• Dalton’s Atomic Theory

In 1808, Dalton published ‘A New System of Chemical Philosophy’ in which he proposed the
following:
1. Matter consists of indivisible atoms.
2. All the atoms of a given element have identical properties including identical mass. Atoms of
different elements differ in mass.
3. Compounds are formed when atoms of different elements combine in a fixed ratio.
4. Chemical reactions involve reorganisation of atoms. These are neither created nor destroyed in a
chemical reaction.
• Atomic Mass
The atomic mass of an element is the number of times an atom of that element is heavier than an
atom of carbon taken as 12. It may be noted that the atomic masses as obtained above are the
relative atomic masses and not the actual masses of the atoms.
One atomic mass unit (amu) is equal to l/12th of the mass of an atom of carbon-12 isotope. It is also
known as unified mass.
Average Atomic Mass
Most of the elements exist as isotopes which are different atoms of the same element with different
mass numbers and the same atomic number. Therefore, the atomic mass of an element must be its
average atomic mass and it may be defined as the average relative mass of an atom of an element
as compared to the mass of carbon atoms (C-12) taken as 12w.
Molecular Mass
Molecular mass is the sum of atomic masses of the elements present in a molecule. It is obtained by
multiplying the atomic mass of each element by number of its atoms and adding them together.
For example,
Molecular mass of methane (CH4)
= 12.011 u + 4 (1.008 u)
= 16.043 u
Formula Mass
Ionic compounds such as NaCl, KNO3, Na2C03 etc. do not consist of molecules i.e., single entities but
exist “as ions closely packed together in a three dimensional space.
In such cases, the formula is used to calculate the formula mass instead of molecular mass. Thus,
formula mass of NaCl = Atomic mass of sodium + atomic mass of chlorine
= 23.0 u + 35.5 u = 58.5 u.
• Mole Concept
It is found that one gram atom of any element contains the same number of atoms and one gram
molecule of any substance contains the same number of molecules. This number has been
experimentally determined and found to be equal to 6.022137 x 1023 The value is generally called
Avogadro’s number or Avogadro’s constant.
It is usually represented by NA:
Avogadro’s Number, NA = 6.022 × 1023

Limiting Reactant/Reagent
Sometimes, in alchemical equation, the reactants present are not the amount as required according
to the balanced equation. The amount of products formed then depends upon the reactant which has
reacted completely. This reactant which reacts completely in the reaction is called the limiting
reactant or limiting reagent. The reactant which is not consumed completely in the reaction is called
excess reactant.

.
 Differentiate between Molarity and Molality:
Molarity Molality
1. Molarity of solution is defined as the total no. of Molality is defined as the total moles of a solute
moles of solute present per litre of solution. present per kilogram of solvent.
2. Mathematical expression is 2. The mathematical expression is
M = number of moles of the solute /Volume of m = Numbers of moles of solute/Mass of solvent in Kg.
solution in litres. ✕✕✕✕m=(g✕1000)(W✕m)
M=nV
3. Molarity has a unit of mol L-1. 3. Molality has a unit of mol Kg-1.
4. It depends on the volume of the solution. 4. It depends on the mass of the solvent.
5. Molarity is affected by the change in temperature. 5. Molality has no effect on temperature.

Photoelectric Effect

When light of a suitable frequency is allowed to incident on a metal, ejection of electrons take place.
This phenomenon is known as photo electric effect.

Observations in Photoelectric Effect

1. Only photons of light of certain minimum frequency called threshold frequency (v 0) can
cause the photoelectric effect. The value of v0 is different for different metals.
2. The kinetic energy of the electrons which are emitted is directly proportional to the
frequency of the striking photons and is quite independent of their intensity.
3. The number of electrons that are ejected per second from the metal surface depends
upon the intensity of the striking photons or radiations and not upon their frequency.

Planck's Theory

According to this theory, energy cannot be absorbed or released continuously but it is emitted or
released in the form of small packets called quanta. In case of light this quanta is known as photon.
This photon travels with speed of light. Energy of the photon is directly proportional to frequency. h
is Planck's constant, value is 6.62 × 10–34 Js

E∝ν
E=hν

Bohr’s Model:- Niels Bohr in 1913, proposed a new model of atom on the basis of Planck’s
Quantum Theory. The main points of this model are as follows:

Atom is of spherical shape having size (of order 10–10 metre).

Whole mass is concentrated in centre called nucleus (having order of size 10–15 metre).

Electron revolves around nucleus only in limited circular path and he assumed that electron does not
radiate energy during its revolution in permitted paths.

When electron absorbs energy, it jumps to higher orbit and when it comes back, it radiates energy.
This postulate explain spectra.

Achievements of Bohr’s Theory

1. Bohr’s theory has explained the stability of an atom.

2. Bohr’s theory has helped in calculating the energy of electron in hydrogen atom and
one electron species.
3. Bohr’s theory has explained the atomic spectrum of hydrogen atom.

Limitations of Bohr’s Model

The theory could not explain the atomic spectra of the atoms containing more than one electron or
multielectron atoms.

