THERMODYNAMICS & THERMOCHEMISTRY

CONTENTS
Particular Page No.

Theory 001 – 041

Thermodynamic Ist law

Exercise 1 to 3 042 – 051
Answers 052 – 053

Thermodynamic IInd & IIIrd law

Exercise 1 to 3 054 – 062
Answers 063 – 064

Thermochemistry
Exercise 1 to 3 065 – 074
Answers 075 – 076

Additional Problems For Self Practice (APSP) 077 – 105

Part - I : PRACTICE TEST-1 (IIT-JEE (MAIN Pattern))
Part - II : NATIONAL STANDARD EXAMINATION IN CHEMISTRY (NSEC) STAGE-I
Part - III : HIGH LEVEL PROBLEMS (HLP)
Part - IV : PRACTICE TEST-2 (IIT-JEE (ADVANCED Pattern))

APSP Answers 106 – 108

APSP Solutions 108 – 129

JEE (Advanced) SYLLABUS

First law of thermodynamics; Internal energy, work and heat, pressure-volume work; Enthalpy; Second
law of thermodynamics, Entropy, Free energy, Criterion of spontaneity; Heat of reaction, fusion and
vapourization, Hess's law.

JEE (Main) SYLLABUS

Thermal equilibrium, Zeroth law of thermodynamics, concept of temperature. Heat, work and internal
energy. First law of thermodynamics. Second law of thermodynamics: reversible and irreversible
processes. Carnot engine and its efficiency.

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Thermodynamics & Thermodynamics

1. THERMODYNAMICS
Thermodynamics Ist Law
Section (A) : Basic definitions
Introduction:
Thermodynamics: The branch of science which deals with different forms of energy & their
interconversion.
THERMODYNAMICS

Application of thermodynamics:
In chemistry using thermodynamics
 We can predict feasibility of the reaction that is if two substances are mixed then the reaction between
them will takes place or not.
 If reaction does take place then what are the energy changes involved during the reaction.
 If in a chemical reaction, equilibrium is going to get attained then what will be the equilibrium
concentrations of different reactants & products, can be calculated with thermodynamics.


Limitations of thermodynamics:
 Laws of thermodynamics are applicable to matter in bulk or on system as a whole, these can not be
applied on individual particles (temperature, pressure, enthalpy etc have meanings only for system as a
whole).
 Using thermodynamics we cannot calculate the time taken for completion of a reaction or for attainment
of chemical equilibrium.

Ex-1 A+B C+ D K1, eq = 103

E+F G+H K2, eq = 10–3
Which of these reaction will attain equilibrium earlier ?
Sol. We cannot predict, because value of equilibrium constant has no relation with time taken to attain
equilibrium.
 More the equilibrium constant K, more will be the concentration of products at equilibrium state.
 Smaller the equilibrium constant K, lesser will be the concentration of products at equilibrium state.

Terms to be used in thermodynamics:

 System : Part of the universe which is under study for energy
changes.

Ex. Air in a room, water in a bottle, any living body.



 Surrounding : Rest of the universe.

 Universe : Universe = System + Surroundings

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 Boundary : Anything which separates system & surroundings is called boundary.
  Boundary can be real or imaginary.
  Boundary can be flexible or rigid
e.g. air in a flexible balloon (flexible boundary) while air in a room (fixed boundary).
  Boundary can be adiabatic (non-conducting; q = 0) or diathermic (conducting; q 0;T= 0).
Types of system :
 Open system: System which can exchange energy & matter both with the surroundings.
e.g. : Living systems( any living organism) are open systems, air in an open room; water flow in pipe.
 Closed system: System which can exchange only energy but cannot exchange matter with the
surroundings is called closed system.
e.g. : any matter in a closed container ; Heating of water in closed container.
 Isolated system: System which cannot exchange energy and matter both with the surroundings.
e.g. : Water in thermos flask.(Though not a perfectly isolated system but can be taken as, for small
interval of time as the energy exchanges are negligible) ; Hot tea in thermos (few time).
Whole of universe is a perfect isolated system.

.
Open System Close System Isolated system

 State of a system:
 It means the condition in which the system is present.
 It can be specified/defined by measuring/ specifying some observable/measurable properties of the
system like pressure, volume, temperature, amount of substance, elasticity, heat capacity etc.
e.g. For an ideal gaseous system state of the system can be defined by specifying volume,
temperature and pressure.
 We may have to specify more properties of the system depending on the complexity of the system.
State function (State variables) :
 Property of a system which is dependent only on the state of the system i.e. it is a point function
 It is independent of the path adopted to attain a particular state.
e.g. In Mechanics, Displacement of any object will a state function but distance travelled by the object
will be a path function.
For any thermodynamic system,
Temperature, Pressure, Volume, Total internal energy (E or U), Enthapy(H), Gibbs free energy (G),
Entropy (S) are all state functions.

e.g.

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Thermodynamics & Thermodynamics
In the above example the final temperature, pressure, and the volume will be same in both the above
ways but the work involved and the heat exchanged during the processes will be different.
 For a cyclic process the change in state functions must be zero.
 dx  0
 State variables can be extensive or intensive.
 Change in state function are not state function.
Eq. T, V, P, H, G, V, etc are not state function.

 Path function :
 Quantities which are dependent on the path/way the system has achieved a particular state.
e.g. Heat, work, Heat capacities (Molar heat capacities, specific heat capacities etc.).
 These quantities are define when there is a process going on.
 These can not have any definite (particular) value in any particular state of the system.

 Types of properties
Extensive properties :
 Functions or properties of the system which are dependent on mass or on size of the system are called
Extensive Properties. 
 Extensive functions are additive in nature (The addition of the volumes of the two parts equals the
volume of the whole of the room.)
e.g. Volume, Mass, Total heat capacity, Total internal energy (E), Enthalpy(H), Gibbs Free
Energy(G), Entropy(S) ; moles etc.
Intensive properties :
 Functions or properties which are not mass dependent or size dependent are called intensive function.
 Intensive properties are not additive in nature.
eg. Temperature, pressure, molar heat capacity, specific heat capacity, density,concentration, vapour
pressure; B.P. ; F.P. ; Viscosity ; pH etc.

How to identify extensive or intensive properties

If a system in a particular state is divided into two equal or unequal
parts, the properties which have value equal to the original value of that
property for the whole of the system is called an Intensive property.
While the properties which have values different from the values for
whole of the system are called Extensive Properties.

 For example consider air in a room at temp of 300K, 1 atm pressure. Now, if the room is
divided by some boundary (imaginary or real) into two parts (equal or unequal) then in these
two parts:
 The temperature, pressure, density of the gas, concentration of gaseous molecules etc. will
have the same value as that of for whole of the system. (intensive)
While the volume of two parts, mass of gas in two parts, total energy of the gaseous
molecules in the two parts, entropy the two parts etc. will be different from the values of these
properties as for the whole of the system initially. (extensive)

 Thermodynamic equilibrium:
 When there is no change in any observable or measurable property of a
system with time then the system is said to be in thermodynamic
equilibrium.
 Thermodynamic equilibrium consist of three types of equilibrium.
(a) Mechanical equilibrium
(b) Thermal equilibrium
(c) Chemical equilirbrium


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Thermodynamics & Thermodynamics
 Mechanical equilibrium:
There should not be any pressure gradient with time or with space
(for any ideal gaseous system, for a liquid system there can be
pressure gradient with space as pressure at the bottom of the
container in which a liquid is filled will be greater than the pressure
at the surface of the liquid.) in the system.
 Thermal equilibrium: There should not be any temperature
gradient (difference).
Temperature may have different values at different
places/locations in a system but it should remain constant with
time.
 Chemical equilibrium: There should not be any concentration gradient of any of the species in the
system.
Section (B) : Thermodynamics processes & graph
Types of thermodynamic process on basis of state/conditions
Thermodynamic process : Any method/process by which system can change its state from one state
of thermodynamic equilibrium to another state of thermodynamic equilibrium.
There can be infinite type of thermodynamic processes, out of these the following are important ones:
1. Isothermal process : T = constant
Ti = Tf
T = 0
2. Isochoric process : V = constant
Vi = Vf
 V = 0
3. Isobaric process : P = constant
Pi = Pf
 P = 0
4. Adiabatic process : q = constant
or heat exchange with the surrounding = 0 (zero)
5. Cyclic Process : A system undergoes a series of changes
and comes back to the initial state.
  V = 0
  H = 0
Types of thermodynamics processes on basis of the way the processes are carried out :
 Reversible process :
The process that can be reversed by a very small change is known as reversible process.
 If a process is carried out in such a manner so that the system is always in thermodynamic
equilibrium at every stage of the process.
 If the process is carried out such that the difference in driving force and opposing force is
infinitesimally small so that process takes place at infinitesimally slow rate.
Fdriving – Fopposing = F and F  0
 An ideal reversible process will take infinite time to get completed.
 It is carried out infinitesimally slowly.
 Strictly speaking there is no ideal reversible process in universe.
To get an idea of a reversible process we can consider the
following system an ideal gas is enclosed in a container and a
massless piston is put on the gas on which a pile of sand is
placed having particles of negligible mass. To carry out a
reversible expansion we will slowing decrease the mass of the
sand lets say by removing the particles one by one, so the
expansion of the gas will take place at infinitesimally small rate
and we can always assume the system to in thermodynamic
equilibrium. So, the expansion will be of reversible type.
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Thermodynamics & Thermodynamics

FBD of piston

For piston to be in equilibrium : Pgas = Patm + Mg/A

Sign : i – f : expainsion
f – i : compression
 Irreversible process: The process can not be reversed by a small change is known as irreversible.
 If a process is carried out in such a manner so that the system is in thermodynamic equilibrium.
(I) Only at initial & final state of the process but not at the intermediate stages.
(II) System may be in thermodynamic equilibrium state at some finite number of intermediate
stages only - for example - n step irreversible expansion of a gas.
 If during the process there is a finite difference in driving force and opposing force so that
process takes place with a finite rate; Fdriving – Fopposing = F.
 Irreversible processes will get completed in finite time.
 At intermediate stages of the irreversible process, different state function such as pressure,
temperature etc. are not defined.
 All real process are irreversible.
Consider the above system. If the stopper placed over the piston is removed, then the piston will move
with almost infinite acceleration and will keep moving to a position where the pressure of the gas
becomes equal to the external pressure. Since the process will get completed in finite time and there
was a finite difference between the driving force and the opposing force so, process is
irreversible.During the process, the pressure of the gas can not be defined as it will be having different
values at different locations.

Sign : i – f : expainsion
f – i : compression


 Modes of energy exchange:

These are two ways by which a system can interact or can exchange energy with its surroundings.
(i) Heat & (ii) Work
Heat & Work both are forms of energy.
Heat: When the energy transfer across a boundary as a result of temperature difference between
system & surroundings is known as heat.
 Modes of heat transfer: Conduction (solids); Convection (fluids); Radiation (vacuum)
Work: Energy transfer which is not heat or which is not because of temperature difference is called
work.
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Thermodynamics & Thermodynamics
Work can be of many types: Mechanical work, Electrical work, Magnetic work, Gravitational work etc.
The same energy transfer can be called work or can also be called heat depending on choice
of the system.
To understand this, consider a system shown below in which
water is taken in a closed container at 25ºC, the
surroundings is also at temperature of 25ºC and there is a
heater coil in the dipped in the water which is connected to a
battery through a switch S.Heater coil is also at 25ºC initially.
Now, there are two ways in which system can be chosen.

–System: All contents of the container (water + Heater coil).

When switch is turned on there will be increment in the temperature of the system. Since the
temperature of the surroundings was equal to temperature of the system so, heat can not flow but still
there is increment in the energy of the system and hence, there is temperature increment. This must be
because of electrical work done by the battery on the system not because of the heat transfer as initially
temperatures were equal.
–System: Water only is our system. Heater coil will be part of the surroundings.
In this case when switch is turned on the temperature of the heater coil will increase first so there will be
a temperature difference between system & surroundings. Hence, this energy transfer will be called
heat.
 IUPAC Sign convention about Heat and Work
Any energy given to system is taken positive so heat given to system = positive
heat taken out from system = Negative
Work done on the system = Positive
Work done by the system = Negative
The sign convention is different from physics, but the meaning always comes
out to be same only in equation we have to use a different sign convention for
work.
So if in any problem, w = – 10 J
It means system has done work of 10 Joule on surroundings.
According to Chemistry : According to Physics :
Q Q

w w
U = Q + W  U = Q – W
IUPAC convention of Heat
1. Heat given to the system = +ve 2. Heat coming out of the system = –ve
3. Work done on the system = +ve 4. Work done by the system = –ve

Section (C) : Work calculation

WORK DONE (w) :
Energy that is transmitted from one system to another in such a way that difference of temperature is
not directly involved is known as work. It is a path function.
This definition is consistent with our understanding of work as dw = Fdx. The force F can arise from
electrical, magnetic, gravitational & other sources.
Units : Heat & work both are forms of energy. Hence, their units are units of energy. i.e.S system:
Joules (J). Much data is available in the old units of calories (cal) as well.
P × V = (litre. atmosphere) term which has unit of energy. It is useful to remember the conversion
1 litre. atm = 101.3 Joules = 24.206 cal

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Thermodynamics & Thermodynamics
 For irreversible processes, state parameters such as P, T etc cannot be defined. Hence, work cannot
be estimated using Pgas. But by the work energy theorem
W gas = – W ext + Kpisston
When the piston comes to rest again Kpiston = 0
 W gas = –W ext = –  Pext dv

as the external pressure is always defined hence, for all processes work can be calculated
using
W gas = –W ext = –  Pext .dv = –PextV

 Calculation of work for different type of process on an ideal gas.

1. ISOTHERMAL PROCESS :
(A) Isothermal expansion: There are many ways in which a gas can be expanded isothermally.
(a) Isothermal reversible expansion :
mg
Pext = P0 + = Pgas = P (always)
A
In reversible process, Pext= Pgas (thermodynamic equilibrium always)
nRT
Since process is isothermal ; P=
V
Vf Vf Vf
nRT
W = –  Pext dV = –  P dV  W = – dV
Vi Vi Vi V

V 
W = –nRT ln  f 
 Vi 

Work = Area under the P–V diagram

In expansion work is done by system on the surroundings and Vf > Vi
W = –ve
(b) Irreversible isothermal expansion :
(i) Single step isothermal expansion
We are assuming expansion against atmospheric pressure which need not be the case
in a given problem.
A mass equal to m0 is placed on piston initially to maintain equilibrium.
Initially, Pi = Pgas = Patm + m0 g/A

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Thermodynamics & Thermodynamics

For expansion to take place, m0 mass is suddenly removed so gas expands against
constant external pressure of Patm
In this case, the pressure of the gas will not be defined as the sudden expansion has
taken place so all the molecules of sample will not get the information of expansion
simultaneously, there will be a time gap and hence, there will be a state of turbulence.
From some intermediate state of volume ‘V’, the work done is slight expansion from
V  (V + dV)
dw = – Pext . dV (IUPAC sign convention)
Vf

So, W =  dw    Pext .dv = – Pext (Vf – Vi)

Vi

Only initial and final states can be located (as at intermediate stages pressure of the
gas is not defined)
(ii) Two step isothermal expansion:
Mass M0 is divided into two mass (may be equal or unequal)
M0 = (m1 + m2)
Now, if m1 only is removed, then the expansion of gas will take place against constant
external pressure
Pext1 = (Patm + m2g/A)
and this expansion will take place only upto volume V1 such that
Pext1 . V1 = Pi Vi (isothermal)
Now, if second mass m2 is also removed then expansion
V1  Vf will take place against constant pressure
So, Pext 2 = Patm
work done is expansion Vi  V1 ; W 1 = –(Patm +M2g/A) (Vi – V1)
& work done is expansion V1  Vf ; W 2 = –Patm (Vf – Vi)
Total work = W 1 + W 2

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Thermodynamics & Thermodynamics

Patm

M1
Vf M0
V
Vi

Work done in this irreversible expansion is greater than work done by gas during
the single stage expansion of gas and so on for three step expansion we divide the
mass m0 into three masses m1, m2 and m3 and remove these step by step and so on.
   (iii) For n step expansion and n  
If n   ; Irreversible process becomes reversible process

(B) Isothermal compression of ideal gas :

(a) Reversible isothermal compression of an ideal gas
This can be achieved by placing particles of sand one by one at a very slow take in the
assembly which keeps the temperature of gas constant in this case the expression of work
done will be exactly similar to as obtained in case of reversible expansion of gas
W = – nRT ln(Vf/Vi)
This will automatically come out to be +ve as Vf < Vi

(Patm + M0g/A) = Pf
Patm

Vi
Vi
Patm

Vf Vi

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Thermodynamics & Thermodynamics
  (b) Irreversible isothermal compression of an ideal gas
(i) Single step compression :
To compress gas a mass m0 is suddenly placed on massless piston
dw = – Pext. dv = – (Patm + m0g/A) dv
so, to calculate total work done on the gas
Vf
W =  dw    Pext . dv ; W = – Pext (Vf – Vi)
Vi

(ii) Two step compression :

Place mass m0 in two fragments (m1+m2) the
graphical representation will make the calculation
of work done. If m1 is placed first, then the first
compression has taken place aganist external
pressure of (Patm + m1g/A)
So, W 1 = – (Patm + m1 g/A) (V1 – Vi)
Simlarly, W 2 = – (Patm + m0 g/A) (Vf – Vi)
Note : If process takes place in n steps and n 
then process will be like reversible compression.

Conclusion :
Whenever work is done on the gas then it will be minimum in case of reversible process.
Thats why different machines/engines are designed to work reversibly so maximum output can be
obtained but minimum input is given to it.
output – work done by engine/machine/system
input – work done by system us a surrounding

  If expansion/compression takes place against constant external pressure then it is

irreversible.
  If there is sudden change then the process is irreversible.
Reversible and irreversible isothermal process.
 Except the infinite stage compression/expansion, all are irreversible.
 We can redefine reversible and irreversible as follows :
Reverssible process: If a process operates is such a fashion that when it is A
reversed
back both the system as well as surroundings are restored to their initial position
w.r.t. both work and heat, is known as reversible process.
If for the process A  B work = w, heat = Q then if for the process B  A, B
work = – w, heat = –Q then the process is reversible.
 If the external pressure is constant in isothermally process, process is irreversible.

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Thermodynamics & Thermodynamics

Ex-2. Calculate the work performed when 2 moles of hydrogen expand isothermally and reversibly at 25ºC
form 15 to 50 litres.
V 50
Sol. We have, W = – 2.303 n RT log 2 = – 2.303 × 2 × 2 × 298 × log = – 1436 calories.
V1 15
Ex-3. If a gas at a pressure of 10 atm at 300 k expands against a constant external pressure of 2 atm from a
vol. of 10 litres to 20 litres find work done ? [Isothermal process]
Sol. Process is irreversible
20
w  –  2dv  –2 [20 – 10] = – 20 L.atm
10
1 litre atm = 101.3 J

2. ISOCHORIC PROCESS :
Since dv = 0
So, w = 0 (for both reversible and irreversible process)
3. ISOBARIC PROCESS :
Since P = constt. = Pext
So, w = –Pext (v f –vi) (for both reversible and irreversible process)

Section (D) : Heat & Internal energy

Calculation of E :
Internal Energy (E, also denoted by U) :
Every system having some quantity of matter is associated with a definite amount of energy, called
internal energy.
 It is the sum of all forms of energies present in the system.
E = ETranslational + ERotational + EVibrational + Ebonding + .....
E = EFinal  EInitial .
 Thermodynamic definition of an ideal gas :
 For a gas the internal energy is directly proportional to its absolute temperature then the gas is
termed as an ideal gas.
 E   E 
so   =0,   =0
 V T  P T
 E = qv, heat supplied to a gas at constant volume, since all the heat supplied goes to
increase the internal energy of the gas.
 It is an extensive property & a state function. It is exclusively a function of temperature.
If T = 0 ; E = 0 as well.
 With change in temperature only kinetic energy changes.
 Degree of freedom : The total no of modes on which a molecule of an ideal gas can exchange energy
during collisons is known as its degrees of freedom.
Translational degree of freedom = 3 (for all type of gases.)
Rotational degree of freedom
=0 – monoatomic gases
=2 – diatomic or linear polyatomic gases
=3 – non-linear polyatomic gases.
If “f” is initial degree of freedom for that gas.
f=3 for monoatomic
=5 for diatomic or linear polyatomic
=6 for non - linear polyatomic

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Law of equipartion of energy :
1
Energy equal to kT is associated with each degree of freedom per ideal gas molecule
2
Where k is Boltzmann constant
1 f
E/molecule = f × kT  E/mole = RT when (R = k × NA)
2 2
 For n moles,
f f
E = nRT only for ideal gas.  E = nRT
2 2

 Calculation of Heat (q)

st
 Heat is a path function and is generally calculated indirectly using I law of thermodynamics.
 First calculate E and W & then q or heat can be calculated if heat capacity of any process is given to
us.


