Module 2 - XI NEET - Chemistry

COMPREHENSIVE
SELF – STUDY MATERIAL

FOR
NEET & AIIMS

CHEMISTRY - XI
Content Page
Module 2 .............................................................................................................................. 2
(1) Thermodynamics and Thermochemistry .............................................................. 3

(2) Redox Reaction ................................................................................................... 70
(3) States of Matter (Gaseous & Liquid) .................................................................. 99
COMPREHENSIVE
SELF - STUDY MATERIAL
FOR
NEET & AIIMS
CHEMISTRY
CHEMISTRY
Module - 2
n Thermodynamics and Thermochemistry

o Redox Reaction
p States of Matter (Gaseous & Liquid)
2
THERMODYNAMICS AND
CHAPTER
05
THERMOCHEMISTRY
The production of motion in the steam engine always occurs in cir-
cumstances in which it is necessary to recognize, namely when the
equilibrium of caloric is restored or when caloric passes from the body
at one temperature to another body at a lower temperature.
“SADI CARNOT”
INTRODUCTION
T
hermodynamics is the branch of chemistry that deals with energy changes occuring
during various physical & chemical processes. It also deals with the transformation
between different forms of energy.Chemical energy stored by molecules can be
released as heat during chemical reaction when a fuel like methane, cooking gas
or coal burns in air . The chemical energy may also be used to mechanical work
when a fuel burns in an engine or to provide electrical energy through a galvenic
cell like dry cell. Thus, various forms of energy are interrelated and under certain
conditions,thease may be transformed from one form into another.The study of
thease energy transformation forms the subject matter of thermodynamics. The laws
of thermodynamic deals with energy changes of macroscopic systems involving
a large number of molecules rather than microscopic systems containing a few
molecules.
In thermochemistry, chemical processes are associated with energy changes in
chemical reactions.
3
CHEMISTRY FOR NEET & AIIMS
BASIC TERMS USED IN THERMODYNAMICS :
System : The part of universe under thermodynamics investigation is called system.
Surrounding : Anything out side the system is called surrounding.
Universe = System + Surroundings
TYPES OF SYSTEM
Depending on Exchange of Energy Between Sstem and Surroundings System can be Classified as:
(h) Open System : A system which can exchange both energy and matter with surrounding.
Ex. Coffee in open glass.
(ii) Closed System : A system which can exchange only energy with surrounding.
Ex. Coffee in close vessel.
(iii) Isolated System : A system which cannot exchange matter or energy with surrounding.
Ex. Coffee in thermoflask.
Depending on the Components of System Involved it can also be Classified as:
Homogeneous System : System consisting of single phase. e.g. Pure solid, a pure liquid a solution, or a mixture
of gases(gases always form homogeneous mixture)
Heterogenous System : A system consisting of more than one phase.
Ex. System of two immiscible liquids, two or more solids, a liquid in contact with its vapour etc. are example of
heterogenous system.
Boundary : Anything which separates system and surrounding is called boundary. Across boundary energy and
mass are transferred between system and surrounding.
A boundary can be real or hypothetical.
Types of Wall or Boundary
Rigid Wall : The wall is immovable.
Non Rigid Wall : The wall is movable .
Adiabatic Wall : No heat exchange across the wall i.e. q = 0.
Diathermic Wall : The heat can be exchanged across the wall i.e. q z 0.
STATE OF SYSTEM :We specify the state of a system - say, a sample of material - by specifying the values of
all the variables describing the system.
If the system is a sample of a pure substance this would mean specifying the values of the Temperature(T),Pressure(P),
Volume(V)and the number of moles of the substance(n).
“When the values of state variables changes the state of system also changes i.e. state of a system depends on
the value of state variables and if their value changes the state of system also changes”
Example Based on Basic Definition :
Ex. When no heat and matter is allowed to enter or leave the system, it is called :-
(A) open system (B) closed system
(C) isolated system (D) may be open or close
Sol. (C)
Ex. A well stoppered thermos flask contains some ice cubes. This is an example of a :-
(A) closed system (B) open system
(C) isolated system (D) non-thermodynamics system
Sol. (C)
STATE FUNCTIONS :
“These are the thermodynamic functions whose value depends only on the state of
system and is independent of the path followed to change the state of system.”
4
THERMODYNAMICS AND THERMOCHEMISTRY
x Both state function and state variables are same.

x Change in value of state function ('A) = Afinal - Ainitial
x Differential of a state function integerated over a cyclic path returns zero. In other words overall change in state
function in a cyclic process is equal to zero.
if v³ dX 0 X is a state function (property of state function)

Ex. Enthalpy(H), Internal Energy(E), Entropy(S), Gibbs free Energy(G), P,T,V etc.
PATH FUNCTIONS :
These are the thermodynamic functions whose value depend on the path connecting two states . There can be infinite
vaules of path function between two states depending upon path or process.
Path functions are also called indefinite quantities since between two fixed state the value of path function is not
fixed. Heat and Work are two important path dependent quantities with which we deal in this chapter.
EXTENSIVE AND INTENSIVE PROPERTIES :
Extensive : The Propterties of system which depend on the amount of the substance (or substances) present in the
system and size of system are called extensive propterties. e.g. Mass, volume, heat capacity, internal energy, entropy,
Gibb's free energy (G), surface area etc.
x These properties will change with change in the amount of matter present in the system.
x It is important to note that the total value of an extensive property of a system is equal to the sum of the values
of different parts into which the system is divided.
Intensive : Properties which are independent of the amount of substance (or substances) present in the system and
size of system are called intensive properties, e.g. pressure, density, temperature, viscosity, surface tension, refractive
index, emf, chemical potential, sp. heat etc. These are intensive properties.
Following are some important characteristics of Intensive & Extensive Properties
A dA
x If A & B are two extensive properties than & will be Intensive.
B dB
x If an extensive property is represented as per unit mass or mole or volume it will become an intensive property.
Ex. Concentration mole / volume
Density = mass / volume
sp.heat capacity = heat capacity / mass
While mole, mass, heat capacity are extensive properties, concentration, density and specific heat capacity are
intensive properties.
Extensive Properties Intensive Properties
Volume (V) Molar volume (Vm)
Number of moles (n) Density (d)
Mass (m) Gibb’s energy per mole (Gm)
Gibb’s Energy (G) Specific heat
Entropy (S) Pressure (P)
Enthalpy (H) Temperature (T)
Internal energy (E or U) All concentration terms (M, N)
Heat capacity (C) Boiling point, freezing point (Tb, Tf)
Force (F) Cell potential (Ecell)
Surface Area (A) Specific conductance (N)
Refractive index
Surface tension, Viscosity
pH value
Vapour pressure
5
Note : Intensive properties of a substance are non-additive in nature while extensive properties are additive in nature.
The ratio of extensive property indicates the intensive property. eg. mass/volume
THERMODYNAMIC EQUILIBRIUM
Thermodynamic generally deals the equilibrium state of the system in which the state variable are uniform and constant
throughout the whole system.
For a system to be in thermodynamic equilibrium all the following three types of equilibrium must co-exist.
(h) Mechanical Equilibrium
When there is no macroscopic movement within the system itself or of the system with respect to
surroundings, the system is said to be in a state of mechanical equilibrium.
(ii) Chemical Equilibrium
When the system consists of more than one substance and the composition of the system does not vary with
time, the system is said to be in chemical equilibrium. The chemical composition of a system at equilibrium must
be uniform and there should be no net chemical reaction taking place.
(iii) Thermal Equilibrium
When the temperature throughout the entire system is the same as that of the surroundings then the system
is said to be in thermal equilibrium.
Ex. Which is the intensive property :-
(A) temperature (B) viscosity (C) density (D) all
Ans. (D)
Ex. A thermodynamic state function is :-
(A) one which obeys all the law of thermodynamics
(B) a quantity which is used in measuring thermal changes
(C) one which is used in thermo chemistry
(D) a quantity whose value depends only on the state of system
Ans. (D)
Ex. A system is changed from state A to state B by one path and from B to A by another path. If DE1 and DE2 are the
corresponding changes in internal energy, then :-
(A) DE2 + E2 = +ve (B) DE1 + DE2 = –ve (C) DE1 + DE2 = 0 (D) none of the above
Ans. (C)
THERMODYNAMIC PROCESS
The path followed to change the state of a system is called a process.
Path of a Process
The exact sequence of steps through which system changes state is called path of a process.e.g. reversible or irrervisible
path
Some Thermodynamic Processes
(1) Isothermal process P
Isothermal process are those processes in which
(a) Temperature remains constant i.e. 'T = 0
(b) Heat is exchanged with surroundings
(c) System is placed at a constant temperature. V
x For ideal gas in Isothermal process 'E = 0 and 'H = 0
P
x All phase transitions are isothermal process but 'E z 0 and 'H z 0
(2) Isobaric process
Osobaric process are those processes in which Pconstant
(a) Pressure remains const i.e. 'P = 0
(b) Volume & temperature are variable.
(c) Process in open system is isobaric in nature.
V
6
P
(3) Isochoric process
Isochoric process are those processes in which
(a) volume remains constant i.e. 'V = 0
(b) pressure & temperature are variable
(c) Work, W = P'V, ''V = 0, ?W = 0 (Zero) V V
constant
(d) Process in closed system is isochoric. Pressure
(4) Adiabatic process

Adiabatic process are those processes in which
(a) No exchange of heat takes place i.e. q = 0
(b) The temperature of the system varies. Work done volume
(c) The system is thermally insulated this can be done by keeping the system in an insulated container.
(5) Cyclic Process : If a system after completing a series of different process returns to its initial state then overall
process is called cyclic process.
“The overall change in value of a state function during the complete cycle is zero”
Ex. 'H = 0, 'E = 0, 'P.E. = 0
(6) Reversible Process :
x These are very slow processes and do not go for completion or take very long time.
x In a reversible process the driving force is greater than the opposing force by a very small value (infinitesimally
small value).
x The reversible process is carried out in such a manner that if at any moment opposing force is increased by a small
amount the direction of process can be reversed
x A reversible process is also called “quasi static” process. A quasi static process is the one in which system remain
infinitesimally closer to the state of equilibrium through out the process.
x Pext = Pint ± dP ; Pext is variable.
x It is an ideal process.
-work
-heat
initial process restoring process

Piston Cylinder
KEY POINTS
(h) During a reversible process, the system and surrounding remain in equilibrium throughout the process.
(ii) The reversible processes are idealized processes which cannot be actually carried out, but nevertheless they
are very important because they help in calculation of change in state function in the process. In other words
the reversible processes are hypothetical processes.
(7) Irreversible Process :

x These are very fast processes and are completed in a short interval of time.
x In an irreversible process the driving force is much greater than the oppsoing force and therefore the process is
completed very fast.
7
d
A
F
Piston Cylinder
x All natural processes are example of irreversible process.
x Pext = Pint ± 'P ; Pext is constant.
S. No. Reversible Process Irreversible Process
1 These are slow processes. These are instantaneous or sudden processes.
Driving force is infinitesimally Driving force is large and finite.
2
small.
3 It is an ideal process. It is a real process.
4 It takes infinite time for completion of process. It takes finite time for completion of the process.
It is an imaginary process and can not be realised It is a natural process and occurs in particular
5
in direction under given set of conditions.
Throughout the process, the system remain The system is far removed from state of equilibrium
6 infinitesimally closer to state of equilibrium. and exact path of process can be drawn.
HEAT AND WORK :

Heat and work both are mode of energy transfer between system and surrounding.
Heat flows due to temperature gradient while work is done due to imbalance of generalized force.
Heat exchange (q) :
Heat is defined as the energy that flow into or out of a system because of a difference in temperature between the
thermodynamic system and its surrounding. It is a path function.
According to IUPAC convention heat given by the system is expressed with negative sign heat given to system
is expressed with positive sign.
x Heat always flows from high temperature to low temperature.
Sign Convention
x Heat flowing into the system or Heat absorbed by the system q = positive
x Heat flowing out of the system or Heat released by the system q = negative
Work is classified into two broad categaroies as :
(H) PV Work – This type of work is done when change in volume ocurrs under the influence of external pressure.
Consider a clylinder(cross section area A) fitted with a frictionless piston, which enclosed n mole of an ideal
gas. Let an external force F pushes the piston inside producing displacement dx in piston.
F
A
(–x) x
small change in volume of gas (dV) = A.dx
Small work done dw = F.dx
8
F
Also P=
A
F = PA
dW = PA.dx
' dV = – A . dx (-ive sign indicates work is done by the system i.e. gas is
expanding against Pext)
dW = – Pext. dV
w ³ PexternaldV
Sign Convention
Work done by the system is ive.
Work done on the system is +ive
KEY POINTS
(1) During expansion dV is +ive and hence sign of w is -ive i.e. work is done by the system and hence Expansion
Work is always negative.
(2) During compression, dV is -ive which gives +ive value of w i.e. work is done on the system and hence
Compression work is always positive.
(II) Non-PV Work - Following are some examples of Non-PV work.

Stretching Tension (J), length (l) w ³ Jdl Nm=J
Surface expansion Surface tension (Jmm), area (V) w ³ ³ JdV (N m–1) (m2) = J
Electrical Electrical potential (I), w=q×V V×C=J
Units of heat & work :
Calorie : It is defined as the quantity of heat required to raise the temperature of 1g of water by 1°C (14.5 to 15.5°C)
1 cal = 4.184 J = 4.2 J
1 L-atm = 101.3 J = 24.206 cal = 101.3 × 107 erg
1 L-atm > 1 cal. > 1 J. > 1 erg
Ex. Find the work done,when one mole of ideal gas in 10 litre container at 1 atm. is allowed to enter a vaccuated bulb of
capacity 100 litre.
Sol. (a) W = – P'V
But since gas enters the vaccum bulb and pressure in vaccum is zero.
W=0
Ex. If 1 mole of gas expands from 1 litre to 5 litre against constant atmospheric pressure than calculate thw work done.
Sol. (b) W = –P'V = –1(5 – 1) = – 4 litre-atm.
Ex. Calculate the work done when 1 mol of zinc dissolves in hydrochloric acid at 273 K in :
(a) an open beaker
(b) a closed beaker at 300 K.
Sol. (a) From one mole of zinc, the no. of moles of H2 gas evolved = 1
Hence volume of hydrogen gas evolved = 22.4 litre (when P = 1 atm and T = 273 K)
? w = –P'V = –1 × 22.4 litre atm
8.314
= –22.4 × J = –2271.14 J
0.082
(b) For a closed system Pext = 0., therefore, w = 0.
9
Ex. Calculate the work performed when 2 moles of hydrogen expand isothermally and reversibly at 25ºC form 15 to 50
litres.
V2 50
Sol. We have, W = – 2.303 n RT log V = – 2.303 × 2 × 2 × 298 × log = – 1436 calories.
1 15
Ex. If a gas at a pressure of 10 atm at 300 k expands against a constant external pressure of 2 atm from a vol. of 10 litres
to 20 litres find work done ? [Isothermal process]
Sol. Process is irreversible
20
w = – ³ 2dv = –2[20 –10] = – 20 L.atm
10
1 litre atm = 101.3 J
INTERNAL ENERGY (U OR E)
Consider a system of mass 'M' is moving in gravitational field with velocity v. The total energy of system (in earth
frame of reference) is given as :
E = K + V + U : (K = kinetic energy, V = potential energy, U = internal energy)
A thermodynamic system is studied generally at rest so K = 0. If effect of gravitation field (or other fields are ignored)
is also ignored then we left with E = U.
So, “In absence of an external field(no external potential energy), when the system is at rest(no external kinetic
energy) the total energy of the system is called its internal energy”
The internal energy of the gas confined in a container is defined relative to a coordinate system fixed on the container.
Viewed at a microscopic(atomic) level, the internal energy can take on a number of forms such as.
x The kinetic energy of the molecules ;
x The potential energy of the constituents of the system ; for example, a crystal consisting of dipolar molecules will
experience a change in its potential energy as an electric field is applied to the system ;
x The internal energy stored in the form of molecular vibrations and rotations;
x The internal energy stored in the form of chemical bonds that can be released through a chemical reaction.
The total of all these forms of energy for the system of interest is given the symbol U and is called the internal
energy.
Hence total internal energy of a system can be written as
U = Utranslational+Urotational+Uvibrational+Uintermolecular+Uelectronic+Urelativistic
out of these Urelativistic and Ueletronic is unaffected by ordinary heating. So basically the kinetic energy terms and Uintermolecur
accommodate the heat provided to the system . Hence heat capacity of a sample depends upon these four terms.
For an ideal gas, Uintermolecular is equal to zero, because of absence of intermolecular force of attraction in ideal gas.
Uintermolecular have large and negative value in solids and liquids.
For an ideal gas U is only function of temperature e.g. U=F(T) +Constant
Due to absence of pressure or volume terms in ideal gas internal energy, U is independent of pressure a nd
volume of ideal gas.
x Internal Energy is an extensive Property and is a state function.

If a system is present in particular thermodynamic state say 'A' it has fixed amount of internal energy UA.
Suppose by a process the system is taken from state A to state B then
'U = UB - UA
10
A q,w
Since U is state function. This implies between any two fixed state, there can be infinite process or path, but 'U
in all process will remain the same.(Property of a function of state)
Consider a system taken from state A to B by nth different paths.
i.e. 'U1 = 'U2 = 'U3 .........
A I
II
III
nth
B
For a given system , Internal Energy can be represented as a function of volume and temperature U = f (T, V)
and the overall change in I.E. can be claculated mathematically as :
§ wU · § wU ·
dU = ¨ ¸ . dT + ¨ ¸ dV
© wT ¹ v © wV ¹T
x For isochoric process : dV = 0
§ wU ·
dU = ¨ ¸ dT
© wT ¹ v
dU = Cv . dT
Overall change in I.E. 'U ³ C v .dT

x For an ideal gas
§ wU ·
¨ ¸ 0
© wV ¹ T
dU = Cv . dT
'U ³ C v .dT
§ wU ·
x For a real gas ¨ ¸ is Positive when attractive forces dominates(in both compression & expansion) and
© wV ¹T
§ wU ·
¨ ¸ is Negative when repulsive forces dominates (in both compression & expansion).
© wV ¹T
11
KEY POINTS
Note that heat and work involve in all the process are different but 'U is same. This mean heat and work are indefinite
quantities while 'U is a definite quantity.
FIRST LAW OF THERMODYNAMICS
The first law of thermodynamics is based on energy conservation principle i.e
"Total energy of universe remain constant."
Let us consider a system whose internal energy is U1. If the system is supplied with heat q, the internal energy of the
system increases to U1 + q. If work (w) is now done on the system, the internal energy in the final state of the system, U2
is given by
U2 = U1 + q + w
or U2 – U1 = q + w
'U = q + w,
According to IUPAC , heat, added to the system and work done on the system are assigned positive values as both
these Modes increase the internal energy of the system.
CONCLUSIONS FROM THE FIRST LAW OF THERMODYNAMICS :
(a) During isothermal process of an ideal gas
During an isothermal process the temperature of the system remains constant and hence
'E = 0
Therefore FLOT : 'E = q + w
? +q = –w or –q = +w
In isothermal process –
(H) Heat absorbed by the system is equal to work done by the system.
OR
(II) Heat evolved by the system is equal to work done on the system.
(b) During isochoric process
At constant volume V1 = V2 i.e. 'V = 0
Hence W = –P ' V = 0 ............... No work done at constant volume of therefore,
FLOT: 'E = q + w 'E = qv
(h) In isochoric process
• At constant volume heat absorbed by the system is equal to increase in internal energy of the
system.
OR
• At constant volume, heat evolved by the system is equal to decrease in internal energy of the
system.
(ii) Heat at constant volume (qv) = 'E
(iii) In isochoric process heat behaves as state function.
(c) During adiabatic process :
During adiabatic process the system acts an isolated and hence q = 0 in such cases. Therefore
FLOT : 'E = q + w 'q=0 'E = w
(h) Work done on the system is equal to increase in internal energy of the system i.e., when a gas is
compressed adiabatically its internal energy increases.
OR
Work done by the system is equal to decrease in internal energy of the system, i.e., when a gas is
expanded adiabatically its internal energy decreases.
(ii) In adiabatic process work behaves as state function.
12
(d) During Cyclic Process :
'E = 0 FLOT : 'E = q + w +q = –w
In cyclic process.
(H) Work done by the system is equal to heat absorbed by the system.
OR
(II) Work done on the system is equal to heat evolved by the system.
(e) During Isobaric process :
P – constant
FLOT : 'E = q + w
'E = q + (–P'V)
qP = 'E + P'V
qP = (E2 – E1) + P(V2 – V1)
qP = (E2 + PV2) – (E1 + PV1)
' Enthalpy H = E + PV
? qP = H2 – H1 qP = 'H
(h) In isobaric process :
• At constant pressure, heat absorbed by the system is equal to increase in enthalpy of the system.
OR
• At constant pressure, heat evolved by the system is equal to decrease in enthalpy of the system.
(ii) Heat at constant pressure (qP) = 'H
(iii) In isobaric process heat behaves as state function.
Ex. A system expands from 5 L to 10 L against a constant external pressure of 2 atom. If it absorbs 800 J of energy in the
process. Calculate the change in its internal energy.
Sol. 'u = q + w
w = – (v2 – v)
= –2 (10 – 5)
= –10 atm -L × 101.3 J = –1013 J
'U = –213 J
Ex. FeCO3(s) decomposes at constant pressure as FeO(s) + CO2(g)
'
FeCO3(s) o FeO(s) + CO2(g)
at 25°C, the heat absorbed during the reaction is 80 kJ.
Calculate 'H & 'V for the reaction.
Sol. FeCO3(s) o FeO(s) + CO2(g)
'H = qp = 80 kJ
'H = 'U + 'ngRT
[1u 8.314 u 298]
80 kJ = 'U kJ
1000
'U = 77.522 kJ
ENTHALPY(H)
Chemical reactions are generally carried out at constant pressure (atmospheric pressure) so it has been found useful to
define a new state function Enthalpy (H) as :
H = U + PV
'H = 'U + '(PV)
at constant pressure
'H = 'U + P 'V ......(1)
13
From First Law 'U = q + w = q - PdV
q = 'U + PdV = 'H.....(2)
combining with first law.
'H = qp
Hence transfer of heat at constant volume brings about a change in the internal energy of the system whereas that at
constant pressure brings about a change in the enthalpy of the system.
x For a given system
H = f (T, P)
§ wH · § wH ·
dH = ¨ ¸ . dT + ¨ ¸ dP
© wT ¹ P © wP ¹ T
x For isobaric process : dP = 0
§ wH ·
dH = ¨ ¸ dT
© wT ¹ P
dH = CP . dT
'H ³ C P .dT
x For an ideal gas
§ wH ·
¨ ¸ 0
© wP ¹ T
dH = CP . dT
'H ³ C P .dT
RELATIONSHIP BETWEEN 'H & 'U

The difference between 'H & 'U becomes significant only when gases are involved (insignificant in solids and
liquids)
'H = 'U + '(PV)
If substance is not undergoing chemical reaction or phase change.
'H = 'U + nR'T
In case of chemical reaction
'H = 'U + 'ng)RT
Where 'H = qp ; at constant p ; 'U = qv ; at constant V+
so the equition can be written as qp = qv +'ng)RT
Heat Exchange at Constant Volume and Constant Pressure (qp and qv)
Heat exchange can be divided into two parts :
Hence heat exchanged at constant pressure and volume are important Definite quantities
14
Heat Capacity
The heat capacity of a system may be defined as the amount of heat required to raise the temperature of the system by
one degree.
If Gq is the small quantity of heat added to the system, let the temperature of the system rises by dT, then heat capacity
C of the system is given by
dq
C= .....(h)
dT
In case of gases we have two types of heat capacity i.e. heat capacity at constant volume and heat capacity at constant
pressure. units = J K–1, cal K–1, J °C–1, cal °C–1.
Heat Capacity at Constant Volume( Cv) :
Molar heat capacity at constant volume is defined by the relation
dq v
CV = ....(ii)
dT
For first law of thermodynamics
dU = dq – dw
But dw = P dV
? dU = dq – P dV ....(iii)
At constant volume
dU = dqv
? Heat capacity at constant volume Cv is given by
dq v § wU ·
Cv = dT ¨ wT ¸
© ¹v
§ wU ·
or Cv = ¨ ¸ .....(iv)
© wT ¹ v
It may be defined as the rate of change of internal energy with temperature at constant volume.
Heat Capacity at Constant Pressure(Cp) :
When pressure is maintained constant, equation (h) takes the form
Gq v
CP = .....(v)
dT
From first law of thermodynamics
At constant pressure
Gqp = (dU + PdV) = dH
['H = U + PV At constant P, dH = dU + PdV]
? Gqp = dH ....(vi)
Heat capacity at constant pressure Cp is given by
Gd p § wH ·
Cp =
dT ¨ wT ¸
© ¹P
§ wH ·
or Cp = ¨ ¸ ....(vii)
© wT ¹ P
from the eq. (vii) and (iv)
15
From equation (vii) Unit From equation (iv)

(h) 'H = CpdT JK–1 'U = CVdT
[Here CP is heat capacity at constant P] [Here CV is heat capacity at constant V]
(ii) For n moles 'H = nCPdT J mol–1K–1 'U=nCVdT
[Here CP is molar heat capacity at constant P] [Here CV is molar heat capacity at constant V]
(iii) For m gram 'H = mCPdT J g–1 K–1 'U = mCVdT
[Here CP is gram specific heat [Here CV is gram specific heat
(specific heatcapacity) at constant P] (specific heatcapacity) at constant V]
It is the rate of change of enthalpy with temperature at constant pressure.

Hence heat capacity of a system at constant volume Cv is equal to the increase in internal energy of the system perdegree
rise of temperature at constant volume. Similarly heat capacity at constant pressure Cp is numerically equally to the
increase in enthalpy of the system per degree rise of temperature.
For one mole of gas Cp – Cv = R Mayer’s formula, CP / CV = J, J = Poisson’s ratio
For ‘n’ moles of gas Cp – Cv = nR
Molar heat capacity (Cm) :

Amount of heat required to raise the temperature of 1 moles of substance by 1°C or 1 K is called as molar heat capacity.
Heat capacity C
Molar heat capacity = Cm
mole of substance n
Units :- Jmol–1 K–1, cal mol–1 K–1, J mol–1 °C–1, cal mol–1 °C–1
Molar heat capacity is an intensive property.
Specific heat capacity (c) : Amount of heat required to raise the temperature of 1 gram of substance of 1°C or 1K is called
as specific heat capacity.
Cm
c
molecular weight
Units :- Jg–1 K–1, cal g–1 K–1, J g–1 °C–1, cal g–1 °C–1
Specific heat capacity is an intensive property.
Degree of Freedom and Equipartition Principle

Degree of Freedom is defined as the total number of modes on which a molecule of an ideal gas exchange energy during
collisions. If a molecule contains only one atom (as in a monatomic gas), it has three degrees of freedom corresponding
to translational motion in the three independent spatial directions X, Y and Z.
Degree of freedom
Translational Rotational Vibrational

Type Molecule trans (ft) rot (fr) vib (fv) Total (3 N )
Monoatomic He 3 0 0 3
Diatomic N2 3 2 1 6
Triatomic linear CO2 3 2 4 9
non-linear H2 O 3 3 3 9
vibrational degree of freedom can be calculated by the following method

fv = 3N – (ft + fr)
16
WORK DONE IN DIFFERENT PROCESS :

WORK
PV work Non-PV work

(change in volume is essential) (change in volume is not essential)
Irreversible Reversible
V
w= –Pext V w= –³VPdV
2
Pext = constant
1
Pext = variable
Pext = P2,(g) Pext P(g)
(H) ISOTHERMAL PROCESS
Reversible Isothermal Process :
If the gas is expanded from initial volume V1 to final volume V2 by gradually changing external pressure infinite steps,
process is called reversible isothermal process.
During reversible process :
Pext = Pint ± dP
nRT
Pext = Pint = for an ideal gas
V
nRT
because Pint = Pideal =
V
dwrev, isothermal = – PdV
nRT
³ dw V
–³dV
Work done
§V ·
w nRT ln ¨ 2 ¸
© V1 ¹
§V ·
or, w 2.303nRT log10 ¨ 2 ¸
© V1 ¹
1
according to Boyle’s law at constant temperature P v or PV = constant
V
V2 P1
? P1V1 = P2V2
V1 P2
17
§P ·
W = –2.303nRTlog ¨ 1 ¸
© P2 ¹
Irreversible Isothermal Expansion : If external pressure over the piston is abruptly changed from the equilibrium
value, the mechanical equilibrium of system is distured and piston rushes out :
This type of P.V. work is irreversible P.V. work.

' Pext remains constant throughout the process, work done is calculated by W irr = – Pext . 'V
(II) ADIABATIC PROCESS
In thermodynamics, an adiabatic process is one that occurs without transfer of heat or matter between a
thermodynamic system and its surroundings. In an adiabatic process, energy is transferred only as work.
Pressure
Work done volume

Reversible Adiabatic Process : In an adiabatic process, no loss or gain of heat takes place i.e., dq = 0.
From first law, we have,
dq = dU + dw
Since dq = 0
? dU = –dw
For an ideal gas,
dU = Cv dT
? Cv dT = – dw = – pdV
or, CvdT = – (nRT/V)dV
or, CvdT/T + nR dV/V = 0
Intergrating the above equation between T1 and T2 and V1 and V2, the initial and final temperature and volumes, we
have,
T2 v2
wT wV
³
T1
Cv
T
nR ³
v1
V
0
T2 V2
or Cv ln T nR ln V 0
1 1
18
Cv
T V V2 § T · nR
C v ln 2 nR ln 2 ln ln ¨ 2 ¸
T1 V1 V1 © T1 ¹
1
V § T · J 1 nR
ln 2 ln ¨ 2 ¸ ('Cv = )
V1 © T1 ¹ J 1
1 1
V2 § T2 · J 1 § T1 · J 1
¨ ¸ ¨ ¸
V1 © T1 ¹ © T2 ¹
J 1
§ V2 · § T1 ·
¨ ¸ ¨ ¸ .......(1)
© V1 ¹ © T2 ¹
or T1V1J–1 = T2V2J–1
T. VJ–1 = constant
For an ideal gas,
P1 V1 P2 V2
T1 T2
T1 P1 V1
or T2 P2 V2 .....(2)
? from equation (1) & (2) we have

P1V1J = P2V2J= constant
In general, for a reversible adiabatic expansion
P. VJ= constant Applicable only on a
TVJ –1= constant reversible adiabatic process
TP1– J/J = constant
' q=0
W = 'U = nCv (T2 – T1)
(T2 T1 )
nR
J 1
nRT2 nRT1
J 1
P2 V2 P1V 1
J 1
Irreversible Adiabatic Process : Suppose an ideal gas is confined in a adiabatic container fitted with friction less
piston. If the thermodynamic equilibrium of system is disturbed by changing external pressure suddenly by finite
value and let the system come to equilibrium the process is irreversible adiabatic process. The work done (w) is
given by
'U = w = – Pext (Vf – Vi)
'U = nCV (Tf – Ti)
nCV (Tf – Ti) = – Pext (Vf – Vi)
nCV (Tf – Ti) = – Pext § nRTf – nRTi ·

¨ P Pi ¸¹
© f
19
First we have to calculate the final temperature (Tf) from this equation.
Now w = 'U = nCV (T2 – T1)
ª Pf Vf – Pi Vi º
w =« »
¬ γ –1 ¼
Ex. Consider the following processes that can be done on an ideal gas: constant volume, 'V = 0; constant pressure,
'P = 0; and constant temperature, 'T = 0.
(a) For which process does W = 0?
(b) For which process does Q = 0?
(c) For which of these process does W + Q = 0?
(d) For which of these process does 'Eint = Q?
(e) For which of these process does 'Eint = W?
(A) 'V = 0 (B) 'P = 0 (C) 'T = 0 (D) None of these
Sol. (A) The correct option is (A) 'V = 0.
The change in work done 'W is defined as,
'W = P'V
Therefore W = 0 for the process where 'V = 0. From the above observation we conclude that, option (A) is
correct.
(B) The correct option is (D) None of these.
In adiabatic process the exchange of heat with surrounding is zero (Q=0). In this process, the change of
volume, pressure and temperature occurs. Therefore option (D) is correct.
(C) The correct option is (C) 'T = 0.

For a thermodynamic system, in which internal energy is the only type of energy the system may have,
the law of conservation of energy may be expressed as,
Q + W = 'Eint
Were Q is the energy transferred (as heat) between the system and its environment, W is the work done
on or by the system and 'Eint is the change in the internal energy of the system.
As W + Q = 0, it signifies that 'Eint = 0 and it is possible only when 'T = 0. Therefor option (C) is correct.
(D) The correct option is (A) 'V = 0.
Q + W = 'Eint
Here Q is the energy transferred (as heat) between the system and its environment, W is the work done
As 'Eint = Q, it signifies that W=0.
The change in work done 'W is defined as,
'W = P'V
Therefore W = 0 for the process where 'V = 0. From the above observation we conclude that, option (A)
is correct.
(E) The correct option is (D) None of these.
Q + W = 'Eint
Here Q is the energy transferred (as heat) between the system and its environment, W is the work done
As 'Eint = W, it signifies that Q=0.
In adiabatic process the exchange of heat with surrounding is zero (Q=0). In this process, the change of
volume, pressure and temperature occurs. Therefore option (D) is correct.
20
Comparison of Isothermal and Adiabatic Process :
Starting from same state, if system is allowed to expand to same final pressure,
|wrev, isothermal|>|wrev,adiabatic|.
In reversible isothermal process, heat is entering from surrounding, while in adiabatic process, work is done on the
expansion of internal energy of system.
Starting from same initial state, if system is compressed to same final pressure, wrev,adia > wrev,iso. During adiabatic
compression, the work done is getting stored in the system, and temperature of system increses, the gas become
less and less compressible, and greater work is required to compress the system.
SPONTANEOUS PROCESS :
The process which has a natural tendency to occur in a particular direction either of its own or after proper initiation
under the given set of conditions.
All natural processes are ir-reversible and spontaneous processes. The natural processes take palce of their own in one
direction only.
NON SPONTANEOUS REACTION :
The process which does not occur of its own in a particular direcion i.e. a process which does not have a natural
tendency to occur in a particular direction either of its own or after initiation is called as non-spontaneous process.
Non-spontaneous process may be made to occur when energy from some external source is supplied continuously
throughout the process.
Example of Natural Processes
(h) Water flowing down hill
(ii) Heat flowing from hot body towards cold body on it's own
(iii) mixing of two gases.
(iv) Rusting of iron
(v) Evaporation of water at room temperature.
(vi) Formation of NH3(g) from N2(g) and H2(g) gas in a closed container.
(vii) Expansion of ideal gas in vacuum
(viii)Burning of coal in O2
Every natural process leads to production of disorder. (During irreversible process system moves from ordered state
to disordered state).
ENTROPY (S)
(h) It is the measure of degree of randomness of a system. More random is the system, higher will be its entropy.
The thermodynamic quantity, which is used to measure degree of randomness or disorderness of the system is
called as entroy.
(ii) The ratio of heat absorbed by the system in isothermal and reversible manner to the temperature at which heat is
absorbed is equals to the change in entropy.
qrev
T
Where qrew = heat absorbed by the system in a reversible manner at the temperature T
Unit : JK–1 or CalK–1
(iii) 'S = Sfinal – Sinital
If Sfinal > Sinitial : Then 'S = positive
If Sfinal < Sinitial : Then 'S = negative
(iv) Entropy is an extensive property and state function.
(v) Entropy change in a chemical reaction 'S = 6Sproduct – 6Sreactant
z Entropy Calculation in Process Involving Ideal Gases.
From First law
dq = dU + PdV
21
dq rev dU PdV
= +
T T T
But for ideal gas
dU nCV dT
= {'dU = nCVdT}
T T
nCV dT nR
dSsys = + dV
T V
Integration gives
T2 § V2 ·
'S = nCV ln T + nR ln ¨ V ¸
1 © 1¹
For isothermal process
V2
'S = nR ln
V1
For adiabatic process
V1 = V 2
T2
'S nC V ln
T1
For isochoric process
T2
'S = nCV ln
T1
For isobaric process
T2
'S = nCp ln
T1
Factors affecting entropy of system
(a) If 'ng > then 'S > 0
If 'Ng < 0 then 'S < 0
(b) Physical state : Ssolid < Sliquid < Sgas
(c) On increasing gaseous moles entropy increases.
(d) On increasing temperature, S will increase.
Ex. Fe(s) o Fe(s) ; 'S = positive
300 K 400 K
(e) On decreasing pressure, S increases.
Ex. N2(g) o N2 (g): 'S = Positive
5atm 2 atm
(f) Mixture : Solid + solid
liquid + liquid S
gas + gas
Examples of entropy change

(h) Entropy of graphite > Entropy of diamond.
(ii) In rusting of iron entropy increases.
(iii) NH4Cl(s) + aq o NH+4(aq) + Cl–(aq)
22
In this process NH+4 and Cl– ions are free to move in solution where as they are not free to move in solid NH4Cl.
Hence 'S is positive for this type of dissolution process.
(iv) On addition of HCl in the aqueous solution of Ag+ ions entropy decreases due to precipitation of AgCl.
(v) On boiling of egg: Denaturation of proteins occur. Thus entropy increases.
(vi) Stretching of rubber : During streching of rubber band its long flexible macromolecules get uncoiled. The uncoiled
form has more specific geometry and more ordered arrangement.
Entropy Change in Phase Transition
(H) FUSION :When solid ice is heated below 273 K at external pressure of 1 atm it's temperature slowly rises. At
273 K however. its start melting into liquid without increase in temperature. The process is reversible phase
transition from solid to liquid represented as :
ZZZ
H2O (s) YZZ XZ H2O(A)
Since process is reversible (you can safely assume that phase transition at constant temperature and pressure
are reversible phase transitions).
ΔH fusion
'Sfustion = entropy of fusion at Melting point.
Tf
(II) VAPOURISATION : From you day to day experience you know that under atmospheric pressure temperature
of H2O (A) can not exceed 373 K. Since at 373 K liquid H2O undergo phase transition.
ZZZ
X
H2O(A) YZZZ H2O(g)
'H vap
'Svap
Tb
(III) SUBLIMATION : It is the process in which solid directly changes into gaseous state
ZZZ
X
X(s) YZZZ X(g)
'H sub
'Ssub
Tsub
ZZZ
X
(IV) PHASE TRANSITION : Allotrope1 YZZZ Allotrope2
'H transition
'Stransition
Ttransition
(V) TOTAL ENTROPY CHANGE IN REVERSIBLE PROCESS :

In reversible process, at every step system and surroundings remain in thermal equilibrium with each other.
Let a system, releases q heat to the surroundings at temperature T.
q q
'Ssystem ; 'Ssurrounding
T T
' 'Stotal = 'Ssystem + 'Ssurroundings
q q
'Stotal 'Stotal = 0
T T
(VI) TOTAL ENTROPY CHANGE IN IRREVERSIBLE PROCESS :
Let a system is at high temperature T1 and surroundings are at low temperature T2.
Let q amount of heat is released by the system.
q q
'Ssystem 'Ssurroundings
T1 , T2
23
q q
' 'Stotal = 'Ssystem + 'Ssurroundings = T T
1 2
? 'Stotal = +ve (' T1 > T2)

Total entropy change for irreversible spontaneous process is always greater than zero.
KEY POINTS
Boiling point at 1 atm pressure is called normal boiling point. There can be infinite boiling points of liquid depending
upon external pressure we applying on boiling vessel.
Entropy and Criteria of Spontanity of Chemical Process

The entropy change of chemical reaction together with entropy change of surrounding determine spontanity of a
chemical process under given set of condition.
'ST > 0 (+ve) the reaction will be Spontaneous.
'ST < 0 (-ve) the reaction will be Non-Spontaneous.
'ST = 0 Equilibrium
Ex. (a) One mole of an idal gas expands isothermally and reversibly at 25ºC from a volume of 10 litres to a volume of 20
litres.
(h) What is the change in entropy of the gas?
(ii) How much work is done by the gas?
(iii) What is q (surroundings)?
(iv) What is the change in the entropy of the surroundings?
(v) What is the change in the entropy of the system plus the surroundings?
(b) Also answer the questions opening a stopcock and allowing the gas to rush into an evacuated bulb of 10 L volume.
V2 20
Sol. (a) (h) 'S = 2.303 nR log = 2.303 ×1 × 8.314 × log = 5.76 J/K.
V1 10
V2
(ii) Wrev = –2.303nRT log
V1
20
= –2.303 × 1 × 8.314 × 298 × log = –1781 J.
10
(iii)For isothermal process, 'E = 0 and heat is absorbed by the gas,
qrev = 'E – W = 0 –(–1718) = 1718 J.
? qrev = 1718 J. (? process is reversible)
1718
(iv) 'Ssurr= – = – 5.76 J/K.
298
As entropy of the system increases by 5.76 J, the entropy of the surroundings decreases by 5.76J, since the
process is carried out reversibly.
(v) 'Ssys + 'Ssurr = 0..... for reversible process
(b) (h) 'S = 5.76 J/K, which is the same as above because S is a state function
(ii) W=0 ( ' pext = 0)
(iii) No heat is exchanged with the surroundings.
(iv) 'Ssurr = 0.
(v) The entropy of the system plus surroundings increases by 5.76 J/K, as we expect entropy to increase in an
irreversible process.
24
Ex. Will 'S be positive or negative in the following processes ? Discuss qualitatively.
(a) H2O(s) o H2O(A)
(b) H2O(A) o H2O(g)
(c) H2(g) + Cl2(g) o 2HCl(g)
1 3
(d) N2(g) + H2(g) o NH3(g)
2 2
(e) 2H2(g) + N2(g) o N2H4(A)
(f) Cl2(g) o 2Cl(g)
Sol. As we have discussed that the entropy of reaction is more if there is a change in value of 'Qg (the change in the
stoichiometric number of gaseous species), since the entropy of gases is much larger than the entropy of the
condensed phases.
? for process (a) 'S is +ve
for process (b) 'S is +ve
for process (c) 'S is zero
for process (d) 'S is negative
for process (e) 'S is negative
for process (f) 'S is positive
Ex. Sulphur exists in more than one solid form. The stable form. The stable form at room temperatrure is rhombic sulphur.
But above room temperature the following reaction occurs :
s (rhombic) os (mono clinic)
Thermodynamic measurements reveal that at 101.325 kPa and 298 K,
'rH = 276.144 J mol–1 and 'rG = 75.312 J mol–1
(a) Compute 'rs at 298 K
(b) Assume that 'rH and 'rs do not vary significantly with temperature, compute Teq, the temperature at which
rhombic and monoclinic sulphur exist in equilibrium with each other.
Sol. (a) Since
'rG = 'rH – T'rS,
Therefore
Δr H – ΔrG 276.144 J mol –1 – 75.312 J mol –1

