CHAPTER NO: 01 STOICHIOMETRY

INTRODUCTION
● Chemistry is the branch of science which deals with the properties, composition and the structure of matter.
● It also deals with the changes in matter and the principles which govern these changes.
ERRORS
● Error arise due to defect in the instrument or lacking in the handling the apparatus or improper functioning of the
instrument.
● There are two types of errors i.e. Systematic error and Random error.
● Systematic errors are caused by the defect in the analytical method or by the improper functioning of instrument.
● Systematic error is determinate and can be avoidable.
● The errors that the remaining variations indicate are called random errors.
● Random errors are indeterminate and unavoidable.
ATOMIC MASS
● Atomic mass is defined as the mass of one atom of the element compared with the mass of one atom of C¹².
● The atomic mass is ratio and hence had no unit.
● Generally atomic masses are expressed in amu.
● One amu equals exactly one twelfth the mass of a carbon-12 atom.
MOLECULAR MASS AND FORMULA MASS
● Molecular mass is defined as the sum of the atomic masses of the atoms of all elements present in a molecule
shown by its molecular formula.
● Formula mass is the sum of the atomic masses as given in the simplest (empirical) formula of the substance.
EMPIRICAL FORMULA
● The empirical formula is that formula which is found by experiment.
● It represents the simplest ratio of the combining atoms in a compound.
● The empirical formula doesn't represent the actual number of atoms in a molecule.
● There are some compounds which have same empirical and molecular formula i.e. MgO, NaCl, etc.
MOLECULAR FORMULA
● A formula that expresses not only the relative number of atoms of each elements but also the actual number of
atoms of each element in one molecule of the compound is called molecular formula.
● The molecular formula is an integral multiple of the empirical formula.
𝑴𝒐𝒍𝒆𝒄𝒖𝒍𝒂𝒓 𝑭𝒐𝒓𝒎𝒖𝒍𝒂 = (𝑬𝒎𝒑𝒊𝒓𝒊𝒄𝒂𝒍 𝑭𝒐𝒓𝒎𝒖𝒍𝒂) × 𝒏
STOICHIOMETRY
● Stoichiometry is taken from Greek, Stoicheion means element and metron means measurement.
● The study of the relationships between the amounts of the reactants and the products in chemical reactions as
given by chemical equations is called Stoichiometry.
● Stoichiometry deals with irreversible reactions.
● Stoichiometry is based on the assumptions that reactant molecules are completely converted into product and no
side reaction occurs.
● There are three relationships involved for the stoichiometric calculations i.e. Mass-Mass relationship, Mass-
Volume relationship and Volume-Volume relationship.
● Gay-Lussac's law: Gases react in the ratio of small whole numbers by volume under similar condition of
temperature and pressure.
● Molar Volume: The volume of one mole of a gas at standard temperature (273K) and pressure (1atm) is referred as
molar volume. Molar volume of all ideal gases at STP is 22.4dm³.
𝑴𝒐𝒍𝒂𝒓 𝑴𝒂𝒔𝒔
𝑴𝒐𝒍𝒂𝒓 𝑽𝒐𝒍𝒖𝒎𝒆 =
𝑫𝒆𝒏𝒔𝒊𝒕𝒚
MOLE AND AVOGADRO'S NUMBER
● Mole is Latin word which means heap or pile. It is SI unit use for measuring the amount of substance of specific
number of particles.
● A mole is defined as gram atomic mass or gram molecular mass or gram formula mass of any substance (atoms,
molecules, ions) which contains 6.02x10²³ particles.
● Mole represents the number of chemical entities in a fixed mass.
● The number of particles present in one mole of any substance is called Avogadro's number and its numerical
value is 6.02x10²³.
● The mass in grams of one mole of any pure substance is known as molar mass. The unit for molar mass is gram
per mole (g/mol).
● Atomic mass of atom is expressed in amu while mass of mole is expressed in grams.
● Interconversion of Mole and Mass;
𝑮𝒊𝒗𝒆𝒏 𝑴𝒂𝒔𝒔 (𝒈)
𝑵𝒐. 𝒐𝒇 𝑴𝒐𝒍𝒆𝒔 =
𝑴𝒐𝒍𝒂𝒓 𝑴𝒂𝒔𝒔 𝒐𝒇 𝑺𝒖𝒃𝒔𝒕𝒂𝒏𝒄𝒆

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 ● Interconversion of Mole and No.of Particles;
𝑵𝒐.𝒐𝒇 𝑷𝒂𝒓𝒕𝒊𝒄𝒍𝒆𝒔
𝑵𝒐. 𝒐𝒇 𝑴𝒐𝒍𝒆𝒔 =
𝑨𝒗𝒐𝒈𝒂𝒅𝒓𝒐′ 𝒔 𝑵𝒖𝒎𝒃𝒆𝒓
● Interconversion of Mole and Molar volume;
𝑽𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝑮𝒂𝒔 𝒐𝒄𝒄𝒖𝒑𝒊𝒆𝒅 𝒂𝒕 𝑺𝑻𝑷
𝑵𝒐. 𝒐𝒇 𝑴𝒐𝒍𝒆𝒔 =
𝑴𝒐𝒍𝒂𝒓 𝑽𝒐𝒍𝒖𝒎𝒆
LIMITING REACTANT
● The reactant which is entirely consumed first during chemical reaction is called limiting reactant or limiting
reagent.
● The reactant that is not completely consumed is often referred as excess reactant.
● Mathematically, limiting reactant is that which gives least number of moles of product in the chemical reaction.
YIELDS
● The maximum amount of product obtained by a balanced chemical reaction by using its limiting reactant is
known as Theoretical Yield.
● The actual amount of product which is formed in experiment is called Practical or Actual Yield.
● Actual Yield is always less than Theoretical Yield.
● The ratio of actual yield to theoretical yield is called Percent Yield.
𝑷𝒓𝒂𝒄𝒕𝒊𝒄𝒂𝒍 𝒀𝒊𝒆𝒍𝒅
𝑷𝒆𝒓𝒄𝒆𝒏𝒕𝒂𝒈𝒆 𝒀𝒊𝒆𝒍𝒅 = × 𝟏𝟎𝟎
𝑻𝒉𝒆𝒓𝒐𝒆𝒕𝒊𝒄𝒂𝒍 𝒀𝒊𝒆𝒍𝒅

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CHAPTER NO: 02 ATOMIC STRUCTURE
INTRODUCTION
● Leucippus and Democritus gave the idea that matter is composed of invisible, indivisible and infinite number of
building blocks called atomos (Greek: a means non and Tom means break).
● Aristotelian has concept that matter is composed of four elements, earth, water, air and fire.
● The modern atomic theory was introduced by John Dalton.
● Robert Andrew Millikan calculated the charge on electron by Oil drop experiment. According to him the charge on
-19
electron is 1.6x10 C.
● In 1911, Ernest Rutherford laid the foundation that the atom consists of extremely small charged region which he
called nucleus wherein the most of the mass of an atom is concentrated while electrons revolve in the extra
nuclear part.
SUBATOMIC PARTICLES AND THEIR CHARACTERISTICS
● The only electron, proton and neutron are considered to be the fundamental particles of an atom which play an
important role for determination of physical and chemical properties of elements.
● All atoms contain neutrons except protium (isotope of hydrogen).
1. Electrons
● The subatomic particle electron was discovered by J.J Thomson in 1897AD, while studying on cathode ray
experiment.
● He called the cathode rays beam as electrons.
● Electrons carry negative charge whose magnitude is equal to positive charge of protons.
● The mass of electron is nearly 1836 times less than proton and 1839 times less than neutron.
2. Protons
● Protons are positively charged subatomic particles which are located in the nuclei of all elements.
● They are discovered by Goldstein by using perforated cathode in Crook’s discharge tube.
● With respect to mass and charge, the protons of all elements are identical to each other.
● Atomic number of elements is related only to protons while mass number is the sum of protons and neutrons.
● About 99.94% mass of an atom exists in nucleus.
● Protons and electrons have same magnitude of charge but have different mass.
3. Neutrons
● The discovery of neutrons were made by James Chadwick in an artificial radioactivity experiment.
9 4 12 1
4Be + 2He → 6C + 0n (neutron)
● Neutrons are also the part of atomic mass but neutron has no charge.
● Neutrons of all elements have same nature and mass.
● Neutrons are slightly heavier than protons.
● They are no deflected by electric or magnetic field.
● The number of neutrons is determined by subtracting the number of protons from the mass number.
Properties of fundamental subatomic particles
Particles Mass (amu) Mass (gram) Relative Charge Electric Charge
-28 -19
Electron 0.00055amu 9.11x10 gram -1 -1.602x10 C
-24 -19
Proton 1.0073amu 1.673x10 gram +1 +1.602x10 C
-24
Neutron 1.0086amu 1.674x10 gram 0 0
BOHR’ATOMIC THEORY
● According to Rutherford, atoms form continuous spectrum but it was wrong. Actually atoms form line spectrum
which was defined by Neil Bohr.
● His atomic model was based on Planck’s theory.
● Electrons revolve around the nucleus in circular orbits situated at fixed distance from nucleus with definite
energy.
● As long as electrons remains in an appropriate orbit, it neither loses, nor gain energy. Hence each orbit has a
fixed energy level, however the energy of orbits increases with the increased distance from nuclei.
● During excitation, electron absorbs some quantized energy and jump from a lower energy orbit to an appropriate
higher energy orbit but when it returns back to lower energy orbit it emit quantized energy.
∆𝑬 = 𝑬𝟐 − 𝑬𝟏 = 𝒉𝒗
● Electron can move only in those orbits in which the angular momentum of electrons (mrv) is integral multiple of
nh/2π.
𝒏𝒉
𝒎𝒗𝒓 =
𝟐𝝅
● Calculation of Radius of atom;
𝒓 = 𝒂𝒐 𝒏𝟐 ∴ 𝒂𝒐 = 𝑩𝒐𝒉𝒓′ 𝒔 𝒓𝒂𝒅𝒊𝒖𝒔 = 𝟎. 𝟓𝟐𝟗 × 𝟏𝟎−𝟖 𝒄𝒎 𝒐𝒓 𝟎. 𝟓𝟐𝟗𝑨𝒐
●
th
Calculation of Energy of n orbital;
𝟏
𝑬 = −𝑲 ∴ 𝑲 = 𝟏𝟑𝟏𝟑𝑲𝑱/𝒎𝒐𝒍
𝒏𝟐

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 ● Calculation of Frequency;
𝑲 𝟏 𝟏
𝒇 = ((𝒏 𝟐
− (𝒏 𝟐
)
𝒉 𝟏) 𝟐)
● Calculation of wave number;
𝟏 𝟏 𝟏
̅=
𝒗 ( − (𝒏 ) ∴ 𝑹𝑯 = 𝟏𝟎𝟗𝟔𝟕𝟖𝒄𝒎−𝟏
𝑹𝑯 (𝒏𝟏 )𝟐 𝟐)
𝟐

● Bohr’s model is only applicable to hydrogen and those species which have single revolving electron around the
+ +2 +3
nucleus (He , Li , Be ). It could not explain the spectra of multi electrons systems like He, Li, Be, B, etc.
● According to Bohr's concept, electron revolves around nucleus in circular orbits. Later on, it was proved that
electron didn't move in single plane but in three dimensional spaces.
● According to Bohr's concept, the electron in an atom is located at a definite distance from the nucleus and
revolves with a definite velocity which is against the Heisenberg uncertainty principle.
● Bohr's theory explains only the particle nature of electron and didn't explain the wave nature of electron (de-
Broglie’s hypothesis).
SPECTRUM AND TYPES OF SPECTRUM
● Spectrum refers to the complete range of wavelength of electromagnetic radiations that a particular substance is
capable of either absorbing or emitting.
1. Continuous Spectrum
● A continues spectrum is a type of spectrum in which all wavelength of electromagnetic radiations are present
without any gap or interruptions. In simpler term, it contains all possible colors or wavelengths of light in a
particular range.
● The visible spectrum of light produced by sun is example of continuous spectrum containing of all colors
(VIBGYOR) ranging from violet (4000A°) to red (7000A°) with no gap in between.
2. Line Spectrum
● It is a type of spectrum which consists of distinct lines of colors. These lines are separated by dark background
and represent the specific wavelength of electromagnetic radiations emitted or absorbed by atom.
● Line spectrum serves as fingerprint that allows to identify the elements present in the sample.
● The absorption spectrum is formed when light passes through a gas and the gas atoms absorb specific
wavelength of radiations, this results in dark lines with a white background. An example of absorption spectrum
is the dark lines seen in the spectrum of sun which are caused by the absorption of light by gases in the sun’s
atmosphere.
● Emission line spectrum is produced when gas atoms are exited, typically by heat or electric discharge, this
spectrum consists of bright lines with dark background. Example of emission spectrum are neon light, florescent
dyes, firework, etc.
HYDROGEN SPECTRUM
● Hydrogens give emission line spectrum.
𝟏 𝟏 𝟏
̅=
𝒗 [ − (𝒏 ]
𝑹𝑯 (𝒏𝟏 )𝟐 𝟐)
𝟐