Bohr's theory failed to explain the fine structure of the spectral lines.

Bohr’s theory could not offer any satisfactory explanation of Zeeman effect and Stark effect.

Line Spectrum of Hydrogen Atom

When electric discharge is passed through hydrogen gas enclosed in discharge tube under low
pressure and the emitted light is analysed by a spectroscope, the spectrum consists of a large
number of lines which are grouped into different series. The complete spectrum is known as
hydrogen spectrum.
On the basis of experimental observations, Johannes Rydberg noted that all series of lines in the
hydrogen spectrum could be described by the following expression:

wave number = 1/λ= R(1/n21−1/n22)

R = Rydberg constant R = 109678 cm–1

. Pauli’s exclusion principle

According to this principle, in an atom, no two electrons have same value of all the four quantum
numbers. In the same orbital, electron always accommodate in opposite spins. An orbital can have a
maximum of two electrons, with opposite spin.

Heisenberg’s Uncertainty Principle

It states that, "It is impossible to measure simultaneously the exact position and exact
momentum of a microscopic particle".

If uncertainty in position = Δx and

Uncertainty in momentum = ΔY

When both are measured simultaneously, According to this principle,

ΔX . ΔY ≥h/4π

Octet Rule
Atoms of different elements take part in chemical combination in order to complete their octet
or to attain the noble gas configuration.

• Dipole Moment
Due to polarity, polar molecules are also known as dipole molecules and they possess dipole
moment. Dipole moment is defined as the product of magnitude of the positive or negative
charge and the distance between the charges.

• The Valence Shell Electron Pair Repulsion (VSEPR) Theory

Sidgwick and Powell in 1940, proposed a simple theory based on repulsive character of
electron pairs in the valence shell of the atoms. It was further developed by Nyholm and
Gillespie (1957).
Main Postulates are the following:
(i) The exact shape of molecule depends upon the number of electron pairs (bonded or non
bonded) around the central atoms.
(ii) The electron pairs have a tendency to repel each other since they exist around the central
atom and the electron clouds are negatively charged.
(iii) Electron pairs try to take such position which can minimize the rupulsion between them.
(iv) The valence shell is taken as a sphere with the electron pairs placed at maximum
distance.
(v) A multiple bond is treated as if it is a single electron pair and the electron pairs which
constitute the bond as single pairs.

Change in Internal Energy by Transfer of Heat

Internal energy of a system can be changed by the transfer of heat from the surroundings to
the system without doing work.
Δu = q
Where q is the heat absorbed by the system. It can be measured in terms of temperature
difference.
q is +ve when heat is transferred from the surroundings to the system. q is -ve when heat is
transferred from system to surroundings.
When change of state is done both by doing work and transfer of heat.
Δu = q + w
First law of thermodynamics (Law of Conservation of Energy). It states that, energy can
neither be created nor be destroyed. The energy of an isolated system is constant.
Δu = q + w.
• Work (Pressure-volume Work)
Let us consider a cylinder which contains one mole of an ideal gas in which a frictionless
piston is fitted.

• Work Done in Isothermal and Reversible Expansion of Ideal Gas

Relation Between Cp and Cv for an Ideal Gas

At constant volume heat capacity = Cv
At constant pressure heat capacity = Cp
At constant volume qv= CvΔT = ΔU
At constant pressure qp = Cp ΔT = ΔH
For one mole of an ideal gas
ΔH = ΔU + Δ (PV) = ΔU + Δ (RT)
ΔH = ΔU + RΔT
On substituting the values of ΔH and Δu, the equation is modified as
Cp ΔT = CvΔT + RΔT
or Cp-Cv = R

Hess’s Law of Constant Heat Summation

The total amount of heat evolved or absorbed in a reaction is same whether the reaction
takes place in one step or in number of steps.
Spontaneous Process: A process which can take place by itself or has a tendency to take
place is called spontaneous process.
Spontaneous process need not be instantaneous. Its actual speed can vary from very slow to
quite fast.
A few examples of spontaneous process are:
(i) Common salt dissolves in water of its own.
(ii) Carbon monoxide is oxidised to carbon dioxide of its own.
• Entropy (S)
The entropy is a measure of degree of randomness or disorder of a system. Entropy of a
substance is minimum in solid state while it is maximum in gaseous state.
The change in entropy in a spontaneous process is expressed as ΔS

Gibbs Energy and Spontaneity

A new thermodynamic function, the Gibbs energy or Gibbs function G, can be defined as G =
H-TS
ΔG = ΔH – TΔS
Gibbs energy change = enthalpy change – temperature x entropy change ΔG gives a criteria
for spontaneity at constant pressure and temperature, (i) If ΔG is negative (< 0) the process
is spontaneous.
(ii) If ΔG is positive (> 0) the process is non-spontaneous.

Henry’s law: The solubility of a gas in a liquid at a certain temperature is governed by

Henry’s law. It states that the mass of a gas that dissolves in a given mass of a solvent at
any temperature is proportional to the pressure of the gas above the surface of the solvent.

