Chapter

5
Thermodynamics

2023

T1/ 1 2022
2019 T1: Fundamentals of Thermodynamics and its
Applications, First Law of Thermodynamics

T2/ 1 T2: Hess's Law and Enthalpy of Reaction

T1/ 1
T1/ 1
T3: Second Law of Thermodynamics and
Entropy

T4: Gibbs Free Energy (G), Spontaneity and

T1/ 1 Equilibrium Constant
T1/ 1
T3/ 1 2021
T2/ 1

2020

Easy Average Difficult

First and Second Law of

Thermodynamics and 4/5 8.1
Hess's Law
Thermodynamic processes pV-plot when pressure is not pV-plot when pressure is not
constant and changes in finite constant and changes in infinite
steps (reversible conditions)
130

steps during compression from

initial volume, Vi to final volume, during compression from initial
Isochoric dV = 0, Adiabatic Vf . Work done on the gas is volume, Vi to final volume, Vf .
dQ = 0, Isothermal dT = 0, represented by the shaded area. Work done on the gas is
Isobaric dP = 0, represented by the shaded area.
Cyclic Process dE = 0, dH = 0 p
p

Hess's Law
Vf Volume (V) Vi Determination of enthalpy
Vf Volume (V) Vi of reaction
E=q+w
rH = rH1 + rH2 + .........

Heat Capacity Heat capacity at

Entropy
THERMODYNAMICS const. volume (CV)
CV
qrev
Measure of disorder or randomness
Heat capacity at
For reversible process SSYS + SSURR = 0 Spontaneity Heat const. pressure (CP)
For irrersible process SSYS + SSURR > 0 U
CP
Standard free energy System to surrounding
q = – ve Cp – Cv = R
Surrounding to system
= – 2.303RT log K q = + ve
Intensive properties
Independent on the
quantity e.g.,
temperature, pressure,
specific heat
Macrascopic properties
of the system Extensive properties
depends on quantity
of substance e.g.,
mass, internal energy,
volume, enthalpy, heat
Chemistry

capacity etc.
 Thermodynamics 131

Fundamentals of Thermodynamics and its Applications, First Law of

TOPIC 5.1 Thermodynamics

It is a branch of physical chemistry which deals with the study

of thermal changes accompanying a physical or chemical
transformation. According to law of conservation of energy

MASS
“Total energy of the system and its surroundings remains
constant, although it can be transformed from one form to the
other.”
FUNDAMENTALS OF THERMODYNAMICS AND
ITS APPLICATIONS HEAT HEAT

System and Surroundings

The part of the universe chosen for thermodynamic study
is called system. It is separated from the rest of the universe
by a real or imaginary boundary. The remaining portion of State of a System and State Variables
the universe excluding the system is called surroundings. The state of a system is determined by its observable
properties. The system in which the values of observable
Types of system : properties are definite is said to be in definite state. The
Isolated system : A system that cannot exchange mass state of a system is specified by state functions or state
and/or energy with the surroundings. For example : variables. Variables like P, V, T are called state variables or
Milk kept in a thermos flask. state functions because their values depend only on the
state of the system and not on how it is reached.
NEET 2008

State Functions
The properties of a system which depend only on initial
MASS and final states and not on its path. For example : free energy,
enthalpy, internal energy, etc.
HEAT

Macroscopic Properties
The properties which are associated with large number of
chemical entities e.g., pressure, temperature, density,
Closed system : It exchanges only energy with the composition, viscosity, surface tension, colour, refractive
surroundings. index, etc.
For example : Extensive properties : The properties which depend
Water in a closed bottle (boundaries of closed on the amount of substance present in the system.
system act as conductor of heat). For example: mass, volume, heat capacity, entropy,
Heating of CaCO3 in sealed tube, etc. enthalpy, free energy, internal energy, etc.
Intensive properties : The properties which are
independent of the amount of substance present in
the system. For example : temperature, density,
viscosity, melting point, boiling point, surface tension,
refractive index, pressure, etc.
MASS
Thermodynamic Processes
The process in which the state of a system gets changed
HEAT HEAT from one state to the another state. These are of the
following types :
Isothermal process : It is the process in which
Open system : It exchanges both energy and mass temperature of the system remains constant. In this
from the surroundings. For example : trees in forest, process, the boundaries of the system are mobile. The
tea in an open cup, etc. energy released in the exothermic process is absorbed
by the surroundings and if the process is endothermic
 132 Chemistry

the system takes the required energy from the Internal energy of one mole of a monoatomic gas at ‘T’
surroundings, therefore the temperature remains 3
constant. Thus, the change in temperature, dT = 0 Kelvin is RT. The internal energy of ideal gases is a
2
Maximum work done in expansion of n moles of an function of temperature only.
ideal gas :
Heat and Work
V P
Wmax = –2.303 nRT log 2 = –2.303 nRT log 1
V1 P2
where, V1 = Initial volume of the gas Heat absorbed by the system (+ q) = positive
V2 = Final volume of the gas Heat released by the system (– q) = negative
P1 = Initial pressure of the gas Work done by the system on the surroundings (–W)
= negative.
P2 = Final pressure of the gas
Work done on the system by the surroundings (+W)
Adiabatic process : The process occurs without
= positive
transfer of heat or mass of substances between a
system and its surroundings. In this, energy is In SI unit, work is expressed in Joule
transferred to surrounding only as work change in 1J = 107 erg = 1 Nm = 1 kgm2s–2
heat (dQ) = 0
Expression for PV Work
Isobaric process: This process takes place at constant
pressure. Change in pressure (dP) = 0. All kinds of PV work is expressed as :
For example : vapourisation of water, heating of W= –P V
water up to its boiling point at same atmospheric The above expression satisfies the sign conventions.
pressure. For expansion, V or (V2–V1) = +ve and W = –ve
Isochoric process: The process which takes place at For compression, V or (V2–V1) = – ve and W = +ve
constant volume. Change in volume, (dV) = 0.
PV Curve
Cyclic process: The process in which a system
proceeds via many intermediate steps and returns to Differene in the work done in reversible expansion and
the initial state. Change in internal energy (dE) = 0, irreversible expansion.
change in enthalpy (dH)=0
A
Reversible process: This process is slow and unreal.
Its direction can be changed at any step and during Isothermal
reversible
process of every stage, system remains in equilibrium expansion
Pext
with surroundings. (Area = ABV 1V 2)
Irreversible process: This process is fast and gets C
completed in a single step. This process cannot B
Pressure

be reversed. All the natural processes are of this Isothermal

type. irreversible
expansion
Internal Energy (U) (Area = BC = V1V2)

The fixed amount of energy stored in a substance is called its

internal energy. Internal energy is present in all the substances.
V1 V2
Internal energy is a state function and depends on the Volume
physical state of the system and is independent of path by
NEET 2022
which state has been attained.
Absolute value of internal energy cannot be determined. Reversible expansion: The external pressure is
Only change in internal energy ( U) can be determined. infinitesimally less than the internal pressure at each
stage. Wrev = Pint × dV
U = Energy in final state – Energy in initial state.
U = U2 – U1 Vf Vf

Internal energy is an extensive property. In most Wrev Pex dV (Pint dp) dV

stable form, internal energy of an element is regarded Vi Vi
as zero. Wrev = Pint × dV
 Thermodynamics 133

Irreversible expansion: Internal pressure is much When a gas expands against a constant pressure, P, then
different from external pressure. Wirr –Pext V (i) Work done by the system = –P V, ( V = V2 – V1)
U=q –P V
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(ii) If a gas expands in vacuum, the work done, W = 0,
The area under the isotherm AB i.e., area ABV1V2 because Pext = 0.
represent the work done reversibly.
The area under the isotherm BC i.e. area BCV1V2 Work Done During Expansion/Compression
represent work done irreversibly. Work done in isothermal reversible expansion
W rev. Wirr. (maximum work)
V P
Reversible work of expansion (Wrev.) is the Wmax 2.303nRT log 2 2.303nRT log 1
maximum work. V1 P2
For isothermal irreversible change
Reversible work of compression is the minimum
q = – W = Pex(V2 – V1)
work.
If an ideal gas expands against vaccum, the Work done in adiabatic reversible expansion:
irreversible expansion is called free expansion. W nCv (T2 T1 )
As Pext = 0, therefore for reversible as well as
Heat Content or Enthalpy, H
irreversible expansion, work done = 0. NEET 2020
The total heat content of a system at constant pressure is
FIRST LAW OF THERMODYNAMICS known as its enthalpy.
According to this law, energy can neither be created nor At constant temperature and pressure,
destroyed, it can only be changed from one form to the other H= U+ P V
i.e.,total energy of an isolated system remains constant. Total U = Change in internal energy
energy of universe remains constant. Whenever some amount
P V = W = Work done
of any form of energy disappears, the same amount of energy is
produced in other form. P = External pressure
Mathematical Form Most of the chemical reactions occur at constant pressure
If energy is absorbed by a system (+q) and work is done (1 atmosphere) and in an open vessel . Thus the measured
on the system (+W), internal energy of the system value of heat evolved or absorbed is the enthalpy change
increases. If U1 is initial value of internal energy and U2 is (qp = H)
the final,
then, U2 = U1 + q + W NEET 2017
U2 – U1 = q + W
or, U=q+ W When V = 0 , H = U
This is the mathematical form of 1st law of thermodynamics For liquids and solids, V = 0, therefore, W = 0
H= U
For gaseous state, PV = nRT; P V = nRT
H = U + ( n) RT NEET 2021
For isothermal process : n=0 H= U
Energy change in system = heat given to system + work n = –ve H < U
done on system n = +ve H > U
U = 0 as temperature is constant
H = –ve, (reaction is exothermic)
0 = q + W or q = –W
H = +ve, (reaction is endothermic)
For isochoric process :
W = 0 (System does not do any work) Enthalpy of a system depends on physical state (solid,
liquid and gas).
U = qv + 0,
Therefore, heat given to system at constant volume changes H is a state function. Therefore, it depends only on initial
internal energy. and final states. Absolute value of enthalpy cannot be
determined
For adiabatic process :
q = 0; Change in enthalpy of the products and reactants at 298 K
and 1 atmospheric pressure is called standard molar
U = 0 + W or U = W i.e., work done on system equals to
enthalpy change.
the change in internal energy NEET 2017
 134 Chemistry

