THERMODYNAMICS

INDEX
Topic Name Page No.

 Chapter at Glance 40-69

 Solved Objective Examples 70-73
 Exercise 74-101

 (Multiple Choice Questions) 74-88

 Previous Year’s Questions 88-101

 Answers 102-103

This Chapter Includes:

 Applications in Chemistry  Limitations of Thermodynamics
 Some Basic Terms  Thermodynamic Equilibrium
 Extensive & Intensive Properties  State Functions or State Variables
 Work & Types of Work  Heat
 Internal Energy or Intrinsic energy (E)  Enthalpy (H) or Heat Content:
 Relation Between H and E  Cyclic Process
 First Law of Thermodynamics  Heat Capacity
 Specific Heat  Pressure-Volume Work
 Work-done in Reversible Isothermal Expansion  Adiabatic Expansion
 Thermochemistry  Factors Affecting Heat of Reaction
 Enthalpy or Heat of Formation  Enthalpy or Heat of Neutralisatoion
 Hess's law of constant heat summation  Spontaneous Process
 Statement of IInd Law Of Thermodynamics  Free Energy Change (G)

Symbol  in Exercise denotes: Class Work

Symbol  in Exercise denotes: Home Work

 Thermodynamics Ch. XI

THERMODYNAMICS
Thermodynamics is concerned only with energy changes accompanying a given process Chemical
thermodynamics is that branch of thermodynamics which deals only with process involving only chemical
energy.
The study of thermodynamics is based on three generalization, called the first, second and third law of
thermodynamics. All these laws are based on human experience and although there is no formal proof for
these laws, nothing contrary to these laws has been found so far and nothing contrary is expected.

APPLICATIONS IN CHEMISTRY

(i) Thermodynamics helps us in predicting the feasibility of a particular process (physical or chemical),
i.e. whether the process can occur or not under a given set of conditions of temperature, pressure and
concentration.
(ii) Thermodynamics also helps in determining the extent to which a reaction would proceed before
attainment of equilibrium and thus it may predict the yields of products.

LIMITATIONS OF THERMODYNAMICS

(i) The laws of thermodynamics are applicable only to matter in bulk, i.e., assemblage of large numbers
of molecules (macroscopic system), and not to individual molecules of atoms. The thermodynamics is
independent of atomic and molecules structure of matter, i.e., it ignores the internal structure of atoms
and molecules
(ii) Although thermodynamics predicts about the feasibility, direction and extent of a given process under
a given set of conditions, it does not tell any thing about the rate at which a given process may
proceed, i.e., it provides no information regarding the time taken to reach equilibrium
(iii) If concerns itself only with the initial and final states of a system and gives no information about the
path taken (mechanism) by a process.

SOME BASIC TERMS

(i) System: A specific portion of matter under study, which is isolated from the rest of the universe
with a bounding surface, is called a system.
(ii) Surroundings: The rest of the universe, which might be in a position to exchange energy and matter
with the system, is called the surroundings.

TYPES OF SYSTEMS:
(i) Open System: A system is said to be open when it can exchange matter as well as energy with
its surroundings.
(ii) Closed System: A system which can exchange energy but not matter with its surroundings is a
closed system.
(iii) Isolated System: A system which can exchange neither matter nor energy with the surroundings
is known as isolated system. Hot coffee in a thermos flask is an example of an isolated system because
it can neither gain or lose matter nor it can lose energy.
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 Thermodynamics Ch. XI

(iv) Homogeneous System: A system is homogeneous when it is completely uniform throughout, i.e.,
consists of only one phase. For example, a pure solid, a pure liquid, a true solution, a mixture of gases.
(v) Heterogeneous System: A system is said to be heterogenous when it is not uniform throughout. i.e.,
a heterogenous system is one which consist of two or more phases. For example, a mixture of two
solids or two or more immisicible liquids, a solid in contact with liquid, a liquid in contact with its
vapours.
 Macroscopic properties: They are the properties associated with a macroscopic system. For example:
Pressure, volume, temperature, density, composition, viscosity surface tension, refractive index, colour
etc.
 State of a system: A system is a said to be in definite state when its macroscopic properties have
definite values. Whenever any one of the macroscopic properties changes, the system is said to
change into a different state. Thus, the macroscopic properties determine the state of a system.
 State variables: The macroscopic properties of a system are state variables since changes in any of
another state. Thus, when a system changes from one state to another state, there is definitely change
in one or more of its macroscopic properties.
 Extensive property: A property, which depends upon the amount of the substance(s) present in the
system, is called extensive property e.g. mass, volume, energy, work, internal energy, enthalpy,
entropy etc.
 Intensive property: A property which is independent of the amount of substance(s) present in the
system is called intensive property, e.g. temperature, pressure, density, concentration, viscosity,
refractive index, surface tension, specific heat, etc.
 State functions: The thermodynamics parameters, which depend only upon the initial and final states
of the system and are independent of how the change is accomplished, are called state functions.
Internal energy (E), enthalpy (H), entropy (S), free energy (G), pressure (P), temperature (T) volume
(V), etc. Work and heat are not state functions because their values do depend merely on the initial
and final states but depend upon the path followed.

THERMODYNAMIC EQUILIBRIUM
A system is said to be in thermodynamic equilibrium when any of its macroscopic properties does not
change with time Heterogeneous systems are in equilibrium when the macroscopic properties in the various
phases remain unchanged with time. Three kinds of thermodynamics equilibrium exist:
(i) Thermal equilibrium: A system is said to be in thermal equilibrium if no heat flows from one
part of the system to another.
(ii) Mechanical equilibrium: When no mechanical work is done by one part of the system on another
part, the system is said to be in mechanical equilibrium. This is possible if pressure remains the same
throughout in all the portions of the system.
(iii) Chemical equilibrium: A system is in chemical equilibrium if the composition of the various
phases in the system is the same throughout.

EXTENSIVE & INTENSIVE PROPERTIES

Extensive properties: Properties which depend on the amount of matter are called extensive properties.
mass, volume, energy, enthalpy, entropy etc.
Intensive properties: Properties which do not depend on the amount of matter are called intensive
properties. e.g. Pressure, temperature, density, specific heat, specific volume, surface tension, velocity,
electromotive force etc.

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 Thermodynamics Ch. XI

STATE FUNCTIONS OR STATE VARIABLES

Those fundamental properties which determine the state of a system are called state variables or state
functions or thermodynamic parameters. The change in the state properties is dependent on the initial; and
final states of the system and not on the path followed.
State variables that are commonly used to be describe the state of the thermodynamic system are
1. Pressure (P) 2. Volume (V)
3. Temperature (T) 4. Internal energy (E)
5. Enthalpy (H) 6. Entropy (S)
7. Free energy (G) 8. Number of moles (m)

WORK & TYPES OF WORK

Work is defined as energy transfer to or from a system with reference to the surroundings.
Work is said to have been done whenever the point of application of a force is displaced in the direction of
the force.
W = (A generalised force)  (A generalised displacement)
W = F  dx

TYPES OF WORK
(a) Gravitational work = mgh
where m = mass of body, g = acceleration due to gravity and h = height moved.
Work is an algebraic quantity. It is +ve if the mass is lifted (h is +ve), in which case it is said that work
has been produced in the surroundings and it is –ve if the mass is lowered (h is –ve), in which case the
work is said to be destroyed in the surroundings or has flowed from the surroundings.
(b) Electrical work = Charge  potential = q  V
Electrical work is important in systems where reaction takes place between ions. Here generalized
force is the E.M.F. and the generalised displacement is the quantity of electricity flowing through the
circuit. Hence.
Electrical work done = E.M.F.  Quantity of electrical charge
(c) Mechanical work = Pext (V2 – V1) = Pext V
where Pext = external pressure and V = increase or decrease in volume.
Work done on a system increases the energy of the system and work done by the system decreases the
energy of the system.
Work done on the system, w = +ve
Work done by the system, w = –ve

HEAT

It is defined as the energy that flows across the boundary of a system during a change in its state by virtue
of a difference in temperature between the system and its surroundings and flows from a point of higher to
a point of lower temperature.
Heat absorbed or evolved, Q = ms t
where m = mass of substance, s = specific heat and t = temperature difference

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(i) endothermic: if heat flows into the system, Q or H is +ve and the process is referred as endothermic
(ii) exothermic: if heat flows out of the system, Q or H is –ve and the process is referred as exothermic
UNIT OF HEAT AND WORK
The unit of heat is calorie. One calorie is defined as the quantity of heat required to raise the temperature of
one gram of water by 1oC.
Since, heat and work are interrelated, SI unit of heat is Joule.
1 cal = 4.184 Joule
1 litre atm = 101.3 J = 1.013 109 erg = 24.206 cal.

INTERNAL ENERGY OR INTRINSIC ENERGY (E):

The total energy stored in a substance by virtue of its chemical nature is called its internal energy.
E = Et + Er + Ev + Ee + En+ EPE
Internal energy is a state function, i.e. depends only upon the state of the system (i.e. conditions of temperature,
pressure, etc.) and is independent of the method by which state has been attained change in internal energy
(difference between the internal energies of the products, E2 or EP and that of reactants, E1 or RR) can be
determined experimentally using a bomb calorimeter.
E = E2(EP) – E1 (ER)
(i) Internal energy of a system depends upon the quantity of substance coined in the system. Hence it is
an extensive property.
(ii) The internal energy of ideal gases is a function of temperature only. Hence in isothermal processes, as
the temperature remains constant, there is no change in internal energy. i.e., E = 0.
(iii) At constant volume, the quantity of heat supplied to a system (isochoric process) is equal to the
increase in the internal energy, i.e., q = E.
(iv) In the adiabatic expansion of a gas, it gets cooled because of decrease in internal energy.
(v) In a reversible (cyclic) process the change in internal energy is zero (E = 0) since E is a state
function.
(vi) If E1 > E2 (or ER > EP), the extra energy of the system in the initial state (or the reactants) would be
given out (exothermic reaction) and hence E will be negative.
(vii) If E1 < E2 (or ER < EP), energy will be absorbed in the process (endothermic reaction) and E will be
positive
(viii)By conversion the internal energy of an element, in most stable form, is zero.

ENTHALPY (H) OR HEAT CONTENT:

The total heat content of a system at constant pressure is known as its enthalpy. It is the sum of internal
energy and the pressure – volume energy.
H = E + PV
Every substance has a definite value of enthalpy in a particular state. It is also a state function like internal
energy. The change in enthalpy accompanying a process can be determined as
H = H2 – H1
where H1 = Enthalpy of a substance in the initial state and H2 = Enthalpy of a substance in the final state.
In the case of a chemical reaction,H = HP – HR
where HP = Enthalpy of products and HR = Enthalpy of reactants.

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(i) The quantity of heat supplied to a system at constant pressure (isobaric process) i.e. QP is equal to the
increase in its enthalpy, H. QP = H.
(ii) For exothermic reactions. the sign of H is negative, i.e., HR > HP.
(iii) For endothermic reactions, the sign of H is positive, i.e., HP > HR.
(iv) In the laboratory mostly of the reactions are carried out at constant pressure. So H is more significant
than E.
5
(v) Enthalpy for a monoatomic gas is RT mole.
2
RELATION BETWEEN H AND E

Let us consider a chemical reaction.

XY
then at constant pressure (P), the enthalpy change would be given as
H = Hy – Hx.
We know that, H = E + PV
Let Ex and Vx be the internal energy and volume of the reactants and Ey and Vy be the respective values of
products. Then.
Hx = Ex + PVx & Hy = Ey + PVy
H = ( Ey + PVy ) – ( Ex PVx )
H = ( Ey – Ex ) + P( Vy – Vx )
H =  + P V ... (i)

APPLICATION OF FIRST LAW OF THERMODYNAMICS TO DIFFERENT TYPES OF PROCESS

(i) For an isochoric process. As volume is kept constant, V = 0. Hence E = q – PV becomes
E = qv.
(ii) For an isobaric process. As pressure is kept constant, P = 0. Under this condition,

Wexp = – Pext(V)
(iii) For an isothermal process. As T = 0, for an ideal gas E = 0

 dE = q + w = 0 or q = –w

(iv) Adiabatic process. Q = 0, E = w

dE = CvdT. Hence w = CvdT for 1 mole or w = n Cv dT for n moles.

T2

 Total work done, w =  nC dT  nC  T

T1
v v 2  T1  .

Further Cp – Cv = R, Dividing by Cv,

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Cp R R R nR(T2  T1 )
—1 or  — 1  or Cv   w rev 
CV Cv Cv  1 (   1)
Thus if T2 > T1, w = +ve i.e. work is done on the system. If T2 < T1, w –ve i.e. work is done by the
system.
(iv) Reversible process: The process is which change is carried out so slowly that the system and
surroundings are always in equilibrium is known as reversible process. A reversible thread and
takes infinite time for completion.
(v) Irreversible process: When a process is completed in a single step and cannot be reversed, it
is called an irrervesible process. In such a process, the system is in equilibrium with surroundings
in the initial an final states. Natural processes are irreversible.

Graphical representation of four basic thermodynamics processes

Illustration:
Calculate the amount of work done in each of the following cases :
(i) One mole of an ideal gas contained in a bulb of 10 litre capacity at 1 bar is allowed to enter into an
evacuated bulb of 100 litre capacity.
(ii) One mole of a gas is allowed to expand from a volume of 1 litre to a volume of 5 litres against the
constant external pressure of 1 bar (1 litre bar = 100 J).
Calculate the internal energy change (U) in each case if the process were carried out adiabatically.
Sol. (i) w   Pext  V
As expansion takes place into the evacuated bulb, i.e., against vacuum, Pext  0 .
Hence, w = 0.
For adiabatic process, q = 0,  U = q + w = 0 + 0 = 0.
(ii) V  V2  V1  5  1  4 litres
P  1 bar ,  w = P V
=  1  4 litre bar = 4 litre bar
=  4  100 J =  400 J (1 L bar = 100 J)
The negative sign implies that the work done by the system.
For adiabatic system, q = 0, Hence, U = q + w = 0 – 405.2 J = – 405.2 J

Illustration:
A 5 L cylinder contained 10 moles of oxygen gas at 27ºC. Due to sudden leakage through the hole, all
the gas escaped into the atmosphere and the cylinder got empty. If the atmospheric pressure is 1.0 atm,
calculate the work done by the gas. (1 L at = 101.3 J)
Sol. Vinitial  5L,T  270 C  27  273K  300K

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nRT 10  0.0821  300

Vfinal    246.3L
P 1.0
V  Vfinal  Vinitial  246.3  5  241.3L
w exp   PV  1  241.3 L atm  241.3  101.3J
=  24443.7 J

CYCLIC PROCESS

If a system returns to its original state undergoing a number of successive changes, it is said to be a
cyclic process. Thus most common example of such process is that of carnot cycle which consists of
the following four states:–
(i) Isothermal expansion (ii) Adiabatic expansion
(iii) Isothermal compression (iv) Adiabatic compression
It may be noted that the internal energy charge or enthalpy change or entropy change in a cyclic
process is zero.

CONVERSION OF HEAT INTO WORK – CARNOT HEAT ENGINE

The fraction of the heat absorbed by a machine that is converted into work is called the efficiency of the
machine. It is given by
W Q 2  Q1 T2  T1
  
Q2 Q2 T2
Where Q2 = heat absorbed from the source at temp. T2 and Q1 = heat rejected to the sink at temp. T1

EFFECT OF TEMPERATURE ON HEAT OF REACTION (KIRCHOFF'S EQUATION )

H 2  H1 E 2  E1
 Cp  and  C v
T2  T2 T2  T2
Where H1 and H2 are enthalpies of reaction at temperature T1 and T2 respectively and Co = Cp
(products) – Cp (Reactants). Similarly, E1 and E2 are internal energy changes at temperature T1
and T2 respectively and Cv = Cp (products) – Cp (Reactants). Similarly E1 and E2 are internal
energy changes at temperature T1 and T2 respectively and Cv = Cv (products) – (Reactants).

CLAUSSIUS CLAPEYRON EQUATION

For liquid Vapour equilibrium.

P2  H v  T2  T1 
log   
P1 2.303R  T1T2 

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 Thermodynamics Ch. XI

Where Hv is the latent heat of vaporization and P1 and P2 are the vapour pressures at temperature T1 and
T2 respectively or T1 and T2 are the boiling points at pressure P1 and P2 respectively.

FIRST LAW OF THERMODYNAMICS

Law of conservation of energy which states that "energy can neither be created nor destroyed although it
can be converted from one form to another. The law may also be stated in the following ways.
(i) The total energy of an isolated system remains constant although it can undergo a change from one
form to another.
(ii) Whenever a quantity of some form of energy disappears, an exactly equivalent amount of some other
form of energy must be produced.
(iii) It is impossible to construct a perpetual motion machine, i.e., a machine which would produce work
continuously without consuming energy.
(iv) There is an exact equivalence between heat and mechanical work, i.e. for every 4,184 joules of work
done, 1 calorie of heat is produced and vice versa.
MATHEMATICAL FORMULATION OF THE FIRST LAW OF THERMODYNAMICS

The change of internal energy, E (i.e. EP = ER) accompanying a process, performing work, W and
involving absorption of heat (Q) i.e. when the work done by the system, is given by the relation.
E = Q – W
In case work is done on the system, then  E = Q + W
This equation is the mathematical formulation of the first law of thermodynamics.
(i) For isothermal reversible process, E = 0
 Q=–W
V2
Since W = –2.303 nRT log V
1

V2
Q = 2.303 nRT log V
1

(ii) For a cyclic process resulting to its original state, i.e., for a process involving isothermal expansion of
an ideal gas.
E = 0, Q = W
(iii) For a process in which volume remains constant (isochoric process), no work of expansion is
done, i.e., W = 0, Hence the equation (i) becomes.
E = Qv (v indicates constant volume)
Since E is a state function, Qv also must be state function.
Thus at constant volume, the increase in internal energy of the gas (as indicated by its rise in
temperature) is equal to the heat absorbed.
(iv) For an adiabatic process, i.e., when no heat is gained or lost to the surrounding which is possible
when the system is well insulated, Q = 0
 E = – W (Q indicates constant heat)
Thus in such cases the decrease in internal energy is exactly equal to the work done. The negative
sign shows that work is done on the system by the surrounding.
(v) (a) When a gas expands against an external pressure P, the work done it is PV
(where V = V2 – V1), i.e., W = –PV
(b) When a gas is compressed, works is done on the system and is given by PV.