'rS = =
T 298 K
= 0.674 J K–1 mol–1
(b) When the rhombic sulphur is in equilibrium with monoclinic sulphur, we would have
'rG = 0 = 'rH – Teq 'rS
Δ r H 276.144 J mol –1
Thus Teq = =
Δ rS 0.674 J mol –1
= 409.7 K
Ex. At 1 atm and 27°C, will the vaporisation of liquid water be spontaneous ? Given 'H = 9710 cal and
's = 26 eu.
Sol. H2O(A) = H2O(g) (P = 1 atm)
'G = 'H – T'S = 9710 – 26 × 300 = +1910 cal
since 'G is positive, at 1 atm, vaporisation is not possible. Rather the reverse process of condensation will occur.
The temperature at which the liquid and vapour will be equiv. can be obtained, by putting 'G = 0, i.e
'G = 9710 – 26T = 0
T = 373.4 °C
This indeed is the boiling point of water at 1 atm.
25
Ex. Gases 'G°f (Cal/mole)
CO –32.80
H2O –54.69
CO2 –94.26
H2 0
Estimate the standard free energy change in the chemical reaction
CO + H2O = CO2 + H2
Sol. Using the necessary data from the table
CO H2O CO2 H2
'G° – 32.8 –54.69 –94.26 0 kcal
?'G° = –94.26 + 0 – (–32.8) – (–54.69)
= –6.8 kcal/mol
SECOND LAW OF THERMODYNAMICS
(h) It states about the direction of flow of heat.
(ii) All natural processes in universe are ir-reversible process or natural processes are spontaneous process.
(iii) Due to spontaneous process entropy of universe is increasing continuously i.e. entropy of an isolated system
increases.
('S)T = + ve or ('S)T > 0 or ('S)system + ('S)surr. > 0
THIRD LAW OF THERMODYNAMICS
Third law of thermodynamics helps in determining absolute entropy of substances. It is based on an assumption
that entropy of every perfectly crystalline substance is zero at zero
Kelvin. This is justified because , at absolute zero every substance is in state of lowest energy and position
of every atom or molecule is defined in solid. Hence at T=0 S(T=0)=0 Third law
If we have sufficient heat capacity data (and the data on phase changes) we could write
r Cp
S (T) = S(T = 0) + ³
0 T
dT ...........(h)
Exceptions :
(h) NO, N2O (ii) CO, CO2 (iii) Mixture of isotopes (iv) Ice
GIBB’S ENERGY (G OR F)
• Gibb’s energy is difined at constant temperature and pressure to predict spontaneity of a process.
• Gibb’s energy is a thermodynamic quantity which is used to measure the capacity of system to do useful
work or Gibb’s energy is that part of the total energy of system which can be converted into useful work.
• The term Gibbs energy was introduced to explain criteria of spontaneity in terms of system.
Since; energy = useful work + randomness energy
H= G + TS
G = H – TS ...(h)
So the function that takes both enthalpy and entropy of system into account is called Gibbs energy.
• Gibbs energy is an extensive property and state function.
• Absolute value of G can’t be measured but change can be measured, So we discuss ('G)
'G = Gfinal – Ginitial
From eq. (h) 'G = 'H – T'S
Where 'G = Change in Gibb’s energy
'H = Change in enthalpy
'S = Change in entropy
26
Relation in between 'G of system and 'Stotal or Gibb’s energy change and spontaneity :
' 'Stotal = DSsystem + 'Ssurroundings
Let system releases heat of constant temperature T and pressure P.
? q = qP = 'H
qsystem = –qsurroundings
'Hsystem = –'Hsurroundings
'Hsurr.
'Ssurr.
T
'H sys.
'Ssurr.
T
§ 'H sys. ·
' 'Stotal 'Ssys. ¨ ¸
© T ¹
T'Stotal = T'Ssys. – 'Hsys.
T'Stotal = –('Hsys. – T'Ssys.)
T'Stotal = –'Gsys.
or 'Gsys. = –T'Stotal
(h) If, 'Stotal = +ve 'Gsystem = –ve spontaneous process
(ii) If, 'Stotal = –ve 'Gsystem = +ve non spontaneous process
(iii) If, 'Stotal = 0 'Gsystem = 0 process is at equilibrium.
'rH4 ' rS 4 'rG4 Description

– + – Reaction spontaneous at all temperature
– – – (at low T) Reaction spontaneous at low temperature
– – + (at high T) Reaction nonspontaneous at high temperature
+ + + (at low T) Reaction nonspontaneous at low temperature
+ + – (at high T) Reaction spontaneous at high temperature
+ – + (at all T) Reaction nonspontaneous at all temperatures.
Relationship between standard Gibb’s energy change ('G°) and Equilibrium constant (K) :-
For a reaction m1A + m2B U n1C + n2D
'G = 'G° + RT An Q
At equilibrium – 'G = 0 and Q = K
0 = 'G° + RT An K
? 'G° = –RT AnK .......(h)
or 'G° = –2.303RT log10K .......(ii)
from equation (h)
'Gq
log K
RT
? K = e–'G°/RT .....(iii)
GIBBS FREE ENERGY CHANGE AT CONSTANT TEMPERATURE :

In order to derive an equation which will enable us to calculate the Gibbs free energy change of an isothermal process
but with varying pressure, we may conveniently start with the equation,
G = E + PV – TS
27
Differentiating the above equation, we get

dG = dE + PdV + VdP – TdS – SdT
According to first law of thermodynamics,
dQ = dE + PdV
? dG = dQ + VdP – TdS – SdT
dQ
Further since dS , we can replace dQ by TdS.
T
? dG = VdP – SdT
At constant temperature, dT = 0
? dG = VdP
§ dG ·
or ¨ dP ¸ = V
© ¹r
Thus Gibb's function of every substance increases on increasing pressure , but this increase is maximum
for gases , compared to solids or liquids since gases have maximum molar volume. On intergrating equation
dG = VdP for very minute changes from state 1 to 2, we have
2
'G = G2 – G1 = ³
1
VdP
In case of one mole of a perfect gas,

RT
V
P
2 dP P2
? 'G = RT ³
1 P
= RT ln P
1
For n moles of a perfect gas, the free energy change is

P2
'G = nRT ln
P1
GIBBS FREE ENERGY CHANGE AT CONSTANT PRESSURE :
From equation which is
dG = VdP – SdT (Only for pure substances)
when pressure is constant, dP = 0
? dG = – SdT
§ dG ·
or ¨ dT ¸ = –S
© ¹p
thus Gibb's function of every substance decreases with temperature, but this decrease is maximum for gases
since they have maximum state of disorder. Hence on increasing temperature, gas phase gain maximum stability
compared to solid or liquid phase.
GIBBS FUNCTION AND NON PV WORK :
Decrease in Gibb's function at constant temperature and pressure in a process gives an estimate or measure
of maximum non-PV work which can be obtained from system in reversible, manner.
The example of non-PV work is electrical work done by chemical battery.
Expansion of soap bubble at for a closed system capable of doing non-PV work apart from PV work first law
can be written as
dU = dq – PdV = dwnon–PV
28
– dwnon–PV = non-PV work done by the system.
dG = d (H – TS)
= dH – TdS – SdT
dG = dU + PdV + VdP – TdS – SdT
dG = dq – PdV – wnon,PV + PdV + VdP – TdS – SdT
for a reversible change at cont. T and P
dG = dqrev. – dwnon + VdP – TdS – SdT
since dqrev = TdS
–(dG)T,P = dwnon-PV
Non-PV work is work done due to chemical energy transformation or due to composition change and decrease
in Gibb's function in a isothermal and isobaric process provide a measure of chemical energy stored in bonds
and intermolecular interaction energy of molecules.
Ex. Ka for CH3COOH at 25ºC is 1.754 × 10-5 . At 50ºC, Ka is 1.633 × 10-5 What are 'Hº and 'Sº for the ionisation of
CH3COOH?
Sol. ('Gº)298 = – 2.303RT log K = – 2.303 ×8.314 × 298 ×log (1.754 ×10-5)
= 27194 J.
('Gº)323 = 2.303 × 8.314 × 323 × log ( 1.633 × 10-5)
= 29605 J.
'Gº = 'Hº – T'Sº
27194 = 'Hº – 298 'Sº
29605 = 'Hº – 323 'Sº
? 'Hº = – 1.55 kJ/mol
'Sº = – 96.44J/mol.K
29
A thermochemical equation, represents both the material change and the energy. While writing a thermochemical
equation, the heat evolved in case of exothermic reaction, or the heat absorbed in case of endothermic reaction,
is indicated on the product side of the balanced chemical equation. For example,
1
(i) H2(g) + O 2 (g) o H2O(A) 'H = –285.91 kJ
2
(ii) C(graphite) + 2S (rhombic) o CS2 'H = +91.96 kJ
The most stable physical state of the reacting species and the products is also indicated in brackets. Thus, a
thermochemical equation gives complete information about the material change and the associated heat change.
It is clear that the first reaction is exothermic and the second one endothermic.
EXOTHERMIC REACTION : The reaction which evolves heat is called exothermic reaction.
'H = –ve
'H = HP – HR
'H = –ve i.e. (HP < HR)
Examples of exothermic reactions :

(I) Combustion reactions
(II) Neutralisation reactons
(III) Respiration reaction eg. C6H12O6 + 6O2 o 6CO2 + 6H2O
endo
(IV) Formation reaction
exo (generally)
Exceptions of formation reaction :

C + S2 o CS2
1 3
N 2 Cl2 o NCl3
2 2
N2 + O2 NO/N2O/NO2/N2O4
O2 + F2 OF2/O2F2
(V) Coal is burnt simply for the large amount of energy available during its combustion :
(VI) When water is added to quick lime (CaO) for preparing whitewash, a considerable amount of heat is produced
during the reaction. The heat produced warms up the water. When we add dilute hydrochloric acid to a
test tube containing granulated zinc, hydrogen gas is evolved. The reaction is accompanied by evolution
of heat.
ENDOTHERMIC REACTION : The reaction which absorb heat is called as endothermic reaction.
'H = +ve
'H = HP – HR = +ve i.e. HP > HR
30
Examples of endothermic reactions.
(I) Dissociation reactions (mostly)
(II) Fusion reactions
(III) Vaporization reactions
(IV) Sublimation reactions
(V) Photosynthesis 6CO2 + 6H2O o C6H12O6 + 6O2, 'H = +ve
(V) When a small quantity of ammonium chloride (NH4Cl) is dissolved in water in a test tube, the tube becomes
colder than before. During this chemical reaction heat is absorbed from the surroundings (test tube).
(VII) When the crystals of sodium thiosulphate (Na2S2O3.5 H2O) commonly called hypo, are dissolved in water,
a cooling effect takes place.
(VIII) One mole of nitrogen reacts with one mole of oxygen to form two moles of nitric oxide. 180.5kJ of heat
is absorbed at constant temperature and the reaction may be expressed as:
or N2(g) + O2(g) o 2NO(g)
'Hr]
HEAT OF REACTION OR STANDARD ENTHALPY OF REACTION ['
Enthalpy of reaction is defined as the quantity of heat evolved or absorbed. When molar quantities of substances
react in amounts represented by chemical equation at constant pressure and temperature, the substances being
in their standard states.
For example : H2(g) + Cl2(g) o 2HCl(g) 'H = –183.92 kJ
Thus, when one mole of gaseous hydrogen reacts with one mole of gaseous chlorine, 183.92 kJ of heat is evolved.
This is the heat of the reaction for the above chemical reaction.
'Hr = 6Hproducts – 6Hreactants
Factors Affecting Heat or Enthalpy Change : The enthalpy change of reaction ('H) depends upon the following factors
(i) Physical state of the reactants and the products : The 'H of a reaction depends upon the physical
states of reactants and products. For example, when hydrogen and oxygen gases combine to give liquid
water, the heat of reaction is different than when they combine to form gaseous water.
H2(g) + O2(g) o H2O(A) 'H = –285.83 kJ
H2(g) + O2(g) o H2O(g) 'H = –241.82 kJ
(ii) Quantities of reactants : The amount of heat evolved or absorbed depends upon the amount of reactants.
For example, the heat of combustion of 2 moles of carbon is double than heat of combustion of 1 mole
of carbon.
(iii) Allotropic modification : The amount of heat evolved or absorbed for different forms of the same substance
are different. For example,
C(diamond) +O2(g) o CO2(g) 'H = –395.41 kJ
C(graphite) +O2(g) o CO2(g) 'H = –393.51 kJ
(iv) Temperature : Effect of temperature on heat of reaction is given by Kirchoff equation
'H T 'H T
(i) at constant pressure : 2 1
'C Pm
T2 T1
31
'CPm = 6(CPm)P – 6(CPm)R
'H T = Heat of reaction at T1 temperature

1
'H T = Heat of reaction at T2 temperature

2
'E T 'E T
2 1
(ii) at constant volume :
T2 T1
'CVm = 6(CVm)P – 6(CVm)R
(v) Pressure or volume: The heat of reaction depends upon the conditions of constant pressure or volume.
'H = 'U+ P'V
'H may be equal, greater than or less than 'U.
Thus, a reaction, which is exothermic in one direction will be endothermic in reverse direction.
Ex. Why does heat get released/absorbed during chemical reactions?

Sol. because the reactants have a fixed enthalpy content before the reaction and when these are converted into the
products which have a different enthalpy content. So, heat gets released or absorbed. Even if temperature of
reactions remains constant yet due to change in bonding energies 'E z 0.
If Hproducts > Hreactants
Reaction should be endothermic as we have to give extra heat to reactants to get these converted into products
and if Hproducts < Hreactants
Reaction will be exothermic as extra heat content of reactants will be released during the reaction.
Enthalpy change of a reaction : 'Hreaction = Hproducts – Hreactants
'H°reactions = H°products – H°reactants
= positive – endothermic
= negative – exothermic
HESS'S LAW OF CONSTANT HEAT SUMMATION

This law put forth by Hess states that "the resultant enthalpy change in a reaction is the same whether it occurs
in one or several steps".
We illustrate this law by considering a example :
(i) The formation of urea from carbon, oxygen and ammonia may take place directly in one step or in two steps
as shown below :
(i) One step reaction (ii) Two step reaction
32
The enthalpy change when the reaction takes place in two steps is given by
'H1 + 'H2 = –393.129 – 812.801 = –1205.93 kJ
This is seen to be equal to 'H, the change involved in one step reaction.
Types of Heat of Reaction :

(I) 'Hf or 'fH)
Enthalpy of Formation ('
The heat evolved or absorbed when 1 mole of a substance is formed from its constituent elements under constant
pressure and temperature conditions is called enthalpy of formation. It is denoted by 'Hf .
For example, heat of formation of carbon dioxide and methane may be expressed as :
C(graphite) + O2 o CO2(g)
C(graphite) + 2H2 o CH4(g)
These equations should always be written for one mole as per the definition of the substance to be formed. If for
balancing, we require the coefficient 2, 3.... etc., in the equation then 'Hf values should also be multiplied by the
same number as discussed earlier.
Application of 'Hf :
Calculation of 'H of any general reaction.
Let us considered a general reaction aA + bB o cC + dD
DHreaction = 6'Hf(products) – 6'Hf(reactant) = [c'Hf(C) + d'Hf(D)] – [a'Hf(A) + b'Hf(B)]
Ex. Calculate the standard heat of formation of carbon disulphide (A). Given that the standard heats of combustion of
carbon (s) sulphur (s) and carbon disulphide (A) are 393.3, –293.72 and –1108.76kJ mol–1 respectively.
Sol. The given data can be written in thermochemical equation form as :
C(s) + O2(g) oCO2(g) 'H = –393.5 kJ ......(i)
S(s) + O2(g) oSO2(g) 'H = –293.72 kJ ......(ii)
CS2(A) + 3O2(g) oCO2(g) + SO2 (g) 'H = –1108.76 kJ ......(iii)
The required equation is:
C(s) + 2S(g) oCS2(A) 'H = ?
Multiplying equation (ii) by 2 and adding to equation (i) we get,
2S(s) + 2O2(g) o2SO2(g) 'H = –587.44 kJ
C(s) + O2(g) oCO2(g) 'H = –393.5 kJ
2S(s) + C(s) + O2(g) o2SO2(g) + CO2 (g) 'H = –980.74 kJ

Subtracting equation (iii) from the above equation we have,
2S(s) + C(s) + O2(g) o2SO2(g) + CO2(g) 'H = –980.74 kJ
CS2(A) + 3O2(g) oCO2(g) + SO2(g) 'H = –1108.76 kJ
C(s) + 2S(g) oCS2(A) 'H = –128.02 kJ
33
Ex. Calculate heat of the following reaction at constant pressure,
F2O(g) + H2O(g) o O2 (g) + 2HF(g)
The heats of formation of F2O (g), H2O(g) and HF (g) are 5.5 kcal, –57kcal and –64 kcal respectively.
1
Sol. Given that (i) F2 (g) + O (g) o F2O (g); 'H = 5.5 kcal
2 2
1
(ii) H2 (g) + O (g) o H2O (g); 'H = – 57 kcal
2 2
1 1
(iii) H (g) + F2 (g) o HF (g); 'H = – 64 kcal
2 2 2
F2O and H2O in eqns. (i) and (ii) and in the eqn. given in the problem are on the opposite sides, while HF in eqn. (iii)
and in the eqn. given in the problem is on the same sides.
Thus applying, [ – Eqn. (i) –Eqn. (ii) + 2 × Eqn. (iii) ], we get
1 1
–F2 (g) – O (g) – H2 (g) – O2(g) + H2 + F2 (g) o –F2O (g) – H2O(g) + 2HF(g);
2 2 2
'H = – 5.5 – (– 57) + 2 × ( – 64)

or F2O (g) + H2O (g) o O2 (g) + 2HF(g); 'H = – 76.5 kcal.
Ex. The 'fH° (N2O5, g) in kJ/mol on the bases of the following data is :
2NO(g) + O2 (g) o 2NO2 (g) 'fH° = –114 kJ/mol
4NO2 (g) + O2(g) o 2N2O5 (g) 'fH° = –102.6 kJ/mol
1 1
Sol. N 2 (g) O 2 (g)
o NO(g) 'fH° = 90.2
2 2
N2(g) + O2(g) o 2NO (g) 'fH° = 90.2 × 2 ...(1)
2NO(g) + O2(g) o 2NO2(g) 'fH° = –114 ...(2)
1 102.6
2NO2(g) + O 2 (g) o N2O5 (g) ' r Hq 51.3 ...(3)
2 2
From Equations (1) + (2) + (3)
5
N2(g) + O 2 (g) o N2O5(g) 'fH° (N2O5, g) = 15.1 kJ/mol
2
(II) Enthalpy of Combustion ('Hcomb)

Enthalpy of combustion of a given compound is defined as follows :
It is the enthalpy change when one mole of this compound combines with the requisite amount of oxygen to
given products in their stable forms.
For example, the standard enthalpy of combustion of methane at 298.15 K is –890.36 kJ mol–1. This implies the
following reaction :
CH4(g) + 2O2(g) o CO2(g) + 2H2O(A) 'H° = – 890.36 kJ mol–1
The standard enthalpy of combustion of methane at 298.15 K may be writen as
'cH°(CH4, g, 298.15 K) = – 890.36 kJ mol–1
34
Application of Enthalpy of Combustion :
Consider a reaction of disproportination of C6H14 into C4H8 and C2H6. The following diagram show how enthalpy
of combustions can be used to estimate entlalpy of reaction.
From the inspection of the above diagram, it is clear that

'Hreaction 'Hcombustion(C6H14) –'Hcombustion (C4H8) –'Hcombustion (C2H6)
Hence 'Hreaction 'Hcombustion(Reactant's) – 'Hcombustion (Products)
Ex. A gas mixture of 4 litres of ethylene and methane on complete combustion at 25ºC produces 6 litres of CO2 . Find out
the amount of heat evolved on burning one litre of the gas mixture. The heats of combustion of ethylene and
methane are – 1464 and –976 kJ mol-1 at 25ºC.
Sol. + O2 o CO2 + H2O
x lit. (4 – x)lit. 6 lit.

(say)
or x moles (4 – x) moles 6 moles
Applying POAC for C atoms,
2 × x + 1 × ( 4 – x ) = 1 × 6 ; x = 2 lit.
Thus, the volume of C2H4 = 2 lit., and volume of CH2 = 2 lit.
? volume of C2H4 in a 1 litre mixture = 2/4 = 0.5 lit.
and volume of CH4 in a 1 litre mixture = 1 –0.5 = 0.5 lit.
Now, thermochemical reactions for C2H4 and CH4 are
C2H4 + 3O2 o 2CO2 + 2H2O; 'H = – 1464 kJ
CH4 + 2O2 o CO2 + 2H2O; 'H = – 976 kJ
As 'H values given are at 25ºC, let us first calculate the volume occupied by one mole of any gas at 25ºC (supposing
pressure as 1atm)
298
Volume per mole at 25ºC = × 22.4 = 24.4 lit.
273
1464
Thus, heat evolved in the combustion of 0.665 lit. of C2H4 = – × 0.5 = – 30 kJ
24.4
976
and heat evolved in the combustion of 0.335 lit.of CH4 = × 0.5 = –20 kJ.
24 .4
? total heat evolved in the combustion of 1 litre of the mixture = –30 + (– 20) = – 50 kJ.
35
Calorific value of a fuel :
Nutritional value of foods, and the usefulness of fuels is determined by the heat (energy) they produce on heating.
The energy released by the combustion of foods or fuels is usually compared in terms of their combustion energy
per gram. It is known as calorific value. It is defined as the amount of heat produced in calories (or joules) when
one gram of a substance (food or fuel) is completely burnt. The calorific value is usually expressed in kcal per
gram or kilojoules per gram (1 kcal = 4.184 kJ).
For example when Methane burns
CH4(g) + 2O2(g) o CO2(g) + 2H2O(A) + 891 kJ energy
therefore calorific value of meathan is 891/16 = 55.6kJ/gm
The fuel are graded according to their calorific value. Greater the calorfic value of a fuel, greater is the prize.
Hydrogen has greatest calorific value.
'H Comb
Calorific value
Molecular weight
unit = K J g–1 or K Cal g–1
KEY POINTS
(i) Heat of combustion reaction is always exothermic
(ii) If conditions are not given then 'Hcomb is considered as 'H°comb.
(iii) H2 has the highest calorific value (150 KJ/gm) but it is not used as domestic or industrial fuel due to some
technical problems.
(III) Bond Energy / Bond dissociation energy

The required amount of energy to dissociate one mole gaseous bond into separate gaseous atoms is called as
bond dissociation energy.
Example : 1H – H(g) o 2H(g) 'HH – H 9
1Cl – Cl(g) o 2Cl(g) 'HCl – Cl 9
1H – Cl(g) o H(g) + Cl(g) 'HH – Cl 9
1H – Cl(g) o H +
(g)
+ Cl –
(g)
'HH – Cl ±
1 1
1H – Cl(g) o H 2(g) Cl 2(g) , 'HH – Cl ±
2 2
1H2O(g) o 2H(g) + O(g) 'H H2 O ±
(IV) Enthalpy of Solution

When a solute is dissolved in a solvent a solution is formed. During dissolution of a solute in any solvent,
a certain amount of heat is either absorbed or evolved. Such heat changes under constant pressure conditions
are known as the enthalpy of solution. ‘The change in enthalpy when one mole of a solute is dissolved in a
specified quantity of a solvent at a given temperature is called enthalpy of solution’.To avoid the amount of
solvent, heat of solution is usually defined for an infinite dilute solution. Thus, heat of solution at infinite dilution
is the heat change when one mole of a substance is dissolved in such a large quantity of solvent so that further
dilution does not give any further heat change.
36
Here ‘aq’ represents aqueous meaning a large excess of water. For substances, which dissolve with the absorption
of heat (endothermic), the enthalpy of solution is positive while for the substances which dissolve by liberating
heat (exothermic), the enthalpy of solution is negative. For example, when KCl is dissolved in water, heat is
absorbed. Thus, the enthalpy of solution of KCl is positive. For a 200 times dilution (water : KCl = 200 : 1),
the enthalpy change during the process, So, the enthalpy of solution of KCl at a dilution of 200 is 18.6 kJ mol–1. The
dissolution of CaCl2(s) in water is an exothermic process. So, the enthalpy of solution of calcium chloride (CaCl2)
is negative. At a dilution of 400, the enthalpy change for the reaction, So, the enthalpy of solution of CaCl 2(s)
at a dilution of 400 is –75.3 kJ mol–1.
KCl(s) + 200H2O o KCl(aq) (200H2O) 'H = +18.6kJ mol–1
CaCl2(s) + 400H2O oKCl(aq) (400H2O) 'H = –75.3kJ mol–1
KEY POINTS
Important points to remember about enthalpy of solution :
(i) It is generally negative for anhydrous salts
(ii) It is generally positive for salts which do not have water of hydration like NaCl
(iii) It is generally positive for hydrated salts like CuSO4.5H2O
(iv) If lattice energy|U|is more than |Hydration energy|of gaseous ions, enthalpy of solution is positive.
(v) If lattice energy|U|is less than |Hydration energy|of gaseous ions, enthalpy of solution is negative.
(vi) Note that even when 'Hsolution is positive, salts are freely soluble in water due to favourable Gibb's free energy
change.
(V) Enthalpy of Hydration

This is defined as the heat change (evolved or absorbed) when one mole of the anhydrous salt combines with
the required number of moles of water to form the specific hydrated salt.
CuSO4(s) + 5H2O(A) o CuSO4.5H2O(s) ; 'HHydration = –78.21 kJ mol–1
Hydration is generally exothermic change.
If integral heat of solution of the hydrated and anhydrous salt is known, then heat of hydration can be calculated.
For example
(a) CuSO4(anhydrous) + 800 H2O(A) o CuSO4 (800 H2O) ; 'H = –66.50 kJ
(b) CuSO4.5H2O(s) + 795H2O (A) o CuSO4 (800 H2O) ; 'H = 11.71 kJ
Thus, (a – b) gives
CuSO4(s) + 5H2O(A) o CuSO4.5H2O(s) ; 'HHydration = –78.21 kJ
(VI) Enthalpy of Neutralisation

The reaction in which an acid and a base react to give a salt and water is called neutralization reaction.
Neutralization reactions are exothermic in nature. The heat change when one gram equivalent of an acid is
completely neutralised by a base or vice versa in dilute solution, is called heat of neutralization. Examples of
heat of neutralization are :
Neutralization of HCl with NaOH
HCl(aq) + NaOH(aq) o NaCl(aq) + H2O(A) 'H = –57.1 kJ
37
Neutralization of CH3COOH with NaOH
CH3COOH(aq) + NaOH(aq) o CH3COONa + H2O(A) 'H = –55.9 kJ
It is important to note that the term gram equivalent is used in the definition of heat of neutralization. This is
because neutralization involves 1 mole of H+ ions and 1 mole of OH– ions to form 1mole of water and 57.1 kJ
of heat is liberated.
H+(aq) + OH– oH2O(A) 'H = –57.1kJ
Now, one gram equivalent of various acids on complete dissociation liberates one mole of H + ions. But one
mole of the acid may produce more than one mole of H+ ions in solution depending upon its basicity; for
example 1mol of H2SO4 gives 2 mol of H+ ions and 1mol of H3PO4 gives 3 mol of H+ ions on complete dissociation.
But 1gram equivalent of both (H2SO4 or H3PO4) produces only 1 mol of H+ ions.Thus, it is more appropriate
to use the term gram equivalent in the definition of enthalpy of neutralization.
The average enthalpy of neutralization of any strong acid by a strong base is found to be –57.7. This is because
strong acids and strong bases are completely ionized in aqueous solutions. The aqueous solution of one gram
equivalent of all strong acids contains the same number of H+ ions. Similarly, aqueous solution of one gram equivalent
of all strong bases also contains same number of OH–. The neutralization reactions between strong acids and strong
bases in aqueous solutions involve simply the combination of H+ ions (from an acid) and OH– ions (from a base)
to form unionized water molecules. For example, the reaction between hydrochloric acid and sodium hydroxide.
The neutralization can be represented as :
H+(aq) + Cl–(aq) + Na+(aq) + OH–(aq) o Na+(aq) Cl–(aq) + H2O(A) 'H = –57.1 kJ
Cancelling common ions :
H+(aq) + OH– oH2O(A) 'H = –57.1 kJ
Experimental determination of enthalpy of neutralization :

In this experiment, an aqueous hydrochloric acid solution will be added to an aqueous sodium hydroxide solution.
The neutralization reaction will occur until either H+ or OH– is entirely consumed. The reactant which is consumed
completely is called the limiting reactant.
The molar enthalpy of neutralization is defined as
'Hneut = qneut/n
Where qneut is the heat of neutralization, measured calorimetrically, and n is the moles of the limiting
reactant.
Approach ' Add a known volume of 3.00 M aqueous HCl to a known volume of 1.00 M aqueous
NaOH.
y Observe the temperature of the system before and after the neutralization reaction occurs.
Calculate the change in temperature ('T) for the system.
y Use the temperature change and heat capacities (C) for the calorimeter and aqueous solution to calculate the heat
of neutralization.
y Divide the heat of neutralization by the moles of the limiting reactant to determine the molar enthalpy of neutralization.
C 'T
'Hneut = –
n
The enthalpy of neutralization of weak acid and weak base :
Consider the neutralisation of weak acid HA with weak base BOH.
Where, 'Hionisation (HA) = Enthalpy of ionization of acid HA
'Hionisation (BOH) = Enthalpy of ionization of base BOH
38
'Hneutralisation (H+/OH) = Enthalpy change for the reaction of H+ and OH– to form water.
Thus for weak acid :

'Hneut (BOH/HA) = 'Hion. (HA) + 'Hion (BOH) + 'Hneut (H+ OH–)O
Ex Enthalpy of neutralization of HCl by NaOH is –57.1 kJ/mol and by NH4OH is –51.1 kJ/mol. Calculate the enthalpy of
dissociation of NH4OH.
Sol. Given that, H+(aq) + NH4OH(aq) o NH4+(aq) + H2O(A) 'H = –51.1 kJ/mole
We may consider neutralization in two steps.
(i) Ionization NH4OH(aq) o NH4+(aq) + OH¯(aq) 'H1 = ?
(ii) Neutralization H+(aq) + OH¯(aq) o H2O(A) 'H2 = – 57.1 kJ/mole

Thus, 'H = 'H1 + 'H2
Therefore, 'H1 = 'H – 'H2 = – 51.1 kJ/mol + 57.1 kJ mol–1 = 6.0 kJ/mol
BORN - HABER CYCLE FOR NaCl

This cycle is based on thermochemical changes taking place in the formation of a lattice. This cycle can be used to
determine lattice energy which cannot be directly measured. It is defined as that energy released when one mole of
the ionic compound (lattice) is formed from its isolated ions in the gaseous state under standard condition.
39
nAm+(g) + mBn–(g) o AnBm(s)
'H = – U (lattice energy)
Formation of NaCl(s) lattice involves thus,
HClCl
S+I+ –E–U=q
2
hence, U can be calculated.
here, S = enthalpy of sublimation of Na(s) = 'Hsublimation
I = ionisation of energy of Na(g) = 'Hionization
H = bond energy of Cl2
U = lattice energy
q = enthalpy of formation of NaCl(s) = 'Hformation
If lattice is MgX2 (s) then
S + (I1 + I2) + H – 2E – U = q
where, (I1 + I2) = total ionisation energy to form Mg2+(g).
Ex. Calculate lattice energy for the change,

Li+(g) + Cl– (g) o LiCl(s)
Given that
'Hsubl. of Li = 160.67 kJ mol–1,
'HDissociation of Cl2 = 244.34 kJ mol–1,
'Hionisation of Li(g) = 520.07 kJ mol–1,
'HE.A of Cl(g) = – 365.26 kJ mol–1,
'Hf of LiCl(s) = – 401.66 kJ mol–1.
Sol. Considering the different changes that occur in the formation of solid lithium chloride based on the data given the
lattice energy of the above can be constituted as:
40
1
'H°f = 'Hsubl. + 'HI.E. + 'HDiss. + 'HE.A + 'Hlattice
2
1
or 'Hlattice = 'H°f –'Hsubl. – 'HI.E. – 'HDiss. – 'HE.A
2
= – 839.31 kJ mol–1
(VII) Enthalpy of hydrogenation ('HHydrogenation) :

The heat evolved during the complete hydrogenation of one mol unsaturated organic compound into its saturated
compound is called as enthalpy of hydrogenation.
Unsaturated organic compound

Change
o Saturated organic compound
(= or { Bond) (– Bond)
C2H2 + 2H2 o C2H6, ' Hhydro 3
C2H2 + H2 o C2H4, ' Hhydro ×
C2H4 + H2 o C2H6, ' Hhydro 3
Note : Heat of hydrogenation is exothermic process.
(VIII) Enthalpy of atomisation

Enthalpy change to covert 1 mole of molecule into gaseous atoms is called enthalpy of atomisation :
Ex. CH4(g) o C(g) + 4H(g) ; 'Hatomisation (CH4(g))
C2H6(g) o 2C(g) + 6H(g) ; 'Hatomisation (C2H6(g))
H2(g) o 2H(g) ; 'Hatomisation (H2(g))
Ex. The heat of solution anhydrous CuSO4(s) is –15.9 kcal/mol and that of CuSO4.5H2O(s) is 2.8 kcal/mol. Calculate the
heat of hydration of CuSO4(s).
Sol. Given CuSO4(s) + aq. o CuSO4 (aq) 'H = – 15.9 K-cal ...(i)
CuSO4.5H2O(s) + aq. o CuSO4 (aq) 'H = + 2.8 K-cal ...(ii)
Subtracting Eq. (ii) from Eq.(i)
CuSO4(s) + 5H2O o CuSO4.5H2O(s); 'H = – 15.9 – 2.8 = – 18.7 K-cal
–1
Heat of hydration of CuSO4 = –18.7 K-cal mol
Ex. The bond dissociation enthalpies of H2(g) and N2 (g) are + 435.95 kJmol–1 and + 941.8 kJ mol–1 and enthalpy of
formation of NH3(g) is –46.024 kJ mol–1.
(a) What is the enthalpy of atomization of NH3(g) ?
(b) What is the bond enthalpy of N – H bond ?
Sol. (a) The desired equation is
NH3(g) o N(g) + 3H(g)
we can consider the reaction as
'H 'H 1 3
NH3(g)
1
o N(g) + 3H(g)
2
o N2(g) + H2(g)
2 2
41
? 'H1 + 'H2 = +46.024 kJ mol–1
3 1
Now 'H2 = – (435.95) – (941.80)
2 2
3 1
? 'H1 = 46.024 + (435.925) + (941.8)
2 2
or 'H1 = 46.024 + 653.925 + 470.9
or 'H1 = 1170.849 kJ mol–1
or 'H1 = 1.170849 MJ mol–1
(b) The average bond enthalpy of N – H bond
117 0.8 49
= = 390.283 kJ mol–1
3
(VIII) Ionisation enthalpy

Enthalpy change when one mole of gaseous atom is converted into gaseous ion be removing one mole electron from
ground state is called ionisation enthalpy.
Ex. Na(g) o Na+ (g) + e ; 'HIonization (Na(g))
H(g) o H (g) + e ; 'HIonization (H(g))
+
Different types of standard enthalpy changes (Based on IUPAC recommendations)
Transition Enthalpy Example Definition Symbol
1
1. Enthalpy of formation K(s) + Cl (g) oKCl(s) One mole of the compound 'fH° or 'H°f
2 2
formed from its elements
2. Enthalpy of combustion C2H6(g) + O2(g) o One mole of the compound 'cH° or 'H°c
CO2(g) + 3H2O(A) (fuel) is burnt completely in
oxygen
3. Enthalpy of fusion H2O(s) o H2O(A) One mole of the liquid is formed 'fusH° or 'H°fus
from the solid without a change
in temperature
4. Enthalpy of vaporisation H2O(A) o H2O(g) One mole of the vapour formed 'vapH° or 'H°vap
from the liquid without a change
in temperature
5. Enthalpy of sublimation I2(s) o I2(g) One mole of the vapour formed 'subH° or 'H°sub
the solid
6. Enthalpy of atomisation H2(g) o 2H(g) One mole of the substance 'atH° or 'H°at
broken into isolated atoms in the
gas phase
42
7. Enthalpy of reaction A oB Enthalpy change taking place in 'rH° or 'H°r

a reaction
8. Enthalpy of HCl(aq) + NaOH(aq) o One mole of water formed by 'nH° or 'H°n
neutralisation H2O + NaCl(aq) the neutralisation of an acid by
a base
9. Enthalpy of Na(g) oNa (g) + e
+ –
One mole atoms ionised - all 'ionH° or 'H°ion
ionisation species in gaseous phase
10. Electron-gain enthalpy X(g) + e– oX–(g) One mole of anions being 'egH° or 'H°eg
formed all species in the
gaseous phase
11. Lattice enthalpy NaCl(s) oNa (g) + Cl (g)
+ –
One mole of a crystal completely 'LH° or 'H°L or U
separated into isolated particles in
the gaseous phase
12. Bond dissociation HCl(g) oH(g) + Cl(g) One mole of bonds broken - all 'H°A – B=HA – B
enthalpy (bond A – B) species in the gaseous phase
13. Enthalpy of solution NaCl(s) + H2O(excess) o One mole of the solute dissolved 'solH° or 'H° sol
NaCl(aq) in excess of solvent so that further
dilution produces no enthalpy
change
14. Enthalpy of hydration X (g) oX (aq)
± ±
One mole of the ion in gaseous 'hydH° or 'H°hyd
phase is hydrated
15. Enthalpy of mixing pure substances omixture One mole each of the two or 'mixH° or 'H°mix
more substances is mixed
43
THERMODYNAMICS
1. First law of Thermodynamics
For a finite change : q = 'E – w = 'E – P'V
where q is heat given to system, 'E is change in internal energy and –w is work done by the system.
dq = dE – dw = dE – PdV
2. Work Done in an Irreversible Process
ª P T – P2 T1 º
w = –Pext × 'V = –Pext × (V2 – V1) = – Pext × R « 1 2 »
¬ P1P2 ¼
Pext is the pressure against which volume changes from V1 to V2
3. Work Done in Reversible Process, i.e., Maximum Work

Isothermal Conditions
wrev = –2.303 nRT log10 (V2/V1)
wrev = –2.303 nRT log10 (P1/P2)
wrev is maximum work done.
Adiabatic Conditions
wrev = [nR/(J – 1)] [T2 – T1]
J is poisson's ratio.
Also for adiabatic process, following conditions hold good :
PVJ= constant
TJPl –J= constant
VJ –l = constant
4. Heat Capacities
At constant pressure Cp = (GH/GH)p
Cp is molar heat capacity at constant pressure.
At constant volume Cv = (GE/GT)v
Cv is molar heat capacity at constant volume.
Cp × cp × M and Cv = cv × M
and Cp – Cv = R/M
Cp/Cv = cp/cv = J (The poisson's ratio)
cp and cv are specific heats at constant pressure and volume respectively.
44
5. Entropy
'S = ¦Sproducts – ¦Sreactants
'S = qrev /T = 2.303 nR log10 (V2/V1) = 2.303 nR log10 (P1/P2)
'Sfusion = 'Hfusion/T
'Svap = 'Hvap/T
'S is entropy change.
6. Free Energy
G = H – TS
'G = 'H – T'S and 'G° = 'H° – T'S° (In standard state)
At equilibrium, 'G = 0
–'G° = RT ln Kp (or KC)
= 2.303 RT log10 KP ( or KC)
'G is free energy change and 'G° is standard free energy change. KC and Kp are equilibrium constants in terms of
concentration and pressure respectively.
7. Unit Conversion
1 cal = 4.1868 J = 4.1868 × 107 erg.
1J = 107 ergs
1 eV = 1.602 × 10–19 = 1.602 × 10–12 ergs.
1 MeV = 106 eV
order : 1 cal > 1 J > 1 erg > 1 eV.
THERMOCHEMISTRY
y 'rH = qP = Heat of reaction at constant pressure

'rE = 'rU = qV = Heat of reaction at constant volume.
y For mix. of reacting ideal gases at constant Temperature :
'rH = 'rU + 'ng) RT.
Exothermic Reaction
HP > HR UP > UR
'rH > 0
'rU > 0
Endothermic Reaction
HP < HR UP < U R
'rH < 0
'rU < 0
Reversible Phase Transition

Isothermal and Isobaric
45
Ex.
(a) Melting or Freezing at MP
(b) Vaporisation or condensation at B.P.
(c) Sublimation at sublimation point.
(d) Interconversion of allotropic forms at Transition temperature.
Sg >> SA > Ss ; Vg >> VA > Vs ;
Vg >> VA < Vs (Water) ; Hg >> HA > Hs ;
Ug >> UA > Us ; 'Hsub >> 'Hvap > 'Hfus.
At same Pressure and Temperature
'Hsub = 'Hvap + 'Hfus.
y For reversible phase transition.
W = – Pext ['V]
'H trans
'Strans. =
Ttrans
q = 'Htrans
'Utrans = 'Htrans + w
y 'rH = ¦VPH (product) – ¦VRH (Reactant)
VP, VR – Stoichiometric coefficient of reactants & products
'rG = ¦VPG (product) – ¦VRG (reactants)
Determining 'rH° for reaction :- 3 methods

(a) 'rH° = ¦VP 'H°f (P) – ¦VR 'H°f (R)
(b) 'rH° = ¦VR 'H°comb. (R) – ¦VP 'H°comb. (P)
(c) 'rH° = ¦'Hatomisation (R) – ¦'Hatomisation (P)
y 'H°f (Element in solid state) = 0.
'H°f (CO2, g) = 'H°comb. (C, grap.)
'H°f (H2O, A) = 'H°comb. (H2, g)
y aA + bB o cC + dD ; 'rH°
'rH° = change in enthalpy when
a mol of A react ; b mol of B react ; c mol of C formed ; d mol of D formed
y 'rG° = ¦VP 'G°f (P) – ¦VR 'G°f (R) OR 'rG° = 'rH° – T'rS°
y Gibbs enthalpy is function of P, T.

