Arihant CBSE Chemistry Term 2 Class 11

CBSE Term II
2022
Chemistry
Class
XI
CBSE Term II
2022
Chemistry
Class
XI
Complete Theory Covering NCERT
Case Based Questions
Short/Long Answer Type Questions
3 Practice Papers with Explanations
Authors
Aditya Jangid
Arshdeep Kaur
ARIHANT PRAKASHAN (School Division Series)

CBSE Term II
2022
ARIHANT PRAKASHAN (School Division Series)
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CBSE Term II
2022
Contents
CHAPTER
States of Matter: Gases and Liquids -
CHAPTER
Chemical Thermodynamics -
CHAPTER
Equilibrium -
CHAPTER
s -Block Elements -
CHAPTER
Some p -Block Elements -
CHAPTER
Hydrocarbons -
Practice Papers - -
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CBSE Term II
2022
Syllabus
CBSE Term II Class XI
Time: hrs Max Marks:

S.No Units Periods Marks
. States of Matter: Gases and Liquids
. Chemical Thermodynamics
. Equilibrium
. s-Block Elements
. Some p-Block Elements
. Hydrocarbons
States of Matter: Gases and Liquids

Three states of matter, intermolecular interactions, types of bonding, melting and boiling points,
role of gas laws in elucidating the concept of the molecule, Boyle s law, Charles law, Gay Lussac s
law, Avogadro s law, ideal behaviour, empirical derivation of gas equation, Avogadro s number,
ideal gas equation and deviation from ideal behaviour.
Chemical Thermodynamics
Concepts of System and types of systems, surroundings, work, heat, energy, extensive and
intensive properties, state functions. First law of thermodynamics -internal energy and enthalpy,
measurement of U and H, Hess s law of constant heat summation, enthalpy of bond dissociation,
combustion, formation, atomization, sublimation, phase transition, ionization, solution and
dilution. Second law of Thermodynamics brief introduction
Introduction of entropy as a state function, Gibb s energy change for spontaneous and non-
spontaneous processes. Third law of thermodynamics brief introduction .
Equilibrium
Equilibrium in physical and chemical processes, dynamic nature of equilibrium, law of mass
action, equilibrium constant, factors affecting equilibrium - Le Chatelier s principle, ionic
equilibrium- ionization of acids and bases, strong and weak electrolytes, degree of ionization,
ionization of poly basic acids, acid strength, concept of pH, buffer solution, solubility product,
common ion effect with illustrative examples .
CBSE Term II
2022
s -Block Elements
Group and Group Elements -General introduction, electronic configuration, occurrence,
anomalous properties of the first element of each group, diagonal relationship, trends in the
variation of properties such as ionization enthalpy, atomic and ionic radii , trends in chemical
reactivity with oxygen, water, hydrogen and halogens, uses.
Some p-Block Elements

General Introduction to p-Block Elements
Group Elements: General introduction, electronic configuration, occurrence, variation of
properties, oxidation states, trends in chemical reactivity, anomalous properties of first element
of the group, Boron - physical and chemical properties.
Group Elements: General introduction, electronic configuration, occurrence, variation of
properties, oxidation states, trends in chemical reactivity, anomalous behaviour of first elements.
Carbon-catenation, allotropic forms, physical and chemical properties.
Hydrocarbons
Classification of Hydrocarbons Aliphatic Hydrocarbons:
Alkanes - Nomenclature, isomerism, conformation ethane only , physical properties,
chemical reactions.
Alkenes - Nomenclature, structure of double bond ethene , geometrical isomerism, physical
properties, methods of preparation, chemical reactions: addition of hydrogen, halogen, water,
hydrogen halides Markovnikov s addition and peroxide effect , ozonolysis, oxidation,
mechanism of electrophilic addition.
Alkynes - Nomenclature, structure of triple bond ethyne , physical properties, methods of
preparation, chemical reactions: acidic character of alkynes, addition reaction of - hydrogen,
halogens, hydrogen halides and water.
Aromatic Hydrocarbons: Introduction, IUPAC nomenclature, benzene: resonance, aromaticity,
chemical properties: mechanism of electrophilic substitution. Nitration, sulphonation,
halogenation, Friedel Craft s alkylation and acylation, directive influence of functional group in
monosubstituted benzene. Carcinogenicity and toxicity.
CBSE Circular
Acad - 51/2021, 05 July 2021
Exam Scheme Term I & II
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CHAPTER 01
States of Matter :
Gases and Liquids
In this Chapter...
l Factors Governing States of Matter
l The Gaseous State
l Ideal Gas and Ideal Gas Equation
l Dalton's Law of Partial Pressure
l Deviation from Ideal Gas Behaviour
There are three states of matter which are in three different the weak forces and generally affect the physical properties
physical forms. These three forms of matter are solid, liquid and some chemical properties of matter.
and gas. Attractive intermolecular forces are known as van der
l
Solid state A matter in solid state possesses a definite size Waals’ forces. van der Waals’ forces vary considerably
(volume), a definite shape and a definite mass. Some common in magnitude. They include dispersion forces or London
examples of solid are iron, silver, common salt etc. forces, dipole-dipole forces and dipole-induced dipole
l
Liquid state A matter in liquid state possesses a definite forces.
volume, a definite mass but not a definite shape. It acquires the
shape of the container in which it is placed. It has a tendency to 1. Dispersion or London Forces
flow. Some common examples are water, oil, milk etc. l
These forces exist in between neutral atoms and
l
Gaseous state A matter in gaseous state neither possesses a non-polar molecules, as in them electronic cloud is
definite volume nor definite shape but it has a definite mass. distributed symmetrically and hence have no dipole
It acquires the shape and volume of the container. Some moment.
common examples are air, oxygen, carbon dioxide etc. l
The interaction energy of these forces is proportional to
1 / r 6 . (where, r is the distance between two particles)
Factors Governing States of Matter
State of a matter is the result of combined effect of 2. Dipole-Dipole Forces
intermolecular forces and thermal energy, thus to understand l
These forces exists between dipole ends of polar
their role in deciding the state of matter, it is necessary to molecules and are the strongest of all van der Waals’
understand the following terms. forces.
l
Dipole-dipole interaction energy between stationary
Intermolecular Forces polar molecules is proportional to 1 / r 3 and that between
Intermolecular forces are the forces of attraction and repulsion rotating polar molecules is proportional to 1 / r 6 where, r
between interacting particles (atoms and molecules). These are is distance between polar molecules.
02 CBSE Term II Chemistry XI
l
This interaction is stronger than London forces but Band Model
weaker than ion-ion interactions. According to this theory, a metal lattice has an extremely large
3. Dipole Induced Dipole Forces number of atoms. The atomic orbitals of these atoms overlap
together due to similar symmetry and similar energy resulting
l
These forces exist between the polar molecules having
to the formation of energy bands.
permanent dipole and the molecules lacking permanent
dipole. The arrangement of electrons in the different energy bands
l
Permanent dipole of the polar molecule induces dipole on determines the characteristic of a metal.
the electrically neutral molecule by deforming its electron Conduction band
cloud.
Empty Empty
band band
Types of Bonding
Forbidden zone Small
There are two types of bonding, i.e. hydrogen bonding and energy gap
(Large energy gap)
metallic bonding.
1. Hydrogen Bond Filled
Energy
band
It is a special case of dipole-dipole interaction. A hydrogen
bond is formed (or such force exist) when a hydrogen is bonded Partially Overlapping
to a more electronegative atom (like, N, O and F). filled bands
band Metal Insulator Semiconductor
d+ d- d+ d-
H ¾F H ¾F (In each case, an unshaded area represents a conduction band)
Distinction among metals, insulators and semiconductors.
H-bond
Energy of hydrogen bond varies between 10 to 100 kJ mol -1 , The highest occupied energy band is called the valence band
i.e. these are strong forces and play a key role in while the lowest unoccupied energy band is called the
determining the structure and properties of many conduction band.
compounds like proteins, nucleic acid etc. The properties of various elemental solids can be explained by
the gap present between the top of valence band and the
2. Metallic Bonding bottom of conduction band, called energy gap (E g ).
The peculiar type of bonding which holds the metal atoms
together in a metal crystal is called metallic bonding. Thermal Energy
Different models have been proposed to explain the nature of l
The energy of a body which arises because of the motion of its
metallic bonding, the two important of them are as follows atoms or molecules, is called the thermal energy.
Electron Sea Model
l
It is infact, the measure of average kinetic energy of the
particles of the matter and hence is responsible for their
According to this model, a metal is regarded as a group of
motion. This movement of particles is called thermal motion.
positive metal ions packed together as closely as possible in
a regular geometric pattern and immersed in a sea of Intermolecular Forces vs Thermal Interactions
electron which move about freely in the vacant valence
The intermolecular forces tend to keep the molecules together
orbitals.
but thermal energy tend to keep them apart.
The attractive force that binds the metal ions to the mobile
Thus, these two compete and the competition between these
electrons is called metallic bond. The positive metal ions, two (i.e. intermolecular forces and thermal energy) results in
are called positive cores or kernels and mobile electrons are three states of matter.
electron pool or electron gas.
+ e
_
+ e
_
+ e
_
+ The Gaseous State
Gases have neither definite shape nor definite volume. They are
_ _ _ _
e + e + e + e characterised by their high diffusibility, large intermolecular
space, high kinetic energy, high compressibility and low density.
_ _ _ Delocalised
+ e + e + e + electrons
Gas Laws
_ _ _ _
e + e + e + e Gas laws are the relationships between measurable properties
Metallic ion
Electron sea model of gases. Let’s discuss the various gas laws.
CBSE Term II Chemistry XI 03
1. Boyle’s Law (Pressure-Volume Relationship) At constant p and T; V µ n (Avogadro’s law)

It states that ‘‘at constant temperature, the pressure of a given mass On combining the above three elations, we get
of a gas is inversely proportional to its volume.’’ nT
Vµ
1 p
i.e. pµ (At constant T)
V nT
or V=R …(i)
or pV = constant p
or p1 V1 = p 2 V2 = constant (Here, R = proportionality constant or gas constant)
2. Charles’ Law (Temperature-Volume Relationship) On rearranging the equation (i), we get
According to this law, “the volume of a given mass of a gas is pV = nRT [ where, n = w / M ]
directly proportional to the absolute temperature at constant The values of R, are
pressure”. R = 8. 314 Pa m 3K - 1 mol - 1
i.e. VµT (at constant pressure) = 8. 314 J K - 1 mol - 1
V
or = constant = 8.20578 ´ 10 - 2 L atm K - 1 mol - 1
T l
Ideal gas equation is a relation between four variables
V1 V2 and it describes the state of any gas, therefore it is also
or =
T1 T2 called equation of state.
The combined gas law is given by,
3. Gay-Lussac’s Law (Pressure-Temperature Relationship) p1 V1 p 2 V2
=
According to this law, “at constant volume, the pressure of a T1 T2
given mass of a gas is directly proportional to its absolute Density and molar mass of a gaseous substance are
temperature”. related as,
i.e. p µT M = dRT / p
p
or = constant (at constant V)
T Dalton’s Law of Partial Pressure
p1 p 2 It states that “the total pressure exerted by the mixture of
or =
T1 T2 non-reactive gases is equal to the sum of the partial
pressure of each gas present in the mixture under the same
4. Avogadro’s Law (Volume-Amount Relationship) conditions of T and V.”
l
It states that, ‘‘equal volumes of all gases under same p total = p1 + p 2 + p 3 . . . . . . . . . . . (At constant T and V)
conditions of temperature and pressure contain equal number In terms of mole fraction,
of molecules.” partial pressure, ( p ) = mole fraction c ´ p total
i.e. Vµn (n = number of moles of gas)
l
The volume of one mole of a gas at STP is known as molar gas Deviation from Ideal Gas Behaviour
volume. Real Gases
l
The number of molecules in one mole of a gas has been Gases that do not obey gas laws under all conditions of
determined as 6.022 ´ 10 23 , is known as Avogadro constant. temperatures and pressures are called real gases.
Most of the gases are real in nature, i.e. they follow gas laws
Ideal Gas and Ideal Gas Equation only at very low pressures and high temperatures.
l
A gas that follows Boyle’s law, Charles’ law and Avogadro’s Under such conditions the gas molecules are far apart, i.e.
law strictly is called an ideal gas. not in the influence of each other and hence, intermolecular
forces of attraction are negligible.
l
The combination of various gas laws such as Boyle’s law,
Charles’ law and Avogadro’s law leads to the ideal gas (i) pV vs p Plot
equation. l
Plots are not straight.
At constant T and n; V µ1 / p (Boyle’s law) l
Gases show deviation from ideal behaviour.
At constant p and n; V µ T (Charles’ law)
CO 2. Volume Correction
CH4
H2 Volume available for compression
He = total volume of the gas - volume of the molecules
Ideal gas Vcorrected = V - nb
pV
where, b is the volume occupied by one mole of the molecules

and n is the number of moles of the molecules (or gas).
0 p 3. van der Waals’ Equation

Plot of pV vs p for real gas
Putting the values of corrected pressure and volume in ideal
and ideal gas gas equation, we get
(ii) Pressure vs Volume Plot
æ an 2 ö
Real gases deviate from ideal gases. ç p + 2 ÷ ( V - nb ) = nRT
è V ø
Real gas
Ideal gas where, a and b = van der Waals’ constants, value of which
depend upon the nature of the gas. This equation is known as
van der Waals’ equation.
Pressure
Measurement of Deviation :
Compressibility Factor
0 Volume l
The extent of deviation shown by real gases from ideal
Plot of pressure vs volume for behaviour is measured in terms of compressibility factor
real and ideal gases ( Z).
l
Z is defined as the ratio of product of pV and nRT.
Causes of Deviations from Ideal Behaviour Mathematically,
pV
Two assumptions on which ideal gases are based are not valid Z=
at high pressure or low temperature. nRT
l
For ideal gas, Z = 1 at all temperatures and pressures.
l
The intermolecular forces of attraction between the
At very low pressure, all gases have Z » 1 and behave as
particles of a gas at ordinary temperature and pressure are
ideal gas. At high pressure, all gases have Z > 1.
negligible.
At intermediate pressure, most gases have Z < 1.
l
Volume of the molecules of a gas is negligibly small in
comparison to the space occupied by the gas.
l
Gases show ideal behaviour when the volume occupied is
large, because then the volume of the molecules can be
The correct assumption at the conditions of high pressure
neglected as comparison to volume of gas.
and low temperature are
l
The forces of attraction or repulsion between the 1.8
N2
molecules may not be negligible. 1.6 H2
1.4 O2
l
The volume occupied by the gas may be so small that the CH4
volume occupied by the molecules may not be negligible. 1.2 CO2
Z = pV/nRT
1.0
Ideal gas
Corrections of Deviations 0.8
1. Pressure Correction 0.6
p ideal = p real + Dp 0.4
Dp µ (Number of particles per unit volume) 2

0 200 400 600 800 1000
or Dp µ ( n / V) 2 where, n is the number of mole of the gas, p/bar
V is the volume of gas. Variation of compressibility factor for some gases .
n2 l
The temperature at which the real gases behave ideally
Dp = a 2 (where, a = constant) over a wide range of pressure is called Boyle temperature
V
p ideal = p red observed pressure + an 2 / V 2 or Boyle point, Tb . It depends upon the nature of the gas
1424 3 and is specific for a particular gas.
Correction term
Solved
Examples
Example 1. What will be the minimum pressure required Now, as p and V are constant, so
to compress 2 L of gas at 1 bar to 1 L at 25°C? 3
n × T1 = n T2 ...(i)
Sol. p1 = 1 bar, p 2 = ?, V1 = 2 L, V2 = 1 L 5
Putting the value of T1 in Eq. (i), we get
From Boyle’s law, p1V1 = p 2 V2 3
1 ´ 2 = p2 ´ 1 n ´ 300 = n ´ T2
5
p 2 = 2 bar 5
or T2 = 300 ´ = 500 K
Example 2. A balloon is filled with hydrogen at room 3
temperature. It will burst, if pressure exceeds 0.2 bar. If at 1 Example 5. A bubble of volume V1 is present in the bottom
bar pressure the gas occupied 2.27 L volume, up to what of a pond at 15°C and 1.5 atm pressure. When it comes at
volume can the balloon be expanded? the surface, it observes a pressure of 1 atm at 25°C and has
Sol. According to Boyle’s law, volume V2 . What is the value of V2 / V1 ?
p1 V1 = p 2 V2 Sol. Given, p1 = 1.5 atm, T1 = 15° C = (15 + 273) K = 288 K
Given, p1 = 1 bar, V1 = 2.27 L, p 2 = 1 atm, T2 = 25° C = (25 + 273) = 298 K
p 2 = 0.2 bar, V2 = ? According to combined gas law,
p V 1 bar ´ 2.27 L p1V1 p 2 V2 p1T2 V2
V2 = 1 1 = = 11.35 L = Þ =
p2 0.2 bar T1 T2 T1p 2 V1
Example 3. On a ship sailing in pacific ocean where V2 1. 5 ´ 298
Þ = = 1. 55
temperature is 23.4°C, a balloon is filled with 2 L air. What V1 288 ´ 1
will be the volume of the balloon when the ship reaches Example 6. A neon dioxygen mixture contains 70.6 g of O 2
Indian ocean, where temperature is 26.1°C ? and 167.5 g neon. If pressure of the mixture of gases in the
Sol. Given, V1 = 2 L, cylinder is 25 bar, what are the partial pressures of O 2 and
T1 = (23.4 + 273) K = 296.4 K Ne in the mixture, respectively?
T2 = (26.1 + 273) K = 299.1 K, V2 = ? Sol. We know that,
From Charles’ law, w
No. of moles (n ) =
V1 V2 VT M
= Þ V2 = 1 2
T1 T2 T1 For O 2 , w = 70. 6 g, M = 32 g mol -1
70. 6 g
2 L ´ 299.1 K No. of moles of O 2 ( n 1 ) = = 2.21mol
Þ V2 = = 2L ´ 1.009 32 g mol -1
296.4 K
For Ne, w = 167.5 g , M = 20 g mol -1
= 2.018 L
167.5 g
No. of moles of Ne ( n 2 ) = = 8.375 mol
Example 4. An open vessel at 27ºC is heated until two fifth 20 g mol -1
of the air (assumed as an ideal gas) in it has escaped from n1
the vessel. Assuming that the volume of the vessel remains Mole fraction of O 2 ( c 1) =
n1 + n 2
constant. What is the temperature at which the vessel has
2.21
been heated ? = = 0.21
2.21 + 8.375
Sol. Given, temperature ( T1 ) = 27 °C = 273 + 27 = 300 K
Mole fraction of Ne (c 2 ) = 1 - c 1
Volume of vessel = constant
Pressure in vessel = constant = 1 - 0.21 [Q c 2 = 1 - c 1]
Volume of air reduced by 2/5 so the remaining volume of air c 2 = 0.79
is 3/5. Partial pressure of a gas = mole fraction ´ total pressure
Let at T1 the volume of air inside the vessel is n so at T2 the Partial pressure of O2 = 0.21 ´ 25 = 5.25 bar
3
volume of air will be n. Partial pressure of Ne = 0.79 ´ 25 = 19.75 bar
5
Exampler 7. 40 L of a gas is stored under a pressure of 150 atm Sol. van der Waals’ equation of state is given below,
at 300 K. How many moles of the gas are present in the cylinder? æ n 2a ö
Sol. According to ideal gas law, pV = nRT ç p + 2 ÷ ( V - nb ) = nRT
è V ø
Given, p = 150 atm, V = 40 L, T = 300 K, n = ? For one mole, n = 1 and b = 0, the above equation
pV 150 ´ 40 becomes
n= = = 243.9 » 244 mol
RT 0.082 ´ 300
æ a ö
ç p + 2 ÷ V = RT
Example 8. For one mole of a van der Waals’ gas when b = 0 è V ø
and T = 300K, the pV vs 1/V plot is shown below. What is the a
Þ pV = RT - …(i)
value of the van der Waals’ constant a (atm L mol -2 ) ? V
1
24.6 Eq. (i) is a straight line equation between pV and
V
pV(L atm mol−1 )
23.1 whose slope is -‘a ’.

21.6 Equate the value of ‘a’ with slope of the straight line
20.1 given in the graph as shown below.
20.1 - 21. 6
-a= = - 1. 5
3-2
0 2.0 3.0 Þ a = 1. 5
1/ V (mol L−1 )
Chapter
Practice
Select the correct statement.
PART 1 (a) I and II (b) II and III
Objective Questions (c) III and IV (d) I and IV

6. Graph of pressure versus volume is given below.
l Multiple Choice Questions A
B
1. Consider the following orders.
Pressure
I. Gas > Liquid > Solid [Thermal energy]
II. Gas > Liquid > Solid [Intermolecular energy]
III. Solid > Liquid > Gas [Intermolecular energy] O Volume
IV. Solid > Liquid > Gas [Thermal energy] The plot that represents an ideal gas behaviour is
Choose the correct order and select the correct (a) A (b) B
statement. (c) A and B (d) Neither A nor B
(a) I and III (b) I and II
7. The pressure in well inflated tyres of automobiles
(c) II and IV (d) III and IV
is almost constant, but on a hot summer day this
2. The interaction energy of London forces is increases considerably and the tyre may burst.
inversely proportional to sixth power of the This phenomena is explained by
distance between two interacting particles but their (a) Boyle’s law (b) Charles’ law
magnitude depends upon (NCERT Exemplar) (c) Gay-Lussac’s law (d) Avogadro’s law
(a) charge of interacting particles 8. Dalton’s law of partial pressure is not applicable to
(b) mass of interacting particles a mixture of
(c) polarisability of interacting particles (a) He and N2 (b) Ar and He
(d) strength of permanent dipoles in the particles (c) N2 and O2 (d) HCl and NH3
3. Boyle’s law is valid, when a graph plotted against 9. Two gases A and B having molar mass 60 and
1 45 g mol -1 , respectively are enclosed in a vessel.
p versus is
V The weight of A is 0.5 g and that of B is 0.2 g.
(a) straight line passing through origin The total pressure of the mixture is 750 mm.
(b) straight line passing through some intercept The partial pressure of gas A and B respectively are
(c) parabola passing through x-axis (a) 260 mm, 490 mm (b) 190 mm, 560 mm
(d) curved line passing through origin (c) 490 mm, 260 mm (d) 520 mm, 290 mm
4. All gases obey Charles’ law at 10. A closed vessel contains equal number of nitrogen
(a) low temperature and high pressure and oxygen molecules at a pressure of p mm.
(b) low temperature and low pressure If nitrogen is removed from the system then the
(c) high temperature and high pressure pressure will be
(d) high temperature and low pressure (a) p (b) 2 p (c) p 2 (d) p/2
5. Avogadro’s law is the combination of 11. The value of universal gas constant (R ) depends on
I. Charles’ law. (a) the pressure of the gas
II. Boyle’s law. (b) the temperature of the gas
(c) the unit of measurement of pressure, temperature and
III. Dalton’s atomic theory. volume
IV. Gay-Lussac’s law of combining volume. (d) the volume of the gas
12. There is 15 L of a gas at STP. At what other 19. Assertion Ideal gas equation is given by the
condition, volume of gas remains the same ? expression :
(a) 546°C and 0.5 atm pV = nRT
(b) 273°C and 2 atm
Reason Ideal gas equation is derived by three laws
(c) 273 K and 2 atm
namely: Charles’, Boyle’s and Gay-Lussac’s law.
(d) 0°C and 0 atm
13. A correct relationship between density and 20. Assertion Exclude volume or co-volume equals to
pressure of a gas is (V - nb) for n moles.
(a) d = K ¢× p at constant volume Reason Co-volume depends on the effective size of
(b) d = K ¢× p at constant temperature gas molecules.
1
(c) d = K ¢× at constant temperature l Case Based MCQs
p
(d) d =
1
× p at constant volume 21. Read the following and answer the questions from
K¢ (i) to (iv) given below
14. At which one of the following temperature pressure On combining Boyle’s, Charles’ and Avogadro’s law,
conditions, the deviation of a gas from ideal we get a single equation, which is called ideal gas
behaviour is expected to be minimum ? equation. This equation gives the simultaneous effect
(a) 350 K and 3 atm (b) 550 K and 1 atm of pressure and temperature on the volume of a gas.
(c) 250 K and 4 atm (d) 450 K and 2 atm We know that,
15. Dominance of strong repulsive forces among the At constant T and n; V µ 1 / p (Boyle’s law)
molecules of the gas At constant p and n; V µ T (Charles’ law)
(a) depends on Z and indicated by Z = 1 At constant p and T; V µ n (Avogadro’s law)
(b) depends on Z and indicated by Z > 1 On combining the above three,
(c) depends on Z and indicated by Z < 1 nT
(d) is independent of Z we get Vµ
p
l
Assertion-Reasoning MCQs nT
or V =R
Direction (Q. Nos. 16-20) For given questions two p
statements are given-one labelled Assertion (A) and the (Here, R = proportionality constant or gas constant)
other labelled Reason (R). Select the correct answer to On rearranging the Eq. (i), we get
these questions from the codes (a), (b), (c) and (d) as pV = nRT
given below.
This equation is called ideal gas equation and is
(a) Both A and R are true and R is the correct
explanation of A. applicable for all gases that behave ideally.
(b) Both A and R are true, but R is not the correct The ideal gas equation was derived on the basis of
explanation of A. certain assumptions of kinetic theory of gases. But
(c) A is true, but R is false. when studied carefully, it was found that two of these
(d) A is false, but R is true. assumptions are not true at high pressure or low
16. Assertion Three states of matter are the result of temperature.
balance between intermolecular forces and thermal These two assumptions are the intermolecular forces
energy of the molecules. of attraction between the particles of a gas at
Reason Intermolecular forces tend to keep the ordinary temperature and pressure are negligible
molecules together but thermal energy of molecules and volume of the molecules of a gas is
tends to keep them apart. negligibly small in comparison to the space occupied
by the gas.
17. Assertion London forces are applicable for short
distances (~500 pm). The correct assumption at the conditions of high
pressure and low temperature are
Reason The magnitude of London forces depends on
the polarisability of the particle.
l
the forces of attraction or repulsion between the
molecules may not be negligible.
18. Assertion NH 3 has higher boiling point than CCl 4 . l
the volume occupied by the gas may be so small that
Reason Dipole-dipole interaction are stronger than
the volume occupied by the molecules may not be
London-dispersion forces.
negligible.
(i) Boyle’s law is expressed as follows concept of an ideal gas as an approximation that
1 helps us model and predict the behaviour of real
p = K1 ×
V gases. The term ideal gas refers to a hypothetical gas
where, p = pressure, composed of molecules.
V = volume Ideal gas molecules do not attract or repel each
K 1 = proportionality constant other. The only interaction between ideal gas
molecules would be an elastic collision upon impact
Which of the following option is true about
with each other or an elastic collision with the walls
constant (K1 ) ? of the container.
(a) Value of K 1 does not depend upon temperature of the
gas Ideal gas molecules themselves take up no volume.
(b) Value of K 1 depends upon the amount of gas The gas takes up volume since the molecules expand
into a large region of space, but the ideal gas
(c) Value of K 1 is independent of the units of p and V
molecules are approximated as point particles that
(d) All of the above have no volume in and of themselves. If this sounds
(ii) Consider the following figure, which shows the too ideal to be true, you’re right. There are no gases
pressure vs temperature (in K) graph of a gas. that are exactly ideal, but there are plenty of gases
that are close enough that the concept of an ideal gas
V1
is an extremely useful approximation for many
Pressure (bar)
V2
situations.
V3
Infact, for temperatures near room temperature and
V4 pressures near atmospheric pressure, many of the
gases we care about are very nearly ideal. If the
pressure of the gas is too large (e.g. hundreds of
0 100 200 300 400
Temperature (K)
times larger than atmospheric pressure), or the
temperature is too low. There can be significant
The above graph explains deviations from the ideal gas law.
(a) Boyle’s law (b) Avogadro’s law An ideal gas is defined as one in which all collisions
(c) Charles’ law (d) Gay-Lussac’s law between atoms or molecules are perfectly elastic and
(iii) The volume occupied by 1.8 g of water vapour at in which there are no intermolecular attractive
374°C and 1 bar pressure will be forces. An ideal gas can be characterised by three
[Use, R = 0. 083 bar L K -1 mol -1 ] state variables: absolute pressure (p), volume (V) and
(a) 96.66 L (b) 55.87 L absolute temperature (T).
(c) 3.10 L (d) 5.3 L The relationship between them may be deduced
(iv) Which one of the following is not the correct from kinetic theory and is called the ideal gas law
value of gas constant (R )? pV = nRT = NkT
(a) 0.0821 L atm K -1 mol -1 l
n = number of moles
-1 -1
(b) 1.99 cal K mol l
R = universal gas constant = 8.3145 J/mol K
-1 -1
(c) 8.3 JK mol l
N = number of molecules
(d) 10.2 JK mol -1 -1 l
k = Boltzmann constant = 1.38066 ´ 10-23 J/K
Or = 8.617385 ´ 10- 5 eV/K
l
k = R /NA
What would be the SI unit for the quantity
pV 2 T 2 / n ?
l
N A = Avogadro’s number = 6.0221 ´ 10 23 /mol
(a) Nm 4 K 2 mol -1 (b) Nm 4 K mol (i) A person living in Shimla observed that cooking
(c) Nm 3 K 2 mol -1 (d) Nm 4 K -2 mol -1 food without using pressure cooker takes more
22. Read the following and answer the questions from (i) time. The reason for this observation is that at
to (iv) given below high altitude
(a) pressure increases
Gases are complicated. They are full of billions and
(b) temperature decreases
billions of energetic gas molecules that can collide
(c) pressure decreases
and possibly interact with each other. Since, it’s hard
(d) temperature increases
to exactly describe a real gas, people created the
(ii) Which of the following figures represent 1 mole 2. If 1 g of each of the following gases are taken at STP,
of dioxygen gas at STP? which of the gases will occupy (a) greatest volume and
(a) 16 g of gas (b) smallest volume?
(b) 22.7 L of gas CO, H 2O, CH 4 , NO (NCERT Exemplar)
(c) 6. 022 ´ 1023 dioxygen molecules
(d) 11.2 L of gas 3. At what temperature centigrade will the volume of a
gas at 0°C double itself, pressure remaining constant?
(iii) The gas constant R is a constant.
(a) Only for real gases 4. For an ideal gas, how does the plot of log p vs log V
(b) Only for ideal gases differ from that of log V vs log T? Explain.
(c) Both for real and ideal gases
(d) Neither real nor ideal gas
5. A mixture of dihydrogen and dioxygen at one bar
pressure contains 20% by weight of dihydrogen.
(iv) A correct relationship between density and Calculate the partial pressure of dihydrogen.
pressure of a gas is
(a) d = K ¢× p at constant volume 6. What will be the pressure exerted by a mixture of 3.2
(b) d = K ¢× p at constant temperature g of methane and 4.4 g of carbon dioxide contained
1 in a 9 dm 3 flask at 27°C?
(c) d = K ¢× at constant temperature
p 7. The variation of pressure with volume of the gas at
1 different temperatures can be graphically
(d) d = × p at constant volume
K¢ represented as shown in figure. On the basis of this
Or graph answer the following questions.
Which of the following expression represents (NCERT Exemplar)
correctly the variation of density of an ideal gas
with change in temperature?
p 2 T1d1 d1T1 Pressure (bar)
(a) d2 = (b) d2 = 600 K
p1T2 T2
400 K
d1T2 d1p 2 T2
(c) d2 = (d) d2 = 200 K
T1 p1T1 0
Volume (dm3)
(i) How will the volume of a gas change if its pressure

PART 2 is increased at constant temperature?
Subjective Questions (ii) At a constant pressure, how will the volume of a

gas change if the temperature is increased from
200 K to 400 K?
l
Short Answer Type Questions
8. Give reasons for the following
1. Use the information and data given below to answer (i) The size of weather balloon becomes larger and
the questions (a) to (c), Stronger intermolecular larger as it ascends into higher altitudes.
forces result in higher boiling point. (ii) Tyres of automobiles are inflated to lesser pressure
Strength of London forces increases with the number in summer than in winter.
of electrons in the molecule. 9. A student carries out an experiment to calculate the
Boiling point of HF, HCl, HBr and HI are 293 K, density of a gas at STP.
189 K, 206 K and 238 K respectively. He found that the density of a gas at 27°C and under 2
(i) Which type of intermolecular forces are present bar pressure is 5.46 g/dm 3 .
in the molecules HF, HCl, HBr and HI? Using the above given information, how can the student
(ii) Looking at the trend of boiling points of HCl, calculate the density at STP?
HBr and HI, explain out of dipole-dipole 10. A mixture of CO and CO 2 is found to have a density
interaction and London interaction, which one is of 1.50 g L-1 at 20°C and 740 mm pressure. Calculate
predominant here.
the composition of the mixture.
(iii) Why is boiling point of hydrogen fluoride highest
while that of hydrogen chloride lowest ?
11. A 2.0 L container at 25°C contain 1.25 moles of O 2
and 3.2 moles of C.
(i) What is the initial pressure in the flask? (i) Arrange the following gases in the increasing
(ii) If the carbon and oxygen react as completely as order of ‘ b ’. Give reason.
possible to form CO, what will be the final O 2 , CO 2 , H 2 , He
pressure in the container? (ii) Arrange the following gases in the decreasing
12. A 5 L vessel contains 1.4 g of nitrogen. When order of magnitude of ‘ a’. Give reason.
heated to 1800 K, 30% of molecules are dissociated CH 4 , O 2 , H 2 (NCERT Exemplar)
into atoms. Calculate the pressure of the gas at 19. The compression factor (compressibility factor) for
1800 K. one mole of a van der Waals’ gas at 0°C and 100 atm
13. The drain cleaner, contains small bits of aluminium pressure is found to be 0.5. Assuming that the
which react with caustic soda to produce volume of a gas molecule is negligible, calculate the
dihydrogen. What volume of dihydrogen at 20ºC van der Waals’ constant a.
and 1 bar will be released when 0.15 g of
20. Compressibility factor, Z of a gas is given as
aluminium reacts ? pV
Z=
14. Pressure versus volume graph for a real gas and an nRT
ideal gas are shown in figure. Answer the following (i) What is the value of Z for an ideal gas?
questions on the basis of this graph.
(ii) For real gas what will be the effect on value of
Z above Boyle’s temperature?
Real gas
Ideal gas l Long Answer Type Questions
21. (i) Pay load is defined as the difference between the
Pressure
mass of displaced air and the mass of the balloon.

Calculate the pay load when a balloon of radius
10 m, mass 100 kg is filled with helium at 1.66 bar
O Volume at 27ºC. (Density of air = 1.2 kg m -3 and
(i) Interpret the behaviour of real gas with respect R = 0.083 bar dm 3 K -1 mol -1 ). (NCERT)
to ideal gas at low pressure. (ii) A mixture in which the mole ratio of H 2 and O 2 is
(ii) Interpret the behaviour of real gas with respect 2 : 1 is used to prepare water by the reaction,
to ideal gas at high pressure. 2H 2 ( g) + O 2 ( g) ¾® 2H 2O ( g)
(iii) Mark the pressure and volume by drawing a line The total pressure in the container is 0.8 atm
at the point where real gas behaves as an ideal gas. at 20°C before the reaction. Calculate the final
15. 1 mole of sulphur dioxide occupies a volume of pressure at 120°C after reaction assuming 80%
350 mL at 27°C and 5 ´ 10 6 Pa pressure. Calculate yield of water.
the compressibility factor of the gas. 22. (i) A human adult breathes in approximately 0.50 L
Is it less or more compressible than an ideal gas? of air at 1 atm with each breath. If an air tank
16. Prove that the excluded volume ‘b’ is four times the holds 10 L of air at 200 atm, how many breaths the
actual volume of the gas molecules. tank will supply?
17. Two moles of a real gas confined in a 5 L flask (ii) A student forgot to add the reaction mixture to the
exerts a pressure 9.1 atm at a temperature of 27°C. round bottom flask at 27ºC but instead he/she
Calculate the value of ‘a’. Given the value of b is placed the flask on the flame. After a lapse of time,
0.052 L mol -1 . he realised his mistake and using a pyrometer he
found the temperature of the flask was 477ºC.
18. For real gases the relation between p, V and T is What fraction of air would have been expelled
given by van der Waals’ equation
out? (NCERT)
æ an 2 ö 23. Nitrogen molecule (N 2 ) has radius of about 0.2 nm.
ç p + 2 ÷ ( V - nb ) = nRT
è V ø Assuming that nitrogen molecule is spherical in
shape, calculate
where, ‘ a’ and ‘ b ’ are van der Waals’ constants, ‘ nb ’
is approximately equal to the total volume of the (i) volume of a single molecule of N 2 .
molecules of a gas. ‘ a’ is the measure of magnitude (ii) the percentage of empty space in one mole of N 2
of intermolecular attraction. gas at STP.
28. Based on the expression æç p +

24. A liquefied petroleum gas (LPG) cylinder weighs a ö
÷ ( V - nb ) = RT,
14.8 kg when empty. When full it weighs 29.0 kg è V2 ø
and shows a pressure of 2.5 atm. answer the following questions.
In the course of use at 27°C, the mass of the full (i) What is the compressibility factor for a real gas at
cylinder is reduced to 23.2 kg. Find out the volume high pressure?
of the gas in cubic metres used up at the normal (ii) If Z is a compressibility factor, how can van der
usage conditions and the final pressure inside the Waals’ equation at low pressure written as?
cylinder. Assume LPG to be n-butane with normal
(iii) Compare values for a and b for Cl 2 and C 2H 6 .
boiling point of 0°C.
25. (i) A gas is enclosed in room. The temperature, l Case Based Questions
pressure, density and number of moles 29. Read the following and answer the questions from
respectively are t°C, p atm, g cm -3 and n moles. (i) to (iv) given below
(a) What will be the pressure, temperature, Intermolecular forces are forces of attraction and
density and number of moles in each repulsion between interacting particles. They are
compartment, if room is partitioned into four weak forces and generally affect the physical and
equal compartments? chemical properties of matter. Attractive
(b) What will be the values of pressure, intermolecular forces are known as van der Waals’
temperature, density and number of moles in forces. They vary considerably in magnitude. They
each compartment if the walls between the include dispersion forces or London-forces,
two compartments (say 1 and 2) are removed? dipole-dipole and dipole induced dipole forces.
(c) What will be the values of pressure, London-forces exist between neutral atoms or
temperature, density and number of moles, if non-polar molecules. The dipole-dipole forces exists
an equal volume of gas at pressure (p) and between dipole ends of polar molecules and are the
temperature (t) is let inside the same room? strongest of all van der Waals’ forces.
(ii) 2.9 g of a gas at 95º C occupied the same volume Dipole induced dipole forces exist between polar
as 0.184 g of dihydrogen at 17º C, at the same molecules having permanent dipole and molecules
pressure. What is the molar mass of the gas? lacking permanent dipole H bonding is a special type
26. A large flask fitted with a stop-cock is evacuated of dipole-dipole interaction.
and weighed; its mass is found to be 134.567 g. It is (i) Why magnitude of interaction energy of London
then filled to a pressure of 735 mm at 31°C with a forces depends on polarisability of particles ?
gas of unknown molecular mass and then reweighed; its (ii) Why are dipole-dipole interaction considered
mass is 137.456 g. The flask is then filled with water and stronger than London-forces but weaker than
weighed again; its mass is now 1067.9 g. ion-ion interaction ?
Assuming that the gas is ideal, calculate the molar
(iii) Out of HF and H 2O, which has stronger
mass of the gas.
H-bonding interaction ?
27. Consider the following table.
(iv) Which type of intermolecular forces are present in
Gas a/(kPa dm 6mol -1) b/(dm 3mol -1) the molecules HF, HCl, HBr and HI ?
A 642.32 0.05196 Or Name the intermolecular forces between Cl 2 and
B 155.21 0.04136 CBr4 .
C 431.91 0.05196 30. Read the following and answer the questions from (i)
to (iv) given below
D 155.21 0.4382
Real gases show deviations from ideal gas law because
a and b are van der Waals’ constants. Which gas will molecules interact with each other. At high pressures
occupy the most volume out of A and C and which molecules of gases are very close to each other and
will be most compressible out of B and D ? molecular interactions start operating.
At high pressure, molecules do not strike the walls of This equation known as van der Waals’ equation. In
the container with full impact because these are this equation, n is number of moles of the gas.
dragged back by other molecules due to molecular Constants a and b are called van der Waals’
attractive forces. This affects the pressure constants and their value depends on the
exerted by the molecules on the walls of the characteristic of a gas.
container. Thus, the pressure exerted by the real gas (i) A gas that follows Boyle’s law, Charles’ law
is lower than the pressure exerted by the ideal gas.
and Avogadro’s law is called an ideal gas.
an 2
p ideal = p real + Under what conditions a real gas would behave
Observed V2 ideally? (NCERT Exemplar)
Correction
pressure term
(ii) What does negative deviation from ideal
Repulsive forces also become significant. Repulsive behaviour mean?
interactions are short-range interactions and are
(iii) Explain the physical significance of van der
significant when molecules are almost in contact. This
Waals’ parameters.
is the situation at high pressure. The repulsive forces
cause the molecules to behave as small but (iv) Two moles of a real gas confined in a 5 L flask
impenetrable spheres. exerts a pressure 9.1 atm at a temperature of
The volume occupied by the molecules also becomes 27°C. Calculate the value of ‘a’. Given the value
significant because instead of moving in volume V, of b is 0.052 L mol -1 .
these are now restricted to volume (V – nb), where, nb Or
is approximately the total volume occupied by the Calculate the temperature of 3 moles of SO 2 at
molecules themselves. Here, b is a constant. So, the 15 bar occupying a volume of 10 L by the van
corrected form of van der Waals’ equation is as follows der Waals’ equation. (a = 6.7 bar L2 mol -2 ,
æ an 2 ö b = 0. 0564 L mol -1 ).
ç p + 2 ÷ ( V – nb ) = nRT
è V ø
EXPLANATIONS
Objective Solutions 10. (d) In the vessel,
1. (a) Thermal energy is greatest in gaseous state followed by Number of molecules of N2 = Number of molecules of O2
liquid and then solid because intermolecular forces of i.e. number of moles of N2 = number of moles of O2
attraction are least in gases, the molecules agitates more. Mole fraction of N2 = Mole fraction of O2
2. (c) Large or more complex the molecules are greater is the p
magnitude of London forces. This is obviously due to the fact Partial pressure of N 2 = Partial pressure of O2 = mm
2
that the large electron clouds are easily distorted or When N2 is removed then only O2 molecules exert the
polarised. pressure.
3. (a) According to Boyle’s law, p
1 i.e. p total = p O 2 = mm
pµ (at constant temperature) 2
V 11. (c) R has a constant value with a unit of that depends upon
T3 p, T , V and no. of moles according to following relation
pV = nRT
T2
pV
p R=
T1 nT
T3 > T2 > T1 \R has different value depending on its units.
e.g. R = 0.08206 L atm/K mol
1/V = 8.314 J/K mol
Above figure represents the graph between p and 1 / V. = 1.9872 cal/K mol
It is a straight line passing through origin.
12. (b) V1 = 15 L, p1 = 1 atm, T1 = 273 K
4. (d) All gases obey Charles’ law at very low pressure and high
temperatures. V2 = 15 L, Let, p 2 = 2 atm and
5. (c) In 1811, Italian scientist Avogadro combined conclusions T2 = 273° C = (273 + 273) K = 546 K
of Dalton’s atomic theory and Gay-Lussac’s law of combining From gas law,
volumes which is now known as Avogadro’s law. p1V1 p 2 V2
=
6. (b) The pressure versus volume plot of experimental data T1 T2
(real gas) and theoretically calculated from Boyle’s law (ideal 1 ´ V1 2 ´ V2
gas) should coincide. At very high pressure, the measured Þ =
273 546
volume is more than the calculated volume.
Þ V1 = V2
At low pressures, measured and calculated volumes
So, at 273°C and 2 atm the volume of gas remains the same.
approach each other.
13. (b) A relationship can be obtained between density and
Therefore, graph ‘B’ shows ideal gas behaviour.
pressure of a gas by using Boyle’s law,
7. (c) Pressure in well inflated tyres of automobiles is 1 m
almost constant, but on a hot summer day, this increases p = K1 × (d = , where d = density)
considerably and the tyre may burst. This phenomena is V V
m d
explained by Gay-Lussac’s law. \ V = , p = K1 ×
d m
8. (d) HCl and NH3 react with each other, whereas the gases
æm ö
given in the other options do not react with each other. \ d = ç ÷ × p = K¢p
The Dalton’s law of partial pressure is applied to è k1 ø
non-reactive gases. This shows that, at a constant temperature, pressure is
w
9. (c) Number of moles of A , n A = A directly proportional to the density of a fixed mass of
MA
the gas.
0.50
= = 0.0083 14. (b) A real gas behave as an ideal gas at low pressure and
60
high temperature. Among the given options 550 K
w 0.20
Number of moles of B , n B = B = = 0.0044 temperature is the highest and 1 atm pressure is the lowest
MB 45 pressure.
Total pressure (p T ) = 750 mm of Hg 15. (b) At high pressure, all the gases have Z > 1. These are
p A = mole fraction of A ( c A ) ´ total pressure ( p T ) most difficult to compress, i.e. dominance of strong repulsive
forces among the molecules of the gas.
nA
Mole fraction of A,( c A ) = ´ pT 16. (a) Both A and R are true and R is the correct explanation of A.
n A + nB
Gases have high thermal energy and low intermolecular
0.0083 forces thus, their molecules are farther from each other.
c= ´ 750 = 490 mm
0.0083 + 0.0044 Solids have low thermal energy and high intermolecular
pB = 750 - 490 = 260 mm forces thus, their molecule are closer to each other.
17. (b) Both A and R are true, but R is not the correct (iii) (c) R is a constant and depends only on measuring-units
explanation of A. of pressure, temperature and volume which are same
London forces are applicable only for short distances for both gases.
(~500 pm) and its magnitude depends on the polarisability (iv) (b) pV = nRT
of the particle.
m
18. (b) Both A and R are true, but R is not correct explanation of A. pV = RT
M
NH3 has intermolecular H-bonding while CCl 4 has London
dispersion forces thus, NH3 has higher boiling point. m RT dRT
p= ´ =
H-bonding is stronger than dipole-dipole followed by V M M
London dispersion forces. pM
d=
19. (c) A is true, but R is false. RT
Ideal gas equation is given as, pV = nRT. \ d µ p at constant temperature
Ideal gas equation is obtained by combining Charles’, d = K¢p
Boyle’s and Avogadro’s law. Or
20. (d) A is false, but R is true. (a) Relationship of density and temperature from ideal
Excluded volume for n molecules of gas is 4 times the actual gas equation.
volume occupied by a molecule while ( V – nb ) is the pM
d=
corrected volume of the free volume available to the gas RT
molecules for movement. Considering density at T1 p1 and T2 p 2 .
21. (i) (b) In the given expression, value of K 1 depends upon pM pM
the amount of gas, temperature of gas and units in d1 = 1 d2 = 2
RT1 RT2
which p and V are expressed.
d2 p 2 T1
(ii) (d) Graph follows Gay-Lussac’s law. Lower curves =
correspond to higher volume. d1 p1T2
(iii) (d) According to ideal gas equation , p 2 T1d1
d2 =
pV = nRT p1T2
nRT w RT é w ù
Subjective Solutions
or V= = ...(i) êQ n =
p M. wt. p ë M. wt. úû
1. From the information and data given in the question,
Given, w = 1. 8 g , T = 374° C we concluded that
= ( 374 + 273) K = 647 K (i) In HCl, HBr and HI, dipole-dipole and London forces
p = 1 bar, R = 0. 083 bar LK -1 mol -1 are present because molecules possess permanent
On substituting the given values in Eq. (i), we get dipole. In HF molecule, dipole-dipole, London forces
1. 8 g 0. 082 bar LK -1 mol -1 ´ 647 K and hydrogen bonding are present.
V= ´
18 g mol -1 1 bar (ii) Electronegativity of chlorine, bromine and iodine
= 5. 3 L decreases in the following order
(iv) (d) The different values of gas constant (R ) are Cl > Br > I
Therefore, dipole moment should decrease from HCl to
R = 8.3 JK-1 mol -1 = 1.99 cal K-1 mol -1 HI. As a result, dipole-dipole interaction should also
= 0.0821 L atm K-1 mol -1 decrease from HCI to HI. But boiling point increases
Thus, the option (d) is incorrect. on moving from HCl to HI. This means that London
Or forces are predominant.
pV 2 T 2 (Nm -2 )( m 3 )2 (K )2 This is so because London forces increases as the
(a) = = Nm 4 K 2 mol -1 number of electrons in a molecule increases and in this
n mol
case, number of electrons is increasing from HCl
22. (i) (c) Pressure at the top of a mountain [or at high towards HI.
altitude] is low. This suggests that boiling takes place at
lower temperature, due to which things take more time (iii) Hydrogen fluoride has highest dipole moment is due to
to boil. highest electronegativity of fluorine as well as due to the
However, in a pressure cooker, pressure is increased presence of hydrogen bonding in HF. Therefore, HF has
and hence, boiling point increases. highest boiling point.
Thus, things comes to boil in a pressure cooker in a less 2. From Avogadro’s law, we know that
period of time. Volume of 1 mole of the gas = gram molecular mass
(ii) (c) It is known that, 1mole of a gas = gram molecular = 22.4 L at STP
mass = Avogadro's number of molecules Volume occupied by 28 g CO (1 mol CO) = 22.4 L at STP
= 22.4 L at STP (Q Molar mass of CO = 12 + 16 = 28 g mol -1 )
Thus, 1 mole of O2 gas = 32 g of O2 22.4
= 6.022 ´ 1023 molecules = 22.4 L of O2 at STP \ Volume occupied by 1 g CO = L at STP
28
22.4 n 1 + n 2 = 0.3 = n T
Similarly, volume occupied by 1 g H 2 O = L at STP
18 pV = n T RT
[Q Molar mass of H 2 O = (2 ´ 1) + 16 = 18 g mol –1 ] p ´ 9 = 0.3 ´ 0.082 ´ 300
22.4 p = 0.8214 atm
Volume occupied by 1g CH 4 = L at STP
16 7. (i) In accordance with Boyle’s law, pressure of a gas is
[Q Molar mass of CH 4 = 12 + (4 ´ 1) = 16 g mol -1 ] inversely proportional to its volume if temperature is
22.4 kept constant.
Volume occupied by 1g NO = L at STP
30 Thus, the volume of a gas will decrease, if the pressure
(Q Molar mass of NO = 14 + 16 = 30 g mol -1 ) on the gas is increased keeping the temperature
Thus, 1 g CH 4 will occupy maximum volume while 1 g of constant. e.g. At 200 K when pressure increases from p1
NO will occupy minimum volume at STP. to p 2 , volume of the gas decreases, V2 < V1.
3. Let the volume of the gas at 0°C = V mL (ii) In accordance to Charles’ law, volume of a gas is
directly proportional to its temperature if pressure is
Thus, we have V1 = V mL, V2 = 2 V mL kept constant.
T1 = 0 + 273 = 273 K Thus, on increasing temperature, the volume of a gas
T2 = to be calculated will increases when pressure is kept constant.
V1 V2 At constant p when we increase the temperature from
By Charles’ law, = 200 K to 400 K, the volume of the gas increases,
T1 T2
V4 > V3 .
Substituting the corresponding values, we have
V 2V 2 V ´ 273 p
= Þ T2 = = 546 K
273 T2 V p2
\ T2 = 546 - 273 = 273° C p (constant) 600 K
4. The plot of log p vs log V is based on Boyle’s law, whereas p1 400 K
that of log V vs log T is based on Charles’ law. 200 K
Boyle’s law Charles’ law 0
V2 V1 V4 V
V V3
pV = k =k
T
8. (i) As we go to higher altitudes, the atmospheric pressure
log p + log V = log k log V - log T = log k decreases. Thus, the pressure outside the balloon
log p = - log V + log k log V = log T + log k decreases. To regain equilibrium with the external
Both Eqs. (i) and (ii) are comparable to y = mx + c and pressure, the gas inside expands to decrease its
therefore, they represent straight lines. Their plots are as follows pressure. Hence, the size of the balloon increases.
(ii) In summer, due to higher temperature, the average
kinetic energy of the air molecules inside the tyre
log p
log V
increases, i.e. molecules start moving faster. Hence, the

pressure on the walls of the tube increases. If pressure
inside is not kept low at the time of inflation, at higher
0 0 temperature, the pressure may become so high that the
log V log T
tyre may burst.
5. p T = 1 bar
9. The density of a gas at STP can be calculated as,
20 80 We know that,
m1 = g H2 m 2 = g O2
100 100 pM pM
density, d1 = 1 ; d2 = 2
0.2 0. 8 RT1 RT2
n1 = = 0.1 n 2 = = 0.025
2 32 d1 p1T2 d Tp
or = Þ d2 = 1 1 2
n 1 + n 2 = 0.125 d2 p 2 T1 T2 p1
n1
c1 = = 0.8, c 2 = 0.2 dRT
n1 + n 2 10. Molecular mass of the mixture, M =
p
p i = cp T 1.50 L-1 ´ 0.0821 L atm K -1mol -1 ´ 293 K
= = 37. 06
p O 2 = 0.2 ´ 1 = 0.2 bar (740 / 760) atm
6. m 1 = 3.2 g CH4 , m 2 = 4.4 g CO 2 Calculation of percentage composition
M1 = 16 g/mol,M 2 = 44 g/mol Suppose mol % of CO in the mixture = x
m 1 3.2 m 2 4.4 Then, mol % of CO 2 in the mixture = (100 - x )
n1 = = n2 = =
M1 16 M 2 4.4 x ´ 28 + (100 - x ) ´ 44
Average molecular mass =
= 0.2 = 0.1 100
28x + 4400 - 44x (ii) At high pressure, the real gas show large deviations
\ = 37. 06
100 from ideal behaviour as the curves are far apart.
or 16x = 4400 - 3706 = 694 (iii) At point ‘ A ’, both the curves intersect each other. At
or x = 694 / 16 = 43. 38 this point real gas behaves as an ideal gas. p1 and V1 are
the pressure and volume which corresponds to this
\ Mole % of CO = 43.38 and
point A.
Mole % of CO 2 = 100 - 43.38 = 56.62.
11. (i) The container contains 1.25 moles of O2 and 3.2 moles
Real gas
of C. Since, only oxygen is gaseous and carbon will not
Ideal gas
exert any pressure.
n = 1.25 mol , V = 2.0 L ,
Pressure
T = 273 + 25 = 298 K
nRT
\ p=
V
(1.25 mol) ´ (0.0821 L atm mol -1K-1 )(298 K) O Volume
=
(2.0 L)
pV
= 15.3 atm 15. Compressibility factor, Z =
nRT
1
(ii) The reaction is C + O 2 ¾® CO. n = 1 mol, p = 5 ´ 10 6 Pa, V = 350 mL = 0.350 ´ 10 -3 m 3
2
R = 8.314 Nm K-1mol -1, T = 27 + 273 = 300 K
According to the equation, 1 mole of CO will be
produced for every 1/2 mole of O2 used. 5 ´ 106 ´ 0. 350 ´ 10-3
\Z = = 0.702
1 1. 0 ´ 8. 314 ´ 300
mole of O 2 gives 1 mole of CO
2 Thus, SO2 is more compressible than an ideal gas (which has
1.25 moles of O 2 will give CO = 1 ´ 2 ´ 1.25 = 2.50 mol Z = 1).
\ Final pressure 16. Consider two molecules A and B. Taking the molecules to be
(2.50 mol) ´ (0.0821 L atm K-1mol -1 ) ´ (298 K) spherical, if r is the radius of the molecules then the distance
p= of closest approach between the two molecules = 2 r (as
2.0 L
shown in Figure). This is the distance between the centres of
= 30.6 atm their nuclei.
12. N2 e 2N Excluded
1. 4 volume
Initial moles = 0. 05 0
28
30
Final moles 0.05 - ´ 0.05 2 ´ 0.015 A B
100
Dissociation = 0. 05 - 0. 015 = 0. 035 = 0.030
\ Total number of moles = 0.035 + 0.030 = 0.065
i.e. n = 0.065 mol, V = 5 L , T = 1800 K , p = ?
2r
From pV = n RT , we get
Since, the molecules cannot come closer than distance 2r,
nRT 0.065 mol ´ 0.0821 L atm K-1mol -1 ´ 1800 K
p= = the excluded volume for a pair of molecules = volume of
V 5L sphere of radius 2r.
= 1.92 atm 4 4
= p (2 r ) 3 = 8 ´ p r 3
13. 2Al + 2 NaOH + 2 H2 O ¾® 2NaAlO 2 + 3 H2 3 3
2 mol 3 mol \ Excluded volume per molecule (b)
2 ´ 27 g 3´ 2g 1æ 4 ö 4
0.15 ´ 3 = ç 8 ´ pr 3 ÷ = 4 ´ pr 3
0.15 g 2è 3 ø 3
2 ´ 27
= 0.00833 mol
4 3
But pr = Vm , i.e. the actual volume of the gas molecule.
pV = nRT 3
0.00833 mol ´ 0.0821 dm 3 atm K-1 mol -1 ´ 293 K \ b = 4Vm
VH 2 =
1 ´ 0.987 atm æ an 2 ö
(Q 1 bar = 0 . 987 atm) 17. ç p + 2 ÷( V - nb ) = nRT
è V ø
VH 2 = 0. 202 dm 3
æ nRT ö V2
14. (i) At low pressure, the real gas shows very small deviation or a = ç - p÷ ´ 2
è V - nb ø n
from ideal behaviour because the two curves almost
coincide at low pressure. n = 2 mol, V = 5 L, p = 9.1 atm, T = 273 + 27 = 300 K
R = 0.082 L atm mol -1K-1 m He = 1117 . 46 kg

