THERMODYNAMICS

Thermodynamics is the branch of science which deals with all changes in energy or transfers of energy that
accompany physical and chemical processes

SECTION I
First Law of thermodynamics and Hess Law
System, Surrounding and Boundary
A system is defined as a specified part of the universe which is under experimental investigation and the rest of the
universe, i.e. all other matter which can interact with the system, is surroundings.
Isolated System :
A system which neither exchanges energy nor matter with its surroundings is called an isolated system. For
example, a liquid in contact with its vapour in an insulated closed vessel is an isolated system. No exchange of
matter and energy is possible with the surroundings. However, if allowed, it can exchange energy with the
surrounding in the form of work.
Closed System :
A system which may exchange energy but not matter with its surroundings is called a closed system. If in the above
example the vessel containing liquid in contact with its vapour is closed but not insulated, it is a closed system as it
can exchange energy (gain or lose heat) with the surroundings but it is incapable of exchanging matter with
surroundings.
Open System :
A system which may exchange both energy and matter with its surroundings is called an open system.
One such example is of evaporation of water in an open beaker. The water in open beaker absorbs heat for
evaporation from the surroundings and escapes into the surroundings as water vapour.
State Functions :
The fundamental properties which determine the state of a system are referred to as state variables or state functions
or thermodynamic parameters. The change in the state function depends upon the initial state and final state of the
system, but is independent of the manner in which the change has taken place. It means that the state properties do
not depend upon the path followed. Examples: pressure, volume, temperature, number of moles, internal energy,
enthalpy, entropy, free energy etc.
State of a System :
The system is said to have a definite state when it is in such a condition where all of its macroscopic properties
have definite values.
It follows that under any other condition where the value of any one of its macroscopic properties changes, the
system is said to have a different state. Thus, the state of a system is defined when its macroscopic properties are
specified, i.e. the state of a system is fixed by its macroscopic properties.
Extensive Properties :
The properties whose magnitude depends upon the quantity of matter present in the system. Examples: mass,
volume, total energy, enthalpy, internal energy, entropy, work, mole, heat capacity etc.
Intensive Properties :
Are those properties which do not depend upon the quantity of matter present in the system or size of the system.
Examples: pressure, temperature, density, specific heat, surface tension, refractive index, viscosity, concentration,
melting point, boiling point, volume per mole, molarity, normality, molar enthalpy, mole fraction etc.
THERMODYNAMIC PROCESS
Adiabatic Process :
When a process is carried out under such conditions no exchange of heat takes place between the system and its
surrounding, the process is called adiabatic.
Example :
The sudden bursting of a cycle tube. If the process is exothermic the heat evolved will remain in the system and,
therefore the temperature of the system rises and vice-versa.
Isothermal Process :
The process which occurs at constant temperature is called isothermal process. In an isothermal change the
temperature is kept constant by adding heat or taking it away from the substance. So, in an isothermal process the
system exchanges heat with the surroundings.
Isobaric Process :
If the pressure of the system remains constant during each step of the change in the state of a system, this process is
said to be an isobaric process.
Isochoric Process :
A.K.Pradhan , SUCCESS STUDY CIRCLE, 9438224466

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THERMODYNAMICS
A process is defined to be isochoric if the volume of the system remains constant during the process.
Graphical representation of four basic thermodynamic processes

Isochoric

P ressure

Isobaric

Isothermal
Adiabatic

Volume

FIRST LAW OF THERMODYNAMICS:

Mathematical formulation of the first law:
E q w

where w is the work done on the system, q is the heat transferred and E is the change in internal energy. In non- SI
convention above equation is written as
E q w

WORK DONE IN ISOTHERMAL REVERSIBLE EXPANSION OF AN IDEAL GAS

The small amount of work done, dw, when the gas expands through a small volume, dV, against the external
pressure, P, is given by
dw = PdV
Total work done when the gas expands from initial volume V 1 to final volume V2 will be given as
v2

PdV

w= v
From ideal gas equation, PV = nRT
1

nRT
P = V
v2
nRT
v V dV
1

Hence w =

w = nRT ln

V2
V1

[As T is constant]

= 2.303 nRT log

V2
V1

= 2.303 nRT log

(At constant temperature, P1V1 P2 V2 , therefore,

V2 P1

V1 P2

P1
P2

WORK DONE IN IRREVERSIBLE ISOTHERMAL EXPANSION

w Pext V2 V1

HEAT CAPACITY
The heat capacity of a system is defined as the quantity of heat required for increasing the temperature of the
system through 1C. Heat capacity may be given as
dq
C = dT

(1)
Heat required to increase the temperature of one mole of the system by 1 0 is called Molar heat capacity.
Molar heat capacity at constant volume (Cv) :
If the volume is kept constant then
dE

Cv = dT

(4)
Hence, the heat capacity at constant volume of a given system may be defined as the rate of change of internal
energy with temperature.
Molar heat capacity at constant pressure (Cp)
REVERSIBLE ADIABATIC PROCESS :
In adiabatic change there is no transfer of heat, i.e. q = 0, it follows from the first law,
E dw

A.K.Pradhan , SUCCESS STUDY CIRCLE, 9438224466

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THERMODYNAMICS
Let, only mechanical work of expansion or contraction is involved, dW = PV . Moreover,
E C v dT

CvdT = PdV
For a system of 1 mole of an ideal gas, expanding adiabatically and reversibly from temperature T 1 to T2 and
volume V1 to V2, we have
RT
dV
CvdT = V

ln

V2
V1

or

C v T2 Cv T1
ln

ln
R
T1
R T2

or
ln

Cp Cv = R
V2
T
ln 1
V1
T2

ln

or

(-1)
V2

V1

Also,

ln

T1V11

T2 V 1
2

V2

T2

or

dV C v

V
R
V1

or

V1T1Cv / R V2 T2 Cv / R

dT
T
T1

/R

Cv
V2
T

ln 1
V1 Cp Cv T2

Cp Cv
Cv

or

ln

=K

V2
T
ln 1
V1
T2

( = Cp/Cv)

T1
T2

ln

dV C v dT

V
R . T
C
V
T
ln 2 ln 1
V1
T2

or

V2

V1

T1

T2

T2 V1

T1 V2

V1

V2

T2 T1

TV 1 constant
PV
Substituting, T by R
PV 1
V
R
= constant

PV = constant
Similarly,

T P

RT

TV 1 T

= constant

constant

Also, TP

1
1

Also, from

= constant

Cv T W

w Cv T2 T1

(for one mole)

T T
1 2 1

For n moles
nR

T T
1 2 1
IRREVERSIBLE ADIABATIC EXPANSION
In free expansion, the external pressure is zero, i.e. work done is zero. Accordingly E which is equal to w is also
zero. If E is zero, T should be zero. Thus, in free expansion (adiabatically) T = 0, E = 0, w = 0, H 0 .
w

In intermediate expansion, the volume changes from V1 to V2 against external pressure, Pext
w Pext V2 V1

T2 P1 T1P1
R
P1P2

RT2 RT1

P1
P2

Pext

Pext

T2 P1 T1P2

P1P2

w C p T2 T1 RPext

Limitations of first law of thermodyanamics

This law fails to tell us under what conditions and to what extent it is possible to bring about conversion of
one form of energy into the other.
The first law fails to contradict the existence of a 100% efficient heat engine or a refrigerator.

