1.

SOME BASIC CONCEPTS OF CHEMISTRY

Chemistry is the branch of Science that deals with the properties, structure and composition of matter.
There are a large number of branches for Chemistry. Some of them are: The International System of Units
(SI)

Matter: Matter is anything that occupies space, has a definite mass and can be perceived by any of our
sense organs.
Chemical Classification of matter---

Classification of matter
Matter can be divided into two categories – pure substances and mixtures.

Pure substances contain only one type of particles. These are further divided into two – elements and
compounds.

Elements are pure substances which contain only one type of particles. These particles may be atoms or
molecules. E.g. Hydrogen, Nitrogen, Oxygen (diatomic), Sodium, Potassium, Lithium, Calcium
(monoatomic), Phosphorus, Sulphur (polyatomic) etc.

Compounds are pure substances which contain more than one type of atoms in a fixed ratio by mass. E.g.
CO2, H2O, NH3, H2SO4 etc.

Mixtures contain more than one type of particles. There are two types of mixtures –Mixtures having
uniform composition throughout are called homogeneous mixtures. E.g. all type of solutions, air etc.
Mixtures having different compositions at different parts are called heterogeneous mixtures. E.g. sea
water, soil etc.

Mass and Weight :Mass is the amount of matter present in a body. It is a constant quantity. Its SI unit is
kilogram (kg). Weight is the gravitational force acting on a body. It is a variable quantity. i.e. it changes
with place. Its SI unit is newton (N).
Temperature (T)
It is the degree of hotness or coldness of a body. It is commonly expressed in degree Celsius (0C). Other
units are degree Fahrenheit (0F), Kelvin (K) etc. its SI unit is Kelvin (K).
Degree Celsius and degree Fahrenheit are related as:
0
F = 9/5(0C) + 32
Degree celsius and Kelvin are related as:
 K = 0C + 273.15
Precision and Accuracy
Precision refers to the closeness of various measurements for the same quantity. But, accuracy is the
agreement of a particular value to the true value of the result.
Scientific Notation: In which any number can be represented in the form N × 10n
e.g. We can write 232.508 as 2.32508 x102 in scientific notation. Similarly, 0.00016 can be written as 1.6
x 10–4.
Significant Figures
The uncertainty in the experimental or the calculated values is indicated by mentioning the number of
significant figures. Significant figures are meaningful digits which are known with certainty.
There are certain rules for determining the number of significant figures. These are:
1. All non-zero digits are significant.
2. Zeros preceding to first non-zero digit are not significant. Such zero indicates the position of
decimal point.
3. Zeros between two non-zero digits are significant.
4. Zeros at the end or right of a number are significant if they are on the right side of the decimal
point; otherwise, they are not significant.
5. Exact numbers have an infinite number of significant figures.
6. When numbers are written in scientific notation, the number of digits between 1 and 10 gives the
number of significant figures.
LAWS OF CHEMICAL COMBINATIONS
The combination of elements to form compounds is governed by the following five basic laws:
1. Law of Conservation of Mass : This law was proposed by Antoine Lavoisier. It states that matter can neither be
created nor destroyed. We can only convert one form of matter into another form. Or,in a chemical reaction, the total
mass of reactants is equal to the total mass of products.
Consider the reaction 2H2 + O2 → 2H2O
Total mass of reactants = 4 + 32 = 36g
Total mass of products = 36 g

2. Law of Definite Proportions (Law of definite composition): This law was proposed by Joseph Proust. It states
that a given compound always contains exactly the same proportion of elements by weight. Or, the same
compound always contains the same elements combined in afixed ratio by mass.
Illustration: Carbon dioxide contains only two elements Carbon and Oxygen combined in a mass ratio
3:8.
3. Law of Multiple Proportions: This law was proposed by John Dalton. It states that if two elements can
combine to form more than one compound, the different masses of one of theelements that combine
with a fixed mass of the other element, are in small whole number ratio.
Illustration: Hydrogen combines with oxygen to form two compounds – water and hydrogen peroxide.
Hydrogen + Oxygen → Water
2g 16g 18g
Hydrogen + Oxygen → Hydrogen Peroxide
2g 32g 34g
Here, the masses of oxygen (i.e. 16 g and 32 g) which combine with a fixed mass of hydrogen (2g) bear
a simple ratio, i.e. 16:32 or 1: 2.
4. Gay Lussac’s Law of Gaseous Volumes: This law was proposed by Gay Lussac. It states thatwhen gases
combine to form gaseous products, their volumes are in simple whole number ratio at constant
temperature and pressure.
Illustration:
2H2(g) + O2(g) → 2H2O(g). the volumes of hydrogen and oxygen which combine together bear a
simple ratio of 2:1.
5. Avogadro’s Law: It states that equal volumes of all gases at the same temperature andpressure
should contain equal number of moles or molecules.
 DALTON’S ATOMIC THEORY
The important postulates of this theory are:
1. Matter is made up of minute and indivisible particles called atoms.
2. Atoms can neither be created nor be destroyed.
3. Atoms of same element are identical in their properties and mass. While atoms of different
elements have different properties and mass.
4. Atoms combined to form compound atoms called molecules.
5. When atoms combine, they do so in a fixed ratio by mass.
Atomic mass
Atomic mass of an element is a number that expresses how many times the mass of an atom of the
element is greater than 1/12th the mass of a C12 atom.

For e.g. atomic mass of Nitrogen is 14, which means that mass of one N atom is 14 times greater
than 1/12th the mass of a C12 atom. 1/12th the mass of a C12 atom is called atomic mass unit (amu). Today,
‘amu’ has been replaced by ‘u’ which is known as unified mass.
Average atomic mass: All most all the elements have isotopes. So we can calculate an average atomic
mass of an element by considering the atomic mass of the isotopes and their relative abundance. For e.g.
chlorine has two isotopes Cl35 and Cl37 in the ratio 3:1. So the average atomic mass Cl = (3x35 +
1x37)/4 =35.5

Molecular mass: Molecular mass is the sum of atomic masses of the elements present in a molecule.
For e.g. molecular mass of H2SO4 is calculated as: 2 x 1 + 32 + 4 x 16 = 98 u.

Formula mass:
In the case of ionic compounds (like NaCl), there is no discrete (separate) molecules. Here the
positive ions and the negative ions are arranged in a three-dimensional structure. So we can calculate only
formula mass by taking molecular formula of the compound.
Mole concept
Mole is the unit of amount of substance. It is defined as the amount of substance that contains as
many particles as there are atoms in exactly 12 g C12 isotope. 1 mole of any substance contains 6.022 x
1023 atoms. This number is known as Avogadro number or Avogadro constant (NA or N0).
1 mol of hydrogen atoms = 6.022×1023 atoms
1 mol of water molecules = 6.022×1023 water molecules
1 mol of sodium chloride = 6.022 × 1023 formula units of sodium chloride

Molar mass: The mass of one mole of a substance in gram is called its molar mass (gram molecular mass).
Molar volume: It is the volume of 1 mole of any substance at STP. molar volume of any gas = 22.4
For e.g. 22.4 L of hydrogen gas = 1 mole of H2 = 6.022x1023 molecules of hydrogen = 2 g of H2
Percentage composition
It is the percentage of each element present in 100g of a substance.
percentage of an element =

Empirical Formula and Molecular Formula—

An empirical formula represents the simplest whole number ratio of various atoms present in a
compound. Eg. 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. Eg. C6H6 is the molecular formula of benzene.
Relationship between empirical and molecular formulae
The two formulas are related as Molecular formula = n x empirical formula
 n=

Stoichiometry and Stoichiometric calculations

The study about the quantitative relationship between the masses or the volumes of reactants and the
products.
Limiting Reagent- The reactant which gets consumed first or limits the amount of product formed is
known as limiting reagent.

Reactions in solutions
Solutions are homogeneous mixture containing 2 or more components. The component which is present
in larger quantity is called solvent and the other components are called solutes.For e.g. in NaCl
solution, NaCl is the solute and water is the solvent.
Concentration of solution
It is defined as the amount of solute present in a given volume of solution. Concentration can be expressed
in the following ways:
1. Mass Percent is the mass of the solute in grams per 100 grams of the solution.
Mass % =

2. Volume percent is the number of units of volume of the solute per 100 units of the volume of
solution.
Volume% =

3. Molarity of the solution is defined as the number of moles of solute dissolved per litre (dm3) of
the solution.
Molarity (M) =

Molarity equation
To calculate the volume of a definite solution required to prepare solution of other molarity, the
following equation is used:
M1V1 = M2V2,
1. Molality- Molality is defined as the number of moles of solute dissolved per 1000 g (1 kg) of
solvent. Molality is expressed as 'm'.
Molality =

6. Mole Fraction. It is the ratio of number of moles of one component to the total number of
moles (solute and solvents) present in the solution. It is expressed as 'x'. If nA and nB are the
number of moles of solute and solvent. then

Mole fraction of the solute = XB =

Mole fraction of the solvent = XA =

for a binary solution XA+ XB =1

 Questions Answer
1. Which of the following is dependent on temperature? (a)
(a) Molarity (b) Molality (c) Mole fraction (d) Mass percentage

2. If the concentration of glucose (C6H12O6) in blood is 0.9 g L molarity of

glucose in blood? (c)
a) 5M b) 50M c) 0.005 M d) 0.5 M

3. What is the mass percent of carbon in carbon dioxide? (b)

a) 0.034% b) 27.27% c) 3.4% d) 28.7%

4. The empirical formula and molecular mass of a compound are CH2O and 180 (c )
g respectively. What will be the molecular formula of the compound?
a) C9H18O9 b) CH2O c) C6H12O6 d) C2H4O2

5. the total number of ions present in 111 g of CaCl2 is (c)

(a) One Mole (b) Two Mole (c) Three Mole (d) Four Mole

6. Which one will have maximum numbers of water molecules?

(a) 18 molecules of water (b) 1.8 grams of water (d)
(c) 18 grams of water (d) 18 moles of water

7. There are two chlorides of sulphur S2Cl2 and SCl2. What is the equivalent mass of
Sin SCl2 (c)
(a) 64.8 g/mole (b) 32 g/mole (c) 16 g/mole (d) 8 g/mole

8. Which is not a unit of pressure:

(a) Bar (b) N/m² (c) Kg/m² (d) Torr (c)

9. What is the normality of a 1 M solution of H3PO4

(a) 0.5 N (b) 1.0 N (c) 2.0 N (d) 3.0 N (d)

10. The significant figures in 3400 are

(a) 2 (b) 5 (c) 6 (d) 4 (d)

11. Which of the following contains the same number of carbon atoms as are in 6.0 g
of carbon (C – 12)? (b)
(a) 6.0 g Ethane (b) 8.0g Methane (c) 21.0g Propane (d) 28.0 g CO

ASSERTION AND REASON QUESTIONS

In the following questions a statement of Assertion (A) followed by a statement of Reason (R) is given.
Choose the correct option out of the choices given below each question.
a) If both Assertion & Reason are true and the reason is the correct explanation of the assertion.
b) If both Assertion & Reason are true but the reason is not the correct explanation of the assertion.
c) If Assertion is a true statement but Reason is false.
d) If both Assertion and Reason are false statements.
1. Assertion (A): The empirical mass of ethene is half of its molecular mass.
Reason (R): The empirical formula represents the simplest whole number ratio of various atoms present in
a compound. Answer : (b)
2.Assertion (A) : One atomic mass unit is defined as one twelfth of the mass of one carbon-12 atom.
Reason (R) : Carbon-12 isotope is the most abundant isotope of carbon and has been chosen as standard.
Answer : (b)
3.Assertion (A) : Significant figures for 0.200 is 3 whereas for 200 it is 1.
Reason (R) : Zero at the end or right of a number are significant provided they are not on the right side of
the decimal point. Answer: (c)
4. Assertion (A): Combustion of 16 g of methane gives 28 g of water.
Reason (R): In the combustion of methane, hydrogen is one of the products. Answer: (d)
5. Assertion: Molarity is number of moles of solute in 1 lit of solution
Reason: Molality does not change with temperature. Answer: (b)
One Mark questions with answers
1. Calculate the molecular mass of the of the following
(i)H2SO4 (ii)NaOH
Ans: Molar mass of H2SO4= 2+32+4*16=98 amu
Molar mass of NaOH = 23+16+1=40amu
2. What do mean by Mole fraction?
Ans. Mole Fraction is the ratio of number of moles of one component to the total number of moles
(solute and solvents) present in the solution. It is
expressed as 'x'.
3. What is the limiting reagent?
Ans. The reactant which gets consumed first or limits the amount of product formed is known as
limiting reagent
4. What is the relation between temperature in degrees Celsius and degree Fahrenheit?
Ans.

5. Define one mole?

Ans. One mole is the amount of a substance that contains as many particles as there are atoms in
exactly 12 g of the carbon-12.
6. Write the empirical formula of the following:
(a)N2O4 (b)6H12O6 (c) H2O (d) H2O2
Ans. (a)NO2 (b) CH2O (c) H2O (d) HO
7. Briefly explain the difference between precision and accuracy.
Ans. Precision refers to the closeness of various measurements for the same quantity. However,
accuracy is the agreement of a particular value to the true value of the result.
8. Define the law of multiple proportions. Explain it with one example. Ans.When two
elements combine to form two or more compounds, then the different masses of one
element, which combine with a fixed mass of the other, bear a simple ratio to one another.
For example- carbon combines with oxygen to form two compounds CO and CO2.
Compound CO CO2
Mass of C 12 12
Mass of O 16 32
Masses of oxygen which combine with a fixed mass of carbon (12g) bear a simple ratio of
16:32 or 1:2.
9. Chlorine has two isotopes of atomic mass units 34.97 and 36.97. The relative abundance of the
isotopes is 0.755 and 0.245 respectively. Find the average atomic mass of chlorine.
Ans. Average atomic mass = 34.97 x 0.755 +36.97 x 0.245 = 35.46 u
10. How are 0.50 mol Na2CO3 and 0.50 M Na2CO3 different?
Ans. Molar mass of Na2CO3= 2 x 23 +12 + 3 x 16 = 106 g / mol
0.50 mol Na2CO3 and 0.50 x 106 = 53 g
0.50 M Na2CO3 means 0.50 mol i.e. 53 g of Na2CO3 are present in I L of the solution.
 Three Marks questions with answers-
1. How many molecules approximately do you expect to be present in a small crystal of sugar which
weighs 10 mg?
Answer:
10 mg sugar (C12H22O11) = 0.01 g = 0.01/342 mol
= 2.92 × 10-5 mole
= 2.92 × 10-5 × 6.02 × 1023 molecules
= 1.76 × 1019 molecules.

2. What do mean by molarity .Calculate the molarity of NaOH in the solution prepared by dissolving its
4 g in enough water to form 250 mL of the solution.
And. The number of moles of solute dissolved per litre (dm3) of the solution is called molarity
Since molarity (M) =
.3. Express the following in the scientific notation with 2 significant figures-
(a) 0.0048 (b) 234,000 (c) 200.0
Ans. (a) 4.8 x 10-3 (b) 2.3 x 105 (c) 2.0 x 102
4. Calcium carbonate reacts with aqueous HCl according to the reaction
CaC03 (s) + 2HCl (aq) ———->CaCl2 (aq) +C02(g) +H2O(l).
What mass of CaC03 is required to react completely with 25 mL of 0.75 M
Step 1. To calculate mass of HCl in 25 mL of 0.75 m HCl
1000 mL of 0.75 M HCl contain HCl = 0.75 mol = 0.75 x 36.5 g = 24.375 g

Step 2. To calculate mass of CaC03reacting completely with 0.9125 g of HCl

CaC03 (s) + 2HC1 (aq)———->CaCl2(aq) +C02(g) + H2O
2 mol of HCl, i.e., 2 x 36.5 g = 73 g HCl react completely with CaC03 = 1 mol = 100 g

5. Chlorine is prepared in the laboratory by treating manganese dioxide (Mn02) with aqueous hydrochloric
acid according to the reaction.
4 HCl (aq) + Mn02 (s) ———–> 2 H2O (l) + MnCl2(aq) +Cl2(g)
How many grams of HCl react with 5.0 g of manganese dioxide? (Atomic mass of Mn = 55 u)
Answer: 1 mole of Mn02, i.e., 55 + 32 = 87 g Mn02 react with 4 moles of HCl, i.e., 4 x 36.5 g = 146 g of
HCl.

Case based questions with answers

1.The mass of one mole of a substance in grams is called its molar mass. the molar mass in grams is
numerically equal to atomic molecular/formula mass in u. An empirical formula represents the simplest
whole number ratio of various atoms present in a compound, whereas, the molecular formula shows the
exact number of different types of atoms present in a molecule of a compound. If the mass per cent of
various elements present in a compound is known, its empirical formula can be determined. Molecular
formula can further be obtained if the molar mass is known. Many a time, reactions are carried out with the
Amounts of reactants that are different than The amounts as required by a balanced chemical reaction. In
such situations, one Reactant is in more amount than the amount required by balanced chemical reaction.
The reactant which is present in the least amount Many a time, reactions are carried out with the amounts
of reactants that are different than the amounts as required by a balanced chemical reaction. In such
situations, one reactant is in more amount than the amount required by balanced chemical reaction. The
reactant which is present in the least amount gets consumed after sometime and after that further reaction
does not take place whatever be the amount of the other reactant. Hence, the reactant, which gets consumed
first, limits the amount of product formed and is, therefore, called the limiting reagent.

1) One atomic mass unit (amu) is defined as a mass exactly equal to one-twelfth of the mass of one …atom.
(a) Hydrogen – 1 (b) carbon – 12 (c) Oxygen -12 (d) Chlorine – 35
Ans – b) carbon – 12
2) The mass of one mole of a substance in grams is called its..
(a) Atomic mass (b) Molecular Weight (c) Molecular mass (d) molar mass.
Ans – d) molar mass
3) … is the sum of atomic masses of the elements present in a molecule.
(a) Atomic mass (b) Molecular Weight (c) Molecular mass (d) molar mass.
Ans – c) Molecular mass
4) One mole contains exactly …elementary entities.
(a) 02214076 × 1021 (b) 02214076 × 1022 (c) 02214076 × 1023 (d) 02214076 × 1024
Ans – c) 6.02214076 × 1023

Five Marks questions with answers-

1. What is the difference between empirical and molecular formula? A compound contains 4.07
% hydrogen, 24.27 % carbon and 71.65 % chlorine. Its molar mass is 98.96 g. What are its
empirical and molecular formulas?
Ans. An empirical formula represents the simplest whole number ration of various atoms present in a
compound whereas the molecular formula shows the exact number of different types of atoms present
in a molecule of a compound

The empirical formula of the above compound is CH2Cl. empirical formula

mass is 12 + (1x2) + 35.5 = 49.5
n= molecular mass/ empirical formula mass =98.96/49.5 = 2 Hence molecular
formula is C2H4Cl2
2. . Dinitrogen and dihydrogen react with each other to produce ammonia according to the
following chemical equation:(i) N2 (g) + 3H2(g) —–> 2NH3 (g)
(ii) Will any of the two reactants remain unreacted?
(iii) If yes, which one and what would be its mass?
Answer:
 3.A welding fuel gas contains carbon and hydrogen only. Burning a small sample of it in oxygen
gives 3.38 g carbon dioxide, 0.690 g of water and no other products. A volume of 10.0 L
(measured at STP) of this welding gas is found to weigh 11.6 g. Calculate (i) empirical formula,
(ii) molar mass of the gas, and (iii) molecular formula.
We know that
44g of CO2 contains 12 g of carbon.
3.38 g of CO2 will contain carbon
18 g of water contains 2 g of hydrogen.
0.690 g of water will contain hydrogen =

Since carbon and hydrogen are the only constituents of the compound, the total mass of

the compound is:= 0.9217 g + 0.0767 g= 0.9984 g

Percent of C in the compound =

Percent of H in the compound =

Moles of carbon in the compound =

Moles of hydrogen in the compound =

Ratio of carbon to hydrogen in the compound = 7.69: 7.68= 1: 1 Hence, the
empirical formula of the gas is CH.
(ii) Given,
Weight of 10.0L of the gas (at S.T.P) = 11.6 g
Weight of 22.4 L of gas at STP = = 25.984 g=26g
Hence, the molar mass of the gas is 26 g.
Empirical formula mass of CH = 12 + 1 = 13 g
n= =2
Molecular formula of gas = (CH)n= C2H2

HOTS (Higher Order Thinking Skills

1. A compound made up of two elements A and B has A= 70 %, B = 30 %. Their relative number
of moles in the compound are 1.25 and 1.88. calculate
a. Atomic masses of the elements A and B
 b. Molecular formula of the compound , if its molecular mass is found to be 160
Ans: No. of moles = , Atomic mass =
Atomic mass of A = =

Atomic mass of B = =
Empirical formula
Element Relative Simplest molar ratio Simplest whole
no. of no.
moles molar ratio
A 1.25 1.25/1.25 = 1 2
B 1.88 1.88/1.25 = 1.5 3
Empirical formula = A2B3
Calculation of molecular formula-
Empirical formula mass = 2 x 56 + 3x 16 = 160
N= =
Molecular formula = A2B3
2. STRUCTUREOF ATOM
1. Discovery of Electron by cathode ray discharge tubes

In 1879, William Crooks studied the conduction of electricity through gases at low pressure. A cathode ray
tube is made of glass containing two thin pieces of metal, called electrodes, sealed in it. The electrical
discharge through the gases could be observed only at very low pressures and at very high voltages. When
sufficiently high voltage is applied across the electrodes, current starts flowing through a stream of
particles moving in the tube from the negative electrode (cathode) to the positive electrode (anode). These
were called cathode rays or cathode ray particles.

Properties of cathode rays:

(i) The cathode rays start from cathode and move towards the anode.
(ii) These rays themselves are not visible but they produce fluorescence on ZnS screen.
(iii) In the absence of electrical or magnetic field, these rays travel in straight lines
(iv) In the presence of electrical or magnetic field, the behavior of cathode rays are similar to that expected
from negatively charged particles, suggesting that the cathode rays consist of negatively charged particles,
called electrons.
(v) The characteristics of cathode rays(electrons) do not depend upon the material of electrodes and the
nature of the gas present in the cathode ray tube.
Charge to Mass Ratio of Electron
J.J. Thomson measured the ratio of electrical charge (e) to the mass of electron (me ) by using cathode ray
tube and applying electrical and magnetic field perpendicular to each other as well as to the path of
electrons .
e/me = 1.758820 x 1011 C kg-1
where me = Mass of the electron in kg
e = magnitude of charge on the electron in coulomb (C).

Discovery of proton anode ray

In 1886, Goldstein modified the discharge tube by using a perforated cathode. On reducing the pressure, he
observed a new type of luminous rays passing through the holes or perforations of the cathode and moving
in a direction opposite to the cathode rays. These rays were named as positive rays or anode rays or as
canal rays. Anode rays are not emitted from the anode but from a space between anode and cathode.
Properties of Anode Rays
(i) The value of positive charge on the particles constituting anode rays depends upon the nature of the gas
in the discharge tube.
(ii) The charge to mass ratio of the particles is found to depend on the gas from which these originate.
(iii) Some of the positively charged particles carry a multiple of the fundamental unit of electrical charge.
(iv)The behavior of these particles in the magnetic or electric field is opposite to that observed for electron
or cathode rays.
Proton: The smallest and lightest positive ion was obtained from hydrogen and was called proton. Mass of
proton = 1.676 x 10-27 kg
Charge on a proton = (+) 1.602 x 10-19 C
Neutron: It is a neutral particle. It was discovered by Chadwick (1932).
By the bombardment of thin sheets of beryllium with fast moving a-particles he observed • that highly
penetrating rays consist of neutral particles which were named neutrons.
 Thomson Model of Atom: An atom possesses a spherical shape (radius approximately 10–10 m) in which
the positive charge is uniformly distributed. The electrons are embedded into it in such a manner as to give
the most stable electrostatic arrangement

An important feature of this model is that the mass of the atom is assumed to be uniformly distributed over
the atom.

Drawback of Thomson Model of Atom

This model was able to explain the overall neutrality of the atom, it could not satisfactorily, explain the
results of scattering experiments carried out by Rutherford in 1911.
Rutherford’s Nuclear Model of Atom
Rutherford in 1911, performed some scattering experiments in which he bombarded thin foils of metals
like gold, silver, platinum or copper with a beam of fast moving a-particles. The thin gold foil had a
circular fluorescent zinc sulphide screen around it. Whenever a-particles struck the screen, a tiny flash of
light was produced at that point.

The important observations are:

(i) Most of the a-particles passed through the foil without undergoing any deflection,
(ii) A few a-particles underwent deflection through small angles.
(iii) Very few mere deflected back i.e., through an angle of nearly 180°.
Conclusions:
(i) Since most of the a-particles passed through the foil without undergoing any deflection, there must be
sufficient empty space within the atom.
(ii) A small fraction of a-particles was deflected by small angles. The positive charge has to be
concentrated in a very small volume that repelled and deflected a few positively charged a-particles. This
very small portion of the atom was called nucleus.
(iii) The volume of nucleus is very small as compared to total volume of atom..

Rutherford’s Nuclear Model of an Atom

(i) The positive charge and most of the mass of the atom was densely concentrated in an extremely small
region. This very small portion of the atom was called nucleus by Rutherford.
(ii) The nucleus is surrounded by electrons that move around the nucleus with a very high speed in circular
paths called orbits.
(iii) Electrons and nucleus are held together by electrostatic forces of attraction
Drawbacks of Rutherford Model
(i) Rutherford’s model cannot explain the stability of atom if the motion of electrons is described on the
basis of classical mechanics and electromagnetic theory.
(ii) Rutherford’s model does not give any idea about distribution of electrons around the nucleus and about
their energies.
Atomic Number: The number of protons present in the nucleus is equal to the atomic number (z). In
order to keep the electrical neutrality, the number of electrons in an atom is equal to the number of protons
(atomic number, z)
Atomic Number (z) = Number of protons in the nucleus of an atom.= Number of electrons in a neutral
atom
Mass Number :Number of protons and neutrons present in the nucleus are collectively known as nucleons.
The total number of nucleons is termed as mass number (A) of the atom.
Mass Number (A) = Number of protons (p) + Number of neutrons (n).
Isotopes :Atoms with identical atomic number but different atomic mass number are known as Isotopes.
Isotopes of Hydrogen: protium, deuterium and tritium.
Isobars :Isobars are the atoms with same mass number but different atomic number for Example

Developments Leading to the Bohr’s Model of Atom -Two developments played a major role in the
formulation of Bohr’s model of atom. These were:
(i) Dual character of the electromagnetic radiation which means that radiations possess both wave like and
particle like properties.
(ii) Experimental results regarding atomic spectra which can be explained only by assuming quantized
electronic energy levels in atoms.
Nature of Electromagnetic Radiation (Electromagnetic Wave Theory)
This theory was put forward by James Clark Maxwell in 1864. The main points of this theory are as
follows:
(i) The energy is emitted from any source (like the heated rod or the filament of a bulb through which
electric current is passed) continuously in the form of radiations and is called the radiant energy.
(ii) The radiations consist of electric and magnetic fields oscillating perpendicular to each other and both
perpendicular to the direction of propagation of the radiation.
(iii) The radiations possess wave character and travel with the velocity of light 3 x 108 m/sec.
(iv) These waves do not require any material medium for propagation. For example, rays from the sun
reach us through space which is a non-material medium.

Characteristics of a Wave –
(i) Wavelength: It is defined as the distance between any two consecutive crests or troughs. It is
represented by X and its S.I. unit is metre.
(ii) Frequency: Frequency of a wave is defined as the number of waves passing through a point in one
second. It is represented by v (nu) and is expressed in Hertz (Hz).
1 Hz = 1 cycle/sec. Velocity:
(iii) Velocity of a wave is defined as the linear distance travelled by the wave in one second.
It is represented by c and is expressed in cm/sec or m/sec.
(iv) Amplitude: Amplitude of a wave is the height of the crest or the depth of the through. It is represented
by V and is expressed in the units of length.
(v) Wave Number: It is defined as the number of waves present in 1 metre length. Evidently it will be

equal to the reciprocal of the wavelength. It is represented by bar v (read as nu bar).

