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.

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

Isobaric

Isochoric

Isothermal
Pressure

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 V1 to final volume V2 will be given as
v2

w = PdV
v1

From ideal gas equation, PV = nRT

nRT
P =
V
v2
nRT
Hence w = dV [As T is constant]
v1 V

V2 V2 P1
w = nRT ln = 2.303 nRT log = 2.303 nRT log
V1 V1 P2

V2 P1
(At constant temperature, P1V1 P2 V2 , therefore, )
V1 P2

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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
C = dq (1)
dT
Heat required to increase the temperature of one mole of the system by 10 is called Molar heat capacity.
Molar heat capacity at constant volume (Cv) :
If the volume is kept constant then
dE
Cv = (4)
dT
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
Let, only mechanical work of expansion or contraction is involved, dW = PV . Moreover,
E Cv 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 C v dT V2
dV C v
T2
dT
CvdT = dV or . or
V V R T V1
V R T1
T

Cv T2 Cv T1 V2 T1
Cv / R

ln V2 = ln ln or ln ln or V1T1Cv /R V2T2Cv /R = K
V1 R T1 R T2 V1 T2
Cv
Cp Cv = R ln V2 T
ln 1 or Cp Cv
ln
V2 T
ln 1
V1 C p C v T2 Cv V1 T2

V2 T
or ( 1) ln ln 1 ( = Cp/Cv)
V1 T2
1 1 1 1
V T1 V2 T T2 V1 V
ln 2 ln or 1 T2 T1 1
V1 T2 V1 T2 T1 V2 V2

Also, T1V11 T2 V1 K
2

TV1 constant
PV
Substituting, T by
R
PV 1
V = constant
R

PV = constant
1
Similarly, RT = constant
TV 1 T
P

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T P1 constant
1
1
Also, TP = constant
Also, from Cv T W
w Cv T2 T1 (for one mole)
R
T T
1 2 1

For n moles
nR
w T2 T 1
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 .
In intermediate expansion, the volume changes from V1 to V2 against external pressure, Pext
w Pext V2 V1

RT RT T P T P
Pext 2 1 Pext 2 1 1 1 R
P2 P1 P1P2

T P TP
w Cp T2 T1 RPext 2 1 1 2
P1P2
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.
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
V2 P
W nRT ln nRT ln 1
V1 P2
So, to apply the above equation first we calculate n by using PV= nRT
10 4 10
So, W 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

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Solution :
(a) dW = Du
nCVT = 3
1 20 T = 3 103
3000
T = 300 T2 (Since after expansion the temperature will be lowered)
20
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 2 T T
(a) T (b) T (c) (d)
3 0.0821 3 0.0821 5 / 31 5 / 31
2 2
Solution:
(b) U = W = nCv [T2 T1] = P(V2 V1)
3/2R [T2 T1] = 1
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.

Standard Enthalpy of formation Hformation

o

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
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

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 THERMODYNAMICS
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

O2
=C
2
/2O
+1

Enthalpy
CO

-II
2 =C

th
Pa
/2O -I O 2
th
Pa = C
C+ 1

O2
C+

Thermodynamic parameter

APPLICATIONS OF HESSS LAW

For determination of enthalpies of extremely slow reactions.
Horeaction H products
formation H
reactants
formation

Hreaction 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
= Cp
T2 T1

E2 E1
= Cv
T2 T1

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

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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
H U = ngRT = = 7.4327 kJ mol1.
1000
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 :
15
(c) C6H5COOH(s) + O2 7CO2(g) + 3H2O(l)
2
15 1
ng = 7 = .
2 2
1
H = U + ng.RT ; ng = ; H = 321.30 150 R.
2
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) + O2(g) H2O(l) ; H = 68.3 kcal mol1
2
CH4(g) + 2O2(g) CO2(g) + 2H2O(l) ; H = 210.8 kcal mol1
(a) 45.9 (b) 47.8 (c) 20.0 (d) 47.3
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)
so, H f H1 (2 H 2 ) H 3 = 20 kcal mol1.
CH3
Example : 9 Using bond energy data, calculate heat of formation of isoprene CH2=C CH=CH2. 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 :
CH3
(b) 5C (graphite) + 4H2 CH2=C CH=CH2
H = 5(171) + 4 (104) [(147 2) + (83 2) + (8 98.8)] = 20.6 kcal

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Numerical-Problem for Practice :

1. If C O2 CO2 94 .2 kcal
1
H2 O2 H 2 O 68 . 3 kcal
2
CH 4 2O2 CO2 2 H2O 210 .8 kcal

then the possible heat of methane will be

(a) 47.3 kcal (b) 20.0 kcal (c) 45.9 kcal (d) 47.3 kcal
2. If S O2 SO 2 ; (H 298 .2)
1
SO 2 O 2 SO 3 ; (H 98 . 2)
2
SO 3 H2O H2SO 4 ; (H 130 .2)

