) contains 1 mol.
 23g of Sodium ion (Na+) contains 1 mol.
 58.5g of Sodium Chloride (NaCl) contains 1 mol.
Explanation:
 The atomic, molecular or formula weight of a substance expressed in grams is equal to 1 mole.
 If the weight of a substance is known, its number of moles can be calculated by following
expression.
Mass of a subs tan ce in grams
Number of moles =
Molar mass of subs tan ce
Symbol and unit of mole: Mole is represented by “n” whereas its unit is “mol”.

AVOGADRO’S NUMBER
Introduction:
An Italian Physicist Amedo Avogadro (1776–1856) suggested the number of particles in one mole
of a substance, called Avogadro’s number.
Definition:
The number of particles (atoms, ions or molecules) present in one mole of a substance is called
Avogadro’s number. i.e.: 6.02 × 1023.
Example:
 1 mol of Glucose (C6H12O6) contains 6.02 x 1023 molecules of Glucose.
 0.5 mol of Sodium atom (Na) contains ½ x 6.02 x 1023 (3.01 × 1023) atoms of Na.
 1 mol of CaCl2 contains 6.02 x 1023 ions of Ca+2 and 2 × 6.02 x 1023 ions of Cl-.
Explanation:
 It is a fixed number of particles in one mol of a substance whether the particles are smaller or
larger, lighter or heavier.
 The number of particles in one mole of any substance remains same (6.02 x 1023) whether the
particles are heavier or lighter.
 In case of ionic compounds (salts) the concept of mole is little bit different. For example 58.5g
(23+35.5) of NaCl contains 6.02 x 1023 ions of Sodium (Na+) & 6.02 x 1023 ions of Chlorine
(Cl-).
 Avogadro’s number is very useful in estimating the number of particles in a given quantity
(mole or mass or volume) of a substance. Following expression is applied for this purpose.
Number of particles = Number of moles x Avogadro’s number
Symbol and unit of Avogadro’s number:
Avogadro’s number is denoted by “Na” It is a number so it has no unit.

CHEMICAL FORMULA
Definition: The symbolic representation of one molecule of a compound is called chemical
formula.
Explanation:
 Chemical formula is composed of symbols of elements present in one molecule of a
compound.
 Chemical formula shows the no. of atoms of each element present in one molecule of a
compound. For example, the chemical formula of Glucose is C6H12O6. It represents that one
molecule of Glucose consists of six atoms of Carbon, twelve atoms of Hydrogen and six atoms
of Oxygen.
Types of chemical formula: There are two types of chemical formula.
1. Empirical “or” Simple formula
2. Actual “or” True “or” Molecular formula

EMPIRICAL FORMULA
Definition: The formula that shows the simplest ratio between the numbers of atoms of different
elements present in one molecule of a compound is called empirical formula.

Compound Molecular formula Divide no. of atoms by Empirical formula

Glucose C6H12O6 6 CH2O
Octance C8H18 2 C4H9
Water H2O 1 H2O
Acetic Acid CH3COOH(C2H4O2) 2 CH2O
Potassium Iodide KI 1 KI
Sugar C12H22O11 1 C12H22O11

MOLECULAR FORMULA
Definition: The formula which shows the actual or exact number of atoms of different elements
present in one molecule of a compound is called molecular formula.
Explanation:
 It is the actual formula of the compound that shows the actual or exact number of atoms of
elements in the compound.
 Molecular formula is simple multiple of a whole number (n) to its empirical formula.
Molecular formula = (Empirical formula)n
 The ionic compounds (salts) do not posses molecular formula due to not occurring in the
molecular form.

STOICHIOMETERY
Introduction:
The term Stoichiometery is taken from Greek language. (Stoichoin- element; metery- amount)
Definition:
The study of relationships between the amounts of reactants and products is called stoichiometery.

Explanation:
 From the chemical equation for a certain reaction, the ratio of moles can be determined. On
the basis of this ratio, the mass or volume of the reactants or products can be calculated.
 Stoichiometery is a quantitative study of relationships between the reactants and products.
 Stoichiometric amounts in the following reaction are:

2C2H6 + 7O2  4CO2 + 6H2O

In terms of moles => 2mol 7mol 4mol 6mol
In terms of mass => 2x30g 7x32g 4x44g 6x18g
In terms of volume => 2x22.4 dm3 7x22.4 dm3 4x22.4 dm3 6x22.4dm3

Relationships for stoichiometric calculations:

Stoichiometric calculations are classified into following three groups (relationships).
1. Mass–Mass relationship
2. Mass–Volume relationship
3. Volume–Volume relationship

LIMITING REACTANT “OR” LIMITING REAGENT

In a reaction, the reactant that is in less amount as
Where we apply the method of limiting
compared to its stoichiometric amount is called limiting reactant:-
reactant.
Those calculations in which the amounts
Explanation: of more than one reactant are given, we
will apply the method of limiting reactant
In a chemical reaction such reactant that consumes
for calculation and if the amount of only
earlier (due to the less in amount than the required one reactant or product is given, we will
amount) is called limiting reactant and the reactant apply simple stoichiometric calculations.
whose some amount remains un reacted (due to the (Mass–Mass, Mass–Volume, Volume–
greater amount than its stoichiometric amount) is called Volume relationships)
excess reagent “or” excess reactant.
 (CHAPTER#2)
THREE STATES OF MATTER GASES, LIQUIDS AND SOLIDS

Matter exists in three states i.e gases, liquids and solids. Plasma as the fourth state of matter
has also been discovered. It is a jelly like matter. It is an intermediate state of solid and liquid.
Protein in egg yolk and fat in our body are the examples of plasma.

Differences in gases, liquids and solids:

Characteristics Gases Liquids Solids
Volume Indefinite Definite Definite
Shape Not fixed Not fixed Own
Intermolecular distances High Less Negligible
Intermolecular attractions Very less High Very high
Compressibility High Less Negligible
Diffusion Very high Less Negligible at high pressure

Miscibility Very high Less Negligible at high pressure

KINETIC MOLECULAR THEORY (KMT)

Introduction: Kinetic Molecular Theory was first proposed by
Bernoulli in 1738. It was then extended by Boltzmann, Maxwell,
Clausius and Vander Waals. This theory explains the behavior of ideal
gases.

Kinetic Molecular Theory of Gases

Postulates: Kinetic molecular theory consists of following postulates.
1. Gas molecules are widely separated throughout the container
at ordinary conditions.
2. The effect of gravity on gas molecules is negligible due to very less weight of an
individual molecule.
3. Volume of gas molecules is negligible as compared to the volume of container.
4. The gas molecules are continuously in the state of random motion and they travel in the
straight line.
5. There are no attractive or repulsive forces between the gas molecules.
6. The collisions between gas molecules is perfectly elastic, and there is no loss of kinetic
energy.
7. The collision of molecules cause gas pressure.
8. The average kinetic energy of gas molecules is ½ mv2.

Kinetic molecular theory of Liquids

1. The particles of liquids are randomly arranged but in more ordered form than the gas
particles.
2. The liquid particles are arranged in the form of clusters, therefore forms a definite
volume.
3. Liquid does not have its own shape due to free motion of its particles.

Kinetic molecular theory of Solids

1. There are strong attractive forces among solid particles, hence they are closely packed.
2. The movement in solid particles is negligible due to very less inter particle distances.
3. The solids have their definite shape and own volume due to the closely packed particles.

BEHAVIOR OF GASES
1. Diffusibility
Definition: The ability of spreading or distribution of gas
molecules throughout the vessel is called diffusibility.
Example: When we spray perfume, its fragrance spreads
throughout the room. It is an example of diffusion of perfume
vapors through air.
Explanation: The gas molecules are free to move due to the
large empty spaces between gas molecules. This is the fact
that gas molecules intermix with one another to cause
diffusion.

2. Effusion
Definition: The passing (escaping) of gas molecules from the tiny hole or pore of the
container. It is the opposite of diffusion.
Example: Puncturing of tire is an example of effusion of air from tire.
Explanation: The gas molecules are free to move due to the large empty s paces between
gas molecules. This causes the passage of gas molecules from tiny hole of container to
give effusion.

3. Compressibility
Definition: The ability of gas molecules to come closer on
applying pressure is called compressibility.
Examples:
 CNG (Compressed Natural Gas) fuel is an example of
compressed gas.
 Air is compressed in automobile tires.
Explanation: There are large empty spaces between gas molecules,
so they can come closer to each other on applying pressures.

4. Expansibility
Definition: The ability of increasing volume of gases on releasing pressure is called
expansibility.
Explanation: There are very weak intermolecular attractions in gases, so they cannot remain
closer to each other. Hence they go away from each other on decreasing pressure over them.

5. Pressure
Definition: The force exerted by the gas molecules, per unit area is called pressure.
Force
Mathematically: Pr essure 
Area
Explanation: According to Kinetic molecular theory, the gas pressure is produced by the
collisions of molecules with one another and with the walls of container.

Different units of Pressure Symbols Different units of Pressure Symbols

Atmosphere atm Pounds per square inch Psi (lb/in2)
Newton per meter square N/m2 Pascal Pa
Torr torr Millimeter of mercury mmHg

Kilogram per square meter Kg/m2 Kilogram per square centimeter Kg/cm2

SI Units of pressure
Force Newton
Pr essure   Pr essure  2
 N.m 2
Area m
Relationship among the units of pressure
1atm = 760torr = 760mmHg = 14.7psi = 101325Pa = 101325N/m2 = 1.033Kg/cm2 = 0.001033Kg/m2
Temperature
 The degree of hotness and coldness is called temperature.
 The property which determines the flow of heat is called temperature.
 SI unit of temperature is Kelvin (K).
Scale of temperature: There are three common scales of temperature:
 Celsius scale or Centigrade scale (0C)
 Fahrenheit scale (0F):
 Kelvin scale (K):
Inter conversion of temperature
1. Centigrade to Fahrenheit scale 0F = (0C x 1.8) + 32
2. Fahrenheit to Centigrade scale 0C = (0F – 32) ÷ 1.8
3. Centigrade to Kelvin scale K = 0C + 273
4. Kelvin to centigrade scale 0
C = K – 273

Difference between ideal gases and real gases

No. IDEAL GASES REAL GASES
1. Ideal gases obey all gas laws in all Real gases do not obey all gas laws in
conditions. variable conditions.
2. Ideal gases obey all gas laws even at low Real gases deviate from ideal behavior at
temperature and high pressure. very low temperature and very high
pressure.
3. There is no any gas ideal in the universe. All gases in the universe are real.
4. The concept of ideal gases is imaginary. The concept of these gases is real.
5. These gases are also known as perfect These gases are also known as non-perfect
gases. gases.

IDEAL GAS LAWS: The laws explaining the behavior of ideal gases are known as ideal
gas laws. There are three major following laws about the ideal gases.

1. Boyle’s law 2. Charles’s law 3. Avogadro’s law

BOYLE’S LAW
(The relationship of volume and pressure)

Introduction: In 1960, Robert Boyle explained the relationship between the volume of
given mass of a gas and pressure at constant temperature, called Boyle’s law.
Statement: The volume of a given mass of a gas is inversely proportional to the pressure
exerted on it at constant temperature.

Experimental verification of the Boyle’s law:

Robert Boyle took a J-shaped tube closed at smaller end.
 A scale was fixed at smaller limb.
 He inserted mercury from the open (longer) end and the gas (air) which was inside the
tube was captured in the smaller end. He noted the volume of air through scale.
 He inserted more
mercury from the open
(longer) end and noted
that the volume of air is
reduced.
 He further inserted
mercury from the open
(longer) end and noted
the further decrease in
volume of air.

Conclusion: - Robert Boyle concluded from above experiment that the decrease in volume
is due to the increase in pressure by the mercury.

Graphical representation of Boyle’s law:

(i) A parabolic curve is obtained when volume of a gas is plotted v/s pressure exerted on it.
(ii) Straight line is obtained when volume of a gas is plotted v/s inverse of pressure exerted
(1/P) on it.
Mathematical representation of Boyle’s law:

V α 1/P (at constant pressure)

V = K x 1/P (K is constant)
 PV = K
This shows that at constant temperature, the product of volume of a gas and pressure exerted on it
is always constant. For two conditions:
For condition 1: K = P1V1  Equation # 1
For condition 2: K = P2V2  Equation # 2
By combining equation # 1 and equation # 2

P1V1 = P2V2
Where 
P1 = Exerted pressure on gas for 1st condition
P2 = Exerted pressure on gas for 2nd condition
V1=Volume of the gas for 1st condition
V2=Volume of the gas for 2nd condition

Explanation of Boyle’s law on the basis of Kinetic molecular theory:

When pressure is increased, the volume will be decreased at constant temperature because
when high pressure is applied the gas molecules come closer to each other due to larger
empty space between them so the volume of gas is decreased.
When volume is decreased, the pressure of the gas is increased constant temperature
because of decrease in volume, the gas molecules will come closer to each other and collide
more frequently with one another and with the walls of container, and hence gas pressure
is increased. Whereas the average velocity of the molecules remains unchanged due to
constant temperature.

CHARLES LAW
(The relationship of volume of a gas and temperature)

Introduction: In 1787, a French Physicist Charles explained the relationship between the
volume of a given mass of a gas and its temperature at constant pressure, called Charles law.
Statement
“The volume of a given mass of a gas is directly proportional to the temperature of that gas”

The straight line in the graph of

volume v/s temperature shows the
direct relationship between
temperature and volume of the gas.
By extra plotting, it is seen that the
volume of the gas becomes zero at –
273 0 C (0 K) called zero Kelvin.

Absolute Scale “or” Absolute zero

“or” Zero degree temperature:
At absolute zero, the volume of all
gases is considered to be zero and all the motion ceases to exist.
Mathematical representation of Boyle’s law:

VαT (P is taken constant)

 V=KT (K is constant)

V
K
T
This shows that at constant pressure, the ration between volume of a gas and temperature is
constant.
i.e. K. for two conditions.

V1
For condition 1: K  Equation # 1
T1
V2
For condition 2: K  Equation # 2
T2

V1 V2
By comparing equation # 1 and equation # 2 
T1 T2

Explanation of Charles’s law on the basis of Kinetic molecular

theory:
When temperature is increased, the kinetic energy of gas molecules
also increases. Hence molecular velocity increases which causes
expansion of gas to occupy greater volume.

Avogadro’s Law
(The relationship of volume of a gas and no. of molecules)

Introduction: In 1811, Amadeo Avogadro explained the relationship between the volume
of a given mass of a gas and the no. of molecules at constant pressure and
temperature, called Avogadro law.
Statement: Equal volumes of all gases at same temperature and pressure contain the same
no. of molecules.
Explanation: Equal number of molecules means equal no. of moles, which changes
with volume at constant temperature and pressure.

Mathematically representation of Avogadro’s law:

Vαn (T and P are constant)

V=Kn (K=constant, n = no. of moles/molecules)
V
K
n
This shows that at constant temperature and pressure the ratio between volume of a gas and
number of moles / molecules is constant i.e. K. At STP, the kinetic energy of molecules of
all gases is same. Therefore, volume of one mole of all gases is similar i.e 22.4dm3. This is
called molar volume or molar gas volume.

Mass/Volume Oxygen Sulfur trioxide Carbon dioxide Hydrogen

(O2) (SO3) (CO2) (H2)
 Molar Mass (a.m.u) 32 80 44 2

Volume (dm3) 22.4 22.4 22.4 22.4

Applications of Avogadro’s law: Avogadro’s law is applied to determine the relative

molecular masses of the gases. For example, at standard conditions, 1dm3 of O2 have 1.43g
but 1 dm3 of CO have 1.25g weight. According to Avogadro’s law at standard conditions
1 dm3 of all gases will have same number of molecules. So;

Molecular mass of CO Weight of CO


Molecular mass of O 2 Weight of O 2

Molecular mass of CO 1.25


32 1.43

1.25
Molecular mass of CO   32
1.43

Molecular mass of CO = 28 amu

IDEAL GAS EQUATION “or” GENERAL GAS EQUATION “or” EQUATION OF STATE

Definition: It is an equation which is generally derived from ideal gas laws.

Derivation:
1
Boyle’s law is Vα (T is constant)  Equation # 1
P

Charles’s law is VαT (P is constant)  Equation # 2

Avogadro’s law is Vαn (T & P is constant)  Equation # 3

By combining equation # 1, 2 and 3,

1
Vα .T.n
P
1
OR V= R. .T.n. (RGeneral gas constant)
P
OR PV = RTn

OR PV = nRT

Where, P = Pressure of the gas, V=Volume of the gas

n = no. of moles of the gas, T = Temperature of the gas

For one mole of a gas

PV = RT
 PV
OR R=
T
For 1st condition
P1V1
R  Equation # 1
T1
P2V2
R  Equation # 2
T2

P1 V1 P2 V2
By comparing equation # 1 and equation # 2 
T1 T2

General Gas Constant (R) - different units:

1mol of a gas at S.T.P.
For For
0.0821 dm3.atm/mol.K OR 0.0821 L.atm/mol.K 8.314 Nm / mol.K OR 8.314 J / mol.K
Data Data
n = 1 mol n = 1 mol
T = 273 K T = 273 K
P = 1atm V= 22.4 dm3 P = 101300 Nm-2
R=? 22.4 3
V  22.4dm3  m  0.0224m3
1000
Solution R=?
PV = nRT
1atm  22.4dm 3 Solution
R
1 mol  273K PV = nRT
101300 Nm 2  0.0224 m3
1 22.4 atm  dm 3 R
R  1 mol  273K
1  273 mol  K
101300  0.0224 Nm 2  m3
R  0.0821 dm .atm / mol.K
3
R 
1 273 mol  K
R  8.314 Nm / mol.K

Ideal behavior: The behavior of a gas according to the gas laws is called ideal behavior.
Which gases are more ideal? The gases those have low boiling points such as nitrogen (-
1960C), Hydrogen (-2520C) & Helium (-268.50C) behave more ideally than the gases which
have high boiling points, e.g Chlorine (-350C) and Sulfur dioxide (-100C).

GRAHAM’S LAW OF DIFFUSION

Introduction: In 1881, a Chemist Graham established a relationship between the rates of

diffusion of gases and their densities (molecular mass), called Grahams law
of diffusion.
Statement: The rates of diffusions of gases are inversely proportional to the square root
of their densities or molecular weights at constant temperature and pressure.
1
r
d
Explanation:
 Lighter will be the gas, higher will be the rate of
diffusion with another gas. Heavier will be the
gas, less will be the rate of diffusion.
 All gases mix with one another in all proportions.
Whenever two or more gases are put together in
a container, they readily intermingle with one
another forming a homogenous mixture of the
gases.
 This intermingle of gases depends upon their
densities or molecular weights, at constant temperature and pressure.

Example

If Ammonia and Hydrochloric acid gases are inserted from two ends of a horizontally placed
glass tube, we will see that ammonia (M.Wt: 17amu) will reach earlier at the diffusion point
than hydrochloric acid (M.Wt: 36.5amu) due to less molecular weight.