Electromagnetic Spectrum: When electromagnetic radiations are arranged in order of their increasing
wavelengths or decreasing frequencies, the complete spectrum obtained is called electromagnetic
spectrum.
Limitations of Electromagnetic Wave Theory
Electromagnetic wave theory was successful in explaining properties of light such as interference,
 diffraction etc; but it could not explain the following:
(i) The phenomenon of black body radiation.
(ii) The photoelectric effect.
(iii) The variation of heat capacity of solids as a function of temperature.
(iv) The line spectra of atoms with reference to hydrogen.
Black Body Radiation
The ideal body, which emits and absorbs all frequencies is called a black body and the radiation
emitted by such a body is called black body radiation. The exact frequency distribution of the emitted
radiation from a black body depends only on its temperature.
At a given temperature, intensity of radiation emitted increases with decrease of wavelength, reaches a
maximum value at a given wavelength and then starts decreasing with further decrease of wavelength as
shown in Fig

Planck’s Quantum Theory

The main points of this theory was as follows:
i. Atoms and molecules could emit (or absorb) energy only in discrete quantities and not in a continuous
manner.
ii.The smallest quantity of energy that can be emitted or absorbed in the form of electromagnetic radiation
is called quantum.
The energy (E ) of a quantum of radiation is proportional to its frequency (ν ) and is expressed by equation
(2.6).
E = nhν , ‘h’ is known as Planck’s constant = 6.626×10–34 J s.
Photoelectric effect
It is the phenomenon of ejection of electrons by certain metals (like potassium, rubidium, caesium
etc.) when light of suitable frequency incident on them. The electrons ejected are called photoelectrons.
This phenomenon was first observed by H.Hertz.
The important characteristics of photoelectric effect are:
1. Only photons of light of certain minimum frequency called threshold frequency (v0) can cause the
photoelectric effect. The value of v0 is different for different metals.
2. The kinetic energy of the electrons which are emitted is directly proportional to the frequency of the
striking photons and is quite independent of their intensity.
3. The number of electrons that are ejected per second from the metal surface depends upon the intensity of
the striking photons or radiations and not upon their frequency.

Explanation of Photoelectric Effect

Einstein in (1905) was able to give an explanation of the different points of the photoelectric effect using
Planck’s quantum theory as under:
(i) Photoelectrons are ejected only when the incident light has a certain minimum frequency (threshold
frequency v0)
 (ii) If the frequency of the incident light (v) is more than the threshold frequency (v0), the excess energy
(hv – hv0) is imparted to the electron as kinetic energy.
(iii) On increasing the intensity of light, more electrons are ejected but the energies of the electrons are not
altered.
Following the law of conservation of energy principle, the kinetic energy of the ejected electron is given by
K.E = hν - hν0
hν = hν0 + 1/2mev2
Dual Behaviors of Electromagnetic Radiation
Light possesses both particle and wave-like properties, i.e., light has dual behaviour.
The particle nature of light could be explained the black body radiation and photoelectric effect. The wave
behavior of light could be explained by the phenomena of interference and diffraction.
Atomic spectrum
When a ray of white light is passed through a prism, we get a series of colored bands called
spectrum. This spectrum is called continuous spectrum, because here violet merges into blue, blue into
green and so on.
Emission and Absorption Spectra
Emission Spectra Emission Spectra is noticed when the radiations emitted from a source are passed
through a prism and then received on the photographic plate. Radiations can be emitted in a number of
ways such as:
(i) from sun or glowing electric bulb.
(ii) by passing electric discharge through a gas at low pressure.
(iii) by heating a substance to high temperature.
The emission spectra of atoms in the gas phase do not form a continuous spectrum.
Absorption Spectra -When white light is passed through the vapours of a substance and the transmitted
light is then allowed to strike a prism, dark lines appear in the otherwise continuous spectrum. The dark
lines indicate that the radiations corresponding to them were absorbed by the substance from the white
light. This spectrum is called absorption spectrum. Dark lines appear exactly at the same positions where
the lines in the emission spectra appear.
Each element has a unique line emission spectrum. So line emission spectra are also called finger
print of atoms.
Line Spectrum of Hydrogen
When electric discharge is passed through hydrogen gas enclosed in discharge tube under low pressure and
the emitted light is analysed by a spectroscope, the spectrum consists of a large number of lines which are
grouped into different series. The complete spectrum is known as hydrogen spectrum.

On the basis of experimental observations, Johannes Rydberg noted that all series of lines in the hydrogen
spectrum could be described by the following expression: where Z is the atomic number of the species.
Here RH = constant, called Rydberg constant for hydrogen and n1 , n2 are integers (n2 > n1)
For any particular series, the value of n1 is constant while that of n2 changes. For example,
For Lyman series, n1= 1, n2= 2, 3, 4, 5………..
For Balmer series, n1 = 2, n2 = 3, 4, 5, 6………..
For Paschen series, n1= 3, n2 = 4, 5, 6, 7………..
For Brackett series,n1 = 4, n2 = 5, 6, 7, 8………..
For Pfund series, n1 =5, n2 = 6, 7, 8, 9………..
Thus, by substituting the values of n1 and n2 in the above equation, wavelengths and wave number of
different spectral lines can be calculated. When n1 = 2, the expression given above is called Balmer’s
formula.
 Bohr’s Model of Atom Niels Bohr in 1913, proposed a new model of atom on the basis of Planck’s
Quantum Theory. The main points of this model are as follows:
(i) In an atom, the electrons revolve around the nucleus in certain definite circular paths called orbits.
(ii) Each orbit is associated with definite energy and therefore these are known as energy
levels or energy shells. These are numbered as 1, 2, 3, 4……….. or K, L, M, N………..
(iii) Only those energy orbits are permitted for the electron in which angular momentum of the electron is a
whole number multiple of h/2π
Angular momentum of electron (mvr) = (n = 1, 2, 3, 4 etc).
m = mass of the electron v = tangential velocity of the revolving electron.
r = radius of the orbit. h = Planck’s constant. n is an integer.
(iv) As long as electron is present in a particular orbit, it neither absorbs nor loses energy and its energy,
therefore, remains constant.
(v) When energy is supplied to an electron, it absorbs energy only in fixed amounts as quanta and jumps to
higher energy state away from the nucleus known as excited state. The excited state is unstable, the
electron may jump back to the lower energy state and in doing so, it emits the same amount of energy. (∆E
= E2 – E1).
vi. The radius of orbits can be given by the equation: rn= a0 n2 where a0 = 52.9 pm.
Thus the radius of the first stationary state is 52.9 pm (called the Bohr radius). As n increases, the value of r
will increase.
vii. It is also possible to calculate the velocities of electrons moving in these orbits. Qualitatively the
magnitude of velocity of electron increases with increase of positive charge on the nucleus and decreases
with increase of principal quantum number
Achievements of Bohr’s Theory
1. Bohr’s theory has explained the stability of an atom.
2. Bohr’s theory has helped in calculating the energy of electron in hydrogen atom and one electron
species.
Limitations of Bohr Atom Model
Bohr atom model could explain the stability and line spectra of hydrogen atom and hydrogen like ions (e.g.
He+,Li2+, Be3+ etc). But it has the following limitations:
1. It could not explain the fine spectrum of hydrogen atom.
2. It could not explain the spectrum of atoms other than hydrogen.
3. It was unable to explain the splitting of spectral lines in the presence of electric field (Stark effect) and
in magnetic field (Zeeman effect).
4. It could not explain the ability of atoms to form molecules by chemical bonds.
5. It did not consider the wave character of matter and Heisenberg’s uncertainty principle.
Dual Behaviour of Matter (de Broglie Equation)
de Broglie in 1924, proposed that matter, like radiation, should also exhibit dual behaviour i.e., both
particle like and wave like properties. This means that like photons, electrons also have momentum as well
as wavelength.

λ= =

Heisenberg’s Uncertainty Principle

It states that, “It is impossible to determine simultaneously, the exact position and exact momentum (or
velocity) of an electron”.
 Δx.Δp ≥ , Δx.mΔv ≥ Δx.Δv ≥

Significance of Uncertainty Principle

(i) It rules out existence of definite paths or trajectories of electrons and other similar particles.
(ii) The effect of Heisenberg’s uncertainty principle is significant only for microscopic objects and is
negligible for macroscopic objects.
Reasons for the Failure of Bohr Model
(i) The wave character of the electron is not considered in Bohr Model.
(ii) According to Bohr Model an orbit is a clearly defined path and this path can completely be defined only
if both the position and the velocity of the electron are known exactly at the same time. This is not possible
according to the Heisenberg’s uncertainty principle.
Quantum Mechanical Model of Atom
Quantum mechanics: 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.
Important Features of Quantum Mechanical Model of Atom:
(i) The energy of electrons in atom is quantized i.e., can only have certain values.
(ii) The existence of quantized electronic energy level is a direct result of the wave like properties of
electrons.
(iii) Both the exact position and exact velocity of an electron in an atom cannot be determined
simultaneously.
(iv) An atomic orbital has wave function φ. There are many orbitals in an atom. Electron occupy an atomic
orbital which has definite energy. An orbital cannot have more than two electrons. The orbitals are filled in
increasing order of energy. All the information about the electron in an atom is stored in orbital wave
function φ.
(v) The probability of finding electron at a point within an atom is proportional to square of orbital wave
function i.e., |φ2|at that point. It is known as probability density and is always positive.
From the value of φ2 at different points within atom, it is possible to predict the region around the nucleus
where electron most probably will be found.
Quantum Numbers
Atomic orbitals can be specified by giving their corresponding energies and angular momentums which are
quantized (i.e., they have specific values). The quantized values can be expressed in terms of quantum
number. These are used to get complete information about electron i.e., its location, energy, spin etc.
The principal quantum number gives us the following information:
The following information’s are obtained from n.
1. It gives the size the orbit.
2. It gives the energy of electron in an orbit.
3. It gives the shell in which the electron is found.
4. It also gives the average distance between the electron and the nucleus. As the value of n increases, the
distance between the electron and the nucleus also increases.
The possible values of n are 1, 2, 3, 4, 5 etc.
If n = 1 the electron is in K shell
n = 2 the electron is in L shell
n = 3 the electron is in M shell and so on.
5. The maximum number of electrons in the shell with principal quantum number n is equal to 2n2.
Azimuthal or Subsidiary or Orbital Angular Quantum Number (l)
The following information’s are obtained from Ɩ.
1. It gives the shape of the orbital.
2. It gives the sub shell or sub level in which the electron is located.
3. It also gives the orbital angular momentum of the electron.
4. the values of l = 0 to (n-1)
The number of sub shells in a principal shell is equal to the value of n. For example,
When n = 1, Ɩ= 0. i.e. K shell contains only one sub shell - s sub shell
when n = 2, Ɩ = 0 and1. i.e. L shell contains two sub shells - s and p sub shells
when n = 3, Ɩ = 0, 1 and 2. i.e. M shell contains three sub shells – s, p and d sub shells
 when n = 4, Ɩ = 0, 1, 2 and 3. i.e. N shell contains four sub shells – s, p,d and f sub shells
4. the number of electrons that can be accommodated in sub-energy level is equal to 2(2l+1).
If l = 0 for s orbital then= 2(2*1+1)=2 electrons
If l =1 for p orbital then= 2(2*2+1)=6 electrons
If l = 2 for d orbital then= 2(2*3+1)=10 electrons
if l = 3 for f orbital then= 2(2*3+1)=14 electrons

Magnetic Orbital Quantum Number (m or m1)

1. The magnetic orbital quantum number determines the number of preferred orientations of the electrons
present in a sub-shell.
2. The magnetic quantum number is denoted by letter m and for a given value of l, it can have all the values
ranging from – l to + l including zero.
Thus, for energy value of l, m has 2l + 1 values.
For example,
For l = 0 (s-sub-shell), m can have only one value i.e., m = 0.
This means that s-sub-shell has only one orientation in space. In other words, s-subshell has only one
orbital called s-orbital.
Spin Quantum Number (S or ms)
This quantum number helps to explain the magnetic properties of the substances. A spinning electron
behaves like a micro-magnet with a definite magnetic moment. If an orbital contains two electrons, the two
magnetic moments oppose and cancel each other.
• Shapes of s-orbitals s-orbital with only one orientation has a spherical shape with uniform electron
density along all the three axes.
The plots of probability density (ψ2) against distance from the nucleus (r) for 1s and 2s atomic orbitals are
as follows:

The probability of 1s electron is found to be maximum near the nucleus and decreases with the increase in
the distance from the nucleus. In 2s electron, the probability is also maximum near the nucleus and
decreases to zero probability. The spherical empty shell for 2s electron is called nodal surface or simply
node.

Shapes of p-orbitals
p-orbitals are present in the p-subshell for which l = 1 and m1 can have three possible orientations – 1, 0, +
1.
Thus, there are three orbitals in the p-subshell which are designated as px, py and pz orbitals depending
upon the axis along which they are directed. The general shape of a p-orbital is dumb-bell consisting of two
portions known as lobes. Moreover, there is a plane passing through the nucleus along which finding of the
electron density is almost nil. This is known as nodal plane as shown in the fig.
 From the
dumb-bell pictures, it is quite obvious that unlike s-orbital, a p-orbital is directional in nature and hence it
influences the shapes of the molecules in the formation of which it participates.
Number of radial nodes = n - Ɩ – 1Number of
angular nodes = Ɩ Total number of nodes = n-
1
• Shapes of d-orbitals
For d-orbitals, Ɩ = 2 and mƖ = -2, -1, 0, +1 and +2. i.e., there are five possible orientations for d orbitals. So
there are 5types of d-orbitals. They are dxy, dxz, dyz, dx2-y2 and dz2. . The shapes of the first four d-
orbitals are double dumb-bell and that of the fifth one, dz2, is dumb-bell having a circular collar in the XY-
plane. The five d-orbitals have equivalent energies. For d orbitals the number of radial nodes is 2 and the
total number of nodes is n-2. Boundary surface diagrams for d-orbitals are as follows.

f-orbitals:
For f-orbitals, Ɩ = 3 and mƖ = -3, -2,-1.0.+1,+2 and +3. i.e., there are seven possible orientations for f
orbitals.so there are 7 types of f-orbitals. They have diffused shapes.
Electronic Configuration of Atoms
The distribution of electrons into orbitals of an atom is called its electronic configuration. The electronic
configurationis explained based on Aufbau principle, Hund’s rule, Pauli’s exclusion principle and stability
concept.
1. Aufbau principle:
The principle states: In the ground state of the atoms, the orbitals are filled in order of their increasing
energies.
In other words, electrons first occupy the lowest energy orbital available to them and enter into higher
energy orbitals only after the lower energy orbitals are filled.
This rule has two sub rules:
a) The various orbitals are filled in the increasing order of their (n+l) value.
b) If two orbitals have the same (n+l) values, the orbital with the lower n value is filled first.The increasing
order of orbitals is as follows.
Pauli Exclusion Principle
According to this 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 spins.If 2 electrons
have same values for n, Ɩ and m, they should have different values for s. i.e. if s = +1/2. for the first
electron, it should be -1/2. for the second electron.
3. Hund’s rule of maximum multiplicity
It states that: pairing of electrons in the orbitals belonging to the same sub-shell (p, d or f) does not take
place until each orbital belonging to that sub-shell has got one electron each with parallelspin. For example
the electronic configuration of N is 1s2 2s2 2px1p y1p z1 and not 1s2 2s2 2p x2p y1.

Stability of Completely Filled and Half Filled Subshells

For atoms having half filled or completely filled electronic configurations have extra stability compared to
other atoms. This is due to their symmetrical distribution of electrons and greater exchange energy. For
example, the electronic configuration of Cr is [Ar] 3d54s1 and not 3d44s2. This is because d5 represents a
half filled configuration and has extra stability. Similarly for Cu the electronic configuration is [Ar] 3d104s1
and not 3d94s2.

Cr(24) = [Ar] 3d5 4s1 not [Ar] 3d4 4s2

Similarly
Cu(29) = [Ar] 3d10 4s1 not [Ar] 3d94s2

MCQ

1. Which of the following options does not represent ground state electronic configuration of an atom?
(a) 1s2 2s2 2p6 3s2 3p6 3d8 4s2 (b) 1s2 2s2 2p6 3s2 3p6 3d9 4s2
(c) 1s2 2s2 2p6 3s2 3p6 3d10 4s1 (d) 1s2 2s2 2p6 3s2 3p6 3d5 4s1
Ans .(b) 1s2 2s2 2p6 3s2 3p6 3d9 4s2

2. Number of angular nodes for 4d orbital is .

(a) 4 (b) 3 (c) 2 (d) 1
Ans: (c) 2 Angular nodes = ‘l’ = 2 for d-orit.
3. The number of radial nodes for 3p orbital is .
(a) 3 (b) 4 (c) 2 (d) 1
Ans: d) 1. Number of radial nods = n – l – 1 = 3 – 1 – 1 = 1
4. g subshell is characterised by:
(a)n = 5 (b) m = 3 (c) l = 4 (d)l = 5
Ans: (c)
5. Which expression represents de Brogile relationship?
(a) h/mu = p (b) λ = h/mv (c)λ = h/mp (d)λ = u/p
Ans: (b)
6. Which of the following is responsible to rule out the existence of definite paths or trajectories of
electrons? (a) Pauli’s exclusion principle. (b) Heisenberg’s uncertainty principle. (c) Hund’s rule of
maximum multiplicity. (d) Aufbau principle
Ans: (b) Heisenberg’s uncertainty principle.
7. For which of the following sets of quantum numbers, an electron will have the highest energy?
(a) 3, 2, +1, +1/2 (b) 4, 2,-1,+1/2 (c) 4,1,0,-1/2 (d ) 5,0,0,+1/2
Ans: (b)
8. Which of the following atoms or atom/ion have identical ground state configuration ?
(a) Li+ and He+ (b) Cl- and Ar (c)Na and K 9d)F+ and Ne
Ans: (b)
 9. The number of spherical nodes for 4d orbital is
(a) zero (b) one (c)two (d)three
Ans: (b)
10. The configuration 1s2 2s22p53s1 shows:
(a)ground state of fluorine (b)exited state of fluorine
(c)exited state of neon (d)exite state of O2- ion
Ans: (c)
11. Which of the following orbitals has dumb-bell shape?
(a)s (b)p (c)d (d) f
Ans: (b)
12. The total number of orbitals in a shell having principal quantu number n is
(a) 2n (b)n2 (c)2n2 (d)n+1
Ans: (b)
13..What is the wavelength of light.Given energy =3.03x10-19 J, h=6.6x10-34 JS,c=3x108m/s
(a) 6.54 nm (b)654nm (c)0.654nm (d)65.4nm
Ans: (b)
14.Azimuthal quantum number defines:
(a) e/m ratio of electron (b)spin of electron
(c) angular momentum of electron (d)magnetic momentum of electron
Ans: (c)
15..The correct order of increasing energy energy of atomic orbital is:
(a)5p<4f<6s<5d (b)5p<6s<4f<5d
(c)4f<5p<5d<6s (d)5p<5d<4f<6s
Ans: (b)
16. Iso-electronic species are:
(a)F- ,O-2 (b)F-,O (c)F-,O+ (d)F-,O+2
Ans: (a)
17. Quantum numbers n=2,l=1 represent:
(a)1s orbital (b)2s orbital (c) 2p orbital (d)3d orbital
Ans: ©
18. The quantum number m of a free gaseous atom is associated with:
(a) The effective volume of the orbital
(b) The shape of the orbital
(c) The spatial orientation of the orbital
(d) The energy of the orbital in the absence of the magnetic field.
Ans: (c)
19. The energy of second Bohr orbit of hydrogen atom is -328 KJ/mol. Hence the energy of forth orbit
would be:
(a)-41 KJ/mol (b)-82 KJ/mol (c)-164 K/mol (d)-1312 KJ/mol
Ans: (b)
20. The orientation of an atomic orbital is governed by:
(a) Principal quantum number b) Azimuthal quantum number
C) Spin quantum number d) Magnetic quantum number
Ans : (d)
Assertion –Reason type question
The questions given below consist of assertion (A)and reason (R).Use the following key to select the
correct answer.
(a) If both assertion and reason are correct and reason is correct explanation for assertion.
(b) If both assertion and reason are correct and reason is not correct explanation for assertion.
(c) If assertion is correct and reason is in correct
(d) If both assertion and reason are incorrect.

1. A: Photoelectric effect is most readily shown by cesium.

R: Photon have easiest access to the surface of cesium metal. Answer: (c)
2. A: An orbital cannot have more than 2 electrons and their spin must be opposite.
R: No two electrons in an atom can have same set of all four quantum numbers. Answer:(a)
3. A: Both position and momentum of an electron can not be determined simultaneously with maximum
accuracy.
R: This is because of microscopic nature of electron. Answer: (a)
4 .A: The energy of an electron is mainly determined by principal quantum number.
R: The principal quantum number is the measure of the most probable distance of finding the electron
around the nucleus. Answer: (a)
5. A: Fe3+ ion is more stable than Fe2+ ion in ground state.
R: Fe3+ ion has more number of unpaired electrons than Fe2+ ion. Answer:(b)
6. A: An orbital cannot have more than two electrons.
R: The two electrons in an orbital create opposite magnetic field Answer: (c)
7. A: The 19th electron in potassium atom enters 4s-orbital and not 3d orbital’
R: The energies of the orbitals can be compared with the help of(n+l) rules. Answer:(a)

Short answer questions - (2 marks)

1. We don’t see a car moving as a wave on the road why?
According to de Broglie’s relation, λ=h/mv i.e. λα1/mλ=h/mv i.e. λα1m the mass of the car is very large
and its wavelength (λ) or wave character is negligible. Therefore, we do not see a car moving like a wave.

2.What is the physical significance of Ψ2?

Ans: Ψ2 represents the probability of finding an electron. It is the probability of finding a particle specified
by a particular wave function.

3.Which orbital is non directional?

Ans: S- orbital is spherically symmetrical i.e. it is non-directional. It has a spherical shape, like a hollow
ball.

4.What is quantisation of energy?

Ans: Quantization of energy means the energy is distributed and transmitted in the form of packets. These
packets are called photons.

5.Why spectral lines are considered as finger print?

Ans: identification of the elements can be done from these lines. Just like fingerprints, the spectral lines of
no two elements resemble each other.

6. The two electrons in the 1s orbital of He have anti-parallel spin. Why do not they have parallel spin ?
Ans Two electrons present in same orbital cannot have parallel spin since they tend to repel each other. The
inter-electronic repulsion will be high leading to increase in energy of the atom and decrease instability.
7.Why are 2d and 3f orbitals not possible?
Ans For n=2 ,the permitted value of l are 0 and 1.this means that 2nd shell has only s and p orbitals and not
d .Similarly for n=3 ,the permissible values are 0,1and2 .thus only s,p and d orbitals are permitted not f.

8. Heinsberg uncertainity principle has no significance in our every day life. Explain.
Ans; In our daily life we can see only the moving macro and semi-micro-obejcts. The mass of the striking
photons of light is too small to cause any shift in their position by the time the reflected photons form the
image of the object. For such particles, there is no problem in measuring the exact momentum
simultaneously. Thus, the principle has no relevance for such objects.

9.Out of 3d and 4s orbitals which is filled first?

Ans: 4s orbital is filled first because it has lower energy. The energies of the orbitals can be compared by
their n+l values. For 4s orbital n+l(4+0) value is 4 while for 3d orbital, n+l (3+2) value is 5,Therefore 4s
orbital is filled before3d orbital.

10. A certain element A undergoes photoelectric emission when bombarded by one photon of indigo light.
When the material containing the same element was bombarded by two photons of red light with a total of
same energy as that of indigo photon , no electron was emitted. Explain.
Ans: It may be noted that an electron can absorb only one photon at a time and not two photons. Since the
energy of the incident red light is less than the threshold energy, photoelectric effect will not take place or
no electron will be emitted.

11. How many electrons can be filled in all the orbitals with n+l=5?
Ans: (n+l)=5 has 5s,4p and 3d orbitals with two, six and ten electrons respectively. Therefore, the total
number of electrons=18.
Short answer questions (3marks)
1Which of the followings are iso-electronic species, i.e. those having the same number of electrons?
Na+, K+, Mg2+, Ca2+, S2–, Ar.
ANS: Na+ (11 – 1 = 10), Mg2+ (12 – 2 = 10) have same number of electrons.
K+ (19 – 1 = 18), Ca2+ (20 – 2 = 18),
S2– (16 + 2 = 18), Ar (18) are iso-electronic, i.e. they have same number of electrons.
2. What is the uncertainty in locating its position? [Given, me = 9.11 × 10–31 kg] An electron speed of 40 m
s–1 accurate upto 99.9 percent

3. An atom of an element contains 29 electrons and 35 neutrons. Deduce

(i) number of protons.
(ii) electronic configuration of the element.
(iii) number of paired electrons.
(iv) number of unpaired electrons.
ANS: (i) Electrons = 29, Neutrons = 35, Protons = Electrons = 29
(ii) Electronic configuration is

(iii) There are 28 paired electrons

(iv) There is one unpaired electron.
4. Yellow light emitted from a sodium lamp has a wavelength (2) of 580 nm. Calculate the frequency (v)
and wave number (v) of yellow light.
Answer:
 5. What is the number of photons of light with wavelength 4000 pm which provide 1 Joule of energy ?
Answer:
Energy of photon (E) =

h = 6.626 × 10-34 Js, c = 3 × 108 m s-1, λ = 4000 pm = 4000 × 10-12 = 4 × 10-9 m

6. Calculate the wave number for the longest wavelength transition in the Balmer series of atomic hydrogen.
Answer:

7. Show that the circumference of the Bohr orbit for the hydrogen atom is an integral multiple of the de
Broglie wavelength associated with the electron revolving around the orbit.
Answer:

Thus, the circumference (2πr) of the Bohr orbit for hydrogen atom is an integral multiple of the de Broglie
wavelength.

8. Calculate the energy required for the process :

He+fe) → He2+(g) + e–
The ionisation energy’ for the H atom in the ground state is 2.18 × 10-18 J atom-1
Answer:
For H atom (Z = 1), En =2.18 × 10-18 × (l)2 J atom-1 (given)
For He+ ion (Z = 2), En =2.18 × 10-18 × (2)2 = 8.72 × 10-18 J atom-1 (one electron species)

9. Red light has wavelength 750 nm, whereas violet light has wavelength 400 nm. Calculate their frequency

and energy (c = 3 × 108 m s–1, h = 6.63 × 10 –34 J s). Th

10.The threshold frequency v0 for a metal is 7.0 × 1014 s–1. Calculate the kinetic energy of an electron

emitted when radiation of v = 1.0 × 1015 s–1 hits the metal

11. The mass of an electron is 9.1 × 10-31 kg. If its kinetic energy is 3.0 × 10-25 J, calculate its wavelength.
Answer:

12. Calculate the wavelength of an electron moving with a velocity of 2.05 × 107 m s-1
Answer:

13. Table-tennis ball has a mass 10 g and a speed of 90 m/s. If speed can be measured within an accuracy of
 4%, what will be the uncertainty in speed and position?
Case study based question
The presence of positive charge on the nucleus is due to the protons in the nucleus. As established earlier,
the charge on the proton is equal but opposite to that of electron .Atomic number (Z) = number of protons
in the nucleus of an atom = number of electrons in a nuetral atom. protons and neutrons present in the
nucleus are collectively known as nucleons.The total number of nucleons is termed as mass number (A) of
the atom.
mass number (A) = number of protons (Z) + number of neutrons (n).
Isobars are the atoms with same mass number but different atomic number for example, 614C and 714N. On
the other hand, atoms with identical atomic number but different atomic mass number are known as
Isotopes. For example, considering of hydrogen atom again, 99.985%of hydrogen atoms contain only one
proton. This isotope is called protium (11H). Rest of the percentage of hydrogen atom contains two other
isotopes, the one containing 1 proton and 1neutron is called deuterium (21D, 0.015%) and the other one
possessing 1 proton and 2neutrons is called tritium (13T ).The studies of interactions of radiations with
matter have provided immense information regarding the structure of atoms and molecules. Neils Bohr
utilized these results to improve upon the model proposed by Rutherford. Two developments played a
major role in the formulation of Bohr’s model of atom.
1. The pair of ions having same electronic configuration is .
(a) Cr3+, Fe3+ (b) Fe3+, Mn2+ (c) Fe3+, Co3+ (d) Sc3+,Cr3+
Ans: (b) Fe3+, Mn2+

2.They have same mass number, different atomic number. These are isobars.
.In which of the following pairs, the ions are isoelectronic?
(a) Na+, Mg2+ (b) Al3+, O– (c) Na+, O2– (d) N3–, Cl–
Ans: (a) and (c).
3.Two atoms are said to be isobars if.
(a) they have same atomic number but different mass number.
(b) they have same number of electrons but different number of neutrons.
(c)they have same number of neutrons but different number of electrons.
(d)sum of the number of protons and neutrons is same but the number of protons is different.
Ans (d) sum of number of protons and neutrons is same but the number of protons is different.
Long answer question (5 marks)
1. (i) List two main differences between orbit and orbital.
(ii) If an electron is moving with a velocity 600 m/s which is accurate upto 0.005%, then calculate the
uncertainty in its position.
(h = 6.626 × 10–34 J s and mass of electron = 9.11 × 10–31 kg)
ANS: (i) Differences between orbit and orbitals:
Orbit Orbital
Orbit is a well defined 2-D circular path Orbital is a3-D space around the atom where
around the nucleus in which the electron the probability of finding electron is
revolve. maximum.
It is not in accordance of wave character It is in accordance with wave character.
Orbits do not have direction Except s orbital ,all orbitals are direction.