1
H2 O2 H 2 O; (H 287 .3)
2

then the enthalpy of formation of H2SO 4 at 298K will be

(a) 433 .7 kJ (b) 650 .3 kJ (c) 320 .5 kJ (d) 813 .9 kJ
3. The heat evolved in the combustion of benzene is given by
1
C6 H 6 7 O 2 6 CO 2 (g) 3 H 2 O(l); H 3264 . 6 kJ
2

Which of the following quantities of heat energy will be evolved when 39 g C6 H 6 are burnt
(a) 816.15 kJ (b) 1632.3 kJ (c) 6528.2 kJ (d) 2448.45 kJ
4. Thermochemical reactions
1
C(graphite ) O 2 (g) CO (g); H 110 .5 kJ
2
1
CO (g) O 2 (g) CO 2 (g); H 283 .2 kJ
2

From the above reaction, the heat of reaction for C(graphite ) O2 (g) CO 2 (g) will be
(a) 393.7 kJ (b) + 393.7 kJ (c) 172.7 kJ (d) + 172.7 kJ
5. 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
6. H f (298 K) of methanol is given by the chemical equation
(a) CH 4 (g) 1 / 2O2 (g) CH 3 OH(g) (b) C (graphite) 1 / 2O2 (g) 2H 2 (g) CH 3 OH(l)
(c) C (diamond) 1 / 2O2 (g) 2H 2 (g) CH 3 OH(l) (d) CO(g) 2H 2 (g) CH 3 OH(l)

7. If H of for H 2 O 2 and H 2 O are 188 kJ / mole and 286 kJ / mole . What will be the enthalpy change of the
reaction 2H 2 O2 (l) 2H 2 O(l) O2 (g)
(a) 196 kJ / mole (b) 146 kJ / mole (c) 494 kJ / mole (d) 98 kJ / mole
8. The heat of transition (H t ) of graphite into diamond would be, where
C(graphite ) O2 (g) CO 2 (g); H x kJ

C(diamond ) C2 (g) CO 2 (g); H y kJ

(a) (x y ) kJ mol 1 (b) (x y ) kJ mol 1 (c) (y x ) kJ mol 1 (d) None of these

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9. Given that
2C(s) 2O2 (g) 2CO 2 (g); H 787 kJ

1
H 2 (g ) O 2 (g) H 2 O(l); H 286 kJ
2
1
C 2 H 2 (g ) 2 O 2 (g) 2CO 2 (g) H 2 O(l); H 1301 kJ
2
Heat of formation of acetylene is
(a) 1802 kJ (b) 1802 kJ (c) 800 kJ (d) 228 kJ
10. Heat of formation of CO 2 (g), H 2 O(l) and CH 4 (g) are 94.0, 68.4 and 17.9 kcal respectively. The heat
of combustion of methane is
(a) 212.9 kcal (b) 136.8 kcal (c) 304.3 kcal (d) 105.2 kcal
11. Heat of neutralisation for the given reaction NaOH HCl NaCl H 2 O is 57 .1 kJ mol 1 . What will be the heat
released when 0.25 mole of NaOH is titrated against 0.25 mole of HCl
(a) 22 .5 kJ mol 1 (b) 57 . 1 kJ mol 1 (c) 14 . 3 kJ mol 1 (d) 28 .6 kJ mol 1
12. The heat of combustion of CH 4 (g) ,C(graphite ) and H 2(g ) are 20 kcal, 40 kcal and 10 kcal respectively. The heat of
formation of methane is
(a) 4.0 kcal (b) 40 kcal (c) 80 kcal (d) 80 kcal
13. The enthalpy of formation of ammonia is 46 .0 kJ mol 1 . The enthalpy change for the reaction
2 NH 3 (g) 2 N 2 (g) 3 H 2 (g) is

(a) 46.0 kJ mol 1 (b) 92.0 kJ mol 1 (c) 23.0 kJ mol 1 (d) 92.0 kJ mol 1

14. The heat of combustion of benzene determined in a bomb calorimeter is 870 kcal mol 1 at 25 o C . The value
of E for the reaction is
(a) 1740 kcal (b) 870 kcal (c) 872 kcal (d) 874 kcal
15. The standard heats of formation in kcal mol 1 of NO 2 (g) and N 2 O4 (g) are 8.0 and 2.0 respectively. The heat
of dimerization of NO 2 in kcal is
2 NO 2 (g) N 2 O4 (g)

