Chapter 6

Thermodynamics
Chapter Contents
z Chemical Thermodynamics CHEMICAL THERMODYNAMICS
z System and Surroundings The branch of science which deals with the study of the quantitative
z Thermodynamic Process relationship between heat and other forms of energy is known as
z Reversible and Irreversible Thermodynamics. When the study is confined to chemical changes
Process only, the branch is known as Chemical Thermodynamics.

z Internal Energy
SYSTEM AND SURROUNDINGS
z First Law of Thermodynamics
A system in thermodynamics refers to that part of universe in which
z Pressure-volume Work
observations are made and remaining universe constitutes the
z Free Expansion surroundings. The surroundings include everything other than the system.
z Enthalpy System and the surroundings together constitute the universe.
z Heat Capacity The universe = The system + The surroundings.
z Enthalpy Change, rH of a z Types of system : Depending on the interactions between system and
Reaction - Reaction Enthalpy its surroundings, three kinds of system are distinguishable.
z Bond Energy (i) Isolated system : A system which neither exchanges energy nor
z Hess’s Law of Constant Heat matter with its surroundings is called an isolated system. For
Summation example a liquid in contact with its vapour in an insulated closed
z Spontaneous Processes vessel is an isolated system.
z Second Law of (ii) Closed system : A system which may exchange energy but not
Thermodynamics matter with its surroundings is called a closed system. If in the
z Entropy Change during Phase above example the vessel containing liquid in contact with its vapour
is closed one but is not insulated. It is a closed system.
Transformations
z Gibb's Free Energy (iii) Open system : A system which may exchange both energy and
matter with its surrounding is called an open system. The
z Third Law of Thermodynamics
evaporation of water in an open vessel is an example of open
system. Water absorbs heat from the surroundings and escapes
into surroundings as water vapour.
z State of a system : The system is said to have a definite state when
it is in such a condition where all of its macroscopic properties have
definite values. When the value of any one of its macroscopic properties
changes, the system is said to have a different state. Thus the state of
a system is defined when its macroscopic properties are specified.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
140 Thermodynamics NEET

z State variables : The macroscopic properties of a system are often called state variables, since the state
of a system changes with the change in any of the macroscopic properties. Of all the macroscopic properties
(state variables) pressure, volume, temperature and composition, assume particular importance in
thermodynamics, since they can be controlled more easily.
z State function : A state function is a property of the system whose value depends only upon the state of
the system and is independent of the path or manner by which the state is reached. The change in the value
of these properties (state functions) depends only upon the initial and final states of the system and not on
the path by which the change from initial to final state is brought about. Some common state functions are
pressure (P), volume (V), temperature (T), internal energy (E), enthalpy (H), entropy (S) etc.
z Intensive & Extensive Properties
The properties of the system can be classified into two types:
(i) Intensive properties : The properties of the system whose value is independent of the amount of
substance present in the system are called intensive properties. For example : temperature, pressure,
viscosity, etc. are intensive properties.
(ii) Extensive properties : The properties of the system whose value depends upon the amount of
substance present in the system are called extensive properties. For example : mass, volume, surface
area and energy are extensive properties.

THERMODYNAMIC PROCESS
Let us consider a system having P1V1 and T1 state functions if T1 is changed to T2 then the resulting system
is characterized by state functions P1V1 and T2 and the process of changing state is called as thermodynamic
process that is thermodynamic process can be defined as a process having change in state of system. These
are of following types.
Isothermal Process : The thermodynamic process in which temperature remains constant throughout are
called isothermal process.
Adiabatic Process : The thermodynamic process in which heat exchange between system and surrounding
is not possible.
Isobaric Process : The thermodynamic process occurring at constant pressure are called isobaric process.
Isochoric Process : The thermodynamic process occurring at constant volume are called isochoric process.
Cyclic Process : The thermodynamic process having same initial and final state are called cyclic process.

REVERSIBLE AND IRREVERSIBLE PROCESS

(i) Reversible process : Process where change is carried out so slowly that system and surrounding are
always in equilibrium.
(ii) Irreversible process : Process other than reversible process are irreversible process.
Differences between Reversible and Irreversible Processes

S.No. Reversible process Irreversible process

1. It takes place in infinite number of infinitesimally It takes place in a single step.

small steps and it would take infinite time to
occur.
2. It is imaginary as it assumes the presence of It is real and can be performed actually.
frictionless and weightless piston.
3. It is in the state of equilibrium at all the stages It is in equilibrium state only at the initial and
of operation. final stages of the operation.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Thermodynamics 141

S.No. Reversible process Irreversible process

4. All changes are reversed when the process is After the occurring of the process changes do
carried out in reversible direction. not return to the initial state by themselves.
5. It is extremely slow. It proceeds at measurable speed.
6. Work done by a reversible process is greater Work done in irreversible process is smaller
than the corresponding irreversible process. than the corresponding reversible process.

INTERNAL ENERGY (U)

The inherent energy which is possessed by a substance by virtue of its existence is called its Internal Energy.
The total energy possessed by a substance is known as internal or intrinsic energy. In case of a molecule,
it is equal to the sum of kinetic energy, [translational (Et), rotational (Er), vibrational (Ev)], potential energy (Ep),
chemical bond energy (Ec), electronic energy (Ee), and nuclear energy (En). Thus
U = Et + Er + Ev + Ep + Ec + Ee + En
The internal energy of a system is a state function, i.e., it depends only on the state of the system and is
independent of the path or the manner in which the state is reached.
z U) : It may be mentioned that the absolute value of internal energy of a substance
Internal Energy Change (
cannot be determined. When a system undergoes a change of state, the change in internal energy, U is given
by:
U = U2 – U1
Where U1 and U2 are internal energies in the initial and final states respectively.
During a reaction taking place at constant temperature and at constant volume (i.e., in a closed vessel), the
internal energy change is equal to the amount of heat evolved or absorbed (qv) in it, i.e.
U = qv = Heat absorbed in a reaction at constant temperature and volume.
z Heat : The change in internal energy of a system can be brought about by the transfer of heat from the
surroundings to the system or vice-versa. This exchange of energy between the system and surroundings is
possible as a result of the temperature difference between them. This energy called heat is represented by q.

FIRST LAW OF THERMODYNAMICS

(i) Energy can neither be created nor be destroyed.
(ii) The total energy of universe is constant.
(iii) The mass and energy of an isolated system remains constant.
(iv) The total energy of a system and its surrounding must remain constant, although it may be changed from
one form to other.

Mathematically, U  q  W …(1)

Sign Convention :

W = +ve, work done on the system

W = –ve, work done by the system

q = +ve, heat is absorbed by the system

q = –ve, heat is evolved by the system.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
142 Thermodynamics NEET

Example 1 : A system gives out 20 J of heat and also does 40 J of work. What is the internal energy change?
Solution : U = q + w
= –20 J + (–40) J
= –60 J

PRESSURE-VOLUME WORK
It is the work done when the gas expands or contracts against the external pressure (usually atmospheric
pressure). To understand this, consider a cylinder containing one mole of an ideal gas fitted with a frictionless
and weightless piston. Pressure of the gas inside is p. Let the external pressure acting on the piston is pex.
If the external pressure pex is slightly greater than p(i.e., pex > p), piston moves downward till the pressure
inside the cylinder becomes equal to pex. During this compression, suppose the piston moves a very small
distance l.

Cross-section
pex area of
piston A
pex
Vi

Pressure, p
pex
Area = pex × V
V = Vf – Vi l

Vi, p Vf
Vf, p
Vf Vi
Fig. : (a) Fig. : (b) Fig. : (c)
Initial status Final status Work done on an ideal gas in a cylinder
when it is compressed by a constant
Pressure-Volume work external pressure, pex (in a single step)
is equal to the shaded area
It, w is the work done on the sytem by the movement of the piston, then
Work, w = force × displacement
= pex × A × l
= pex × (–V)
= –pex V
= –pex(Vf – Vi)
For irreversible isothermal process : W = –Pext.V

V2
For reversible isothermal process : W = –2.303nRT log
V1
FREE EXPANSION
Expansion of a gas in vacuum (where pex = 0) is called free expansion. No work is done during free expansion
of an ideal gas whether the process is reversible or irreversible.
wirrev = –pex V
= 0 × V = 0
Vf

and wrev =  pex dV  0

Vi

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Thermodynamics 143

Example 2 : Calculate the amount of work done when one mole of an ideal gas contained in a bulb of 2 L
capacity at 1 atm is allowed to enter in evacuated bulb of 10 L capacity and in another case it
is allowed to expand from 1 L to 5 L against a pressure of 1 atm.
Solution : Case I
w = –pex V
As expansion is taking place in the evacuated bulb, i.e., against vacuum, pex = 0. Hence w = 0.
Case II
V = V2 – V1
=5L–1L
=4L
p = 1 atm
 w = –pV
= –1 × 4
= –4 L-atm
1 L-atm = 101.3 J
= –4 × 101.3 J
= –405.2 J
The negative sign implies that work is done by the system.

ENTHALPY (H)
Many of the reactions are carried out at constant pressure. To measure heat changes at constant pressure
it is useful to define new state function called enthalpy (H).
The thermodynamic quantity U + PV is called the heat content or enthalpy of the system denoted by H.
H = U + PV

For a reaction : H  U  ngRT

Where, ng = number of moles of gaseous product – number of moles of gaseous reactant.

Note : H is a state function and is an extensive property.

Example 3 : If water vapour is assumed to be a perfect gas, molar enthalpy change for vaporization of 1 mol
of water at 1 bar and 100°C is 41 kJ mol–1. Calculate the internal energy, when 1 mol of water
is vapourised at one bar pressure and 100°C.
Solution : The change H2O(l)  H2O(g)
H = U + ngRT
or U = H – ngRT
= 41 kJ mol–1 – 1 × 8.314 J mol–1 K–1 × 373 K
= 41 kJ mol–1 – 3101 J mol–1
= 41 kJ mol–1 – 3.101 kJ mol–1
= 37.9 kJ mol–1

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
144 Thermodynamics NEET

HEAT CAPACITY
Heat capacity of a system is defined as the quantity of heat required to raise the temperature of the system
by one degree. Let a very small quantity of heat dq be given to a system and the temperature of the system
rises by dT.
dq
Thus, Heat capacity (C) =
dT
 Q = C T = mCsT = nCmT
Where C = Heat capacity (Cal °C–1)
Cs = Specific heat capacity (Cal gm–1°C–1)
Cm = Molar heat capacity (Cal mol–1°C–1)

Example 4 : Calculate the amount of heat required to raise the temperature of 13.5 g aluminium from 300 K
to 400 K, if specific heat of aluminium is 0.9 J (°C)–1 g–1.
Solution : q = C m T
= 0.9 × 13.5 × (T2 – T1)
= 0.9 × 13.5 × 100
= 1215 J

z Relation between Cp and Cv for an ideal gas

If the volume of the system is kept constant and heat is added to a system, then no work is done by the
system. Thus the heat absorbed by the system is used up completely to increase the internal energy of the
system. If the pressure of the system is kept constant and heat is supplied to the system, then some work
of expansion will be done by the system in addition to the increase in internal energy. Therefore, heat given
at constant pressure will be more than that of constant volume. And for one mole of gas and 1°C temperature
to increase that extra heat will be equal to the extra work done by the system and it is ‘R’. So the relation
between heat capacity at constant pressure and constant volume is
Cp – Cv = R

z Ratio of Molar Heat Capacity : It is represented by  and gives idea about atomicity of gas.

Cp

Cv

Cp
Value of Cp Value of C v = Atomicity
Cv
5R 3
R 1.66 Monoatomic
2 2
7 5
R R 1.40 Diatomic
2 2
4R 3R 1.33 Triatomic

z Kirchoff's equation :
U2  U1
Cv 
T2  T1
H2  H1
Cp 
T2  T1
Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Thermodynamics 145

EXERCISE

1. Which of the following is an example of open system?

(1) Human body (2) The earth

(3) Pond (4) All of these

2. Which of the following is not a state function?

(1) H (2) U

(3) q (4) G

3. Which of the following is intensive property?

(1) Temperature (2) Heat

(3) Mass (4) Volume

4. Closed system can exchange (with surroundings)

(1) Heat (2) Matter

(3) Heat and matter (4) Neither heat nor matter

5. System and surroundings together constitute

(1) The earth (2) The solar system

(3) Galaxy (4) Universe

6. E and H both are zero in

(1) Isobaric process (2) Adiabatic process

(3) Isochoric process (4) Cyclic process

7. The work done in an open vessel at 300 K, when 56 g iron reacts with dilute HCl is

(1) 600 cal (2) 300 cal

(3) 150 cal (4) 100 cal

8. Work done in reversible isothermal expansion is given by

V2 nR
(1) –2.303 RT log (2) (T2  T1)
V1 (   1)

V2
(3) 2.303 RT log V (4) None of these
1

9. When a gas undergoes adiabatic expansion, it gets cooled. This is because

(1) It is an exothermic process (2) It is an endothermic process

(3) Internal energy of the system decreases (4) Ideal gas becomes a real gas

10. Which of the following is correct expression for 1st law of thermodynamics under adiabatic condition?

(1) U = Q + W (2) U = Q – W

(3) Q = –W (4) U = W

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
146 Thermodynamics NEET

ENTHALPY CHANGE, rH OF A REACTION – REACTION ENTHALPY

The enthalpy change accompanying a reaction is called the reaction enthalpy. The enthalpy change of a
chemical reaction, is given by the symbol rH.

rH = (Sum of enthalpies of products) – (Sum of enthalpies of reactants)

S.No. Name of Enthalpy H Definition Example

Changed
1. Enthalpy of Combustion HCº Enthalpy change when (i) C(s) + O2(g)  CO2(g)
1 mole o f substan ce
is completely burned with (ii) CH4(g)+2O2(g)CO2(g)
required amount of oxygen + 2H2O()

2. Enthalpy of Formation Hºf 1

Enthalpy change when 1 (i) H2(g) + O2(g)  H2O()
mole of substance is formed 2
from its element in their (ii) S(s) + O2(g)  SO2(g)
most stable physical state

3. Enthalpy of atomisation Haº Enthalpy change when 1 Na(s)  Na(g)

mole of substance broken
up into its isolated atoms in
the gas phase

4. Enthalpy of neutralization HNº Enthalpy change (fix for

strong acid - strong base
neutralization i.e. –57.1 kJ or CH3COONa(aq) + H2O()
–13.7 kcal) when one mole (ii) H SO (aq) + 2NaOH(aq) 
of water is formed by the 2 4

neutralization of an acid by a Na2SO4(aq) + 2H2O()

base.

5. Enthalpy of fusion Hºf Enthalpy change when 1 H2O(s)  H2O()

mole of substance
u n de r g o es m e l t i n g i n
standard state.

6. Enthalpy of Vapourization HVap

º Enthalpy change when H2O()  H2O(g)
1 mole of liquid at constant
temperature of boiling point
and under pressure
undergoes vapourization.

7. Enthalpy of Sublimation º Enthalpy change when 1 CO2 (s)  CO2 (g)

HSub
mole of solid substance is
directly converted into
gaseous state at a constant
temperature and standard
pressure.

8. Enthalpy of Solution HºSol Enthalpy change when 1 KCl + aq  KCl (aq)

mole of sub stance is
dissolved in specif ied
quantity of solvent.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Thermodynamics 147
BOND ENERGY
The amount of energy required to break one mole of a particular type of a bond in the gaseous state is called
bond dissociation energy.
It is generally expressed in terms of kJ/mol. For example, 433 kJ of energy is required to dissociate the
H–H bonds in one mole of H2 molecules, therefore, the bond dissociation energy is 433 kJ mol–1.

Bond energy and bond dissociation energy : The bond dissociation energy depends upon the bond and
also the molecule in which the bond is present. When a molecule contains a number of bond of the same
kind, average value of the dissociation energies of a given bond is taken. The dissociation energy required to
dissociate each bond in a substance is called bond energy. In water, there are two O–H bonds. The bond
dissociation energies of two O–H bonds in water.

H2O(g)  H(g) + OH(g); H = 497.8 kJ

OH(g)  H(g) + O(g); H = 428.5 kJ
The bond energy is the average of these two bond dissociation energies, i.e.

Bond energy of O–H bond = (497.8 + 428.5)/2

= 463.15 kJ mol–1.

Note:

rH = (Hf)P – (Hf)R

rH = (BE)R – (BE)P

rH = (Hc)R – (Hc)P

Ionization enthalpy : However, when 1 g equivalent each of weak acid and strong base or a strong
acid and weak base or weak acid and weak base are allowed to react, the apparent value of heat
of neutralization is lesser than 13.7 kcal, e.g.,

HCl(aq)  NH4OH(aq) 
 NH4Cl(aq)  H2O; H  12.3 kcal ...(i)
Strong Weak

CH3COOH(aq)  NaOH(aq) 
 CH3COONa(aq)  H2O; H  13.4 kcal ...(ii)
Weak Strong

CH3COOH(aq)  NH4OH(aq) 
 CH3COONH4 (aq)  H2O; H  11.9 kcal ...(iii)

The lower values of apparent heat of neutralization are explained on the basis of the fact that a part of heat given
out during neutralization is utilized to bring in complete dissociation of weak component used in reaction.
CH3COOH(aq)  CH3COO–(aq) + H+ (aq); H = q
Thus, by eq. (ii)
CH3COO–(aq) + H+ (aq);
H = q + Na+ (aq) + OH– (aq)  CH3COO– (aq) + Na+ (aq) + H2O; H = –13.4 kcal
 H+ + OH–  H2O; H = –13.4 –q
 –13.4 – q = – 13.7 or q = + 0.3 kcal
Thus, heat of dissociation of acetic acid is 0.3 kcal/mol.

Lattice Enthalpy (Symbol : latticeHs)

The lattice enthalpy of an ionic compound is the enthalpy change which occurs when one mole of an ionic
compound dissociates into ions in the gaseous state.
Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
148 Thermodynamics NEET

Max Born and Fritz Haber put forward a method based on Hess’s law for the calculation of lattice enthalpy.
Since it is not possible to determine it directly, an indirect method is used by constructing an enthalpy
diagram called as Born-Haber Cycle. It is briefly described by taking the example of NaCl.
Heat of formation of NaCl is found to be –410 kJ mol–1 i.e.,
1
Na(s) + Cl (g)  NaCl(s); fHs = –410 kJ mol–1
2 2
Suppose that one mole of NaCl(s) is prepared through the following steps
(i) Na(s)  Na(g); subHs = 108.4 kJ mol–1
Sodium undergoes sublimation.
(ii) Na(g)  Na+(g) + e–(g); iHs = 496.0 kJ mol–1
Sodium atom undergoes ionization.

1
(iii) Cl (g)  Cl(g); aHs = 121 kJ mol–1
2 2
Chlorine molecule dissociates to produce Cl atom.
1
The reaction enthalpy will be half of the bond dissociation enthalpy. Hence,  Hs = 121 kJ mol–1
2 bond
(iv) Cl(g) + e–(g)  Cl–(g); egHs = –348.6 kJ mol–1
Chlorine atom gains an electron.
The electron gain enthalpy, egHs, is negative.
(v) The gaseous Na+ and Cl– ions combine to form 1 mole of crystalline sodium chloride.
Na+(g) + Cl–(g)  NaCl(s)
latticeH = U (lattice enthalpy or lattice energy)
Applying Hess’s law, we get
fHs = subHs + iHs + aHs + egHs + latticeHs
So,latticeHs = 411.2 + 108.4 + 121 + 496 – 348.6
= +788 kJ

Na(s) s –1
Na(g) s –1
Na+(g) + e–(g)
subH = +108.4 kJ mol iH = 496 kJ mol

Na+(g) + Cl–(g)
–
1 +e
Cl–(g)
s
Cl (g) Cl(g) latticeH = +788 kJ
2 2 1

s
H = +121 kJ mol
–1 s
egH = –348.6 kJ mol
–1

2 bond
Na+Cl–(s)
Now we use the value of lattice enthalpy to calculate enthalpy of solution from the expression
solHs = latticeHs + hydHs
For one mole of NaCl(s)
Lattice enthalpy = +788 kJ mol–1
and hydHs = –784 kJ mol–1
solHs = +788 kJ mol–1 – 784 kJ mol–1
= +4 kJ mol–1
Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Thermodynamics 149
The dissolution of NaCl(s) is accompanied by very little heat change.
Resonance enthalpy :

  
HRe sonance  Hf (experimental)  Hf (calculated)

HESS’S LAW OF CONSTANT HEAT SUMMATION

The enthalpy change accompanying a given chemical process is always the same, no matter whether it takes
place in one or more ways involving one or several steps Suppose a substance A is changed into D (i) directly
and (ii) indirectly.
(i) Direct change A  D + Q1 kJ
(ii) Indirect change A  B + q1 kJ
B  C + q2 kJ
C  D + q3 kJ
Thus total heat evolved = q1 + q2 + q3 = Q2 kJ (say). Then, according to Hess’s law, Q1 = Q2.
z Calorific values : The energy released due to oxidation of any fuel is measured in terms of calorific values.
It may be defined as the amount of heat given out when one gram of substance is burnt completely in oxygen.
This is expressed in kilocalories or kilo joules per gram of the fuel.

Example 5 : Calculate the enthalpy change where the standard heat of formation for gaseous NH3 is
–11.02 kcal / mol at 298 K. The reaction given is

1 3
N2(g) + H2(g)  NH3(g)
2 2
Solution : rHs = fHsProduct – fHsReactant

1  3 
= [fHs(NH3)] –  Hof (N2 )   Hof (H2 )
2  2 

1  3 
= [–11.02 kcal mol–1] –   (0)    (0)
2  2 
= –11.02 kcal mol–1 – 0
= –11.02 kcal mol–1
The standard enthalpies of formation of element in its reference state is taken as zero, therefore
fHs for N2 and H2 has been taken as zero.

Example 6 : If 150 kJ of energy is needed for muscular work to walk a distance of one km, then how much
of glucose one has to consume to walk a distance of 5 km. Provided only 30% energy is available
for muscular work. The enthalpy of combustion of glucose is 3000 kJ mol–1.
Solution : Energy consumed for walking a distance of 5 km = 150 × 5 kJ = 750 kJ
1 mole of glucose, C6H12O6 (180 g) gives theoretically energy = 3000 kJ
30
Actual energy available = × 3000 = 900 kJ
100
Thus, for 900 kJ of energy, glucose required = 180 g
180
 For 750 kJ of energy glucose required = × 750 = 150 g
900
Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
150 Thermodynamics NEET

Example 7 : Calculate amount of heat evolved when

(a) 500 cm3 of 0.5M hydrochloric acid is mixed with 200 cm3 of 0.8M NaOH solution.
(b) 250 cm3 of 0.4M H2SO4 is mixed with 500 cm3 of 0.2 M NaOH solution.
Solution : (a) 500 cm3 of 0.5 M HCl provides

500  0.5
=
1000

= 0.25 mol H+ ions

200 cm3 of 0.8 M NaOH solution provides

200  0.8
=
1000

= 0.16 mol (OH)– ions

So amount of heat produced = 57.1 × 0.16 = 9.136 kJ.
(b) 250 cm3 of 0.4 M H2SO4 provides

(250  0.4)
= ×2
1000

= 0.2 mol H+ ions

500 cm3 of 0.2 M NaOH provides

500  0.2
=
1000

= 0.1 mol OH– ions.

So amount of water formed = 0.1 mol
and amount of heat evolved = 57.1 × 0.1 = 5.71 kJ.

Example 8 : Determine the enthalpy change for the given reaction,

CH4(g) + Cl2(g)  CH3Cl(g) + HCl(g)
Bond energies are given as follows :
C – H = 412 kJ mol–1
C – Cl = 338 kJ mol–1
Cl – Cl = 242 kJ mol–1
H – Cl = 431 kJ mol–1
Solution : rHs = [Total energy used in dissociation of bonds] – [Total energy used in formation of bonds]
= [4HC – H + HCl – Cl] – [3HC – H + HC – Cl + HH – Cl]
= [4(412) + 1(242)] – [3(412) + 1(338) + 1(431)]
= [1648 + 242] – [1236 + 338 + 431]
= [1890] – [2005]
= –115 kJ mol–1

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Thermodynamics 151

Example 9 : When 1 mole of anhydrous CuSO4 is dissolved in excess of water, –66.4 kJ heat is evolved. When
one mole of CuSO4  5H2O is dissolved in water, the heat change is +11.7 kJ. Calculate enthalpy
of hydration of CuSO4 (anhydrous).
Solution : We have to calculate enthalpy of reaction for
CuSO4 + 5H2O  CuSO4 5H2O; H = ?
Given that
CuSO4 (anhyd.) + aq.  CuSO4 (aq.); H1 = –66.4 kJ ...(i)
CuSO4 5H2O + aq.  CuSO4 aq.; H2 = +11.7 kJ ...(ii)
On the basis of two equations
H = H1 – H2
= –66.4 kJ – (+11.7 kJ)
= –78.1 kJ
The enthalpy of hydration of CuSO4 = –78.1 kJ

SPONTANEOUS PROCESSES
The term spontaneity means the feasibility of a process. A process which can take place by itself under the
given set of conditions once it has been initiated if necessary, is said to be a spontaneous process. The
spontaneous processes are called feasible or probable processes. The actual rate of the process may vary
from very slow to extremely fast.
z Spontaneous processes where no initiation is needed
Sugar dissolves in water and forms a solution
Sugar + water  Solution of sugar in water
Water keep on evaporating from ponds, rivers, sea and open vessels
H2O (l)  H2O (g)
z Spontaneous processes where some initiation is required
Once a reaction between hydrogen and oxygen is initiated by passing electric spark through it, then it
occurs itself spontaneously even at room temperature.
Electric
2H2 (g) + O2(g) 
Spark
 2H O (l)
2

In domestic oven, coal (carbon) keeps on burning once initiated

ignition
C (s) + O2(g)   CO2(g)
Energy and Spontaneity :
z It is a well known fact that all physical and chemical processes are accompanied by energy changes. Let us
try to interpret various spontaneous processes on the basis of changes in energy. Think of spontaneous
process such as falling of a cricket ball from our hands to the ground ; flowing of water from higher level to
lower level. We know that the ball or water possesses more potential energy at higher level than at lower
level. This suggests that these spontaneous processes proceed by decrease of energy.
z Moreover, the state of lowest energy corresponds to the state of maximum stability. Therefore, the natural
tendency of all systems in this universe to go from instability to stability supports the fact that any process
which involves a decrease in energy should have an inherent tendency to take place.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
152 Thermodynamics NEET

Most of the spontaneous chemical reaction are found to be exothermic. For example :
C(s) + O2(g)  CO2 (g) ; H = –394 kJ mol–1
N2(g) + 3H2(g)  2NH3 (g) ; H = –92.4 kJ mol–1
1
H2(g) + O (g)  H2O (l) ; H = –285.7 kJ mol–1
2 2
z Thus, it may be concluded that all those processes which are accompanied by decrease of energy
(exothermic reactions, having negative value of H) occur spontaneously. In other words, the sign of
H may
H may be taken as a criterion for the spontaneity of a process and decrease of enthalpy i.e. –
be regarded as the driving force behind the spontaneous processes.
z But there are many reactions which occurs endothermically and are spontaneous for example evapouration
of H2O. Thus decrease in energy alone cannot define a spontaneous process.

Randomness-Disorder and Entropy

z The thermodynamic property Entropy is the measure of disorderness or randomness.
z Entropy is the state function and is extensive property.
z Increase in disorderness increases entropy, thus solid < liquid < gas.

q rev
z The entropy change, S is given by S  .
T
Where qrev is heat absorbed when the process is reversible and isothermal.
z Entropy change is given in unit of J/K or JK–1 or calK–1.

1
z Heat absorbed at low temperature it becomes more disordered than at higher temperature i.e., S  ,
T
if compared for two systems.
z The use of entropy change for determining direction of spontaneity of a process leads to second law
of thermodynamics.

SECOND LAW OF THERMODYNAMICS

z The second law of thermodynamics introduces the concept of entropy and its relation with spontaneous
processes.
z In an isolated system such as mixing of gases, there is no exchange of energy or matter between the
system and the surroundings. But due to increase in randomness, there is increase in entropy. Thus,
we can say that for a spontaneous process in an isolated system, the change in entropy is positive. i.e.,
S > 0.
z However, if the system is not isolated, we have to take into account the entropy changes of the system
and the surroundings. Then, the total entropy change (Stotal) will be equal to the sum of the change in
entropy of the system (Ssystem) and the change in entropy of the surroundings (Ssurroundings) i.e.,
Stotal = Ssystem + Ssurroundings
z For a spontaneous process, Stotal must be positive, i.e.,
Stotal = Ssystem + Ssurroundings > 0
z But system and surroundings constitute universe for thermodynamic point of view so that for spontaneous
change
Suniverse > 0
Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Thermodynamics 153
Statement of Second Law of Thermodynamics : This states that the entropy of the universe always
increases in the source of every spontaneous (natural) change.
Thus, combining the first and second law of thermodynamics, the combined statement becomes :
The energy of the universe is conserved whereas the entropy of the universe always increases in any natural
process.
Characteristics of Entropy :
The important characteristics of entropy are summed up below :
z Entropy is an extensive property. Its value depends upon the amount of the substance present in the
system.
z Entropy of a system is a state function. It depends upon the state variables (T, P, V, n). Thus, the change
in entropy is given as :
S = Sfinal state – Sinitial state
z In a reversible process, Suniverse = 0 and therefore, Ssystem = –Ssurroundings

dqrev w V
z For a reversible process,S = =  2.303nR log 2
T T V1
dqp(rev )
z At constant pressure, dS rev =
T
dH
dS =
T
H
 S =
T
This is normally for transition process.

Example 10 : The entropy change in the conversion of water to ice at 272 K for the system is –21.85 JK–1mol–1
and that of surrounding is +21.93 JK–1mol–1. State whether the process is spontaneous or not?
Solution : Stotal = Ssys + Ssurr
= –21.85 JK–1mol–1 + (+21.93 JK–1mol–1)
= 0.08 JK–1mol–1
∵ Sprocess > 0 at 272 K, the freezing of ice
H2O(l)  H2O(s) is a spontaneous process at 272 K.

ENTROPY CHANGE DURING PHASE TRANSFORMATIONS

The change of matter from one state (solid, liquid or gas) to another is called phase transition. Such changes
occur at definite temperatures such as melting point (solid to liquid), boiling point (liquid to vapours) etc., and
are accompanied by absorption or evolution of heat.
The entropy change for these may be calculated as :

Entropy changes during phase transformations

 fusH
(i) Entropy of fusion : fus S = (Tm = melting point of solid in K)
Tm

 vapH
(ii) Entropy of vaporisation : vap S = (Tb = boiling point of liquid in K)
Tb

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
154 Thermodynamics NEET

 sub H
(iii) Entropy of sublimation : sub S = (T = temperature in K at which sublimation occurs).
T
Similarly for a given chemical reaction
S = Sproduct – Sreactant
Ex. A2 + B2 2AB
Sreaction = [2 entropies of formation of AB] – [Entropies of formation of A2 and B2]
Driving force as the overall tendency for a process
We have learnt that the spontaneous processes occur because of the two tendencies :
(i) Tendency of a system to acquire a state of minimum energy.
(ii) Tendency of a system to acquire a state of maximum randomness.
The overall tendency for a process to take place by itself is called the driving force.

GIBB'S FREE ENERGY

z Free energy of a system is defined as the maximum amount of energy available to a system during a
process that can be converted into useful work.
z In the words, it is a measure of capacity of a system to do useful work. It is denoted by symbol G and
is given by
G = H – TS
where H is the enthalpy of the system, S is its entropy and T is the absolute temperature.
Now H = U + PV
G = U + PV – TS
z Free energy change. The change in free energy may be expressed as
G = U + (PV) – (TS)
z If the process is carried out at constant temperature and pressure, the terms (PV) and (TS) become
(PV) = PV and
(TS) = TS
G = U + PV – TS

or G  H  TS

z Free energy (G) :

When G is +ve, then the free energy of reactant is less than free energy of product (non spontaneous).
When G is –ve, then free energy of product is less than free energy of reactant (Spontaneous).
When G = 0, free energy of reactant is equal to free energy of product hence reaction exists at
equilibrium.
Spontaneity : When G < 0 the reaction will be spontaneous:
Spontaneity of the reaction

H S G = H – T S Reaction Spontaneity
– + – Spontaneous at all temperature
Spontaneous at low temperatures where H outweighs TS (T S <  H)
– – – or +
Nonspontaneous at high temperatures where TS outweighs H
+ – + Nonspontaneous at all temperatures
Spontaneous at high temperatures where TS outweighs H (T S >  H)
+ + – or +
Nonspontaneous at low temperatures where H outweighs T S

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Thermodynamics 155
Note :
z Relation between G and G°
G = G° + 2.303RT logQ (Q = concentration coefficient)
z G° and equilibrium constant
at equilibrium G = 0 and Q = K
 Gº = –RTlnK = –2.303RTlogK

z Gro  Gfo (products)  Gfo (reactants)

Example 11 : For the reaction

N2(g) + 3H2  2NH3(g)
H = –95.4 kJ and S = –198.3 JK–1
Calculate the temperature at which Gibbs energy change (G) is equal to zero. Predict the nature
of the reaction at this temperature and above it.
Solution : G = H – TS
G = 0
H – TS = 0
or H = TS

H
T
S
95.4  1000 J

198.3 JK 1
 481 K

At this temperature, the reaction would be in equilibrium and with the increase in temperature
the opposing factor TS would become more and hence, G would become positive and the
reaction would become non-spontaneous. The reaction would be spontaneous at the temperature
below 481 K.

THIRD LAW OF THERMODYNAMICS

At absolute zero the entropy of a perfectly crystalline substance is taken as zero (Nernst). The third law
helps to calculate the absolute entropies of pure substances at different temperatures. The entropy (S)
of the substance at different temperature T may be calculated by the measurement of heat capacity
changes. If S0 be the entropy of the substance at 0 K and S be its entropy at T K, then

T
Cp
S = S – S0 =  T
dT
0

Since S0 is 0 according to third law

T
Cp
S=  T
dT
0

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
156 Thermodynamics NEET

When the entropy of one mole of the substance is expressed in its standard state, it is called
standard entropy of the substance and is denoted as S0.

Sum of the standard  Sum of the standard 

S° =   – entropies of reactants  or
entropies of products   

S° = S° (products) – S° (reactants)

EXERCISE

11. The enthalpy of reaction is maximum in which of the following reaction?

(1) NaOH + HCl  NaCl + H2O

(2) NaOH + HF  NaF + H2O

(3) NaOH + HBr  NaBr + H2O

(4) All have same value

H = a
A P

12. H = b H = d
H = c
Q B

On the basis of Hess’s law of constant heat summation, choose the correct relation:

(1) b = a – d + c (2) c = a – b + d

(3) d = a + b + c (4) a – c = b + d

13. In which of the following H = U?

(1) N2(g) + 3H2(g)  2NH3(g) (2) C(s) + O2(g)  CO2(g)

(3) PCl5(g)  PCl3(g) + Cl2(g) (4) CaCO3(s)  CaO(s) + CO2(g)

14. Heat of combustion of CH4, C2H4 and C2H6 are –890, –1411 and –1560 kJ/mol respectively. Which has the lowest
calorific fuel value in kJ/g?

(1) CH4 (2) C2H4

(3) C2H6 (4) All of these

15. The heat of neutralisation of four acids P, Q, R, S are –13.7, –9.4, –11.2 and –12.4 kcal, respectively when
they are neutralised by a common base. The acidic character obeys the order

(1) P > Q > R > S (2) P > S > R > Q

(3) S > R > Q > P (4) S > Q > R > P

16. When H and TS both are negative, then for spontaneous process which option is true?

(1) H > TS (2) H < TS

(3) H = TS (4) H = U

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Thermodynamics 157
17. Which of the following relation is false?
(1) G = H – TS (2) S = q + T
(3) H = U + ngRT (4) H = U + PV
18. In a reversible process, the value of Ssys + Ssurr is
(1) > 0 (2) < 0
(3) = 0 (4) All of these
19. A boiled egg shows a/an ______ in entropy
(1) Increase (2) Decrease
(3) No change (4) None of these
20. The G in the process of melting of ice at –15°C is
(1) G < 0 (2) G > 0
(3) G = 0 (4) All of these

‰‰‰

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
 t
en
nm nment
ssigAssig
Assignment

Assignment
A

5. Consider the following

SECTION - A
H°sol = u kJ/mol + –
AB(s) A (aq) + B (aq)
NCERT Based MCQs
1. Consider the given reaction

ol
H

/m
kJ
° LE
PCl5(g)  PCl3(g) + Cl2(g)

v
=

=
w

n
kJ

tio
If the enthalpy change (i.e. H) for the given

ra
/m

yd
ol

°h
reaction is –x J at T K then the value of U is

H
+ –
A (g) + B (g)
[NCERT Pg. 167]
The correct relation between u, v & w is
(1) (–x + 8.314 T) J (2) –(x + 8.314 T) J
[NCERT Pg. 180]
(3) (x + 8.314 T) kJ (4) –(x + 8.314 T) kJ
(1) w = v + u (2) u = w + v
2. The heat of combustion of ethene from the given
(3) v = 2(u + w) (4) v = w + u
data is
6. For a reaction to be non-spontaneous
CH2 = CH2(g) + 3O2(g)  2CO2(g) + 2H2O(l)
[NCERT Pg. 185]
Bond Bond energy
(1) TS < H & both H & S are +ve
C=C x kJ/mol
(2) TS = 0
C–H y kJ/mol
(3) TS = H & both H & S are +ve
O=O z kJ/mol
(4) TS > H & both H & S are +ve
C=O a kJ/mol
7. Which of the following are state function?
O–H b kJ/mol [NCERT Pg. 177]
[NCERT Pg. 162]
(1) x – a + b + 4y – 3z
(a) q (b) q + w
(2) x + b – 3z + a + 4y
(c) H – TS (d) w
(3) x + 4y + 3z – 4(a + b)
(1) Only (a) (2) Only (b) & (c)
(4) a + b – (x + 4y + 3z)
(3) Only (d) (4) Only (c)
3. If energy required to dissociate 16 g of gaseous
8. Among the following, which is not a state function?
hydrogen into free atoms is 3488 kJ at 25°C then
the bond energy of H – H bond will be [NCERT Pg. 162]
[NCERT Pg. 177] (1) Volume (2) Temperature
(1) 384 kJ/mol (2) 436 kJ/mol (3) Pressure (4) Heat
(3) 384 J/mol (4) 436 J/mol 9. If an ideal gas expands isothermally from 50 L to
4. The correct relation between molar heat capacities 100 L against 2 atm external pressure, then values
CP and CV is [NCERT Pg. 169] of W, U and Q respectively will be

(1) CP + CV = R [NCERT Pg. 166]

(2) CP – CV = 2R (1) –100 L atm, zero and +100 L atm

(3) CP – CV = R (2) –50 L atm, zero and +50 L atm

(3) +100 L atm, zero and –100 L atm
R
(4) CP  CV  (4) +50 L atm, zero and –50 L atm
2
Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Thermodynamics 159
10. If 1 mol of an ideal gas at constant temperature 2. Consider the following statements :
changes its pressure from 5 atm to 2 atm and
a. q and w are state function
volume from 4 L to 10 L, then enthalpy change will
be [NCERT Pg. 167] b. q + w is a state function.
(1) 20 L-atm (2) 120 L-atm c. G is a state function
(3) Zero (4) 100 L-atm The correct statements is/are
11. If equal moles of following gases are taken at (1) a only
constant temperature and pressure then gas of (2) a & b only
highest entropy is [NCERT Pg. 182]
(3) b & c only
(1) He(g) (2) H2(g)
(4) All of these
(3) CO2(g) (4) PCl5(g)
3. The incorrect statement is
12. Correct expression of enthalpy of combustion is
[NCERT Pg. 176] (1) wrev > wirr in isothermal process

5 (2) U = wadiabatic
(1) C2H6 (g)  O  g  2CO  g  3H2O   
2 2 (3) q = 0 for cyclic process
1 (4) Work and heat appear only at the boundary of
(2) C(s)  O  g  CO  g
(diamond) 2 2 the system
4. Which of the following statement is correct?
1
(3) C(s)  O2  g  CO  g
graphite 2 (1) Entropy of egg decreases on boiling

S(s)  O2 g  SO2  g

(2) Entropy of rubber band decreases on
(4)
r hombic stretching
13. Select the pair of intensive properties (3) Entropy decreases during fusion of ice
[NCERT Pg. 168] (4) All of these
(1) Volume, entropy 5. Enthalpy of formation of NO2, SO2, CO2 and NH3
(2) Refractive index, density are 33.18, –296, –393 and –46 kJ/mol respectively.
The order of their increasing stabilities are
(3) Temperature, enthalpy
(1) NO2 < NH3 < SO2 < CO2
(4) Enthalpy, Gibbs free energy
(2) NH3 < SO2 < CO2 < NO2
14. If calorific fuel value of C2H6 is x kJ/g then the heat
of combustion of C2H6 is [NCERT Pg. 176] (3) NO2 < SO2 < CO2 < NH3
(1) x (2) 30 x (4) SO2 < CO2 < NH3 < NO2
(3) x/30 (4) 30/x 6. Enthalpy of solution of BaCl2 and BaCl2.2H2O are
–x and y kJ/mol respectively. The enthalpy of
15. Work done is always zero for [NCERT Pg. 166]
hydration of BaCl2 to BaCl2.2H2O is
(1) Isobaric process (2) Adiabatic process (1) (x – y) kJ (2) (y – x) kJ
(3) Isochoric process (4) Cyclic process (3) –(x + y) kJ (4) (x + y) kJ
7. Enthalpies of combustion of propane, butane and
SECTION - B pentane are –2220, –2878, –3537 kJ/mol
respectively. Order of calorific value (per gram) of
Objective Type Questions fuel will be
1. Correct option for an endothermic gaseous reaction (1) Propane > Butane > Pentane
A + B  3C will be (2) Butane > Pentane > Propane
(1) H > 0; S < 0 (2) H = 0; S > 0 (3) Propane < Butane < Pentane
(3) H > 0; S > 0 (4) S = 0; S < 0 (4) Pentane > Butane < Propane
Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
160 Thermodynamics NEET

8. For the process 13. The respective examples of extensive and intensive
properties are
X Y
(1) Enthalpy, entropy
(2) Entropy, enthalpy
A B
(3) Entropy, temperature
H for (A  X) = 50 kJ
(4) Temperature, entropy
H for (Y  X) = 20 kJ
14. According to first law of thermodynamics
H for (B  Y) = 30 kJ
(1) U = q – w (2) U = q + H
Then H for A  B will be
(3) U = q + w (4) U = q – H
(1) 100 kJ
15. Consider the following reactions
(2) –100 kJ
C (graphite) + O2(g)CO2(g) : H = – x1 cal
(3) Zero kJ
C (diamond) + O2(g) CO2(g) : H = – x2 cal
(4) –50 kJ
What is the heat of transition of graphite into
9. Which of the following methods for calculation of diamond?
heat of reaction is not correct?
(1) x1 + x2 (2) x2 – x1
(1) Hreaction =  Hf(products) –  Hf(reactants) (3) x1 – x2 (4) x1x2
(2) Hreaction =  B.E(reactants) –  B.E(products) 16. A system absorbs 10 kJ of heat and does 4 kJ of
work. The internal energy of the system
(3) Hreaction =  Hcomb(reactants) –  Hcomb(products)
(1) Decreases by 6 kJ
(4) Hreaction =  Hsolution (reactants) +  Hsolution (products) (2) Increases by 6 kJ
10. Enthalpy changes for two reactions are given by (3) Decreases by 14 kJ
the equation
(4) Increases by 14 kJ
3
2Cr(s)  O2 (g)  Cr2O3 (s), H  1130 kJ 17. For the given reactions, A 
 D, H = x. Steps
2 involved are
1
C(s)  O2 (g)  CO(g), H  110 kJ A 
 B H1 = x1
2
The enthalpy change for the reaction B 
 C H2 = ?
Cr2O3 + 3C  2Cr + 3CO will be
C 
 D H3 = x3
(1) –1460 kJ (2) –800 kJ
The value of H2 is
(3) +800 kJ (4) 1020 kJ
(1) H2 = x – (x1 + x3) (2) H2 = x + x1 + x3
11. If temperature of the system is T, then the process
will be spontaneous at all temperature only if (3) H2 = x1 – x3 – x (4) H2 = (x1 + x) – x3
(1) H < 0 and S > 0 18. Energy required to dissociate 4 g of gaseous H2
into free gaseous atoms is 872 kJ at 25°C. The
(2) H > 0 and S > 0 bond energy of H-H bond will be
(3) H < 0 and S < 0 (1) 8.72 kJ (2) 4.36 kJ
(4) H = 0 and S < 0 (3) 436 kJ (4) 43.6 kJ
12. Tea placed in thermoflask is an example of 19. The difference between H and U for the reaction
(1) Open system 2C6H6 (l) +15O2(g)  12 CO2(g) + 6H2O (l) at 25°C
(2) Close system in kJ is
(3) Isolated system (1) –7.43 kJ (2) +3.72 kJ

(4) It can't act as system (3) –3.72 kJ (4) +7.43 kJ

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Thermodynamics 161
20. An athlete takes 100 gm of glucose of energy 27. The specific heat of a gas is found to be
equivalent to 1560 kJ. How much amount of energy 0.075 calories at constant volume and its formula
is uptaken by 1 gm molecule of glucose? wt is 40. The atomicity of the gas would be
(1) 15.6 kJ (2) 2808 kJ (1) One (2) Two
(3) 1560 kJ (4) 28.08 kJ (3) Three (4) Four
21. The dissociation energy of CH4 (g) is 360 kcal mol–1 28. Under the same condition heats of formation of
and that of C2H6 (g) is 620 kcal mol–1. The C – C water & CO 2 are –285 and –394 kJ mol —1
bond energy is respectively. The heat of combustion of methane is
–890 kJ mol—1. The heat of formation of methane
(1) 260 kcal mol–1 (2) 180 kcal mol–1
(in kJ mol–1) is
(3) 130 kcal mol–1 (4) 80 kcal mol–1
(1) –964 (2) –890
22. The enthalpy of formation of ammonia is
–46.0 kJ mol–1. The enthalpy for the reaction (3) –222 (4) –74

2N2(g) + 6H2(g)  4NH3(g) is 29. Specific heat at constant volume (Cv) of a mono
atomic gas is
(1) –46 kJ (2) 46 kJ
3 5
(3) 184 kJ (4) –184 kJ (1) R (2) R
2 2
23. The volume of a gas expands by 0.25m3 at a
constant pressure of 103N m-2. The work done is 7 4
equal to (3) R (4) R
5 3
(1) 2.5 erg (2) 250 J 30. At 298 K the standard enthalpies of formation of
(3) 250 eV (4) 250 cal H 2 O(l) and H 2 O 2 (l) are –286.0 kJ mol –1 and
–188.0 kJ mol–1. The enthalpy change for reaction
24. Using bond energy data, calculate heat of formation
of isoprene 2H2O2(l)  2H2O(l) + O2(g) will be

5C(s) + 4H2(g) H2C==C—CH ==CH2 (1) – 948 kJ/mol

CH 3 (2) – 196 kJ mol–1

Given : BE for C–H, H–H, C–C, C = C and C(s)  (3) + 196 kJ mol–1
C(g) respectively as 98.8 kcal, 104 kcal, 83 kcal, (4) + 948 kJ mol–1
147 kcal, 171 kcal
31. The standard entropies of N2 (g), H 2 (g) and
(1) – 20.6 kcal
NH3 (g) are 191.5, 130.5, 192.6 JK–1 mol–1. The
(2) 20.6 kcal value of Sº of formation of ammonia is
(3) 40 kcal (1) –98.9 JK–1 mol–1 (2) Zero
(4) 50 kcal (3) +129.4 JK–1 mol–1 (4) –29.4 JK–1 mol–1
25. When 1 g of anhydrous oxalic acid is burnt at 32. For the melting of NaCl heat required is
25°C, the amount of heat liberated is 2.835 kJ. H 7.26 kcalmol–1 and S increases by 6.73 cal mol–1
combustion is K–1. The melting point of the salt is
(1) 255.15 kJ (2) 445.65 kJ (1) 805.75°C (2) 500 K
(3) 295.24 kJ (4) 155.16 kJ (3) 1.77 K (4) 1.77°C
26. The most exothermic neutralisation reaction would 33. The standard free energy change G° is related to
be between K (equilibrium constant) as
(1) NH4OH and HCl (1) G° = –2.303 RT logK
(2) CH3COOH and NaOH (2) G° = 2.303 RT logK
(3) NH4OH and H2SO4 (3) G° = RT logK
(4) NaOH and HCl (4) G° = –RT logK
Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
162 Thermodynamics NEET

34. It is impossible for a reaction to take place if 2. In which case change in entropy is negative?
[NEET-2019]
(1) H is +ve and S is +ve
(1) Evaporation of water
(2) H is –ve and S is +ve
(2) Expansion of a gas at constant temperature
(3) H is +ve and S is –ve
(3) Sublimation of solid to gas
(4) H is –ve and S is –ve
(4) 2H(g)  H2(g)
35. The least random state of H2O is
3. The bond dissociation energies of X2, Y2 and XY are
(1) Ice
in the ratio of 1 : 0.5 : 1. H for the formation of XY is
(2) Liquid water –200 kJ mol–1. The bond dissociation energy of X2
(3) Steam will be [NEET-2018]

