GrADE- XI

chemistry NOTES
VoL-i
(2022- ’23)

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 Chapter 1: Some Basic concepts of Chemistry

Main points:

1. Matter: Anything that occupies space and has mass is called matter.

2. Mass and Weight:

• Mass of a substance is the amount of matter present in it while weight is the force exerted by gravity on
an object.
• The mass of a substance is constant whereas its weight may vary from one place to another due to change
in gravity.
• The mass of a substance can be determined very accurately by using analytical balance.
3. Density:

• Density of a substance is its amount of mass per unit volume.

• SI unit of density = SI unit of mass/SI unit of volume = kg/m 3 or kg m–3
4. Temperature: There are three common scales to measure temperature. These are °C (degree celsius),
°F (degree Fahrenheit) and K (kelvin).
• Kelvin is the SI unit of temperature. K = °C + 273.
• Temperature below 0 °C (i.e. negative values) are possible in Celsius scale but in Kelvin scale, negative
temperature is not possible.
5. Physical Classification of Matter:

Properties Solid Liquid Gas

1.Volume Definite Definite Indefinite

2.Shape Definite Indefinite Indefinite

Density High Moderate Least

Intermolecular Very small Slightly greater Large

Space

Movement Cannot move but Moves fast as it is Moves faster as it is

vibrate fluid fluid

Force of attraction Very high Moderate Negligible / Very low

Arrangement of Orderly arranged Free to move within Free to move

molecules the given volume everywhere

Kinetic energy Very small Moderate Larger kinetic energy

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 Rigidity Very rigid Not rigid and known Not rigid and known
as fluid as fluid

Compressibility Not compressible Not compressible Highly compressible

Expansion on Very little Slightly greater Highly expand

heating

Fluidity Can’t flow Can flow Can flow

Diffusion Can diffuse due to Can diffuse and rate Can diffuse and rate
kinetic energy of of diffusion is fast of diffusion is very
liquid/gas but not fast
between two solids

6. Chemical Classification of matter:

Elements:

• An element is the simplest form of matter that cannot be split into simpler substances or built from
simpler substances by any ordinary chemical or physical method.
• There are 114 elements known to us, out of which 92 are naturally occurring while the rest have been
prepared artificially.
• Elements are further classified into metals, non-metals and metalloids.

Compounds:

• A compound is a pure substance made up of two or more elements combined in a definite proportion by
mass, which could be split by suitable chemical methods.
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• Compounds always contain a definite proportion of the same elements by mass. The properties of
compounds are totally different from the elements from which they are formed.
• Compounds are homogeneous.
• Compounds are broadly classified into inorganic and organic compounds.
• Inorganic compounds are those, which are obtained from non-living sources such as minerals. For
example, common salt, marble and limestone.
• Organic compounds are those, which occur in living sources such as plants and animals. They all contain
carbon. Common organic compounds are oils, wax, fats etc.

Mixtures:

• A mixture is a combination of two/ more elements or two/ more compounds or elements and compounds
in any proportion so that the components do not lose their identity.
• Air is an example of a mixture.
• Mixtures are of two types, homogeneous and heterogeneous.
• Homogeneous mixtures have the same composition throughout the sample. The components of such
mixtures cannot be seen under a powerful microscope. They are also called solutions. Examples of
homogeneous mixtures are air, seawater, gasoline, brass etc.
• Heterogeneous mixtures consist of two or more parts (phases), which have different compositions. These
mixtures have visible boundaries of separation between the different constituents and can be seen with
the naked eye e.g., sand and salt, chalk powder in water etc.

7. SI system of units:

• Metric System was based on the decimal system. The International System of Unit, SI unit (in French Le
Systeme International d’Unites–abbreviated as SI) was established by the 11th General Conference on
Weights and Measures (CGPM from Conference Generale des Poids at Measures).
• The SI system has seven base units which pertain to the 7 fundamental scientific quantity.

Base Physical Quantity Symbol for quantity Name of SI unit Symbol for SI unit

Length l Metre M

Mass m Kilogram Kg

Time t Second S

Electrical current I Ampere A

Thermodynamic temperature T Kelvin K

Amount of substance n Mole Mol

Luminous Intensity Iv Candela Cd

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• A common unit, litre (L) is not a SI unit that is used for measurement of volume of liquids. 1 L = 1000 mL,
1000 cm3= 1 dm3
• The SI system allows the use of prefixes to indicate the multiples or submultiples of a unit.
Prefixes in SI system:

Multiple Prefix Symbol

10-12 pico pm

10-9 nano nm

10-6 micro μm

10-3 mili mm

10-2 centi cm

• 1 Angstrom (A0) = 10-10 metre

8. Scientific Notation:

• Scientific notation is the proper representation of a number in its exponential form.

• It is the notation in which any number can be represented in the form N × 10n (Where n is an
exponent having positive or negative values and N can vary between 1 to 10).
• We can write 232.508 as 2.32508 x102 in scientific notation.
• Similarly, 0.00016 can be written as 1.6 x 10–4.

9. Precision: Precision refers to the closeness of various measurements for the same quantity.

10. Accuracy: Accuracy is the agreement of a particular value to the true value of the result.

11. Significant Figures:

• The reliability of a measurement is indicated by the number of digits used to represent it. To express it
more accurately we express it with digits that are known with certainty. These are called as Significant
figures. They contain all the certain digits plus one doubtful digit in a number.

Rules for Determining the Number of Significant Figures:

• All non-zero digits are significant. For example, 6.9 has two significant figures, while 2.16 has three
significant figures. The decimal place does not determine the number of significant figures.
• A zero becomes significant in case it comes in between non zero numbers. For example, 2.003 has four
significant figures, 4.02 has three significant figures.

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• Zeros at the beginning of a number are not significant. For example, 0.002 has one significant figure while
0.0045 has two significant figures.
• All zeros placed to the right of a number are significant. For example, 16.0 has three significant figures,
while 16.00 has four significant figures. Zeros at the end of a number without decimal point are
ambiguous.
• In exponential notations, the numerical portion represents the number of significant figures. For example,
0.00045 is expressed as 4.5 x 10-4 in terms of scientific notations. The number of significant figures in this
number is 2, while in Avogadro's number (6.023 x 1023), it is four.
• The decimal point does not count towards the number of significant figures. For example, the number
345601 has six significant figures but can be written in different ways, as 345.601 or 0.345601 or 3.45601
all having same number of significant figures.

Retention of Significant Figures and Rounding off Figures:

• The rounding off procedure is applied to retain the required number of significant figures.
• If the digit coming after the desired number of significance is its am figures happens to be more than 5,
the preceding significant figure is increased by one, 4.317 is rounded off to 4.32.
• If the digit involved is less than 5, it is neglected and the preceding significant figure remains unchanged,
4.312 is rounded off to 4.31.
• If the digit happens to be 5, the last mentioned or preceding significant figure is increased by one only in
case it happens to be odd. In case of even figure, the preceding digit remains unchanged. 8.375 is rounded
off to 8.38 while 8.365 is rounded off to 8.36.

12. Dimensional Analysis:

During calculations generally there is a need to convert units from one system to other. This is called
factor label method or unit factor method or dimensional analysis. For example, 5 feet and 2 inches is
to converted in SI unit as 1 inch = 2.54 x 10-2 m then, 5 feet and 2 inch = 62 inches.

13. Laws of chemical combinations:

• A chemical change in which two or more substances combine to give a new single compound is called
chemical combination.
• Lavoisier and Proust established two important laws of chemical combination after much experiment.

Daltons Atomic Theory: All matter is made up of very tiny indivisible particles is called atomic theory of
matter.

The postulates of Dalton’s atomic theory are as follows:

• All matter is made up of very tiny particles called atoms.

• Atoms are indivisible; they cannot be created or destroyed in a chemical reaction.
• Atoms of a given element are identical in chemical properties and mass.
• Atoms of different elements have different elements have different mass and chemical properties.

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• Atoms combine in small whole no. ratio to form compounds.
• The relative no. and kind of atoms are constant in a given compound.

Draw backs of Daltons Atomic Theory:

• Sub-atomic particles (electron, proton and neutron) exist which were not mentioned in this theory.
• Atoms of the same element can have different masses. Such atoms of the same element having same
atomic number but different mass number are called isotopes.
e.g. 35 37
17𝐶𝑙 and 17𝐶𝑙

• Atoms of different elements can have same mass. Such atoms of different elements having different
atomic number but same mass number are called isobars.
e.g 40Ar and 40Ca
18 20

• Atoms may not always combine in simple whole number ratios to form compounds.
e.g., C: H: O in sugar (C12H22O11) = 12:22:11 which is not a simple ratio.

Law of Conservation of Mass (Given by Antoine Lavoisier in 1789):

• It states that matter (mass) can neither be created nor destroyed.
• According to the law of conservation of mass, the mass of the products in a chemical reaction must equal
the mass of the reactants.

Law of Definite Proportions or Law of Constant Proportions:

• This law was proposed by Louis Proust in 1799, which states that a chemical compound always consists
of the same elements combined together in the same ratio, irrespective of the method of preparation or
the source from where itis taken.
• For example, in NO2 molecule, the ratio of the number of nitrogen and oxygen atoms is 1:2 but the mass
ratio is 14:32 (or 7:16).

Law of multiple proportion:

• It states that when two different elements combined to form more than one compound and if mass of
one element is fixed then other elements mass bears simple whole no. ratio.
• Example:
Carbon monoxide (CO): 12 parts by mass of carbon combines with 16 parts by mass of oxygen.
Carbon dioxide (CO2): 12 parts by mass of carbon combines with 32 parts by mass of oxygen.

Hence, the ratio of the masses of oxygen that combines with a fixed mass of carbon (12 parts) is
16:32 = 1:2 which is a simple whole no. ratio.

Gay Lusaac’s Law of Gaseous volumes:

• When gases combine, they bear simple whole number ratio of their volumes provided all the gases are at
the same temperature and pressure.
• For example, in the following reaction, the ratio of volumes of hydrogen, chlorine, and hydrogen chloride
is 1:1:2 (a simple ratio).

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• Laws of Reciprocal Proportion: It states that If two different elements combine separately with a fixed
mass of a third element, the ratio of the masses in which they do so are either the same as or a simple
multiple of the ratio of the masses in which they combine with each other.
• Example:
Consider 3 grams of C reacting with 1 g of H to form methane.
Also, 8 g of O reacting with 1 g of H to form water.
Here, the mass ratio of carbon and oxygen is 3:8.
Similarly, 12 g of C reacts with 32 g of O to form CO2.
The mass ratio of carbon and oxygen is 12:32 = 3:8
The mass ratio in which C and O combine with each other is the same as the mass ratio in which they
separately combine with a fixed mass of H.

Avogadro’s law:

• Avogadro’s law, also known as Avogadro’s principle or Avogadro’s hypothesis, is a gas law which states
that the total number of atoms/molecules of a gas (i.e. the amount of gaseous substance) is directly
proportional to the volume occupied by the gas at constant temperature and pressure.

• At constant pressure and temperature, Avogadro’s law can be expressed via the following formula:
V∝n
V/n = k
Where V is the volume of the gas, n denotes the amount of gaseous substance (often expressed in moles),
and k is a constant. When the amount of gaseous substance is increased, the corresponding increase in
the volume occupied by the gas can be calculated with the help of the following formula:
V1/n1 = V2/n2 = k (as per Avogadro’s law)

• 6.022×1023 is known as Avogadro’s number.

14. Mole concept:

• A group of 6.022×1023 particles (atoms/molecules/ions) of a substance is called a mole of that substance.

• This no. (6.022×1023) is known as Avogadro’s constant and it is represented as N0.
• The mass of one mole of any substance is also fixed and it equals to the gram atomic mass (for atoms) or
the gram molecular mass (for molecules) of any substance.
• The symbol of an element represents 1 mole of atoms of that element.
• The molecular formula of a substance represents 1 mole of molecules of that substance.
• A mole of a substance is that amount of a substance which contains the same number of particles
(atoms/molecules/ions) as there are carbon atoms in 12 gm of C-12.
• The mass of one mole of a substance in grams is called its molar mass.
• The volume occupied by one mole of any substance is called its molar volume. One mole of all gaseous
substances at 273 K and 1 atm pressure occupies a volume equal to 22.4 litre or 22,400 ml. The unit of
molar volume is litre per mol or millilitre per mol.

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15. Percentage composition, Empirical Formula and Molecular Formula:

• The mass percentage of each constituent element present in any compound is called its percentage
composition.
• An empirical formula represents the simplest whole number ratio of various atoms present in a
compound. E.g. CH is the empirical formula of benzene.
• The molecular formula shows the exact number of different types of atoms present in a molecule of a
compound. E.g. C6H6 is the molecular formula of benzene.
• Molecular formula = n x empirical formula where n = number of moles
16. Limiting Reagent: The reactant which gets consumed first or limits the amount of product formed is
known as limiting reagent.

17. Concentration of Solutions: Concentration of a solution can be expressed in any of the following ways:

• Mass Percent: It is the mass of the solute in grams per 100 grams of the solution.
𝑴𝒂𝒔𝒔 𝒐𝒇 𝒕𝒉𝒆 𝒔𝒐𝒍𝒖𝒕𝒆
Mass percent = 𝑴𝒂𝒔𝒔 𝒐𝒇 𝒕𝒉𝒆 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏 × 100
For example, A 5 % solution of sodium chloride means that 5 g of NaCl is present in 100 g of the solution.
• Volume percent: It is the number of units of volume of the solute per 100 units of the volume of solution.
𝑽𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒕𝒉𝒆 𝒔𝒐𝒍𝒖𝒕𝒆 (𝒎𝒍)
• Volume percent = 𝑽𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒕𝒉𝒆 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏 (𝒎𝒍) × 100
• For example, 5 % (v/v) solution of ethyl alcohol contains 5 cm3 of alcohol in 100 cm3 of the solution.
• Molarity: Molarity of the solution is defined as the number of moles of solute dissolved per litre (dm 3) of
the solution. It is denoted by the symbol M.
• Measurements in Molarity can change with the change in temperature because solutions expand or
contract accordingly.
Number of moles of the solute 𝑛
• Molarity of the solution = =
Volume of the solution in litre 𝑣

• The Molarity of the solution can also be expressed in terms of mass and molar mass.
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑒
Molarity of the solution = 𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑒 × 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑖𝑛 𝑙𝑖𝑡𝑟𝑒

• Molarity equation

To calculate the volume of a definite solution required to prepare solution of other molarity, the following
equation is used:
M1V1 = M2V2 where M1= initial molarity, M2= final molarity
V1 = Initial volume, V2 = final volume

• Molality: Molality of the solution is defined as the number of moles of solute dissolved per kg of the
solution. It is denoted by the symbol m.
Number of moles of the solute
• Molality of the solution = Mass of the solution in kg

𝑀𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑒

• Molality of the solution = 𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑒 × 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑡ℎ𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑖𝑛 𝑘𝑔
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• Mole fraction: It is a ratio of no of moles of a particular component to the total number of moles of the
solution (solute + solvent).
• If a substance ‘A’ dissolves in substance ‘B’ and their number of moles are nA and nB respectively, then
the mole fractions of A and B are given as follows:

Number of moles of A
• Mole fraction of ‘A’ = Number of moles of the solution

𝑛A
= 𝑛A + 𝑛B

Number of moles of B
Also, Mole fraction of ‘B’ = Number of moles of the solution

𝑛B
= 𝑛A + 𝑛B

Numerical Problems:

1. A piece of copper wire is 2.00 inch long. What is its length in centimeter?

Ans: 1 inch = 2.54 cm

Therefore, 2 inch = 2.54 x 2 = 5.08 cm
2. A plastic Jug contains 3.5 L of milk. Calculate the volume of milk in meter3.

Ans: 1 L = 1000 cm3

3.5 L = 1000 x 3.5 cm3 = 3500.0 cm3 = 3.5 x 1000 x 1 / 106 m3 = 3.5 x 10-3 m3
(1m3 = 1m x 1m x 1m = 100cm x 100cm x 100cm = 106 cm3)

3. Calculate the molecular mass of the following:

a) Ethane (C2H6) b) Ammonia (NH3)

Ans: a) Ethane (C2H6) = 2 x atomic mass of carbon + 6 x atomic mass of hydrogen

= 2 x (12u) + 6 x (1U) = 24u + 6u = 30u
b) Ammonia (NH3) = 1x atomic mass of nitrogen + 3 x atomic mass of hydrogen
= 1x(14u) + 3 x (1u) = 14u + 3u = 17u
4. Calculate the formula mass of KCl (Potassium chloride).

Ans: Formula mass of KCl = Atomic mass of K + Atomic mass of Cl = 39u + 35.5u = 74.5u

5. Calculate the no of molecules present in 2.5 moles of water (H2O).

Ans: 1 mole of water = 6.022 x 1023 no. of H2O molecules

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 Therefore, 2.5 moles of water = 2.5 x 6.022 x 1023 no. of H2O molecules
= 15.055 x 1023 no. of H2O molecules
6. Calculate the percent (%) composition of elements in methanol (CH3OH).

Ans: Molecular formula of methanol = CH3OH

Molecular mass of methanol = 1 x 12+ 4 x 1+ 1x16 = 32 gm
Percent composition of carbon = Mass of carbon x 100 /Molecular mass of CH3OH
= 12.01 X 100/32 = 37.48%
Percent composition of Hydrogen = Mass of Hydrogen x 100/ Molecular mass of CH3OH
= 4.032 x 100 /32 = 12.5%
Percent composition of Oxygen = 16 x 100 /32 = 49.93%
7. Calculate the amount of water in gm produced by the combustion of 8 gm of ethane.

Ans: Reaction: C2H6 (g) + 3½ O2 (g) → 2CO2 (g) + 3H2O (g)

Now, 30 gms of ethane or 1 mole ethane produces 3 moles of H2O
1 mole of H2O = 18 gm of H2O
3 mole of H2O = 18x3 = 54 gm of water
‫؞‬30 gm of ethane produces 54 gm of water
‫ ؞‬8 gm ethane produces = 8 x 54 = 14.4 gm of water
8. How many moles of methane required to produce 88 gm of CO2 after combustion?

Ans: Combustion reaction: CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (g)

16 gm of CH4 = 1 mole CH4 produces 1 mole of CO2 = 44 gm of CO2

So, 44 gm of CO2 is produced from 1 mole of methane

88 gm of CO2 is produced from 2 moles of methane

9. 25 Kg of N2 (gm) and 5 Kg of H2 are mixed to produce Ammonia (NH3). Calculate the amount of ammonia
formed.