● Where;
-1
RH=Rydberg constant=109678cm
n1=lower energy level
n2=higher energy level
Series of the Hydrogen Spectrum
No: Series Region n1 n2
01 Lymen Ultraviolet 1 2, 3, 4…
02 Balmer Visible 2 3, 4, 5….
03 Paschen Near IR 3 4, 5, 6…
04 Bracket Mid IR 4 5, 6, 7…
05 P-fund Far IR 5 6, 7, 8…
PLANCK'S QUANTUM THEORY
● This theory was given by Max Plank to describe the emission and absorption of radiations.
● Atoms can't absorb or emit energy continuously.
● The absorption of emission of energy takes place in specified amounts called quanta. A quantum of light is often
called photon.
● The amount of energy of quantum is directly proportional to the frequency of the radiations emitted or absorbed
by the body.
𝑬 = 𝒉𝒇 ∴ 𝒉 = 𝑷𝒍𝒂𝒏𝒄𝒌′ 𝒔 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕 = 𝟔. 𝟔𝟐𝟓 × 𝟏𝟎−𝟑𝟒 𝑱𝒔𝒆𝒄
X-RAYS
● In 1895, Roentgen observed that when fast moving electrons (cathode rays) collide with metal anode in discharge
tube, highly penetrating short wavelength radiations are produced known as X-rays or Roentgen rays.
● Moseley used anodes of different elements and analyzed the wavelength of X-rays emitted from anode. On the
basis of wavelength there are two main types of spectral line of X-rays i.e. K-series and L-series.

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 ● K-series are produced by the elements having large atomic number. These spectral lines have short wavelengths
and high energy because there is big difference between two energy levels.
● L-series are produced by anodes having small atomic number. They have long spectral wavelength and low
energy because there is small difference between two energy levels.
● X-rays can be produced in a special type of discharge tube under 5000volt and 0.001mm.
● These are short wavelength and high energy electromagnetic radiations.
● The range of their wavelength lies between 0.1-10A°.
● They travel with the speed of light.
● X-rays travel in straight line.
● These rays are unaffected by electric or magnetic field.
● Initially, X-rays were used to assist in the setting of broken arm of a person.
● These are used for the analysis of metallic substance or bullets in flesh.
● Dentists use them to examine the defective or damaged teeth.
● These are used for destroying the cancer cells.
● In crystallography, these are used for the determination of structure of crystal.
MOSELEY'S LAW AND ATOMIC NUMBER
● Moseley studied on the wavelengths of X-rays produced from the anodes of 38 different elements from Aluminum
to Gold.
● He introduced the term atomic number of elements.
● The wavelength of X-rays is inversely proportional to atomic mass of anode OR the frequency of X-ray is directly
proportional to the atomic mass number.
● Moseley’s law states that the square root of the frequency is directly proportional to the atomic mass of elements.
√𝒗 ∝ (𝒁 − 𝒃) √𝒗 = 𝒂(𝒁 − 𝒃) ∴ (𝒂) 𝒂𝒏𝒅 (𝒃)𝒂𝒓𝒆 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕𝒔
RADIOACTIVITY
● The phenomenon of radioactivity was given by Henry Becquerel while working on uranium mineral called
pitchblende.
● The spontaneous distingeration of those elements having atomic number greater than 82 are called radioactivity.
● Marrie Curie and Pierre Curie isolated the radioactive components of the pitchblende mineral and separated two
new radioactive elements Polonium and Radium.
Properties of different radioactive radiations
Properties Alpha-particle Beta-particle Gamma-particle
Mass 4amu 0.00055amu Zero
Charge +2 -1 Neutral
Composition 2 protons and 2 neutrons Electrons Photons
Deflection Yes Yes No
Ionization power Highest Moderate Lowest
Penetration power Lowest Moderate Highest
th th th
Speed 1/10 -1/20 of light speed 9/10 of light speed Same as light speed
 Alpha-particle can blocked by a thin layer of paper or few centimeters of air.
● Beta-particle can blocked by thin sheet of aluminum or few meters of air.
● Gamma-particle can blocked by thick lead sheet or by concrete.
● Carbon-14 isotope is used to measure the age of fossils and artifacts.
QUANTUM NUMBERS AND ORBITALS
● An orbital is the region of three dimensional space around the nucleus where maximum probability of electron
finding is possible.
● Schrodinger through his wave equation calculated some mathematical integers which are called quantum
numbers. Quantum number is a numerical value that describe energy levels, sublevels and orbitals available for
electrons.
1. Principal Quantum Number
● The principal quantum number describes the size and energy of an orbital.
● It is denoted by n.
● Its value start form 1,2,3,4 ...
●
2
The maximum number of orbitals in an orbit can be calculated by the formula of n and the maximum number of
2
electrons in an orbit are determined by using the formula of 2n .
2. Azimuthal Quantum Number
● The azimuthal quantum number describes the shape of orbital in an atom.
● It is denoted by L.
● Its value start from 0,1,2,3 ...
● The maximum number of orbitals in an orbit are determined by the formula (2L+1) whereas maximum number of
electrons in a given subshell are calculated by 2(2L+1).

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 3. Magnetic Quantum Number
● The magnetic quantum number describes the orientation of orbitals in an atom.
● It is denoted by m.
● Its value is +L to -L.
4. Spin Quantum Number
● The spin quantum number describes the spin of electron in an orbital.
● It is denoted by s.
● This spinning of electron is associated with magnetic field. In the some orbital one electron may spin in
clockwise (-½) or anticlockwise (+½), but in the same orbital, two electrons can't have same spin quantum
number.
Quantum Numbers
Orbitals n L m
S 1 0 0 (1)
P 2 1 +1, 0 -1 (3)
d 3 2 +2, +1, 0, -1, -2 (5)
f 4 3 +3, +2, +1, 0, -1, -2, -3 (7)
 S-orbital has spherical shape in which the probability of finding the electron is uniformly distributed around the
nucleus. It has no nodal plane.
● The p-orbitals has dumbbell shape and they are oriented in space along the three mutually perpendicular axes (x,
y, and z) and are called px, py and pz orbitals. Each p-orbital has two lobes.
● The point when the two lobes meet each other is usually referred to as the nodal plane along which the
probability of finding the electron is zero.
● The d-orbital have double dumbbell shape. Under the influence of magnetic field they have five directional dxy,
2 2 2
dyz, dxz, dx y and dz in space.
● The f-orbital has complex shape. These orbitals exist in seven directions when placed in magnetic field.
ELECTRONIC CONFIGURATION
● The distribution of electrons in the available orbitals and orbits is called electronic configuration.
1. Pauli’s Exclusion Principle
● This principle states that in an orbital of an atom, no two electrons can have the same set of four quantum
numbers.
● According to this principle, two electrons in an orbital may have same values of three quantum numbers (n, L, m)
but the value of spin quantum number(s) must be different.
● From the Pauli's principle, it is concluded that an orbital can accommodate only two electrons and these two
electrons must have opposite spin.
2. Aufbau Principle
● The Aufbau is a German word which means building up. Pauli named this principle as Aufbau Principle.
● According to this principle, electrons are filled progressively to the various subshells in the order of the
increasing energy, starting with the 1s subshell having lowest energy
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p, 7s
3. (n+L) Rule
● This rule reminds us that the energy of an orbital depends upon both principal quantum number and azimuthal
quantum number.
● This law states that those orbitals which have lower (n+L) value are filled first. In case, if two orbitals which have
same (n+L) value, the orbital having lower (n) value will be filled first.
4. Hund’s rule of Maximum Multiplicity
● According to this rule, in degenerates orbitals, electrons are distributed in such a way that maximum number of
half-filled orbitals (single electron in orbital) are obtained.

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CHAPTER NO: 03 THEORIES OF COVALENT BONDING
INTRODUCTION
● The attractive force that holds atoms together in a compound is known as the chemical bond.
● Lewis gave the concept of valency and said that electrons in atoms are responsible for chemical bonding.
● Electronic theory of chemical bonding which is proposed independently by Kossel and Lewis tell that a chemical
bond is formed between two atoms to acquire noble gas configuration.
VALENCE BOND THEORY (VBT)
● This theory was introduced by London and Heitler in 1927.
● A covalent bond is formed due to the overlap of half-filled orbital of combining atoms.
● A single covalent bond is formed by the overlap of two half-filled atomic orbitals whereas a multiple bond is
formed by the overlap of more than two half-filled orbitals.
● The electrons present in both overlapped orbital should be in opposite spin.
● The strength of bond is determined by the extent of overlap. The greater the overlap, the stronger is the bond.
● VBT fails to describe the valencies in Carbon, Boron and Beryllium.
● VBT doesn't tell about paramagnetic behavior of oxygen.
● It fails to describe the delocalization of electrons in the molecules.
1. Sigma Bond
● This bond is established when the two atomic orbital overlap linearly in such a way that both orbital lie along the
line joining the two nuclei.
● It defines as the bond formed by head to head overlapping of half-filled atomic orbitals.
● The electron density in sigma bonded atoms found highest between the two bonded nuclei.
● There are three types of sigma overlapping i.e. s-s overlapping, s-p overlapping and p-p overlapping.
● The s-s overlapping found is H2.
● The s-p overlapping found in HF, HCl, etc.
● The p-p overlapping found in F2.
● Bond strength: s-s overlapping > s-p overlapping > p-p overlapping.
2. Pi Bond
● This bond is formed by the lateral or side way overlap of the p-orbital between the two atoms which already
bonded through sigma bond.
● The condition for the formation of pi-bond is that the two p-orbital should be parallel to each other.
● The electron cloud of pi-bond is unsymmetrical and is concentrated above and below the plane of pi-bond.
● It is relatively weaker than sigma bond.
Some essential features of Sigma Bona and Pi-Bond
Sigma Bond Pi-Bond
It is formed by head to head overlapping of half-filled It is formed by lateral or parallel overlapping of half-filled
atomic orbital. atomic orbital.
Only one sigma bond can exist between the bonded Maximum two pi-bonds can form between the two atoms.
atoms.
It is stronger due to greater overlap of atomic orbitals. It is weaker due to lesser overlap of atomic orbitals.
Electron cloud is denser around the bond axis. Electron cloud is denser at above and below the bond axis
MOLECULAR ORBITAL THEORY (MOT)
● Mullikan and Hund developed an alternate theory known as molecular orbital theory.
● Atomic orbitals of similar energies linearly combine together to produce molecular orbitals.
● Combination of two atomic orbitals gives two molecular orbitals (MO), one of them has lower energy and other
has higher energy than any of the atomic orbital from which they formed.
● The molecular orbital with lower energy is called bonding molecular orbital (BMO) and the orbital with higher
energy is called antibonding molecular orbital (ABMO).
● The movement of electrons in molecular orbital is influenced by both nuclei of combining atoms.
● The filling of electrons into the molecular orbital is followed by fundamental rules of electronic configuration i.e.
Aufbau Principle, Hund’s rule and Pauli rule.
● Bonding molecular orbital has lower energy than atomic orbital from which it is formed. Electrons in the bonding
molecular orbitals favor bonding because combining orbital interact constructively thus the probability of
electron density is maximum between the two nuclei.
● Antibonding molecular orbital has higher energy than the two combining atomic orbital. It is produced due to
destructive interaction and hence electron density in the region between two nuclei is zero.
● Molecular orbital theory (MOT) is best to predict the bond order and the magnetic properties of molecules.
● The formula used in determining the bond order is given as;
𝑵(𝒃)−𝑵(𝒂)
𝑩𝒐𝒏𝒅 𝒐𝒓𝒅𝒆𝒓 =
𝟐
● The bond order of H2 molecules is 1, it is diamagnetic in nature and the electrons of H2 molecules are
accommodate in bonding molecular orbital while antibonding molecular orbital remains empty.