æ 2 ´ 0.082 ´ 300 ö ( 5) 2 Total mass of filled balloon, m balloon
a=ç - 9.1÷ ´
è (5 - 2 ´ 0.052) ø (2 ) 2 = Mass of balloon + Mass of He filled in the balloon
49.2 25 25 m balloon = 100 kg + 1117.46 kg = 1217.46 kg
= - 9.1 ´ = (10.05 - 9.1) ´
4. 896 4 4 Pay load = Mass of displaced air - mass of balloon
= 5.94 atm L2 mol -2 = 5028 .57 kg - 1217 .46 kg = 3811.11 kg
18. (i) Molar volume occupied by the gas molecules µ size of (ii) 2 H2 ( g) + O2 ( g) ¾® 2 H2 O( g)
the molecules and van der Waals’ constant ‘ b ’ represents Initial moles 2 1 0
molar volume of the gas molecules. Hence, value of ‘ b ’ Final moles 2 - 1.6 1 - 0.8 1.6
increases in the following order = 0.4 = 0.2
H 2 < He < O2 < CO2 Total moles after reaction = 0. 4 + 0.2 + 1. 6 = 2.2
(ii) van der Waals’ constant ‘ a ’ is the measure of magnitude Let the initial pressure at 20° C = p1
of intermolecular attraction. The magnitude of
intermolecular attractions increases with increase in Pressure at 120° C = p 2
size of electron cloud in a molecule. Hence, for the According to Gay-Lussac’s law,
given gases magnitude of ‘ a ’ decreases in the following p1 T1 0.8 293
= or =
order p 2 T2 p 2 393
CH 4 > O2 > H 2 0. 8 ´ 393
or p2 = = 1.073 atm
Greater the size of electron cloud, greater is the 293
polarisability of the molecule and greater are the initial moles initial pressure
dispersion forces or London forces. Now, =
final moles final pressure
pV 100 ´ V 3 1. 073
19. Z = , i.e. 0.5 = =
nRT 1 ´ 0.082 ´ 273 2.2 p final
or V = 0.1119 L 1. 073 ´ 2.2
or p final = = 0.787 atm
æ a ö 3
ç p + 2 ÷ ( V - b ) = RT for 1 mol
è V ø 22. (i) p1V1 = p 2 V2 Þ 200 ´ 10 = 1 ´ V2 or V2 = 2000 L
æ a ö 2000 L
Neglecting b, ç p + 2 ÷ V = RT Therefore, number of breaths = = 4000
è V ø 0.5 L
a (ii) Suppose volume of the air in flask = V cm 3 at
or pV + = RT
V 27° C (300 K).
pV a V1 = V cm 3 , V2 = ?, T1 = 300 K, T2 = 750 K
or + =1
RT VRT V1 V2
æ pV ö =
or a = ç1 - ÷ VRT T1 T2
è RT ø V V
or = 2
= (1 - 0.5) 0.1119 ´ 0. 082 ´ 273 300 750
= 1.252 atm L2 mol -2 or 300 V2 = 750 V
20. (i) For ideal gas, compressibility factor, Z = 1. or V2 = 2 .5 V (final volume)
(ii) Above Boyle’s temperature, real gases show positive Volume expelled = 2.5 V - V = 1.5 V
deviation. 1.5 V
So, Z >1 Fraction of air expelled = = 0. 6
2.5 V
21. (i) R balloon = 10m 4
23. (i) The volume of a sphere = pr 3 where, r is the radius of
4 4 22 the sphere. 3
Vballoon = pr 3 = ´ ´ (10)3 = 4190.476
3 3 7 For N2 molecule,
Vballoon = Vdisplaced air (by balloon) r = 0.2 nm = 0.2 ´ 10 -9 m = 2 ´ 10 -8 cm
\ Mass of displaced air = Vdisplaced air ´ density of air Volume of a molecule of N 2
m displaced air = 4190. 476 m 3 ´ 1.2 kg m -3 4 22
= ´ ´ (2 ´ 10 -8 ) 3 cm 3 = 3.35 ´ 10 -23 cm 3
m = 5028.57 kg 3 7
Mass of He filled in balloon, (ii) To calculate the empty space, let us first find the total
pVM æ mRT ö volume of 1 mole ( 6. 02 ´ 1023 molecules) of N 2 .
m He = ç pV = ÷
RT è M ø Volume of 6.02 ´ 1023 molecules of
1.66 bar ´ 4190.476 ´ 10 3 dm 3 N 2 = 3.35 ´ 10 -23 ´ 6.02 ´ 10 23 = 20.17 cm 3
´ 4 ´ 10 -3 kg mol -1 Now, volume occupied by 1 mole of gas at STP
m He =
0.083 bar dm 3 K-1 mol -1 ´ 300 K = 22.4 litre = 22400 cm 3
Empty volume = Total volume of gas 2.9 g ´ R ´ 368 K 0.184 g ´ R ´ 290 K

=
- volume occupied by molecules M1 2 g mol -1
= (22400 - 20.17) cm 3 = 22379.83 cm 3 Molar mass of unknown gas,
empty space 2.9 g ´ 368 K ´ 2 g mol -1
\ Percentage empty space = ´ 100 M1 =
total volume 0.184 g ´ 290 K
=
22379. 83
´ 100 = 99. 9% = 40 g mol -1
22400 26. Mass of empty flask = 134.567 g
Thus, 99.9% of space of 1 mole of N2 at STP is empty.
Mass of flask with gas = 137.456 g
24. Weight of LPG originally present = 29. 0 - 14. 8 = 14.2 kg
Mass of inside flask = 2.889 g
Pressure = 2.5 atm Mass of flask with water = 1067.9 g
Weight of LPG present after use = 23.2 - 14. 8 Mass of water inside flask = 933.33 g
= 8.4 kg Mass
Density =
Since, volume of the cylinder is constant, applying Volume
pV = nRT 933.33
1=
p1 n 1 w1 / m w Volume
Þ = = = 1
p2 n 2 w 2 / m w 2 V = 933.33 mL = 0.933 L
2.5 14.2 2.5 ´ 8.4 Volume of flask = 0.933 L
Þ = or p 2 = = 1. 48 atm
p2 8. 4 14.2 Mass of gas at 735 mm and 31°C in 0.933 L flask is 2.889 g.
Q Weight of used gas = 14.2 - 8. 4 = 5. 8 kg pV = nRT
5. 8 ´ 103 735
Moles of gas = = 100 mol ´ 0.933 = n ´ 0.08214 ´ 304
58 760
735 ´ 0.933
Normal conditions p = 1 atm ; n=
760 ´ 0.08214 ´ 304
T = 273 + 27 = 300 K 735 ´ 0.933
Volume of 100 moles of LPG at 1 atm and 300 K n= = 0.0361
18977.625
nRT 100 ´ 0.082 ´ 300 w
V= = = 0.0361
p 1 M
= 2460 L = 2. 460 m 3 2.889
M= = 80.25 g mol -1
25. (i) (a) l Pressure in each compartment is same, (p atm) . 0.0361
l Temperature will remain same (t °C). 27. For 1 mole of a real gas, the van der Waals’ equation is
l Density will remain same (d g cm-3 ). æ a ö
ç p + 2 ÷ ( V - b ) = RT
Because of partition, volume of each compartment
l è V ø
becomes 1/4 and the number of molecules also The constant ‘a’ measures the intermolecular force of
become 1/4. The number of moles in each attraction of gas molecules and the constant ‘b’ measures the
compartment will be n / 4. volume correction by gas molecules after a perfectly inelastic
(b) l Pressure will remain same (p atm). binary collision of gas molecules.
l Temperature will remain same (t °C). For gas A and gas C given value of ‘b’ is
l Density will remain same (d g cm ).
-3
0.05196 dm 3 mol -1. Here,
l The number of moles in each compartment will a µ intermolecular force of attraction
be n /2. 1
µ compressibility µ real nature µ
(c) l Pressure will be doubled (2p atm). volume occupied
l Temperature will remain same (t°C).
-3
Value of a/(kPa dm 6 mol -1) for gas A (642.32) > gas C (431.91).
l Density will remain same (d gcm )
So, gas C will occupy more volume than gas A. Similarly, for a
l Number of moles will be doubled, i.e. 2n.
given value of a say 155.21 kPa dm 6 mol -1 for gas B and gas D
(ii) Unknown gas; H2 gas 1
m RT m RT µ intermolecular force of attraction
p1V1 = 1 1 ; p 2 V2 = 2 2 b
M1 M2 1
µ compressibility µ real nature µ
Q p1V1 = p 2 V2 volume accupied
m 1RT1 m 2RT2 b/(dm 3 mol -1) for gas B (0.04136) < gas D (0.4382)
\ =
M1 M2 So, gas B will be more compressible than gas D.
28. (i) van der Waals’ equation for one mole of real gas is (iv) In HCl, HBr and HI, dipole-dipole and London-forces
æ a ö are present because molecules possess permanent dipole.
ç p + 2 ÷ ( V - b ) = RT
è V ø In HF molecule, dipole-dipole, London-forces and
a hydrogen bonding are present.
When pressure is high p >> 2 .
V Or
æ a ö Cl 2 and CBr4 both have zero dipole moment and thus are
Such that ç p + 2 ÷ » p
è V ø non-polar compounds. Therefore, the intermolecular
Thus, p ( V - b ) = RT forces between them are London forces.
pV - pb = RT 30. (i) At low pressure and high temperature, a real gas behaves
as an ideal gas.
pV = RT + pb
(ii) The negative deviation from an ideal behaviour means that
\ Compressibility factor,
the value of pV decreases with increase in pressure.
pV æ pb ö
Z= = ç1 + ÷ (iii) a is a measure of magnitude of intermolecular forces of
RT è RT ø
attraction while b is a measure of the effective volume of
(ii) van der Waals’ equation is given by the gas molecules. Value of a and b depends upon the
æ a ö characteristics of a gas.
ç p + 2 ÷ ( V - b ) = RT
è V ø æ an 2 ö
a (iv) ç p + 2 ÷( V - nb ) = nRT
At low pressure, V decreases. Thus, 2 increases. è V ø
V
However, V is still large enough in comparison to ‘b’, æ nRT ö V2
or a = ç - p÷ ´ 2
hence, ‘b’ can be neglected. Thus, van der Waals’ è V - nb ø n
equation becomes n = 2 mol, V = 5 L, p = 9.1 atm, T = 273 + 27 = 300 K
æ a ö a
R = 0.082 L atm mol -1K-1
ç p + 2 ÷ V = RT Þ pV + = RT
è V ø V æ 2 ´ 0.082 ´ 300 ö ( 5) 2
a pV a a=ç - 9.1÷ ´
Þ pV = RT - Þ =1- è (5 - 2 ´ 0.052) ø (2 ) 2
V RT RTV
49.2 25
a é pV ù = - 9.1 ´
Z =1- êëQ RT = Z úû 4. 896 4
RTV
25
(iii) van der Waals’ constant a is due to force of attraction = (10.05 - 9.1) ´
4
and b due to finite size of molecules. -2
= 5.94 atm L mol
2
Thus, a (Cl 2 ) > a (C 2H 6 )
Or
and b (Cl 2 ) < b (C 2H 6 ) Given, n = 3
29. (i) Large or more complex the molecules are greater is the p = 15 bar
magnitude of London forces. This is obviously due to V = 10 moles
the fact that the large electron clouds are easily
a = 6.7 bar L2 mol -2
distorted or polarised.
b = 0.0564 L mol -1
(ii) It is because only partial charges are involved in
dipole-dipole interaction. e.g. HCl molecules. T =?
(iii) HF has stronger H-bonding than H 2 O because F is æ an 2 ö
ç p + 2 ÷ ( V - nb ) = nRT [van der Waals’ gas equation]
more electronegative than O and hence creates more è V ø
significant partial charges on the molecule leading to æ 6.7 ´ 9 ö
stronger H-bonding. ç15 + ÷ (10 - 3 ´ 0. 0564) = 3 ´ 0. 082 ´ T
è 100 ø
d+ d- Odd -
H ¾F 15.603 ´ 9.838 = 3 ´ 0.082 ´ T
H H dd + T = 623.5 K
Chapter Test 6. Assertion At constant temperature, pV versus p
plot for ideal gas is a straight line.
Reason At high pressure all gases have Z < 1 but at
intermediate pressure most gases have Z > 1.
Multiple Choice Questions 7. Assertion Compressibility factor for the helium gas
1 varies with pressure along with positive slope.
1. Consider a graph plotted between p and as shown
below V Reason Repulsive forces dominate in helium gas,
even at low pressure.
T3
T2
p 8. A gas occupies a volume of 250 mL at 745 mm of
T1 Hg and 25°C. What additional pressure is required
to reduce the gas volume to 200 mL at the same
temperature ? [Ans. 186.25 mm Hg]
1/V 9. Answer the following
The correct order of temperature T1 , T2 , T3 will be (i) What is the physical significance of gas constant
(a) T3 > T2 > T1 (b) T1 > T2 > T3 ( R ), write its value in L and K -1 mol -1 and JK -1 mol -1
(c) T1 = T2 = T3 (d) T1 > T2 = T3 of units? [Ans. 8.314 JK -1 mol -1 ]
2. The pressure of a 1 : 4 mixture of dihydrogen and (ii) Calculate the total presure in a mixture of 8 g of
dioxygen enclosed in a vessel is one atmosphere. What dioxygen and 4 g of dihydrogen confined in a
would be the partial pressure of dioxygen? vessel of 1 dm 3 at 27°C. [Ans. 56.025 bar]
(a) 0 .8 ´ 10 5 atm (b) 0.008 Nm -2 10. The relation between pressure exerted by an ideal
(c) 8 ´ 10 Nm
4 -2
(d) 0.25 atm gas ( pideal ) and observed pressure ( preal ) is given by
an 2
the equation, pideal = preal + 2
3. The negative deviation from ideal behaviour means that the V
(a) value of pV decreases with decrease in pressure
(i) If pressure is taken in Nm -2, number of moles in
(b) value of pV decreases with increase in pressure
mol and volume in m 3, calculate the unit of ‘ a’.
(c) value of pV increases with increase in pressure
(d) value of pV remains constant with increase in pressure (ii) What will be the unit of ‘ a’ when pressure is in
atmosphere and volume in dm 3 ?
4. van der Waals’ real gas, act as an ideal gas, at which
condition? 11. Calculate the pressure exerted by 10.2 g of ammonia
(a) High temperature, low pressure contained in 0.5 L vessel at 315 K. For ammonia,
(b) Low temperature, high pressure a = 5 atm L2mol-2, b = 0.036 L mol-1 . Compare the value
(c) High temperature, high pressure
with the calculated value, if the gas was considered as
ideal. [Ans. 30.996 atm]
(d) Low temperature, low pressure
Long Answer Type Questions
Assertion-Reasoning MCQs
Direction (Q. Nos. 5-7) Each of these questions contains
12. (i) Two closed bulbs of equal volume (V)
containing an ideal gas initially at pressure pi
two statements Assertion (A) and Reason (R). Each of and temperature T1 are connected through a
these questions also has four alternative choices, any one narrow tube of negligible volume as shown in
of which is the correct answer. You have to select one of the figure below. The temperature of one of the
the codes (a), (b), (c) and (d) given below. bulbs is then raised to T2. What is the final
(a) Both A and R are true and R is the correct explanation of A. pressure pf ?
(b) Both A and R are true, but R is not the correct explanation
T1 T2 T1 T2
of A.
(c) A is true, but R is false. pi, V pi, V pf, V pf ,V
(d) A is false, but R is true.
5. Assertion Real gases show ideal behaviour under low (ii) An open vessel at 27°C is heated until two fifth of
pressure and high temperature.
the air (assumed as an ideal gas) in it has escaped
Reason Ideal gases have no forces of interaction. from the vessel. Assuming that the volume of the
vessel remains constant, the temperature at
Answers which the vessel has been heated is
Multiple Choice Questions
1. (a) 2. (c) 3. (b) 4. (a)
For Detailed Solutions
Scan the code
5. (a) 6. (c) 7. (a)
CHAPTER 02
Chemical
Thermodynamics
In this Chapter...
l Thermodynamic Terms Thermochemical Equation
l Heat and Work l Spontaneity
Internal Energy Entropy
First Law of Thermodynamics Second Law Thermodynamics
Enthalpy Third Law of Thermodynamics
Thermodynamics deals with the study of different energy l

The state of a system is described by its measurable
transformations and the quantitative relationship between properties such as T, V, p etc., of the system.
them. l
These properties of the system are called state variables or
state functions as their values depends upon the state of the
Thermodynamic Terms system and not on the path followed.
l
A system in thermodynamics refers to that part of universe l
The variables, values of which are affected by the path
in which observations are made and remaining universe followed are called path functions, e.g. work ( W ), heat ( q ),
constitutes the surroundings. etc.
l
The wall that separate the system from the surroundings is
called boundary. Thermodynamic Process
l
Depending upon the movement of matter or energy in or The state of a system can be changed via thermodynamic
out of the system, the system can be classified as process. These processes are of the following types
(i) Open system In which energy and matter both can be l
Adiabatic process The process in which system does not
exchanged with surroundings, e.g. reactants in an open exchange heat with its surrounding is called adiabatic
beaker. process. For adiabatic process, dq = 0 and DU = U 2 - U1 = W
(ii) Closed system In which only energy can be exchanged l
with surroundings, e.g. hot water kept in closed container. Isothermal process This process is carried out at constant
temperature, i.e. dT = 0 and thus, dE = 0.
(iii) Isolated system In which neither matter nor energy can
be exchanged with surroundings, e.g. thermos flask.
l
Isobaric process In this process, change of state is brought
about at constant pressure, i.e. dp = 0
l
Extensive properties are those properties which depend
upon the quantity or size of matter, e.g. mass, volume,
l
Isochoric process In this process, volume of the system
internal energy, enthalpy, heat capacity, etc. remains constant, i.e. dV = 0
l
Intensive properties are those which do not depend upon
l
Cyclic process When a system has undergone a number of
the quantity or size of matter, e.g. pressure, temperature, different states and finally returns to its initial state the
concentration, viscosity, etc. process is called cyclic process.
dE or dU = 0 and dH = 0
l
Reversible process A system where change takes place First Law of Thermodynamics
infinitesimally slow and the direction of which at any point
can be reversed by infinitesimal change in the state of the According to first law of thermodynamics, the energy can
system. neither be created nor be destroyed but can be converted
into one form to another.
l
Irreversible process An irreversible process is one in
which direction of that process cannot be reversed by small That’s why, it is also called law of conservation of energy.
changes in variables. The mathematical expression of first law of thermodynamics
is given as,
Heat and Work DU = q + W
l
Heat is defined as the quantity of energy which flows where, DU = change in internal energy
between system and surroundings on account of q = heat consumed
temperature difference. It is a path function. W = work done on the system
l
When work of the system involves gaseous substances and If there is no heat transfer or work done (i.e. in an isolated
there is a difference of pressure between system and system), DU will be zero.
surroundings, this type of work is referred as If a process is carried out at constant volume, then DU = q V .
pressure-volume work. (Here, q denotes heat that is supplied at constant volume).
l
If mechanical work is done in a single step. For isothermal irreversible change,
W = - p ext DV q = - W = p ext ( Vf - Vi )
or W = - p ext ( Vf - Vi ) and for isothermal reversible change.
V
l
The negative sign (–ve) represents the work is done by the q = - W = 2.303 nRT log f
system in case of expansion. In case of compression, the Vi
sign should be positive (+ve).
Sign Convention
l
If the pressure changes in number of steps, then work done
on the gas will be given as
l
q is +ve = heat is supplied to the system.
l
q is - ve = heat is lost by the system.
W = - Sp D V l
W is +ve= work is done on the system.
l
If pressure is not constant at each stage of compression and l
W is - ve = work is done by the system
the process is reversible isothermal, then work done is l
DU is - ve = energy transfer from system to surrounding.
given as l
DU is +ve = energy transfer from surrounding to system.
Vf
Wrev = - ò p int dV
Vi
Vf Enthalpy
or Wrev = - 2.303 nRT log
Vi The total heat content of a system at constant pressure is
pi called enthalpy of the system.
or Wrev = - 2.303 nRT log It is a state function and is given by the expression
pf
DH = DU + pDV.
where, n = number of moles of gas
R = gas constant, T = temperature (in K) Note DH = q p , heat absorbed by the system at constant pressure.
l
At constant volume; DU = q V , i.e. heat supplied at constant
Vi = initial volume, Vf = final volume
volume.
p i = initial pressure, p f = final pressure l
DH = - ve for an exothermic reaction and DH = + ve for an
l
Work done is maximum in case of reversible isothermal endothermic reaction.
expansion of a gas. l
For solids and liquids, DH and DU is insignificant but for
l
In case of free expansion, a gas expands under vacuum gases, if pressure and temperature remain constant, then
(p ext = 0). In this case, W is also zero, i.e. no work is done. pDV = Dn g RT
Here, Dn g = n p - n R
Internal Energy
where, n A is the total number of moles of gaseous product
In thermodynamics, energy of the system is called internal
and n B is total the number of moles of gaseous product;
energy (E or U). It is a state function. It is the sum of
chemical, electrical, mechanical or any other form of energy D n g is the total number of moles of gaseous product minus
that anyone may think of. that of reactants.
Moreover, DH = DU + Dn g RT Standard Enthalpy Changes for Different Types Processes

This equation is helpful for calculating DH from DU and Transition Enthalpy Examples Symbol
vice-versa.
If case I D ng = 0, then DH = DU
l Enthalpy of fusion H2 O(s) ¾® H2 O( l ) D fus H° or DH°fus
case II D ng < 0, then DH < DU l Enthalpy of H2 O(l ) ¾® H2 O( g) D vapH° or DH°vap

case III D ng > 0, then DH > DU. vaporisation
l Enthalpy of H2 O(s) ¾® H2 O( g) D subH° or DH°sub
Thermochemical Equation sublimation
O 2 (g) ¾® H 2 O(l ) D f H° or DH°f

Enthalpy of 1
A thermochemical equation is a balanced chemical equation l
H 2 (g ) +
in which the value of D r H ° is also mentioned. formation 2
e.g. C 2 H5 OH( l) + 3O 2 ( g) ¾® 2CO 2 ( g) + 3H 2 O( l) ; l Enthalpy of H2 ( g) ¾® 2 H( g) D aH° or DH°a

D r H ° = - 1367 kJ/ mol atomisation (In this case enthalpy of
atomisation is same as the
Note Negative (–ve) sign indicates, it is an exothermic reaction.
bond dissociation enthalpy)
Some conventions related to thermochemical equations are
Na(s) ¾® Na( g)
as follows
(Here, enthalpy of
l
Negative D r H s means the reaction is exothermic and atomisation is same as that
positive D r H s means the reaction is endothermic. of sublimation enthalpy.)
l
The coefficients of different substances in a balanced
thermochemical equation show only their number of
l Bond dissociation HX( g) ¾® H( g) + X( g) DH°A -B
enthalpy (for
moles (never molecules) involved in that reaction. diatomic molecule)
l
On reversing a reaction, the sign of DH is also reversed but
its magnitude remain the same. l Lattice enthalpy KCl(s) ¾® K+ ( g) + Cl - ( g) D latticeH°
l
Enthalpy is an extensive property, thus if a thermochemical or DH°lattice
equation is multiplied or divided by an integer, n, the value
of D r H s is also multiplied or divided by the integer, n.
l Enthalpy of A(s) + H2 O(excess) ¾® A( aq) D H° or DH°
sol sol
solution
D solH° = D latticeH°
Enthalpy Change of a Reaction, D r H + D hydH°
It is the heat change that accommpanies a chemical reaction
represented by a balanced chemical equation. l
Enthalpy of 13 D cH° or DH°c
CH4 ( g) + O2 ( g) ¾®
combustion 2
D r H = S x i HP - S y i HR
i i 4CO2 ( g) + 5H2 O(l )
where, x i and y i = stoichiometric coefficients of products and
reactants respectively in a balanced equation. l
Standard enthalpy CuSO4 (s) + 5H 2 O( l ) ¾® D H° or DH °hyd
hyd
of hydration CuSO × 5H O(s)
HP = enthalpy of formation of products 4 2
HR = enthalpy of formation of reactants -

D n H° or DH°n
+
l
Standard enthalpy H ( aq) + OH ( aq) ¾®
l
Molar enthalpy change (H m ) is the enthalpy change when of neutralisation H 2 O( l )
quantities (in moles) of reactants have reacted completely
as indicated by the balanced chemical equation.
l
Standard enthalpy KCl (200 H 2 O) ¾® D dil.H or DH dil.
of dilution KCl (300 H 2 O)
e.g. CH 4 ( g ) + 2O 2 ( g ) ¾® CO 2 ( g ) + 2H 2 O( l )
D r H = [H m (CO 2 ( g )) + 2H m (H 2 O ( l ))] l
Standard enthalpy CH 3 COOH ( aq) e D ion H° or DH °ion
of ionisation
- [H m (CH 4 ( g )) + 2H m (CO 2 ( g ))]
CH 3 COO- ( aq) + H + ( aq)
l
The enthalpy change occurring during a reaction when all
the involved substances are in their standard states, is Note Enthalpy change of reaction can also be calculated by bond
called the standard enthalpy of the reaction. enthalpy as
l
The purest and most stable form of a substance at 1 bar and at D r H° = SBond enthalphies of reactants - SBond enthalpies of products
a specified temperature is called its standard state, e.g. the or D r H° = S D f HBonds
° of products - SD f HBonds
° of reactants.
standard state of solid iron at 500 K is pure iron at 1 bar.
Hess’s Law of Constant Heat Summation positive, i.e. enthalpy of the system increases but there are
several endothermic reactions that are spontaneous.
According to this law, “the total heat change ( DH) l
The enthalpy diagram for such reactions is shown below
accompanying a chemical reaction is the same, whether the
reaction takes place in one or more steps.”
Total enthalpy H
For a reaction, A ¾® B of products P
∆r H
∆H
A B Net heat absorbed
H from the surroundings
∆H1 ∆H3 in the reaction
Total enthalpy
HR
of reactants
C D
∆H2
It can be represented as,
DH = DH1 + DH 2 + DH 3 + ¼ Reactants Products
Born-Haber Cycle Enthalpy diagram for endothermic reactions

l
It is an approach to calculate energy involved during a
process and is based on the Hess’s Law of constant heat Entropy
summation. Another thermodynamic function, entropy is introduced for
l
Lattice enthalpy can be indirectly calculated by determining spontaneous reaction. It is the measure of
Born-Haber cycle. It can be explained by using an example degree of randomness or disorderness in an isolated system
of NaCl as shown below and is represented by the symbol (S).
∆f H°
Na(s) + 1/2 Cl2 (g) Na + Cl– (s) The greater the degree of randomness, higher is the entropy.
1/2 ∆bond H° ∆lattice H° It is also a state function.
∆sub H°
∆ eg H
Cl (g) Cl– (g) Entropy Change in Reversible Process
∆i H° + Consider an isothermal reversible process, let the system
Na(g) Na+ (g) absorbs q amount of heat from surroundings at temperature,
T. The increase in the entropy of the system will be
Spontaneity DS system = +
q sys, rev
l
A spontaneous process is an irreversible process and may T
only be reversed by some external agency, e.g. burning of Surroundings lose the same amount of heat at the same
carbon giving CO 2 , heat flow, rolling ball, gas flow etc. temperature. The decrease in the entropy of the surroundings
will be
l
A tendency to attain the minimum energy, i.e. decrease in q surroundings, rev
energy is responsible for the spontaneity or feasibility of a DS surroundings = -
T
reaction.
l
The enthalpy diagram for an exothermic reaction, showing Total change in entropy of the process = entropy change in
the decrease in enthalpy when reactants are converted into system + entropy change in surroundings
products is shown below q q
DS total = DS system + DS surroundings = - = 0
T T
Total enthalpy H When the reversible process is adiabatic, there will be no
P
of reactants
∆r H heat exchange between system and surroundings,
H Net heat evolved i. e. q=0
Total enthalpy in the reaction
HR
of products \ DS system = 0
DS surroundings = 0
DS total = DS system + DS surroundings = 0
Reactants Products
Reaction coordinates Entropy Change in Irreversible Processes
Enthalpy diagram for exothermic reactions
Consider a system at higher temperature T1 and its
l
Decrease in energy, the criteria for spontaneity has the surroundings at lower temperature T2 . q amount of heat goes
following limitation. In case of endothermic reactions, DH is irreversibly from system to surroundings.
q q Standard Free Energy Change

\ DS system = - ; DS surroundings = +
T1 T2
The free energy change for a process at 298 K and 1 atm
q q é T - T2 ù pressure in which the reactants in their standard state are
DS total = DS system + DS surroundings = - + = qê 1 ú
T1 T2 ë T1 T2 û converted into products in their standard state is called
standard free energy change.
But T1 > T2
\ T1 - T2 = + ve or DS total > 0 It is denoted by DG°.
éSum of the standard free energy ù
Hence, entropy increases in an irreversible process. D r G° = ê ú
ë of formation of products û
Entropy Change During Phase Transition
é Sum of the standard free energy of ù
l
The change of matter from one state to another is called -ê ú
phase transition. The entropy changes at the time of phase ë formation of reactants û
change can be summarised as = S f G°(products) - SD f G°(reactants)
DH fusion
DS melting = S liq - S sol = The criteria of spontaneity through Gibbs free energy is as
Tm follows
where, Tm = melting point of substance, S liquid = molar At a given temperature and pressure.
entropy of the liquid, S solid = molar entropy of the solid (i) If DG is negative, ( < 0 ) the process is spontaneous.
DH vaporisation (ii) If DG is positive ( > 0 ), the process is non-spontaneous.
DS vaporisation = S vap - S liq =
Tb (iii) If DG is zero, the process is in equilibrium state.
where, Tb = boiling point of substance The various conditions in which a reaction occur
DH sublimation
Similarly, DS sublimation = S vap - S sol = spontaneously are tabulated below
Tsub
Effect of Temperature on Spontaneity of Reactions
where, Tsub = sublimation temperature.
l
The total entropy change for the spontaneous process is given as, D r H s D r Ss D rGs Description
DS total = DS sys + DS surr > 0
- + - (at all T ) Reaction is spontaneous at all
l
The change in entropy at equilibrium, i.e. DS = 0. temperature.
Second Law of Thermodynamics - - - (at low T ) Reaction is spontaneous at low

temperature.
The second law of thermodynamics can be stated as
l
whenever a spontaneous process takes place, it is always - - + (at high T ) Reaction is non-spontaneous at
high temperature.
accompanied by an increase in total entropy of the universe.
In the above statement, the term universe means the system + + + (at low T ) Reaction is non-spontaneous at low
and the surroundings. Thus, DS univ = DS sys + DS surr temperature.
l
it is impossible to take heat from a hotter reservoir and
+ + - (at high T ) Reaction is spontaneous at high
completely convert into work by a cyclic process without temperature.
transferring a part of heat to a cooler reservoir. This
statement of second law is called Kelvin’s statement. The + - + (at all T ) Reaction is non-spontaneous at all
above statements (i. e. the second law) in simplified form can temperature.
be stated as ‘‘for a spontaneous process in an isolated
system, the change in entropy is positive.’’
Third Law of Thermodynamics
Gibbs Energy and Spontaneity According to third law of thermodynamics, ‘‘the entropy of a
Gibbs function or Gibbs energy is introduced because perfectly crystalline substance approaches zero as the
decrease in enthalpy and increase in entropy cannot absolute zero of temperature is approached’’.
determine the spontaneity of the reaction. It forms the basis from which entropies at other
It is given as, temperatures can be measured.
DG = DH - TDS [Gibbs Helmholtz equation] Lim S = 0
T® 0
where, DG = change in Gibbs energy Note In case of CO and NO molecules in solid state, there is
DH = change in enthalpy and DS = change in entropy randomness even at 0 K due to their dipole moment, hence
entropy in such cases is not zero even at 0 K.
It is an extensive property and a state function.
Solved
Examples
Example 1. Two litres of an ideal gas at a pressure of Example 5. If water vapour is assumed to be a perfect gas,
10 atm expands isothermally against a constant external molar enthalpy change for vaporisation of 1 mole of water at
pressure of 1 atm, until its total volume is 10 L. How much 1 bar and 100°C is 41 kJ mol -1 . Calculate the internal
work is done during the expansion? energy change, when
Sol. W = - p ext + ( DV ) = - 1(10 - 2 ) = - 1( 8) = - 8 L atm (i) 1 mole of water is vaporised at 1 bar pressure and 100°C.
(ii) 1 mole of water is converted into ice.
Example 2. (i) 5.2 mol of ideal gas at 3 atm and 25° C
Sol. (i) For the change H2 O ( l ) ¾® H2 O ( g)
expands isothermally to 3 times of its original volume
against the external pressure of 1 atm. Calculate work done. DH = DU + Dn gRT
(ii) If the same gas expands isothermally in a reversible or DU = DH - Dn gRT
manner, then what will be the value of work done? DU = 41.000 kJ mol -1- 8.3 J mol -1 K-1 ´ 373 K
Sol. (i) W = - p ext ( V2 - V1 ) = 41.00kJ mol -1 - 3.096 kJ mol -1
nRT
Now initial volume ( V1 ) = = 37.904 kJ mol -1
p
(ii) In the conversion H2 O ( l ) ¾® H2 O (s)
5.2 ´ 0.082 ´ 298
= = 42.35L There is negligible change in the volume,
3
Final volume ( V2 ) = 42.35 ´ 3 = 127.05 So, we can put pDV = Dn gRT » 0 in this case,
Now, W = - 1(127. 05 - 42. 35) = 84.7 DH ~ = DU
= - 84.7 ´ 101.325 J So, DU = 41. 00 kJ mol -1
= - 8582.22 J Example 6. Standard vaporisation enthalpy of benzene at
(ii) For isothermal reversible expansion of ideal gas boiling point is 30.8 kJ mol -1 . For how long would 100 W
V electric heater have to operate in order to vaporise a 100 g
Wrev = - 2. 303 nRT log 2
V1 sample at that temperature
æ 127. 05 ö
= - 2. 303 ´ 5.2 ´ 8. 314 ´ 298 log ç ÷ (power= energy/time and 1 W = 1 Js -1 )?
è 42. 35 ø
= 14156.38 J Sol. D vapH° ( benzene) = 30.8 kJ mol -1
Example 3. Two litre of an ideal gas at a pressure of 10 atm Molar mass of benzene,
expands isothermally into a vacuum until its total volume is C 6H 6 = (6 ´ 12 + 6 ´ 1) g mol -1
10 L. How much heat is absorbed and how much work is
done in the expansion? = 78 g mol -1
Sol. For isothermal process, DU = 0, so from first law of Energy needed to vaporise benzene
thermodynamics 0 = q + W 100 g
= 30.8 kJ mol -1 ´ = 39. 49 kJ
or q = - W = p ext (10 - 2 ) 78 g mol -1
energy
= 0 ( 8) = 0 So Time =
power
Thus, no work is done; and hence, no heat is absorbed.
39.49 kJ 39.49 ´ 103 J
Example 4. In a process, 701 J of heat is absorbed by a = =
100 W 100 Js -1
system and 394 J of work is done by the system. What is the
change in internal energy for the process? = 394.9 s = 6.6 min
Sol. Given, q = + 701 J (heat is absorbed, hence q is positive). Example 7. A swimmer coming out from a pool is covered
W = - 394 J (work is done by the system, hence W is with a film of water weighing about 18 g. How much heat
negative). By first law of thermodynamics; must be supplied to evaporate this water at 298 K?
Internal energy change, DU = q + W Calculate the internal energy of vaporisation at 100°C ?
= + 701 J + ( - 394 J) = + 307 J
D vap H s for water at 373 K = 40. 66 kJ mol -1 (NCERT)
Hence, internal energy of the system increases by 307 J.
Sol The process of evaporation can be represented as 1

l Br 2 ( g) ¾® Br( g); D diss H s
Vaporisation 2
18 g H 2 O( l ) ¾¾¾¾¾® 18 g H 2O( g) l Br ( g) + e- ( g) ¾® Br - (g); D egH s
18 g Given that, D subH s for Na metal = 108.4 kJ mol -1
Number of moles in 18 g H 2 O( l ) = = 1 mol
18 g mol -1 IE of Na = 496 k J mol -1, Deg H s of
and D vapH s is the amount of heat required to vaporise 1 mole
Br = - 325 kJ mol -1,
of a substance. Thus, 40.66 kJ mol -1 heat is required for
192
evaporation of 18 g of water. D diss H s of Br = 192 kJ mol -1 = = 96 kJ mol -1
2
Further, we know that
D f H s for NaBr = - 360.1 kJ mol -1
D vap U = D vapH s - pDV = D vapH s - Dn gRT
l Applying Hess’s law
(assuming steam behaving as an ideal gas).
D f H s = D sub H s + IE + D diss H s + D e g H s + U
\ D vap U= 40.66 kJ mol -1 - (1) (8.314 JK -1 mol -1 )
(373 K) (10-3 ) - 360.1 =108.14+496+96( -325) - U
D vap Us = 40.66 kJ mol -1 - 3.10 kJ mol -1 = 37.56 kJ mol -1 U = 735.5 kJ/mol
Example 8. The enthalpy of formation of carbon monoxide Example 10. For oxidation of iron,
and steam are - 110. 5 and - 243. 0 kJ respectively. Calculate 4Fe (s ) + 3O 2 ( g) ¾® 2Fe 2O 3 (s )
the heat of the reaction when steam is passed over coke as entropy change is -549.4 JK -1 mol -1 at 298 K. Inspite of
C (s ) + H 2O ( g) ¾® CO( g) + H 2 ( g) negative entropy change of this reaction, why is the reaction
Sol. We are given spontaneous? (D r H s for this reaction is - 1648 ´ 10 3 J mol -1 )
1
(i) C (s ) +O2 ( g) ¾® CO2 ( g); DH = - 110. 5 kJ Sol. The spontaneity of the reaction is decided by considering
2
1 DStotal( DS sys + DS surr ). At temperature T, entropy change of
(ii) H 2 ( g) + O2 ( g) ¾® H 2 O ( g); DH = - 243.0 kJ the surroundings.
2
Subtracting Eq. (ii) from Eq. (i), we get D Hs
DSsurr = r (at constant pressure)
C(s) + H 2 O ( g) ¾® CO( g) + H 2 ( g); DH = + 132.5 kJ T
- 1
( -1648 ´ 10 Jmol )
3
Example 9. Use the following data to calculate D lattice H s for =-

298 K
NaBr. D sub H s for sodium metal = 108.4 kJ mol -1 , = 5530.20 JK-1mol -1
ionisation enthalpy of sodium = 496 kJ mol -1 , electron gain Thus, total entropy change for this reaction
enthalpy of bromine = -325 kJ mol -1 , bond dissociation DStotal = 5530 JK-1mol -1 + ( -549.4 JK -1mol -1 )
enthalpy of bromine = 192 kJ mol -1 , D f H s for
= 4980.8 JK-1mol -1
NaBr(s ) = - 360.1 kJ mol -1
Positive value of DStotal shows that the above reaction is
Sol. l Na (s) ¾® Na (g); D sub H s
spontaneous.
l Na (g) ¾® Na + (g) + e- (g); IE
Chapter
Practice
PART 1 6. In an exothermic reaction, heat is evolved, and
system loses heat to the surrounding. For such
Objective Questions system
(a) qp will be negative (b) D r H will be zero
(c) qp will be positive (d) D r H will be positive
l
7. The combustion of benzene (l ) gives CO 2 (g) and
1. On which of the following factor(s) does the internal H 2O ( l ). Given that heat of combustion of benzene at
energy of the system depend? constant volume is -3263. 9 kJ mol -1 at 25° C; heat
(a) Matter enters or leaves the system of combustion (in kJ mol -1 ) of benzene at constant
(b) Work is done on or by the system pressure will be (R = 8.314 JK -1 mol -1 )
(c) Heat passes into or out of the system (a) 4152.6 (b) -452.46
(d) All of the above (c) 3260 (d) - 3267.6
2. The state of a gas can be described by quoting the 8. The heat of formations of CO (g) and CO 2 (g) are
relationship between - 26.4 kcal and – 94.0 kcal respectively. The heat of
(a) pressure, volume, temperature combustion of carbon monoxide will be
(b) temperature, amount, pressure (a) - 46.5 kcal (b) 36.5 kcal
(c) amount, volume, temperature (c) - 36.5 kcal (d) - 67.6 kcal
(d) pressure, volume, temperature, amount 9. Enthalpy change for the reaction,
3. The correct inference that can be observed from the 4H ( g ) ¾® 2H 2 ( g ) is - 869.6 kJ
given figure is The dissociation energy of H ¾ H bond is
(a) - 869.6 kJ (b) + 434.8 kJ
V, T Partition (c) + 217.4 kJ (d) - 434.8 kJ
10. Which of the following statements is correct?

(a) Each part has double the temperature of the gas (a) Combustion reactions are endothermic in nature
(b) Each part has the same temperature of the gas (b) During complete combustion of 1 mole of butane,
2658 kJ of heat is released
(c) Each part only have half the temperature of the gas
(c) Our body generates energy from food by the process of
(d) Each part has one-fourth the temperature of the gas atomisation
4. In an adiabatic process, no transfer of heat takes (d) All of the above
place between system and surroundings. Choose 11. Standard enthalpy of vaporisation D vapH° for water
the correct option for free expansion of an ideal gas
under adiabatic condition from the following at 100ºC is 40.66 kJ mol -1 . The internal energy of
(a) q = 0, DT ¹ 0, W = 0 (b) q ¹ 0, DT = 0, W = 0
vaporisation of water at 100°C (in kJ mol -1 ) is
(c) q = 0, DT = 0, W = 0 (d) q = 0, DT < 0, W ¹ 0
(Assume water vapour to behave like an ideal gas).
(a) +37.56 (b) - 43.76
5. The enthalpies of elements in their standard states (c) + 43.76 (d) + 40.66
are taken as zero. The enthalpy of formation of a
compound 12. If the sublimation energy and enthalpy of fusion of
(a) is always negative
I 2 are 57.3 kJ mol -1 and 15.5 kJ mol -1 , respectively
(b) is always positive
then, the enthalpy of vaporisation of I 2 will be
(c) may be positive or negative (a) –72.8 kJ mol -1 (b) 72.8 kJ mol -1
(d) is never negative (c) – 41.8 kJ mol -1 (d) +41.8 kJ mol -1
13. The enthalpy of fusion of water is 1.435 kcal/mol. 20. Assertion Combustion of all organic compound is an
The molar entropy change for the melting of ice at exothermic reaction.
0° C is Reason The enthalpies of all elements in their
(a) 10.52 cal/mol K (b) 21.04 cal/mol K standard state are zero.
(c) 5.260 cal/mol K (d) 0.526 cal/mol K
l
Case Based MCQs
14. In the given equation,
4Fe (s ) + 3O2 ( g) ¾® 2Fe 2O 3 (s ) 21. Read the following and answer the questions from (i)
to (iv) given below
The entropy change is –549.4 JK -1 mol -1 at 298 K.
(D r H° = -1648 ´ 10 3 J mol –1 ). The above reaction is Enthalpy is the sum of the internal energy and the
(a) spontaneous
product of the pressure and volume of a
(b) non-spontaneous
thermodynamic system. Enthalpy is an energy-like
(c) non-spontaneous at 500 K
property or state function, it has the dimensions of
(d) None of these
energy (and it thus measured in units of joules or ergs)
and its value is determined entirely by the
15. Which of the following is not correct? temperature, pressure and composition of the system.
(a) DG is zero for a reversible reaction. In symbols, the enthalpy, H, equals the sum of the
(b) DG is positive for a spontaneous reaction. internal energy, E and the product of the pressure, p
(c) DG is negative for a spontaneous reaction. and volume, V of the system H = E + pV.
(d) DG is positive for a non-spontaneous reaction. According to the law of energy conservation, the
change in internal energy is equal to the heat
l
transferred to, less than work done by, the system. If
Direction (Q. Nos. 16-20) For given questions two the only work done is a change of volume at constant
statements are given-one labelled Assertion (A) and pressure, the enthalpy change is exactly equal to the
the other labelled Reason (R). Select the correct heat transferred to the system. When energy needs
answer to these questions from the codes (a), (b), (c) to be added to a material to change its phase from
and (d) as given below. liquid to gas, that amount of energy is called
(a) Both A and R are true and R is the correct enthalpy or latent heat of vaporisation and is
explanation of A. expressed in units of joules per mole.
(b) Both A and R are true, but R is not the correct
explanation of A.
Other phase transitions have similar associated
(c) A is true, but R is false.
enthalpy changes, such as the enthalpy (or latent
(d) A is false, but R is true. heat) of fusion for changes from a solid to a liquid.
As with other energy functions, it is neither
16. Assertion Volume of water in a pond is not a state convenient nor necessary to determine absolute
function.
values of enthalpy. By looking at whether q is
Reason Volume of water is independent of the exothermic or endothermic we can determine a
route by which water is filled in the pond either by relationship between DH and Dq. If the reaction
rain or by tubewell or by both. absorbs heat it is endothermic meaning the reaction
17. Assertion Internal energy is an extensive property. consumes heat from the surroundings so q > 0
Reason Internal energy depends upon the amount (positive). Therefore, at constant temperature and
of the system. pressure, by the equation above, if q is positive then
DH is also positive. And the same goes for the
18. Assertion There is no exchange in internal energy reaction which are exothermic, meaning the system
in a cyclic process. gives off heat to its surroundings, so q < 0 (negative).
Reason Cyclic process is the one in which the If q is negative, then DH will also be negative.
system returns to its state after a number of (i) In the given reaction,
reactions.
Na(s) ¾® Na(g)
19. Assertion For an isothermal reversible process The enthalpy of atomisation is same as the
Q = - W, i.e. work done by the system equals the (a) enthalpy of dissociation
heat absorbed by the system. (b) enthalpy of sublimation
Reason Enthalpy change (DH) is zero for isothermal (c) enthalpy of association
process. (d) enthalpy of vaporisation
∆H
(ii) The standard enthalpy change for the formation A B
of one mole of a compound from its elements in ∆H1 ∆H3
their most stable states of aggregation is called C D
(a) standard molar enthalpy of condensation ∆H2
(b) standard molar enthalpy of formation Then according to Hess’s law
(c) molar enthalpy of condensation DH = DH1 + DH 2 + DH 3
(d) molar enthalpy of formation It clearly indicates that when chemical equations are
(iii) The enthalpy change that accompanies melting added, subtracted or multiplied, the heat changes can
of one mole of a solid substance in standard also be added, substracted or multiplied accordingly.
state is called standard enthalpy of ……… Hess’s law is used for the determination of
(a) sublimation (b) vaporisation enthalpies of formation of compounds and also for
(c) formation (d) fusion the determination of enthalpies of extremely slow
(iv) Which of the following statement(s) is/are reactions.
correct? (i) The standard enthalpy of formation of NH 3 ( g) is
(a) Unit of D r H s is kJ mol -1 - 81.9 kJ mol -1 . The amount of heat required to
(b) Enthalpy is an intensive quantity decompose 26 g of NH 3 ( g) into its elements
(c) When a chemical equation is reversed the value of (in kJ), is
D r H s remain same in magnitude
(a) 122.9 (b) 143.8 (c) 164.7 (d) 105.6
(d) All of the above
(ii) How much of heat is required by the chemical
Or D f U s of formation of CH 4 ( g) at certain
reaction in order to decompose CaCO 3 to lime
temperature is -393 kJ mol -1 . The value of
and CO 2 ? (Standard molar enthalpies of
D f H s is (NCERT Exemplar)
formation is given in the table).
(a) zero (b) < D f U s
Substance D f H°/(kJ mol -1)
(c) > D f U s (d) equal to D f U s
CaCO3 (s) – 1206.92
22. Read the following and answer the questions from CaO (s) – 635.09
(i) to (iv) given below
CO2 (g) – 393.51
Entropy is the measure of degree of randomness or
-1
disorderness in an isolated system and is (a) 187 kJ mol (b) 170.0 kJ mol -1
represented by the symbols. Greater the degree of (c) 178.3 kJ mol -1 (d) Cannot be determined
randomness, higher is the entropy. (iii) Hess’s law is based on
In case of chemical reactions, it shows the (a) law of conservation of mass
rearrangement of atom or ions from one pattern in (b) law of conservation of energy
the reactants to another. If the structure of product (c) law of active mass
is more disordered as compared to reactants (d) Both (a) and (b)
entropy of reaction increases and if the structure of (iv) The reaction A ¾® C proceeds through two
reactant is more disordered than products, it results paths I and II as shown below
in decreased entropy. Path I
A C
According to Hess’s law of constant heat summation, DH
‘‘the total heat change (DH) accompanying a DH1 DH2
chemical reaction is the same whether the reaction B
takes place in one or more steps’’.
Path II
If a reaction takes place in several steps then its
standard reaction enthalpy is the sum of the The correct relationship between DH, DH1 and DH 2
standard enthalpies of the intermediate reactions will be
into which the overall reaction may be divided at the (a) DH = DH 2 - DH1 (b) DH = DH1 / DH 2
same temperature. Suppose, enthalpy change for (c) DH = DH1 + DH 2 (d) DH = DH1 ´ DH 2
direct conversion A ¾® B is DH, Or
B can also be prepared from A through AB(s)
I
A+ (aq) + B – (aq)
intermediates C and D, for which enthalpy changes
II III
are DH1 , DH 2 and DH 3 respectively as shown in the
above side figure.
A+ (g) + B – (g)
Identify I, II, III in the above diagram. 7. Give the appropriate reason
I II III (i) It is preferable to determine the change in enthalpy
D sol H° rather than the change in internal energy.
(a) D lattice H° D hyd H°
(ii) It is necessary to define the ‘standard state’.
(b) D lattice H° D sol H° D hyd H°
(iii) It is necessary to specify the phase of reactants and
(c) D sol H° D lattice H° D hyd H° products in a thermochemical equation.
(d) D sol H° D hyd H° D lattice H ° 8. 10 g of argon is compressed isothermally and
reversibly at a temperature of 27°C from 10 L to
5 L. Calculate q, W , DU and DH for this process.
PART 2 R = 2. 0 cal K -1 mol -1 , log 2 = 0. 30,
atomic weight, of Ar = 40.
Subjective Questions 9. Given, N 2 (g)+3H2 (g) ¾® 2NH 3 (g);
D r H° = - 92.4 kJ mol -1
l
Short Answer Type Questions What is the standard enthalpy of formation of NH 3
1. 1 mole of an ideal gas undergoes reversible gas ? (NCERT)
isothermal expansion from an initial volume of V1 to 10. The value of D f H s for NH 3 is - 91.8 kJ mol -1 .
a final volume of 10 V1 and does 10 kJ of work. The Calculate enthalpy change for the following reaction.
initial pressure was 1 ´ 10 7 Pa. 2NH 3 ( g) ¾® N 2 ( g) + 3H 2 ( g) (NCERT Exemplar)
(i) Calculate V1
(ii) If there were 2 moles of gas, what must its temperature 11. Enthalpies of formation of CO (g), CO 2 (g), N 2O (g)
have been? and N 2O 4 ( g) are - 110, - 393, 81 and 9.7 kJ mol -1
respectively. Find the value of D r H for the reaction.
2. 1.0 mole of a monoatomic ideal gas is expanded
N 2O4( g ) + 3CO( g ) ¾® N 2O( g ) + 3 CO2( g )
from state (1) to state (2) as shown in figure.
Calculate the work done for the expansion of gas 12. 18.0 g water completely vaporises at 100°C and
from state (1) to state (2) at 298 K. (NCERT Exemplar) 1 bar pressure and the enthalpy change in the
2.0 State (1) process is 40.79 kJ mol -1 . What will be the enthalpy
change for vaporising two moles of water under the
p (bar)
same conditions? What is the standard enthalpy of