Ans: Equation: N2 (g) +3H2(g) → 2NH3 (g)

1 Kg of N2 = 1000gm N2
25 Kg of N2 = 25 x 1000 gm N2
= 25000/28 = 892.85 mol N2
1 Kg of H2 = 1000 gm H2
5 Kg of H2 = 5x 1000 gm H2
= 5000/2 = 2500 mol H2

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 According to above equation,
1 mol of N2(g) requires 3 moles of H2(g)
Hence 892.85 mole of N2 will require 892.85 x 3 mol of H2 = 2678.55 mol = 2.67855 x 103 mol H2
But we have 2500 mol of H2 and in this process 2678.55 mol of H2 is required.
Now, 3 moles of H2(g) produces 2 moles of NH3
2500 mole of H2 produces 2500 x 2/3 = 1666.66 mol of NH3
10. A solution is prepared by adding 4.00 gm of a substance A to 18 gm of water. Calculate the mass
percent of the solute.

Ans: Mass % of solute (A) = Mass of solute (A) x 100/ Mass of solution = 4 x 100/22
= 400/22 = 18.18 %
Mass % of solute = 18.18%
11. Calculate the molarity of sodium Hydroxide (NaOH) in a solution prepared by dissolving 4 gm in 500
ml of the solution.

Ans: Molarity = No of moles of solute /Volume of solution in litre

No. of moles of NaOH = Mass of NaOH/molar mass of NaOH = 4/40 = 0.1
Volume of solution =0.5 Litre
Molarity = 0.1/0.5 = 1/5 = 0.2 mol / litre

12. The density of 2M solution of sodium chloride (NaCl) is 1.13 g mol/litre. Calculate molality of the
solution. (2M= 2 mol per litre).

Ans: Mass of NaCl in 1 litre solution = 2 x 58.5 = 117.0 gm as the solution is 2M

Mass of 1 litre solution = 1000 x 1.13 = 1130 g as density is 1.13 g mol/litre
Mass of water in solution = 1130 g – 117.0 g = 1013 g
Molality = No of moles of solute /Mass of solvent in Kg
= 2 mol / 1.013 Kg = 1.9743

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 Chapter 2: Structure of atom

Main points:

• Atom is the smallest indivisible particle of the matter.

• Atoms are made up of three subatomic particles: electrons, protons and neutrons.
• The mass of an electron is about 1/1840 of the mass of hydrogen atom i.e 1/1840 u since the mass of a
hydrogen atom is 1 u.
• The absolute mass of an electron is 9.1×10-28 gm.
• The absolute charge of an electron is 1.6×10-19coulomb. The relative charge of an electron is -1.
• The mass of a proton is equal to the mass of a hydrogen atom i.e 1 u.
• The absolute mass of a proton is 1.6×10-24 gm.
• The absolute charge of a proton is 1.6×10-19coulomb. The relative charge of a proton is +1.
• The formation of cathode rays and anode rays on passing electricity at very low pressure tells us that
atom is not indivisible; it is made up of smaller particles.

Discovery of electrons:
• Discovery of electrons in an atom was done by J.J Thomson through cathode ray discharge tube
experiment.

Cathode ray discharge tube experiment:

• A cathode ray discharge tube made of glass is taken with two electrodes.
• At very low pressure and high voltage, current is passed through it.
• A stream of particles was seen moving in the tube from cathode to anode. These rays were called cathode
rays.
• When a perforated anode was taken, the cathode rays struck the other end of the glass tube at the
fluorescent coating of ZnS and a bright spot on the coating was developed.

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Deflection of cathode ray in the presence of electric and magnetic field:

Results:
• Cathode rays consist of negatively charged electrons.
• Cathode rays themselves are not visible but their behaviour can be observed with help of fluorescent or
phosphorescent materials.
• In absence of electrical or magnetic field cathode rays travel in straight lines.
• In presence of electrical or magnetic field, behaviour of cathode rays is similar to that shown by electrons.
• The characteristics of the cathode rays do not depend upon the material of the electrodes and the nature
of the gas present in the cathode ray tube.
• Charge to mass ratio of an electron was determined by Thomson. The charge to mass ratio of an electron
as 1.758820 x 1011 C kg-1.
• Charge on an electron was determined by R. A. Millikan by using an oil drop experiment. The value of the
charge on an electron is -1.6 x 10-19 C.
• The mass on an electron was determined by combining the results of Thomson’s experiment and
Millikan’s oil drop experiment and it is 9.1094 x 10-31 kg.

Discovery of protons:
• Discovery of protons in an atom was done by Goldstein.
• Goldstein passed electricity at high voltage through a gas at very low pressure taken in a discharge tube.
• Streams of heavy particles were given out by the anode which is known as anode rays.

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Characteristics of Canal rays:
• Charge to mass ratio of the particles present in canal ray depends on gas from which they originate.
• The positively charged particles depend upon the nature of gas present in the cathode ray discharge tube.
• Some of the positively charged particles carry a multiple of fundamental of electrical charge.
• Behaviour of positively charged particles in electrical or magnetic field is opposite to that observed for
cathode rays.

Discovery of neutrons:
• Neutrons were discovered by James Chadwick by bombarding a thin sheet of beryllium by α- particles.
• They are electrically neutral particles having a mass slightly greater than that of the protons. The relative
mass of a neutron is 1 u while the absolute mass of a neutron is 1.674×10-24 gm.
• Discovery of these sub atomic particles inside the atom led to the failure of Dalton’s atomic theory.
• Many scientists proposed various atomic models. Thomson was the first one to propose a model for the
structure of an atom.

Comparison of the properties of electron, proton and neutron:

S. No Property Electrons Protons Neutrons

1. Relative Charge -1 +1 0

2. Absolute Charge -1.6×10-19 C +1.6×10-19 C 0

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3. Relative mass times the mass of an Equal to the mass Equal to the mass
1840
H atom of a H atom of a H atom

4. Absolute mass 9.1×10-31kg 1.67×10-27kg 1.67×10-27kg

Thomson’s atomic model:

• An atom is considered to be a sphere of a uniform positive

charge and the electrons are embedded in the sphere.
• He compared the atom with a water melon where the positive
charge was compared with the pulp of the water melon and the
negative charge was compared with the seeds of the water
melon. It is also known as plum pudding model.

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Postulates:
• An atom consists of a positively charged sphere and the electrons are embedded in it.
• The magnitude of the negative and positive charge is equal.
• The mass of the atom is uniformly distributed.

Drawbacks:
This model cannot explain the results of experiments carried out by other scientists.

Rutherford’s α-ray scattering experiment and atomic model:

A stream of high energy α- particles (He2+ion) was bombarded at a thin foil (thickness 100nm) of gold metal.

Observations:
• Most of the α- particles passed through the gold foil undeflected.
• A small fraction of the α-particles was deflected by small angles.
• A very few α-particles (1 in 12000) bounced back.

Rutherford’s Gold foil experiment

Conclusion:
• Most of the space in the atom is empty as most of the α- particles passed through the foil undeflected.
• Some of the positively charged α-particles were deflected by small or large angles. For this to happen, the
α-particles must approach a heavy positively charged mass, inside the atom so that it repels the α-rays.
• Since the number of the α-particles which bounced back was very small it was concluded that the volume
occupied by the positive charge of the atom is very small as compared to the total volume of the atom.

Postulates of Rutherford’s atomic model:

• There is a positively charged part in an atom called the nucleus. Nearly all the mass of an atom resides in
the nucleus.
• The electrons revolve around the nucleus in well-defined circular orbits.
• The size of the nucleus is very small as compared to the size of the atom.
• The electrons and the nucleus are held together by electrostatic force of attraction.
• Atom as a whole is electrically neutral. So, the magnitude of the positive and negative charges is equal in
the atom.

Draw backs of Rutherford’s model:

16
• According to the electromagnetic theory of Maxwell, charged particles when accelerated should emit
radiation and loose energy. Since the energy carried by radiation comes from electronic motion, the orbit
will thus continue to shrink. Hence the electron should follow a spiral path and ultimately it should fall
into the nucleus. But this does not happen. Atoms are stable and Rutherford could not explain the stability
of the atom.
• Rutherford did not say anything about the arrangement of electrons and the energies of these electrons.

Electromagnetic radiations:
• The radiations which are associated with electrical and magnetic fields are called electromagnetic
radiations.
• When an electrically charged particle moves under acceleration, alternating electrical and magnetic fields
are produced and transmitted. These fields are transmitted in the form of waves. These waves are called
electromagnetic waves or electromagnetic radiations.

Properties of electromagnetic radiations:

• Oscillating electric and magnetic field are produced by oscillating charged particles. These fields are
perpendicular to each other and both are perpendicular to the direction of propagation of the wave.
• They do not need a medium to travel. That means they can even travel in vacuum.

Characteristics of electromagnetic radiations:

• Wavelength: It may be defined as the distance between two neighbouring crests or troughs of wave as
shown. It is denoted by λ.
• Frequency (ν): It may be defined as the number of waves which pass through a particular point in one
second.
• Velocity (c): It is defined as the distance travelled by a wave in one second. In vacuum all types of
electromagnetic radiations travel with the same velocity. Its value is 3 X108 m sec-1. It is denoted by c.
Velocity = frequency x wavelength

17
 c=ν×λ
• Wave number (𝝂̅) Wave number is defined as the number of wavelengths per unit length.
𝝂̅ = 1/λ

Dual behaviour of electromagnetic radiation:

• The light possesses both particle and wave like properties, i.e, light has dual behaviour.
• Whenever radiation interacts with matter, it displays particle like properties. (Black body radiation and
photoelectric effect)
• Wave like properties are exhibited when it propagates (interference or diffraction).

Planck's Quantum Theory:

• The radiant energy is emitted or absorbed not continuously but discontinuously in the form of small
discrete packets of energy called ‘quantum’. In case of light energy, the quantum of energy is called a
‘photon’.
• The energy of each quantum is directly proportional to the frequency of the radiation, i.e. E α υ or E= hυ
where h= Planck’s constant = 6.626 x 10-34 J s.
• Energy is always emitted or absorbed as integral multiple of this quantum. E=nhν Where n=1,2,3, 4, ....

Black body radiation:

• An ideal body, which emits and absorbs all frequencies, is called a black body. The radiation emitted by
such a body is called black body radiation.

• As the temperature is increased the energy emitted increases thereby increasing the frequency of the
emitted radiations.
• As the frequency increases the wavelength shifts to lower values.

Photoelectric effect:
• The phenomenon of ejection of electrons from the surface of metal when light of suitable frequency
strikes it is called photoelectric effect. The ejected electrons are called photoelectrons.
• When a beam of light falls on a metal surface, electrons are ejected immediately.
• Number of electrons ejected is proportional to intensity or brightness of light.

18
• Threshold frequency (vo): For each metal there is a characteristic minimum frequency below which
photoelectric effect is not observed. This is called threshold frequency.
• If frequency of light is less than the threshold frequency there is no ejection of electrons; no matter how
long it falls on surface or how high is its intensity.
• Photoelectric work function (Wo): The minimum energy required to eject electrons is called photoelectric
work function.
Wo= hvo
• If the frequency of the incident light (ν) is more than the threshold frequency (vo), the excess energy is
imparted to the electron as kinetic energy. Hence,
Energy of one quantum = Threshold Energy + Kinetic Energy
• When ν > vo, then on increasing the intensity the number of quanta incident increases thereby increasing
the number of photoelectrons ejected.
• When ν > vo , then on further increasing the frequency, the
energy of each photon increases and thus kinetic energy of each ejected electron increases.
𝟏
• Energy of the ejected electrons= 𝒉(𝝂 − 𝝂𝟎 ) = 𝟐 𝒎𝒆 𝒗𝟐

Spectrum:
• When a white light is passed through a prism, it splits into a series of coloured bands known as spectrum.
Spectrum is of two types: continuous and line spectrum.
• The spectrum which consists of all the wavelengths is called continuous spectrum.
• A spectrum in which only specific wavelengths are present is known as a line spectrum. It has bright lines
with dark spaces between them.
• Spectrum is also classified as emission and absorption spectrum.
• The spectrum of radiation emitted by a substance that has absorbed energy is called an emission
spectrum.
• The study of emission or absorption spectra is referred as spectroscopy.
• Absorption spectrum is the spectrum obtained when radiation is passed through a sample of material.
The sample absorbs radiation of certain wavelengths. The wavelengths which are absorbed are missing
and come as dark lines.

19
Electromagnetic spectrum:
• It is a continuous spectrum. It consists of a range of electromagnetic radiations arranged in the order of
increasing wavelengths or decreasing frequencies.
• It extends from radio waves to gamma rays.

Bohr’s model of atom:

Postulates:

• In an atom, the electrons revolve around the nucleus in certain definite circular path of fixed radius
and energy called orbits or energy levels. These orbits are also known as stationary states and are
arranged concentrically around the nucleus.
• As long as an electron remains in a particular orbit, it does not lose or gain energy and its energy
remains constant which means while revolving in these orbits the electrons do not radiate energy.
• When transition occurs between two stationary states that differ in energy, the frequency of the
radiation absorbed or emitted can be calculated as
𝛥𝐸 𝐸2 − 𝐸1
𝜈= =
ℎ ℎ
• An electron can move only in those orbits for which its angular momentum is an integral multiple of
h/2π
ℎ
‫ 𝑛 = 𝑟𝑣 𝑒𝑚 ؞‬2𝜋 , where n = Integral numbers = 1, 2, 3, ……that denotes the stationary states for
electrons and are known as Principal quantum numbers.

Expression derived from Bohr’s theory for hydrogen atom:

• The radii of the stationary states are expressed as rn = n2. a0 where a0 is the radius of the first
stationary state and is called Bohr’s orbit which is equal to 52.9 p.m.
𝑛2
• The radius of the nth orbit is given by rn =52.9 x pm (For hydrogen atom Z = 1)
𝑍

20
 • The energy of an electron is the energy of its stationary state and is given by
1
En = -RH (𝑛2 ) ; n = 1, 2, 3, ……n; RH = Rydberg constant = 2.18 × 10-18 J
1
• The energy of the lowest state (n = 1) known as the ground state is 2.18 × 10-18 (12) J = 2.18 × 10-18 J
𝑧2
• The energy of the electron in nth orbit is En = -2.18 × 10-18 (𝑛2 ) J (For hydrogen atom Z = 1)

Drawbacks of Bohr’s model:

• It fails to account for the finer details of the hydrogen atom spectrum.
• Bohr’s model was also unable to explain spectrum of atoms containing more than one electron.

Line spectrum of hydrogen:

• When an electric discharge is passed through gaseous hydrogen, the H2 molecules dissociate and the
energetically excited hydrogen atoms produced, emit electromagnetic radiation of discrete
frequencies.
• The hydrogen spectrum consists of several series of lines named after their discoverers. Balmer
showed in 1885 on the basis of experimental observations that if spectral lines are expressed in terms
of wavenumber(𝜈̅ ), then the visible lines of the hydrogen spectrum obey the following formula:
1 1
1/ν = 𝜈̅ = 109,677 ( 22 - 𝑛2 ) cm-1, where n is an integer equal to or greater than 3 (i.e., n = 3,4,5,....)
• The series of lines described by this formula are called the Balmer series. The Balmer series of lines are
the only lines in the hydrogen spectrum which appear in the visible region of the electromagnetic
spectrum.
• The Swedish spectroscopist, Johannes Rydberg, noted that all series of lines in the hydrogen spectrum
could be described by the following expression:
1 1 1 1
𝜈̅ = 109,677 ( 𝑛 2 - 𝑛 2 ) cm-1 or 𝜈̅ = 2.18 × 10-18 ( 𝑛 2 - 𝑛 2 ) J where ni=1,2.., nf = n1 + 1, n1 + 2...
𝑖 𝑓 𝑖 𝑓

• The value 109,677 cm–1 or is called the Rydberg constant for hydrogen. The first five series of lines
that correspond to n1 = 1, 2, 3,4, 5 are known as Lyman, Balmer, Paschen, Bracket and Pfund series,
respectively.
1 1
• The energy of transition, E = 2.18 × 10-18 ( 𝑛 2 - 𝑛 2
)J
𝑖 𝑓

21
Atomic Number and Mass Number:

• The atomic number is defined as the total number of protons present in the nucleus of an atom.
• The mass number is defined as the sum of the total number of protons and neutrons present in the
nucleus of an atom.
• In the notation for an atom, atomic number and mass number are represented as
𝑀𝑎𝑠𝑠 𝑁𝑜

𝑺𝒚𝒎𝒃𝒐𝒍 𝒐𝒇 𝒕𝒉𝒆 𝒆𝒍𝒆𝒎𝒆𝒏𝒕

𝐴𝑡𝑜𝑚𝑖𝑐 𝑁𝑢𝑚𝑏𝑒𝑟

Isotopes:
• Isotopes are the atoms of an element having the same atomic number but different mass numbers.
Examples are as follows:
a) 35 37
17𝐶𝑙 and 17𝐶𝑙

𝑏) 126𝐶 and 146𝐶

c) 11𝐻 , 21𝐻 and 31𝐻

Name Isotope Proton Neutrons Electrons

1
Protium 1𝐻 1 0 1
Deuterium 21𝐻 1 1 1
3
Tritium 1𝐻 1 2 1

Characteristics:
• The isotopes of an element have the same number of protons and electrons but the different number of
neutrons.
• Since the number of valence electrons is same, they show same chemical properties.
• The isotopes differ in their physical properties because of the difference in their masses.

Radioactive isotopes:
• The isotopes which are unstable due to the presence of extra neutrons in their nuclei and emit various
types of radiation (e.g α ray, β ray and γ ray) are called radioactive isotopes. Some of the common
radioactive isotopes are carbon-14, Sodium-23, cobalt-60 and uranium-235.
• The high energy radiations emitted by radioactive isotopes are harmful to human beings.
• So, radioactive isotopes have to be used very carefully by taking suitable precautions and at proper
concentration to avoid damage.
• Radioactive isotopes are used as a fuel in in nuclear reactors of nuclear power plants for generating
electricity.

Uses:
• It is used to estimate the age of Archaeological samples.
• It is used for the treatment of diseases. For e.g
22
 ➢ The isotope of Cobalt, 60𝐶𝑜 is used to cure cancer.
➢ The isotope of Iodine, 131𝐼 is used to study disorders of thyroid gland and hence the treatment
of Goitre.
➢ The isotope of Arsenic 74𝐴𝑠 is used to detect the presence of tumors.
➢ The isotope of Sodium 24𝑁𝑎 is used to detect the presence of blood clots.
• The isotope of Uranium is used to produce energy in the nuclear reactor.