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(c) When a gas expands into vacuum, work done by it is zero since P = 0; therefore W = 0.
(d) In case of expansion of a gas, maximum work is done is the process is isothermal and reversible.
Illustration :
A gas expands by 0.5 litre against a constant pressure one atmosphere. Calculate the work done in
joule and calorie.
Solution: Work = – Pext × volume change
= – 1 × 0.5 = – 0.5 litre-atm
= – 0.5 × 101.328 J = – 50.644 J
0.5 lit-atm = – 0.5 × 24.20 cal = – 12.10 cal
Illustration:
One mole of an ideal gas is put through a series of changes as shown in the graph in which A, B,
C mark the three stages of the system. At each stage the variables are shown in the graph.
(a) Calculate the pressure at three stages of the system.
(b) Name the processes during the following changes:
(i) A to B (ii) B to C (iii) C to A, and (iv) overall change.

Solution :
(a) At stage A;
V = 24.0 L; T = 300 K; n = 1 ; R = 0.0821 lit-atm K–1 mol–1
Substituting these values in the ideal gas eqation,
1 0.0821 300
P= = 1.026 atm
24.0
At stage B : Volume remains the same but temperature change from 300 K to 600 K . Thus,
according to pressure law, the pressure will be double at B with respect to A.
Pressure at B = 2 × 1.026 = 2.052 atm
At stage C : Temperature is 300 K and volume is half that of stage A. Thus, according to
Boyle’s law, the pressure at C will be double with respect to A.
Pressure at C = 2 × 1.026 = 2.052 atm
(b) (i) During the change from A to B, volume remains constant, the process is
isochoric.

(ii) During the change from B to C the pressure remains constant, the process is isobaric.
(iii) During the change from C to A, the temperature remains constant, the process
is isothermal.
(iv) Overall, the process is cyclic as it returns to initial state.

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Illustration:
The diagram shows a P-V graph of a thermodynamic behaviour of an ideal gas. Find out form this
graph :
(i) work done in the process A B, B C, C D and D A
(ii) work done in the complete cycle A B C D A.
Solution:

12 A B
10

P(105Newton/m2)
8
6
4

2 D C

1 2 3 4 5 6
V (litre)

Work done in the process AB (the process is expansion, hence work is done by the gas)
= – P × V = –12 × 105 × 5 × 10–3
= – 6000 J
Work done in the process B  C is zero as volume remains constant.
Work done in the process C  D (The process is contraction, hence work is one on the gas)
= P × dV = 2 × 105 × 5 × 10–3
= 1000 J
Work done in teh process D  A is zero a volume remains constant.
Net work one in the whole cycle = – 6000 + 1000 = – 5000 J
i.e. net work is done by the gas.

Illustration:
Calculate the work done when 1.0 mole of water at 373K vaporizes against an atmospheric
pressure of 1.0 atmosphere. Assume ideal gas behaviour.
Solution :
The volume occupied by water is very small and thus the volume change is equal to the volume
occupied by one gram mole of water vapour.
nRT 1.0  0.821 373
V= = = 31.0 litre
P 1.0
W = –Pext × V
= –(1.0) × (31.0) litre-atm
= –(31.0) × 101.3 J
= 3140.3 J

Illustration:
Calculate the work done when 50 g of iron is dissolved in HCl at 25ºC in :
(i) a closed vessel and
(ii) an open beaker when the atmospheric pressure is 1 atm.
Solution:
(i) When the reaction is carried in a closed vessel, the change in volume is zero. Hence,
the work done by the system will be zero.

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(ii) When iron dissolves in HCl, hydrogen is produces.

Fe + 2HCl FeCl2 + H2
56 g 1 mole
1
50 g × 50 mole
56
Volume of hydrogen produced at 25ºC
nRT 50 0.0821 298
= = ×
P 56 1
= 21.84 L
This is equal to volume change when the reaction is carried in open beaker.
Work done by the system = – PV = – 1.0 × 21.84
= – 21.84 litre–atm
= – 2212.39 J

Illustration:
Calculate the amount of work done by 2 mole of an ideal gas at 298 K in reversible isothermal
expansion from 10 litre to 20 litre.
Solution:
Amount of work done in reversible isothermal expansion
V2
w = –2.303nRT log
V1
Given n = 2, R = 8.314 JK–1 mol–1, T = 298 K, V2 = 20 L and V1 = 10L.
Substituting the values in above equation
20
w = –2.303 × 2 × 8.314 × 298 log
10
= –2.303 × 2 × 8.314 × 298 ×0.3010
= –3434.9 J
i.e., work is done by the system.

HEAT CAPACITY

It is defined as the quantity of heat required to raise the temperature of the system by one degree.
dq
i.e. C =
dT
where C = Heat capacity, dq = Amount of heat absorbed by the system and dT = Rise in temperature
Its unit is J K–1 or J / oC
Larger the sample, greater is its heat capacity. It is therefore, common to use specific heat capacity
(specific heat) or molar heat capacity.

SPECIFIC HEAT

The amount of heat required to raise the temperature of 1 gm of a substance by 1 degree is called specific
heat.
Heat capacity Heat absorbed
 Specific heat = =
mass (in gm) Rise in temperature  mass (in gm)
Heat capacity
Molar heat capacity =
Molar mass
Units of specific heat & molar heat capacity are JK–1 g–1 and JK–1 mol–1 respectively.
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 Thermodynamics Ch. XI

Now, heat supplied = Mass  Specific heat  rise in temperature

i.e. q = m  Cs  T ... (v)
The heat capacity of a system, especially in a gaseous system determined at constant time is different from
that at constant pressure.
At constant volume qv = E.
so, heat capacity at constant volume per mole,

 dE 
Cv    ... (vi)
 dT  v
At constant pressure, qp = H.
so, heat capacity at constant volume per mole,

 dH 
Cp    ... (vii)
 dT  p
where Cp & Cv are molar heat capacities of constant pressure & constant volume respectively. The heat
capacity at constant pressure (Cp) is "generally" larger than that at constant volume (Cv) because at constant
pressure, a part of heat added to the substance may be used in work of expanding whereas at constant
volume all the added heat produces a rise in temperature. The term "generally" has been used because
substances generally expand with increase of temperature at constant pressure, but in exceptional cases,
there may be a contraction, e.g. water between 1o & 4oC.

Illustration:
A gas expands from a volume of 3.0 dm3 to 5.0 dm3 against a constant pressure of 3.0 atm. The
work done during expansion is used to heat 10.0 mole of water of temperature 290.0 K. Calculate
the final temperature of water .
[ specific heat of water = 4.184 JK–1 g–1 ]
Solution:
Work done = P ×dV = 3.0 × (5.0 – 3.0) = 6.0 litre–atm = 6.0 × 101.3 J = 607.8 J
Let T be the change in temperature.
Heat absorbed = m × S × T = 10.0 × 18 × 4.184 × T
Given P × dV = m × S × T
P  dV 607.8
or T = = = 0.807
mS 10.0  18.0  4.184
Final temperature = 290 + 0.807 = 290.807 K

Illustration:
How much heat is required to change 10 g ice 0ºC to steam at 100ºC? Latent heat of fusion and
vaporization for H2O are 80cal/g and 540cal/g respectively. Specific heat of water is 1 cal/g.
Solution:
Total heat absorbed
= Hfusion + Htemp.rise + Hvap.
= 10 × 80 + 10 × 1 ×100 + 10 + 540 = 7200 cal.

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 Thermodynamics Ch. XI

PRESSURE-VOLUME WORK

Isothermal Expansion
No heat flows out of or into the system in an isothermal expansion, so that temperature remains constant
throughout the process of expansion. Since for an ideal gas, the internal energy (E), depends only on
temperature, the internal energy of the gas remains constant.
i.e.  = 0
From Ist law of thermodynamics
E = q + w
For isothermal process, E = 0, hence
q = –w
In the case of isothermal expansion, work is done by the system at the cost of heat absorbed. The magnitude
of 'q' or 'w' depends on the manner in which the process of expansion is carried out i.e. reversibly or
irreversibly.
H can be calculated as follows
We know, H = E + ngRT
For isothermal process, E = 0 & T = 0 thus, H = 0

Illustration:
The heat of combustion of ethylene at 18ºC and at constant volume is –335.8 kcal when
water is obtained in liquid state. Calculate the heat of combustion at constant pressure
and at 18ºC.
Solution:
The chemical equation for the combustion of C2H4 is
C2H4(g) + 3O2(g) = 2CO2(g) + 2H2O (l); E = –335.8 kcal
1mole 3 mole 2 mole
No. of moles of gaseous reactants = (1 + 3 ) = 4
No. of moles of gaseous products = 2
So n = (2 – 4) = –2
Given E = –335.8 kcal, n = –2, R = 2 × 10–3 kcal
and T = (18 + 273) = 291 K
H = E + nRT
= –335.8 + (–2) (2×10–3) (291) = –336.964 kcal

Illustration :
The enthalpy of formation of methane at constant pressure and 300 K –75.83 kJ. What will
be the heat of formation at constant volume ? [ R = 8.3 JK–1 mol–1 ]
Solution :
The equation for the formation of methane is
C(s) + 2H2(g) = CH4(g) ; H = –75.83 kJ
2 mole 1 mole
n = (1 – 2) = –1
Given H = –75.83 kJ, R = 8.3 × 10–3 kJ K–1 mol–1
T = 300 K
Applying H = E + nRT
–75.83 = E + (–1) (8.3 × 10–3) (300)
E = –75.83 + 2.49
So = –73.34 kJ
52 COLLEGES: ANDHERI / BORIVALI / CHEMBUR / DADAR / KALYAN / KHARGHAR / NERUL / POWAI / THANE
 Thermodynamics Ch. XI

WORK-DONE IN REVERSIBLE ISOTHERMAL EXPANSION

Let us consider a non-isolated cylinder fitted with a

weightless and frictionless piston containing an ideal
gas. Let P be the pressure of the gas which equals
external pressure. Pext.
Pext = P
An infinitesimal expansion in volume, dV results from
an infinitesimal decrease in the external pressure, say
dP. Consequently, the pressure of the gas inside the
cylinder falls to (Pext – dP) i.e. it equals again to the
external pressure and the piston come to rest again.
The work done by the gas in each step of expansion is given as
dw = – (Pext – dP) dV = –Pext. dV = – PdV
dP.dV is the product of two infinitesimal quantities and hence neglected.
The total amount of work done during the isothermal reversible expansion of the gas from volume V1 to V2
is given by
2 v2 v2
nRT
 dw   PdV   dV PV  nRT 
1 v1 v1
v
2 v2
dV
 dw   nRT 
1 v1
V

V2
w = –nRT ln V
1

V2
wrev= – 2.303 nRT log10 V ... (viii)
1

At constant temperature,
P1V1 = P2V2
V2 P1

V1 P2

P1
 wrev = –2.303 nRT log10
P2
For isothermal compression, work done by an ideal gas is same as isothermal expansion but with positive
sign. Thus equation (viii) & (ix) is the maximum work done in an expansion, or the minimum work needed
to effect a compression. This equation tells us that the work required to compress a gas from 10 atmto 100
atm is just the same as that required to compress a gas from 1 atm to 10 atm.

Work done in Irreversible isothermal expansion

Irreversible isothermal expansions observed are
(i) Free expansion
(ii) Intermediate expansion

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 Thermodynamics Ch. XI

Since the external pressure is zero in free expansion, the work done is zero e.g. expansion of a gas in
vacuum.
The external pressure is less than gas pressure in the case of intermediate expansion. Thus, the work done
when volume changes from V1 to V2 is
v2

Wirrev   P ext  dV
v1

= – Pext (V2 – V1)

Since, Pext is less than the pressure of the gas, the work done during intermediate expansion is numerically
less than that during reversible isothermal expansion in which Pext is almost equal to P.

ADIABATIC EXPANSION

From first law of thermodynamics, E = q + w

In an adiabatic expansion, q = 0, E = w
The molar heat capacity at constant volume of an ideal gas is given by

 dE 
Cv   
 dT  v
or dE = Cv. dT
and for finite changes, E = Cv  T = w ... (x)
The value of T depends upon the nature of process (i.e. reversible or irreversible)

REVERSIBLE ADIABATIC EXPANSION

If P be the external pressure and V be the increase in volume, then work done by the system is
w = – PV
If T is the fall in temperature, then
CvT = – PV
For every small changes in a reversible process and for one mole of a gas.
RT
CvdT = – PdV = .dV
V
dT dV
or, C v R
T V
For a process that takes the gas from a volume V1 at a temperature T1 to a new volume V2 at a temperature
T2, we have
T2 2 v
dT dV
Cv  R
T1
T v1
V

T2 V
C v ln   R ln 2
T1 V1

T2 R V
log  log 2 ... (xi)
T1 C v V1

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 Thermodynamics Ch. XI
We know that
CP – CV = R
Dividing it by Cv gives
CP R
1
CV CV

R  Cp 
 1   
CV  Cv 
Putting the value of R/Cv in equation (x)

T2 V V 
log     1 log 1  log  1 
T1 V2  V2 
1
T2  V1 
 
T1  V2 

T1 V FG IJ  1

T2
 log 2
V1H K ... (xii)

T1V1 – 1 = T2V2 – 1
or T1V1 – 1 = constant
 1
P1V1 V 
  2 or P1V1  P2 V2 or PV = constant
P2 V2  V1 
The above integration assumes that Cv is a constant and not a function of T. We know, for isothermal
expansion, PV = constant
On plots of P versus V, curves for reversible adiabatic process are steeper than those for normal
process as given below.

When a gas expands isothermally, thermal energy is supplied to make up for the energy delivered to the
mechanical surroundings. For a balanced adiabatic expansion, work is done by the system on the surroundings
(–w) i.e. the energy delivered to the surroundings must come from the internal of the gas. As a result, the
temperature falls (–E) and the pressure change for a given expansion is greater than that in the
corresponding isothermal expansion. From equation (xii).
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 Thermodynamics Ch. XI

 1
T1  T2 T1   RT1 
    V1  
T2  T2 T2   P1 

 1
 T1   P2 
or      ... (xiii)
 T2   P1 

R
Now, work done = Cv  T = Cv (T2 – T1) = (T – T1)
 1 2

nR
For n moles of a gas, work done = (T – T1)
 1 2

IRREVERSIBLE ADIABTIC EXPANSION

In free expansion, the external pressure is zero, i.e., work done is zero.
 E = w = 0
& T = 0 & H = 0
In intermediate expansion, suppose the pressure is suddenly released to 1 atm and the gas expands
adiabatically against this constant pressure. Since this is not a reversible expansion equation (xii) cannot be
used
Since q = 0, E = w
w = Cv (T2 – T1) ... (xiv)
Let the volume changes from V1 to V2 against external pressure, Pext.

FG RT  RT IJ = – P R FG T P  T P IJ
H PP K
2 1 1 2

HP PK
2 1
w = –Pext (V2 – V1) = – Pext ext
... (xv)
1 2
2 1

Equating equations (xiv) & (xv), we get

FG T P  T P IJ
H PP K
2 1 1 2
w = Cv (T2 – T1) = – R Pext ... (xvi) (For one mole)
1 2

THERMOCHEMISTRY

It is a branch of physical chemistry that deals with energy changes accompanying chemical
transformations. It is also known as "Chemical Energetics". It is based on the first law of
thermodynamics.
Physicochemical changes are classified as endothermic, accompanied by absorption of heat and
exothermic, accompanied by the evolution of heat. For example.
H2(g) + ½ O2 (g)  H2O (g) ; H = –57.8 kcal
H2O (g)  H2 (g) + ½ O2 (g); H = 57.8 kcal
Like any other transfer of hear, the heat of a chemical reaction depends upon the conditions that hold
during the process by which it is carried out.
Condition I:
If the volume of the system is 'kept constant, no work is done on the system and the first law of
thermodynamics reduces to
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 Thermodynamics Ch. XI
E = qv
This condition is excellently approximated when the reaction is carried out in a bomb calorimeter, where
the volume remains constant.
Condition II:
During the course of an experiment under ordinary bench-top conditions, the pressure is kept constant.
Many calorimeters operate at this constant atmospheric pressure. Then, we have
H = qp
The heat of reaction measured at constant pressure if exactly equal to the change in enthalpy of the reaction
system.
It is often necessary to use data obtained with bomb calorimeter which given E in order to calculate H.
We know that, H = E + (PV)
If all the reactants and products are liquids or solids, the PV values change only slightly during the reaction,
provided the pressure is low (say 1 atm). In such cases qp  qv.
For reactions in which gases are involved, the values of (PV) depends on the change in the number
of moles of gas as a result of reaction.
 (PV) = ng (RT)
 H = E + ng RT
Constant pressure processes are much common in chemistry,. Therefore, usually when ever we speak
of heat of reaction, it implies enthalpy change at constant pressure.

HEAT OF REACTION
It is defined as the amount of heat evolved or absorbed when the reacting species, as represented by
a balanced chemical equation have completely reacted.
Enthalpy of heat of reaction is given by H = HP –  HR

STANDARD STATES
In the calculations of reaction. It is a convention to assume that the heat of formation of element in their
standard state is zero. A pressure of 1 atm and a constant temperature is taken as standard state.
State Standard state
Gas Ideal gas at the given temperature & 1 atm.
Liquid Pure liquid at the given temperature & 1 atm.
Gas Stable crystalline form at given temperature and 1 atm pressure.

FACTORS AFFECTING HEAT OF REACTION

(I) Physical state of Reactants and Products

Physical state always affects the heat of reaction as heat energy is involved in changing the physical state of
a substance. For example,
H2 (g) + ½ O2 (g)  H2O (g) ; H = – 57.8 kcal
H2 (g) + ½ O2 (g)  H2O (l) ; H = – 68.32 kcal
Difference in the value of H is observed because heat is evolved when steam condenses.
(II) Alloptropic forms of the Elements
The value of H also depends on the allotropic form used in the reaction. For example,
C (diamond) + O2 (g)  CO2 (g) ; H = – 94.3 kcal
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 Thermodynamics Ch. XI

C (amorphous) + O2 (g)  CO2 (g) ; H = – 97.6 kcal

The difference between the two values is equal to the heat absorbed when 12 g of diamond is converted
into 12 g of amorphous carbon. This is called heat of transition.
C (diamond)  C (amorphous) ; H = 3.3 kcal
(III)Enthalpies of Solution
Enthalpies of solution differ depending on whether the substances react together in dry state of in solution.
For example.
H2S (g) + I2 (g)  2HI (solution) + S (s) ; H = – 17.2 kcal
H2S (g) + I2 (solution)  2HI (solution) + S (s) ; H = – 21.93 kcal
(IV)Temperature
Enthalpy of reaction also depends on temperature at which the reaction is carried out. This is due to
variation in the heat capacity of the system with temperature.
Relation between H and E and temperature are given by Kirchoff's equation.
( H2 – H1 ) = CP ( T2 – T1 )
( 2 – 1 ) = CV ( T2 – T1 )
The above relations may be derived as follows:
For a reaction at constant pressure, H = HP – HR
Differentiating in w.r.t. T at constant P, we get

FG dH IJ  FG dH IJ  FG dH IJ  bC g  bC g
H dT K H dT K H dT K
P R
P P P R  C P
P P P

or d(H) = CP dT
Integrating this equation within appropriate limits, we get

zb z
T2 T2

g
d H  C P dT
T1 T1

H T2  H T1  C P T2  T1 b g
H T2  H T1
bT  T g
2 1
 C P ... (xvii)

This equation is used to find heat of reaction at a temperature when it is known at another temperature.
E T2  E T1
Similarly
bT  T g
2 1
= Cv ... (xviii)

In the limits as ( T2 – T1)  0., equation (xvii) yields the differential form

d H b g
 C P
dT
This shows that the rate of change of the enthalpy of a reaction is equal to the difference in heat capacities
of products and reactants.
Since actually the heat capacities themselves vary with temperature, it is sufficiently accurate to use the
average value of the heat capacity over the range of temperature considered.