1.0
vaporisation for water ?
State (2)
13. The net enthalpy change of a reaction is the energy
22.7 V(L)
required to break all the bonds in reactant
3. How will you calculate the work done on an ideal molecules minus amount of energy required to
gas in a compression, when change in pressure is form all the bonds in the product molecules. What
carried out in infinite steps? (NCERT Exemplar) will be the enthalpy change for the following
reaction.
4. The enthalpy change for the reaction, H 2 ( g) + Br2 ( g) ¾® 2HBr ( g)
Zn(s ) + 2H + ( aq) ¾® Zn 2+ ( aq) + H 2 ( g), is
Given that bond energy of H 2 , Br2 and HBr is
- 154. 40 kJ mol -1 . The formation of 2 g of
hydrogen expands the system by 22.4 L at 1 atm 435 kJ mol -1 , 192 kJ mol -1 and 368 kJ mol -1
pressure. respectively. (NCERT Exemplar)
What is the internal energy change of the reaction? 14. Calculate the enthalpy change for the process
5. Calculate the work done when 11.2 g of iron CCl 4 ( g) ¾® C( g) + 4Cl( g)
dissolves in hydrochloric acid in and calculate the bond enthalpy of C—Cl in CCl 4 ( g)
(i) a closed vessel D vap H° (CCl 4 ) = 30.5 kJ mol -1
(ii) an open beaker at 25°C (Atomic mass of Fe = 56 u ) D f H° (CCl 4 ) = - 135.5 kJ mol -1
6. Although heat is path function but heat absorbed by D aH° (C) = 715.0 kJ mol -1
the system under certain specific conditions is
independent of path. What are those conditions? where, D aH° is enthalpy of atomisation,
Explain. (NCERT Exemplar) D aH° (Cl 2 ) = 242 kJ mol -1 (NCERT Exemplar)
15. Use the following data to calculate D lattice H° for NaBr. 22. (i) A cylinder of gas supplied by a company is assumed
D sub H° for sodium metal = 108.4 kJ mol -1 to contain 14 kg of butane. If a normal family
Ionisation enthalpy of sodium = 496 mol -1 requires 20000 kJ of energy per day for cooking,
Electron gain enthalpy of bromine = - 325 kJ mol -1 how long will the cylinder last?
Bond dissociation enthalpy of bromine = 192 kJ mol -1 (ii) If the air supplied to the burner is insufficient, a
D f H° for NaBr(s ) = - 360.1 kJ mol -1 (NCERT Exemplar) portion of gas escapes without combustion.
Assuming that 25% of the gas is wasted due to this
16. Calculate the entropy change in surroundings when inefficiency, how long will the cylinder last (Heat of
1.00 mole of H 2O( l ) is formed under standard
combustion of butane = 2658 kJ/mol.)?
conditions. D f H° = - 286 kJ mol -1 . (NCERT)
17. Taking a specific example, show that DS total is a 23. (i) An athlete is given 100 g of glucose of energy
criterion for the spontaneity of a change. equivalent to 1560 kJ. He utilises 50% of this
gained energy in the event. In order to avoid
18. Calculate the standard Gibbs energy change for the storage of energy in the body, calculate the weight
formation of propane at 298 K.
of water that would need to perspire. The enthalpy
3C(graphite) + 4H 2 ( g) ¾® C 3H 8 ( g)
of vaporisation of water is 44 kJ mol -1 .
D f H° for propane, C 3H 8 ( g) is -103.8 kJ mol -1
(ii) Compound with carbon-carbon double bond, such
Given, S°m C 3H 8 ( g) = 270.2 JK -1 mol -1 as ethylene,C 2H 4 , react with hydrogen in a reaction
S°m C (graphite) = 5.70 JK -1 mol -1 called hydrogenation,
C 2H 4 ( g) + H 2 ( g) ¾® C 2H 6 ( g)
and S°m H 2 (g) = 130.7 JK -1 mol -1 Calculate enthalpy change for the reaction, using the
19. For the reaction, 2 A(g) + B(g) ¾® 2D(g); following combustion data
C 2H 4 ( g) + 3O 2 ( g) ¾® 2 CO 2 ( g) + 2 H 2O( l );
DU° = - 10.5 kJ and DS° = - 44.1 JK -1 . D cH° = - 1401 kJ mol -1 …(i)
Calculate DG° for the reaction and predict whether 7
the reaction may occur spontaneously. C 2H 6 ( g) + O 2 ( g) ¾® 2 CO 2 ( g) + 3 H 2O ( l )
2
(R = 8. 314 ´ 10 -3 kJ K -1 mol -1 , T = 298 K ) (NCERT)
D cH° = - 1550 kJ mol -1 …(ii)
20. Justify the following statements 1
(i) Many thermodynamically feasible reactions do not H 2 ( g) + O 2 ( g) ¾® H 2O ( l );
2
occur under ordinary conditions.
D cH° = - 286.0 kJ mol -1 …(iii)
(ii) At low temperature, enthalpy change dominates
the value of DG and at high temperature, it is the 24. Using the data (all values are in kilocalories per mole
entropy which dominates the value of DG in at 25°C) given below, calculate the bond energy of
Gibbs-Helmholtz equation. C— C and C—H bonds.
DH°comb (ethane) = - 372. 0
l
Long Answer Type Questions DH°comb (propane) = - 530.0
21. The figure given below represents pV diagram DH° for C(graphite) ¾ ¾® C( g) = 172. 0
of different stages of a thermodynamic Bond energy of H—H = 104. 0
process. Calculate the work done in each stage and
also the net work done in the complete cyclic D f H° of H2 O ( l ) = - 68. 0
process. DH° for CO 2 ( g) = - 94. 0
25. (i) Calculate D r H° for the reaction,
× 105
H ¾ C == C ¾ H + 3O == O ¾ ¾®
Pressure (Nm–2)
12 A B
10
½ ½ 2O == C == O + 2H—O —H
8 H H
6 The average bond enthalpies of various bonds are
4 D C Bond C ¾H O == O C == O O ¾H C == C
2
1 2 3 4 5 6 7 8 Bond enthalpy
414 499 724 460 419
(kJ mol -1)
Volume (L)
(ii) The standard molar enthalpies of formation of mechanical or any other form of energy that anyone
cyclohexane ( l ) and benzene (l) at 25° C are may think of. However, gravitational energy is
-156 and + 49 kJ mol -1 respectively. The standard generally neglected.
enthalpy of hydrogenation of cyclohexene ( l ) at It is a state function, i.e. independent of the path
25°C is - 119 kJ mol -1 . Use these data to estimate followed. It may change when
the magnitude of the resonance energy of benzene. (i) heat flows in or out of the system,
26. Sodium carbonate, Na 2CO 3 can be obtained by (ii) work is done on or by the system,
heating sodium hydrogen carbonate, NaHCO 3 as (iii) matter enters or leaves the system.
2NaHCO 3 (s ) ¾® Na 2CO 3 (s ) + H 2O( g)+CO 2 ( g). It is an extensive property, i.e. depends upon the
The essential data are mass of the substance. It depends only on
NaHCO3 (s ) Na 2 CO3 (s) CO2 (g) H 2 O(g)
temperature. The absolute value of internal energy
possessed by a substance cannot be calculated
D f H° -947.7 -1130.9 -393. 51 -241.82
(kJ mol -1 ) because it is not possible to predict the exact
values of different forms of energy.
S °m 102.1 136 188.83 213.74
(J mol -1 ) Thus, we can just calculate the change in internal
Calculate the temperature above which NaHCO 3 energy, which is achieved by changing the state of a
system.
decomposes to give products at 1 bar.
First law of thermodynamics was proposed by
27. (i) A gas expands isothermally against a constant Helmholtz and Robert-Mayer who stated that the
external pressure of 1 atm from a volume of 10
energy of an isolated system is constant, i.e. energy
dm 3 to a volume of 20 dm 3 . It absorbs 800 J of
can neither be created nor be destroyed but can be
thermal energy from its surroundings. Calculate
converted from one form to another. That’s why it is
the change in internal energy (DE).
also called law of conservation of energy. When a
(ii) DH for the reaction, system undergoes isothermal change DU = 0, i.e.
C(graphite)+2H2 ( g) ¾® CH4 ( g) at 298 K and there is no increase or decrease in the internal
1 atm is -17900 cal. Calculate DE for the above energy of the system then the first law of
conversion. thermodynamics reduces to 0 = q + W or q = - W.
(iii) DG for a reaction at 300 K is -16 kcal and DH is (i) Neither q nor W is a state function but q + w is a
-10 kcal. What is the entropy of the reaction? state function. Explain why?
28. (i) 10 moles of an ideal gas expand isothermally and (ii) Out of mass and density, which is an intensive
reversibly from a pressure of 5 atm to 1 atm at property and why?
300 K. What is the largest mass that can be lifted (iii) Explain thermodynamically how is the heat
through a height of 1 m by this expansion? absorbed by system is used in doing work at
(ii) Predict in which of the following, entropy constant temperature and pressure.
increases/decreases. (iv) What is the change in the energy of system if
(a) A liquid crystallises into a solid. 500 cal of heat energy are added to a system
(b) Temperature of a crystalline solid is raised and system does 350 cal of work on the
from 0 K to 115 K. surroundings?
(c) 2NaHCO 3 (s ) ¾® Na 2CO 3 (s ) Or
+ CO 2 ( g) + H 2O (g) For the same increase in volume, why work done is
(d)H 2 (g) ¾® 2H(g) (NCERT) more if the gas is allowed to expand reversibly at
higher temperature?
l
Case Based Questions 30. Read the following and answer the questions from
29. Read the following and answer the questions from (i) to (iv) given below
(i) to (iv) given below Thermodynamics is the study of the relationship
Every system is associated with a definite amount between heat and work. The change in the enthalpy
of energy, called the internal energy (U or E) of the of the system during a chemical reaction is defined
system. It is the sum of chemical, electrical, as the change in its internal energy plus the change
in the product of the pressure times the volume of their more regular crystalline structure liquids have
the system. As enthalpy is a state function and it is an intermediate entropy as they are more ordered
dependent on the change between the initial and than gas but less ordered than solids. Gases are
the final state. Based on this, we can define two known to have the highest entropy as they have the
types of chemical reactions exothermic and most disorder.
endothermic. In order to define the relationships that exists
Exothermic reactions are those in which there is a between entropy and enthalpy.
release of heat and energy is given out of the Gibbs free energy is used to measure the amount of
surroundings. Endothermic reactions are those in available energy that a chemical reaction provides.
what there is an absorption of heat from the
(i) Is enthalpy a state function?
surroundings environment.
(ii) Draw enthalpy diagram for endothermic
Entropy refers to the measure of the level of
reaction.
disorder in a thermodynamic system. It is measured
as Joules per Kelvin (J/K) and denoted by the (iii) Are all exothermic reaction spontaneous?
symbol ‘S’. For any spontaneous process, the (iv) Why is molar entropy of vaporisation for water
entropy of the system should increase. more than ethanol?
Entropy is the measure of the number of possible Or
microscopic configurations of the atoms and For the reaction, 2Cl( g) ¾® Cl 2 ( g),
molecules or accordance with the microscopic state What are the signs of DH and DS ? (NCERT)
of the system. Solids have lowest entropy due to
EXPLANATIONS
Objective Solutions Q We have to find DH for the reaction
1
1. (c) Among the given option internal energy depend on heat. CO + O2 ¾® CO2 ; DH = ?
When no exchange of heat takes place between the system 2
and surroundings, i.e. dq = 0 then the system exist in a \ On subtracting Eq. (i) from Eq. (ii), we get
thermally isolated state. DH = - 94 - ( - 26. 4) = - 67. 6 kcal
2. (d) The state of a gas can be described by quoting the
9. (b) Given, 4H (g ) ¾® 2H 2 (g ); DH = -869.6 kJ
relationship between pressure, volume, temperature and
amount. The ideal gas equation is \ 2H 2 ( g) ¾® 4H( g); DH = 869.6 kJ
pV = nRT Thus, dissociation energy of H ¾ H bond
Thus, p,V,T and n describe the state of the system. 869.6
= = +434.8 kJ
3. (b) Temperature ( T ) will still remain the same, because 2
volume is an extensive property and temperature is an 10. (b) Statement (b) is correct, while the other statements are
intensive property. incorrect. Corrected form are as follows
Thus, statement (b) is correct. l Combustion reactions are exothermic in nature.
4. (c) Free expansion, W = 0 l Our body generates energy from food by the same overall
process as combustion, although, the final products are

Adiabatic process, q = 0
produced after a series of complex biochemical reaction
DU = q + W = 0, this means that internal energy remains involving enzymes.
constant. Therefore, DT = 0. In ideal gas there is no 100 ° C
intermolecular attraction. 11. (a) Given, H2 O(l ) ¾¾® H2 O(g )
Hence, when such a gas expands under adiabatic As we know that, D vapH° = D vap U°+ Dn gRT
conditions into a vacuum, no heat is absorbed or D vapH° = enthalpy of vaporisation
evolved since no external work is done to separate the
= 40.66 kJ mol -1
molecules.
For the above reaction,
5. (c) Combustion of elements to form a compound can be Dn g = n p - n r = 1 - 0 = 1
exothermic or endothermic.
R = 8. 314 J/mol K
e.g. C + O2 ¾® CO2 is exothermic.
T = 100° C = 273 + 100 = 373K
whereas, C + 2S ¾® CS2 is endothermic. \ 40. 66 kJ mol -1 = D vap U°+1 ´ 8. 314 ´ 10-3 ´ 373
Hence, enthalpy of formation can be positive or negative. D vap U° = 40.66 -3.1 = + 37.56 kJ mol -1
6. (a) Exothermic reactions are those reactions which are 12. (d) (i) I2 (s) ¾® I2 ( g) ; DH1 = +57.3 kJ mol –1
accompanied by the evolution of heat.
e.g. C(s) + O2 ( g) ¾® CO2 ( g) + 393.5 k J (ii) I2 (s) ¾® I2 ( l ) ; DH 2 = +15.5 kJ mol –1
(iii) I2 ( l ) ¾® I2 ( g) ; DH = ?
1
H 2 ( g) + O2 ( g) ¾® H 2 O( l ) + 285.8kJ Eq. (iii) will be obtained, if we substract Eq. (ii) from (i), i.e
2
(iii) = (i) - (ii)
q p and D r H are negative for exothermic reaction.
Now, DH = 57.3 - 15.5 = + 41.8 kJ mol –1
7. (d) From the equation, 13. (c) Molar entropy change for the melting of ice,
15 DH fusion 1.435 kcal / mol
C6 H6 ( l ) + O2 ( g) ¾® 6CO 2 ( g) + 3H2 O( l ) DSmelt = =
2 T (0 + 273)K
Change in the number of gaseous moles, i.e.
= 5.26 ´ 10-3 kcal/ mol K
15 3
Dn g = 6 - =- or -1. 5 = 5.260 cal/mol K
2 2
14. (a) As we know that,
Now we have Dn g and other values given in the question are
DStotal = DSsys + DS surr
DU = - 3263. 9 kJ/mol
For DSsurr, we have to consider the heat absorbed by the
T = 25° C surroundings which is equal to - D r H°. At temperature
= 273 + 25 = 298 K ( T ), entropy change of the surroundings is
R = 8. 314 JK-1mol -1 D H°
DSsurr = - r (at constant pressure)
So, DH p = ( -3263. 9) + ( -1. 5) ´ 8. 314 ´ 10-3 ´ 298 T
= - 3267. 6 kJ mol -1 -( -1648 ´ 103 J mol –1 )
= = 5530 JK–1 mol –1
8. (d) Given, 298 K
1 D r Stotal = 5530 + ( -549.4)
C(s) + O2 ( g) ¾® CO( g); DH1 = - 26.4 kcal ...(i)
2 = 4980.6 JK –1 mol –1
C(s) + O2 ( g) ¾® CO2 ( g); DH 2 = -94.0 kcal ...(ii) Hence, the above reaction is spontaneous.
15. (b) DG gives a criteria for spontaneity at constant pressure (ii) (c) CaCO3 (s) ¾® CaO(s) + CO2 ( g)
and temperature.
°
D r H° = S a i D f H(Products) - S b i D f H°(Reactants)
(i) If DG is negative (< 0), the process is spontaneous. i i
(ii) If DG is positive (> 0), the process is at where, a and b are represent the coefficients of the
non-spontaneous. products and reactants in the balanced equation.
(iii) If DG is zero then reaction is at equilibrium. D r H° = D f H° [ CaO(s)] + D f H° [CO2 ( g)]
16. (d) A is false, but R is true. - D f H° [CaCO3 (s)]
Volume of water in a pond is a state function because change = 1 ( -635.1 kJ mol –1 ) + (1) ( -393.5 kJ mol –1 )
in volume of its water is independent of the route by which -1 ( -1206.9 kJ mol –1 )
-1
water is filled in the pond, either by rain or by tubewell or = 178.3 kJ mol
by both. (iii) (b) Hess’s law is based on conservation of energy.
17. (a) Both A and R are true and R is the correct explanation of A. According to this law, total heat change is independent of
The properties whose magnitude depends upon the quantity the path followed by chemical reaction.
are extensive property. (iv) (c) According to Hess’s law; the total heat change ( DH )
18. (a) Both A and R are true and R is the correct explanation of A. accompanying a chemical reaction is the same, whether
As internal energy is a state function so, its value depends on the reaction takes place in one or more steps or follows
initial and final state of the system. As in case of cyclic one or more paths.
system initial and final state are same. Therefore, the correct relation between DH and
So, DE = 0. DH1 , DH 2 will be
19. (b) Both A and R are true, but R is not the correct explanation D H = D H1 + D H 2
of A. Or
20. (b) Both A and R are true, but R is not the correct D sol H°
explanation of A. (c) AB (s) ¾¾¾® A + ( aq) + B - ( aq)
In a combustion reaction, sum of enthalpies of reactants is D latticeH° D hydH°
greater than the sum of the enthalpies of products and
therefore is an exothermic reaction. Moreover, enthalpies of
A + ( g) + B - ( g)
the elements in the standard state are zero.
The enthalpy of solution AB(s), D solH° in water is
21. (i) (b) Here, as Na transforms from solid to gaseous state,
determined by the selective values of the lattice
this process is called sublimation.
enthalpy, ( D latticeH° ) and enthalpy of hydration of ions
(ii) (b) The standard enthalpy change for the formation of
( D hydH° ) as D sol H° = D latticeH°+ D hyd H°
one mole of a compound from its elements in their most
stable states of aggregation is called standard molar Subjective Solutions
enthalpy of formation.
V2
(iii) (d) Conversion or melting of solid to liquid state is 1. (i) We know that W = -2.303 nRT log
called fusion. V1
10 V1
(iv) (c) Unit of D r H is kJ mol - 1 enthalpy is an extensive 10 ´ 10 3 J = 2.303 ´ 1 ´ 8.314 ´ T ´ log
V1
quantity. The sign of D r H changes but magnitude or T = 522.3 K
remains same on reversing the chemical reaction. For initial conditions, p1V1 = n 1RT ,
Or i.e. (10 7 Pa) V1 = 1 ´ 8.314 ´ 522.3
(b) The reaction is
CH 4 ( g) + 2 O2 ( g) ® CO2 ( g) + 2H 2 O( l ) or V1 = 4.342 ´ 10 -4 m 3
Dn g = ( n p - n r )g = 1 - 3 = - 2 = 4.342 ´ 10 2 cm 3
D f H - s = D f U s + Dn g RT = 434.2 cm 3
As Dn g = -2 (ii) If there were 2 moles of the gas, applying p1V1 = n 1RT ,
we get (10 7 Pa)(4.342 ´ 10 -4 m 3 ) = 2 ´ 8.314 ´ T
\ D f H s < D f Us
or T = 261.1 K, i.e. half of the first value.
22. (i) (a) Given, DH°f (NH 3( g)) = - 81.9 kJ mol -1; 2. The given diagram represents that the process is carried out
Mass of NH 3 = 26 g in infinite steps, hence, it is isothermal reversible expansion
Mass of the ideal gas from pressure 2.0 atm to 1.0 atm at 298 K.
Q Number of moles of NH 3 = p
Molecular mass W = - 2.303 nRT log 1
26 p2
= = 1.53
17 W = - 2.303 ´ 1 mol ´ 8.314 JK-1mol -1
æ p 2ö
Now, heat of decomposition for 1.5 moles of NH 3 ´ 298 K log 2 çQ 1 = ÷
è p2 1 ø
= number of moles ´ standard enthalpy W = -1717.63 J
= 1. 5 ´ 81. 9 = 122. 9 kJ
3. When compression is carried out in infinite steps with \ q p = D H.

change in pressure, it is a reversible process. Work done on As DH is a state function, therefore, q p is a state function.
the gas is represented by the shaded area.
7. (i) Yes it is preferable to determine the change in enthalpy
pf because it is easier to make measurement under constant
pressure (DH) than under constant volume DV conditions.
p
(ii) Yes it is necessary because enthalpy change depends upon
the conditions in which a reaction is carried out. For making
the comparison of results obtained by different people
meaningful, the reaction conditions must be well defined.
pi
(iii) Yes it necessary to specify the phase of reactants and
Vf Vi products in a thermochemical equation because enthalpy
Volume (V)
change depends upon the phase of reactants and products.
4. Taking the initial volume as negligible (as no gaseous V
reactant is present), change in volume during expansion 8. q = 2.303 nRT log 2
V1
( DV ) = 22. 4 L. External pressure ( p ext ) = 1 atm
10 5
DH = DU + pDV or DU = DH - pDV = 2.303 ´ ´ 300 ´ log = - 103.635 cal
pDV = 1 atm ´ 22.4 L = 22.4 L atm 40 10
= 22. 4 ´ 101. 3 J = 2307 J = 2.31 kJ For isothermal expansion, DU = 0
\ DU = - 154. 4 - 2 . 31 = - 156.71 kJ W = DU - q = 0 - ( - 103.635) = + 103.635 cal
5. Iron reacts with hydrochloric acid to produce H2 gas as Also, when temperature is constant,
Fe (s) + 2HCl( aq) ¾® FeCl 2 ( aq) + H2 ( g) p1V1 = p 2 V2 or pV = constant
Thus, 1 mole of Fe, i.e. 56 g Fe produces H2 gas = 1 mol. DH = DE + D( pV ) = 0 + 0 = 0
1 ¾® 2NH3 ( g); D r H° = -92.4 kJ mol -1
9. Given, N 2 ( g) + 3H2 ( g) ¾
\ 11.2 g Fe will produce H2 gas = ´ 11.2 = 0.2 mol
56 Chemical reaction for the enthalpy of formation of NH3 (g) is as
(i) If the reaction is carried out in closed vessel, DV = 0 follows
1 3
\ W = - p ext DV = 0 N 2 ( g) + H2 ( g) ¾® NH3 ( g)
2 2
(ii) If the reaction is carried out in an open beaker (external -92.4
pressure being 1 atom). Therefore, D f H° = = -46.2 kJ mol -1
2
Initial volume = 0 1 3
Final volume can be calculated as follows 10. Given, N2 (g) + H2 (g) ¾® NH 3 (g);
2 2
pV = nRT D f H s = - 91.8 kJ mol -1
nRT (D f H s means enthalpy of formation of 1 mole of NH3 )
V=
p \ Enthalpy change for the formation of 2 moles of NH3
0.2 mol ´ 0.0821L atm K -1mol -1 ´ 298K N 2 (g) + 3H2 (g) ¾® 2NH3 (g);
=
1 atm D f H s = 2 ´ -91. 8 = - 183.6 kJ mol -1
= 4.89 L And for the reverse reaction,
\ DV = Vf - Vi = 4.89 2NH 3 (g) ¾® N 2 (g) + 3H 2 (g); D f H s = + 183.6 kJ mol – 1
W = - p ext DV ° °
11. Heat of reaction, D r H° = SD f HProducts - SD f HReactants
= -1 ´ 4.89
= [ D f H° (N 2 O) + 3D f H° (CO 2 ) ] - [ D f H° (N 2 O 4 ) + 3D f H° (CO) ]
= - 489 L atm
= [81 + (3 ´ - 393)] - [9.7 + (3 ´ - 110)] kJ
= - 4.89 ´ 101.35
= - 495.4 J = - 777.7 kJ » - 778 kJ
6. The two conditions under which heat becomes independent 12. 18.0 g H2 O = 1 mol H2 O
of path are Enthalpy change for vaporising 1 mole of H2 O = 40.79 kJ
(i) when volume remains constant \ Enthalpy change for vaporising 2 moles of
(ii) when pressure remains constant H2 O = 2 ´ 40.79 kJ = 81.58 kJ
(a) At constant volume By first law of thermodynamics, Standard enthalpy of vaporisation at 100°C and 1 bar pressure,
DU = q + W or q = DU - W. But W = - pDV.
D vapH° = + 40.79 kJ mol -1
Hence, q = DU + pDV. But as volume remains
constant, DV = 0. 13. H2 ( g) + Br2 ( g) ¾® 2HBr ( g)
\ q V = DU. But DU is state function. Hence, q V is D r H° = SBE (reactants) - SBE (products) = BE(H 2 )
state function. + BE(Br 2 ) - 2BE(HBr)
(b) At constant pressure q p = DU + pDV. = 435 + 192 - (2 ´ 368) kJ mol -1
But DU + pDV = DH. = - 109 kJ mol -1
14. Given, 18. 3C(graphite) + 4H2 (g) ¾® C3 H8 (g)

(i) CCl 4 ( l ) ¾® CCl 4 ( g) ; D vapH° = + 30.5 kJ mol -1 D r S = SS°m (products) - S°m (reactants)
(ii) C(s) + 2Cl 2 ( g) ¾® CCl 4 ( l ); D f H° = - 135.5 kJ mol -1 D r S = S°m [C 3 H8 (g) - 3S°m [ C (graphite)] + 4S°m [ H2 ]]
(iii) C(s) ¾® C( g); D aH° = 715.0 kJ mol -1 = (270.2 - 3 ´ 5.70 - 4 ´ 130.7 ) JK-1mol -1
(iv) Cl 2 ( g) ¾® 2Cl( g) ; D aH° = 242 kJ mol -1 = (270.2 - 17.10 - 522. 80) JK-1mol -1
Multiplying Eq. (iv) by 2, we get = (270.2 - 539. 90) = - 269.7 JK-1mol -1
-1
(v) 2Cl 2 ( g) ¾® 4Cl( g) ; D aH° = 484.0 kJ mol D r H° = D f H° products - D f H° reactants
Adding Eqs. (iii) and (v), we get D r H° = D f H° (C 3 H8 ) - 4D f H° [ H2 ( g)] - 3D f H° [C (graphite)]
(vi) C(s) + 2 Cl 2 ( g) ¾® C( g) + 4Cl( g) ;DH = 1199 kJ mol -1 D r H° = - 103.8 kJ mol -1; D r G° = D r H° - TD r S°
Reversing Eqs. (i) and (ii), we get æ 298 ´ ( - 269.7) ö -1
= ç - 103.8 - ÷ kJ mol
(vii) CCl 4 ( g) ¾® CCl 4 ( l ) ; DH = - 30.5 kJ mol -1 è 1000 ø
(viii) CCl 4 ( l ) ¾® C(s) + 2 Cl 2 ( g) ; DH = + 135.5 kJ mol -1 = ( - 103.80 + 80.370) kJmol -1 = - 23. 43 kJ mol -1
Adding Eqs. (vi), (vii) and (viii), we get 19. We know that DG° = DH° - TDS° so first find DH° by using
CCl 4 ( g) ¾® C( g) + 4Cl( g) ; DH = 1304 kJ mol -1 the formula, DH = DU + Dn gRT and then DG° by putting
Bond enthalpy of C— Cl bond in the values of DH°, T and DS°.
1304 For a spontaneous reaction DG £ 0.
CCl 4 = = 326 kJ mol -1
4 2 A( g) + B( g) ¾® 2D( g); Dn g = n p - n r = 2 - 3 = - 1
Cl
DH° = DU° + Dn gRT;
½
(Q There are four C—Cl bonds in CCl 4 , Cl ¾ C ¾ Cl.) DH° = - 10.5 kJ + ( -1 ´ 8.314 ´ 10 -3 kJ K-1mol -1 ´ 298 K)
½ = - 12.977 kJ mol -1
Cl DG° = DH°- TDS°;
15. Born-Haber cycle for the formation of NaBr is as
DG° = –12.977 kJ mol -1 - (298 K ´ - 44.1 ´ 10 -3 kJ K-1mol -1 )
∆f H ° = – 360.1 kJ
Na(s) + 1 Br2(g) NaBr(s) = 0.16 kJ mol - 1
2
∆subH° = 108.4 kJ mol–1 ∆dissH° = 192/2 kJ The reaction will not occur spontaneously because DG° is
positive.
Na(g) Br(g)
IE = 496 kJ mol–1 ∆egH ° = – 325 kJ mol–1
20. (i) Many thermodynamically feasible reactions do not
occur under ordinary conditions because under
Na+(g) Br–(g)
ordinary conditions, the average energy of the reactants
–U (Lattice enthalpy) may be less than threshold energy.
Thus, they require some activation energy to initiate
By applying Hess’s law,
the reaction.
D f H° = D subH° + IE + D dissH° + D e g H° + U
(ii) From Gibbs-Helmholtz equation, we have
- 360.1 = 108.4 + 496 + 96 + ( - 325) - U; U = + 735.5 kJ mol -1
DG = DH - TDS.
16. Enthalpy change for the formation of 1 mole of H2 O ( l ), At low temperature, TDS is small, hence, DH
1 dominates. At high temperature, TDS is large, i.e. DS
H2 ( g) + O2 ( g) ¾® H2 O( l ); D f H° = - 286 kJ mol -1 dominates the value of DG.
2
Energy released in the above reaction, is absorbed by the 21. Process A ¾® B (isobaric expansion),
surroundings. p = 12 ´ 105 Nm -2 , DV = 8 - 2 = 6 L = 6 ´ 10-3 m 3
It means q surr = + 286 kJ mol -1 \ Work done = - pDV= - (12 ´ 105 ) ´ ( 6 ´ 10-3 ) J = - 7200 J
q + 286 kJ mol -1 Isochoric process B ¾® C.
DS = surr =
T 298 K No change in volume, i.e. DV = 0
= 0.9597 = 959.7 JK-1mol -1 \ Work done = 0
17. For spontaneous process, DStotal must be positive, Process C ¾® D (isobaric contraction)
i.e. DStotal = DS system + DS surroundings > 0. DV = 8 - 2 = 6L = 6 ´ 10 -3 m 3 , p = 4 ´ 10 5 Nm -2
Consider the freezing of water at 272 K and 1 atm pressure. \ Work done, pDV = ( 4 ´ 105 )( 6 ´ 10-3 ) = 2400 J
For this process, DSsystem = - 21. 85 J K-1mol -1 Process D ® A is isochoric because there is no change in
DSsurroundings = + 21. 93 J K-1mol -1 volume. No change in volume, i.e. DV = 0
\ DStotal = - 21. 85 + (21. 93) \ Work done = 0
= + 0. 08 J K-1mol -1 \ Net work done in the complete cyclic process
As DStotal is positive, the freezing of water at 272 K and 1 atm = -7200 + 2400 J = -4800 J
pressure is spontaneous. Minus sign shows that net work has been done by the gas.
22. (i) Molecular formula of butane = C 4 H10 H H

| |
Molecular mass of butane = 4 ´ 12 + 10 ´ 1 = 58 i.e. H ¾ C ¾ C ¾ H ¾® 2 C( g) + 6H;
Heat of combustion of butane = 2658 kJ mol -1 | |
1 mole or 58 g of butane on complete combustion gives H H
heat = 2658 kJ DH = x + 6y …(vii)
and for C 3H 8 ( g) ; i.e.
\ 14 ´ 103 g of butane on complete combustion will
2658 ´ 14 ´ 103 H H H
give heat = = 641586
58 | | |
The family needs 20000 kJ of heat per day. H ¾ C ¾ C ¾ C ¾H ¾® 3 C ( g) + 8 H ( g);
| | |
Q 20000 kJ of heat is used for cooking by a family in 1 day H H H
\ 641586 kJ of heat will be used for cooking by a family DH = 2 x + 8y ...(viii)
641586 To get Eq. (vii), operate Eq. (i) + 2 ´ Eq. (iii) + 3 ´ Eq.
in = 32 days
20000 (iv) - 3 ´ Eq. (v) - 2 ´ Eq. (vi).
The cylinder will last for 32 days.
It gives DH = 676 kcal
(ii) 25 per cent of the gas is wasted due to inefficiency. This To get Eq. (viii), operate Eq. (ii) + Eq. (iii) + 4 ´ Eq (iv)
means that only 75% of butane gets combusted. - 4 ´ Eq. (v) - 3 ´ Eq (vi).
Therefore, the energy produced by 75% combustion of It gives DH = 956 kcal
641586 ´ 75 Thus, x + 6y = 676, 2 x + 8y = 956
butane = = 481189. 5 kJ
100 On solving these equations, we get
\ The number of days the cylinder will last x = 82 , y = 99
481191
= 24.05 days Hence, C—C bond energy = 82 kcal mol -1 and C—H
20000 bond energy = 99 kcal mol -1.
23. (i) 100 g of glucose is equivalent to 1560 kJ of energy 25. (i) In the given reaction, four C—H bonds, one C == C
1560 ´ 50 bond and three O== O bonds are broken and four C == O
Energy utilised in the event = = 780
100 bonds and four O—H bonds are formed. Thus,
Energy left unutilised = 1560 - 780 = 780 kJ DH° = [4 ´ (bond enthalpy of C—H) + (bond enthalpy
44 of C == C) + 3 ´ (bond enthalpy of O== O)] - [4 ´ (bond
Enthalpy of vaporisation of water = 44 kJ/mol = kJ/g enthalpy of C == O) + [ 4 ´ (bond enthalpy of O—H)]
18
44
\Water needed to perspire = ´ 780 = 1906.66 g DH = ( 4 ´ 414 + 619 + 3 ´ 499) - ( 4 ´ 724 + 4 ´ 460)
18 = - 964 kJ mol -1
(ii) Adding Eqs. (i), (iii) and substract Eq. (ii), (ii) Standard enthalpy of hydrogenation of cyclohexene
1
C 2 H4 ( g) + 3 O 2 ( g) + H2 ( g) + O 2 ( g) - C 2 H6 ( g) = - 119 kJ mol -1. This is the observed enthalpy of
2 hydrogenation of one double bond in cyclohexene
7
- O 2 ( g) ¾®2 CO 2 ( g) + 2 H2 O ( l ) + H2 O( l ) (present in cyclohexene).
2
If benzene is considered as cyclohexatriene, then
- 2 CO 2 ( g) - 3 H2 O( l )
observed enthalpy of the reaction would be
and D r H° = - 1401 kJ mol – 286.0 kJ mol -1
-1
= 3 ´ ( - 119) = - 357 kJ mol -1
- ( - 1550 kJ mol -1 )
These equations give,
C 2 H4 ( g) + H2 ( g) ¾® C 2 H6 ( g) ; D r H° = - 137 kJ mol -1 + 3H2
24. We are given, Benzene Cyclohexane

7
(i) C 2H 6 ( g) + O2 ( g) ¾® 2 CO2 ( g) + 3 H 2 O ; Calculated enthalpy of the above reaction is
2
DH° = - 372.0 kcal D r H = DH°f (C 6H14 ) - [ DH°f (C 6H 6 ) + 3 DH°f (H 2 )]
(ii) C 3H 8 ( g) + 5O2 ( g) ¾® 3CO2 ( g) + 4H 2 O; = - 156 - ( 49 + 0)
DH° = - 530. 0 kcal = - 205 kJ mol -1
(iii) C (s) ¾® C ( g) ; DH° = 172. 0 kcal \Resonance energy
(iv) H 2 ( g) ¾® 2 H ( g) ; DH° = 104.0 kcal = Observed D r H° – calculated D r H°
1
(v) H 2 ( g) + O2 ( g) ¾® H 2 O( l ) ; DH° = - 68.0 kcal = ( - 357 ) - ( - 205) kJ mol -1
2
= - 152 kJ mol -1
(vi) C ( g) + O2 ( g) ¾® CO2 ( g) ; DH° = - 94.0 kcal
26. 2NaHCO 3 (s) ¾® Na 2 CO 3 (s) + CO2 (g) + H2 O(g)
Suppose the bond energy of C—C bond = x kcal mol -1
and that of C—H bond = y kcal mol -1. D r H° = D f H° (Na 2 CO 3 ) + D f H° (CO 2 )
Then for C 2H 6 ( g), + D r H° (H2 O) - 2 D f H° (NaHCO 3 )
= - 1130.9 + ( - 393.51) + ( - 241.82) - 2 ´ ( - 947.7) (c) At reactant side only solid NaHCO 3 is present
= - 1766.23 + 1895.4 = 129.17 kJ mol -1 whereas at product side Na 2 CO3 ,CO2 and H 2 O are
D r S° = D r S°m (Na 2 CO 3 ) + S °m (CO 2 ) + S °m (H2 O) present. CO2 and H 2 O are in gaseous state and
- 2S°m (NaHCO 3 ) gases because of more randomness of constituent
particles have more entropy. Thus, in this reaction
= 136.0 + 188.83 + 213.74 - 2 ´ 102.1
entropy the system increases.
= 538.57 - 204.2 = 334.37 J K-1mol -1
(d) At reactant side, there is only one gaseous molecule
From second law of thermodynamics
and at product side there are two gaseous
D H°
D r S° = r atoms. Thus, randomness is more towards product
T side, i.e. entropy of two moles of H-atoms is higher
D r H° 129.17
\ T= = = 386.3 K than one mole of dihydrogen molecule.
D r S° 334.37 ´ 10 - 3
29. (i) From first law of the thermodynamics,
\ Reaction will be spontaneous above 386.3 K. DU = q + W
27. (i) Given ( r ) , p = p ext = 1 atm as q + W is equal to DU which is a state function, it
V1 = 10 dm 3 , V2 = 20 dm 3 , q = 800J does not depend upon path of reaction and only
As we know that, depends upon initial and final state.
V2 (ii) Density is an intensive property as it characteristic of a
W = – ò pext dV = – pext ( V2 – V1 ) material and does not change with amount whereas
V1
mass does change.
\ W = – 1 (20 – 10) = – 10 dm 3 atm
(iii) DU = q + W (From 1st law of thermodynamics)
= – 1013 J (Q 1 L atm = 101 . 3 J)
From the first law of thermodynamics, 0=q+ W (DU = 0, at constant temperature)
0 = q - pdV
DE = q + W
q=-W
\DE = 800 J + ( -1013 J) = – 213 J
(ii) C (graphite) + 2H 2 (g) ¾® CH 4 ( g) \Heat absorbed is used to do work by the system.
Methane (iv) According to the first law of thermodynamics ,
DH = - 17900 cal; DE = ?, Dn g = 1 - 2 = - 1 DE = q + W = 500 + ( -350) = +150 cal
Q DH = DE + Dn gRT Or
\ DH = DE – 1 ´ R ´ T For isothermal reversible expansion, W = - p int ´ DV.
– 17900 = DE – 1 ´ 298 ´ 2 At higher temperature, internal pressure of the gas is
– DE = 17900 – 596 more so work done is more.
\ DE = - 17304 cal 30. (i) Enthalpy is a state function as it depends only on initial
(iii) Given, DG = -16 kcal; DH = -10 kcal and final states of the system and is independent of path.
According to Helmholtz-Gibbs equation, (ii)
\ DG = DH - T × DS or T × DS = DH - DG Total enthalpy H
P
DH - DG -10 - ( -16) of products ∆r H
\ DS = = kcal K -1 Net heat
T 300 absorbed from
6 6 ´ 1000 the surroundings
= kcal K -1 = cal K -1 = 20 cal K -1
300 300
28. (i) W = -2. 303 nRT log p1 Total enthalpy
exp HR
p2 of reactants
5
= -2. 303 (10 ) ´ (8. 314) (300) log = -40.15 ´ 103 J
1 (iii) The condition for spontaneity does not depend on DH
If M is the mass that can be lifted by this work through but on DG. The free energy of system should decrease
a height of 1 m, then work done = Mgh and thus not all exothermic reactions are necessarily
40.15 ´ 103 J = M ´ 9. 81 ´ m s-1 ´ 1 m spontaneous.
40.15 ´ 103 kg m 2 s-2 (iv) Molar entropy of water is higher as it has greater
or M = (Q J = kg m2 s-2 ) intermolecular forces of attraction than ethanol.
9. 81 m s-2 ´ 1 m
= 4092.76 kg Or
(ii) (a) Solids have more ordered arrangement of In the given reaction, a molecule of Cl 2 is formed from
constituents as compared to liquids, thus, entropy its two gaseous atoms and the energy is released with
decreases when a liquid crystallises into a solid. the formation of bond.
(b) On raising temperature, the oscillation of constituent Hence, DH is - ve. In this reaction, randomness
particles about their equilibrium positions in the (entropy) also decreases because 2 mole atoms of Cl
lattice increases, thus the system becomes more have more randomness than one mole molecule of
disordered and hence, the entropy increases. chlorine. Hence, DS is –ve.
Chapter Test Short Answer Type Questions
8. An ideal gas is allowed to expand against a constant
pressure of 2 bar from 10 L to 50 L in one step.
Multiple Choice Questions Calculate the amount of work done by the gas. If the
1. The value of DE for an open and isolated system same expansion were carried out reversibly, will the
respectively is work done be higher or lower than the earlier case
(a) zero; non-zero (b) zero (given that 1 L bar = 100 J)? [Ans. W = - 8 kJ]
(c) non-zero; zero (d) non-zero 9. Determine the value of DH and DU for the reversible
2. The change in the energy of system if 500 cal of heat isothermal evaporation of 90.0 g of water at 100°C.
energy are added to a system and system does 350 cal Assume that water vapour behave as an ideal gas and
of work on the surroundings will be heat of evaporation of water is 540 cal
(a) –150 cal (b) +150 cal (c) + 850 cal (d) –850 cal ( R = 2.0 cal mol -1 K -1 ). [Ans. 44870 cal]
3. Which of the following statement is incorrect for the 10. Two moles of an ideal gas initially at 27°C and one
reaction? atmospheric pressure are compressed isothermally
H2( g ) + Br2(l ) ¾® 2HBr( g ); D r H ° = - 178.3 kJ mol- 1 and reversibly till the final pressure of the gas is
(a) The enthalpy change given is equal to D f H°(HBr). 10 atm. Calculate q , W and DU for the process.
(b) D rH ° = 2D f H ° (HBr) 11. (i) Enthalpy of combustion of carbon to CO 2 is
(c) D f H° of an element in refrence state is taken as zero - 393.5 kJ mol-1 . Calculate the heat released upon
(d) None of the above formation of 35.2 g of CO 2 from carbon and
4. Which of the following reactions will have the value of dioxygen gas. [Ans. 314.8 kJ mol -1 ]
DS with a negative sign? (ii) The enthalpy of a vaporisation of CCl4 is
(a) H 2O( l ) ¾® H 2O( g) 30.5 kJ mol –1 . Calculate the heat required for the
vaporisation of 284 g of CCl 4 at constant
(b) 2SO 2 ( g) + O 2 ( g) ¾® 2SO 3 ( g)
pressure. (Molar mass of CCl4 = 154 g mol –1 )
(c) Cl 2 ( g) ¾® 2Cl( g) [Ans. 56.25 kJ mol -1 ]
(d) CaCO 3 ( s ) ¾® CaO( s ) + CO 2 ( g)
(iii) Carbon monoxide is allowed to expand
Assertion Reason isothermally and reversibly form 10 m 3 to 20 m 3
Direction (Q. Nos. 5-7) Each of these questions contains at 300 K and work obtained is 4.754 kJ. Calculate
two statements Assertion (A) and Reason (R). Each of the number of moles of carbon monoxide.
[Ans. n = 2.75 mol]
these questions also has four alternative choices, any
one of which is the correct answer. You have to select Long Answer Type Questions
one of the codes (a), (b), (c) and (d) given below. 12. (i) The heat of atomisation of PH3(g) is 228 kcal mol –1
(a) Both A and R are true and R is the correct explanation of A. and that of P2H4 (g) is 335 kcal mol –1 . What is the
(b) Both A and R are true, but R is not the correct explanation energy of P ¾ P bond? [Ans. 31 kcal mol -1 ]
of A. (ii) The free energy change for the following
(c) A is true, but R is false. reactions are given below
(d) A is false, but R is true. 5
C 2H2( g ) + O 2( g ) ¾® 2CO 2( g ) +H2O(l ) ;
5. Assertion First law of thermodynamics is applicable to 2
an electric fan or a heater. DG° = - 1234 kJ
Reason In an electric fan, the electrical energy is C( s) + O 2( g ) ¾® CO 2(g); DG° = - 394 kJ
converted into mechanical work that moves the blades. In 1
a heater, electrical energy is converted into heat energy. H2( g ) + O 2( g ) ¾® H2O(l); DG° = - 237 kJ
2
6. Assertion In the equation, H = U + pV , H is a state What is the standard free energy change for the
function and independent of path. following reaction?
Reason U, p, V all are state functions.
H2( g ) + 2C( s) ¾® C 2H2( g ) [Ans. DG°= 209 kJ]
7. Assertion Chlorine when solidified does not have zero
entropy even at absolute zero. (iii) Why for predicting the spontaneity of a reaction
free energy criteria is better than the entropy
Reason Chlorine is a pungent smelling gas and it is
criteria?
difficult to solidify.
Answers
1. (c) 2. (b) 3. (a) 4. (b) For Detailed Solutions
Assertion-Reasoning MCQs Scan the code
5. (a) 6. (a) 7. (b)
CHAPTER 03
Equilibrium
In this Chapter...
l Equilibrium in Physical Processes
l Equilibrium in Chemical Processes
l Le-Chatelier's Principle
l Ionic Equilibrium
Buffer Solutions
l Solubility and Solubility Product
In a reversible reaction, the point at which there is no further Solid-Vapour Equilibrium

change in concentration of reactants and products is called Certain solids on heating directly change from solid to vapour
equilibrium state. state (sublimation).
It may be represented by
e.g. I 2 (s) r I 2 (vap.)
H 2 O( l) r H 2 O(vap.)
The mixture of reactants and products in the equilibrium
General Characteristics of Equilibria
state is called an equilibrium mixture. The concept of
equilibrium is applicable for both physical and chemical Involving Physical Processes
processes. Some important characteristics of physical equilibrium are
as follows
Equilibrium in Physical Processes l
Equilibrium is possible only in a closed system at a given
A physical equilibrium is a state at which two phases of a temperature.
compound can co-exist and an equilibrium is established l
All the measurable properties remain constant.
between these two states. Physical equilibrium may be l
Both the opposing processes occur at the same rate and
obtained by the following phase transformation processes. there is a dynamic but stable condition.
Solid-Liquid Equilibrium l
The physical equilibrium is characterised by constant value
Ice(s) r Water(l) of one of its parameter (such as melting point) at a given
Rate of melting of ice = rate of freezing of water temperature.
Liquid-Vapour Equilibrium Equilibria in Chemical Processes

H 2 O( l) r H 2 O (vap.) The equilibrium that involves only chemical change is
Rate of evaporation of water = rate of condensation of water called chemical equilibrium. It is also called dynamic
vapours equilibrium.
The variation of concentration of reactants and products in a Law of Mass Action

reversible reaction can be seen as
According to this law, ‘the rate at which a substance reacts is
proportional to its active mass and hence the rate of a
Products chemical reaction is proportional to the product of the active
Concentration
masses of the reactants’.

The term active mass means the molar concentration, i.e.
Equilibrium
Reactants reached
number of moles per litre. It is expressed by enclosing the
formula of substance in square brackets.
Thus, active mass of H 2 is represented as [H 2 ].
Time Active masses of pure solids and liquids are taken as unity
Variation of concentration of reactants and products because their concentration (or density) remain same
throughout the reaction. This is because Gibbs’ function for
Note Use of isotope (deuterium) in the formation of ammonia clearly pure solid and liquid are defined at stipulated pressure of
indicates that, chemical reactions reach a state of dynamic
1.00 bar and as the pressure of system changes, Gibbs
equilibrium in which rates of forward and reverse reactions are
function remain constant.
equal and there is no net change in composition.
Characteristics of Chemical Equilibrium Law of Chemical Equilibria and

Equilibrium Constant
The important characteristics of chemical equilibrium are as
follows Law of chemical equilibrium states that, the value obtained by
l
At a given temperature, the measurable properties like dividing the product of concentration of products raised to the
pressure, concentration, density or colour remain constant. respective stoichiometric coefficient in a balanced chemical
l
Chemical equilibrium can be attained from either side. equation by the product of concentration of reactants raised to
their individual stoichiometric coefficients is constant,
l
Chemical equilibrium remains unaffected if the
[ C] c [D] d
reaction occurs in the presence of a catalyst. However, For a reaction, aA + bB z cC + dD ; K C =
equilibrium can be attained in a lesser time by the use of [ A] a [B] b
a catalyst. where, [A], [B], [C] and [D] are molar concentration of A, B, C
l
Chemical equilibrium is dynamic in nature (i. e. the reaction and D at equilibrium and K C is equilibrium constant. The unit
does not stop but continues in both the directions with same of K C is mol L-1 .
speed). Note The above equilibrium equation is also known as law of mass
l
The chemical equilibrium will continue indefinitely if the action.
conditions such as temperature and concentration are not The characteristics of equilibrium constant are as follows
changed. l
The value of equilibrium constant for a particular reaction
l
The magnitude of such quantities at any stage indicates the is always constant and depends only upon the temperature
extent to which the reaction has proceeded before reaching of a reaction.
equilibrium. l
If the reaction is reversed, the value of equilibrium
1
constant is reversed, i.e. K C¢ = .
Types of Chemical Equilibrium KC
Depending upon the number of phases, chemical equilibrium l
If an equation is divided by a factor of ‘n’, the new
can be of following two types. equilibrium constant is the nth root of the previous value.
(i) Homogeneous Equilibrium If all the reactants and i.e. K ¢ C = (K C )1/ n .
products of an equilibrium reaction are in the same phase, l
If the equation is multiplied by a factor of ‘n’, the new
the equilibrium is called homogeneous equilibrium. equilibrium constant is nth root of the previous value.
i.e. K ¢ C = (K C ) n .
e.g. H 2 ( g ) + I 2 ( g ) r 2HI ( g )
(ii) Heterogeneous Equilibrium If all the reactants and Applications of Equilibrium Constant
products of an equilibrium reaction are not in the same The value of equilibrium constant is helpful in many ways
phase, i. e. they are present in two or more phases
Predicting the Extent of Reaction
then the equilibrium is called heterogeneous
equilibrium.
l
If K C >10 3 , products predominates over reactants and
reaction proceeds completion.
e.g. MgCO3 (s ) r MgO(s ) + CO2 ( g ) l
If K C <10 -3 , then reactants predominates over products
H 2 O( l) r H 2 O( g ) and reaction proceeds rarely.
l
If K C is in the range10 -3 to10 3 , appreciable concentrations At equilibrium, DG = 0 and Q C = K C , therefore the equation
of both reactants and products are present. becomes
Predicting the Direction of a Reaction -DG°
DG° = - RT ln K or ln K =
l
Q = K C , reaction in equilibrium. RT
l
Q < K C , reaction proceeds in forward direction. Taking antilog on both sides, we get
l
Q > K C , reaction proceeds in backward direction. K = e -DG °/ RT
Here, Q is reaction quotient. The equation, K = e -DG °/ RT helps in predicting the
spontaneity of the reaction as
Equilibrium Constant in Gaseous Systems l
If DG° < 0 ; e -DG °/ RT > 1 Þ K > 1
When all the products and reactants of a reaction are in Therefore, forward reaction is spontaneous.
gaseous state, their concentration is expressed in term of
partial pressures. If in the following reaction,
l
If DG° > 0 ; e -DG °/ RT < 1 Þ K < 1
Therefore, backward reaction is spontaneous.
aA + bB r cC + dD
The partial pressure of A, B, C and D are p A , p B , p C and p D
Factors Affecting Equilibria
respectively, then, the expression of equilibrium constant,
pc ×pd (Le-Chatelier’s Principle)
K p is given as K p = Cc Db
p A × pB According to Le-Chatelier’s principle, if any of the factors
that determine the equilibrium condition of a system is
Relation between Kp and KC changed, the system will move in such a direction, so that
For a gaseous phase reaction, effect of the change is reduced or nullified or opposed.
n1 A + n 2B r m1 C + m 2D Different factors affecting equilibrium are as follows
According to law of mass action, (i) Effect of Concentration Change Change in the
m m concentration of either reactant(s) or product(s), shift the
p 1p 2
K p = C n Dn reaction in such a direction in which the effect of change
p A 1 pB 2 is minimised or nullified.
In terms of molar concentration, (ii) Effect of Pressure Change Increase in pressure, shifts
m m
[ C] 1 [D ] 2 the equilibrium in that direction, where the number of
KC = n n
[ A ] 1 [B ] 2 moles of the gas or pressure decreases and vice-versa.
K p = K C (RT )
Dn g (iii) Effect of Temperature Change High temperature
favours endothermic reaction and low temperature
If, Dng = 0 then K p = K C favours exothermic reaction.
If, Dng = + ve then K p > K C (iv) Effect of Inert gas Addition At constant volume, there is
If, Dng = - ve then K p < K C no effect of addition of inert gas. While, at constant
pressure, when inert gas is added, reaction goes in the
Units of Equilibrium Constant direction in which there is an increase in the number of
The units of K p and K c also depend upon the value of Dng . moles of the gases.
If number of moles of reactants and products are equal (i.e. (v) Effect of Catalyst A catalyst increases the rate of forward
Dn g = 0) e.g. 2NO ( g ) N 2 ( g) + O2 ( g) reaction as well as the backward reaction, so it does not
º effect the equilibrium and equilibrium constant.
then, K p as well as K c have no units.
If a reaction proceeds with increase or decrease in number of Ionic Equilibrium
Dn
moles then, unit of K p is (atmosphere) g and unit of K c is Equilibria that involve ions only are studied under different
Dn g
(mol per litre) . class called ionic equilibrium. Michael Faraday classified the
substances into two categories based on the ability to conduct
Relationship between Equilibrium electricity, i.e. electrolytes and non-electrolytes.
Constant ( K ), Reaction Quotient (Q ) Degree of dissociation/Ionisation
and Gibbs Energy (G) An electrolyte AB ionises as,
Gibbs free energy and reaction quotient are related as, AB r A + + B -
DG = DG° + RT ln Q The equilibrium established between AB and A + and B - is
called ionic equilibrium. The fraction of total number of
where, DG° = Standard Gibbs energy
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molecules that undergo ionisation or dissociation is called The extent of ionisation also depends upon the strength of
the degree of ionisation or dissociation (a ). the bond and the extent of solvation of ions obtained.
number of molecules of electrolyte ionised as ions The substance that dissociate into ions when dissolved in
Thus, a = water, are called electrolytes. Such substance conduct
total number of molecules of electrolyte dissolved
electricity in aqueous solution. Depending upon the extent of
amount of electrolyte ionised ionisation, the electrolytes are further classified into two
or a =
initial amount classes by Faraday.
Degree of ionisation (a ) increases with dilution and reaches Strong electrolytes on dissolution in water are ionised almost
to maximum limit (unity) at infinite dilution for weak completely, while the weak electrolytes are only partially
electrolytes. dissociated.
Different theories Related to Acids and Bases
Concept Acids Bases Examples
Arrhenius concept Furnish/release H+ Furnish/release OH- ions HCl s H+ + Cl - ; NaOH s Na + + OH-

ions in their aqueous in their aqueous solution. ( Acid) ( Base)
solution. Strong acids HClO4 , HCl , HBr , HI , HNO3
Weak acids HF , CH 3 COOH
Strong bases NaOH, KOH, Ba(OH) 2
Weak bases NH 4 OH , Al(OH)3
Lewis concept Accept a pair of Donate a pair of electrons H+ + OH- ¾® H2 O

electrons, i.e. acids are to form coordinate bond, (Acid) ( Base)
electron deficient i.e. bases are electron rich Acids BF3 , AlCl 3 , Fe3+ , Al 3 + , Cu 2 + ,SF6 (vacant
compounds. compounds.
d-orbitals)
·· ··
Bases H2 O·· , NH3 , OH -
Add proton
Bronsted-Lowry Acid is a proton donor. Base is a proton acceptor.
NH3(aq) + H2O(l) NH4++ (aq) +O H – (aq)
Base Acid Conjugate Conjugate
acid base
Loses proton
Note The acid-base pair which differ by a proton are said to form a conjugate acid-base pair.
If Bronsted acid is a strong acid, then its conjugate base is weak and vice-versa.
Ionisation Constant of Acids and Bases The pH Scale

For acid and bases, ionisation constant can be determined as In order to represent, the hydronium ion concentration more
follows conveniently in terms of molarity, Sorensen introduced scale,
H 2SO 4 ( aq )a H + ( aq ) + HSO-4 ( aq ) a called pH scale.
pH = - log [H + ]
[H + ][SO 24- ]
H + ( aq ) + SO 24- ( aq ) ; K C = If pH < 7, acidic solution, pH = 7 neutral, if pH > 7, basic
[H 2SO 4 ]
solution.
Similarily, for the base like NaOH, the ionisation constant
pK w is a very important quantity for aqueous solutions and
can be written as
controls the relative concentrations of hydrogen and hydroxyl
[Na + ][ OH - ] ions as their product is a constant. i.e.
NaOH( aq ) a Na + + OH - ( aq ) ; K C =
[NaOH] pK w = pOH + pH = 14
Ionic Product of Water
Ionisation Constants of Weak Acids
The ionisation constant of water and its ionic product is
given as For a reaction,
K w = [H + ] [ OH - ] HX( aq ) + H2 O( l ) H3 O+ ( aq ) + X - ( aq )
a
= 1.0 ´ 10 -14 at 298 K Initial conc. C 0 0
where, K w is the ionic product of water. At equil. C(1 - a) Ca Ca
The ionisation or dissociation constant is given as, Factors Affecting Acid Strength
[H+ ][ X - ] Ca 2
Ka = = In general, the strength of an acid is affected by two main
[HX] 1 -a factors.
If a < < 1 Þ (1 - a ) = 1 and degree of ionisation is given as, (i) In a group of the periodic table, the acidic strength is
Ka 1 æ 1ö decided by the strength of H—A bond. On moving down
a= or µ µ V ç\ C µ ÷ the group, as the size of A atom increases, H—A bond
C C è Vø
length and hence the tendency to give a proton increases.
K a is a dimensionless quantity. The larger the value of K a , i.e. acidic strength increases.
stronger is the acid. e.g. ¾ ¾ ¾ ¾Size increases ¾®
¾¾¾¾¾¾
Ionisation Constant of Weak Base HF << HCl << HBr << HI
¾¾¾¾¾¾¾¾¾¾¾ ¾®
For a reaction, Acid strength increases
MOH( aq ) M + ( aq ) + OH- ( aq )
- Similarly, H 2O << H 2 S < H 2 Se < H 2 Te.
Initial conc. C 0 0
At equil. C(1 - a) Ca Ca (ii) Along a period of the periodic table, the acidic strength
is decided by the polarity of the H—A bond. In general,
The base ionisation constant is represented by K b and is as the electronegativity of atom A increases, polarity
given as charge separation in H—A bond increases. Thus, the
[M + ][OH- ] Ca 2
Kb = = bond cleaved readily and hence, the strength of acid
[MOH] 1 -a
increases. e.g.
and degree of ionisation is given as
Electronegativity of A increases
Kb ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾®
a= CH 4 < NH 3 < H 2O < HF
C ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾ ¾®
Higher the value of K b , more basic is the base. Acid strength increases
Relation between Ka and Kb Buffer Solutions

l
In case of a conjugate acid-base pair, The solutions which resist change in their pH on dilution or
K a ´K b = K w an addition of small amounts of acid or alkali are called buffer
l
The pK value of the conjugate acid and base are related to solutions.
each other by the equation, The different types of buffer solutions are as follows
pK a + pK b = pK w = 14 (at 298 K ) l
A buffer solution having pH less than 7 is called as an
Here, pK a = - log K a and pK b = - log K b acidic buffer, e.g. CH3 COOH + CH3 COONa.
Polybasic Acids and Polyacidic Bases l
A buffer solution having pH greater than 7 is called as
l
Acids having more than one ionisable proton per basic buffer, e.g. NH4 OH + NH4 Cl. The pH of basic.
molecule of acids are known as polybasic or polyprotic
acids. Solubility and Solubility Product
l
For dibasic acids, like H 2 X have two ionisation constants Lattice enthalpy and solvation enthalpy play a key role in
and for tribasic acids like H 3 PO 4 , have three ionisation deciding the solubility of salts in a particular solvent.
constants.
For a salt to be able to dissolve in a particular solvent, its
l
It is more difficult to remove a positively charged proton solvation enthalpy must be higher than its lattice enthalpy.
from a negative ion due to electrostatic forces. i.e. ion solvent interaction must be higher than the
That’s why, the higher order ionisation constants (K a2 , K a3 ) interaction between the ions.
are smaller than lower order ionisation constant (K a1 ). Non-polar solvent have very small solvation enthalpy
Note The equilibrium constant for a net reaction obtained after which is not sufficient to overcome the lattice enthalpy of
adding two (or more) reactions equals the products of the salt.
equilibrium constant for individual reactions, i.e.
Hence, salts are generally insoluble in non-polar solvents.
Knet = K1 ´ K2 ´ ...........
Depending upon the solubility, salts are categories into three In general,
groups if Q > K sp , then precipitation takes place.
Category I. Soluble Solubility > 0.1M
if Q < K sp , then no precipitation takes place.
Category II. Slightly soluble 0.01 M < Solubility < 0.1M
if Q = K sp , the reaction is at equilibrium.
Category III. Sparingly soluble Solubility < 0.01M
Effect of pH on Solubility
A solid salt of the general formula, M px + X qy - with molar
The solubility of salts of weak acids like phosphates increases
solubility ‘S’ in equilibrium with its saturated solution may be
with decrease in pH as at lower pH, the anion gets
represented by the equation.
p+ q-
protonated and, hence its concentration decreases.
A x B y (s ) z xA ( aq ) + yB ( aq ).
K sp = [ A p + ] x [B q - ] y = ( xS) x ( yS) y = x x y y S ( x + y ) Common Ion Effect
( x+ y ) The decrease in the ionisation of a weak electrolyte by the
S = K sp / x y
x y
presence of a common ion from a strong electrolyte is called
S = (K sp / x x y y )1/ x + y common ion effect.
e.g. Ionisation of a weak acid (HA) decreases in the
where, K sp is called the solubility product.
presence of a strong acid such as HCl because H+ as
common ion combines with A- to formHA. It is used in (a)
Applications of K sp purification of common salt (b) in qualitative analysis (c)
The value of Q (ionic product) and K sp (solubility) product are salting out of soap.
helpful for predicting, whether a precipitate is formed or not.
Solved
Examples
x
Example 1. The following concentrations were obtained for or = 0.14 = 0.374
the formation of NH 3 from N 2 and H 2 at equilibriun at 500 K. (0.78 - 2 x )
[N 2 ] = 1.5 ´ 10 -2 M. [H 2 ] = 3.0 ´ 10 –2 M or x = 0.29172 - 0.748x