Pn Gn
Tn Gp
y 'H°f (H+, aq) = 0 º
»
'G°f (H , aq) = 0
+
»
EqH 2 | H = 0 » By convention
»
S°m (H+, aq) = 0 »¼
46
y q = ³ ms dt
= ³ n C m dt
= ³ C dt
mS = nCm = C
p p p
specific molar Total
heat heat heat
capacity capacity capacity
y For strong Acid and strong base
'H°neutr. = – 57.1 kJ/mol.
when 1 eq. H+ (acid) reacts with 1 eq. OH– (base)
y If acid or base is weak
'H°neut. = – 57.1 + 'Hionisation + ve
y 'rH° (Actual) – 'rH° (theoretical) = >¦VP RE (P) – ¦VR RE (R)
'H°hydration [CuSO4, s]
'H°solution [CuSO4, s] – 'H°solution [CuSO4 5H2O, s]
Enthalpy of atomisation
'H°atomisation (O2, g) = BE (O = O)
'H°atomisation (C6H6, A) = 'H°vap. + 3 (C = C) + 3 (C – C) + 6 (C – H) = Bond enthalpy
'H°atomisation (Fe, s) = 'H°sub
'H°atomisation (I2, s) = 'H°sub + (I – I)
47
SOLVED EXAMPLE
Ex. 1 During 200J work done on the system, 140 J of heat NaCl is dissolved in water at 25ºC. Lattice energy of
is given out. Calculate the change in internal energy. NaCl = 777.8 kJ mol–1 ; 'S for dissolution = 0.043 kJ
Sol. w = 200 J; q = –140 J; mol–1 and hydration energy of NaCl = –774.1 kJ mol–1.
' q = 'E + (–w); where –w is work done by the Sol. 'Hdissolution = Lattice energy + Hydration energy
system = 777.8 – 774.1 = 3.7 kJ mol–1
'E = q + w Now 'G = 'H – T'S
'E = –140 + 200 = +60J = 3.7 – 298 × 0.043 = 3.7 – 12.814
'G = –9.114 kJ mol–1
Ex. 2 A gas absorbs 200 J of heat and expands against the
external pressure of 1.5 atm from a volume of 0.5 Ex. 6 The equilibrium constant for the reaction given
litre. Calculate the change in internal energy. below is 2.0 × 10–7 at 300 K. Calculate the standard
Sol. w = –P'V = –1.5 × (1.0 – 0.5) = –0.75 litre atm free energy change for the reaction;
= –0.75 × 101.3 J = –75.975 J
ZZZ
PCl5(g) YZZ XZ PCl3(g) + Cl2(g)
' 1 litre atm = 101.3 J
Now, 'E = 200 – 75.975 = +124.025 J Also, calculate the standard entropy change if 'Hº
= 28.40 kJ mol–1.
Ex. 3 Two litre of N2 at 0 oC and 5 atm pressure are Sol. 'Gº = –2.303 × 8.314 × 300 log [2.0 × 10–7]
expanded isothermally against a constant external = +38479.8 J mol–1 = +38.48 kJ mol–1
pressure of 1 atm until the pressure of gas reaches 1 Also, 'Gº = 'Hº – T'Sº
atm. Assuming gas to be ideal, calculate work of
expansion. ΔHo – ΔG o 28.40 – 38.48
? 'Sº = =
Sol. Since the external pressure is greatly different from T 300
–1
the pressure of N2 and thus, process is irreversible. = –0.0336 kJ = –33.6 JK
w = –Pext (V2 – V1)
Ex. 7 One mole of a perfect monoatomic gas is put through
w = –1 × (V2 – V1)
a cycle consisting of the following three reversible
Given V1 = 2 litre V2 = ? T = 273 K steps :
P1 = 5 atm P2 = 1 atm
T1 T2
? P1V1 = P2V2 (20, 1) (20, 10)
2 u5 A B
? V2 = = 10 litre
1
P
? w = –1 × (10 – 2) = –8 litre atm
8 u 1.9 8 7 C
? calorie
0.08 21 T1 (2, 10)
8 u 1.98 7 u 4 .1 84 V
J = –810.10 joule (CA) Isothermal compression from 2 atm and 10 litres
0.08 21
to 20 atm and 1 litre.
Ex. 4 The enthalpy of vaporisation of liquid diethyl ether (AB) Isobaric expansion to return the gas to the
–(C2H5)2O, is 26.0 kJ mol–1 at its boiling point (35.0ºC). original volume of 10 litres with T going from T1 to
Calculate 'S for conversion of : (A) liquid to vapour, T2.
and (B) vapour to liquid at 35ºC. (BC) Cooling at constant volume to bring the gas to
Sol. (A) 'Svap. = the original pressure and temperature.
'H vap. 26 u 10 3 The steps are shown schematically in the figure
84 .41 JK 1 mol1 shown.
T 3 08
(A) Calculate T1 and T2.
'H cond. 26 u 10 3 (B) Calculate 'E, q and w in calories, for each step
(B)'Scond. = (' Hcond = –26 kJ)
T 308 and for the cycle.
= –84.41 JK–1 mol–1 Sol. We know,
Ex. 5 Calculate the free energy change when 1 mole of
48
Path CA – Isothermal compression through a cyclic process starting from A as shown
Path AB – Isobaric expansion VB V
Path BC – Isochoric change in figure. The volume ratios are = 2 and D
VA VA
Let Vi and Vf are initial volume and final volume at
respective points, = 4. If the temperature TA at A is 27ºC, calculate :
For temperature T1 (For C) : PV = nRT1 V
2 × 10 = 1 × 0.0821 × T1
? T1 = 243.60K VD
D C
PV P V
For temperature T2 (For C and B) : 1 1 = 2 2
T1 T2
VB
B
2 ×10 20 ×10 VA
= A
T1 T2
O T
T2 TA TB
? = 10 (A) The temperature of the gas at point B.
T1
? T2 = 243.60 × 10 = 2436.0 K (B) Heat absorbed or released by the gas in each
process.
V
Path CA : w = +2.303 nRT1 log i (C) The total work done by the gas during complete
Vf cycle.
10 Sol. For the given cyclic process,
= 2.303 × 1 × 2 × 243.6 log
1 VB VD
= +1122.02 cal 2, 4 , T = 300 K
'E = 0 for isothermal compression ; Also q = w VA VA A
Path AB : w = –P(Vf – Vi) (A) For isobaric process AB

= –20 × (10 – 1) = –180 litre atm
180 u 2 VA VB
= = –4384.9 cal TA TB
0.0821
Path BC : w = –P (Vf – Vi) = 0
(' Vf – Vi = 0) VB
? TB = T A × = 300 × 2 = 600 K
since volume is constant for monoatomic gas heat VA
change at constant volume = qv = 'E.
Thus for path BC qv = Cv × n × 'T = 'E (B) The following process are there in complete cycle
(i) A o B Isobaric expansion
3
? qv = R × 1 × (2436 – 243.6) (ii) B o C Isothermal expansion
2
(iii) C o D Isochoric compression
3
qv = × 2 × 1 × 2192.4 = 6577.2 cal (iv) D o A Isothermal compression
2
Since process involves cooling 5
For (i) qA o B = +n × CP × 'T = +2 × × R × 300
? qv = 'E = –6577.2 cal 2
Also in path AB, the intenal energy in state A and = +1500 × 2 = +3000 cal (R = 2 cal)
state C is same. Thus during path AB, an increase in (ii) qBoC = 'E – w ('E = 0)
internal energy equivalent of change in internal
? qBoC = 'E – w
energy during path BC should take place. Thus 'E
for path AB = +6577.2 cal VD 4
Now q for path AB = 'E – wAB = 6577.2 + 4384.9 = = + ³ PdV nRT ln 2 u 2 u 600 ln
VB 2
10962.1 cal
Cycle : 'E = 0 ; q = –w = +1.663 + 103 cal
= – [wPath CA + wPath AB + wPath BC] 3
= – [+1122.02 + –4384.9 + 0] (iii) qCoD = n × Cv × 'T = 2 × × 2 × – 300
2
? q = –w
= –1800 cal
= +3262.88 cal
Ex. 8 A monoatomic ideal gas of two moles is taken
49
VA 1 1
(iv) qDoA = +nRTA ln = +2 × 2 × 300 ln Ex. 11 For a reaction M2O(s) o 2M(s) + O (g); 'H
VD 4 2 2
3
= –2 × 2 × 300 × 1.386 = –1.663 × 10 cal = 30kJ mol–1 and 'S = 0.07 kJ K–1 mol–1 at 1 atm.
? Q = qAoB + qBoC + qCoD + qDoA Calculate upto which temperature, the reaction
= 3000 + 1663 – 1800 – 1663 = 1200 cal would not be spontaneous.
(C) Since the process ABCDA is a cyclic process Sol. Given, for the change, 'H = 30 × 103 J mol–1, 'S = 70
? 'E = 0 or Q = 'E – Q = –w or JK–1 mol–1
Q = –1200 cal For a non-spontaneous reaction
i.e., work done on the system = 1200 cal 'G = +ve
Since 'G = 'H – T'S
Ex. 9 Calculate the work done when 50 g of iron reacts
with hydrochloric acid in : ? 'H – T'S should be +ve
(i) a closed vessel of fixed volume, or 'H > T'S
(ii) an open beaker at 25°C. 'H 30 u 10 3
Sol. We know, or T< T <
'S 70
(i) Vessel is of fixed volume, hence 'V = 0. No work
is done, w = 0 T < 428.57 K
(ii) The H2 gas formed drives back the atmosphere Ex. 12 Predict whether the entropy change of the system
hence. in each of the following process is positive or
w = –Pext . 'V negative.
Also 'V = Vfinal – Vinitial ~ Vfinal (' Vinitial = 0) (A) CaCO3(s) o CaO(s) + CO2(g)
nRT (B) N2(g) + 3H2(g) o 2NH3(g)
? 'V =
Pext (C) N2(g) + O2(g) o 2NO(g)
(D) HCl(g) + NH3(g) o NH4Cl(s)
nRT
or w = –Pext . = –nRT
T (E) 2SO2(g) + O2(g) o 2SO3(g)
Pext (F) Cooling of N2(g) from 20°C to –50°C
where n is the number of mole of H2 gas obtained Sol. Gaseous substances generally possess more
from n mole of Fe(s). entropy than solids. So whenever the products
Fe(s) = 2HCl(aq) o FeCl2(aq.) + H2(g) contain more moles of a gas than the reactants, the
1 mole 1 mole entropy change is probably positive. And hence,
50 'S is
? n= = 0.8929 mole (A) positive
56
? w = –0.8929 × 8.314 × 298 (B) negative
= –2212.22 J (C) small, the sign of 'S is impossible to predict
The reaction mixture in the given system does 2.212 (D) negative
kJ of work driving back to atmosphere. (E) negative
(F) negative
Ex. 10 The internal energy change in the conversion of 1.0 [Note : For a given substance at a given temperature,
mole of the calcite form of CaCO3 to the aragonite Sgas > Sliquid > Ssolid]
form is +0.21 kJ. Calculate the enthalpy change when
the pressure is 1.0 bar; given that the densities of Ex. 13 Calculate the boiling point of bromine from the
the solids are 2.71 g cm–3 and 2.93 g cm–3 respectively. following data :
Sol. 'H = 'E + P'V 'Hº and 'Sº values of Br2(l) o Br2(g) are 30.91 kJ/
Given 'E = +0.21 kJ mol–1 = 0.21 × 103 J mol–1 mole and 93.2 J/mol. K respectively. Assume that
'H and 'S do not vary with temperature.
P = 1 = 1.0 × 105 Pa
Sol. Consider the process : Br2(l) o Br2(g)
'V = V(aragonite) – V(Calcite)
The b.p. of a liquid is the temperature at which the
§ 10 0 100 · liquid and the pure gas coexist at equilibrium at 1
=¨ 3 –1
¸ cm mol of CaCO3
© 2.93 2.71 ¹ atm.
= –2.77 cm3 = –2.77 × 10–6 m3 ? 'G = 0
? 'H = 0.21 × 103 – 1 × 105 × 2.77 × 10–6 = 209.72 J As it is given that 'H and 'S do not change with
= 0.20972 kJ mol–1 temperature
50
'H = 'H° = 30.91 kJ (iii) For isothermal process, 'E = 0 and heat is
'S = 'S° = 93.2 J/K = 0.0932 kJ/K absorbed by the gas,
We have, 'G = 'H – T'S = 0 qrev = 'E – W = 0 – (–1718) = 1718J
? qsurr = 1718 J. ('process is reversible)
'H 30 .9 1
? T= = 331.6 K.
'S 0.0 93 2 1 71 8
(iv) 'Ssurr = – = –5.76 J/K.
This is the temperature at which the system is in 2 98
equilibrium, that is, the b.p of bromine. As entropy of the system increases by 5.76 J, the
Ex. 14 The efficiency of the Carnot engine is 1/6. On entropy of the surroundinig decreases by 5.76 J,
decreasing the temperature of the sink by 65K, the since the process is carried out reversible.
efficiency increases to 1/3. Find the temperature of (v) 'Ssys + 'Ssurr = 0 ....... for reversible process.
the source and the sink. (B) (i) 'S = 5.76 J/K, which is the same as above
Sol. We have, because S is a state function.
T2 T1 (ii) w = 0. (' pext = 0)
K= , where T1 and T2 are the temperatures (iii) No heat is exchanged with the surroundings.
T2
(iv) 'Ssurr = 0
of sink and source respectively.
(v) The entropy of the system plus surroundings
T2 T1 1 increases by 5.76 J/K, as we expect entropy to
? K= ............(i) increases in an irreversible process.
T2 6
Now the temperature of the sink is reduced by 65 K.
Ex. 16 From the following data at 25ºC
? temp. of the sink = (T1 – 65)
Reaction 'r Hº/KJ mol–1
T2 (T1 65 ) 1 1/2 H2(g) + 1/2O2(g) o OH(g) 42.09
? K= ............(ii)
T2 3 H2(g) + 1/2O2(g) oH2O(g) –241.84
On solving eqns. (i) and (ii), we get, H2(g) o 2H(g) 435.88
T1 = 325 K O2(g) o 2O(g) 495.04
T2 = 390 K Calculate 'r H° for the following reactions
(A) OH(g) o H(g) + O(g)
Ex. 15 (A) One mole of an ideal gas expands isothermally
and reversible at 25ºC from a volume of 10 litres to a (B) H2O(g) o 2H(g) + O(g)
volume of 20 litres. (C) H2O(g) o H(g) + OH(g)
(i) What is the change in entropy of the gas ? Sol. (A) The desired equation is
(ii) How much work is done by the gas ? OH(g) o H(g) + O(g)
(iii) What is q(surroundings) ? We are to develop the desired equation by using
(iv) What is the change in the entropy of the the four given equations
surroundings ?
1 435.88
(v) What is the change in the entropy of the system (i) H 2 (g) o H(g) 'rH° =
plus the surroundings ? 2 2
(B) Also answer the questions (i) to (v) if the 1 1
expansion of the gas occurs irreversibly by simply (ii) OH(g) o H2(g) + O2 (g) 'rH° = –42.09
opening a stopcock and allowing the gas to rush 2 2
into an evacuated bulb of 10-L volume.
1 495.04
V (iii) O2(g) o O(g) 'rH° =
Sol. (i) 'S = 2.303nR log 2 2 2
V1
By adding equation (i), (ii) & (iii), we get
20 OH(g) o H(g) + O(g)
= 2.303 × 1 × 8.314 × log = 5.76 J/K.
10
435.88 495.04
V 'rH° o – 42.09 +
(A) (ii) wrev = 2.303 nRT log 2 2 2
V1
or 'rH° = 423.37 kJ/mol. Ans.
20 (B) The desired equation is
= –2.303 × 1 × 8.314 × 298 × log = –1718 J.
10 H2O(g) o 2H(g) + O(g)
51
Ex. 19 Using bond enthalpy data given below, estimate
1 495.04
(i) O2(g) o O(g) 'rH° = enthalpy of formation of acetic acid.
2 2
(ii) H2(g) o 2H(g) 'rH° = 435.88 Bond Bond enthalpies
–1
C–H 413.38 kJ moll
1 C–C 347.69 kJ moll
–1
(iii) H2O(g) o H2(g) + O (g) 'rH° = 241.88 C=O 728.02 kJ moll

–1
2 2 –1
C–O 351.46 kJ moll
The net equation is, O– H 462.75 kJ moll
–1
H2O(g) o 2H(g) + O(g) 'rH° = 925.28 kJ/mol Ans.

(C) The desired equation is Enthalpy of atomization
H2O(g) o H(g) + OH(g) –1
(i) H2O(g) o 2H(g) + O(g) C 718.39 kJ atom
–1
'rH° = 925.28 kJ/mol H 217.94 kJ atom
–1
(ii) H(g) + O(g) o OH(g) 'rH° = 423.37 kJ/mol O 247.52 kJ atom
By adding eqn (i) and (ii)
The observed 'fH° for acetic acid is –438.15 kJ mol–
H2O(g) o H(g) + OH(g) 1
. Compute the resonance energy of acetic acid.
'rH° = 1348.65 kJ/mol Ans.
Sol. The desired reaction for the formation of CH3COOH
Ex. 17 From the given data prove that graphite is more is
stable allotrope of carbon than diamond from the
2C(s) + 2H2(g) + O2(g) o CH3COOH (A)
given data
'rHº = –3 × 413.38 – 1 × 347.69 – 728.02 – 351.46 –
Cdia + O2 o CO2 'H1° = –94500 cal
462.75 + 2 × 718.39 + 4 × 217.94 + 2 × 247.52
Cgra + O2 o CO2 'H2° = –94050 cal
Sol. Cdia + O2(g) o CO2 = – 326.48 kJ mol–1
'H1° = –94500 cal Resonance energy = 'H°obs – 'H°
Cgra + O2(g) o CO2 = –438.15 + 326.48
'H2° = –94050 cal = –111.67 kJ mol–1
on substraction
Cdia o Cgra Ex. 20 At 25º C, 1 mole MgSO4 was dissolved in water. The
'rHº = –450 cal heat evolved was found to be 91.211 kJ. One mole of
MgSO4. 7H2O on dissolution gives a solution of the
same composition accompained by an absorption
of 13.807 kJ. Find the enthalpy of hydration, i.e., 'H
for the reaciton
MgSO4(s) + 7H2O(A) o MgSO4 . 7H2O(s)
since heat content of diamond > graphite Given that
Therefore diamond is less stable than graphite. (i) MgSO4 (s) + aq o MgSO4 (aq)
'rH1 = –91.211 kJ mol–1
Ex. 18 Calculate 'rH° for the reaction
(ii) MgSO4 . 7H2O (s) + aq o MgSO4 (aq)
Ag+(aq) + Cl–(aq) = AgCl (s) at 25°C.
'rH2 = +13.807 kJ mol–1
Given :
'fH° (Ag+, aq) = 105.58 kJ mol–1, Sol. MgSO4 . 7H2O (s) + aq o MgSO4 (aq)
'fH° (Cl–, aq) = –167.16 kJ mol–1 and 'fH° 'rH2 = +13.807 kJ mol–1 ...........(ii)
(AgCl, s) = –127.07 kJ mol–1 Equation (i) can be written as follows :
Sol. For the reaction MgSO4(s) + 7H2O(A) + aq o MgSO4(aq)
Ag+(aq) + Cl–(aq) o AgCl(s) 'rH = –91.211 kJ mol–1 ...........(iii)
We have eqn (iii) – (ii) will give
'rH° = (AgCl, s)– 'fH° (Ag+, aq) –'fH° (Cl–, aq) MgSO4(s) + 7H2O(A) o MgSO4. 7H2O(s)
= [–127.07 – 105.58 – (–167.16)] 'rH = –91.211 – 13.807 = –105.018 kJ mol–1.
= –65.49 kJ mol–1
52
Ex. 21 Enthalpy of neutralization of HCl by NaOH is –57.32 Ex. 23 The specific heats of iodine vapour and solid are
kJ mol–1 and by NH4OH is –51.34 kJ mol–1. Calculate 0.031 and 0.055 cal/g respectively. If heats of
the enthalpy of dissociation of NH4OH. sublimation of iodine is 24 cal/g at 200°C, what is its
Sol. Given that value at 250ºC ?
H+(aq) + NH4OH(aq) o NH4+ (aq) + H2O(A) Sol. Given
'rH = –51.34 kJ mol–1 I 2 (s ) o I2 (v ) ; 'H = 24 cal/g at 200ºC
we may consider neutralization in two steps :
'CP(cal/g) = CP of product – CP of reatant
(i) ionization
= 0.031 – 0.055
NH4OH(aq) o NH4+(aq) + OH–(aq) 'rH1 ?
= –0.024 cal/g
(ii) neutralization Now 'H2 – 'H1 = 'CP (T2 – T1)
H+ (aq) + OH–(aq) o H2O(A) 'H2 – 24 = –0.024 × (523 – 473)
'rH2 = –57.32 kJ mol–1 ? 'H2 = 24 – 1.2 = 22.8 cal/g.
Thus, 'rH = 'rH1 + 'rH2
Ex. 24 The molar heat of formation of NH 4 NO 3 (s ) is –367.54
Therefore,
'rH1 = 'rH – 'rH2 kJ and those of N2O(g), H2O(l) are 81.46 and –285.8 kJ
respectively at 25°C and 1 atmosphere pressure.
= –51.34 + 57.32 = 5.98 kJ/mol–1
Calculate 'H and 'E of the reaction
Ex. 22 The enthalpy of formation of ethane, ethylene and NH 4 NO 3 (s ) o N 2 O (g ) 2 H 2 O (A )
benzene from the gaseous atoms are –2839.2, –2275.2
and –5536 kJ mol–1 respectively. Calculate the Sol. We have to find 'H for
resonance energy of benzene, compared with Kekule NH 4 NO3(s)
o N 2 O(g) + 2H 2O (l) ; 'H = ?
structure. The bond enthalpy of C – H bond is given
'Hreaction = 'HProducts – 'HReactants
as equal to 410.87 kJ mol–1.
Sol. Bond enthalpy of C – C bond = ΔH N 2O + ΔH H 2O × 2 – ΔH NH 4 NO3
= Enthalpy required to break C2H6 into gaseous Given, ΔH N 2O = +81.46 kJ ,
atoms –6 × bond enthalpy of C – H bond
= 2839.2 kJ mol–1 – 6 × 410.87 kJ mol–1 ΔH H 2O = –285.8 kJ , ΔH NH 4 NO3 = –367.54 kJ
= 373.98 kJ mol–1 ? 'Hreaction = +81.46 + 2(–285.8) – (–367.54)
Bond enthalpy of C = C bond = Enthalpy requried to 'H = –122.6 kJ
break C2H4 into gaseous atoms –4 × bond enthalpy Further 'H = 'E + 'nRT
of C – H bond ('n = 1 – 0 = 1, R = 8.314 J, = 298 K)
= 2275.2 kJ mol–1 – 4 × 410.87 kJ mol–1 ? –122.6 × 103 = 'E + 1 × 8.314 × 298
= 631.72 kJ mol–1 ? 'E = –125077 joule
For the formation of benzene having Kekule = 125.077 kJ
structure, we have to form 3 C – C bonds, 3 C = C
bonds and 6 C – H bonds for which enthalpy
released is
[3 (–373.98) + 3(–631.72) + 6(–410.87)]
= –5482.32 kJ mol–1
But the given value of 'fH is
'fH (actual) = –5536 kJ mol–1
Hence resonance energy compared to Kekule
structure
= 'fH (actual) – 'fH (Kekule structure)
= (–5536 + 5482.32)
= –53.68 kJ mol–1
53
Exercise PART - 1 PREVIOUS YEAR (NEET/AIPMT)
1. The denisties of graphite and diamond at 298 K are 7. Considering entropy (S) as a thermodynamic
2.25 and 3.31 g cm–3, respectively. If the standard parameter, the criterion for the spontaneity of any
free energy difference ('G°) is equal to 1895 J mol–1, process is [CBSE AIPMT 2004]
the pressure at which graphite will be transformed (A) 'Ssystem + 'Ssurrounding > 0
into diamond at 298 K is [CBSE AIPMT 2003]
(B) 'Ssystem – 'Ssurrounding > 0
(A) 9.92 × 106 pa (B) 9.92 × 105 pa
(C) 'Ssystem > 0
(C) 9.92 × 108 pa (D) 9.92 × 107 Pa
(D) 'Ssurrounding > 0
2. What is the entropy change (in J K–1 mol–1) when
8. The work done during the expansion of a gas from a
one mole of ice is converted into water at 0°C? (The
volume of 4 dm3 to 6 dm3 against a constant external
enthalpy change for the converstion of ice to liquid
pressure of 3 atm, is [CBSE AIPMT 2004]
water is 6.0 kJ mol–1 at 0°C) [CBSE AIPMT 2003]
(A) – 6 J (B) –608 J
(A) 2.198 JK–1 mol–1 (B) 21.98 JK–1 mol–1
(C) + 304 J (D) – 304 J
(C) 20.13 JK–1 mol–1 (D) 2.013 JK–1 mol–1
9. A reaction occurs spontaneously if
3. For which one of the following equestions 'H°r equal
to 'Hf° for the product? [CBSE AIPMT 2003] [CBSE AIPMT 2005]
(A) Xe(g) + 2F2(g) o XeF4(g) (A) T'S < 'H and both 'H and 'S are +ve
(B) 2CO(g) + O2(g) o 2CO2(g) (B) T'S > 'H and both 'H and 'S are +ve
(C) N2(g) + O3(g) o N2O3(g) (C) T'S = 'H and both 'H and 'S are +ve
(D) CH4(g) +2Cl2(g) o CH2Cl2 + 2HCl(g) (D) T'S > 'H and 'H is +ve and 'S is –ve
4. For the reaction, 10. Which of the following pairs of a chemical reaction
C3H8(g) + 5O2(g) o 3CO2(g) + 4H2O(l) is certain to result in a spontaneous reaction?
at constant temperature, 'H – 'E is [CBSE AIPMT 2006]
[CBSE AIPMT 2003] (A) Exothermic and decreasing disorder
(A) + 3RT (B) –RT (B) Endothermic and increasing disorder
(C) +RT (D) –3RT (C) Exothermic and increasing disorder
(D) Endothermic and decreasing disorder
5. If the bond energies of H – H, Br – Br and H–Br are
433, 192 and 364 kJ mol–1 respectively, then 'H° for 11. The absolute enthalpy of neutralisation of the
the reaction H2(g) + Br2(g) o 2HBr(g) is reaction
[CBSE AIPMT 2004] MgO(s) + 2HCl(aq) o MgCl2(aq) + H2O(l)
(A) –261 kJ (B) + 103 kJ will be [CBSE AIPMT 2005]
(C) +261 kJ (D) – 103 kJ (A) less than –57.33 kJ mol–1

(B) –57.33 kJ mol–1
6. Standard enthalpy and standard entropy changes (C) greater than –57.33 kJ mol–1
for the oxidation of ammonia at 298 K are –382.64 kJ
(D) 57.33 kJ mol–1
mol–1 and –145.6 JK–1 mol–1, respectively. Standard
Gibbs energy change for the same reaction at 298 K 12. Identify the correct statement for change of Gibbs
is [CBSE AIPMT 2004] free energy for a system ('G system) at constant
(A) –221.1 kJ mol–1 (B) – 339.3 kJ mol–1 temperature and pressure. [CBSE AIPMT 2006]
(C) – 439.3 kJ mol–1 (D) – 523.2 kJ mol–1
54
(A) If 'Gsystem > 0, the process is spontaneous 17. Given that bond energies of H–H and Cl–Cl are 430
(B) If 'G system = 0, the system has attained kJ mol–1 and 240 kJ mol–1 respectively and 'Hf for
equilibrium HCl is –90 kJ mol–1. Bond enthalpy of HCl is
(C) If 'Gsystem = 0, the system is still moving in a [CBSE AIPMT 2007]
particular direction (A) 290 kJ mol –1
(B) 380 kJ mol–1
(D) If 'Gsystem < 0, the process is not spontaneous (C) 425 kJ mol–1 (D) 245 kJ mol–1
13. Assume each reaction is carried out in an open 18. Which of the following are not state functions?
container. For which reaction will 'H = 'E? [CBSE AIPMT 2008]
[CBSE AIPMT 2006] I. q + W II. q
(A) H2(g) + Br2(g) o 2HBr (g) III. W IV. H – TS
(B) C(s) + 2H2O(g) o 2 H2(g) + CO2(g) (A) I and IV (B) II, III and IV
(C) PCl5(g) o PCl3(g) + Cl2(g) (C) I, II and III (D) II and III
(D) 2CO(g) + O2(g) o 2 CO2(g)
19. For the gas phase reaction,
14. The enthalpy and entropy change for the reaction, PCl5(g)  PCl3 (g) + Cl2(g)
Br2(l) + Cl2(g) o 2 BrCl(g) which of the following conditions are correct?
are 30 kJ mol–1 and 105 JK–1 mol–1 respectively. The [CBSE AIPMT 2008]
temperature at which the reaction will be in
(A) 'H = 0 and 'S < 0 (B) 'H > 0 and 'S > 0
equilibrium is [CBSE AIPMT 2006]
(C) 'H < 0 and 'S < 0 (D) 'H > 0 and 'S < 0
(A) 285.7 K (B) 273 K
(C) 450 K (D) 300 K 20. From the following bond energies
H–H bond energy : 431.37 kJ mol–1
15. The enthalpy of combustion of H2, cyclohexene
(C6H10) and cyclohexene (C6H10) and cyclohexane C=C bond energy : 606.10 kJ mol–1
(C6H12) are –241, –3800 and –3920 kJ per mol C–C bond energy : 366.49 kJ mol–1
respectively. Heat of hydrogenation of cyclohexene C–H bond energy : 410.50 kJ mol–1
is [CBSE AIPMT 2006] Enthalpy for the reaction,
(A) – 121 kJ per mol (B) + 121 kJ per mol
(C) + 242 kJ per mol (D) – 242 kJ per mol H H H H
C C H H H C C H
16. Consider the following reactions,
(i) H+(aq) + OH–(aq) o H2O(l), –x1 kJ mol–1 H H H H
will be [CBSE AIPMT 2009]
1 1
(ii) H 2 (g) O 2 (g) o H 2O(l), x 2 kJ mol (A) 1523.6 kJ mol –1
(B) –245 kJ mol–1
2
(C) –93 kJ mol–1 (D) 245 kJ mol–1
(iii) CO2(g) + H2(g) o CO(g) + H2O(l), –x3 kJ mol–1
5 21. The values of 'H and 'S for the reaction, C(graphite) +
(iv) C2H2(g) O (g) o 2 CO2(g) + H2O(l), + x4 kJ mol–1 CO 2(g) o 2CO(g) are 170 kJ and 170 JK –1 ,
2 2
respectively. This reaction will be spontaneous at
Enthalpy of formation of H2O(l) is
[CBSE AIPMT 2009]
[CBSE AIPMT 2007]
(A) 710 K (B) 910 K
(A) –x2 kJ mol–1 (B) + x3 kJ mol–1
(C) 1110 K (D) 510 K
(C) – x4 kJ mol–1 (D) + x1 kJ mol–1
55
22. Enthalpy change for the reaction,
1
4H (g) o 2H2 (g) is – 869.6 kJ (C) Mg(s) O 2 (g) o MgO(s)
2
The dissociation energy of H–H bond is
[CBSE AIPMT 2011] 1 1 1
(D) C(graphite) O 2 (g) o CO 2 (g)
2 2 2
(A) – 869.6 kJ (B) + 434.8 kJ
(C) + 217.4 kJ (D) – 434.8 kJ 28. A reaction having equal energies of activation for
forward and reverse reactions has [NEET 2013]
23. Which one of the following is correct option for free
expansion of an ideal gas under adiabatic condition? (A) 'S = 0 (B) 'G = 0
[CBSE AIPMT 2011] (C) 'H = 0 (D) 'H = 'G = 'S = 0
(A) q z 0, 'T = 0, W = 0 29. For a given exothermic reaction, Kp and Kp' are the
(B) q 0, 'T = 0, W = 0 equilibrium constant at temperatures T 1 and T2,
(C) q 0, 'T < 0, W z 0 respectively. Assuming that heat of reaction is
(D) q 0, 'T z 0, W = 0 constant in temperature range between T1 and T2, it
is readily observed that [CBSE AIPMT 2014]
24. If the enthalpy change for the transition of liquid
(A) K p ! K 'p (B) K p K 'p
water to steam is 30 kJ mol–1 at 24°C, the entropy
change for the process would be
1
[CBSE AIPMT 2011] (C) K p K 'p (D) K p K 'p
(A) 1.0 J mol–1K–1 (B) 0.1 J mol–1K–1
(C) 100 J mol–1K–1 (D) 10 J mol–1 K–1
30. For the reaction, X2O4(l) o 2XO2(g), 'U = 2.1 kcal,
25. Standard enthalpy of vaporisation 'vapH° for water 'S = 20 cal K–1 at 300 K. [CBSE AIPMT 2014]
at 100°C is 40.66 kJ mol–1. The internal energy of (A) 2.7 kcal (B) – 2.7 kcal
vaporisation of water at 100°C (in kJ mol–1) is (assume (C) 9.3 kcal (D) –9.3 kcal
water vapour to behave like an ideal gas).
[CBSE AIPMT 2012] 31. Which of the following statements is correct for the
spontaneous absorption of a gas?
(A) + 37.56 (B) – 43.76
[CBSE AIPMT 2014]
(C) + 43.76 (D) + 40.66
(A) 'S is negative and therefore, 'H should be
26. The enthalpy of fusion of water is 1.435 kcal/mol. highly positive
The molar entropy change for the melting of ice at (B) 'S is negative and therefore, 'H should be
0°C is [CBSE AIPMT 2012] highly negative
(A) 10.52 cal/mol K (B) 21.04 cal/mol K (C) 'S is positive and therefore, 'H should be
(C) 5.260 cal/mol K (D) 0.526 cal/mol K negative
(D) 'S is positive and therefore, 'H should also be
27. In which of the following reactions, standard highly positive
reaction entropy changes ('S°) is positive and
standard Gibbs energy change ('G°) decreases 32. Which of the following statements is correct for a
sharply with increasing temperature? reversible process in a state of equilibrium?
[CBSE AIPMT 2012] [CBSE AIPMT 2015]
1 (A) 'G = – 2.30 RT log K (B) 'G = 2.30 RT log K

(A) C(graphite) O 2 (g) o CO(g) (C) 'G° = – 2.30 RT log K (D) 'G° = 2.30 RT log K
2
1
(B) CO(g) O 2 (g) o CO 2 (g)
2
56
33. The heat of combustion of carbon to CO2 is –393.5kJ 38. For a given reaction, 'H = 35.5 kJ mol–1 and 'S =
/ mol. The heat released upon the formation of 35.2 83.6 JK–1 mol–1. The reaction is spontaneous at :
g of CO2 from carbon and oxygen gas is (Assume that 'H and 'S do not vary with
[CBSE AIPMT 2015] temperature) [NEET 2017]
(A) –315 kJ (B) + 315 kJ (A) T < 245 K (B) T > 425 K
(C) –630 kJ (D) –3.15 kJ (C) all temperatures (D) T > 298 K
34. For a sample of perfect gas when its pressure is 39. Considering Ellingham diagram, which of the
changed isothermally from pi to pf , the entropy following metals can be used to reduce alumina ?
change is given by [NEET 2016, Phase II]
[NEET 2018]
§p · §p · (A) Mg (B) Zn
(A) 'S nR ln ¨ f ¸ (B) 'S nR ln ¨ i ¸
(C) Fe (D) Cu
© pi ¹ © pf ¹
§p · §p · 40. Which one of the following conditions will favour

(C) 'S nRT ln ¨ f ¸ (D) 'S RT ln ¨ i ¸
maximum formation of the product in the reaction,
© pi ¹ © pf ¹
A2 (g) + B2 (g) U X2 (g) 'rH = – X kJ ?
35. Consider the following liquid-vapour equilibrium [NEET 2018]
Liquid  Vapour (A) High temperature and high pressure
Which of the following relations is correct ? (B) Low temperature and low pressure
[NEET 2016, Phase I] (C) Low temperature and high pressure
(D) High temperature and low pressure
dlnP 'H v dlnP 'H v
(A) (B)
dT RT dT 2 T2
dlnP 'H v dln G 'H v

(C) (D)
dT RT 2 dT 2 RT 2
36. The addition of a catalyst during a chemical reaction

alters which of the following quantities?
[NEET 2015, Phase I]
(A) Internal energy (B) Enthalpy
(C) Activation energy (D) Entropy
37. A gas is allowed to expand in a well insulated

container against a constant external pressure of
2.5 atm from an initial volume of 2.50 L to a final
volume of 4.50 L. The change in internal energy 'U
of the gas in joules will be [NEET 2017]
(A) 1136.25 J (B) – 500 J
(C) – 505 J (D) + 505 J
57
Exercise PART - 2 PREVIOUS YEAR (AIIMS)
1. One gram sample of NH4NO3 is decomposed in a 6. For a spontaneous process the correct statement is
bomb calorimeter. The temperature of the calorimeter (A) entropy of the system always increases
increases by 6.12 K. The heat capacity of the system (B) free energy of the system always increases
is 1.23 kJ/g/deg. What is the molar heat of (C) total entropy change is always negative
decomposition for NH4NO3?
(D) total entropy change is always positive.
(A) – 7.53 kJ/mol (B) – 398.1 kJ/mol [2006]
(C) – 16.1 kJ/mol (D) 602 kJ/mol 7. For a phase change
[2003]
H2O (l ) H2O (s)
2. Which one of the following has 'S° greater than 0°C, 1 bar
zero ? (A) 'G° = 0 (B) 'S° = 0
(A) CaO(s) + CO2(g) UCaCO3(s) (C) 'H° = 0 (D) 'U° = 0
(B) NaCl(aq) U NaCl(s) [2006]
(C) NaNO3 (s) U Na+( aq) + NO–3 (aq)
8. The enthalpy change ('H) for the reaction,
(D) N2 (g) + 3H2 (g) U 2NH3(g) [2003]
N2(g) + 3H2(g) o 2NH3(g)
3. How much energy is released when 6 moles of is – 92.38 kJ at 298 K. The internal energy change
octance is burnt in air ? Given 'Hof for CO2(g), H2O(g) 'U at 298 K is
(A) –92.38 kJ (B) –87.42 kJ
and C8H18(l) respectively are –490, –240 and +160 kJ/
mol. (C) –97.34 kJ (D) –89.9 kJ
[2006]
(A) –6.22 kJ (B) 37440 kJ/mol
(C) – 35502 kJ (D) – 20.0 kJ 9. Calculate change in internal energy if 'H = – 92.2 kJ,
[2004] P = 40 atm and 'V = – 1L.
(A) –42 kJ (B) –88 kJ
4. 'Hof (298 K) of methanol is given by the chemical (C) +88 kJ (D) +42 kJ
equation [2007]
1 10. 'Hfusion of a substance is ‘x’ and 'Hvap is ‘y’, then