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 ● The bond order of O2 molecules is 2, it is paramagnetic in nature and the 10 electrons of O 2 molecules are
accommodate in bonding molecular orbital while 8 electrons are accommodate in antibonding molecular orbital.
● The bond order of N2 molecules is 3, it is diamagnetic in nature and 8 electrons are accommodate in bonding
molecular orbital and 2 electrons are accommodate in antibonding molecular orbital.
VALENCE SHELL ELECTRON PAIR REPULSION THEORY (VSEPR)
● This approach to the structure of a covalent molecule is due to Sidgwick and Powell. They pointed out that the
shapes of molecules can be determined by the repulsion between the electron pairs present in valence shell of
central atom.
● There may be two types of electron pairs surrounding the central atom;
1. Bond Pairs: These are the result of the sharing of unpaired electrons of central atom with unpaired
electrons of surrounding atoms. These are also called active set of electrons.
2. Lone Pairs: These are the paired electrons of central atom which don't take part in sharing. They are also
called nonbonding pairs or active set of electrons.
● Being similarly charged, the bond pairs as well as the lone pairs repel each other.
● Due to repulsion, the electron pairs of central atom try to be as far apart as possible, hence the orient themselves
in space in such a manner that force of repulsion between them is minimized.
● Repulsion order: L-L pairs > B-L pairs > B-B pairs.
● In case of molecules with double and triple bonds, the pi-electron pairs are not considered to be active set of
electrons, hence not included in the count of total electron pairs.
● The shape of molecules depends upon total number of electrons pairs i.e. bonding pairs and lone pairs.
Shape of molecules according to VSEPR Theory
Types Active Pair Bond Pair Lone Pair Geometry Bond angle Examples
o
AX2 2 2 0 Linear 180 BeCl2, CO2, C2H2, etc
o
AX3 3 3 0 Trigonal planar 120 BF3, AlCl3, BH3, C2H4, etc
o
AX4 4 4 0 Tetrahedral 109 CH4, C2H6, CCl4, SiCl4, etc
o
AX3E 4 3 1 Trigonal pyramidal 107 NH3, NF3, PH3, etc
o
AX2E2 4 2 2 Angular or Bent 104.5 H2O, H2S, etc
HYBRIDIZATION
● The valency is generally regarded as the number of unpaired electrons in the valence shell of an atom.
● The mixing of different atomic orbital to produce the same number of equivalent orbital, having same shape and
energy is called hybridization.
Types of Hybridization
Mixing orbitals No; of hybrid Hybridization Shape Bond angle S% + P% Examples
orbitals
3 3 o
1s+3p 4sp Sp Tetrahedral 109.5 25% + 75% CH4,NH3,H2O
2 2 o
1s+2p 3sp Sp Trigonal 120 33.33%+66.67% C2H4, BF2
o
1s+1p 2sp Sp Linear 180 50% + 50% C2H2, BeCl3
BOND ENERGY
● Bond formation is exothermic process and bond breaking is endothermic process.
● The energy involved for the breaking or formation of 1 mole of particular type of bonds in the molecule is known
as bond energy. OR the energy released in the formation of a bond from its free atoms is called bond energy.
● The bond energy is generally considered as bond dissociation energy.
● Its unit is KJ/mole.
● Bond energy is directly proportional to polarity of molecules and presence of multiple bond while bond energy is
inversely proportional to size of bonded atoms.
BOND LENGTH
● The distance between the nuclei of two bonded atoms in a molecule is known as bond length.
● Bond length is experimentally determined by x-rays diffraction technique.
●
-10
The unit use for its measurement is Angstrom (A°) which is equal to the 10 m
● Bond length is inversely proportional to bond order, bond polarity and bond strength.
DIPOLE MOMENT
● Dipole moment is a measuring scale use for the degree of polarity of polar bond.
● It is defines as the product of magnitude of charge and the distance between positive and negative centers.
● Dipole moment is a vector quantity.
●
-18
The dipole moment of all polar molecules found in the limit of 10 esu.cm.
● The unit of dipole moment is Debye and Coulomb meter (SI Unit).
-18 -30
1D=1×10 esu.cm, 1D=3.336×10 Cm
● Dipole moment of a molecules depends not only upon the polarity of its bonds but it also depends upon the
geometry of molecules.
● The H2O has dipole moment of 1.85D due to its angular shape while CO2 has no dipole moment due to its linear
shape.

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CHAPTER NO: 04 STATE OF MATTER (GASES)
INTRDUCTION
● The anything which has mass and occupies space is called matter. In universe, there are four fundamental states
of matter solid, liquid, gas and plasma.
● The word gas is derived from Greek Language khaos which means emptiness or gap.
● Helium, Neon, Argon, etc are monoatomic gases.
● Nitrogen, Hydrogen, Oxygen, Fluorine, Chlorine, etc are diatomic gases.
● Methane, Ethane, Carbon dioxide, etc are polyatomic gases.
KINETIC MOLECULAR THEORY OF GASES
● The general behavior and properties of gases are explain by kinetic molecular theory. This theory was given by
Daniel Bernoulli and then extended by Maxwell and Boltzmann.
● Gases consist of a large number of tiny particles called molecules.
● Gas molecules are far apart from each other and occupy negligible volume as compared to the total volume of the
container.
● Gas molecules are in continuous random motion, traveling in a straight line until they collide with each other or
with the walls of the container. The average distance covered by the gas molecules between successive
collisions is known as mean free path.
● Gas particles undergo elastic collisions.
● Gas exerts pressure when molecules collide with the walls of container.
● There is no force of attraction or repulsion found among gas molecules.
● The average kinetic energy of gas molecules depends upon absolute temperature. The kinetic energy is directly
proportional to the absolute temperature.
● The R.J. Clausius derived a kinetic equation;
𝟏 ̅̅̅𝟐̅
𝑷𝑽 = 𝒎𝑵𝑪
𝟑
PRESSURE AND ITS UNITS
● At 0°C on sea level our body bears a pressure of 760torr.
● The pressure of air is measured by Barometer.
● A monometer is a type of Barometer that can be used to measure the pressure of a gas enclosed in a container.
● Pressure is defined as the magnitude of force that is applied on the surface of an object per unit area.
𝑭𝒐𝒓𝒄𝒆
𝑷𝒓𝒆𝒔𝒔𝒖𝒓𝒆 = (𝑺𝑰 𝒖𝒏𝒊𝒕: 𝑷𝒂𝒔𝒄𝒂𝒍, 𝑵𝒎−𝟐 )
𝑨𝒓𝒆𝒂
● Pascal is defined as one newton force that is distributed at an area of one square meter.
101325Pa=1atm=760mm Hg=14.7psi
● An area which has low atmospheric pressure is generally warmer. Since this area has a suffocating weather it
invites winds, clouds and precipitation. During day time there is comparatively moderate temperature while
nights are warmer.
● The area which experiences a high air pressure is generally dry and cold. Thus, clear sky can be observed and
clam weather is developed.
TEMPERATURE
● The measure of the hotness or coldness of a body is called temperature.
● Scales of temperature: Celsius, Fahrenheit and Kelvin
K=°C + 273
GAS LAWS
1. Boyle's Law
● Robert Boyle studied the effect of pressure changes on the volumes of ideal gases.
● Statement: The volume of the given mass of gas is inversely proportional to the pressure at constant
temperature.
𝟏
𝑽∝ (𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕 𝒕𝒆𝒎𝒑𝒆𝒓𝒂𝒕𝒖𝒓𝒆)
𝑷
𝑲 𝑽𝟏 𝑽𝟐
𝑽= , =
𝑷 𝑷𝟐 𝑷𝟏
2. Charle's Law
● The change in volume of gases due to change in temperature at constant pressure were studied by Charles.
● 1st Statement: The volume of given mass of a gas increases or decreases by 1/273 times of its original volume at
0°C for every degree rise and fall of temperature at given pressure.
● 2nd Statement: The volume of given mass of gas is directly proportional to the absolute temperature at a given
pressure.
𝑽 ∝ 𝑻𝒂𝒃𝒔: (𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕 𝒑𝒓𝒆𝒔𝒔𝒖𝒓𝒆)
𝑽𝟏 𝑽𝟐
𝑽 = 𝑲𝑻, =
𝑻𝟏 𝑻𝟐
● When the graph is plotted between temperature and volume, a straight line is obtained.

