THERMODYNAMICS

AND
THERMO CHEMISTRY
Table of Contents

 Theory ................................................................................................................................ 2

 Solved Examples ................................................................................................................ 9

 Exercise - 1 : Basic Objective Questions ........................................................................... 22

 Exercise - 2 : Previous Year JEE MAINS Questions ........................................................... 32

 Exercise - 3 : Advanced Objective Questions .................................................................. 37

 Exercise - 4 : Previous Year JEE Advanced Questions ...................................................... 44

 Answer Key .......................................................................................................................... 50

 THEORY

1. THERMODYNAMICS 4.2 Intensive Properties

It is the study of flow of energy. It encompasses the study of flow Such properties of a system which depends on concentration
of heat as well as mass. and does not depend on the mass or the total number of particles
in the system are categorized as Intensive properties. eg. Pressure,
Density, Reractive Index.
2. THERMODYNAMICS TERMINOLOGY
5. STATE AND PATH FUNCTIONS
2.1 System
Such thermodynamic functions which depend only on the initial
and final states of the system and not on the path followed are
The part of the Universe under observation is called system. called state functions eg. Internal energy, Enthalpy and the
functions which depend on the path followed while changing
2.2 Surrounding from one state to the other are called path functions. eg. work
heat.
The part of the Universe not under observation is called
Surrounding. 6. THERMODYNAMIC EQUILIBRIUM
System + Surrounding = Universe
A system is said to be under thermodynamic equilibrium when
2.3 Types of system none of the state variables are changing and it satisfies the three
equilibriums.
2.3.1 Open System : A system in which both flow of mass and
heat is possible. 6.1 Mechanical Equilibrium
2.3.2 Closed System : A system in which flow of heat is possible
but flow of mass is not possible. There is no mechanical motion and the pressure and the volume
of the system is not changing.
2.3.3 Isolated System : A system in which neither heat nor mass
can flow in or out. 6.2 Thermal Equilibrium
3. STATE OF A SYSTEM There is no flow of heat and the temperature of the system does
not change with time.
The state variables (P, V, T, n) describes the condition of a system.
On changing any one or more of these variables the state of the 6.3 Chemical Equilibrium
system changes.
If any chemical reaction is taking place in the system then the rate
4. PROPERTIES OF SYSTEM of forward reaction is equal to the rate of backward reaction which
means that the overall moles of the system is constant.
All the properties of a system can be categorized into one of the
following two types : 7. INTERNAL ENERGY
4.1 Extensive Properties
It is the sum total of the components of energy of the system due
to the internal factors. It is denoted by U (sometimes by E). Since
Such properties of a system which depends on the mass or the the system under observation is an ideal gas thus the internal
total number of particles in the system are categorized as Extensive energy of the system is dependent only on the kinetic energy of
Properties. eg. Total Energy, volume. the gas and therefore is only a function of temperature. U  T.
Since internal energy depends only on temperature thus, it is a
state function.
 8. MODES OF ENERGY TRANSFER 11. EXPANSION WORK

It is the work done due to the volume changes of the gas. The
There are two methods to alter the internal energy of a system viz.
Heat and work.

mathematical expression for the expansion work is w   Pex dV.
8.1 Heat
Always remember, be it expansion or compression we always take
the external pressure as the driving force. For a reversible process,
Heat is the energy transferred due to temperature difference
between the system and the surrounding. On heating, the kinetic 
Pex  PGAS and w   PGASdV.
energy of the molecules increases and therefore the internal energy
increases. If we draw a process curve between P and V then the work done
is represented by the area covered under the P-V graph as shown
8.2 Work in Fig.

Work is the energy spent to overcome an external force. When

the system does work against an external pressure (expansion) it
tends to reduce the internal energy and on the other hand when
the system contracts due to the external pressure it tends to
increase the internal energy.

9. FIRST LAW OF THERMODYNAMICS

The first law of Thermodynamics states that Energy can neither
be created nor destroyed.
U = q + w
Conventions : In the above system if work is done by the system
then w is negative and if work is done on the system then w is NOTE
positive. Also, if heat flows into the system then q is positive and
Sign of w : If the volume of the system is increasing
if heat flows out of the system then q is negative.
then the sign of w is –ve and if volume is decreasing
w is +ve
10. REVERSIBILITY
Sign of U : If the temperature of the system is
A process whose direction can be changed by an infinitesimal decreasing or the product pressure and volume (PV) is
change to the system or surroundings and which can be reversed reducing then the sign of U is –ve else, the sign of
by retracing the original path and the system is restored to the U is +ve.
initial state. The driving force of a reversible process is very-very
Sign of q : The sign of q needs to be determined using
small and such a process is extremely slow. For a process to be
the first law of thermodynamics.
reversible there must not be any dissipative forces and also the
system should be in a Quasi Static State.
12. CYCLIC PROCESS
10.1 Quasi Static State
A cyclic process is one which comes back to its initial state. The
A quasi static state means that the system seems to be static at all graph of a cyclic process is always a closed graph. For a cyclic
intervals of time but actually is not. The motion is so slow that it process, Unet = 0 and qnet = – wnet.
is almost impossible to detect the motion and the system seems
to be in equilibrium with the surroundings at all instants of time.
 13. ENTHALPY (H) 15.1 Isothermal Process

Enthalpy is another thermodynamic function (like internal energy, These processes are the ones in which the temperature is constant
work and heat) which we study in various thermodynamic throughout the process.
processes. It is also a state function like internal energy. It is
U = 0; H = 0
defined as the sum of the energy stored in the system and the
energy used in doing work. Mathematically, H = U + PV. At constant w = –2.303 nRT log10(V2/V1) = – 2.303 nRT log10 (P1/P2)
pressure H = qp and at constant volume U = qV. q = +2.303 nRT log10 (V2/V1) = + 2.303 nRT log10 (P1/P2)

14. HEAT CAPACITY (C) 15.2 Adiabatic Process

The heat capacity of the system is the amount of heat needed to These processes are the ones in which the heat exchanged with the
raise the temperature of the system by 1ºC or 1K. surroundings is zero. Such processes are defined by the equation

C = q/T. TV–1 = constant, TP1– = constant, PV = constant.

q=0  w = U
14.1 Molar Heat Capacity
U = nCVT = (P2V2 – P1V1)/(–1). = (nRT)/( – 1)

The molar heat capacity of a system (CM) is the amount of heat H = nCPT
needed to raise the temperature of one mole gas by 1ºC or K.
15.3 Isochoric Process
q
CM 
nT
These processes are the ones in which the volume remains constant.
The molar heat capacity of a system at constant pressure (Cp) is Since the change in volume is zero therefore we can say that
the amount of heat needed to raise the temperature of one mole w=0
gas the system by 1ºC at constant pressure.
U = nCVT = qV H = nCPT
Cp = qp /nT.
The molar heat capacity of a system at constant volume (CV) is 15.4 Isobaric Process
the amount of heat needed to raise the temperature of one mole
gas by 1ºC at constant volume. These are the processes in which the pressure remains constant.
CV = qV /nT. w = – PV = – nRT
Thus, we can say that : H = nCPT and U = nCVT and U = nCVT
CP = CV + R.
H = nCPT

NOTE
All these processes are happening on a system containing an
ideal gas therefore we can apply PV = nRT at any stage that
we find suitable.

15. TYPES OF THERMODYNAMIC PROCESSES

There are four important types of processes to be studied in this

chapter. The basic meanings and difference of these four
processes are :
 4. A cyclic process should remain cyclic whichever graph we
NOTE make.
Although the graph of isothermal and adiabatic processes are
similar in nature it should be noted that the P-V graph of an
adiabatic process is steeper than that of an isothermal process.

16. GRAPH TRANSFORMATION

When a thermodynamic process is plotted in terms of two state

variable it can be transformed into a graph involving the other
state variable by doing the following :
Note : From the given P–V graph.
1. Identify the type of curve given, whether it is P-V, V-T or P-T
graph. Process 12 is isothermal expansion; 23 adiabatic expansion;

2. Then, Identify every step of the process 34 isothermal compression & 41 adiabatic compression.

3. Then one by one convert every step into the required graph
bearing in mind critical points like, an expansion process will
remain an expansion process and so on.
 17. IRREVERSIBLE PROCESS 22. CONCEPT OF ENTROPY
For an irreversible process the work done is given by
 Matter has a natural tendency to get disordered or randomised
W=– P EXT dV. We cannot take the external pressure to be
 Energy has a tendency to become disordered or dispersed.
equal to the pressure of the gas in these processes.
It was concluded that any such process in which the total
18. FREE EXPANSION randomness of the universe (system + surrounding) increases is
a spontaneous process. Entropy is a measure of randomness or
If the external pressure of the gas is zero that is the gas is expanding disorder. It is a state function represented by S. We can safely
against vaccum then the work done is always zero, this is called say that in a spontaneous process there is a tendency for increase
the case of free expansion. In this process the gas does no work in entropy. Hence the statement of second law :
as there is no effort put in expansion process. If no heat is supplied
The entropy of an isolated system/Universe tends to increase
to the gas then there is no change in temperature too. That is why
OR In a spontaneous process the entropy of the Universe
such a process is both Isothermal and Adiabatic.
increases.
19. POLYTROPIC PROCESS S = qrev/T.

It is a generalized form of any thermodynamic process which has STOTAL  SSYSTEM  SSURROUNDING  0
a form PVn = constant where n is a real number. For an isothermal (for a sponataneous change)
process n = 1 and for an adiabatic process n = . The heat capacity
Thus, In a reversible process the entropy of the Universe remains
of a polytropic process can be calculated using the first law of
thermodynamics and comes out to be : constant i.e. STotal = 0
C = CV – R/(n – 1).
22.1 Entropy changes in a Thermodynamic Process

20. NEED FOR SECOND LAW

The entropy changes in an thermodynamic process can be
mathematically calculated by the equation :
The first law talks about the conservation of energy in a process
but does not speak of the feasibility of a process. It does not tell S = nCV ln (T2/T1) + nR ln (V2/V1). This expression can be
whether a process will happen on its own i.e. whether the process simplified for the four processes studied earlier as :
is spontaneous or not. A spontaneous process is one which
Isothermal process : S = nR ln (V2/V1)
happens on its own. Example, heat always flows spontaneously
from higher temperature to lower temperature : Nothing in the first Isochoric process : S = nCV ln (T2/T1)
law mentions that the opposite process cannot happen. According
to first law any process where energy remains conserved is feasible. For isobaric process : S = nCP ln (T2/T1)
But we need some other basis for feasibility of a process. This is Adiabatic process : S = 0 (qrev = 0)
where the second law is important.
22.2 Important points to Remember
21. TYPES OF PROCESSES
1. Entropy of a system remains constant in a reversible adiabatic
21.1 Spontaneous processes process. Therefore, it is also known as “isentropic process”.
2. Entropy of an ideal gas will always increase in isothermal
Spontaneous processes have a natural tendency to take place expansion.
and no external work is needed to carry out these processes. All
3. In a reversible adiabatic process the entropy of both system
natural processes are spontaneous.
and surroundings remains the same and there is no overall
21.2 Non-Spontaneous processes change in entropy as well.
SSYSTEM = SSURROUNDINGS = STOTAL = 0
They are driven by external work and cannot take place naturally.
4. In a reversible isothermal expansion the entropy of
surroundings will always decrease to balance the increase in 25.1 Enthalpy of Formation Hf0
system’s entropy to make the overall entropy constant.
5. In free expansion the entropy of the system always increases It is the heat absorbed or released when one mole of a compound
and that of surrounding remains constant. Free expansion is is formed from its constituent elements under their standard
elemental forms. The enthalpy for formation of the following
both isothermal and adiabatic and is irreversible.
substances is taken to be zero under 1 bar pressure and 298 K.
23. GIBB’S FREE ENERGY Hf0 (O2, g) = 0 Hf0 (S, Rhombic) = 0
Hf0 (C, graphite) = 0 Hf0 (P, white) = 0
Gibb’s Free energy function gives us a very convenient parameter
Hf0 (Br2, l) = 0 Hf0 (H+, aq) = 0
to judge the spontaneity of a process from system’s perspective.
At a constant temperature and pressure, G = –TSTOTAL and for 25.2 Enthalpy of Combustion
a process to be spontaneous, G < 0. The change in Gibb’s free
energy can also be represented in terms of the system parameters It is the heat released or absorbed when one mole of a substance
as : undergoes combustion in presence of oxygen.
GSYS = H – TSsys at a constant temperature. CH4 (g) + 2O2 (g)  CO2 (g) + 2H2O (g) H = – 890 kJ/mol

24. THERMOCHEMICAL EQUATION 25.3 Enthalpy of Solution

A chemical equation which gives us all the information like energy It is the heat released or absorbed when 1 mole of a compound is
changes associated with a chemical reaction and phases of various dissolved in excess of a solvent (water).
reactants and products is called Thermochemical Equation. MgSO4 (s) + H2O (excess) Mg2+ (aq) + SO42– (aq)
All reactions can be categorized into one of the following two
H0Sol = – 91.211 kJ/mol
categories :
25.4 Enthalpy of Hydration
24.1 Endothermic Reactions
It is the energy released or absorbed when 1 mole of anhydrous
Are those chemical reactions which absorb energy. or partially hydrated salt undergoes hydration by the addition of
(H = positive) water of crystallisation. e.g.
CuSO4(s) + 5H2O(l)  CuSO4. 5H2O(s)
24.2 Exothermic Reactions
HHYD = –78.9 kJ/mol
Are those chemical reactions which release energy.
25.5 Enthalpy of Neutralization
H = negative)
For a chemical reaction, HREACTION = HPRODUCTS – HREACTANTS It is the heat released or absorbed when one equivalent of an acid
The change in enthalpy during a chemical reaction occurs due to undergoes neutralisation with one equivalent of a base. e.g.
breaking and making of bonds. H+ (aq) + OH– (aq)  H2O (l )
Also, H = U + ngRT. HR = – 57.3 kJ/mol

25. ENTHALPY OF REACTIONS 26. HESS LAW OF CONSTANT HEAT SUMMATION

Enthalpy change can be calculated for all reactions and is Since enthalpy is a state function thus for a reaction which takes
sometimes called the Heat of Reaction. Let’s take a look at various place in steps the net change in enthalpy can be calculated by
types of reactions and enthalpy changes associated with them : adding the enthalpy changes of each step. This is called the Hess
Law.
 27. BORN HABER CYCLE 29. HEAT OF ATOMIZATION

The entire thermodynamics process of formation of an ionic crystal It is defined as the energy required to convert any substance to
lattice is called Born Haber cycle. An ionic compound is formed gaseous atoms. This is defined per mol of the gaseous atoms. For
from its constituents through a series of steps involving example Heat of atomisation of H will be 218 kJ/mol atoms.
conversion of atoms/molecules into gaseous phase for ion
formation, ionisation and electron gain to form ions and then the 30. RESONANCE ENERGY
reaction of gaseous ions to form solid lattice.
Many compounds exhibit resonance. Due to resonance they exist
28. BOND DISSOCIATION ENTHALPY
in a structure which is different from the expected one and more
stable.
The energy needed to break the bonds of one mole molecules is
called the Bond Dissociation Enthalpy of the substance. It is Resonance energy = H0f (actual) – H0f (calculated)
defined per mol of molecule. eg. Bond dissociation enthalpy of
H2 is 436 kJ/mol
 SOLVED EXAMPLE

20
Example : 1 – 4754 = – 2.303 × n × 8.314 × 300 log .
10
Calculate the internal energy change in each of the This given n = 2.75 moles.
following cases :
(i) A system absorbs 15 kJ of heat and does 5 kJ of work. Example : 4
(ii) 5 kJ of work is done on the system and 15 kJ of heat A 5-litre cylinder contained 10 moles of oxygen gas at
is given out by the system. 27oC. Due to sudden leakage through the hole, all the gas
escaped into the atmosphere and the cylinder got empty. If
Sol. (i) Here, q = +15 kJ the atmospheric pressure is 1.0 atmosphere, calculate
w = – 5 kJ the work done by the gas. (1 L atm = 101.3 J)
 According to first law of thermodynamics,
U = q + w = 15 + (–5) = 10 kJ Sol. Vinitial = 5L, T = 27oC = 27 + 273 K = 300 K
Thus, internal energy of the system increases by 10 kJ.
nRT 10  0.0821 300
(ii) Here, w = + 5 kJ Vfinal =   246.3 L
P 1.0
q = – 5 kJ
V = final – Vinitial = 246.3 – 5 = 241.3 L
 According to first law of thermodynamics,
U = q + w = – 15 + (+ 5) = – 10 kJ wexp = – PV = – 1 × 241.3 L atm = – 241.3 × 101.3 J
Thus, the internal energy of the system decreases by 10 kJ. = – 24443.7 J.
Example : 2 Example : 5

Calculate w, q and U when 0.75 mol of an ideal gas Two moles of an ideal gas initially at 27oC and one
expands isothermally and reversibly at 27oC from a volume atmospheric pressure are compressed isothermally and
of 15 L to 25 L. reversibly till the final pressure of the gas is 10 atm.
Calculate q, w and U for the process.
Sol. For isothermal reversible expansion of an ideal gas,
V2 Sol. Here, n = 2 moles T = 27oC = 300 K, P1 = 1 atm, P2 = 10 atm
w = – 2.303 nRT log V Putting n = 0.75 mol, V1 = 15 L,
1 P1
V2 = 25 L, T = 27 + 273 = 300 K and R = 8.314 J K–1 mol–1, w = –2.303 n RT log  2.303  2  8.314 JK 1 mol–1 ×
P2
we get
25 1
w = – 2.303 × 0.75 × 8.314 × 300 log  955.5 J
15 300 K × log = 11488 J
10
(–ve sign represents work of expansion)
For isothermal expansion of an ideal gas, U = 0 For isothermal compression of ideal gas, U = 0
U = q + w gives q = – w = + 955.5 J. Further, U = q + w  q = – w = – 11488 J.

Example : 3
Example : 6
Carbon monoxide is allowed to expand isothermally and
10g of argon gas is compressed isothermally and
reversibly from 10 m3 to 20 m3 at 300 K and work obtained
reversibly at a temperature of 27ºC from 10L to 5L.
is 4.754 kJ. Calculate the number of moles of carbon
Calculate q, W, U and H for this process.
monoxide.
R = 2.0 cal K–1 mol–1. log10 2 = 0.30 Atomic wt. of Ar = 40
V2
Sol. w = – 2.303 n RT log V V2
1 Sol. W = – 2.303 nRT log10
V1
 U = H = 0 (temperature is constant)
10 5
= – 2.303 × × 2 × 300 log10 w = – nRT ln (V2/V1)
40 10
= – 5 × 8.314 × 300 × ln 5
W = 103.991 cal
= – 20071.3 J
U = 0 ; H = 0 (Constant temperature)
q = + 20071.3 J
 q = U – W q = – W = – 103.991 cal

Example : 7 Example : 9
The state of a mole of an ideal gas changed from state A
A gas present in a cylinder fitted with a frictionless piston (2p, v) through four different processes and finally returns
expands against a constant pressure of 1 atm from a volume to initial State A reversibly as shown below.
of 2 litre to a volume of 6 litre. In doing so, it absorbs
800 J heat from surroundings. Determine increase in
internal energy of process.