(4) Randomness is same in all states (1) 200 kJ mol–1 (2) 100 kJ mol–1

36. Entropy of vaporisation of water at 100°C, if molar (3) 400 kJ mol–1 (4) 800 kJ mol–1
heat of vaporisation is 9710 cal mol—1 will be 4. A gas is allowed to expand in a well insulated
(1) 20 cal mol–1 K–1 container against a constant external pressure of 2.5
atm from an initial volume of 2.50 L to a final volume
(2) 26 cal mol–1 K–1 of 4.50 L. The change in internal energy U of the
(3) 24 cal mol–1 K–1 gas in joules will be [NEET-2017]
(4) 28 cal mol–1 K–1 (1) 1136.25 J (2) –500 J
37. The heat of neutralisation of HCl by NaOH is (3) –505 J (4) +505 J
–55.9 kJ/mole. If the heat of neutralization of HCN by 5. For a given reaction, H = 35.5 kJ mol –1 and
NaOH is –12.1 kJ/mole, the energy of dissociation S = 83.6 JK–1 mol–1. The reaction is spontaneous
of HCN is at : (Assume that H and S do not vary with
(1) –43.8 kJ (2) 43.8 kJ temperature) [NEET-2017]
(3) 68 kJ (4) –68 kJ (1) T < 425 K (2) T > 425 K
38. Molar heat capacity of water in equilibrium with ice (3) All temperatures (4) T > 298 K
at constant pressure is 6. For a sample of perfect gas when its pressure is
(1) Zero (2) Infinity changed isothermally from pi to pf, the entropy change
is given by [NEET (Phase-2) 2016]
(3) 40.45 kJ K–1 mole–1 (4) 75.48 J K–1 mole–1
39. Identify intensive quantity from the following p  p 
(1) S  nRln  f  (2) S  nRln  i 
(1) Enthalpy (2) Temperature  pi   pf 
(3) Volume (4) Heat capacity
p  p 
(3) S  nRT ln  f  (4) S  RTln  i 
 pi   pf 
SECTION - C
7. The correct thermodynamic conditions for the
Previous Years Questions spontaneous reaction at all temperatures is
1. Under isothermal condition, a gas at 300 K expands [NEET-2016]
from 0.1 L to 0.25 L against a constant external (1) H < 0 and S < 0 (2) H < 0 and S = 0
pressure of 2 bar. The work done by the gas is
(3) H > 0 and S < 0 (4) H < 0 and S > 0
[NEET-2019]
(Given that 1 L bar = 100 J) 8. The heat of combustion of carbon to CO 2 is
–393.5 kJ/mol. The heat released upon formation of
(1) –30 J 35.2 g of CO2 from carbon and oxygen gas is
(2) 5 kJ [Re-AIPMT-2015]
(3) 25 J (1) –630 kJ (2) –3.15 kJ
(4) 30 J (3) –315 kJ (4) +315 kJ
Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Thermodynamics 163
9. For the reaction, X2O4(l)  2XO2(g) 15. If the enthalpy change for the transition of liquid
U = 2.1 k cal, S = 20 cal K–1 at 300 K water to steam is 30 kJ mol–1 at 27°C, the entropy
change for the process would be
Hence, G is [AIPMT-2014]
[AIPMT (Prelims)-2011]
(1) 2.7 kcal (2) –2.7 kcal
(1) 100 J mol –1 K–1
(3) 9.3 kcal (4) –9.3 kcal
(2) 10 J mol –1 K–1
10. In which of the following reactions, standard reaction
(3) 1.0 J mol –1 K–1
entropy change (S°) is positive and standard Gibb's
energy change (G°) decreases sharply with (4) 0.1 J mol –1 K–1
increasing temperature? [AIPMT (Prelims)-2012] 16. Enthalpy change for the reaction, 4 H(g) 2H2 (g)
1 is –869.6 kJ. The dissociation energy of H – H
(1) Mg(s)+ O (g)MgO(s) bond is [AIPMT (Prelims)-2011]
2 2
1 1 1 (1) + 217.4 kJ
(2) C graphite + O2(g) CO2(g)
2 2 2 (2) – 434.8 kJ
1 (3) – 869.6 kJ
(3) C graphite + O (g)CO(g)
2 2 (4) + 434.8 kJ
1 17. Consider the following process
(4) CO(g)+ O (g)CO2(g)
2 2 H(kJ/mol)
11. Standard enthalpy of vapourisation vapH(0) for
1
water at 100C is 40.66 kJmol –1 .The internal A B + 150
energy of vapourisation of water at 100C (in 2
kJmol–1) is [AIPMT (Prelims)-2012] 3B  2C + D – 125

(1) +43.76 (2) +40.66 E + A  2D + 350

(3) +37.56 (4) –43.76 For; B + D  E + 2C, H will be

12. The enthalpy of fusion of water is 1.435 kcal/mol. [AIPMT (Mains)-2011]

The molar entropy change for the melting of ice at (1) –325 kJ/mol (2) 325 kJ/mol
0C is [AIPMT (Prelims)-2012] (3) 525 kJ/mol (4) –175 kJ/mol
(1) 5.260 cal/(mol K) 18. Standard entropies of X2, Y2 and XY3 are 60, 40
(2) 0.526 cal/(mol K) and 50 JK–1 mol–1 respectively. For the reaction

(3) 10.52 cal/(mol K) 1 3

X2  Y2  XY 3 ; H = –30kJ to be at
2 2
(4) 21.04 cal/(mol K)
equilibrium, the temperature should be
13. Equal volumes of two monoatomic gases, A and B,
[AIPMT (Prelims)-2010]
at same temperature and pressure are mixed. The
ratio of specific heats (Cp/Cv) of the mixture will be (1) 750 K (2) 1000 K
[AIPMT (Mains)-2012] (3) 1250 K (4) 500 K

(1) 0.83 (2) 1.50 19. A monatomic gas at pressure P1 and volume V1 is

(3) 3.3 (4) 1.67 1

compressed adiabatically to th its original volume.
8
14. Which of the following is correct option for free
expansion of an ideal gas under adiabatic What is the final presssure of the gas ?
condition? [AIPMT (Prelims)-2011] [AIPMT (Mains)-2010]
(1) q = 0, T < 0, w  0 (1) 64 P1
(2) q = 0, T  0, w = 0 (2) P1
(3) q  0, T = 0, w = 0 (3) 16 P1
(4) q = 0, T  0, w = 0 (4) 32 P1

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
164 Thermodynamics NEET

20. Match List-I (Equations) with List-II (Type of 25. From the following bond energies
process) and select the correct option H–H bond energy : 431.37 kJ mol–1
List-I List-II C = C bond energy : 606.10 kJ mol–1
(Equations) (Type of process)
C – C bond energy : 336.49 kJ mol–1
a. Kp > Q (i) Non-spontaneous
C – H bond energy : 410.50 kJ mol–1
b. G< RT ln Q (ii) Equilibrium
Enthalpy for the reaction,
c. Kp = Q (iii) Spontaneous and
H H H H
endothermic
C=C+H–H H–C–C–H
H H H H H
d. T > (iv) Spontaneous
S will be [AIPMT (Prelims)-2009]
[AIPMT (Mains)-2010] (1) –243.6 kJ mol–1 (2) –120.0 kJ mol–1
(1) a(i), b(ii), c(iii), d(iv) (2) a(iii), b(iv), c(ii), d(i) (3) 553.0 kJ mol–1 (4) 1523.6 kJ mol–1
(3) a(iv), b(i), c(ii), d(iii) (4) a(ii), b(i), c(iv), d(iii) 26. Bond dissociaton enthalpy of H2, Cl2 and HCl are
21. Three moles of an ideal gas expanded 434, 242 and 431 kJ mol–1 respectively. Enthalpy
spontaneously into vacuum. The work done will be of formation of HCl is [AIPMT (Prelims)-2008]
(1) 245 kJ mol–1 (2) 93 kJ mol–1
[AIPMT (Mains)-2010]
(3) –245 kJ mol–1 (4) –93 kJ mol–1
(1) Infinite (2) 3 joules
27. For the gas phase reaction,
(3) 9 joules (4) Zero

PCl 5(g)  
 PCl 3(g) + Cl 2(g), which of the
22. For vaporization of water at 1 atmospheric following conditions is correct ?
pressure, the values of H and S are 40.63 kJ
mol –1 and 108.8 JK –1 mol –1 respectively. The [AIPMT (Prelims)-2008]
temperature when Gibbs energy change (G) for (1) H > 0 and S < 0 (2) H = 0 and S < 0
this transformation will be zero, is (3) H > 0 and S > 0 (4) H < 0 and S < 0
[AIPMT (Mains)-2010] 28. Which of the following are not state functions?
(1) 273.4 K (2) 393.4 K (I) q + w (II) q
(3) 373.4 K (4) 293.4 K (III) w (IV) H–TS
23. The following two reactions are known : [AIPMT (Prelims)-2008]
Fe2O3(s) + 3CO(g)  2Fe(s) + 3CO2(g) ; (1) (II) and (III) (2) (I) and (IV)

H = –26.8 kJ (3) (II), (III) and (IV) (4) (I), (II) and (III)
29. Consider the following reactions :
FeO(s) + CO(g)  Fe(s) + CO2(g);H = –16.5 kJ
(i) H+(aq) + OH– (aq) = H2O(l); H = –X1 kJ mol–1
The value of H for the following reaction
1
Fe2O3(s) + CO(g)  2FeO(s) + CO2(g) is (ii) H2(g) + O (g) = H2O(l); H = –X2 kJ mol–1
2 2
[AIPMT (Mains)-2010]
(iii) CO2(g) + H2(g) = CO(g) + H2O(l);
(1) +10.3 kJ (2) –43.3 kJ H = –X3 kJ mol–1
(3) –10.3 kJ (4) +6.2 kJ
5
(iv) C2H2(g) + O (g) = 2CO(g) + H2O(l);
24. The values of H and S for the reaction, 2 2
C(graphite) + CO2(g)  2CO(g) H = +X4 kJ mol–1

are 170 kJ and 170 JK–1 respectively. This reaction Enthalpy of formation of H2O(l) is
will be spontaneous at [AIPMT (Prelims)-2009] [AIPMT (Prelims)-2007]
(1) 910 K (2) 1110 K (1) +X1 kJ mol–1 (2) +X2 kJ mol–1
(3) 510 K (4) 710 K (3) +X3 kJ mol–1 (4) +X4 kJ mol–1
Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Thermodynamics 165
30. Given that bond energies of H–H and Cl – Cl are 35. A reaction occurs spontaneously if
430 kJ/mol and 240 kJ/mol respectively and fH of [AIPMT (Prelims)-2005]
HCl is –90 kJ/mol. Bond enthalpy of HCl is
(1) TS < H and both H and S are +ve
[AIPMT (Prelims)-2007]
(2) TS > H and both H and S are +ve
(1) 245 kJ mol–1
(3) TS = H and both H and S are +ve
(2) 2909 kJ mol–1
(4) TS > H and H is +ve and S is –ve
(3) 380 kJ mol–1
36. Which of the following pairs of a chemical reaction
(4) 425 kJ mol–1 is certain to result in a spontaneous reaction ?
31. Identify the correct statement for change of Gibbs [AIPMT (Prelims)-2005]
energy for a system (G system ) at constant
(1) Exothermic and decreasing disorder
temperature and pressure
(2) Endothermic and increasing disorder
[AIPMT (Prelims)-2006]
(3) Exothermic and increasing disorder
(1) If Gsystem > 0, the process is spontaneous
(4) Endothermic and decreasing disorder
(2) If G system = 0, the system has attained
equilibrium 37. The absolute enthalpy of neutralisation of the reaction
(3) If Gsystem = 0, the system is still moving in MgO(s) + 2HCl(aq)  MgCl2(aq) + H2O(l)
a particular direction will be [AIPMT (Prelims)-2005]
(4) If G system < 0, the process is not (1) Less than – 57.33 kJ mol–1
spontaneous
(2) –57.33 kJ mol–1
32. Assume each reaction is carried out in an open
container. For which reaction will H = E? (3) Greater than –57.33 kJ mol–1
(4) 57.33 kJ mol–1
[AIPMT (Prelims)-2006]
(1) H2(g) + Br2(g)  2HBr(g) Questions asked Prior to Medical Ent. Exams. 2005
(2) C(s) + 2H2O(g)  2H2(g) + CO2(g) 38. Which reaction, with the following values of H,
S, at 400 K is spontaneous and endothermic?
(3) PCl5(g) PCl3(g) + Cl2(g)
(1) H = –48 kJ; S = + 135 J/K
(4) 2CO(g) + O2(g) 2CO2(g)
(2) H = –48 kJ; S = – 135 J/K
33. The enthalpy and entropy change for the reaction
(3) H = +48 kJ; S = + 135 J/K
Br2(l) + Cl2(g)  2BrCl(g)
(4) H = +48 kJ; S = – 135 J/K
are 30 kJ mol–1 and 105 JK–1 mol–1 respectively.
The temperature at which the reaction will be in 39. Three thermochemical equations are given below:
equilibrium is [AIPMT (Prelims)-2006] (i) C(graphite) + O2(g)  CO2(g); rH° = x kJ mol–1
(1) 285.7 K (2) 273 K
1
(ii) C(graphite) + O (g)  CO(g); rH° = y kJ mol–1
(3) 450 K (4) 300 K 2 2
34. The enthalpy of combustion of H2, cyclohexene
(C6H10) and cyclohexane (C6H12) are – 241, –3800 1
(iii) CO (g) + O (g)  CO2(g); rH° = z kJ mol–1
and –3920 kJ per mol respectively. Heat of 2 2
hydrogenation of cyclohexene is
Based on the above equations, find out which of
[AIPMT (Prelims)-2006] the relationship given below is correct:
(1) – 121 kJ per mol (1) x = y – z
(2) + 121 kJ per mol (2) z = x + y
(3) + 242 kJ per mol (3) x = y + z
(4) – 242 kJ per mol (4) y = 2z – x

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
166 Thermodynamics NEET

40. Following reaction occurring in an automobile 46. One mole of an ideal gas at 300 K is expanded
2C8H18(g) + 25O2(g)  16CO2(g) + 18H2O (g). The isothermally from an initial volume of 1 litre to 10 litres.
sign of H, S and G would be The E for this process is (R = 2 cal. Mol–1K–1)
(1) –, +, + (2) +, +, – (1) 1381.1 cal (2) Zero
(3) +, –, + (4) –, +, – (3) 163.7 cal (4) 9 L atm
41. When 5 litres of a gas mixture of methane and 47. In the reaction : S + 3/2 O2  SO3 + 2x kcal and
propane is perfectly combusted at 0°C and SO 2 + 1/2 O 2  SO 3 + y kcal, the heat of
1 atmosphere, 16 litre of oxygen at the same formation of SO2 is
temperature and pressure is consumed. The
(1) (2x + y) (2) (x – y)
amount of heat released from this combustion in kJ
(H comb (CH 4) = 890 kJ mol –1, H comb (C 3H8) (3) (x + y) (4) (y – 2x)
= 2220 kJ mol–1) is 48. At 27°C latent heat of fusion of a compound is
(1) 32 (2) 38 2930 J/mol. Entropy change is
(3) 317 (4) 477 (1) 9.77 J/mol·K (2) 10.77 J/mol·K
42. If enthalpies of formation for C2H4(g), CO2(g) and (3) 9.07 J/mol·K (4) 0.977 J/mol·K
H2O(l) at 25°C and 1 atm pressure are 52, –394
49. For the reaction
and –286 kJ/mol respectively, then enthalpy of
combustion of C2H4(g) will be C2H5OH(l) + 3O2(g)  2CO2(g) + 3H2O(l), which
one is true?
(1) + 14.2 kJ/mol
(1) H = E – RT (2) H = E + RT
(2) + 1412 kJ/mol
(3) H = E + 2RT (4) H = E – 2RT
(3) – 141.2 kJ/mol
(4) – 1412 kJ/mol 50. Change in enthalpy for reaction, 2H2O2 (l )  2H2O (l )
+O2 (g) if heat of formation of H2O2(l ) and H2O(l ) are
43. For a reaction to occur spontaneously –188 and –286 kJ/mol respectively, is
(1) H must be negative
(1) –196 kJ/mol
(2) S must be negative
(2) +196 kJ/mol
(3) (H – TS) must be negative
(3) +948 kJ/mol
(4) (H + TS) must be negative
(4) –948 kJ/mol
44. Given that C + O2  CO2, H° = –x kJ
51. When 1 mol of gas is heated at constant volume
2CO + O2  2CO2, H° = –y kJ temperature is raised from 298 to 308 K. Heat
What is heat of formation of CO? supplied to the gas is 500 J. Then which
statement is correct?
y  2x
(1) (2) 2x – y (1) q = U = –500 J, w = 0
2
(2) q = U = 500 J, w = 0
2x  y
(3) y – 2x (4) (3) q = w = 500 J, U = 0
2
45. Identify the correct statement regarding entropy (4) U = 0, q = w = –500 J

(1) At absolute zero of temperature, the entropy of 1

all crystalline substances is taken to be zero 52. Enthalpy of CH4 + O  CH3OH is negative. If
2 2
(2) At absolute zero of temperature, the entropy enthalpy of combustion of CH4 and CH3OH are x
of a perfectly crystalline substance is +ve and y respectively. Then which relation is correct?
(3) At absolute zero of temperature, entropy of a (1) x > y
perfectly crystalline substance is taken to be
(2) x < y
zero
(3) x = y
(4) At 0°C, the entropy of a perfectly crystalline
substance is taken to be zero (4) x  y

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Thermodynamics 167
53. Unit of entropy is 61. Considering entropy (S) as a thermodynamic
parameter, the criterion for the spontaneity of any
(1) JK–1 mol–1 (2) J mol–1
process is
(3) J–1 K–1 mol–1 (4) JK mol–1
(1) Ssystem + Ssurroundings > 0
54. In a closed insulated container a liquid is stirred
(2) Ssystem – Ssurroundings > 0
with a paddle to increase the temperature which of
the following is true? (3) Ssystem > 0 only
(1) E = W  0, q = 0 (2) E = W = q  0 (4) Ssurroundings > 0 only
(3) E = 0, W = q  0 (4) W = 0, E = q  0 62. The work done during the expansion of a gas from
a volume of 4 dm3 to 6 dm3 against a constant
55. 2 mole of ideal gas at 27°C temperature is
external pressure of 3 atm is (1 L atm = 101.32 J)
expanded reversibly from 2 lit. to 20 lit. Find
entropy change (R = 2 cal/mol K) (1) –6 J (2) –608 J
(1) 92.1 (2) 0 (3) +304 J (4) –304 J
(3) 4 (4) 9.2 63. The enthalpy of hydrogenation of cyclohexene is
–119.5 kJ mol–1. If resonance energy of benzene is
56. Heat of combustion for C(s), H2(g) and CH4(g) are
–150.4 kJ mol–1, its enthalpy of hydrogenation
–94, –68 and –213 kcal/mol, then H for
would be
C(s) + 2H2(g)  CH4(g) is
(1) –358.5 kJ mol–1 (2) –508.9 kJ mol–1
(1) –17 kcal (2) –111 kcal
(3) –208.1 kJ mol–1 (4) –269.9 kJ mol–1
(3) –170 kcal (4) –85 kcal
64. 2Zn + O2  2ZnO; G° = –616 J
57. For the reaction
2Zn + S2  2ZnS; G° = –293 J
C3H8(g) + 5O2(g)  3CO2(g) + 4H2O(l)
S2 + 2O2  2SO2; G° = –408 J
at constant temperature, H – E is
G° for the following reaction
(1) + RT (2) – 3RT
2ZnS + 3O2  2ZnO + 2SO2 is
(3) + 3RT (4) – RT
(1) –1462 J (2) –1317 J
58. What is the entropy change (in JK–1 mol–1) when
one mole of ice is converted into water at 0°C? (3) –501 J (4) –731 J
(The enthalpy change for the conversion of ice to
liquid water is 6.0 kJ mol–1 at 0°C) SECTION - D
(1) 20.13 (2) 2.013 NEET Booster Questions
(3) 2.198 (4) 21.98 1. U = 0 always when in a process

59. For which one of the following equations is Hreact (1) T  0 (2) T = 0
(3) V = 0
equal to H for the product?
(4) W = 0
f
2. The value of H and U will be same for
(1) N2(g) + O3(g)  N2O3(g)
(1) N2(g) + 3H2(g)  2NH3(g)
(2) CH4(g) + 2Cl2(g)  CH2Cl2(l) + 2HCl(g)
(2) H2(g) + I2(g)  2HI(g)
(3) Xe(g) + 2F2(g)  XeF4(g)
(3) CaCO3(s)  CaO(s) + CO2(g)
(4) 2CO(g) + O2(g)  2CO2(g)
1
60. Standard enthalpy and standard entropy changes (4) SO2 (g) + O2 (g)  SO3 (g)
for the oxidation of ammonia at 298 K are 2
–382.64 kJ mol–1 and –145.6 J mol–1, respectively. 3. Expansion of ideal gas takes place from 1 L to
Standard Gibb’s energy change for the same 10 L in vacuum isothermally at 300 K. Which of
reaction at 298 K is the following is correct?
(1) –221.1 kJ mol–1 (2) –339.3 kJ mol–1 (1) H = 0 (2) q = 0
(3) –439.3 kJ mol–1 (4) –523.2 kJ mol–1 (3) w = 0 (4) All of these
Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
168 Thermodynamics NEET

4. If HC–H = 300 kJ/mol, Hatm of C(s) = 500 kJ and 12. In which of the following both species have zero
HH–H = 200 kJ/mol then the fH(CH4) will be standard enthalpy of formation?
(1) –500 kJ (2) –300 kJ (1) H2(g), H (aq) (2) D2(g), D2O(l)
(3) –200 kJ (4) –100 kJ (3) P(s) (white), I2(g) (4) O2(g), O3(g)
5. The difference between the value of Cp of H2 and 13. For the combustion of C 3 H 8 (g) at constant
Cv of He will be temperature H – U is

(1) R (2) 2 R (1) – RT (2) + RT

(3) – 3RT (4) + 3RT
(3) 3 R (4) 4 R
14. Incorrect among the following is
6. Which of the following can be correct?
(1) H  U = nRT 1
(1) C(s)  O2 (g)  CO(g) Hro  Hof CO
2
(2) CP – CV = R
(2) C(s)  O2 (g)  CO2 (g) Hro  Hof CO2  Hco C(s)
 dH   dU 
(3)  dT    dT   R
 P  V 1
(3) CO(g)  O2 (g)  CO2 (g) Hro  Hof CO2  Hoc CO(g)
2
(4) All of these
(4) Both (1) & (2)
7. Zeroth law of thermodynamics states that
15. 100 ml of 3 mol H2SO4 reacts with 100 ml of 3
(1) Heat is path function mol NaOH. Enthalpy of neutralisation of reaction will
(2) Energy is conserved be
(3) Heat transfer takes place till thermal equilibrium (1) – 57.1 kJ/mol (2) –2 × 57.1 kJ
is achieved (3) – 0.3 × 57.1 kJ (4) – 3 × 57.1 kJ
(4) Entropy is conserved 16. One mole of a perfect gas expands isothermally to
8. In which of the following maximum amount of heat ten times its original volume. The change in
is released if one mole of each reactant is taken? entropy at 298 K will be
(1) H2SO4 + NaOH (2) HCl + NaOH (1) 0.1 × 298 × R (2) 2.303 × 298 × R
(3) HF + NaOH (4) CH3COOH + KOH (3) 2.303 R (4) 0.1 R
9. Consider the following statements 17. Strongest bond among the following is
(a) q is state function in isochoric process
(1) O—H (2) C—H
(b) w is state function in isobaric process
(3) C—C (4) N N
(c) Work done by the system will be zero in
18. Correct for an endothermic gaseous reaction
adiabatic free expansion
A + B  3C will be
Correct among the following is/are
(1) (a) only (2) (b) only (1) H > 0; S < 0 (2) H = 0; S > 0

(3) (b) & (c) (4) (a), (b) & (c) (3) H > 0; S > 0 (4) S = 0; S < 0
10. When an ideal gas undergoing expansion in 19. Heat of formation of benzene; assuming no
vacuum shows resonance. Given that
(1) U = 0 (2) w = 0 BE (C–C) = 83 k cal
(3) q = 0 (4) All of these BE (C=C) = 140 k cal
11. Which of the following correctly represents the BE (C–H) = 99 kcal
standard enthalpy of formation of CCl4? Heat of atomisation of C = 170.9 kcal
(1) C(graphite) + 2Cl2(l)  CCl4(g) Heat of atomisation of H = 104.2 kcal
(2) C(graphite) + 4Cl(g)  CCl4(g) will be
(3) C(diamond) + 2Cl2(g)  CCl4(g) (1) 39 kcal (2) 75 kcal
(4) C(graphite) + 2Cl2(g)  CCl4(g) (3) 1263 kcal (4) 421 kcal
Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Thermodynamics 169
20. At 0°C, ice and water are in equilibrium and (1) Wisothermal > Wadiabatic
H fusion of ice = 6 kJ/mol. Correct among the
(2) Ratio of slope of adiabatic to isothermal will be r
following is/are
(1) G = S = 0 (3) T1 = T2 = T3
(2) Ssurr = – 21.98 JK–1 (4) Uisothermal > Uadiabatic
(3) G = 0 26. When an ideal gas is compressed adiabatically
(4) Both (2) & (3) and reversibly, the final temperature is

21. Volume of gas is doubled from its original volume. (1) Higher than the initial temperature
The specific heat will be (2) Lower than the initial temperature
(1) Reduced to half (2) Doubled (3) The same as the initial temperature
(3) Remain same (4) Increased four times (4) Dependent on the rate of compression
22. 5.6 dm3 of gas at STP requires 52.25 J of heat to 27. A closed flask contains a substance in all its three
raise its temperature by 10ºC at constant volume.
states, solids, liquids and vapour at its triple point.
Gas can be
In this situation the average KE of the water
(1) He (2) H2 molecule will be
(3) NO2 (4) CO2 (1) Maximum in vapour state
23. Two moles of an ideal gas undergoes following
(2) Maximum in solid state
process as
(3) Greater in the liquid than in vapour state
A (T1)
1.0 B (4) Same in all the three states
P  (atm)

T1 = T2 28. In thermodynamics a process is called reversible

when
0.5 C (T2) (1) System and surrounding change into each
other
20 L 40 L (2) There is no boundary between system and
V(L) surrounding
Correct among the following is/are (3) The surroundings are always in equilibrium with
(1) U = S = 0 (2) WBC = 0 the system

(3) Wcycle  0 (4) All of these (4) The system changes into the surroundings
spontaneously
24. Exothermic reaction among the following is
29. 16 kg oxygen gas expands at STP (1 atm)
(1) Combustion of N2 to form NO
isobarically to occupy double of its original volume.
(2) Decomposition of water The work done during the process is nearly
(3) Conversion of diamond to graphite (1) 260 kcal (2) 180 kcal
(4) Dehydrogenation of ethane to ethene
(3) 130 kcal (4) 271 kcal
25. Expansion of an ideal gas under isothermal and 30. One mole of a non ideal gas undergoes a change
adiabatic condition is given below. Incorrect of state (2.0 atm, 3.0 L, 95 K)  (4.0 atm,
 CP  5.0 L, 245 K) with a change in internal energy
statements is r  C 
 V U = 30.0 L atm. The change in enthalpy of the
process in L atm is
(P1, V1 , T1) (1) 40.0 (2) 42.3
(3) 44.0 (4) 56.0
P Isothermal
31. Which of the following can be zero for isothermal
P2,V2, T2 reversible expansion?
Adiabatic
P3,V3, T3 (1) E (2) H
v (3) T (4) All of these
Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
170 Thermodynamics NEET

32. In an isulated container water is stirred with a rod The A and B systems respectively are
to increase the temperature. Which of the following
(1) Open system, Closed system
is true?
(2) Isolated system, Closed system
(1) U = W  0, q = 0 (2) U = W = q  0
(3) U = 0, W = q  0 (4) W = 0, U = q  0 (3) Adiabatic system, Isolated system

33. Two atoms of hydrogen combine to form a (4) Closed system, Isolated system
molecule of hydrogen gas the energy of the H2 38. Set of intensive properties is shown by
molecule is
(1) Mole fraction, standard electrode potential, heat
(1) Greater than that of separate atoms capacity
(2) Equal to that of separate atoms (2) Viscosity, refractive index, specific heat
(3) Lowers than that of separate atoms (3) Density, Gibbs free energy, internal energy
(4) Sometimes lower and sometimes higher (4) Number of moles, molarity, electrode potential
34. Vapour density of a gas is 8. Its molecular mass 39. For the expansion occurring from initial to final
will be stage in finite time, which is incorrect?
(1) 8 (1) Equilibrium exist in initial and final stage
(2) 16 (2) Work obtained is maximum
(3) 32 (3) Driving force is much greater than the opposing
(4) 64 force
35. If x mole of ideal gas at 27°C expands isothermally (4) Both (1) & (2)
and reversibly from a volume of y to 10y, then the
40. For one mole of an ideal gas
work done is
(Cp and Cv are molar heat capacities at constant
(1) w = x R 300 ln y
presure and constant volume respectively)
y
(2) w = – 300 x R ln 10 y R
(1) Cp – Cv = R (2) Cp – Cv =
2
(3) w = – 300 x R ln 10
(3) Cp – Cv = –2R (4) Cp – Cv = 0
1 41. The molar heat capacity of water at constant
(4) w = 100 x R ln y
pressure P is 75 J K–1 mol–1. When 1.0 kJ of heat
is supplied to 1000 g of water, which is free to
36. A system X undergoes following changes
expand, the increase in temperature of water is
X  W  Z  X (1) 1.2 K (2) 2.4 K
(P1V1T1 ) (P2 V2T1 ) (P3 V2T2 ) (P1V1T1 )
(3) 4.8 K (4) 0.24 K
The overall process may be called as
42. Which statement is correct?
(1) Reversible process
 dH   dE 
(2) Cyclic process (1)    
 dT P  dT  V
(3) Cyclic reversible process
(4) Isochoric process
 dH   dE 
(2)     R
37. Different types of systems are given below  dT P  dT  V
Surrounding Surrounding
Work Matter  dE 
(3)   for ideal gas is zero
Heat Energy  dV  T
System System
(4) All of these
A B
Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Thermodynamics 171
43. S° will be highest for the reaction 50. For a gaseous reaction
1 A(g) + 3B(g)  3C(g) + 3D(g)
(1) Ca(s)  O2 (g)  CaO(s)
2 E is 17 kcal at 27°C. Assuming R = 2 cal K–1
(2) CaCO3(s)  CaO(s) + CO2(g) mol–1 the value of H for the above reaction will be
(3) C(s) + O2(g)  CO2(g) (1) 15.8 kcal
(4) N2(g) + O2(g)  2NO(g) (2) 16.4 kcal
44. In an irreversible process, the value of (3) 18.2 kcal
Ssystem + Ssurr is
(4) 20.0 kcal
(1) +ve (2) –ve
51. A mixture of 2 mole of CO and 1 mol of O2 is
(3) Zero (4) All of these ignited. Correct relationship is
45. The enthalpy and entropy change for a chemical (1) H = U
reaction are –2.5 × 10 3 cal and 7.4 cal K –1
respectively. Predict the nature of reaction at (2) H > U
298 K is (3) H < U
(1) Spontaneous (2) Reversible (4) The relationship depends upon the capacity of
(3) Irreversible (4) Non-spontaneous vessel

46. The temperature at which the given reaction is at 52. Bond dissociation energy of XY, X2 and Y2 (all
equilibrium diatomic molecules) are in the ratio of 1 : 1 : 0.5
and H f of XY is –200 kJ mol –1 . The bond
1 dissociation energy of X2 will be
Ag2O(s)  2Ag(s) + O (g)
2 2
(1) 800 kJ mol–1
H = 30.5 kJ mol–1 and S 0.066 kJ mol–1 K–1 (2) 200 kJ mol–1
(1) 462.12 K (2) 362.12 K
(3) 300 kJ mol–1
(3) 262.12 K (4) 562.12 K
(4) 400 kJ mol–1
47. The temperature of 15 ml of a strong acid
53. Enthalpy of formation of NH 3 is – X kJ and
increases by 2°C when 15 ml of a strong base is
HH–H, HN–H are respectively Y kJ mol–1 andZ kJ
added to it. If 5 ml of each are mixed, temperature
mol–1. The value of HN  N is
should increase by
(1) 0.6°C (2) 0.3°C X
(1) Y – 6Z +
(3) 2°C (4) 6°C 3

48. The standard heat of formation of NO2(g) and (2) – 3Y + 6Z – 2X

N2O4(g) are 8.0 and 4.0 kcal mol–1 respectively.
(3) 3Y + 6Z + X
The heat of dimerisation of NO2 in kcal is
(4) Y + 6X + Z
(1) –12 kcal (2) 12 kcal
(3) 4 kcal (4) 16 kcal 54. The heat of neutralisation for strong acid and strong
base forming 2 moles of water is
1 1 (1) – 2 × 57.1 kJ
49. If X O(s)  X(s) + O2(g); H = 90 kJ.
2 2 4
(2) – 57.1 kJ
Then heat change during reaction of metal X with
one mole of O2 to form oxide to maximum extent 57.1
(3)  kJ
is 2
(1) 360 kJ (2) –360 kJ (4) Strong acid and strong base will not undergo
(3) –180 kJ (4) +180 kJ neutralisation
Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
172 Thermodynamics NEET

55. The value of H° in kJ for the reaction will be 58. A schematic representation of enthalpy changes for
CS2(l) + 4NOCl(g)  CCl4(l) + 2SO2 (g) + 2N2(g) 1
the reaction, C( graphite ) 
O (g)  CO (g) is given
if 2 2
below. The missing value is
Hf (CS2 )   x Hf (NOCl)   y Cgraphite + O2(g)

??
Hf (CCl4 )   z Hf (SO2 )   r CO(g) + ½O(g)
– 393.5 kJ
(1) x + 4y – z – 2r – 283.0 kJ
CO2(g)
(2) r + z + 4y – x
(1) + 10.5 kJ
(3) 2r + z + 4y + x
(2) – 11.05 kJ
(4) x + 4y + z – 2r
56. The heat liberated on complete combustion of (3) – 110.5 kJ
1 mole of CH4 gas to CO2(g) and H2O(l) is 890 kJ. (4) – 10.5 J
Calculate the heat evolved by 2.4 L of CH4 on
59. Which of the following equations represent
complete combustion.
standard heat of formation of CH4?
(1) 95.3 kJ
(1) C(diamond) + 2H2(g)  CH4(g)
(2) 8900 kJ
(2) C(graphite) + 2H2(g)  CH4(g)
(3) 890 kJ
(3) C(diamond) + 4H(g)  CH4(g)
(4) 8.9 kJ
(4) C(graphite) + 4H(g)  CH4(g)
57. The work done in an open vessel at 300 K, when
112 g iron reacts with dil HCl to give FeCl2, is 60. Calorific value of ethane, in kJ/g if for the reaction
nearly 2C2H6 + 7O2  4CO2 + 6H2O; H = –745.6 kcal
(1) 1.1 kcal (1) –12.4
(2) 0.6 kcal (2) –52.2
(3) 0.3 kcal (3) –24.8
(4) 0.2 kcal (4) –104.1

‰ ‰ ‰

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
Chapter 7

Equilibrium
Chapter Contents
z Physical Equilibrium z Reversible processes : Reaction in which the products of the reaction
can react with one another under same conditions of the reaction to give
z Equilibrium in Chemical back the reactants e.g. formation of NH3, HI, SO3, etc. do not go to
Process completion.
z Homogeneous Equilibria z Irreversible processes : Those in which the products formed do not
react to give back the reactants e.g. 2KClO3  2KCl + 3O2. Such
z Heterogeneous Equilibria
processes go to completion e.g. precipitation, the reactions involving
z Applications of Equilibrium evolution of gases, etc.
Constant z Types of Equilibria
z Relationship between (1) Physical equilibrium e.g., H2O(l) H2O(g)
Equilibrium constant (K), (2) Chemical equilibrium e.g., PCl5(g) PCl3(g) + Cl2(g)
Reaction Quotient (Q) and
Gibbs Energy (G) (3) Ionic equilibrium e.g., CH3COOH(aq.) CH3COO–(aq.) + H+(aq.)

z Ionic Equilibria
PHYSICAL EQUILIBRIUM
z Ionization Constants of Weak
Acids and Weak Bases Process Property becoming
constant at equilibrium
z Common ion effect in the
ionisation of Acids and Bases Solid Liquid Melting point at constant
e.g., H2O(s) H2O(l) pressure
z Hydrolysis of Salts and the
pH of their Solution Liquid Vapour Vapour pressure (e.g., pH2O)
z Buffer Solution e.g., H2O() H2O(g) at constant temperature
z Solubility of Sparingly Soluble Solute (s) Solute (solution) Concentration of the solute
Salts e.g., Sugar(s) Sugar (solution) in the solution at the given
temperature

 Gas(aq) 
Gas(g) Gas(aq)  Gas(g)  at the given
 
e.g., CO2(g) CO2(aq) temperature, e.g.,
 CO2 (aq) 
 CO (g)  at the given
 2 
temperature

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
 2 Equilibrium NEET

General Characteristics of Equilibria involving Physical processes

(i) At equilibrium, some observable property of the system becomes constant.
(ii) Equilibria involving gases can be attained only in closed vessels.
(iii) Equilibrium is dynamic in nature i.e., there are two opposing processes taking place at equal rates.
(iv) At equilibrium, the concentrations of the different substances become constant at constant temperature.
(v) At equilibrium, the ratio of the species present in two different phases is constant at a constant
temperature.
For example,
For CO2(g) CO2(aq.)

[CO2 (aq)]
Ratio of = Constant
[CO2 (g)]

This constant is known as equilibrium constant.

(vi) The magnitude of the equilibrium constant represents the extent to which the process proceeds before
equilibrium is attained.

EQUILIBRIUM IN CHEMICAL PROCESS

Law of chemical equilibrium
“The rate at which a substance reacts is proportional to its active mass and the rate of a chemical reaction
is proportional to the product of the active masses of the reacting substances”. Active mass means molar
concentration i.e., the number of gram moles of the solute per unit volume. It is expressed by enclosing the
formula of the substance in square brackets. For example, [A] represents the active mass of the substance
A. The active mass of solids is taken as one.

Chemical Equilibrium
At same given set of condition, the rate at which products are produced from reactants equals the rate at which
reactants are produced from products is known as equilibrium of reaction.

e.g., aA + bB cC + dD

kf
(i) aA + bB  cC + dD …(1)

kb
(ii) cC + dD  aA + bB …(2)

Rate of forward reaction (1) 

rf  k f [A]a [B]b 
According to law of mass action
Rate of backward reaction (2)
c d
rb  k b [C] [D] 

At equilibrium rf = rb

kf [C]c [D]d
 
k b [A]a [B]b

kf [C]c [D]d
K 
kb [A]a [B]b
where K = equilibrium constant, kf and kb are rate constants for forward and backward reaction

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Equilibrium 3

[Pr oduct]
 K
[Reactant]

[HI]2
e.g., H2(g) + I2(g) 2HI(g); K 
[H2 ][I2 ]

Note : Solid and liquid (in excess) entities are not taken in this equation as their activity is taken as 1.

Characteristics of equilibrium constant

(i) The equilibrium constant does not depend upon initial concentration and has a definite value for every
chemical reaction at a given temperature.
Van't Hoff Equation
It gives variation of K with temperature.

K2 H  T2  T1 
log   
K1 2.303R  T1T2 

R is gas constant, H is enthalpy change, K1 and K 2 are equilibrium constants at temperatures

T1 and T2 respectively.
(ii) If the reaction is reversed, the value of equilibrium constant is reciprocated.
Example :
For reaction, H2(g) + I2(g) 2HI(g)
Kc = 50
If reaction is reversed
2HI(g) H2(g) + I2(g)
Now, the value of the equilibrium constant will be

1 [H ][I ] 1
Kc   2 22   0.02
Kc [HI] 50

(iii) If the reaction is multiplied by a factor (n) then the value of equilibrium constant becomes Kc = (Kc)n
Example :



A  B 
 2C ; Keq = Kc



2A  2B 
 4C ; Keq = Kc

Kc = (Kc)2
or



A  B 
 2C ; Keq = Kc

1 1 
A  B 
C ; Keq = Kc
2 2
Kc = (Kc)1/2

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
4 Equilibrium NEET

(iv) The pure solids and liquids are not considered for calculation of Kc because they have constant
concentration, if one of the reactant or product is gas.
(v) If any chemical reaction is completed in more than one step, then equilibrium constant for overall reaction
is equal to the product of equilibrium constant of all steps.
Example :
Step 1 : N2 + O2 2NO ; K1
Step 2 : 2NO + O2 2NO2 ; K2

N2 + 2O2 2NO2 Overall reaction; K

Here, K1 × K2 = K

[NO]2 [NO2 ]2 [NO2 ]2

  K
[N2 ][O2 ] [NO]2 [O2 ] [N2 ][O2 ]2

HOMOGENEOUS EQUILIBRIA
“When in an equilibrium reaction, all the reactants and the products are present in the same phase (i.e.,
gaseous or liquid) it is called a homogeneous equilibrium.”
For example, N2(g) + 3H2(g) 2NH3(g)
In the gaseous reaction, reactants and products are in the homogeneous phase. Similarly, for the reactions,
CH3COOC2H5(aq) + H2O (l) CH3COOH (aq) + C2H5OH (aq)

and, Fe3+(aq) + SCN–(aq) [Fe(SCN)]2+(aq)

all the reactants and products are in same phase. We shall now consider them in equilibrium constant for
some homogeneous reactions.

HETEROGENEOUS EQUILIBRIA
“When in an equilibrium reaction, the reactants and the products are present in two or more than two phases,
it is called a heterogeneous equilibrium.”
The equilibrium between water vapour and liquid water in a closed container is an example of heterogeneous
equilibrium.
H2O(l) H2O(g)
Let us take thermal dissociation of calcium carbonate which is an interesting and important example of
heterogeneous chemical equilibrium.



CaCO3(s)  
 CaO(s) + CO2(g)

On the basis of the stoichiometric equation, we can write,

[CaO(s)][CO2 (g)]
Kc 
[CaCO3 (s)]

Since [CaCO3(s)] and [CaO(s)] are both constant, therefore modified equilibrium constant for the thermal
decomposition of calcium carbonate will be

Kc = [CO2(g)] or Kp = pCO

2

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Equilibrium 5
Relation between Kp and Kc
Kp and Kc for same reaction are related as;

ng
K p  K c (RT)

ng = Number of moles of gaseous products – number of moles of gaseous reactants

Units of Equilibrium Constant

The units of equilibrium constant (Kc) can be determined by expressing the molar concentration in terms of
mol L–1. Similarly, the units of Kp can be expressed in terms of partial pressures as Pa, kPa, bar or
atmosphere.

Example 1 : Write the unit of equilibrium constant (Kc) for the given reaction.
BaCO3(s) BaO(s) + CO2(g)
Solution : Kc = [CO2] i.e. mol L–1

Example 2 : Write the relation between Kp and Kc for the following reactions.
(i) N2(g) + 3H2(g) 2NH3(g)
(ii) 2H2O(g) 2H2(g) + O2(g)
Solution : (i) Kp = Kc(RT)–2
(ii) Kp = Kc(RT)1

EXERCISE

1. In a closed system: A(s) 2B(g) + 3C(g) if the partial pressure of C is doubled then partial pressure of
B will be
(1) Twice the original pressure
(2) Half of its original pressure

1
(3) times the original pressure
2 2

(4) 2 2 times its original pressure

2. Sulphide ion reacts with solid sulphur

S2– (aq)  S(s) S2–

2 (aq) ; K1 = 10

S2– (aq)  2S(s) S32– (aq) ; K2 = 130

The equilibrium constant for the formation of S32–(aq) from S22–(aq) and sulphur is
(1) 10
(2) 13
(3) 130
(4) 1300

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
 6 Equilibrium NEET

3. For the reaction, CaCO3(s) CaO(s) + CO2(g), Kp is equal to

(1) K c (2) KcRT
(3) Kc(RT)2 (4) Kc(RT)–1
4. For the system 3A + 2B C, the expression for equilibrium constant K is
3 A ]  [2B]  A ]3  [B]
(1) (2)
[C] [ C]
[ C] [C]
(3) 3 2 (4)
 A ]  [B] 3 A ]  [2B]
5. A state of equilibrium is reached when
(1) The rate of forward reaction is greater than the rate of the reverse reaction
(2) The concentration of the products and reactants are equal
(3) More product is present than reactant
(4) The concentration of the products and reactants have reached constant value
6. In which of the following cases, the reaction goes farthest to completion?
(1) A B (K = 103) (2) P Q (K = 10–2)
(3) A + B C + D (K = 10) (4) X + Y XY2 (K = 10–1)
7. For the reaction A + 3B 2C + D, initial mole of A is twice that of B. If at equilibrium moles of B and C
are equal, then percent of B reacted is
(1) 10% (2) 20%
(3) 40% (4) 60%
8. The equilibrium A(g) + 4B(g) AB4(g) is attained by mixing equal moles of A and B in a one litre vessel.
Then at equilibrium
(1) [A] = [B] (2) [A] > [B]
(3) [A] < [B] (4) [AB4] > [A]

APPLICATIONS OF EQUILIBRIUM CONSTANT

Predicting the Direction of Reaction
Qc or reaction quotient is defined in the same way as equilibrium constant Kc except that the concentration
in Qc are not necessarily equilibrium values.
[Product]
Qc =
[Reactant]
The direction of reaction is predicted as,
z If Qc < Kc, net reaction goes from left to right.
z If Qc > Kc, net reaction goes from right to left.
z If Qc = Kc, no net reaction occurs.
ent Qc
o vem ds
M ar
nt Qc Kc tow brium
Kc
o veme s ili Kc
M ard equ
tow brium
Qc ili
equ

Reactants  Products Reactants  Products

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Equilibrium 7

Predict the extent of a reaction

The magnitude of the equilibrium constant gives an idea of the relative amounts of the reactants and the
products.

(i) Large value of the equilibrium constant > 103 shows that forward reaction is favoured i.e., concentration
of products is much larger than that of the reactants at equilibrium e.g., for the reactions

300 K

H2(g) + Br2(g)  
 2HBr(g); Kc = 5.4 × 1018

1 500 K
H2(g) + 
O (g)  
 H2O(g); Kc = 2.4 × 1047
2 2

This shows that at equilibrium, concentration of the products i.e., HBr and H2O, are very high and hence
the reactions has gone almost to completion.

(ii) Intermediate value of K(10–3 to 103) shows that the concentrations of the reactants and products are
comparable, e.g., for the reaction.

Fe+3(aq) + SCN–(aq) [Fe(SCN)]2+(aq); Kc = 138 at 298 K

H2(g) + I2(g) 2HI(g); Kc = 57.0 at 700 K

(iii) Low value of K(<10–3) shows that backward reaction is favoured i.e., concentration of reactants is much
larger than that of the products i.e., the reaction proceeds to a very small extent, e.g., for the reaction

N2(g) + O2(g) 2NO(g); Kc = 4.8 × 10–31 at 298 K

This shows that at equilibrium, the mixture contains mainly N2 and O2 and very little of NO.

These generalisations may be represented as follows

Negligible Kc Kc Extremely large Kc

–3 3
10 1 10
Reaction hardly Both reactants and Reaction proceeds
proceeds products are present almost to completion
at equilibrium
Fig. : Dependence of extent of reaction on Kc

Calculating equilibrium concentrations

We can calculate the value of equilibrium concentrations of all the reactants and products by knowing the initial
concentrations of reactants through the following steps :

Step-1 : Write the balanced equation for the reaction.

Step-2 : Assume ‘x’ as the amount of the reactant reacted or as the product formed.

Step-3 : Calculate the equilibrium concentration of each reactant and product from the stoichiometry of the
equation.

Step-4 : Write expression for Kc or Kp.

Step-5 : Substitute equilibrium concentrations and calculate ‘x’.

Step-6 : Calculate values of equilibrium concentrations by putting the value of x in the expression of Kc.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
 8 Equilibrium NEET

For example :
PCl5 PCl3 + Cl2
Initial 1 mol L–1 0 0
At equilibrium 1–x x x
[PCl3 ][Cl2 ]
Kc 
[PCl5 ]

xx x2
 
1 x 1 x

Example 3 : Two moles of PCl5 were heated to 327°C in a closed two litre vessel and when equilibrium was
achieved, PCl5 was found to be 40% dissociated into PCl3 and Cl2. Calculate the equilibrium
constant (Kc ) for the reaction.
n
Solution : PCl5 PCl3 + Cl2 Here concentration of PCl5 =
V
2
1 0 0 = 1
2
1–x x x
x = 40% = 0.4
1 – x = 1 – 0.4 = 0.6
[PCl3 ][Cl2 ]
Kc 
[PCl5 ]
0.4  0.4

0.6
1.6 0.8
 
6 3
 0.267 mole/L

Degree of dissociation and its relation with vapour density

Moles dissociated
z Degree of dissociation () 
Initial moles taken
z % dissociation =  × 100

Dd

(n  1)d

where D = Vapour density before dissociation

d = Vapour density after dissociation
n = Number of moles obtained from one mole of dissociating species
Le Chatelier’s Principle
“When the reaction is already their at equilibrium and if it is subjected to a change of concentration, pressure
or temperature, the equilibrium shifts in the direction that tends to undo the effect of the change”.
Factors influencing Equilibrium Reaction
1. Concentration; 2. Pressure; 3. Inert Gas; 4. Catalyst; 5. Temperature

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Equilibrium 9
1. Concentration
(i) If concentration of reactant increased reaction shifts in forward direction.
(ii) If concentration of reactant decreased reaction shifts in backward direction.
(iii) If concentration of product increased reaction shifts in backward direction.
(iv) If concentration of product decreased reaction shifts in forward direction.
2. Pressure : Effect of pressure depends on the ng of reaction
3. Inert Gas : Effect of inert gas is studied by adding it either at constant pressure or at constant volume
at equilibrium.
Inert gas ng  0 ng   ve ng   ve
At constant V No effect No effect No effect
Backward Forward
At constant P No effect    
4. Catalyst : A catalyst increases the speed of both the forward and backward reactions to the same extent
in a reversible reaction. Thus, a catalyst does not alter the concentration of the reactants and products
in a state of equilibrium.
5. Temperature : With increase or decrease in temperature reaction either shifts in forward or backward
direction and it also changes the equilibrium constant.

Endothermic Reaction Exothermic Reaction

(1) Increase in temperature, Increase in temperature,

shifts reaction in forward shifts reaction in backward
direction direction

(2) Decrease in temperature, Decrease in temperature,

shifts reaction in backward shifts reaction in forward
direction direction
(3) Increase in temperature, Increase in temperature,
increase the equilibrium decrease the equilibrium
constant constant

Note : Only temperature factor changes equilibrium constant value and rest only shifts the direction of reaction.

Example 4 : In the reaction A + B C + D, what will happen to the equilibrium if concentration of A is

increased?
Solution : It will shift to the right.

Example 5 : What will be the effect of increased pressure in the following equilibrium reaction?

(i) H2(g) + I2(g) 2HI(g)

(ii) N2(g) + 3H2(g) 2NH3(g)

(iii) N2O4(g) 2NO2(g)

Solution : (i) No effect.
(ii) Will shift to the right.
(iii) Will shift to the left.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
10 Equilibrium NEET

RELATIONSHIP BETWEEN EQUILIBRIUM CONSTANT (K), REACTION QUOTIENT (Q) AND

GIBBS ENERGY (G)
 If G = 0; the reaction is in a state of equilibrium.

