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CHAPTER 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
oursenseorgans.

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.

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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
Laws of chemical combination

Law of Conservation of Mass : In a chemical change total mass remains conserved. i.e. mass before
reaction is always equal to mass after reaction.

Law of Definite Proportions: It states that a given compound always contains exactly the same
proportion of elements by weight. All chemical compounds are found to have constant composition
irrespective of their method of preparation or sources
Example: In water (H2O), Hydrogen and Oxygen combine in 2 : 1 molar ratio, this ratio remains constant
whether it is tap water, river water or sea water or produced by any chemical reaction.
Law of Multiple Proportions: States that if two elements can combine to form more than one compound,
the masses of one element that combine with a fixed mass of the other element, are in the ratio of small
whole numbers. For example, hydrogen combines with oxygen to form two compounds, namely, water
and hydrogen peroxide.

➢ Hydrogen(2g) + Oxygen(16g) → Water(18g)

➢ Hydrogen(2g) + Oxygen(32g) →Hydrogen Peroxide(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.

Gay Lussac’s Law of Gaseous Volumes: According to him elements combine in a simple ratio of atoms,
gases combine in a simple ratio of their volumes provided all measurements should be done in the same
temperature and pressure.

H2(g) + Cl2(g) → 2HCl


1 vol 1 vol2 vol
Avogadro’s hypothesis: Equal volumes of all gases have equal number of molecules (not atoms) at same
temperature and pressure condition. S.T.P. (Standard Temperature and Pressure) At S.T.P. condition:
temperature = 0ºC or 273 K Pressure = 1 atm = 760 mm of Hg and volume of one mole of gas at STP is
found to be experimentally equal to 22.4 litres which is known as molar volume.

DALTON’S ATOMIC THEORY

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 The important postulates of this theory are:


 Matter is made up of minute and indivisible particles called atoms.
 Atoms can neither be created nor be destroyed.
 Atoms of same element are identical in their properties and mass. While atoms of different elements
have different properties and mass.
 Atoms combined to form compound atoms called molecules.
 When atoms combine, they do so in a fixed ratio by mass.
Atomic mass unit/unified mass: One atomic mass unit is defined as a mass exactly equal to one twelfth
the mass of one carbon - 12 atom.
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 isotopesCl35and Cl37inthe ratio 3:1. So the average atomic mass Cl = (3x35 +1x37)/4
=35.5
Molecular mass: It is the sum of atomic masses of the elements present in a molecule. It is obtained by
multiplying the atomic mass of each element by the number of its atoms and adding them together.
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: Mole is the unit of amount of substance. It is defined as the amount of substance that contains
asmany particles as there are atoms in exactly 12 g C12 isotope. 1 mole of any substance contains 6.022
x1023 atoms. This number is known as Avogadro numberor Avogadro constant (NAor N0).

1mol of hydrogen atoms =6.022×1023 atoms


1molof water molecules =6.022×1023 water molecules
1mol of sodium chloride =6.022 ×1023formulaunits 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 = 22.4L
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

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n=
Stoichiometry and Stoichiometric calculations
The study about the quantitative relationship between the masses or the volumes of reactants and
theproducts
Limiting reagent : The reactant which is consumed first and limits the amount of product formed in the
reaction, and is therefore, called limiting reagent. .

PRACTICE QUESTIONS

Section-A(MCQ TYPE)
01. What is the mass percentage of carbon in carbon dioxide?
(A) 0.034% (B) 27.27% (C) 3.4% (D) 28.7%
02. The empirical formula and molecular mass of a compound are CH2O and 180 g respectively.
What will be the molecular formula of the compound?
(A) C9H18O9 (B) CH2O (C) C6H12O6 (D) C2H4O2
03. The total number of moles of ions present in 111 g of CaCl2 is
(A)One Mole (B) Two Mole (C) Three Mole (D) Four Mole
04. Which one will have maximum numbers of water molecules?
(A)18 molecules of water (B) 1.8 grams of water
(C) 18 grams of water (D) 18 moles of water
05. Which of the following contains the same number of carbon atoms as are in 6.0 g of carbon
(C – 12)?
(A) 6.0 g Ethane (B) 8.0g Methane
(C) 21.0g Propane (D) 28.0 g CO
06. A mixture having 2 g of H2 and 32 g of oxygen occupies a volume of__ at NTP.
(A) 22.4 L (B) 44.8 L (C) 11.2 L (D) 67.2 L
07. In a reaction A + B2→ AB2if 2 moles of A and 3 moles of B2 are used then which one will be a
limiting reagent?
(A) no limiting reagent (B) B2 (C) A (D) Data is insufficient
08. The amount of water produced by the combustion of 32 gram of methane CH4 + 2O2→ CO2
+ 2H2O
(A) 30 g (B) 36 g (C) 72 g (D) 70 g
09. 4.6 x 1022 atoms of an element weigh 13.8 g. The atomic mass of the element is:
(A) 290 (B) 180 (C) 34.4 (D) 10.4
0
10. 35 C in Fahrenheit will be
(A) 90 (B) 91 (C) 95 (D) 99
11. Which of the following statements about a compound is incorrect?
(A) A molecule of a compound has atoms of different elements
(B) A compound cannot be separated into its constituent elements by physical methods of
separation.
(C) A compound retains the physical properties of its constituent elements.
(D) The ratio of atoms of different elements in a compound is fixed.
12. Which of the following statements is correct about the reaction given below:
4Fe(s) + 3O2(g) → 2Fe2O3(g)

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(A) Total mass of iron and oxygen in reactants = total mass of iron and oxygen in product
therefore it follows law of conservation of mass.
(B) Total mass of reactants = total mass of product; therefore, law of multiple proportions is
followed.
(C) Amount of Fe2O3 can be increased by taking any one of the reactants (iron or oxygen) in
excess.
(D) Amount of Fe2O3 produced will decrease if the
13. Which of the following statements indicates that law of multiple proportions is being
followed?
(A) Sample of carbon dioxide taken from any source will always have carbon and oxygen in
the ratio 1:2.
(B) Carbon forms two oxides namely CO2 and CO, where masses of oxygen which combine
with fixed mass of carbon are in the simple ratio 2:1.
(C) When magnesium burns in oxygen, the amount of magnesium taken for the reaction is
equal to the amount of magnesium in magnesium oxide formed.
(D) At constant temperature and pressure 200 mL of hydrogen will combine with 100 mL
oxygen to produce 200 mL of water vapour.
14. One of the statements of Dalton’s atomic theory is given below: “Compounds are formed
when atoms of different elements combine in a fixed ratio” Which of the following laws is
not related to this statement?
(A) Law of conservation of mass (B) Law of definite proportions
(C) Law of multiple proportions (D) Avogadro law
15. What is the weight of oxygen required for the complete combustion of 2.8 kg of ethylene?
(a) 2.8kg (b) 6.4kg (c) 9.6kg (d) 96kg
ANSWERS:-
Q.NO. ANS Q.NO. ANS Q.NO. ANS
1 B 6 A 11 C
2 C 7 B 12 A
3 C 8 C 13 B
4 D 9 B 14 D
5 B 10 C 15 C

MULTIPLE CHOICE QUESTIONS (ASSERTION–REASON)


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 incorrect
D. If assertion is incorrect and reason is correct.
01. 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.
02. Assertion (A) : One atomic mass unit is defined as one twelfth of the mass of one
carbon-12 atom.

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Reason (R) : Carbon-12 isotope is the most abundant isotope of carbon and has been
chosen as standard.
03. Assertion(A): Combustion of16g of methane gives 28 gm of water.
Reason(R): In the combustion of methane, hydrogen is one of the products.
04. Assertion(A): NaHCO3 has the same empirical and molecular formula.
Reason(R): NaHCO3 evolves CO2 gas on heating.

Answers:-
Q.NO. 1 2 3 4
ANS. B B D B

SHORT ANSWER TYPE-I QUESTIONS (2 MARKS)


S.N. Q&A
01. 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: Averageatomic mass =34.97 x0.755 +36.97 x0.245 =35.46 u
02. Calculate the number of moles in the following masses –
(i)7.85g of Fe (ii) 7.9mg of Ca

Ans: (i) 7.85g of Fe


(ii) 7.9mg of Ca
Mole = 7.9x10-3/40
=1.91x10-4
03. Explain law of multiple proportions with an example.
Ans: The law of multiple proportions rays that if two elements can combine to form
more than one compound, the masses of one element that combine with a fixed
mass of other element are in a ratio of small whole numbers. e.g. hydrogen and
oxygen can combine to form water as well as hydrogen peroxide
04. How many molecules approximately do you expect to be present in a small crystal of
sugar which weighs 10 mg?
Ans:
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.
05. An inorganic salt gave following percentage composition on analysis:
Na= 29.11,S=40.11, O=30.38

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Calculate Emperical formula of the salt.

SHORT ANSWER TYPE-II QUESTIONS(3 MARKS)


01. 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 5.0gof manganese dioxide?(Atomic mass of
Mn=55 u)
Ans: 1 mole of Mn02, i.e., 55 +32 =87g Mn02react with 4 moles of HCl, i.e., 4
x36.5g=146 gofHCl.

02. Vitamin C is essential for the prevention of scurvy. Combustion of 0.2000g of vit.C
gives 0.2998g of CO2 and 0.819g of H2O. What is the empirical formula of vitamin C?

03. Find the mass percentage of each component in the calcium phosphate.

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04. Write the three points of difference between compound and mixture.

Case based questions (4 marks)


01. Read the given passage and answer the questions that follow:
Chemistry plays an important role in human needs for food, health care products and
improving life. Cis platin and taxol are used in chemotherapy, AZT (Azidothymidine) is
used for AIDS. SI units are international units of measurement. Matter is classified
into elements, compounds and mixtures, which can be homogeneous as well as
heterogeneous. A mixture can be separated by physical methods; compounds can be
separated by chemical methods only. Atomic mass is average of masses of isotopes
depending upon their natural abundance. Empirical formula is calculated with the
help of percentage composition of elements in a compound and molecular mass
helps to calculate molecular formula. A chemical equation must be balanced so as to
follow laws of chemical combination.
(a) Express 2.54 mm into S.I units.
Ans. 2.54 × 10–3 m.
(b) Out of milk, diamond, air, petrol which is pure substance?
Ans. Diamond
(c) Balance the equation: NO2 + H2O → HNO3 + NO
Ans. 3NO2 + H2O → 2HNO3 + NO
(d) Chlorophyll contains 2.68% magnesium atoms. Calculate mass of magnesium
atoms in 2 g of chlorophyll.
Ans:

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02. Read the given passage and answer the questions that follow:
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.
Ans – carbon – 12
2) The mass of one mole of a substance in grams is called its..
Ans – molar mass
3) … is the sum of atomic masses of the elements present in a molecule.
Ans – Molecular mass
4) One mole contains exactly …elementary entities.
Ans –6.02214076 × 1023
LONG ANSWER TYPE QUESTIONS(5 MARKS)
01. Dinitrogen and dihydrogen react with each other to produce
ammonia according to thefollowingchemical equation:
(i) N2(g)+3H2(g)—–>2NH3(g)
(ii)Willanyofthetworeactantsremain unreacted?
If yes, which one and what would be its mass?

02. 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

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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

CHAPTER 2- STRUCTURE OF ATOM

DISCOVERY OF SUB ATOMIC PARTICLES


01. DISCOVERYOFELECTRON: J.J. Thomson is credited with discovering the electron and its characteristics
through tests conducted in a discharge tube. Subatomic particles with an elementary charge of -1 are
known as electrons.
02. CHARGETOMASS RATIOOF 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 x1011Ckg-1
Where me=Mass of the electron in kg
e=magnitude of charge on the electron in coulomb (C).
03. Discoveryof proton
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.
Proton: The smallest and lightest positive ion was obtained from hydrogen and was called proton. Mass
ofproton= 1.676 x10-27kg
Chargeon aproton =(+)1.602 x10-19C
04. Neutron: Itisaneutralparticle. Itwasdiscovered by Chadwick(1932).
By the bombardment of thin sheets of beryllium with fast moving a-particles he observed • that
highlypenetratingraysconsist ofneutralparticles whichwerenamed neutrons.
Properties of Fundamental Particles

Relative
Mass Relative
Symbol Mass (amu) Location
Particle (proton Charge
= 1)

inside the
proton p+ 1 1 +1
nucleus

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Relative
Mass Relative
Symbol Mass (amu) Location
Particle (proton Charge
= 1)

outside the
electron e− 5.45 × 10−4 0.00055 −1
nucleus

inside the
neutron n0 1 1 0
nucleus

Atomic number (Z): Number of protons in the nucleus of an atom = Number of electrons in the extra
nuclear part of the electrically neutral atom.

Mass number (A) : Number of protons + Number of neutrons in the nucleus of an atom.

TYPES OF ATOMIC SPECIES

01. Isotopes: Atoms of same element having same atomic number but different mass number.
For example, isotopes of Hydrogen are 1 H1, 1H2, 1H3
02. Isobars: Atoms of different elements having the same mass number but different atomic number,
e.g., 18Ar40, 19K40, 20Ca40
03. Isotones: Atoms of different elements which contain the same number of neutrons.
e.g., 6C14, 7N15, 8O16
04. Isoelectronic Species: Atoms or ions containing the same number of electrons+ For example, N3–, O-2 , F2–
, Na+ , Mg2+ , Al 3+ and Ne, having 10 electrons each are isoelectronic

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 Model of atom: This model was based upon the results of the famous alpha-rays scattering
experiment. It is also known as ‘Planetary model’ and can be summarized in following points.
(i) Most of the mass and all the positive charge of an atom are present in a very small region called
the nucleus.
(ii) The magnitude of the charge on the nucleus is different in atoms of different elements.
(iii) Electrons revolve in the space around nucleus in different circular orbits and the number of
electrons is equal to the number of units of positive charge in the nucleus.
Drawbacks of Rutherford Model
(iv) Rutherford’s model cannot explain the stability of atom if the motion of electrons is described on

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the basis of classical mechanics and electromagnetic theory.


(v) Rutherford’s model does not give any idea about distribution of electrons around the nucleus
and about their energies.
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.
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 ofh/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=a0n2wherea0=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.
(viii) The energy of different orbits in an atom in given by the expression

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Achievements of Bohr’sTheory
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 characterof matter and Heisenberg’s uncertainty principle.
Dual Behaviour of Matter (deBroglie 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 ≥

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Significance of Uncertainty Principle


 It rules out existence of definite paths or trajectories of electrons and other similar particles.
 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
 The wave character of the electron is not considered in Bohr Model.
 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.
QuantumMechanicalModelof 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 occupies 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 wavefunction𝚿.
(v) The probability of finding electron at a point within an atom is proportional to square of orbital wave
functioni.e.,|𝚿2|at that point.It is known as probability density and is always positive.
From the value of 𝚿2 at different points within atom, it is possible to predict the region around the
nucleus where electrons 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,
spinetc.
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 soon.
5. The maximum number of electrons in the shell with principal quantum number n is equal to 2(n2).
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 and 1.i.e.L shell contains two sub shells-sandp sub shells

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When n =3, Ɩ=0, 1 and 2. i.e. M shell containsthreesubshells– s,p anddsub shells
When n=4,Ɩ=0,1, 2and 3.i.e.Nshellcontainsfoursubshells–s, p,dandf subshells
4. The number ofelectronsthat can beaccommodated in sub-energylevelis equal to2(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 ml)


1. The magnetic orbital quantum number determines the number of preferred orientations of the
electronspresentin asub-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 ero.
Thus, for energy value of l, m has 2l + 1 values. For example,
Forl = 0 (s-sub-shell), mcan 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 ORBITALS
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

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finding of the electron density is almost nil. This is known as nodal planeas 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 – 1
Number 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 areas follows.

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
configuration is explained based on Aufbau principle, Hund’s rule, Pauli’s exclusion principle and
stabilityconcept.
1.Aufbau principle:

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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.

PauliExclusionPrinciple
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 forn, 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 parallel spin. For
example the electronic configuration of N is 1s22s22p1p1p1 and not 1s22s22p2p1

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 4s1not [Ar] 3d4 4s2


Similarly Cu(29)=[Ar]3d10 4s1not [Ar]3d94s2

MULTIPLE CHOICE QUESTIONS

S.N. QUESTIONS
1. Which of the following options does not represent ground state electronic configuration of
an atom?
(A)1s2 2s2 2p63s2 3p6 3d84s2 (B)1s22s22p63s23p63d94s2
(C)1s2 2s2 2p6 3s2 3p6 3d104s1 (D)1s2 2s2 2p6 3s2 3p6 3d5 4s1
2. Numberofangularnodes for4d orbitalis .
(A)4 (B) 3 (C) 2 (D)1
3. The number of radial nodes for 3p orbital is.
(A) 3 (B) 4 (C) 2 (D) 1
4. g subshell is characterised by:
(A)n = 5 (B) m = 3 (C) l = 4 (D)l = 5

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5. Which expression represents de Broglie relationship?


(A) h/mu = p (B) λ = h/mv (C)λ = h/mp (D)λ = u/p
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
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
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 (D)F+ and Ne
9. The number of spherical nodes for 4d orbital is
(A) zero (B) one (C)two (D)three
10. The configuration 1s2 2s22p53s1 shows:
(A)ground state of fluorine (B)exited state of fluorine
(C)exited state of neon (D)exited state of O2- ion
11. Which of the following orbitals has dumb-bell shape?
(A)s (B)p (C)d (D) f
12. The total number of orbitals in a shell having principal quantu number n is
(A) 2n (B)n2 (C)2n2 (D)n+1
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)65.4nm (C)0.654nm (D)654nm
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
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
16. Iso-electronic species are:
(A)F- ,O-2 (B)F-,O (C)F-,O+ (D)F-,O+2
17. Quantum numbers n=2,l=1 represent:
(A)1s orbital (B)2s orbital (C) 2p orbital (D)3d orbital
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.
19. The energy of second Bohr orbit of hydrogen atom is -328 KJ/mol. Hence the
energy of forth orbit would be:

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(A)-41 KJ/mol (B)-82 KJ/mol (C)-164 K/mol (D)-1312


KJ/mol
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
ANSWERS:-
Q.NO. ANS Q.NO. ANS Q.NO. ANS Q.NO. ANS
1 B 6 B 11 B 16 A
2 C 7 B 12 B 17 C
3 D 8 B 13 D 18 C
4 C 9 B 14 C 19 B
5 B 10 C 15 B 20 D

MULTIPLE CHOICE QUESTIONS (ASSERTION–REASON)

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 incorrect
D. If assertion is incorrect and reason is correct.
01. Assertion (A): An orbital cannot have more than 2 electrons and their spin must be opposite.
Reason (R) : No two electrons in an atom can have same set of all four quantum
numbers
02. Assertion (A): Both position and momentum of an electron cannot be determined simultaneously
with maximum accuracy
Reason (R): This is because of microscopic nature of electron.
03. Assertion (A): The energy of an electron is mainly determined by principal quantum number.
Reason (R): The principal quantum number is the measure of the most probable distance of
finding the electron around the nucleus.
04. Assertion (A): Fe3+ ion is more stable than Fe2+ ion in ground state.
Reason (R): Fe3+ ion has more number of unpaired electrons than Fe2+ ion.
05. Assertion (A): Anorbital cannot have more than two electrons.
Reason (R) : The two electrons in an orbital create opposite magnetic
th
06. Assertion (A): The 19 electron in potassium atom enters 4s-orbital and not 3 d-orbital.
Reason (R) : The energies of the orbitals can be compared with the help of (n+l) rules
07. Assertion (A): All isotopes of a given element show the same type of chemical
behaviour. Reason (R) : The chemical properties of an atom are controlled by the
number of electrons in the atom
ANSWERS:-

Q.NO. 1 2 3 4 5 6 7
ANS. A A A B C A A

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SHORT ANSWER TYPE-I QUESTIONS(2 MARKS)


S.N Q&A
.
01. Why Pauli Exclusion Principle is called exclusion principle?
Ans: This is because according to this principle, if one electron in an atom has some particular
values for the four quantum numbers, then all the other electrons in that atom are excluded
from having the same set of values.

02. 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.
03. 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
Ans:

04. Heinsberg uncertainty principle has no significance in our everyday life. Explain.
Ans: In our daily life we can see only the moving macro and semi-micro-objects. 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.
05. 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.
06. 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 TYPE QUESTIONS-II (3 MARKS)
01.
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

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(iv) There is one unpaired electron.


02. 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?
Ans:

03. Distinguish between orbit and orbital.


Orbit
Orbital
Orbit is a well-defined 2-D circular path Orbital is a 3-D space around the atom
Around the nucleus in which the electron where the probability of finding electron is
revolve. maximum.
It is in accordance with wave
It is not in accordance of wave character
character. Except s-orbital, all orbitals
Orbits do not have direction
are direction.

04. 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).
Ans:

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

CASE BASED QUESTION

01. Read the given passage and answer the questions that follow based on passage and related
studied concepts.

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Orbitals are region or space where there is maximum probability of finding electrons.
Qualitatively, these orbitals can be distinguished by their size, shape and orientation. An
orbital of small size means there is more chance of finding the electron near the nucleus.
Shape and orientation means the direction in which probability of finding electron is
maximum. Atomic orbitals can be distinguished by quantum numbers. Each orbital is
designated by three quantum numbers n, l and ml (magnetic quantum number) which define
energy, shape and orientation but these are not sufficient to explain spectra of multi-electrons
atoms. Spin quantum number (ms) determines the spin of electron. Spin angular momentum
of electron has two orientations relative to chosen axis which are distinguished by spin
quantum numbers ms which can take values +1/2 and –1/2

(a) How many orbitals are associated with n = 3?


Ans. Number of orbitals = n 2 = 32 = 9 orbitals, 3s, 3px, 3py, 3pz, 3dx2-y2, 3dz2, 3dxy, 3dyz and
3dzx.
(b) Describe the orbitals represented by (i) n = 2, l = 1 (ii) n = 4, l = 0.
Ans. (i) 2p (ii) 4s
(c) How many electrons are possible in an orbital? Why?
Ans. Orbital can have maximum two electrons which must be of opposite spin.
(d) What is shape of ’s’ and 'p' orbitals?
Ans. 's' orbitals are spherical and 'p' orbitals have dumb-bell shaped.
(e) Name two d-orbitals which are on axis.
Ans. dx2–y2, dz2
02. Read the following passage and answer the questions that follow:
Bohr's model explained electrons can revolve only in certain permitted orbits whose angular
momentum is integral multiple of h/2π, associated with fixed amount of energy. Bohr theory
could successfully explain stability of atoms and spectrum of unielectron species. Hydrogen
spectrum consists of Lyman, Balmer, Paschen, Brackett and Pfund series. Bohr's theory could
not explain spectrum of multi-electron species, Stark effect, Zeeman effect, dual nature of
matter, de Broglie equation and Heisenberg uncertainty principle which lead to orbital
concept. Electrons were filled in orbitals according to Aufbau's principle, Hund's Rule and
Pauli's exclusion principle. Each electron is identified by four quantum numbers n, l, ml and
ms out which n, l, ml were derived from Schrodinger's wave equation. Half filled and
completely filled orbitals are more stable due to exchange energy and symmetrical
distribution of electrons.

(a) Heat treatment of muscular pain involves radiation of wavelength 900 nm which spectral
line of H-atom is suitable for this purpose.
Ans:

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(b) Arrange 4d, 3d, 4p and 3p in increasing order of energy.


Ans. 3p < 3d < 4p < 4d.
(c) What is name of spectrum of radiation emitted by substance that has absorbed
radiation? Ans. Emission spectrum.
(d) What rules out the probability of existence of definite path of electrons?
Ans. Heisenberg's uncertainty principle.
(e) State de Broglie equation.

Ans. the wavelength of matter waves is inversely proportional to momentum.

LONG ANSWER QUESTION (5 MARKS)


01. (I) Write outer electronic configuration of Cr atom. Why are half filled orbitals more
stable
(II) A 25 watt bulb emits monochromatic yellow light of wavelength 0.57 μm.
Calculate the rate of emission of quanta per second.
Ans:

(II)

02. 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.
Ans:

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UNIT -3 CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES

1. Dobereiner's Triads: In 1817 a German chemist Doberneiner identified certain groups of three
elements.
These groups of three elements having similar properties were called triads. When three elements were
arranged in order of their increasing atomic masses, the atomic mass of the middle element was roughly
the mean of the atomic masses of the other two element Examples
Elements Li Na K
At.mass 7 23 39 7 + 39 / 2 = 23
Elements Fe Co Ni
At.mass 55.85 58.93 58.71 nearly same atomic masses It was restricted to few elements, therefore,
discarded.
2. New Lands Law of octaves: When elements were arranged in order of their increasing relative atomic
masses. The properties of every eight elements were similar to the first one, like the eighth note of a
musical scale.This repetition in the properties of elements is just like the repetition of eighth node in an
octave of music.
This arrangement of elements is called as Newland’s law of Octave.
Li Be B C N O F
Na Mg Al Si P S Cl
K Ca
This classification worked quite well for the lighter elements but it failed in case of heavier elements and
therefore, discarded.
3. Mendeleev's Periodic Law: The physical and chemical properties of elements are the periodic function of
their atomic masses.
4. Mendeleev's Periodic Table: When mendeleev started his work, 63 elements were known at that time. He
selected hydrogen and oxygen as they are very reactive and formed compounds with most elements.
Mendeleev's periodic table contains vertical columns called groups and horizontal rows called periods.

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There were 7 periods and 8 groups. Noble gases were not known at that time. So there was no group of
noble gases.The elements in each group of the periodic tables are similar to one another in many
properties. The similar properties of the elements are repeated periodically
(a).Merits of mendeleev's classification
 Mendeleev's periodic law predicted the existence of some elements that had not been discovered
at that time
 Could accommodate noble gases when they were discovered.
 Mendeleevs predicted the properties of those missing elements from the known properties of the
other elements in the same group. Eka – aluminium and Eka-silicon names were given for gallium
and germanium (not discovered at the time of Mendeleevs). Properties predicted by Mendeleevs
for these elements and those found experimentally were almost similar.
PROPERTY EKA- GALLIUM EKA-SILICON GERMANIUM
ALUMINIUM (FOUND) (PREDICTED) (FOUND)
(PREDICTED)
Atomic 68 70 72 72.6
Mass
Density / 5.9 5.94 5.5 5.36
(g/cm3)
Melting Low 30.2 High 1231
point (K)
Formula of E2O3 Ga2O3 EO2 GeO2
oxide
Formula of ECl3 GaCl3 ECl4 GeCl4
Chloride
(b) .Limitations of Mendeleev's classification:-
 The correct position could not be assigned to the hydrogen in the periodic table.
 Wrong order of the atomic masses of some elements could not be explained.
 Anomalous position of lanthanides and actinides in periodic table.
 The position of isotopes could not be explained.
 Order of increasing atomic weights is not strictly followed in the arrangement of elements in the
periodic table. For example Ar(39.94) is placed before K(39.08) and Te (127.6) is placed before I
(126.9)
 Similar elements were placed in different groups (Cu lB an Hg llB) and the elements with different
properties were placed in same groups (alkali metals lA and coinage metals lB)
 It didn’t explain the cause of periodicity. Uncertainity in prediction of new elements was there.
5. Modern Periodic law (Moseley’s Periodic Law) : Physical and chemical properties of elements are the
periodic functions of their atomic number. If the elements are arranged in order of their increasing
atomic number, after a regular interval, elements with similar properties are repeated.
6. Cause of Periodicty: The periodic repetition of the properties of the elements is due to the reocurrence of
similar valence shell electronic configuration after certain regular intervals. For example, alkali metals
have same electronic configuration ns1, therefore, have similar properties.
7. Modern Periodic Table: The long form of periodic table is the contribution of Range, Werner, Bohr and
Bury.This table is also referred to as Bohr’s table since it follows Bohr’s scheme of the arrangements of
elements into four types based on electronic configuration of elements.
 The table consists of 18 vertical columns called groups Elements having similar outer electronic
configurations in their atoms are arranged in vertical columns, referred to as groups.According to the
recommendation of International Union of Pure and Applied Chemistry (IUPAC), the groups are
numbered from 1 to 18 .

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 The table consists of 7 horizontal rows called periods. Each period starts with an alkali metal having
outermost electronic configuration ns1. Each period ends with a noble gas with outer most electronic
configuration ns2np6 except helium having outermost electronic configuration 1s2. The first period
contains 2 elements. The subsequent periods consists of 8, 8, 18, 18 and 32 elements, respectively.
The seventh period is incomplete and like the sixth period would have a theoretical maximum (on the
basis of quantum numbers) of 32 elements. In this form of the Periodic Table, 14 elements of both
sixth and seventh periods (lanthanoids and actinoids, respectively) are placed in separate panels at
the bottom.

8. Notation for IUPAC Nomenclature of Elements With Z > 100


Digit Name Abbreviation
0 Nil n
1 un u
2 bi b
3 tri t
4 quad q

5 pent p
6 hex H
7 sept S
8 oct O
9 enn E

The latin words for various digits of the atomic number are written together in the order of which
makes the atomic number and suffix ‘ium’ is added at the end. In case of bi and tri one ‘i’ is omitted.
We can classify the elements into four blocks viz., s-block, p-block, d-block and f-block depending on the
typeof atomic orbital that are being filled with electrons.
9. s-Block Elements (s-block elements lie on the extreme left of the periodic table.)
 Group 1 (alkali metals) & 2 (alkaline earth metals) elements constitute the s-block.
 General electronic configuration is [inert gas] ns1-2

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 This block includes metals.


10. p-Block Elements (P-block elements lie on the extreme right of the periodic table)
 Group 13 to 18 elements constitute the p-block.
 General electronic configuration is [inert gas] ns2np1-6
 This block includes some metals, all non-metals and metalloids.
11. The p-Block Elements together with the s-Block Elements are called the Representative Elements or
MainGroup Elements.
12. d-Block Elements
 Group 3 to 12 elements constitute the d-block.
 General electronic configuration is [inert gas] (n - 1) d1-10 ns0-2
 All the transition elements are metals and most of them formed coloured complexes or ions.
 d-block elements are classified into four series
Series Elements (n-1) d being
filled
3d 21Sc – 30Zn 3d
4d 39 Y – 48Cd 4d
5d 6d 57La, 72Hf -
80Hg 5d 6d (incomplete
89Ac, 104Rf-112 series)
Uub
 Those elements which have partially filled d-orbitals in neutral state or in any stable oxidation
state are called transition elements.
13. f-Block Elements
 General electronic configuration is (n - 2) f1-14 (n - 1) d0,1 ns2
 All f-block elements belong to 3rd group. They are metals.
 Within each series, the properties of the elements are quite similar.
 The elements coming after uranium are called transuranic elements.
 They are also called as inner-transition elements as they contain three outer most shell
incomplete and were also referred to as rare earth elements since their oxides were rare in
earlierdays.
 The elements of f-blocks have been classified into two series, lanthanoids and actinoids.
 Ist inner transition or 4 f-series or lanthanoids, contains 14 elements 58Ce to 71Lu. Filling of
electrons takes placein 4f subshell.
 IInd inner transition or 5 f-series or actinoids, contains 14 elements 90Th to103Lr. Filling of
electrons takes place in 5f subshell. The actinides and lanthanides have been placed at the
bottom of the periodic tableto avoid the undue expansion of the periodic table.
14. Prediction of period, group and block :
 Period of an element corresponds to the principal quantum number of the valence shell.
 The block of an element corresponds to the type of subshell which receives the last electron.
 The group is predicted from the number of electrons in the valence shell or/and penultimate shell
asfollows.
(a) For s-block elements
Group number = the no. of valence electrons
(b) For p-block elements
Group number = 10 + no. of valence electrons
(c) For d-Block elements
Group number = no. of electrons in (n - 1) d sub shell + no. of electrons in valence shell.
15. PERIODICITY: The repetition of similar properties after regular intervals is called periodicity.
16. Cause of Periodicity: The properties of elements are the periodic repetition of similar electronic

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configuration of elements as the atomic number increases.