A.K.Pradhan , SUCCESS STUDY CIRCLE, 9438224466

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THERMODYNAMICS
Example:1. One mole of a gas is heated at constant pressure to raise its temperature by 2C. The work done by the
system in joules
(a) 4.157
(b) 8.314
(c) 12.471
(d) 16.628
Solution :
(d) W = PV = nRT = 1 8.314 2 = 16.628 J.
Example : 2 1m3 of neon gas initially at 273.2 K and 10 atm undergoes expansion isothermally and reversibly to
final pressure of 1 atm. The work done by the gas is
(a) 232.85 kJ
(b) 2332 kJ
(c) 914.1 kJ
(d) 2.32 kJ
Solution :
(b) Work done in isothermal reversible process is

W nRT ln

V2
P
nRT ln 1
V1
P2

So, to apply the above equation first we calculate n by using PV= nRT
So,

10 4
10
8.314 2.303 log
0.0821
1

W = 2332 kJ
Example : 3 One mole of an ideal gas is allowed to expand reversibly and adiabatically from a temperature of
27C. If the work done during the process is 3 kJ, the final temperature will be equal to
(Cv = 20 JK1)
(a) 150 K
(b) 100 K
(c) 26.85 K
(d) 295 K
Solution :
(a) dW = Du
nCVT = 3
1 20 T = 3 103

3000
300 T2
T = 20
(Since after expansion the temperature will be lowered)
300
T2
300 150 K
2

Example: 4 One mole of an ideal monoatomic gas at temperature T and volume 1 L expands adiabatically to
2 L against a constant external pressure of one atmosphere, then final temperature of gas will be

2
3 0.0821

2
3 0.0821

(a)
(b)
Solution:
(b) U = W = nCv [T2 T1] = P(V2 V1)
3/2R [T2 T1] = 1

T
(c)

5 / 31

T
(d) 2

5 / 31

2
T2 = T 3 .0821 .

SECTION II
Heat of Reaction
THERMOCHEMISTRY
Thermochemistry deals with the transfer of heat between a chemical system and its surroundings when a change of
phase or a chemical reaction takes place within the system. In general, a chemical reaction can be either exothermic
or endothermic. In the former case, heat is released to the surroundings when the reactants at a given temperature
and pressure are converted to the products at the same temperature and pressure, and in the latter heat is absorbed
by the system, from the surroundings.

Hoformation

Standard Enthalpy of formation

The change in enthalpy when one mole of any substance is formed at 298 K and 1 atm pressure from its constituent
atoms in there standard elemental form.
Enthalpy change when one mole of a given compound is formed from its elements.
H2(g) + 1/2O2(g)
2H2O(l), H = 890.36 kJ/mol
Enthalpy of Combustion
Enthalpy change when one mole of a substance is burnt in oxygen
A.K.Pradhan , SUCCESS STUDY CIRCLE, 9438224466

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THERMODYNAMICS

E n th a lp y

CH4(g) + 2O2(g) CO2(g) + 2H2O(l), H = 890.36 kJ/mol

Enthalpy of Neutralization
Enthalpy change when one equivalent of an acid is neutralized by a base in dilute solution. This is constant and its
values are 13.7 kcal for neutralization of any strong acid by a base since in dilute solutions they completely
dissociate into ions.
H+ (aq) + OH (aq) H2O (l)
H = 13.7 kcal
Enthalpy of Transition
Enthalpy change when one mole of a substance is transformed from one allotropic form to another allotropic form.
C (graphite)
C (diamond) H = 1.9 kJ/mol
HESSS LAW OF CONSTANT HEAT SUMMATION
The total enthalpy change of a reaction is the same, regardless of whether the reaction is completed in one step or in
several steps. It has been experimentally verified and is also a consequence of the law of conservation of energy. It
is of particular utility in calculation of the heats of reactions which are difficult for practical calorimetric
measurements.
For example, carbon can be converted into CO2 in a single step
C(s) + O2(g) CO2(g)
H = 94 kcal
or in two steps
C(s) + 1/2 O2(g) CO(g)
H1 = 26.4 kcal
CO(g) + 1/2 O2(g)

CO2(g) H2 = 67.6 kcal

According to Hesss law, H = H1 + H2 = 26.4 67.6 = 94 kcal

T h e rm o d y n a m ic p a ra m e te r

APPLICATIONS OF HESSS LAW

For determination of enthalpies of extremely slow reactions.

Horeaction
Hreaction

products
formation

reactants
formation

bond dissociation energy of reactant

bond dissociation energy of product

SECTION III

Bond-Energy
For determination of enthalpies of extremely slow reactions.
Hreaction

bond dissociation energy of reactant

bond dissociation energy of product

VARIATION OF HEAT OF REACTION WITH TEMPERATURE

The heat of reaction depends on the temperature. The relation between the two is known as Kirchhoffs equation.
H2 H1
T2 T1

= Cp

E2 E1
T2 T1

= Cv
Cp = molar heat capacity of products molar heat capacity of reactants (at constant pressure)
Cv = molar heat capacity of products molar heat capacity of reactants (at constant volume)
Example.5. The enthalpies of combustion of C(graphite) and C(diamond) are 393.5 and 395.4 kJ/mol
respectively. The enthalpy of conversion of C(graphite) to C(diamond) in kJ/mol is
(a) 1.9
(b) 788.9
(c) 1.9
(d) 788.9
Solution:
(c) Cgraphite + O2

CO2 ;
H = 393.5
Cdiamond + O2

CO2
;
H = 395.4
Cgraphite Cdiamond = 393.5 + 395.4 = 1.9
A.K.Pradhan , SUCCESS STUDY CIRCLE, 9438224466

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THERMODYNAMICS
Example: 6. The difference between heats of reaction at constant pressure and constant volume of the
following reaction would be
2C6H6(l) + 15O2(g)

12CO2(g) + 6H2O(l) at 25C in kJ mol1 is

(a) 7.43
(b) +3.72
(c) 3.72
(d) +7.43
Solution:
(a) H = U + ngRT

3 8.314 298
1000
H U = ngRT =
= 7.4327 kJ mol1.

Example :7 The heat of combustion of solid benzoic acid (C7H6O2) at constant volume is 321.30 kJ at 27C.
The heat of combustion at constant pressure is.
(a) 321.30 300R
(b) 321.30 + 300R
(c) 321.30 150R
(d) 321.30 + 900R
Solution :
(c)

15
C6H5COOH(s) + 2 O2

15
1

ng = 7 2 = 2 .

7CO2(g) + 3H2O(l)

1
2 ;

H = U + ng.RT ; ng =
H = 321.30 150 R.
Example: 8 Calculate the heat of formation of methane in kcal mol 1 using the following thermo chemical
reactions.
C(s) + O2(g)

CO2(g) ;
H = 94.2 kcal mol1

1
H2(g) + 2 O2(g)

H2O(l) ; H = 68.3 kcal mol1

CO2(g) + 2H2O(l) ; H = 210.8 kcal mol1
(b) 47.8
(c) 20.0

CH4(g) + 2O2(g)

(a) 45.9
Solution :
(c) C(s) + O2(g)
CO2(g) + 94.2 kcal
(1)
H2(g) + O2(g)
H2O(l) + 68.3 kcal
(2)
CH4(s) + 2O2(g)

CO2(g) + 2H2O(l) + 210.8 kcal (3)

The required equation is
C(g) + 2H2(g)
CH4(g)

(d) 47.3

H H ( 2 H ) H

f
1
2
3 = 20 kcal mol1.
so,
Example : 9 Using bond energy data, calculate heat of formation of isoprene

. Given bond

energy of CH = 98.8 kcal, HH = 104 kcal, CC = 83 kcal, C=C = 147 kcal and H of
C(s) C(g) = 171 kcal
(a) 28.3 kcal mol1
(b) 20.6 kcal mol1
(c) 283 kcal mol1
(d) 206 kcal mol1
Solution :
5C (graphite) + 4H2
(b)
H = 5(171) + 4 (104) [(147 2) + (83 2) + (8 98.8)] = 20.6 kcal

Numerical-Problem for Practice :

1.