(a) 10.0 (b) 6.0 (c) 12.0 (d) 14.0

16. The difference between heats of reaction at constant pressure and at constant volume for the reaction
2C6 H 6 (l) 15 O2 (g) 12 CO 2 (g) 6 H 2 O(l) at 25 o C in kJ is

(a) 7.43 (b) + 3.72 (c) 3.72 (d) + 7.43

17. If the bond dissociation energies of XY , X 2 and Y2 (all diatomic molecules) are in the ratio of 1 : 1 : 0.5 and
f H for the formation of XY is 200 kJ mole 1 . The bond dissociation energy of X 2 will be

(a) 100 kJ mol 1 (b) 800 kJ mol 1 (c) 300 kJ mol 1 (d) 400 kJ mol 1
18. Energy required to dissociate 4 gm of gaseous hydrogen into free gaseous atoms is 208 kcal at 25 o C . The
bond energy of H H bond will be
(a) 104 kcal (b) 10.4 kcal (c) 1040 kcal (d) 104 cal
19. 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
20. 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
reaction Li(g) Cl(g) Li Cl is (if resulting ions do not combine with each other) (1 eV 1 .6 10 19 J )
(a) 70 (b) 100 (c) 170 (d) 270

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 THERMODYNAMICS
21. Given that C(g) 4 H(g) CH 4 (g); H 166 kJ
The bond energy C H will be
(a) 208 kJ/mole (b) 41.6 kJ/mole (c) 832 kJ/mole (d) None of these
22. The H H bond energy is 430 kJ mol and Cl Cl bond energy is 240 kJ mol 1 . H for HCl is 90 kJ . The
H Cl bond energy is about

(a) 180 kJ mol 1 (b) 360 kJ mol 1 (c) 213 kJ mol 1 (d) 425 kJ mol 1
23. If the bond energies of H H , Br Br and HBr are 433, 192 and 364 kJ mol 1 respectively, the H o for the
reaction, H2 (g) Br2 (g) 2HBr (g) is
(a) + 261 kJ (b) 103 kJ (c) 261 kJ (d) + 103 kJ
24. 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
25. The relation between E and H is
(a) H E P V (b) H E P V (c) E V H (d) E H P V
26. At constant T and P, which one of the following statements is correct for the reaction,
1
CO (g) O2 (g) CO 2 (g)
2
(a) H is independent of the physical state of the reactants of that compound
(b) H E (c) H E (d) H E

27. 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

28. The work done in ergs for the reversible expansion of one mole of an ideal gas from a volume of 10 litres to
20 litres at 25 o C is
(a) 2.303 298 0.082 log 2 (b) 298 10 7 8 . 31 2 . 303 log 2

(c) 2.303 298 0.082 log 0.5 (d) 8 .31 10 7 298 2 .303 log 0 .5

(e) 2.303 298 2 log 2

29. 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

30. 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.
31. In an adiabatic expansion of an ideal gas
(a) W E (b) W E (c) E 0 (d) W 0
32. For the reaction, CH 3 COOH (l) 2O2 (g) 2CO 2 (g) 2H 2 O(l) at 25 o C and 1 atm. pressure, H 874 kJ.
Then the change in internal energy (E ) is
(a) 874 kJ (b) 871.53 kJ (c) 876.47 kJ (d) + 874 kJ
33. 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 (c) E W 0, Q 0 (d) E Q 0, W 0
34. Hess law is based on

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 THERMODYNAMICS
(a) Law of conservation of mass (b) Law of conservation of energy
(c) Enthalpy is a state function (d) None of these
35. For the reaction, C3 H 8 (g) 5O2 (g) 3CO 2 (g) 4 H 2 O(l) at constant temperature, H E is
(a) RT (b) + RT (c) 3RT (d) + 3RT
36. 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
37. The value of H E for the following reaction at 27 C will be 2 NH 3 (g) N 2 (g) 3 H 2 (g)
o

(a) 8 . 314 273 (2) (b) 8 . 314 300 (2) (c) 8 . 314 27 (2) (d) 8 . 314 300 (2)

38. For which of the following E H

(a) N 2 O 4 (g) 2 NO 2 (g) (b) 2SO 2 (g) O2 (g) 2SO 3 (g)

H 2 (g) Cl 2 (g) 2 HCl (g) (d) H 2 (g) H 2 O(l)

1
(c) O 2 (g )
2
39. 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
40. 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
41. 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
42. 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
43. At 27 o 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. One mole of an ideal gas is allowed to expand reversibly and adibatically from a temperature of 27 o 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
45. An ideal gas expands in volume from 1 10 3 m 3 to 1 10 2 m 3 at 300 K against a constant pressure of
1 10 5 Nm 2 . The work done is