17. ATOMIC RADIUS -
 The distance from the centre of the nucleus to the outermost shell of the electrons in the atom
of any element is called its atomic radius.
 Probability of finding the electron is never zero even at large distance from the nucleus. Based
on probability concept, an atom does not have well defined boundary. Hence exact value of the
atomic radius can’t be evaluated.
 Atomic radius is taken as the effective size which is the distance of the closet approach of one
atom to another atom in a given bonding state.
18. COVALENT RADIUS- It is one-half of the distance between the centres of two nuclei (of like atoms)
bonded by a single covalent bond. Covalent radius is generally used for non-metals .

19. VAN DER WAALS’ RADIUS: It is one-half of the internuclear distance between two adjacent atoms in two
nearest neighbouring molecules of the substance in solid state.

20. Comparision of covalent radius and van der Waal’s radius


 The van der Waal’s force of attractions are weak, therefore, their internuclear distances in case of
atoms held by van der Waal’s force are much larger than those of between covalently bonded atoms.
Therefore van der Waal’s radii are always larger than covalent radii.
 A covalent bond is formed by the overlapping of two half-filled atomic orbitals, a part of the orbital
becomes common. Therefore, covalent radii are always smaller than the van der Waals radii. For
example,
Elements H O F S B
r
Covalent 0 0 0 1 1
radius (Å) . . . . .
3 6 6 0 1
7 6 4 4 1
Van der 1 1 1 1 1
Waals . . . . .
2 4 3 8 9
0 0 5 5 5
21. METALLIC RADIUS: It is one-half of the distance between the nuclei of two adjacent metal atoms in the
metallic crystal lattice.

22. Van der Waals’radius > Metallic radius > Covalent radius, rcovalent < rcrystal <rvander Walls

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23. IONIC RADIUS: The effective distance from the centre of the nucleus of an ion upto which it
has aninfluence on its electron cloud is called its ionic radius
24. Variation in Atomic Radius

Variation in Atomic Radius in Period Variation in Atomic Radius in Group


Atomic size decreases with increase in atomic Atomic size atom increases from top to bottom
number in a period from left to right in agiven group.

25. The atomic radii of noble gases are not considered here. Being monoatomic, their (non-bonded radii)
values are very large. In fact radii of noble gases should be compared not with the covalent radii but
with the van der Waals radii of other elements.
26. Ionic radius: The effective distance from the centre of nucleus of the ion up to which it has an influence
in the ionic bond is called ionic radius.
27. A cation is smaller than its parent atom because in a Cation, the number of positive charges on the
nucleus is greater than the number of orbital electrons leading to increased inward pull of remaining
electrons causing contraction in size of the ion. For example the atomic radius of sodium is 186 pm
compared to the ionic radius of 95 pm for Na+.
For example : Na Na+
Number of Electrons : 11 10
Number of Protons : 11 11
28. The size of an anion will be larger than that of the parent atom because the addition of one or more
electrons would result in increased repulsion among the electrons and a decrease in effective nuclear
charge. For example, the ionic radius of fluoride ion (F– ) is 136 pm whereas the atomic radius of
fluorine is only 64 pm.
Cl Cl-
Number of Electrons : 17 18
Number of Protons : 17 17
29. Isoelectronic species: The species containing the same number of electrons but differ in the
magnitude of their nuclear charges are called as isoelectronic species. For example, N3-, O2- , F- , Ne, Na+
, Mg2+ and Al3+ are all isoelectronic species with same number of electrons (i.e. 10) but different
nuclear charges of +7, +8, +9, +10, +11, +12 and +13 respectively
Variation in ionic radii of isoelectronic species Within a series of isoelectronic species as the nuclear charge
increase, the force of attraction by the nucleus on the electrons also increases. As a result, the ionic radii of
isoelectronic species decrease with increase with increases in the magnitude of nuclear charges. For
example,
Al3+ Mg2+ Na+ F- O2- N3-
Ionic radii increase
As effective nuclear charge decrease.

30. Ionization Enthalpy:


 It represents the energy required to remove an electron from an isolated gaseous atom (X) in its
ground state. In other words, the first ionization enthalpy for an element X is the enthalpy change
(ΔiH) for the reaction depicted in equation. X(g)-> X+(g) + e– .
 The ionization enthalpy is expressed in units of kJ mol–1.
 M(g) -> M+(g) + e- ; M+ + lE2 -> M2+ + e- ; M2+ + lE3 -> M+3 + e-
 lE2 & lE3 are the llnd & lllrd ionization energies to removed electron from monovalent and
divalentcations respectively.
 In general : (IE)1 < (IE)2 < (lE)3 < ............. because, as the number of electrons decreases, the

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attraction between the nucleus and the remaining electrons increases considerably and hence
subsequent l.E. (s) increase.
 The second ionization enthalpy will be higher than the first ionization enthalpy because it is more
difficult to remove an electron from a positively charged ion than from a neutral atom. In the same
way the third ionization enthalpy will be higher than the second and so on. The term “ionization
enthalpy”, if not qualified, is taken as the first ionization enthalpy.
31. Factors Influencing Ionisation energy
 Size of the Atom : Ionisation energy decreases with increase in atomic size. As the distance
between the outermost electrons and the nucleus increases, the force of attraction between the
valence shell electrons and the nucleus decreases. As a result, outer most electrons are held less
firmly and lesser amount of energy is required to knock them out. For example, ionisation
energy decreases in a group from top to bottom with increase in atomic size.
 Nuclear Charge : The ionisation energy increases with increase in the nuclear charge. The is
due to the fact that with increase in the nuclear charge, the electrons of the outer most shell are
more firmly held by the nucleus and thus greater amount of energy is required to pull out an
electron from the atom. For example, ionisation energy increases as we move from left to right
along a period due to increase in nuclear charge.
 Shielding effect : The electrons in the inner shells act as a screen or shield between the nucleus
and the electrons in the outermost shell. This is called shielding effect. The larger the number of
electrons in the inner shells, greater is the screening effect and smaller the force of attraction
and thus (IE) decreases.
 Penetration Effect of the Electron : The ionisation energy increases as the penetration effect of the
electrons increases. It is a well known fact that the electrons of the s-orbital has the maximum
probability of being found near the nucleus and this probability goes on decreasing in case of P, d
and f orbitals of the same energy level. Within the same energy level, the penetration effect
decreases in the order S > P > d > f Greater the penetration effect of electrons more firmly the
electron will be held by the nucleus and thus higher will be the ionisation energy of the atom. For
example, ionisation energy of aluminium is comparatively less then magnesium as outer most
electron is to be removed from p-orbital (having less penetration effect) of same energy level.
 Electronic Configuration : If an atom has exactly half-filled or completely filled orbitals, then such
an arrangement has extrastability. The removal of an electron from such an atom requires more
energy then expected. For example, Be IE1 > B IE1 Be (Z = 4) 1s2 , 2s2 B(Z  5) 1s2 , 2s2 , 2p1
completaly filled Partially filled
orbital more stable orbital less stable
As noble gases have completely filled electronic configurations, they have highest ionisation
energies in their respective periods.
32. Variation in Ionization Enthalpy
Variation in Ionization Enthalpy in Group Variation in Ionization Enthalpy in Period
As we descend in a group the first ionization The first ionization enthalpy generally
enthalpygenerally decreases increases aswe go across a period.

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33. Electron Gain Enthalpy: When an electron is added to a neutral gaseous atom (X) to convert it into a
negative ion, the enthalpy change accompanying the process is defined as the electron gain enthalpy.
Electron gain enthalpy provides a measure of the ease with which an atom adds an electron to form
anion. X (g) + e- X-(g) ; eg H
34. When an electron is added to the atom and the energy is released, the electron gain enthalpy is
negative and when energy is needed to add an electron to the atom, the electron gain enthalpy is
positive.
35. The addition of second electron to an anion is opposed by electrostatic repulsion and hence the energy
has to be supplied for the addition of second electron. For example :
(a)O(g) + e+ O- (g) + energy - - 2-
eg H =-ve (b)O (g) + e + energy O (g) eg H =+ve
36. Group 17 (halogens) have very high negative electron gain enthalpies because they can attain
stablenoble gas electronic configuration by picking up an electron.
37. Noble gases have large positive electron gain enthalpies because the electrons have to enter the
nexthigher energy level leading to a very unstable electronic configuration.
38. Variation in electron gain enthalpies in Group & period:
Variation in electron gain enthalpies in Group Variation in electron gain enthalpies in
Period
We should also expect electron gain enthalpy to As a general rule, electron gain enthalpy
become less negative as we go down a group becomes more negative.
because the size of the atom increases and the Reason: because left to right across a
added electron would be farther from the nucleus. period effective nuclear charge increases
This is generally the case . Exceptions : and consequently it will be easier to add an
Electron gain enthalpy of O or F is less than S or Cl. electronto a small atom.
This is due to the fact that when an electron is added
to O or F, the added electron goes to the smaller n =
2 energy level and experiences significant repulsion
from the other electrons present in this level. In S or
Cl, the electron goes to the larger n = 3 energy level
and consequently occupies a larger region of space
leading to much less electron
repulsion.
1
 Factors Influencing electron gain enthalpies (i) Electron gain enthalpy α (ii) Electron gain
Atomic size
enthalpy α Effective nuclear charge (zeff) (iii) Electron gain enthalpy α 1 (iv) stability of
screening effect
half filled and completely filled orbitals of a subshell is comparatively more and the addition of an extra electron to
such an system is difficult and hence the electron affinity value decreases.

39. Electronegativity: Electronegativity is a measure of the tendency of an element to attract electrons


towards itself in a covalent bonded molecules. There is no direct method to measure the value of
electronegativity, however, there are some scales to measure its value. Linus Pauling, an American
scientist, in 1922 assigned arbitrarily a value of 4.0 to fluorine, the element considered to have the
greatest ability to attract electrons.

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40. VALENCE ELECTRONS: The electrons present in outermost shell are called as valence electron. Because
the electrons in the outermost shell determine the valency of an element.
41. VALENCY OF AN ELEMENT: The number of hydrogen or halogen atom or double the number of
oxygen atom, which combin with one atom of the element is taken as its valency. According to the
electronic concept of valency, “ the number of electrons which an atom loses or gains or shares with
other atom to attain the noble gas configuration is termed as its valency.” Periodicity:
 In period- The valency first increases then decreases from left to right in a period.
 In group- The valency remains constant from top to bottom in a group.
42. ELECTROPOSITIVE OR METALLIC CHARACTER: The tendency of an element to lose electrons and forms
positive ions (cations) is called electropositive or metallic character. The elements having lower
ionisation energies have higher tendency to lose electrons, thus they are electropositive or metallic in
their behaviour. Alkali metals are the most highly electropositive elements.
 Periodicity: In period- The electropositive or metallic characters decreases from left to right in a
period.
 In group- The electropositive or metallic characters increases from top to bottom in a group.
43. ELECTRO-NEGATIVE OR NON- METALLIC CHARACTERS: the tendency of an element to accept electrons to
form an anion is called its non metallic or electronegative character. The elements having high electro-
negativity have higher tendency to gain electrons and forms anion. So, the elements in the upper right
hand portion of the periodic table are electro-negative or non-metallic in nature. Periodicity:
 In period- The electro-negative or non- metallic characters increases from left to right in a
period.
 In group- The electro-negative or non-metallic characters decreases from top to bottom in a
group.
44. REACTIVITY OF METALS: Periodicity:
 In period- The tendency of an element to lose electrons decreases in a period. So the reactivity
ofmetals decreases from left to right in a period.
 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.
45. 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.
46. Anomalous Properties of Second Period Elements: The first element of each of the groups 1 (lithium)
and 2 (beryllium) and groups 13-17 (boron to fluorine) differs in many respects from the other members
of their respective group. For example, lithium unlike other alkali metals, and beryllium unlike other
alkaline earth metals, form compounds with pronounced covalent character; the other members of
these groups predominantly form ionic compounds. In fact the behaviour of lithium and beryllium is
more similar with the second element of the Group 1, 2 ,13, 14, 15, 16 ,17. following group i.e.,
magnesium and aluminium, respectively. This sort of similarity is commonly referred to as diagonal
relationship in the periodic properties. The anomalous behaviour is attributed to their small size, large
charge/ radius ratio and high electronegativity of the elements. In addition, the first member of group
has only four valence

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orbitals (2s and 2p) available for bonding, whereas the second member of the groups have nine valence
orbitals (3s, 3p, 3d). As a consequence of this, the maximum covalency of the first member of each
group is 4 (e.g., boron can only form [BF4]- , whereas the other members of the groups can expand their
valence shell to accommodate more than four pairs of electrons e.g., aluminium forms [AlF6]3- ).
Furthermore, the first member of p-block elements displays greater ability to form p∏ – p∏ multiple
bonds to itself (e.g.,
subsequent members of the same group.

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
theiradjacent 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 beliquefied 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

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8. 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

9. 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

10.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

11. The least electron affinity is found in


(A) Kr (B) O (C) N (D) B ANSWER- C

12. 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

13. Which oxide of N is isoelectronic with CO2 -


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

14. 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

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

REASONING–ASSERTION TYPE QUESTIONS:

(A) Assertion is correct, Reason is correct; Reason is a correct explanationfor Assertion.


(B) Assertion is correct, Reason is correct; Reason is not a correctexplanation for Assertion
(C) Assertion is correct, Reason is incorrect
(D) Assertion is incorrect, Reason is correct.
Q1. Assertion: Electron gain enthalpy becomes less negative as we go down a group.
Reason: Size of the atom increases on going down the group and the added electron would be
farther from the nucleus.
Q2. Assertion: Smaller the size of an atom greater is the electronegativity.
Reason: Electronegativity refers to the tendency of atom to share electrons with other atom.
Q3. Assertion: Atomic number of the element ununbium is 112.
Reason: Name for digits 1 and 2 is un– and bi–respectively in latin words.

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Q4. Assertion: Hydrogen can be placed in group 1.


Reason: Hydrogen can gain an electron to achieve a noble gas arrangement.
Q5. Assertion: Second ionization enthalpy will be higher than the first ionization enthalpy.
Reason: Ionization enthalpy is a quantitative measure of the tendency of an element to lose
electron.
Q1- A Q2- A Q3- A Q4-B Q5-B

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.

Q2.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.

Q3.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

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Q4.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.

Q5.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)/Iso electronic species. Hence, the given species
are isoelectronic. (b) Al3+ < Mg2+ < Na+ < F– < O2– < N3–

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.
Q.2. The first (ΔiH1) and the second (ΔiH) ionization enthalpies (in kJ mol–1) and the (ΔegH) electron
gain enthalpy (in kJ mol–1) of a few elements are given below:

Elements iH1 iH2 egH


I 520 7300 –60
II 419 3051 –48
III 1681 3374 –328
IV 1008 1846 –295
V 2372 5251 +48
VI 738 1451 –40

Which of the above elements is likely to be :

(a) the least reactive element. (b) the most reactive metal.
(c) the most reactive non-metal. (d) the least reactive non-metal.
(e)the metal which can form a stable binary halide of the formula MX2, (X=halogen).

Ans- (a) Element V is likely to be the least reactive element. This is because it has the highest first
ionization enthalpy (ΔiH1) and a positive electron gain enthalpy (ΔegH).

b)Element II is likely to be the most reactive metal as it has the lowest first ionization enthalpy (ΔiH1)
and a low negative electron gain enthalpy (ΔegH).

c)Element III is likely to be the most reactive non–metal as it has a high first ionization enthalpy (ΔiH1)
and the highest negative electron gain enthalpy (ΔegH).

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d)Element V is likely to be the least reactive non–metal since it has a very high first ionization enthalpy
(ΔiH2) and a positive electron gain enthalpy (ΔegH).

e)Element VI has a low negative electron gain enthalpy (ΔegH). Thus, it is a metal. Further, it has the
lowest second ionization enthalpy (ΔiH2). Hence, it can form a stable binary halide of the formula
MX2(X=halogen).

CASE BASED QUESTION 1


PASSAGE
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
electronegativity while the metallic character is inversely related to it.
a.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)
b.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)
c.The least, metallic element of group-13 is
(a) Aluminium(b) Boron (c) Gallium (d) Indium.
ANSWER: (b)
d.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)

CASE BASED QUESTION 2


PASSAGE

Read the passage and answer the questions that follow:


The atomic and ionic radii decrease with increase in atomic number along a period from left to right.
Atomic size and ionic size increases down the group.
Ionisation enthalpy decreases down the group and increases along a period from left to right. It also
depends upon shielding effect as well as stability of electronic configuration.
Electronegativity decreases down the group but increases along the period.
(a) Arrange the elements of second period in increasing order of first ionisation enthalpy.
Ans. Li < B < Be < C < O < N < F < Ne.
(b) Arrange the elements of group 13 in increasing order of atomic size.
Ans. B < Ga < Al < In < Tl
(c) Select the amphoteric oxides among the following:
NO, B2O3, Cr2O3, BeO, ZnO, CO2, Al2O3
Ans. Cr2O3, BeO, ZnO and Al2O3.
–1 –1 –1 4 –1
(d) For an element I.E = 738 kJ mol , IE = 1450 kJ mol , IE = 7700 kJ mol , IE = 1.1 × 10 kJ mol . Name
1 2 3 4
the main group to which element belong. Why?
Ans. Group 2, because its third ionisation is very high as compared to second because after losing 2
electrons it acquires nearest noble gas configuration.

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Unit - 4.Chemical bonding and Molecular Structure


Important Points and Terms of the Chapter

1. CHEMICAL BOND- The chemical force which keeps the atoms in any molecule
together is called a chemical bond.
2. Lewis dot structures are a shorthand to represent the valence electrons of an atom. The
structures are written as the element symbol surrounded by dots that represent the valence
electrons.
3. Electrovalent bond or Ionic Bond: The chemical bond as result of transfer of electron
from one atom(electropositive) to another atom (electronegative).Ionic bonds will be
formed more easily between elements with comparatively low ionization enthalpies and
elements with comparatively high negative value of electron gain enthalpy. Most ionic
compounds have cations derived from metallic elements and anions from non-metallic
elements.

4. Electrovalency: The number of electrons lost or gain by an atom of an element is called


as electrovalency. The element which give up electrons to form positive ions are said to
have positive valency, while the elements which accept electrons to form negative ions are
said to have negative valency
5. Formation of Ionic Bond : It is favoured by, (i) the low ionisation enthalpy of a metallic
element which forms the cations, (ii) High electron gain enthalpy of non- metallic element
which forms the anions, (iii) Large lattice enthalpy i.e; the smaller size and the higher
charge of the atoms

6. Covalent Bonds- The bond formed between two atoms by mutual sharing of electrons
between them so as to complete their octets or duplets.
7. COVALENCY: The number of electrons which an atom contributes towards mutual
sharing during the formation of a chemical bond called its covalency in that compound.
8. SINGLE COVALENT BOND: A covalent bond formed by the mutual sharing of one
pair of electrons is called a single covalent bond, or simply a single bond. A single covalent
bond is represented by a small line (−) between the two atoms. H2

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9. DOUBLE COVALENT BOND: A covalent bond formed by the mutual sharing of two
pair of electrons is called a double covalent bond, or simply a double bond. A double
covalent bond is represented by two small horizontal lines (=) between the two atoms. E.g.
O=O, O=C=O etc.
10. TRIPLE COVALENT BOND: A covalent bond formed by the mutual sharing of three
pair of electrons is called a triple covalent bond, or simply a triple bond. A triple covalent
bond is represented by three small horizontal lines (≡) between the two atoms. E.g. N≡N, H-
C≡C-H etc.

11. FORMATION OF A COVALENT BOND: Formation of a covalent bond is favoured


by (i) High ionisation enthalpy of the combining elements. (ii) Nearly equal electron gain
enthalpy and equal electro-negativities of combining elements. (iii) High nuclear charge and
small atomic size of the combining elements.
12. Octet Rule- Kossel and Lewis in 1916 developed an important theory of chemical
combination between atoms known as electronic theory of chemical bonding. According to
this, atoms can combine either by transfer of valence electrons from one atom to another or
by sharing of valence electrons in order to attain their octet. This is known as octet rule.
13. Limitations of octet rule-
a) Incomplete octet of the central atom: In some compounds the number of electrons
surrounding the central atom is less than eight. This is especially the case with elements
having less than four valence electrons. Examples- LiCl ,BeCl2 , BCl3
b) Odd-electron molecules: In molecules with an odd number of electrons like nitric oxide,
NO and nitrogen dioxide, the octet rule is not satisfied for all the atoms.
c) The expanded octet : Elements in and beyond the third period of the periodic table have,
apart from 3s and 3p orbitals, 3d orbitals also available for bonding. In a number of
compounds of these elements there are more than eight valence electrons around the central
atom. This is termed as the expanded octet. Some of examples of such compounds are :
PF5, SF6.
d) This theory does not account for the shape of molecules.
14. POLAR COVALENT BOND: The bond between two unlike atoms which differ in their
affinities for electrons is said to be polar covalent bond. E.g. H-Cl
15. COORDINATE BOND: The bond formed when one sided sharing of electrons take
place is called a coordinate bond. Such a bond is also known as dative bond. It is represented
by an arrow (→) pointing towards the acceptor atom. Example :O3 (ozone)

16. Bond length is defined as the equilibrium distance between the nuclei of two bonded
atoms in a molecule.
17. Bond Angle: It is defined as the angle between the orbital containing bonding electron
pairs around the central atom in a molecule/complex ion. It gives some idea regarding the
distribution of orbital around the central atom in a molecule/complex ion and hence it helps
us in determining its shape
18. 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

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19. Bond Order :The Bond Order is given by the number of bonds between the two atoms in
a molecule. E.g.: Bond Order Of O2= 2. With increase in bond order, bond enthalpy
increases and bond length decreases.
20. Covalent character in ionic compounds (Fajan’s rule) :
 There is no compound which is 100% ionic.
 Covalent character in ionic compound can be explained with the help of Fajan’s rule.
 Small size of cation  polarisation :
e.g. BeCl2 MgCl2 CaCl2 SrCl2 BaCl2
Size of cation  Polarisation  Covalent character 

 Large size of anion  Polarisation

LiF LiCl LiBr Lil


- size of anion 
e.g. - polarisation 
- covalent character 
 Charge on cation or anion  polarisation.

(a) charge on cation :


NaCl MgCl2 AlCl3

Na+ Mg+2 Al+3


- Charge of cation 

- Polarisation 

- Covalent character 

(a) Charge on anion :


AlF3 Al2O3 AlN

F-, O-2, N-3

- Charge on anion 
- Polarisation 

- Covalent character 

 Cation which has pseudo inert gas configuration, shows more polarising power
incomparison of cation that has inert gas configuration. CuCl > NaCl (Covalent
character)
Cu+ = [Ne] 3s2p6d10 Na+ = 1s2, 2s2p6
18e- 8e-
Pseudo inert inert gas configuration
gas configuration

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21. Resonance: According to the concept of resonance, whenever a single Lewis structure
cannot describe a molecule accurately, a number of structures with similar energy, positions
of nuclei, bonding and the non- bonding pairs of electrons are taken as the canonical
structures of the hybrid which describes the molecule accurately.

22. Polarity of bonds:In case of heteronuclear molecules like HCl, the shared pair of electron
between the two atoms gets displaced more towards chlorine since the electronegativity of chlorine
is far greater than that of hydrogen. The resultant covalent bond is called a polar covalent bond.
23. Dipole moment : As a result of polarization, the molecule possesses the dipole
moment which can be defined as the product of charge and the distance between the centers
of positive and negative charge. It is usually designated by a Greek letter ‘µ’.
Mathematically, it is expressed as follows:
Dipole moment (µ ) = charge (Q) X distance of separation (r)

24. Sigma( ) bond : This type of covalent bond is formed by the end to end (hand-on)
overlap of bonding orbitals along the internuclear axis. This is called as head on overlap or
axial overlap.

25. pi(π ) bond : In the formation of π bond the atomic orbitals overlap in such a way that
their axes remain parallel to each other and perpendicular to the internuclear axis. The
orbitals formed due to sidewise overlapping consists of two saucer type charged clouds
above and below the plane of the participating atoms.

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26. In case of sigma bond, the overlapping of orbitals takes place to a larger extent. Hence, it
is stronger as compared to the pi bond where the extent of overlapping occurs to a smaller
extent.
27. VSEPR theory
 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 minimize
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 distancefrom 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: Lone pair (lp) –
Lone pair (lp) > Lone pair (lp) – Bond pair (bp) > Bond pair (bp) –Bond pair (bp)
 Geometry of Molecules on the basis of VSEPR Theory

Bond pair Lone pair Shape Examples
2 0 Linear BeCl2
3 0 Trigona l BCl3
Planar

2 1 Bent SO2

4 0 Tetrahedral CH4

3 1 Pyramidal NH3, ,PH3,

2 2 V-shape H2 O

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5 0 Trigonal PCl5
bipyramidal

4 1 See saw SF4

3 2 T-shaped CIF3,

2 3 Linear XeF2
6 0 Octahedral SF6

5 1 Square CIF5,
pyramidal IF5

4 2 Square planar XeF4


,

6 1 Distorted XeF6
Octahedral

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28. Hybridization: It can be defined as the process of intermixing of the orbitals of slightly
different energies so as to redistribute their energies, resulting in the formations of new set of
orbitals of equivalent energies and shape.
 Salient Features of hybridization :
 The number of hybrid orbitals is equal to the number of the atomic orbitals that get
hybridised.
 The hybridised orbitals are always equivalent in energy and shape.
 The hybrid orbitals are more effective in forming stable bonds than the pure atomic
orbitals.
 These hybrid orbitals are directed in space in some preferred direction to have
minimum repulsion between electron pairs and thus a stable arrangement.
29. Types of Hybridisation
(a) sp hybridisation: This type of hybridisation involves the mixing of one s and one p
orbital resulting in the formation of two equivalent sp hybrid orbitals. Each sp hybrid
orbitals has 50% s- character and 50% p-character. Such a molecule inwhich the central
atom is sp-hybridised and linked directly to two other central atoms possesses linear

geometry. Example BeCl2 molecule


(b) sp2 hybridisation : In this hybridization there is involvement of one s and two p-
orbitals in order to form three equivalent sp2 hybridised orbitals. Each sp2 hybrid orbitals
has 33.33% s- character and 66.66 % p-character. Such a molecule in which the central
atom is sp2 hybridised and linked directly to three other central atoms possesses trigonal
planar geometry. Example BCl3 molecule.

(c) sp3 hybridisation: In this type of hybridisation there is mixing of one s-orbital and
three p- orbitals of the valence shell to form four sp3 hybrid orbital of equivalent energies
and shape. There is 25% s-character and 75% pcharacter in each Sp3 hybrid orbital. The
four Sp3 hybrid orbitals so formed are directed towards the four corners of the tetrahedron
Example CH4 molecule

3
30. sp hybridisation in C2H6 molecule
31. sp2 hybridisation in C2H4 molecule

32. sp hybridisation in C2H2 molecule

33. Formation of PCl5

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34. Molecular orbital. It gives electron probability distribution around a group of nuclei in a
molecule. They are filled in the same way as atomic orbitals. Molecular orbitals are formed
bylinear combination of atomic orbitals.
35. Conditions for the Combination of Atomic Orbitals. The linear combination of atomic
orbitals takes place only if the following conditions are satisfied :
(i) The combining atomic orbitals must have same or nearly same energy.
(ii) The combining atomic orbitals must have the same symmetry about the molecular
axis. Byconvention, z-axis is taken as the molecular axis.
(iii) The combining atomic orbitals must overlap to the maximum extent. Greater the
extent of overlapping, the greater will be electron density between the nuclei of a molecular
orbital.
36. Sigma ( ) molecular orbitals. A molecular orbital which is formed from the overlap of
two s atomic orbitlas or head to head overlap of one s and p-atomic orbitals or head to head
overlap of two p-atomic orbitals, is known as sigma molecular orbital.
37. pi (  ) molecular orbitals. A molecular orbital which is formed by lateral overlap of two
parallel p-orbitals is known as pi(  ) molecular orbital.

38. Bonding molecular orbital. A molecular orbital that is formed by addition overlap (i.e.,
when the lobes of atomic orbitals overlap with the same sign) of two atomic orbitals is known
as bonding molecular orbital. It is represented as
MO  A  B Its energy is lower than the atomic orbitals from which it is formed. It
favours bonding.

39. Anti-bonding molecular orbital. A molecular orbital that is obtained by the subtraction overlap
(i.e., when the lobes of atomic orbitals overlap with the opposite sign) of two atomic orbitals is
know as anti-bonding molecular orbital. It is represented as *MO  A  B Its energy is higher

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than the atomic orbitals from which it is formed. It does not favour bonding.

40. Bond order. It is defined as half of the difference between number of electrons in bonding and anti-
bonding orbitals, i.e., B.O. = ½ (Nb – Na) ‘where Nb are number of electrons in bonding
orbitals’ and Na are number of electrons in anti-bonding orbitals. Bond order helps in estimating stability of
atom.
41. Significance of Bond Order
 It bond order = 0, it means species does not exist.
 Bond order of 1, 2 & 3 corresponds to a single bond, double & triple bondrespectively



 Bond order increases  stability of molecule increases  Bond length decreases 
 If the molecule has one or more unpaired electron, it will be paramagnetic, while ifall
the electrons are paired it will be diamagnetic.

42. Energy level Diagrams for Molecular Orbitals. The increasing order of energies of various
molecular orbitals for O2 and F2 is given below.
* * * * *
1s   1s   2s   2s   2 pz   2 px   2 p y   2 p x   2 p y   2 p z
However, this sequence of energy levels of molecular orbitals is not correct for remaining molecules
Li2, Be2, B2, C2, N2. For instance, it has been observed experimentally that for molecules such as B 2, C2,
N2 etc., the increasing order of energies of various molecular orbitals is

44. Energy level Diagrams for Molecular Orbitals. B2, C2, N2 is given below

45. Energy level Diagrams for Molecular Orbitals. O2 F2 and Ne2 is given below

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46. Hydrogen bond can be defined as the attractive force which binds hydrogen atom of one
molecule with the electronegative atom (F, O or N) of another molecule. For example, in HF
molecule, the hydrogen bond exists between hydrogen atom of one molecule and fluorine
atom
of another molecule as depicted below :
47. Conditions required for H-bond.
a) Molecule should have more electronegative atom (F, O, N) linked to the H-atom
b) Size of electronegative atom should be smaller.
c) A lone pair should be present on electronegative atom.
48. Types of H-Bonds There are two types of H-bonds (i) Intermolecular hydrogen bond (ii)
Intramolecular hydrogen bond
49. Intermolecular hydrogen bond: It is formed between two different molecules of the same or
different compounds. For example, H-bond in case of HF molecule, alcohol or water
molecules, etc.

50. Intramolecular hydrogen bond : It is formed when hydrogen atom is in between the two
highlyelectronegative (F, O, N) atoms present within the same molecule. For example, in o-
nitrophenol the hydrogen is in between the two oxygen atoms.

MCQ TYPE EACH CARRY 1 MARK EACH

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

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(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-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

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(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 – REASON TYPE Q.


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 ANSHWER Q. – 2 MARK EACH

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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(a)
Which electrons take part in bond formation?

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(a) Name the method generally used for the calculation of lattice energy or
electron affinity.