If

C O2 CO2 94.2 kcal

H2

1
O2 H 2O 68.3 kcal
2

A.K.Pradhan , SUCCESS STUDY CIRCLE, 9438224466

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THERMODYNAMICS
CH 4 2O2 CO2 2H 2O 210.8 kcal

then the possible heat of methane will be

(a) 47.3 kcal
(b) 20.0 kcal
2.

If

(c) 45.9 kcal

S O2 SO2; (H 298.2)

(d) 47.3 kcal

1
O2 SO3; (H 98.2)
2
SO3 H 2O H 2SO4 ; (H 130.2)
SO2

H2

1
O2 H 2O;(H 287.3)
2

then the enthalpy of formation of H 2SO4 at 298K will be

3.

(a) 433.7 kJ
(b) 650.3 kJ
(c)
The heat evolved in the combustion of benzene is given by

320.5 kJ

(d) 813.9 kJ

1
C6 H 6 7 O2 6CO 2(g) 3H 2O(l);H 3264.6kJ
2

4.

Which of the following quantities of heat energy will be evolved when 39gC6 H 6 are burnt
(a) 816.15 kJ
(b) 1632.3 kJ
(c) 6528.2 kJ
(d) 2448.45 kJ
Thermochemical reactions
C(graphite
)
CO(g)

5.

6.

1
O2(g) CO(g);H 110.5kJ
2

1
O2 (g) CO 2 (g);H 283.2kJ
2

) O2(g) CO 2(g)
From the above reaction, the heat of reaction for C(graphite
will be
(a) 393.7 kJ
(b) + 393.7 kJ
(c) 172.7 kJ
(d) + 172.7 kJ
Evaporation of water is
(a) An endothermic change
(b) An exothermic change
(c) A process where no heat change occurs
(d) A process accompanied by chemical reaction
H f

(a)

(298 K) of methanol is given by the chemical equation

CH 4 (g) 1 / 2O2(g) CH 3OH (g)

(c) C (diamond) 1 / 2O2(g) 2H 2(g) CH 3OH (l)

7.

If

H of

(d)

CO(g) 2H 2(g) CH 3OH (l)

for H 2O2 and H 2O are 188kJ / mole and 286kJ / mole. What will be the enthalpy change of the

reaction 2H 2O2(l) 2H 2O(l) O2(g)

(a) 196kJ / mole

8.

(b) C (graphite) 1 / 2O2(g) 2H 2(g) CH 3OH (l)

(b) 146kJ / mole

(c)

494kJ / mole

The heat of transition (H t ) of graphite into diamond would be, where

(d) 98kJ / mole

C(graphite
) O2(g) CO 2(g); H x kJ

C(diamond
) C 2(g) CO 2(g); H ykJ
1

9.

1
(b) (x y)kJ mol

(a) (x y)kJ mol

Given that

(c)

(y x)kJ mol1

(d) None of these

2C(s) 2O2(g) 2CO 2(g); H 787kJ

1
O2(g) H 2O(l); H 286kJ
2
1
C 2H 2(g) 2 O2(g) 2CO 2(g) H 2O(l);H 1301kJ
2
H 2 (g)

Heat of formation of acetylene is

(a) 1802kJ
10.

11.

(b)

1802kJ

(c)

Heat of formation of CO 2(g), H 2O(l) and CH 4 (g) are

of combustion of methane is
(a) 212.9 kcal
(b) 136.8 kcal
Heat of neutralisation for the given reaction
released when
(a)

0.25mole

22.5kJ mol1

of

NaOH

(b)

800kJ

94.0, 68.4 and 17.9 kcal respectively. The heat

(c) 304.3 kcal

NaOH HCl NaCl H 2O

is titrated against
57.1kJ mol1

(d) 228kJ

0.25mole

(c)

A.K.Pradhan , SUCCESS STUDY CIRCLE, 9438224466

of

is

(d) 105.2 kcal

57.1kJ mol1

. What will be the heat

HCl

14.3kJ mol1

1
(d) 28.6kJ mol

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THERMODYNAMICS
12.

The heat of combustion of

formation of methane is

CH 4(g),C(graphite)

(a) 4.0kcal
13.

40kcal

are 20kcal, 40kcal and 10kcal respectively. The heat of

(c)

80kcal

(d) 80kcal

The enthalpy of formation of ammonia is 46.0kJ mol . The enthalpy change for the reaction
2NH 3 (g) 2N 2(g) 3H 2 (g)
mol1

is
1
(b) 92.0 kJ mol

1
(c) 23.0 kJ mol

1
(d) 92.0 kJ mol

1
o
The heat of combustion of benzene determined in a bomb calorimeter is 870kcalmol at 25 C . The value
of E for the reaction is

(a) 1740kcal
15.

H 2(g)

(a) 46.0 kJ
14.

(b)

and

(b)

870kcal

(c)

872kcal

(d) 874kcal

1
The standard heats of formation in kcal mol of NO2(g) and N 2O4 (g) are 8.0 and 2.0 respectively. The heat

of dimerization of NO2 in kcal is

2NO2(g) N 2O4 (g)

16.

(a) 10.0
(b) 6.0
(c) 12.0
(d) 14.0
The difference between heats of reaction at constant pressure and at constant volume for the reaction
2C 6 H 6 (l) 15O2(g) 12CO 2 (g) 6H 2O(l)

o
at 25 C in kJ is
(b) + 3.72
(c) 3.72

(a) 7.43
17.

If the bond dissociation energies of

fH

XY , X 2

19.
20.

(d) + 7.43

(all diatomic molecules) are in the ratio of 1 : 1 : 0.5 and

for the formation of XY is 200kJ mole . The bond dissociation energy of X 2 will be
1

18.

and

Y2

(a) 100kJ mol

(b) 800kJ mol
(c) 300kJ mol
(d) 400kJ mol
o
Energy required to dissociate 4 gm of gaseous hydrogen into free gaseous atoms is 208 kcal at 25 C . The
bond energy of H H bond will be
(a) 104 kcal
(b) 10.4 kcal
(c) 1040 kcal
(d) 104 cal
The bond dissociation energies of gaseous H 2,Cl 2 and HCl are 104, 58 and 103 kcal respectively. The
enthalpy of formation of HCl gas would be
(a) 44 kcal
(b) 44 kcal
(c) 22 kcal
(d) 22 kcal
The first ionization energy for Li is 5.4 eV and electron affinity of Cl is 3.61eV. The H (in kJ/mol) for the
19

reaction Li(g) Cl(g) Li Cl is (if resulting ions do not combine with each other) (1eV 1.6 10 J )
(a) 70
(b) 100
(c) 170
(d) 270

21.

22.