(A) CH 4(g) O 2(g) o CH 3 OH (g)
2 'Hsublimation will be
(A) x + y (B) x – y
1
(B) C (graphite) O 2(g) 2H 2(g ) o CH 3 OH ( l ) (C) x/y (D) y/x [2007]
2
11. 'Ssurr for an exothermic reaction is
1 (A) always positive
(C) C (diamond) O 2(g) 2H 2(g) o CH 3OH (l )
2 (B) always negative
(D) CO(g) + 2H2(g) o CH3OH(l) [2005] (C) zero
5. For the reaction of one mole of zinc dust with one (D) may be positive or negative [2007]
mole of sulphuric acid in a bomb calorimeter, 'U 12. In an isobaric process, when temperature changes
and w corresponds to from T1 to T2, 'S is equal to
(A) 'U < 0, w = 0 (B) 'U < 0, w < 0 (A) 2.303 CP log (T2/T1) (B) 2.303 CP ln (T2/T1)
(C) 'U > 0, w = 0 (D) 'U > 0, w > 0 (C) CP ln (T1/T2) (D) CV ln (T2/T1)
[2005, 2015] [2009]
58
13. The variation of volume V, with temperature T,
18. Which of the following is intensive property ?
keeping pressure constant is called the coeffcient
(A) Enthalpy (B) Entropy
of thermal expansion ($ $ ) of a gas. i.e.,
(C) Specific heat (D) volume
1 § wV · [2011]
D ¨ ¸ . For an ideal gas D is equal to
V © wT ¹ P
19. Bond dissociation energy of CH4 is 360 kJ/mol and
(A) T (B) 1/T C2H6 is 620 kJ/mol. Then bond dissociation energy
(C) P (D) 1/P [2009] of C – C bond is
(A) 170 kJ/mol (B) 50 kJ/mol
14. Mathc List I with List II and select the correct answer
using the codes given below the lists : (C) 80 kJ/mol (D) 220 kJ/mol
[2012]
List I List II
20. Which thermodynamic parameter is not a state
§ GG ·
A. ¨ ¸ 1. PJT function ?
© GP ¹T
(A) q at constant pressure
§ GG · (B) q at constant volume
B. ¨ ¸ 2. T (C) W at adiabatic
© GT ¹P
(D) W at isothermal [2013]
§ GH · 21. A diatomic gas at pressure P, compressed
C. ¨ ¸ 3. –S adiabatically to half of its volume, what is the final
© GS ¹P
pressure ?
§ GT · (A) (2)1.4P (B) P/(2)1.4
D. ¨ ¸ 4. P
© GP ¹H (C) (2) P (D) P/(2)5/3
5/3
[2014]
5. V
22. The heat liberated when 1.89 g of benzoic acid is
A B C D
burnt in a bomb calorimeter at 25°C and it increases
(A) 5 1 2 4
the temperature of 18.94 kg of water by 0.632°C. If
(B) 5 3 2 4 the specific heat of water at 25°C is 0.998 cal/g-deg,
(C) 3 5 2 1 the value of the heat of combustion of benzoic acid
(D) 5 3 2 1 [2010] is
(A) 881.1 kcal (B) 771.124 kcal
15. The enthalpy of formation of CO(g), CO2(g), N2O(g)
and N2O4(g) is – 110, –393, +811 and 10 kJ/mol (C) 981.1 kcal (D) 871.2 kcal
respectively. For the reaction, [1994, 2016]
N2O4(g) + 3CO(g) o N2O(g)+ 3CO2(g).'Hr(kJ/mol) is
(A) – 212 (B) + 212 23. The molar heat capacity of water at constant
pressure is 75 JK–1 mol–1. When 1kJ of heat is supplied
(C) + 48 (D) – 48 [2011]
to 100 g of water, which is free to expand, the increase
16. For adiabatic process, which is correct ? in temperature of water is [2017]
(A) 'T = 0 (B) 'S = 0 (A) 6.6 K (B) 1.2 K
(C) q = 0 (D) qP = 0 (C) 2.4 K (D) 4.8 K
[2011]
24. The 'f H° for CO2(g) , CO(g) and H2O(g) are – 393.5,
17. Which of the following is not a thermodyanmic –110.5 and –241.8 kJ/mol respectively, the standard
function ? enthalpy change (in kJ) for the reaction [2017]
(A) Internal energy (B) Work done CO2(g) + H2(g) o CO(g) + H2O(g) is :
(C) Enthalpy (D) Entropy (A) 524.1 (B) 41.2
[2011] (C) – 262.5 (D) – 41.2
59
25. One monoatomic gas is expanded adibatically from energy, i.e., 'H has a high positive value and T'S a
2L to 10 L at 1 atm external pressure find 'U (in atm low negative value. [2007]
L) ? [2018]
32. Assertion : Many endothermic reaction that are not
(A) –8 (B) 0
spontaneous at room temperature become
(C) –66.7 (D) 58.2
spontaneous at high temperature.
Reason : Entropy of the system increases with
26. Which are extensive properties [2018] increase in temperature. [2008]
(A) V & E (B) V & T
(C) V & Cp (D) P and T. 33. Assertion : Heat of neutralisation of nitric acid with
NaOH is same as that of HCl and NaOH.
ASSERTION AND REASON Reason : In both cases strong acid and strong bases
In each of the following questions, two statement are neutralised.
are given one is assertion and the other is reason. H+ + OH– o H2O [2009]
Examine the statement carefully and mark the correct
answer according to the instruction given below 34. Assertion : A reaction which is spontaneous and
(A) If both the assertion and reason are true and accompanied by decrease of randomness must be
reason explains the assertion exothermic.
(B) If both the assertion and reason are true but Reason : All exothermic reactions are accompanied
reason does not explain the assertion by decrease of randomness. [2009]
(C) If assertion is true but reason is false 35. Assertion : Entropy is always constant for a closed
(D) If assertion is false but reason in true system.
(E) Both assertion & reason are false Reason : Closed system is always reversible.
[2011]
27. Assertion : The increase in internal energy ('E) for
the vaporization of one mole of water at 1 atm and 36. Assertion : For an isolated system, q is zero.
373 K is zero. Reason : In an isolated system, change in U and V is
Reason : For all isothermal processes, 'E = 0. zero [2013]
[2003] 37. Assertion : Entropy of system increases for a
spontaneous reaction.
28. Assertion : 'H and 'E are almost the same for the
reaction, N2(g) + O2(g) U 2NO(g). Reason : Enthalpy of reaction always decreases for
spontaneous reaction. [2013]
Reason : All reactants and products are gases.
[2003] 38. Assertion : A process is called adiabatic if the
system does not exchange heat with the
29. Assertion : Water in liquid state is more stable than
surroundings.
ice at room temperature.
Reason : It does not involve increase or decrease in
Reason : Water is more polar than ethanol.
temperature of the system. [2013]
[2004]
39. Assertion : A reaction which is spontaneous and
30. Assertion : Water in liquid state is more stable than accompanied by decrease of randomness must be
ice at room temperature. exothermic.
Reason : Water is liquid form has higher entropy Reason : All exothermic reactions are accompanied
than ice. [2004] by decrease of randomness. [2016]
31. Assertion : As a salt such as NaCl dissolves, the
Na+ and Cl– ions leaving the crystal lattice acquire 40. Assertion : Heat of neutralisation for both H2SO4
far greater freedom. and HCl with NaOH is 53.7 kJ mol–1.
Reason : In thermodyanamic terms, the formation of Reason : Both HCl and H2SO4 are strong acids.
solution occurs with a favourable change in free [2016]
60
EXERCISE : PART - 1
1. D 2. B 3. A 4. D 5. D 6. B 7. A 8. B 9. B 10. C 11. A 12. B 13. A
14. A 15. A 16. A 17. B 18. D 19. B 20. C 21. C 22. B 23. B 24. C 25. A 26. C
27. A 28. C 29. A 30. B 31. B 32. A 33. A 34. B 35. C 36. C 37. C 38. B 39. A
40. C
PART - 2
1. D 2. C 3. B 4. B 5. A 6. D 7. A 8. B 9. B 10. A 11. D 12. A 13. B
14. D 15. D 16. C 17. B 18. C 19. C 20. D 21. A 22. B 23. C 24. B 25. A 26. A
27. A 28. B 29. B 30. A 31. C 32. B 33. A 34. C 35. D 36. B 37. A 38. C 39. C
40. A
61
40-65*0/4 THERMODYNAMICS AND THERMOCHEMISTRY
EXERCISE
5. (D) : For reaction,
P-1 (NEET/AIPMT)
H2(g) + Br2(g) o 2HBr(g) 'H° = ?
1. (D) : According to heat capacity rule, 'H° = – [(2 × bond energy of HBr) – (bond energy of H2
q + bond energy oc Cl2)]
q = mc'T, c
m(T2 T1 ) 'H° = – [2 × (364) – (433 + 192)] kJ
= – [728 – (625)] kJ = – 103 kJ
Given that, c = 75 JK–1 mol–1
q = 1.0 kJ = 1000 J 6. (B) : 'G° = 'H° – T'S° ...(i)
Mass = 100 g water Given that, DH° = – 382.64 kJ mol–1
Molar mass of water = 18 g 'S° = – 145.6 J K–1 mol–1
= – 145.6 × 10–3 kJ K–1
1000
75 T = 298 K
5.55 u 'T
On putting the given values in eq. (i) we get,
§ 100 · or 'G° = – 382.64 – [298 × (– 145.6 × 10–3)]
¨ Number of moles = 5.55 ¸
= – 339.3 kJ mol–1
© 18 ¹
7. (A) : For spontaneous process, 'S must be positive. In
1000
? 'T 2.4 K reversible process
5.55 u 75
' Ssystem + ' Ssurrounding = 0
2. (B) : 'Hf = 6.0 kJ mol –1 Hence, system is present in equilibrium.
T = 0 + 273 = 273 K (i.e. it is not spontaneous process)
While in irreversible process
'H f 6.0
'S 0.02198 kJ K 1 mol1 'Ssystem + 'Ssurrounding > 0
T 273
Hence, in the process DS is positive.
(T = 0 °C + 273 = 273 K)
= 0.2198 × 1000 JK–1 mol–1 8. (B) : Work done (W) = – pext (V2 –V1)
= 21.98 JK–1 mol–1 = – 3 × (6 – 4) = – 6 L atm
= – 6 × 101.32 J
3. (A) : When one mole of a substance is directly formed (' 1 L atm = 101.32 J)
from its constituent elements, then the enthalpy change
= – 607.92 | – 608 J
is called heat of formation.
For the reaction, 9. (B) : The spontaneity of a reaction is based upon the
negative value of 'G and 'G is based upon T. 'S and
Xe(g) 2F2 (g) o XeF4 (g)
1 mol 'H according to following equation (Gibbs - Helmholtz
equation)
'Hq react 'Hqf 'G = 'H – T'S
If the magnitude of 'H – T'S is negative, then the reac-
4. (D) : For the reaction, tion is spontaneous.
C3H8(g) + 5O2(g) o 3CO2(g) + 4H2O(l) when T'S > 'H or we can say that 'H and 'S are posi-
'ng = number of gaseous moles of products tive, then 'G is negative.
– number of gaseous moles of reactants
10. (C) : If reaction is exothermic, therefore 'H is negative
=3–6=–3
and on increasing disorder, 'S is positive thus, at these
? 'H = 'E + 'nRT
condition, 'G is negative according to following equa-
or 'H – 'E = 'nRT
tion.
? 'H – 'E = – 3RT
62
'G = 'H – T'S = – [– 3921 – (– 3800 – 24)] kJ
'G = negative, and for spontaneous reaction DG must = – [–3920 + 4041] kJ = – [121] kJ = – 121 kJ
be negative.
16. (A) : Enthalpy of formation : The amount of heat evolved
11. (A) : Heat of neutralisation of strong acid and strong or absorbed during the formation of 1 mole of a com-
base is –57.33 kJ. MgO is weak base while HCl is strong pound from its constituent elements is known as heat of
acid, so the heat of neutralisation of MgO and HCl is formation So, the correct answer is
lower than –57.33 kJ because MgO requires some heat
1
for ionisation, therefore the net released amount of heat H 2 (g) O 2 (g) o H 2 O(l),
2
is decreased.
'H = – x2 kJ mol–1
12. (B) : If the Gibbs free energy for a system ('Gsystem) is
equal to zero, then system is present in equilibrium at a 17. (B) : 'Hreaction = 'H–H + 'HCl–Cl – 2'HHCl
constant temperature and pressure.
430 240 ( 90)
'G = 'r G° + RT ln K ; 'G = 0 or 'H H Cl
2
'rG° = – RTln K
K = equilibrium constant 760
380 kJ mol 1
If 'Gsystem < 0, then the process is spontaneous 2
13. (A) : As we know that, 18. (D) : The thermodynamic parameters which depend only
'H = 'E + p'V or 'H = 'E + 'ngRT upon the initial and final states of system, are called
where, 'ng o number of gaseous moles of product state functions, such as enthalpy (H = q + W), Gibbs free
– number of gaseous moles of reactant energy (G = H – TS), etc. While those parameters which
If 'ng = 0 (for reactions in which the total number of depend on the path by which the process is performed
moles of gaseous product are equal to total number of rather than on the initial and final states, are called path
moles of gaseous reactants), therefore 'H = 'E functions, such as work done, heat, etc.
So, for reaction (A) 'n = 2 – 2 = 0 19. (B) : From enthalpy equation, 'H = 'E + ngRT
Hence, for reaction (A), 'H = 'E For the reaction, PCl5(g)  PCl3(g) + Cl2(g)
14. (A) : At equilibrium Gibbs free energy change ('G) is 'ng = product mole – reactant mole 'n = 2 – 1 = 1
equal to zero. Thus, the value of 'H is positive or > 0.
'G = 'H – T'S 'G = 'H – T'S
0 = 30 × 103 (J mol–1) – T × 105 (J K–1 mol–1) For a spontaneous reaction 'G must be negative. Since
in this reaction 'H is positive, so for the negative value
30 u 103 of 'G, 'S must be positiver or > 0.
? T K 285.71K
105
Hence, 'H > 0, 'S > 0
20. (C) : For reaction,
15. (A) : + H2 H H H H
C C H H H C C H
Cyclohexene Cyclohexane
H H H H
'H = ?
'H = ['H of combustion of cyclohexane 'Hreaction
– ('H of combustion of cyclohexene
¦ BE(reactant) ¦ BE (Pr oduct) ,[BE bond energy]
+ 'H of combustion of H2)]
63
'Hr = [4 × BE(C–H) + 1 × BE(C=C) + 1 × BE(H–H)] = + 37.56 kJ mol–1
– [6 × BE(C–H) + 1 × BE(C–C)]
26. (C) : Molar entropy change for the melting of ice,
= (4 × 410.50 + 1 × 606.10 + 1 × 431.37)
– [(6 × 410.50) + 1 (1 × 336.49)]kJ mol–1 'H fusion 1.435 kcal / mol
'Smelt
= [1642 + 606.1 + 431.37] – [2463 + 336.49]kJ mol –1 T (0 273) K
= [2679.47] – [2799.49] kJ mol–1 = – 120.0 kJ mol–1 = 5.26 × 10–3 kcal/mol K
21. (C) : Given, 'H = 170 kJ = 170 × 103 J = 5.26 cal/mol K
'S = 170 JK–1; T = ? 27. (A) : Among the given reactions only in the case of
'G = 'H – T'S
1
For spontaneous reaction, C (graphite) O1 (g) o CO g
2
'G < 0 0 < 170 × 103 – T × 170 ; T > 1000
? T = 1110 K entropy increases because randomness (disorder) in-
creases. Thus, standard entropy change ('S°) is posi-
22. (B) : 4H(g) o 2 H2(g), 'H = – 869.6 kJ tive. Moreover, it is a combustion reaction and all the
2 H2(g) o 4H(g), 'H = 869.6 kJ combustion reactions are generally exothermic, i.e. 'H°
H2(g) o 2H(g), = – ve
Dissociation energy of H–H bond We know that,
'G° = 'H° – T'S°
869.6
434.8 kJ 'G° = – ve – T(+ ve)
2
Thus, as the temperature increases, the value of 'G°
23. (B) : In adiabatic process, heat exchange is constant, so decreases.
q = 0 and for free expanion, W = 0, ? 'T = 0
28. (C) : energy profile diagram for a reaction is as
24. (C) : 'G° = 'H° – T'S°
Given, 'Hvap.= 30 kJ mol–1
T = 27 + 273 = 300 k
'G° = 0 at equilibrium, (Ea)f
(Ea)b
'H vap 30 u 103 J mol1 H
'Svap
T 300 K
= 100 J mol–1 K–1 Progress of the reaction
100q C
25. (A) : H 2O(l) o H 2O(g) From the figure, it is clear that
'vapH° = 'vapE° + 'ngRT (Ea)b = (Ea)f + 'H
'vapH° = enthalpy of vaporisation [Here (Ea)b = activation energy of backward reaction and
= 40.66 kJ mol–1 (Ea)f = activation energy of forward reaction].
For the above reaction, If (Ea)b = (Ea)f
'ng = np – nr = 1 – 0 = 1 then 'H = 0
R = 8.314 29. (A) : The equilibrium constant at two different tempera-
T = 100°C = 273 + 100 = 373 K tures for a thermodynamic process is given by
? 40.66 kJ mol–1 = 'vapE° + 1 × 8.314 × 10–3 × 373
'vapE° = 40.66 kJ mol–1 –3.1 kJ mol–1 K2 'Hq ª 1 1 º
log « »
K1 2.303R ¬ T1 T2 ¼
64
Here, K1 and K2 are replaced by Kp and K'p. then 'G = 'G° + 2.303 RT log K = 0
'G° = – 2.303 RT log K
K 'p 'H q ª 1 1 º
Therefore, log « » 33. (A) : Given, C(s) + O2(g) o CO2(g);
Kp 2.303R ¬ T1 T2 ¼
'f H = – 393.5 kJ mol–1
For exothermic reaction,
' Heat released on formation of 44 g or 1 mole
T2 > T1 and H = – ve
CO2 = –395.5 kJ mol
? Kp > K'p
' Heat released on formation of 35.2 g of CO2
30. (B) : The change in Gibbs free energy is given by
393.5kJmol1
'G = 'H – T'S u 35.2g 315 kJ mol 1
44g
where, 'H = change enthalpy of the reaction
'S = change entropy of the reaction 34. (B) : Entropy change is given as,
Thus, in order to determine 'G, the values of 'H must be
known. The value of 'H can be calculated by using Tf p
'S nCp ln nR ln i ...(i)
equation Ti pf
'H = 'U + 'ngRT ...(i) for isothermal process, Ti = Tf
where, 'U = change in internal energy using
Tf Tf
'ng = number of moles of gaseous products – ? nC p ln nC p ln 0 [ln 1 = 0]
Ti Ti
number of moles of gaseous reactants
=2–0=2
pi
R = gas constant = 2 cal For Eq. (i) 'S nR ln
pf
given, 'U = 2.1 kcal
= 2.1 × 103 cal [' 1 kcal = 103 cal] 35. (C) : The given phase quilibria is Liquid  Vapour.
By putting the values in eq. (i) we get, This equilibrium states that, when liquid is heated, it
converts into vapour but on cooling, it further converts
? 'H = (2.1 × 103) + (2 × 2 × 300)
into liquid, which is derived by Calusius Clapeyron and
= 3300 cal
the relationship is writtern as,
Hence, 'G = 'H – T'S
'G = (3300) – (300 × 20) d ln p 'H v

'G = – 2700 cal dT RT 2
? 'G = – 2.7 kcal where, 'Hv = Heat of vaporisation
31. (B) : 'S [change in entropy] and 'H [change in enthalpy] 36. (C) : A catalyst is a substance which alters the reaction
as related by the equation 'G = 'H – T'S rate but itself remains unchanged in amount and chemi-
[Here, 'G = change in Gibbs free energy] cal composition at the end of the reaction. It provides a
For adsorption of a gas, 'S is negative because random- new reaction path with a lower energy barrier (lowering
ness decreases. Thus, in order to make 'G negative [for actavation energy).
spontaneous reaction], 'H must be highly negative.
Hence for the adsorption of a gas, if 'S is negative,
therefore, 'H should be highly negative.
32. (A) : Mathematical expression of the thermodynamic equi-

librium is
'G = 'G° + 2.303RT log Q
At equilibrium when 'G = 0 and Q = K
65
B Activated complex without catalyst 39. (A) : Because graph for 'fG°, of BeO is below then graph
Activated complex with catalyst of 'fG°, of Al2O3 in ellingham diagram.
Lowest energy of activation
provided by the catalyst
Ea
through ne reaction pathway 40. (C) : for exothermic reaction lower temperature favours
Energy
ER
product
Reactants
EP
Products
Progress of reaction
37. (C) : Key concept According to first law of thermody-

namics,
'U = q + w
where, 'U = internal energy
q = heat absorbed or evolved, w = work done.
Also, work done against constant external pressure (ir-
reversible process).
w = – pext DV.
Work done in irrversible process.
w = – pext 'V = – pext (V2 – V1)
= – 25 atm (4.5 L – 2.5 L)
= – 5 L atm = – 5 × 1013 J
= – 505 J
Since, the system is well insulated, q = 0
? 'U = w = – 505 J
Hence, change in internal energy, 'U of the gas
is – 505 J.
38. (B) : According to Gibbs-Helmholtz equation,

Gibbs energy ('G) = 'H – T'S
Where, 'H = Enthalpy change
'S = Entropy change
'S = Entropy change
T = Temperature
For a reaction to be spontaneous
'G < 0
? Gibbs – Helmholtz equation becomes,
'G = 'H – T'S < 0
or, 'H < T'S
'H 35.5 kJ mol1 35.5 u 1000

or, T!
'S 8.6 JK 1mol 1 83.6
T > 425 K
66
EXERCISE
7. (A) : 'G° = – RTlnk['G° = standard free energy change,
P-2 (AIIMS) K = equilibrium constant]
Ir a substance is in equilibrium between two phases at
1. (D) : Heat of decomposition, 'E = m.s.'T
constant temperature and pressure, its chemical potential
= 1 u 1.23 u6.12 = 7.5276 kJ
must have the same value in both the phases.
Molar heat of decomposition for NH4NO3 = 7.5276 u 80
? DG° = 0.
= 602.2 kJ
8. (D) : 'H = 'U + 'nRT
2. (C) : Here, the number of product species is greater than
the number of reactant species. So it leads to positive [where 'n = no. of molecules of products
value of entropy. – no. of molecules of reactants]
or, – 92.38 u 1000 = 'U – 2 u 8.314 u 298
3. (B) : C + O2 o CO2, or, DU = – 87424 J = – 87.424 kJ
'Hqf – kJ/mol u 8 (i)
9. (B) : 'H = 'E + P'V
1 'E = 'H – P'V = – 92.2 – 40 u (–1) u 101 u 10–3
H 2 O 2 o H 2 O, = – 92.2 + 4.04 = – 88.16 kJ | – 88 kJ
2
'Hqf 240 kJ/mol u 9 (ii) 10. (A) : Solid

fusion
o Liquid 'Hfusion = x
8C + 18H o C8H18, Liquid o
vaporisation
Gas 'Hvap = y
q
'H 160 kJ/mol (iii) 'Hsub = ?
f Solid
sub lim ation
o Gas
9 So, 'Hsub = 'Hfusion + 'Hvap, 'Hsub = x + y
8C + 8O2 + 9H + O – 8C – 18H
2 2 11. (D) : In exothermic processes, heat released by the
o 8CO2 + 9H2O – C8H18 reaction increases the entropy of the surrounding. The
overall entropy change is certainly positive when the
'Hqf 3920 2160 160
entropy of the system is positive when the entropy of
the system is positive. In some exothermic reaction,
25
C8 H18 O 2 o 8CO 2 9H 2 O; 'Hq 6240 kj / mol entropy of the system may decrease. If reaction is highly
2
exothermic and increase in entropy of the surroundings
'H° for 6 moles of octane = 6240 u 6 = 37440 kJ/mol is very high, the total entropy change will be positive
and the reaction will be spontaneous.
4. (B) : Methanol can be prepared synthetically by heating
carbon monoxide and hydrogen gas under pressure in 12. (A) : The entropy change for a process, when T and P
the presence of a catalyst. are the variables is given by
C (graphit) + 1/2 O2(g) o CO(g) ....(i)
T2 P
CO(g) + 2H2(g) o CH3OH(l) ....(ii) 'S C P ln R ln 2
T1 P1
C(graphite) + 1/2 O2(g) + 2H2(g) o CH3OH(l)
For an isobaric process P1 = P2, Hence the above equation
5. (A) : Bomb calorimeter is commonly used to find the
reduces to
heat of combustion of organic substances which
consists of a sealed combustion chamber, called a bomb. T2 T2
C P ln 'S or 'S 2.303C P log
If a process is run in a sealed container then no expansion T1 T1
of compression is allowed, so w = 0 and 'U = q.
'U < 0, w = 0 13. (B) : For n moles of an ideal gas PV = nRT
6. (D) : 'Stotal = 'Ssystem + 'Ssurroundings RT

or V n
For a spontaneous process 'Stotal must be positive. i.e. P
'Stotal > 0. Differentiating with respect to T at constant P, we have
67
20. (D) : H and U are state function but W and q are not state
§ wV · nR V
¨ ¸ functions.
© wT ¹P P T
From the equation, 'H = 'U + 'PV
At constant pressure, 'H = 'U + P'V
1 § wV · 1 V 1
D ¨ ¸ u At constant volume, 'H = 'U + V'P
V © wT ¹ P V T T
At constant pressure, 'P = 0, 'U = qv
14. (D) : From thermodynamics, dG = VdP – SdT so, it is a state function.
work done in any adiabatic process is state function.
§ GG · 'U = q – W (? q = 0)
At constant T, dT = 0 so that ¨ GP ¸ V
© ¹T 'U = – W
Work done in isothermal process is not a state function.
§ GG ·
At constant P, dP = 0 so that ¨ GT ¸ S W=–q (' 'T = 0, z 0)
© ¹P
21. (A) : For adiabatic conditions, PVJ = Constant
§ GT ·
Also PS ¨ ¸ 1
© GP ¹H P1V1J P2 V2J ; V2 V1
2
15. (D) : N2O4(g) + 3CO(g) o N2O(g) + 3CO2(g) J
'Hreaction = 6Heat of formation of products – 6Heat of formation of reactants §V ·
P2 P1 ¨ 1 ¸ [For diatomic gas, J = 1.4]
DHreaction = ['HfN2O + 3 u 'HfCO2] – © V2 ¹
['HfN2O4 + 3 u 'HfCO]
1.4
'Hr = [+ 811 + 3(–393)] – [10 + 3(–110)] § V u2 ·
P2 P1 ¨ 1 ¸
= [811 – 1179] – [– 320] = – 368 + 320 © V1 ¹
= – 48 kJ/mol
P2 = P1 (2)1.4 = (2)1.4 P
16. (C) : For adiabatic process, no exchange of heat takes
place between the system and surroundings. i.e. q = 0. 22. (B) : Given : Weight of benzoic aicd = 1.89 g; Temperature
of bomb calorimeter = 25°C = 298 K; Mass of water (m) =
17. (B) : Thermodynamic function are : internal energy,
18.94 kg = 18940 g; Increase in temperature ('T) = 0.632°C
enthalpy, entropy, pressure, volume, temperature, free
and specific heat of water (s) = 0.998 cal/g-deg.
energy, number of moles.
We know that heat gained by wate or heat liberated by
18. (C) : Intensive property : Specific heat benzoic acid (Q) = m s'T
Extensive property : Enthalpy, entropy, volume. = 18940 u 0.998 u 0.632 = 11946.14 cal.
Since 1.89 g of acid liberates 11946.14 cal of heat, therefore
19. (C) : Dissociation energy of methane = 360 kJ mol–1
heat liberated by 122 g of acid
360
? Bond energy of C–– H bond 90 kJ 11946.14 u 22
4
1.89
Bond energy of ethane,
= 771126.5 cal = 771.12 kcal
1(C –– C) + 6 (C –– H) = 620 kJ/mol
(where 122 g is the molecular weight of benzoic acid)
C –– C + 6 u 90 = 620
C –– C = 540 = 620 23. (C) Given Cp = 75 JK–1 mol–1
C –– C = 620 – 540
100
C –– C = 80 kJ mol–1 n= mole, Q = 1000 J 'T = ?
18
Bond dissociation of C –– C bond = 80 kJ mol–1
1000 u18
Q = nCp'T 'T = = 2.4 K
100 u 75
68
–ve = 'H – [T (–ve)] (as spontaneous)
24. (B) 'H ¦ ª¬ 'H f products º¼ ¦ ª¬ 'H f reactants º¼
0 0
Exothermic reactions may be accompanied by increase

or decrease of randomness.
'H° = ª¬ 'H f (CO)(g) 'H f (H 2 O)(g) º¼ –
0 0
35. (D) : For a closed system, the entropy can increase,

ª¬ 'H 0f (CO 2 )(g) 'H 0f (H 2 )(g) º¼ decrease or remain constant.
= [– 110.5 + ( – 241.8)]– [– 393.5 + 0] = 41.2 Closed system can be reversible or irreversible.
36. (B) : For an isolated system,

25. (A) : Process is adiabatic ? Q = 0
W=q=0
? 'U = W = – Pext 'V
'U = q + W
= – 1 (10 – 2) atm L
Hence, 'U = 0
= – 8 atm L
W = P'V
26. (A) : Extensive quantities depend upon quantity of
as W = 0 so, 'V = 0
substance.
37. (A) : 'S is +ve and 'H is –ve for a spontaneous reaction
27. (A) : At 373 K or 100°C, the water starts boiling and at
at all temperatures.
this temperature the vapourzation of water is an
isothermal process. 38. (C) : It may involve increase or decrease in temperature
The internal energy change ('E), depend only on of the system. Systems in which such process occur, are
temperature, it follows that at constant temperature, the thermally insulated from the surroundings.
internal energy of the gas remains constant, i.e. 'E is
39. (C) : 'G = 'H – T'S
zero.
As the reaction is accompanied by decrease in
28. (B) : 'H = 'E + 'nRT
randomness,
'n = change in number of moles of products and reactant
'G = 'H + T'S [' 'S is negative]
species.
For reaction to be spontaneous 'G should be negative
N2(g) + O2(g) U 2NO(g)
which is possible only if reaction is highly exothermic
'n = 2 – 2 = 0
i.e. 'H is negative.
'H = 'E + 0 u RT or, 'H = 'E
Exothermic reactions may be accompanied by increase
29. (B) : Molar entropy of vaporization of water is more than or decrease of randomness.
ethanol, as water has greater forces of attraction than
40. (A)
ethanol.
30. (A) : Fusion of ice is a spontaneous process, because

the process again proceeds in the direction of more
random state, i.e. liquid state is more random (higher
entropy) in comparison to solid state. i.e. ice.
31. (C) : In thermodynamic terms, formation of solution

occurs with a favourable change in free energy
'G = 'H – T'S
where 'H has a small positive value and T'S a large
positive value; thus 'G is negative.
32. (B) : The factor T'S increases with increase in

temperature.
33. (A)
34. (C) : 'G = 'H – T'S
69
REDOX REACTION
CHAPTER
06
The meeting of two personalities is like the contact of two chemical
substances; if there is any reaction, both are transformed
“CARL JUNG”
INTRODUCTION
A
number of phenomena, both phtysical as well as biological, are concerned with redox
reaction. These reactions find extensive use in pharmaceutical, biological, industrial,
metallurgical and agricultural areas. The importance of these reactions is apparent
from the fact that burning of different types of fuels for obtaining energy for domes-
tic, transport and other commercial purposes, electrochemical processes for extrac-
tion of highly reactive metals and non-metals, manufacturing of chemical compounds
like caustic soda, operation of dry and wet batteries and corrosion of metals fall
within the purview of redox processes. Of late, environmental issues like Hydrogen
Economy (use of liquid hydrogen as fuel) and development of ‘Ozone Hole’ have
started figuring under redox phenomenon.
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Redox Reaction (Oxidation-Reduction) :
Many Chemical reactions involved transfer of electrons from one chemical substance to another. These electron-
transfer reactions are termed as Oxidation-Reduction or Redox reactions.
Or
Those reactions which involves oxidation and reduction both simultaneously are known as oxidation and reduction or
Redox Reaction.
Or
Those reaction which involves increase in oxidation number and decrease in oxidation number simultaneously are
known as Oxidation & Reduction or Redox Reaction.
Oxidation and Reduction :

There are four concepts for oxidation and reduction reactions.
(I) Classical concept (II)Modern concept
(III)Valency concept (IV)Oxidation number concept.
(I) Classical concept : According to this concept, oxidation and reduction can be explained as:
(A) Oxidation : Oxidation is a process which involves.
(i) Addition of Oxygen :
Ex. 2Mg + O2 o2MgO (Oxidation of Magnesium)
C + O2 o CO2 (Oxidation of Carbon)
Na2SO3 + H2O2 o Na2SO4 + H2O (Oxidation of Sodium sulphite)
(ii) Removal of Hydrogen :
Ex. H2S + Cl2 o 2HCl + S (Oxidation of Hydrogen sulphide)
4HI + O2 o 2H2O + 2I2 (Oxidation of Hydrogen iodide)
(iii) Addition of Electronegative element :
Ex. Fe + S o FeS (Oxidation of iron)
SnCl2 + Cl2 o SnCl4 (Oxidation of stannous chloride)
2FeCl2 + Cl2 o 2FeCl3 + 2H2O (Oxidation of ferric chloride)
(iv) Removal of Electropositive element :
Ex. 2NaI + H2O2 o2NaOH + I2 (Oxidation of NaI)
2KI + Cl2 o2KCl + I2 (Oxidation of KI)
2K2MnO4 + Cl2 o2KCl + 2KMnO4 (Oxidation of Potassium magnate)
(v) Increment in oxidation state of Electropositive element :
Ex. SnCl2 + Cl2 oSnCl4
Sn+2 Sn+4
(B) Reduction : Reduction is a process which involves
(i) Removal of Oxygen :
Ex. CuO + C oCu + CO (Reduction of cupric oxide)
H2O +C o CO + H2 (Reduction of water)

Water gas
Steam coke
Fe3O4 + 4H2 o3Fe + 4H2O (Reduction of Fe3O4)
(ii) Addition of Hydrogen
Ex. N2 + 3H2 o2NH3 (Reduction of Nitrogen)
Cl2 + H2 o2HCl (Reduction of Chlorine)
S + H2 o H2S (Reduction of Sulphur)
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REDOX REACTION
(iii) Removal of Electronegative element
Ex. 2HgCl2 + SnCl2 o Hg2Cl2 + SnCl4 (Reduction of mercuric chloride)
2FeCl3 + H2 o 2FeCl2 + 2HCl (Reduction of ferric chloride)
(iv) Addition of Electropositive element
Ex. HgCl2 + Hg oHg2Cl2 (Reduction of mercuric chloride)
CuCl2 + Cu oCu2Cl2 (Reduction of cupric chloride)
2HgCl2 + SnCl2 oHg2Cl2 + SnCl4 (Reduction of mercuric chloride)
(v) Decrement in oxidation state of Electropositive element
Ex. CuSO4 + Fe o FeSO4 + Cu (Reduction of CuSO4)
Cu+2 Cu°
FeCl3 + H2S oFeCl2 + 2HCl + S (Reduction of FeCl3)
Fe+3 Fe+2
(II) Modern concept or Electronic concept :-
(A) Oxidation : According to this concept the process which involves the loss of one or more electrons from an
atom or an ion or molecule is called oxidation (de-electronation).
Ex. M o M+n + ne–
Mg o Mg++ + 2e–
M n1 o M n 2 + (n2 – n1)e–

Fe ++ o Fe+++ + e–
(ferrous) (ferric)
A o A + ne–
–n
2Cl– o Cl2 + 2e –
A n1 o A n 2 + (n1 – n2) e–

[Fe(CN)6] o[Fe(CN)6]3– + e–
4–
(B) Reduction : According to this concept, the process which involves gain of one or more electrons by an atom
or ion or molecule is called reduction (electronation).
Ex. M n 2 + (n2 – n1)e–o M n1
Sn+4 + 2e– o Sn++
(Stannic ion) (Stannous ion)
A + ne– o A–n
Cl + e– o Cl–
n2
A n1 + (n2 – n1) e– o A
MnO4– + e– o MnO4–2
[Fe(CN)6]3– + e– o[Fe(CN)6]–4
(III) Valency concept of oxidation and reduction :
(A) Oxidation : According to this concept, it is the process in which increase in (+) ve valency or decrease in (–) ve
valency of a substance takes place called oxidation.
Ex. 2Mg + O2 o2MgO
(0) (2)
(ii) Reduction : According to this concept, the process in which (+) ve valency decreases whereas
(–) ve valency increases is called reduction.
Ex. 2HgCl2 + SnCl2 oHg2Cl2 + SnCl4
(+2) (+1)
(IV) Oxidation number concept :-
(A) Oxidation : According to this concept, the oxidation no. of an element in a reaction increases is called oxidation.
(B) Reduction : According to this concept, the oxidation no. of an element in a reaction is decrease is called
reduction.
72
Ex..
6H+ + 2MnO4– + 5H2S o 2Mn+2 + 5S + 8H2O
Mn+2 S–2 Mn+2 S°
Special Note :
Redox reaction involves two half reactions, one involving loss of electron called half oxidation reaction and the other
involving gain of electron called half reduction reaction.
–2e–
Oxidation
+2 +2
Ex. 2Hg + Sn Hg2+2 + Sn+4
–2e–
Reduction
Oxidising agent (oxidant) and reducing agent (Reductant)
Oxidising agent or Oxidant
Oxidising agents are those compounds which can oxidise others and reduce itself during the chemical reaction. Those
reagents in which for an element, oxidation number decreases or which undergoes gain of electrons in a redox reaction
are termed as oxidants.
Some important oxidising agents or oxidant :
(a) All high electronegative elements like N, O, F, Cl etc.
(b) All metallic oxides like Li2O, Na2O, Na2O2, CO2, CaO, MgO, BaO2 etc.
(c) Some nonmetallic oxides like CO2, SO2, H2O2, O3.
(d) All neutral compound or ion in which element shows their highest oxidation no or state, will act as oxidant or
oxidising agent like KMnO4, H2SO4, SnCl4,H3PO4, K2Cr2O7, HClO4, CuCl2, HNO3, H2SO5, FeCl3, HgCl2, etc.
Reducing agent or Reductant
Reducing agents are those compounds which can reduce other and oxidise itself during the chemical reaction. Those
reagents in which for an element, oxidation number increases or which undergoes loss of electrons in a redox reaction are
termed as reductants.
Ex. KI , Na2S2O3 etc are the powerful reducing agents.
Some important reducing agent or reductant :
(a) All metals like, K, Mg, Ca, etc.
(b) All metallic hydrides like NaH, CaH2, LiAlH4, NaBH4, AlH3 etc.
(c) All hydroacids like HF, HCl, HBr, H2S, etc.
(d) Some organic compound like Aldehyde, formic acid, oxalic acid, tartaric acid.
(e) All neutral compounds or ions, in which element shows their lowest oxidation no. or state, will act as reductant or
reducing agent
MnO, HClO, HClO2, H3PO2, HNO2, H2SO3, FeCl2, SnCl2, Hg2Cl2, CH2Cl2 etc.
Some important compound which can acts as oxidant and reductant both :
HNO2, SO2, H2O2, O3, Al2O3, CrO2, MnO2, ZnO, CuO
Note : Al2O3, CrO2, MnO2,ZnO, CuO are called as amphoteric oxide.
Ex. Oxidation is defined as –
(1) Gain of electrons (2) Decreases in positive valency
(3) Loss of electrons (4) Decreases in negative valency
Ans. (3)
Ex. Reduction is defined as –
(1) Increases in positive valency (2) Gain of electrons
(3) Loss of protons (4) Decreases in negative valency
Ans. (2)
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REDOX REACTION
Ex. In the reaction MnO4– + SO3–2 + H+ oSO4–2 + Mn2+ + H2O
(1) MnO4– and H+ both are reduced (2) MnO4– is reduced and H+ is oxidised
(3) MnO4 is reduced and SO3 is oxidised (4) MnO4– is oxidised and SO32– is reduced
– 2–
Ans. (3)
Ex. The charge on cobalt in [Co(CN)6]–3 is –
(1) –6 (2) –3 (3) +3 (4) +6
Ans. (3)
Ex. Which of the following halogen always show only one oxidation state –
(1) Cl (2) F (3) Br (4) I
Ans. (2)
Ex. Which of the following reactions do not involved oxidation-reaction –
(1) 2Rb + 2H2O o2RbOH + H2
(2) 2CuI2 o2CuI + I2
(3) NH4Cl + NaOH oNaCl + NH3 + H3O
(4) 3KCN + Fe (CN)2 o K4[Fe(CN)6]
Ans. (3)
Redox reaction in terms of electronic concept
Let us consider a redox reaction :
Reduction
2Na + Cl2 2NaCl
Oxidation
According to chemical bonding, here NaCl is an ionic compound. Hence, the above reaction can be written as
Gain of 2e---
+ --
2Na + Cl2 2Na + Cl
---
Loss of 2e
Here the above processes can be considered as two separate steps, one involving the loss of electrons and the other, the
gain of electrons.
2Na –o 2Na+ (loss of e–)
Cl2 –o 2Cl– (gain of e–)
Each of the above steps is called a half reaction. Sum of the half reactions gives the overall redox reaction. From the
above reaction it is clear that, “Half reactions that involve loss of electrons are called oxidation reactions”.
Similarly, “the half reactions that involve gain of electrons are called reducation reactions”.
For example :
Reduction
4Na + O2 2Na+2 O--2

(Reducing (Oxidising
agent) agent)
Oxidation
According to electronic concept, “oxidising agent is a substance which can accept one or more electrons”. And “the
reducing agent is a substance which can give one more electrons”.
Note : In short
74
Oxidation/Reducing agent – loss of electron
Reduction/Oxidising agent – gain of electron
Ex. In the given reaction, identify the species undergoing oxidation and reduction
(i) Mg + S ––o MgS
(ii) 2HgO ––o 2Hg + O2
Reduction
+2 ---2
Mg + S Mg S
Sol. (i)
Oxidation
Oxidation
2Hg+2 O---2 2Hg + O2

(ii)
Reduction
Ex. Using electronic concept, identify the oxidant and reductant in the following redox reactions.
(i) Zn + 2H+ ––o Zn+2 + H2
(ii) BrO3– + F2 + 2OH– ––o BrO4– + 2F– + H2O
Sol. (i) Zn 2H
o Zn 2 H 2
Reducing Oxidising
agent agent

(ii) BrO 3 F 2 2OH
o BRO 4 2F H 2 O
Reducing Oxidising
agent agent
Oxidation number
It is an imaginary or apparent charge developed over atom of an element when it goes from its elemental free state to
combined state in molecules.
It is calculated on basis of an arbitrary set of rules.
It is a relative charge in a particular bonded state.
In order to keep track of electron-shifts in chemical reactions involving formation of compounds, a more practical
method of using oxidation number has been developed.
In this method, it is always assumed that there is a complete transfer of electron from a less electronegative atom to a
more electronegative atom.
Rules governing oxidation number
The following rules are helpful in calculating oxidation number of the elements in their different compounds. It is to be
remembered that the basis of these rule is the electronegativity of the element .
Fluorine atom
Fluorine is most electronegative atom (known). It always has oxidation number equal to –1 in all its compounds
Oxygen atom
In general and as well as in its oxides , oxygen atom has oxidation number equal to –2.
In case of (I) peroxide (e.g. H2O2, , Na2O2 ) is –1,
(II) super oxide (e.g. KO2) is –1/2
(III) ozonide (e.g. KO3) is –1/3
(IV) in OF2 is + 2 & in O2F2 is +1
Hydrogen atom
In general, H atom has oxidation number equal to +1. But in metallic hydrides ( e.g. NaH, KH), it is –1.
Halogen atom
In general, all halogen atoms (Cl, Br , I) have oxidation number equal to –1.
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REDOX REACTION
But if halogen atom is attached with a more electronegative atom than halogen atom, then it will show positive oxidation
numbers.
+5 +5 +7 +5
Ex. K ClO , HIO , HCIO , KBrO
3 3 4 3
Metals
(a) Alkali metal (Li , Na, K, Rb, .......) always have oxidation number +1
(b) Alkaline earth metal (Be , Mg , Ca .......) always have oxidation number +2.
(c) Aluminium always has +3 oxidation number
Note : Metal may have negative or zero oxidation number
Oxidation number of an element in free state or in allotropic forms is always zero
0 0 0 0
Ex. O , S , P , O
2 8 4 3
Sum of the oxidation numbers of atoms of all elements in a molecule is zero.