Sol. Since, work is done against constant pressure and thus,

irreversible.
Given, V = (6 – 2) = 4 litre; P = 1 atm
 W = – 1 × 4 litre-atm = – 4 × 1.01325 × 102 J
= 405.3 J
Now from first law of thermodynamics
q = U – W
800 = U + 405.3  U = 394.7 Joule Calculate the total work done by the system and heat
absorbed by the system in the cyclic process.
Example : 8
5 moles of an ideal gas at 300 K are expanded isothermally Sol. State A to State B (Isobaric expansion)
from an initial pressure of 500 Pa to a final pressure of Pressure is held constant at 2p and the gas is heated
100 Pa against a constant external pressure of 100 Pa. until the volume v becomes 2v.
Calculate w, q, U and H for the process. What will be the
difference if the same process is carried out irreversibly ?  W1 = – pV = – 2p (2v – v) = – 2pv
What are the values of w, q, U, H for the irreversible
process ? State B to State C (Isochoric process)

Volume is held constant at 2v and the gas is coolled

Sol. For an isothermal irreversible expansion : until the pressure 2P reaches p.
U = H = 0 W2 = 0 ( V = 0)
w = – PEXT (V2–V1)
State C to State D (Isobaric compression)
V2 and V1 can be calculated from ideal gas equation.
Pressure is held constant at p and the gas is further
V1 = nRT/P1 = 5 × 8.314 × 300/500 = 24.9 m 3 cooled until the volume 2v becomes v.

V2 = nRT/P2 = 124.7 m3 W3 = – p (v – 2v) = pv

Therefore, w = – 100 × (124.5 – 24.9) State D to State A (Isochoric process)

= – 9980 J Volume is held constant at v and the gas is heated
until the pressure p reaches 2p.
q = + 9980 J
W4 = 0 ( V = 0)
If this process is done reversibly then the internal and
external pressure should be same throughout.
 Total work done by the gas = W = W1 + W2 + W3 + W4 n = 2 mol.

or W = – 2pv + 0 + pv + 0 = – pv (= area ABCD) At point C : P = 0.5 atm, V = 40L

As the process is cyclic E = 0 PV = nRT

q = – w q = + pv 0.5  40

T = (0.0821) (2) = 121.8 K.
where q is the heat absorbed in the cylic process.
 20 
Example : 10 WCA = – 2.303 (2) (8.314) (121.8) log10  
 40 
Two mole of a perfect gas undergo the following processes: = 1404.07 J
(a) a reversible isobaric expansion from
Total work, W = – 2026.5 + 0 + 1404.07
(1.0 atm, 20.0L) to (1.0 atm, 40.0L).
(b) a reversible isochoric change of state from = – 622.43 J
(1.0 atm, 40.0L) to (0.5 atm, 40.0L) For cyclic process : U = 0
(c) a reversible isothermal compression from  q=–w
(0.5 atm, 40.0L) to (1.0 atm, 20.0L).
q = + 622.43 J
(i) sketch with labels each of the processes on the same
P-V diagram. Example : 11
(ii) Calculate the total work (w) and the total heat change
Calculate the amount of work done in each of the following
(q) involved in the above processes.
cases :
(iii) What will be the value of U, H and S for the
overall process ? (i) One mole of an ideal gas contained in a bulb of 10
litre capacity at 1 bar is allowed to enter into an
Sol. The overall is cyclic one, i.e., initial state is regained, thus evacuated bulb of 100 litre capacity.
U = 0; H = 0 and S = 0.
(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 atm (1 litres atm = 101.3 J)
Calculate the internal energy change (U) in each
case if the process were carried out adiabatically.

Sol. (i) w = –Pext × V

As expansion taks place into the evacuated bulb, i.e.,
against vacuum, Pext = 0. Henc, w = 0.
For adiabatic process, q = 0 U = q + w = 0 + 0 = 0.

Now, total work W = WAB + WBC + WCA (ii) V = V2 – V1 = 5 – 1 = 4 litres

WAB = – P (VB – VA) P = 1 atm  w = – PV
= – 1 (40 – 20) = – 20L atm = –1 × 4 litre atm = – 4 litres atm
= – 20 × 1.01325 × 102 J = – 4 × 101.3 J = – 405.2 J (1 L – atm = 101.3J)
= – 2026.5 J The negative sign implies that the work is done by the
WBC = O (Isochoric) system.

VA For adiabatic process, U = q + w = 0 – 405.2 J = – 405.2 J.

WCA = – 2.303 nRT log10 V
C
 Example : 12 Example : 14
An ideal gas is originally confined to a volume V1 in an
5.6 dm3 of an unknown gas at S.T.P. required 52.25 J of
insulated container of volume V1 + V2. The remainder of
heat to raise its temperature by 10oC at constant volume.
the container is evacuated. The portion is then removed
Calculate Cv, Cp and  of the gas
and the gas expands to fill the entire container. If the
initial temperature of the gas was T, what is the final
Sol. The 22.4 dm3 of a gas at S.T.P. = 1 mol temperature. Also predict qualitatively, the entropy change
of system, surroundings and the universe.
1
 5.6 dm3 of the gas at S.T.P. =  5.6  0.25 mol
22.4
Thus, for 10o rise, 0.25 mol of the gas at constant volume
require heat = 52.25 J
 For 1o rise, 1 mol of the gas at constant volume will
52.25
require heat =  20.9
10  0.25 Sol. This is a process of adiabatic free expansion of an ideal
 Cv = 20.9 J K mol –1 –1 gas. The internal energy does not change thus the
temperature also stays the same, i.e., the final temperature
Now, Cp = Cv + R = 20.9 J K–1 mol–1 + 8.314 J K–1 mol–1 = is still T.
29.214 J K–1 mol–1
V1  V2
Cp 29.214 Ssystem = nR ln V1 > 0  V1 + V2 > V1
   = 1.4
Cv 20.9
Ssurr = 0  qsurr. = 0
Example : 13 Suniv > 0

A heated copper block at 130oC loses 340 J of heat to the

Example : 15
surroundings which are at room temperature of 32oC.
Calculate 1.0 mol of an ideal gas, initially present in a 2.00 L insulated
cylinder at 300 K is allowed to expand against vacuum to
(i) the entropy change of the system (copper block) 8.00 L. Determine W, E, H, Suniv and G .
(ii) the entropy change in the surroundings

(iii) the total entropy change in the universe due to this

process
Sol.
Assume that the temperature of the block and the
surroundings remains constant.
W = – pext V = 0, q = 0, E = 0 = H
Sol. Tsystem = 130o C = 130 + 273 K = 403 K, Tsurr = 32oC = 32 +
273 K = 305 K qsystem = – 340 J, qsurr = + 340 J  Tf = 300 K

qsystem 340 J V2
(i) Ssystem  T   -0.84 JK -1 Ssys = R ln V = R ln 4 = 11.52 JK–1
system 403K 1

Ssurr = 0  qsys = qsurr = 0

qsurr 340J -1
(ii) Ssurr  T  305K  +1.11 J K
surr Suniv = 11.52 JK–1
(iii) Stotal or Suniverse = Ssystem + Ssurr = – 0.84 + (+1.11)
G = – TSuniv = – 300 × 11.52 = – 3456 J/mol.
J K–1 = 0.27 J K–1
 Thus, 0.04 mole of H+ ions will combine with 0.04 mole
Example : 16
of OH– ions to from 0.04 mole of H2O and 0.01 mole of
The heat of combustion of benzene in a bomb calorimeter H+ ions will remain unreacted.
(i.e., constant volume) was found to be 3263.9 kJ mol–1 at
 Heat evolved when 1 mole of H+ ions combine with
25oC. Calculate the heat of combustion of benzene at
constant pressure. 1 mole of OH– ions = 57.1 kJ.
 Heat evolved when 0.04 mole of H+ ions combine
Sol. The reaction is: with 0.04 mole of OH– ions = 57.1 × 0.04 = 2.284 kJ

1
C6 H 6     7 O 2  g  
 6CO 2  g   3H 2 O    (ii) 200 cm3 of 0.2 M H2SO4  0.2  200 mole of H2SO4
2
1000
In this reaction, O2 is the only gaseous reactant and CO2 = 0.04 mole of H2SO4 = 0.08 mole of H+ ions
is the only gaseous product.
0.5
400 cm3 of 0.5 M KOH   400 mole of KOH =
1 1 3 1000
 n g  n p  n r  6  7  1  
2 2 2 0.2 mole of KOH = 0.2 mole of OH– ions
Also, we are given U (or qv) = – 3263.9 kJ mol–1 Thus, 0.08 mole of H+ ions will neutralize 0.08 mole of
T = 25oC = 298K OH– ions. (out of 0.2 mole of OH– ions) to form 0.08
mole of H2O.
8.314
R = 8.314 J K–1 mol– = kJ K 1 mol 1 Hence, heat evolved = 57.1 × 0.08 = 4.568 kJ
1000
In case (i), heat produced = 2.284 kJ = 2284 J
H (or qp) = U + ng RT = – 3263.9 kJ mol–1 +
Total volume of the solution = 500 + 200 = 700 mL

 3   8.314  Assuming density of solution = 1g/mL

  mol   kJ K 1 mol 1   298 K 
 2   1000  So mass of solution = 700g
Specific heat = 4.18 J K–1 g–1
–1 –1
= – 3263.9 – 3.7 kJ mol = – 3267.6 kJ mol .
Q 2284
Q  m  C   T  T   = 0.78ºC
m  C 700  4.18
Example : 17
In case (ii), heat produced = 4.568 kJ = 4568 J
Calculate the amount of heat evolved when
Total mass of the solution = 200 + 400 = 600 g
(i) 500 cm3 of 0.1 M hydrochloric acid is mixed with 200
cm3 of 0.2 M sodium hydroxide solution Q 4568
 T   = 1.82ºC
3
(ii) 200 cm of 0.2 M sulphuric acid is mixed with 400 m  C 600  4.18
cm3 of 0.5 M potassium hydroxide solution.
Example : 18
Assuming that the specific heat of water is 4.18 J K–1 g–1
and ignoring the heat absorbed by the container, Calculate the enthalpy change accompanying the
thermometer, stirrer etc., what would be the rise in transformation of C (graphite) to C(diamond). Given that
temperature in each of the above cases ? the enthalpies of combustion of graphite and diamond are
393.5 and 395.4 kJ mol–1 respectively.
0.1
Sol. (i) moles of HCl =  500 = 0.05 = 0.05 mole of H+ ions
1000
Sol. Remember, enthalpy of combustion is always negative
0.2 we are given
200 cm3 of 0.2 M NaOH   200
1000
 CO2(g) ; c Ho = – 393.5 kJ mol–1
(i) C (graphite) + O2 (g) 
–
mole of NaOH = 0.04 mole = 0.04 mole of OH ions
 CO2(g) ; c Ho = – 395.4 kJ mol–1
(ii) C (diamond) + O2 (g) 
 In order to get this thermochemical equation, multiply
We aim at  C(diamond), trans Ho = ?
C(graphite)  eqn. (iii) by 2 and add it to eqn. (ii) and then subtract
Subtracting eqn. (ii) from eqn. (i), we get eqn. (i) from their sum. We get :

C + 2 H2 
 CH4,
C(graphite – C(diamond) 
 0;
H = – 393.4 + 2 (–285.7)
r Ho = – 393.5 – (–395.4) = + 1.9 kJ
– (–890.2) kJ mol–1 = –74.6 kJ mol–1
or C(graphite) 
 (diamond) ; trans H = + 1.9 kJ Hence, the heat of formation of methane is :
f H = –74.6 kJ mol–1
Example : 19
Example : 21
Calculate the enthalpy of hydration of anhydrous copper
sulphate (CuSO 4) into hydrated copper sulphate Calculate the heat of formation of KCl from the following
(CuSO4.5H2O). Given that the enthalpies of solutions of data :
anhydrous copper sulphate and hydrated copper sulphate
are –66.5 and + 11.7 kJ mol–1 respectively (i) KOH (aq) + HCl (aq) 
 KCl (aq) + H2O

   , H = – 57.3 kJ mol–1
Sol. We are given
1
(i) CuSO4 (s) + aq  (ii) H2 (g) +  H2O    ,
O 2  g  
 CuSO4 (aq) ; 2
1
sol H1 = – 66.5 kJ mol–1 H = 286.2 kJ mol
1 1
(ii) CuSO4.5H2O (s) + aq 
 CuSO4 (aq) ; (iii) H 2  g   Cl 2  g   aq 
 HCl  aq  ,
2 2
sol H2 = + 11.7 kJ mol–1 H = – 164.4 kJ mol–1
1 1
We aim at CuSO4 (s) + 5H2O (l) 
 CuSO4.5H2O(s) ;
(iv) K (s)  O 2  g   H 2  g   aq 

2 2
hyd H = ? KOH (aq), H = – 487.4 kJ mol–1

H = H1 – H2 = – 66.5 – (+11.7) = – 78.2 kJ/mol  KCl (aq), H = + 18.4 kJ mol–1
(v) KCl (s) + aq 

1
Example : 20 Sol. We aim at : K(s) + Cl 2  g  
 KCl  s  ,  f H  ?
2
Calculate the enthalpy of formation of methane, given that In order to get this thermochemical equation, we follow
the enthalpies of combustion of methane, graphite and the following two steps :
hydrogen are 890.2 kJ, 393.4 kJ and 285.7 kJ mol–1 Step 1. Adding Eqns. (iii) and (iv) and subtacting Eq. (v).
respectively. we have

Sol. Remember : Enthalpy of combustion is always negative. 1 1

K (s) + Cl2  g   H 2  g   O 2  g  
 KCl  s  
2 2
We are given : HCl (aq) + KOH (aq) – KCl (aq)
H = – 487.4 + (–164.4) – (18.4) = – 670.2 kJ mol–1 ... (vii)
 CO2 + 2 H2O, H = – 890.2 kJ mol–1
(i) CH4 + 2O2  Step 2. To cancel out the terms of this equation which do
not appear in the required equation (vi), add eqn. (i) to eqn.
 CO2, H = – 393.4 kJ mol–1
(ii) C + O2  (vii) and subtract eqn. (ii) from their sum. This gives
1 1
 H 2 O, H  285.7 kJ mol1
(iii) H 2  O 2  K  s   Cl 2  g  
 KCl  s  ;
2 2

We aim at : C + 2H2 
 CH4, H = ? fH = 670.2  57.3   286.2  = – 441.3 kJ
 Example : 22 We aim at : C2H4 (g) + 3O2 (g) 
 2CO2 (g) + 2H2O(g)
The combustion of 1 mole of benzene takes place at 298 K H = – H3 + 2H1 + 2H2
and 1 atm. After combustion, CO2 (g) and H2O (l) are
produced and 3267.0 kJ of heat is liberated. Calculate = –1322.9 kJ mol–1
the standard enthalpy of formation, f Ho of benzene.
Standard enthalpies of formation of CO2 (g) and H2O (l) Example : 24
are – 393.5 kJ mol–1 and –285.83 kJ mol–1 respectively.
Given the following thermochemical equations:
Sol.  C6H6    , H = ?
Aim : 6 C (s) + 3 H2 (g)   SO2 (g), H = – 297.5 kJ mol–1
(i) S (rhombic) + O2 (g) 
Given :  SO2 (g), H = – 300.0 kJ mol–1
(ii) S(monoclinic) + O2 

15 Calculate H for the transformation of one gram atom of

(i) C6H6 (l) + O (g) 
 6 CO2 (g) + 3 H2O (l), H rhombic sulphur into monoclinic sulphur.
2 2

= –3267.0 kJ mol–1 Sol. We aim at

S (rhombic)  S (monoclinic), H = ?
 CO2 (g), H = – 393.5 kJ mol–1
(ii) C (s) + O2 (g) 
Equation (i)  Equation (ii) gives
1 S(rhombic) – S(monoclinic) 
 0,
(iii) H2 (g) + O 2  g  
 H2O (l), H = –285.83 kJ mol–1
2 H = 297.5 – (–300.0) = 2.5 kJ mol–1
or  S(monoclinic), H = + 2.5 kJ mol–1
S(rhombic) 
In order to get the required thermochemical equation,
Thus, for the transformation of one gram atom of rhombic
multiply Eq. (ii) by 6 and Eq. (iii) by 3 and subtract Eq.
sulphur into monoclinic sulphur, 2.5 kJ mol–1 of heat is
(i) from their sum, i.e. operating 6 × Eqn. (ii) + 3 × Eqn. absorbed.
(iii) – Eqn. (i), we get
Example : 25
6C (s) + 3H2 (g) 
 C6H6 (l) ;
Enthalpy of solution (H) for BaCl2.2H2O and BaCl2 are
H = 6 (–393.5) + 3 (–285.83) – (–3267.0) 8.8 and –20.6 kJ mol–1 respectively. Calculate the heat of
= – 2361 – 857.49 + 3267.0 = 48.51 kJ mol–1 hydration of BaCl2 to BaCl2.2H2O.
Thus, the enthalpy of formation of benzene is
Sol. We are given
f H = – 48.51 kJ mol–1
 BaCl2(aq), sol H1o = 8.8 kJ mol–1
(i) BaCl2.2H2O (s) + aq 
Example : 23
 BaCl2(aq), sol H o2 = – 20.6 kJ mol–1
(ii) BaCl2 (s) + aq 
Calculate the enthalpy of combustion of ethylene (gas) to
We aim at
form CO2 (gas) and H2O (gas) at 298 K and 1 atmospheric
pressure. The enthalpies of formation of CO2, H2O and C2H4  BaCl2.2H2O (s), hyd Ho = ?
BaCl2 (s) + 2H2O 
are –393.5, –241.8, + 52.3 kJ per mole respectively.
H = H2 – H1 = – 29.4 kJ mol–1
Sol. We are given :
Example : 26
 CO2 (g), H1o = – 393.5 kJ mol–1
(i) C (s) + O2 (g) 
Calculate the enthalpy of hydrogenation of ethylene, given
that the enthalpy of combustion of enthylene, hydrogen
1 and ethane are – 1410.0, – 286.2 and – 1560.6 kJ mol–1
(ii) H 2  g   O 2  g  
 H2O(g), H o2 = – 241.8kJ mol–1
2 respectively at 298 K.