Answer: Borh-Haber cycle.


(b) Which type of forces holds the atoms together in an ionic compound?
Answer: Electrostatic forces of attraction.
5(a) Write the Lewis structure of the polyatomic ions CN–, SO 2-.
4

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

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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 ANSHWER Q. CARRY 3 MARKS

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?

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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?
(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-.

VERY LONG ANSHWER TYPE Q. CARRY 5 MARK EACH


1 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.

Q2. What is meant by term bond order ? Calculate the bond order of N 2, O2, O2+, O2-

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CASE BASED QUESTIONS

Read the following passage and anshwer the questions given below:

1. 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 of electrons. 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.

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(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 2 and NO+ are 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 anshwer 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

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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

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CHAPTER – CHEMICAL THERMODYNAMICS


THERMODYNAMIC 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.
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 arecalled 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:
Thermodynamic variable used to describe the behavior of a system at a particular time.
or
The conditions of existence of the system are 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 a process in which the thermodynamic state of a system is
changed.
Isothermal process: In which temperature remains constant, i.e., (Δ T = 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
ofchange.

Reversible process: 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: An irreversible process can be defined as a process in which the system and the
surroundings do not return to their original condition once the process is initiated.

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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 (ΔU)
can be determined by ΔU = U2 – U1 or ΣUP – ΣUR

Modes of energy exchange : These are two ways by which a system can interact or can exchange
energy with its surroundings.
Heat : when the energy transfer takes place because of temperature difference between system &
surroundings. It is known as heat.
Work : Energy transfer which is not heat or which is not because of temperature difference is called
work
First Law of Thermodynamics:
Energy can neither be created nor destroyed although it can be converted from one form to the other.
OR
The energy of an isolated system is constant.
Mathematically, ΔU = q + W
Where, ΔU = internal energy change q = heat added to
systemW = 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): A thermodynamic quantity equivalent to the total heat content of a system. It is
the sum of internal energy of the system and the product of pressure and volume.
At constant volume ∆V = 0, qv =∆ U
So H = U + p∆V,
qp = H2- H1 = ∆H
∆H = ∆U + P.∆ V.
The enthalpy change accompanying a reaction is called the reaction enthalpy
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 is the quantity of heat required to raise the temperature by one degree Celsius.(or 1K).
Specific heat capacity (s): It is the quantity of heat required to raise the temperature of one unit mass of a
substance by one degree celsius (or one kelvin). For finding out the heat, q, required to raise the
temperatures of a sample, we multiply the specific heat of the substance, c, by the mass m, and
temperatures change,

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ΔT as q=c×m×ΔT =CΔT .
Relation between Cp and Cv and ideal gas Cp -CV=R
Measurement of ∆H and ∆U The process is carried out in a vessel called calorimeter,
immersed in aknown volume of a liquid.
(a) ∆U measurements: The energy changes are measured at constant volume. No work is done
.A bomb calorimeter is used.
(b) ∆H measurements: In exothermic reaction, heat is evolved, so q and H will be negative. In
endothermicp 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
participatingsubstances 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, Enthalpy of fusion is
defined as the enthalpy change when one mole of a solid substance in standard
state melts and changes to liquid.
 Standard enthalpy of vaporization or molar enthalpy of vaporization. ∆H vap is the
amount ofheat 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 ofone 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 solidsubstance 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 reactiontakes 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
bondsbetween 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
ioniccompound 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 nonSpontaneous.

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Enthalpy of Solution (symbol : ∆solH0 ) Enthalpy of solution of a substance is the enthalpy


change whenone 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 andpressure
Enthalpy of combustion: It is the enthalpy change when one mole of a compound combines with the
requisite amount of oxygen to given products in their stable forms.
CH4 (g) + 2O2(g) → CO2(g) + 2H2O (l) H o = - 890 kJ mol-1
Enthalpy of atomization (symbol: ΔaH 0 ): It is the enthalpy change on breaking one mole of bonds
completely to obtain atoms in the gas phase. In case of diatomic molecules, like dihydrogen the
enthalpy of atomization is also the bond dissociation enthalpy.
Ionization Enthalpy: The ionization enthalpy of an element can be defined as the amount of energy
required to remove an electron from an isolated gaseous atom in its gaseous state.
Driving forces for spontaneous process:
(i) Tendency for minimum energystate. (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 by its own.
Gibb’s free energy (∆G): It is defined as maximum amount of energy available to a system during
the process that can be converted into useful work. It is a measure of capacity to do useful
work.
∆G = H – T∆S (Gibb’s Helmholts equation) it is equal useful work i.e. - ∆G = W(useful) = W(max.)
Criteria of spontaneity :
(i)If Gsystem is (-ve) < 0  process is spontaneous
(ii) If Gsystem is (+ve) > 0  process is non-spontaneous
(iii) If Gsystem = 0  system is at equilibrium
Effect of Temperature on Spontaneity of Reactions (∆rG0 = ∆rH0 – T∆rS0)

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Gibbs Energy Change and Work rG0 = -nFE  cell ,Here E  cell is the standard cell potential.
Gibbs Energy Change and Equilibrium Constant  G0 = − 2.303RT log K
Third Law of Thermodynamics: The entropy of perfect crystals of all pure elements & compounds is
zero at the absolute zero of temperature.

PRACTICE QUESTIONS
Section-A(MCQ TYPE)

01. A ...................... in thermodynamics refers to that part of universe in which observations are made
and remaining universe constitutes the……………...
(A) surroundings, system
(B) system, surroundings
(C) system, universe
(D) system, boundary

02. Tea place in a thermos flask is an example of


(A) Open system
(B) closed system
(C) isolated system
(D) it cannot act as system

03. Which of the following statements is correct?


(A) The presence of reacting species in a covered beaker is an example of open system.
(B) There is an exchange of energy as well as matter between the system and the surroundings in a
closed system.
(C) The presence of reactants in a closed vessel made up of copper is an example of a closed system.
(D) The presence of reactants in a thermos flask or any other closed insulated vessel is an example of
a closed system

4. Among the following, the intensive properties are


(i) molar conductivity (ii) electromotive force
(iii) resistance (iv) mass
(A) (i) and (ii)
(B) (i), (ii) and (iii)
(C) (i) and (iv)
(D) (i) only

05. The following two reactions are known:


Fe2O3(s) + 3CO (g)  2Fe(s) + 3CO2(g); H = –26.8 kJ
FeO (s) + CO(g)  Fe(s) + CO2(g); H = –16.5 kJ
The value of  H for the following reaction
Fe2 O3 (s) + CO (g)  2FeO + CO2(g) is;
(A) + 6.2 kJ
(B) + 10.3 kJ
(C) – 43.3 kJ

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(D) – 10.3 kJ

06. A reaction cannot take place spontaneously at any temperature when


(A) both H and S are positive
(B) both H and S are negative
(C) H is negative and S is positive
(D) H is positive and S is negative

07.Amount of heat required to vaporize one mole of a liquid at constant temperature and under
standard pressure (1bar) is called
(A) Standard enthalpy of sublimation
(B) standard enthalpy of fusion
(C) standard enthalpy of vaporization
(D) none of the above

07. The standard enthalpy change for the formation of one mole of a compound from
its elements in their most stable states of aggregation is called:
(A) Standard enthalpy of combustion
(B) standard enthalpy of formation
(C) standard enthalpy of vaporization
(D) standard enthalpy of solution

08.For which of the process, ΔS is negative?


(A) H2 (s)→ 2H(g) (B) N2 (g, 1 atm)→ N2 (g, 8 atm)
(C) 2SO3 (g)→ 2SO2 (g) + O2 (g) (D) d. C(diamond) → C(graphite)

09.The favourable conditions for a spontaneous reaction are


(A) TΔS > ΔH, ΔH = + ve, ΔS = + ve (B) TΔS > ΔH, ΔH = + ve, ΔS = - ve
(C) TΔS = ΔH, ΔH = - ve, ΔS = - ve (D) TΔS = ΔH, ΔH = + ve, ΔS = + ve

10.The values of ΔH and ΔS for the reaction C(graphite) + CO2 (g)→ 2 CO (g) are 170 kJ and 170 JK-1
respectively. This reaction will be spontaneous at
(A) 910 K (B) 1110 K
(C) 510 K (D) 710 K

11.The value of enthalpy change (ΔH) for the reaction:


C2H5OH(l) + 3O2 (g) → 2CO2 (g) + 3H2 O(l)
at 27 C is - 1366.5 kJ mol-1 . The value of internal energy change for the above reaction at this
temperature will be :
(A) -1364.0 kJ (B) -1361.5 kJ
(C) -1371.5 kJ (D) -1369.0 kJ

12. If an endothermic reaction occurs spontaneously at constant T and P, then which of the following
is true?
(A) ΔG > 0 (B) ΔH < 0
(C) ΔS > 0 (D) ΔS < 0

13. When 1 mole of crystalline NaCl is obtained from sodium and chlorine gas, 410 kJ of heat is
released. The heat of sublimation of sodium metal is 108 kJ mol-1 and Cl-Cl bond enthalpy is 242

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kJ mol–l . If the ionization energy of Na is 493.0 kJ mol–l and the electron affinity of chlorine is 368
kJ mol–l , the lattice energy of NaCl is
(A) 764 kJ mol–l (B) -764 kJ mol–l
(C) 885 kJ mol–l (D) -885 kJ mol–l

14. Under which of the following condition is the relation ΔH = ΔU + pΔV valid for a closed system?
(A) constant pressure
(B) constant temperature
(C) constant temperature and pressure
(D) constant temperature, pressure and composition

15. Which one of the following equations does not correctly represent the first law of
thermodynamics for the given process?
(A) Isothermal process : q = -w (B) Cyclic process : q = -w
(C) Isochoric process : ΔU = q (D) Adiabatic process : ΔU = -w

16 One mole of an ideal gas expands freely and isothermally at 300 K from 10 litres to 100 litres. If
ΔU = 0, the value of ΔH is
(A) 10 kJ (B) 200 kJ
(C) zero (D) 300 Kj
17. An insulated container is divided into two compartments. One compartment contains an ideal
gas at a pressure P and temperature T while in the other compartment there is perfect vacuum. If
a hole is made in the partition wall, which of the following will be true?
(A) ΔU = O (B) w = 0
(C) ΔT = 0 (D) All the three are true

18. Read the following statements carefully and choose the correct option
(i) In case of diatomic molecules, the enthalpy of atomization is also the bond dissociation enthalpy.
(ii) In case polyatomic molecules, bond dissociation enthalpy is different for different bonds within the
same molecule.
(A) Both (i) and (ii) are correct
(B) (i) is correct but (ii) is incorrect
(C) (ii)is correct but (i) is incorrect
(D) Both (i) and (ii) are incorrect19. Enthalpy of sublimation of a substance is equal to
(A) enthalpy of fusion + enthalpy of vaporization
(B) enthalpy of fusion
(C) enthalpy of vaporization
(D) twice the enthalpy of vaporization

20.‘At absolute zero the entropy of perfectly crystalline substance is taken as zero’ is statement of
(A) zeroth law of thermodynamics
(B) 1st law of thermodynamics
(C) 2nd law of thermodynamics
(D) 3rd law of thermodynamics

21. The standard free energy change is related to equilibrium constant(K) as


(A) ΔrG0 = – 2.303 RT log K
(B) ΔrG0 = 2.303 RT log K
(C) ΔrG0 = RT log K
(D) ΔrG0 = – RT log K

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In FOLLOWING questions (Q. (22) to (25) 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.

22. Assertion (A) : A liquid crystallizes into a solid and is accompanied by decrease in entropy.
Reason (R) : In crystals, molecules organize in an ordered manner.

23. Assertion (A) :Work is a state function


Reason (R) :Work done during the process depends upon the path followed

24. Assertion (A) :Molar entropy of vaporization of water is different from ethanol
Reason (R):Water is more polar than ethanol.

25. Assertion: Many endothermic reactions that are not spontaneous at room temperature
become spontaneous at high temperature.
Reason: Entropy of the system increases with increase in temperature

QN 1 2 3 4 5 6 7 8 9 10
ANS B C C A A D B B A B
QN 11 12 13 14 15 16 17 18 19 20
ANS A C B A D C D A A D
QN 21 22 23 24 25
ANS A A D B B

SECTION- B (SHORT ANSWER QUESTIONS-2MARKS)

Q1. Given that ∆H = 0 for mixing of two gases. Explain whether the diffusion of these
Gases into each other in a closed container are a spontaneous process or not?

ANS: 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.

Q2. 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?
ANS: 1665/4 kJ mol–1 = 416.2 kJ mol–1

Q3. The standard molar entropy of H2O (l ) is 70 J K–1 mol–1. Will the standard molar entropy of H2O(s)
be more, or less than 70 J K–1 mol–1?
ANS: Less, because ice is more ordered than H2O (l ).

Q4. Identify the state functions and path functions out of the following :
enthalpy, entropy, heat, temperature, work, free energy.

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ANS: State Functions : Enthalpy, Entropy, Temperature, Free energy


Path Functions : Heat, Work
Q5. The value of ∆f H0 for NH3 is – 91.8 kJ mol–1. Calculate enthalpy change for the following reaction :
2NH3(g) →N2(g) + 3H2(g)

ANS: ∆r H0 = +91.8 kJ mol–1

Q6. 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.

ANS: Q= n x C X ΔT
= 60/27 x 24 x (55-35)
= 1066.7 J = 1.07 KJ

SECTION- C (SHORT ANSWER QUESTIONS-3MARKS)

1. The fH° for CO2(g) CO(g) and H2O(g) are –393.5, – 110.5 and –241.8 kJ/mol
respectively, the standard enthalpy change (in kJ) for the reaction
CO2(g) + H2(g) → CO(g) + H2O(g) is
Ans: H° = [H0f (CO)(g) + H0f (H2O)(g)] – [H0f (CO2 )(g) + H0f (H2 )(g)]
= [– 110.5 + ( – 241.8)]– [– 393.5 + 0]
= 41.2 kJ/mol

2. ) Bond dissociation enthalpy of H2, Cl2 and HCl are 434 , 242 and 431 kJ mol–1 respectively. Enthalpy
of formation of HCl is:
Ans: H2 + Cl2 → 2HCI
Substituting the given values, we get enthalpy of formation of 2 moles of HCl is – ( 862 – 676)
= –186 kJ.so for one mole of HCl is -186/2=-93 kJmol–1

3. 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?

Ans: ∆G =∆ H – T∆S
Assume that the equation is at equilibrium then ΔG = 0
ΔG=ΔH−TΔS=0
Therefore ΔH =TΔS
T= ΔH/ΔS =2000K
At 2000 K ΔG = 0
Reaction to be spontaneous ΔG must be negative. Therefore temperature should be greater than
2000 K

4. Calculate ΔrG0 for conversion of oxygen to ozone,


3/2 O2(g) → O3(g) at 298 K. if Kp for this conversion is 2.47 × 10–29.
Ans: ΔrG = – 2.303 RT log Kp
0

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ΔrG0= – 2.303 (8.314 J K–1 mol–1) × (298 K) (log 2.47 × 10–29)


= 163000 J mol–1
= 163 kJ mol–1.

SECTION- D (CASE BASED QUESTION-4MARKS)

1.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, whichis 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

(a)The quantity of of heat required to raise the temperature of one unit mass of a
substance by one degreeCelsius is called
(a)Heat capacity (b)Specific heat capacity
(c)Molar heat capacity ( d)Heat content

Answer
b)Specific heat capacity

2. Derive relation between Cp and Cv.

At constant volume, the heat capacity, C is denoted by CV and at constant pressure, this
is denoted by Cp
We can write equation for heat,
q at constant volume as qV = Cv ΔT= ΔU
at constant pressure as qp= Cp ΔT= ΔH
The difference between Cp and CV can be derived for an ideal gas as:
For a mole of an ideal gas, ΔH = ΔU + Δ(PV ) as PV=RT
ΔH = ΔU + Δ(RT )
ΔH = ΔU + R Δ T
On putting the value of ΔH & ΔU
Cp ΔT = Cv ΔT+ R Δ T
Cp = Cv + R
Cp - Cv = R

2. In a chemical reaction, reactants are converted into products and is represented by,
Reactants Products
The enthalpy change accompanying a reaction is called the reaction enthalpy. The
enthalpy change of a chemical reaction, is given by the symbol rH.
r H = (sum of enthalpies of products) – (sum of enthalpies of reactants)
r H =  aiH product -  biH reactant
(Here symbol Σ (sigma) is used for summation and ai and bi are the stoichiometric
coefficients of the products and reactants respectively in the balanced chemical equation. For
example, for the reaction
CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (l)
r H =  aiH product -  biH reactant

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= [Hm (CO2 ,g) + 2Hm (H2O, l)]– [Hm (CH4 , g) + 2Hm (O2, g)]
where Hm is the molar enthalpy’
1. Write the factors affecting enthalpy of reaction.
2.Define Standard Enthalpy of reaction.
3. CaO (s) + CO2 (g) → CaCO3 (s) , f H0 = -178.3 kJmol-1
Can Enthalpy of reaction for above reaction consider as enthalpy of formation of CaCO 3. Explain?
Or
Does entropy increase or decrease when egg is boiled?
Ans.: On boiling egg, entropy decreases as due to denaturation, the helical structure of protein
become more complicated and random coiled structure

SECTION- E (LA-5MARKS)

1.Predict the sign of ΔS for the following changes:


(i) Freezing of water.
(ii) C(graphite) → C(diamond)
(iii) H2(g) at 298 k and 1 bar ___→ H2(g) at 298 k and 10 bar
(iv) H2(g) + I2(g) ___→ 2HI(g)
(v) 2NaHCO3(s) ___→ Na2CO3(s) + CO2(g) + H2O(g)

Ans(i) ΔS= negative


(ii) ΔS= negative
(iii) ΔS= negative
(iv) ΔS= negative
(v) ΔS=positive

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) ; ∆fH0 = –286 kJ mol–

ANS:
(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 above eq.
CO2(g) + 2H2O(l) → CH3OH (l) +3/2 O2(g); ∆rH0 = 726 kJ mol–1 ……….eq. 1
C(graphite) + O2(g) → CO2(g) ; ∆cH0 = –393 kJ mol–1 ………….eq.2
H2(g) +1/2 O2(g) → H2O(l) ; ∆fH0 = –286 kJ mol– ………….eq.3
.
Multiply eq. 3 by 2
2H2(g)+O2(g)→2H2O(l);2ΔfH0=2×−286kJmol−1=−572kJmol−1 ………….eq.4

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On adding eq. 1,eq. 2 and eq. 4 we get

C(graphite)+2H2(g)+1/2 O2(g)→CH3OH(l)

so
Enthalpy of formation of CH3OH ΔfH0=+726−393−572kJmol−1=−239kJmol−1

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CHAPTER --EQUILIBRIUM
KEY NOTES-
 Equilibrium is the state of a process in which the properties like temperature, pressure, and
concentration etc of the system do not show any change with passage of time.
 In all processes which attain equilibrium, two opposing processes are involved .
 Equilibrium is attained when the rates of the two opposing processes become equal.
 If the opposing processes involve only physical changes, the equilibrium is called Physical
Equilibrium.
 If the opposing processes are chemical reactions, the equilibrium is called Chemical
Equilibrium.
Physical Equilibrium
Solid – liquid Equilibrium: H2 O(s) H2 O(l)
Liquid – Gas Equilibrium: H2 O(l) H2 O(g)
Solid – Solution Equilibrium: Salt(Solid) Salt(in solution)
Gas –Solution equilibrium: CO2(g) CO2(in solution)
Equilibrium in Chemical Process
 Reversible reaction: A reaction in which not only the reactants react to form the products
under certain conditions but also the products react to form reactants under the same conditions
Examples: 3Fe(s) + 4H2O(g) Fe3 O4 (s) + 4H 2(g)
 Irreversible reaction: A reaction cannot take place in the reverse direction, i.e. the products
formed do not react to give back the reactants under the same condition.
Example: AgNO3(aq) + NaCl(aq) → AgCl(s) + NaNO 3(g)
 Generally, a chemical equilibrium is represented as
Where A, B are reactants and C, D are products.
Note: The double arrow between the left hand part and right hand part shows that changes are taking
place in both the directions.
On the basis of extent of reaction, before equilibrium is attained chemical reactions may be classified
into three categories.
 . Those reactions which proceed to almost completion.
 Those reactions which proceed to almost only upto little extent.
Those reactions which proceed to such an extent, that the concentrations of reactants and
products at equilibrium are comparable
 The equilibrium state is dynamic and not static in nature.
 Homogeneous equilibrium: All the reactants and products of any reaction under equilibrium are
in same physical state. Example: N2 (g) + 3H2 (g) 2NH 3 (g)
 Heterogeneous equilibrium? :Physical state of one or more of the reacting species may differ
i.e. all the reactants and products are not in same physical state.Example
2NaHCO 3(s) Na2CO3 (s) + CO2(g) + H2 O(l)?
Characteristics of Equilibrium State
 It can be attained only if the reversible reaction is carried out in closed vessel.
 It can be attained from either side of the reaction.
 A catalyst can hasten the approach of equilibrium but does not alter the state of equilibrium.
 It is dynamic in nature i.e. reaction does not stop but both forward and backward reactions
take place at equal rate.
 Change of pressure, concentration or temperature favours one of the reactions (forward or
backward) resulting in shift of equilibrium point in one direction.
Law of Mass Action & Equilibrium Constant

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“The rate at which a substance reacts is directly proportional to its active mass and rate of a chemical
reaction is directly proportional to product of active masses of reactants each raised to a power equal
to corresponding stoichiometric coefficient appearing in the balanced chemical equation”.

Fore reaction
Rate of reaction ∝ [A]a.[B]b
or rate of reaction = K[A] a[B]b
where K is rate constant or velocity constant of the reaction at that temperature.
Applying Law of mass action for general reversible reaction
aA + bB cC + dD

Rate of forward reaction [A]a[B]b


or R f = Kf [A]b [B]b
Similarly for backward reaction
Rb = Kb [C]c [D]d
Equilibrium Quotient or Mass Action Ratio:
aA +bB cC +dD
At equilibrium

When the reaction is not at equilibrium this ratio is called ‘Q C ’ i.e., Q C is the general term used for the
above given ratio at any instant of time. And at equilibrium Q C becomes KC .
 If the reaction is at equilibrium, Q = K c
 A net reaction proceeds from left to right (forward direction) if Q < KC .
 A net reaction proceeds from right to left (the reverse direction) if Q >Kc
The Le–Chatelier’s Principle:Statement:
“When a chemical reaction at equilibrium is subjected to any stress, then the equilibrium shifts in that
direction in which the effect of the stress is reduced.”
Effect of Addition of Inert Gases:
 Addition of inert gas at constant volume: No effect on equilibrium.
 Addition of inert gas at constant pressure: Equilibrium shifts in a direction where there is
increase in number of moles of gases.
Effect of Change in Temperature:
 In a system at equilibrium, both exothermic and endothermic reactions take place
simultaneously.
 Increase in temperature would shift the equilibrium in the direction of endothermic reaction.
 Decrease in temperature would shift the equilibrium in the direction of exothermic reaction.
Effect of Change in Concentration:
 When the concentration of reactants increased, equilibrium shifts in forward direction.
 When the concentration of the products is increases, equilibrium shifts in backward direction.
Effect of Change in Pressure:
 Increase in pressure shifts the equilibrium in the direction of lesser number of gaseous
molecules.
 Decrease in pressure shifts the equilibrium in the direction of larger number of gaseous
molecules.
Effect of Catalyst:
Catalyst does not change the equilibrium.
Summary of Le Chatelier’s Principle

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Type of Effect or Change Direction of Equilibrium


Addition of more reactants Forward direction

Addition of more products Backward direction

Increase in temperature Towards endothermic reaction


Decrease in temperature Towards exothermic reaction
Addition of Catalyst No effect
Increase in Pressure where the no. of gaseous moles are less

Decrease in Pressure where the no. of gaseous moles are more

Addition of Inert gas at const.Volume No effect

Addition of Inert gas at const.pressure where the no. of gaseous moles are more

Thermodynamics of chemical equilibrium:


ΔG = ΔG 0 + 2.303 RT log Q
At equilibrium:
ΔG = ΔG 0 + 2.303 RT log K = 0
or
ΔG 0 = - 2.303 RT log K
Acids and Bases:
1. Arrhenius Definition:
a. Acids give H + ions aqueous solutions.
b. Bases give OH - ions in aqueous solution.
2. Bronsted – Lowry Definition:
a. Acid is a proton donor .
b. Base is a proton acceptor.
3. Strong and Weak Acids:
a. Strong acid dissociate completely in aqueous solution.
Example: HCl
b. Weak acid dissociates partially in aqueous solution.
Examples: CH 3COOH
Degree of dissociation (a) =(Ka/C) 1/2
Where,
Ka = [CH 3COO-][H +]/[CH3COOH] and
C = Initial concentration of acid.
Also

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[H+] = Ca = (Ka×C) 1/2


c. Ionic Product of Water:
H 2 O H + + OH –
K[H2 O] = [H +] [OH–] = 10-14
Common Ion effect:
The addition of an ion to equilibrium, having the same ion makes the equilibrium `reaction move in
a direction to consume that ion.
This implies that water would dissociate less in the presence of HCl.
Hydrolysis of salts:
1. Salt of a Weak Acid and Strong Base:
[H+] = (Kw Ka / C )1/2
2. Salt of a Weak Base and Strong Acid
[H+] = (Kw / Kb C )1/2
3. Salt of a Weak Acid and Weak Base
[H+] = (Kw Ka / Kb ) 1/2
 Buffer Solutions: Resists change in its pH when such a change is caused by the addition of a small
amount of acid or base.
1. Weak acid–Salt buffer:
Formed by combination of a weak acid and a salt of the acid with a strong base. Example, CH 3COOH &
CH 3COONa
pH = pKa + log [Conjugated base]/ [Acid]
For weak dibasic acid
pH = (pKa1 + pKa2 )/2
Where pKa1 and pKa2 are 1 st and 2nd dissociation constant of the acid.
2. Weak base–salt buffer: Formed by combination of a weak base and a salt of the base with a strong
acid. Example, NH 4 OH and NH 4Cl
pH = pKb + log [Conjugated acid]/ [Base]
Solubility and Solubility Product :
1. Amount (moles) of the salt that has made the solution saturated per liter of solution is called the
solubility of the salt.
2. For salt AB.
AB ↔A + +B-
Ksp = [A +][B-]
3. Solution cannot have the product of the concentration of the ions more than K SP of the salt in
solution.
Ionic Product:
a) Product of ionic concentration due to ions already present in water or from a salt.
b) I.P. may be and may not be equal to K sp .
c) If ionic Product (IP) > K sp ; precipitation takes place till I.P. equals K sp
d) If Ionic Product < K sp ; a precipitate will not be formed and the solution will be unsaturated.
e) If Ionic Product = K sp ; a precipitate will not form an the solution is satuated in that salt.

MULTIPLE CHOICE QUESTIONS (1 MARKS)


1. When rain is accompanied by a thunderstorm, the collected rain water will have pH value
(A) slightly higher than that when the thunderstorm is not there.
(B) uninfluenced by the thunderstorm

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(C) which depends upon the amount of dust in air


(D) slightly lower than that of rain water without thunderstorm.
2. Water is a
(A) Protophobic solvent (B) Protophilic solvent
(C) Amphiprotic solvent (D) Aprotic solvent
3. In the hydrolysis of a salt of weak acid and weak base the hydrolysis constant Kb is equal to
(A) Kw/Kb (B) Kb/Kw (C) Kw/Kab (D) KaKb
4. Solubility of Pbl2 is 0.0013 M. Then solubility product of Pbl2 is
(A) 2.2 × 10-9 (B) 8.8 × 10-9 (C) 6.8 × 10-6 (D) 8.8 × 10-6
5. Which of the following is a Lewis base?
(A) AlCl3 (B) Ag+ (C) Al(OH)3 (D) NH3
6. CO2 is
(A) Lewis acid(B) Lewis base(C) Bronsted acid(D) Bronsted base.
7. Which is not Lewis acid?
(A) BF3 (B) AgCl (C) BeCl2 (D) MgCl2
8. A base according to Bronsted concept is a substance which can
(A) lose a pair of electrons (B) donate protons
(C) gain a pair of electrons (D) accept protons.
9. Aluminium chloride is
(A) Bronsted Lowry acid (B) Arrhenius acid
(C) Lewis acid (D) Lewis base
10. What happens to the yield of this reaction when temperature is increased?
N2 + O2 ⇌ 2NO; 43 k cal
(A) increases (B) decreases (C) remains same (D) none of these
11. For a reversible reaction, if the concentrations of the reactants are doubled, the equilibrium
constant will be
(A) halved (B) doubled (C) the same (D) one fourth
12. The rate of forward reaction is two times that of the reverse reaction at a given temperature and
identical concentration, k(equilibrium) is
(A) 0.5 (B) 1.5 (C) 2.5 (D) 2.0
13. 1 mole of N2 and 2 moles of H2 are allowed to react in a 1 dm³ vessel. At equilibrium 0.8 mole of
NH3 is formed. The concentration of H2 in the vessel is
(A) 0.6 mole (B) 0.8 mole (C) 0.2 mole (D) 0.4 mole.
14. In which of the following equilibrium, change in the volume of the system does not alter the number
of moles?
(A) N2 (g) + O2 (g) ⇌ 2NO (g) (B) PCl5 (g) ⇌ PCl3 (g) + Cl2 (g)
(C) N2(g) + 3H2 ⇌ 2NH3 (g) (D) SO2Cl2 (g) ⇌ SO2 (g) + Cl2 (g)
15. The reaction quotient (Q) for the reactionN2 (g) + 3H2 (g) ⇌ 2NH3 (g) is given by
Q = [NH3]²/[N2][H2]³The reaction will proceed from right to left if
(A) Q = Kc. (B) Q < Kc (C) Q > Kc. (D) Q = 0
16. One mole of N2O4 (g) at 300 K is kept in a closed container under one atmosphere. It is heated to 600
K when 20% by mass of N2O4 (g) decomposes to NO2 (g). The resultant pressure is
(A) 1.2 atm (B) 2.4 atm (C) 2.0 atm (D) 1.0 atm.
17. In which manner, the increase of the pressure will affect the following equilibrium?
C(s) + H2O (g) ⇌ CO (g) + H2 (g)

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(A) Shifts in the forward direction (B) Shifts in the reverse direction
(C) Increase the yield of hydrogen (D) No effect.
18. For the chemical reaction3X (g) + Y (g) ⇌ X3Y (g) the amount of X3Y at equilibrium is affected by
(A) Temperature and pressure (B) Pressure only
(C) Temperature only (D) Temperature, pressure and catalyst.
19. When two reactants A and B are mixed to give products C and D, the concentration quotient (Q) at
initial stage of the reaction
(A) Is zero (B) Decreases with time
(C) Is independent of time (D) Increases with time.
20. The following reaction occurs in the blast furnace where iron ore is reduced to iron metal: 3Fe 2O3(s) +
3CO(g) ⇌ 2Fe(l) + 3CO2(g)
Using the Le Chatelier’s principle, predict which one of the following will NOT disturb the equilibrium?
(A) Removal of CO (B) Removal of CO2 (C) Addition of CO2 (D) Addition of Fe2O3

ANSWERS OF MCQ

1.D 2.C 3.C 4.B 5.D 6.A 7.D 8.D 9.C 10 A


11.C 12.D 13.B 14.A 15.C 16.B 17.B 18.A 19.D 20 D
ASSERTION AND REASON TYPE QUESTIONS(1 MARKS):-
Directions:- In the following questions, a statement of assertion is followed by a statement of reason Mark
the correct choice as:
A) If both assertion and reason are true and reason is the correct explanation of assertion
B) If both assertion and reason are true and reason is the not the correct explanation of assertion
C) If assertion is true but reason is false
D) If assertion is false but reason is true
1) Assertion: - benzoic acid is stronger than acetic acid
Reason: - Ka for benzoic acid is 6.5 x 10-5 and for acetic acid is 1.74 x 10-5
2) Assertion: - a solution of NH4Cl in water is acidic in nature
Reason: - ammonium ions undergo hydrolysis to form Ammonium hydroxide.
3) Assertion :- weak acids have a very strong conjugate base while strong acid have a very weak conjugate
base
Reason:-conjugate acids and bases are differ by only one proton
4) Assertion: - if the reaction quotient for a particular reaction is greater than Kc than thereaction will
Proceed in the direction of reactants
Reason: - Reaction Quotient is defined in the same way as the equilibrium constant Kcexcept that the
concentrations in Qc are not necessarily the equilibrium values.
ANSWERS OF ASSERTION AND REASON TYPE QUESTIONS-
1 (A) both assertion and reason are true and reason is the correct explanation of assertion
2 (A) both assertion and reason are true and reason is the correct explanation of assertion
3 (B) both assertion and reason are true and reason is the not the correct explanation of assertion.