Example 1
For the reaction

C3 H8 (g) 5O 2 (g) 3CO 2 (g) 4H 2O(l) dE E

Heat capacity at constant volume C v
at constant temperature, H – U is dt T v
(a) – RT (b) + RT dq dH H
Heat capacity at constant pressure C p
(c) – 3 RT (d) + 3 RT dt dt T p
Sol. (c) H E nRT Also C p c p M and C v cv M
n = 3 – (1 + 5) = 3 – 6 = –3
where cP and cv are specific heats at constant pressure and
H E ( 3RT )
constant volume respectively. CP and Cv are molar heat capacities
Relationship between H and Heat at constant pressure and constant volume respectively.
At constant pressure
H= U+ P V
According to first law of thermodynamics Molar Heat Capacity of a Monoatomic Gas at
U = q + W and W = –P V Constant Volume :
U=q –P V 3
Cv R
2
Substituting the value of U in Molar Heat Capacity of a Monoatomic Gas
H= U+ P V at Constant Pressure :
H= q– P V+ P V 5
Cp R
2
H= q Molar Heat Capacity for Polyatomic Gas at
Heat Capacity of a System Constant Volume :
3
It is the amount of heat required to raise the temperature of Cv R X
the system by 1 degree (K or °C) 2
Molar Heat Capacity for Polyatomic Gas at
q Constant Pressure :
C .
m(T2 T1 ) 5
Cp R X
In case of single substance, when m=1 g, C is the specific 2
For monoatomic gas X = 0, for diatomic gas X=R and for
heat of system; when m = M or 1 mole, it is molar heat
3
capacity. Since heat capacity varies with temperature, its triatomic gas X R
true value is given by 2
Relation Between CP and CV for an Ideal Gas
dq CP – CV = R (For 1 mole of an ideal gas) NEET 2021
C (differential equation);
dt CP – CV = nR (For n moles of gas)

Classroom Discussion Questions

1. One mole of a non-ideal gas undergoes a change of state 3. Identify the correct statements from the following.
from (1.0 atm, 3.0 L, 200 K) to (4.0 atm, 5.0 L, 250 K) with a (i) For adiabatic process, U = W adiabatic
change in internal energy ( U) = 40 L-atm. The change in
(ii) Work is a path function.
enthalpy of the process in L–atm :
(a) 43 (b) 57 (iii) Volume is an extensive property.
(c) 42 (d) None of these (a) i, ii, iii (b) i, iii only
2. The difference between the reaction enthalpy change ( rH) (c) ii, iii only (d) i, ii only
and reaction internal energy change ( rU) for the reaction: 4. Two moles of an ideal gas is expanded isothermally and
2C6H6 (l) + 15O2 (g) 12CO2 (g) + 6H2O (l) reversibly from 1 litre to 10 litre at 300 K. The enthalpy
–1
at 300 K is (R = 8.314 J mol K ) –1 change (in kJ) for the process is
(a) 0 J mol–1 (b) 2490 J mol–1 (a) 11.4 kJ (b) – 11.4 kJ
(c) – 2490 J mol –1 (d) –7482 J mol–1 (c) 0 kJ (d) 4.8 kJ
 Thermodynamics 135

TOPIC 5.2 Hess's Law and Enthalpy of Reaction

HESS’S LAW OF CONSTANT HEAT SUMMATION Relation between qp and qv :

According to this law when a chemical reaction gets H = U + P V or H = U + nRT
completed directly in one step or indirectly in two or more where n = n2 – n1
steps, the total enthalpy change in the reaction remains n2 and n1 are the number of moles of gaseous products and
same. i.e., the enthalpy change does not depend on the gaseous reactants respectively.
path of a chemical reaction.” Thus when, n = 0, i.e., when there is no change in the
A q2 B number of gaseous moles, then
q1 q3 H= U
Reactant, R Product, P Types of Enthalpy of Reaction
Enthalpy of combustion : Amount of Enthalpy released on
Q total combustion of 1 mole substance at constant
Q q1 q 2 q3 temperature (change in total heat) is called Enthalpy of
combustion. Its value is always negative. AIPMT 2015
Example – Combustion of carbon
Combustion of hydrocarbon,
Method 1 :
CH4(g) + 2O2(g) CO2(g) + 2H2O(l),
C(s) + O2(g) –––– CO2(g) + 94 kcal
H = –94 kcal cH = –210.8 kcal/mol
(at 25º C and 1 atmospheric pressure)
Method 2 :
CS2(l) + 2O2(g) CO2(g) + 2 SO2(g)
1 CH3SH(g) + 3O2(g) CO2(g) + 2H2O(l) + SO2(g)
C(s) + O2(g) –––– CO(g) + 26.4 kcal .......... (i)
2 Enthalpy of solution : One mole of a substance is
1 dissolved in such excess amount of water that no heat
CO(g) + O (g) –––– CO2(g) + 67.6 kcal ......... (ii) change takes place on further dilution. In this process, total
2 2
heat change is called Enthalpy of solution.
On summing up equations (i) and (ii),
KCl(s) + H2O(l) –––– KCl (aq.) –4.4 kcal
H = –94 kcal
For KCl, solH = 4.4 kcal (Absorption)
Example 2 Enthalpy of dilution : Difference of two integral heats is
An imaginary reaction X Y takes place in three steps called Enthalpy of dilution.
Enthalpy of hydration : The amount of Enthalpy released
X A, H q ;B A, H q ; on complete hydration of one mole of an anhydrous
1 2
substance is called Enthalpy of hydration.
B Y, H q
3 ZnSO4(s) + 5H2O(l) –––– ZnSO4. 5H2O(s)
If Hess' law is applicable, then the heat of the reaction (X Y) H = –30.0 kJ
is : BaCl2(s) + 2H2O (l) –––– BaCl2. 2H2O(s)
(a) q1 – q2 + q3 (b) q2–q3–q1 hydH = –30.0 kJ
(c) q1–q2–q3 (d) q3–q2–q1 Enthalpy of sublimation : The amount of enthalpy required
Sol. (b) X A + q1 to change one mole of a solid substance into vapour state
q2 + A B is called enthalpy of sublimation
B Y + q3 I2(s) I2(g) subH = +62.07 kJ/mol
q2 + X Y + q1 + q3, H = q2 – q1 – q3 Enthalpy of fusion : The amount of enthalpy required to
completely change one mole of a solid substance into liquid
ENTHALPY OF REACTION at its melting point is called enthalpy of fusion
It is the amount of enthalpy evolved or absorbed when the H2O(s) –––– H2O( ) fusH = 6.0 kJ
number of moles of reactants in the balanced equation are Enthalpy of vapourisation : The amount of enthalpy required
completely reacted. to completely change one mole of a liquid into its vapours
At constant pressure : at its boiling point is called enthalpy of vapourisation
H2O(l) –––– H2O(g) vapH = +44 k cal
H = HP(Product) – HR(Reactant) NEET 2020, 2018
Enthalpy of formation: It is the change of enthalpy during
At constant volume : the formation of 1 mole of the substance from its constituent
U = Up(Product) – UR(Reactant) elements in their most stable states of aggregation with all
Standard Enthalpy of Reaction substances in their standard states. NEET 2013
Change in total Enthalpy ( H) of reaction at 25 °C is called C (Graphite) + O2(g) ––– CO2(g) f H = –94.3 kcal
standard Enthalpy of reaction. It is represented by H° or (Exothermic)
H at 298 K. This is also the heat of combustion of graphite.
 136 Chemistry

Exothermic
Na+ (g) + Cl (g)
1
H2(g) + O2(g) –––– H2O (l) ;

121 kJ mol–1

348.6 kJ mol–1
2
1/2 bond H
1 1 H
H2(g) + Cl2(g) –––– HCl (g) EA

2 2
C(Graphite) + 2S(s) –––– CS2(l) Na+ (g) + 1/2 Cl2(g)
S(Orthorhombic) + O2(g) –––– SO2 (g)

+ 496 kJ mol–1
Na+ (g) + Cl– (g)
C(Graphite) + 2H2(g) –––– CH4(g) H
i
1 3
N2(g) + H2(g) –––– NH3(g)
2 2
Endothermic Na (g) + 1/2 Cl2(g)

+ 108.4 kJ mol–1
1 1
H2(g) + I2(g) –––– HI(g)
2 2
sub H
1 1 lattice H
N2(g) + O2(g) –––– NO(g)
2 2
Na (s) + 1/2 Cl2(g)
2C(g) + 2H2(g) –––– C2H4(g)

–411.2 kJ mol –1
Enthalpy of atomization: When one mole of a given
substance dissociate into gaseous atoms, the enthalpy f H
change accompanying the process is called enthalpy of
atomization. For example,
H2(g) 2H(g) °
aH = 435.0 KJ/mol NaCl (s)
Bond energy: bond energy is the amount of energy
released when one mole of bonds are formed from the Born Haber cycle of NaCl
isolated atoms in the gaseous state. Let us now calculate the lattice energy of NaCl(s) by
Or following steps given below:
The amount of energy required to dissociate one mole of Na(s) Na(g), sublimation of sodium metal,
–1
bonds present between the atoms in th e gaseous subH = 108.4 kJ mol
+ –
Na(g) Na (g) + e , the ionization of sodium atoms,
molecules.
For diatomic molecules like H2,N2,O2 etc., the bond energies ionization energy
–1
are equal to their dissociation energies. These may also i H = 496 kJ mol
called as their enthalpy of atomisation. 1
Cl2 (g) Cl(g), the dissociation of chlorine, the
For polyatomic molecules, the bond energy of a particular 2
bond is not same when present in different type of reaction energy is half the bond dissociation energy.
compounds. 1
bond H 121 kJ mol 1
rH = bond energies of the reactants – bond energies 2
of the products NEET 2020 Ph II, 2018 Cl(g) + 1e– Cl– ; EAH– = –348.6 kJ mol–1
Electron affinity (EA) is the energy released, so H is
Lattice Energy of a Crystal negative
The lattice energy of an ionic compound is the energy Thus, according to Hess's law;
change which occurs when one mole of an ionic compound 1
dissociates into its ions in gaseous state. fH = subH + iH + 2 bondH + EAH + latticeH
NaCl(s) Na+(g) + Cl–(g); –411.2 kJ = 108.4 kJ + 496 kJ + 121kJ – 348.6 kJ + latticeH
–1
H = +788 kJ mol–1 lattice H = –788 kJ mol
lattice
The amount of heat released when requisite amount of
ions in the gaseous state combine to give one mole of
crystal lattice.
Na+(g) + Cl–(g) NaCl(s); H– = –788 kJ mol–1 According to Kirchoff’s equation, heat of reaction at constant
Since it is impossible to determine crystal lattice energy pressure at temperature T1 = H1
directly by experiment, we use an indirect method where Heat of reaction at constant pressure at temperature T2 = H2
we construct an enthalpy diagram called a Born-Haber At constant pressure, H2 – H1 = CP (T2 – T1)
Cycle. At constant volume, E2 – E1 = Cv (T2 – T1)
 Thermodynamics 137

Classroom Discussion Questions

5. Hess's law states that : (b) the dissociation energy of hydrogen molecule, H2.
(a) the standard enthalpy of an overall reaction is the (c) the dissociation energy of H2 and enthalpy of
sum of the enthalpy changes in individual reactions. sublimation of carbon.
(b) enthalpy of formation of a compound is same as the (d) latent heat of vapourization of methane.
enthalpy of decomposition of the compound into 7. Calculate the standard enthalpy change (in kJ mol–1) for
constituent elements, but with opposite sign.
the reaction H2(g) + O2(g) H2O2(g), given that bond
(c) at constant temperature the pressure of a gas is enthalpy of H–H, O=O, O–H and O–O (in kJ mol–1) are
inversely proportional to its volume.
respectively 438, 498, 464 and 138.
(d) the mass of a gas dissolved per litre of a solvent is
(a) – 130 (b) – 65 (c) + 130 (d) – 334
proportional to the pressure of the gas in equilbrium
with the solution. 8. The values of heat of formation of SO2 and SO3 are
6. The standard enthalpy of formation ( fHº) at 298 K for –298.2kJ and –98.2 kJ. The heat of formation of the reaction
methane, CH4(g) is –74.8 kJ mol –1. The additional SO 2 (1 / 2)O 2 SO 3 will be
information required to determine the average energy for (a) –200 kJ (b) –356.2 kJ
C – H bond formation would be
(c) + 200 kJ (d) – 396.2 kJ
(a) the first four ionization energies of carbon and electron
gain enthalpy of hydrogen.