(ii) Uncertainity in speed,

According to Heisenberg uncertainity principal
Δx.mΔv ≥

Δx = = = 1.93x10-3m

2. The electronic energy in hydrogen atom is given by En (-2.18 × 10-18 s) / n2J. Calculate the energy
required to remove an electron completely from the n = 2 orbit. What is the longest wavelength of light in
cm that can be used to cause this transition?
Answer:

3. What is the energy in joules required to shift the electron of the hydrogen atom from the first Bohr orbit
to the fifth Bohr orbit and what is the wavelength of light emitted when the electron returns to the ground
state ? The ground state electronic energy is – 2.18 × 11-11 ergs.
Answer:

4. How much energy is required to ionise a hydrogen atom if an electron occupies n = 5 orbit ? Compare
your answe r with the ionisation energy of H atom (energy required to remove the electron from n = 1
orbit)
Answer:
5(i) Write outer electronic configuration of Cr atom. Why are half filled orbitals more stable?
Ans:
(ii)A 25 watt bulb emits monochromatic yellow light of wavelength 0.57 μm. Calculate the rate of
emission of quanta per second.
Answer:

HOTS
1.The work function for cesium atom is 1.9 eV. Calculate (a) the threshold wavelength and (b) the
threshold frequency of the radiation. If the cesium element is irradiated with a wavelength 500 nm,
calculate the kinetic energy and the velocity of the ejected photoelectron
Answer:
 3.CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES OF ELEMENTS

Earlier classifications
1) Dobereiner’s classification:
Johann Dobereiner classified elements into small groups each containing three elements. These small
groups were called triads.
7 23
E.g. for triads are: i) Li Na 39K
40
ii) Ca 88Sr 137Ba
In triads, the atomic mass of the middle element is approximately the average of the other two
elements. This is known as Law of Triads. This classification was applicable to very few elements and so it
was rejected.
2) Newlands classification:
Newland arranged elements in the increasing order of their atomic masses. The properties of every
eighth element are similar to that of the first element. The relationship is just like the resemblance of first
and eighth musical notes. He named this as law of octaves.
It was rejected since the law of octaves was applicable to elements upto calcium.

Mandeleev’s Periodic Law:-

The periodic law states that “The properties of elements are the periodic functions of their atomic
weights.” That is, when elements are arranged in the increasing order of their atomic weights, their
properties repeat after a regular interval.
Merits of Mendeleev’s periodic table
1It was the first comprehensive classification of elements.
2. He corrected the wrong atomic weights of some elements and placed them in correct position in the
periodic table.
3. He left vacant places for undiscovered elements and predicted some of their properties. 4)Elements with
similar properties are placed in the same group.
Demerits of Mendeleev’s periodic table
1.Elements with dissimilar properties are found in same group.
2.He could not give an exact position for hydrogen.
3.He could not give exact position for Lanthanoids and Actinoids and also for isotopes.
4.Mendeleev’s periodic table did not strictly obey the increasing order of atomic weights.
Modern Periodic table (Henry Moseley)
Modern Periodic lawstates that“the physical and chemical properties of elements are the periodic
functions of their atomic numbers”.
In this periodic table, the elements are arranged in the increasing order of their atomic number. It
contains 7 horizontal rows called periods and 18 vertical columns called groups. Elements having similar
outer electronic configurations are arranged in same group or family and have similar properties.
The blocks in the Modern periodic table
The Modern periodic table is divided into 4 blocks based on the subshell in which the last electron
enters. They are s block, p block, d block and f block.
1. The s block elements
These are elements in which the last electron enters in the outer most s sub shell. They include elements
of the groups 1 and 2. Their general outer electronic configuration is ns1 or ns2.
They are all reactive metals with low ionization enthalpies.
They lose their outer most electrons readily to form +1 and +2 ions.
Their metallic character and reactivity increases down the group.
They mainly form ionic compounds (except Li and Be).
2. The p block elements
These are elements in which the last electron enters in the outer most p sub shell. They include elements
 of the groups 13 to 18. They are also called Representative elements.
Their general outer electronic configuration is ns2 np1 to 6. The 18th group elements are called Noble
gases.
The d block elements
These are elements in which the last electron enters in the penultimate d sub shell. They include
elements of the groups 3 to 12. They are also called Transition elements, since they show a transition
(change) from the most electropositive s block elements to the least electropositive p block elements. Their
general outer electronic configuration is (n-1)d1 to 10 ns0 to 2.
They are all metals, form-coloured compounds or ions,
They show variable oxidation states and valencies,
They show paramagnetism and catalytic properties.
The f block elements
These are elements in which the last electron enters in the anti-penultimate f sub shell. They include
lanthanides of 6th period and actinides of 7th period. They are also called Inner transition elements. Their
general outer electronic configuration is (n-2)f1 to 14(n-1)d0 to 1 ns2. They are all metals.
Periodic properties of Elements
The properties which repeat after a regular interval are called periodic properties. Some of the
important periodic properties of elements are atomic and ionic radii, ionization enthalpy, electron gain
enthalpy, electro positivity, electronegativity etc.
1. Atomic Radius
It is defined as the distance from the centre of the nucleus to the outermost shell having electrons. Atomic
radius of individual atoms cannot be determined. So it is expressed in any of the following methods:
Covalent radius: It is half of the inter nuclear distance between two covalently bonded (single
bonded)atoms. It is used to express the atomic radius of non-metal atoms. For e.g. the bond distance of Cl2
molecule is 198 pm. So the covalent radius is 99 pm.

Metallic radius: It is the half of the inter nuclear distance between two metallic ions in a metal
crystal.
van der Waal’s radius: It is defined as the half of the inter nuclear distance between two non
bonded atoms of separate molecules in the solid state.

Atomic radius is commonly expressed in picometre (pm) or angstrom (A0).it is measured by x-ray
diffraction method or by spectroscopic methods.
Variation of atomic radius along a group and period
The atomic size decreases from left to right in a period. This is because in a period, the electrons are
added to the same valence shell. Thus the number of shells remains same, but the effective nuclear charge
increases. So the atomic radius decreases.
Down a group, the atomic radius increases from top to bottom. This is because of the increase in no.
of shells and shielding effect.

Atomic radius of noble gases is larger than that of halogens. This is because noble gases are
monoatomic . So van der Waal’s radius is used to express the atomic radius which is greater than covalent
radius or metallic radius.
 2. Ionic radius
It is defined as the half of the inter nuclear distance between cations and anions of an ionic crystal. The
variation of ionic radius is same as that of atomic radius.
Generally a cation is smaller than its parent atom (e.g. Na+is smaller than Na atom). This is because a
cation has fewer electrons, but its nuclear charge remains the same as that of the parent atom.
An anion is larger than its parent atom (e.g. Cl-is larger than Cl atom). This is because the addition of
one or more electrons would result in an increased electronic repulsion and a decrease in effective nuclear
charge.
Isoelectronic species:
Atoms and ions having the same number of electrons are called isoelectronic species. E.g. O2-, F-,
Ne, Na , Mg2+ etc. (All these contain 10 electrons)
+

Among isoelectronic species, the cation with greater positive charge will have the smaller radius.
This is because of the greater attraction of electrons to the nucleus. The anion with greater negative charge
will have the larger radius. Here the repulsion between electrons is greater than the attraction of the nucleus.
So the ion will expand in size.
3. Ionisation enthalpy (∆iH)
It is defined as the energy required to remove an electron from the outer most shell of an isolated
gaseous atom in its ground state. It may be represented as: X(g)+ ∆iH → X+(g)+ e–
Its unit is kJ/mol or J/mol.
The energy required to remove the first electron from the outer most shell of a neutral atom is called
first ionisation enthalpy (∆iH1)
X(g)+ ∆iH1→ X+(g)+ e–
Second ionization enthalpy (∆iH2) is the amount of energy required to remove an electron from a
unipositive ion.X+(g) + ∆iH2 → X2+(g) + e–
The second ionisation enthalpy is always higher than first ionization enthalpy. This is because it is
more difficult to remove an electron from a positive charged ion than from a neutral atom.
Similarly third ionisation enthalpy is higher than second ionisation enthalpy and so on. i.e. ∆iH1< ∆iH2<
∆iH3…………
As the ease of removal of electron increases, the ionisation enthalpy decreases.
Factors affecting ionisation enthalpy
The important factors which affect ionisation enthalpy are:
Atomic size: Greater the atomic size (atomic radius), smaller will be the ionisation enthalpy.
Nuclear charge: The value of ionisation enthalpy increases with nuclear charge.
Shielding effect: As the shielding effect increases, the electrons can easily be removed and so
theionisation enthalpy decreases.
Presence of half filled or completely filled orbitals increases ionisation enthalpy.
Variation of ∆iH along a period and a group
Along a period, ionisation enthalpy increases from left to right. This is because of the decrease in
atomicradius and increase in nuclear charge. Thus alkali metals have the least ∆iH and noble gases have
the most.
Down a group, ∆iH decreases due to increase in atomic radius and shielding effect. Thus among
alkali metals, lithium has the least ∆iH and francium has the most.

In the second period of modern periodic table, the first ionisation enthalpy of Boron is slightly less
thanthat of Beryllium. This is because of the completely filled orbitals in Be (1s22s2).
 Similarly the first ionisation enthalpy of N is greater than that of Oxygen. This is because N has half
filled electronic configuration (1s22s22p3), which is more stable and so more energy is required to remove
an electron.

4. Electron gain enthalpy (∆egH)

It is the heat change (enthalpy change) when an electron is added to the outer most shell of an
isolated gaseous atom. It can be represented as X(g)+ e–→ X-(g)
For most of the elements, energy is released when electron is added to their atoms. So ∆egH is
negative. Noble gases have large positive electron gain enthalpy because of their completely filled (stable)
electronic configuration.
Electron gain enthalpy also depends on atomic size, nuclear charge, shielding effect etc. As the
atomic size increases ∆egH decreases.
1. When nuclear charge increases, electron gain enthalpy increases and become more negative.
2.Shielding effect decreases ∆egH.
3.Presence of half filled or completely filled orbitals makes ∆egH less negative.
Periodic variation of ∆egH
1. From left to right across a period, ∆egH become more negative. This is because of decrease in
atomic radius and increase in nuclear charge. So the ease of addition of electron increases and hence the
∆egH.
2. Down a group, ∆egH becomes less negative. This is due to increase in atomic radius and shielding
effect.
3. Electron gain enthalpy of fluorine is less negative than chlorine. This is because, when an electron
is added to F,it enters into the smaller 2nd shell. Due to the smaller size, the electron suffers more repulsion
from the other electrons. But for Cl, the incoming electron goes to the larger 3rd shell. So the electronic
repulsion is low and hence Cl adds electron more easily than F. Due to the same reason ∆egH of Oxygen is
less negative than S.
4. Thus in modern periodic table, alkali metals have the least –ve ∆egH and halogens have the most –
ve ∆egH. Among halogens, the negative ∆egH decreases as follows.
Cl> F > Br > I
The negative electron gain enthalpy is also called electron affinity.

5. Electronegativity
Electronegativity of an atom in a compound is the ability of the atom to attract shared pair of
electron of electrons.
Electronegativity depends on atomic size and nuclear charge. As the atomic radius increases,
electronegativity decreases. Greater the nuclear charge, greater will be the electronegativity.
Periodicity:
(i) In period- The electro-negativity increases from left to right in a period.
(ii) In group- The electro-negativity decreases from top to bottom in a group.

6. Electropositivity
It is the tendency of an atom to lose the most loosely bound electron (valence electron). It is directly
related to the metallic character of elements. It depends on atomic size and nuclear charge. As the atomic
radius increases, electropositivity increases.
Along a period, electro positivity decreases from left to right. But down a group, it increases. So
francium is the most electropositive element and fluorine is the least electropositive element.
7. Valency
It is the combining capacity of an element. Or, it is the number of electrons lost or gained by an atom
during a chemical reaction.
Along a period, valency first increases upto the middle and then decreases (for s and p block elements
only). In a group, valency remains constant. Transition elements can show variable valency.
REACTIVITY OF METALS:
Periodicity:
(i) In period- The tendency of an element to lose electrons decreases in a period. So the reactivity of metals
decreases from left to right in a period.
(ii) In group- The tendency of an element to lose electrons increases in a period. So the reactivity of metals
increases from top to bottom in a group.

REACTIVITY OF NON- METALS:

(i) In period- The tendency of an element to gain electrons increases in a period. So the reactivity of non-
metals increases from left to right in a period.
(ii) In group- The tendency of an element to gain electrons decreases in a group. So the reactivity of non-
metals increases from top to bottom in a group.

1. The solubility of alkali metal carbonates and bicarbonates in water increases down the group (From
Lithium to Caesium).
2. The solubility of alkaline earth metal hydroxide and sulphates in water increases down the group (From
Beryllium to Barium).
3. 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

The periodic trends of elements in the periodic table

 MULTIPLE CHOICE QUESTIONS (MCQ)

1. The screening effect of d - electrons is -

(A) equal to the p - electrons (B) much more than p - electron
(C) same as f – electrons (D) less than p – electrons ANSWER- D

2. The increasing order of effective nuclear charge in Na, Al, Mg and Si atoms
(A) Na < Mg < Si <Al (B) Na < Mg <Al < Si
(C) Mg < Na <Al< Si (D) Na = Mg =Al = Si ANSWER- B

3.The Vander Waal’s radii of O, N, Cl, F and Ne increase in the order

(A) F, O, N, Ne, Cl (B) N, O, F, Ne, Cl
(C) Ne, F, O, N, Cl (D) F, Cl, O, N, Ne ANSWER- C

4. Whenever a list of radii is given, we find that the size of the noble gases is larger than the size of their
adjacent halogens. The reason is
(A) Noble gases have a complete octet
(B) They have a higher inter electronic repulsion
(C) In halogens it is covalent radii and in noble gases it is Vander walls radii (D)Noble gases cannot be
liquefied ANSWER- B

5. Which of the following has the largest size

(A) N–3 (B) O–2 (C) K+1 (D) Ca+2 ANSWER- A

6. Which one of the following is correct order of the size of iodine species?
(A) I > I– > I+ (B) I > I+ > I– (C) I+ > I– > I (D) I– > I > I+ ANSWER- D

7. Which of the following should be the order of increasing values of second ionisation potential of C6, N7,
O8 and F9.
(A) C > N > F > O (B) C < F < N < O (C) C < F < N < O (D) C < N < F< O ANSWER- D

8. One mole of magnesium in the vapour state absorbed 1200 kJ of energy. If the first and second ionization
enthalpies of magnesium are 750 and 1450 kJ mole–1 respectively, the final composition of the mixture is
(A) 69% Mg+, 31% Mg2+ (B) 59% Mg+, 41% Mg2+
(C) 49% Mg+, 51% Mg2+ (D) 29% Mg+, 71% Mg2+ ANSWER- A

9.The incorrect statement in the following is

(A) The third ionisation potential of Mg is greater than the third ionisation potential of Al
(B) The first ionisation potential of Na is less than first I.P of Mg
(C) The first I.P. of Al is less than the first I.P. of Mg
(D) The second I.P. of Mg is greater than the second I.P. of Na ANSWER- D

10. O(g) + 2e– O–2(g) –E = + 744.7

The reason for the positive value of E is
(A) endothermic reaction (B) exothermic reaction
(C) both 1 and 2 (D) All of the above are wrong ANSWER- A

11. The increasing order of electron affinity values of O, S and Se is

(A) O < S < Se (B) S < O < Se (C) O < Se < S (D) Se < O > S ANSWER- C

12. The least electron affinity is found in

(A) Kr (B) O (C) N (D) B ANSWER- C
 13. Of the following element of which electronic configuration will have the highest electron affinity
(A) 1s2 2s2 2p3 (B) 1s2 2s2 2p5 (C) 1s2 2s2 2p6 3s2 3p5 (D) 1s2 2s2 2p6 3s2 3p3 ANSWER- C

14. Which oxide of N is isoelectronic with CO2 -

(A) NO2 (B) NO (C) N2O (D) N2O3 ANSWER- A

15. The correct order of ionic radius is -

(A) Ce > Sm > Tb > Lu (B) Lu > Tb > Sm > Ce
(C) Tb > Lu > Sm > Ce (D) Sm > Tb > Lu > Ce ANSWER- A

16. According to the Modern Periodic Law of elements, the Variation in properties of elements is related to
them?
(A)Nuclear masses (B)Atomic numbers
(C)Nuclear neutron-proton number ratio (D)Atomic masses ANSWER- B

17. Atomic radius decreases in a period, but after halogens, the atomic radius suddenly increases. Thus,
inert gases have almost highest radius in a period. The explanation for such an increase is-
(A) Inert gases have most stable configuration.
(B) Inert gases do not take part in bonding.
(C) Vander Wall’s radius is reported in case of inert gases.
(D) None of these. ANSWER- C
18. Which one of the following groups represent a collection of isoelectronic species?
(At. no. Cs = 55, Br = 35)
(A) N 3–, F–, Na+ (B) Be, Al3+, Cl– (C) Ca2+, Cs+, Br ( D) Na+, Ca2+, Mg2+ ANSWER- A

19. Consider the following statements:

I. The radius of an anion is larger than that of parent atom
II. The I.E. increases from left to right in a period generally
III. The electronegativity of an element is the tendency of an isolated atom to attract an electron
The correct statements are -
(A)I alone (B) II alone (C) I and II (D) II and III ANSWER- C

20. For the same value of n, the penetration power of orbital follows the order
(a) s = p = d = f (b) p > s > d > f (c) f < d < p < s (d) s < p < d < f ANSWER- C

REASONING AND ASSERTION TYPE QUESTIONS

The following questions consist of two statements, one labelled as Assertion A and the other labelled as
Reason R. Examine both the statements and mark the correct choice according to the instructions given
below:
(a) if both A and R are correct and R is the correct reason of A
(b) if both A and R are correct but R is not the correct reason of A
(c) if A is correct and R is wrong
(d) if A is wrong and R is correct.
1. Assertion A: Noble gases have highest ionization energies in their respective periods.
Reason R.: Noble gases have stable electronic configurations. ANSWER: (a)
2.Assertion A: Nitrogen has higher I.E. than that of oxygen.
Reason R: Nitrogen atom has smaller atomic size than that of oxygen. ANSWER: (c)
3.Assertion A: Chlorine has higher greater negative electron gain enthalpy than that of fluorine.
Reason R: Fluorine is stronger oxidizing agent than chlorine. ANSWER: (b)
4.Assertion A: Helium has the highest value of ionization enthalpy among all the elements.
Reason R: Helium has the highest value of electron affinity among all the elements. ANSWER: (c)
5.Assertion A: Sixth period is the longest period of the periodic table.
Reason R: Sixth period involves the filling of all the orbitals of sixth energy level.
ANSWER: (c)
6. Assertion A: F atom has a less negative electron affinity than Cl atom.
Reason R: Additional electrons are repelled more effectively by 3p electron in Cl atom than by 2p electrons
in F atom. ANSWER: (c)
7. Assertion A: Alkali metals impart characteristic flame colourations to the flame.
Reason R: Alkali metals have low ionization enthalpies and hence their electrons can be excited to higher
levels easily. ANSWER: (a)
8. Assertion A: Noble gases have highest first ionization enthalpies in their respective periods.
Reason R: Noble gases have stable electronic configurations. ANSWER: (a)

TWO MARKS QUESTIONS

Q.1. Describe the two merits of long form periodic table over the Mendeleev’s periodic table?
Ans- 1. It removed the anomalies about the position of isotopes which existed in the Mendeleev’s table. 2.
It relates the position of an element in the periodic table with its electronic configuration.

Q.2. What is meant by periodicity in properties of elements? What is the reason behind this?
Ans- The repetition of similar properties after regular intervals is called as periodicity. It is due to the
similarity in the outer electronic configurations which gives rise to the periodic properties of the elements.

Q.3. How do atomic radii vary in a group and a period?

Ans- In group- Atomic size increases on moving from top to bottom. In period- Atomic size decreases on
moving left to right in a period.

Q.4. Name the factors which affect the ionisation enthalpy of an element.
Ans- (i) Size of atom or ion (ii) Nuclear charge (iii) Electronic configuration (iv) Screening effect (v)
Penetration effect of the electrons

Q.5. Noble gases have zero electron gain enthalpy values. Explain.
Ans- Because the outer most shell of noble gases is completely filled and no more electrons can be added.

THREE MARKS QUESTIONS

Q.1. The first ionisation enthalpy of magnesium is higher than that of sodium. On the other hand, the second
ionisation enthalpy of sodium is very much higher than that of magnesium. Explain.
Ans- The 1st ionisation enthalpy of magnesium is higher than that of Na due to higher nuclear charge and
slightly smaller atomic radius of Mg than Na. After the loss of first electron, Na+ formed has the electronic
configuration of neon (2,8). The higher stability of the completely filled noble gas configuration leads to very
high second ionisation enthalpy for sodium. On the other hand, Mg+ formed after losing first electron still
has one more electron in its outermost (3s) orbital. As a result, the second ionisation enthalpy of magnesium
is much smaller than that of sodium.

Q.2. Among the elements of the second period Li to Ne pick out the element:
(i) with the highest first ionisation energy
(ii) with the highest electronegativity
(iii) with the largest atomic radius Give the reason for your choice.
Ans- (i) Ne .due to higher nuclear charge.
(ii) F. due to small size
(iii) Li .due to less nuclear charge.

Q.3. Arrange the following as stated:

(i) N2, O2, F2, Cl2 (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

Q.4. Explain why are cations smaller and anions larger in size than their parent atoms?
Ans- (a) The cations are smaller than their parent atoms due to the following reasons:
(i) Disappearance of the valence shell.
(ii) Increase of effective nuclear charge

(b) The anions are larger than their parent atoms due to the following reason: An increase in the number of
electrons in the valence shell reduces the effective nuclear charge due to greater mutual shielding by the
electrons. As a result, electron cloud expands, i.e., the ionic radius increases.

Q.5. Consider the following species: N3–, O2–, F–, Na+, Mg2+ and Al3+
(a) What is common in them?
(b) Arrange them in the order of increasing ionic radii.
Ans- (a) the same number of electrons (10 electrons). Hence, the given species are isoelectronic.
(b) Al3+ < Mg2+ < Na+ < F– < O2– < N3–

CASE BASED QUESTIONS

PASSAGE II
Read the passage given below and answer the following questions:
In the periodic table electronegativity increases from left to right in a period and decreases from top to bottom
in a group. The non-metallic character of an element is directly related to the electronegativitywhile the
metallic character is inversely related to it.
1. The element with maximum electronegativity belongs to
(a) Period-1, Group-18 (b) Period-2, Group-17
(c) Period-3, Group-17 (d) Period-2, Group-1.
ANSWER: (b)
2. Which of the following groups contains metals, non-metals as well as metalloids?
(a) Group-1 (b) Group-17 (c) Group-14 (d) Group-2.
ANSWER: (c)
3. The least, metallic element of group-13 is
(a) Aluminium(b) Boron (c) Gallium (d) Indium.
ANSWER: (b)
4. The electronegativity increases with
(a) decrease in nuclear charge (b) increase in atomic mass
(c) decrease in atomic size (d) increase in atomic number.
ANSWER: (c)

FIVE MARKS QUESTIONS

Q.1. What is the cause of the periodicity in the properties of the elements? How do the following properties
vary in (a) a group and (b)in a period
(i) electronegativity
(ii) ionisation enthalpy
(iii) Atomic size
Ans- It is due to the similarity in the outer electronic configurations which gives rise to the periodic
properties of the elements.
(a) In a group:
(i) Electronegativity- It decreases down the group.
(ii) Ionisation enthalpy- It decreases down the group.
(iii) Atomic size- It increases down the group.
 (b) In a period:
(i) Electronegativity- Increases
(ii) Ionisation enthalpy- Increases
(iii) Atomic size- Decreases.

4. CHEMICAL BONDING AND MOLECULAR STRUCTURECHEMICAL BOND

The attractive force which holds various constituents (atoms, ions, etc.) together in different chemical
species is called a chemical bond.

KÖSSEL-LEWIS APPROACH TO CHEMICAL BONDING

Kossel and Lewis developed the electronic theory of valence to explain the formation of chemical
bonds between the two atoms. According to this theory, every atom tries to attain octet configuration
(presence of eight electrons) in its valence shell by losing or gaining or by sharing of electrons.

Lewis Symbols:

A Lewis Symbol is constructed by placing dots representing electrons in the outer energy
around the symbol for the element.

Octet Rule

The tendency of atoms to have eight electrons in the valence shell is known as the "Octet rule.

Formal Charge

The formal charge is the difference in the number of valence electrons in the atom and the number
of valence electrons in the Lewis structure.
For example,

Limitations of the Octet Rule

The incomplete octet of the central atom

For example: In some polyatomic molecules like LiCl, BeH2 and BCl3, the number of electrons
surrounding the central atom is less than eight. Li, Be and B have 1,2 and 3 valence electrons only.

Odd-electron molecules

Molecules having an odd number of electrons like nitric oxide, NO and nitrogen dioxide, NO2, do
not satisfy the octet rule for all the atoms.

The expanded atom

 Born Haber cycle

Born Haber cycle is a cycle of enthalpy change of process that leads to the formation of a solid
crystalline ionic compound from the elemental atoms in their standard state and of the enthalpy of formation
of the solid compound such that the net enthalpy becomes zero.

BOND PARAMETERS

Bond Length

Bond length is defined as the equilibrium distance between the nuclei of two bonded atoms in a
molecule.

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. The unit of bond enthalpy is kJ mol–1. For example, the H – H bond enthalpy
in hydrogen molecule is 435.8 kJ mol–1. H2(g) → H(g) + H(g); ∆H = 435.8 kJ mol–1

Bond Order

Bond Order is given by the number of bonds between the two atoms in a molecule. The bond order,
for example in H2 (with a single shared electron pair), in O2 (with two shared electron pairs) and in N2
(with three shared electron pairs) is 1,2,3 respectively.

Resonance

According to the concept of resonance, whenever a single Lewis structure cannot describe amolecule
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.

Dipole moment

Dipole moment (µ) = charge (Q) × distance of separation ®

Debye units (D). The conversion factor is 1 D = 3.33564 × 10–30 C m where C is coulomb and m is meter.

Fagan’s rule:

⮚ 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.

THE VALENCE SHELL ELECTRON PAIR REPULSION (VSEPR) THEORY

The main postulates of VSEPR theory are as follows:

⮚ The shape of a molecule depends upon the number of valence shell electron pairs (bonded or
nonbonded) around the central atom.
⮚ Pairs of electrons in the valence shell repel one another since their electron clouds are negatively
charged.
⮚ These pairs of electrons tend to occupy such positions in space that minimise repulsion and thus
maximise distance between them.
⮚ The valence shell is taken as a sphere with the electron pairs localising on the spherical surface at
maximum distance from one another

The repulsive interaction of electron pairs decrease in the order: Lone pair (lp) – Lone pair (lp) > Lone pair
(lp) – Bond pair (bp) > Bond pair (bp) – Bond pair (bp)
Hybridisation

The process of intermixing of the orbitals of slightly different energies so as to redistribute their
energies, resulting in the formation of new set of orbitals of equivalent energies and shape

Hybridisation of Elements involving d Orbitals

 (i) Formation of PCl5 (sp3d hybridisation):
The ground state and the excited state outer electronic configurations of phosphorus (Z=15) are
represented below.

Now the five orbitals (i.e., one s, three p and one d orbitals) are available for hybridisation to yield a set of
five sp3d hybrid orbitals which are directed towards the five corners of a trigonal bipyramidal as depicted in
the above fig.

Molecular Orbital Theory

According to this theory, the atomic orbitals combine to form the molecular orbitals. The number of
molecular orbitals formed is equal is the number of atomic orbitals involved. According to this theory.

1. The molecular orbitals are formed by LCAO (Linear combination of atomic orbitals) method, i.e., by
addition or subtraction of wave functions of individual atoms, thus
Ψ MO = ΨA ± Ψ B
Ψb=ΨA+ΨB
Ψa=ΨA–ΨB
 2. Molecular orbital of lower energy is known as bonding molecular orbital and that of higher energy is
known as anti-bonding molecular orbital.
3. Aufbau rule, Pauli’s exclusion principle and Hund’s rule are all applicable for molecular orbitals.
4. The shape is governed by the shape of atomic orbitals, e.g., s-s and p-p overlapping.
(i) Combination between s-atomic orbitals

(ii) Combination between 2s and 2s orbitals gives σ2s and σ 2s orbitals.

(iii) Combination between p-atomic orbitals

(iv) Combination between 2p x and 2p y atomic orbitals

2py atomic orbitals will also overlap in the same way and thus, resulting molecular orbitals are π2p y and
π2py .

If molecular orbital has symmetry with respect to centre, it is called gerade (g) otherwise ungerade (u). All
σ bonding and π anti-bonding MO are g while all π bonding and σ anti-bonding MO are u.