Sum of the oxidation numbers of atoms of all elements in an ion is equal to the charge on the ion .
If the group number of an element in modern periodic table is n, then its oxidation number may vary from (n – 10) to
(n – 18) (but it is mainly applicable for p-block elements )
Ex. N- atom belongs to 15th group in the periodic table, therefore as per rule, its oxidation number may vary from
3 2 3 4 5
–3 to +5 ( N H3 ,NO , N 2 O 3 , N O 2 , N 2 O 5 )
The maximum possible oxidation number of any element in a compound is never more than the number of electrons in
valence shell.(but it is mainly applicable for p-block elements )
Calculation of average oxidation number
Ex. Calculate oxidation number of underlined element :

(a) Na2 S2O3 (b) Na2 S4O6
Sol. (a) Let oxidation number of S-atom is x. Now work accordingly with the rules given before .
(+1) × 2 + (x) × 2 + (–2) ×3 =0
x=+2
(b) Let oxidation number of S-atom is x

? (+1) × 2 + (x) × 4 + (–2) × 6 = 0
x = + 2.5
It is important to note here that Na2S2O3 have two S-atoms and there are four S-atom in Na2S4O6. However none of
the sulphur atoms in both the compounds have + 2 or + 2.5 oxidation number, it is the average of oxidation number,
which reside on each sulphur atom. Therefore, we should work to calculate the individual oxidation number of each
sulphur atom in these compounds.
Calculation of individual oxidation number

1. It is important to note that to calculate individual oxidation number of the element in its compound one should know
the structure of the compound and use the following guidelines.
Formula
Oxidation Number = Number of electrons in the valence shell – Number of electrons taken up after bonding
Guidelines : It is based on electronegativity of elements.
If there is a bond between similar type of atom and each atom has same type of hybridisation, then bonded pair electrons
are equally shared by each element.
76
Ex. Calculate oxidation number of each Cl-atom in Cl2 molecule
sp3 hybridised
sp3 hybridised
•• xx
Structure : Cl x Cl x
••
•• xx x
I II
, : Number of electrons in the valence shell = 7.
Number of electrons taken up after bonding = 7.
? oxidation number = 7 – 7 = 0.
,, : similarly, oxidation number = 7 – 7 = 0
2. If there is a bond between different type of atoms :
Ex. A – B (if B is more electronegative than A)
Then after bonding, bonded pair of electrons are counted with B - atom .
Ex. Calculate oxidation number of each atom in HCl molecule
xx
x
H x Cl x
Structure : xx
Note : Electron of H-atom is now counted with Cl-atom, because Cl-atom is more electronegative than H-atom
H : Number of electrons in the valence shell = 1
Number of electrons taken up after bonding = 0
Oxidation number of H = 1 – 0 = + 1
Cl : Number of electrons in the valence shell = 7
Number of electrons taken up after bonding = 8
Oxidation number of Cl = 7– 8 = – 1
Ex. Calculate individual oxidation number of each S-atom in Na2S2O3 (sodium thiosulphate) with the help of its structure
• •S• sp 2 hybridised
•• •
II
••
Sol. Structure : –•• • •– +
Na x•O
+
S O •• Na
•• ••
I ••
••
sp 3 hybridised
••O
••
Note : , (central S-atom) is sp3 hybridised (25% s-character) and ,, (terminal S-atom) is sp2 hydbridised (33%
s-character). Therefore, terminal sulphur atom is more electronegative than central sulphur atom. Now, the
shared pair of electrons are counted with terminal S-atom.
? ,, S-atom : Number of electrons in the valence shell = 6
Number of electrons left after bonding = 0
Oxidation number of central S-atom = 6 – 0 = + 6
,,, S-atom : Number of electrons in the valence shell = 6
Number of electrons left after bonding = 8
Oxidation number of terminal S-atom = 6 – 8 = – 2
6 + (–2)
Now, you can also calculate Average Oxidation number of S = = + 2 (as we have calculated before)
2
77
REDOX REACTION
KEY POINTS
Miscellaneous Examples
In order to determine the exact or individual oxidation number we need to take help from the structures of the
molecules. Some special cases are discussed as follows:
O O
(I) The structure of CrO5 is Cr
||
O O O
From the structure, it is evident that in CrO5 there are two peroxide linkages and one double bond. The contribution
of each peroxide linkage is –2. Let the oxidation number of Cr is x.
? x + (–2)2 + (–2) = 0 or x = 6
? Oxidation number of Cr = + 6.
O
(II) The structure of H2SO5 is H O O S
O
H O
From the structure, it is evident that in H2SO5, there is one peroxide linkage, two sulphur-oxygen double bonds
and one OH group. Let the oxidation number of S = x.
? (+ 1) + (– 2) + x + (–2) 2+ (–2) + 1 = 0
or x + 2 – 8 = 0 or x–6=0 or x=6
? Oxidation number of S in H2SO5 is + 6 .
Oxidation State as a periodic property :

Oxidation state of an atom depends upon the electronic configuration of an atom i.e. why it is periodic properties.
(a) I A group of alkali metals show +1 oxidation state.
(b) II A group or alkaline earth metals show +2 oxidation state
(c) The maximum normal oxidation state, show by III A group elements is +3. These elements also show +2 to +1
oxidation states also.
(d) Elements of IV A group show their maximum and minimum oxidation states +4 and –4 respectively.
(e) Non metals shows number of oxidation states, the relation between maximum and minimum oxidation states for non
metals is equal to (maximum oxidation state – minimum oxidation state = 8).
For example sulphur has maximum oxidation number +6 as being in VI A group element.
Paradox of fractional oxidation number :
Fractional oxidation number is the average of oxidation state of all atoms of element under examination and the structural
parameters reveal that the atoms of element for whom fractional oxidation state is realised a
actually present in different oxidation states. Structure of the species C3O2, Br3O8 and S4O62– reveal the following
bonding situations :
The element marked with asterisk (*) in each species is exhibiting different oxidation number from rest of the atoms of the
same element in each of the species. This reveals that in C3O2, two carbon atoms are present in +2 oxidation state each
whereas the third one is present in zero oxidation state and the average is + 4/3. However, the realistic picture is +2 for
two terminal carbons and zero for the middle carbon.
2 0 2
O C C* C O
Structure of C3O2
(Carbon suboxide)
78
Likewise in Br3O8, each of the two terminal bromine atoms are present in +6 oxidation state and the middle bromine is
present in +4 oxidation state. Once again the average, that is different from reality, is + 16/3.
In the same fashion, in the species S4O62–, average oxidation number of S is + 2.5, whereas the reality being +5,0,0 and
+5 oxidation number respectively for respective sulphur atoms.
In general, the conclusion is that the idea of fractional oxidation state should be taken with care and the reality is
revealed by the structures only.
Ex. Oxidation number of cobalt in [Co(NH3)6] Cl2Br is –
(1) +6 (2) Zero (3) +3 (4) +2
Sol. (3) Let the oxidation number of Co be x

Oxidation number of NH3 is zero
Oxidation number of Cl is –1
Oxidation number of Br is –1
Hence, x + 6 (0) – 1 × 2 – 1 = 0
? x = +3
So, the oxidation number of corbalt in the given complex compound is +3.
Ex. The order of increasing oxidation number of S in S8, S2O8–2, S2O3–2, S4O6–2 is given below –
(1) S8 < S2O8–2 < S2O3–2 < S4O6–2 (2) S2O8–2 < S2O3–2 < S4O6–2 < S8.
(3) S2O8 < S8 < S4O6 < S2O3
–2 –2 –2
(4) S8 < S2O3–2 < S4O6–2 < S2O8–2
Sol. (4) The oxidation number of S are shown below along with the compounds
S8 S2O8–2, S2O3–2, S4O8–2
0 +7 +2 +2.5
Hence the order of increasing of oxidation number of S is –
S8 < S2O3–2 < S4O6–2 < S2O8–2
Ex. The oxidation number of Cl in NOClO4 is –
(1) +11 (2) +9 (3) +7 (4) +5
Sol. (3) The compound may be written as NO+ ClO4–.
For ClO4–, Let oxidation number of Cl = a
a + 4 × (–2) = –1
a = +7
Hence, the oxidations number of Cl in NOClO4 is + 7
Ex. The two possible oxidation numbers of N atoms in NH4NO3 are respectively –
(1) +3, +5 (2) +3, –5 (3) –3, +5 (4) –3, –5
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REDOX REACTION
Sol. (3) There are two N atoms in NH4NO3, but one N atom has negative oxidation number (attached to H) and the other
has positive oxidation number (attached to O). Therefore evaluation should be made separately as –
oxidation number of N is NH4+ Oxidation number of N in NO3–
a + 4 × (+1) = +1 and a + 3 (–2) = 1
? a = –3 ? a=+5
Here the two oxidation number are –3– and +5 respectively.
Ex. The oxidation number of S in H2S2O8 is –
(1) +8 (2) –8 (3) +6 (4) +4
Sol. (3) In H2S2O8, two O atoms form peroxide linkage i.e.
O O
n n
H – O – S – O – O –S – O – H
p p
O O
2 × 1 + 2a + 6 (–2–) + 2 (–1) = 0
? a = +6
Thus the oxidation number of S in H2S2O8 is +6
Ex. The oxidation number of S in (CH3)2 SO is –
(1) 1 (2) 2 (3) 0 (4) 3
Sol. (3) Let the oxidation number of S is 'a'
Oxidation number of CH3 = +1
Oxidation number of O = –2
2 (+1) + a + (–2) = 0
a=0
Hence the oxidation no of S in Dimethyl sulphoxide is zero.
HOW TO IDENTIFY WHETHER A PARTICULAR SUBSTANCE IS AN OXIDISING OR A REDUCINGAGENT :
Find the oxidation state (O.S.) of the central atom
If O.S.= Maximum O.S. If O.S. = Minimum O.S. If O.S. = Intermediate between maximum & minimum
It is oxidizing It is a reducing It can act both as

agent agent reducing agent
& oxidising agent
It can
disproportionate
as well
Application of Oxidation number :-
(1) To compare the strength of acid and base :
Strength of acid v Oxidation Number
1
Strength of base v Oxidation Number
80
Ex. Order of acidic strength in HClO, HClO2, HClO3, HClO4 will be.
Sol. Oxidation Number of chlorine
HClO (Hypo chlorus acid) +1
HClO2 (Chlorous acid) +3
HClO3 (Chloric acid) +5
HClO4 (Perchloric acid) +7
? Strength of acid D Oxidation Number
So the order will be
HClO4 > HClO3 > HClO2 > HClO
(2) To determine the oxidising and reducing nature :
Group Range of Oxidation Number
(n – 8) to n
IA +1
II A +2
III A +1, +3
IV A –4 to + 4
VA –3– to +5
VI A –2 to +6
[Exception oMaximum Oxidation Number of Oxygen is 2]
VII A –1 to +7
[Exception o Oxidation of F is –1]
• If any compound is in maximum oxidation state (n), then it will act as only oxidant.
• If, compound is in minimum oxidation state (n – 8) then it will act as only reductant.
• If oxidation state is intermediate then compound can act as reductant as well as oxidant both.
Ex. Oxidation number of S in H2S = –2 (min)
So act as reducant.
Ex. Oxidation number of N in HNO2 = +3
So act as reductant as well as oxidant both.
• Oxidising strength v Oxidation Number
1
• Reducing strength v Oxidation Number
(3) To calculate the equivalent weight :
Equivalent weights of oxidising and reducing agents.
The equivalent weight of an oxidising agent is that weight which accepts one mole electron in a chemical reaction.
Molecular weight
(a) Equivalent weight of an oxidant (get reduced) =
Number of electrons gained by one mole
Ex. In acidic medium
6e– + Cr2O72– + 14H+ o2Cr3+ + 7H2O
Here atoms which undergoes reduction is Cr its oxidation state is decreasing from +6 to +3
Molecular weight of K2 Cr2 O 7 Molecular weight
Equivalent weight of K2Cr2O7 =
3 u2 6
Note : [6 in denominator indicates that 6 electrons were gained by Cr2O72– as it is clear from the given balanced equation]
Molecular weight
(b) Similarly equivalent weight of a reducant (gets oxidised) =
Number of electrons lost by one mole
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REDOX REACTION
Ex. In acidic medium, C2O42– o2CO2 + 2e–
Molecular weight
Here, Total electrons lost = 2 So, equivalent weight =
2
(c) In different condition a compound may have different equivalent wts. Because, it depends upon the number of
electrons gained or lost by that compound in that reaction.
Ex. Molecular weight of KMnO4 in acidic medium and neutral medium will be respecitvely –
(1) 7 × equivalent weight and 2 × equivalent weight
Ans. (2)
Ex. Equivalent weight of H3PO4 in each of the reaction will be respectively –
H3PO4 + OH– oH2PO4– + H2O
H3PO4 + 2OH– oHPO42– + 2H2O
H3PO4 + 3OH– oPO43– + 3H2O
(1) 98, 49, 32.67 (2) 49, 98, 32.67 (3) 98, 32.67, 49 (4) 32.67, 49, 98
Ans.(1)
Ex. In acidic medium, equivalent weight of K2Cr2O7 (Molecular weight = M) is –
(1) M/3 (2) M/4 (3) M/6 (4) M/2
Ans. (3)
(4) To determine the molecular formula of compound :

Ex. Suppose that there are three atoms A, B, C and their oxidation number are 6, –1, –2, respectively. Then the molecular
formula of compound will be.
Sol. Since, the charge on a free compound is zero. So
+6 = (–1 × 4) + (–2)
+6 = –6
or +6 = (–1 × 2) + (–2 × 2)
= –2 + (–4)= –6
So molecular formula, AB4C or AB2C2.
KEY POINTS
• When metals participate in chemical reaction, they are always oxidised. Thus metals always behave like reducing
agents.
• The acidic nature of non-metal oxide increases with increasing oxidation state of the non-metal.
• The strength of oxy-acid of an element increases with increasing oxidation state of the element.
Strength of oxy-acids of nitrogen increases in the following order.
+1 +3 +5
H2N2O2 < HNO2 < HNO3
Hyponitrous acid Nitrous acid Nitric acid
(weakest acid) (strongest acid)
• An element in its lowest state in its compound behave like a reducing agent only.
• Metals exist in mixed oxidation states in non-stoichiometric compounds.
For example : Oxidation state of Fe in Fe0.94 O is +2 and +3
• The oxidation state of iron in ferro compounds is +2 while in ferric compounds, it is in +3 oxidation state.
82
• The formula of the anhydride of an oxy-acid of an element can be calculated as follows :
Oxy-acid Acid-anhydride
+1
H ClO 1 2
Cl O
Cl2 O
Oxy-acid Acid anhydride
H+1 NO2 3 2
N O
N2 O3
Redox Reactions
(a) The reactions in which oxidation and reduction both occur simultaneously are called redox reactions.
(b) Most of the chemical reactions are redox because if one element is there to lose electrons, other element has to be
there to accept them.
(c) Any redox reaction may be divided in two parts.
(i) Oxidation half reaction.
(ii) Reduction half reaction.
Now, we will study some reaction.
S. No. Reaction Oxidant Reductant

(Getting Reduced) (Getting Oxidised)
1. C + O2 o CO2 O [0 o–2] C [0 o+4]
2. PbS + 4H2O2 o PbSO4 + 4H2O O [–1 o–2] S [–2 o+6]
3. Sn + 2F2 o SnF4 F [0 o–1] Sn [0 o+4]
4. SO2 + 2H2O + Cl2 o 2HCl + H2SO4 Cl [0 o–1] S[+4 o+6]
5. I2 + 10HNO3 o 2HIO3 + 10NO2 + 4H2O N [+5 o+4] I [0 o+5]
6. CuO + H2 o Cu + H2O Cu [+2 o0] H [0 o+1]
7. 2KMnO4 + 3H2SO4 + 5H2S o
K2SO4 + 2MnSO4 + 8H2O + 5S Mn [+7 o+2] S [–2 o0]
8. H2O2 + Ag2O o 2Ag + H2O + O2
(Oxygen of H2O2) Ag [+1 o0] O [–1 o0]
9. H2SO4 + 2HI o SO2 + I2 + 2H2O S [+6 o+4] I [–1 o0]
Note : In reaction 2 oxygens of ozone have different oxidation state.

Structure of Ozone is
O3 mO1 = O2
Oxidation state of O1 = +2
Oxidation state of O2 = 0
Oxidation state of O3 = –2
Types of Redox reaction :
(a) Intermolecular redox reaction :- When oxidation and reduction take place separately in the different compounds,
called intermolecular redox reaction.
SnCl2 + 2FeCl3 o SnCl4 + 2FeCl2
83
REDOX REACTION
Sn+2 o Sn+4 (Oxidation)
Fe+3 o Fe+2 (Reduction)
(b) Intra molecular redox reaction :- During the chemical reaction, if oxidation and reduction take place in single
compound then reaction is called intramolecular redox reaction.
2KClO3 KCl + 3O2
+5 –2 –1
Cl O Cl O°
Oxidation
Reduction
(c) Disproportionation reaction :- When reduction and oxidation takes place on same element of a compound is called
disproportionation reaction.
H2O2 H2O + 1/ 2 O2
–1 –2
O O O°
Reduction
Oxidation
Ex. The fast reaction between water and sodium is the example is –
(1) Oxidation (2) Reduction (3) Redox (4) none
Ans. (3)
Ex. Choose the redox reaction from the following –
(1) Cu + 2H2SO4 o CuSO4 + SO2 + 2H2O (2) BaCl2 + H2SO4 o BaSO4 + 2HCl
(3) Zn + H2SO4 o ZnSO4 + H2 (4) KNO3 + H2SO4 o 2HNO3 + K2SO4
Ans. (1,3)
Ex. Which of the following not a redox reaction –
(1) MnO4– o MnO2 (2) Cl2 + H2O o HCl + HClO
(3) 2CrO42– + 2H+ o Cr2O72– + H2O (4) MnO4– + 8H+ + 5Ag o Mg+2 + 4H2O
Ans. (3)
Ex. In the reaction 6Li + N2 o 2Li3N
(1) Li undergoes reduction (2) Li undergoes oxidation
(3) N undergoes oxidation (4) None of these
Ans. (2)
Balancing of redox equation :
(A) Oxidation number change method.
(B) Ion electron method.
(a) Oxidation number change method :-
This method was given by Jonson. In a balanced redox reaction, total increase in oxidation number must be equal to
total decreases in oxidation number. This equivalence provides the basis for balancing redox reactions.
The general procedure involves the following steps :-
(i) Select the atom in oxidising agent whose oxidation number decreases and indicate the gain of electrons.
(ii) Select the atom in reducing agent whose oxidation number increases and write the loss of electrons.
(iii) Now cross multiply i.e.multiply oxidising agent by the number of loss of electrons and reducing agent by
number of gain of electrons.
(iv) Balance the number of atoms on both sides whose oxidation numbers change in the reaction.
(v) In order to balance oxygen atoms, add H2O molecules to the side deficient in oxygen. Then balance the number
of H atoms by adding H+ ions in the hydrogen.
Ex. Balance the following reaction by the oxidation number method –
Cu + HNO3 o Cu(NO3)2 + NO2 + H2O
Sol. Write the oxidation number of all the atoms.
0 +1+5+2 +2+5–2 +4 –2 +1 –2
Cu + HNO3 o Cu(NO3)2 + NO2 + H2O
84
There is change in oxidation number of Cu and N.
0 +2+5–2
Cu o Cu(NO3)2 ..........................(1) (Oxidation number of Cu is increased by 2)
+5 +4
HNO3 o NO2 ..........................(2) (Oxidation number of N is decreased by 1)
To make increase and decrease equal, eq. (2) is multiplied by 2.
Cu + 2HNO3 o Cu(NO3)2 + 2NO2 + H2O
Balancing nitrates ions, hydrogen and oxygen, the following equation is obtained.
Cu + 4HNO3 o Cu(NO3)2 + 2NO2 + 2H2O
This is the balanced equation.
Ex. malance the following reaction by the oxidation number method –
MnO4– + Fe+2 o Mn+2 + Fe+3
Sol. Write the oxidation number of all the atoms.
+7 –2
MnO4– + Fe+2 o Mn+2 + Fe+3
change in oxidation number has occured in Mn and Fe.
+7 +2
MnO4– o Mn+2 (1) (Decrement in oxidation number by 5)
Fe+2 o Fe+3 (2) (Increment in oxidation number by 1)
To make increase and decrease equal, eq. (2) is multiplied by 5.
MnO4– + 5Fe+2 o Mn+2 + 5Fe+3
To balance oxygen, 4H2O are added to R.H.S. and to balance hydrogen, 8H+ are added to L.H.S.
MnO4– + 5Fe+2 + 8H+ o Mn+2 + 5Fe+3 + 4H2O
This is the balanced equation.
(b) Ion-Electron method :
This method was given by Jette and La mav in 1972.
The following steps are followed while balancing redox reaction (equations) by this method.
(i) Write the equation in ionic form.
(ii) Split the redox equation into two half reactions, one representing oxidation and the other representing reduction.
(iii) Balance these half reactions separately and then add by multiplying with suitable coefficients so that the
electrons are cancelled. Balancing is done as follows.
(iv) Add both half reaction and then balance the atoms other 'O' and 'H'.
(v) Then balance oxygen atoms by adding H2O molecules to the side deficient in oxygen. The number of H2O
molecules added is equal to the deficiency of oxygen atgms.
(vi) Balance hydrogen atoms by adding H+ ions equal to the deficiency in the side which is the deficient in
hydrogen atoms.
(vii) If the medium of reaction is basic, OH– ions are added to both sides of balanced equation equal in number of H+
in balanced equation.
(viii)Balance the charge by electrons to the side which is rich in +ve charges. i.e. deficiency in electrons. Number of
electrons added is equal to the deficiency.
(ix) Multiply the half equations with suitable coefficients to equalize the number of electrons.
(x) Add these half equations to get an equation which is balanced with respect ot charge and atoms.
(i) Acidic Medium :-
(a) Cr2O72– + C2O42– oCr3+ + CO2
(b) Write both the half reaction.
Cr2O72– oCr3+ (Reduction half reaction)
C2O42– oCO2 (Oxidation half reaction)
85
REDOX REACTION
(c) Atoms other than H and O are balanced.
Cr2O72– o2Cr3+
C2O42– o2CO2
(d) Balance O-atoms by the addition of H2O to another side
Cr2O72– o2Cr3+ + 7H2O
C2O42– o2CO2
(e) Balance H-atoms by the addition of H+ to another side
Cr2O72– + 14 H+ o2Cr3+ + 7H2O
C2O42– o2CO2
(f) Now, balance the charge by the addition of electron (e–).
Cr2O72– + 14 H+ + 6e– o2Cr3+ + 7H2O
C2O42– o2CO2 + 2e–
(g) Multiply equations by a constant to get the same number of electrons on both side. In the above case second
equation is multiplied by 3 and then added to first equation.
Cr2O72– + 14 H+ + 6e– o2Cr3+ + 7H2O
3C2O42– o6CO2 + 6e–
Cr2O7 + 3C2O42– + 14 H+ o2Cr3+ + 6CO2 + 7H2O
2–
(ii) Alkaline Medium :

(a) Consider the reaction

Cr(OH)3 + IO3– o I– + CrO42–
OH
(b) Separate the two half reactions.

Cr(OH)3 o CrO42– (Oxidation half reaction)
IO3– o I– (Reduction half reaction)
(c) Balance O-atoms by adding H2O.
H2O + Cr(OH)3 o CrO42–
IO3– o I– + 3H2O
(d) Balance H-atoms by adding H2O to side having deficiency and an equal number of OH– ions to the other side
(? medium is known)
5OH– + H2O + Cr(OH)3 o CrO42– + 5OH–
or 5OH– + Cr(OH)3 o CrO42– + 4H2O
IO3– + 6H2O o I– + 3H2O + 6OH–
or IO3– + 3H2O o I– + 6OH–
(e) Balance the charges by electrons
5OH– + Cr(OH)3 o CrO42– + 4H2O + 3e–
IO3– + 6H2O + 6e– o I– +3H2O + 6OH–
(f) Multiply first equation by 2 and add to second to give
10OH– + 2Cr(OH)3 o 2CrO42– + 8H2O + 6e–
IO3 + 6H2O + 6e o I + 3H2O + 6OH–
– – –
4OH– + 2Cr(OH)3 + IO3– o 5H2O + 2CrO42– + I–
86
Oxidation :
(i) Addition of Oxygen
(ii) Removal of Hydrogen
(iii) Addition of Electronegative element
(iv) Removal of Electropositive element
(v) Increment in oxidation state of Electropositive element
(vi) increase in (+) ve valency or decrease in (–) ve valency of a substance takes place called oxidation.
Reduction :
(i) Removal of Oxygen :
(ii) Addition of Hydrogen
(iii) Removal of Electronegative element
(iv) Addition of Electropositive element
(v) Decrement in oxidation state of Electropositive element
(vi) decrease in (+) ve valency or increase in (–) ve valency of a substance is called reduction.
Oxidising agent (oxidant) and reducing agent (Reductant)
Oxidising agent or Oxidant
Oxidising agents are those compounds which can oxidise others and reduce itself during the chemical reaction. Those
reagents in which for an element, oxidation number decreases or which undergoes gain of electrons in a redox reaction
are termed as oxidants.
Reducing agent or Reductant
Reducing agents are those compounds which can reduce other and oxidise itself during the chemical reaction. Those
reagents in which for an element, oxidation number increases or which undergoes loss of electrons in a redox reaction are
termed as reductants.
Ex. KI , Na2S2O3 etc are the powerful reducing agents.
Oxidation number change method :-(method of balancing redox equation)
This method was given by Jonson. In a balanced redox reaction, total increase in oxidation number must be equal to total
decreases in oxidation number. This equivalence provides the basis for balancing redox reactions.
The general procedure involves the following steps :-
(i) Select the atom in oxidising agent whose oxidation number decreases and indicate the gain of electrons.
(ii) Select the atom in reducing agent whose oxidation number increases and write the loss of electrons.
(iii) Now cross multiply i.e.multiply oxidising agent by the number of loss of electrons and reducing agent by number of
gain of electrons.
(iv) Balance the number of atoms on both sides whose oxidation numbers change in the reaction.
(v) In order to balance oxygen atoms, add H2O molecules to the side deficient in oxygen. Then balance the number of
H atoms by adding H+ ions in the hydrogen.
87
REDOX REACTION
SOLVED EXAMPLE
Ex. 1 The weight of sodium bromate required to prepare Ex. 4 A 0.1097 g sample of As2O3 required 36.10 mL of
55.5 mL of 0.672 N solution for cell reaction, KMnO4 solution for its titration. The molarity of
BrO3– + 6H+ + 6e– o Br– + 3H2O, is KMnO4 solution is.
(A) 1.56 g (B) 0.9386 g (A) 0.02 (B) 0.04
(C) 1.23 g (D) 1.32 g (C) 0.0122 (D) 0.3
Sol. Meq. of NaBrO3 = 55.5 × 0.672 = 37.296 Sol. n-factor = 5
Let weight of NaBrO3 = W
W As2O3 + MnO4– 2AsO4 3– + Mn2+
? × 6 × 1000 = 37.296 (equivalent weight = n-factor = 4
M NaBrO3
M/6) of n-factor = 6 Let, molarity of KMnO4 solution be M
? Eq. of As2O3 = Eq. of KMnO4 solution
M
? × 6 × 1000 = 37.296 0.1097 36.10 × M × 5
151 ×4= (Equivalent weight
? W = 0.9386 g 198 1000
Hence, (B) is the correct answer. 198
As2O3 = )
Ex. 2 NaIO3 reacts with NaHSO3 according to equation 4
Molarity = 0.0122 M
IO3– + 3HSO3– o I – + 3H+ + 3SO42–
Hence, (C) is the correct answer.
The weight of NaHSO3 required to react with 100 mL
of solution containing 0.68 g of NaIO3 is Ex. 5 In basic medium, CrO42– oxidize S2O32– to form SO42–
(A) 5.2 g (B) 0.2143 g and itself changes to Cr(OH)4– . How many mL of
(C) 2.3 g (D) none of the above 0.154 M CrO42– are required to react with 40 mL of
0.246 M S2O32– ?
0.68 (A) 200 mL (B) 156.4 mL
Sol. Meq. of NaHSO3 = Meq. of NaIO3 = N × V = ×
198 (C) 170.4 mL (D) 190.4 mL
6 × 1000 (I 5+ + 6e– o I –) Sol. 40 × 0.246 × 8 = V × 0.154 × 3 (Meq. of S2O32– = Meq.
WNaHSO3 0.68 of CrO42–)
? × 2 × 1000 = × 6 × 100 ? V = 170.4 mL
M NaHSO3 198 Hence, (C) is the correct answer.
0.68 × 6 × 100 × 104 Ex. 6 10 mL of 0.4 M Al2(SO4)3 is mixed with 20 mL of 0.6 M
WNaHSO 3 = = 0.2143
198 × 1000 BaCl2. Concentration of Al3+ ion in the solution will
Hence (B) is the correct answer. be.
(A) 0.266 M (B) 10.3 M
Ex. 3 If 0.5 moles of BaCl2 is mixed with 0.1 moles of (C) 0.1 M (D) 0.25 M
Na3PO4, the maximum amount of Ba3(PO4)2 that can
Sol. Al2(SO4)3 + BaCl2 o BaSO4 p + AlCl3
be formed is
Initial Meq.10 × 0.4 × 6 20 × 0.6 × 2 0 0
(A) 0.7 mol (B) 0.5 mol
= 24 = 24
(C) 0.2 mol (D) 0.05 mol
Final Meq. 0 0 24 24
Sol. Let us first solve this problem by writing the
complete balanced reaction. 24
[Al3+] = = 0.266 M
3BaCl2 + 2Na3PO4 o Ba3(PO4)2 p + 6NaCl 30 × 3
3 Hence (A) is the correct answer.
We can see that the moles of BaCl2 used are Ex. 7 0.52 g of a dibasic acid required 100 mL of 0.2 N
2
times the moles of Na3PO4. Therefore, to react with NaOH for complete neutralization.
0.1 mol of Na3PO4, the moles of BaCl2 required would The equivalent weight of acid is
3 (A) 26 (B) 52
be 0.1 × = 0.15. Since BaCl2 is 0.5 mol, we can (C) 104 (D) 156
2 Sol. Meq. of Acid = Meq. of NaOH
conclude that Na3PO4 is the limiting reagent.
3 0.52
× 1000 = 100 × 0.2
Therefore, moles of Ba3(PO4)2 formed is 0.1 × E
2
? E = 26
= 0.05 mol.
Hence (A) is the correct answer.
Hence, (D) is the correct answer.
88
Ex. 8 34 g hydrogen peroxide is present in 1120 mL of Ex. 12 8 g of O2 has the same number of molecules as
Solution : This solution is called (A) 7 g of CO (B) 14 g of CO
(A) 10 volume (B) 20 volume (C) 28 g of CO (D) 11 g of CO2
(C) 30 volume (D) 32 volume Sol. (A) and (D)
34 Ex. 13 What volume of 0.1 M KMnO4 is needed to oxidize
Sol. Wt. of H2O2 in 1 mL = g
1120 100 mg of FeC2O4 in acid solution ?
(A) 4.1 mL (B) 8.2 mL
1
H 2O 2 o H 2O + O2 (C) 10.2 mL (D) 4.6 mL
2
Sol. Meq. of KMnO4 = Meq. of FeC2O4
34 g of H2O2 gives 11200 mL of O2 at STP
34 11200 34 n-factor = 2
? g of H2O2 { × = 10 mL of 2×3 2×4
1120 34 1120 – + 2+ 3+
MnO4 + Fe C2 O4 + H Mn + Fe + 2 C O2 + H2O
O2 at STP.
n-factor = 5
Hence, (A) is the correct answer.
n-factor = 1
Ex. 9 The number of moles of KMnO4 that will be required
to react with 2 mol of ferrous oxalate is
6 2 ? V = 4.1 mL
(A) (B)
5 5 Hence, (A) is the correct answer.
4
(C) (D) 1 Ex. 14 What volume of 6 M HNO3 is needed to oxidize 8 g
5 of Fe2+ to Fe3+, HNO3 gets converted to NO?
Sol. Mn + 5 e o Mn ] × 3
7+ – 2+
Fe2+ o Fe3+ + e– (A) 8 mL (B) 7.936 mL

(C) 32 mL (D) 64 mL
º Sol. Meq. of HNO3 = Meq. of Fe2+
»
C2O o 2CO2 + 2e
4
2– –
¼ 8
3 moles of KMnO4 = 5 moles of FeC2O4 or 6 × 3 × V = × 1000
56
6 V = 7.936 mL
? 2 mol of ferrous oxalate { mole of KMnO4
5
n-factor = 3
Hence, (A) is the correct answer.
Ex. 10 The minimum quantity of H2S needed to precipitate +5 2+
–
63.5 g of Cu2+ will be nearly. (NO3 NO)
(A) 63.5 g (B) 31.75 g Hence, (B) is the correct answer.
(C) 34 g (D) 2.0 g
Ex. 15 0.5 g of fuming H2SO4 (oleum) is diluted with water.
Sol. Meq. of H2S = Meq. of Cu2+ This solution is completely neutralized by 26.7 mL
WH 2S 63.5 of 0.4 N KOH. The percentage of free SO3 in the
? × 1000 = × 1000 sample is
34 / 2 63.5 / 2
(A) 30.6% (B) 40.6%
? WH 2 S 34 g (C) 20.6% (D) 50%
Hence, (C) is the correct answer. Sol. Meq. of H2SO4 + Meq.of SO3 = Meq. of KOH
Ex. 11 Which of the following is / are correct? (0.5 – x) x

? × 1000 + × 1000 = 26.7 × 0.4
(A) g mole wt. = mol. wt. in g = wt. of 6.02 × 1023 98 / 2 80 / 2
molecules ? x = 0.103
(B) mole = N molecule = 6.02 × 1023 molecules
0.103
(C) mole = g molecules ? % of SO3 = × 100 = 20.6%
0.5
(D) none of the above
Hence, (C) is the correct answer.
Sol. (A), (B) and (C)
89
REDOX REACTION
Ex. 16 A 20 g sample of only CuS and Cu2S was treated Applying POAC for C atom,
with 100 mL of 1.25 M K2Cr2O7. The products Moles of C in BaCO3 + Moles of C in CaCO3 = Moles
obtained were Cr3+, Cu2+ and SO2. The excess oxidant of C in CO2
was reacted with 50 mL of Fe2+ Solution : 25 mL of
the same Fe2+ solution required 0.875 M KMnO4 x y 168
? + =
under acidic condition, the volume of KMnO4 used 197 100 22400
was 20 mL. Find the % of CuS and Cu2S in the sample. 200 x + 294 y = 295.5 ....(2)
Sol. Equivalents of dichromate initially From equation (1) and (2)
y = 0.416 g
1.25× 6 ×100
= = 0.75 ? 0.657 + 0.416 + z = 2.249
1000
z = 1.176
Equivalents of Fe2+ in 25 mL
1.176
0.875 × 5 × 5 × 20 % of CaO = = 52.29 %
= = 0.0875 2.249
1000
Equivalents of Fe2+ in 50 mL = 0.0875 × 2 = 0.175 Ex. 18 For estimating ozone in the air, a certain volume of
air is passed through an alkaline KI solution when
Equivalents of excess dichromate = 0.175
O2 is evolved and iodide is oxidized to iodine. When
? Equivalents of dichromate consumed by such a solution is acidified, free iodine is evolved
(CuS and Cu2S) which can be titrated with standard Na2S2O3 Solution
= 0.75 – 0.175 = 0.575 : In an experiment, 10 L of air at 1 atm and 27°C were
If x g is the mass of CuS, the mass of Cu2S is (10 – x) g passed through an alkaline KI solution, and at the
end, the iodine was entrapped in a solution which
x (10 – x) on titration as above required 1.5 mL of 0.02 N
× 6+ × 8 = 0.575
95.5 159 Na2S2O3 solution. Calculate volume percentage of
? x = 5.74 g ozone in the sample.
Sol. The chemical reaction is,
5.74 H2O + KI + O3 o I2 + O2 + KOH
% CuS = × 100 = 28.7 %
20 Milliequivalents of iodine = Milliequivalents of KI
% Cu2S = 71.3 % = Milliequivalents of O3 reacted
Ex. 17 2.249 g of a sample of pure BaCO 3 and impure Milliequivalents of Na2S2O3 = 1.5 × 0.02 = 3 × 10–2
CaCO3 containing some CaO was treated with dil. 3 × 1 0 –2
HCl and it evolved 168 mL of CO2 at N.T.P. From Millimoles of iodine = = 1.5 × 10–2
2
this solution, BaCrO4 was precipitated filtered and
['n-factor for iodine = 2]
washed. The precipitate was dissolved in dil.
Millimoles of ozone = 1.5 × 10–2
H2SO 4 and diluted to 100 mL. 10 mL of this
solution when treated with KI solution liberated Volume of ozone
iodine which required exactly 20 mL of 0.05 N nRT 1.5 × 10 –5 × 0.0821 × 300
Na2S2O3. Calculate the percentage of CaO in the = =
P 1
sample. –5
= 36.945 × 10 litre
Sol. Let, weight of BaCO3, CaCO3 and CaO are x,y and z
Volume percent of ozone
respectively.
? x + y + z = 2.249 36.945 × 10 –5
= × 100 = 3.6945 × 10–3
BaCO3 o BaCrO4 10
Redox change Cr6+ + 3e– o Cr3+
Ex. 19 What volume of 0.40 M H2SO4 is required to produce
2I– o I2 + 2e– 34.0 g of H2S by the reaction,
Meq. of BaCO3 = Meq. of BaCrO4 = Meq. of I2 8 KI + 5 H2SO4 o 4 K2SO4 + 4 I2 + H2S + 4 H2O ?
x 100 Sol. 1 mole of H2S { 5 moles of H2SO4
? × 1000 = 20 × 0.05 ×
197 / 3 10 34 g of H2S { 5 moles of H2SO4
? x = 0.657 g ....(1) 0.40 × VH 2SO 4 = 5
The equivalent weight of BaCrO4 is M/3, therefore
for BaCO3, it should be M/3 also because mole ratio 5
? VH 2 SO 4 = = 12.5 litre
of BaCO3 and BaCrO4 is 1 : 1. 0.40
90
Ex. 20 To 50 L of 0.2 N NaOH, 2.5 L of 2N HCl and 15 L of Ex. 22 A 2.18 g sample contains a mixture of XO and X2O3. It
0.1 N FeCl3 solutions are added. What weight of reacts with 0.015 moles of K2Cr2O7 to oxidize the sample
Fe2O3 can be obtained from the precipitate? Also completely to form XO4– and Cr3+. If 0.0187 mole of
report the normality of NaOH left in resultant XO4– is formed, what is the atomic mass of X ?
solution :
Sol. XO + K2Cr2O7 o Cr3+ + XO4–
Sol. Eq. of NaOH = 50 × 0.2 = 10
X2O3 + K2Cr2O7 o Cr3+ + XO4–
Eq. of HCl = 2.5 × 2 = 5
Eq. of NaOH left after reaction with HCl = 10 – 5 = 5 Let, wt. of XO in the mixture be x g
'
Equivalent of K2Cr2O7 consumed by the mixture
FeCl3 + NaOH o Fe (OH)3 p o Fe2O3 = 0.015 × 6
FeCl3 reacts with NaOH to give Fe(OH)3 which on
ignition gives Fe2O3 x
Equivalents of XO = ×5
? Eq. of NaOH used for FeCl3 = Eq. of Fe(OH)3 x + 16
= Eq. of Fe2O3
= 15 × 0.1 = 3.5 2.18 – x
Equivalents of X2O3 = u8
? Eq. of NaOH left finally = 5 – 1.5 = 3.5 2x 48
Normality of NaOH in the resultant solution x 2.18 – x
? ×5 + × 8 = 0.015 × 6
3.5 x + 16 2x – 148
= = 0.05
70 Since 1 mole of XO gives 1 mole XO4– and 1 mole of
WFe 2O3 X2O3 gives 2 moles of XO4–,
× 6 = 1.5 (n-factor for Fe2O3 = 6)
M Fe 2O3 x 2x(2.18 – x)
? + = 0.0187
x + 16 2x + 48
1.5 × 160
WFe 2 O 3 = = 40g On solving, x = 99
6
Ex. 23 An aqueous solution containing 0.10 g KIO3 (formula
Ex. 21 One litre of a mixture of O2 and O3 at NTP was allowed
wt. = 214.0) was treated with an excess of KI Solution
to react with an excess of acidified solution of KI.
The iodine liberated required 30 mL of M/10 Na2S2O3 : The solution was acidified with HCl. The liberated
solution for titration. What is the weight percent of I2 consumed 55 mL of thiosulphate solution to
ozone in the mixture ? decolourize the blue starch-iodine complex.
Ultraviolet radiation of wavelength 300 mm can Calculate molarity of the sodium thiosulphate
decompose ozone. Assuming that one photon can solution :
decompose one ozone molecule, how many photons
0.1
would have been required for the complete Sol. Moles of KIO3 = = 0.00047
decomposition of ozone in the original mixture? 214
Sol. O3 + 2 KI + H2O o 2KOH + I2 + O2
0.00047
2Na2S2O3 + I2 o Na2S4O6 + 2Nal ? Moles of I2 liberated from KIO3 =
Millimoles of O3 = Millimoles of I2 = ½ × Millimoles
2
of Na2S2O3 = 0.000235
= ½ × 30 × 1/10 = 1.5 millimoles Moles of KI reacting = 0.00047 × 5 = 0.00235
= 0.0015 moles (' n-factor for KIO3 and KI are 5 and 1 respectively)
Total moles of O3 and O2 in the mixture Moles of I2 produced from KI
PV = n RT
0.00235
1 × 1 = n × 0.0821 × 273 = = 0.001175
? n = 0.044 2
Moles of O2 = 0.044 – 0.0015 = 0.0425 Total moles of I2 produced and reacted = 0.000235 +
WO 2 = 0.0425 × 32 g = 1.36 g 0.001175 = 0.00141 equivalents of I2 reacted = 0.00141
× 2 = 0.00282 = equivalents of thiosulphate Solution
WO 3 = 0.0015 × 48 g = 0.072 g :
0.072 0.00282 × 1000