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 Thermodynamics Ch. XI

ENTHALPY OR HEAT OF FORMATION

The amount of heat evolved or absorbed when one mole of a substance is formed from its constituent
elements is called heat of formation.
H2 (g) + Cl2 (g)  2HCl (g) ; H = – 44 kcal
Thus, enthalpy of formation of HCl is – 22 kcal
The formation reaction of a compound has only one mole of the compound and nothing else on the product
side., Only elements in their stable states of aggregations appear on the reactant side.

STANDARD ENTHALPY OF FORMATION ( H of )

It is enthalpy change of a reaction by which a compound if formed when its constituents elements, that
reactants and products all being in a given, standard state (i.e., at 298 K and 1 atm pressure). For example.
S (s) + O2 (g)  SO2 (g) ; H of = – 296.9 kJ

3
2AI (s) + O (g)  Al2O3 (s) ; H of = – 1669.8 kJ
2 2
Let us consider a reaction, C(s) + O2 (g)  CO2 (g) ; H of = – 393.5 kJ

H of  H oP  H oR  3935
. kJ
Enthalpies of free elements in their standard states are assumed to be zero.
so, H of  H oP  393.5 kJ
The compounds having positive enthalpies of formation are called endothermic compounds and are
less stable than the reactants and those having negative enthalpies of formation are known as exothermic
compounds and are more stable than the reactants.
If we know that standard heats of formation of various substances, we can calculate heat of reactions
under standard conditions.
Thus,

FG Sum of the standard heatsIJ  FGSum of the standard heatsIJ

Ho of a reaction =
H of formation of products K H of formation of reactants K
  H b Productsg   H b reactantsg
o o
i.e. H o f f

The heat of formation of all the elements in their standard states are arbitrarily taken to be zero, For
example, at 1 atm and 298 K, the stable state if aggregation of bromine is the liquid state. Hence liquid
bromine, gaseous hydrogen solid zinc, solid (rhombic) sulphur and solid (graphite) carbon, all have H o298
=0
For elementary solids that exists in more than one crystalline form, the modification that is stable at 25oC
and 1 atm is assigned Ho = 0,. For example, zero assignment goes to rhombic sulphur rather than to
monoclinic sulphur, to graphite rather than diamond. In cases in which more than one molecules species
exists (e.g. O2 and O3) , the zero enthalpy value goes to the most stable form at 25oC and 1 atm pressure
i.e. for O2, H o298 (O2, g) = 0.

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 Thermodynamics Ch. XI

Once, the value of the standard enthalpy of the elements at 298 K has been assigned, the value at any other
temperature can be calculated using Kirchoff's equation

z z
T T
o
dH  C op dT
298 298

z
T

H oT  H o298  C opdT
298

z
T
o o
H H T 298  C op dT
298

This expression holds good for both elements as well as compounds. For elements, the first term on the
right hand side is zero.

ENTHALPY OR HEAT OF COMBUSTION

The amount of heat evolved or decrease in enthalpy when one mole of a substance is completely oxidised.
Organic compounds containing only carbon, hydrogen and oxygen are burnt to gaseous carbon dioxide
and liquid water. For example.
CH4 (g) + 2O2 (g) CO2 (g) + 2 H2O (l) ; Ho = – 890.36 kJ/mol
The measurements of the heat of combustion is used to determine the heats of formation of all organic
compounds containing C, H, O, N, etc.

ENTHALPY OR HEAT OF SOLUTION

The amount of heat evolved or absorbed when one mole of solute is dissolved in excess of solvent so that
further addition of solvent makes no heat change. For example
H2SO4 (l) + aqueous H2SO4 (aq); H = – 20.2 kcal
KCl (s) + aqueous KCl (aq); H = 4.4 kcal
Heat of an ideal solution is taken as zero.

HEAT OF DILUTION
The amount of heat evolved or absorbed when solution containing one mole of solute is diluted from one
concentration to another. For example
HCl (g) + 10 H2O HCl.10H2O ; H1 = – 69.01 kJ/mol
HCl (g) + 25 H2O HCl.25H2O ; H2 = – 72.03 kJ/mol
HCl (g) + 40 H2O HCl.40H2O ; H3 = – 72.79 kJ/mol
. . . . .
. . . . .
. . . . .
HCl (g) +  H2O HCl.H2O ; H = – 74.85 kJ/mol
If we subtract first equation from the second in the above set, we get
HCl . 10H2O + 15 H2O HCl. 25H2O ; H = ( H2 – H1 ) = – 3.02 kJ/mol
This value of H is the heat of dilution. The heat of dilution of a solution is dependent on the original
concentration of the solution and on the amount of the solvent added.

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 Thermodynamics Ch. XI

ENTHALPY OR HEAT OF NEUTRALISATOION

The amount of heat evolved or absorbed when one gram equivalent of an acid is completely neutralised by
one gram equivalent of a base in dilute solution is called heat of neutralisation. For example
HNO3 (aqueous) + NaOH (aqueous)  NaNO3 (aqueous) + H2O ( l ) ; H = – 13.7 kcal
Heat of neutralisation of a string acid and a string base is 13.7 kcal, or 57 kJ. The constant value is due to
the fact that heat of neutralisation of strong acid and strong base is merely the heat of formation of H2O
from H+ of an acid and OH– of a base.
H+ (aqueous) + OH– (aqueous)  H2O ( l ); H = – 13.7 kcal.

ENTHALPIES OR PHASE TRANSITION

(I) Enthalpy of Fusion
It is the enthalpy change involved in the conversion of one mole of a substance from solid state to
liquid state at its melting point. This equals latent heat of fusion per gram multiplied by the molar mass.
For example.
H2O (s)  H2O ( l ) ; H = 1.44 kcal / mol
(II) Enthalpy of Vapourisation
It is the enthalpy change involved in the converting one mole of a substance from liquid state to
gaseous state at its boiling point. For example
H2O ( l )  H2O (g) ; H = 10.5 kcal / mol
(III) Enthalpy of Sublimation
It is the enthalpy change involved in the conversion of one mole of a solid directly into its
vapour at a given temperature below its melting point. For example
I2 (s)  I2 (g) ; H = 14.9 kcal / mol
Hsublimation = Hfusion + Hvapourization
(IV) Enthalpy of Atomisation
The amount of heat required for the formation of one mole of atoms in gaseous state from its elements
is known as heat of atomization of that element.
C(s)  C(g) ; H = 171.7 kcal / mol
H2 (g)  2H (g) ;H = 104 kcal
In this case, heat of atomization of hydrogen is 52 kcal /mol.

Illustration:
The standard enthalpies of formation at 298 K for CCl4(g), H2O(g), CO2(g) and HCl(g) are –
106.7, – 241.8, –393.7 and –92.5 kJ mol–1, respectively. Calculate ΔH °298K for the reaction,
CCl4(g) + 2H2O(g)  CO2(g) + 4HCl(g)
Solution:
The enthalpy change of the given reaction will be given as
H  H 0f  CO2 , g   4H 0f  HCl,g   H 0f  CCl4 , g   2H0f  H 2O, g 
= ( – 393.7 – 4 × 92.5 + 106.7 + 2 × 241.8 ) kJ mol–1 = – 173.4 kJ mol–1.

Illustration:
Calculate the heat of formation of acetic acid from the following data:
(i)  2CO2(g) +2H2O(l) ; H = –207.9 kcal
CH3COOH(l) + 2O2(g) 
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 Thermodynamics Ch. XI

(ii) C(s) + O2(g) 

 CO2(g) H = –94.48 kcal
(iii) H2(g) + 12 O2(g)   H2O(l) H = –68.4 kcal
Solution:
First method : The required eqation is
2C(s) + 2H2(g) + O2(g) = CH3COOH(l); H = ?
This equation can be obtained by multiplying Eq. (ii) by 2 and also Eq. (iii) by 2 and adding both
and finally substracting Eq.(i)
[2C + 2O2 + 2H2 + O2 – CH3COOH(l) –2O2 = 2CO2 + 2H2O –2CO2 – 2H2O]
H CH3COOH (l ) = 2 × (–94.48) + 2 (–68.4)– (–207.9)
= –188.96 – 136.8 + 207.9
= –325.76 + 207.9 = –117.86 kcal
Second method : From eq. (ii) and (iii)
Enthalpy of CO2 = – 94.48 kcal
Enthalpy of H2O = – 68.4 kcal
Enthalpy of O2 = 0 (by convention)
H of Eq. (i) = Enthalphies of products = Enthalpies of reactants
–207.9 = 2 × (–94.48) + 2(–68.4) – H CH3COOH (l )

H CH3COOH (l ) = –188.96 – 136.8 + 207.9 = –235.76 + 207.9 = –117.86 kcal

Illustration:
How much heat will be required to make 2 kg of calcium carbide (CaC2) according to the following
reaction ?
CaO (s) + 3C(s)  CaC2(s) + CO(g)
The heats of formation of CaO (s), CaC2(s) and CO(g) are –151.6, –14.2 and –26.4 kcal
respectively.
Solution: H = H°f(products) – H°f(reactants)
= [H°f(CaC2) + H°f(CO)] – [H°f(CaO) + 3H°f(C)]

= [–14.2 –26.4] – [–151.6 + 3 × 0]

= –40.6 + 151.6 = 111.0 kcal
For formation of 64 g of CaC2 111.0 ckal of heat is required.
So, heat required for making 2000 g of
111.0
CaC2 = × 2000 = 3468.75 kcal
64

HESS'S LAW OF CONSTANT HEAT SUMMATION

The change in state of a system produced by a specified chemical reaction is definite. The corresponding
enthalpy change is definite, since the enthalpy is a state function.
Thus " if a specified set of reactants is transformed to a specified set of products by more than one
sequence of reactions, the total enthalpy change must be the same for every sequence."
This rule, which is a consequence of the first law of thermodynamics, is known as Hess's law, More
precisely. "The enthalpy change in a chemical or physical process is same whether the process is carried
out in one step or in several steps". For example

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 Thermodynamics Ch. XI

 H = H1 + H2
This property is due to the fact that the enthalpy change in a system is independent of the path followed.

APPLICATION OF HESS'S LAW

(i) Using Hess's law, enthalpy changes for the reactions, which are experimentally not possible, can be
calculated.
e.g. for compounds such as C2H6, C6H6 etc. whose direct synthesis from their constituent elements is
not possible, the enthalpy of formation of such compounds can be calculated.
(ii) Calculation of Heat of Reaction
Hreaction =  Heat of formation of Products –  Heat of formation of reactants
Hreaction =  Heat of combustion of reactants –  Heat of combustion of products

BOND ENERGIES
The quantity of heat evolved when one mole of a bond of particular type is formed between the two
free atoms in gaseous state to give molecule in gaseous state, is called as the bond energy of bond
formation energy –
Bond energy may be alternatively defined as "the amount of energy required to break one mole of a
type of a bond in gaseous state."
APPLICATION OF BOND ENERGIES
(i) Determination of Heat of Reactions
Hreaction = Sum of bond energies of reactants – Sum of bond energies of products.
(ii) Determination of Resonance Energy
Resonance Energy = (Experimental or actual heat of formation) – (Calculated heat of formation)

Illustration:
Calculate heat of combustion of ethene:
H H
C=C + 3O = O  2O=C=O + 2H –O–H
H H
From bond energy data : C=C C–H O=O C=O O–H
–1
K.E. KJ mol 619 414 499 724 460
Solution :
H = sum of bond energies of reactants – Sum of bond energies of products
= [H(C=C) + 4H(C–H) + 3 × H(O=O)] – [4 × H(C=O) + 4 × H(O–H)]
= [619 + 4 × 414 + 3 × 499] – [ 4× 724 + 4 × 460]
= –964 kJ mol–1

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 Thermodynamics Ch. XI

Illustration:
Bond dissociation enthalpies of H2(g) & N2(g) are 436.0 kJ mol–1 and 941.8 kJ mol–1 and enthalpy
of formation of NH3(g) is – 46 kJ mol–1. What is enthalpy of atomization of NH3(g)? What is the
average bond enthalpy of N–H bond?
Solution :
N2(g) + 3H2(g)  2NH3(g) ; H = –2 × 46 kJ/mol
H = (B.E.)R – (B.E.)P
= (941.8 + 3 × 436) – (6x) = –2 × 46 kJ/mol
(here x = average B.E. of N–H bonds)
x = 380.3 kJ mol–1
NH3  N + 3(H)
Heat of atomization = 3 × 390.3 = 1170.9 kJ mol–1

Illustration:
Compute the resonance energy of gaseous benzene from the following data.
 (C — H) = 416.3 kJ mol–1
 (C — C) = 331.4 kJ mol–1
 (C = C) = 591.1 kJ mol–1
ΔΗ °sub  C, graphite  = 718.4 kJ m ol -1
°
ΔH diss  H 2 , g  = 435.9 kJ mol -1
ΔH °f  benzene, g  = 82.9 kJ mol -1
Solution:
To compute resonance energy, we compare the calculated value of ΔH °f (benzene, g) with

the given one. To calculate ΔH °f (benzene, g), we add the following reactions.
6C(g)  6H(g)  C6H 6 (g) H    3 CC  3C C  6C H 

6C(graphite)  C(g) H  6  718.4 kJ mol1

Add 3H 2 (g)  6H(g) H  3  435.9 kJ mol1

6C(graphite) + 3H2(g)  C6H6(g)

The corresponding enthalpy change is
 f H    3CC  3CC  6CH   6  718.4 + 3× 435.9  kJ mol 1
= [ – ( 3 × 331.4 + 3 × 591.1 + 6 × 718.4 + 3 × 435.9] kJ mol–1
The given H 0f is H 0f (benzene, g) = 82.9 kJ mol–1
This means benzene becomes more stable by (352.8 – 82.9) kJ mol–1,
i.e.,269.7 kJ mol–1 . This is its resonance energy.

SPONTANEOUS PROCESS

A process which can proceed by itself under given set of conditions once it has been properly initiated, if
necessary, is known as spontaneous process. They are also called feasible or probable processes.

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 Thermodynamics Ch. XI

STATEMENT OF IIND LAW OF THERMODYNAMICS

Second law of thermodynamics is concerned with the direction and spontaneity of processes. There are
many ways of formulating the law based on our experience of the direction or manner in which natural
processes occur. Clausius stated the law as "The transference of heat from a cold to a hot body
cannot be achieved without the performance of work".
Because natural or spontaneous processes occur over a period of time, they must be thermodynamically
irreeverersible. Another way of formulating the second law is "Any process occurring on its
thermodynamically irreversible".
The basic concept of the second law of thermodynamics is that all spontaneous processes are
unidirectional and thermodynamically irreversible.

ENTROPY (S):

It is a thermodynamic property and is a measurement of the disorder or randomness of system. The more
disordered system has a higher entropy. For example, entropy increase in the order.
Solid < liquid < gas.
Entropy of a system is a state function, i.e., it depends upon the initial and final states of the system. When
the state of a system changes, the entropy also changes. The change in entropy S, is defined as
q
S  iso.rev
T
Where qiso.rev = heat supplied isothermally and reversibly. T is the temperature on absolute scale.

ENTROPY AS THE CAPACITY FOR SPONTANEOUS CHANGE

Let us consider the following examples of spontaneous change.
(i) Expansion of a gas from a region of high pressure to a region of low pressure Suppose, there
are two bulbs filled with a gas at different pressures. If the two bulbs are connected, the gas from the
bulb at high pressure will flow into the bulb at low pressure till the pressures in the two bulbs become
equal. The greater the pressure difference, the greater the flow of gas, the greater is the capacity
of the system for spontaneous change and the greater is the entropy change.
(ii) Solute spreading from a region of high concentration to a region of low concentration If the
concentration differences two solution is considerable, there is obviously a much greater flow of solute
from the high concentration to the lower concentration region.
Since energy of universe is constant and some processes occur to increase their entropy without
change in enthalpy, Ssystem + Ssurr > 0.
 For an irreversible spontaneous change Stotal is +ve
 For a reversible change at equilibrium Stotal = 0
 Entropy change in the isothermal reversible expansion of a gas is given by–
V2
S = 2.303 nR log V
1
Illustration:
A heated copper black at 130ºC loses 340 J of heat to the surrounding which are at room temperature
of 32ºC. Calculate :
(i) the entropy change of the system (copper block)
(ii) the entropy change in the surroundings.
(iii) the total entropy change in the universe due to this process
Assume that the temperature of the block and the surroundings remains constant.
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 Thermodynamics Ch. XI

Sol. Tsystem  130º C  130  273K  403K,Tsurr  32º C  32  273K  305K

qsystem  340J, q surr  340J

q system 340J
(i) Ssystem    0.84JK 1
Tsystem 403K

qsurr 340J
(ii) Ssurr    1.11 J K 1
Tsurr 305K
(iii) Stotal or Suniverse = Ssystem + Ssurr. = 0.84 + (+1.11) JK–1 = 0.27 J K–1

Illustration:
At 0ºC, ice and water are in equilibrium and H = 6.00 kJ mol–1 for the process
H2O(s)  H2O(l). What will be S and G for the conversion of ice to liquid water ?
Sol. Since the given process is in equilibrium, G = 0
Putting the value in the relationship, G = H  TS, we get
0 = H TS or TS = H or S = H/T
we are given H = 6.0 kJ mol–1 = 6000 J mol–1 and T = 0ºC = 273 K
6000 J mol 1
 S   21.98 J K 1mol 1
273 K

FREE ENERGY CHANGE (G)

The two thermodynamics quantities, which affect the spontaneity of a reaction, are enthalpy (H) and
entropy (S). The next problem is how to arrange two quantities in such a way as to arrive at a single
function, which can be used to determine whether a reaction is spontaneous, or not. J. Willard Gibbs
introduced a new quantity called the Gibbs free energy and gave it the symbol G. The free energy of
a substance, like its enthalpy or entropy is a characteristics property of the substance, In any reaction,
the change in free energy, G is the difference in free energies of products and reactants.
G = Gproducts – Greactants
Gibbs showed that the sign G can be used to determine whether a reaction is spontaneous or not. For a
reaction carried out at constant temperature an pressure.