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4 (B) both assertion and reason are true and reason is the not the correct explanation of assertion
VERY SHORT ANSWER TYPE QUESTIONS(2 MARKS)-
1. Identify the type of equilibrium in the following physical processes:
i. Camphor(s) ⇌ Camphor(g)
ii. Ammonium chloride(s) ⇌ Ammonium chloride(g)
iii. Carbon dioxide gas ⇌ Dry ice
iv. Water ⇌ Ice
2. Explain the law of mass action and give its mathematical representation.
3. Write the rate equation for the following reactions:
i. C + O2 → CO2
ii. 2KClO3 → 2KCl + 3O2
4. Explain in short homogeneous equilibrium and heterogeneous equilibrium.
5. What are the characteristics of equilibrium constant?
6. Given the equilibrium reaction, H2O(g) + CH4(g) ⇌ CO(g) + 3H2(g)
Using Le Chatelier’s principle, predict how concentration of CO will change when the equilibrium is
disturbed by
i. adding CH4 ii. adding H2 iii. removing H2O iv. removing H2
ANSWER VERY SHORT ANSWER TYPE QUESTIONS-
ANS 1 :
i. Solid – vapour equilibrium
ii. Solid – vapour equilibrium Solid
iii. Solid – vapour equilibrium
iv. Solid – liquid equilibrium
ANS 2-Statement: The law of mass action states that the rate of a chemical reaction at each instant is
proportional to the product of concentrations of all the reactants.
Explanation: A rate equation can be written for a reaction by applying the law of mass action as follows:
Consider a reaction, A + B → C
Here A and B are the reactants and C is the product. The concentrations of chemical species are expressed
in mol L-1 and denoted by putting the formula in square brackets. On applying the law of mass action to this
reaction, a proportionality expression can be written as: Rate ∝ [A] [B]
This proportionality expression is transformed into an equation by introducing a proportionality constant, k,
as follows: Rate = k [A] [B]
This equation is called the rate equation and the proportionality constant, k, is called the rate constant of
the reaction.
ANS 3- The rate equation is written by applying the law of mass action.
i. The reactants are C and O2
Rate ∝ [C] [O2]
∴ Rate = k [C] [O2]
ii. The reactant is KClO3 and its 2 molecules appear in the balanced equation.
∴ Rate ∝ [KClO3]2
∴ Rate = k [KClO3]2

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ANS 4- i. In a homogeneous equilibrium, the reactants and products are in the same phase.
e.g. Dissociation of HI:
2HI(g) ⇌ H2(g) + I2(g)
ii. In a heterogeneous equilibrium, the reactants and products exist in different phases, e.g. Formation of
NH4Cl:
NH3(g) + HCl(g) ⇌ NH4Cl(s)
ANS 5- Characteristics of equilibrium constant:
 The value of equilibrium constant is independent of initial concentrations of either the reactants or
products.
 Equilibrium constant is temperature dependent. Hence, KC and KP change with change in
temperature.
 Equilibrium constant has a characteristic value for a particular reversible reaction represented by a
balanced equation at a given temperature.
 Higher value of KC or KP means more concentration of products is formed and the equilibrium point
is more towards right hand side and vice versa.
ANS 6- i. Adding CH4: Adding CH4 will favour the forward reaction and the yield of CO and H2 will increase.
ii. Adding H2: Adding H2 will favour the reverse reaction and the yield of CO and H2 will decrease.
iii. Removing H2O: Removing H2O will favour the reverse reaction and the yield of CO and H2 will decrease.
iv. Removing H2: Removing H2 will favour the forward reaction and the yield of CO and H2 will increase.
SHORT ANSWER TYPE QUESTIONS-(3 MARKS)
1.Determine the concentration of CO2 which will be in equilibrium with 2.5 × 10-2, mol L-1 of CO at 100°C for
the reaction FeO (s) + CO (g) ⇌ Fe (s) + CO2 (g); Kc = 5.0.
2. Prove that the pressure necessary to obtain 50% dissociation of PCl5 at 500 K is numerically equal to the
three times the value of the equilibrium constant, Kp.
3. A solution is found to contain 0.63 g of nitric acid in 100 mL of the solution. What is the pH of the
solution.
4. The ionization constant at 298K is 1.8 x 10 -4 .Calculate the ionization constant of the
correspondingconjugatebase.

ANSWER SHORT ANSWER TYPE QUESTIONS-


ANS 1.

ANS 2-

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Total no. of moles = 1.5


If P is the total required pressure, then

ANS 3.HNO3 → H+ + NO3 completely


∴ [HNO3] = [H+] as nitric acid is a strong acid.
Cone, of HNO3 = 0.63 g per 100 mL
Strength L-1 = 6.3
[HNO3] = 6.3/63 = 0.1 = 10-1 M
∴ [H+] = 10-1 M
∴ pH = – log 10-1 = 1.
ANS 4. Ka x Kb =Kw
Kb= Kw/Ka
= (1 x10 -14) /1.8x10 -8
= 5.55x10 -7
CASE BASED QUESTIONS (4 MARKS)
Read the given passage and answer the questions that follow:
Equilibrium can be established for both physical and chemical processes and at equilibrium rate of forward
and reverse processes are equal. Equilibrium constant (KC) is expressed as the concentration of products
divided by reactants, each raised to Stoichiometric Coefficient. KC has fixed value of constant temperature
and at this stage concentration, pressure etc. become constant. KP is equilibrium constant in terms of partial
pressure of gases or vapours. The direction of reaction can be predicted by reaction quotient Q C and QP. QC
= KC at equilibrium and QP = KP. Le Chatelier's principle states 'Equilibrium' will shift in the direction so as to
counter balance the effect of change in T, P and conc. The equilibrium between ions and unionised
molecules in weak electrolyte is called ionic equilibrium
1. When Q (concentration quotient) is smaller than equilibrium constant reaction will proceed in which
direction?
Ans- backward direction
2. In the equilibrium H2(g) + I2(g) 2HI(g), if at a given temperature, the concentration of the reactants are
increased, what will be the value of equilibrium constant Kc .
Ans. Kc will remain the same. It changes only with change in temperature.
3. If the value of an equilibrium constant for a particular reaction is 1.6 × 1012, what will be present in the
system at equilibrium.
Ans. The system will contain mostly products, since value of Kc is high.

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4. The Ksp of AgCl, AgBr, AgI are 1.8 × 10–10, 5.0 × 10–13, 8.3 × 10–17, which will precipitate last if AgNO3
solution is added to NaCl, NaBr, NaI?
Ans. AgI will precipitate because its Ksp is low, ionic product will exceed Ksp.
OR
Write the solubility product expression for:
Ag2CrO4 (s) ⇌ 2Ag+ (aq) + CrO42- (aq)
Answer: Ksp = [Ag+]2[CrO42-].
Read the following passage and answer the questions that follow:
Arrhenius acids give H+ ion in aqueous solution where as bases give OH– in aqueous solution. Bronsted acids
are proton donor where as Bronsted bases are proton acceptors. Acids, on donating proton form conjugate
base where as bases form conjugate acid after accepting proton. Buffer solution is a solution whose pH does
not change by adding small amount of H+ or OH– . The decrease in conc. of one of the ion by adding other
ion as common ion is called common ion effect. Lewis acids are electron deficient or +vely charged. Lewis
bases are electron rich or negatively charged. Ksp (solubility product) is product of molar concentration of
ions raised to power number 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 is ionic product of water, 1 × 10–14 at 298 K. Kw increases with increase in temperature. pH is –log
[H3O+ ] where [H3O+] = Ca in mono protic acid 'C' is molar conc., 'a' is degree of ionisation. A salt is said to be
hydrolysed if pH of solution changes. KH is hydrolytic constant. pH of salts of strong acid and strong base is
equal to 7. pH of other salts can be 7. pH of buffer solution can be calculated with the help of Henderson
equation.
(1) What will be conjugate base of (i) H2SO4 (ii) HCO3– ?
Ans. (i) HSO4– (ii) CO32–
(2) What are conjugate acids of (i) NH2 – (ii) NH3
Ans. (i) NH3 (ii) NH4+
(3) What is the pH of 0.1 M HCl?
Ans.pH = – log [H+] = – log 10-1 = 1.
(4)What is pOH? What is its value for pure water at 298 K?
Answer:
pOH = – log [OH–]
pH + pOH = 14 for pure water at 298 K
pH = 7
or
pOH of water at 298 = 7.
OR
Calculate the pH of a buffer solution containing 0.1 moles of acetic acid and 0.15 mole of sodium acetate.
The ionization constant for acetic acid is 1.75 × 10-5.

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Answer:

LONG ANSWER TYPE QUESTIONS (5 MARKS )


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+.
Answer
(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) BF3, H+ NH4+.
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.
Answer:
(a) It is defined as the product of molar conc. 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 forsolubility.
Equilibrium
Zr3(PO4)4⇌3Zr4+ + 4PO43-
Ksp = [Zr4+]3[ PO43-]4
(b) pH = -log[H3O+]
= -log Cα
= -log√Ka x C
= -log√1.74 x 10-5 x 0.01= 3.3783

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(c ) It is due to common ion,Cl- increase, rate of backward reaction increases, solubility of NaCl decreases.

CH: 8 Redox- Reaction

1 Key Notes:

Classical concept of oxidation and reduction:


The term “oxidation” is defined as the addition of oxygen/electronegative element to a substance or
removal of hydrogen/electropositive element from a substance for eg.

………….. 1

In the above reactions, the elements magnesium and sulphur are oxidised on account of addition of
oxygen to them

……………2

The oxidation of magnesium with fluorine, chlorine is due to addition of electronegative element to
Mg.

The oxidation of H2S is due to removal of hydrogen

………3
oxidation due to the removal of electropositive element potassium from potassium ferrocyanide
before it changes to potassium ferricyanide.

The term “Reduction” is defined as the removal of oxygen/electronegative element from a substance or
addition of hydrogen/ electropositive element to a substance.

…………..4

……..5

(removal of electronegative element, chlorine from ferric chloride)

………………6

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(addition of mercury to mercuric chloride)

Oxidising agents (Oxidant): Oxidising agents is the substance which supplies oxygen to other elements or
removes hydrogen from other element .It is the substance which itself get reduced in the reaction. For
example O2 in eq.1,Cl2 and F2 in eq.2 and H2O2 in eq.3 are Oxidising agents

Reducing agents (Reductant): Reducing agents is the substance which supplies hydrogen to other
elements or removes oxygen from other element .It is the substance which itself get oxidised in the
reaction. For example H2 in eq.5, SnCl2 in eq.6 are reducing agents agents

2 Redox reactions: oxidation and reduction taking place simultaneously thus these reactions are called
redox reactions.
3 REDOX REACTIONS IN TERMS OF ELECTRON TRANSFER REACTIONS:

Above reaction is a redox reactions because in this reactions sodium is oxidised due to the addition of
more electronegative element (Cl) to sodium. Simultaneously, chlorine is reduced because to it, the
electropositive element sodium has been added.

For convenience, each of the above processes can be considered as two separate steps, one involving
the loss of electrons and the other the gain of electrons.Each of the steps is called a half reaction

The half reactions that involve loss of electrons are called oxidation reactions. Similarly, the half
reactions that involve gain of electrons are called reduction reactions.
Thus from electronic concept:

Oxidation: Loss of electron(s) by any species. ( De- electronation)


Fe → Fe2+ + 2e-
Sn 2+ → Sn4+ +2e-
Reduction: Gain of electron(s) by any species. (electronation)
Fe3+ +e- → Fe2+
Sn4+ +2e- → Sn 2+
Cl2+2e- → 2Cl-
Oxidising agent: Acceptor of electron(s).
Reducing agent: Donor of electron(s).
Competitive Electron Transfer Reactions: Place a strip of metallic zinc in an aqueous solution of copper

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nitrate for about one hour. You may notice that the strip becomes coated with reddish metallic copper
and the blue colour of the solution disappears. Formation of Zn 2+ ions among the products can easily be
judged when the blue colour of the solution due to Cu2+ has disappeared.
The reaction between metallic zinc and the aqueous solution of copper nitrate is

In above reaction, zinc has lost electrons to form Zn 2+ and, therefore, zinc is oxidised.
Evidently, now if zinc is oxidised, releasing electrons, something must be reduced,
accepting the electrons lost by zinc. Copper ion is reduced by gaining electrons from the
zinc.

Oxidation –Number Concept:


Oxidation –Number of an element is the charge which an atom of an element has in its ion or appears to
have when present in the combined state with other atoms. It is also called oxidation state.
oxidation state of an element in a compound ascertained according to a set of rules formulated on the
basis that electron in a covalent bond belongs entirely to more electronegative element.

Following rules are applied to determine the oxidation of an atom in an ion or a molecule.
1 In elements, in the free or the uncombinedstate, each atom bears an oxidationnumber of zero.
Evidently each atom in H2, O2, Cl2, O3, P4, S8, Na, Mg, Al has theoxidation number zero.
2 For ions composed of only one atom, theoxidation number is equal to the chargeon the ion. Thus Na+
ion has an oxidationnumber of +1, Mg2+ ion, +2, Fe3+ ion, +3, Cl– ion, –1, O2– ion, –2; and so on.
3 The oxidation number of oxygen in mostcompounds is –2. However, we come across
two kinds of exceptions here in peroxides (e.g., H2O2, Na2O2), eachoxygen atom is assigned an
oxidationnumber of –1, in superoxides (e.g., KO2,RbO2) each oxygen atom is assigned anoxidation
number of –(½). When oxygenis bonded to fluorine. In such compounds e.g., oxygen difluoride (OF2)
and dioxygen difluoride (O2F2), the oxygen is assignedan oxidation number of +2 and +1, respectively.
4 The oxidation number of hydrogen is +1, except when it is bonded to metals in binary compounds (that
is compounds containingtwo elements). For example, in LiH, NaH, and CaH2, its oxidation number is –1.
5 In all its compounds, fluorine has anoxidation number of –1. Other halogens (Cl, Br, and I) also have an
oxidation numberof –1, when they occur as halide ions in their compounds. Chlorine, bromine
andiodine when combined with oxygen, for example in oxoacids and oxoanions, havepositive oxidation
numbers
6 The algebraic sum of the oxidation numberof all the atoms in a compound must bezero
7 In polyatomic ion, the algebraic sumof all the oxidation numbers of atoms ofthe ion must equal the
charge on the ion

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8 It is clear that the metallic elements have positive oxidation number and nonmetallic elements have
positive or negative oxidation number The highest oxidation number of a representative element is the
group number for the first two groups ( S-Block elements) and the group number minus 10 (following
the long form of periodic table) for the other groups (P-Block elements).Highest negative oxidation state
of P-block elements is equal to 8- no. of valence electrons.

Calculate the oxidation number of underlined element in the following:

S.N. Formula Calculation Oxidation state


1 H 2S 2(+1)+x=0 X = -2
2 CO2 X+2(-2)=0 X = +4
3 Na3PO4 3(+1)+x+4(-2) =0 X = +5
4 NO3- X+3(-2)= -1 X = +5
5 CO3 2- X+3(-2)= -2 X = +4
6 CIO4- X+4(-2)= -1 X = +7
7 Cr2O7 2- 2X+7(-2)= -2 X = +6
8 MnO4- X+4(-2)= -1 X = +7
9 [Fe(CN)6]4- X+6(-1)= -4 X = +2
10 H3P2O7- +3+2x+7(-2)= -1 X = +5
11 CrO5 X+4(-1)+1(-2)=0 X = +6
12 Na2S2O8 +2+2X+6(-2)+2(-1) = 0 X = +6

The idea of oxidation number can be apply to define oxidation, reduction, oxidising agent (oxidant),
reducing agent (reductant) and the redox reaction.
we may say that:
Oxidation: An increase in the oxidation number of the element in the given substance.
Reduction: A decrease in the oxidation number of the element in the given substance.

Oxidation number of the Zn is increases from 0 to +2 so Zn is oxidized while Oxidation number of the
Cu is decreases from +2 to0 so Cu is reduced.

Oxidising agent: A reagent which can increase the oxidation number of an element in a given substance.
Or the substance O.N.of whose atom decreases

Reducing agent: A reagent which lowers the oxidation number of an element in a given
Substance Or the substance O.N.of whose atom increases.

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Redox reactions: Reactions which involve change in oxidation number of the interacting
Species
Types of Redox Reactions :
1. Combination reactions : A combination reaction may be denoted in the

Either A and B or both A and B must be in the elemental form for such a reaction to be a redox reaction

2. Decomposition reactions:
Decomposition reaction leads to the breakdown of a compound into two or more
components at least one of which must be in the elemental state. Examples of this class of reactions are

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. It may be denotedas:
Y

(a) Metal displacement:

(b) Non-metal displacement: The non-metal displacement redox reactions include hydrogen
displacement. All alkali metals and some alkaline earth metals (Ca, Sr, and Ba) which are very good
reductants, will displace hydrogen from cold water.

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The power of these elements as oxidising agents decreases as we move down from fluorine to
iodine in group 17 of the periodic table. This implies that fluorine is so reactive that it can replace
chloride, bromide and iodide ions in solution. In fact, fluorine is so reactive that it attacks water and
displaces the oxygen of water :

Chlorine can displace bromide and iodide ions in an aqueous solution as shown below:

As Br2 and I2 are coloured and dissolve in CCl4, can easily be identified from the colour of the solution
above reactions form the basis of identifying Br– and I– in the laboratory through the test popularly
known as ‘Layer Test’.

4. Disproportionation reactions:
Disproportionation reactions are a special type of redox reactions. In a disproportionation reaction an
element in one oxidation state is simultaneously oxidised and reduced. One of the reacting substances
in adisproportionation reaction always containsan element that can exist in at least threeoxidation
states. The element in the form ofreacting substance is in the intermediateoxidation state; and both
higher and lower oxidation states of that element are formed inthe reaction.

Phosphorous and chlorine undergo disproportionation in the alkaline medium as shown below :

fluorine that, being the most electronegative element, it cannot exhibit any positive oxidation
state. This means that among halogens, fluorine does not show a disproportionation tendency
(a) Half Reaction Method: In this method, the two half equations are balanced separately and then
added together to give balanced equation.

Step 1: Produce unbalanced equation for the reaction in ionic form :


Fe 2+(aq) + Cr2O72– (aq) → Fe 3+ (aq) + Cr 3+(aq)

1.Separate the equation into half reactions:

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2. Balance the atoms other than O and H in each half reaction individually

Balance the O atoms in each half reaction individually by adding required of water molecules to the side
deficient in terms of oxygen
Cr2O72– (aq) → 2Cr 3+(aq) + 7H2O (l)

Balance hydrogen atom (a)For reactions occurring in acidic medium, add H+ to balance H atoms to the
side deficient in term of hydrogen.
Cr2O72– (aq) +14H+ → 2Cr 3+(aq) + 7H2O (l)

Balance charge : Add electrons to one side of the half reaction to balance the charges. The oxidation half
reaction is thus rewritten to balance the charge:

Fe 2+ (aq) → Fe 3+ (aq) + e Cr2O72– (aq) +14H+ +6e → 2Cr 3+(aq) + 7H2O (l)
If need be, make the number of electrons equal in the two half reactions by multiplying one or both half
reactions by appropriate coefficients.
6Fe 2+ (aq) →6 Fe 3+ (aq) +6 e Cr2O72– (aq) +14H+ +6e → 2Cr 3+(aq) + 7H2O (l)
We add the two half reactions to achieve the overall reaction and cancel the electrons on each side. This
gives the net ionic equation as :
Cr2O72– (aq)+ 6Fe 2+ (aq) +14H+ → 2Cr 3+(aq) +6 Fe 3+ (aq) + 7H2O (l)
Verify that the equation contains the same type and number of atoms and the same charges on both
sides of the equation. This last check reveals that the equation is fully balanced with respect to number
of atoms and the charges.
For the reaction in a basic medium, first balance the atoms as is done in acidic medium. Then for each H +
ion, add an equal number of OH– ions to both sides of the equation. Where H+ and OH– appear on the
same side of the equation, combine these to give H2O.
(ii) Half Reaction Method in basic medium : In this method, the two half equations are balanced
separately and then added together to give balanced equation.
Step 1: Produce unbalanced equation for the reaction in ionic form :
for eg. Permanganate (VII) ion, MnO4– in basic solution oxidises iodide ion, I– to produce molecular
iodine (I2) and manganese (IV) oxide (MnO2). Write a balanced ionic equation to represent this redox
reaction.
MnO4– (aq) + I– (aq) → MnO2(s) + I2(s)
1.Separate the equation into half reactions:
I– (aq) → I2(s) MnO4– (aq) → MnO2(s)

2. Balance the atoms other than O and H in each half reaction individually
2I– (aq) → I2(s) MnO4– (aq) → MnO2(s)
Balance the O atoms in each half reaction individually by adding required of water molecules to
the side deficient in terms of oxygen
2I– (aq) → I2(s) MnO4– (aq) → MnO2(s) + 2H2O (l)
Balance hydrogen atom (b) For the reaction in a basic medium, first balance the H atoms as is done
in acidic medium. Then for each H+ ion, add an equal number of OH– ions to both sides of the
equation.

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2I– (aq) → I2(s) MnO4– (aq) +4H+ → MnO2(s) + 2H2O (l)


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

Where H+ and OH– appear on the same side of the equation, combine these to give H2O
2I– (aq) → I2(s) MnO4– (aq) ++ 2H2O (l) → MnO2(s) + 4OH-

Balance charge : Add electrons to one side of the half reaction to balance the charges. The
oxidation half reaction is thus rewritten to balance the charge:

2I– (aq) → I2(s) +2e MnO4– (aq) + 2H2O (l) +3e → MnO2(s) + 4OH-
If need be, make the number of electrons equal in the two half reactions by multiplying one or both
half reactions by appropriate coefficients.
[2I– (aq) → I2(s) +2e ]x3 [MnO4– (aq) + 2H2O (l) +3e → MnO2(s) + 4OH- ] x2
6I– (aq) → 3 I2(s) +6e 2MnO4– (aq) + 4H2O (l) +6e → 2MnO2(s) + 8OH-
We add the two half reactions to achieve the overall reaction and cancel the electrons on each
side. This gives the net ionic equation as :

2MnO4– (aq) + 4H2O (l) + 6I– (aq) → 2MnO2(s) + 3 I2(s) +8OH-

Verify that the equation contains the same type and number of atoms and the same charges on
both sides of the equation. This last check reveals that the equation is fully balanced with respect
to number of atoms and the charges.

(2)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.
Cr2O72–(aq) + SO32–(aq) → Cr3+(aq) + SO42–(aq)

Step 3: Calculate the increase or decrease in the oxidation number per atom and for the entire
molecule/ion in which it occurs.

This indicates that the dichromate ion is the oxidant and the sulphite ion is the reductant.

(a) Increase in oxidation number per atom : 2


(b) decrease in oxidation number per atom : 3
calculate total Increase/decrease in oxidation number by multiplying it with total number of atoms
(c) Total Increase in oxidation number: 2 x 1(no. of sulpher atoms) = 2
(d) Total decrease in oxidation number: 3 x 2 (no.of chromium atoms) = 6
Make atoms other than O and H equal on both side
Cr2O72–(aq) + SO32–(aq) → 2 Cr3+(aq) + SO42–(aq)
Make total increase in oxidation number equal to total decrease in oxidation number by
Multiplying (c ) by 3 and multiply the species involved in increase in o.n. by three.
Cr2O72–(aq) + 3SO32–(aq) → 2Cr3+(aq) + 3SO42–(aq)
Balance the O atoms both side by adding required of water molecules to the side deficient in terms
of oxygen
Cr2O72–(aq) + 3SO32–(aq) → 2Cr3+(aq) + 3SO42–(aq) +4H2O

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Balance hydrogen atom (a)For reactions occurring in acidic medium, add H+ to balance H atoms to
the side deficient in term of hydrogen
Cr2O72–(aq) + 3SO32–(aq) + 8H+ → 2Cr3+(aq) + 3SO42–(aq) +4H2O
Verify that the equation contains the same type and number of atoms and the same charges on
both sides of the equation. This last check reveals that the equation is fully balanced with respect
to number of atoms and the charges.
For the reaction in a basic medium, first balance the atoms as is done in acidic medium. Then for
each H+ ion, add an equal number of OH– ions to both sides of the equation. Where H+ and OH–
appear on the same side of the equation, combine these to give H2O.

Application of redox reactions:


The redox reactions find wide applications:
(a) In the study of electrode processes and cells.
(b)Extraction of metals
(c) supply of energy: by oxidation of fuels
(d)Production of Chemicals
(e) quantitative analysis : in redox systems, the titration method can be adopted to
determine the strength of a reductant/oxidant using a redox sensitive indicator
In one situation, the reagent itself is intensely coloured, e.g., permanganate ion, MnO4– .
Here MnO4– acts as the self indicator. The visible end point in this case is achieved after the last of the
reductant (Fe 2+ or C2O42–) is oxidised and the first lasting tinge of pink colour appears.

SECTION :A (MCQ and AR)


1. The oxidation number of Cl in Cl2O7 is
(a) + 7 (b) + 5 (c) + 3 (d) – 7

2. Which of the following processes does not involve either oxidation or reduction?
(a) Formation of slaked lime from quick lime
(b) Heating Mercuric Oxide
(c) Formation of Manganese Chloride from Manganese oxide
(d) Formation of Zinc from Zinc blende

3. The oxidation state of Cr in Cr (CO)6 is


(a) 0 (b) 2 (c) 2 (d) 6
4. Which of the following processes does not involve oxidation of iron?
(a) Formation of Fe(CO)5 from Fe.
(b) Liberation of H2 from steam by iron at high temperature.
(c) Rusting of iron sheets.
(d) Decolourisation of blue CuSO4 solution by iron.
5. The number of moles of KMnO4 reduced by one mole of KI in alkaline medium is
(a) One (b) Two (c) Five (d) One fifth
6. The oxidation number of Mn is maximum in
(a) MnO2 (b) K2MnO4 (c) Mn3O4 (d) KMnO4
7. Which of the following reactions does not involve either oxidation or reduction?
(a) VO2+ → V2O3 (b) Na → Na+
(c) CrO2–4 → Cr2O7–2 (d) Zn2+ →Zn

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8.H2O2 changes Cr2O72– ion to CrO5 in an acidic medium, the oxidation state of Cr in CrO5 is
(a) +6 (b) +5 (c) –10 (d) +3
8. Which among the following is the strongest oxidising agent?
(a) H2O2 (b) O3 (c) K2Cr2O7 (d) KMnO4
9. Which among the following compounds is the most reducing compound?
(a) H2S (b) HNO2 (c) SnCl2 (d) H2SO3
11.In which of the following complex, the oxidation number of Fe is +1?
(a) Fe4[Fe(CN)6]3 (b) [Fe(H2O)5NO]SO4 (c) [FeBr4]– (d) [Fe(H2O)6]2–
12. Find the oxidation state of I in H4IO6–
(a) +7 (b) +5 (c) +1 (d) –1
13. H2SO4 acts as a strong oxidising agent. In which of the reaction, is it not acting as an oxidising agent?
(a) C + 2H2SO4 → CO2 + 2SO2 + 2H2O (b) CaF2 + 2H2SO4 → CaSO4 + 2HF
(c) S + 2H2SO4 → 3SO2 + H2O (d) Cu + 2H2SO4 → CuSO4 + SO2 + 2H2O

14. Zn gives H2 gas with H2SO4 and HCl but not with HNO3 because

(a) Zn acts as an oxidising agent when it reacts with HNO3


(b) HNO3 is a weaker acid than H2SO4 and HCl
(c) In electrochemical series, Zn is above hydrogen
(d) NO3– is reduced in preference to hydronium ion

15. In the reaction


3Br2 + 6CO32– + 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 oxidized
16. Among the following, identify the species with an atom in + 6 oxidation state:
(a) MnO4– (b) Cr(CN)63− (c) NiF62− (d) CrO2Cl2
In FOLLOWING questions (Q. (17) to (20) 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.
(E) IF both Assertion and reason are false

17.Assertion (A): SO2 and Cl2 are both bleaching agents.


Reason (R): both are reducing agent.

18.Assertion (A): F2 undergoes deprotonation reaction


Reason (R): Fluorine shows both positive and negative oxidation state.

19 Assertion (A): In Basic medium colour of K2Cr2O7 is changed from orange to yellow.
Reason (R): In basic medium K2Cr2O7 is changed in chromate ion.

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20 Assertion(A): SO2 can be used as reductant as well as oxidant.


Reason (R): The oxidation number of S is +4 in SO2 which lies in between its minimum (–2) and maximum
(+6)values.
ANSWER:
Q 1 2 3 4 5 6 7 8 9 10
N
A A A A A B D C A B A
N
S
Q 11 12 13 14 15 16 17 18 19 20
N
A B A B D D A C E A A
N
S
SECTION:B (2MARKS)

Q1. Explain why F cannot undergo disproportionation reaction?


F is most electronegative element and cannot possess three oxidation
states.Hence it cannot undergo disproportionation reactions.
2.Write short notes on :
(a) redox reactions (b) oxidizing agents
Ans.
(a)Reactions in which both Oxidation and reduction take place simultaneously are REDOX REACTIONS.
(b)Oxidizing agents : chemical specie which can oxidize the other one or can reduce itself.

3. Calculate the oxidation number of underlined element in the following:


(a) Na2S2O8 (b) Cr2O7 2-

(a)Na2S2O8
+2+2X+6(-2)+2(-1) = 0
X = +6
(b) Cr2O7 2-
2X+7(-2)= -2
X = +6
4. Fluorine reacts with ice and results in the change:
H2O(s) + F2(g) → HF(g) + HOF(g)
Justify that this reaction is a redox reaction.
O.N. of fluorine in F2 =0
O.N. of flourine in HF=-1
O.N. of flourine in HOF=+1
So in above reaction F2 is reduced as well as Oxidised so it is a redox reaction more over it is a
disproportionation reaction.
5. Which of the following species, do not show disproportionation reaction and
why ?
ClO–, ClO2–, ClO3– and ClO4–
Also write reaction for each of the species that disproportionate.
Ans: Among the oxoanions of chlorine listed above, ClO4– does not disproportionate because in this

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oxoanion chlorine is present in its highest oxidation state that is, +7.so it cannot further increase its
oxidation number.
Section :c (3 marks )
1.Answer the following:
(a) What is the oxidation number of S in S8
(b) Name an indicator which can act as self-indicator.
(c) In the reaction 3Mg + N2 ––→ Mg3N2, Nitrogen is oxidised or reduced.
Ans:
(a)ON of S =0
(b)KMnO4 (Potassium per magnate)
(c) reduced (O.N. decreases from 0 to -3.)
2. Calculate oxidation number of Fe in Fe3O4 and write a suitable justification of your answer.
oxidation number of Fe in Fe3O4 = 3x+(-2x4)=0
3x-8=0
X =8/3
this fractional oxidation state is the average oxidation state of the Fe and the structural parameters
reveal that the element for whom fractional oxidation state is realised is present in different oxidation
states. Here Fe is a mixed oxide
of FeO and Fe2O3 so oxidation state of Fe is +2 and +3 respectively.