 If G is negative, the reaction is spontaneous in the forward direction.

The relation between free energy change and reaction quotient (Q) may be given as

G  G  RT lnQ

If the reaction has attained equilibrium under the reaction conditions, then G = 0

G  2.303 RT logK

K  e G /RT

 If G° < 0, then –G°/RT is positive and e–G°/RT > 1 making K > 1 which implies a spontaneous
reaction or the reaction which proceeds in the forward direction to such an extent that the products are
present predominantly.

 If G° > 0, then –G°/RT is negative and e–G°/RT < 1, i.e., K < 1, which implies a non-spontaneous
reaction or a reaction which proceeds in the forward direction to such a small degree that only a very
minute quantity of product is formed.

EXERCISE
9. The oxidation of SO2 and O2 to SO3 is an exothermic reaction. The yield of SO3 will be maximum if
(1) Temperature and pressure both are increased (2) Temperature decreased, pressure increased
(3) Temperature increased, pressure constant (4) Temperature and pressure both decreased

10. A + B C + D, Kc for this reaction is 10. If 1, 2, 3, 4 mole/litre of A, B, C and D respectively are present
in a container at 25ºC, the direction of reaction will be
(1) From left to right (2) From right to left
(3) Reaction is at equilibrium (4) Unpredictable

11. The equilibrium constant for the reaction, H2(g) + I2(g) 2HI(g)
is 32 at a given temperature. The equilibrium concentration of I 2 and HI are 0.5 × 10 –3 and
8 × 10–3 M respectively. The equilibrium concentration of H2 is
(1) 1 × 10–3 M (2) 0.5 × 10–3 M
(3) 2 × 10–3 M (4) 4 × 10–3 M

P
12. For the reaction equilibrium, 2NOBr(g) 2NO(g) + Br2(g). If PBr2  at equilibrium and P is total
9
Kp
pressure, the ratio of is equal to
P
1 1
(1) (2)
9 81
1 1
(3) (4)
27 3

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Equilibrium 11
13. At temperature T K, PCl5 is 50% dissociated at an equilibrium pressure of 4 atm. At what pressure it would
dissociate to the extent of 80% at the same temperature?
(1) 0.05 atm (2) 0.60 atm
(3) 0.75 atm (4) 2.50 atm
14. For the equilibrium, CH3CH2CH2CH3(g) CH3 –CH–CH 3 (g)
CH3
iso-butane
If the value of KC is 3.0, the percentage by mass of iso-butane in the equilibrium mixture would be
(1) 75% (2) 90%
(3) 30% (4) 60%
Fe2O3
15. In the manufacture of NH3 by Haber’s process involving the reaction. N 2 (g) + 3H 2 (g) 2NH 3 (g);
H = –22.08 kcal. The favourable conditions are
(1) High pressure and low temperature (2) Low pressure and low temperature
(3) High pressure and high temperature (4) Low pressure and high temperature
16. Ice and water are placed in a closed container at a pressure of 1 atm and 273.15 K temperature. If pressure
of the system is increased by 2 atm keeping temperature constant the correct observation would be
(1) The liquid phase disappears completely
(2) The amount of ice increases
(3) The solid phase (ice) disappears completely
(4) Volume of the system increases
17. A cylinder filled with a movable piston contains liquid water in equilibrium with water vapour at 25ºC. Which
one of the following operations results in a decrease in the equilibrium vapour pressure?
(1) Moving piston downward a short distance
(2) Removing a small amount of vapour
(3) Removing a small amount of the liquid water
(4) Dissolving salt in the water
18. Choose the correct statement
(1) Catalyst increases the rate of reaction
(2) Catalyst decreases the time of attainment of equilibrium
(3) Catalyst decreases the activation energy
(4) All are correct
19. If K1 is the equilibrium constant at temperature T1 and K2 is the equilibrium constant at temperature T2, and
if T2 > T1 and reaction is endothermic then
(1) K2 < K1 (2) K2 = K1
(3) K2 > K1 (4) All of these

IONIC EQUILIBRIA
Electrolytes are substances which in the dissolved state or in molten state conduct electricity. In fact they
dissociate into ions which cause conductance. Strong electrolytes are completely ionisable, e.g. HCl, H2SO4,
NaOH, KOH, NaCl, KNO3, HNO3, HI, HClO4, KCl, NaNO3, Na2SO4 etc.
Weak electrolytes : only slightly ionised CH3COOH, NH4OH, NH3,CH3NH2,(CH3)2NH,(CH3)3N etc.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
12 Equilibrium NEET

Acid Base Concept :

z Arrhenius concept of Acids & Bases : Acids are substances which dissociate in water to produce H+ ions
while bases give OH– ions.
z Bronsted Lowry concept:
(i) An acid is a substance which can donate proton (H+) while a base is a subtance which can accept a
proton (H+). HCl + NH3 NH4+ + Cl–, CH3COOH + H2O CH3CO O O + H3O+.
(ii) Water is amphoteric. It can donate as well as accept protons.
(iii) Conjugate acid-base pairs are the pairs of substances which differ by one proton e.g. H3O+ and H2O, H2O
and OH○ , NH4+ and NH3, CH3COOH and CH3COO–, HCl and Cl– etc.
(iv) A strong acid has weak conjugate base and a strong base has weak conjugate acid and vice-versa.
+ –
HA ( aq) + H2O(l) H 3O (aq) + A (aq)
Acid Base Acid Base

Conjugate acid-base pairs

z Lewis concept: Acid is a substances which can accept a pair of electrons while a base can donate a pair
of electrons.
Acids: H+,Ag+, Cu2+, BF3, FeCl3, SnCl4, SiF4, CO2, SO2 etc.
.. .. ..
Bases: OH¯, Cl¯, SO42—, CH3COO—, H2 O,
..
NH3 , RNH2 , etc.
–
Acid, HA Base, A
Stronger
HClO4  Strong acids. ClO4–  Very weak bases.
acid
HCl  100% dissociated Cl–  Negligible tendency
H2SO4  in aqueous HSO4–  to be protonated in
 solution. –  aqueous solution.
HNO3  NO3 
H3O+ H2O
HSO4–  SO42– 
H3PO4  H2PO4– 
HNO2  NO2
–

HF  F
– 
 Weak acids.  Weak bases.
CH3CO2H  Exist in solution CH3CO2–  Moderate tendency
H2CO3  as a mixture of HCO3–  to be protonated in
 HA, A–, and H3O +. –  aqueous solution.
H2S  HS 
+
NH4  NH 3 
HCN  CN– 
 
HCO3–  CO32– 
–
H2O OH
–
NH3  Very weak acids. NH 2  Strong bases.
 Negligible tendency  100% protonated in
OH–  O 2–

Weaker H2  to dissociated H–  aqueous solution.
acid

Properties of water : Pure water is always neutral at all temperatures.

z Ionisation constant of water (Kw)
Kw = [H3O+] [OH–]
pKw = – log Kw
[HO] = Kw/[H3O+] or [H3O+] = Kw/[OH]–
Kw depends on the temperature. Kw increase with increase in temperature.
z Degree of ionization of water increase with increase of temperature.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Equilibrium 13
pH Scale (Sorensen in 1909)

The pH is defined as negative logarithm 10 base of the activity (aH ) of hydrogen ion. At low concentration
the activity of hydrogen ion is numerically equal to its molarity which represented by [H+].

pH   log[H ] and pOH   log[OH ]

At 298K :

pH
0 acidic 7 basic 14

Neutral

e.g., pH for 10–3 M HCl is 3.

Note : pH + pOH = pKw i.e. pH + pOH = 14 (at 298K).
Kw changes with temperature and accordingly the pH scale also changes.

Example 6 : The concentration of H+ ion in a sample of soft drink is 3.8 × 10–3 M. What is its pH?
Solution : pH = –log[H+]
= –log [3.8 × 10–3]
= 3 – 0.58 = 2.42

Example 7 : If hydrogen ion concentration in a solution is 1 × 10–5 mole/litre, calculate the concentration of
OH– ion in this solution (Kw = 10–14 mole2 L–2).

Solution : Kw = [H+][OH–] = 10–14

10 14 10 14
[OH–] =   10 9 mol L1

[H ] 10 5

IONIZATION CONSTANTS OF WEAK ACIDS AND WEAK BASES

The dissociation of a weak acid in water can be represented by the equilibrium
HA + H2O H3O+ + A–
Initial concentration c 0 0
Concentration at equilibrium (c – c) c c (Here  is degree of ionisation)
c(1 – )
[H3 O  ][A  ] c  c  2c 2
Ka   
[HA] c(1   ) c(1   )
Hence for,  <<< 1
Ka = 2c
1/2
K 
   a
 c 

  (K a  V)1/2

1
Here, V is the volume of the solution in litres containing 1 mole of the electrolyte, c = .
V
Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
14 Equilibrium NEET

In case of a weak electrolyte, at a given temperature, the degree of ionisation is inversely proportional to the
square root of the molar concentration or directly proportional to square root of the volume of the solution which
contains one mole electrolyte.
This is called Ostwald’s dilution law.
Similarly, the dissociation of a weak base in water can be represented by the equilibrium


  
 B  OH
BOH 
Initial concentration c 0 0
Concentration at equilibrium c(1 – ) c c

[B  ][OH ]  c   c  2c
Now, K b   
[BOH] c(1   ) 1  
For a weak electrolyte, if  is very small, it can be neglected.

 K b   2c

1/2
Ka Ka
Degree of ionisation for acid () = or and c = [H3O+]
c c
1/2
Kb Kb
Degree of ionisation for base () = or and c = [OH–]
c c
1
For weak acid pH = (pKa  logc)
2
1
For weak base pOH = (pKb  logc)
2

Example 8 : If Ka of a weak acid is 4 × 10–6 and its concentration is 0.1 M. Find pH of solution.
1
Solution : pH = [pKa – logc]
2
1
= [–log4 × 10–6 – log10–1]
2
1
= [–0.6020 + 6 + 1]
2
1
= [7 – 0.602] = 3.199
2

Relation between Ka and Kb of acid-base conjugates pair

Consider the weak acid, HF. Its conjugate base is F–. They dissociate as follows :

  
H F
HF 
[H ][F  ]
Ka  ...(i)
[HF]


and F– + H2O 
 OH– + HF
[OH ][HF]
Kb  ...(ii)
[F ]
Now, K w  K a  K b
pK a  pK b  pK w  14 at 298 K

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Equilibrium 15

Example 9 : The dissociation constant of a base MOH is 4 × 10–6, then calculate the dissociation constant
of its conjugate acid.
Solution : Kw = Ka × Kb

10 14
Ka   2.5  10 9
4  10 6

Example 10 : The dissociation constant of 0.01 M CH3COOH is 1.8 × 10–5, then calculate the dissociation
constant of its conjugate base (CH3COO–).
Solution : Kw = Ka × Kb

Kw 10 14
Kb    5.6  10 10
K a 1.8  10 5

Di and Polybasic Acids and Di and Polyacidic Bases

Some acids like sulphuric acid (H2SO4), carbonic acid (H2CO3), oxalic acid (COOH)2, phosphoric acid H3PO4
and some bases like Ca(OH)2, Al(OH)3 etc. contain more than one ionisable proton and hydroxide ion. Such
type of acids and bases are called polybasic or polyprotoic acids and polyacidic bases respectively. They ionise
in steps.
For example, the dibasic acid (H2X) may ionise in two steps as follows :

H2X(aq) H+(aq) + HX–(aq)

HX–(aq) H+(aq) + X–2(aq)

Their ionisation constant, K a1 and K a2 called the 1st and the 2nd ionisation constant respectively, will be given
by the equations.

[H ][HX ] [H ][X2 ]

K a1  and K a2 
[H2 X] [HX ]

The overall equilibrium may be obtained by adding the stepwise dissociation equilibria. Thus, for the above
process, the overall equilibrium will be
H2X(aq) 2H+(aq) + X–2(aq)

[H ]2 [X 2 ]
Ka 
[H2 X]

Therefore, K a  K a  K a
1 2

Similarly, a tribasic acid like H3PO4 has three ionisation constants. The overall ionisation constant (Ka) will
be the product of the ionization constants of the three steps. i.e.,

K a  K a1  K a2  K a3

Similarly, for polybasic acids

K a  K a1  K a2 .....
Similarly, for polyacidic bases
K b  Kb1  K b2  K b3  .....

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
16 Equilibrium NEET

COMMON ION EFFECT IN THE IONISATION OF ACIDS AND BASES

“The suppression in the dissociation of a weak electrolyte by the addition of a strong electrolyte having a
common ion is called common ion effect”.
For example : Ionisation of acetic acid (CH3COOH) and effect of addition of a small amount of acetate ion

CH3COOH(aq) CH3COO–(aq) + H+(aq)

CH3COONa(aq) CH3COO–(aq) + Na+(aq)

Common ion

Due to the presence of common CH3COO–(aq) ions, the equilibrium will be shifted to the left according to Le
Chatelier’s principle.

Example 11 : The dissociation constant of 0.01 M CH 3COOH is 1.8 × 10 –5 , then calculate CH 3COO –
concentration in 0.1 M HCl solution.

Solution : CH3COOH CH3COO– + H+

HCl Cl– + H+
Common ion

CH3COOH CH3COO– + H+
0.01 0 0
0.01 – x x x
Here x is very small value.

[CH3 COO ][H ]

ka 
[CH3 COOH]

1.8  10 5  0.01
[CH3 COO ]  ([H+] is taken from 0.1 M HCl)
0.1
[CH3COO ] = 1.8 × 10–6 mol/L
–

EXERCISE
20. With increase in temperature, pH of pure water
(1) Increases
(2) Decreases
(3) Remains constant
(4) May increase or decrease
21. The pH of a solution is increased from 3 to 6, its H+ concentration will be
(1) Reduced to half
(2) Doubled
(3) Reduced by 1000 times
(4) Increased by 1000 times

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Equilibrium 17
22. Which pair will show common ion effect?
(1) BaCl2 + Ba(NO3)2 (2) NaCl + HCl
(3) NH4OH + NH4Cl (4) NaCN + KCN
23. The compound that is not a Lewis acid
(1) AlCl3 (2) BF3
(3) NF3 (4) SnCl4
24. Fear and excitement generally cause one to breathe rapidly and it results in the decrease of CO2 concentration
in the blood. In what way will it change the pH of the blood?
(1) pH will decreases
(2) pH will increases
(3) pH will adjust to 7
(4) pH will remain unchanged

HYDROLYSIS OF SALTS AND THE pH OF THEIR SOLUTION

Hydrolysis is a process in which a salt reacts with water to form acid and base.



Salt + Water 
 Acid + Base

Thus, the salt hydrolysis is the reverse of neutralisation reaction. The nature of the solution after hydrolysis
depends upon the relative strengths of the acid and base formed. On this basis, the salts are divided into four
categories.
1. Salts of strong acid and strong bases :
The examples of these salts are NaCl, KNO3, Na2SO4, K2SO4, NaNO3 etc.
In general salts of strong acid and strong base do not undergo hydrolysis. They simply form ions in
solution.
2. Salts of strong acid and weak base :
The salts belonging to this type are NH4NO3, NH4Cl, (NH4)2SO4, CuSO4, AlCl3 etc.
It is known as cationic hydrolysis and proceeds as follows


B+ + H2O 
 BOH + H+

[BOH][H ]
Now, Kh 
[B ]

For the dissociation of weak base,



 B+ + OH–
BOH 

[B  ][OH ]
Kb 
[BOH]

Ionic product (Kw) for water is

Kw = [H+][OH–]

K h  K b [BOH][H ] [B ][OH ] 1 Kw

Now,     1 Kh 
Kw 
[B ] [BOH] [H ][OH ] Kb

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
18 Equilibrium NEET

K

h
B+ + H2O 
 BOH + H+
Initial concentration c 0 0
Concentration at equilibrium c(1 – h) ch ch

H ][BOH] ch  ch ch2

Now, Kh  
 
[B ] c(1  h) 1  h

Kh = ch2 (1 – h  1 for weak electrolyte)

Kh
h
c
Kw
h
Kb  c
1/2
Kw Kw  c
[H ] = ch = c  
Kb  c Kb
1/2
Kw  c
pH = –log[H+] = –log
Kb
1
pH =  [logKw – logKb + logc]
2
1
pH  7  [pK b  logc] at 298 K
2
The resulting solution after hydrolysis is acidic and its pH will be less than 7.
3. Salt of strong bases and weak acids :
The salts belonging to this type are CH3COONa, Na2CO3, Na3PO4, K2CO3 etc.
It is called anionic hydrolysis and proceeds as follows


A– + H2O 
 HA + OH–



 H+ + A–
HA 

[H ][A  ]
Ka 
[HA]

Kh  Ka [HA][OH ] [H ][A  ] 1

Now,     1
Kw [A  ] [HA] [H ][OH ]

Kw
Kh 
Ka

Kh Kw
and h 
c Ka  c

[OH–] = ch

Kw Kw
 [H ]  

[OH ] ch

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Equilibrium 19

Kw Ka  c K w  Ka
[H ]   
c Kw c
pH = –log[H+]

K w  Ka
  log
c
1
pH =  [logKw + logKa – logc]
2
1
pH  7  [pK a  logc]
2
It involves anionic hydrolysis. The resulting solution after hydrolysis is basic (pH > 7).
4. Salts of weak acid and weak base :
The salts belonging to this type are CH3COONH4, (NH4)2CO3, Ca3(PO4)2 etc.
It is called cationic as well as anionic hydrolysis and proceeds as follows



B+ + A– + H2O 
 BOH + HA
Initial concentration c c 0 0
Concentration at equilibrium c(1 – h) c(1 – h) ch ch

Kw
Kh 
K a  Kb

Kw
h  Kh 
Ka  Kb
Dissociation of weak acid
HA H+ + A–

[H ] [A ] K [HA]

 Ka =  [H ] = a 
[HA] [A ]
K a  ch
[H ] 
c(1  h)
[H+] = Ka × h [As (1 – h) = 1]

[H+] = Ka × Kh
1/2
Kw K w  Ka
[H ] = K a  
K a  Kb Kb
1/2
K w  Ka
pH = – log[H+] = – log
Kb
1
pH =  [logKa + logKw – logKb]
2
1
pH  7  [pK a  pK b ]
2
It involves cationic as well as anionic hydrolysis. The nature of the solution or its pH depends upon the
relative strengths of the acid and base that are formed on hydrolysis.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
20 Equilibrium NEET

Example 12 : Calculate the degree of hydrolysis of 0.1 M solution of acetate at 298 K.

Given : Ka = 1.8 × 10–5

Kw 1  10 14
Solution : Hydrolysis constant (Kh) =   5.5  10 10
K a 1.8  10 5

Kh 5.5  10 10
Degree of hydrolysis (h) =  = (55 × 10–10)1/2 = 7.42 × 10–5
c 0.1

Example 13 : Calculate the pH of 0.10 M solution of NH4Cl. The dissociation constant (Kb) of NH3 is 1.8 × 10–5.
Solution : NH4Cl is a salt of strong acid and weak base.
1
pH = 7 – [pkb + logc]
2
1
=7– [–log(1.8 × 10–5) + log 0.10]
2
1
=7– (5 – 0.26 – 1) = 5.12
2

Example 14 : The pKa of acetic acid and pKb of ammonium hydroxide are 4.76 and 4.75 respectively. Calculate
the pH of ammonium acetate solution.
Solution : As CH3COONH4 is a salt of weak acid and weak base,

1
pH = 7 + [pKa – pKb]
2

1
=7+ (4.76 – 4.75)
2

= 7 + 0.005 = 7.005

Example 15 : Calculate the percentage hydrolysis of decinormal solution of ammonium acetate given that
Ka = 1.75 × 10–5, Kb = 1.8 × 10–5, Kw = 1 × 10–14.
Solution : Ammonium acetate is a salt of weak acid and weak base

Kw 1 1014
Kh    3.175  105
K a  K b 1.75  105  1.8  105

h  k h  (3.175  10 5 )1/2

h = 5.63 × 10–3

BUFFER SOLUTION
Solutions which resist the change in pH value by the addition of a small amount of an acid or base or the
solvent. Buffers may be acidic or basic. Acidic buffer is made by mixing a weak acid and its salt with a strong
base (CH3COOH + CH3COONa) while a basic buffer is the solution of a weak base and its salts with a strong
acid (NH4OH + NH4Cl). pH of buffers can be determined by using Henderson’s equation e.g. for the acidic
buffer,

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Equilibrium 21
Example : CH 3COOH + CH 3COONa, COOH COOK etc.
+
COOH COOK

pH = pK a + log [Salt]/[Acid]
For basic buffer (e.g. : NH4OH + NH4Cl, etc.)
pH = 14 – pKb + log [Base]/[Salt]

[Salt]
or pOH = pKb + log
[Base]

Note : z For preparing the buffer solution of the required pH we select that acid whose pKa is close to the
required pH.
z pH of the buffer solution is not affected by dilution.

z Buffer capacity. It is defined as number of equivalents of acid or base to be added to 1 litre of buffer solution
so as to change its pH by 1.

No. of moles of acid or base added L–1

Buffer capacity = .
change in pH.
z Application of buffer solutions
(i) pH of blood is maintained with the help of buffer (HCO3– and H2CO3). pH of blood is 7.42.
(ii) It is used to precipitate group III radicals as hydroxides.
(iii) It is maintained for manufacture of dyes and drugs.

Example 16 : Calculate the pH of buffer solution formed by mixing 60 g CH3COOH and 82 g CH3COONa (pKa
of CH3COOH is 4.75)
60
Solution : z mol of CH3COOH = 1
60
82
mol of CH3COONa = 1
82
z pH of acid buffer of CH3COOH and CH3COONa is

 CH COONa 
pH  pKa  log  3 
 CH3 COOH 
 1
= 4.75 + log    4.75
 1

SOLUBILITY OF SPARINGLY SOLUBLE SALTS

Solubility Product : Ksp
Different salts dissolve to different extent in a solvent. Some salts are highly soluble while the others dissolve
to smaller extent. The relative solubilities of the salts is compare with the help of a constant known as solubility
product (Ksp).
Solubility product is calculated for sparingly soluble salt.
Solubility product constant is equal to the product of the ionic concentration in the saturated salt solution at
a given temperature.
The solution in which any solid is in equilibrium with it's ions is called as saturated solution.
AB(Solid) AB A   B
unionised  
dissolved ions

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
22 Equilibrium NEET

Since the solution is saturated, the concentration of unionised molecules of the electrolyte is constant at a
particular temperature i.e. [AB] is constant.
 Ksp = [A+] [B–]
where Ksp = solubility product.
For general electrolyte AxBy which is dissociated as
A xB y xA+y + yB–x
 Ksp = [A+y]x [Bx–]y
z Relation between solubility (s) and solubility product (Ksp)
(i) AgBr (s) Ag+ + Br– ; Ksp = [Ag+][Br–]

Ksp = s × s = s2 therefore s = K sp
Where 's' is solubility in mol L–1.
(ii) Ag2CrO4 2Ag+ + CrO42- Ksp = [Ag+]2[CrO42–]
K sp
Ksp = (2s)2 (s) = 4s3 therefore s = 3
4
(iii) Al(OH)3 Al3+ + 3OH–
Ksp = [Al3+][OH¯]3

K sp
Ksp = s (3s)3 = 27 s4 therefore s = 4
27
(iv) Ca3 (PO4)2 3Ca2+ + 2PO43–

K sp
Ksp = [Ca2+]3 [PO43-]2 = (3s)3 (2s)2 = 108s5 therefore s = 5
108

Example 17 : The solubility of AgCl in water at 298 K is 1.06 × 10–5 mole per litre. Calculate its solubility product
at this temperature.

Solution : AgCl(s) Ag+ + Cl–

s s
Ksp = [Ag+][Cl–]
= s × s = s2
= (1.06 × 10–5)2
= 1.12 × 10–10 mol2 L–2

Example 18 : Calculate the solubility product of PbCl2 at a certain temperature if the solubility of PbCl2 is
4.4 g/L at the same temperature. (Pb = 207, Cl = 35.5)
Solution : Molar concentration of PbCl2 = 1.6 × 10–2 M
4.4
[Concentration of PbCl2 = 4.4 g/L = = 1.6 × 10–2 mol/L]
278
PbCl2 Pb+2 + 2Cl–
s 2s
Ksp = [Pb+2][Cl–]2
= s × (2s)2 = 4s3
= (1.6 × 10–2)3 × 4 = 1.63 × 10–5

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Equilibrium 23

Example 19 : Calculate the solubility of A2X3 in pure water, assuming that neither kind of ion reacts with water.
The solubility product of A2X3, ksp = 1.1 × 10–23.

Solution : 

 2A+3 + 3X–2
A2X3 
2s 3s
Ksp = [A+3]2 [X–2]3
(2s)2 × (3s)3
= 4s2 × 27s3
= 108s5 = 1.1 × 10–23
1/5 1/5
K sp  1.1 1023 
s    105 mol L1
108  108 

Example 20 : Give reason why BaSO4 will precipitate out when equal volumes of 2 × 10–3 M BaCl2 solution and
2 × 10–4 M Na2SO4 solution are mixed. Given that the solubility product of BaSO4 is 1 × 10–10.
Solution : BaCl2 and Na2SO4 are ionises completely in the solution
BaCl2  Ba+2 + 2Cl–
[Ba+2] = [BaCl2] = 2 × 10–3 M
Na2SO4  2Na+ + SO4–2
[Na2SO4] = [SO4–2] = 2 × 10–4 M
Equal volumes of the two solutions are mixed together, therefore, the concentration of Ba+2 ions
and SO4–2 ions after mixing will be
2  10 3
[Ba+2] =  10 3 M
2
2  10 4
and [SO4–2] =  10 4 M
2
 Ionic product of BaSO4 = [Ba+2][SO4–2] = 10–7 M
Here, ionic product of BaSO4 is greater than solubility product value. Hence, a precipitate of BaSO4
will be formed.

Example 21 : Two sparingly soluble salts AB and xy2 have the same solubility product. Which salt will be more
soluble?
Solution : Let the solubility of AB = s1 mol L–1
The solubility of xy2 = s2 mol L–1
AB A+ + B–
s1 s1
Ksp = [A+] [B–]
Ksp = s12

s1  (K sp )1/2

xy2 x+2 + 2y–1

s2 2s2
Ksp = [x+2] [2y–]2
= 4s23
1/3
 K sp 
s2   
 4 
Obviously s2 > s1 (as Ksp have values with negative power of 10). Hence, salt xy2 is more soluble.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
24 Equilibrium NEET

Example 22 : Calculate solubility of AgCl in 0.1 M NaCl at 25°C if its solubility product at same temperature
is 2.0 × 10–10.

Solution : In presence of common ion

K sp 2.0  1010
s   2.0  109 mol L1
Concentration of common ion 0.1

Example 23 : What is the minimum concentration of Ba+2 ions required in order to initiate the precipitation of
BaSO4 from a solution containing 0.002 mol L–1 of SO4–2 ions? (Given Ksp for BaSO4 = 1.4 ×
10–10)

Solution : If ionic product of [Ba+2] [SO 4–2 ] is greater than Ksp for BaSO4, then the precipitation occur.

[Ba 2 ]  (2  10 3 )  1.4  10 10

[Ba 2 ]  0.7  10 7 mol L1

Thus, minimum concentration of Ba+2 ions required for the precipitation of BaSO4 is 0.7 × 10–7 M.

z Criteria of Precipitation of an Electrolyte

(1) When IP < Ksp then solution is unsaturated in which more solute can be dissolved.
(2) When IP = Ksp then solution is saturated in which no more solute can be dissolved.
(3) When IP > Ksp then solution is supersaturated and precipitation takes place.
[IP = Ionic product; Ksp = Solubility product]

Common Ion Effect on Solubility of Ionic Salts

The common ion effect helps in purification of an impure sample of NaCl (common salt) containing the impurities
of soluble salts. A saturated solution of the impure sample is first prepared and is then transferred to another
container. HCl(g) is now passed through the solution with the help of a pipe, Cl– ions will act as common
ion.

NaCl(s) Na+(aq) + Cl–(aq)

(Saturated
solution)

HCl(aq) H+(aq) + Cl–(aq)

Common ion

As a result, pure sodium chloride will get precipitated from the solution leaving behind the impurities in the solution.

K sp  [Na  ][Cl ]

If HCl gas is passed through the saturated solution of NaCl, Cl– ion concentration will increase so that
I.P. > Ksp. In order that I.P. may become equal to Ksp, equilibrium will shift in the backward direction and
the concepts of solubility product and common ion effect combined together play an important role in the
inorganic quantitative analysis. For example,

Precipitation of Hydroxides of group-III

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Equilibrium 25
The radicals of group-III (Fe+3, Cr+3, Al+3) are precipitated as their hydroxides by the addition of NH4OH in
excess. But before this, solid NH4Cl is added. This is necessary as otherwise the radicals of group-IV may
precipitate as hydroxides.

NH4OH NH4+ + OH–

NH4Cl NH4+ + Cl–

Common
ion

By the addition of NH4Cl, the dissociation of NH4OH is further suppressed and [OH–] concentration becomes
low. But this low concentration of [OH–] ions is sufficient to precipitate the radical of 3rd group (Ksp of their
hydroxide being low) and not the radicals of group IV. So, NH4Cl is added to prevent the precipitation of
radicals of group IV as their hydroxides.
z Phenolphthalein is suitable indicator for titration of strong base and weak acid because phenolphthalein is
a weak organic acid. e.g. NaOH and oxalic acid titration, it is suitable.
z Methyl orange is a weak organic base therefore, it is used for titration of strong acid and weak base
e.g. HCl and NH4OH titration.

EXERCISE

25. For a MX2 type salt if Ksp is solubility product, then solubility will be

K sp K sp
(1) s  (2) s  3
2 4

K sp K sp
(3) s  3 (4) s  3
6 8

26. The compound whose 0.1 M solution is basic is

(1) Ammonium acetate (2) Ammonium chloride
(3) Ammonium sulphate (4) Sodium acetate
27. The correct order of increasing solubility of AgCl in
(A) Water (B) 0.1 M NaCl
(C) 0.1 M BaCl2 (D) 0.1 M NH3
is
(1) A < B < C < D (2) B < C < A < D
(3) C < B < D < A (4) C < B < A < D

28. Which of the following increasing order of pH of 0.1 M solution of the compound A HCOONH 4 ,

B CH3COONH4, C CH3COONa, D NH4Cl is correct?

(1) A < D < B < C (2) D < A < C < B

(3) A < D < C < B (4) D < A < B < C

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
26 Equilibrium NEET

29. Ksp of Mg(OH)2 is 4.0 × 10–12. The number of moles of Mg2+ ions in one litre of its saturated solution in 0.1
M NaOH is
(1) 4.0 × 10–10 (2) 1.0 × 10–4
(3) 2.0 × 10–6 (4) 8.0 × 10–6
30. Which of the following is correct for the solution of the salt of weak acid & weak base?

1 1
(1) pH =
2
pK w  pKa – pKb  (2) pH =
2
pK w – pK a – pKb 

1 1
(3) pH =
2
pK w  pK a  pKb  (4) pH =
2
pK w  pK a  pKb 

‰‰‰

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
 nt
me nment
sigAnssig
Assignment
As

Assignment
4. Ammonium carbamate decomposes as
SECTION - A
NCERT Based MCQs 

NH2COONH4(s)  2NH3(g) + CO2(g)
For this reaction, KP = 108 × 10–6 atm3. If we start
1. 

For a chemical reaction of the type A 
 B, with 1 mole of the compound, the total pressure at

 equilibrium would be [NCERT Pg. 203, 204]
K 1 = 3.0 and B 
 C, K 2 = 0.03, then
(1) 0.058 atm (2) 0.048 atm


equilibrium constant for the reaction 2C 
 2A
(3) 0.09 atm (4) 0.03 atm
is (K1 and K2 are equilibrium constant)
5. In a reversible reaction, two substances are in
[NCERT Pg. 201]
equilibrium. If the concentration of one of them is
reduced to half, then the equilibrium constant will
1
(1)
81 104 [NCERT Pg. 205]
(1) Reduce to half of its initial value
(2) 81 × 104
(2) Become twice of its initial value
1
(3) (3) Remain same
9  104
(4) Reduce to one-fourth of its initial value
(4) 9 × 104
6. Inert gas has been added to the following
2. Which of the following values of equilibrium
equilibrium system at constant volume
constant predict almost completion of the reaction?
[NCERT Pg. 205] 

SO2(g) + 1/2 O2(g) 
 SO3(g)

(1) K = 10–2 To which direction will the equilibrium shift?

(2) K = 100 [NCERT Pg. 211]
(3) K = 10 (1) Forward
(4) K = 104 (2) Backward
3. What will be the total pressure of the gaseous (3) No effect
mixture at equilibrium if AB2 is 20% dissociated
according to the following reaction, (4) Unpredictable


 7. Which of the following reactions has minimum
AB2 (g)  A(g)  2B(g) ? (K P represents the
KP
equilibrium constant of the reaction) value of K ? [NCERT Pg. 202]
C
[NCERT Pg. 207]
(1) 4 KP 

(1) 2NO2 (g)  N2O4 (g)

(2) 7KP1/2 


(2) SO2Cl2 (g)  SO2 (g)  Cl2 (g)

(3) 2KP1/2 


(3) N2 (g)  3H2 (g)  2NH3 (g)

(4) 3KP1/2 


(4) 2HBr(g)  H2 (g)  Br2 (g)

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
28 Equilibrium NEET

8. Consider the following graph for the chemical reaction 11. The dissociation constant of a weak monoacidic
base is 10–5. The pH of its 0.1 M solution will be


H2(g) + I2(g)  2HI(g) approximately equal to [NCERT Pg. 221]
(1) 11 (2) 8
(3) 7.5 (4) 10
Concentration
HI
H2, I2
12. K1
HF  H2O  H3 O  F

F  H2O 
K2
HF  OH

Time Equilibrium Time For the above two reactions which of the given
relation is correct? [NCERT Pg. 223]
The inference that can be obtained from this graph
(2) K 2  1
about chemical equilibrium is that
(1) K2 = Kw
[NCERT Pg. 198] Kw

(1) Equilibrium can be attained only when it starts K1

(3) Kw = K1K2 (4) K w 
from pure product K2
(2) Equilibrium can be attained only when it starts
13. pH of solution formed by mixing 40 ml of 0.1 M
from pure reactants
HCl with 10 ml of 0.45 M of NaOH is
(3) Equilibrium can be attained from both sides,
[NCERT Pg. 218]
either it starts from pure product or from pure
reactants (1) 10 (2) 12
(4) Equilibrium can’t be attained in reverse (3) 8 (4) 6
direction if it starts from pure reactants
14. What is the pH of 10–6 M HCl at 25°C?
9. Out of the following, choose an incorrect statement.
[NCERT Pg. 218]
[NCERT Pg. 195]
(1) 6 (2) 7

(1) For solid  liquid equilibrium, there is (3) < 6 (4) > 7
only one temperature that is melting point at
which the two phases can coexist at a given 15. The solubility of sparingly soluble salt Bi2S5 is
pressure S mol dm3. Its solubility product is
[NCERT Pg. 229]

(2) For liquid 
 vapour equilibrium, the vapour
pressure is constant at a given temperature (1) 6250 S5 (2) 3125 S6

(3) When radioactive sugar is dissolved into (3) 108 S7 (4) 12500 S7
saturated solution of non-radioactive sugar,
then after some time radioactivity is observed SECTION - B
both in the solution and in the solid sugar
Objective Type Questions

(4) For Ice(s)  
 water (), on increasing the
1. The equilibrium constant K C for the following
pressure melting of ice decreases
reaction will be
10. The pK a and pK b value of acetic acid and
K2CO3(aq) + BaSO4(s)  BaCO3(s) + K2SO4(aq)
ammonium hydroxide are 4.78 and 4.7 respectively,
then the pH of ammonium acetate solution is [CO23 – ] [K 2CO3 ]
(1) (2)
[NCERT Pg. 226] [SO24– ] [K 2SO4 ]
(1) 8.04 (2) 6.02 [BaSO 4 ] [SO24– ]
(3) (4)
(3) 7.04 (4) 5.04 [CO23 – ] [CO23 – ]

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Equilibrium 29
2. When 3.00 mole of A and 1.00 mole of B are mixed 8. For the equilibrium AB(g) A(g) + B(g), Kp is
in a 1.00 litre vessel, the following reaction takes equal to four times the total pressure. The number
place of moles of 'A' formed is
A(g) + B(g)  2C(g)
5
(1) (2) 2
The equilibrium mixture contains 0.5 mole of C. 2
What is the value of equilibrium constant for the
reaction? 2
(3) 5 (4)
(1) 0.12 (2) 6 5

(3) 1.5 (4) None of these 9. Kp is how many times equal to Kc for the given
reaction?
3. In which of the following does the reaction go
almost to completion? N2(g) + 3H2(g) 2NH3(g)
(1) Kc = 103 (2) Kc = 102
1
(3) Kc = 10–2 (4) Kc = 10–3 (1) (2) R2T2
R2T 2
4. 4.0 moles of PCl5 dissociate at 760 K in a 2 litre
flask PCl5 (g)  PCl3(g) + Cl2(g) at equilibrium. R
(3) (4) RT
0.8 mole of Cl 2 was present in the flask.The T
equilibrium constant would be
10. 4 gm H2, 32 gm O2, 14 gm N2 and 11gm CO2 are
(1) 1.0 × 10–1 (2) 1.0 × 10–4 taken in a bulb of 500 ml. Which one of these has
maximum active mass?
(3) 1.0 × 10–2 (4) 1.0 × 10–3
(1) H2 (2) O2
5. Two moles of NH 3 gas are introduced into a
previously evacuated one litre vessel in which it (3) N2 (4) CO2
partially dissociates at high temperature as 11. At temperature T, a compound AB2(g) dissociates
2NH3 (g)  . N2 (g) + 3H2 (g). At equilibrium, one according to the reaction
mole of NH3(g) remain. The value of Kc is
2AB2(g) 2AB(g) + B2(g) with a degree of
(1) 3
dissociation 'x' which is small as compared to
(2) 27/16 unity. The expression for Kp in terms of 'x' and total
(3) 3/2 pressure P is

(4) 27/64 Px3

(1)
6. 1 mole of NO2 and 2 moles of CO are enclosed in 2
a one litre vessel to attain the following equilibrium
NO2 + CO  NO + CO2. It was estimated that Px2
(2)
at the equilibrium, 25% of initial amount of CO is 3
consumed. The equilibrium constant Kp is
Px3
(1) 1 (3)
3
(2) 1/2
(3) 1/4 Px2
(4)
2
(4) 1/3
12. When ethyl alcohol and acetic acid mixed together
7. In a chemical equilibrium the rate constant of the in equimolecular proportions, equilibrium is attained
backward reaction is 7.5 × 10–4 and the equilibrium when two–third of the acid and alcohol are
constant is 1.5. So the rate constant of the forward consumed. The equilibrium constant of the reaction
reaction is will be
(1) 2 × 10–3 (2) 15 × 10–4 (1) 0.4 (2) 4
(3) 1.125 × 10–3 (4) 9.0 × 10–4 (3) 40 (4) 0.04

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
30 Equilibrium NEET

13. XY2 dissociates as, 19. By the addition of an inert gas to the system
2HI  H2 + I2, the degree of dissociation of HI
XY2(g) XY(g) + Y(g)
will be
Initial pressure of XY2 is 600 mm of Hg. The total
(1) Suppressed (2) Not altered
pressure at equilibrium is 800 mm of Hg. Assuming
volume of system to remain constant, the value of (3) Increased (4) Doubled
Kp is
20. Kc for A(g) + B(g) 3C(g) is 30 at 298 K. If a two
(1) 50 (2) 100
litre vessel contains 1, 2 and 5 moles of A, B and C
(3) 20 (4) 400 respectively, the reaction at 298 K shall
14. Ammonium carbamate dissociates as (1) Proceed from left to right
NH2COONH4(s)  2NH3(g) + CO2(g) (2) Proceed from right to left
In a closed vessel containing ammonium carbamate (3) Be at equilibrium
in equilibrium, ammonia is added such that the
partial pressure of NH3 now equals to the original (4) Can’t be predicted
total pressure. The ratio of total pressure now to
21. In the equilibrium, Ice Water, on increasing
the original pressure is
pressure, melting point of ice
27 31
(1) (2) 27 (1) Decreases
31
(2) Increases
4 5P
(3) (4)
9 9 (3) Remains same
15. By the addition of an inert gas to the system (4) May increase or decrease
PCl5  PCl3 + Cl2 at constant volume the degree 22. Select the species which can act both as an acid
of dissociation of PCl5 will and as a base
(1) Increase (2) Decrease (1) H2SO4 (2) HSO4–
(3) Double (4) Not change (3) H3O+ (4) CO32–
16. Which one of the following equilibrium moves
23. BF3 is
backward when pressure is applied?
(1) Lewis acid (2) Lewis base
(1) N2 (g) + 3H2 (g)  2NH3 (g)
(3) Bronsted acid (4) Arrhenius acid
(2) N2 (g) + O2 (g)  2NO (g)
24. The decreasing order of strength of following bases
(3) Water  Ice
(4) I2 (g)  I2 (s) NH3, CH3COO– and Cl– is

17. When 1 mole of N2 and 1 mole of H2 is enclosed (1) Cl–, CH3COO–, NH3 (2) CH3COO—, NH3, Cl–
in 3L vessel and the reaction is allowed to attain (3) CH3COO–, Cl– , NH3 (4) NH3 , CH3COO–, Cl–
equilibrium, it is found that at equilibrium there is
'x' mole of H2. The number of moles of NH3 formed 25. An example of a salt dissolved in water to give
would be acidic solution is
(1) Ammonium chloride
2x 2(1  x)
(1) (2)
3 3 (2) Sodium acetate

2(1  x) (1  x) (3) Potassium nitrate

(3) (4)
3 2 (4) Barium bromide
18. What is the unit of K for the following equilibria?
26. If 100 ml of 1N H2SO4 were mixed with 100 ml of
2NO(g) + Cl2 (g)  2NOCl (g) 1M NaOH, the solution will be
(1) Mol–1 (2) L mole–1 (1) Acidic (2) Basic
(3) L cm–1 (4) Mol–1 lit–1 (3) Neutral (4) Slightly acidic

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Equilibrium 31
27. At 100°C, K w = 10 –12 . pH of pure water at 35. The solubility product of AgCl is Ksp. Then the
100° C will be solubility of AgCl in x M KCl is
(1) 7.0 (2) 6.0 x
(1) Ksp × x2 (2) K
(3) 8.0 (4) 12.0 sp

28. Calculate the percentage ionization of 0.01 M acetic K sp K sp

acid in 0.1 M HCl K a of acetic acid is (3) 2 (4)
x x
1.8 × 10–5
36. Degree of hydrolysis (h) of a salt of weak acid and
(1) 0.18% (2) 0.018%
a strong base is given by
(3) 1.8% (4) 18%
29. A solution of NaOH contain 0.04 gm of NaOH per (1) h  K h (2) h  K h
litre. Its pH is c
(1) 10 (2) 9 c Kw
(3) h  (4) h 
(3) 11 (4) 12 Kh Kb
30. The number of hydrogen ions in 10 ml of a solution 37. The K SP for a sparingly soluble Ag 2 CrO 4 is
with pH = 13 is 4 × 10–12. The molar solubility of the salt is

(1) 1013 (2) 6.023 × 108 (1) 2.0 × 10–6 mol L–1 (2) 1.0 × 10–4 mol L–1
(3) 6.023 × 1010 (4) 6.023 × 1013 (3) 2.0 × 10–12 mol L–1 (4) 1.0 × 10–15 mol L–1
31. 1 c.c of 0.1 N HCl is added to 1 litre solution of 38. A solution of pH = 2 is more acidic than of
sodium chloride. The pH of the resulting solution pH = 6 by a factor of
will be
(1) 4 (2) 12
(1) 7 (2) 0
(3) 400 (4) 10,000
(3) 10 (4) 4
39. An acidic solution of pH 6 is diluted thousand
32. The following reactions are known to occur in the times. The pH of solution becomes approx
body
(1) 9 (2) 6
CO2 + H2O  H2CO3  H+ + HCO3
(3) 3 (4) 6.96
If CO2 escapes from the system
40. Solubility product of
(1) pH will decrease
(a) MnS is 1.4 × 10–10 (b) ZnS is 1.2 × 10–28
(2) Hydrogen ion concentration will diminish
(c) CdS is 3.6 × 10–28 (d) CuS is 8.5 × 10–36
(3) H2CO3 concentration will be promoted
(4) The forward reaction will be promoted Which of these has maximum solubility?

33. The precipitate of CaF 2 (K sp = 1.7 × 10 –10) is (1) (a) (2) (b)
obtained when equal volumes of the following are (3) (c) (4) (d)
mixed
41. For preparing a buffer of pH = 6 by mixing sodium
(1) 10–4 M Ca2+ + 10–4 M F– acetate and acetic acid the ratio of the
(2) 10–2 M Ca2+ + 10–3 M F– concentration of salt and acid should be (Ka = 10–5)

(3) 10–4 M Ca2+ + 10–3 M F– (1) 1 : 100 (2) 10 : 1

(4) 10–3 M Ca2+ + 10–5 M F– (3) 100 : 1 (4) 1 : 100
34. A monoprotic acid in a 0.1 M solution ionises to 42. The salt whose aqueous solution has highest pH
0.001%. Its ionisation constant is is
(1) 1.0 × 10–3 (2) 1.0 × 10–6 (1) KCl (2) NH4Cl
(3) 1.0 × 10–8 (4) 1.0 × 10–11 (3) (NH4)2CO3 (4) Na2CO3

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
32 Equilibrium NEET

43. In which solution, AgCl has minimum solubility? 7. Which one of the following conditions will favour
(1) 0.01 M NaCl (2) 0.01 M CaCl2 maximum formation of the product in the reaction,

(3) 0.05 M AgNO3 (4) Pure water  X2 (g) r H = –X kJ?

A 2 (g) + B2 (g) 
[NEET-2018]
SECTION - C (1) Low temperature and high pressure
Previous Years Questions (2) Low temperature and low pressure
1. THe pH of 0.01 M NaOH (aq) solution will be (3) High temperature and low pressure

[NEET-2019 (Odisha)] (4) High temperature and high pressure

8. The solubility of BaSO4 in water is 2.42 × 10–3 gL–1 at
(1) 9 (2) 7.01
298 K. The value of its solubility product (Ksp) will
(3) 2 (4) 12 be
2. Which of the following cannot act both as (Given molar mass of BaSO4 = 233 g mol–1)
Bronsted acid and as Bronsted base? [NEET-2018]
[NEET-2019 (Odisha)] (1) 1.08 × 10–10 mol2L–2
(2) 1.08 × 10–12 mol2L–2
(1) HSO4 (2) HCO3
(3) 1.08 × 10–8 mol2L–2
(3) NH3 (4) HCl (4) 1.08 × 10–14 mol2L–2
3. The molar solubility of CaF2(Ksp = 5.3 × 10–11) in 9. Following solutions were prepared by mixing
0.1 M solution of NaF will be different volumes of NaOH and HCl of different
[NEET-2019 (Odisha)] concentrations :

(1) 5.3 × 10–10 mol L–1 (2) 5.3 × 10–11 mol L–1 M M
a. 60 mL HCl + 40 mL NaOH
10 10
(3) 5.3 × 10–8 mol L–1 (4) 5.3 × 10–9 mol L–1
M M
4. pH of a saturated solution of Ca(OH)2 is 9. The b. 55 mL HCl + 45 mL NaOH
solubility product (Ksp) of Ca(OH)2 is: [NEET-2019] 10 10

(1) 0.5 × 10–15 (2) 0.25 × 10–10 M M

c. 75 mL HCl + 25 mL NaOH
5 5
(3) 0.125 × 10–15 (4) 0.5 × 10–10
M M
d. 100 mL HCl + 100 mL NaOH
5.
ii
Conjugate base for Br onsted acids H2O and HF 10 10
are : [NEET-2019] pH of which one of them will be equal to 1?