TOPIC 5.3 Second Law of Thermodynamics and Entropy

SECOND LAW OF THERMODYNAMICS When a solute gets dissolved in the solvent, the entropy
According to Clausius – “transfer of heat from a cold body increases.
to a hot body is not possible without doing some work.” When the number of gaseous products increases in a
Entropy of a system increases in every spontaneous process chemical reaction, the entropy also increases. For example,
or entropy of universe increases in every spontaneous (NH4)2S(s) –––– 2NH3(g) + H2S(g)
process. Entropy decreases when gases react to form liquids or solids.
The first law deals with the conservation of energy whereas For example,
the second law tells the direction of flow of energy. NH3(g) + HCl(g) –––– NH4Cl(s),
For a reversible process, For a reaction, change in entropy S = Total entropy of the
dq products – Total entropy of the reactants.
dS = or dq = T dS
T Unit of entropy is JK–1mol–1
For an irreversible process, At equilibrium, for a reversible process, S = 0
dq dq
dS > dS >
T T
This is the mathematical statement of the second law
of thermodynamics.
ENTROPY, (S) Entropy Change for an Ideal Gas Under Different
Conditions: With Change in P, V and T
It is a thermodynamic property and is a measure of disorder
or randomness of a system, i.e., greater the disorder in a T2 V2
S C V ln R ln (when T and V are two variables)
system, higher is the entropy of that system. T1 V1
Solid < Liquid < Gas T2 P1
Entropy is a state function. It does not depend on path S C P ln R ln (when T and P are two variables)
T1 P2
q(reversible)
S S2 S1 V2 P1
T For isothermal process ( T 0), S R ln R ln
V1 P2
q = amount of heat (at temperature T) absorbed by the
system in a reversible way. T2
For isobaric process ( P 0), S C P ln
Entropy change, S = S(Final state) – S(Initial state) T1
S = + ve if entropy of system increases
T2
S = – ve if entropy of system decreases For isochoric process ( V 0), S CV ln
T1
 138 Chemistry

Spontaneous Processes (a) 88.3 J/mol K (b) (88.3)2 J/mol K

A reaction that occurs under the given set of conditions is
1
called a spontaneous reaction. (c) – 88.3 J/mol K (d) J/mol K
If a reaction does not occur under specified conditions, it 88.3
Sol. (c) For reverse reaction signs will be changed.
is said to be non-spontaneous.
A process which has an urge or a natural tendency to For a spontaneous process in an isolated system, the
occur either of its own or after proper initiation under the change in entropy is positive, i.e., S > 0.
given set of conditions is known as spontaneous process. However, if a system is not isolated, the entropy changes
Spontaneous processes where no initiation is of both the system and surroundings are to be taken into
required account because system and surroundings together
Dissolution of sugar or salt in water constitute the isolated system. Thus, the total entropy
Sugar + water Aqueous solution of sugar change ( Stotal) is sum of the change in entropy of the
Salt+ water Aqueous solution of salt system ( S sys) and the change in entropy of the
surroundings ( Ssurr), i.e.,
Evaporation of water from water reservoirs such
as ponds, lakes, rivers, sea, open vessels, etc. Stotal = Ssys + Ssurr
H2O (l) H2O (g) For a spontaneous process, Stotal must be positive, i.e.,
Spontaneous processes where initiation is required Stotal = Ssys + Ssurr > 0
Reaction between H2 and O2: This reaction is Stotal is also termed as Suniverse
initiated by passing electric spark through the During a spontaneous process, the entropy of the system
mixture. goes on increasing till the system attains the equilibrium
state, i.e., entropy of the system becomes maximum and
Electric
2H 2 (g) O 2 (g) spark
2H 2 O (l) therefore, no more increase in the entropy of the system is
possible. The mathematical condition for equilibrium is,
Coal burns in oxygen or air when ignited. Coal
keeps on burning once initiated. S = 0 (at equilibrium for an isolated system)
Ignition
C(s) O 2 (g) CO2 (g)

More disorder More Entropy Spontaneous Process

Total Entropy = Entropy of the System + Entropy of Surroundings

Entropy changes during phase transition : In phase transition
process,
q (reversible) H
S = S2 – S1 = =
T T Always or

H(fusion) Cyclic Process

S(fusion) =
T If a system returns to its original state after undergoing a number
Where, H(fusion) = Latent heat of fusion of solid of successive changes; it is said to be a cyclic process. The
T = Melting point of solid in Kelvin most common example of such a process is that of carnot cycle.
(I) Isothermal expansion
H(vapourisation)
S (vapourisation) = (II) Adiabatic expansion
T (III) Isothermal compression
where, H (vapourisation) = Latent heat of vapourisation (IV) Adiabatic compression
T = Boiling point of liquid in Kelvin
A (V1)
H(sublimation)
S (sublimation) =
T I
H (sublimation) = Enthalpy of sublimation
IV B (V2)
T = Temperature in Kelvin.
Pressure

Example 3 II
(V4) D
The S for the vaporisation of 1 mol of water is
III
88.3 J/mol K. The value of S for the condensation of 1 mol of C (V3)
vapour will be Volume
 Thermodynamics 139

Classroom Discussion Questions

9. Predict which of the following reaction(s) has a negative (b) Ssystem Ssurroundings 0
entropy change?
(c) Ssystem 0 only
I. CH 4 (g) 2O 2 (g) CO 2 (g) 2H 2O (l)
(d) Ssurroundings 0 only
II. NH 3 (g) HCl(g) NH 4 Cl(g) 11. Which of the following one mole has the highest entropy?
(a) Mercury (b) Diamond
III. 2KClO4 (s) 2KClO3 (s) O 2 (g) (c) Liquid nitrogen (d) Hydrogen gas
(a) III (b) II 12. The process with negative entropy change is:
(c) I and II (d) I (a) Dissociation of CaSO4(s) to CaO(s) and SO3(g)
10. Considering entropy (S) as a thermodynamic parameter, (b) Sublimation of dry ice
the criterion for the spontaneity of any process is (c) Dissolution of iodine in water
(a) Ssystem Ssurroundings 0 (d) Synthesis of ammonia from N2 and H2

TOPIC 5.4 Gibbs Free Energy (G), Spontaneity and Equilibrium Constant

GIBBS FREE ENERGY (G), SPONTANEITY AND Criteria of Feasibility or Spontaneity in Terms of
EQUILIBRIUM CONSTANT
Entropy : S sys S surr 0 or S total 0
The available amount of energy to the system during the
process which can be used to do work, is called free energy Stotal = 0, the process is reversible and system is in
of the system. equilibrium when internal energy and volume are kept
Thus, free energy change in the system ( G), is the measure constant
of the capability of doing useful work by the system ( S)U,V > 0 the process is irreversible and if ( S)U,V = 0, the
G = H – TS [Gibbs-Helmoholtz equation] process is reversible.
G = H – T S NEET 2021, 2020, 2019 Internal energy : When entropy and volume kept constant.
If ( U)S,V < 0, the process is irreversible and if ( U)S,V = 0,
If G = Negative, then the reaction is spontaneous in
the process is reversible.
forward direction NEET 2016
Enthalpy (H) : When entropy and pressure are kept
G = 0, at equilibrium
constant.
G = Positive, then the reaction is non-spontaneous in
If ( H)S,P < 0, the process is irreversible and if ( H)S,P = 0,
forward direction.
the process is reversible.
The standard free energy change ( G°) is related to
Free energy (G) : When pressure and temperature are kept
equilibrium constant K as
constant
G° = – RT ln K
If ( G)P, T < 0,the process is irreversible and if ( G)P, T = 0,
G° = – 2.303 RT log K the process is reversible.
Following table shows under which conditions, G becomes
negative and thus process is spontaneous. Example 4
At the sublimation temperature, for the process
S H H–T S) Remark CO2(s) CO2(g)
G (a) H, S and G are all positive
High – spontaneous (b) H > 0, S > 0 and G < 0
+ + Low + non-spontaneous (c) H < 0, S > 0 and G < 0
– – High + non-spontaneous
(d) H > 0, S > 0 and G = 0
– – Low – spontaneous
– any Sol. (d) Since the process is at equilibrium G = 0 for G 0,
+ + non-spontaneous
– any – they should be H > 0, S > 0.
spontaneous
 140 Chemistry

Classroom Discussion Questions

13. The free energy change G = 0, when (a) 910 K (b) 1110 K
(a) the system is at equilibrium (c) 510 K (d) 710 K
(b) catalyst is added 15. The correct relationship between free energy and
(c) reactants are initially mixed thoroughly equilibrium constant K of a reaction is
(d) the reactants are completely consumed (a) G RT ln K (b) G RT ln K
14. The values of H and S for the reaction, C(graphite) +
CO2(g) 2CO(g) are 170 kJ/mol and 170 Jk–1mol–1, (c) G RT ln K (d) G RT ln K
respectively. This reaction will be spontaneous at