3. Split the reaction 2 K (s) + Cl2 (g) ––→ 2 KCl (s) into oxidation and
reduction half reactions and identify oxidising and reducing agents.
Ans:
oxidation half reactions: K (s)→K+ +e-
reduction half reactions : Cl2 +2e- (g) ––→ 2Cl-
oxidising agents : Cl2
reducing agents : K
Section:D (Case based questions -4 marks)
1.Read the given passage and answer the questions.
Redox reactions are reactions in which oxidation and reduction takes place
Simultaneously. Oxidation number is assigned in accordance with the set of rules. Oxidation number
and ion electron methods both are used in balancing ionic equations. Redox reactions are classified as
combination, decomposition, displacement and disproportionation reactions. The concept of redox
couple and electrode processes is basis of electrolysis and electrochemical cells.
(a) What are oxidation number of each individual Br in

Ans. +6, +4, +6


(b) If electrolysis of CuSO4, solution is carried out using Cu electrodes, what will be reaction taking place
at anode.
Ans. Cu → Cu2+ + 2e–
(c) What is oxidation number of Cr in CrO5?

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Ans. +6
It has peroxide linkage.

2. Oxidation reaction involves loss of electrons; reduction reaction involves gain of electrons. The
reaction in which a species disproportionate in two oxidation states (lower and higher) is called
disproportionation reaction.
(a) Iron turning on addition to CuSO4 solution decolourises.Why
(b) define oxidizing agent in terms of
(c) justify that following reaction is an example of disproportionation reaction.
2H2O2 (aq) → 2H2O(l) + O2(g)
(a) Iron turning on addition to CuSO4 solution decolorizes it as Cu+2 (blue in colour) ions reduced by Fe
in Cu metal
Fe + Cu+2 (blue) → Fe+2 (green) +Cu
(b)oxidizing agent in acceptor of electron(s).
(c)

Ans: Here the oxygen of peroxide, which is present in –1 state, is converted to zero oxidation state
in O2 and decreases to –2 oxidation state inH2O.sooxygensimultaneously oxidised and reduced in this
reaction thus it is disproportionation reaction
SECTION:E (LA-5MARKS)
1. (a) Define oxidation and reduction in terms of oxidation number.
(b) Balance the following redox reactions by ion – electron method:
MnO4– (aq) + SO2 (g) → Mn 2+ (aq) + HSO4– (aq) (in acidic solution)
(a) Oxidation: An increase in the oxidation number of the element in the given substance.
Reduction: A decrease in the oxidation number of the element in the given substance
(b)Balance the following redox reactions by ion – electron method:
MnO4– (aq) + SO2 (g) → Mn 2+ (aq) + HSO4– (aq) (in acidic solution)

1.Separate the equation into half reactions:

MnO4– (aq) → Mn 2+ (aq) SO2 (g) → HSO4– (aq)

2. Balance the atoms other than O and H in each half reaction individually
MnO4– (aq) → Mn 2+ (aq) SO2 (g) → HSO4– (aq)
Balance the O atoms in each half reaction individually by adding required of water molecules to the
side deficient in terms of oxygen
MnO4– (aq) → Mn 2+ (aq) + 4H2O SO2 (g)+ 2H2O → HSO4– (aq)
Balance hydrogen atom (a)For reactions occurring in acidic medium, add H+ to balance H atoms to the
side deficient in term of hydrogen.
MnO4– (aq) +8H+ → Mn 2+ (aq) + 4H2O SO2 (g)+ 2H2O → HSO4– (aq) +3H+
Balance charge : Add electrons to one side of the half reaction to balance the charges. The oxidation
half reaction is thus rewritten to balance the charge:

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MnO4– (aq) +8H+ +5e- → Mn 2+ (aq) + 4H2O SO2 (g)+ 2H2O → HSO4– (aq) +3H+ + 2e-
If need be, make the number of electrons equal in the two half reactions by multiplying one or both half
reactions by appropriate coefficients.
2MnO4– (aq) +16H+ +10e- →2 Mn 2+ (aq) + 8H2O 5SO2 (g)+ 10H2O →5 HSO4– (aq) +15H+ + 10e-
We add the two half reactions to achieve the overall reaction and cancel the electrons on each side.
This gives the net ionic equation as :
2MnO4– (aq) +H+ +5SO2 (g)+ 2H2O →2 Mn 2+ (aq) +5 HSO4– (aq)
Verify that the equation contains the same type and number of atoms and the same charges on both
sides of the equation. This last check reveals that the equation is fully balanced with respect to number
of atoms and the charges.
(a)Refer to the periodic table given in your book and now answer the following questions:
(i) Select the possible non metals that can show disproportionation reaction.
(ii) Select metals that can show disproportionation reaction.
(b) Balance the following equations in basic medium by ion-electron method:
Cl2O7 (g) + H2O2(aq) → ClO2 –(aq) + O2(g)
ANSWER:
(a) (i) P4,S8,O2,Cl2.
(b) (ii) Cu,Mn

(b)
1.Separate the equation into half reactions:

Cl2O7 (g) → ClO2 – H2O2(aq) → O2(g)

2. Balance the atoms other than O and H in each half reaction individually
Cl2O7 (g) →2ClO2 – H2O2(aq) → O2(g)
Balance the O atoms in each half reaction individually by adding required of water molecules to the
side deficient in terms of oxygen
Cl2O7 (g) →2ClO2– + 3 H2O H2O2(aq) → O2(g)
Balance hydrogen atom For the reaction in a basic medium, first balance the atoms as is done in acidic
medium. Then for each H+ ion, add an equal number of OH– ions to both sides of the equation. Where
H+ and OH– appear on the same side of the equation, combine these to give H2O.
Cl2O7 (g)+ 6H++ 6OH- →2ClO2– + 3 H2O+6OH- H2O2(aq) + 2OH- → O2(g)+ 2H++ 2OH-
Cl2O7 (g)+ 3 H2O →2ClO2– +6OH- H2O2(aq) + 2OH- → O2(g)+ 2 H2O
Balance charge : Add electrons to one side of the half reaction to balance the charges. The oxidation
half reaction is thus rewritten to balance the charge:
Cl2O7 (g)+ 3 H2O +8e- →2ClO2– +6OH- H2O2(aq) + 2OH- → O2(g)+ 2 H2O+2e-
If need be, make the number of electrons equal in the two half reactions by multiplying one or both
have reactions by appropriate coefficients.
Cl2O7 (g)+ 3 H2O +8e- →2ClO2– +6OH- 4H2O2(aq) + 8OH- → 4O2(g)+ 8 H2O+8e-
We add the two half reactions to achieve the overall reaction and cancel the electrons on each side.
This gives the net ionic equation as :
Cl2O7 (g)+ 4H2O2(aq) + 2OH- → 2ClO2– +4O2(g)+ 5 H2O
Verify that the equation contains the same type and number of atoms and the same charges on both
sides of the equation. This last check reveals that the equation is fully balanced with respect to
number of atoms and the charges.

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ORGANIC CHEMISTRY: SOME BASIC PRINCIPLES AND TECHNIQUES


KEY NOTES

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

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

The Shapes of Carbon Compounds: CH4 is sp3 hybridized and has tetrahedral structure. In
ethene, eachcarbon 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 dependsupon hybridization.
sp hybridized: Carbon has 50% s character, and hence it is close to the nucleus and forms
shorter andstronger bond. It is most electronegative
sp2hybridized: Carbon has 33% s- character, and hence it is less close to the nucleus and forms
slightlylonger 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 andleast strong bonds. It is bigger in size and is less electronegative than sp2 and sp
hybridized carbon.

Characteristic features of – bonds:


- Pi-bond is formed by sideways or lateral overlapping of parallel p-orbitals.
- The p-orbitals should be parallel and perpendicular to the plane of the molecule.
- Rotation of C=C is restricted.
- 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.
- pi bonds are more reactive than Sigma bond in unsaturated molecules.
-
STRUCTURAL REPRESENTATIONS OF ORGANIC COMPOUNDS: Complete structural formula:

Condensed structural formula:

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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


functionalgroup,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 andthe successive members differ from each other in molecular formula by a –CH2 unit.
Eg : Alkanes, alkenes, alkynes.

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NOMENCLATURE OF ORGANIC COMPOUNDS:


The IUPAC name consists of four parts:
Prefix Word root Suffix(primary, secondary)
Number of Word root Number Word root
carbons of
carbons
One Meth Six carbons Hex
carbon
Two Eth Seven Hept
carbons carbons
Three Prop Eight Oct
carbons carbons
Four But Nine Non
carbons carbons
Five Pent Ten Dec
carbons carbons
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 arealready 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 withsuffix ‘-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 alkaneand 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

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the functional groups is numbered in such a way that the functional group attached to the
carbon atom gets thelowest 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-.

Aromatic compounds:
Nomenclature of aromatic compounds: Benzene forms only one mono-substituted derivative. It
can formthree 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 propertiesare called isomers and this phenomenon is called isomerism.
Classification of isomerism: Isomerism is basically classified into 2 types i.e,
1) Structural isomerism

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2) Stereo isomerism

Structural isomerism: Compounds having same molecular formula but different structures are
calledStructural isomers..
Chain isomerism: When two or more compounds having same molecular formula but different
carbonskeletons, 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 ofdouble 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 groupare 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 themolecule 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
electronremains 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 carbanionis generally sp3 hybridised . Carbanions are also unstable

and reactive species.


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

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Alkyl radicals are classified as primary, secondary, or tertiary. Alkyl radical stability increases
fromprimary 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 morestrongly 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 api 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 substituentgroup 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
3) Electrometric effect: It involves the complete transfer of shared pair of electrons to one
of the atomsjoined 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 atleast 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
havingsufficient 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 anddecomposes at or below their boiling points.
Steam distillation: This method is used to separate substances which are steam volatile and are
immisciblewith water

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Differential Extraction: When an organic compound is present in an aqueous medium it is


separated byshaking 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
anadsorbent to different degrees. Silica gel or alumina is used as adsorbents.
Partition Chromatography: It is based on the continuous differential partitioning of components
of amixture 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 thecompound 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 fusiontube 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
withConcsulphuric 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. Ablack 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. insolublein 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 grespectively;

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Dumass method: A known mass of organic compound is heated with excess of CuO in an
atmosphere ofcarbon 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 solutionfrom 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
presenceof 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:

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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 one is wrong pair
(A) Amides –carbamoyl
(B) Carboxylic–acid –carboxy
(C) Nitriles –cyano
(D) Aldehydes– oxo
Answer: (D) Aldehydes– oxo
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

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(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
11) The correct decreasing order of priority for the functional groups of organic
compounds in the IUPAC system of nomenclature is:
(A) –CHO, –COOH, –SO3H, –CONH2
(B)–SO3H, –COOH, –CONH2, –CHO
(C)–COOH, –SO3H, –CONH2, –CHO
(D)–CONH2, –CHO, –SO3H, –COOH
Answer: C)–COOH, –SO3H, –CONH2, –CHO
12) IUPAC name of compound CH3CH = CH – CHO is
(A) But–2–enal.
(B) Prop–2–enal
(C) But–1–enal
(D) But–2–enol
Answer: A) But–2–enal.
13) The C–H bond distance is longest in
(A) C2H2
(B) C2H4
(C) C2H6
(D) C2H2Br2
Answer: (C) C2H6
14) Which of the following can act as an electrophile?
(A) CN–
B) OH–
(C) H2O
(D) BF3
Answer: (D) BF3
15) The I.U.P.A.C name of the compound is

(A) 3, 3, 3– Trimethyl propene


(B) 1,1, 1–Trimethylpent-2-ane
(C) 3, 3–Dimethylbut-1-ene
(D) 2, 2–Dimethylbut-3-ane.
Answer: (C) 3, 3–Dimethylbut-1-ene
16) The I.U.P.A.C. name of CH3COCH(CH3)2 is
(A) 3–methylbutan-2-one

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(B) Isopropyl methyl ketone


(C) 2–methylbutan-3-one
(D) 4–methyl isopropyl ketone
Answer: (A) 3–methylbutan-2-one

17) Which of the following cannot be represented by resonance structures?


(A) Toluene
(B) Nitrate anion
(C) Carboxylate anion
(D) Dimethyl ether
Answer: (D) Dimethyl ether

18) which one is an inorganic compound?


(A) Ammonium cyanate
(B)Ethane
(C)Acetic acid
(D)DNA
Answer: (A) Ammonium cyanate

19)The IUPAC name of CH3– CH = CH – C ≡ CH is:


(A) pent–3–en–4–yne
(B) pent–3–en–1–yne
(C)pent–2–en–4–yne
(D) pent–2–en–3–yne
Answer: (B) pent–3–en–1–yne
20) First organic compound to be synthesised was
(a) urea (b) cane sugar (c) methane (d) acetic acid
Answer: (a) urea
ASSERTION AND REASON QUESTIONS
In the following questions the assertion and reason have been put forward read the statements
carefully andchoose 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 of a 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−Hbond 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.

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

2mark question

1) Draw the structure of the following compounds


a) Hex-3enoic acid
b) 2-chloro-2-methyl butan-1-ol
Answer 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
cannotoverlap 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 1πbond
b) 8 sigma and 1πbond

4) It is not advisable to use sulphuric acid in place of acetic acid for acidification while
testing sulphur bylead acetate test. Give reason.
Lead acetate on reacting with sulphuric acid will give a white precipitate of lead sulphate which
interfere n
i 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) ii) Distillation under reduced pressure.

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

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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
immisciblewith water.
Distillation under reduced pressure is used to purify those liquids which decompose at or
belowtheir normal boiling points.
3. Write IUPAC name of each of the following compound.
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 ofBromine. (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 givenorganic compound

5. Distinguish between inductive effect and resonance effect.


Inductive effect Resonance effect
1.Involves displacement of sigma 1. Involves delocalization of pi
electrons andhence occurs only electrons and lonepair and hence
in saturated compound occurs in unsaturated
compounds
and conjugated systems.
2. Electronegativity difference 2. It takes place due to
induces this effect interaction between two pibonds
towards the more or a pi bond and a lone pair of
electronegative atom to give electron
partial +ve or –ve charges.
3.Inductive effects are 3. The resonance effects are
transmitted over short distances transmitted all along the length
in saturated carbon chains and in the conjugated system. The
the magnitude of the effect electron pair is completely
decreases rapidly as thedistance transferred to form positive and
from the halogen atom increases negative charge centres.

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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 ferricferrocyanide.

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 itwill 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.

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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 isascertained 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 toseparate 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.

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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

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UNIT-XIII HYDROCARBON

 Hydrocarbons: These compounds are composed of Carbon and hydrogen only.


 Petrol, kerosene, coal gas, CNG, LPG etc. are all hydrocarbons or their mixture.
Sources: Aliphatic hydrocarbon: Petroleum and natural gas
Aromatic hydrocarbons: Coal
The main constituents of the natural gas are methane, ethane, propane and butane.
CLASSIFICATION OF HYDROCARBONS:
HYDROCARBON

Acyclic or Aliphatic Carbocyclic or Cyclic


( Open chain)

Alicyclic Aromatic
Alkanes Alkenes Alkyne
(C-C) (C=C) (C≡C)

Cycloalkanes Cycloalkenes Cycloalkynes


Alkanes:
General Paraffins
Name
General CnH2n+2
Formula
Hybridisation sp3
Bond angle 109.5°
C–C bond 154 pm
length
C–H bond 112 pm
length
Reactivity Chemically unreactive
Isomerism Chain, position and
optical isomerism
No. of Heptane has 9 isomer,
Isomers Octane 18 and Decane
75. Ethane

Nomenclature: P R B = Prefix + Root Name + Bond Name


(Branch) (no. of Carbon) ( Bond)

Compound IUPAC Name


CH4 Methane
CH3- CH3 Ethane
CH3- CH2- CH3 Propane
CH3- CH2- CH2- CH3 Butane
CH3- CH- CH3 2-MethylPropane
CH3
2,3-Diethylbutane

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Isomerism:
(1) Chain Isomerism: In this isomerism compounds have same molecular formula but different
structure. Ex- Pentane, 2-Methylbutane, 2,2-Dimethylpropane
(2)Position Isomerism: In this isomerism compounds have same molecular formula but position of
substituent group. Ex- 2-Methylpentane, 3-Methylpentane

Type of carbon:
Primary carbon (1°): The carbon atom attached to only one other carbon.
Secondary carbon (2°): The carbon atom attached to only two other carbons.
Tertiary carbon (3°): The carbon atom attached to only three other carbons.
Quaternary carbon (4°): The carbon atom attached to only four other carbons.

Preparation:-
1. From unsaturated hydrocarbons:-

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

(ii) Wurtz reaction : This reaction is used for preparation of higher alkanes.
 Useful in preparing an alkane containing even number of carbon atoms
 Stepping up reaction

Dry
2CH3CH2Br  2Na 
 CH3CH2CH2CH3  2NaBr
ether
3. From carboxylic acids- (i) By decarboxylation.-

(ii) Kolbe’s electrolytic method-

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 Physical Properties:-
(1) Nature:- Non-Polar due to covalent nature of C—C bond and C—H bond.
C1—C4 are gases, C5—C17 are colourless odourless liquid and higher are Solids.
(2) Solubility:- Like dissolve like Viz, Polar compounds dissolve in polar solvent and Non-Polar
compound dissolve in non polar solvent.
(3) Boiling point:- Low boiling point due to non polar in nature and weak Van der Waals’ forces.
The boiling point increases with increase the molecular mass as the magnitude of Van der
Waals’ forces is directly proportional to the molecular size.
The boiling points of the branched chain Alkanes are less than the straight chain isomers
because branching of the chain makes the molecule more compact and thereby decreases
the surface area and consequently, the magnitudes of Van der Waals’ forces get decreased.
Ex- n-pentane (309.1K), isopentane(301K), neopentane (282.5 K)

Chemical properties
1. Substitution reactions: Halogenation: Produce Mixture of halo alkanes.
CH4 + Cl2 → 3
Chloromethane
3 → →
2 2 → 3 4
Chloromethane Dichloromethane Trichloromethane TetraChloromethane
CH3- CH3 + Cl2 → 3-CH2-
Chloroethane 
Note:- Iodination is a slow and reversible reaction. So it is carried out by heating alkane in the
presence of some oxidizing agent like iodic acid (HIO3) or nitric acid (HNO3) which oxidizes HI
formed during the reaction.
CH4 + I2 3
5HI + HIO3 2 2
Note:- Fluorination of alkane takes place explosively so it is difficult to control.
 Features of Halogenations:-
(i) The reactivity of Halogens:- F2 > Cl2 > Br2 > I2.
(ii) The rate of replacement of hydrogen of alkanes is: 3° > 2° > 1°
Mechanism:- halogenations reaction take place by free radical mechanism. The reaction proceeds in
the following steps:
(i) Chain initiation step:-
h
Cl — Cl 2Cl
(ii) Chain Propagation step:-

CH4  Cl  CH3  HCl

CH3  Cl2  CH3Cl  Cl 
(iii) Chain Termination step:-

Cl  Cl  Cl2


 
CH3  CH3  CH3  CH3

CH3  Cl  CH3Cl

2.Combustion: CO2 , H2O and heat is produced.


CH4 (g)+ 2 (g) → 2 (g) 2

3. Controlled oxidation: Different Products are formed using different catalysts.

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2CH4 + O2 → 2CH3- OH (Methanol)

CH4 + O2 → 2 HCHO (Methanal)


CH3 COO)2 n
CH3 CH3 + 3O2 → 2 CH3 COOH (Ethanoic acid)

CH3)3CH → (CH3)3COH (2-Methylpropan-2-ol)


4. Isomerisation:

5. Aromatization (Reforming): The process of converting aliphatic compounds into aromatic


compounds iscalled aromatisation.

6. Reaction with steam

7. Pyrolysis or cracking: It is process of decomposing higher hydrocarbons into lower


hydrocarbons withlow boiling point by strong heating. Products depend on reaction situations.

General reactions of Methane

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Conformations
Spatial arrangements which are obtained by rotation around sigma bonds are called conformation or
conformational isomers and this phenomenon is called conformational isomerism.
There are three conformers of ethane.
Eclipsed Staggered Skew
H-atoms H-atoms are Any other
attached to as far apart as intermediate
two carbons possible is conformation
are as closed known as the is called a
together as staggered skew
possible is conformation. conformation.
called
eclipsed
conformation
Dihedral 120° 0- 120°
angle =0°
High torsional Low torsional In between
strain strain
more stable less stable -

Sawhorse projections Newman projection


The molecule is viewed The molecule is viewed at the C-C
along the molecular axis bond head on.

ALKENES

These are unsaturated hydrocarbons containing at least one double bond.


General Oleffins
Name
General CnH2n
Formula
Hybridisation sp2
Bond angle 120°
C=C bond 134 pm
length
Reactivity Attacked by
electrophiles
Isomerism Chain, position
and geometrical
isomerism

Nomenclature: P R B = Prefix + Root Name + Bond Name


(Branch) (no. of Carbon) ( ene)

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Compound IUPAC Name


CH2= CH2 Ethene
CH3- CH= CH2 Propene
CH3- CH2- CH= CH2 But-1-ene
CH3-CH= CH-CH3 But-2-ene
CH3- C= CH3 2-Methylprop-1-ene
CH3

Isomerism: structural isomerism. CH3


CH3- CH2- CH= CH2 CH3-CH= CH-CH3 CH3- C= CH3
I. But-1-ene II. But-2-ene III. 2-Methylprop-1-ene
I & II are position isomers. I & III are chain isomers.
Geometrical isomerism
Cis-isomers Trans-isomer
Same groups are in same side Same groups are in opposite
of double bond. side of double bond.
Polar (µ= 0.33 D) Non polar ( µ= 0 )

Preparation From alkynes: Use of palladised charcoal gives cis-product and Na/NH3 gives trans
product.

2. From alkyl halides: This reaction is also known as dehydrohalogenation i.e., removal of
halogen acid(HX). This is example of β-elimination reaction, since hydrogen atom is
eliminated from the β carbon atom.

Reactivity
R-I >R-Br>R-Cl
tert. >secondary
>primary RX

3.From vicinal dihalides by dehalogenation:


Br CH2 CH2 → CH2= CH2 2

CH3 CHBr CH2 → CH3 CH= CH2 2

4. From alcohols by acidic dehydration: HOH molecule is eliminated from alcohol on heating
with con. H2SO4.

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 Physical Properties
Resembles alkane except their polar nature.
1. Addition of Hydrogen: Produce alkane.

R CH= CH2 H2 → R CH2 CH3

2.Addition of halogens: vicinal dihalides are formed. Discharge of redish brown colour of
bromine is used as test for unsaturation .

3. Addition of hydrogen halides:


Major product

Minor product

Markovnikov rule: The major product will be that in which negative part of the addendum
(adding molecule) gets attached to that double bonded carbon which has lesser number of
hydrogen atoms.
Mechanism:
I. Electrophilic attack of H+ :
Since secondary
carbocation is more
stable so it is formed
faster.

II. Attack of Br- on carbocation:

Anti Markovnikov addition or peroxide effect or Kharash effect: In the presence of peroxide,
addition of HBr to unsymmetrical alkenes Br- gets attached to double bonded carbon having
more number of hydrogen atoms.

CH3 -CH= CH2 → CH3 -CH- CH2 - 1-Bromopropane (Major)

Mechanism:

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(less stable 1° free (more stable 2° free radical)


radical)

CH3 -CH(Br)- CH3 + CH3 -CH- CH2 - + Br


Br Major product
Minor product

4.Addition of sulphuric acid: As per markovnikovs rule.

Ethyl hydrogen sulphate Propyl hydrogen sulphate

5.Addition of water: As per Markovnikov’s rule.

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


Decolouration of KMnO4 is used as test of unsaturation.
CH2 =CH2 H2 → HO CH2 CH2 OH (Glycol)

(b) Acidic KMnO4 or K2Cr2O7 oxidises alkenes to ketones or acids.

(CH3)2CH =CH2 → (CH3)2C=O + CO2 +H2O


2-methylpropene Propan-2-one
CH3 CH =CH CH3 → 2CH3COOH
But-2-ene Ethanolic acid

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7.Ozonolysis: Two moles of carbonyl compounds are formed.

8. Polymerisation: Polymers are formed.

ALKYNES :

General CnH2n-2
Formula
Hybridisation sp
Bond angle 180°
C≡C bond 120 pm
length
Reactivity Attacked by
electrophiles
Isomerism Chain and
position

Preparation
1.From calcium carbide:

2.From vicinal dihalides:

Chemical properties
1.Acidic character of alkyne:

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Order of acidity

2.Addition of dihydrogen:

3.Addition of halogens:

4.Addition of hydrogen halides:

5.Addition of water:
6.Cyclic polymerisation:

AROMATIC HYDROCARBON
These hydrocarbons are also known as ‘arenes’.
Position isomerism:

1,2- 1,3- 1,4-


Dimethylbenzene Dimethylbenzene Dimethylbenzene
(o-Xylene) (m-Xylene) (p-Xylene)

Resonance and stability of benzene:


1. The six π electrons are thus delocalised and can move freely about the six carbon nuclei.
The delocalised π electron cloud is attracted more strongly by the nuclei of the carbon atoms
than the electron cloud localized between two carbon atoms. Therefore, presence of

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delocalised π electrons in benzene makes it more stable.


2. All bonds have same bond length i.e.between single and double bond (139 pm)
3. Show reluctance to addition reaction.

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, 2,3..)This is often
referred to as Hückel Rule.

Preparation of Benzene
1.Decarboxylation of aromatic acids:

2. Reduction of phenol:

3.cyclic polymerisation of ethyne: See in ethyne.

Chemical properties
Nitration:

Halogenation:

If Cl2 is taken in excess,C6Cl6 is formed.

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Sulphonation:

Friedel-Crafts alkylation reaction:

Friedel-Crafts acylation reaction

Mechanism of electrophilic substitution reaction


Step-I Generation of electrophile

Step II Formation of Carbocation (arenium ion):

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Removal of proton:

Addition reactions

Combustiuon: produce sooty flame.

Directive influence of a functional group in monosubstituted benzene


Ortho and para directing groups: The groups which direct the incoming group to ortho and
para positions are called ortho and para directing groups.
Ex: -OH , NH2 , -OCH3

Meta directing group: The groups which direct the incoming group to meta position are called
meta directing groups. Some examples of meta directing groups are –NO2, –CN, –CHO, –COR,
–COOH, –COOR, –SO3H, etc.

Activating groups: These groups activates the benzene ring for the attack by an electrophile.
examples–NH2, –NHR, –NHCOCH3, –OCH3, –CH3, –C2H5, etc
Deactivating groups: These groups decrease the overall electron density on benzene ring
making further substitution difficult. Ex: NO2, –CN, –CHO, –COR, –COOH, –COOR, –SO3H, etc.
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.
Ex-1,2-Benzanthracene , 1,2-benzpyrene
Practice Questions
MCQ

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1. Which of the following will not show geometrical isomerism?


A. B. C. D.

2. The correct IUPAC name of the following alkane is-


CH3- CH2-C(CH3)2CH(CH3)2
A. 3,3,4,4-Tetramethylbutane B. 3,3,4-Trimethylpentane
C. 2,3,3-Trimethylpentane D. 3-Ethyl-2,3-Dimethylbutane

3. An alkyl bromide [x] reacts with sodium in ether to form 2,3–dimethylbutane, the compound
'x' is .
A. CH3 CH2Br B. (CH3)2 CH Br
C. CH3 CH2CH2Br D. CH3CH2 CH(Br) CH2 CH2CH3

4. Alkyl halides react with sodium metal to give :


A. alkenes B. alkyl sodium halide
C. alkenyl halides D. alkanes

5. Which one of the following cannot be prepared by Wurtz reaction?


A. CH4 B. C2H6 C. C3H8 D. C4H10

6. Identify the compound B in the following reaction.


CH3-CH = CH-CH3 →
A. CH3COCH3 B. CH3CH2COCH3
C. CH3CHO D. CH3CH2CHO
7. The reaction of HBr with CH3 – C(CH3) = CH2 in the presence of peroxide will give :
A. B. C.

D .

8. But-2-ene on reaction with HBr gives-


A.1-Bromobutane B. 2-Bromobutane
C. Mixture of A & B D. 1,2-Dibromobutane

9. Which peroxide is used in Kharasch effect-


A. Hydrogen peroxide B. Benzoyl peroxide
C. sodium peroxide D. Barium peroxide

10. Arrange the following hydrogen halides in order of their decreasing reactivity with
propene.
(A) HCl > HBr > HI (B) HBr > HI > HCl (C) HI > HBr > HCl (D) HCl > HI > HBr

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11. Some oxidation reactions of methane are given below. Which of them is/are
controlled oxidation reactions?
(A) CH4 (g) + 2O2 (g) → CO2 (g) + 2H2O (l)
(B) CH4 (g) + 2O2 (g) → C(g) + 2H2O (l)
(C) CH4 (g) + O2 (g) → HCHO + H2O
(D) 2CH4 (g) + O2 (g) → 2CH3OH
12. For an electrophilic substitution reaction, the presence of a halogen atom in the
benzene ring _______.
(A) Deactivates the ring by inductive effect
(B) Deactivates the ring by resonance
(C) Decreases the charge density at ortho and para position relative to meta position by
resonance
(D) Directs the incoming electrophile to meta position by increasing the charge density
relative to ortho and para position
13. Arrange the following in decreasing order of their boiling points.
(A) n–butane (B) 2–methylbutane (C) n-pentane (D) 2,2–dimethylpropane
(i) A > B > C > D (ii) B > C > D > A
(iii) D > C > B > A (iv) C > B > D > A

14. Benzene + CH3Cl → ?


A.Benzoic acid B. Chlorobenzene C. Toluene D. Benzene hexachlorid
15. Identify the following reaction.
CH ≡CH → 6 6

A. Hydrogenation B. Halogenation
C. Linear Polymerisation D. Cyclic Polymerisation

16. Identify [X] in the following reaction


CH ≡CH → → 3
4
A. CH3CH2OH B. CH3–O–CH3
C. CH3CH2CHO D. CH2 = CHOH
17. The position of double bond in alkenes can be located by :
(A) Hydrogenation of oil (B) Ozonolysis
(C) Photolysis (D) Hydration
18. Which one of these is not true for benzene?
(A) There are three localised carbon-carbon single bonds and three carbon-carbon double
bonds.
(B) Heat of hydrogenation of benzene is less than the theoretical value
(C) It forms only one type of mono substituted product
(D) The bond angle between carbon-carbon bonds is 120 Degree
19. Which is not meta-directing group in aromatic substitution?
(A) –C ≡ N (B) –OH (C) –COOH (D) -NO2
20. Presence of a nitro group in a benzene ring
(a) Activates the ring towards electrophilic substitution
(b) Renders the ring basic
(c) Deactivates the ring towards nucleophilic substitution
(d) Deactivates the ring towards electrophilic substitution

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Assertion Reason Questions


From Q.21 to 24 choose options from following.
(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.