Sol. We are given (i) C2H4 (g) + 3O2 (g) 

 2CO2(g) + 2H2O
 C2H4(g), H 3o = + 52.3 kJ mol–1
(iii) 2C (s) + 2H2 (g)  (l) , H = – 1410 kJ mol–1
 890.3 kJ of heat is produced from 1 mole of CH4, i.e.,
1 12 + 4 = 16 g of CH4
 H2O (l), H = – 286.2 kJ mol–1
(ii) H2 (g)  O 2  g  
2  445.15 kJ of heat is produced from 8 g of CH4
1 (b) From the given equation, when 890.3 kJ of heat is
(iii) C2H6 (g) + 3 O2  g  
 2CO2  g  + 3H2O (l), H evolved, CO2 formed = 1 mole = 44 g
2
= – 1560.6 kJ mol–1  When 445.15 kJ of heat is evolved, CO2 formed = 22 g
(c) From the equation, O2 used in the production of
We aim at: C2H4 + H2(g) 
 C2H6 (g), H = ? 890.3 kJ of heat = 2 moles = 2 × 22.4 litres at STP
Equation (i) + Equation (ii) – Equation (iii) gives = 44.8 litres at STP
Hence, O2 used in the production of 445.15 kJ of heat =
C2H4 (g) + H2 (g) 
 C2H6 (g),
22.4 litres at STP.
H = – 1410.0 + (–286.2) – (1560.6) = – 135.6 kJ mol–1
Example : 29
Example : 27
From the thermochemical equation,
The thermite reaction used for welding of metals involves
the reaction 1
C6 H 6     7 O 2  g  
 3H 2 O     6CO 2 (g),
2
2 Al (s) + Fe2O3 (s) 
 Al2O3 (s) + 2Fe (s)
cH = – 3264.64 kJ mol–1,
What is Ho at 25oC for this reaction ? Given that the calculate the energy evolved when 39 g of C6H6 are burnt
standard heats of formation of Al2O3 and Fe2O3 are in an open container.
– 1675.7 kJ and –828.4 kJ mol–1 respectively.
Sol. From the given equation,
Sol. We aim at 2Al (s) + Fe2O3(s) 
 Al2O3 (s) + 2Fe
When 1 mole of C6H6 (78 g of C6H6) is burnt, heat evolved
(s), r Ho = ? = 3264.64 kJ
r H = Sum of f Ho of products – Sum of  When 39 g of C 6H 6 is burnt, heat evolved =

f Ho of reactants 3264.64
 39 = 1632.32 kJ
78
=[f Ho (Al2O3) + 2 × f Ho (Fe)] –
[2 × f Ho (Al) + f Ho (Fe2O3)] Example : 30
–1
= [–1675.7 + 0] – [0 + (–828.4)] = – 847.3 kJ mol The thermochemical equation for solid and liquid rocket
fuel are given below :
Example : 28
1
The heat evolved in the combustion of methane is given by 2Al  s   1 O 2  g  
 Al2 O3  s  ;
2
the equation :
H  1667.8 kJ mol1
 CO2 (g) + 2H2O (l), H = – 890.3 kJ mol–1
CH4 (g) + 2O2 (g) 
1
H 2  g   O 2  g  
 H 2 O 1 ;
(a) How many grams of methane would be required to 2
produce 445.15 kJ of heat of combustion ?
H  285.9 kJ mol1
(b) How many grams of carbon dioxide would be formed (a) If equal masses of aluminium and hydrogen are used,
when 445.15 kJ of heat is evolved ? which is a better rocket fuel ?
(c) What volume of oxygen at STP would be used in the (b) Determine H for the reaction :
combustion process (a) or (b) ?
1
 2Al (s) + 1 O 2  g  .
Al2O3(s) 
2
Sol. (a) From the given equation.
Sol. (a) From the first given equation,
 2 moles of Al (i.e., 2 × 27 g = 54 g) on combustion give Writing the reverse reaction, we have
heat = 1667.8 kJ
1667.8 6CO2 (g) + 6H2O(g) 
 C6H12O6 (s) + 6O2(g) ;
 1 g of Al on combustion gives heat   30.9 kJ
54 r H = + 2840 kJ mol–1
From the second given equation, 1 mole of H2 (= 2 g) on
combsution gives heat = 285.9 kJ Thus, for production of 1 mole of C6H12O6 (= 72 + 12 + 96
285.9 = 180 g), heat required (absorbed) = 2840 kJ.
1 g of H2 on combustion gives heat   142.95 kJ
2

Thus, H2 is a better rocket fuel.  For production of 0.36 g of glucose, heat absorbed
(b) Writing the reverse of the first reaction, we have 2840
=  0.36  5.68 kJ
180
1
 2Al  s   1 O 2  g  ; H  1667.8 kJ mol 1
Al2 O3  s  
2
Example : 33
Thus, for the reaction given in part (b) of the problem,
H = + 1667.8 kJ mol–1 Calculate the bond energy of C–H bond, given that the
heat of formation of CH4, heat of sublimation of carbon
and heat of dissociation of H2 are – 74.8, + 719.6 and
Example : 31
435.4 kJ mol–1 respectively.
When 1 g liquid naphthalene (C10H8) solidifies. 149 joules
of heat is evolved. Calculate the enthalpy of fusion of Sol. Here, we are given
naphthalene.

 CH4(g), r Ho = – 74.8 kJ
C (s) + 2H2 (g) 
Sol. Molar mass of naphthalene (C10H8) = 128 g mol–1
When 1 g of liquid naphthalene solidified, heat evolved
= 149 joules. H = esub(C) + 2eH–H – 4eC–H

When 1 mole, i.e., 128 g of naphthalene solidifies, heat

evolved = 149 joules. – 74.8 = 719.6 + 2 (435.4) – 4eC–H

When 1 mole, i.e., 128 g of naphthalene solidifies, heat

evolved = 149 × 128 joules = 19072 joules eC–H = 416.3 kJ/mol

Since fusion is reverse of solidification, therefore, heat

absorbed for fusion of one mole of naphthalene = 19072 Example : 34
joules.
Calculate the enthalpy change for the reaction
i.e., Enthalpy of fusion (fus H) = + 19072 joules/mole

H2 (g) + Br2 (g) 

 2HBr (g)
Example : 32
Given that the bond enthalpies of H–H, Br–Br, H–Br are
The heat evolved in the combustion of glucose is shown in
435, 192 and 364 kJ mol–1 respectively.
the equation :

 6CO2 (g) + 6 H2O (g), c H

C6H12O6 + 6O2 (g)  Sol. r H = B.E. (Reactants) – B.E. (Products)

= – 2840 kJ mol–1 = [B.E. (H2) + B.E. (Br2)] – 2 B.E. (HBr) =

What is the energy requirement for production of 0.36 g
of glucose by the reverse reaction ? 435 + 192 – 2 × 364 = – 101 kJ

Sol. The given equation is :

C6H12O6 + 6O2(g) 
 6CO2(g) + 6H2O (g) ;
r H = – 2840 kJ mol–1
 Example : 35 40.626 kJ mol1
  vap S =  0.1089 kJ K –1
373 K
Propane has the structure H3C–CH2 –CH3. Calculate the
change in enthalpy for the reaction: mol–1 = 108.9 J K–1 mol–1.

C3H8 (g) + 5 O2 (g) 

 3 CO2 (g) + 4 H2O (g) Example : 38

Given that average bond enthalpies are: 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
C–C C–H C = O O = O O–H and G for the conversion of ice to liquid water ?
347 414 741 498 464 kJ mol–1
Sol. Since the given process is in equilibrium, G = 0
Putting this value in the relationship, G = H – TS, we
get
Sol. +5 O=O3O=C=O+4H–O–H
H
0 = H – TS or TS = H or S =
T
H = (2eC–C + 8eC–H + 5eO=O) – (6eC=O + 8eO–H) We are given H = 6.0 kj mol = 6000 J mol and T = 0oC
–1 –1

= 2 (347) + 8 (414) + 5 (498) – 6 (741) – 8 (464) = 273 K

= – 1662 kJ mol–1 6000 J mol1

   21.98 J K –1 mol –1
273K
Example : 36

Calculate the entropy change involved in conversion of Example : 39

one mole (18 g) of solid ice at 273 K to liquid water at the
 C + D ; H = – 10,000 J mol–1,
A + B 
same temperature (latent heat of fusion = 6025 J mol–1).
S = – 33.3 J mol–1 K–1
f H
Sol. Entropy change for ice  water is given by  f S 
Tf (i) At what temperature the reaction will occur
spontaneously from left to right ?
Here, f H = 6025 J mol–, Tf = 273 K 
(ii) At what temperature, the reaction will reverse?
1 1
6025 J K mol
f S   22.1 J K -1 mol -1 . Sol. G = H – TS
273K
At equilibriu, G = 0 so that H = TS or
Example : 37
H 10000 J mol1
Calculate the entropy change involved in the conversion of T   300.03K
S 33.3JK 1 mol 1
one mole of liquid water at 373 K to vapour at the same
temperature (latent heat of vaporization of water
(i) For spontaneity from left to right. G should be –ve
vap H = 2.257 kJ/g)
for the given reaction. This will be so if T < 300.3 K

Sol. For the conversion of water  vapour, the entropy (ii) For reverse reaction to occur, G should be +ve
forward reaction. This will be so if T > 300.3 K.
 vap H
change is given by vap S =
Tb

Here, vap H = 2.257 kJ/g = 2.257 × 18 kJ/mol =

40.626 kJ/mol, Tb = 373 K
 = – 1648000 + 163721 J K–1 mol–1 =
Example : 40 – 1484279 J K–1 mol–1
Calculate the standard free energy change for the As Go is –ve, the reaction is spontaneous.
reaction,
4NH3 (g) + 5O2 (g) 
 4NO (g) + 6H2O (l)
Example : 42
Given that the standard free energies of formation (f Go)
for NH3 (g), NO (g) and H2O (l) are – 16.8, + 86.7 Calculate the standard enthalpy of formation of CH3OH
and – 237.2 kJ mol–1 respectively. Predict the feasibility (l) from the following data :
of the above reaction at the standard state.
3
(i) CH 3OH     O 2  g  
 CO 2  g  
Sol. Here, we are given 2

f Go (NH3) = – 16.8 kJ mol–1 2 H 2 O    ;  r H o  726 kJ mol1

f Go (NO) = + 86.7 kJ mol–1  CO 2  g  ;  c H o 
(ii) C  s   O 2  g  
f Go (H2O) = – 237.2 kJ mol–1 – 393 kJ mol–l
 r Go =  f Go (Products) –  f Go (Reactants) = 1
 H2 O    ; f Ho 
(iii) H 2  g   O 2  g  
[14 × f Go (NO) + 6 × f Go (H2O)] – [4 × f Go (NH3) 2
+ 5 × f Go (O2)] – 286 kJ mol–1.
1
= [4 × (86.7) + 6 × (–237.2)] – [4 × (– 16.8) + 5 × Sol.  CH 3OH    ,
Aim : C (s) + 2H2 (g)  O 2  g  
0] = – 1009.2 kJ 2

Since r Go is negative, the process is feasible. f Ho  ?

Eqn. (ii) + 2 × Eqn. (iii) – Eqn. (i) gives the required eqn.
Example : 41
with H = – 393 + 2 (–286) – (– 726) kJ mol–1 =
Calculate the entropy change for the rusting of iron – 239 kJ mol–1.
according to the reaction :
Example : 43
 2 Fe2O3 (s), Ho = –1648 kJ mol–1
4 Fe (s) + 3 O2 (g) 
Calculate enthalpy of formation of methane (CH4) from
Given that the standard entropies of Fe, O2 and Fe2O3 are the following data :
27.3, 205.0 and 87.4 J K–1 mol–1 respectively. Will the
reaction be spontaneous at room temperature (25oC) ?  CO2(g), r Ho = – 393.5 kJ mol–1
(i) C (s) + O2 (g) 
Justify your answer with appropriate calculations.
1
 H2 O    ,
(ii) H 2  g   O2  g  
2
Sol. r So =  So (Products) –  So (Reactants) =
r Ho = – 285.8 kJ mol–1
o o o
2 S (Fe2O3) – [4 S (Fe) + 3 S (O2)]
 CO2 (g) + 2 H2O (  ),
(iii) CH4 (g) + 2O2 (g) 
= 2 × 87.4 – [4 × 27.3 + 3 × 205.0] J K–1 mol–1 = r Ho = –890.3 kJ mol–1
– 549.4 J K–1 mol–1
Sol.  CH4 (g) ; f Ho = ?
We aim at : C (s) + 2 H2 (g) 
This is the entropy change of the reaction, i.e., system
(Ssystem) Multiplying eqn. (ii) with 2, adding to eqn. (i) and then
subtracting eqn. (iii) from the sum, i.e., operating eqn.
Now, rGo = r Ho – Tr So
(i) + 2 × eqn. (ii) – eqn. (iii), we get
= – 1648000 J mol–1 – 298 K ×
(–549.4 J K–1 mol–1)
C (s) + 2 H2 (g) – CH4 (g)   0; r Ho = – 393.5 + 2
(–285.8) – (–890.3) – 74.8 kJ mol–1
 or  CH4 (g); f Ho = – 74.8 kJ mol–1
C (s) + 2 H2 (g) 
Example : 46
Hence, enthalpy of formation of methane is : The heat librerated on complete combustion of 7.8g
o –1 benzene is 327 kJ. This heat has been measured at
f H = – 74.8 kJ mol
constant volume and at 27ºC. Calculate heat of
Example : 44 combustion of benzene at constant pressure at 27ºC.

Calculate the enthalpy of formation of carbon monoxide (R = 8.3 J mol–1 K–1).

(CO) from the following data :
15
Sol. C6H6 (l ) + O (g) 6CO2(g) + 3H2O (l )
o
 CO2 (g); r H = – 393.5 kJ mol
(i) C (s) + O2 (g)  –l 2 2

1 15 3
(ii) CO (g) + O 2  g  
 (g); r Ho = – 283.0 kJ mol–l n = 6 – 
2 2 2
327  78
Also, U per mol = – = – 3270 kJ
7 .8
1
Sol. We aim at : C (s) +  CO  g  ;  f H o  ?
O 2  g   Now, H = U + nRT
2
 3
Subtracting eqn. (ii) from eqn. (i), we get = – 3270 +    × 8.3 × 300 × 10–3
 2

1 H = – 3273.735 kJ
C (s) + O 2  g   CO  g  
 0;
2 Example : 47

r Ho = –393.5 – (– 283.0) = – 110.5 kJ mol–1 Calculate standard heat of formation of CS2. Given that
standard heat of combustion of C, S and CS2 are – 393.3,
1 – 293.72 and – 1108.76 kJ mol–1.
or  CO  g  ;  r Ho  110.5 kJ.
C  s   O2  g  
2 Sol. We have to find H for
 Heat of formation of CO is : f Ho = – 110.5 kJ mol–1 C + 2S CS2; H = ?
Given, C + O2 CO2; H = – 393.3 kJ ......... (1)
Example : 45 S + O2 SO2; H = – 293.72 kJ ........ (2)
Determine whether or not, it is possible for sodium to CS2 + 3O2 CO2 + 2SO2 ; H = – 1108.76 kJ ......... (3)
reduce aluminium oxide to aluminium at 298 K. Given
Multiply Eq. (2) by 2 and add in Eq. (1)
that G 0f of Al2O3 at 298 K = – 1582 kJ mol–1; G 0f of
Na2O(s) at 298 K = –377 kJ mol–1. C + 2S + 3O2 CO2 + 2SO2; H = – 980.74 kJ .......... (4)
Subtract Eq. (3) from Eq. (4)
Sol. The given reaction is :
C + 2S CS2; H = + 128.02 kJ
Al2O3 (s) + 6Na(s) 3Na2O (s) + 2Al(s)
Hf of CS2 = + 128.02 kJ
Hence, Gº = 3 × G 0f (Na2O) – G 0f (Al2O3)
Example : 48
(Gº for Na and Al = 0) Estimate the average S–F bond energy in SF6. The standard
= 3 × (– 377) – (– 1582) = 451 kJ mol –1 heat of formation value of SF6(g), S (g) and F (g) are : – 1100,
275 and 80 kJ mol–1 respectively.
The reaction cannot occur since Gº (298 K) is positive.
Sol. H = esub(s) + 6eF – 6eS–F
–1100 = 275 + 6 (80) – 6eS–F
eS–F = 309.17 kJ/mol
 Example : 49 Example : 50
From the following themochemical equations, calculate The standard molar enthalpies of formation of
the enthalpy of formation of cane sugar (C12H22O11) : cyclohexane (l) and benzene (l ) at 25ºC are – 156 and +
(i) C12H22O11 (s) + 12 O2(g) 12 CO2(g) + 11 H2O (l) 49 kJ mol–1 respectively. The standard enthalpy of
hydrogenation of cyclohexene (l ) at 25ºC is – 119 kJ
rH1 = – 5644 kJ mol–1 mol–1. Use these data to estimate the magnitude of the
resonance energy of benzene.
(ii) C (s) + O2 (g) CO2(g) rH2 = – 393 kJ mol–1
(iii) H2(g) + 1/2 O2(g) H2O (l) rH3 = – 286 kJ mol–1 Sol. Enthalpy of formation of 3 carbon-carbon double bonds

Sol. AIM : 12C (s) + 11 H2 (g)  C12 H22 O11 (s) H = ? Hf ( ) – Hf ( )

H = 12H2 + 11 H3 – H1 = – 156 – (+49) kJ

= 12 (–393) + 11 (–286) – (–5644)
= – 205 kJ.
= –2218 kJ/mol
Given, that,

+ H2   ; H = – 119 kJ

Theoretical enthalpy of formation of 3 double bonds in

benzene ring

= 3 × (– 119) kJ = – 357 kJ.

 resonance energy of benzene = – 357 – (– 205) kJ

= – 152 kJ mol–1.
 EXERCISE - 1 : BASIC OBJECTIVE QUESTIONS

State Function (c) The system loses heat and performs work.