0.29172
and [NH 3 ] = 1.2 ´ 10 -2 M. or 1.748x = 0.29172 or x = = 0.1668
1.748
Calculate equilibrium constant. [ I2 ] equiv = [ Cl 2 ] equiv = 0.1668
Sol. The equilibrium constant for the reaction of formation of [ICl] equili. = 0. 45
ammonia
N 2 (g) + 3H2 (g) r 2NH3 ( g) is Example 4. One of the reaction that takes place in producing
[ NH3 ]2 steel from iron ore is the reduction of iron(II) oxide by carbon
KC =
[ N2 ][H2 ]3 monoxide to give iron metal and CO 2 .
On substituting the values, we get FeO (s ) + CO ( g) r Fe (s ) + CO 2 ( g) ;
(1.2 ´ 10 - 2 )2 K p = 0.265 atm at 1050 K
KC = = 3.55 ´ 10 2
(1.5 ´ 10 - 2 ) (3.0 ´ 10 - 2 )3 What are the equilibrium partial pressures of CO and CO 2
Example 2. At 500 K, equilibrium constant, K C , for the at 1050 K if the initial partial pressures are, p CO = 1.4 atm
following reaction is 5. and p CO2 = 0.80 atm?
1 1 Sol. FeO(s) + CO ( g) r Fe(s) + CO2 ( g);
H 2 ( g) + I 2 ( g) s HI( g)
2 2 Initial pressure 1.4 atm 0.80 atm (K p = 0.265 at 1050
K)
What would be the equilibrium constant K C for the reaction? p CO 2 0.80
2HI ( g) s H 2 ( g) + I 2 ( g) Qp = = = 0.571 [Q Fe and FeO are solids.]
p CO 1.4
1 1
Sol. For the reaction, H2 (g) + I 2 (g) s HI (g) Q Qp > K p , the reaction will go in reverse direction. Due to
2 2
this, pressure of CO 2 will decrease and that of CO will
[HI]
KC = =5 increase to attain equilibrium.
[H2 ]1/ 2 [I 2 ]1/ 2
Suppose p is the decrease in pressure of CO 2 and p is the
Thus, for the reaction, 2HI (g) s H2 (g) + I 2 (g)
[H2 ] [I 2 ] increase in pressure of CO. Hence,
K C1 = p CO 2 = ( 0.80 - p) and p CO = (1.4 + p).
[ HI ]2
p CO 2
æ 1 ö
2
æ1ö 1
2 Now, from K p =
=ç ÷ =ç ÷ = = 0. 04 p CO
èKC ø è 5ø 25 (0.80 - p)
Þ 0.265 =
Example 3. What is the equilibrium concentration of each (1.4 + p)
of the substances in the equilibrium when the initial p=
0.429
= 0.339 atm
concentration of ICl was 0.78 M ? 1.265
2ICl( g) r I 2 ( g) + Cl 2 ( g) ; K c = 0.14 Hence, at equilibrium, p CO 2 = 0.80 - 0.339 = 0.461 atm
and p CO = 1.4 + 0.339 = 1.739 atm
Sol. 2ICl(g) r I2 (g) + Cl 2 (g)
Initial. conc. 0.78 M 0 0
Example 5. Hydrolysis of sucrose gives,
Equil. conc. 0.78 - 2x x x Sucrose + H 2O r Glucose + Fructose
[I2 ] [Cl 2 ] x. x Equilibrium constant K C for the reaction is 2 ´ 1013 at
KC = = = 0.14 300 K. Calculate DG s at 300 K. (NCERT)
[ICl]2 (0.78 - 2 x )2
Sol. DG s = -RT ln K C
x2
Þ = 0.14 DG s = -8.314 J mol -1K-1 ´ 300 K ln (2 ´ 1013 )
( 0.78 - 2 x )2
DG s = -7.64 ´ 10 4 J mol -1
Example 6. At 363 K, pure water has [H 3O + ] = 10 -6 M. Example 9. What is the maximum concentration of
Calculate the value of K w at this temperature. equimolar solutions of ferrous sulphate and sodium sulphide
+ -
Sol. Given, [ H3 O ] = [ OH ] = 10 M -6 so that when mixed in equal volumes, there is no
From K w = [ H3 O+ ] [ OH- ] = 10-12 M precipitation of iron sulphide?
(For iron sulphide, K sp = 6. 3 ´ 10 -18 ) (NCERT)
Example 7. Calculate the pH of the resultant mixtures Sol. FeS is at the point of precipitation when
(i) 10 mL of 0.2 M Ca(OH) 2 + 25 mL of 0.1 M HCl [Fe 2+ ] [S2- ] = K sp
(ii) 10 mL of 0.01 M H 2SO4 + 10 mL of 0.01 M
[Fe2+ ] = [S2 - ] = K sp = 6.3 ´ 10-18
Ca(OH) 2 (NCERT)
Sol. (i) Millimoles of base, Ca (OH)2 = M1V1 = 2 ´ 0.2 ´ 10 = 4 [Fe2+ ] = [S2 - ] = 2.51 ´ 10-9 M
Millimoles of acid, HCl = M 2 V2 = 0.1 ´25 = 2.5 Since, equimolar solutions are to be mixed, hence on mixing
4 > 2.5 concentration is halved. Thus, in original solution
i.e. M1V1 > M 2 V2 hence, solution is basic. [FeSO4 ] = [Na 2 S] = 2 ´ 2.51 ´ 10-9 ; M = 5.02 ´ 10-9 M
M V - M 2 V2 4 - 2.5 Example 10. A sparingly soluble salt gets precipitated only
\ [OH- ] = 1 1 = = 0.043 M
V1 + V2 10 + 25 when the product of concentration of its ions in the solution
\ pOH = - log [4.3 ´ 10 ] -2 (Q sp ) becomes greater than its solubility product. If the
= - 0.6335 + 2 = 1.3665 solubility of BaSO 4 in water is 8 ´ 10 –4 mol dm –3 . Calculate
pH = 14 - pOH its solubility in 0.01 mol dm –3 of H 2SO 4 .
= 14 - 1.3665 = 12.6335 Sol. BaSO 4 (s) a Ba 2 + ( aq)+ SO 24 – (aq)
» 12.63 K sp for BaSO 4 = [Ba 2+] [SO 24 –] = S ´ S = S2
(ii) Millimoles of acid, H2 SO4 = M1V1 = 2 ´ 0.01 ´ 10 = 0.2 But S = 8 ´ 10– 4 mol dm –3
Millimoles of base, Ca(OH2 ) = M 2 V2 \ K sp = ( 8 ´ 10– 4 )2 = 64 ´ 10–8
= 2 ´ 0.01 ´ 10 = 0.2 In the presence of 0. 01 M H2 SO 4 , the expression for K sp will be
Q M1V1 = M 2 V2 , hence solution is neutral. K sp = [Ba 2+] [SO 24 –]
\ pH = 7 K sp = (S) × (S + 0.01)
Example 8. The pH of 0.004 M hydrazine solution is 9.7. (0.01 M SO 24 – ions from 0.01 M H2 SO 4 )
Calculate its ionisation constant K b and pK b . Þ 64 ´ 10 = S × (S + 0. 01)
–8
Sol. Hydrazine undergoes ionisation in the following manner. Þ S + 0. 01S – 64 ´ 10–8 = 0

2
NH2 NH2 + H2 O r NH2 NH+3 + OH- - 0. 01 ± ( 0. 01)2 + ( 4 ´ 64 ´ 10–8 )

\ S=
[H+ ] = antilog (- pH) = antilog ( - 9.7) = 1.67 ´ 10 -10 2
K 1 ´ 10 -14 – 0. 01 ± 10– 4 + (256 ´ 10–8 )
[OH- ] = w+ = =
[ H ] 1.67 ´ 10 -10 2
= 5.98 ´ 10 -5 = [NH2 NH3+ ] – 0. 01 ± 10–4 (1 + 256 ´ 10–4 )
[NH2 NH+3 ] [OH- ] =
Kb = 2
[NH2 NH2 ] – 0. 01 ± 10–2 1 + 0. 0256 10–2 (–1 ± 1. 012719)
= =
(5.98 ´ 10 -5 ) 2 2 2
= = 8.96 ´ 10 -7
0.004 = 5 ´ 10 (–1 + 1. 012719) = 6. 4 ´ 10 mol dm –3
–3 –5
pK b = - log K b = - log (8.96 ´ 10 -7 ) = 6.04

Chapter
Practice
PART 1 5. For reaction in equilibrium,
H 2 ( g) + I 2 ( g) g 2HI( g)
Objective Questions Choose the correct option.
[HI(g)]2
(a) K C =
l Multiple Choice Questions [H2 (g)] [I2 (g)]
[ HI(g)]2 [RT ]2
1. Which of the following statements is incorrect? (b) K p =
(NCERT Exemplar) [ H2 (g)]RT × [ I2 ( g)]RT
(a) In equilibrium mixture of ice and water kept in perfectly (c) In this reaction, K p = K C, i.e. both equilibrium constants
insulated flask, mass of ice and water does not change are equal
with time (d) All of the above
(b) The intensity of red colour increases when oxalic acid is
added to a solution containing iron (III) nitrate and
6. For the reaction,
1
potassium thiocyanate SO 2 ( g) + O 2 ( g) r SO 3 (g)
(c) On addition of catalyst, the equilibrium constant value is 2
not affected if K p = K C (RT)x where the symbols have usual
(d) Equilibrium constant for a reaction with negative DH meaning, then the value of x is (assuming ideality).
value decreases as the temperature increases 1 1
(a) -1 (b) - (c) (d) 1
2. For the reversible reaction, 2 2
N 2 ( g) + 3H 2 ( g) r 2NH 3 ( g) + Heat 7. For the reaction,
The equilibrium shifts in forward direction H 2 ( g) + I 2 ( g) s 2HI( g); K C = 57.0 at 700 K.
(a) by increasing the concentration of NH3 ( g) The molar concentration of [H 2 ] = 0.10 M,
(b) by decreasing the pressure [I 2 ] = 0.20 M and [HI] = 0.40 M.
(c) by decreasing the concentrations of N2 (g) and H2 (g) The reaction quotient, Q C of the reaction is
(d) by increasing pressure and decreasing temperature (a) 10.0 (b) 7.0 (c) 8.0 (d) 12.0
3. Given the reaction between two gases represented 8. Hydrolysis of sucrose gives,
by A 2 and B 2 to give the compound AB ( g) as Sucrose + H 2O s Glucose + Fructose
A 2 ( g) + B 2 ( g) r 2AB ( g) Equilibrium constant (K C ) for the reaction is 2 ´ 1013
At equilibrium, the concentration of at 300 K. The value of DG° at 300 K is
A 2 = 3.0 ´ 10 -3 M, of B 2 = 4.2 ´ 10 -3 M and of (a) 3.52 ´ 105 J mol -1 (b) 5.12 ´ 105 J mol -1
AB = 2.8 ´ 10 -3 M. If the reaction takes place in a (c) 7.64 ´ 104 J mol -1 (d) -7.64 ´ 104 J mol -1
sealed vessel at 527°C, then the value of K C will be
(a) 2.0 (b) 1.9 9. Strong acid dissociates completely in water, the
(c) 0.62 (d) 4.5 resulting base formed would be very weak. The
reason is that
4. The equilibrium constants for the reaction, (a) strong acids have strong conjugate bases
Zn(s ) + Cu 2+ ( aq) l Zn 2+ ( aq) + Cu(s ) (b) strong acids have strong conjugate acids
and Cu(s ) + 2Ag + ( aq) s Cu 2+ ( aq) + 2Ag(s ) (c) strong acids have very weak conjugate bases
(d) strong acids have very weak conjugate acids
are K1 and K 2 respectively. The equilibrium constant
for the combined reaction is 10. The concentration of hydrogen ion in a sample of
(a) K 1 ´ K 2 (b) K 1 + K 2 soft drink is 3.8 ´ 10 -3 M. The value of its pH is
(c) K 1 - K 2 (d) K 1 / K 2 (a) 4.32 (b) 5.12 (c) 3.31 (d) 2.42
11. K a , K a and K a are the respective ionisation

1 2 3
16. Assertion There is an equilibrium between the
constants for the following reactions. (NCERT Exemplar) gaseous molecules and dissolved molecules of the
H 2S s H + + HS - gas under pressure.
HS - s H + + S 2- Reason Such equilibrium is governed by Henry’s law.
H 2S s 2H + + S 2- 17. Assertion N 2O 4 (g) s 2NO 2 (g) is the example of
The correct relationship between K a1 , K a2 , K a3 is homogeneous equilibria.
(a) K a 3 = K a1 ´ K a 2 (b) K a 3 = K a1 + K a 2 Reason For this reaction, K C has unit L/mol and K p
(c) K a 3 = K a1 - K a 2 (d) K a 3 = K a1 / K a 2 has unit bar.
12. Which of the following is correct regarding buffer 18. Assertion In the dissociation of PCl 5 at constant
sol ? pressure and temperature, addition of helium at
(a) It contains a weak acid and its conjugate base equilibrium increases the dissociation of PCl 5 .
(b) It contains a weak base and its conjugate acid Reason Helium removes Cl 2 from the field of action.
(c) It shows little change in pH on adding small amount of (NCERT Exemplar)
acid or base
19. Assertion When a catalyst is added to a reaction
(d) None of the above
mixture in equilibrium the amount of the products
13. Which of the following will produce a buffer increases.
solution when mixed in equal volumes ? Reason The forward reaction becomes faster on
(NCERT Exemplar)
adding the catalyst.
(a) 0.1 mol dm -3 NH4 OH and 0.1 mol dm -3 HCl
(b) 0.05 mol dm -3 NH4 OH and 0.1 mol dm -3 HCl 20. Assertion The ionisation of hydrogen sulphide in
(c) 0.1 mol dm -3 NH4 OH and 0.05 mol dm -3 HCl water is low in the presence of hydrochloric acid.
(d) 0.1 mol dm -3 CH4 COONa and 0.1 mol dm -3 NaOH Reason Hydrogen sulphide is a weak acid.
14. Dissolution of sodium sulphate is an exothermic (NCERT Exemplar)
process. If a saturated solution of sodium sulphate l Case Based MCQs
containing extra undissolved sodium sulphate is
heated, then 21. Read the following and answer the questions from (i)
(a) more of sodium sulphate will dissolve to (iv) given below
(b) some sodium sulphate will be precipitated out
Throughout the history of chemistry, various acid-base
(c) concentration of the solution will not change
(d) the solution will become supersaturated
theories have been deduced and utilised based upon
structure and composition of the substance. Some
15. The values of K sp of two sparingly soluble salts important one of these are Arrhenius theory, Bronsted
Ni(OH) 2 and AgCN are 2.0 ´ 10 -15 and 6 ´ 10 -17 theory and Lewis concept. The main idea in Arrhenius
respectively. Which salt is more soluble ? theory is when an electrolyte is dissolved in H 2O, it
(a) Ni(OH)2 is more soluble than AgCN dissociates into charged ions. Acid and base are called
(b) AgCN is more soluble than Ni(OH)2 strong and weak based upon their dissociation.
(c) Both Ni(OH)2 and AgCN soluble to same extent According to Bronsted-Lowry concept, the two
(d) Ni(OH)2 is soluble but AgCN is insoluble species differ in the way that one accepts H + ion while
other donates it. The counterions of acid and bases are
l
Assertion-Reasoning MCQs called conjugate base and conjugate acid respectively.
Direction (Q. Nos. 16-20) For given questions two Lewis theory suggests that it is the richness or
statements are given-one labelled Assertion (A) and the deficiency of electron pair which differentiates acid
other labelled Reason (R). Select the correct answer to and bases. Still, no single theory is valid in all the cases
these questions from the codes (a), (b), (c) and (d) as and thus we utilise each theory in its own application.
given below. (i) Acidity of BF 3 can be explained on the basis of
(a) Both A and R are true and R is the correct which of the following concepts? (NCERT Exemplar)
explanation of A. (a) Arrhenius concept
(b) Bronsted-Lowry concept
explanation of A.
(c) Lewis concept
(d) Bronsted-Lowry as well as Lewis concept
(ii) What will be the conjugate bases for the following (ii) The addition of NaCl to AgCl decreases the
Bronsted acids? solubility of AgCl because
HF, H 2SO 4 and HCO –3 (a) solubility product decreases
- 2- 2- - 2- (b) solubility product remains constant
(a) F , SO and CO
4 3 (b) F , SO and H2 CO 3
4
(c) solution becomes unsaturated
(c) F –, HSO and H2 CO 3
–
4 (d) F –, HSO and CO2-
–
4 3
(d) solution becomes supersaturated
(iii) Which of the following cannot act both as
(iii) The solubility product of a sparingly soluble salt
Bronsted acid and as Bronsted base?
- AB at room temperature is 1.21 ´ 10 -6 , its molar
(a) HCO 3 (b) NH3
(c) HCl (d) HSO-4
solubility is
(a)1.21 ´ 10 -6 M (b)1.1 ´ 10 -4 M
(iv) In the following reaction, (c)1.1 ´ 10 -3 M (d) None of these
H2 O ( l ) + H2 O( l ) f H3 O+ ( aq ) + OH- ( aq ) Or
Acid X Conjugate acid Y
X and Y respectively are What will be the molar solubility S of a solid salt
(a) base and conjugate acid with general formula M px + X qy - ?
1/ x + y x+ y
(b) acid and conjugate base æ K ö æ K sp ö
(a) ç y sp x ÷ (b) ç x y ÷
(c) base and conjugate base èx ×y ø èx ×y ø
(d) acid and conjugate acid 1/ x + y x+ y
æ K ö æ K ö
Or (c) ç x sp y ÷ (d) ç y sp x ÷
èx ×y ø èx ×y ø
Carboxylic acids readily dissolve in aqueous sodium
bicarbonate, liberating carbon dioxide. Which one of (iv) In which of the following solvents, silver chloride
the following statement is correct? is most soluble?
(a) The free carboxylic acid and its conjugate base are of (a) 0.1 mol dm -3 AgNO3 solution
comparable stability (b) 0.1 mol dm -3 HCl solution
(b) The free carboxylic acid is more stable than its conjugate (c) H2 O
base (d) Aqueous ammonia
(c) The conjugate base of the carboxylic acid is more stable
than the free carboxylic acid
(d) The conjugate acid of the carboxylic acid is more stable
than the free carboxylic acid
PART 2
22. Read the following and answer the questions from Subjective Questions
(i) to (iv) given below
Solubility can be throught of as the amount of l
solute dissolved in certain volume of solvent. Ionic 1. A liquid is in equilibrium with its vapour in a sealed
compounds gets dissolved in aqueous solution and container at a fixed temperature. The volume of the
organic compound in organic solvent. container is suddenly increased.
If AgCl (sparing soluble salt) is stirred in water then (i) What is the initial effect of change on vapour
only a small amount of it is dissolved and most of it pressure?
is undissolved. In other words, there exists a
(ii) How do rates of evaporation and condensation
dynamic equilibrium between undissolved salt and
change initially?
ion which it furnished in the solution. This can be
represented as: (iii) What happens when equilibrium is restored finally
AgCl f Ag + + Cl - and what will be the final vapour pressure?
(NCERT)
K sp = [ Ag + ] [ Cl - ]
2. The value of K C for the reaction,
K sp is the solubility product and is defined as the
3O 2 ( g) r 2O 3 ( g) is 2.0 ´ 10 -50 at 25°C. If the
product of the concentration of furnished ions in
equilibrium concentration of O 2 in air at 25°C is
given saturated solution.
1.6 ´ 10 -2 , what is the concentration of O 3 ? (NCERT)
(i) When no more solute can be dissolved in solution
at a given temperature the solution is known as 3. For the following equilibrium,
(a) supersaturated solution NO(g) + O 3 ( g) r NO 2 ( g) + O 2 ( g) at 1000 K
(b) saturated solution Both the forward and reverse reactions in the
(c) unsaturated solution equilibrium are elementary bimolecular reactions.
(d) Both (a) and (b) What is K C for the reverse reaction? (NCERT)
4. The reaction, 11. Ionisation constant of a weak base MOH ,is given
+ -
CO ( g) + 3 H 2 ( g) r CH 3 (g) + H 2O (g) by the expression K b =
[M ] [OH ]
is at equilibrium at 1300 K in a 1L flask. It also [MOH]
contains 0.30 mole of CO, 0.10 mole of H 2 and Values of ionisation constant of some weak bases at a
0.02 mole of H 2O and an unknown amount of CH 4 in particular temperature are given below.
the flask. Determine the concentration of CH 4 in the Base Dimethyl amine Urea Pyridine Ammonia
mixture. The equilibrium constant, K C for the
Kb 5.4 ´ 10 -4 1.3 ´ 10 -14 1.77 ´ 10 -9 1.77 ´ 10 -5
reaction at the given temperature is 3.90.
5. Find out the value of K C for each of the following Arrange the bases in decreasing order of the extent
equilibria from the value of K p (NCERT) of their ionisation at equilibrium. Which of the above
base is the strongest? (NCERT Exemplar)
(i) 2NOCl(g) r 2NO(g) + Cl 2 ( g);
K p = 1.8 ´ 10 -2 at 500 K
12. Calculate
(i) Dissociation constant of conjugate base of HF,
(ii) CaCO 3 (s ) r CaO (s ) + CO 2 ( g) ; K a = 6.8 ´ 10 -4 .
K p = 167 at 1073 K (ii) Dissociation constant of conjugate acid of CO 2-
3 ,
6. Nitric oxide reacts with Br2 and gives nitrosyl K b = 2.1 ´ 10 -4 .
bromide as per reaction given below 13. The pH of a sample of vinegar is 3.76. Calculate the
2NO ( g) + Br2 ( g) r 2NOBr( g) concentration of hydrogen ion in it.
When 0.087 mole of NO and 0.0437 mole of Br 2 are 14. Ionic product of water at 310 K is 2.7 ´ 10 -14 . What
mixed in a closed container at constant temperature, is the pH of neutral water at this temperature?
0.0518 mole of NOBr is obtained at equilibrium.
Calculate the equilibrium amount of NO and Br 2 .
15. Calculate the pH of a solution containing 0.1 M
acetic acid and 0.1 M benzoic acid, K a for
7. The equilibrium constant for the following reaction CH 3COOH and C 6 H 5COOH are 1.8 ´ 10 -5 and
is 1.6 ´ 10 5 at 1024 K (NCERT) 6.5 ´ 10 -5 respectively.
H 2 ( g) + Br2 ( g) r 2HBr( g) 16. The ionisation constant of dimethylamine is
Find the equilibrium pressure of all gases if 10.0 bar 5. 4 ´ 10 -4 . Calculate its degree of ionisation in its
of HBr is introduced into a sealed container at 1024 K. 0.02 M solution. What percentage of
8. At 473K, equilibrium constant K C for dimethylamine is ionised if the solution is also
decomposition of phosphorus pentachloride, PCl 5 0.1 M in NaOH?
is 8.3 ´ 10 -3 . If decomposition is depicted as, 17. (i) Sulphuric acid is a very strong acid, yet it can also
PCl 5 ( g) r PCl 3 ( g) + Cl 2 ( g); act as base in some reactions. Explain how?
DH° = 124.0 kJ mol -1 (ii) All Bronsted acids are not Lewis acids. Explain.
(i) Write an expression for K C for the reaction.
18. The solubility of Sr(OH)2 at 298 K is 19.23 g/L of
(ii) What is the value of K C for the reverse reaction at solution. Calculate the concentrations of strontium
the same temperature? and hydroxyl ions and the pH of the solution.
(iii) What would be the effect on K C if (a) more PCl 5
is added (b) pressure is increased (c) the 19. What is the minimum volume of water required to
temperature is increased ? dissolved 1g of calcium sulphate at 298 K?
(For calcium sulphate, K sp is 9.1 ´ 10 -6 ).
9. Does the number of moles of reaction products
increase, decrease or remain same when each of the 20. The solubility product of Fe(OH)3 is 1 ´ 10 -36 . What
following equilibria is subjected to a decrease in is the minimum concentration of OH - ions required
pressure by increasing the volume? to precipitate Fe(OH)3 from a 0.001 M solution of
(i) PCl 5 ( g) r PCl 3 ( g) + Cl 2 ( g) FeCl 3 ?
(ii) CaO(s ) + CO 2 ( g) r CaCO 3 (s ) l
(iii) 3Fe(s ) + 4H 2O( g) r Fe3 O 4 (s ) + 4H 2 ( g)
21. Write a relation between DG and Q and define the
10. The ionisation constant of HF, HCOOH and HCN at meaning of each term and answer the following.
298 K are 6.8 ´ 10 -4 , 1.8 ´ 10 -4 and 4.8 ´ 10 -9
(i) Why a reaction proceeds forward when Q < K
respectively. Calculate the ionisation constants of the
corresponding conjugate base. (NCERT)
and no net reaction occurs when Q = K ?
(ii) Explain the effect of increase in pressure in terms (ii) Ionisation constant of a weak base MOH, is given
of reaction quotient Q. (NCERT Exemplar) by the expression
For the reaction, [M + ][OH - ]
Kb =
CO( g) + 3 H 2 ( g) s CH 4 ( g) + H 2O( g) [MOH ]
22. On the basis of Le-Chatelier principle explain how Values of ionisation constant of some weak bases
temperature and pressure can be adjusted to at a particular temperature are given below.
increase the yield of ammonia in the following
reaction. Base Dimethyl amine Urea Pyridine
N 2 (g) + 3H 2 (g) s 2NH 3 (g); DH = - 92.38 kJ mol -1 Kb 5.4 ´ 10 -4
1.3 ´ 10 - 14
1.77 ´ 10- 9
What will be the effect of addition of argon to the
above reaction mixture at constant volume? Arrange the bases in decreasing order of the extent
(NCERT Exemplar) of their ionisation at equilibrium. Which of the above
23. (i) Describe the effect of base is the strongest?
(a) addition of H 2 28. K1 and K 2 for dissociation of H 2S are 4 ´ 10 -3 and
(b) addition of CH 3OH 1 ´ 10 -5 . Calculate sulphide ion concentration in 0.1
(c) removal of CO M H 2S solution.
(d) removal of CH 3OH on the equilibrium of the
reaction, 2H 2 ( g) + CO( g)s CH 3OH( g)
l Case Based Questions
(NCERT) 29. Read the following and answer the questions from (i)
(ii) What happens to an equilibrium in a reversible to (iv) given below
reaction if a catalyst is added to it? Equilibrium represents the state of a process in
24. (i) For the reaction, N 2 (g) + 3H 2 (g) r 2NH 3 (g), which properties like temperature, pressure,
the partial pressures of N 2 and H 2 are 0.80 and concentration of a system do not show any change.
0.40 atmosphere respectively at equilibrium. The Any reaction at equilibrium can be represented as
total pressure of the system is 2.80 atmosphere. aA + bB r cC + dD
What is K p for the above reaction ? Equilibrium is characterised by equilibrium constant
(ii) An equilibrium mixture at 300 K contains N 2O 4 K C (reactant in solution) or K p (reactants as gases).
and NO 2 at 0.28 and 1.1 atm pressure respectively. This constant is the ratio of concentration of product
If the volume of the container is doubled, calculate to reactant raised to the power of their stoichiometric
the new equilibrium pressure of two gases. quotient. This same ratio at condition other than
25. When ammonia is heated from 27°C to 327°C in a equilibrium is known as reaction quotient and their
closed vessel under a pressure of 15 atm, it partially difference shows if the reaction goes forward or
decomposes to H 2 and N 2 . The pressure inside the backward.
vessel increases to 50 atm but the volume remains (i) Write the expression for the equilibrium constant,
constant. Calculate the percentage of NH 3 K C for the following reactions.
decomposed. 2Cu(NO 3 ) 2 (s ) r 2CuO(s ) +4NO 2 ( g )+O 2 ( g )
26. Calculate the pH of the following solutions. (ii) What is the unit of K p and K C for the reaction
(i) 2 g of TlOH dissolved in water to give 2 L of 2NO( g ) r N 2 ( g ) + O 2 ( g )
solution.
Or
(ii) 0.3 g of Ca(OH) 2 dissolved in water to give
Compare equilibrium constant (K C ) with reaction
500 mL solution.
quotient ( Q) when (a) reaction goes forward
(iii) 0.3 g of NaOH dissolved in water to give 200 mL (b) reaction goes backwards.
of solution.
(iii) For the equilibrium,
(iv) 1 mL of 13. 6 M HCl is diluted with water to give
1 L of solution. (NCERT)
2 NOCl (g) r 2 NO(g) + Cl 2 ( g)
the value of the equilibrium constant, K C is
27. (i) Calculate the pH of 0.08 M solution of 3.17 ´ 10 - 6 at 1069 K.
hypochlorous acid, HOCl. The ionisation constant
of the acid is 2.5 ´ 10 - 5 . Determine the percent Calculate the K p for the reaction at this
dissociation of HOCl. temperature?
(iv) The value of K C for the reaction 2A r B + C is reactions having different number of moles of
2 ´ 10 -3 . At a given time, the composition of gaseous reactants and products. It has no effect on
reaction mixture is [ A] = [B] = [ C] = 3 ´ 10 - 4 M. In solids / liquids as the volume (and concentration) of
which direction the reaction well proceed? liquids is nearly independent of pressure.
30. Read the following and answer the questions from In general, increase in pressure shifts the
(i) to (iv) given below equilibrium in that direction where the number of
According to Le-Chatelier’s principle, ‘if any of the moles of the gas or pressure decreases and
factors that determine the equilibrium condition, of vice-versa.
a system (like temperature, pressure, concentration (i) What will happen to the equilibrium constant if an
etc.,) is changed, the system will move in such a inert gas is added into the reaction at constant
direction so that effect of the change is reduced or volume?
nullified.’ (ii) What happens to the following reaction on
According to Le-Chatelier’s principle, the increasing pressure ?
concentration stress due to the addition of Ice r Water
reactant/product in relieved by shifting of the net Or
reaction in that direction where the added
What is the effect of heating on the equilibria,
substance is consumed.
solid s liquid?
The concentration stress due to the removal of
(iii) For the reaction,
reaction /product is relieved by shifting of the net
reaction in that direction where the removed 1
SO 2 ( g ) + O 2 ( g ) r SO 3 ( g ) + Heat
substance is replenished or in other words, “change 2
in the concentration of either reactant(s) or What happens when temperature of reaction
product(s) shift the reaction in such a direction in mixture is increased ?
which the effect of the change is minimised or (iv) What is the effect of reducing volume on the
nullified.” following system ?
Pressure change, that is achieved by changing the 2C(s ) + O 2 ( g ) r 2CO( g )
volume of the system, generally affect the gaseous
EXPLANATIONS
Objective Solutions 7. (c) Consider the gaseous reaction of H2 with I2 .
1. (c) Statement (c) is not correct. H2 ( g) + I 2 ( g) s 2HI( g); K C = 57.0 at 700 K
It’s correct form is as follows [HI ]2 (0.40)2
Þ QC = = = 8.0
At the stage of equilibria, physical processes like melting of [H 2 ] [I 2 ] (0.10) ´ (0.20)
ice and freezing of water etc., do not stop but the opposite
processes, i.e. forward and reverse process occur with the 8. (d) Sucrose + H2 O ¾® Glucose + Fructose
same rate. The other given statements are the characteristics We know that, R = 8. 314 J mol -1K -1
of physical equilibrium and stand correct. Given, T = 300 K; K C = 2 ´ 10 13
2. (d) According to Le-Chatelier’s principle, equilibrium shifts Q DG° = - RT ln K C or -2.303 RT logK C
in the opposite direction to undo the change. \ DG° = - 2. 303 ´ 8.314 J mol –1 K–1
N2 ( g) + 3H2 ( g) r 2NH 3 ( g) ´ 300 K ´ log (2 ´ 1013 )
On increasing pressure, equilibrium shifts in the forward Þ DG° = - 7.64 ´ 10 J mol
4 –1
direction where number of moles decreases, while on
decreasing temperature, it moves in forward direction where 9. (c) According to Bronsted theory, if Bronsted acid is a strong
temperature increases. acid then its conjugate base is weak and vice-versa.
3. (c) A 2 ( g) + B 2 ( g) r 2 AB( g) 10. (d) Q pH = - log[ H+ ]
The equilibrium constant is given by, \ pH = - log [3.8 ´ 10-3 ] = - {log (3.8) + log (10-3 )}
[ AB ] 2 = - {(0.58) + (-3.0)} = - {-2.42} = 2.42
KC = Therefore, the pH of the soft drink is 2.42 and it can be
[ A 2 ][B 2 ]
inferred that, it is acidic.
Given,
[ AB ] = 2. 8 ´ 10-3 11. (a) For the reaction,
[ A 2 ] = 3 ´ 10-3 H2 S s H+ + HS-
[H ] [HS- ]
+
[B 2 ] = 4.2 ´ 10-3 K a1 =
(2.8 ´ 10-3 )2 [H2 S]
\ KC =
(3 ´ 10-3 ) (4.2 ´ 10-3 ) For the reaction, HS - s H+ + S2-
7.84 [H+ ] [S2 - ]
KC = = 0.62 Ka2 =
12.6 [HS- ]
4. (a) The equilibrium constant for combined reaction is When, the above two reactions are added, their equilibrium
K 1 ´ K 2 . This is because, when two reaction are added, their constants are multiplied,
equilibrium constants are multipled. [H+ ]2 [S2 - ]
K a3 = = K a1 ´ K a2
5. (d) For reaction in equilibrium, [ H2 S ]
H 2 ( g) + I 2 ( g) s 2HI ( g) Hence, K a 3 = K a1 ´ K a 2
we can write
12. (c) A buffer solution shows little change in pH on adding
[ HI( g)]2 small amount of acid or base.
KC =
[ H2 ( g)][ I2 ( g)] 13. (c) When the concentration of NH4 OH (weak base) is higher
Further, since p HI = [ HI( g)]RT than the strong acid (HCl), a mixture of weak base and its
p I 2 = [ I2 ( g)] RT conjugate acid is obtained, which acts as basic buffer.
p H 2 = [ H2 ( g)] RT NH4 OH + HCl ¾® NH4 Cl + H 2 O
[ p HI ]2 [ HI ( g)]2 [RT ]2 Initially 0.1 M 0.05 M 0
Therefore, K p = =
[ p H 2 ][ p I 2 ] [ H2 ( g)]RT × [ I2 ( g)]RT After reaction 0.05 M 0 0.05 M
[ HI( g)] 2 14. (b) Na 2 SO4 (s) + ( aq) s Na 2 SO4 (aq) + Heat
= = KC
[ H2 ( g)][ I2 ( g)] According to Le-Chatelier principle, on heating, equilibrium
shifts in the backward direction. So, some sodium sulphate
6. (b) For the given reaction,
will be precipitated out.
Dn g = n P - n R
15. (a) AgCN s Ag+ + CN– ; K sp = [Ag+ ][CN- ] = 6 ´ 10-17
where, n P = number of moles of products and n R = number
of moles of reactants Ni(OH)2 s Ni 2 + + 2 OH- ; K sp = [Ni 2 + ][OH - ] 2 = 2 ´ 10-15
Q
Dn
K p = K C(RT ) g Let [Ag+ ] = S 1 , then [CN- ] = S 1
1 Let [Ni 2+ ] = S2 , then [OH- ] = 2S2
\ Dn g = - S 12 = 6 ´ 10-17 , S 1 = 7.7 ´ 10-9
2
1 (S2 )(2 S2 )2 = 2 ´ 10-15 , S2 = 7.9 ´ 10-6
Thus, the value of x = - \ Ni(OH)2 is more soluble than AgCN.
2
16. (a) Both A and R are true and R is the correct explanation of A. (iii) (c) S = K sp = 1.21 ´ 10-6 = 1.1 ´ 10-3 M
When a gas is dissolved in water, an equilibrium is developed
between the gaseous molecules and dissolved molecules of the Or
gas under pressure, e.g. CO2 (g) CO2 (solution). Such
- (c) A solid salt of the general formula, M px + X qy - with
equilibrium is governed by Henry’s law. molar solubility S in equilibrium with its saturated
17. (c) A is true but R is false. solution may be represented by the equation,
For the homogeneous equilibrium, M x X y (s) ¾® xM p + ( aq) + yX q - ( aq)
N2 O4 ( g) l 2NO2 ( g), (where, x ´ p + = y ´ q - )
K C has unit mol/L and K p has unit bar. and its solubility product constant is given by
18. (c) A is true but R is false. K sp = [M p + ]x [ X q - ]y = ( xS)x ( yS)y
PCl 5 ¾® PCl 3 + Cl 2 K sp = x x × y y × S( x + y )
At constant pressure, when He is added to the equilibrium, K sp
S( x + y ) = x y or S = (K sp / x x × y y )1/ x + y
volume increases. Thus, in order to maintain the K constant, x ×y
degree of dissociation of PCl 5 increases. Moreover, He (iv) (d) Among the given solvents, AgCl is most soluble in
(helium) is unreactive towards chlorine gas. aqueous ammonia solution. AgCl react with aqueous
19. (c) A is true but R is false. Addition of inert gas shifts the ammonia to form a complex, [ Ag ( NH3 )2 ]+ Cl - .
equilibrium to backward direction.
20. (b) Both A and R are true but R is not correct explanation of Subjective Solutions
A. 1. A( l ) ¾¾¾® A( g)
HCl gives the common H + ions and hence ionisation Low pressure High pressure
equilibrium H 2S a 2H + + S2 - is suppressed. If volume is increased at constant temperature, pressure
21. (i) (c) G N Lewis defined an acid as a species which decreases, since, p µ 1 / V at constant temperature.
accepts an electron pair and base which donates an (i) Decrease in pressure shifts the equilibrium in the
electron pair. As BF3 is an electron deficient compound, direction of high pressure, i.e. more vapours are formed
hence, it is a Lewis acid. hence vapour pressure increases.
(ii) (d) The conjugate bases should have one proton less in (ii) Rate of evaporation increases and rate of condensation
each case and therefore, the corresponding conjugate decreases.
bases are F- , HSO-4 and CO 23 - respectively. (iii) When equilibrium is finally restored the rate of
(iii) (c) HCl can only act as Bronsted acid because it can evaporation again becomes equal to the rate of
only donate proton. condensation and the final vapour pressure becomes
HCl + H2 O - H3 O+ + Cl - equal to the vapour pressure that was before the
Acid Base sudden increase in the volume of the container.
The remaining options contains substances which act 2. 3O2 ( g) r 2 O3 ( g)
both as Bronsted acid and Bronsted base. [O 3 ]2
(a) HCO–3 + HCO–3 - H2 CO3 + CO2– KC =
3 [O 2 ]3
(b) NH3 + NH3 - NH4 + NH-2
+
or O3 = K C[ O2 ]3 = (2. 0 ´ 10- 50 )(1. 6 ´ 10- 2 )3
(c) HSO–4 + HSO–4 - H2 SO4 + SO2–
[O 3 ] = 2.86 ´ 10-28 mol L-1
4
(iv) (c) H2 O
Acid
- OH
Conjugate base 3. For the reaction,
Y NO (g) + O 3 (g) r NO 2 (g) + O 2 (g)
H2 O + H2 O- H3 O+ K C = 6.3 ´ 1014 at 1000 K)
Acid Base Conjugate acid
[NO2 ][O2 ]
X KC = = 6.3 ´ 1014 …(i)
Or [NO][O3 ]
(c) RCOOH + NaHCO3 r RCOONa + H2 O + CO 2 For reverse reaction,
or RCOOH + HCO-3 r RCOO- + H2 O + CO 2 NO 2 ( g) + O 2 ( g) r NO ( g) + O 3 ( g)
conjugate base, RCOO- is more stable than the free [NO][O 3 ]
K ¢C = …(ii)
carboxylic acid. [NO 2 ][O 2 ]
That’s why, equilibrium shifts in forward direction. From Eqs. (i) and (ii), we get
Thus, statement (c) is correct. 1 1
22. (i) (b) Saturated solution are those in which no more solute K ¢C = = = 1.587 ´ 10-15
K C 6.3 ´ 1014
can be dissolved at given temperature.
As the value of reaction quotient is greater than the value of
(ii) (b) [Cl - ] increases but K sp = [Ag+ ][Cl - ] remains
K C, i.e. 1 ´ 10– 4 the reaction will proceed in the reverse
constant. So, [Ag+ ] decreases. direction.
4. CO (g) + 3 H2 (g) r CH4 (g) + H2 O(g) ; K C = 3.90 at 1300 K. 2 ´ 2 ´ 10 ´ 10 ´ 0. 625 ´ 10- 5 = x 2

[CH 4 ] × [H 2 O] or x = 0.050
KC = x 0.050
[CO] [H 2 ]3 p H 2 = p Br2 = = = 0.025 bar = 2.5 ´ 10-2 bar
[CH 4 ] [0.02] 2 2
Þ 3.90 = p HBr = 10 - 0.050 = 9.95 » 10 bar
[0.30] [0.10]3
3.90 ´ 0.30 ´ (0.10) 3 8. PCl 5 (g) r PCl 3 (g) + Cl 2 (g) ; K C = 8.3 ´ 10-3
[CH4 ] = = 0.0585 M
0.02 [PCl 3 ] [Cl 2 ]
(i) K C =
[CH4 ]eq = 5.85 ´ 10 -2 M [PCl 5 ]
5. (i) 2NOCl( g) r 2 NO( g) + Cl 2 ( g) ; (ii) For the reverse reaction,
K p = 1.8 ´ 10-2 at 500 K K C¢ =
1
=
1
= 120.48
Dn g = n P - n R = 3 - 2 = 1 K C 8.3 ´ 10-3
Kp 1.8 ´ 10-2 (iii) (a) Addition of PCl 5 has no effect on K C because K C is
KC = Dn g
= = 4.38 ´ 10-4
(RT ) 0.0821 ´ 500 constant at constant temperature.
(ii) CaCO3 (s) r CaO (s) + CO 2 (g) ; (b) K C does not change with pressure.
K p = 167 at 1073 K (c) The given reaction is endothermic, hence on
increasing the temperature, K f will increase, this
Dn g = n P - n R = 1
æ K ö
Kp 167 results in increase in K C çK C = f ÷ .
KC = Dn g
= = 1.89 è Kbø
(RT ) 0.0821 ´ 1073
6. In order to solve such problems, following steps are 9. According to Le-Chatelier's principle, on decreasing pressure
involved. equilibrium shifts in that direction where pressure increases
(i.e. number of moles in gaseous state are more). Therefore,
Step I Set up a balance sheet using symbols for the expected
number of moles of reaction products in (i) increases
equilibrium amounts of reactants and products.
(ii) decreases (iii) remains the same (If Dn g = 0, there is no
2NO + Br2 2NOBr effect of change in pressure).
Initial moles 0.087 0.0437 0 (as no reaction occur)
10. If K a is the ionisation constant of a weak acid (HA) and K b is
At equilibrium (0.087–2x) (0.0437 – x) 2x
moles the ionisation constant of its conjugate base (A - ) then,
[Remember to multiply the value of x with the K a ×K b = K w
stoichiometric coefficient of the molecule]. Kw 1 ´ 10-14
K b (F- ) = = = 1.47 ´ 10-11
Step II Compare with the given information K a (HF) 6.8 ´ 10-4
Given, equilibrium moles of NOBr = 0.0518 Kw 1 ´ 10-14
0.0518 K b (HCOO- ) = =
\ 2x = 0.0518 and x = = 0.0259 K a (HCOOH) 1.8 ´ 10-4
2
= 5.56 ´ 10-11
Step III Put the value of x to obtained equilibrium Kw 1 ´ 10-14
concentration of other species. K b( CN- ) = = = 2.08 ´ 10-6
K a ( HCN) 4.8 ´ 10-9
Moles of NO at equilibrium = (0.087 - 2x )
11. Greater the ionisation constant (K b ) of a base, greater is its
= 0.087 - 0.0518 = 0.0352 mol
ionisation. Hence, dimethyl amine is the strongest base.
Moles of Br2 at equilibrium = (0.0437 - x ) Dimethyl amine > ammonia > pyridine > urea
= 0. 0437 - 0. 0259 = 0. 0178 mol K b : 5.4 ´ 10-4 1.77 ´ 10-5 1.77 ´ 10-9 1.3 ´ 10-14
7. H2 (g) + Br2 (g) r 2HBr(g) ; 12. (i) HF r H+ + F-
K p = 1.6 ´ 10 at 1024 K5
K a (acid) ´K b (conjugate base) = 1.0 ´ 10 -14
\ 2HBr(g) r H2 (g) + Br2 (g) ; 1.0 ´ 10 -14
1 K b( F - ) = = 1.47 ´ 10 -11
K ¢p = at 1024 K 6.8 ´ 10 -4
1.6 ´ 105 (ii) CO 23 - + H+ r HCO 3-
Initial pressure 10.0 bar 0 0 K b( CO 23 - ) ´ K a ( HCO 3- ) = 1 ´ 10-14
x x
Equil. pressure ( 10 - x ) 1 ´ 10 -14
2 2 K a ( HCO -3 ) = = 4.76 ´ 10-11
x x 2.1 ´ 10 -4
×
p H 2 × p Br2
Kp = = 2 2 13. pH = - log [H + ] = 3.76 and log [H + ] = - 3.76
2
p HBr (10 - x )2 [Before taking antilog add -1 in characteristic ( - 3) and +1
x x in mantissa (0.76) , i.e. - 3.76 - 1 + 1 = 4.24]
×
1 -5 2 2 log[H+ ] = 4.24
= 0.625 ´ 10 =
1.6 ´ 10 5
10 ´ 10 or [H+ ] = antilog 4.24
[(10 - x ) » 10 because magnitude of K p is small.)] [H ] antilog(3.76) = 1.738 ´ 10 -4 M
+
14. K w = [H3 O+ ] × [OH- ] = 2.7 ´ 10-14 at 310 K 19. CaSO4 r Ca 2 + + SO24 - ; K sp = 9.1 ´ 10-6
S S S
+ - + -
H2 O + H2 O r [H3 O ] [OH ] [H3 O ] = [OH ]
where S is the solubility of CaSO4
Therefore, [H3 O + ] = 2.7 ´ 10 -14 = 1.643 ´ 10 -7 M
K sp = [Ca 2 + ] [SO 24 - ] = S × S = S 2
pH = - log [H3 O + ] = - log 1.643 ´ 10 -7
pH = 7 + ( - 0.2156) = 6.7844 S = K sp = 9.1 ´ 10 -6
15. [ H3 O+ ] = K a1 C1 + K a 2 C 2 Þ S = 3.017 ´ 10 -3 M
= (1.8 ´ 10 -5 ) (0.1) + (6.5 ´ 10 -5 ) (0.1) \Solubility of CaSO4 = 3.017 ´ 10 -3 mol L-1
= 3.017 ´ 10 -3 ´ 136 g L -1
= 1.8 ´ 10 -6 + 6.5 ´ 10 -6
(Molar mass of CaSO 4 = 136 g mol -1)
= 8.3 ´ 10 -6 = 2.88 ´ 10 -3 M = 410.3 ´ 10 -3 gL -1
pH = - log [H3 O + ] = - log ( 2.88 ´ 10 -3 ) -3
Q 410.3 ´ 10 g CaSO 4 is dissolved in = 1 L
= 3 - 0.4594 = 2.5406 1´ 1
\1g CaSO 4 is dissolved in = = 2.437 L
16. Given, K b for dimethylamine = 5.4 ´ 10-4 , 410.3 ´ 10 -3
C for dimethylamine = 0.02 M 20. K sp for Fe(OH)3 = [Fe3 + ] [OH- ]3 .
-4
5.4 ´ 10 Precipitation will occur when ionic product,
a = Kb / C = = 1.64 ´ 10-1 = 0.164
0.02 [Fe3+ ][OH- ]3 becomes greater than K sp .
In the presence of 0.1 M NaOH, [Fe3 + ] = [FeCl 3 ] = 0.001 M
+ The concentration of OH- ions required to start the
(CH3 )2 NH + H2 O r (CH3 )2 N H2 + OH-
precipitation is
Initial conc. 0.02 M 0 0 K sp 1 ´ 10-36
[OH- ]3 = = = 1 ´ 10-33
Equili. conc. (0.02 - Ca) Ca Ca + 0.1 3+
[Fe ] 0.001
» 0.02 » 0.1 \ [OH- ] = (1 ´ 10-33 )1/ 3 = 1 ´ 10-11 mol L-1
(0.1 from 0.1 M NaOH)
+
Thus, concentration of OH- required to start precipitation of
[(CH3 )2 N H2 ] [OH- ] Fe(OH)3 is 1 ´ 10-11 mol L-1.
Kb =
[(CH3 )2 NH] 21. The relation between DG and Q is
0. 02 a ´ 0.1 DG = DG s + RT ln Q
\ 5. 4 ´ 10-4 =
0. 02 DG = change in free energy as the reaction proceeds
5.4 ´ 10-4 ´ 0.02 DG s = standard free energy
a= = 54 ´ 10-4 = 5.4 ´ 10-3
0.02 ´ 0.1 Q = reaction quotient
a = 0.54% R = gas constant
17. (i) Sulphuric acid (H2 SO4 ) is weaker acid in comparison to T = absolute temperature in K
perchloric acid (HClO4 ) × H2 SO4 can take up a proton
(i) Since, DG s = - RT ln K
from HClO4 to form H3 SO+4 . Hence, it acts as a base in Q
this reaction. \ DG = - RT ln K + RT ln Q; DG = RT ln
K
(ii) Bronsted acids can donate H+ easily but they may not If Q < K , DG will be negative and the reaction
be able to donate electrons, e.g. HCl, H2 SO4 , HNO3 . proceeds in the forward direction. If Q = K , DG = 0
Therefore all Bronsted acids are not Lewis acids. reaction is in equilibrium and there is no net reaction.
18. Solubility of Sr(OH)2 = 19.23 g/L (at 298 K) (ii) CO( g) + 3H2 (g) l CH4 (g) + H2 O( g)
[Molar mass of Sr (OH)2 = 87.6 + 2 ´ (16 + 1) [CH4 ] [H2 O]
KC =
=121.6 g mol -1] [CO] [H2 ]3
19.23 On increasing pressure, volume decreases. If we
Molarity, M = = 0.1581mol L-1
121.6 ´ 1 doubled the pressure, volume will be halved and the
molar concentrations will be doubled. Then,
Sr(OH) 2 ¾® Sr 2 + + 2OH-
2[CH4 ] × 2[H2 O]
0.1581 M 0.1581 M 2 ´ 0.1581 M QC =
2[CO] {2[H2 ]} 3
Here, [Sr 2 + ] = 0.1581 M and [OH- ] = 0.3162 M
1 [CH4 ] [H2 O] 1
From, [H+ ] ´ [OH- ] = 10-14 = = KC
4 [CO] [H2 ]3 4
10 -14
[H + ] = = 3.16 ´ 10 -14 Therefore, QC is less than K C , so QC will tend to
0.3162 increase to re-establish equilibrium and the reaction
pH = - log [H+ ] = - log [3.16 ´ 10 -14 ] will go in forward direction.
CO( g) + 3H2 ( g) a CH4 ( g) + H2 O( g)
pH = - 0.4997 + 14 =13.5003 »13.5
22. N2 (g) + 3H2 (g) r 2NH3 (g) ; DH = - 92.38 kJ mol -1 On solving, p = 0.045
It is an exothermic process as DH is negative. \ p (N 2 O 4 ) = 0.14 - 0.045 = 0.095 atm
Effect of temperature According to Le-Chatelier’s
principle, low temperature is favourable for high yield of p (NO 2 ) = 0.55 + 2 ´ 0.045 = 0.64 atm
ammonia, but practically very low temperature slow down 25. Ammonia undergoes decomposition as shown below :
the reaction. So, optimum temperature 700 K is favourable 2NH 3 ( g) 3H 2 ( g) + N 2 ( g)
e
in attainment of equilibrium. NH 3 NH 3 e
Effect of pressure Similarly, high pressure about 200 atm is at 27 °C at 327 °C
(15 atm) ( p = ?)
favourable for high yield of ammonia. On increasing
pressure, reaction goes in the forward direction because the p µ T ( V is constant)
number of moles decreases in the forward direction. p1 p 2
=
Addition of argon At constant volume addition of argon T1 T2
does not affect the equilibrium because it does not change pT
the partial pressures of the reactants or products involved in Þ p2 = 1 2
T1
the reaction and the equilibrium remains undisturbed.
15 ´ 600
23. (i) 2H2 (g) + CO(g) s CH3 OH(g) p2 = = 30 atm
300
According to Le-Chatelier’s principle,
Partial pressure NH 3 H2 N2
(a) Addition of H2 (increase in concentration of
Initial 30 0 0
reactants) shifts the equilibrium in forward 3 1
direction (more product is formed). At equilibrium 30 - x x x
2 2
(b) Addition of CH3OH (increase in concentration of
Final equilibrium pressure = 50 atm
product) shifts the equilibrium in backward 3x x
direction. 50 = 30 - x + +
2 2
(c) Removal of CO also shifts the equilibrium in
Þ x = 20 atm
backward direction.
20
(d) Removal of CH3 OH shifts the equilibrium in % NH 3 decomposed = ´ 100 = 66.7%
30
forward direction.
26. (i) Molecular mass of TlOH = 204 + 16 + 1 = 221 g
(ii) When catalyst is added, the state of equilibrium is not
disturbed but equilibrium is attained quickly. This is conc. in mol L -1 (molarity)
because the catalyst increases the rate of forward and mass of TlOH (g)
=
backward reaction to the same extent. molar mass of TlOH ´ volume of solution (in L)
24. (i) N2 ( g) + 3H2 ( g) r 2NH3 ( g) 2
= = 0. 00452 = 4. 52 ´ 10-3 M
0.8 0.4 x 221 ´ 2
Let the partial pressure of NH3 at equilibrium be x then, Q pOH = - log[OH - ] = - log[4.52 ´ 10-3 ] = 2.344
0.8 + 0.4 + x = 2.8 From, pH + pOH =14
x = 1.6 pH = 14 - 2. 334 = 11. 656 » 11. 66
[ p NH 3 ]2 (ii) Molecular mass of Ca(OH) 2
Kp =
[ p N 2 ] ´ [ p H 2 ]3 = 40 + [(16 + 1) ´ 2] = 74 g mol -1
x 1.6 2 Mass of Ca(OH)2 (g) ´ 1000
Kp = = = 50 Molarity, M =
0. 8 ´ 0. 4 3
0.8 ´ 0.4 3 Molar mass of Ca(OH)2
(ii) N 2 O 4 ( g) r 2NO 2 ( g) ´ volume of solution (in mL)
Pressure at equil. 0.28 1.1 0. 3 ´ 1000
M= = 0. 0081
p ( N O 2 )2 (1.1) 2 74 ´ 500
Kp = = = 4.32 atm
p ( N2 O 4 ) (0.28) One mole of Ca(OH) 2 gives 2 moles of OH - .
If volume of the container is doubled, the pressure will So, [OH - ] = 2 ´ 0. 0081 = 0. 0162 M
be reduced to half. pOH = - log[OH - ] = - log[0.0162]
N 2 O4 r 2NO 2 = 1.7905 » 1.79
From, pH + pOH =14
New pressure æç - p ö÷ æ 1.1 + 2p ö
0.28
ç ÷
è 2 ø è2 ø or pH = 14 - 1.79 = 12.21
2 (iii) Molecular mass of NaOH = 23 + 16 + 1 = 40
æ1.1 ö
ç + 2p ÷ M=
Mass of NaOH (g) ´ 1000
è 2 ø
Kp = = 4.32 Molar mass of NaOH ´ volume of solution (mL)
æ 0.28 ö 0. 3 ´ 1000
ç - p÷ = = 0. 375
è 2 ø 40 ´ 20
pOH = -log [0.0375] [H r ][S2 - ]