Mathematically: According to Graham’s law:

1
r Where d  Density of the gas
d
1
OR r  K. K  Pr oportionality cons tan t
d
OR K  r. d For two conditions
K  r1. d1 Equation # 1
K  r2 . d 2 Equation # 2
By comparing equation # 1 & equation # 2

r1. d1  r2 . d 2 by re aranging
r1 d2
OR 
r2 d1
M2
r1 V2  M
OR  d  
r2 M1  V 
V1
r1 M 2 V1
 
r2 V2 M1
Since volumes of both gases are taken same (V1 = V2) then above equation can be written as
 r1 M2

r2 M1
r1 = Rate of diffusion of 1st gas r2 = Rate of diffusion of 2nd gas
M1 = Molecular mass of 1st gas M2 = Molecular mass of 2nd gas
d1 = Density of 1st gas d2 = Density of 2nd gas

Explanation of Graham’s law on the basis of kinetic molecular theory:

According to kinetic molecular theory of gases, the energies of the same quantities of gases
are the same at constant temperature and pressure, so the rate of diffusion depends upon the
densities or molecular weights. The gas which
has comparatively less density (or molecular
mass) will move more frequently than other
gas to give diffusion with higher rate.

DALTON’S LAW OF PARTIAL

PRESSURE

Introduction: This law was suggested by John

Dalton in 1801 about the pressures of the
mixture of gases.
Statement: The total pressure of the
mixture of gases is the sum of the partial
pressure of the gases in the mixture.
Explanation:
 In a mixture of different gases, each gas behavior is independently of other gases and
exerts its own pressure.
 The individual pressure of the gas in the mixture is called partial pressure (Pgas).
 All the partial pressures in the gaseous mixture is collectively called total pressure (PT).

Mathematically:
PT = pa + pb + pc . . . . pn

Pgas n gas

PT nT
PT = Total pressure of the mixture pA = Partial pressure of gas A
pB = Partial pressure of gas B pC = Partial pressure of gas C
pn = Partial pressure of nth gas pgas = Partial pressure of gas A
ngas = No. of moles of gas in mixture nT = Total no. of moles in mixture

Explanation of Dalton’s law on the basis of kinetic molecular theory:

In a mixture of non-reacting gases, each gas exerts own pressure due to the collision of
molecules with one another and with the walls of container. Hence, total pressure of the
mixture is because of sum of all collisions.
Application of Dalton’s law of partial pressure:
The most important application of Dalton’s law of partial pressure is
“Determination of pressure of the gas collected over water”.
A water insoluble gas (O2, H2, CO2 etc) is collected over water in
laboratory preparation. It contains water vapors as well, called “ moist
gas”. Hence the pressure of moist gas is the sum of pressure of dry gas
and the pressure of water vapors. Therefore the pressure of dry gas can
be calculated as follows.

P moist gas = P drg gas + P water

P dry gas = P moist gas - Pwater

LIQUID

Introduction: It is the intermediate state of gas and solid state. It has a definite volume but
does not have any fixed shape. It occupies the shape of container.

Liquification: Gas can only be converted into liquids at low temperature. This conversion
of gases into liquids on cooling is called “Liquification”.
Gas Cool
 Liquid Cool
 Solid

Behavior of liquids:
1. Diffusibility: The mixing of liquids to make homogenous mixture is the diffusion of
liquids. Rate of diffusion of liquids is lesser than gases due to less intermolecular distances.
Example: Mixing of colored solution with water.
Explanation on the basis of kinetic molecular theory: The free movement of liquid
molecules causes diffusion but the slow rate of diffusion is due to closeness of molecules.

2. Compressibility The ability of molecules of liquids to come closer on applying high

pressure is called compressibility of liquids. Liquids are very less compressible on
applying high pressures.
Explanation on the basis of kinetic molecular theory: The molecules of liquids are
close to one another and there is not enough space between molecules to come closer on
applying high pressure.

3. Contraction: The decrease in volume of a liquid on decreasing temperature is called

contraction. When a liquid is cooled it contracts and solidifies on further cooling.
Explanation on the basis of kinetic molecular theory: When a liquid is cooled its
kinetic energy decreases so the velocity of molecules also decreases. Therefore the
molecular volume decreases to give contraction.

4. Expansion: The increase in volume of a liquid on increasing temperature is called

expansion. When a liquid is heated it expands and vaporizes on further heating.
Explanation on the basis of kinetic molecular theory: When a liquid is heated, its
kinetic energy increases so the velocity of molecules also increases. Therefore the
molecular volume increases to give expansion.

VISCOSITY
Introduction: All liquids can flow less or more. When they flow, the layers of liquid slide
over one another and layers resist each other to flow; this resistance is named as viscosity.
Symbol: Viscosity of liquid is represented by eta (η).
Definition: The internal resistance between the parallel layers of liquid to flow is called
viscosity.
Explanation: When a liquid moves in a
thin pipe, it moves in the form of layers.
The layer attached to the walls of pipe is
almost stationary. But at center, t h e layers
move with gradually higher resistance to
flow. This resistance to flow is called
viscosity of that moving liquid in the pipe.
S.I. Unit Kilogram per meter per second Kg / m. Sec
Newton seconds per square meter N.Sec / m2
Gram per centimeter per second g / cm. Sec
CGS system Dynes second per centimeter square dyne. Sec / cm2
Poise Poise
Unit equivalents: 1 poise = 1 dyne. Sec / cm2
1 poise = 100 centi poise
1 centi poise = 0.001 N. Sec / m2
1 poise = 0.1 N. Sec / m2
1 poise = 1 g / cm. Sec
Factors affecting viscosity:
1
1. Temperature: Vis cos ity 
Temperatur e
Viscosity of liquid decreases 2% per degree rise of temperature of liquid.
When temperature is increased, the intermolecular distances also increases that causes
less resistance between the layers of liquid to flow, hence viscosity also decreases.

Viscosities of some liquids in centi poise at different temperatures

Viscosity (centi poise)
Liquid
00 C 200C 500C
Water 1.789 1.005 0.55
Ethyl alcohol 1.78 1.19 0.701
Glycerin 12100 1499 -------
Acetone 0.395 0.322 0.246

2. Intermolecular attraction: Viscosity α Intermolecular attractions; Greater will be the

intermolecular attractions, higher will be the viscosity due to less intermolecular distances
that causes higher resistance between liquid layers.
Water is more viscous than ethyl alcohol due to the greater no. of hydrogen bonds in water
than ethyl alcohol.

3. Size of molecules: Viscosity α size of molecules

Liquids of lager molecules have higher viscosity due to more resistance to layers of
molecules of liquid to flow.
Glycerin is more viscous than water due to larger molecules of glycerin than the molecules of
water.

4. Shape of molecules:
Liquids of simple and spherical molecules have low viscosity due to less resistance to layers
of molecules of liquid to flow but the liquids of complex, elongated and branched
molecules have high viscosity due to comparatively higher resistance to layers of molecules
of liquid to flow.
Water is less viscous than honey due to less complicated shape of molecules of water than
the molecules of honey.
 SURFACE TENSION
Definitions:
 The force per unit length acting at the surface of a liquid is called
surface tension. OR
 The energy per unit acting at the surface of a liquid is called
surface tension.
Explanation: All molecules of liquid are attracted by all sides;
hence attractions are balanced from each side but at surface,
attractions are not balanced vertically due to not having any layer
of molecules above the surface layer in liquid. This imbalanced
attraction at surface of liquid is called surface tension. Surface tension reduces the surface area
of the liquids. It is represented by gamma (γ).

Units of surface tension:

CGS System Dynes per centimeter (Force per unit length) dynes / cm
Ergs per centimeter square (Energy per unit area) ergs/cm2
SI System Newton per meter (Force per unit length) N/m
Joule per meter square (Energy per unit area) J / m2
Unit equivalents: 1 dyne/cm = 0.001 N/m
1 dyne/cm = 1 erg/cm2

Factors affecting surface tension:

1
1. Temperature: Surface Tension 
Temperatur e
When temperature is increased, the intermolecular distances increases and intermolecular
attractions decreases which causes less unbalanced pull (surface tension) at the liquid
surface.
2. Intermolecular attractions: Surface tension α Intermolecular attractions
Stronger will be intermolecular attractions, higher will be surface tension due to greater
unbalanced pull at the liquid surface.
The surface tension in carbontetrachloride is less than the surface tension of water due
to non-polar nature of carbon tetra chloride whereas water is polar and hydrogen bonds
are also there in water, due to this inter-molecular attractions becomes strong.

Cohesive forces are the attractive forces between same molecules. e.g. between water
molecules.
Adhesive forces are the attractive forces between different molecules. e.g. between water
molecules and the walls of container.
Wetting liquids are those which stick with the walls
of container. These liquids have higher adhesive
forces than their cohesive forces, e.g. water. These
liquids make concave meniscus in the capillary tube.
Non wetting liquids are those which do not stick
with the wall of container. These liquids have
higher cohesive forces than their adhesive forces,
e.g. Mercury. This liquid makes convex meniscus
in the capillary tube.

Applications of surface tension: There are two major applications of surface tension;
Capillary action and Formation of drops of a liquid.

1. Capillary action: The rising of a liquid in the narrow cylindrical tube (capillary
tube) is called capillary action. Wetting liquids rise up in the capillary tube when it is dipped
into the liquid because their cohesive forces are higher than their adhesive forces so their
molecules are attracted towards the walls of container and pulled up.
Non wetting liquids falls down in the capillary tube when it is dipped into the liquid because
their adhesive forces are higher than their cohesive forces so their molecules are attracted to
each other with a greater rate to go down and do not attract much towards the walls of
container to be pulled up.

2. Drop formation: The surface tension

keeps the liquid molecules together to form a drop.
In a free falling drop of liquid, the surface tension
reduces the surface area of liquid. Therefore, the free
falling drop is spherical in shape.
VAPOUR PRESSURE
Definitions:
 The pressure exerted by the vapours when they are at equilibrium with liquid phase.
 The pressure exerted by the vapours when rate of evaporation and rate of
condensation are equal to one another.

Example: Liquid water   

Evaporation
Water vapour
Condensation

Explanation: When a liquid is heated in an open container, some of the vapours convert back
to the liquid state but most of the vapours escape into surroundings and equilibrium is not
established between liquid and vapour phase. When a liquid is heated in a closed container,
about all the vapours convert back to the liquid state hence condensation takes place and
equilibrium is established between evaporation and condensation. When liquid and vapour
phases are at equilibrium to each other, at that time the pressure exerted by the vapours is
called vapour pressure. Vapour pressure is independent of the amount of liquid.

Evaporation is the conversion of liquid into the vapours on heating.

Rate of evaporation is the amount of liquid converted into the vapours per unit time.
Condensation is the conversion of vapours into the liquid on cooling.
Rate of condensation is the amount of vapours converted per unit time into liquid.

Units of vapour pressure:

Atmosphere (atm), Torr, Millimeter of mercury (mmHg), Pounds per square inch (lb/in2),
Newton per meter square (N/m2) etc.

Factors affecting vapour pressure:

1. Temperature:
Vapour pressure α Temperature
Vapour pressure increases with the increase of temperature due to increase in average
kinetic energy of liquid molecules.
2. Intermolecular attractions: Those liquids which have stronger intermolecular forces
will show low vapour pressure and those liquids which have weaker intermolecular forces
will show high vapour pressure.
3. Boiling point of the liquid: 1
Vapour Pr essure 
Boiling po int of liquid
The liquids those have higher boiling points, those molecules have low vapour pressure.

Change of state of liquid

Liquid is an intermediate state of solid and gas states. It can be converted into both solid and
gas. On heating at a certain temperature it converts into gas state and on cooling at a certain
temperature it converts into solid state.
Gas Cool
 Liquid Cool
 Solid
 Boiling is the conversion of liquid into gas on heating.
 Boiling point: The point of temperature at which liquid converts into gas state.
“OR” The point of temperature at which the vapour pressure of the liquid becomes equal
to the atmospheric pressure.
 Normal boiling point: The point of temperature at which the vapour pressure of the
liquid becomes equal to the one atmospheric (Standard pressure).

Factors affecting boiling point:

1. Atmospheric pressure: Boiling point α Atmospheric pressure
2. Impurity: Impurity causes the variation in boiling point of a liquid

SOLID STATE
It is the third state of matter which has a definite shape and fixed volume.
It possesses the characteristic of hardness. There particles (atoms /
molecules / ions) are very much packed together. This closeness of solid
particles causes definite shape, fixed volume and hardness in it.

Behavior of solids
1. Compressibility: Solids are negligible compressible at very high pressures at very
long time due very less antiparticle distances. In terms of kinetic molecular theory, the
unfilled space in solid particles is very less so they are very less compressible at very high
pressure for very long time. Otherwise, on applying high force solids show deformity.

2. Deformity: On applying high force on solids,

they change their shapes; this ability of solids is called
deformity. In terms of kinetic molecular theory, there
are strong attractive forces in solid molecules so they
do not easily leave each other on applying pressure,
therefore they show the characteristic of deformity.

3. Diffusibility: There is negligible diffusibility in solid which takes very long time. In
terms of kinetic molecular theory, there is vibrational motion in solids and free movement
in solid particles is restricted. Therefore diffusion takes place at negligible rate.

4. Melting: On heating the solids are converted into liquids, this phenomenon is called
melting. In terms of kinetic molecular theory, on heating the kinetic energy of solid particles
increases which minimizes the attractive forces between particles, so they don’t remain
packed and therefore melts up.
 Melting point: It is the point of temperature at which solid is converted into liquid state.

5. Sublimation: It is the direct conversion of solid into vapors. Some solids show the
property of sublimation, called sublimates.
Examples: Solid carbon dioxide, naphthalene, iodine, camphor, ammonium chloride
In terms of kinetic molecular theory, those solids which have less intermolecular forces than
ordinary solids, their high energy molecules overcome the attractive forces between particles
on heating and directly convert into the vapors.

Classification of solids
Solids are classified into two groups.
1. Crystalline solids: The three dimensional homogenous structure having the definite
geometrical shape, regular atomic or molecular structure and proper chemical composition
forming edges with definite angles with each other.
Example: the crystals of sugar and urea etc.
2. Amorphous solids: The amorphous solids do not have the definite geometrical shape
and irregular atomic or molecular structure and improper chemical composition. For
example, Rubber, plastics, glass etc.
Difference between crystalline and amorphous solids
No. Characteristics Crystalline Solids Amorphous Solids
1. Shape Definite Not definite
2. Geometry Proper Improper
3. Particle arrangement Three dimensional Random
4. Atomic / Molecular structure Regular Irregular
5. Chemical composition Definite Indefinite
6. Melting point High and sharp Low and not sharp
7. Stability More due to less free energy Less due to high free energy
8. Boundaries Sharp Not sharp
9. Cleavage They show cleavage They don’t show cleavage
10. Cleavage plane Fixed Not fixed
11. Anisotropy & Isotropy Anisotropic Isotropic
Symmetrical and rotate
12. Symmetry through an axis Not symmetrical

 Cleavage: The breaking of big crystals into small identical crystals is called cleavage.
 Cleavage plane: The direction, along which crystals are divided into small identical
crystals, is called cleavage plane.
 Anisotropy: Those solids in which some physical properties (like refractive index,
electrical conductivity etc) move different in different directions are called
anisotropic solids and this property is called anisotropy. Crystalline solids are
anisotropic solids.
 Isotropy: Those solids in which some physical properties (like refractive index,
electrical conductivity etc) remain same with change of directions, are called
isotropic solids and this property is called isotropy. Amorphous solids are isotropic
solids.
 Symmetry: When a crystalline solid is rotated about an axis, its appearance does not
change; this solid is known as symmetrical.

Internal arrangement of the crystals

1. Space lattice or crystal lattice: The regular three dimensional arrangements of
similar points (atoms, ions, molecules) is called space lattice or crystal lattice.
2. Unit cell: The smallest
geometrical portion of the crystal
which generates a complete three
dimensional structure by repeating
itself.
When a crystal is continuously
divided small crystals will obtain, a
point will come when crystal cannot
be further divided into smaller
crystals. This smallest crystal is the building unit which is called unit cell.

TYPES OF CRYSTALS/ SOLIDS

Crystals are divided into four major following classes.
1. Atomic / Metallic crystals / Solids
2. Ionic crystals / Solids
3. Covalent crystals / Solids
4. Molecular crystals / Solids
Molecular crystals are further divided into non polar molecular crystals and polar molecular
crystals.
Atomic / Metallic crystals / Solids
Definition: It is the collection of metal atoms in the three
dimensional crystalline form. The metallic bond forms by the
attractive force that holds two or more metal atoms together,
produced by the cluster of free electrons over the metal surface
Examples: Metals like Mg, Co, Zn, Cd, Cu, Ag, Au, Al etc.
Characteristics:
1. These are lustrous, silvery and high reflectivity due to the
mobility of free electrons over the metallic surface.
2. These are good conductor of electricity and heat because
surface electrons are free to migrate throughout the crystal
lattice.
3. They possess high melting point due to strong binding forces in crystal lattice.
4. These crystals show the property of malleability (can be drawn into sheets) and ductility
(can be drawn into wires).

Ionic Crystals / Solids

Definition: It is the collection of ions (+ve & -ve) of salts in the three
dimensional crystalline form. These ionic crystals are bonded by
electrostatic force that holds +ve & -ve ions together, produced by the
transfer of electron(s) from one atom to another.
Examples: Salts like NaCl, KCl, CuSO4, MgBr2 etc.
Characteristics:
1. These crystals are very hard and brittle due to strong electrostatic
attractions between positive and negative ions.
2. These are bad conductor of electricity in their pure state but can conduct electric current
in their solutions and in molten form.
3. They possess high melting point due to strong binding forces in crystal lattice which are
because of opposite charged ions.
4. These crystals are insoluble in non-polar solvents but are highly soluble in water and other
polar solvents.
Covalent Crystals / Solids
Definition: It is the collection of atoms of non- metals in the three dimensional
crystalline form. These crystals are bonded by the attractive force that holds two or more
atoms together, produced by the sharing of valence electron(s) with one another.
Examples: Diamond, Graphite silicon, Germanium etc.
Characteristics:
1. These crystals are usually hard and possess high melting
point due to large number of covalent bonds.
2. Some covalent crystals (like diamond) are bad conductor
of electricity
3. Some crystals (Graphite) are good conductor of
electricity.
4. These crystals possess low density and high refractive
index.
Refractive index: It is the measure of ability of refracting the
light radiations by it.

Molecular Crystals / Solids

Definition: It is the collection of molecules in the three dimensional crystalline form.
They are connected to each other by Hydrogen bonding or Weak Vander waals’ force
Examples: Water (H2O), dry ice (CO2) etc.
Characteristics:
1. These are bad conductor of electricity due to not having any charged particle.
2. They possesses low melting point due to weak binding forces in crystal lattice which
are because of hydrogen bond.

The crystal systems

On the basis of shapes and dimensions (length of edges a, b, c and angles between them α,
β, γ), the crystals are known into seven groups which are known as crystal systems.
Tabular description of the crystal systems:

No. Crystal
Edges Angles Diagram Examples
system
1. Cubic a=b=c α = β = γ = 900 NaCl, ZnS and diamond etc

2. Tetragonal a=b≠c α = β = γ = 900 SnO2(White), BaSO4.4H2O

etc

3. Orthorhombic a≠b≠c α = β = γ = 900 FeSO4.7H2O, ZnSO4.7H2O,

KNO3 etc

4. Trigonal “OR” a=b=c α = β = γ ≠ 90° KNO3, AgNO3, ice etc

Rhombohedral (>90°< 120°)

5. Hexagonal a=b≠c α=β=90° γ=120° Graphite, snow flakes, quartz

(SiO2) etc

6. Monoclinic a≠b≠c α=γ=90° β≠90° CuSO4.5H2O, Sugar cane

Na2CO3.10H2O etc

7. Triclinic a≠b≠c α≠β≠γ≠90° CuSO4.5H2O), K2CrO7 etc

Change of state (Melting)

 The conversion of a solid into liquid on heating is called melting.
 The point of temperature at which a solid is converted into liquid state is called melting
point.
Factors affecting melting point:
Impurity and external pressure affects the melting point of the solid.
 The melting point of impure solid will be different from the pure solid.
 Melting point increases with the rise of external pressure on solid.
Sublimation: There are some solids which directly convert into vapors on heating are known
as sublimates and this phenomenon is known as sublimation.
 The direct conversion of a solid into vapor state is called sublimation.
Solid Sub
limation
 Vapors
Latent heat of fusion: It is the amount of heat required to convert one gram of a solid into
liquid state at its melting point is called latent heat of fusion.
CHAPTER # 03

Atomic Structure

FARADAY’S EXPERIMENT A clue of presence of electrons in atom

Introduction: It gives the clue (proof / evidence) of the presence of electrons in an atom.
Faraday passed electricity from electrolytic solutions.