(1) OH– and H2F+, respectively [NEET-2018]

(1) b (2) a
(2) H3O+ and F–, respectively
(3) c (4) d
(3) OH– and F–, respectively
10. A 20 litre container at 400 K contains CO2(g) at
(4) H3O+ and H2F+, respectively pressure 0.4 atm and an excess of SrO (neglect
6. Which will make basic buffer? [NEET-2019] the volume of solid SrO). The volume of the
containers is now decreased by moving the
(1) 50 mL of 0.1 M NaOH + 25 mL of 0.1 M
movable piston fitted in the container. The
CH3COOH
maximum volume of the container, when pressure
(2) 100 mL of 0.1 M CH3COOH + 100 mL of 0.1 M of CO2 attains its maximum value, will be
NaOH


(Given that : SrCO3(s)  SrO(s) + CO2(g).
(3) 100 mL of 0.1 M HCl + 200 mL of 0.1 M Kp = 1.6 atm) [NEET-2017]
NH4OH (1) 5 litre (2) 10 litre
(4) 100 mL of 0.1 M HCl + 100 mL of 0.1 M NaOH (3) 4 litre (4) 2 litre
Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Equilibrium 33
11. The equilibrium constants of the following are. 17. MY and NY3, two nearly insoluble salts, have the

 same K SP values of 6.2 × 10 –13 at room
N2 + 3H2 
 2NH3 K1
temperature. Which statement would be true in


N2 + O2 
 2NO K2 regard to MY and NY3? [NEET-2016]
(1) The addition of the salt of KY to solution of MY
1
H2  O2  H2O K3 and NY3 will have no effect on their solubilities
2
The equilibrium constant (K) of the reaction: (2) The molar solubilities of MY and NY3 in water
are identical
5 K

2NH3  O2  2NO  3H2O, will be (3) The molar solubility of MY in water is less than
2 that of NY3
[NEET-2017] (4) The salts MY and NY3 are more soluble in
0.5 M KY than in pure water
(1) K1K33 / K2 (2) K2K33 / K1
18. Consider the following liquid-vapour equilibrium.
(3) K2K3 / K1 (4) K32K3 / K1


Liquid 
 Vapour
12. Concentration of the Ag + ions in a saturated
solution of Ag 2 C 2 O 4 is 2.2 × 10 –4 mol L –1 . Which of the following relations is correct?
Solubility product of Ag2C2O4 is [NEET-2017]
[NEET-2016]
(1) 2.42 × 10–8 (2) 2.66 × 10–12
(3) 4.5 × 10–11 (4) 5.3 × 10–12 dlnP Hv dlnG Hv
(1)  (2) 
13. The percentage of pyridine (C5H5N) that forms
dT RT 2 dT 2 RT 2
pyridinium ion (C5H5N+H) in a 0.10 M aqueous
pyridine solution (Kb for C5H5N = 1.7 × 10–9) is dlnP – Hv dlnP – Hv
(3)  (4) 2

dT RT dT T2
[NEET (Phase-2) 2016]
19. If the equilibrium constant for
(1) 0.0060% (2) 0.013%


N2 (g)  O2 (g)  2NO(g) is K, the equilibrium
(3) 0.77% (4) 1.6%
1 1 
14. The solubility of AgCl(s) with solubility product constant for N2 (g)  O2 (g)  NO(g) will
2 2
1.6 × 10–10 in 0.1 M NaCl solution would be be [Re-AIPMT-2015]
[NEET (Phase-2) 2016] (1) K (2) K2
(1) 1.26 × 10–5 M (2) 1.6 × 10–9 M 1
(3) K1/2 (4) K
(3) 1.6 × 10–11 M (4) Zero 2
15. Boric acid is an acid because its molecule 20. Which one of the following pairs of solution is not
an acidic buffer? [Re-AIPMT-2015]
[NEET (Phase-2) 2016]
(1) Contains replaceable H+ ion (1) H2CO3 and Na2CO3

(2) Gives up a proton (2) H3PO4 and Na3PO4

(3) Accepts OH– from water releasing proton (3) HClO4 and NaClO4

(4) Combines with proton from water molecule (4) CH3COOH and CH3COONa
16. Which of the following fluoro-compounds is most 21. What is the pH of the resulting solution when
likely to behave as a Lewis base? equal volumes of 0.1 M NaOH and 0.01 M HCl are
[NEET (Phase-2) 2016] mixed? [Re-AIPMT-2015]

(1) BF3 (2) PF3 (1) 7.0 (2) 1.04

(3) CF4 (4) SiF4 (3) 12.65 (4) 2.0

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
34 Equilibrium NEET

22. Which of the following statements is correct for a 28. For the reversible reaction
reversible process in a state of equilibrium?


N2(g)+3H2(g) 
 2NH3(g) + heat
[AIPMT-2015]
The equilibrium shifts in forward direction
(1) G° = 2.30 RT log K
[AIPMT-2014]
(2) G = –2.30 RT log K
(1) By increasing the concentration of NH3(g)
(3) G = 2.30 RT log K
(2) By decreasing the pressure
(4) G° = –2.30 RT log K
(3) By decreasing the concentrations of N2(g) and
23. The K sp of Ag 2CrO 4, AgCl, AgBr and AgI are
H2(g)
respectively, 1.1 × 10–12, 1.8 × 10–10, 5.0 × 10–13,
8.3 × 10–17. Which one of the following salts will (4) By increasing pressure and decreasing
precipitate last if AgNO3 solution is added to the temperature
solution containing equal moles of NaCl, NaBr, NaI
29. Identify the correct order of solubility in aqueous
and Na2CrO4? [AIPMT-2015]
medium [NEET-2013]
(1) Ag2CrO4 (2) AgI
(1) ZnS > Na2S > CuS
(3) AgCl (4) AgBr
(2) Na2S > CuS > ZnS
24. If the value of an equilibrium constant for a
particular reaction is 1.6 × 1012, then at equilibrium (3) Na2S > ZnS > CuS
the system will contain [AIPMT-2015]
(4) CuS > ZnS > Na2S
(1) Similar amounts of reactants and products
30. KMnO4 can be prepared from K2MnO4 as per the
(2) All reactants reaction,
(3) Mostly reactants 

3MnO24 + 2H2O  
 2MnO4 +MnO2 + 4OH–
(4) Mostly products
The reaction can go to completion by removing
25. Which of the folowing salts will give highest pH in OH – ions by adding [NEET-2013]
water? [AIPMT-2014]
(1) KOH (2) CO2
(1) KCl (2) NaCl
(3) SO2 (4) HCl
(3) Na2CO3 (4) CuSO4
31. Buffer solutions have constant acidity and alkalinity
26. For a given exothermic reaction, Kp and Kp are because [AIPMT (Prelims)-2012]
the equilibrium constants at temperatures T1 and
T2, respectively. Assuming that heat of reaction is (1) They have large excess of H+ or OH– ions
constant in temperature range between T1 and T2,
(2) They have fixed value of pH
it is readily observed that [AIPMT-2014]
(3) These give unionised acid or base on reaction
(1) Kp > Kp (2) Kp < Kp
with added acid or alkali
1
(3) Kp = Kp (4) Kp = (4) Acids and alkalies in these solutions are
K p shielded from attack by other ions
27. Using the Gibbs energy change, G = +63.3 kJ, 32. pH of a saturated solution of Ba(OH)2 is 12. The
for the following reaction, value of solubility product (Ksp) of Ba(OH)2 is

 2
 2Ag+ (aq) + CO3 (aq)
Ag2CO3(s)  [AIPMT (Prelims)-2012]

the Ksp of Ag2CO3(s) in water at 25C is (1) 4.0 × 10–6

(R = 8.314 J K–1 mol–1) [AIPMT-2014] (2) 5.0 × 10–6

(1) 3.2 × 10–26 (2) 8.0 × 10–12 (3) 3.3 × 10–7

(3) 2.9 × 10–3 (4) 7.9 × 10–2 (4) 5.0 × 10–7

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Equilibrium 35
33. Given that the equilibrium constant for the reaction 37. In qualitative analysis, the metals of group  can be
 separated from other ions by precipitating them as
2SO2(g) + O2(g)   2SO3(g), has a value of
chloride salts. A solution initially contains Ag+ and
278 at a particular temperature. What is the value
Pb2+ at a concentration is 0.10 M. Aqueous HCl is
of the equilibirum constant for the following reaction
added to this solution until the Cl– concentration is
at the same temperature ?
0.10 M. What will the concentration of Ag+ and
1 Pb2+ be at equilibrium ?


SO3(g) 
 SO2(g) + 2 O2(g)
(Ksp for AgCl = 1.8×10–10, Ksp for PbCl2 = 1.7×10–5)
[AIPMT (Mains)-2012]
[AIPMT (Mains)-2011]
(1) 1.8 × 10–3 (2) 3.6 × 10–3
(3) 6.0 × 10–2 (4) 1.3 × 10–5 (1) [Ag+] = 1.8 × 10–9 M [Pb2+] = 1.7 × 10–3 M

34. Given the reaction between 2 gases represented by (2) [Ag+] = 1.8 × 10–11 M [Pb2+] = 1.7 × 10–4 M
A2 and B2 to give the compound AB(g). (3) [Ag+] = 1.8 × 10–6 M [Pb2+] = 1.7 × 10–11 M


A2(g) + B2(g) 
 2AB(g) (4) [Ag+] = 1.8 × 10–11 M [Pb2+] = 8.5 × 10–5 M
At equilibrium, the concentration
38. The value of H for the reaction
of A2 = 3.0 × 10–3 M
X2(g) + 4Y2(g)  2XY4 (g)
of B2 = 4.2 × 10–3 M
is less than zero. Formation of XY 4(g) will be
of AB = 2.8 × 10–3 M
favoured at: [AIPMT (Prelims)-2011]
If the reaction takes place in a sealed vessel at
(1) High pressure and low temperature
527C, then the value of Kc will be
[AIPMT (Mains)-2012] (2) High temperature and high pressure

(1) 2.0 (2) 1.9 (3) Low pressure and low temperature

(3) 0.62 (4) 4.5 (4) High temperature and low pressure

35. A buffer solution is prepared in which the 39. In which of the following equilibrium Kc and Kp are
concentration of NH 3 is 0.30 M and the not equal? [AIPMT (Prelims)-2010]
concentration of NH4+ is 0.20 M. If the equilibrium


(1) 2NO(g) 
 N2 (g) + O2 (g)
constant, Kb for NH3 equals 1.8 × 10–5, what is
the pH of this solution? (log 2.7 = 0.43)


(2) SO2 (g) + NO2 (g) 
 SO3 (g) + NO(g)
[AIPMT (Prelims)-2011]
(1) 8.73 (2) 9.08 

(3) H2 (g) + I2 (g) 
 2HI(g)
(3) 9.43 (4) 11.72


(4) 2C(s) + O2 (g) 
 2CO2(g)


36. For the reaction, N2 (g)  O2 (g)  2NO(g) ,
the equilibrium constant is K1. The equilibrium 40. What is [H+] in mol/L of a solution that is 0.20 M
constant is K 2 for the reaction
CH3COONa and 0.10 M in CH3COOH ? (Ka for


2NO(g)  O2 (g) 
 2NO2 (g) . What is K for the CH3COOH = 1.8×10–5) [AIPMT (Prelims)-2010]

 1
 N2 (g)  O2 (g) ?
reaction NO2 (g)  (1) 3.5 × 10–4 (2) 1.1 × 10 –5
2
[AIPMT (Prelims)-2011] (3) 1.8 × 10–5 (4) 9.0 × 10–6

1 1 41. In a buffer solution containing equal concentration

(1) (K K ) (2) (2K K ) of B– and HB, the Kb for B– is 10–10. The pH of
1 2 1 2
buffer solution is [AIPMT (Prelims)-2010]
1/2
1  1  (1) 10 (2) 7
(3) (4)  K K 
(4K1K 2 )  1 2 (3) 6 (4) 4
Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
36 Equilibrium NEET



42. The reaction, 2A(g) + B(g) 
 3C(g) + D(g) 48. The values of KP and KP for the reactions
1 2
is begun with the concentrations of A and B both 

X 
 Y+Z ...(i)
at an initial value of 1.00 M. When equilibrium is
reached, the concentration of D is measured and 

A 
 2B ...(ii)
found to be 0.25 M. The value for the equilibrium are in ratio of 9:1. If degree of dissociation X and
constant for this reaction is given by the A be equal, then total pressure at equilibrium (i)
expression [AIPMT (Mains)-2010] and (ii) are in the ratio [AIPMT (Prelims)-2008]
(1) [(0.75)3(0.25)]  [(1.00)2(1.00)] (1) 1 : 1 (2) 3 : 1
(2) [(0.75)3(0.25)]  [(0.50)2(0.75)] (3) 1 : 9 (4) 36 : 1
(3) [(0.75)3(0.25)]  [(0.50)2(0.25)] 49. If the concentration of OH– ions in the reaction
(4) [(0.75)3(0.25)]  [(0.75)2(0.25)] 

Fe(OH) 3 (s) 
 Fe 3+ (aq) + 3OH – (aq) is
43. The dissociation constants for acetic acid and 1
HCN at 25C are 1.5×10 –5 and 4.5×10 –10 decreased by times, then equilibrium
4
respectively. The equilibrium constant for the
concentration of Fe3+ will increase by

equilibrium, CN–+ CH COOH 
 HCN + CH COO–
3 3 [AIPMT (Prelims)-2008]
would be [AIPMT (Prelims)-2009] (1) 4 times (2) 8 times
(1) 3.0 × 10–5 (2) 3.0 × 10–4 (3) 16 times (4) 64 times
(3) 3.0 × 104 (4) 3.0 × 105 50. The dissociation equilibrium of a gas AB2 can be
44. The ionization constant of ammonium hydroxide is represented as, 2AB2(g)   
 2AB (g) + B2(g).
1.77 × 10 –5 at 298 K. Hydrolysis constant of The degree of dissociation is 'x' and is small
ammonium chloride is [AIPMT (Prelims)-2009] compared to 1. The expression relating the degree
(1) 6.50 × 10–12 (2) 5.65 × 10–13 of dissociation (x) with equilibrium constant KP and
total pressure P is [AIPMT (Prelims)-2008]
(3) 5.65 × 10–12 (4) 5.65 × 10–10
45. What is the [OH–] in the final solution prepared by  KP   2K P 
(1)   (2)  
mixing 20.0 mL of 0.050 M HCl with 30.0 mL of  P   P 
0.10 M Ba(OH)2? [AIPMT (Prelims)-2009] 1/3 1/2
 2K P   2K P 
(1) 0.40 M (2) 0.0050 M (3)   (4)  
 P   P 
(3) 0.12 M (4) 0.10 M
51. Equimolar solutions of the following were prepared
46. The value of equilibrium constant of the reaction in water separately. Which one of the solutions will
record the highest pH? [AIPMT (Prelims)-2008]
1 1


Hl(g) 
 H2 (g)  l2 is 8.0. The equilibrium (1) CaCl2 (2) SrCl2
2 2


constant of the reaction, H2(g) + l2(g)  (3) BaCl2 (4) MgCl2
 2Hl(g)
will be [AIPMT (Prelims)-2008] 52. The following equilibrium constants are given
1 1 N2 + 3H2  2NH3 ; K1
(1) (2)
8 16 N2+ O2  2NO ; K2
1 1
(3) (4) 16 H2 + O  H2O ; K3
64 2 2
47. Equal volumes of three acid solutions of pH–3, 4 The equilibrium constant for the oxidation of NH3 by
and 5 are mixed in a vessel. What will be the H+ oxygen to give NO is [AIPMT (Prelims)-2007]
ion concentration in the mixture?
K1 K 2 K 2 K 33
[AIPMT (Prelims)-2008] (1) K3 (2)
K1
(1) 1.11 × 10–3 M (2) 1.11 × 10–4 M
K 2 K 32 K 22 K 3
(3) 3.7 × 10–4 M (4) 3.7 × 10–3 M (3) (4)
K1 K1
Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Equilibrium 37
53. Calculate the pOH of a solution at 25C that 59. At 25C, the dissociation constant of a base, BOH,
contains 1 × 10–10 M of hydronium ions, i.e. H3O+ is 1.0 × 10–12. The concentration of hydroxyl ions
in 0.01M aqueous solution of the base would be
[AIPMT (Prelims)-2007]
[AIPMT (Prelims)-2005]
(1) 1.000 (2) 7.000
(1) 2.0 × 10–6 mol L–1 (2) 1.0 × 10–5 mol L–1
(3) 4.000 (4) 9.000
(3) 1.0 × 10–6 mol L–1 (4) 1.0 × 10–7 mol L–1
54. A weak acid, HA has a Ka of 1.00 × 10–5. If 0.100
60. Equilibrium constants K1 and K2 for the following
mol of this acid is dissolved in one litre of water,
equilibria:
the percentage of acid dissociated at equilibrium is
closest to [AIPMT (Prelims)-2007] 1 K1
NO(g) + O   NO2(g) and
(1) 0.100% (2) 99.0% 2 2 
K2
(3) 1.00% (4) 99.9% 
2NO2(g)  2NO(g) + O2(g)

55. Which one of the following ionic species has the are related as [AIPMT (Prelims)-2005]
greatest proton affinity to form stable compound ?
1
[AIPMT (Prelims)-2007] (1) K2 = (2) K2 = K12
K1
(1) – (2) HS–
K1 1
(3) K2 = (4) K2 =
(3) NH2– (4) F– 2 K12
56. For the reaction, 61. H 2 S gas when passed through a solution of
cations containing HCl precipitates the cations of


CH4(g) + 2O2(g) 
 CO2(g) + 2H2O(l), second group of qualitative analysis but not those
rH = –170.8 kJ mol–1 belonging to the fourth group. It is because

Which of the following statements is not true ? [AIPMT (Prelims)-2005]

[AIPMT (Prelims)-2006] (1) Presence of HCl decreases the sulphide ion

concentration
(1) At equilibrium, the concentrations of CO2(g)
(2) Presence of HCl increases the sulphide ion
and H2O(l) are not equal
concentration
(2) The equilibrium constant for the reaction is (3) Solubility product of group II sulphides is more

given by Kp =
CO2  than that of group IV sulphides
CH4 O2  (4) Sulphides of group IV cations are unstable in
(3) Addition of CH4(g) or O2(g) at equilibrium will HCl
cause a shift to the right
Questions asked Prior to Medical Ent. Exams. 2005
(4) The reaction is exothermic 62. The dissociation constant of a weak acid is 1 × 10–4.
57. Which of the following pairs constitutes a buffer ? In order of prepare a buffer solution with a pH = 5 the
[Salt]/[Acid] ratio should be
[AIPMT (Prelims)-2006]
(1) 1 : 10 (2) 4 : 5
(1) HNO2 and NaNO2 (2) NaOH and NaCl
(3) 10 : 1 (4) 5 : 4
(3) HNO3 and NH4NO3 (4) HCl and KCl
63. Which one of the following is not acid-base
58. The hydrogen ion concentration of a 10–8 M HCl conjugate pair?
aqueous solution at 298 K (Kw = 10–14) is (1) HONO, NO2–
[AIPMT (Prelims)-2006] (2) CH3NH3+, CH3NH2
(1) 1.0 × 10–6 M (2) 1.0525 × 10–7 M (3) C6H5 – COOH, C6H5COO–

(3) 9.525 × 10–8 M (4) 1.0 × 10–8 M (4) H3O+, OH–

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
38 Equilibrium NEET

64. For the reactions 69. Which one of the following species acts only as a
base?


I2(aq) 
 I2(oil) Equilibrium constant is K1
(1) H2S (2) HS–


I2(oil) 
 I2(ether) Equilibrium constant is K2
(3) S2– (4) H2O
for the reaction
70. At 100°C the Kw of water is 55 times its value at


I2(aq) 
 I2(ether) Equilibrium constant is K3 25°C. What will be the pH of neutral solution?
(log 55 = 1.74)
The relation between K1, K2, K3 is
(1) 6.13 (2) 7.00
(1) K3 = K1 + K2
(3) 7.87 (4) 5.13
(2) K3 = K1K2
71. Which one of the following is most soluble?
(3) K3 = K1/K2
(1) Bi2S3 (Ksp = 1 × 10–70)
(4) K3 = K2/K1
(2) Ag2S (Ksp = 6 × 10–51)
65. Given exothermic reaction
(3) CuS (Ksp = 8 × 10–37)


CoCl24 (aq)  6H2 O(l)  2
 [Co(H2 O)6 ]  4Cl


(4) MnS (Ksp = 7 × 10–16)

Which one of the following will decrease the
equilibrium concentration of CoCl24 ? 72. At 80°C, distilled water has [H3O+] concentration
equal to 1 × 10–6 mole/litre. The value of Kw at this
(1) Addition of HCl temperature will be
(2) Addition of Co(NO3)2 (1) 1 × 10–12 (2) 1 × 10–15
(3) The solution is diluted with water (3) 1 × 10–6 (4) 1 × 10–9
(4) The temperature is increased 73. The pH value of blood does not appreciably change
by a small addition of an acid or a base, because
66. For preparing a buffer solution of pH = 7.0, which
the blood
buffer system you will choose?
(1) Can be easily coagulated
(1) H3PO 4 , H2PO 4– (2) H2PO 4– , HPO2–
4
(2) Contains iron as a part of the molecule
(3) HPO 2– 3–
4 , PO 4
(4) H3PO 4 , PO3–
4 (3) Is a body fluid

67. For a chemical reaction of the type (4) Contains serum protein which acts as buffer

A B, K = 2.0 and B C, K = 0.01 74. The pH value of 10–7 M solution HCl is

Equilibrium constant for the reaction 2C 2A (1) Equal to 1

is (2) Equal to 2
(1) 25 (2) 50 (3) Less than 7
(3) 2500 (4) 4 × 10–4 (4) Equal to 0
68. A solution is 0.1 M with respect to Ag+, Ca2+, Mg2+ 75. Standard state Gibb’s free energy change for
and Al 3+ which will precipitate at lowest isomerization reaction cis-2-pentene trans-2-
concentration of [PO3–4 ]
when solution of Na3PO4 pentene is –3.67 kJ/mol at 400 K. If more
is added? trans-2-pentene is added to the reaction vessel, then
(1) Ag3PO4(Ksp = 1 × 10–6) (1) Equilibrium remains unaffected
(2) Ca3(PO4)2(Ksp = 1 × 10–33) (2) Equilibrium is shifted in the forward direction
(3) Mg3(PO4)2(Ksp = 1 × 10–24) (3) More cis-2-pentene is formed
(4) AlPO4(Ksp = 1 × 10–20) (4) Additional trans-2-pentene is formed

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Equilibrium 39
76. The equilibrium constant for the reaction 82. The concentration of [H+] and concentration of [OH– ]
N2 + 3H 2 2NH 3 is K, then the equilibrium of a 0.1 M aqueous solution of 2% ionised weak acid
constant for the equilibrium 2NH3 N2 + 3H2 is is [ionic product of water = 1 × 10–14]
(1) 2 × 10–3 M and 5 × 10–12 M
1
(1) K (2) (2) 1 × 10–3 M and 3 × 10–11 M
K
(3) 0.02 × 10–3 M and 5 × 10–11 M
1 1
(3) (4) (4) 3 × 10–2 M and 4 × 10–13 M
K K2
83. The values of K sp of CaCO 3 and CaC 2O4 are
77. The ionic product of water at 25°C is 10–14. Its
4.7 × 10–9 and 1.3 × 10–9 respectively at 25°C. If
ionic product at 90°C will be
the mixture of these two is washed with water,
(1) 1 × 10–14 (2) 1 × 10–16 what is the concentration of Ca2+ ions in water?
(3) 1 × 10–20 (4) 1 × 10–12 (1) 7.746 × 10–5 M (2) 5.831 × 10–5 M
78. If  is degree of dissocliation, then the total number (3) 6.856 × 10–5 M (4) 3.606 × 10–5 M
of moles for the reaction starting with 1 mole of HI
2HI = H2 + I2 will be 84. The solubility of a saturated solution of calcium
fluoride is 2 × 10–4 moles per litre. Its solubility
(1) 1 (2) 1 –  product is
(3) 2 (4) 2 –  (1) 22 × 10–11 (2) 14 × 10–4
79. Which of the following is not a Lewis acid? (3) 2 × 10–2 (4) 32 × 10–12
(1) SiF4 (2) C2H4 85. Equilibrium constant Kp for following reaction
(3) BF3 (4) FeCl3
MgCO3(s) MgO(s) + CO2(g)
80. The solubility product of CuS, Ag2S and HgS are
10–31, 10–44, 10–54 respectively. The solubilities of (1) K p  PCO
2
these sulphides are in the order
(1) HgS > Ag2S > CuS PCO2  PMgO
(2) K p  PCO2 
(2) CuS > Ag2S > HgS PMgCO3

(3) Ag2S > CuS > HgS

PCO2  PMgO
(4) AgS > HgS > CuS (3) K p 
PMgCO3
81. If K 1 and K 2 are the respective equilibrium
constants for the two reactions,
PMgCO3
XeF6(g) + H2O(g) XeOF4(g) + 2HF(g) (4) K p 
PCO2  PMgO
XeO4(g) + XeF6(g) XeOF4(g) + XeO3F2(g).
The equilibrium constant of the reaction, 86. Correct relation between dissociation constants of
a di-basic acid
XeO4(g) + 2HF(g) XeO3F2(g) + H2O(g), will be
(1) K a1  K a2 (2) K a1  K a2
K1
(1) K 1
2 (3) K a1  K a2 (4) K a1 
K a2
(2) K1 · K2
87. Conjugate acid of NH2–
K1
(3) (1) NH4OH
(K 2 )2
(2) NH4+
K2 (3) NH2–
(4)
K1 (4) NH3

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
40 Equilibrium NEET

88. Which statement is wrong about pH? 94. The solubility product of AgI at 25°C is
(1) pH of pure water is not zero 1.0 × 10–16 mol2 L–2. The solubility of AgI in 10–4 M
solution of KI at 25ºC is approximately (in mol L–1)
(2) Adding 1 N, solution of CH3COOH and 1 N
NaOH pH will be seven (1) 1.0 × 10–16

(3) pH of dilute and hot H2SO4 is less than 7 (2) 1.0 × 10–12

(4) Mixing solution of CH3COOH and HCl, pH will (3) 1.0 × 10–10
be less than 7 (4) 1.0 × 10–8
89. In HS–, I–, R – NH2, NH3 order of proton accepting 95. The solubility product of a sparingly soluble salt
tendency will be AX2 is 3.2 × 10–11. Its solubility (in moles/litre) is
(1) I– > NH3 > R – NH2 > HS– (1) 5.6 × 10–6
(2) NH3 > R – NH2 > HS– > I– (2) 3.1 ×10–4
(3) R – NH2 > NH3 > HS– > I– (3) 2 × 10–4
(4) HS– > R – NH2 > NH3 > I– (4) 4 × 10–4
90. Ionisation constant of CH3COOH is 1.7 × 10–5 and 96. The rapid change of pH near the stoichiometric point
concentration of H+ ions is 3.4 × 10–4. Then find of an acid-base titration is the basis of indicator
out initial concentration of CH3COOH molecules detection. pH of the solution is related to ratio of the
concentration of the conjugate acid (HIn) and base
(1) 3.4 × 10–4
(In–) forms of the indicator by the expression
(2) 3.4 × 10–3
(3) 6.8 × 10–4 [ln – ]
(1) log  pK ln  pH
(4) 6.8 × 10–3 [HIn]

91. Solution of 0.1 N NH4OH and 0.1 N NH4Cl has

[Hln]
pH 9.25. Then find out pKb of NH4OH (2) log  pK ln  pH
[In – ]
(1) 9.25
(2) 4.75 [Hln]
(3) log  pH  pK ln
(3) 3.75 [In – ]
(4) 8.25
92. Which one of the following compounds is not a [ln – ]
(4) log  pH  pK ln
protonic acid? [HIn]
(1) B(OH)3 97. What is the correct relationship between the pHs
(2) PO(OH)3 of isomolar solutions of sodium oxide (pH 1),
sodium sulphide (pH2), sodium selenide (pH3) and
(3) SO(OH)2
sodium telluride (pH4)?
(4) SO2(OH)2
(1) pH1 > pH2 > pH3 > pH4
93. The reaction quotient (Q) for the reaction
(2) pH1 > pH2  pH3 > pH4
N 2 (g) + 3H 2 (g) 2NH 3 (g) is given by
(3) pH1 < pH2 < pH3 < pH4
[NH3 ] 2
Q . The reaction will proceed from (4) pH1 < pH2 < pH3  pH4
[N 2 ][H 2 ] 3
98. Which of the following molecules acts as a Lewis
right to left if acid?
(1) Q = Kc (1) (CH3)3 N
(2) Q < Kc (2) (CH3)3 B
(3) Q > Kc (3) (CH3)2 O
(4) Q = 0 (4) (CH3)3 P

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Equilibrium 41
4. If pressure applied on the following reaction
SECTION - D
becomes four times H2 (g) + I2 (g)  2HI(g) then
NEET Booster Questions
1. Which of the following graph may be correct for (1) Reaction moves forward
A B? (2) Reaction moves backward
(3) No change
A
(4) Can’t be predicted
(1) Conc.
5. pH of an acidic buffer solution is 5.74 and
Time pK a (CH 3 COOH) = 4.74 then the ratio of
B
[Salt]/[Acid] will be
(1) 10
A
(2) 20
(2) Conc.
(3) 30
B Time (4) 40
6. pH of which salt is same for 1 M and 5 M solution
A both?
(1) HCOONa
Conc.
(3)
(2) C6H5NH3+Cl
B Time

(3) NH4CN
(4) All of these
(4) NaCN
2. For the following reaction,
7. NH4OH is highly soluble in
Ag2SO4 (s)  2Ag+ (aq) + SO24 (aq) (1) CuSO4 (aq)

more SO24 can be produced by (2) AgNO3(aq)

(3) NH4Cl
(1) Adding Na2SO4
(4) Both (1) & (2)
(2) Adding NH3
8. If the value of Ka of 1 M HCN is 10–5 then its degree
(3) Adding AgNO3
of dissociation in 0.1 M HCl will be ( < < < 1)
(4) Adding K2SO4
(1) 10–5
3. For two reactions in equilibrium in same container
(2) 10–4
(i) A(s)  2B(g) + C(g); (K p )1 = 27 atm3 (3) 10–3
(4) 10–2
3
(ii) D(s)  2B(g) + E(g); (K p )2 = 81 atm
9. Which of the following salt will have pH less than
Pressure of B(g) at equilibrium will be 7 when dissolved in water?

(1) 6 atm (1) CuSO4

(2) 3 atm (2) K2CO3

(3) 5 atm (3) Na3PO4

(4) 9 atm (4) KCN

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
42 Equilibrium NEET

10. For 15. Vapour density of PCl5 at 400 K is found to be 90.

Degree of dissociation of PCl5 will be
(i) A + B  C; K C = K1
(1) 15.8% (2) 13.6%
(ii) 2C  D; K C = K 2 . (3) 14.25% (4) 90%

Then the value of KC for 2D + A + B  5C will 16. Correct basic strength order will be
be (1) HSO4– < ClO4– < NO3– < NH3
(2) ClO4– < HSO4– < NO3– < NH3
K 22 K1
(1) (2)
K1 K22 (3) ClO4  HSO4  NO3  NH3

K1 1
(3) (4) (4) NO3  ClO4  NH3  HSO4
K2 K1K 22
17. In 10 ml of pH = 4 HCl solution 990 ml of 0.2 M
11. Kp for the equation A(s)  B(g) + C(g) + D(s) is NaCl solution is added the pH of resulting solution
9 atm2. Then the total pressure at equilibrium will will be
be (1) pH = 5 (2) pH = 5.5
(1) 3 atm (2) 9 atm (3) pH = 6 (4) pH = 4
(3) 6 atm (4) 12 atm 18. For the gaseous reaction
12. In the equilibirum mixture A(g) + 2B(g) 2C(g) + D(g),

CaCO3(s)  
 CaO(s) + CO2(g). Pressure of Initial concentration of B was 1.5 times of A. At
CO2(g) at 27°C is 2 atm. What will be the pressure equilibrium concentration of A and C is equal. The
of CO2(g) when 2 moles of CO2 are added into value of Kp will be
equilibirum mixture? (1) 0.32 (2) 0.64
(1) 4 atm (2) 2 atm (3) 6 (4) 8
(3) 6 atm (4) 5 atm 19. Buffer capacity of buffer containing acid with
pKa = 4.75 will be highest when its pH is equal to
13. 1 mol of HI converts into H2 and I2 at 400 K. Value
(1) 6 (2) 4.75
2
of K p will be, if rd of HI left at gaseous (3) 5 (4) 8
3
20. On adding 0.1 M solution each of Ag, Ba2+, Ca2+
equilibrium 2HI  H2  I2 ions in a Na 2 SO 4 solution, species first
precipitated will be (Given Ksp of BaSO4 = 10–11,
1 1 Ksp of CaSO4 = 10–6, Ksp of Ag2SO4 = 10–5)
(1) (2)
4 2
(1) Ag2SO4
1 (2) BaSO4
(3) (4) 1
16
(3) CaSO4
14. Consider the following statements
(4) All will precipitate simultaneously
(i) Melting point of ice decreases on increasing
21. Correct statement(s) among the following is/are
pressure
(a) Solubility of CaF2 increases in acidic medium
(ii) Melting point of Fe increases on increasing
pressure (b) pH of CH 3COONH 4 is independent of salt
concentration
(iii) Increasing pressure will increase the boiling
point of liquid (c) Buffer action of blood is due to H2CO3 and

Correct statement(s) among the following is/are HCO3 ion

(1) (i) only (2) (i), (ii) & (iii) (1) (a) & (b) (2) (a) & (c)
(3) (ii) only (4) (iii) only (3) (a), (b) & (c) (4) (a) only

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Equilibrium 43
22. If new equilibrium concentration of OH– in the 28. Ammonium carbamate dissociates as
following reaction NH2COONH4(s) 2NH3(g) + CO2(g)
Fe(OH)3(s) Fe3+(aq) + 3OH– (aq) is increased In a closed vessel containing ammonium carbamate
by 4 times, then equilibrium concentration of Fe3+ in equilibrium, ammonia is added such that the
ion will decrease by partial pressure of NH3 now equals to the original
(1) 8 times total pressure. The ratio of total pressure now to the
original pressure is
(2) 16 times
(3) 64 times 27 31
(1) (2) 27
(4) 4 times 31

23. Which of the following will act as buffer? 4 5

(3) (4)
(1) H2CO3 + Na2CO3 (2) Borax + Boric acid 9 9
(3) NH4Cl + NH4OH (4) All of these 29. When 1 mole of N2 and 1 mole of H2 is enclosed
24. The pH at which Ni(OH)2 begins to precipitate from in 3 L vessel and the reaction is allowed to attain
a solution containing 10–3M Ni2+ ions. equilibrium, it is found that at equilibrium there is
'x' mole of H2. The number of moles of NH3 formed
[Ksp of Ni(OH)2 = 10–11]
would be
(1) pH = 3 (2) pH = 10
2x
(3) pH = 13 (4) pH = 11 (1)
3
25. In what volume ratio NH4Cl and NH4OH having 1 M
concentration should be mixed to get a buffer 2(1  x)
(2)
solution of pH = 9.26? (pKb of NH4OH = 4.74) 3
(1) 1 : 2.5 (2) 2.5 : 1
2(1  x)
(3) 1 : 1 (4) 3.5 : 1 (3)
3
26. The equilibrium constant K C for the following
reaction will be (1  x)
(4)
2
K2CO3(aq) + BaSO4(s) BaCO3(s)+ K2SO4(aq)
30. 1 mole of 'A', 1.5 mole of 'B' and 2 mole of 'C' are
taken in a vessel of volume one litre. At equilibrium
[CO32– ] [K 2CO3 ]2 concentration of C is 0.5 mole/L. Equilibrium
(1) (2)
[SO2–
4 ] [K 2SO4 ] constant for the reaction, A(g) + B(g) C(g) is
(1) 0.66
[BaSO4 ] [SO 24– ]
(3) (4) (2) 0.066
[CO32– ]2 [CO 32 – ]
(3) 66
27. At temperature T, a compound AB2(g) dissociates (4) 6.6
according to the reaction,


31. N2  3H2 
 2NH3 ; K c  1.2
2AB2(g) 2AB(g) + B2(g) with a degree of
dissociation 'x' which is small as compared to At the start of a reaction, there are 0.249 mol N2,
unity. The expression for Kp in terms of 'x' and total 3.21 × 10–2 mol H2 and 6.42 × 10–4 mol NH3 in a
pressure P is 3.50 L reaction vessel at 375°C. Hence reaction
will proceed in
Px 3 Px 2 (1) Forward direction
(1) (2)
2 3 (2) Backward direction
3 2 (3) At equilibrium
Px Px
(3) (4)
3 2 (4) Stops

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
44 Equilibrium NEET

32. Solid ammonium carbamate dissociated according 37. Following three gaseous equilibrium reactions are
to the given reaction occurring at 27°C


 A; 2CO + O2 2CO2
 2NH3 (g)  CO2 (g)
NH2COONH4 (s) 

Total pressure of the gases in equilibrium is 5 atm. B; PCl5 PCl3 + Cl2

Hence Kp is
C; 2HI H2 + I2
(1) 18.5
(2) 25 KP
The correct order of K for the following
(3) 1/ 5 C

(4) 12.5 reactions is

33. 1.1 mole of A is mixed with 1.2 mol of B and the (1) A < C < B (2) A < B < C
mixture is kept in a 1 L flask till the equilibrium (3) C < B < A (4) B < C < A


A  2B 
 2C  D is reached. At equilibrium 

38. C(s)  H2 O(g) 
 CO(g)  H2 (g); H  0 .
0.1 mol of D is formed. The Kc of the reaction is
The above equilibrium will proceed in forward
(1) 0.002 (2) 0.004
direction when
(3) 0.001 (4) 0.003
(1) It is subjected to high pressure


 SO2 (g)  Cl2 (g)
34. In the equilibrium SO2 Cl2 (g)  (2) It is subjected to high temperature
at 2000 K and 10 atm pressure, % Cl2 = % SO2 (3) Inert gas (Argon) is added at constant pressure
= 40 (by volume). Then correct option is
(4) Carbon (solid) is added
(1) Kc = 0.1 mol L–1
39. Le-Chatelier's principle is not applicable to
n(SO2Cl2 ) 1
(2)  at equilibrium (1) 

Fe(s)  S(s) 
 FeS(s)
n(SO2 ) 4

(3) n(SO2Cl2) = n(SO2) = n(Cl2) (2) 


H2 (g)  I2 (g) 
 2HI(g)
(4) Kp = 8 atm
(3) 

N2 (g)  3H2 (g) 
 2NH3 (g)


35. For the reaction, N2 (g)  O2 (g) 
 2NO(g)
(4) 

N2 (g)  O2 (g) 
 2NO(g)
Equilibrium constant Kc = 2.
Degree of association is 40. Which causes the change in the value of
equilibrium constant of any equilibria?
1 1 (1) Adding of inert gas at constant pressure
(1) (2)
1 2 1 2
(2) Increasing the pressure

2 2 (3) Adding of inert gas at constant volume

(3) (4)
1 2 1 2 (4) Decreasing the temperature

36. The value of Kp for the reaction, 41. The equilibrium constants for A2 (g) 2A (g)
at 400 K and 600 K are 1 × 10–8 and 1 × 10–2
2SO2(g) + O2(g) 2SO3(g) is 5.
respectively. The reaction is
What will be the partial pressure of O 2 at
(1) Exothermic
equilibrium when equal moles of SO2 and SO3 are
present at equilibrium? (2) Endothermic

(1) 0.5 (2) 0.3 (3) May be exothermic or endothermic

(3) 0.2 (4) 0.1 (4) No heat is evolved or abosorbed

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Equilibrium 45
42. The number of hydrogen ions in 10 ml of a solution 49. The pH of a mixture of 100 ml 1M H2SO4 and 200
with pH = 13 is ml 1N NaOH at 25°C is
(1) 1013 (1) More than 7 (2) Less than 7
(2) 6.023 × 108 (3) Equal to 7 (4) Can’t predict
(3) 6.023 × 1010 50. The pH of a mixture of 0.01M HCl and 0.1M
(4) 6.023 × 1013 CH3COOH is approximately
43. In the following reaction (1) 1 (2) 2
(3) 4 (4) 7
HC2 O 4  PO34 

 2 2
 HPO 4  C2O 4
51. Two samples of CH3COOH each of 10 g were
which pair can act as Bronsted bases only? taken separately in two vessels containing water of
(1) HC2O4– and PO43– (2) HPO42– and C2O42– 6 litre and 12 litre respectively at 27°C. The degree
of dissociation of CH3COOH will be
(3) HC2O4– and HPO42– (4) PO43– and C2O42–
(1) More in 12 litre vessel
44. Which of the following solutions will have pH close
to 1? (2) More in 6 litre vessel

M M (3) Equal in both vessels

(1) 100 ml, HCl  100 ml, NaOH
5 5 (4) Half in 6 litre vessel than in 12 litre vessel

M M 52. Which is incorrect?

(2) 55 ml, HCl  45 ml, NaOH
10 10 (1) Conjugate acid of H2O is H3O+
(2) Conjugate base of HCO3– is CO32–
M M
(3) 10 ml, HCl  90 ml, NaOH
10 10 (3) Conjugate base of NH3 is NH2
(4) Conjugate base of HOCl is Cl–
M M
(4) 75 ml, HCl  25 ml, NaOH
5 5 53. When a small amount of HCl is added to a buffer
solution of acetic acid and sodium acetate
45. If ionic product of water is Kw = 10–16 at 4°C, then
a solution with pH = 7.5 at 4°C will (1) pH Increases

(1) Turn blue litmus red (2) Turn red litmus blue (2) [H+] decreases

(3) Be neutral to litmus (4) Be alkaline (3) Dissociation of acetic acid decreases

46. The pH of 10–11 M HCl at 25°C is (4) [CH3COO–] increases

(1) 11 54. A buffer solution can be obtained from
(2) 3 (1) HCN and KCN (2) CH3COONH4
(3) Slightly greater than 7 (3) NH4Cl and NH4OH (4) All of these
(4) Slightly less than 7 55. At 30°C, the solubility of Ag2CO3 (Ksp = 8 × 10–12)
47. When equal volumes of pH = 4 and pH = 6 are would be maximum in 1 litre of
mixed together then the pH of the resulting solution (1) 0.05 M Na2CO3 (2) 0.05 M AgNO3
will be [log 5 = 0.7]
(3) Pure water (4) 0.05 M NH3
(1) 4.3 (2) 4.7
56. Silver nitrate is gradually added to an aqueous
(3) 5 (4) 5.3 solution containing 0.01 M each of chloride,
bromide and iodide ions. The correct sequence
M (decreasing order) in which the halides will be
48. The pH of Ca(OH)2 is
100 precipitated is
(1) 1.699 (2) 12 (1) Br–, Cl–, I– (2) I–, Cl–, Br–
(3) 12.301 (4) 12.699 (3) I–, Br–, Cl– (4) Cl–, Br–, I–

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
46 Equilibrium NEET

57. The solubility product of AgBr is 4.9 × 10–9. The 59. The solubility product of BaSO4 is 4 × 10–10. The
solubility of AgBr will be solubility of BaSO4 in presence of 0.02 N H2SO4
(1) 7 × 10–4 mole/litre will be

(2) 7 × 10–5 g/litre (1) 4 × 10–8 M (2) 2 × 10–8 M

(3) 1.316 × 10–2 g/litre (3) 2 × 10–5 M (4) 2 × 10–4 M

(4) 1 × 10–3 mole/litre 60. Solubility product of the salt, A x B y will be
represented most suitably, if the solubility is
58. In which of the following solution, AgCl has
represented by s
minimum solubility?
(1) 0.05 M AgNO3 (1) Ksp = xyyx(s)x×y

(2) 0.01 M CaCl2 (2) Ksp = xy + yx + sx+y

(3) 0.01 M NaCl (3) Ksp = xxyy(s)x+y

(4) 0.01 M NH4OH (4) Ksp = x·sx+y·y

‰‰‰

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
Chapter 8

Redox Reactions
Chapter Contents
z Oxidation and Reduction OXIDATION AND REDUCTION REACTIONS
Reactions
Oxidation Reduction
z Disproportionation Reaction
(i) Loss of electron (i) Gain of electron
– –
z The Paradox of Fractional 2+ 3+
e.g., Fe  Fe + e
–
e.g., Cl2 + 2e  2Cl
Oxidation States (ii) Loss of hydrogen (ii) Gain of hydrogen
z Balancing of Redox Reactions (iii) Gain of oxygen (iii) Loss of oxygen
(iv) Gain of electronegative element (iv) Loss of electronegative element
z Redox Reactions as the Basis OR OR
of Titrations Loss of electropositive element Gain of electropositive element
z Redox Reactions and z Redox reaction
Electrode Processes The reaction in which oxidation as well as reduction takes place
together is known as redox reaction.
z Oxidising agent or oxidant
The substance which oxidises others and themself get reduced.
z Reducing agent or reductant
The substance which reduces others and themself get oxidised.
e.g., Reduction

2+ 2+
Zn(s) + Cu (aq) Zn (aq) + Cu

Oxidation
In the above redox reaction Zn is acting as reducing agent and Cu2+ as
oxidising agent.
Oxidation

Fe2O3 + 2Al Al2O3 + 2Fe

(Oxidising (Reducing
agent) agent)

Reduction
Reduction

+ –2
4Na + O2 2Na2O
(Reducing (Oxidising
agent) agent)

Oxidation

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
48 Redox Reactions NEET

z Rules to determine oxidation state

(1) In uncombined state or free state, oxidation number of an element is zero (H2, O2, Cu, Zn, S).
(2) In combined state, oxidation number of .......
(i) F is always –1.

1
(ii) O is –2, in peroxide (–O–O–) it is –1, in superoxide it is  . However in F2O it is +2.
2
(iii) H is +1, in ionic hydrides it is – 1.
(iv) Metal is positive.
(v) Alkali metal (Li, Na, K, Rb, Cs, Fr) is always +1.
(vi) Alkaline earth metal (Be, Mg, Ca, Sr, Ba, Ra) is always +2.
(vii) Halogen in halides is –1, sulphur in sulphides is –2.
(3) The sum of oxidation number of all the atoms of a neutral molecule is equal to zero.
(4) For ionic species sum is equal to total cationic or anionic charge.
Note : Oxidation number of some of the atoms is determined by their structure.
e.g., Compound Structure Oxidation state
O
O O
(i) CrO5 Cr +6
O O
O

(ii) H2 SO5 H—O—S—O—O—H +6

O
O O

(iii) H2 S2O8 H—O—S—O—O—S—O—H +6

O O

OCl
(iv) CaOCl2 +1 and –1
Ca
Cl
(v) NOCl NO+Cl– +3

DISPROPORTIONATION REACTION
A reaction in which the atom of same element is simultaneously oxidised as well as reduced is called
disproportionation reaction.
Phosphorus, sulphur and halogens (X = Cl, Br, I) undergoes disproportionation reactions in alkaline medium
as shown below.
0 – –3 +1 –
(i) P4 + 3OH (aq) + 3H 2O PH3 + 3H 2PO 2

0 +2
– –2 2–
(ii) S8 + 12OH (aq) 4S + 2S2O3 + 6H2O
– – –
(iii) X2 + 2OH (aq) XO + X + H2O

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Redox Reactions 49

Example 1 : Calculate the oxidation number of N in (NH4 )2SO4 molecule.

Solution : Let the oxidation number of N in (NH4)2SO4 molecule is x.
Now,
2x + (+1 × 8) + 6 + (–2 × 4) = 0
2x + 8 + 6 – 8 = 0

x  3

Example 2 : Calculate the oxidation number of Mn in KMnO4 molecule.

Solution : KMnO4
+1 + x – 2 × 4 = 0

x  7

Example 3 : Identify the species undergoing oxidation & reduction and oxidising agent & reducing agent in the
reaction.
I2(g) + H2S(g)  2HI(g) + S(s)

Oxidation

0 –2 –1 0
Solution : I2 + H2S 2HI + S
Oxidising Reducing
agent agent

Reduction

Example 4 : Justify that the reaction is a redox reaction.

2Cu2O(s) + Cu2S(s)  6Cu(s) + SO2(g)

Oxidation

+1 0 +4
–2
Solution : 2Cu2O + Cu2S 6Cu + SO2

Reduction

In this reaction oxidation and reduction both take place together. So, above reaction is redox
reaction.

THE PARADOX OF FRACTIONAL OXIDATION STATES

In certain compounds, the oxidation number of a particular element is in fraction and it is not a whole number.
The concept of fractional oxidation numbers or oxidation states is quite difficult to digest because we know
that the electrons are neither shared nor transferred in fractions. When we analyse the structure of such
species, we find that the atoms of the same element are involved in different bonding in these species. Though
their actual oxidation states or numbers are whole numbers, but an average of these is fractional. The actual
oxidation number of elements in compounds can be determined on the basis of the bonds present in their
molecules. For example,

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
50 Redox Reactions NEET

(i) Carbon Suboxide (C3O2):

2 2 0 2 2
OCCCO
In C3O2, the oxidation number of two ‘C’ atoms in terminal position is +2 while that of the atom present
in the centre is zero.

(2  2  0) 4
The average oxidation number of carbon atoms is 
3 3
(ii) Tetrathionate ion (S4O6–2):
–2 –2
O O
– +5 0 0 +5 –
O S S S S O

O–2 O–2
InS4O6–2 ion, the oxidation number of two terminal sulphur atoms is +5 while that of the other two
sulphur atoms present in the centre is 0. The average oxidation number of sulphur atom in the ion is
(5 + 5 + 0 + 0)
= 2.5.
4
(iii) Tribromooctaoxide (Br3O8):
–2 –2 –2
O O O
–2 –2
O Br+6 Br+4 Br+6 O

O O O
–2 –2 –2

Similarly, in Br3O8, the oxidation number of two bromine atoms in the terminal position is +6 while that of
(6  6  4) 16
the third one atom is +4. The average oxidation number of bromine atom is  . From the
3 3
examples that we have considered, it becomes quite clear that fractional oxidation number of a particular
element can be calculated only if we know about the structure of the compound/ion in which it is present.

Example 5 : Which one of the two, ClO2– or ClO4– shows disproportionation reaction and why?
Solution : The oxidation state of Cl in ClO2– is +3. So, chlorine can get oxidised as well as reduced and
can act as reductant and oxidant both.
The disproportionation reaction of ClO2– is
+3 +5
– – –
3ClO 2 Cl + ClO 3
In ClO4 , Cl is in its highest oxidation state, so it can only be an oxidant.