1. Which of the following is not a state function ? (d) The system loses heat and has work performed on it.

(a) Heat (b) Internal energy PV-Work

(c) Enthalpy (d) Entropy 9. A given mass of gas expands from the state A to the state
2. Which of the following quantities is not a state function ? B by three paths 1, 2 and 3 as shown in the figure. If w1, w2
(a) Temperature (b) Entropy and w3 respectively be the magnitudes work done by the
(c) Enthalpy (d) Work gas along three paths then :

Extensive/Intensive
3. Which of the following is not an intensive property ?
(a) Entropy (b) Pressure
(c) Temperature (d) Molar volume
4. Which of the following is a state function and also an (a) w1 > w2 > w3 (b) w1 < w2 < w3
extensive property?
(c) w1 = w2 = w3 (d) w2 < w3 < w1
(a) Internal energy (b) Pressure
10. An ideal gas is taken around the cycle ABCA as shown in
(c) Molar heat capacity (d) Temperature
P-V diagram
System The net work done by the gas during the cycle is equal to :
5. Warming ammonium chloride with sodium hydroxide in a
test tube is an example of :
(a) Closed system (b) Isolated system
(c) Open system (d) None of these
6. A tighly closed thermoflask contains some ice cubes. This
constitutes
(a) closed system (b) open system
(c) isolated system
(a) 12 P1V1 (b) 6P1V1
(d) Non-thermodynamic system
(c) 5P1V1 (d) P1V1
Internal Energy 11. Two moles of Helium gas undergo a reversible cyclic
7. A sample of gas changes from p1, V1 and T1 to p2, V2 and process as shown in figure. Assuming gas to be ideal.
What is the work for the process C to D ?
T2 by one path and then back to p1, V1 and T1, U for the
process is :
(a) Infinite (b) > 0
(c) < 0 (d) equal to 0
8. Which of the following changes would definitely increase
the internal energy of a system?
(a) –800 Rn2 (b) zero
(a) The system gains heat and performs work.
(b) The system gains heat and has work performed on it. (c) +200 Rn2 (d) –600 Rn2
12. A heat engine carries one mole of an ideal mono-atomic 17. A sample of liquid in a thermally insulated container (a
gas around the cycle as shown in figure, the amount of calorimeter) is stirred for 2 hr. by a mechanical linkage to a
heat added in the process AB and heat removed in the motor in the surrounding, for this process;
process CA are:
(a) w < 0; q = 0; U = 0 (b) w > 0; q > 0; U > 0
(c) w < 0; q > 0; U = 0 (d) w > 0; q = 0; U > 0
18. For a particular process q = –10 kJ and w=25 kJ. Which of
the following statements is true?
(a) Heat flows from the surroundings to the system.
(b) The system does work on the surroundings.
(c) E= –35 kJ
(d) None of the above is true
19. An ide al gas is taken through the cycle A  B  C  A
(a) qAB = 450 R and qCA = –450 R as shown in fig. If the net heat supplied to the gas in cycle
is 5 J, the work done by the gas in the process C  A.
(b) qAB = 450 R and qCA = –225 R

(c) qAB = 450 R and qCA = –375 R

(d) qAB = 375 R and qCA = –450 R

First Law
13. A system absorb 10 kJ of heat at constant volume and its
temperature rises from 27°C to 37°C. The value of U is
(a) 100 kJ (b) 10 kJ (a) –5 J (b) –10 J

(c) 0 (d) 1 kJ (c) –15 J (d) –20 J

14. An ideal gas receives 10 J of heat in a reversible isothermal 20. In a system where E = –51.0 kJ, a piston expanded against
expansion. Then the work done by the gas : a pext of 1.2 atm giving a change in volume of 32.0 L. What
was the change in heat of this system?
(a) would be more than 10 J
(a) –36 kJ (b) –13 kJ
(b) 10 J
(c) –47 kJ (d) 24 kJ
(c) would be less than 10 J Isothermal Process
(d) cannot be determined 21. In an isothermal expansion of an ideal gas
15. As per the First Law of thermodynamics, which of the (a) q = 0 (b) V = 0
following statement would be apropriate : (c) U = 0 (d) w = 0
(a) Energy of the system remains constant 22. The maximum work obtained by an isothermal reversible
(b) Energy of the surroundings remains constant expansion of 1 mole of an ideal gas at 27°C from 2.24 to
22.4 L is (R = 2 cal)
(c) Entropy of the universe remains constant
(a) – 1381.8 cal (b) – 600 cal
(d) Energy of the universe remains constant
(c) –138.18 cal (d) – 690.9 cal
16. What is the change in internal energy when a gas contracts o
from 377 mL to 177 mL under a constant pressure of 1520 23. 2 mole of an ideal gas at 27 C expands isothermally and
torr, while at the same time being cooled by removing 124 reversibly from a volume of 4 litres to 40 litre. The work
J heat? done (in kJ) is:
(a) 40.52 J (b) –83.48 J (a) w = –28.72 kJ (b) w = –11.488 kJ

(c) –248 J (d) None of these (c) w = –5.736 kJ (d) w = –4.988 kJ

24. 5 mole of an ideal gas expand isothermally and irreversibly 32. During the adiabatic expansion of an ideal gas against
from a pressure of 10 atm to 1 atm against a constant atmospheric pressure, the internal energy will
external pressure of 1 atm. wirr at 300 K is: (a) Increase (b) decrease
(c) stay the same (d) Impossible to say
(a) –15.921kJ (b) –11.224 kJ
33. One mole of an ideal gas expands reversibly and
(c) –110.83 kJ (d) None of these
adiabatically from a temperature of 27oC. If the work done
25. 10 mole of ideal gas expand isothermally and reversibly during the process is 3 kJ, then final temperature of the
from a pressure of 10 atm to 1 atm at 300 K. What is the gas is:(CV = 20 J/K )
largest mass which can lifted through a height of 100 meter? (a) 100 K (b) 150 K
(a) 31842 kg (b) 58.55 kg (c) 195 K (d) 255 K
(c) 342.58 kg (d) None of these Heat Capacities
Processes 34. Molar heat capacity of water in equilibrium with ice at
26. Which of the following statement is true? constant pressure is
(a) A thermodynamic process is defined by initial and (a) zero (b) 
final states. (c) 40.45 kJ K–1 mol–1 (d) 75.48 J K–1 mol–1
(b) E=0 for a reversible phase change at constant T and 35. Ice–Water mass ratio is maintained as 1 : 1 in a given
P. system containing water in equilibrium with ice at constant
–1 –1
(c) q must be zero for an isothermal process. pressure. If CP (ice) = CP (water) = 4.18 J mol K molar
(d) A reversible adiabatic process is also isentropic. heat capacity of such a system is
27. In the thermodynamic sense of the word, an irreversible (a) Zero (b) Infinity
–1 –1 –1 –1
process (c) 4.182 JK mol (d) 75.48 JK mol
(a) does the same work (but of opposite sign) as a 2nd Law
reversible process
36. The statement “A heat engine always loses some of its
(b) violates the 1st law of thermodynamics, unlike a heat energy to the surroundings.” is an example of which
reversible process of the following laws?
(c) involves non-ideal gases (as opposed to ideal gases (a) The Law of Corresponding States
in a reversible process) (b) The Zeroth Law of Thermodynamics
(d) exchanges the same amount of heat (but of opposite
(c) The First Law of Thermodynamics
sign) as a reversible process.
(d) The Second Law of Thermodynamics
28. The temperature of the system decreases in an
(a) Isothermal compression (b) Isothermal expansion 37. Heat cannot by self flow from a body at lower temperature
to a body at higher temperature a statement of
(c) Adiabatic compression (d) Adiabtic expansion
consequence of:
First Law (a) 1st law of thermodynamics
29. For a chemical reaction at constant P and V, H is equal to
(b) 2nd law of thermodynamics
(a) U (b) zero
(c) conservation of momentum
(c) U + PV (d) p/T
(d) conservation of mass
Adiabatic Process
30. In an adiabatic expansion of an ideal gas 38. When steam condenses to water at 90oC, the entropy of
(a) T = 0 (b) w = 0 the system decreases. What must be true if the second
law of thermodynamics is to be satisfied?
(c) q = 0 (d) U = 0
(a) Entropy of the universe also decreases.
31. 1 mole of NH3 gas at 27°C is expanded in reversible
(b) Entropy of the surroundings also decreases.
adiabatic condition to make volume 8 times ( = 1.33). Final
temperature and work done by the gas respectively are : (c) Entropy of the surroundings increases to same extent
(a) 150 K, 900 cal (b) 150 K, 400 cal to which entropy of the system decreases.
(c) 250 K, 1000 cal (d) 200 K, 800 cal (d) Increase in entropy in the surroundings is greater than
decrease in entropy of the system.
Entropy 47. The entropy change for the conversion of 1 mol of –tin
(at 13°C, 1 atm) to 1 mol of –tin (13°C, 1 atm), if enthalpy
39. The entropy of the universe –1
of transition is 2.095 kJ mol is :
(a) tends towards a maximum –1 –1 –1 –1
(a) 7.32 J mol K (b) 14.62 J K mol
(b) tends towards a minimum
–1 –1
(c) tends to be zero (d) remains constant (c) 56.3 J mol K (d) 0

40. Which of the following has highest entropy ? 48. The following data is known about the melting of a
–1 –1 –1
compound AB. H = 9.2 kJ mol . S = 0.008 kJ K mol . Its
(a) Mercury (b) Hydrogen
melting point is :
(c) Water (d) Graphite
(a) 736 K (b) 1050 K
41. Which of the following processes is not accompanied by
(c) 1150 K (d) 1150°C
increase of entropy ?
(a) dissolution of NH4Cl in water  5 
49. When two mole of an ideal gas  Cp,m.  R  heated from
(b) burning of rocket fuel  2 

(c) sublimation of dry ice 300 K to 600 K constant pressure. The change in entropy
of gas (S) is :
(d) condensing steam
42. For a reversible process at equilibrium, the change in 3 3
(a) R n 2 (b)  R n 2
entropy may be expressed as : 2 2

q rev 5
(a) S = Tqrev (b) S  (c) 5 R n 2 (d) R n 2
T 2

H 50. In the above question calculate Sgas if process is carried

(c) S   (d) S = G out at constant volume :
T
43. Entropy is a measure of 3
(a) 5 R n 2 (b) R n 2
(a) disorder (b) internal energy 2

(c) efficiency (c) 3 R n 2 (d) – 3 R n 2

(d) useful work done by the system 51. The entropy change when two moles of ideal monoatomic
44. When a solid is converted directly into gaseous state, the gas is heated from 200°C to 300°C reversibly and
process is called sublimation. The entropy change during isochorically ?
the process is :
3  300  5  573 
(a) zero (b) negative (a) R n   (b) R n  
2  200  2  273 
(c) positive (d) may be negative or zero
45. The enthalpy of vaporisation of a substance is  573  3  573 
–1 (c) 3R n   (d) R n  
8400 J mol and its boiling point is –173ºC. The entropy  473  2  473 
change for vaporisation is :
–1 –1 –1 –1  5 
(a) 84 J mol K (b) 21 J mol K 52. If one mole of an ideal gas  Cp.m.  R  is expanded
–1 –1 –1 –1  2 
(c) 49 J mol K (d) 12 J mol K
isothermally at 300 K until it’s volume is tripled, then
46. The enthalpy of vaporisation of a compound AB at its change in entropy of gas is :
–1
boiling point (127°C) is 6.4 kJ mol . Its entropy of
(a) zero (b) infinity
vaporisation is :
–1 –1
(a) 2.56 kJ mol (b) 16 J mol 5
(c) R n 3 (d) R n 3
–3 –1 3 –1 2
(c) 16 × 10 J mol (d) 1.6 × 10 kJ mol
53. When one mole of an ideal gas is compressed to half of its 59. When potassium chloride is dissolved in water
initial volume and simultaneously heated to twice its initial (a) Entropy increases (b) Entropy decreases
temperature, the change in entropy of gas (S) is : (c) Entropy increases and then decreases
(d) Free energy increases
(a) Cp,m ln2 (b) Cv,m ln2
60. Which of the following is true for the reaction ?
(c) R ln2 (d) (Cv,m –R) ln2
 H2O(g) at 100°C and 1 atm pressure
H2O() 
54. Two mole of a monoatomic ideal gas is expanded
(a) S = 0 (b) H = TS
irreversibly and isothermally at T Kelvin until its volume
(c) H = U (d) H = 0
is doubled and q joules heat is absorbed from surrounding.
61. For a reaction to be spontaneous at all temperatures
Stotal (J/K) (system + surrounding) is :
(a) G and H should be negative
(a) zero (b) 2 Rln2–q/T (b) H = G = 0
(c) 3Rln2–q/T (d) –2 Rln2 + q/T (c) G and H should be positive

55. One mole of an ideal diatomic gas (Cv = 5 cal) was (d) H < G
transformed from initial 25°C and 1 L to the state when 62. For isothermal expansion in case of an ideal gas :
temperature is 100°C and volume 10 L. The entropy change (a) G = S (b) G = H
of the process can be expressed as (R = 2 calories/mol/K)
(c) G = – T.S (d) None of these
298 373 63. A reaction has H = – 33 kJ and S = +58 J/K. This reaction
(a) 3n  2 n10 (b) 5n  2 n10
373 298 would be :
(a) spontaneous below a certain temperature
373 1 373 1
(c) 7n  2 n (d) 5n  2 n (b) non-spontaneous at all temperature
298 10 298 10
(c) spontaneous above a certain temperature
Gibbs Energy (d) spontaneous at all temperature
56. Which of the following conditions is not favourable for Relation b/w H & E
the feasibility of a process ? 64. For the reaction :
(a) H = –ve, TS = –ve and TS < H
C  s   O2  g  
 CO2  g 
(b) H = +ve, TS = +ve and TS > H
(a) H < U (b) H > U
(c) H = –ve, TS = +ve and H > TS
(c) H = U (d) H = 0
(d) H = +ve, TS = +ve and H > TS
65. For which of the following reactions, H is greater than
57. In which of the following cases, the reaction is U ?
spontaneous at all temperatures ? (a) N2(g) + 3H2(g) 
 2NH3(g)
(a) H > 0, S > 0 (b) H < 0, S > 0
(b) CH2(g) + 2O2(g) 
 CO (g) + 2H O(l)
2 2
(c) H < 0, S < 0 (d) H > 0, S < 0
(c) PCl5(g) 
 PCl3(g) + Cl2(g)
58. For an endothermic reaction, S is positive. The reaction
is : (d) HCl(aq) + NaOH(aq) 
 NaCl(aq) + H2O(aq)
(a) feasible when TS > H 66. For the reaction,
(b) feasible when H > TS
PCl5  g  
 PCl3  g   Cl 2  g 
(c) feasible at all temperatures
(a) H = U (b) H > U
(d) not feasible at all
(c) H < U (d) None of these
67. (U – H) for the formation of NH3 from N2 and H2 is : 74. Calculate the heat required to make 6.4 Kg CaC2 from
CaO(s) and C(s) from the reaction :
(a) –2 RT (b) 2 RT
CaO(s) + 3 C(s) 
 CaC2(s) + CO(g) given that
1
(c) RT (d) RT
T
2  f H º  CaO  = –151.6 kcal,  f H º  CaC2  = –14.2kcal.

68. The difference between heats of reaction at constant  f H º  CO  = –26.4 kcal.

pressure and constant volume for the reaction. 4
(a) 5624 kcal (b) 1.11 × 10 kcal
2C2H6(l) + 15O2(g) 
 12CO2(g) + 6H2O(l) at 25°C is 3
(c) 86.24 × 10 (d) 1100 kcal
(a) –7.43 kJ (b) +3.72 kJ
75. Given :
(c) –3.72 kJ (d) 7.43 kJ
H2(g) + ½O2(g) = H2O(g) + q1
69. For the reaction :
H2(g) + ½O2(g) = H2O (l) + q2
 2CO 2  g   2H 2 O   
C2 H 4  g   3O 2  g  
The enthalpy of vaporisation of water is equal to
at 298 K, U = – 1415 kJ.
–1 (a) q1 + q2 (b) q1 – q2
If R = 0.0084 kJ K , then H is equal to
(a) –1400 kJ (b) –1410 kJ (c) q2 – q1 (d) q1q2
– –
(c) –1420 kJ (d) –1430 kJ 76. If CH3COOH + OH 
 CH COO + H O + x kJ
3 2
70. The difference between H and E on a molar basis for + –
H + OH 
 H O + y kJ
2
the combustion of methane gas at 300K (kelvin) would be :
(a) zero (b) –RT The enthalpy change for the reaction :
– +
(c) –2RT (d) –3RT CH3COOH 
 CH COO + H is
3

71. Consider the reaction at 300 K (a) x + y (b) x – y

(c) y – x (d) x – y/2
H2(g) + Cl2 (g) 
 2HCl(g); Hº = –185 kJ
77. The enthalpies of elements in their standard states are
If 2 mole of H2 completely react with 2 mole of Cl2 to form taken as zero. Hence the enthalpy of formation of a
HCl. What is U° for this reaction ? compound

(a) 0 (b) –185 kJ (a) should always be negative

(c) 370 kJ (d) –370 kJ (b) should always be positive

H Reaction (c) will be equal to twice the energy of combination

72. The enthalpies of formation of N2O and NO at 298 K are 82 (d) may be positive or negative
–1
and 90 kJ mol . The enthalpy of the reaction : 78. Which of the following reactions represents enthalpy of
formation of AgCl ?
N 2 O  g   ½O 2  g  
 2NO  g 
(a) Ag   aq   Cl   aq  
 AgCl  s 
(a) –8 kJ (b) 98 kJ
(c) –74 kJ (d) 8 kJ 1
(b) AgCl  s  
 Ag  s   Cl2  g 
73. The enthalpies of solution of anhydrous CuSO4 and 2
–1
CuSO4.5H2O are –15.89 and 2.80 k cal mol respectively. (c) Ag  s   AuCl  s  
 AgCl  s   Au  s 
The enthalpy of hydration of CuSO4 to CuSO4.5H2O is :
(a) –18.69 kcal (b) 13.09 kcal 1
(d) Ag  s   Cl2  g  
 AgCl  s  .
(c) –13.09 kcal (d) 18.69 kcal 2
79. Which of the following equations represents standard heat 84. When 0.5 g of sulphur is burnt to SO2 4.6 kJ of heat is
of formation of methane ? liberated. What is the enthalpy of formation of sulphur
dioxide ?
(a) C (diamond) + 2H2(g) 
 CH4(g)
(a) –147.2 kJ (b) +147.2 kJ
(b) C (graphite) + 2H2(g) 
 CH4(g) (c) +294.4 kJ (d) –294.4 kJ

(c) C (diamond) + 4H(g) 

 CH4(g) H reaction & formation
–1
85. The heat of formation of Fe2O3(s) is –824.2 kJ mol . H
(d) C (graphite) + 4H(g) 
 CH4(g)
for the reaction.
80. For the reaction,
2Fe2 O3  s  
 4Fe  s   3O2  g  is :
2H 2 O  g  
 2H 2  g   O 2  g  H = 571.6 KJ
(a) –412.1 kJ (b) –1648.4 kJ

f H of water is : (c) –3296.8 kJ (d) 1648.4 kJ


86. The H for the reaction,
(a) 285.8 kJ (b) –285.8 kJ

(c) 1143.2 kJ (d) –1143.2 kJ 4S(s) + 6O2 (g) 

 4 SO3(g)

81. H for the reaction, is –1583.2 kJ. Standard enthalpy of formation of sulphur
trioxide is :
1  SO3  g  (a) –3166.4 kJ (b) 3166.4 kJ
SO 2  g   O 2  g   H = –98.3 kJ
2
(c) –395.8 kJ (d) 395.8 kJ
If the enthalpy of formation of SO3(g) is –395.4 kJ then the
87. Calculate the heat of formation of PCl5(s) from the
enthalpy of formation of SO2(g) is : following data :
(a) –297.1 kJ (b) 493.7 kJ 2P(s) + 3Cl2(g) 
 2PCl (l) H = –151.8 kcal
3

(c) –493.7 kJ (d) 297.1 kJ PCl3(l) + Cl2(g) 

 PCl (s) H = –32.8 kcal
5
–2
82. The standard heat of formation at 101.3 kNm and 298 K (a) –108.7 kcal (b) 108.7 kcal
is arbitrarily taken to be zero for :
(c) –184.6 kcal (d) 184.6 kcal
(a) gaseous bromine atoms
88. If S + O2 
 SO2 H = –298.2 kJ
(b) gaseous bromine molecules

(c) liquid bromine 1

SO 2  O 2 
 SO3 H = –98.2 kJ
2
(d) solid bromine.