FREE ENERGY AND SPONTANEITY

The concept of free energy has been introduced to predict the spontaneity of feasibility of a process.
Enthalpy alone or entropy alone can not predict the spontaneity of a lot of reactions.
A spontaneous change may be accompanied by evolution of absorption or heat, it may result in an increase
(S positive) or decrease (S negative) in disorder or randomness of a system. Free energy of a system is
defined, as "the maximum amount of energy available to a system during a process that can be converted
into useful work."
Thus free energy is a measure of the capacity of system to do useful work. It is represented by symbol
G and is related to enthalpy H and entropy S as follows:
G = H – TS
Now H = E + PV
G = E + PV – TS, change in free energy may be expressed as:
G =E +  (PV) –  (TS)
In the process is carried out at constant temperature and pressure, then

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 Thermodynamics Ch. XI
 PV = P  V and  (TS) = T  S
G=E+ PV– TS or G= H –TS
This equation is called Gibbs Helmhottz equation.
 Stotal  Ssys  Ssurr

H sys is the enthalpy change when energy is gained by system.

H sys
 Stotal  Ssys 
T

or TStotal  TSsys  H sys

or G sys  TStotal
(i) If G is negative, the process is spontaneous
(ii) If G is zero, the process is in equilibrium. There is no net reaction in either direction.
(iii)If G is positive, the does not occur in the forward direction. It may however proceed in the backward
direction.

STANDARD FREE ENERGY CHANGE (DG) AND EQUILIBRIUM CONSTANT (K)

They are related as follows:
Gº = – 2.303 RT log K.
where Go = Free energy change for a reaction
K = equilibrium constant f or the reaction
G = {Free energy of formation of products – Free energy of formation of reactants}

ABSOLUTE ENTROPIES AND THIRD LAW OF THERMODYNAMICS

The entropy of a substance varies directly as its temperature changes. According to the third law of
thermodynamics, first formulated by Nernst in 1906, "the entropy of a perfectly crystalline substance
is zero at absolute zero."
The absolute value of entropy of any pure substance can be calculated at room temperature by virtue of
third law. For this, we have to measure changes in heat capacities. The standard absolute entropy of a
substance, So is the entropy of the substance in its standard state at 298 K and 1 atm pressure.
VAN'T HOFF REACTION
Isotherm G = Go + RT ln KP.

Illustration: Highest entropy is in

(A) Water (B) Hydrogen
(C) Mercury (D) Graphite
Solution: Randomness or disoder is maximum in gaseous phase.
 (B)

Illustration:
Show that the reaction, CO(g) + ( 1/2 ) O2(g)  CO2(g)
at 300 K is spontaneous and exothermic, when the standard entropy change is – 0,094 kJ mol–
1
K–1. The standard Gibb’s free energies of formation of CO2 and CO are – 394.4 and
–137.2 kJ mol–1 respectively.

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 Thermodynamics Ch. XI

Solution :
The given reaction is ,
CO(g) + (1/2) O2(g)  CO2(g)
 1 
G  (for reaction) = G CO2  G CO    G O2
2
= – 394.4 – ( – 137.2 ) – 0
= – 257.2 kJ mol–1
Gº = Hº – TS
– 257.2 = H – 298 × (0.094)
or Hº = –288.2 kJ
Gº is –ve, hence the process is spontaneous, and H is also –ve, hence the process is
also exothermic.

Illustration:
Calculated the standard free energy change for the reaction
4NH 3 (g)  5O2 (g) 
 4NO(g)  6H 2O(l ) .
Given that the standard free energies of formation (f G 0 ) for NH 3 (g) , NO(g) and H 2 O(l ) are –
16.8, +86.7 and –237.2 kJ mol–1 respectively. Predict the feasibility of the above reaction at the
standard state.
Solution: Given, f G 0 (NH 3 )  16.58 kJ mol1
f G 0 (NO)  86.7 kJ mol1
f G 0 (H 2 O)  237.2 kJ mol1
r G 0  f G 0 ( Products )  f G 0 ( Reactants )
 [4 f G 0 (NO)  6 f G 0 (H 2O)]  [4 f G 0 (NH 3 )  5 f G 0 (O 2 )]
 [4  (86.7)  6  (237.2)]  [4  (16.8)  5  (0)]  1009.2 kJ
Since, r G 0 is negative, the process is feasible.

Illustration:
3
Calculate r G 0 for conversion of oxygen to ozone O2 (g)  O3 (g) at 298 K, If Kp for this
2
conversion is 2.47 × 10–29.

Solution: r G 0  2.303 RT log K p  (2.303)(8.314 JK 1mol1 )(298 K)log(2.47 1029 )

 163.2 kJmol1
For standard conditions, T = 298 K and log(2.47 1029 )  29  0.3927  28.6073

Illustration:
 PCl3 (g)  Cl 2 (g) at 298 K, K c  1.8107. What is G 0 for
For the equilibrium, PCl5 (g) 
the reaction ? (R = 8.314 J K–1 mol–1)

Solution: K p  K c (RT)n

Here, n  n p  n r  2 1  1, T  298 K, R  8.314 JK1mol1

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 Thermodynamics Ch. XI

 K p  (1.8107 )(8.314  298)  4.46104

 r G 0  2.303 RT log K p  2.3038.314  298 log(4.46104 )
 19118.6 J mol1  19.12 kJ mol1

Illustration:
Calculate the equilibrium constant, K for the following reaction at 400 K ?
 2NO(g)  Cl 2 (g)
2NOCl(g) 
Given that r H 0  80.0 kJ mol1 and rS0  120 J K1 mol1 at 400 K.
Solution: r G 0  r H 0  T rS0  80000J  400 120 J  32000 J
Now, r G 0  2.303 RT log K
 32000  2.3038.314  400  log K or log K  4.1782  5.8218
 K  anti log 5.8218  6.634 105

Illustration:
At 60ºC, dinitrogen tetroxide is 50% dissociated. Calculate the standard energy change at this
temperature and one atmosphere.

Solution:  2NO 2 (g)

N 2O4 (g) 
Initial amount 1 mole 0

At eqm. 1  0.5 = 0.5 mol 0.5  2 = 1 mol Total = 1.5 mol

0.5 1 1 2
PN2O4  1 atm  atm, PNO2  1 atm  atm
1.5 3 1.5 3
PNO2 (2 / 3) 2
Kp    1.33 atm
PN2O4 (1 / 3)

 r G 0  2.303 RT log K p  2.303 (8.314 JK 1 )(333K) log1.33  790 J mol1

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 Thermodynamics Ch. XI

SOLVED OBJECTIVE EXAMPLES

Problem 1:
If 1.00 kcal of heat is added to 1.2 L of oxygen in a cylinder at constant pressure of 1.000
atm, the volume increases to 1.5 L, Hence E for this process is:
(A) 0.993 kcal (B) 1.0073 kcl (C) 0.0993 kcal (D) 1.00073 kcal
Solution : (A)
H = E + PV
1(1.5  1.2) L atm
1.00 = E + × 2 × 10–3 kcal
0.082 L atm
E = 0.993 kcal

Problem 2 :
Using only the following data:
(I) Fe2O3(s) + 3CO (g) 2Fe(s) + 3CO2 (g) ; H° = – 26.8 kJ
(II) Fe(s) + CO(g) FeO(s) + CO(g) ; Hº = + 16.5 kJ
the H° value, in kilojoules, for the reaction Fe2O3(s) + CO(g) 2FeO(s) + CO2(g) is
calculated to be:
(A) –43.3 (B) –10.3 (C) +6.2 (D) +10.3
Solution : (C)
from equation (I) + (2 × II) ; Hº = 6.2 kJ

Problem 3 :
Enthalpy change when 1.00 g water is frozen at 0ºC, is : (Hfus = 1.435 kcal mol–1)
(A) 0.0797 kcal (B) –0.0797 kcal (C) 1.435 kcal (D) – 1.435 kcal
Solution : (B)
 1.435
H (per g) = kcal = 0.0797 kcal g–
18

Problem 5:
The C–Cl bond energy can be calculated from:
(A) H°f (CCl4, l) only
(B) º f (CCl4, l) and D(Cl2)
(C) H°f (CCl4, l) D(Cl2)
(D) H°f (CCl4, l) D(Cl2), H°f (C, g) and H°vap (CCl4)
Solution : (D)
C(s) + 2Cl2(g)  CCl4(l)
Hf (CCl4, l) = Hº[C(s)  C(g)] + 2(BE)Cl–Cl – [H°vap (CCl4) + 4(BE)Cl–Cl]

Problem 6 :
Enthalpy of fusion of a liquid is 1.435 kcal mol–1 and molar entropy change is 5.26 cal
mol–1 K–1. Hence melting point of liquid is :
(A) 100ºC (B) 0ºC (C) 373 K (D) –273º

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 Thermodynamics Ch. XI
Solution : (B)
H H 1435cal
S = T=  = 273 K 0ºC
T S 5.26

Problem 7 :
For the reaction
X2O4 (l) 2XO2(g)
E = 2.1 kcal. S = 20 cal/K at 300 K
Hence G is :
(A) 2.7 kcal (B) –2.7 kcal (C) 9.3 kcal (D) –9.3 kcal
Solution : (B)
H = E + ng RT = 2.1 + 2 × 0.002 × 300 = 3.03 kcal
G = H – TS = 3.3 – 300 × (0.02) = –2.7 kcal

Problem 9 :
1 g H2 gas at S.T.P. is expanded so that volume is doubled. Hence work done is:
(A) 22.4 L atm (B) 5.6 L atm (C) 11.2 L atm (D) 44.8 L atm
Solution : (C)
V1 (volume of 1 g H2) = 11.2 L at NTP
V2 (volume of 1 g H2) = 22.4 L
 W = PV = 11.2 L atm

Problem 10 :
Following reaction occurs at 25ºC :
2N O(g, 1 × 10–5 atm) + Cl2(g, l × 10–2 atm) 2NOCl(g, l × 10–2 atm)
ºG is:
(A) –45.65 kJ (B) –28.53 k J (C) –22.82 kJ (D) –57.06 kJ
Solution : (A)
2
PNOCl
G° = –2.303 RT log Keq Keq = 2 = 108 Hence Gº = –45.65 kJ
PNO PCl 2

Problem 11 :
1 mol of NH3 gas at 27ºC is expanded under adiabatic condition to make volume 8 times ( =
1.33). Final temperature and work done respectively are:
(A) 160 K, 900 cal (B) 150K, 400 cal (c) 250 K, 1000 cal (D) 200 K, 800 cal
Solution : (A)
 1 1.331
 V1  1

T2 = T1  
 = 300 ×   = 150 K
 V2  8
 = –CvT = –Cv(T2 – T1) (  for adabatic process w = –q)
Cv  R
= – 3 × 2 × (150 – 300) = 900 cal ( = 1.33  CV = 3 × R)
Cv

Problem 12 :
Temperature of 1 mol of gas is increased by 1º at constant pressure. Work done is:
(A) R (B) 2R (C) R 2 (D) 3R

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 Thermodynamics Ch. XI

Solution : (A)
W = P (V)
PV = RT
P(V + V) = R(T + 1)  PV + PV = RT + R
 PV = R

Problem 13 :
The gas absorbs 100 J heat and is simultaneously compressed by a constant external pressure of
1.50 atm from 8 L to 2L in volume. Hence E will be:
(A) – 812 J (B) 812 J (C) 1011 J (D) 911 J
Solution : (C)
H = E + PV
1.5 6 
100 = E + × 8.314
0.0821
E = 1011.4 J

Problem 14 :
The standard heat of combustion of solid boron is equal to:
(A) Hº f (B2O3) (B) 12 Hºf (B2O3) (C) 2H°f (B2O3) (D) – 12 Hº f (B2OP3)
Solution : (B)

Problem 15 :
CP – Cv = R . This R is :
(A) Change in K.E.
(B) Change in rotational energy
(C) work done which system can do on expanding the gas per mol per degree
increase in temperature
(D) All correct
Solution : (C)
PV = RT at temp T for one mol
P(V + V) = R(T + 1) at temp. (T + 1) for one mol
 PV = R

Problem 16 :
For A  B , H = 4 kcal mol–1 , S = 10 cal mol–1K–1.
Reaction is spontaneous when temperature can be :
(A) 400K (B) 300K (C) 500K (D) none is correct
Solution : (C)
G = –ve for spontaneous charge
G = H – TS
H 4000
 TS > H, T >  T >  T > 400 K
S 10

Problem 17 :
If a process is both endothermic and spontaneous , then :
(A) S > 0 (B) S < 0 (C) H < 0 (D) G > 0

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 Thermodynamics Ch. XI
Solution : (A)
As G = H – TS
For spontaneous process, G = negative
For endothermic process, H = positive
Therefore S > 0

Problem 18 :
For which change H  E
(A) H2 + I2 2HI (B) HCl + NaOH  NaCl + H O
2
(C) C(s) + O2(g) CO2(g) (D) N2 + 3H2 
 2NH
3
Solution : (D)
H  E  nRT

Problem 19 :
If a chemical change is brought about by one or more methods in one or more steps, then the
amount of heat absorbed or evolved during the complete course of reaction is same, which ever
method was followed. This law is known as
(A) Le Chatelier’s principle (B) Hess’s law
(C) Joule Thomson effect (D) Trouton’s law
Solution : (B)
The statement is definition of Hess’s law

Problem 20 :.
The Kirchhoff’s equation gives the effect of ..... on heat of reaction.
(A) Pressure (B) Temperature (C) Volume (D) Molecularity
Solution : (B)
Kirchhoff’s equation is : H2  H1 = CP (T2  T1)

Problem 21 :.
The heats of neutralisation of four acids A , B , C , D are – 13.7, – 9.4, – 11.2 and – 12.4 kcal
respectively when they are neutralised by a common base. The acidic character obeys the
order :
(A) A > B > C > D (B) A > D > C > B (C) D > C > B > A (D) D > B > C > A
Solution : (B)
Lower is heat of neutralisation , more is dissociation energy, weaker is acid

Problem 22 :.
The Hf for CO2(g), CO(g), and H2O(g) are – 393.5, –110.5 & – 241.8 kJ mol–1 respectively..
The standard enthalpy change (in kJ) for the reaction ,
CO2(g) + H2(g)  H2O(g) is :
(A) 524.21 (B) 41.2 (C) – 262.5 (D) – 41.2
Solution : (B)
Given
C + O2  CO2 ; Hº = – 393.5 kJ . . . . (i)
C + (1/2)O2  CO ; Hº = – 110.5 kJ . . . . (ii)
H2 + (1/2)O2  H2O ; Hº = – 241.8 kJ . . . . (iii)
By (ii) + (iii) – (i),
CO2 + H2  CO + H2O ; Hº = + 41.2

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 Thermodynamics Ch. XI

EXERCISE
MULTIPLE CHOICE QUESTIONS

1. Heat produced in calories by the combustion of one gram of carbon is called

(1) Heat of combustion of carbon (2) Heat of formation of carbon
(3) Calorific value of carbon (4) Heat of production of carbon

2. Conditions of standard state used in thermo chemistry is

(1) 0o C and 1 atm (2) 20o C and 1 atm
(3) 25o C and 1 atm (4) 0 K and 1 atm

3. The temperature of the system decreases in an

(1) Adiabatic compression (2) Isothermal compression
(3) Isothermal expansion (4) Adiabatic expansion

4. For the isothermal expansion of an ideal gas

(1) E and H increases (2) E increases but H decreases
(3) H increases but E decreases (4) E and H are unaltered

5. The cooling in refrigerator is due to

(1) Reaction of the refrigerator gas
(2) Expansion of ice
(3) The expansion of the gas in the refrigerator
(4) The work of the compressor

6. Point out the wrong statement in relation to enthalpy

(1) It is a state function
(2) It is an intensive property
(3) It is independent of the path followed for the change
(4) Its value depends upon the amount of substance in the system

7. In thermodynamics which one of the following is not an intensive property

(1) Pressure (2) Density (3) Volume (4) Temperature

8. If in a container neither mass and nor heat exchange occurs then it constitutes a
(1) Closed system (2) Open system
(3) Isolated system (4) Imaginary system

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

(1) S (2) G (3) H (4) Q

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

(1) Internal energy (2) Enthalpy (3) Work (4) Entropy

11. Which of the following is always negative for exothermic reaction?

(1) H (2) S (3) G (4) None of these

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 Thermodynamics Ch. XI
12. At constant T and P, which one of the following statements is correct for the reaction,
1
CO(g)  O2 (g)  CO2 (g)
2
(1) H is independent of the physical state of the reactants of that compound
(2) H  E
(3) H  E
(4) H  E

13. For the reaction N2  3H2 ⇌ 2NH3 ; H 

(1) E  RT (2) E  2RT (3) E  RT (4) E  2RT

14. “The resultant heat change in a reaction is the same whether it takes place in one or several
stages.” This statement is called
(1) Lavoisier and Laplace law (2) Hess's law
(3) Joule's law (4) Le–chatelier's principle

15. Which of the following is the correct equation?

(1) U  Q  W (2) W  U  Q (3) U  W  Q (4) None of these

16. During an isothermal expansion of an ideal gas its

(1) Internal energy increases (2) Enthalpy decreases
(3) Enthalpy remains unaffected (4) Enthalpy reduces to zero

17. 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 25o C is
(1) 2.303  298  0.082log 2 (2) 298 107  8.31 2.303log 2
(3) 2.303  298  0.082log 0.5 (4) 8.31107  298  2.303log0.5
(5) 2.303  298  2log 2

18. The law of conservation of energy states that

(1) The internal energy of a system is constant
(2) The heat content of a system is constant
(3) Energy is neither created nor destroyed
(4) There is an equivalence between energy and mass

19. A schematic plot of ln K eq versus inverse of temperature for a reaction is shown below
6.0
ln Keq

2.0
1.5×10–3 1/T (K–1) 2.0×10–3

The reaction must be

(1) Exothermic
(2) Endothermic
(3) One with negligible enthalpy change
(4) Highly spontaneous at ordinary temperature

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 Thermodynamics Ch. XI
20. In which of the following E  H
(1) N 2 O 4 (g) ⇌ 2NO2 (g) (2) 2SO2 (g)  O2 (g) ⇌ 2SO3 (g)
1
(3) H2 (g)  I2 (g) ⇌ 2HI(g) (4) H2 (g)  O2 (g) ⇌ H2O(l)
2

21. In an adiabatic expansion of an ideal gas

(1) W  E (2) W  E (3) E  0 (4) W  0

22. For the reaction

CH3COOH(l)  2O2 (g) ⇌ 2CO2 (g)  2H2O(l) at 25o C and 1 atm. pressure, H  874 kJ. Then
the change in internal energy ( E) is ….
(1) – 874 kJ (2) – 871.53 kJ (3) – 876.47 kJ (4) + 874 Kj