EXERCISE

1. Oxidation state of nitrogen in H—N C is

(1) – 4 (2) + 3
(3) – 3 (4) – 2
2. The pair of compounds in which both the metals are in the highest possible oxidation state is
(1) FeSO4, CuS2 (2) CrO2Cl2, MnO4–
(3) TiO2, MnO2 (4) [Co(CN)6]3–, MnO42–

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Redox Reactions 51
3. When ethane is burnt in excess of oxygen, the oxidation number of carbon changes by
(1) +8 (2) +7
(3) +3 (4) +4
4. The oxidation state of oxygen in the following reaction changes, K + O2  KO2
(1) From 0  –1 (2) From 0  –2
1
(3) From 0   (4) From 0  +1
2
5. The number of electrons involved when 1 mole of H2O2 decomposes as
H2O2  H2O + O2, is
(1) 1 (2) 8
(3) 6 (4) 4
6. Which of the following elements never show positive oxidation number?
(1) O (2) Fe
(3) Ga (4) F
7. When SO2 is passed in acidified K2Cr2O7 solution oxidation state of S changed from
(1) +4 to 0 (2) +4 to +2

(3) +4 to +6 (4) +6 to +4

BALANCING OF REDOX REACTIONS

1. Oxidation number method

The various steps involved in the balancing of redox equations by oxidation number method are
Step-1 : Write the skeleton equation of all the reactants and products of the reaction.
Step-2 : Indicate the oxidation number of each element above its symbol and identify the elements which
undergo a change in the oxidation number.
Step-3 : Calculate the increase or decrease in oxidation number per atom and identify the oxidising and
reducing agents.
If more than one atom of the same element is involved, find out the total increase or decrease in
oxidation number by multiplying this increase or decrease in oxidation number per atom by the
number of atoms undergoing that change.
Step-4 : Multiply the formulae of the oxidising and the reducing agents by suitable integers so as to equalise
the total increase or decrease in oxidation number as calculated in Step-3.
Step-5 : Balance all atoms other than ‘H’ and ‘O’.
Step-6 : Finally balance ‘O’ by adding H2O molecules using hit and trial method.
Step-7 : In case of ionic reactions
(a) For acidic medium :
First balance O atoms by adding H2O molecules to the side deficient in O atoms and then
balance H-atoms by adding H+ ions to the side deficient in H atoms.
(b) For basic medium :
First balance O atoms by adding H2O molecules to whatever side deficient in O atoms. The H
atoms are then balanced by adding H2O molecules equal in number to the deficiency of H atoms
and an equal number of OH– ions are added to the opposite side of the equations. Remove the
duplication, if any

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
52 Redox Reactions NEET

Example 6 : Balance the equation

Mg + HNO3  Mg(NO3)2 + N2O + H2O
0 +5 +2 +5 +1
Solution : Step-1, 2 : Mg + HNO3 Mg(NO3)2 + N2O + H2O
O.N. decreases by 4 unit
(Hence total change in O.N. = 4 × 2)

0 +5 +2 +1
Step-3 : Mg + HNO3 Mg(NO3)2 + N2O + H2O

O.N. increases by 2
Step-4 : Mg equation is multiplied by 4 and HNO3 equation is multiplied by 2. Now,
4Mg + 2HNO3  4Mg(NO3)2 + N2O + H2O
Step-5 : Balance all atoms other than O and H.
4Mg + 10HNO3  4Mg(NO3)2 + N2O + H2O
Step-6 : Balance H and O by adding H2O molecules
4Mg + 10HNO3  4Mg(NO3)2 + N2O + 5H2O

Example 7 : Balance the ionic equation

Fe2+ + Cr2O72– + H+  Fe3+ + Cr 3+ + H2O
O.N. decreases by 3 × 2 = 6

2+ +6 2– 3+ 3+
Solution : Step-1, 2 : Fe + Cr2O7 Fe + Cr

O.N. increases by 1
Fe equation multiplied with 6 and Cr2O7–2 equation multiplied with 1.
+6
2+ 2– 3+ 3+
6Fe + Cr2O7 6Fe + 2Cr
Balance all the atoms other than O and H.
2+ 2– 3+ 3+
6Fe + Cr2O7 6Fe + 2Cr
Balance the O by adding H2O molecule.
2+ 2– 3+ 3+
6Fe + Cr2O7 + 14H + 6Fe + 2Cr + 7H2O

Example 8 : Balance the ionic equation in alkaline medium

Cr(OH)3 + IO3–  I – + CrO42–
Decreases by 6

+3 +5 – – +6 2–
Solution : Cr(OH)3 + IO3 I + CrO4

Increases by 3

2Cr(OH)3 + IO3–  I– + 2CrO42–

Balancing of O and H
2Cr(OH)3 + IO3– + 4OH–  I– + 2CrO42– + H2O + 4H2O
Now,
2Cr(OH)3 + IO3– + 4OH–  I– + 2CrO42– + 5H2O

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Redox Reactions 53
2. Balancing Equation by Ion Electron Method
Step-1 : Write the skeleton equation and indicate the oxidation number of all the elements which appear in
the skeletal equation above their respective symbols.
Step-2 : Find out the species which are oxidised and which are reduced.
Step-3 : Split the skeleton equation into two half reactions, i.e., oxidation half reaction and reduction half
reaction.
Step-4 : Balance the two half reaction equations separately by the rules described below
(i) In each half reaction, 1st balance the atoms of the elements which have undergone a change
in oxidation number.
(ii) Add electrons to whatever side is necessary to make up the difference in oxidation number in
each half reaction.
(iii) Balance oxygen atoms by adding required number of H2O molecules to the side deficient in O
atoms.
(iv) In the acidic medium, H atoms are balanced by adding H+ ions to the side deficient in H-atoms.
However, in the basic medium, H atoms are balanced by adding H2O molecules equal in number
to the deficiency of H atoms and an equal number OH– ions are included in the opposite side
of the equation. Remove the duplication if any.
Step-5 : The two half reactions are then multiplied by suitable integers so that the total number of electrons
gained in one half of the reaction is equal to the number of electrons lost in the other half reaction.
The two half reactions are then added up. These rules are illustrated by the following examples.
Step-6 : (Verification) : To verify whether the equation thus obtained is balanced or not, the total charge on
either side of the equation must be equal.

Example 9 : Balance the redox reaction by half reaction method

Br2 + H2O2  BrO3– + H2O (in acidic medium)
Reduction

0 +1 –1 +5
– –2
Solution : (i) Br 2 + H2O 2 BrO3 + H2O

Oxidation
(ii) Br2  2BrO3– (Oxidation half)
H2O2  2H2O (Reduction half)
Oxidation half
Br2  2BrO3– + 10e–
Br2 + 6H2O  2BrO3– + 10e– (Balancing oxygen)
Br2 + 6H2O  2BrO3– + 10e– + 12H+ (Balancing hydrogen)
Reduction half
H2O2  H2O
H2O2 + 2e–  2H2O (Balancing charge and oxygen)
H2O2 + 2e– + 2H+  2H2O (Balancing hydrogen)
Balancing total charge
(iii) [Br2 + 6H2O  2BrO3– + 12H+ + 10e–] × 1
[H2O2 + 2H+ + 2e–  2H2O] × 5
(iv) Br2 + 5H2O2 + 10H+ + 10e– + 6H2O  2BrO3– + 12H+ + 10e– + 10H2O
Now, we get
Br2 + 5H2O2  2BrO3– + 4H2O + 2H+

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
54 Redox Reactions NEET

Example 10 : In passing chlorine gas through a concentrated solution of alkali we get chloride and chlorate ions.
Obtain balanced chemical equation for this reaction.
Oxidation
Solution : (i)
0 – – +5 –
Cl 2 + OH Cl + ClO 3

Reduction
(ii) Cl2  2Cl– (Reduction half)
Cl2  2ClO3– (Oxidation half)
(iii) Balancing e–
Cl2  2e   2Cl
Cl2  2ClO3– + 10e–
(iv) Balancing ‘O’
Cl2 + 2e–  2Cl–
Cl2  6H2 O  2ClO3  10e 
(v) Balancing ‘H’
Cl2 + 2e–  2Cl–
Cl2 + 6H2O + 12OH–  2ClO3– + 10e– + 12H2O
Now,
[Cl2 + 2e–  2Cl– ] × 5
Cl2 + 12OH–  2ClO3– + 10e– + 6H2O

6Cl2 + 12OH–  10Cl– + 2ClO3– + 6H2O

or 3Cl2 + 6OH–  5Cl– + ClO3– + 3H2O

Example 11 : Balance the equation by ion electron method

Zn + NO3–  Zn2+ + NH4+ (in basic medium)
Reduction

0 +5 –3
– +2 +
Solution : (i) Zn + NO 3 Zn + NH 4

Oxidation
(ii) Zn  Zn2+ (Oxidation half reaction)
NO3–  NH4+ (Reduction half reaction)
(iii) Balancing e–
Zn  Zn2+ + 2e–
NO3– + 8e–  NH4+
(iv) Balancing ‘O’
Zn  Zn2+ + 2e–
NO3– + 8e–  NH4+ + 3H2O
(v) Balancing ‘H’
NO3– + 8e– + 10H2O  NH4+ + 3H2O + 10OH–
Zn  Zn2+ + 2e–
NO3– + 7H2O + 8e–  NH4+ + 10OH–
Now,
[Zn  Zn2+ + 2e–] × 4
NO3– + 7H2O + 8e–  NH4+ + 10OH–

4Zn + NO3– + 7H2O  4Zn2+ + NH4+ + 10OH–

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Redox Reactions 55
REDOX REACTIONS AS THE BASIS OF TITRATIONS
1. Potassium Permanganate (KMnO4)
It is a versatile and strong oxidising agent used in estimation of many reducing agents such as Fe2+ ions,
oxalates ions etc. In these titrations, no indicator is used because KMnO4 itself is deeply coloured. So,
KMnO4 acts as a self indicator and when it is titrated against a reducing agent its colour disappears.
The reaction for titration of MnO4– against Fe2+ ions is
MnO4– + 8H+ + 5e–  Mn+2 + 4H2O
[Fe+2  Fe+3 + e–] × 5

MnO4– + 5Fe+2 + 8H+  Mn+2 + 5Fe+3 + 4H2O

2. Acidified Potassium Dichromate
K2Cr2O7 is also used as an oxidising agent in redox titrations. It is a relatively weaker oxidising agent as
compared to KMnO4, it does not act as a self indicator because no dramatic auto-colour change occurs in
its titrations. In these titrations, indicators such as diphenylamine, potassium ferricyanide K3[Fe(CN)6] are
commonly used. The chemical equation showing Cr2O72– as an oxidising agent is
Cr2O72– + 14H+ + 6e–  2Cr3+ + 7H2O
3. Iodine (I2)
It also acts as a mild oxidising agent in solution according to the reaction.
I2 + 2e–  2I–
Iodine can be used for titrating strong reducing agents like sodium thiosulphate according to the reaction.
I2(aq) + 2S2O32–(aq)  2I–(aq) + S4O62–(aq)
These titration in which iodine is directly titrated against a reducing agent are called iodimetric titrations.
There is another method in which iodine is liberated from potassium iodide by some oxidising agent and
liberated iodine is titrated against standard sodium thiosulphate solution. These are called iodometric titrations.
Cu2+ ion concentration is estimated by oxidising I– ions (from KI) to liberate I2, which is titrated against
Na2S2O3.
2Cu2+(aq) + 4I–(aq)  Cu2I2(s) + I2(aq)
2Na2S2O3 + I2  2NaI + Na2S4O6

In these iodimetric titrations, end point can be detected by adding freshly prepared starch solution. It reacts
with iodine to form intensely blue-coloured complex. Appearance or disappearance of iodine can be identified
accurately by this method.

Note :

Mol. wt
z Eq. wt. of oxidizing or reducing agent =
Change in oxidation state or no.
of electrons gained or lost.

158
e.g., Eq. wt. of KMnO4 in acidic medium = = 31.6
5
∵ Mn7+ + 5e–  Mn2+

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
56 Redox Reactions NEET

REDOX REACTIONS AND ELECTRODE PROCESSES

When a zinc rod is placed in Cu(NO3)2 solution, a redox reaction occurs. During this reaction, Zn is oxidised
to Zn2+ ions while Cu2+ ions are reduced to Cu by direct transfer of electrons from Zn to Cu2+ ions. Here the
chemical energy of the reaction evolves as heat.
Now, we modify the experiment in such a manner that for the same redox reaction transfer of electrons takes
place indirectly. For indirect redox reaction place zinc rod in 1M ZnSO4 solution in the left beaker and a copper
rod in a 1M CuSO4 solution in the right beaker. No reaction takes place in either of the two beakers and at the
interface of the metal and its salt solution in each beaker where both the reduced and oxidised forms of the same
species are present. Each beaker constitutes a half cell. It is also called as an electrode or a redox couple.
Now, set the experiment according to the figure.
Electron
V flow

Current
flow
–
e SO2–
4 Salt bridge K
+ e–

– Containing +
K2SO4
Anode Cathode

Zinc rod Copper rod

Zn2+ SO2–
4
ZnSO4 CuSO4
Cu2+
solution solution
Fig. : An electrochemical or galvanic cell
And connect the solutions in the two beakers by a salt bridge which provides electric contact between the
two solutions without allowing them to mix with each other. A salt bridge is a U-tube containing solutions of
an inert electrolyte such as KCl, KNO3, K2SO4 etc. in agar-agar or gelatin.
Function of salt bridge
(i) To complete the circuit.
(ii) To maintain electrical neutrality in the solutions of both the half-cells.
(iii) To prevent intermixing of the solutions of both the half cells.
“The tendency of an electrode to lose or gain electrons is called electrode potential”.
The electrode potential of any electrode depends upon the concentrations of the ions and temperature. If the
concentration is taken as unity i.e., 1 mol L–1 (if any gas appears in the electrode reaction, it is taken at
1 atm pressure) and temperature is taken as 298 K, the electrode potentials thus determined are called
standard electrode potentials and denoted by E°.
The standard electrode potentials of a large number of electrodes have been determined using standard
hydrogen electrode as the reference electrode. By convention, the standard electrode potential (E°) of hydrogen
electrode is 0.00 volts.
Standard electrode potential is given a positive sign if reduction occurs at that electrode w.r.t. the standard
hydrogen electrode and is given a negative sign if oxidation occurs at that electrode w.r.t. the standard
hydrogen electrode.
The standard electrode potentials of a number of electrodes at 1 M concentration of the dissolved ions at
298 K are given in table.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Redox Reactions 57
Table : The Standard Electrode Potentials at 298 K

Es/V
–
Reaction (Oxidised form + ne  Reduced form)
–
F2(g) + 2e–  2F 2.87
3+ – 2+
Co + e  Co 1.81
+ –
H2O2 + 2H + 2e  2H2O 1.78
– + – 2+
MnO4 + 8H + 5e  Mn + 4H2O 1.51
3+ –
Au + 3e  Au(s) 1.40
– –
Cl2(g) + 2e  2Cl 1.36
2– + – 3+
Cr2O7 + 14H + 6e  2Cr + 7H2O 1.33
+ –
O2(g) + 4H + 4e  2H2O 1.23
+ – 2+
MnO2(s) + 4H + 2e  Mn + 2H2O 1.23
– –
Br2 + 2e  2Br 1.09
– + –
NO + 4H + 3e
3  NO(g) + 2H2O 0.97
2+ – 2+
2Hg + 2e  Hg2 0.92
+ –
Ag + e  Ag(s) 0.80
3+ – 2+
Fe + e  Fe 0.77
Increasing strength of oxidising agent

Increasing strength of reducing agent

+ –
O2(g) + 2H + 2e  H2O2 0.68
– –
I2(s) + 2e  2I 0.54
+ –
Cu + e  Cu(s) 0.52
2+ –
Cu + 2e  Cu(s) 0.34
– –
AgCl(s) + e  Ag(s) + Cl 0.22
– –
AgBr(s) + e  Ag(s) + Br 0.10
+ –
2H + 2e  H2(g) 0.00
2+ –
Pb + 2e  Pb(s) –0.13
2+ –
Sn + 2e  Sn(s) –0.14
2+ –
Ni + 2e  Ni(s) –0.25
2+ –
Fe + 2e  Fe(s) –0.44
3+ –
Cr + 3e  Cr(s) –0.74
2+ –
Zn + 2e  Zn(s –0.76
– –
2H2O + 2e  H2(g) + 2OH –0.83
3+ –
Al + 3e  Al(s) –1.66
2+ –
Mg + 2e  Mg(s) –2.36
+ –
Na + e  Na(s) –2.71
2+ –
Ca + 2e  Ca(s) –2.87
+ –
K +e  K(s) –2.93
+ –
Li + e  Li(s) –3.05

1. A negative E° means that the redox couple is a stronger reducing agent than the H+/H2 couple.
2. A positive E° means that the redox couple is a weaker reducing agent than the H+/H2 couple.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
58 Redox Reactions NEET

Application of Electrochemical Series

1. Activity of metals : Lower the standard reduction potential value higher will be the activity of metal as
it will have higher tendency to lose electrons e.g., Li > K > Na > Zn > Fe.
2. Predicting whether a metal can liberate hydrogen from an acid or not, all those metals whose reduction
potential are less than hydrogen (i.e., have negative values) will have higher tendency to lose electron
than hydrogen and so H+ ions will gain electrons to form H2.
3. Predicting feasibility of a redox reaction : A redox reaction is feasible only if the species having
higher reduction potential is gaining electrons and the species to release electrons must have lower
reduction potential. For example;
Cu(s) + 2Ag+(aq)  Cu+2(aq) + 2Ag(s)
Here Ag have higher reduction potential than Cu. Therefore, Ag is reduced here.
4. Calculation of EMF of the cell : Every galvanic or voltaic cell is made up of two half cells, the oxidation
half cell (anode) and the reduction half cell (cathode). The potentials of these half cells are always
different. The difference in potentials of the two half cells is known as the electromotive force (emf) of
the cell or cell potential.
The standard emf of the cell (E°cell) may be obtained by substracting the standard electrode potential
of the anode from that of the cathode i.e.,
E°cell = (Standard electrode potential of cathode – Standard electrode potential of anode)

Ecell  Ecathode  Eanode

EXERCISE
8. An electrochemical cell has two half cell reactions as,
A2+ + 2e–  A ; E° = 0.34 V
X  X2+ + 2e– ; E° = +2.37 V
The cell voltage will be
(1) 2.71 V (2) 2.03 V
(3) –2.71 V (4) –2.03 V
9. Choose the correct statement for galvanic cell
(1) Oxidation : cathode (2) Positive electrode : cathode
(3) Flow of electron : cathode to anode (4) All are correct
10. Which of the following is true about salt bridge?
(1) It maintains the electrical neutrality (2) It completes the circuit
(3) It contains salt (4) All are correct
11. The electrochemical cell representing the given reaction

Ni(s)  Cu2  Ni2  Cu(s)

(1) Ni(s) | Cu2+ || Ni2+ | Cu(s) (2) Ni(s) | Ni2+ || Cu2+ | Cu
(3) Cu(s) | Cu2+ || Ni(s) | Ni2+ (4) Cu(s) | Cu2+ || Ni2+ | Ni(s)

‰ ‰ ‰

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
 nt
me nment
sigAnssig
Assignment
As

Assignment
7. Which of the given reaction is an example of
SECTION - A
disproportionation reaction? [NCERT Pg. 272]
NCERT Based MCQs
(1) 3Cl2 + 6OH–  5Cl – + ClO3– + 3H2O
1. The reducing agent in the given reaction is
(2) CuSO4 + Zn  ZnSO4 + Cu
Fe2O3 + 2 Al Al2O3+ 2 Fe
[NCERT Pg. 265] (3) 2H2O  2H2 + O2

(1) Fe2O3 (2) Al (4) 3Mg + N2  Mg3N2

(3) Al2O3 (4) Fe 8. Consider the given reaction [NCERT Pg. 276]
2. Metal which will easily release electron(s) in
Zn + NO –3  Zn2  NH4 (Basic medium)
aqueous solution, is [NCERT Pg. 279]
(1) Zn (2) Ag The balanced equation for the given reaction is
(3) Cu (4) Au (1) 4Zn + NO –3  H2O  4Zn2  NH4  10 OH–
3. The oxidation number of N in (NH4)2SO4 is
[NCERT Pg. 268] (2) 4Zn + NO –3  10H  4Zn2  NH4  3H2O

(1) 3 (2) –3 (3) 4Zn + NO–3  7H2O  4Zn2  NH4  10 OH–

(3) 0 (4) 1
(4) Zn + NO –3  H2O  Zn2  NH4
4. Consider the given reaction as balanced equation
in acidic medium 9. Consider the given diagram
a Cr  OH3  bIO3  c OH  dI  aCrO24  eH2O A

The ratio of b to a is [NCERT Pg. 274]

(1) 2 : 1 (2) 1 : 2 +
B (aq)
(3) 2 : 5 (4) 5 : 2
5. The standard reduction potentials at 25°C of Li+/Li, If on dipping A in B2SO4(aq), the colour of the
Ba2+/Ba, Na+/Na and Mg2+/Mg are –a, (–a + 0.15), solution changes from colourless to blue then
(–a + 0.34) and (–a + 0.68) volt respectively. The A and B respectively are [NCERT Pg. 279]
strongest oxidising agent among the following is (1) Ag and Cu
[NCERT Pg. 279]
(2) Cu and Ag
(1) Li+ (2) Mg2+
(3) Cu and Au
(3) Na+ (4) Ba2+
6. The oxidation number of C marked as (1) and (2) (4) Fe and Cu
in the compound O = C = C = C = O, respectively 10. The oxidant in the given reaction is
(1) (2) (3)
are [NCERT Pg. 273]
2FeCl3(aq) + H2(g)  2FeCl2(aq) + 2HCl(aq)
(1) 2, 0
[NCERT Pg. 265]
(2) 0, 2
(3) 2, 2 (1) H2 (2) FeCl3

(4) 2, 4 (3) FeCl2 (4) HCl

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
60 Redox Reactions NEET

11. In which of the following compounds, the underlined 2. The oxidation state of sulphur in H2S2O8 is
element can undergo disproportionation reaction? (1) +7 (2) +6
[NCERT Pg. 272] (3) –6 (4) +4
(1) KMnO4 3. In which of the following compounds iron has
(2) HNO3 lowest oxidation state?

(3) HClO4 (1) FeSO4.(NH4)2SO4.6H2O

(4) HNO2 (2) K4[Fe(CN)6]

12. How many moles of KMnO4 are reacted with one (3) Fe2O
mole of ferrous oxalate in acidic medium? (4) K2FeO4
[NCERT Pg. 274] 4. Phosphorus has the oxidation state + 3 in
1 5 (1) Orthophosphoric acid
(1) (2)
5 3 (2) Phosphorous acid
3 2 (3) Metaphosphoric acid
(3) (4)
5 5 (4) Pyrophosphoric acid
13. The number of electrons lost or gained during the 5. The oxidation states of phosphorus vary from
change, 3Fe + 4H2O  Fe3O4 + 4H2 is
(1) – 3 to + 5 (2) – 1 to + 1
[NCERT Pg. 268]
(3) – 3 to + 3 (4) – 5 to + 1
(1) 2 (2) 4
6. White P reacts with caustic soda, the products are
(3) 6 (4) 8 PH3 and NaH2PO2. The reaction is an example of
14. Oxidation number of S in H2S2O8 is (1) Oxidation (2) Reduction
[NCERT Pg. 268] (3) Disproportionation (4) Neutralization
(1) +2 (2) +4 7. Oxidation number of oxygen atom in O3 molecule is
(3) +6 (4) +7 (1) 0 (2) –2
15. When fluorine reacts with ice, following chemical (3) + 2 (4) – ½
reaction takes place
8. The brown ring complex compound is formulated as
H2O(s) + F2(g)  HF(g) + HOF(g) [Fe(H2O)5NO]SO4. The oxidation state of iron is
The oxidation state of fluorine changes from (1) 1 (2) + 2
[NCERT Pg. 268] (3) + 3 (4) + 6
(1) 0 to –1 9. The oxidation number of C in CH4, CH3Cl, CH2Cl2,
CHCl3 and CCl4 is respectively
(2) 0 to +1
(1) –4, –2, 0, +2, +4 (2) +2, 4, 0, –2, –4
(3) –1 to 0
(3) 4, 2, 0, –2, 4 (4) 0, 2, –2, 4, 4
(4) +1 to 0
10. Chlorine is in +3 oxidation state in
SECTION - B (1) HCl (2) HClO4
Objective Type Questions (3) ICl (4) ClF3
1. The process in which oxidation number increases 11. Given that the oxidation state of sulphur is –2, the
is eq. wt. of sulphur is
(1) Reduction (2) Hydrolysis (1) 16 (2) 32
(3) Oxidation (4) Decomposition (3) 9 (4) 4
Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Redox Reactions 61
12. In alkaline solution KMnO4 reacts as follows 20. How many mole of FeSO4 reacted with one mole
2KMnO4 + 2KOH  2K2MnO4 + H2O + O of KMnO4 in acidic medium?

Therefore, its eq. wt. will be 2

(1) (2) 5
5
(1) 31.6 (2) 52.7
1 1
(3) 79.0 (4) 158.0 (3) (4)
2 5
13. In a reaction between zinc and iodine, zinc iodide
21. Oxidation number of Cr in CrO5 is
is formed. What is being oxidised?
(1) +10 (2) +6
(1) Zinc ions (2) Iodide ions
(3) +4 (4) +5
(3) Zinc atom (4) Iodine

OH
14. 0.2 g of sample of H 2 O 2 required 10 ml of 22. In reaction Cl2 + IO3–   IO4– + 2Cl–. The
1N KMnO4 solution in a titration in presence of dil. oxidising and reducing agent respectively are
H2SO4. The percentage purity of H2O2 is
(1) Cl–, IO3– (2) Cl2, IO3–
(1) 25% (2) 65%
(3) Cl–, IO4– (4) Cl2, IO4–
(3) 85% (4) 95%
23. For the reaction
15. In the following equation xMnO 4– + yC 2O 42– + 16H +  Mn 2+ + zCO 2 +
2Br2+6CO32– +3H2O  5Br¯ + BrO3¯+6HCO3¯ 8H2O. The x, y, z are
(1) Bromine is oxidised and carbonate is reduced (1) 2, 5, 10 (2) 2, 5, 16
(2) Bromine is reduced and carbonate is oxidised (3) 1, 2, 5 (4) 2, 5, 5
(3) Bromine is neither reduced nor oxidised 24. Oxidation state of Fe in Fe3O4 is
(4) Bromine is reduced as well oxidised
1 1
(1) , (2) +2, +3
16. When SO 2 is passed in acidified potassium 2 2
dichromate solution, the oxidation state of S is
changed from (3) +2 (4) +4, +2

(1) +4 to zero (2) +4 to +2 25. Each chromium in K2Cr2O7  Cr2O3 is changing

from
(3) +4 to +6 (4) +6 to +4
(1) +6 to +12 (2) +12 to +6
17. Which of the following reactions involves oxidation
(3) +6 to +3 (4) None of these
and reduction?
26. Oxidation state of oxygen in H2O2 and OF2 is
(1) NaBr + HCl  NaCl + HBr
(1) +1, –1 (2) +2, +1
(2) HBr + AgNO3  AgBr + HNO3
(3) –2, +2 (4) –1, +2
(3) H2 + Br2  2HBr
(4) Na2O + H2SO4  Na2SO4 + H2O
18. Given 2Ce4+ + Co  2Ce3+ + Co2+, Eº = 1.89 V.
SECTION - C
The standard reduction potential for Co 2+ is
Previous Years Questions
–0.28 V. The standard reduction potential of Ce4+ to
Ce3+ is
1. The standard electrode potential Es  values of
(1) –1.61 V (2) 1.61 V Al3+/Al, Ag+/Ag, K+/K and Cr3+/Cr are –1.66 V, 0.80 V,
(3) 2.17 V (4) –2.17 V –2.93 V and –0.74, respectively. the correct
decreasing order of reducing power of the metal is
19. Which of the following involves the reduction of
copper? [NEET-2019 (Odisha)]
(1) Cu(s) + ½ O2(g)  CuO(s) (1) Al > K > Ag > Cr
(2) Cu2+(aq) + 2I—(aq)  2CuI(aq) (2) Ag > Cr > Al > K
(3) CuCl2(s) + 2F—(aq)  CuF2 + Cl2(g) (3) K > Al > Cr > Ag
(4) None of these (4) K > Al > Ag > Cr

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
62 Redox Reactions NEET

2. The oxidation state of Cr in CrO6 is 7. Assuming complete ionization, same moles of

which of the following compounds will require the
[NEET-2019 (Odisha)]
least amount of acidified KMnO4 for complete
(1) +4 (2) –6 oxidation? [Re-AIPMT-2015]
(3) +12 (4) +6 (1) FeC2O4 (2) Fe(NO2)2
3. The correct structure of tribromooctaoxide is
(3) FeSO4 (4) FeSO3
[NEET-2019]
8. Which of the following processes does not involve
O O O O O O oxidation of iron? [AIPMT-2015]
–
(1) O = Br – Br – Br = O (2) O = Br – Br – Br – O
O O
– (1) Liberation of H2 from steam by iron at high
O O O O
–

–
temperature
O O O
–
O O O
– (2) Rusting of iron sheets
(3) O – Br – Br – Br = O (4) O = Br – Br – Br – O–
– –
O O O O O
– O (3) Decolourization of blue CuSO4 solution by iron
4. Which of the following reactions are (4) Formation of Fe(CO)5 from Fe
disproportionation reaction? [NEET-2019]
9. (a) H2O2+O3  H2O + 2O2
(a) 2Cu  Cu2  Cu0
(b) H2O2 + Ag2O  2Ag + H2O + O2

(b) 3MnO24  4H  2MnO 4  MnO2  2H2O Role of hydrogen peroxide in the above reactions is
respectively [AIPMT-2014]

(c) 2KMnO 4   K 2MnO 4  MnO2  O2 (1) Oxidizing in (a) and reducing in (b)
(2) Reducing in (a) and oxidizing in (b)
(d) 2MnO 4  3Mn2   2H2O  5MnO2  4H
(3) Reducing in (a) and (b)
Select the correct option from the following
(1) (a) and (b) only (4) Oxidizing in (a) and (b)

(2) (a), (b) and (c) 10. In which of the following compounds, nitrogen exhibits
highest oxidation state? [AIPMT (Prelims)-2012]
(3) (a), (c) and (d)
(4) (a) and (d) only (1) N3H (2) NH2OH

5. The correct order of N-compounds in its decreasing (3) N2H4 (4) NH3
order of oxidation states is [NEET-2018] 11. A solution contains Fe , Fe3+ and – ions. This
2+

(1) HNO3, NO, N2, NH4Cl solution was treated with iodine at 35C. E for Fe3+/
Fe2+ is +0.77 V and E for I2/2I– = 0.536 V. The
(2) HNO3, NO, NH4Cl, N2
favourable redox reaction is [AIPMT (Mains)-2011]
(3) NH4Cl, N2, NO, HNO3
(1) – will be oxidised to 2
(4) HNO3, NH4Cl, NO, N2
(2) Fe2+ will be oxidised to Fe3+
6. For the redox reaction
(3) 2 will be reduced to –
MnO 4  C 2 O 24  H  Mn2   CO 2  H2 O
(4) There will be no redox reaction
The correct coefficients of the reactants for the
balanced equation are [NEET-2018] 12. Oxidation states of P in H4P2O5, H4P2O6, H4P2O7 are
respectively [AIPMT (Prelims)-2010]
MnO 4 C2O24 H+
(1) +3, +5, +4
(1) 16 5 2
(2) 2 5 16 (2) +5, +3, +4

(3) 5 16 2 (3) +5, +4, +3

(4) 2 16 5 (4) +3, +4, +5

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Redox Reactions 63
19. Which change requires an oxidising agent?
13. Oxidation numbers of P in PO34 , of S in SO24 and

that of Cr in Cr2O72 , are respectively 


(1) 2S2 O32   2
 S 4 O6

[AIPMT (Prelims)-2009] 


(2) Zn2  
 Zn
(1) + 3, + 6 and + 5 (2) + 5, + 3 and + 6
(3) - 3, + 6 and + 6 (4) + 5, + 6 and + 6 

(3) ClO  
 Cl


14. The number of moles of KMnO4 that will be needed

to react with one mole of sulphite ion in acidic solution 

(4) SO3  2
 SO4
is [AIPMT (Prelims)-2007]
20. Given the following reactions involving A, B, C and D
3
(1) 1 (2) (i) C + B+  C+ + B
5
(ii) A+ + D  No reaction
4 2
(3) (4) (iii) C+ + A  No reaction
5 5
Questions asked Prior to Medical Ent. Exams. 2005 (iv) D + B+  D+ + B
15. Standard reduction potentials of the half reactions The correct arrangement of A, B, C, D in order of
are given below their decreasing ability as reducing agent
F2(g) + 2e–  2F–(aq) ; Eo = +2.85 V (1) D > B > C > A (2) A > C > D > B
Cl2(g) + 2e–  2Cl–(aq) ; Eo = +1.36 V (3) C > A > B > D (4) C > A > D > B
Br2(l) + 2e–  2Br–(aq) ; Eo = +1.06 V 21. Which element undergoes disproportionation in
I2(s) + 2e–  2I–(aq) ; Eo = +0.53 V water?
The strongest oxidising and reducing agents (1) Cl2 (2) F2
respectively are
(3) K (4) Cs
(1) F2 and I– (2) Br2 and Cl–
22. Standard reduction potentials at 25°C of Li+ / Li,
(3) Cl2 and Br– (4) Cl2 and I2 Ba2+ / Ba, Na+ / Na and Mg2+ / Mg are –3.05, –2.90,
–2.71 and –2.37 volt respectively. Which one of the
16. Standard electrode potential for Sn4 / Sn2 couple
following is the strongest oxidizing agent?
is +0.15 V and that for the Cr 3 / Cr couple is
(1) Ba2+ (2) Mg2+
–0.74 V. These two couples in their standard state
are connected to make a cell. The cell potential (3) Na+ (4) Li+
will be 23. Which substance is serving as a reducing agent in
(1) +1.83 V (2) +1.19 V the following reaction?
(3) +0.89 V (4) +0.18 V 14H+ + Cr2O72– + 3Ni  7H2O + 3Ni2+ + Cr3+
17. Standard reduction electrode potential of three (1) H+ (2) Cr2O72–
metals X, Y and Z are –1.2 V, +0.5 V and –3.0 V
(3) H2O (4) Ni
respectively. The reducing power of these metals
will be 24. The oxide, which cannot act as a reducing agent, is
(1) X > Y > Z (2) Y > Z > X (1) CO2 (2) ClO2
(3) Y > X > Z (4) Z > X > Y (3) NO2 (4) SO2
18. In the reaction 25. Oxidation state of Fe in Fe3O4 is
2H2O2  2H2O + O2
5 4
(1) Oxygen is oxidised only (1) (2)
4 5
(2) Oxygen is reduced only
(3) Oxygen is neither oxidised nor reduced 3 8
(3) (4)
(4) Oxygen is both oxidised and reduced 2 3

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
64 Redox Reactions NEET

26. Oxidation numbers of A, B, C are +2, +5 and –2 M M

respectively. Possible formula of compound is (1) (2)
42 55
(1) A2(BC2)2 (2) A3(BC4)2 M M
(3) (4)
(3) A2(BC3)2 (4) A3(B2C)2 45 50
4. Which of the following is correct if
27. The oxidation states of sulphur in the anions SO32–,
E° + > E° > E°  ?
S2O42– and S2O62– follow the order x x y+ y z z

(1) S2O42– < SO32– < S2O62– (1) Z acts as stronger reducing agent

(2) SO32– < S2O42– < S2O62– (2) Z acts as stronger reducing agent

(3) S2O42– < S2O62– < SO32– (3) X acts as stronger oxidizing agent

(4) S2O62– < S2O42– < SO32– (4) Both (1) & (3)
5. In which metal container we can store salt of
28. Electrode potential for the following half-cell
Sn2+?
reactions are
(1) Al (2) Fe
Zn  Zn2+ + 2e–; E° = + 0.76 V;
(3) Cu (4) Mg
Fe  Fe2+ + 2e–; E° = + 0.44 V
6. In which of the following compound the oxidation
The EMF for the cell reaction Fe2+ + Zn  Zn2+ + Fe state of sulphur is different from other three?
will be
(1) K2SO4 (2) SF6
(1) – 0.32 V (2) + 1.20 V
(3) Na2S2O3 (4) Na2S2O7
(3) – 1.20 V (4) + 0.32 V
7. How many grams of NaOH is required to react with
3.1 g of P4 to form PH3 and NaH2PO2?
29. In acidic medium, H2O2 changes Cr2O7–2 to CrO5
which has two (—O—O—) bonds. Oxidation state (1) 4 g (2) 3 g
of Cr in CrO5 is (3) 2 g (4) 1 g
(1) +5 (2) +3 8. Best oxidizing agent out of the following is
(3) +6 (4) –10 (1) Au3+ (2) Cu2+
(3) Na+ (4) Fe3+
SECTION - D 9. Which of the following has oxidation number of
NEET Booster Questions central atom zero?
(1) C3O2 (2) CH2Cl2
1. n-factor of HCl in the given reaction is
K2Cr2O7 + HCl  KCl + CrCl3 + Cl2 + H2O (3) HOF (4) All of these
10. What is the equivalent mass of ClO 3 – in the
7 3 following reaction?
(1) (2)
3 7
ClO3–  Cl– + ClO4–
(3) 1 (4) 6
(M = molar mass of CIO3 )
2. Equivalent weight of H2SO4 in the reaction
2M 3M
H2SO4  H2S (1)
3
(2)
2
M M M
(1) (2) (3) (4) 2 M
2 3 2
M M 11. What will be the stoichiometric coefficient of HCl
(3) (4) and PbCl2 in Pb3O4 + HCl  PbCl2 + Cl2 +
4 8
3. What is the equivalent weight of the reactant in the H2O?
following equation? (1) 7 & 4 (2) 8 & 3
[Fe(CN)6]4–  Fe2O3 + CO2 + NO2 (3) 6 & 2 (4) 5 & 3

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
NEET Redox Reactions 65
12. What can be ‘X’ in the following reaction? 20. Oxidation number of Cr atom in CrO5 and K3CrO8
MnO4– + H+ + X  No reaction respectively

(1) S2O32– (2) SO2 (1) +6, +6 (2) +5, +6

(3) SO42– (4) SO32– (3) +6, +5 (4) +5, +5

13. What is the oxidation state of chlorine in bleaching 21. Find the incorrect statement
powder? (1) Higher reduction potential of non-metal means
(1) – 1 only (2) + 1 only stronger reducing agent

1 (2) Lower oxidation potential of a metal means

(3)  (4) – 1, + 1 strong oxidising agent
2
(3) Oxidation state of oxygen in O3 is –1
o
14. Ered of SHE is zero because
(4) All of these
(1) H2 is lighter than O2 22. In case of CH3COOH, the oxidation number of carbon
(2) H2 is explosive of carboxylic group is

(3) It is assumed (1) –3 (2) Zero

(4) Concentration of HCl is 1M (3) +1 (4) +3

15. The metal rod does not dissolve, then it should be 23. Which compound acts as oxidising agent only?
Metal (1) SO2 (2) H2S
(3) H2SO4 (4) HNO2

CuSO4 (aq) 24. The average oxidation state of chlorine in Cl2O7 is

(1) –1 (2) +1

(1) Pb (2) Ag (3) +7 (4) +5

(3) Sn (4) Al 25. When benzaldehyde is oxidised to give benzoic

acid then the oxidation state of carbon of aldehydic
16. What are cathode and anode respectively in Daniell group is changed from
cell?
(1) +2 to +3 (2) +1 to +3
(1) Zn, Cu (2) Fe, Zn
(3) Zero to +2 (4) No change
(3) Zn, Fe (4) Cu, Zn
26. When an alkali metal is reacted with hydrogen then
17. Which of the following is the product of metallic hydride is formed. In this reaction
C6H5CHO + [Ag(NH3)2]+ + OH–  product + Ag (1) Hydrogen is oxidised
+ H2O + NH3
(2) Hydrogen is reduced
(1) C6H5COO– (2) C6H5CH2O–
(3) Hydrogen is neither oxidised nor reduced
(3) C6H5COOAg (4) C6H5O–
(4) Hydrogen is oxidised as well as reduced
18. Oxidation states of carbon in C3O2 will be
27. Cl2 (g) + XOH  YClO3– + ZH2O + 10e–
(1) +2, 0, +2 (2) +2, +2, +2
The coefficient X, Y and Z are
(3) 0, 0, +2 (4) 0, 0, 0
(1) 6, 2, 2 (2) 5, 1, 3
19. 4O2– (aq) + 2H2O  3O2(g) + 4OH–(aq).
(3) 12, 2, 6 (4) 12, 1, 6
In above reaction, superoxide ion
28. The ratio of number of moles of KMnO 4 and
(1) Shows oxidation only K2Cr2O7 required to oxidise 0.1 mol Sn2+ to Sn+4 in
(2) Shows reduction only acidic medium
(3) Shows disproportionation (1) 6 : 5 (2) 5 : 6
(4) Does not show redox reaction (3) 1 : 2 (4) 2 : 1

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
66 Redox Reactions NEET

NaOH 35. Three metals A, B and C are arranged in increasing

29. Cl2   NaCl  NaClO3  H2O
order of standard reduction electrode potential,
The equivalent mass of Cl2 in the above reaction is hence their chemical reactivity order will be
M (1) A < B < C (2) A > B > C
(1) M (2)
3
(3) B > C > A (4) A = B = C
M 3M
(3) (4) 36. How many moles of KMnO4 are required to oxidise
2 5
one mole of SnCl2 in acidic medium?
30. KCl is used as an electrolyte in salt bridge
because 1 2
(1) (2)
(1) K+ and Cl– are isoelectronic 5 5

(2) Monovalent ions are required 3 4

(3) (4)
5 5
(3) Both the ions have almost same velocity
37. Which of the following is incorrect regarding salt
(4) They are having similar size
bridge solution?
31. Eocell of the given cell
(1) Solution must be a strong electrolyte
2 2
A (s) | A (aq) || B(aq) | B(s) (2) Solution should be inert towards both
electrodes
Given EA / A 2 : 1.4 V 
and EB/B 2 : 1.4 V

(3) Size of cations and anions of salt should be

(1) 2.8 V (2) 1.8 V
much different
(3) 0 V (4) –1.8 V
(4) Salt bridge solution is prepared in gelatin or
32. Electrode potential depends upon agar-agar to make it semi-solid
(1) Size of electrode
38. Standard electrode potentials of redox couples
(2) Surface area of electrode A2+/A, B2+/B, C/C2+ and D2+/D are 0.3 V, –0.5 V,
(3) Temperature –0.75 V and 0.9 V respectively. Which of these is
best oxidising agent and reducing agent respectively?
(4) Shape of electrode
(1) D2+/D and B2+/B (2) B2+/B and D2+/D
33. Number of electrons involved in the reaction when
0.1 mol NH3 dissolved in water (3) D2+/D and C2+/C (4) C2+/C and D2+/D
(1) 2 (2) 0.4 39. The number of moles of H 2 O 2 required to
(3) 0.9 (4) Zero completely react with 400 ml of 0.5 N KMnO4 in
acidic medium are
1
34. F2  e  F ; E  3.02 V (1) 0.1 (2) 0.2
2
(3) 1.0 (4) 0.5
Standard electrode potential for given reaction
40. The oxidation numbers of oxygen in KO3 and BaO2
F2  2e   2F is respectively are

(1) 3.02 V (2) 6.04 V (1) 3, 2 (2) 1, 0

(3) 1.5 V (4) –3.02 V (3) 0, 1 (4) – 0.33, – 1

‰‰‰

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph.011-47623456
Chapter 24

Hydrogen
Chapter Contents
z Introduction Introduction
z Position of Hydrogen in the Hydrogen is the first element of the periodic table. The atomic structure
Periodic Table of hydrogen is the most simplest one with only one proton and one
electron. Hydrogen occurs in its atomic form only at very high
z Dihydrogen (H2 )
temperatures. Normally hydrogen found in nature is dihydrogen i.e.,
z Hydrides in its elemental form it exists as a diatomic molecule (H2). It is the
element which forms the highest number of compounds amongst all
z Water (H2O)
the elements. Water is one of the most important compounds formed
z Hydrogen Peroxide (H2O2) by hydrogen. Even its name hydrogen was given by Lavoisier because
of its ability to form water as in Greek, hydro means water and gene
z Heavy Water (D2O)
means forming.
z Dihydrogen as a Fuel In this chapter we will study the preparation, properties of dihydrogen
and of some important compounds formed by hydrogen like H2O and
H2O2.

POSITION OF HYDROGEN IN THE PERIODIC TABLE

We know that the elements in the periodic table are placed according to their
electronic configuration. The electronic configuration of hydrogen is 1s1, yet
its position in the periodic table is not certain and unsatisfactory. Hydrogen
exhibits properties similar to both alkali metals (Group 1) and halogens
(Group 17).

Resemblance with Alkali Metals

1. Like alkali metals, hydrogen has only one electron in its outer shell.
2. Alkali metals have a strong tendency to lose one electron from their
outermost shell to form unipositive ions (Li+, Na+, K+, Rb+, Cs+) and
attain nearest noble gas configuration. Similarly, hydrogen also loses
electron to form H+ ion.
3. Alkali metals form stable oxides, halides and sulphides, for example
sodium forms Na2O, NaCl and Na2S. Similarly, hydrogen also forms
stable oxide (H2O), halides (HF) and sulphide (H2S).

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
194 Hydrogen NEET

Differences From Alkali Metals

1. The ionisation energy of hydrogen is very high in comparison to alkali metals. Example : iH of Li is
520 kJ mol–1 and that of hydrogen is 1312 kJ mol–1.

This is because the 1s electron of hydrogen is tightly held by the nucleus due to its small size.

2. The size of H+ ion is very small (1.5 × 10–3 pm) as compared to that of alkali metal ions. Therefore,
H+ does not exist freely and is always associated with other atoms or molecules.

Resemblance With Halogens

1. Halogens with general outer electronic configuration (ns2 np5) have a tendency to gain one electron and
attain nearest noble gas configuration. Similarly, hydrogen (1s1) gains one electron to form H– ion and
attain nearest noble gas (helium gas) configuration.

2. The ionization energy of hydrogen (1312 kJ mol–1) is of nearly same order as that of the halogens (iH
of F is 1680 kJ mol–1).

3. Hydrogen molecule is diatomic (H2) and so are the molecules of halogens (say F2).

4. Hydrogen forms hydrides with carbon (e.g., CH4), just like halogens form halides with carbon (CCl4).

Differences From Halogens

1. Hydrogen is less reactive as compared to halogens.

2. The electron affinity of hydrogen is less than those of halogens.

So, seeing the unique behaviour of hydrogen, it is best placed separately in the periodic table.

Example 1 : On the basis of electron affinity, comment on the resemblance of hydrogen with halogens.

Solution : Halogens have electronic configuration ns2 np5. So, they have strong tendency to gain one electron
to attain stable nearest noble gas configuration. Similarly, hydrogen with 1s1 electronic configuration
has a tendency to gain one electron and form H– ion and attain helium gas configuration.

Isotopes of Hydrogen
Isotopes are the different forms of the same element having same atomic number but different mass numbers.
The different isotopic forms of an element have different number of neutrons.

The chemical properties of all the isotopes of an element are same as they have same number of electrons
but due to the difference in their mass numbers they have different physical properties. Despite having same
chemical properties their reactivity is different because of difference in their enthalpy of bond dissociation. There
are three isotopes of hydrogen namely protium, deuterium and tritium.

(i) Protium or ordinary hydrogen (11H) : The predominant form of hydrogen is ordinary hydrogen, protium.
It has one proton and no neutron in the nucleus and one electron revolves around the nucleus.

(ii) Deuterium (12 H or D) : It is also known as heavy hydrogen. It has one proton and one neutron in the
nucleus around which one electron revolves. Terrestrial hydrogen contains 0.0156% of deuterium mostly
in the form of HD.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Hydrogen 195

(iii) Tritium (13 H or T) : This isotope of hydrogen is radioactive and emits low energy – particles having half
life period of 12.33 years. It has one proton and two neutrons in the nucleus. The concentration of tritium
is very low. It is just about one atom per 1018 atoms of protium.
Property Hydrogen Deuterium Tritium
–15
Relative abundance (%) 99.985 0.0156 10
–1
Relative atomic mass (g mol ) 1.008 2.014 3.016
Melting point/K 13.96 18.73 20.62
Boiling point/K 20.39 23.67 25.0
–1
Density/gL 0.09 0.18 0.27
–1
Enthalpy of fusion/kJ mol 0.117 0.197 –
–1
Enthalpy of vaporization/kJ mol 0.904 1.226 –
Enthalpy of bond
–1
dissociation/kJ mol at 298.2 K 435.88 443.35 446.9
Internuclear distance/pm 74.14 74.14 –
–1
Ionization enthalpy/kJ mol 1312 – –
–1
Electron gain enthalpy/kJ mol –73 – –
Covalent radius/pm 37 – –
–
Ionic radius(H )/pm 208

Note : In the year 1934, an American scientist Harold C. Urey, got Nobel Prize for separating
hydrogen isotope of mass number 2 by physical methods.

Example 2 : Which isotope of hydrogen is radioactive?

Solution : Tritium. (1H3 or T)

Example 3 : Which isotope of hydrogen contains equal number of protons and neutrons?

Solution : Deuterium (12 D) . It has one proton and one neutron.

DIHYDROGEN (H2)
Occurrence
Dihydrogen is the most abundant element in the universe. It constitutes about 70% of the total mass of the
universe. But its abundance in earth’s atmosphere is very less. This is because the earth’s gravitational field
is too small to hold so light an element. So, it is just 0.15% by mass in the earth’s atmosphere. In free state
hydrogen is present in volcanic gases and in the combined form it constitutes 15.4% of the earth’s crust and
the oceans. However, it is also present in the plant and animal tissues, carbohydrates, proteins etc. Even
hydrogen is present in mineral resources like coal and petroleum.
Hydrogen is the principal element in the solar atmosphere. It is present in the outer atmosphere of Sun and
other stars of the universe like Jupiter and Saturn.
Ortho and Para Hydrogen
The nuclei of a molecule also have spins like electrons. If the spins of the nuclei of two H-atoms of H2 molecule
are in the same direction, the dihydrogen is called ortho hydrogen. But if the spins of the nuclei of two atoms
are in the opposite dirrections, it is called para hydrogen.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
196 Hydrogen NEET

Ortho hydrogen Para hydrogen

Ordinary dihydrogen contains 75% ortho and 25% para hydrogen. While at low temperature (20 K) ortho and
para hydrogens are 0.18% and 99.82% respectively. Pure para form can be obtained at very low temperature
but pure ortho form cannot be obtained. The physical properties are same for both nuclear spin isomer except
thermal conductivity. Thermal conductivity of para hydrogen is 50% greater and melting point is 0.15 K less
than ortho hydrogen. ortho and para hydrogen also called as allotrope.
Preparation of Dihydrogen
Dihydrogen can be prepared by the following methods :
1. Laboratory Preparation of Dihydrogen :
(i) In laboratory dihydrogen is prepared by the reaction of granulated zinc with dilute hydrochloric acid
or dilute sulphuric acid.
Zn + 2H+(dil)  Zn2+ + H2
(ii) Zinc reacts with aqueous alkali to give dihydrogen

Zn + 2NaOH  Na2 ZnO2  H2

Sodium
zincate

Note : During the laboratory preparation of dihydrogen, following few points should be
remembered.
(i) Pure zinc is not used in the preparation of dihydrogen because it reacts very slowly with
sulphuric acid. Therefore, the addition of some impurities enhances the rate of reaction.
(ii) During the reaction zinc is reacted with dilute sulphuric acid only because it reacts with
concentrated sulphuric acid to form SO2 gas instead of dihydrogen
Zn + 2H2SO4 (conc.)  ZnSO4 + SO2 + 2H2O

2. Commercial Production of Dihydrogen:

(i) By the electrolysis of water : Electrolysis of acidified water using platinum electrodes is used for
the bulk preparation of hydrogen.