 Electrolyte is any compound that dissociates into their ions in their aqueous solutions (when
dissolved in water). Acids, bases and salts are the examples of electrolytes.

Experiment:When Faraday passed electricity through the electrolytic solutions, the ions of the
solution started moving towards the electrodes and became neutral.

Observation: He observed that these ions are associated with some unit of elementary charge
can be calculated.

Conclusion:Faraday concluded that this elementary charge is due to a particle which carries
negative charge.

DISCHARGE TUBE EXPERIMENTS

Discharge tube was used for the discoveries of electron and proton both.

1. CROOK’S TUBE EXPERIMENT Discovery of electrons

Introduction:It gives the proof about the presence of electrons in an atom. This experiment
was done by passing the electricity through gases at low pressure by W. Crook.
Experiment:W. Crook took a gas tube containing two electrodes. Most of the gas of tube was
discharged out by the vacuum pump (This is the reason that this tube is called gas discharge
tube). When high voltage of current was passed through the low pressure of gas, i-e 0.01 torr, it
was noted that a yellowish gas was produced
from cathode surface and shown a florescence
on striking with the walls of glass tube.

Conclusion: - These rays were named as

“Cathode rays”, which was later called
“electrons” by G. J. Stoney in 1891.

2. GOLDSTEIN’S EXPERIMENT Discovery of protons

Introduction: It gives the proof about the presence of protons in an atom. This experiment was
done by passing the electricity through gases at very low pressure by Goldstein.

Experiment:Goldstein took a gas discharge tube containing anode and perforated cathode
(Cathode having holes in it). He discharged the gas out of tube still less pressure than 0.01 torr
by the vacuum pump. When high voltage of current was passed through this very low pressure
of gas, it was noted that beside a yellowish gas
(cathode rays) some glowing rays are also
producing behind cathode from its holes.

Conclusion: - These glowing rays were named as

“Positive rays or canal rays”, which were named
as “protons” by Gold stein.

CHARACTERISTICS OF CATHODE RAYS

1. These rays travel in straight lines.
2. These can be focused by placing concave
cathode.
3. These rays produce a sharp shadow on the
object placed in their path.
4. These rays can penetrate into the thin foil of
aluminum or gold.
5. These rays exert mechanical pressure on the
object placed into their paths, this shows that
these possess kinetic energy.
6. These rays can be deflected by the positive
terminal of the electrical and magnetic field,
this shows that it carries –ve charge.
7. These rays produce fluorescence on sticking
with the glass tube.
8. These rays are independent of the nature of gas
present in the discharge tube.
9. The charge on these rays is 1.6022 x 10–19
Coulomb mass is 9.1096 x 10–31 Kg.

CHARACTERISTICS OF CANAL RAYS “OR” POSITIVE RAYS

These rays travel in straight lines.

1. These rays produce a glow on

striking against the glass tube.
2. These rays are deflected by the
magnetic and electric field.
3. These rays deflect opposite to
the cathode this shows that these
rays carry +ve charge.
4. These rays ionize the gases.
5. The nature of these rays
dependent upon the nature of gas present in the discharge tube.

COMPARISON BETWEEN CATHODE AND CANAL RAY

1. The charge to mass ratio (e/m) of canal rays is very small as compared to the charge to mass
ratio of cathode rays (electrons).
2. The charge on canal rays (protons) is equal to the charge on cathode rays (electrons) is same.
3. The mass of canal rays (protons) is higher than the charge on cathode rays (electrons).

RADIOACTIVITY
Confirmation of presence of electrons and protons in the atom

Introduction:In 1895 Henry Becquerel first gave an idea, that atom can disintegrate into
smaller atoms, then Pierre Curie and Marie Curie (husband & wife) first isolated an atom
Radium (Ra88) from an atom and proved the idea of Henry Becquerel.
Definition: The emission of invisible (radioactive) rays from the elements (radioactive
element) is called radioactivity.

These rays cause fogging on photographic film. The radioactive rays are alpha (α), Beta (β) and
Gamma (γ).

Types of radioactivity: There are two types of radioactivity.

(1) Natural radioactivity is the emission of radioactive rays from the element (natural
radioactive) spontaneously, e-g
238
U92 → 234
Th90 + 4
He2 (α rays)

(2) Artificial radioactivity is the emission of radioactive rays from the element (artificial
radioactive) non spontaneously, e-g

9 4 12 1
Be4 + He2 (α rays) C6 + n0 (Neutron)

EXPERIMENT OF RADIOACTIVITY
Rutherford used a simple method for the detection and separation of these radiations. He placed
a piece of radioactive substance in a pot of lead. These
rays were allowed to pass through a magnetic or electric
field.

OBSERVATION

In the presence of a strong magnetic field, three distinct

lines will be found on photographic plate.

CONCLUSION

From the above experiment, it was concluded that atoms

disintegrates and evolves radiations, its mean atom is a dividable particle.

The presence of three distinct lines on the photographic plate suggests that the beam split into
three components, two bending in the opposition directions and the third not changing its
direction. This shows that the radiation of the un-deflected beam carries no charge (the gamma
‘γ’ ray), the component of the beam deflected upward contains positively charged particles
(alpha ‘α’ particles), and the component deflected downward contains negatively charged
particles (Beta ‘β’ particles electrons).

Difference between alpha, beta and gamma rays

No. Characteristics Alpha rays Beta rays Gamma rays

1. Charge +ve – ve Neutral

2. Nature He nucleus Fast moving electrons Electromagnetic rays

3. Mass Heavy particles Light particles Very light particles

4. Effect of Deflected to Deflected to anode Un deflected

Magnetic & cathode

Electric Field

5. Velocity 1/10th to velocity of More velocity than More velocity than beta

light alpha rays rays

6. Penetration Low (1-2 cm in air) High (1–2 m in air) Very high (15–20 cm in
Power
lead)

7. Electron to Equal to protons Equal to electrons Zero due to NO

Mass Ratio
CHARGE
(e/m)

CHADWICK EXPERIMENT
Discovery of Neutron
Introduction:In 1932 Chadwick done artificial
radioactivity of beryllium.

Experiment:He bombarded alpha particles on an

artificial radioactive element Beryllium and noticed that
penetrating radiations are emitting which contains mass
as compared to the mass of proton and electrons. These
were the material particles.
 9
Be4 + 4
He2 (α rays) → 12
C6 + 1n0

(Neutron)

Conclusion:By this experiment it was concluded that atom consists charge less particle(s)
called neutron, beside charged particles electrons and protons.

DIFFERENCES BETWEEN ELECTRON, PROTON AND NEUTRON

No. Characteristics Electron Proton Neutron

1. Charge Negative Positive No any

2. Magnitude of Charge 1.6022x10 – 19 Colmb 1.6022x10 – 19Colmb Zero

3. Mass (a.m.u) 5.5 x 10 – 4 1.0073 1.0087

PLANK’S QUANTUM THEORY

Introduction:In 1900, a Germen scientist gave a theory about observed radiations from heated
bodies.

Postulates:Plank’s quantum theory contains following postulates.

1. The emission and absorption of the energy (in the form of radiations) by an atom is not a
continuous process.
2. The emission and absorption of the energy (in the form of radiations) by a body occurs in the
form of packets of energy called “quantum”.
3. The energy released or absorbed by a body is directly proportional to the frequency of the
radiations emitted or absorbed. Mathematically
Eαν

E=hν
Where; E = Energy absorbed or evolved

ν = Frequency of energy radiations

 h = Plank’s constant = 6.625x10– 27 erg. Sec=6.625x10– 34J. Sec

Conclusion: - The energy absorbed or evolved from an atom is quantized.

SPECTROSCOPY
It is the branch of Science which deals with the study of the spectrum. This is used to determine
the electronic structure of the atom.

SPECTRUM:A band of rays of different wavelengths produced from the decomposition of

radiations by a substance.

EMISSION SPECTRUM

Definition:A band of rays of different wavelengths produced from the radiations emitted by a
substance.

Types:Spectra have two following types.

1. Continuous spectrum is the

band of radiations of different
wavelengths in which
wavelengths are diffused in one
another and no any dark space is
found between two wavelengths.
The visible portion of the
continuous spectrum can be
obtained from sunlight or
ordinary lamp. Rainbow is also
an example of continuous spectrum.
2. Discontinuous spectrum“OR”
Line spectrum is the band of radiations
of different wavelengths in which
wavelengths are not diffused in one
another and a dark space is found
between two wavelengths. Neon lamp,
Sodium lamp, Crook’s tube (ordinary
Tube light) is the sources of
discontinuous spectrum.

RUTHERFORD’S MODEL OF AN ATOM

Discovery of nucleus

Introduction:In 1911
Rutherford scattered the alpha
rays on thin foil of Gold and
provided evidence about the
arrangement of the fundamental
particles (Electrons, Protons and
Neutrons) in the atom.

Experiment: Rutherford
bombarded alpha rays on 4 x 10–5
cm thick foil. He noticed that
many of radiations (which struck
at the center of atom) deflected
but some of these (which struck outside the center) passed without any deflection.

RUTHERFORD’S MODEL OF AN ATOM (ASSUMPTIONS)

1. Nucleus of an atom is positively charged means it contains positive particles, i-e protons.
2. Outside the centre (nucleus) negative particles (electrons) are present in large empty spaces.
3. The total no. of electrons and protons are equal in an atom.
4. The whole mass of an atom is present at the centre of an atom, means beside protons, neutrons
are also present in the nucleus.
5. All the particles except electrons are present in the nucleus and these particles are called
nucleons.
WEAKNESSES OF RUTHERFORD’S MODEL OF AN ATOM
No. Weakness by Rutherford Improvement by Bohr

1. When electron moves around the nucleus it It does not true because if energy is
continuously evolves energy. continuously

Liberated, the electron will fall into

nucleus at the end which does not
happen actually.

2. The emitted radiations from an atom give continuous Actually the emitted radiations from
spectrum on passing from prism. atom give discontinuous spectrum.

X-RAYS “OR” ROENTGEN RAYS

Introduction: In 1895 W. C. Roentgen discovered these rays from crook’s tube.

Definition: The unknown rays of very short wavelength discovered from the crook’s tube are
called as X-Rays.
Experiment:When the electric current
was passed from the crook’s tube at very
low pressure, cathode rays were emitted
from cathode and moved towards anode.
When these rays were strike to the anode
and with the glass tube, it emitted the
radiations of very short wavelength called
X- rays.

Properties of X-Ray:

1. These rays possess very short wavelength.

2. These rays possess very high frequency and high energy.
3. These can be deflected from electrical and magnetic field this shows that these rays are
electromagnetic (having both electrical & magnetic properties) in nature.
4. These can affect photographic film.
5. The frequency of these rays depends upon the nature of gas in discharge tube.
6. The frequency of these rays increases with the increase in atomic no. of the gas in discharge
tube.
7. These rays can ionize gases.
8. These rays have high penetration power.

Conclusion (Atomic number):

Discovery of atomic number: In 1913 Mosley noticed that frequency of these rays increases
with the increase in no. of protons in the nucleus of the gas in discharge tube. Hence it is
concluded that frequencies of X-Rays depends upon the positive charge in the nucleus of atom
of gas. Thus he named this no. of positive charge (protons) as “atomic number”.

Symbol: Atomic no. is represented by “Z”.

Expression: Atomic number (Z) = No. of protons

BOHR’S THEORY
Introduction:In 1913, a Danish scientist Neil Bohr improved the Rutherford’s model of an
atom.

Postulates:

1. When an electron revolves round the nucleus, it neither loss nor gain energy.
2. Electrons revolve around the nucleus in the circular paths which are highly stable therefore he
named these orbits as “stationary states”.
3. Each circular path (orbit) around the nucleus have its own energy, therefore these orbits are
also named as :energy levels”
4. When electron absorbs ΔE energy (equal to the energy
difference of two orbits), it becomes exited and jumps to
the next higher energy level and when it comes back to
the lower energy level same amount of energy is liberated
in the form of radiations, which was absorbed during
excitation.
ΔE = E High energy level – E Lower energy level

5. Those orbits whose product of momentum (mv) and circumference (2 π r) is equal or some
integer multiple to the Plank’s constant.

Momentum x Circumference = Plank’s constant

mvx2πr=h

For nth orbit m v x 2 π r = nh

nh

OR mvr = ---- Where, mvr = Angular momentum

2π

This shows that the angular momentum of an electron is equal to the integral multiple of h_

2π

Some important definitions

 Excitation: The jumping of electron from lower energy level to the higher energy level by
absorbing energy equal to the energy difference of lower and higher energy levels.

 Ground state: The lower stable energy level from where jumping of electron towards higher
energy level takes place.

 Exited state: The higher unstable energy level where electron jumps from lower energy level.

Example: If an electrons jumps from 3rd energy level to the 4th energy level, this is named as
excitation whereas 3rd energy level is ground state and 4th energy level is excited state.
DERIVATION FOR THE EXPRESSION OF THE RADIUS OF AN ATOM
BY BOHR’S THEORY

Suppose an atom have atomic no. “Z” and “Ze” is the charge on nucleus, “m” is the mass of
electron and “”e” is the charge on electron revolving around the nucleus in the orbit at a radius
“r”.

According to the Coulombs law the attractive force (Centripetal force) and the repulsive force
(Centrifugal force) are equal for a revolving electron.

Therefore,

Centripetal force = Centrifugal force

𝑍𝑒.𝑒 𝑚𝑣 2
= --------(1)
𝑟2 𝑟

According to the Bohr theory;

𝑛ℎ
𝑚𝑣𝑟 =
2π

Or,
𝑛ℎ
𝑣=
2πmr
Putting the value in equation 1:

𝑛ℎ 2
𝑍𝑒𝑒 𝑚 (2π𝑚𝑟 )
=
𝑟2 𝑟
𝑛 2 ℎ2
𝑍𝑒𝑒 𝑚
4π2 𝑚2 𝑟2
=
𝑟2 𝑟

𝑍𝑒𝑒 𝑚𝑛2 ℎ2
=
𝑟2 4π2 𝑚2 𝑟 2 𝑟

2
𝑛2 ℎ2
𝑍𝑒 =
4π2 𝑚𝑟

𝑛2 ℎ2
𝑟=
4π2 𝑚 𝑍𝑒 2

Where r = Radius of an atom

n = Number of orbit (i.e. 1, 2, 3 etc)

h = Plank’s constant

π = Pi (Constant = 3.14)

m = Mass of electron = 9.11 x 10-31 Kg Z = atomic number of atom

e = Charge on electron = 1.6022 x 10-19 Coulombs

r = n2 0.529 Ao

DERIVATION FOR THE EXPRESSION OF THE ENERGY OF AN ATOM

BY BOHR’S THEORY
 1
When an electron revolves around the nucleus its kinetic energy is 2 𝑚𝑣 2 whereas its
−𝑍𝑒 2
potentialenergy is and the total energy of electron is the sum of its kinetic and potential
𝑟
energies.

Total energy = Kinetic energy + Potential energy

1 −𝑍𝑒 2
𝐸 = 𝑚𝑣 2 + ( )
2 𝑟

(-ve sign indicates the decrease in potential energy)

1 𝑍𝑒 2
𝐸 = 𝑚𝑣 2 − − − − − − −(1)
2 𝑟

According to Bohr’s theory;

Centripetal force = Centrifugal force

𝑍𝑒𝑒 𝑚𝑣 2
=
𝑟2 𝑟

𝑍𝑒 2
= 𝑚𝑣 2
𝑟

Putting this in equation 1

1 𝑍𝑒 2 𝑍𝑒 2
𝐸= ( )−
2 𝑟 𝑟

𝑍𝑒 2 𝑍𝑒 2
𝐸= −
2𝑟 𝑟
By taking L.C.M

𝑍𝑒 2 − 2𝑍𝑒 2
𝐸=
2𝑟
 −𝑍𝑒 2
𝐸= -------- (2)
2𝑟

𝑛2 ℎ2
𝑊𝑒 𝑘𝑛𝑜𝑤 𝑡ℎ𝑎𝑡: 𝑟=
4π2 𝑚 𝑍𝑒 2

Putting the value of ‘r’ in equation 2:

−𝑍𝑒 2
𝐸=
𝑛2 ℎ2
2( 2 )
4π 𝑚𝑍𝑒 2

−𝑍𝑒 2
𝐸= 𝑥 2π2 𝑚𝑍𝑒 2
𝑛2 ℎ2

−2π2 𝑚𝑍 2 𝑒 4
𝐸=
𝑛2 ℎ2
`

DERIVATION FOR THE EXPRESSION OF THE FREQUENCY OF

RADIATIONS EMITTED BY AN ATOM
When an atom absorbs energy its electron become excited by absorbing energy in the form of
radiations and this amount of energy is equal to the energy difference of the energies of lower
and higher energy levels. When that excited electron comes back to the ground state, it evolves
same amount of energy which was absorbed at the time of excitation but in the form of
radiations and the frequency of these radiations can be calculated by the following expression.
According to Bohr’s theory
 ΔE = hν where: E1 = Ground state & E2 = Excited state

Or E2 – E1 = hν --------- (1)

We know that,

−2π2 𝑚𝑍 2 𝑒 4 −2π2 𝑚𝑍 2 𝑒 4
𝐸2 = 𝑎𝑛𝑑 𝐸1 =
𝑛22 ℎ2 𝑛12 ℎ2

Putting these values in equation 1:

−2π2 𝑚𝑍 2 𝑒 4 −2π2 𝑚𝑍 2 𝑒 4
ℎ𝑣 = −
𝑛22 ℎ2 𝑛12 ℎ2

−2π2 𝑚𝑍 2 𝑒 4 2π2 𝑚𝑍 2 𝑒 4
ℎ𝑣 = +
𝑛22 ℎ2 𝑛12 ℎ2

2π2 𝑚𝑍 2 𝑒 4 2π2 𝑚𝑍 2 𝑒 4
ℎ𝑣 = −
𝑛12 ℎ2 𝑛22 ℎ2

Taking common;

2π2 𝑚𝑍 2 𝑒 4 1 1
ℎ𝑣 = [ − ]
ℎ2 𝑛12 𝑛22
 2π2 𝑚𝑍 2 𝑒 4 1 1
𝑣= 3
[ 2 − 2]
ℎ 𝑛1 𝑛2

DERIVATION FOR THE EXPRESSION OF THE WAVE NUMBER OF

RADIATIONS EMITTED BY AN ATOM BY BOHR’S THEORY

The expression for the wave number of emitted radiations from an atom can derived as follows.
We know that

v = C ῡ------ (1)

Where, C = Speed of light radiations; v = Frequency of radiations; ῡ= Wave number

We know that:

2π2 𝑚𝑍 2 𝑒 4 1 1
𝑣= [ − ]
ℎ3 𝑛1 𝑛22
2

Putting the values from equation 1:

2π2 𝑚𝑍 2 𝑒 4 1 1
𝐶ῡ = [ − ]
ℎ3 𝑛12 𝑛22

2π2 𝑚𝑍 2 𝑒 4 1 1
ῡ= [ − ] − − − − − (2)
𝐶ℎ3 𝑛12 𝑛22

We know that:

2π2 𝑚𝑒4
= 𝑅𝐻 (𝑅𝑦𝑑𝑏𝑒𝑟𝑔 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡)
𝐶ℎ3

Putting value in equation 2:

 1 1
ῡ = 𝑅𝐻 𝑍 2 [ 2 − 2]
𝑛1 𝑛2

For Hydrogen, Z =1;

Therefore,

1 1
ῡ = 𝑅𝐻 [ 2 − 2 ]
𝑛1 𝑛2

BOHR’S THEORY AND HYDROGEN ATOM SPECTRUM

When an atom absorbs energy (equal to the energy difference of two orbits) it becomes excited,
when it comes back to the ground state it emitted same amount of energy in the form of
radiations which was absorbed at the time of excitation. On the basis of this Bohr’s statement
various scientists took different following observations on hydrogen atom.