Isobars:
• Isobars are the atoms of different elements of the same mass but different atomic numbers.
• Examples: (a) 40 40 24 24
18𝐴𝑟 and 20𝐶𝑎 (b) 11𝑁𝑎 and 12𝑀𝑔

Isobar Proton Electron Neutrons Mass Number

40
18𝐴𝑟 18 18 40 -18 = 22 18 + 22= 40
40
20𝐶𝑎 20 20 40 – 20 = 20 20+ 20= 40

Isotones:
• Isotones are the atoms of different elements having the same number of neutrons.
• Thus 37 39
17𝐶𝑙 and 19𝐾 are isotones. The nucleus of Chlorine contains 17 protons and 20 neutrons, whereas
the nucleus of potassium contains 19 protons and 20 neutrons.

Isotone Proton Electron Neutrons Mass Number

37
17𝐶𝑙 17 17 37 -17 = 20 17 + 20= 37
40
20𝐶𝑎 20 20 40 – 20 = 20 20 + 20 = 40

Problem:

Which two of the following atomic species are isotopes of each other and which two are isobars?
𝟐𝟑𝟏 𝟐𝟑𝟎 𝟐𝟑𝟎 𝟐𝟑𝟑
𝟗𝟎𝒁, 𝟗𝟏𝒁, 𝟖𝟖𝒁, 𝟗𝟎𝒁

Ans: The isotopes are the atoms of same atomic number but different mass number. There are two atoms
of atomic number 90. Hence, these two i.e 231 233
90𝑍 and 90𝑍 are isotopes.The isobars are the atoms of same
mass number but different atomic numbers. There are two atoms of mass number 230. Hence, these two
i.e 230 230
91𝑍 and 88𝑍 are isobars.

Fractional atomic mass:

• The atomic mass is calculated by adding the number of protons and neutrons. So, if an element has no
isotope, then the mass of its atom would be the same as the sum of protons and neutrons in it. But, many
elements consist of a mixture of isotopes. So, knowing the percentage of each isotopic form the average
mass is calculated.
• If an atom X exists in two isotopic forms X1 and X2, then the average atomic mass of X is given by the
formula below.
(% 𝒐𝒇 𝑿𝟏 )×(𝒎𝒂𝒔𝒔 𝒐𝒇 𝑿𝟏 )+(% 𝒐𝒇 𝑿𝟐 )×(𝒎𝒂𝒔𝒔 𝒐𝒇 𝑿𝟐 )
Avg. Atomic mass = 𝟏𝟎𝟎

23
Dual behaviour of matter:
• Classical mechanics is based on Newton’s laws of motion. It successfully describes the motion of
macroscopic particles but fails in the case of microscopic particles.
• Classical mechanics ignores the concept of dual behaviour of matter especially for sub-atomic particles
and the Heisenberg’s uncertainty principle.
• de Broglie proposed that matter exhibits dual behaviour i.e. matter shows both particle and wave nature.
𝒉 𝒉
de Broglie’s relation is 𝝀 = 𝒎𝒗 = 𝒑

• For microscopic particles, mass is very less; therefore 𝜆 is more showing more wave character.
• For macroscopic particles, mass is large; therefore 𝜆 is less showing more particle character.

Heisenberg’s uncertainty principle:

• It states that it is impossible to determine simultaneously, the exact position and exact momentum (or
velocity) of an electron. The product of their uncertainties is always equal to or greater than h/4π.
• Heisenberg’s uncertainty principle rules out the existence of definite paths or trajectories of electrons
and other similar particles
𝐡
• Mathematically, 𝚫𝐱. 𝚫𝐩 ≥ 𝟒𝛑 where Δx = uncertainty in position
𝐡
𝚫𝐱. 𝐦𝚫𝐯 ≥ 𝟒𝛑 Δp = uncertainty in momentum
𝐡
𝚫𝐱. 𝚫𝐯 ≥ 𝟒𝛑𝐦 Δv = uncertainty in velocity

Quantum mechanical model of an atom:

• Quantum mechanics is a theoretical science that deals with the study of the motions of the microscopic
objects that have both observable wave like and particle like properties.
• Quantum mechanics is based on a fundamental equation which is called Schrodinger equation.
• Schrödinger equation: For a system (such as an atom or a molecule whose energy does not change with
time) the Schrödinger equation is written as:
𝑯𝜳 = 𝑬𝝍 where H = Hamiltonian operator, E = Total energy of the system,
ψ = wave function which is the amplitude of the electron wave
• When Schrödinger equation is solved for hydrogen atom, the solution gives the possible energy levels the
electron can occupy and the corresponding wave function(s) of the electron associated with each energy
level. Out of the possible values, only certain solutions are permitted. Each permitted solution is highly
significant as it corresponds to a definite energy state. Thus, we can say that energy is quantized.
• ψ gives us the amplitude of wave. The value of ψ has no physical significance. This wave function (ψ)
stores all the information about an electron like energy, position, orbital etc. The information stored in ψ
about an electron can be extracted in terms of quantum numbers.
• Ψ2gives us the region in which the probability of finding an electron is maximum. It is called probability
density.
• The region where this probability density function reduces to zero is called nodal surfaces or simply
nodes.
• Radial nodes: Radial nodes occur when the probability density of wave function for the electron is zero
on a spherical surface of a particular radius. Number of radial nodes = n – l – 1

24
• Angular nodes: Angular nodes occur when the probability density wave function for the electron is zero
along the directions specified by a particular angle. Number of angular nodes = l
• Total number of nodes = n – l -1 + l = n-1
• Orbital: The region of space around the nucleus where the probability of finding an electron is maximum
is called an orbital.
• Degenerate orbitals: Orbitals having the same energy are called degenerate orbitals.

Characteristics of the quantum mechanical of an atom:

• Energy of the electron in an atom is quantized.
• The existence of quantized electronic energy levels is a direct result of Schrödinger equation and wave
like properties of electrons.
• Both the exact position and exact velocity of an electron cannot be determined simultaneously.
• An atomic orbital is the wave function ψ for an electron in an atom.
• Ψ2gives us the region in which the probability of finding an electron is maximum which is called
probability density.

Quantum numbers:
• They may be defined as a set of four quantum numbers which specify the energy, size, shape and
orientation of an orbital. To specify an orbital only three quantum numbers are required while to specify
an electron all four quantum numbers are required.

Principal quantum number (n):

• It identifies shell, determines sizes and energy of orbitals.
• Number of shells is equal to the value of n.

N 1 2 3 4
Shell name K L M N
Total number of orbitals = n2 1 4 9 16
Maximum number of electrons = 2n2 2 8 18 32

Azimuthal quantum number (l):

• Azimuthal quantum number ‘l’ is also known as orbital angular momentum or subsidiary quantum
number. It identifies sub-shell, determines the shape of orbitals, energy of orbitals in multi-electron
ℎ
atoms along with principal quantum number and orbital angular momentum,√𝑙(𝑙 + 1) 2𝜋.
• The number of orbitals in a subshell = 2l + 1.
• For a given value of n, l can have values ranging from 0 to n-1.

Subshell notation S p D f g
l value 0 1 2 3 4
Number of orbitals 1 3 5 7 9

25
Magnetic quantum number or Magnetic orbital quantum number (ml):
• It gives information about the spatial orientation of the orbital with respect to standard set of co-ordinate
axis.
• For any sub-shell (defined by ‘l’ value) 2l+1 values of ml are possible.
• For each value of l, ml = – 1 to 0 to + 1

Electron spin quantum number (ms):

• It refers to orientation of the spin of the electron.
• It can have two values +½ and -½. +½ identifies the clockwise spin and -½ identifies the anti- clockwise
spin.

N l ( 0 to n-1) ml = -l ,…, 0, …,+ l s ( +½ , - ½)

1 0 (s) 0 +½ , - ½
2 0 (s) 0 +½ , - ½
1 (p) -1 (px) +½ , - ½
0 (py) +½ , - ½
+1 (pz) +½ , - ½
3 0 (s) 0 +½ , - ½
1 (p) -1 (px) +½ , - ½
0 (py) +½ , - ½
+1 (pz) +½ , - ½
2(d) -2 (dxy) +½ , - ½
-1 (dyz) +½ , - ½
0 (dz2) +½ , - ½
+1 (dxz) +½ , - ½
+2 (dx2- y2) +½ , - ½

Shape of the orbitals:

s orbital p orbital

d orbitals f orbitals
26
s-orbitals:
• They are non-directional and spherically symmetric i.e. probability of finding the electron at a given
distance is equal in all directions.
• 1s orbital and 2s orbital have same shape but size of 2s is larger.
• There is a spherical shell within 2s orbital where electron density is zero and is called a node.
• The value of azimuthal quantum number(l) is zero (l=0) and magnetic quantum number can have only one
value i.e. m = 0

p-orbitals:
• It consists of two lobes present on either side of the plane that passes through the nucleus. The p-orbital
is dumb-bell shaped.
• There are three possible orientations of electron cloud in p-orbitals. Therefore, the lobes of p-orbital may
be considered to be along x,y and z axis. Hence, they are designated as px,py,pz. The three p-orbitals are
oriented at right angles to one another.
• First main energy level (Principal quantum number n = 1) does not contain any p-orbital.
• The three p-orbitals of a particular energy level have same energy in absence of an external electric and
magnetic field and are called degenerate orbitals.
• Like s orbitals, p-orbitals increase in size with increase in the energy of main shell of an atom. Thus, value
of azimuthal quantum number is one (l=1) and magnetic quantum number has three values
(m= -1, 0, +1)

d-orbitals:
• They are designated as dxy, dyz, dzx and dx2- y2, dz2. They have a shape like a four leaf clover. The fifth d
orbital designated as dz2 looks like a doughnut.
• All five d orbitals have same energy in the absence of magnetic field.
• The d orbitals have azimuthal quantum numbers l = 2 and magnetic quantum number values –2, –1, 0,
+ 1, + 2.
• For principal quantum number 1 and 2, there are no d orbitals.

Shielding effect or screening effect:

• Due to the presence of electrons in the inner shells, the

electron in the outer shell will not experience the full
positive charge on the nucleus. So, due to the screening
effect, the net positive charge experienced by the electron
from the nucleus is lowered and is known as effective
nuclear charge.
• Effective nuclear charge experienced by the orbital
decreases with increase of azimuthal quantum number (l).

27
Aufbau Principle:
• In the ground state of the atoms, the orbitals are filled in order of their increasing energies.
• n+l rule: Orbitals with lower value of (n+l) have lower energy. If two orbitals have the same value of (n+l),
then orbital with lower value of n will have lower energy.
• The order in which the orbitals are filled is as follows:
1s < 2s < 2p < 3s < 3p < 4s < 3d < 4p < 5s < 4d < 5p < 6s < 4f < 5d < 6p < 7s < 5f < 6d < 7p,……

Pauli Exclusion Principle:

• No two electrons in an atom can have the same set of four quantum numbers. Only two electrons may
exist in the same orbital and these electrons must have opposite spin.

Hund’s rule of maximum multiplicity:

• Pairing of electrons in the orbitals belonging to the same subshell (p, d or f) does not take place until each
orbital belonging to that subshell has got one electron each i.e., it is singly occupied.

Electronic configuration of atoms:

Arrangement of electrons in different orbitals of an atom. The electronic configuration of different atoms
can be represented in two ways.
a) sa pb dc fd notation.
b) Orbital diagram: each orbital of the subshell is represented by a box and the electron is represented by
an arrow (↑) a positive spin or an arrow (↓) a negative spin.

28
Stability of completely filled and half- filled subshells:
• Symmetrical distribution of electrons- the completely filled or half- filled sub-shells have symmetrical
distribution of electrons in them and are more stable.

Exchange energy:
• The two or more electrons with the same spin present in the degenerate orbitals of a sub-shell can
exchange their position and the energy released due to this exchange is called exchange energy.
• The number of exchanges is maximum when the subshell is either half- filled or completely filled. As a
result, the exchange energy is maximum and so is the stability.

Electronic Configuration of ions:

• Cations: They are formed when outermost electrons are removed from an atom. While removing the
electrons, we must remove the electrons from the highest principal quantum number.
• Anions: They are formed when electrons are added to the innermost empty shell.

29
Magnetic moment:
• Magnetic moment = √𝑛(𝑛 + 2) B.M (Bohr Magneton) Where n = number of unpaired electrons.
• Species with unpaired electrons are called paramagnetic and the species with no unpaired electrons are
called diamagnetic.

Numerical Problems:

1. Chlorine exists in two forms 𝟑𝟓 𝟑𝟕

𝟏𝟕𝑪𝒍 and 𝟏𝟕𝑪𝒍. They exist as 75% and 25% respectively. Calculate the
average atomic mass of Chlorine.
(% 𝒐𝒇 𝑿𝟏 )×(𝒎𝒂𝒔𝒔 𝒐𝒇 𝑿𝟏 )+(% 𝒐𝒇 𝑿𝟐 )×(𝒎𝒂𝒔𝒔 𝒐𝒇 𝑿𝟐 )
Ans. Avg. Atomic mass = 100

75 25
= (35 × 100 + 37 × 100)

= 26.25 +9.25

= 35.5

2. Calculate wave number of yellow radiations having wavelength of 5800 A0.

Ans. Wave number = 1/ wavelength

Wavelength = 5800 A0= 5800 x 10-10 m
Wave number = 1/5800 x 10-10 m
= 1.72 x 106 m-1

30
3. The energy associated with the first orbit in the hydrogen atom is -2.18 x 10-18 J/atom.
a) What is the energy associated with the fifth orbit.
b) Calculate the radius of Bohr’s fifth orbit for hydrogen atom.

Ans. a) En = -2.18 x 10-18/ n2

E5 = -2.18 x 10-18/ 52
= -8.72 x 10-20 J

b) For H atom, rn= 0.529 x n2

‫؞‬r5 = 0.529 x 52
= 13.225 A0
= 1.3225 nm

4. Calculate the uncertainty in the position of an electron if the uncertainty in its velocity is 5.7 x 10 5 m/s.

h
Ans. Δx. Δp ≥ 4π where Δx = uncertainty in position, Δp = uncertainty in momentum
𝐡
‫ ؞‬Δx. mΔv ≥ 𝟒𝛑 Δv = uncertainty in velocity
h
‫ ؞‬Δx. Δv ≥ 4πm

‫ ؞‬Δx = 6.626 x 10-34/ 9.1 × 10-31 × 4 × 3.14 m

= 1.0 x 10-10 m

5. Calculate the number of electrons which will together weigh one gram.

Ans. Mass of one electron = 9.10939 × 10–31 kg

9.10939 × 10–31 kg = 9.10939 × 10–31 × 103 gm =1 electron
1gm = 1 /9.10939 × 10–28 no. of electrons
= 0.1098 × 1028
= 1.098 × 1027 no. of electrons

6. Calculate the mass and charge of one mole of electrons

Ans. Mass of one electron = 9.10939 × 10–31 kg

Mass of one mole of electron = (6.022 × 1023) × (9.10939 ×10–31 kg) = 5.48 × 10–7 kg
Charge on one electron = 1.6022 × 10–19coulomb
Charge on one mole of electron = (1.6022 × 10–19C) × (6.022 × 1023)
= 9.65 × 104 C

31
7. Find energy of each of the photons which
(i) correspond to light of frequency 3× 1015Hz.
(ii) have wavelength of 0.50 Å.

Ans.
(i) Energy (E) of a photon is given by the expression, E = h𝜈
where h = Planck’s constant = 6.626 × 10–34Js, ν = frequency of light = 3 × 1015Hz
Substituting the values in the given expression of E = h𝜈
E = (6.626 × 10–34) × (3 × 1015) J
E = 1.988 × 10–18J
ℎ𝑐
(ii) Energy (E) of a photon having wavelength (λ)is given by the expression, E =
𝜆
Given h = Planck’s constant = 6.626 × 10–34Js
c = velocity of light in vacuum = 3 × 108m/s
ℎ𝑐
Substituting the values in the given expression of E =
𝜆
= (6.626 × 10–34) × (3 × 108) /0.50 × 10-10 J

‫ ؞‬E = 3.976 × 10-15 J

8. What is the wavelength of light emitted when the electron in a hydrogen atom undergoes transition
from an energy level with n = 4 to an energy level with n = 2?

Ans. ni= 4 to nf= 2 transition will give rise to a spectral line of the Balmer series. The energy involved in the
transition is given by the relation,
1 1
E = 2.18 × 10-18 ( 2
- )J
𝑛𝑖 𝑛𝑓 2
1 1
Substituting the values of ni and nf in the given expression, E = 2.18 × 10-18 ( - )J
42 22

−3
= 2.18 × 10-18 × J
16

‫ ؞‬E = – 4.0875 × 10–19 J

(The negative sign indicates the energy of emission)
ℎ𝑐 ℎ𝑐
Now, we know E = or λ =
𝜆 𝐸
(6.626 × 10−34 ) × (3 × 108 )
Substituting the values of E, h and C in the given expression, λ = m
4.0875 × 10−19

= 4.8631 × 10−7 m
= 486 nm

32
9. The work function for caesium atom is 1.9 eV. Calculate (a) the threshold wavelength and (b) the
threshold frequency of the radiation. (c) If the caesium element is irradiated with a wavelength 500 nm,
calculate the kinetic energy and the velocity of the ejected photoelectron.

(a) It is given that the work function (W0) for caesium atom is 1.9 eV.
ℎ𝑐 ℎ𝑐
W0 = or 𝜆0 = Where, λ0 = threshold wavelength, h = Planck’s constant, c = velocity of radiation
𝜆0 W0

(6.626 × 10−34 ) × (3 × 108 )

Substituting the values of h, c and W0 in the given expression, λ0 =
1.9 × 1.6 × 10−19
= 6.53 × 10–7 m
= 653 nm
Hence, the threshold wavelength is 653 nm

𝑊0
(b) From the expression Wo= h𝜈0 , we get 𝜈0 = Where, 𝜈0 = threshold frequency, h = Planck’s constant
ℎ
1.9 × 1.6 × 10−19
Substituting the values of Wo and h in the given expression, 𝜈0 = −34 s-1
6.626 × 10

= 4.593 × 1014s–1

Hence, the threshold frequency of radiation , 𝜈0 is 4.593 × 1014s–1.