  Total Heat Capacity (CT )

Heat required to raise the temperature of system by 1ºC under the given process is known as total heat
capacity.
dq
Mathematically, CT = J/ºC
dT
 It is extensive properties and path function.
So, dq = CTdT
on integrating 
q  CT dT

  Molar heat capacity (C)

Heat required to raise temperature of 1 mole of a subtance by 1ºC
dq
Mathematically, C = J mole–1 K–1
ndT
So, dq = nCdT
q =  nCdT  nCT
C is intensive path function.
Cp is molar heat capacity at constant pressure
CV is molar heat capacity at constant volume
Cp and CV are intensive but not a path function
  Specific heat capacity (s) :
Heat required to raise temperature of unit mass (generally 1 g) of a substance by 1ºC.
dq
S= Jg–1 K–1
mdT
So, dq = msdT
q=  dq   ms dT msT
S is intensive path function
SP is specific heat capacity at constant pressure
SV is specific heat capacity at constant volume
SP & SV are intensive but not a path function
Total heat capacity, molar heat capacity & specific heat capacity of a process on a substance are
related as
CT = nC = ms & C = Ms
Where m – weight of substance, M – molar mass of substance, n – no. of moles of the substance

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For isothermal process C = ± For isobaric process C = Cp
For isochoric process C = Cv For adiabatic process C=0
Heat capacity can have value from –to + depending on the process.

Note :
(1) Heat capacity is a path function and different type of heat capacities are defined
(2) Remember heat capacity of a substance is not fixed it is dependent on type of process which is being
performed on that substance.

Ex-4. During an expansion of ideal gas the work done by gas is 100 J and the heat capacity of process is
found to be +2 J/ºC. Find E of gas if the final temperature of gas is 25ºC higher than its initial
temperature.
Sol. E = q + W
q = 2 × 25 = 50 J & W = –100 J
E = 50 – 100 = – 50 J

Section (E) : First law of thermodynamics

Zeroth Law of Thermodynamics (ZLOT) :
 If two systems are in thermal equilibrium with third system, then they are also in thermal equilibrium
with each other.

First Law of Thermodynamics (FLOT) :

Law of energy conservation :
Energy of total universe is always conserved.
or
Total energy of an isolated system is always conserved.
or
Hence absolute value of E can never be calculated only change in value of E can be calculated for a
particular process.
Mathematical form of First Law of thermodynamics.
If a system is initially in a particular state in which its total internal energy is E1. Now q amount of heat is
given to it and w amount of work is done on it so that in new state its total internal energy becomes E2.
Then according to 1st Law of thermodynamics.
E2 = E1 + q + w
so E = (E2 – E1) = q + w
Application of First Law
U = Q + W Since W = –PV
U = Q – PV

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Section (F) : Adiabatic, isothermal, polytropic & free expansion processes
4. Adiabatic process :
dQ = 0 (no heat changed b/w system and surrounding
dU = dQ + dW
nRT
 nCV dT = – PdV   nc V dT    .dv
V
T2 V2
Cv .dT R T V
 T T = – V V . dV  Cv ln 2 = – R ln 2
1 1
T1 V1
R / c v 1
T2 V   T2   V1 
ln = ln  2     
T1  V1   T1   V2 
–1 –1
T 2 V2 = T1 V1 or T V–1 = constant

PV = constant
 This is only valid when the quantity PV or TV–1 is constant only for a quasi-static or reversible process.
 For irreversible adiabatic process these equations are not applicable.
Operation of adiabatic process
(a) Reversible Adiabatic
 Operation wise adiabatic process and isothermal process
are similar hence all the criteria that is used for judging an
isothermal irreversible processes are applicable to
adiabatic process.
 Also, volume in case of isothermal volume is more than
that of adiabatic at constant pressure and no of moles,
V T
K
w = –  Pext. dv , but Pext = Pint = 
V
K
 w = –   . dv ,
V
 V2 1  V1 1  1 
P V  .V  P1V1 .V11
 W=–K  = 2 2 2
1     1
P2 V2  P1V1
 Work done = (as K = P2V2 = P1V1 )
 1
(b) Irreversible Adiabatic
 Adiabatic irreversible expansion –
W =  Pext.dv = – Pext (V2 – V1)
and  du   dw
 W = u
nR(T2  T1 ) P V  P1V1 )
W = nCv (T2 – T1) = = 2 2
 1  1
Note: If two states A and B are connected by a
reversible path then they can never be connected by
an irreversible path.

If the two states are linked by an adiabatic reversible and irreversible path then
wrev. = urev.
But as u is a state function
 urev. = uirrev.  wirrev. = wrev.

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as work is a path function.
If we assume that
wirrev. = wrev.  It implies that
 urev.  uirrev. Which again is a contradiction as U is a state function.


 Two states A and B can never lie both on a reversible as will as irreversible adiabatic path.
 There lies only one unique adiabatic path linkage between two states A and B.
 Comparison of Adiabatic Expansion (single stage Vs Infinite stage)
Single stage means irreversible process
Infinite stage means reversible process
In adiabatic compression process,
(W gas)rev < (W gas)irrev urev. < uirrev.
 (T2)rev. < (T2) irrev
(P2)rev.< (P2) irrev (If volume change are same)
(V2)rev.< (V2) irrev (If pressure change are same)

 Comparison of single stage Vs two stage expansion(adiabatic).

If the expansion is carried out in two stages then work done in two stage by the gas > work done in one
stage by the gas. So, Utwo stage > Usingle stage
  Tf in two stage < Tf in single stage because decrease in internal energy in two stage is > decrease in
internal energy in one stage.
Adiabatic Irreversible process (calculation of state parameters)
irrev
State A   State B
P1,V1,T1 P2,V2,T2
nR(T2  T1 ) P2 V2  P1V1 PV PV
W=  = – Pext. (V2 – V1) , 1 1 = 2 2
 1  1 T1 T2
 Free expansion :
Always going to be irrerversible and since Pext = 0
So, dW = – Pext.dV
=0
If no heat is supplied q = 0
then E = 0 So, T = 0.
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Section (G) : Enthalpy
Calculation of Cp and CV
(a) Constant volume process (Isochoric)
dU = dq + dw
 dU = (dq)v (Heat given at constant volume = change in internal energy)
 dU = (nCdT)v
dU = nCvdT
Cv is Specific molar heat capacity at constant volume.
1 dU 1 d (fnRT) / 2 fR
Cv = .  =
n dT n dT 2
(b) Constant pressure process (Isobaric) :
dU = dQ + dW
dU = dQ – PdV
 dQ = dU + PdV ............... (i)
Defining a new thermodynamic function
H  Enthalpy
  It is a state function and extensive property
 It is mathematically defined as :
H = U + PV
as dH = dU + d (Pv)
as P = constant
dH = dU + PdV .............. (ii)
from equation (i) & (ii)
 dH = (dq)p only at constant pressure.
Heat given at constant pressure = Change in enthalpy
dH = (nCdT)p
dH = nCp dT

 Relation between Cp and Cv for an ideal gas

H = U + PV
 dH = dU + d(PV)
for an ideal gas
PV = nRT
d(PV) = d(nRT) = nRdT
nCp dT = nCvdT + nRdT
 Cp – Cv = R only for ideal gas  Mayer’s Relationship

Table # 1 At Normal temperature

Degree of  fR  Cp,m  f  2  R  =  f  2 
S.No. Gas Cv,m   Examples
freedom  2   2   f 
3R 5R 5
1. Monoatomic 3 He; Ne
2 2 3
5R 7R 7
2. Diatomic 5  N2; O2; H2
2 2 5
5R 7R 7
3. Linear polyatomic 5 CO2; HCl
2 2 5
Non-Linear 6R 8R 8
4. 6 H2O; NH3; CH4
polyatomic 2 2 6

Note : At high temperature vibrational degree of freedom is also included.

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Calculation of H, U, work, heat etc.
Case - I For an ideal gas undergoing a process.
the formula to be used are
f
dU = nCvdT = nRdT 
2
f 
dH = nCpdT =   1 nRdT
2 
W = –  Pext . dV
dH = dU + d (PV)
du = dQ + dw

Ex-5. Calculate the maximum work done when pressure on 10 g of hydrogen is reduced from 20 atm to
1 atm at a constant temperature of 273 K. The gas behaves ideally. Will there be any change in internal
energy? Also, calculate ‘q’.
P
Sol. We have, W = – 2.303 nRT log 1
P2
wt. in grams 10
n = number of moles of hydrogen = = = 5 moles.
mol. wt. 2
20
Thus, W = – 2.303 × 5 × 2 × 273 × log = – 8180 calories.
1
Further, the change in state of the system at constant temperature will not change internal energy i.e.,
U = 0.
Again, q = U – W = 0 – (– 8180) = 8180 calories.

Case - II For solids and liquid system :

f
dU = nCvdT  nRdT (as it is not an ideal gas)
2
f 
dH = nCp dT    1 nRT (as it is not an ideal gas)
 2 
W = –  Pext . dV
 H = U + (P2V2 – P1V1)
dU = dq + dw

Ex-6. A liquid of volume of 100 L and at the external pressure of 10 atm–Lt the liquid is confined inside an
adiabatic bath. External pressure of the liquid is suddenly increased to 100 atm and the liquid gets
compressed by 1 L against this pressure then find,
(i) work (ii) U (iii) H
Sol. Work done = –100 × – 1 = 100 L. atm
q = 0 w = U
 100 = U
H = U + (P1V2 – P1V1 )
= 100 + (100 × 99 – 100 × 10)
= 100 + 100 × 89 = 9000 lit atm.
1 L. atm = 101.3 Joule.

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Case - III For chemical reactions :
aA (s) + bB() + cC(g) a’A’(s) + b’B’ () + c’ C’ (g)
W = –  Pext. dV =  P ext.  Vf  Vi 
= – Pext. [(VA’(s) + (VB’() + (VC’(g)– (VA(s) + (VB() + (VC(g)]
 W = – Pext. [VC’(g) – VC(g)]
 n' RT nc RT  Pext. (n'c  nc )RT
= – Pext.  c  = –
 Pext Pext  Pext.
W = – (n’c – nc)RT
  W = – ng RT
dU = dq + dw
if at constant pressure
dq = dH
  dU = dH – pdV
dU = dH – ng RT
  dH = dU + ng RT

Ex-7. For the combustion of 1 mole of liquid benzene at 25ºC, the heat of reaction at constant pressure is
1
given by, C6H6() + 7 O2 (g)  6CO2 (g) + 3H2O (); H = –780980 cal.
2
What would be the heat of reaction at constant volume?
Sol. We have, H = E + ng RT
Here,  ng = 6 – 7.5 = – 1.5.
Thus,  E = H – ng RT = – 780980 – (–1.5) × 2 × 298 = – 780090 calories.

Section (H) : Phase transition

Case - IV During phase transformation.
Phase transitions generally take place at constant pressure (unless specified) and at constant
temperature. So, T = 0.
But still H and E are non zero (different from process on an ideal gas)
Because during phase transitions though the kinetic energy of molecules of substance remains same
but the potential energy gets modified or changed and since E is summation of all type of energies. So,
E  0. Also, during this phase transition (PV)  0
Hence, H  0.
Now, to calculate heat – generally latent heats of transitions are given and since process is taking place
at constant pressure. So, q = H.
To calculate W, use dW = – Pext dV and then calculate E using Ist law of thermodynamics.

Ex-8. Calculate q, W, E and H when 100 g of CaCO3 is converted into its aragonite form given density of
calcite = 2 g/cc and density of aragonite = 2.5 g/cc
Sol. CaCO3 CaCO3
Calcite Aragonite H = 2 kJ/mole
Generally for solid  Solid
solid  Liquid
solid  Liquid
transitions W << q So,  E  q = H
while for gaseous conversion for example
Solid  gas
Liquid  gas
q = H  E, as W will be significant
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S.No. Process w q U H Molar heat capacity

1. Isochoric 0 nCv,m  Tf  Ti  qv nCp,m  Tf  Ti  Cv,m

2. Isobaric Pext  V2  V1  nCp,m  Tf  Ti  q + w nCp,m  Tf  Ti  Cp,m

V 
Wrev  nRT ln  f 
3. Isothemal  Vi  –w 0 0 ± 
Wirrev  Pext  Vf  Vi 

Pf Vf  PV
i i
4. Adidatic 0 w 0 0
 1

Pf Vf  PVi i
R
5. Polytropic U – w nCv,m (T2–T1) nCp,m(T2 – T1) Cv,m+
(n  1) 1 

Thermodynamics IInd & IIIrd Law

Section (A) : Introduction about entropy
IInd Law of thermodynamics :
Requirement : Ist law insufficient to Explain
Neutralization, Melting of ice > 0°
Combustion, Freezing of water < 0°
Fall of water, Boiling of water > 100° C
Cooling of a hot body, Free expansion of a gas, mixing of gases.
Spontaneous /Natural /Irreversible Processes :
If a system moves along in a direction on its own and system, surrounding interactions without the help
of any external agency, then that direction is known as spontaneous direction and the process is knwon
as a spontaneous process.
Limitation :
First law cannot predict the direction of any process. But in nature a process is found to have a specific
direction at certain conditions.
1. Energy can be the factor : To achieve stability
* All exothermic processes are spontaneous.
* All endothermic processes are non spontaneous.
Exceptions
* melting of ice (above 0°C) although H > 0, E > 0
* Vaporization of water (above 100°C) H > 0, E > 0
* Spreading of ink in water H = 0, E = 0
* Mixing of two gases
* Endothermic solution of salt H > 0, E > 0
2. It is observed that nature tries to distribute energy and matter uniformaly (randomization)
Second law of thermodynamics :
Entropy of the universe is constantly inereasing.
 S universe = S system + S surrounding > 0 for a spontaneous process.
Where (S) = entropy is the measure of randomness or disorder. It is a state function and extensive
property.
Mathematically
dqrev dq dq
ds = or S =  rev , is state function only for reversible process
T T T
1
dS  dqrev , dS 
T
At Higher T - entropy is already high. Therefore, heat addition will not introduce much change in the
entropy.
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Section (B) : Entropy Calculation
 Calculation of Ssystem

As ‘S’ is a state function. Hence ’S’ will also be a state function.

 S irrev = Srev
B
dq
S =  rev reversible path
A T
  Entropy calculation for an ideal gas undergo in a process.
irr S
State A   State B
P1, V1, T1 P2, V2, T2
As ‘S’ is a state function.So, S will not depend upon path
B
dq
 Sirrev = Srev, system =  rev rev path.
A T
from the first law
dU = dQ + dw
dQ = dU – dw
for reversible path
dq = dqrev
dqrev = dU + Pgas dV {Pext = Pgas reversible}
B
dU  Pgas dV
  Srev, system = 
A
T
for an ideal gas
Pgas nR
 & du = ncV dT
T V
T2 V2
nc v dT nRdV
  Ssys = 
T1
T


V1
V

T2 V
 Ssystem = nCvn + nRn 2
T1 V1

 Calculation of Ssurrounding : As the surrounding is an infinite heat reservoir hence, no. amount of heat
given to the surrounding can cause turbulance in it, hence all heat exhanges with surroundings are
considered to be reversible.
dqsurrounding
Ssurrounding = 
T
For surrounding T is constant
1 qsurrounding
 Ssurr =  dqsurr =
T T
But according to the law of conservation of energy
qsurr = – qsystem
qsystem
 Ssurr =
T

 Isothermal process :
(a) Reversible
Re v
State A   State B
P1,V1,T P2,V2,T

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T2 V
 S system = nCVn + nRn 2
T1 V1
Since T1 = T2
V2
S system = nRn
V1
q system
 Ssurrounding = 
T
du = dq + dw (since T1 = T2 . So, du = 0)
 dq = – dw
V
 q = –w as w = – nRTn 2
V1
V2
q = nRTn
V1
V2
nRTn
V1 V2
 Ssys. =  –nRn
T V1
Suniverse = Ssystem + Ssurr
V V
= nRn 2 –nRn 2 = 0
V1 V1
(b) rreversible
irrev
State A   State B
P1,V1,T P2,V2,T
V2
 Ssystem = nRn
V1
 qsystem
 SSurrounding =
T
qsystem is calculated using FLOT
qsystem = Pext(V2– V1)
pext (V2  V1 )
 Ssurrounding =
T
V2 pext (V2  V1 )
 Suniverse = nRn –
V1 T
1  V2  1
= (nRT n )  Pext (V2  V1 ) = [W irrev – W rev ] > 0
T  V1  T
As irreversible work of gas is more than reversible work.
 Adiabatic Process (Isoentropic process)
(a) Reversible Adiabatic
rev
State A   State B
P1,V1, T1 P2,V2, T2
T V
 Ssystem = nCV n 2 + nR n 2
T1 V1
TV–1 = constant
 1
T2  V1 
=  
T1  V2 
 1
V  V2
(S)system = nCVn  1  + nRn =0
 V2  V1
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Thermodynamics & Thermodynamics
qsys
 S surr = – = 0 (qsys= 0) Suniverse = 0 + 0 = 0
T
(b) Irreversible Adiabatic
irre
State A   State B
P1,V1,T1 P2,V2,T2
Using irreversible adiabatic process it is not possible to reach same state B which was reached by
reversible adiabatic.
T V
 S system = nCV n 2 + nR n 2 > 0 [(T2)irrev > (T2)rev]
T1 V1
q sys
 S surr = – =0 as q = 0
T
For irreversible expansion the decrease in temprature will be lesser as work done is lesser hence,
decrease in entropy due to fall in temprature will be lesser in case of irrversible expansion. Hence, net
entropy would increase.
 Isobaric process :
(a) Reversible Isobaric
irre
State A   State B
P, V1, T1 P, V2, T2
dq nCp dT T
 Ssys =  rev =  = nCpn 2
T T T1
T2
dqrev –dqsys T2
Ssurrounding =  T =  = – nCpn
T1 T T1
Suniverse = Ssys + Ssurrounding = 0
(b) Irreversible Isobaric
T2
dq nCp dT T
Ssys =  rev =  = nCpn 2
T T1 T T1
dqrev –nCp  T2 – T1 
Ssurrounding  =
T T2
 Suniverse = Ssys + Ssurrounding > 0

 Isochoric Process
(a) Reversible Isochoric
rev
State A   State B
P1,V, T1 P2,V, T2
T2
dq nCv dT T
 Ssys =  rev =  = nCvn 2
T T1 T T1
T
dqrev 2
–dqsys T
Ssurrounding =  = = – nCvn 2
T T1 T T1
Suniverse = Ssys + Ssurrounding = 0

(b) Irrversible Isochoric

T2
dqrev nCv dT T
Ssys =  =  = nCpn 2
T T1 T T1
–nCv  T2 – T1 
Ssurrounding =
T2
 Suniverse = Ssys + Ssurrounding > 0
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 Entropy Calculation for phase transformations
dq 1 Q
 Sfusion=    dq  T
T T
Hfus
For constant pressure Sfus. =
T
Ufusion
For constant volume Sfus. =
T
dq 1 Q
 Svap = T 
T  dq  T
Hvap
For constant Pressure, Svap =
T
Uvap
For constant Volume, Svap =
T
 Entropy Calculation solid or liquid systems:
(a) ‘Cu’ block kept in open atmosphere
T2
msdT T
 Ssystem =  = mn 2
T1 T T1
dqsurr q surr
 Ssurr =  
T T2
but q surr = – qsystem = – ms (T2 – T1) = ms (T1 – T2)
ms (T1 – T2 )
Hence, Ssurr =
T2
Suniverse = Ssystem + Ssurr
T2 ms (T1  T2 )
 Suniverse = ms n + >0
T1 T2
(b) Two copper block kept in contact in thermostat
Two blocks are of same mass
Ssurr = 0 (since no heat is lost to surrounding)
S system = SA + SB
System will reach a common temperature (Tf )
and T1 > Tf > T2
Tf Tf
dq dqB
 S system = T TA + 
T2 T
1

Tf T
msdT f msdT  T T 
= + = ms  n f  n f 
T1 T T2 T  T1 T2 
Tf2
Ssystem = msn
T1T2
2

Since Tf =
T1  T2
 Ssystem = msn
 T1  T2 
2 4T1T2


Ex-9. (a) One mole of an idal gas expands isothermally and reversibly at 25ºC from a volume of 10 litres to a
volume of 20 litres.
(i) What is the change in entropy of the gas?
(ii) How much work is done by the gas?
(iii) What is q (surroundings)?
(iv) What is the change in the entropy of the surroundings?
(v) What is the change in the entropy of the system plus the surroundings?

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(b) Also answer the questions opening a stopcock and allowing the gas to rush into an evacuated bulb
of 10 L volume.
V2 20
Sol. (a) (i) S = 2.303 nR log = 2.303 ×1 × 8.314 × log = 5.76 J/K.
V1 10
V2
(ii) W rev = –2.303nRT log
V1
20
= –2.303 × 1 × 8.314 × 298 × log = –1781 J.
10
(iii) For isothermal process, U = 0 and heat is absorbed by the gas,
qrev = U – W = 0 –(–1718) = 1718 J.
 qrev = 1718 J. ( process is reversible)
1718
(iv) Ssurr = – = – 5.76 J/K.
298
As entropy of the system increases by 5.76 J, the entropy of the surroundings decreases by
5.76J, since the process is carried out reversibly.
(v) Ssys + Ssurr = 0..... for reversible process
(b) (i) S = 5.76 J/K, which is the same as above because S is a state function
(ii) W = 0 ( pext = 0)
(iii) No heat is exchanged with the surroundings.
(iv) Ssurr = 0.
(v) The entropy of the system plus surroundings increases by 5.76 J/K, as we expect entropy to
increase in an irreversible process.