1. Lyman series:Lyman was a scientist who studied the series of spectral lines obtained from
the radiations emitted when electron jumps from 2nd, .3rd, 4th, 5th or 6th orbit to the 1st orbit.
He studied ultraviolet region of the hydrogen atom spectrum and gave following formula to
calculate the wave no. of emitted radiations.

1 1
ῡ = 𝑅𝐻 [ 2 − 2]
𝑛1 𝑛2

Here, n1 = 1, n2 = 2, 3,4,5….

2. Balmer Series:Balmer was a scientist who studied the series of spectral lines obtained
from the radiations emitted when electron jumps from 3rd, 4th, 5th or 6th orbit to the 2nd orbit.
He studied visible region of the hydrogen atom spectrum and gave same formula as given by
Lyman, to calculate the wave no. of emitted radiations.

1 1
ῡ = 𝑅𝐻 [ 2 − 2]
𝑛1 𝑛2

Here, n1 = 2, n2 = 3,4,5,6 ….

3. Paschen Series: Paschen was a scientist who studied the series of spectral lines obtained
from the radiations emitted when electron jumps from 4th, 5th or 6th orbit to the 3rd orbit. He
studied Infrared region of the hydrogen atom spectrum and gave following formula to calculate
the wave no. of emitted radiations.

1 1
ῡ = 𝑅𝐻 [ 2 − 2]
𝑛1 𝑛2

Here, n1 = 3, n2 = 3,4,5,6 ….

4. Brackett Series: Brackett was a scientist who studied the series of spectral lines obtained
from the radiations emitted when electro jumps from 5th or 6th orbit to the 4th orbit. He also
studied infrared region of the hydrogen atom spectrum and gave same formula as given by
Lyman, to calculate the wave no. of emitted radiations.

1 1
ῡ = 𝑅𝐻 [ − ]
𝑛12 𝑛22

Here, n1 = 4, n2 = 3,6 ….

5. Pfund Series: Pfund was a scientist who studied the series of spectral lines obtained from
the radiations emitted when electron jumps from 6th orbit to the 5th orbit. He studied infrared
region of the hydrogen atom spectrum and gave same formula as given by Lyman, to calculate
the wave no. of emitted radiations.

1 1
ῡ = 𝑅𝐻 [ 2 − 2]
𝑛1 𝑛2

Here, n1 = 5, n2 = 6 ….
Conclusion: - From above all series of spectral lines of Hydrogen atom spectrum studied by
the various scientists, it is concluded that following expression can be used for the calculation of
wave no. of emitted radiations from an atom.
 1 1
ῡ = 𝑅𝐻 [ 2 − 2]
𝑛1 𝑛2

DEFECTS OF BOHR’S THEORY:

Bohr’s theory successfully explains the spectra of hydrogen atom and other smaller atoms like
Helium, Beryllium and Lithium etc but it is failed to explain the spectra of more complicated
atoms.

ADVANTAGES “OR” USEFULNESS OF BOHR’S THEORY: -

1. Bohr’s theory removes the weaknesses of Rutherford’s model of atom.

2. It helps to calculate the radius of an atom.
3. It helps to calculate the energy of revolving electrons.
4. It helps to calculate the energy, frequency, wave no. of the radiations emitted from an atom.
5. It also explains the spectra of smaller and simple atoms, e-g Hydrogen, Lithium and Beryllium
etc.

HEISENBERG UNCERTAINTY PRINCIPLE

Introduction: In 1925 Heisenberg put forwarded this principle about the nature of electron.

Statement:It is uncertain to determine the position and momentum of an electron

simultaneously.

Explanation: Both position and momentum of an electron cannot be determined accurately. If

we determine the momentum of the electron through an analytical instrument accurately, then
the position will uncertain to determine accurately.

Mathematically: Δpx.Δx≈ h

Where, Δpx = Momentum of electron, Δx = Position of electron, h = Plank’s Constant

Conclusion:This principle shows that electron is not at zero energy (at rest).

Advantage:It finishes the incompleteness of Bohr’s theory.

 Chemical Bonding
(Chapter # 4)

Chemical Bonding: - An attractive force that holds two or more atoms together in a
molecule.
Why bond forms? OR Octet rule: - Every atom tends to achieve stable outer most
configuration therefore it make bond to other atom(s) to complete its octet or duplet.
 Octet is the group of eight electrons. OR The configuration equal to the valence
configuration of noble gases.
 Duplet is the group of two electrons. OR The configuration equal to the configuration
of Hydrogen atom.

Types of chemical bond: - There are following three types of chemical bonds.
1. Ionic bond
2. Covalent bond
3. Co-ordinate covalent bond

1. Ionic bond OR Electrovalent bond

Introduction: - This bond was suggested by Kossel.
Definition: - The attractive electrostatic force between two or more atoms produced by
the complete transfer of electron(s) from the valence shell of one atom into the valence
shell of another atom.
Explanation: -
 This bond forms between low electronegative and high electronegative atom.
 Low electronegative atom is a metal and high electronegative atom is a metal.
 Low electronegative atom losses the valence electron (forms positive charged) and high
electronegative atom gains the electron (forms negative charged).
 The electronegativity difference between the bonded atoms through ionic bond is 1.7
or higher.

Formation of NaCl
Na 11 Na 
i) 
1s 2 ,2s 2 ,2p 6 ,3s1 1s 2 ,2s 2 ,2p 6 ,3s 0
Cl17 Cl 
ii) 
1s 2 ,2s 2 ,2p 6 ,3s 2 ,3p 5 1s 2 ,2s 2 ,2p 6 ,3s 2 ,3p 6
Na  Cl  Na  Cl 
 
Sodium ion Chloride ion Sodium Chloride

Formation of MgO
Stability of ionic bond: - The stability of the ionic bond can be calculated by energy
changes in the formation of ionic compound. For example NaCl;
Step # 1:- Na  Na+ + 1e- H  496 KJ / mol
Step # 2:- Cl + 1e-  Cl- H  348 KJ / mol
Step # 3:- The energy released in 2nd step will compensate with the energy absorbed in
1st step, so the Na+ and Cl- formed, hence they attract each other to make a bond.
Na+ + 1e-  NaCl H  788 KJ / mol
By summing all three steps;
Na  Na+ + 1e- H  496 KJ / mol
Cl + 1e-  Cl- H  348 Kj / mol
Na+ + Cl-  NaCl H  788 KJ / mol
Na + Cl-  NaCl H  640 KJ / mol
This (-640 KJ/mol) is the energy released for the formation of NaCl which is
different from the energy change of Na and Cl separately, hence the NaCl bond formed is
stable.

Characteristics of ionic compounds: -

 Ionic compounds occur in the form of solids due to strong electrostatic force between
cation and anion.
 Ionic compounds have high melting and boiling points.
 Ionic compounds are soluble in polar solvents, like water.
 Ionic compounds are the bad conductor of electricity in their pure state.
 Ionic compounds can conduct electricity in their aqueous solutions and molten state.

2. COVALENT BOND
Introduction: - This bond was suggested by an American Scientist G. N. Lewis.
Definition: - The attractive force that holds two or more atoms together produced by the
mutual sharing between the valence electrons of the atoms is called covalent bond.
Explanation: -
 This bond forms between two or more atoms together in such a way that electrons are
not completely transferred from one atom to another.
 The mutual sharing between the valence shell of two atoms causes the noble gas
configuration.
 This is an ordinary covalent bond.
 A covalent bond involves a balance between attraction and repulsion.

Types of covalent bond: - Covalent bond is classified into different types on the basis of;
A) Number of electrons shared
B) Electronegativity of atoms taking part in bonding

A) Types of covalent bond on the basis of number of electrons shared: -

There are following three types of covalent bonds on the basis of number of
electrons shared between atoms.
I. Single covalent bond
II. Double covalent bond
 III. Triple covalent bond
I. Single covalent bond
Definition: - The attractive force that holds two or more atoms by the mutual sharing of
one electron by each atom is called single covalent bond.
Symbol: - It is denoted by single line ( – ).
Example: - Formation of Hydrogen molecule (H2) H–H
Formation of Hydrogen Chloride molecule (HCl) H–Cl
Formation of Chlorine molecule (Cl2) Cl–Cl

II. Double covalent bond

Definition: - The attractive force that holds two or more atoms together by the mutual
sharing of two electrons from each atom is called double covalent bond.
Symbol: - It is denoted by double line (=)
Example: - Formation of Oxygen molecule (O2) O=O
Formation of Carbon dioxide molecule (CO2) O=C=O
Formation of Ethene (C2H4) H2C=CH2

III. Triple covalent bond

Definition: - The attractive force that holds two or more atoms together by mutual sharing
of
three electrons from each atom is called triple covalent bond.
Symbol: - It is denoted by three line (  )
Example: - Formation of Nitrogen molecule (N2) N N
Formation of Ethyne (C2H2) HC  CH

B. Types of covalent bond on the basis of electronegativity of atoms:

There are following three types of covalent bonds on the basis of electronegativity
of atoms taking part in bonding.
I. Non polar OR Pure covalent bond
II. Polar covalent bond

I. Non polar OR Pure covalent bond

Definition: - The attractive force that holds two or more atoms together by the mutual
sharing of one or more electrons between the similar atoms is called non polar or pure
covalent bond.
The molecules which are bonded by a non polar covalent bond have zero electronegativity
difference.
Examples: H2, Cl2, N2, O2, CO2, CH4

II. Polar covalent bond (Ionic character of covalent bond)

Definition: - The attractive force that holds two or more atoms together by mutual sharing
of one or more electrons between dissimilar electronegative atoms is called polar covalent
bond.
  The molecules which are bonded by a non polar covalent bond have
electronegativity difference in between zero and 1.7.
 There are partial charges on the atoms bonded in polar covalent bond.
 Ionic character depends upon the electro negativity difference of the bonded atoms.
Examples:
σ+
H2 O H – Oσ-– H σ+
σ+
HCl H – Cl σ-
σ+
HF H – Fσ-

Characteristics of covalent compounds: -

 These compounds are liquids or gases at room temperature.
 Polar covalent compounds (e.g. HCl, HBr etc) are soluble in water whereas non-polar
covalent compounds (e.g. H2, O2 etc) are insoluble in water.
 Covalent compounds have low melting and boiling points.
 Covalent compounds are bad conductor of electricity in their pure state.
 Polar covalent compounds are good conductor of electricity in their aqueous solutions.

Covalent Bond Covalent Bond

Bond Energy Bond Energy
Bond Distance Bond Distance
C–C 1.54 AO 347 KJ/mol Cl–Cl 1.99 AO 242 KJ/mol
O O
C=C 1.34 A 598 KJ/mol O=O 1.21 A 498 KJ/mol
C≡C 1.20 AO
820 KJ/mol N≡N 1.10 AO
946 KJ/mol

3. Co-ordinate covalent OR dative bond

Introduction: - This bond was first suggested by “Sedgwick”.

Definition: - The attractive force that holds two or more atoms together produced by the
sharing of lone pair of electron by only one atom, is called co-ordinate Covalent Bond.
 Lone pair of electron is that pair of electrons which is not involved in bonding.
 Bond pair of electron is that pair of electrons which is formed by the bonding.
Explanation: -
 The atom that losses (donates) the electron pair is called donor atom.
 The atom that gains (accepts) the electron pair is called accepter atom.
 Donor atom carries positive (+ve) charge where as accepter atom carries negative
charge (-ve).
 It is represented by an arrow from donor to the accepter atom  .

Co-ordinate covalent bond in Hydronium ion (H3O+)

H2O + H+      H3O+
Water Hydrogen ion Hydronium ion
Electronic configuration of oxygen (Z=8) = 1s2, 2s2, 2px2, 2py1, 2pz1

K L
 Valence shell of oxygen atom (L) contains two lone pairs of electrons and two
unpaired electrons which makes two single covalent bond with two hydrogens.

H
O + H+ O H

H H H
Hydronium ion can also be represented as:
See old notes…
Co-ordinate covalent bond between Phosphorous trichloride (PCL3) and Oxygen (O)
Electronic configuration of Phosphorous (Z=15) = 1s2, 2s2,2p6, 3s2, 3px1, 3py1, 3pz1
Electronic configuration of Oxygen (Z=8) = 1s2, 2s2, 2px2, 2py1, 2pz1 Electronic
configuration of Chlorine (Z=17) = 1s2, 2s2,2p6, 3s2, 3px2, 3py2, 3pz1

In the valence shell of Phosphorous three unpaired electrons are covalently bonded with
three Chlorines whereas one lone pair of electron is there which will make co-ordinate
covalent bond with Oxygen atom.

Above structure can also be represented as:

DIPOLE MOMENT
Definition: - The measure of polarity of a molecule is called dipole moment.
Symbol: - it is represented by “mue” (μ).
Mathematically: - It is the product of the distance between two opposite charged poles
and amount of charge on them. μ = d × e
Where=> d = Distance between two oppositely charged poles
 e = Amount of charge on poles
μ = Dipole moment

Unit: - Dipole moment is measured in following units,

 Debye denoted by “d”, suggested by Dutch Physicist Debye.
 Coulomb meter / Coulomb centi meter denoted by Cm or Ccm.
1 debye = 3.34 x 10–30 Cm

Representation: - Dipole moment is represented by an arrow (→) from positive to the

negative pole of the bond.
Factors on which dipole moment depends: -
 Electronegativity: Dipole moment α Electronegativity
 Structure of molecule: Linear molecules will have less value of dipole moment
whereas angular molecules will have higher values of dipole moment. For example,
Carbon dioxide has zero dipole moment due to balanced attractions whereas water
has some value of dipole moment due to its angular structure.

OCO
Significance of dipole moment: Dipole moment helps to determine
the geometry of a molecule.
For example:
 Zero dipole moment of a tri atomic molecule (like CO2, CS2
etc) suggests its linear structure.
 Greater than zero dipole moment suggest the angular structure
of molecule. For example, SO2 has 1.63 D and H2S has
0.95 D.
 Triangular planer molecules (like BF3) and tetrahedral molecules (like CH4)
have zero dipole moments because resultant dipole moments cancel out each
other.

Dipole moments of some molecules are given below:

Dipole moment Shape of
Molecule Reason to show dipole moment
(In dybes) molecules
H2 0 Linear Because of zero electronegativity difference
Cl2 0 Linear Because of zero electronegativity difference
N2 0 Linear Because of zero electronegativity difference
O2 0 Linear Because of zero electronegativity difference
HF 1.78 Linear Because of greater than zero
electronegativity difference
CS2 0 Linear Because of balanced attractive forces at
all sides of central atom.
 CO2 0 Linear Because of balanced attractive forces at
all sides of central atom.
H2O 1.84 Angular Because of angular structure
H2S 0.095 Angular Because of angular structure
SO2 1.63 Angular Because of angular structure
NH3 1.63 Pyramidal Because of angular structure
BF3 0 Trigonal Because of balanced attractive forces at
planner all
sides of central atom.
CH4 0 Tetrahedral Because of balanced attractive forces at
all sides

Explain why CO2 have zero dipole moment but not SO2?
In CO2 carbon-oxygen attractive pull is balanced at both sides due to the linear structure
of CO2, so overall molecule becomes non polar and the dipole moment of CO2 is zero.
Whereas in SO2 the attractive pull at both sides is not balanced due to angular structure of
molecule.

BOND ENERGY
Definition: - the amount of energy required to break a bond is called bond energy.
Explanation:
 Bond energy is also known as bond dissociation energy.
 The amount of energy evolved when a bond forms is called bond formation energy.
 Bond formation is exothermic in nature:
H + H  H2 ΔH= – 435 KJ/mol
O + O  O2 ΔH= – 498 KJ/mol
 Bond dissociation is endothermic in nature:
H + H  H2 ΔH= + 435 KJ/mol
O + O  O2 ΔH= + 498 KJ/mol
 Bond energy is the measure of strength of the chemical bond, which is dependent
upon bond distance. Greater will be bond distance, weaker will be the strength of
bond.
Units: Kilo Joule per mol (KJ/mol)
Kilo Cal per mol (Kcal/mol)
Factors affecting bond energy: -
1. Electronegativity Difference: - Greater will be the electronegativity difference,
greater will be the bond energy.
2. Bond length OR Bond distance: - Bond length α 1
Bond energy
Bond Bond distance (Ao) Bond energy (KJ/mol)
C–C 1.54 347
C=C 1.34 611
CC 1.20 837
 NN 1.10 946

In both C  C and N  N have triple covalent bond but the bond energy of C  C bond is less
than N  N bond due to high electronegativity of nitrogen than carbon.

Sigma Bond (δ)

Definition: It is the bond produced by the head by head or lateral overlapping of orbitals
Example: s-s, s-p, p-p overlapping
Pi Bond (π)
Definition: It is the bond produced by the parallel overlapping of orbitals
Example: py-py, pz-pz overlapping

Difference between pi (π) and sigma (δ) bond

Characteristics Sigma (δ) Bond Pi (π) Bond
More stable due to maximum Less stable due to less
Stability
overlapping of orbitals overlapping of orbitals
Reactivity Less reactive due to more stability More reactive due to less stability
Formation of
Sigma bond forms earlier than pi Pi bond forms later than sigma
Bonds
The orbital making sigma bond is The orbital making pi bond is
called sigma orbital called pi orbital
Names
The electrons making sigma The electrons making pi bond are
bond are called sigma electrons called pi electrons

Overlapping of orbital (sigma or pi bonds)

Orbitals used in bond -bond, showing head to head overlapping
formation
s-orbital - s-orbital

s-orbital - p-orbital

p-orbital - p-orbital

Orbitals used in bond formation -bond, showing parallel overlapping

py-orbital - py-orbital

overlap also illustrated like so

HYBRIDIZATION
Mixing of two different atomic orbitals to produce equivalent orbitals in same number,
 all having same shape & energy, is known as Hybridization. Example: CH4,
H2O, C2H4 etc

Types of hybridization
There are three types of hybridization
Sp3 hybridization
Sp2 hybridization
Sp hybridization
Difference among sp3, sp2 and sp hybridization
Characteristics Sp3 Hybridization Sp2 Hybridization Sp Hybridization
Definition Mixing of one s and Mixing of one s and Mixing of one s and
three p orbitals two p orbitals one p orbitals
Mixing ration b/w s 1 : 3 1:2 1:1
and p orbitals
No. of hybridized 4 3 2
orbitals produced
Shape Tetrahedral Trigonal Diagonal / Linear
Diagram

Nature Non co planner Co planner Coplanner

Examples All alkanes, e-g All alkenes, e-g All alkynes, e-g
methane (CH4), Ethene (C2H4) etc Ethyne (C2H2) etc
Ethane (C2H6) etc
Bonds All are sigma bonds, One pi bond, Two pi bonds,
no remaining remaining sigma
pi bond sigma
Stability of the More due to no pi Less due to one pi Very less due to two
molecule bond bond pi bonds
Reactivity of the Less due to high High due to less Very high due to very
molecule stability stability less stability
Type of reaction Substitution Addition Addition
undergoes in the
molecule

Shapes of simple molecules

Shapes of simple molecules can be determined by the following theory and model.
 Hybrid orbital model
 Valence shell electron pair repulsion theory (VSEPR theory)

Hybrid orbital model

According to this model, the shape of a molecule is determined by re nature of
hybridization in central atom.