Given that C(g) 4H (g) CH 4 (g);H 166kJ

The bond energy C H will be
(a) 208 kJ/mole
(b) 41.6 kJ/mole

24.

25.
26.

(d) None of these

1

The H H bond energy is 430 kJ mol and Cl Cl bond energy is 240kJ mol . H for HCl is 90kJ . The
H Cl bond energy is about
1
(a) 180kJ mol

23.

(c) 832 kJ/mole

(b)

360kJ mol1

(c)

213kJ mol1

1
(d) 425kJ mol

1
o
If the bond energies of H H , Br Br and HBr are 433, 192 and 364 kJ mol respectively, the H for the

reaction, H 2(g) Br2(g) 2HBr(g) is

(a) + 261 kJ
(b) 103 kJ
(c) 261 kJ
(d) + 103 kJ
A mixture of two moles of carbon monoxide and one mole of oxygen, in a closed vessel is ignited to convert
the carbon monoxide to carbon dioxide. If H is the enthalpy change and E is the change in internal
energy, then
(a) H E
(b) H E
(c) H E
(d) The relationship depends on the capacity of the vessel

E
The relation between
and H is
(a) H E P V
(b) H E P V
(c) E V H
(d) E H P V
At constant T and P, which one of the following statements is correct for the reaction,
1
O2(g) CO2(g)
2
H is independent

CO(g)

(a)
(b)

H E

of the physical state of the reactants of that compound

(c)

H E

(d)

A.K.Pradhan , SUCCESS STUDY CIRCLE, 9438224466

H E

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THERMODYNAMICS
27.
28.

Which is not the correct relation between enthalpy (H ) and intrinsic energy E)

(a) H E P V
(b) H E n RT
(c) H E P V
(d) E H P V
The work done in ergs for the reversible expansion of one mole of an ideal gas from a volume of 10 litres to
o
20 litres at 25 C is
(a) 2.303 298 0.082log2

(b)

(c) 2.303 298 0.082log0.5 (d)

29.
30.
31.
32.

33.

34.

35.
36.

37.
38.

For the reaction, CH 3COOH (l) 2O 2 (g) 2CO 2 (g) 2H 2O(l) at 25 C and 1 atm. pressure, H 874kJ . Then
the change in internal energy (E) is
(a) 874 kJ
(b) 871.53 kJ
(c) 876.47 kJ
(d) + 874 kJ
In a closed insulated container, a liquid is stirred with a paddle to increase its temperature. In this process,
which of the following is true
(a) E W Q 0
(b) E 0, Q W 0
Hess law is based on
(a) Law of conservation of mass
(c) Enthalpy is a state function

41.
42.

(c)

E W 0, Q 0

(d) E Q 0,W 0

(b) Law of conservation of energy

(d) None of these

For the reaction, C 3 H 8 (g) 5O2 (g) 3CO 2 (g) 4H 2O(l) at constant temperature, H E is
(a) RT
(b) + RT
(c) 3RT
(d) + 3RT
According to Hesss law, the heat of reaction depends upon
(a) Initial condition of reactants
(b) Initial and final conditions of reactants
(c) Intermediate path of the reaction
(d) End conditions of reactants

o
The value of H E for the following reaction at 27 C will be 2NH 3 (g) N 2 (g) 3H 2 (g)
(a) 8.314 273 (2)
(b) 8.314 300 (2)
(c) 8.314 27 (2)
(d) 8.314 300 (2)
For which of the following E H

N 2O4 (g)

2NO2 (g)

H 2 (g) Cl 2 (g)

40.

8.31 107 298 2.303log0.5

(e) 2.303 298 2log2

Which of the following expressions represents the first law of thermodynamics
(a) E q W
(b) E q W
(c) E q W
(d) E q W
Work done during isothermal expansion of one mole of an ideal gas from 10 atm to 1 atm at 300 K is (Gas
constant = 2)
(a) 938.8 cal.
(b) 1138.8 cal.
(c) 1381.8 cal.
(d) 1581.8 cal.
In an adiabatic expansion of an ideal gas
(a) W E
(b) W E
(c) E 0
(d) W 0

(a)

39.

298 107 8.31 2.303log2

(b)

2SO2 (g) O2 (g)

H 2 (g)

2SO3 (g)

1
O2 (g)
2

(c)

H 2O(l)
The work done by a system is 8 joule, when 40 joule heat is supplied to it. What is the increase in internal
energy of system
(a) 25 J
(b) 30 J
(c) 32 J
(d) 28 J
A system absorb 600J of heat and work equivalent to 300J on its surroundings. The change in internal energy
is
(a) 300 J
(b) 400 J
(c) 500 J
(d) 600 J
Work done during isothermal expansion of one mole of an ideal gas from 10 atom. to 1 atm at 300K is
(a) 4938.8 J
(b) 4138.8 J
(c) 5744.1 J
(d) 6257.2 J
One mole of an ideal gas is allowed to expand freely and adiabatically into vacuum until its volume has
doubled. A statement which is not true concerning this expression is
(a) H 0
(b) S 0
(c) E 0
(d) W 0
2HCl (g) (d)

43.

At 27 C, one mole of an ideal gas is compressed isothermally and reversibly from a pressure of 2 atm to 10
atm. The values of E and q are (R 2)
(a) 0, 965.84 cal
(b) 965.84 cal, + 965.84 cal
(c) + 865.58 cal, 865.58 cal
(d) 865.58 cal, 865.58 cal

44.

o
One mole of an ideal gas is allowed to expand reversibly and adibatically from a temperature of 27 C . If the

work done during the process is 3 kJ , then final temperature of the gas is (CV 20 J / K )
(a) 100 K
(b) 150 K
(c) 195 K
(d) 255 K

A.K.Pradhan , SUCCESS STUDY CIRCLE, 9438224466

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THERMODYNAMICS
45.

46.

47.

An ideal gas expands in volume from 1 10 m to 1 10 m at 300 K against a constant pressure of

1 105 Nm2 . The work done is
(a) 270 kJ
(b) 900 kJ
(c) 900 J
(d) 900 kJ
3
3
4dm
6dm
The work done during the expansion of a gas from a volume of
to
against a constant external
pressure of 3atm is ( 1L atm 101.32J )
(a) + 304 J
(b) 304 J
For the reaction,
(a) H U

A(s) 2B(g) 4C(s) D(l) H

.
and U

3RT
(b)

(c) 6 J
are related as
(c) H U RT

(d) 608 J
(d) H U 3RT

ANSWER:
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.

b
d
b
a
a
b
a
b
d
a
c
c

13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.

b
b
d
a
b
a
c
c
b
d
b
b

25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.

b
c
c
b
c
c
b
a
c
b
c
b

37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.

d
c
c
a
c
d
a
b
c
d
d

48. SECTION IV

49. Second law of thermodynamics and Hess Law :

50.
It has been stated in several forms as mentioned below:
All the spontaneous processes are irreversible in nature.
It is impossible to obtain work by cooling a body below it lowest temperature.
It is impossible to take heat from a hot reservoir and convert it completely into work by a cyclic process
without transferring a part of it to cold reservoirs.
51. Entropy is a thermodynamic state function which is measure of randomness or disorder of molecules of the
system. Mathematically it may be defined as the integral of all the terms involving heat exchanged (q)
divided by the absolute temperature (T) during each infinitesimally small change of the process carried out
reversibly at constant temperature.
1

ds T q

rev

52.

qrev
T

53.
54. Entropy change in phase transformation when a solid changes into liquid at its fusion temperature, there is
absorption of heat (latent of heat). Let, Hf be the molar heat of fusion
S f

55.