83. The enthalpy of formation of two compounds A and B are  H 2SO4 H = –130.2 kJ
SO3  H 2 O 
–84 kJ and –156 kJ respectively. Which one of the following
statements is correct ? 1
H 2  O 2 
 H2O H = –287.3 kJ
(a) A and B are endothermic compounds 2

(b) A is more stable than B the enthalpy of formation of H2SO4 at 298 K will be

(c) A is less stable than B (a) –433.7 kJ (b) –650.3 kJ

(d) Both A and B are unstable (c) +320.5 kJ (d) –813.9 kJ

H formation & Combustion 95. The enthalpy of neutralisation of HCl by NaOH is –57.1 kJ
–1
and that of HCN by NaOH is –12.1 kJ mol . The enthalpy
89. The enthalpies of combustion of carbon and carbon
–1 of ionization of HCN is :
monoxide are –393.5 and –283.0 kJ mol respectively. The
enthalpy of formation of carbon monoxide is : (a) –69.2 kJ (b) –45.0 kJ
(a) –676.5 kJ (b) 110.5 kJ (c) 69.2 kJ (d) 45.0 kJ
(c) –110.5 kJ (d) 676.5 kJ
96. The enthalpy of neutralisation of NH4OH and HCl is :
90. On combustion, carbon forms two oxides CO and CO2.
–1 –1
Heat of formation of CO2 is –393.5 kJ and that of CO is – (a) 57.1 kJ mol (b) < 57.1 kJ mol
110.5 kJ. Heat of combustion of CO is : –1
(c) > 57.1 kJ mol (d) zero
(a) –393.5 kJ (b) –504.0 kJ
–1
(c) –283.0 kJ (d) 2830.0 kJ 97. The heat of neutralisation of NaOH and HCl is 57.3 kJ mol .
The amount of heat liberated when 0.25 mol of H2SO4
H dissolution reacts with 1 mole of NaOH is
91. Which of the following compounds will absorb maximum
(a) 57.3 kJ (b) 14.325 kJ
quantity of heat when dissolved in the same amount of
water. The enthalpies of solution of these compounds at (c) 28.65 kJ (d) 114.6 kJ
25°C in kJ/mole are given in brackets ?
–1 –1
98. The heat of neutralisation of strong base and strong acid
(a) P(H = –32.6 kJ mol ) (b) Q (H = –17.3 kJ mol ) is 57.0 kJ. The heat released when 0.5 mol of HNO3 is
–1 –1
(c) R (H = +2.56 kJ mol ) (d) S (H = +25.6 kJ mol ) added to 0.2 mol of NaOH solution is :

92. Which of the following salts will have maximum cooling (a) 57.0 kJ (b) 11.40 kJ
effect when 0.5 mole of the salt is dissolved in same amount
(c) 28.5 kJ (d) 34.9 kJ
of water. Integral heat of solution at 298 K is given for
each salt ? 99. In which of the following neutralisation reaction, the heat
–1 of neutralisation will be highest ?
(a) KNO3 (H = 35.4 kJ mol )

(b) NaCl
–1
(H = 5.35 kJ mol ) (a) NH4OH and H2SO4 (b) HCl and NaOH
–1
(c) HBr (H = –83.3 kJ mol ) (c) CH3COOH and KOH (d) CH3COOH and NH4OH
–1
(d) KOH (H = –55.6 kJ mol ) 100. The enthalpies of neutralization of a weak base AOH and
a strong base BOH by HCl are –12250 cal/mol and –13000
H neutralisation cal/mol respectively. When one mole of HCl is added to a
93. Which of the following pairs has heat of neutralisation solution containing 1 mole of AOH and 1 mole of BOH,
equal to –57.1 kJ ? the enthalpy change was –12500 cal/mol. In what ratio is
the acid distribution between AOH and BOH?
(a) HNO3,KOH (b)HCl, NH4OH
(a) 2:1 (b) 2:3
(c) H2SO4,NH4OH (d) CH3COOH,NaOH
(c) 1:2 (d) None of these
94. Which of the following neutralisation reactions is most
exothermic ? 101. In what proportion 1 M NaOH and 0.5 H2SO4 are mixed so
(a) HCl and NaOH as to release maximum amount of energy and to form 100
mL solution ?
(b) HCN and NaOH
(a) 33 and 67 (b) 67 and 33
(c) HCl and NH4OH
(c) 40 and 60 (d) 50 and 50
(d) CH3COOH and NH4OH
H of Physical Transition 108. For the process : CO2(s) 
 CO2(g)
102. The enthalpy change for the reaction,
(a) Both H and S are +ve
 H 2 O    is called
H 2 O  s  
(b) H is –ve, S is +ve
(a) Enthalpy of formation
(c) H is +ve, S is –ve
(b) Enthalpy of fusion
(d) Both H and S are –ve.
(c) Enthalpy of vaporisation
o o
(d) Enthalpy of transition 109. Given rS = –266 and listed [ Som values] calculate S for
103. The enthalpies of combustion of rhombic sulphur and Fe3O4(s) :
–1
monoclinic sulphur are –295.1 and –296.4 kJ mol
respectively. The enthalpy of allotropic transformation of 4Fe3 O 4 (s)[.......]  O 2 (g)[205]  6Fe 2 O3 (S)[87]
monoclinic to rhombic sulphur is :
(a) +111.1 (b) 
(a) 1.3 kJ (b) –1.3 kJ
(c)  (d) 248.25
(c) –591.5 kJ (d) 0
Enthalpy (Reaction Based) Gibss Energy (Reaction Based)
104. In an endothermic reaction 110. For the reaction at 300 K
(a) H is negative
A(g) + B(g) 
 C(g)
(b) Heat is given to the surroundings
(c) Enthalpy of the reactants is less than that of the U = –3.0 kcal S = –10.0 cal/K
products –1 –1
(R  2 cal mol K )
(d) E is negative
G is :
105. Which of the following enthalpies is always negative ?
(a) Enthalpy of solution (a) –600 cal (b) –3600 cal
(b) Enthalpy of combustion (c) 2400 cal (d) 3000 cal
(c) Enthalpy of sublimation
Bond Energy
(d) Enthalpy of formation
111. The standard enthalpies of formation of HCl(g), H(g) and
106. In the reaction : –1
Cl(g) are –92.2, 217.7 and 121.4 kJ mol respectively. The
CO 2  g   H 2  g  
 CO  g   H 2 O  g  bond dissociation energy of HCl is :

H = 2.8 kJ (a) +431.3 kJ (b) 236.9 kJ

then H represents (c) –431.3 kJ (d) 339.1 kJ
(a) heat of formation (b) heat of reaction
112. The enthalpy changes at 25°C in successive breaking of
(c) heat of solution (c) heat of combustion O–H bonds of water are :
107. Calculate the entropy change (J/mol K) of the given H2O(g) 
 H(g) + OH(g) H = 498 kJ mol
–1
reaction. The molar entropies [J/K–mol] are given in
brackets after each substance. –1
OH(g) 
 H(g) + O(g) H = 428 kJ mol
2 Pb S(s) [91.2] + 3O2(g)[205.1] 
 the bond enthalpy of the O–H bond is :
–1 –1
2PbO(s) [66.5] + 2SO2(g)[248.2] (a) 498 kJ mol (b) 463 kJ mol
(a) –113.5 (b) –168.3 –1 –1
(c) 428 kJ mol (d) 70 kJ mol
(c) +72.5 (d) –149.2
113. Calculate the heat of the reaction Born Haber
CH2 = CH2(g) + H2(g) 
 CH3CH3(g) 118. Using the following energy values, determine the lattice
energy of KF(s):
given that bond energy of C – C, C = C, C – H and H – H is –1
80, 145, 98 and 103 kcal. Property Energy (kJ mol )
–1 –1
(a) –28 kcal mol (b) –5.6 kcal mol Hatomization of K(s) 90
–1 –1
(c) –2.8 kcal mol (d) –56 kcal mol Hatomization of F2(s) 158
114. The enthalpy change for the following reaction is 368 kJ. Hf of KF(s) –567
Calculate the average O–F bond energy.
IE of K(s) 419
OF2 (g)  O(g)  2F(g) EA of F(g) 328
(a) 184 kJ/mol (b) 368 kJ/mol (a) 51 kJ (b) + 827 kJ
(c) 536 kJ/mol (d) 736 kJ/mol (c) + 1145 kJ (d) + 1483 kJ
115. The enthalpy change for the reaction, 119. The lattice enthalpy and hydration enthalpy of four
C2H6(g)  2C(g) + 6H(g) is X kJ. The bond energy of C– compounds are given below:
H bond is:
Compound Lattice enthalpy Hydration enthalpy
X X (kJ/mol) (kJ/mol)
(a) (b)
2 3 P +780 –920
X Q +1012 –812
(c) (d) data insufficient
6 R +828 –878
o
116. Based on the values of B.E. given, fH of N2H4(g) is: S +632 –600
–1 –1
Given: N–N = 159 kJ mol ; H–H = 436 kJ mol The pair of compounds which is soluble in water is
–1 –1 (a) P and Q (b) Q and R
N  N = 941 kJ mol , N–H = 398 kJ mol
–1 –1 (c) R and S (d) P and R
(a) 711 kJ mol (b) 62 kJ mol
(c) –98 kJ mol
–1
(d) –711 kJ mol
–1 Hess’ Law
120. An imaginary reaction X  Y takes place in three steps
117. The dissociation energy of CH4 and C2H6 are respectively
360 and 620 kcal/mole. The bond energy of C–C is X  A, H = –q1; B  A, H = –q2, B  Y,, H = –q3
(a) 260 k cal/mole (b) 180 k cal/mole If Hess’ law is applicable, then the heat of the reaction
(c) 130 k cal/mole (d) 80 k cal/mole (X  Y) is:
(a) q1–q2+q3 (b) q2–q3–q1
(c) q1–q2–q3 (d) q3–q2–q1
 EXERCISE - 2 : PREVIOUS YEAR JEE MAINS QUESTION

1. A reaction is non-spontaneous at the freezing point of (c) nature of intermediate reaction steps
water but is spontaneous at the boiling point of water,
then (2002) (d) difference in initial or final temperatures of involved
substances
H S
8. The enthalpies of combustion of carbon and carbon
(a) + ve + ve monoxide are – 393.5 and – 283 kJ mol–1 respectively. The
(b) – ve – ve enthalpy of formation of carbon monoxide per mole is
(c) – ve + ve (2004)
(d) + ve – ve (a) 110.5 kJ (b) 676.5 kJ
2. A heat engine absorbs heat q1 from a source at temperature (c) – 676.5 kJ (d) – 110.5 kJ
T1 and heat q2 from a source at temperature T2. Work done
9. An ideal gas expands in volume from 1 × 10–3 m3 to
is found to be J (q1 + q2). This is in accordance with
1 × 10–2 m3 at 300 K against a constant pressure of
(2002)
1 × 105 Nm–2. The work done is (2004)
(a) First law of thermodynamics
(a) – 900 J (b) – 900 kJ
(b) Second law of thermodynamics
(c) 270 kJ (d) 900 kJ
(c) Joules equivalent law
10. For a spontaneous reaction the G, equilibrium constant
(d) None of the above
(K) and Eºcell will be respectively (2005)
3. Heat required to raise the temperature of 1 mole of a
substance by 1º is called (2002) (a) –ve, >1, –ve (b) –ve, <1, –ve
(a) specific heat (b) molar heat capacity (c) +ve, >1, –ve (d) –ve, >1, + ve
(c) water equivalent (d) specific gravity 11. If the bond dissociation energies of XY, X2 and Y2 (all
4. The correct relationship between free energy change in a diatomic molecules) are in the ratio of 1 : 1 : 0.5 and Hf for
reaction and the corresponding equilibrium constant Kc is the formation of XY is –200 kJ mol–1. The bond dissociation
(2003) energy of X2 will be (2005)

(a) G = RT ln Kc (b) –G = RT ln Kc (a) 400 kJ mol–1 (b) 300 kJ mol–1

(c) Gº = RT ln Kc (d) – Gº = RT ln Kc (c) 200 kJ mol–1 (d) None of these
5. If at 298 K the bond energies of C—H, C—C, C C and 12. Consider the reaction : N2 + 3H2  2NH3 carried out at
H—H bonds are respectively, 414, 347, 615 and constant temperature and pressure. If H and E are the
435 kJ mol–1, the value of enthalpy change for the reaction, enthalpy and internal energy changes for the reaction,
H2 C CH2(g) + H2(g) H3C —CH3(g) at 298 K will which of the following expressions is true ? (2005)
be (a) H > E (b) H < E
(a) + 250 kJ (b) – 250 kJ (c) H = E (d) H = 0
(c) + 125 kJ (d) – 125 kJ
13. The standard enthalpy of formation (Hºf) at 298 K for
6. The internal energy change when a system goes from state methane, CH4(g) is – 74.8 kJ mol–1.
A to B is 40 kJ/mol. If the system goes from A to B by a
reversible path and returns to state A by an irreversible The additional information required to determine the
path, what would be the net change in internal energy ? average energy for C—H bond formation would be(2006)
(2003) (a) the dissociation energy of H 2 and enthalpy of
(a) 40 kJ (b) > 40 kJ sublimation of carbon
(c) < 40 kJ (d) zero (b) latent heat of vaporisation of methane
7. The enthalpy change for a reaction does not depend upon (c) the first four ionisation energies of carbon and electron
the (2003) gain enthalpy of hydrogen
(a) physical state of reactants and products (d) the dissociation energy of hydrogen molecule, H2
(b) use of different reactants for the same product
14. The enthalpy changes for the following processes are listed R = 8.3 J mol–1 K–1) will be (2007)
below :
(a) 4.100 kJ mol–1 (b) 3.7904 kJ mol–1
Cl2 (g) = 2Cl(g), 242.3 kJ mol–1
(c) 37.904 kJ mol–1 (d) 41.00 kJ mol–1
I2(g) = 2I(g), 151.0 kJ mol–1
20. Standard entropy of X2, Y2 and XY3 are 60, 40 and
ICl (g) = I(g) + Cl (g), 211.3 kJ mol–1 50 JK–1 mol–1, respectivley. For the reaction,
I2(s) = I2(g), 62.76 kJ mol–1
1 3
Given that the standard states for iodine and chlorine are X 2  Y2  XY3 , H   30 kJ, to be at equilibrium,
2 2
I2(s) and Cl2(g), the standard enthalpy of formation of the temperature will be (2008)
ICl (g) is (2006) (a) 1250 (b) 500 K
(a) – 14.6 kJ mol–1 (b) – 16.8 kJ mol–1 (c) 750 K (d) 1000 K
(c) + 16.8 kJ mol–1 (d) + 244.8 kJ mol–1 21. Oxidising power of chlorine in aqueous solution can be
determined by the parameters indicated below :
15. (H – E) for the formation of carbon monoxide (CO) from
its elements at 298 K is (R=8.314 JK–1 mol–1) (2006) 1 0
1  H  EA H0
2 diss  Cl (g) 
Cl2 (g)  
(a) – 1238.78 J mol–1 (b) 1238.78 J mol–1 2
(c) – 2477.57 J mol–1 (d) 2477.57 J mol–1 Cl  (g) 
hydH 0
 Cl  (aq)
16. An ideal gas is allowed to expand both reversibly and
irreversibly in an isolated system. If T i is the initial 1
The energy involved in the conversion of Cl (g) to
temperature and Tf is the final temperature, which of the 2 2
following statements is correct ? (2006) 0
Cl– (aq) will be (using the data, diss HCl 2
 240 kJ mol1
(a) (Tf)irrev > (Tf)rev
 EA H0Cl  349kJ mol1 ,  hyd H 0Cl  381 kJ mol 1 )
(b) Tf > Ti for reversible process but Tf = Ti for irreversible (2008)
process
(a) + 152 kJ mol–1 (b) – 610 kJ mol–1
(c) (Tf)rev = (Tf)irrev
(c) – 850 kJ mol–1 (d) + 120 kJ mol–1
(d) Tf = Ti for both reversible and irreversible processes
22. On the basis of the following thermochemical data
17. In conversion of limestone to lime, [fGº H+ (aq) = 0]
CaCO3(s)  CaO (s) + CO2 (g) H2O(l)  + –
 H (aq) + OH (aq); H = 57.32 kJ
–1
the values of Hº and Sº are + 179.1 kJ mol and 160.2 J/K
1
respectively at 298 K and 1 bar. Assuming that Hº and H2(g) + O (g)   H2O(l);
Sº do not change with temperature, temperature above 2 2
which conversion of limestone to lime will be spontaneous H = – 286.02 kJ
is (2007)
The value of enthalpy of formation of OH– ion at 25ºC is
(a) 1008 K (b) 1200 K
(a) – 22.88 kJ (b) – 228.88 kJ
(c) 845 K (d) 1118 K
(c) + 228.88 kJ (c) – 343.52 kJ
18. Identify the correct statement regarding a spontaneous
23. In a fuel cell methanol is used as fuel and oxygen gas is
process. (2007)
3
(a) For a spontaneous process in an isolated system, the used as an oxidiser. The reaction is CH3OH(l) + O2(g)
change in entropy is positive 2
(b) Endothermic processes are never spontaneous   CO2(g) + 2H2O(l). At 298 K standard Gibb’ss
energies of formation for CH3OH(l), H2O (l) and CO2(g)
(c) Exothermic processes are always spontaneous
are – 166.2, –237.2 and –394.4 kJ mol–1 respectively.
(d) Lowering of energy in the reaction process is the only If standard enthalpy of combustion of methanol is
criterion for spontaneity – 726 kJ mol–1, efficiency of the fuel cell will be (2009)
19. Assuming that water vapour is an ideal gas, the internal (a) 80% (b) 87%
energy change (E) when 1 mole of water is vaporised at 1
(c) 90% (d) 97%
bar pressure and 100ºC, (Given : molar enthalpy of
vaporisation of water at 1 bar and 373 K = 41 KJ mol–1 and
24. For a particular reversible reaction at temperature T, H 31. The hottest region of Bunsen flame shown in the figure
and S were found to be both +ve. If Te is the temperature
at equilibrium, the reaction would be spontaneous when below is: (2016)
(2010)
(a) Te > T (b) T > Te
(c) Te is 5 times T (d) T = Te
25. The standard enthalpy of formation of NH3 is – 46.0 kJ mol–1.
If the enthalpy of formation of H2 from its atoms is
– 436 kJ mol–1 and that of N2 is –712 kJ mol–1, the average
bond enthalpy of N—H bond in NH3 is (2010)
(a) – 964 kJ mol–1 (b) + 352 kJ mol–1
(a) region 2 (b) region 3
(c) + 1056 kJ mol–1 (d) – 1102 kJ mol–1
26. Consider the reaction (c) region 4 (d) region 1
4NO2(g) + O2(g)  2N2O5(g), rH = – 111 kJ. If N2O5(s) is 32. U is equal to : (2017)
formed instead of N2O5(g) in the above reaction, the rH
value will be (a) Isobaric work (b) Adiabatic work
(Given, H of sublimation for N2O5 is 54 kJ mol–1) (2011)
(a) – 165 kJ (b) + 54 kJ (c) Isothermal work (d) Isochoric work
(c) +219 kJ (d) – 219 kJ
33. Given
27. The value of enthalpy change (H) for the reaction
C2H5OH(l) + 3O2(g)  2CO2(g) + 3H2O(l), C(graphite) + O2 (g)  CO2(g) ;
at 27ºC is – 1366.5 kJ mol–1. The value of internal energy
change for the above reaction at this temperature will be rH° = –393.5 kJ mol–1
(2011)
1
(a) – 1371.5 kJ (b) – 1369.0 kJ H2  g   O2  g   H2O 1 ;
(c) – 1364.0 kJ (d) – 1361.5 kJ 2
28. In view of the signs of rGº for the following reactions rH° = – 285.8 kJ mol–1
PbO2 + Pb  2PbO, rGº < 0, CO2(g) + 2H2O(l)  CH4(g) + 2O2(g);
SnO2 + Sn  2 SnO, rGº > 0
Which oxidation states are more characteristic for lead and rH° = +890.3 kJ mol–1
tin ? (2011) Based on the above thermochemical equations, the
(a) For lead + 4, For tin + 2 (b) For lead + 2, for tin + 2 value of rH° at 298 K for the reaction
(c) For lead + 4, for tin + 4 (d) For lead +2, for tin + 4
C(graphite) + 2H2(g)  CH4(g) will be : (2017)
29. The entropy change involved in the isothermal reversible
expansion of 2 moles of an ideal gas from a volume of (a) + 144.0 kJ mol–1 (b) –74.8 kJ mol–1
10 dm3 to a volume of 100 dm3 at 27º C is (2011)
(c) –144.0 kJ mol–1 (d) +74.8 kJ mol–1
(a) 38.3 J mol–1K–1 (b) 35.8 J mol–1K–1
(c) 32.3 J mol–1K–1 (d) 42.3J mol–1K–1 34. The combustion of benzene (I) gives CO2(g) and H2O(l).
30. For complete combustion of ethanol, Given that heat of combustion of benzene at constant
C2H5OH(l )  3O2 (g)  2CO2 (g)  3H2O(l ), volume is –3263.9 kJ mol–1 at 25°C; heat of combustion (in
the amount of heat produced as measured in bomb kJ mol–1) of benzene at constant pressure will be:
calorimeter, is 1364.47 kJ mol–1 at 25ºC. Assuming ideality
(R = 8.314 JK–1 mol–1) (2018)
the Enthalpy of combustion,  CH, for the reaction will be :
(R = 8.314 kJ mol–1) (2014) (a) – 3267.6 (b) 4152.6
(a) –1361.95 kJ mol–1 (b) –1460.50 kJ mol –1
(c) –452.46 (d) 3260
(c) – 1350.50 kJ mol–1 (d) – 1366.95 kJ mol–1
JEE MAINS ONLINE QUESTION (b) the dissociation energy of the hydrogen molecule,
H2.
Online 2014 SET (1)
(c) the first four ionisation energies of carbon and
1. The standard enthalpy of formation of NH3 is –46.0 kJ electron affinity of hydrogen.
mol–1. If the enthalpy of formation of H2 from its atoms
(d) the first four ionisation energies of carbon.
is –436 kJ mol–1 and that of N2 is – 712 kJ mol–1, the
average bond enthalpy of N — H bond in NH3 is: 5. The H and S for a reaction at one atmospheric pressure
are +30.558 kJ and 0.066 kJk–1 respectively. The temperature
Online 2014 SET (1) at which the free energy change will be zero and below of
(a) – 1102 kJ mol–1 (b) – 964 kJ mol–1 this temperature the nature of reaction would be
Online 2015 SET (1)
(c) + 352 kJ mol–1 (d) + 1056 kJ mol–1
(a) 483 K, spontaneous
2. The molar heat capacity (Cp) of CD2O is 10 cals at 1000
K. The change in entropy associated with cooling of 32 (b) 443 K, spontaneous
g of CD2O vapour from 1000 K to 100 K at constant (c) 463 K, spontaneous
pressure will be: Online 2014 SET (2)
(d) 463 K, non-spontaneous
(D = deuterium, at. Mass = 2 u)
6. A reaction at 1 bar is non-spontaneous at low temperature
(a) 2.303 cal deg–1 (b) 23.03 cal deg–1 but becomes spontaneous at high temperature. Identify
the correct statement about the reaction among the
(c) –23.03 cal deg–1 (d) –2.303 cal deg–1 following : Online 2016 SET (1)
3. The entropy (So) of the following substances are: (a) Both “H and “S are negative.