\ K 2 = 1 ´ 10-5 =
= - log [3.75 ´ 10-2 ] = 1. 426 » 1. 43 [HSs ]
From, pH + pOH =14 Because [Hr ] already in solution = 0.018 and thus,
pH = 14 - 1.43 = 12.57 dissociation of HSs further suppresses due to common ion
(iv) In case of dilution, M1V1 = M 2 V2 effect and 1 - a » 1.
0. 018 ´ C1a1
13. 6 ´ 1 = M 2 ´ 1000 \ 1 ´ 10-5 = = 0. 018 ´ a1
C1 (1 - a1 )
13. 6 ´ 1
M2 = = 0. 0136 1 ´ 10-5
1000 \ a1 = = 5. 55 ´ 10-4
0. 018
= 1. 36 ´ 10-2 M
\ [S2 - ] = C1a1 = 0. 018 ´ 5. 55 ´ 10-4 = 0. 099 ´ 10- 4
pH = - log[1. 36 ´ 10-2 ] 29. (i) K C = [NO2 ] 4 [O2 ]
= - 0.1335 + 2 (because molar concentrations of pure solids are
=1. 8665 pH =1. 87 constant)
27. (i) The ionisation equation of HOCl is as follows: (ii) Number of moles of reactants and products are equal
HOCl(aq) + H2 O(l ) S H3 O+ ( aq) + ClO- ( aq) (i.e. Dn g = 0)
Initial conc. 0.08 0 0 2 NO( g) N 2 ( g) + O 2 ( g)
Change in conc. - x +x +x
º
then, K p as well as K C have no units.
to reach equil.
Equil. conc. 0.08- x x x Or
For a reaction moving forward, (a) K C > Q and for a
[ H O + ] [ ClO - ] x2
\ Ka = 3 = reaction moving backwad (b) K C < Q.
[ HOCl ] (0.08 - x ) Dn
(iii) We know that, K p = K C (RT ) g
Q x << 0.08 For the above reaction,
\0.08 - x ~- 0.08 Dng = (2 + 1) - 2 = 1
x 2 = 2.0 ´ 10- 6 or x = 1.41 ´ 10- 3 K p = 3.17 ´ 10-6 (0.0831 ´ 1069)
[ H+ ] = 1.41 ´ 10 - 3 M
K p = 3.33 ´ 10-4
[HOCl]Dissociated
Percentage dissociation = ´ 100 (iv) For the reaction the reaction quotient,
[HOCl]Initial
QC = [B ] [ C ] / [ A ]2
1.41 ´ 10 - 3 as [ A ] = [B ] = [ C ] = 3 ´10- 4 M
= = 1.76%
0.08 QC = ( 3 ´ 10- 4 ) ( 3 ´ 10- 4 ) / ( 3 ´ 10-4 )2 = 1
pH = - log [ H+ ] = - log(1.41 ´ 10- 3 ) = 2.85 As QC > K C so the reaction will proceed in the reverse
(ii) Greater the ionisation constant (K b ) of a base, greater is direction.
its ionisation. The decreasing order of the extent of 30. (i) If the volume is kept constant and an inert gas such as
ionisation at equilibrium is argon is added which does not take part in the reaction,
Dimethylamine > Urea > Pyridine > Ammonia. the equilibrium remains undisturbed. It is because the
Hence, dimethyl amine is the strongest base. addition of an inert gas at constant volume does not
28. The first step of the dissociation of H 2 S is change the partial pressure or the molar concentrations
of the substance involved in the reaction. The reaction
H 2S r Hr + HSs
quotient changes only if the added gas is reactant or
[Hr ] [HSs ]
K1= = 4 ´ 10-3 product involved in the reaction.
[H 2S] (ii) Increase in pressure favours melting of ice into water
Q[Hr ] = Ca , [HSs ] = Ca , [H 2S] = C (1 - a ) because at higher pressure melting point of ice is
Ca × Ca Ca 2 lowered.
\ 4 ´ 10-3 = =
C (1 - a ) (1 - a ) Or
0.1 ´ a 2 The equilibria involves heating of reactant, i.e.
4 ´ 10-3 = (1 - a should not be neglected) Solid + heat 1 liquid. So on heating forward
(1 - a )
reaction is favoured and amount of solid will decrease.
or a = 0.18
(iii) As reaction is exothermic, low temperature favours
\ [Hr ] = Ca = 0.1 ´ 0.18 = 0.018 M
forward reaction. High pressure favours forward
[HSs ] = Ca = 0.1 ´ 0.18 = 0.018 M reaction as it is accompanied by decrease in the
[H 2S] = C (1 - a ) = 0.1 (1 - 0.18) = 0. 082 M number of moles.
Now, HSs further dissociates to Hr and S2- (iv) On reducing volume, pressure will increase. According
C1 = [HSs ] = 0.018 M to Le-Chatelier principle, equilibrium will shift to the
HSs r Hr + S2 - side where number of moles of gas can be increased. In
1 0 0 the above reaction, equilibrium will shift in forward
(1 - a 1) a1 a1
direction.
Chapter Test 6. Assertion A solution containing a mixture of acetic
acid and sodium acetate maintains a constant value
of pH on addition of small amounts of acid or alkali.
Reason A solution containing a mixture of acetic
acid and sodium acetate acts as buffer solution
Multiple Choice Questions around pH 4.75.
1. For the reaction, 7. Assertion Increasing order or acidity of hydrogen
I2 (g ) g 2I(g ) ; KC = 37.6 ´ 10 -6 halides is HF < HCI < HBr < HI.
at 1000 K. If 1.0 mole of I2 is introduced into a 1.0 L flask at Reason While comparing acids formed by the
1000 K, at equilibrium elements belonging to the same group of periodic
(a) [I 2 ] > [I] (b) [I 2 ] = [I] table, H¾ A bond strength is a more important
(c) [I 2 ] < [I] (d) Unpredictable factor in determining acidity of an acid than the
polar nature of the bond.
2. For the following equilibrium,
N2O 4 ( g ) z 2NO 2( g ) Short Answer Type Questions
Kp is found to be equal to KC . This is attained when 8. One mole of H2O and one mole of CO are taken in
(a) T = 1 K (b) T = 273 K (c) T = 12. 18 K (d) T = 17. 15 K 10 L vessel and heated to 725 K. At equilibrium,
3. On increasing the pressure, in which direction will the gas 40% of water (by mass) reacts with CO according to
phase reaction proceed to re-establish equilibrium, is the equation,
predicted by applying the Le-Chatelier’s principle. H2O ( g ) + CO( g ) r H2( g ) + CO 2( g )
Consider the reaction, Calculate the equilibrium constant for the reaction.
[Ans. Kc = 0.444]
N2 (g ) + 3H2 (g ) s 2NH3 (g )
9. Some processes are given below. What happens to
Which of the following statement is correct, if the total the process if it is subjected to a change given in
pressure at which the equilibrium is established is the brackets?
increased without changing the temperature? (i) Ice Melting point water (Pressure is increased)
s
(a) K will remain same
(b) K will decrease (ii) Dissolution of NaOH in water (Temperature is
increased)
(c) K will increase
(iii) N2( g ) + O 2( g ) r 2NO( g ) -180.7 kJ (Pressure is
(d) K will increase initially and decrease when pressure is very high
increased and temperature is decreased.)
4. Which of the following combinations of CH3COOH + NaOH
10. Calculate the pH of a solution formed by mixing
would result in the formation of acidic buffer? equal volumes of two solutions, A and B of a strong
(a) 1 : 1 mol ratio (b) 2 : 1 mol ratio acid having pH = 6 and pH = 4 respectively.
(c) 1 : 2 mol ratio (d) Both (a) and (c) [Ans. pH = 4.2967]
Assertion-Reason 11. The solubility product of lead bromide is 8 ´ 10 -5 at
Direction (Q. Nos. 5-7) Each of these questions contains 298 K. If the salt is 80% dissociated in saturated
two statements Assertion (A) and Reason (R). Each of solution, calculate the solubility of the salt (in g/L).
these questions also has four alternative choices, any one [Ans. 8.04 gL -1 ]
of which is the correct answer. You have to select one of Long Answer Type Questions
the codes (a), (b), (c) and (d) given below. 12. (i) At a certain temperature and total pressure of
(a) Both A and R are true and R is the correct explanation of A. 105 Pa, iodine vapour contains 40% by volume of I
(b) Both A and R are true, but R is not the correct explanation atoms.
of A. I2( g ) r 2I ( g )
(c) A is true, but R is false. Calculate Kp for the equilibrium. [Ans. » 2.67 ´10 4 Pa]
(d) A is false, but R is true. (ii) 2 NO (g ) + O 2 (g ) r 2NO 2 (g ); DH = -117 kJ
5. Assertion For any chemical reaction at a particular (a) Predict the effect of an increase in concentration
temperature, the equilibrium constant is fixed and is a of NO on the equilibrium concentration of NO 2.
characteristic property. (b) Predict the effect of pressure decrease as a
Reason Equilibrium constant is independent of result of increased volume on the equilibrium
temperature. concentration of NO 2.
Answers
Multiple Choice Questions For Detailed Solutions
1. (a) 2. (c) 3. (a) 4. (b)
Scan the code
5. (c) 6. (a) 7. (a)
CHAPTER 04
s -Block Elements
In this Chapter...
l Group 1 Elements : Alkali Metals
l Group 2 Elements : Alkaline Earth Metals
l Anamolous behaviour of Beryllium
The elements in which the last electron enters the Ionisation Enthalpy
outermost s-orbital are called s-block elements. Group 1 l
They have low ionisation enthalpies and it decreases on moving
elements (alkali metals) and group 2 elements (alkaline down the group.
earth metals) constitute s-block elements. l
This is because the effect of increasing size outweight
increasing nuclear charge.
Group 1 Elements : Alkali Metals
Li, Na, K, Rb, Cs and Fr belong to alkali earth metals. Hydration Enthalpy
They are collectively known as alkali metals because Hydration enthalpy of these metal ions decreases with increase in
they form hydroxides on reaction with water which are ionic size. Hence, the order for increasing hydration enthalpy is
strongly alkaline in nature.
Li + > Na + > K + > Rb + > Cs + .
The general electronic configuration is ns 1 .
Metallic Character
Occurrence
They are the most electropositive elements in the periodic table
l
They are never found in free state as they are highly
and their metallic character increases down the group as tendency
reactive.
to lose valence electron increases.
l
Sodium and potassium are the most abundant
alkali metals in the earth’s crust. Physical Properties
l
Francium, the longest lived isotope with half-life of l
They are silvery white, soft and light metals.
21 minutes occurs only in traces. l
They have low density which increases down the group.
Atomic and Ionic Radii l
The melting and boiling point of the alkali metals are low due
They have the largest sizes in a particular period of the to weak metallic bonding and impart characteristics colour to an
periodic table. The atomic and ionic radii increases on oxidising flame.
moving down the group. This is because as atomic l
Characteristic colour are given as valence electron is loosely
number increases along a period, nuclear charge also bound and gets excited to higher energy levels by heat energy
increases resulting in decreased size. of flame.
Metal Li Na K Rb Cs (vi) Solution in Liquid Ammonia The solution of alkali

Colour Crimson red Yellow Violet Red violet Blue metals in liquid ammonia is blue, paramagnetic and has
high reducing capacity.
λ / nm 670.8 589.2 766.5 780.0 455.5 This is because of the presence of solvated electrons.
M + ( x + y)NH 3 → [M (NH 3 ) x ] + + [e (NH 3 ) y ] −
Chemical Properties Solvated electrons
The alkali metals are highly reactive due to their large size In concentrated solution, the blue colour changes to
and low ionisation enthalpy. The reactivity of these metals bronze and becomes diamagnetic.
increases down the group.
(i) Reactivity Towards Air On combustion lithium forms Uses of Alkali Metals
monoxide (Li 2 O), sodium forms peroxide (Na 2 O2 ) and l
Li metal is used to make useful alloys, in thermonuclear
the other metals form superoxides ( KO2 , RbO2 , CsO2 ). reactions, to make electrochemical cells.
4Li + O 2 → 2 Li 2 O (monoxide) l
Liquid Na is used as a coolant in fast breeder nuclear reactors.
2Na + O 2 → Na 2 O 2 (peroxide) l
KOH is used as a fertilizer.
M + O 2 → MO 2 (superoxides) l
Cs is used in devising photoelectric cells.
(M = K , Rb , Cs )
The stability of peroxides and superoxides increases with General Characteristics of the
increase in atomic number of alkali metals. Compounds of the Alkali Metals
(ii) Reactivity Towards Water Alkali metals react with
Most of the compounds of alkali metals are ionic in nature.
water to form metal hydroxide and dihydrogen. The general characteristics of some of these compounds are
2M + 2H 2 O → 2M + + 2OH − + H 2 ↑ discussed below
Because of their high reactivity towards air and water,
alkali metals are kept in kerosene oil. Oxides and Hydroxides
(iii) Reactivity Towards Dihydrogen All the alkali metal
l
The stability of peroxides and superoxides of alkali metals
hydrides are ionic solids with high melting points. increases down the group. Order of solubility :
2M + H 2 → 2M + H − Normal oxides > peroxides > superoxides
l
Alkali metal oxides hydrolysed with water to give alkali
(iv) Reactivity Towards Halogens Alkali metals react metal hydroxides.
vigorously with halogens to form ionic halides M + X − .
Lithium halides are somewhat covalent due to small size M 2 O + H 2 O → 2 M + + 2 OH −
and high polarisation of Li. Halides
(v) Reducing Nature It depends upon the value of standard l
All metal chlorides of group-I elements are ionic except
electrode potential or standard reduction electrode LiCl, which is covalent in nature.
potential (E° or E° red). l
The order of melting and boiling point of metal halides is
Higher the negative value of E°, more will be the MF > MCl > MBr > MI.
reducing nature. Electrode potential mainly depends l
All the halides are water soluble. The low solubility of LiF
upon the following three factors, i.e.
in water is due to high lattice enthalpy, whereas low
(i) Li (s ) → Li( g ) ; Sublimation enthalpy solubility of CsI is due to smaller hydration enthalpy.
(ii) Li( g ) → Li + ( g ) + e − ; Ionisation enthalpy
Salts of Oxoacids
(iii) Li + ( g ) + H 2O → Li + ( aq ) ; enthalpy of hydration
l
The alkali metals form salts with all the oxo-acids which are
With the small size of its ion, lithium has the highest generally soluble in water and thermally stable. Their
hydration enthalpy. However, ionisation enthalpy of Li carbonates and in most cases the hydrogen carbonate are
is highest among alkali metals but hydration enthalpy also highly stable to heat.
predominates over ionisation enthalpy. l
As the electropositive character increases down the group,
Therefore, lithium is the strongest reducing agent in the stability of the alkali metal carbonates and hydrogen
aqueous solution mainly because of its high enthalpy of carbonates also increases down the group.
hydration. l
Lithium carbonate (Li 2 CO 3 ) is thermally unstable and leads
Among other elements of the group, E° is least negative to the formation of more stable Li 2 O and CO 2 on heating. Its
for sodium and hence, sodium has the least reducing hydrogen carbonate does not exist as solid.
tendency.
Anomalous Behaviour of Lithium l

Their oxides and hydroxides are much less soluble and
their hydroxides decompose on heating
Due to smallest size of lithium, it shows very high ionisation ∆
enthalpy and highest electronegativity in the group. 2 LiOH → Li 2O + H 2O
It also shows following properties which differentiates it from ∆
Mg (OH) 2 → MgO + H 2O
other alkali metals
l
It is harder than other alkali metals due to strong metallic bond.
l
On heating nitrates of Li and Mg decomposes that gives
l
Unlike other alkali metals, it reacts with nitrogen to form mixture of nitrogen dioxide and oxygen.
∆
nitride. 4 LiNO3 → 2 Li 2O + 4 NO 2 + O 2
l
Li 2 CO 3 , LiF, LiSO 4 and Li 3PO 4 are insoluble in water, ∆
while the corresponding salts of other alkali metals are 2 Mg ( NO3 ) 2 → 2 MgO + 4 NO 2 + O 2
soluble in water.
l
Its melting and boiling points are higher than that of other Group 2 Elements : Alkaline
alkali metals.
l
It is least reactive but strongest reducing agent among all Earth Metals
alkali metals. Be, Mg, Ca, Sr, Ba and Ra belong to group II. They are
l
LiCl is deliquescent and crystallises as LiCl ⋅ 2H 2 O, whereas collectively known as alkaline earth metals because their
other alkali metal chlorides do not form hydrates. oxides and hydroxides are alkaline in nature and these metal
l
Li unlike other alkali metals does not form ethynide on oxides are found in the earth’s crust.
reaction with ethyne. The general electronic configuration is ns 2 .
l
LiNO 3 on heating gives Li 2 O, while other alkali metal
nitrates give nitrites. Atomic and Ionic Radii
l
Bicarbonates and carbonates of Li are unstable towards l
They have smaller atomic and ionic radii than those of
heat and decomposes to give Li 2 O. corresponding alkali metals because of increased nuclear
charge.
Points of Similarities between l
Within the group, the atomic and ionic radii increases with
Lithium and Magnesium increase in atomic number due to addition of extra shells of
Lithium resembles magnesium in many of its properties due electrons in succeeding element.
to their almost similar atomic and ionic radii as shown below
i.e. shows diagonal relationship. Ionisation Enthalpy
Atomic radii (pm) Li = 152 pm ; Mg = 160 pm
l
They have low ionisation enthalpies due to large size of the
atoms but larger than that of alkali metals.
Ionic radii (pm) Li = 76 pm ; Mg 2+ = 72 pm
+
l
Second ionisation enthalpy is more than alkali metals as
These properties are as follows alkali metals acquire noble gas configuration while their
l
Both Li and Mg are harder and lighter than the other configuration becomes ns 1 after losing one electron.
metals in their respective groups. Their melting points l
Down the group, the ionisation enthalpy decreases.
are higher than the other members of their respective
groups. Hydration Enthalpy
l
Both decompose water slowly to liberate hydrogen. Hydration enthalpy of these metal ions decreases with
2 Li + 2 H 2O → 2 LiOH + H 2 increase in ionic size.
Mg + 2 H 2O → Mg (OH) 2 + H 2 Be 2+ > Mg 2+ > Ca 2+ > Sr 2+ > Ba 2+
l
Both form only monoxide when heated in presence of The hydration enthalpies of alkaline earth metal ions are
oxygen. The monoxides are less soluble in water and do not lower than those of alkali metal ions.
combine with excess of oxygen to form superoxide.
Physical Properties
4 Li + O 2 → 2 Li 2O
l
Alkaline earth metals are silvery white lustrous and
2 Mg + O2 → 2 MgO relatively soft but harder than the alkali metals.
l
Carbonates of Li and Mg decompose on heating to give l
The melting and boiling points are higher than
oxide and carbon dioxide gas. corresponding alkali metals.
∆ Melting and boiling point trend is not regular due to
Li 2CO 3 → Li 2O + CO 2
l
different crystal structure of metal.

∆
MgCO3 → MgO + CO 2 l
The electropositive character increases down the group
l
Their bicarbonate do not exist in solid state. from Be to Ba.
l
In Bunsen flame, all alkaline earth metals (except Be and In concentrated form, the colour of these solutions
Mg) give coloured flame. become bronze because of the formation of metal clusters.
Electrons in Mg and Be are tightly bound due to their 1
e − ( NH 3 ) y → NH 2− + H 2 + ( y − 1 ) NH 3
l
small size and hence do not impart colour. 2

l
They have high electrical and thermal conductivities. If ammonia is evaporated from the solution,
hexammoniates of the formula [M( NH 3 ) 6 ] 2+ are obtained
Chemical Properties which slowly decomposed to give corresponding metal
The alkaline earth metals are less reactive than alkali metals. amides.
The reactivity of these elements increases on going down the [M ( NH 3 ) 6 ] 2+ + 2 e − → M ( NH 2 ) 2 + 4 NH 3 + H 2
group.
(i) Reactivity Towards Air and Water Be and Mg are Uses of Alkaline Earth Metals
kinetically inert towards oxygen and water because of l
Be is used in the manufacture of alloys, Mg is used in flash
the formation of an oxide film, while Ca, Sr and Ba are powders and bulbs, MgCO 3 is an ingredient of toothpaste.
readily attacked by air to form oxide and nitride. l
Calcium is used in the extraction of metals from oxides.
As compare to alkali metal, alkaline earth metal have less l
Ca and Ba metals have often been used to remove air from
tendency to react with water.
vacuum tubes.
Be shows no reaction with water (cold as well as hot in l
Ra salts are used in radiotherapy. e.g., in treatment of cancer.
the form of steam); Mg does not react with cold water,
i.e. it reacts with hot water (steam) only to give its
hydroxide while rest of the members react with cold
General Characteristics of Compounds
water to give their hydroxide and hydrogen gas. of the Alkaline Earth Metals
Ca + 2 H 2 O → Ca(OH) 2 + H 2 ↑ The general characteristics of compounds of alkaline earth
Like, alkali metal hydroxides, these hydroxides are basic metals are discussed below
in nature.
Oxides and Hydroxides
(ii) Reactivity Towards Halogens All alkaline earth metals
combine with halogen at elevated temperatures forming l
All the alkaline earth metals, oxides and hydroxides are
halides of type, MX 2 . basic except BeO and Be(OH) 2 which are amphoteric in
nature.
M + X 2 → MX 2
l
The solubility, thermal stability and basic character of these
(iii) Reactivity Towards Hydrogen Except beryllium, all hydroxides increases from Mg(OH) 2 to Ba(OH) 2 .
alkaline earth metals combine with hydrogen upon l
The basic character of these hydroxides increases on
heating to form their hydrides.
moving from Mg to Ba. This is because as the size of
∆
M + H 2 → MH 2 metal atom increases, M—O bond length increases or
the M—O bond become weaker thus, readily breaks to
BeH 2 can be prepared by the reaction of BeCl 2 with release ions which are responsible for the basicity of these
LiAlH 4 . solutions.
2BeCl 2 + LiAlH 4 → 2BeH 2 + LiCl + AlCl 3 l
Solubility increases on moving down the group because
(iv) Reactivity Towards Acids Alkaline earth metals readily both lattice and hydration enthalpy decreases down the
react with mineral acids liberating dihydrogen. group but the decrease in lattice enthalpy is more rapid
M + 2 HCl → MCl 2 + H 2 ↑ than that in hydration enthalpy.
(v) Reducing Nature Alkaline earth metals are strong Halides
reducing agents but their reducing power is less than l
All halides of alkaline earth metals are ionic except Be
those of their corresponding alkali metals. Reducing
which are covalent and electron deficient.
nature increases from Be to Ba, as the ionisation
enthalpies decreases and electrode potential become
l
Beryllium chloride has a chain structure in the solid state.]
more and more negative with increasing atomic number. Hydrides
(vi) Solutions in Liquid Ammonia The solution of alkaline l
The stability of hydrides of alkaline earth decreases from
earth metals is deep blue black. Be to Ba due to decrease in lattice enthalpy.
M + ( x + y )NH3 → [M (NH3 ) x ] 2 + + 2[ e (NH3 ) y ] − l
BeH 2 and MgH 2 are covalent in nature and CaH 2 , SrH 2
2+ −
M + ( x + 2 y ) NH 3 → [M( NH 3 ) x ] + 2 [ e ( NH 3 ) y ] and BaH 2 are ionic in nature.
Salts of Oxoacids Some such properties are given below.

l
Like aluminium, the surface of beryllium is also covered by
l
Solubility of carbonates and sulphates of alkaline earth
a thin layer of its oxide, which makes it resistive toward
metals decreases on moving down the group.
acids.
l
The thermal stability of carbonates increases with increase l
Hydroxides of both beryllium and aluminium dissolve in
in cationic size. This is because the size of sulphate and
excess of alkali to give soluble complexes, i.e. beryllate ion
carbonate is much larger and hence, small change in cation
[Be (OH) 4 ] 2− in case of Be and aluminate ion [ Al (OH) 4 ] −
size do not make a difference.
l
The nitrates of alkaline earth metals are made by in case of Al.
dissolution of carbonates in dilute nitric acid. l
In vapour phase, chlorides of both have chlorine bridged
l
Nitrates decompose on heating to give oxide. structures as shown below.
2M(NO 3 ) 2 → 2MO + 4NO 2 + O 2 Cl Cl Cl Cl
Cl—Be Be—Cl Al Al
Cl
Anomalous Behaviour of Beryllium Cl Cl Cl
l
Beryllium has exceptionally small atomic and ionic size, Both the chlorides are soluble in organic solvents
high charge density and absence of vacant d-orbitals. like benzene, chloroform etc., and behave as strong Lewis
l
It forms covalent compounds. Its oxide and hydroxide are acid.
amphoteric. It does not exhibit coordination number more l
The oxides of both beryllium (BeO) and aluminium ( Al 2O 3 )
than four. are hard, high melting insoluble solids.
l
It shows diagonal relationship with aluminium. l
The oxides and hydroxides of both Be and Al are
e.g. both Al and Be are not readily attacked by acids. amphoteric and dissolve in sodium hydroxide solution as
l
The chloride of both Be and Al have bridged chloride (Cl − ) well as in hydrochloric acid.
structure in vapour state. BeO + 2 HCl → BeCl 2 + H 2O
l
Be and Al ions have strong tendency to form complexes.
BeO + 2 NaOH → Na 2BeO2 + H 2O
Sodium beryllate
Diagonal Relationship between Beryllium
and Aluminium Al 2O3 + 6 HCl → 2 AlCl 3 + 3 H 2O
The atomic and ionic radii and charge/radius ratio of Al 2O 3 + 2 NaOH → 2 NaAlO 2 + H 2O
beryllium and aluminium are almost similar. That’s why these Sodium
meta aluminate
two resemble in some of their properties.
Chapter
Practice
7. When sodium is dissolved in liquid ammonia, a
PART 1 solution of deep blue colour is obtained. The colour
Objective Questions of the solution is due to
(a) ammoniated electron (b) sodium ion
(c) sodium amide (d) ammoniated sodium ion
l Multiple Choice Questions 8. Alkali metals react with water vigorously to form
1. Alkali metals show regular trend in their physical hydroxides and dihydrogen. Which of the following
and chemical properties with the alkali metals reacts with water least vigorously?
(a) increasing atomic number (a) Li (b) Na (NCERT Exemplar)
(b) increasing s-electrons (c) K (d) Cs
(c) decreasing atomic number
9. Alkali metals are kept in kerosene oil. Which of the
following reason(s) is/are correct regarding this
2. The order of decreasing ionisation enthalpy in alkali statement?
metals is (a) Due to high reactivity of alkali metal
(a) Na > Li > K > Rb (b) Rb < Na < K < Li (b) Due to high ionisation enthalpy of alkali metals
(c) Li > Na > K > Rb (d) K < Li < Na < Rb (c) Due to large size of alkali metals
(d) Both (a) and (b)
3. The alkali metals have low melting point. Which of
the following alkali metal is expected to melt if the 10. Which of the following properties of hydroxides of
room temperature rises to 30°C ? (NCERT Exemplar) alkaline earth metals increases from top to bottom?
(a) Na (b) K (a) Thermal stability (b) Basic character
(c) Rb (d) Cs (c) Solubility in water (d) All of these
4. The alkali metals and their salts show characteristic 11. Which of the following element(s) is used as
colour to electrode(s) in photoelectric cells?
(a) an oxidising flame (a) Sodium (b) Caesium
(b) a reducing flame (c) Potassium (d) Both (b) and (c)
(c) they don’t show any colour to any flame 12. Powder of beryllium burns in air frequently to
(d) Both (a) and (b) produce
5. The reducing power of a metal depends on various (a) BeO (b) Be3N 2
factors. Suggest the factor which makes Li the (c) Be2O (d) Both (a) and (b)
strongest reducing agent in aqueous solution ? 13. Some of the group 2 metal halides are covalent and
(a) Sublimation enthalpy (NCERT Exemplar) soluble in organic solvents. Among the following
(b) Ionisation enthalpy metal halides, the one which is soluble in ethanol is
(c) Hydration enthalpy (a) BeCl 2 (b) MgCl 2 (c) CaCl 2 (d) SrCl 2
(d) Electron-gain enthalpy
14. Which one of the following alkaline earth metal
6. When sodium is dissolved in liquid ammonia, a sulphates has its hydration enthalpy greater than its
solution of deep blue colour is obtained. The colour lattice enthalpy?
of the solution is due to (a) CaSO 4 (b) BeSO 4 (c) BaSO 4 (d) SrSO 4
(a) ammoniated electron
(b) sodium ion 15. The main pigment for the absorption of light in
(c) sodium amide plants is chlorophyll which contains
(d) ammoniated sodium ion (a) Mg (b) Mn (c) Ca (d) Fe
l Assertion-Reasoning MCQs In the periodic table below, the s-block is coloured pink.
s-block
Direction (Q. Nos. 16-20) Each of these questions 1A p-block 8A
contains two statements Assertion (A) and Reason 1s 2A 3A 4A 5A 6A 7A 1s
2s 2p
(R). Each of these questions also has four alternative d-block
3s 3B 4B 5B 6B 7B 8B 1B 2B 3p
choices, any one of which is the correct answer. You 4s 3d 4p
have to select one of the codes (a), (b), (c) and (d) 5s 4d 5p
given below. 6s 5d 6p
(a) Both A and R are true and R is the correct 7s 6d
explanation of A.
f-block
4f
explanation of A.
5f
(d) A is false, but R is true. The s-block elements are the 14 elements contained
16. Assertion The elements of s-block do not occur within these columns. All of the s-block elements are
free in nature. unified by the fact that their valence electrons (outermost
Reason The s-block elements are highly electrons) are in s-orbital. The s-orbital is spherical and
electropositive in nature. can be occupied by a maximum of two electrons.
17. Assertion The alkali metals lose their valence Element in column 1 have one electron in the s-orbital
and elements in column 2 (plus helium) have two
electron to form monovalent cation.
electrons in the s-orbital. The s-block elements include
Reason All the alkali metals have electronic
hydrogen (H), helium (He), lithium (Li), beryllium (Be),
configuration, ns 1 outside the noble gas core. sodium (Na), magnesium (Mg), potassium (K), calcium
18. Assertion Alkali metals are soft and have low (Ca), rubidium (Rb), strontium (Sr), cesium (Cs), barium
melting points. (Ba), francium (Fr) and radium (Ra). The periodic table
Reason Alkali metals have low ionisation shows exactly where these elements are within the
enthalpy than other metals. s-block.
19. Assertion Alkali metals cannot be extracted by All of the s-block elements are metals. In general, they
reduction of their oxides and other compounds. are shiny, silvery, good conductors of heat and electricity
and lose their valence electrons easily. In fact, they lose
Reason Alkali metals are strong oxidising agents.
their trademark s-orbital valence electrons so easily that
20. Assertion All alkali metal compounds are easily the s-block elements are considered to be some of the
soluble in water. most reactive elements on the periodic table.
Reason The compounds of alkali metals are (i) Which of the followings-block elements has the highest
ionic in nature as well as covalent in nature. melting point ?
(a) Be (b) Mg `(c) Ca (d) Ba
l
Case Based MCQs (ii) The electronic configurations of two neutral elements
A and B are A = 1s 2 , 2s 2 , 2 p 6 , 3s 2 andB = 1s 2 ,2s 2 , 2 p 5 .
21. Read the following and answer the questions
from (i) to (iv) given below Which of the following represents the structure of the
compound formed by them?
Within the periodic table, the s-block is located
to the far left and includes all of the elements in (a) A − B (b) B 2+ ( A − )2 (c) A 2+ (B − )2 (d) A + B −
the first two columns (columns 1 and 2) plus (iii) AmongstLiCl, RbCl, BeCl 2 and MgCl 2 , the
helium, which is located in the top right corner compounds with largest and smallest ionic character
in column 8A (column 18 on some versions of respectively are
the periodic table). (a) LiCl and RbCl (b) RbCl and BeCl 2
(c) RbCl and MgCl 2 (d) MgCl 2 and BeCl 2
(iv) The ion having highest mobility in aqueous solution. Or

(a) Be2+ (b) Mg2+ (c) Ca 2+ (d) Ba 2+
Identify correct formula of halide of alkaline earth
Or metal from following
Cation which gives a yellow precipitate with (a) BaCl 2 ⋅ H2O (b) BaCl 2 ⋅ 4H2O
potassium chromate is (c) SrCl 2 ⋅ 4H2O (d) CaCl 2 ⋅ 6H2O
(a) NH+4 (b) Ba 2+ (c) Ca 2+ (d) Na+
22. Read the following and answer the questions from

(i) to (iv) given below PART 2
The group 2 elements are known as alkaline earth
metals which include beryllium, magnesium, Subjective Questions
calcium, barium, strontium and radium. These
metals are soft, silvery white that are less metallic in l Short Answer Type Questions
character than the group 1 alkali metals. Although
many characteristics are common throughout the 1. What happens, when
group, the heavier metals such as Ca, Sr, Ba and Ra (i) sodium metal is dropped in water?
are almost as reactive as the group 1 alkali metals. (ii) sodium metal is heated in free supply of air?
All the elements in group 2 have two electrons in their (iii) sodium peroxide dissolves in water? (NCERT)
valence shells, and show an oxidation state of + 2. 2. The stability of peroxide and superoxide of alkali
Alkaline earth metals are shiny, soft or semi-soft metals increase as we go down to group. Explain by
metals that are insoluble in water. They are generally giving reason. (NCERT Exemplar)
harder and less reactive than the metals of group IA, 3. Write the balanced equations for the reactions between
such as sodium, and are softer and more reactive (i) Na 2 O 2 and water (ii)KO 2 and water (NCERT)
than the metals in group IIIA, such as aluminium.
When the alkaline earth metals combine with oxides
4. Explain the following:
(molecules of oxygen and another element) they (i) Sodium metal is stored under kerosene.
make up some of the most common minerals on (ii) Sodium wire is used to dry benzene but cannot be used
earth, with a variety of uses in industry, medicine to dry ethanol.
and consumer goods. Some compounds give off a 5. Comment on each of the following observations.
great deal of light when heated which makes them (i) The mobilities of the alkali metal ions in aqueous
key ingredients in fireworks. solution are
(i) Alkali metals are generally silvery white but Li+ <Na+ <K+ <Rb+ <Cs+ .
beryllium and magnesium appears to be
(ii) Lithium is the only alkali metal which forms nitride
(a) reddish (b) greyish directly.
(c) yellowish (d) pink
6. (i) Which colour is imparted to flame by sodium?
(ii) Which of the following reason is true about the low
second ionisation enthalpy of the alkaline earth (ii) Why are lithium salts commonly hydrated and those
metals? of the other alkali metal ions usually anhydrous?
(a) Large size of alkali metals (iii) Out of KOH and NaOH, which is a stronger base and
(b) Stable configuration of alkali metal ions why? (NCERT)
(c) Small size of alkaline earth metals
7. When a metal of group 1 was dissolved in liquid
(d) Stable configuration of monocation of alkaline earth
metal ammonia, the following observations were obtained
(iii) Be and Mg are kinetically inert to oxygen and water (i) Blue solution was obtained initially.
because of the formation of (ii) On concentrating the solution, blue colour changed to
(a) oxide film on their surface bronze colour.
(b) hydrated salt How do you account for the blue colour of the
(c) hydroxide film on their surface solution? Give the name of the product formed on
(d) None of the above keeping the solution for some time.
(iv) Magnesium powder burns in air with blinding white
8. Answer the following:
light and give
(i) Li 2 CO 3 decomposes at lower temperature, whereas
(a) MgO and Mg3N 2 (b) Mg(NO3 )2 and Mg3N 2
Na 2 CO 3 at higher temperature. Explain.
(c) Only MgO (d) MgO and Mg(NO3 )2 (ii) Which is radioactive element of alkali metals?
9. How would you explain? 20. Explain the following

(i) BeO is insouble butBeSO 4 is soluble in water. (i) The hydroxides and carbonates of sodium and potassium
(ii) BaO is soluble butBaSO 4 is insoluble is water. are easily soluble in water, while the corresponding salts
of magnesium and calcium are sparingly soluble in
10. All compounds of alkali metals are easily soluble in water. Evaluate the above statement.
water but lithium compounds are more soluble in (ii) Salts of alkaline earth metals are colourless and
organic solvents. Explain. diamagnetic. Explain.
11. Given reason for the following :
(i) The mobilities of the alkali metal ions in aqueous
l Long Answer Type Questions
solutions are 21. (i) Name the groups which constitutes-block
Li + <Na + < K + < Rb + < Cs + elements?
(ii) Lithium is the only alkali metal which forms nitride (ii) Why cannot sodium and potassium be prepared by
directly. the electrolysis of their aqueous solutions?
(iii) Lithium is strongest reducing agent. (iii) Why is the density of potassium less than sodium?
12. Account for the following : (iv) Why are alkali metals soft and have low melting
(i) When burnt in air, lithium forms normal oxide, points?
Na forms peroxide and K forms superoxide. Why ? (v) What happens when K burns in air? Give chemical
(ii) LiH, LiF andLi 3N show exceptional thermal equation?
stabilities. Explain. 22. (i) Complete the following reactions
(iii) Mg 2+ is much more hydrated than Na + . Why ? Heat
(a) LiOH →
13. Which member of the alkaline earth metals family has
(b) Li + HC ≡≡ CH→
(i) least reactivity
(ii) lowest density (c) Na + O 2 →
(iii) highest boiling point (ii) Lithium resembles magnesium in some of its
properties. Mention two such properties and give
(iv) maximum reduction potential ?
reasons for this resemblance.
14. Arrange the following in the increasing order of the
properties mentioned in the brackets 23. (i) Complete the following reactions :
(i) oxides of group 2 (basicity) (a) Na 2 O 2 + 2H 2 O →
(ii) alkaline earth metal carbonate (thermal stability) (b) 2KO 2 + 2H 2 O →
15. Give reason for the following : (c) LiH + Al 2 Cl 6 →
(i) LiCl has lower melting point than NaCl. (ii) Arrange the following in the decreasing order of
(ii) The second ionisation enthalpy of magnesium is more the property mentioned
than that of first and yet magnesium forms MgCl 2 not (a) Be, Mg, Ca, Sr (melting point)
MgCl. (b) Be, Mg, Ca (metallic radius)
16. Explain E° for M 2+ (aq) + 2 e − → M(s ) 24. (i) Complete and balance following reactions?
∆
(where, M = Ca, Sr or Ba) is nearly constant. (NCERT) (a) Li 2 CO 3  →
17. Complete the following reactions (b) Li 3N + 3H 2 O →
2− −
(i) O2 + H2 O → (ii) O2 + H2 O → (c) Na + O 2 →
(ii) Give reasons for the following
18. Explain, why alkaline earth metals have higher first (a) Alkaline earth metal when dissolve in liquid
ionisation enthalpies than the corresponding alkali ammonia give deep blue black solution.
metals? (b) Beryllium doesn’t impart colour to the flame.
19. An element of group II forms covalent oxide which is (c) Alkaline earth metals are weaker reducing agents
amphoteric in nature and dissolves in water to give than alkali metals.
an amphoteric hydroxide. 25. Ions of an element of group 1 participate in the
Identify the element and write chemical reactions of transmission of nerve signals and transport of sugars
the hydroxide of the element with an alkali and an and amino acids into cells. This element imparts
acid. yellow colour to the flame in flame test and forms an
oxide and a peroxide with oxygen. Identify the element (i) Name an ion of alkali metal which has maximum
and write chemical reaction to show the formation of degree of hydration?
its peroxide. Why does the element impart colour to (ii) Why alkali metals have low melting point?
the flame? (iii) What type of oxides are formed by alkali metals?
26. (i) Complete the following equation (iv) Arrange the following alkali metals in increasing
(a) Ca + 2 H 2 O → electropositive character.
(b) BeO + 2 NH 3 + 4HF → Na, Li, K, Cs
(c) 2BeCl 2 + LiAlH 4 → Or
(ii) Give the chemical equations involved in reaction of Why are alkali metals not found in nature ?
alkaline earth metals withNH 3 . 30. Read the following and answer the questions from
27. (i) Discuss the trend of the following: (i) to (iv) given below
(a) Thermal stability of carbonates of group 2 elements. The oxides and hydroxides of alkaline earth metals
(b) The solubility and the nature of oxides of group 2 are alkaline in nature and found in the earth’s crust.
elements. Beryllium is extracted from beryl by roasting the
(ii) Why do beryllium and magnesium not impart colour mineral with Na 2SiF6 at 700-750°C, followed by
to the flame in the flame test? leaching the soluble fluoride with water and then
28. Compare the solubility and thermal stability of the precipitating Be(OH) 2 at bout pH 12. The largest
following compounds of the alkali metals with those of use of Be is in high-strength alloys of copper and
alkaline earth metals. (NCERT) nickel.
(i) Nitrates (ii) Carbonates (iii) Sulphates Calcium is used in the extraction of metals from
oxides. It is produced by electrolysis of fused
l Case Based Questions CaCl 2 . It is less reactive than strontium or barium,
forming a protective oxide-nitride coating in air
29. Read the following and answer the questions from (i) to
that enables it to be machined in a lather or
(iv) given below
handled by other standard metallurgical
Alkali metals have been studied since 1807. They are techniques. Beryllium metal is relatively
highly conductive soft metals, which have a high lustre unreactive at room temperature, particularly in its
that oxidises quickly when they are exposed to air. massive form. Magnesium is more electropositive
They are the most reactive metals in the periodic table. than the amphoteric beryllium and reacts more
They have tendency to give away their valence
readily with most of the non-metals. Except
electron.
beryllium, all alkaline earth metals combine with
Hence, they are electropositive and they are rarely hydrogen upon heating to form hydrides.
found in elemental form. They are mostly found in
(i) Give the chemical reaction for burning of beryllium
compounds with other elements. They react strongly
powder in air.
with water to form hydroxides and directly with
oxygen to produce oxides. (ii) What type of compounds like oxide is formed by
beryllium and magnesium?
These metals show increase in reactivity on moving
(iii) Arrange the following alkaline earth metals in
down the group in periodic table. Alkali metals also
increasing order of reactivity.
have high conductivity and low melting points. They
are so reactive due to their electronic configuration. Ba, Ca, Mg, Sr.
They are also relatively soft metals. (iv) Name an amphoteric compound of alkaline earth
metals.
However, in their respective periods, they are the Or
largest elements and have the lowest ionisation Which alkali earth metal hydroxide is soluble in
energies. NaOH ?
EXPLANATION
Objective Solutions Beryllium halides have covalent character due to small size
1. (a) The alkali metals show regular trend in their physical and high effective nuclear charge. Hence, BeCl 2 is most
and chemical properties with the increasing atomic number. covalent among all other chlorides.
2. (c) On moving down in the group (from Li to Cs), the 14. (b) As we move down the group, size of metal increases.
ionisation energy value decreases from Li to Cs, size of the Be has lower size while SO 42− has bigger size, that's why
atom increases and so valence electron is less tightly held. BeSO4 breaks easily and lattice energy becomes smaller. Due
Increased screening effect from Li to Cs also makes the to smaller size of Be, water molecules gathered around Be and
removal of electron easier. hence, hydration energy increases.
3. (d) Alkali metals have low melting and boiling points. 15. (a) Main pigment for the absorption of light in plant is
The melting point of alkali metals decreases from Li to Cs as chlorophyll which contains Mg.
cohesive force decreases with increase in atomic size. 16. (a) Both A and R are true and R is the correct explanation of A.
Melting point of Cs = 302 K , i.e. 29°C. As s-block elements are highly electropositive they react
4. (a) Alkali metals and their salts impart characteristic colour vigorously and hence do not occur in free state.
to an oxidising flame. This is because heat from the flame 17. (a) Both A and R are true and R is the correct explanation of A.
excites the outermost electron to a higher energy level.
As they have only 1 electron in their valence shell they
5. (c) Standard reduction potential (E °RP ) is a measure of forms monovalent cation and acquires stable noble gas
tendency of an element to lose electron in aqueous solution. configuration.
Higher the negative E °RP , greater is the ability to lose
18. (b) Both A and R are true but R is not the correct explanation
electrons. of A.
6. (a) The blue colour of the solution of alkali metals in liquid The binding energy of alkali metals ions in the close-packed
ammonia is due to the ammoniated electron which absorbs metal lattices are weak. Hence, these are soft and have low
energy in the visible region of light and thus imparts blue melting points.
colour to the solution.
19. (c) A is true but R is false.
7. (a) All alkali metal dissolve in liquid NH 3 giving highly
Alkali metals are strong reducing agents. Hence, cannot be
conducting deep blue solution. extracted by reduction of their oxides and other compounds.
Na + (x + y ) NH 3 → [ Na (NH 3 )x ] + + e(NH 3 )−y 20. (d) A is false and R is true.
Ammoniated cation Ammoniated electron
All alkali metal compounds except lithium compounds are
When light fall on these solutions, the ammoniated electrons easily soluble in water because they are ionic in nature while
excite in higher energy level by absorbing red wavelengths lithium compounds being relatively covalent are soluble in
and so transmitted light is blue. alcohol and other organic solvents.
8. (a) Li has most negative standard reduction potential due to 21. (i) (a) Being small and hard, Be atoms are packed very closely
very high enthalpy of hydration. Thus, reaction of Li with
water will be most exothermic, but surprisingly Li reacts with in the lattice and as such has highest melting point.
water gently, whereas Na and K vigorously reacts with water. (ii) (c) A loses two electrons to form A 2+ while two atoms of
9. (a) Because of their high reactivity towards air and water, B lose one electron each to form 2B − . Therefore, the
alkali metals are kept in kerosene oil. formula of the compound will be A 2+ (B − )2.
10. (d) On moving from top to bottom (iii) (b) RbCl and BeCl 2. Larger the cation, more will be the
Be(OH)2 ionic character or smaller the cation greater will be the
covalent character. (As per Fajan’s rule).
Mg(OH)2 • Thermal stability increases
(iv) (d) Though Ba 2+ is the heaviest ion but it is least
Ca(OH)2 • Basic character increases
hydrated. As a result, its size becomes lesser than any
Sr(OH)2 • Solubility in water increases other hydrated alkaline earth metal cation and hence has
Ba(OH)2 highest ionic mobility.
11. (d) When Cs and K are irradiated with light, the light Or
energy absorbed may be sufficient to make the metal atom (b) Ba 2+ gives yellow precipitate of barium chromate,
lose an electron. This property makes Cs and K useful as when reacted with potassium chromate.
electrodes in photoelectric cell. K 2CrO4 + Ba 2+ → BaCrO4 + 2K +
12. (d) Powdered beryllium burns brilliantly in air to give BeO 22. (i) (b) Beryllium and magnesium are greyish in appearance.
and Be3N 2. Be2O is not formed as both Be and O have (ii) (b) The second ionisation enthalpies of alkaline earth
valency equal to 2. metals are smaller than alkali metals. This is due to stable
13. (a) Ethanol is an organic compound, i. e. of covalent completely filled ns 2 configuration of alkali metal cations.
character ‘‘Like dissolves like’’. To dissolve in ethanol the
compound should have more covalent character.
(iii) (a) Be and Mg are kinetically inert to water and oxygen (ii) Sodium metal removes moisture from benzene by
due to formation of protective oxide film on the surface reacting with water. However, ethanol cannot be dried
of it. by using sodium because it reacts with sodium.
(iv) (a) Magnesium powder burns in air to give MgO and 2Na + C 2H 5OH → 2C 2H 5ONa + H 2
Mg3N 2 ⋅ MgO does not combine with excess oxygen to 5. (i) Smaller the size of the ion, more highly it is hydrated
give any superoxide. Mg reacts with nitrogen to form and greater the hydration of the ion, lower is its ionic
magnesium nitride (Mg3N 2 ). mobility.
Mg+O2 → MgO Since, the extent of hydration decreases in the order
3Mg+N 2 → Mg3N 2 Li+ > Na+ > K+ > Rb+ > Cs+
Or Therefore, ionic mobility increases in the reverse order
(d) All chloride of alkaline earth metals are hydrated to Li+ < Na+ < K+ < Rb+ < Cs+
different extent. This extent of hydration decreases (ii) Because of its smaller size, lithium just like magnesium
from Mg to Ba. forms a nitride while other alkali metals do not.
∆
Subjective Solutions 6Li (s) + N 2( g) → 2Li 3N(s)
1. (i) H 2 gas is evolved which catches fire due to the 6. (i) Sodium imparts a golden yellow colour to the flame.
liberation of extreme heat in the reaction. (ii) Because of its smallest size among alkali metals. Li + has
the maximum degree of hydration. That’s why lithium
2 Na (s) + 2H 2 O ( l ) → 2NaOH ( aq) + H 2 ( g)
salts are commonly hydrated and those of other alkali
(ii) Na 2O2 along with a small amount of Na 2O is formed. metal ions usually anhydrous.
4 Na (s) + O 2 ( g) → 2 Na 2 O (s) Li + > Na + > K + > Rb + > Cs +
  →
(Minor)
1 ∆H hydration (in decreasing order)
Na 2 O (s) + O 2 (s) → Na 2 O 2 (s)
2 (Major) (iii) KOH is a stronger base than NaOH. Due to large size
of K, K—O bond is weaker than Na—O bond. KOH
(iii) H 2 O 2 is formed when sodium peroxide is dissolved in
has more concentration of OH than NaOH. Therefore,
water.
KOH is a stronger base than NaOH.
Na 2 O 2 (s) + 2 H 2 O ( l ) → 2 NaOH ( aq) + H 2 O 2 ( l )
7. (i) The reaction that takes place when alkali metal is
2. The stability of peroxide or superoxide increases as the size dissolved in liquid ammonia is
of metal ion increases, i.e. M + (x + y )NH 3 → [M(NH 3 )x ] + + [(NH 3 )y ] − e
KO 2 < RbO 2 < CsO 2 The blue colour of the solution is due to the presence of
The reactivity of alkali metals toward oxygen to form ammoniated electron which absorb energy in the
different oxides is due to strong positive field around each visible region of light and thus, impart blue colour to
alkali metal cation. the solution.
(ii) In concentrated solution, the blue colour changes to
Li+ is the smallest, it does not allow O 2 − ion to react with O 2
bronze colour due to the formation of metal ion
further. Na + is larger than Li, its positive field is weaker
clusters. The blue solution on keeping for some time
than Li+ .
liberate hydrogen slowly with the formation of amide.
It cannot prevent the conversion of O 2 − into O 2 . The large
2−
1
+ + + 2−
ions such as K , Rb and Cs permit O 2 ion to react with O 2 M+ + e-- + NH 3 → MNH 2 + H 2
2
forming superoxide ion O −2 .
Ammoniacal Amide
1
8. (i) Na 2CO3 is an ionic compound whereas, Li 2CO3 is a
2
O2 O2 covalent compound. Lattice energy of Na 2CO3 is higher
O 22 − → O 2 − → 2O −2 than that of Li 2CO3. Therefore, Li 2CO3 decomposes at
Oxide Peroxide Superoxide lower temperature.
Furthermore, increased stability of the peroxide or superoxide (ii) Francium is the radioactive element among alkali metals.
with increase in the size of metal ion is due to the stabilisation 9. (i) BeO has higher lattice enthalpy than hydration
of large anions by larger cations through lattice energy effect. enthalpy and hence is insoluble in water. BeSO4 on the
3. (i) Na 2 O 2 (s) + 2H 2 O ( l ) → 2NaOH ( aq) + H 2 O 2 ( aq) contrary, is soluble because the lattice enthalpy is less
(ii) 2 KO 2 (s) + 2H 2 O ( l ) → 2 KOH ( aq) due to bigger sulphate ion.
+ H 2 O 2 ( aq) + O 2 ( g) (ii) In barium oxide, BaO, due to larger size of barium ion
the lattice enthalpy is less than hydration enthalpy and
or 4KO 2 (s) + 2H 2 O ( l ) → 4KOH ( aq) + 3O 2 ( g) hence it is soluble in water. On the other hand, in
4. (i) Because of its reactivity with moisture and oxygen BaSO4 due to larger size of barium as well as sulphate
present in the air, sodium metal is stored under kerosene. ion, the magnitude of hydration enthalpy is much
4Na + O2 → 2Na 2O smaller than the lattice enthalpy and hence it is
Na 2O + H 2O → 2NaOH insoluble in water.
10. Exceptionally small size of Li + ion and high polarising (ii) Superoxide ion react with water to form H 2O2 and O2
power, these are the two factors which develops covalent 2O2− + 2H 2O → 2OH − + H 2O2 + O2
character in the lithium compounds. Compounds of other Hydrogen
peroxide
alkali metals are ionic in nature.
18. Since, the atoms of the alkaline earth metals have smaller size
So, they are soluble in water, while lithium compounds as compared to alkali metals, electrons in the outermost shells
being relatively covalent are soluble in alcohol and other of the alkaline earth metals are tightly held. Moreover,
organic solvents. alkaline earth metals have relatively stable electronic
11. (i) Smaller the size of ion more highly it is hydrated, configurations. Consequently, their ionisation enthalpies are
greater the hydration of ion lower is its ionic mobility. higher than those of alkali metals.
Therefore, mobility increases in this order. 19. An element of group II which forms covalent oxide is
(ii) Because of its smaller size, lithium like magnesium beryllium (Be). Except BeO, all other oxides are ionic in
forms a nitride while other alkali metals do not nature. The amphoteric nature of BeO is shown by the
∆ 2 Li N (s) following reactions :
6 Li(s) + N (g) →
2 3
BeO + 2HCl → BeCl 2 + H 2O
(iii) Lithium has small size which results in highest Beryllium Hydrochloric Beryllium
oxide acid chloride
hydration enthalpy. However, ionisation enthalpy of Li
is highest among alkali metal but hydration enthalpy BeO + 2NaOH → Na 2BeO2 + H 2O
Sodium Sodium beryllate
predominates over ionisation enthalpy. Therefore, Li hydroxide
(Alkali)
is the strongest reducing agent.
12. (i) Li + is very small in size. It can stabilise only small The chemical reactions of Be( OH )2, i.e. beryllium hydroxide
sized oxide ion and therefore, forms only Li 2O. with an alkali and an acid are as follows :
It cannot stabilise other large anions such as peroxide Be(OH)2 + 2OH − → [Be(OH)4 ]2−
and superoxide. Na + being larger in size can stabilise Beryllium
hydroxide
Beryllate ion
large peroxide ion and therefore forms peroxides,