Hf
Tf

56. Similarly, if the latent heat of vapourization and sublimation are denoted by
The entropy of vapourization and sublimation are given by
Svap

57.
58.

Ssub

Hvap

and Hsub respectively.

Hvap
Tb

Hsub
Ts

vap
Since Hf ,
and Hsub are all positive, these processes are accompanied by increase in entropy.
59. As for an isothermal process, the change in entropy is

60.

qrev
T

A.K.Pradhan , SUCCESS STUDY CIRCLE, 9438224466

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THERMODYNAMICS
61. where qrev is the heat absorbed during the reversible path.
62. Since E = 0 in a reversible path, hence by first law of thermodynamics
qrev w rev 2.303nRT log

63.

V2
V1

64. Entropy change associated with change in temperature from T2 to T1 at constant pressure P is given by
S 2.303Cp log

65.

T2
T1

Entropy change for one mole of ideal gas

S Cv ln

T2
V
T
P
Rln 2 Cp ln 2 Rln 1
T1
V1
T1
P2

At constant temperature (isothermal process)

S Rln

V2

Rln

P1
P2

V1
66.
67. M2. Enthalpy change for the transition of liquid water to steam is 41 kJ mol 1 at 100C. The entropy change
for the above process is
68.
(a) 110 JK1 mol1
(b) 410 JK1 mol1
(c) 0.41 JK1 mol1
(d) 0.1099 JK1 mol1
69.

2.

S t

(a)

41000

373 J K1 mol1

= 110 J K1 mol1

70.Numerical-Problem for Practice :

71. 1. For a reversible spontaneous change S is

E
T

P V
T

q
T

72.
(a)
(b)
(c)
(d)
RT log K
73. 2. An irreversible process occuring isothermally in an isolated system leads to
74.
(a)
Zero entropy
75.
(b)
An increase in the total entropy of the syst
76.
(c)
A decrease in the total entropy of the system
77.
(d)
None of these
78. 3. The entropy values (in JK-1 mol-1) of H2(g) = 130.6, Cl2(g) = 223.0 and HCl(g) = 186.7 at 298 K and 1 atm
pressure. Then entropy change for the reaction
79.
80.
81.

H 2(g) Cl 2(g) 2HCl (g)

is

(a)

+ 540.3
(b) + 727.3
(c) 166.9
(d)
+
19.8
4. When one mole of monoatomic ideal gas at T K undergoes adiabatic change under a constant external
pressure
of
1
atm
changes
volume
from
1
litre
to
2
litre.
The final temperature in Kelvin would be
T

82.

(2 / 3)

(a)

(b) T + 3 0.0821

(c) T

(d)

2
3 0.0821

83.

5.

o
9.0 gm of H 2O is vaporised at 100 C and 1 atm pressure. If the latent heat of vaporisation of water is

x J / gm

, then S is given by

84.

(a)

x
373

(b)

18x
100

(c)

18x
373

(d)

1 18x

2 373

85.

6. The S for the vaporisation of 1 mol of water is 88.3 J/mole K. The value of S for the condensation
of 1 mol of vapour will be

86.

(a)

88.3 J/mol K

2
(b) (88.3) J/mol K

(c)

88.3

J/mol

1
88.3

87.

7.

(d)
J/mol K
For which reaction from the following, S will be maximum

A.K.Pradhan , SUCCESS STUDY CIRCLE, 9438224466

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THERMODYNAMICS
88.

(a)

89.
90.
91.

8.

92.
ve
9.

95.

1
O2(g) CaO(s)
2

(b)

CaCO3(s) CaO(s) CO 2(g)

C(s) O2(g) CO 2(g)

(c)
(d) N 2(g) O2(g) 2NO(g)
The occurrence of a reaction is impossible if
H is +ve ; S is also + ve but H TS
(a)

(b)

93.
94.

Ca(s)

is ve ; S is also ve but H TS

(c) H is ve ; S is +

H is + ve ; S is ve
(d)
1
If the enthalpy of vaporization for water is 186.5 kJ mol , the entropy of its vaporization will be

(a)

0.5 JK 1mol1
1

1
1
(b) 1.0 JK mol

1
1
(c) 1.5 JK mol

2.0 JK mol
(d)
10. Which of the following statement is true. The entropy of the universe
(a)
Increases and tends towards maximum value
to be zero
(c)
Remains constant
increases with a periodic rate

96.
97.
98.

(b) Decreases and tends

(d) Decreases

and

3
1
11. When enthalpy and entropy change for a chemical reaction are 2.5 10 cal and 7.4 cal deg
respectively.

99.

Predict the reaction at 298K is

(a)
Spontaneous
(b) Reversible
(c) Irreversible (d)
Non-spontaneous
102. 12. The total entropy change for a system and its surroundings increases, if the process is
103.
(a)
Reversible
(b) Irreversible
(c) Exothermic (d)
Endothermic
100.
101.

104. 13. The enthalpy change for the transition of liquid water to steam,
entropy change for the process is
105.

(a)

111.9 J mol1K 1
1

(b)

H vap 37.3kJ mol1

37.3 J mol1 K 1

at 373K . The

1 1
(c) 100J mol K

74.6 J mol K
(d)
106. 14. The positive value of S indicates that
107.
(a)
The system becomes less disordered
108.
(b)
The system becomes more disordered
109.
(c) The system is in equilibrium position
110.
(d) The system tends to reach at equilibrium position

111.
112.

15.

For reaction 2Cl(s) Cl 2(s) , the signs of H and S respectively are

(a) +,
(b) +, +
(c) , (d)
, +

113.
114.

16.

The enthalpy of water is 386kJ . What is entropy of water

(a) 0.5 kJ
(b) 1.03 kJ
(c) 1.5 kJ

(d)

22.05 kJ
17.

115.
Identify the correct statement regarding entropy
o
116.
(a) At 0 C , the entropy of a perfectly crystalline substance is taken to be zero
117.
(b) At absolute zero of temperature, the entropy of a perfectly crystalline

ve
substance is
118.
(c) At absolute zero of temperature, the entropy of all crystalline substances is
taken to be zero
119.
(d) At absolute zero of temperature, the entropy of a perfectly crystalline
substance is taken to be zero
120. 18. One mole of an ideal gas at 300K is expanded isothermally from an initial volume of 1 litre to 10 litres.
1 1
The change in energy for this process is (R 2calmol K )
121.
(a)
163.7 cal
(b) 850.2 cal
Zero

(c) 1381.1 cal (d)

122. 19. If 900J / g of heat is exchanged at boiling point of water, then what is increase in entropy

A.K.Pradhan , SUCCESS STUDY CIRCLE, 9438224466

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THERMODYNAMICS
123.