CH4 (g) 186.2 J K–1 mol–1 (b) Both “H and “S are positive.
(c) “H is positive while “S is negative.
O2 (g) 205.0 J K–1 mol–1
(d) “H is negative while “S is positive
CO2 (g) 213.6 J K–1 mol–1
7. For the reaction, A(g) + B(g)  C(g) + D(g), H° and S°
H2O (l) 69.9 J K–1 mol–1 are respectively, –29.8 kJ mol–1 and –0.100 kJ K–1 mol–1
The entropy change (So) for the reaction at 298 K. The equilibrium constant for the reaction at
298 K is : Online 2016 SET (1)
CH4(g) + 2O2(g) ’! CO2(g) + 2H2O (l) is:
(a) 1.0 × 10–10 (b) 1.0 × 1010
Online 2014 SET (3)
(c) 10 (d) 1
(a) –37.6 J K–1 mol–1
8. lf 100 mole of H2O2 decompose at 1 bar and 300 K, the
(b) –312.5 J K–1 mol–1 work done (kJ) by one mole of O2(g) as it expands against
1 bar pressure is :
(c) –242.8 J K–1 mol–1

2H2O2 (l )  2H2O(l )  O2 (g)
(d) –108.1 J K–1 mol–1

4. The standard enthalpy of formation (fHo298) for methane, (R  8.3 JK 1mol 1 ) Online 2016 SET (2)
CH4 is –74.9 kJ mol–1. In order to calculate the average
energy given out in the formation of a C – H bond from (a) 62.25 (b) 124.50
this it is necessary to know which one of the following? (c) 249.00 (d) 498.00
Online 2014 SET (3) 9. For a reaction, A(g) ’! A(l); “H = “ 3RT. The correct
statement for the reaction is : Online 2017 SET (1)
(a) The dissociation energy of H 2 and enthalpy of
sublimation of carbon (graphite) (a) “H = “U `” O (b) “H = “U = O
(c) |”H| < |”U| (d) |H| > |U|
10. What is the value of change in internal energy at 1 atm
in the process? UBC = -5kJ mol-1 , qAB = 2kJ mol-1

H2O  , 323 K   H2O  g, 423 K  WAB = -5 kJ mol-1 ,WCA = 3 kJ mol-1

Given : Heat absorbed by the system during process CA is :
Cv,m  H2O,    75.0 JK mol ; 1 1
Online 2018 SET (1)
-1
(a) -5 kJ mol (b) +5 kJ mol-1
Cp,m  H2O, g   33.314 JK 1mol1 ;
(c) 18 kJ mol-1 (d) -18 kJ mol-1
Hvap at 373 K = 40.7 kJ/mol Online 2017 SET (1)
(a) 42.91 kJ/mol (b) 43086 kJ/mol
15.  f G0 at 500 K for substance ‘S’ in liquid state and
(c) 42.6 kJ/mol (d) 49.6 kJ/mol gaseous state are +100.7 kcal mol-1 and +103 kcal mol-1,
respectively. Vapour pressure of liquid ‘S’ at 500 K is
11. An ideal gas undergoes isothermal expansion at
approximately equal to :
constant pressure. During the process :
Online 2017 SET (2) (R = 2 cal K-1 mol-1) Online 2018 SET (2)
(a) enthalpy increases but entropy decreases. (a) 0.1 atm (b) 1 atm
(b) enthalpy remains constant but entropy increases. (c) 10 atm (d) 100 atm
(c) enthalpy decreases but entropy increases. 16. Given
(d) Both enthalpy and entropy remain constant.
(i) 2Fe2O3(s)  4Fe(s) + 3O2(g);  r G0
12. A gas undergoes change from state A to state B. In this
process, the heat absorbed and work done by the gas is = + 1487.0 kJ mol-1
5J and 8J, respectively. Now gas is brought back to A by
another process during which 3J of heat is evolved. In (ii) 2CO(g) + O2(g) 2CO2(g) ; = -514.4 kJ mo l-1
this reverse process of B to A : Online 2017 SET (2) Free energy change, for the reaction 2Fe2O3(s) + 6CO(g)
(a) 10J of the work will be done by the gas. 4Fe(s) + 6CO2(g) will be : (Online 2018 SET (2)
(b) 6J of the work will be done by the gas.
(a) -112.4 kJ mol-1 (b) -56.2 kJ mol-1
(c) 10J of the work will be done by the surrounding on
gas. (c) -168.2 kJ mol-1 (d) -208.0 kJ mol-1
(d) 6J of the work will be done by the surrounding on 17. For which of the following processes,  S is negative ?
gas.
(Online 2018 SET 3)
13. For which of the following reactions, H is equal to
U ? Online 2018 SET (1) (a) H2(g)  2H(g)
(b) N2(g, 1 atm) N2(g, 5 atm)
(a) N2  g  + 3H2  g   2NH3  g 
(c) C(diamond) C(graphite)
(b) 2HI  g   H2  g  + I2  g  (d) N2(g, 273 K) N2(g, 300 K)

(c) 2NO2  g   N2 O4  g  18. At 320 K, a gas A2 is 20 percent dissociated to A(g).

The standard free energy change at 320 K and 1 atm in
(d) 2SO2  g  + O2  g   2SO3  g  J mol-1 is approximately :
14. An ideal gas undergoes a cyclic process as shown in (R=8.314 JK”1 mol”1; ln 2=0.693; ln 3=1.098)
Figure.
(Online 2018 SET 3)
(a) 4763 (b) 2068
(c) 1844 (d) 4281
 EXERCISE - 3 : ADVANCED OBJECTIVE QUESTIONS
1. All questions marked “S” are single choice questions
2. All questions marked “M” are multiple choice questions
3. All questions marked “C” are comprehension based questions
4. All questions marked “A” are assertion–reason type questions
(A) If both assertion and reason are correct and reason is the correct explanation of assertion.
(B) If both assertion and reason are true but reason is not the correct explanation of assertion.
(C) If assertion is true but reason is false.
(D) If reason is true but assertion is false.
5. All questions marked “X” are matrix–match type questions
6. All questions marked “I” are integer type questions

Extensive/Intensive (a) A (b) B

1. (A) Assertion : The extensive properties of a single pure (c) C (d) D
substance will not only depend upon the number of
First Law
moles of the substance present but also on any two
of the three variables. 5. (S) Consider an ideal gas. When dW = 0 and dq < 0,
Reason : Any extensive property if (a) the temperature will decrease
expressed as per mole or per gram becomes an
(b) the volume will increase
intensive property.
(c) the pressure will remain constant
(a) A (b) B
(d) the temperature will increase
(c) C (d) D
Isothermal Process
Internal Energy 6. (S) When heat is supplied to an ideal gas in an isothermal
2. (S) An ideal gas at constant temperature and pressure process, the
expands, then its (a) gas will do positive work
(a) Internal energy remains same (b) gas will do negative work
(b) Internal energy decreases (c) kinetic energy of the gas will increase
(c) Internal energy increases (d) gas will not obey the law of conservation of energy
(d) Entropy first increases and then decreases Adiabatic Process
3. (S) The internal energy of a substance 7. (S) The magnitudes of enthalpy changes for irreversible
(a) Increases with increase in temperature adiabatic expansion of a gas from 1L to 2L is H1 and
(b) Decreases with increase in temperature for reversible adiabatic expansion for the same expansion
is H2. Then
(c) Can be calculated by the relation E = mc2
(a) H1 > H2 (b) H1 < H2
(d) Remains unaffected with change in temperature
4. (A) Assertion : There is no change in internal energy (c) H1 = H2, enthalpy being a state function
for an ideal gas at constant temperature.
(d) H1 = E1 & H2 = E2 where E1 & E2 are
Reason : Internal energy of an ideal gas is a function magnitudes of change in internal energy of gas in
of temperature only. these expansions respectively.
8. (S) A liquid which is confined inside an adiabatic piston is Processes
suddenly taken from state 1 to state 2 by a single stage
12. (A) Assertion : A reversible process produces more work
process. If the piston comes to rest at point 2 as shown. than the same process if it is carried out irreversibly
Then the enthalpy change for the process will be : for the same increase in volume.
Reason : A reversible process is exothermic while
P irreversible process is endothermic
2P0 1 (a) A (b) B
(c) C (d) D
P0 2 COMPREHENSION
V0 4V0 V Observe the following graphic representation of four
basic thermodynamic processes.

2 P0 V0 3P0 V0
(a) H    1 (b) H    1 Isobaric

Isochoric
Pressure Isothermal
Adiabatic
(c) H = – P0 V0 (d) None of these

9. (S) A gas expands adiabatically at constant pressure such

–1/2
that T  V . The value of (Cp,m/Cv,m) of the gas will
be : Volume
13. (C) Which of the following is true for isochoric process ?
(a) 1.30 (b) 1.50
(a) V = 0 (b) U = q + PV (c) U = qv
(c) 1.70 (d) 2 (d) All of these
14. (C) Which of the following is not true for isothermal process ?
10. (S) 1 mole of an ideal gas A (Cv,m = 3 R) and 2 mole of an
3  V2
 (a) wexp = –2.303 nRT log V
ideal gas B  C v,m  R  are taken in a container and
 2  1

expanded reversible and adiabatically from 1 litre to 4

litre starting from initial temperature of 320 K. E or U P1
(b) wexp = –2.303 nRT log P
for the process is : 2

(a) –240 R (b) 240 R

(c) T = 0 (d) T1V11  T2 V21
(c) 480 R (d) –960 R
CP
15. (C) If the ratio  1.30 , the atomicity of gas is
 5  CV
11. (S) 0.5 mole each of two ideal gases A  C v,m  R  and B
 2 
(a) 1 (b) 2
(Cv,m = 3R) are taken in a container and expanded
reversibly and adiabatically, during this process (c) 3 (d) 4
temperature of gaseous mixture decreased from 350 K 16. (S) 2 mole of an ideal monoatomic gas undergoes a
2
and 250 K. Find H (in cal/mol) for the process : reversible process for which PV = C. The gas is expnaded
from initial volume of 1 L to final volume of 3L starting
(a) –100 R (b) –137.5 R
from initial temperature of 300 K. Find H for the process:
(c) –375 R (d) None of these (a) –600R (b) –1000R

(c) –3000R (d) None of these

Heat Capacity 22. (S) 10 mole of an ideal gas is heated at constant pressure of
o o –
one atmosphere from 27 C to 127 C. If Cv,m = 21.686 + 10
17. (S) A certain gas in expanded from (lL, 10 atm) to (4L, 5 atm) 3
T, then H for the process is :
against a constant external pressure of 1 atm. If the
initial temperature of gas is 300 K and heat capacity for (a) 3000 J (b) 3350 J
the process is 50 J/ºC, the enthalpy change during the (c) 3700 J (d) 30350
process is : (Use : 1L atm 100 J)
Entropy (Reaction based)
(a) 15 kJ (b) 15.7 kJ
23. (S) For an ideal gas undergoing adiabatic expansion
(c) 14.3 kJ (d) 14.7 kJ in vaccum,
18. (S) The molar heat capacities at constant pressure (assumed (a) U = 0 (b) q = 0
constant with respect to temperature) for A, B and C are
in ratio of 3 : 1.5 : 2.0. The enthalpy change for the (c) W = 0 (d) all the above are true
exothermic A + 2B  3C at 300 K and 310 K is H300 and 24. (S) What is the change in molar entropy of helium in the
H310 (magnitudes) respectively then : following process ?
(a) H300 > H310 (b) H300 < H310 1 He (298 K, 1 bar)  1 He (100 K, 10 bar)

(c) H300 = H310 (a) 41.8 J K–1 mol–1 (b) 4.18 J K–1 mol–1

(d) if T2 > T1 then H310 > H300 and if T2 < T1 (c) – 41.8 J K–1 mol–1 (d) – 4.18 J K–1 mol–1

then H310 < H300 H

25. (S) S  holds good for
T
COMPREHENSION
(a) an adiabatic process
Molar heat capacity is heat required to raise the
temperature of one mole of material by one degree, since (b) an isothermal reversible-phase change
heat is not a state function, the amount of heat required (c) a process at constant pressure
to produce a given change in its state depends on the
path followed. (d) a process under any condition

CP = Specific heat × Molecular weight. It is measured at 26. (S) rH0 for solid-to-liquid transition for proteins A and B
constant pressure. are 2.73 kcal mol–1 and 3.03 kcal mol–1. The two melting
points are 0ºC and 30ºC respectively. The entropy
CV - Specific heat × Molecular weight. It is measured at
constant volume. changes SA and SB at two transition temperatures
are related as :
19. (C) Which of the following is correct ?
(a) SA = SB (b) SA < SB
CP
(a) CP – CV = R (b) C   303SA
V (c) SB > SA (d) SB =
273
(c) CP > CV (d) All of these 27. (A) Assertion : Entropy change in reversible adiabatic
20. (C) CP for monoatomic gas is expansion of an ideal gas is zero.