(a) 270 kJ (b) 900 kJ (c) 900 J (d) 900 kJ

3 3
46. The work done during the expansion of a gas from a volume of 4dm to 6dm against a constant external
pressure of 3atm is ( 1L atm 101 .32 J )
(a) + 304 J (b) 304 J (c) 6 J (d) 608 J
47. For the reaction, A(s) 2 B(g) 4 C(s) D(l) . H and U are related as
(a) H U (b) H U 3 RT (c) H U RT (d) H U 3 RT
ANSWER:
1. b 5. a 9. d 13. b
2. d 6. b 10. a 14. b
3. b 7. a 11. c 15. d
4. a 8. b 12. c 16. a

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 THERMODYNAMICS

17. b 25. b 33. c 41. c

18. a 26. c 34. b 42. d
19. c 27. c 35. c 43. a
20. c 28. b 36. b 44. b
21. b 29. c 37. d 45. c
22. d 30. c 38. c 46. d
23. b 31. b 39. c 47. d
24. b 32. a 40. a

SECTION IV
Second law of thermodynamics and Hess Law :
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.
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.

ds T q
1
rev

qrev
S
T
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
Hf
S f
Tf

Similarly, if the latent heat of vapourization and sublimation are denoted by Hvap and Hsub respectively. The
entropy of vapourization and sublimation are given by
Hvap
Svap
Tb

Hsub
Ssub
Ts

Since Hf , Hvap and Hsub are all positive, these processes are accompanied by increase in entropy.
As for an isothermal process, the change in entropy is
qrev
S
T
where qrev is the heat absorbed during the reversible path.
Since E = 0 in a reversible path, hence by first law of thermodynamics

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 THERMODYNAMICS
V2
qrev wrev 2.303nRTlog
V1

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

Entropy change for one mole of ideal gas

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

At constant temperature (isothermal process)

V2 P1
S Rln Rln
V1 P2
M2. Enthalpy change for the transition of liquid water to steam is 41 kJ mol1 at 100C. The entropy change for
the above process is
(a) 110 JK1 mol1 (b) 410 JK1 mol1 (c) 0.41 JK1 mol1 (d) 0.1099 JK1 mol1
41000
2. (a) S t = J K1 mol1 = 110 J K1 mol1
373
Numerical-Problem for Practice :
1. For a reversible spontaneous change S is
E P V q
(a) (b) (c) (d) RT log K
T T T
2. An irreversible process occuring isothermally in an isolated system leads to
(a) Zero entropy
(b) An increase in the total entropy of the syst
(c) A decrease in the total entropy of the system
(d) None of these
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
H 2(g) Cl 2(g) 2 HCl(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 2 2
(a) (b) T + (c) T (d) T
2 (2 / 3 ) 3 0 .0821 3 0 .0821

5. 9.0 gm of H 2 O is vaporised at 100 o C and 1 atm pressure. If the latent heat of vaporisation of water is
x J / gm , then S is given by

x 18 x 18 x 1 18 x
(a) (b) (c) (d)
373 100 373 2 373

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
1
(a) 88.3 J/mol K (b) (88 .3)2 J/mol K (c) 88.3 J/mol K (d) J/mol K
88 . 3

7. For which reaction from the following, S will be maximum

1
(a) Ca(s) O 2 (g) CaO (s) (b) CaCO 3 (s) CaO(s) CO 2 (g)
2

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 THERMODYNAMICS
(c) C(s) O2 (g) CO 2 (g) (d) N 2 (g) O2 (g) 2 NO(g)