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 ● If a gas is cooled at -273.15°C, the volume will become zero. This temperature (-273.15°C) is called absolute zero
or zero kelvin.
● Absolute zero is a theoretical temperature and defines as the temperature at which volume of an ideal become
equal to zero.
3. Avogadro's Law
● Amedeo Avogadro gave a relationship between volume and number of moles of gases at fixed temperature and
pressure.
● 1st Statement: Under the similar conditions of temperature and pressure, equal volume of all gases contain equal
number of moles.
● 2nd Statement: The volume of a gas is directly proportional to the number of moles if the pressure and
temperature are kept constant.
𝑽 ∝ 𝒏 (𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕 𝒕𝒆𝒎𝒑𝒆𝒓𝒂𝒕𝒖𝒓𝒆 𝒂𝒏𝒅 𝒑𝒓𝒆𝒔𝒔𝒖𝒓𝒆)
𝑽𝟏 𝑽𝟐
𝑽 = 𝑲𝒏, =
𝒏𝟏 𝒏𝟐
IDEAL GAS EQUATION
𝑷𝟏 𝑽𝟏 𝑷𝟐 𝑽𝟐
𝑷𝑽 = 𝒏𝑹𝑻, =
𝑻𝟏 𝑻𝟐
𝑷𝑽 = 𝑹𝑻 (𝒇𝒐𝒓 𝒐𝒏𝒆 𝒎𝒐𝒍𝒆, 𝒏 = 𝟏)
𝒎𝑹𝑻 𝑷𝑴
𝑴= , 𝒅= ∴ 𝑹 = 𝑼𝒏𝒊𝒗𝒆𝒓𝒔𝒂𝒍 𝑮𝒂𝒔 𝑪𝒐𝒏𝒔𝒕𝒂𝒏𝒕
𝑷𝑽 𝑹𝑻
●
3
Pressure is in ATM and volume is in dm ;
3
R=0.0821atm.dm /mol.K
●
-2 3
Pressure is in Nm and volume is in m ;
R=8.31Nm/mol.K OR R=8.31J/mol.K
DEVIATION FROM IDEAL GAS BEHAVIOR
● A gas which strictly obeys gas laws or general gas equation under all conditions of temperature and pressure is
known as an ideal gas.
● A gas which don't exactly follow the ideal gas laws is called real gas.
● Real gas shows deviation from ideal gas particularly at high pressure and low temperature.
𝑷𝑽
𝑷𝑽 = 𝒁𝒏𝑹𝑻, 𝒁 = ∴ 𝒁 = 𝒄𝒐𝒎𝒑𝒓𝒆𝒔𝒔𝒊𝒃𝒊𝒍𝒊𝒕𝒚 𝒇𝒂𝒄𝒕𝒐𝒓
𝒏𝑹𝑻
● The values of Compressibility factor (Z);
1. Z=1, for ideal gases
2. Z<1, for real gases showing negative deviation
3. Z>1, for real gases showing positive deviation
● All real gases act like ideal gases at low pressure and high temperature.
VANDER WAAL’S EQUATIONS
1. Volume Correction
𝑽(𝒇𝒓𝒆𝒆) = 𝑽(𝒄𝒐𝒏𝒕𝒂𝒊𝒏𝒆𝒓) − 𝒃 ∴ 𝒃 = 𝟒𝑽(𝒂𝒄𝒕𝒖𝒂𝒍 𝒗𝒐𝒍𝒖𝒎𝒆)
𝑽(𝒇𝒓𝒆𝒆) = 𝑽(𝒄𝒐𝒏𝒕𝒂𝒊𝒏𝒆𝒓) − 𝒏𝒃
𝑽(𝒓𝒆𝒂𝒍) = 𝑽(𝒊𝒅𝒆𝒂𝒍) − 𝒏𝒃
2. Pressure Correction
𝒂𝒏𝟐
(𝑷 + ) (𝑽 − 𝒏𝒃) = 𝒏𝑹𝑻
𝑽𝟐
𝒂
(𝑷 + ) (𝑽 − 𝒃) = 𝑹𝑻 → 𝒇𝒐𝒓 𝒐𝒏𝒆 𝒎𝒐𝒍𝒆, 𝒏 = 𝟏
𝑽𝟐
6 2 3
SI unit of a= atmdm /mol , SI unit of b= dm /mol
DALTON'S LAW OF PARTIAL PRESSURE
● John Dalton gave a law dealing with the pressure exerted by non-reactive mixture of gases.
● Statement: The total pressure exerted by a mixture of nonreactive gases in a closed vessel of fixed volume is
always equal to the sum of their individual pressure at a constant temperature.
𝑷𝒕 = 𝑷𝑨 + 𝑷𝑩 + 𝑷𝑪 + ⋯
● The pressure exerted by each individual gas in a mixture is called partial pressure.
● The partial pressure of any gas of the mixture is equal to the product of mole fraction of that gas and total
pressure of mixture.
𝑷 = 𝑿𝑷𝒕 ∴ 𝑿 = 𝒎𝒐𝒍𝒆 𝒇𝒓𝒂𝒄𝒕𝒊𝒐𝒏
● Mole fraction is the ratio of number of moles of individual gas to the total number of moles of all gases present in
mixture.
● It should be noted that mole fraction of any gas in the mixture is less than one but sum of mole fraction is always
equal to one.
● Applications of Dalton's law of partial pressure:
1. Pressure of gases collected over water
2. Maintenance of oxygen pressure at high altitude
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 3. Maintenance of oxygen pressure for deep sea drivers
GRAHAM'S LAW OF DIFFUSION AND EFFUSION
● The movement of gas molecules through tiny hole into the region of low pressure is termed as effusion. The
diameter of tiny hole is considerably smaller then mean free path.
● The process in which molecules of different gases homogenously intermix with each other is known as diffusion.
● Lighter gases diffuse more rapidly than heavier gases.
● Thomas Graham introduced a quantitative relationship between the rate of effusion or diffusion of gases and
their densities by maintaining the temperature and pressure.
● This law states that at constant temperature and pressure, the rate of effusion or diffusion of a gas is inversely
proportional to the square root of its density of molar mass.
𝟏
𝒓∝ (𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕 𝒕𝒆𝒎𝒑𝒆𝒓𝒂𝒕𝒖𝒓𝒆 𝒂𝒏𝒅 𝒑𝒓𝒆𝒔𝒔𝒖𝒓𝒆)
√𝒅
𝒓𝟏 √𝒅𝟐
=
𝒓𝟐 √𝒅𝟏
𝒓𝟏 √𝑴𝟐
=
𝒓𝟐 √𝑴𝟏
 Applications of Graham's law;
1. Densities and molar masses of different gases can be determined by using Graham's law.
2. The effect of toxic gases can be reduced by diffusing them into air.
LIQUEFACTION OF GASES
● Liquefaction is a physical process or technique in which gases are converted into liquids.
● The process of liquefaction requires high pressure and low temperature.
● The temperature above which a gas can't be liquefied no matter how much pressure is applied is called its critical
temperature.
1. Joule-Thomson Effect
● When a compressed gas is allowed to enter from a region of higher pressure to a lower pressure through a
nozzle, it expands and causes a fall in temperature. This is known as Joule Thomson Effect.
2. Linde’s Method of liquefaction of Gases
● This method is based on the principle of Joule-Thomson Effect for the liquefaction of gases.
● In this method pure dry air is passed through compressor where it compressed to 200atm. The heat produced
due to compression is removed by passing the air through cooler. Compressed air is then passed through a
spiral pipe having a nozzle at the end. When the gas comes out from nozzle of spiral pipe into expansion
chamber, its pressure reduces from 200atm to 1atm. In this way fall of temperature occurs.
● Liquefied natural gas, LNG is used as fuel.
● Liquefied petroleum gas, LPG used as a fuel for portable heaters.
● Liquid ammonia is used as refrigerant.
● Liquid oxygen is used for welding purpose.
● Liquid nitrogen is used in medical science.
PLASMA (FOURTH STATE OF MATTER)
● This state of matter was identified by William Crooks while he was working on discharge tube experiment.
● More than 99% of the visible universe is composed of plasma.
● Plasma occurs naturally in the sun, starts and ionosphere, but rarely on our earth.
● Plasma is the mixture of positive ions, electrons and neutral particles.
● Plasma as a whole is neutral because it contains equal number of negatively charged electrons and positive
charged ions.
● It is influenced by electric and magnetic field.
● Particles of plasma has neither definite shape nor volume.
● Plasma show characteristics glow in discharge tube depending upon the nature of gas i.e. hydrogen exhibit
green, oxygen red and nitrogen purple.

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CHAPTER NO: 05 STATES OF MATTER (LIQUIDS)
INTRODUCTION
● Liquid state is the state of matter having definite volume, but no definite shape.
● A pure liquid is said to be a single phase substance composed by identical molecules.
● Water is the most abundant liquid compound present on the earth's crust.
● Mercury and Bromine are liquid elements present in periodic table.
● Brownian motion is the result of unequal number of collision of liquid molecules with each other from different
sides.
INTERMOLECULAR FORCES IN LIQUIDS
● The forces of attraction among liquid molecules are collectively called intermolecular force of secondary force or
Vander Waal force.
● These attractive forces are actually physical bonds and are electrostatic in nature.
1. Dipole-Dipole Interaction
● The electrostatic force of attraction between the positive end of one polar molecule and the negative end of other
polar molecules is called Dipole-Dipole Interaction.
● The strength of Dipole-Dipole Interaction is about 1% of a normal covalent bond.
● An example of liquid in which Dipole-Dipole forces exist is iodine monochloride, which is reddish brown oily
liquid.
2. Hydrogen Bonding
● The force of attraction between partially positive charged hydrogen atom of one molecules and lone pair of
electron of highly electronegative atom of another molecules is called hydrogen bonding.
● Hydrogen bond is represented by the dotted lines.
● It is the strongest among all intermolecular forces however much weaker than ordinary covalent bond.
● The strength of hydrogen bond is about 5-10% of the strength of covalent bond.
● Specific heat is the amount of heat energy required to raise the temperature of one gram of any substance by 1°C.
Water doesn't warm or cool rapidly, this is due to high specific heat of water which is due to hydrogen bonding.
● A water molecule can form a maximum four hydrogen bonds in three dimensional spaces.
●
3
At 20°C the density of water is 1g/cm .
● When water is heated from 0°C to 4°C, its volume decreases.
● When water is cooled from 4°C to 0°C, its volume increases.
● The water molecule show maximum density at 4°C.
● In the form of ice, water molecules are arranged in the more hexagonal patterns in the manner that empty spaces
are created in the structure of ice and its volume expands Upto 10%. The low density of ice can be seen when ice
float on water.
3. London Dispersion Forces
● These forces were first reported by Fritz London. These attractive forces existing among nonpolar molecules
which become polar temporarily.
● The attractive force which develops between an instantaneous dipole and an induce dipole is known as London
dispersion forces.
● London Dispersion Force is directly proportional to size of atoms and number of atoms in molecules.
EVAPORATION
● At any given temperature, a certain number of the molecules in a liquid possess sufficient kinetic energy to
escape from the surface. This process is called evaporation.
● The liquids have higher vapor pressure and evaporate readily are called violet liquids i.e. ethanol, acetone,
gasoline, etc.
● The liquids have low vapor pressure and don't readily evaporate are called non-volatile liquids i.e. mobil oil,
Mercury, etc.
● Evaporation is an endothermic process.
● Evaporation is directly proportional to surface area and temperature while inversely proportional to
intermolecular forces.
VAPOR PRESSURE
● The pressure exerted by the vapors when they are in equilibrium with liquid phase at that temperature is called as
vapor pressure.
● Vapor pressure of water at 20°C is 17.5torr but at 100°C it is 760torr.
● Vapor pressure is independent of the amount of liquid but it is directly proportional to temperature and inversely
proportional to intermolecular forces.
BOILING POINTS
● Boiling point is the temperature at which the vapor pressure of liquid becomes equal to the atmospheric
pressure.
● When atmospheric pressure is 1atm, the boiling point is referred to as normal boiling point.
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 ● The boiling point is directly proportional to the pressure.
● Glycerin boils at 290°C at 760torr but it decomposed at this temperature. If it is heated under reduce pressure,
50torr, it boils at 210°C without decomposition.
VISCOSITY
● Viscosity is the measure of internal resistance of a liquid to flow.
●
-2
The unit of viscosity is poise and centipoise. The SI unit of viscosity is N.s.m .
● Viscosity is directly proportional to intermolecular forces and molecular size but inversely proportional to
temperature.
SURFACE TENSION
● Surface tension is the force acting at right angle on the unit length of surface of liquid. OR the amount of energy
that cause to increase the unit area of liquid is called surface tension.
●
2
The unit of surface tension is dyne/cm or erg/cm .
● Surface tension is directly proportional to the intermolecular forces while inversely proportional to the
temperature.
● The spherical shape of free falling drop of liquid and capillary action of liquid is due to surface tension.
ENERGETIC OF PHASE CHANGE
1. Molar Heat of Fusion (∆Hfusion)
● It is the amount heat required to convert one mole of a solid completely into liquid at its melting point.
● The molar heat of fusion when ice is converted into water is +6.02KJ/mol.
2. Molar Heat of Vaporization (∆Hvaporization)
● The amount of heat required to convert one mole of a liquid into its vapor at boiling point is referred as molar
heat of vaporization.
● The molar heat of vaporization when water is converted into vapors is +40.7KJ/mol.
3. Molar Heat of Sublimation (∆Hsublimation)
● The amount of heat absorbed when one mole of solid is directly converted into vapors without going through a
liquid state is known as molar heat of Sublimation.
● The molar heat of sublimation when solid carbon dioxide is converted into gas carbon dioxide is +25.2KJ/mol.
LIQUID CRYSTALS
● A liquid crystal is a state of matter between liquid and solid.
● It was first discovered by Friedrich Reintzer while he was examining physico-chemical properties of different
derivative of cholesterol.
● Liquid crystals are usually organic in nature or may be sometimes mixture of both organic and inorganic
materials.
● Liquid crystals exist both naturally or they can be synthetically developed.
● They have ability to flow like liquid but the molecular arrangement is similar to crystalline solids.
● Liquid crystal have optical properties as found in crystalline solid but exhibit anisotropy.