(a) 5/2 R (b) 3/2 R Reason : The increase in entropy due to volume
increase just componsate the decrease in entropy
(c) 7/2 R (d) R due to fall in temperature.
21. (C) The specific heat of a gas at constant volume is 0.075 cal/ (a) A (b) B
g. Predict the atomicity of the gas. Molar mass of gas is
–1
40 g mol . (c) C (d) D
(a) 1 (b) 2
(c) 3 (d) None of these
Relation b/w H & E (a) – 904 kJ/mol (b) – 602 kJ/mol

28. (S) For the real gases reaction (c) – 334 kJ/mol (d) – 30 kJ/mol

2CO (g) + O2(g) 

 2CO2 (g) H combustion
H = –560 kJ.
1
In 10 litre rigid vessel at 500 K the initial pressure is 70 33. (S) The enthalpy of reaction CH4(g) + O (g) CH3OH
2 2
bar and after the reaction it becomes 40 bar. The change
in internal energy is : (l ) is negative. If enthalpy of combustion of CH4 and
CH3OH are x and y respectively then which of the
(a) –557 kJ (b) –530 kJ
following relations is correct?
(c) –563 kJ (d) None of these
29. (A) Assertion : When internal energy of reactants (a) x > y (b) x < y
becomes greater than that of products the energy is
given out to the surrounding. (c) x = y (d) x  y

Reason : All exothermic reactions take place at 34. (S) For the allotropic change represented by the equation
constant temperature, E will be positive.
C (diamond)  (graphite) the enthalpy change is
(a) A (b) B
H = – 1.89 kJ
(c) C (d) D
If 6g of diamond and 6 g of graphite are separately burnt
30. (S) At 5 × 105 bar pressure, density of diamond and graphite to yield carbon dioxide, the heat, liberated in the first
are 3 g/cc and 2 g/cc respectively, at certain temperature case is
‘T’. Find the value of U–H for the conversion of
1 mole of graphite to 1 mole of diamond at temperature (a) less than in the second case by 1.89 kJ
‘T’ :
(b) more than in the second case by 1.89 kJ
(a) 100 kJ/mol (b) 50 kJ/mol
(c) – 100 kJ/mol (d) None of these (c) less than in the second case by 11.34 kJ

H formation (d) more than in the second case by 0.945 kJ

31. (S) The enthalpy of formation of NH3(g) at constant pressure 35. (S) The enthalpy of combustion for octane (a major
and 3500C temperature is –50.0 kJ mol–1. What will be the component of gasoline) is – 47.8 kJ/g. How much energy
enthalpy of formation of NH3(g) at constant volume at is released by burning 1.0 L of octane (density
the same temperature ? 0.740 g/mL) ?

(a) – 50.0 kJ mol–1 (b) – 45 kJ mol–1 (a) – 35400 kJ (b) – 64600 kJ

(c) – 60.4kJ mol–1 (d) – 54 kJ mol–1
(c) – 47800 kJ (d) – 57200 kJ
H reaction & formation
H formation & combustion
32. (S) Mg(s) + 2HCl(aq.) MgCl2(aq) + H2(g);
36. (S) Standard molar enthalpy of formation of CO2 is equal to
rH0 = – 467 kJ/mol
(a) zero
MgO (s) + 2HCl (aq) MgCl2 (aq) + H2O (l ) ;
(b) the standard molar enthalpy of combustion of
rH0 = – 151 kJ/mol
gaseous carbon
According to the information, and given the fact that
(c) the sum of standard enthalpies of formation of CO and
for water, fH0 = – 286 kJ/mol, what is the fH0 for
O2
MgO(s) ?
(d) the standard molar enthalpy of combustion of
carbon (graphite)
37. (S) Given that H0f (CO2, g) ionization of HCN in water is

= – 393.509 kJ mol–1, H0f (H2O, l ) (a) 10.5 kcal (b) 16.3 kcal

(c) 9.5 kcal (d) 11.5 kcal

= – 285.830 kJ mol–1, H0f (C2H5OH, l )
43. (A) Assertion : Heat of neutralization of HF is more than
= – 277.800 kJ mol–1. that of HCl by NaOH.
Calculate the Hº (combustion) of liquid ethanol. The Reason : HCl is stronger acid than HF.
following is the required reaction.
(a) A (b) B
C2H5OH (l ) + 3O2 (g) 2CO2 (g) + 3H2O (l )
(c) C (d) D
(a) – 1366.82 kJ mol–1 (b) – 278.82 kJ mol–1
44. (A) Assertion : Enthalpy of neutralization of CH3COOH
(c) – 2264.66 kJ mol–1 (d) – 1155.78 kJ mol–1 by NaOH is less than that of HCl by NaOH.
H neutralisation Reason : Enthalpy of neutralization of CH3COOH is
less because of the absorption of heat in the
38. (S) The enthalpy of neutralization of a strong acid by a
ionization process.
strong base is –57.32 kJ mol–1. The enthalpy of formation
of water is –285.84 kJ mol–1. The enthalpy of formation (a) A (b) B
of the hydroxyl ion is (c) C (d) D
(a) + 228.52 kJ mol–1 (b) – 114.26 kJ mol–1 H of Physical Transition
(c) – 228.52 kJ mol–1 (d) + 114.26 kJ mol–1 45. (S) Calculate the enthalpy change when 1.0 g of water is
39. (S) Heat of neutralisation of NaOH and HCl is –57.46 kJ/ frozen at 00C ( H0f = 1.435 kcal mol–1) ?
equivalent. The heat of ionisation of water will be :
(a) – 1.435 cal g–1 (b) – 80.0 cal g–1
(a) – 57.46 kJ/mol (b) 57.46 kJ/mol
(c) 80.0 cal g–1 (d) – 55.6 cal g–1
(c) – 114.92 kJ/mol (d) 114.92 kJ/mol
46. (S) The mathematical expression for the standard enthalpy
40. (S) In which case of mixing of a strong acid and strong of sublimation is given by
base, each of 1N concentration, temperature increase is (a) Hº (sublimation) = Hº (fusion) – 2Hº
the highest ? (vaporization)
(b) Hº (sublimation) = Hº (fusion) – Hº
(a) 20 ml acid and 30 ml alkali
(vaporization)
(b) 10 ml acid and 40 ml alkali (c) Hº (sublimation) = Hº (fusion) + Hº
(vaporization)
(c) 25 ml acid and 25 ml alkali
(d) Hº (sublimation) = Hº (combustion) + Hº
(d) 35 ml acid and 15 ml alkali (dissociation)
Entropy (Rx Based)
41. (S) Heat of neutralization of a strong dibasic acid in dilute
47. (S) Given are the following entropy values at 298 K and 1
solution by NaOH is nearly atm:

(a) – 27.4 kcal/eq (b) 13.7 kcal/mol H2 (g) = 130.6 J K–1 mol–1; Cl2 (g) = 223.0 J K–1 mol–1;
HCl (g) = 186.7 J K–1 mol–1
(c) – 13.7 kcal/eq (d) – 13.7 kcal/mol
The entropy change for the reaction
42. (S) Heat released in neutralization of strong acid and strong H2 (g) + Cl2 (g)  2HCl (g) would be
base is 13.4 kcal/mol. The heat released on neutralization (a) +540.3 J K–1 mol–1 (b) +727 J K–1 mol–1
of NaOH with HCN is 2.9 kcal/mol, then H° of (c) –166.9 J K–1 mol–1 (d) +19.8 J K–1 mol–1
COMPREHENSION Gibb’s Energy (Rx Based)
Standard Gibb’s energy of reaction (  r G o ) at a certain 51. (S) The free-energy change for the conversion of maleate
o o o
temperature can be computed as  r G   r H  T. r S into fumarate is 3.0 kJ. In metabolism, this reaction is

and the change in the value of  r H o and  r So for a coupled with the conversion fumarate to asparate,
reaction with temperature can be computed as follow: which is exergonic by 15.5 kJ. Calculate G 0 for the
overall reaction.
 r H To2   r H To1   r Cop (T2  T1 )
(a) – 185. kJ (b) + 18.5 KJ

T  (c) – 12.5 kJ (d) – 25.0 kJ

 r SoT2   r SoT1   r Cop ln  2 
 T1  52. (S) The G for the following reactions at 8000C are given as
S2 (s) + 2O2 (g) 2SO2 (g); G = – 544 kJ
 r G o   r H o  T. r So
2Zn (s) + S2 (s) 2ZnS (s) ; G = – 293 kJ
and by  r G o  RT ln K eq . 2Zn (s) + O2 (g) 2ZnO (s); G = – 480 kJ
Consider the following reaction: The G for the reaction

 CH3 OH(g)

CO(g)  2H 2 (g)  2Zn S + 3O2 (g) 2ZnO (s) + 2SO2 (g) will be
(a) – 357 kJ (b) – 731 kJ
Given:  f H o (CH3 OH, g) = –201 kJ/mol;
(c) – 773 kJ (d) – 229 kJ
o
 f H (CO, g) = –144 kJ/mol 53. (S) Consider the reaction below at 298 K :
o o –1 –1
S (CH3OH, g) = 240 J/K-mol; S (H2, g) = 29 JK mol C (graphite) + 2H2 (g)  CH4 (g)
o
S (CO, g) = 198 J/mol-K; Cop, m (H 2 ) =28.8 J/mol-K fHº (kJ/mol) – 74.9

Cop, m (CO) =29.4 J/mol-K; Cop, m (CH3 OH) = 44 J/mol-K S0m (J/K/mol) + 5.6 + 130.7 + 186.3
Which statement below is correct ?
 320  (a) rG0 is – 50.8 kJ and the reaction is driven by
and ln    0.06 , all data at 300 K
 300  enthalpy only.

48. (C)  r So at 300 K for the reaction is : (b) rG0 is – 50.8 kJ and the reaction is driven by entropy
only.
(a) 152.6 J/K-mol (b) 181.6 J/K-mol
(c) rG0 is + 50.8 kJ and the reaction is driven by both
(c) –16 J/K-mol (d) None of these enthalpy and entropy.
49. (C)  r H o at 300 K for the reaction is : (d) rG0 is – 50.8 kJ and the reaction is driven by both
enthalpy and entropy.
(a) –87 kJ/mol (b) 87 kJ/mol
54. (S) Given fH0 (KJ/mol) S0m (J/K/mol)
(c) –315 kJ/mol (d) –288 kJ/mol
CCl4 (l ) – 135.4 215.4
50. (C)  r So at 320 K is:
CCl4 (g) – 103.0 308.7
(a) 155.18 J/mol-K (b) 150.02 J/mol-K
What is the boiling point of carbon tetrachloride ?
(c) 172 J/mol-K (d) None of these (a) 8.25ºC (b) 74.3ºC
(c) 92.3ºC (d) 45.8ºC
55. (S) Calculate  f G o for (NH4Cl, s) at 310 K. 59. (S) What is the bond enthalpy of Xe–F bond?

XeF4  Xe  (g)  F (g)  F2 (g)  F(g);

Given :  f H o (NH4Cl, s)= –314.5 kJ/mol;  r C p =0
 r H  292 kcal / mol

SoN2 (g) =192 JK–1 mol–1; SoH2 (g) =130.5JK–1 mol–1 Given: Ionization energy of Xe=279 kcal/mol
B.E. (F–F) = 38 kcal/mol, Electron affinity of F=85 kcal/
SoCl2 (g) =233 JK–1 mol–1 SoNH4 Cl(s) = 99.5 JK–1 mol–1 mol

(All data given at 300K) (a) 24 kcal/mol (b) 34 kcal/mol

(a) – 198.56 kJ/mol (b) –426.7 KJ/mol (c) 8.5 kcal/mol (d) None of these
(c) –202.3 KJ/mol (d) None of these
Lattice Energy
Bond Energy
60. (S) The lattice energy of solid NaCl is 180 kcal per mol. The
56. (S) The bond energy of H2 is 104.3 kcal/mol. It means that dissolution of the solid in water in the form of ions is

(a) 104.3 kcal heat is needed to break one bond to form two endothermic to the extent of 1 kcal per mol. If the

atoms solvation energies of Na+ and Cl– ions are in the ratio
6 : 5, what is the enthalpy of hydration of sodium ion ?
(b) 104.3 kcal is required to break 6.02 × 1023 molecules
(a) – 85.6 kcal/mol (b) – 97.5 kcal/mol
into atoms of hydrogen
(c) 82.6 kcal/mol (d) + 100 kcal/mol
(c) 104.3 kcal is required to break 3.015 × 1023 hydrogen
molecules to 6.02 × 1023 hydrogen atoms 61. (A) Assertion : When a salt dissolves in water, the
temperature of solution decreases.
(d) none of these Reason : Energy equal to lattice energy is required
to ionize the salt in solution.
57. (S) Energy required to dissociate 4g of gaseous hydrogen
into free gaseous atoms is 208 kcal at 25°C. The bond (a) A (b) B
energy of H — H bond will be (c) C (d) D
(a) 104 kcal (b) 10.4 kcal
Resonance Energy
(c) 1040 kcal (d) 1.04 kcal
62. (S) If enthalpy of hydrogenation of C6H6(l) into C6H12(l) is
58. (S) Determine C–C and C–H bond enthalpy (in kJ/mol) –205 kJ and resonance energy of C6H6(l) is –152 kJ/mol

Given:  f H o (C2 H 6 , g) = –85 kJ/mol then enthalpy of hydrogenation of is

 f H o (C3 H8 , g) = –104 kJ/mol

Assume Hvap of C6H6(l), C6H8(l), C6H12(l) all are equal:
o
 sub H (C,s) =718 kJ/mol B.E.(H  H) =436 kJ/mol
(a) – 535.5 kJ/mol (b) – 238 kJ/mol
(a) 414, 345 (b) 345, 414
(c) – 357 kJ/mol (d) – 119 kJ/mol
(c) 287, 404.5 (d) None of these
 EXERCISE - 4 : PREVIOUS YEAR JEE ADVANCED QUESTION
1. The difference between heats of reaction at constant 7. Which of the following reactions defines Hºf ? (2003)
pressure and constant volume for the reaction (a) C(diamond) + O2(g)  CO2 (g)
2C6H6 (l ) + 15O2  12CO2(g) + 6H2O (l )
1 1
at 25º C in kJ is (1991) (b) H 2 (g)  F2 (g)  HF(g)
2 2
(a) – 7.43 (b) + 3.72
(c) N2 (g) + 3H2 (g)  2NH3(g)
(c) – 3.72 (d) + 7.43
1
2. For an endothermic reaction, where H represents the (d) CO(g)  O2 (g)  CO2 (g)
2
enthalpy of the reaction in kJ/mol, the minimum value for
8. Spontaneous adsorption of a gas on solid surface is an
the energy of activation will be (1992) exothermic process because (2004)
(a) less than H (b) zero (a) H increases for system (b) S increases for gas
(c) more than H (d) equal to H (c) S decreases for gas (d) G increases for gas
3. The Hºf for CO2(g), CO(g) and H2O (g) are – 393.5, – 110.5 9. H vap = 30 kJ/mol and S vap = 75 Jmol –1 K–1 . Find
–1 temperature of vapour, at one atmosphere. (2004)
and – 241.8 kJ mol respectively. The standard enthalpy
change (in kJ mol–1) for the reaction (a) 400 K (b) 350 K

CO2 (g) + H2(g)  CO(g) + H2O(g) is. (2000) (c) 298 K (d) 250 K

(a) 524.1 (b) + 41.2 10. 2 moles of an ideal gas expanded isothermally and reversibly
(c) – 262.5 (d) – 41.2 from 1 L to 10 L at 300 K. What is the enthalpy change ?
4. In thermodynamics, a process is called reversible when (2004)
(2001)
(a) 4.98 kJ (b) 11.47 kJ
(a) surroundings and system change into each other
(b) there is no boundary between system and surroundings (c) – 11.47 kJ (d) 0 kJ
(c) the surroundings are always in equilibrium with the
11. When one mole of monoatomic ideal gas at TK undergoes
system
adiabatic change under a constant external pressure of
(d) t he s ys tem c ha ng es in to t he su r r o u nd in gs
spontaneously 1 atm changes volume from 1 L to 2 L. The final temperature
5. Which of the following statements is false ? (2001) in kelvin would be (2005)
(a) Work is a state function
T 2
(b) Temperature is a state function (a) 2/3 (b) T 
2 3  0.0821
(c) Change in the state is completely defined when the
2
initial and final states are specified (c) T (d) T 
3  0.0821
(d) Work appears at the boundary of the system
6. One mole of a non-ideal gas undergoes a change of state 12. A monoatomic ideal gas undergoes a process in which the
(2.0 atm, 3.0 L, 95 K)  (4.0 atm, 5.0 L, 245 K) with a change ratio of p to V at any instant is constant and equals to 1.
in internal energy, E = 30.0L-atm. The change in enthalpy
What is the molar heat capacity of the gas ? (2006)
(H) of the process in L-atm is (2002)
(a) 40.0 (b) 42.10 4R 3R
(a) (b)
2 2
(c) 44.0
(d) not defined, because pressure is not constant 5R
(c) (d) 0
2
 The standard state means that the pressure should be 1
13. The direct conversion of A to B is difficult, hence it is bar, and substance should be pure at a given temperature.
carried out by the following shown path The conversion of graphite [C(graphite)] to diamond
C D [C(diamond)] reduces its volume by 2 × 10–6 m3 mol–1. If
C(graphite) is converted to C(diamond) isothermally at
A B T = 298 K, the pressure at which C(graphite) is in equilibrium
Given S(AC) = 50 eu with C(diamond), is
S(CD) = 30 eu [Useful information : 1 J = 1 kg m2s–2,