21.Assertion (A) : Nitration of benzene with nitric acid requires the use of concentrated
sulphuric acid. Reason
(R) : The mixture of concentrated sulphuric acid and concentrated nitric acid produces the
electrophile, NO2 +.
22.Assertion (A): Toluene on Friedal Crafts methylation gives o– and p–xylene.
Reason (R) : CH3-group bonded to benzene ring increases electron density at o– and p–
position.

23. Assertion(A): But-1-ene does not show geometrical isomerism.


Reason(R): Carbon –carbon double bond restrict the free rotation of groups around it.

24. Assertion(A): Ethyne is acidic in nature.


Reason(R): Ethyne has sp2 hybridisation.

ANSWER KEY
1.A 2.C 3.B 4.D 5.C
11.C&D 12.A 13.IV 14.C 15.D
21.A 22.A 23.B 24.C

TWO MARKS QUESTIONS

1. Write the IUPAC names of the following-

a. b.
Ans. a .Pent-en-3-yne b. 2-methylphenol

2. What are the necessary conditions for any system to be aromatic?


Ans. A compound is said to be aromatic if it satisfies the following three conditions:
(i) Planar structure.
(ii) Completely delocalized π electrons in the ring.
(iv)Follow Huckel Rule.The total π electron s present in should be equal to (4n + 2) π, where n =
0, 1, 2 … etc.

3. What effect does branching of an alkane chain has on its boiling point?
Ans. As branching increases, the surface area of the molecule decreases which results in a
small area of contact. As a result, the Van der Waals force also decreases which can be
overcome at a relatively lower temperature. Hence, the boiling point of an alkane chain
decreases with an increase in branching.

4. How would you convert the following compounds into benzene?


a. Ethyne (ii) Ethene

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Ans. (i) Benzene from Ethyne:

(ii) Benzene from Ethene:

5. function of Lewis acids anhydrous aluminium chloride which can be used during alkylation
of benzene. Suggest some other Lewis acids also.
Ans. It is used as catalyst.
anhydrous FeCl3, SnCl4, BF3 etc.
6. Although benzene is highly unsaturated, it does not undergo addition reactions, why?
Ans. Because of extra stability due to delocalization of π-electrons.

THREE MARKS QUESTIONS

1. What is Wurtz reaction? How can it be used to prepare butane? Can pentane be prepared by
this reaction?
Ans- When alkyl halides is treated with metallic Na in presence of dry ether, alkanes are
formed. This reaction is called Wurtz reaction.
Butane is prepared by following reaction

No pentane can’t be prepared by wurtz reaction.

2. An alkene ‘A’ contains three C – C, eight C – H σ bonds and one C – C π bond. ‘A’ on
ozonolysis gives two moles of an aldehyde of molar mass 44 u. Deduce IUPAC name of ‘A’.
Write the chemical reaction.
Ans.. The formation of two moles of an aldehyde indicates the presence of identical structural
units on both sides of the double bond containing carbon atoms. Hence, the structure of ‘A’
can be represented as:
XC = CX
There are eight C–H σ bonds. Hence, there are 8 hydrogen atoms in ‘A’. Also, there are three
C–C bonds. Hence, there are four carbon atoms present in the structure of ‘A’.
Combining the inferences, the structure of ‘A’ can be represented as:

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the IUPAC name of ‘A’ is But-2-ene.


Ozonolysis of ‘A’ takes place as:

The final product is ethanal with molecular mass

3. Complete the reactions-


A. CH3—CH=CH2 →
B. CH=CH + Br2 water→

C. CH3CH2I + Na →
Ans: A.CH3—CH(OH)CH2 OH B. Br -CH2—CH2 Br C. CH3CH2 CH2CH3

4. Complete the following reactions.


(i) CH3COO-Na+ →
(ii) →
(iii) →
- +
Ans. (a) (i)CH3COO Na → CH4 + Na2CO3
(ii) → )
(iii) →

FIVE MARKS QUESTIONS

1. An alkyl halide C5H11Br (A) reacts with ethanolic KOH to give an alkene ‘B’, which reacts
with Br2 to give a compound ‘C’, which on dehydrobromination gives an alkyne ‘D’. On
treatment with sodium metal in liquid ammonia one mole of ‘D’ gives one mole of the sodium
salt of ‘D’ and half a mole of hydrogen gas. Complete hydrogenation of ‘D’ yields a straight
chain alkane. Identify A,B, C and D. Give the reactions invovled.
Ans:

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2. (a) State the Huckle Rule.


(b) Show the resonance in phenol.
(c) Draw geometrical isomers of But-2-ene.
(d) Arrange the following in increasing order of acidic character.
CH3–CH3 , H2C=CH2 , HC ≡ CH
(e)How will you distinguish between ethane and ethane?
Ans: (a) Huckel Rule: Cyclic compounds having (4n+2) pi electrons are aromatic. n= 0, 1, 2,
3….

(b)

(c) Geometrical isomers of But-2-ene.


(d) Increasing order of acidic character.
CH3–CH3 < H2C=CH2 < HC ≡ CH
(e) Ethene decolourise the Bromine water while ethane can’t.
Case based questions
1.Read the passage carefully and answer the questions.
1Alkanes contain carbon-carbon sigma (σ) bonds. Electron distribution of the sigma molecular
orbital is symmetrical around the internuclear axis of the C–C bond which is not disturbed
due to rotation about its axis. This permits free rotation about C–C single bond. This rotation
results into different spatial arrangements of atoms in space which can change into one
another. Such spatial arrangements of atoms which can be converted into one another by
rotation around a C-C single bond are called conformations or conformers or rotamers.
Alkanes can thus have infinite number of conformations by rotation around C-C single bonds.
However, it may be remembered that rotation around a C-C single bond is not completely
free. It is hindered by a small energy barrier of 1-20 kJ mol–1 due to weak repulsive interaction
between the adjacent bonds. Such a type of repulsive interaction is called torsional strain.
1. What is the reason of confermation?
2. Draw two confermers of ethane.
3. Which confermer of ethane is more stable?
4. Why ethene cant show confermation?

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Or
What is dihedral angle?
ANS: 1. Free rotation of C-C sigma bond.

2.
3. staggered form is more stable due to less torsional strain.
4. Due to restricted rotation

2.Read the passage carefully and answer the questions.


Geometrical isomerism: Doubly bonded Carbon atoms have to satisfy the remaining two
Valences by joining with two atoms or groups. If the two atoms or groups attached to each
Carbon atom are different, they can be Represented by YX C = C XY like structure.
If the two identical atoms i.e., both the X or both the Y lie on the same side of the Double
bond but in (b) the two X or two Y lie Across the double bond or on the opposite Sides of the
double bond. This results in Different geometry of (a) and (b) i.e. disposition Of atoms or
groups in space in the two Arrangements is different. Therefore, they are Stereoisomers.
They would have the same Geometry if atoms or groups around C=C bond Can be rotated
but rotation around C=C bond Is not free. It is restricted.

1. What is the reason of geometrical isomerism?


2. Draw two geometrical isomers of but-2-ene.
3. Which geometrical isomer is non-polar?
4. Why ethene cant show geometrical isomerism?
Ans:1. Due to restricted rotation around double bond.
2.

3. Trans-But-2-ene is non polar.


4. Because group attached to doubly bonded carbon are same.

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BLUEPRINT
CHEMISTRY SAMPLEPAPER-1
CLASSXI
S.No Name of the chapters MCQ A/R VSAI SAI Case LA Total
based
1 1 2 3 4 5 Weig
Mark Mark Marks Marks Marks Marks htag
e
1. Some basic concepts of 2(2) 2(1) 3(1) 7
chemistry
2. Structure of atom 1(1) 3(1) 5(1) 9
3 Classification of elements 2(2) 1(1) 3(1) 6
And periodicity in properties
4 Chemical bonding and 2(2) 5(1) 7
Molecular structure
5 Chemical thermodynamics 2(2) 4(2) 3(1) 9
6 Equilibrium 1(1) 2(1) 4(1) 7
7 Red-oxreactions 1(1) 3(1) 4
8 Organic chemistry – 2(2) 1(1) 4(2) 4(1) 11
Some basic principles
and Techniques
9 Hydrocarbons 2(2) 1(1) 2(1) 5(1) 10
14 4 14 15 8 15 70

Kendriya Vidyalaya Sangathan Jaipur Region


Sample paper-1
MM: 70 Subject –Chemistry Time: 3.00 Hours

General Instructions:-
Read the following instructions carefully.
a) There are 35 questions in this question paper. All questions are compulsory.
b) Section A: Q. No. 1 to 18 are objective type questions carry 1 mark.
c) Section B: Q. No. 19 to 25 are short answer questions and carry 2 marks each.
d) Section C: Q. No. 26 to 30 are short answer questions and carry 3 marks each.
e) Section D: Q. No. 31 to 32 are case based questions carrying 4 marks each.
f) Section E: Q. No. 33 to 35 long answer questions carrying 5 marks each.
g)There is no overall choice. However, internal choices have been provided.
h) Use of calculators and log tables is not permitted.
Section A(OBJECTIVE TYPE)

1 What is unit of molarity? 1


(A) mol/kg (B) mol/l (C) g/l (D) No unit
2 Which one will have maximum number of atoms? 1
(A) 4 grams He (B) 4 moles of He (C) 8 grams He (D) 2 moles of He
3 Maximum number of electrons in a subshell of an atom is determined by the following 1
(A) 2l + 1 (B) 4l – 2 (C) 2n2 (D) 4l + 2
4 The number of spherical nodes in 3p orbitals are 1
(A) one (B) three (C) two (D) None of these
5 Which of the elements belong to the d–block but are not transition metals 1
(A)n, Cd, Hg (B) Sc, V, Ti (C)Cu, Ag, Au (D)Mn, Fe, Co

6 What are representative elements? 1

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(A) s–block and p–block elements are called representative elements.


(B) d–block elements.
(C) f–block elements
(D) None of these

7 Which of the following molecule doesn’t involve covalent bond? 1


(a) O2 (b) CCl4 (c) H2O (d) KCl

8 What is the criteria for a reaction to be spontaneous- 1


(A) G = -ve (B) G = 0 (C) G= + ve (D) G=0

9 Which of the following factor favours the reaction: 1


N2 (g) + 3H2 (g) ⇌ 2NH3 (g) ; ΔrH = -92.4 KJ
(A) decrease in pressure (B) increase in temperature
(C) increase in volume (D) decrease in temperature
10 The oxidation number of Mn is maximum in 1
(A) KMnO4 (B) K2MnO4 (C) Mn3O4 (D) MnO2
11 The shape of carbanion is- 1
(A) Pyramidal (B) Linear (C) Trigonal Planar (D) Tetrahedral
12 Benzene + CH3Cl → X. What is X? 1
A.Benzoic acid B. Chlorobenzene
C. Toluene D. Benzene hexachlorid
13 Identify the following reaction. CH ≡CH → 1

A. Hydrogenation B. Halogenation
C. Linear Polymerisation D. Cyclic Polymerisation
14 The position of double bond in alkenes can be located by : 1
(A) Hydrogenation of oil (B) Ozonolysis
(C) Photolysis (D) Hydration
In the following questions (Q. No. 14 - 18) 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.

15 Assertion: Smaller the size of an atom greater is the electronegativity. 1


Reason: Electronegativity refers to the tendency of atom to share electrons with other
atom
16 Assertion: Tertiary carbocation is more stable than primary. 1
Reason: The 3ºcarbocation has greater + I effect.
17 Assertion: Equilibrium is a static state. 1
Reason: At equilibrium rate of forward and backward reaction is equal.
18 Assertion: Toluene gives mixture of o and p xylene on alkylation. 1
Reason: methyl is a o & p directing group.
19 A.What do mean by Mole fraction? 2
B.What is the limiting reagent?
20 (a) Write designation of an orbital having n = 5, l = 3. 2
(b) Name the spectral line series in the spectrum of H-atom obtained when an electron

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jumps from n = 4 to n = 2.
21 (a ) Define Zeeman effect. 2
(b) Which equation tell about the dual nature of matter?
22 Using VSEPR theory draw the shape of the SF4 and PCl5.molecules. 2
23 (a)State Hess Law of constant heat summation.. 2
(b)What will be the sign of ΔU if-
(i)q heat is released by the system to surrounding.
(ii)W dork is done on the system.
24 (a)Why the value of second ionisation constant of H2SO4 is lower than first? 2
(b) If value of equilibrium constant (Kc) is 4.0 for a reaction A--->B , calculate the value of
equilibrium constant (Kc’) for the reverse reaction B-->A.

25 Complete the following reactions. 2


(i) CH3COO-Na+→
(ii) →

26 50.0 kg of N2 (g) and 10.0 kg of H2 (g) are mixed to produce NH3 (g). Calculate the 3
amount of NH3 (g) formed. Identify the limiting reagent in the production of NH3 in this
situation.
OR
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?
27 Table-tennis ball has a mass 10 g and a speed of 90 m/s. If speed can be measured 3
within an accuracy of 4%, what will be the uncertainty in speed and position?
28 Consider the following species: 3
N3-, O2-, F–, Na+, Mg2+, Al3+
(a) What is common in them?
(b) Arrange them in order of increasing ionic radii?
(c)Pridict the group and period of element Z= 53.
29 (i) Calculate the oxidation No. of ClamdMn in HClO3 and in K2MnO4 3
(ii) Balance the following ionic equation by ion electron method or oxidation method.
Cr2O7 2-(aq) + SO32- (aq)  Cr3+(aq)+ SO42-(aq) (Acidic medium)

30 (a)Define the term functional group 3


(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.
31 Case based questions. 4
In atoms, electrons occupy atomic orbitals, but in molecules they occupy similar
molecular orbitals which surround the molecule. There are two molecular orbitals for
hydrogen, the lower energy orbital has its greater electron density between the two
nuclei. This is the bonding molecular orbital - and is of lower energy than the two 1s
atomic orbitals of hydrogen atoms making this orbital more stable than two separated
atomic hydrogen orbitals. The upper molecular orbital has a node in the electronic wave
function and the electron density is low between the two positively charged nuclei. The
energy of the upper orbital is greater than that of the 1s atomic orbital and such an
orbital is called an anti bonding molecular orbital. Molecular orbitals are filled in
accordance with Aufbau principle, Pauli’s exclusion principle, and Hund’s rule of
maximum multiplicity.The molecular orbital configuration of O2 isσ1s2 σ∗1s2
,σ2s2,σ∗2s2,σ2pz2,π2px2,π2py 2, π*2px1,π*2py1
1. Write molecular orbital configuration of O2+ion.
2. Why Ne2 molecule does not exist?

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3. Calculate the bond order of super oxide ion.


4. Which is more stable O2, or O2+and why?
OR
N2 is diamagnetic while O2 paramagnetic. Explain.

32 An Arrhenius acid is a substance which furnishes hydrogen ions (H ions) in aqueous 4


solution, An Arrhenius base is a substance which furnishes hydroxyl (OH ) ions in
aqueous solution The strength of an acid or base depends upon its tendency to furnish H
or OH ions in solution, respectively.
A Bronsted acid is proton donor whereas, a Bronsted base is proton acceptor.
A pair of Bronsted acid-base which differ by a proton is known as conjugate pair of
Bronsted acid and Bronsted base
A Lewis base is defined as a substance which can furnish a pair of electrons to form a
coordinate bond whereas a Lewis acid is a substance which can accept a pair of
electrons.
1. AlCl3 is a Lewis acid. Give reason.
2. Write conjugated acid and base of ammonia.
3. What do you mean by strong acid?
4. Categorise following as Lewis base and Arhenius base. NH4OH, NH3Ca(OH)2, ROH
OR
How acidic strength of acid depends on (H ions)?

33 (a) Out of 1 mole of H2O(g) and 1 mole of H2O(l) which one will have greater entropy? 5
(b) What will be the value of ΔG° for boiling water?
(c) What is meant by the term state function? Give one example.
(d)Define entropy. And prove that entropy is an extensive property.
OR
(a) State third law of Thermodynamics.
(b) U is a state function but work is not?
(c) Calculate the enthalpy of the reaction:
N204(g) + 3CO(g)  N20(g) + 3CO2(g)
Given that; ∆fHº CO (g) = – 110 kj mot-1; ∆fH C02(g) = – 393 kj mol-1
∆fH N20(g) = 81 kj mot-1; ∆fH N2O4(g) = 9.7 kj mol-1

34 d) What are electrophiles? Give an example. 5


e) Explain the principle of paper chromatography.
f) Write the chemistry of lassaigne’s test for qualitative analysis of nitrogen.
Or
e) What are nucleophiles? Give one example of nucleophile.
f) Will CCl4 give white ppt of AgCl on heating with silver Nitrate. Give reason for your
answer.
g) Define hyper conjugation.
h) Draw the condensed formula and bond-line structural formula for hexane and 2,3,
dimethylpentane.

35 5
a. CH ≡ CH red hot iron tube, 873K X CH3COCl, Anhyd.AlCl3 -> Y
Find X and Y in the above sequence of reaction.
b.Explain Markovnikov’s rule with an example .
c. Convert phenol to benzene.

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Marking scheme

1B 2B 3D 4A 5A 6A 7D 8A 9D
10 A 11 A 12 C 13 D 14 B 15 C 16 A 17 D 18 A

19. A.Mole Fraction is the ratio of number of moles of one component to the total 1
number of moles (solute and solvents) present in the solution. It is
expressed as 'x'
B. The reactant which gets consumed first or limits the amount of product formed is
known as limiting reagent 1
20 (a) 5f -orbital 1
(b) Balmer Series 1
21 (a) splitting of spectral lines in presence of magnetic field (fine splitting) 1
(b) de Broglie relationship wave length = h/p 1
22

PCl5 trigibal bipyramidal


SF4 = see-saw
23 (a)Hess Law: If a reaction takes place in several steps then its standard reaction 1
enthalpy is the sum of the standard enthalpies of the intermediate reactions into +
which the overall reaction may be divided at the same temperature. ½+½
(b)(i) + Ve (ii) – Ve
24 (a)It is difficult to remove positively charged proton from a negative ion HSO4-. 1
(b) Kc’=1/ Kc = 1/4.0 =0.25 1
25 (i)CH3COO-Na+→ CH4 + Na2CO3 1

(ii) → ) 1

26 Number of moles of H2 =4.96×103 mol ½


Number of moles of N2 17.86×102 mol ½
3.30×103 mol NH3 (g) is obtained. ½
56.1 kg NH3 ½
dihydrogen is the limiting reagent 1
OR
Step 1. Conversion of mass per cent to grams
Step 2. Convert into number moles of each element Divide the masses obtained
above by respective atomic masses of various elements. This gives the number of
moles of constituent elements in the compound 1
Moles of hydrogen =4.07 g/1.008g = 4.04 1
Moles of carbon = 24.27 g/12. 01g = 2 .021 1
Moles of chlorine = 71.65g/ 35 453 g = 2 021
Step 3. Divide each of the mole values obtained above by the smallest number
amongst them
Since 2.021 is smallest value, division by it gives a ratio of 2:1:1 for H:C:Cl .
In case the ratios are not whole numbers, then they may be converted into whole
number by multiplying by the suitable coefficient.

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27 1
1
1

28 (a) All of them are isoelectronic in nature and have 10 electrons each. 1
(b) In isoelectronic species, greater the nuclear charge, lesser will be the atomic or 1
ionic radius. 1
Al3+ < Mg2+ < Na+ < F– < O2- < N3-
(c) group=17 period=5
29 (i)Cl=+5 Mn=+6 ½+½
(ii) Calculation of Oxidation no.
Balance of atoms other than H and O ½X4
Balance of H and O
Complete balanced reaction
30 a) The atom or group of atom attached to carbon chain which is responsible for 1
specific chemical properties of organic compounds. 1
b) –CHO,-NO2 1
c) Sp3 , sp2 ,sp2 ,sp3.
31 1.O2 = σ1s2 σ∗1s2 ,σ2s2,σ∗2s2,σ2pz2,π2px2,π2py 2, π*2px1,π*2py0
+

2. because bond order of Ne2 is zero. 1


3. super oxide ion .O2-=10-7/2=1.5 1
4. O2is less stable than O2+as its bond order is 2 and O2+2.5. 1
OR 1
N2 is diamagnetic as it has no unpaired e- while O2 paramagnetic as it has two
unpaired e in π*ABMO.
32 1. AlCl3 has incomplete octet and has tendency to accept e pair. 1
2. NH4+ and NH2- respectively. 1
3. The acid which dissociates completely in its aq. Solution. 1
4. Lewis base , NH3 ROHand Arhenius base. NH4OH, Ca(OH)2, 1
OR
PH=-log [H+] concentration of H+ ion determine the PH of acid.
33 a) H2O(g) will have greater entropy. 1
(b) at equilibrium ΔG° is zero 1
(c) A state function is a thermodynamic property that depends upon the state of the 1
system and is independent of the path followed to bring about the change. Internal
energy change (ΔU), enthalpy change (ΔH) entropy change (ΔS), and free energy
change (ΔG) are examples. 2
(d) Entropy is a measure of randomness of a system
Any one example to show (as per NCERT book) that entropy is an extensive property.
OR
(a)Third law of thermodynamics: The entropy of crystalline substance at absolute 1
zero temp is zero. 1
(b) U depends on initial and final state but work on the path followed. 1+1+1
(c) Enthalpy of reaction (∆r,H) = sum of ∆fH of products - sum of ∆fH of reactants
[81 + 3 (- 393)] – [9.7 + 3 (- 110)]
= [81 – 1179] – [9.7 – 330] = – 778 kj mol-1

34 d. The species which are positively charged or electron deficient are called 1
electrophiles (electron seeking agent).example: H+, Cl+,AlCl3 .

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e. In paper chromatography, chromatographic paper dipped in solvents act as a 2


stationary phase whereas mixture of compounds dissolved in suitable solvents 2
forms the mobile phase. Different compounds have different adsorbing power,
therefore they move with different speeds and gets separated.
f. 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.
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). 1
c. Hyperconjugation is a general stabilising interaction. It involves delocalisation of σ 1
electrons of C—H bond of an alkyl group directly attached to an atom of unsaturated 1
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. 2
d. Correct structure
35 X= C6H6 Y=C6H5 CO CH3 2

b. During hydrohalogenation of alkene, the negative part of addendum ,HX is added 2


to the carbon having least no of hydrogen
CH3-CH= CH2 + HBr CH3-CH (Br) CH3 1
c.

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BLUE PRINT
CHEMISTRY SAMPLE PAPER-2
CLASS XI
S.No Name of the chapters MCQ A/R VSA I SA I Case LA Total
based
1 1 2 3 4 5 Weig
Mark Mark Marks Marks Marks Marks htage
1. Some basic concepts of 2 (2) 2(1) 3(1) 7
chemistry
2. Structure of atom 1(1) 3(1) 5(1) 9
3 Classification of elements 2(2) 1(1) 3(1) 6
and periodicity in properties
4 Chemical bonding and 2(2) 5(1) 7
molecular structure
5 Chemical thermodynamics 2(2) 4(2) 3(1) 9
6 Equilibrium 1(1) 2(1) 4(1) 7
7 Red-ox reactions 1(1) 3(1) 4
8 Organic chemistry –Some 2(2) 1(1) 4(2) 4(1) 11
basic principles and
Techniques
9 Hydrocarbons 2(2) 1(1) 2(1) 5(1) 10
14 4 14 15 8 15 70

KENDRIYA VIDYALAYA SANGATHAN, JAIPUR REGION


SAMPLE PAPER -02
CLASS: XI SUB:CHEMISTRY TIME:3 HRS M.M:70
Read the following instructions carefully.
a) There are 35 questions in this question paper with internal choice.
b) SECTION A consists of18 multiple-choice questions carrying 1mark each.
c) SECTION B consistsof7very short answer questions carrying2markseach.
d) SECTION C consists of5shortanswer questions carrying 3marks each.
e) SECTION D consists of 2case-based questions carrying 4 marks each.
f) SECTION E consists of3 long answer questions carrying 5 marks each.
g) All questions are compulsory.
h) Use of log tables and calculators is not allowed

Q.No QUESTIONS Marks

SECTION A
The following questions are multiple-choice questions with one correct answer. Each question carries 1
mark.There is no internal choice in this section.

Q.1 What is the percentage composition by mass of carbon present in urea? 1M


(A) 25% (B) 28% (c) 42% (D) 20%

Q.2 Equal volume of all gases contain equal no of molecules at constant temperature and 1M
pressure This is stated by
(A) Gay Lussac law (B) Boyle ‘s Law
(C)Avogadro law (D) None of the above

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Q.3 Chloride ion is isoelectronic with 1M


(A) Na+ (B) Mg (C) Ar (D) Al 3+
Q.4 The atomic number of the element Unbinilium is 1M
(A) 020 (B) 120 (C) 123 (D) 102

Q.5 The number of sigma bond and pi bond in ethyne is 1M


(A) 3 sigma two Pi bond (B) only 2 Pi bonds
(C) one sigma and two pi bond (D) Five sigma bonds one pi bonds

Q.6 Which of the following molecule is has zero dipolemoment. 1M


(A) Water (B) NH3
(C)NF3 (D) Carbon Tetra Chloride And CO2
Q.7 Which is correct about ∆G 1M
(A)It is negative for non-spontaneous process
(B) It is positive for spontaneous process
(C) It is zero for a reversible process
(D) It is zero for a spontaneous process
Q.8 At what temperature the entropy of perfect crystalline substance is zero 1M
(A) O K (B)273 K(C) O 0 C (D) 250 K
Q.9 The P H of aqueous solution of ammonium acetate is 1M
(A)Equal To Zero (B) Greater Than 7
(C) Equal To 7 (D) 14
Q.10 The Redox reaction in which a single substance undergoes both oxidation as well as reduction 1M
is called
(A) Exothermic reaction (B) combination reaction
(C) decomposition reaction (D) Disproportionation reaction
Q.11 The displacement of electrons in a multiple bond in the presence of attacking reagent is 1M
called
(A) Inductive effect (B) Electromeric effect
(C) Resonance (D) Hyper conjugation.
Q.12 The type of isomerism not found in alkenes is : 1M
(A) Chain isomerism(B)Geometrical isomerism
(C) Metamerism(D)Position isomerism
Q.13 The catalyst used in Friedel – Crafts reaction is 1M
(A)Aluminium Chloride
(B)Anhydrous Aluminium Chloride
(C)Ferric Chloride
(D) Copper .
Q.14 What is the correct decreasing order of boiling point? 1M
(A) Neopentane>Isopentane>Pentane
(B)Pentane>Isopentane>Neopentane
(C)Isopentane>Neopentane>Pentane
(D) None Of The Above
In these questions (Q. No 15- 18), a statement of assertion followed by a statement of reason is given. Choose
the correct answer out of the following choices.

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(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

Q.15 Assertion: An orbit cannot have more than two electrons. 1M


Reason: No two electrons in an atom can have same set of all four Quantum numbers.

Q.16 Assertion: Noble gas elements have positive electron gain enthalpy. 1M
Reason: Inert gas elements stable octet configuration.
Q.17 Assertion: The reaction between haloalkanes and sodium metal in presence of dry ether 1M
alkanes having even number are produced.
Reason: propane can be prepared by Wurtz reaction
Q.18 Assertion: Resonance hybrid cannot be presented by a single structure 1M
Reason: Energy of resonance hybrid is equal to the average of energiesof all canonical forms.

SECTIONB
This section contains 7 questions with internal choice in two questions. The following
questions are veryshortanswer typeand carry2 marks each.
Q.19 (i) What do you mean by limiting reagent? 2M
(ii)In the reaction 2A +4B --- 3C + 4D, when 5 moles of A react with 6 moles of B, then
which is limiting reagent and also calculate the amount of C formed.
Q.20 (i) Explain the term entropy. 2M
(ii)Write the mathematical form of first law of thermodynamics.
(OR)
Predict whether entropy change is positive or negative
(i)Heating a substance from 0k to 115K
(ii) H2 (g)-----2H (g)
Q.21 Derive the Relation Between Cp and Cv for an Ideal Gas. 2M

Q.22 The concentration of hydrogen ions in a sample of soft drink is 3.8 x 10-3 M. 2M
What is the pH value?

Q.23 Draw the Newman projection formulae of ethane. Which conformation is stable? 2M
(OR)
Explain ozonolysis of alkene and also give reaction.

Q.24 (i) WriteIUPACname for CH3-CH2-CO-CH2-CH2-COOH. 2M


(ii)Drawthebond line structure of 2,4–dimethyl heptane.
Q.25 Explain heterolytic cleavage with an example. 2M

SECTIONC
This section contains 5 questions with internal choice in two questions. The following questions are short answer
type and carry 3 marks each.
Q.26 A compound contains 4% hydrogen 24% carbon and 71.6% chlorine its molar mass is 3M
98.96g.What is its molecular formula?

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Q.27 (i) What do you mean by dual nature of electron? 3M


(ii) Calculate the wavelength of an electron moving with the velocity 2.05X10 7 m/s.
Q.28 What are transition metals? Write any four characteristics of transition metals. 3M
(OR)
(i) Name the element having the highest electronegativity value.
(ii) Write general electronic configuration of inner transition elements.
(iii) The ionization enthalpy of Boron is less than that of Beryllium. Why?

Q.29 Balance the following red-ox reaction in acid medium by ion electron method. 3M
Cr2O7+2 + Fe2+ -------- Fe3+ + Cr3+
(OR)
Explain the following reaction with suitable reaction
(I)decomposition reaction
(II) displacement reaction
(III) disproportion reaction

Q.30 Calculate the heat of combustion of ethylene (gas) to from CO2 (gas) and H2O (gas) at 298k 3M
and 1 atmospheric pressure. The heats of formation of CO2, H2O and C2H4are– 393.7,–241.8,
+52.3kJ per mole respectively.
SECTION D
(Case Based Questions)
The following questions are case-based questions. Each question has an internal choice and carries 4 (1, 1, 2)
marks each.

Q.31 Read the passage carefully and answer the questions that follow. 4M
According to Arrhenius concept, acids give H+ ions while bases produce OH˗ ions in their
aqueous solutions. Bronsted-Lowry defined an acid as a proton donor and a base as a proton
acceptor. When a Bronsted – Lowry acid reacts with a base, it produces its conjugate base
and a conjugate acid corresponding to the base with which it reacts. Thus, a conjugate pair
of acid - base differs only by a proton. The strength of acids and bases can be measured in
terms of their dissociation constants Ka (or pKa) and Kb (or pKb). Larger value of Ka or lower
value of pKa corresponds to greater strength of acids. Similarly, larger value of Kb or lower
value of pKb corresponds to stronger base. PH finds vital role in cosmetic formulations and
buffer solution is used in blood bank.
(i) Write the conjugate acid-base pair for the following
(a) NH3(b) HSO4˗

(ii) What are buffer solutions?