(a)
Zero

43.4 J/mole

(b) 87.2 J/mole

(c) 900 J/mole (d)

124. 20. If 0.75 mole of an ideal gas expands isothermally at 27 C from 15 litres to 25 litres, the maximum work
obtained is
125.
(a)
8.40 J
(b) 9.34 J
(c) 10.86 J
(d)
10.43 J
126. 21. In which of the following conditions a chemical reaction can not occur
H and S increase and TS H
127.
(a)
(b) H and S decrease

S
and
H increases and S decreases
128.
(c)
(d) H decreases and
S increases
o
o
129. 22. An engine operating between 150 C and 25 C takes 500 J heat from a higher temperature reservoir if
there are no frictional losses, then work done by engine is
130.
(a)
147.7 J
(b) 157.75 J
(c) 165.85 J
(d)
169.95 J
131. 23. The entropy of a perfectly crystalline solid at absolute zero is
132.
(a)
Positive
(b) Negative
(c) Zero
(d)
Not definite
133. 24. Which of the following conditions will always lead to a non-spontaneous change
134.
(a)
Positive H and positive S
(b) Negative H and
negative S
H
135.
(c)
Positive H and negative S (d)
Negative
and

S
positive
1
1
1
136. 25. Following data is known about melting of a compound AB. H 9.2kJ mol , S 0.008kJ K mol . Its
melting point is

137.

(a)

736 K

(c) 1150K

(b) 1050 K

(d)

1150 C

138. 26. The volume of a gas decreases from 500cc to 300cc when a sample of gas is compressed by an average
pressure of 0.6 atm. During this process 10 J of heat is liberated. The change in internal energy is
139.
(a)
2.16 J
(b) 12.156 J
(c) 2.16 J
(d)
101.3 J
1
140. 27. The standard entropies of CO 2 (g),C(s) and O2 (g) are 213.5, 5.690 and 205JK respectively. The standard

entropy of formation of CO 2 (g) is

141.

(a)
2.86JK

1.86JK

1
(b) 1.96JK

1
(c) 2.81JK

(d)

o
142. 28. One mole of an ideal gas is allowed to expand reversibly and adiabatically from a temperature of 27 C . If
1

the work done during the process is 3 kJ, the final temperature will be equal to (Cv 20JK )
o
143.
(a)
150 K
(b) 100 K
(c) 26.85 C
(d)
295 K
144. 29. The entropy change, in the conversion of one mole of liquid water at 373 K to vapour at the same
temperature is (Latent heat of vaporization of water,
145.

(a)

105.9 Jk

H vap 2.257kJ / g)

(b)

107.9 Jk 1

(c)

108.9 Jk 1

(d)

109.9 Jk 1

146. 30. The entropy changed involved in the conversion of 1 mole of liquid water at 373 K to vapour at the
same temperature will be
147.
148.

[H vap 2.257kJ / gm]

(a)
0.120 kJ

0.119 kJ

(b) 0.109 kJ
1

(c) 0.129 kJ

(d)

149. 31. The molar heat capacity of water at constant pressure is 75 JK mol . When 1.0 kJ of heat is supplied to
100 g of water which is free to expand the increase in temperature of water is
150.
(a)
6.6 K
(b) 1.2 K
(c) 2.4 K
(d)
4.8 K
A.K.Pradhan , SUCCESS STUDY CIRCLE, 9438224466

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THERMODYNAMICS
151. 32. The work done to contract a gas in a cylinder, is 462 joules. 128 joule energy is evolved in the process.
What will be the internal energy change in the process
152.
(a)
+ 590 joules
(b) 334 joules
(c) +
334
joules
(d)
590 joules
H (aq)

S o (298K ) K 1mol1

OH (aq) H 2O(l)

10.7
70
153. 33.
154.
Standard entropy change for the above reaction is

155.

60.3 JK 1mol1

(a)

(b)

80.7 JK 1mol1

(c)

70 JK 1mol1

10.7 JK mol
(d)
o
o
156. 34. One mole of water at 100 C is converted into steam at 100 C at a constant pressure of 1 atm. The

change in entropy is [heat of vaporisation of water at

157.
(a)
8.74 (b)
26.06

100o C 540cal/ gm

18.76

(c) 24.06

(d)

1
158. 35. The standard entropies of CO2(g),C(s) and O2(g) are 213.5, 5.740 and 205 JK respectively. The

standard entropy of formation of CO2 is

159.

2.76 JK 1

(a)

(b)

2.12JK 1

(c)

1.12JK 1

(d)

1.40 JK 1

160. ANSWER:
1.
2.
3.
4.
5.
6.
7.
8.
9.

c
b
d
d
d
c
b
d
a

10.
11.
12.
13.
14.
15.
16.
17.
18.

a
a
d
c
b
c
b
d
d

19.
20.
21.
22.
23.
24.
25.
26.
27.

a
b
c
a
c
c
c
c
c

28.
29.
30.
31.
32.
33.
34.
35.

a
c
b
c
c
b
d
a

36.

37. SECTION V
38.

Free-Energy :
39. It is general observation that chemical reactions tend to seek minimum energy and maximum randomness,
i.e. a reaction will be more probable to occur if it is exothermic or there is an increase in entropy. A reaction
will occur if the value of H is negative and the value S is positive. But the endothermic reactions in
which H is positive also takes place. There are reactions in which there is decrease in entropy, i.e. S is
negative but still they occur. It is, thus, clear that for the spontaneity of a reaction both H and S should
be considered simultaneously. The function that takes both enthalpy and entropy into account is called
Gibbs free energy (G)
40. Gibbs free energy (G) is defined as
G H TS
41.
42. For any Chemical Reaction :
0
43. G for a reaction under non-standard state conditions is G under standard state condition by relation
o
44. G G 2.303RTlogQ
45. where Q is called reaction-quotient before equilibrium is attained
46. For a general reaction,

47.

aA bB

48.

cC dD

C c D d
A a B b

49. When Q = 1, RT log Q 0,

G G o

A.K.Pradhan , SUCCESS STUDY CIRCLE, 9438224466

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THERMODYNAMICS

G 0, Q K K p or K c

50. When equilibrium is reached,

o
51. G 2.303RT logK
52. where K is called thermodynamic equilibrium constant.
53. EFFECT OF TEMPERATURE ON SPONTANEITY
55.
56.
57. Spontaneity of reaction
54. H

58. -ve
(exothermic)

G H TS

59.

62. Spontaneous at all temperature

65.

66. Spontaneous at low temperature

70. Non-spontaneous at high temperature

60.
64.

71. +
ve
(endothermic
)

61.

72.

69. +
74. +

75. Non-spontaneous at low temperature

73.
79.

80. Non-spontaneous at high temperature

82.

83.

84. Non-spontaneous at all temperature

86.

87. 0

88. Equilibrium

77.

78.

85. H TS

89. Example:10. For adsorption of a gas on solid adsorbent

90.
(a)
H is positive
(b) S is positive
(d)
E is positive
91. Solution : (c)
92. Example: 11. Consider the reaction:
93.
2Cl(g)

Cl2(g)
94. The sign of H and S of the above reaction respectively are
95.
(a)
+ and
(b) + and +
and +
96. Solution :
(c) G = H TS
97. S is ve because when two atoms form a molecule then degree of randomness
bond formation.
98. Example : 12 Consider the following:
99.
2Zn + O2 2ZnO;
G = 616 J
100.
2Zn + 2S 2ZnS;
101.
2S + 2O2 2SO2(g);
102. G for the following reaction 2ZnS + 3O2 2ZnO + 2SO2 would be
103.
(a) 731 J
(b) 1317 J
1317 J

2G

2G

(c) G

(c) and

is

negative

(d)

decreases is ve for the

..... (i)
G = 293 J ..... (ii)
G = 408 J ..... (iii)
(c) + 731 J

(d)

2G

ZnO
SO 2
ZnS
104. Solution : (a) G =
= [ 616 408] [ 293] = 731 J.
105. Example : 13 A chemical reaction can not occur at all if its
106.
(a) H value is positive and S value is negative
107.
(b) H value is negative and S value is positive
108.
(c) H and S value are negative but H > TS
109.
(d) H and S value are positive but H > TS
110. Solution: (a) G is always positive if H is positive and S is negative. Thus, the reaction is
nonspontaneous.