 Third Law Of Thermodynamics :
The entropy of perfect crystals of all pure elements & compounds is zero at
the absolute zero of temperature.
Thus, absolute value of entropy unlike the absolute value of enthalpy for
any pure substance can be calculated at any given temperature. In
standard state (298 K, 1 atm), it is standard absolute entropy Sº.
T
nCdT
S = ST(K)– S0(K) = 
0
T
 For chemical reaction
aA + bB  cC + dD
Sºsystem = ( S0m ni)product – ( S0m ni)reactant
where S0m = standard molar entropy. It can calculated using third law of thermodynamics.
Qsystem Hsystem
 Ssurr = =
T T
* For a perfactly crystline substance at 0 K, entropy = 0

 For phase transformations

dp 1 Q
 Sfusion=    dp 
T T T
Hfus
for constant pressure Sfus. =
T
Ufusion
for constant volume Sfus. =
T
dQ 1 Q
 Svap =    dQ  T
T T
Hvap
for constant Pressure, Svap =
T
Uvap
for constant Volume, Svap =
T
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Section (C) : Free energy
  Gibb’s free energy (G) :
A system parameter to predict the spontaneity of chemical reaction was introduced by Gibb’s so that
entropy calculation for the surrounding need not be carried out.
It is a free energy at constant pressure.
G = H – TS
dG = dH – TdS – SdT
& H = U + PV
dH = dU + PdV + VdP  dG = dU + PdV + VdP –TdS –SdT
From Ist law of thermodynamics
dq = dU + PdV
& from 2nd law, dq = TdS
dG = dq + VdP –TdS – SdT
dG = – SdT + VdP
At constant temperature,
dG = VdP
nRT
For ideal gas, V =
P
RT
dGm = VmdP = dP
P
2 P2
dP
 dGm = RT 
1 P1 P

P2
Gm2 – Gm1 = RTn
P1
Where Gm is free energy for 1 mole
If Gm1 is free energy for 1 mole in standard state and Gm2 is free energy for one mole in any other state.
P P
Gm – G°m = RTln & G – G° = nRTn
1 1
For the reaction, aA(g) + bB(g) C(g) + dD(g)
(G)reaction = (G)product – (G)reactant
(G)reaction = GC + GD – GA – GB
P
GC – G°C = cRTln C  GC = G°C + cRTln PC
1
Similarly, GD= G°D + dRTln PD ; GA= G°A + aRTln PA , GB= G°B + bRTln PB
(G)reaction = (G°C + cRTln PC) + (G°D + dRTln PD ) – (G°A + aRTln PA ) – (G°B + bRTln PB)
Pc C .PdD
= (G)°reaction + RTln a b
P A .P B
Greaction = G°reaction + RTlnQ
Gibb’s Helmholtz Equation :
dG = VdP – SdT
At constant Pressure
 dG   G 
dG = – SdT    =–S&   = – S
 dT P  T P
G–H
& G = H – TS  =–S
T
G – H  G 
= 
T  T P
 G 
G = H + T 
 T P
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 G 
G = H + T  
 T P
G = H –T S

Suniverse = Ssystem + Ssurrounding

Qsystem Hsystem
 Ssurr = =
T T
TS univ = TS system – Hsystem
Introducing a new thermodyamic function G = Gibb’s free energy (State function and an extensive
property)
Gsystem = H system – TS system
 G = H – TS
Gsystem = H system – TS system .................. (ii)
Comparing equation (i) and (ii)
 Gsystem = – TS universe
New criteria of spontaneity :
(i) If G system is (–ve) < 0   process is spontaneous
(ii) If G system is > 0   process is non spontaneous
(iii) If G system = 0   system is at equilibrium
So, at every temparature G  0
  H system S system G system = H system – TS system
+ Ve – Ve +
– Ve + Ve –
+ Ve + Ve – Ve at high temprature
– Ve – Ve + Ve at high temprature
 Gº = standrad free energy change :
 When the reactants under standrad conditions gets converted into products which is also under
standared condition, then the free energy change is known as Gº (it is a constant) for 1 mole at 1 bar.
At standared conditions :
 G° = H° – TS°
= constant for a GIVEN REACTION
 AB  C +  D
 G° = (Gbb’s energy of product) – (Gibb’s energy of reactant)
0
G° =  Gm,C 0
+ Gm,D – G0m,A – G0m,B , where Gm0 can not be calculated as H0m cannot be calculated.
Hence, we can convert this relation in to Gibb’s energy of formation of substance.
 G° = G0f,C + G0f,D – G0f,A – G0f,B
G0f : standared Gibb’s energy of formation.
G0f (elements in their standard states) = 0
 G° = G0f,product – G0f,reac tan ts
For a reaction in progress
 G = Gº + RT n Q
Q is reaction quotient , G > 0 backward is feasible , G < 0 forward is feasible
At equilibrium G = 0  Q = K  Gº = – RT n K at equilibrium.

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Ex-10. Ka for CH3COOH at 25ºC is 1.754 × 10–5. At 50ºC, Ka is 1.633 × 10–5. What are Hº and Sº for the
ionisation of CH3COOH?
Sol. (Gº)298 = – 2.303RT log K = – 2.303 × 8.314 × 298 ×log (1.754 ×10–5) = 27194 J.
-5
(Gº)323 = 2.303 × 8.314 × 323 × log ( 1.633 × 10 ) = 29605 J.
Gº = Hº – TSº  27194 = Hº – 298 Sº
29605 = Hº – 323 Sº  Hº = – 1.55 kJ/mol  Sº = – 96.44J/mol.K

2. THERMOCHEMISTRY
Section (A) : Calculation U, H & W for chemical reaction
 Enthalpy of a substance :
 Every substance has a fixed value of enthalpy under any particular state. Though, its exact value
cannot be calculated but it has some finite fixed value.
 The enthalpy of one mole of a substance called molar enthalpy in any particular state can be assigned
symbol
 Hm(substance) : For example molar enthalpy of water vapours at 398 K and 1 atm pressure may be
represented as Hm (H2O, g, 398 K, 1 atm). In very simple words, enthalpy can be considered as heat
constant (amount) of substance, and during reaction this heat is being released or absorbed.
 Molar enthalpy of substance under standard conditions is called standard molar enthalpy of a
substance. Standard state of any substance means.
  For a GAS standard state means ideal gas at 1 bar partial pressure at any give temperature.
  For a LIQUID – pure liquid at one bar pressure at 1 bar pressure at any given temperature.
  For a PURE CRYSTALLINE SOLID – pure crystalline solid at 1 bar pressure and at any given
temperature
  For any SUBSTANCE or ION IN SOLUTION – the species should be in unit molality (can also be
taken as 1M concentration), at one bar pressure and at any given temperature.
 Molar standard enthalpy of water vapours at 398 K will be represented as H°(H2O, g , 398 K) and molar
standard enthalpy of liquid water at 398 K will be represented as Hm° (H2O, l, 398 K)
(It is hypothetical but can be calculated).
 We cannot exactly calculate enthalpy content of a substance only the change in enthalpy can be
calculated when substance is taken from one state to other.
For example :

Let enthalpy content initially be H0m, 1 & finally enthalpy content be H0m, 2
Then, H° = H0m, 2 – H0m, 1
= heat added at constant pressure to change temperature from 25°C to 50°C.
= CPT = (18 cal/mole °C) (25°C) = 450 cal

Ex-11. Why does heat get released/absorbed during chemical reactions?

Sol. Because the reactants have a fixed enthalpy content before the reaction and when these are converted
into the products which have a different enthalpy content. So, heat gets released or absorbed. Even if
temperature of reactions remains constant yet due to change in bonding energies E  0.
If Hproducts > Hreactants
Reaction should be endothermic as we have to give extra heat to reactants to get these converted into
products and
if Hproducts < Hreactants

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Reaction will be exothermic as extra heat content of reactants will be released during the reaction.
Enthalpy change of a reaction :  
H°reactions = H°products – H°reactants
= positive – endothermic
= negative – exothermic
Section (B) : Basics & Kirchoff’s law
 Hess’s Law of constant heat summation :
 The heat absorbed or evolved in a given chemical equation is the same whether the process occurs in
one step or several steps.
 The chemical equation can be treated as ordinary algebraic expressions and can be added or
subtracted to yield the required equation. The corresponding enthalpies of reactions are also
manipulated in the same way so as to give the enthalpy of reaction for the desired chemical equation.
 Since rH stands for the change of enthalpy when reactants (substances on the left hand side of the
arrow) are converted into products (substances on the right hand side of the arrow) at the same
temperature and pressure, if the reaction is reversed (i.e., products are written on the left hand side and
reactants on the right hand side), then the numerical value of rH remains the same, but its sign
changes.
 The utility of Hess’s law is considerable. In almost all the thermochemical numericals, Hess’s law is
used.
 One of the important applications of Hess’s law is to determine enthalpy of reaction which is difficult to
determine experimentally. For example, the value rH for the reaction
1
C(graphite) + O2 (g)  CO(g)
2
which is difficult to determine experimentally, can be estimated from the following two reactions for
which rH can be determined experimentally.
C(graphite) + O2(g)  CO2(g) rH1
1
CO(g) + O2(g)  CO2(g) rH2
2
Substracting the latter from the former, we get
1
C(graphite) + O2(g)  CO (g)
2
Consequently, rH = rH1 – rH2

Ex-12. Calculate heat of the following reaction at constant pressure,

F2O(g) + H2O(g)  O2 (g) + 2HF(g)
The heats of formation of F2O (g), H2O(g) and HF (g) are 5.5 kcal, –57kcal and –64 kcal respectively.
1
Sol. Given that (i) F2(g) + O2(g)  F2O(g); H = 5.5 kcal
2
1
(ii) H2(g) + O2(g)  H2O(g); H = – 57 kcal
2
1 1
(iii) H2(g) + F2(g)  HF(g); H = – 64 kcal
2 2
F2O and H2O in eqns. (i) and (ii) and in the eqn. given in the problem are on the opposite sides, while
HF in eqn. (iii) and in the eqn. given in the problem is on the same sides.
Thus applying, [– Eqn. (i) –Eqn. (ii) + 2 × Eqn. (iii)], we get
1 1
–F2(g) – O2(g) – H2(g) – O2(g) + H2 + F2(g) –F2O(g)  – H2O(g) + 2HF(g);
2 2
H = – 5.5 – (– 57) + 2 × (– 64)
or F2O(g) + H2O(g)  O2(g) + 2HF(g); H = – 76.5 kcal.

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 Relation between energy and enthalpy of a reaction :
rH = rU + (vg)RT
where v g is the change in the stoichiocmetric number of gaseous species in going from reactants to
products.
It should be noted that while computing vg of a reaction, only the stoichiometric numbers of gaseous is
counted and those of liquids and solids are completely ignored.
Kirchoff’s equation (Variation of Hº with temprature)
Since the enthalpy (or standard enthalpy) of a substance is dependent on state of the substance, value
of enthalpy of a substance changes with temperature and hence the enthalpy change of reaction is also
dependent on temperaturte at which the reaction is being carried out. This change is enthalpy change
(or E of reaction is carried out at constant volume) is represented by Kirchoff’s Equations.
P + Q  R + S
at temperature T1 let the standard enthalpy of reaction be H°1 , then
H1° = H°m (R, T1) + H°m (S, T1) – H°m (P, T1) – H°m (Q, T1)
If the same reaction is carried out at temperature T2, then
H2° = H°m (R,T2) + H°m (S, T2) – H°m (P, T2) – H°m (Q, T2)
Then, the change in enthalpy (or difference in enthalpy at these two temperatures)
 H° = H2° – H1° =  {Hm° (R, T2) – Hm° (R, T1)} + {Hm° (,T2) – Hm° (,T1)}
–  {Hm° (P, T2) – Hm° (P, T1)} -  {Hm° (Q, T2) – Hm° (Q,T1)}
Hm° (R, T2) – Hm° (R, T1) = CP, R (T2 – T1) = Heat required at constant pressure to increase temperature
of one mole of R from T1 to T2
Similarly
Hm°(S, T2) – Hm° (S, T1) = CP,S(T2 – T1)
Hm°(P, T2) – Hm° (P, T1) = CP,P(T2 – T1) and
Hm°(Q, T2) – Hm° (Q, T1) = CP,Q(T2 – T1)
so H° = H2° – H1° =  CP,R(T2 – T1) + CP,S(T2 – T1) – CP,P(T2 – T1) – CP,Q(T2 – T1)
= [ CP,R + CP,S –  CP,P – CP,Q] (T2 – T1) = CP (T2 – T1)
CP = CP, R + CP,S – CP,P – CP,Q
= Difference in molar heat capacities of products and reactants.
so H2° = H1° +  CP .dT
For example for the reaction
N2 (g) + 3H2 (g)  2NH3 (g)
 H2° = H1° + CP (T2 – T1)
where CP = 2CP, NH3  CP, N2  3CP, H2
* for a constant volume reaction, E02  E10   CV .dT 

Section (C) : Enthalpy of formation & combustion

 Enthalpy of formation :
It is not possible to determine the absolute value of the molar enthalpy of a substance. However, based
on the following convention, the relative values of standard molar enthalpies of formation of various
substances can be built.
 “The standard enthalpy of formation of every element in its stable state of aggregation at one bar
pressure and at specified temperature is assigned a zero value”.The specified temperature is usually
taken as 25°C.
A few exmaples are Hf° (O2, g) = 0
Hf° (C, graphite) = 0 Hf° (C, diamond)  0
Hf° (Br2, liquid) = 0
Hf° (S, rhombic) = 0 Hf° (S, monoclinic)  0
Hf° (P, white) = 0 Hf° (P, black)  0
“The standard enthalpy of formation of a compound is the change in the standard enthalpy when one
mole of the compound is formed starting from the requisite amounts of elements in their stable state of
aggregation”.

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The chemical equations corresponding to enthalpy of formation of few substances are given below.
1 1
Enthalpy of formation of HBr(g) : H2 (g) + Br2 (  )  HBr(g)
2 2
1 0 1 0
Hf°(HBr, g) = Hm (HBr, g) – Hm (H2, g) – Hm (Br2,  )
0
...(1)
2 2
Enthalpy of formation of SO2 (g) : S (rhombic) + O2 (g)  SO2 (g)
Hf° (SO2, g) = H0m (SO2, g) – H0m (S, rhombic) – H0m (O2, g) ...(2)
But above equations cannot be for calculation of enthalpy of reaction as the molar enthalpies of
different species can not be exactly known.

 Enthalpy of Reaction from Enthalpies of Formation:

The enthalpy of reaction can be calculated by

Hr° =  B Hf°,products –  B Hf°,reactants 


B is the stoichiometric coefficient

above equation holds good for any reaction as

the same reference state is used for reactants
and products (shown in figure).

Ex-13. Calculate the standard enthalpy of reaction ZnO(s) + CO(g)  Zn(s) + CO2 (g).
Given, Hf° (ZnO, s) = – 350 KJ/mole, Hf° (CO2, g) = – 390 KJ/mole, Hf° (CO, g) = – 110 KJ/mole.
Sol. H° = {Hf°(CO2, g) –Hf° (ZnO, s) +Hf° (CO, g))}
 H°reaction = –390 – (–350 –110) = 70 KJ


 Enthalpy of Combustion :
 It is the enthalpy change when one mole of a compound combines with the requisite amount of oxygen
to give products in their stable forms.
–1
For example, the standard enthalpy of combustion of methane at 298 K is – 890 kJ mol . This implies
the following reaction :
–1
CH4 (g) + 2O2(g)  CO2(g) + 2H2O () H° = – 890 kJ mol
The standard enthalpy of combustion of methane at 298 K may be written as
Hc° (CH4, g, 298 K) = – 890 kJ mol–1
 The data on the enthalpy of combustion can be determined experimentally.
 With the help of such data, we can determine the enthalpy of formation of a compound, which otherwise
is difficult or impossible to determine experimentally. Consider for example, the enthalpy of formation of
CH4(g):
C(graphite) + 2H2(g)  CH4(g)
First of all, the combination of carbon and hydrogen does not occur readily. Secondly, if the reaction is
even completed, the end product would not be pure methane. Therefore, the enthalpy of formation of
methane can be determined indirectly through the enthalpy of combustion of methane :
CH4(g) + 2O2(g)  CO2(g) + 2H2O()
  HC°(CH4, g) = Hf°(CO2, g) + 2Hf°(H2O , ) – Hf° (CH4, g)
therefore Hf°(CH4, g) = Hf°(CO2, g) + 2Hf°(H2O , ) – HC° (CH4, g)


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 The enthalpies of formation of CO2 and H2O can be determined experimentally by the combustion of
carbon (graphite) and hydrogen. Thus, knowing the mesured value of HC°(CH4, g), the enthalpy of
formation of CH4 can be calculated. The value is
Hf°(CH4, g) = Hf°(CO2, g) + 2 Hf°(H2O , ) – HC° (CH4, g)
= [– 393 + 2 (–285) – (–890)] kJ mol–1 = – 73 kJ mol–1
or, equivalently, we may add the following three chemical equations.
C(graphite) + O2 (g)  CO2 (g) CH° = – 393 kJ mol–1
1 –1
2[H2(g) + O2 (g)  H2O()] rH° = 2(– 285) kJ mol
2
– [CH4(g) + 2O2 (g)  CO2 (g) + 2H2O()] rH° = –(– 890) kJ mol–1
––––––––––––––––––––––––––––––––––––––– ––––––––––––––––––––––
C(graphite) + 2H2(g)  CH4 (g) fH° = – 73 kJ mol–1

 Measurement of Enthalpy of Combustion :
Enthalpy of combustion are usually measured by
placing a known mass of the compound in a closed
steel container (known as bomb calorimeter) which is
filled with oxygen at about 30 bar pressure.
The calorimeter is surrounded by a known mass of
water. The entire apparatus is kept in an insulated
jacket to prevent heat entering into or leaving from the
container, as shown in figure. The sample is ignited
electrically to bring about the combustion reaction. The
heat evolved is used in raising the temperature of
water and the calorimeter.
If total heat capacity of calorimeter and all of its
contents = C,
rise in temperature = T
then heat released = q = CT of this heat is because
of mass m of substance then :

M
due to 1 mole, heat released =   q = EC°
m
(Constant volume reaction).
Now, HC° can be calculated by using HC° = EC° + ng RT.
Where ng is the change in stoichiometric number of gaseous species in the balanced chemical
equation representing the combustion process.

Ex-14. A gas mixture of 4 litres of ethylene and methane on complete combustion at 25ºC produces
6 litres of CO2. Find out the amount of heat evolved on burning one litre of the gas mixture. The heats
of combustion of ethylene and methane are – 1464 and –976 kJ mol-1 at 25ºC. [IIT-1991 ]

Sol. + O2 CO2 + H2O

x lit. (4 – x)lit. 6 lit.
(say)
or x moles (4 – x) moles 6 moles
Applying POAC for C atoms,
2 × x + 1 × ( 4 – x ) = 1 × 6 ; x = 2 lit.
Thus, the volume of C2H4 = 2 lit., and volume of CH2 = 2 lit.
volume of C2H4 in a 1 litre mixture = 2/4 = 0.5 lit.
and volume of CH4 in a 1 litre mixture = 1 –0.5 = 0.5 lit.

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Now, thermochemical reactions for C2H4 and CH4 are
C2H4 + 3O2 2CO2 + 2H2O; H = – 1464 kJ
CH4 + 2O2CO2 + 2H2O; H = – 976 kJ
As H values given are at 25ºC, let us first calculate the volume occupied by one mole of any gas at
25ºC (supposing pressure as 1atm)
298
Volume per mole at 25ºC = × 22.4 = 24.4 lit.
273
1464
Thus, heat evolved in the combustion of 0.5 lit. of C2H4 = – × 0.5 = – 30 kJ
24.4
976
and heat evolved in the combustion of 0.5 lit.of CH4 = × 0.5 = –20 kJ.
24.4
 total heat evolved in the combustion of 1 litre of the mixture = –30 + (– 20) = – 50 kJ.