Hybridization Bond angle Shape of molecule Examples

Sp3 109.280 Tetrahedral All alkanes, e-g Methane (CH4) ,

Ethane (C2H6) etc
Sp2 120 0 Trigonal All alkenes, e-g Ethene (C2H4) etc
Sp 180 0 Diagonal / Linear All alkynes, e-g Ethyne (C2H2) etc
Valence shell electron pair repulsion theory (VSEPR theory)
Introduction: - This theory was put forwarded by Powell and Sedgwick in 1940 about
the structure of simple molecules.
Postulates: -
 The electrons present in the valence (outer most) shell of an atom are called active sets
of electron.
Here are following two types of active set of electrons.
o Lone pair of electrons: - Those pairs of electrons which form without chemical
bonding in the valence shell of atom. This is also known as non-bonding pair of
electron.
o Bond pair of electrons: - Those pairs of electrons which form at the result of
chemical bonding in the valence shells of two atoms.
For example:

 Both lone pair & bond pair carry –ve charge & repel each other. The order of repulsion
is as under:
Lone pair-Lone pair repulsion > Lone pair-Bond pair repulsion > Bond pair-Bond pair
repulsion
 Shape of molecule depends upon total number of active set of electron pairs (lone and
Bond pairs)
Linear molecules

 Beryllium Chloride has the simplest shapes,

Cl-Be-Cl
2 bonding pairs around
involving only 2 bonding pairs.
central be atom

 Carbon dioxide (CO2) is another example of linear

shaped molecule. It has two bonding pairs which all
repel equally.
Carbon Atom have four bond
pairs, two at side, no lone pair so
repulsion is balanced.
Crooked shaped (Bent) molecules
Any molecule with two bonding pairs and two lone pairs
will have a crooked shape, giving a bond angle less than
the normal angle of a tetrahedral structure.
 Water molecule has three atoms, so the structure
should be linear but the two lone pairs in the
valence shell of oxygen causes repulsion to the two
bond pairs to bend the structure and bond angle
becomes 104.5o.
Trigonal Pyramidal molecules
The molecules having three bond pairs and one lone pair will
have trigonal pyramidal structure.
 Ammonia molecule have one lone pair in the valence shell
of nitrogen which repeal three bond pairs to give trigonal
pyramidal structure and the bond angle becomes 1070.
 Phosphine (PH3) and Sulphite ( SO32 ) are some other
examples of trigonal pyramidal molecules.

Tetrahedral molecules
The molecules, in which four bond pairs are there, all with
equal repulsions, give a tetrahedral structure with a bond angle
of 109.28.
 Methane molecule (CH4) have four bond pairs but no lone
pair in the valence orbital therefore all repulsions are balanced
so the bond angle is 109.280.
 Ammonium ion ( NH 4 ), Sulphate ion ( SO 24 ), Phosphate ion 4 bonding pairs around a
3 central atom = tetrahedral
( PO 4 ) are some other examples of the tetrahedral
molecules.
Trigonal Planner molecules
The molecules, in which three bonding pairs are there, all with equal repulsions, give a
planner trigonal structure with a bond angle of 1200.
 Boron trifluoride molecule (BF3) has three bond pairs but no lone pair in the valence
orbital therefore repulsions are balanced so the bond angle is 1200.
 Sulpher trioxide (SO3), Nitrate ion ( NO 3 ), Carbonate ion ( CO 32 ), Ethene or Ethylene
(C2H4) are some other examples of planner trigonal molecules.

Summary table, Valence shell electron pair repulsion theory

Bond angle
Shape Bond pairs Lone pairs Examples
(deg)
 BeCl2, CO2,
Linear 2 0 180
HCN, C2H2
Non-linear
2 2 104.5 H2S, SO2, H2O
(Crooked)
BF3, SO3, NO 3 ,
Trigonal planar 3 0 120
CO 32 , C2H4
Trigonal
3 1 107 PH3, SO 32 , NH3
pyramidal
NH 4 , SO 24 , PO 34 ,
Tetrahedral 4 0 109.5
Ni(CO)4, CH4

Hybridization and associated Molecular Geometry

Hybridization Orbitals (simplified) Molecular

Geometry

Sp1 Linear

one s + one p = two sp1 hybrids

sp2 Trigonal Planar

one s + two p = 3 sp2 hybrids

sp3 Tetrahedral

one s + three p = 4 sp3 hybrids

Hybridization, Lone Pairs and associated Molecular Geometry

Molecular geometry is determined by the positions of atomic nuclei in three dimensional
space
 Hybridization Orbitals with Lone Pairs Molecular Geometry
One Lone Pair

sp2

Angular (e-g SO2)

One Lone Pair

sp3

Trigonal Pyramidal
(e.g NH3)

sp3

Two Lone Pairs V-shape (e.g H2O)

HYDROGEN BOND
Definition: The attractive force between hydrogen of a molecule and high
electronegative atom of that molecule in which that high electronegative atom is already
covalently bonded with anther hydrogen.
Explanation: -
 It is not a true bond.
 It creates the association among molecules.
 This bond forms due to the high electronegative atom (i.e - δ) which attracts the
hydrogen (i-e + δ) of adjacent molecule.
 The association of molecules (containing hydrogen bond) is through the hydrogen ion
(H+), therefore this is also known as Protonic bridge.
Examples: -
Hydrogen bond in water (H2O)
Hydrogen bond in hydrogen fluoride (HF)

Characteristics of Hydrogen bond: -

 It is a secondary or physical (not true) bond.
 This is a weak bond than a normal covalent bond.
 Only the molecules having high electronegative atom (like F, O, N etc) are
capable to make this bond.
 Strength of hydrogen bond depends upon the electronegativity of atom (other
than Hydrogen) in the molecule.
 Hydrogen Fluoride (HF), Water (H2O) and Ammonia (NH3) are the best
examples of those molecules which contain hydrogen bond.
Effect of Hydrogen bonding on boiling and melting points of a molecule: -
Those substances whose molecules are associated with hydrogen bond have
comparatively higher melting and boiling points.
Difference between Atomic orbitals and Molecular orbitals
Characteristics Atomic orbitals Molecular orbitals
Definition The space surrounded by one The space surrounded by more
nucleus than one nucleus
Filling of electrons According to Hund’s rule According to Pauli exclusion
principle
Contribution to the No as such contribution Shape of molecule is due to
shape of molecule the molecular orbital
Hybridization They can be hybridized They cannot be hybridized
Combination By combination of atomic A bonding molecular orbital,
orbitals, molecular orbitals and itself contains sigma bond.
bonds are produced
Magnetic nature It helps to explain the magnetic It helps to explain the magnetic
nature of atom nature of molecule
Difference between Valence Bond Theory (VBT) & Molecular Orbital Theory (MOT)
Valence bond theory (VBT) Molecular orbital theory (MOT)
According to this theory half filled orbitals According to this theory two atomic orbitals
of atoms overlap to form covalent bond. The combine to produce two molecular orbitals in
overlapping of two atomic orbitals forms which electrons are distributed according to
single covalent bond whereas the the rules of electronic configuration.
overlapping of more than two atomic
orbitals forms multiple covalent bond
The electron cloud (Electron density) is Valence electrons (Electron cloud) are
maximum at the point of meeting of orbitals associated with all the nuclei concerned.
 of atoms.

Chapter No. 5
Energetic of Chemical Reactions
THERMO CHEMISTRY”
“The branch of chemistry which deals with energy changes in chemical reactions is called
thermo chemistry”
THERMODYNAMICS”
“Study based on the principal of conservation of energy is known as thermodynamics”
THERMOCHEMICAL REACTIONS”
“The chemical reaction that occurs with the evolves or absorption of energy is known as
thermo chemical reaction”
TYPES OF CHEMICAL REACTIONS”
There are two types o chemical reaction.
 Exothermixc reaction
 Endothermic reaction

EXOTHERMIC REACTION”
“The thermo chemical reaction in which heat is released is called exothermic reaction”
CHARACTERSTICS OF EXOTHERMIC REACTION:
 In exothermic reactions the enthalpy of product is lower than the reaction. ▲H is therefore
negative for an exothermic reaction.
 During exothermic reaction, the system becomes warmer and net P.E of substance
decreases.
 The energy is evolved during these reactions.
EXAMPLES:
All the types of combustion reactions are exothermic.
 Combustion of natural gas:
CH4 + O2 → CO2 + 2H2O ▲H = -890.4KJ
 Formation of ammonia:
N2 + 3H2 → 2NH3 ▲H = -22Kcal
 Burning of coal:
C + O2 → CO2 ▲H = -393.5 KJ
 Formation of water:
2H2 + O2 → 2H2O ▲H = -571.6 KJ
SIGNIFICANCE OF EXOTHERMIC REACTION:
(a) Exothermic explosion used for blasting rock in mining.
(b) Heat released during respiration is used to warm us.
(c) Heat released in the burning of fuel is used to cook food.
ENDOTHERMIC RTEACTION”
“The thermo chemical reaction in which heat is absorbed is called exothermic reaction”
CHARACTERSTICS OF ENDOTHERMIC REACTION:
 In endothermic reactions the entropy of reactants is lower than the products.
 ▲H is therefore positive, for an exothermic reaction.
 The energy is absorbed during these reactions.
 The temperature of these reactions therefore decreases.
EXAMPLES:
 Formation of nitric oxide:
N2 + O2 →2NO ▲H = +43.23 K.cals
 Formation of carbondi sulphide:
C + 2S →CS2 ▲H = +22.0 K.cals
 Reaction of coal with steam:
C + H2O →CO+ H2 ▲H = + 118KJ
 Changing in physical state of water:
H2O(l) →H2O ▲H = +40.7KJ
SYSTEM”
“Part of universe, which is under thermodynamics study is called system”
EXPLAINATION:
A system usually consists of a definite amount of substance and is separated from the
surrounding by real or imaginary boundary through which matter and energy can flow from
the system to the surrounding.

SURROUNDINGS”
“The universe other than the system is known as surroundings”
TYPES OF SYSTEM:
There are following three types of system.
 Isolated system
 Close system
 Open system
ISOLATED SYSTEM”
“The system which can neither exchange matter nor energy with its surrounding is called
isolated system”

EXPLIANATION:
If water is placed in a vessel which is closed as well as insulated, no exchange of matter or
energy can take place between the system and surroundings.
EXAMPLE:
An example of an isolated system would be an insulated container, such as an insulated gas
cylinder

CLOSED SYSTEM”
“The system which can exchange only energy and not matter with its surrounding is called
a closed system”
EXPLIANATION:
Some reaction is allowed to take place in a cylinder enclose by a piston. As the vessel is
closed, no exchange of matter between the system energy can take place between the
system and surroundings.

EXAMPLE:
A greenhouse is an example of a closed system exchanging heat but not work with its
environment
OPEN SYSTEM”
“The system which can exchange both matter and energy with the surrounding is called on
open system”
EXPLIANATION:
If some water is heated in an open vessel, exchange of both matter and energy takes place
between the system and the surrounding.
EXAMPLE:
The ocean would be an example of an open system
MACROSCOPIC PROPERTIES”
“The macroscopic properties of the system which is easily measurable, and in bulk is
known as macroscopic properties”
EXAMPLES:
Pressure, Volume, Temperature
TYPES OF MACROSCOPIC PROPERTIES”
There are two types of macroscopic properties.
 Intensive properties
 Extensive properties
INTENSIVE PROPERTIES”
“Properties of system, which are independent of the amount of material, are known as
intensive properties”
EXAMPLES:
Density, Temperature, Surface tension, Pressure
EXTENSIVE PROPERTIES”
“Properties of system, which depends upon the amount of the subtance present in the
system, are known as extensive properties”
EXAMPLES:
Mass, Volume, Mole, Enthalpy, Internal energy
STATE OF A SYSTEM”
“The properties which describes a system completely under a given set of conditions is
known as state of a system”
EXPLAINATION:
The state of system is completely describe by a set of variables such as pressure, volume,
temperature, number of moles e.t.c
TYPES OF STATE”
There are two types of state,
 Initial state
 Final sate
INITIAL STATE”
“The description of a system before it undergoes a change is called initial state”
FINAL STATE”
“The descriptions of a system after it undergoes a change is called final state”
THE CHANGE IN STATE:
The change in state = final state – initial state
Change in temperature ▲T = T2 –T1
Change in pressure ▲P = P2 – P1
Change in volume ▲V = V2 – V1
THERMODYNAMIC STATE:
“The set of conditions which completely describe a system is called Thermodynamics
state”
INTERNAL ENERGY:
“The energy stored within a substance is called its internal energy”
OR
“The sum of all kinds of K.E and P.E of all atoms, molecules or ions the system is known
as internal energy”
NOTATION:
It is denoted by E.
DEPENDENCE:
I is value depends upon temperature, pressure chemical nature and amount of the
subtance.
CHANGE IN INTERNAL ENERGY:
The change in internal energy ▲E is given by,
∆𝐸 = 𝐸2 − 𝐸1
“FIRST LAW OF THERMODYNAMICS”
STATEMENT:
“The total amount of energy in an isolated system remains constant”
OR
“The total amount of system and surrounding remains constant”
MATHEMATICAL FORM:
Consider a thermodynamic system initially have internal energy E1 absorbs ∆Q amount
of heat from its surroundings and performs ∆W amount of work and at the same time its
internal energy increases to E1 to E2 then according to the first law of thermodynamics
q =▲E + ∆W
This is the mathematical form of the first law of thermodynamics, this is also written as,
▲E = q -∆ W
SIGN CONVENTION:
 When heat is absorbed by the system, the q = positive
 When heat is given out by the system, the q = negative
 When energy is absorbed by the system, then ▲E = positive
 When energy is given out by the system, then ▲E = negative
 Work done by the system, then ∆W = positive
 Work done on the system, then ∆ W = negative
PRESSURE, VOLUME AND WORK
Consider a cylinder of gas having an area of cross-sectional ‘A’ fitted with a frictionless
and weightless piston bearing a pressure ‘P’ the total force ‘F’ acting on the piston will be,

d
V2
V1

𝑓𝑜𝑟𝑐𝑒
𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 =
𝑎𝑟𝑒𝑎
𝐹
𝑃=
𝐴
𝐹 = 𝑃×𝐴
∆𝑊 = 𝐹. 𝑑
∆𝑊 = 𝑃𝐴𝑑
𝐴𝑑 = ∆𝑉
∆𝑊 = 𝑃∆𝑉
This is the equation of pressure- volume and work According to the first law of
thermodynamics,
𝑞 = ∆𝐸 + 𝑃∆𝑉
PROCESS AT CONSTANT VOLUME:
Heat supplied at constant volume is also known as "isochoric system". An isochoric process
is one in which the volume of system during the supply of heat does not change. This is
achieved only when the piston of cylinder is fixed.
In order to supply heat at constant volume piston of cylinder is fixed at a certain position
so that during heat supply volume of system remains constant.
𝑞𝑣 = ∆𝐸 + ∆𝑊
𝑞𝑣 = ∆𝐸 + 𝑃∆𝑉
At constant volume,
∆𝑉 = 0
Therefore,
𝑞𝑣 = ∆𝐸 + 𝑃 × 0
𝑞𝑣 = 0
CONCLUSION:
From the above expression we conclude that the heat absorbed by the system at constant
volume is completely utilized to increase the internal energy of the system.

PROCESS AT COSTANT PRESSURE:

Heat supplied at constant pressure is also known as "isobaric process". An isobaric process
is one in which no pressure change takes place during the supply of heat to system.
In order to understand an isobaric process considers a cylinder fitted with a frictionless
piston, the piston is free to move. An ideal gas is enclosed in the cylinder
▲E = q –W
At costant pressure,
▲E = qp – W
qp = ▲E + W (i)
Where qp is the heat change at constant pressure,
W = P▲V (ii)
Substitute the eq (ii) in (i),
qp = E + P▲V (iii)
But,
∆E = E2 – E1 , ▲V = V2 – V1
Subsitute the value of E and V in eq (iii),
= (E2 – E1) + P (V2 – V1)
= E2 – E1 + PV1 – PV2
= ( E2 + PV2) – (E1 + PV1)
H1 = E1 + PV1 , H2 = E2 + PV2
= H2 –H1
= ▲H
Where ▲H is the change in enthalpy,

CONCLUSION:
The above equation shows that heat given top or taken from a system at constant pressure
is equal to the change in enthalpy of the system.
ENTHALPY (HEAT CONTENT)”
“The internal energy of a system and its capacity of doing work is called enthalpy it is
also called heat content”
NOTATION:
IT is represented by ‘H’
MATHEMATICAL FORM:
 It is mathematically equal to the sum of energy and product of pressure and volume of a
system.
H = E+PV
CHANGE IN ENTHALPY:
▲H = H2 – H1
SIGN OF ▲H:
 For all exothermic process ▲H would be negative.
 For all endothermic process ▲H would be positive.
“HESS’S LAW”
INTRODUCTION:
In 1846 a Russian chemist german Hess states a law of constant heat summation.
STATEMENT:
“The enthalpy change in reaction is the same whether the reaction occurs in one step Or in
more than one step”
MATHEMATICAL FORM:
Consider a system chemical whose initial and final states are represented by "A" and "E"
respectively. The change from A to E may take place in single step.

In single step change in enthalpy is ∆H.

This change of reactant (A) to product (E) may take place in more than one steps :

According to Hess's law of constant summation:

H = H1 H2+ H3 + H4

EXPERIMENT VERIFICATION:
Consider the chemical reaction between NaOH and CO2 this reaction may be represented
in two ways.
COMPLETE IN ONE STEP:
2NaOH + CO2 →Na2CO3 + H2O ▲H = -89.06 KJ
 COMPLETE IN TWO STEPS:
STEP # 01:
2NaOH + CO2 →NaHCO3 ▲H1 = -48.06KJ
STEP #
NaHCO3 + NaOH →Na2CO3 + H2O ▲H2 = -41.02KJ
THE ENTHALPY CHANGES:
▲H = ▲H1 + ▲H2
-89.16 = -48.06 + (-41.02)
APPLICATIONS OF HESS’S LAW:
With help of Hess’s law we can calculate,
 Calculate the heat of formation of compound.
 Calculate the heat of combustion.
 Calculate the heat of reaction.
HEAT OF FORMATION”
“It is the amount of heat evolved or absorbed during the formation of one mole of
compound from its components”
NOTATION:
It is denoted by HF
UNIT:
Heat of formation measured in kj/mole.
EXAMPLE:
Heat of formation of CH4 = -79.9 KJ/mole.