(iii) What are Lewis acids and Lewis Bases?
(OR)
Which of the following are Lewis acid and bases.
NH3,BF3,AlCl3, CH3NH2
Q.32 Read the passage carefully and answer the questions that follow. 4M
In an organic reaction a covalent bond between two carbon atoms or a carbon and some
other atom is broken and a new bond is formed. A sequential account of each step,
describing details of electron movement, energetics during bond cleavage and bond
formation, and the rates of transformation of reactants into products kinetics) is referred to
as reaction mechanism. A species having a carbon atom possessing sextext of electrons and a

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positive charge is called a carbocation (earlier called carbonium ion). The CH3+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. Some other examples of carbocations are: CH3CH2+(ethyl cation, a
primary carbocation), (CH3)2CH+ (isopropyl cation, a secondary carbocation), and (CH3)3C+
(tert–butyl cation, a tertiary carbocation).Carbocations are highly unstable and reactive
species. Alkyl radiradicals are classified as primary, secondary, or tertiary. Alkyl radical
stability increases as we proceedfromprimary to tertiary: Organic reactions, which proceed by
homolytic fission are called free radical or homopolaror nonpolar reactions.
(i) Write any two reactive intermediates which are unstable.
(ii) State the hybridation of carbonium ion.
(iii) Explain tertiary carbocation is more stabe than secondary and in turn primary .Explain
(OR)
What are electrophiles and nucleophiles .Give an example each

SECTION E
The following questions are long answer type and carry 5 marks each. Two questions have an internal choice.

Q.33 (i) Calculate the radius of the first orbit of He+. 2


(ii) State Heisenberg uncertainty Give any one significance of it. 2
(iii) Write electronic configuration ofCr3+ion .(Z=24) 1
(OR)
(i) What is the significance of magnetic quantum number?
(ii) If n=5,l=3 what is the designation of the orbital. 1
(iii) State aufbau principle. 1
(iv) Calculate the wave number of yellow radiation having wavelength 5800 A 0 1
2

Q.34 (i) Write two types of hydrogen bonding with its examples. 2
(ii) Though NH3 involves Sp3hybridisation, the shape is pyramidal .Explain with the help of 2
VSEPR theory.
(iii) Axial bonds in PCl 5 are slightly elongated than equatorial bonds .Give reason. 1
(OR)

(i) Compare the relative stability of O2 , O2 –,O2+, O2 –2 in terms of molecular orbit theory.
3
(ii) Write the resonance structures for NO2 and CO32-.
2

Q.35 Addition of HBr to propene yields 2-bromopropane, while in the presence of benzoyl 5M
peroxide, the same reaction yields 1-bromopropane. Explain and give mechanism

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Marking scheme Sample paper-2 chemistry–XI(2022-23)


1 d) 20% 1
2 c) Avogadro law 1
3 c) Ar 1
4 b) 120 1
5 a) 3 sigma two Pi bond 1
6 d) carbon tetrachloride and CO2 1
7 c. It is zero for a reversible process 1
8 a) OK 1
9 c) equal to7 1
10 d) Disproportionation reaction 1
11 (b) Electromeric effect 1
12 (c) Metamerism 1
13 (b) Anhydrous Aluminium Chloride 1
14 b)Pentane>Isopentane>NeoPentane 1
15 d. A is false but R is true 1
16 a. Both A and R are true and R is the correct explanation of A 1
17 c. A is true but R is false. 1
18 c. A is true but R is false 1
19 a. Reactant consumed fully in a reaction 1
b. 1

20 a. Measure of degree of 1
disorder b.∆U=q+w 1
(OR)
a. Positive 1
b. Positive 1
21 At constant volume heat capacity = Cv At constant pressure heat capacity = Cp
At constant volume qv= CvΔT =ΔU ½
At constant pressure qp= CpΔT =ΔH For one mole of an ½
idealgasΔH=ΔU+Δ(PV) =ΔU+Δ(RT) ½
ΔH=ΔU+RΔT
On substituting the values of ΔHandΔu, the equation is modified asCp ΔT = ½
CvΔT+RΔT
orCp-Cv =R
22 pH =– log[H+]=– log(3.8 x10-3)=– log3.8+3 =3 – 0.5798 =2.4202=
2.42
23 Staggered conformer is more stable 1+1

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(OR)

24 a. 4-Oxo hexanoic acid 1

b. correct structure 1

25 In this cleavage the shared pair of electrons goes with any one of the two bonded 1
atom
CH3- - 1

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26 ½
½
1
1

27 a. Having both particle as well as wave nature 1


b. =h/mv=6.626 x10 -34j-s ½
9.1x10-31kgx2.05x107m/s ½
=3.55x10 -11m 1

a. Elements having partially filled d orbital either in ground state or oxidation 1


28 state
Formation of coloured ion, complex, alloy, showing paramagnetism (any
Four) 2
(OR)
a. Flourine 1
b, (n-2 )f 1-14 (n-1)d 1or o ns2 1
c. In boron the differentiating electron to be removed is in p subshell which is 1
less penetrating.
29 Balancing each half reaction of oxidation and and reduction 1=1
Cr2 O 7 2- + 6Fe 2+ 14 H+ 6Fe 3+ +2 Cr 3+ +7H2O 1
(OR)
a. .1Salt bridge maintains electrical neutrality2.It prevents accumulation 1
ofcharges around the electrode. Any one point.
1
b. +7
c. Zn(S) I Zn 2+ (aq) II Cu2+ (aq) I Cu(S) 1

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30
.

31 a. Answer: i) Conjugate acid: NH4+ Conjugate base: NH2˗ ½


ii) Conjugate acid: H2SO4 Conjugate base: SO42˗ ½
b.The solution which resists the change in PH on the addition of small amount of
acid or base or dilution 1
c. Electron pair acceptor is Lewis acid 1
Electron pair donor is Lewis base. 1
(OR)
c.
Answer: Lewis acid: BF3, AlCl3 1
Lewis base: NH3, CH3NH2 1

32 a. Carbonium ion, carbanion, free radical (any two) ½+1/2


b. Sp2 1
c. Since alkyl groups are electron releasing groups, positive charge of carbonium 1
ion is dispersed by inductive and hyperconjugation.
Greater the no of alkyl groups ,greater is the stability,Hence 30 carbonium is
more stable than 20 and in turn 1 0 1
(OR)
c. Electrons loving species are electrophiles. H+ ,Cl +
Nucleous loving species or electron rich species are nucleophiles NH3, CN - 4x1/2

33 a. r =52.9 n2/ ZPm ½


=52.9 1 2/2 Pm ½
=26.45 Pm

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b. It is impossible to determine the exact position and velocity of sub 1


atomicparticles simultaneously.
It rules out the definite path for an electron. 1
It is applicable for micro sized particles only (any one
point)c.1S2 2S2 2P63S2 3P6 3d3 1
(OR)
a,It signifies the orientation of 1
orbitalb.5f orbital
1
c.In building up of an atom, electrons enter into various atomic orbitals in
1
theincreasing of energy.
d. wave number = 1/
1
= 1/ 5800 x 10 -10 m
=1.72x10 6 m -1 ½
½
1
34 a. Intra molecular hydrogen bonding O=nitro phenol 1
Inter molecular hydrogen bonding water ,ammonia 1
b.Ammonia has one lone pair of electron .Since the repulsion between bond pair 1
– bond pair is less than lone pair –bond pair , the shape becomes 1
pyramidal.c.The axial bond pairs suffers more repulsion tha equatorial 1
bond pairs,
(OR) ½
a.Bond order =1/2 [Nb-Na] ½
O2=1/2 [10-6] =2 with Mo ½
configurationO2- =1/2[10=7]=1.5 ½
O2 2- =1/2 [10-8] =1
Increasing order of 1
stabilityO2 2- < O2- < O2

Sigma bond Pi bond

1. axial overlapping of orbits 1.lateral or sidewise overlapping of orbitals 1+1


2. Strong bond 2. Weak bond
3. pure and and hybrid orbitals 3. Only pure orbitals are
involvedMay form sigma bond
(any Two)
35 1+1

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KENDRIAYA VIDYALAYA SANGATHAN JAIPUR REGION


BLUE PRINT SAMPLE PAPER NO. 3 CHEMISTRY -XI
SN M M AR MA SA MA SA MA CAS MA LA- MAR TOT
C A RK -2 RK -3 RKS E RKS 5 KS AL
Q RK S S BAS
S ED-
4
1 Some 2 2 0 1 2 1 3 0 0 7
Basic
Concepts
of
Chemistr
y
2 Structure 2 2 1 1 1 2 0 1 4 0 9
of Atom
3 Classifica 0 0 1 2 1 3 0 0 5
tion of
Elements
and
Periodicit
y in
Propertie
s
4 Chemical 1 1 0 1 2 0 1 4 0 7
Bonding
and
Molecula
r
Structure
5 Chemical 0 1 1 1 2 0 0 1 5 8
Thermod
ynamics
6 Equilibriu 3 3 0 1 2 1 3 0 0 8
m
7 Redox 1 1 0 0 1 3 0 0 4
Reaction
s
8 Organic 2 2 1 1 0 1 3 0 1 5 11
Chemistr
y: Some
basic
Principles
and
Techniqu
es
9 Hydrocar 3 3 1 1 1 2 0 0 0 1 5 11
bons
TOTAL 1 14 4 4 7 14 5 15 2 8 3 15 70
4

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SAMPLE PAPER NO. 3 (2022-23)


KENDRIYA VIDYALAYA SANGHATHAN,JAIPUR REGION
CHEMISTRY THEORY
MM:70 Time:3 hours
General Instructions: Read the following instructions carefully.
There are 35 questions in this question paper with internal choice.
SECTION A consists of 18 multiple-choice questions carrying 1 mark each.
SECTION B consists of 7 very short answer questions carrying 2 marks each.
SECTION C consists of 5 short answer questions carrying 3 marks each.
SECTION D consists of 2 case- based questions carrying 4 marks each.
SECTION E consists of 3 long answer questions carrying 5 marks each.
All questions are compulsory.
Use of log tables and calculators is not allowed
SECTION A
1 The shape of carbocation is-
(A) Pyramidal (B) Linear (C) Trigonal Planar (D) Tetrahedral
2 What is the criteria for a reaction to be spontaneous-
(A) G = -ve (B) G = 0 (C) G= + ve (D) G=0
3 For a given principal level n = 4, the energy of its subshells is in the order
(a) s > p > d > f (b) s < p < d < f
(c) s < p < f < d (d) f < p < d < s
4 Which one of the following ion has electronic configuration [Ar], 3d6.
(A) Fe3+ (B) Co3+ (C) Cr3+ (D) Mn3+
5 The oxidation number of Mn is maximum in
(A) KMnO4 (B) K2MnO4 (C) Mn3O4 (D) MnO2
6 BF3 is a Lewis acid because it-
(A) donates proton (B) accepts Proton
-
(C) donates e pair (D) accepts e- pair
7 The ionization enthalpy of nitrogen is greater than that of oxygen because of-
(A) greater attraction of nucleus for electrons
(B) the smaller size of the nitrogen atom
(C) more penetrating effect
(D) the extra stability of half- filled p-orbitals
8 Formation of CO and CO2 illustrates the law of ————–.
(a) Law of conservation of mass (b) Law of Reciprocal proportion
(c) Law of Constant Proportion (d) Law of Multiple Proportion

9 Which of the Following Statements about a Compound is Incorrect One?


(a) A molecule of a compound has atoms of different elements.
(b) The ratio of atoms of different elements in a compound is fixed
(c) A compound retains physical properties of its associated constituent elements
(d) A compound cannot be separated into its constituent elements by physical methods of separation

10 The group number, number of valence electrons, and valency of an element with the atomic number 15,
respectively, are:
(a) 16, 5 and 2 (b) 15, 5 and 3 (c) 16, 6 and 3 (d) 15, 6 and 2
11 The most polar bond is
(a) C – F (b) C – O (c) C – Br (d) C – S
12 The property of self–linkage among identical atoms to form long chain compounds is known as:

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(A) Catenation (B) Isomerisation


(C) Superposition (D) Halogenation
13 Paraffins is the name of
(A) Alkane (B) Alkene
(C) Alkyne (D) Benzene
14 What is the general formula of alkynes?
(A) CnH2n+2 (B) CnH2n
(C) CnH2n-1 (D) CnH2n-2
In the following questions (Q. No. 15 - 18) 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.
15 Assertion: Tertiary carbocation is more stable than primary .
Reason: The 3ºcarbocation has greater + I effect.
16 Assertion: But-1-ene does not show geometrical isomerism.
Reason: Carbon –carbon double bond restrict the free rotation of groups around it.
17 Assertion (A): According to Mendeléev, the properties of elements are a periodic function of their atomic
masses.
Reason (R) : Atomic number is equal to the number of protons
18 Assertion (A) : Entropy increases when Temperature of a crystalline solid is raised from 0 K to 115 K.
Reason (R) : When temperature is raised to 115 K, molecule begin to move and oscillate about their
equilibrium positions in the lattice and system becomes more
disordered
SECTION B
19 (i) State pauli’s exclusion principle.
(ii) Draw the boundary line diagram of dz2 orbital.
20 (i) Explain Hund’s rule of maximum multiplicity .
(ii) Write the value for n and l for 4d orbital.
21 (i)Draw the orbital diagram of ethene.
(ii)What are deactivating groups. Give an example.
22 State law of multiple proportion with example.
23 Answer following.
(i) Write the electronic configuration of O2 molecule according to MOT.
(ii)Justify the Paramagnetism of O2 molecule on the basis of MOT
OR
(i) What is the state of hybridization of Cl in ClF3.
(ii) Write two differences between sigma and pi bond.
24 (i) Write the expression for equilibrium constant for following reaction.
CO(g) + 3H2 (g) ⇌ CH4 (g) + H2O(g)
(ii) Consider the following reactions
C+ ½O2 CO; Kc= 20
CO+ ½O2 CO2; Kc= 30.
Calculate the value of equilibrium constant for the reaction C+O2 CO2
0R
(i) H2 (g) +I2(g) 2HI(g). Write the relationship between Kp and Kc for the given
reaction.
(ii) Write the conjugated acid and base of NH3.
25 For the reaction at 298 K,
2A + B →C

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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?
SECTION C
26 (i). Write the IUPAC names of following compounds.
(i) CH3- CH- CH2 - CH- CH3 (ii) CH3 – CH – CH2–CH2 – CHO
| | |
Br COOH CH3

(iii) CH3- CH2-COOCH3


27 (i) Calculate the oxidation No. of Cl amd Mn in HClO4 and in KMnO4
(ii) Balance the following ionic equation by ion electron method or oxidation method.
Cr2O7 2-(aq) + SO32- (aq)  Cr3+(aq)+ SO4 2-(aq) (Acidic medium)
28 50.0 kg of N2 (g) and 10.0 kg of H2 (g) are mixed to produce NH3 (g). Calculate the amount of
NH3 (g) formed. Identify the limiting reagent in the production of NH3 in this situation.
OR
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?
29 (a) Write designation of an orbital having n = 5, 1 = 3.
(b) Name the spectral line series in the spectrum of H-atom obtained when an electron
jumps from n = 4 to n = 2.
(c ) Define Zeeman effect.
30 Explain the following
a) Chlorine have more negative electron gain enthalpy than fluorine
b) Write the symbol and IUPAC name for atom with atomic no 102.
c) Write the electronic configuration of trivalent ion of element for Z= 26
SECTION:D
31 In order to explain the characteristic geometrical shapes of polyatomic molecules like
CH4, NH3 and H2O etc., Pauling introduced the concept of hybridisation. According to
him the atomic orbitals combine to form new set of equivalent orbitals known as
hybrid orbitals. Unlike pure orbitals, the hybrid orbitals are used in bond formation.
The phenomenon is known as hybridisation which can be defined as 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. For example when one 2s and three 2p-orbitals of carbon hybridise,
there is
the formation of four new sp3 hybrid orbitals.

(a) Why axial bonds are weaker than equatorial bonds in PCl5
(b) What is the shape of compound undergoing sp3d hybridization?
(c) Explain conditions for Hybridisation (any two )
32 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.

(a)Write the equilibrium constant expression for the reaction taking place during
Haber process.
(b)How does the value of Kc for this reaction change with increase in temperature?
(c)Write the expression which represents the relationship between Kp and Kc for this reaction.

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(d)starting with two mol each (N2, H2, NH3) predict the direction of reaction?
SECTION:E
33 (i) What is the criterion for a reaction to be spontaneous?
(ii) Write expression for work done in isothermal reversible process.
(iii) For the reaction, 2 Cl(g) → Cl2 (g), what are the signs of ∆H and ∆S ?
(iv) Consider the following thermochemical equation.
N2 (g) + 3H2 (g)  2 NH3 (g) ; rH° = - 92.4 kJ /mol
and Calculate the standard enthalpy of formation of ammonia.
Or
(a) State third law of Thermodynamics.
(b) U is a state function but work is not?
(c) Calculate the enthalpy of the reaction:
N204(g) + 3CO(g)  N20(g) + 3CO2(g)
Given that; ∆fHº CO (g) = – 110 kj mol-1; ∆fH C02(g) = – 393 kj mol-1
∆fH N20(g) = 81 kj mol-1; ∆fH N2O4(g) = 9.7 kj mol-1
34 (a) Complete the following reactions.
(i) CH3COO-Na+ →
(ii) →
(iii) →
(b) State the Huckle Rule.
(c) Show the resonance in phenol.

OR
(a) Explain the following reaction with examples
(i) Friedal-craft alkylation reaction
(ii) Wurtz reaction
(iii) ozonolysis of propene
(c) Draw geometrical isomers of But-2-ene.
(d) arrange the following in increasing order of acidic character.
CH3–CH3 , H2C=CH2 , HC ≡ CH
35 (a)How can ethene be prepared from (i) ethanol (ii) ethyl bromide?
(B)What is Wurtz reaction? How can it be used to prepare butane?
Or
(A) Which alkene upon ozonalysis will give CH3CH2 CHO and CH3 CO CH3
(B) How will you convert ethyne to benzene?
(C) Write chemical reaction to exemplify Friedel-Crafts alkylation of benzene.
(D) Complete the following reactions:
(i) CH3CH2Br + Alc.KOH →
(ii) CH3CH = CHCH3 + O3 →

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MARKING SCHEME N0. 3(2022-23)


KENDRIYA VIDYALAYA SANGHATHAN,JAIPUR REGION
CHEMISTRY THEORY
MM:70 Time:3 hours
SECTION A
1 C 1
2 A 1
3 (B) s<p<d<f 1
4 (B) Co3+ 1
5 (A) KMnO4 1
6 (D) accepts e- pair 1
7 (D) the extra stability of half- filled p-orbitals 1
8 D 1
9 C 1
10 B 1
11 A 1
12 A 1
13 A 1
14 D 1
15 A 1
16 B 1
17 B 1
18 A 1
SECTION B
19 (i) pauli’s exclusion principle- one orbital can have only two e- but with opposite 1
spin.
1

(ii)
20 (i) Hund’s rule: in degenerated orbitals pairing of does not takes place until each 1
orbital get one e.

(ii)for 4d orbital, n=4 , l=2 ½+½

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21 1

½
(ii)Deactivating groups: these groups deactivate benzene ring towards
electrophilic substitution reaction by decreasing e density on it. Ex- NO2 / X / -CN ½
etc (any other)
22 Law of multiple proportion: when two elements combine to form more than two 1+1
compounds then the ratio of the masses of the second element which combine
with a fixed mass of the first element will be ratio of small whole numbers.
ex - H20
H2O2 (Hydrogen Peroxide)
Here the ratio of oxygen in both compounds= 1 : 2
23 1+1

(ii) oxygen has two unpaired pi antibonding MO.


OR
3
(i)ClF3 sp d hybridization
(ii) any two difference
24 (i) Kc=[CH4 ][ H2O] /[CO] [H2 ] 3 1+1
(ii) K= K1 X K2 = 20x30 =600
OR
(i)Kp= Kc
(ii) conjugated acid NH4+ conjugated base NH2-
25 Ans: ∆G =∆ H – T∆S 1/2
Assume that the equation is at equilibrium then ΔG = 0
ΔG=ΔH−TΔS=0 1.5
Therefore ΔH =TΔS
T= ΔH/ΔS =2000K
At 2000 K ΔG = 0
Reaction to be spontaneous ΔG must be negative. Therefore temperature should
be greater than
2000 K

SECTION C
26 (i)4-Bromo-2-methylpentanoic acid 1
(ii) 4- Methylpentanal 1
(iii) methyl propanoate 1
27 (i)Cl=+7 Mn=+7 ½ +½
(ii) Calculation of Oxidation no.
Balance of atoms other than H and O ½ x 4=2
Balance of H and O
Complete balanced reaction
28 Number of moles of H2 =4.96×103 mol ½

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Number of moles of N2 17.86×102 mol ½


3.30×103 mol NH3 (g) is obtained. ½
56.1 kg NH3 ½
1
dihydrogen is the limiting reagent
OR
Step 1. Conversion of mass per cent to grams
Since we are having mass per cent, it is convenient to use 100 g of the compound
as the starting material. Thus, in the 100 g sample of the above compound, 4.07g
hydrogen, 24.27g carbon and
71.65g chlorine are present.
Step 2. Convert into number moles of each element Divide the masses obtained
above by respective atomic masses of various elements. This gives the number of
moles of constituent elements in the compound
Moles of hydrogen =4.07 g/1.008g = 4.04
Moles of carbon = 24.27 g/12. 01g = 2 .021
Moles of chlorine = 71.65g/ 35. 453 g = 2. 021
Step 3. Divide each of the mole values obtained above by the smallest number
amongst them
Since 2.021 is smallest value, division by it gives a ratio of 2:1:1 for H:C:Cl .
In case the ratios are not whole numbers, then they may be converted into whole
number by multiplying by the suitable coefficient.
Step 4. Write down the empirical formula by mentioning the numbers after
writing the symbols of respective elementsCH2Cl is, thus, the empirical formula of
the above compound.
Step 5. Writing molecular formula
(a) Determine empirical formula mass by adding the atomic masses of various
atoms present in the empirical formula. For CH2Cl, empirical formula mass is
12.01 + (2 × 1.008) + 35.453 = 49.48 g
(b) Divide Molar mass by empirical formula mass 98.96/49.48 = 2 = (n)
(c) Multiply empirical formula by n obtained above to get the molecular formula 3
Empirical formula = CH2Cl, n = 2. Hence molecular formula is C2H4Cl2.
29 (a) 5f -orbital 1
(b) Balmer Series 1
(c ) splitting of spectral lines in presence of magnetic field (fine splitting 1

30 a) It is due to small size of fluorine atom. As a result, there are strong inter
electronic repulsions in the relatively small 2p orbitals of fluorine and thus, the 1
incoming electron experience much repulsion. 1
b) Unnilbium ( Unb) 1
c) Fe3+ 1s22s22p63s23p63d5
SECTION:D
31 (a) more repulsions produced by electrone pair of equatorial position 1
( vsepr theory)
(b) trigonal bipyramidal 1
(c)(i) The orbitals present in the valence shell of the atom are hybridised.
(ii) The orbitals undergoing hybridisation should have almost equal energy. 2

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(iii) Promotion of electron is not essential condition prior to hybridisation.


(iv) It is not necessary that only half filledorbitals participate in hybridisation.
Insome cases, even filled orbitals of valence shell take part in hybridisation
(ANY TWO)
32 Answer 1
(a). Kc = [ NH3]2/[ N2][H2]3 1
(b)Decreases 1
(c) Kp = Kc/(RT)2 1
(d) Backward direction
SECTION:E
33
(i) G =-Ve
1
(ii) W= 1
1
(iii) ∆H = -ve and ∆S=-ve 1+1
(iv) fH°= rH°/2 = - 92.4 /2 = -46.2 KJ/mol
OR
(a)Third law of thermodynamics: The entropy of crystalline substance at absolute 1
zero temp is zero.
(b) U depends on initial and final state but work on the path followed. 1
(c) Enthalpy of reaction (∆r,H) = sum of ∆fH of products - sum of ∆fH of reactants
[81 + 3 (- 393)] – [9.7 + 3 (- 110)] 1+1+1=3
= [81 – 1179] – [9.7 – 330] = – 778 kj mol-1

34 (a) (i)CH COO-Na+→ CH4 + Na2CO3 1


3
1
(ii) → ) 1
(iii) →

(b) Cyclic compounds having (4n+2) pi electrons are aromatic. n= 0,1,2,3….


(c) 1
1

OR
i) Friedal-craft alkylation reaction

1X 3

ii) Wurtz reaction

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(iii) ozonolysis of propene

(c) geometrical isomers of But-2-ene. 1

(d) Increasing order of acidic character.


CH3–CH3 <H2C=CH2 < HC ≡ CH
35 (i) Ethene from ethanol- by acidic dehydration of alcohols 1+1+3

(II)Ethene from ethyl bromide- by dehydrohalogenation of ethyl bromide


CH3CH2Br + KOH (alc) → CH2 = CH2 + KBr + H2

(B)When alkyl halides is treated with metallic Na in presence of dry ether, alkanes
are formed. This reaction is called Wurtz reaction.
Butane is prepared by the reaction of bromoethane with metallic Na in presence
of dry ether

OR 1+1+1+2
(A) CH3-CH2-CH=C (CH3)2

(B)

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(C)

(D) (i) CH3CH2Br + Alc.KOH→ CH2=CH2+KBr+H2O


(ii) ) CH3CH = CHCH3 + O3→ 2 CH3CHO

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KENDRIAYA VIDYALAYA SANGATHAN JAIPUR REGION

BLUE PRINT SAMPLE PAPER 4 CHEMISTRY -XI


CAS M M
E A A
BAS R R
SA- MA SA- MA ED- K LA- K
SN MCQ MARKS AR MARKS 2 RKS 3 RKS 4 S 5 S TOTAL
Some Basic
Concepts of
1 Chemistry 2 2 0 1 2 1 3 0 0 7
Structure of
2 Atom 2 2 0 2 4 1 3 0 0 9
Classification of
Elements and
Periodicity in
3 Properties 2 2 1 1 0 1 3 0 0 6
Chemical
Bonding and
Molecular
4 Structure 1 1 0 1 2 0 1 4 0 7
Chemical
5 Thermodynamics 1 1 1 1 1 2 0 0 1 5 9

Equilibrium
6 1 1 0 1 2 0 1 4 0 7

Redox Reactions
7 1 1 0 0 1 3 0 0 4
Organic
Chemistry: Some
basic Principles
8 and Techniques 2 2 1 1 0 1 3 0 1 5 11

Hydrocarbons
9 2 2 1 1 1 2 0 0 0 1 5 10
1
TOTAL 14 14 4 4 7 14 5 15 2 8 3 5 70

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CHEMISTRY SAMPLE QP 4 CLASS 11


General Instructions: Read the following instructions carefully.
a) There are 35 questions in this question paper with internal choice.
b) SECTION A consists of 18 multiple-choice questions carrying 1 mark each.
c) SECTION B consists of 7 very short answer questions carrying 2 marks each.
d) SECTION C consists of 5 short answer questions carrying 3 marks each.
e) SECTION D consists of 2 case- based questions carrying 4 marks each.
f) SECTION E consists of 3 long answer questions carrying 5 marks each.
g) All questions are compulsory.
h) Use of log tables and calculators is not allowed

SECTION A

The following questions are multiple-choice questions with one correct answer. Each questioncarries
1 mark. There is no internal choice in this section

1. .Which of the following pairs of gases contains the same number of molecules?

(i) 8 g of O2 and 7 g of N2 (ii) 8 g of O2 and 4.4 g of CO2

(iii) 28 g of N2 and 22 g of CO2 (iv) 32 g of O2 and 14g of N2

2. . Which of the following statement about a compound is incorrect ?


(i) A molecule of a compound has atom of different elements.

(ii) A compound cannot be separated into its constituent elements by physical method of separation.

(iii) A compound retained the physical properties of the constituents

(iv) The ratio of atoms of different elements in a compound is fixed.

3. The pair of ions having same electronic configuration is .

(i) Cr3+ , Fe3+


(ii) Fe3+, Mn2+

(iii) Fe3+, Co3+

(iv) Sc3+, Cr3+

4. Which of the following statements concerning the Quantum numbers are correct ?

(i) Angular quantum number determines the three dimensional shape of the orbital.

(ii) The principal quantum number determines the orientation and energy of the orbital.

(iii) Magnetic quantum number determines the size of the orbital.

(iv) Spin quantum number of an electron determines the orientation of the orbital.

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5. The elements in which electrons are progressively filled in 5f-orbital are called -
(i) Actinoids

(ii) transition elements

(iii) lanthanoids

(iv) halogens

6. The period number in the long form of the periodic table is equal to
(i) magnetic quantum number of any element of the period.

(ii) atomic number of any element of the period.

(iii) maximum Principal quantum number of any element of the period.

(iv) maximum Azimuthal quantum number of any element of the period.

7.Which of the following species does not have tetrahedral geometry?


(i) CCl4

(ii) NH3

(iii) CH43

(iv) NH4+

8. In Which of the following substances will hydrogen bond be strongest?


(i) HCl

(ii) H2O

(iii) HI

(iv) H2S
9.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

10. 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

11. We know that the relationship between Kc and Kp is Kp = Kc(RT)∆n

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What would be the value of ∆n for the reaction

PCl5 (s) → PCl3 (g) + Cl2 (g)


(i) 1

(ii) 0.5

(iii) 1.5

(iv) 2

12. For the reaction H2(g) + I2(g) → 2HI (g), the standard free energy is ∆G0 > 0.

The equilibrium constant (K ) would be .

(i) K = 0
(ii) K > 1

(iii) K = 1

(iv) K < 1

13. Which of the following is not an example of redox reaction?


(i) CuO + H2 → Cu + H2O

(ii) Fe2O3+ 3CO → 2Fe + 3CO2

(iii) 2K + F2 → 2KF

(iv) BaCl2 + H2SO4→ BaSO4 + 2HCl

14. Choose the correct oxidation state of the Underlined atoms of the given molecules –

PCI5 and SF6

(i) +5 & +3

(ii) +5 & +6

(iii) +5 & -3

(iv) -5 & -6

15.Assertion (A) : Energy of resonance hybrid is equal to the average of energies of all canonical
forms.

Reason (R) : Resonance hybrid cannot be presented by a single structure.


(i) Both A and R are correct and R is the correct explanation of A.

(ii) Both A and R are correct but R is not the correct explanation of A.

(iii) Both A and R are not correct.

(iv) A is not correct but R is correct

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16.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.
(i) Both A and R are correct and R is the correct explanation of A.

(ii) Both A and R are correct but R is not the correct explanation of A.

(iii) Both A and R are not correct.

(iv) A is not correct but R is correct.is not correct but R is correct.

17. Assertion (A) : Toluene on Friedal Crafts methylation gives o– and p–xylene.
Reason (R) : CH3-group bonded to benzene ring increases electron density at o– and p– position.
(i) Both A and R are correct and R is the correct explanation of A.

(ii) Both A and R are correct but R is not the correct explanation of A.

(iii) Both A and R are not correct.

(iv) A is not correct but R is correct.

18. Assertion (A): Nitration of benzene with nitric acid requires the use of concentrated
sulphuric acid.Reason (R) : The mixture of concentrated sulphuric acid and concentrated
nitric acid produces theelectrophile, NO2+.
(i) Both A and R are correct and R is the correct explanation of A.

(ii) Both A and R are correct but R is not the correct explanation of A.

(iii) Both A and R are not correct.

(iv) A is not correct but R is correct.

SECTION B
This section contains 7 questions with internal choice in two questions. The following
questionsare very short answer type and carry 2 marks each.
19. The empirical formula and molecular mass of a compound are CH2O and 180 g respectively.What will be
the molecular formula of the compound?

20. Arrange s, p and d sub-shells of a shell in the increasing order of effective nuclear charge (Zeff)
experienced by the electron present in them.

Or
Calculate the total number of angular nodes and radial nodes present in 3p orbital?
21. Explain why the electron gain enthalpy of oxygen is less negative than that of Sulphur.Or

All transition elements are d-block elements, but all d-block elements are not transition
elements.Explain.

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22. Calculate the total number of sigma and Pi bonds in Ethene, CH2=CH2 ?