A.K.Pradhan , SUCCESS STUDY CIRCLE, 9438224466

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THERMODYNAMICS
111. Example:14 Sulphur exists in more than one solid form. The stable form at room temperature is
rhombic sulphur. But above room temperature the following reaction occurs.

112.
113. If H = 276.144 J at 298 K and 1 atm and G = 75.312 J
114. (a)
Calculate S at 298 K
115. (b) Assume that H and S do not vary significantly with temperature, calculate T eq., the temperature at
which rhombic and monoclinic sulphur exist in equilibrium with each other.
116. Solution:
117.
(a)
Since G H TS
S r hom bic

118.

119.
120.

121.

S monoclinic

H G
T

276.144 75.312
298

= 0.674 JK-1
Under equilibrium condition G 0

(b)

H Teq S 0

122.

Teq

123.
124.

H 276.144

S
0.674

= 409.7 K

125. Example : 15 Assume H and S to be independent of temperature, at what temperature will the
reaction given below become spontaneous ?
o

S / JK

126.

129.
130.

mol

N2 g O2 g

2NO g

191.4

210.5

204.9

Ho = 180.8 kJ mol 1

127.

128.

Solution :
o
So 2SNO
SNo 2 SOo 2 2 210.5 191.4 204.9

= 24.7 JK 1 mol 1
Q Go Ho TSo

131.

G o 180.8 T 24.7 103 kJ mol1

132.
when

o
for spontaneity, G 0 and this occurs

TSo Ho

133.
134.

Ho
So

180.8 103
7320 K
24.7

135.
136.

The reaction becomes spontaneous above a temperature of 7320 K.

137.

Example: 16 Calculate the standard entropy change for a reaction X Y , if the value of
Ho 28.40 kJ

7
and equilibrium constant is 1.8 10 at 298 K.

138.

Solution:

139.

o
We know that G 2.303RT log K

2.303 8.314 298 log1.8 107

140.
141.

= 38.498 kJmol.

142.

o
o
o
Also, G H TS

143.
144.

So

28.40 38.498
H o G o

0.0338 kJmol1K 1 =33.8 J K-1mol-1

298
T

Example:17 Calculate the temperature, at which the reaction given below is at equilibrium,
Ag 2 O s

1
O2 g
2

A.K.Pradhan , SUCCESS STUDY CIRCLE, 9438224466

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THERMODYNAMICS
1
1
1
Given, H 30.5 kJmol and S 0.066 kJK mol .
Solution:

145.
146.
147.
148.
149.

G H TS

At equilibrium, G = 0
H = T S
T

150.

H 30.5

462.12 K
S 0.066

151.
152. Numerical-Problem for Practice:
153.
154.

1.

The free energy change for a reversible reaction at equilibrium is

(a) Large positive
(b) Small negative
(c) Small
0
For a spontaneous change, free energy change G is
(a) Positive
(b) Negative
(c) Zero
(d) Can be positive or negative
The relation between G and H is not

(d)
2.

155.
156.
157.
158.

3.

159.

(a)

161.

(a)

H G T S

(b)

G H T S

positive

(c) T S G H

H T G S
(d)
160. 4.
At 300 K, the reactions which have following values of thermodynamic
parameters occur spontaneously
G o 400kJ mol1

H o 200kJ mol1, S o 4 JK

162.

mol1

H o 200kJ mol1, S o 4 JK

(c)
H o 200J mol1, S o 40JK

(b)

mol1

(d)

mol1

o
What is the free energy change G when 1.0mole of water at 100 C and 1atm pressure is converted

163. 5.

o
into steam at 100 C and 1atm pressure

164.

540cal

(a)

(b)

9800cal

(c) 9800cal

(d)

0cal
G o

165. 6.
o

227 C

166.

is
(a)

for the reaction X Y Z is 4.606 kcal . The value of equilibrium constant of the reaction at
(R 2.0 cal. mol1 K 1 )

100 (b)

10
N 2O 4

(c)

(d) 0.01

NO2

167. 7. The standard enthalpy of the decomposition of

to
is 58.04 kJ and standard entropy of this
o
reaction is 176.7 J/K. The standard free energy change for this reaction at 25 C is
168.
(a)
539 kJ
(b) 539 kJ
(c) 5.39 kJ (d)
5.39 kJ
1

169. 8. For a reaction at 25 C enthalpy change and entropy changes are 11.7 10 J mol and 105J mol K
respectively. What is the Gibbs free energy
170.
(a)
15.05 kJ
(b) 19.59 kJ
(c) 2.55 kJ
(d)
22.55 kJ
171. 9. The correct relationship between free energy change in a reaction and the corresponding equilibrium
o

constant K c is
172.

(a)

G RT ln K c

(d)

Go RT ln K c

(b)

G RT ln K c

(c)

Go RT ln K c

173. 10. The free energy change for the following reactions are given below,

C2H 2(g)

5
O2(g)
2

2CO2(g) H 2O(l);Go 1234kJ

174.
175.

C(s) O2 (g) CO 2 (g) G o 394kJ

H 2 (g)

1
O2 (g) H 2O(l) G o 237kJ
2

What is the standard free energy change for the reaction H 2 ( g) 2C (s) C 2 H 2 (g)

A.K.Pradhan , SUCCESS STUDY CIRCLE, 9438224466

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THERMODYNAMICS
176.

(a)
209 kJ

209 kJ

(b) 2259 kJ

(c) + 2259 kJ (d)

177. 11. The equilibrium concentration of the species in the reaction A B C D are 3, 5, 10 and 15
178.
179.
180.
181.

moleL1

respectively at 300K the G for the reaction is

(a)
13.81
(b) 1381.8
(c) 138.18 (d)
1391.6
12. Two mole of an ideal gas is expanded isothermally and reversibly from 1 litre ot 10 litre at 300K . The
enthalpy change (in kJ ) for the process is:
(a)
11.4 kJ
(b) 11.4 kJ
(c) 0 kJ
(d)
4.8 Kj
13. Heat of neutralization of strong acid against strong base is constant and is equal to
4

(a)
13.7 kcal
(b) 57 kJ
(c) 5.7 10 J (d)
All of the above
183. 14. To calculate the amount of work done in joules during reversible isothermal expansion of an ideal gas,
the volume must be expressed in
3
3
m3 only
184.
(a)
(b) dm only
(c) cm only (d)
Any one of them
182.

185. 15. The enthalpy change for the reaction of 50.00 ml of ethylene with 50.00 ml of H 2 at 1.5 atm pressure is
H 0.31kJ

186.

(a)
0.0076 kJ

. The value of E will be

0.3024 kJ

187. 16. For a reaction

S 35.7 JK

188.
189.
190.