? % of O3 = × 100 = 5.028 % Molarity = =0.0512 M
1.432 55
No. of photons required for decomposition of Ozone (For thiosulphate n-factor = 1)
molecules = 0.0015 × 6.023 × 1023 = 0.90 × 1021
91
REDOX REACTION
Ex. 24 Mg can reduce NO3– to NH3 in basic medium. 206.06
NO3– + Mg (s) + H2O o Mg (OH)2 (s) + OH– (aq.) Meq. of I – formed using n-factor 1 =
6
+ NH3(g)
– 206.06
A 25.0 mL sample of NO3 solution was treated with Meq. of NaIO3 used in 2nd step =
Mg. The NH3 (g) was passed into 100 mL of 0.15 N 6
HCl. The excess of HCl required 32.10 mL of 0.10 N 6.8 206.06
NaOH for neutralization. What was the molarity of × 5×V=
198 6
NO3– ions in the original sample ? ? VNaIO = 199.99 mL
Sol. Meq. of NH3 formed = Meq. of HCl used 3
= 100 × 0.15 – 32.10 × 0.10 Ex. 26 A sample of Mg was burnt in air to give a mixture of
MgO and Mg3N2. The ash was dissolved in 60 Meq.
= 11.79 of HCl and the resulting solution was back titration
Here, n-factor of NH3 is 1 (acid - base reaction) with NaOH. 12 Meq. of NaOH were required to reach
For redox change, the end point. An excess of NaOH was then added
and the solution was distilled. The ammonia released
was then trapped in 10 Meq. of acid. Back titration
5
3 of this solution required 6 Meq. of base. Calculate
NO 3
8 e
o NH 3 (n - factor = 8) the % of Mg burnt to the nitride.
Sol. Let, total moles of Mg used for MgO and Mg3N2 be
? Meq. of NH3 for n-factor 8 = 8 × 11.79
a and b respectively
94.32 2Mg + O2 o 2MgO
? Normality of NO3– = = 3.77 a 0
25
0 a
3.77 3Mg + N2 o Mg3N2
Molarity of NO3– = = 0.47125
8 b 0
0 b/3
Ex. 25 Chile salt peter a source of NaNO3 also contains
NaIO3. The NaIO3 can be used as a source of iodine b
Now a, moles respectively of MgO and Mg3N2
produced in the following reactions : 3
Step 1 : IO3– + 3HSO3– o I – + 3H+ + 3SO42– are present in the mixture.
Step 2 : 5I – + IO3– + 6H+ o 3I 2 + 3H4O MgO + 2HCl o MgCl2 + H2O
One litre of chile salt peter solution containing 6.80 Mg3N2 + 8HCl o 3MgCl2 + 2NH4Cl
g NaIO3, is treated with stoichiometric quantity of or solution contains (A) moles of MgCl2 from MgO
NaHSO3. Now additional amount of same solution 2b
is added to the reaction mixture to bring about the and (B) moles of MgCl2 from Mg3N2 and moles
3
second reaction. How many grams of NaHSO3 are of NH4Cl.
required in step 1 and what additional volume of Now, moles of HCl or Meq. of HCl (monobasic) = 30
chile salt peter must be added in step 2 to bring in – 12 = 48
complete conversion of I– to I2 ? 8b
Sol. Meq. of NaHSO3 = Meq. of NaIO3 2a + = 48 ..........(1)
3
6.8 Moles of NH4Cl formed = Moles of NH3 liberated =
=N×V= × 6 × 1000 Moles of HCl used for absorbing NH3.
198
I5+ + 6e– o I – (For KIO3, n-factor = 6) 2b
= (10 – 6) = 4 ..........(2)
? Meq. of NaHSO3 = 206.06 3
WNaHSO3 8× 6
× 1000 = 206.06 From (1), 2a + = 48 or a = 16
M/2 3
6
206.06 × 104 ? % of Mg used for Mg3N2 = × 100 =
WNaHSO 3 = = 10.715 g (6 +16)
2 × 1000
Also, Meq. of I – formed using n-factor 6 = 206.06 27.27%
In step 2, n-factor I – is 1 and n-factor for IO3– is 5
? Oxalate salt is KH3(C2O4)2.2H2O
92
Ex. 27 Hydrogen peroxide solution (20 mL) reacts Ex. 28 1.0 g of moist sample of mixture of potassium chlorate
quantitatively with a solution of KMnO4 (20 mL) (KClO3) and potassium chloride (KCl) was dissolved
acidified with dilute H2SO4. The same volume of the in water and solution made upto 250 mL. This
KMnO4 solution is just decolourized by 10 mL of solution was treated with SO2 to reduce all ClO3– to
MnSO4 in neutral medium simultaneously forming a Cl– and excess of SO2 was removed by boiling. The
dark brown precipitate of hydrated MnO2. The brown total chloride was precipitated as silver chloride.
precipitate is dissolved in 20 mL of 0.2 M sodium The weight of precipitate was found to be 1.435 g.
In another experiment, 25 mL of the original solution
oxalate under boiling condition in the presence of
was heated with 30 ml 0.2 N FeSO4 and unused FeSO4
dilute H2SO4. Write the balanced equations involved
required 37.5 mL of 0.08 N KMnO4 solutions.
in the reactions and calculate the volume strength
Calculate the molar ratio of the ClO3– to the given
of H2O2.
mixture.
Sol. Meq. of MnO2 = Meq. of Na2C2O4
Given that, ClO3– + 6Fe2+ + 6H+ o
= 20 × 0.2 × 2 = 8 – 3+
Cl + 6Fe + 3H2O
(C2O42– o 2CO2, n-factor = 2) 3SO2 + ClO3– + 3H2O
o Cl + 3SO4 + 6H
– 2– +
8
Millimoles of MnO2 = 4 Sol. ClO3– is reduced to Cl– by SO2 and ClO3– is also
2
reduced to Cl– by Fe2+, hence AgCl is formed due to
total Cl–
n-factor = 3
Meq. of Fe2+ initially taken = 30 × 0.2 = 6
Meq. of Fe2+ unused = 37.5 × 0.08 = 3
MnO4 + Mn H O MnO2 brown (ppt.)
– +2 2
? Meq. of Fe2+ = 6.0 – 3.0 = 3.0

Thus, Meq. of ClO3– in 25 mL = 3.0
n-factor = 2
3 .0
Moles of ClO3– in 25 mL = = 0.0005
or 2MnO + 3Mn o 5MnO2
4
– 2+
(Mole ratio is 100 0 u 6
reciprocal of n-factor ratio) +5
ClO3– o –1
Cl– (n-factor = 6)
O.N. 5 –1
Millimoles of MnO 4– 2 –
= Thus, moles of ClO3 in 25 mL solution = 0.0005
Millimoles of MnO 2 5
ClO3– is also reduced to Cl– by SO2 in first experiment
and precipitated as AgCl.
2
Millimoles MnO4– = × Millimoles of MnO2 Thus, Cl– formed from ClO3– = AgCl from ClO3– = 1.435
5 g
2 8 Total AgCl formed both from actual and Cl– from
= × 4= ClO3– = 1.435 g
5 5
2KMnO4 + 5H2O2 + 3H2SO4 o 2 MnSO4 + K2SO4 + 1.435
= = 0.01 mol
8H2O + 5O2 143.5
Thus, AgCl formed due to Cl– only = 0.01 – 0.0005 =
Millimoles of H 2O 2 5
–
= 0.0095 mol
Millimoles of MnO 4 2
Thus, ClO3– and Cl– are in molar ratio = 1 : 19
5 8
? Millimoles of H2O2 = × =4
2 5
N H 2 O 2 × 20 = 4 × 2 (n-factor for
H2O2 = 2)
? N H 2 O 2 = 0.4
Volume strength of H2O2 = 5.6 × N H 2 O 2

= 5.6 × 0.4 = 2.24
93
1. The number of moles of KMnO4 that will be needed 6. In which of the following compounds, nitrogen
to react with one mole of sulphite ion in acidic exhibits highest oxidation state ?
solution [AIPMT (Prelims)–2007] [AIPMT (Prelims) –2012]
3 (A) N3H (B) NH2OH
(A) 1 (B)
5 (C) N2H4 (D) NH3
4 2 7. (a) H2O2 + O3 o H2O + 2O2 [AIPMT - 2014]
(C) (D)
5 5 (b) H2O2 + Ag2O o 2Ag + H2O + O2
2. Oxidations numbers of P in PO43–, of S in SO42– and Role of hydrogen peroxide in the above reactions
that of Cr in Cr2O72–, are respectively is respectively
[AIPMT (Prelims)–2009] (A) Oxidizing in (a) and reducing in (b)
(A) +3 , +6 and +5 (B) +5 , +3 and +6 (B) Reducing in (a) and oxidising in (b)
(C) –3 , +6 and +6 (D) +5 , +6 and +6 (C) Reducing in (a) and (b)
(D) Oxidising in (a) and (b)
3. Oxidation states of P in H4P2O5, H4P2O6, H4P2O7 are
respectively [AIPMT (Prelims)–2010]
8. Which of the following processes does not involve
(A) +3 , +5 ,+4 (B) +5 , +3, +4
oxidation of iron ? [AIPMT - 2015]
(C) +5, +4, +3 (D) +3 , +4 ,+5
(A) Liberation of H2 from steam by iron at high
4. How much amount of CuSO4.5H2O required for temperature
liberation of 2.54 g I2 when titrated with KI (B) Rusting of iron sheets
[AIPMT-2011] (C) Decolourization of blue CuSO4 solution by
(A) 2.5 gm (B) 4.99 gm iron
(C) 2.4 gm (D) 1.2 gm (D) Formation of Fe(CO)5 from Fe
5. A solution contains Fe2+, Fe3+ and I– ions. This 9. Assuming complete ionization, same moles of which
solution was treated with iodine at 35°C. E° for Fe3+/ of the following compounds will require the least
Fe2+ is 0.77 V and E° for I2/2I– = 0.536 V. The amount of acidified KMnO4 for complete oxidation ?
favourable redox reaction is [Re -AIPMT - 2015]
[AIPMT (Mains)–2011] (A) FeC2O4 (B) Fe(NO2)2
(A) I– will be oxidised to I2 (C) FeSO4 (D) FeSO3
(B) Fe2+ will be oxidised to Fe3+
(C) I2 will be reduced to I– 10. For the redox reaction
(D) There will be no redox reaction
MnO 4 C 2 O 24 H o Mn 2 CO 2 H 2 O the
correct coefficients of the reactants for the
balanced equation are [NEET-2018]
MnO 4 C2 O 42 H+
(A) 2 16 5
(B) 2 5 16
(C) 16 5 2
(D) 5 16 2
94
REDOX REACTION
1. MnO42 – (1 mole) in neutral aqueous medium is 9. Consider the following reaction occuring in basic
disproportionated to medium [2017]
(A) 2/3 mole of MnO4– and 1/3 mole of MnO2 2MnO 4 (aq)+Br (aq) o2MnO2(s) + BrO 3(aq)
– – –
(B) 1/3 mole of MnO4– and 2/3 mole of MnO2 How the above reaction can be balanced further?
(C) 1/3 mole of Mn2O7 and 1/3 mole of MnO2 (A) By adding 2 OH– ions on right side
(D) 2/3 mole of Mn2O7 and 1/3 mole of MnO2 (B) By adding one H2O molecule to left side
[2003] (C) By adding 2H+ ions on right side
(D) Both (a) and (b)
2. For decolourization of 1 mole of KMnO4, the moles
of H2O2 required is 10. On the basis of the following E° values, the strongest
(A) 1/2 (B) 3/2 oxidizing agent is : [2017]
(C) 5/2 (D) 7/2 [2004] [Fe(CN)6] o[Fe(CN)6] + e ; E° = – 0.35 V
4– 3– –
Fe2+ o Fe3+ + e–; E° = – 0.77 V

3. In the balanced chemical reaction :
(A) [Fe(CN)6] 4–
(B) Fe2+
IO3 aI bH o cH 2 O dI 2 (C) Fe3+ (D) [Fe(CN)6]3–
a, b, c and d respectively correspond to
ASSERTION AND REASON
(A) 5, 6, 3, 3 (B) 5, 3, 6, 3
In each of the following questions, two statement
(C) 3, 5, 3, 6 (D) 5, 6, 5, 5
are given one is assertion and the other is reason.
[2005]
Examine the statement carefully and mark the correct
4. When KMnO4 reacts with KBr in alkaline medium answer according to the instruction given below
gives bromate ion, then oxidation state of Mn (A) If both the assertion and reason are true and
changes from +7 to reason explains the assertion
(A) +6 (B) +4 (B) If both the assertion and reason are true but
(C) +3 (D) +2 [2011]
reason does not explain the assertion
(C) If assertion is true but reason is false
5. Oxidation state of iron in haemoglobin is (D) If assertion is false but reason in true
(A) 0 (B) +2 (E) Both assertion & reason are false
(C) –2 (D) +3 [2013]
11. Assertion : Reaction of SO2 and H2S in the presence
6. K2Cr2O7 in acidic medium converts into of Fe2O3 catalyst gives elementsl sulphu.
(A) Cr2+ (B) Cr3+ Reason : SO2 is a reducing agent. [2005]
(C) Cr4+ (D) Cr5+ [2013]

12. Assertion : The formal oxidation number of sulphur
7. What is the oxidation number of Br in KBrO4 ? in Na2S4O6 is 2.5
(A) +6 (B) +7 Reason : Two S-atoms are not directly linked with
(C) +5 (D) +8 [2014] O-atoms. [2011]
8. Substances that are oxidised and reduced in the 13. Assertion : Fluorine is a stronger oxidizing agent
following reaction are respectively than iodine.
N2H4(l) + 2H2O2(l) o N2(g) + 4H2O(l) Reason : Fluorine has greater electronegativity than
(A) N2H4, H2O (B) N2H4, H2O2 iodine. [2012]
(C) N2, H2O2 (D) H2O, N2 14. Assertion : Cl2 gas bleaches the articles permanently.
[2016] Reason : Cl2 is a strong reducing agent. [2012]
15. Assertion : Cu is stronger reducing agent than H2.

Reason : E° of Cu2+/Cu is negative. [2013]
95
REDOX REACTION
ANSWER KEY
EXERCISE : PART - 1
1. D 2. D 3. D 4. A 5. A 6. A 7. C 8. D 9. C 10. B
PART - 2
1. A 2. C 3. A 4. B 5. B 6. B 7. B 8. B 9. D 10. C 11. B 12. A 13. B
14. C 15. D
96
EXERCISE
P-1 (NEET/AIPMT)
1. (D) 2KMnO 4 5H 2SO 4 o H 2SO 4 2MnSO 4
2H 2SO 4 3H 2 O
2moles of KMnO4 reacts with 5 moles of sulphite ion in
acidic solution. Thus, 2/5 moles of KMnO4 will react with
1 mole of sulphition.
2. (D) 3. (D) 4. (A)
5. (A) 2I o I2 + 2e (Oxidation half – reaction)
– –
E 0oxidation 0.536V
Fe3+ e–o Fe2+ (reducation half – reaction)
E 0reduction 0.77V
2Fe3 2I o 2Fe 2 l2 ;
E 0 E oxidation
0
E 0reduction
+ ve
So, reaction will take place.
6. (A)
7. (C) N3H = –1/3 NH2OH = –2
N2H4 = –2 NH3 = –3
8. (D) The chemical reactions representing the given
processes can be written as :
Rusting of iron sheets :
[0] [III]
4PMVUJPOT Fe
Moist air
o Fe 2 O3 .xH 2 O
Rust
Decolourisation of blue CuSO4 solution by iron :
[0] [II]
Fe CuSO 4 o FeSO 4 Cu
Formation of Fe(CO)5 from Fe :
[0] [II]
Fe 5CO o Fe(CO)5
Liberation of H2 from steam by iron at high temperature :
[0] [2.66]
3Fe 4H 2 O
1000 K
o Fe3O 4 4H 2
Thus, among the given processes, formation of Fe(CO)5
from Fe does not involve oxidation of iron.
Hence, the correct option is (D).
9. (C) MnO 4
o Mn 2 ; Change in O.N. 5
In option
(A) Fe2
o Fe3 ; Changein O.N. 1 °½
2 ¾3
C2 O 4
o 2CO 2 ; Changein O.N. 2 °¿
(B) Fe
2
o Fe3 ; Changein O.N. 1½°
¾5
2NO 2 o 2NO3 ; Changein O.N. 4 °¿
(C) Fe 2
o Fe3 ; Change in O.N. 1 }1
(D) Fe 2
o Fe ; 3
Change in O.N. 1 ½°
2 2 ¾3
SO
3o SO ; 4 Change in O.N. 2 °¿
10. (B) MnO4– + C2O42– + H+ o Mn2+ + CO2 + H2O

2MnO4– + 5C2O42– + 16H+ o 2Mn2+ + 10CO2 + 8H2O
2 : 5 : 16
97
REDOX REACTION
EXERCISE 9. (D) : Since reaction is occuring in basic medium there-
P-2 (AIIMS) fore 2OH– are added on right side.
2MnO 4 (aq) + Br– (aq) o
1. (A) : 3MnO24 2H 2 O o MnO2(s) 2MnO4 4OH
2MnO2(s) + BrO–3 (aq) + 2OH–(aq)
for one mole
Now, hydrogen atoms can be balanced by adding one
2 1 2 4 H2O molecule to the left side
MnO 24 H 2 O o MnO 2(s) MnO 4 OH 2MnO–4 (aq) + Br– (aq) H2O(A) o
3 3 3 3
2MnO2(s) + BrO–3 (aq) 2OH– (aq)
2. (C) : Acidified KMnO4 is decolourised by H2O2 in
following way. 10. (C) : From the given data we find Fe3+ is strongest
2KmNO4 + 3H2SO4 o K2SO4 + 2MnSO4 + 3H2O + 5O oxidising agent. More the positive value of E°, more is
5H2O2 + 5O o 5H2O + 5O2 the tendency to get oxidized. Thus correct option is (c).
2KMnO4 + 3H2SO4 + 5H2O2 o K2SO4 + 2MnSO4 + 8H2O 11. (B) : SO2 shows both oxidising as well as reducing nature.
+ 5O2 The reaction given in assertion is due to oxidising nature
Thus, of SO2.
for 2 moles of KMnO4, required H2O2 = 5 moles 2H2S + SO2 o 2H2O + 3S
? For 1 mole of KMnO4 required H2O2 = 5/2 moles
O O
3. (A) : IO 3 al bH o cH 2 O dI 2 +5 0 0 +5
+ +
Step 1 : I– o I2 (oxidation) 12. (A) : NaO S S S S O Na
IO3–o I2 (reduction) O O
Step 2 : 2IO3– + 12H+ o I2 + 6H2O
Step 3 : 2IO3– + 12H+ + 10e– o I2 + 6H2O Formal oxidation number of sulphur
2I– o I2 + 2e– 2u5 2u0
2.5
Step 4 : 2IO3– + 12H+ + 10e– o I2 + 6H2O 4
[2I– o I2 + 2e–]5
Step 5 : 2IO3– + 10I– + 12H+ o 6I2 + 6H2O 13. (B) : Fluorine has higher standard electrode potential
(reduction jpotential) than iodine.
IO3– + 5I– + 6H+ o 3I2 + 3H2O
On comparing, a = 5, b = 6, c = 3, d = 3 14. (C) : Cl2 is an oxidising agent. It bleaches the articles
permanently by oxidation in presence of moisture.
4. (B) : 2MnO4– + Br– + H2O o
+4 15. (D) : E° of Cu2+/Cu is + 0.34 V and positive E° means that
2MnO2 + BrO3– + 2OH– the redox couple is a weaker reducing agent than the H+/
H2 couple.
5. (B) : Oxidation state of iron in haemoglobin is +2.
6. (B) : Cr2 O 72 14H 6e o 2Cr 3 7H 2 O
7. (B) : Let the oxidation no. of Br be x.

In KBrO4, + 1 + x + 4 (–2) = 0, 7 + x = 0, x = + 7
Decrease in O.N. (Reduction)
0
8. (B) : N2H4 + 2H2 O2 N2 + 4H2 O
Increase in O.N. (Oxidation)
98
STATES OF MATTER
CHAPTER
07
(GASEOUS AND LIQUID)
If molecules can be structurally identical and yet possess dissimilar
properties, this can be explained only on the ground that the difference
is due to a different arrangement of the atoms in space.
“ JOHANNES WISLICENUS”
INTRODUCTION
M
atter is made up of atoms or molecules. The arrangement of these molecules determines
the state of matter. There are three recognised state of matter : Solid, Liquid and Gas.
Matter can change between states when the temperature or pressure is changed.
State changes of matter are physical rather than chemical.
For example Water can exist as ice, which is a solid; it can exist as liquid; or it can
exist in the gaseous state as water vapour or steam.Physical properties of ice, water
and steam are very different,In all the three states of water chemical composition of
water remain the same. Charecteristics of the three states of water depands on the
energies of molecules and on the manner in which water molecules aggregate.
Chemical properties of a substance do not change with the change of its physical
state; but rate of chemical reactions depands upon the physical state.
99
DIFFERENCE BETWEEN STATES OF MATTER
. No. Gas Liquid Solid
i. Assumes the shape and volume Assumes the shape of the Retains a fixed volume and
of its container. part of the container which shape.
it occupies
ii. Particles can move past one Particles can move/slide past Rigid-particles locked into
another. one another. place.
iii. Compressible, lots of free space Not easily compressible, little Not easily compressible, little
between particles space between particles. free space between particles.
iv. Flows easily, particles can move Flows easily, particles can Does not flow easily, rigid-
past one another. move/slide past one another particles cannot move/slide one
past another
v. Low density. Intermediate density. High density.
vi. Very small intermolecular Considerable intermolecular Intermolecular forces are high,
attraction but high kinetic attraction, kinetic energy vibrational motion only.
energies. is less.
GASEOUS STATE
Important Properties of Gases :
(a) Mass : Mass in gm = Moles × Molecular mass.
(b) Volume : Volume of the gas is the volume of container in which they are filled in.
(c) Temperature : Temperature of a gas is the measure of kinetic energy of gas.
Kinetic energy v Temperature
(d) Pressure : Pressure of gas is defined as the force exerted by the gas on the walls of its container. It is often
assumed that pressure is isotropic, i.e. it is the same in all the three directions.
Force
Pressure = ,
Area
Mg v×d×g A×h×d×g
P= = =
A A A
P = hdg
Where.... h = height of the mercury column supported by the barometer.
d = density of mercury.
g = acceleration due to gravity.
Units and Determination of Pressure of Gas :
(a) In SI unit the unit of pressure is the pascal (N/m2) instead, the unit bar, kPa or MPa is used.
1 bar = 105 N/m2 = 100 kN/m2 = 100 kPa
(b) Pressure are also stated in mm or cm of mercury.
1 atm = 760 mm Hg = 1.01325 bar = 1.01325 × 105 Pa = 101.325 KN/m2 = 1.0332 Kgf/cm2
1 Pa = 1 Nm–2 = 1 Kgm–1 S–1
1L = 1dm3 = 10–3 m3 (SI unit)
1L atm = 101.325 J
KN 3
N 1×103 × kg 1
1 2 = 1 × 10 2 = = kgf/cm2
m m 9.8 ×104 cm 2 98
101325
1Torr = Pa = 133.322 Pa
760
100
STATES OF MATTER (GASEOUS & LIQUID)
(c) The pressure relative to the atmosphere is called gauge pressure. The pressure relative to the perfect vacuum is
called absolute pressure.
Absolute pressure = Gauge pressure + Atmosphere pressure
(d) When the pressure in a system is less than atmospheric pressure, the gauge pressure becomes negative, but is
frequently designated and called vacuum.
For example, 16 cm vacuum will be -
Gas
Pgas
h
2.4mL Patm
Hg Patm+ P = Pgas
(Patm+ hdg = Pgas )
An open arm manometer

76 – 16
× 1.013 = 0.80 bar
76
(e) Pressure is measured using a manometer which is
a simple device with a horizontal arm and a U-tube
carrying mercury or any other suitable liquid.
Ex. Calculate the mass of mercury in a uniform column 760 mm high and 1.00 cm2 in cross-sectional area. Is there
any change in.
(a) mass and
(b) pressure of column of same height but with 2.00cm2 cross sectional area is taken ?
(density of Hg = 13.6 g/cm3)
Sol. 760 mm = 76 cm
? V = 76 × 1 = 76 cm3
? Mass = V × d = 76 × 13.6 = 1033.6 g
(a) If area of cross-section is 2cm2 (doubled) then volume is also doubled hence,
? Mass = 76 × 2 × 13.6 = 2067.2 g
(b) This mass would rest on twice the area and so exert the same pressure.
GAS LAWS
The gas laws are a set of laws that describe the relationship between thermodynamic temperature (T), pressure (P) and
volume (V) of gases.
(I) Boyle's Law
It states "at a constant temperature (T), the pressure (P) of a given mass (or moles, n) of any gas varies inversely
with the volume (V)". Pressure (P) and volume (V) of gases.
1
i.e. P v (for given n and T)
V
or, PV = K = constant
For two or more gases at constant temperature
P1V1 = P2V2 = ..... = K
1
Also, density d v
V
Hence P v d
P1 P2
or = = ......... = K
d1 d 2
101
yGraphical Representation
T2 > T1
V V
T2
1/P P P
log P log P
P log 1/V
These plots drawn at constant temperature for a gas are called Isotherms.
Ex. A 10 cm volume of air is trapped by a column of Hg, 8 cm long in capillary tube horizontally fixed as shown
below at 1 atm pressure. Calculate the length of air column when the tube is fixed at same temperature.
10cm 8cm
(fig. 1)
(a) Vertically with open end up

(b) Vertically with open end down
(c) At 45ºC from with open end up
Sol. (a) When the capillary tube is held as vertically open end up (fig.2),
The pressure on the air column = atmospheric pressure + pressure of 8 cm Hg column
= 76 + 8 = 84 cm of Hg.
8cm
(fig. 2)
Let, at this condition the length of the air column = A2 and the length of air column when capillary is
horizontally fixed = A1 = 10 cm and pressure on air column = 1atm.
Let the cross section of the capillary = a cm2
? 76 × 10 × a = 84 × A2 × a
76 ×10
or A2 = = 9.04 cm
84
(b) When the capillary tube is held as vertically open end down (fig.3), the pressure on the air column
= atmospheric pressure – pressure of 8 cm Hg column
= 76 – 8 = 68 cm of Hg.
Let at this condition the length of air column = A3.
? 68 × A3 × a = 76 × 10 × a
102
8cm
(fig. 3)
76 ×10
or A 3 = = 11.17 cm
68
(c) When the capillary is held at 45º with open end up, the weight of Hg is partially borne by, the gas
and partially by the Hg. The pressure on the gas due to Hg column
= 8 × cos 45º
1 8
=8× = = cm of Hg
2 2
§ 8 ·
? total pressure on the gas = ¨ 76 + ¸ cm of Hg.
© 2¹
Let length of air column at this pressure = A4.
m
8c
•
º
45
4
A
(fig. 4)
§ 8 ·
? A4 × a × ¨ 76 + ¸ = 10 × a × 76
© 2¹
Ex. A rubber balloon contains some solid marbles each of volume 10 ml. A gas is filled in the balloon at a pressure of
2 atm and the total volume of the balloon is 1 litre in this condition. If the external pressure is increased to 4atm the
volume of Balloon becomes 625 ml. Find the number of marbles present in the balloon.
Sol. Let the no. of marbles be = n .
volume of marble = 10 n ml.
volume of balloon earlier = 1000 ml.
later = 625 ml.
Now for the gas inside the balloon temperature and amount of the gas is constant, hence boyles law can be applied
P1V1 = P2V2
4× (625 – 10n) = 2 × (1000 – 10n)
625 × 4 = 2000 – 20n + 40n
625 × 4 – 2000 = 20n
625× 4 – 2000 125
= n. =n ; n = 25
20 5
103
(II) Charles' Law
1
It states "at constant pressure, the volume of a given mass of a gas, increases or decreases by th of its
273.15
volume at 0ºC for every rise or fall of one degree in temperature".
Vt 1
V0 = 1 + 273.15 t (at constant n and P)
§ t ·
or Vt = V0 ¨1 + ¸
© 273.15 ¹
V0 (273.15 + t)
or Vt =
273.15
0ºC on the Celsius scale is equal to 273.15 K at the Kelvin or absolute scale.
i.e. Tt (Temperature in Kelvin scale) = 273.15 + t
Vt Tt
? From the above equation we get =
V0 T0
Vt V0
or =
Tt T0
i.e. The volume of a given gas is proportional to the absolute temperature.
V1 V 2
= (at constant P)
T1 T2
y Graphical Representation
V
V log V
22.4 L mol–1 =V0
0 T (K) –273.15º 0 t(ºC) 0 log T
Graphs between V and T at constant pressure are called Isobars.

Ex. If the temp. of a particular amount of gas is increased from 27ºC to 57ºC, find final volume of the gas, if initial volume
= 1 lt and assume pressure is constant.
V1 V2
Sol. =
T1 T2
1 V2
= So V2 = 1.1 lt.
(273 + 27) (273 + 57)
Ex. An open container of volume 3 litre contains air at 1 atmospheric pressure. The container is heated from initial
temperature 27ºC or 300 K to tºC or (t + 273) K the amount of the gas expelled from the container measured 1.45 litre
at 17ºC and 1 atm.Find temperature t.
Sol. ? T01 = 300 K
It can be assumed that the gas in the container was first heated to (t + 273), at which a volume ‘'V’ escaped from the
container
hence applying charles law :
104
3 3 + ΔV
=
300 t + 273
Now, this volume ‘'V’ which escapes when the container get cooled
ΔV 1.45
? =
t + 273 290
Solve the two equations and get the value of 'V and t.
determine ' V & calculate t that will be the answer.
(III) Gay-Lussac's Law : Dependence of Pressure on Temperature

It states "at constant volume, the pressure of a given mass of a gas is directly proportional to the absolute
temperature of the gas".
P v T or P = KT
P1 P2
or =
T1 T2
y Graphical Representation
V1
V2
P
P
P0
T T
The plots drawn at constant volume for a gas is called as Isochore.
THE COMBINED GAS LAW :
It states "for a fixed mass of gas, the volume is directly proportional to absolute temperature and inversely proportional
to the pressure".
1
Boyle's Law, V v (at constant n, T)
P
Charle's Law, V v T (at constant n, P)
T T PV P1V1 P2 V2
Therefore, V v or V = K or =K or =
P P T T1 T2
VOLUME COEFFICIENT (Dv) OFA GAS :
The ratio of increase in volume of a gas at constant pressure per degree rise of temperature to its volume at 0ºC is the
volume coefficient of the gas.
Vt – V0
Dv = V × t or Vt = V0 (1 + Dvt)
0
1
For all gases, Dv =
273
PRESSURE COEFFICIENT (Dp) OFA GAS :

The ratio of increase in pressure of the gas at constant volume per degree rise of temperature to its pressure at 0ºC is the
pressure coefficient of the gas.
Pt – P0
Dp = or Pt = P0 (1 + Dpt)
P0 × t
105
1
For all gases, Dp =
273
(IV) Avogadro's Law

It states "equal volumes of any two gases at the same temperature and pressure contain the same number of
molecules".
V v n (At constant P and T)
V1 V2
or, =
n1 n 2
Ex. The temperature of a certain mass of a gas is doubled. If the initially the gas is at 1 atm pressure. Find the % increase
in pressure ?
P1 P2 1 P2
Sol. T1 = T2 ; =
T 2T
2 –1
% increase = x 100 = 100%
1
Ex. The temperature of a certain mass of a gas was increased from 27°C to 37°C at constant volume. What will be the
pressure of the gas.
P1 P2 P P2 31
Sol. T1 = T2 ; = ; P2 = P
300 310 30
IDEAL GAS EQUATION

An ideal gas is defined to be a system in which there are no inter molecular/interatomic forces. Such a system can only
exist as a gas. Any real system will approach ideal gas behaviour in the limit that the pressure is extremely low and the
temperature is high enough to overcome attractive intermolecular forces.
An ideal gas is a gas to go which the laws of Boyle and Charles are strictly applicable under all conditions of temperatures
and pressures.
From Boyle's law we get,
V v1/P (at constant n and T)
From charles law we get,
V v T (at constant n and P)
From Avogadro's law we get,
V v n (at constant T and P)
Combining the above three equations we get
nT nT
V v or V = R [Where R = ideal gas constant]
P P
or PV = nRT
Ideal gas equation is a relation between four variables and it describes the state of any gas. For this reason, it is also
called Equation of State.
Dimension of R
PV Pressure × Volume
R= =
nT Mole × Temperature
106
(Force / Area) × (Area × Length)

=
Mole × Degree(K)
Force × Length Work or energy

= = Mole × Degree (K)
Mole × Degree(K)
Physical Significance of R
The dimentions of R are energy per mole per kelvin and hence it represents the amount of work (or energy) that can be
obtained from one mole of a gas when its temperature is raised by 1K.
KEY POINTS
Units of R
1 atm × 22.4 lit
(i) In lit-atmR = = 0.0821 lit-atm mol–1K–1
273 K
1× 76 ×13.6 × 980 dyne cm –2 × 22400 cm3

(ii) In C.G.S system R =
273 K
= 8.314 × 107 erg mole–1K–1.
(iii) In M.K.S. system R = 8.314 Joule mole–1K–1. [107 erg = 1 joule]
8.314 ×107 erg mole –1K –1

(iv) In calories R=
4.184 ×107 erg
= 1.987 | 2 calorie mol–1K–1.
Ex. Some spherical balloons each of volume 2 litre are to be filled with hydrogen gas at one atm & 27°C from a cylinder
of volume 4 litres. The pressure of the H2 gas inside the cylinder is 20 atm at 127°C. Find number of balloons which
can be filled using this cylinder. Assume that temperature of the cylinder is 27°C.
20× 4
Sol. No. of moles of gas taken initially = = 2.43 L
R × 400
1× 4
No. of moles of gas left in cylinder = = 0.162L
R ×300
No. of moles of gas to be filled in balloons = 2.43 – 0.162 = 2.268
Let we have 'n' balloons that we can fill
1× 2
No. of moles of gas that can be filled in 1 balloon = = 0.081
0.082×300
? 0.081 × n = 2.268
n = 28 balloons.
Ex. At room temperature following reaction goes to completion
2NO + O2 o 2NO2 o N2O4

Dimer N2O4 at 262 K is solid. A 250 ml flask and a 100 ml flask are separated by a stop cock. At 300 K, the
nitric oxide in the large flask exerts a pressure of 1.053 atm and the smaller on contains O2 at 0.789 atm. The
gases are mixed by opening the stop cock and after the end of the reaction, the flasks are cooled to 220 K.
Neglecting the vapour pressure of dimer. Find out the pressure and composition of gas remaining at 220 K
(Assume gases behave ideally).
107
Sol. For NO gas :-
PV 1.053× 250
nNO = = = 1.069 × 10–2
RT 0.0821× 300 ×1000
0.789 ×100
For O2 gas :- n O 2 = = 0.32 × 10–2
0.0821× 300 ×1000
Now, 2NO + O2 o N2O4

Mole before reaction 1.069 × 10–2 0.32 × 10–2 0
Mole after reaction 1.069 × 10–2 – 2 × 0.32 × 10–2 0 0.32 × 10–2
= 0.429 × 10–2
Moles of NO left= 4.29 × 10–3
PNO × V = nRT Given T = 220 K
250 + 100 350
V= = litre
1000 1000
350
PNO × = 4.29 × 10–3 × 0.821 × 220
1000
PNO (left) = 0.221 atm.
DALTON'S LAW OF PARTIAL PRESSURES

Dalton's law of partial pressure states "at a given temperature, the total pressure exerted by two or more non-reacting
gases occupying a definite volume in equal to the sum of the partial pressures of the component gases."
PTotal = p1 + p2 + p3 + ...... (At constant V and T)
§ n1 n 2 n 3 · RT nRT
=¨ + + + ..... ¸ RT = (n + n + n + ......) =
©V V V ¹ 1 2 3 V V
Where n = n1 + n2 + n3 + ...... = Total moles, V = Total volume
RT
PTotal = ¦p i
V
=¦ ni
Dalton's law of partial pressure is applicable only to non-reacting gases.
If the two non-reacting gases A and B having nA and nB number of moles respectively are filled in a vessels of volume V
at temperature T, Then
PV = (nA + nB) RT ....(i)
Partial pressure may be calculated as
pAV = nART, pBV = nBRT
Total pressure (pA + pB) V = (nA + nB)RT .....(ii)
from (i) and (ii)
P = pA + pB
pA n A RT / V nA
= = = xA (mole fraction of A)
P (n A + n B )RT / V n A + n B
pA = xA × P, similarly pB = xB × P
Partial pressure of a component = Mole fraction × total pressure.
It has been observed that gases are generally collected over water and therefore are moist.
Pdry gas = P moist gas – Pwater vapour
The pressure exerted by water vapour is constant with water at a particular temperature is called as aqueous tension,
which varies directly with the temperature and becomes 760 mm at 100ºC.
108
Partial pressure of water in air

Relative Humidity (RH) =
Vapour pressure of water
Pressure of dry gas = Pressure of moist gas – aqueous tension.
Moist
(Gas + water vapour)
Ex. A mixture of NO2 & CO having total volume of 100 ml contains 70 ml of NO2 at 1 atm, mixture is left for some time and
same NO2 get dimerised to N2O4 such that final volume of the mixture become 80 ml at 1 atm, calculate the mole
fraction of NO2 in final equilibrium mixture.
Sol. Initial volume of NO2 = 70 ml
Initial volume of CO = 100 – 70 = 30 ml
Final volume of mixture = 80 ml
Let the volume of NO2 in final mixture be x
Let ‘v’ ml NO2 be converted to N2O4
2NO2 o N2O4
V V/2
Hence final volume
= volume of CO + volume of NO2 left + volume of N2O4 formed = 30 + 70 – V + V/2 = 80
V = 40 ml
Hence volume of NO2 left = 70 – V = 30 ml
Now as volume v moles
30 3
? mole fraction = volume fraction = =
80 8
Ex. A vessel of 2 lit capacity contains hydrogen at 380 mm pressure at 27ºC. 16gm of O2 is added to the container
then find the total pressure and partial pressure where R = 0.0821 L atm mol–1 k–1.
Sol. For H2 gas :
380 1
Given V = 2L and p H 2 = = atm
760 2
p H 2 V n H 2 RT
10000 1
1 = n H 2 × 0.0821 × 300 ; n H 2 = =
821× 300 24.6
16 1
Moles of O2 =
32 2
1 n H2
Partial pressure of H2 gas (p H2 ) = = ×P
2 n H 2 + n o2
1
1 24.6 × P
= or P = 6.65 atm
2 1 1
+
24.6 2
109
Ex. A 500 ml bulb is filled with CH 4 at a pressure of 1 atm and oxygen at a pressure of 4 atm at
27ºC. The mixture is then exploded, when the reaction CH4 + 2O2 o CO2 + 2H2O (A) occurs. Calculate the
pressure if the final temperature is 27ºC. Aqueous tension at 27ºC is 26.7 mm.
Sol. Partial pressure of CH4, ( p CH 4 )= 1 atm
Partial pressure of O2, ( p O2 ) = 4 atm
1× 0.5 0.5
? moles of CH4 present, ( n CH 4 ) = =
RT RT
4 × 0.5 2
? moles of O2 present ( n O 2 ) = =
RT RT
CH4(g) + 2O2(g) = CO2(g) + 2H2O(A)
0.5 2
Initially
RT RT
1 0.5
Finally –
RT RT
2 1 1
After the reaction, moles of residual O2 = – =
RT RT RT
0.5
After the reaction, moles of CO2 produced =
RT
1.5
Hence total no. of moles of O2 and CO2 =
RT
1.5 RT
? total pressure due to O2 and CO2 × = = 3 atm
RT 0.5
? pressure exerted by the entire gaseous components
26.7
=3+ = 3 + 0.03513 = 3.0513 atm
760
Ex. A mixture of CO and CO2 is found to have a density of 1.50 g/litre at 30ºC and 730 mm. Calculate the composition
of mixture.
Sol. For mixture, P = (730/760) atm,
T = 303 K, d = 150 g litre–1
d
? PV = nRT = (w/M) RT P(w/VM) RT P = RT
M
730 1.50
? = × 0.0821 × 303
760 M
? M = 38.85
Let n1 moles of CO and (100 – n1) moles of CO2 are present in 100 moles.
n1 × 28 + (100 – n1 ) × 44
? Average molecular weight (M) = = 38.85 n1 = 32.19
100
? mole % of CO = 32.19, and mole % of CO2 = 67.81.
110
Ex. An open vessel at 27ºC is heated until 3/5th of the air in it has been expelled. Assuming that the volume of
the vessel remains constant. Find
(a) the temperature at which vessel was heated ?
(b) the air escaped out if vessel is heated to 900 K ?
(c) temperature at which half of the air escapes out ?
Sol. One should clearly note the fact that on heating a gas in a vessel there are the number of moles of gas which
go out, the volume of vessel remains constant.
Let initial moles of air at 300 K be 'n'. On heating 3/5 moles of air are escaped out at temperature T.
§ 3 · 2n
? Moles of air left at temperature T = ¨ n – n ¸ =
© 5 ¹ 5
(a) Under simillar conditions of P and V
n1T1 = n2T2
2n
n × 300 = ×T T = 750 K
5
(b) On heating vessel to 900 K, let n1 moles be left again n1T1 = n2T2
1
n1 × 900 = 300 × n n1 = n
3
n 2
? moles escaped out = n – = n moles
3 3
(c) Let n/2 moles are escaped out at temperature T then
n1T1 = n2T2
n/2 × T = n × 300
T= 600 K
GRAHAM'S LAW OF DIFFUSION AND EFFUSION
Diffusion
The process of mixing of gases by random motion of the molecules is called diffusion.
Effusion
When gas is confined to a container at high pressure than in the surrounding atmosphere it will escape from a small hole
which is opened in the container until the pressure outside and inside have been equalised. This process is called
effusion.
The difference between diffusion and effusion is that in the former case, the gas spontaneously passes through a
porous partition while in the case of effusion, the gas is passed out through a small orifice or hole by applying some
external pressure.
Graham's law of diffusion states "under the same conditions of temperature and pressure, the rates of diffusion of
different gases are inversely proportional to the square roots of their molecular masses or their densities."
1 1 r1 M2 d2
Mathematically , r v or or,, r = M1 = d1
M d 2
Where r1 and r2 are the rates of diffusion of gases 1 and 2.