23. Predict the relationship between ΔU and ΔH for the following reactions.
(i) S(s) + O2(g) → SO2(g)
(ii) PCl5(g) → PCl3 (g) + Cl2(g)

24. The following concentrations were obtained for the formation of NH3 from N2 and H2 at
equilibriumat 500K. [N2 ] = 1.5 × 10–2M. [H2 ] = 3.0 ×10–2 M and [NH3 ] = 1.2 ×10–2M. Calculate
equilibrium constant.

25. What is the oxidation state of oxygen in oxides and peroxides?

SECTION C
This section contains 5 questions with internal choice in 2 questions. The following
questions are short answer type and carry 3 marks each.
26. Name the spectral series which appear in the region of electromagnetic spectrum.
(a) Visible region
(b) UV region
(c) Far IR region.

27. What is meant by hybridisation of atomic orbitals? Describe the shapes of sp, sp2, sp3 hybridorbitals.

28. At 473 K, equilibrium constant Kc for decomposition of phosphorus pentachloride, PCl5 is


8.3 ×10-3. If decomposition is depicted as, PCl5 (g)→ PCl3 (g) + Cl2 (g) ∆rH 0 = 124.0 kJ mol–1
a) Write an expression for Kc for the reaction.
b) What is the value of Kc for the reverse reaction at the same temperature?
c) What would be the effect on Kc if (i) more PCl5 is added (ii) pressure is increased (iii) the
temperatureis increased.

29. Write bond line formulas for: Isopropyl alcohol, 2,3-Dimethylbutanal, Heptan-4- one.

OR
Write bond line formulas for: Isobuty alcohol, 2 pentanone, 3-pentene
30. Draw the cis and trans structures of hex-2-ene. Which isomer will have higher b.p. and why?

OR

Explain geometrical isomerism in alkene by using the example of 2- butene ?

SECTION D

The following questions are case-based questions. Each question has an internal choice
and carries 4 (1+1+2) marks each. Read the passage carefully and answer the questions
that follow.

31. Read the passage and answer the questions.


Molecular orbitals are formed by the overlap of atomic orbitals. Two atomic orbitals combine
to form two molecular orbitals called bonding molecular orbital (BMO) and anti bonding

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molecular orbital (ABMO). Energy of anti bonding orbital is raised above the parent atomic
orbitals that have combined and the energy of the bonding orbital is lowered than the parent
atomic orbitals. Energies of various molecular orbitals for elements hydrogen to nitrogen
increase in the order:
Different atomic orbitals of one atom combine with those atomic orbitals of the second atom
which have comparable energies and proper orientation. Further, if the overlapping is head
on, the molecular orbital is called ‘Sigma’, (σ) and if the overlap is lateral, the molecular orbital
is called ‘pi’, (π). The molecular orbitals are filled with electrons according to the same rules as
followed for filling of atomic orbitals. However, the order for filling is not the same for all
molecules or their ions. Bond order is one of the most important parameters to compare the
strength of bonds.

Answer the following.


a. Calculate the bond order for Hydrogen molecule.

b. Calculate the bond order for He


c. Calculate the bond order and magnetic nature of Oxygen molecule

or
Calculate the bond order and magnetic nature of Nitrogen molecule

Read the passage and answer the questions.


32. The Lewis structure or dot structure, dash structure, condensed structure and bond line structural
formulas are some of the specific types. The Lewis structures, however, can be simplified by
representing the two-electron covalent bond by a dash (–). Such a structural formula focuses on the
electrons involved in bond formation. A single dash represents a single bond, double dash is used for
double bond and a triple dash represents triple bond. Lone- pairs of electrons on heteroatoms (e.g.,
oxygen, nitrogen, sulphur, halogens etc.) may or may not be shown. Thus, ethane (C2H6), ethene (C2H4),
ethyne (C2H2) and methanol (CH3OH) can be represented by the following structural formulas. Such
structural representations are called complete structural formulas. For simplification, organic chemists
use another way of representing the structures, in which only lines are used. In this bond-line structural
representation of organic compounds, carbon and hydrogen atoms are not shown and the lines
representing carbon-carbon bonds are drawn in a zig-zag fashion. The only atoms specifically written
are oxygen, chlorine, nitrogen etc. The terminals denote methyl (–CH3) groups (unless indicated
otherwise by a functional group), while the line junctions denote carbon atoms bonded to appropriate
number of hydrogens required to satisfy the valency of the carbon atoms.

a. How many sigma and pi bonds are there in but- 2-ene?

b. The terminal group denote which group in bond line formula?

c. Represent the bond line formula of 2- bromo butane.

Or
Represent the bond line formula of cyclopropane.

33.The first ( iH1) and the second ( iH2) ionization enthalpies (in kJ mol–1)and the ( egH) electrongain
nthalpy (in kJ mol–1) of a few elements aregiven below:Elements

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H1 H2 egH

I 520 7300 –60


II 419 3051 –48
III 1681 3374 –328
IV 1008 1846 –295
V 2372 5251 +48
VI 738 1451 –40

Which of the above elements is likely to be:

(a) the least reactive element.


(b) the most reactive metal.
(c) the most reactive non-metal.
(d) the least reactive non-metal.

(e) the metal which can form a stable binary halide of the formulaMX2(X=halogen).

Or

Predict the formulas of the stable binary compounds that would be formed by the
combination of thefollowing pairs of elements.
(a) Lithium and oxygen (b) Magnesium and nitrogen
(c) Aluminium and iodine (d) Silicon and oxygen
(e) Phosphorus and fluorine

34.a). What is Chain isomerism?


b). What type isomerism is shown by propanone and
propanal
c). Identify the type of isomerism in propa-1-ol and propan-2-ol
d). In which C-C bond of bromopropane the inductive
effect is least?
e). Write the resonance structure of acetate ion.

Or

Give a brief description of the principles of the following techniques taking an example in each case.
(a) Crystallisation (b) Distillation (c) Chromatography

35.a). Write IUPAC names of the products obtained by addition reactions of HBr to hex-1-ene
(i) in the absence of peroxide and (ii) in the presence of peroxide
b). How will you convert ethanoic acid into benzene.
c). Write Friedel craft alkylation and acylation reaction.

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SAMPLE PAPER 4 (2022-23)


ANSWER KEY
(SECTION A each correct answer 1 mark)
1. I
2. III
3. II
4. II
5. I
6. III
7. II
8. II
9. I
10. I
11. IV
12. IV
13. IV
14. II
15. II
16. I
17. I
18. I

SECTION B

19. For correct empirical formula assign 1 mark + 1 mark for molecular formula C6H12O6 (2)
20. d < p < s OR For 3p orbital n = 3, l = 1 (2)
Number of angular nodes = l = 1
Number of radial nodes = n – l – 1 = 3–1–1=1
21. The
added electron in oxygen goes to second quantum level. Due to small lsize of oxygen itexperiences
repulsion from other electrons much more in comparison to that in sulphur because in sulphur, the
electron is added to 3rd quantum level in which larger space is available for movement. (2)
Or
Elements with fully filled d orbitals are not transition elements. (2)
22. 5 sigma bonds and 1 pi bond present in ehene (1+1)

23. (i) Δng = 0 Therefore , ΔU = ΔH + Δng RT , ΔU = ΔH 1+1

(i) Δng = 1 Therefore , ΔU = ΔH + Δng RT , ΔU > ΔH

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24. The equilibrium constant for the reaction, (1)


N2(g) + 3H2(g) 2NH3(g) can be written

Write kc Substitute and final answer 1.06 x10 3 ( refer TEXT BOOK (1)

25. -2 and -1 respectively (1)+(1)


SECTION C

26.(a) Balmer Series 1x3


(b) Lymen Series
(c) Pfund Series

27. correct explanation (1)


Correct shape (2)

28 a).kc= [ PCl3] [ Cl2]/ [ PCl5] (1)


b) Kc” = 1/kc (1)
c) no change / no change /kc will increase (1)

29.
(Each correct Answer 1 mark)

OR For each correct structure assign 1 mark .


30. (2)

Cis- form is more polar than trans-form i.e., cis-form has higher dipole moment than trans-form.
Thus, the boiling point of cis-isomer is greater than that of trans-isomer because of the greater
dipole-dipole interactions between the molecules in it. further more trans-
isomer of hex-2-ene is almost non-polar (1)

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OR
Correct explanation with example 2+1

31.a) Bond order for H2 is 1


b) Bond order for He is 0 (1+1+2)
c) Bond order for O2 is 2
or
Bond order for N2 is 3
32. a) 1 pi bond and 11 sigma bond (1)
b) methyl group (1)
c) (2)

OR

( 1 mark for each correct answer)


33. a) The element V has highest first IE and p ositive electron gain enthalpy and hence least
reactive. Since inert gases have positive electron gain enthalpy so the element must be a inert gas. So
may be He

b)The element II which has least first IE and low negative electron gain enthalpy is most
reactive so it must be K

c) The element III which has high first IE and very high negative EG is most reactive non metal so it
must be fluorine
d) The element IV has a high negative electron gain enthalpy but so high first IE .So it the least
reactive non metal ,it is Iodine
e) The element VI has low first IE but higher than that of alkali metal. So It is Alkaline
Earthmetal and forms binary halide. It is Mg

OR
a) Li2O
b) Mg3N2
c) AlI3
d) SiO2
e) PF3 or PF5

34. a) Chain isomers are those compounds with same chemical formula but differ in the name of parent chain
of the compound. (1 )
b) Functional isomerim (1)
c) Position isomerism (1)
d) C2-C3 (1)
e) Refer NCERT text book (1)

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OR

(a) Crystallisation Crystallisation is one of the most commonly used techniques for the purification of solid
organic compounds. Principle: It is based on the difference in the solubilities of the compound and the
impurities in a given solvent. The impure compound gets dissolved in the solvent in which it is sparingly
soluble at room temperature but appreciably soluble at higher temperature. The solution is concentrated to
obtain a nearly saturated solution. On cooling the solution, the pure compound crystallises out and is
removed by filtration.
(b) Distillation This method is used to separate volatile liquids from non-volatile impurities or a mixture of
those liquids that have a sufficient difference in their boiling points. Principle: It is based on the fact that
liquids having different boiling points vaporise at different temperatures. The vapours are then cooled and
the liquids so formed are collected separately down
(c) Chromatography It is one of the most useful methods for the separation and purification of organic
compounds. Principle: It is based on the difference in movement of individual components of a mixture
through the stationary phase under the influence of mobile phase. (2+2+1)

35. For each correct anshwer, assign – (1+1+1+2)

KENDRIAYA VIDYALAYA SANGATHAN JAIPUR REGION


BLUE PRINT SAMPLE PAPER 5 CHEMISTRY -XI
M CA M
A SE A
R BA R
MC K MA SA- MA SA- MA SE K LA- MA
SN Q S AR RKS 2 RKS 3 RKS D-4 S 5 RKS TOTAL
Some Basic
Concepts of
1 Chemistry 2 2 0 1 2 1 3 0 0 7
Structure of Atom
2 2 2 1 1 1 2 0 1 4 0 9
Classification of
Elements and
Periodicity in
Properties
3 1 1 0 1 2 1 3 0 0 6
Chemical Bonding
and Molecular
4 Structure 1 1 0 1 2 0 1 4 0 7
Chemical
5 Thermodynamics 1 1 1 1 1 2 0 0 1 5 9

6 Equilibrium 2 2 0 1 2 1 3 0 0 7

7 Redox Reactions 1 1 0 0 1 3 0 0 4
Organic Chemistry:
Some basic
Principles and
8 Techniques 2 2 1 1 0 1 3 0 1 5 11

9 Hydrocarbons 2 2 1 1 1 2 0 0 0 1 5 10
TOTAL 14 1 4 4 7 14 5 15 2 8 3 15 70

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4
KENDRIYA VIDYALAYA SANGATHAN JAIPUR REGION
SAMPLE PAPER 5 2022-2023
XI- CHEMISTRY Max.marks:70
Max.time:3hrs
Read the following instructions carefully.
There are 35 questions in this question paper with internal choice.
SECTION A consists of 18 multiple choice questions carrying 1 mark each.
SECTION B consists of 7 very short answer questions carrying 2 marks
each.SECTION C consists of 5 short answer questions carrying 3 marks
each.
SECTION D consists of 2 case-based questions carrying 4 marks
each. SECTION E consists of 3 long answer questions carrying 5
marks each. All questions are compulsory.
Use of log tables and calculators is not allowed.
SECTION A
The following questions are multiple-choice questions with one correct answer. Each question carries
1mark. There is no internal choice in this section.
1. What is the mass percentage of carbon in carbon dioxide?
(A) 0.034% (B) 27.27% (C) 3.4% (D) 28.7%

2. Which of the following parameters is temperature dependent?


A. Molarity B. Mole fraction. C. Weight percentage D. Molality

3. Which of the following statements does not form a part of Bohr's model of hydrogen atom?
A. Energy of the electrons in the orbit is quantized.
B. The electron in the orbit nearest to the nucleus has the lowest energy.
C. Electrons revolve in different orbits around the nucleus.
D. The position and velocity of the electrons in the orbit cannot be determined simultaneously.

4. In photoelectric effect, the kinetic energy of photoelectrons increases linearly with the
A.Wavelength of incident light B. Frequency of incident light
C. Velocity of incident light D. Atomic mass of an element

5. BCl3 is a planar molecule whereas NCl3 is pyramidal because:


A. nitrogen atom is smaller than boron atom
B. BCl3 has no lone pair of electrons whereas NCl3 has a lone pair of electrons
C. N-Cl bond is more covalent than B-CI bond
D. B-Cl bond is more polar than N-Cl bond

6. Which of the following is not an actinoid?


A. Curium (Z=96) B. Californium (Z=98) C. Uranium (Z=92) D. Terbium (Z=65)

7. When equal volumes of 0.002 M solutions of sodium iodate and cupric chlorate are mixed together (Ksp
(cupric iodate) = 7.4 × 10–8 ), from the following, the correct observation would be
A. Precipitation will occur
B. Precipitation will not occur
C. There are 50 % chances of precipitation
D.Data is not sufficient to make any conclusive observation

8.When a buffer solution of CH3COOH and CH3COONa is diluted with water:


A. CH3COO- ion concentration increases B. [H+] ion concentration increases
C. OH- ion concentration increases D. H+ion concentration does not change

9. Select the compound in which chlorine shows oxidation state is: + 7:

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A. HCIO4 B. HCIO3 C. HCIO2 D. HCIO

10. The pair of structures given below represents

A. Enantiomers B. Conformers C. Position isomers D. None of the above

11. For the process to occur under adiabatic conditions, the correct condition is
A. T=0 B. p=0 C. q=0 D. w=0

12. The most suitable method used for the separation of 1:1 mixture of ortho and para-nitro phenol is:
A. Chromatography B. Crystallization C. Steam distillation D. Sublimation

13. The reactants used in Friedel-Craft`s alkylation are-


A. C6H6+NH2 B. C6H6+CH4 C. C6H6+CH3Cl D. C6H6+CH3COCl

14. The reaction of toluene with Cl2 in presence of FeCl3 gives ‘X' and the reaction in presence of light
gives 'Y'. 'X' and 'Y' are respectively-
A. X= Benzal chloride, Y= o-chlorotoluene
B. X= m-chlorotoluene, Y= p-chlorotoluene
C. X= o and p-chlorotoluene, Y= trichloromethyl benzene
D. X= Benzyl chloride, Y= m-chlorotoluene

The questions given below consist of an 'Assertion' (A) and the 'Reason' (R). Use the following keys for
theappropriate answer:
(A) .If both (A) and (R) are correct and (R) is the correct reason for (A).
(B) .If both (A) and (R) are correct but (R) is not the correct explanation
for (A).(C). If (A) is correct but (R) is incorrect.
(D). If(A) is incorrect but (R) is correct.
15. Assertion (A) :In Rutherford's gold foil experiment, very few a-particles are deflected back.
Reason (R) :Nucleus present inside the atom is heavy. (A)

16. Assertion (A) The thermodynamic factor which determines the spontaneityty of a process is the free
energy. For a process to be spontaneous the free energy must be -ve.
Reason (R) The change in free energy is related to the change in enthalpy and change in entropy. Thechange in
entropy for a

17. Assertion (A) : Energy of resonance hybrid is equal to the average of energies of all canonical forms.
Reason (R) : Resonance hybrid cannot be presented by a single structure.

18. Assertion (A) : Nitration of benzene with nitric acid requires the use of concentrated sulphuric acid.
Reason (R) : The mixture of concentrated sulphuric acid and concentrated nitric acid produces the
electrophile,

SECTION B
19) What is the number of photons of light with a wavelength of 4000 pm that provide 1 J of energy?
20) Define the following terms: i. Molarity ii. Limitng reagent
21) Name the factors which affect the ionisation enthalpy of an element.
22. What is mean by bond order? Calculate the bond order of O2
molecule OR

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Discuss the shape of the following molecules using the VSEPR


model:SiCl4, AsF5, ClF3, NH3

23) Define entropy. predict whether entropy change in the following processes would be positive or
negative.
i. N2O3(g)N2O(g) +O2(g)
ii. NH3(g) +HCl(g) NH4Cl(s)

24) What is meant by the conjugate acid-base pair? Find the conjugate acid and base of NH3

25) What is ozonolysis? Write the names of the products obtained when 2-Methyl propene undergoes
ozonolysis?
OR

SECTION-C
26) An inorganic salt gave the following percentage composition-Na =29.11,S = 40.51 and O =30.38
.Calculate the empirical formula of the salt.(At .mass of Na=23,S=32 and O=16)

27) Explain the following with proper reasons:


i. Halogens have very high negative electron gain enthalpies.
ii. Mg2+ ion is smaller than O2-ion although both have the same electronic configuration.
iii. Electron gain enthalpy of fluorine is less negative than that of chlorine.

28) i) Define the pH of the solution. The pH of a sample of vinegar is 3.76. Calculate the concentration of
hydrogen ion in it.
iii) Write the expression for equilibrium constant, Kc for the
reaction4 NH3(g) + 5 O2(g) ⇌4 NO(g) + 6 H2O(l)
OR
a) State Le-Chatlier’s principle.
b) What is the effect of:
(i) addition of H2 (ii) addition of CH3OH
(iii) removal of CO (iv) removal of CH3OH

29. Balance the following redox reactions by ion – electron method :


Cr2O7 2- (aq) + S02 (g)——> Cr3+ (aq) + SO
4
2-
(aq) (in acidic solution)

30. In the estimation of sulphur by carius method,0.468 gof an organic sulphur compound gave 0.668 g of
barium sulphate.find the percentage of sulphur in the given compound.
OR
0.3780 g of an organic chloro compound gave 0.5740 g of silver chloride in carius estimation.calculate
thepercentage of chlorine present in the compound.

SECTION D

31) When anions and cations approach each other, the valence shell of anions are pulled towards
cation nucleus and thus, shape of anion is deformed. The phenomenon of deformation of anion by a
cation is known as polarization and the ability of the cation to polarize the anion is called as polarizing
power of cation. Due to polarization, sharing of electrons occurs between two ions to some extent and
the bond shows some covalent character. The magnitude of polarization depends upon a number of

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factors. Thesefactors were suggested by Pajan and are known as Fajan's rules.
i. Greater is the polarization in a molecule, more is covalent character.
ii. As the charge on cation increases, its tendency to polarize the anion increases.
iii. The size of the cation decreases or size of the anion increases, the polarization increases.
iv.The cations with 18 electrons in the outermost shell bring greater polarization of the anion than those
with inert gas configuration even both the cations have same size and same charge.

1. Considering BeCl2 , MgCI2, CaCl2 and BaCl2, predict which of the following statements is true?
A. BeCl2 is least ionic out' of the given chlorides
B. Covalent character increases as the atomic number of the metal atom increases
C. BeCl2 has the highest melting point among the given chlorides
D. All are highly ionic compounds

2. In which of the halides, there is maximum polarization?


A. AlF3 B. AlCl3 C. AlBr3 D. AlI3

3. Which is most covalent in nature?


A. NaCl B. AICl3 C. MgCl2 D. CaCl2

4. Non-aqueous solvent like ether is added to the mixture of LiCl, NaCl and KCI. Which will be extracted
into ether?
A. NaCI B. LiCI C. KCI D. None

32. Dual nature of matter was proposed by de Broglie in 1923, it was experimentally verified by Davisson
and Germer by diffraction experiment. Wave character of matter has significance only for microscopic
particles. de Broglie wavelength or wavelength of matter wave can be calculated using the following
relation:
A=
where, 'm' and v' are the mass and velocity of the particle. de Broglie hypothesis suggested that
electron.Waves were being diffracted by the target, much as X-rays are. Diffracted by planes of atoms
in the crystals.
Answer the following questions:
1. Planck's constant has same dimension as that of:
A. work B. energy C. power D. angular momentum

2. Wave nature of electrons is shown by:


A. photoelectric effect B. Compton effect C. diffraction experiment D. Stark effect

3. de 'Broglie equation is obtained by combination of which of the following theories?


A. Planck's quantum theory B. Einstein's theory of mass-energy equivalence
C. Theory of interference D. Theory of diffraction'

4. Which among the following is not used to calculate the de Broglie wavelength?

SECTION –E

33)
i. Give the criteria for spontaneity of a process in terms of free energy change (∆G).

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ii. Exothermic reactions associated with a decrease in entropy are spontaneous at lower temperatures.
Justify on the basis of Gibbs equation.
iii. For the reaction 2 A(g) + B(g) → 2D(g) ∆U0 = –10.5 kJ and ∆S0 = –44.1 JK–1 . Calculate ∆G0 for the
reaction, and predict whether the reaction may occur spontaneously.
OR
a. For a reaction both ΔH and ΔS are negative. Under what conditions does the reaction occur
spontaneously?
b. Define- Lattice enthalpy
c.

34. i. Explain the terms Inductive and Electromeric effects. Which electron displacement effect explains the
following correct orders of acidity of the carboxylic acids? Cl3CCOOH > Cl2CHCOOH > ClCH2COOH
ii. Explain why alkyl groups act as electron donors when attached to a π system.
iii. Give condensed and bond line structural formula of 2-Hydroxy-1,2,3-propanetricarboxylic acid

35) Explain the following with suitable examples:


i. Decarboxylation ii. Aromatization iii. Kharash effect
iv. Sulphonation v. Friedel-Craft’s Acylation reaction

OR

What happens when?


a.The vapours of Phenol are passed over heated zinc dust.
b. Ethyne (acetylene) on passing through red hot iron tube at 873K.
c. n-Alkanes on heating in the presence of anhydrous aluminium chloride and hydrogen chloride gas
d. Benzene on treatment with excess of chlorine in the presence of anhydrous AlCl3 in dark
e. Propene is treated with HBr
KENDRIYA VIDYALAYA SANGATHAN CHENNAI REGION
SAMPLE PAPER 5 2022-23
XI CHEMISTRY-ANSWER KEY
SECTION A

Q.No Answer Marks

1 B-27.27% 1

2 A-Molarity 1
3 D-The position and velocity of the electrons in the orbitcannot be determined 1
simultaneously.
4 A-Frequency of incident light 1

5 B-BCl3 has no lone pair of electrons whereas NCl3 has a lone pair of electrons 1
6 D- Terbium (Z=65) 1

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7 A-Precipitation will occur 1

8 D- H+ion concentration does not change 1


9 B- HCIO3 1
10 A-Position isomers 1

11 C- q=0 1
12 A-Steam distillation 1

13 A-C6H6+CH3Cl 1
14 C-X= o and p-chlorotoluene, Y= trichloromethyl benzene 1
15 A-If both (A) and (R) are correct and (R) is the correct reason for (A). 1

16 C- If (A) is correct but (R) is incorrect. 1


17 D-A is not correct but R is correct. 1
18 A-Both A and R are correct and R is the correct explanation of A. 1
SECTION B
19 Energy (En) of ‘n’ photons = nhν 1/5
n= =
λ = wavelength of light = 4000 pm = 4000 ×10–12 m
c = velocity of light in vacuum = 3 × 108 m/s
h = Planck’s constant = 6.626 × 10–34Js
Substituting the values in the given expression of n:
n= = 1 J X 4000 ×10–12 m
6.626 × 10–34Js X 3 × 108 m/s 1/5
n =2.012 × 1016
20 i. Molarity:it can be defined as the number of moles of his solute present in 1
one litre of solution .
ii. Limitng reagent:The limiting reagent in a chemical reaction is a reactant 1
that is totally consumed when the chemical reaction is completed. The
amount of product formed is limited by this reagent, since the reaction cannot
continue without it.
21 i) Size of atom or ion (ii) Nuclear charge 1

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iii) Electronic configuration (iv) Screening effect 1

22 bond order: the number of bonds between two atoms in a molecule of an 1


element or compound.
Determining the electronic configuration of O2 1/5
[σ(1s)]2[σ∗(1s)]2[σ(2s)]2[σ∗(2s)]2[σ(2pz)]2[π(2px)]2[π(2py)]2[π∗(2px)]1[π∗(2p
y)]1
The number of bonding electrons = 10
The number of anti-bonding electrons = 6
Step 3: Calculating the bond order of O2 1/5
Bond order =
Bond order =
Bond order = 2
Hence, the bond order for O2 is 2.
OR

SiCl4

AsF5 triagonal bipyramidal

ClF3

NH3

23 a) Entropy is a measure of the randomness or disorder of a system. 1,


b) N2O3(g)N2O(g) +O2(g) -positive 1/5,
c) NH3(g) +HCl(g) NH4Cl(s)--negative 1/5
24 1
Conjugate acid base pairs differ by a proton.For example, HCl,Cl− represents
conjugate acid base pair.

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NH4+ is a conjugate acid of NH3 and NH2- is a conjugate base of acid NH3 1
25 Ozonolysis: Alkenes add ozone to form an ozonide which on hydrolysis in presence of 1
Zn to form carbonyl compounds (Aldehydes or ketones).

OR

OR

i.CH3CH2Br+2Na+Br CH2CH3 CH3CH2 CH2CH3 +2NaBr 1


n-butane
ii.CH3CH2I CH2 = CH2 +HI 1
Ethene

SECTION C
26 elements symbol % of At.mass No.of Simplest Simplest
element of moles molar whole
elemets = ratio no.ratio

Sodium Na 29.11 23 2 1

Sulphur S 40.51 32 2 1

oxygen O 30.38 16 3 1

Empirical formula of the salt= Na2S2O3


27 i. Halogens have very high negative electron gain enthalpies because 1
they can attain stable noble gas electronic configurations by picking up an 1
electron.
ii. Mg2+ ion is smaller than O2-ion although both have the same 1
electronic configuration because of higher nuclear charge.
iii. Electron gain enthalpy of fluorine is less negative than that of
chlorine. This is because when an electron is added to F, the added electron
goes to the smaller n = 2 quantum level and suffers significant repulsion from
the other electrons present in this level.

28 i. The pH of a solution is defined as the negative logarithm to base 10 of the 1


concentration of hydrogen ion [H+].
pH = -log[H+].

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pH = – log [H+] or log [H+] = – pH = – 3.76 = 4.24


[H+] = Antilog 4.24 = 1.738 x 10-4 = 1.74 x 10-4 M 1
ii.

1
OR
OR
a. Le Chatelier's principle states that if a dynamic equilibrium is disturbed by
changing the conditions, the position of equilibrium shifts to counteract the 1
change to reestablish an equilibrium.
b. (i) Equilibrium will be shifted in the forward direction. 2
(ii) Equilibrium will be shifted in the backward direction.
(iii) Equilibrium will be shifted in the backward direction.
(iv) Equilibrium will be shifted in the forward direction.
29 Oxidation half equation:
SO2(g) + 2H2O(l) ————> SO42-(aq) + 4H (aq) + 2 e – …(i)
+
1
Reduction half equation: 1
Cr2O72–(aq) + 14H+(aq) + 6e– ————> 2Cr3+(aq) + 7H 20(l) …(ii)
Multiply Eq. (i) by 3 and add it to Eq. (ii), we have, 1
Cr2O72–(aq) + 3SO2(q) + 2H+(aq) ————> 2Cr3+(aq) + 3SO 42-(aq) + H 20(l)

30 Mass of the compound = 0.468 g


Mass of barium sulphate= 0.668 g
1

2
Or
Mass of the compound = 0.3780 g OR
Mass of silver chloride = 0.5740 g
1

SECTION D
31 1. (a) BeCl2 is least ionic out' of the given chlorides 1
2. (D) AlI3 1
3. (B) AlCl3 1
4. (B) LiCI 1
32 1. (D) angular momentum 1
2. (C) diffraction experiment 1
3. (A) Planck's quantum theory 1
(B) Einstein's theory of mass-energy equivalence 1

4. (A) λ=
SECTION E
33 i. For a reaction to be spontaneous ΔG should be negative. 1
ii. if both ΔH and ΔS are negative, ΔG can be negative only if TΔS < ΔH in
1
magnitude.
ΔG = ΔH – TΔS, ΔG = (−) − T(−)

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This is possible only if either ΔH has a large negative value or T is so low


that TΔS < ΔH.
iii.

OR
a. Both ΔH and ΔS are positive so ΔG will be negative only if TΔS > ΔH in
magnitude. 1

ΔG = ΔH−TΔS
1
ΔG = (+) − T(+)
OR
Thus either ΔS should be very large so that even if T is low, TΔS is greater
than ΔH, or if ΔS is small, T should be high so that TΔS > ΔH. 1
b. Lattice energy can be defined as the energy required to convert one mole
of an ionic solid into gaseous ionic constituents.
c.
1

34 i. Inductive effect is a partial shifting/displacement of σ electrons 1


towards a more electronegative atom of σ bond.
ii. The spontaneous formation of a dipole molecule of the organic compound
because of the complete transfer of shared pi electrons pairs to other atoms
in the influence of attacking reagent present is referred to as Electromeric 1
effect.
iii. Electron withdrawing inductive (-I) effect 1
iv. When an alkyl group is attached to a π system, it acts as an

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electron-donor group by the process of hyperconjugation. 1

v. heptan-4-one

35 a) Decarboxylation:
Sodium salt of carboxylic acids (R-COONa) on heating with soda lime (a mixture of
NaOH and CaO), we get an alkane containing one carbon atom less than that of the 1
carboxylic acid.
e.g. CH3COONa CH4 + Na2CO3
Sodium acetate methane
b) Aromatization:
n-Alkanes having six or more carbon atoms on heating to 773K at 10-20
atmospheric pressure in the presence of oxides of vanadium, molybdenum or
chromium supported over alumina, we get aromatic compounds.

c) Kharash effect:
In the presence of peroxide, addition of HBr to unsymmetrical alkenes takes
place against Markovnikov rule. This is known as peroxide or Kharash effect or anti-
Markovnikov addition reaction.
1
e.g. CH3-CH= CH2 + HBr CH3-CH2-CH2
d) Sulphonation: It is the introduction of sulphonic acid (-SO3H) group to a
benzene ring. It is carried out by heating benzene with fuming sulphuric
acid (H2S2O7 or oleum).

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(e) Friedel-Craft’s Acylation reaction: The reaction of benzene with an acyl halide or
acid anhydride in the presence of Lewis acids (AlCl3) yields acylbenzene.

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OR

(a) Phenol is reduced to benzene by passing its vapours over heated zinc dust.

OR

(b) Ethyne (acetylene) on passing through red hot iron tube at 873K,
undergoescyclic polymerisation to form benzene (C6H6).
1

(c) n-Alkanes on heating in the presence of anhydrous aluminium chloride and


hydrogen chloride gas isomerise to branched chain alkanes.

(d) Benzene on treatment with excess of chlorine in the presence of


anhydrous AlCl3 in dark 1

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(e) Propene is treated with HBr

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