H 9.08kJ mol1

(b) 0.3024 kJ

(c) 2.567 kJ

(d)

and

mol1

Which of the following statements is correct for the reaction

(a)
Reversible and Isothermal
(b)
Exothermic
191.
(c)
Spontaneous and Endothermic (d)
Exothermic

Reversible

and

Spontaneous

and

192. 17. The enthalpies of formation of Al2O3 and Cr2O3 are 1596kJ and 1134kJ respectively. H for the
reaction 2Al Cr2O3 2Cr Al2O3 is

193.

(a)

[KCET 2003]

2730kJ

(b)

2730kJ

462kJ

(c) 1365kJ

(d)

194. 18. For a hypothetic reaction A B , the activation energies for forward and backward reactions are 19
kJ/mole and 9 kJ/mole respectively. The heat of reaction is
195.
(a)
28 kJ
(b) 19 kJ
(c) 10 kJ
(d)
9
kJ
1

196. 19. The enthalpy of neutralization of HCN by NaOH is 12.13kJ mol . The enthalpy of ionisation of HCN
will be
197.
(a)
4.519 kJ
(b) 45.10 kJ
(c) 451.9 kJ
(d)
45.19 kJ
198. 20.

C(graphite) O2(g) CO2(g)

199.

H 94.05kcalmol1

200.
201.

therefore

202.

(a)

C(diamond) O 2 (g) CO 2 (g); H 94.50kcalmol1

o
1
C(graphite) C(diamond) H 298
K 450calmol

(b)

C(diamond) C(graphite);

o
1
H 298
K 450calmol

203.

(c)
graphite

Graphite is the stabler allotrope(d)

Diamond is harder than

3
5
204. 21. The equilibrium constant of a reaction at 298K is 5 10 and at 1000K is 2 10 . What is the sign of
H for the reaction

A.K.Pradhan , SUCCESS STUDY CIRCLE, 9438224466

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THERMODYNAMICS
205.
206.

H 0

(a)
(d)
22.

(b)

H is negative

is

positive

None of these
Consider the reactions

C(s) 2H 2(g) CH 4 (g),H x kcal

207.
208.

C(g) 4H (g) CH 4 (g),H x1 kcal

209.
210.

The bond energy of C H bond is

211.

(a)

CH 4 (g) CH 3(g) H (g),H y kcal

ykcalmol1

(b)

x1 kcalmol1

(c)

x / 4 kcalmol1

x1 / 4 kcalmol1

(d)

212. 23. Given the bond energies N N, H H and N H bonds are 945, 436 and
enthalpy of the following reaction
213.

(c) H

N 2 (g) 3H 2(g) 2NH 3 (g)

93kJ

(a)

391kJ mole1

respectively, the

is

(b) 102kJ

(c) 90kJ

(d)

105kJ

214. 24. Which of the following is not a correct statement ?

215.
(a)
When G is negative, the process is spontaneous
216.
(b)
When G is zero, the process is in a state of equilibrium
217.
(c)
When G is positive, the process is non-spontaneous
218.
(d)
None of these

219. 25. If at 298 K the bond energies of C H , C C, C C and H H bonds are respectively 414, 347, 615 and

435 kJ mol , the value of enthalpy change for the reaction H 2C CH 2 (g) H 2 (g) H 3C CH 3 (g) at 298 K
will be
220.
(a)
+ 250 kJ
(b) 250 kJ
(c) + 125 kJ (d)

125 kJ
1

221. 26. The H 2O(g) molecule dissociates as

222.
223.
224.
225. 27.
226.

(i) H 2O(g) H (g) OH (g);H 490kJ

The average bond energy (in kJ) for water is
(a)
490 (b)
For the reaction
H 2 (g)

change at
227.

(a)

(ii) OH (g) H (g) O(g);H 424kJ

424 (c)

1
O2 (g) H 2O(l),H 285.8 kJ mol1
S 0.163kJ mol1K 1.
2

27o C

914 (d) 914/2

What is the value of free energy

for the reaction

236.9 kJ mol1

(b)

281.4 kJ mol1

(c)

334.7 kJ mol1

228.
229.
230.
231.
232.
233.
234.
235.
236.
237.

334.7 kJ mol
(d)
28. If H is the enthalpy change and E the change in internal energy accompanying a gaseous reaction
then
H is always less than E .
(a)
(b) H is always greater

E
than
.
H is less than E if the number of moles of gaseous products is greater than
(c)
the number of moles of
gaseous reactants.
H is less than E if the number of moles of gaseous products is less than the
(d)
number of moles of
gaseous reactants.
29. The latent heat of vapourization of a liquid at 500 K and 1 atm pressure is 10 kcal/mol. What will be the
change in internal energy of 3 moles of liquid at same temperature ?
(a) 13.0 kcal
(b) 13.0 kcal
(c) 27.0 kcal
(d) 27.0 kcal
30. Given:
(i) C + O2 CO2
Ho = x kJ
(ii) 2CO + O2

2CO2 Ho = y kJ
The enthalpy of formation of CO2 will be
y
(y 2x)
2x
2
2
(a)
y 2x
(b)
(c)
(d)
2x y

A.K.Pradhan , SUCCESS STUDY CIRCLE, 9438224466

Page 19

THERMODYNAMICS
238. 31. 5 mole of an ideal gas expand reversibly from a volume of 8 dm 3 to 80 dm3 at a temperature of 27C.
Calculate the change in entropy.
239.
(a) 70.26 JK1
(b) 82.55 JK1
(c) 95.73 JK1
(d) 107.11 JK1240. 32. The spontaneous nature of reaction is impossible if
241.
(a)
H is + ve, S is also + ve
(b) H is + ve, S is ve
242.
(c)
H is ve, S is + ve
(d) H is + ve, S is ve
243. 33. An ideal gas undergoing expansion in vacuum shows
244.
(a)
E =0
(b) W = 0
(c) q = 0
(d)
All of the above
245. 34. A system is provided 50 joule of heat and work done on the system is 10 J. The change in internal
energy during the process is
246.
(a)
40 J (b)
60 J (c)
80 J
(d)
50 J
247. 35. Molar heat capacity for a gas at constant temperature and pressure is
248.
(a)
3/2R
(b)
5/2R
249.
(c)
depends on atomicity of gas
(d) infinity ()
250. 36. The work done in an open vessel at 300 K, when 112 g iron reacts with dil. HCl is
251.
(a)
1200 cal
(b) 600 cal
(c) 300 cal
(d)
200 cal
252. 37. The difference between heat of reaction at constant pressure and constant volume for the reaction given
below at 25C in kJ is
2C6H6 l 15O2 g
12CO2 g 6H2O l
253.
254.
(a)
7.43
(b) +3.72
(c) 3.72
(d)
7.43
255. 38. One mole of an ideal gas expand spontaneously into a vacuum. The work done is
256.
(a)
2 J (b)
4 J (c)
zero
(d)
infinity

257. ANSWERS
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.

d
b
b
b
d
a
d
b
d
d

11.
12.
13.
14.
15.
16.
17.
18.
19.
20.

b
c
d
d
a
c
b
c
d
c

A.K.Pradhan , SUCCESS STUDY CIRCLE, 9438224466

21.
22.
23.
24.
25.
26.
27.
28.
29.
30.

b
a
a
d
d
d
a
d
c
c

31.
32.
33.
34.
35.
36.
37.
38.

c
b
d
a
c
a
a
c

Page 20

258.
259. ***********
260.
261.
262.
263.
264.
265.
266.
267.
268.
269.
270.
271.
272.
273.
274.
275.
276.
277.