Example 1 Example 4
A mixture of two moles of carbon monoxide and one mole of For the reaction :
oxygen, in a closed vessel is ignited to convert the carbon H2(g) + Cl2(g) 2HCl(g), H at 298K = –44.12 kcal
monoxide to carbon dioxide. If H is the enthalpy change At 298 K, the enthalpy of formation of HCl will be
and E is the change in internal energy, then
(a) –44.12 (b) –22.06
(a) H > E (b) H < E
(c) +44.12 (d) –10.06
(c) H = E (d) the relationship depends
on the capacity of the vessel Sol. (b) Enthalpy of HCl will be half of –44.12 kcal. So its value
Sol. (b) H = E + ngRT is
2CO(g) + O2 (g) 2CO2 (g) –22.06 kcal.
ng = 2 – 3 = – 1; H = E – RT; E > H. Example 5
Example 2 Consider the following data
What will be the entropy change accompanying the heating H2O(s) H2O (l), H = 6.05 kJ
of one mole of He gas, assuming ideal from a temperature H2O (l) H2O(g), H = 43.7 kJ
of 298 K to a temperature of 1000 K at constant pressure. At 273 K, the sublimation energy of H2O(s) H2O(g) will
(Assume, Cv = 3/2R). be
(a) 25.17 (b) 20.25 (a) 56.75 (b) 75.20
(c) 19.25 (d) 2.50 (c) 49.75 (d) 100.20
Sol. (a) For an ideal gas, Cp – Cv = R Sol. (c) H2O(s) H2O (l), H = 6.05 kJ ...(i)
3 H2O (l) H2O(g), H = 43.7 kJ ...(ii)
Cp = Cv + R R R 2.5R
2 By adding eq. (i) and (ii) we get
At constant pressure, S = Cpln (T2/T1) H2O(s) H2O(g), H = 49.75 kJ
S = (2.5 × 8.314) ln (1000/298) = 25.17 J K–1 mol–1
Example 6
Example 3
The sublimation energy of I2(s) is 57.3 kJ/mol and the
The direct conversion of A to B is difficult, hence it is carried
out by the following shown path enthalpy of fusion is 15.5 kJ/mol. The enthalpy of
vaporisation of I2 is
C D
(a) 41.8 kJ/mol (b) – 41.8 kJ/mol
A B (c) 72.8 kJ/mol (d) – 72.8 kJ/mol
Given, S(A C) 50 eu Sol. (a) According to Hess's law, total heat changes during a
S(C D) 30 eu chemical reaction are independent of path of reaction.
Given,
S(B D) 20 eu
I2 (s) I2 (g), H1 = + 57.3 kJ mol–1 ...(i)
Where eu is entropy unit, then S(A B) is –1
I2 (s) I2 (l), H2 = + 15.5 kJ mol ...(ii)
(a) + 100 eu (b) + 60 eu
Required Eq. I2 (l) I2 (g), H = ?
(c) – 100 eu (d) – 60 eu
I2 (l) I2 (g),
Sol. (b) SA B S(A C) S(C D) S(D B) H = 57.3 – 15.5 = + 41.8 kJ mol–1
S(A C) S(C D) S(B D)
= 50 + 30 – 20 = 60 eu
 Thermodynamics 141

Exercise 1 Home Assignment (NCERT Based MCQs)

Fundamentals of Thermodynamics and its Applications, First Law of

TOPIC 5.1 Thermodynamics

1. Which of the following statements is not true regarding 8. According to the first law of thermodynamics which of the
the laws of thermodynamics ? NCERT Page-160 / N-136 following quantities represents change in a state function?
(a) It deals with energy changes of macroscopic systems. NCERT Page-164 / N-140

(b) It deals with energy changes of microscopic systems. (a) qrev (b) qrev – Wrev
(c) It does not depends on the rate at which these energy (c) qrev/Wrev (d) qrev + Wrev
transformations are carried out. 9. Statement I : Internal energy, U, of the system is a state
(d) It depends on initial and final states of a system function.
undergoing the change. Statement II : –w shows, that work is done on the system.
2. Which of the following is closed system? (a) Both statement I and II are correct.
(b) Both statement I and II are incorrect.
(a) Jet engine NCERT Page-161 / N-137
(c) Statement I is correct but statement II is incorrect.
(b) Tea placed in a steel kettle
(d) Statement II is correct but statement I is incorrect.
(c) Pressure cooker
10. Figure below is showing that one mole of an ideal gas is
(d) Rocket engine during propulsion fitted with a frictionless piston. Total volume of the gas is
3. The state of a thermodynamic system is described by its Vi and pressure of the gas inside is p. If external pressure is
measurable or macroscopic (bulk) properties. These are Pex which is greater than p, is applied, piston is moved
(a) Pressure and volume NCERT Page-162 / N-138 inward till the pressure inside becomes equal to Pex.
(b) Pressure, volume, temperature and amount NCERT Page-164 / N-40
(c) Volume, temperature and amount
(d) Pressure and temperature
Pex
4. Enthalpy change ( H) of a system depends upon its
Pressure, P

(a) Initial state NCERT Page-167 / N-143

(b) Final state Area = Pex V
(c) Both on initial and final state
(d) None of these
5. Which of the following factors affect the internal energy Vf Vi Volume, V
of the system ? NCERT Page-162 / N-138
Pex
(a) Heat passes into or out of the system.
(b) Work is done on or by the system.
(c) Matter enters or leaves the system.
(d) All of the above Pex
6. Adiabatic expansions of an ideal gas is accompanied by
(a) decrease in E NCERT Page-164 / N-140
(b) increase in temperature l
(c) decrease in S
(d) no change in any one of the above properties What does the shaded area represents in the figure ?
(a) Work done (b) Pressure change
7. Among the following, the state function(s) is (are)
(c) Volume change (d) Temperature change
(i) Internal energy NCERT Page-162 / N-138
11. When 1 mol of a gas is heated at constant volume,
(ii) Irreversible expansion work temperature is raised from 298 to 308 K. If heat supplied to
(iii) Reversible expansion work the gas is 500 J, then which statement is correct ?
(iv) Molar enthalpy NCERT Page-164 / N-140
(a) (ii) and (iii) (b) (i), (ii) and (iii) (a) q = w = 500 J, U = 0 (b) q = U = 500 J, w = 0
(c) (i) and (iv) (d) (i) only (c) q = –w = 500 J, U = 0 (d) U = 0, q = w = –500 J
 142 Chemistry

12. Which of the following statements/relationships is not (a) A – (p), B – (s), C – (r), D – (q)
correct in thermodynamic changes ? (b) A – (p), B – (q), C – (r), D – (s)
NCERT Page-166 / N-142 (c) A – (p), B – (r), C – (s), D – (q)
(a) U = (isothermal reversible expansion of a gas) (d) A – (p), B – (r), C – (q), D – (s)
V2 17. For the reaction NCERT Page-167 / N-143
(b) w = – nRT ln (isothermal reversible expansion of
V1 C3 H8 (g) 5O2 (g) 3CO2 (g) 4H 2 O(l)
an ideal gas) at constant temperature, H – E is
V2 (a) – RT (b) + RT (c) – 3 RT (d) + 3 RT
(c) w = nRT ln (isothermal reversible expansion of 18. Which is an extensive property of the system ?
V1
NCERT Page-168 / N-144
an ideal gas)
(a) Volume (b) Viscosity
(d) For a system of constant volume, heat involved
directly changes to internal energy. (c) Temperature (d) Refractive index
13. An ideal gas expands in volume from 1×10–3 to 1 × 10–2 m3 19. If H is the change in enthalpy and E, the change in
at 300 K against a constant pressure of 1×105 Nm–2. The internal energy accompanying a gaseous reaction, then
work done is NCERT Page-165 / N-141 (a) H is always greater than E NCERT Page-167 / N-143
(a) 270 kJ (b) – 900 kJ (b) H < E only if the number of moles of the products
(c) – 900 J (d) 900 kJ is greater than the number of moles of the reactants
14. The difference between H and U is usually significant (c) H is always less than E
for systems consisting of NCERT Page-167 / N-143 (d) H < E only if the number of moles of products is
less than the number of moles of the reactants
(a) only solids (b) only liquids
20. Calorie is equivalent to :
(c) both solids and liquids (d) only gases
(a) 0.4184 Joule (b) 4.184 Joule
15. Match Column-I with Column-II
(c) 41.84 Joule (d) 418.4 Joule
Column-I Column-II
21. Equal volumes of two monoatomic gases, A and B, at same
(A) Reversible isothermal (p) w = –2.303 nRT
temperature and pressure are mixed. The ratio of specific
V2 heats (Cp/Cv) of the mixture will be :
expansion of an ideal gas log
V1 NCERT Page-169 / N-145
(a) 0.83 (b) 1.50 (c) 3.3 (d) 1.67
(B) Reversible adiabatic (q) PV = constant
22. If a reaction involves only solids and liquids which of the
compression of an
following is true ? NCERT Page-167 / N-143
ideal gas
(a) H< E (b) H = E
nR (c) H> E (d) H = E + RT n
(C) Irreversible adiabatic (r) w= (T2 – T1 )
( –1) 23. During isothermal expansion of an ideal gas, its
compression of an (a) internal energy increases NCERT Page-166 / N-142

ideal gas (b) enthalpy decreases

(D) Irreversible isothermal (s) H = 0 (c) enthalpy remains unaffected
compression of an ideal gas (d) enthalpy reduces to zero.
(a) A – (p); B – (q); C – (r); D – (s) 24. Consider the reaction : N 2 3H 2 2 NH 3 carried out
(b) A – (p, s); B – (q, r); C – (r); D – (s) at constant temperature and pressure. If H and U are
(c) A – (s); B – (r); C – (p); D – (q) the enthalpy and internal energy changes for the reaction,
(d) A – (q); B – (p); C – (r); D – (s) which of the following expressions is true ?
16. Match Column-I with Column-II. NCERT Page-167 / N-143
Column-I Column-II (a) H> U (b) H < U
(A) pext = 0 (p) Free expansion of an (c) H= U (d) H = 0
ideal gas 25. Among the following, the intensive properties are
(B) q = pext (Vf – Vi) (q) Adiabatic change NCERT Page-168 / N-144
(C) q = 2.303 nRT log (Vf / Vi) (r) Isothermal reversible (i) molar conductivity (ii) electromotive force
change (iii) resistance (iv) heat capacity
(D) U = Wad (s) Isothermal irreversible (a) (i) and (ii) (b) (i), (ii) and (iii)
change (c) (i) and (iv) (d) (i) only
 Thermodynamics 143