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CHAPTER NO: 06 STATES OF MATTER (SOLIDS)
INTRODUCTION
 Solid is a condense state of matter in which particles are closely arranged in fixed position and have very little
freedom of movement due to strong interionic, interatomic and intermolecular forces.
● Solids are identified by their rigid structure and mechanical strength.
● The process in which solids directly change into vapors on heating without passing through liquid phase is
called sublimation i.e. naphthalene, iodine, camphor and solid CO2.
TYPES OF SOLIDS
1. Crystalline Solids
● Crystalline solids are characterized by definite geometrical shape and sharp melting points.
● They are also known as true solids.
● Example: Sugar, Salts, Metals, etc.
2. Amorphous Solids
● The solids which don't have a three dimensional regular arrangement of particles are known as amorphous
solids.
● These solids don't have sharp melting point which means that they melt over a wide range of temperature.
● Examples: Rubber, Plastic, Glass, Charcoal, etc.
● Glass is also called super cooled liquid.
● Amorphous silica is one of the best materials for converting sunlight into electricity in photovoltaic cell.
Comparative study of Crystalline and Amorphous solids
Crystalline Solids Amorphous Solids
They exist in definite geometrical shape They don’t have definite shape
They have sharp melting points They don’t have sharp melting points
They have anisotropic nature They show isotropic nature
They can cut at fixed cleavage plane They can’t cut at fixed cleavage plane
PROPERTIES OF CRYSTALLINE SOLIDS
1. Symmetry
● When a crystal is rotated to a certain angle, a regular repetition of edges and faces is observed, this is known as
symmetry.
● The symmetry of an individual crystal is determined by three elements known as plane of symmetry, axis of
symmetry and center of symmetry.
● Plane of symmetry is an imaginary plane which divides the crystal into two equal parts in such a way that one is
the image of other.
● Axis of symmetry is an imaginary line on which the crystal can be rotated through 360°.
● Centre of symmetry is a point in the crystal from which we can draw a line. This line intersects the surface of the
crystal at equal distance on either side.
2. Geometrical shape of crystals
● Since the particles in crystalline solids are orderly organized in a repeating pattern in three dimensions, they
possess geometrical shape.
● The shape of unit cell of diamond is cubic and the shape of unit cell of graphite is hexagonal.
3. Sharp Melting Point
● Crystalline solids have sharp melting point because attractive forces between the particles are long ranged and
uniform.
4. Cleavage Plane
● A big crystal can be cut into smaller crystals of identical shape, this process is called as cleavage and the line or
point which has direction of cleavage is known as cleavage plane.
5. Crystal growth
● When a hot saturated solution of salt or a molten solid is allowed to cool slowly, crystals are grown in various
directions it is called crystal growth.
● A slow cooling of hot saturated solution of table salt gives cubic crystal.
6. Anisotropy
● The variation in certain physical properties along different directions in the crystal lattice. This phenomenon is
known as anisotropy.
● An isotropic behavior of a crystalline solid depends upon the orientation of crystal lattice with respect to applied
force.
7. Isomorphism
● The phenomenon in which different solid substances exist in the same crystalline structure is called
isomorphism.
● The substances which exhibit this behavior are referred as isomorphous.

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 ● Although the isomorphous substances have different physical and chemical properties but they mostly have
same atomic ratio.
Isomorphism in different crystalline solids
Isomorphic Substance Atomic ratio Geometry of unit cell
NaCl and MgO 1:1 Cubic
NaNO3 and CaCO3 1:1:3 Rhombohedral
ZnSO4 and NiSO4 1:1:4 Orthorhombic
Ag2SO4 and Na2SO4 2:1:4 Hexagonal
8. Polymorphism
● The phenomenon in which a substance under different conditions can exist in more than one crystalline structure
is known as Polymorphism.
● They have same chemical properties but different physical properties.
● Lime (CaCO3) has two crystalline forms;
A. Calcite (trigonal)
B. Aragonite (orthorhombic)
ALLOTROPHIC MODIFICATION AND TRANSITION TEMPERATURE
● Allotropy is limited to pure elements only.
● Allotropy is defines as the existence of the same elements in two or more different crystal structures having the
same chemical nature but different physical properties.
● Carbon exists in two crystalline allotropic forms i.e. diamond and graphite.
● Sulphur exists in two crystalline allotropic forms i.e. rhombic sulphur (Alpha-sulphur) and monoclinic sulphur
(Beta-sulphur).
● The temperature at which two allotropic forms of the same element coexist in equilibrium with each other is
known as transition temperature.
● The transition temperature of rhombic and monoclinic sulphur is 95.5°C.
IONIC SOLIDS
● These solids consist of positive and negative charged ions.
● These solids have electrostatic force of attraction.
● They are hard at room temperature.
● They are brittle and can be shattered easily by hammering.
● They possess high melting point.
● They are soluble in water and similar polar solvent.
● They are unable to conduct electricity and heat in solid state.
● In molten or aqueous state they conduct electricity since the ions move freely.
● Radius ratio is the ratio of radius of cation to that of radius of anion in the given ionic solid. It helps in predicting
the shape of ionic solids.
● Example: NaCl, KBr, CaCl2, etc.
COVALENT SOLIDS
● Covalent or atomic solids consist of atoms of the same or different elements which are bonded to each other by
strong covalent bond.
● In diamond, each carbon atom is covalently bonded with four other carbon atoms at an angle of 109.5° to form
basic tetrahedral unit.
● In graphite, each carbon is bonded to three other carbon atoms at 120° forming layers of hexagons. These layer
are held together by weak Vander Waal forces and are 3.35°A apart from each other.
● They possess high melting point and high density.
● They are bad conductors of electricity.
● They are insoluble in water.
● Graphite however, conducts electricity parallel to the layers due to availability of delocalized electron.
● Example: Diamond, Graphite, Silicon, Carbide, etc.
METALLIC SOLIDS
● Particles of metallic solids are metal atoms held together by metallic bond.
● Metallic solids are identified by their malleability, ductility and luster.
● Metallic solids are good conductor of heat and electricity.
● Example: Na, Al, Zn, Fe, Cu, etc.
MOLECULAR SOLIDS
● In these solids, constituent particles are molecules of the same substance.
● In molecular solids, molecules are held together by Dipole-Dipole Interaction or hydrogen bonding or London
force.
● Molecular solids metal under relatively low temperature.
● Molecular solids have low density, low melting point and serve as bad conductor of electricity.
● Example: Ice, Iodine, Dry ice, etc.
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CRYSTAL LATTICE AND UNIT CELL
● A crystal lattice is a three dimensional structural arrangement of the particles of a crystalline solid.
● The smallest structural part of a crystal lattice is known as unit cell.
● The smallest repeating pattern from which the lattice is built is known as unit cell.
● The shape of a unit cell is associated with the length of three sides (a, b and c) and the angles between these
sides (𝜶, 𝜷 𝒂𝒏𝒅 𝜸).
● The angel between b and c is𝜶 , the angle between a and c is 𝜷 and the angle between a and b is𝜸.
Seven Crystal Systems of Solids
Shape Axis Angles
Cubic 𝒂=𝒃=𝒄 𝜶 = 𝜷 = 𝜸 = 𝟗𝟎°
Tetragonal 𝒂=𝒃≠𝒄 𝜶 = 𝜷 = 𝜸 = 𝟗𝟎°
Orthorhombic 𝒂≠𝒃≠𝒄 𝜶 = 𝜷 = 𝜸 = 𝟗𝟎°
Rhombohedral 𝒂=𝒃=𝒄 𝜶 = 𝜷 = 𝜸 ≠ 𝟗𝟎°
Hexagonal 𝒂=𝒃≠𝒄 𝜶 = 𝜷 = 𝟗𝟎° 𝒃𝒖𝒕 𝜸 = 𝟏𝟐𝟎°
Monoclinic 𝒂≠𝒃≠𝒄 𝜶 = 𝜸 = 𝟗𝟎° 𝒃𝒖𝒕 𝜷 ≠ 𝟗𝟎°
Triclinic 𝒂≠𝒃≠𝒄 𝜶 ≠ 𝜷 ≠ 𝜸 ≠ 𝟗𝟎°
UNIT CELL OF NaCl CRYSTAL
● The shape of unit cell of sodium chloride is face centered cubic in which each sodium ion is surrounded by six
chloride ions and each chloride ion is surrounded by six sodium ion.
● There are eight chloride ions at the eight corner of cube while six chloride ions at the center of six faces of cube.
● There is one sodium ion in the center of cube while twelve sodium ions at the edges of cube.
● Sodium chloride unit cell contains a total of eight ions, with four being sodium ions and the other four beings
chloride ions. This distribution follows the 1:1 ratio specified by its chemical formula.
Close packing of Metallic solids
Type Layer arrangement Coordination Number Space Used
Hexagonal ABA 12 74%
Face centered cubic ABCA 12 74%
Body centered cubic ABAC 08 68%
LATTICE ENERGY
● It is the energy associated with electrostatic interaction between the ions in a crystal and may be defined as the
quantity of energy released when one mole of the ionic crystal is formed from the gaseous ions.
● It is also defined as the energy required to break one mole of crystalline solid into isolated ions in the gas phase.
● It is expressed in KJ/mole.
● The lattice energy is directly proportional to charge on ions and inversely proportional to size of cation or anion.

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CHAPTER NO: 07 CHEMICAL EQUILIBRIUM
INTRODUCTION
 Those reactions in which products ones formed can’t be reversed into the reactant is called irreversible reactions
or unidirectional reactions. These reactions are carried out in open vessels.
𝑪𝑯𝟒 + 𝟐𝑶𝟐 → 𝑪𝑶𝟐 + 𝟐𝑯𝟐 𝑶
 Those reactions in which product can be reversed and change into reactant again, such reactions are called
reversible reactions or bidirectional reactions. These reactions are carried out in close vessels.
𝑪𝑯𝟑 𝑪𝑶𝑶𝑯 + 𝑪𝟐 𝑯𝟓 𝑶𝑯 ⇋ 𝑪𝑯𝟑 𝑪𝑶𝑶𝑪𝟐 𝑯𝟓 + 𝑯𝟐 𝑶
𝑵𝟐 𝑶𝟒 ⇋ 𝟐𝑵𝑶𝟐
𝑵𝟐 + 𝟑𝑯𝟐 ⇋ 𝟐𝑵𝑯𝟑
𝑵𝟐 + 𝑶𝟐 ⇋ 𝟐𝑵𝑶
 Chemical equilibrium is a state of reversible reaction where no net change in the concentration of reactants and
products occurs with time.
Macroscopic Characteristics of forward and reverse reaction
Forward Reaction Reverse Reaction
Forward reaction in a reversible reaction represents the Backward reaction in a reversible reaction specifies the
transformation of reactants into products conversion of products into reactants
It takes place from left to right It takes place from right to left
At initial stage, the rate of this reaction is found to be very At initial stage, the rate of this reaction is found to be very
fast slow
As the time goes on, this reaction becomes slow down As the time goes on, this reaction becomes fast
 Necessary conditions for Equilibrium;
(1) Chemical equilibrium can only establish if it is carried out in a closed vessel because in this system reactant
or product particles can’t be escaped out.
(2) Temperature, pressure and volume should be constant be equilibrium state. If any one of these variable is
changed, the system will not remain in equilibrium.
(3) The concentration of both reactants and products should remain constant. The addition or removal of any
one of them causes the equilibrium to be disturbed.

LAW OF MASS ACTION

 C.M Guldberg and Peter Wage found out that reversible reaction reaches a state where the ratio of its products
concentration to that of reactants concentration becomes constant.
 They derived a quantitative relationship between the rate of reaction and active masses of reacting substance
known as law of mass action.
 The law of mass action states that the rate of chemical reaction is directly proportional to the product of the
active masses of reacting species.