Electronic Configuration and Bond Order (BO) Of Molecular

The order of energy of molecular orbitals has been determined experimentally by spectroscopy for
the elements of the second period. The increasing order of energies of the molecular orbitals in homonuclear
diatomic molecules is
 (
  2p  2p )  ( 2p  2p ) For O , F 
*
* *
1s   *1s   2s   * 2s   2 p z x y x y z
2p
2 2

Hydrogen Bond

It is defined as the force of attraction existing between hydrogen atom covalently bonded to highly
electronegative atom (N, O or F) and the electronegative atom belonging to another molecule of the same
or different substance. It is represented by dotted lines. The chains possess a zig – zag structure.

(Hydrogen bond is purely electrostatic and a weak bond.

Types of hydrogen bonds are

(i) Intermolecular H-bonding : H-bonding involving two or more molecules.

(ii) Intramolecular H-bonding : H-bonding within a molecule.

Applications of Intermolecular H-bonding

(i) Melting point and boiling point of water has the lowest molecular weight among the hydrides of group
16 elements yet it has the highest melting and boiling points. It is due to intermolecular H- bonding
in H2O.
(ii) Melting point and boiling point of alcohols The marked difference between the melting and boiling
points of alcohols is also due to H-bonding.
Applications of Intramolecular H-bonding

Volatile character of nitrophenols o-nitrophenol is more volatile (b.p. 214°C) as compared to meta
(b.p. 290°C) and para (b.p. 279°C). It is due to chelation.
Metallic Bond

Metallic bond is the force of attraction between a metal ion to a number of electrons within its
sphere of influence. Electron-sea theory of metallic bond explains number of the properties of the metal

Strength of bonds

Ionic bond > covalent bond > metallic bond > H-bond

Multiple Choice Questions

1. Molecules are held together in a crystal by

(a) hydrogen bond
(b) electrostatic attraction
(c) Van der Waal’s attraction
(d) dipole-dipole attraction
Answer: (c) Van der Waal’s attraction
2. Find the molecule with the maximum dipole moment
(a) CH4
(b) NH3
(c) CO2
(d) NF3
Answer: (c) CO2
3. MX 6 is a molecule with octahedral geometry. How many X – M – X bonds are at
180°?
(a) four
(b) two
(c) three
(d) six
Answer: (c) three
4. The formal charge and P-O bond order in PO43- respectively are
(a) 0.6, -0.75
(b) -0.75, 1.25
(c) 1.0, -0.75
(d) 1.25, -3
Answer: (b) -0.75, 1.25
5. Which of the molecules does not have a permanent dipole moment?
(a) SO3
(b) SO2
(c) H2S
(d) CS2
Answer: (d) CS2
6. Which one has a pyramidal shape?
(a) SO3
(b) PCl3
(c) CO32-
(d) NO3–
Answer: (b) PCl3
7. Polarity in a molecule and hence the dipole moment depends primarily on
electronegativity of the constituent atoms and shape of a molecule. Which of the
following has the highest dipole moment?
(i) CO2
(ii) HI
(iii) H2O
(iv) SO2
Answer: (iii) H2O
8. Hydrogen bonds are formed in many compounds e.g., H2O, HF, NH3. The boiling
point of such compounds depends to a large extent on the strength of hydrogen bond
and the number of hydrogen bonds. The correct decreasing order of the boiling points
of above compounds is
(i) HF > H2O > NH3
(ii) H2O > HF > NH3
(iii) NH3 > HF > H2O
(iv)NH3 > H2O > HF
Answer: (ii) H2O > HF > NH3
9. Which of the following attain the linear structure:
(i) BeCl2
(ii) NCO+
(iii) NO2
(iv) CS2
Answer: (i) BeCl2
10. Which of the following statements are not correct?
(i) NaCl being an ionic compound is a good conductor of electricity in the solid
state.
(ii) In canonical structures there is a difference in the arrangement of atoms.
(iii) Hybrid orbitals form stronger bonds than pure orbitals.
(iv) VSEPR Theory can explain the square planar geometry of XeF4.
Answer: (i) NaCl being an ionic compound is a good conductor of electricity in the
solid state.
11. The bond length between hybridised carbon atom and other carbon atom is
minimum in
(a) Propane
(b) Butane
(c) Propene
(d) Propyne
Answer: (d) Propyne
12. The number of nodal planes present in s × s antibonding orbitals is
(a) 1
(b) 2
(c) 0
(d) 3
Answer: (a)1
13. Which one of the following does not have sp² hybridised carbon?
(a) Acetone
(b) Acetic acid
(c) Acetonitrile
(d) Acetamide
Answer: (c) Acetonitrile
14. Which of the following will have the lowest boiling point?
(a) 2-MethylButane
(b) 2-MethylPropane
(c) 2,2-Dimethylpropane
(d) n-Pentane
Answer: (b) 2-MethylPropane
15. Among the following mixtures, dipole-dipole as the major interaction, is present in
(a) benzene and ethanol
(b) acetonitrile and acetone
 (c) KCl and water
(d) benzene and carbon tetrachloride
Answer: (c) KCl and water
16. Which of the following types of hybridisation leads to three dimensional geometry
of bonds around the carbon atom?
(a) sp
(b) sp²
(c) sp³
(d) None of these
Answer: (c) sp³
17. The maximum number of hydrogen bonds that a molecule of water can have is
(a) 1
(b) 2
(c) 3
(d) 4
Answer: (d) 4
18. The number of types of bonds between two carbon atoms in calcium carbide is
(a) Two sigma, two pi
(b) One sigma, two pi
(c) One sigma, one pi
(d) Two sigma, one pi
Answer: (b) One sigma, two pi
19. Dipole-induced dipole interactions are present in which of the following pairs?
(a) H2O and alcohol
(b) Cl2 and CCl4
(c) HCl and He atoms
(d) SiF4 and He atoms
Answer: (c) HCl and He atoms
20. The structure of IF7 is
(a) Pentagonal bipyramid
(b) Square pyramid
(c) Trigonal bipyramid
(d) Octahedral
Answer: (a) Pentagonal bipyramid
 Assertion and Reason Questions

Directions: Each of these questions contain two statements, Assertion and Reason. Each of these questions
also has four alternative choices, only one of which is the correct answer. You have to select one of the
codes (a), (b), (c) and (d) given below.
(a) Assertion is correct, reason is correct; reason is a correct explanation for assertion.
(b) Assertion is correct, reason is correct; reason is not a correct explanation for assertion
(c) Assertion is correct, reason is incorrect
(d) Assertion is incorrect, reason is correct.

1 Assertion : The bond order of helium is always zero.

Reason : The number of electrons in bonding molecular orbital and antibonding
molecular orbital is equal.
Answer: (a)
2 Assertion : The lesser the lattice enthalpy more stable is the ionic compound.
Reason : The lattice enthalpy is greater, for ions of highest charge and smaller radii.
Answer: (d) Assertion is false but reason is true.
The greater the lattice enthalpy, more stable is the ionic compound.
3 Assertion : BF3 molecule has zero dipole moment.
Reason : F is electronegative and B–F bonds are polar in nature.
Answer: (b)
4 Assertion : Lone pair-lone pair repulsive interactions are greater than lone pair-
bond pair and bond pair-bond pair interactions.
Reason : The space occupied by lone pair electrons is more as compared to bond
pair electrons.
Answer: (a) While the lone pairs are localised on the central atom, each bonded
pair is shared between two atoms. As a result, the lone pair electrons in a molecule
occupy more space as compared to the bonding pairs of electrons. This results in
greater repulsion between lone pairs of electrons as compared to the lone pair -
bond pair and bond pair – bond pair repulsions.
5 Assertion : pi bonds are weaker than σ bonds.
Reason : pi bonds are formed by the overlapping of p-p orbitals side wise
Answer: (a) Both assertion and reason are true and reason is the correct
explanation of assertion. pi bonds are formed by the overlapping of p-p orbitals
perpendicular to their axis i.e., sidewise overlap.
 VERY SHORT ANSWER QUESTIONS

1(a) What change in energy takes place when a molecule is formed from its atoms?
Answer: There is a fall in energy.
1(b) Name the shapes of the following molecules: CH4, C2H2, CO2.
Answer: CH4: Tetrahedral; C2H2: Cylindrical; CO2: linear
Arrange the following in order of increasing strengths of hydrogen bonding O, F, S,
2(a)
Cl, N.
Answer: Cl < S < N < O < F

2(b) Which orbitals can overlap to form a cr-bond and which orbitals can do so to form a
π bond?
Answer: s-s, s-p, p-p form a bond, and only p-p form π bond
3
Which electrons take part in bond formation?
(a)
Answer: Valence electrons present in the outermost shell.
How is bond length is related to bond order ?
b)
Answer: Greater the bond order ,lesser the bond length.
4 Name the method generally used for the calculation of lattice energy or electron
(a) affinity.
Answer: Borh-Haber cycle.
(b) Which type of forces holds the atoms together in an ionic compound?
Answer: Electrostatic forces of attraction.
5
Write the Lewis structure of the polyatomic ions CN–, SO42-.
(a)
Answer:

(b) Arrange the following in order of decreasing C-C bond length: C2H6, C2H2, C2H4
Answer: H3C – CH3 > H2C = CH2 > HC ≡ CH.
6
Write down the resonance structures of nitrous oxide.
(a)
Answer:

(b) What kind of bond exists between two non-metallic elements?

 Answer: Covalent bonds because the difference of electronegativity between two
non-metals is usually very small.

7(a) Define valency

Answer: The number of electrons that an atom gains or loses or shares with other
atoms to attain noble gas configuration is termed its valency.
(b) Though chlorine has nearly the same electronegativity as nitrogen, yet there is no
hydrogen bonding in HCl. Why?
Answer: The size of the chlorine atom (3 orbits) is bigger than N (2 orbits).
8
On what factors the polarity of the bond depends?
(a)

Answer: Difference of electronegativity of the two atoms.

(b) What type of orbitals can overlap to form a covalent molecule?
Answer: Half-filled atomic orbitals containing electrons with opposite spins.

Short Answer Questions-II

1 (a) Which out of CH3F and CH3Cl has a higher dipole moment and why?
Answer: The dipole moment of CH3Cl is greater than that of CH3F. The C-F bond
length in CH3F is smaller than the C-Cl bond length in CH3Cl. The charge separation
in the C-F bond is more than in the Cl-C bond- fluoride being more electronegative
than chlorine. The bond length has a greater effect than the charge
separation. Hence the dipole moment of CH3C1 is greater than that of CH3F.
(b) Why covalent bonds are called directional bonds whereas ionic bonds are called
non-directional?
Answer: A covalent bond is formed by the overlap of half-filled atomic orbitals which
have definite directions. Hence covalent bond is directional. In ionic compounds,
each ion is surrounded by a number of oppositely charged ions and
hence there is no definite direction.
(c) Account for the following: The experimentally determined N-F bond length in
NF3 is greater than the sum of the single covalent radii of N and F.
Answer: This is because both N and F are small and hence have high-electron
density. So they repel the bond pairs thereby making the N-F bond length larger.
2(a) Why HCl is polar whereas the Cl2 molecule is non-polar?
Answer: In Cl2 both atoms have the same electronegativity. Hence the shared pair of
electrons is attracted equally by both and remains exactly in the center. NO end
acquires a negative or positive charge. In HCl, chlorine is more electronegative than
H. Hence shared pair of electrons is more attracted towards chlorine, which,
therefore acquires a negative charge while H acquires a positive charge.
(b) Out of sigma and pi bonds, which one is stronger and why?
 Answer: Sigma (a) bond is stronger This is because a bond is formed by head-on
overlapping of atomic orbitals and such overlapping being on the internuclear axis is
large, n bond is formed by sidewise overlapping which is small and so a Pi bond is
weaker.
(c) Out of p-orbital and sp-hybrid orbital which has greater directional character and
why?
Answer: sp orbital has a greater directional character than p-orbital. This is because
the p-orbital has equal-sized lobes with equal electron density in both the lobes
whereas the sp-hybrid orbital has greater electron density on one side.
3 (a) Explain giving reasons whether BH4 and H3O+ will have the same/different
geometry?
Answer: The central atom in both the ions is surrounded by the same number of
pairs of electrons, that is, 4. Hence they have the same tetrahedral geometry.
(b) Out of peroxide ion (O22- ) and superoxide ion (O2 - ) which has larger bond length
and why?
9 (c) Answer: The bond order of O2– is 1.5 while that of O22- is 1.0.
The lesser the bond order, the greater is the bond length as the bond order is
inversely proportional to bond length. ( Hence O22- has a larger bond length than
O22-.

Long Answer

1 Discuss the shape of the following molecules using the VSEPR model:BeCl2, BCl3 , SiCl4,
AsF5,
 H2S, PH3

2 What is meant by hybridisation of atomic orbitals? Describe the shapes of sp,sp2, sp3
hybrid orbitals.
Answer: Hybridisation: It is defined as the process of intermixing of atomic
oribitals of slightly different energies to give rise to new hybridized orbitals having
equivalent energy and identical shapes.
Shapes of Orbitals:
sp hybridisation: When one s-and one p-orbital, intermix then it is called sp-
hybridisation. For example, in BeF2, Be atom undergoes sp-hybridisation. It has
linear shape. Bond angle is 180°.
sp2 hybridisation: One s-and two p-orbitals get hybridised to form three equivalent
hybrid orbitals. The three hybrid orbitals directed towards three corners of an
equilateral triangle. It is, therefore, known as trigonal hybridisation.
sp3 hybridisation: One s-and three p-orbitals get hybridised to form four equivalent
hybrid orbitals. These orbitals are directed towards the four corners of a regular
tetrahedron.
3 Which hybrid orbitals are used by carbon atoms in the following molecules?
(a) CH3-CH3 (b) CH3-CH = CH2 (c) CH3-CH2-OH (d) CH3-CHO (e) CH3COOH.

4 What is meant by the term bond order? Calculate the bond order of N2, O2, O2+,O –
2

Answer: Bond order is defined as the half of the difference between the number of
electrons present in bonding and antibonding molecular orbitals.
 Case study

1. Read the passage and answer the questions that follow:

The attractive force which holds the two atoms together is called a chemical bond. A covalent bond is
formed by an equal sharing of electrons. A coordinate bond is formed by unequal sharing ofelectrons.
An ionic bond is formed by the transfer of electrons from one atom to another. Octet rule, although
very useful but is not universally applicable. According to valence bond theory, a covalent bond is
formed by overlapping of half-filled atomic orbitals resulting in a lowering of energy and more
stability. Bond order is the number of bonds between atoms in a molecule. The higher the bond order
more will be stability and bond dissociation enthalpy but the smaller the bond length. The polarity of
a covalent bond depends upon the difference in electronegativity. The covalent character of a bond
depends upon polarising power, smaller cation and bigger anions have higher polarising power.
VSEPR theory helps to predict the shapes of molecules.

(a) Write the electron dot structure of N2O.

Ans (a). N≡N+ — O–
 (b) What are the ions present in CsI3?
Ans (b). Cs+ and I3–.

(c) Out of CN+, CN–, NO, which has the highest bond order?
Ans (c). CN– (14): σ(1s)2, σ*(1s)2, σ(2s)2, σ*(2s)2, π(2px)2= π(2py)2, σ (2pz)2.

(d) What is the correct order of repulsion bp – bp, lp – lp, and lp – bp?
Ans (d). lp – lp > lp – bp > bp – bp (bp is bond pair, lp is lone pair).

(e) Draw the structure of XeOF4 on the basis of VSEPR theory.

Ans (e).

2–
f) Which out of B2, CO, O and NO+ are
2 paramagnetic and why?
Ans (f). B2(10): σ(1s)2, σ*(1s)2, σ(2s)2, σ*(2s)2, π(2px)1= π(2py)1

2. Read the following passage and answer the questions given below:

This theory provides a simple procedure to predict the shapes of covalent molecules. Based on the
repulsive interactions of the electron pairs in the valence shell of the atoms. The shape of a molecule
depends upon the number of valence shell electron pairs (bonded or non–bonded) around the central
atom. Pairs of electrons in the valence shell repel one another since their electron clouds are
negatively charged. These pairs of electrons tend to occupy such positions in space that minimize
repulsion and thus maximize distance between them. The valence shell is taken as a sphere with the
electron pairs localising on the spherical surface at maximum distance from one another.A multiple
bond is treated as if it is a single electron pair and the two or three electron pairs of a multiple bond
are treated as a single super pair. Where two or more resonance structures can represent a molecule,
the VSEPR model is applicable to any such structure. The repulsive interaction of electron pairs
decrease in the order:

lp – lp>lp –bp>bp – bp
lone pairs are localised on the central atom and each bonded pair is shared between two atoms.
As a result, the lone pair electrons in a molecule occupy more space as compared to the bonding pairs
of electrons. These results in greater repulsion between lone pairs of electrons as compared to the lone
pair – bond pair and bond pair – bond pair repulsions.

1. Percentage of s–character in sp2 hybrid orbital is

a) 25
b) 50
c) 33
d) 75 Answer:

c) 33

2. Shape of XeF4 molecule is

a) Linear
b) Pyramidal
c) Tetrahedral
d) Square planar

Answer: d) Square planar

3. Shape of methane molecule is

a) Pyramidal
b) Tetrahedral
c) Octahedral
d) Square planer Answer:

b) Tetrahedral

4. Hybridisation involves
a) Mixing up of atomic orbitals

b) Addition of an electron pair

c) Removal of an electron pair
d) Separation of orbitals
Answer: a)Mixing up of atomic orbitals

5. Number of lone pair (s) in XeOF4 is/are

a) 0
b) 1
c) 2
d) 3
Answer: b)1
 5. CHEMICAL THERMODYNAMICSTHERMODYNAMIC
TERMS
• System It refers to the part of universe in which observations are carried out.
• Surroundings The part of universe other than the system is known as surroundings.
• Boundary The wall that separates the system from the surroundings is called boundary.
• Thermodynamic equilibrium A system in which the macroscopic properties do not undergo any
change with time is called thermodynamic equilibrium.
• Thermal equilibrium If there is no flow of heat from one portion of the system to another, the
system is said to be in thermal equilibrium.
Types of Systems
Open system The system in which energy and matter both can be exchanged with the surroundings.
Closed system The system in which only energy can be exchanged with the surroundings.
Isolated system The system in which neither energy nor matter can be exchanged with the surroundings.
Intensive Properties
Properties of the system which depend only on the nature of matter but not on the quantity of matter are
called Intensive properties, e.g., pressure, temperature, specific heat, etc
Extensive Properties
Properties of the system which are dependent on the quantity of matter are called extensive properties, e.g.,
internal energy, volume, enthalpy, etc.
State of System:
When microscopic properties have definite value, the conditions of existence of the system is known as
state of system.
State functions: When values of a system is independent of path followed and depend only on initial and
final state, it is known as state function, e.g., Δ U, Δ H, Δ G etc.
Path functions: These depend upon the path followed only, e.g., work, heat, etc.
Thermodynamic Process It is the operation which brings change in the state of the system.
Thermodynamic processes are
Isothermal process: In which temperature remains constant, i.e., (dT = 0, Δ U = 0).
Isochoric process: In which volume remains constant, i.e., (Δ V = 0).
Isobaric process: In which pressure remains constant, i.e., (Δp = 0).
Adiabatic process: In which heat is not exchanged by system with the surroundings(Δq= 0).
Cyclic process: It is a process in which system returns to its original state after undergoing a series of
change.
 Reversible process: A process that follows the reversible path, i.e., the process which occurs in infinite
number of steps in this Way that the equilibrium conditions are maintained at each step, and the process
can be reversed by infinitesimal change in the state of functions.
Irreversible process: The process which cannot be reversed and amount of energy increases. All natural
processes are Irreversible.
Internal Energy (E or U) :
It is the total energy within the substance. It is the sum of many types of energies like vibrational energy,
translational energy. etc. It is a extensive property and state function.
Its absolute value cannot be determined but experimentally change in internal energy (Δ) can be
determined by ΔU = U2 – U1 or ΣUP – ΣUR
First Law of Thermodynamics:
Energy can neither be created nor destroyed although it can be converted from one form to the other.
Mathematically, ΔU = q + W
where, ΔU = internal energy change q = heat added to system
W = work added to system
Sign convention:
(i) q is + ve = heat is supplied to the system
(ii) q is – ve = heat is lost by the system
(iii) W is + ve = work done on the system
(iv) W is – ve =work done by the system
Enthalpy (H): At constant volume ∆V = 0, qv =∆ U
So H = U + p∆V, qp = H2- H1 = ∆H
∆H = ∆U + P.∆ V.
Exothermic and Endothermic reactions: ∆H = –Ve for exothermic and∆ H
= +Ve for endothermic reaction i.e. evolution and absorption of heat respectively
HEAT CAPACITY
• Heat Capacity of a System
Specific heat, also called specific heat capacity is the quantity of heat required to raise the temperature of
one unit mass of by one degree celsius (or one kelvin).
The enthalpy change accompanying a reaction is called the reaction enthalpy
Measurement of ∆H and ∆U The process is carried out in a vessel called calorimeter, immersed in a
known volume of a liquid.
(a) ∆U measurements: The energy changes are measured a t c o n s t a n t v o l u m e. No work is d o n e
.A bomb calorimeter is used.
(b) ∆H measurements: In exothermic reaction, heat is evolved, so q and H will be negative. In endothermic
p reaction, heat is absorbed, so q and H will be positive

Standard Enthalpy of Reactions

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
Enthalpy changes during phase transformations:
• Standard enthalpy of fusion / molar enthalpy of fusion, H is the enthalpy _fus_ change that
accompanies melting of one mole of a solid substance in standard state.
• Standard enthalpy of vaporization or molar enthalpy of vaporization. ∆H vap is the amount of
heat required to vaporize one mole of a liquid at constant temperature and under standard pressure.
• Standard molar enthalpy of formation ∆Hr_ is the standard enthalpy change for the formation of
one mole of a compound from its elements in their most stable state of aggregation
• Standard enthalpy of sublimation, ∆subH0 is the change in enthalpy when one mole of a solid
substance sublimes at a constant temperature and under standard pressure (1bar.
Hess’s Law of constant heat summation: 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 + --------
Bond enthalpy: 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. Further ∆H r = B.E. (Reactants) - B.E. (Products)
Lattice Enthalpy
The lattice enthalpy of an ionic compound is the enthalpy change which occurs when one mole of an ionic
compound dissociates into its ions in gaseous state.
Spontaneous & Non Spontaneous Processes: A process which can take place by itself is called
spontaneous process. A process which can neither take place by itself or by initiation is called non
Spontaneous.
Enthalpy of Solution (symbol : ∆solH0 ) Enthalpy of solution of a substance is the enthalpy change when
one mole of it dissolves in a specified amount of solvent
Enthalpy of Dilution It is known that enthalpy of solution is the enthalpy change associated with the
addition of a specified amount of solute to the specified amount of solvent at a constant temperature and
pressure
Driving forces for spontaneous process: (i) Tendency for minimum energy
state. (ii) Tendency for maximum randomness.
Entropy (S): It is measure of randomness or disorderness of a system.
i.e. Gas>Liquid>Solid.
Entropy change ( ∆S) = q(rev.)J.K-1 .mol -1
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.
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): defined as G = H – T.S & ∆G = H – T∆S (Gibb’s
Helmholts equation) it is equal useful work i.e. - ∆G = W(useful) = W(max.)
If ∆G = - ve the process is spontaneous.If it is positive the process is non spontaneous.For reversible
process ∆G = 0

SOME IMPORTANT FORMULAE

∆U=q+w

∆H=∆U+P∆V

∆H=∆U+∆ngRT

CP-CV=R

∆H r=Σa i Hproducts- Σb i Hreactants

∆rHo=∆r1H1+∆r2H2+∆r3H3……

∆Sfusion=∆Hfusion
T

∆S = qrev
T

∆G = H – T∆S

∆Gr=-RT lnK
 MCQ
1. Thermodynamics is not concerned about .
(i) energy changes involved in a chemical reaction.
(ii) the extent to which a chemical reaction proceeds.
(iii) the rate at which a reaction proceeds.
(iv) the feasibility of a chemical reaction.
(Answer) (iii) the rate at which a reaction proceeds
2. Which of the following statements is correct?
(i) The presence of reacting species in a covered beaker is an example of open system.
(ii) There is an exchange of energy as well as matter between the system and the surroundings in a closed
system.
(iii) The presence of reactants in a closed vessel made up of copper is an example of a closed system.
(iv) The presence of reactants in a thermos flask or any other closed insulated vessel is an example of a
closed system.

(Answer) (iii) The presence of reactants in a closed vessel made up of copper is an example of a closed system.

3. The state of a gas can be described by quoting the relationship between_ .

(i) pressure, volume, temperature (ii) temperature, amount, pressure
(iii) amount, volume, temperature (iv) pressure, volume, temperature, amount

(Answer) (iv) pressure, volume, temperature, amount

4. The volume of gas is reduced to half from its original volume. The specific
heat will be .
(i) reduce to half (ii) be doubled (iii) remain constant (iv) increase four times

(Answer) (iv) pressure, volume, temperature, amount

5. The enthalpies of elements in their standard states are taken as zero. The
enthalpy of formation of a compound
(i) is always negative (ii) is always positive
(iii) may be positive or negative (iv) is never negative

(Answer) (iii) may be positive or negative

6. Enthalpy of sublimation of a substance is equal to
(i) enthalpy of fusion + enthalpy of vapourisation (ii) enthalpy of fusion
(iii) enthalpy of vapourisation (iv) twice the enthalpy of vapourisation
(Answer) (i) enthalpy of fusion + enthalpy of vapourisation
7. Which of the following is not correct?
(i) ∆G is zero for a reversible reaction
(ii) ∆G is positive for a spontaneous reaction
(iii) ∆G is negative for a spontaneous reaction (iv)
∆G is positive for a non-spontaneous reaction
(Answer) (ii) ∆G is positive for a spontaneous reaction
 8. A thermodynamic state function is a quantity
(i) used to determine heat changes (ii) whose value is independent of path
(iii) used to determine pressure volume work (iv) whose value depends on temperature only.
(Answer) (ii) whose value is independent of path

9. The work done in case of isothermal free expansion is

a)maximum b)minimum c)zero d)positive
(Answer) c)zero

10. The enthalpies of all elements in their standard states are:

(i) unity (ii) zero (iii) < 0 (iv) different for each element
(Answer) (ii) zero
11. ∆U0of combustion of methane is – X kJ mol–1. The value of ∆H0 is
(i) = ∆U0 (ii) > ∆U0 (iii) < ∆U0 (iv) = 0
(Answer) (iii) < ∆U0
12. The enthalpy of combustion of methane, graphite and dihydrogen at 298 K
are, –890.3 kJ mol–1 –393.5 kJ mol–1, and –285.8 kJ mol–1 respectively. Enthalpy
of formation of CH4(g) will be
(i) –74.8 kJ mol–1 (ii) –52.27 kJ mol–1 (iii) +74.8 kJ mol–1 (iv) +52.26 kJ mol–1.
(Answer) (i) –74.8 kJ mol–1
13. A reaction, A + B →C + D + q is found to have a positive entropy change. The
reaction will be
(i) possible at high temperature (ii) possible only at low temperature
(iii) not possible at any temperature (iv) possible at any temperature
(Answer) (iv) possible at any temperature
14. Which of the following is an extensive property
a) Molar heat capacity b) Temperature c) Enthalpy d) All of these
(Answer) c) Enthalpy
15. In an open system, for maximum work, the process must be entirely
a) irreversible b) reversible c) adiabatic d) none of the mentioned
(Answer) b) reversible

(II) In the following questions a statement of Assertion (A) followed by a statement

of Reason (R) is given. Choose the correct option out of the choices given below each question
(i) Both A and R are true and R is the correct explanation of A.
(ii) Both A and R are true but R is not the correct explanation of A.
(iii) A is true but R is false.
(iv) A is false but R is true.
1. Assertion (A): Combustion of all organic compounds is an exothermic reaction.
Reason (R) : The enthalpies of all elements in their standard state are zero
(Answer) Both A and R are true but R is not the correct explanation of A
2. Assertion (A) :Spontaneous process is an irreversible process and may be reversed by some external
agency.
Reason (R) : Decrease in enthalpy is a contributory factor for spontaneity
(Answer) (ii) Both A and R are true but R is not the correct explanation of A.
 3 Assertion (A) : A liquid crystallises into a solid and is accompanied by decrease in entropy.
Reason (R) : In crystals, molecules organise in an ordered manner
(Answer) (i) Both A and R are true and R is the correct explanation of A.

SA(I) 2 MARK QUESTIONS

1. Given: N2(g) + 3H2(g)→ 2NH3(g), ∆H0 = –92.4KJ.mol–1 What is the standard enthalpy of formation
of NH3(g).
(Answer)
The reaction for formation of one mole of ammonia is
½ N2(g) + 3/2 H2(g)→ NH3(g)
The standard enthalpy of formation of ammonia is
∆ fH 0 NH3(g)= -92.4= 46.2 KJmol-1
2
2. Predict the entropy change in- (i) A liquid crystallizes into solid
(ii) Temperature of a crystallize solid raised from OK to 115K
(Answer)
(i) Entropy decreases because molecules attain an ordered state.
(ii)Entropy increase because from OK to 115K particles begin to move.