(c) According to the question, wavelength used in irradiation (λ) = 500 nm

We know, kinetic energy = h (ν – ν0)
1 1
= hc ( - )J
𝜆 𝜆0
1 1
= 6.626 × 10−34 ) × (3 × 108 ) [ - ] nm
500 653
(653−500)×10−9
= 1.9878 × 10−26 [ ]J
653 ×500 × 10−18

= 9.3149 × 10–20J
‫ ؞‬Kinetic energy of the ejected photoelectron = 9.3149 × 10–20J

Since K.E = ½ m v2 = 9.3149 × 10–20J

2 ×9.3149 × 10−20
v= √
9.1 × 10−31

v = 4.52 × 105ms–1

Hence, the velocity of the ejected photoelectron (v) is 4.52 × 105ms–1.

33
 Chapter 3: Classification of elements and periodicity in the properties of elements

Main points:

• The periodic table is a chart of elements prepared in such a way that the elements having similar properties
occur in the same vertical column or group.
• A periodic table consists of horizontal rows of elements called periods and vertical columns called groups.

Dobereiner’s Law of triads:

• When elements are arranged in order of their increasing atomic masses, groups of three elements (known
as triads) having similar chemical properties are obtained. The atomic mass of the middle element of the
triad is equal to the arithmetic mean of the atomic masses of the other two elements.

• The element Li, Na and K have similar chemical properties and form a triad. They belong to the ‘alkali metal
group’. Also, arithmetic mean of the atomic masses of Li and K is 23 which is equal to the actual atomic mass
of Na.
➢ Atomic mass of Li = 7
➢ Atomic mass of K = 39
➢ So, arithmetic mean of the atomic masses of Li and K = (7+39)/2 = 46/2 = 23
• The element Ca, Sr and Ba have similar chemical properties and form a triad. They belong to the ‘alkaline
earth metal group’. Also, arithmetic mean of the atomic masses of Ca and Ba is 88.5 which is almost equal
to the actual atomic mass of Sr i.e 88.
➢ Atomic mass of Ca = 40
➢ Atomic mass of Ba = 137
➢ So, arithmetic mean of the atomic masses of Ca and Ba = (40+137)/2
= 177/2 = 88.5
• The element Cl, Br and I have similar chemical properties and form a triad. They belong to the ‘halogen
group’. Also, arithmetic mean of the atomic masses of Cl and I is 81.2 which is almost equal to the actual
atomic mass of Br i.e 80.
➢ Atomic mass of Cl = 35.5
➢ Atomic mass of I = 127
➢ So, arithmetic mean of the atomic masses of Cl and I = (35.5+127)/2
= 162.5/2 = 81.2

Limitations of Dobereiner’s Triad:

• Dobereiner’s classification failed to arrange all the elements discovered upto that time in the form of triad.
Only three triads were identified.
34
Newland’s Law of octaves:
• When elements are arranged in the order of increasing atomic masses, the properties of the eighth element
(starting from a given element) are a repetition of the properties of the first element.

• If ‘Li’ is the given element for the first row, the eighth element is ‘Na’ which has almost the same property as
that of ‘Li’.
• Again, for the second row, if ‘Na’ is taken as the first element then the eighth element is ‘K’ and it has been
found that ‘Na’ and ‘K’ have similar chemical properties.
• Also, for the first row, if ‘Be’ is taken as the first element then the eighth element is ‘Mg’ and it has been
found that ‘Be’ and ‘Mg’ have similar chemical properties.

Merits of Newland’s law of octaves:

Newland’s classification of elements based on his law of octaves, however gave a very important conclusion
that there is some systematic relationship between the order of atomic masses and repetition of properties of
elements.

Demerits of Newland’s law of octaves:

• Newland’s law of octaves was applicable to the classification of elements up to Ca only.
• In order to fit elements into his table, Newland put even two elements together in one slot and that to in the
column of unlike elements having very different properties. For example, Co and Ni were put together in one
slot and too in the column of elements like F, Cl and Br which have very different properties from these
elements.
• Fe which resembles Co and Ni in properties was placed far away from these elements.
• Newland assumed that only 56 elements existed in nature and no more elements would be discovered in the
future. But later on, several new elements were discovered whose properties did not fit into Newland’s law
of octaves.

Mendeleev’s periodic table:

• There were seven periods (horizontal rows) and eight groups (vertical columns) in the original periodic table
of Mendeleev.
• Out of eight groups, first seven groups are normal elements and eighth group is of transition elements.
• Noble gases were not known at that time. So, there was no group of noble gases in Mendeleev’s original
periodic table.
• The elements in each group of the periodic table are similar to one another in many properties.
• The similar properties of the elements are repeated periodically.

35
• In order to make sure that the elements having similar properties fell in the same vertical column or group,
Mendeleev left some gaps in his periodic table.
• Mendeleev thought that these elements would be discovered later on and even predicted the properties of
those unknown elements by studying the properties of neighbouring elements.
• The undiscovered element at that time for which gaps were left in the periodic table were named by
Mendeleev as ‘eka-boron’, ‘eka-aluminium’ and ‘eka-silicon’ by prefixing the term ‘eka’ to the name of the
preceding element in the same group. After discovering of those elements ‘eka-boron’ was named as
scandium (Sc), ‘eka aluminium’ was named as Gallium (Ga) and ‘eka-silicon’ was named as germanium (Ge).

Mendeleev’s periodic law: The properties of elements are a periodic function of their atomic masses.

Merits of Mendeleev’s periodic table:

• Mendeleev’s periodic law predicted the existence of some elements e.g ‘eka-boron’, ‘eka aluminium’ and
‘eka-silicon’ that had not been discovered at that time.
• Mendeleev’s periodic table could predict the properties of several elements on the basis of their positions in
the periodic table.
• Mendeleev’s periodic table could accommodate noble gases when they were discovered.

Demerits of Mendeleev’s periodic table:

• The position of isotopes could not be explained. If the elements are arranged according to atomic masses,
the isotopes should be placed in different groups of the periodic table since they have different atomic
masses.
• Wrong order of atomic masses of some elements could not be explained. For example, Co having atomic
mass of 58.9 comes first and Ni with slightly lower atomic mass (58.7) comes later. Similarly, Te (atomic mass
127.6) appeared before I (atomic mass 126.9).
• A correct position could not be assigned to hydrogen in the periodic table.
• In Mendeleev’s periodic table Hydrogen (H) has been placed in group I with alkali metals. This is because like
alkali metals, hydrogen also combines with halogens, oxygen and sulphur to form compounds having similar
formulae.

36
• Hydrogen also resembles halogens in some of the properties. Like halogens, it exists as a diatomic molecule.
Also, it combines with certain metals to form ionic compounds (called hydrides) and reacts with non-metals
to form covalent molecules like halogens.
• All these properties show that hydrogen can be placed either with alkali metals or with halogens. Certainly,
no fixed position can be given to hydrogen.

Modern Periodic table:

• Modern periodic table or long form of periodic table is prepared by Neils Bohr.
• There are 7 periods and 18 groups in the modern periodic table.
• Classification of elements according to their atomic number helps in arranging the elements according to
their electronic configuration.
• When elements are arranged according to increasing atomic numbers, there is a periodicity in the electronic
configurations of elements. This is because, the elements having same number of valence electrons occur at
regular intervals and this periodicity in the electronic configurations of elements leads to the periodicity in
their properties.
• All the elements of a given period have different number of valence electrons, so they have different
electronic configurations.
• All the elements of a given group have same number of valence electrons, so they have same electronic
configuration in the outer shell.
• Group 1 is the group of ‘alkali metals’. All the alkali metals have 1 valence electron each.
• Group 2 is the group of ‘alkaline earth metals’. All the alkaline earth metals have 2 valence electrons
each.
• Group 3 to 12 elements are called ‘transition elements’. In these elements the outermost shell as well as the
next to outermost shell (penultimate shell) is incomplete and in the process of being filled with electrons.
• Group 13 to 17 elements are non-metals. Their inner shells are completely filled with electrons, only the
outermost shells are incomplete. All the elements of a particular group have the same number of valence
electrons and therefore show similar properties. Group 13 to 17 elements have 3 to 7 valence electrons in
the outermost shell respectively.
• Group 16 elements are known as chalcogens.
• Group 17 elements are known as ‘halogens’.
• Group 18 is the group of ‘noble gases’. The valence shell of all the noble gases is completely filled with 8
electrons.
• Metals have been separated from non-metals by some elements called ‘metalloids’ which are placed
diagonally in the periodic table. These metalloids are Boron (B), Silicon (Si), Germanium (Ge), Arsenic (As),
Antimony (Sb), Tellurium (Te) and Pollonium (Po). The properties of metalloids are intermediate between
those of metals and non-metals.
• The elements with atomic numbers 57 to 71 are called lanthanide series and the elements with atomic
numbers 89 to 103 are called actinide series.
• Elements of 2nd and 3rd transition series belonging to same vertical columns are similar in size and properties
due to lanthanide contraction.
• The elements in a period have same number of energy shells, i.e., principal quantum number (n). These are
numbered 1 to 7.
37
 ➢ 1st period - 1s - 2 elements
➢ 2nd period-2s, 2p - 8 elements
➢ 3rd period 3s, 3p - 8 elements
➢ 4th period 4s, 3d, 4p - 18 elements
➢ 5th period 5s, 4d, 5p - 18 elements
➢ 6th period 6s, 4f, 5d, 6p - 32 elements
➢ 7th period 7s, 7f, 6d, 7p - 32 elements

Modern Periodic law: The properties of elements are a periodic function of their atomic numbers.

Electronic Configuration of the elements:

• There are four blocks of elements - s, p, d and f block depending on the orbital which gets the last electron.
• The general electronic configuration of these blocks are as follows:
➢ s-block: [Noble gas] ns1 or ns2. However, hydrogen has 1s1 configuration.
➢ p-block: [Noble gas] ns2np1–6
➢ d-block: [Noble gas] (n – 1) d1- 10 ns1 or [Noble gas] (n – 1) d1- 10ns2
➢ f-block: [Noble gas] (n – 2) f1–14(n – 1) d1-10 ns1 or [Noble gas] (n – 2) f1–14(n – 1) d1-10 ns2

Nomenclature of elements with Atomic Numbers > 100:

• The naming of the new elements had been traditionally the privilege of the discoverer and the suggested
name was ratified by the IUPAC.

38
Trends in the properties in the periodic table:

Valency:
• The valency of an element is determined by the number of valence electrons present in the outermost shell
of its atom.
• On moving from left to right in a period, the number of valence electrons in elements increases from 1 to 8
(from 2nd period onwards).
• On moving from left to right in a period, the valency of elements increases from 1 to 4 (group 1 to group 4)
and then decreases from 3 to 0 (group 5 to group 8).

Periodicity of valence or oxidation states:

• The electrons present in the outermost shell of an atom are called valence electrons and the number of these
electrons determine the valence or the valency of the atom.
• It is because of this reason that the outermost shell is also called the valence shell of the atom and the orbitals
present in the valence shell are called valence orbitals.
• In case of representative elements, the valence of an atom is generally equal to either the number of valence
electrons (s and p block elements) or equal to eight minus the number of valence electrons.
• In contrast, transition and inner transition elements, exhibit variable valence due to involvement of not only
the valence electrons but d or f electrons as well. However, their most common valence are 2 and 3. Let us
now discuss periodicity of valence along a period and within a group.

Variation along a period:

• As we move across a period from left to right, the number of valence electrons increases from 1 to 8. But the
valence of elements with respect to H or O first increases from 1 to 4 and then decreases to zero.
39
• In the formation of Na2O molecule, oxygen being more electronegative accepts two electrons, one from each
of the two sodium atoms and thus shows an oxidation state of –2.
• On the other hand, sodium with valence shell electronic configuration as 3s 1 loses one electron to oxygen
and is given an oxidation state of +1. Thus, the oxidation state of an element in a given compound may be
defined as the charge acquired by its atom on the basis of electronegativity of the other atoms in the
molecule.

Variation within a group:

• When we move down the group, the number of valence electrons remains the same, therefore, all the
elements in a group exhibit the same valence.
• For example, all the elements of group 1 (alkali metals) have valence one while all the elements of group 2
(alkaline earth metals) exhibit a valence of two.
• Noble gases present in group 18 are zerovalent, i.e., their valence is zero since these elements are chemically
inert.

Anomalous Properties of Second Period Elements:

• It has been observed that some elements of the second period show similarities with the elements of the
third period placed diagonally to each other, though belonging to different groups.
• For example, lithium (of group 1) resembles magnesium (of group 2) and beryllium (of group 2) resembles
aluminium (of group 13) and so as. This similarity in properties of elements placed diagonally to each other
is called diagonal relationship.
• The anomalous behaviour is due to their small size, large charge/radius ratio and high electronegativity of
the elements.
• In addition, the first member of group has only four valence orbitals (2s and 2p) available for bonding,
whereas the second member of the groups have nine valence orbitals (3s, 3p, 3d).
• As a consequence of this, the maximum covalency of the first member of each group is 4; e.g, boron can only
form [BF4]–, whereas the other members of the groups can expand their valence shell to accommodate more
than four pairs of electrons; e.g, aluminium forms [AlF6]3–. Furthermore, the first member of p-block elements
displays greater ability to form p-p multiple bonds to itself (e.g, C=C, CC, N=N, NN) and to other second
period elements (e.g, C=O, C=N, CN, N=O) compared to subsequent members of the same groups.

Atomic size:
• The size of an atom is known as atomic size.
• Atomic size is the distance between the centre of the nucleus and outermost electron shell of an isolated
atom.
• Hence, it refers to the radius of the atom and is indicated by ‘atomic radius’ which is expressed in picometre
unit.
1 pm= 10-12 metre
• On moving from left to right in a period of the periodic table, the atomic size or atomic radii decreases. This
is due to an increase in the nuclear charge which tends to pull the electrons closer to the nucleus and reduces
the size of the atom.

40
• On moving down in a group of the periodic table, atomic size or atomic radii increases. This is because new
shells are added gradually as we go down a group. Hence, the distance between the outermost electrons and
the nucleus also increases which leads to an increase in the atomic size in spite of the increase in nuclear
charge.

Atomic Radius:
• The distance from the centre of the nucleus to the outermost shell of the electrons in the atom of any
element is called its atomic radius.

Covalent Radius:
• Half the inter-nuclear distance between two similar atoms of any element which are covalently bonded
to each other by a single covalent bond is called covalent radius.

Van der Waal’s Radius:

• Half the inter-nuclear separation between two similar adjacent atoms belonging to the two
neighbouring molecules of the same substance in the solid state is called the van der Waal’s radius of
that atom.

Metallic Radius:
• Half the distance between the nuclei of the two adjacent metal atoms in a close packed lattice of the
metal is called its metallic radius.

Van der Waals ’radius > Metallic radius > Covalent radius

Ionic Radius:
• The effective distance from the centre of the nucleus of an ion up to which it has an influence on its
electron cloud is called its ionic radius.
• A cation is smaller but the anion is larger than the parent atom. In case of iso-electronic species, the
cation with greater positive charge has smaller radius but anion with greater negative charge has the
larger radii.
• Cations are smaller and anions are larger than neutral atoms of the elements.

Metallic and non-metallic character:

• On moving from left to right in a period, the metallic character of elements decreases and the non-metallic
character increases.
• The greatest metallic character is found in the elements on the extreme left side of a period and the greatest
metallic character is found in the elements on the extreme right side of a period.
• Metals lose electrons and form positive ions. So, metals are called electropositive elements.
• On the other hand, non-metals accept electrons and form negative ions. So, non-metals are called
electronegative elements.
• Hence, on moving from left to right in a period, the electropositive character of the elements decreases and
electronegative character increases.

41
• As the effective nuclear charge acting on the valence shell electrons increases across a period, the tendency
of the atoms to lose electrons decreases and to gain electron increases.
• On moving down in a periodic table, the metallic character as well as the electropositive character of the
elements increases. Hence, the greatest metallic character is found in the elements in the lowest part of a
group.
• Similarly, on moving down in a periodic table, the non-metallic character as well as the electronegative
character of the elements decreases. Hence, the greatest non-metallic character is found in the elements in
the top part of a group.
• Down the group, the effective nuclear charge experienced by valence electrons decreases because the
outermost electrons are farther away from the nucleus. Therefore, the tendency of an atom to lose electrons
increases and to gain electrons decreases on moving down in a group of the periodic table.
• In the modern periodic table, a zig-zag line separates metals from non-metals. For example, in the second
period, the metals like Na and Mg are towards the left- hand side of the periodic table while the non-metals
like S and Cl are found on the right-hand side. Si is present in the middle which is classified as a metalloid
because it exhibits some properties of both metals and non-metals. So, the borderline elements e.g B, Si, Ge,
As, Sb, Te and Po known as metalloids or semi metals.

Chemical reactivity:
• On moving from left to right in a period, the chemical reactivity of elements first decreases and then
increases. For example, in the second period, chemical reactivity decreases from Na to Si and again it
increases from P to Cl. Hence, both Na and Cl are highly reactive and Si is the least reactive element in that
period.
• Across a period, since the number of electrons in a given shell increases, the tendency to lose the electron
decreases and hence the reactivity also decreases. After group 4, the tendency to lose the electrons increases
and hence the reactivity also increases.
• The chemical reactivity of metals increases on going down in a group of the periodic table. For example, in
group 1 of alkali metals, the chemical reactivity increases from Li to Fr.
• As we go down in a group of metals, the tendency of their atoms to lose electrons increases, due to which
their reactivity also increases.
• The chemical reactivity of non-metals decreases on going down in a group of the periodic table. For example,
in group 17 of halogens, the chemical reactivity decreases from F to I.
• As we go down in a group of non-metals, the tendency of their atoms to gain electrons decreases, due to
which their reactivity also decreases.

Nature of oxides:
• On moving from left to right in a period, the basic nature of the oxides decreases and the acidic nature of the
oxides increases. For example, in the second period, oxides of Na and Mg are basic, oxides of Al and Si are
amphoteric and oxides of P, S and Cl are acidic.
• On moving down in a group of the periodic table, there is no change in the nature of oxides of elements. The
nature of oxides of all the elements of a group is the same. For example, all the elements of group 1form
basic oxides whereas all the elements of group 17 form acidic oxides.