3
The term active mass refers to molar concentration that is the number of moles of reactant and product per dm .
𝒂𝑨 + 𝒃𝑩 ⇋ 𝒄𝑪 + 𝒅𝑫
[𝑪]𝒄 [𝑫]𝒅
𝑲𝒄 = [𝑨]𝒂 [𝑩]𝒃
→ 𝑬𝒒𝒖𝒊𝒍𝒊𝒃𝒓𝒊𝒖𝒎 𝒆𝒙𝒑𝒓𝒆𝒔𝒔𝒊𝒐𝒏 𝑶𝑹 𝑬𝒒𝒖𝒊𝒍𝒊𝒃𝒓𝒊𝒖𝒎 𝒍𝒂𝒘
 Where Kc is called equilibrium constant.
 The values of equilibrium constant (Kc) varies with temperature.
 If the number of moles of reactants are equal to the number of moles of product then K c has no unit.
 If the number of moles of reactants are different from number of moles of product then the unit of K c is
3 ∆n
determined by using the formula (mol/dm ) .
[𝑪𝑯 𝑪𝑶𝑶𝑪𝟐 𝑯𝟓 ][𝑯𝟐 𝑶] 𝒙𝟐
𝑪𝑯𝟑 𝑪𝑶𝑶𝑯 + 𝑪𝟐 𝑯𝟓 𝑶𝑯 ⇋ 𝑪𝑯𝟑 𝑪𝑶𝑶𝑪𝟐 𝑯𝟓 + 𝑯𝟐 𝑶 , 𝑲𝒄 = [𝑪𝑯 𝟑 = (𝒂−𝒙)(𝒃−𝒙)
𝟑 𝑪𝑶𝑶𝑯][𝑪𝟐 𝑯𝟓 𝑶𝑯]
𝒂𝑨 + 𝒃𝑩 ⇋ 𝒄𝑪 + 𝒅𝑫
[𝑷𝑪 ]𝒄 [𝑷𝑫 ]𝒅
𝑲𝑷 = [𝑷𝑨 ]𝒂 [𝑷𝑩 ]𝒃
 KP is defines as the ratio of partial pressure of product gases to that of partial pressure of reactant gases each
raised to the power equal to its own coefficient in the balanced chemical equation.
[𝒏𝑪 ]𝒄 [𝒏𝑫 ]𝒅 [𝑿𝑪 ]𝒄 [𝑿𝑫 ]𝒅
𝑲𝒏 = [𝒏𝑨 ]𝒂 [𝒏𝑩 ]𝒃
, 𝑲𝑿 = [𝑿𝑨 ]𝒂 [𝑿𝑩 ]𝒃
 Relation between KP and Kc;
𝑲𝑷 = 𝑲𝑪 (𝑹𝑻)∆𝒏
 Relation between KP and KX;
𝑲𝑷 = 𝑲𝑿 (𝑷)∆𝒏
 Relation between KP and Kn;
𝑷 ∆𝒏
𝑲𝑷 = 𝑲𝒏 ( )
𝒏
 The reaction quotient (QC) is an expression representing the ratio of molar concentration of products to that of
reactants in a reversible reaction.
𝒂𝑨 + 𝒃𝑩 ⇋ 𝒄𝑪 + 𝒅𝑫
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 [𝑪]𝒄 [𝑫]𝒅
𝑸𝑪 = [𝑨]𝒂[𝑩]𝒃
 A comparison of magnitude of QC and KC tells the direction in which the reaction proceed to attain an equilibrium;
(1) Kc > QC → show forward reaction
(2) KC < QC → show reverse reaction
(3) KC = QC → show dynamic equilibrium
 The KC is also used in the prediction of extent of reaction;
(1) KC = Very large → shows that ratio of product to reactants at equilibrium is very large and the reaction is
near to completion.
𝑪𝑯𝟒 + 𝑪𝒍𝟐 ⇋ 𝑪𝑯𝟑 𝑪𝒍 + 𝑯𝑪𝒍 (𝑲𝑪 = 𝟏. 𝟐 × 𝟏𝟎𝟏𝟖 )
(2) KC = Very small → shows that the ratio of product to reactants at equilibrium is very small and the
reaction proceeds very little in the forward direction.
𝑵𝟐 + 𝑶𝟐 ⇋ 𝟐𝑵𝑶 (𝑲𝑪 = 𝟒. 𝟓 × 𝟏𝟎−𝟑𝟏 )
(3) KC = Intermediate → shows that appreciable amount of both reactants and products are present in the
equilibrium.
𝟐𝑵𝑶𝟐 ⇋ 𝑵𝟐 𝑶𝟐 (𝑲𝑪 = 𝟒𝟑. 𝟒𝟒)

LE-CHATELIER’S PRINCIPLE

 Le-Chatelier’s principle states that if an external stress such as concentration, pressure or temperature is applied
to a system at equilibrium, the equilibrium is disturbed and tends to shift in a direction to undo the effect of
stress imposed.
1. Effect of Change in Concentration
 The equilibrium position shifts towards the right (forward) if the amount of reactant is added or product is
removed.
 The equilibrium position shifts to the left (reverse) if reactant is removed or product is added.
2. Effect of Change in Pressure
 When the number of moles of reactant is greater than the number of moles of product then if pressure is applied,
reaction will shift towards right (forward).
 When the number of moles of reactant is less than the number of moles of product then if pressure is applied,
reaction will shift toward left (reverse).
 When the number of moles of reactant is equal to the number of moles of product then there will be no effect of
applying pressure.
3. Effect of Change in Temperature
 For exothermic reactions, an increase in temperature shifts the equilibrium to the left (reverse) and decreases in
temperature shifts the equilibrium to the right (forward).
 For endothermic reactions, an increases in temperature shifts the equilibrium to the right (forward) whereas
decreases in temperature shifts the equilibrium to the left (reverse).
4. Effect of Catalyst
 A catalyst minimizes the time to reach equilibrium but doesn’t effect on change in equilibrium position of the
system.

HABER’S PROCESS

 The synthesis of ammonia by the Haber’s process is an industrial application of Le-Chatelier’s principle.
𝑵𝟐 + 𝟑𝑯𝟐 ⇋ 𝟐𝑵𝑯𝟑 (∆𝑯 = −𝒗𝒆)
 For the maximum yield of ammonia;
A. Pressure Increases (200-300atm)
o
B. Temperature decreases (400-500 C)
C. Catalyst iron is used

SOLUBILITY PRODUCT

 Solubility product is defined as the product of molar concentration of its positive and negative ions of sparingly
soluble sat.
𝑪𝒂𝑺𝑶𝟒 ⇋ 𝑪𝒂+𝟐 + 𝑺𝑶𝟒 −𝟐
𝑲𝑺𝒑 = [𝑪𝒂+𝟐 ][𝑺𝑶𝟒 −𝟐 ]
 Precipitation is a kind of double displacement reaction in which two solutions of different salts mixed together to
form two products, one of these product is insoluble in solution and called as precipitate.
 Ionic product (QSp) is the product of molar concentration of the ions of two different salts.
 Relations between KSp and Qsp;
I. QSp < KSp → Unsaturated solution, no ppt form
II. QSp > KSp → Supersaturated solution, ppt form
III. QSp = KSp → Saturated solution

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COMMON ION EFFECT

 To decrease the solubility of a sparingly soluble salt in solution by the addition of a highly soluble salt with one
common ion refers as common ions effect.
 Common ion effect plays versatile roles in many areas of analytical chemistry, such as buffering of solutions,
purification of salts, soap precipitation and other quantitative analysis.

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CHAPTER NO: 09 CHEMICAL KINETICS
INTRODUCTION
 The study of rate of chemical reaction, mechanism of reaction and the factors that influence on the rate of
chemical reactions is known as chemical kinetics.

RATE OF REACTION
 The rate of reaction is defined as increases in the molar concentration of products or decreases in the molar
concentration of reactant per unit time.
 The rate of reaction may also define as the ratio of change in the concentration of product or reactant to change
in time.
∆𝒙 𝒎𝒐𝒍
𝑹𝒂𝒕𝒆 = (𝑺𝑰 𝒖𝒏𝒊𝒕: . 𝒔𝒆𝒄)
∆𝒕 𝒅𝒎𝟑
 The reaction rate is expressed in the following two specific ways;
𝑨 →𝑩
(1) The rate of appearance of products which indicates that concentration of product increases with time.
∆𝑩
𝑹𝒂𝒕𝒆 =
∆𝒕
(2) The rate of disappearance of reactants which means concentration of reactant decreases with time.
−∆𝑨
𝑹𝒂𝒕𝒆 =
∆𝒕

RATE LAW

 Rate law is mathematical expression that explains the quantitative relationship of molar concentration of reacting
species with the rate of reaction.
𝒙𝑨 + 𝒚𝑩 → 𝑷𝒓𝒐𝒅𝒖𝒄𝒕
𝑹 = 𝑲 [𝑨]𝒙 [𝑩]𝒚
 Where ‘K’ is called rate constant.
 Rate law is an equation which specifies the rate in term of reactant concentration with each term raised to some
power.
 Specific rate constant at given temperature may be defined as the rate of reaction when the molar concentration
of each reactant is unity.
Rate = K
 Each reaction has a fixed value of specific rate constant (K) at a particular temperature. Its value changes with the
temperature, however independent upon change in concentration of reactant.

ORDER OF REACTION
 The order of reaction defines as the sum of all the exponents of the concentration in terms of reactants involves
in the rate law.
 The rate of zero order reactions is entirely independent of the concentration of reactants. They most often occurs
on the surface of metals. Photochemical reactions are also zero order reaction because they proceed by
absorbing light of certain wavelength instead of collisions of reactant molecules.
 The simple and common method for determining rate law and order of reaction is initial rate method.
 A single step reaction is known as elementary reaction while the reaction which complete in two or more steps is
called complex reaction.
 Order of Reactions;
i. Zero Order Reaction
𝑹𝒂𝒕𝒆 = 𝑲 → (𝑼𝒏𝒊𝒕: 𝒎𝒐𝒍. 𝒔𝒆𝒄−𝟏 )
𝑯𝟐 + 𝑪𝒍𝟐 → 𝑯𝑪𝒍
ii. Frist Order Reaction
𝑹𝒂𝒕𝒆 = 𝑲 [𝑨] → (𝑼𝒏𝒊𝒕: 𝒔𝒆𝒄−𝟏 )
𝑵𝑯𝟒 𝑵𝑶𝟐 → 𝑵𝟐 + 𝟐𝑯𝟐 𝑶
iii. Second Order Reaction
𝑹𝒂𝒕𝒆 = 𝑲 [𝑨][𝑩] 𝑶𝑹 𝑹𝒂𝒕𝒆 = 𝑲 [𝑨]𝟐 → (𝑼𝒏𝒊𝒕: 𝒎𝒐𝒍−𝟏 . 𝒔𝒆𝒄−𝟏 )
𝟐𝑯𝑰 → 𝑯𝟐 + 𝑰𝟐
iv. Third Order Reaction
𝑹𝒂𝒕𝒆 = 𝑲 [𝑨]𝟐 [𝑩] 𝑶𝑹 𝑹𝒂𝒕𝒆 = 𝑲[𝑨][𝑩]𝟐 → (𝑼𝒏𝒊𝒕: 𝒎𝒐𝒍−𝟐 𝒔𝒆𝒄−𝟏 )
𝟐𝑵𝑶 + 𝑪𝒍𝟐 → 𝟐𝑵𝑶𝑪𝒍

FACTORS AFFECTING THE RATE OF REACTION

 Generally substances having ionic bond reacts quickly as compared to the covalent bond.
 The rate of reaction is directly proportional to the concentration of reactant.
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  The rate of reaction is directly proportional to the surface area of solids.
 Radiations only effect zero order reactions. The rate of zero order reaction is directly proportional to radiation
intensity.
 The rate of reaction is directly proportional to temperature.

o
At room temperature, the rate of many chemical reactions roughly double with every rise in 10 C.

COLLISION THEORY, TRANSITION STATE AND ACTIVATION ENERGY

 Collision theory postulated that the rate of chemical reactions increases with the increased number of collision
per unit time.
 Transition state is an unstable short lived time species formed by the effective collision of reactant molecules. It
is an intermediate state between reactant and product and the substance at this stage is neither reactant nor
product, it is known as activated complex.
 The minimum amount of energy required to convert reactant molecules into activated complex is known as
activation energy. It is represented by Ea and measured in KJ/mole.