Section (D) : Bond enthalpy method & Resonance energy
 Bond Enthalpies :
The bond enthalpy is the average of enthalpies required to dissociate the said bond present in
different gaseous compounds into free atoms or radicals in the gaseous state. While bond
dissociation enthalpy is the enthalpy required to dissociate a given bond of some specific
compound.for example the enthalpy of dissociation of the O–H bond depends on the nature of
molecular species from which the H atom is being separated. For example, in the water molecule.
H2O(g)  H(g) + OH(g) Hrº = 501.87 kJ mol–1
However, to break the O–H bond in the hydroxyl radical required a different quantity of heat :
OH(g)  O(g) + H(g) Hrº = 423.38 kJ mol–1
The bond enthalpy, HH, is defined as the average of these two values, that is :
501.87mol1  423.38kJmol1
HH = = 462.625 kJ mol–1
2
In the case of diatomic molecules, such as H2, the bond enthalpy and bond dissociation enthalpy are
identical because each refers to the reaction.
H2(g)  2H(g) HH – H = Hr0 = 435.93 kJ mol–1
Thus, the bond enthalpy given for any particular pair of atoms is the average value of the dissociation
enthaplies of the bond for a number of molecules in which the pair of atoms appears.
 Estimation of Enthalpy of a reaction from bond Enthalpies :
Let the enthalpy change for the gaseous reaction

be required from the bond enthalpy data. This may be calculated as follows :
 Enthalpy required to break reactants   Enthalpy released to form products 
H =   
 into gasesous atoms   from the gasesous atoms 
= [4HC–H + HC=C + HH–Cl]R + [–5HC–H – HC–C – HC–Cl]P
= (HC=C + HH–Cl) – (HC–H + HC–C + HC–Cl)
Enthalpy of Transition :
Enthalpy of transition is the enthalpy change when one mole of one allotropic form changes to another.
For example : C(graphite)  C(diamond) Htrsº = 1.90 kJ mol–1
-1
so if C(graphite) + O2(g)  CO2(g) HCº = – 393.51 kJ mol
–1
and C(diamond) + O2(g)  CO2(g) HCº = – 395.41 kJ mol
–1
Subtracting, we have, C(graphite)  C(diamond) Htrsº = 1.90 kJ mol

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Ex-15. Using the bond enthalpy data given below, calculate the enthalpy change for the reaction
C2H4(g) + H2(g)  C2H6(g)
Data : Bond Bond enthalpy
C–C 336 kJ mol–1
C=C 606 kJ mol–1
C–H 410 kJ mol–1
–1
H–H 431 kJ mol
Sol. Diagrammatically, we represent the given reaction as follows :
H H H H
| |
C=C (g) + H H(g) H H C C H
| |
H H H H
Break Break
make bond
bonds bonds
H H

2C(g) + 4H(g) + 2H(g) H C C H

H H
Hr = (4HC–H +HC=C + HH–H) – (6HC–H +HC–C)
= (4 × 410 + 606 + 431) – ( 6× 410 + 336)
= 2677 – 2796 = – 119 kJ/mol.
Ex-16. Using the bond enthalpy data given below, estimate the enthalpy of formation of gaseous isoprene
CH2  C  CH  CH2
|
CH3
Data: Bond enthalpy of C – H bond = 413.38 kJ mol–1
Bond enthalpy of C – C bond = 347.69 kJ mol–1
Bond enthalpy of C = C bond = 615.05 kJ mol–1
Enthalpy of sublimation of carbon (graphite) = 718.39 kJ mol–1
Enthalpy of dissociation of H2(g) = 435.97 kJ mol–1
Sol. For isoprene, we have to form
2C – C bonds ; 2C = C bonds and 8C – H bonds
Method-1 For which energy released is
[2(+347.69) + 2(+615.05) + 8(+413.38)] kJ mol–1 = 5 232.52 kJ mol–1
–1
that is, H (from gaseous atoms) = + 5232.52 kJ mol
The reaction corresponding to this is
5C(g) + 8H(g)  C5H8(g) fH1 = – 5232.52 kJ mol–1
But we want fH corresponding to the following equation
5C(graphite) + 4H2(g)  C5H8(g) fH = ?
This can be obtained by the following manipulations :
5C(g) + 8H(g) C5H8(g) rH2 = – 5232.52 kJ mol–1
5C(graphite)  5C(g) rH3 = 5 × 718.39 kJ mol–1
4H2(g)  8H(g) rH4 = 4 × 435.97 kJ mol–1
Adding, we get
5C(graphite) + 4H2(g)  C5H8(g) fH = 103.31 kJ mol–1
Method-2 Diagrammatically, the above calculations may be represented as follows.

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Applying Hess’s law, we get
fH = 5H3 + 4H4 – 2HC = C – 2HC – C – 8HC – H
= (5 x 718.39 + 4 x 435.97 – 2 x 615.05 – 2 x 347.69 – 8 x 413.38) kJ mol–1
fH = 103.31 kJ mol–1
Ex-17. Find the bond enthalpy of S – S bond from the following data :
C2H5 – S – C2H5(g) fH° = – 147 kJ mol–1
C2H5 – S – S – C2H5(g) fH° = –201 kJ mol–1
S(g)    fH° = 222 kJ mol–1
Sol. Given that
Method-1 (i) 4C(s) + 5H2(g) + S(s)  C2H5 – S – C2H5(g) fH° = –147 kJ mol–1
(ii) 4C(s) + 5H2(g) + 2S(s)  C2H5 – S – S – C2H5(g) fH° = –201 kJ mol–1
Subtracting Eq. (i) from Eq. (ii), we get
C2H5 – S – C2H5(g) + S(s)  C2H5 – S – S – C2H5(g) rH° = –54 kJ mol–1
Adding to this, the following equation
S(g)  S(s) fH° = –222 kJ mol–1
We get
–1
C2H5 – S – C2H5(g) + S(g)  C2H5 – S – S – C2H5(g) rH° = –276 kJ mol
In the last equation 276 kJ of heat evolved because of the S–S bond formation.
–1
Hence, the bond enthalpy of S – S is 276 kJ mol .
Method-2 Diagrammatically, we may represent the above calculation as follows :

According to Hess’s law :

 rH° = Enthalpy involved in bond breaking vapHº(s) – Enthalpy involved in bond making
rH° = [2HC – C + 10HC–H + 2HC–S + vapH(S)] + [–2HC–C – 10HC–H – 2HC–S – HS–S]
= vapH°(S) – HS–S
or HS–S = vapH°(S) – H°
= vapH°(S) – [fH°(C2H5 – S – S – C2H5] – fH°(C2H5 – S – C2H5)]
= [222 – {–201 – (–174)}] kJ mol–1 = 276 kJ mol–1


 Resonance energy :

Difference between energy of resonance hybrid and resonating structure in which resonance hybrid
have lower energy because stabilised by resonance.
 H°resonance = H°f, experimental – H°f, calclulated
= H°combustion, calclulated– H°combustion, experimental

Ex-18. Calculate the heat of formation of benzene from the following data, assuming no resonance. Bond
energies :
C – C = 83 kcal, C C = 140 kcal, C – H = 99 kcal
Heat of atomisation of C = 170 .9 kcal
Heat of atomisation of H = 52.1 kcal

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Sol. We have to calculate H for the reaction
6C(s) + 3H2(g) C6H6(g)
For reactants :
Heat of atomisation of 6 moles of C = 6 × 170.9 kcal
Heat of atomisation of 6 moles of H = 6 × 52.1 kcal
For products :
Heat of formation of 6 moles of C – H bonds = – 6 × 99
Heat of formation of 3 moles of C–C = – 3 × 83
Heat of formation of 3 moles of C C bonds = –3 × 140
on adding, we get heat of formation of C6H6,i.e.,
fH = 6 ×170.9 + 6 × 52.1– 6 × 99 – 3 × 83 –3 × 140 = –75 kcal

Section (E) : Enthalpy of solution & Born Haber’s cycle

 Integral enthalpy of solution
The integral enthalpy of solution at the given concentration is the enthalpy change when one mole of
the solute is dissolved in a definite quantity of solvent to produce a solution of a desired concentration.
While recording integral enthalpies of solution it is a general practice to state the amount of the solvent
in which 1 mole of solute is dissolved ; Thus
HCl(g) + 10H2O()  HCl (10H2O) H1 = –69.5 kJ mol–1
indicates that when 1 mole of hydrogen chloride gas is dissolved in 10 mol of water, there is an
evolution of 69.5 kJ of heat. Other values are
(i) HCl(g) + 25 H2O()  HCl (25H2O) H2 = –72.3 kJ mol–1
(ii) HCl(g) + 40 H2O()  HCl (40H2O) H3 = –73.0 kJ mol–1
(iii) HCl(g) + 200 H2O()  HCl (200H2O) H4 = –74.2 kJ mol–1
(iv) HCl(g) + aq  HCl (aq) H5 = –75.0 kJ mol–1
Whenever amount of solvent is not specified then take its amount to be very large just like in
equation no. (iv).

 Enthalpy of Hydration :

Enthalpy of hydration is used in following two ways.
 Enthalpy of hydration of anhydrous or partially hydrated salts :
Enthalpy of hydration of a given anhydrous or partially hydrated salt is the enthalpy change when it
combines with the requisite amount of water to form a new hydrated stable salt.
For example, the hydration of anhydrous cupric sulphate is represented by
CuSO4(s) + 5H2O()  CuSO4.5 H2O(s)
There is a almost invariably a liberation of heat in such reactions, i.e. the value of H is negative.
–1
CuSO4(s) + 800 H2O()  CuSO4 (800 H2O) Hr° = – 68 kJ mol
CuSO4.5H2O(s) + 795 H2O()  CuSO4 (800 H2O) Hr° = + 10 kJ mol–1
by subtraction, we get
CuSO4(s) + 5H2O()  CuSO4.5 H2O(s)  Hr° = – 78 kJ mol–1
 Enthalpy of hydration of gaseous ions.
Enthalpy of hydration of any gaseous ion is the enthalpy change when 1 mole of the gaseous ion is
hydrated in large amount of water to form aqeous ion.
By convention, the standard enthalpy of formation of H+(aq) is taken to be zero.
Enthalpy of hydration of Cl– gaseous ions will be represented by :
– – –
Cl (g) + aq. — Cl (aq) Hr° = Hf° (Cl , aq)

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Section (F) : Enthalpy of neutralization
 The amount of heat released when one gram equivalent of an acid is neutralised by one gram
equivalent of a base.
or
 The amount of heat released in formation of one mole of water when an acid is neutralised by a base.
or
 Enthalpy of neutralization is defined as the enthalpy change when one mole of H+ in dilute solution
combines with one mole of OH¯ to give rise to undissociated water, i.e.
H+(aq) + OH¯(aq)  H2O() H= –57.1 kJ/mole = –13.7 kcal/mol
Remember : 
 For Strong Acid + Strong Base, heat of neutralisation is always equal to –13.7 kcal/mole or –57.1
kJ/mole.
 For any other combination of acid and base this heat is less than –13.7 kcal/mole or –57.1 kJ/mole.
 Enthalpy of Ionization of Weak electrolyte :
 Whenever a weak acid (or base) reacts with a strong base (or acid), the release of heat is less than
57.1 kJ mol–1.
 It is because of the fact that these acids or bases are not completely ionized in solution. Some of the
heat is consumed in ionizing there acids and bases this heat is known as enthalpy of ionization.
Examples are :
HCN + Na+OH–  Na+ + CN– + H2O   rH° = – 12 kJ mol–1
+ – + – –1
CH3COOH + Na OH  Na + CH3COO + H2O rH° = – 49 kJ mol
 The enthalpy of ionization can be calculated as follows. The neutralization of a weak acid, say HCN,
may be represented in two steps, namely,
Ionization HCN  H+ + CN¯ H°1 = x
Neutralization H+ + OH¯  H2O H°2 = – 57.1 kJ/mole
The complete reaction is obtained by adding the above two steps. Thus
HCN + OH¯  H2O + CN¯ H° = – 12 kJ/mole
Obviously, H° = H°1 + H°2
H°1 = H°H°2 = [–12 – (–57.1)] = 45.1 kJ/mole
 Greater the enthalpy of ionization of any weak acid or weak base, weaker will be the acid or
base.

Ex-19. Enthalpy of neutralization of HCl by NaOH is –57.1 kJ/mol and by NH4OH is –51.1 kJ/mol. Calculate the
enthalpy of dissociation of NH4OH.
+ +
Sol. Given that, H (aq) + NH4OH(aq)  NH4 (aq) + H2O() H = –51.1 kJ/mole
We may consider neutralization in two steps.
(i) Ionization NH4OH(aq) — NH4+(aq) + OH¯(aq) H1 = ?
(ii) Neutralization H+(aq) + OH¯(aq) — H2O() H2 = – 57.1 kJ/mole
Thus,  H = H1 + H2
Therefore, H1 = H – H2 = – 51.1 kJ/mol + 57.1 kJ mol–1 = 6.0 kJ/mol

Enthalpy of Precipitation :
Enthalpy of precipitation is the enthalpy change when one mole of a precipitate is formed.
0 –1
For example : BaCl2(aq.) + Na2SO4(aq)  BaSO4(s) + 2NaCl(aq) rH =–24.27 kJ mol

Ex-20. Calculate H° for the reaction, Ag+(aq) + Cl¯(aq)  AgCl(s) at 25°C.
Given fH°(Ag+, aq) = 105 kJ mol–1, fH°(Cl¯, aq) = –167 kJ mol–1 and fH°(AgCl, s) = –127 kJ mol–1
+
Sol. For the reaction Ag (aq) + Cl¯(aq)  AgCl(s)
We have H° = fH° (AgCl, s) – fH°(Ag+, aq) – fH°(Cl¯, aq)
–1 –1
= [–127 – 105 – (–167)] kJ mol = –65 kJ mol
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 Enthalpy of Formation of ions :
The enthalpy change when one mole of hydrated ions is obtained from element in its standard state as.
½ Cl2 (g) + aq  Cl– (aq) Hr° = Hf° (Cl–, aq)
By convention, the standard enthlpy of formation of H+(aq) is taken to be zero.
+ – –1
We have seen that H (aq) + OH (aq)  H2O(l) rHº = – 57.1 kJ mol
For this reaction, Hrº = Hfº(H2O,l) – {Hfº(H+, aq) + Hfº(OH–,aq)}
+ – 0
Hence, at 25ºC, we get Hfº(H , aq) + Hfº(OH , aq) = Hfº(H2O, l) – Hr
– –1 –1
so  Hfº(OH ,aq) = {– 286.1 – (– 57.1)} kJ mol = – 229.00 kJ mol
 With the enthalpies of formation of these two ions, the enthalpy of formation of any other ion can be
found from the enthalpies of formation and solution of its pure compound with H+ or OH–. For example,
+
the enthalpy of formation of Na can be calculated from the enthalpy of formation and enthalpy of
infinite dilute solution of NaOH. The two values are :
 The chemical equation for the formation of infinite dilute solution of NaOH(s) is
NaOH(s) + nH2O()  Na+(aq) + OH¯(aq) aqH°(NaOH, s) = –44.50 kJ mol–1
 Since there are equal amounts of water on both sides of the above equation, the two enthalpies give no
net effect and thus
aqH°(NaOH, s) = fH°(Na+, aq) + fH°(OH¯, aq) – fH°(NaOH, s)
or fH° (Na+, aq) = aqH° (NaOH, s) – fH°(OH°, aq) + fH°(NaOH, s)
–1 –1
= [–44.50 – (–229.99) + (–425.61)] kJ mol = –240.12 kJ mol
 Similarly, from NaCl(aq) or HCl(aq), the enthalpy of formation of Cl¯(aq) can be determined, and so on.
The changes in enthalpy of any ionic reaction can then be found from these ionic enthalpies of
formation and the usual enthalpies of formation of compounds.

Ex-21. The enthalpy of formation of H2O(l) is –285 kJ mol–1 and enthalpy of neutralization of a strong acid and
a strong base is –55 kJ mol–1. What is the enthalpy of formation of OH– ions ?
Sol. Given that, H+(aq) + OH¯(aq)  H2O()
fH 0 –285 kJ mol–1
neutH = fH(H2O, ) – fH(OH¯, aq)
Hence fH (OH¯, aq) = fH(H2O, ) – neutH
= [–285 – (–55 )] kJ mol–1 = –230 kJ mol–1
Ex-22. Calculate the enthalpy change when one mole of HCl(g) is dissolved in a very large amount of water at
+
25°C. The change in state is : HCl(g) + aq  H (aq) + Cl¯(aq)
Given : fH (HCl, g) = – 92 kJ mol and fH° (Cl¯, aq) = – 167 kJ mol–1
–1

Sol. For the reaction, HCl(g) + aq  H+(aq) + Cl¯(aq)

We have H° = fH°(Cl¯,aq) – fH°(HCl, g)
H° = [–167 – (–92 )] kJ mol–1 = – 75 kJ mol–1

MISCELLANEOUS SOLVED EXAMPLES

1. Find (in terms of "a") the amount of energy required to raise the temperature of a substance from 3 K to
3
5 K. At low temperatures. CP = aT .
Sol. q =  nCp · dT =  naT 3 · dT
5
 T4  na
= na   = [(5)4 – (3)4]
 4 3 4

na  625 – 81
= = 136 na. Ans. q = 136 na.
4
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Thermodynamics & Thermodynamics

2. A thermally isolated vessel contains 100 g of water at 0°C. When air above the water is pumped out,
some of the water freezes and some evaporates at 0°C itself. Calculate the mass of the ice formed
6
such that no water is left in the vessel. Latent heat of vaporization of water at 0°C = 2.10 × 10 J/kg and
5
latent heat of fusion of ice = 3.36 × 10 J/kg.
Sol. Total mass of the water = M = 100 g
Latent heat of vaporization of water at 0°C
= L1 = 21.0 x 105 J/Kg
5
& Latent heat of fusion of ice = L2 = 3.36 x 10 J/Kg
Suppose, the mass of the ice formed = m
Then, the mass of water evaporated = M – m.
Heat lost by the water in freezing = Heat taken by water in evaporation.
Thus, mL2 = (M – m) L1 or m = 86 g. Ans. 86.2 g
3. Work done in expansion of an ideal gas from 4 litre to 6 litre against a constant external pressure of 2.1
atm was used to heat up 1 mole of water at 293 K. If specific heat of water is 4.2 J g–1 K–1, what is the
final temperature of water ?
Sol. W = – 2.1 [6 – 4] = – 2.1 × 2
= – 4.2 atm × lit.
= – 4.2 × 101. 325 J
This work is used to heat up the water
J
Specific heat of H2O = 4.2
gram · K.
Heat required for increasing temperature by 1°C of 1 mole = 4.2 × 18 = 75.6 J
4.2 × 101.325 = 75.6 [T – 293]
5.63 = T – 293
T = 298.63 K Ans. 298.63 K
4. 1 mole of ice at 0°C and 4.6 mm Hg pressure is converted to water vapour at a constant temperature
and pressure. Find H and E if the latent heat of fusion of ice is 80 cal/g and latent heat of
vaporisation of liquid water at 0°C is 596 cal/g and the volume of ice in comparison to that of water
(vapour) is neglected.
Sol. No. of mole = 1 mole
T = 273 K.
Pv = nRT.
4.6
v = 1 × 0.0821 × 273
760
v = 3699 lit [3700 lit]
latent heat of fusion = 80 cal/gram Latent heat of vaporisation = 596 cal/gram
 H = 80 × 18 + 596 × 18 = [80 + 596] × 18
 H = 12168 cal
 H = E + P [V2 – V1]
4.6
12168 = E + [3699] × 24.24
760
4.6
 E = 12168 – × 3699 × 24.24
760
= 12168 – 542.72 = 11625.28 cal. Ans. 12168 cal, 11625.28 cal

5. For Ag, CP (JK–1 mol–1) is given by 24 + 0.006 T. Calculate H if 3 mol of silver are raised from 27°C to
its melting point 927°C under 1 atm pressure.
T2 T2
1
Sol. H   nCp dT   3(24  .006T)dT = 3 [24 (T2–T1) + × 0.006 ( T22  T12 )]
T1 T1 2
= 3 × 25650 = 76950 J Ans. 76950 J

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Thermodynamics & Thermodynamics
6. Calculate the amount of heat evolved during the complete combustion of 100 ml of liquid benzene from
the following data.
(i) 18 g of graphite on complete combustion evolve 590 KJ heat
(ii) 15889 KJ heat is required to dissociate all the molecules of 1 litre water into H2 and O2.
(iii) The heat of formation of liquid benzene is 50 kJ/mol
(iv) Density of C6H6 () = 0.87 g/m
Sol. (i) C(s) + O2(g)  CO2(g) ; Hºf = – 393.33 KJ/mol
1
(ii) H2(g) + O2(g)  H2O () ; Hºf = – 286 KJ/mol
2
15
(iii) C6H6() + O2(g)  6CO2 (g) + 3H2O ()
2
 Hº = [6(–393.33) + 3 (–286)] – 50 = –3268 KJ/mole
 Heat evolved from 87 g benzene = 3645 KJ Ans. 3645 KJ
7. For the equations
C(diamond) + 2H2(g)  CH4(g) H1
C(g) + 4H(g) CH4(g) H2
Predict whether
(A) H1 = H2 (B) H1 > H2
(C) H1 < H2 (D) H1 = H2 + vapH(C) + dissH(H2)
Ans. (B)
8. The standard molar enthalpies of formation of cyclohexane (l) and benzene (l) at 25ºC are – 156 and +
49 KJ mol–1 respectively. The standard enthalpy of hydrogenation of cyclohexene (l) at 25º is –119 kJ
mol–1. Use these data to estimate the magnitude of the resonance energy of benzene.
Sol. Enthalpy of formation of 3 carbon-carbon double bonds
= HF ( ) –  Hf ( )
= –156 – (+ 49) kJ = –205 kJ.
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 mole–1 Ans. –152 kJ mole–1

9. Following graph shows a single stange expansion process, then P(atm)

workdone by the system is
(A) – 9104 J 5
(B) – 202.6 J
1
(C) – 506 J
(D) – 101.3 J 2 4 V(ltr)

Sol. Ans. (B)

1

V (Lit)
0 2 4
W = – Pext (V2 – V1) = – 1 × 2 × 101.325 J = – 202.6 J

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Thermodynamics & Thermodynamics
10. A sample of 2 kg of helium (assumed ideal) is taken through the
process ABC and another sample of 2 kg of the same gas is taken B C
through the process ADC. Then the temperature of the states A and B 10

P(10 N/m )
2
are (Given R = 8.3 joules/mol K) :
(A) TA = 120.5 K, TB = 120.5 K

4
(B) TA = 241 K, TB = 241 K 5 A D
(C) TA = 120.5 K, TB = 241 K
(D) TA = 241 K, TB = 482 K 10 3
20V(m )
0.5  105 2  1000
Sol. 5
× 10 × 103 = × 0.082 TA
1.01 10 2
1
= 0.082 TA
1.01
TA = 120.5 K
at constant volume
PA PB