Be(OH)2 + 2HCl + 2H 2O → [Be(OH)4 ]Cl 2 + 4H +
Na 2O2. Beryllium Hydrogen
K + being large in size can also stabilise large hydroxide chloride
superoxide ion forming superoxides, KO2. 20. (i) Sodium and potassium have large size as compared to
(ii) Li + is very small in size. Therefore, its salts with small magnesium and calcium. Therefore, the lattice enthalpies
anions such as F − , H − and N 3− are exceptionally stable of hydroxides and carbonates of sodium and potassium are
due to their high lattice energies. much lower than those of hydroxides and carbonates of
(iii) The extent of hydration depends upon the charge magnesium and calcium.
density. Mg2+ ion is smaller in size than Na + and has As a result, the hydroxides and carbonates of sodium and
twice the charge than Na + . Therefore, its charge potassium are easily soluble in water, whereas the
density is high and hence is extensively hydrated. corresponding salts of magnesium and calcium are
13. (i) Be, (ii) Ca, (iii) Be, (iv) Be sparingly soluble in water.
14. (i) The basicity of oxides of group 2 increase down the (ii) Alkaline earth metals form dipositive ions in their salts.
group, i.e. BeO < MgO < CaO < SrO <BaO. These dipositive ions have noble gas configurations with
no unpaired electrons. Therefore, these compounds are
(ii) The increasing order of thermal stability of alkaline
colourless and diamagnetic in nature.
earth metal carbonate is
21. (i) s-block contains only two groups; group 1 (alkali metals)
BeCO3 < MgCO3 < CaCO3 < SrCO3 < BaCO3. and group 2 (alkaline earth metals).
15. (i) LiCl has more covalent character than NaCl and, (ii) The electrode potential, i.e. reduction potential of Na
hence LiCl has lower melting point than NaCl. (− 2.71 V) or K (− 2.92) is much lower than that of
(ii) This is because, after removing two electrons from H2O (− 0.83V), therefore, upon electrolysis, water gets
Mg, it acquire stable noble gas configuration. reduced in preference to Na + or K + ions. In other words,
16. E° forM 2+ ( aq) + 2 e− → M(s) (where,M = Ca, Sr, Ba) sodium and potassium can not be obtained by electrolytic
reduction of Na + and K+ ions in aqueous solution.
is almost same because, E° of any M 2+ / M electrode
depends upon three factors (i) enthalpy of vaporisation, (iii) This is due to abnormal increase in the atomic size of
(ii) ionisation enthalpy (iii) enthalpy of hydration. potassium.
(iv) Alkali metals have only one valence electron per metal
Since, the combined effect of these factors is approximately
atom. As a result, the binding energy of alkali metal ions
the same for Ca, Sr and Ba, therefore, their electrode
in the close-packed metal lattices are weak. Therefore
potentials are nearly constant. these are soft and have low melting points.
17. O22 − represents a peroxide ion (v) K + O 2 → KO 2 , potassium superoxide will be formed.
O2− represents a superoxide ion
22. (i) ∆
(i) Peroxide ion react with water to form H 2O2. (a) LiOH → Li 2O + H 2O
O22− + 2H 2O → 2OH − +H 2O2 + −
(b) Li + HC ≡≡ CH → LiC ≡≡ CLi + H 2
− +
Hydrogen
peroxide (c) 2 Na + O2 → Na 2O2
(ii) Lithium resembles with magnesium as its charge size excitation of the outermost electron which on reverting back to
ratio is closer to Mg. Its resemblance with Mg is known its initial position gives out the absorbed energy as visible light
as diagonal relationship. and complementary colour of absorbed colour from the light
Generally, the periodic properties show either radiation is seen.
increasing or decreasing trend along the group and That’s why sodium imparts yellow colour to the flame.
vice-versa along the period which brought the 26. (i) (a) Ca + 2H 2O → Ca(OH)2 + H 2
diagonally situated elements to closer value.
∆
Period Group I Group II (b) BeO + 2NH 3 + 4HF → (NH 4 )2BeF4 → BeF2
2 Li Be + 2 NH 4F
3 Na Mg (c) 2 BeCl 2 + LiAlH 4 → 2 BeH 2 + LiCl + AlCl 3
Following characteristics can be noted (ii) Alkaline earth metals dissolve in liquid ammonia to give
Due to covalent nature, chlorides of Li and Mg are deep blue black solution because of ammoniated ions.
deliquescent and soluble in alcohol and pyridine. M + ( x + 2 y )NH 3 → [M(NH 3 )x ]2+ + 2 [ e(NH 3 )4 ]−
Carbonates of Li and Mg decompose on heating 27. (i) (a) All the alkaline earth melals form carbonates (MCO3 ).
and liberate CO2. All these carbonates decompose on heating to
Li 2CO3 → Li 2O + CO2 give CO2 and metal oxide.
The thermal stability of these carbonates increases down
MgCO3 → MgO + CO2
the group, i.e. from Be to Ba.
23. (i) (a)Na 2O2 + 2H 2O → 2NaOH + H 2O2
BeCO3 < MgCO3 < CaCO3 < SCO3 < BaCO3
(b)2 KO2 + 2H 2O → 2 KOH + H 2O2 + O2
BeCO3 is unstable to the extent that it is stable only in
(c)8LiH + Al 2Cl 6 → 2 LiAlH 4 + 6LiCl
atmosphere of CO2. These carbonates however show
(ii) (a)Be > Ca > Sr > Mg reversible decomposition in closed container.
There is no regular trend in melting point due to BeCO3 g BeO + CO2
different crystal lattice of metals.
Hence, more is the stability of oxide formed, less will be
(b) Ca > Mg > Be stability of carbonates. Stability of oxides decreases down
The radii increases down the group due to addition the group is beryllium oxide, i.e. high stable making
of extra shell of electrons in succeeding elements. BeCO3 unstable.
∆ (b) All the alkaline earth metals form oxides of formula
24. (i) (a) Li 2CO3 → Li 2O + CO2
MO. The oxides are very stable due to high lattice energy
(b) Li 3N + 3H 2O → 3Li(OH) + NH 3 and are used as refractory material.
(c) 2Na + O2 → Na 2O2 Except BeO (predominantly covalent) all other oxides are
(Peroxide)
ionic and their lattice energy decreases as the size of
(ii) (a) Alkaline earth metal when dissolve in liquid
cation increases.
ammonia give deep blue black solution because of
The oxides are basic and basic nature increases from BeO
ammoniated electrons formed during the reaction.
to BaO (due to increasing ionic nature).
M + ( x + y ) NH 3 → [M(NH 3 )x ]2+ + 2[ e(NH 3 )y ] BeO < MgO < 1 CaO< Sr
123 12
4 4 3 444 2O444
< BaO
3
(b) Beryllium being smaller in size and have high Amphoteric Weak basic Strong basic
ionisation enthalpy, doesn’t impart colour to the
flame. BeO dissolves both in acid and alkalies to give salts and is
amphoteric.
(c) Alkaline earth metals are smaller in size which
The oxides of the alkaline earth metals (except
leads to higher ionisation enthalpies and less
BeO and MgO) dissolve in water to form basic hydroxides
negative electrode potential than corresponding
and evolve a large amount of heat.
alkali metals. Thus, they are weaker reducing agent
than alkali metals. BeO and MgO possess high lattice energy and thus
insoluble in water.
25. Yellow colour flame in flame test indicates that the alkali
(ii) All alkaline earth metals (except Be and Mg) impart a
metal must be sodium. It reacts with O 2 to form a mixture of
characteristic colour to the Bunsen flame. The different
sodium peroxide, Na 2O2 and sodium oxide Na 2O.
colours arise due to different energies required for
∆
4Na + O2 → 2Na 2O (Minor) electronic excitation and de-excitation.
∆ Be and Mg atoms due to their small size, bind their
2Na 2O + O2 → 2Na 2O2 (Major) electrons more strongly (because of higher effective
∆ nuclear charge).
2Na + O2 → Na 2O2
Hence, require high excitation energy and are not excited
Ionisation enthalpy of sodium is low. When sodium metal or by the energy of the flame with the result that no flame
its salt is heated in Bunsen flame, the flame energy causes an colour is shown by them.
28. (i) Nitrates of alkali metals and alkaline earth metals 1

Li 2 SO 4 → Li 2 O + SO 2 + O2
(a) Alkali metal and alkaline earth metal nitrates are 2
∆
highly soluble in water. 2MgSO 4 → 2MgO + 2SO 2 + O 2
(b) Alkali metal nitrates on strong heating decompose (b) The alkali metal sulphates are soluble in water
to nitrites (except LiNO3 ). (except Li 2SO4 ). The solubility of alkaline earth
On heating further at higher temperature, the metal sulphates in water decreases down the group.
products formed are oxides. BeSO4 and MgSO4 are fairly soluble while BaSO4 is
500 ° C completely insoluble.
2NaNO 3 r 2NaNO 2 + O 2
29. (i) The hydration enthalpies of alkali metal ions decrease
800 ° C with increase in ionic size.
4NaNO 3 r 2Na 2 O +5O 2 + 2N 2
Thus, the decreasing order of hydration enthalpies is
∆ 1 Li + > Na + > K + > Rb + > Cs +
2LiNO 3 → Li 2 O + 2NO 2 + O 2
2 Hence, Li + has maximum degree of hydration.
Alkaline earth metal nitrates on heating decompose (ii) Alkali metals have low melting point due to the
into their corresponding oxide with the evolution of presence of only one valence electron which causes
mixture of NO 2 and O 2 (except Be(NO 3 ) 2 ). weak metallic bonding.
∆ (iii) Alkali metals form three types of oxides; monoxides
2Mg(NO 3 ) 2 → 2MgO + 4NO 2 + O 2
(M 2O), peroxides (M 2O2 ) and superoxides (MO2 ).
(ii) Carbonates of alkali metals and alkaline earth metals (iv) The electropositive character of alkali metals increases
(a) Alkali metal carbonates are thermally quite stable down the group. Hence, the increasing order of
upto 1273 K; above which they melt and then electropositive character of given metals is
convert into oxides. Li < Na < K < Cs
∆ , >1273 K Or
Na 2 CO 3 → Na 2 O + CO 2
Due to high chemical reactivity alkali metals do not
Li 2 CO 3 is considerably less stable and decompose occur free in nature. They are found in the earth’s crust
readily. in the form of halide, sulphate, carbonate, silicate,
∆ borate, oxide ores etc.
Li 2 CO 3 → Li 2 O + CO 2
∆
30. (i) Be → BeO + Be3N 2
All alkaline earth metal carbonates are less stable as Air
compare to alkali metals and decomposes on (ii) Oxides and other compounds of Be and Mg are more
heating to give CO 2 and metal oxide. covalent than those of rest heavier large sized atom.
∆ CaO + CO Covalent character is due to small size and large e/r
CaCO 3 → 2 ratio.
Thermal stability of alkaline earth metal carbonates (iii) The alkaline earth metals are very reactive because
increases down the group. BeCO3 is least stable. they readily lose their two valence electrons to achieve
(b) All the alkali metal carbonates are generally soluble stable electronic configuration.
in water and their solubility increases down the The increasing order of reactivity of given alkaline
group because their lattice energy decreases more earth metals is
readily than the hydration energy. Mg < Ca < Sr < Ba
Alkaline earth metal carbonates are sparingly (iv) Be(OH)2, beryllium hydroxide is amphoteric in nature
soluble in water and their solubility decreases as it reacts with both acid and alkali.
down the group. However, these are more soluble Due to small size of Be, it shows amphoteric character.
in the presence of CO 2 . The other hydroxides of alkaline earth metals are basic
(iii) Sulphates of alkali and alkaline earth metals in nature.
(a) Sulphates of alkali metals are thermally quite stable Or
except Li 2 SO 4 while sulphates of alkaline earth Be(OH)2, an amphoteric hydroxide is soluble in NaOH
metals are decomposed on heating. Their thermal as it reacts with it.
stability increases down the group. Be(OH)2 + 2 NaOH → Na 2BeO2 + 2H 2O
Chapter Test 8. Assertion Sodium and potassium ions are present in
opposite side of the cell.
Reason Sodium and potassium ions operate Na K
Multiple Choice Questions pump across the membrane.
1. Which of the following element(s) form stable Short Answer Type Questions
superoxide?
(a) K (b) Rb 9. (i) Give reason
(c) Cs (d) All of these Li+ ion is smallest in its group but moves
slowly in aqueous solution as compared to other
2. Which compound will liberate oxygen when reacted alkali ions under the influence of an electric
with water? current.
(a) KO 2 (b) Na 2O (c) Cs 2O 2 (d) Na 2O 2 (ii) Give the decreasing order of ionic size of alkali
3. Which of the alkali metal chloride (MCl) forms its metals in aqueous solution.
dihydrate salt ( MCl ⋅ 2H2O ) easily? 10. Sodium forms peroxide, whereas lithium can only form
(a) LiCl (b) CsCl (c) RbCl (d) KCl monoxide. Explain by giving reasons.
4. Which of the following metal is used to form an alloy 11. Name an element from group 2 which forms an
with lead (Pb), known as white metal? amphoteric oxide and a water soluble sulphate.
(a) Na (b) K
12. An element of group 2 forms covalent oxide which is
(c) Li (d) All of these
amphoteric in nature and dissolves in water to give an
5. Which of the following order is correct regarding amphoteric hydroxide.
electropositive character of alkaline earth metals? Identify the element and write chemical reactions of
(a) Be < Mg > Ca < Sr < Ra (b) Be > Mg > Ca > Sr > Ba the hydroxide of the element with an alkali and an
(c) Be < Mg < Ca < Sr < Ba (d) None of these acid.
Assertion-Reasoning MCQs Long Answer Type Questions
Direction (Q. Nos. 6-8) Each of these questions 13. (i) The Eº for Cl2 / Cl− is + 1.36, for 1 / 2 I2 / I − it is
contains two statements Assertion (A) and Reason (R). + 0.53, for Ag+ / Ag is + 0.76, for Na+ / Na is − 2.71
Each of these questions also has four alternative and for Li+ / Li is − 3.04. Arrange the following ionic
choices, any one of which is the correct answer. You species in decreasing order of reducing-strength
have to select one of the codes (a), (b), (c) and (d) I− , Ag+, Cl− , Li +, Na+ .
given below. (ii) Describe the following
(a) Both A and R are true and R is the correct explanation of A. (a) Alkali metals are prepared by electrolysis of
(b) Both A and R are true, but R is not the correct explanation their fused chlorides.
of A. (b) Sodium is found to be more useful than
(c) A is true, but R is false. potassium.
14. Present a comparative account of the alkali and
6. Assertion Na+ and Al3+ are isoelectronic. alkaline earth metals with respect to the following
Reason The nuclear attraction on the outermost shell characteristics.
electrons of Al3+ is greater than that of Na+ . (i) Tendency to form ionic/covalent compounds
7. Assertion Fluorides are less soluble than chlorides of (ii) Nature of oxides and their solubility in water
alkaline earth metals. (iii) Formation of oxosalts
Reason Fluorides of alkaline earth metals have less (iv) Solubility of oxosalts
hydration alkaline earth metals have less hydration (v) Thermal stability of oxosalts
energy.
Answers
For Detailed Solutions
1. (a) 2. (a) 3. (a) 4. (c) 5. (c)
Scan the code
6. (a) 7. (c) 8. (b)
CHAPTER 05
Some p-Block
Elements
In this Chapter...
l General Characteristics of p-block Elements
l Anomalous Behaviours of First Member of Each Family
l Group 13 Elements: The Boron Family
l Anomalous Behaviour of Boron
Group 14 Elements: The Carbon Family
Anomalous Properties and Allotropes Carbon
General Characteristics of Anomalous Behaviours of First

p-block Elements Member of Each Family
l
In p-block elements, the last electron enters in the outermost The first member of each group of p-block differs from rest of
p-orbital. the members of its corresponding group due to its very small
l
There are six groups of p-block elements in the periodic table size and unavailability of d-orbitats.
numbering from 13 to 18. Their valence shell electronic Few of such anomalies are as follows
configuration is ns 2np1- 6 (except for He). (i) Maximum Covalency Because of the absence of
l
Differences in the inner core of their electronic configuration d-orbitals, the elements of second period (i.e. first
greatly influence their physical and chemical properties. member of each group) cannot expand its covalency
l
The maximum oxidation state shown by a p-block element is
beyond four, i.e. their maximum covalency is four
(because of the availability of one 2s and three
equal to the total number of valence electrons.
2p-orbitals).
l
The number of possible oxidation states increases towards the
Other members of the groups because of the presence of
right of the periodic table.
d-orbitals can expand their covalence above four.
l
In addition to this, so called group oxidation state, p-block
(ii) Formation of pp -pp Bonds The first member of each
elements may show other oxidation states as well.
group have a unique tendency to form pp-pp multiple
l
The tendency of the two electrons in the outermost atomic
bonds with itself or with the other elements of second
s-orbital to remain unshared in compounds of post-transition
period.
metals is called inert pair effect.
In case of heavier members, since d-orbitals are
l
The combined effect of size and availability of d-orbitals
available, so they form pp-dp bond or dp-dp bond
considerably influences the ability of these elements to form
instead of pp-pp bond.
p-bonds.
l
Non-metals have higher ionisation enthalpies and Since, the energy of d-orbitals is higher as compared to
electronegativities than metals. p-orbitals, the pp-dp or dp-dp bonding contribute less
towards the overall stability of the molecules as compared
l
Non-metal oxides are acidic or neutral, whereas metal oxides
to pp-pp bonding.
are basic in nature.
Group 13 Elements : The Boron Family

l
Group 13 contains six elements, viz., B, Al, Ga, In, Tl, Nh and is collectively called boron family.
l
Nh has been prepared in small amounts and its half-life of most stable isotope is 20 seconds. Due to these reasons, its chemistry has
not been established yet.
l
Aluminium is the most abundant metal and third most abundant element in Earth’s crust, after oxygen and silicon.
General Properties
(i) Electronic Configuration Their general electronic configuration is [inert gas] ns 2 np1 .
(ii) Atomic Radii It increases on moving down the group from B to Tl. However, the atomic radius of Ga is less than that of
Al. The presence of additional10 d-electrons offer only poor screening effect for the outer electrons from the increased
nuclear charge in gallium (Ga).
(iii) Ionisation Enthalpy It follows the trend given below
In < Al < Ga < Tl < B
The discontinuity in the ionisation enthalpy values between Al and Ga and that between In and Tl are due to inability of
d-and f -electrons, having low screening effect to compensate the increased nuclear charge.
(iv) Electronegativity It first decreases from B to Al and then increases marginally.
Physical Properties
l
Density of the elements increases down the group from boron to thallium.
l
Boron is non-metallic, extremely hard and has high melting point. Rest of the members are soft metals with low melting point.
Chemical Properties
l
Due to inert pair effect, on moving down the group, stability of lower oxidation state increases.
The trend is as follows B+ < Al + < Ga + < In + < Tl +
Important Chemical Reactions of Group 13
Reactions Properties
Reaction with oxygen l
Crystalline boron is unreactive.
D
4E(s) + 3O2 ( g) ¾¾ ® 2 E 2 O 3 (s ) l
Tl forms thallium (I) oxide and thallium (III) oxide but Tl 2O is more stable than
For thallium, 4Tl(s) + O2 ( g) ¾® 2 Tl 2 O(s) Tl 2O 3.
l
B 2O 3 is acidic, Al and Ga oxide are amphoteric and those of In and Tl are basic.
Reaction with nitrogen l

All elements readily form nitrides at high temperature.
D
2E(s) + N2 ( g) ¾
¾® 2EN(s)
Reaction with halogen l

The covalent trihalides, e.g. BF 3 being electron deficient are strong Lewis
2E (s) + 3X 2 (g) ¾® 2EX 3 (s) (X = F, Cl, Br I ) acids and the tendency to behave as Lewis acids decreases with increase in size
(Exception TlI3 ) down the group.
l
The trihalides of B exist as dicrete molecules while the trihalides of
other elements exists as dimeric form, both in vapour state and in non-polar
solvent.
l
These halides have an ability of complex formation. The boron trihalides have
the tendency to form BX 3L type complexes (where, L is neutral or anionic
donor).
Reaction with Water l

M( OH )3 type hydroxide follow the same trend of basicity
l
They form hydroxide of the type M( OH )3. as shown by oxides.
l
Tl also gives hydroxide of TlOH type. l
Aluminium is very reactive even at lower temperature.
l
No reaction occurs between boron and water. 2 Al(s ) + 3H 2 O( l ) ¾® Al 2 O 3 + 3H 2 ( g )
Reaction with acids and alkalies It exhibits the following similarities

l
2M(s ) + 6HCl ( aq ) ¾® 2M 3+ ( aq ) + 6 Cl - ( aq ) + 3H 2 ( g ) l
Like Si, it is also a typical non-metal with high melting and
( Exception boron )
boiling points and low atomic volumes.
2M(s ) + 2 NaOH( aq )+ 2 H 2 O( l ) ¾® 2NaMO 2 ( aq ) + 3H 2 ( g ) l
It is a bad conductor of electricity and exhibits allotropy like Si.
(Exception In and Tl)
l
Chlorides of both B and Si forms fume in moist air and readily
l
Boron neither reacts with acids nor with alkalies even at hydrolysed by water.
moderate temperature. l
Carbides of B and Si both are very hard and used as a abrasive.
l
Aluminium, being amphoteric, reacts with both.
Anomalous Behaviour of Boron Group 14 Elements : The Carbon

l
Due to its extremely small size, high electron density, high Family
electronegativity and non-availability of d-electron, boron Group 14 includes C, Si, Ge, Sn, Pb, Fl. Flerovium (Fl) has
exhibits following anomalous properties. been prepared in small amount and its half-life is short, thus
l
Boron is a typical non-metal, while other members of the its chemistry has not been established. The general electronic
group are metals. configuration of these elements is ns 2 np 2 .
l
Its melting and boiling points are higher than the other General and Chemical Properties
members of the group. (i) Covalent Radius It increases considerably from C to Si
l
It forms only covalent compounds while other members can thereafter from Si to Pb a small increase in radius is
form covalent as well as ionic compounds. The maximum observed. This is because of the poor shielding effect of
covalency of B is four. intervening d and f-orbitals.
l
Only boron exhibits allotropy and exists in crystalline as well (ii) Ionisation Enthalpy It decreases down the group.
as amorphous forms. However, there is small decrease in D1H from Si to Ge to
l
Except boron all other halides of the group elements are Sn and slight increase in D1H from Sn to Pb is observed.
hydrolysed in water and exist as tetrahedral species [M (OH)4 ]- Thus, the trend is, C > Si > Ge > Sn < Pb.
and octahedral species [M (H2O)6 ]3 + , in aqueous medium. (iii) Electronegativity While moving down the group
l
The monomeric trihalides are electron deficient and act as electronegativity decrease upto Si and from Si to Pb it is
almost the same. Carbon and silicon are non-metals,
strong Lewis acids. Boron trifluoride easily reacts with Lewis
germanium is a metalloid, whereas Sn and Pb are soft
bases, such as NH3, to complete its octet around boron
metals with low melting points.
F3 B + :NH3 ¾® F3 B ¬ NH3 (iv) Oxidation State Carbon and silicon mostly show +4
oxidation state while other elements show both +2 and
Similarity with Silicon +4 oxidation states.
Boron due to its small size and similar e/m ratio, shows
Stability of +2 oxidation state increases down the group
resemblance with silicon, present diagonally opposite to it.
due to inert pair effect.
Important Chemical Reactions of Group 14
Reactions Properties
Reaction with oxygen l
Forms two types of oxides, i.e. monoxide and dioxide.
1
M(s ) + O ( g) ¾® MO (Limited supply) l
Nature of monoxide is : CO-neutral, GeO-acidic, SnO and PbO-amphoteric
2 2
l
Nature of dioxides is : CO2 , SiO2 , GeO2 , SnO2 , and PbO2
M(s ) + O2 ( g) ¾® MO2 (Excess) 144 42444
Acidic
3 1442443
Amphoteric
Reaction with water l
C, Si, Ge are not affected by water.
M(s ) + 2H2 O(l ) ¾¾
D
® MO2 + 2H2 ( g) (Exception-Pb) l
Sn decomposes steam to form dioxide and H 2 gas.
l
Pb is unaffected by H2 O due to the formation of oxide film.
Reaction with halogen l
MX 4 are covalent in nature (exception SnF4 and PbF4 ).
M + X 2 ¾® MX 2 l
Stability of dihalides increases down the group.
M + 2X 2 ¾® MX 4 (Exception-PbI 4 as it does not exist) l
The order of thermal stability of halides is
(where, X = F, Cl , Br, I) CX 4 > SiX 4 > GeX 4 > SnX 4 > PbX 4
l
Except CCl 4 , other tetrachlorides are easily hydrolysed by water.
l
Thermal stability of tetrahalides of the same element decreases with increase in
molecular mass of the tetrahalide. e.g. CF4 > CCl 4 > CBr4 > CI 4 .
l
The stability of dihalides increases down the group.
Anomalous Properties and Allotropes of l

Each layer has sp 2-hybridised carbon atoms in hexagonal ring
Carbon and adjacent layers are held together by van der Waals’ forces,
thus graphite shows lubricating properties.
Carbon is a typical non-metal forming covalent bonds l
It is a good conductor of electricity, so used in making
employing all its four valence electrons. It shows the property
electrodes.
of catenation.
The order of catenation power is C > > Si > Ge » Sn. Uses
The important allotropes of carbon and their properties are
l
Graphite fibres embedded in plastic material form high strength,
described below light weight composites.
l
Being a good conductor, graphite is used for electrodes in
1. Diamond batteries and industrial electrolysis.
l
It has crystalline lattice.
3. Fullerenes
l
It has rigid 3-D network of sp 3-hybridised C-atoms. l
It contains 60 carbon atoms with sp 2-hybridisation.
l
It is the hardest substance known. l
C 60 molecule has a shape, like soccer balls are called
l
It is an insulator of electricity, but a conductor of heat. Buckminster fullerene.
l
C¾ C bond length is 154 pm. l
It contains 25 six-membered and 12 five-membered rings.
Uses l
Other forms of elemental carbon like carbon black, coke and
l
Diamond used as gem stone. charcoal are all impure forms of graphite or fullerenes.
l
Impure diamonds are used in knives for cutting glass and rock
Uses
borers etc.
l
It act as wonderful lubricants.
2. Graphite l
The alkali compounds of C 60 are used as supper conducting
l
It is soft material having layered structure. substance at the temperature rang of 10-40 K.
84
Chapter
Practice
PART 1 8. Boron forms only [BF4 ]- which one of the following
is formed by aluminium?
Objective Questions (a) [AlF 4 ] - (b) [AlF 6 ] 3-
(c) [AlF 4 ] 3- (d) [AlF 6 ] -
l Multiple Choice Questions 9. The element which exists in liquid state for a wide
1. The second period elements of p-block starting range of temperature and can be used for
from boron, are restricted to a maximum measuring high temperature is
covalency of (a) B (b) Al (c) Ga (d) In
(a) four (using 1s, 2s and two 2p-orbitals)
10. Which of the following oxides is acidic in nature?
(b) six (using 1s and 2s -orbitals) (NCERT Exemplar)
(c) four (using 2s and three 2p-orbitals) (a) B 2 O3 (b) Al 2 O3
(d) six (using 1s and three 2p-orbitals) (c) Ga 2 O3 (d) In 2 O3
2. The correct order of atomic radii in group 13 11. AlCl 3 achieves stability by forming a dimer.
elements is
(a) B < Ga < Al < Tl < In (b) B < Al < Ga < In < Tl
Structure of this dimer is
Al Al Cl Cl Cl
(c) B < Al < In < Ga < Tl (d) B < Ga < Al < In < Tl Al
(a) Cl Cl Cl (b) Al
3. BF3 easily reacts with a Lewis base such as NH 3 to
Al Al Cl Cl Cl
complete octet around boron. This can be expressed
as Al Al — Cl Cl
(c) Cl Al (d) None of these
(a) F3 B + NH3 ¾® F3 B ¬ NH 3
·
·
· Al Al — Cl Cl
(b) F3 B + NH3 ¾® F3 B ® NH 3
·
(c) ·· BF3 + NH3 ¾® BF3 ® NH 3 12. In which of the following allotropes of carbon, each
(d) ·· BF3 + NH3 ¾® BF3 ¬ NH 3 carbon atom undergoes sp 3 -hybridisation and linked
-1
4. First ionisation enthalpy (D i H kJ mol ) for the to four other carbon atoms by using hybridised
elements of group 13 follows the order orbitals in tetrahedral fashion?
(a) B > Al > Ga > In > Tl (a) Diamond (b) Graphite
(b) B < Al < Ga < In < Tl (c) Fullerene (d) None of these
(c) B < Al > Ga < In > Tl 13. The tendency of catenation in group 14 elements
(d) B > Al < Ga > In < Tl follows the order
5. Between which of the following elements is the (a) C > Si > Ge > Sn (b) C >> Si > Ge » Sn
discontinuity in the ionisation enthalpy values (c) Si > C > Sn > Ge (d) Ge > Sn > Si > C
observed? 14. Graphite conducts electricity due to the
(a) Al and Ga (b) In and Tl (a) highly delocalised nature of p-electrons
(c) B and Al (d) Both (a) and (b) (b) highly localised nature of p-electrons
6. The electronegativity of aluminium is similar to (c) highly polarised nature of p-electrons
(a) lithium (b) carbon (c) beryllium (d) boron (d) None of the above
7. The relative stability of +1 oxidation state of group 15. The tendency of Ge, Sn and Pb to show +2
13 elements follows the order oxidation state increases in the sequence
(a) Al < Ga < Tl < In (b) Al < Ga < In < Tl (a) Ge = Sn < Pb (b) Ge < Sn < Pb
(c) Tl < In < Ga < Al (d) Ga < Al < In < Tl (c) Ge > Sn > Pb (d) Ge > Sn = Pb
16. Which of the following is used to make transistor diagonal relationship is also seen. B compounds like
and semiconductor devices? halides are not hydrolysed by water unlike other
(a) Ultrapure form of germanium group 13 members. Catenation is an exclusive
(b) Ultrapure form of silicon property of C which it does not share with any other
(c) Both (a) and (b) element of its group.
(d) Neither (a) nor (b) (i) The property which support anomalous behaviour
of boron is
l Assertion-Reasoning MCQs (a) formation of trihalides (b) small size
Direction (Q. Nos. 17-21) For given questions two (c) high electronegativity (d) All of these
statements are given-one labelled Assertion (A) and the (ii) Carbon has no tendency to form complex
other labelled Reason (R). Select the correct answer to compounds due to
these questions from the codes (a), (b), (c) and (d) as (a) its small size
given below. (b) the availability of vacant d-orbitals
(a) Both A and R are true and R is the correct (c) non-availability of vacant d-orbitals
explanation of A.
(d) no tendency to form covalent bonds
explanation of A. (iii) Choose the correct statement about boron.
(c) A is true, but R is false. (a) Its melting and boiling points are higher than other
(d) A is false, but R is true. member of the group
(b) Only boron exhibits allotropy while other member not
17. Assertion Metal borides are used in nuclear (c) It form only ionic while other members can form
industry as protective shields and control rods. covalent as well as ionic compounds
Reason The boron-10 ( 10 B) isotope has high ability (d) All of the above
to absorb neutrons. Or Which of the following statement about carbon is
18. Assertion In bivalent state, most of the halides of correct?
group 13 elements are hydrolysed in water. (a) It has a maximum covalency of six
Reason These are covalent in nature. (b) Diamond is its amorphous form
(c) The distance between two successive layer in graphite
19. Assertion On going down in group 13, inert pair is 141.5 pm
effect increases. (d) Fullerenes act as wonderful lubricants
Reason On going down the group, there is poor (iv) Which of the following is the incorrect?
shielding effect of intervening d and f -orbitals. (a) Anhydrous AlCl 3 is less soluble in diethyl ehter
Due to this, the effective nuclear charge increases (b) Gallium undergo disproportionation reactions
which holds ns-electrons tightly. (c) Boron is unable to form BF63- ion
20. Assertion Sulphur forms many compounds in which (d) Boron trifluoride behave as Lewis acid
the octet rule is obeyed. 23. Read the following and answer the questions from
Reason Due to the absence of d-orbitals in sulphur, (i) to (iv) given below
it follows the octet rule. Carbon can exist in free as well as in combined
21. Assertion The elements of the group 14 are slightly state. In elemental state, it exists in allotropic form
more electronegative than group 13 elements. and in combined form, it exists in the form of
Reason Group 14 elements are larger in size than carbonates, hydrogen carbonates and carbon
group 13 elements. dioxide gas (which is only 0.03% in the air).
Thus, carbon is a versatile element in the world and
l
Case Based MCQs essential constituent of all living organisms.
22. Read the following and answer the questions from Allotropes are the different forms of same element
(i) to (iv) given below having different physical properties but almost
p-block elements are the ones in which the last similar chemical properties. And phenomenon of
electron enters in a p-orbital of valence shell. The existence of allotropic forms of an element is called
first members of each group of p-block differs from allotropy carbon exist in two types of allotropic
rest of the members of its corresponding group due forms, i.e. crystalline and amorphous allotropes. (or
to small size. B and C are the first members of group microcrystalline forms) C has three crystalline
13 and 14 respectively. Their properties differ from allotropes, namely—diamond, graphite and
rest of the members of their group and sometimes a fullerences. Diamond is a three dimensional giant
molecule of carbon in which C-atom are arranged

tetrahedrally. Unlike diamond, graphite, has a two
PART 2
dimensional layered structure.
Fullerenes are prepared by heating graphite in an
Subjective Questions
electric arc in the presence of inert gases like He or l Short Answer Type Questions
Ar. The vapours on condensation gives sooty
material that mainly contains C60 with smaller 1. Discuss the pattern of variation in the oxidation
quantity of C 70 and traces of fullerenes have even states of B to Tl.
number of carbon atoms upto 350 or above. 2. How does electron deficient compound BF3 achieve
(i) C60 an allotrope of carbon contains electronic saturation, i.e. fully occupied outer
(a) 16 hexagons and 16 pentagons electron shells ?
(b) 20 hexagons and 12 pentagons
(c) 12 hexagons and 20 pentagons 3. If B ¾ Cl bond has a dipole moment, explain why
(d) 18 hexagons and 14 pentagons BCl 3 molecule has zero dipole moment? (NCERT)
-
Or 4. Describe the shapes of BF3 and [BH 4 ] . Assign the
Following are the figures of two different allotropes of hybridisation of boron in these species. (NCERT)
carbon. Identify these allotropes from the following
options. 5. Account for the following.
14.15 pm (i) Graphite is used as lubricant.
(ii) Diamond is used as an abrasive.
340 pm
154 pm 6. What is the oxidation state of carbon in each of the

following
(i) CO 2 (ii) CaC 2
(iii) H 2CO 3 (iv) HCN
(v) CO
7. Explain the following
(A) (B)
(i) SiF62- exist but SiCl62- not exist.
(a) A ® Graphite; B ® Diamond (ii) Although, diamond is covalent, yet it has very
(b) A ® Diamond; B ® Graphite high melting point.
(c) A ® Graphite; B ® Fullerene 8. Consider the compounds, BCl 3 and CCl 4 . How will
(d) A ® Diamond; B ® Fullerene
they behave with water? Justify. (NCERT)
(ii) Which of the following statements is correct ?
(a) Fullerenes have dangling bonds
9. Account for the following.
(b) Fullerenes are cage-like molecules (i) Write two factors that can influence the ionic
(c) Graphite is thermodynamically least stable allotrope radius of an element.
of carbon
(ii) Among the elements B, Al, C and Si which has
(d) Graphite is slippery and hard
the highest ionisation enthalpy.
(iii) Which of the following statement is incorrect for
diamond? 10. In some of the reactions, thallium resembles
(a) The C¾ C bond length is 141.5 pm aluminium, whereas in others it resembles with
(b) It is a bad conductor of electricity group I metals. Support this statement by giving
(c) Have high thermal conductivity some evidences. (NCERT)
(d) It have high density 11. Suggest reason, why the B¾F bond lengths in BF3
(iv) Which of the following are amorphous form of (130 pm) and BF4- (143 pm) differ? (NCERT)
carbon?
(a) Coke, fullerenes and charcoal 12. Which of the following is not hydrolysed by water
(b) Coke, diamond and graphite and why?
(c) Graphite, charcoal and lamp-black BF3 , BCl 3 and BBr3
(d) Charcoal, lamp-black and coke
13. When BCl 3 is treated with water, it hydrolyses and 20. Explain the difference in properties of diamond and
-
forms [B(OH)4 ] only, whereas AlCl 3 in acidified graphite on the basis of their structures.
aqueous solution forms [Al(H 2O)6 ]3+ ion. Explain 21. (i) Explain the following
what is the hybridisation of boron and aluminium in (a) Carbon has a strong tendency for catenation as
these species? (NCERT Exemplar) compared to silicon.
14. Three pairs of compounds are given below. Identify (b) The atomic radius increases considerably form C to
that compound in each of the pairs, which has Si and there after from Si to Pb small increase is
group 13 element in more stable oxidation state. observed.
Give reason for your choice. State the nature of (c) Compounds of group 14 elements in + 4 oxidation
bonding also. are generally covalent.
(i) TlCl 3 , TlCl (ii) Arrange the following in the increasing order of
(ii) AlCl 3 , AlCl the property mentioned.
(iii) InCl 3 , InCl (NCERT Exemplar) (a) Ge 2 + , Pb 2 + , Sn 2 + (stability)
(b) C, Si, Pb, Sn, Ge (metallic character)
15. What is the state of hybridisation of carbon in ?
(i) CO 2-
22. (i) Answer the following for group 14 elements.
3
(a) the most electronegative element
(ii) Diamond
(b) the most metallic element
(iii) Graphite (c) the element having tendency to form pp - pp bonds.
16. The +1 oxidation state in group 13 and +2 (ii) Give reason for the following
oxidation state in group 14 becomes more and more (a) PbO 2 is a stronger oxidising agent than SnO 2.
stable with increasing atomic number. Explain. (b) Diamond is covalent, yet it has high melting point.
17. Explain the following 23. (i) Select the member(s) of group 14 that
(i) Pb 4+ acts as an oxidising agent but Sn 2+ acts as a (a) forms the most acidic dioxide.
reducing agent. (b) is commonly found in +2 oxidation state.
(ii) Tl(NO 3 )3 acts as an oxidising agent. (c) used as semiconductor.
(iii) Carbon shows catenation property but lead does (ii) Describe the following
not. (a) White fumes appear around the bottle of aluminium.
(b) Boron is unable to form BF 3-
6 .
l
24. (i) Give reasons for the following
18. (i) Select the member of group 13 that
(a) Third-period elements expand their covalence
(a) shows diagonal relation with silicon above four.
(b) is commonly found in +1 oxidation state. (b) Heavier elements of p-block elements form p bonds.
(ii) Give reason in each of the following (c) Lead is unaffected by water.
(a) There is a phenomenal decrease in ionisation (ii) Discuss the pattern of variation in the oxidation
enthalpy from carbon to silicon. states of
(b) Gallium has high ionisation enthalpy than (a) B to Tl (b) C to Pb
aluminium.
(iii) What is the general outer valence sheet electronic l
configuration of group 14 ?
19. (i) What happen, when (i) to (iv) given below
(a) Boron reacts with sodium hydroxide.
Boron is the first member of group 13 of the
(b) Boron trichloride reacts with hydrogen at high
temperature.
periodic table. As it is the only non-metal of the
group, its properties vary with rest of the members.
(ii) Give reasons for the following
B compounds are generally electron deficient and
(a) Boron shows anomalous behaviour than rest of its
group members.
because of this deficiency, there compound accept
(b) Graphite is used as lubricant.
electrons from other molecules capable of donating
(c) BCl 3 is more stable than TlCl 3. a lone pair.
Boron is a hard refractory solid possessing high All the members of this family are well known.
melting point, low density and very low electrical Silicon is the second and carbon is the seventeenth
conductivity. Because of these many properties it most abundant element (by mass) in the Earth’s
find application in many ways like boron fibres, crust.
nuclear industry, heat resistant glasses. This group not only contains metals and non-metal
(i) Why the elements of the second row (first short but one metalloid (Ge) too. The difference in atomic
period) show a number of differences in properties radii give rise to various trend like ionisation
from other members of their respective families? enthalpy. This follows even in oxidation state trend,
(ii) Among the elements of group 13, why boron where some are stable at + 2 while others at + 4 due
possesses a high melting point. to inert pair effect.
(iii) Boron fluoride exists as BF 3 but boron hydride Even C is quite different from rest of its group
does not exists as BH 3 . members owing to its properties. Hence, even
though these elements are in same group they still
(iv) Why are metal borides used in nuclear industry?
show discrepancies.
Or
(i) Why does silicon show a higher covalency than
Write one similarity of boron with silicon.
carbon?
26. Read the following and answer the questions from (ii) Why is there a small increase in covalent radii
(i) to (iv) given below from Si to Pb?
The group 14 contains 5 elements namely carbon (iii) Arrange the hydrides of group 14 in increasing
(C), silicon (Si), germanium (Ge), tin (Sn) and order of reducing power.
lead (Pb).
(iv) Why does C differ from rest of elements?
Carbon is an essential constituent of all organic Or
matter while silicon is an important constituent of
Write two important uses of fullerenes.
inorganic matter.
EXPLANATIONS
Objective Solutions B+ << Al + < Ga + < In + < Tl +
1. (c) The second period elements of p-block starting from (order of + 1 oxidation state)
boron are restricted to a maximum covalency of four Boron shows consistently +3 oxidation state in its
(using one 2s and three 2p-orbitals). compound, while rest of the elements show +1 as well as +3
2. (d) The atomic radii as well as ionic radii of group 13 oxidation states.
elements increases on moving down the group because of The +1 oxidation state becomes more and more stable as we
the successive addition of one extra shell of electrons. move down the group.
However, there is an anomaly in case of Ga. Atomic radius of This is because of the presence of intervening d and
Ga is lesser as compared to that of Al. Gallium (Ga) with f-orbitals which donot shield the nucleus effectively.
electronic configuration, [Ar]18 3d10 4s 2 4p1 has extra Consequently effective nuclear charge increases, that holds
d-electrons which do not screen the nucleus effectively. the ns electrons tightly so that they do not participate in
Consequently, electrons of Ga are more attracted by nucleus. bonding (inert pair effect).
Thus, the increasing order of atomic radii of the group 13 8. (b) Boron forms [BF4 ] - , while aluminium forms [AlF6 ]3- as it
elements is B (85 pm) < Ga (135 pm) < Al (143 pm) < In expands its covalency beyond four by utilising 3d-orbitals for
(167 pm) < Tl (170 pm). bond formation.
3. (a) The monomeric trihalides of elements of group 13, being 9. (c) In gallium, the crystal structure is different, suggesting
electron deficient, are strong Lewis acids. Boron trifluoride that Ga consists of almost discrete Ga 2 molecule, that’s why
(BF 3 ) easily reacts with Lewis base such as NH3 to complete its melting point is lowest. Ga exists as liquid from 30°C upto
its octet around boron. This can be expressed as shown 2000°C and hence, it is used in high temperature
below thermometry.
F3 B + ·· NH3 ¾® F3 B ¬ NH 3 10. (a) The nature of oxides changes from acidic to basic through
4. (d) On moving from B to Al, the ionisation enthalpies amphoteric on moving down the group.
decreases as expected and this decrease is due to an increase B2 O3 , Al 2 O3 and Ga 2 O 3 , In 2 O3 and Tl 2 O3
in atomic size and shielding effect. 123 144 42444 3 1442443
More acidic Amphoteric Basic
On moving from Al to Ga, the ionisation enthalpy increases less basic
slightly due to increase in effective nuclear charge. 11. (b) Dimeric structure of AlCl 3 is stable in nature and can be
On moving from Ga to In, again there is slight decrease in represented as
ionisation enthalpies due to increased shielding effect. Cl Cl Cl
Al Al
On moving from ln to Tl, ionisation enthalpies show the
increase again because fourteen 4f-electrons shield valence Cl Cl Cl
electron poorely and so effective nuclear charge increases.
12. (a) Diamond has a crystalline lattice. In diamond, each
5. (d) The ionisation enthalpy values as expected from the carbon atom undergoes sp 3 -hybridisation and linked to four
general trends, do not decrease smoothly down the group for other carbon atoms by using hybridised orbitals in
group-13 element. tetrahedral fashion. The structure extends in space and
The decrease from B to Al is associated with increase in size. produces a rigid three dimensional network of carbon atoms.
The observed discontinuity in the ionisation enthalpy values
13. (b) The tendency to form long, open or closed, chains by
between Al and Ga, and that between In and Tl are due to the
combination of some atoms in themselves is known as
inability of d-and f-electrons, which have low screening catenation. The catenation is maximum in carbon and
effect, to compensate the increase in nuclear charge down the decreases down the group.
group.
C >> Si > Ge » Sn > Pb
6. (c) Let, us consider the electronegativity values of the given
elements, This is due to high bond energy of C—C bonds. Down the
Group 1 Group 2 Group 13 Group 19 group, size increases and electronegativity decreases,
Period 2 Þ Li Be B C thereby, tendency to show catenation decreases.
(1.0) (1.5) (2.0) ( 2 .5 )
14. (a) Graphite conducts electricity due to the highly
Period 3 Þ Al delocalised nature of p-electrons.
(1.5)
Be and Al show diagonal relationship which is based on their 15. (b) The tendency of Ge, Sn, Pb to show +2 oxidation state
Z* increases on moving from Ge to Pb. Thus, the correct
same value ( Z * is effective nuclear charge,
r sequence is Ge < Sn < Pb.
r = atomic radius) 16. (c) Ultrapure form of Ge and Si are used to make transistors
So, they have similar electronegativity. and semiconductor devices.
7. (b) The stability order of + 3 and + 1 oxidation states of group 17. (a) Both A and R are true and R is the correct explanation of
13 elements will be A. The boron-10 (10 B) isotope has high ability to absorb
B3 + > Al 3 + > Ga 3 + > In 3 + >> Tl 3 + neutrons and therefore, metal borides are used in nuclear
industry as protective shields and control rods.
(order of + 3 oxidation state)
18. (d) A is false, but R is true. In trivalent state most of the Subjective Solutions
halides of group 13 are hydrolysed in water as they are 1.
covalent in nature. B Al Ga In Tl
Element
19. (a) Both A and R are true and R is the correct explanation of
A. On moving down the group, due to poor shielding effect Oxidation state +3 +3 + 3, + 1 + 3, + 1 +1
of intervening d and f-orbitals, the increased effective
nuclear charge holds electrons tightly (responsible for inert Boron and aluminium show an oxidation state of +3 only
pair effect) and thereby, restricting their participation in because they do not exhibit inert pair effect due to the
bonding. As a result of this, only p-orbital electron may be absence of d or f-electrons. Elements from Ga to Tl show
involved in bonding. So, inert pair effect increases on going two oxidation states, i.e. +1 and +3.
down the group 13. The tendency to show +1 oxidation state increases down the
20. (c) A is true, but R is false. group due to the inability of ns 2 electrons of valence shell to
Sulphur has vacant d-orbital, so it can expand its octet. participate in bonding which is called inert pair effect.
In general, it forms many compounds which obey octet rule. Therefore, Tl + is more stable than Tl 3 + .
21. (c) A is true, but R is false. Group 14 elements are actually 2. BF 3 achieve it by the following ways.
smaller in size than group 13 elements. Group 14 elements (i) Multiple bonding or pp -pp back bonding, e.g. BF3 in
are slightly more electronegative than the latter. which a lone pair of electrons present in 2p-orbital of
22. (i) All the given properties support the anomalous one of the fluorine atoms may be transferred to the
behaviour of boron. vacant p-orbital on the boron atom.
(ii) (c) As C is first member of group 13, so it doesn’t have (ii) Formation of complexes in which electrons are received
d-orbitals. from a donor molecule, e.g. F3 B ¬ NH3 . Boron
(iii) (d) All of the given statements are correct about boron. compounds, thus, behave as Lewis acids.
It show anomalous behaviour because of its extremely 3. Boron in BCl 3 is sp 2 -hybridised, due to this the shape of BCl 3
small size, high electron density, high electronegativity
and non-availability of d-electrons. molecule is trigonal planar. It is symmetrical in shape.
Or (d) Among the given statement and (d) is correct while The net dipole moment for symmetrical molecule is zero
other are incorrect. (because individual dipole moments cancel out due to the
symmetry of the molecule).
(a) Carbon has a maximum covalency of four.
Cl
(b) Diamond is its crystalline form. Cl B 120°
(c) The distance between two successive layer in Cl
graphite is 340 pm. m=0
(iv) (a) Among the given statement (a) is incorrect. Its correct Thus, dipole moment of BCl 3 is zero.
form is anhydrous AlCl 3 is more soluble in diethyl ether
4. In BF3 , boron is sp 2 -hybridised as it contains three bond pairs
because the oxygen atom of ether donates a pair of
electrons to the vacant p -orbital on the Al atom. and therefore, BF3 molecule is trigonal planar in shape.
Cl Cl On the other hand, in [BF4 ]- boron is sp 3 -hybridised because
Al of the presence of four bond pairs and hence, [BF4 ]- species
C2H5
Cl is tetrahedral in shape.
O
Empty p-orbital –
H
C2H5 F
23. (i) (b) C60 is aromatic allotrope of carbon containing 12 B F B
pentagons and 20 hexagons. It is a fullerene having a F H H
H
shape like soccer ball and called Buckminster fullerene.
BF3 sp2-hybridised [BH4 ]– , sp3-hybridised
Or (b) The figures A and B represent diamond and
(Trigonal planar shape) (Tetrahedral shape)
graphite rspectively.
(ii) (b) Fullerene an allotrope of carbon with finite number 5. (i) Graphite has layered structure. Layers are held
of carbon atoms with closed cage structure has been
together by weak van der Waals’ forces and hence, can
identified. The structure is nearly spherical, (like
be made to slip over one another. Therefore, graphite
football).
Sphere is formed by the combination of 20 hexagons acts as a dry lubricant.
and 12 pentagons. Graphite is thermodynamically more (ii) In diamond, each sp 3 -hybridised carbon atom is linked
stable than all allotropes of carbon. to four other carbon atoms. It has three-dimensional
(iii) (a) Among the given statement (a) is incorrect. network of carbon atoms. It is very difficult to break
The C¾ C bond length in diamond is 154 pm. extended covalent bonding and therefore, diamond is a
hardest substance on the Earth. That’s why it is used as
(iv) (d) Charcoal, lamp-black and coke are the amorphous
an abrasive.
form of carbon.
11. In BF3 , boron is sp 2 -hybridised. It has a vacant 2p-orbital.

Carbon Oxidation state
6. Each fluorine in BF3 has completely filled unutilised
compounds (of carbon)
2p-orbitals. Since, both of these orbitals belong to same
(i) CO2 +4 energy level so pp-pp back bonding occurs in which a lone
pair of electrons is transferred from unutilised completely
(ii) CaC 2 -1 filled 2p-orbital of F to vacant 2p-orbital of B. This type of
bond formation is known as back bonding.
(iii) H 2 CO3 +4
Therefore, B¾F bond has some double bond character.
(iv) HCN +2 That’s why all the three boron-fluorine bonds are shorter in
BF3 than the usual single boron-fluorine bond.
(v) CO +2 In [BF4 ]- ion, boron is sp 3-hybridised. It does not have empty
2p-orbital so there is no back bonding. In [BF4 ]- ion, all the
7. (i) SiF62- exists but SiCl 2-
6 does not due to the following four B¾F bonds are purely single bonds and double bonds
reasons are shorter than single bonds. Therefore, B¾F bond length in
(a) Silicon being small in size can accomodate six BF3 is shorter (130 pm) than B¾F bond length (143 pm) in
F atoms but cannot accomodate larger six Cl atoms. [BF4 ]- .
(b) Due to smaller size of F, steric repulsions will be 12. BF3 is not easily hydrolysed by water. It forms an adduct
less in SiF62- . BF3 × OH2 , whereas BCl 3 and BBr3 are hydrolysed to given
(c) Interaction of lone pair of electrons of F with Si is boric acid and HCl or HBr respectively.
stronger than that of Cl lone pairs. This is because the B ¾ F bond in BF3 is very strong due to
(ii) Diamond has three dimensional network structures extensive pp-pp back bonding. As a result, it is not
involving strong carbon-carbon bonds. These bonds are hydrolysed by water. The B¾F bond energy is far greater
difficult to break and, therefore the melting point of than B¾ OH bond energy and cannot be compensated.
diamond is very high. F OH
F—B + H2O HO—B + 3HF
8. BCl 3 is an electron deficient molecule. It easily accepts a OH
F
pair of electrons from water and hence, BCl 3 undergoes (Not possible)
hydrolysis to form boric acid (H3 BO3 ) and HCl.
However, in BCl 3 and BBr3 , the corresponding B¾ Cl and
BCl 3 + 3H2 O ¾® H3 BO 3 + 3HCl B¾Br bond energy is relatively less than B¾F because of
CCl 4 is an electron precise molecule and also have absence inefficient pp-pp back bonding. Therefore, these get
of d-orbitals in C atom and hence, it neither accepts nor hydrolysed.
donates a pair of electrons. Thus, CCl 4 does not undergo 13. In trivalent state, most of the compounds being covalent are
hydrolysis in water. hydrolysed in water, e.g. BCl 3 on hydrolysis in water forms
9. (i) The two factors that can influence the ionic radius of an tetrahedral [M (OH)4 ]- species, in which the hybridisation
element are state of B is sp 3 .
(a) effective nuclear charge, i.e. as effective nuclear BCl 3 + 3H2 O ¾® B(OH) 3 + 3HCl
charge increases, ionic radius decreases. B(OH) 3 + H2 O ¾® [B(OH) 4 ]- + H+
(b) shielding effect, i.e. more be the shielding effect, AlCl 3 in acidified aqueous solution forms octahedral
smaller is the ionic radius. [Al(H2 O) 6 ]3 + ion. In this complex, the 3d-orbitals of Al are
(ii) Ionisation enthalpy increases along a period with involved and the hybridisation state of Al is change to sp 3 d2 .
decrease in atomic size and decreases down the group AlCl 3 + Water ¾® [Al(H2 O) 6 ]3 + + 3Cl - ( aq)
with increase in atomic size. B and C belongs to 2nd 2p
Electronic 1s 2s 3s 3p 3d
period, while Al and Si belong to 3rd period. configuration
Also, carbon lies more towards right side in a period. of Al3+
Hence, carbon (C) has the highest first ionisation
enthalpy. Formation of
[Al(H2O)6]3+
10. Thallium and aluminium both the elements belong to group sp3d 2 -hybridisation
13. Their general electronic configuration for the valence
shell is ns 2 np1. Like Al, thallium also shows +3 oxidation 14. (i) Due to strong inert pair effect, +1 oxidation state of Tl is
more stable than +3. Since, compounds in lower oxidation
state in some compounds like Tl 2 O3 , TlCl 3 , etc. It also
state are ionic but covalent in higher oxidation state,
forms octahedral ions like [TlF6 ]3- as it form by
therefore, TlCl 3 is less stable and covalent in nature but
aluminium, i.e. [ AlF6 ]3- .
TlCl is more stable and is ionic in nature.
Like group-I alkali metals, thallium shows +1 oxidation state (ii) Due to absence of d-orbitals, Al does not show inert
due to inert pair effect in some compounds like TlCl, Tl 2 O pair effect. Therefore, its most stable oxidation state is
etc., like alkali metal hydroxides, TiOH is water soluble and +3. Thus, AlCl 3 is much more stable than AlCl. Further,
its aqueous solution is strongly alkaline. Tl 2 SO4 also forms in the solid or the vapour state, AlCl 3 is covalent in
alums like alkali metal sulphates. Tl 2 CO3 is soluble in water nature but in aqueous solutions, it ionises to form Al 3 +
like alkali metal carbonates. ( aq) and Cl - ( aq) ions.
(iii) Due to inert pair effect, indium exists in both +1 and (iii) Property of catenation depends upon the atomic size of
+3 oxidation states, out of which + 3 oxidation state is the element. Size of carbon is much smaller than that of
more stable than +1 oxidation state. In other words, lead therefore carbon-carbon bond strength is much
InCl 3 is more stable than InCl. Being unstable, InCl higher than that of lead-lead bond. In other words, down
undergoes disproportionation reaction. the group size increases and the tendency to show
3InCl (aq) ¾® 2In(s) + In 3 + (aq) + 3Cl - (aq) catenation decreases. That’s why carbon show property
of catenation but lead does not show catenation.
15. The state of hybridisation of carbon in CO2- 3 , diamond and
18. (i) (a) Boron shows diagonal relation with silicon.
graphite is sp 2 , sp 3 and sp 2 respectively.
(b) Thallium (Tl) is commonly found in + 1oxidation state.
O–
O C (ii) (a) Ionisation energy decreases sharply as we move from
O – carbon to silicon because of large difference in
CO2–
3 atomic size.
14.15 pm The size of C-atom is about 77 pm, whereas that of
silicon is 118 pm. As a result, the electrons in silicon
are less attracted by the nucleus, therefore it has, low
340 pm
154 pm ionisation energy as compared to carbon.