Electrolysis
2H2O(l) 
Traces of acid/base
 2H2(g) + O2(g)

(ii) Electrolysis of aqueous barium hydroxide solution : Hydrogen of high purity (>99.95%) is
obtained by electrolysing warm aqueous barium hydroxide between nickel electrodes.
(iii) Electrolysis of brine : It is also produced as a by-product during the manufacture of Cl2 and NaOH
by the electrolysis of brine (aq. NaCl).
During electrolysis, the following reactions takes place :
At anode : 2Cl–(aq)  Cl2(g) + 2e–
At cathode : 2H2O(l) + 2e–  H2(g) + 2OH–(aq)

Overall reaction : 2Cl–(aq) + 2H2O(l)  Cl2(g) + H2(g) + 2OH–(aq)

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Hydrogen 197
(iv) By the action of steam on coke : Dihydrogen is prepared by passing steam over coke or
hydrocarbons at high temperature (1270 K) in the presence of Nickel catalyst.

1270 K
C  H2 O(g)   CO(g)  H2 (g)
Coke
Ni 
Water gas

1270 K
CnH2n  2  nH2 O(g) 
Ni
 nCO(g)  (2n  1)H2 (g)
Hydrocarbon

1270 K
e.g., CH4(g) + H2O(g) 
Ni
 CO(g) + 3H2(g)

The mixture of CO(g) and H2(g) is called water gas. It is also known as synthesis gas or simply
‘syn gas’ because it is used in the synthesis of methanol and many other hydrocarbons.
Nowadays ‘syn gas’ is produced from sewage, saw-dust, scrap wood and newspapers also. When
‘syn gas’ is produced from coal, then this process is known as ‘coal gasification’.
C(s) + H2O(g) 1270

K
 CO(g) + H2(g)
It is difficult to obtain dihydrogen from a mixture of CO and H2 (i.e., water gas). Therefore, the
production of dihydrogen is increased by reacting carbon monoxide of syn gas mixtures with steam
in the presence of iron chromate as catalyst
673 K
CO(g) + H2O(g) FeCrO
 CO2(g) + H2(g)
4

The above reaction is called water-gas shift reaction. The CO2 formed in the above reaction is
removed by scrubbing with sodium arsenite solution.
Note :
Atomic Hydrogen: It is formed by passing H2 gas through electric arc struck between two
tungsten filaments as
5000 K
H2 (g) 
Electric arc
 2H (g) ; H  436 kJ

The life period of atomic hydrogen is 0.3 second. Hence it converts to molecular hydrogen readily
liberating large amount of energy, which is used for welding purposes (in Atomic Hydrogen Torch).
Atomic hydrogen is very reactive and can reduce oxides, chlorides, sulphides, sulphates of
metals.
Nascent Hydrogen: It is the newly born hydrogen formed during chemical reactions in aqueous
solutions. It is also a better reducing agent than molecular hydrogen. For example the addition
of Zn and dil. H2SO4 to KMnO4 decolourises it due to its oxidation but H2(g) cannot do so.
Zn  H2SO4  ZnSO4  2[H]
[Nascent hydrogen]

2KMnO4  3H2SO4  10[H]  K 2SO4  2MnSO4  8H2O

In general the reactivity order of these hydrogens is
H2 < Nascent hydrogen < Atomic hydrogen

Properties of Dihydrogen
Physical Properties:
(i) It is a colourless, odourless, tasteless gas.
(ii) It is insoluble in water.
(iii) It is highly combustible.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
198 Hydrogen NEET

Chemical Properties :
The chemical behaviour of a molecule is determined mainly by its bond dissociation enthalpy. Dihydrogen is
quite stable and dissociates into hydrogen atoms only when heated at 5000 K.
5000 K
H2   H+H; H = 435.9 kJ mol–1
Due to its high bond dissociation enthalpy, it is inert at room temperature.
However, hydrogen reacts with many elements because of its electronic configuration which is 1s1. Therefore,
it accomplishes the reactions in the following three ways :
(i) Loss of the only electron to form H+.
(ii) Gain of an electron to form H–.
(iii) Sharing of electron to form single covalent bond.
Note : The dissociation of dihydrogen into its atoms is only ~0.081% around 2000 K which increases to
95.5% at 5000 K.
Hydrogen undergoes a number of reactions, out of which few are mentioned below :
1. Reaction with halogens : Hydrogen reacts with halogens to give hydrogen halides with general formula
HX.
H2(g) + X2(g)  2HX(g) (X = F, Cl, Br, I)
In case of fluorine, reaction occurs even in dark.
H2 + F2  Dark
 2HF
With chlorine, it occurs in presence of sunlight.
Sunlight
H2 + Cl2   2HCl
Bromine reacts only upon heating.
673 K
H2 + Br2   2HBr
With iodine, it requires catalyst for the reaction.
Pt
H2 + I2 
673 K
 2HI

This shows that F2 is more reactive than Cl2 which is further more reactive than Br2 and least reactive
amongst halogens is I2 which requires a catalyst for the reaction.
2. Reaction with dioxygen : It reacts with oxygen to form water. This reaction is accompanied with
release of heat, so it is exothermic in nature.
Catalyst or
2H2(g) + O2(g) 
Heating
 2H2O(l) ; H = –285.9 kJ mol–1

3. Reaction with dinitrogen : Dihydrogen is employed in Haber’s process for the formation of ammonia
673 K, 200 atm
3H2(g) + N2(g) 
Fe
 2NH3(g) ; H = –92.6 kJ mol–1

4. Reactions with metals : Dihydrogen reacts with metals to yield hydrides at high temperature.
H2(g) + M(g)  Metal hydride
where M is an alkali metal.
For example :

2Na(s) + H2(g)  Heat

 2NaH

Ca(s) + H2(g)  Heat

 CaH2

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Hydrogen 199
5. Reactions with metal ions and metal oxides : Dihydrogen is a strong reducing agent, so it reduces
metal ions and metal oxides (less active than iron) into their corresponding metals.
H2(g) + Pd2+(aq)  Pd(s) + 2H+(aq)
yH2(g) + MxOy(s)  xM(s) + yH2O(l)
For example :

H2 + CuO  Heat
 Cu + H2O
H2 + PbO  Pb + H2O
Dihydrogen reacts with many unsaturated hydrocarbons with atleast one multiple bond in them. Such
reactions are even employed for the formation of products of commercial importance.
(i) With unsaturated hydrocarbons : Vapours of dihydrogen are passed through unsaturated hydrocarbons
with CC or C=C, in the presence of catalyst to form saturated hydrocarbons.

H H
| |
473 K
H  C  C H(g)  H2 (g) 
Ni
 H3 C  CH3 (g)
Ethene Ethane

The above reaction is called catalytic hydrogenation.

(ii) Hydrogenation of vegetable oils : Edible oils (unsaturated) like cotton seed oil, groundnut oil are
converted into solid fat (saturated) also called vegetable ghee by passing hydrogen through it in the
presence of Ni at 473 K.

Ni
Vegetable oil  H2 
473 K
 Fat
(Liquid) (Solid)

(iii) Hydroformylation of olefins to aldehydes : Olefins react with carbon monoxide and dihydrogen in
presence of catalyst to give aldehydes.
RCH == CH2 + H2 + CO  RCH2CH2CHO
The above reaction is called hydroformylation of olefins.
The aldehyde then further gets reduced to alcohol
Pt
RCH2CH2CHO + H2  RCH2 CH2 CH2 OH
Alcohol

Uses of Dihydrogen
1. Synthesis of ammonia : Dihydrogen is used in Haber’s process in the synthesis of ammonia. A
mixture of N2 and H2 in ratio of 1 : 3 is taken for the production of ammonia. Ammonia is further used
in the manufacture of nitric acid and nitrogenous fertilizers.

Catalyst

N2 + 3H2  
 2NH3
500 C

2. Hydrogenation of oils : Oils are polyunsaturated hydrocarbons. Dihydrogen is added to oils like
soyabean oil, cotton seed oil for manufacturing vanaspati fat which are saturated hydrocarbons.
3. Manufacture of methyl alcohol : Water gas enriched with hydrogen gas in the presence of cobalt
catalyst gives methanol.

Cobalt
CO(g) + 2H2(g) 
Catalyst
 CH3OH(l)

4. Manufacture of hydrogen chloride : It is used in the manufacturing of hydrogen chloride which is a

very important chemical.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
200 Hydrogen NEET

5. Manufacture of metal hydrides : It is used in the manufacture of many metal hydrides.

6. Metallurgical processes : Since, dihydrogen is used to reduce heavy metal oxides to metals, as it
is a reducing agent. Therefore, it finds its use in metallurgical processes.
7. For cutting and welding purposes : It is used in the atomic hydrogen torch and oxyhydrogen torches
for cutting and welding purposes. Dihydrogen gets dissociated into atomic hydrogen by an electric arc
and so the hydrogen atoms which are produced are allowed to combine on the surface to be welded
to generate the temperature of 4000 K.
8. Rocket fuel : It is used as a rocket fuel for space research in the form of liquid hydrogen and liquid oxygen.
9. Fuels cells : Dihydrogen is used in fuel cells for the generation of electrical energy. It does not produce
pollution and produces greater energy per unit mass of fuel, therefore, it is advantageous over
conventional fuels like gasoline.
Note : When vegetable oils are exposed to air for prolonged periods, the double bonds present in
oils undergo oxidation and oils become rancid, i.e., they develop unpleasant odour and taste due to
the formation of lower aldehydes and carboxylic acids.

Example 4 : Comment on the reaction of dihydrogen with fluorine.

Solution : Dihydrogen reacts with fluorine even in dark to form hydrogen fluoride. In the reaction dihydrogen
reduces fluorine and itself gets oxidised, thereby forming a covalent bond between H and F of HF.

Example 5 : Explain the use of hydrogen in the formation of vegetable fats.

Solution : Hydrogen is employed for the conversion of polyunsaturated vegetable oils like soyabean, cotton
seeds into vegetable fats like dalda, gagan etc.

Ni
Vegetable oil  H2 
473 K
 Fat
(Liquid) (Solid)

The reaction occurs in the presence of nickel catalyst and at a temperature of 473 K.

HYDRIDES
Hydrogen combines with a large number of other elements including metals and non-metals, except noble
gases to form binary compounds called hydrides. If ‘E’ is the symbol of the element then hydrides are
represented as EHx(e.g., BeH2) or EmHn (e.g., B2H6).
Based on their physical and chemical properties, the hydrides have been classified into three main categories:
(i) Ionic or saline or salt like hydrides
(ii) Covalent or molecular hydrides
(iii) Metallic or non-stoichiometric hydrides

Ionic or Saline Hydrides

The ionic hydrides are stoichiometric which are formed when hydrogen combines with elements of s-block
which are highly electropositive in nature. There are some elements in s-block like Li, Be, Mg which do not
form ionic hydrides. The hydrides formed by Be and Mg (BeH2 and MgH2) are polymeric in structure. Ionic
hydrides are formed by transfer of electrons from metals to hydrogen atoms and contain hydrogen as H– ion
e.g., sodium hydride (Na+H–), calcium hydride (Ca2+2H–) etc. Some of the properties of saline hydrides are
as follows :
(i) These are white crystalline solids, have ionic lattices and behave like salts.
(ii) They have high melting and boiling points.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Hydrogen 201
(iii) These are non-volatile and non-conducting in solid state, however they conduct electricity in fused state
liberating hydrogen at anode which confirms the existence of H– ion.
NaH Na+ + H–

Cathode Anode
+ – –
Na + e Na 2H H2 + 2e–
(iv) These hydrides react violently with water producing dihydrogen gas.
NaH(s) + H2O(aq)  NaOH(aq) + H2(g)
(v) They burn spontaneously in air on heating on account of their decomposition into hydrogen which is
inflammable
CaH2  Ca + H2
(vi) Lithium hydride is used in the synthesis of some useful hydrides since it is rather unreactive at moderate
temperatures with O2 and Cl2. For example
8LiH + Al2Cl6  2LiAlH4 + 6LiCl
2LiH + B2H6  2LiBH4

Covalent or Molecular Hydrides

Covalent or molecular hydrides are the compounds of hydrogen with p-block elements. The most common
hydrides are CH4, H2O, NH3 etc. Covalent hydrides are volatile compounds.
Molecular hydrides are further classified according to their relative number of electrons and bonds in their Lewis
structures.
(i) Electron deficient hydrides : These hydrides have lesser number of electrons than that required for
writing the conventional Lewis structure. All the hydrides of group 13 form electron deficient compounds
like BH3 which polymerise to form B2H6. As these are electron deficient, so they have a tendency to
accept the electrons, therefore, act as Lewis acids.
(ii) Electron-precise hydrides : Such compounds have required number of electrons to write their
conventional Lewis structures. The elements of group 14 form such hydrides. The hydrides have
tetrahedral geometry. e.g., CH4
(iii) Electron-rich hydrides : Electron-rich hydrides have excess electrons in the form of one or more lone
pairs of electrons around the central electronegative element. Therefore, these hydrides due to the
presence of lone pair of electrons form electron-rich hydrides. Infact the presence of lone pair of electrons
on electronegative element results in the association of molecules due to hydrogen bonding. These types
of hydrides are formed by elements of group 15-17 (NH3 has 1 lone pair, H2O has 2 lone pairs, HF has
3 lone pairs).

O
104.5°
H H
Metallic or Non-Stoichiometric (or Interstitial) Hydrides
The elements of group 3, 4, 5 (d-block) and f-block elements form metallic hydrides. In group 6, only
chromium forms hydride (CrH). Metals of group 7, 8, 9 do not form hydrides called as hydride gap. These
hydrides are known as metallic hydrides because they conduct electricity. These hydrides are less dense
than the parent metal because the crystal lattice has expanded the inclusion of hydrogen. This distortion of
the crystal lattice may make the hydride brittle. Moreover these hydrides are non-stoichiometric with variable
composition, being deficient in hydrogen.
For example, LaH2.87, YbH2.55, TiH1.5 – 1.8, ZrH1.3 – 1.75, VH0.56, NiH0.6 – 0.7, PdH0.6 – 0.8 etc.
So, in case of metallic hydrides, the law of constant composition does not hold good.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
202 Hydrogen NEET

There is lot of ambiguity in the nature of bonding in non-stoichiometric transition metal hydrides. Earlier it was
thought that hydrogen occupies interstices in the metal lattice producing distortion without any change in its
type. These hydrides are, therefore, sometimes called interstitial hydrides. But recent studies have disproved
this fact.
Transition metals have a property of adsorption of hydrogen which is used in catalytic reduction and
hydrogenation reactions. There are some metals like Palladium (Pd) and Platinum (Pt) which can adsorb a
large volume of hydrogen and therefore used as its storage media, especially in cars working on fuel cells.

Example 6 : Which class of covalent hydrides are considered as Lewis acids?

Solution : Electron deficient hydrides.

Example 7 : Why does water exists as association of molecules?

Solution : Water exists as association of molecules because of the presence of lone pair of electrons on
its electronegative element (oxygen) which results in the formation of hydrogen bonds between
oxygen atom of one water molecule and hydrogen atoms of other water molecule.

Example 8 : Describe the nature of ionic hydrides.

Solution : Ionic hydrides are crystalline, non-volatile and non-conducting in the solid state.

WATER (H2O)
Water is one of the most readily available chemical. Water is an oxide of hydrogen. It is an important
component of all living organisms. Water constitutes about 65% of human body and 95% of plants. It is
therefore essential for life. The ability of water to dissolve so many other substances makes it a compound
of great importance. Almost three-fourth of the earth’s surface is covered with water. The estimated world water
supply is given in the following table :
Estimated World Water Supply

Source % of Total
Oceans 97.33
Saline lakes and inland seas 0.008
Polar ice and glaciers 2.04
Ground water 0.61
Lakes 0.009
Soil moisture 0.005
Atmospheric water vapour 0.001
Rivers 0.0001
Physical Properties of Water
1. Pure water is colourless, odourless and tasteless.
2. Water is present in the liquid state at room temperature.
3. Water boils at 100°C and changes into the gaseous state whereas it freezes at 0°C to form ice.
4. Water molecules undergo extensive hydrogen bonding i.e., one H2O molecule forms four H-bonding.
5. The existence of hydrogen bonding is responsible for high freezing point, high boiling point, high value
of specific heat, high latent heat of fusion and high latent heat of vaporisation of water, in comparison
to those of H2S and H2Se.
6. The high heat of vaporisation and heat capacity are responsible for moderation of the climate and body
temperature of the living beings.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Hydrogen 203
7. Being an excellent solvent it is essential for the transportation of metabolites in plants.
8. Alcohols, ammonia and carbohydrates dissolve in water due to the formation of hydrogen bonding.
Note : By the time a person feels thirsty, his or her body has lost over 1% of its total water amount.
Structure of Water
The structure of water is studied in its three phases.
Gas Phase : In gas phase, water exists as discrete molecule. Due to the presence of two lone pairs, the
geometry of the water gets distorted and acquires a bent geometry with a bond angle of 104.5° and O–H
bond length of 95.7 pm. In water, each O–H bond is polar because of high electronegativity of oxygen in
comparison to that of hydrogen.

–2

O 95.7 pm
O
O
104.5° 
+

+

H H H H

(a) (b) (c)

Fig. : (a) The bent structure of water; (b) the water molecule as a dipole and
(c) the orbital overlap picture in water molecule
Liquid Phase : In the liquid phase, the large number of water molecules are associated together by hydrogen
bonds.

H
177 pm
95.7 pm O H H
H H H O H
O O
H H
Fig. : Structure of water in liquid state
Solid Phase : The solid or crystalline form of water is ice. At atmospheric pressure ice crystallises in the
hexagonal form, but at very low temperatures it condenses to cubic form.
Structure of Ice
In ice, each oxygen atom is surrounded tetrahedrally by four other oxygen atoms at a distance of 276 pm.
Moreover each oxygen atom is attached to four hydrogen atoms, two by covalent bonds and two by hydrogen
bonds. Due to extensive hydrogen bonding the resulting structure of ice is open cage-like structure having
a number of vacant spaces. Thus, ice has a highly ordered three-dimensional hydrogen bonded structure.
Vacant spaces
O
H H H
O O
H H H H
O O
H H H H
O O
H H H H
O O
H H
Fig. : Tetrahedral arrangement of oxygen atoms in ice

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
204 Hydrogen NEET

Ice is less denser than water : As ice has an open cage-like structure with vacant spaces, therefore less
number of molecules are packed per mL. Melting of ice results in breaking of hydrogen bonds. In this way
the molecules come closer to each other in the liquid state than they were in the solid state. Thus, ice has
lower density than water. This fact is of great ecological significance as ice formed on the surface of lakes
is less denser, so it does not sink to the bottom and provides thermal insulation for the water below it which
ensures the survival of the aquatic life.
Density of water is maximum at 4°C : The density of water is maximum at 4°C. The density of water is
affected by two factors.
(i) The breaking of hydrogen bonds resulting into closer packed structure.
(ii) The thermal expansion: With the rise in temperature, ice melts, the hydrogen bonds breaks and
molecules comes closer, decreasing the volume and increasing the density until 4°C. With further
increase in temperature the kinetic energy of the molecules increases progressively and they start moving
away from each other increasing the volume and thus decreasing the density.
Thus, at 4°C, the two effects thermal expansion and breaking of hydrogen bonds balance each other
and water is at maximum density.
Chemical Properties
Water has a unique property of reacting with a large number of substances. It can act both as a base as
well as an acid. Moreover, it can be easily oxidised and reduced and further acts as ligand to metals.
1. Amphoteric nature : Water can act both as an acid as well as a base and is thus said to be an
amphoteric substance.
According to Lowry Bronsted concept, it can act as an acid by losing a proton and as a base by
accepting a proton.
Water as base : Water acts as a base towards acids stronger than it as shown below,


  
H2O(l)  H2S(aq) 
 H3 O (aq)  HS (aq)
Base Acid


  
H2O(l)  HCl(aq) 
 H3 O (aq)  Cl (aq)
Base Acid

Water as an acid : Water acts as an acid towards bases stronger than it


  
H2O(l)  NH3 (aq) 
 OH (aq)  NH4 (aq)
Acid Base

The auto-protolysis (self-ionization) of water takes place as follows :


  
H2 O(l)  H2 O(l) 
 H3 O (aq)  OH (aq)
Acid-1 Base-2 Acid-2 Base-1
(Acid) (Base) (Conjugate (Conjugate
acid) base)

However, water is neutral towards litmus and its pH is 7 at 25°C.

2. Redox reactions involving water : Water can act both as oxidising as well as reducing agent.
Oxidising agent : Water acts as an oxidising agent when it gets reduced.
2H2O(l)  2Na(s) 
 2NaOH(aq)  H2 (g)
Oxidising
agent

In the above reaction H2O gets reduced to dihydrogen by highly electropositive metal.
Reducing agent : Water acts as a reducing agent when it gets oxidised.

 4H (aq)  4F  (aq)  O2 (g)

2H2O(l)  2F2 (g) 
Reducing
agent

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Hydrogen 205
In the above reaction of fluorine with water, it acts as a reducing agent as it gets oxidised to O2. Water
is oxidised to O2 during photosynthesis
Sunlight
6CO2 (g)  12H2O(l) 
Chlorophyll
 C6H12O6 (aq)  6H2O(l)  6O2 (g)

3. Hydrolysis reaction : Water is an excellent solvent due to its high dielectric constant (78.39). In
addition, water can easily hydrolyse many ionic and covalent compounds.
(i) Water hydrolyses oxides and halides of non-metals forming their respective acids
P4O10(s) + 6H2O(l)  4H3PO4(aq)
SiCl4(l) + 2H2O(l)  SiO2(s) + 4HCl(aq)
SO3(g) + H2O(l)  H2SO4(aq)
(ii) Water hydrolyses the carbides, hydrides, nitrides and phosphides of some metals with the liberation
of acetylene, hydrogen, ammonia, phosphine respectively.

CaC2  2H2 O  Ca(OH)2  C2H2

Calcium Acetylene
carbide

CaH2 (s)  2H2 O(l) 

 Ca(OH)2 (aq)  2H2 (g)
Calcium
hydride

AlN  3H2O  Al(OH)3  NH3

Aluminium Ammonia
nitride

Ca3P2  6H2 O  3Ca(OH)2  2PH3

Calcium Phosphine
phosphide

4. Hydrates Formation : There are three main types of hydrates

(i) Compounds in which water molecules are co-ordinated to the metal ion e.g.,
[Cr(H2O)6]3+ 3Cl–
[Fe(H2O)6] Cl3
(ii) In some compounds, water molecule occupies interstitial sites in the crystal lattice e.g.,
BaCl22H2O.
(iii) Compounds in which the water molecules are hydrogen bonded to certain oxygen containing
anions. For example
CuSO45H2O, four H2O molecules are co-ordinated to Cu2+ ion while the fifth H2O molecule is
hydrogen bonded to SO42– ion. So, CuSO45H2O is written as
[Cu(H2O)4]2+ SO42– H2O

2+
H H
–
H–O O–H H O O
Cu O S
–
H–O O–H H O O
H H

Example 9 : Why do alcohol dissolves in water?

Solution : Alcohol being a polar covalent compound, dissolves in water because of the formation of hydrogen
bonds between them.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
206 Hydrogen NEET

Example 10 : Which properties of hydrogen are responsible for moderation of the climate and body temperature
of living beings?
Solution : High heat of vaporisation and high heat capacity.

Example 11 : Compare the density of ice and water.

Solution : Water is denser than ice. Ice forms an open cage like structure because of extensive hydrogen
bonding which results in the large number of vacant spaces between them. Because of these vacant
spaces the density of ice is lesser than that of water.

Example 12 : Does water gets oxidised in the process of photosynthesis?

Solution : Yes, water gets oxidised to O2 in the process of photosynthesis
6CO2(g) + 12H2O(l)  C6H12O6(aq) + 6H2O(l) + 6O2(g)

Hard and Soft Water

Water is an excellent solvent. Rain water which is the pure form of water when comes on the surface of earth,
dissolves many salts in it. This dissolution of salts (specific salts) makes the water hard.
Hard water is the one which does not produce lather with soap easily due to the presence of calcium and
magnesium salts in the form of their bicarbonates, chlorides and sulphates. For example, sea water etc.
Soft water is the one which is free from the soluble salts of calcium and magnesium. It gives lather with
soap easily. For example, distilled water, rain water etc.
Effects of Hard Water
1. Unsuitable for laundry : Soaps are sodium or potassium salts of long chain fatty acids. Soap
containing sodium stearate (C17H35COONa) reacts with hard water to form insoluble precipitates called
scum.

M2 (aq)  2C17H35 COONa  (C17H35 COO)2 M()  2Na  (aq)
(From hard Sodium stearate Metal stearate
water ) (Soap) (ppt)

where M2+ = Ca2+ or Mg2+

Therefore, no lather is produced until all the calcium and magnesium ions are precipitated. This also
results in wastage of lot of soap.
2. Harmful for boilers : Water is used in producing steam. When hard water is used for production of
steam in boilers, it reduces the efficiency of the boilers as lot of deposition of salts in the form of scale
takes place within the boilers.
Types of Hardness
1. Temporary hardness : It is due to the presence of bicarbonates of calcium and magnesium. {Ca(HCO3)2
and Mg(HCO3)2} Temporary hardness is called so because it can be easily removed by boiling.
2. Permanent hardness : This type of hardness is due to the presence of chlorides and sulphates of
calcium and magnesium dissolved in water. As this type of hardness cannot be removed by simple
boiling, therefore it is known as permanent hardness.
Softening of Water
The process of removal of hardness from water is called softening of water.
1. Removal of temporary hardness : Temporary hardness can be removed by the following methods :
(a) Boiling : The temporary hardness of water can easily be removed by boiling the water in large
boilers. During boiling the soluble Mg(HCO3)2 is converted into Mg(OH)2 instead of MgCO3

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Hydrogen 207
Mg(OH)2 is precipitated easily, whereas Ca(HCO3)2 is changed to insoluble CaCO3 and gets
precipitated. These precipitates can be removed by filtration process. So, the filtrate obtained will
be soft water.

Mg(HCO3)2 Heating
  Mg(OH)2  + 2CO2 

Ca(HCO3)2 Heating
  CaCO3  + H2O + CO2 

(b) Clark’s method : In this process the calculated amount of slaked lime is added to hard water
containing bicarbonates of calcium and magnesium. It precipitates out calcium carbonate and
magnesium hydroxide which are then filtered to obtain soft water.
Ca(HCO3)2 + Ca(OH)2  2CaCO3  + 2H2O
Mg(HCO3)2 + 2Ca(OH)2  2CaCO3  + Mg(OH)2  + 2H2O
2. Permanent hardness : Permanent hardness of water is due to the presence of chlorides and sulphates
of calcium and magnesium. It cannot be removed by simple boiling. So, the following methods are
employed for removing permanent hardness :
(a) Treatment with washing soda : When calculated amount of Na2CO3 (washing soda) is added
to hard water containing soluble sulphates and chlorides of calcium and magnesium, then these
soluble salts get converted into insoluble carbonates which get precipitated.

CaCl2 + Na2CO3  CaCO3  + 2NaCl

ppt

MgSO4 + Na2CO3  MgCO3  + Na2SO4

ppt

Thus, water free from metal ion is soft water.

(b) Calgon’s method : Calgon is the commercial name of sodium hexametaphosphate (Na6P6O18).
Calcium and magnesium salts present in hard water react with calgon to give complex salts.
Na6P6O18  2Na+ + Na4P6O18
2–

2–  [Na MP O ]2– + 2Na+

M2+ + Na4P6O18 2 6 18
(M  Mg, Ca)

The complex anion keeps the Mg2+ and Ca2+ ions in solution.
(c) Ion-exchange method : Ion-exchange method of softening the water works on the principle of
exchanging the ions responsible for the hardness of water with the less damaging ions present
in some compounds.
This process employs the use of zeolite or permutit which is hydrated sodium aluminium silicate
(NaAlSiO4), therefore, it is also known as zeolite/permutit process. For the sake of simplicity
sodium aluminium silicate is written as NaZ. When zeolite is added to hard water, the cations
present in hard water are exchanged for sodium ions.
2NaZ(s) + M2+(aq)  MZ2(s) + 2Na+(aq) (M = Mg, Ca)
Regeneration of Permutit : As the reaction progresses, the zeolite gets exhausted because the
whole of sodium zeolite gets converted to calcium or magnesium zeolite. It is regenerated for further
use by treating with an aqueous sodium chloride solution.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
208 Hydrogen NEET

MZ2(s) + 2NaCl(aq)  2NaZ(s) + MCl2(aq)

NaCl
solution
Hard
water

Zeolite
Soft
water
Gravel
Sand

Waste
Fig. : Permutit process for water softening
(d) Synthetic resins method : This method of softening of water is prevalent nowadays. The method
is superior to zeolite method because they remove all types of unwanted cations as well as
anions present in water.
Synthetic resins are insoluble polymeric solids having giant hydrocarbon network containing reactive
acidic or basic groups. Synthetic resins are of two types :
 Cation exchange resins : Cation exchange resins contain large organic molecule with
–SO3H group and are water insoluble. The hard water is first passed through a bed of cation
exchanger. First ion exchange resin (RSO3H) gets changed to RNa after treating it with NaCl.
Now, RNa resin exchanges Na+ ions with Ca2+ and Mg2+ ions present in hard water to make
water soft.
2RNa(s) + M2+(aq)  R2M(s) + 2Na+(aq)
In order to obtain pure de-mineralised water free from all soluble mineral salts, the cation
exchange (in the H+ form) is used.

2RH(s) + M2+(aq) MR2(s) + 2H+(aq)

For example :

2R  COOH  Ca2  (RCOO)2 Ca  2H


(Cation exchange resin) (From hard water) (Exhausted resin)

In the above process as proton is released, it makes the water acidic. This water is then
passed through another bed containing anion exchanger.
 Anion exchange resin : These resins contain giant hydrocarbon framework attached to basic
groups such as –NH2 group or OH– group.
RNH2(s) + H2O(l) RNH3+OH–(s)

RNH3+OH–(s) + X–(aq) RNH3+X–(s) + OH–(aq)

For example :


R  NH3 OH  Cl  R  NH3 Cl  OH

(Anion exchange (From hard (Exhausted
resin) water) resin)

In the above reaction OH– ion exchanges for the anions in the water. OH– ions are liberated
which neutralise H+ ions set free in the cation exchange resin.
H+(aq) + OH–(aq)  H2O(l)

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Hydrogen 209
 Regeneration of resin : The cation exchanger is regenerated by the action of dilute acid
and the anion exchanger is regenerated by treating it with dilute alkali.
+ – 2–
H , Cl , SO4
Hard water

Dil. HCl or H2SO4 Dil. NaOH

for regeneration for
regeneration
Cation exchange Anion exchange
resin resin

Gravel Gravel

Waste Waste Soft water

Fig. : Ion exchange process for water softening using organic resins

Example 13 : What type of water forms scum with soap?

Solution : Hard water.

Example 14 : Write the reaction that takes place on adding lime to water containing magnesium bicarbonate.
Solution : Mg(HCO3)2 + 2Ca(OH)2  2CaCO3 + Mg(OH)2  + 2H2O

Example 15 : Explain with the help of reactions that how heavy water is used in the preparation of deuterium
compounds.
Solution : CaC2 + 2D2O  C2D2 + Ca(OD)2
SO3 + D2O  D2SO4
Al4C3 + 12D2O  3CD4 + 4Al(OD)3

Example 16 : What is ‘calgon’?

Solution : Calgon is the commercial name of sodium hexametaphosphate (Na6P6O18).

HYDROGEN PEROXIDE (H2O2)

Hydrogen peroxide was discovered by a French chemist L.J. Thenard. It is an important chemical used in
pollution control treatment of domestic and industrial effluents.

Preparation
Hydrogen peroxide is prepared by the following three main methods :
(i) By the action of cold and dilute sulphuric acid on hydrated barium peroxide
BaO28H2O(s) + H2SO4(aq)  BaSO4(s) + H2O2(aq) + 8H2O(l)
The excess water is removed by evaporation under reduced pressure.
(ii) During the electrolytic oxidation of acidified sulphate solutions at high current density gives
peroxodisulphate, which on further hydrolysis gives hydrogen peroxide

2HSO4–(aq) Electrolysis
  HO3SOOSO3H(aq)

HO3SOOSO3H(aq) Hydrolysis
  2HSO4–(aq) + 2H+(aq) + H2O2(aq)

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
210 Hydrogen NEET

The laboratory preparation of D2O2 is also done by this method

K2S2O8(s) + 2D2O(l)  2KDSO4(aq) + D2O2(l)
(iii) On the industrial scale, hydrogen peroxide is prepared by the auto-oxidation of 2-ethylanthraquinols
O2 (air)

2-ethylanthraquinol   H2O2 + oxidised product
H /Pd 2

Concentration of Hydrogen Peroxide

In the above case the H2O2 obtained is 1%. So, it needs to be concentrated. H2O2 is first extracted with water
and concentrated to ~30% and then 85% (by mass) by distillation under reduced pressure. Then to obtain
pure H2O2, the remaining water can be frozen out.

Physical Properties
(i) Pure hydrogen peroxide is a syrupy liquid. It is colourless but gives a bluish tinge in thick layers.
(ii) It is soluble in water, alcohol and ether in all proportions.
(iii) It is more viscous than water. This is due to the fact that molecules of H2O2 are more associated through
H-bonding.
Physical Properties of Hydrogen Peroxide
–3
Melting point/K 272.4 Density (liquid at 298 K)/g cm 1.44

Boiling point (extrapolated)/K 423 Viscosity (290 K)/centipoise 1.25

2 2
Vapour pressure (298 K)/mmHg 1.9 Dielectric constant (298 K)/C /N m 70.7

–3 –1 –1 –8
Density (solid at 268.5 K)g cm 1.64 Electrical conductivity (298 K) cm 5.1 × 10

Strength of H2O2 Solution

The strength of the sample of H2O2 is generally expressed in terms of the volume of oxygen at STP that one
volume of the sample of hydrogen peroxide gives on heating.
% Strength of H2O2 of 10 volume H2O2 solution
2H2O2  2H2O  O2
22.4 litres
2(2  32)  68 g
Thus 22.4 litres of oxygen at STP is obtained from 68 g

68
10 litres of oxygen at STP is obtained from  10
22.4
The concentration of 10 volume H2O2 solution is therefore = 30.35 g / litre
= 3.035 g / 100 ml
= 3.035 %.

Example 17 : Calculate the strength of 30 volume solution of hydrogen peroxide.

Solution : 30 volume solution of H2O2 means that 1 L of this H2O2 solution will give 30 L of oxygen at STP.
The decomposition of H2O2 takes place as follows
2H2O2  2H2O  O2
2  34 g 22.4 L
= 68 g at STP

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Hydrogen 211
From the equation,
22.4 L of O2 at STP is obtained from H2O2 = 68 g

68
 30 L of O2 at STP is obtained from H2O2 =  30 = 91 g
22.4
Therefore, strength of 30 volume H2O2 solution = 91 g/L

Example 18 : What is the percentage strength of a solution of 100 volume H2O2?

Solution : 100 volume solution means that 1 L of this H2O2 solution will give 100 L of oxygen at STP.
2H2O2  2H2O + O2
2 × 34 g 22.4 L
= 68 g at STP
From equation,
22.4 L of O2 at STP is obtained from H2O2 = 68 g

68
100 L of O2 at STP is obtained from H2O2 =  100
22.4
= 303.57 g/L
= 30% H2O2 solution

Structure
Hydrogen peroxide is non-linear, non-planar molecule. It has an open book type of structure. The molecular
dimensions of H2O2 in the gas phase and solid phase slightly differ from each other as shown below.

H H
95.0 pm 98.8 pm
147.5 pm 111.5° 145.8 pm 90.2°
O O O O
94.8° 101.9°
H H

(a) Gas phase (b) Solid phase

Fig. : (a) H2O2 structure in gas phase, dihedral angle is 111.5°,
(b) H2O2 structure in solid phase at 110 K, dihedral angle is 90.2°.
Chemical Properties
(i) Oxidising nature : The oxidising nature of hydrogen peroxide is due to the possession of labile oxygen
atom. The potential equation for its oxidising nature can be written as
H2O2  H2O + (O)
It is a strong oxidising agent. It acts as an electron acceptor in acidic as well as alkaline medium.
H2O2 + 2H+ + 2e–  2H2O (in acidic medium)
H2O2 + OH– + 2e–  3OH– (in alkaline medium)
In acidic medium :
2Fe2+(aq) + 2H+(aq) + H2O2(aq)  2Fe3+(aq) + 2H2O(l)
PbS(s) + 4H2O2(aq)  PbSO4(s) + 4H2O(l)

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
212 Hydrogen NEET

In alkaline medium :
2Fe2+ + H2O2  2Fe3+ + 2OH–
MnSO4 + H2O2 + 2NaOH  MnO2 + Na2SO4 + 2H2O
(ii) Reducing nature : It acts as a reducing agent in both acidic and alkaline medium towards powerful
oxidising agents.
H2O2  2H+ + O2 + 2e– (in acidic medium)
H2O2 + 2OH–  2H2O + O2 + 2e– (in alkaline medium)
The potential equation when H2O2 acts as a reducing agent is expressed as
H2O2 + O  H2O + O2
In all the reactions, molecular oxygen is always produced by the combination of H2O2 and oxygen atom
given by strong oxidising agents.
In acidic medium :
2MnO4– + 6H+ + 5H2O2  2Mn2+ + 8H2O + 5O2
HOCl + H2O2  H3O+ + Cl– + O2
In alkaline medium :
I2 + H2O2 + 2OH–  2I– + 2H2O + O2
2MnO4– + 3H2O2  2MnO2 + 3O2 + 2H2O + 2OH–
(iii) Bleaching agent : H2O2 also acts as a very good bleaching agent for delicate materials like ivory, silk,
wool, feather etc.
The bleaching action of H2O2 is due to nascent oxygen which it liberates on decomposition.
H2O2  H2O + (O)
The nascent oxygen combines with colouring matter which in turn gets oxidised. Thus, the bleaching
action of H2O2 is due to the oxidation of colouring matter by nascent oxygen and is permanent.

Storage
As the decomposition of H2O2 is catalysed by the presence of sunlight, metal surfaces, glass, alkali, dust
etc., the storage of H2O2 in appropriate containers away from sunlight is necessary. H2O2 slowly decomposes
on exposure to light in the following way
2H2O2(l)  2H2O(l) + O2(g)
Therefore, instead of being stored in glass bottles which may contain alkali metal oxides H2O2 is stored in
wax-lined glass or plastic vessels in dark. Urea is often added as a stabiliser. Precautions are taken to keep
away the dust since dust induces explosive decomposition of the compound.

Uses
Hydrogen peroxide in the form of aqueous solution has many uses like few given below :
(i) In daily life it is used as a material to bleach delicate materials like hair, cotton, wool, silk etc.
(ii) It is used as a mild disinfectant. It is also a valuable antiseptic which is sold under the name of perhydrol.
(iii) In the manufacture of sodium perborate, sodium percarbonate. These are used in high quality detergents.
(iv) In the synthesis of hydroquinone, tartaric acid and certain food products and pharmaceuticals
(cephalosporin) etc.
(v) It is used in industries as a bleaching agent for paper pulp, leather, oils, fats and textiles etc.
(vi) It is also useful in Environmental (green) chemistry. For pollution control of domestic effluents where it
restores the aerobic conditions of sewage wastes. For pollution control of industrial effluents containing
CN– ions. H2O2 oxidises CN– ions to harmless products.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Hydrogen 213

Example 19 : Why H2O2 is kept away from dust?

Solution : H2O2 is kept away from dust because dust induces explosive decomposition of the compound.

Example 20 : PbS(s) + 4H2O2(aq)  PbSO4(s) + 4H2O(l)

In the above reaction, H2O2 acts as a/an ________ agent.
Solution : Oxidising.

HEAVY WATER (D2O)

Heavy water is chemically deuterium oxide (D2O). It was discovered by Urey in 1932.
Preparation :
(i) It is prepared by the exhaustive electrolysis of ordinary water. It was shown that ordinary water contains
very small proportion of D2O. So, when prolonged electrolysis of water is done, then H2 is liberated much
faster than D2 and the remaining water becomes enriched in heavy water.
(ii) It is obtained as a by-product in some fertilizer industries.
Uses : It has some important uses as :
(i) Moderator : Heavy water is used as a moderator in nuclear reactors. The job of the moderator is to
slow down the fast moving neutrons and therefore controls the nuclear fission process.
(ii) Tracer compound : It is used as a tracer compound, in studying the reaction mechanisms.
(iii) For the preparation of deuterium compounds : It is used as a starting material for the preparation
of a number of deuterium compounds
CaC2 + 2D2O  C2D2 + Ca(OD)2
SO3 + D2O  D2SO4
Al4C3 + 12D2O  3CD4 + 4Al(OD)3

DIHYDROGEN AS A FUEL
Nowadays, dihydrogen as a fuel is also used because of its various advantages over conventional fuels like
petrol, diesel, coal etc.
1. First of all dihydrogen releases large quantities of heat on combustion. The energy released by
combustion of fuels like dihydrogen, methane, LPG etc., are compared in terms of the same amounts
in mole, mass and volume as shown in the table below :

Energy released on Dihydrogen Dihydrogen LPG CH4 gas Octane

combustion (in kJ) (in gaseous (in liquid (in liquid
state) state) state)
per mole 286 285 2220 880 5511
per gram 143 142 50 53 47
per litre 12 9968 25590 35 34005
It is clear from the above table that on a mass for mass basis, dihydrogen can release about three times
more energy than petrol (here octane).
2. Secondly, burning of hydrogen in air yields water as the only product. This way being non-polluting is
beneficial in contrast to burning coal in power stations, petrol or diesel in motor engines which release
lot of pollutants in the environment.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
214 Hydrogen NEET

On the other hand their are certain limitations also. The production of dihydrogen is very costly. Moreover
the cylinder of compressed dihydrogen weighs about 30 times as much as a tank of petrol containing
the same amount of energy. Even the liquefaction of dihydrogen gas requires cooling to 20 K temperature,
which is quite expensive. Dihydrogen must be kept out of contact with oxygen or air with which it forms
explosive mixtures. So, tanks of metal alloy like those of NaNi5, Ti–TiH2, Mg–MgH2 etc., are used for
the storage of dihydrogen.
So, word Hydrogen Economy is used nowadays for the transportation and storage of energy in the form
of liquid or gaseous dihydrogen. The further advantage of hydrogen economy is that energy is
transmitted in the form of dihydrogen and not as electric power. It was for the first time in the history
of India that a pilot project using dihydrogen as fuel is launched in Oct, 2005 for running automobiles.
Initially 5% dihydrogen was mixed with CNG for use in four-wheeler vehicles. But, now the percentage
of dihydrogen appears to increase.
Nowadays, it is also used in fuel cells for generation of electric power. Thus, if a cheap source of large
scale production of hydrogen is discovered in the years to come then hydrogen economy will become
the common source of energy.

EXERCISE
1. What is the half life period of tritium?
(1) 13.33 years (2) 12.33 years
(3) 12 years (4) 22.33 years
2. Zn + 2NaOH  A + B
What is A and B?
(1) NaH and H2 (2) Na2Zn and H2
(3) Na2ZnO2 and H2 (4) Reaction rarely occurs
3. Which element forms electron rich hydride?
(1) C (2) O
(3) B (4) Al
4. Formula of calgon is
(1) Na6P6O18 (2) Na5P5O18
(3) Na4P4O18 (4) Na2MP6O18
5. What is the amount of O2 liberated at STP by “30 volume” 1 L solution of H2O2?
(1) 1.5 L (2) 2.5 L
(3) 30 L (4) 3 L
6. Among the following which is/are interstitial hydride?
(1) LaH3 (2) CaH2
(3) NaH (4) HF
7. Among the following in which hydrates H2O molecules only occupy the interstitial site
(1) BaCl2.2H2O (2) [[Ni(H2O)6]2+](NO3–)2
(3) CuSO4.5H2O (4) All of these
8. Which property of hydrogen makes it to resemble with halogen among the following statements?
(1) Hydrogen has strong affinity for non-metals (2) Hydrogen has high ionisation potential
(3) Hydrogen has low value of electron affinity (4) Hydrogen acts as reducing agent

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Hydrogen 215
9. Which of the following is electron precise hydride?
(1) BH3 (2) CH4
(3) H2O (4) HF
10. Demineralised H2O is obtained when
(1) Water is passed through R–SO3H resin
+
(2) Water is passed through R–NH3OH resin

(3) Water is passed through both RSO3H resin and R NH3OH resin
(4) We can’t get demineralised H2O artificially by resins

Note :
1. Hydrogen has the simplest atomic structure with only one proton and one electron. It is the only element
which has no neutron.
2. Hydrogen in its elemental form exists as dihydrogen. Dihydrogen is the most abundant element in the
universe. In free state it is not found in the earth crust. However, in the combined form, it constitutes 15.4%
of the earth’s crust and oceans.
3. Dihydrogen is colourless, odourless and combustible gas. The H–H bond dissociation enthalpy is the
highest for a single bond between two atoms of any element. Therefore, atomic hydrogen is prepared only
at high temperature.
4. Atomic hydrogen and oxyhydrogen torches are used for cutting and welding purpose.
5. It acts as a rocket fuel and even has a promising potential for use as a non-polluting fuel of the near future
(hydrogen economy).
6. Water dissolves many salts in it making it hard. Hard water is the one which contains calcium and
magnesium salts in the form of hydrogencarbonate, chlorides and sulphates.
7. Hydrogen peroxide good bleaching agent and is used in pollution control treatment of industrial and
domestic effluents.

‰ ‰ ‰

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
 t
en
nm nment
sig ssig
As A Assignment

Assignment
6. PbS on reaction with H2O2 gives
SECTION - A
[NCERT Pg. 294]
NCERT Based MCQs
(1) Pb (2) PbO
1. High purity dihydrogen is obtained by
[NCERT Pg. 286] (3) PbSO3 (4) PbSO4

(1) Electrolysing warm aqueous barium hydroxide 7. In which of the following type of hydrides the law
with nickel electrode. of constant composition does not hold good?
[NCERT Pg. 288]
(2) Byproduct in the manufacture of sodium
hydroxide (1) Electron rich covalent hydride

(3) Reaction of steam on hydrocarbon (2) Ionic hydride

(4) Electrolysis of acidified water using platinum (3) Electron deficient covalent hydride
electrode (4) Metallic hydride
2. Water gas shift reaction is [NCERT Pg. 286] 8. Maximum boiling point among the following is of
(1) CO(g) + H2O(g)  CO2(g) + H2(g) [NCERT Pg. 289]
(2) H2(g) + CO2(g)  CO(g) + H2O(g) (1) NF

(3) CH4(g) + H2O(g)  CO(g) + 3H2(g) (2) NH3

(4) CO(g) + 3H2(g) CH4(g) + H2O(g) (3) H2O

3. Which of the following groups do not form hydride? (4) HCl

[NCERT Pg. 288] 9. Most ionic hydride is [NCERT Pg. 288]
(1) 7 (1) LiH (2) NaH
(2) 8 (3) KH (4) CsH
(3) 9 10. Highest bond dissociation enthalpy is of
(4) All of these [NCERT Pg. 286]
4. Maximum number of hydrogen bonds per molecule (1) H2 (2) F2
of water is [NCERT Pg. 286] (3) Cl2 (4) Br2
(1) 1 11. Hydrogen resembles with halogen because of the
(2) 2 reason that [NCERT Pg. 288]
(3) 3 (1) It forms diatomic molecules
(4) 4 (2) Combine with elements to form hydrides
5. CaC2 + 2D2O  Products possible products of (3) Forms a large number of covalent compound
above reaction is/are [NCERT Pg. 294] (4) All of these
(1) C2D2 12. ‘5 Vol’ H2O2 solution is equivalent to
(2) CO2 [NCERT Pg. 293]

(3) Ca(OD)2 (1) 3% H2O2 (2) 1.5% H2O2

(4) Both (1) and (3) (3) 5% H2O2 (4) 6% H2O2

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Hydrogen 217
13. Which reaction is showing reducing action of H2O2 4. Choose the incorrect reaction
[NCERT Pg. 294]
D2O
(1) SO3 
(1) 2Fe2+(aq) + 2H+(aq) + H2O2(aq)  2Fe3+(aq)  D2SO4
+ 2H2O(l)
(2) Zn  H2SO4  ZnSO4 + H2
(2) 2Fe2+ + H2O2  2Fe3+ + 2OH– (Conc.)