8. The occurrence of a reaction is impossible if

(a) H is +ve ; S is also + ve but H TS
(b) H is ve ; S is also ve but H TS (c) H is ve ; S is + ve
(d) H is + ve ; S is ve
9. If the enthalpy of vaporization for water is 186.5 kJ mol 1 , the entropy of its vaporization will be
(a) 0 .5 JK 1 mol 1 (b) 1 .0 JK 1 mol 1 (c) 1 .5 JK 1 mol 1 (d) 2 .0 JK 1 mol 1
10. Which of the following statement is true. The entropy of the universe
(a) Increases and tends towards maximum value (b) Decreases and tends to be zero
(c) Remains constant (d) Decreases and increases with a periodic rate
11. When enthalpy and entropy change for a chemical reaction are 2 .5 10 3 cal and 7.4 cal deg 1 respectively.
Predict the reaction at 298 K is
(a) Spontaneous (b) Reversible (c) Irreversible (d) Non-spontaneous
12. The total entropy change for a system and its surroundings increases, if the process is
(a) Reversible (b) Irreversible (c) Exothermic (d) Endothermic
13. The enthalpy change for the transition of liquid water to steam, H vap 37 .3 kJ mol 1 at 373 K . The entropy
change for the process is
(a) 111 .9 J mol 1 K 1 (b) 37 .3 J mol 1 K 1 (c) 100 J mol 1 K 1 (d) 74 .6 J mol 1 K 1
14. The positive value of S indicates that
(a) The system becomes less disordered
(b) The system becomes more disordered
(c) The system is in equilibrium position
(d) The system tends to reach at equilibrium position
15. For reaction 2Cl(s) Cl 2 (s) , the signs of H and S respectively are
(a) +, (b) +, + (c) , (d) , +
16. The enthalpy of water is 386 kJ . What is entropy of water
(a) 0.5 kJ (b) 1.03 kJ (c) 1.5 kJ (d) 22.05 kJ
17. Identify the correct statement regarding entropy
(a) At 0o C , the entropy of a perfectly crystalline substance is taken to be zero
(b) At absolute zero of temperature, the entropy of a perfectly crystalline substance is ve
(c) At absolute zero of temperature, the entropy of all crystalline substances is taken to be zero
(d) At absolute zero of temperature, the entropy of a perfectly crystalline substance is taken to be zero
18. One mole of an ideal gas at 300 K is expanded isothermally from an initial volume of 1 litre to 10 litres. The
change in energy for this process is (R 2 cal mol 1 K 1 )
(a) 163.7 cal (b) 850.2 cal (c) 1381.1 cal (d) Zero
19. If 900 J / g of heat is exchanged at boiling point of water, then what is increase in entropy
(a) 43.4 J/mole (b) 87.2 J/mole (c) 900 J/mole (d) Zero
o
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
(a) 8.40 J (b) 9.34 J (c) 10.86 J (d) 10.43 J
21. In which of the following conditions a chemical reaction can not occur

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 THERMODYNAMICS
(a) H and S increase and TS H (b) H and S decrease and H TS
(c) H increases and S decreases (d) H decreases and S increases
22. An engine operating between 150 o C and 25 o C takes 500 J heat from a higher temperature reservoir if there
are no frictional losses, then work done by engine is
(a) 147.7 J (b) 157.75 J (c) 165.85 J (d) 169.95 J
23. The entropy of a perfectly crystalline solid at absolute zero is
(a) Positive (b) Negative (c) Zero (d) Not definite
24. Which of the following conditions will always lead to a non-spontaneous change
(a) Positive H and positive S (b) Negative H and negative S
(c) Positive H and negative S (d) Negative H and positive S
25. Following data is known about melting of a compound AB. H 9 .2 kJ mol 1 , S 0 .008 kJ K 1 mol 1 . Its
melting point is
(a) 736 K (b) 1050 K (c) 1150 K (d) 1150 o C

26. The volume of a gas decreases from 500 cc to 300 cc 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
(a) 2.16 J (b) 12.156 J (c) 2.16 J (d) 101.3 J
27. The standard entropies of CO 2 (g), C(s) and O 2 (g) are 213.5, 5.690 and 205 JK 1 respectively. The standard
entropy of formation of CO 2 (g) is
(a) 1 .86 JK 1 (b) 1 .96 JK 1 (c) 2 . 81 JK 1 (d) 2 .86 JK 1
28. One mole of an ideal gas is allowed to expand reversibly and adiabatically from a temperature of 27 o C . If the
work done during the process is 3 kJ, the final temperature will be equal to (C v 20 JK 1 )
(a) 150 K (b) 100 K (c) 26 . 85 o C (d) 295 K
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, H vap 2.257 kJ / g)
(a) 105.9 Jk 1 (b) 107 .9 Jk 1 (c) 108 .9 Jk 1 (d) 109 .9 Jk 1
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
[H vap 2.257 kJ / gm]

(a) 0.119 kJ (b) 0.109 kJ (c) 0.129 kJ (d) 0.120 kJ

1 1
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
(a) 6.6 K (b) 1.2 K (c) 2.4 K (d) 4.8 K
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
(a) + 590 joules (b) 334 joules (c) + 334 joules (d) 590 joules
33. H (aq) OH (aq) H 2 O(l)
S o (298 K ) K 1mol 1 10 .7 70

Standard entropy change for the above reaction is

(a) 60 .3 JK 1mol 1 (b) 80 . 7 JK 1mol 1 (c) 70 JK 1mol 1 (d) 10 .7 JK 1mol 1
34. One mole of water at 100 o C is converted into steam at 100 o C at a constant pressure of 1 atm. The change in
entropy is [heat of vaporisation of water at 100 o C 540 cal / gm ]
(a) 8.74 (b) 18.76 (c) 24.06 (d) 26.06