26. Which of the following factors do not affect heat capacity? 34. According to the first law of thermodynamics, U = q + W.
(a) Size of system NCERT Page-168 / N-144 In special cases the statement can be expressed in different
ways. Which of the following is not a correct expression ?
(b) Composition of system
NCERT Page-164 / N-140
(c) Nature of system
(a) At constant temperature q = –W
(d) Temperature of the system
(b) When no work is done U = q
27. Which of the following relation is not correct?
(c) In gaseous system U = q + P V
(a) H= U– P V (b) U= q+ W
(d) When work is done by the system : U = q + W
(c) Ssys = Ssurr 0 (d) G= H– T S 35. Assume each reaction is carried out in an open container.
28. The internal energy change when a system goes from state For which reaction will H = E ? NCERT Page-167 / N-143
A to B is 40 kJ/mol. If the system goes from A to B by a (a) C(s) + 2H2O (g) 2H2 (g) + CO2 (g)
reversible path and returns to state A by an irreversible (b) PCl5 (g) PCl3 (g) + Cl2 (g)
path, what would be the net change in internal energy ? (c) 2CO (g) + O2 (g) 2CO2 (g)
(a) > 40 kJ (b) < 40 kJ (c) Zero (d) 40 kJ (d) H2 (g) + Br 2 (g) 2 HBr (g)
29. Under isothermal condition for one mole of ideal gas what 1
36. For the reaction CO (g ) O 2 (g ) CO 2 (g )
is the ratio of work done under reversible to irreversible 2
process, initially held at 20 atm undergoes expansion from Which one of the statement is correct at constant T and P?
1L to 2L, at 298K, under external pressure of 10 atm?
NCERT Page-167 / N-143
NCERT Page-166 / N-142
(a) H E
(a) 1.7 (b) 2.0 (c) 1.4 (d) 1.0
(b) H E
30. Five moles of an ideal gas at 1 bar and 298 K is expanded
into vacuum to double the volume. The work done is : (c) H E
NCERT Page-166 / N-141 H is independent of physical state of the reactants
(d)
(a) CV(T2 – T1) (b) –RT (V2 – V1)
37. 17.0 g of NH3 completely vapourises at – 33.42 °C and 1
(c) –RT ln V2/V1 (d) zero bar pressure and the enthalpy change in the process is
31. How many molecules of ATP, undergo hydrolysis to raise 23.4 kJ mol–1. The enthalpy change for the vapourisation
the temperature of 180 kg of water which was originally at of 85 g of NH3 under the same conditions is
room temperature by 1°C ? C{P,m} water = 75.32 J/mol/K, (a) 111 kJ (b) 117 kJ
H{P} for ATP hydrolysis= 7 kcal/mol (c) 115 kJ (d) 123 kJ
NCERT Page-168 / N-145 38. A system does 200 J of work and at the same time absorbs
150 J of heat. The magnitude of the change in internal energy is
(a) 1.5 × 1025 (b) 2.00 × 1023
(a) 20 J (b) 50 J (c) 30 J (d) 40 J
(c) 3.4 × 1025 (d) 4.0 × 1024
39. Five moles of an ideal gas at 1 bar and 298 K is expanded
32. What is the amount of heat (in Joules) absorbed by 18 g into vacuum to double the volume. The work done is :
of water initially at room temperature heated to 100°C ? If
NCERT Page-168 / N-144
10 g of Cu is added to this water , than decrease in
(a) CV(T2 – T1) (b) –RT (V2 – V1)
temperature (in Kelvin) of water was found to be? C (p,m)
(c) –RT ln V2/V1 (d) zero
for water 75.32 J/mol K ; C (p,m) for Cu = 24.47 J/mol K.
40. An ideal gas is allowed to expand from 1 L to 10 L against
NCERT Page-169 / N-145 a constant external pressure of 1 bar. The work done in kJ
(a) 5649, 369 (b) 5544, 324 is : NCERT Page-166 / N-142
(c) 5278, 342 (d) 3425, 425 (a) – 9.0 (b) + 10.0
33. The molar heat capacity of water at constant pressure is (c) – 0.9 (d) – 2.0
75 JK–1 mol–1. When 1kJ of heat is supplied to 100 g of 41. During compression of a spring the work done is 10 kJ
water, which is free to expand, the increase in temperature and 2 kJ escaped to the surroundings as heat. The change
of water is NCERT Page-169 / N-145
in internal energy, U (in kJ) is: NCERT Page-166 / N-142

(a) 6.6 K (b) 1.2 K (c) 2.4 K (d) 4.8 K (a) –12 (b) –8
(c) 8 (d) 12
 144 Chemistry

TOPIC 5.2 Hess's Law and Enthalpy of Reaction

42. At 25°C and 1 atm pressure, the enthalpy of combustion of (b) The enthalpy of atomization is same as the enthalpy
benzene (1) and acetylene (g) are –3268 kJ mol–1 and of sublimation.
–1300 kJ mol–1, respectively. The change in enthalpy for (c) The enthalpy of atomization is same as the bond
the reaction 3 C2H2(g) C6H6(l), is enthalpy
NCERT Page-178 / N-154 (d) The enthalpy of atomization is same as the enthalpy
(a) + 324 kJ mol–1 (b) + 632 kJ mol–1 of solution
(c) – 632 kJ mol –1 (d) – 732 kJ mol–1 48. Diborane is a potential rocket fuel which undergoes
43. What is the internal energy (kJ) change occurs when 36 g combustion according to the equation
of H2O(l) at 100°C converted to H2O(g)? NCERT Page-176 / N-152
H° (vapourisation) = 40.79kJ/mol NCERT Page-172 / N-143
B2 H 6 (g) 3O 2 (s) B2 O 3 (s) 3H 2O(g)
(a) (b)
(c) (d) Calculate the enthalpy change for the combustion of
diborane. Given
44. Consider the reaction :
3
4NO2 (g) O2 (g) 2N 2O5 (g), (i) 2B(s) O 2 (g) B2 O3 (s); H = –1273 kJ per mol
2
rH = – 111kJ.
If N2O5(s) is formed instead of N2O5(g) in the above 1
(ii) H 2 (g) O 2 (g) H 2O(l); H = –286 kJ per mol
reaction, the rH value will be : 2
(given, H of sublimation for N2O5 is –54 kJ mol–1) (iii) H 2 O(l) H 2 O(g); H = 44 kJ per mol
(a) + 54 kJ (b) + 219 kJ
(iv) 2B (s) + 3H2 (g) B2H6 (g); H = 36 kJ per mol
(c) – 219 J (d) – 165 kJ
(a) + 2035 kJ per mol (b) – 2035 kJ per mol
45. Standard enthalpy of vapourisation vap H° for water at
100°C is 40.66 kJ mol–1. The change in internal energy of (c) + 2167 kJ per mol (d) – 2167 kJ per mol
vaporisation of water at 100°C (in kJ mol–1) is : 49. Which of the following is not true regarding thermo-
chemical equations?
NCERT Page-172 / N-143
(a) The coefficients in a balanced thermo-chemical
(a) + 37.56 (b) – 43.76
equation refer to the number of moles of reactants
(c) + 43.76 (d) + 40.66 and products involved in the reaction
(Assume water vapour to behave like an ideal gas). (b) The coefficients in a balanced thermo-chemical
46. Consider the following reactions: NCERT Page-173 / N-149 equation refer to the number of molecules of reactants
(i) H +(aq) + OH–(aq) = H2O(l), and products involved in the reaction
H = – X1 kJ mol–1 (c) The numerical value of r H refers to the number of
1 moles of substances specified by an equation.
(ii) H2(g) + O (g) = H2O(l),
2 2 (d) Standard enthalpy change rH will have units as
H = – X2 kJ mol–1 kJ mol-1.
(iii) CO2(g) + H2(g) = CO(g) + H2O(l) 50. If enthalpies of formation of C 2 H 4 (g) , CO2(g) and
H = – X3 kJ mol–1 H 2 O(l) at 25°C and 1atm pressure are 52, – 394 and
5 – 286 kJ/mol respectively, the change in enthalpy for
(iv) C2 H 2 (g) O2 (g) = 2CO2(g) + H2O(l)’
2 combustion of C2H4 is equal to NCERT Page-176 / N-154
H = + 4X4 kJ mol–1 (a) – 141.2 kJ/mol (b) – 1412 kJ/mol
Enthalpy of formation of H2O (l) is (c) + 14.2 kJ/mol (d) + 1412 kJ/mol
(a) + X3 kJ mol– 1 (b) – X4 kJ mol– 1 51. The following two reactions are known :
(c) + X1 kJ mol – 1 (d) – X2 kJ mol– 1 Fe2O3(s) + 3CO (g) 2Fe(s) + 3CO2(g); H = –26.8 kJ
47. Which of the following statements is true for the given FeO(s) + CO(g) Fe(s) + CO2(g); H = –16.5 kJ
reaction? NCERT Page-177 / N-153 The value of H for the following reaction
–1
Na s Na g ; H 108.4 kJ mol Fe2O3(s) + CO(g) 2FeO(s) + CO2(g) is;
(a) The enthalpy of atomization is same as the enthalpy (a) + 6.2 kJ (b) + 10.3 kJ
of vaporisation (c) – 43.3 kJ (d) – 10.3 kJ
 Thermodynamics 145

52. Hess’s law is used to calculate : NCERT Page-175 / N-151 Enthalpy for the reaction,
(a) enthalpy of reaction
(b) entropy of reaction H H H H
| | | |
(c) work done in reaction C C H H H C C H
(d) All of the above | | | |
53. Given that bond energies of H – H and Cl – Cl are H H H H
430 kJ mol– 1 and 240 kJ mol–1 respectively and Hf for HCl
is – 90 kJ mol– 1, bond enthalpy of HCl is will be: NCERT Page-176 / N-154
(a) – 243.6 kJ mol –1
NCERT Page-177 / N-154
(b) –120.0 kJ mol–1
(a) 380 kJ mol–1 (b) 425 kJ mol–1
–1 (c) 553.0 kJ mol–1
(c) 245 kJ mol (d) 290 kJ mol–1
(d) 1523.6 kJ mol–1
54. From the following bond energies: NCERT Page-178 / N-156 55. If the standard molar enthalpy change for combustion of
H – H bond energy: 431.37 kJ mol–1 graphite powder is –2.48 × 102 kJ mol–1, the amount of heat
C = C bond energy: 606.10 kJ mol–1 generated on combustion of 1 g of graphite powder is
C – C bond energy: 336.49 kJ mol–1 (a) 26 kJ (b) 21 kJ
C – H bond energy: 410.50 kJ mol–1 (c) 23 kJ (d) 24 kJ

TOPIC 5.3 Second Law of Thermodynamics and Entropy

56. In which of the following, entropy decreases? 59. Unit of entropy is NCERT Page-182 / N-159
NCERT Page-182, 183 / N-158, 159 (a) JK–1 mol–1 (b) J mol–1
(a) Crystallization of sucrose solution (c) J–1 K–1 mol–1 (d) JK mol–1
(b) Rusting of iron 60. Considering entropy (S) as a thermodynamic parameter,
(c) Melting of ice the criterion for the spontaneity of any process is
(d) Vaporization of camphor NCERT Page-183 / N-159
57. Choose the reaction with negative S value. (a) Ssystem Ssurroundings 0
(a) 2NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(g)
(b) Ssystem Ssurroundings 0
(b) Cl2(g) 2Cl(g)
(c) 2SO2(g) + O2(g) 2SO3(g) (c) Ssystem 0 only
(d) 2KClO3(s) 2KCl(s) + 3O2(g) (d) Ssurroundings 0 only
58. For the gas phase reaction, 61. A reaction is spontaneous at low temperature but non-
PCl5(g) PCl3(g) + Cl2(g) spontaneous at high temperature. Which of the following
which of the following conditions are correct ? is true for the reaction? NCERT Page-183 / N-160
(a) H = 0 and S < 0 (b) H > 0 and S > 0 (a) H > 0, S > 0 (b) H < 0, S > 0
(c) H < 0 and S < 0 (d) H > 0 and S < 0 (c) H > 0, S = 0 (d) H < 0, S < 0

TOPIC 5.4 Gibbs Free Energy (G), Spontaneity and Equilibrium Constant

62. At the sublimation temperature, for the process 64. A reaction with H = 0, is found to be spontaneous. This
CO2(s) CO2(g) NCERT Page-186 / N-162 is due to NCERT Page-183 / N-160

(a) H, S and G are all positive (a) S is negative (b) S is positive

(b) H > 0, S > 0 and G < 0 (c) T S is positive (d) Both (b) and (c)
(c) H < 0, S > 0 and G < 0 65. Match Column-I with Column-II.
Column-I Column-II
(d) H > 0, S > 0 and G = 0
(A) H = –ve ; S = –ve (p) Reaction will be
63. What is the equilibrium constant if ATP hydrolysis by
G = –ve non-spontaneous at
water produces standard free energy of –50 kJ/mol under
high temperature
normal body conditions ? NCERT Page-185 / N-162 (B) H = –ve ; S = –ve (q) Reaction will be
(a) 2.66 × 108 (b) 5.81 × 108 G = +ve non-spontaneous at
(c) 1.18 × 107 (d) 1.98 × 108 low temperature
 146 Chemistry