TA TB
PB .TA 10
TB = = × 120.5 = 241 K. Ans. (C)
PA 5

11. In an isothermal expansion of a gaseous sample the correct relation is (consider w (work) with sign
according to new IUPAC convention)
[The reversible and irreversible processes are carried out between same initial and final states.]
(A) wrev > wirrev (B) wirrev > wrev (C) qrev < qirrev (D) can not be predicted
Ans. (B)

12. One mole of an ideal monoatomic gas is caused to go through the

cycle shown in figure. Then, the change in the internal energy in 2P0 c
expanding the gas from a to c along the path abc is :
(A) 3 P0V0 (B) 6 RT0
Pressure

(C) 4.5 RT0 (D) 10.5 RT0 T0

Sol. Pv = nRT at point C P0 b
a
2P0 × 4v 0 = 1 × RTC
 8P V  V0 4V0
TC =  0 0 
 R  Volume
at point a
P0V0 = 1 × RT0
P0 V0
T0 = ; TC = 8 T0
R
Change in internal energy = [nCVdT]
3 9
For path a to b = 1 × R × [3T0] = RT0
2 2
3
For path b to c = 1 × R × [4T0] = 6T0 R
2
9 21 RT0
Total change = RT0 + 6RT0 = = 10.5 RT0.
2 2
So total change in internal energy
U = 10.5 RT0 Ans. (D)
13. A certain mass of gas is expanded from (1L, 10 atm) to (4L, 5 atm) against a constant external pressure
of 1 atm. If initial temperature of gas is 300 K and the heat capacity of process is 50 J/°C. Then the
enthalpy change during the process is (1L atm ~ 100 J)
(A) H = 15 kJ (B) H = 15.7 kJ (C) H = 14.4 kJ (D) H = 14.7 kJ

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Sol. H = E + (PV) & E = q + W = (50 × 300 – 3 ×100) J [as Tf = 2 × 300 K = 600 K] = 14.7 kJ
H = 14700 + 10 × 100 = 15700 J = 15.7 kJ. Ans (B)
14. One mole of an ideal monoatomic gas expands isothermally against constant external pressure of 1
atm from initial volume of 1L to a state where its final pressure becomes equal to external pressure. If
initial temperature of gas is 300 K then total entropy change of system in the above process is :
–1 –1 –1 –1
[R = 0.082 L atm mol K = 8.3 J mol K ].
(A) 0 (B) Rn (24.6) (C) R n (2490) (D) 3/2 Rn (24.6)
V   Pi   300R 
Sol. S = nR n  f  = Rn   = R n  = Rn (24.6) Ans. (B)
 Vi   Pf   1 L  1 atm 
3
15. For a perfectly crystalline solid Cp.m. = aT , where a is constant. If Cp.m. is 0.42 J/K–mol at 10 K, molar
entropy at 10 K is :
(A) 0.42 J/K-mol (B) 0.14 J/K-mol (C) 4.2 J/K-mol (D) zero
Sol. 0.42 = a(10)3  a = 0.42 × 10–3
10 10
Cp.m. a 0.42
Sm =  dT =  aT 2  [103  0]   0.14 J / K  mol Ans. (B)
0 T 0 3 3

16. Given the following data :

Substance H° (kJ/mol) S°(J/mol K) G° (kJ/mol)
FeO(s) – 266.3 57.49 – 245.12
C (Graphite) 0 5.74 0
Fe(s) 0 27.28 0
CO(g) – 110.5 197.6 – 137.15
Determine at what temperature the following reaction is spontaneous ?
FeO(s) + C(Graphite)Fe(s) + CO(g)
(A) 298 K (B) 668 K (C) 966 K
(D) G° is +ve, hence the reaction will never be spontaneous
Sol. FeO(s) + C(graphite)  Fe(s) + CO(g)
(1) H = 0 + [– 110.5] – (– 266.3)
= –110.5 + 266.3
= + 155.8 kJ/mole
(2) S = 27.28 + 197.6 – 57.49 – 5.74 = 161.65 J/mole
(3) G = H – TS = 0 = 155.8 – T × 161.65 × 10–3
T × 161.65 × 10–3 = 155.8  T = 963.8 K Ans. (C)
+
17. If Hfº for Ag (infinitely diluted), NO3– –
(infinitely diluted), Cl (infinitely diluted) and AgCl(s) are 105.579,
–207.36, –167.159 and –127.068 respectively. Calculate the enthalpy change for the reaction
AgNO3(aq.) + HCl(aq.)  AgCl(s) + HNO3 (aq.)
(A) 21.471 KJ/mol (B) 145.688 KJ/mol (C) –65.488 KJ/mol (D) None
Sol. Hºreaction = [Hf (AgCl) + Hf (H+) + Hf(NO3¯)] – [Hºf (Ag+)] + Hºf (NO3¯) + Hºf (Cl¯) + Hºf (H+)]
= – 127.068 – [105.579 –167.159] = – 65.488 KJ / mol. Ans. (C)
18. What is the work done against the atmosphere when 25 grams of water vaporizes at 373 K against a
constant external pressure of 1 atm ? Assume that steam obeys perfect gas laws. Given that the molar
enthalpy of vaporization is 9.72 kcal/mole, what is the change of internal energy in the above process ?
(A) 1294.0 cal, 11247 cal (B) 921.4 cal, 11074 cal
(C) 1025.6 cal ; 12474.3 cal (D) 1129.3 cal, 10207 cal
Sol. Mole of H2O = 1.39
Pv = nRT
1 × v = 1.39 × 0.082 × 373  v = 42.51 lit
42.80  101.325
w = Pext. dv = 1 × [42.80] atm × lit. = 42.80 × 101.325 J = = 1025.6 cal
4.2
H = U + [Pv]. = 12470.6 cal.
U = H – Pv = 13500–1025.6 =12474.3 cal Ans. (C)

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THERMODYNAMICS Ist LAW

 Marked Questions may have for Revision Questions.

PART - I : SUBJECTIVE QUESTIONS

Section (A) : Basic definitions
A-1. Categorize these properties into state and path functions.
(a) Internal energy (b) Volume (c) Heat (d) Enthalpy
(e) Temperature (f) Work (g) Molar heat capacity
A-2. Categorize these properties into extensive and intensive
(a) Temperature (b) Internal energy (c) Heat (d) Density
(e) Molar volume (f) molar enthalpy (g) viscosity
A-3. Identify the state functions and path functions.
(a) The potential energy of a book in shelf.
(b) The heat evolved when a cube of sugar is oxidized to CO2(g) and H2O(g).
(c) The work accomplished in burning a litre of gasoline.

Section (B) : Thermodynamics processes & graph

Draw the P-V diagram for the following cyclic processes
B-1. Isothermal expansion from state A to B, isochoric pressure increment from B to C, isothermal
contraction from C to D, isobaric contraction from D  A.
B-2. Isobaric expansion from A  B, isochoric pressure increase from B  C, isobaric compression from
C  D, isochoric pressure drop from D  A.
B-3. Isobaric expansion from A  B, isochoric pressure drop from B  C, isothermal compression C  A.

Section (C) : Work calculation

C-1. Calculate the work done by 0.1 mole of a gas at 270 C to double its volume at constant pressure (in
isobaric process) (R = 2 cal mol–1 K–1)
C-2. Calculate the work done during isothermal reversible expansion of one mole ideal gas from 10 atm to 1
atm at 300 K.
C-3. At 25ºC, a 0.01 mole sample of a gas is compressed in volume from 4.0 L to 1.0 L at constant
temperature. What is work done for this process if the external pressure is 4.0 bar ?

Section (D) : Heat & Internal energy

D-1. Calculate the heat necessary to raise the temperature of 60 g of aluminimum from 35ºC to 55ºC. Molar
heat capacity of Al is 24 mole–1 K–1.
D-2. In a container, two mole of a diatomic ideal gas is allowed to expand against 1 atm pressure & volume
change from 2 litre to 5 litre isobarically then calculate change in internal enrgy.
Section (E) : First law of thermodynamics
E-1. The work done by a system is 8 joule, when 40 joule heat is supplied to it. What is the increase in
internal energy of system.
E-2. A gas expands from 2 L to 6 L against a constant pressure of 0.5 atm on absorbing 200 J of heat.
Calculate the change in internal energy.

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Thermodynamics & Thermodynamics
Section (F) : Adiabatic, isothermal, polytropic & free expansion processes
 5  7
F-1. One mole of an ideal monoatomic gas     is mixed with one mole of a diatomic gas     .
 3  5
( denotes the ratio of specific heat at constant pressure, to that at constant volume) find  for the
mixture ?
F-2. A piston freely move in a insulated cylinder from volume 5 lit to 10 lit then calculate work done & heat
during this expansion.
Section (G) : Enthalpy
G-1. If 1.0 kcal of heat is added to 1.2 L of O2 in a cylinder at constant pressure of 1 atm, the volume
increases to 1.5 L. Calculate U and H of the process. (1 L-atm = 100 J, 1 cal = 4.2 J)
G-2. 10 g of argon gas is compressed isothermally and reversibly at a temperature of 27ºC from 10 L to 5L.
–1 –1
Calculate enthalpy change. Assume ideal behaviour (H) for this process R = 2.0 cal K mol . log102 =
0.30 (Atomic mass of Ar = 40)

Section (H) : Phase transition

H-1. What is U when 2.0 mole of liquid water vaporises at 100ºC ? The heat of vaporisation (H vap.) of
water at 100ºC is 40.66 KJmol–1.

PART - II : ONLY ONE OPTION CORRECT TYPE

Section (A) : Basic definitions
A-1. 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
A-2. Out of boiling point (), entropy (), pH () and e.m.f. of a cell (V), intensive properties are :
(A) ,  (B) , ,  (C) , , V (D) All of the above
A-3. In which case bodies become hot due to mechanical energy losses
(i) Rub our hands for sometime (ii) Two vehicles collide with each other
(iii) Aeroplane crash (iv) Sliding of legs on roof surface
(v) Transfer of energy from hot body to cold body
(A) 5 (B) 4 (C) 3 (D) 2
A-4. Predict the total number of intensive properties :
(i) Free energy (ii) Critical density (iii) Viscosity (iv) Specific heat capacity
(v) molar heat capacity (vi) Kinetic energy (vii) Specific gravity (viii) Dielectric constant
(ix) pH
(A) 9 (B) 8 (C) 7 (D) 6
A-5. An ideal gas filled at pressure of 2 atm and temp of 300 K, in a balloon is kept in vacuum with in a large
insulated container. Wall of balloon is punctured then container temperature :
(A) Decreases (B) Increases (C) Remain constant (D) Unpredictable
Section (B) : Thermodynamics processes & graph
B-1. A gaseous system changes from state A (P1, V1, T1) to B (P2, V2, T2), B to C (P3, V3, T3) and finally from
C to A. The whole process may be called :
(A) Reversible process (B) Cyclic process (C) Isobaric process (D) Spontaneous process
B-2. A well stoppered thermos flask contains some ice cubes. This is an example of a-
(A) Closed system (B) Open system
(C) Isolated system (D) Non-thermodynamic system

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B-3. Five moles of a gas is put through a series of changes as shown graphicallay in a A B
cyclic process the A  B, B  C and C  A respectively are
(A) Isochoric, Isobaric, Isothermal

Volume
(B) Isobaric, Isochoric, Isothermal C
(C) Isothermal, Isobaric, Isochoric
(D) Isochoric, Isothermal, Isobaric
Temperature

B-4. A cyclic process ABCD is shown in P-V diagram for an ideal gas. Which of the diagram represent the
same process.

(A) (B) (C) (D)

B-5. The P–T graph as given below was observed for a process on an ideal gas,
which of the following statement is true.
(A) w = +ve, H = +ve
(B) w = –ve, H = – ve
(C) w = –ve, H = + ve
(D) w = +ve, H = –ve

Section (C) : Work Calculation

C-1. A thermodynamic system goes from states (i) P1, V to 2P1, V (ii) P, V1 to P, 2V1. Then work done in the
two cases is
(A) Zero, Zero (B) Zero, – PV1 (C) – PV1, Zero (D) –PV1, –P1V1
C-2. The work done in ergs for the reversible expansion of one mole of an ideal gas from a volume of 10
litres to 20 litres at 25ºC is :
7
(A) – 2.303 × 298 × 0.082 log2 (B) – 298 × 10 × 8.31 × 2.303 log2
(C) – 2.303 × 298 × 0.082 log0.5 (D) – 8.31 × 107 × 298 × 2.303 log0.5
C-3. An ideal gas is taken around the cycle ABCA as shown in P-V diagram. The
net work done by the gas during the cycle is equal to :
(A) 12P1V1
(B) 6P1V1
(C) 5P1V1
(D) P1V1

Section (D) : Heat & Internal energy

D-1. For freezing of liquid in a system :
(A) q = 0 (B) q > 0
(C) q < 0 (D) q > 0 or q < 0 (depending on the nature of liquid)
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D-2. For 2 mole of an ideal gas; the relation between Cp & Cv (non-molar) are :
(A) Cp – Cv = 2R (B) Cv – Cp = 2R (C) Cp – Cv = R (D) Cv – Cp = R
Section (E) : First law of thermodynamics
E-1. A system absorb 600J of heat and does work equivalent to 300J on its surroundings. The change in
internal energy is
(A) 300 J (B) 400 J (C) 500 J (D) 600 J
E-2. In an isochoric process the increase in internal energy is
(A) Equal to the heat absorbed (B) Equal to the heat evolved
(C) Equal to the work done (D) Equal to the sum of the heat absorbed and work done
E-3. In an isothermal expansion of an ideal gas. Select wrong statement :
(A) there is no change in the temperature of the gas
(B) there is no change in the internal energy of the gas
(C) the work done by the gas is equal to the heat supplied to the gas
(D) the work done by the gas is equal to the change in its internal energy
E-4. A system undergoes a process which absorbed 0.5 kJ of heat and undergoing an expansion against
external pressure of 1 atm, during the process change in internal energy is 300 J. Then predict the
change in volume (lit.)
(A) 1 (B) 2 (C) 3 (D) 4
E-5. When two moles of Hydrogen atoms join together to form a mole of hydrogen molecules in a closed
rigid vessel with diathermic walls.
H (g) + H (g)  H2 (g)
(A) w < 0 (B) U = negative (C) qsystem = positive (D) qsurrounding = negative
Section (F) : Adiabatic, isothermal, polytropic & free expansion processes
F-1. The temperature of the system decreases in an
(A) Adiabatic compression (B) Isothermal compression
(C) Isothermal expansion (D) Adiabatic expansion
F-2. 1 mole of NH3 gas at 27°C is expanded in reversible adiabatic condition to make volume 8 times ( =
1.33). Final temperature and work done respectively are :
(A) 150 K, 900 cal (B) 150 K, 400 cal (C) 250 K, 1000 cal (D) 200 K, 800 cal
F-3. In figure, A and B are two adiabatic curves for two different gases. Then A and B
corresponds to :
(A) Ar and He respectively
(B) He and H2 respectively
(C) O2 and H2 respectively
(D) H2 and He respectively

Section (G) : Enthalpy

G-1. One mole of non-ideal gas undergoes a change of state (1.0 atm, 3.0 L, 200 K) to (4.0 atm, 5.0 L, 250
K) with a change in internal energy (U) = 40 L-atm. The change in enthalpy of the process in L-atm ;
(A) 43 (B) 57 (C) 42 (D) None of these
G-2. For the isothermal expansion of an ideal gas
(A) U and H increases (B) U increases but H decreases
(C) H increases but U decreases (D) U and H are unaltered
G-3. A vessel contains 100 litres of a liquid X. Heat is supplied to the liquid in such a fashion that, Heat given
= change in enthalpy. The volume of the liquid increases by 2 litres. If the external pressure is one atm,
and 202.6 Joules of heat were supplied then, [U - total internal energy]
(A) U = 0 , H = 0 (B) U = + 202. 6J , H = + 202.6 J
(C) U = – 202.6J, H = – 202.6J (D) U = 0, H = + 202.6J
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Section (H) : Phase transition
H-1. H2O(s)  H2O()
This phase transition is carried out at constant temp and pressure then work done during the process :
(A) W < 0 (B) W > 0 (C) W = 0 (D) can’t detamined
H-2. At 1 atm pressure n mole of water (0ºC) is forzen to ice(0ºC) then heat transfer is :
(A) nHfusion (B) – n Hfusion (C) nCv, mT (D) Hfusion

PART - III : MATCH THE COLUMN

1. Match the column:
Columm-I Columm-II
V 
(A) Reversible isothermal expansion of an ideal gas (p) w = –2.303 nRT log  2 
 V1 

(B) Reversible adiabatic compression of an ideal gas (q) PV = constant
nR
(C) Irreversible adiabatic expansion of an ideal gas (r) w= (T2 – T1)
(   1)
(D) Irreversible isothermal compression of an ideal gas (s) H = 0
2. Match the column:
Column-I Column-II
(A) A process carried out infinitesimally slowly (p) Adiabatic
(B) A process in which no heat enters or leaves the system (q) E = 0, H = 0
(C) A process carried out at constant temperature (r) Reversible
(D) Cyclic process (s) Isothermal

PART - I : ONLY ONE OPTION CORRECT TYPE

1. In which one of the following sets, all the properties belong to same category (all extensive or all
intensive)?
(A) Mass, volume, pressure (B) Temperature, pressure, volume
(C) Heat capacity, density, entropy (D) Enthalpy, internal energy, volume.

2.

The plots between P and V which represent isochoric and isobaric process respectively :
(A) I, II (B) IV, I (C) I, IV (D) II, III
3. Match the enteries of column I with appropriate entries of column II and choose the correct option out of
the four options (A), (B), (C) and (D).
Column-I Column-II
(X) Isothermal (p) T = 0
(Y) Isobaric (q) V = 0
(Z) Adiabatic (r) P = 0
(W) Isochoric (s) q=0
(A) X–p, Y–q, Z-r, W-x (B) X–p, Y–r, Z-s, W-q (C) X–s, Y–p, Z-r, W-q (D) X–s, Y–p, Z-q, W-r
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4. Consider the cyclic process R  S R as shown in the Fig. You are told
that one of the path is adiabatic and the other one isothermal. Which one of
the following is(are) true?
(A) Process R  S is isothermal
(B) Process S  R is adiabatic
(C) Process R  S is adiabatic
(D) Such a graph is not possible

5. Work for the following process ABCD on a monoatomic gas is :

P
P0 A B

Isothermal

C
D

V0 2V0 4V0 V
(A) w = – 2 P0 V0 ln 2, (B) w = – 2 P0 V0 ln 4,
(C) w = – P0 V0 (1+ ln 2), (D) w = – P0 V0 ln 2,
6. 50 L of a certain liquid is confined in a piston system at the external pressure 100 atm. This pressure is
suddenly released and liquid is expanded against the constant atmospheric pressure, volume of the
liquid increases by 1 L and the final pressure on the liquid is 10 atm. Find the workdone.
(A) 1L.atm (B) 5 L.atm (C) 500 L.atm (D) 50 L.atm
7. Which one of the following equations does not correctly represent the first law of thermodynamics for
the given process in ideal gas ?
(A) Isothermal process : q = – w (B) Cyclic process : q = – w
(C) Adiabatic process : E = q (D) Expansion of a gas into vacuum : E = q

 5 
8. One mole of an ideal gas  Cv, m  R  at 300 K and 5 atm is expanded adiabatically to a final pressure
 2 
of 2 atm against a constant pressure of 2 atm. Final temperature of the gas is :
(A) 270 K (B) 273 K (C) 248.5 K (D) 200 K
9. The magnitudes of enthalpy changes for irreversible adiabatic expansion of a gas from 1L to 2L is H1
and for reversible adiabatic expansion for the same expansion is H2. Then
(A) H1 > H2
(B) H1 < H2
(C) H1 = H2, enthalpy being a state function (H1 = H2½
(D) H1 = E1 & H2 = E2 where E1 & E2 are magnitudes of change in internal energy of gas in
these expansions respectively.

PART - II : SINGLE AND DOUBLE VALUE INTEGER TYPE

1. How many statements are false ?
(i) Thermodynamics is concerned only with total energy of the system.
st
(ii) I law of thermodynamics can be applied on the individual particle enclosed in vessel.
(iii) Many thermodynamic properties can not be measured absolutely, so change in thermodynamic
property is required for calculation.
(iv) Feasibility of any chemical reaction can not be explained by thermodynamics.
(v) When surrounding is always in equilibrium with the system, the process called reversible.
(vi) Thermodynamics predict the time of attain the equilibrium.

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2. How many of the following physical properties are extensive :
(i) Free energy (ii) vapour pressure (iii) mole (iv) Kinetic energy
(v) Entropy (vi) Internal energy (vii) Enthalpy (viii) specific heat capacity
(ix) Coefficient of viscosity (x) Total heat capacity
3. How many of the following are state function :
(i) Internal energy (ii) Heat (iii) Enthalpy (iv) Entropy
(v) Pressure (vi) Temp. (vii) volume (viii) Work
(ix) specific heat capacity (x) molar heat capacity
4. Two moles of He gas (= 5/3) are initially at temp 27ºC and occupy a volume of 20 litres. The gas is
first expanded at constant pressure until its volume is doubled. Then it undergoes reversible adiabatic
change, until the volume become 110 lit, then predict the value of T/100 (where T is the final
2/3
 4 1
temperature,   = )
 11  2
3 3 3
5. A sample of an ideal gas is expanded from 1dm to 3 dm in a reversible process for which P = KV ,
with K = 1/5 (atm/dm3), what is work done by gas (L atm).
6. The valve on a cylinder containing initially 1 liters of an ideal gas at 7 atm and 25ºC is opened to the
atmosphere, Whose the pressure is 760 torr and the temperature is 25ºC. Assuming that the process is
isothermal, how much work (in L.atm) is done on the atmosphere by the action of expansion ?
7. The work done (in Cal) in adiabatic compression of 2 mole of an ideal monoatomic gas by constant
external pressure of 2 atm starting from intial pressure of 1 atm and initial temperature of 30 K (R = 2
cal/mol-degree)
8. One mole of a non-ideal gas undergoes a change of state (2.0 atm, 3.0 L, 95 K)  (4.0 atm, 5.0 L,
245 K) with a change in internal energy, U=30.0 L. atm. Calculate change in enthalpy of the process
in L. atm.