(3) Mn2+ + H2O2  Mn4+ + 2OH– 

H
(3) MnO4–  H2O2  Mn+2 + O2 + H2O
(4) HOCl + H2O2  H3O+ + Cl– + O2
14. Hydrogen bonding in water is responsible for which HO
(4) NaH 
2
 NaOH + H2
of the given properties? [NCERT Pg. 290]
(1) High value of surface tension 5. Which of the following is prepared by hydrocarbon-
steam process?
(2) High latent heat of evaporation
(1) Producer gas
(3) High boiling point
(2) Synthesis gas
(4) All of these
(3) Coal gas
15. Maximum energy released per g by the
combustion of among the following substance is in (4) Marsh gas
[NCERT Pg. 295]
6. Which of the following is a non-planar molecule?
(1) H2(g)
(1) T2O2
(2) H2(l)
(2) D2O2
(3) CH4(g)
(3) H2O2
(4) LPG (4) All of these
7. Which of the following method can be used to
SECTION - B remove permanent hardness of water?
Objective Type Questions (1) Clark's process
1. Which of the following hydride is known as (2) Heating
'hydrolith'?
(3) Washing soda method
(1) CaH2
(4) All of these
(2) MgH2
8. Which of the following is used as a stabiliser in the
(3) NaH
decomposition of hydrogen peroxide?
(4) AlH3
(1) Dust
2. Ionic hydrides are formed by all s-block elements,
(2) Alkali
except
(3) Light
(1) Ca and Sr (2) Mg and Be
(3) K and Cs (4) Li and Rb (4) Urea

3. Which of the following isotopic form of hydrogen 9. PbS + H2O2  (A) + H2O
has the slowest rate of reaction? Species (A) is
(1) H2 (1) PbO2
(2) D2 (2) H2S
(3) T2 (3) PbSO4
(4) All react with the same rate (4) PbSO3

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
218 Hydrogen NEET

10. The basic principle of hydrogen economy is 16. Hydrogen peroxide hydrate exists as
(1) Saving hydrogen for future use (1) H2O2.H2O

(2) Storage and transportation of energy in the (2) H2O2.3H2O

form of dihydrogen (3) H2O2.5H2O
(3) To reduce the cost of hydrogen usage (4) Hydrate of hydrogen peroxide does not exist
(4) To minimize the consumption of dihydrogen 17. The least reactive form of hydrogen is
11. A solution of H2O2 is labelled 5 volume. Its strength (1) H2
in gL–1 (grams/litre) is nearly
(2) Nascent hydrogen
(1) 10
(3) Atomic hydrogen
(2) 15.2
(4) All are equally reactive
(3) 20
(4) 12.6 SECTION - C
12. The ratio of ortho and para hydrogen in a given Previous Years Questions
sample of dihydrogen gas above room
1. The method used to remove temporary hardness of
temperature is
water is [NEET-2019]
(1) 1 : 1
(1) Calgon's method
(2) 3 : 1
(2) Clark's method
(3) 1 : 2
(3) Ion-exchange method
(4) 2 : 1
(4) Synthetic resins method
13. The difference in the rate of reaction of H2, D2 & T2
2. Which of the following statements about hydrogen
due to their different mass numbers is called
is incorrect? [NEET-2016]
(1) Allotropic effect
(1) Dihydrogen does not act as a reducing agent
(2) Isotopic effect
(2) Hydrogen has three isotopes of which tritium is
(3) Kinetic effect the most common

(4) Nuclear spin effect (3) Hydrogen never acts as cation in ionic salts

14. Which of the following hydride is a very powerful (4) Hydronium ion, H3O+ exists freely in solution
reducing agent?
3. In acidic medium, H2O2 changes Cr2O72 to CrO5
(1) NaH which has two (–O–O–) bonds. Oxidation state of Cr
(2) MgH2 in CrO5 is [AIPMT-2014]
(1) +5 (2) +3
(3) AlH3
(3) +6 (4) –10
(4) NiH0.6
4. The ease of adsorption of the hydrates alkali metal
15. Which of the following acts as an inorganic cation ions on an ion-exchange resins follows the order
exchanger for removing hardness of water?
[AIPMT (Prelims)-2012]
(1) RSO3H
+ + + +
(1) K < Na < Rb < Li
(2) Na6P6O18
(2) Na+ < Li+ < K+ < Rb+
(3) NaAlSiO4
(3) Li+ < K+ < Na+ < Rb+
(4) RNH3OH (4) Rb+ < K+ < Na+ < Li+
Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Hydrogen 219
5. Some statements about heavy water are given below 10. Which one of the following pairs of substances on
reaction will not evolve H2 gas?
a. Heavy water is used as a moderator in nuclear
reactors (1) Copper and HCl (aqueous)
b. Heavy water is more associated than ordinary (2) Iron and steam
water (3) Iron and H2SO4 (aqueous)
c. Heavy water is more effective solvent than (4) Sodium and ethyl alcohol
ordinary water
11. Zn gives H2 gas with H2SO4 and HCl but not with
Which of the above statements are correct ? HNO3 because
[AIPMT (Mains)-2010] (1) Zn act as oxidizing agent when react with HNO3
(1) a and b (2) HNO3 is weaker acid than H2SO4 and HCl
(2) a, b and c (3) In electrochemical series Zn is above hydrogen

(3) b and c (4) NO3 is reduced in preference to hydronium ion

(4) a and c 12. Which pair of substances gives same gaseous
product, when these react with water?
Questions asked Prior to Medical Ent. Exams. 2005
(1) K and KO2
6. Hydrogen is prepared from H2O by adding
(2) Ba and BaO2
(1) Ca, which acts as reducing agent (3) Ca and CaH2
(2) Al, which acts as oxidising agent (4) Na and Na2O2
(3) Ag, which acts as reducing agent 13. Ortho and para hydrogen differ in
(4) Au, which acts as oxidising agent (1) Proton spin
7. The hydride ion H – is stronger base than its (2) Electron spin
hydroxide ion OH–. Which of the following reaction
(3) Nuclear charge
will occur if sodium hydride (NaH) is dissolved in
water? (4) Nuclear reaction

(1) H– + H2O  No reaction 14. Action of water or dilute mineral acids on metals
can give
(2) H– (aq) + H2O  H2O
(1) Monohydrogen
(3) H– (aq) + H2O(l)  OH– + H2
(2) Tritium
(4) None of these
(3) Dihydrogen
8. Which of the following statements about the (4) Trihydrogen
interstitial compounds is incorrect?
15. Deuterium resembles hydrogen in chemical
(1) They are chemically reactive properties but reacts
(2) They are much harder than the pure metal (1) More vigorously than hydrogen
(3) They have higher melting points than the pure (2) Faster than hydrogen
metal
(3) Slower than hydrogen
(4) They retain metallic conductivity
(4) Just as hydrogen
9. The volume strength of 1.5 NH2O2 solution is 16. Spin isomerism is shown by
(1) 8.8 (1) Dichloro benzene
(2) 8.4 (2) Hydrogen
(3) 4.8 (3) Dibasic acid
(4) 5.2 (4) n-butane

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
220 Hydrogen NEET

17. Hydrogen can be fused to form helium at 24. Hydrogen peroxide is reduced by
(1) High temperature and high pressure (1) Ozone
(2) High temperature and low pressure (2) Barium peroxide
(3) Low temperature and high pressure (3) Acidic solution of KMnO4
(4) Low temperature and low pressure (4) Lead sulphide suspension

18. What is formed when calcium carbide reacts with 25. The volume of oxygen liberated from 15 ml of 20
heavy water volume H2O2 is

(1) C2D2 (1) 250 ml

(2) CaD2 (2) 300 ml

(3) Ca2D2O (3) 150 ml

(4) CD2 (4) 200 ml

19. Maximum number of hydrogen bonding in H2O is 26. The volume of oxygen liberated from 0.68 g of H2O2
is
(1) 1
(1) 112 ml
(2) 2
(2) 224 ml
(3) 3
(3) 56 ml
(4) 4
(4) 336 ml
20. In which of the following reaction hydrogen peroxide
is a reducing agent? 27. 20 volume H2O2 solution has a strength of about
(1) 2FeCl2 + 2HCl + H2O2  2FeCl3 + 2H2O (1) 30%
(2) Cl2 + H2O2  2HCl + O2 (2) 6%
(3) 2HI + H2O2  2H2O + I2 (3) 3%
(4) H2SO3 + H2O2  H2SO4 + H2O (4) 10%
21. There is a sample of 10 volume of hydrogen 28. The H – O – O bond angle in H2O2 (g) is
peroxide solution. Calculate its strength.
(1) 107.28° (2) 109.28°
(1) 3.00%
(3) 104.5° (4) 94.8°
(2) 4.045%
(3) 2.509% SECTION - D
(4) 3.035% NEET Booster Questions
22. In lab H2O2 is prepared by 1. Occlusion is
(1) Cold H2SO4 + BaO2 (1) Hydrogenation of oils
(2) HCl + BaO2 (2) Hydrolysis of hydrocarbon
(3) Conc. H2SO4 + Na2O2 (3) Adsorption of gas by metals
(4) H2 + O2 (4) Electrolysis of acidified water
23. H2O2 acts as an oxidising agent in 2. Hydride gap region is
(1) Acidic medium only (1) Group 1 and 17
(2) Alkaline medium only (2) Group 7, 8, 9
(3) Neutral medium only (3) Group 5, 6, 7
(4) Acidic and alkaline medium (4) Group 8, 9, 10
Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Hydrogen 221
3. 5 L of water contains 11.1 mg of CaCl2 and 12 mg 9. Which hydride can form banana bond?
of MgSO 4. Find out its degree of hardness(in
(1) LiH
ppm).
(2) NaH
(1) 20
(3) CaH2
(2) 10
(4) BeH2
(3) 4
10. Which reaction is called autoprotolysis?
(4) 15
4. Which of the following is correct regarding (1) 2H2O H3O+ + OH–
hydrogen bonding in HF?
(2) H2O H+ + OH–
H H (3) H2O + H+ H3O+
F F
(1) F F
H H (4) OH– + H+ H2O

11. LaH2.87 hydride belongs to

(2) Metal fluorides are solvated by HF giving HF2
(1) Ionic hydride (2) Covalent hydride
(3) HF is a high melting solid at room temperature
(3) Metallic hydride (4) Saline hydride
(4) All of these
12. The product of the following reaction
5. Terrestrial hydrogen contains 0.0156% of deuterium
HOCl + H2O2  H3O+ + Cl– + X, here X is
in the form of
(1) ClO– (2) H2O
(1) D2O
(3) OH– (4) O2
(2) D2
13. Hydrogen can be prepared by
(3) HD
(1) Electrolysis of acidified water
(4) HOD
(2) Bosch's process
6. Which of the following will produce H2?
(3) Lane's process
(1) Al2O3 + NaOH
(4) All of these
(2) Cu + dil HCl
14. Commercial hydrogen is obtained from
(3) Zn + NaOH
(1) Coal gas
(4) Ag + dil H2SO4
(2) Water gas
7. Which reaction is called coal gasification?
(3) Air
(1) C(s) + H2O(g)  CO(g) + H2(g)
(4) Producer gas
(2) CO(g) + H2(g) + H2O(g)  CO2(g) + 2H2(g)
15. Which is a source of nascent hydrogen?
(3) CO2(g) + C(g)  2CO(g)
I. Zn + dil HCl
1 II. CH3OH + Na
(4) C(g)  O2 (g) CO(g)
2
III. Electrolysis of H2O
8. The reactants in Lane's process are IV. Silent electric discharge of H2O2
(1) Fe + H2O (l) (1) I & II
(2) Fe + H2O (g) (2) II & III
(3) Fe3O4 + H2 (3) I, II, III
(4) Fe2O3 + H2 (4) IV

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
222 Hydrogen NEET

16. Electrolysis of 50% H2SO4 gives 23 Which of the following is correct?

(1) H2O (1) LiH is thermally more stable than CsH
(2) D2O 1
(2) Density of H2 is about th of that of air
(3) H2O2 14
(3) Atomic hydrogen is much more reactive than
(4) SO2
ordinary hydrogen
17. Maximum number of hydrogen bonds formed by a
(4) All of these
single molecule of water is
24. When same amount of zinc is treated separately
(1) 1
with excess of sulphuric acid and excess of sodium
(2) 2 hydroxide solution, the ratio of volumes of hydrogen
(3) 3 evolved is

(4) 4 (1) 1 : 1

18. In water gas shift reaction reactant is (2) 1 : 2

(1) H2 + H2O (3) 2 : 1

(2) H2 + CO2 (4) 9 : 4

h
(3) CO + H2O(g) 25. CH3D  Cl2  Product.
(1 mole)
(4) H2 + D2
The product is
19. In Ortho and Para hydrogen, the nuclear spin
respectively are (1) CH2DCl

(1) Parallel and opposite (2) CH3Cl

(2) Opposite and parallel (3) CDCl3

(3) It may be parallel or opposite (4) CCl4

(4) They do not differ in nuclear spin 26. Which of the following is most reactive?

20. When hydrolith is treated with water it yields (1) H2

(1) H2 (2) H2O2 (2) H (nascent)

(3) NaH (4) N2 (3) D2

21. Which of the following will determine whether the (4) H (atomic)
given colourless liquid is water or not? 27. When 50% solution of H2SO4 is electrolysed by
(1) Melting passing a current of high density at low temperature
then main products of electrolysis are
(2) Tasting
(1) Oxygen & Hydrogen
(3) Phenolphthalein
(2) H2 and peroxy disulphuric acid
(4) Adding a pinch of anhydrous CuSO4
(3) H2 and SO2
22. Select the correct statement.
(4) O2 and peroxy disulphuric acid
(1) O–H bond is stronger than O–D bond
28. Interstitial hydrides are formed by
(2) O–H bond is weaker than O–D bond
(1) s-block metals
(3) Permanent hardness of water is due to the
presence of bicarbonates of calcium and (2) p-block metals
magnesium (3) d-block metals
(4) O–H and O–D bond strength is same (4) All of these

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET Hydrogen 223
29. The group of elements responsible for hydride gap 36. Both cations and anion impurities can be removed
from hard water by using
(1) Mn, Ca, Ni
(1) Zeolites
(2) Mn, Fe, Li
(3) Mn, Fe, Co (2) Organic ion exchanges

(4) Mn, Cu, Cl (3) Calgon

30. Which of the following is interstitial hydride? (4) All of these

(1) CaH2 37. H2O2 acts as

(2) CuH (1) Oxidising agent (2) Reducing agent

(3) PH3 (3) Bleaching agent (4) All of these

(4) NaH 38. Structure of blue vitriol shows presence of
31. Hydrogen exists in atomic state in which of the (1) Coordinate bond
following compounds?
(2) Covalent bond
(1) Metallic hydrides
(3) Hydrogen bond
(2) Ionic hydride
(4) All of these
(3) Molecular hydrides
39. Hydrogen peroxide is used as
(4) H2O
(1) Oxidising agent only
32. The velocity of neutrons in nuclear reactor is slowed
down by (2) Reducing agent only

(1) Heavy water (3) Both as oxidising and reducing agent

(2) Ordinary water (4) Drying agent

(3) Zinc rod 40. H2O2 is manufactured these days
(4) Fused caustic soda (1) By the action of H2O2 on BaO
33. Heavy water has maximum density at (2) By the action of H2SO4 on Na2O
(1) 4°C (3) By electrolysis of 50% H2SO4
(2) 11.6°C (4) By burning hydrogen in excess of oxygen
(3) 0°C 41. H2O2 restores the colour of old lead paintings,
(4) 273 K blackened by the action of H2S gas by

34. Heavy water is (1) Converting PbO2 to Pb

(1) H2O (2) Oxidising PbS to PbSO4

(2) D2O (3) Converting PbCO3 to Pb

(3) Water at 4°C (4) Oxidising PbSO3 to PbSO4
(4) Water obtained by repeated distillation 42. In the reaction
35. Heavy water is called as heavy because it is 2K3[Fe(CN)6] + 2KOH + H2O2 
(1) A heavy liquid 2K4[Fe(CN)6] + 2H2O + O2
(2) An oxide of heavier isotope of oxygen H2O2 acts as
(3) An oxide of deuterium (1) Reducing agent (2) Oxidising agent
(4) Less denser than H2O (3) Knocking agent (4) Bleaching agent

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
224 Hydrogen NEET

43. Decomposition of H2O2 can be slowed down by 47. The normality of 10 volume H2O2 is nearly
addition of small amount phosphoric acid which act
(1) 2.15
as
(2) 3.41
(1) Stopper (2) Inhibitor
(3) 1.78
(3) Detainer (4) Promotor
(4) 5.15
44. H2O2 H2O + O2
48. The amount of H2O2 present in 1 L of 1.5 N H2O2
This represents
solution is
(1) Oxidation of H2O2
(1) 2.5 g
(2) Reduction of H2O2
(2) 25.5 g
(3) Disproportionation of oxygen
(3) 3.0
(4) Acidic nature of H2O2
(4) 8.0
45. 20 volume hydrogen peroxide means
49. H2O and H2O2 resemble in
(1) 1 ml of H2O2 solution gives 20 L of O2 at NTP
(1) Hybridisation of oxygen
(2) 1 mole of H2O2 give 20 ml of O2 at NTP
(2) Oxidation state of oxygen
(3) 1 g of H2O2 give 20 ml of O2 at NTP
(3) Structure
(4) 1 ml of H2O2 solution give 20 ml of O2 at NTP
(4) Bond angle
46. Which of the following hardness of water can be
simply removed by boiling? 50. Boiling point of D2O is

(1) Mg(HCO3)2 (2) CaCl2 (1) 100°C (2) 105.5°C

(3) CaSO4 (4) All of these (3) 101.4°C (4) 102.6°C

‰ ‰ ‰

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
Chapter 22

The s-Block Elements

Chapter Contents
z Introduction Introduction
z The s-Block Elements In this chapter we will study the general characteristics of the alkali
and alkaline earth metals and their compounds. We will also study
z Group-1 Elements : Alkali the compounds of s-block elements, their uses and importance,
Metals commercially and industrially. The biological significance of sodium,
z General Characteristics of potassium, calcium and magnesium will also be discussed is this
the Compounds of the Alkali chapter.
metals

z Anomalous Properties of THE s-BLOCK ELEMENTS

Lithium s-block is located at extreme left hand side of the periodic table. Since
z Some Important Compounds s orbital can accommodate only two electrons, the elements having one electron
of Sodium in their outermost s-orbital are grouped into group-1 and those having two
electrons are grouped into group-2 of periodic table.
z Biological Importance of
Sodium and Potassium Group-1 of periodic table contains : Lithium (Li), Sodium (Na), Potassium (K),
Rubidium (Rb), Caesium (Cs) and Francium (Fr). Together these elements are
z Group-2 Elements : Alkaline called alkali metals because they form hydroxides on reaction with water, which
Earth Metals
are strongly alkaline in nature. Sodium and Potassium are abundant in nature
z General Characteristics of while Lithium, Rubidium and Caesium have lower abundance. Francium, the last
Compounds of the Alkaline element of group-1, is radioactive.
Earth Metals
The group-2 includes Beryllium (Be), Magnesium (Mg), Calcium (Ca), Strontium
z Anomalous Behaviour of (Sr), Barium (Ba) and Radium (Ra). Except Beryllium, rest of the elements of
Beryllium group-2 are called the alkaline earth metals. These are called so because
their oxides and hydroxides are alkaline in nature and these metal oxides are
z Some Important Compounds
found in the earth crust.
of Calcium
Beryllium is not considered alkaline earth metal because its oxide i.e., BeO
z Biological Importance of
is amphoteric is nature, which can be explained by its reaction with acids as
Magnesium and Calcium
well as alkalies.
BeO + 2HCl  BeCl2 + H2O
BeO + 2NaOH + H2O  Na2[Be(OH)4]
sodium beryllate

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
76 The s-Block Elements NEET

Out of alkaline earth metals, calcium and magnesium are ranked 5th and 6th respectively as per their
abundance in the Earth’s crust, Strontium and Barium have comparatively lower abundance, Beryllium is rare
and Radium is the rarest of all alkaline earth metals.

Example 1 : What are s-block elements?

Solution : s-Block elements are those is which the last electron enters the outermost s-orbital.

Example 2 : Name alkali metals in increasing order of atomic number.

Solution : Lithium, Sodium, Potassium, Rubidium, Caesium and Francium.

Example 3 : Which element of group 2 is not considered as alkaline earth metal?

Solution : Beryllium.

General electronic configuration for alkali metals is [noble gas] ns1 and that for alkaline earth metals is
[noble gas]ns2.
The first element in each group shows some anomalous behaviour or properties as compared to other
members of the respective group due to
(i) Smaller size of the atom
(ii) Their higher ionization enthalpies
(iii) Their higher electronegativities
(iv) Absence of vacant d-orbitals in their valence shells
In these anomalous properties they resemble the second element of the next group. Thus lithium shows
similarities to magnesium and beryllium to aluminium in many of their properties, and this similarty is known
as diagonal relationship.
Group-1 Group-2 Group-13 Group-14

Period-2 Li Be B

Period-3 Mg Al Si

Cause of Diagonal Relationship

In moving along the period from left to right the electropositive character decreases while in descending a
group, electropositivity of the elements increases. These two effects tend to cancel each other in moving
diagonally from top left to bottom right. Therefore, the elements diagonally related in this way tend to have
similar properties or we can say that diagonal relationship is due to the similarity in ionic sizes.

Example 4 : Write the general electronic configuration of alkali metal and alkaline earth metal.
Solution : General electronic configuration of alkali metal is [noble gas] ns1 and that of alkaline earth metal
is [noble gas]ns2.

Example 5 : Lithium show diagonal relationship with which element?

Solution : Magnesium

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET The s-Block Elements 77
GROUP-1 ELEMENTS : ALKALI METALS
The alkali metals show a regular trend in their physical and chemical properties with the increasing atomic
number.

1. Electronic Configuration
The alkali metals have one valence electron, outside the noble gas core.

[Noble gas]ns1 ; where n = 2 to 7

Since the outermost electron is loosely held, alkali metals readily lose electron to give monovalent M+ ions,
that is why they are most electropositive metals and are never found in free state in nature.

The electronic configurations of alkali metals are given below in table

Element Symbol Electronic configuration

Lithium Li 1s22s1 or [He]2s1

Sodium Na 1s22s22p63s1 or [Ne]3s1

Potassium K 1s22s22p63s23p64s1 or [Ar]4s1

Rubidium Rb 1s22s22p63s23p63d104s24p65s1 or [Kr]5s1

Caesium Cs 1s22s22p63s23p63d104s24p64d105s25p66s1 or [Xe]6s1

Francium Fr 1s22s22p63s23p63d104s24p64d104f145s25p65d106s26p67s1 or [Rn]7s1

2. Atomic and Ionic Radii

The atoms of alkali metals have the largest size in their respective periods. The atomic radius increases on
moving down the group.

Reason : On moving down the group there is a progressive addition of new energy shells. Although, the nuclear
charge also increases down the group but the effect of addition of new shells is more dominant and hence
atomic radii of alkali metals increases on going down the group from top to bottom

Within the group, the ionic radii increase with increase in atomic number.

Example 6 : Why the alkali metals are never found in free state in nature?

Solution : The alkali metals readily lose electron to give monovalent M+ions, hence they are highly reactive
and therefore they are never found in free state in nature.

3. Ionization Enthalpy
The first ionisation enthalpies of alkali metals are low as compared to the elements of other groups belonging
to the same period. However, within the group the ionization enthalpies of the alkali metals decrease down
the group.

The radii of atoms of alkali metals are the largest in their respective periods, therefore, the outermost electrons
which are far away from the nucleus experience a less force of attraction from the nucleus and hence can
be easily removed.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
78 The s-Block Elements NEET

4. Hydration Enthalpy
The alkali metal ions are extensively hydrated in aqueous solutions. Smaller the ion more is the extent of
hydration. The hydration enthalpies of alkali metal ions decrease with increase in ionic size
Li+ > Na+ > K+ > Rb+ > Cs+ (hydration energy decreases)
Li+ has maximum degree of hydration and for this reason many lithium salts exist as hydrated salts. For
example, LiCl. 2H2O

5. Physical Properties
Alkali metals are silvery white in colour and are generally soft and light metals. Softness of alkali metals is
due to weak metallic bonding in them because of large size of the atoms. As we move down the group metallic
bonding weakens and hence, softness increases. Potassium is softer than sodium. The densities of alkali
metals are low and increase down the group. Potassium, however, is lighter than sodium. Lithium is the
lightest metal having a density of 0.534 g/cm3. It cannot be stored in kerosene oil because it floats on the
surface. It is kept wrapped in paraffin wax. The low density of alkali metals is attributed to their large atomic
size and weak metallic bond. However, going down the group, atomic size as well as atomic mass increases
but the corresponding increase in atomic mass is not neutralised by the increase in atomic volume : Thus,
the ratio, mass/volume, i.e., density gradually increases.
Alkali metals have low melting and boiling point. The low melting point are attributed to their larger atomic
size, due to which the binding energies of their atoms in the crystal lattice are low. Further, in moving down
the group, their atomic size increase and the strength of metallic bond decreases which causes decrease
in melting points. The boiling points of the members of this group also follow the same order due to same
reasons.

Example 7 : Why alkali metals are soft?

Solution : Because they have weak metallic bond.

Flame Colouration
When alkali metals and their salts are heated in the oxidizing flame of a Bunsen burner, they impart
characteristic colours to the flame. This happens because the heat from the flame excites the outermost orbital
electron to a higher energy level. When the excited electron comes back to the ground state, there is emission
of radiation in the visible region as given below.

Metal Li Na K Rb Cs
Colour Crimson red Yellow Violet Red violet Blue
/nm 670.8 589.2 766.5 780.0 455.5

This particular property of alkali metals is helpful in detecting them by respective flame tests and can be
determined by flame photometry or atomic absorption spectroscopy.

Photoelectric Effect
Alkali metals (except Li) exhibit photoelectric effect (a phenomenon of emission of electrons from surface by
exposing it to visible light). These elements when irradiated with light, the light energy absorbed may be
sufficient to make an atom lose electron. This property makes caesium and potassium useful as electrodes
in photoelectric cells.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET The s-Block Elements 79
Atomic and Physical Properties of the Alkali Metals

Property Lithium Sodium Potassium Rubidium Caesium Francium

Li Na K Rb Cs Fr

Atomic number 3 11 19 37 55 87
–1
Atomic mass (g mol ) 6.94 22.99 39.10 85.47 132.91 (223)
1 1 1 1 1 1
Electronic configuration [He] 2s [Ne] 3s [Ar] 4s [Kr] 5s [Xe] 6s [Rn] 7s
Ionization 520 496 419 403 376 375
–1
enthalpy/kJ mol

Hydration –506 –406 –330 –310 –276 –

–1
enthalpy/kJ mol

Metallic 152 186 227 248 265 –

radius / pm
+
Ionic radius M / pm 76 102 138 152 167 (180)
m.p. / K 454 371 336 312 302 –
b.p / K 1615 1156 1032 961 944 –

Density / g cm –3 0.53 0.97 0.86 1.53 1.90 –

Standard potentials –3.04 –2.714 –2.925 –2.930 –2.927 –
+
E / V for (M / M)
Occurrence in 18* 2.27** 1.84** 78-12* 2-6* ~10–18*
lithosphere†

*ppm (part per million), ** percentage by weight; † Lithosphere : The Earth’s outer layer : its crust and part
of the upper mantle

Example 8 : Why does alkali metals impart characteristic colour to the flame?
Solution : This happens because the heat from the flame excites the outermost orbital electron to a higher
energy level. When the excited electron comes back to the ground state, there is emission of
radiation in the visible region.

Example 9 : How flame test helps in distinguishing alkali metals?

Solution : Alkali metals give characteristic colour on flame, which helps in distinguishing them.

6. Chemical Properties
The alkali metals are highly reactive elements. The cause for their high chemical reactivity is (i) Low value
of first ionisation enthalpy (ii) Large size (iii) low heat of atomisation. The reactivity of these metals increases
down the group.
(i) Reactivity towards air : You might have seen that alkali metals tarnish in dry air because of formation
of their oxides and when these oxides react with moisture they form hydroxides.
Alkali metals burn very fast in oxygen and form different kind of oxides like monoxides, peroxides and
superoxides. Lithium forms monoxide, sodium forms peroxide and other metals form superoxides. The
superoxide O2– ion generally remain stable only in the presence of large cations like K, Rb, Cs. This
stability is related to the compatibility of size and higher lattice energy

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
80 The s-Block Elements NEET

4Li + O2  2Li2O (oxide)

2Na + O2  Na2O2 (peroxide)
M + O2  MO2 (superoxide)
(M = K, Rb, Cs)
In all the compounds formed by alkali metals with oxygen, their oxidation state is +1.
Due to diagonal relationship with magnesium, lithium like magnesium forms its nitride, Li3N. Rest of the
alkali metals do not behave in this way.
Alkali metals are generally kept immersed in kerosene oil because they are highly reactive towards air
and water.

Example 10 : Why do alkali metal tarnishes in air?

Solution : They tarnish because of formation of their oxides.

(ii) Reactivity towards water: The alkali metals on reaction with water form their respective hydroxide and
dihydrogen.
2M + 2H2O  2M+ + 2OH– + H2
(M = an alkali metal)
This tendency of forming hydroxide with water depends upon their electrode potential (E0) and this
electrode potential is a measure of the tendency of an element to lose electron in the aqueous solution.
Thus, more negative is the electrode potential, higher is the tendency of the element to lose electron
and hence stronger is the reducing agent, with decrease in negative value of Eº, the reaction with water
become more vigorous. Lithium has most negative Eº value therefore its reaction with water is less
vigorous than that of sodium which has the least negative Eº value among the alkali metals. This behaviour
of lithium is due to its small size and very high hydration energy. Rest of the members of the alkali metal
react vigorously with water and may sometimes catch fire, they also react with proton donors or acidic
hydrogen such as alcohol, gaseous ammonia, hydrogen halide and alkynes.
2M + 2C2H5OH  2C2H5OM + H2
2M + HC CH  M+ –C  C–M+ + H2
2M + 2HX  2 MX + H2

Example 11 : Name the product formed when alkali metals reacts with water.
Solution : Their respective hydroxides and dihydrogen is produced.

(iii) Reactivity towards dihydrogen: Alkali metal react with dry di-hydrogen at about 673 K (lithium at
1073 K) to form crystalline hydrides which are ionic in nature and have high melting points.
Heat
2M  H2   2MH–

(iv) Reactivity towards halogens : The alkali metals react vigorously with halogens and form halides which
are ionic in nature, M+X–. But the halides of lithium are a bit covalent in nature, this is due to the fact
that lithium ion has high polarisation capability (The distortion of electron cloud of the anion by the cation
is called polarisation). Since the Li+ ion is very small in size, it has high tendency to distort electron
cloud around the negative halide ion. Since anion with large size can be easily distorted, among halides,
lithium iodide is the most covalent in nature.

Example 12 : The alkali metal halides are ionic or covalent?

Solution : Ionic

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET The s-Block Elements 81
(v) Reducing Nature : The alkali metals have strong tendency to get oxidised, that is why they act as
strong reducing agents, among these lithium is the strongest and sodium is the least powerful reducing
agent. The standard electrode potential (Eº) measures the reducing power and represents the changes.
M(s)  M(g) Sublimation enthalpy
M(g)  M+(g) + e– ionization enthalpy
M+(g) + H2O  M+(aq) hydration enthalpy
Since lithium ion has small size, it has the highest hydration enthalpy which gives an explanation for
its high negative Eº value and its high reducing power.
Higher the negative value of Eº value more reducing will be the ionic species.
(vi) Solutions in liquid ammonia : All alkali metals dissolve in liquid ammonia and give deep blue colour
solution which are conducting in nature. These solutions contain ammoniated cations and ammoniated
electrons as shown below
M + (x + y)NH3  [M(NH3)x]+ + [e(NH3)y]–
The blue colour of the solution is considered to be due to ammoniated electrons which absorb energy
corresponding to red region of visible light for their excitation to higher energy levels. The transmitted
light thus, imparts blue colour to the solution. The electrical conductivity of the solution is due to both
ammoniated cations and ammoniated electrons. The blue solution on standing slowly liberates hydrogen
resulting in the formation of amide.

1
M+(am) + e– + NH3(l)  MNH2 + H (g)
2 2
(Metal amide)

(where ‘am’ denotes solution in ammonia). At concentrations above 3M, the solution of alkali metals in
liquid ammonia are copper bronze coloured. These solutions contain cluster of metal ions and hence
possess metallic lusture. The blue solutions are paramagnetic whereas bronze coloured solutions are
diamagnetic.

USES
1. Lithium is used as a metal in a number of alloys. Its alloys with magnesium, containing about 14% lithium
is extremely tough and corrosion resistant which is used for armour plate and aerospace components;
with lead to make white metal with aluminium to make aircraft parts.
2. Lithium hydroxides is used in the ventilation systems of space crafts and submarines to absorb
carbondioxide
3. Lithium aluminium hydride (LiAlH4) is a powerful reducing agent which is commonly used in organic
synthesis.
4. Liquid sodium or its alloys with potassium is used as a coolant in nuclear reactors.
5. Sodium-lead alloy is used for the preparation of tetraethyl lead, Pb(C2H5)4, which is used as an
antiknocking agent in petrol.
(Pb + 4Na) + 4C2H5Cl  (C2H5)4 Pb + 4NaCl
Lead-sodium alloy tetraethyl lead
6. Sodium is used in the production of sodium vapour lamps.
7. Potassium chloride is used as fertilizer.
8. Potassium hydroxide is used in the manufacture of soft soaps and also as absorbent of carbon dioxide.
9. Potassium ions play a vital role in biological systems.
10. Caesium is used in photoelectric cells.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
82 The s-Block Elements NEET

GENERAL CHARACTERISTICS OF THE COMPOUNDS OF THE ALKALI METALS

All the common compounds of the alkali metals are generally ionic in nature
(i) Oxides and hydroxides
Alkali metals when burnt in air form different kinds of oxides, for example, the alkali metals on reaction
with limited quantity of oxygen form normal oxides of the formula, M2O
4M + O2  2M2O
(where M = Li, Na, K, Rb, Cs)
However, when heated with excess of air lithium forms normal oxide, (Li2O) and some peroxide Li2O2
sodium forms peroxide, Na2O2 and some superoxide NaO2 whereas potassium, rubidium and caesium
form superoxide having general formula MO2.
4Li + O2  2Li2O
Lithium oxide

2Na + O2  Na2O2
Sodium peroxide

K + O2  KO2
Potassium superoxide

The temperature required for the reaction to take place decrease on descending the group.
The stability of peroxide or superoxide increases as the size of the alkali metal increases. This is due
to stabilization of large anions by large cations through lattice energy effects.
The oxides and the peroxides are colourless when pure but superoxides are yellow or orange in colour,
peroxides are diamagnetic whereas superoxide are paramagnetic in nature.
The normal oxides of alkali metal dissolve readily in water to form hydroxides and a large amount of heat
is produced.
M2O(s) + H2O(l)  2MOH(aq) + Heat
 2M+ + 2OH–
The peroxides and superoxides are also readily hydrolysed by water as shown below:
M2O2 + 2H2O  2M+ + 2OH– + H2O2
Na2O2 + 2H2O  2NaOH + H2O2
2MO2 + 2H2O  2M+ + 2OH– + H2O2 + O2
2KO2 + 2H2O  2KOH + H2O2 + O2
The higher oxides generally act as good oxidising agent, sodium peroxide is widely used as an oxidising
agent in inorganic chemistry.
The hydroxides which are obtained by reaction of the oxides with water are all white crystalline solids.
The hydroxides of alkali metals are strong bases. The basic character of alkali metal hydroxides
increases in going down the group.
LiOH
NaOH Basic character
KOH increases
RbOH
CsOH
Alkali metal hydroxides are freely soluble in water and their dissolution in water is accompanied by
evolution of much heat due to intense hydration.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET The s-Block Elements 83

Example 13 : What kind of oxides are formed by lithium?

Solution : Lithium form Li2O and Li2O2

(ii) Halides
The alkali metals combine with halogens to form metal halides, which are ionic colourless, crystalline
solids having high melting point and general formula MX.
(X = F, Cl, Br, I)
2M + X2  2 MX
2Na + Cl2  2NaCl
Reactivity of alkali metals with particular halogen increases from Li to Cs. On the other hand, reactivity
of halogens with particular alkali metal M decreases from F2 to I2.
Reactivity with particular halogen X2
Li < Na < K < Rb < Cs
Reactivity with particular alkali metal M
F2 > Cl2 > Br2 > I2
The alkali metal halides can be prepared by the reaction of the appropriate oxide, hydroxide or carbonate
with aqueous hydro halic acid (HX). All of these halides have high negative enthalpies of formation; the
fH value for fluorides become less negative as we go down the group, whilst the reverse is true for
fH for chlorides, bromides and iodides. For a given metal fH always becomes less negative from
fluoride to iodide. The melting and boiling points always follow the trend, fluoride > chloride > bromide
> iodide.
All halides of the alkali metals except lithium fluoride (LiF) are freely soluble in water. The low solubility
of lithium fluoride is attributed to greater force of attraction between lithium ions and fluoride ions in the
crystal lattice or high lattice enthalpy. Caesium iodide (CsI) also has relatively low solubility in water.
This is attributed to smaller hydration energy of its large sized ions. LiCl, LiBr and LiI are soluble in
ethanol, acetone and other solvents of low polarity. This is due to predominant covalent character of these
halides. The predominant covalent character of lithium halides is due to greater polarizing power of Li+
ion. Among lithium halides LiI has maximum covalent character due to large polarizability of iodide ion.
LiCl is soluble in pyridine also.
(iii) Salts of oxo-acids
Oxo-acids are those acids in which the acidic proton is on a hydroxyl group with an oxo group attached
to the same atom e.g., carbonic acid, H2CO3[OC(OH)2], sulphuric acid, H2SO4[O2S(OH)2]. The alkali
metals form salts with all the oxo-acids.
The salts of oxo-acids are generally soluble in water and thermally stable.
The carbonates (M2CO3) and bicarbonates (MHCO3) of alkali metals are quite stable towards heat. Li2CO3,
however, is considerably less stable and decomposes readily on heating. Lithium being very small in
size polarises a large CO32– ions leading to the formation of stable Li2O and CO2 on heating

Li2CO3   Li2O  CO2

As the electropositive character increases down the group, the stability of the carbonates and hydrogen
carbonates increases.

Example 14 : What are oxo-acids?

Solution : Oxo acids are those acids in which the acidic proton is on a hydroxyl group with an oxo-group
attached to the same atom.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
84 The s-Block Elements NEET

ANOMALOUS PROPERTIES OF LITHIUM

Lithium shows properties which are very different from the other members of its group. This is due to the (i)
exceptionally small size of its atom and ion and (ii) greater polarizing power of lithium ion (i.e., charge/radius
ratio). Due to these factors, there is increased covalent character of lithium compounds which is responsible
for their solubility in organic solvents. Further, lithium shows diagonal relationship to magnesium which has
been discussed subsequently.
Points of difference between Lithium and other Alkali Metals
(i) As compared to other alkali metals, lithium is harder and its melting point and boiling point are higher.
(ii) Among all the alkali metals lithium is least reactive but the strongest reducing agent. When burnt in air
it forms mainly monoxide, Li2O and the nitride, Li3N unlike other alkali metals.
(iii) LiCl is deliquescent and crystallises as a hydrate, LiCl·2H2O whereas other alkali metal chlorides do
not form hydrates.
(iv) Except for lithium, rest of alkali metal’s hydrogen carbonates are obtained in the solid form.
(v) Lithium unlike other alkali metals forms no ethynide on reaction with ethyne.
(vi) Lithium nitrate when heated gives lithium oxide, Li2O, whereas other alkali metal nitrates decompose to
give the corresponding nitrite.
4LiNO3  2Li2O + 4NO2 + O2
2NaNO3  2NaNO2 + O2
(vii) LiF and Li2O are comparatively much less soluble in water than the corresponding compounds of other
alkali metals
Points of similarities between Lithium and Magnesium
The similarity between lithium and magnesium is because of their similar sizes; comparable atomic radii and
electronegativities.
Li = 152 pm
Mg = 160 pm
Ionic radii :Li+ = 76 pm
Mg2+ = 72 pm
The major similarities are
(i) Both lithium and magnesium are harder and lighter than other elements of the respective groups.
(ii) Both lithium and magnesium react slowly with water. Their oxides and hydroxides are less soluble and
their hydroxides decompose on heating. Both lithium and magnesium form nitride, Li3N and Mg3N2, by
direct combination with nitrogen.
(iii) Their oxides like Li2O and MgO do not combine with excess oxygen to give their superoxide.
(iv) The carbonates of both decompose easily on heating and form oxides and CO2 and both do not form
solid hydrogen carbonates.
(v) Both LiCl and MgCl2 are soluble in ethanol, are deliquescent and crystallise from aqueous solution as
hydrates, LiCl·2H2O and MgCl2·8H2O.

Example 15 : Why lithium show anomalous properties?

Solution : It show anomalous behaviour due to the exceptionally small size of its atom and ion, and high
polarising power (i.e., charge/radius ratio)

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET The s-Block Elements 85
SOME IMPORTANT COMPOUNDS OF SODIUM
Commercially important compounds of sodium are sodium carbonate, sodium hydroxide, sodium chloride and
sodium bicarbonate.
Sodium Carbonates (Washing soda), Na2CO3·10H2O
It is prepared by Solvay process which exploits the low solubility of sodium hydrogencarbonate whereby it
gets precipitated in the reaction of sodium chloride with ammonium hydrogen carbonate. The ammonium
hydrogen carbonate is prepared by passing CO2 to a concentrated solution of sodium chloride saturated with
ammonia, where ammonium carbonate followed ammonium hydrogen carbonate are formed.
2NH3 + H2O + CO2  (NH4)2CO3
(NH4)2CO3 + H2O + CO2  2NH4HCO3
NH4HCO3 + NaCl  NH4Cl + NaHCO3
Sodium hydrogen carbonate crystal separates. These are heated to give sodium carbonate.
2NaHCO3  Na2CO3 + CO2 + H2O
When solution having NH4Cl is treated with Ca(OH)2, NH3 is produced and recovered and CaCl2 is obtained
as a by product.
2NH4Cl + Ca(OH)2  2NH3 + CaCl2 + H2O
Potassium carbonate cannot be manufactured by solvay process because potassium hydrogen carbonate is
too soluble to be precipitated by the addition of ammonium hydrogen carbonate to a saturated solution of
potassium chloride.
Properties of Sodium Carbonate : Sodium carbonate is a white coloured crystalline solid which is found
as a decahydrate, Na2CO3·10H2O. This is also called as washing soda. It is easily soluble in water. When
heated decahydrate loses, its water of crystallisation and form monohydrate. Above 375 K, the monohydrate
becomes completely anhydrous and changes to a white powder called soda ash.
375 K
Na2CO3·10H2O   Na2CO3·H2O + 9H2O

 375 K
Na2CO3·H2O  Na2CO3 + H2O
Carbonate part of sodium carbonate get hydrolysed by water to form an alkaline solution

CO32–  H2O  HCO3–  OH–

Uses of Sodium Carbonate :

(i) It is used for softening hard water, for washing purposes in laundry and cleaning
(ii) It is used in the manufacture of glass, soap, borax and caustic soda.
(iii) It is used in paper, paints and textile industries.
(iv) As an important laboratory reagent both in qualitative and quantitative analysis.

Example 16 : Which process is used for preparation of sodium carbonate?

Solution : Solvay process.

Sodium Chloride, NaCl

The main source of sodium chloride is sea water which contains 2.7 to 2.9% by mass of the salt. It also
occurs as salt beds. In tropical countries like India, common salt is generally obtained by evaporation of sea
water. Approximately 50 lakh tons of salt are produced annually in India by solar evaporation. Crystallisation
of brine solution gives crude sodium chloride which contains calcium sulphate (CaSO4), sodium sulphate
(Na2SO4), calcium chloride (CaCl2), and magnesium chloride (MgCl2) etc. as impurities. CaCl2 and MgCl2

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
86 The s-Block Elements NEET

are undesirable impurities because they are deliquescent (i.e., they absorb moisture from the atmosphere).
For purification, a saturated solution of the crude salt is prepared and the insoluble impurities are removed
by filtration. The solution is then saturated with HCl gas. Due to common ion effect crystals of pure NaCl
separate out, chlorides of calcium and magnesium, being more soluble, remain in the solution.
Sodium chloride is a white crystalline solid. It melts at 1081 K. It has a solubility of 36.0 g in 100 g of water
at 273 K. The solubility does not increase much with increase in temperature.
Uses of sodium chloride
(i) It is an essential constituent of our food. It is used as common salt or table salt for domestic purposes.
(ii) It is used for the preparation of Na2O2, NaOH and Na2CO3.

Example 17 : What impurities are present in brine solution?

Solution : Sodium sulphate, calcium sulphate, calcium chloride and magnesium chloride.

Sodium Hydroxide (Caustic soda), NaOH

Sodium hydroxide is manufactured by the electrolysis of sodium chloride solution (brine) in a specially
designed cell called Castner-Kellner cell. A brine solution is electrolysed using a mercury cathode and a
carbon anode. Sodium metal discharged at the cathode combines with mercury to form sodium amalgam.
Chlorine gas is evolved at the anode.
Hg
Cathode; Na   e –   Sodium amalgam

1
Anode; Cl–  Cl2  e –
2
The amalgam is treated with water to give sodium hydroxide and hydrogen gas.
2Na - amalgam + 2H2O  2NaOH + 2Hg + H2
Properties of sodium hydroxide :
Sodium hydroxide is a white, translucent solid. It melts at 591 K. It is readily soluble in water to give a strong
alkaline solution. Crystals of sodium hydroxide are deliquescent. On prolonged exposure, CO2 is absorbed
resulting in the formation at the surface a layer of Na2CO3. It is highly soluble in water and the solution has
a very corrosive action on animal tissue.
Uses of sodium hydroxide
(i) It is used in the manufacture of paper, soap and artificial silk.
(ii) It is used for petroleum refining.
(iii) It is used for mercerizing cotton.
(iv) It is used in purification of bauxite.
(v) It is used for the preparation of pure fats and oils.
(vi) It is used as a laboratory reagent.

Example 18 : Which cell is used for manufacture of sodium hydroxide?

Solution : Castner-Kellner cell

Sodium hydrogen carbonate (Baking soda), NaHCO3

Sodium hydrogen carbonate is obtained as intermediate product in Solvay’s process for the manufacture of
sodium carbonate. It can also be made by saturating a solution of sodium carbonate with carbon dioxide.
The white crystalline powder of sodium hydrogen carbonate, being less soluble, gets separated out.
Na2CO3 + H2O + CO2  2NaHCO3

Note : KHCO3 and K2CO3 can’t be prepared by Solvay’s process as KHCO3 is highly soluble in water.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET The s-Block Elements 87
Uses of sodium hydrogen carbonate
(i) It is used as component of baking powder
(ii) It is used in fire extinguishers
(iii) It is used in medicines. It acts as a mild antiseptic for skin infections.

BIOLOGICAL IMPORTANCE OF SODIUM AND POTASSIUM

Sodium ions are found primarily on the outside of cells, being located in blood plasma and in the interstitial
fluid which surrounds the cells. These ions participate in the transmission of nerve signals. They also regulate
flow of water across cell membranes and in transport of sugars and amino acids into the cells. Potassium
ions are the most abundant cations within cell fluids, where they activate many enzymes, participate in
oxidation of glucose to produce ATP (adenosine triphosphate), potassium ions, in combination with sodium
ions are responsible for transmission of nerve signals. There is a considerable variation in the concentrations
of Na+ and K+ ions found on the opposite sides of cell membranes. The functional features of nerve cells
depend upon the sodium-potassium ion gradient that is established on the cell. These ionic gradients are
maintained by sodium-potassium pumps that operate across the cell membranes. As a typical example, in
blood plasma, sodium is present to the extent of 143 m mol L–1 whereas the potassium level is only 5 m
mol L–1 within the red blood cells. These concentration change to 10 m mol L–1 (Na+) and 105 m mol L–1
(K+). Sodium-potassium pump consumes more than one-third of the ATP used by a resting animal and about
15 kg per 24 h in a resting human. A typical 70 kg man contains about 90 g of Na and 170 g of K, compared
with only 5 g of iron and 0.06 g of copper.

EXERCISE
1. Among the following which element is the rarest of all?
(1) Na (2) Cs
(3) Fr (4) K
2. Among the chlorides of alkali metals, what is the decreasing order of hydration?
(1) NaCl > KCl > RbCl > LiCl > CsCl (2) LiCl > CsCl > KCl > RbCl > NaCl
(3) LiCl > NaCl > KCl > RbCl > CsCl (4) All are equally hydrated as halide is same
3. What is the correct order of density?
(1) Li > Na > K (2) K > Na > Li
(3) Na > K > Li (4) Na = K > Li
4. Among the following which metal forms superoxides of type MO2?
(1) K (2) Rb
(3) Cs (4) All of these
5. Among the alkali metal halides which of the alkali metal halide is the most covalent?
(1) LiCl (2) NaI
(3) KI (4) LiI
6. The concentrated solution of alkali metals in liquid ammonia becomes blue due to
(1) Ammoniated electron (2) Ammoniated metal cations
(3) Diamagnetic nature of solution (4) Alkaline nature of metal
7. What is correct statement?
(1) Iodides of alkali metals have highest ionic character among halides
(2) LiF is highly soluble in H2O
(3) Low solubility of CsI is due to smaller hydration enthalpy of its two ions
(4) All of these

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
88 The s-Block Elements NEET

8. The hybridisation of BeCl2 in solid state and above 1200 K is respectively

(1) sp3, sp3 (2) sp3, sp2
(3) sp2, sp2 (4) sp3, sp
9. On heating alkali metal nitrates product formed are (except LiNO3)
(1) NO2 and O2 only (2) NO2 only
(3) NO2 and MO only (4) MNO2 and O2
10. Paramagnetic behaviour of KO2 is due to the fact that unpaired electron is present in
(1) 2p molecular orbital (2) *2p molecular orbital
(3) *2p molecular orbital (4) 2p molecular orbital

GROUP-2 ELEMENTS : ALKALINE EARTH METALS

The elements of group-2 are Beryllium (Be), Magnesium (Mg), Calcium (Ca), Strontium (Sr), Barium (Ba) and
Radium (Ra). Except for Be, rest are known as alkaline earth metals, because they were alkaline in nature
and existed in the earth. Be differs from rest of the members and show diagonal relationship with aluminium.
Atomic and Physical Properties of the Alkaline Earth Metals

Property Beryllium Magnesium Calcium Strontium Barium Radium

Be Mg Ca Sr Ba Ra

Atomic number 4 12 20 38 56 88
–1
Atomic mass (g mol ) 9.01 24.31 40.08 87.62 137.33 226.03
2 2 2 2 2 2
Electronic [He] 2s [Ne] 3s [Ar] 4s [Kr] 5s [Xe] 6s [Rn] 7s
configuration

Ionization 899 737 590 549 503 509

–1
enthalpy (I)/kJ mol

Ionization 1757 1450 1145 1064 965 979

–1
Enthalpy (II)/kJ mol

Hydration enthalpy –2494 –1921 –1577 –1443 –1305 –

(kJ/mol)
Metallic 111 160 197 215 222 –
Radius / pm
2+
Ionic radius M / pm 31 72 100 118 135 148

m.p. / K 1560 924 1124 1062 1002 973

b.p / K 2745 1363 1767 1655 2078 (1973)

–3
Density / g cm 1.84 1.74 1.55 2.63 3.59 (5.5)

Standard potentials –1.97 –2.36 –2.84 –2.89 –2.92 –2.92

2+
E / V for (M / M)

Occurrence in 2* 2.76** 4.6** 384* 390* 10–6*

lithosphere
*ppm (parts per million); ** percentage by weight

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET The s-Block Elements 89
Electronic Configuration
The alkaline earth metals have 2 electrons in the s-orbital of the valence shell. Their general electronic
configuration may be represented as [Noble gas]ns2; where n = 2 to 7
Element Symbol Electronic configuration
Beryllium Be 1s22s2 or [He]2s2
Magnesium Mg 1s22s22p63s2 or [Ne]3s2
Calcium Ca 1s22s22p63s23p64s2 or [Ar]4s2
Strontium Sr 1s22s22p63s23p63d104s24p65s2 or [Kr]5s2
Barium Ba 1s22s22p63s23p63d104s24p64d105s25p66s2 or [Xe]6s2
Radium Ra 1s22s22p63s23p63d104s24p64d104f145s25p65d106s26p67s2 or [Rn] 7s2

Atomic and Ionic Radii

The atomic radii as well as ionic radii of the members of the family are smaller than the corresponding
members of alkali metals. This is due to the fact that the alkaline earth metals have a higher nuclear charge
due to which the electrons are more strongly attached towards the nucleus causing a decrease in atomic
size. Within the group, the atomic and ionic radii increase with increase in atomic number.