23. 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
(1) E  W  Q  0 (2) E  0,Q  W  0 (3) E  W  0,Q  0 (4) E  Q  0, W  0

24. For the reaction, C3H8 (g)  5O2 (g)  3CO2 (g)  4H2O(l) at constant temperature, H  E is
(1) – RT (2) + RT (3) – 3RT (4) + 3RT

25. At 27o 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)
(1) 0, – 965.84 cal ` (2) – 965.84 cal, + 965.84 cal
(3) + 865.58 cal, – 865.58 cal (4) – 865.58 cal, – 865.58 cal

26. 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
(1) 25 J (2) 30 J (3) 32 J (4) 28 J

27. A system absorbs 600J of heat and work equivalent to 300J on its surroundings. The change in
internal energy is
(1) 300 J (2) 400 J (3) 500 J (4) 600 J

28. Work done during reversible isothermal expansion of one mole of an ideal gas from 10 atm. to 1
atm at 300K is
(1) 4938.8 J (2) 4138.8 J (3) 5744.1 J (4) 6257.2 J

29. E o of combustion of isobutylene is XkJ mol1 . The value of H o is

(1)  E o (2)  E o (3)  0 (4)  E o

30. One mole of an ideal gas is allowed to expand reversibly and adiabatically from a temperature of
27o C . If the work done during the process is 3kJ , then final temperature of the gas is
(CV  20J / K)
(1) 100 K (2) 150 K (3) 195 K (4) 255 K

31. 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  105 Nm 2 . The work done is
(1) 270 kJ (2) –900 kJ (3) –900 J (4) 900 kJ

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 Thermodynamics Ch. XI
-1 -1
32. The entropy values (in JK mol ) 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 H2(g)  Cl2(g)  2HCl(g) is
(1) + 540.3 (2) + 727.3 (3) – 166.9 (4) + 19.8

33. Which of the following is the least random state of water?

(1) Ice (2) Liquid water
(3) Steam (4) All present same random state

34. The entropy of crystalline substances at absolute zero going by the third law of thermodynamics
should be taken as
(1) 100 (2) 50
(3) Zero (4) Different for different substances

35. Which of the following pairs of a chemical reaction is certain to result in spontaneous reaction?
(1) Exothermic and decreasing disorder (2) Endothermic and increasing disorder
(3) Exothermic and increasing disorder (4) Endothermic and decreasing disorder

36. 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
(1) (2) T + (3) T (4) T 
2(2/3)
3  0.0821 3  0.0821

37. 9.0 gm of H 2 O is vaporised at 100o C and 1 atm pressure. If the latent heat of vaporisation of
water is x J / gm , then S is given by
x 18x 18x 1 18x
(1) (2) (3) (4) 
373 100 373 2 373

38. 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
(1) 88.3 J/mol K (2) (88.3)2 J/mol K (3) – 88.3 J/mol K (4) J/mol K
88.3

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

1
(1) Ca(s)  O2 (g)  CaO(s) (2) CaCO3 (s)  CaO(s)  CO2 (g)
2
(3) C(s)  O2 (g)  CO2 (g) (4) N2 (g)  O2 (g)  2NO(g)

40. The occurrence of a reaction is impossible if

(1) H is +ve ; S is also + ve but H  TS
(2) H is – ve ; S is also – ve but H  TS
(3) H is – ve ; S is + ve
(4) H is + ve ; S is – ve

41. Which of the following statement is true. The entropy of the universe
(1) Increases and tends towards maximum value
(2) Decreases and tends to be zero
(3) Remains constant
(4) Decreases and increases with a periodic rate

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42. When enthalpy and entropy change for a chemical reaction are 2.5103 cal and 7.4cal deg1
respectively. Predict the reaction at 298 K is
(1) Spontaneous (2) Reversible
(3) Irreversible (4) Non-spontaneous

43. The enthalpy change for the transition of liquid water to steam, H vap  37.3kJ mol1 at 373K .
The entropy change for the process is
(1) 111.9J mol1K1 (2) 37.3J mol1 K1 (3) 100J mol1K 1 (4) 74.6J mol1K1

44. For reaction 2Cl(s)  Cl2 (s) , the signs of H and S respectively are
(1) +, – (2) +, + (3) –, – (4) –, +

45. For which of the processes is S negative

(1) H2 (g)  2H(g) (2) N2 (g)1atm  N2 (g)8atm
(3) 2SO3 (g)  2SO2 (g)  O2 (g) (4) C(diamond)  C(graphite)

46. Identify the correct statement regarding entropy

(1) At 0o C , the entropy of a perfectly crystalline substance is taken to be zero
(2) At absolute zero of temperature, the entropy of a perfectly crystalline substance is ve
(3) At absolute zero of temperature, the entropy of all crystalline substances is taken to be zero
(4) At absolute zero of temperature, the entropy of a perfectly crystalline substance is taken to
be zero

47. One mole of an ideal gas at 300K is expanded isothermally from an initial volume of 1 litre to
10 litres. The change in energy for this process is (R  2calmol1K1 )
(1) 163.7 cal (2) 850.2 cal (3) 1381.1 cal (4) Zero

48. Following data is known about melting of a compound AB. H  9.2kJ mol1 ,
1 1
S  0.008kJ K mol . Its melting point is
(1) 736 K (2) 1050 K (3) 1150 K (4) 1150o C

49. The volume of a gas decreases from 500cc to 300cc when a sample of gas is compressed by an
average pressure of 0.6 atm. During this process 10 J of heat is liberated. The change in internal
energy is
(1) – 2.16 J (2) 12.156 J (3) 2.16 J (4) 101.3 J

50. The standard entropies of CO2 (g),C(s) and O2 (g) are 213.5, 5.690 and 205JK 1 respectively. The
standard entropy of formation of CO2 (g) is
(1) 1.86JK1 (2) 1.96JK1 (3) 2.81JK1 (4) 2.86JK1

51. Which of the following endothermic processes are spontaneous?

(1) Melting of ice (2) Evaporation of water
(3) Heat of combustion (4) Both (1) and (2)

52. 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, Hvap  2.257kJ / g)
(1) 105.9 Jk 1 (2) 107.9 Jk 1 (3) 108.9 Jk 1 (4) 109.9 Jk 1

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 Thermodynamics Ch. XI
53. The unit of entropy is
(1) J mol1 (2) JK mol1 (3) J mol1K1 (4) J 1K 1mol1

54. When a liquid boils, there is

(1) An increase in entropy (2) A decrease in entropy
(3) An increase in heat of vaporization (4) An increase in free energy

55. Which one of the following has So greater than zero
(1) CaO  CO2 (g) ⇌ CaCO3 (s) (2) NaCl (aq) ⇌ NaCl(s)
(3) NaNO3 (s) ⇌ Na  (aq)  NO3 (aq) (4) N2 (g)  3H2 (g) ⇌ 2NH3 (g)

56. The molar heat capacity of water at constant pressure is 75 JK1mol1 . 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
(1) 6.6 K (2) 1.2 K (3) 2.4 K (4) 4.8 K

57. One mole of water at 100o C is converted into steam at 100o C at a constant pressure of 1 atm.
The change in entropy is [heat of vaporisation of water at 100o C  540cal / gm ]
(1) 8.74 (2) 18.76 (3) 24.06 (4) 26.06

58. For a carnot engine, the source is at 500K and the sink at 300K . What is efficiency of this
engine
(1) 0.2 (2) 0.4 (3) 0.6 (4) 0.3

59. Considering entropy (S) as a thermodynamic parameter, the criterion for the spontaneity of any
process is
(1) Ssystem  0 only (2) Ssurroundings  0 only
(3) Ssystem  Ssurroundings  0 (4) Ssystem  Ssurroundings  0

60. The enthalpy of vapourization of a liquid is 30kJ mol1 and entropy of vapourization is
75J mol1K . The boiling point of the liquid at 1 atm is
(1) 250K (2) 400K (3) 450K (4) 600K

61. If C  O2  CO2  94.2kcal

1
H2  O2  H2O  68.3kcal
2
CH4  2O2  CO2  2H2O  210.8kcal
Then the possible heat of methane will be
(1) 47.3 kcal (2) 20.0 kcal (3) 45.9 kcal (4) – 47.3 kcal

62. In which of the following neutralisation reactions, the heat of neutralisation will be highest
(1) NH4OH and CH3COOH (2) NH4OH and HCl
(3) NaOH and CH3COOH (4) NaOH and HCl

63. If S  O2  SO2 ;(H  298.2)

1
SO2  O2  SO3 ;(H  98.2)
2
SO3  H2O  H2SO4 ;(H  130.2)
1
H2  O2  H2O;(H  287.3)
2

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 Thermodynamics Ch. XI
Then the enthalpy of formation of H2SO4 at 298K will be
(1) 433.7 kJ (2) 650.3kJ (3) 320.5 kJ (4) 813.9 kJ

64. From Kirchhoff's equation which factor affects the heat of reaction?
(1) Pressure (2) Temperature (3) Volume (4) Molecularity

65. An exothermic reaction is one in which the reacting substances

(1) Have more energy than the products
(2) Have less energy than the products
(3) Are at a higher temperature than the product
(4) None of the above

66. The heat evolved in the combustion of benzene is given by

1
C6 H6  7 O2  6CO2 (g)  3H2O(l); H  3264.6kJ
2
Which of the following quantities of heat energy will be evolved when 39gC6 H6 are burnt
(1) 816.15 kJ (2) 1632.3 kJ (3) 6528.2 kJ (4) 2448.45 kJ

67. The following is (are) exothermic reaction

(1) Combustion of methane (2) Decomposition of water
(3) Dehydrogenation of ethane to ethylene (4) Conversion of graphite to diamond

68. Hf (298 K) of methanol is given by the chemical equation

(1) CH4 (g)  1/ 2O2 (g)  CH3OH(g)
(2) C (graphite) 1/ 2O2 (g)  2H2 (g)  CH3OH(l)
(3) C (diamond) 1/ 2O2 (g)  2H2 (g)  CH3OH(l)
(4) CO(g)  2H2 (g)  CH3OH(l)

69. If H of for H 2 O 2 and H 2 O are 188kJ / mole and 286 kJ / mole . What will be the enthalpy
change of the reaction 2H2O2 (l)  2H2O(l)  O2 (g)
(1) 196 kJ / mole (2) 146 kJ / mole (3) 494 kJ / mole (4) 98kJ / mole

70. The heat of transition (Ht ) of graphite into diamond would be, where
C(graphite)  O2 (g)  CO2 (g); H  x kJ ; C(diamond)  C2 (g)  CO2 (g); H  ykJ
(1) (x  y)kJ mol1 (2) (x  y)kJ mol1
(3) (y  x)kJ mol1 (4) None of these

71. Correct relationship between heat of fusion (Hfus ) , heat of vaporization (H vap ) and heat of
sublimation (Hsub ) is
(1) Hfus  Hvap  Hsub (2) Hvap  Hfus  Hsub
(3) Hsub  Hvap  Hfus (4) Hsub  Hvap  Hfus

72. Given that

1
2C(s)  2O2 (g)  2CO2 (g); H  787kJ ; H2 (g)  O2 (g)  H2 O(l); H  286kJ ;
2
1
C2 H2 (g)  2 O2 (g)  2CO2 (g)  H2O(l); H  1301kJ
2
Heat of formation of acetylene is
(1) 1802 kJ (2) 1802 kJ (3) 800 kJ (4) 228 kJ
80 COLLEGES: ANDHERI / BORIVALI / CHEMBUR / DADAR / KALYAN / KHARGHAR / NERUL / POWAI / THANE
 Thermodynamics Ch. XI
1 1
73. Enthalpy change for reaction, H2  Cl2  HCl , is called
2 2
(1) Enthalpy of combination (2) Enthalpy of reaction
(3) Enthalpy of formation (4) Enthalpy of fusion

74. The enthalpy of neutralization is about 57.3 kJ for the pair

(1) HCl and NH4OH (2) NH4OH and HNO3
(3) HCl and NaOH (4) CH3COOH and NaOH

75. The mutual heat of neutralisation of 40 gm of NaOH and 60 gm CH3COOH will be

(1) 56.1 kcal (2) Less than 56.1 kcal
(3) More than 56.1 kcal (4) 13.7 kcal

76. The enthalpy of combustion at 25°C of H2, cyclohexane (C6H12) and cyclohexene (C6H10) are –
241, –3920 and –3800 KJ / mole respectively. The heat of hydrogenation of cyclohexene is
(1) – 121 KJ / mole (2) + 121 KJ / mole
(3) – 242 KJ / mole (4) + 242 KJ / mole

77. Heat of combustion H of CH4 ,C2H6 ,C2H4 and C2H2 gases are – 212.8, – 373.0, – 337.0 and –
310.5 kcal respectively at the same temperature. The best fuel among these gases is
(1) CH4 (2) C2H6 (3) C2H4 (4) C2H2

78. The standard molar heat of formation of ethane, CO2 and water (l) are respectively – 21.1, –
94.1 and – 68.3 kcal. The standard molar heat of combustion of ethane will be
(1) – 372 kcal (2) 162 kcal (3) –240 kcal (4) 183.5 kcal

79. The heat of combustion of carbon is –94 kcal at 1 atm pressure. The intrinsic energy of CO2 is
(1) 94 kcal (2)  94 kcal (3) 47 kcal (4) 47 kcal

80. The heat of neutralisation of a strong acid and a strong alkali is 57.0kJ mol1 . The heat released
when 0.5 mole of HNO3 solution is mixed with 0.2 mole of KOH is
(1) 57.0 kJ (2) 11.4 kJ (3) 28.5 kJ (4) 34.9 kJ

81. A solution of 500ml of 0.2 M KOH and 500 ml of 0.2 M HCl is mixed and stirred; the rise in
temperature is T1 . The experiment is repeated using 250 ml each of solution, the temperature
raised is T2 . Which of the following is true?
(1) T1  T2 (2) T1  2T2 (3) T1  4T2 (4) T2  9T1

82. Which is the best definition of “heat of neutralization?”

(1) The heat set free when one gram molecule of a base is neutralized by one gram molecule of
an acid in dilute solution at a stated temperature
(2) The heat absorbed when one gram molecule of an acid is neutralized by one gram molecule
of a base in dilute solution at a stated temperature
(3) The heat set free or absorbed when a normal solution containing one gram equivalent of an
acid is neutralized by a normal solution containing one gram equivalent of a base at a stated
temperature
(4) The heat set free when one gram equivalent of an acid is neutralized by one gram equivalent
of a base in dilute solution at a stated temperature

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 Thermodynamics Ch. XI
83. The heat of formation is the change in enthalpy accompanying the formation of a substance from
its elements at 298 K and 1 atm pressure. Since the enthalpies of elements are taken to be zero,
the heat of formation (H) of compounds
(1) Is always negative (2) Is always positive
(3) May be negative or positive (4) Is zero

84. If a chemical reaction is accompanied by the evolution of heat, it is

(1) Catalytic (2) Photochemical (3) Endothermic (4) Exothermic

85. A reaction that takes place with the absorption of energy is

(1) Burning of a candle (2) Rusting of iron
(3) Electrolysis of water (4) Digestion of food

86. Which of the following reaction can be used to define the heat of formation of CO2 (g)
(1) C(graphite)  O2 (g)  CO2 (g) (2) CH4 (g)  2O2 (g)  CO2 (g)  2H2O(l)
1 1
(3) CO(g)  O2 (g)  CO2 (g) (4) C6 H6 (l)  7 O2 (g)  6CO2  3H2O(l)
2 2

87. The enthalpy of formation of ammonia is 46.0kJ mol1 . The enthalpy change for the reaction
2NH3 (g)  2N2 (g)  3H2 (g) is
(1) 46.0 kJ mol1 (2) 92.0 kJ mol1 (3) – 23.0 kJ mol1 (4) – 92.0 kJ mol1

88. The formation of water from H2 (g) and O2 (g) is an exothermic reaction because
(1) The chemical energy of H2 (g) and O2 (g) is more than that of water
(2) The chemical energy of H2 (g) and O2 (g) is less than that of water
(3) Not dependent on energy
(4) The temperature of H2 (g) and O2 (g) is more than that of water

89. In the reaction for the transition of carbon in the diamond form to carbon in the graphite form,
H is 453.5cal . This points out that
(1) Graphite is chemically different from diamond
(2) Graphite is as stable as diamond
(3) Graphite is more stable than diamond
(4) Diamond is more stable than graphite

90. The standard heats of formation in kcal mol1 of NO2 (g) and N 2 O 4 (g) are 8.0 and 2.0
respectively. The heat of dimerization of NO 2 in kcal is
2NO2 (g)  N2O4 (g)
(1) 10.0 (2) – 6.0 (3) – 12.0 (4) – 14.0

91. The difference between heats of reaction at constant pressure and at constant volume for the
reaction 2C6H6 (l)  15O2 (g) 12CO2 (g)  6H2O(l) at 25o C in kJ is
(1) –7.43 (2) + 3.72 (3) –3.72 (4) + 7.43

92. C (diamond) C2 (g)  CO2 (g); H  395 kJ

C (graphite) O2 (g)  CO2 (g); H  393.5 kJ
From the data, the H when diamond is formed from graphite, is
(1) 1.5 kJ (2)  1.5 kJ (3)  3.0 kJ (4) 3.0 kJ

82 COLLEGES: ANDHERI / BORIVALI / CHEMBUR / DADAR / KALYAN / KHARGHAR / NERUL / POWAI / THANE
 Thermodynamics Ch. XI

93. Which of the following equations correctly represents the standard heat of formation (Hof ) of
methane?
(1) C(diamond)  2H2 (g)  CH4 (g) (2) C(graphite)  2H2 (g)  CH4 (l)
(3) C(graphite)  2H2 (g)  CH4 (g) (4) C(graphite)  4H  CH4 (g)

94. In which of the following reactions does the heat change represent the heat of formation of water
(1) 2H2 (g)  O2 (g)  2H2O(l); H  116kcal
1
(2) H2 (g)  O2 (g)  H2O(l); H  58kcal
2
(3) H (aq.)  OH (aq.)  2H2O(l); H  13.7kcal
1
(4) C2 H2 (g)  2 O2 (g)  2CO2 (g)  H2O(l) ; H  310 kcal
2

95. Heat of transition is the heat evolved or absorbed when a substance is converted from
(1) Solid to liquid
(2) Solid to vapour
(3) Liquid to vapour
(4) One allotropic form to another allotropic form

96. If enthalpies of formation of C2H4 (g),CO2 (g) and H2O(l) at 25o C and 1atm pressure be 52, –
394 and 286kJ mol1 respectively, the enthalpy of combustion of C2 H4 (g) will be
(1) 1412kJ mol1 (2) 1412kJ mol1 (3) 141.2kJ mol1 (4) 141.2kJ mol1