3. Identify the state functions and path functions out of the following :
enthalpy, entropy, heat, temperature, work, free energy
(Answer)
State Functions : Enthalpy, Entropy, Temperature, Free energy
Path Functions : Heat, Work
4. For the reaction, 2 Cl(g) → Cl2(g), what are the signs of ∆H and ∆S ?
(Answer)
ΔH and ΔS are negative

5. Predict the change in internal energy for an isolated system at constant volume.
(Answer)

For isolated system, there is no transfer of energy as heat or as work i.e.,

w=0 and q=0. According to the first law of thermodynamics.
ΔU = q + w
=0+0=0
ΔU = 0

SA(II) 3 Marks
1. Calculate the number of kJ of heat necessary to raise the temperature of 60.0 g of aluminium from
35°C to 55°C. Molar heat capacity of Al is 24 J mol–1 K–1..
(Answer)
Given: T1=35oC=(35+273)K=308 K
T2=55oC=(55+273)K=328 K
 Cp=24 J mol–1 K–1
Number of mole of Aluminium =60 g/mol =2.23 mole
27 g
△H=nCp△T
△H=2.23 mole×24 Jmol−1K−1×20 K
△H=1.07KJ

2.For the reaction at 298 K, 2A + B →C ∆H = 400 kJ mol–1 and ∆S = 0.2 kJ K–1 mol–1
At what temperature will the reaction become spontaneous considering ∆H and ∆S to be constant over the
temperature range.

(Answer)
ΔG=ΔH−TΔS
Assume that the equation is at equilibrium then
ΔG = 0
ΔG=ΔH−TΔS=0
Therefore T=ΔS=400=2000K
ΔH 0.2 For the
reaction to be spontaneous ΔG must be negative.
Therefore temperature should be greater than 2000 K.

3.For the reaction 2 A(g) + B(g) → 2D(g) ∆U 0 = –10.5 kJ and ∆S0 = –44.1 JK–1. Calculate ∆G0 for the
reaction, and predict whether the reaction may occur spontaneously.

∆ng = 2 – (3) = –1 mole

∆Ho = ∆Uo + ∆ngRT
= (–10.5 kJ) – (–1) (8.314 × 10–3 kJ K–1 mol–1 ) (298 K) = –10.5 kJ – 2.48 kJ
∆Ho= –12.98 kJ
Substituting the values of ∆Ho and ∆So in the expression of ∆Go
∆Go = ∆Ho– T∆So = –12.98 kJ – (298 K) (–44.1 J K–1 ) = –12.98 kJ + 13.14 kJ
∆Go= + 0.16 kJ
Since ∆Gofor the reaction is positive, the reaction will not occur spontaneously.

CASE BASES STUDY

We can measure energy changes associated with chemical or physical processes by an experimental
technique called calorimetry. In calorimetry, the process is carried out in a vessel called calorimeter, which
is immersed in a known volume of a liquid. Knowing the heat capacity of the liquid in which calorimeter
is immersed and the heat capacity of calorimeter, it is possible to determine the heat evolved in the process
by measuring temperature changes. Measurements are made under two different conditions
i) at constant volume, qV
ii) at constant pressure, qp
1. The quantity of of heat required to raise the temperature of one unit mass of a substance by one degree
Celsius is called a)Heat capacity b)Specific heat capacity c)Molar heat capacity d)Heat content
(Answer) b)Specific heat capacity

2. For
adiabatic change a)q=0,w ad =0 b) q=0, w ad =ΔU c) q=0, w ad =ΔH d) q=-w=ΔU
(Answer) a)q=0 w ad =0
 3. In bomb calorimeter which quantity is kept constant to calculate ΔU?
a)volume b)pressure c)temperature d) all of these
(Answer) a)volume

4. What is the relation between heat capacity and temperature

a)q=CΔT b) q=mcΔT c)q=C/n ΔT (d) q=mc/ΔT
(Answer) a)q=CΔT

LONG ANSWER (5 MARKS)

1.(a) Define standard molar enthalpy of formation.

(b) Calculate the enthalpy change for the process
CCl4(g) → C(g) + 4 Cl(g) and calculate bond enthalpy of C – Cl in CCl4(g).
∆vapH0(CCl4) = 30.5 kJ mol–1. ∆fH0 (CCl4) = –135.5 kJ mol–1. ∆aH0 (C) = 715.0 kJ mol–1 , where ∆aH0 is
enthalpy of atomisation ∆aH0 (Cl2) = 242 kJ mol–1

(Answer)

(a) 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

(b) CCl4(l) → CCl4(g) ∆vapH0 = 30.5 kJ mol-1→eqn I

C(s) → C(g) ∆aH0 = 715.0 kJ mol-1→eqn II
Cl2(g) → 2Cl(g) ∆aH0 = 242 kJ mol-1→eqn III
C(g) + 4Cl(g) → CCl4(g) ∆fH0 = -135.5 kJ mol-1→eqn IV
Enthalpy change for the given process C(g) + 4Cl(g) → CCl4(g) can be calculated as given below
ΔH =Equation (II) + 2 × Equation (III) - Equation (I) - Equation (IV)
ΔH = ΔaH0 (C) + 2ΔaH0 (Cl2) - ΔvapH0 - ΔfH0
= (715.0 kJ mol-1) + 2(242 kJ mol-1) - (30.5 kJ mol-1) - (-135.5 kJ mol-1)
∴ ΔH = 1304 kJ mol-1
Bond enthalpy of C-Cl bond in CCl4(g) = 1304 kJ mol-1=326 kJ mol-1
4

2. (a) What are extensive property and intensive properties?

(b) Calculate the standard enthalpy of formation of CH3OH(l) from the following data:
CH3OH (l) +3/2 O2(g) → CO2(g) + 2H2O(l) ; ∆rH0 = –726 kJ mol–1

C(graphite) + O2(g) → CO2(g) ; ∆cH0 = –393 kJ mol–1

H2(g) +1/2 O2(g) → H2O(l) ; ∆f H0 = –286 kJ mol–

(Answer)

a) Intensive Properties
Properties of the system which depend only on the nature of matter but not on the quantity of matter are
called Intensive properties, e.g., pressure, temperature, specific heat, etc
 Extensive Properties Properties of the system which are dependent on the quantity of matter are called
extensive properties, e.g., internal energy, volume, enthalpy, etc.

(b)CH3OH (l) +3/2 O2(g) → CO2(g) + 2H2O(l) ; ∆rH0 = –726 kJ mol–1

On reversing the eqn 1
CO2(g)+2H2O(l)→CH3OH(l)+ 3/2O2(g); ΔrHo=+726kJmol−1 →eqn 1

C(graphite)+O2(g)→CO2(g);ΔcH0=−393kJmol−1 →eqn 2
–1
H2(g) +1/2 O2(g) → H2O(l) ; ∆f H = –286 kJ mol . -→eqn 3
0

Multiply eqn 3 by 2

2H2(g)+O2(g)→2H2O(l);2ΔfH0=2×−286kJmol−1=−572kJmol−1 → eqn 4

On adding eqn 1,eqn 2 and eqn 4,

C(graphite)+2H2(g)+1/2 O2(g)→CH3OH(l)

Enthalpy of formation of CH3OH

ΔfH0=+726−393−572kJmol−1=−239kJmol−1

HOTS
1. The difference between CP and CV can be derived using the empirical relation H = U + pV.
Calculate the difference between CP and CV for 10 moles of an ideal gas.

(Answer)

CP – CV = nR
= 10 × 4.184 J

2. The enthalpy of atomisation for the reaction CH4(g)→ C(g) + 4H (g) is 1665 kJ mol–1. What is the
bond energy of C–H bond?

(Answer)
1665 kJ mol = 416.2 kJ mol
–1 –1

3. Given that ∆H= 0 for mixing of two gases. Explain whether the diffusion of these gases into each
other in a closed container is a spontaneous process or not?

(Answer)

It is spontaneous process. Although enthalpy change is zero but randomness or disorder (i.e., ∆S)
increases. Therefore, in equation ∆G = ∆H – T∆S, the term T∆S will be negative. Hence, ∆G will be
negative

4. Enthalpy diagram for a particular reaction is given in the figure below. Is it possible to decide
spontaneity of a reaction from the given diagram. Explain
 (Answer)

No.
Enthalpy is one of the contributory factors in deciding spontaneity but it is not the only factor. One must
look for contribution of another factor i.e., entropy also, for getting the correct result

****************************************************************************
6.EQUILIBRIUM

KEY POINTS
• Equilibrium in physical processes:
• Solid-liquid equilibrium
• Liquid-vapour equilibrium
• Solid-vapour equilibrium
• Dynamic equilibrium
• law of chemical equilibrium and equilibrium constant
• homogeneous equilibrium
• Equilibrium constant in gaseous systems
• Factors affecting equilibrium-Le Chatteliers principle
• Ionic equilibrium-ionisation of acids and bases
• Strong and weak electrolytes
• Degree of ionisation
• Ionisation of polybasic acids
• Acid strength –pH
• Hydrolysis of salt, buffer solution
• Henderson equation
• Solubility product
• Common ion effect
Chemical Equilibrium: In a chemical reaction chemical equilibrium is defined as the state at which
there is no further change in concentration of reactants and products.

Characteristics of equilibrium:
i) equilibrium can be achieved only in a closed vessel
ii) equilibrium is reversible in nature
iii) equilibrium is dynamic in nature. ie., the system is always in motion in both directions at the
microscopic level
iv) at equilibrium the rate of forward reaction = rate of backward reaction.
 v) Equilibrium state can be recognised by the constancy of measurable properties like colour
,concentration, pressure, density etc.
Types:
• Physical equilibrium
• Chemical equilibrium
Physical equilibrium
It is the equilibrium between same chemical species in different physical states
➢ Solid-liquid equilibrium
H2O(s) ⇌ H2O(l)
➢ Liquid-vapour equilibrium
H2O(l) ⇌ H2O(g)
➢ Solid-vapour equilibrium
H2O(s) ⇌ H2O(g)
Camphor (solid) ⇌ Camphor (vapour)
➢ Solid –solution equilibrium
Sugar in its saturated solution
➢ Gas-solution equilibrium
CO2 dissolved in H2O
Some features of physical equilibrium

Chemical equilibrium: Equilibrium between reactants and products in a chemical reaction.

Characteristics:
a) It’s a dynamic equilibrium i.e. at this stage , the reaction take place in both the direction
with same speed
b) At equilibrium the reaction proceed both side ,equally
c) At equilibrium ,both reactant and products are present and their concentration do not change
with respect to time
d) The state of equilibrium is not effected by the presence of catalyst :it only helps to attain the
equilibrium state faster
e) Change in pressure, temperature and concentration favours one of the reactions and thus
shift the equilibrium point in one direction
 Types:
Homogeneous equilibrium:
the equilibrium between reactants and products in the same physical state is called homogeneous
equilibrium
2SO2(g) + O2(g) ⇌ 2SO3(g)
Heterogeneous equilibrium:
The equilibrium between reactants and products in different physical states is called heterogeneous
equilibrium
CaCO3(s) ⇌ CaO(s)+CO2(g)
Law of Chemical Equilibrium.
At a given temperature, the product of concentrations of the reaction products raised to the respective
stoichiometric coefficient in the balanced chemical equation divided by the product of concentrations of
the reactants raised to their individual stoichiometric coefficients has a constant value. This is known as
the Equilibrium Law or Law of Chemical Equilibrium.
For a reaction A+B ⇌ C+D,rate of forward reaction, Rf =kf[A][B], rate of backward reaction
Rb = kb [C][D]
At equilibrium = Rb,
ie: kf[A][B]= kb[C][D]
Or, kc = kb = [C][D]
kf [A][B]
for a reaction with non-unitary stoichiometric coefficient: aA +bB⇌c C + dD,
kc= [C]c[D]d
[A]a[B]b
Eg: Kc for the reaction, 4NH3(g)+ 5O2(g)⇌ 4NO(g) + 6H2O(g)
is written as Kc=[NO]4 [H2O]6 / [NH3]4 [O2]5
Equilibrium constant for reverse reaction is the inverse of the equilibrium constant for the reaction in
the forward reaction.
Equilibrium Constant in Gaseous Systems
If an equilibrium involves gaseous species then the concentration terms are replaced by partial
pressures
Kp= pCc pDd
pAa pBb
Relation between Kp and Kc: Kp = Kc(RT)Δn
Units: For Kp: Pa,kPa,bar or atm
For Kc: mol L-1
Reaction Quotient Qc : It is the ratio of product of molar concentration of products to the ratio of product
of molar concentration of the reactants at any stage of reaction.
For a reaction aA+bB ⇌ cC+dD, Qc = [C]c[D]d
[A]a[B]b
Application of Kc:
i) Higher the value of Kc,higher will be the extent of reaction. ,smaller value of K indicates, reactant
concentration is predominant.
ii) If Qc > Kc, the reaction proceeds in the backward reaction
iii) If Qc < Kc, the reaction proceeds in the forward reaction
iv)If Qc = Kc, the reaction is at equilibrium.

• Factors affecting equilibrium-Le Chateliers principle

If a system in equilibrium is subjected to a change of concentration, pressure or temperature ,the
equilibrium shifts in the direction to minimise the the effect the change.
Factors:
1.Concentration Reactant concn Forward direction
increased
Product concn. Backward direction
increased
2.Pressure For reactions P∞1/v ,so to the
involving gases direction where there is
decrease in no.of moles
3.Temperature Exothermic Rn. Backward
Endothermic Rn. Forward
4. Catalyst No effect

5.Addition of a) at constant volume No effect

inert gas Towards larger no. of
b) at constant volume gaseous molecules
• Ionic equilibrium-ionisation of acids and bases
• Strong and weak electrolytes
• Degree of ionisation
• Ionisation of polybasic acids
• Acid strength –pH
• Hydrolysis of salt, buffer solution
• Henderson equation
• Solubility product
• Common ion effect
• Factors affecting equilibrium-Le Chateliers principle
IMPORTANT FORMULAE
1. aA+bB ⇌ c C+ d D, Kc = [C]c[D]d
[A]a[B]b
2. Kp = Kc(RT)Δn
3. ΔG0 = -RT ln K =-2.303RTlog K
4. Ka x Kb= Kw
5. pH = -log[H+], pOH = -log[OH-]
6. pKw = pH + pOH = 14
7. x - +H2O ⇌ OH- +HX
Degree of hydrolysis h=√kw/ka x c(for salts of strong acid and weak base)
pH = ½ (pKw + pKa +log c)
pH = ½( pKw - pKb -log c)
Degree of hydrolysis h=√Kw/Ka x Kb(for salts of weak acid and weak base)
pH = ½ (pKw + pKa – log pKb)
pH of buffer solution of salt of weak acid and and its salt:
pH = pKa + log [salt]
[Base]
pOH = pKb + log [salt] (for basic buffers)
[Base]
 Solubility:

Salt type Relation between Example

Ksp and S

AB Ksp=s x s=s2 AgCl,ZnS

AB2 Ksp=s x(2s)2= 4s3 PbCl2,HgCl2
A2B Ksp=(2s)2x(s)= 4s3 Ag2SO4
AB3 Ksp=(s)x(3s)3=
Fe(OH)3
27s3

Multiple Choice Questions:

1. At equilibrium,rate of forward reaction will be ……rate of backward reaction.

a) less than b) greater than c) equal to d) none of these
2. For a pure substance ,at atmospheric pressure the temperature at which the solid and liquid phases are at
equilibrium at is called:
a) freezing point b)boiling point c) kraft temperature d) absolute temperature
3) Henry’s Law is applicable for
a) solid-liquid equilibrium b) solid-gas equilibrium c) gas –liquid equilibrium d) gas –
solution of gas equilibrium
4. Kp=Kc when :
a) Δn=1 b) Δn>1 c)Δn=0 d) Δn<1
5. If Qc > Kc,the reaction proceeds in the
a) forward reaction b) backward reaction c) at equilibrium d) none of these .
6. For the reaction N2(g) + 3H2(g) ⇌2NH3: ΔH = -92.38kJmol-1, raising the temperature ……the
equilibrium concentration of ammonia
a) increases b) decreases c) doesnot change d) all of these
7. The acid –base pair that differs by one …is called a conjugate acid –base pair
a)electron b)proton c) hydronium ion d) hydroxyl ion
8. Which of the following is amphoteric in nature:
a)H3O+ b)HCl c) SO42- d) HSO4-
9. Which of the following salts will give the highest pH in water.
a) KCl b) NaCl c) Na2CO3 d) CuSO4
10. 0.10 M CH3COOH is 1.34% ionised, calculate its Ka.
a) 1.8 x 10-5 b) 5x10-4 c) 1.8x 10-4 d)4x10-5
11. In which of the following equilibrium, Kc and Kp are not equal?
a. 2C (s) + O2 (g) ⇌ 2CO2 (g)
b. 2NO (g) ⇌ N2 (g) + O2 (g)
c. SO2 (g) + NO2 (g) ⇌ SO3(g) + NO(g)
d. H2(g) + I2 (g) ⇌ 2 HI(g)
12. For the reversible reaction, N2(g) + 3 H2(g) ⇌ 2 NH3 (g) at 5000C, the value of Kp is 1.44 × 10-5 when
partial pressure is measured in atmospheres. The corresponding value of Kc, with concentration in mole
litre-1, is :
(a)1.44 × 10-5 / (0.082 × 500)-2 (b) 1.44 × 10-5/(8.314 × 773)-2
-5 2
(c) 1.44 × 10 / (0.082 × 773) (d) 1.44 × 10-5 / (0.082 × 773)-2
13. Kp/Kc for the reaction, CO(g) + ½ O2 (g) ⇌CO2(g) is :
 (a) 1 (b) RT (c) 1/ (
d
)
(
R
T
)
1
/
2

14. For the reaction, N2(g) + O2(g) ⇌2NO(g), the production of NO will be favoured by
(a) High pressure. (b) Low pressure.
(c) Presence of catalyst (d) High concentration of N2.
15.In a reversible reaction, two substances are in equilibrium. If the concentration of each one is doubled
the equilibrium constant will be
(a) Reduce to half its original value. (b) Reduced to one fourth of its original value.
(c) Doubled. (d) Constant.
16. The solubility product of CaSO4 is 6.4 x 10-5.The solubility of salt in mol/Lis
(a)8x10-16 (b) 8x10-2 (c) 8x10-3 (d)16x 10-3
17. Among the following ,the weakest Bronsted acid is
(a)F-(b)Cl- (c)Br- (d)I-
18. For a buffer solution which of the following is true?
(a) pH does not change at all on addition of acid or base
(b) pH change is very little on addition of acid or base
(c) It is a mixture of strong acid with its salt.
(d) It is a mixture of strong base with its salt.
19. For Zr3(PO4)4 the solubility product is Ksp and solubility product is S. Find the correct relation.
(a) S=[Ksp/6912]1/7 (b) S=[ Ksp/216]1/7
( c) S= [ Ksp/216]1/8 (d) S=[ Ksp/912]1/3
20. The pKa of acetic acid and pKb of ammonium hydroxide are 4.76 and 4.75 respectively. The pH of
ammonium acetate solution will be
(a)6.0 (b) 6.05 (c)7.05 (d)7.005.
ANSWERS

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
c a d c b b b d c a a a c d d c d b a d
ASSERTION –REASONING QUESTIONS

In each of the following questions, a statement of Assertion (A) is given followed by a corresponding
statement of Reason (R) just below it. Of the statements, mark the correct answer as –
a. If both assertion and reason are true, and reason is the true explanation of the assertion.
b. If both assertion and reason are true, but reason is not the true explanation of the assertion.
c. If assertion is true, but reason is false.
d. If both assertion and reason are false.
1. Assertion (A). The equilibrium constant is fixed and characteristic for any given chemical reaction at a
specified temperature
Reason (R). The composition of the final equilibrium mixture at a particular temperature depends upon the
starting amount of reactants.
2. Assertion (A). When a catalyst is added to a reaction mixture in equilibrium, the amount of the products
increases.
Reason (R). The forward reaction becomes faster on adding the catalyst.
3. Assertion (A). If standard free energy change of a reaction is zero, this implies that equilibrium constant
of the reaction is unity.
Reason (R). For a reaction in equilibrium, equilibrium constant is always unity.
4. Assertion (A). If to the equilibrium PCl5 (g) → PCl3(g) + Cl2 (g), in a closed vessel, an inert gas is
added, total pressure will increase and hence, equilibrium will shift backward.
Reason (R). Addition of an inert gas to an equilibrium mixture at constant volume shifts the equilibrium in
the backward direction
5. Assertion (A). If reaction quotient (Qc) is less than the equilibrium constant (Kc), the equilibrium tends
to shift in the direction of products.
Reason (R). The expression for equilibrium constant is different than the expression for reaction quotient.
6. Assertion (A). Kp can be equal to or less than or even greater than the value of Kc.
Reason (R). Kp = Kc (RT) ∆n.
 Relation between Kp and Kc depends on the change in the number of moles of gaseous reactants and
products.
7. Assertion (A). For N2 (g) + 3H2 (g) → 2NH3 (g), the equilibrium constant is ‘K’, then for
1/2 N2(g) + 3/2 H2(g) → NH3 (g) the equilibrium constant will be .
Reason (R). If concentrations are changed to half the equilibrium, equilibrium constant will be halved.
8. Assertion (A). A catalyst does not influence the values of equilibrium constant.
Reason (R). Catalysts influence the rate of both forward and backward reactions equally.
9. Assertion (A). The active mass of pure solid and pure liquid is taken unity.
Reason (R). The active mass of pure solids and liquids depends on density and molecular mass. The
density and molecular mass of pure liquids and solids are constant.
10. Assertion (A). For PCl5(g) → PCl3(g) + Cl2 (g). If more Cl2 is added, the equilibrium will shift in
backward direction, hence equilibrium constant will decrease.
Reason (R). Addition of inert gas to be equilibrium mixture at constant volume, does not alter the
equilibrium.
.
ANSWERS

1 2 3 4 5 6 7 8 9 10

a d c d c a c a a c

2 marks questions:

1. For the following equilibrium, K =6.3 x 1014 at 1000 K. NO(g)+O3⇌NO2(g) + O2(g) Both the forward
and reverse reactions in the equilibrium are elementary bimolecular reactions. What is reaction? Kc for the
reverse reaction?
Answer: For the reverse reaction
K’c=1/Kc =1/6.3 x 1014 =1.59 x 10-15

2. What is Kc for the following equilibrium when the equilibrium concentration of each substance is:
[SO2]=0.60M
[O2]=0.82 M and [SO3] =1.90M?
2SO2(g)+O2(g) ⇌2SO3(g)
Kc= [SO3]2
[SO2]2[O2] =(1.9X1.9)/0.60x0.6.x0.82 =12.23 L/mol

3. Find out the value of Kc for each of the following equilibria from the value of Kp:
(a) 2NOCl(g)⇌2NO+Cl2, Kp=1.8 x 10-2 at 500k
(b) CaCO3(s) ⇌ CaO (s) + CO2. Kp=167 at 1073k

4. The value of Kc for the reaction, 2A ⇌ B +C is 2 x 10-3.At a given time, the composition of reaction
mixture
is[A]=[B]=[C]=3 x 10-4 M. In which direction the reaction will proceed?
Qc=(3 x 10-4) x (3 x 10-4)/( 3 x 10-4)2=1
Given, Kc=2 x 10-3
Qc > Kc, so the reaction will proceed in the reverse direction.

5. What is Le Chatelier’s principle?

Le Chatelier's principle states that if a reaction at equilibrium is subjected to change in parameters like
temperature, pressure or concentration of reactants and products, then the reaction equilibrium shifts in a
direction in which the change is counteracted upon.
 6. Classify the following species into Lewis acids and bases.
(a) OH- (b) F- (c) H+ (d) BCl3

7. Explain common ion effect?

The common ion effect is an effect that suppresses the ionization of an electrolyte when another electrolyte
(which contains an ion which is also present in the first electrolyte, i.e. a common ion) is added. It is
considered to be a consequence of Le Chatelier's principle.

8. Why is NH4Cl added in excess before addition of NH4OH in qualitative analysis of group III?
Due to common ion effect (NH4+ ions), NH4Cl supresses the ionisation of NH4OH. Then hydroxides of III
group only (but not of those of IV group) are precipitated.

9. The solubility product of A2B is 32 x 10-9mol3/L. Calculate its solubility.

A2B ⇌ 2A+ + B2-
s 2s s

Ksp = [ A+]2 x [B2-]/ [A2B]

32 x 10-9 = (2s)2 (s)
4S3 = 32 x 10-9
S =2 x 10-3
10. Arrange in the increasing order of pH.
KNO3(aq), NH4Cl(aq), C6H5COONH4(aq),, CH3COONa(aq),
Ans. NH4Cl(aq), < C6H5COONH4(aq), < KNO3(aq), < CH3COONa(aq)

3 MARKS QUESTIONS

1. A sample of pure PCl5 was introduced into an evacuated vessel at 473 K. After equilibrium was reached,
the concentration of PCl5 was found to be 0.5 x 10-1 mol L-1. If Kc is 8.3 x 10-3 what are the concentrations
of PCl3 and Cl2 at equilibrium?

Answer:
Let the initial molar concentration of PCl5 per litre = x mol
Molar concentration of PCl5 at equilibrium = 0.05 mol
... Moles of PCl5 decomposed = (x – 0.05) mol
Moles of PCl3 formed = (x – 0.05) mol
Moles of Cl2 formed = (x – 0.05) mol
The molar conc./litre of reactants and products before the reaction and at the equilibrium point are:
PCl5 PCl3 + Cl2
Applying Law of equilibrium, Kc=[PCl3][Cl2]/PCl5
8.3 x 10-3 = (x-0.05)2/.05
Solving ,X = 0.07 mol
At equilibrium,[PCl5] = [Cl2]=0.07-0.05 =0.02 mol/L

2. It has been found that the pH of a 0.01 M solution of an organic acid is 4.15. Calculate the concentration
of the
anion, the ionization constant of the acid and its PKa.
Answer: HA ⇌ H+
pH= - log[H+]
4.15 = - log[H+]
Log [H+]= - 4.15
[H+] = antilog (-4.15)
=7.08 x 10-5 M
Ka =( 7.08 x 10-5 x 7.08 x 10-5)/0.01= 5 x 10-7
pKa = -log Ka = -log 5 x 10-7=6.301
3. The values of Ksp of two sparingly soluble salts Ni(OH)2 and AgCN are 2.0 x 10-15 and
 6 x 10-17 respectively.
Which salt is more soluble? Explain.
Answer:
AgCN ⇌ Ag+ + CN-
Ksp=[Ag+][CN-]=6 x10-17
let [Ag+] =[CN-]=x
Ni(OH)2 ⇌ [Ni2+] + 2[OH-]
Let [Ni2+] = y, [OH-]=2y
x2 = 6 x10-17, x = 7.8 x 10-9
(y ) x ( 2y)2 = 2 x 10-15, y=0.58 x 10-4
y > x, Ni(OH)2 is more soluble.
4. The ionization constant at 298K is 1.8 x 10 -4 . Calculate the ionization constant of the
corresponding conjugate base.
Ka x Kb =Kw
Kb= Kw/Ka
= (1 x10 -14) /1.8x10 -8
= 5.55x10 -7
5. Ionic product of water at 363K is 10-12 . What will be the pH? Will it be the acidic?
[H + ] [OH - ] = 10 -12
[H + ] =10 -12 /10 -7 =10 -5
pH = - log(H +)
= - log(10 -5 )
pH =5 Acidic
6. A solution is found to contain 0.63 g of nitric acid per 100ml of solution. What is the pH of
solution if acid is completely dissociated?
No. of moles n =w2/M2
= 0.63/63=0.01
Molarity =n/v
= 0.01 x 1000/100
=0.1 molL -1
+
[H ] =[HNO 3 ]
=10 -1
pH = - log(H + )
= - log(10 -1)
= -(-1)log10
pH =1
7. For a water gas reaction at 1000k, the standard Gibb’s free energy change is -8.1kJ/mol. Calculate the
Value of equilibrium constant Kc,for the reaction.
ΔG0 = -8.1 x 1000J/mol
R = 8.314J/mol/k,
T = 1000k
ΔG 0
= -2.303RT logKc
Log Kc = -ΔG0
2.303RT
= 0.4230
Kc = 2.65
8 Calculate the pH at the equivalence point when a solution of 0.10M acetic acid is titrated with a
solution of 0.10M NaOH.Ka for acetic acid is1.9 x 10-5.
pH = 1/2(pKw + pKa +log C)
= 1/2(14-log(1.9 x 10-5) + log(0.05)
= 8.71
Case Based Questions:
 1. According to Arrhenius theory, acids are substances that dissociate in water to give hydrogen ions H +
(aq) and bases are substances that produce hydroxyl ions OH – (aq). The ionization of an acid HX (aq) can
be represented by the following equations:
HX (aq) → H+ (aq) + X – (aq) or HX(aq) + H2O(l) → H3O + (aq) + X – (aq)
Similarly, a base molecule like MOH ionizes in aqueous solution according to the equation:
MOH(aq) → M+ (aq) + OH– (aq)
Bronsted acids are proton donors where as Bronsted bases are proton acceptors. Acids on donating proton
form conjugate bases whereas bases form conjugate acids after accepting proton. Buffer solution is a solution
whose pH does not change.
By adding small amount of H+ or OH-.The decrease in concentration of the ion by adding other ion as
common ion is called common ion effect. Ksp (solubility product) is product of molar concentrations of ions
raised to power no. of ions per formula of ions per formula of the compound in sparingly soluble salt.
Precipitation occurs only if ionic product exceeds solubility product. Solubility of salt decreases in presence
of common ion. Kw the ionic product of water is 1x10-14 at 298 k. Kw increases with increase in temperature.
pH is –log[H3O+]where [H3O+]=cα in monoprotic acid , is molar conc., α is degree ofionisation.
(a) What will be the conjugate base of
(i)H2SO4 (ii) HCO3-?
(b) What will be the conjugate acid of
(i)NH2- (ii)NH3?
(c) The conc. Of H3O+ is 4x 10-4 find its pH
(d) Kb forNH3 is1.80 x 10-5, what will be Ka? [Kw is 1 x10-14]
Answer:
(a) (i)HSO4 – (ii) CO32-
(b) (i)NH3 ii) NH4+
(c) 3.398
d)5.5x10 -10

2. Read the passage given below and answer the following questions.
The Haber process for the synthesis ammonia from molecular hydrogen and nitrogen is represented by the
following thermochemical equations.
N2(g)+3H2(g) ⇌ 2NH3(g): ΔH0=-92.6kJ/mol the reaction is carried out in the presence of a heterogeneous
catalyst containing iron the value of Kc for the reaction is 1.2 at 3750c.
1. Write the equilibrium constant expression for the reaction taking place during Haber process.
2. How does the value of Kc for this reaction change with increase in temperature?
3. Write the expression which represents the relationship between Kp and Kc for this reaction.
4. starting with two mol each (N2, H2, NH3) predict the direction of reaction?
Answer
1. Kc = [ NH3]2/[ N2][H2]3
2. Decreases
3. Kp = Kp/(RT)2
4. Backward direction

5mark Questions
1. (i) State Henry’s law.
(ii) A solution of NH4Cl in water shows pH less than 7.why?
(iii) What is the effect of increasing pressure in the given reactions? Give reasons.
(a)PCl5(g) ⇌ PCl3(g)+Cl2(g)
(b)N2(g)+O2(g) ⇌2NO(g)
(iv) Which of the following are lewis acids?H2O,BF3,H+,NH4+.
Answers:
(i) The mass of Gas dissolved in given mass of a solvent at any temperature is proportional to the
pressure of the gas above the solvent.
 (ii) NH4Cl is salt of weak base NH4OH and strong acid HCl, therefore H+ ions are more than OH-
ions thus,
pH is less than 7.
(iii) (a)The equilibrium will shift in backward reaction because number of moles of products are
more than reactants Δn>0.
(b)No effect because number of moles of reactants and products are equal, i.e.,
Δn=0.
(iv) H2O, BF3, H+

2. (a)Define solubility product. Write solubility product expression for Zr3(PO4)4.