42
Ionization Enthalpy:
• The ionization enthalpy is the molar enthalpy change accompanying the removal of an electron from a
gaseous phase atom or ion in its ground state. Thus, enthalpy change for the reaction M (g)→ M++ e- is
the ionisation enthalpy of the element M.
• Like ionisation energies for successive ionisation, the successive ionisation enthalpy may also be termed
as 2nd ionisation enthalpy (ΔiH2), third ionisation enthalpy (ΔiH3) etc.
• The term ionisation enthalpy is taken for the first ionisation enthalpy, (Δ iH1) is expressed in kg mol-1or in
eV.
• X (g) - e → X +(g) leads to ΔH= ΔiH1
X + (g) – e → X 2+(g) leads to ΔH= ΔiH2
X 2+ (g) – e → X 3+(g) leads to ΔH= ΔiH3

Periodicity in Ionization Enthalpy:

• Generally, the ionisation enthalpies follow the order (ΔiH1) < (ΔiH2) < (ΔiH3).
• The ionisation enthalpy decreases on moving top to bottom in a group.
• The ionisation enthalpy increases on moving from left to right in a period.
• Removal of electron from filled and half-filled shells requires of higher energy. For example, the ionisation
enthalpy of nitrogen is higher than oxygen. Be, Mg and noble gases have high values.
• Metals have low ionisation enthalpy values while non-metals have high ionisation enthalpy values.

Electron gain enthalpy:

• The electron gain enthalpy (∆egH) is the molar enthalpy change when an isolated gaseous atom or ion in its
ground state adds an electron to form the corresponding anion thus the enthalpy change for the reaction
X(g)+ e- → X(g)- is called the electron gain enthalpy (ΔegH) of the element X.
• The ΔegH may be positive or negative.
• The successive values for the addition of second, third etc. electron are called second, third etc. electron
gain enthalpies.

Periodicity in electron gain enthalpy:

• In period- The electron gain enthalpy increases from left to right in a period.
• In group- The electron gain enthalpy decreases from top to bottom in a group.
• Electron gain enthalpy becomes more negative from left to right in a period and less negative
from top to bottom in a group.
• Successive electron gain enthalpies are always positive.
• The elements with higher ionization enthalpy have higher negative electron gain enthalpy.
• X (g) + e → X -(g) leads to ΔH= ΔiH1
X + (g) + e → X 2-(g) leads to ΔH= ΔiH2
X 2+ (g) + e → X 3- (g) leads to ΔH= ΔiH3

43
Electronegativity:
• The relative tendency of an atom in a molecule to attract the shared pair of electrons towards itself is
termed as its electronegativity.

Periodicity in electronegativity:
• In period- The electro-negativity increases from left to right in a period.
• In group- The electro-negativity decreases from top to bottom in a group.
• The elements having high electronegativity have higher tendency to gain electrons and forms anion. So,
the elements in the upper right side of the periodic table are electronegative being non-metallic in nature.

Electropositivity:
• The tendency of an element to lose electrons and forms positive ions (cations) is called electropositive or
metallic character.
• The elements having lower ionisation energies have higher tendency to lose electrons, thus they are
electropositive and thus metallic in their behaviour.
• Alkali metals are the most highly electropositive elements.

Periodicity in Electropositivity :
• In period- The electropositive or metallic characters decreases from left to right in a period.
• In group- The electropositive or metallic characters increases from top to bottom in a group.

Solubility of alkali metals carbonates and bicarbonates:

• Periodicity in group: The solubility of alkali metal carbonates and bicarbonates in water increases down
the group (From Lithium to Caesium).

Solubility of alkaline earth metal hydroxides and sulphates:

• Periodicity in group: The solubility of alkaline earth metal hydroxide and sulphates in water increases
down the group (From Beryllium to Barium).

Basic strength of alkaline earth metal hydroxides:

• Periodicity in group: The basic strength of alkaline earth metal hydroxide in water increases down the
group (From Beryllium to Barium), i.e,
Be(OH)2 < Mg(OH)2 < Ca(OH)2 < Sr(OH)2 <Ba(OH)2

Basic strength increases

Thermal stability of carbonates of alkali and alkaline earth metals:

• Except lithium carbonate, (Li2CO3), the carbonates of all other alkali metals are stable towards heat,
i.e., carbonates of alkali metals (except Li2CO 3) do not decompose on heating. Li2CO3 decomposes on
heating to give lithium oxide (Li2O).
• The carbonates of alkaline earth metals are relatively less stable. On heating, they decompose to give
corresponding oxide and CO2 gas. The decomposition temperature for alkaline earth metal
carbonates increases as we go down the group.
44
Anomalous Properties of Second Period Elements:
• Second period elements anomalous behaviour is attributed to their small size, large charge/radius ratio,
high electro negativity, non- availability of d- orbitals in their valence shell.
• The first member of each group of p-Block elements displays greater ability to form p𝜋-pπ multiple bonds
to itself (e.g. C=C, C≡C O=O, N≡N) and to other second period elements (e.g. C=O, C≡N, N=O) compared
to subsequent member of the group.
• Lithium unlike other alkali metals and beryllium unlike other alkaline earth metals, form compounds with
pronounced covalent character; the other members of these groups predominantly form ionic
compounds.
• Behaviour of lithium and beryllium is more similar with the second element of the following group i.e.,
magnesium and aluminium, respectively. This sort of similarity is commonly referred to as diagonal
relationship in the periodic properties.

Merits of the modern periodic table:

• The modern periodic table is based on the atomic numbers of the elements which is the most fundamental
property of the elements.
• It helps us to understand why elements in a group show similar properties but elements in different groups
show different properties.
• It explains the reasons for the periodicity of the properties of the elements.
• The type of compounds formed by an element can be predicted by knowing its position in the periodic table.

Problems:

1. Select the species which are iso-electronic (same number of electron) with
each other.
(1) Ne (2) Cl- (3) Ca2+ (4) Rb+

Ans: Cl- and Ca2+. Both have 18 e each.

2. Arrange the following as stated:

(i) N2, O2, F2, Cl2 s(Increasing order of bond dissociation
energy)
(ii) F, Cl, Br, I (Increasing order of electron gain
enthalpy)
(iii) F2, N2, Cl2, O2 (Increasing order of bond length)

Ans- (i) F2 < Cl2 < O2 < N2

(ii) I < Br < F < Cl
(iii) N2 < O2 < F2 < Cl2

45
 Chapter 4: Chemical bonding and molecular structure

Key Points:

Chemical bond:
• The chemical force which keeps the atoms in any molecule together is called a chemical bond.

Ionic bond:
• The columbic force of attraction which holds the oppositely charged ions together is called an ionic bond.
An ionic bond is formed by the complete transfer of one or more electrons from the atom of a metal to
an atom of non- metal.

Lattice enthalpy:
• The molar enthalpy change accompanying the complete separation of the constituent particles that
compose of the solids (such as ions for ionic solid, molecules for molecular solids) under standard
conditions is called lattice enthalpy (ΔlHo). The lattice enthalpy is a positive quantity.

Electrovalency:
• The number of electrons lost or gain by an atom of an element is called as electrovalency.
• The elements which give up electrons to form positive ions are said to have positive valency
• The elements which accept electrons to form negative ions are said to have negative valency.

Formation of an ionic bond- It is favoured by the following factors:

• The low ionization enthalpy of a metallic element which forms the cations.
• High electron gain enthalpy of non- metallic element which forms the anions.
• Large lattice enthalpy i.e; the smaller size and the higher charge of the atoms.

Ionic bond & Ionic compound:

• The chemical bond formed by the transfer of electrons from one atom to another is known as ionic bond
and compounds containing such bond are known as ionic compound or electrovalent compound.
• Examples of ionic compounds are NaCl, MgCl2, MgO, CaO, Al2O3 etc.

Formation of NaCl:
• Na has total 11 electrons. It has 1 electron its outermost shell.
• Therefore, it loses 1 elctron and forms Na+ ion which has 8 electrons in its outermost shell.
• Cl has total 17 electrons. It has 7 electrons in its outermost shell.
• Therefore, it accepts 1 elctron and forms Cl- ion which also has 8 electrons it its outermost shell.
• Na+ and Cl- attract each other by electrostatic force of attraction and form NaCl.

Formation of MgCl2:
• Mg has total 12 electrons. It has 2 electrons its outermost shell.
• Therefore, it loses 2 elctrons and forms Mg+2 ion which has 8 electrons in its outermost shell.
• Cl has total 17 electrons. It has 7 electrons in its outermost shell.

46
• Therefore, two Cl atoms accept 1 elctron each and forms two Cl- ion. Each Cl- has 8 electrons it its
outermost shell.
• Mg+2 and 2 Cl- attract each other by electrostatic force of attraction and form MgCl 2.

Lewis dot representation of NaCl:

Electron dot representation of MgCl2:

Covalent character in ionic bonds (Fajan’s Rules):

The partial covalent character of ionic bonds was explained by Fajans in terms of the following rules:
• The smaller the size of the cation and the larger the size of the anion, the greater the covalent character
of an ionic bond.
• The greater the charge on the cation, the greater the covalent character of the ionic bond.
• For cations of the same size and charge, the ion with electronic configuration (n-1) dnns0 is more polarising
than the ion with a noble gas configuration (ns2 np6 ).

Covalency:
• The number of electrons which an atom contributes towards mutual sharing during the formation of a
chemical bond called its covalency in that compound.

Octet rule:
• During a chemical reaction the atoms tend to adjust their electronic arrangement in such a way that
they achieve 8 e- in their outermost electron. This is called octet rule.

Limitations of Octet Rule:

• The rule failed to predict the shape and relative stability of molecules.
• It is based upon the inert nature of noble gases. However, some noble gases like xenon and krypton
form compounds such as XeF2, KrF2 etc.
• The octet rule cannot be applied to the elements in and beyond the third period of the periodic table.

47
• The elements present in these periods have more than eight valence electrons around the central atom.
For example: PF5, SF6 etc.
• The octet rule is not satisfied for all atoms in a molecule having an odd number of electrons. For example,
NO and NO2 do not satisfy the octet rule.
• This rule cannot be applied to those compounds in which the number of electrons surrounding the central
atom is less than eight. For example, LiCl, BeH2, AlCl3 etc. do not obey the octet rule.

Single covalent bond:

• A covalent bond formed by the mutual sharing of one pair of electrons is called a single covalent bond, or
simply a single bond. A single covalent bond is represented by a small line (−) between the two atoms.

Double covalent bond:

• A covalent bond formed by the mutual sharing of two pair of electrons is known as double covalent bond,
or simply a double bond. A double covalent bond is represented by two small horizontal lines (=) between
the two atoms. E.g. O=O, O=C=O etc.

Triple covalent bond:

• A covalent bond formed by the mutual sharing of three pair of electrons is called a triple covalent bond,
or simply a triple bond. A triple covalent bond is represented by three small horizontal lines (≡) between
the two atoms. E.g. N≡N, H-C≡C-H etc.

Formation of a covalent bond:

It is favoured by
• High ionisation enthalpy of the combining elements.
• Nearly equal electron gains enthalpy and equal electro-negativities of combining elements.
• High nuclear charge and small atomic size of the combining elements.

Lewis Formula:
• A Lewis Structure is a very simplified representation of the valence shell electrons in a molecule. It is used
to show how the electrons are arranged around individual atoms in a molecule.
• Electrons are shown as "dots" or for bonding electrons as a line between the two atoms.
• The goal is to obtain the "best" electron configuration, i.e. the octet rule and formal charges need to be
satisfied.
• Lewis structure does NOT attempt to explain the geometry of molecules, how the bonds form, or how
the electrons are shared between the atoms. It is the simplest and most limited theory on electronic
structure.
• For example, when two chlorine atoms form a chlorine molecule, they share one pair of electrons.

48
• The Lewis structure indicates that each Cl atom has three pairs of electrons that are not used in bonding
(called lone pairs) and one shared pair of electrons (written between the atoms).
• A dash (or line) is sometimes used to indicate a shared pair of electrons.

• A single shared pair of electrons is called a single bond. Each Cl atom interacts with eight valence
electrons; the six in the lone pairs and the two in the single bond.

Formal Charge:
• The formal charge is a hypothetical charge assigned from the dot structure.
• The formal charge is the electrical charge difference between the valence electrons in an isolated atom
and the number of electrons assigned to that atom in a Lewis Structure.
• Formal Charge = [Number of valence electrons on atom] – [non-bonded electrons + number of bonds].
• For Example, in BH4
➢ The number of valence electrons for boron is 3.
➢ The number of non-bonded electrons is zero.
➢ The number of bonds around boron is 4.
➢ So formal charge = 3 – (0 + 4) = 3 – 4 = –1

How to draw Lewis Diagrams:

The following is an example of how to draw the "best" Lewis structure for NO 3- (learning by example).
• First determine the total number of valence electrons in the molecule. This will be the sum of the group
number a of all atoms plus the charge.
• Draw a skeletal structure for the molecule which connects all atoms using only single bonds. The central
atom will be the one that can form the greatest number of bonds and/or expand its octet. This usually
means the atom lower and/or to the right in the Periodic Table, N in this case.

• Now we need to add lone pairs of electrons. Of the 24 valence electrons available in NO3-, 6 were used to
make the skeletal structure. Add lone pairs of electrons on the terminal atoms until their octet is complete
or you run out of electrons.

• If there are remaining electrons, they can be used to complete the octet of the central atom. If you have
run out of electrons you are required to use lone pairs of electrons from a terminal atom to complete the

49
 octet on the central atom by forming multiple bond(s). In this case the N is short 2 electrons so we can
use a lone pair from the left most O atom to form a double bond and complete the octet on the N atom.

• Now you need to determine the formal charges for all of the atoms. The formal charge is calculated by:
(group number of atom) - (½ number of bonding electrons) - (number of lone pair electrons), i.e. see the
figure below.

• No Lewis structure is complete without the formal charges.

• In general, we want the fewest number of formal charges possible, i.e. formal charges of 0 for as many of
the atoms in a structure as possible.
• The formal charges should match the electronegativity of the atom, that is negative charges should be on
the more electronegative atoms and positive charges on the least electronegative atoms if possible.
• Charges of -1 and +1 on adjacent atoms can usually be removed by using a lone pair of electrons from the
-1 atom to form a double (or triple) bond to the atom with the +1 charge.
• Note: the octet can be expanded beyond 8 electrons but only for atoms in period 3 or below in the
periodic table. In our present example, N cannot expand beyond 8 electrons, so retains a formal charge
of +1, but the S atom below can expand its octet.

• We have determined the "best" Lewis structure (octets completed and lowest formal charges) for NO 3-,
but there are a number of ways to show this structure. Although it is most common to use a line to
indicate a bonding pair of electrons they can be shown as electrons, see the left most image below. It is
also common to show only the net charge on the ion rather than all of the formal charges, i.e. see the
right most figure below.

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Polar covalent bond:
• The bond between two unlike atoms which differ in their affinities for electrons is said to be polar covalent
bond. e.g. H-Cl

Coordinate bond:
• The bond formed when one sided sharing of electrons take place is called a coordinate bond. Such a bond
is also known as dative bond. It is represented by an arrow (→) pointing towards the acceptor atom. e.g.
H3N→BF3

Hydrogen bond:
• The bond between the hydrogen atom of one molecule and a more electro- negative element of same or
another molecule is called as hydrogen bond.

• The dipole interaction happens between molecules when H is bounded with highly electronegative atoms
(F, O, N only).
• Intramolecular hydrogen bond: When hydrogen bonding happens in between the same molecule. Hence,
molecules are independent and with less melting point, boiling point and less soluble in water.
• Intermolecular hydrogen bonding: When hydrogen bonding happens in between the different molecules
and results a close packing of molecules. Therefore, compounds show more melting point and point; thus,
more soluble in water.

Resonance:
• Whenever a single Lewis structure cannot describe a molecule accurately, a number of structures with
similar energy, positions of nuclei, bonding and non-bonding pairs of electrons are taken as the canonical
structures of the hybrid which describes the molecule accurately.
• Resonance is a method of describing the delocalized electrons in some molecules where the bonding
cannot be explicitly expressed by a single Lewis structure. Each individual Lewis structure is called a
51
 contributing structure of the target molecule or ion. Contributing structures are not isomers of the target
molecule or ion, since they only differ by the position of delocalized electrons. Resonance is a key
component of valence bond theory and arises when no single conventional model using only single,
double or triple bonds can account for all the observed properties of the molecule.
• In the case of some compounds, all the observed properties cannot be explained by a single structure.
Here we use more than one structures of the compound. These different structures are called resonance
structures or canonical structures or contributing structures. The phenomenon is known as resonance.
• Resonating structures are separated by double headed arrows.
• For example, in ozone (O3), the actual structure of ozone is not I or II. It is a resonance hybrid of the
structures I and II.

I II

• Carbonate ion has the following resonating structures:

• Carbon dioxide (CO2), Benzene (C6H6) also shows resonance.

Characteristics of resonance:
• Resonance stabilizes the molecule. As the number of resonating structures increases, the stability also
increases.
• Resonance changes the bond length.
• The difference in energy between the actual structure and the most stable canonical structure is called
resonance energy.
• Greater the resonance energy, more stable will be the molecule.

Dipole moment:
• The product of the magnitude of the charge and the distance between the centres of positive and negative
charge. It is a vector quantity and is represented by an arrow with its tail at the positive centre and head
pointing towards a negative centre.
• Dipole moment (μ) = charge (Q) × distance of separation (r)
52
• For example, HCl has a dipole moment of 1.03 D.

• In the case of poly atomic molecules, dipole moment depends on the individual bond dipoles and the
spatial arrangement of bonds. Here the dipole moment of the molecule is the vector sum of the bond
dipoles of various bonds.
➢ For example, H2O has a dipole moment of 1.8 D.

➢ For BeF2, the net dipole moment is zero, since the two equal bond dipoles are in opposite
directions and cancel each other.

➢ In BCl3, the net dipole moment is zero. Here the resultant of any 2 bond dipoles is equal and
opposite to the third.

➢ NH3 has μ = 1.47D and NF3 has μ = 0.23D. Both ammonia (NH3) and nitrogen fluoride (NF3) are
pyramidal in shape. Even though F is more electro negative than H, the net dipole moment of NF 3
is smaller than that of NH3. This is because in the case of NH3, the orbital dipole due to lone pair
is in the same direction as the resultant dipole moment of the three N – H bonds. But in NF3, the
orbital dipole is in the opposite direction to the resultant dipole moment of the three N-F bonds.
So, the dipole moments get partially cancelled.