97. Heat of formation in the reaction

H2  Cl2  2HCl  44kcal is
(1) 44 kcal (2) 44000 kcal (3) 22 kcal (4) 11 kcal

98. When water is added to quick lime, the reaction is

(1) Exothermic (2) Endothermic (3) Explosive (4) None of these

99. The heat change for the following reaction C(s)  2S(s)  CS2 (l) is known as
(1) Heat of vaporization (2) Heat of solution
(3) Heat of fusion (4) Heat of formation

100. The enthalpy of combustion of benzene from the following data will be
1
(i) 6C(s)  3H2 (g)  C6H6 (l); H  45.9kJ (ii) H2 (g)  O2 (g)  H2O(l); H  285.9kJ
2
(iii) C(s)  O2 (g)  CO2 (g); H  393.5kJ
(1) + 3172.8 kJ (2) – 1549.2 kJ (3) – 3172.8 kJ (4) – 3264.6 kJ

101. 2.2016gm of acetaldehyde produced 13.95 kcal of heat on combustion in O2 . Calculate the heat
of combustion of CH3CHO
(1) 279 kcal (2) 972 kcal (3) 27.9 kcal (4) 2.79 kcal

1
102. C  O2  CO; H  42kJ
2
1
CO  O2  CO2 ; H  24kJ
2
The heat of formation of CO2 is
(1) – 16 kJ (2) + 66 kJ (3) + 16 kJ (4) – 66 kJ
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 Thermodynamics Ch. XI
103. Standard molar enthalpy of formation of CO2 is equal to
(1) Zero
(2) The standard molar enthalpy of combustion of gaseous carbon
(3) The sum of standard molar enthalpies of formation of CO and O2
(4) The standard molar enthalpy of combustion of carbon (graphite)

104. C  O2  CO2 ; H  X
1
CO  O2  CO2 ; H  Y
2
Then the heat of formation of CO is
(1) X  Y (2) Y  2X (3) X  Y (4) 2X  Y

105. Calculate the standard heat of formation of carbon disulphide (l) , given that the standard heat of
combustion of carbon (s) , sulphur (s) and carbon disulphide (l) are 393.3,  293.72 and
1108.76kJ mol1 respectively
(1) 128.02kJ mol1 (2) 12.802kJ mol1 (3) 128.02kJ mol1 (4) 12.802kJ mol1

106. 8gm of CH4 is completely burnt in air. The number of moles of water produced is
(1) 0.5 (2) 1 (3) 2 (4) 18

107. For the reaction A(g)  2B(g)  2C(g)  3D(g) , the value of E at 27o C is 19.0 kcal. The value
of H for the reaction would be (R  2.0calK1mol1 )
(1) 20.8 kcal (2) 19.8 kcal (3) 18.8 kcal (4) 20.2 kcal

108. The enthalpy of solution of BaCl 2 (s) and BaCl2 .2H2O(s) are 20.6 and 8.8kJ mol1 respectively.
The enthalpy change for the reaction BaCl2 (s)  2H2O  is
(1) 29.4 kJ (2) – 11.8 kJ (3) – 20.6 kJ (4) – 29.4 kJ

109. The enthalpy change of a reaction does not depend on

(1) The state of reactants and products
(2) Nature of reactants and products
(3) Different intermediate reaction
(4) Initial and final enthalpy change of a reaction

3
110. S  O2  SO3  2x kcal
2
1
SO2  O2  SO3  ykcal
2
Find out the heat of formation of SO 2
(1) 2x  y (2) 2x  y (3) x  y (4) 2x / y

111. Combustion of glucose takes place according to the equation,

C6H12O6  6O2  6CO2  6H2O , H  72 kcal . How much energy will be required for the
production of 1.6 g of glucose (Molecular mass of glucose = 180 g)
(1) 0.064 kcal (2) 0.64 kcal (3) 6.4 kcal (4) 64 kcal

112. When 50cm3 of a strong acid is added to 50cm3 of an alkali, the temperature rises by 5o C . If
250cm3 of each liquid are mixed, the temperature rise would be
(1) 5o C (2) 10o C (3) 25o C (4) 20o C

84 COLLEGES: ANDHERI / BORIVALI / CHEMBUR / DADAR / KALYAN / KHARGHAR / NERUL / POWAI / THANE
 Thermodynamics Ch. XI
113. Enthalpy of neutralisation of acetic acid by NaOH is 50.6 kJ / mol. and the heat of
neutralisation of a strong acid with a strong base is – 55.9 kJ/mol. What is the value of H for
the ionisation of CH3COOH
(1) + 5.3 kJ/mol (2) + 6.2 kJ/mol (3) + 8.2 kJ/mol (4) + 9.3 kJ/mol

114. The heat change for the following reaction at 298o K and at constant pressure is 7.3kcal
A2 B(s) 2A(s)  1/ 2B2 (g) , H  7.3kcal
The heat change at constant volume would be
(1) 7.3 kcal (2) More than 7.3 (3) Zero (4) None of these

115. H2 (g)  Cl2 (g)  2HCl(g). H  44kcal

2Na(s)  2HCl(g)  2NaCl(s)  H2 (g), H  152 kcal
1
For the reaction Na(s)  Cl2 (g)  NaCl(s), H 
2
(1) – 108 kcal (2) – 196 kcal (3) – 98 kcal (4) 54 kcal

116. The H of for CO2 (g),CO(g) and H2O(g) are – 393.5, –110.5 and – 241.8kJmol–1 respectively.
The standard enthalpy change (in kJ) for the reaction CO2 (g)  H2 (g)  CO(g)  H2O(g) is
(1) 524.1 (2) 41.2 (3) – 262.5 (4) – 41.2

117. Which of the following compounds will absorb the maximum quantity of heat when dissolved in
the same amount of water? The heats of solution of these compounds at 25o C in kJ/mole of each
solute is given in brackets
(1) HNO3 (H  33) (2) KCl(H  17.64)
(3) NH4 NO3 (H  25.5) (4) HCl(H  74.1)

118. The heat of formation of methane C(s)  2H2 (g) CH4 (g) at constant pressure is 18500 cal at
25o C . The heat of reaction at constant volume would be
(1) 17904 cal (2) 18202 cal (3) 18798 cal (4) 19096 cal

119. In order to decompose 9 g water 142.5 kJ heat is required. Hence the enthalpy of formation of
water is
(1) – 142.5 kJ (2) + 142.5 kJ (3) – 285 kJ (4) + 285 kJ

120. What is n for combustion of 1 mole of benzene, when both the reactants and the products are
gas at 298 K
(1) 0 (2) 3/2 (3) – 3/2 (4) ½

121. A system is changed from state A to state B by one path and from B to A another path. If E1 and
E2 are the corresponding changes in internal energy, then
(1) E1  E2  ve (2) E1  E2  ve (3) E1  E2  0 (4) None of these

122. A cylinder of gas is assumed to contain 11.2 kg of butane (C4H10 ) . If a normal family needs 20000
kJ of energy per day. The cylinder will last: (Given that H for combustion of butane is – 2658
kJ)
(1) 20 days (2) 25 days (3) 26 days (4) 24 days

123. Compounds with high heat of formation are less stable because
(1) High temperature is required to synthesise them
(2) Molecules of such compounds are distorted

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 Thermodynamics Ch. XI
(3) It is difficult to synthesis them
(4) Energy rich state leads to instability

124. One gram sample of NH4 NO3 is decomposed in a bomb calorimeter. The temperature of the
calorimeter increases by 6.12 K the heat capacity of the system is 1.23 kJ/g/deg. What is the
molar heat of decomposition for NH4 NO3
(1) – 7.53 kJ/mol (2) – 398.1 kJ/mol (3) – 16.1 kJ/mol (4) – 602 kJ/mol

125. If the heat of formation of CO2 is 393kJ . The amount of heat evolved in the formation of 0.176
kg of CO2 is
(1) 1357.9 kJ (2) 1275.9 kJ (3) 1572.0 kJ (4) 1165.5kJ

126. If (i) C  O2  CO2 , (ii) C  1/ 2O2  CO , (iii) CO  1/ 2O2  CO2 , the heats of reaction are
Q,  12,  10 respectively. Then Q 
(1) – 2 (2) 2 (3) – 22 (4) – 16

127. How much energy is released when 6 mole of octane is burnt in air? Given H of for
CO2 (g),H2O(g) and C8 H18 (l) respectively are – 490,– 240 and + 160 J/mol
(1) – 6.2 kJ (2) – 37.4 kJ (3) – 35.5 kJ (4) – 20.0 kJ

128. If the bond dissociation energies of XY,X2 and Y2 (all diatomic molecules) are in the ratio of 1 :
1 : 0.5 and f H for the formation of XY is 200kJ mole1 . The bond dissociation energy of X 2
will be
(1) 100kJ mol1 (2) 800kJ mol1 (3) 300kJ mol1 (4) 400kJ mol1

129. Energy required to dissociate 4 gm of gaseous hydrogen into free gaseous atoms is 208 kcal at
25o C . The bond energy of H  H bond will be
(1) 104 kcal (2) 10.4 kcal (3) 1040 kcal (4) 104 cal

130. Which one of the following bonds has the highest average bond energy (kcal/mol)
(1) S  O (2) C  C (3) C  N (4) N  N

131. The bond dissociation energies of gaseous H2 ,Cl2 and HCl are 104, 58 and 103 kcal
respectively. The enthalpy of formation of HCl gas would be
(1) – 44 kcal (2) 44 kcal (3) – 22 kcal (4) 22 kcal

132. Given that C(g)  4H(g) CH4 (g); H  166kJ

The bond energy C  H will be
(1) 208 kJ/mole (2) – 41.6 kJ/mole (3) 832 kJ/mole (4) None of these

133. If enthalpies of methane and ethane are respectively 320 and 560 calories then the bond energy
of C  C bond is
(1) 80 calories (2) 40 calories (3) 60 calories (4) 120 calories

134. 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
(1) + 261 kJ (2) – 103 kJ (3) – 261 kJ (4) + 103 kJ

86 COLLEGES: ANDHERI / BORIVALI / CHEMBUR / DADAR / KALYAN / KHARGHAR / NERUL / POWAI / THANE
 Thermodynamics Ch. XI
135. For a spontaneous change, free energy change G is
(1) Positive (2) Negative
(3) Zero (4) Can be positive or negative

136. A minus sign of the free energy change denotes that

(1) The reaction tends to proceed spontaneously (2) The reaction is non-spontaneous
(3) The system is in equilibrium (4) The reaction is very much unlikely

137. The relation between G and H is

(1) H  G  T S (2) G  H  T S (3) T S  G  H (4) H  T G  S

138. At 300 K, the reactions which have following values of thermodynamic parameters do not occur
spontaneously
(1) Go  400 kJ mol1
(2) Ho  200 kJ mol1 , So  4 JK1mol1
(3) Ho  200kJ mol1 , So  4JK1mol1
(4) Ho  200J mol1 , So  40JK1mol1

139. For precipitation reaction of Ag  ions with NaCl , which of the following statements is correct?
(1) H for the reaction is zero (2) G for the reaction is zero
(3) G for the reaction is negative (4) [G]  [H]

140. For the change H2O(l) H2O(g);P  1atm , T  373K , the free energy change G  0 . This
indicates that
(1) H2O(l) is in equilibrium with H2O(g)
(2) Water boils spontaneously at 373K
(3) Water does not boil spontaneously at 373K
(4) Condensation of water vapour occurs spontaneously at 373K

141. G o for the reaction X  Y ⇌ Z is – 4.606 kcal . The value of equilibrium constant of the
reaction at 227o C is (R  2.0cal.mol1K1 )
(1) 100 (2) 10 (3) 2 (4) 0.01

142. For a reaction at 25o C enthalpy change and entropy changes are 11.7 103 J mol1 and
105J mol1K1 respectively. What is the Gibbs free energy
(1) 15.05 kJ (2) 19.59 kJ (3) 2.55 kJ (4) 22.55 kJ

143. Born-Haber cycle is used to determine

(1) Crystal energy (2) Electron affinity (3) Lattice energy (4) All of these

144. The free energy change for the following reactions are given below,
5
C2 H2 (g)  O2 (g)  2CO2 (g)  H2O(l); Go  1234kJ
2
C(s)  O2 (g)  CO2 (g) Go  394kJ
1
H2 (g)  O2 (g)  H2O(l) G o  237kJ
2
What is the standard free energy change for the reaction H2(g)  2C(s)  C2H2(g)
(1) – 209 kJ (2) – 2259 kJ (3) + 2259 kJ (4) 209 kJ

COLLEGES: ANDHERI / BORIVALI / CHEMBUR / DADAR / KALYAN / KHARGHAR / NERUL / POWAI / THANE 87
 Thermodynamics Ch. XI
145. The equilibrium concentration of the species in the reaction A  B C  D are 3, 5, 10 and 15
moleL1 respectively at 300 K . The standard G for the reaction is (in cal.)
(1) 13.81 (2) – 1381.8 (3) – 138.18 (4) 1391.6

146. Standard enthalpy and standard entropy changes for the oxidation of ammonia at 298 K are
382.64kJ mol1 and 145.6JK1mol1 , respectively. Standard Gibbs energy change for the same
reaction at 298 K is
(1) – 439.3 kJ mol1 (2) – 523.2 kJ mol1 (3) – 221.1 kJ mol1 (4) – 339.3 kJ mol1

147. For spontaneity of a cell, which is correct?

(1) G  0, E  0 (2) G   ve, E  0
(3) G   ve, E   ve (4) G   ve, E   ve

148. The H and S for a reaction at one atmospheric pressure are +30.558 kJ and 0.066kJk 1
respectively. The temperature at which the free energy change will be zero and below of this
temperature the nature of reaction would be
(1) 443 K, non-spontaneous (2) 443 K, spontaneous
(3) 463 K, non-spontaneous (4) 463 K, spontaneous

PREVIOUS YEARS QUESTIONS

1. In which of the following entropy decreases? [MP PMT 2000]
(1) Crystallization of sucrose from solution (2) Rusting of iron
(3) Melting of ice (4) Vaporization of camphor

2. The heat liberated when 1.89 g of benzoic acid is burnt in a bomb calorimeter at 25o C increases
the temperature of 18.94 kg of water by 0.632o C .If the specific heat of water at 25o C is 0.998
cal/g-deg, the value of the heat combustion of benzoic acid is [BHU 2000]
(1) 771.1 kcal (2) 871.2 kcal (3) 881.1 kcal (4) 981.1 kcal

3. 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 [CBSE PMT 2000]
(1) 28 kJ (2) 19 kJ (3) 10 kJ (4) 9 kJ

4. In thermodynamics, a process is called reversible when [AIIMS 2001]

(1) Surroundings and system change into each other
(2) There is no boundary between system and surroundings
(3) The surroundings are always in equilibrium with the system
(4) The system changes into the surroundings spontaneously

5. Which of the following unit represents largest amount of energy [AMU 2001]
(1) Calorie (2) Joule (3) Erg (4) Electron volt

6. Enthalpy of formation of two compounds x and y are – 84 kJ and – 156 kJ respectively. Which
of the following statements is correct [CBSE PMT 2001]
(1) x is more stable than y (2) x is less stable than y
(3) Both x and y are unstable (4) x and y are endothermic compounds

7. For melting of 3 moles of water at 0o C the G o is [MP PMT 2001]

(1) Zero (2) + ve (3) – ve (4) Unpredictable

88 COLLEGES: ANDHERI / BORIVALI / CHEMBUR / DADAR / KALYAN / KHARGHAR / NERUL / POWAI / THANE
 Thermodynamics Ch. XI
8. When a gas undergoes adiabatic expansion, it gets cooled due to [DCE 2002]
(1) Loss of kinetic energy (2) Fall in temperature
(3) Decrease in velocity (4) Energy used in doing work

9. The heat required to raise the temperature of a body by 1 K is called [AIEEE 2002]
(1) Specific heat (2) Thermal capacity
(3) Water equivalent (4) None of these

10. For conversion C (graphite)  C (diamond) the S is [MP PET 2003]

(1) Zero (2) Positive (3) Negative (4) Unknown

11. 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
H2C  CH2 (g)  H2 (g)  H3C  CH3 (g) at 298 K will be [AIEEE 2003]
(1) + 250 kJ (2) – 250 kJ (3) + 125 kJ (4) – 125 kJ

12. The process carried out in perfect insulation is [RPMT-2003]

(1) Isothermal (2) isobaric (3) isochoric (4) adiabatic

13. The molar heat capacity of water at constant pressure, C is 75 J mol–1, 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
[CBSE AIPMT 2003]
(1) 4.8 K (2) 6.6 K (3) 1.2 K (4) 2.4 K

14. Formation of a solution from two components can be considered as

(a) pure solvent  separated solvent molecules, H1
(b) pure solute  separated solute molecules, H2
(c) separated solvent and solute molecules  solution, H3
Solution so formed will be ideal if [CBSE AIPMT 2003]
(1) Hsoln  H1  H2  H3 (2) Hsoln  H3  H1  H2
(3) Hsoln  H1  H2  H3 (4) Hsoln  H1  H2  H3

15. For the reaction, [CBSE AIPMT 2003]

C3H8  g   5O2  g  
3CO2  g   4H2O  l 
at constant temperature, H  E is
(1) +3 RT (2) – RT (3) + RT (4) –3RT

16. One gram sample of NH4NO3 is decomposed in a bomb calorimeter. The temperature of the
calorimeter increases by 6.12 K. The heat capacity of the system is 1.23 kJ/g/deg. What is the
molar heat of decomposition for NH4NO3? [AIIMS 2003]
(1) –7.53 kJ/mol (2) –398.1 kJ/mol (3) –16.1 kJ/mol (4) –602 kJ/mol

17. The enthalpies of formation of Al2O3 and Cr2O3 are –1596 kJ and –1134 kJ respectively. H for
the reaction [KCET 2003]
2Al  Cr2O3  2Cr  Al2O3 is
(1) –2730 kJ (2) –462 kJ (3) –1365 kJ (4) +2730 kJ

18. Enthalpy change when 1 g water is frozen at 0°C is ( Hfus  1.4354 kcal mol1 ) [BCECE 2003]
(1) 0.0797 kcal (2) –0.0797 kcal (3) 1.435 kcal (4) –1.435 kcal

COLLEGES: ANDHERI / BORIVALI / CHEMBUR / DADAR / KALYAN / KHARGHAR / NERUL / POWAI / THANE 89
 Thermodynamics Ch. XI
19. The bond energy of an O—H bond is 109 kcal/mol. When a mole of water is formed, then
(1) 109 kcal is released (2) 218 kcal is absorbed
(3) 109 kcal is absorbed (4) 219 kcal is released

20. The enthalpy change for the reaction of 50.00 ml of ethylene with 50.00 ml of H 2 at 1.5 atm
pressure is H  0.31kJ . The value of E will be [DPMT 2004]
(1) –0.3024 kJ (2) 0.3024 kJ (3) 2.567 kJ (4) –0.0076 kJ

21. Enthalpy of solution of NaOH (solid) in water is 41.6kJ mol1 . When NaOH is dissolved in
water, the temperature of water [UPSEAT 2004]
(1) Increase (2) Decreases
(3) Does not change (4) Fluctuates indefinitely

22. When 50cm 3 of 0.5N H2SO4 is mixed with 50cm 3 of 1N KOH , the heat liberated is
[KCET 2004]
(1) 11.46 kJ (2) 57.3 kJ (3) 573 kJ (4) 573 J

23. How much energy is released when 6 moles of octane is burnt in air? Given H of for CO2(g),
H2O(g) and C8H18(l) respectively are –490, –240 and + 160 J/mol [AIIMS 2004]
(1) –6.2 kJ (2) –37.4 kJ (3) –35.5 kJ (4) –20.0 kJ

24. The enthalpy change for the reaction of 50.00 mL of ethylene with 50.00 mL of H2 at 1.5 atm
pressure is H = –0.31 kJ. the value of E will be [DUMET 2004]
(1) –0.3024 kJ (2) 0.295 kJ (3) 2.567 kJ (4) – 0.0076 kJ

25. G  H  TS was given by [AFMC 2004]

(1) Faraday (2) Kirchoff (3) Einstein (4) Gibbs-Helmholtz

26. For the equilibrium, [CBSE AIPMT-2004]

H2O  l  H 2 O  g  at 1 atm and 298 K
(1) standard free energy change is equal to zero (Go  0).
(2) free energy change is less than zero (G  0).
(3) standard free energy change is less than zero (Go  0).
(4) standard free energy change is greater than zero (Go  0).