(C) H = +ve ; S = +ve (r) Reaction will be 68. Identify the correct statement for change of Gibbs energy
G = +ve spontaneous at low for a system ( Gsystem) at constant temperature and
temperature pressure NCERT Page-186 / N-161
(D) H = +ve ; S = +ve (s) Reaction will be (a) If Gsystem = 0, the system has attained equilibrium
G = –ve spontaneous at high (b) If Gsystem = 0, the system is still moving in a particular
temperature direction
(a) A – (q), B – (r), C – (p), D – (s) (c) If Gsystem < 0, the process is not spontaneous
(b) A – (r), B – (p), C – (q), D – (s) (d) If Gsystem > 0, the process is not spontaneous
(c) A – (r), B – (q), C – (s), D – (p) 69. In an irreversible process taking place at constant T and P
(d) A – (q), B – (s), C – (p), D – (r) and in which only pressure-volume work is being done,
66. For th e reaction 2NO 2(g) N 2O 4 (g), when the change in Gibbs free energy (dG) and change in entropy
S = –176.0 JK–1 and H = –57.8 kJ mol–1, the magnitude (dS), satisfy the criteria
of G at 298 K for the reaction is_____ kJ mol –1. (a) (dS)V, E > 0, (dG)T, P < 0 (b) (dS)V, E = 0, (dG)T, P = 0
(Nearest integer) NCERT Page-184 / N-160 (c) (dS)V, E = 0, (dG)T, P > 0 (d) (dS)V, E < 0, (dG)T, P < 0
(a) 2 (b) –5 (c) 8 (d) 10 70. A process has H = 200 J mol–1 and S = 40 JK–1mol–1.
67. A reaction occurs spontaneously if NCERT Page-186 / N-162 Out of the values given below, choose the minimum
temperature above which the process will be spontaneous:
(a) T S < H and both H and S are + ve
(b) T S > H and H is + ve and S is ve NCERT Page-187 / N-162

(c) T S > H and both H and S are + ve (a) 20 K (b) 12 K (c) 5 K (d) 4 K
(d) T S = H and both H and S are + ve

Exercise 2 NEET Past Year MCQs

1. Which amongst the following options is the correct 4. For irreversible expansion of an ideal gas under isothermal
relation between change in enthalpy and change in condition, the correct option is: 20 21
internal energy? NCERT Page-167 / N-143 | 2023 (a) U 0, Stotal = 0 (b) U = 0, Stotal = 0
(a) H = U – ngRT (b) H = U + ngRT (c) U 0, Stotal 0 (d) U = 0, Stotal 0
(c) H – U = – nRT (d) H + U = nR 5. The correct option for free expansion of an ideal gas under
2. Which of the following p-V curve represents maximum adiabatic condition is NCERT Page-166 / N-142 | 2020

work done? NCERT Page-165 / N-141 | 2022 (a) q = 0, T < 0 and w > 0
(b) q < 0, T = 0 and w = 0
(c) q > 0, T > 0 and w > 0
Isothermal
p (d) q = 0, T = 0 and w = 0
p Isothermal
6. At standard conditions, if the change in the enthalpy for the
(a) (b) following reaction is –109 kJ mol–1.
H2(g) + Br2(g) 2HBr(g)
V V Given that bond energy of H2 and Br2 is 435 kJ mol–1 and 192
kJ mol –1 , respectively, what is the bond energy
(in kJ mol–1) of HBr? NCERT Page-177 / N-154 | Ph-II 2020
(a) 259 (b) 368 (c) 736 (d) 518
p Isothermal p Isothermal
7. For the reaction, 2Cl(g) Cl2(g), the correct option is :
(c) (d) 2020
(a) rH > 0 and rS < 0
(b) rH < 0 and rS > 0
V V (c) rH < 0 and rS < 0 (d) rH > 0 and rS > 0
3. Which one among the following is the correct option for 8. An ideal gas expands isothermally from 10–3 m3 to 10–2 m3 at
right relationship between CP and CV for one mole of ideal 300 K against a constant pressure of 105 Nm–2. The work
gas? NCERT Page-169 / N-145 | 2021 done on the gas is NCERT Page-165 / N-142 | Odisha 2019
(a) CV = RCP (b) CP + CV = R (a) –900 kJ (b) +270 kJ
(c) CP – CV = R (d) CP = RCV (c) –900 J (d) +900 kJ
 Thermodynamics 147

9. Reversible expansion of an ideal gas under isothermal and 14. For a given reaction, H = 35.5 kJ mol-1 and S = 83.6
adiabatic conditions are as shown in the figure. JK–1 mol–1. The reaction is spontaneous at: (Assume that
Odisha 2019 H and S do not vary with temperature)
NCERT Page-186 / N-160 | 2017
A(PA VA TA)
(a) T > 425 K (b) All temperatures
P B(PB VB TB) (c) T > 298 K (d) T < 425 K
C(PC VC TC) 15. Consider the following liquid - vapour equilibrium.
V 2016
Which of the following relations is correct ?
AB Isothermal expansion
AC Adiabatic expansion dlnG Hv dlnP Hv
(a) 2 (b)
Which of the following options is not correct? dT RT 2 dT RT
(a) TC > TA
(b) Sisothermal > Sadiabatic dlnP Hv dlnP Hv
(c) 2 2 (d)
(c) TA = TB dT T dT RT 2
(d) Wisothermal > Wadiabatic 16. The correct thermodynamic conditions for the
10. Under isothermal condition, a gas at 300 K expands front spontaneous reaction at all tempertures is
0.1 L to 0.25 L against a constant external pressure of 2
NCERT Page-186 / N-160 | 2016
bar. The work done by the gas is [Given that 1 L bar = 100 J]
(a) H > 0 and S > 0 (b) H > 0 and S < 0
NCERT Page-165 / N-142 | 2019
(c) H < 0 and S > 0 (d) H < 0 and S < 0
(a) –30 J (b) 5 kJ
17. The heat of combustion of carbon to CO2 is –393.5 kJ/mol.
(c) 25 J (d) 30 J
The heat released upon formation of 35.2 g of CO2 from
11. In which case change in entropy is negative ?
carbon and oxygen gas is 2015 RS
NCERT Page-183 / N-158 | 2019
(a) –315 kJ (b) +315 kJ
(a) Evaporation of water
(c) –630 kJ (d) –3.15 kJ
(b) Expansion of a gas at constant temperature
18. For the reaction : 2014
(c) Sublimation of solid to gas
X2O4(l) 2XO2(g)
(d) 2H(g) H2(g)
U = 2.1 k cal, S = 20 cal K–1 at 300 K
12. The bond dissociation energies of X2, Y2 and XY are in the
Hence G is:-
ratio of 1 : 0.5 : 1. H for the formation of XY is –200 kJ mol–1.
The bond dissociation energy of X2 will be 2018
(a) 2.7 k cal (b) – 2.7 k cal
(a) 200 kJ mol –1 (b) 100 kJ mol –1 (c) 9.3 k cal (d) – 9.3 k cal
(c) 400 kJ mol–1 (d) 800 kJ mol–1 19. When 5 litres of a gas mixture of methane and propane is
13. A gas is allowed to expand in a well insulated container perfectly combusted at 0°C and 1 atmosphere, 16 litre of
against a constant external pressure of 2.5 atm from an oxygen at the same temperature and pressure is consumed.
initial volume of 2.50 L to a final volume of 4.50 L. The The amount of heat released from this combustion in kJ
change in internal energy U of the gas in joules will be:- ( Hcomb (CH4) = 890 kJ mol–1,
NCERT Page-165 / N-142 | 2017 Hcomb (C3H8) = 2220 kJ mol–1) is Kar. 2013

(a) – 500 J (b) – 505 J (a) 32 (b) 38

(c) + 505 J (d) 1136.25 J (c) 317 (d) 477
 148 Chemistry

Exercise 3 Multi-Concept Exercise

1. Which of the following relation is not correct?

8. If the standard enthalpy change rH for a certain
(a) H= U– P V (b) U= q+ W
(c) Ssys = Ssurr 0 (d) G= H– T S reaction at 298 K and constant pressure is –1860 kJ mol–1,
2. Which among the following is note state variable ?
the standard entropy change sysS of the same reaction
(a) Internal energy (U) (b) Volume (V)
(c) Heat (q) (d) Enthalpy (H) is –550 J K–1 mol–1, which one of the following statements
3. The molar heat capacity for an ideal gas at constant is correct?
pressure is 20.785 J K–1 mol–1. The change in internal energy
(a) sysS surr S = –7692 J mol–1 K–1, the reaction
is 5000 J upon heating it from 300K to 500K. The number of
moles of the gas at constant volume is is spontaneous
(a) 6 (b) 2 (c) 8 (d) 10
(b) sysS surr S = –5692 J mol–1 K–1, the reaction is
4. If the enthalpy and entropy change for a reaction at 298 K
are –145 kJ mol–1 and –650 J K–1 mol–1 respectively, which non–spontaneous
one of the following statements is correct?
(a) G = – 50 kJ mol–1, the reaction is spontaneous (c) sysS surr S = +5692 J mol–1 K–1, the reaction is
(b) G = – 48.7 kJ mol–1, the reaction is non–spontaneous spontaneous
(c) G = + 50 kJ mol–1, the reaction is spontaneous
(d) G = 48.7 kJ mol–1, the reaction is non–spontaneous (d) sysS surr S = +7692 J mol–1 K–1, the reaction is
5. If G and S for the reaction A(g) B(g) + 2C(g) at 2000 non–spontaneous
K are –40 kJ mol–1 and 0.22 kJ K–1 mol–1 respectively, the 9. 2.2 g of nitrous oxide (N2O) gas is cooled at a constant
change in internal energy for the same reaction pressure of 1 atm from 310 K to 270 K causing the
approximately (in kJ mol–1) is compression of the gas from 217.1 mL to 167.75 mL. The
(a) 366.7 (b) –366.7(c) 433.3 (d) –433.3 change in internal energy of the process, U is '–x' J. The
6. For the reaction value of 'x' is
H2F2(g) H2(g) + F2(g) (Given: atomic mass of N = 14 g mol–1 and of O = 16 g mol–1.
Molar heat capacity of N2O is 100 JK–1 mol–1)
U = –59.6 kJ mol–1 at 27 °C.
(a) 200 J (b) 195 J
The enthalpy change for the above reaction is
(c) 192 J (d) 198 J
(a) –57 kJ mol–1 (b) –63 kJ mol–1
10. 4.0 L of an ideal gas is allowed to expand isothermally into
(c) –55 kJ mol–1 (d) –50 kJ mol–1 vacuum until the total volume is 20 L. The amount of heat
7. 1.0 mol of monoatomic ideal gas is expanded from state 1 absorbed in this expansion is ___________ L atm.
to state 2 as shown in the figure. The magnitude of the (a) 0 (b) 2 (c) 20 (d) 80
work done for the expansion of gas from state 1 to state 2 11. When 5 moles of He gas expand isothermally and
at 300 K is reversibly at 300 K from 10 litre to 20 litre, the magnitude
of the maximum work obtained is
6.0 State 1 (a) 8662 J (b) 8630 J
(c) 8540 J (d) 8723 J
12. 200 mL of 0.2 M HCl is mixed with 300 mL of 0.1 M NaOH.
The molar heat of neutralization of this reaction is –57.1 kJ.
P(bar)