Chapter # 05
Energetic of Chemical Reactions
Thermo Chemistry:-
It is the branch of chemistry that deals with the study of heat energy changes in the chemical
reactions.
Thermodynamics:-
This term is a combination of two Greek words therm which mean “heat” and dynamics which
mean “interaction / relationship”.
It is the branch of physical chemistry that deals with the study of inters conversion of heat and
other forms of energy.
Thermo Chemical Reaction:
Those reactions which complete by absorbing or evolving of heat energy.
For example,
Burning of natural gas, reaction of nitrogen and oxygen etc.
Types of Thermo Chemical Reactions:
1. Exothermic Reaction: The term exothermic is a combination of two words, Exo which means
“outside” and therm which means “heat”. Those chemical reactions that evolve heat energy for its
completion are called exothermic reactions.
For example:
 N2(g) + 3H2(g)  NH3(g) + Heat OR N2(g) + 3H2(g)  NH3(g) H  ve
2SO2(g) + O2(g)  2SO3(g) + Heat OR 2SO2(g) + O2(g)  2SO3(g) H  ve

2. Endothermic Reaction: The term endothermic is a combination of two words Endo which means
“inside” and them which means “heat”. Those chemical reactions that absorb heat energy for its completion
are called endothermic reactions,
for example,
N2(g) + O2(g) Heat  2NO(g) OR N2(g) + O2(g)  2NO(g) H  ve
H2(g) + I2(g) Heat 
 2HI(g) OR H2(g) + I2(g) 
 2HI(g) H  ve

The factors upon which energy changes in a chemical reaction depends

 The mass of reactants involved in the chemical reaction.
 The physical states of the reactants, i-e gas, liquid or solid.
 Temperature at which the chemical reaction is carried out.
 Conditions of the chemical in which it carried out, i-e constant volume or constant
pressure.

Units of Energy
 In S.I system, the unit of energy is “Joule”(J).
 In M.K.S system, the unit of energy is “Calorie” (Cal)
 1 Cal = 4.814J OR 1J = 0.28 Cal

Thermodynamical Terms
1. System: Any real or imaginary portion of the universe that is under observation is called system
For example
 In the determination of boiling point of water, the sample of wate is system.
 In the study of thermal decomposition of lime stone (CaCO3), the sample of lime stone is
system.
2. Surrounding: The environment around the system that can affect the system but is not a part of
system. For example, temperature, pressure, humidity etc.
3. State: It is the description of the system in its surroundings. There are two types of states.
 Initial State: The description of the system before change in the system is called initial
state.
 Final State: The description of the system after change in the system is called final state.
The difference between the initial and final state is called change of state that is represented by 
. The change in state is equal to the difference between final and initial states. For example
V  V2  V1 P  P2  P1 T  T2  T1 E  E2  E1
Where;
V1 = Initial state of volume
V2 = Final state of volume
P1 = Initial state of pressure
P2 = Final state of pressure
T1 = Initial state of temperature
T2 = Final state of temperature
E1 = Initial state of internal energy
E2 = Final state of internal energy
Enthalpy
Definition: - It is the total heat content of the system. It is a state function.
Symbol: - Enthalpy is represented by “H” whereas change in enthalpy is represented as ∆H.
Mathematically: - It is the sum of the internal energy (E) and the product of pressure (P) and volume
(V) of the system.
H = E + PV
Macroscopic properties
Definition: - Those properties of the system that can easily be measured. For example, Pressure,
Temperature, Volume, Density, Viscosity, Surface tension, Boiling point, Melting point etc.
Types of macroscopic properties: - There are following two types of macroscopic properties.
1. Intensive properties: - Those macroscopic properties which do not depend upon the amount of
the system. For example, Density, Pressure, Temperature, Viscosity, Surface tension, Refractive
index, Melting point, Boiling point and etc.
2. Extensive properties: - Those macroscopic properties which depends upon the amount of the
system. For example, Mass, Volume, Mole numbers, Enthalpy, Entropy, Internal energy, Gibb’s
free energy and etc.
Extensive properties become half when the amount of the material is reduced to half.

First law of thermodynamics OR Law of conservation of

energy Introduction: - This law was suggested by “Helmholtz”
in 1847.
Statement: - Energy can neither be created nor be destroyed during any physical or chemical
change but it can be changed from one form to another but the total energy remains same.
Explanation:
Suppose a system has E1 internal energy. If “q” amount of heat is supplied to the
system its internal energy will be raised to E2 (the change in internal energy will be E ). System will
also do “w” work.
Mathematically:-
q = (E2 – E1) + w
OR q = E w

Conclusion: - This shows that heat energy is concerting into internal energy and work done, so this
law is
also called law of conversation of energy.
First law of thermodynamics (Pressure volume work): - OR
Energy conservation (Pressure volume work): -
Consider a cylinder having area of cross section “A” with
movable and frictionless piston having volume “V1”. When
“q” heat energy is supplied to the system, internal energy of
the system increases by ∆E, hence system exerts “P” pressure on
the piston so piston moves upward and its volume increases to
“V2”.
According to 1st law of thermodynamics;
q = ∆E + W Equation # 1
As work is done by applying the force “f” by the system with changing the
length “dl” of the system. So
W = F.dl Equation # 1
As we know that; Pressure =
Force F
OR P OR F  PA
Area A
Hence equation # 2 can be written as
W = PA .dl
Since A dl = ∆V
So
W = P ∆V Putting in equation # 1
q = ∆E + P ∆V
Where q = Amount of heat energy
P = Pressure of the system
∆E = Change in internal energy
∆V = Change in volume of the system
Conclusion: - P∆V is called Pressure volume work of a system.
First law of thermodynamics at constant volume: - OR
Energy change of a system at constant volume: - OR
Prove that qV = ∆E
As we know that pressure volume work of first law of
thermodynamics; qV = ∆E + P ∆V
At constant Volume, ∆V = 0; so above equation can be
written as; qV = ∆E + P (0)
qV = ∆E
Conclusion:- At constant volume, the heat energy will only change the internal energy and there
will be no work done.
First law of thermodynamics at constant pressure:- OR Enthalpy of the System
OR
Energy change of a system at constant pressure: OR Prove that qp = H
For pressure volume work according to first law of thermodynamics:
qp = ∆E + P∆V At constant pressure, q = qp
qp = (E2 – E1) +P(V2 – V1)
qp = E2 – E1 +PV2 – PV1 By rearranging the terms
qp = E2 + PV2 - E1 – PV1 By taking common terms
qp = (E2+PV2) – (E1 + PV1) Equatin # 1.
We know that enthalpy (H) = E + PV; therefore; H1 = E1 + PV1 & H2 = E2 + PV2
Hence equatin # 1 can be written as:
qp = H2 – H1
qp = ∆H
Conclusion: - At constant pressure, the heat energy will only change the enthalpy of
the system and there will be no work done.
Hess’s law of heat of summation
Introduction: - this law was suggested by G. N. Hess in 1846 about the
enthalpies of those reactions which occur in more than one step.
Statement: -
1. The heat absorbed or evolved in a reaction is same whether the reaction is
occurring in one or several steps.
2. The overall enthalpy change for a process depends only on the initial
and final states of the system, and is independent of the route or pathway
between these states. Mathematically: - ∆H = ∆H1 + ∆H2 + ∆H3 . . . . . . + ∆Hn
Explanation: -
 The sum of heat energy change in all steps of a reaction is same as the total heat energy
change in the reaction.
 The energy absorbed or evolved in a chemical reaction depends upon the initial and final
states of the system.
 The energy absorbed or evolved in a chemical reaction is independent to its path.
General example: - Suppose a reaction; A   D ∆H = x
KJ / mol If this reaction completes in following three steps;
Step # 1 A  B ∆H1 = yKJ / mol
Step # 2 B  C ∆H2 = z KJ / mol
The sum of energy changes in all steps is equal to the
total energy change in the reaction.
∆Hx = ∆H1 + ∆H2
X KJ/mol = (y + z) KJ / mol
Another example:- The reaction of caustic soda (NaOH) and carbon dioxide (CO2).
2NaOH + CO2   Na2CO3 + H2O ∆H = -90Kj/mol
This reaction occurs in following two steps
Step # 1 CO2 + NaOH   NaHCO3 ∆H1 = -49 KJ / mol
Step # 2 NaHCO3 + NaOH   Na2CO3 + H2O ∆H2 = -41 KJ/mol
 According to Hess’s law of summation;
∆H = ∆H1+ ∆H2
-90KJ / mol = [(-49) + (-41)] KJ / mol
-90KJ/mol = -90 KJ / mol
Application of Hess’s Law of heat of summation:
 It is successfully applied in thermochemistry for the calculation of heat of
reaction (like heat of formation, heat of neutralization etc), where direct
measurement is not possible.
Heat of formation:
Definition:- The amount of heat absorbed or evolved (enthalpy change)when one mole of a
substance is formed from its elements at 250C in called Heat of formation.
Explanation:
 It is represented by ∆H.
 The unit of heat of formation is KJ / mol or Kcal / mol
Example: 2H2(g) + O2(g)   2HO(l) ∆H = -394 KJ/mol
N2(g) + 3H2(g)   2NH3(g) ∆H = -92KJ/mol
Standard heat of formation:
The amount of heat absorbed or evolved (enthalpy change) when a substance is formed
from one mole of all reactants involved at 250C is called standard heat of formation it is
represented by ∆Hf for example
C(g) + O2(g) 
 CO2(g) ∆H = -394 KJ/mol
Numerical:
Calculation the heat of formation of the ethyne (C2H2) by the following data.
i) 2C + H2 
 C2H2 ∆H = ?
ii) C + O2 
 CO2 ∆H = -394 KJ/mol
iii) H2 + ½ O2 
 H2O ∆H = -286KJ/mol
iv) C2H2 + 5/2 O2   2CO2 + H2O ∆H = -1298 KJ / mol
Step # 1: Multiply the equation (ii) & (iii) by 2 and 1 respectively, then add these equations
2C + 2O2  2CO2 ∆H = -788 KJ / mol
H2 + ½ O2  H2O ∆H = -286 KJ / mol
2C + H2 + 2 ½ O2  2CO2 + H2O ∆H = -1074 KJ/mol Equation (v)
Step # 2: Subtract equation (iv) from equation (v)
2C + H 2 + 2 ½ O2   2CO2 + H2O ∆H = – 1074 KJ / mol
_C2H2  /2 O2 
5
 _2CO2  _H2O ∆H =  1298 KJ / mol
2C + H2 
 C2H2 ∆H = +224 KJ/mol

CHAPTER # 06
Chemical Equilibrium
Types of reactions on the basis of its direction
Chemical reactions are classified into two types on the basis of their direction.
1. Irreversible reactions:-
Definition: those reactions, which go only in the forward direction, are called irreversible
reactions.

Explanations:
  The term “Irreversible” is a combination of two words; “Ir” means “Not”, “Reverse”
means “Back”.
 These are “one way reactions”.
 The products of these reactions cannot be converted into the reactants back.
 These reactions go for completion.
 These reactions are represented by ‘single headed arrow” (  ).
 Few examples of irreversible reactions are;
HCl + NaOH   NaCl + H2O
Hydrochloric acid Sodium Hydroxide Sodium Chloride Water

2. Reversible Reaction:
Definition: Those reactions, which go in the forward as well as in backward direction, are
called reversible reactions.

Explanation:
 The term “reversible” is taken from “Reverse” which means “back”.
 These are “two way reactions”.
 The products of these reactions can be converted into the reactants back.
 These reactions never go for completion.
 These reactions are represented by “double headed arrow” (  )
 Few examples of reversible reactions are;
H2 + I2  2HI
Hydrogen Iodine Hydrogen Iodide

N2 + 3H2  2NH3

Nitrogen Hydrogen Ammonia

CH3COOH + C2H5OH  CH3COOC2H5 + H2O

Acetic acid Ethyl alcohol Ethyl acetate Water

Rate of Reaction
The concentration of the reactants converted into the products per unit time is called rate
of reaction.
Rate of forward Reaction
The concentrations of the reactants converted into the products per unit time is called rate
of forward reaction.
Rate of Backward Reaction
The concentrations of the products converted into the reactants per unit time is called rate
of backward reaction.
Concentration:
Concentration is defined as number of moles of a substance in one liter (dm 3) of the
solution.

Chemical Equilibrium “OR” Dynamic Equilibrium

Definition: The point in a reversible reaction at which rate of forward and backward
reactions are equal is called chemical equilibrium.

Explanation: Consider a reaction

A + B  C + D
 The graph shows that initially the The forward process: A + B C+D
concentration of A and B decrease and the decrease in rate, as time increases.
concentrations of the products increase. But At equilibrium, the
after some time at “Te”, the concentrations of forward and reverse
rates become equal
both reactants and products are same and A+B C +D
constant, hence these are the equilibrium Equilibrium Point
concentrations and this point is “equilibrium
point”.

Law of mass action (Equilibrium law)

Introduction: Te
Scandinavian scientists “Guldberg” and Time

“Waage” suggested this law in 1864

about the rates of reversible reactions.
Statement:
The rate of reaction is directly proportional to the product of the active masses of the
reactants raised by their number of moles.
Explanation:
 Those concentrations, which take part in a chemical reaction, are called active
masses.
 The active masses are represented by [ ].
 The unit used for active masses is mol/L or mol/dm3.
Derivation of expression of Equilibrium constant (Kc)
Consider a general equation xA + yB  aC +
bD
Where x, y, a and b are number of moles of A, B, C and D respectively.

Here two reactions are going on

Forward Reaction: xA + yB  aC + bD
Backward reaction: aC + bD  xA + yB

According to the law of mass action;

Rate of forward reaction  [A]x.[B]y
Rate of forward reaction = K1 [A]x.[B]y Equation # 1
Rate of backward reaction  [C]a.[D]b
Rate of backward reaction = K2 [C]a.[D]b Equation # 2
Where,
K1 = Forward rate of reaction, K2 = Backward rate constant

At equilibrium point;
Rate of forward reaction = Rate of backward reaction
K1[A]x.[B]y = K2[C]a.[D]b
by rearranging

K 1 C a .D b C a .D b
 or Kc 
K 2  Ax .B  y Ax .B  y
Here:
K 
K2 =  1 
K 
  Kc is Equilibrium constant that is defined as the ratio between the concentration of
reactants and products raised by their number of moles.
K1
 Kc is the ratio between the forward and backward equilibrium constant
K2
 Kc is the overall equilibrium constant of reversible reaction.
 Kc can be represented for both gaseous and non-gaseous reactions
 Kp is Equilibrium constant for gaseous reactions that is defined as the ratio between
the pressures of reactants and products raised by their number of moles.

Kc and Kp expressions for few reversible reactions

1. H2(g) + I2(g)  2HI2(g)
[ HI ] 2
PHI 
Kc=
H 2 . I 2  Kp=
P P 
H2 I2

2. N2(g) + 3H2(g)  2NH3(g)

NH 3  2
P  NH 3
Kc =
N 2 . H 2 3 Kp =
P P 
H2 N2

Relation between Kc and Kp

1. If Kc = Kp It means the volumes of both the reactants and products are equal
For example:
H2(g) + I2(g)  2HI(g)

2. If Kc > Kp (Kp < Kc) It means the volumes of products are lesser then that of
reactants.
For example:
2SO2(g) + O2(g)  2SO3(g)

3. If Kc < Kp (Kp > Kc) it means the volumes of products are greater than that of
reactants.
For example:
2NH3(g)  N2(g) + 3H2(g)

Problems related to Equilibrium Constant (Kc)

Example # 1: If the equilibrium concentrations for the reaction;

A + B  2C was [A] = [B] = 4
3 3
Mol/dm and [C] is 6 mol/dm . What will be the value of Kc?
Date: [A]equilibrium =4 mol / dm3
[B]equilibrium = 4 mol / dm3
[C]equilibrium = 6 mol/dm3
Kc =?

Kc 
C
2

6
2
36
 2.25
Solution:
B. A 4. 4 =
16
Example # 2: In a reaction, N2 + 3H2  2NH3, 0.1 mol of N2, 3.0 mol of H2 and 1.0 mol of
NH3 were present at equilibrium. What is the value for Kc of the reaction?
N2 + 3H2  2NH3

Mole at Equilibrium  0.1 mol 3.0 mol 1.0 mol

n 0.1 mol 3.0 mol 1 mol

Conc. at Equilibrium   
V  1L 1L 1L

0.1 mol/L 3.0 mol/L 1 mol/L

Now Kc 
NH 3 2 
12 
1
 11.11
N 2 H 23 0.1. 33 0.9

Example # 3: If 30g of SO2, 20g O2 and 38g of SO3 were present at equilibrium in 12 dm3
container in the following reaction? What is the value for Kc of the reaction?
2SO2 + O2  2SO3
Mass at Equilibrium  30g 20g 38g
m 30 20 38
Moles at Equilibrium   
M  64 32 80
0.47mol 0.625 mol 0.475 mol
Volume of container  12dm3 12dm3 12dm3
n 0.47 0.625 0.475
Conc. At equilibrium   
V  12 12 12
3
3.92 mol/dm 0.05mol/dm 0.004 mol/dm3
3

Kc 
SO3 2 
0.0042  0.000016
 2.08  10 5
SO2  .O2 
2
3.92 .0.05
2
0.768
Calculation of equilibrium concentrations and initial concentrations from Kc
Example#1: If 20g of Nitrogen is mixed with 4g of Hydrogen in the following reactions. If Kc
for the reaction is 9.5, what will be the equilibrium concentrations of each substance?
 N2(g) + 3H2(g)   2NH3(g)

Initial mass  20g 4g 0

m 20 4 0
Initial moles    mol mol
M  28 2 17

0.71 mol/L 2 mol/L 0 mol/L

n 0.71mol 2 mol 0 mol

Initial Concentrations   
V  1L 1L 1L

0.71 mol/L 2 mol/L 0 mol/L

Let,
Change in concentrations  -X -3X +2X
To reach at equilibrium

Concentrations at equilibrium  0.71-X mol/L 2-3Xmol/L 2Xmol/L

Kc 
NH 3 2
N 2 . H 2 3

9.5 
2 X 2
0.71  X . 2  3 X 3
Now apply the mathematical formula (a – b)3 = (a – b)2 (a - b) = (a2 - 2ab + b2) (a-b)
9.5 (4 – 12X + 9X2) (2 – 3X) (0.71 – X) = 4X2
9.5[8 – 24X + 18X2 – 12X + 36X2 – 27X3 (0.71 – X)] = 4X2
9.5[5.68 – 25.56X + 38.34X2 – 19.17X3 – 8X – 36X2 – 54X3 – 27X4] = 4X2
9.5[5.68 – 33.56X + 2.34X2 – 73.17X3 – 27X4] = 4X2
9.5[5.68 – 33.56X + 2.34X2 – 73.17X3 – 27X4] = 4X2
53.96 – 318.82X + 22.23X2 – 695.11X3 – 256.25X4 = 4X2
53.96 – 318.82X + 22.23X2 – 4X2 – 695.11X3 – 256.25X4 = 0
53.96 – 318.82X + 18.23X2 – 695.11X3 – 256.25X4 = 0
By ignoring higher terms
18.23X2 – 318.82X + 53.96 = 0
Now apply quadratic formula to solve this quadratic equation.
Here a = 18.23, b= -318.82, c = 53.96
 b  b 2  4ac
X
2a
 (318.82)  318.822  4(18.23)(53.96)
X=
218.23
318.82  101646  3936.76)
X
218.23
Now we can write this into two following ways.
318.82  312.58
X
218.23
318.82  312.58 318.82  312.58
X OR X
218.23 218.23
X  2.89 OR X  0.023
X = 0.023
Now put the values of “x” in the equilibrium concentrations of all reactants and products.
N2 = 0.71 – X = 0.71 – 0.023 = 0.687 mol/L
H2 = 2-3Xmol/L = 2 – 3(0.023) = 1.931 mol/L
NH3 = 2Xmol/L = 2 x 0.023 = 0.046 mol/L

Related information
1. If both values of “x” are positive, we will take smaller value.
2. If one value of “x” is positive and other is negative, we will take positive one.