27. For the reaction of one mole of zinc dust with one mole of sulphuric acid in a bomb calorimeter,
U and W corresponds to [AIIMS-2005]
(1) U < 0, W = 0 (2) U < 0, W < 0 (3) U > 0, W =0 (4) U > 0, W > 0

28. The absolute enthalpy of neutralization of the reaction

MgO(s) + 2HCl(aq)   MgCl2(aq) +H2O(l) [CBSE AIPMT-2005]
will be
(1) Less than –57.33 kJ mol-1 (2) –57.33 kJ mol-1
(3) greater than –57.33 kJ mol-1 (4) 57.33 kJ mol-1

29. H0f (298K) of methanol is given by the chemical equation, [AIIMS-2005]

1
(1) CH4(g) + O2(g)   CH3OH(g)
2
1
(2) C(graphite) + O2(g) + 2H2(g)   CH3OH(l)
2

90 COLLEGES: ANDHERI / BORIVALI / CHEMBUR / DADAR / KALYAN / KHARGHAR / NERUL / POWAI / THANE
 Thermodynamics Ch. XI
1
(3) C(diamond) + O2(g) + 2H2(g) —CH3OH(l)
2
(4) CO(g) + 2H2(g)  CH3OH(l)

30. Minimum work is obtained when 1 kg of … gas expanded under 500 kPa to 200 kPa pressure at
0°C. [MHT CET 2005]
(1) chlorine (2) oxygen (3) nitrogen (4) methane

31. If the value of ΔCp for nitrogen gas is 7 JK–1 mol–1, then the value of H on heating 28 g of
nitrogen gas from 0°C to 100°C at constant pressure will be [AMU 2005]
(1) 1200 J (2) 1300 J (3) 700 J (4) 1500 J

32. Given the following thermochemical equations, [JCECE 2005]

1
Zn  O2 
 ZnO  84000 cal
2
1
Hg  O2 
 HgO  21700cal
2
Accordingly the heat of reaction for the following reaction Zn + HgO  ZnO + Hg + heat is
(1) 105700 cal (2) 61000 cal (3) 105000 cal (4) 62300 cal

33. Which of the following pairs of a chemical reaction is certain to result in a spontaneous reaction
? [CBSE AIPMT 2005]
(1) Exothermic and decreasing disorder (2) endothermic and increasing disorder
(3) Exothermic and increasing disorder (4) Endothermic and decreasing disorder

34. One mole of an ideal gas is initially at 0°C and 1 atm pressure. If it absorbs 1000 cal heat during
a reversible isothermal expansion, what will be its final volume? [MHT CET 2006]
(1) 102.5 L (2) 242.5 L (3) 22.4 L (4) 140 L

35. Which is correct for an endothermic reaction? [RPMT-2006]

(1) H is positive (2) H is negative (3) E is negative (4) H = zero

36. The enthalpy change (H) for the reaction

N2(g) + 3H2(g)   2NH3(g)
Is –92.38 kJ at 298K. The internal energy change U at 298 K is [AIIMS-2006]
(1) –92.38 kJ (2) –87.42 kJ (3) –97.34 kJ (4) –89.9 kJ

37. Assume each reaction is carried out in an open container. For which reaction will  H =  E?
[CBSE AIPMT-2006]
(1) H2(g) + Br2(g)   2HBr(g) (2) C(s) + 2H2O(g)   2H2(g) + CO2(g)
(3) PCl5(g)   PCl3(g) + Cl2(g) (4) 2CO(g) + O2(g)   2CO2(g) 3)

38. Identify the correct statement for change of Gibbs energy for a system  Gsystem at constant
temperature and pressure. [CBSE AIPMT-2006]
(1) If  Gsystem > 0, the process is spontaneous
(2) If  Gsystem= 0, the system has attained equilibrium
(3) If  Gsystem = 0, the system is still moving in a particular direction.
(4) If  Gsystem < 0, the process is not spontaneous

COLLEGES: ANDHERI / BORIVALI / CHEMBUR / DADAR / KALYAN / KHARGHAR / NERUL / POWAI / THANE 91
 Thermodynamics Ch. XI
39. A cylinder of gas supplied by Bharat petroleum is assumed to contain 14 kg of butane. It is
normal family requires 20,000 kJ of energy per day for cooking, butane gas in the cylinder last
for … days, ( Hc of C4H10 = – 2658 kJ per mole) [BHU 2006]
(1) 15 days (2) 20 days (3) 32 days (4) 40 days

3
40. S  O2 SO3 ; H  2x,
2
1
SO2  O2 
SO3 ; H  y,
2
then heat of formation of SO2 is [JCECE 2006]
2x  y
(1) 2x – y (2) 2x + y (3) x + y (4)
2

41. Calculate H (in Joules) for,

C (graphite)   C (diamond),
from the following data [J&K CET 2006]
C  graphite   O2  g  
 CO2  g  ; H  393.5kJ
C  diamond   O2  g  
 CO2  g  ; H  395.4kJ
(1) 1900 (2) –788.9 × 103 (3) 190000 (4) +788.9 × 103

42. Calculate the entropy change for [Punjab PMET 2006]

CH4  g   H2O  g  
3H2  g   CO  g  ,
using the following data
Substance CH4(g) H2O(g) H2(g) CO(g)
–1 –1
S°/JK mol 186.2 188.7 130.6 197.6
The entropy change is
(1) –46 JK–1 mol–1 (2) +46 JK–1 mol–1
(3) –214.5 JK–1 mol–1 (4) +214.5 JK–1 mol–1

43. Which of the following is combustion reaction? [CPMT-2007]

(1) C + O2   CO2 (2) CH4+ O2   CO2+ H2O
(3) Mg + O2   MgO (4) All of these

44. The enthalpy of hydrogenation of cyclohexene is –119.5 kJ mol-1. If resonance energy of

benzene is –150.4 kJ mol-1, its enthalpy of hydrogenation would be [AIIMS-2007]
(1) –208.1 kJ mol-1 (2) –269.9 kJ mol-1
(3) –358.5 kJ mol-1 (4) –508.9 kJ mol-1

45. One mole of methanol when burnt in O2, gives out 723 kJ mol-1 heat. If one mole of O2 is used,
what will be the amount of heat evolved? [AIIMS-2007]
(1) 723 kJ (2) 924 kJ (3) 482 kJ (4) 241 kJ

46. Which of the following is a path function ? [MHT CET 2007]

(1) Internal energy (2) Enthalpy (3) Work (4) Entropy

47. A gas expands isothermally against a constant external pressure of 1 atm from a volume of 10
dm3 to a volume of 20 dm3. It absorbs 800 J of thermal energy from its surroundings. The  U is
(1) – 312 J (2) + 123 J (3) – 213 J (4) + 231 J

48. Hess law deals with [AFMC 2007]

(1) change in heat of reaction (2) rate of reaction
(3) equilibrium constant (4) influence of pressure on volume of gas
92 COLLEGES: ANDHERI / BORIVALI / CHEMBUR / DADAR / KALYAN / KHARGHAR / NERUL / POWAI / THANE
 Thermodynamics Ch. XI
49. If 150 kJ of energy is needed for muscular work to walk a distance of one km, then how much of
glucose one has to consume to walk a distance of 5 km, provided only 30% of energy is
available for muscular work. (The enthalpy of combustion of glucose is 3000 kJ mol–1 is)
[Kerala CEE 2007]
(1) 75 g (2) 30 g (3) 180 g (4) 150 g
(5) 45 g

50. Calculate the difference between E and H for the following reaction at 27°C (in kcal)
C  graphite   H2  g   CH4  g  [EAMCET 2007]
(1) –0.6 (2) –1.2 (3) +0.6 (4) +1.2

51. The bond energy is the energy required to [MHT CET 2007]
(1) dissociate one mole of the substance (2) dissociate bond in 1 kg of the substance
(3) break one mole of similar bonds (4) break bonds in one mole of substance

52. For the reaction,

2H2  g   O2  g  
 2H2O  g  ; Ho  573.2 kJ
The heat of decomposition of water per mole is [MHT CET 2007]
(1) 286.6 kJ (2) 573.2 kJ (3) –28.66 kJ (4) zero

53. The quantity of heat measured for a reaction in a bomb calorimeter is equal to [J&K CET 2007]
(1) G (2) H (3) pV (4) E

54. The Gibbs free energy for a reversible reaction at equilibrium is [BHU 2007]
(1) positive (2) negative
(3) zero (4) can be positive or negative

55. The decomposition of limestone

CaCO3  s  CaO  s   CO2  g  [Kerala CEE 2007]
is non-spontaneous at 298 K. The H and S values for the reaction are 176.0 kJ and 160 JK–
o o

1
respectively. At what temperature the decomposition becomes spontaneous?
(1) At 100 K (2) Below 500°
(3) At 500°C (4) Between 500°C and 600°C
(5) Above 827°C

56. All naturally occurring processes, proceed in a direction, which leads to [J&K CET 2007]
(1) increase of enthalpy (2) increase of free energy
(3) decrease of free energy (4) decrease of entropy

57. What will be the heat of formation of methane, if the heat of combustion of carbon is ‘–x’ kJ,
heat of formation of water is ‘–y’ kJ and heat of combustion of methane is ‘z’ kJ?
[AIIMS-2008]
(1) (–x–y + z)kJ (2) (–z–x + 2y)kJ (3) (–x–2y–z)kJ (4) (–x–2y+z)kJ

58. For the gas phase reaction, PCl5(g) PCl3(g) + Cl2(g)

which of the following conditions are correct? [CBSE AIPMT-2008]
(1)  H = 0 and  S < 0 (2)  H > 0 and  S > 0
(3)  H < 0 and  S < 0 (4)  H > 0 and  S < 0

COLLEGES: ANDHERI / BORIVALI / CHEMBUR / DADAR / KALYAN / KHARGHAR / NERUL / POWAI / THANE 93
 Thermodynamics Ch. XI
59. Identify the reaction for which H  E. [AFMC 2008]
(1) S rhombic   O2  g  
SO2  g  (2) N2  g   O2  g  
 2NO  g 
1
(3) H2  g   Cl2  g  
 2HCl  g  (4) CO  g   O2  g  
 CO2  g 
2

60. If one mole of ammonia and one mole of hydrogen chloride are mixed in a closed container to
form ammonium chloride gas, then [KCET 2008]
(1) H  U (2) H  U
(3) H  U (4) there is no relationship

61. 100 cm3 of 0.1 M HCl and 100 cm3 of 0.1 M NaOH solutions are mixed in a calorimeter. If the
heat liberated is "Q" kcal, the heat of neutralisation  H  (in kcal) of HCl (aq) and NaOH (aq) is
[EAMCET 2008]
(1) –10Q (2) –100Q (3) –1000Q (4) –Q

62. One mole of which of the following has the highest entropy ? [KCET 2008]
(1) Liquid nitrogen (2) Hydrogen gas (3) Mercury (4) Diamond

63. From the following bond energies,

H—H bond energy ; 431.37 kJ mol-1
C = C bond energy ; 606.10 kJ mol-1
C—C bond energy; 336.49 kJ mol-1
C—H bond energy; 410.50 kJ mol-1
Enthalpy for the reaction
H H H H
will be [CBSE AIPMT-2009]
C C + H—H H C C H

H H H H
(1) 1523.6 kJ mol-1 (2) –243.6 kJ mol-1 (3) –120.0 kJ mol-1 (4) 553.0 kJ mol-1

64. The value of  H and  S for the reaction C(graphite) + CO2(g)  CO(g) are 170 kJ and 170
-1
JK , respectively. This reaction will be spontaneous at [CBSE AIPMT 2009]
(1) 710 K (2) 910 K (3) 1110 K (4) 510 K

65. Calculate the work done when 1 mol of an ideal gas is compressed reversibly from 1 bar to 4 bar
at a constant temperature of 300 K [DUMET 2009]
(1) 4.01 kJ (2) – 8.02 kJ (3) 18.02 kJ (4) None of these

66. Consider the following reactions, [CPMT 2009]

1
I. C  s   O2  g    CO  g  ; H1  a
2
1
II. CO  g   O2  g    CO2  g  ; H2  b
2
III. C  s   CO2  g  
 2CO  g  ; H 3  c
Select the correct statement
(1) Heat of formation of CO2 is (a + b) (2) Heat of combustion of C is (a + b)
(3) H3  H1  H2 (4) All the above are correct statements

67. An endothermic reaction has a positive internal energy change U. In such a case, what is the
minimum value that activation energy can have ? [DUMET 2009]
(1) U (2) U  H  nRT
(3) U  H  nRT (4) U  Ea  RT

94 COLLEGES: ANDHERI / BORIVALI / CHEMBUR / DADAR / KALYAN / KHARGHAR / NERUL / POWAI / THANE
 Thermodynamics Ch. XI
–1 –1
68. The heats of atomization of PH3(g) and P2H4(g) are 953 kJ mol and 1485 kJ mol respectively.
The P—P bond energy in kJ mol–1 is [Kerala CEE 2009]
(1) 213 (2) 426 (3) 318 (4) 1272
(5) 1272

69. Given that Hf  H   218 kJ / mol, express the H—H bond energy in kcal/mol
[EAMCET 2009]
(1) 52.15 (2) 911 (3) 104 (4) 52153

70. The heat change for the following reaction at 298 K and constant pressure is +7.3 kcal.
1
A2 B  s  
 2A  s   B2  g  ; H  7.3kcal
2
The heat change at constant volume would be [Manipal 2009]
(1) +7.3 kcal (2) more than 7.3 kcal
(3) less than 7.3 kcal (4) zero

71. Entropy changes for the process, H2O  l  

 H2 O  s 
at normal pressure and 274 K are given below Ssystem  22.13, Ssurr  22.05, the process is
spontaneous because [AMU 2009]
(1) Ssystem is –ve (2) Ssurr is +ve (3) Su is –ve (4) Ssystem  Ssurr

72. Pick out the wrong statement. [Kerala CEE 2009]

(1) The standard free energy of formation of all element is zero
(2) A process accompanied by decrease in entropy is spontaneous under certain conditions.
(3) The entropy of perfectly crystalline substance at absolute zero is zero
(4) A process that leads to increase in free energy will be spontaneous.
(5) Enthalpy of combustion is always negative.

73. In thermodynamics, a process is called reversible when [CG PMT, Haryana PMT 2009]
(1) surrounding and system change into each other
(2) there is no boundary between system and surrounding
(3) the surrounding are always in equilibrium with the system
(4) the system changes into surrounding spontaneously

74. The incorrect statement among the following is [J & K CET 2009]
(1) The entropy of the universe remains constant
(2) Heat cannot be completely converted into work
(3) The absolute entropy of a perfectly crystalline solid at absolute zero temperature is zero
(4) The total energy of an isolated system remains constant

75. Under which of the following sets of conditions, G is always negative ? [OJEE 2009]
(1) H  ve and S   ve (2) H   ve and S   ve
(3) H   ve and S   ve (4) H   ve and S   ve .