PART - III : ONE OR MORE THAN ONE OPTIONS CORRECT TYPE

1. Which of the following properties of a system are intensive ?
(A) color (B) kinetic energy per mole
(C) X (where X = U + H) (D) specific volume (volume per unit mass)
2. Choose the correct statement :
(A) system and surrounding are always separated by a real or imaginary boundary.
(B) perfectly isolated system can never be created.
(C) in reversible process, energy change in each step can be reversed.
(D) irreversible process is also called quasi-equilibrium state.
3. In an isothermal expansion of a gaseous sample, the correct relation is : (consider w (work) with sign
according to new IUPAC convention)
[The reversible and irreversible processes are carried out between same initial and final states.]
(A) wrev > wirrev (B) wirrev > wrev (C) qrev < qirrev (D) Erev = Eirrev
4. During the isothermal expansion of an ideal gas :
(A) The internal energy remains unaffected (B) The temperature remains constant
(C) The enthalpy remains unaffected (D) The enthalpy increases

5. P-V plot for two gases (assuming ideal) during adiabatic processes are given
in the figure. Plot A and plot B should correspond respectively to :
(A) He and H2
(B) H2 and He
(C) SO3and CO2
(D) N2 and Ar

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6. An ideal gas undergoes adiabatic expansion against constant external pressure. Which of the following
is incorrect :
(A) Temperature of the system decreases.
(B) The relation PV = constant will be valid (where P and V are gas variables)
(C) E + PextV = 0
(D) Enthalpy of the gas remains unchanged.
7. For the sublimation of a solid at 1 atm, which of the following may be correct
(A) U > 0 at low temperature (B) q > 0
(C) U < 0 at high temperature (D) H > 0

PART - IV : COMPREHENSION
Read the following passage carefully and answer the questions.
Comprehension #
When a system is taken from state A to state B along path ACB as shown in figure below, 80 J of heat
flows into the system and the system does 30 J of work.

C B
P
A D
V
1. How much heat flows into the system along path ADB if the work done by the system is 10 J :
(A) 40 J (B) 60 J (C) 80 J (D) 100 J
2. When the system is returned from state B to A along the curved path, the work done on the system is
20 J. Does the system absorb or liberate heat and by how much ?
(A) –70 J ; heat is liberated. (B) –60 J ; heat is liberated.
(C) +70 J ; heat is absorbed. (D) +60 J ; heat is absorbed.
3. If ED – EA = +40J, the heat absorbed in the processes AD and DB are respectively :
(A) qAD = 30 J and qDB = –90 J (B) qAD = +60 J and qDB = 0 J
(C) qAD = –30 J and qDB = 90 J (D) qAD = +50 J and qDB = 10 J

* Marked Questions may have more than one correct option.

PART - I : JEE (ADVANCED) / IIT-JEE PROBLEMS (PREVIOUS YEARS)
1. The given reaction
2CO + O2  2CO2 H = – 560 kJ
2moles 1 mole
is carried out in one litre container, if the pressure in the container gets changes from 70 atm to 40 atm
as reaction gets completed. Calculate U of the reaction. [1L atm = 0.1 kJ] [JEE 2006, 6/184]
2.* Among the following, the state function(s) is(are) : [JEE 2009, 4/160]
(A) Internal energy (B) Irreversible expansion work
(C) Reversible expansion work (D) Molar enthalpy
3.* Among the following, the intensive property is (properties are) : [JEE 2010, 3/163]
(A) molar conductivity (B) electromotive force
(C) resistance (D) heat capacity

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4. One mole of an ideal gas is taken from a and b along two paths denoted by the solid and the dashed
lines as shown in the graph below. If the work done along the solid line path is ws and that along the
dotted line path is wd, then the integer closest to the ratio wd / ws is : [JEE 2010, 3/163]

5.* The reversible expansion of an ideal gas under adiabatic and

isothermal conditions is shown in the figure. Which of the following
statement(s) is (are) correct ? [JEE 2012, 4/136]
(A) T1 = T2
(B) T3 > T1
(C) wisothermal > wadiabatic
(D) Uisothermal > Uadiabatic

6.* An ideal gas in a thermally insulated vessel at internal pressure = P1, volume = V1 and absolute
temperature = T1 expands irreversibly against zero external pressure, as shown in the diagram. The
final internal pressure, volume and absolute temperature of the gas are P2, V2 and T2, respectively. For
this expansion, [JEE(Advanced) 2014, 3/120]

(A) q = 0 (B) T2 = T1 (C) P2V2 = P1V1 (D) P2 V2 = P1V1

7.* An ideal gas is expanded from (p1, V1, T1) to (p2, V2, T2) under different conditions. The correct
statement(s) among the following is (are) [JEE(Advanced) 2017, 4/122]
(A) The work done by the gas is less when it is expanded reversibly from V1 to V2 under adiabatic
conditions as compared to that when expanded reversibly from V1 to V2 under isothermal conditions
(B) The change in internal energy of the gas is (i) zero, if it is expanded reversibly with T1 = T2, and (ii)
positive, if it is expanded reversibly under adiabatic conditions with T1  T2
(C) If the expansion is carried out freely, it is simultaneously both isothermal as well as adiabatic
(D) The work done on the gas is maximum when it is compressed irreversibly from (p2, V2) to (p1, V1)
against constant pressure p1

PART - II : JEE (MAIN) / AIEEE PROBLEMS (PREVIOUS YEARS)

1. Assuming that water vapour is an ideal gas, the internal energy change (U) when 1 mol of water is
vapourised at 1 bar pressure and 100°C, (Given : Molar enthalpy of vapourization of water at 1 bar and
–1 –1 –1
373 K=41 kJmol and R = 8.3 J mol K ) will be : [AIEEE 2007, 3/120]
–1
(1) 37.904 kJ mol (2) 41.00 kJ mol–1 (3) 4.100 kJ mol–1 (4) 3.7904 mol–1
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2. A piston filled with 0.04 mol of an ideal gas expands reversibly from 50.0 mL to 375 mL at a constant
temperature of 37.0ºC. As it does so, it absorbs 208 J of heat. The values of q and w for the process
will be: (R = 8.314 J/mol K) (ln 7.5 = 2.01) [JEE 2013, (Main), 4/120]
(R = 8.314 J/mol K) (ln 7.5 = 2.01)
(1) q = +208 J, w = – 208 J (2) q = –208 J, w = – 208 J
(3) q = –208 J, w = + 208 J (4) q = +208 J, w = + 208 J
3. U equal to : [JEE(Main) 2017, 4/120]
(1) Isobaric work (2) Adiabatic work (3) Isothermal work (4) Isochoric work

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EXERCISE - 1
PART - I
A-1. State function : (a) (b) (d) (e) ; Path function : (c) (f) (g)
A-2. Extensive Property : (b) (c) ; Intensive Property : (a) (d) (e) (f) (g)
A-3. (a) Potential energy is state function.
(b) Heat is a path function because a part of it may be used in work.
(c) Work is not a state function.

B-1. B-2. B-3.

C-1. 60 cal. C-2. – 5744.4 J C-3. 1.2 × 103 J D-1. 1.066 kJ

3
D-2. 760 J E-1. 32 J E-2. – 2.6 J F-1.
2
F-2. W=0;q=0 G-1. U = 4170 J, H = 1 kcal G-2. Zero H-1. U = 75.12 kJ

PART - II
A-1. (C) A-2. (C) A-3. (B) A-4. (C) A-5. (C)
B-1. (B) B-2. (C) B-3. (A) B-4. (C) B-5. (C)
C-1. (B) C-2. (B) C-3. (C) D-1. (C) D-2. (A)
E-1. (A) E-2. (A) E-3. (D) E-4. (B) E-5. (B)
F-1. (D) F-2. (A) F-3. (B) G-1. (B) G-2. (D)
G-3. (D) H-1. (B) H-2. (B)
PART – III
1. (A – p, s) ; (B – q, r) ; (C – r) ; (D – s) 2. (A – r) ; (B – p) ; (C – s) ; (D – q)

EXERCISE – 2
PART - I
1. (D) 2. (B) 3. (B) 4. (D) 5. (A)
6. (A) 7. (C) 8. (C) 9. (B)
PART – II
1. 4 (i, ii, iv, vi) 2. 7 (i, iii, iv, v, vi, vii, x) 3. 6 (i, iii, iv, v, vi, vii)
4. 3 5. 4 6. 6 7. 72 8. 44

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PART - III
1. (ABD) 2. (ABC) 3. (BD) 4. (ABC) 5. (BCD)
6. (BD) 7. (ABCD)

PART – IV
1. (B) 2. (A) 3. (D)

EXERCISE – 3
PART – I
1. H = U + (PV)
so, U = H – (PV) = – 560 – [40 – 70] (L atm) = (– 560 + 30 × 0.1) kJ = – 557 kJ.
2. (AD) 3. (AB) 4. 2 5. (AD) 6. (ABC)
7. (ACD)

PART – II
1. (1) 2. (1) 3. (2)

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THERMODYNAMICS IInd & IIIrd LAW

PART - I : SUBJECTIVE QUESTIONS

Section (A) : Introduction about entropy
A-1. The entropy of a gas increases on its expansion. Why ?
A-2. Entropy of the solutions is higher than that of pure liquid. Why ?
A-3. What are the signs of S for the system and for the surrounding in each of the following processes ?
(a) Water boils in a teakettle on a hot stove.
(b) Ice in an ice cube tray, left an a table melts.
(c) A cup of coffee is reheated in a microwave oven.
A-4. State the second law of thermodynamics.
rd
A-5. Write statement of III law of thermodynamics ?
A-6. State the thermodynamic condition of spontaneous occurance of a process ?
A-7. If H for a reaction has a positive value, how would you know the sign requirement of S for it so that
the reaction is spontaneous ?
Section (B) : Entropy Calculation
B-1. The entropy of vaporization of benzene is 85 JK–1 mol–1. When 117 g benzene vaporizes at it’s normal
boiling point, calculate the entropy change of surrounding.
B-2. Calculate standard entropy change in the reaction
Fe2O3 (s) + 3H2 (g)  2Fe (s) + 3H2O ()
Given : Sºm(Fe2O3, S) = 87.4 , Sºm(Fe, S) = 27.3, Sºm(H2, g) = 130.7, Sºm(H2O, ) = 69.9 JK–1 mol–1.

B-3. One mole of liquid iron at its boiling point was vaporized in an oven at 3500 K. If iron boils at 3133 K
and enthalpy of vaporization is 349 KJ mol–1, determine Ssystem, Ssurrounding and Suniverse.(Oven is
considered as surroundings).

B-4. Calculate the entropy change in surroundings when 1.00 mol of H2O() is formed under standard
–1
conditions at 298 K. Given rHº = – 286 kJ mol .
B-5. Order of increasing of entropy among given condition of substance is :
(I) 1 mole of H2O(l) at 298 K and 0.101 M Pa (II) 1 mole of ice at 273 K and 0.101 M Pa
(III) 1 mole of H2(g) at 298 K and 1 atm (IV) 1 mole of C2H6(g) at 298 K and 1 atm
B-6. Oxygen & ozone are gases at standard temperature. Their molar entropies are in the sequence O2 <
O3. Using molecular properties, explain why ozone is more disordered than oxygen.

Section (C) : Free energy

C-1. What will be the states of a chemical reaction occuring at constant pressure and temperature conditions
when :
(i) G = 0 (ii) G > 0 (iii) G < 0
C-2. A gaseous reactant A forms two different product, in parallel reaction, B and C as follows :
A  B; Hº = –3kJ, Sº = 20JK–1 ; A  C; Hº = –3.6 kJ, Sº = 10 JK–1
Discuss the relative stability of B and C on the basis of Gibb’s free energy change at 27ºC.

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C-3. With the following informations, determine standard Gibb’s free energy of formation of N2O4(g).
1 1
N2(g) + O2(g)  NO(g) Gº = 86.6 kJ .....(i)
2 2
1
NO(g) + O2(g)  NO2(g) Gº = –34.82 kJ .....(ii)
2
2NO2(g)  N2O4(g) Gº = –5.77 kJ .....(iii)
C-4. For the equilibrium : PCl5(g) PCl3(g) + Cl2(g) at 298 K, equilibrium constant, K = 1.8 × 10–7. What
is G0for the reaction ?

PART - II : ONLY ONE OPTION CORRECT TYPE

Section (A) : Introduction about entropy
A-1. In which state, matter have highest entropy
(A) Solid (B) Liquid (C) Gas (D) Equal in all
A-2. Predict which of the following reaction (s) has a positive entropy change ?
I. Ag+(aq) + Cl–(aq)  AgCl(s)
II. NH4Cl(s)  NH3(g) + HCl(g)
III. 2NH3(g)  N2(g) + 3H2(g)
(A) I and II (B) III (C) II and III (D) II
A-3. Mixing of non-reacting ideal gases is generally accompanied by
(A) Decrease in entropy (B) Increase in entropy
(C) Change in enthalpy (D) Increase in free energy
A-4. Which of the following reactions is associated with the most negative change in entropy ?
(A) 2SO2(g) + O2(g)  2SO3(g) (B) C2H4(g) + H2(g) C2H6(g)
(C) C(s, graphite) + O2  CO2(g) (D) 3C2H2(g)  C6H6(  )

A-5. For the gas - phase decomposition, PCl5(g) PCl3(g) + Cl2(g) :

(A) H < 0, S < 0 (B) H > 0, S > 0 (C) H > 0, S < 0 (D) H < 0, S > 0
A-6. Which one of the following has Sº greater than zero.
(A) CaO (s) + CO2(g) CaCO3 (s) (B) NaCl (aq) NaCl (s)
+ –
(C) NaNO3(s) Na (aq) + NO3 (aq) (D) N2 (g) + 3H2 (g) 2NH3 (g)

A-7. For which reaction from the following, will be maximum entropy change :
1
(A) Ca(s)  O 2 (g)  CaO(s) (B) CaCO3 (s)  CaO(s)  CO 2 (g)
2
(C) C(s)  O2 (g)  CO2 (g) (D) N2 (g)  O2 (g)  2NO(g)

A-8. Which of the following statement is true. The entropy of the universe
(A) Increases and tends towards maximum value
(B) Decreases and tends to be zero
(C) Remains constant
(D) Decreases and increases with a periodic rate

Section (B) : Entropy Calculation

B-1. An isolated system comprises the liquid in equilibrium with vapours. At this stage the molar entropy of
the vapour is :
(A) Less than that of liquid (B) more than that of liquid
(C) Equal to zero (D) Equal to that of liquid

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 5 
B-2. When two mole of an ideal gas  Cp,m  R  heated from 300 K to 600 K at constant pressure. The
 2 
change in entropy of gas (S) is :
3 3 5
(A) R ln 2 (B) – R ln 2 (C) 5R ln 2 (D) R ln 2
2 2 2
B-3. The entropy change when two moles of ideal monoatomic gas is heated from 200 to 300ºC reversibly
and isochorically ?
3  300  5  573   573  3  573 
(A) R ln   (B) R ln   (C) 3R ln   (D) R ln  
2  200  2  273   473  2  473 

 5 
B-4. If one mole of an ideal gas  Cp,m  R  is expanded isothermally at 300 K until it’s volume is tripled,
 2 
then change in entropy of gas is :
5
(A) zero (B) infinity (C) R ln 3 (D) R ln 3
2
B-5. Calculate the total entropy change for the transition at 368 K of 1 mol of sulphur from the monoclinic to
the rhombic solid state and H = – 401.7 J mol–1 for the transition. Assume the surroundings to be an
ice-water bath at 0ºC :
–1 –1 –1
(A) – 1.09 JK (B) 1.47 JK (C) 0.38 JK (D) None of these
Section (C) : Free energy
C-1. Which of the follwing is incorrect regarding Gibbs free energy
(A) it is a state function (B) it is extensive property
(C) it is macroscopic property (D) it is intensive property
C-2. Which of the following conditions regarding a chemical process ensures its spontaneity at all
temperature ?
(A) H > 0, S < 0 (B) H < 0, S > 0 (C) H < 0, S < 0 (D) H > 0, S < 0
C-3. When reaction in standard state is at equilibrium, then :
(A) Hº = 0 (B) Sº = 0
(C) equilibrium constant K = 0 (D) equilibrium constant K = 1
C-4. What is the free energy change (G) when 1.0 mole of water at 100ºC and 1 atm pressure is converted
into steam at 100ºC and 1 atm pressure ?
(A) 80 cal (B) 540 cal (C) 620 cal (D) Zero
C-5. A reaction has H = – 33 kJ and S = – 58 J/K. This reaction would be :
(A) spontaneous at all temperatures (B) non-spontaneous at all temperatures
(C) spontaneous above a certain temperature (D) spontaneous below a certain temperature
C-6. For a reaction A(g) B(g) at equilibrium. The partial pressure of B is found to be one fourth of the
partial pressure of A. The value of G° of the reaction A  B is
(A) RT n 4 (B) – RT n 4 (C) RT log 4 (D) – RT log 4

3
C-7. If Gº = – 177 K cal for (1) 2 Fe(s) +
O2 (g)  Fe2O3 (s)
2
and Gº = – 19 K cal for (2) 4 Fe2O3 (s) + Fe(s) 3 Fe3O4 (s)
What is the Gibbs free energy of formation of Fe3O4(s) ?
(A) + 229.6 kcal/mol (B) – 242.3 kcal/mol (C) – 727 kcal/mol (D) – 229.6 kcal/mol
–1
C-8. For a paticular reaction H° = – 76.6 KJ and S° = 226 JK . This reaction is :
(A) Spontaneous at all temperatures (B) Non spontaneous at all temperatures
(C) Spontaneous at temperature below 66°C (D) Spontaneous at temperature above 66°C

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PART - III : MATCH THE COLUMN

1. Match the column:
Columm-I Columm-II
(A) (Gsystem)T,P = 0 (p) Process is in equilibrium
(B) Ssystem + Ssurrounding > 0 (q) Process is nonspontaneous
(C) Ssystem + S surrounding < 0 (r) Process is spontaneous
(D) (Gsystem)T,P > 0 (s) System is unable to do useful work
2. Match the column :
Columm-I Columm-II
(A) Reversible adiabatic compression (p) Ssystem > 0
(B) Reversible vaporisation of liquid (q) Ssystem < 0
(C) 2N(g) N2(g) (r) Ssurrounding < 0
(D) MgCO3(s)  
 MgO(s) + CO2(g) (s) Ssurrounding = 0

PART - I : ONLY ONE OPTION CORRECT TYPE

1. Which of the following option the first compound has less entropy than second :
(A) (i) aqueous solution of 1 M of MgCl2 (ii) aqueous solution of 1 M of NaCl
(B) (i) Br2 liquid at 25ºC (ii) Br2 liquid at 20ºC
(C) (i) HgO solid (ii) HgS solid
(D) (i) Br2 liquid (ii) I2 solid
2. Isentropic process is
(A) adiabatic and irreversible process (B) isothermal and reversible process
(C) adiabatic and reversible process (D) isothermal and reversible for which Q = 0
3. Third law of thermodynamics states that :
(A) the entropy of a perfectly crystalline pure substance at zero K is zero.
(B) absolute entropy of hydrogen ion is zero at zero K.
(C) net change in entropy in coverssion H2(g) (130 K)  H2(g) (200K) is zero.
(D) entropy generally decrease in combustion reactions.
4. Select correct statements :
S1 : For every chemical reaction at equilibrium, standard gibbs energy of reaction is zero
S2 : At constant temperature and pressure, chemical reactions are spontaneous in the direction of
decreasing gibbs energy.
S3 : Spontaneity is related to change in entropy of universe.
(A) S1 S2 S3 (B) only S1 (C) S2, S3 (D) S1, S3

PART - II : SINGLE AND DOUBLE VALUE INTEGER TYPE

1. The equilibrium constant for a reaction is 10. What will be the magnitude value of Gº ?
R = 8.31 JK–1 mol–1, T = 314 K. (Approximate integer value in KJ mol–1)
2. For the reaction at 298 K
A (g) + B (g) C (g) + D (g)
If Hº = – 29.8 Kcal and Sº = – 0.1 Kcal K–1 then calculate equilibrium constant (K) :
–1
3. Calculate the magnitude of free energy in KJ mol when 1 mole of an ionic salt MX (s) is dissolved in
water at 27°C. Given
Lattice energy of MX = 780 kJ mol–1
Hydration energy of MX = – 775.0 kJ mol–1
Entropy change of dissolution at 27°C = 40 J mol–1 K–1
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4. For the formation of C (g) at 300 K.
A (g) + 3 B (g)  2C (g)
Calculate the magnitude of Gº (Kcal) if given data :
A B C
-1
Hfº (Kcal mol ) 0 0 –10
–1 -1
Sfº (Cal K mol ) 40 30 45
–1 –1
5. The entropies of H2(g) and H(g) are 60 and 50 J mole K respectively at 300 K. Using the data given
below calculate the bond enthalpy of H2 (g) in Kcal mole–1.
H2 (g)  2H (g) ; Gº = 21.6 KJ mole–1
6. The free energy change for a reaction is –213.3 kJ mol–1 at 25ºC. If the enthalpy change of the reaction
–1 –1
is –217.77 kJ mole . Calculate the magnitude of entropy change for the reaction in Joule mole .
7. Calculate the magnitude of standard entropy change for reaction X Y if Hº = 25 KJ and Keq is
10–7 at 300 K.
8. Calculate the magnitude of standard free energy of formation of ammonium chloride at 25ºC
(approximate integer in Kcal mol–1), the equation showing the formation of NH4Cl from its elements is
½N2(g) + 2H2(g) + ½Cl2(g)  NH4Cl(s)
For NH4Cl, Hºf is – 313 kJ mol–1, Also given that
SN0 2  191.5 JK 1 mol1 SH0 2  130.6 JK 1 mol1
S0Cl2  223.0J K 1 mol1 0
SNH4 Cl
 94.6 JK 1 mol1

1 3
9. For the reaction N2(g) + H2(g)NH3(g) ; H = – 30 kJ to be at equilibrium at 477ºC. If standard
2 2
entropy of N2 (g) and NH3 (g) are 60 and 50 J mole–1 K–1 respectively then calculate the standard
entropy of H2(g) in Jmole–1K–1.