3.0 State 2
The increase in temperature in °C of the system on mixing
is x × 10–2.
22.7 V(L) The value of x is
(a) 82 (b) 72 (c) 83 (d) 80
(a) 1732 J (b) 1723 J (c) 1718 J (d) 1717 J
 Thermodynamics 149

13. For water vap H = 41 kJ mol–1 at 373 K and 1 bar pressure. 19. For combustion of one mole of magnesium in an open
Assuming that water vapour is an ideal gas that occupies container at 300 K and 1 bar pressure, = – 601.70 kJ
C H°
a much larger volume than liquid water, the internal energy
mol–1, the magnitude of change in internal energy for the
change during evaporation of water is_____kJ mol–1
reaction is _____
(a) 36 (b) 63 (c) 42 (d) 38
(a) 250 kJ (b) 300 kJ (c) 600 kJ (d) 400 kJ
14. At 25 ºC, 50 g of iron reacts with HCl to form FeCl 2. The
20. Workdone for the conversion of 0.5 mole of water at 100ºC
evolved hydrogen gas expands against a constant
to steam at 1 atm pressure is (heat of vaporisation of water
pressure of 1 bar. The work done by the gas during this
at 100ºC is 40670 J mol–1)
expansion is _____.
(a) –1.54 kJ (b) 1.54 kJ
(a) 2218 J (b) 2220 J
(c) 1.25 kJ (d) –1.35 kJ
(c) 2348 J (d) 2210 J
21. At 25°C and 1 atm pressure, the enthalpy of combustion of
15. Match List-I with List-II
benzene (1) and acetylene (g) are –3268 kJ mol–1 and
List-I List-II
–1300 kJ mol–1, respectively. The change in enthalpy for
(A) Spontaneous process (p) H< 0
the reaction 3 C2H2(g) C6H6(l), is
(B) Process with P = 0, (q) GT,P < 0
(a) + 324 kJ mol–1 (b) + 632 kJ mol–1
T=0
(c) – 632 kJ mol–1 (d) – 732 kJ mol–1
(C) Hreaction (r) Isothermal and
22. At 298 K, the enthalpy of fusion of a solid (X) is 2.8 kJ
isobaric process mol–1 and the enthalpy of vaporisation of the liquid (X) is
(D) Exothermic process (s) [Bond energies of 98.2 kJ mol–1. The enthalpy of sublimation of the substance
molecules in reactants]- (X) in kJ mol–1 is ________ .
[Bond energies of (a) 101 (b) 132 (c) 142 (d) 124
product molecules] 23. The heat of atomisation of Bi is 207 kJ mol–1. It forms Bi 2
Choose the correct answer from the options given below: molecules in the gas phase and for the reaction,
(a) A – (r), B – (q), C – (s), D – (p)
2Bi(s) Bi2(g), H = 125 kJ mol–1 of Bi(s). The
(b) A – (q), B – (r), C – (s), D – (p)
Bi – Bi bond energy in Bi2(g) is
(c) A – (q), B – (r), C – (p), D – (s)
(a) 170 J mol–1 (b) 170 kJ mol–1
(d) A – (q), B – (p), C – (r), D – (s)
(c) 164 J mol–1 (d) 164 kJ mol–1
16. If H is the change in enthalpy and E is change in internal
24. The heat of combustion of ethanol into carbon dioxide
energy accompanying a gaseous reaction, then
and water is – 327 kcal at constant pressure. The heat
(a) H is always greater than E evolved (in cal) at constant volume and 27 °C (if all gases
(b) H < E only if the number of moles of the products behave ideally) is
is greater than the number of moles of the reactants (a) –326400 (b) –323000
(c) H is always less than E (c) –342500 (d) –354200
(d) H < E only if the number of moles of products is 25. For a given chemical reaction A B at 300 K the free
less than the number of moles of the reactants. –1
energy change is –49.4 kJ mol and the enthalpy of reaction
17. At constant volume, 4 mol of an ideal gas when heated is 51.4 kJ mol–1. The entropy change of the reaction is
from 300 K to 500 K changes its internal energy by 5000 J. ______ J K–1 mol–1.
The molar heat capacity at constant volume is ______. (a) 336 (b) 338 (c) 342 (d) 346
(a) 6.37 (b) 5.42 (c) 6.25 (d) 6.30 26. For the reaction A(g) B(g), the value of the equilibrium
18. The enthalpy of combustion of propane, graphite and constant at 300 K and 1 atm is equal to 100.0. The value of
dihydrogen at 298 K are – 2220.0 kJ mol–1, –393.5 kJ mol–1 –1
rG for the reaction at 300 K and 1 atm in J mol is – xR,
and – 285.8 kJ mol–1 respectively. The magnitude of where x is _____
enthalpy of formation of propane (C3H8) is ____ kJ mol–1. (a) 1263 (b) 1380 (c) 1542 (d) 1340
(a) –103.7 (b) –110.4 (c) –108.9 (d) –114.4
 150 Chemistry

27. The true statement amongst the following is : 32. The process with negative entropy change is:
(a) Both S and S are functions of temperature. (a) Dissociation of CaSO4(s) to CaO(s) and SO3(g)
(b) Both S and S are not functions of temperature. (b) Sublimation of dry ice
(c) S is not a function of temperature but S is a function (c) Dissolution of iodine in water
of temperature. (d) Synthesis of ammonia from N2 and H2
(d) S is a function of temperature but S is not a function 33. Which of the following statements/relationships is not
of temperature. correct in thermodynamic changes ?
28. The standard entropy change for the reaction (a) U = (isothermal reversible expansion of a gas)
4Fe(s) + 3O2(g) 2Fe2O3(s) is –550 JK–1 at 298 K. V
(b) w = – nRT ln 2 (isothermal reversible expansion of
[Given : The standard enthalpy change for the reaction is – V1
an ideal gas)
165 kJ mol–1]. The temperature in K at which the reaction
V
attains equilibrium is (c) w = nRT ln 2 (isothermal reversible expansion of
V1
(a) 372 (b) 300 (c) 342 (d) 363 an ideal gas)
29. For the reaction 2NO 2 (g) N 2 O 4 (g), when (d) For a system of constant volume heat involved
directly changes to internal energy.
S = –176.0 JK–1 and H = –57.8 kJ mol–1, the magnitude of
34. For which of the following processes, S is negative?
G at 298 K for the reaction is_____ kJ mol–1.
(a) 9 (b) 1 (c) 5 (d) 7 (a) C(diamond) C(graphite)
30. A process will be spontaneous at all temperatures if :
(b) N 2 (g,1 atm) N 2 (g,5 atm)
(a) H < 0 and S < 0 (b) H > 0 and S < 0
(c) H < 0 and S > 0 (d) H > 0 and S > 0 (c) N 2 (g, 273 K) N 2 (g,300 K)
31. The reaction
(d) H 2 (g) 2H(g)
MgO (s) + C(s) Mg(s) + CO (g), for which
35. The molar heat capacity (Cp) of CD2O is 10 cals at 1000 K.
H° = +491.1 kJ mol–1 and S° = 198.0 JK–1mol–1,
The change in entropy associated with cooling of 32 g of
is not feasible at 298 K. Temperature above which reac-
CD2O vapour from 1000 K to 100 K at constant pressure
tion will be feasible is
will be: (D = deuterium, atomic mass = 2 u)
(a) 2040.5 K (b) 1890.0 K
(a) 23.03 cal deg–1 (b) – 23.03 cal deg–1
(c) 2480.3 K (d) 2380.5 K
(c) 2.303 cal deg–1 (d) – 2.303 cal deg–1

Exercise 4 Assertion Reason MCQs

Directions : These questions consist of two statements, each 3. Assertion : A process is called adiabatic if the system
printed as Assertion and Reason. While answering these does not exchange heat with the surroundings.
questions, you are required to choose any one of the following Reason : It does not involve increase or decrease in
four responses. temperature of the system.
(a) If both Assertion and Reason are correct and the Reason 4. Assertion : There is exchange in internal energy in a cyclic
is a correct explanation of the Assertion. process.
(b) If both Assertion and Reason are correct but Reason is Reason : Cyclic proces is the one in which the sytem returns
not a correct explanation of the Assertion. to its initial state after a number of reactions.
(c) If the Assertion is correct but Reason is incorrect. 5. Assertion : First law of thermodynamics is applicable to
(d) If both the Assertion and Reason are incorrect. an electric fan or a heater.
Reason : In an electric fan, the electrical energy is converted
1. Assertion : T, P and V are state variables or state functions.
into mechanical work that moves the blades. In a heater,
Reason : Their values depend on the state of the system
electrical energy is converted into heat energy.
and how it is reached.
6. Assertion : When a solid melts, decrease in enthalpy is
2. Assertion : At constant temperature and pressure whatever
observed.
heat absorbed by the system is used in doing work.
Reason : Melting of a solid is exothermic.
Reason : Internal energy change is zero.
 Thermodynamics 151

7. Assertion : An exothermic process which is non- 9. Assertion : H and E are almost same for the reaction
spontaneous at high temperature may become
N 2 (g) O2 (g) 2NO(g)
spontaneous at a low temperature.
Reason : There occurs a decrease in entropy factor as the Reason : All reactants and products are gases.
temperature is decreased. 10. Assertion : When a salt such as NaCl dissolves, the Na+
and Cl– ions leaving the crystal lattice acquire far greater
8. Assertion : During an adiabatic process, heat energy is
freedom.
not exchanged between system and its surroundings.
Reason : In thermodyanamic terms, the formation of
Reason : The temperature of a gas increases when it solution occurs with a favourable change in free energy,
undergoes an adiabatic expansion. i.e., H has a high positive value and T S a low negative
value.