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 THERMODYNAMICS
35. The standard entropies of CO 2 (g), C(s) and O2 (g) are 213.5, 5.740 and 205 JK 1 respectively. The standard
entropy of formation of CO 2 is
(a) 2 .76 JK 1 (b) 2 . 12 JK 1 (c) 1 .12 JK 1 (d) 1 .40 JK 1

ANSWER:
1. c 10. a 19. a 28. a
2. b 11. a 20. b 29. c
3. d 12. d 21. c 30. b
4. d 13. c 22. a 31. c
5. d 14. b 23. c 32. c
6. c 15. c 24. c 33. b
7. b 16. b 25. c 34. d
8. d 17. d 26. c 35. a
9. a 18. d 27. c

SECTION V
Free-Energy :
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)
Gibbs free energy (G) is defined as
G H TS
For any Chemical Reaction :
G for a reaction under non-standard state conditions is G0 under standard state condition by relation

G Go 2.303RTlogQ
where Q is called reaction-quotient before equilibrium is attained
For a general reaction,
aA bB cC dD

Q
Cc Dd
A a Bb
When Q = 1, RTlog Q 0, G Go

When equilibrium is reached, G 0,Q K Kp or Kc

Go 2.303RTlogK
where K is called thermodynamic equilibrium constant.
EFFECT OF TEMPERATURE ON SPONTANEITY
H S G H TS Spontaneity of reaction

-ve (exothermic) Spontaneous at all temperature

Spontaneous at low temperature

+ Non-spontaneous at high temperature

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 THERMODYNAMICS
+ ve (endothermic) + Non-spontaneous at low temperature

Non-spontaneous at high temperature

Non-spontaneous at all temperature

H TS 0 Equilibrium
Example:10. For adsorption of a gas on solid adsorbent
(a) H is positive (b) S is positive (c) G is negative (d) E is positive
Solution : (c)
Example: 11. Consider the reaction:
2Cl(g) Cl2(g)
The sign of H and S of the above reaction respectively are
(a) + and (b) + and + (c) and (d) and +
Solution : (c) G = H TS
S is ve because when two atoms form a molecule then degree of randomness decreases is ve for the bond
formation.
Example : 12 Consider the following:
2Zn + O2 2ZnO; G = 616 J ..... (i)
2Zn + 2S 2ZnS; G = 293 J ..... (ii)
2S + 2O2 2SO2(g); G = 408 J ..... (iii)
G for the following reaction 2ZnS + 3O2 2ZnO + 2SO2 would be
(a) 731 J (b) 1317 J (c) + 731 J (d) + 1317 J

Solution : (a) G = 2G ZnO 2GSO

2G ZnS = [ 616 408] [ 293] = 731 J.
2

Example : 13 A chemical reaction can not occur at all if its

(a) H value is positive and S value is negative
(b) H value is negative and S value is positive
(c) H and S value are negative but H > TS
(d) H and S value are positive but H > TS
Solution: (a) G is always positive if H is positive and S is negative. Thus, the reaction is
nonspontaneous.
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.
S r hombic
S monoclinic

If H = 276.144 J at 298 K and 1 atm and G = 75.312 J

(a) Calculate S at 298 K
(b) Assume that H and S do not vary significantly with temperature, calculate Teq., the temperature at which
rhombic and monoclinic sulphur exist in equilibrium with each other.
Solution:
(a) Since G H TS
H G
S
T

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 THERMODYNAMICS
276.144 75.312

298
= 0.674 JK-1
(b) Under equilibrium condition G 0
H Teq S 0

H 276.144
Teq
S 0.674
= 409.7 K
Example : 15 Assume Ho and So to be independent of temperature, at what temperature will the reaction given
below become spontaneous ?
N2 g O2 g
2NO g
o 1 1
S / JK mol 191.4 204.9 210.5
Ho = 180.8 kJ mol 1
Solution :
So 2SNO
o
SNo 2 SoO2 2 210.5 191.4 204.9

= 24.7 JK 1 mol 1
Go Ho TSo
G o 180.8 T 24.7 103 kJ mol 1 for spontaneity, Go 0 and this occurs when

TSo Ho
Ho
T
So
180.8 103
T 7320 K
24.7
The reaction becomes spontaneous above a temperature of 7320 K.
Example: 16 Calculate the standard entropy change for a reaction X Y , if the value of Ho 28.40 kJ and
equilibrium constant is 1.8 107 at 298 K.
Solution:
We know that Go 2.303RTlog K
2.303 8.314 298 log1.8 107
= 38.498 kJmol.
Also, Go Ho TSo
Ho Go 28.40 38.498
So 0.0338 kJmol1K1 = 33.8 JK -1mol-1
T 298
1
Example:17 Calculate the temperature, at which the reaction given below is at equilibrium, Ag 2 O s
O2 g
2
Given, H 30.5 kJmol1 and S 0.066 kJK1mol1 .
Solution:
G H TS
At equilibrium, G = 0
H = TS