Applications of Equilibrium Constant

1. To predict the direction of reaction: [Product]initial
i) if KInitial > Kc (Kc < Kinitial), Here, Kinitial =
[Reactant]initial

The reaction will go backward to achieve equilibrium position.

ii) if K < Kc (Kc > Kinitial)
The reaction will go forward to achieve equilibrium position

iii) If K = Kc
The reaction is at equilibrium position.

2. To predict the extent of reaction:

i) If Kc is very large,
This means that forward reaction is almost completed and backward reaction is
proceeding with negligible speed.
For example:
2O3  3O2 Kc = 1055
ii) If Kc is very small,
This means that backward reaction is almost completed and forward reaction is
proceeding with negligible speed.
For example:
2HF   H2 + F2 Kc = 10-13
iii) If Kc is neither very large nor very small (moderate),
This means that both forward and backward reactions are going on with almost
same speed.
N2(g) + 3H2(g)   2NH3(g)

Numerical The Kc for the dissociation of Hydrogen Iodide (HI) at 350 0C is 1.3 x 10-2. If there
are 5 mol/dm3 Hydrogen, 1.5 mol/dm3 Iodine an 5 mol/dm3 hydrogen Iodide, predict
the direction of reaction.
2HI 
 H2 + I2
Date: Kc = 1.3 x 10-3
[H2]initial = 0.5mol/dm3
[I2]initial = 1.5 mol/dm3
[HI]initial = 5 mol/dm3
Direction of reaction= ?
H  .I  (0.5).(1.5) 0.75
K initial  2 initial 2 2 initial    3  10  2
Solution:
HIinitial 5 2
25
Here,
Kc < Kinitial

1.3 10 -2
< 3  10-2
Therefore reaction will go in backward direction (towards left / reactant side)
Numerical: Kc for the reaction 2HI   H2 + I2 at 4480C is 0.0194. if one liter
container contains 0.2 moles of Hydrogen, 12 moles Iodine and 15 moles of Hydrogen Iodide,
predict the direction of reaction.
2HI  H2 + I2
Initial moles  15 mol 0.2 mol 12mol
Volume  1L 1L 1L
n
Initial concentration    15 mol/L 0.2 mol/L 12 mol/L
V 
Solution KInitial =
H 2 initial .I 2 initial 0.2. 12  2.4
  1.06  10 2  0.0106
HI initial
2
152 225

Here
Kc < K0

1.3 10 -2
< 3  10-2
Therefore reaction will go in backward direction (towards left / reactant side)

Le-Chatelier’s principle

Introduction: Le-Chatelier proposed this principle in 1884 about the factors those disturb the
equilibrium position of the reversible reaction.
Statement: “When external stress (Concentration, temperature, pressure and Catalyst) is applied
to the equilibrium mixture, its equilibrium positing gets disturb and moves to the forward or
backward direction to reestablish equilibrium”.

Effect of concentration Change:

Species Change in Effect on the reaction to reestablish
concentration equilibrium
Increase Reaction will go forward (Products side)
Reactants
Decrease Reaction will go backward (Reactant side)
Increase Reaction will go backward (Reactant side)
Products
Decrease Reaction will go forward (Products side)

Effect of temperature Change:

Nature of reaction Change in Effect on the reaction to reestablish
temperature equilibrium
Endothermic Increase Reaction will go forward (Products side)
N2+O2   2NO Decrease Reaction will go backward (Reactant side)
Exothermic Increase Reaction will go backward (Reactant side)
2NO+O2   2NO2 Decrease Reaction will go forward (Products side)

Effect of pressure Change:

Volume Change Change in Effect on the reaction to reestablish
pressure equilibrium
V Reactants > V Products Increase Reaction will go forward (Products side)
2NO+O2   2NO2 Decrease Reaction will go backward (Reactant side)
V Reactants < V Products Increase Reaction will go backward (Reactant side)
2O3  3O2 Decrease Reaction will go forward (Products side)
V Reactants = V Products Increase No Equilibrium position
2HI  H2+I2 Decrease No Effect on equilibrium position

Important applications of Le-Chatelier’s Principle:

Haber’s process (formation of Ammonia):
The main reaction in the formation of Ammonia (NH3) through Haber’s process is following:
 N2(g) + 3H2(g)   2NH3(g)  H=-46.2 KJ/mol
1 Volume 3 Volume 2 Volume
To obtain maximum concentration of product (Ammonia - NH3), Le-Chatelier’s principle is
applied in the following manner.
i) Effect of concentration: If more nitrogen and hydrogen are added at equilibrium, the
reaction will move forward to produce more products (NH3).
ii) Effect of temperature: This is an exothermic reaction, therefore in this case temperature is
decreased to force the reaction in forward direction to get high yield of product (NH3)
iii) Effect of pressure: In this reaction the volume (Number of moles) of reactants (N2 and H2)
is greater than the volume of products (NH3), therefore in this case pressure is increased
to force the reaction in forward direction to get high yield of product (NH3).

Contact process (formation of Sulphuric acid)

The main reaction in the formation of Sulphuric acid (H2SO4) through contact process is
following.
2SO2(g) + O2(g)   2SO3(g)  H = -46.2 KJ/mol

2 volume 1 volume 2 volume

To obtain maximum concentration of product (sulphuric acid-H2SO4), Le-Chatelier’s principle is

applied in the following manner.

i) Effect of concentration: If more sulpher dioxide and oxygen are added at equilibrium, the
reaction will move forward to produce more product (H2SO4).

ii) Effect of temperature: This is an exothermic reaction, therefore in this case temperature
decreased to force the reaction in forward direction to get high yield of product (H2SO4).

iii) Effect of Pressure: In this reaction, the volume (Number of moles) of reactants (SO2 and
O2) is greater than the volume of products (H2SO4). Therefore in this case pressure is increased
to force the reaction in forward direction to get high yield of product (H2SO4).

Effect of Catalyst on Equilibrium:-

Catalyst does not create any effect on the equilibrium position of the reversible reaction
but it only alters (Changes) the rate of reaction.

SOLUBILITY PRODUCT
It is the product of ionic concentrations of a salt in its aqueous solution, when dissolved
and undissolved ions are at equilibrium.

Derivation of expression of Ksp:

Consider a general reaction

xAB(s) 
 +
yA (aq) + -
zB (aq)

Undissolved Dissolved

Where=> x, y and z are the number of moles

When excess of salt AB is dissolved into the solvent (water), the equilibrium establishes between
undissolved (salt) and dissolved (ions) forms of that salt and equilibrium constant is represented
as:
 Kc 
A  .B 
 y  z

AB x
x
  
K c . AB   A  . B 
y z
Here, K SP  K c .AB 
x

 A  .B 
 y
 z
K SP
Units of Solubility Product:-
It is measured in the chemical units of concentration. e.g:
For, For,
A2B   2A+ + B-2 AB  A+ + B-1
Ksp = [A+]2[B-2] Ksp = [A+][B-]
Ksp = (mol/dm3)2(mol/dm3) Ksp = (mol/dm3) (mol/dm3)
Ksp = mol3/dm3 Ksp = (mol2/dm6)

Effect of temperature on the solubility product: Ksp  Temperature

Solubility product of a salt increases on increasing temperature due to increase in solubility
of the salt in solution.

Expression of solubility product for various salts:

AgCl   Ag+ + Cl- CaSO4 
 Ca+2 + SO4-2
Ksp = [Ag+] [Cl-1] Ksp = [Ca+2][SO4-2]
PbI2   Pb+2 + 2I- PbCrO4  Pb+2 + CrO4-2
Ksp = [Pb+2] [I-]2 Ksp = [Pb+2] [CrO4-2]

Calculation of solubility product from solubility:

Solubility can be defined as; the mass of a solid dissolved in unit volume of a solvent. i.e. gm/L
(gm/dm3).
Numerical:
The solubility of AgCl is 1.4 x 10-3 g/dm3 at 250C. What will be its solubility product?
[Hint: First convert the solubility of AgCl from mass to concentration]
Here 1.4 x 10-3 g/dm3.
Means => Mass = 1.4 x 10-3g & Volume = 1dm3
Mass in gram
Moles of AgCl =
Molar Mass
1.4 10 3
Moles of AgCl =  7.86  10 6
178
Now converting these moles into concentration
Moles of AgCl
Concentration of AgCl =
Volume
7.86  10 6 mol
Concentration of AgCl = 3
 7.86  10 6 mole / dm 3
1dm
This is the concentration of undissolved salt.
AgCl  Ag+ + Cl-
7.86  10-6 mol/dm3 7.86  10-6 mol/dm3 7.86  10-6 mole /dm3
After complete solubility
Ksp = [Ag+][Cl-]
Ksp = (7.86  10-6) (7.86  10-6)
Ksp = 6.2  10-11 mol2/dm6
Applications of Solubility Product
Solubility product is applied to know whether the salt will be precipitated out from its solution or
not.

1. If the product of ionic concentration = Ksp:

This means that the solution is saturated and no precipitation will be taken place.
2. If the product of ionic concentration > Ksp:
This means that the solution is super saturated and precipitation will be taken place.
3. If the product of ionic concentration < Ksp:
This means that the solution is unsaturated and no precipitation will be taken place.
Numerical:
Should CaSO4 precipitate whose concentration is 1.5  10-5 mol/dm3? Ksp of CaSO4 is
2.4  10-5 mole2/dm6 at 250C.CaSO4  Ca+2 + SO 42
At equilibrium the concentration of CaSO4 will be same as the concentration of Ca+2 and SO 42 is:
1.5  10-5 mol/dm3, therefore solubility product is;
Ionic product = [Ca+2] [SO 42 ]
Ionic product = (1.5  10-5) (1.5 x 10-5)
Ionic product = 2.25  10-10

Hence; Ionic product < Ksp

2.25  10-10 < 2.4  10-5
Therefore, Solution is unsaturated and no precipitation will be taken place.
COMMON ION EFFECT
Definition: The effect by which the solubility of the salt decreases in the solution that contains
already a common ion.
Explanation: The solubility of a partially soluble salt in water is reduced in the presence of more
soluble salt containing common ion.
Example: Calcium oxalate (CaC2O4) is partially soluble in water. It ionizes as follows
CaC2O4  Ca+2 + C2O 42
If CaCl2 (containing a common ion of CaCl2 i-e Ca+2) is added which is highly soluble in water.
It ionizes as:
CaCl2   Ca+2 + 2Cl-
This increases the concentration of Ca+2 in the mixture which pushes back the first reaction for
the formation of CaC2O4. Therefore, the solubility of CaC2O4 further reduces; this is called
common ion effect.
Why solubility of salt reduces on the addition of a common ion:
Explanation on the basis of Le-Chatelier’s Principle: When a common ion is added to the solution
of a salt, the concentration of dissolved ions increases, therefore the reaction goes backward
towards undissolved particles which settle down to give precipitates of solid.
Explanation on the basis of Solubility product: When a common ion is added to the solution a salt,
the ionic product of that salt increases than its solubility product. We know that the salt precipitates
out from its solution if its ionic product becomes greater than its solubility product.

Application of the common ion effect:

There are two following applications of common ion effect.
1. In salt analysis 2. In purification of common salt (NaCl)
 CHAPTER # 07
Solutions and Electrolytes
Solution: - Solution is a homogeneous mixture of two or more components having
uniform composition and Physical properties.

Solvent: - The component of a solution in which solute is dissolved

Solute: - The component of a solution which is dissolved in the solvent
Concentrated solution: - A solution having relatively more amount of solute; is called
dilute solution.
Saturated solution: - A solution that may not dissolve more quantity of solute at specific
temperature, is called saturated solution.
Unsaturated solution: - A solution that has a capacity of dissolving more quantity of
solute in solution is called unsaturated solution
Supersaturated solution: - A saturated solution that dissolves more quantity of solute by
increasing the temperature is called supersaturated solution.
Concentration: - Concentration is defined as the amount (mole / mass) of solute in a
specific quantity solvent.
Types of concentration: - There are three types of concentration.
1. Percentage solution (%): - A quantity of solute in specific volume of solvent if
presented in percentage is called percentage solution. For example;
10g sugar in 100ml solution = 10% aqueous solution of sugar
10g sugar in 200ml solution = 5% aqueous solution of sugar
2. Molarity (M): - No. of moles of a solute present in one dm3 (1Liter) of solution
is called molarity and the solution is called molar solution.
  Mass of solute (in gm ) 
Number of moles of solute  Molecular mass of solute 
M  
Volume of solutionin dm 3  
3
Volume of solution (in dm )
 
For Example: - If 20g of glucose is dissolved in 500 milliliter solution. What will be the
molar concentration of solution?
Data:
Mass of solute in grams
Molecular Mass of solute = 20g
Volume of the solution = C6H12O6 = 12  6 + 1  12 + 16  6 =
18amu
Molarity of solution = 500ml
Solution
Mass of Solute (in gram ) 1
M 
Molecular mass of solute Volumeof solution (in dm 3 )

20 1
M   0.22M
180 0.5
3. Molality (m): - No. of moles of a solute present in one Kg of solvent is called
molality and the solution is called molal solution.
Mass of Solute (in gram )
Number of moles of Solute Molecular mass of Solute
m 
Mass of Solvent (in Kg ) Mass of Solvent (in Kg )
For Example:
If 10g of NaCl is dissolved in 800g of water, what will be the molal concentration
of solution.
Data:-
Mass in grams of solute = 10g
Molecular mass of solute (NaCl) = 23 + 35.5 = 58.5 amu
Volume of the solvent = 800g = 0.8 Kg
Molality of solution = ?
Solution:
Mass of solute (in gram ) 1
m 
Molecular mass of Solute Mass of solvent in Kg
10 1
m   0.214m
58.5 0.8

Hydration
Definition: - The combination of water molecules to a substance without breaking O–
H bond in water; is called hydration.
Explanation: -
Those substances which are combined with water
molecules are called hydrated substances.
 The polar nature of water causes hydration.
 Ionic compounds dissolve into the water because of
hydration.
 Normally water molecules are associated with
cations but it is also noted that water can also
associate with anions.
 Cations associate with Oxygen water whereas anions
associate with hydrogen
Factors affecting hydration: -
1. Charge density: - Hydration ability α Charge density

Greater will be the charge density on ions, greater will be the attraction to the
water molecules to give high rate of hydration.
For example; order of hydration in Al, Mg and Na ions is; Al+3 > Mg+2 > Na+
1
2. Size of ion: - Hydration ability 
Size of ion
The ion having small size shows high rate of hydration due to closeness of
water molecules to the ionic nuclei.
 Water of crystallization: - The number of water molecules hydrated with an ion
is called water of crystallization. When aqueous solution of a salt is heated, water
(solvent) evaporates but some water Molecules remain attached with the ions.
These numbers of water molecules are called water of Crystallization.
Molecular Water of
Salts crystallization
Formula
Copper Sulfate penta hydrated CuSO4.5H2O 5
Copper Chloride tetra hydrated CuCl2.4H2O 4
Magnesium hydroxide hexa hydrated Mg(OH)2.6H2O 6
Sodium Carbonate deca hydrated Na2CO3.10H2O 10

Hydrolysis
 Definition: - The reaction of cation or anion (or both) of a salt with water
molecules to form an acid and a base is called hydrolysis.
Explanation: -
 All salts cannot react with water. Those which react they produce strong acid or
strong base. Due to the formation of acid and base, pH of the mixture changes.
2

 Change in pH of mixture shows that salt has reacted with water.

 If strong acid is produced the mixture becomes acidic (pH < 7) and if strong
base is produced the mixture becomes basic (pH > 7).
Examples: - Reaction of Ammonium Chloride (NH4Cl) with Water (H2O)
NH4Cl + H2O   NH4OH + HCl
Ammonium Water Ammonium Hydrochloric
Chloride Hydroxide Acid
(Acidic Salt) (Weak base) (Strong acid)
This reaction will be followed by the decrease in pH from 7 due to the formation of strong
acid (HCl).
Reaction of Sodium Carbonate (Na2CO3) with Water (H2O)
Na2CO3 + 2H2O   2NaOH + H2CO3
Sodium Water Sodium Carbonic
Carbonate Hydroxide Acid
(Basic Salt) (Strong base) (Weak acid)
This reaction will be followed by the increase in pH from 7 due to the formation of strong
base (NaOH).
Theory of ionization “OR” ionic theory “OR” Arrhenius theory of ionization
Introduction: - This theory was put forwarded by Swedish Chemist “Svante August
Arrhenius” in 1880 about the ionization of electrolytes on dissolving into the water.
Postulates: -
 The electrolytes on dissolving into the water, give electrically charged (–ve and
+ve) particles called ions. +ve from electropositive atoms and –ve from
electronegative atom. For example;
NaOH(g)  
H O
2
Na (aq ) + OH (aq )
NaCl(s) 
H 2O
Na (aq ) + Cl (aq )

 No. of electrical charges carried out by the ion is equal to valency of their atoms.
 The number of positive and negative charges on the ions must be equal so
that the solution as a whole remains neutral.
 In a solution ions are in the disorder motion.
 In solutions, the +ve and –ve ions combinetogether to give unionized molecules,
hence ionization is a reversible process.
FACTORS AFFECTING IONIZATION OF ELECTROLYTE
(i) Nature of electrolyte: - Degree of ionization (extent of ionization) depends upon
the nature of electrolyte. Strong electrolytes, e-g HCl, H2SO4, NaOH, KOH
etc, give maximum ionization whereas weak electrolytes-e.g CH3COOH, NH4OH
etc give less ionization.
(ii) Degree of dilution:- Ionization  1/Dilution (Amount of water)
Greater will be the amount of water, greater will be the volume for ions to move
hence they will not form unionized electrolyte.
(iii) Temperature:- Ionization  Temperature
At higher temperature, kinetic energy of electrolytic ions increase, hence they
move more frequently to stay away from one another.
Factors affecting Electrical conductivity of the electrolytic solution
(i) Number of ions present in the solution: -
1
Electrical conductivity Number of ions present in the solution