VSEPR theory:
• In order to predict the geometry of molecules, Nyholm and Gillespie developed a qualitative model known
as Valence Shell Electron Pair Repulsion Theory (VSEPR Theory). The basic assumptions of this theory are
summarized below.
53
 ➢ The electron pairs in the valence shell around the central atom of a molecule repel each other
and tend to orient in space so as to minimize the repulsions and maximize the distance between
them.
➢ There are two types of valence shell electron pairs viz., i) Bond pairs and ii) Lone pairs.
➢ Bond pairs are shared by two atoms and are attracted by two nuclei. Hence, they occupy less space
and cause less repulsion.
➢ Lone pairs are not involved in bond formation and are in attraction with only one nucleus. Hence,
they occupy more space. As a result, the lone pairs cause more repulsion. The order of repulsion
between different types of electron pairs is as follows:

Lone pair - Lone pair > Lone Pair - Bond pair > Bond pair - Bond pair

Prediction of geometry of molecules using VSEPR theory:

54
Molecules containing only bond pairs of electrons:

• AB2 type:
➢ Here there are 2 VSEPs.
➢ In order to reduce the repulsion, these electron pairs are arranged at an angle of 180 0. Thus, the
shape of the molecule is linear with bond angle 1800
➢ e.g. BeCl2, HgCl2 etc.

• AB3 type:
➢ Here there are 3 VSEPs.
➢ In order to reduce the repulsion, these electron pairs are arranged at an angle of 120 0. Thus, the
shape of the molecule is planar triangular (trigonal planar) with bond angle 120 0. For example,
BF3, BCl3. etc.

AB4 type:

➢ Here there are 4 VSEPs.

➢ These are arranged at the four corners of a tetrahedron and hence the shape of the molecule is
tetrahedral with bond angle 1090 28l. For example, CH4, NH4+ etc.

AB5 type:

➢ Here there are 5 VSEPs.

➢ To reduce the repulsion, they are arranged at the five corners of a trigonal bipyramid with bond
angles 1200 and 900. For example, PCl5

AB6 type:

➢ Here there are 6 VSEPs.

➢ To reduce the repulsion, they are arranged at the six corners of an octahedron with bond angles 90 0.
For example, SF6

Explanation of shapes of ammonia and water molecules by VSEPR theory:

• In ammonia (NH3), the central atom N (2,5) has 5 valence electrons. Among these electrons, three are
used for the formation of bonds with hydrogen atoms and the remaining 2 electrons stay as lone pairs.
So, there are 4 VSEPs. Hence the expected shape of the molecule is tetrahedral. But due to the presence
of lone pairs, the shape is distorted to trigonal bipyramidal and the bond angle changes from 109 028l to
1070.
• In water (H2O), the central atom O (2,6) has 6 valence electrons. Two of them are used for the formation
of bonds with hydrogen atoms and the remaining 4 electrons stay as lone pairs. So, there are 4 VSEPs.
Hence, the expected shape of the molecule is tetrahedral. But due to the presence of 2 lone pairs, the
shape is distorted bent or angular or inverted V shape and the bond angle changes from 1090 28l to 104.50

Valence Bond theory:

• Valence bond theory assumes that electrons occupy atomic orbitals of individual atoms within a molecule,
and that the electrons of one atom are attracted to the nucleus of another atom.
55
• This attraction increases as the atoms approach one another until the atoms reach a minimum distance
where the electron density begins to cause repulsion between the two atoms.
• This electron density at the minimum distance between the two atoms is where the lowest potential
energy is acquired and it can be considered to be what holds the two atoms together in a chemical bond.
• The overlap of atomic orbitals is given by the following postulates:
➢ The atoms which unite to form a molecule completely retain their identities in the resulting
molecule.
➢ The formation of a covalent bond is due to overlap of atomic orbitals.
➢ If the two atoms, each having on unpaired electron, come together, the AO’s accommodating
these unpaired electrons overlap (i.e, electron waves interact) and the spins of the two electrons
get mutually neutralized, resulting in the formation of covalent bond which is localized between
the two atoms.
➢ If the electrons present in the AO’s have parallel spins, no bond formation will occur and no
molecule will be formed.
➢ If the AO’s possess more than one unpaired electron, more than one bond can be formed.
➢ Thus, in N2 molecule there are three bonds, since N atom has three unpaired electrons.
N = 2s2, 2px 1, 2py 1, 2pz 1
➢ Electrons already paired in the valence shell cannot take part in the bond formation.
➢ Electrons can only take part in the bond formation if they can be unpaired with the use of lot of
energy. This is seen in the case of Phosphorus, which forms PF5 by sharing 5 electrons (three from
the three unpaired P electrons and two from paired).
➢ The strength of the covalent bond is related to the extent of overlapping of the atomic orbitals.
➢ The more the two bonding orbitals overlap, more the bonding electrons are concentrated
between the nuclei where they can minimize the nuclear repulsion and maximize the attractive
forces between themselves and both nuclei jointly. Thus, greater the overlap of the atomic
orbitals, the greater will be the strength of the resulting covalent bond.

Hybridization:
• According to the valence bond theory, a covalent bond resulting from the overlap of atomic orbitals
requires the presence of unpaired electron in the overlapping atomic orbital of an atom.
• Thus carbon, with four electrons in the valence shell would have only two unpaired p electrons.
C = 2s2,2px 1,2py 1.
• To account for the third and fourth valency, it is believed that the ‘s’ electron in the same main level, gets
unpaired and occupies the Pz which is empty, thus creating four unpaired levels for the incoming electrons
to occupy.
• The arrangement of electrons in the atom obtained after the promotion of electrons is sometimes
referred to as an excited valence state of the atom. C*(excited state) = 2s1, 2px 1, 2py 1, 2pz 1.
• In order to account for the equivalence of the four C-H sigma bonds in CH4 molecule, we assume that the
four orbitals of C* atom, 2s, 2px, 2py and 2pz are mixed together or hybridized to form four orbitals of
equal energy called as the hybrid orbitals.
• The mixing of pure atomic orbitals to give equal number of hybrid orbitals is referred to as hybridization.

56
• The carbon atom in methane (CH4) is sp3 hybridized, because one s and three p orbitals are involved in
hybridization.
• All hybrid orbitals of a particular kind have equal energy, identical shapes and are symmetrically oriented
in shape.
• The hybrid orbitals are designed according to the type and the atomic orbitals merging together as given
below:

Hybridization Rules:
• Only orbitals of similar energies belonging to the same atom or ion can hybridize together.
• Number of hybrid orbitals produced is equal to the number of orbitals undergoing hybridization.
• Hybrid bonds are stronger than the single- non- hybridized bonds of comparable energy.
• Most of the hybrid orbitals are similar but they are not necessarily identical in shape. They differ from
one another in their orientation in space.
• For equivalent hybrids the orientation in space is determined by the number of orbitals mixed and
consequently the number of hybrids obtained and which of x, y and z axis are preferred by the orbitals.
• From the type of hybridization one can predict the geometry and bond angles of a molecule.
• An orbital which has been used to build up a hybrid orbital is no longer available to hold electron in its
pure form.

57
Sigma (σ) bond:
• A covalent bond formed due to the overlapping of orbitals of the two atoms along the line joining the two
nuclei (orbital axis) is called sigma (σ) bond. For example, the bond formed due to s-s and s-p, p-p
overlapping along the orbital axis are sigma bonds.

Pi (π) bond:
• A covalent bond formed by the side wise overlapping of p or d orbitals of two atoms is called as pi (π)
bond. For example, the bond formed due to the sideways overlapping of the two p orbitals is a pi bond.

Molecular orbital theory:

• An approach to bonding in which orbitals encompass the entire molecule, rather than being localized
between atoms.
• Molecular Orbital (MO) theory predicts the actual properties of molecules better than VB theory depicting
electron transitions because of the differences in the energy levels of orbitals in the molecule.
• Molecular orbitals are formed when the atomic orbitals of two (or more) different atoms are joined
together. The orbitals are then spread across all of the atoms that contributed the atomic orbitals.
• The same number of molecular orbitals are formed as there were atomic orbitals joined together and
their net energy is the same.
• The relative energies of molecular orbitals depend upon the following two factors:
(i) the energies of the atomic orbitals combining to form molecular orbitals.
(ii) the extent of overlapping between the atomic orbitals. The greater the overlap, the more the bonding
orbital is lowered and the antibonding orbital is raised in energy relative to atomic orbitals.

• Bonding molecular orbitals:

➢ Bonding M.O’s have electron density between the atom.
➢ They are lower in energy than the original atomic orbitals.
➢ when these orbitals are occupied by electrons, it holds the atoms together, forming a bond.

• Nonbonding molecular orbitals:

➢ Non-bonding M.O’s may occur when three or more atomic orbitals are combined.
➢ They have the same energy as the original atomic orbitals.
➢ Electrons occupying these orbitals do not stabilize or destabilize the molecule.

• Antibonding molecular orbitals:

➢ They have electron density which is not between the atoms (a node between the atoms).

58
 ➢ They are higher in energy than the original atomic orbitals.
➢ If these orbitals are occupied by electrons, it pulls the atoms away from each other and weakens
or prevents bonding.

Energy order of various Molecular Orbitals:

• The increasing order of energies of various molecular orbitals are given below:
σ1s < σ*1s < σ2s < σ*2s <σ2pz< (π *2px= π *2py) < σ*1s < σ2s < σ*2s < (π 2px = π 2py)
< (π *2px= π *2py) < σ*2pz

H2 molecule: He2 molecule:

O2 molecule: F2 molecule:

Bond Length:
• Bond length is defined as the equilibrium distance between the nuclei of two bonded atoms in a molecule.
• Bond length depends upon the following factors:
➢ Bond multiplicity: Bond length decreases with increase in bond multiplicity. C - C bond length is
shorter than C=C bond which in turn is shorter than C Ξ C.

59
 ➢ Size of the atom: The bond length increases with increase in the size of the atom. From the above
values it is clear that the bond lengths for a given family increase with increase in atomic number.
For example, C - C < Si - Si < Ge – Ge. This is because with the increase in size of the atom, the
distance of the electrons from the nucleus increases successively with the addition of a new shell.
Therefore, the average distance between the bonding nuclei (bond length) increases.

Bond Angle:
• It is defined as the angle between the orbitals containing bonding electron pairs around the central atom
in a molecule/complex ion.

Bond Enthalpy:
• It is defined as the amount of energy required to break one mole of bonds of a particular type between
two atoms in a gaseous state.
• It is expressed in terms of kJ mol-1.
• When a bond is formed between the atoms, energy is released and the bonded atoms have lesser energy
than the separated individual atoms. Then, same amount of energy will be needed to form the bond. This
energy is called the bond dissociation energy and is a measure of bond strength.
• Larger the bond dissociation energy, stronger will be the bond in the molecule.
• Bond dissociation enthalpy depends upon the size of bonded atoms, bond length and bond polarity.

Bond Order:
• In the Lewis description of covalent bond, the Bond Order is given by the number of bonds between the
two atoms in a molecule.
• Bond order is a measurement of the number of electrons involved in bonds between two atoms in a
molecule. Most of the time, bond order is equal to the number of bonds between two atoms. Exceptions
occur when the molecule contains antibonding orbitals.
• Bond order is calculated by the equation:
Bond order = (number of bonding electrons - number of antibonding electrons) /2
• Bond order is useful in predicting the stability of the molecules. If B.O = 0, then the molecule is unstable
and the two atoms are not bonded.
• If B.O > 0, then the molecule is stable. The bond order between the two carbons in acetylene is equal to
3 and the bond order between the carbon and hydrogen atoms is equal to 1.
• Thus, higher the bond order, greater will be the stability of the molecule.

Diamagnetic and Paramagnetic:

• Atoms or molecules which consist of paired electrons are called as “Diamagnetic” and which consist of
one or more unpaired electrons are known as “Paramagnetic”.

Saturated molecules:
• The molecules in which all the valence electrons are involved for single bond formation. Non-bonded lone
pairs are absent. These molecules have less energy, hence are more stable.

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 Chapter 6: Thermodynamics

Main points:

Thermodynamics: Science which deals with study of different forms of energy and quantitative
relationship.

System & Surroundings: The part of universe for study is called system and remaining portion is
surroundings.

Isolated System: Isolated system is a system which can exchange neither matter nor energy with the
surroundings. For example: Reactants in a thermos flask.
Closed System: Closed system is a system which do not exchange any matter but exchange energy with
the surroundings. For example: Reactants in a closed vessel.
Open System: Open system is a system which exchanges matter or energy with the surroundings. For
example: Reactant in an open test tube.

State of System: The state of a system means the condition of the system which is described in terms of
certain observable properties like temperature(T), pressure (P), volume(V) etc. of the systems. These
properties are called sate variables.

State function: The property which depends only on the state of a system and does not depend upon the
path through which it is attained is called state function. For example: pressure (P), volume (V),
temperature (T), enthalpy (H), free energy (G), internal energy (U), entropy (S), amount (n) etc.

Extensive Properties: Properties which depends on quantity of matter called extensive property. eg. mass,
volume, heat capacity, enthalpy, entropy etc.

Intensive Properties: The properties which do not depends on matter present but depends upon the
nature of the substance is called Intensive properties. E.g. temperature, pressure, density, refractive index,
viscosity, boiling point, pH, mole fraction etc.

Internal energy:

• It is the sum of all kind of energies possessed by the system. U is a state function and extensive
properly.
• U = U2 – U1 or UP – UR ; If U1 > U2 energy is released

Heat (q): It is a form of energy which is exchanged between system and surrounding due to difference of
temperature. Unit of heat is Joule (J) or Calorie. (1 Calorie = 4.18 J).

First Law of Thermodynamics:

• It is the law of conservation energy. Energy can neither be created not destroyed, it may be
converted from one from into another.
• In other words, the energy of an isolated system is constant.

61
 • Mathematically, ΔU = q + w and w = –p. ΔV

‫ ؞‬ΔU = q – p.ΔV
or q = ΔU + p. Δ V q, w are not state functions, but ΔU is a state function.

Work of expansion/compression:
• w = – Pex (Vf - Vi). The negative sign of this expression is required to obtain conventional sign for w,
which will be positive. It indicates that in case of compression work is done on the system. Here (Vf – Vi)
will be negative and negative multiplied by negative will be positive. Hence, the sign obtained for the work
will be positive.
• If the pressure is not constant at every stage of compression, but changes in number of finite steps,
work done on the gas will be summed over all the steps and will be equal to – Σ pΔV.

Free expansion:
• Expansion of a gas in vacuum (pex = 0) is called free expansion. No work is done during free expansion of
an ideal gas whether the process is reversible or irreversible.
Reversible Process:

• Process which proceeds infinitely slowly by a series of equilibrium steps.

• In a reversible process, the initial and the final states are connected through a succession of
equilibrium states. All changes occurring in any part of the process are exactly reversed when it
is carried out in the opposite direction. Thus, both the systems and its surroundings must be
restored exactly to their original state, when the process has been performed and then reversed.
• A reversible process proceeds infinitely slowly by a series of equilibrium states such that system
and the surroundings are always in near equilibrium with each other.
• If the pressure is not constant but changes during the process such that it is always infinitesimally
greater than the pressure of the gas, then, at each stage of compression, the volume decreases
by an infinitesimal amount, dV. In such a case we can calculate the work done on the gas by the
𝑉
relation w = − ∫𝑉 𝑓 𝑝𝑒𝑥 dV. Here, pex at each stage is equal to (pin + dp) in case of compression.
𝑖
In an expansion process under similar conditions, the external pressure is always less than the
pressure of the system i.e., pex = (pin– dp). In general case, we can write, pex = (pin + dp). Such
processes are called reversible processes.
𝑉
• So, we can write w = − ∫𝑉 𝑓 (𝑝𝑖𝑛 ± dp)dV
𝑖
𝑉
Or, w = - ∫𝑉 𝑓 𝑝𝑖𝑛 dV as dp.dV is negligible
𝑖
Now, for ‘n’ mole of an ideal gas we know pV= nRT

𝑛𝑅𝑇
‫؞‬p=
𝑉
𝑉𝑓 𝑛𝑅𝑇
So, w = ∫𝑉 dV
𝑖 𝑉
𝑉𝑓 𝑑𝑉 𝒅𝒙
w = nRT∫𝑉 (∫ = ln x = 2.303 log x )
𝑖 𝑉 𝒙
𝑉 𝑽 𝑽
= nRT ln[𝑉]𝑉𝑓𝑖 ( [𝐥𝐧 𝒙]𝑽𝒇𝒊 = ln𝑽𝒇 – ln𝑽𝒊 = ln 𝑽𝒇 )
𝒊
𝑉𝑓
= nRT ln 𝑉
𝑖
𝑉
= 2.303 nRT log 𝑉𝑓
𝑖

62
Irreversible Processes:
• Process which proceeds rapidly and the system does not have chance to achieve equilibrium.
• Sudden decrease or increase of the external pressure, will lead to non-uniformity in temperature
and pressure within the system and the equilibrium will be disturbed. Such processes are called
as irreversible processes.
• Work done during an irreversible process: w = – Pex (Vf - Vi).

Isothermal process:
• When the temperature of the system remains constant during various operations, then the
process is said to be isothermal. This is attained either by removing heat from the system or by
supplying heat to the system.
• For isothermal (T = constant) expansion of an ideal gas into vacuum, w = 0 since pex = 0. Also,
Joule determined experimentally that q = 0; therefore, ΔU = 0
• For isothermal irreversible change q = – w = pex (Vf – Vi)
𝑉𝑓 𝑉𝑓
• For isothermal reversible change q = – w = nRT ln = 2.303 log
𝑉𝑖 𝑉𝑖

Adiabatic process:

• In an adiabatic process there is no exchange of heat between the system and the surroundings.
Thus, in adiabatic processes there is always a change in temperature.
• For adiabatic change, q = 0, ΔU = wad
Isochoric process: Process during which the volume is kept constant.
Isobaric process: Process during which the pressure is kept constant.