(b) Calculate pH of 0.01 M CH3COOH solution[ka (CH3COOH) = 1.74 x 10-5]
(c ) Explain why NaCl is precipitated when HCl (g) is passed through the saturated solution of NaCl.

Answers:
(a) It is defined as the product of molar concn. Of the ions (formed in the saturated solution at a given
temperature). Raised to the power equal to the no.of times each ion occurs in the equation for
solubility
equilibrium
Zr3(PO4)4⇌3Zr4+ + 4PO43-
4+ 3- 4
Ksp = [Zr ][ PO4 ]
(b) pH = -log[H3O+]
= -log Cα
= -log√Ka x C
= -log√1.74 x 10-5 x 0.01
= 3.3783
(c ) It is due to common ion ,Cl- increase, rate of backward reaction increases, solubility of NaCl
decreases.

3. The equilibrium constant at 298k for the reaction Cu(s)+2Ag+(aq) ⇌ Cu2+(aq) + 2Ag(s) is 2.0 x 1015. In
a solution in which Cu has displaced some Ag ions from solution , the concentration of Ag+ ions is 3.0 x
10- 9mol/L Is this system at equilibrium?
Answer:
Cu(s)+2Ag+(aq) ⇌Cu2+(aq)+2Ag(s)
According to the Law of Chemical Equilibrium,
Kc = [Cu2+(aq)]
[Ag+(aq)]2
Qc =1.8 x 10-2
( 3.0 x 10-9 )2
= 2 x 1015
Since Qc= Kc, the reaction is in equilibrium.

4. The ionization constant of propanoic acid is 1.32×10−5. Calculate the degree of ionization of the acid in
its 0.05 M solution and also its pH. What will be its degree of ionization if the solution is 0.01M in HCl ?
Answer:
Let x be the degree of dissociation.
x=√Ka/c=√1.32×10−5 /0.05 = 0.0162
[H+]=cx=0.05×0.0162=8.12×10−4
pH= log[H+]= −log(8.12×10−4)=3.09
If the solution is 0.01M in HCl solution, then, x=√Ka/c =√1.32×10−5/0.01=0.00132

5. The ionization constant of chloroacetic acid is 1.35×10−3. What will be the pH of 0.1 M acid and its 0.1
M sodium salt solution?
Answer:
(i) For acid solution,[H+]=√Ka C =√1.35×10−3 x 0.1=0.0116 m
 pH = -log[H+] =-log[0.0116]= 1.936
(ii) For 0.1M sodium salt solution, the solution contains sodium salt of chloroacetic acid which is
weak acid and strong base,
pKa = - logKa = -log(1.35×10−3) =2.8697
pKw = 14, logC= log 0.1 = -1
pH = 0.5(pKa+pKw+log C)
=0.5(2.8697+14+-1)
= 7.935
6. The pH of 0.1 M solution of cyanic acid (HCNO) is 2.34. Calculate the ionization constant of the acid
and its degree of ionization in the solution.

HCNO H2O H3O+ CNO-

Initial conc. 1 0 0

1- α α α

Final Conc. c( 1- α) cα cα

c= 0.1 M pH = 2.34

pH= -log[ H3O+]

Answer:
log[ H3O+]= -2.34

[ H3O+] =4.571 x 10-3 mol L-1

[ H3O+] = cα a= [H3O+] = (4.57 x 10-3) =4.57 x 10-2 =0.0457

C 0.1

Kα = cα x cα = cα2
c( 1- α) 1-a

Since a<<<1 1- α =1
Ka = cα2 = 0.1 x (0.0457)2
Ka = 2.088x 10-4 = 2.09 x 10-4
 7. R
E
KEY POINTS D
O
X
R
E
A
C
T
I
O
N
S

The chemical changes that occur when electrons are transferred between reactants are called oxidation –
reduction reactions.

OXIDATION REDUCTION
1. Addition of oxygen 1. Removal of oxygen
2. Removal of hydrogen 2. Addition of hydrogen
3. Addition of an electronegative element 3. Removal of an electronegative element
4. Removal of an electropositive element 4. Addition of an electropositive element
5. Loss of electron 5. Gain of electron

Oxidation number denotes the charge assigned to an atom of a compound or an ion according to some
arbitrary rules. It is equal to the number of electrons in the valence shell of an atom, that are gained or lost
while forming a bond in a compound.
Calculation of oxidation number:
1. Oxidation state (O.S) of all the elements in their elemental form (in standard state) is taken as zero. Ex:
O. S. of elements in Cl2, F2, O2, P4, O3, Fe(s), H2, N2, C(graphite) is zero.
2. Common O. S. of elements of group one (1st) is one. Common O. S. of elements of group two (2nd) is
two.
3. For ions composed of only one atom, the oxidation number is equal to the charge on the ion.
4. The oxidation number of oxygen in most compounds is –2.While in peroxides (e.g., H2O2, Na2O2), each
oxygen atom is assigned an oxidation number of –1, in superoxides (e.g., KO2,RbO2) each oxygen atom is
assigned an oxidation number of –(½).
5. In oxygen difluoride (OF2) and dioxygen difluoride (O2F2), the oxygen is assigned an oxidation number
of +2 and +1,respectively.
6. The oxidation number of hydrogen is +1 but in metal hydride its oxidation no. is–1.
7. In all its compounds, fluorine has an oxidation number of –1.
8. The algebraic sum of the oxidation number of all the atoms in a compound must be zero.
9. In polyatomic ion, the algebraic sum of all the oxidation numbers of atoms of the ion must equal the
charge on the ion.
Oxidation: An increase in the oxidation number
Reduction: A decrease in the oxidation number
Stock notation: The oxidation number is expressed by putting a Roman numeral representing the
oxidation number in parenthesis after the symbol of the metal in the molecular formula. Thus aurous
 chloride and auric chloride are written as Au(I)Cl and Au(III)Cl3. Similarly, stannous chloride and stannic

chloride are written as Sn(II)Cl2andSn(IV)Cl4.

Oxidising agent: A reagent which can increase the oxidation number of an element in a given substance.
These reagents are also called as oxidants .

Reducing agent: A reagent which lowers the oxidation number of an element in a given substance. These
reagents are also called as reductants.

Redox reactions: Reactions which involve change in oxidation number of the interacting species

Types of redox reactions

1. Combination reactions: A reaction in which two atoms or molecules combine together form
molecule or compound. For e.g. C (s) + O2 (g) → CO2 (g)
2. Decomposition reactions: They are the opposite reactions of combination reactions .or
breakdown of a compound into two or more components at least one of which must be in the
elemental state. For e.g. 2H2O(l) → 2H2(g) + O2(g)
3. Displacement reactions: In a displacement reaction, an ion (or an atom) in a compound is
replaced by an ion (or an atom) of another element. For e.g.
(i) Metal displacement : CuSO4(aq.) + Zn(s) → Cu(s) + ZnSO4(aq.)

(ii) Non metal displacement : 2Na(s) + 2H2O(l) → 2NaOH(aq.) + H2(g)

4.Disproportionation reactions :In a disproportionation reaction an element in one oxidation
state is simultaneously oxidized and reduced.
- -
For e.g. P4(s) + 3OH (aq.) +3H2O(l) → PH3(g) + 3H2PO2 (aq.)

Balancing of redox reactions:

Balance the following ionic equation

2– 2– 2–
Cr2O7 (aq) + SO3 (aq) → Cr3+(aq)+ SO4 (aq) (acidic medium)

Method :1 Oxidation Number Method

Step 1: Write the correct formula for each reactant and product.
Step 2: Identify atoms which undergo change in oxidation number in the reaction by
assigning the oxidation number to all elements in the reaction.
Step 3: Calculate the increase or decrease in the oxidation number per atom and for the
entire molecule/ion in which it occurs. If these are not equal then multiply by suitable
number so that these become equal.
Step 4: Ascertain the involvement of ions if the reaction is taking place in water, add H+ or
OH– ions to the expression on the appropriate side so that the total ionic charges of reactants
and products are equal. If the reaction is carried out in acidic solution, use H+ ions in
the equation; if in basic solution, use OH– ions.
Step 5 : Make the numbers of hydrogen atoms in the expression on the two sides equal by
adding water (H2O) molecules to the reactants or products. Now, also check the number of
oxygen atoms. If there are the same number of oxygen atoms in the reactants and
products, the equation then represents the balanced redox reaction.
Step 1: The skeletal ionic equation is:
2– 2– 2–
Cr2O7 (aq) + SO3 (aq) → Cr3+(aq)+ SO4 (aq)

Step 2: Assign oxidation numbers for Cr and S

+6 –2 +4 –2 +3 +6-2

Cr2O72–(aq) + SO32–(aq) → Cr3+(aq)+ SO42–(aq)

Step 3: Calculate the increase and decrease of oxidation number, and make them equal:
2– 2– 2–
Cr2O7 (aq) + 3SO3 (aq) → 2Cr3+(aq)+ 3SO4 (aq)

Step 4: Balance the charge by adding H+as the reaction occurs in the acidic medium,
2– 2– 2–
Cr2O7 (aq) + 3SO3 (aq) + 8H+→ 2Cr3+(aq)+ 3SO4 (aq)

Step 5: Balance the oxygen atom by adding water molecule.

Cr2O72–(aq) + 3SO32–(aq) 8H+→ 2Cr3+(aq)+ 3SO42–(aq)+ 4H2O(l)

METHOD : 2 Half Reaction Method(or) Ion Electron Method

In this method, the two half equations are balanced separately and then added together to give balanced
equation.
Ex : Balance the following ionic equation

MnO4–(aq) + I– (aq) MnO2(s) + I2(s) (basic medium)

Step 1: First we write the skeletal ionic equation, which is

MnO4–(aq) + I– (aq) MnO2(s) + I2(s)

Step 2: The two half-reactions are:
–1 0

Oxidation half cell : I–(aq ) I2 (s)

+7 +4
–
Reduction half cell : MnO4 (aq) MnO2(s)
Step 3: To balance the I atoms in the oxidation half reaction, we rewrite it as:

2I– (aq) I2 (s)

Step 4: To balance the O atoms in the reduction half reaction, we add two water molecules on the right:
MnO4– (aq) MnO2 (s) + 2 H2O (l)

To balance the H atoms, we add four H+ions on the left:

MnO4–(aq) + 4 H+ (aq) MnO2(s) + 2H2O (l)

As the reaction takes place in a basic solution, therefore, for four H+ ions, we add four OH– ions to both
sides of the equation:
– + – –
MnO4 (aq) + 4H (aq) + 4OH (aq) MnO2 (s) + 2 H2O(l) + 4OH (aq)
Replacing the H+ and OH– ions with water, the resultant equation is:
– –
MnO4 (aq) + 2H2O (l) MnO2 (s) + 4 OH (aq)
Step 5 : In this step we balance the charges of the two half-reactions in the manner depicted as:
2I–(aq) I2 (s) + 2e–
– – –
MnO4 (aq) + 2H2O(l) + 3e MnO2(s)+ 4OH (aq)
Now to equalise the number of electrons, we multiply the oxidation half-reaction by 3 and the reduction
half-reaction by 2.
6I–(aq) 3I2 (s) + 6e–

2 MnO4–(aq) + 4H2O (l) +6e– 2MnO2(s)+ 8OH–(aq)

Step 6: Add two half-reactions to obtain the net reactions after cancelling electrons on both sides.
6I–(aq) + 2MnO4–(aq) + 4H2O(l) 3I2(s) +2MnO2(s) +8 OH–(aq)
Step 7: A final verification shows that the equation is balanced in respect of the number of atoms and
charges on both sides.
A redox couple is defined as having together the oxidised and reduced forms of a substance taking part in
an oxidation or reduction half reaction. Represented as
Zn2+/Zn // Cu2+/Cu.

Electrochemical cells are the devices which are used to get

electric current by using chemical reaction .
The potential associated with each electrode is known as
electrode potential. If the concentration of each species
taking part in the electrode reaction is unity (if any gas
appears in the electrode reaction, it is confined to 1
atmospheric pressure) and further the reaction is carried out at 298K, then the potential of each electrode is
said to be the Standard Electrode Potential (SHE).SHE is used to measure electrode potential and its
standard electrode potential is taken as 0.00 V.
Redox titrations :In redox systems, the titration method can be adopted to determine the strength of a
reductant/oxidant using a redox sensitive indicator.
 MULTIPLE CHOICE QUESTIONS :
1. The oxidation number of an atom in the elemental state is
a) -1 b) 0 c) 1 d) 2
2. The oxidation number of an element in a compound is evaluated on the basis of certain rules. Which of
the following rules is not correct in this respect?

(a) The oxidation number of hydrogen is always +1.

(b) The algebraic sum of all the oxidation numbers in a compound is zero.

(c) An element in the free or the un combined state bears oxidation number zero.

(d) In all its compounds, the oxidation number of fluorine is – 1.

3. In the reaction

3Br2 + 6CO3 2–+ 3H2O → 5Br– + BrO3– + 6HCO3–

(a) bromine is oxidised and carbonate is reduced (b) bromine is reduced and water is oxidised
(c) bromine is neither reduced nor oxidised (d) bromine is both reduced and oxidised
4. The oxidation number of iron in Fe3O4 is

(a) +2 (b) +3 (c) 8/3 (d) 2/3

5. H2SO4 acts as a strong oxidising agent. In which of the reaction, is it not acting as an oxidisingagent?
(a) C + 2H2SO4 → CO2 + 2SO2 + 2H2O (b) CaF2 + 2H2SO4 → CaSO4 + 2HF

(c) S + 2H2SO4 → 3SO2 + H2O (d) Cu + 2H2SO4 → CuSO4 + SO2 + 2H2O

–
6. Find the oxidation state of I in H4IO 6

(a) +7 (b) +5 (c) +1 (d) –1

7. In which of the following compounds, ‘Mn’ exhibits highest oxidation state?

(a) KMnO4 (b) K2MnO4 (c) MnO2 (d) MnO

8. Standard electrode potential of three metals X,Y and Z are -1.2V,+0.5V and -3.0Vrespectively.
The reducing power of these metals will be
(a) X>Y>Z (b) Y>Z>X (c) Y>X>Z (d) Z>X>Y
9. The values of x and y in the following reaction,
- - -
x Cl2 + 6OH (hot & conc.) → ClO3 + y Cl +3 H2O are
(a) x = 2, y = 4 (b) x = 5, y = 3 (c) x = 3, y = 5 (d) x = 4, y = 2
10.A standard hydrogen electrode has zero electrode potential because
(a) Hydrogen is easiest to oxidize(b) this electrode potential is assumed to be zero
(c) Hydrogen atom has only one electron (d) hydrogen is the lightest element

Answers : 1(b) 2(a) 3(d) 4(c) 5(b) 6(a) 7(a) 8(d) 9(c) 10(b)
 ASSERTION – REASONING TYPE QUESTIONS
In the following questions a statement of assertion followed by a statement of reason is given. Choose the
correct answer out of the following choices.
(a) Assertion and reason both are correct statements and reason is correct explanation for
assertion.
(b) Assertion and reason both are correct statements but reason is not correct explanation for assertion.
(c) Assertion is correct statement but reason is wrong statement
(d) Assertion is wrong statement but reason is correct statement

1. Assertion (A): Among halogens fluorine is the best oxidant.

Reason (R) : Fluorine is the most electronegative atom.
2. Assertion (A): In the reaction between potassium permanganate and potassium iodide, permanganate
ions act as oxidising agent.
Reason (R) : Oxidation state of manganese changes from +2 to +7 during the reaction.
3. Assertion (A): Lithium is a strong reducing agent
Reason(R): Lithium has lowest value of the standard reduction potential
4.Assertion(A): Zinc liberates hydrogen from a dilute solution of hydrochloric acid.
Reason(R): E0 of Zn is higher than that of H2

5.Assertion(A): The decomposition of hydrogen peroxide to form water and oxygen is an example of a
disproportionation reactions.
Reason(R): The oxygen of peroxide is in -1 oxidation state and it converted to zero oxidation
state in O2 and -2 oxidation in water
Answers 1 (b) 2(c) 3(a) 4(c) 5(a)

2 MARK QUESTIONS
1. Show that F cannot undergo disproportionation reaction?
F is most electronegative element and cannot possess three oxidation states. Hence it cannot undergo
disproportionation reactions.

2. What is a redox couple?

Ans. A redox couple consists of oxidized and reduced form of the same substance taking part in
an oxidation or reduction half reaction.

3. Write formulas for the following compounds:

(a) Mercury(II) chloride (b) Iron(II)sulphate

Ans a) HgCl2 b) FeSO4

 4. Consider the elements: Cs, Ne, I and F

(a) Identify the element that exhibits only negative oxidation state.
(b) Identify the element that exhibits only positive oxidation state.
(c) Identify the element that exhibits both positive and negative oxidation states.
(d) Identify the element which exhibits neither the negative nor does the positive
oxidation state.
Ans a - F b - Cs c- I d-Ne
5.Given the standard electrode potentials,
K+/K = –2.93V, Ag+/Ag = 0.80V, Hg2+/Hg = 0.79V, Mg2+/Mg = –2.37V, Cr3+/Cr = –0.74V
arrange these metals in their increasing order of reducing power.

Ans : Lower the electrode potential, better the reducing agent .Therefore increasing order of reducing
power is Ag< Hg< Cr<Mg<K

6. Define EMF of the cell.

Ans. It is defined as the difference in the electrode potentials of the two half cells when the cell is not
sending current through the circuit.
7. Arrange the following metals in which they displace each other from the solution of their salts: Al,Cu, Fe, Mg, Ag
and Zn.
Ans. Metals which have lower electrode potentials can displace others which have higher
electrode potentials from the solutions of their salts. Thus the order is: Mg, Al, Zn, Fe, Cu, Ag.
8.Using Stock notation, represent the following compounds: HAuCl4, FeO, Fe2O3 and CuI.
Ans. HAu(III)Cl4 , Fe(II)O, Fe2(III)O3, Cu(I)I respectively.
9.In the reaction given below, identify the species undergoing oxidation and reduction
(i) H2S (g) +Cl2 (g) → 2HCl (g) +S (s) (ii) 2Na(s) + H2 (g) → 2NaH(s)

Ans (i) H2S is oxidized to S while Cl2 is reduced to HCl

(ii) Sodium is oxidized to sodium ion while hydrogen is reduced to hydride ion.
10.Suggest a scheme of classification of the following redox reactions
(i) N2(g) + O2 (g) → 2NO(g)

(ii) 2 Pb(NO3)2(s) → 2PbO(s) + 4NO2(g) + O2(g)

(iii) NaH(s) +H2O (l) → NaOH(aq.) +H2(g)

- - -
(iv) 2NO2(g) + 2OH (aq.) → NO2 (aq.) +NO3 (aq.) +H2O(l)

Ans. (i) Combination reaction(ii) Decomposition reaction

(iii) Displacement reaction(iv) Disproportionation reaction
 11. What is galvanization?
Ans: Coating of a less reactive metal with a more reactive metal e.g.- coating of iron surface with Zn to
prevent rusting of iron.

12. Calculate the standard e.m.f. of the cell formed by the combination of Zn/Zn2+ ⎤⎤ Cu2+/Cu.

Solution : E0cell = E0cathode – E0anode =0.34 – (-0.76) = 1.10V.

3 MARK QUESTIONS
1. Depict the galvanic cell in which the reaction Zn(s) + 2Ag +(aq) → Zn2+(aq) +2Ag(s) takes place,Further show:
(i) which of the electrode is negatively charged,
(ii) the carriers of the current in the cell, and
(iii) individual reaction at each electrode

Ans :i) Oxidation occurs at Zinc electrode .Therefore Zinc electrode is negatively charged.
(ii) The ions carry current. The electrons flow from Zn to Ag while the current flows from Ag to Zn.
(iii) Zn →Zn2+ + 2 e- (Anode) Ag+ + e- → Ag (Cathode)
2. What is meant by ‘Salt Bridge’? Give its function.

Ans : Salt bridge is a U-shaped tube. It consists of Agar-agar and inert electrolyte like KCl or KNO3.
Functions: (i) To complete the circuit
(ii) It helps to maintain the electrical neutrality of the solutions in the two half cells.
3.Write short notes on :
(a) Electrochemical series (b) redox reactions (c) oxidizing agents
Ans :(a) Electrochemical series :- arrangement of metals(non-metals also) in increasing order of their
reducing power or vice versa.
(b) Reactions in which both Oxidation and reduction take place simultaneously are REDOX REACTIONS.
(c) Oxidizing agents : chemical specie which can oxidize the other one or can reduce itself.
4.Account for the followings:
(i) Sulphur exhibits variable oxidation states.
Ans. Due to the presence of vacant d - orbitals in S
(ii) Fluorine exhibits only -1 oxidation state.. Ans . It is most electronegative element
(iii) oxygen can’t extend its valency from 2.
Ans. Small size and non-availability of vacant d-orbitals in Oxygen.
5.Identify the oxidizing and reducing agents in the following equations:
(i) Fe + H2SO4→FeSO4 + H2

(ii)H2 + Cl2 →2HCl

(iii) MnO2 + 4HCl→MnCl2 + 2H2O + Cl2
 Ans :(i) O.A. =H2SO4 ; R.A.= Fe (ii) O.A. = Cl2; R.A.=H2 (iii)O.A. = MnO2; R.A. =HCl
6.What is SHE? What is its use? Explain with the help of a diagram.
Ans :Standard Hydrogen Electrode (SHE) has been selected to have zero standard potential at all
temperatures. It consists of a platinum foil coated with platinum black (finely divided platinum) dipping
partially into an aqueous solution in which the activity (approximate concentration 1M) of hydrogen ion is
unity and hydrogen gas is bubbled through the solution at 1 bar pressure. The potential of the other half cell
is measured by constructing a cell in which reference
electrode is standard hydrogen electrode. The potential of the
other half cell is equal to the potential of the cell.
8. (i) Define electrochemical series .
(ii) Write down the reaction occurring in Daniel cell . What
is the direction of flow of current in it ?
Ans. :- The arrangement of elements in the order of
increasing standard reduction potential is known as
electrochemical series .
(i) At Anode :- Zn → Zn+2 + 2e-

(ii) At Cathode :- Cu+2 + 2e- → Cu

The current will flow from Cu electrode to Zn electrode
CASE BASED QUESTIONS -4 MARKS
Read the following passage and answer the questions that follow:

Redox reactions are important class of reactions which are taking place in our daily life. Metals are good
reducing agents because they can lose electrons easily whereas non-metals are good oxidising agents which
can gain electrons easily. In electrolytic cells, electricity is passed to bring about redox reaction. All
rechargeable batteries act as electrolytic cells while recharging. Electrochemical cells produce electricity as
a result of redox reaction. Salt bridge is used in electrochemical cell to complete internal circuit and
prevents accumulation of charges.

1. In an Electrochemical Cell ,Oxidation takes place at and Reduction takes place at

a) Cathode , Anode b) Anode , Cathode c) Anode , Anode d) Cathode, Cathode
2. What is direction of flow of current and electrons?
a) Electrons flow from anode to cathode whereas current flows from cathode to anode
b) Electrons flow from cathode to anode whereas current flows from anode to cathode
c) Electrons flow from anode to cathode and current also flows from anode to cathode
d) Electrons flow from cathode to anode and current also flows from anode to cathode
3. Electrochemical cell is
a) The cell in which electrical energy is converted into chemical energy
 b) The cell in which chemical energy is converted into electrical energy
c) The cell in which chemical energy is converted into mechanical energy
d) The cell in which mechanical energy is converted into chemical energy
4.E°Zn2+/Zn= –0.76V, What is meaning of –ve value of reduction potential?

a) Zn is stronger oxidising agent than H2

b) Zn is weaker reducing agent than H2 .

c) Zn is stronger reducing agent than H2

d) None of the above
Ans : 1(b) 2(a) 3(b) 4(c)

5 MARKS QUESTIONS

1.Balance the equation

– - 2+
MnO4 + I → Mn +I2 + H2O by ion electron method in acidic medium.
Ans :
Step-I Balancing of reduction half reaction by adding protons and electrons on LHS and more
water molecules on RHS: 8H++ MnO4– +5e-→ Mn2+ + 4H2O
Step-II Balancing of oxidation half reaction by adding electrons on RHS: 2I-→ I2 +2e-
Step-III To multiply the Oxidation Half Reaction by 5; Reduction Half reaction by2 and to add both
to get overall redox reaction(cancellation of electrons of RH & OH reactions):
[8H+(aq)+ MnO4–(aq) +5e-→ Mn2+(aq) + 4H2O(l)] x 2
[ 2I-→ I2 +2e-] x 5
OVERALL : MnO4–(aq) +5Fe2+(aq) + 8H+(aq) → Mn2+(aq)+ 5Fe3+(aq) + 4H 2O(l)
HOTS
1. Justify that the reaction: 2Cu2O(s) + Cu2S(s) → 6Cu(s) + SO2(g) is a redox reaction. Identify thespecies oxidised/
reduced, oxidant and /reductant.

Ans. Cu2O helps sulphur in Cu2S to increase its oxidation number, therefore, Cu(I) is an oxidant; and

sulphur of Cu2S helps copper both in Cu2S itself and Cu2O to decrease its oxidation number; therefore,

sulphur of Cu2S is reductant.

2. Match the items in Column I with relevant items in Column II

Ans .:- (i) - (e) , (ii) - (d) , (iii) - (c) , (iv) - (b) , (v) - (f)
2. Write short note on working of SHE .
Ans. (I)It can behave as anode and cathode depending upon another electrode taken.