PART - III : ONE OR MORE THAN ONE OPTIONS CORRECT TYPE

1. In which of the following entropy increases :
(A) Fe(s) + O2(g)  Fe2O3(s). (B) Melting of ice
(C) Crystallisation of sugar from solution (D) Vaporisation of camphor
2. When a liquid solidifies, generally, there is :
(A) Decrease in enthalpy (B) Decrease in entropy
(C) Increase in enthalpy (D) Increase in entropy
3. Which of the following is false about molar entropy ?
(A) It is same for all type of gases
(B) For the gas of comparable mass. It decreases with the increase in atomicity.
(C) Under identical condition, it is greater for heavier gas.
(D) For ideal gas of comparable molar mass it decreases with the increase in thermo molecular
attractions.
4. Which of the following statements is/are correct.
(A) Reversible adiabatic process is iso entropic process
(B) Ssystem for irreversible adiabatic compression is greater than zero
(C) Ssystem for free expension in zero
(D) Ssurrounding for irreversible isothermal compression is greater than zero
5. The normal boiling point of a liquid `X` is 400 K. Which of the following statement is true about the
process X(l)  X(g)?
(A) at 400 K and 1 atm pressure G = 0 (B) at 400 K and 2 atm pressure G = + ve
(C) at 400 K and 0.1 atm presure G = – ve (D) at 410 K and 1 atm pressure G = + ve

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6. For isothermal expansion in case of an ideal gas :
(A) H = 0 (B) E = 0 (C) G = –T.S (D) Tfinal = Tinitial

PART - IV : COMPREHENSION
Read the following passage carefully and answer the questions.
Comperhension # 1
Entropy is a state function and its value depends on two or three variables temperature (T), Pressure
(P) and volume (V). Entropy change for an ideal gas having number of moles (n) can be determined by
the following equation.
T  V 
 S = 2.303 nCV log  2  + 2.303 nR log  2 
 T1   V1 
T  P 
S = 2.303 nCp log  2  + 2.303 nR log  1 
 T1   P2 
Since free energy change for a process or a chemical equation is a deciding factor of spontaneity,
which can be obtained by using entropy change (S) according to the expression, G = H – TS at a
temperature T.
1. What would be the entropy change involved in thermodynamic expansion of 2 moles of a gas from a
volume of 5 L to a volume of 50 L at 25°C [Given R = 8.3 J/mole – K]
(A) 38.23 J/K (B) 26.76 J/K (C) 20J/K (D) 28.23J/K
2. An isobaric process having one mole of ideal gas has entropy change 23.03 J/K for the temperature
range 27°C to 327°C. What would be the molar specific heat capacity (CV) ?
10 10
(A) J/K mol (B) – 8.3 J/ K mol
log2 log2
(C) 10 × log2 J/K mol (D) 10 log2 + 8.3 J/K mol
1
3. For a reaction M2O(s)  2M(s) + O2(g); H = 30 kJ/mol and S = 0.07 kJ/K-mol at 1 atm. Calculate
2
upto which temperature the reaction would not be spontaneous.
(A) T > 428.6 K (B) T > 300.8 K (C) T < 300.8 K (D) T < 428.6 K
Comprehension # 2
Dependence of spontaneity on temperature :
For a process to be spontaneous, at constant temperature and pressure, there must be decrease in
free energy of the system in the direction of the process, i.e. GP, T < 0. GP, T = 0 implies the
equilibrium condition and GP, T > 0 corresponds to non-spontaneity.
Gibbs-Helmholtz equation relates the free energy change to the enthalpy and entropy changes of the
process as : G P,T = H – TS ...(1)
The magnitude of H does not change much with the change in temperature but the entropy factor TS
changes appreciably. Thus, spontaneity of a process depends very much on temperature.
For endothermic process, both H and S are positive. The energy factor, the first factor of equation,
opposes the spontaneity whereas entropy factor favours it. At low temperature the favourable factor
TS will be small and may be less than H, G will have positive value indicating the nonspontaneity of
the process. On raising temperature, the factor TS increases appreciably and when it exceeds H, G
would become negative and the process would be spontaneous.
For an exothermic process, both H and S would be negative. In this case the first factor of
eq. 1 favours the spontaneity whereas the second factor opposes it. At high temperature, when TS >
H, G will have positive value, showing thereby the non-spontaneity of the process. However, on
decreasing temperature, the factor TS decreases rapidly and when TS < H, G becomes negative
and the process occurs spontaneously. Thus, an exothermic process may be spontaneous at low
temperature and non-spontaneous at high temperature.
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4. When CaCO3 is heated to a high temperature, it undergoes decomposition into CaO and CO2 whereas
it is quite stable at room temperature. The most likely explanation of it, is
(A) The enthalpy of reaction (H) overweighs the term TS at high temperature.
(B) The term TS overweighs the enthalpy of reaction at high temperature.
(C) At high temperature, both enthalpy of reaction and entropy change become negative.
(D) None of these.

5. For the reaction at 25°C, X2O4()  2XO2(g)

–1
H = 2.1 Kcal and S = 20 cal K . The reaction would be
(A) spontaneous (B) non-spontaneous (C) at equilibrium (D) unpredictable
6. For the reaction at 298 K, 2A + B C
H = 100 kcal and S = 0.050 kcal K–1. If H and S are assumed to be constant over the temperature
range, above what temperature will the reaction become spontaneous ?
(A) 1000 K (B) 1500 K (C) 2000 K (D) 2500 K
7. A reaction has a value of H = – 40 kcal at 400K. Above 400 K, the reaction is spontaneous, below this
temperature, it is not. The values of G and S at 400 K are respectively.
(A) 0, – 0.1 cal K–1 (B) 0,100 cal K–1
–1
(C) – 10 kcal, – 100 cal K (D) 0, – 100 cal K–1
8. The enthalpy change for a certain reaction at 300 K is – 15.0 K cal mol–1. The entropy change under
–1 –1
these conditions is – 7.2 cal K mol . The free energy change for the reaction and its
spontaneous/non-spontaneous character will be
(A) – 12.84 kcal mol–1, spontaneous (B) 12.84 kcal mol–1, non-spontaneous
–1
(C) – 17.16 kcal mol , spontaneous (D) None of these

* Marked Questions may have more than one correct option.

PART - I : JEE (ADVANCED) / IIT-JEE PROBLEMS (PREVIOUS YEARS)
1. The direct conversion of A to B is difficult, hence it is carried out by the following shown path:

S(A  C) = 50 ; S(C  D) = 30; S(B D) = + 20

The entropy change for the process A B is [JEE 2006, 3/184]
(A) 100 (B) – 60 (C) – 100 (D) + 60
6
2. N2 + 3H2 2 NH3 K = 4 × 10 at 298
K = 41 at 400 K
Which statements is correct ? [JEE 2006, 3/184]
(A) If N2 is added at equlibrium condition, the equilibrium will shift to the forward direction because
according to IInd law of thermodynamics the entropy must increases in the direction of spontaneous
reaction.
(B) The condition for equilibrium is 2GNH3 = 3GH2 + GN2 where G is Gibbs free energy per mole of the
gaseous species measured at that partial pressure.
(C) Addition of catalyst does not change Kp but changes H.
(D) At 400 K addition of catalyst will increase forward reaction by 2 times while reverse reaction rate will
be changed by 1.7 times.
3. The value of log10K for a reaction A B is :
(Given : rHº298 K = –54.07 kJ mol , rSº298 K = 10 JK–1 mol–1 and R = 8.314 JK–1 mol–1 ; 2.303 × 8.314 ×
–1

298 = 5705) [JEE 2007, 3/162]

(A) 5 (B) 10 (C) 95 (D) 100
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4. For the process H2O() (1 bar, 373 K)  H2O(g) (1 bar, 373 K), the correct set of thermodynamic
parameters is : [JEE 2007, 3/162]
(A) G = 0, S = +ve (B) G = 0, S = –ve (C) G = +ve, S = 0 (D) G = –ve, S = +ve

5. Statement-1 : For every chemical reaction at equilibrium, standard Gibbs energy of reaction is zero.
Statement-2 : At constant temperature and pressure, chemical reactions are spontaneous in the
direction of decreasing Gibbs energy. [JEE 2008, 3/163]
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True

6. Statement-1 : There is a natural asymmetry between converting work to heat and converting heat to
work.
Statement-2 : No process is possible in which the sole result is the absorption of heat form a reservoir
and its complete conversion into work. [JEE 2008, 3/163]
(A) Statement-1 is True, Statement-2 is True; Statement-2 is a correct explanation for Statement-1.
(B) Statement-1 is True, Statement-2 is True; Statement-2 is NOT a correct explanation for Statement-1
(C) Statement-1 is True, Statement-2 is False
(D) Statement-1 is False, Statement-2 is True
7.* For an ideal gas, consider only P-V work in going from an initial state X to
the final state Z. The final state Z can be reached by either of the two paths
shown in the figure. Which of the following choice(s) is (are) correct? [take
S as change in entropy and w as work done]. [JEE 2012, 4/136]
(A) Sxz =Sxy + Syz
(B) wxz = wxy + wyz
(C) wxyz = wxy
(D) Sxyz =Sxy

8. For the process, H2O()  H2O(g) at T = 100C and 1 atmosphere pressure, the correct choice is :
[JEE(Advanced) 2014, 3/120]
(A) Ssystem > 0 and Ssurroundings > 0 (B) Ssystem > 0 and Ssurroundings < 0
(C) Ssystem < 0 and Ssurroundings > 0 (D) Ssystem < 0 and Ssurroundings < 0
9. Match the thermodynamic processes given under Column-I with the expressions given under
Column-II. [JEE(Advanced) 2015, 8/168]
Column-I Column-II
(A) Freezing of water at 273 K and 1 atm (P) q=0
Expansion of 1 mol of an ideal gas into a vacuum under isolated
(B) (Q) w=0
conditions
Mixing of equal volumes of two ideal gases at constant
(C) (R) Ssys < 0
temperature and pressure in an isolated container
Reversible heating of H2(g) at 1 atm from 300 K to 600 K,
(D) (S) U = 0
followed by reversible cooling to 300 K at 1 atm
(T) G = 0
10. One mole of an ideal gas at 300 K in thermal contact with surroundings expands isothermally from 1.0 L
to 2.0 L against a constant pressure of 3.0 atm. In this process, the change in entropy of surroundings
(Ssurr) in JK–1 is : (1 L atm = 101.3 J) [JEE(Advanced) 2016, 3/124]
(A) 5.763 (B) 1.013 (C) –1.013 (D) –5.763

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Thermodynamics & Thermodynamics
11.* For a reaction taking place in a container in equilibrium with its surroundings, the effect of temperature
on its equilibrium constant K in terms of change in entropy is described by
[JEE(Advanced) 2017, 4/122]
(A) With increase in temperature, the value of K for endothermic reaction increases because
unfavourable change in entropy of the surroundings decreases
(B) With increase in temperature, the value of K for exothermic reaction decreases because favourable
change in entropy of the surroundings decreases
(C) With increase in temperature, the value of K for endothermic reaction increases because the
entropy change of the system is negative
(D) With increase in temperature, the value of K for exothermic reaction decreases because the entropy
change of the system is positive

PART - II : JEE (MAIN) / AIEEE PROBLEMS (PREVIOUS YEARS)

1. Identify the correct statement regarding a spontaneous process : [AIEEE 2007, 3/120]
(1) Exothermic processes are always spontaneous.
(2) Lowering of energy in the reaction process is the only criterion for spontaneity.
(3) For a spontaneous process in an isolated system, the change in entropy is positive.
(4) Endothermic processes are never spotaneous.
2. In conversion of lime-stone to lime, CaCO3(s) CaO(s) + CO2(g) the values of Hº and Sº are +
179.1 kJ mol–1 and 160.2 J/K respectively at 298 K and 1 bar. Assuming that H° and S° do not
change with temperature, temperature above which conversion of limestone to lime will be spontaneous
is : [AIEEE 2007, 3/120]
(1) 845 K (2) 1118 K (3) 1008 (4) 1200 K
3. Standard entropy of X2, Y2 and XY3 are 60, 40 and 50 JK–1 mol–1, respectively. [AIEEE 2008, 3/105]
1 3
For the reaction, X2 + Y2  XY3 H = – 30 kJ. To be at equilibrium the temperature will be :
2 2
(1) 500 K (2) 750 K (3) 1000 K (4) 1250 K
4. For a particular reversible reaction at temperature T, H and S were found to be both +ve. If Te is the
temperature at equilibrium, the reaction would be spontaneous when. [AIEEE 2010, 4/144]
(1) Te > T (2) T > Te (3) Te is 5 times T (4) T = Te
5. The entropy change involved in the isothermal reversible expansion of 2 moles of an ideal gas from a
volume of 10 dm3 to a volume of 100 dm3 at 27°C is : [AIEEE 2011, 4/120]
(1) 38.3 J mol–1 K–1 (2) 35.8 J mol–1 K–1 (3) 32.3 J mol–1 K–1 (4) 42.3 J mol–1 K–1
6. In view of the signs of rGº for the following reactions :
PbO2 + Pb  2PbO, rGº < 0 ; SnO2 + Sn  2SnO, rGº > 0,
which oxidation states are more characteristics for lead and tin ? [AIEEE 2011, 4/120]
(1) For lead +2, for tin +2 (2) For lead +4, for tin +4
(3) For lead +2, for tin +4 (4) For lead +4, for tin +2
7. The incorrect expression among the following is : [AIEEE 2012, 4/120]
Gsystem V
(1) =–T (2) In isothermal process, wreversible = –nRT ln f
S total Vi
Hº TSº
(3) lnK = (4) K = e–Gº/RT
RT
8. The following reaction is performed at 298 K.
2NO(g) + O2(g) 2NO2(g)
The standard free energy of formation of NO(g) is 86.6 kJ/mol at 298 K. What is the standard free
energy of formation of NO2(g) at 298 K ? (KP = 1.6 × 1012) [JEE(Main) 2015, 4/120]
(1) R(298) in (1.6 × 1012) – 86600 (2) 86600 + R(298) ln (1.6 x 1012)
ln (1.6  1012 )
(3) 86600 – (4) 0.5 [2 × 86,600 – R (298) ln (1.6 × 1012)]
R (298)
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EXERCISE - 1
PART – I
A-1. Because larger space creates more disorder.
A-2. Dissolution of solute makes the motion of solute particles free. Also the increased number of particles in
mixed state increases disorderness.
A-3. (a) Ssys is positive; Ssurr is negative, (b) Ssys is positive; Ssurr is negative;
(c) Ssys is positive; Ssurr is negative.
A-4. Entropy of the universe is constantly increasing. Suniverse = Ssystem + Ssurrounding > 0 for a spontaneous
process.
A-5. At 0 K, entropy of a perfect crystalline pure substance is taken to be zero.
A-6. GT,P = (–)ve or Stotal > 0
A-7. G = H – TS
For spontaneous reaction G = (–) ve 
S Should be positive
B-1. – 1.5 × 85 J/K
B-2. – 215.2 JK–1 mol–1
B-3. Ssystem = 111.4 JK–1, Ssurr = –99.71 JK–1, Suniv = +11.69 JK–1
B-4. Entropy change in surroundings = 959.73 JK–1.
B-5. II < I < III <IV
B-6. Ozone has three atoms per molecule, whereas O2 has only two.
C-1. (i) Chemical reaction in equilibrium state (ii) non-spontaneous (iii) Spontaneous.
C-2. Gº indicates that B is more stable than C.
C-3. 97.79 kJ
C-4. Gº of reaction is 38477 J/mol.

PART - II
A-1. (C) A-2. (C) A-3. (B) A-4. (D) A-5. (B)
A-6. (C) A-7. (B) A-8. (A) B-1. (B) B-2. (C)
B-3. (C) B-4. (D) B-5. (C) C-1. (D) C-2. (B)
C-3. (D) C-4. (D) C-5. (D) C-6. (A) C-7. (B)
C-8. (A)
PART - III
1. (A)  (p, s); (B)  (r) ; (C)  (q, s) ; (D) (q, s).
2. (A)  (s); (B)  (p, r); (C)  (q); (D)  (p, r)

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EXERCISE – 2

PART - I
1. (C) 2. (C) 3. (A) 4. (C)

PART - II
–1
1. 6 2. 1 3. 7 kJ mol . 4. 8 5. 8
6. 15 7. 51 8. 48 9. 40
PART - III
1. (BD) 2. (AB) 3. (ABD) 4. (ABD) 5. (ABC)
6. (ABCD)

PART - IV
1. (A) 2. (B) 3. (D) 4. (B) 5. (A)
6. (C) 7. (D) 8. (A)

EXERCISE – 3
PART - I
1. (D) 2. (B) 3. (B) 4. (A) 5. (D)
6. (A) 7. (AC) 8. (B)
9. (A-R,T); (B-P,Q,S); (C-P,Q,S); (D-P,Q,S,T) 10. (C) 11. (AB)
PART - II
1. (3) 2. (2) 3. (2) 4. (2) 5. (1)
6. (3) 7. (3) 8. (4)

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THERMOCHEMISTRY

PART - I : SUBJECTIVE QUESTIONS

Section (A) : Calculation U, H & W for chemical reaction
A-1_. For the reaction : C2H5OH() + 3O2(g)  2CO2(g) + 3H2O(g)
ifUº = –1373 kJ mol–1 at 298 K. Calculate Hº
A-2. 2 mole of zinc is dissolved in HCl at 25ºC. Calculate the work done in open vessel.

Section (B) : Basics & Kirchoff’s law

B-1. Diborane is a potential rocket fuel which undergoes combustion according to the reaction
B2H6(g) + 3O2(g)  B2O3(s) + 3H2O(g)
From the following data, calculate the enthalpy change for the combustion of diborane
2B(s) + (3/2) O2(g)  B2O3(s) H = – 1273 kJ mol–1
H2(g) + (1/2)O2(g)  H2O(l) H = – 286 kJ mol–1
H2O(l)  H2O(g) H = 44 kJ mol–1
2B(s) + 3H2(g) B2H6(g) H = 36 kJ mol–1
B-2. Predict the standard reaction enthalpy of 2 NO2(g)  N2O4(g) at 100°C. H° at 25°C is –57.2 kJ.mol–1
Cp(NO2) = 37.2 J.mol–1 K–1 Cp(N2O4) = 77.28 J.mol–1 k–1.
Section (C) : Enthalpy of formation & combustion
C-1. The heat of combustion of ethyl alcohol is –300 kcal. If the heats of formation of CO2 (g) and H2O() are
–94.3 and –68.5 kcal respectively, calculate the heat of formation of ethyl alcohol.
C-2. If H2 + 1/2 O2 H2O,    H = – 68 kcal
K + H2O + water  KOH (aq) + 1/2 H2, H = – 48 kcal
KOH + water KOH (aq),   H = – 14 kcal
Find the heat of formation of KOH.
C-3. The standard enthalpy of decomposition of the yellow complex H3NSO2 into NH3 and SO2 is + 40 kJ
mol–1. Calculate the standard enthalpy of formation of H3NSO2. H0f(NH3) = – 46.17 kJ mol–1,
H0f(SO2) = –296.83.
C-4. When 12.0 g of carbon (graphite) reacted with oxygen to form CO and CO2 at 250C and constant
pressure, 252 kJ of heat was released and no carbon remained. If H0f (CO, g) = – 110.5 kJ mol–1 and
H0f (CO2,g) = – 393.5 kJ mol–1, calculate the mass of oxygen consumed.
Section (D) : Bond enthalpy method & Resonance energy
D-1. Calcualte the bond energy of Cl–Cl bond from the following data :
CH4(g) + Cl2(g)  CH3Cl(g) + HCl(g); H = – 100.3 kJ. Also the bond enthalpies of C–H, C–Cl, H–Cl
–1
bonds are 413, 326 and 431 kJ mol respectively.
D-2. Calculate Hºr for the reaction CH2Cl2(g) C(g) + 2H(g) + 2Cl(g). The average bond enthalpies of
C–H and C–Cl bonds are 414 kJ mol–1 and 330 kJ mol–1.
D-3. Calculate the enthalpy change (H) of the following reaction 2C2H2(g) + 5O2(g) 4CO2(g) + 2H2O(g)
given average bond enthalpies of various bonds, i.e., C–H, CC, O=O, C=O, O–H as 414, 814, 499,
724 and 640 kJ mol–1 respectively.