76. The second law of thermodynamics says that in a cyclic process [WB JEE 2009]
(1) work cannot be converted into heat
(2) heat cannot be converted into work
(3) work cannot be completely converted into heat
(4) heat cannot be completely converted into work

COLLEGES: ANDHERI / BORIVALI / CHEMBUR / DADAR / KALYAN / KHARGHAR / NERUL / POWAI / THANE 95
 Thermodynamics Ch. XI
77. When 400 mL of 0.2 N solution of a weak acid is neutralized by a dilute aqueous solution of
sodium hydroxide under standard conditions, 4.4 kJ amount of heat is liberated. Therefore, the
standard enthalpy of neutralization of this weak acid in kJ equiv–1 is [J&K CET 2009]
(1) –11 (2) –44 (3) –55 (4) –22

78. Equal volumes of molar hydrochloric acid and sulphuric acid are neutralized by dilute NaOH
solution and x kcal and y kcal of heat are liberated respectively. Which of the following is true ?
[WB JEE 2009]
y
(1) x = y (2) x  (3) x = 2y (4) None of these
2

79. For endothermic reaction, energy of activation is Ea and enthalpy of the reaction is H (both of
these in kJ/mol). Minimum value of Ea will be [CBSE AIPMT-2010]
(1) equal to zero (2) less than H (3) equal to H (4) more than H

80. Which equation is correct for adiabatic process? [MP PMT, Haryana PMT 2010]
(1) Q = +W (2) Q = O (3) E = Q (4) p + V = 0

81. Standard entropies of X2, Y2 and XY3 are 60, 40 and 50 JK-1 mol1 respectively. For the reaction
1 3
X2  Y2 XY3 , H  30kJ to be a equilibrium, the temperature should be
2 2
[CBSE AIPMT-2010]
(1) 500K (2) 750 K (3) 1000 K (4) 1250 K

82. If W is the amount of work done by the system and q is the amount of heat supplied to the
system, identify the type of the system [AMU 2010]
(1) isolated system (2) closed system
(3) open system (4) system with thermally conducting walls

83. Thermodynamically the most stable form of carbon is [AMU 2010]

(1) diamond (2) graphite (3) fullerenes (4) coal

84. If 1 mole of an ideal gas expands isothermally at 37°C from 15 L to 25 L, the maximum work
obtained is [AFMC 2010]
(1) 12.87 L-atm (2) 6.43 L-atm (3) 8.57 L-atm (4) 2.92 L-atm

85. The pressure of a gas is 100 kPa. If it is compressed form 1 m3 to 10 dm3, find the work done
[MHT CET 2010]
(1) 990 J (2) 9990 J (3) 9900 J (4) 99000 J

86. The heat liberated when 1.89 g of benzoic acid is burnt in a bomb calorimeter at 25°C increase
the temperature of 18.94 kg of water by 0.632°C. If the specific heat of water at 25°C is 0.998
cal/g-deg, the value of the heat of combustion of benzoic acid is [AFMC 2010]
(1) 881.1 kcal (2) 771.4 kcal (3) 981.1 kcal (4) 871.2 kcal

87. The heat of combustion of methane, if the heat of formation of CH4, CO2 and H2Oare
respectively –18.4 kcal, –94.0 kcal, –68.4 kcal is [CPMT 2010]
(1) –212.4 kcal (2) +212.4 kcal (3) –249.2 kcal (4) +249.2 kcal

88. The amount of heat evolved when 500 cm3 of 0.1 M HCl is mixed with 200 cm3 of 0.2 M NaOH
is [KCET 2010]
(1) 2.292 kJ (2) 1.292 kJ (3) 0.292 kJ (4) 3.392 kJ

96 COLLEGES: ANDHERI / BORIVALI / CHEMBUR / DADAR / KALYAN / KHARGHAR / NERUL / POWAI / THANE
 Thermodynamics Ch. XI
89. The heat of neutralization of four acids A, B, C and D when neutralized against a common base
are 13.7, 9.4, 11.2 and 12.4 kcal respectively. The weakest among these acids is
(1) A (2) B (3) C (4) D

90. The bond energies of C—C, C = C, H—H and C—H linkages are 350, 600, 400 and 410 kJ/mol
respectively. The heat of hydrogenation of ethylene is [BVP 2010]
(1) -170 kJ /mol (2) -400 kJ /mol (3) -260 kJ /mol (4) -450 kJ /mol

91. According to second law of thermodynamics, a process (reaction) is spontaneous, if during the
process [Manipal 2010]
(1) Suniverse  0 (2) Suniverse  0 (3) Hsystem  0 (4) Suniverse  Ssystem

92. Calculate the free energy change for the following reaction at 300 K. [Manipal 2010]
1
2CuO  s  
 Cu 2 O  s   O2  g 
2
Given, H  145.6 kJ mol1
and S  116 JK1mol1
(1) 110.8 kJ mol–1 (2) 221.5 kJ mol–1 (3) 55.4 kJ mol–1 (4) 145.6 kJ mol–1

93. Which one of the following is correct ? [JCECE 2010]

(1) G  H  TS (2) H  G  TS
1 1
(3) S  [G  H] (4) S  [H  G]
T T

94. Which of the following is the correct option for free expansion of an ideal gas under adiabatic
condition. [CBSE AIPMT-2011]
(1) q = 0, T <0 , w  0 (2) q = 0, T 0, w =0
(3) q  0, T = 0 , w = 0 (4) q = 0, T = 0, w = 0

95. Enthalpy change for the reaction 4H(g) 

 2H2(g) is –869.5 kJ. The dissociation energy of
H—H bond is [CBSE AIPMT-2011]
(1) + 217.4 kJ (2) –434.8 kJ (3) –869.6 kJ (4) +434.8 kJ

96. If the enthalpy change for the transition of liquid water to steam is 300 kJ mol -1 at 27oC, the
entropy change for the process would be [CBSE AIPMT-2011]
-1 -1
(1) 100 JK mol (2) 10 JK-1mol-1
(3) 1.0 JK-1mol-1 (4) 0.1 JK-1mol-1.

97. Based on the first law of thermodynamics, which one of the following is correct? [KCET 2011]
(1) For an isothermal process q = + w (2) For an isochoric process,  U = –q
(3) For an adiabatic process,  U = –w (4) For a cyclic process, q = –w

98. The enthalpy of solution of sodium chloride is 4 kJ mol–1 and its enthalpy of hydration of ions is
–784 kJ mol–1. Then the lattice enthalpy of NaCl (in kJ mol–1) is [Kerala CEE 2011]
(1) + 788 (2) +4 (3) +98 (4) +780
(5) +394

99. Which reaction, with the following values of H, S at 400 K is spontaneous and endothermic?
[DUMET 2011]
(1) H  48kJ; S  135 J / K (2) H  48kJ; S  135 J / K
(3) H  48kJ; S  135 J / K (4) H  48kJ; S  135 J / K

COLLEGES: ANDHERI / BORIVALI / CHEMBUR / DADAR / KALYAN / KHARGHAR / NERUL / POWAI / THANE 97
 Thermodynamics Ch. XI
100. The enthalpy of vaporisation of benzene is +35.3 kJ/mol at its boiling point of 80°C. The
entropy change in the transition of vapour to liquid at its boiling point is … (in J mol–1 K–1).
[KCET 2011]
(1) –100 (2) +100 (3) +342 (4) –342

101. For the reversible reaction, [KCET 2011]

A s  Bg  C  g   D  g  , G  350kJ.
o

which one of the following statement is true?

(1) The reaction is thermodynamically non-feasible
(2) the entropy change is negative
(3) Equilibrium constant is greater than one
(4) The reaction should be instantaneous

102. A reaction is spontaneous at low temperature but non-spontaneous at high temperature. Which
of the following is true for the reaction? [Kerala CEE 2011]
(1) H  0, S  0 (2) H  0, S  0
(3) H  0, S  0 (4) H  0, S  0
(5) H  0, S  0

103. A reaction having equal energies of activation for forward and reverse reactions has
[NEET 2013]
(1) H = G = S = 0 (2) S = 0
(3) G = 0 (4) H = 0

104. Which of the following statement is correct for the spontaneous adsorption of a gas?
[AIPMT 2014]
(1) S is positive and, therefore, H should be negative.
(2) S is positive and, therefore, H should also be highly positive.
(3) S is negative and, therefore, H should be highly positive.
(4) S is negative and therefore, H should be highly negative.

105. For the reaction: [AIPMT 2014]

X2O4(l)  2XO2(g)
U = 2.1 k cal, S = 20 cal K–1 at 300 K. Hence, G is:
(1) 9.3 kcal (2) –9.3 kcal (3) 2.7 kcal (4) –2.7 kcal

106. Which of the following statements is correct for a reversible process in a state of equilibrium?
[AIPMT 2015]
(1) G  2.30RT log K (2) G  2.30RT log K
(3) G  2.30RT log K (4) G  2.30RT log K

107. The heat of combustion of carbon to CO2 is –393.5 kJ/mol. the heat released upon formation of
35.2 g of CO2 from carbon and oxygen gas is: [RE-AIPMT 2015]
(1) –630 kJ (2) –3.15 kJ (3) –315 kJ (4) +315 kJ

108. The correct thermodynamic conditions for spontaneous reaction at all temperatures is
[NEET-UG 2016]
(1) H < 0 and S < 0 (2) H < and S = 0
(3) H > 0 and S < 0 (4) H < 0 and S > 0

98 COLLEGES: ANDHERI / BORIVALI / CHEMBUR / DADAR / KALYAN / KHARGHAR / NERUL / POWAI / THANE
 Thermodynamics Ch. XI
109. Consider the following liquid – vapour equilibrium. [NEET-UG 2016]
Liquid Vapour
Which of the following relations is correct?
d ln P H v d ln G H v d ln P H v d ln P H v
(1)  (2)  (3)  (4) 
dT RT 2 dT 2 RT 2 dT RT dT 2 T2

QUESTIONS ASKED IN 2018 to 2021

1. Which one of the following characteristics is associated with adsorption? [AIPMT 2016]
(1) G, Hand S all are negative
(2) Gand H are negative but S is positive
(3) Gand S are negative but H is positive
(4) G is negative but Hand S are positive

2. The correct thermodynamic conditions for the spontaneous reaction at all temperatures is:
[AIPMT 2016]
(1) H  0and S  0 (2) H  0and S  0
(3) H  0and S  0 (4) H  0and S  0

3. For a sample of perfect gas when its pressure is changed isothermally from pi to pf , the entropy
change is given by [NEET 2016]
p  p  p  p 
(1) S  nR1n  f  (2) S  nR1n  i  (3) S  nRT1n  f  (4) S  RT1n  f 
 pi   pf   pi   pi 

4. If the Ecell for a given reaction has a negative value, which of the following gives the correct
relationships for the values of G and K eq [NEET 2016]
(1) G  0; K eq 1 (2) G 0; K eq 1 (3) G 0; K eq 1 (4) G 0; K eq 1

5. Which one of the following is incorrect for ideal solution? [NEET 2016]
(1) Hmix  0 (2) Umix  0
(3) P  Pobs  Pcalculated by  0 (4) Gmix  0

6. Mathematical equation of first law of thermodynamics for isochoric process is

[MH-CET 2016]
(1) U  q v (2) U  q v (3) q  W (4) U  W

7. The criterion for a spontaneous process is [MH-CET 2016]

(1) G  0 (2) G  0 (3) G  0 (4) Stotal  0

8. Identify an extensive property amongst the following [MH-CET 2016]

(1) Viscosity (2) Heat capacity (3) Density (4) Surface tension

9. What is the amount of work done when 0.5 mole of methane, CH4 (g), is subjected to combustion
at 300 K ? (given, R = 8.314 J K–1 mol–1) [MH-CET 2016]
(1) – 2494 J (2) – 4988 J (3) + 4988 J (4) + 2494 J

COLLEGES: ANDHERI / BORIVALI / CHEMBUR / DADAR / KALYAN / KHARGHAR / NERUL / POWAI / THANE 99
 Thermodynamics Ch. XI
10. A gas is allowed to expand in a well insulated container against a constant external pressure of
2.5 atm from an initial volume of 2.50 L to a final volume of 4.50 L. The change in interval
energy U of the gas in joule will be : [NEET 2017]
(1) 1136.25 J (2) –500 J (3) –505 J (4) +505 J

11. For a given reaction, H  35.5kJ mol1 and S  83.6 JK1mol1 . The reaction is spontaneous
at : (Assume that H and S do not vary with temperature) [NEET 2017]
(1) T  425K (2) T  425K (3) all temperature (4) T  298K

12. The bond dissociation energies of X 2 , Y2 and XY are in the ratio of 1:0.5:1. H for the
1
formation of XY is -200 kJ mol . The bond dissociation energy of X 2 will be
[NEET 2018]
1 1 1 1
(1) 800 kJ mol (2) 400 kJ mol (3) 100 kJ mol (4) 200 kJ mol

13. Under isothermal condition, a gas at 300 K expands from 0.1 L to 0.25 L against a constant
external pressure of 2 bar. The work done by the gas is
(Given that 1 L bar = 100 J) [NEET (National) 2019]
(1) 5 kJ (2) 25J (3) 30J (4) –30J

14. An ideal gas expands isothermally from 10–3 m3 to 10–2 m3 at 300 K against a constant
pressure of 105 Nm–2. The work done on the gas is [NEET (Odisha) 2019]
(1) +270 kJ (2) –900 J (3) +900 kJ (4) –900 kJ

15. In which case change in entropy is negative? [NEET (National) 2019]

(1) Expansion of a gas at constant temperature (2) Sublimation of solid to gas
(3) 2H(g)  H2 (g) (4) Evaporation of water

16. For an ideal solution, the correct option is [NEET (National) 2019]
(1) mix V  0 at constant T and p (2) mix H  0 at constant T and p
(3) mix G  0 at constant T and p (4)  mixS  0 at constant T and p

17. Reversible expansion of an ideal gas under isothermal and adiabatic conditions are as shown in
the figure [NEET (Odisha) 2019]

AB  Isothermal expansion
AC  Adiabatic expansion
Which of the following option is not correct?
(1) Sisothermal  Sadiabatic (2) TA = TB
(3) Wisothermal  Wadiabatic (4) TC  TA

18. For the reaction, 2Cl(g)  Cl2 (g), the correct option is [NEET (Sep.)2020]
(1) r H  0and rS  0 (2) r H  0and rS  0
(3) r H  0and rS  0 (4) r H  0and rS  0
100 COLLEGES: ANDHERI / BORIVALI / CHEMBUR / DADAR / KALYAN / KHARGHAR / NERUL / POWAI / THANE
 Thermodynamics Ch. XI
19. Hydrolysis of sucrose is given by the following reaction.
Sucrose  H2O Glu cos e  Fructose
If the equilibrium constant (Kc) is
2 1013 at300K, the value of  r G  at the same temperature will be [NEET (Sept.) 2020]
1 1 1 1
(1) 8.314J mol K  300K  ln(2 10 ) (2) 8.314J mol K  300K  ln(3 10 )
13 13

1 1 1 1
(3) 8.314J mol K  300K  ln(4 10 ) (4) 8.314J mol K  300K  ln(2 10 )
13 13

20. If for a certain reaction  r H is 30 kJ mol–1 at 450 K, the value of rS (in JK–1 mol–1) for which
the same reaction will be spontaneous at the same temperature is [NEET (Oct.) 2020]
(1) 70 (2) –33 (3) 33 (4) –70

21. The correct option for free expansion of an ideal gas under the adiabatic condition is
[NEET (Sept.) 2020]
(1) q  0, T  0and w  0 (2) q  0, T  0and w  0
(3) q  0, T  0and w  0 (4) q  0, T  0and w  0

22. At standard conditions, if the change in the enthalpy for the following reaction is –109 kJ mol–1.
H2 (g)  Br2 (g)  2HBr(g)
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 ? [NEET (Oct.) 2020]
(1) 368 (2) 736 (3) 518 (4) 259

23. Which one among the following is the correct option for right relationship between Cp and Cv
for one mole of ideal gas ? [NEET 2021]
(1) Cp + Cv = R (2) Cp – Cv = R
(3) Cp = RCv (4) Cv = RCp

24. For irreversible expansion of an ideal gas under isothermal condition the correct option is
[NEET 2021]
(1)  U  0, S total  0 (2) U  0, Stotal  0
(3) U  0, Stotal  0 (4) U  0, Stotal  0

――

COLLEGES: ANDHERI / BORIVALI / CHEMBUR / DADAR / KALYAN / KHARGHAR / NERUL / POWAI / THANE 101
 Thermodynamics Ch. XI

EXERCISE KEY
Multiple Choice Questions

1. (3) 2. (3) 3. (4) 4. (4) 5. (3)

6. (2) 7. (3) 8. (3) 9. (4) 10. (3)
11. (1) 12. (3) 13. (2) 14. (2) 15. (3)
16. (3) 17. (2) 18. (3) 19. (1) 20. (3)
21. (2) 22. (1) 23. (3) 24. (3) 25. (1)
26. (3) 27. (1) 28. (3) 29. (4) 30. (2)
31. (3) 32. (4) 33. (1) 34. (3) 35. (3)
36. (1) 37. (4) 38. (3) 39. (2) 40. (4)
41. (1) 42. (1) 43. (3) 44. (3) 45. (2)
46. (4) 47. (4) 48. (3) 49. (3) 50. (3)
51. (4) 52. (3) 53. (3) 54. (1) 55. (3)
56. (3) 57. (4) 58. (2) 59. (3) 60. (2)
61. (2) 62. (4) 63. (4) 64. (2) 65. (1)
66. (2) 67. (1) 68. (2) 69. (1) 70. (2)
71. (3) 72. (4) 73. (3) 74. (3) 75. (2)
76. (1) 77. (1) 78. (1) 79. (2) 80. (2)
81. (1) 82. (4) 83. (3) 84. (4) 85. (3)
86. (1) 87. (2) 88. (1) 89. (3) 90. (4)
91. (1) 92. (2) 93. (3) 94. (2) 95. (4)
96. (2) 97. (3) 98. (1) 99. (4) 100. (4)
101. (1) 102. (4) 103. (4) 104. (1) 105. (3)
106. (2) 107. (4) 108. (4) 109. (3) 110. (1)
111. (2) 112. (1) 113. (1) 114. (4) 115. (3)
116. (2) 117. (3) 118. (4) 119. (3) 120. (4)
121. (3) 122. (3) 123. (4) 124. (4) 125. (3)
126. (3) 127. (2) 128. (2) 129. (1) 130. (4)
131. (3) 132. (2) 133. (1) 134. (2) 135. (2)
136. (1) 137. (2) 138. (2) 139. (3) 140. (1)
141. (1) 142. (2) 143. (4) 144. (4) 145. (2)
146. (4) 147. (4) 148. (3)

Previous Year’s Questions

1. (1) 2. (1) 3. (3) 4. (3) 5. (1)

6. (2) 7. (1) 8. (4) 9. (2) 10. (3)
11. (4) 12. (4) 13. (4) 14. (3) 15. (4)
16. (4) 17. (2) 18. (2) 19. (4) 20. (1)
21. (1) 22. (2) 23. (3) 24. (1) 25. (4)
26. (2) 27. (1) 28. (1) 29. (2) 30. (1)
31. (3) 32. (4) 33. (3) 34. (4) 35. (1)
36. (2) 37. (1) 38. (2) 39. (3) 40. (1)
41. (1) 42. (4) 43. (4) 44. (1) 45. (3)
46. (3) 47. (3) 48. (1) 49. (4) 50. (3)
51. (3) 52. (1) 53. (4) 54. (3) 55. (5)
56. (3) 57. (3) 58. (2) 59. (4) 60. (3)
61. (2) 62. (2) 63. (3) 64. (3) 65. (4)

102 COLLEGES: ANDHERI / BORIVALI / CHEMBUR / DADAR / KALYAN / KHARGHAR / NERUL / POWAI / THANE
 Thermodynamics Ch. XI
66. (4) 67. (1) 68. (1) 69. (3) 70. (3)
71. (3) 72. (4) 73. (3) 74. (1) 75. (1)
76. (4) 77. (3) 78. (2) 79. (4) 80. (2)
81. (2) 82. (2) 83. (2) 84. (1) 85. (4)
86. (2) 87. (1) 88. (1) 89. (2) 90. (1)
91. (1) 92. (1) 93. (4) 94. (4) 95. (4)
96. (1) 97. (4) 98. (1) 99. (3) 100. (1)
101. (3) 102. (4) 103. (4) 104. (4) 105. (4)
106. (2) 107. (3) 108. (4) 109. (1)

QUESTIONS ASKED IN 2016 to 2021

1. (1) 2. (2) 3. (2) 4. (1) 5. (4)

6. (1) 7. (2) 8. (2) 9. (4) 10. (3)
11. (2) 12. (1) 13. (4) 14. (2) 15. (3)
16. (2) 17. (4) 18. (3) 19. (4) 20. (1)
21. (4) 22. (1) 23. (2) 24. (3)

――

COLLEGES: ANDHERI / BORIVALI / CHEMBUR / DADAR / KALYAN / KHARGHAR / NERUL / POWAI / THANE 103