S(DB) = 20 eu 1 Pa = 1 kg m–1 s–2; 1 bar = 105 Pa] (2017)

where eu is entropy unit, then S(AB) is (2006) (a) 58001 bar (b) 1450 bar

(a) + 100 eu (b) + 60 eu (c) 14501 bar (d) 29001 bar

(c) – 100 eu (d) – 60 eu Objective Questions (One or more than one

correct option)
14. For the process H2O (l ) (1 bar, 273 K)  H2O(g) (1 bar, 373
19. Identify the intensive quantities from the following (1993)
K), the correct set of themodynamic parameters is(2007)
(a) enthalpy (b) temperature
(a) G = 0, S = +ve (b) G = 0, S = –ve (c) volume (d) refractive index
(c) G = + ve, S = 0 (d) G = – ve, S = +ve 20. The following is (are) endothermic reaction (s) (1999)
15. The value of log10 K for a reaction A  B is (a) combustion of methane
–1
(Given : rHº298K = – 54.07 kJ mol , (b) decomposition of water
–1 –1 –1
rSº298 K = 10 JK mol and R = 8.314 JK–1 mol ; (c) dehydrogenation of ethane to ethylene
2.303 × 8.314 × 298 = 5705 (2010)
(d) conversion of graphite to diamond
(a) 5 (b) 10
(c) 95 (d) 100 21. Among the following, the state function(s) is (are) (2009)
16. One mode of an ideal gas at 300 K in thermal contact with (a) internal energy
surroundings expands isothermally from 1.0 L to 2.0 L
against a constant pressure of 3.0 atm. In this process, the (b) irreversible expansion work
change in entropy of surroundings (Ssurr) in JK–1 is (c) reversible expansion work
(1L atm = 101.3 J) (2016)
(d) molar enthalpy
(a) 5.763 (b) 1.013
(c) –1.013 (d) –5.763 22. An ideal gas in a thermally insulated vessel at internal
17. For the pocess pressure=P1, volume = V1, and absolute temperature =T1
expands irreversibly against zero external pressure as
H 2O     H2O  g  shown in the diagram. The final internal pressure, volume
and absolute temperature of the gas are P2, V2 and T2,
at T = 100°C and 1 atmosphere pressure, the correct choice respectively. For this expansion, (2014)
is (2014)
(A) Ssystem > 0 and Ssurroundings > 0
(B) Ssystem > 0 and Ssurroundings < 0
(C) Ssystem < 0 and Ssurroundings > 0
(D) Ssystem < 0 and Ssurroundings < 0
18. The standard state Gibbs free energies of formation of
C(graphite) and C(diamond) at T = 298 K are
 f G o [C(graphite)] = 0 kJ mol–1 (a) q = 0 (b) T2 = T1

 f G o [C(diamond)] = 2.9 kJ mol–1 (c) P2V2 = P1V1 (d) P2 V2   P1V1

23. An ideal gas is expanded from (p1, V1, T1) to (p2, V2, T2) 26. Assertion : For every chemical reaction at equilibrium
under different conditions. The correct statement(s) among standard Gibbs’ energy of reaction is zero.
the following is (are) (2017)
(a) The work done by the gas is less when it is expanded Reason : At constant temperature and pressure, chemical
reversibly from V1 to V2 under adiabatic conditions as reactions are spontaneous in the direction of decreasing
compared to that when expanded reversibly from V1 to V2 Gibbs’ energy. (2008)
under isothermal conditions. (a) A (b) B
(b) The change in internal energy of the gas is (i) zero, if it
(c) C (d) D
is expanded reversibly with T1 = T2, and (ii) positive, if it is
expanded reversibly under adiabatic conditions with 27. Assertion : There is a natural asymmetry between
T 1  T 2. converting work to heat and converting heat to work.
(c) If the expansion is carried out freely, it is simultaneously Reason : No process is possible in which the sole result is
both isothermal as well as adiabatic
(d) The work done on the gas is maximum when it is the absorption of heat from a reservoir and its complete
compressed irrversibly from (p2, V2) to (p1, V1) against conversion into work. (2008)
constant pressure p1. (a) A (b) B
24. A reversible cyclic process for an ideal gas is shown below, (c) C (d) D
Here, P, V, and T are pressure, volume and temperature,
respectively. The thermodynamic parameters q, w, H and Fill in the Blanks
U are heat, work, enthalpy and internal energy, respectively.
28. The total energy of one mole of an ideal monatomic gas at
27ºC is ..................... cal. (1984)
29. Cp – CV for an ideal gas is .................. (1984)
30. A system is said to be ............. if it can neither exchange
matter nor energy with the surroundings. (1993)
31. The heat content of the products is more than that of the
reactants in an ................. reaction. (1993)
32. When Fe(s) is dissolved in aqueous hydrochloric acid in a
closed vessel, the work done is .................. . (1997)
The correct option(s) is (are) (2018) 33. Enthalpy is an ............... property. (1997)
(a) qAC = U BC and wAB = P2 (V2 – V1) True/False
(b) w BC  P2 (V2  V1 ) and q BC  H AC
34. First law of thermodynamics is not adequate in predicting
(c) H CA  U CA and q BC  H AC the direction of a process. (1982)
(d) q BC  H AC and H CA  U CA 35. Heat capacity of a diatomic gas is higher than that of a
Assertion Reason monatomic gas. (1985)
(A) If both ASSERTION and REASON are true and Subjective Questions
reason is the correct explanation of the assertion.
36. The enthalpy for the following reactions (Hº) at 25ºC are
(B) If both ASSERTION and REASON are true but reason
given below
is not the correct explanation of the assertion.
(C) If ASSERTION is true but REASON is false. 1 1
(i) H (g) + O2(g)  OH(g) Hº = –10.06 kcal
(D) If both ASSERTION and REASON are false. 2 2 2
25. Assertion : The heat absorbed during the isothermal
(ii) H2(g)  2H(g) Hº = 104.18 kcal
expansion of an ideal gas against vacuum is zero.
Reason : The volume occupied by the molecules of an (iii) O2 (g)  2O(g) Hº = 118.32 kcal
ideal gas is zero.
Calculate the O — H bond energy in the hydroxyl radical.
(a) A (b) B
(c) C (d) D (1981)
37. The standard heats of formation of CCl4(g), H2O(g), CO2(g) 45. The standard enthalpy of combustion at 25ºC of hydrogen,
and HCl(g) at 298 K are –25.5, –57.8, – 94.1 and –22.1 cyclohexene (C6H10) and cyclohexane (C6H12) are –241,
kcal/mol respectively. Calculate Hº (298 K) for the reaction – 3800 and –3920 kJ/mol respectively. Calculate the heat of
CCl4(g) + 2H2O(g)  CO2(g) + 4HCl(g) (1982) hydrogenation of cyclohexene. (1989)

38. The molar heats of combustion of C2H2(g), C (graphite) 46. Using the data (all values are in kilocalories per mol at
and H2(g) are 310.62 kcal, 94.05 kcal and 68.32 kcal 25ºC) given below, calculate the bond energy of C—C and
respectively. Calculate the standard heat of formation of C—H bonds.
C2H2(g). (1983)
C(s) 
 C(g), H = 172
39. Following statement is true only under some specific
conditions. Write the conditions for that in not more than H2 (g) 
 2H (g), H = 104
two sentences
“The heat energy q, absorbed by a gas is H.” (1984) 1
H2 (g) + O (g) 
 H2O (l), H = – 68.0
2 2
40. Given the following standard heats of reactions
(i) heat of formation of water = – 68.3 kcal C(s) + O2 (g) 
 CO2 (g), H = – 94.0

(ii) heat of combustion of acetylene = – 310.6 kcal Heat of combustion of C2H6 = – 372.0
(iii) heat of combustion of ethylene = – 337.2 kcal Heat of combustion of C3H8 = – 530.0 (1990)
Calculate the heat of reaction for the hydrogenation of 47. A gas mixture of 3.67L of ethylene and methane on complete
acetylene at constant volume (25º C). (1984) combustion at 25ºC produces 6.11L of CO2. Find out the
41. The bond dissociation energies of gaseous H2, Cl2 and amount of heat evolved on burning 1L of the gas mixture.
HCl are 104, 58 and 103 kcal/mol respectively. Calculate the The heat of combustion of ethylene and methane are
enthalpy of formation of HCl gas. (1985) – 1423 and –891 kJ mol–1 at 25ºC. (1991)
42. The standard molar heat of formation of ethane, carbon 48. Determine the enthalpy of the reaction,
dioxide and liquid water are –21.1, –94.1, and –68.3 kcal
respectively. Calculate the standard molar heat of C3H8(g) + H2(g)  C2H6(g) + CH4(g), at 25ºC, using the
combustion of ethane. given heat of combustion values under standard conditions.

43. An intimate mixture of ferric oxide, Fe2O3, and aluminium, Compound : H2(g) CH4(g) C2H6(g) C(graphite)
Al, is used in solid fuel rockets. Calculate the fuel value Hº (kJ/mol) : –285.8 –890.0 –1560.0 –393.0
per gram and fuel value per cc of the mixture. Heats of
formation and densities are as follows : The standard heat of formation of C3H8(g) is –103 kJ/mol.
(1992)
Hf (Al2O3) = – 399 kcal/mol
49. In order to get maximum calorific output, a burner should
Hf (Fe2O3) = – 199 kcal/mol
have an optimum fuel to oxygen ratio which corresponds
Density of Fe2O3 = 5.2 g/cc, to 3 times as much oxygen as is required theoretically for
complete combustion of the fuel. A burner which has been
Density of Al = 2.7 g/cc (1989)
adjusted for methane as fuel (with x litre/hour of CH4 and
44. An athlete is given 100g of glucose (C6H12O6) of energy 6x litre/hour of O2) is to be readjusted for butane, C4H10. In
equivalent to 1560 kJ. He utilizes 50 percent of this gained order to get the same calorific output, what should be the
energy in the event. In order to avoid storage of energy in rate of supply of butane and oxygen ? Assume that losses
the body, calculate the weight of water the would need to due to incomplete combustion etc., are the same for both
perspire. The enthalpy of evaporation of water is 44 kJ/mol. fuels and that the gases behave ideally. Heats of
(1989) combustions :
CH4 = – 809 kJ/mol, C4H10 = – 2878 kJ/mol (1993)
50. The polymerization of ethylene to linear polyethylene is 56. Show that the reaction,
represented by the reaction,
1
CO(g) + O2 (g) 
 CO2 (g) at 300 K, is spontaneous
n [CH2 CH2] 
 2
where, n has large integral value. Given that the average and exothermic, when the standard entropy change is
enthalpies of bond dissociation for C C and C—C at –0.094 kJ mol–1 K–1. The standard Gibbs’ free energies of
298 K are + 590 and +311 kJ/mol respectively, calculate the formation for CO2 and CO are –394.4 and –137.2 kJ mol–1,
enthalpy of polymerization per mole of ethylene at 298 K. respectively. (2000)
(1994)
57. Diborane is a potential rocket fuel which undergoes
51. The standard enthalpies of formation of cyclohexane (l) combustion according to the reaction
and benzene (l) at 25ºC are –156 and +49 kJ mol–1
respectively. The standard enthalpy of hydrogenation of B2 H 6 (g) + 3O2 (g) 
 B2O3 (s) + 3H 2O(g)
cyclohexene (l) at 25ºC is –119 kJ mol–1. Use these data to From the following data, calculate the enthalpy change for
estimate the magnitude of the resonance energy of the combustion of diborane. (2000)
benzene. (1996)
52. Compute the heat of formation of liquid methyl alcohol in 3
2B(s) + O2 (g)  B2O3 (s), H  1273 kJ mol1
–1 2
kJ mol , using the following data. Heat of vaporization of
liquid methyl alcohol = 38 kJ/mol. Heat of formation of
1
gaseous atoms from the elements in their standard states :  H 2 O(l ),
H 2 (g) + O2 (g)  H  286 kJ mol1
2
H = 218 kJ/mol, C = 715 kJ/mol, O = 249 kJ/mol.
Average bond energies : H 2 O(l ) 
 H 2 O(g), H  44 kJ mol1
C—H = 415 kJ/mol
C—O = 356 kJ/mol
 B2 H6 (g), H = 36 kJ mol –1
2B (s) + 3H2 (g) 

O—H = 463 kJ/mol (1997) 58. When 1-pentyne (A) is treated with 4 N alcoholic KOH at
53. From the following data, calculate the enthalpy change for 175ºC, it is converted slowly into an equilibrium mixture of
the combustion of cyclopropane at 298 K. The enthalpy of 1.3% 1-pentyne (A), 95.2% 2-pentyne (B) and 3.5% of 1, 2-
formation of CO2(g), H2O (l) and propane (g) are –393.5, pentadiene (C). The equilibrium was maintained at 175ºC.
Calculate Gº for the following equilibria.
–285.8 and 20.42 kJ mol–1 respectively. The enthalpy
of isomerization of cyclopropane to propene is  A,
B  G1o  ?
–1
–33.0 kJ mol . (1998)
54. Estimate the average S–F bond energy in SF6. The values  C,
B  G o2  ?
of standard enthalpy of formation of SF6(g), S(g) and F(g)
are : From the calculated value of G1o and G o2 indicate the

– 1100, 275 and 80 kJ mol–1 respectively. (1999) order of stability of (A), (B) and (C). Write a reasonable
reaction mechanism showing all intermediates leading to
55. A sample of argon gas at 1 atm pressure and 27ºC expands
(A), (B) and (C) (2001)
reversibly and adiabatically from 1.25 dm3 to 2.50 dm3.
59. Two moles of a perfect gas undergo the following
Calculate the enthalpy change in this process C Vm for processes :
argon is 12.49 JK–1 mol–1. (2000) (a) a reversible isobaric expansion from (1.0 atm, 20.0L) to
(1.0 atm, 40.0 L)
(b) a reversible isochoric change of state from (1.0 atm,
40.0 L) to (0.5 atm, 40.0 L)
 (c) a reversible isothermal compression from (0.5 atm, 63. In a constant volume calorimeter, 3.5g of a gas with
40.0L) to (1.0 atm, 20.0 L) molecular weight 28 was burnt in excess oxygen at 298.0 K.
(i) Sketch with labels each of the processes on the same The temperature of the calorimeter was found to increases
p-V diagram. from 298.0 K to 298.45 K due to the combustion process.
Given that the heat capacity of the calorimeter is 2.5 kJ K–1,
(ii) Calculate the total work (W) and the total heat change
the numerical value for the enthalpy of combustion of the
(Q) involved in the above processes.
gas in kJ mol–1 is (2009)
(iii) What will be the values of U, H and S for the
overall process ? (2002) 64. The surface of copper gets tarnished by the formation of
copper oxide. N2 gas was passed to prevent the oxide
3R 3R formation during heating of copper at 1250 K. However,
60. CV value of He is always but CV value of H2 is at
2 2 the N2 gas contains 1 mole % of water vapour as impurity.
The water vapour oxidises copper as per the reaction given
5R
low temperature and at moderate temperature and more below : (2018)
2
2Cu(s) + H2O(g)  Cu2O(s) + H2(g)
5R
than at higher temperature. Explain in two or three
2 pH 2 is the minimum partial pressure of H2 (in bar) needed
lines. (2003)
to prevent the oxidation at 1250 K. The value of ln (pH2 ) is
61. 100 mL of a liquid contained in an isolated container at a
pressure of 1 bar. The pressure is steeply increased to 100 ......... .
bar. The volume of the liquid is decreased by 1 mL at this (Given : total pressure = 1 bar, R (universal gas constant) =
constant pressure. Find the H and U. (2004) 8J K–1 mol–1, ln (10) = 2.3. Cu(s) and Cu2O(s) are mutually
62. For the reaction, 2CO + O2  2CO2; H = – 560 kJ. Two immiscible.
moles of CO and one mole of O2 are taken in a container of At 1250 K : 2Cu(s) + ½ O2(g)  Cu2O(s);
volume 1L. They completely form two moles of CO2, the –1
G  = –78,000 J mol
gases deviate appreciably from ideal behaviour. If the
pressure in the vessel changes from 70 to 40 atm, find the H2(g) + ½ O2(g)  H2O(g) ; G  = – 1,78,000 J mol–1;
magnitude (absolute value) of U at 500 K.
G is the Gibbs energy
(1 L-atm = 0.1 kJ) (2006)
 ANSWER KEY

EXERCISE - 1 : (Basic Objective Questions)

1. (a) 2. (d) 3. (a) 4. (a) 5. (c) 6. (c) 7. (d) 8. (b) 9. (b) 10. (c)

11. (a) 12. (c) 13. (b) 14. (b) 15. (d) 16. (b) 17. (d) 18. (d) 19. (a) 20. (c)

21. (c) 22. (a) 23. (b) 24. (b) 25. (b) 26. (d) 27. (c) 28. (d) 29. (a) 30. (c)

31. (a) 32. (b) 33. (b) 34. (b) 35. (b) 36. (d) 37. (b) 38. (d) 39. (a) 40. (b)

41. (d) 42. (b) 43. (a) 44. (c) 45. (a) 46. (b) 47. (a) 48. (c) 49. (c) 50. (c)

51. (c) 52. (d) 53. (d) 54. (b) 55 (b) 56. (d) 57. (b) 58. (a) 59. (a) 60. (b)

61. (a) 62. (c) 63. (d) 64. (c) 65. (c) 66. (b) 67. (c) 68. (a) 69. (c) 70. (c)

71. (d) 72. (b) 73. (a) 74. (b) 75. (c) 76. (c) 77. (d) 78. (d) 79. (b) 80. (b)

81. (a) 82. (c) 83. (c) 84. (d) 85. (d) 86. (c) 87. (a) 88. (d) 89. (c) 90. (c)

91. (d) 92. (a) 93. (a) 94. (a) 95. (d) 96. (b) 97. (c) 98. (b) 99. (b) 100. (a)

101. (d) 102. (b) 103. (b) 104. (c) 105. (b) 106. (b) 107. (b) 108. (a) 109. (c) 110. (a)

111. (a) 112. (b) 113. (a) 114. (a) 115. (d) 116. (b) 117. (d) 118. (b) 119. (d) 120. (b)

EXERCISE - 2 : (Previous year JEE MAINS Questions)

1. (a) 2. (c) 3. (b) 4. (d) 5. (d) 6. (d) 7. (c) 8. (d) 9. (a) 10. (d)
11. (d) 12. (b) 13. (a) 14. (c) 15. (b) 16. (a) 17. (d) 18. (a) 19. (c) 20. (c)
21. (b) 22. (b) 23. (d) 24. (b) 25. (b) 26. (d) 27. (c) 28. (d) 29. (a) 30. (d)

31. (a) 32. (b) 33. (b) 34. (a)

JEE Mains Online

1. (c) 2. (b) 3. (c) 4. (a) 5. (d) 6. (b) 7. (d) 8. (b) 9. (d) 10. (c)
11. (b) 12. (d) 13. (b) 14. (b) 15. (a) 16. (b) 17. (b) 18. (a)

EXERCISE - 3 : (Advanced Objective Questions)

1. (b) 2. (a) 3. (a) 4. (a) 5. (a) 6. (a) 7. (b) 8. (c) 9. (b) 10. (d)

11. (c) 12. (c) 13. (d) 14. (d) 15. (c) 16. (b) 17. (b) 18. (c) 20. (d) 20. (a)
 21. (a) 22. (d) 23. (d) 24. (c) 25. (b) 26. (a) 27. (a) 28. (b) 29. (c) 30. (a)

31. (b) 32. (b) 33. (a) 34. (d) 35. (a) 36. (d) 37. (a) 38. (c) 39. (b) 40. (c)

41. (c) 42. (a) 43. (b) 44. (a) 45. (b) 46. (c) 47. (d) 48. (c) 49. (a) 50. (d)

51. (c) 52. (b) 53. (a) 54. (b) 55. (a) 56. (b) 57. (a) 58. (b) 59. (b) 60. (b)

61. (d) 62. (d)

EXERCISE - 4 : (Previous year JEE ADVANCED Questions)

1. (a) 2. (c) 3. (b) 4. (c) 5. (a) 6. (c) 7. (b) 8. (c) 9. (a) 10. (d)

11. (d) 12. (a) 13. (a) 14. (a) 15. (b) 16. (c) 17. (b) 18. (c) 19. (b, d) 20. (b, c, d)

21. (a, c, d) 22. (a,b,c) 23. (a,b,d) 24. (b,c) 25. (b) 26. (d) 27. (b) 28. 900 29. R 30. isolated

31. exothermic reaction 32. zero 33. extensive 34. True 35. True 36. 121.31 kcal

37. –41.4 kcal 38. 54.2 kcal 40. –41.7 kcal 41. – 22 kcal/mol 42. –372 kcal/mol

43. 3.94 kcal/cc 44. 17.72 mole 45. –121 kJ/mol 46. C–H = 99 kcal, C–C = 82 kcal

47. 49.82 kJ 48. – 55 kJ 49. 5.46 x L/h 50. –32 kJ/mol 51. – 152 kJ/mol

52. –266 kJ/mol 53. –2091.32 kJ 54. 309.16 kJ/mol 55. –116.4 J 56. –285.4 kJ < 0

57. – 2035 kJ 58. 12.3 kJ 61. 9900 bar mL, 100 bar mL 62. – 557 kJ

63. 9 kJ 64. –14.6