CATALYSIS
 A substance which alters the rate of chemical reaction without undergoing permanent changes in its chemical
nature is called catalyst and the process involving the use of catalyst is referred as catalysis.
 Positive catalyst increases the rate of reaction by lowering activation energy whereas the negative catalyst
decreases the rate of reaction by higher activation energy.
𝑵𝟐 + 𝟑𝑯𝟐 → 𝟐𝑵𝑯𝟑 (𝑪𝒂𝒕𝒂𝒍𝒚𝒔𝒕: 𝑰𝒓𝒐𝒏 𝒑𝒐𝒘𝒅𝒆𝒓, +𝒗𝒆 𝒄𝒂𝒕𝒂𝒍𝒚𝒔𝒕)
𝟐𝑺𝑶𝟐 + 𝑶𝟐 → 𝟐𝑺𝑶𝟑 (𝑪𝒂𝒕𝒂𝒍𝒚𝒔𝒕: 𝑽𝟐 𝑶𝟓 , +𝒗𝒆 𝒄𝒂𝒕𝒂𝒍𝒚𝒔𝒕)
𝟐𝑲𝑪𝒍𝑶𝟑 → 𝟐𝑲𝑪𝒍 + 𝟑𝑶𝟐 (𝑪𝒂𝒕𝒂𝒍𝒚𝒔𝒕: 𝑴𝒏𝑶, +𝒗𝒆 𝒄𝒂𝒕𝒂𝒍𝒚𝒔𝒕)
𝑪𝑯𝑪𝒍𝟑 + 𝟏/𝟐𝑶𝟐 → 𝑪𝑶𝑪𝒍𝟐 + 𝑯𝑪𝒍 (𝑪𝒂𝒕𝒂𝒍𝒚𝒔𝒕: 𝟐% 𝑪𝟐 𝑯𝟓 𝑶𝑯, −𝒗𝒆 𝒄𝒂𝒕𝒂𝒍𝒚𝒔𝒕)
𝑯𝟐 𝑶𝟐 → 𝑯𝟐 + 𝑶𝟐 (𝑪𝒂𝒕𝒂𝒍𝒚𝒔𝒕: 𝑮𝒍𝒚𝒄𝒆𝒓𝒊𝒏𝒆, −𝒗𝒆 𝒄𝒂𝒕𝒂𝒍𝒚𝒔𝒕)
 There are two types of catalysis i.e. homogenous catalysis and Heterogeneous catalysis.
(1) Homogenous Catalysis
 All those catalytic reactions in which both catalyst and reactants are in the same phase refer as homogenous
catalysis.
 In Acid-Base catalysis, both reactants and catalyst are present in the same aqueous phase.
𝑯𝟐 𝑺𝑶𝟒
𝑪𝑯𝟑 𝑪𝑶𝑶𝑪𝟐 𝑯𝟓 + 𝑯𝟐 𝑶 → 𝑪𝑯𝟑 𝑪𝑶𝑶𝑯 + 𝑪𝟐 𝑯𝟓 𝑶𝑯
 In some chemical reactions one of the product itself serves as catalyst, these are known as auto catalyzed
+2
reactions. For example, in redox titration between KMnO4 and oxalic acid, Mn ion of MnSO4 catalyzed the
reaction.
𝟐𝑲𝑴𝒏𝑶𝟒 + 𝟓𝑯𝟐 𝑪𝟐 𝑶𝟒 + 𝟑𝑯𝟐 𝑺𝑶𝟒 → 𝟐𝑴𝒏𝑺𝑶𝟒 + 𝟏𝟎𝑪𝑶𝟐 + 𝟖𝑯𝟐 𝑶 + 𝑲𝟐 𝑺𝑶𝟒
(2) Heterogeneous Catalysis
 All those catalytic reactions in which both catalyst and reactants are not in the same phase refers as
heterogeneous catalysis.
𝑽𝟐 𝑶𝟓
𝟐𝑺𝑶𝟐 + 𝑶𝟐 → 𝟐𝑺𝑶𝟑
𝑭𝒆
𝑵𝟐 + 𝟑𝑯𝟐 → 𝟐𝑵𝑯𝟑

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CHAPTER NO: 11 THERMOCHEMISTRY
INTRODUCTION
 The study of energy transformation as heat during a chemical process is known as thermochemistry.
 Thermodynamics is an essential branch of science which deals with the study of inter transformation of heat,
work and other forms of energies.
 Thermodynamics is a macroscopic science.

SYSTEM, SURROUNDINGS AND BOUNDARY

 The distinct part of our universe which is under particular experimental debate and separated from surrounding
by an imaginary or real surface and can change its shape or size is called system.
 All systems contain a certain quantity of matter and are characterized by particular macroscopic properties.
 There are three types of system i.e. Open system, Close system and isolated system.
 Open system is that system in which mass and energy both can transfer. A boiling tea kettle is an open system.
 Closed system is that system in which energy can transfer but mass can’t transfer. A pressure cooker is a closed
system.
 Isolated system is that system in which mass and energy both can’t transfer. A perfect isolated system doesn’t
exist but thermoflask and insulated drink cooler are considered as isolated system.
 Everything outside the arbitrarily selected boundaries of the system that effects the system or is affected by it is
called surrounding. It is referred to as the remaining part of the universe other than a system from which energy
or matter can be exchanged with the system.
 Boundary is real or imaginary close surface that separates a system from its surrounding.

MACROSCOPIC PROPERTIES
 Those properties which are present as bulk amount in system and can be measured easily are called
macroscopic properties.
 These are further divided into two class i.e. intensive properties and extensive properties.
 Intensive properties are those whose values are not dependent on quantity of matter in the given system i.e.
pressure, density, refractive index, surface tension, melting points, etc.
 Extensive properties are those whose values for the entire system depend on the quantity of matter i.e. mass,
volume, energy, enthalpy, moles, etc.

ENTROPY AND STATE FUNCTION

 Entropy is a measure of the disorder of the system. It is directly proportional to temperature.
 A state function is thermodynamic parameter which is dependent on initial and final state of system and is
independent of how the change is occurred i.e. internal energy, enthalpy, temperature, volume, etc.

ENTHALPY
● The total heat contents of system is called enthalpy OR the sum of internal energy and algebraic product of
pressure and volume is called enthalpy.
𝑯 = 𝑬 + 𝑷𝑽
● Enthalpy is a state function property.
● The units used for measuring enthalpy of a system are Joule, Calorie and KJ/mole.
𝟏𝑪𝒂𝒍𝒐𝒓𝒊𝒆 = 𝟒. 𝟏𝟖𝑱𝒐𝒖𝒍𝒆𝒔
THERMOCHEMICAL REACTIONS
1. Exothermic Reactions
● Exothermic reactions are those in which heat is given out making the surrounding warmer.
● In these reactions, product contain less energy as compared to the reactant.
● These reactions are represented by -∆H.
● These reactions rise the temperature of surrounding.
● Examples: Burning of fuel and coal, oxidation of suigas, etc.
2. Endothermic Reactions
● Endothermic reactions are those in which heat is put into the system making surrounding cooler.
● In these reactions, product contain more energy as compared to reactant.
● These reactions are represented by +∆H.
● These reactions fall the temperature of surrounding.
● Examples: Photosynthesis, etc.
FIRST LAW OF THERMODYNAMICS
● The first law of thermodynamics is an adaptation of the law of conservation of energy.
● This concept was enunciated by J.R.Mayer and formulated by Helmholtz.
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COMPOSED BY: MUNEER AHMED LEGHARI (FOUNDER OF MK TESTING SERVICE) 0307-3224114 / 0302-1483336
 ● This law may be stated as in any physical or chemical process, the net energy of a system and its surroundings
must remain constant OR a system can't create or destroy energy, however it can exchange energy with its
surrounding in the form of heat and work.
∆𝑬 = 𝒒 + 𝑾
● Pressure-Volume Work Equation;
𝑾 = −𝑷𝑽 (𝟏𝒂𝒕𝒎. 𝒅𝒎𝟑 = 𝟏𝟎𝟏. 𝟑𝟐𝟓𝑱𝒐𝒖𝒍𝒆𝒔)
INTERNAL ENERGY
● The total sum of all microscopic kinetic energies and potential energies of a system is called internal energy OR
the total energy content of a thermodynamic system under given set of conditions is known as internal energy.
∆𝑬 = 𝑬𝟐 − 𝑬𝟏
● Internal energy is a state function property.
APPLICATIONS AT CONSTANT VOLUME AND CONSTANT PRESSURE
1. The Process at Constant Volume
𝒒𝒗 = ∆𝑬 ∴ ∆𝑽 𝒂𝒏𝒅 𝑾 𝒂𝒓𝒆 𝒄𝒐𝒏𝒔𝒕𝒂𝒏𝒕
2. The Process at Constant Pressure
𝒒𝒑 = ∆𝑬 + 𝑷∆𝑽 ∴ ∆𝑬 + 𝑷∆𝑽 = ∆𝑯
𝒒𝒑 = ∆𝑯
∆𝑯 = ∆𝑬 + 𝑷∆𝑽 (𝑭𝒐𝒓 𝒐𝒏𝒍𝒚 𝑮𝒂𝒔𝒆𝒔)
∆𝑯 = ∆𝑬 (𝑭𝒐𝒓 𝑳𝒊𝒒𝒖𝒊𝒅𝒔 𝒂𝒏𝒅 𝑺𝒐𝒍𝒊𝒅𝒔)
HESS’S LAW
● G.H.Hess introduced a law of thermochemistry based on his observations on cyclic thermochemical changes
which involves two or more different routes. This is known as Hess’s law of enthalpy summation.
● This law states as if a chemical reaction can be brought about in more than one pathways, the net enthalpy
change is the same provided that the initial and final states are the same.
∆𝑯 = ∆𝑯𝟏 + ∆𝑯𝟐 + ∆𝑯𝟑 + ⋯
● The application of Hess’s law;
1. It is used in the determination of heat of reaction.
2. It is used in the determination of heat of formation.
3. It is used in the determination of lattice energy of ionic solids (Born-Haber cycle).
STANDARD ENTHALPIES OF FORMATION
● It defines as the enthalpy change of a chemical reaction in which one mole of pure substance is formed from its
elements with all substances in their standard state.
● It is represented by ∆H
o
f.

● The standard enthalpy of formation of most elements (H2, O2, N2, etc) is zero.
● The standard enthalpy of formation of most stable allotropic form of an element is zero.
● In carbon (graphite), in oxygen (O2) and in sulphur (Rhombic sulphur), all these three allotropic forms are stable
than other allotropic forms of same element so these (graphite, O2 and rhombic sulphur) has zero ∆H°f.
STANDARD ENTHALPY OF REACTION
● It is the enthalpy absorbed or evolved when fixed number of moles of reactants as represented in balance
chemical equation are completely reacted to form product with the conditions that all reactants and products are
in their standard state.
● It is represented by ∆H°.
∆𝑯𝒐 𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏 = [(∑ 𝒏𝒑∆𝑯𝒇 𝒐 ) − (∑ 𝒏𝒓∆𝑯𝒓 𝒐 𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕 )]
𝒑𝒓𝒐𝒅𝒖𝒄𝒕
BORN-HABER CYCLE
● Born-Haber cycle is developed by Max Born and Fritz Haber to correlate the lattice energy of ionic solids with
some other energies involved in there formation.
● It is a cycle of enthalpy change in which an ionic solid is theoretically formed from its elements in their standard
states.
● It is a specific application of Hess's law and generally use to determine lattice energy of ionic solids.