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 THERMODYNAMICS
H 30.5
T 462.12 K
S 0.066

Numerical-Problem for Practice:

1. The free energy change for a reversible reaction at equilibrium is
(a) Large positive (b) Small negative (c) Small positive (d) 0
2. For a spontaneous change, free energy change G is
(a) Positive (b) Negative
(c) Zero (d) Can be positive or negative
3. The relation between G and H is not
(a) H G T S (b) G H T S (c) T S G H (d) H T G S
4. At 300 K, the reactions which have following values of thermodynamic parameters occur spontaneously
(a) G o 400 kJ mol 1 (b) H o 200 kJ mol 1 , S o 4 JK 1 mol 1

(c) H o 200 kJ mol 1 , S o 4 JK 1 mol 1 (d) H o 200 J mol 1 , S o 40 JK 1 mol 1

5. What is the free energy change G when 1.0 mole of water at 100 o C and 1 atm pressure is converted into
steam at 100 o C and 1 atm pressure
(a) 540 cal (b) 9800 cal (c) 9800 cal (d) 0 cal

6. G o for the reaction X Y Z is 4.606 kcal . The value of equilibrium constant of the reaction at 227 o C
is (R 2 .0 cal. mol 1 K 1 )
(a) 100 (b) 10 (c) 2 (d) 0.01
7. The standard enthalpy of the decomposition of N 2 O4 to NO 2 is 58.04 kJ and standard entropy of this
reaction is 176.7 J/K. The standard free energy change for this reaction at 25 o C is
(a) 539 kJ (b) 539 kJ (c) 5.39 kJ (d) 5.39 kJ
8. For a reaction at 25 o C enthalpy change and entropy changes are 11 .7 10 3 J mol 1 and 105 J mol 1 K 1
respectively. What is the Gibbs free energy
(a) 15.05 kJ (b) 19.59 kJ (c) 2.55 kJ (d) 22.55 kJ
9. The correct relationship between free energy change in a reaction and the corresponding equilibrium constant
K c is

(a) G RT ln Kc (b) G RT ln Kc (c) G o RT ln K c (d) G o RT ln Kc

5
10. The free energy change for the following reactions are given below, C 2 H 2 (g ) O 2 (g )
2
2CO 2 (g) H 2O(l); G o 1234 kJ

1
C(s) O 2 (g) CO 2 (g) G o 394 kJ , H 2 (g) O 2 (g) H 2 O(l) G o 237 kJ
2

What is the standard free energy change for the reaction H 2 (g) 2 C (s) C2 H 2 (g)
(a) 209 kJ (b) 2259 kJ (c) + 2259 kJ (d) 209 kJ
11. The equilibrium concentration of the species in the reaction A B C D are 3, 5, 10 and 15 mole L1
respectively at 300 K 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 300 K . The
enthalpy change (in kJ ) for the process is:
(a) 11.4 kJ (b) 11.4 kJ (c) 0 kJ (d) 4.8 Kj

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 THERMODYNAMICS
13. Heat of neutralization of strong acid against strong base is constant and is equal to
(a) 13.7 kcal (b) 57 kJ (c) 5.7 10 4 J (d) All of the above
14. To calculate the amount of work done in joules during reversible isothermal expansion of an ideal gas, the
volume must be expressed in
(a) m3 only (b) dm 3 only (c) cm 3 only (d) Any one of them
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 0.31 kJ . The value of E will be

(a) 0.3024 kJ (b) 0.3024 kJ (c) 2.567 kJ (d) 0.0076 kJ

1
16. For a reaction H 9 .08 kJ mol and
S 35 .7 JK 1 mol 1

Which of the following statements is correct for the reaction

(a) Reversible and Isothermal (b) Reversible and Exothermic
(c) Spontaneous and Endothermic (d) Spontaneous and Exothermic
17. The enthalpies of formation of Al 2 O3 and Cr2 O3 are 1596 kJ and 1134 kJ respectively. H for the reaction
2 Al Cr2 O3 2Cr Al 2 O3 is [KCET 2003]

(a) 2730 kJ (b) 462 kJ (c) 1365 kJ (d) 2730 kJ

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
(a) 28 kJ (b) 19 kJ (c) 10 kJ (d) 9 kJ
19. The enthalpy of neutralization of HCN by NaOH is 12 .13 kJ mol 1 . The enthalpy of ionisation of HCN will
be
(a) 4.519 kJ (b) 45.10 kJ (c) 451.9 kJ (d) 45.19 kJ