M1 and M2 are their molecular masses.
d1 and d2 are their densities.
Effect of Volume on Rate of Diffusion :
Volume of gas diffused
Rate of diffusion = Time taken for diffusion
V
or r =
t
111
Let V1 be the volume of gas 1 and V2 be the volume of gas 2, then
V1 V
r1 = r2 = 2
t1 t2
r1 M2 Vt
? = = 1 2
r2 M1 V2 t 1
(i) Comparison of Times Taken for the Same Volume of Two Gases
Let the times of diffusion for the same volume of two gases be t1 and t2 respectively. Then
r1 V / t1 d2 M2 r1 t 2 d2 M2
= = = or = = =
r2 V / t 2 d1 M1 r2 t1 d1 M1
(ii) Comparision of the Volumes of the Gases that Diffuse in Same Time
Let V1 and V2 be the volume of two gases that diffuse in same time t. Then,
r1 V1 / t d2 M2 r1 V1 d2 M2
= = = or = = =
r2 V2 / t d1 M1 r2 V2 d1 M1
(iii) Effect of Pressure on Rate of Diffusion

Rate of diffusion is proportional to the pressure of the gas in the container.
1 P r1 P1 M2
rv P ; again, r v or rv or =
M M r2 P2 M1
LIMITATIONS OF THIS LAW :

(i) The laws of diffusion and effusion are applicable only when the pressure difference is very small.
(ii) Correctly speaking the rate of diffusion and effusion are not constant throughout the time interval, but
these rates may be assumed constant for a small time interval.
Ex. The pressure in a bulb dropped from 2000 to 1500 mm of mercury in 47 minutes when the contained oxygen
leaked through a small hole. The bulb was then completely evacuated. A mixture of oxygen and another gas
of molecular weight 79 in the molar ratio of 1 : 1 at a total pressure of 4000 mm of mercury was introduced.
Find the molar ratio of the two gases remaining in the bulb after a period of 74 minutes.
Sol. The molar ratio of oxygen and the other gas in the evacuated bulb = 1 : 1 and the total pressure of the gas
mixture is 4000 mm, hence the partial pressure of each gas is 2000 mm.
The drop in the pressure of oxygen after 74 minutes
(2000 – 1500) × 74
= = 787.2 mm of Hg
47
? After 74 minutes, the pressure of oxygen = 2000 – 787.2 = 1212.8 mm of Hg
Let the rate of diffusion of other gas be rn, then
rn 32
=
rO2 79
32
? Drop in pressure for the other gas = 787.2 × = 501.01 mm of Hg
79
? Pressure of the other gas after 74 minutes = 2000 – 501.01 mm = 1498.99 mm of Hg
Moles of unknown gas 1498.99
Molar ratio = = = 1.236 : 1
Moles of O 2 1212.8
112
Ex. One mole of nitrogen gas at 0.8 atm takes 38 s to diffuse through a pinhole, whereas one mole of an unknown
compound of xenon with fluorine at 1.6 atm takes 57 s to diffuse through the same hole. Determine the molecular
formula of the compound.
Sol. Rate of diffusion, r v p
p
r v 1 / M or r v M
1/2
r2 p 2 § M1 ·
=
or r1 p1 ¨© M 2 ¸¹
1
Again, r v
t
1/2
t1 § p 2 ·§ M1 ·
or t2 = ¨ p ¸¨ M ¸
© 1 ¹© 2 ¹
2
§ p2t 2 ·
or M2 = ¨ p t ¸ M1
© 11¹
2
§ 1.6 57 ·
M2 = ¨ × ¸ × 28 = 252 g mol–1
© 0.8 38 ¹
Let the molecular formula of the unknown compound be XeFn.
Mxe + nMF = 252
or 131 + 19 n = 252
252 – 131
n= = 6.36 6
19
Hence, the molecular formula of the gas is XeF6.
Ex. A mixture containing 1.12 litre D2 and 2.24 litre of H2 at NTP is taken inside a bulb connected to another bulb
through a stop cock with a small opening. The second bulb is fully evacuated. The stop cock is opened for
a certain time and then closed. The first bulb is now found to contain 0.10 g of D2. Determine the % by weight
of the gases in second bulb.
Sol. At STP
D 2 = 1.12 lit.at STP = 0.2 g = 0.05 mole ½
Before diffusion ¾ in I bulb
H 2 = 2.24 lit.at STP = 0.2 g = 0.1mole ¿
(I) (II)
When these moles are placed in the bulb, the partial pressure of gas will be different because V and T are
constant. Also P v n
PD2 0.05 1
Thus, = =
PH2 0.10 2
After diffusion D2 left in I bulb = 0.1 g
or D2 diffuses from I into II (bulb) = 0.2 – 0.1 = 0.1 g
113
Now for diffusion of D2 and H2
rD2 M H2 PD2
= ×
rH2 M D2 PH2
w D2 t H2 M D2 PD2
' × = ×
t D2 w H2 M H2 PH2
0.1 t §4· 1
? × = ¨ ¸×
t w H2 ©2¹ 2
? w H2 = 0.14 g
? Wt. of gases in II bulb = wt. of D2 + wt. of H2
= 0.10 g + 0.14 g = 0.24 g
0.10
' % D2 by wt. = × 100 = 41.66 %
0.24
% H2 in bulb II = 58.33%
Ex. A spherical balloon of 21 cm diameter is to be filled up with hydrogen at NTP from a cylinder containing the
gas at 20 atmpsphere at 27ºC. If the cylinder can hold 2.82 litre of water at NTP, calculate the number of balloons
that can be filled up.
21
Sol. Radius of the balloon = cm = 10.5 cm
2
4 3 4 22
Volume of the balloon = πr = × × (10.5)3cc = 4851 cc
3 3 7
Pressure = 1 × 76 × 13.6 × 981 = 1.014 × 106 dynes/cm2
PV 1.014 ×106 × 4851
? No. of mole of H2, the balloon can contain at NTP = = = 0.2167
RT 8.314 ×107 × 273
20 × 76 ×13.6 × 981× 2820
No. of mole in the cylinder = = 2.2929
8.314 ×107 × 300
When the balloons are being filled, the pressure in the cylinder will decreases, when the pressure of the cylinder
will drop to 1 atm, gas cannot be withdrawn.
1.014 ×106 × 2820
Now, no. of moles of H2 remaining in the cylinder unused = = 0.1146
8.314 ×107 × 300
No.of moles of H 2 in the cylinder that can be used
? No. of balloons that can be filled =
No.of moles of H 2 in one balloon can contain
2.2929 – 0.1146
= = 10
0.2167
Ex. (a) How much H2 (in moles) is needed to inflate a balloon of radius 3.0 m to a pressure of 1.0 atm in an ambient
temperature of 25ºC at sea level ?
(b) What mass can the balloon lift at sea level, where the density of air is 1.22 kg m–3 ?
(c) What would be the payload if He were used instead of H2 ?
114
Sol. (a) PV = n H 2 RT
T
where P = 1 atm = 1.0132 × 105 N m–2,
4
V= × S × (3)3 m3,
3
R = 8.314 J mol–1 K–1, T = 298 K
5 4 22 3
PV 1.0132 ×10 × 3 × 7 × (3)
n H2 = = = 4.62 × 103 mol
RT 8.314 × 298
(b) Density of air = 1.22 kg m–3

hence, mass of air = volume of balloon × density
4 3 4 22
= πr × d = × × (3)3 × 1.22 kg = 138.03 kg
3 3 7
mass of H2 = n H 2 × Mw of H2 = 4.62 × 103× 2 = 9.24 kg

hence, the mass that the balloon can lift
= mass of air – mass of H2 = 138.03 – 9.24 = 128.79 kg
(c) Payload if He were used instead of H2 = 138.03 – 18.48 = 119.55 kg
[Mass of He = nHe × Mw of He = 4.62 × 103 × 4 = 18.48 kg]
KINETIC THEORY OF GASES

The theoretical model for all the experimental gas laws can be analys with the help of kinetic theory of gases which
is based on following assumptions :
(a) All the gases consists of very small molecules or atoms whose volume is negligible compared to volume of
container (in case volume of container is very small, then this assumption will be violated)
(b) There is no interaction between gaseous particles (the interaction may appreciably affected under certain
conditions of temperature and pressure).
(c) The gaseous molecules are under a continuous state of motion which is unaffected by gravity (the random
straight line motion is known as brownian motion)
(d) Due to the continuous motion, collision between gaseous molecules with the wall of cantainer occurs. The
collision with the wall of container are responsible for pressure exerted by the gas on the wall of container.
(e) The molecule moves with different speed, however the speed of each molecule keep on changing as the collision
occur.
(f) All the collision occuring are considered to be perfectely elastic which implies that there is no loss of energy.
(g) The average kinetic energy of gas will depends on absolute temperature only.
Derivation of Equation for Kinetic Molecular Theory :

Let us consider a cube of side L, that has N0 molecules each of mass m moving with velocity u in all direction and
thus colliding with one each other and against sides of the container. Velocity u can be resolved into three
components ux, uy and uz along there axes such that
u2 = u 2x + u2y + u2z (assume velocity in ms–1 and distance in meter)
115
y
L
Z
Before collision After collision

+ ux – ux
Face B Face A
For a simplest case we consider motion of a molecule along x-axis only in which it moves towards face B with velocity
ux. After collision against face B it moves towards face A with velocity (– ux) collissions being elastic (which results
in change in direction but not velocity)
? Momentum before collision on face B = mux
Momentum after collision on face B = – mux
Change in momentum due to one collision on face B
= mux – (– mux) = 2mux
To strike face B again distance travelled = 2L
2L
Time taken to strike face B again = seconds
ux
ux
? Number of collisions per second on face B along x-axis =
2L
ux ux mu 2x
? Change in momentum due to collisions per second on face B along x-axis = 2mux · =
2L 2L L
2mu 2x
Change in momentum per second due to collisions of one molecule on opposite faces A and B along x-axis =
L
2mu 2y 2mu 2z
Similarly for y-axis change in momentum per second = and for z-axis =
L L
Total change in momentum per second due to collisions of a single molecule on six faces along three axes
2mu 2x 2mu 2y 2mu 2z

= + +
L L L
2m 2 2mu 2
= (u x + u 2y + u 2z ) =
L L
But rate of change in momentum per second = Force
116
2mu 2
? Force =
L
2mu 2
Force L mu 2 mu 2
? Pressure = = = = [L3 = volume V]
Area of six faces 6L2 3L3 3V
1
? Pressure due to collisions of N0 molecules on six faces of a cube = mN0u2
3
1 1
PV = mN0u2 = Mu2
3 3
mN0 = M (molar mass)
N0 = Avogadro's number
u = root mean square velocity (Urms)
Translational Kinetic Energy of n Moles

1 3 3
Mu2 = PV = nRTT
2 2 2
Average Translational Kinetic Energy Per Molecule
3 RT 3
= = KT
2 N0 2
§ R ·
Where K ¨ = ¸ is called Boltzmann's constant.
© N0 ¹
Its numerical value is 1.38 × 10–16 erg K–1 molecule–1
Thus average K.E. is proportional to absolute temperature.
If T = 0 K (i.e., – 273.15ºC), then average KE = 0
Thus, absolute zero (0 K) is the temperature at which molecular motion ceases.
DIFFERENT TYPES OF MOLECULAR VELOCITIES

1
PV = MU 2rms
3
(i) Root mean square velocity (Urms) : It is defined as the square root of the mean of the squares of the
velocities possessed by all the molecules present in the given sample of gas
U12 + U 22 + ...U n2
Urms =
N
3PV 3RT 3P
? Urms (root mean square velocity) = = =
M M d
Where d is the density.
y If N1 molecules have velocity u1 and N2 molecules have velocity u2, then
N1u12 + N 2 u 22
Urms =
N1 + N 2
117
(ii) Average velocity (Uav) : It is given by the arithmetic mean of square of the different velocities possessed
by the molecules of the gases at a particular temperature.
U12 + U 22 + ...U 2n
Uav =
n
8RT
y Uav (average velocity) =
πM
(iii) Most probable velocity (Ump) : It is defined as the velocity possessed by the maximum number of
molecules of a gas at a given temperature.
2RT
y Ump (most probable velocity) =
M
y If P and T both are given, use equation in terms of temperature i.e. use
3RT 3PV
Urms = and not
M M
y To have velocity in ms–1 (MKS) take R = 8.314 J mol–1K–1, M in kg.
y If density is in kg m–3 and P in N m–2, velocity will be in ms–1.
Relation between rms velocity, average velocity and most probable velocity.
3RT 8RT 2RT 8

y Urms : Uav : Ump = : : = 3: : 2 = 1.2248 : 1.1284 : 1
M πM M π
Urms = 1.2248 Ump
Uav = 1.1284 Ump
Ump = 1.0854 Uav
Ex. (a) Calculate the pressure exerted by 1023 gas molecules, each of mass 10–25 kg, in a container of volume 1×
10–3 m3 and having root mean square velocity of 103 ms–1.
(b) Also calculate total kinetic energy and
(c) temperature of the gas.
Sol. (a) By kinetic theory
1 mNu 2 1 u 1 0 2 5 u 10 23 u (10 3 )2
P= = = 3.33 × 106 N m–2
3 V 3 u 10 3
§1 2 ·
(b) Total KE = ¨ mu ¸ × N
©2 ¹
1 1
= × 10–25 × (103)2 × 1023 = × 104 = 0.5 × 104 J
2 2
3 10 23 1023
(c) Also total KE = nRT, where n (mole) = =
2 NA 6.023×1023
3 1023
0.5 × 104 = × × 8.314 × T
2 6.023 ×1023
0.5 ×104 × 2 × 6.023

?T= = 2415 K
3× 8.314
118
Ex. A gas bulb of 1 litre capacity contains 2.0 × 10 21 molecules of nitrogen exerting a pressure of
7.57 × 103 Nm–2. Calculate the root mean square velocity of the gas molecules.
Sol. No. of gas molecules = 2 × 1021
6.023 × 1023 molecules of nitrogen weight = 28 g
28 × 2 ×1021
2 × 1021 molecules of N2 weights = g = 0.093 g
6.023×10 23
Mass 0.093 0.093×10 –3
? Density= = g/L = = 0.093 kg/m3
Volume 1 10 –3
3RT 3PV 3P 3 × 7.57 ×103

Urms = = = = Urms = = 494.16 m/s
M M d 0.093
Ex. In a container of capacity 1 litre there are 1023 molecules each of mass 10–22 gms. If root mean square speed is 105 cm/
sec then calculate pressure of the gas.
1
Sol. PV = MN U2
3
P=?
V = 10–3 m3
m = 10–25 kg
N = 1023
U 2 = 10 cm/sec = 10 m/sec
5 3
U2 = 106 m2 /sec2
1
P × 10–3 = × 10–25 × 1023 × 106
3
1
P= × 10–2 × 106 × 103
3
1
P= × 107 pascals
3
IDEAL AND REAL GAS
An ideal gas is a hypothetical gas whose pressure, volume and temperature behaviour is completely described by the
ideal gas equation. Actually no gas is ideal or perfect in nature. All gases are real gases.
Real gases do not obey the ideal gas laws exactly under all conditions of tamperature and pressure.
Real gases deviates from ideal behaviour because of mainly two assumptions of "Kinetic theory of gases".
(i) The volume of gas particle is negligible compared to volume of container (while the real gas particle have some
significant volume).
(ii) There is no interaction between gaseous particles (while attraction forces exist between real gas particles).
y Deviation from Ideal Behaviours
Compressibility Factor
The extent to which a real gas departs from the ideal behaviour may be expressed in terms of compressibility factor
(Z), where Z is
Vm PVm
Z= [Vm = molar volume]
Vm (ideal) RT
When Z > 1, Vm > 22.4 lit at STP ; When Z < 1, Vm < 22.4 lit at STP
119
Plots of Compressibility Factor vs Pressure
(i) For an ideal gas Z = 1 and is independent of temperature and pressure.
(ii) Exceptional behaviour of H2 and He :
for these gases Z > 1. For such gases repulsive forces predominants.
(iii) Effect of pressure :
At very low P, PV | RT i.e. Z | 1
At low P, PV < RT i.e. Z < 1
At moderate P, PV | RT i.e. Z | 1
At high P, PV > RT i.e. Z > 1
(iv) For the gases which are easily liquefied (e.g. CO2) Z dips sharply below the ideal line in the low pressure region.
(v) Effect of temperature : An increase in temperature shows a decrease in deviation from ideal behaviours i.e. PV
approaches unity or Z approaches unity with increase in temperature.
T4
H2 T3
T 1 > T2 > T3 > T4
He T2
N2
CH4 T1
1.0 ideal gas Z = 1 1.0
Z CO 2 ideal gas
Z <1 Z
0 100 200 300 0 200 400 600

P P
Boyle's Temperature
The temperature at which a real gas behaves like an ideal gas over an appreciable range of pressure is known
as Boyle's temperature (TB). It means that at this temperature, the value of PV remains constant for an
appreciable range of pressure, i.e. Boyle's Law is abeyed. Mathematically we may express the Boyle temperature
w (PV)
or Boyle point as the temperature where = 0 when P o 0.
wP
So to use ideal gas equation for real gas, we will use some correction factor for volume as well as for pressure.
(A) Volume Correction :
In the ideal gas equation, PiVi = nRT, Vi represents the ideal volume where the molecules can move freely. In
real gases, a part of the total volume is occupied by the gas molecules. Hence the free volume Vi is the total
volume V minus the volume occupied by the gas molecules.
i.e. Real volume of gas = Actual volume of container – volume occupied by N molecules in motion.
Vi = V – b for one mole of gas
Vi = V – nb for n mole of gas
d
excluded
volume
d
Illustration of excluded volume
Where b is termed the 'excluded volume' or 'co-volume'.
It is constant and characteristic for each gas.
120
§4 3·
b = ¨ πr ¸ × 4N
©3 ¹
[where r = radius of gas molecule, N = Avogadro's number]
(B) Pressure Correction
In order to take account the effect of intermolecular forces of attraction, let us consider a molecule A is the midst
of the vessel.
A • •
• • •
• • • B
• • •
• •
This molecule is surrounded by other molecules in a symmetrical manner and is being attracted uniformly on
all sides by the neighbouring molecules with the result that this molecule on the whole experiences no net force
of attraction.
Now, consider a molecule B near the side of the vessel, which is about to strike one of its sides, thus
contributing towards the total pressure of the gas. There are molecules only on one side of the vessel, i.e.
towards its centre, with the result that this molecule experiences a net force of attraction towards the centre
of the vessel. This results in decreasing the velocity of the molecule, and hence its momentum. Thus, the
molecule does not contribute as much force as it would have, had there been no force of attraction. Thus, the
pressure of a real gas would be smaller than the corresponding pressure of an ideal gas.
REAL GAS EQUATION OR VAN DER WALLS GAS EQUATION
Van der Walls noted that the total force of attraction on any molecule about to hit a wall is proportional to the
concentration of neighbouring molecules, n/V. However, the number of molecules about to hit the wall per unit
wall area is also proportional to the concentration n/V. Therefore, the force per unit wall area, or pressure, is
reduced from that assumed in the ideal gas wall by a factor proportional to n2/V2. Letting a be the proportionality
constant, we can write
P (actual) = P(ideal) – n2a/V2
or P (ideal) = P(actual) + n2a/V2
'a' is a constant which depends upon the nature of the gas, V is the volume of 1 mole of gas.
Combining the two corrections, for 1 mole of gas
§ a ·
¨ P + 2 ¸ (V – b) = RT
T
© V ¹
§ n 2a ·
For n mole of gas ¨ P + 2 ¸ (V – nb) = nRT Van der wall gas equation
© V ¹
• At high temperature and low pressure, it acts as ideal gas equation.
• a, b are van der Waal’s gas constant depends on nature of gas.
van der Waal’s gas constant (a) :
where a is a van der waal gas constant which indicates the inter molecular force of attraction.
an 2
Pr essure
V2
unit of a = atm lit2 / mol2
an 2
Pi P
V2
Pi > PR
• an, Fattn, liquefactionn.
121
van der Waal gas constant (b)

It tells about molecular volume of gas molecules.
lit.
Unit of b
mol.
b = correction volume
b = incompressible volume
Vi > VR
• If bn, effective size of moleculen
Incompressible volumen
compressible volumep
• Order of b is 10–2 to 10–4 L/mol
Effect of pressure on van der Wall gas equation
Case I At very-very low pressure
(Z = 1) Z>1
§ n 2a · III
¨P 2 ¸ (V nb ) nRT PV Z=1
¨ V ¸ II
© ¹
PV = nRT I
PV Z<1
1
nRT P
Z 1
Case II At low pressure/ moderate pressureq Case III At very high pressure
(Z < 1) (Z > 1)
§ n 2a · § n 2a ·
¨ P 2 ¸ (V nb ) nRT ¨P 2 ¸ (V nb) nRT
© V ¹ ¨ V ¸
© ¹
n 2a
PV nRT PV – nPb = nRT
V
PV na PV Pb
1 1
nRT VRT nRT RT
na Pb
Z 1 Z 1
VRT RT
LIQUEFACTION OF GASES
The phenomenon of converting a gas into liquid is iknown as liquefaction. The liquefaction of gas takes place when
the intermolecular forces of attraction become so high that exist in the liquid. A gas can be liquefied by :
(a) Increasing Pressure : An increase in pressure results in an increase in attraction among molecules.
(b) Decreasing Temperature : A decrease in temperature results in a decrease in kinetic energy of molecueles.
• A gas may be liquefied by cooling or by the application of high pressure or by the combined effect of both.
The first successful attempt for liquefying gases was made by Faraday.
• Gases for which the intermolecular forces of attraction are small such as H2, N2, Ar and O2, have low values
of Tc and cannot be liquefied by the application of pressure are known as “permanent gases” while the gases
for which the intermolecular forces of attraction are large, such as polar molecules NH3, SO2, and H2O have
high values of Tc and can be liquefied easily.
122
Methods of liquefaction of gases : The modern methods of cooling the gas to or below their Tc and hence of
liquefaction of gases are done by Linde’s method and Claude’s method.
(i) Linde’s method : This process is based upon Joule-Thomson effect which states that “When a gas is
allowed to expand adiabatically from a region of high pressure to a region of extremely low pressure, it
is accompanied by cooling.”
(ii) Claude’s method : This process is based upon the principle that when a gas expands adiabatically against
an external pressure (as a piston in an engine), it does some external work. Since work is done by the
molecules at the cost of their kinetic energy, the temperature of the gas falls causing cooling.
(iii) By adiabatic demagnetisation.
Uses of liquefied gases : Liquefied gases compressed under a high pressure are of great importance in industries.
(i) Liquid ammonia and liquid sulphur dioxide are used as refrigerants.
(ii) Liquid carbon dioxide finds use in soda fountains.
(iii) Liquid chlorine is used for bleaching and disinfectant purposes.
(iv) Liquid air is an important source of oxygen in rockets and jet-propelled planes and bombs.
(v) Compressed oxygen is used for welding purposes.
(vi) Compressed helium is used in airships.
Critical Temperature (TC) : The maximum temperature at which gas can be liquefied by the application of
pressure alone i.e. the temperature above which a liquid cannot exit is called the critical temperature T C.
8a
Tc
27bR
Critical Pressure (PC) :The minimum pressure required to liquefy the gas at the temperature T C is called the
critical pressure PC.
a
Pc
27b 2
Critical Volume (VC) :The volume occupied by one mole of the gas at critical temperature, TC and critical
pressure, PC is called the critical volume (VC) of the gas.
Vc = 3b
CRITICAL CONSTANTS OF GASES
Gas PC (atm) Vm,c (cm3mol–1) TC (K)
He 2.26 57.9 5.2
Ne 26.9 41.7 44.4
Ar 48.1 75.2 150.7
Xe 58.0 119.0 289.7
H2 12.8 65.5 33.3
O2 50.1 78.2 154.8
N2 33.5 90.1 126.2
CO2 72.8 94.0 304.2
H2O 218.0 55.6 647.3
NH3 111.5 72.5 405.0
CH4 45.6 98.7 190.6
C2H6 48.2 148.0 305.4
Ex. Calculate the pressure exerted by 5 mole of CO2 in one litre vessel at 47ºC using van der waal's equation. Also
123
report the pressure of gas if it behaves ideal in nature.
Given that a = 3.592 atm lt2 mol–2, b = 0.0427 L/mol. Also, if the volume occupied by CO2 molecules is negligible,
then calculate the pressure exerted by one mole of CO2 gas at 273 K.
Sol. Vander waal's equation
ª n 2a º
« p + V 2 » [V – nb] = nRT
T
¬ ¼
n CO 2 = 5, V = 1 litre, T = 320 K, a = 3.592, b = 0.0427
ª 3.592 º
? «¬ P + 25 × 1 »¼ [1 – 5 × 0.0427] = 5 × 0.0821 × 320
? P = 77.218 atm
For ideal behaviour of gas, PV = nRT
? P × 1 = 5 × 0.0821 × 320
? P = 131.36 atm
ª a º
For one mole « P + 2 » [V – b] = RT
T
¬ V ¼
RT a
? P= – 2
V V
0.0821× 273 3.592
? P= –
22.4 (22.4) 2
? P = 0.9922 atm
The volume occupied by 1 mole at 273 K is 22.4 litre if b is negligible.
Ex. Two moles of ammonia gas are enclosed in a vessel of 5 litre capacity at 27ºC. Calculate the pressure exerted
by the gas, assuming that
(i) the gas behaves like an ideal gas (using ideal gas equation).
(ii) the gas behaves like a real gas (using van der Waal’s equation)
Given that for ammonia, a = 4.17 atm litre2 mol–2 and b = 0.037 litre mol–1.
Sol. Given,
n = 2 moles
V = 5 litres
T = 27ºC = (27 + 273) K = 300 K
a = 4.17 atm litre2 mol–2
b = 0.037 litre mol–1
Also, we know that
R = 0.0821 litre atm K–1 mol–1
(i) If the gas behaves like an ideal gas, we have
PV = nRT
nRT 2 × 0.0821× 300
? P= = = 9.85 atm
V 5
(ii) If the gas behaves like a real gas, we apply van der Waal's equation i.e.
§ an 2 ·
¨ P + 2 ¸ (V – nb) = nRT
T
© V ¹
nRT an 2 2 × 0.0821× 300 4.17 × (2)

2
or P = – 2 = – 2 = 9.33 atm.
V – nb V 5 – 2 × 0.037 (5)
124
Ex. 1 mole of CCl 4 vapours at 77ºC occupies a volume of 35.0 L. If vander waal's constants are
a = 20.39 L2 atm mol–2 and b = 0.1383 L mol–1, calculate compressibility factor Z under,
(a) low pressure region. (b) high pressure region.
Sol. (a) Under low pressure region, V is high
? (V – b) | V
§ a ·
¨ P + 2 ¸ V = RT
T
© V ¹
a
PV + = RT
T
V
PV a
+ =1
RT RTV
PV § a · 20.39
Z= = ¨1 – ¸ =1– = 0.98
RT © RTV ¹ 0.0821× 350 × 35
(b) Under high pressure region, P is high,
§ a ·
¨P + 2 ¸ |P
© V ¹
? P (V – b) = RT
PV – Pb = RT
PV Pb
– =1
RT RT
PV Pb § PV P 1·
? Z= =1+ ¨' = 1, or = ¸
RT RT © RT RT V ¹
b 0.1383
Z=1+ =1+ = 1 + 0.004 = 1.004
V 35
Ex. The critical temperature and pressure of CO2 gas are 304.2 K and 72.9 atm respectively. What is the radius of
CO2 molecule assuming it to behave as vander Waal’s gas ?
Sol. TC = 304.2 K PC = 72.9 atm
8a a
TC = PC =
27Rb 27b 2
8a
TC 27Rb 8a 27b 2 8b
? PC = = × =
a 27Rb a R
2
27b
RTC 1 0.082× 304.2

or b = = × = 0.04277 lit mol–1
8PC 8 72.9
4 3
b = 4 NA × πr = 42.77 cm3
3
4 3
? 4 × NA × πr = 42.77
3
125
3 × 42.77 × 10 –23
or r3 =
16 × 6.023 × 3.14
or r3 = 0.424 × 10–23 = 4.24 × 10–24
or r = (4.24)1/3 × 10–8 cm = 1.62 × 10–8 cm
? radius of CO2 molecule = 1.62 Å
Ex. The vander waals constant for HCI are a = 371.843 KPa.dm6 mol–2 and b = 40.8 cm3 mol–1 find the critical constant
of this substance.
a 371.843 ×103 371.843 ×109

Sol. The critical pressure, PC = = 2 –6 = = 8.273 x 106
27b 2 27 × (40.8) ×10 27 × (40.8) 2
PC = 8.273 MPa
8a
The critical pressure, T C =
27Rb
R = 8.314 KPa dm3 K–1 mol–1
8a 8×371.843
TC = = = 324.79 = 324.8 K
27Rb 8.314× 27 × 40.8×10 –3
The critical volume, VC = 3b = 3 x 40.8 = 122.4 cm3
Ex. In a container of capacity 1 litre, air and some liquid water is present in equilibrium at total pressure of 200 mm of Hg.
This container is connected to another one litre evacuated container. Find total pressure inside the container when
equilibrium is again stablised (aqueous tension or vapour pressure at this temp. is 96 mm Hg).
Sol. Total pressure = 200 mm of Hg = Pgas + Pvapour water
Pgas + 96 = 200
Pgas = 104 mm of Hg Initially
when second container is connected
P1 = 104 mm of Hg P2 = ?
V1 = 1 V2 = 2 litre
P1 V1 = P2 V2
104 × 1 = P2 × 2
52 = P2
After equilibrium is established
Ptotal = 52 + 96 = Pgas + Pwater = 148 mm of Hg at equilibrium.
Ex. Carbon dioxide gas (CO2) measuring 1 litre is passed over heated coke the total volume of the gases coming out
becomes 1.6 litre. Find % conversion of CO2 into carbon monoxide.
Sol. CO2 + C o 2CO CO2 CO
1 0 at time t 1–x 2x
Initial volume = 1 litre
final volume = 1.6 litre Final volume = (1 + x) litres
1 + x = 1.6
x = 0.6
x = 0.6
0.6
× 10 = 60% of CO2 will be converted into CO
1
126
Ex. 100 ml of hydrocarbon is mixed with excess of oxygen and exploded. On cooling, the mixture was reported to have
a contraction of 250 ml. The remaining gas when passed through a solution of aqueous KOH, the mixture shows a
further contraction of 300 ml. Find molecular formula of the hydrocarbon.
§ Y· y
Sol. Cx Hy + ¨ x + ¸ O2 o x CO2 + H2O
© 4¹ 2
y
100 ml x 100 100.
2
mixture contains CO2 , H2O & excess O2
on cooling, H2O is separated, volume of H2O = 250 ml
y
× 100 = 250 ; y = 5,
2
as KOH absorbs CO2, hence 300 ml contraction is because of CO2 that has been absorbed.
Volume of CO2 = 100 x = 300 ; x = 3
Empirical formula = C3 H5 ; molecular formula = C6 H10.
Note : If water is already condensed out then total contraction in reaction mixture = {volume of reactants} – {volume of
products + volume of unused species excluding volume of H2O}.
127
LIQUID STATE
Liquid state is intermediate between gaseous and solid states. The liquids posses fluidity like gases but incompressibility
like solids.
The behaviour of liquids explained above gives some characteristic properties to the liquids such as definite shape,
incompressibility, diffusion, fluidity (or viscosity), evaporation (or vapour pressure), surface tension, etc.
Properties of liquids can be explained on the basis of kinetic molecular theory which has the following postulates:
(i) A liquid is made up molecules; atoms in rare cases, e.g., Hg (mercury)
(ii) The molecules of the liquid are quite close together.
(iii) The intermolecular forces of attraction in a liquid are quite large.
(iv) The molecules of liquids are in a state of constant rapid motion.
(v) The average kinetic energy of the molecules of a liquid is directly proportional to their absolute tempera
ture.
Vapour Pressure : When the space above the liquids is closed, the molecules cannot escape into open but strike the
walls of the container, rebound and may strke the surface of the liquid, where they are trapped. The return of the
molecules from the vapour state of the liquid state is known as condensation. As evaporation proceeds, the number of
molecules in the vapour state increases and, in turn, the rate of condensation increases.
The rate of condensation soon becomes equal to the rate of the evaporation, i.e., the vapour inthe closed container is in
equilibrium with the liquid.
Evaporation
Equilibrium
Rate
Condensation
Time
At equilibrium the concentration of molecules in the vapour phase remains unchanged. The pressure exerted by the
vapour in equilibrium with liquid, at a given temperature, is called the vapour pressure. Mathematically, it is given by the
gas equation.
n
P RT CRT
V
Where C is the concentration of vapour, in mol/litre.
Since the rate of evaporation increases and rate of condensation decreases with increasing temperature, vapour pressure
of liquids always increases as temperature increases. At any given temperature, the vapour pressure of different liquids
are different because their cohesive forces are different. Easily vaporised liquids are called volatile liquids and they have
relatively high vapour pressure. Vapour pressure values (in mm of Hg) for water, alcohol and ether at different temperature
are given in the following table :
It is observed that non-polar or less polar liquids such as diethyl ether alcohol possess fairly high vapour pressure on
account of weak intermolecular forces (cohesive forces) whereas polar molecules such as water which have stronger
intermolecular forces posses relatively lower vapour pressure.
The simplest method for measuring vapour pressure is the barometric method.
Surface Tension : It is the property of liquids caused by the intermolecular attractive forces. A molecule within the bulk
of the liquid is attracted equally in all the directions by the neighbouring molecules. The resultant force on any one
molecule in the centre of the liquid is, therefore, zero. However, the molecules on the surface of the liquid are attracted
only inward and sideways. This unbalanced molecular attraction pulls some of the molecules into the bulk of the liquid,
i.e., are pulled inward and the surface area is minimized.
Surface tension is a measure of this inward force on the surface of the liqud. It acts downwards perpendicular to the
plane of the surface. The unit of surface tension is dyen cm–1. Surface tension is, thus defined as the force in dyen acting
on the surface at right angles to any line of unit length. As the intermolecular forces of attraction decreases with the rise
128
of temperature, the surface tension of a liquid, thus, decreases with increase in temperature. Similarly, addition of
chemicals to a liquid reduce its surface tension. For example, addition of chemicals like soaps, detergents, alcohol,
camphor, etc., lowers the surface tension of water.
Many common phenomena can be explained with the help of surface tension. Some are described here :
(a) Small droplets are spherical in shape : The surface tension acting on the surface of the liquid tries to minimise the
surface area of a given mass of a liqud. It is known that for a given volume, a sphere has the minium surface area. On
account of this, drops of liquids acquire a spherical shape.
(b) Insects can walk on the surface of water : Many insects can walk on the surface of water without drowing. This is
due to the existence of surface tensio. The surface tension makes the water surface to behave like an elastic
membrane and prevents the insects from drowing.
(c) Cleaing action of soap and detergents : Soap and detergent solutions due to their lower surface tensions penetrate
into the fibre and surround the greasy substances and was them away.
(d) Capilarly action : The tendency of a liquid to rise into narrow pores and tiny openings is called capillary action. The
liquids rise in the capillary tubes due to the surface tension. The molecules of glass of the capillary tube is greater
than the force of cohesion between water molecules. Due to this, surface of water in a glass capillary tube curves
upwards in convex shape and then the force of surface tension of water pulls the water up into the tube. The water
rises into a capillary tube to such a height that the weight that the weight of resulting water column is just balanced
by the force of surface tension.
The rise of a oil in a lamp wick and flow of water from the roots of a tree to upper parts are also the examples of
capillary action. In general, the liquids which wet the material show capillary always show depression, e.g., glycerine,
honey, mercury, etc.
When a liquid reises in a column, its upper surface becomes concave and when the liquid goes down in a capillary,
its upper surface becomes conves.
(e) Surface Energy : The work in erg required to be done to increase or extend surface area by 1 sq. cm is called surface
energy. The units of surface energy are, therefore, erg per sq. cm (or joule per sq. metre, i.e. J m–2 in S.I. system)
Measurement of surface tension : The surface tension of aliquid is measured by the drop count method using a
stalagmometer.
Ley J1 and d1 be the surface tension and density of water and J2 and d2 be surface tension and density of the liquid
whose surface tension is to the determined. Using a stalagmometer the number of drops formed by the same volume
of water and liquid is determined.
J1 n1d 2
J2 n 2d1
Using the above relation, the surface tension of the liquid, J2, can be calculated.
Viscosity
All the liquids have a characteristic property of flow. Some liquids like water, alcohol, ether, etc. flow quickly while
glycerine, castor oil, molasses, etc, flow very slowly. The Property of the liquids which determines their resistance to
flow, is called viscosity.
When a liquid flows trhough a pipe, all parts of it do not move at the same rate. The thin layer in imediate contact with
the wall of the pipe is almost stationary. The velocity of flow of each successive layer of liquid increases progressively
as we proceed inward towards the centre. At the centre the flow becomes fastest. Each layer of liquid moving with greater
velocity over the one having lower velocity will experience a retarding effect due to the internal friction between the
friction between the two layers. This internal friction or resistance is called viscosity.
Imagine a liquid to be made up of a friction ‘f’ between two cylindrical layers each having area ‘A’ sq. cm separated by
a distance ‘x’ cm and having a velocity difference X cm/sec. is given by
129
X
fD A
x
X
f KA
x
Here K is a constant known as coefficient of viscosity. If x = 1 cm, A = 1 cm2 and X = 1 cm/sec then f =K . Thus, coefficient
of viscosity can be defined as the force per unit area need to maintain unit difference of velocity between two cinsecutive
parallel layers of the liquid which are one centimetre apart. Coefficient of viscosity is expressed in dyne cm–2 sec. It is
more commonly expressed to poise, centripoise (10–2 poise) and millipoinse (10–3 poise), after the name of Poiseuille who
derived the formula and gave the method for its determination. One poise is equal to a force of one dyne per unit area
which maintains a velocity of one cm per second between two parallel consecutive layers of the liquid one cm apart.
The reciprocal of the coefficient of viscosity is called Fluidity (I).
1
I Fluidity
K
Liquids with low viscosity are termed mobile and others with high viscosity are called viscous.
Viscosity depends on the following factors :
(a) Intermolecular forces : the liquids with high intermolecular attractive forces offer greater resistance to the
flow of molecules and thus possess high viscosity.
(b) Molecular mass : The flow of molecules inversely proportional to its mass. Liquids having high molecular
mass possess greater viscosity.
(c) The structure and shape of molecules : Viscosity generally increases as the branching in the chain
increases. Symetrical molecules have low viscosity.
130
1. GAS LAW
(I) Boyle’s Law
1
Vv (n,T co nst)
P
P1V1 = P2V2
(II) Charle’s Law
V v T (n, P = const)
V2 T2
V1 T1
(III) Gay lussac’s Law

P v T (n, V = const)
P2 T2
P1 T1
(IV) Avogadro’s Law

V v moles v number of molecules (P, T = cosnt)
Ideal gas equation PV = nRT
R = 0.0821 lit atm mol–1 K–1
R = 8.314 J K–1 mol–1 or 8.314 N × K–1 mol–1
–1
R = 2 cal K mol –1
R = 8.314 × 107 erg K–1 mol–1

2. GRAHAM’S DIFFUSION LAW
It is applicable for non reacting gases
1
rv
d
1
rv
VD
1
rv (P, T = const)
Mw
dgas Mw
VD
dH 2 2
A diffused gas
rate of diffusion r
t time taken
(Where, A = distance travelled by differed gas)
Vdiffused gas
r
t time taken
n diffused gas
r
t time taken
131
3. DALTON’S LAW OF PARTIAL PRESSURE
Pmixture = P1 + P2 + P3 ........ (T & V const)
Pt = Pmoist gas = P dry gas + P water vapours
It is applicable for non racting gases.
Methods of determination of partial pressure
(PA & PB are partial pressure)
(I) from ideal gas equation
PAV = nA RT and PBV = nBRT
(II) In the form of mole fraction.
nA
PA = XA PT = n PT
t
nB
PB = XB PT = n PT
t
PT = sum of partial pressure of al gases

(III) In the form of volume fraction
VA VA
PA = PT and PB = PT
V V
(IV) In individual pressure and individual volume are given
VA VB
PA = P1 and PB = P2
V V
P1, P2 = pressure of gases before mixing
PA, PB = pressure of gases after mixing
4. Kinetic gas equation
1
PV = mN V2rms
3
5. Average KE (KEav)
3
KEav = nRT
T (m moles)
2
3
KEav = RT
T ( 1 mol or NA molecules)
2
3
KEav = KT (1 molecules)
2
K = 1.38 × 10–23 JK–1 molecule–1
V12 V22 ...Vn2 V1 V2 V3 ...Vn

6. Vrms Vav
N N
3RT 8RT 2RT

Vrms Vav Vmp
Mw S Mw Mw
3PV 8PV 2PV

Vrms Vav Vmp
Mw S Mw Mw
132
3P 8P 2P
Vrms Vav Vmp
d Sd d
8
Vrms : Vav : Vmp = 3 : : 2
S
=1 : 0.92 : 0.82
8
Vmp : Vav : Vrms = 2 : : 3
S
=1 : 1.128 : 1.224
(Vm )obs P(Vm )obs

7. Compressibility factor (z) = Vi RT
If z = 1, the gas show ideal gas behaviour.
If z > 1, the gas show positive deviatioin.
If z < 1, the gas show negative deviation.
8. Vanderwaal’s Sequation
§ an 2 ·
¨ P 2 ¸ (V – nb) = nRT
T
© V ¹
an 2
Pi = PR + Pi > P R
V2
a n force of attraction n , liquification n
b n , effective size of molecule n
incompressible vol n , compressible vol p
(I) At high pressure, Vanderwaal’s equation is PVm – Pb = RT
a
(II) At low pressure Vanderwaal’s equation is PVm + RT
Vm
133
SOLVED EXAMPLE
Ex. 1 A gas column is trapped between closed end of a Ex. 3 A gas is initially at 1 atm pressure. To compress it to
tube and a mercury column of length (h) when this 1/4 th of initial volume, what will be the pressure
tube is placed with its open end upwards the length required ?
of gas column is (A1), the length of gas column Sol. P1 = 1 atm V1 = V
becomes (A 2 ) when open end of tube is held
downwards. Find atmospheric pressure in terms of V
P2 = ? V2 =
height of Hg column. 4
P1V1 = P2V2 at const. T & n
P1V1 1 atm × V
P2 = = = 4 atm Ans.
V2 V
4
Ex. 4 Find the lifting power of a 100 litre balloon filled with
He at 730 mm and 25°C. (Density of air = 1.25 g /L).
Sol. Since, PV = nRT
Sol. for gas P1 = (PO + h) P2 = (PO – h) W PVM 730 100× 4
PV = RT ?W = = × g
V1 = Sr A1
2 V2 = Sr2A2 M RT 760 0.082× 298
at const T. and moles. i.e., Wt. of He = 15.72 g
P1V1 = P2V2 ; (PO + h) Sr2A1 = (PO – h) Sr2A2 Wt. of air displaced = 100 × 1.25 g/L = 125 g
POA2 + hA1 = POA2 – hA2 ?Lifting power of the balloon = 125 g – 15.72 g
POA2 – PoA1 = hA, + hA2 = 109.28 g Ans.
h ( A1 + A 2 ) Ex. 5 A weather balloon filled with hydrogen at 1 atm and
P0 = cm of Hg column Ans.
( A 2 – A1 ) 300 K has volume equal to 12000 litres. On ascending
it reaches a place where temperature is 250 K and
Ex. 2 The diameter of a bubble at the surface of a lake is 4 pressure is 0.5 atm. The volume of the balloon is :
mm and at the bottom of the lake is 1 mm. If (A) 24000 litres (B) 20000 litres
atmospheric pressure is 1 atm and the temperature
(C) 10000 litres (D) 12000 litres
of the lake water and the atmosphere are equal. what
is the depth of the lake ? P1V1 P2V2 1 atm × 12000 L
Sol. Using = ;
(The density of the lake water and mercury are 1 g/ T1 T2 300 K
ml and 13.6 g/ml respectively. Also neglect the
contribution of the pressure due to surface tension) 0.5 atm × V2
=
Sol. P1V1 = P2V2 250 K
4 ? V2 = 20,000 L
?(760 mm × 13.6 × g) S (4 mm/2)3 Hence Ans. (B)
3
4 Ex. 6 If water is used in place of mercury then what should