(a) When it acts as anode, reaction will be :- H2 → 2H+ + 2e-

Representation will be :-Pt, H2 (1atm.) / H+ ( 1M)
(b) When it acts as cathode, reaction will be
2H+ + 2e- → H2 Representation will be :- / H+ ( 1M) / H2 (1atm.), Pt
3. In the following cell : - Cu / Cu+2 (1M) // Ag+ (1M) / Ag Write down each half cell reactionand overall
reaction .

Ans. :- At anode :- Cu → Cu+2 + 2e-

At Cathode :- 2 Ag+ + 2e- → 2Ag
Overall reaction :- Cu + 2 Ag+ → Cu +2 + 2Ag
4. Using the given standard electrode potentials predict if the reaction between the following isfeasible :
i) Fe3+ and Cu ii) Ag and Fe3+

Given : EoCu+2 / Cu = 0.34 V, EoFe+3 / Fe2+ = 0.77 V , EoAg+/Ag = + 0.80V

Ans. :- (i) Fe3+ + Cu → Fe2+ + Cu2+

Eo Cell = EoFe+3 / Fe2+ - EoCu2+/Cu

Eo Cell = 0.77 - 0.34 = 0.43 V

o
As E Cell comes out to be +ve so reaction between Fe 3+ and Cu is feasible .

(ii) Fe3+ + Ag → Fe2+ + Ag

+3 2+
Eo Cell = EoFe o
/ Fe - E Ag+/Ag

Eo Cell = 0.77 – 0.80 = - 0.03 V

As EoCell comes out to be - ve so reaction between Fe3+ and Ag is not feasible

 8. ORGANIC CHEMISTRY SOME BASIC PRINCIPLES AND TECHNIQUES

Organic compounds are the hydrocarbons and their derivatives and organic chemistry is that branch of
chemistry that deals with the study of these compounds.
Synthesis of first Organic compounds: Wohler synthesized an organic compound, urea from an inorganic
compound, ammonium cyanate.

Tetravalency of Carbon :The atomic number of Carbon is 6 and its electronic configuration is 2,4 i.e. it
has 4 valence electrons. It can share 4electrons with the other atoms to form 4 covalent bonds. It is called
tetravalency of carbon.

Catenation- The self-linking property of carbon is known as catenation. This is the main reason of
existence of such large number of compound

The Shapes of Carbon Compounds: CH4 is sp3 hybridized and has tetrahedral structure. In ethene, each
carbon is sp2hybridized and it has planar structure. In C2H2, carbon is sp hybridized and it is linear
molecule.

Effect of hybridization on bond length and bond enthalpy: The bond length and bond strength depends
upon hybridization.
sp hybridized: Carbon has 50% s character, and hence it is close to the nucleus and forms shorter and
stronger bond. It is most electronegative
sp2hybridized: Carbon has 33% s- character, and hence it is less close to the nucleus and forms slightly
longer and less strong bonds than sp hybridized carbon. It is less electronegative than sp hybridized.
sp3 hybridized: Carbon has 25% s-character and hence it is least close to the nucleus and forms longer and
least strong bonds. It is bigger in size and is less electronegative than sp2 and sp hybridized carbon.

Characteristic features of 𝑟 –bonds:

i) Pi-bond is formed by sideways or lateral overlapping of parallel p-orbitals.
ii) The p-orbitals should be parallel and perpendicular to the plane of the molecule.
iii) Rotation of C=C is restricted.
iv) The electron cloud of the pi-bond lies above and below the plane of the bonding atom.
This results in the electrons being easily available to attacking agents. bonds are more reactive
than Sigma bond in unsaturated molecules.
 STRUCTURAL REPRESENTATIONS OF ORGANIC COMPOUNDS:

Complete structural formula:

Condensed structural formula:

Bond-line structural formula:

2-bromo butane 3-methyl octane

Classification of organic compounds

Functional group: Atom or group of atoms that largely decide the chemical properties.
Class of organic Name of functional Structure
compounds group

Homologous Series:A group or a series of organic compounds each containing a characteristic functional
group,show a gradation in physical and similarity in chemical properties.
The members of the series are called homologues. It can be represented by general molecular formula and
the successive members differ from each other in molecular formula by a –CH2 unit.
Eg : Alkanes, alkenes, alkynes.

NOMENCLATURE OF ORGANIC COMPOUNDS:

The IUPAC name consists of four parts:
Prefix Word root Suffix(primary, secondary)
Number of carbons Word root Number of carbons Word root
One carbon Meth Six carbons Hex
Two carbons Eth Seven carbons Hept
Three carbons Prop Eight carbons Oct
Four carbons But Nine carbons Nona
Five carbons Pent Ten carbons Dec
Primary suffix: Indicates saturation or unsaturation of the compound.
Saturation: All single bonds
Unsaturation: At least one carbon - carbon double bond or one carbon -carbon triple bond
Saturated / Unsaturated Primary suffix
All single bond (alkanes) ane
C =C (alkenes) ene
C≡C (alkynes) yne
Secondary suffix: Indicates functional group present in the organic compound(many functional groups are
already mentioned in the previous topics)
Suffixing functional groups Secondary suffix
-OH ol
-CHO al
>C=O one
-COOH oic acid

PREFIX: Some functional groups like halogens are prefixing functional groups
Prefixing functional groups Prefix
-Cl Chloro
-Br Bromo
-I Iodo
-OR Alkoxy
-NO2 Nitro
Order of writing the name of the organic compounds.
 NOMENCLATURE OF ALKANES
Straight chain alkanes: The names of such compounds is based on their chain structure, and end with
suffix ‘-ane’ and carry a prefix indicating the number of carbon atoms present in the chain.
Branched chain hydrocarbons:
1) The longest carbon chain in the molecule is identified.
2) The numbering is done in such a way that the branched carbon atoms get the lowest possible value.
3) The names of the alkyl groups attached as a branch are then prefixed to the name of the parent alkane
and its position is indicated by numbers.
4) The lower number is given to the first in alphabetical order.
5) The carbon atom of the branch that attaches to the root alkane is numbered
Organic compounds having Functional Groups: The longest chain of carbon atoms containing the
functional groups is numbered in such a way that the functional group attached to the carbon atom gets the
lowest possible number in the chain.
When there are more functional groups then a priority order is followed as:
-COOH, -SO3H, -COOR,- COCl, -CONH2, -CN, -HC=O, =C=O, -OH, -NH2, -C=C, -CΞ C-.
Prefix, word root, primary suffix, secondary suffix
Formula Prefix Word root Primary Secondary suffix (pri Name
suffix suffix e to be replaced
by s. suffix)
CH4 Meth Ane Methane
CH3-CH3 Eth Ane Ethane
CH3-CH2-CH3 Prop Ane Propane
CH3-OH Meth Ane ol Methanol
CH3-CH2-OH Eth Ane ol Ethanol
HCOOH Meth Ane oic acid Methanoic acid
CH3-COOH Eth Ane oic acid Ethanoic acid
HCHO Meth Ane al Methanal
CH3-CHO Eth Ane al Ethanal
CH3-Cl Chloro meth Ane Chloromethane
CH3-CO-CH3 Prop Ane one Propanone
CH2=CH2 Eth Ene Ethene
CH3-CH=CH2 Prop Ene Propene
CH≡CH Eth Yne Ethyne
CH3-C≡CH Prop Yne Propyne

Aromatic compounds:
Nomenclature of aromatic compounds: Benzene forms only one mono-substituted derivative. It can form
three di-substituted derivatives ;ortho(1,2), meta(1,3) ,para(1,4).
ISOMERISM
Two or more compounds having the same molecular formula but different physical and chemical properties
are called isomers and this phenomenon is called isomerism.
Classification of isomerism: Isomerism is basically classified into 2 types i.e,
1) Structural isomerism
2) Stereo isomerism

Structural isomerism: Compounds having same molecular formula but different structures are called
Structural isomers..
Chain isomerism: When two or more compounds having same molecular formula but different carbon
skeletons, these are referred to as chain isomers and this phenomenon is called chain isomerism.
Eg : Butane and isobutane.
Position Isomerism: Compounds which have the same structure of carbon chain but differ in position of
double or triple bonds or functional group are called position isomers and this phenomenon is called
Position Isomerism.
eg :CH3-CH2-CH=CH2 ,CH3-CH = CH – CH3
Functional Isomerism: Compounds which have the same molecular formula but different functional group
are called functional isomers and this phenomenon is called functional Isomerism
eg :CH3 – CH2 – OH , CH3 – O – CH3
Metamerism: It is due to the presence of different alkyl groups on either side of functional group in the
molecule eg. C4H10O represents C2H5OC2H5 and CH3OC3H7.

FISSION OF COVALENT BOND

Heterolytic cleavage: In this cleavage the bond breaks in such a way that the shared pair of electron
remains with one of the fragment.
 A species having a carbon atom possessing sextet of electrons and a positive charge is called a carbocation
( carbonium ion). The C + H3 ion is known as a methyl cation or methyl carbonium ion. Carbocations are
classified as primary, secondary or tertiary depending on whether one, two or three carbons are directly
attached to the positively charged carbon.
The observed order of carbocation stability is:
C + H3< CH3C + H2< (CH3)2C + H < (CH3 ) 3C + .
The heterolytic cleavage can also give a species in which carbon gets the shared pair of electrons. For
example, when group Z attached to the carbon leaves without electron pair, the methyl anion is formed.
Such a carbon species carrying a negative charge on carbon atom is called carbanion. Carbon in carbanion
is generally sp 3 hybridised . Carbanions are also unstable and reactive species.

Homolytic Cleavage: This involves breaking of a covalent bond in such a way that each atom separates
one electron of the shared pair.

Alkyl radicals are classified as primary, secondary, or tertiary. Alkyl radical stability increases from
primary to tertiary

Attacking reagents:
Nucleophiles: A reagent that brings an electron pair is called nucleophile eg –OH- ,-CN-
Electrophiles: A reagent that takes away an electron pair is called electrophile eg

Electronic displacements:
Inductive Effect: The permanent electron displacement along a chain due to the presence of a polar
covalent bond that is bond polarity is known as inductive effect. If an atom or group attracts electron more
strongly than hydrogen, it is said to have –I Effect.

If an atom or group of atom attracts electron less strongly than hydrogen it is said to have +I Effect.
Resonance Effect: The polarity produced in the molecule by the interaction of two pi bonds or between a
pi bond and lone pair of electron present on an adjacent atom.
There are two types of resonance effect:
1) Positive resonance effect: In this effect the transfer of electrons is away from an atom or substituent
group attached to the conjugated system. The atoms or groups which shows +R effect are halogens,
-OH , -OR,- NH2.
2) Negative resonance effect: In this effect the transfer of electrons is towards the atom or substituent
group attached to the conjugated system. The atoms or groups which shows -R effect are –COOH , -CHO ,
-CN.
Electrometric effect: It involves the complete transfer of shared pair of electrons to one of the atoms
joined by a multiple bond at the requirement of the attacking reagent. It is temporary effect.
 Hyperconjugation: Electron release by an alkyl group attached to unsaturated system. There should be at
least one-H at alpha carbon with respect to sp2 hybrid carbon.

METHODS OF PURIFICATION OF ORGANIC COMPOUNDS:

Sublimation: This method is used to separate the sublimable compounds from non sublimable compounds.
Crystallisation: This method is based on the difference in the solubilities of compound and impurities in a
suitable solvent.
Distillation: This method is used to separate volatile liquids from non-volatile liquids and liquids having
sufficient difference in their boiling points.
Fractional distillation: If the boiling points of two liquids is not much, they are separated by this method.
Distillation under reduced pressure: This method is used to purify liquids having high boiling points and
decomposes at or below their boiling points.
Steam distillation: This method is used to separate substances which are steam volatile and are immiscible
with water
Differential Extraction: When an organic compound is present in an aqueous medium it is separated by
shaking it with organic solvent in which it is more soluble than in water.

Chromatography:
Adsorption Chromatography: It is based on the fact that different compounds are adsorbed on an
adsorbent to different degrees. Silica gel or alumina is used as adsorbents.
Partition Chromatography: It is based on the continuous differential partitioning of components of a
mixture between stationary and mobile phase.

QUALITATIVE ANALYSIS OF ORGANIC COMPOUNDS

Detection of carbon and hydrogen: The carbon and hydrogen present in the organic compound is
deducted by heating the compound with copper (II) oxide in a hard glass tube when carbon present in the
compound is oxidized to carbon dioxide which can be tested with lime water and hydrogen converted to
water which can be tested with anhydrous copper sulphate which turns blue.

Detection of other elements:

Sodium fusion extract: A small piece of dry sodium metal is heated with an organic compound in a fusion
tube for 2-3 minutes and the red hot tube is plunged into distilled water contained in a China dish the
content of the China dish is boiled ,cooled and filtered. The filtrate is called as sodium fusion extract.

Test for Nitrogen: The sodium fusion extract is boiled with iron II sulphate and then acidified with
Concsulphuric acid, the formation of Prussian blue colour confirms the presence of nitrogen.

Test for Sulphur: The sodium fusion extract is acidified with acetic acid and lead acetate is added to it. A
black precipitate of lead sulphide indicates the presence of sulphur.
 Test for halogens: The sodium fusion extract is acidified with nitric acid and then treated with silver
nitrate. A white precipitate, soluble in ammonium hydroxide shows the presence of chlorine, a yellowish
ppt. sparingly soluble in ammonium hydroxide shows the presence of bromine, a yellowish ppt. insoluble
in ammonium hydroxide shows the presence of iodine.

QUANTITIVE ANALYSIS
1]Carbon and Hydrogen
Let the mass of organic compound be m g. Mass of water and carbon dioxide produced be m1 and m2 g
respectively;

Dumass method: A known mass of organic compound is heated with excess of CuO in an atmosphere of
carbon dioxide, when nitrogen of the organic compound is converted into N2 gas .The volume of N2thus
obtained is converted into STP and the percentage of nitrogen is determined by the following equation:

Kjeldahl’s Method: A known mass of organic compound is heated with concentrated sulphuric acid in
presence of potassium suplhate and little copper sulphate in a Kjeldahl flask when nitrogen is present in
the organic compound is converted into ammonium sulphate. Ammonium sulphate thus obtained is boiled
with excess of NaOH to liberate ammonia gas which is absorbed in an excess of standard acid such as
sulphuric acid or HCl. The volume of the acid unused is found by titration against a standard alkali solution
from the volume of the acid used the percentage of nitrogen is determined by applying the equation.

Estimation of Halogen:
Carius method: A known mass of an organic compound is heated with fuming nitric acid in the presence
of silver nitrate contained in a hard glass tube known as Carius tube, in a furnace. Carbon and hydrogen
present in the compound are oxidised to carbon dioxide and water. The halogen present forms the
corresponding silver halide (AgX). It is filtered, washed, dried and weighed.
Estimation of sulphur:

Estimation of phosphorous:

Estimation of oxygen:

MULTIPLE CHOICE QUESTIONS

1) The displacement of electrons in a multiple bond in the presence of attacking reagent is called
(A) Inductive effect (B) Electromeric effect (C) Resonance (D) Hyper conjugation
Answer: b) Electromeric effect
2) Homolytic fission leads to the formations of
a) nucleophile b) carboanion c) free radical d) carbocation
Answer: c) free radical
3) Which of the following cannot be represented by resonance structures?
(A) Dimethyl ether (B) Nitrate anion (C) Carboxylate anion (D) Toluene
Answer: (A) Dimethyl ether
4) Which one is strongest acid among following options?
(A) CH2FCOOH (B) CH2ClCOOH (C) CHCl2COOH (D) CHF2COOH
Answer:(D) CHF2COOH
5) Which of the following behaves both as a nucleophile and as an electrophile?
(A) CH3C ≡ N (B) CH3OH (C) CH2 = CHCH3 (D) CH3NH2
Answer:(A) CH3C ≡ N
6) The I.U.P.A.C. name of

(A) 3–Methyl cyclohexene (B) 1–methyl cylohex–2–ene.

C) 6–methyl cyclohexene (D) 1–methyl cyclohex5–ene.
Answer: A) 3–Methyl cyclohexene

7) The increasing order of electron donating inductive effect of alkyl group is:
(A) −H<−CH3<−C2H5<−C3H7 (B) −H>−CH3>−C2H5>−C3H7
(C) −H<−C2H5<−CH3<−C3H7 (D)−H>−C2H5>−CH3>−C3H7
Answer: (A) −H<−CH3<−C2H5<−C3H7
8) Which one is the correct order of acidity?
(a) CH2=CH2> CH3-CH=CH2> CH3C≡CH > CH≡C
(b) CH≡CH > CH3-C≡CH > CH2=CH2> CH3CH3
(c) CH≡CH > CH2=CH2 > CH3-C≡CH > CH3-CH3
(d) CH3-CH3> CH2=CH2> CH3-C≡CH > CH≡CH
Answer: (b) CH≡CH > CH3-C≡CH > CH2=CH2> CH3CH3
9) Which of the ion is the most resonance stabilized?
a) C2H5O - b) C6H5O-
c) (CH3)3CO- d) (CH3)2CHO-
Answer: b) C6H5O-
10) Which one of the following is least stable?
a) C H3 b) HC≡C c) (C6H5)3C d) (CH3)3C

Answer: d) (CH3)3C

ASSERTION AND REASON QUESTIONS

In the following questions the assertion and reason have been put forward read the statements carefully and
choose the correct answer from the following choices
(A) Both A and R are correct and R is the correct explanation of A.
(B) Both A and R are correct but R is not the correct explanation of A.
(C) Both A and R are not correct.
(D) A is not correct but R is correct.

1) Assertion: IUPAC name of compound CH3CH = CH – CHO is But–2– enal.

Reason: Functional group gets preference over multiple in IUPAC name ofa compound.
Answer: (A) Both A and R are correct and R is the correct explanation of A.

2) Assertion: pi– bond stronger than sigma bond.

Reason: The extent of overlapping in sigma bond is greater than in pi– bond.
Answer:(D) A is not correct but R is correct.
3) Assertion: Though the central atom of both NH3 and H2O molecule are sp3 hybridized, yet H−N−H
bond angle is greater than that of H−O−H.
Reason: This is because nitrogen atom has one lone pair and oxygen atom has two lone pairs.

Answer: (A) Both A and R are correct and R is the correct explanation of A.
4) Assertion: Tertiary carbonations are generally formed more easily than primary carbocations.
Reason: Hyperconjugation as well as inductive effect due to additional Alkyl groups stabilize
tertiary carbocations
Answer: (A) Both A and R are correct and R is the correct explanation of A.

5) Assertion: Alkyl carbanions like ammonia have pyramidal shape.

Reason: The carbon atom carrying negative charge has an octet of electrons.
Answer:(B) Both A and R are correct but R is not the correct explanation of A.

6) Assertion: The components of a mixture of red and blue ink can be separated by distributing the
components between stationary and mobile phase in paper chromatography.
Reason: The colored components of ink migrates at different rates because paper selectively retains
different components according to the difference in the partition between the two phases.
Answer: (A) Both A and R are correct and R is the correct explanation of A.

7) Assertion (A): Pent- 1- ene and pent- 2- ene are position isomers.
Reason (R): Position isomers differ in the position of functional group or a substituent.
Answer: (A) Both A and R are correct and R is the correct explanation of A.

8) Assertion: a mixture of ortho-nitrophenol and para- nitrophenol can be separated by steam

distillation
Reasons: para -nitrophenol is steam volatile while ortho -nitro phenol is not steam volatile.
Answer: (D) A is correct but R is not correct.

9) Assertion: Heterolytic fission involves the breaking of a covalent bond in such a way that both the electrons
of the shared pair are carried away by one of the atoms.
Reason: Heterolytic fission occurs readily in polar covalent bonds. Heterolytic fission involves the
breaking of a covalent bond in such a way that both the electrons of the shared pair are carried away by one
of the atoms.
Answer:(B) Both A and R are correct but R is not the correct explanation of A.

10) Assertion:The order of stability of carbocation is 3>2>1.

Reason:Carbon atom in carbocation is in sp3 state of hybridization.
Answer: (D) A is correct but R is not correct.

2mark question

1) Draw the structure of the following compounds

a) Hex-3enoic acid
b) 2-chloro-2-methyl butan-1-ol
a) CH3-CH2-CH=CH-CH2-COOH b)CH3-CH2-CCl(CH3)-CH2-OH

2. Explain.Why (CH3)3 –C+ is more stable than CH3-CH2+and CH3+ is the least stable cations.
 Hyper conjugation interaction in (CH3)3 –C+ is greater than inCH3-CH2+ has(CH3)3 –C+
9 CH bonds. In CH3+,vacant p-orbital is perpendicular to the plane in which C-H- lie; hence cannot
overlap with it thus C+H3 lacks hyper conjugative stability.

3) Give the number of sigma and pi bond in the following molecules

a) CH3-NO2 b) HCONHCH3
a) 6 sigma and 1𝑟bond
b) 8 sigma and 1 𝑟bond

4) It is not advisable to use sulphuric acid in place of acetic acid for acidification while testing sulphur by
lead acetate test. Give reason.
Lead acetate on reacting with sulphuric acid will give a white precipitate of lead sulphate which interfere
in the detection of sulphur.

5) Under what condition can the process of steam distillation is used.

Steam distillation is used to purify the liquids which has steam volatile and immiscible in water.
6) Suggest a method to purify
(i) Kerosene containing water
(ii) A liquid that decomposes at its boiling point.

i) By solvent extraction using a separating funnel.

ii)Distillation under reduced pressure.

7) 0.15g of an organic compound gave 0.12g of AgBr by carius method. Find the percentage of bromine
in the compound.
Mass of AgBr formed = 0.12g
188 g of AgBr contains bromine = 80g.
Therefore, 0.12g of AgBr will contain bromine
= 80×0.12/188
= 0.051 g
Percentage of bromine = 0.051× 100/0.15
= 34%

8. Define homologous series?

A group or a series of organic compounds each containing a characteristic functional group forms a
homologous series and the members of the series are called homologues. The members of a homologous
series can be represented by general molecular formula and the successive members differ from each other
in molecular formula by a –CH2 unit.

9. What is the cause of geometrical isomerism in alkenes?

In alkenes there is a double bond between two carbon atoms, due to presence of pi-electrons, the rotation
between these C=C is not possible. Thus, geometrical isomerism in alkenes exists due to nonrotating
double bond.

10.a. Define Sodium fusion extract.

b.Why is sodium fusion extract made acidic with acetic acid before the addition of lead acetate
in the detection of sulphur?
 a. A small piece of dry sodium metal is heated with an organic compound in a fusion tube for 2-3
minutes and the red hot tube is plunged into distilled water contained in a China dish the content of
the China dish is boiled ,cooled and filter this filtrate is called as sodium fusion extract.
b. Lead acetate is hydrolyzed by NaOH present in Sodium extract. It is neutralized first with acetic
acid before the addition of lead acetate.

Three marks question

1. a. Name the type of isomerism exhibited by acetone and propanal.

b. Distinguish between position and functional isomerism with example.
a) Functional isomerism
b) The isomers which differ in position of functional groups are called position isomers.
e.g But-1-ene and But-2-ene
The isomers which differ in functional group are called functional group isomers.
e.g C2H5OH and CH3OCH3

2. a. Which distillation method is used to separate a mixture of o-nitro phenol and p-nitro phenol?
b. Distinguish between Steam distillation and distillation under reduced pressure.
a. Steam Distillation
b. Steam distillation is used to separate substances which are steam volatile and are immiscible
with water.
Distillation under reduced pressure is used to purify those liquids which decompose at or below
their normal boiling points.
3. Write IUPAC name of each of the following compound.
a. b. c. CH2 =CHCH2CH (OH)CH3 .

.
a.3,5-Dimethyl-4-propylheptane b. 4-chloro-2,2-dimethylpentane c.) Pent-4-en-2-ol.

4. a) 0.546 g of silver Bromide is obtained from 0.5372 g of an organic .compd. Calculate the percentage of
Bromine. (At. mass Br=80g/mol Ag =108g/mol)
b) How is the presence of chlorine detected in an organic .compound?
a) Mass of org compound = 0.5372g Mass of AgBr = 108 +80=188g/mol

b) Sodium fusion extract of the given organic compd. is treated with dilute nitric acid and then Silver
nitrate solution is added. Formation of white ppt indicates the presence of Chlorine in the given
organic compound
.
5. Distinguish between inductive effect and resonance effect.
Inductive effect Resonance effect
1.Involves displacement of sigma electrons and 1. Involves delocalization of pi electrons and lone
hence occurs only in saturated compound pair and hence occurs in unsaturated compounds
and conjugated systems.
2. Electronegativity difference induces this effect 2. It takes place due to interaction between two pi
towards the more electronegative atom to give bonds or a pi bond and a lone pair of electron
partial +ve or –ve charges.
3.Inductive effects are transmitted over short 3. The resonance effects are transmitted all along
distances in saturated carbon chains and the the length in the conjugated system. The electron
magnitude of the effect decreases rapidly as the pair is completely transferred to form positive and
distance from the halogen atom increases negative charge centres.

6. In Dumas’ method for estimation of nitrogen, 0.3g of an organic compound gave 50mL of nitrogen
collected at 300K temperature and 715mm pressure. Calculate the percentage composition of nitrogen in
the compound. (Aqueous tension at 300K=15 mm)
Volume of nitrogen collected at 300K and 715mm pressure is 50 mL
Actual pressure = 715-15 =700 mm
Volume of nitrogen at STP= 273 X700X 50
300X 760

== 41.9 mL

22,400 mL of N2 at STP weighs = 28 g

41.9 mL of nitrogen weighs= 28 X41.9

22400
Percentage of nitrogen = 28X 41.9X100
22 ,400X0.3
=17.46%

7. a. Why is organic compound fused with Na metal during detection of nitrogen, sulphur halogens?
B. Sometimes red colouration is obtained when Ferric Chloride is added during Lassaigne’s test for
detection of nitrogen. Why?
Organic compound is fused with sodium metal to convert nitrogen, sulphur,halogens present
it into ionisable form.
When nitrogen and sulphur both are present in an organic compound, sodium thiocyanate is formed
which gives red colouration with FeCl3.

8. During estimation of nitrogen present in an organic compound by Kjeldahl’s method, the ammonia
evolved from 0.5 g of the compound in Kjeldahl’s estimation of nitrogen, neutralized 10 mL of 1 M
H2SO4 . Find out the percentage of nitrogen in the compound.
9. On complete combustion, 0.246 g of an organic compound gave 0.198g of carbon dioxide and 0.1014g
of water. Determine the percentage composition of carbon and hydrogen in the compound.

Percentage of carbon =12 X0.198X100

44X0.246
=21.95%
Percentage of hydrogen =2 X0.1014X 100
18X0.246
=4.58%
10. a)Define the term functional group
b) What is the functional group of an aldehyde and an nitro compound.
c) What is the state of hybridization of carbon atom in CH3-CH=CH-CH3.
a) The atom or group of atom attached to carbon chain which is responsible for specific chemical
properties of organic compounds.
b) –CHO,-NO2
c) Sp3 , sp2 ,sp2 ,sp3.
5 marks questions
Q.No 1
a) What are electrophiles? Give an example.
b) Explain the principle of paper chromatography
c) Write the chemistry of lassaigne’s test for qualitative analysis of nitrogen

a. The species which are positively charged or electron deficient are called electrophiles(electron seeking
agent).example: H+, Cl+,AlCl3 .
b. In paper chromatography, chromatographic paper dipped in solvents act as a stationary phase whereas
mixture of compounds dissolved in suitable solvents forms the mobile phase. Different compounds have
different adsorbing power, therefore they move with different speeds and gets separated.
c. Lassaigne’s test for qualitative analysis of nitrogen: Fuse the organic compound with sodium metal.
sodium reacts with C and N present in organic compound to form NaCN.

Add FeSO4 to lassaigne’s extract

Dilute H2SO4 is added to convert Fe2+ to Fe3+ and blue color is formed due to the formation of ferric
ferrocyanide.

Q.No 2
a) What are nucleophiles? Give one example of nucleophile.
b) Will CCl4 give white ppt of AgCl on heating with silver Nitrate. Give reason for your answer.
c) Define hyper conjugation.
d) Draw the condensed formula and bond-line structural formula for
a) 2,2,4-trimethylpentane
 b) 2-hydroxy-1,2,3-propanetricarboxylic acid.

a. Nucleophiles: Nucleophiles are negatively charged or neutral species with lone pair of electrons.
example: Br- , H2O
b. No, it is because CCl4 is non-polar compound, does not give Cl- in aqueous solution, therefore it
will not form any precipitate with silver nitrate (aq).
c. Hyperconjugation is a general stabilising interaction. It involves delocalisation of σ electrons of C—
H bond of an alkyl group directly attached to an atom of unsaturated system or to an atom with an unshared
p orbital. The σ electrons of C—H bond of the alkyl group enter into partial conjugation with the attached
unsaturated system or with the unshared p orbital. Hyperconjugation is a permanent effect.
d.