DH1 for carbon is 1086 kJ mol -1, while that of Si is
786 kJ mol -1.
(b) Gallium has higher ionisation entalphy than
aluminium because of higher effective nuclear
charge. This is due to addition of 3 d10 electrons
which do not shield the nuclear charge effectively,
Diamond so, the outer electrons are strongly held.
Graphite
(iii) + 3 oxidation is common in Ga and In.
16. The term inert pair effect is often used in relation to the 19. (i) (a) When boron reacts with sodium hydroxide, sodium
increasing stability of oxidation states that are 2 less than the borate is formed with the evolution of hydrogen gas.
group valency for the heavier elements of groups 13, 14,
15 and 16. 2B + 6 NaOH ¾® 2Na 3BO3 + 3 H 2
(b) When boron trichloride reacts with hydrogen at high
The outershell s-electrons (ns 2 ) penetrate to (n - 1) temperature then boron and hydrogen chloride is
d-electrons and thus becomes closer to nucleus and are formed.
more effectively pulled towards the nucleus. This results in High temp.
2BCl 3 + 3 H 2 ¾¾¾® 2B + 6 HCl
less availability of ns 2 -electrons pair for bonding or ns 2
electron pair becomes inert. This reluctance in the (ii) (a) Boron shows anomalous behaviour than rest of its
participation of ns 2 eletrons in bonding is termed as inert group member because of its small size high electron
pair effect. The inert pair is more effective after n ³ 4 and density, high electronegativity and non-availability of
increases with increasing value of n. d-electrons.
In group 13 all the elements show +3 oxidation state (b) Graphite has layered structured. The layers are held
whereas Ga, In and Tl show +1 oxidation state also. together by weak vander Waals’ forces and hence,
Boron, being small in size can lose its valence electrons to can be made to slip over each other. Therefore,
form B 3 + ion and shows +3 oxidation state. graphite acts as a dry lubricant.
+1 oxidation state of Tl, Ga is due to inert pair effect. (c) On moving down the group 13, the stability of + 3
For groups 14, in spite of four valence electrons, they do oxidation state decreases and that of + 1 oxidation state
not form M 4+ or M 4- ionic compounds. They form covalent increases. This is due to inert pair effect. Therefore,
compounds with four bonds. the + 3 oxidation of B is stable than the + 3 oxidation
Ge, Sn and Pb also exhibit +2 oxidation state due to inert state of Tl. Thus, BCl 3 is more stable than TlCl 3 .
pair effect. Sn 2+ and Pb 2+ show ionic nature. The tendency 20.
to form + 2 ionic state increases on moving down the Diamond Graphite
group due to inert pair effect.
3
17. (i) Due to inert pair effect tendency to form + 2 ions C is sp -hybridised. C is sp 2 -hybridised.
increases down the group, hence Pb2+ is more stable Three dimensional, Two dimensional, sheet like (layer
than Pb4+ . That’s why Pb4+ acts as an oxidising agent tetrahedral structure. like structure).
while Sn 2+ is less stable than Sn 4+ and hence Sn 2+
acts as a reducing agent. Crystalline, transparent Crystalline, opaque and shiny
with extra brilliance (due substance.
Sn 2 + ¾® Sn 4 + + 2 e- ; Pb4 + + 2 e- ¾® Pb2 + to high refractive index).
R.A. O.A.
(ii) Due to inert pair effect Tl in + 1 oxidation state is Hardest substance with Soft having soapy touch with low
more stable than that of + 3 oxidation state. Therefore, high density and high density and high melting point.
Tl(NO3 )3 acts as an oxidising agent. melting point.
21. (i) (a) Carbon has a strong tendency for catenation as (c) Lead is unaffected by water, because of a
compared to silicon. This is because with increase in protective oxide film formation.
atomic size and decrease in electronegativity, the
(ii) (a) B to Tl
tendency to show catenation decreases.
Common oxidation states are +1 and +3. The
(b) The general outer electronic configuration of
group 14 elements is ns 2 np 2 . stability of +3 oxidation state decreases from B to
Tl whereas +1 oxidation increases from B to Tl.
(c) The compounds of group 14 elements in + 4
oxidation states are generally covalent. This is (b) C to Pb
because the sum of first four ionisation enthalpies of The common oxidation states are +4 and +2.
these elements is very high.Thus, it is not easy for Stability of +4 oxidation state decreases from C to
them to lose four electron and form ionic compound. Pb.
(ii) (a) The order of stability of given ions of group 14 25. (i) The differences in the properties of the first member
elements of a group from those of the other members are due to
Ge2 + < Sn 2 + < Pb 2 + (a) the smaller size of the atom, (b) presence of one
This is due to inert pair effect, inner shell of only two electrons and (c) absence of
(b) The increasing order of metallic character is d-orbitals.
C < Si < Ge < Sn < Pb (ii) B possess a high melting point because it has small
This is because down the group metallic character atomic size due to which its individual atoms are
increases. strongly bonded in the solid state and hence, large
22. (i) (a) Among group 14 elements carbon is the most energy is required to break the lattice.
electronegative element. (iii) BF3 exists as a monomer due to pp-pp back bonding.
(b) Lead is the most metallic element. Fluorine transfers two electrons to vacant 2p-orbital of
(c) Carbon has the tendency to form pp - pp bonds. boron.
(ii) (a) In PbO2 and SnO2 , both Pb and Sn are present in +4 The delocalisation reduces the deficiency of electrons
oxidation state. But due to stronger inert pair effect, on boron therby increasing the stability of BF3
Pb 2+ ion is more stable than Sn 2+ ion. Thus, PbO2 is molecule. Whereas, electron deficiency of boron
more easily reduced to Pb 2+ ions than Sn 4+ ions are remains and BH 3 does not exist. It exist as B 2H 6
reduced to Sn 2+ ions. Thus, PbO2 acts a stronger (dimeric form).
oxidising agent than SnO2 . (iv) Metal borides of isotope 10 B, which have high ability
(b) Diamond has a three-dimensional network with to absorb neutron are used in nuclear industry as
strong C— C bonds which are very difficult to break protective shields and control rods.
and thus it has high melting point. Or
23. (i) (a) Among the members of group 14, carbon forms the Chlorides of both B and Si forms fume in moist air and
most acidic dioxide. readily hydrolysed by water.
(b) Among the elements of group 14, the element that is BCl 3 + 3H 2 O ¾® B( OH )3 + 3HCl
commonly found in +2 oxidation is lead. SiCl 4 + 4H 2 O ¾® Si( OH )4 + 4HCl
(c) The elements from group 14 that is used as 26. (i) Si because of the presence of vacant d-orbitals can
semiconductor are silicon or germanium. show a covalency upto six while C because of the
(ii) (a) Anhydrous aluminium chloride is partially absence of d-orbitals cannot have a covalency of more
hydrolysed with atmospheric moisture and liberates than four.
HCl gas. Moist HCl appears white in colour and (ii) There is a considerable increase in covalent radius
gives white fumes around the Al bottle. from C to Si, thereafter from Si to Pb a small increase
AlCl 3 (s) + 3H 2 O( l ) ¾® Al( OH )3 (s) + 3HCl( g) in radius is observed. This is due to the presence
(b) Boron does not have vacant d-orbitals in its valence of completely filled d and f -orbitals in heavier
shell. Therefore, it cannot expand its octet. members.
Therefore, maximum covalency of boron cannot (iii) CH4 < SiH4 < GeH4 < SnH4 < PbH 4 .
exceed four and it does not form BF 36 - ion. (iv) Carbon has smallest size, highest ionisation enthalpy
24. (i) (a) The third period elements of p-block include and high electronegativity and does not have
d-orbital, which can be utilised to form bond and d-orbitals, therefore, it differs from rest of the
expand octet. Thus, they can expand their covalence elements.
above four. Or
(b) The heavier elements of p-block elements forms (i) Fullerenes act as wonderful lubricants.
p-bonds because of the combined effect of size and (ii) The alkali compounds of C 60 are used as super
availability of d-orbitals considerably influence the conducting substance at the temperature range of
ability of their elements to form p-bonds. 10-40 K.
Chapter Test Short Answer Type Questions
9. BCl3 is trigonal planar while AlCl3 is tetrahedral in
dimeric state. Explain.
1. Which of the following is a Lewis acid?
10. Which one is more soluble in diethyl ether,
anhydrousAlCl3 or hydrated AlCl 3? Explain in terms of
(a) AlCl 3 (b) MgCl 2 (c) CaCl 2 (d) BaCl 2
bonding.
2. The exhibition of highest coordination number depends
11. Give reasons for the following.
on the availability of vacant orbitals in the central atom.
Which of the following elements is not likely to act as (i) CCl4 is immiscible in water, whereas SiCl4 is easily
central atom in MF63- ? hydrolysed.
(a) B (b) Al (c) Ga (d) In (ii) Carbon has a strong tendency for catenation as
compared to silicon.
3. The small increase in the covalent radii from Si to Pb is
due to the presence of 12. Explain the following.
(a) half-filled d-orbitals in heavier members (i) CO 2 is a gas whereas SiO 2 is a solid.
(b) completely filled d and f-orbitals in heavier members
(ii) Silicon forms SiF62- ion whereas corresponding
(c) presence of completely filled d-orbitals in lighter members
chloro compound of carbon is not known.
13. Explain the following.
4. Which of the following is the correct order of first
ionisation enthalpy of group 14 elements? (i) Gallium has higher ionisation enthalpy than
(a) Si > Ge > Sn > Pb (b) Si > Ge > Sn < Pb
aluminium.
(c) Si < Ge < Sn < Pb (d) Si < Ge < Sn > Pb (ii) Aluminium forms [AlF6 ] 3- ion but boron does not
form [BF6 ] 3- ion.
5. Which of the following does not exist?
(a) PbI 4 (b) PbCl 4 (c) CCl 4 (d) CBr4 Long Answer Type Questions
Assertion Reason 14. (i) Answer the following

Direction (Q. Nos. 6-8) Each of these questions contains (a) Why the elements of the second row (first short
two statements Assertion (A) and Reason (R). Each of period) show a number of difference in
these questions also has four alternative choices, any properties from other members of their respective
one of which is the correct answer. You have to select families?
one of the codes (a), (b), (c) and (d) given below. (b) Atomic radius of gallium (135 pm) is less than that of
aluminium (143 pm).
(a) Both A and R are true and R is the correct explanation of A.
(b) Both A and R are true, but R is not the correct explanation (ii) Write the chemical equation for the following
of A. reaction:
(c) A is true, but R is false. (a) Boron reacts with oxygen.
(d) A is false, but R is true. (b) Boron reacts with nitrogen.
6. Assertion Boron always forms covalent bond. (iii) Write the two important minerals of aluminium.
Reason The small size of B3+ favours formation of 15. (i) Carbon has a strong tendency for catenation as
covalent bond. compared to silicon. Explain.
7. Assertion Graphite fibres embedded in plastic material (ii) Standard electrode potential value E° for Al3+ / Al is
form high strength, light weight composites. - 1.66 V and that of Tl 3+ / Tl is + 1.26 V predict
Reason The composites are used in products such as about the formation of M 3+ ion in solution
tennis rackets, fishing rods, aircrafts and canoes. and compare the electropositive character of two
metal.
8. Assertion Except CCl4 , other tetrachlorides are easily
(iii) Arrange the following in the increasing order of
hydrolysed by water. the property mentioned.
Reason During hydrolysis, the central atom can (a) Ge 2 + , Pb 2 + , Sn 2 + (stability)
accommodate the lone pair of electrons from oxygen (b) C, Si, Pb, Sn, Ge (metallic character)
atom of water molecule in d-orbital.
Answers
Multiple Choice Questions For Detailed Solutions
1. (a) 2. (a) 3. (b) 4. (b) 5. (a)
Scan the code
6. (c) 7. (b) 8. (a)
CHAPTER 06
Hydrocarbons
In this Chapter...
l Classification of Hydrocarbon
l Alkanes
l Alkenes
Alkynes
Aromatic Hydrocarbons
Carcinogenicity and Toxicity
Hydrocarbons are the compounds of carbon and hydrogen. They are obtained from coal and petroleum.
Classification of Hydrocarbon
Hydrocarbons are classified into three main categories, i.e. saturated (C ¾ C and C ¾ H single bonds), unsaturated
(C ¾ C multiple bonds-double and triple) and aromatic hydrocarbons.
Hydrocarbons
(Compounds of C and H only)
Saturated hydrocarbons Unsaturated hydrocarbons Aromatic hydrocarbons

(Carbon atoms are (Two or more bond(s) are (Alternate single, double
joined together through present between the carbon bond and (4n + 2)π
single bonds only). atom). electrons are present)
Alkanes (CnH2n+2) e.g.

Alkenes (CnH2n)
[Open chain, e.g. (have atleast one double bond (Benzene)
CH3— CH3 (ethane)] between carbon atoms). e.g.
CH2 CH2 (ethene),
Cycloalkanes CH3 — CH CH2( propene)
(Closed chain), etc. (Naphthalene)
e.g. or H2C Alkynes (CnH2n–2)

CH2
H2C (have atleast one triple bond
(Cyclopropane) between carbon atoms).
e.g. CH CH (acetylene),
CH3— C CH (propyne), etc.
Alkanes
l
From alkyl halides
Alkanes are saturated open chain hydrocarbons
Zn, H+
containing C ¾ C single bonds. CH 3 ¾ Cl + H 2 ¾¾® CH 4 + HCl
In alkanes, C-atoms are tetrahedraly joined together in Chloromethane Methane
which C ¾ C and C ¾ H bond lengths are 154 pm and l
Wurtz reaction
112 pm respectively. Dry ether
CH 3 Br + 2 Na + BrCH 3 ¾¾¾® CH 3 ¾ CH 3 + 2 NaBr
All the C-atoms in alkanes are sp 3 -hybridised. Bromomethane Ethane
H l
From carboxylic acids
H
CH 3 COO - Na + + NaOH ¾¾¾¾¾® CH 4 + Na 2 CO 3
CaO
D
sp3-hybridised 109°28′
Sodium ethanoate
Decarboxylation
C
C H
H H H Physical Properties
l
Alkanes are non-polar molecules.
H H l
Due to the weak forces, the first four members, C1 to C4 are gases.
Structure of methane (CH4 ) molecule C5 to C17 are liquids and those containing 18 carbon atoms or
more are solids at 298 K.
Nomenclature and Isomerism l
Alkanes possess weak van-Der Waals’ forces.
Steps to be followed while writing IUPAC names are as l
Alkanes are colourless and odourless.
follows l
Boiling point of alkanes increases with increase in molecular mass.
(i) First of all, the longest chain of carbon atoms
corresponding to the parent alkane is identified.
Chemical Reactions
(ii) The substituents attached to the carbon atoms are
Halogenation
numbered such that the branched C-atoms get the CH 4 + Cl 2
hν
CH 3Cl
hν
Cl 2, HCl
lowest possible numbers.
Cl 2 / hν Cl 2 / hν
(iii) The substituents are written in alphabetical order CH 2Cl 2 CHCl 3 CCl 4
–HCl –HCl
before the name of parent alkane. Controlled
Cu/523K/100 atm
oxidation
l
The phenomenon in which hydrocarbons possess same 2CH 4 + O 2 2CH 3OH
molecular formula but different structures is known as Mo 2O 3
CH 4 + O 2 ∆
HCHO + H 2O
isomerism.
l
Alkanes show structural position and chain isomerism. (CH 3COO) 2Mn
2CH 3CH 3+3O 2 ∆ 2CH 3COOH+2H2O
Alkanes
Difference in properties is due to difference in their

KMnO 4
structures and chain of carbon atoms. (CH 3) 3CH + O2 oxidation
(CH 3) 3COH
l
Based upon the number of carbon atoms attached to a Combustion (3n + 1) Complete
C nH 2n+2 + O2 nCO 2 + (n+1)H2O
carbon atom, the carbon atom is termed as primary (1°), 2 combustion
secondary (2°), tertiary (3°) or quaternary (4°). CH 4 (g) + O 2(g) C(s) + 2H 2O(l)
Incomplete
l
Terminal carbon atoms are primary. Carbon attached to combustion
two carbon atoms is known as secondary. Tertiary C is
attached to three carbon atoms and quaternary C to four Aromatisation
Hexane
V 2O 5 or
Benzene
C-atoms. Al 2O 3 or Cr 2O 3
773 K, 10-20 atm
Isomerisation
Preparation of Alkanes CH3(CH2)4CH3
Anhyd. AlCl 3
CH3CH (CH2)2CH3
HCl
From unsaturated hydrocarbons
CH3
Pt/ Pd/ Ni
CH 2 == CH 2 + H 2 ¾¾¾¾® CH 3 ¾ CH 3 + CH3 CH2CHCH2CH3
Ethene Hydrogenation Ethane
Reaction with Ni
CH3
CH4 + H2O CO + 3H2
steam ∆
Pt /Pd/Ni
CH 3 ¾ CH== CH 2 + H 2 ¾¾¾® CH 3 ¾ CH 2 ¾ CH 3 C6H12 + H2
Propene Propane Pyrolysis 773 K
C6H14 C4H8 + C2H6
Pt /Pd/Ni
CH 3 ¾ Cºº C ¾ H + 2 H 2 ¾¾¾® CH 3 ¾ CH 2 ¾ CH 3 C3H6 + C2H4 + CH4
Propyne Propane
Conformations of Ethane l
The double bond is shorter in bond length (134 pm)
l
Electron distribution of the sigma MO in alkane is symmetrical then the C ¾ C single bond (154 pm).
which is not disturbed due to rotation about its axis. The rotation s-sp2
results into different spatial arrangements of atoms in space which σ π-bond σ
can change into one another. These are called conformations or H H
sp2
conformers or rotamers.
l
There are infinite number of conformations of ethane.
l
The two extreme cases are : eclipsed (hydrogen atoms attached to
two carbons are as close together as possible) and staggered
(hydrogens are as far apart as possible). H sp2-sp2(σ) H
σ σ
l
Any other intermediate conformation is called a skew π-bond
conformation. Eclipsed and staggered conformations can be Orbital diagram of ethene molecule
represented by Sawhorse and Newmann projections as shown
below Nomenclature
H
H
l
For nomenclature of alkenes in IUPAC system, the longest
H
H H chain of carbon atoms containing the double bond is
H selected.
H H
l
Numbering is done from the end which is nearer to double
H H H H bond. The suffix ‘ene’ replaces ‘ane’.
(i) Eclipsed (ii) Staggered
Isomerism
Sawhorse projection of ethane l
Alkenes show both structural and geometrical isomerism.
Angle of rotation or angle
HH H of torsion or dihedral angle l
Alkenes exhibit geometrical (cis-trans) isomerism due
to restricted rotation around the C ¾ C double bond.
H H l
cis-form of alkene is found to be more polar than trans-form
H because dipole moment of trans-form is almost zero.
H H δ+
H H H H3C CH3 H3C δ– H
δ–
H C C C C δ+
(i) Eclipsed (ii) Staggered H H H CH3
(µ=0.33D) (µ = 0D)
Newmann projection of ethane [cis-but-2-ene] [trans-but-2-ene]
Relative Stability of Conformations Preparation of Alkenes

l
In staggered form of ethane, the electron clouds of C ¾ H bonds It can be summarised as follows
are as far apart as possible and have minimum repulsive forces.
conc. H2SO4
l
The repulsive interaction between the electron clouds, which From alcohol C2H5OH
160°-170°C
affects stability of conformation is called torsional strain.
Magnitude of torsional strain depends upon the angle of rotation Alc. KOH
l
From alkylhalide C2H5Br
about C ¾ C bond. This angle is called dihedral angle or torsional
CH2 CH2
angle. From vicinal dihalide CH2Br Zn
l
Out of staggered and eclipsed conformations of ethane, staggered
conformation is more stable as H-atoms are farthest. CH2Br
H2, Pd/C
Alkenes From alkynes CH CH
Lindlar’s catalyst
Alkenes are unsaturated hydrocarbons containing at least one
double bond. Alkenes are also known as olefins, since the first Physical Properties
member, ethylene or ethene was found to form an oily liquid. l
First three members are gases, the next fourteen are
Structure of Double Bond liquids and higher ones are solids.
l
Carbon-carbon double bond in alkenes consists of one strong l
Alkenes are colourless, odourless, insoluble in water but
sigma (s ) bond due to head on overlapping of sp 2 -hybridised fairly soluble in non-polar solvents.
orbitals and one weak pi ( p ) bond obtained by lateral or sideways l
They show a regular increase in boiling point with increase
overlapping of the two 2p-orbitals of the two carbon atoms. in size.
Chemical Properties
Addition of hydrogen H2/Ni, Pt or Pd
H2C CH2 H3C CH3
Rate of hydrogenation 523-573K
—HC==CH2 > — CH == CH—> ring double bond
—CH2 ==CH2 < RCH==CHR
(trans > cis) < R2CH==CH2 < R2CH ==CHR < R2C == CR2
Addition of halogen CCl4

H3CCH CH2 + Cl Cl CH3CH CH2
Cl Cl
(For unsymmetrical Br
alkene-Markownikoff’s rule)
Addition of hydrogen halides
H3CCH CH2 + HBr H3C CH CH3
(In presence of peroxide-reverse of
Markownikoff’s rule)
Peroxide
H3CCH CH2 + HBr CH3CH2CH2Br
Alkenes Note Markownikoff’s rule states that during the addition of hydrogen halides
to unsymmetrical alkenes, the negative part of the addendum gets attached
to that carbon atom which possesses lesser number of hydrogen atoms.
CH3
Addition of water H+
C CH2 + H2O H 3C C CH3
H 3C
CH3 OH
Oxidation Dil. KMnO4

H2C CH2 + H2O + [O] CH2 CH2
273K
OH OH
Ozonolysis H3C Zn/H2O H3C

C CH2 + O3 C O + HCHO + H2O2
H3C H3C
High temperature/
Polymerisation reaction pressure, catalyst
nCH2 CH2 [ CH2 CH2 ]n
O
Addition of H2SO4
CH2 CH2 + H—O—S—O—H C2H5HSO4
Alkynes
Alkynes are unsaturated hydrocarbons that contain at least one triple bond between two carbon atoms.
Nomenclature and Isomerism
l
In IUPAC system, they are named as derivatives of the corresponding alkanes replacing ‘ane’ by the suffix ‘yne’.
l
They generally show position isomerism. In which, two compounds differ in their structures due to the position of triple bond.
Structure of Triple Bond

l
Each carbon atom of ethyne has two sp-hybridised orbitals.
l
C ¾ C (s ) bond is obtained by the head on overlapping of two sp-hybridised orbitals of two carbon atoms.
l
The remaining sp-hybridised orbital of each carbon atom undergoes overlapping along the internuclear axis with1s-orbital of each
of the two hydrogen atoms forming two C ¾ H sigma bonds.
l
2p-orbital of one carbon atom is parallel to the 2p-orbital of other carbon atom.
l
These orbitals undergo lateral or sideways overlapping to form two p bonds between two carbon atoms.
l
Ethyne molecule consists of one C ¾ C s bond, two C ¾ H s bonds and two C ¾ C p bonds as shown below
In the plane Below the plane
of paper Sideways overlap of paper
2px π
2px
π 2py
2py
σ σ
σ
H 1s sp sp sp sp 1s H
σ-bond π
π-bonds
Orbital diagram of ethyne
Physical Properties
l
First three members are gases, next eight are liquids and higher ones are solids.
l
All alkynes are colourless.
l
These are weakly polar in nature.
l
They are lighter than H 2 O and immiscible with water but soluble in organic solvent.
l
Their melting and boiling point increases with increase in molar mass.
Preparation and Chemical Reactions of Alkynes
Chemical reactions
H2/Ni
250°-300°C
CH3 — CH3
HBr HBr
CH2 CHBr CH3 — CHBr2
Preparation Dil. H2SO4/Hg2+
CH3CHO
H2O H2O
CaC2 Br Br (Addition reactions)
Br2 Br2
CH CH BrCH CHBr H—C—C—H
CH2Br Alc. KOH
Br Br
CH2Br Ozonolysis CHO
Vicinal dihalide
CHO
1
Na, – H
2 2 – + Na + – – +
HC CNa 1
NaC CNa (Acidic nature)
– H2 Sodium
2 acetylide
Red hot Fe tube
Polymerisation
C6H6
Aromatic Hydrocarbons
Aromatic hydrocarbons, also known as arenes, were found to contain benzene ring (highly unsaturated). Aromatic compounds
containing benzene ring are known as benzenoids and those not containing a benzene ring are known as non-benzenoids.
Nomenclature and Isomerism
l
In IUPAC nomenclature, the substituent is placed as prefix to the word benzene.
l
When two hydrogen atoms in benzene are replaced by two similar or different monovalent atoms or groups, three different
position isomers are possible.
l
The 1, 2 or 1, 6 is known as the ortho ( o- ), the 1, 3 or 1, 5 as meta ( m- ) and the 1, 4 as para ( p- ) disubstituted compounds.
Structure of Benzene
l
Kekule suggested the structure of benzene by the concept of oscillating nature of double bonds as shown below
l
Benzene has unusual stability due to resonance.
l
X-ray diffraction data reveals that benzene is a planar molecule. C ¾ C bond length is intermediate between C ¾ C single bond
and C ¾ C double bond.
l
For a compound to be aromatic, it must possess the following characteristics
(i) Planarity
(ii) Complete delocalisation of the p-electrons in the ring.
(iii) Presence of ( 4 n + 2 ) p electrons in the ring, where n is an integer ( n = 0 , 1 , 2 , K )
l
Examples of a few aromatic compounds are given below
Benzene Cyclopentadienyl anion Naphthalene Anthracene

n=1 n=1 n=2 n=3
6π-electrons 6π-electrons 10π-electrons 14π-electrons
Preparation and Chemical Reactions

Chemical reactions
HNO3/H2SO4 NO2
323-333 K
(Nitration)
Cl
Cl2/Anhyd. AlCl3
(Halogenation)
SO3H
Fuming H2SO4
Preparation (Sulphonation)
Zn-dust, ∆ R
C6H5OH RCl, Anhyd. AlCl3
Red hot Fe (Friedel-Crafts
C2H2 alkylation)
tube
− + COR
∆ RCOCl, Anhyd. AlCl3
C6H5COONa
NaOH, CaO Benzene (Friedel-Crafts
(Decarboxylation) acylation)
H2, Ni
Cl
Cl2, UV rays Cl Cl
6Cl2, Anhyd. 500 K

AlCl3, dark, cold Cl Cl
Cl
(BHC or gammaxane)
Cl
Cl Cl
Cl Cl
Cl
Physical Properties l
They reduce the electron density in the benzene ring due to
l
These are non-polar molecules and are colourless liquids or its strong -I -effect.
solids.
l
These are immiscible with water but are readily miscible with Carcinogenicity and Toxicity
organic solvents. The polynuclear hydrocarbons having two or more fused
benzene rings are toxic and have carcinogenic (cancer
Directive Influence of a Functional Group producing) property. These are obtained by incomplete
in Monosubstituted Benzene combustion of organic materials like tobacco, coal and
petroleum.
In general, two types of behaviour are observed. Either o/p or m
They reach into the human body and undergo several
product is obtained predominantly. This behaviour depends upon
biochemical reactions. They damage DNA and cause cancer.
the nature of the group already present in the benzene ring and is
Some examples of carcinogenic hydrocarbons are as follows.
called the directive influence of substituents.
ortho and para-directing Groups
l
The groups, e.g. ¾ OH, ¾ NH 2 , ¾ NHR, ¾ NHCOCH 3 ,
¾ OCH 3 , ¾ CH 3 , ¾ C2H 5 etc., are called ortho and
para-directing as well as activating groups. CH3
1, 2-benzanthracene
l
They activate benzene ring towards electrophilic substitution.
3-methylcholanthrene
Exception Halogens are deactivating but they are ortho CH3
and para directing groups.
meta-directing Groups
l
The groups, e.g., ¾ NO2 , ¾ CN, ¾ CHO, ¾ COR,
¾ COOH, ¾ COOR, ¾ SO 3 H etc., are called
meta-directing as well as deactivating groups. CH3
9, 10-dimethyl-1,2-benzanthracene
Chapter
Practice
6. Arrange the halogens F2 , Cl 2 , Br2 , I2 , in order of
PART 1 their increasing reactivity with alkanes.
(NCERT Exemplar)
Objective Questions (a) I 2 < Br2 < Cl 2 < F 2 (b) Br2 < Cl 2 < F 2 < I 2
(c) F 2 < Cl 2 < Br2 < I 2 (d) Br2 < I 2 < Cl 2 < F 2
l
Multiple Choice Questions 7. Which of the following reactions of methane is
incomplete combustion? (NCERT Exemplar)
1. The correct IUPAC name of the following alkane is (a) 2CH4 + O 2 ¾Cu /523 K /100 atm
¾¾¾¾¾ ® 2CH3 OH
(NCERT Exemplar)
Mo O
H3C—CH2—CH—CH2—CH2—CH—CH2—CH3 (b) CH4 + O 2 ¾ ¾¾¾® HCHO + H 2 O
2 3
(c) CH4 + O 2 ¾
¾® C(s) + 2H 2 O (l)
CH CH2
(d) CH 2 + 2O 2 ¾
¾® CO 2 ( g) + 2H 2 O(l)
CH3 CH3 CH3
(a) 3,6-diethyl-2-methyloctane
8. The IUPAC name of CH2 ==C ¾ CH 3 is
(b) 5-isopropyl -3-ethyloctane ½
(c) 3-ethyl-5-isopropyloctane CH 3
(d) 3-isopropyl-6-ethyloctane (a) 2-methylbutene (b) 1-methylpropene
2. The given structures, (c) 2-methylbut-2-ene (d) 2-methylprop-1-ene
CH 3 9. Which of the following has higher dipole moment;

½ cis-2-butene and trans-2-butene?
CH 3 — CH — CH 3 and CH 3CH 2CH 2CH 3 are (a) cis-but-2-ene
(a) conformational isomers (b) chain isomers (b) trans-but-2-ene
(c) position isomers (d) functional isomers (c) Both have same dipole moment
3. Among the following, which hydrocarbon is not
produced by Wurtz reaction? 10. Arrange the following alkyl halides in decreasing
(a) Methane order of the rate of b-elimination reaction with
(b) Ethane alcoholic KOH. (NCERT Exemplar)
(c) Propane CH 3
(d) All given options can be prepared ½
4. Soda lime is a mixture of A. CH 3 ¾ C ¾ CH 2Br B. CH 3 — CH 2 — Br
(a) NaOH + Ca(OH) 2 (b) NaOH + Mg(OH) 2 ½
(c) NaOH + CaO (d) NaOH + MgO CH 3
5. Arrange the following in decreasing order of their C. CH 3 — CH 2 — CH 2 — Br
boiling points. (NCERT Exemplar) (a) A > B > C (b) C > B > A
A. n-butane (c) B > C > A (d) A > C > B
B. 2-methylbutane 11. What are A and B in following reaction?
C. n-pentane H
D. 2, 2-dimethylpropane ½ Alcohol NaNH2
(a) A > B > C > D H 2C —C—H + KOH ¾¾® A ¾¾® B
(b) B > C > D > A ½ ½
(c) D > C > B > A Br Br
(d) C > B > D > A
A B 17. Assertion Propene reacts with HBr to give

(a) H2C == CH2 CH ºº CH isopropyl bromide.
(b) CH2 == CHBr CH ºº CH Reason Addition of hydrogen halide to get alkenes
(c) CH2 == CHBr CH2 == CH2
follows Markowonikov’s rule.
(d) CH2 == CH2 CH ºº CBr
18. Assertion 1-butene on reaction with HBr in the
12. When CH 3 — C ºº CH reacts with one mole of presence of a peroxide, produces 1-bromobutane.
HBr then product obtained is Reason It involves the formation of a 1° free radical.
(a) bromoethene
19. Assertion Polymerisation of ethylene gives
(b) dibromopropane
polythene.
(c) 2-bromopropene
(d) 1-bromopropane Reason Polythene formation is a substitution reaction.
20. Assertion 1-hexyne is converted to cis-1-hexene by
NaNH2 Red hot iron Lindlar’s catalyst.
13. CH2 CHBr A
tube, 873 K
Reason 1-hexyne is converted to n-hexene by the
Here, A refers to reduction with hydrogen gas in the presence of Pd/Ni.
(a) CH ºº CH (b) CH3 — C ºº CH l
Case Based MCQs
(c) CH3 — CH3 (d) CH ºº C — NH2
14. The IUPAC name of (i) to (iv) given below
CH3
The rotation of carbon-carbon single bond (s-bond),
due to cylindrical symmetry of s-MOs (molecular
is orbitals) long internuclear axis, in alkanes results
CH3 into different spatial arrangements of atoms in
(a) dimethylbenzene space, that are interconvertible.
(b) methyltoluene These arrangements are called conformations.
(c) 1, 3-dimethylbenzene However, weak repulsive interaction are present
(d) 1, 4-dimethylbenzene between the adjacent bonds in alkanes so the
15. Attack of electrophile on benzene results in the rotation of C—C single bond is not completely free
formation of and is hindered by a small energy barriers of 1-20
(a) s complex kJ mol -1 . The repulsive interaction between the
(b) arenium ion adjacent bond is due to electron cloud. The two
(c) p complex type of conformations are very common, i.e.
(d) Both (a) and (b) staggered and eclipsed.
The conformation in which the hydrogen atoms
l
Assertion-Reasoning MCQs attached to the two carbon atoms are as far apart as
Direction (Q. Nos. 16-24) For given questions two possible is called the staggered conformation. The
statements are given-one labelled Assertion (A) and the conformations in which the hydrogen atoms
other labelled Reason (R). Select the correct answer to attached to the two carbon atoms are as closed as
these questions from the codes (a), (b), (c) and (d) as possible is called eclipsed conformation.
given below. Any intermediate conformation between the above
(a) Both A and R are true and R is the correct two is called skew or gauche conformation.
explanation of A. (i) The electronic distribution of the sigma molecular
(b) Both A and R are true, but R is not the correct orbital is symmetrical around the internuclear axis of
explanation of A. C¾ C bond which permits free rotation around
(c) A is true, but R is false. C ¾ C bond. Such spatial arrangements of atoms in
(d) A is false, but R is true. which conversion of one another takes place by
rotation around C¾ C bond is known as
16. Assertion Among isomeric pentanes,
(a) rotamers
2, 2-dimethylpentane has the lowest boiling point.
(b) conformers
Reason Branching in hydrocarbon does not affect the (c) conformations
boiling point. (d) All of these
(ii) The possible rotamers of ethane is/are Geometric isomerism (also known as cis-trans isomerism
(a) 2 (b) 3 or E-Z isomerism) is a form of stereoisomerism. This
(c) 4 (d) ¥ passage explains what stereoisomers are and how you
(iii) The different conformations of ethane cannot be recognise the possibility of geometric isomers in a
separated and isolated because molecule.
(a) small energy barrier (b) large energy barrier (i) Which of the statement(s) is correct regarding the
(c) Both (a) and (b) (d) Neither (a) nor (b) following structures?
H3 C CH H C H
Or 3 3
C == C C == C
The repulsive interaction between the electron
clouds, which affects stability of a conformation is H H H CH3
cis trans
termed as A B
(a) torsional strain (b) dihedral angle (a) A and B are stereoisomers of each other
(c) torsional angle (d) conformation (b) A has more boiling point than B
(iv) Which form of ethane has the least torsional strain? (c) B has more boiling point than A
(a) Staggered (b) Skew boat (d) Both (a) and (b)
(c) Eclipsed (d) Boat (ii) Which of the following has higher dipole moment;
26. Read the following and answer the questions from cis-2-butene and trans-2-butene?
(i) to (v) given below (a) cis-but-2-ene
(b) trans-but-2-ene
In stereoisomerism, the atoms making up the isomers
(c) Both have same dipole moment
are joined up in the same order, but still manage to
have a different spatial arrangement. Geometric
isomerism is one form of stereoisomerism. Geometric (iii) Which of the following statement is correct
isomers are the isomers occur where you have regarding cis and trans isomer ?
restricted rotation somewhere in a molecule. (a) trans-isomer is more stable than cis
(b) cis-isomer is more stable than trans
At an introductory level in organic chemistry,
(c) Both isomers have equal stability
examples usually just involve the carbon-carbon
double bond and that's what this passage will
concentrate on. Think about what happens in (iv) Which of the following compounds will exhibit
molecules where there is unrestricted rotation geometrical isomerism?
(a) 1-phenyl-2-butene (b) 3-phenyl-1-butene
about carbon bonds in other words where the
(c) 2-phenyl-1-butene (d) 1, 1-diphenyl-1-propene
carbon-carbon bonds are all single. The next
diagram shows two possible configurations of l, Or
2-dichloroethane. Which of the following will not show geometrical
isomerism?
F H F F
(a) CC (b) CC
Cl D Cl Cl
H3C C2H5 CH3 CH3
(c) CC (d) CC
Free rotation about this single bond H3C2 CH3 CH3 C2H5
These two models represent exactly the same molecule.
You can get from one to the other just by twisting
around the carbon-carbon single bond. These
molecules are not isomers. If you draw a structural
PART 2
formula instead of using models, you have to bear in
mind the possibility of this free rotation about single Subjective Questions
bonds. You must accept that these two structures
represent the same molecule
l
H Cl H H
1. Write IUPAC names of the following compounds
½ ½ ½ ½
H¾C ¾C ¾H H¾C ¾C ¾H (i) (CH 3 ) 3 CCH 2 C(CH 3 ) 3
½ ½ ½ ½ (ii) (CH 3 ) 2 C(C 2 H 5 ) 2
Cl H Cl Cl (iii) Tetra-tert-butylmethane
2. An alkane C 8H18 is obtained as the only product 14. Complete the following reactions
on subjecting a primary alkyl halide to Wurtz NaNH 2 CH 3Br
reaction. On monobromination this alkane (i) HC ºº CH ¾¾® A ¾¾® B
yields a single isomer of a tertiary bromide. HBr Na
Write the structure of alkane and the tertiary (ii) CH 3CH == CH 2 ¾® A ¾¾® B
Dry ether
bromide. (NCERT Exemplar)
15. (i) Give the IUPAC names for the following
3. Write the structures and names of products compounds.
obtained in the reactions of sodium with a mixture O
of 1-iodo-2-methylpropane and 2-iodopropane.
(NCERT Exemplar) (a) (b) Cl H
4. Write IUPAC name of the products obtained by the (ii) What is hybridisation of each carbon in
ozonolysis of the following compounds
CH 2 == C == CH 2 .
(i) Pent-2-ene
(ii) 3,4-dimethylhept-3-ene
16. Despite their - I effect, halogens are o- and
p-directing in haloarenes. Explain.
(iii) 2-ethylbut-1-ene (NCERT)
5. Give structural formula of all the isomers of C 5H10 . 17. Which of the following compounds are aromatic
6. Why unsaturated hydrocarbons are more reactive according to Huckel's rule?
than saturated hydrocarbons?
(A) (B)
7. Which among the two trans-but-2-ene or cis
but-2-ene is non-polar ? N
H
8. Predict the major product(s) of the following
reactions and explain their formation. (NCERT Exemplar) (C) H2C CH2 (D)
(Ph ¾ CO ¾ O) 2
H 3C ¾ CH == CH2 ¾¾¾¾¾®
HBr
HBr
H 3C ¾ CH == CH2 ¾ ¾
¾®
9. An alkene A contains three C¾C s-bonds, eight (E) (F)
C¾H s-bonds and one C¾C p-bond. A on
ozonolysis gives two moles of an aldehyde of molar
mass 44 u. Write IUPAC name of A. (NCERT)
10. For the following compounds, write structural 18. 7-bromo-1, 3, 5-cycloheptatriene exists as an ion,
formulae and IUPAC names for all possible isomers whereas 5-bromo-1, 3-cyclopentadiene does not
having the number of double or triple bond as form an ion even in presence of Ag + . Explain.
indicated.
19. Arrange the following compounds in the increasing
(i) C 4 H 8 (one double bond)
order of their property as indicated:
(ii) C 5H 8 (one triple bond) (NCERT)
(i) C 6 H 5CH 3 , C 6 H 5COOH, C 6 H 6 and C 6 H 5 NO 2
11. Give two tests to detect unsaturation in a (reactivity towards monobromination).
compound. (ii) (CH 3 ) 2 C == CH 2 , CH 3CH == CH 2 and CH 2 == CH 2
12. But-1-yne gives its sodium salt with NaNH 2 , (reactivity towards acid catalysed hydration).
which on reaction with ethylbromide gives
hex -3-yne.
l
Hex-3-yne on reduction with H 2 /Pd - BaSO 4 gives 20. (i) An alkyl halide (X) of formula C 6 H13Cl on
cis-hex-3-ene which on hydrolysis using treatment with alcoholic KOH or potassium
alk. KMnO 4 gives hexane-3, 4-diol. tert-butoxide gives two isomeric alkenes Y and Z
Write the related chemical equations. (C 6 H12 ). Both alkenes on hydrogenation give 2,
13. Why is benzene extra ordinarily stable even though 3-dimethylbutane. Predict the structure of X, Y
it contains three double bonds? (NCERT) and Z.
(ii) Give the structures of A and B. (ii) Give an example of

(i) O
(a) b-elimination reaction
Hot KMnO
C + D ¬¾¾¾¾
4
A ¾¾¾®
3
(b) Rearrangement reaction
(C6H 12 ) (ii) Zn, H 2O
B +C 26. (i) How will you convert?
(Isomers of formula C 3H6O)
(a) Benzene into acetophenone.
21. (i) How will you convert, (b) Benzene into p-nitrotoluene.
(a) 2-methylpropene to propan-2-one? (c) Benzene into m-nitrochlorobenzene.
(b) But-2-ene to ethanoic acid? (ii) Write the structures of A and B.
(c) Prop-1-ene to propan-1, 2-diol? Red hot Fe tube
(a) 3CH==CH ¾¾¾¾¾® A
(ii) Write the structures of A and B in the following 873 K
conc. HNO3 + conc. H2 SO4
(a) CH2 == CH2 + H2 SO4 ¾® A ¾¾¾¾¾¾¾¾® B
333 K
(C6H 5CO) 2O2
(b) B + HBr ¾¾¾¾® CH3 CH2 CH2 Br (b) + I2
HNO3 or
A+B
HIO3
22. A compound X reacts with alc.KOH to yield an
alkene Y. Y reacts with Br 2 to yield E, which on l
dehydrobromination yields alkyne Z. One mole of Z
yields one mole of sodium salt of Z and half a mole 27. Read the following and answer the questions from
of H 2 gas on treatment with Na metal in liquid NH 3 . (i) to (iv) given below
On complete hydrogenation, Z yields a straight Alkenes generally undergo electrophilic addition
chain alkane. Identify X, Y, Z and E and write the reactions because of the presence of a double bond
reactions involved. (a strong s and a weaker p-bond), p-electrons,
23. Assign the structures to the following which being loosely held are easily polarised.
These reactions involve cleavage of a p-bond and
(i) An alkene (molecular weight = 56) on reaction
formation of two new s-bonds.
with trioxygen followed by zinc/ CH 3COOH gave
only ethanal. Identify the structure of the alkene. In polar solvents, addition proceed by ionic
(ii) An alkyne (B ) has molecular formula C 5 H8 . It mechanism (at low temperature), whereas in the
reacts neither with sodamide nor with ammoniacal presence of light or non-polar solvents, the
cuprous chloride. addition occurs by free radical mechanism (at high
temperature).
(iii) A hydrocarbon (C ) has molecular formula C 8 H10 .
It does not decolourise bromine water and is Apart from addition reactions alkenes also
oxidised to benzoic acid on heating with K 2Cr 2O 7 . participate in the oxidation, ozonolysis and
It can also have three isomers X , Y , Z. What are polymerisation reaction.
the structures of C , X , Y and Z ? (i) Give the reaction of 1-butene with HBr in the
presence of a peroxide.
24. (i) How will you carry out the following conversion? (ii) Name the organic products of the reaction of
(a) Acetylene into nitrobenzene. but-2-ene with bromine dissolved in
(b) Ethene into benzene. tetrachloromethane
(c) Benzene into acetophenone. (iii) Addition of unsymmetrical reagent to
(ii) Complete the following reactions unsymmetrical alkene takes place according to
Soda lime
which rule?
(a) H3C COO–Na+ Heat (iv) Write the reaction of polymerisation of ethylene.
Or
Zn dust
(b) OH An alkene A on ozonolysis gives a mixture of
ethanal and pentan-3-one. Write structure and
25. (i) Write the structures A to C in the following IUPAC name of A.
reaction 28. Read the following and answer the questions from
Br (i) to (iv) given below
conc. HNO3 +
(a) ‘A’
conc. H2SO4, ∆ Aromaticity is defined as a property of the
Zn conjugated cycloalkenes which enhances the
(b) CH3CH == CH2 + O3 ¾¾® ‘ B ’
H 2O stability of a molecule due to the delocalisation of
hn
(c) CH4 + Cl 2 ¾¾ ® ‘C’ electrons present in the p-p orbitals.
Aromatic molecules are said to be very stable and l

Each element of the ring within the structure must
they do not break so easily and also reacts with and should have a p-orbital ring which is in
other types of substances. The organic compounds perpendicular form to the ring and this makes it a
which are not said to be aromatic are known as planar molecule.
aliphatic compounds. These might be in cyclic l
All the compounds obey the Huckel’s rule, i.e. all the
form, but only the aromatic rings have a special aromatic compounds should have the (4 n + 2) p
kind of stability. number of electrons.
We encounter aromaticity in our day-to-day lives. l
The last one is that the organic compound has to be flat.
Even our bodies function with the help of certain (i) Why C6H6 doesn’t undergo addition like all alkenes.
aromatic compounds. (ii) Which of the following follows Huckel’s rule?
Aromatic compounds are essential in the industry
and around 35 million tonnes of these compounds A. B.
are known to be produced worldwide every year in
the form of polymers and chemicals, such as the
nylon and polyester. These compounds are
(iii) Explain why CH2 is not aromatic.
important even in the field of the biochemistry of
all the living things. Or
Aromatic compounds are less stable compounds Is Azulene an aromatic compound?
and they have many kinds of chemicals as well as (iv) Compound X forms a white ppt. on reacting with
synthetic uses. AgNO3 however Y does not. Give reaction.
In fact, the nucleic acids and the amino acids that
Br
make up our cell structure make use of these
aromatic compounds. But, the main thing is what X-
makes aromatic compounds? The aromatic
compounds are said to exhibit some special Br
characteristics or called as rules which are given
below Y-
l
The aromatic compounds are always cyclic structures.
EXPLANATIONS
Objective Solutions
δ+ δ+ δ+
1. (a) The correct IUPAC name is H3 C δ– δ– CH3 H3C δ– δ– H
C C C C
H3C—CH2—CH—CH2—CH2—CH—CH2—CH3
3 4 5 6 7 8 H H H CH3
2
CH CH2 cis-but-2-ene trans-but-2-ene δ+
(µ = 0.33 D) (µ = 0)
1
CH3 CH3 CH3 10. (d) Alkyl halides on heating with alcoholic potash eliminates
3,6-diethyl-2-methyloctane one molecule of halogen acid to form alkene. Hydrogen is
eliminated from b-carbon atom. Nature of alkyl group
CH3
determines rate of reaction, i.e. 3° > 2° > 1° or A > C > B.
½
2. (b) CH3 ¾ CH ¾ CH3 , CH3 ¾ CH 2 ¾ CH 2 ¾ CH3 11. (b) The reactant is symmetrical alkane. On reacting with
2-methylpropane n -butane
alcoholic KOH, dehydrohalogenation reaction will occur. It
Molecular formula ¾® Same will give monobromoalkene.
Chain of C-atom ¾® Different CH 2 ¾ CH 2 + KOH ¾¾® CH 2 == CHBr
Alcohol
Hence, these are chain isomers. ½ ½ ( A)

3. (a) By Wurtz reaction, higher alkanes are prepared. i.e. Br Br
R — Cl + 2Na + R — Cl ¾® R — R + 2NaCl CH 2 == CHBr on reaction with NaNH 2 releases sodium
Alkane
bromide and ammonia and forms ethyne.
Thus, methane cannot be prepared by this reaction. NaNH2
4. (c) Soda lime is a mixture of sodium hydroxide and calcium CH 2 == CHBr ¾¾® CH ºº CH + NaBr + NH 3
(B )
oxide.
Soda lime = NaOH + CaO Br
5. (c) As the number of carbon atom increases, boiling point ½
increases. Boiling point decreases with branching 12. (c) CH3 ¾ C ºº CH + HBr ¾® CH2 == C ¾ CH3
2, 2 -dimethylpropane, n-pentane, 2- bromopropene
CH 3 NaNH2
13. (a) CH2== CHBr ¾¾® H — C ºº CH + NaBr + NH 3
½ A
H 3C ¾ C ¾ CH 3 > H3 C ¾ CH 2 ¾ CH 2 ¾ CH 2 ¾ CH3 >
½ b.pt = 309.1 K ½ Red hot iron tube, 873 K
CH 3 ¯
b.pt = 282.5 K Benzene
2-methylbutane, n-butane 14. (c)
CH3
H3 C ¾ H 2 C ¾ HC ¾ CH3 > H3 C ¾ H 2 C ¾ CH 2 ¾ CH3 1
| b.pt = 273 K
6 2
CH3
b.pt = 301 K 5
(4 carbon atoms with no branching) 3 CH3
4
Hence, D > C > B > A. 1,3-dimethylbenzene
6. (c) Rate of reaction of alkanes with halogens is 15. (d) Attack of electrophile on benzene nucleus results in the
F 2 > Cl 2 > Br2 > I 2 formation of s-complex or arenium ion, in which one of the
7. (c) During incomplete combustion of alkanes with carbon is sp 2 -hybridised. e.g.
insufficient amount of air or dioxygen, carbon black is sp2 -hybridised
formed which is used in the manufacture of ink, printer ink, H carbon
black pigments and as filters. Thus, + E ⊕ → E
Incomplete ⊕
CH4 ( g) + O 2 ( g) ¾ ¾¾¾® C(s) + 2H 2 O ( l ) H
combustion
Arenium ion
1 2 3
or σ-complex
8. (d) CH 2 == C — CH 3
½ 16. (c) A is true, but R is false.
CH3 Boiling point of alkane
2-methylprop-1-ene 1
µ
9. (a) cis form of alkene is found to be more polar than the branching in isomeric alkanes
trans form. e.g. dipole moment of cis-but-2-ene is 0.33 2, 2-dimethylpentane has lower boiling point while
Debye, whereas, dipole moment of the trans form is n -heptane has higher boiling point because the former
almost zero or it can be said that trans-but-2-ene is involves branching. Both are isomeric alkanes.
non-polar.
17. (a) Both A and R are true and R is the correct explanation of A. (iv) (a) The staggered form of ethane has the least torsional
Addition of unsymmetrical reagent to unsymmetrical alkene strain and the eclipsed form has the maximum torsional
takes place according to Markownikoff ’s rule, i.e. negative strain.
part of addendum goes to carbon atom with less number 22. (i) (d) Statements (a) and (b) are correct, while the
hydrogen atoms. statement (c) is incorrect.
CH3CH == CH2 + HBr ¾® CH3 ¾ CH ¾ CH3 It’s correct form is as follows
½ Arrangement of atoms or groups in space in the two
Br structures is different.
18. (c) A is true, but R is false.
2 2 H O Therefore, they are stereoisomers.
CH2 ==CHCH2CH3 + HBr ¾¾® CH 3CH 2CH 2CH 2Br
1-bromobutane The isomer of the type (A) in which two identical
·
½ Br (Anti-Markownikoff ’s rule) atoms or groups lie on the same side of the double
¯ bond is called cis-isomer and the other isomer of
or Kharash effect
·
C H 2 — C H — CH 2 — CH3 HBr the type (B), in which identical atoms or groups lie on
½ (Secondary radical) the opposite sides of the double bond is called trans
Br (more stable) isomer.
H3C CH3 H3C H
19. (c) A is true, but R is false.
C == C C == C
Alkenes in the presence of trace of oxygen and at high
H H H CH3
temperature and pressure undergo self addition.
473 K ,1500 atm
cis - but-2-ene trans - but-2-ene
nCH2 == CH2 ¾¾¾¾® ¾
( CH2 ¾ CH2 ¾)n (b. p. 277 K) (b. p. 274 K)
traces of O 2 Polyethene
Ethene
Boiling point of cis form is higher than that of trans form.
20. (c) A is true, but R is false
(ii) (a) cis form of alkene is found to be more polar than the
In the Lindlar’s catalyst, syn-addition takes place due to trans form.
which cis-product is formed as follows
Lindlar's
e.g. Dipole moment of cis-but-2-ene is 0.33 Debye,
CH 3CH 2CH 2CH 2C ºº CH ¾¾¾® whereas, dipole moment of the trans form is
catalyst (H2 )
1-hexyne almost zero or it can be said that trans-but-2-ene is
CH 3CH 2 CH 2CH 2CH == CH 2 non-polar.
cis-1-hexene
δ+ δ+ δ+
Also, 1-hexyne is converted to n-hexane (not n-hexene) by H3C δ– δ– CH3 H3 C δ– δ– H
the reduction with hydrogen gas in the presence of Pd/Ni. C C C C
Pd / Ni H H H CH3
CH 3CH 2CH 2CH 2C ºº CH n-hexane cis-but-2-ene trans-but-2-ene δ+
2H2
(µ = 0.33 D) (µ = 0)
21. (i) (d) Difference in spatial arrangement of atoms around (iii) (a) trans-isomer is more stable than cis-isomer because in
C ¾ C bond is known as conformations, conformers or cis-isomer, the bulky groups are on the same side of the
rotamers. e.g. double bond.
H
H H The steric repulsion of the groups makes cis-isomer less
H
H stable than the trans-isomer in which the bulky groups
H H
H are far apart (They are on the opposite side of the double
H H H H bond).
Eclipsed Staggered (iv) (a) The compound 1-phenyl-2-butene exhibits geometrical
isomerism.
(ii) (d) Infinite number of conformations/rotamers are
possible due to rotation around C ¾ C single bond by The structure of compound is given below
every small change in angle between two C—H bonds. 4 3 2 1
(iii) (a) Because the energy barrier between the two forms CH3 ¾ C == C ¾ CH2C6H5
½ ½
is 12.5 kJ/mol which is so small that small thermal or H H
kinetic energy is sufficient to overcome it by Or
intermolecular collision.
(d) In option (d), a carbon with double bond has two same
Or
functional groups (CH3 ) attached. The rotation around
(a) The repulsive interaction between the electron
carbon will not produce a new compound. Hence,
clouds, which affect the stability of conformation is
geometrical isomerism is not possible.
called torsional strain.
Subjective Questions CH3—CH— CH2—CH— CH3 + 2NaI

| |
1. The expanded structures of these alkanes are
2 1
CH3 CH3
CH3 CH3 CH2— CH3 2, 4-dimethyl pentane
1 2 3 4 5 3 4 5
(i) CH3—C—CH2—C—CH3 5 4 3 2 1 (i) O3 /CH2Cl 2 , 196 K
(ii) CH3—C—CH2CH3
4. (i) CH3 ¾ CH2 ¾ CH == CH ¾ CH3 ¾¾¾¾¾¾¾¾®
Pent-2-ene (ii) Zn /H2O
CH3 CH3 CH3
2,2,4,4-tetramethylpentane 3,3-dimethylpentane 3 2 1 1 2
CH3 ¾ CH2 ¾ CH == O + O == CH ¾ CH3
CH3 Propanal Ethanal
H3C CH3—C—CH3 CH3 7 6 5 4 3 2 1