20. C(graphite) O2 (g) CO 2 (g)

H 94 .05 kcal mol 1

C (diamond) O 2 (g) CO 2 (g); H 94 .50 kcal mol 1

therefore
1 1
(a) C(graphite) C(diamond) ; H 298
o
K 450 cal mol (b) C(diamond) C(graphite) ; H 298
o
K 450 cal mol

(c) Graphite is the stabler allotrope (d) Diamond is harder than graphite
21. The equilibrium constant of a reaction at 298 K is 5 10 3 and at 1000 K is 2 10 5 . What is the sign of H
for the reaction
(a) H 0 (b) H is negative (c) H is positive (d) None of these
22. Consider the reactions
C(s) 2 H 2 (g) CH 4 (g), H x kcal

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

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

The bond energy of C H bond is

(a) y kcal mol 1 (b) x 1 kcal mol 1 (c) x / 4 kcal mol 1 (d) x 1 / 4 kcal mol 1
23. Given the bond energies N N, H H and N H bonds are 945 , 436 and 391 kJ mole 1 respectively, the
enthalpy of the following reaction N 2 (g) 3 H 2 (g) 2 NH 3 (g) is

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 THERMODYNAMICS
(a) 93 kJ (b) 102 kJ (c) 90 kJ (d) 105 kJ
24. Which of the following is not a correct statement ?
(a) When G is negative, the process is spontaneous
(b) When G is zero, the process is in a state of equilibrium
(c) When G is positive, the process is non-spontaneous
(d) None of these
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 1 , the value of enthalpy change for the reaction H 2 C CH 2 (g) H 2 (g) H 3 C CH 3 (g) at 298 K will be
(a) + 250 kJ (b) 250 kJ (c) + 125 kJ (d) 125 kJ
26. The H 2 O(g) molecule dissociates as
(i) H 2 O(g) H(g) OH(g); H 490 kJ (ii) OH(g) H(g) O(g); H 424 kJ
The average bond energy (in kJ) for water is
(a) 490 (b) 424 (c) 914 (d) 914/2
27. For the reaction
1
H 2 (g ) O 2 (g) H 2 O(l), H 285 . 8 kJ mol 1 S 0 .163 kJ mol 1 K 1 . What is the value of free energy change
2
at 27 o C for the reaction
(a) 236 .9 kJ mol 1 (b) 281 .4 kJ mol 1 (c) 334 . 7 kJ mol 1 (d) 334 .7 kJ mol 1
28. If H is the enthalpy change and E the change in internal energy accompanying a gaseous reaction then
(a) H is always less than E . (b) H is always greater than E .
(c) H is less than E if the number of moles of gaseous products is greater than the number of moles of
gaseous reactants.
(d) H is less than E if the number of moles of gaseous products is less than the 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)
(a) y 2x (b) 2x (c) (d) 2x y
2 2
31. 5 mole of an ideal gas expand reversibly from a volume of 8 dm3 to 80 dm3 at a temperature of 27C.
Calculate the change in entropy.
(a) 70.26 JK1 (b) 82.55 JK1 (c) 95.73 JK1 (d) 107.11 JK1-
32. The spontaneous nature of reaction is impossible if
(a) H is + ve, S is also + ve (b) H is + ve, S is ve
(c) H is ve, S is + ve (d) H is + ve, S is ve
33. An ideal gas undergoing expansion in vacuum shows
(a) E =0 (b) W = 0 (c) q = 0 (d) All of the above
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
(a) 40 J (b) 60 J (c) 80 J (d) 50 J

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35. Molar heat capacity for a gas at constant temperature and pressure is
(a) 3/2R (b) 5/2R
(c) depends on atomicity of gas (d) infinity ()
36. The work done in an open vessel at 300 K, when 112 g iron reacts with dil. HCl is
(a) 1200 cal (b) 600 cal (c) 300 cal (d) 200 cal
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
(a) 7.43 (b) +3.72 (c) 3.72 (d) 7.43
38. One mole of an ideal gas expand spontaneously into a vacuum. The work done is
(a) 2 J (b) 4 J (c) zero (d) infinity
ANSWERS
1. d 11. b 21. b 31. c
2. b 12. c 22. a 32. b
3. b 13. d 23. a 33. d
4. b 14. d 24. d 34. a
5. d 15. a 25. d 35. c
6. a 16. c 26. d 36. a
7. d 17. b 27. a 37. a
8. b 18. c 28. d 38. c
9. d 19. d 29. c
10. d 20. c 30. c

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