CASE BASED QUESTIONS

1)
Once an organic compound is extracted from a natural resource or synthesized in the laboratory,it is
essential to purify it.Various methods used for the purification of organic compounds are based on the
nature of the compound and the nature of the impurity present in it. Finally, the purity of a compound is
ascertained by determining its boiling point and melting point. Most of the pure compounds have sharp
melting and boiling points.New methods of checking the purity of an organic compound are based on
different types of chromatographic and spectroscopic methods.

a) How will you separate mixture of camphor and benzoic acid?

b) Boiling point of Chloroform is 334K and that of aniline is 457K. Which method will be suitable to
separate mixture of aniline and chloroform?
c) Which method is used to separate mixture of glycerol and spent-lye in soap industry is separated?
d) Name the method used to purify aniline.
a) As by the process of sublimation, both will get sublime. We can separate them by mixing them in hot
water and then filtering the solution. Residue will be camphor and filtrate will be mixture of water &
benzoic acid and we can get benzoic acid by crystallization method.
b) As the difference in their boiling point is sufficiently large, simple distillation method is used.
c) By distillation under reduced pressure.
d) Steam distillation method because it is steam volatile and immiscible with water.

2)
Carbon compounds show the phenomenon of isomerism. The phenomenon of existence of two or more
compounds possessing the same molecular formula but different properties is known as isomerism. Such
compounds are called as isomers. It shows mainly two types of isomerism structural and stereo
isomerism. Compounds having same molecular formula and structure are classified as structural isomers.
Compounds that have same composition and sequence of covalent compounds but differ in relative
position of the atom in space are called stereo isomers.

i. Classify the following pairs as position, chain, functional isomers or metamers.

a) Diethyl amine and methylpropylamine
b) Ethanol and dimethyl ether

ii. Name the chain isomers of C5H12 which has a tertiary hydrogen atom.
iii. In which of the following functional group isomerism is not possible.
a) Alcohol b)Aldehydes
c) Alkyl halides d) Cyanides

i. a)

They are Metamers

b) C2H5OH , CH3-O-CH3
They are Functional isomers

ii. The chain isomers of C5H12 which has a tertiary hydrogen atom is 2-Methylbutane.

iii. c) alkyl halides

 H
O
1) In pyrrole
T
S
(h
ig
h
er
or
d
er
th
in
ki
n
g
sk
ill
)

The electron density is maximum on

(1)2 and 3 (2) 3 and 3 (3) 2 and 4 (4) 2 and 5
Answer:(4)

2) A mixture contains two components A and B. The solubilities of A and B in water near its boiling
point are 10 grams per 100 ml 2 g per 100 ml respectively How will you separate A and B from this
mixture ?
Answer:A and B from the mixture can be separated by using fractional crystallization. When the
saturated hot solution of this mixture is allowed to cool, the less soluble compound B crystallizes out
first leaving the more soluble component A in the mother liquor.

3) With proper justification arrange the following in order of increasing stability

CH3-CH2-, CH≡C- , CH2=C-
Answer:In acetylide ,CH≡C- ,the carbon atom carrying the –ve charge is sp hybridized and has 50%
s-character in CH2=C-, the carbon atom is sp2 hybridized and has 33% s-character while in
CH3-CH2-, the carbon atom bearing a –ve charge is sp3 and has 25% of s-character. Since s-
electrons, on the average are close to the nucleus than p-electron, therefore a carbon atom with s-
character can accommodate or stabilize the –ve charge better than a carbon atom with small s-
character in other words the stability of the carbo-anion increases as the s-character of the carbon
atom carrying the –ve charge increases. Since the s-character of the carbon decreases as we move
from sp2 to sp2 to sp3 –carbon therefore the relative stability three carbo-anion follows the
sequence CH≡C->CH2=C->CH3-CH2-.
 9.HYDROCARBON
Hydrocarbons are the chemical compounds composed of Carbon and Hydrogen.:

Classifications of Hydrocarbons

Alkanes
 Alkanes are saturated, open chain hydrocarbons containing carbon-carbon single bonds. e.g., methane
(CH4), ethane (C4H6) propane (C3H8), etc. Common formula for alkanes is CnH2n+2.

Preparation of Alkanes

From unsaturated hydrocarbons:

From alkyl halides: Alkyl halide on reduction with zinc and dil. HCl give alkanes.

Wurtz reaction : This reaction is used for preparation of higher alkanes.

From carboxylic acids: Degradation reactions/ decarboxylation reaction.

Kolbe’s electrolytic method: An aqueous solution of sodium or potassium salt of a carboxylic acid on
electrolysis gives alkane containing even number of carbon atoms at the anode.
Chemical Properties

Alkanes being saturated compounds can undergo only substitution reactions.

Halogenation:

The rate of reaction of alkanes with halogens is F2 > Cl2 > Br2 > I2. Rate of replacement of hydrogens of
alkanes is: 3° > 2° > 1°.

Mechanism halogenation of alkanes: it can be explained with free radical mechanism as below:
Combustion:

Controlled oxidation:

Isomerisation:

Aromatization (Reforming): The process of converting aliphatic compounds into aromatic compounds is
called aromatisation.

Reaction with steam:

Pyrolysis or cracking: It is process of decomposing higher hydrocarbons into lower hydrocarbons with
low boiling point by strong heating. Products depend on reaction situations.
 General reactions for methane:

General reactions for Ethane:

Conformations

Spatial arrangements which are obtained by rotation around sigma bons are called conformation or
conformational isomers and this phenomenon is called conformational isomerism.
 Sawhorse projections of ethane: In this projection, the molecule is viewed along the molecular axis.

Newman projections of ethane:

ALKENES

Alkenes are unsaturated hydrocarbons containing at least one double bond. General formula for alkenes is
CnH2n.

Isomerism: Alkenes show both structural isomerism and geometrical isomerism.

Structural isomer Geometrical isomer

 Preparation

From alkynes:

From alkyl halides:

From alcohols by acidic dehydration:

Chemical properties Addition of

halogens:

Addition of hydrogen halides:

Markovnikov rule: The rule states that negative part of the addendum (adding molecule) gets attached to
that carbon atom which possesses lesser number of hydrogen atoms.
 Anti Markovnikov addition or peroxide effect or Kharash effect: In the presence of peroxide, addition
of HBr to unsymmetrical alkenes like propene takes place contrary to the Markovnikov rule.

Addition of sulphuric acid:

Addition of water:

Oxidation: In alkaline solution of KMnO4 (Baeyer’s Reagent)

Ozonolysis:
 Polymerisation:

General reactions for Ethene:

ALKYNES :

Alkynes are also unsaturated hydrocarbons. They contain at least one triple bond between two carbon
atoms. Their general formula is CnH2n–2.

Preparation

From calcium carbide:

From vicinal dihalides:

Chemical properties

Acidic character of alkyne:

Addition of dihydrogen:

Addition of halogens:

Addition of hydrogen halides:

 Addition of water:

Cyclic polymerisation:

General reactions for Ethyne:

AROMATIC HYDROCARBON

These hydrocarbons are also known as ‘arenes’.

Aromaticity : Aromaticity compounds possessing following characteristics –

(i) Planarity

(ii) Complete delocalisation of the π electrons in the ring

 (iii) Presence of (4n + 2) π electrons in the ring where n is an integer (n = 0, 1, 2, . . .). This is often referred
to as Hückel Rule.

Preparation of Benzene Decarboxylation of

aromatic acids:

Reduction of phenol:

Chemical propertiesNitration:

Halogenation:

Sulphonation:
 Friedel-Crafts alkylation reaction:

Friedel-Crafts acylation reaction:

Addition reactions:
 General reactions for Benzene

CARCINOGENICITY AND TOXICITY: Benzene and polynuclear hydrocarbons containing more than
two benzene rings fused together are toxic and said to possess cancer producing (carcinogenic) property.

Let’s Practice:

1. Ozonolysis of acetylene gives-

a) None of these b) CHO-CHO
c) CH3CHO d) HCHO
2. Arrange the halogens F2, Cl2, Br2, I2, in order of their increasing reactivity with alkanes.
a) Br2 < Cl2 < F2 < I2 b) F2 < Cl2 < Br2 < I2 c) Br2 < I2
< Cl2 < F2 d) I2 < Br2 < Cl2 < F2
3. Both ethane and methane can be obtained in a one-step reaction from .
a) CH3OH b) C2H5OH
c) CH3Br d) C2H5Br
4. Hydrocarbon which is liquid at room temperature is-
a) butane b) propane
 c) ethane d) pentane
5. Phenol on heating with NaNO2 and a few drops of conc. H2SO4 gives-
a) p - Nitrosophenol b) m – Nitrosophenol
c) o - Nitrophenol d) p – Nitrophenol
6. Which branched chain isomer of the hydrocarbon with molecular mass 72u gives only one
isomer ofmonosubstituted alkyl halide?
a) Tertiary butyl chloride b) Neohexane
c) Neopentane d) Isohexane
7. An olefin on reductive ozonolysis gives only ethanal as the major product. Name the olefin.
a) But-1-ene b) Propene
c) Ethene d) But-2-ene
8. Photochemical fluorination is explosive while iodination is too slow to occur. The reason for
this is:
a) bond dissociation energy of I2 is minimum.
b) formation of CH3 — F is most exothermic.
c) formation of H — F is most exothermic while formation of HI is endothermic.
d) F2 has lower bond dissociation energy than Cl2 and Br2.
9. Isomerization of n-hexane on heating with anhydrous AICI3 and HCl gas gives .
a) 2-methylpentane b) 3-methylpentane

c) 2-methylhexane d) mixture of 2-methylpentane and 3-methylpentane

10. The IUPAC name of is:

a) 1-methylcyclohex-2-ene b) 1-methylcyclohex-5-ene
c) 3-methylcyclohexene d) 6-methylcyclohexene

11. A dibromo derivative of an alkane reacts with sodium metal to form an alicyclic
hydrocarbon. The derivative is .
a) 2, 2-dibromobutane b) 1, 1-dibromopropane
c) 1, 4-dibromobutane d) 1, 2-dibromoethane
12. The position of double bond in alkenes can be located by:
a) Hydrogenation of oil b) Ozonolysis
c) Photolysis d) Hydration
13. Some meta-directing substituents in aromatic substitution are given. Which one is most
deactivating?
a) –C ≡ N b) -SO3H
c) -COOH d) -NO2
14. The first fraction obtained during the fractionation of petroleum is:
a) Gasoline b) Diesel Oil
c) Hydrocarbon Gases d) Kerosene Oil
15. The catalyst used in Friedel – Crafts reaction is
a) Aluminium Chloride b) Anhydrous Aluminium Chloride
c) Ferric Chloride d) Copper
16. When acetylene is treated with HBr, the product is ———-
a) Methyl bromide b) Ethylene bromide
c) Ethyl bromide d) Ethylidene bromide
17. The dihedral angle in the staggered conformation of C2H6 is
a) 1200 b) 600
c) 00 d) 900
18. Which one of the following is not an isomer of 3-Methylbut-1-yne?
a) Pent-1-yne b) Buta-1,3-diene
c) Pent-2-yne d) Penta-1,3-diene
19. Which of the following compounds will exhibit cis-trans isomerism?
a) Butanol b) 2- Butyne
c) 2-Butenol d) 2-Butene
20. The reaction, CH2= CH – CH3 + HBr → CH3CHBr – CH3 is-
a) electrophilic substitution b) free radical addition
c) nucleophilic addition d) electrophilic addition.
21. Geometrical isomers differ in-
a) position of functional group b) position of atoms
c) spatial arrangement of atoms d) length of carbon chain
22. The compound that will react most readily with gaseous bromine has the formula
a) C3H6 b) C2H2
c) C4H10 d) C2H4
23. 2-Bromopentane is heated with potassium ethoxide in ethanol. The major product obtained
is-
a) trans-2-pentene b) 1-pentene
c) 2-ethoxy pentane d) 2-cis-pentene.
24. Which is maximum stable?
a) 1-Butene b) cis-2-Butene
c) trans-2-Butene d) All have same stability.
25. A gas decolourised by KMno4 solution but gives no precipitate with ammoniacal cuprous chloride is-
a) Ethene b) Propane
c) Propene d) Methane
26. Addition reaction of hydrogen Bromide to the unsymmetrical alkene follows
a) anti markovnikov’s rule b) markovnikov’s rule
c) kharish effect d) peroxide effect
27. Which of the following is a Bayer’s reagent?
a) The neutral solution of HCL
b) An alcoholic solution of sodium carbonate
c) An acidic solution of potassium hydroxide
d) An aqueous solution of potassium permanganate
 28. What is the intermediate conformation between eclipsed and staggered?
a) Staggered b) Skew
c) Eclipse d) Newman
29. Which of the following statement is true regarding the reactivity order in order to form alkyl halides?
a) Hydrogen iodide is less than that of hydrogen Bromide
b) Hydrogen Bromide is less than that of HCL
c) HCL is greater than that of hydrogen iodide
d) Hydrogen Bromide is less than that of hydrogen iodide
30. Arrange the following in decreasing order of their boiling points.
(A) n–butane (B) 2–methylbutane (C) n-pentane (D) 2,2–dimethylpropane
a) A > B > C > D b) B > C > D > A
c) D > C > B > A d) C > B > D > A
31. Which of the following conformation of n-butane is the most stable?
a) eclipsed b) gauche
c) staggered d) skew boat
32. The bond angle between H-C-C bonds in ethane is-
a) 120° b) 180°
c) 109° d) 109.5°
33. Alkanes undergo halogenation. It is an example of-
a) nucleophilic substitution b) elimination
c) free-radical substitution d) electrophilic substitution
34. Which of the following is the most volatile compound?
a) n-pentane b) Isobutane
c) 2-methyl butane d) 2, 2-dimethyl propane
35. Paraffin wax is-
a) Saturated hydrocarbons b) Unsaturated hydrocarbons
c) Alcohol d) Ester

Assertion-Reason type questions-

Note: select correct answer from the below options for question no 36 to 40.
a) Both A and R are true and R is the correctexplanation of A
b) Both A and R are true but R is not thecorrect explanation of A.
c) A is true but R is false.
d) A is false but R is true.
36. Assertion (A): Alkylbenzene is not prepared by Friedel Crafts alkylation of benzene.
Reason (R): Alkyl halides are less reactive than acyl halides.

37.Assertion (A): Addition of HBr on in presence of peroxide give as major

product.
Reason (R): Addition of HBr on alkene proceed by carbocation intermediate.
38. Assertion (A): Alkanes having more than three carbon atoms exhibit chain isomerism.
Reason (R): All carbon atoms in alkanes are sp-hybridized.
 39. Assertion (A): Addition of Br2 to but-1-ene gives two optical isomers.

Reason (R): The product contains one asymmetric carbon atom.

40. Assertion (A): The addition of one equivalent of HCl to 1,3-butadiene at 80°C gives
3-chloro-1-butene as amajor product.
Reason (R): 3-chloro-1-butene is a kinetically controlled product.

Some important questions

41. Write IUPAC name: CH3CH − C(CH3)2.

Ans. 2-methylbutane
43. How would you convert ethene to ethane molecule?
Ans. Unsaturated alkene (ethene) is get converted into saturated alkane (ethane) by the
process of reduction in the presence of reducingagents like Pt/Pd/Ni etc.
Pt/Pd/Ni
CH2 = CH2 (ethene) + H2 −−− →CH3 - CH3 (ethane)
44. How is alkene produced by vicinal dihalide?

Ans. Alkene are produced from Vicinal dihalide by the process of dehalogenations. Vicinal
dihalide on treatment with Zn metal lose amolecule of ZnX2 to from an alkene.
CH2Br-CH2Br + Zn → CH2=CH2 + ZnBr2.
45. How will you distinguish between propene and propane?

Ans. Pass them through dilute cold KMnO4 solution (purple) or Br2in CCl4 solution (rud).
Propene will decolourise both the solutions but propane does not react.
46. Suggest a route for the preparation of nitrobenzene starting from acetylene?

Ans.

47. How will you distinguish between acetylene and ethylene?

Ans. Acetylene forms precipitate with ammoniacal silver nitrate solution, ethylene does not
react with these reagents.
48. Arrange the following: HCl, HBr, Hl, HF in order of decreasing reactivity towards alkenes.
Ans. HI > HBr > HCl > HF
49. Which type of isomerism is exhibited by but-1-yne and but-2-yne?
Ans. Position isomerism.
50. How will you convert ethanoic acid into ethene?
Ans.
 Two marks questions

51. State Kharasch effect.

Ans. Kharasch effect: In the presence of peroxides such as benzoyl peroxide, the
addition of HBr to unsymmetrical alkenes occurscontrary to Markovnikov's rule.
According to Kharasch effect, the negative part of the adding molecule gets attached to
that carbon atom which possesses greater number of hydrogen atoms.
CH3CH = CH2 + HBr CH3 – CH2 – CH2- Br

52. How will you convert benzene to iodobenzene? Give a chemical equation.

Ans.

53. An unsaturated hydrocarbon A adds two molecules of H2 and on reductive ozonolysis

gives butane-1, 4-dial,ethanal, and propanone. Give the structure of A, write its IUPAC
name, and explain the reactions involved.
Ans. Compound A on ozonolysis gives
CH3 CHO + O = CH - CH2 - CH2 - CH=O + O = C (CH3)2
The structure of compound A is CH3 - CH = CH2 - CH2 - CH2 - CH = C
(CH3)2 IUPAC name: 2 -methyl octa 2,6 diene.

54. The boiling point of hydrocarbons decreases with an increase in branching. Give

reason.

Ans. The effective surface area of hydrocarbon reduces due to increase in branching and hence the
strength of the Vander wall’s forces decreases. Thus, less energy is required to separate the molecules of
compound from its liquid surface and thereby leading to adecrease in the boiling point.

55. Which is more acidic: ethene or ethyne and why?

Ans. Ethyne is more acidic than ethene because it has 'sp' hybridised 'C' which is more
electronegative.

57. What do you understated by Resonance energy?

Ans. The difference between the energy of the most stable contributing structure and the
energy of the resonance hybrid is known as resonance energy. Example: The
resonance energy of benzene is 147KJ/mole

58. Unsaturated compounds undergo addition reactions. Why?

 Ans. Unsaturated hydrocarbon compounds undergo addition reactions because they
contain carbon-carbon double or triple bonds. By addition reactions, these unstable
π-bonds get broken and makes stable saturated hydrocarbons.

59. How will you distinguish between Ethene and benzene?

Ans. Ethene discharges bromine water colour and Baeyer’s reagent colour. Benzene does
not discharge bromine water colour and Baeyer’s reagent colour.
60. What is Lindlar's catalyst? Give its use.

Ans. Pb/BaSO4 is known as Lindlar's catalyst. It is used in the conversion of alkynes to

alkenes with the help of H2 .

Three marks questions

61. Define substitution reactions. Why do benzene undergo substitution reactions even
though they contain doublebonds?
Ans. Substitution reactions are those reactions in which an atom or groups of atoms
directly attached to carbon in the substratemolecule is replaced by another atom
or group of atoms, for example

A hydrogen atom of the methane molecule is replaced by chlorine atom. Benzene undergoes
electrophilic substitution reactions because benzene ring has delocalized electrons is an electron-rich
system.It is attached by electrophiles giving substitution products.

62. N-pentane has a higher boiling point than neopentane but the melting point of neopentane is higher
than that of n-pentane.
Ans. The boiling point of hydrocarbons depends upon extent of van der Waal’s forces. Lesser the
branching, greater the surface area and greater the van der Waal’s forces. Because of the presence of
branches in neo-pentane the surface area and van der Waal’s forces of attraction are very weak in
neopentane than in n-pentane. Therefore the b.p of neopentane is lower than that of n-pentane.
But, melting point depends upon the packing of the molecules in the crystal lattice. Since neopentane
are more symmetrical thann-pentane therefore, it packs much more closely in the crystal lattice than
n-pentane and hence neopentane has much higher m.pthan n-pentane.

63. Write structures of different chain isomers of alkanes corresponding to the molecular formula C6H14.
Also, writetheir IUPAC names.
Ans.

64. In the presence of peroxide, addition of HBr to propene takes place according to Anti-Markovnikov's
rule butperoxide effect is not seen in the case of HCl and HI. Explain.
Ans. The mechanism of addition of HX in the presence of Peroxide is not observed in addition of
HCl and HI. This is due to the fact that the H—Cl bond being stronger (430.5 kJ mol-1) than H—Br
bond (363.7 kJ mol-1) is not cleaved symmetrically by the free radical and in case of H—I bond is
weaker (296.8 kJ mol-1) and iodine free radicals have greater tendency to combine to form iodine
molecules instead of adding to the double bond.

65. Explain Wurtz reaction with an example.

Ans.

66. Why do alkenes prefer to undergo electrophilic addition reaction while arenes prefer electrophilic
substitutionreactions? Explain.
Ans. Alkenes are rich source of loosely held pi(π) electrons, due to which they show electrophilic
addition reaction. For example, HBrprovides an electrophile H+ which attacks the double bond to form
carbocation as shown below:

On the other hand, arenes have delocalized (4n+2)π electrons which gives to the great stability of the
ring systems by resonance.Therefore, electrophilic substitution take place.
The arenium ion gets stablished by resonance:
 67. Account for the following: a. Gabriel phthalimide synthesis is not preferred for preparing aromatic
primary amines. b. On reaction with benzene sulphonyl chloride, primary amine yields product soluble in
alkali whereas secondary amine yields product insoluble in alkali.
Ans. CH3, group is electron-donating while- NO2 group is electron-withdrawing. Therefore, maximum
electron density will be in toluene, followed by benzene and least in m-dinitrobenzene. Therefore, the ease
of nitration decreases in the order: toluene > benzene > m-dinitrobenzene.
68. Why does benzene undergo electrophilic substitution reactions easily and nucleophilic substitutions with
difficulty?
Ans. Due to the presence of an electron cloud containing 6 -electrons above and below the plane of the ring,
benzene is a rich source of electrons. Consequently, it attracts the electrophiles (electron - deficient) reagents
towards it and repels nucleophiles (electron rich) reagents. As a result, benzene undergoes electrophilic
substitution reactions easily and nucleophilic substitutions with difficulty.

69. Draw the cis- and trans-structures for hex-2-ene. Which isomer will have higher b.p and why?

Ans. The structures of cis- and trans-isomer of hex-2-ene are:

The boiling point of a molecule depends upon dipole dipole interactions. Since cis-isomer has higher dipole
moment, therefore, it has higher boiling point.
70. Complete the following reactions:

Ans.
71. Read the text carefully and answer the questions:
In staggered conformation, since the electron clouds of carbon-hydrogen bonds are as far apart as possible,
so ithas minimum repulsive forces, minimum energy and maximum stability.
On the other hand, eclipsed conformation has maximum repulsive forces, maximum energy and minimum
stability because in it, the electron clouds of carbon hydrogen bonds are too close to each other.
The angle of rotation about C-C bond is called the dihedral angle or torsional angle and is maximum, i.e.
180o in staggered conformation and minimum (0o) in eclipsed conformation. Thus, torsional strain is
minimum in staggered conformation and maximum in eclipsed form. The two forms differ in energy by
12.5kJ mol-1. This energy barrier is so small that small thermal or kineticenergy is sufficient to overcome it
by intermolecular collisions.
(i) The most stable conformation of ethane.
a) staggered b) can't say
c) eclipsed d) Both are equally stable

(ii) The reason of more stability of chair form of cyclohexane than boat form is-
a) free of angle strain
b) Neither free of torsional train nor freeof angle strain
c) Both free of torsional strain and free ofangle strain
d) free of torsional strain
(iii) The most stable conformation of ethylene glycol is-
a) eclipsed b) all are equally stable
c) gauches d) staggered

(iv) Which is more stable among conformers butane?

a) Fully eclipsed b) Ecllipsed

c) Anti d) Skew

72. Read the text carefully and answer the questions:

Alkenes generally undergo electrophilic addition reactions because of the presence of a double bond (a
strong σ and a weaker π-bond), π electrons of which being loosely held are easily polarisable. These
reactions involvecleavage of a π-bond and formation of two new σ-bonds.
In polar solvents, addition proceed by ionic mechanism (at low temperature), whereas in
the presence of light or non-polar solvents, the addition occurs by free radical mechanism
(at high temperature). Apart from addition reactions alkenes also participate in the
oxidation, ozonolysis and polymerisation reaction.
(i) Assertion (A): 1-butene on reaction with HBr in the presence of a peroxide, produces
bromobutane.
Reason (R): It involves the formation of a primary radical.

a) Both A and R are true and R is thecorrect explanation of A.

b) Both A and R are true but R is not thecorrect explanation of A.
c) A is true but R is false.
d) A is false but R is true.
 (ii) Assertion (A): Propene reacts with HI in the presence of peroxide to give 1-

iodopropane.

Reason (R): 1o free radical is less stable than 2o free radical.

a) Both A and R are true and R is thecorrect explanation of A.

b) Both A and R are true but R is not thecorrect explanation of A.
c) A is true but R is false.
d) A is false but R is true.
(iii) Assertion (A): Propene reacts with HBr to give isopropyl bromide.
Reason (A): Addition of hydrogen halide to alkenes follows Markownikoff's rule.

a) Both A and R are true and R is thecorrect explanation of A.

b) Both A and R are true but R is not thecorrect explanation of A.
c) A is true but R is false.
d) A is false but R is true.

(iv) Assertion (A): Ethene on treating with Br2 in presence of NaCl forms CH2ClCH2Br

and CH2BrCH2Br.

Reason (R): This addition involves the formation of free radicals.

a) Both A and R are true and R is thecorrect explanation of A.
b) Both A and R are true but R is not thecorrect explanation of A.
c) A is true but R is false.
d) A is false but R is true.

73. Read the text carefully and answer the questions:

Benzene (also called cyclohexatriene) is an organic chemical compound with the molecular formula C 6H6.
The benzene molecule is composed of six carbon atoms joined in a planar ring with one hydrogen atom
attached to each. Because it contains only carbon and hydrogen atoms, benzene is classed as a hydrocarbon.
Benzene is a natural constituent of crude oil and is one of the elementary petrochemicals. Due to the cyclic
continuous pi bonds between the carbon atoms, benzene is classed as an aromatic hydrocarbon. It is
sometimes abbreviated PH. Benzene is a colorless and highly flammable liquid with a sweet smell and is
partially responsible for the aroma around petrol (gasoline) stations. It is used primarily as a precursor to
the manufacture of chemicals with more complex structures, such as ethylbenzene and cumene, of which
billions of kilogramsare produced annually. Although a major industrial chemical, benzene finds limited
use in consumer itemsbecause of its toxicity.

(i) What happens when benzene is treated with acetyl chloride in the presence of AlCl3?
Ans. Acetophenone is formed.
 (ii) Benzene undergoes electrophilic substitution reactions easily and nucleophilic substitutions
with difficulty.Why?
Ans. The orbital structure of benzene shows that the π-electrons cloud lying above and below the
benzene ring is loosely held and is thus available to the π-electron seeking reagents i.e.,
electrophiles. Therefore, benzene undergoes electrophilic reactions readily and nucleophilic
substitution reactions with difficulty.
(iii) How would you convert Ethyne into benzene?
Ans. Ethyne is converted into benzene by passing its vapours through red hot tube at 873 K.
(iv) How would you convert Ethene into benzene?
Ans. Ethene is first converted into
ethyne and then to benzene as:

Five marks questions:

74. Assign structures for the following:

i. An alkyne (X) has a molecular formula C5H8. It reacts neither with sodamide nor with ammoniacal
cuprous chloride.
ii. A hydrocarbon 'Y' decolourises bromine water. On ozonolysis it gives 3-methyl butanal and
formaldehyde. Give the name of the compound.
iii. A hydrocarbon (Z) has molecular formula C8H10. It does not decolourise bromine water and is oxidised
to benzoic acid on heating with K2Cr2O7. It can also have three other isomers A, B and C. Write the structures
of Z, A, B and C.
Ans. i. Since the given alkyne (X) does not react with sodamide or ammoniacal cuprous chloride, thus, in Alkyne
C5H8, the triple bond cannot be terminal. Pent-2-yne
ii. Hydrocarbon 'Y’ is alkene (unsaturated hydrocarbon) because it decolourises bromine water. From the products
of ozonolysis, the structure of alkene can be predicted.

iii. The given compound (Z) is arene (Ethylbenzene) as it does not decolourise bromine water.

The other three isomers of Ethylbenzene are:

 75. i. Draw cis and trans isomers of hex-2-ene. Which isomer will have higher boiling point and why?

ii. Classify the following as Z or E isomers:

Ans.

The cis form will have a higher boiling point due to the more polar nature of the molecular leading to
strong intermolecular dipole-dipole interactions. As a result of stronger intermolecular interactions, it
requires more energy to separate the molecules.

ii.

a. Z

b. Z

c. E
Interconversion of Hydrocarbons
Interconversion of Hydrocarbons