Exercise 5 Master Stroke

1. Enthalpy of sublimation of iodine is 24 cal g–1 at 200°C. If 5. For the reaction taking place at certain temperature
specific heat of I2(s) and I2(vap) are 0.055 and 0.031 cal NH 2 COONH 4 s 2NH 3 g CO 2 g ,
g–1K–1 respectively, then enthalpy of sublimation of iodine
if equilibrium pressure is 3X bar then rG° would be
at 250°C in cal g–1 is : NCERT Page-172 / N-147
NCERT Page-186 / N-162
(a) 2.85 (b) 5.7 (c) 22.8 (d) 11.4
(a) – RT ln 9 – 3RT ln X (b) RT ln 4 – 3RT ln X
2. Which of the following expressions is true for an ideal
(c) – 3RT ln X (d) None of these
gas?
6. The heat of combustion of ethane gas is 368 kcal/mol.
dV dP Assuming that 60% of the heat is useful, how many m3 of
(a) 0 (b) 0
dT P dT V ethane measured at STP must be burnt to supply enough
heat to convert 50 kg of water at 10oC to steam at 100oC?
dU dU (Specific heat of water is 1 cal/g, heat of vaporisation of
(c) 0 (d) 0
dV T dT V H2O is 540 cal/g)
(a) 2.196 m3 (b) 1.196 m3
5 (c) 4.196 m3 (d) 3.196 m3
3. 0.5 mole each of two ideal gases A Cv , m R and
2
7. If bond enthalpies of N N, H – H and N – H bonds are x1,
B (Cv,m = 3R) are taken in a container and expanded x2 and x3 respectively, H°f for NH3 will be
reversibly and adiabatically, during this process NCERT Page-178 / N-154
temperature of gaseous mixture decreased from 350 K to
250 K. Find H (in cal/mol) for the process: 1
(a) x1 + 3x2 – 6x3 (b) x + 3/2x2 – 3x3
2 1
(a) – 100 R (b) – 137.5 R
(c) – 375 R (d) None of these 1
(c) 3x3 – x – 3/2x2 (d) 6x3 – x1 – 3x2
4. A heating coil is immersed in a 100 g sample of H2O (l) at 2 1
1 atm and 100°C in a closed vessel. In this heating process, 8. Match Column-I with Column-II
60% of the liquid is converted into gaseous form at Column-I Column-II
constant pressure of 1 atm. Densities of liquid and gaseous (Process) (Entropy change)
water under these conditions are 1000 kg/m 3 and
(A) Reversible isothermal
0.60 kg/m3 respectively. Magnitude of the work done for
ideal gas expansion (p) Ssurrounding = 0
the process is :
(B) Reversible adiabatic
(a) 4997 J (b) 4970 J
ideal gas compression (q) Ssurrounding < 0
(c) 9994 J (d) None of these
 152 Chemistry

(C) Adiabatic free expansion (a) Both statement I and II are correct.
(Pext = 0) of an ideal gas (r) Ssurrounding > 0 (b) Both statement I and II are incorrect.
(D) Irreversible isothermal (c) Statement I is correct but statement II is incorrect.
ideal gas compression (s) Ssystem = 0 (d) Statement II is correct but statement I is incorrect.
(a) A – (q); B – (p, s); C – (p); D – (r) 14. Fixed mass of an ideal gas contained in a 24.63 L sealed
(b) A – (p); B – (q); C – (r); D – (s) rigid vessel at 1 atm is heated from – 73°C to 27°C. Calculate
(c) A – (s); B – (r); C – (p); D – (q) change in Gibb's energy if entropy of gas is a function of
(d) A – (q); B – (p); C – (r); D – (s) temperature as S = 2 + 10–2 T (J/K): (Use 1 atm L = 0.1 kJ)
9. If the ratio of molar heat capacities of a gas at constant (a) 1231.5 J (b) 1281.5 J
C (c) 781.5 J (d) 0
pressure and constant volume i.e., P , the respective
CV 15. The densities of graphite and diamond at 298 K are 2.25
values of CP and CV are
and 3.31 g cm–3, respectively. If the standard free energy
R R R R difference ( Gº) is equal to 1895 J mol–1, the pressure at
(a) , (b) ,
1 1 1 1 which graphite will be transformed into diamond at 298 K
is
1 1 1 1 (a) 9.92 × 105 Pa (b) 11.094 × 108 Pa
(c) , (d) ,
R R R R (c) 10.952 × 107 Pa (d) 9.92 × 106 Pa
16. If H is considered as the function of P and T, then which of
10. The bond dissociation energies of CH4 and C 2H 6
the following relations is /are correct?
respectively are 360 and 620 k cal mol–1. The C – C bond
energy would be NCERT Page-177, 178 / N-154, 155 dH dH
(a) dH = dT + dP
(a) 260 k cal/mol (b) 180 k cal/mol dT P dP T
(c) 130 k cal/mol (d) 80 k cal/mol
11. Given that: dH
(b) dH = C p dT + dP
–1 dP T
(i) f H of N2 O is 82 kJ mol

(ii) Bond energies of N N, N=N, O = O and N = O are

dH
946, 418, 498 and 607 kJ mol–1 respectively, (c) =0
dP T
The resonance energy of N2O is :
(a) –88 kJ (b) – 66 kJ (d) all
(c) –62 kJ (d) –44 kJ 17. Two flasks I and II shown below are connected by a valve
12. Calculate enthalpy change for the change of negligible volume.

8S(g) S8(g), given that

NCERT Page-170, 171 / N-147, 148

1;
H 2S2 (g) 2H(g) 2S(g), H 239.0 k cal mol
1
H 2 S(g) 2H(g) S(g), H 175.0 k cal mol

(a) + 512.0 k cal (b) – 512.0 k cal

(c) 508.0 k cal (d) – 508.0 k cal
When the valve is opened, the final pressure of the system
13. Statement I: The value of enthalpy of neutralization of
in bar is x × 10–2. The value of x is ______.
weak acid and strong base is numerically less than 57.1 kJ.
(a) 84 atm (b) 85 atm
Statement II: All the OH– ions furnished by 1 g equivalent
(c) 83 atm (d) 80 atm
of strong base are not completely neutralized.
 Thermodynamics 153

18. The magnitude of work done by a gas that undergoes a UBC = –5 kJ mol–1, qAB = 2 kJ mol–1
reversible expansion along the path ABC shown in the WAB = –5 kJ mol–1, WCA = 3 kJ mol–1
figure is _______. NCERT Page-165, 166 / N-142, 143 Heat absorbed by the system during process CA is:
(a) –5 kJ mol–1 (b) +5 kJ mol–1

Pressure
(c) 18 kJ mol–1 (d) –18 kJ mol–1
(Pa)
10 22. While performing a thermodynamics experiment, a
A B
8 student made the following observations,
6 HCl + NaOH NaCl + H2O, H = –57.3 kJ mol–1
4
CH3COOH + NaOH CH3COONa + H2O
C
H = –55.3 kJ mol–1
(2, 2) 4 6 8 10 12 Volume
(m3) The enthalpy of ionization of CH3COOH as calculated by
the student is _____ kJ mol–1.
(a) 7 (b) 2
(a) 42 (b) 54 (c) 48 (d) 56
(c) 4 (d) 8
19. On the basis of the following graph (P–V graph), choose
23. Assuming ideal behaviour, the magnitude of log K for the
the correct statements.
following reaction at 25°C is x × 10–1. The value of x is
________. (Integer answer). NCERT Page-186 / N-162
P
A B 3HC CH (g) C 6 H 6 (l)
1atom

0
0.5 atom
[Given : fG (HC CH) 2.04 105 J mol 1;
C
0
V fG (C6 H 6 ) 1.24 105 J mol 1; R = 8.314 J K–1 mol–1]
202 402
(a) 855 (b) 842 (c) 845 (d) 832

(a) The entropy change for the over all process is zero. 24. For the reaction at 25 °C, X 2 O 4 l 2XO 2 g , U
(b) For the over all process H > E.
and S are 2.1 K. Cal and 20 Cal/K respectively. What is
(c) Total work done, W = q G for the reaction at the same temperature? (R = 2 Cal K–1
(d) Total work = – 620.77 J mol–1)
20. Among the following, the set of parameters that represents (a) –2.67 k. Cal (b) +2.67 k. Cal
path functions, is: NCERT Page-164, 184 / N-138, 160 (c) –1.67 k. Cal (d) +3.67 k. Cal
(A) q + w (B) q 25. Choose the correct statements.
(C) w (D) H – TS (a) First law of thermodynamics is also known as the law
(a) (B) and (C) (b) (B), (C) and (D) of thermal equilibrium.
(c) (A) and (D) (d) (A), (B) and (C) (b) It is not possible to find out the heat of combustion
21. An ideal gas undergoes a cyclic process as shown in figure. at room temperature.
(c) The triple point of water is one of the reference points
A B on the thermodynamic scale of temperature.
1
P (d) One degree kelvin is equal to of the triple
273.16
C point of water.
V
 154 Chemistry

ANSWER KEYS
CDQs 5.1 Classroom Discussion Questions
1 (b) 2 (d) 3 (a) 4 (c)
CDQs 5.2 Classroom Discussion Questions
5 (a) 6 (c) 7 (a) 8 (c)
CDQs 5.3 Classroom Discussion Questions
9 (c) 10 (a) 11 (d) 12 (d)
CDQs 5.4 Classroom Discussion Questions
13 (a) 14 (b) 15 (a)
Exercise 1 Home Assignment (NCERT Based MCQs)
1 (b) 8 (d) 15 (b) 22 (b) 29 (a) 36 (b) 43 (a) 50 (b) 57 (c) 64 (b)
2 (c) 9 (d) 16 (a) 23 (c) 30 (d) 37 (b) 44 (d) 51 (a) 58 (b) 65 (b)
3 (b) 10 (a) 17 (c) 24 (b) 31 (a) 38 (b) 45 (a) 52 (a) 59 (a) 66 (b)
4 (c) 11 (b) 18 (a) 25 (a) 32 (a) 39 (d) 46 (d) 53 (b) 60 (a) 67 (c)
5 (d) 12 (c) 19 (d) 26 (d) 33 (c) 40 (c) 47 (b) 54 (b) 61 (d) 68 (a)
6 (a) 13 (c) 20 (b) 27 (a) 34 (d) 41 (c) 48 (b) 55 (b) 62 (d) 69 (a)
7 (c) 14 (d) 21 (d) 28 (c) 35 (d) 42 (c) 49 (b) 56 (a) 63 (a) 70 (c)
Exercise 2 NEET Past Year MCQs
1 (b) 3 (c) 5 (d) 7 (c) 9 (a) 11 (d) 13 (b) 15 (d) 17 (a) 19 (c)
2 (a) 4 (d) 6 (b) 8 (c) 10 (a) 12 (d) 14 (a) 16 (c) 18 (b)
Exercise 3 Multi-Concept Exercise
1 (a) 5 (N) 9 (b) 13 (d) 17 (c) 21 (c) 25 (a) 29 (c) 33 (c)
2 (c) 6 (a) 10 (a) 14 (a) 18 (a) 22 (a) 26 (b) 30 (c) 34 (b)
3 (b) 7 (c) 11 (b) 15 (b) 19 (c) 23 (d) 27 (a) 31 (c) 35 (b)
4 (d) 8 (c) 12 (a) 16 (d) 20 (a) 24 (a) 28 (b) 32 (d)
Exercise 4 Assertion Reason MCQs
1 (c) 2 (a) 3 (c) 4 (a) 5 (a) 6 (d) 7 (b) 8 (c) 9 (b) 10 (c)
Exercise 5 Master Stroke
1 (c) 4 (c) 7 (b) 10 (d) 13 (b) 16 (d) 19 (a, d) 22 (b) 25 (b, c)
2 (c) 5 (d) 8 (a) 11 (a) 14 (c) 17 (a) 20 (a) 23 (a)
3 (c) 6 (d) 9 (b) 12 (b) 15 (b) 18 (c) 21 (b) 24 (a)