1 2 3
5 4
(ii) CH3 ¾ CH2 ¾ CH2 ¾ C == C ¾ CH2 ¾ CH3
(iii) CH3—C————C————C—CH3 ½ ½
1
CH3 CH3
H3C CH3—C—CH3 CH3 3,4-dimethylhept-3-ene
(i) O3 /CH2Cl 2 , 195 K
CH3 ¾¾¾¾¾¾¾¾®
3, 3-di-tert-butyl-2,2,4,4-tetramethylpentane (ii) Zn /H2O
or 3,3-bis (1, 1-dimethylethyl)-2,2,4,4-tetramethylpentane
O O
2. Since, alkane C 8H18 on monobromination yields a single 5 4 ½½2 1
3 4 3 ½½2 1
isomer of a tertiary bromide, therefore alkane must contain CH3 ¾ CH2 ¾ CH2 ¾ C ¾ CH3 + CH3 ¾ CH2 ¾ C ¾ CH3
tertiary hydrogen. Pentan -2-one Butan -2-one
This is possible if primary alkyl halide (which undergoes 4 3 2 1 (i) O3 /CH2Cl 2 , 195 K
Wurtz reaction) has a tertiary hydrogen. (iii) CH3 ¾ CH2 ¾ C == CH2 ¾¾¾¾¾¾¾¾®
CH 3 CH 3 ½ (ii) Zn /H2O
| ½ CH2 ¾ CH3
CH 3 ¾ CH ¾ CH 2 ¾ X + 2Na + X ¾ CH 2 ¾ CH ¾ CH 3 2-ethylbut-1-ene
1-halo-2-methylpropane
O
CH 3 CH 3 1 ½½3 4
2 5
6 ½5 4 3 ½ 1
CH3 CH2 ¾ C ¾ CH2 CH3 + HCHO
D, - 2NaX 2 Methanal
¾¾¾¾¾® CH 3 ¾ CH ¾ CH 2¾ CH 2 ¾ CH ¾ CH 3 Pentan -3-one
Wurtz reaction 2,5-dimethylhexane (alkane) 5.
CH 3 CH 3
Br2 , hv ½ ½
¾¾¾® CH 3 ¾ C ¾ CH 2 ¾ CH 2 ¾ CH ¾ CH 3
- HBr 1
½2 3 4 5 6 (1) pentene (5) 2-methylbut-2-ene (8) 2-methylbut-2-ene
Br
2-bromo-2,5-dimethylhexane
(3° bromide)
(2) pent-2-ene
∆
3. (i) CH3 CH CH2 I + 2Na + I CH2 ¾ CH ¾ CH3 ¾®
| |
CH3 CH3 (6) cyclopentane (9) 1,2-methylcyclopropane
1-iodo-2-methyl propane
(3) 3-methylbutene
CH3— CH — (CH2 )2 — CH— CH3 + 2NaI
| |
CH3 CH3
2, 5 -dimethyl hexane (7) methylcyclobutane
D (10) dimethylcyclopropane
(ii) CH3 — CH— I + 2Na + I — CH— CH3 ¾¾® (4) 2-methylbutene
| | Dry ether
CH3 CH3 6. All the alkanes have C—C bonds and C—H bonds which are
2-iodopropane also strong and weakly polarised. On the other hand, alkenes
CH3—CH—CH—CH3 + 2NaI have C == C bond, which are weaker bonds than the single
| | bond .
CH3 CH3
Due to presence of p-character in double bond, alkenes are
2, 3-dimethyl butane
more reactive.
∆
(iii) CH3—CH—CH2 – I + 2Na + I —CH—CH3 ¾¾® These double and triple bonds are the reactive sites in the
| | Dry ether
unsaturated hydrocarbons which easily give addition
CH3 CH3 reactions.
1-iodo-2-methyl propane 2-iodopropane
7. In trans but-2-ene, the dipole moments of the two C ¾ CH 3 CH3

bonds are equal and opposite. Therefore, they cancel out CH3 H ½
each other. Hence, trans but-2-ene is non-polar. (c) C == C (d) CH3 ¾ C ==CH2
H3C H H CH3 2-methylprop-1-ene
C µ=0 trans -but-2-ene
H trans-form CH3 5 4 3 2 1
(ii) (a) CH3 CH2CH2C ºº CH
While cis but-2-ene has a non-zero dipole moment thus it is
Pent-1-yne
polar.
H3C CH3 5 4 3 2 1
C C µ=0 (b) CH3 CH2 ¾ C ºº C¾ CH3
H cis-form H Pent-2-yne
8. In presence of organic peroxides, the addition of HBr to CH3
propene follows anti-Markownikoff ’s rule (or peroxide 4 ½ 2
3 1
effect) to form 1-bromopropane (n-propyl bromide) (c) CH3 ¾ CH ¾ C ºº CH
O O 3-methylbut-1-yne
|| || Homolytic 11. The two tests to detect unsaturation in a compound are as
Ph  C  O  O  C  Ph follows
fission
O (i) Unsaturated compounds (alkenes/alkynes) decolourises
|| bromine water that is, a colour change is observed from
2Ph  C  O 2Ph + 2CO2
orange-red to colourless. The reaction involved is
Ph + HBr C6H6 + Br shown below
Br Br
H3C  CH==CH2 + Br
Slow
H3C  CH  CH2Br H2 O
½ ½
2° Free radical
CH 2 == CH 2 + Br2 ¾® CH 2 ¾ CH 2
(more stable) Ethene 1, 2- dibromoethane
(Colourless)
H-Br
H3C  CH2  CH2Br + Br
(ii) Also, unsaturated compounds decolourises KMnO4
1-bromopropane
solution (purple).
However, in absence of peroxides, addition of HBr to 2KMnO4 + H 2O ¾® 2KOH + 2MnO2 + 3 [O]
propene follows Markownikoff ’s rule and gives Potassium Potassium
permanganate (Purple) hydroxide
2-bromopropane as major product.
+ CH 2 == CH 2 + H 2O + [O] ¾® H 2 C ¾ CH 2
CH3 ¾ CH == CH2 + H+ ¾®
Slow
CH3 ¾ CH ¾ CH3 Ethene ½ ½
Propene More stable 2° carbocation OH OH
Br - Ethane - 1, 2- diol
¾¾® CH3 ¾ CH ¾ CH3 ( Colourless )
Fast
½ NaNH
Br 12. I. CH 3CH 2 ¾ C ºº CH ¾¾®
2
CH 3CH 2 ¾ C ºº CNa
2 - bromopropane But-1-yne - NH 3 Sodium salt
CH3× CH2× Br
9. An aldehyde having molar mass 44 u is ethanal, CH3CHO. II. CH 3CH 2C ºº CNa ¾¾¾¾®
the structures of two molecules of ethanal is written in - NaBr
such a way that their oxygen atoms point towards each CH 3CH 2C ºº C ¾ CH 2CH 3
Hex-3-yne
other. Join the two ends are joined through the double bond
H2 /Pd-BaSO 4
with the removal of both of the oxygen atoms to obtain III. CH 3CH 2C ºº C — CH 2CH 3 ¾¾¾¾¾®
alkene A.
CH 3CH 2CH == CHCH 2CH 3
CH3CH== O + O==CHCH3 ¬¾ CH3¾ CH == CH¾ CH3 cis- hex -3-ene
Ethanal Ethanal ( A ) But-2-ene H2 O
IV. CH 3CH 2CH == CHCH 2CH 3 ¾ ¾¾®
H H H H Alkaline KMnO 4
σ σ σ σ
σ σ σ C—σH CH 3CH 2 C H ¾ C H CH 2 ¾( CH 3 )
H— C—C π C— | |
σ σ
OH OH
H H Hexane-3, 4-diol
Hence, alkene ( A ) is but-2-ene which contains three C¾C, 13. Resonance and delocalisation of electrons generally lead to
eight C¾H, s-bonds and one C¾C p-bond (as given in the the stability of benzene molecule.
question).
10. (i) Isomers of C4H8 having one double bond are
4 1
4 3 2 1 CH3 3 2 CH3 Hybrid structure
(a) CH3CH2 ¾ CH == CH2 (b) C == C
But-1-ene H H The dotted circle in the hybrid structure represents the six
cis -but-2-ene electrons which are delocalised between the six carbon
atoms of the benzene ring.
Therefore, presence of delocalised p-electrons in benzene Br

makes it more stable than the hypothetical cyclohexatriene. +
2NaNH2
5
14. 2CH3Br
(i) HC ºº CH ¾¾®NaC ºº CNa ¾¾® CH 3C ºº CCH 3 4 1 Ag+
Ethyne Disodium But-2-yne + AgBr
acetylide (B )
( A) 3 2
1, 3-cyclopentadienyl cation
HBr 5-bromo-1, 3- (4π-electrons, aromatic,
(ii) CH 3CH == CH 2 ¾¾¾¾¾¾® cyclopentadiene
Propene Markownikoff addition highly stable)
CH 3 CH CH 3 ¾Na, Dry ether
¾¾¾¾ ¾® In contrast, 5-bromo-1,3-cyclopentadiene, on ionisation, will
CH3 CH ¾ CH3
½ ½
give 1, 3-cyclopentadienyl cation which contains 4p-electrons
Br Br and hence, is anti-aromatic. Being anti-aromatic, it is highly
2-bromopropane unstable and hence not formed even in the presence of Ag +
( A)
ion which otherwise facilitates ionisation.
CH 3 ¾ CH ¾ CH ¾ CH 3
½ ½ 19. (i) Monobromination of the aromatic compound is an
CH 3 CH 3 electrophilic substitution reaction. The electron
15. (i) (a) Propylbenzene 2, 3 -dimethylbutane donating group (like ¾ CH 3 ) will increase the
(B )
(b) 3-chloropropanal reactivity of benzene ring, while electron withdrawing
(ii) groups (like ¾NO2) decrease the reactivity of that ring.
σ σ σ σ
H C π C π C3 H Order of electron withdrawing capacity of the given
1 σ 2 σ groups is
H H
¾ NO2 > ¾ COOH > ¾ H > ¾ CH 3.
The hybridisation of C1 carbon is sp 2 , for C 2 it is sp and for
Hence, the increasing order of reactivity of ring
C 3 it is sp 2.
towards monobromination is
16. Halogens have (-I) and ( +R ) effect, these groups are
C 6H 5NO2 < C 6H 5COOH < C 6H 6 < C 6H 5CH 3.
deactivating due to their ( -I ) effect and they are ortho, para
directing due to ( +R ) effect. (ii) Acid catalysed hydration of alkenes involves the
+ + + formation of carbocation intermediate. Higher the
Cl Cl Cl Cl stability of carbocation intermediate, more is the
reactivity towards acid catalysed hydration. The order
of stability of carbocation formed is
+ + +
(CH 3 ) 2 C CH 3 > CH 3 CHCH 3 > CH 2 ¾ CH 3.
Thus, the order of reactivity towards acid catalysed
ortho, para-directing influence hydration is
17. A. The compound has 8p-electrons. It will be CH 2 == CH 2< CH 3CH == CH 2 < (CH 3 ) 2 C == CH 2
non-aromatic. Both rings are non-benzenoid.
CH 3 CH 3
B. The compound is aromatic. It has 6pe- delocalised ½ ½
electron (4pe- + 2 lone pair electrons), all the four 20. (i) CH 3 ¾ C ¾ C ¾ CH 3 + KOH ¾¾¾®
Heat
carbon atoms and the N-atom are sp 2-hybridised. ½ ½ (Alc.) Elimination
C. The compound contains 6p-electrons but not in the Cl H
ring hence it is non-aromatic. ( X)
D. 10p electron obeying Huckel rule and the ring is planar. CH 3 CH 3 CH 3 CH 3
It is aromatic. ½ ½ | |
E. In this compound, one six membered planar ring has CH 3 ¾ C == C ¾ CH 3 + CH 2 == C ¾ C ¾ CH 3
6p electron although it has total 8p-electrons in two 2,3-dimethyl but-2-ene |
H
rings. It is therefore aromatic.
2,3-dimethylbut-1-ene
F. It has 14p-electrons in conjugation and in the planar ( Z)
ring, Huckel rule is verified. It will be aromatic. (ii) Isomers of the formula (C 3H 6 O) are CH 3CH 2CHO(B )
18. 7-bromo-1, 3, 5-cycloheptatriene, on ionisation, gives and CH 3COCH 3 ( C ). Hence, A is
tropylium ion. Since, tropylium ion contains 6p-electrons CH3
which are completely delocalised. Therefore, according to
Huckel rule, it is aromatic and hence stable. Being highly CH3CH2CH C CH3 (2-methyl pent-2-ene).
stable, it is easily formed.
CH 3
Br | Ozonolysis
7 + CH 3CH 2CH == C ¾ CH 3 ¾¾¾¾¾®
6 1 Ionisation ( A)
–
5 2 + Br CH 3CH 2CHO + CH 3COCH 3
4 3 Propanal Propanone
Tropylium ion ( B) ( C)
7-bromo-1, 3, 5- (6π-electrons, aromatic,
cycloheptatriene
highly stable)
CH 3 Z is CH 3CH 2CH 2C ºº CH.

| Hot KMnO 4 E is CH 3CH 2CH 2 ¾ C HCH 2 ¾Br .
CH 3CH 2CH == C ¾ CH 3 ¾ ¾¾¾¾¾ ® |
( A)
CH 3 Br
|
CH 3CH 2COOH + CH 3 ¾ C == O 23. (i) First of all we will derive the molecular formula of
Propanoic acid Propanone alkene, Cn H2n ; 12 n + 2 n = 56 or 14n = 56
( D) ( C) \ n=4
21. (i) (a) 2-methylpropene to propan-2-one Thus, the molecular formula of alkene is C4H8 .
CH3 H3C O Zn/H2O As it is giving only ethanal on reaction with O3 followed by
C CH2 + O3 C CH2 reduction, the alkene is symmetrical and its structure is
CH3 Ozone H3C
2-methylpropene O O H H
Ozonide | |
H3C
C O + HCHO H ¾ C ¾ C == C ¾ C ¾ H
H3C Formaldehyde | | | |
Propan-2-one H H H H
But-2-ene
(b) But-2-ene to ethanoic acid
KMnO /H+
(ii) Alkyne B is C 5H 8. Since, it does not react with sodamide
4
CH 3 — CH == CH — CH 3 ¾¾¾® 2 CH 3COOH or ammoniacal, cuprous chloride, the triple bond cannot
But-2-ene Ethanoic acid be terminal.
(c) Prop-1-ene to propan-1, 2-diol \ X is CH 3CH 2C ºº CCH 3.
Dil. KMnO 4 Pent-2-yne
CH 3 — CH == CH 2 + H 2O ¾¾¾® (iii) Since, it does not decolourise bromine water, it is arene.
Prop-1 -ene 273 K
CH 3CH(OH)CH 2OH Its formula is
Propan -1,2-diol CH2CH3 COOH
(ii) (a) CH 2 == CH 2 + H 2SO4 ¾®
Ethene CH 3 — CH 2 — OSO2 — OH
Ethyl hydrogen sulphate [O]
( A) K2Cr2O7,H+
(C6 H5 CO)2 O 2
(b) CH 3 — CH == CH 2 + HBr ¾¾¾¾¾¾¾¾® (C) Benzoic acid
Prop-1 -ene Anti -Markownikoff addition Ethyl benzene
( B) The other three isomers are
CH 3CH 2CH 2Br
22. The reactions are as follows Bromopropane CH3 CH3 CH3
Alc. Br 2 Alc.
C 5H11Br ¾¾® C 5H10 ¾¾® C 5H10Br2 ¾¾® C 5H 8 CH3
( X) KOH (Y) (E) KOH ( Z)
1
C 5H 8 ¾Na ¾® C 5H 7Na + H 2 CH3
( Z ) liquid NH3 2 (X) (Y)
1, 2-dimethyl benzene 1, 3-dimethyl benzene
The reactions show that Z is a terminal alkyne. The possible CH3
(o-xylene) (m-xylene)
structures are (Z)
CH 3CH 2CH 2C ºº CH and CH 3CHC ºº CH 1, 4-dimethyl benzene
| (p -xylene)
CH 3 24. (i) (a) Conversion of acetylene into nitrobenzene.
It is given that alkyne Z gives a straight chain on complete
Conc.HNO3 NO2
hydrogenation. Therefore, the structure of alkyne Z is, Red hot Fe tube +Conc.H2SO4
3CH CH
CH 3CH 2CH 2C ºº CH Acetylene
873K 333K
(Cyclic (Nitration)
The reactions can be written as shown below polymerisation) Benzene Nitrobenzene
CH3CH2CH2CH2CH2Br Alc.KOH CH3CH2CH2CH CH2 Br2/CCl4 Alc.KOH, ∆
(X) (Y)
(b) CH2 CH2 CH2—CH2 CH2 CHBr
Br2 Dehydrobro-
Alc.KOH Ethylene mination Vinyl bromide
CH3CH2CH2 CHCH2 Br Br Br
NaNH2/liqNH3
Br 196K,
(E) Dehydrobromination
Red hot iron tube
Na CH CH
CH3CH2CH2C CH CH3CH2CH2C C–Na+ Ethyne
(Z) liq. NH3 (Z) Benzene
COCH3
2H2
CH3CH2CH2C CH CH3CH2CH2CH2CH3
Anhyd. AlCl3
(c) + CH3COCl + HCl
Thus, the structure of X , Y , Z and E are
X is CH 3CH 2CH 2CH 2CH 2Br. Y is CH 3CH 2CH 2CH == CH 2. Benzene Acetophenone
(ii) (a) (b)

–+ Soda lime CH3
H3C COONa Heat
CH3
CH3Cl, Dil. HNO3 +
Toluene anhyd. AlCl3 Dil. H2SO4
(b) ∆, Nitration
Zn dust
OH + ZnO Benzene Toluene
CH3 CH3
25. Br Br NO2
NO2 +
Conc. HNO3
(i) (a)
+ conc. H2SO4 o-nitrotoluene
(A)
(Minor) NO2
p-nitrotoluene
(b) CH3CH CH2+O3 (Major)
O (c) Since, the two substituents in the benzene ring are

Zn
present at m -positions, therefore the first substituent
CH3 CH CH2 CH3CH + HC  H in the benzene ring should be m -directing.
H2O
NO2
O O O O conc. HNO3 +
Ethanal Methanal conc. H2SO4, D
Ozonide (B)
(Nitration)
hν Benzene Nitrobenzene
(c) CH4 + Cl2 –HCl CH3Cl NO2
Methane Chloromethane
(C)
Cl2, anhyd. AlCl3, D
Conc. H2SO 4
(ii) (a) H ¾CH ¾ CH 2 ¾ H ¾ ¾¾¾¾® Chlorination
Cl
| m-nitrochloro-
OH benzene
Ethanol CH 2 == CH 2 + H 2O Red hot Fe tube
Ethene (ii) (a) 3CH CH 873 K
Acetylene (Cyclic polymerisation)
The above reaction is an example of b-elimination
Benzene
reaction. NO2 (A)
Anhyd.AlCl 3
(b) CH 3 ¾ CH 2 ¾ CH 2 ¾ CH 2 ¾ Br ¾ ¾¾¾¾®
1- bromobu tane 575 K
conc. HNO3 + conc. H2SO4
Br
| 333 K (Nitration)
CH 3 ¾ CH 2 ¾ C H ¾ CH 3 Nitrobenzene
2-bromobu tane (B)
I
The above reaction is an example of rearrangement
reaction.
HNO3 or
26. (i) (a) Acetophenone can be prepared by Friedel-Crafts (b) + I2 + HI
HIO3
acylation. Hydrogen iodide
COCH3 Benzene Iodobenzene (B)
(A)
Anhyd. AlCl3 27. (i) The complete reaction is given below

+ CH3COCl + HCl
D
Acetyl chloride H2O2
Benzene Acetophenone CH2 — CHCH2CH3 + HBr CH3CH2CH2CH2Br
Anti-Markownikoff’s
COCH3 But-1-ene rule or Kharasch effect
Br
(CH3CO)2O, Anhyd. AlCl3
D + CH3COOH
CH2 — CH — CH2 — CH3
HBr
—
Acetophenone (Secondary radical)

Br (more stable)
(ii) CH3 ¾ CH == CH¾ CH3 + HBr ¾® (ii) Only B follows Huckel’s rule. According to Huckel’s rule,
But-2-ene
CH3 ¾ CH ¾ CH2 ¾ CH3 all aromatic compounds should have ( 4n + 2 )p electrons
| B has 10 electron or 5p bonds.
Br \ 4n + 2 = 10 Þ 4n = 8 Þ n = 2
2- bromobutane As n is a natural number. B follows Huckel’s rule.
(iii) Addition of unsymmetrical reagent to unsymmetrical (iii) The molecule is non-planar because of the presence
alkene takes place according to Markownikoff ’s rule, i.e. of sp 3-hybridised carbon atom. It contains six p-electron
negative part of addendum goes to carbon atom with less cloud does not surround all the carbon atoms of the ring.
number hydrogen atoms. Therefore, it is not an aromatic compound.
CH3CH == CH2 + HBr ¾® CH3 ¾ CH ¾ CH3 Or Azulene is an aromatic compound. It has 10 electrons, so
½ it follows Huckle's rule. It is cyclic and as each carbon
Br atom is sp 2-hybridised it is a planar molecule. Thus, it is
(iv) Alkenes in the presence of trace of oxygen and at high an aromatic compound.
temperature and pressure undergo self addition. (iv) X forms an aromatic species on loosing Br which forms a
473 K ,1500 atm white precipitate with Ag+ ion of AgNO3.
nCH2 == CH2 ¾¾¾¾® ¾
( CH2 ¾ CH2 ¾)n
traces of O 2 Br
r
CH3¾ CH2

Or C == O + O == CH¾ CH3 ¾® + Ag+ + AgBr
Ethanal
CH3¾ CH2 (Aromatic)
5 4
Pentan-3-one CH3 ¾ CH2 Y cannot loose Br because resulting compound is not
3 2 1
C == CH¾ CH3 aromatic and hence not stable. Therefore, it does not
CH3 ¾ CH2 form ppt.
3-ethylpent-2-ene Br
(A ) r
28. (i) C 6H 6 being on aromatic compound does not react with
any electrophile like alkene as then it would lose its + Ag+ + AgBr
aromaticity which makes the compound very stable.
(Not aromatic)
Chapter Test 5. Assertion Among isomeric pentanes,
2, 2-dimethylpentane has the lower boiling point.
Reason Branching in hydrocarbon does not affect the
Multiple Choice Questions boiling point.
1. The major product formed when 3,3-dimethyl 6. Assertion Boiling points of cis-isomers are higher than
butan-2-ol is heated with concentrated sulphuric acid trans-isomers.
is
Reason Dipole moments of cis-isomers are higher
(a) 2,3-dimethylbut-1-ene
then trans-isomers.
(b) 2,3-dimethylbut-2-ene
(c) 3,3-dimethylbut-1-ene 7. Assertion Alkynes show geometrical isomerism.
(d) cis and trans-isomers of 2,3-dimethylbut-1-ene Reason Geometrical isomerism arises due to the
restricted rotation of a double bond.
2. The correct IUPAC name of the given structure
H3C —CH —C ºº CH is Short Answer Type Questions
½
CH3 8. Write structural formulae of the following compounds.
(a) 2-methylbut-1-yne (b) 1-methylbut-3-yne (i) 3, 4, 4, 5-tetramethylheptane
(c) 2-methylbut-3-yne (d) 3-methylbut-1-yne (ii) 2, 5-dimethylhexane
3. Consider the following reaction : 9. Complete the reactions
CaC 2 + H2O ¾® X (i) CH3CH2CH3 + HNO 3 ¾¾¾¾¾¾®
Vapour phase
Here, X refers to Copper tube

(ii) CH4 + O 2 ¾¾¾¾¾®
(a) ethene (b) ethyne 723 - 773 K
(c) methyne (d) None of these – + CaO
(iii) C 2H5CO O N a + NaOH ¾¾¾¾®
4. The aromatic compound among the following is
10. Draw the Newman projection of 1, 2-diiodoethane.
Out of the two eclipsed conformations, which is of
(a) (b) higher energy?
s 11. Give the major product for each of the following reaction:
Alc. KOH
(i) CH3 CH CH3 ¾ ¾¾¾ ®
heat
½
(c) (d) All of these Br Hg2+ /H+
(ii) CH ºº CH+H2O ¾ ¾¾¾ ¾®
r 333 K
Assertion Reasoning MCQs Long Answer Type Questions

Direction (Q. Nos. 5-7) Each of these questions 12. Write the IUPAC names of the following compounds.
contains two statements Assertion (A) and Reason (i) (CH3 ) 2 CH ¾CH==CHCH2 CH==CH ¾CHCH3
(R). Each of these questions also has four alternative |
choices, any one of which is the correct answer. You (ii) C 2H5
have to select one of the codes (a), (b), (c) and (d)
given below. (iii) CH2 == C(CH2CH2CH3 ) 2
(a) Both A and R are true and R is the correct explanation of A. (iv)
(b) Both A and R are true, but R is not the correct explanation CH3  CH2CH2CH2 CH2CH3 CH3
of A.
(c) A is true, but R is false. CH3CHCH —
— CCH2 CH CH3
Also calculate the number of s and p-bonds.
Answers
1. (b) 2. (d) 3. (b) 4. (d) For Detailed Solutions
Assertion-Reasoning MCQs Scan the code
5. (c) 6. (a) 7. (d)
Chemistry
Class 11th ( Term II)
Practice Paper 1 *
(Solved)
General Instructions Time : 2 Hours
Max. Marks : 35
1. There are 9 questions in the question paper. All questions are compulsory.
2. Question no. 1 is a Case Based Questions, which has four MCQs. Each question carries one mark.
3. Question no. 2 to 6 are Short Answer Type Questions. Each question carries 3 marks.
4. Question no. 7 to 9 are Long Answer Type Questions. Each question carries 5 marks.
5. There is no overall choice. However, internal choices have been provided in some questions. Students have to attempt
only one of the alternatives in such questions.
* As exact Blue-print and Pattern for CBSE Term II exams is not released yet. So the pattern of this
paper is designed by the author on the basis of trend of past CBSE Papers. Students are advised
not to consider the pattern of this paper as official, it is just for practice purpose.
1. Read the following and answer the questions from (i) to (v) given below
Group 1 includes Li, Na, K, Rb, Cs and Fr. They are collectively called alkali metals as they form hydroxides
on reaction with water which are strongly alkaline in nature.
These metal occurs in nature only in the form of their compounds, i.e. these never found in free states as
they are highly reactive. The less electropositive alkali metals like lithium exists in the form of their silicates
whereas the more electropositive element are found in the form of their chlorides.
The general configuration of these elements are [inert gas]ns 1 . Their atomic and ionic radii metals are
largest and ionisation enthalpy is lowest among the corresponding period.
These are white silvery, soft and malleable metals. They are so soft that they can easily be cut with a knife.
They have very low density melting and boiling points.
These metals give characteristic colour to the flame.
(i) Among the alkali metals, caesium is the most reactive because
(a) its incomplete shell is nearest to the nucleus.
(b) it has a single electron in the valence shell.
(c) it is the heaviest alkali metal.
(d) the outermost electron is more loosely bound than the outermost electron of the other alkali metals.
(ii) The yellow coloured flame is of
(a) Na (b) K (c) Ca (d) Ba
(iii) For alkali metals, which one of the following trends is incorrect?
(a) Hydration energy, Li > Na > K > Rb
(b) Ionisation energy, Li > Na > K > Rb
(c) Density, Li < Na < K < Rb
(d) Atomic size, Li < Na < K < Rb
(iv) The ionic mobility of alkali metal ions in aqueous solution is maximum for
(a) K+ (b) Rb+
(c) Li + (d) Na +
(v) In the reaction, M + O 2 → MO 2 (superoxide), (a) Which type of intermolecular forces are
the metal M is present in the molecules HF, HCl, HBr and
(a) lithium (b) sodium HI?
(c) potassium (d) barium (b) Looking at the trend of boiling points of
2. (i) Carbon monoxide is readily absorbed by HCl, HBr and HI, explain out of dipole-dipole
ammoniacal cuprous chloride solution but interaction and London interaction, which one
carbon dioxide is not. Explain. is predominant here.
(ii) Classify the following oxides as neutral acidic (c) Why is boiling point of hydrogen fluoride
basic or amphoteric. highest while that of hydrogen chloride
lowest?
CO, B2O 3 , SiO 2 , CO 2 , Al 2O 3 , PbO 2 , Tl 2O 3 .
(ii) How will you distinguish the following pair of
Or organic compounds by giving chemical tests?
(i) Which allotrope of carbon is used as moderator Propane and propene.
in atomic reactors?
5. (i) Out of benzene, m-dinitrobenzene and toluene
(ii) Explain why is there a phenomenal decrease in which will undergo nitration most easily and
ionisation enthalpy from carbon to silicon? why?
3. (i) Calculate the pressure exerted by 10.2 g of (ii) Arrange benzene, n-hexane and ethyne in
ammonia (NH 3 ) contained in 0.5 L vessel at decreasing order of acidic behaviour. Also give
315 K. For ammonia a = 5 atm L2 mol −2 , reason for this behaviour.
b = 0. 036 L mol −1 . Compare the value with the Or
calculated value if the gas were considered as (i) Why does benzene undergo electrophilic
ideal. substitution reactions easily and nucleophilic
(ii) What would have happened to the gas if the substitution with difficulty?
molecular collisions were not elastic? (ii) Despite their −I effect, halogens are o-and
Or p-directing in haloarenes. Explain
The variation of pressure with volume of the gas at 6. (i) Out of PbCl 2 , SnCl 2 , SnCl 4 and PbCl 4 which one
different temperatures can be graphically is most commonly used as a reducing agent and
represented as shown in figure. On the basis of this why?
graph answer the following questions. (ii) Diamond is covalent, yet it has high melting
(i) How will the volume of a gas change if its point and why?
pressure is increased at constant temperature?
7. (i) Why is benzene extra ordinarily stable though it
(ii) At a constant pressure, how will the volume of a contains three double bonds?
gas change if the temperature is increased from
(ii) Write down the products of ozonolysis of
200 K to 400 K?
1, 2-dimethyl benzene (o-xylene). How does the
result support Kekule structure of benzene?
Or
Pressure (bar)
(i) Complete the following

600 K
400 K −+ Soda lime
(a) H3C COONa
Heat
200 K
0
Volume (dm3)
4. (i) Use the information and data given below to (b) OH Zn dust
answer the questions (a) to (c), stronger
intermolecular forces result in higher boiling (ii) Why iodination of benzene is carried out in the
point. presence of nitric acid or iodic acid?
Strength of London forces increases with the (iii) Suggest a route for the preparation of
number of electrons in the molecule. nitrobenzene starting from acetylene?
Boiling point of HF, HCl, HBr and HI are 293 K, (iv) On converting benzene to toluene, state whether
189 K, 206 K and 238 K respectively. there will be a rise or fall in the melting point.
8. (i) 100 mL of a liquid is contained in an insulated What are the equilibrium partial pressures of CO
container at a pressure of 1 bar. The pressure is and CO 2 at 1050 K if the initial partial pressures
steeply increased to 100 bar. The volume of are, pCO = 1.4 atm and pCO 2 = 0.80 atm?
the liquid is decreased by 1 mL at this constant (ii) Some processes are given below. What happens
pressure. Find ∆H and ∆U. to the process if it is subjected to a change given
(ii) One mole of acetone requires less heat to in the brackets?
vaporise than 1 mole of water. Which of the two Melting point
liquids has higher enthalpy of vaporisation? (a) Ice Water (Pressure is increased)
(iii) At 1 atm will the ∆ f H° be zero for Cl 2 ( g) and (b) Dissolution of NaOH in water (Temperature is
Br 2 ( g). Explain. increased)
Or (i) For the same increase in volume, why work Or
done is more if the gas is allowed to expand
(i) Show that the degree of dissociation (α ) for the
reversibly at higher temperature?
dissociation of PCl 5 into PCl 3 and Cl 2 in
(ii) Predict the change in internal energy for an
 K p  1/2
isolated system at constant volume. pressure p is given by α =   .
(iii) If the combustion of 1g of graphite produces  p +Kp 
20.7 kJ of heat, what will be molar enthalpy (ii) At 473K , equilibrium constant K c for decomposition
change? Give the significance of sign also. of phosphorus pentachloride, PCl 5 is 8.3 × 10 −3 .
(iv) Given that the enthalpy of formation of H 2O is If decomposition is depicted as,
− 68 kcal/mol. Calculate the enthalpy of
PCl 5 ( g) r PCl 3 ( g) + Cl 2 ( g) ;
formation of OH − ions.
∆H ° = 124.0 kJ mol −1
9. (i) One of the reaction that takes place in producing
steel from iron ore is the reduction of iron(II) (a) Write an expression for K C for the reaction.
oxide by carbon monoxide to give iron metal and (b) What is the value of K C for the reverse reaction at the
CO 2 . same temperature?
(c) What would be the effect on K G if (a) more PCl 5 is
FeO (s ) + CO ( g) r Fe (s) + CO 2 ( g) ; added (b) pressure is increased (c) the temperature is
K p = 0.265 atm at 1050 K increased ?
Explanations
1. (i) (d) On moving down a group, size of metal increases, 10.2
3. (i) Number of moles of ammonia n = = 0. 6 mol
i.e. the distance between nucleus and valence shell 17
increases. As, Cs lies towards the bottom of group According to van der Waals’ equation,
1, the outermost shell electron of caesium is more  an 2 
loosely bound than the outermost shell electron of  p + 2  ( V − nb ) = nRT
 V 
the other alkali metals. That’s why, caesium is most
nRT an 2
reactive among the alkali metals. p= − 2
( V − nb ) V
(ii) (a) On burning, sodium imparts yellow colour to the
0. 6 × 0. 082 × 315 5( 0. 6)
flame, potassium imparts pale violet colour, calcium = −
imparts brick red colour and barium imparts grassy ( 0. 5 − 0. 6 × 0. 036) ( 0. 5)2
green colour. = 20. 395 atm
(iii) (c) In general, density increases on moving down in a If the gas were considered ideal, then the value of
group but density of potassium (K) is lesser than pressure ( p) can be obtained by using ideal gas
that of sodium (Na). This is because of the equation as
abnormal increase in atomic size on moving from nRT
p=
Na (86 pm) to K (227 pm).Thus, the correct order of V
density is Li < K < Na < Rb. 0.6 × 0.082 × 315
= = 30.996 atm
(iv) (b) Smaller the size of the ion, more highly it is 0.5
hydrated due to high polarising power and hence, (ii) On every collisions, there would have been loss of
its hydrated ionic radius will be greater and its energy. As a result the molecules would have slowed
ionic mobility is lesser in aqueous solution. down and ultimately settle down in the vessel.
Thus, the order of ionic mobility is, Moreover, the pressure would have gradually reduced
Li + < Na + < K+ < Rb+ < Cs+ to zero.
(v) (c) In superoxide, oxygen is in O−2 form. Since, Or
superoxide is of MO2 type, it is clear that, it is alkali (i) In accordance with Boyle’s law, pressure of a gas is
metal superoxide. As the size of metal ions inversely proportional to its volume if temperature is
increases, tendency to form superoxides increases. kept constant. Thus, the volume of a gas will decrease if
Hence, it is potassium superoxide (KO2 ). the pressure on the gas is increased keeping the
temperature constant. e.g. At 200 K when pressure
2. (i) Due to the presence of a lone pair of electrons on
increases from p1 to p 2, volume of the gas decreases,
carbon in CO, it acts as a Lewis base (or ligand) and thus
V2 < V1.
forms a soluble complex with ammoniacal cuprous chloride
solution. (ii) In accordance to Charles’ law, volume of a gas is
directly proportional to its temperature if pressure is
CuCl + NH 3 + •• CO → [Cu(CO)NH 3 ]+ Cl − kept constant.
Soluble complex
Thus, on increasing temperature, the volume of a gas
On the other hand, CO2 does not act as a Lewis base will increase when pressure is kept constant.
since it does not have a lone pair of electrons on the
carbon atom and hence, does not dissolve in At constant P when we increase the temperature from
ammoniacal cuprous chloride solution. 200 K to 400 K, the volume of the gas increases,
V4 > V3.
(ii) Neutral oxides CO
Acidic oxides B2O3, SiO2 and CO2 p
p2
Amphoteric oxides Al 2O3 and PbO2
p (constant) 600 K
Or p1
(i) Graphite. 400 K
(ii) As we move from carbon to silicon atomic size 200 K
0
increases, i.e. the distance between the outermost V2 V1 V4 V
electron and nucleus increases. V3
Thus, this electron experience very small attraction 4. (i) From the information and data given in the question,
from the nucleus and hence, easy to remove. we concluded that
Since, the size of Si-atom is larger, the outer electron (a) In HCl, HBr and HI, dipole-dipole and London
experience lesser attraction and hence, its ionisation forces are present because molecules possess
enthalpy (energy required to remove an electron) is permanent dipole. In HF molecule, dipole-dipole,
smaller. London forces and hydrogen bonding are present.
(b) Electronegativity of chlorine, bromine and iodine (ii) Halogens are moderately deactivating group. Because
decreases in the following order. Cl > Br > I of their strong −I-effect, overall electron density on
Therefore, dipole moment should decrease from benzene ring decreases.
HCl to HI. As a result, , dipole-dipole interaction However, due to resonance the electron density on
should also decrease from HCI to HI. But boiling o and p-positions is greater than that at m -position.
point increases on moving from HCl to HI. This Hence, they are also o and p-directing groups.
means that London forces are predominant. This is 3p +Cl +Cl
so because London forces increases as the number Cl 2p
of electrons in a molecule increases and in this
case, number of electrons is increasing from HCl s
towards HI.
(c) Hydrogen fluoride has highest dipole moment is due s
to highest electronegativity of fluorine as well as +Cl Cl
due to the presence of hydrogen bonding in HF.
Therefore, HF has highest boiling point. s
(ii) Propane and propene can be distinguished by bromine
water test and alkaline KMnO4 test.
CH3CH2CH3 + Br2 / H2O → No change
CH3  CH == CH2 + Br2 / H2O → CH3  CH  CH2 6. (i) Sn 4 + is more stable than Sn 2 + thus Sn 2 + have a great
Propene Brown | | tendency to get converted into Sn 4 + by losing two
Br Br electrons hence, from the given compounds, SnCl 2 is
(Colourless) used as reducing agent.
Pink colour of alkaline KMnO4 turns colourless in the (ii) Diamond has a three-dimensional network with strong
presence of unsaturated compound. C  C bonds, which are very difficult to break and thus,
5. (i) Nitration of benzene is an electrophilic substitution diamond has high melting point.
reaction. Presence of electron releasing group such as 7. (i) Resonance and delocalisation of electrons generally
 CH3 activates the benzene nucleus towards lead to the stability of benzene molecule.
electrophilic substitution while presence of
electron withdrawing group such as NO2
deactivates the benzene nucleus towards electrophilic
substitution.
Hybrid structure
Therefore, the ease of nitration decreases in the order
Toluene > benzene > m -dinitrobenzene The dotted circle in the hybrid structure represents the
six electrons which are delocalised between the six
Thus, toluene will undergo nitration most easily.
carbon atoms of the benzene ring. Therefore, presence
(ii) The hybridisation state of carbon in the given of delocalised π-electrons in benzene makes it more
compounds is stable than the hypothetical cyclohexatriene.
(ii)
; CH3 (CH2)4  CH3; H C CH CH3
n-hexane Ethyne CH3
Benzene (i) O3, CH2Cl2 , 196 K
Type of hybridisation sp 2 sp 3 sp
s-character 33.33% 25% 50% 1,2-dimethyl benzene
Acidic character increases with increase in s-character O CH3

of the orbital. Hence, decreasing order of acidic
O CH3 CH3
behaviour of ethyne > benzene > hexane. O O 1° CHO
Or C 2° CH3 + 2
O C
(i) Due to the presence of delocalised 6π-electrons, O CHO
O O
benzene acts as a rich source of electrons. O
Glyoxal
So, it attracts the electrophilic reagent (electron O 1,2-dimethyl glyoxal
deficient species) towards itself but repels the O
nucleophilic reagents. That’s why benzene gives Zn/H2O
electrophilic substitution reactions easily and
nucleophilic substitution reaction with difficulty.
CH3 ∆H = ∆U + ∆pV = 100 + p 2V2 − p1V1

CH3 = 100 + (100 × 99) − (1 × 100)
(i) O3, CH2Cl2, 196 K
Similarly, = 100 + 9900 − 100 = 9900 bar mL
(ii) Zn/H2O
O (ii) Less the heat required to vaporise 1 mole of a liquid,
CHO less is its enthalpy of vaporisation. Hence, water has
2CH3C CHO + higher enthalpy of vaporisation.
Methyl glyoxal CHO (iii) ∆ f H° for Cl 2(g) will be zero but ∆ f H° for Br2( g) will not
Glyoxal
be zero because liquid bromine is its elementary state
All the three products cannot be obtained from any and not gaseous bromine.
one of the two Kekule structures. This indicates that Or
o-xylene is a resonance hybrid of two Kekule structures
(i) For isothermal reversible expansion, W = − p int × ∆V.
I and II.
At higher temperature, internal pressure of the gas is
more so work done is more.
CH3 CH3 CH3
(ii) For isolated system there is no transfer of energy as
CH3 CH3 CH3 heat or work, so according to the first law of
thermodynamics,
∆U = q + W ⇒ ∆U = 0 + 0 = 0
I II Resonance hybrid (iii) Molar enthalpy change for the combustion of graphite,
Or ∆H = enthalpy of combustion of 1 g graphite × molar
mass
−+ Soda lime
(i) (a) H3C COONa CH3 ∆H = − 20.7 kJ g−1 × 12 g mol −1
Heat
= − 2.48 × 102 kJ mol −1
Toluene
Negative sign in the value of ∆H indicates that the
reaction is exothermic.
Zn dust (iv) For neutralisation reaction, we know that
(b) OH + ZnO
H+ + OH− → H2O ; ∆ r H° = − 13.7 kcal
Benzene ∴ ∆ r H ° = ∆ f H ° ( H2O) − [ ∆ f H ° ( H+ ) + ∆ f H ° ( OH− )]
(ii) The iodination of benzene is usually brought about by
refluxing benzene with iodine and conc. HNO3 or HIO3. i.e. − 13.7 = − 68 − [0 + ∆ f H ° (OH− )]
I [Q + ∆ f H ° ( H+ ) = 0]
or ∆ f H° ( OH− ) = − 68 + 13.7 = − 54.3 kcal mol −1
HNO3 or
+ I2 + HI 9. (i) FeO(s) + CO (g) r Fe (s) + CO2 ( g);
HIO3
Initial pressure 1.4 atm 0.80 atm (K p = 0.265 at 1050
K)
p CO 2 0.80
(iii) 3CH CH
Red hot Fe tube Qp = = = 0.571 [Q Fe and FeO are solids.]
873 K p CO 1.4
Acetylene
(Cyclic polymerisation)
Benzene Q Qp > K p , the reaction will go in reverse direction.
NO2 Due to this, pressure of CO2 will decrease and that of
Conc. HNO3 + Conc. H2SO4
CO will increase to attain equilibrium.
333 K (Nitration) Suppose p is the decrease in pressure of CO2 and p is
Nitrobenzene the increase in pressure of CO. Hence,
(iv) On converting benzene to toluene, there is a fall in the p CO 2 = ( 0.80 − p) and p CO = (1.4 + p).
melting point although toluene has the higher molecular p CO 2 (0.80 − p)
mass. This is because the planar molecules of benzene Now, from K p = ⇒ 0.265 =
p CO (1.4 + p)
can pack more closely in the crystal lattice and the
0.429
cohesive forces are strong, whereas the methyl group in p= = 0.339 atm
toluene prevents such close packing. 1.265
8. (i) p1 = 1 bar, p 2 = 100 bar, V1 = 100 mL, V2 = 99 mL Hence, at equilibrium, p CO 2 = 0.80 − 0.339 = 0.461 atm
For adiabatic process, q = 0, ∆U = q + W and p CO = 1.4 + 0.339 = 1.739 atm
∆U = W (ii) (a) Equilibrium will shift in the forward direction, i.e.
W = − p∆ V more of ice will melt.
= − 100 ( 99 − 100) = 100 bar mL (b) Solubility will decrease because it is an exothermic
process.
Or or ( p + K p )α 2 = K p
(i) PCl 5 r PCl 3 + Cl 2 1/ 2
 Kp 
Initial moles 1 0 0 or α =  
 p + Kp 
Moles after diss. 1−α α α (Total = 1 + α)
(ii) PCl 5 (g) r PCl 3 (g) + Cl 2 (g) ; K C = 8.3 × 10−3
∴ p PCl = 1 − α × p, p =
α
× p,
5
1+ α PCl 3
1+ α [PCl 3 ] [Cl 2 ]
• Kc =
p Cl = α × p, [PCl 5 ]
2
1+ α • For the reverse reaction,
p PCl × pCl 1
Kp = 3 2
K C′ =
p PCl KC
5
 α  α  1
= = 120.48
 p  p 8.3 × 10−3
1+ α  1+ α 
= (a) Addition of PCl 5 have no effect on K C because K C is
 1−α 
 p constant at constant temperature.
1+ α 
(b) K C does not change with pressure.
α 2p (c) The given reaction is endothermic, hence on
=
1 − α2 increasing the temperature, K f will increase,
or (1 − α 2 )K p = α 2p  K 
this results in increase in K C K C = f  .
 Kb 
Chemistry
Practice Paper 2 *
(Unsolved)

Max. Marks : 35
1. Read the following and answer the questions from (i) to (v) given below.
Elements in which the last electrons enters in p-orbitals of outermost shell are called p-block elements.
Since, p-orbitals can accommodate a maximum of 6 electrons, so a total of 6 groups are belong to this group.
Most of the elements of this block are non-metals. However, it also contains metals as well as metalloids.
Heavier members of each group also exhibit an oxidation state which is two less than group oxidation state.
This oxidation state is more stable as compared to their group oxidation states. The first member of each
group of p-block differ from rest of the members of its corresponding group due to its very small size and
unavailability of d-orbitals.
(i) The correct order of atomic radii in group 13 elements is
(a) B < Ga < Al < Tl < In (b) B < Al < Ga < In < Tl
(c) B < Al < In < Ga < Tl (d) B < Ga < Al < In < Tl
(ii) Which of the following is a least stable compound?
(a) BCl 3 (b) GaCl 3 (c) InCl 3 (d) TlCl 3
(iii) Which species does not exist?
(a) [BF6 ]3− (b) [AlF6 ]3− (c) [GaF6 ]3− (d) [InF6 ]3−
(iv) The tendency of BF3 , BCl 3 and BBr3 to behave as Lewis acid decreases in the sequence
(a) BF3 > BCl 3 > BBr3
(b) BCl 3 > BF3 > BBr3
(c) BBr3 > BCl 3 > BF3
(d) BBr3 > BF3 > BCl 3
(v) Which of the following statements is correct?
(a) BCl 3 is more stable than TlCl 3
(b) AlF3 is high melting solid but AlCl 3 is low melting
(c) BX bonds distance in BX 3 is shorter than the theoretical value
(d) All of the above statements
2. (i) How would you distinguish between (iii) What happens when iso-butene is treated with hot
(a) Be(OH)2 and Ba(OH)2 alkaline KMnO4 ?
(b) BeSO4 and BaSO4 7. (i) Which one of the following is not extensive state
(ii) Why does the solubility of alkaline earth metal function?
hydroxides in water increase down the group? Enthalpy change, internal energy change and
Or pressure
(i) All compounds of alkali metals are easily soluble in (ii) 10 moles of an ideal gas expand isothermally and
water but lithium compounds are more soluble in reversibly from a pressure of 5 atm to 1 atm at 300 K.
organic solvents. Explain. What is the largest mass that can be lifted through a
(ii) Why are potassium and caesium, rather than height of 1 m by this expansion? [Ans. 4092.70 kg]
lithium used in photoelectric cells? (iii) Calculate the standard enthalpy of formation of
C2 H4 ( g ) from the following thermochemical
3. 135 mL of a gas is collected over water at 25°C and equation.
0.993 bar. If the gas weighs 0.160 g and the aqueous
C4 H8 ( g ) + 6O2 ( g ) → 4CO2 + 4 H2 O
tension at 25°C is 0.0317, calculate the molar mass
of the gas. [Ans. 30.49 g mol −1] Given that ∆ f H s of CO2 ( g ), H2 O ( g ) as − 393. 5 and
Or − 249 kJ mol −1 respectively. [Ans. ∆Η f° (C2H4 ) =76 kJ mol −1]
An equilibrium mixture at 300 K contains N 2O 4
and NO 2 at 0.28 and 1.1 atm pressure respectively. Or
If the volume of the container is doubled, calculate (i) When an ideal gas expands into vacuum, there is
the new equilibrium pressure of two gases. neither absorption nor evolution of heat. Why?
[Ans. p ( N 2O 4 ) = 0.95 atm, p ( NO 2 ) = 0.64 atm] (ii) The standard heat of formation of CH 4 ( g ), CO 2 ( g )
and H 2 O( g ) are − 76.2 , − 394. 8 and − 241. 6 kJ mol −1
4. (i) Sodium fire in the laboratory should not be
extinguished by pouring water. Why? respectively.
(ii) Comment on each of the following observations. Calculate the amount of heat evolved by burning 1 m
3
(a) The mobilities of the alkali metal ions in aqueous of methane measured at NTP. [Ans. 35794.6 kJ]
solution are Li+ < Na+ < K + < Rb+ < Cs+. (iii) Predict in which of the following, entropy
(b) Lithium is the only alkali metal which forms increases/decreases. Give reason.
nitride directly. (a) Temperature of crystalline solid is raised from
5. (i) For an ideal gas, how does the plot of log p vs log V 0 K to 115 K.
differ from that of log V vs log T? Explain. (b) H 2 ( g ) → 2H( g )
(ii) What happens, when 8. (i) The equilibrium constant for the following reaction
(a) ethyl alcohol is heated in the presence of H2 SO4 is 1. 6 × 10 5 at 1024 K.
at 443 K?
H 2 ( g ) + Br 2 ( g ) r 2HBr ( g )
(b) ethyl bromide is heated with alcoholic KOH?
Find the equilibrium pressure of all gases if 10.0 bar
Or of HBr is introduced into a sealed container at 1024 K.
(i) Explain, why Boyle’s law cannot be used to [Ans. pHBr = 10 Bar]
calculate the volume of a real gas when it is (ii) Explain the following
converted from initial state to final state by an
(a) Ice melts slowly at higher altitudes.
adiabatic expansion ?
(b) Pure liquids and solids can be ignored while
(ii) Predict the major product(s) of the following writing the equilibrium constant expressed.
reactions and explain their formation.
(Ph  CO  O)
Or
H3 C CH == CH2  
2
→ (i) Bromine monochloride, BrCl decomposes into
HBr
bromine and chlorine and reaches the equilibrium,
H3 C CH == CH2 HBr
→
2BrCl( g ) r Br 2 ( g ) + Cl 2 ( g )
6. (i) Arrange the following in order of increasing ease of
dehydrohalogenation C2 H5 I, C2 H 5 Br, C2 H 5 Cl. for which K C = 32 at 500 K. If initially pure BrCl is
(ii) Write the structure and IUPAC name of X ? present at a concentration of 3. 3 × 10 −3 molL −1 ,
what is its molar concentration in the mixture at
Diethyl ether
HC ≡≡ C − Na + + CH 3 CH 2 CH 2Br → equilibrium? [Ans. BrCl = 2.68 × 10 −4 mol L −1]
X + NaBr
(ii) The value of K C for the reaction. Or

−3
2A r B + C is 2 × 10 . Assign structures to the following
At a given time, the composition of reaction (i) An alkyne (X) has molecular formula C5 H8 . It reacts
mixture is [ A] = [B] = [ C] = 3 × 10 − 4 M. In neither with sodamide nor with ammoniacal cuprous
chloride.
which direction the reaction well proceed?
(ii) A hydrocarbon ‘Y’ decolourises bromine water. On
9. (i) 7-bromo-1, 3, 5-cycloheptatriene exists as an ion ozonolysis it gives 3-methyl butanal and
whereas 5-bromo-1, 3-cyclopentadiene does not formaldehyde. Give the name of the compound.
form an ion even in presence of Ag + . Explain.
(iii) A hydrocarbon (Z) has the molecular formula C8 H10 . It
(ii) Explain why the following systems are not does not decolourise bromine water and is oxidised to
aromatic? benzoic acid on heating with K 2 Cr2 O7 . It can also
have three other isomers. A, B and C write the
(a) CH2 (b)
structures of Z, A, B and C.
Answers
1. (i) -(d); (ii)-(d); (iii)-(a); (iv)-(c); (v)-(d)
Chemistry
Practice Paper 3 *
(Unsolved)

Max. Marks : 35
1. Read the following and answer the questions from (i) to (v) given below.
Gases that do not obey gas laws under all conditions of temperatures and pressures are called real gases.
Most of the gas are real in nature that means they follows gas laws only at very low pressures and high
temperatures.
It is also noticed that easily liquefiable gases exhibit larger deviation as compared to gases that liquify with
difficulty.
To study the deviation of real gases from ideal behaviour. We plot the pV vs p and p vs V for different gases.
This analysis helps to conclude how for the relation pV = nRT reproduce actual p − V − T relationship of
gases.
The ideal gas equation was derived on the basis of certain assumption of kinetic theory of gases. But when
studied carefully, it was found that two of these assumptions are not true at high pressure or low
temperature.
In 1983, van der Waals’ modified the ideal gas equation by introducing corrections in it for the failure of the
two assumptions, i.e. (a) pressure correction (b) volume correction.
(i) The correction factor ‘a’ to the ideal gas equation corresponds to
(a) electric field present between the gas molecules
(b) volume of the gas molecules
(c) density of the gas molecules
(d) forces of attraction between the gas molecules
(ii) Given van der Waals’ constant of NH3 , H2 , O2 and CO2 are respectively 4.17, 0.244, 1.36 and 3.59. Which one
of the following gases is most easily liquefied?
(a) O2 (b) H2 (c) NH3 (d) CO2
(iii) Which among the following gases can be liquefied easily?
(a) Chlorine (b) Nitrogen
(c) Oxygen (d) Hydrogen
(iv) In van der Waals’ equation of state for non-ideal 6. K p for the reaction,
gas, the term that accounts for intermolecular
N 2 ( g) + 3 H 2 ( g) e2NH (g)3
force is
(a) ( V = b ) (b) (RT ) −1 at 400°C is 1. 64 × 10 atm − 2 . Find K C , also calculate
−4
 a ∆G ° using ∆G ° using K p and K C values and interpret

(c)  p + 2  (d) RT
 V  the difference. [Ans. ∆G = 3479 Jmol −1]
Or
(v) Maximum deviation from ideal gas is expected
from On the basis of the equation. pH = − log[ H + ], the pH
(a) H 2( g) (b) N 2( g) of 10 − 8 mol dm − 3 solution of HCl should be 8.
(c) CH 4( g) (d) NH 3( g) However, it is observed to be less than 7.0 ? Explain
the reason.
2. (i) Account for the following
(a) Graphite is used as lubricant. 7. (i) Predict in which of the following, entropy
(b) Diamond is used as an abrasive. increases/decreases.
(ii) Write the resonance structures of CO23 − and HCO−3 . (a) A liquid crystallises into a solid.
(b) Temperature of a crystalline solid is raised from 0 K to
Or
115 K.
(i) Consider the compounds, BCl 3 and CCl 4 . How (c) 2NaHCO3 (s ) → Na 2 CO3 (s ) + CO2 (g) + H 2 O ( g )
will they behave with water?
(d) H 2 ( g ) → 2H ( g )
(ii) Why carbon has no tendency to form complex
(ii) The enthalpy of atomisation for the reaction,
compounds?
CH4 ( g ) → C( g ) + 4 H( g ) is 1665 kJ mol −1 . What is
3. How will you convert benzene into the bond energy of C—H bond ? [Ans. 416.25 kJmol −1]
(i) p-nitrobromobenzene
(iii) Determine the value of ∆H and ∆U for the reversible
(ii) m-nitrochlorobenzene isothermal evaporation of 90.0 g of water at 100°C.
(iii) p-nitrotoluene Assume that water vapour behave as an ideal gas
(iv) acetophenone? and heat of evaporation of water is 540 cal
(R = 2.0 cal mol −1 K −1 ). [Ans. ∆H = 44870 cal]
Or
What happens, when benzene is treated with Or
(i) Br2 in presence of anhyd. AlCl 3 ? (i) Carbon monoxide is allowed to expand isothermally
and reversibly from 10 m 3 to 20 m 3 at 300 K and work
(ii) conc. H2 SO4 at 330 K?
obtained is 4.754 kJ. Calculate the number of moles
(iii) chloroethane and anhyd. AlCl 3 ? of carbon monoxide. [Ans. n = 2.75 mol]
4. (i) What is the effect of reducing volume on the (ii) Establish a relationship between ∆H and ∆U in
following system? Haber ‘s process of synthesis of ammonia assuming
2C(s ) + O2 ( g ) 2 CO ( g )
- that gaseous reactants and products are ideal.
(ii) Under what conditions, K C = K p for a gaseous (iii) Standard vaporisation enthalpy of benzene at boiling
reaction? point is 30.8 kJ mol −1 . For how long would 100 W
electric heater have to operate in order to vaporise a
(iii) Explain, why p-xylene has higher melting point
100 g sample at that temperature (power= energy/time
than the corresponding ortho or meta-isomers. and 1 W = 1 Js −1 )? [Ans. Time = 6.6 min]
Or
8. (i) Arrange the following set of compounds in order of
(i) At a certain temperature and total pressure of their decreasing relative reactivity with an
10 5 Pa, iodine vapour contains 40% by volume of electrophile, E + .
I-atoms. (a) Chlorobenzene, 2, 4-dinitrochlorobenzene,
Calculate K p for the equilibrium. p-nitrochlorobenzene
(ii) Suggest the name of a Lewis acid other than (b) Toluene, p-H 3 CC 6 H 4 NO 2 ,p-O 2 NC 6 H 4
anhydrous aluminium chloride which can be used NO 2
during ethylation of benzene. Also explain your answer.
5. (i) Like CO, why its analog of SiO is not stable? (ii) Which of the two trans-but-2-ene or trans-pent-2-ene
(ii) PbO2 is a stronger oxidising agent than SnO2 . is non-polar?
(iii) Explain, why alkynes are less reactive than alkenes (ii) Why is Li 2 CO3 decomposed at a lower
toward addition of Br 2 . temperature whereas Na 2 CO3 at higher
Or temperature?
(i) Write IUPAC names of the following compounds. (iii) Write the formulae of
(a) CH3 CH == C(CH3 )2 (a) Albite
(b) CH 2 == CH  C ≡≡ C  CH 3 (b) Chile saltpetre
(ii) Hydrocarbon A (molecular formula is C 5H 8 ) gave Or
a white precipitate with ammoniacal silver nitrate. (i) Complete the following reactions.
Oxidation of A with hot alkaline KMnO4 gave
(a) O 22− + H 2 O →
2-methyl propanoic acid. What is the structural
formula of A? (b) O −2 + H 2 O →
(iii) What happens when 2-bromobutane is being (ii) What is the structure of BeCl 2 molecule in
treated with KOH (alcoholic)? gaseous and solid state?
9. (i) Write the Lewis structure of O−2 ion and find out (iii) Arrange the alkaline earth metal carbonates in the
decreasing order of thermal stability.
oxidation state of each oxygen atom? What is the
average oxidation state of oxygen in this ion?
Answers
1. (i)-(d); (ii)-(c); (iii)-(a); (iv)-(c); (v)-(d)
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CBSE Term II

Case Based Questions

Short/Long Answer Type Questions

3 Practice Papers with Explanations

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States of Matter: Gases and Liquids

Some p-Block Elements

Exam Scheme Term I & II

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1. Boyle’s Law (Pressure-Volume Relationship) At constant p and T; V µ n (Avogadro’s law)

where, b is the volume occupied by one mole of the molecules

0 p 3. van der Waals’ Equation

Dp µ (Number of particles per unit volume) 2

23.1 whose slope is -‘a ’.

Objective Questions (c) III and IV (d) I and IV

(i) How will the volume of a gas change if its pressure

Subjective Questions (ii) At a constant pressure, how will the volume of a

mass of displaced air and the mass of the balloon.

28. Based on the expression æç p +

increases, i.e. molecules start moving faster. Hence, the

R = 0.082 L atm mol -1K-1 m He = 1117 . 46 kg

Empty volume = Total volume of gas 2.9 g ´ R ´ 368 K 0.184 g ´ R ´ 290 K

Thermodynamics deals with the study of different energy l

Moreover, DH = DU + Dn g RT Standard Enthalpy Changes for Different Types Processes

case II D ng < 0, then DH < DU l Enthalpy of H2 O(l ) ¾® H2 O( g) D vapH° or DH°vap

O 2 (g) ¾® H 2 O(l ) D f H° or DH°f

e.g. C 2 H5 OH( l) + 3O 2 ( g) ¾® 2CO 2 ( g) + 3H 2 O( l) ; l Enthalpy of H2 ( g) ¾® 2 H( g) D aH° or DH°a

HR = enthalpy of formation of reactants -

Born-Haber Cycle Enthalpy diagram for endothermic reactions

q q Standard Free Energy Change

Second Law of Thermodynamics - - - (at low T ) Reaction is spontaneous at low

Sol The process of evaporation can be represented as 1

Example 9. Use the following data to calculate D lattice H s for =-

10. Which of the following statements is correct?

same conditions? What is the standard enthalpy of

process as combustion, although, the final products are

3. When compression is carried out in infinite steps with \ q p = D H.

14. Given, 18. 3C(graphite) + 4H2 (g) ¾® C3 H8 (g)

22. (i) Molecular formula of butane = C 4 H10 H H

24. We are given, Benzene Cyclohexane

In a reversible reaction, the point at which there is no further Solid-Vapour Equilibrium

Liquid-Vapour Equilibrium Equilibria in Chemical Processes

The variation of concentration of reactants and products in a Law of Mass Action

masses of the reactants’.

Characteristics of Chemical Equilibrium Law of Chemical Equilibria and

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Arrhenius concept Furnish/release H+ Furnish/release OH- ions HCl s H+ + Cl - ; NaOH s Na + + OH-

Lewis concept Accept a pair of Donate a pair of electrons H+ + OH- ¾® H2 O

Ionisation Constant of Acids and Bases The pH Scale

Relation between Ka and Kb Buffer Solutions

[N 2 ] = 1.5 ´ 10 -2 M. [H 2 ] = 3.0 ´ 10 –2 M or x = 0.29172 - 0.748x

Sol. Hydrazine undergoes ionisation in the following manner. Þ S + 0. 01S – 64 ´ 10–8 = 0

NH2 NH2 + H2 O r NH2 NH+3 + OH- - 0. 01 ± ( 0. 01)2 + ( 4 ´ 64 ´ 10–8 )

pK b = - log K b = - log (8.96 ´ 10 -7 ) = 6.04

11. K a , K a and K a are the respective ionisation

4. CO (g) + 3 H2 (g) r CH4 (g) + H2 O(g) ; K C = 3.90 at 1300 K. 2 ´ 2 ´ 10 ´ 10 ´ 0. 625 ´ 10- 5 = x 2