Sign Conventions for Heat (q) and Work (w):

• W = + ve, if work is done on the system
• W = - ve, if work is done by the system
• q = + ve, if heat is absorbed by the system
• q = -ve, if heat is evolved by the system

Conditions of thermodynamic Processes:

• Isothermal process: T = 0
• Adiabatic process: q = 0
• Isobaric process: P = 0
• Isochoric process: V = 0
• Cyclic process: U = 0

Enthalpy (H):
• The enthalpy of a system may be defined as the sum of the internal energy and the product of its
pressure and volume. It is denoted by the symbol H and is given by H = U + PV
• For finite changes at constant pressure, we can write the equation H = U + PV as Δ H = Δ U + Δ (pV)
Since p is constant, we can write it again as Δ H = Δ U + p Δ V
63
Relationship between qp, qv i.e. Δ H & Δ U:

• According to the first law of thermodynamics, Δ U = q + w

At constant volume Δ V = 0, So ΔU = qv + (-p. Δ V) = qv + 0
‫ ؞‬ΔU = qv (heat supplied at constant volume)

• At constant pressure, the equation becomes Δ U = qp + (-p. Δ V) where qp is heat absorbed by the
system and -p. ΔV represent expansion work done by the system.
• Let us assume, the energy of the system in the initial state as U1 = qp + pV1 and the energy of the system
in the final state as U2 = qp + pV2
‫ ؞‬U2–U1 = qp – p (V2 – V1)
On rearranging, we get
qp = (U2 + pV2) – (U1 + pV1)
= H2 – H1
‫؞‬
qp = Δ H

• Δ H = Δ U + Δ PV = Δ U + P Δ V (at constant P)
Now, qv = Δ U and qp = Δ H

‫؞‬ qp= qv+ P Δ V

• PV = n R T
At constant pressure and temperature, the equation becomes P Δ V = R T Δng
Now, Δ H = Δ U + P Δ V
= Δ U + R T Δng where Δng = Number of moles of gaseous products – Number of moles of
gaseous reactants
‫؞‬
Δ H = Δ U + (Δng) R T

Again, qp= qv+ P Δ V = qv+ (Δng) R T

qp = qv+ (Δng) R
‫؞‬
T
Exothermic and Endothermic reactions:
• Δ H = –ve for exothermic and Δ H = +ve for endothermic reaction i.e. evolution and absorption of heat.
• Exothermic reaction:
C + O 2 → CO2 + 393.5 kJ (i.e. Δ H = - 393.5 kJ)
• Endothermic reaction:
N2 + O2 → 2 NO – 180.7 kJ, (i.e. Δ H = 180.7 kJ)

Enthalpy of reaction (ΔrH):

• The enthalpy change accompanying a reaction is called the reaction enthalpy.

• The amount of heat evolved or absorbed when the reaction is completed.
• Reaction enthalpy (ΔrH) = (sum of enthalpies of products) - (sum of enthalpies of reactants).
• A balanced chemical equation with the value of ΔrH is called a thermochemical equation.
64
Standard Enthalpy of reaction (ΔrHϴ):
• The standard enthalpy of reaction is the enthalpy change for a reaction when all the participating
substances are in their standard states.
• The standard state of a substance at a specified temperature is its pure form at 1 bar. At 1 bar pressure
and specific temp.(298K) i.e. standard state.

Hess’s Law of Constant Heat Summation:

• If a reaction takes place in several steps then its standard reaction enthalpy is the sum of the standard
enthalpies of the intermediate reactions into which the overall reaction may be divided at the same
temperature.
• The total amount of heat change is same whether the reaction takes place in one step or in several
steps. i.e. H = H1 + H2 + H3 + --------
• Enthalpy change for chemical reactions can be determined by
ΔrH = sum of enthalpies of products - sum of enthalpies of reactants
= ∑𝑖 𝑎𝑖 𝐻𝑝 − ∑𝑖 𝑏𝑖 𝐻𝑟

Here symbol Σ(sigma) is used for summation and ai and bi are the stoichiometric coefficients of the
products and reactants respectively in the balanced chemical equation (thermochemical equation).

Different types of Enthalpies of reactions:

Standard Enthalpy of combustion (ΔcHϴ):

• Standard enthalpy of combustion is defined as the enthalpy change per mole (or per unit amount) of a
substance, when it undergoes combustion and all the reactants and products being in their standard
states at the specified temperature.

Standard Enthalpy of formation (ΔfHϴ):

• The standard enthalpy change for the formation of one mole of a compound from its elements in their
most stable states of aggregation (also known as reference states) is called Standard Molar Enthalpy of
Formation.
• The equation ΔfHϴ = ∑𝑖 𝑎𝑖 𝛥𝑓 𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
𝛳 𝛳
− ∑𝑖 𝑎𝑖 𝛥𝑓 𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 can be used for the enthalpy change
calculation due to formation.

Standard Enthalpy of neutralization (ΔnHϴ):

• The enthalpy of neutralization is the change in enthalpy that occurs when one equivalent of an acid
and one equivalent of a base undergo a neutralization reaction to form water and a salt.
• It is a special case of the enthalpy of reaction. When a reaction is carried out under standard condition
at the temperature of 298 K (25 degrees Celsius) and 1 atm of pressure and one mole of water is formed
it is called the standard enthalpy of neutralization (ΔHn⊖).

Enthalpy of solution (ΔsolHϴ):

65
• Enthalpy of solution of a substance is the enthalpy change when one mole of it dissolves in a specified
amount of solvent.
• The enthalpy of solution at infinite dilution is the enthalpy change observed on dissolving the substance
in an infinite amount of solvent when the interactions between the ions (or solute molecules) are
negligible.

Enthalpy of atomization (ΔaHϴ):

• It is the enthalpy change on breaking one mole of bonds completely to obtain atoms in the gas phase.
• The enthalpy of atomization is also the bond dissociation enthalpy for diatomic molecule.

Enthalpy of ionization (ΔiHϴ):

• Ionization Enthalpy of elements is the amount of energy that an isolated gaseous atom requires to lose
an electron in its ground state.
• Losing of electrons results in the formation of cations. Hence, the ionization enthalpies of chemical
elements are always positive.

Enthalpy of hydration (ΔhydHϴ):

• The hydration enthalpy is the enthalpy change when 1 mole of gaseous ions dissolve in sufficient water
to give an infinitely dilute solution.
• The heat energy released when new bonds are made between the ions and water molecules is known as
the hydration enthalpy of the ion.
• Hydration enthalpies are always negative.

Standard Enthalpy of fusion (Δfus.Hϴ):

• The enthalpy change that accompanies melting of one mole of a solid substance in standard state is
called standard enthalpy of fusion or molar enthalpy of fusion, Δfus.H.

Standard Enthalpy of vaporization (Δvap.Hϴ):

• Amount of heat required to vaporize one mole of a liquid at constant temperature and under standard
pressure (1bar) is called its standard enthalpy of vaporization or molar enthalpy of vaporization, Δvap.H.

Standard Enthalpy of sublimation (Δsub.Hϴ):

• Standard enthalpy of sublimation, Δsub.H is the change in enthalpy when one mole of a solid substance
sublimes at a constant temperature and under standard pressure (1bar).
• (Δ sub.H) = Δ fus.(H) - Δ vap(H)

Bond enthalpy (ΔbondHϴ):

• The bond dissociation enthalpy is the change in enthalpy when one mole of covalent bonds of a gaseous
covalent compound is broken to form products in the gas phase.
• In other words, it is amount of energy released when gaseous atoms combines to form one mole of
bonds between them or heat absorbed when one mole of bonds between them are broken to give free
gaseous atoms.
• For diatomic molecule, the bond dissociation enthalpy is also the same as the enthalpy of atomization.
• For polyatomic molecule, the bond dissociation enthalpy is considered as mean bond enthalpy.

66
• The net enthalpy change of a reaction is the amount of energy required to break all the bonds in the
reactant molecules minus the amount of energy required to break all the bonds in the product
molecules provided all substances (reactants and products) in the reaction are in gaseous state.
So, ΔbondHϴ = Σ Bond Enthalpy (Reactants) – Σ Bond Enthalpy (Products)

Lattice enthalpy:
• It is simply the change in Enthalpy associated with the formation of one mole of an ionic compound
from its gaseous ions under standard conditions.
• Lattice enthalpy is a measure of the strength of the forces between the ions in an ionic solid. The
greater the lattice enthalpy, the stronger the forces.
• The lattice dissociation enthalpy is the enthalpy change needed to convert 1 mole of solid crystal into its
scattered gaseous ions. Lattice dissociation enthalpies are always positive.
• The lattice formation enthalpy is the enthalpy change when 1 mole of solid crystal is formed from its
separated gaseous ions. Lattice formation enthalpies are always negative.

Born - Haber Cycle:

• The Born–Haber cycle is an approach to analyze reaction energies.
• A Born–Haber cycle applies Hess's law to calculate the lattice enthalpy by comparing the standard
enthalpy change of formation of the ionic compound (from the elements) to the enthalpy required to
make gaseous ions from the elements.
• The Born–Haber cycle applies only to fully ionic solids such as certain alkali halides.

Spontaneous & Non-spontaneous Processes:

67
• A process which can take place by itself is called spontaneous process.
• A spontaneous process is an irreversible process and may only be reversed by some external agency.
• A process which can neither take place by itself or by initiation is called non- spontaneous.

Driving forces for spontaneous process:

• Tendency for minimum energy state.

• Tendency for maximum randomness.

Entropy (S):

• It is measure of randomness or disorder of system. i.e. Gas>Liquid>Solid.

• The greater the disorder in an isolated system, the higher is the entropy.
• For a given substance, the crystalline solid state is the state of lowest entropy (most ordered) and the
gaseous state is state of highest entropy. i.e. Gas>Liquid>Solid.
• Entropy, like any other thermodynamic property such as internal energy U and enthalpy H is a state
function and ΔS is independent of path.
• The entropy change (ΔS) is inversely proportional to the temperature as temperature is the measure of
average chaotic motion of particles in the system.
𝑞𝑟𝑒𝑣 𝛥𝐻
• ΔS is related with q and T for a reversible reaction as ΔS = = (as qp = ΔH)
𝑇 𝑇

Spontaneity in term of (S):

• S(total) = S(universe) = S(system) + S(surrounding)

• If S(total) is +ve, the process is spontaneous.
• If S(total) is –ve, the process is non spontaneous.
• The total entropy change ΔS total for the system and surroundings of a spontaneous process is given by
ΔS(total) = ΔS system + ΔS surrounding > 0
• When a system is in equilibrium, the entropy is maximum, and the change in entropy, ΔS = 0.
• Increase in enthalpy of the surrounding is equal to decrease in the enthalpy of the system.
Now, ΔS(total) = ΔS system + ΔS surrounding
ΔHsurrounding
‫ ؞‬ΔS(total) = ΔS system + T
−ΔHsystem
= ΔS system + ( )
T
T ΔS(total) = T ΔS system - ΔHsystem
= - ( ΔHsystem - T ΔS system )
=-ΔG

Second Law of thermodynamics:

• In any spontaneous process, the entropy of the universe always increases. A spontaneous process
cannot be reversed.

Gibb’s free energy (G):

• It is defined as G = H – T.S (Gibb’s Helmholtz equation).

68
• Gibbs function, G is an extensive property and a state function.
• It is equal to the useful work i.e. - G = W(useful) = W(max.)
• If G = - ve, process is spontaneous.

Absolute entropy and third law of Thermodynamics:

• The entropy of any pure crystalline substance approaches zero as the temperature approaches absolute
zero. This is called third law of thermodynamics. The statement is confined to pure crystalline solids
because theoretical arguments and practical evidences have shown that entropy of solutions and super
cooled liquids is not zero at 0 K.

Gibbs free energy change and Equilibrium:

• When applied to a chemical reaction, the term ‘reversible’ indicates that a given reaction can proceed in
either direction simultaneously, so that a dynamic equilibrium is set up. This means that the reactions in
both the directions should proceed with a decrease in free energy, which seems impossible.
• It is possible only if at equilibrium the free energy of the system is minimum. If it is not, the system
would spontaneously change to configuration of lower free energy. So, the criterion of equilibrium for
the reaction A + B ⇋ C + D is ΔGr = 0.
• Gibbs energy for a reaction in which all reactants and products are in standard state, ΔGrϴ is related to
the equilibrium constant of the reaction as follows:
0 = ΔGrϴ + RT ln K
Or, ΔGrϴ = – RT ln K
Or, ΔGrϴ = – 2.303 RT log K
Or, Δr Hϴ – TΔrS = – 2.303 RT log K

• For strongly endothermic reactions, the value of Δr Hϴ may be large and positive. In such a case, value of
K will be much smaller than 1 and the reaction is unlikely to form much product.
• In case of exothermic reactions, Δr Hϴ is large and negative, and ΔGrϴ is likely to be large and negative
too. In such cases, K will be much larger than 1 and hence can go to near completion.
• ΔGrϴ also depends upon ΔrSϴ. If the changes in the entropy of reaction is also taken into account, the
value of K or extent of chemical reaction will also be affected, depending upon whether ΔrSϴ is positive
or negative.

Effects of T on spontaneity of a process:

ΔG = ΔH – TΔS
• Endothermic process may be non- spontaneous at low temperature
• Exothermic process may be non- spontaneous at high temperature and spontaneous at low
temperature.
• So, many reactions which are non-spontaneous at low temperature are made spontaneous at high
temperature for systems having positive entropy of reaction.

Numerical Problems:

1. For oxidation of iron, 4 Fe + 3O2 → 2Fe2O3(s), ΔS is –549.4J.K-1 mol-1at 298K. In spite of –ve entropy
change of this reaction, why is the reaction spontaneous? (ΔrH0 = - 1648 x 103 J mol-1)

69
 𝛥𝑓 𝐻0 −1648 × 103 𝐽 𝑚𝑜𝑙 −1
Ans: ΔS(surr) = = = 5530 JK-1mol-1
𝑇 298 𝐾

& Δ S(system) = - 549.4 JK-1mol-1

Δ S(total) = 5530 – 549.4 = 4980.6 JK-1mol-1
Since Δ S(total) is + ve, so the reaction is spontaneous.

2. Using the bond energy of H2 = 435 KJ mol-1, Br2 = 192 KJ mol-1, HBr = 368 KJmol-1, calculate the enthalpy
change for the reaction H2(g) + Br2(g)→2HBr(g)

Ans: ΔrH0 = Sum of bond enthalpies of reactants – Sum of bon enthalpies of products
= [435 – 192] – [2 x 368] KJ mol-1
= 627 – 736
= –109 kJmol-1

3. Enthalpies of formation of CO(g), CO2(g), N2O(g) and N2O4(g) and –110, –393, 81 and 9.7 KJ mol-1
respectively. Find value ΔrH for the reaction N2O4(g) + 3CO(g)→ N2O (g) + 3 CO2(g).

Ans: ΔrH = ΔrH0(product) - ΔrH0(reactant)

= [ 81 + 3(-393)] – [9.7 + 3(- 110)]
= - 777.7 kJ

4. Calculate the enthalpy of formation of benzene from data

C6H6(l) + O2 → 6 CO2(g) + 3 H2O (l); ΔcH0 (C6H6) = - 3266.0 kJ/mol
C (s) + O2 (g) → CO2(g); ΔfH0(CO2) =-393.1 kJ/mol
H2(g) + O2 (g) → H2O (l); ΔfH0 (H2O) = -286.0 kJ/mol

Ans: ΔfH0 (C6H6) = - ΔcH0 (C6H6) + 6 x ΔfH0(CO2) + 3 x ΔfH0 (H2O)

= 3266 + 6 (- 393.1) + 3 (-286) = 49.4 kJ/mol

70
 Chapter 7: Equlibrium

Main points:

Chemical equlibrium:

• In a chemical reaction chemical equilibrium is defined as the state at which there is no further change in
concentration of reactants and products.
For example,

• At equilibrium the rate of forward reaction is equal to the rate of backward reaction.
• Equilibrium can be established for both physical and chemical processes and at this stage rate of forward
and reverse reactions are equal.

Equilibrium mixture:

• The mixture of reactants and products in the equilibrium state is called an equilibrium mixture.
• Based on the extent to which the reactions proceed to reach the state of equilibrium, these may be
classified in three groups:
➢ The reactions which proceed almost to completion and the concentrations of the reactants left
are negligible.
➢ The reactions in which most of the reactants remains unchanged, i.e. only small amounts of
products are formed.
➢ The reactions in which the concentrations of both the reactants and products are comparable
when the system is in equilibrium.

Equilibrium in Physical Processes:

• When equilibrium is attained for physical process, it is characterised by constant value of one of its
parameters at a given temperature.
• Different types of equilibrium for physical process are as follows:

(i) Solid-Liquid Equilibrium:

• When there is an equilibrium between a solid and a liquid, it is called solid- liquid equilibrium.
• The equilibrium is represented as
• Rate of melting of ice = Rate of freezing of water.
• The system here is in dynamic equilibriums and following can be inferred.
(a) Both the opposing processes occur simultaneously.
(b) Both the processes occur at the same rate so that the amount of ice and water remains constant.

(ii) Liquid-Vapour Equilibrium:

• When there is an equilibrium between liquid and vapours, it is called liquid-vapour equilibrium.
• When the number of molecules leaving the liquid to vapour equals the number of molecules
returning to the liquid from vapour, equilibrium is said to be attained and is dynamic in nature.
71
 • The equilibrium can be represented as
• Rate of evaporation = Rate of condensation

(iii) Solid-Vapour Equilibrium:

• This type of equilibrium is attained where solids sublime to vapour phase.

• For example, when solid iodine is placed in a closed vessel, violet vapours start appearing in the
vessel whose intensity increases with time and ultimately, it becomes constant.
• The equilibrium can be represented as
• Rate of Sublimation of solid I2 to form vapour = Rate of condensation of I2 vapour to give solid I2.

Equilibrium involving Dissolution of Solid in Liquid:

• Solution: When a limited amount of salt or sugar or any solute dissolves in a given amount of water
solution is formed.
• At a given temperature, a state is reached when no more solute can be dissolved then the solution is
called saturated solution.
• The equilibrium between a solid and its solution is indicated by the saturated solution and may be
represented as

• Here dissolution and precipitation takes place with the same speed.
• On adding a small amount of radioactive sugar to the saturated solution it will be found that the sugar
present in the solution as well as in the solid state is radioactive.

Equilibrium between a Gas and its Solution in Liquid:

• This type of equilibrium can be seen by the following example:

Let us consider a sealed soda water bottle in which CO2 gas is dissolved under high pressure. A state of
equilibrium is attained between CO2 present in the solution and vapours of the gas.

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.

Characteristics of Equilibria Involving Physical Processes:

• The equilibrium can be attained only in closed systems at a given temperature.

• At the equilibrium the measurable properties of the system remain constant.
72
• The equilibrium is dynamic since both the forward and backward processes occur at same rate.
• At equilibrium, the concentrations of substances become constant at constant temperature.
• The value of equilibrium constant represents the extent to which the process proceeds before
equilibrium is achieved.