 Greater will be the ions into the solution, less will be the mobility (movement) of
ions into the solution; hence less electric current will move from the solution.
(ii) Speed (movility) of ions:
Electrical conductivity  Speed of ion present in the solution
Greater will be the speed (mobility) of ions into the solution, greater electric current
will pass from solution.
Limitations of theory of ionization: -
 This theory says that ions of an electrolyte move into the aqueous solution but this
theory does not tell us the interaction of solvent molecules with the ions of an
electrolyte (Hydration).
 This is mostly applicable on strong electrolytes. It does not explain clearly the
behavior of weak electrolytes in water.
Difference between weak and strong electrolytes
Strong electrolytes Weak Electrolytes
Allow a large amount of electricity ti flow Allow a small amount of electricity to flow
through them. through them.
Are completely dissociated. Are party dissociated.
Solutions contain only free mobile ions. Partly ionized and partly unionized
molecules are present.
Examples Examples
Acids – HCl, HNO3 Acids – Acetic, Oxalic
Bases – NaOH, KOH solution Bases – NH4OH
Salts – CuCl, PbBr2 Salts – Na2CO3, NaHCO3
Colligative properties: - Those properties of solution that depends upon the amount
of solute are called Colligative properties. For example; Elevation in boiling point,
depression in freezing point, lowering of vapor pressure, osmosis and etc.
Conductance of electric current through solution
Electrical conductance from thr electrolytic solutions depends upon the following factors.
(i) Degree of dilution: - Electrical conductance α Dilution (Amount of water)
Greater will be the amount of water, greater will be the volume for ions to move
hence the ions will carry more electrical current into the solution.
(ii) Absolute velocity of the ions: - Electrical conductance α Absolute velocity of the
ions Greater will the absolute velocity
Electrolysis
Definition: - The movement of ions towards their electrodes by passing electric current
through electrolytic solution is called electrolysis.
Explanation: - An electrolytic solution contains cations (+ve ions) and anions (-ve
ions); when electric current is passed from their solution, these ions become mobile
and move towards opposite charged metal plate (electrodes) where they become
neutralized by gaining or losing electron(s). This whole process is carried out in an
electrolytic cell.
  Electrolytic cell is s device in which electrolysis of electrolytic solution is carried
out. It contains two types of metal plates; cathode (+ve plate) and anode (–ve plate)
to carry the neutralized atoms.
Examples: -
Electrolysis of CuCl2
CuCl2(g) 

H 2O
Cu aq2 + 2Cl (aq )
At Cathode: - Cu (aq2 ) + 2e-  Cu(g)
At Anode: - 2Cl (aq )  Cl2(g) + 2e-
Overall reaction: - Cu (aq2 ) + 2Cl (aq )  Cu(g) +
Cl2(g)

Difference between Anode and Cathode

Anode Cathode
Connected to the positive terminal of the battery Connected to the negative terminal of the battery
Acquires positive charge during electrolysis Acquires negative charge during electrolysis
Migration point for anions Migration point for cations
Oxidation Number (O.N): - The (unreal) formal charge on the atom in the compound
is called oxidation number or oxidation state.
Groups Name O.N Groups Name O.N
SO4–2 Sulfate –2 PO4–3 Phosphate –3
CO3–2 Carbonate –2 C2O4–2 Oxalate –2
–1 –2
HCO3 Bicarbonate –1 CrO4 Chromate –2
– –2
MnO4 Permanganate –1 Cr2O7 Dichromate –2
Example: - Give the oxidation numbers of Phosphorous, Carbon and Sulfur in
PO 43 , CO 32 , SO 42 respectively.
Oxidation number of Phosphorous in PO 43
Oxidation number of P + Oxidation number of O4 = –3
Oxidation number of P + (–2)  4 = –3
Oxidation number of P – 8 = –3
Oxidation number of P = –3 + 8
Oxidation number of P = +5
Oxidation number of Carbon in CO 32
Oxidation number of C + Oxidation number of O3= –2
Oxidation number of C + (–2)  3 = –2
Oxidation number of C – 6 = –2
Oxidation number of C = –2 + 6
Oxidation number of C = + 4
Oxidation number of Sulfur in SO 42
Oxidation number of S + Oxidation number of O4 = –2
Oxidation number of S + (–2)  4 = –2
Oxidation number of S – 8 = –2
Oxidation number of S = –2 +8
Oxidation number of S = + 6
Oxidation and Reduction reactions
Oxidation and reduction reactions can be defined in the four following ways:

On the basis of Oxidation Reduction

Electron Loss of electron is called oxidation. Gain of electron is called reduction.
Oxygen Gain of oxygen is called oxidation. Loss of oxygen is called reduction.
Hydrogen Loss of Hydrogen is called oxidation. Gain of Hydrogen is called reduction.

Redox reactions: - Those reactions in which both oxidation and reduction are going on
simultaneously. For example;
MnO 41 + Fe+2  Mn+2 + Fe+3
Here Mn is reducing due to decrease in its oxidation number from +7 to +2.
Fe is oxidizing due to increase in its oxidation number from +2 to +3.
pH
Definition: - The reciprocal of the log of hydrogen ion concentration is called p H .
It is abbreviated from “Power of Hydrogen”.
Mathematically: -
pH = – log [H+] and pOH = – log [OH-]
Explanation: - p H is represented in the form of a scale called p H scale. Its values are
from 0 to 14.
Prove that pH + POH = 14
Dissociation of water is;
H2O  H+ + OH-
By applying law of mass action;

Kc 
H OH 
 

H O
2

Kc [H2O] = [H+] [OH–]

Kw = [H+] [OH-] (Kw = Dissociation of water = 1  10-14)
By putting this value in above equation,
1  10-14 = [H+] [OH-]
By taking –log at both sides; we get’  We know that; log a  b = log a + log b
– log 1  10 = –log ([H+] [OH-])
-14

– (–14) = (–log [H+]) + (–log [OH-])

14 = pH + pOH
pH + pOH = 14
pH Scale:-
The solution having pH below 7 (0 to 6.9) is acidic solution and the solution having
pH above 7 (7.1 to 14) is basic.
0  7.0  14
Acid Neutral Base
PH of few common solutions: -
Solution Distille
 HCl H2SO CH3COO Milk d Blood Sea Na2CO
PH 1.0 41.2 H 2.9
6.6 7.0 7.3 Water
7.9 to 3 11.6
 Water 8.4
Solution Distilled Sea
HCl H2SO4 CH3COOH Milk Blood Na2CO3
 Water Water
PH 7.9 to
1.0 1.2 2.9 6.6 7.0 7.3 11.6
 8.4

What will be the pH of HCl whose Find the pH of solution of Ba(OH)2 whose
pOH is 11 pH is 12.
pH + pOH = 14 pH + pOH = 14
pH = 14 – pOH pOH = 14 – pH
pH = 14 – 11 pOH = 14 – 12
pH = 3 pOH = 2
Find out the pH of 0.001 M solution Find out the pOH of 0.1M solution of NaOH.
of HCl. NaOH  Na+ + OH-
HCl  H+ + Cl- 0.1M 0.1M 0.1M
0.001M 0.001M 0.001M pOH = – log [OH ]
-

pH = – log [H ]
+
pOH = – log (0.1)
pH = – log (0.001) pOH = – (–1)
pH = – (–3) pOH = 1
pH = 3
Find out the pOH of 0.2 M solution of Find out the pH of 0.01M solution of
H2SO4 Ca(OH)2
H2SO4  2H+ + SO 42 Ca(OH)2  Ca+2 + 2OH-
0.2M 2x0.2 0.2M 0.01M 0.01M 2x0.01M
0.4M 0.02M
First we will calculate pH. First we will calculate pOH.
pH = – log [H+] pOH = – log [OH-]
pH = – log (0.4) pOH = – log (0.02)
pH = – (–0.398) pOH = – (–1.699)
pH = 0.398 pOH = 1.7
Now we will calculate pOH. Now we will calculate pH.
pH + pOH = 14 pH + pOH = 14
pOH = 14 – PH pH = 14 – pOH
p O H = 14 – 0.398 pH = 14 – 1.7
pOH = 13.6 pH = 12.3
 Buffer “OR” Buffer solution

Definition: - A solution which does not change its pH by the addition of small amount
of an acid or base is called buffer or buffer solution.
Types of buffer: - There are two types of buffer solutions.
1. Acidic buffer 2. Basic buffer
Formation: - When an acid or base is added to the solution of its salt, the buffer is
formed. Generally weak acids or bases are used for this purpose.
 Acidic buffer is formed by mixing of an acid with its salt. For example;
CH 3 COOH  CH 3COO  Na  
   Acidic buffer
Acetic buffer Sodium acetate 
 Basic buffer is formed by the mixing of a base with its salt. For example;
NH 4 OH  NH 4 Cl 
   Basic buffer
Ammonium Hydroxide Ammonium Chloride 
Neutralization

Definition: - The reaction between acid and base to form salt and water is called
neutralization. Explanation: - When an acid (pH = < 7) is mixed with a base (pH > =
7), the solution becomes neutral (pH = 7) due to the formation of a salt and water.
 Salt is produced by the combination of cation from base and anion from acid.
 Water is produced by the combination of H+ from acid and OH– from base.
Example:- Reaction between HCl and NaOH

HCl  NaOH  NaCl  H 2O

Hydrochlor ic Acid Sodium Hydroxide Sodium Chloride Water
Types of neutralization: - There are two types of neutralization;.
 Partial neutralization: If acid and/or base are weak in nature, they show partial
neutralization and the produced salt is partial neutralized.
Step # 1 (Partial Neutralization):
H 2SO 4  NaOH  NaHSO 4  H 2O
Sulfuric acid Sodium hydroxide Sodium Bisulfate (Acidic salt ) Water
Step # 2 (Complete Neutralization):-
NaHSO 4  NaOH  Na 2SO 4  H 2O
Sodium bisulfate Sodium hydroxide Sodium Sulfate ( Normal salt ) Water
 Complete neutralization: - If acid and base both are strong, they show complete
neutralization. The produced salt in complete neutralization will have a cation and
anion, no free H+ or OH– ion will be there in the salt, such salt is called normal
salt.
Step # 1 (Partial Neutralization):
H 2SO 4  NaOH  NaHSO 4  H 2O
Sulfuric acid Sodium hydroxide Sodium Bisulfate (Acidic salt ) Water
Step # 2 (Complete Neutralization):-
 NaHSO 4  NaOH  Na 2SO 4  H 2O
Sodium bisulfate Sodium hydroxide Sodium Sulfate ( Normal salt ) Water

Electrode potential or Half Cell Potential

Definition: - The potential difference produced when an electrode is placed into the
solution of its own salt is called electrode potential.
Symbol: - “E”
Types of electrode potential: - There are two types of electrode potential.
1. Oxidation potential (Eox): - The potential difference produced by the oxidation at
the electrode when it is placed into the solution of its own salt is called oxidation
potential.
2. Reduction potential (Ered): - The potential difference produced by the reduction
at the electrode when it is placed into the solution of its own salt is called reduction
potential.
 Standard Electrode Potential (0E): - The potential difference produced when an
electrode is placed into its one molar solution of its own salt at 250C is called
standard electrode potential.
Types of reactions on the basis of electrode potential
On the basis of electrode potential, reactions are classified into following two
types.
1. Spontaneous reaction: - Reaction at that electrode which has positive potential
value is called spontaneous reactions.
2. Non-spontaneous reaction: - Reaction at that electrode where electrode
potential is negative, is called non-spontaneous reaction.
Indicator
Definition: - The chemical compound that represents end point of a reaction is called
indicator.
End point is the point of a reaction at which reactions completes.
Explanation: - Indicators are the weak acids or bases; they change their color by
dissociation into their ions at a certain range of pH.
Color of indicators in acidic and basic solutions: -

Color in
Indicators PH Range Acidic solution Basic solution
Phenolphthalein 8.3 – 10.0 Colorless Red
Methyl Orange 3.1 – 4.4 Red Orange
Methyl Red 4.2 – 6.3 Red Yellow
Litmus 5.0 – 8.0 Red Blue

Behavior of indicators: - Indicators show change in colour by dissociation into ions.

Dissociation of Methyl Orange

 Dissociation of Phenolphthalein

Types of Solution:- There are following nine types of solutions are there.

No. Solute Solvent Examples

1 Gas Gas Air, Natural gas etc
2 Liquid Gas Fog (Water vapors in air) etc
3 Solid Gas Smoke (Carbon particles) in air etc
4 Gas Liquid Cold drinks; For example Coca Cola, Pepsi etc
5 Liquid Liquid Petrol, Dilute Sulfuric acid etc
6 Solid Liquid Sugar or salt in water etc
7 Gas Solid Bricks, Biscuits, Foam etc
8 Liquid Solid Pastes, Gels etc
9 Metal alloys; For example Satin less steel that is the
Solid Solid
mixture of Copper, Aluminum and Iron etc
 CHAPTER 8

INTRODUCTION TO CHEMICAL KINETICS

CHEMICAL KINETICS

The branch of physical chemistry which deals with the study of reactions and effect of
different factors is known as chemical kinetics.

Types of Reaction:

The chemical reactions are classified on the basis of reaction rates. There are three types
of reactions:

i. Fast reaction
ii. Slow reaction
iii. Moderate reaction

i. Faster Reaction:

All ionic reactions are very fast reaction. These reactions are instantaneous reaction.
Their rate cannot be determined, for examples precipitation and neutralization
reaction are very fast reactions.

HCl + NaOH  NaCl + H2O

Acid base

AgNO3(aq) + NaCl(aq)  AgCl + NaNO3(aq)

ii. Slow Reaction:

Those reactions which take very long time for completion they have very slow
speed. It is difficult to determine experimentally velocity of such reaction.

For examples:

o
C2H4 800
 C
 C2 H2 + H2

2SO2 + O2 
 2SO3

Reactions occurring in the earth’s crust takes many years to complete.

ii. Moderate Reaction:

 Those reactions which proceed at experimentally of measurable rate are known as
moderate speed reaction. Generally reactions of organic and covalent compounds
are of such type.

For example:

C12 H22 O11 + H2 O  C6 H12 O6 + C6 H12 O6

Sucross glucose glucose

CH3 COOH + C2H5 OH  CH3 COOC2 H5 + H2O

Acetic acid Ester

Rate of Reaction:

Rate of reaction is defined as:

“The rate of reaction is the rate of decrease in the concentration of a reactant, or the
rate of increase in the concentration of a products”.

The concentration of reactants decrease with time and the concentration of products
increases with time.

Increase in the concentrat ion of products or decrease in the concentrat ion of reac tan ts
Rate =
Time taken for change

Consider a general chemical reaction:

A 
 B

Above graph shows rate of reaction changes with time. Initially the rate of appearance of
product [B] or rate of disappearance of reactant [A] is fast, after some time it falls. Overall
rate of reaction is known as average rate of reaction.

Velocity of Reaction:

Rate of reaction is defined as:

“The rate of reaction at a particular given moment i.e. at a specific time is know as
velocity of reaction.”

dx
Velocity of Reaction =
dt

Where;
dx = change in concentration
dt = very small interval of time

Velocity of reaction may also be termed as instantaneous rate of reaction

Units of Rate of Reaction:

The concentration is usually expressed in moles / dm3 and time in second.

Change in concentrat ion

Rate of reaction =
Time taken for change

moles / dm 3 mole 1
 3
 3
  moles (dm 3 ) 1 s 1
dm dm s

Rate Constant and Rate Expression:

According to law of Mass action:

“The rate of reaction is directly proportional to the active mass (molar concentration)
of reactants”

Consider a reaction:

A+B 
 C

Thus the rate or velocity of reaction:

Velocity of reaction  [A] [B]

dx
[A] [B]
dt

dx
 k [A] [B]
dt

This expression is known as rate expression and k is called as rate or velocity constant. If
the concentration of reactants are unit.

A = 1 mol / dm3
 B = 1 mol / dm3
Then:
dx
 k [ I] [ I]
dt
dx
k
dt

The k is called as specific rate constant.

Energy of Activation:

“The minimum amount of energy which molecules must have to form an activated
complex is called activation energy”.

OR

“The minimum amount of energy in addition to average energy required to convert the
reactants into products.

According to kinetic molecular theory reactants molecules undergo constant and random
motion. Acording to collision theory chemical reaction occur as a result of collision
between reactants molecules. If two molecules one to react chemically they formed a
complex. This activated complex than dissociates into products thus only an effective
molecular collision can result in the formation of a product.

A B A B A B
+   +
A B A B A B
Reactants Complex state Products

The value of activation energy is much greater than the average kinetic energy of the
molecules. The reaction therefore, does not take place. But if same molecules acquire
energies more than the average kinetic energy then there molecules do react and formed
activated complex which dissociates into products.

When a catalyst is used the energy of activation is lowered. The energy of activation is
usually expressed in joules and kilo joules.

FACTORS AFFECTING RATE OF REACTION

There are following five factors which strongly influence the rates of reaction.

i. The concentration of reactants

ii. The nature of reactants.
iii. The temperature for the system.
iv. The presence of catalyst
v. Surface area of reactants

i. The Effect Concentration of Reactants:

According to law of Mass Action.

“The rate of chemical reaction is proportional to the product of molar

concentration of the reacting substance.”

The greater the number of molecules of the reacting substance per unit volume the
faster the reaction will proceed. This is because with the increase in concentration.
So as we increase the concentration effective collision will be increased.

ii. The Nature of the Reactants:

Activation energy is different for different reacting substances. Ionic reactions are
very fast and molecular reaction occurs slowly. So the rates of reaction are highly
dependent upon the nature of reactants.

Examples:

2NO + O2 fast
 2NO2

2CO + O2 slow
 2CO2

iii. The Temperature of the System:

At high temperature effective collision increases so the rate of reaction generally

increases with rise in temperature. Generally at 10oC in temperature approximately
 doubles the reaction rate the reasons are:

1. The velocity of molecules increase when temperature increases, this results

in the increase of frequency of collision.
2. The kinetic energy of each molecule also increase, the fraction of the
molecules possessing threshold or activation energy becomes doubles, as a
result number of effective collisions are also double, hence rate is double.

iv. The Presence of Catalyst:

“A catalyst is a substance which alters the rate of a chemical reaction without

itself being consumed in the process.”
Catalysts are of two types:
a. Positive catalysts:

In the presence of these catalysts the rate of reaction increase. Positive catalyst
provided an alternative path way of lowering energy o activation. As a result more
reactants molecules posses the energy required for a successful collision. So
effective collision increases, thus the rate of reaction increased.
For example:

Vanadium pentaoxide is used as a catalyst for the oxidation of Sulphur dioxide to

sulphur trioxide.


VO
2SO2 + O2 2 5
2SO3
b. Negative catalyst:

In the presence of negative catalyst the rate of reaction decreases, because energy
of activation does not decreases by the addition of them.

Negative catalyst combine with reactant molecules so number of colliding reactant

molecules decreases and effective collision also decreases so resultant rate of
reaction decreases. Negative catalyst also known as inhibitors.

v. Surface Area of Reactant:

When surface area of the reactants increase the rate of reaction also increases in a
heterogeneous reactions. For example reaction between pieces of marble (CaCO3)
and an aid is slow.

CaCO3 + 2HCl 
 CaCl2 + H2O + CO2

But powder marble reacts with vigorously because the powdered marble has greater
surface area for HCl to act upon.

Order of the Reaction:

Order of reaction is the sum of exponents in general rate equation:
aA + bB  C

Rate of reaction = K [A]a [B]b ------------ (i)

Order of reaction = (a + b)

Equation number (1) shows the relationship between the concentration of the
reacting substance involved in the reaction and the rate is called “Rate Expression”.
For a reaction the minimum order of reaction may be zero and maximum upto three
order.

For example:

First order reaction:

1
N2 O5   2NO2 + O2(g)
2
dx
 K [N2O5]
dt
The order of reaction is first

Second order reaction:

2CH3 CHO 
 2CH4 + 2CO

dx
 K [CH3CHO]2
dt

The order of reaction is second.

Third order reaction:

2NO + O2  2NO3

dx
K [NO]2 [O2]
dt

The order of reaction is third.