Ionization Enthalpies
The alkaline earth metals owing to their large size of atoms have fairly low values of ionization enthalpies.
Within the group, the ionization enthalpy decreases as the atomic number increases. It is because of increase
in atomic size due to addition of new shells and increase in the magnitude of screening effect of the electrons
in inner shells.
The first ionization enthalpies of the alkaline earth metals are higher than those of the corresponding group
1 metals. This is due to their small size as compared to the corresponding alkali metals. It is interesting to
note that the second ionization enthalpies of the alkaline earth metals are smaller than those of the
corresponding alkali metal.

Hydration Enthalpies
The hydration enthalpies of alkaline earth metal ions are larger than those of alkali metal ions. Therefore,
compounds of alkaline earth metals are more extensively hydrated, for example, magnesium chloride and
calcium chloride exist as hexahydrates (MgCl2·6H2O and CaCl2·6H2O) whereas sodium chloride and potassium
chloride do not form such hydrates.
Like alkali metal ions, the hydration enthalpies of alkaline earth metal ions decrease with increase in ionic
size down the group.
Be2+ > Mg2+ > Ca2+ > Sr2+ > Ba2+

Physical Properties
The alkaline earth metals are silvery white, lustrous and relatively soft but harder than the alkali metals.
Beryllium and magnesium appear to be some what greyish. The melting and boiling points of these metals
are higher than the corresponding alkali metals due to smaller sizes. But this trend is not systematic, because
of the low ionization enthalpies, they are strongly electropositive in nature. The electropositive character
increases down the group from Be to Ba.
Calcium, strontium and barium impart characteristic brick red, crimson and apple green colours respectively
to the flame. In flame the electrons are excited to higher energy levels and when they drop back to the ground
state, energy is emitted in the form of visible light. The electrons in beryllium and magnesium are too strongly
bound to get excited by flame. Hence, these elements do not impart any colour to the flame. Ca, Sr and
Ba give flame test which helps in their detection in qualitative analysis and estimation by flame photometry.
The alkaline earth metals just like those of alkali metals have high electrical and thermal conductivities which
are a typical characteristics of metals.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
90 The s-Block Elements NEET

Chemical Properties
As compared to alkali metals, alkaline earth metals are less reactive due to their relatively higher ionization
enthalpies. The reactivity of alkaline earth metals increases on going down the group because their ionization
enthalpies decreases and electropositive character increases.
(i) Reactivity towards air and water:
Due to the formation of an oxide film over their surface, Be and Mg are kinetically inert to oxygen and
water. But Be in powdered form burns brilliantly and give Beryllium monoxide (BeO) and Beryllium nitride
(Be3N2). Since magnesium is more electropositive, it burns with dazzling brilliance in air and form MgO
and Mg3N2. Calcium, strontium and barium are attacked very fast by the air and consequently they form
the oxides and nitrides.
Note : Beryllium, magnesium and calcium form monoxides while strontium and barium form peroxides.
2M + O2  2MO (M = Be, Mg or Ca)
(Monoxide)

M + O2  MO2 (M = Ba or Sr)
(Peroxide)

The monoxide can also be prepared by decomposition of their respective carbonates.

MCO3  MO + CO2
(M = Be, Mg, Ca, Sr or Ba)
The reactivity of alkaline earth metals towards oxygen increases as we move down the group.

The alkaline earth metals react with water with increasing vigour even in cold to form hydroxide. All the alkaline
earth metal hydroxides are bases except Be(OH)2 which is amphoteric.
Note : The solubilities of hydroxide of alkaline-earth metals increase markedly on moving down the group
as shown below.
Hydroxide Solubility in water at 298 K (gL–1)
Be(OH)2 Insoluble
Solubility in water increases
Basic strength increases

Mg(OH)2 0.03

Ca(OH)2 1.3

Sr(OH)2 8

Ba(OH)2 380

Among the hydroxides of this group it is observed that the magnitude of hydration enthalpy remains almost
unaltered whereas the magnitude of lattice enthalpy decreases significantly down the group due to increase
in size. Thus, the net effect of the two factors, (Hlattice – Hhydration = Hsolution); Hsolution becomes more
negative from Be to Ba accounting for increase in solubility.

Example 19 : Why alkaline earth metals have smaller ionic and atomic radii as compared to that of alkali metals?
Solution : The alkaline earth metals have a higher nuclear charge due to which the electrons are more
strongly attracted towards the nucleus causing decrease in atomic size.

Example 20 : What colours are imparted by calcium, strontium and barium to the flame?
Solution : Calcium  Brick red
Strontium  Crimson
Barium  Apple green

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET The s-Block Elements 91
(ii) Reactivity towards the halogens
All the alkaline earth metals react with halogens directly, on heating, to form halides having general
formula, MX2
M + X2  MX2 (X = F, Cl, Br, I)
Thermal decomposition of (NH4)2BeF4 is the best route for the preparation of BeF2,

(NH4)2BeF4   BeF2 + 2NH4F
Beryllium chloride is prepared indirectly, from its oxide as follows
600–800 K

BeO + C + Cl2  
 BeCl2 + CO

(iii) Reactivity towards hydrogen

All the members of the group, except beryllium, combine with hydrogen on heating to form metal
hydrides, MH2.

M + H2  MH2
BeH2 can be produced by the reduction of BeCl2 with LiAlH4

2BeCl2 + LiAlH4  2BeH2 + LiCl + AlCl3

BeH2 is covalent and polymeric (lewis acid) in nature whereas other hydrides are ionic in nature.

Example 21 : What products are formed on thermal decomposition of (NH4)2BeF4?


Solution : (NH4)2BeF4  BeF2 + 2NH4F

(iv) Reactivity toward acids

The alkaline earth metals readily react with acids liberating dihydrogen.

M + 2HCl  MCl2 + H2

(v) Reducing nature
The alkaline earth metals just like alkali metals are strong reducing agent due to their large negative
values of reduction potentials, but their reducing power is less than those of their corresponding alkali
metals. Among the alkaline earth metals Be has less negative value but its reducing nature is due to
large hydration energy associated with the small size of Be2+ ion and relatively large value of the
atomization enthalpy of the metal.
(vi) Solutions in liquid ammonia
Like alkali metals, the alkaline earth metals dissolve in liquid ammonia to give deep blue black solution.
These solutions contain ammoniated cations and ammoniated electrons.

M + (x + y)NH3  [M(NH3)x]2+ + 2[e(NH3)y]–

It is possible to isolate metal ammoniates, [M(NH3)6]2+ from these solutions
Uses of alkaline earth metals
(i) Beryllium is used in the manufacture of alloys. Cooper-Beryllium alloys are used in the making of high
strength springs.
(ii) Metallic beryllium is used for making windows of X-rays tubes.
(iii) Magnesium, being a light metal, forms many light alloys with aluminum, zinc, manganese and tin.
(iv) Magnesium (Powder and ribbon) is used in flash powders and bulbs, incendiary bombs and signals).

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
92 The s-Block Elements NEET

(v) Magnesium-aluminium alloys are used in aircraft construction.

(vi) Magnesium is used as sacrificial anode for the prevention of corrosion of iron.
(vii) A suspension of magnesium hydroxide in water (called milk of magnesia) is used as an ant-acid to control
excess acidity in stomach.
(viii) Magnesium carbonate is an ingredient of tooth-paste.
(ix) Calcium is used in the extraction of metals from oxides which are difficult to reduce with carbon.
(x) Calcium and barium metals are used to remove air from vacuum tubes, due to their tendency to react
with oxygen and nitrogen at high temperature.
(xi) Radium salts are used for radio therapy of cancer.

GENERAL CHARACTERISTICS OF COMPOUNDS OF THE ALKALINE EARTH METALS

The most common valence of group 2 element is 2+ i.e., dipositive oxidation state.
The alkaline earth metals commonly form ionic compounds but ionic character of their compounds is lesser than
that of the alkali metals. This is due to high ionization energy due to increased nuclear charge and smaller size.
The tendency to form ionic compounds increases down the group, that is the reason why the oxides and other
compounds of beryllium and magnesium are more covalent than those formed by the heavier and larger sized
members (Ca, Sr, Ba)
The general characteristics of some of the compound of the alkaline earth metals are described below.
(i) Oxides and hydroxides
The alkaline earth metals being less electro positive than alkali metals react with air or oxygen slowly
upon heating to form monoxides, MO and except for BeO, all alkaline earth metals have rock-salt
structure
The BeO is essentially covalent in nature. The enthalpies of formation of these oxides are quite high and
consequently they are very stable to heat.
BeO is amphoteric in nature and oxides of other elements are ionic and basic in nature, and react with
water to form sparingly soluble hydroxides.
MO + H2O  M(OH)2
The solubility, thermal stability and the basic character of these hydroxides increase with increasing
atomic number from Mg(OH)2 to Ba(OH)2. The hydroxides of alkaline earth metals are less basic and
less stable when compared with that of the alkali metals. Beryllium hydroxide is amphoteric in nature.

Be(OH)2 + 2OH–  [Be(OH)4]2–

Beryllate ion

Be(OH)2 + 2HCl  BeCl2 + 2H2O

Example 22 : What is the trend of formation of ionic compound in alkaline earth metals?
Solution : The tendency to form ionic compounds increases down the group.

(ii) Halides : Beryllium forms covalent halides, all other members forms ionic halides. Beryllium halides are
soluble in organic solvents.
Beryllium chloride has a chain structure

Cl Cl Cl Cl

Be Be Be Cl – Be Be – Cl 1200K Cl – Be – Cl
Cl Cl Cl Cl

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET The s-Block Elements 93
BeCl2 in vapour phase form a chloro-bridged dimer which at high temperatures of the order of 1200 K
dissociates into linear monomer. The tendency to form halide hydrates gradually decreases, (for example,
MgCl2·8H2O, CaCl2·6H2O, SrCl2·6H2O and BaCl2·2H2O) down the group. The hydrated chlorides,
bromides and iodides of Ca, Sr and Ba can be dehydrated by heating but the corresponding hydrated
halides of Be and Mg on heating undergoes hydrolysis. The fluorides of alkaline earth metals are less
soluble than chlorides due to their high lattice energies.

Example 23 : Write two characteristics of halides of Beryllium.

Solution : Beryllium halides are covalent and soluble in organic solvents.

(iii) Salts of oxoacids

Carbonates : Carbonates of alkaline earth metals are insoluble in water and can be precipitated by the
addition of a sodium or ammonium carbonate solution to a solution of a soluble salt of these metals.
The solubility of carbonates in water decreases as the atomic number of the metal ion increases. All
the carbonates decompose on heating to give carbon dioxide and the oxide. Beryllium carbonate is
unstable and can be kept only in the atmosphere of CO2. The thermal stability increases with increasing
cationic size.
Sulphates : The sulphates of the alkaline earth metals are all white solids and stable to heat. BeSO4
and MgSO4 are readily soluble in water; the solubility decreases from CaSO4 to BaSO4. The greater
hydration enthalpies of Be2+ and Mg2+ ions overcome the lattice enthalpy factor and therefore their
sulphates are soluble in water
Nitrates : The nitrates are made by dissolution of the carbonates in dilute nitric acid. Magnesium nitrate
crystallises with six molecules of water, whereas barium nitrate crystallises as the anhydrous salt. This
again shows a decreasing tendency to form hydrates with increasing size and decreasing hydration
enthalpy. All of them decompose on heating to give metal oxide, NO2 and oxygen.

2M(NO3)2  2MO + 4NO2 + O2

(M = Be, Mg, Ca, Sr, Ba)

ANOMALOUS BEHAVIOUR OF BERYLLIUM

Beryllium shows different behaviour from the rest members of its group and shows diagonal relationship to
aluminium due to reasons discussed below.
(i) Beryllium has exceptionally small atomic and ionic sizes and therefore does not compare well with other
members of the group, because of high ionisation enthalpy and small size it forms compounds which
are largely covalent and get easily hydrolysed.
(ii) Beryllium does not exhibit coordination number more than four as in its valence shell, there are only four
orbitals. The remaining members of the group can have a coordination number of six by making use of
d-orbitals.
(iii) The oxides and hydroxide of beryllium unlike the hydroxide of other elements in the group, are amphoteric
in nature.
Diagonal relationship between Beryllium and Aluminium
The ionic radius of Be2+ is approx. 31 pm; the charge/radius ratio is nearly the same as that of the Al3+ ion.
Hence beryllium resembles aluminium in some ways. Similarities between Al and Be is given below.
(i) Like aluminium, beryllium is not readily attacked by acids because of the presence of an oxide film on
the surface of the metal.
(ii) Beryllium hydroxide dissolves in excess of alkali to give a beryllate ions, [Be(OH)4]2– just as aluminium
hydroxide gives aluminate ion, [Al(OH)4]–.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
94 The s-Block Elements NEET

(iii) The chlorides of both beryllium and aluminium have Cl– bridged chloride structure in vapour phase. Both
the chlorides are soluble in organic solvents and are strong lewis acids. They are used as Friedal craft
catalysts.
(iv) Beryllium and aluminium ions have strong tendency to form complexes, BeF42–, AlF63–.

Example 24 : Why beryllium is different from other members of its group in some properties?
Solution : It is due to small atomic and ionic size.

SOME IMPORTANT COMPOUNDS OF CALCIUM

Calcium Oxide or Quick Lime (CaO)
It is prepared on a commercial scale by heating limestone (CaCO3) in a rotary kiln at 1070 – 1270 K.
Heat

CaCO3  CaO + CO2

The carbon dioxide is removed as soon as it is produced to enable the reaction to proceed to completion.
Calcium oxide is a white amorphous solid. It has a melting point of 2870 K. On exposure to atmosphere, it
absorbs moisture and carbon dioxide.

CaO + H2O  Ca(OH)2

CaO + CO2  CaCO3

When small amount of water is added to lime it breaks the lump, this process is called slaking of lime. Quick
lime slaked with soda gives solid soda lime. Being a basic oxide, it combines with acidic oxides at high
temperature.
CaO + SiO2  CaSiO3
6CaO + P4O10  2Ca3(PO4)2
Uses of Calcium Oxide
(i) Calcium oxide is the cheapest form of alkali, it is also important primary material for manufacturing
cement.
(ii) it is used in the manufacture of sodium carbonate from caustic soda.
(iii) It is used in the purification of sugar and in the manufacture of dye stuffs.

Example 25 : Why CO2 is removed when CaCO3 is heated in a rotary kiln?

Solution : The carbon dioxide is removed to enable the reaction to proceed to completion

Calcium Hydroxide (Slaked Lime), Ca(OH)2

Calcium hydroxide is prepared by adding water to quick lime, CaO
Calcium hydroxide is a white amorphous powder. It is sparingly soluble in water. The aqueous solution is
known as lime water and a suspension of slaked lime in water is known as milk of lime.
When carbon dioxide is passed through lime water it turns milky due to the formation of calcium carbonate.
Ca(OH)2 + CO2  CaCO3 + H2O
When excess of CO2 is passed, the precipitate dissolves to form calcium hydrogen carbonate.
CaCO3 + CO2 + H2O  Ca(HCO3)2
Milk of lime reacts with chlorine to form hypochlorite, a constituent of bleaching power
2Ca(OH)2 + 2Cl2  CaCl2 + Ca(OCl)2 + 2H2O

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET The s-Block Elements 95
Uses of Calcium Hydroxide
(i) It is used in preparation of building material called mortar.
(ii) Due to its disinfectant nature, it is used in white wash.
(iii) It is used in making glass, in tanning industry, for the purification of bleaching powder and for the
purification of sugar.

Example 26 : How calcium hydroxide is prepared?

Solution : Calcium hydroxide is prepared by adding water to quick lime (CaO).

Calcium Carbonate, CaCO3

Calcium carbonate is found in various forms like limestone, chalk, marbles etc. It can be prepared by passing
carbon dioxide through slaked lime or by the addition of sodium carbonate to calcium chloride.
Ca(OH)2 + CO2  CaCO3 + H2O
CaCl2 + Na2CO3  CaCO3 + 2NaCl
In this preparation, excess of carbon dioxide is avoided because it lead to the formation of water soluble
calcium hydrogen carbonate. Calcium carbonate is a white fluffy powder. It is almost insoluble in water. When
heated to 1200 K, it decomposes to evolve carbon dioxide.
1200 K
CaCO3   CaO  CO2

It reacts with dilute acid to liberate carbon dioxide.

CaCO3 + 2HCl  CaCl2 + H2O + CO2
CaCO3 + H2SO4  CaSO4 + H2O + CO2
Uses of Calcium Carbonate, CaCO3
In the form of marble and in the manufacture of quick lime, it is used as a building material. It is used as
flux in extraction of iron when mixed with magnesium. Specially precipitated CaCO3 is extensively used in
the manufacture of high quality paper. It is also used as an antacid; mild abrasive in tooth paste, a constituent
of chewing gum, and as filler in cosmetics.

Example 27 : How calcium carbonate is prepared?

Solution : It can be prepared by passing carbon dioxide through slaked lime or by the addition of sodium
carbonate to calcium chloride.

1
Calcium Sulphate (Plaster of Paris), CaSO4· HO
2 2
It is a hemihydrate of calcium sulphate. It is obtained when gypsum, CaSO4·2H2O, is heated at 393 K.
2(CaSO4·2H2O)  2(CaSO4)·H2O + 3H2O
Above 393 K, no water of crystallisation is left and anhydrous calcium sulphate, CaSO4 is formed. This is
known as ‘dead burnt plaster’.
It has a unique property of setting with water. On mixing with a sufficient quantity of water it forms a plastic
mass that gets into a hard solid in 5 to 15 minutes.
Uses of Plaster of Paris
Used in building industry and in plasters. It is used for immobilising the affected part of organ where there
is a bone fracture or sprain. It is also used in dentistry, in ornamental work and for making casts of statues
and busts.
Cement : Cement was first introduced in England in 1824 by Joseph Aspdin. It is also called Portland cement
because it resembles with the natural lime tone quarried in the Isle of Portland, England.

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
96 The s-Block Elements NEET

Cement is obtained by combining CaO with clay, which contains silica, SiO2 along with oxides of aluminium,
iron and magnesium. The average composition of Portland cement is
CaO  50 – 60%
SiO2  20 – 25%
Al2O3  5 to 10%
MgO  2 – 3%
Fe2O3  1 – 2%
SO3  1 – 2%
For a good quality cement the ratio of silica (SiO2) to alumina (Al2O3) should be between 2.5 and 4 and the
ratio of lime (CaO) to the total of the oxides of silicon (SiO2) aluminium (Al2O3) and iron (Fe2O3) should be
close as possible to 2.
During manufacture of cement clay and lime are strongly heated together, they fuse and react to form cement
clinker. This clinker is mixed with 2-3% by weight of gypsum (CaSO4·2H2O) to form cement. Thus important
ingredient present in Portland. Cement are dicalcium silicate (Ca2SiO4) 26%, tricalcium silicate (Ca3SiO5) 51%
and tricalcium aluminate (Ca3Al2O6) 11%.

Setting of Cement
When mixed with water the setting of cement takes place which gives a hard mass. This is due to hydration
of the molecules of the constituents and their rearrangement. The reason of adding gypsum is only to slow
down the process of setting of the cement so that it gets sufficiently hardened.

Uses of cement
It has become an important commodity next to iron and steel. It is used in concrete and reinforced concrete,
in plastering and in the construction of bridges, dams and buildings.

Example 28 : How Plaster of Paris is obtained?

Solution : It is obtained when gypsum CaSO4·2H2O is heated at 393 K.
2(CaSO4·2H2O)  2(CaSO4)·H2O + 3H2O

BIOLOGICAL IMPORTANCE OF MAGNESIUM AND CALCIUM

An adult body contains about 25 g of Mg and 1200 g of Ca compared with only 5 g of iron and 0.06 g of
copper. The daily requirement in the human body has been estimated to be 200-300 mg.
All enzymes that uses ATP in phosphate transfer require magnesium as the cofactor. The chlorophyll contain
magnesium. About 99% of body calcium is present in bones and teeth. It also plays important roles in
neuromuscular function, inter neuromal transmission, cell membrane integrity and blood coagulation. The calcium
concentration in plasma is regulated at about 100 mg L–1. It is maintained by two hormones: calcitonin and
parathyroid hormone. Bone is continuously solublised and redeposited to the extent of 400 mg per day in man.

EXERCISE
11. Aqueous solution of soda lime is
(1) Acidic (2) Alkaline
(3) Neutral (4) Initially acidic changes to alkaline after some time
12. On heating gypsum above 393 K, the product formed is
1
(1) 2(CaSO4).H2O (2) CaSO4 H2O
2
(3) CaSO4.H2O (4) Dead burnt plaster

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET The s-Block Elements 97
13. In which process Ca(OH)2 is used to produce NH3?
(1) Solvay process (2) Bosch process
(3) Lane’s process (4) Castner - Kellner process
14. Which of the following carbonate is thermally most unstable?
(1) BeCO3 (2) CaCO3
(3) K2CO3 (4) Rb2CO3
15. Given two reactions, describe them
(i) Na2CO3 + 2 H2O  2 NaOH + H2CO3 (ii) CuSO4 + 5 H2O  CuSO4 ·5 H2O
(1) Both are hydration reactions
(2) Both are hydrolysis reactions
(3) Both are crystallisation reactions
(4) Reaction (i) is hydrolysis and reaction (ii) is hydration to form hydrated salt
16. The aqueous solution of baking soda is
(1) Acidic (2) Alkaline
(3) Neutral (4) Amphoteric
17. Halides of Be dissolve in organic solvent while of Ba do not
(1) High hydration energy of Be halides (2) High lattice energy of barium halides
(3) Large size of Ba2+ (4) Halides of Be are covalent but that of Ba are ionic
18. M + 2H2O  M(OH)2 + H2.
Which metal among the following cannot undergo this reaction at high temperatures?
(1) Mg (2) Ba
(3) Be (4) Ca
19. The ratio of moles of water as water of crystallisation in LiCl and BaCl2 is
(1) 1 : 1 (2) 1 : 2
(3) 1 : 4 (4) 1 : 3
20. Ca is the good reducing agent, because
(1) It has small size
(2) It is the first member of group 2
(3) It has one electron in outermost shell
(4) It has the negative reduction potential

Note :
Important Solubility Orders :
z LiF < NaF < KF < RbF < CsF
z LiCl > CsCl > RbCl > NaCl > KCl
z LiBr > NaBr > KBr > RbBr > CsBr
z NaI > LiI > KI > RbI > CsI
z MgF2 < CaF2 < SrF2 < BaF2 < BeF2
z BeX2 > MgX2 > CaX2 > SrX2 > BaX2 (where X = Cl, Br, I)

‰ ‰ ‰

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
 t
en
nm nment
sig ssig
As A Assignment

Assignment
8. Which of the following alkali metal is used in
SECTION - A
photoelectric cell? [NCERT Pg. 303]
NCERT Based MCQs
(1) Cs (2) Rb
1. When gypsum is heated above 393 K, the product
(3) Na (4) Li
formed is [NCERT Pg. 311]
9. Which of the following alkaline earth metal is
(1) Plaster of Paris (2) Dead burnt plaster
present in chlorophyll? [NCERT Pg. 312]
(3) Cement (4) Mortar (1) Ba (2) Ca
2. Most unstable carbonate is [NCERT Pg. 309] (3) Mg (4) Be
(1) BeCO3 (2) MgCO3 10. Which of the following gives the correct order of
(3) CaCO3 (4) BaCO3 mobility? [NCERT Pg. 300]
3. Which of the following is added to delay the (1) Cs+(aq) > Rb+(aq) > Na+(aq) > Li+(aq)
setting time of cement? [NCERT Pg. 312] (2) Cs+(aq) < Rb+(aq) < Na+(aq) < Li+(aq)
(1) Clay (2) Limestone (3) Li+(aq) < Na+(aq) < Cs+(aq) < Rb+(aq)
(3) Al2O3 (4) Gypsum (4) Na+(aq) < Rb+(aq) < Cs+(aq) < Li+(aq)
4. In which of the following property, Li does not show 11. Hybridisation of Be in solid BeCl2 is
diagonal relationship with Mg? [NCERT Pg. 304] [NCERT Pg. 309]
(1) Nature of hydride (1) sp3 (2) sp2
(2) Stability of carbonates (3) sp (4) sp3d
(3) Number of H 2 O molecules as water of 12. Which of the following gives NO2 gas on heating?
crystallisation in chlorides [NCERT Pg. 309]
(4) Covalent nature of halides (1) Be(NO3)2 (2) Mg(NO3)2
5. Slaked lime is [NCERT Pg. 311] (3) Ca(NO3)2 (4) All of these
(1) CaO (2) CaCO3 13. Correct order of solubility is [NCERT Pg. 302]
(3) Ca(OH)2 (4) CaSO4 (1) KOH > NaOH > LiOH
6. Find the incorrect order [NCERT Pg. 307] (2) LiOH > NaOH > KOH
(1) Be < Mg < Ca (Density) (3) KOH > LiOH > NaOH
(2) Na < K < Rb (Electropositivity) (4) NaOH > LiOH > KOH
(3) Be < Mg < Ca (Melting point) 14. In Caster-Kellner cell Na+ is reduced at electrode of
(4) Ca < Sr < Ba (Metallic radius) [NCERT Pg. 305]

7. Which of the following gives the correct order of (1) Platinum (2) Zinc
density? [NCERT Pg. 301] (3) Gold (4) Mercury
(1) Li < Na < K < Rb < Cs 15. The set of elements in which all of them forms
(2) Li > Na > K > Rb > Cs superoxides is [NCERT Pg. 301]

(3) Li < K < Na < Rb < Cs (1) Li, K, Ca (2) K, Ca, Mg

(4) Li > K > Na > Rb > Cs (3) K, Rb, Cs (4) K, Mg, Ba

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET The s-Block Elements 99
10. Soda ash is
SECTION - B
(1) Na2CO3 (2) CaSO4
Objective Type Questions
(3) Na2SO4 (4) LiOH
1. Which of the following is the weakest reducing
agent in aqueous solution? 11. Which of the following alkali metals has maximum
boiling point among the following?
(1) Li (2) Na
(1) Cs (2) K
(3) Rb (4) Cs
(3) Rb (4) Na
2. Which one of the following hydrated ions has the
smallest size? 12. Which of the following bicarbonate does not exist
in the solid state?
(1) Cs+ (2) Rb+
(1) NaHCO3 (2) LiHCO3
(3) Na+ (4) K+
(3) CsHCO3 (4) RbHCO3
3. Which of the following species is paramagnetic?
13. Which of the following ion has the largest effective
(1) Na2O2 (2) BaO2 ionic radius in aqueous solution?
(3) CsO2 (4) K2O (1) Cs+ (2) Na+
4. Which statement is correct? (3) Li+ (4) Rb+

(1) Li is only alkali metal which forms nitride 14. Sodium nitrate upon thermal decomposition gives
directly (1) Na2O (2) NaNO2
(2) An aqueous solution of Na2CO3 is alkaline (3) NaN3 (4) Na
(3) LiI is more soluble in ethanol than KI 15. Which of the following chloride is soluble in
(4) All of these pyridine solvent?

5. Which of the following hydroxide reacts with (1) CsCl (2) NaCl
NaOH? (3) SrCl2 (4) LiCl
(1) Mg(OH)2 (2) LiOH 16. What is the correct order of density of alkali
metals?
(3) CsOH (4) Be(OH)2
(1) Li > Na > K > Rb (2) K > Na > Li > Rb
6. Glauber’s salt is
(3) Na > K > Rb > Li (4) Li < K < Na < Rb
(1) Na2SO4.10H2O (2) SrCl2.6H2O
17. Which of the following is most basic in nature?
1 (1) LiOH (2) KOH
(3) MgSO4.7H2O (4) CaSO4 . H2O
2
(3) CsOH (4) NaOH
7. Which of the following species is prepared in
18. Nitrate which does not evolve NO 2 gas upon
Castner-Kellner cell?
heating?
(1) KCl (2) NaOH (1) LiNO3 (2) NaNO3
(3) NaCl (4) KHCO3 (3) Ca(NO3)2 (4) Be(NO3)2
8. Which one of the following alkali metals gives 19. The chemical formula of Plaster of Paris is
hydrated salts?
(1) CaSO4·2H2O
(1) Li (2) Na
1
(3) K (4) Cs (2) CaSO4 · H2O
2
9. Lime water is an aq. solution of (3) CaSiO3
(1) Mg(OH)2 (2) Ca(OH)2 3
(4) CaSO4 · H2O
(3) LiOH (4) NaOH 2

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
100 The s-Block Elements NEET

20. Which of the following alkali metals, forms

SECTION - C
superoxide?
(1) Li (2) Na Previous Years Questions

(3) Rb (4) All of these 1. Crude sodium chloride obtained by crystallisation

of brine solution does not contain
21. The percentage of CaO in Portland cement is
[NEET-2019 (Odisha)]
(1) 50 – 60% (2) 20 – 35%
(3) 70 – 80% (4) 15 – 25% (1) CaSO4 (2) MgSO4

22. Which of the following statement is correct? (3) Na2SO4 (4) MgCl2

(1) K, Rb and Cs form superoxides 2. Which of the alkali metal chloride (MCl) forms its
dihydrate salt (MCl  2 H2O) easily?
(2) K 2 CO 3 like Na 2 CO 3 can be prepared by
Solvay’s process. [NEET-2019 (Odisha)]
(3) Lithium is the most reactive alkali metal as its (1) KCl (2) LiCl
ionisation potential is lowest amongst alkali
metals. (3) CsCl (4) RbCl

(4) Sodium metal when dissolved in liquid 3. Enzymes that utilize ATP in phosphate transfer
ammonia forms a green coloured solution require an alkaline earth metal (M) as the cofactor.
M is : [NEET-2019]
23. Which of the following hydroxides is amphoteric in
nature? (1) Be (2) Mg
(1) Ba(OH)2 (2) Sr(OH)2 (3) Ca (4) Sr
(3) Be(OH)2 (4) Mg(OH)2 4. Which of the following oxides is most acidic in
nature? [NEET-2018]
H2O
24. Metal + N2  Metal nitride   NH3
(1) MgO (2) BeO
+ Metal hydroxide
(3) CaO (4) BaO
The metal can be
5. Among CaH 2, BeH 2, BaH 2, the order of ionic
(1) Na
character is [NEET-2018]
(2) Li
(1) BeH2 < CaH2 < BaH2
(3) Mg
(2) CaH2 < BeH2 < BaH2
(4) Both (2) and (3)
(3) BaH2 < BeH2 < CaH2
25. Which of the following is least soluble in water?
(4) BeH2 < BaH2 < CaH2
(1) NaF (2) KF
6. Ionic mobility of which of the following alkali metal
(3) LiF (4) CsF
ions is lowest when aqueous solution of their salts
26. Which of the following will have largest atomic are put under an electric field? [NEET-2017]
size?
(1) Na (2) K
(1) Na
(3) Rb (4) Li
(2) K
7. The suspension of slaked lime in water is known
(3) Ca
as [NEET-(Phase-2)-2016]
(4) Ba
(1) Limewater
27. Which of the following alkaline earth metal cannot
exhibit colour when heated in flame? (2) Quicklime

(1) Sr (2) Mg (3) Milk of lime

(3) Ca (4) Ba (4) Aqueous solution of slaked lime

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET The s-Block Elements 101
8. In context with beryllium, which one of the 15. Which of the following compounds has the lowest
following statements is incorrect? melting point? [AIPMT (Prelims)-2011]
[NEET-(Phase-2)-2016] (1) CaF2 (2) CaCl2
(1) It is rendered passive by nitric acid (3) CaBr2 (4) CaI2
(2) It forms Be2C 16. Which one of the following is present as an active
ingredient in bleaching powder for bleaching action?
(3) Its salts rarely hydrolyze
[AIPMT (Prelims)-2011]
(4) Its hydride is electron-deficient and polymeric
(1) CaCl2 (2) CaOCl2
9. Which of the following statements is false?
(3) Ca(OCl)2 (4) CaO2Cl
[NEET-2016]
17. Which of the following statements is incorrect?
(1) Mg2+ ions are important in the green parts of
plants [AIPMT (Mains)-2011]

(2) Mg2+ ions form a complex with ATP (1) Aluminium reacts with excess NaOH to give
Al(OH)3
(3) Ca2+ ions are important in blood clotting
(2) NaHCO3 on heating gives Na2CO3
(4) Ca2+ ions are not important in maintaining the
regular beating of the heart (3) Pure sodium metal dissolves in liquid
ammonia to give blue solution
10. On heating which of the following releases CO2
most easily? [Re-AIPMT-2015] (4) NaOH reacts with glass to give sodium silicate

(1) MgCO3 (2) CaCO3 18. Match list-I with list-II for the composition of
substances and select the correct answer using
(3) K2CO3 (4) Na2CO3 the code given below the lists
11. The function of "Sodium pump" is a biological [AIPMT (Mains)-2011]
process operating in each and every cell of all
animals. Which of the following biologically List-I List-II
important ions is also a constituent of the pump? (Substances) (Composition)
[AIPMT-2015] (A) Plaster of paris (i) CaSO4.2H2O
(1) Fe2+ (2) Ca2+
1
(3) Mg2+ (4) K+ (B) Epsomite (ii) CaSO4. HO
2 2
12. Solubility of the alkaline earth's metal sulphates in (C) Kieserite (iii) MgSO4. 7H2O
water decreases in the sequence [AIPMT-2015]
(D) Gypsum (iv) MgSO4. H2O
(1) Ba > Mg > Sr > Ca (2) Mg > Ca > Sr > Ba
(A) (B) (C) (D)
(3) Ca > Sr > Ba > Mg (4) Sr > Ca > Mg > Ba
(1) (i) (ii) (iii) (iv)
13. Which one of the alkali metals, forms only, the
normal oxide, M2O on heating in air? (2) (iv) (iii) (ii) (i)

[AIPMT (Prelims)-2012] (3) (iii) (iv) (i) (ii)

(1) Li (2) Na (4) (ii) (iii) (iv) (i)

(3) Rb (4) K 19. Which of the following alkaline earth metal

sulphates has hydration enthalpy higher than the
14. Equimolar solutions of the following substances lattice enthalpy ? [AIPMT (Prelims)-2010]
were prepared separately. Which one of these will
record the highest pH value? (1) CaSO4
[AIPMT (Prelims)-2012] (2) BeSO4
(1) LiCl (2) BeCl2 (3) BaSO4
(3) BaCl2 (4) AlCl3 (4) SrSO4

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
102 The s-Block Elements NEET

20. Property of the alkaline earth metals that increases 27. The correct order of the mobility of the alkali metal
with their atomic number [AIPMT (Prelims)-2010] ions in aqueous solution is [AIPMT (Prelims)-2006]
(1) Solubility of their hydroxides in water (1) Li+ > Na+ > K+ > Rb+ (2) Na+ > K+ > Rb+ > Li+
(2) Solubility of their sulphates in water (3) K+ > Rb+ > Na+ > Li+ (4) Rb+ > K+ > Na+ > Li+
(3) Ionization energy Questions asked Prior to Medical Ent. Exams. 2005
(4) Electronegativity 28. In Castner-Kellner cell for production of sodium
21. Which one of the following compounds is a hydroxide :
peroxide ? [AIPMT (Prelims)-2010]
(1) Brine is electrolyzed with Pt electrodes
(1) KO2 (2) BaO2
(2) Brine is electrolyzed using graphite electrodes
(3) MnO2 (4) NO2
(3) Molten sodium chloride is electrolysed
22. The compound A on heating gives a colourless gas
and a residue that is dissolved in water to obtain (4) Sodium amalgam is formed at mercury
B. Excess of CO2 is bubbled through aqueous cathode
solution of B, C is formed which is recovered in the 29. In the replacement reaction
solid form. Solid C on gentle heating gives back A.
The compound is [AIPMT (Mains)-2010] Cl + MF  CF + MI
(1) CaCO3 (2) Na2CO3
The reaction will be most favourable if M happens
(3) K2CO3 (4) CaSO4.2H2O
to be
23. Which of the following oxides is not expected to
react with sodium hydroxide? (1) Na (2) K

[AIPMT (Prelims)-2009] (3) Rb (4) Li

(1) CaO (2) SiO2 30. The solubility in water of sulphate down the Be
group is Be > Mg > Ca > Sr > Ba. This is due to
(3) BeO (4) B2O3
(1) Decreasing lattice energy
24. The alkali metals from salt-like hydrides by the
direct synthesis at elevated temperature. The (2) High heat of solvation for smaller ions like Be2+
thermal stability of these hydrides decreases in (3) Increase in melting points
which of the following orders?
(4) Increasing molecular weight
[AIPMT (Prelims)-2008]
31. The sodium is made by the electrolysis of a molten
(1) LiH > NaH > KH > RbH > CsH
mixture of about 40% NaCl and 60% CaCl 2
(2) CsH > RbH > KH > NaH > LiH because
(3) KH > NaH > LiH > CsH > RbH (1) Ca++ can displace Na from NaCl
(4) NaH > LiH > KH > RbH > CsH (2) This mixture has a lower melting point than
25. In which of the following the hydration energy is NaCl
higher than the lattice energy?
(3) CaCl2 helps in conduction of electricity
[AIPMT (Prelims)-2007]
(4) Ca++ can reduce NaCl to Na
(1) SrSO4 (2) BaSO4
32. Identify the correct statement
(3) MgSO4 (4) RaSO4
(1) Plaster of Paris can be obtained by hydration
26. The correct order of increasing thermal stability of of gypsum
K2CO3, MgCO3, CaCO3 and BeCO3 is
(2) Plaster of Paris is obtained by partial oxidation
[AIPMT (Prelims)-2007]
of gypsum
(1) K2CO3 < MgCO3 < CaCO3 < BeCO3
(3) Gypsum contains a lower percentage of
(2) BeCO3 < MgCO3 < K2CO3 < CaCO3 calcium than Plaster of Paris
(3) BeCO3 < MgCO3 < CaCO3 < K2CO3 (4) Gypsum is obtained by heating Plaster of
(4) MgCO3 < BeCO3 < CaCO3 < K2CO3 Paris

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET The s-Block Elements 103
33. Calcium is obtained by 5. Which of the following alkaline earth metal does
not exhibit colour when heated?
(1) Reduction of calcium chloride with carbon
(1) Ca (2) Mg
(2) Electrolysis of molten anhydrous calcium
chloride (3) Sr (4) Both (2) & (3)
(3) Roasting of limestone 6. Solution of sodium carbonate is

(4) Electrolysis of solution of calcium chloride in (1) Alkaline due to hydrolysis of Na+
H2O
(2) Alkaline due to hydrolysis of CO32
34. When a substance (a) reacts with water it
produces a combustible gas (b) and a solution of (3) Alkaline due to hydrolysis of both Na+ and
substance (c) in water. When another substance (d)
CO32
reacts with this solution of (c), it also produces the
same gas (b) on warming but (d) can produce gas (4) Neutral due to hydrolysis of both Na+ and
(b) on reaction with dilute sulphuric acid at room CO32
temperature. Substance (a) imparts a deep golden
yellow colour to a smokeless flame of Bunsen 7. Which of the following elements of group-1 show
burner. Then (a), (b), (c) and (d) respectively are maximum tendency for the following half reaction?

(1) Ca, H2, Ca(OH)2, Sn M(g)  M+(aq) + e–

(2) K, H2, KOH, Al (1) Li (2) Na

(3) Na, H2, NaOH, Zn (3) K (4) Rb

(4) CaC2, C2H2, Ca(OH)2, Fe 8. Which of the following is most stable?

(1) Rb3N (2) K3N
SECTION - D (3) Na3N (4) Li3N

NEET Booster Questions 9. Which of the following has highest melting point?

1. Which of the following is not correct for alkali (1) Cs (2) K

metals? (3) Na (4) Li
(1) Low melting point 10. Which of the following is paramagnetic?
(2) Their ions are isoelectronics with noble gases (1) Li2O (2) RbO2
(3) Good reducing agents (3) CO2 (4) SO3
(4) High ionisation energy 11. Cs + NH3(l) gives a conducting solution of colour
2. What is the correct order of size of following ions? (1) Blue (2) Red
(A) = [Li(H2O)n]+ (B) = [Na(H2O)n]+ (3) Green (4) Golden
(C) = [K(H2O)n]+ 12. Hybridisation of Be in BeCl2 at room temperature
(1) A > B > C (2) C > B > A is

(3) A = B = C (4) B > C > A (1) sp (2) sp2

3. Which of the following is the least soluble in water? (3) sp3 (4) dsp2
13. Which of the following has highest melting point?
(1) BaSO4 (2) CaSO4
(1) LiCl (2) NaCl
(3) MgSO4 (4) BeSO4
(3) KCl (4) RbCl
4. A metal ‘X’ forms water soluble sulphate XSO4. It
forms oxide XO which becomes inert on heating. 14. The compound which produces coloured gas upon
Its hydroxide X(OH)2 is soluble in NaOH. ‘X’ is decomposition
(1) Li (2) Be (1) LiNO3 (2) NaNO3
(3) Ba (4) Mg (3) Na2CO3 (4) K2CO3
Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
104 The s-Block Elements NEET

15. Which of the following cannot form nitride? 24. Which is correct order
(1) Li (2) K (1) ZnO > BeO > MgO > CaO : basic strength
(3) Mg (4) Be (2) LiOH > NaOH > KOH > RbOH : solubility
16. The product of the reaction between CaO + P4O10 (3) LiCl > NaCl > KCl > RbCl > CsCl : solubility
will be
(4) BeSO 4 < MgSO 4 < CaSO 4 < SrSO 4 :
(1) Ca3(PO3)2 (2) P4O6 + CaO2 Thermal stability
(3) Ca3(PO4)2 (4) Ca3P2 + O2 25. Which salt does not impart colour to flame?
17. Formula of plaster of Paris is (1) MgCl2 (2) SrCl2
1 (3) BaCl2 (4) LiCl
(1) CaSO4  H2O (2) CaSO4
2
26. What is the formula for the basic anhydride of
(3) CaSO4.2H2O (4) CaSO4.H2O Ba(OH)2?
18. Portland cement has highest content of (1) Ba2O (2) BaO
(1) CaO (2) Al2O3 (3) BaO2 (4) Ba
(3) MgO (4) Fe2O3 27. RbO2 is
19. Which of the following pair, that react with air to (1) Peroxide and Paramagnetic
produce oxide as well as nitride?
(2) Peroxide and Dimagnetic
(1) C, Al (2) Li, K
(3) Superoxide and Paramagnetic
(3) Li, Mg (4) B, Si
(4) Superoxide and Diamagnetic
20. Ratio of number of moles of water in gypsum and
plaster of Paris is 28. In which of the following covalent radii can't be
calculated by any way?
(1) 4 : 1 (2) 1 : 4
(1) Li (2) Na
(3) 2 : 1 (4) 1 : 2
(3) Ne (4) None of these
21. Which is correctly matched?
29. Hardest s-block metal is
(1) Soda ash – Na2CO3
(1) Li (2) Na
(2) Washing soda – Na2CO3.10H2O
(3) Mg (4) Be
(3) Baking soda – NaHCO3
30. Which of the following is/are correct order
(4) All of these
(A) Solubility = BeSO4 < MgSO4 < CaSO4 < SrSO4
22. Calcium hydride, also known as hydrolith is
hydrolysed by water to produce (B) Lattice energy = NaF < MgF2 < AlF3
(1) Ca(OH)2 + H2 (2) CaO + O2 (C) Solubility = LiOH < NaOH < KOH < RbOH <
(3) CaO + H2 (4) Does not hydrolyse CsOH

500°C
(D) Lattice energy = KF > KCl > KBr > KI
23. NaNO 3 A(s) + B(g)
(1) (A) and (B) (2) (B) and (D)
800°C
NaNO 3 C(s) + B(g) + D(g) (3) (A), (B) and (D) (4) (A), (B), (C) and (D)
A, B, C and D are respectively 31. Which of these gives oxide on heating?
(1) Na2O, O2, NaNO2, N2 (1) LiNO3
(2) NaNO2, O2, Na2O, N2 (2) NaNO3
(3) NaNO2, N2, Na2O, O2 (3) KNO3
(4) Na2O2, N2O, NaNO2, N2 (4) RbNO3
Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
NEET The s-Block Elements 105
32. Which among the following shows the tendency to 40. On heating sodium hydrogen carbonate, the
form peroxide? products formed are
(1) Li (2) Mg (1) Na2O + CO2 + H2O
(3) Be (4) Ba (2) Na2CO3 + CO2
33. The solubility order of the chlorides of the alkali (3) Na2CO3 + H2O + CO2
metals is
(4) Na2CO3 + H2O
(1) NaF > KF > RbF > CsF
41. Solvay process is used for formation of
(2) CsF > RbF > KF > NaF
(1) NaCl (2) NaOH
(3) KF > NaF > RbF > CsF (3) Na2SO4 (4) Na2CO3
(4) CsF > RbF > NaF > KF 42. Which is not the compound of sodium?
34. The thermal stability order of the carbonates is (1) Chile salt petre (2) Indian salt petre
(1) Na2CO3 > K2CO3 > BeCO3 > BaCO3 (3) Glauber's salt (4) Soda ash
(2) K2CO3 > Na2CO3 > BaCO3 > BeCO3 43. Aqueous solution of which of the following gives
(3) BaCO3 > BeCO3 > K2CO3 > Na2CO3 H2O2?

(4) BeCO3 > Na2CO3 > BaCO3 > K2CO3 (1) K2O (2) K2O2

35. Which one of the following statements concerning (3) KO2 (4) Both (2) & (3)
the compounds of Lithium is false? 44. Castner-kellner cell is used for formation of
(1) The hydroxide, carbonate, nitrate, decompose (1) Starch (2) Ca(H2PO4)2
to give the oxide on heating
(3) NaOH (4) All of these
(2) It is the most electronegative among alkali
metals 45. Which one of the following statements is correct
for the chlorides of group II metals?
(3) The hydrogen carbonate cannot be isolated as
a stable solid (1) Are all hygroscopic in nature

(4) It forms a peroxide but not superoxide (2) Increase in lattice enthalpy from BeCl2 to BaCl2

36. Which of the following is not an acidic salt? (3) Decrease in m.p. from BeCl2 to BaCl2

(1) NaH2PO2 (2) NaH2PO3 (4) Are all insoluble except BaCl2

(3) NaH2PO4 (4) Na2HPO4 46. The thermal stability of alkaline earth metal
carbonates increases from Be to Ba. This is
37. Sodium is usually kept under because
(1) Alcohol (2) Kerosene oil (1) Covalent nature decreases and Ionic nature
(3) Water (4) All increases

38. Alums are not formed by which alkali metal? (2) Lattice energy increases

(1) Li (2) K (3) Electropositive nature decreases

(3) Na (4) Cs (4) None of these

39. Which of the following statement is true? 47. The solubility of sulphates in water decreases from
MgSO4 to BaSO4. It is due to the fact that
(1) NaHCO3 is strongly basic in nature
(1) Ionic nature increases
(2) Pure NaCl is hygroscopic
(2) Size of M2+ ion increases
(3) On increasing temperature increase in
solubility of NaCl in water occurs (3) Lattice energy decreases

(4) All of these (4) Hydration enthalpy of M2+ ions decreases

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456
106 The s-Block Elements NEET

48. Which of the following order is correct for thermal 54. The electrolysis of molten KCl · MgCl2 · 6H2O gives
stability?
(1) Mg only (2) K only
(1) MgCO3 < CaCO3 < BeCO3
(3) K and Mg only (4) Mg and Cl2
(2) BeCO3 < MgCO3 < CaCO3
55. Alkaline earth metals form hydrated crystalline
(3) CaCO3 < BeCO3 < MgCO3 solids such as MgCl2 · 8H2O and CaCl2 · 6H2O.
(4) CaCO3 < MgCO3 < BeCO3 This is due to

49. Which of the following statements is incorrect (1) Smaller ionic size
for Be? (2) Increased charge on ions
(1) Most of its compound are largely covalent (3) Higher hydration enthalpies
(2) BeCl2 has bridged covalent structure and is a (4) High oxidation potential
linear molecule above 1200 K
56. Compared with the alkaline earth metals, the alkali
(3) It has distinctive group properties due to
metals show
smaller size and high electronegativity
(1) Greater hardness
(4) It forms Be2+ ions because of the lower value
the sum of Ist and 2nd I.E. (2) Higher m.p.
50. Metallic Magnesium is prepared by (3) Smaller ionic radii
(1) Displacement of Mg by iron from MgSO 4 (4) Lower ionization energy
solution

(2) Electrolysis of an aqueous solution of 57. CaCO3 A + B(gas)
Mg(NO3)2
H2O Cl2
(3) Electrolysis of molten MgCl2 C D
40ºC

(4) Reduction of MgO by aluminium

Product D is
51. Chemical ‘A’ is used for water softening to remove
(1) CaCl2 (2) Ca(OH)2
temporary hardness. ‘A’ reacts with sodium
carbonate to generate caustic soda. When carbon (3) CaCl2.6H2O (4) CaOCl2
dioxide is bubbled through ‘A’, it turns cloudy. What
58. Correct order of solubility
is the chemical formula of ‘A’?
(1) BeSO4 > BaSO4 (2) LiCl > LiF
(1) CaCO3 (2) CaO
(3) NaHCO3 < KHCO3 (4) All of these
(3) Ca(OH)2 (4) Ca(HCO3)2
52. Epsom salt’s chemical formula is 59. Among the oxides of group 2, least basic is

(1) MgSO4 · 7H2O (2) Mg(OH)2 (1) MgO (2) CaO

(3) 2CaSO4 · H2O (4) BaSO4 (3) SrO (4) BaO

53. Molecular formula of Glauber’s salt is 60. Beryllium on ignition in air gives

(1) MgSO4 · 7H2O (2) CuSO4 · 5H2O (1) BeO (2) Be3N2

(3) FeSO4 · 7H2O (4) Na2SO4 · 10H2O (3) Both (1) & (2) (4) BeC

‰ ‰ ‰

Aakash Educational Services Limited - Regd. Office : Aakash Tower, 8, Pusa Road, New Delhi-110005 Ph. 011-47623456