= (760 mm × 13.6 × g + h × 1 × g) S (1 mm/2)3 be minimum length of Barometer tube to measure
3
normal atmospheric pressure.
760 × 13.6 × 64 = (760 × 13.6 + h)
h = 64 × 760 × 13.6 – 760 × 13.6 Sol. PHg = PH O = P .
2 atm
h = 63 × 760 × 13.6 mm
0.76 m × 13.6 × g = h H2O × 1 × g
63×760×13.6
h= km = 0.6511 km = 651.1 m Ans. h H2O = 0.76 × 13.6 = 10.336 m Ans.
1000×1000
134
Ex. 7 A car tyre has a volume of 10 litre when inflated. The Ex. 9 An open container of volume V contains air at
tyre is inflated to a pressure of 3 atm at 17°C with air. temperature 27ºC or 300 K.The container is heated
Due to driving the temperature of tyre increases to to such a temperature so that amount of gas coming
47°C. out is 2/3 of
(A) What would be pressure at this temperature ? (A) amount of gas initially present in the container.
(B) How many litres of air measured at 47°C and (B) amount of gas finally remaining in the container.
pressure of 1 atm should be left out to restore the
tyre to 3 atm at 47°C Find the temperature to which the container should
be heated.
Sol. V = 10L P, = 3 atm T, = 17oC = 290K
o
T2 = 47 C = 320K Sol. (A) Here , P & V are constant, n & T are changing.
(A) ' Here v & n are constant Let, initially the amount of gas present be n & temp
is 27ºC or 300K. Finally amount of gas present in
P1 P2 P1T2 3×320
? Using = P2 = = atm 2 §1 ·
T1 T2 T1 290
container = n – n = ¨ × n ¸ & final temp. be T.
i.e. P2 = 3.3103 atm 3 ©3 ¹
i.e. Pressuse at 47oC = 3.3103 atm Ans. Then using n1T1 = n2T2 , we have,
(B) Now, P1 = 3 atm ; V1 = 10L ; T1 = 17oC = 290K
n
Final P2 = 3atm ; V2 = ? ; T2 = 47oC = 320 K n × 300 = × T2 T2 = 900K
3
V1 V2 V ×T 10L×320K
= ? V2 = 2 2 = = 11.035L i.e., final temp = 900K Ans.
T1 T2 T1 290K
Sol. (B) Let there be x moles of gas remaining in the
? Volume of gas should be removed at 47oC & 3atm
= (11.035 – 10) L = 1.035L 2
container, of x come out
Now this vol at 1atm be vc then 3
1.0351 × 3atm = vc × 1atm 2 5x 3n
? (x + x) = n =n ?x=
? vc = 3.105L 3 3 5
? Reqd vol = 3.105 L Ans. 3n
? Using n1 T1 = n2 T2 n × 300 K = × T2
Ex. 8 A tube of length 50 cm is initially in open atmosphere 5
at a pressure 75 cm of Hg. This tube is dipped in a ? T2 = 500K
Hg container upto half of its length. Find the level final temperature = 500 K Ans.
of mercury column in side the tube.
Ex. 10 Four one litre flasks are separately filled with the
Sol.
gases, O 2 , F 2, CH 4 and CO 2 under the same
conditions. The ratio of number of molecules in these
gases :
(A) 2 : 2 : 4 : 3 (B) 1 : 1 : 1 : 1
(C) 1 : 2 : 3 : 4 (D) 2 : 2 : 3 : 4
If after dipping the tube, the Sol. According to avogadro’s hypothesis.
length of air column be x cm (situation shown in the All the flasks contains same no. of molecules
adjoining figure). ? Ratio of no. of molecules of O2, F2, CH4 & CO2
Then by using, Pi Vi = Pf Vf = 1 : 1 : 1 : 1 Ans (B)
We have.
Ex. 11 A sample of water gas has a composition by volume
75 cm Hg × AA = Pf × x × A ....... (1) (A = 50 cm)
of 50% H2, 45% CO and 5% CO2. Calculate the volume
A in litres at STP at which water gas which on treatment
& also, Pf = 75 cm Hg + (x – ) ....... (2)
2 with excess of steam will produce 5 litre of H2. The
equation for the reaction is :
(2) & (1) [75 + (x – 25)] × x = 75 × 50
x2 + 50 x – 3750 = 0 CO + H2O o CO2 + H2
? x = 41.14 or – 91.14 Sol. If x L CO in needed then
But, x can't be – ve ? x = 41.14
§ x ·
? mercury column inside the tube = (50 – 41.14) volume of H2 in water gas = ¨ ×50% ¸ L
cm = 8.86 cm Ans. © 0.45 ¹
135
Ex. 14 Equal volume of two gases which do not react
§ x 1· x
=¨ × ¸L = L together are enclosed in separate vessels. Their
© 0.45 2 ¹ 0.9 pressures are 10 mm and 400 mm respectively. If
the two vessels are joined together, then what
But, from equation : CO + H2O o CO2 + H2
will be the pressure of the resulting mixture
& Gay-Lussac’s law, we get, that the volume of H2 (temperature remaining constant) :
produced = volume of CO taken. (A) 120 mm (B) 500 mm
? Volume of H2 due to reaction = x L (C) 1000 mm (D) 205 mm
§ x · Sol. (D) Let, vol of containers be V & temperature be T
? Total volume of H2 = ¨ + x¸ L= 5 L P1 = 10mm P2 = 400mm
© 0.9 ¹
P1V P2V
1.9x ? n1 = & n2 =
=5L RT RT
0.9
(P1 + P2 )× V
? n1 + n2 =
0.9× 5 RT
? x= After joining two containers final vol = (V+V) = 2V
1.9
(for gases)
x 0.9×5
? Volume of water gas = L= L n1 + n 2 RT
0.45 1.9× 0.45 ? Pfinal =
Vfinal
= 5.263 L Ans.
(P1 + P2 )× V RT P1 + P2
Ex. 12 5 ml of H2 gas diffuses out in 1 sec from a hole. Find = × =
RT 2V 2
the volume of O2 that will diffuse out from the same
hole under identical conditions in 2 sec.
10 + 400 mm
= = 205 mm.
2
5ml
Sol. Rate of diffusion of H2 = = 5ml/s = rH 2 (say) Ex. 15 A vessel contains H2 & O2 in the molar ratio of 8 : 1
1 sec respectively. This mixture of gases is allowed to
diffuse through a hole, find composition of the
1 1 mixture coming out of the hole.
? ro 2 = rH2 × = 5ml/s ×
4 4
rH 2 n H2 M O2
? Volume of O2 diffused in 2.0 seconds Sol. Here, nH2 : n O 2 = 8 : 1 & =
rO2 n O2 M H2
5
= × 2 ml = 2.5 ml Ans.
4 rH 2 8 32 32
= × =
Ex. 13 The partial pressure of hydrogen in a flask rO2 1 2 1
containing two grams of hydrogen and 32 gm of
sulphur dioxide is : no. of molesof H 2 coming out / Δt 32
=
(A) 1/16th of the total pressure no. of molesof O2 coming out / Δt 1
(B) 1/9th of the total pressure ? Required composition of H2 : O2 coming out
(C) 2/3 of the total pressure = 32 : 1 Ans.
(D) 1/8th of the total pressure
Ex. 16 (i) Calculate the pressure exerted by 1023 gas mol-
2g ecules, each mass 10–22 g in a container of volume
Sol. (C) n H2 = = 1mol. n SO 2
2g / mol one litre. The rms velocity is 105 cm/sec.
(ii) What is the total kinetic energy (in cal) of these
32g particles ?
= = 0.5 mol
64g / mol (iii) What must be the temperature ?
n H2 1 2 Sol. (i) Here N = 1023 molecules m = 10–22g , V = 1L = 1000
? PH2 = × PT = × PT = PT. cm3
n H2 + n SO2 (1+ 0.5) 3
rms velocity = 105 cm/second
? (C) 1
? PV = Nm U 2
3
136
1 Ex. 18 A gaseous mixture containing CO, methane CH4 &
?P= Nm U 2 N2 gas has total volume of 40 ml. This mixture is
3
exploded with excess of oxygen on cooling this
1
= × 1023 × 10–22g × (105)2cm2/s2 mixture a contraction of 30 ml is observed & when
3×1000cm 3 this mixture is exposed to aqueous KOH a further
= 3.33 × 107 dyne/cm2 Ans. contraction of 30 ml is observed .find the
(ii) Total K . E of the molecules composition of the mixture.
1 Sol. Let vol of CO be x mL
= Nm U 2
2 vol of CH4 be y mL
1 vol of N2 be z mL
= × 1023 × 10–25 kg × (103m/s)2
2 On explosion with excess of oxygen the following
10000J reactions takes place
= = 5000 J | 1195.0 Cal Ans.
2 1
1 3 CO(g) + O (g) o CO2 (g)
(iii) Avg K . E of one molecule = m U2 = kT 2 2
2 2 (By Gaylussac's law of combing volume)
1 mU 2 x mL x mL
?T= ×
CH4(g) + 2O2(g) o CO2(g) + 2H2O(g)
3 k

2
1 10 Kg× 103 m / s × 6.023×10 23
–25 y mL y mL 2 ymL
= × K N2 remains unreacted
3 8.314
On cooling H2O (g) liquifies hence volume reduc-
§ R ·
tion of 30 mL is observed
¨' k = NA ¸
© ¹ ? 2y = 30 ? y = 15
= 2414.8 K Ans. But, vol of CO2 obtained = (x + y) mL
Ex. 17 The rate of diffusion of a sample of a ozonized This is absorbed in KOH & vol reduction of 30 mL is
oxygen is 0.98 times than that of oxygen. Find the observed.
% ? x + y = 30 x = 30 – y = (30 – 15) = 15
(by volume of ozone in the ozonized sample). and,x + y + z = 40 z = 40 – x – y = 40 – 15 – 15
Sol. Let, rate of diffusion of ozonized oxygen be rg
= 10
& Let, reat of diffusion of oxygen be rO 2 ? Composition of mixture is
rg vol of CO = 15 mL Ans.
? = 0.98 (given) ......... (1) vol of CH4 = 15 mL Ans.
rO 2
vol of N2 = 10 mL Ans.
1/2
rg § M O2 ·
but = ¨¨ ¸ (mean molar mass of ozonized Ex. 19 Under critical states of a gas for one mole of a
¸
rO 2 © Mg ¹ gas, compressibility factor is :
oxygen = Mg)
3 8
32 (A) (B)
8 3
Form (1) 0.98 =
Mg
1
32 32 (C) 1 (D)
4
(0.98)2 = ? Mg = 2 = 33.32
Mg 0.98 PC VC
Sol. For 1 mole of gas Z = (Under critical condi-
Let % of O3 be x ? % O2 = (100 – x) in ozonized RTC
oxygen. tion)
48x + 100 – x × 32 a 8a
? = 33.32 But, PC = , VC = 3b , TC =
100 27b 2 27Rb
132 § a · 3b 27Rb 3
3200 + 16x = 33.32 ? x = = 8.25 % ? Z= ¨ 2 ¸ × × =
16 © 27b ¹ R 8a 8
i.e. % of O3 = 8.25 % Ans. Ans. (A)
137
Ex. 20 One litre of oxygen gas is passed through a ozonizer 8RT
& the final volume of the mixture becomes 820 ml. If But, avg. velocity =
πM
this mixture is passed through oil of turpentine. Find
the final volume of gas remaining. 8×8.314× T
Sol. The reaction that takes place in ozonizer as 1.1 × 104 =
π × 2×10 –3
3O2 o 2O3.
If Vml of O2 out of 1000 ml is ozonized then vol of O3
M H2 2g 2 u 10 – 3 kg
2
1.1×10
2
4
obtained = V × π × 2×10 –3
3 ?T= K = 11430.5 K
? Final vol of ozonized oxygen 8×8.314
2 = 11157.5oC Ans.
= (1000 – V + V) mL = 820 mL
3
1
1000 – V = 820
3
V
= 180 ? V = 540
3
? O2 remaining = (1000 – 540) mL
(' O3 is absorbed in oil of turpentine)
= 460 mL Ans.
Ex. 21 If for two gases of molecular weights MA and MB at
temperature TA and TB ; TAMB = TBMA, then which
property has the same magnitude for both the gases.
(A) Density (B) Pressure
(C) KE per mol (D) RMS speed
TA TB
Sol. Given that TA MB = TB MA =
MA MB
3RT
But, r.m.s. =
M
3RTA
? r.m.sA = &
MA
3RTB
r.m.sB =
MB
? r.m.sA = r.m.sB
? Ans. (D)
Ex. 22 It has been considered that during the formation of
earth H2 gas was available at the earth. But due to
the excessive heat on the earth this had been es-
caped. What was the temperature of earth during its
formation?
(The escape velocity is 1.1 x 106 cm/s)
Sol. Escape velocity of H2 should be equal to average
velocity of H2.
? Avg velocity of H2 = 1.1 × 106 cm/s
= 1.1 × 104 m/s
138
1. The pyknometic density of sodium chloride crystal

S S
is 2.165 × 103 kg m–3 while its X-ray density is 2.178 (A) (B)
6 3 2
× 103 kg m–3. The fraction of unoccupied sites in
sodium chloride crystal is [CBSE AIPMT 2003]
S S
(A) 5.96 × 10–1 (B) 5.96 × 10–3 (C) (D)
4 2 4
(C) 5.96 (D) 5.96 × 10–2
2. A compound formed by elements X and Y crystallises 8. If NaCl is doped with 10–4 mol % of SrCl2, the
in a cubic structure in which the X-atoms are at the concentration of cation vacancies will be (NA = 6.023
corners of a cube and the Y-atoms are at the face × 1023 mol–1) [CBSE AIPMT 2007]
centres. The formula of the compound is
(A) 6.023 × 1015 mol–1 (B) 6.023 × 1016 mol–1
[CBSE AIPMT 2004]
(C) 6.023 × 1017 mol–1 (D) 6.023 × 1014 mol–1
(A) XY3 (B) X3Y
(C) XY (D) XY2 9. If a gas expands at constant temperature, it indicates
that [CBSE AIPMT 2008]
3. The surface tension of which of the following liquids (A) kinetic energy of molecules decreases
is maximum ? [CBSE AIPMT 2005]
(B) pressure of the gas increases
(A) H2O (B) C6H6
(C) kinetic energy of molecules remains the same
(C) CH3OH (D) C2H5OH
(C) number of the molecules of gas increases
4. In a face centred cubic (fcc) lattice, a unit cell is
shared equally by how many unit cells ? 10. Which one of the following statements is an
[CBSE AIPMT 2005] incorrect ? [CBSE AIPMT 2008]
(A) 8 (B) 4 (A) The fraction of the total volume occupied by
the atoms in a primitive cell is 0.48
(C) 2 (D) 6
(B) Molecular solids are generally volatile
5. CsBr crystallises in a body centred cubic lattice. (C) The number of carbon atoms in an unit cell of
The unit cell length is 436.6 pm. Given that the atomic diamond is 4
mass of Cs = 133 u and that of Br = 80 u and Avogadro
(D) The number of Bravais lattices in which a crystal
number being 6.023 × 1023 mol–1, the density of CsBr
can be categorised is 14
is [CBSE AIPMT 2006]
(A) 42.5 g/cm3 (B) 0.425 g/cm3 11. If ‘a’ stands for the edge length of the cubic systems
(C) 8.25 g/cm 3
(D) 4.25 g/cm 3 : simple cubic, body centred cubic and face centred
cubic, then the ratio of radii of the spheres in these
6. The appearance of colour in solid alkali metal halides systems will be respectively,
is generally due to [CBSE AIPMT 2006] [CBSE AIPMT 2008]
(A) F - centres (B) Schottky defect
1 3 1 1 1
(C) Frenkel defect (D) Interstitial positions (A) a: a: a (B) a: 3a: a
2 4 2 2 2 2
7. The fraction of total volume occupied by the atoms
present in a simple sube is 1 3 2
(C) a: a: a (D) 1a : 3 a : 2 a
[CBSE AIPMT 2007] 2 2 2
139
19. Maximum deviation from ideal gas is expected from
12. Percentage of free space in body centred cubic (bcc)
[NEET 2013]
unit cell is [CBSE AIPMT 2008]
(A) H2(g) (B) N2(g)
(A) 30% (B) 32%
(C) CH4(g) (D) NH3(g)
(C) 34% (D) 28%
20. Equal masses of H2, O2 and methane have been taken
13. With which one of the following elements silicon
in a container of volume V at temperature 27°C in
should be doped so as to give p-type of
identical conditions. The ratio of the volumes of
semiconductor ? [CBSE AIPMT 2008]
gases H2 : O2 : CH4 would be [CBSE AIPMT 2014]
(A) Germanium (B) Arsenic
(A) 8 : 16 : 1 (B) 16 : 8 : 1
(C) Selenium (D) Boron
(C) 16 : 1 : 2 (D) 8 : 1 : 2
14. Copper crystallises in a fae centred cubic (fcc) lattice
21. A mixture of gases contains H2 and O2 gases in the
with a unit cell length of 361 pm. What is the radius
ratio of 1 : 4 (w/w). What is the molar ratio of the two
of copper atom in pm? [CBSE AIPMT 2009]
gases in the mixture? [CBSE AIPMT 2015]
(A) 128 pm (B) 157 pm
(A) 1 : 4 (B) 4 : 1
(C) 181 pm (D) 108 pm
(C) 16 : 1 (D) 2 : 1
15. Lithium metal crystallises in a body centred cubic
22. A given metal crystallises out with a cubic structure
(bcc) crysta. If the length of the side of the unit cell
having edge length of 361 pm. If there are four metal
of lithum is 351 pm, the atomic radius of the lithium
atoms in one unit cells, what is the radius of one
will be [CBSE AIPMT 2009]
atom? [CBSE AIPMT 2015]
(A) 240.8 pm (B) 151.8 pm
(A) 40 pm (B) 127 pm
(C) 75.5 pm (D) 300.5 pm
(C) 80 pm (D) 108 pm
16. By what factor does the average velocity of a
gaseous molecule increase when the temperature 23. The vacant space in bcc lattice cell is
(in kelvin) is doubled? [CBSE AIPMT 2011]
[CBSE AIPMT 2015]
(A) 2.8 (B) 4.0
(A) 26% (B) 48%
(C) 1.4 (D) 2.0
(C) 23% (D) 32%
17. Two gases A and B having the same volume diffuse
24. The correct statement regarding defects in the
through a porous partition in 20 and 10s
crystalline solid is [CBSE AIPMT 2015]
respectively. The molecular mass of A is 49 u.
(A) Schottky defects have no effect on the density
Molecular mass of B will be [CBSE AIPMT 2011]
of crystalline solids
(A) 12.25 u (B) 6.50 u
(B) Frenkel defects decreases the density of
(C) 25.00 u (D) 50.00 u
crystalline solids
18. A gaseous mixture was prepared by taking equal (C) Frenkel defect is a dislocation defect
moles of CO and N2. If the total pressure of the (D) Frenkel defect is found in halides of alkaline
mixture was found 1 atom, the partial pressure of the metals
nitrogen (N2) in the mixture is [CBSE AIPMT 2011]
(A) 0.8 atm (B) 0.9 atm
(C) 1 atm (D) 0.5 atm
140
25. In calcium fluoride, having the fluorite structure, 29. A 20 litre container at 400 K contains CO2(g) at
the coordination number for calcium ion (Ca2+) and pressure 0.4 atm and an excess of SrO (neglect the
fluoride ion (F–) are [NEET 2016, Phase II] volume of solid SrO). The volume of the container is
(A) 4 and 2 (B) 6 and 6 now decreased by movind the movable piston fitted
in the container. The maximum volume of the
(C) 8 and 4 (D) 4 and 8
container, when pressure of CO2 attains its maximum
26. The ionic radii of A+ and B– ions are 0.98 × 10–10 m . value, will be [NEET 2017]
The coordination number of each ion in AB is (Given that : SrCO3(s) U SrO(s) + CO2(g), Kp = 16 atm)
[NEET 2016, Phase I] (A) 5 L (B) 10 L
(A) 4 (B) 8 (C) 4 L (D) 2 L
(C) 2 (D) 6
30. Given van der Waals constant For NH3, H2, O2 and
27. Lithium has a bcc structure. Its density is 530 kg m–
CO2 are respectively 4.17, 0.244, 1.36 and 3.59,
3
and its atomic mass is 6.94 g mol–1. Calculate the
which one of the following gases is most easily
edge length of a unit cell of lithium metal.
liquefied ? [NEET 2018]
(NA = 6.02 × 1023 mol–1) [NEET 2016, Phase I]
(A) O2 (B) H2
(A) 352 pm (B) 527 pm (C) NH3 (D) CO2
(C) 264 pm (D) 154 pm
31. The correction factor 'a' to the ideal gas equation
28. Equal moles of hydrogen and oxygen gases are
corresponds to. [NEET 2018]
placed in container with a pin-hole through which
both can escape. What fraction of the oxygen (A) electric field present between the gas mol-
escapes in the time required for one-half of the ecules
hydrogen to escape? [NEET 2016, Phase I] (B) volume of the gas molecules
(A) 1/4 (B) 3/8 (C) density of the gas molecules
(C) 1/2 (D) 1/8 (D) forces of attraction between the gas molecules
141
1. Dominance of strong repulsive forces among the 6. Two flasks X and Y have capacity 1L and 2L
molecules of the gas (Z = compressibility factor) respectively and each of them contains 1 mole of a
[2006] gas. The temperatures of the flasks are so adjusted
(A) depends on Z and indicated by Z = 1 that average speed of molecules in X in twice as
(B) depends on Z and indicated by Z > 1 those in Y. The pressure in flask X would be [2010]
(C) depends on Z and indicated by Z < 1 (A) same as that in Y (B) half of that in Y
(D) is independent of Z. (C) twice of that in Y (D) 8 times of that in Y
2. In P versus V graph, the horizontal line is found in

which _______ exists. [2006] 7. In the van der Waals equation, ‘d’ signifies [2011]
(A) gas (A) intermolecular attraction
(B) liquid (B) intramolecular attraction
(C) equilibrium between gas and liquid (C) attraction between molecules and wall of
(D) super critical temperature container
(D) volume of molecules
3. Critical temperatures for A, B, C and D gases are
25°C, 10°C, –80°C and 15°C respectively. Which gas 8. Arrange the following gases in order of their critical
will be liquefied more easily ? [2006] temperature. [2012]
(A) A NH3, H2O, CO2, O2
(B) B (A) NH3 > H2O > CO2 > O2
(C) C (B) O2 > CO2 > H2O > NH3
(D) D (C) H2O > NH3 > CO2 > O2
(D) CO2 > O2 > H2O > NH3
4. The root mean square speed of the molecules of
diatomic gas is u. When the temperature is doubled,
9 Pure hydrogen sulphide is stored in a tank of 100
the molecules dissociate into two atoms. The new
litre capacity at 20°C and 2 atm pressure.
rms speed of the atom is [2008]
The mass of the gas will be [2017]
(A) 2u (A) 34 g (B) 340 g
(B) u (C) 282.68 g (A) 28.24 g
(C) 2u
(D) 4u 10. A gas (1g) at 4 bar pressure. If we add 2gm of gas B
then the total pressure inside the container is 6 bar.
5. Equal weights of CO and CH4 are mixed together in
Which of the following is true ? [2018]
an empty container at 300 K. The fraction of total
(A) MA = 2MB (B) MB = 2MA
pressure exerted by CH4 is [2010]
(C) MA = 4MB (D) MB = 4MA
16 7
(A) (B)
17 11
8 5
(C) (D)
9 16
142
ASSERTION AND REASON
In each of the following questions, two statement 14. Assertion : At critical point, the densities of
are given one is assertion and the other is reason. substance in gaseous and liquid states are same.
Examine the statement carefully and mark the correct [2013]
answer according to the instruction given below Reason : Critical temperature is the temperature at
(A) If both the assertion and reason are true and which the real gas exhibit ideal behaviour for
reason explains the assertion considerable range of pressure.
(B) If both the assertion and reason are true but
reason does not explain the assertion 15. Assertion : Critical temperature of CO2 is 304 K, it
cannot be liquified above 304 K. [2016]
(C) If assertion is true but reason is false
(D) If assertion is false but reason in true 1
Reason : At a certain temperature, volume v
pressure
(E) Both assertion & reason are false
11. Assertion : Effusion rate of oxygen is smaller than

16. Assertion : Gases do not liquefy above their critical
nitrogen. [2004]
temperature, even on applying high pressure. [2017]
Reason : Molecular size of nitrogen is smaller than
Reason : Above critical temperature, the molecular
oxyge.
speed is high and intermolecular attractions cannot
12. Assertion : compresibility factor for hydrogen varies hold the molecules together because they escape
with pressure with positive slope at all pressures. because of high speed.
[2005, 2009]
Reason : Even at low pressures, repulsive forces 17. Assertion :The surface tension of water is more
dominate for hydrogen gas. than other liquid. [2018]
Reason : Water molecules have strong inter
13. Assertion : If H2 and Cl2 enclosed separately in the
molecular H-bonding as attractive force.
same vessel exert pressure of 100 and 200 mm
(A) If both assertion and reason are true and reason
respectively, their mixture in the same vessel at the
is the correct explanation of assertion.
same temperature will exert a pressure of 300 mm.
(B) If both assertion and reason are true but reason
[2008]
is not the correct explanation of assertion.
Reason : Daloton’s law of partial pressures states
(C) If assertion is true but reason is false.
that total pressure is the sum of partial pressures.
(D) If both assertion and reason are false.
143
ANSWER KEY
EXERCISE: PART - 1
1. B 2. A 3. A 4. D 5. D 6. A 7. A 8. C 9. C 10. A 11. A 12. B 13. D
14. A 15. B 16. C 17. A 18. D 19. D 20. C 21. B 22. B 23. D 24. C 25. C 26. D
27. A 28. D 29. A 30. C 31. D
PART - 2
1. B 2. C 3. A 4. C 5. B 6. D 7. A 8. C 9. C 10. D 11. C 12. A 13. D
14. C 15. B 16. A 17. A
144
40-65*0/4 STATES OF MATTER (GASEOUS & LIQUID)
EXERCISE 3
4 §a·
P-1 (NEET/AIPMT) Volume of the atom S¨ ¸
3 © 2¹
1. (B) : The fraction of unoccupied site in sodium chloride
3
X-ray density pyknometric density 4 §a·
crystal S¨ ¸
X ray density 3 © 2¹ S
? Packing fraction
a3 6
2.178 u 103 2.165 u 103 0.013 u 103
2.178 u 103 2.178 u 103 8. (C) : Doping of NaCl with 10–4 mol% of SrCl2 means, 100
moles of NaCl are doped with 10–4 mol of SrCl2.
13 ? 1 mol of NaCl is doped with
5.96 u 103
2178
10 4
SrCl2 106 mole
1 100
2. (A) : In unit cell, X-atoms at the corners u8 1 As each Sr2+ ion introduces one cation vacancy.
8
? Concentration of cation vacancies
1 = 10–6 mol/mol of NaCl
Y-atoms at the face centres u6 3
2 = 10–6 × 6.023 × 1023 mol–1
Ratio of X and Y = 1 : 3. = 6.023 × 1017 mol–1
Hence, formula is XY3.
3
3. (A) : Surfae tension of H2O is maximum due to maximum 9. (C) : KE RT (for one mole of a gas)
hydrogen bonding in comparison to C6H6, CH 3OH, 2
C2H5OH. The order of H-bonding is H2O > CH3OH > As, the kinetic energy of a gaseous moleculs depends
C2H5OH only on temperature, thus at constant temperature, the
(Benzene does not form H-bond). kinetic energy of the molecules remains the same.
4. (D) : In a face centred cubic (fcc) lattice, a unit cell is 4 3

shared equally by six unit cells. 10. (A) : Volume of atoms in unit cell (V) Sr
3
Zu M a
5. (D) : Density of CsBr
a3 u N0 For primitive cell, r
2
Z o number of atoms in the bcc unit cell = 2 3
M o molar mass of CsBr = 133 + 80 = 2013 4 §a· Sa 3
V S¨ ¸
a o edge length of unit cell = 436.6 pm 3 © 2¹ 6
= 436.6 × 10–10 cm Volume of the unit cell (V) = a3
2 u 213 Thus, total volume occupied by the atoms
? Density
(436.6 u 1010 )3 u 6.023 u 1023 Volume of the atoms in unit cell
= 8.49 × 10 × 10 g/cm
–7 7 3 Volume of unit cell
= 8.50 g/cm3 Sa 3 1 S
u 0.52 100 0.52 0.48
8.50 3 6 a3 6
For a unit cell 4.25g / cm
2
11. (A) : If a = edge length of cubic system
6. (A) : F-centres are the sites where anions are missing
a
and instead electrons are present and the appearance of For simple cubic structure, radius
colour in solid alkali metal halides is generally due to F- 2
centres.
3
For body centred cubic structure, radius a
7. (A) : For simple cube, 4
a a
Radius (r) [a = edge length] For face centred cubic structure, radius
2 2 2
145
17. (A) : According to Graham’s law of diffusion, rate of
1 3 1 diffusion
Hence, the ratio of radii = a: a: a
2 4 2 2
1 V
rv ,r v
12. (B) : In bcc unit cell, the number of atoms = 2 M t
4 3 where, V is the volume of the gas diffused in time t.
Thus, volume of atoms in unit cell (v) 2 u Sr
3
rA MB VA t B MB
or u
3 rB MA t A VB MA
For bcc structure (r) a
4 Given, VA = VB
3
4 § 3 · 3 3 10 MB 1 MB
(V) 2 u S ¨¨ a¸ Sa ?
3 © 4 ¸¹ 8 20 49 4 49
Volume of unit cell (V) = a3 49

MB 12.25u
Percentage of volume occupied by unit cell 4
Volume of the atoms in unit cell 18. (D) : Equal moles of CO and N2
Volume of unit cell nCO = nN
2
then, according to ideal gas equation, pressure of both
3 3 gases CO and N2 becomes equal
Sa
8 3 ? pCO = pN
u 100 S u 100 68%
a3 8 2
Given, pCO + pN2 = Total pressure of mixture.
Hence, the free space in bcc unit cell = 100 – 68 = 32% or 2pN = 1 atm
2
or pN = 0.5 atm
2
13. (D) : p-type of semiconductor are obtained by doping
silicon or germanium with elements of group 13 like B, 19. (D) : The extent to which a real gas deviates from ideal
Al, Ga or In so silicon is doped with boron. behaviour can be understood by a quantity ‘Z’ called
the compressibility factor. Easily liquifiable gases like
14. (A) : In case of face centred cubic (fcc) lattice,
NH3, SO2 etc. exhibit maximum deviation from ideal gas
2a as for them Z < < < 1.
radius CH4 also exhibits deviation but it is less as compared to
4
NH3.
? Radius of copper atom (fcc lattice)
20. (C) : According to Avogadro’s hypothesis,
2 u 361 Volume of a gas (V) v number of moles (n)
128pm
4 Therefore, the ratio of the volumes of gases can be
determined in terms of their moles.
15. (B) : In case of body centred cubic (bcc) crystal, ? The ratio of volumes of H2 : O2 : methane (CH4) is
a 3 4r given by
Given, edge length, a = 351 pm VH2 : VO2 : VCH4 n H2 : n O2 : n CH4
Hence, atomic radius of lithium,
mH2 mO2 m CH4
a 3 351u 1.732 VH 2 : VO2 : VCH 4 : : :
r M H 2 M O2 M CH 4
4 4
= 151.98 pm ª mass º
Given, m H2 m O2 mCH4 m «' n »
¬ molar mass ¼
8RT
16. (C) : Average velocity m m m
SM
Thus, VH 2 : VO2 : VCH 4 : : 16 :1: 2
2 32 16
?
Vav 2 2T
Vav v T or 1.4
Vav 1 T
146
21. (B) : Let the mass of H2 gas be xg and mass of O2 gas 4xg (Z) = 2
Molar H2 : O2 ? We have the formula for density.
mass 2 : 32
ZM
i.e. 1 : 16 U
NAa3
n H2 x/2 x u 32 4
? Molar ratio 4 :1 where a = edge-length of unit cell.
n O2 4x / 32 2 u 4x 1
ZM 2 u 6.94g mol1
or a
22. (B) : Given, edge length = 361 pm UN A 0.56g cm 3 u 6.02 u 10 23 mol 1
Four metal atoms in one unit cell
i.e. effective number in unit cell (z) = 4 (given) 3 4.35 u 1023 cm3
? It is a FCC structure = 3.52 × 10–8 cm
? Face diagonal = 4r a = 352 pm
2a 4r 28. (D) : Given, number of moles of hydrogen (nH ) and that
2
of oxygen (nO ) are equal.
2 u 361 2
? We have, the relation between ratio of number of moles
r 127 pm
4 escaped and ratio of molecular mass.
23. (D) : ' Packing efficiency in bcc lattice = 68% n O2 M H2
? Vacant space in bcc lattice
n H2 M O2
= 100 – 68 = 32%
where, M = Molecular mass of the molecule.
24. (C) : In Frenkel defect, ions in solids dislocate from their
positions. Hence, Frenkel defect is a dislocation defect. n O2 2
n H2 32
25. (C) : In CaF (Fluorite structure), Ca ions are arranged
2 2+
in ccp arrangement (Ca2+ ions are present at all corners

and at the centre of each face of the cube) while F– ions n O2 1
occupy all the tetrahedral sites. n H2 16
n O2 1

0.5 4
Ca2+ 0.5 1
F--- n O2
4 8
29. (A) : For the reaction,
From the above figure, you can clearly see that SrCO3(s) U SrO(s) + CO2(q),
coordination number of F– is 4 while that of Ca2+ is 8. Kp = 1.6 atm = pCO = maximum pressure of CO2
2
Given, p1 = 0.4 atm, V1 = 20 L, T1 = 400 K
26. (D) : Given, ions radius of cation (A+) = 0.98 × 10–10 m
p2 = 1.6 atm, V2 = ?, T2 = 400 K
Ionic radius of anion (B–) = 1.81 × 10–10 m
At constant temperature, p1V1 = p2V2
? Coordination number of each ion in AB = ?
0.4 × 20 = 1.6 × V2
Now, we have
Radius of cation 0.98 u 1010 m
0.4 u 20
Radius ratio V2 5L
= 0.541 1.6
Radius of anion 1.81u 1010 m
Ir radius range is in between 0.441 – 0.732, ion would
have octahedral structure with coordination number ‘six’ 30. (C) : 'ease of liquification depends on' a
? NH3
27. (A) : Given, Li has a bcc structure.
31. (D) : a corresponds to the force of attraction between the
Density (U) = 530 kg-m–3
gas molecules.
Atomic mass (M) = 6.94 g mol–1
Avogadro’s number (NA) = 6.02 × 1023 mol–1
We known that, number of atoms per unit cell in bcc
147
EXERCISE 5. (B) : Let the weight of CO = weight of CH4 = a g
P-2 (AIIMS)
a
1. (B) : When the value of Z < 1, it is due to attractive Moles of CO
28
forces between molecules. At high pressure, when Z > 1,
it is due to repulsive forces between electron clouds of a
Moles of CH4
the molecules of gases. 16
a a
Total moles
2. (C) : DH
Liquid
28 16
48.
1°C
31.
PC 1°C a
(T
C)
16 a 28 u 16 14 7
x CH4 u
21.5°C F a a 16 44a 22 11
G Gas
Pressure
Liquid 13.1°C
28 16
B E
+ C
Gas A ? Fraction of pressure exerted by CH4 = 7/11
VC Volume
1 mnu 2
6. (D) : P
From the graph, at point A, CO2 exists as a gas, As pressure 3 V
is increased, the volume of the gas decreases along the
curve AB. At B liquefaction of the gas starts. Hence, PX n X u X VY (N 0 / 1000) 2
u 2u 8
volume decreases repidly along BC because liquid has PY n Y u Y VX (N 0 / 2000) 1
much less volume than the gas. At point C, liquefaction
is complete. Amount of gas decreased = Amount of liquid 7. (A) : In van der Waals equation, a signifies the
formed or increased. intermolecular force of attraction.
Because along horizontal line, gas converts into liquid.
8. (C) : Greater are the intermolecular forces of attraction,
3. (A) : Critical temperature of gas may be defined as that higher is the critical temperature.
temperature above which it cannot be liquefied
PV m
howsoever high pressure may be applied on the gas. 9. (C) : n = =
RT M
8a
As we know, TC MPV 34 u 2 u 100
27Rb m= = = 282.68 gm
RT 0.082 u 293
where a = van der Waals’ constant which is a measure of
intermolecular forces of atraction. Greater the value of a n1 n2
more easily the gas can be liquefied and hence larger TC 10. (D) : p p2
1
mean larger the value of a.
1 1 2
2RT 3 2 4
4. (C) : u MA M A M B
M MA MA MB
4 6
3R u 2T 1 4
If T = 2T and M = M/2, then u1
M/2 MA M B MB = 4MA
u1
? 4 2
u
11. (B) : Molecular size decreases from left to right while it
increases in a group from top to bottom. Thus, molecular
size of nitrogen is greater than oxyge.
148
12. (A) : In case of H2, compressibility factor increases with

the pressure. At 273 K, Z > 1 which shows that it is
difficult to compress the gas as compared to ideal gas. In
this case, repulsive forces dominate.
13. (D) : H2 and Cl2 react chemically. Hence Dalton’s low is

not applicable. Dalton’s law states that “at a given
temperature, the total pressure exerted by two or more
non-reacting gases occupying a definite volume is equal
to the sum of the partial pressures of the component
gases.”
14. (C) : Temperature at which the real gas exhibits ideal

behaviour for considerable range of pressure is known
as Boyle’s temperature.
a
Tb where a and b are van der Waals’ constant.
bR
Critical temperature is the temperature above which the
gas cannot be liquefied, how so ever high pressure may
8a
be applied : TC .
27Rb
15. (B) : Critical temperature of a gas may be defined as that

temperature above which it cannot be liquified however
high pressure may be applied on the gas.
Hence, CO 2 cannot be liquified above its critical
temperature.
According to Boyle’s law
1 1
Pv or V v (at constant T and n)
V P
16. (A)
17. (A)
149
3PVHI8PSL
3PVHI8PSL
3PVHI8PSL

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Module 2 - XI NEET - Chemistry

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COMPREHENSIVE

SELF – STUDY MATERIAL

NEET & AIIMS

(1) Thermodynamics and Thermochemistry .............................................................. 3

n Thermodynamics and Thermochemistry

x Both state function and state variables are same.

if v³ dX 0  X is a state function (property of state function)

(4) Adiabatic process

initial process restoring process

(7) Irreversible Process :

HEAT AND WORK :

(II) Non-PV Work - Following are some examples of Non-PV work.

1 litre atm = 101.3 J

Hence total internal energy of a system can be written as

x Internal Energy is an extensive Property and is a state function.

Overall change in I.E. 'U ³ C v .dT

RELATIONSHIP BETWEEN 'H & 'U

From equation (vii) Unit From equation (iv)

It is the rate of change of enthalpy with temperature at constant pressure.

Molar heat capacity (Cm) :

Degree of Freedom and Equipartition Principle

Translational Rotational Vibrational

vibrational degree of freedom can be calculated by the following method

WORK DONE IN DIFFERENT PROCESS :

PV work Non-PV work

This type of P.V. work is irreversible P.V. work.

Work done volume

? from equation (1) & (2) we have

nCV (Tf – Ti) = – Pext § nRTf – nRTi ·

(C) The correct option is (C) 'T = 0.

Examples of entropy change

(V) TOTAL ENTROPY CHANGE IN REVERSIBLE PROCESS :

? 'Stotal = +ve (' T1 > T2)

Entropy and Criteria of Spontanity of Chemical Process

Δr H – ΔrG 276.144 J mol –1 – 75.312 J mol –1

'rH4 ' rS 4 'rG4 Description

GIBBS FREE ENERGY CHANGE AT CONSTANT TEMPERATURE :

Differentiating the above equation, we get

In case of one mole of a perfect gas,

For n moles of a perfect gas, the free energy change is

Examples of exothermic reactions :

Exceptions of formation reaction :

(iv) Temperature : Effect of temperature on heat of reaction is given by Kirchoff equation

'H T = Heat of reaction at T1 temperature

'H T = Heat of reaction at T2 temperature

'CVm = 6(CVm)P – 6(CVm)R

Ex. Why does heat get released/absorbed during chemical reactions?

HESS'S LAW OF CONSTANT HEAT SUMMATION

(i) One step reaction (ii) Two step reaction

Types of Heat of Reaction :

2S(s) + C(s) + O2(g) o2SO2(g) + CO2 (g) 'H = –980.74 kJ

C(s) + 2S(g) oCS2(A) 'H = –128.02 kJ

'H = – 5.5 – (– 57) + 2 × ( – 64)

(II) Enthalpy of Combustion ('Hcomb)

From the inspection of the above diagram, it is clear that

Sol. + O2 o CO2 + H2O

x lit. (4 – x)lit. 6 lit.

unit = K J g–1 or K Cal g–1

(III) Bond Energy / Bond dissociation energy

1H2O(g) o 2H(g) + O(g) 'H H2 O ±

(IV) Enthalpy of Solution

(V) Enthalpy of Hydration

(VI) Enthalpy of Neutralisation

Experimental determination of enthalpy of neutralization :

if v³ dX 0 X is a state function (property of state function)

2S(s) + C(s) + O2(g) o2SO2(g) + CO2 (g) 'H = –980.74 kJ

C(s) + 2S(g) oCS2(A) 'H = –128.02 kJ

1H2O(g) o 2H(g) + O(g) 'H H2 O ±

(i) Ionization NH4OH(aq) o NH4+(aq) + OH¯(aq) 'H1 = ?

(ii) Neutralization H+(aq) + OH¯(aq) o H2O(A) 'H2 = – 57.1 kJ/mole

Unsaturated organic compound

7. Enthalpy of reaction A oB Enthalpy change taking place in 'rH° or 'H°r

dlnP 'H v dln G 'H v

'H 35.5 kJ mol1 35.5 u 1000

'Hqf 240 kJ/mol u 9 (ii) 10. (A) : Solid

H2O +C o CO + H2 (Reduction of water)

M n1 o M n 2 + (n2 – n1)e–

2Cl– o Cl2 + 2e –

A n1 o A n 2 + (n1 – n2) e–