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CHAPTER NO: 12 ELECTROCHEMISTRY
INTRODUCTION
● Electrochemistry is the study of interchange of chemical and electrical energy.
OXIDATION-REDUCTION
● Reduction and oxidation reactions, collectively known as redox reactions, are associated with the electrons
transfer from one species to another.
● If one species in a reaction loses electrons, it is said to be oxidized and acts as a reducing agent, at the same
time the other species gains electrons and get reduced, therefore acts as oxidizing agent.
● Rusting of iron, Photosynthesis, Fading of cloth’s color, Generation of electric current in batteries, etc are redox
reactions.
● Oxidation refers to the addition of oxygen or removal of hydrogen from a substance.
● Reduction originally describes the addition of hydrogen or removal of oxygen from a compound.
● According to modern electronic concept, oxidation is the chemical process in which electrons are lost by an
atom or ion whereas reduction involves the gain of electrons.
● Oxidation may result in producing or increasing the positive charge on the species or decreasing its negative
charge. Contrarily reduction involves in producing or increasing the negative charge on the species or
decreasing its positive charge.
● According to oxidation number concept, oxidation is a process in which the oxidation state of an element
increases while reduction is a process in which the oxidation state of an elements decreases.
● In any redox reaction, the species that oxidizes the other substance and itself get reduced is known as oxidizing
agent whereas the species that reduces other substance but itself get oxidized is identified as reducing agent.
● There are some general characteristics of redox reactions;
1. All redox reactions may involve the transfer of electrons.
2. Oxidation and reduction process always occurs side by side thus if one substance is oxidized and other
is reduced at the same time.
3. Not all atoms in a redox reaction need to change their oxidation states but at least one atom should be
oxidized and one should be reduced.
OXIDATION NUMBER
● Oxidation number is an apparent charge on an atom in a compound.
●
° ° ° °
Oxidation number of all elements in Free State (uncombined state) is taken as zero i.e. K , Cl2 , H2 , O2 , etc.
●
+
The oxidation number of a monoatomic ion is the same as the charge appear on it i.e. oxidation number of Na is
2+
+1 and Ca is +2, etc.
●
° o
The sum of oxidation numbers of all elements in a neutral compound is zero i.e. H2SO4 , CO2 .
● The oxidation number of oxygen in most of its compounds is -2, however in peroxides it is -1 (Na2O2, H2O2, etc), in
superoxides is -½ (KO2, etc) and in oxyflouride (OF2) is +2.
● Oxidation number of hydrogen in covalent compounds is assigned as +1. However in metal hybrides its oxidation
+ - + -
number is -1 i.e. Na H , K H , etc.
● The oxidation numbers of group IA and group IIA elements are general assigned +1 and +2 respectively.
● The oxidation number of fluorine in all its compounds is always taken as -1.
● In polyatomic ion, the sum of oxidation numbers of all the atoms present in them is equal to the net ionic charge
on the ion.
ION ELECTRON METHOD
● In ion electron method, only those reactants and products of redox reaction are balanced that contain the
elements undergoing a change in oxidation state.
●
+
In acidic or neutral medium, H2O and H are added for balancing oxygen and hydrogen respectively. In case of
-
basic medium, OH and H2O are added to balance oxygen and hydrogen respectively.
ELECTROLYTIC CELL
● Each electrolytic cell has two electrodes i.e. cathode and anode.
● The electrode which attach with negative terminal of battery is called cathode and the electrode which is attached
with positive terminal of battery is called anode.
● Cathode is negative electrode on which reduction occurs while anode is positive electrode on which oxidation
- +
occurs. (C RA O)
● The passage of electricity through electrodes, break the solution into ions i.e. cations (+ve ions) and anions (-ve
ions).
● Cations move towards cathode where they gain electrons while anion move towards anode where they loss
electrons.
● The movement of cations and anions towards their respective electrode in an electrolytic solution under the
influence of electric current is known as electrolysis.
𝒆𝒍𝒆𝒄𝒕𝒓𝒊𝒄𝒊𝒕𝒚
𝑪𝒂𝑪𝒍𝟐 → 𝑪𝒂+𝟐 + 𝟐𝑪𝒍−
+𝟐
𝑪𝒂 + 𝟐𝒆̅ → 𝑪𝒂 (𝒓𝒆𝒅𝒖𝒄𝒕𝒊𝒐𝒏 𝒂𝒕 𝒄𝒂𝒕𝒉𝒐𝒅𝒆)
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 𝟐𝑪𝒍− → 𝑪𝒍𝟐 + 𝟐𝒆̅ (𝒐𝒙𝒊𝒅𝒂𝒕𝒊𝒐𝒏 𝒂𝒕 𝒂𝒏𝒐𝒅𝒆)
GALVANIC CELL
● A Galvanic cell or Voltaic cell is a type of electrochemical cell in which current is generated by a spontaneous
redox reaction.
● Galvanic cell consist of two half cells connected with each other through salt bridge of KCl.
● A salt bridge is a U-shaped glass tube in which an inert electrolyte is filled along with gel. It allows the flow of
ions but prevent the mixing of solution. It maintains the electrical neutrality in each half cell.
● In Galvanic cell, anode is negative and cathode is positive.
CELL POTENTIAL
● The driving force with which the electrons pushes put from anode into external circuit is known as electromotive
force, cell potential or cell voltage.
● It may be defined as the potential difference between the two electrodes in a voltaic cell.
● The standard electrode potential of a single half-cell is defined as the difference of potential created between
metal electrode and 1 molar solution of its ions at 25°C and 1atm. It is abbreviates by E° and measured in volt.
● The capability of electrode to get oxidized in its electrolytic solution is known as oxidation potential whereas the
tendency of electrode to get reduced and allows the positive ions of solution to deposit on it is called reduction
potential.
● IUPAC convention recommended that electrode potential is taken as reduction potential. Therefore while
constructing a Galvanic cell, cathode should be of higher reduction potential and anode should be of lower
reduction potential.
● The most commonly used reference electrode is standard hydrogen electrode (SHE) which assigned as an
electrode potential of 0.00Volt.
𝑬𝒐 (𝒄𝒆𝒍𝒍) = 𝑬𝒐 (𝒄𝒂𝒕𝒉𝒐𝒅𝒆) − 𝑬𝒐 (𝒂𝒏𝒐𝒅𝒆)
ELECTRODE POTENTIAL OF ZINC
𝒁𝒏 → 𝒁𝒏+𝟐 + 𝟐𝒆̅ (𝒐𝒙𝒊𝒅𝒂𝒕𝒊𝒐𝒏 𝒂𝒕 𝒂𝒏𝒐𝒅𝒆)
𝟐𝑯+ + 𝟐𝒆̅ → 𝑯𝟐 (𝒓𝒆𝒅𝒖𝒄𝒂𝒕𝒊𝒐𝒏 𝒂𝒕 𝒄𝒂𝒕𝒉𝒐𝒅𝒆)
𝒁𝒏| 𝒁𝒏+𝟐 (𝟏𝑴) || 𝟐𝑯+ (𝟏𝑴)| 𝑯𝟐 (𝟏𝒂𝒕𝒎, 𝑷𝒕)
𝑬𝒐 (𝒛𝒊𝒏𝒄) = −𝟎. 𝟕𝟔𝑽𝒐𝒍𝒕
ELECTRODE POTENTIAL OF COPPER
𝑯𝟐 → 𝟐𝑯+ + 𝟐𝒆̅ (𝒐𝒙𝒊𝒅𝒂𝒕𝒊𝒐𝒏 𝒂𝒕 𝒂𝒏𝒐𝒅𝒆)
𝑪𝒖+𝟐 + 𝟐𝒆̅ → 𝑪𝒖 (𝒓𝒆𝒅𝒖𝒄𝒂𝒕𝒊𝒐𝒏 𝒂𝒕 𝒄𝒂𝒕𝒉𝒐𝒅𝒆)
𝑯𝟐 (𝟏𝒂𝒕𝒎, 𝑷𝒕)| 𝟐𝑯+ (𝟏𝑴) || 𝑪𝒖+𝟐 (𝟏𝑴)|𝑪𝒖
𝑬𝒐 (𝒄𝒐𝒑𝒑𝒆𝒓) = +𝟎. 𝟑𝟒𝑽𝒐𝒍𝒕
ELECTROCHEMICAL SERIES
● Electrodes above hydrogen in ECS have negative electrode potential. They have stronger tendency to loss
electrons (oxidation) then hydrogen, these substances thus acts as reducing agent (anode).
● Electrodes which are placed below hydrogen in ECS have positive electrode potential. They have greater ability
to gain electron (reduction) as compared to hydrogen and hence serves as oxidizing agent (cathode).
● Strength of reducing agent increases from bottom to top and vice versa while strength of oxidizing agent
increases from top to bottom and vice versa.
BATTERIES
● A battery consist of two or more Galvanic cells connected in series and used to convert chemical energy into
electrical energy by means of redox reactions.
● There are two types of batteries;
1. Primary Battery
● In this type of batteries, redox reaction takes place in only one direction and can't be reversed. Thus these
batteries can't be recharged or reused.
● The most inexpensive and commonly used primary battery is dry cell.
2. Secondary Battery
● These batteries can be recharged by the electricity flow through the cell by utilizing a source of external power
supply after every use.
● Lead storage battery which is commonly known as car battery is an example of secondary Battery.
DRY CELL
● The common dry cell was first invented by Leclanche.
● The outer body of this cell is made up of zinc which serves as anode whereas a graphite rod located at the center
works as cathode.
● The region between cathode and anode is filled with a paste of MnO2, carbon, NH4Cl and ZnCl2.
𝒁𝒏 → 𝒁𝒏+𝟐 + 𝟐𝒆̅ (𝒂𝒏𝒐𝒅𝒆)
𝟐𝑵𝑯𝟒 + + 𝟐𝑴𝒏𝑶𝟐 + 𝟐𝒆̅ → 𝑴𝒏𝟐 𝑶𝟑 + 𝟐𝑵𝑯𝟑 + 𝑯𝟐 𝑶 (𝒄𝒂𝒕𝒉𝒐𝒅𝒆)

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LEAD STORAGE BATTERY OR CAR BATTERY
● A 12 volt car battery is made up of six Galvanic cells connected in series, each of which has an Emf of 2 volt.
● All anode plates are made up of lead (Pb) while all cathode plates are also made up of lead but coated with PbO 2.
Both groups of plates are alternatively suspended into dilute solution of H2SO4 of specific gravity of 1.25.
𝑷𝒃 + 𝑺𝑶𝟒 −𝟐 → 𝑷𝒃𝑺𝑶𝟒 + 𝟐𝒆̅ (𝒂𝒏𝒐𝒅𝒆)
𝑷𝒃𝑶𝟐 + 𝟒𝑯+ + 𝑺𝑶𝟒 −𝟐 + 𝟐𝒆̅ → 𝑷𝒃𝑺𝑶𝟒 + 𝟐𝑯𝟐 𝑶 (𝒄𝒂𝒕𝒉𝒐𝒅𝒆)
● When the battery is needed to be recharged, its anode (Pb) is connected to negative terminal and cathode (PbO4)
is connected to positive terminal of external power supply.
𝑷𝒃𝑺𝑶𝟒 + 𝟐𝒆̅ → 𝑷𝒃 + 𝑺𝑶𝟒 −𝟐
𝑷𝒃𝑺𝑶𝟒 + 𝟐𝑯𝟐 𝑶 → 𝑷𝒃𝑶𝟐 + 𝟒𝑯+ + 𝑺𝑶𝟒 −𝟐 + 𝟐𝒆̅
FUEL CELL
● A hydrogen oxygen fuel cell is a unique type of Galvanic cell which is based on the reaction between hydrogen
and oxygen to produce water and the heat release in the reaction is used to produce electricity.
● It can't store reactants hence reactants are fed continuously.
● It consists of two porous carbon electrodes having a thin platinum plate. Platinum serves as catalyst.
● The compartment between the two electrodes is filled with concentration solution of KOH which works as
electrolyte.
● Hydrogen gas works as anode while oxygen gas works as cathode.
𝟐𝑯𝟐 + 𝟒𝑶𝑯− → 𝟒𝑯𝟐 𝑶 + 𝟒𝒆̅ (𝒂𝒏𝒐𝒅𝒆)
𝑶𝟐 + 𝟐𝑯𝟐 𝑶 + 𝟒𝒆̅ → 𝟒𝑶𝑯− (𝒄𝒂𝒕𝒉𝒐𝒅𝒆)
𝟐𝑯𝟐 + 𝑶𝟐 → 𝟐𝑯𝟐 𝑶 (𝒐𝒗𝒆𝒓𝒂𝒍𝒍 𝒓𝒆𝒂𝒄𝒕𝒊𝒐𝒏)
CORROSION AND ITS PREVENTION
● A spontaneous process in which surface atoms of metals get oxidized due to the action of surrounding medium
is known as corrosion.
● The most familiar type of corrosion is the rusting of iron. Rust is a brown powdery material produce on the
surface of iron appliances due to an oxidation reaction of iron atoms with moist air.
● Corrosion is an electrochemical process.
● There are two common methods are used to prevention of corrosion i.e. Galvanizing and Electroplating.
● The process of coating a thin layer of zinc on a metal is known as galvanizing.
● Electroplating is the coating of one metal on the surface of another by means of electrolysis.

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