Equilibrium in Chemical Processes:

• Equilibrium involving chemical processes: In chemical equilibrium, when the rates of forward and reverse
reactions become equal, the concentrations of the reactants and the products remain constant.
• Like equilibria in physical systems it can also be achieved in chemical process involving reversible
chemical reactions carried in closed container.
• For example,
• The dynamic nature of chemical equilibrium can be demonstrated in the synthesis of ammonia by
Haber’s process. At regular intervals of time, the amount of ammonia present is determined. The
concentration of unreacted N2 and H2 is also measured. After a certain time it is observed that the
composition of mixture remains the same even though some of the reactants are still present. This
constancy indicates the attainment of equilibrium.
• This can be shown by the given figure:

• In general, for a reversible reaction the chemical equilibria can be shown by

After a certain time the two reactions occur at the same rate and the system reaches a state of
equilibrium.
• The concentrations in an equilibrium mixture are related by the following equilibrium equation,
{𝐶}{𝐷}
Kc = {𝐴}{𝐵}
where Kc is the equilibrium constant and the expression on the right side is called the
equilibrium constant expression.

Law of Chemical Equilibrium:

• At a constant temperature, the rate of a chemical reaction is directly proportional to the product of
the molar concentrations of the reactants each raised to a power equal to the corresponding
73
 stoichiometric coefficients as represented by the balanced chemical equation. Let us consider the
reaction, a A + b B ⇋ c C + d D
• Equilibrium constant, Kc is expressed as the concentration of products divided by reactants, each
term raised to the stoichiometric coefficient.
• Kc is expressed as Kc = [C]c[D]d / [A]a[B]b where [A], [B], [C] and [D] are the equilibrium
concentrations of the reactants and products.
• Equilibrium constant has constant value at a fixed temperature and at this stage all the macroscopic
properties such as concentration, pressure, etc. become constant.
• Equilibrium constant for the reverse reaction is the inverse of the equilibrium constant for the
reaction in the forward direction. Thus, K′c = 1 / Kc
• For a gaseous reaction equilibrium constant is expressed as Kp and is written by replacing
concentration terms by partial pressures in Kc expression.
Kp is expressed as Kp = [pC]c[pD]d / [pA]a[pB]b

Law of mass action:

• It states the rate of a chemical reaction is directly proportional to the product of molar concentration
of the reactants at a constant temperature at any given time.
• The direction of reaction can be predicted by reaction quotient Qc which is equal to Kc at equilibrium.

Homogeneous equilibrium reaction:

• When all reactants and products are in same phase it is called homogeneous equilibrium reaction.

Heterogeneous equilibrium reaction:

• When all reactants and products are in different phases it is called heterogeneous equilibrium
reaction.

Characteristic features of equilibrium constant:

• Equilibrium constant is applicable only when the concentration of reactants and products have
attained their equilibrium state.
• Equilibrium constant has a definite value for every reaction at a particular temperature. Equilibrium
constant is independent of presence of catalyst. The value of equilibrium constant is independent of
initial concentrations of the reactants and products.
• Applications of equilibrium constant
➢ Helps in predicting the extent of a reaction If Kc > 103 , products predominate over reactants,
the reaction proceeds nearly to completion If Kc < 10-3 , reactants predominate over products,
the reaction proceeds rarely to completion If Kc is in the range of 10 -3 to 103 , considerable
concentrations of both reactants and products are present, similar to equilibrium mixture.
➢ Predicting the direction of the reaction Reaction quotient (Q) is the ratio of product of
concentration (or partial pressure) of products to that of reactants at any stage of the reaction
If Qc >Kc , the reaction will proceed in the direction of reactants (reverse reaction). If Qc < Kc

74
 , the reaction will proceed in the direction of the products (forward reaction) If Qc = Kc , the
reaction mixture is already at equilibrium.

Le Chatelier’s principle:

• Le Chatelier’s principle 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 or counteract
the effect of the change.
• It can be used to study the effect of various factors such as temperature, concentration, pressure,
catalyst and inert gases on the direction of equilibrium and to control the yield of products by
controlling these factors.

Factors Affecting Equilibria:

Effect of Change of Concentration:

• When the concentration of any of the reactants or products in a reaction at equilibrium is changed,
the composition of the equilibrium changes so as to minimize the effect.

Effect of Pressure Change:

• If the number of moles of gaseous reactants and products are equal, there is no effect of pressure.
• When the total number of moles of gaseous reactants and total number of moles of gaseous
products are different, on increasing pressure, total number of moles per unit volume increases,
thus the equilibrium will shift in direction in which number of moles per unit volume will be less.
• If the total number of moles of products are more than the total number of moles of reactants, low
pressure will favour forward reaction.
• If total number of moles of reactants are more than total number of moles of products, high
pressure is favourable to forward reaction.

Effect of Inert Gas Addition:

• If the volume is kept constant there is no effect on equilibrium after the addition of an inert
gas. This is because the addition of an inert gas at constant volume does not change the partial
pressure or the molar concentration. The reaction quotient changes only if the added gas is
involved in the reaction.

Effect of Temperature Change:

• When the temperature of the system is changed (increased or decreased), the equilibrium shifts in
opposite direction in order to neutralize the effect of change.
• In exothermic reaction low temperature favours forward reaction e.g.,

but practically very low temperature slows down the reaction and thus a catalyst is used.
• In case of endothermic reaction, the increase in temperature will shift the equilibrium in the
direction of the endothermic reaction.
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 Effect of a Catalyst:

• Catalyst has no effect on the equilibrium composition of a reaction mixture.

Reason: Since catalyst increases the speed of both the forward and backward reactions to the same
extent in a reversible reaction.
• Catalyst does not affect the equilibrium composition of a reaction mixture but increases the rate of
chemical reaction by making available a new lower energy pathway for conversion of reactants to
products and vice-versa.

Ionic Equilibrium in Solution:

Ionic Equilibrium: The equilibrium formed between ions and un-ionised substance is called ionic
equilibrium, e.g.,

Electrolytes:
• Substances which conduct electricity in their aqueous solution.
• Acids, bases and salts are electrolytes and the conduction of electricity by their aqueous solutions is
due to anions and cations produced by the dissociation or ionization of electrolytes in aqueous
solution.

Strong Electrolytes: Electrolytes which on dissolution in water are ionized almost completely are called
strong electrolytes.

Weak electrolyte: Electrolytes which on dissolution in water partially dissociated are called weak
electrolyte.

Arrhenius Concept of Acids and Bases:

• According to Arrhenius theory, acids are substances that dissociate in water to give hydrogen ions
H+(aq).
and bases are substances that produce OH–(aq) after dissociation in water.
• The expressions for ionization (equilibrium) constants of weak acids (Ka) and weak bases (Kb) are
developed using Arrhenius definition.

Limitation of Arrhenius concept:

• The concept is applicable only to aqueous solutions and it does not account for the basicity of
substances like ammonia which does not have hydroxyl group.

Brönsted-Lowry Concept:

• Brönsted-Lowry defined an acid as a proton donor and a base as a proton acceptor.

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 • 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+.
This can be explained by the following example.

Acid and Base as Conjugate Pairs:

• When a Brönsted-Lowry acid reacts with a base, it produces its conjugate base and a conjugate acid
corresponding to the base with which it reacts. Thus, a conjugate pair of acid-base differs only by one
proton.
• The acid-base pair that differs only by one proton is called a conjugate acid-base pair.
Let us consider the example of ionization of HCl in water.

Here water acts as a base because it accepts the proton. Cl- is a conjugate base of HCl and HCl is the
conjugate acid of base Cl-. Similarly, H2O is a conjugate base of an acid H3O+ and H3O+ is a conjugate
acid of base H2O.

Lewis Concept:

• Lewis further generalized the definition of an acid as an electron pair acceptor and a base as an
electron pair donor.
• Electron deficient species like AlCl3, BH3, H+ etc. can act as Lewis acids while species like H2O, NH3 etc.
can donate a pair of electrons can act as Lewis bases.

The ionization constant of water/ The ionic product of water:

• It is defined as the product of the molar concentration of hydrogen ion (hydronium ion) and hydroxyl ion
in water or in any aqueous solution.
• Water is a weak electrolyte and hence it ionizes only partially as: H2O ⇋ H+ + OH-
Or, H2O + H2O ⇋ H3O+ + OH-
The dissociation constant, K = [H+ ][OH- ]
Or, K = [H3O+ ][OH- ] /[H2O] [H2O]
Or, Kw = [H+ ][OH- ]
Or, Kw = [H3O+ ][OH- ]
Where Kw is called ionization constant of water or ionic product of water.
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• For pure water at 298K, [H+ ] = [OH- ] = 10-7M.
Therefore, Kw = [H+ ][OH- ] = 10-7 x 10-7 = 10-14M
The value of Kw is temperature dependent. By knowing the concentrations of H3O + and OH- ions, we can
predict the nature of an aqueous solution.
• If [H3O + ] > [OH- ], the solution is acidic.
• If [H3O+ ] < [OH- ], the solution is basic.
• If [H3O +] = [OH-], the solution is neutral.

The pH scale:

• Strength of acid or base is determined with the help of extent of ionization in aqueous solution.
• Hydrogen ion concentration are measured as the number of gram ions of hydrogen ions present per
litre of solution. Since these concentrations are usually small, the concentration is generally
expressed as the pH of the solution.
• pH is defined as the negative logarithm of the hydrogen ion or hydronium ion concentration in moles
per litre (i.e. molarity). i.e. pH = - log[H+ ] or pH = - log[H3O+]
• For pure water pH = -log[10-7] = 7
• Negative logarithm of hydroxyl ion concentration in mol/L is called pOH . i.e. pOH = -log[OH- ]
• Kw = 1 x 10-14 ‫ ؞‬pKw = –log[Kw] = -log[10-14] = 14 = pH + pOH
• The pH scale was introduced by Sorensen. It contains numbers from 0 to 14. If the pH is less than 7,
the solution is acidic, if it is greater than 7, it is basic and if it is 7, the solution is neutral.
• pKa = –log[Ka] ; pKb = –log[Kb]

The degree of ionization (α):

• The extent up to which an acid or a base or a salt ionize to form ions is called the degree of ionization.
• It is the ratio of the number of moles of the electrolyte dissociated to the total number of moles of
the undissociated molecule.

Ionization constant of weak acids:

• A weak acid HX ionizes only partially as HX + H2O ⇋ H3O + + X-

Let ‘c’ be the initial concentration of HX and ‘α’ is the degree (extent) of dissociation.
HX(aq) + H2O(l) ⇋ H3O + (aq) + X- (aq)
Initial concn c 0 0
n
Eqm. conc c(1-α) cα cα
+ -
‫ ؞‬The dissociation constant, Ka = [H3O ][X ]/ [HX] Where Ka is the dissociation constant of the weak
acid Or, Ka = cα x cα/ c(1-α) = cα2 / 1-α
• The negative logarithm of Ka is called pKa . i.e. pKa = -logKa. Greater the value of Ka, smaller will be
the value of pKa and stronger will be the acid.

Ionization constant of weak bases:

• A weak base MOH ionizes partially as MOH ⇋ M+ + OH-

Let ‘c’ be the initial concentration of MOH and ‘α’ is the degree of dissociation.
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 MOH(aq) + H2O(l) ⇋ M+(aq) + OH- (aq)
Initial concn c 0 0
n
Eqm. conc c(1-α) cα cα
‫ ؞‬The dissociation constant of weak base, Kb = [M+ ][OH- ]/ [MOH]
Or, Kb = cα x cα/ c(1-α) = cα2/ 1-α
• The negative logarithm of Kb is called pKb . i.e. -logKb = pKb . As the value of Kb increases, pKb
decreases and the basic strength increases.

Relation between Ka, Kb and Kw:

• For conjugate acid – base pair Ka and Kb are related as Ka x Kb = Kw

• For the reaction NH4 + + H2O ⇋ NH3 + H3O + , Ka = [NH3][H3O + ] /[NH4 + ]
• Also, for the reaction NH3 + H2O ⇋ NH4 ++ OH- , Kb = [NH4 + ][OH- ] /[NH3]
‫ ؞‬Ka x Kb = [NH3][H3O + ]/ [NH4 + ] x [NH4 + ][OH- ] /[NH3]
= [H3O + ][OH- ]
= Kw
i.e. Ka x Kb = Kw = 10-14
or, pKa + pKb = pKw = 14

Di and Polybasic Acids:

• Acids which contain more than one ionizable proton per molecule are called Dibasic acids or
polybasic acids or polyprotic acids. Common examples are oxalic acid, sulphuric acid, phosphoric
acid etc.
• For example,

Factors Affecting Acid Strength:

• The extent of dissociation of an acid and its acidic strength depend on the strength and polarity of
the H-A bond.
• Weaker the H-A bond, more easily it dissociates to give H+ ion and hence stronger is the acid.
• Also, greater the polarity of the H – A bond (when the electronegativity difference between the atoms
H and A increases), the more easily it dissociates and hence greater is the acidity.
• In a group, acidity is mainly determined by bond strength. From top to bottom in a group, as the
size of A increases, H-A bond strength decreases, the energy required to break the bond decreases
and H-A becomes a stronger acid.
Thus, acidic strength of hydrohalic acids increases in the order: HF < HCl < HBr < HI.

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 • In a period, acidity is mainly determined by polarity of the bond. As the electronegativity of A
increases from left to right in a period, the strength of the acid also increases. So, the acidity of
hydrides of second period elements increases in the order CH4 < NH3 < H2O < HF.

Hydrolysis of Salts:

• Process of interaction between water and cations/anions or both of salts is called hydrolysis.

• Hydrolysis of salt of strong base and weak acid:

➢ Sodium acetate (CH3COONa), sodium carbonate (Na2CO3), potassium cyanide (KCN) etc. are
examples for such type of salts.
➢ Here only the anion of the weak base undergoes hydrolysis (since cation of the strong base
does not hydrolyse).
➢ So, the solution of such salts will be basic. i.e. pH > 7.
➢ pH of such salt solution is given by pH = 7 + ½ (pKa + log C) where C is the concentration of
salt.

• Hydrolysis of salt of weak base and strong acid:

➢ NH4Cl, NH4NO3, CuSO4 etc. are examples for such type of solutions.
➢ Here only cation of weak base undergoes hydrolysis.
➢ So, the solution is acidic. pH of such a solution is given by pH = 7 + ½ (pK b + log C)

• Hydrolysis of salt of weak base and weak acid:

➢ Ammonium acetate (CH3COONH4), ammonium carbonate [(NH4)2CO3] etc. are examples for
such type of salts.
➢ Here both cation and anion undergo hydrolysis and hence weak acid and weak base are
produced in solution.
➢ So, the solution may be neutral, acidic or basic depending upon the relative strength of acid
and base formed. pH of such a solution is given by pH = 7 + ½ (pK a + pKb).

• Hydrolysis of salt of strong base and strong acid:

➢ The cations (e.g., Na+, K+,Ca2+, Ba2+ etc.) of strong bases and anions (e.g., Cl–, Br–, ClO4- etc.) of
strong acids simply get hydrated but do not hydrolyse, and therefore the solutions of salts
formed from strong acids and bases are neutral i.e., their pH is 7.

Common ion Effect:

• The shift in equilibrium position caused by the addition or presence of an ion involved in the
equilibrium reaction is known as common ion effect.
• It is the suppression of the dissociation of a weak electrolyte by the addition of a strong electrolyte
containing a common ion.
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 • If in an aqueous solution of a weak electrolyte, a strong electrolyte is added having an ion common
with the weak electrolyte, then the dissociation of the weak electrolyte is decreased or suppressed.
The effect by which the dissociation of weak electrolyte is suppressed is known as common ion
effect.

• Another example is the dissociation of the weak base ammonium hydroxide (NH4OH).
NH4OH(aq) ⇋ NH4 + (aq) + OH- (aq)
If we add some NH4Cl to the above equilibrium process, the concentration of NH4 + increases and
hence the equilibrium shifted to the left. i.e. the dissociation rate of NH4OH decreases.

Buffer solutions:

• Buffer solutions are the solutions which resist change in pH on dilution or addition of small amount
of acid or alkali.
• Acidic buffers contain equimolar quantities of a weak acid and one of its salt with a strong base. E.g.
a mixture of acetic acid and sodium acetate acts as an acidic buffer around pH 4.75.
• Basic buffers contain equimolar quantities of a weak base and one of its salt with a strong acid. E.g.
a mixture of NH4OH and NH4Cl acts as a basic buffer around pH 9.25.

pH of a Buffer solution– Henderson - Hasselbalch Equation:

• Consider an acidic buffer prepared by mixing a weak acid HA and its conjugate base A- .
• The weak acid HA ionises in water as HA + H2O ⇋ H3O + + A-
The dissociation constant of weak acid, Ka = [H3O +] [A- ] /[HA]
Taking –ve logarithm on both sides, -log Ka = -log [H3O +] – log [A-] /- log [HA]
Or, -log [H3O +] = - logKa + log [A-] – log [HA]
Or, pH = pKa + log [A-]/[HA]
This equation is known as Henderson-Hasselbalch equation.
• For an acidic buffer, the equation can be written in general form as pH = pKa + log [Salt]/[Acid]
• For a basic buffer, pOH = pKb + log [Salt]/[Base]
Or, pH = 14 – [pKb + log [Salt]/[Base]

Solubility Equilibrium:

• The solubility of a salt in solvent mainly depends on the lattice enthalpy and solvation enthalpy.
• As a general rule, for a salt to be able to dissolve in a particular solvent its solvation enthalpy must
be greater than its lattice enthalpy.
• Each salt has its characteristic solubility which depends on temperature.
• We can classify salts on the basis of their solubility in the following three categories:
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 ➢ Category I: Soluble salt where solubility > 0.1M
➢ Category II: Slightly Soluble salt where solubility is in between 0.01M and 0.1M
➢ Category III: Sparingly Soluble salt where solubility < 0.01M

Solubility product:
• The product of the molar concentrations of the ions in a saturated solution, each concentration
term raised to the power equal to the no. of ions produced.
It is applicable to sparingly soluble salt. There is equilibrium between ions and unionised solid
substance.

• For a general salt AxBy, its dissociation can be denoted as

AxBy (s) ⇋ xAy+ (aq.) + yBx- (aq.)
Ksp = [Ay+] x [Bx-] y
• If the concentration in the above equation is not the equilibrium concentration, then K sp is given by
Qsp.
• At equilibrium, Ksp = Qsp.
• If Ksp > Qsp, the dissolution process occurs.
• If Ksp < Qsp, the precipitation of the salt occurs.

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