The Bronsted-Lowry Acids and Bases

According to Bronsted-Lowry, an acid is a substance which is capable of donating a
hydrogen ion H+ and bases are substances capable of accepting a hydrogen ion H+.
In other words, acids are proton donors and bases are proton acceptors

Lewis Acids and Bases

According to Lewis, acid is a substance which accepts electron pair and base is a substance
with donates an electron pair.
Electron deficient species like AlCl3, BH3, H+ etc. can act as Lewis acids while species like
H20, NH3 etc. can donate a pair of electrons, can act as Lewis bases.
Le Chatelier’s principle: It states that the change in any factor such as temperature,
pressure, concentration etc., will cause the equilibrium to shift in such a direction so as to
reduce the effect of the change

Arrhenius Concept: According to Arrhenius, acids give hydrogeneous while bases produce
hydroxyl ions in their aqueous solution.

Conjugate base and Conjugate acid: When a Bronsted-Lowry acid reacts with a base it
produces its conjugate base and conjugate acid.

Electron Displacement Effects in Covalent Bonds: Electronic displacements in covalent

bonds occurs due to the presence of an atom or group of different electronegativity or under
the influence of some outside attaching group.
These lead to a number of effects which are as follows:
(i) Inductive effect (ii) Elecromeric effect
(iii) Resonance or Mesomeric effect (iv) Hyperconjugation effect.
Inductive Effect: It involues c electron. The a electrons which form a covalent bond are
seldom shared equally between the two atoms. Due to different electronegatively electrons
are displaced towards the more electronegative atom. This introduces a certain degree of
polarity in the bond. The more electronegative atom acquires a small negative charge (δ –).
The less electronegative atom acquires a small positive charge (δ+).

Resonance Effect: The polarity produced in the molecule by the interaction of two π-bonds
or between a π-bond and a lone pair of electrons present on an adjacent atom. There are
two types of resonance or mesomeric effects designated as R or M effect.

Electromeric Effect (E Effect):

The electrom’eric effect refers to the polarity produced in a multiple bonded compound when
it is attacked by a reagent when a double or a triple bond is exposed to an attack by an
electrophile E+ (a reagent) the two π electrons which from the π bond are completely
transferred to one atom or the other.

Dumas method: This method is based on fact that the nitrogenous compounds when
heated with copper oxide in an atmosphere of carbon dioxide yield free nitrogen,

Kjeldahl’s Methods: Kjeldahl’s method is based on the fact that when an organic
compound containing nitrogen is heated with con. H2S04 the nitrogen in it is converted to
ammonium sulphate. The resultant liquid is then treated with excess of alkali and the
liberated ammonia gas absorbed in excess of standard acid. The amount of ammonia is
determined by finding the amount of acid neutralised by back filtration with some std. alkali.

Alicyclic Compounds: Compounds containing closed ring of carbon compounds.

Aromatic Compounds: Benzene and its derivatives are called aromatic compounds.
Functional group: A functional group is an atom or group of atoms bonded together in a
unique fashion and which determines the physical and chemical properties of the
compounds.
Heterocyclic Compounds
Cyclic compounds in which the ring atoms are of carbon and some other element (For
example, N, S, or O) are called heterocyclic compounds. Aromatic Hydrocarbons
These hydrocarbons are also known as ‘arenes’. Most of such compounds were found to
contain benzene ring.
Aromatic compounds containing benzene ring are known as benzenoids and those not
containing a benzene ring are known as non-benzenoids. Some examples of arenes are
given below.

Structure of Benzene: By elemental analysis, it is found that molecular formula of benzene

is C6H6. This indicates that benzene is a highly unsaturated compound. In 1865, Kekule gave
the cyclic planar structure of benzene with six carbons with alternate double and single
bonds

Resonance Structure of Benzene: The phenomenon in which two or more structures can
be written for a substance which involve identical positions of atoms is called resonance. In
benzene’s Kekule’s structures (1) and (2) represent the resonance structures. Actual
structure – of the molecule is represented by hybrid of the these two structures.

Aromaticity: It is a property of the sp2 hybridized planar rings in which the p orbitals allow
cyclic delocalization of π electrons.
Conditions for Aromaticity:
(i) An aromatic compound is cyclic and planar.
(ii) Each atom in an aromatic ring has a p orbital. These p orbitals must be parallel so that a
continuous overlap is possible around the ring.
(iii) The cyclic π molecular orbital (electron cloud) formed by overlap of p orbitals must
contain (4n + 2) π electrons. Where n = integer (0, 1, 2, 3, etc.).

Physical Properties of Benzene:

(i) Benzene is a colourless liquid.
(ii) It is’ insoluble in water. It is soluble in alcohol, ether, chloroform etc.
(iii) Benzene itself is a good solvent for many organic and inorganic substances e.g., fat,
resins, sulphur and iodine.
(iv) It bums with a luminous, sooty flame in contrast to alkanes and alkenes which usually
bum with a bluish flame.