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D-4. Calculate change in enthalpy for the reaction at 27ºC
H2(g) + C2(g)  2H–C(g)
by using the bond energy and energy data
Bond energies of H–H, C–C and H–C bonds are 435 kJ mol–1, 240 kJ mol–1 and 430 kJ mol–1
respectively.
D-5. Estimate the average S–F bond enthalpy in SF6. The values of standard enthalpy of formation of
SF6(g), S(g) and F(g) are : –1100, 274 and 80 kJ mol–1 respectively.

Section (E) : Enthalpy of solution & Born Haber’s cycle

–1 0
E-1. Calculate the standard enthalpy of solution of AgCl(s) in water Hºf (AgCl,s) = – 127.07 kJ mol , H f
(Ag+, aq) = 105.58 kJ mol–1, H0f (Cl–, aq) = –167.35 kJ mol–1.
E-2. Enthalpies of solution of BaCl2 (s) and BaCl2.2H2O (s) are – 20 kJ/mole and 8.0 kJ/mole respectively.
Calculate heat of hydration of BaCl2 (s).
E-3. Setup of Born-Haber cycle; calculate lattice energy of MgO(s). The given that - enthalpy of formation of
st nd
MgO(s) = –602, sublimation of Mg(s) = 148 ; 1 & 2 ionization energy of Mg = 738 & 1450 respectively.
st nd
For Oxygen bond dissociation energy = 498; 1 & 2 electron gain enthalpy = –141 & 844 respectively
–1
(all unit in kJmole ).
Section (F) : Enthalpy of neutralization
F-1. 10 mL of each 1 M HCl and 1M H2SO4 are neutralized by 1 M NaOH solution that liberate the heat of
a & b kJ/mol respectively. What is relation between a and b ?
F-2. The enthalpy of neutralization of 1M HCl by 1M NaOH is – 57 kJ/mole. The enthalpy of formation of
water is – 285 kJ/mole. The enthalpy of formation of OH– ion is :
F-3. The standard enthalpy of neutralization of KOH with HCN and HCl in dilute solution is –2480 cal.mol–1
and –13.68 kcalmol–1 respectively. Find the enthalpy of dissociation of HCN at the same temperature.

PART - II : ONLY ONE OPTION CORRECT TYPE

Section (A) : Calculation U, H & W for chemical reaction
A–1. The free energy change for a reversible reaction at equilibrium is :
(A) Positive (B) Negative (C) Zero (D) Cannot say
A-2. Hº for the reaction X(g) + Y(g) Z(g) is – 4.6 Kcal, the value of Uº of the reaction at 227ºC is
(R = 2 cal.mol–1 K–1) :
(A) –3.6 kcal (B) –5.6 kcal (C) –4.6 kcal (D) –2.6 kcal
A-3. Determine which of the following reactions at constant pressure represent surrounding that do work on
the system :
I. 4NH3 (g) + 7O2 (g)  4NO2 (g) + 6H2O (g)
II. CO (g) + 2H2 (g)  CH3OH (  )
III. C (s, graphite) + H2O (g)CO (g) + H2 (g)
IV. H2O (s) H2O (  )
(A) III, IV (B) II and III (C) II, IV (D) I and II, IV
A-4. Consider the reaction at 300 K
H2 (g) + Cl2(g)  2HCl (g) ; Hº = – 185 kJ
If 2 mole of H2 completely react with 2 mole of Cl2 to form HCl. What is Uº for this reaction ?
(A) 0 (B) – 185 kJ (C) 370 kJ (D) – 370 kJ
A-5._ A mixture of 2 mole of CO and 1 mole of O2, in a closed vessel is ignited to convert the CO to CO2. If
H is the enthalpy change and U is the change in internal energy then :
(A) H < U (B) H > U (C) H = U (D) H = 2U
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Section (B) : Basics & Kirchoff’s law
B-1. For which of the following change H  E ?
(A) H2(g) + I2(g)  2HI(g) (B) HCl(aq) + NaOH(aq)NaCl(aq) + H2O()
(C) C(s) + O2(g)  CO2(g) (D) N2(g) + 3H2(g)2NH3(g)
B-2. Calculate the Standard internal energy of formation of liquid methyl acetate (CH3COOCH3) from its
standard enthalpy of formation, which is –442.91 kJ mole–1 at 25ºC.
(A) –433 (B) +433 (C) –452.82 (D) 452.82
B-3. 2C + O2 2CO ; H = – 220 kJ
Which of the following statement is correct for this reaction
(A) Heat of combustion of carbon is 110 kJ (B) Reaction is exothermic
(C) Reaction needs no initiation (D) All of these are correct
B-4. C (s) + O2 (g)  CO2, (g);   H = –94.3 kcal/mol
1
CO (g) + O2(g) CO2 (g);  H = – 67.4 kcal/mo!
2
O2(g)  2O (g);    H = 117.4 kcal/mol
CO (g)  C (g) + O(g) ;   H = 230.6 kcal/mol
 Calculate H for C (s)  C (g) in kcal/mol.
(A) 171 (B) 154 (C) 117 (D)145
Section (C) : Enthalpy of formation & combustion
C-1. In the reaction, CO2(g) + H2(g) CO(g) + H2O(g); H = 2.8 kJ, H represents
(A) heat of reaction (B) heat of combustion (C) heat of formation (D) heat of solution
C-2. Given, H2(g) + Br2(g)  2HBr(g), Hº1 and standard enthalpy of condensation of bromine is Hº2,
standard enthalpy of formation of HBr at 25ºC is
(A) Hº1 / 2 (B) Hº1 / 2 + Hº2 (C) Hº1 / 2  Hº2 (D) (Hº1Hº2) / 2
C-3. For the following reaction, C (diamond) + O2  CO2(g) ; H = –94.3 kcal/mol
C (graphite) + O2  CO2(g) ; H = –97.6 kcal/mol
The heat required to change 1 g of C (graphite) C (diamond) is
(A) 1.59 kcal (B) 0.1375 kcal (C) 0.55 kcal (D) 0.275 kcal
C-4. The standard heat of combustion of solid boron is equal to :
(A) H°f (B2O3) (B) 1/2 H°f (B2O3) (C) 2H°f (B2O3) (D) 4H°f (B2O3)
C-5. The heat of combustion of sucrose (C12H22O11) is 1350 kcal/mol. How much of heat will be liberated
when 17.1 g of sucrose is burnt ?
(A) 67.5 kcal (B) 13.5 kcal (C) 40.5 kcal (D) 25.5 kcal
–1
C-6. If S + O2  SO2,   H = – 298.2 kJ mole
–1
SO2 + 1/2 O2  SO3,  H = – 98.7 kJ mole
SO3 + H2O  H2SO4,  H = – 130.2 kJ mole–1
–1
H2 + 1/2 O2  H2O,   H = – 287.3 kJ mole
the enthalpy of formation of H2SO4 at 298 K will be :
(A) – 814.4 kJ mol–1 (B) + 814.4 kJ mole–1 (C) – 650.3 kJ mole–1 (D) – 433.7 kJ mole–1
C-7. When a certain amount of ethylene was combusted, 5644 kJ heat was evolved. If heat of combustion of
ethylene is 1411 kJ, the volume of O2 (at NTP) that entered into the reaction is :
(A) 268.8 ml (B) 268.8 L (C) 6226 × 22.4 L (D) 22.4 L
C-8. The values of heat of combustion of ethane (C2H6) and ethyne (C2H2) are –341 and –310 Kcal
respectively. Then which of the following is better fuel on mass basis :
(A) C2H2 (B) C2H6 (C) Both (A) & (B) (D) None of these

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Section (D) : Bond enthalpy method & Resonance energy
D-1. If enthalpy of dissociation of CH4 and C2H6 are 320 and 600 calories respectively then bond energy of
C–C bond is :
(A) 80 cal (B) 40 cal (C) 60 cal (D) 120 cal
–1
D-2. The bond dissociation energy of gaseous H2, Cl2 and HCl are 104, 58 and 103 kcal mol
respectively. The enthalpy of formation for HCl gas will be
(A) – 44.0 kcal (B) – 22.0 kcal (C) 22.0 kcal (D) 44.0 kcal
D-3. AB, A2 and B2 are diatomic molecules. If the bond enthalpies of A2, AB & B2 are in the ratio
1 : 1 : 0.5 and enthalpy of formation of AB from A2 and B2 is – 100 kJ/mol–1. What is the bond enthalpy
of A2.
(A) 400 kJ/mol (B) 200 kJ/mol (C) 100 kJ/mol (D) 300 kJ/mol
Section (E) : Enthalpy of Solution & Born Haber’s cycle
E-1. One mole of anhydrous MgCl2 dissolves in water and librates 25 cal/mol of heat. Hhydration of MgCl2 = –
30 cal/mol. Heat of dissolution of MgCl2.H2O is
(A) +5 cal/mol (B) –5 cal/mol (C) 55 cal/mol (D) –55 cal/mol
E-2. The enthalpy of solution of NaOH (s) in water is – 41.6 kJ/mole. When NaOH is dissolved in water then
the temperature of water :
(A) Increase (B) Decrease (C) Does not change (D) Fluctuates
E-3. The enthalpy change for the reaction of 5 liter of ethylene with 5 liter of H2 gas at 1.5 atm pressure is 
H = – 0.5 kJ. The value of U will be : (1 atm Lt = 100 J)
(A) – 1.25 kJ (B) + 1.25 kJ (C) 0.25 kJ (D) – 0.25 kJ
E-4. For which one of the following reaction does the molar enthalpy change of a reaction corresponds to
Lattice energy of KBr ?
(A) KBr(s)  K(s) + ½Br2(g) (B) KBr(g)  K(g) + Br(g)
(C) KBr(s)  K+(g) + Br –(g) (D) KBr(g)  K+(g) + Br –(g)
E-5. Calculate the lattice energy for the reaction
Li+(g) + Cl–(g)  LiCl(s)
Given that :
Hsub (Li) = 160 ; Hdiss (Cl2) = 244 ; IP(Li) = 520 ;
EA (Cl) = –365 and Hf (LiCl) = – 400 (all in kJ mole–1)
(A) –837 (B) –959 (C) –1567 (D) –37

Section (F) : Enthalpy of neutralization

F-1. The enthalpy of neutralization of which of the following acid & base is nearly – 13.6 kcal.
(A) HCN and NaOH (B) CH3COOH and NH4OH
(C) HCl and KOH (D) HCl and NH4OH
F-2. If heat of dissociation of CHCl2COOH is 0.7 kcal/mole then H for the reaction :
CHCl2COOH + KOH  CHCl2COOK + H2O
(A) – 13 kcal (B) + 13 kcal (C) – 14.4 kcal (D) – 13.7 kcal

PART - III : MATCH THE COLUMN

1. Match the column :
Columm-I Columm-II
(A) C (s, graphite) + O2(g)  CO2(g) (p) Hºcombustion
(B) C(s, graphite)  C(g) (q) Hºformation
1
(C) CO(g) + O2(g) CO2(g) (r) Hºatomization
2
(D) CH4(g) C(g) + 4H(g) (s) Hºsublimation
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PART - I : ONLY ONE OPTION CORRECT TYPE

1. Look at the following diagram :
Enthalpy(kJ)

A
40

15 B

Progress of reaction
The enthalpy change for the reaction A  B will be
(A) – 25 kJ (B) – 40 kJ (C) + 25 kJ (D) – 65 kJ
2. In Haber's process of manufacturing of ammonia :
N2(g) + 3H2(g)  2NH3(g) ;  H025 C = –92.2 kJ
Molecule N2(g) H2(g) NH3(g)
CP JK-1 mol–1 29.1 28.8 35.1
If CP is independent of temperature, then reaction at 100°C as compared to that of 25°C will be :
(A) More endothermic (B) Less endothermic (C) More exothermic (D) Less exothermic

3. In the reaction AB2() + 3X2(g) AX2(g) + 2BX2(g) H = – 270 kcal per mol. of AB2(),
the enthalpies of formation of AX2(g) & BX2(g) are in the ratio of 4 : 3 and have opposite sign. The value
of Hf0 (AB2()) = + 30 kcal/mol. Then
(A) Hf0 (AX2) = – 96 kcal /mol
(B) Hf0 (BX2) = + 480 kcal /mol
0
(C) Kp = Kc &Hf (AX2) = + 480 kcal /mol
0 0
(D) Kp = Kc RT & Hf (AX2) + Hf (BX2) = –240 kcal /mol

4. The heat of formation of C2H5OH() is 66 kcal/mole. The heat of combustion of CH3OCH3 (g) is
– 348 kcal/mole. Hf for H2O and CO2 are 68 kcal/mole and 94 kcal/mole respectively. Then, the H
for the isomerisation reaction C2H5OH ()  CH3OCH3(g) and E for the same are at T = 25°C
(A)H = 18 kcal/mole, E = 17.301 kcal/mole (B) H = 22 kcal/mole, E = 21.408 kcal/mole
(C) H = 26 kcal/mole, E = 25.709 kcal/mole (D) H = 30 kcal/mole, E = 28.522 kcal/mole
5. Cesium chlorides is formed according to the following equation Cs(s) + 0.5 Cl2(g)  CsCl(s). The
enthalpy of sublimation of Cs, enthalpy of dissociation of chlorine, ionization energy of Cs and electron
–1
affinity of chlorine are 81.2, 243.0, 375.7 and –348.3 kJ mol . The energy change involved in the
–1
formation of CsCl is –388.6 kJ mol . Calculate the lattice energy of CsCl.
(A) 618.7 kJ mol–1 (B) 1237.4 kJ mol–1 (C) –1237.4 kJ mol–1 (D) –618.7 kJ mol–1
6. The enthalpies of neutralization of a weak base AOH and a strong base BOH by HCI are –12250 cal/
mol and –13000 cal/ mol respecitively. When one mole of HCI is added to a solution containing 1 mole
of AOH and 1 mole of BOH, the enthalpy change was –12500 cal/ mol. In what ratio the acid is
distributed between AOH and BOH ?
(A) 2 : 1 (B) 2 : 3 (C) 1 : 2 (D) None of these
7. The enthalpy of neutralization of 40.0 g of NaOH by 60.0 g of CH3COOH will be :
(A) 57.1 kJ equiv–1 (B) less than 57.1 kJ equiv–1
–1 –1
(C) more than 57.1 kJ equiv (D) 13.7 kJ equiv
8. Given ioniz H° (HCN) = 45.2 kJ mol–1 and ioniz H° (CH3COOH) = 2.1 kJ mol–1. Which one of the
following facts is true ?
(A) pKa (HCN) = pKa (CH3COOH) (B) pKa (HCN) > pKa (CH3COOH)
(C) pKa (HCN) < pKa (CH3COOH) (D) pKa (HCN) = (45.17/2.07) pKa (CH3COOH)
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9. The average O–H bond energy in H2O with the help of following data.
(1) H2O() H2O(g) ; H = + 40.6 KJ mol–1
(2) 2H(g)  H2 (g) ; H = – 435.0 KJ mol–1
–1
(3) O2(g)  2O(g) ; H = + 489.6 KJ mol
(4) 2H2 (g) + O2 (g)  2H2O() ; H = – 571.6 KJ mol–1
(A) 584.9 KJ mol–1 (B) 279.8 KJ mol–1 (C) 462.5 KJ mol–1 (D) 925 KJ mol–1
10. Enthalpy of polymerisation of ethylene, as represented by the reaction, nCH2=CH2  CH2CH2)n
is 100 kJ per mole of ethylene. Given bond enthalpy of C=C bond is 600 kJ mol1, enthalpy of CC
bond (in kJ mol) will be :
(A) 116.7 (B) 350 (C) 700 (D) indeterminate
–1
11. The average energy required to break a P – P bond in P4 (s) into gaseous atoms is 53.2 kcal mol . The
bond dissociation energy of H2(g) is 104.2 kcal mol–1; Hf0 of PH3(g) from P4(s) is 5.5 kcal mol–1. The P-
–1
H bond energy in kcal mol is [Neglect presence of Van der Waals forces in P4(s)]
(A) 85.2 (B) 57.6 (C) 76.9 (D) 63.3

PART - II : SINGLE AND DOUBLE VALUE INTEGER TYPE

1. If heat of reaction for the given acid-base reaciton :
HA + NaOH  NaA + H2O ; H = – 4.7 kcal
The heat of dissociation of HA is______ .
2. The enthalpy of combustion at 25ºC of H2 (g), cyclohexane and cyclohexene are – 241, – 3920 and –
–1
3717 kJmole respectively. The heat of hydrogenation of cyclohexene is (Kcal/mole) approximate
integer :
3. When 0.36g of glucose was burned in a bomb calorimeter (Heat capacity 600 JK1) the temperature
rise by 10 K. Calculate the standard molar enthalpy of combustion (MJ/mole).
0
4. Calculate the enthalpy change when infinitely dilute solution of CaCl2 and Na2CO3 are mixed. H f for
Ca+2(aq), CO–23(aq) and CaCO3(s) are –129.80, –161.7, –288.50 kcal mol–1 respectively.
5. How many of the following have standard heat of formation is zero.
(i) Br2() (ii) CO2 (g) (iii) C(graphite) (iv) Cl2() (v) Cl2(g)
(vi) F2(g) (vii) F(g) (viii) I2(g) (ix) S(monoclinic) (x) N2(g)
(xi) P(Black) (xii) P(red) (xiii) CH4
6. Standard enthalpy of combustion of cyclopropane is – 2091 kJ/mole at 25ºC then calculate the enthalpy
of formation of cyclopropane. If Hºf (CO2) = – 393.5 kJ/mole and Hºf (H2O) = – 285.8 kJ/mole.
7. Bond energies of NN; H–H and N–H bonds are 945, 463 & 391 kJ mol–1 respectively, the enthalpy of
the following reactions is :
N2 (g) + 3H2 (g)  2NH3 (g)
8. The reaction of nitrogen with hydrogen to make ammonia has H = – 92 kJ
N2 (g) + 3H2 (g)  2NH3 (g)
What is the value of U (in kJ) if the reaction is carried out at a constant pressure of 40 bar and the
volume change is – 1.25 litre.
9. Calculate U of reaction for the hydrogenation of acetylene at constant volume and at 77ºC.
Given that Hf(H2O) = –67.8 kcal mole; Hcomb(C2H2) = –310.1 kcal/mole, Hcomb(C2H4) = –337.2
kcal/Mole
10. Calculate the C–C bond enthalpy from the following data :
1
(a) C(s)  C(g) ; H = 170 Kcal (b) H2(g)  H(g) ; H = 52 Kcal
2
(c) Heat of formation of ethane = – 20 Kcal (d) C–H bond enthalpy = 99 Kcal.

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PART - III : ONE OR MORE THAN ONE OPTIONS CORRECT TYPE

1. Which of the following is(are) endothermic reaction :
(A) Combustion of methane (B) Decomposition of water
(C) Dehydrogenation of ethane to ethylene (D) Conversion of graphite to diamond
2. Heat of reaction depend upon :
(A) Physical state of reactants and products
(B) Whether the reaction is carried out at constant pressure or at constant volume
(C) Method by which the final products are obtained from the reactants
(D) Temperature of the reaction
3. Which of the following reaction cannot be used to define the heat of formation of CO2 (g).
1 7
(A) CO (g) + O2 CO2 (g) (B) C6H6 () + O2 (g) 6CO2 (g) + 3H2O ()
2 2
(C) C (diamond) + O2 (g)  CO2 (g) (D) C (graphite) + O2 (g) CO2 (g)
4. Heat of formation of CH4 are :
If given :
C (s) + O2 (g)  CO2 (g) H = – 394 kJ
H2 (g) + ½O2 (g)  H2O () H = – 284 kJ
CH4 (g) + 2O2 (g)  CO2 (g) + 2H2O () H = – 892 kJ
(A) – 70 kJ (B) – 16.7 kcal (C) – 244 kJ (D) – 50 kcal
5. Heat of neutralization of the acid-base reaction is 57.32 kJ for :
(A) HCOOH + KOH (B) CH3COOH + NaOH
(C) HNO3 + LiOH (D) HCl + NaOH
6. For which of the following reaction Hºreaction is not equal to Hºf of product.
(A) 2CO(g) + O2(g)  2CO2(g) (B) N2(g) + O3(g)  N2O3(g)
(C) CH4(g) + 2Cl2(g)  CH2Cl2() + 2HCl(g) (D) Xe(g) + 2F2(g) XeF4(g)

7. The following is (are) endothermic reaction(s) :

(A) Combustion of methane. (B) Decomposition of water
(C) Dehydrogenation of ethane to ethylene. (D) Conversion of graphite to diamond.
8. Which of the reaction defines molar Hf°?
1 1
(A) CaO(s) + CO2(g)  CaCO3 (s) (B) Br2() + H2(g)  HBr(g)
2 2
3 1 1
(C) N2(g) + 2H2(g) + O2(g) NH4 NO3(s) (D) 2(s) + H2(g)  H(g)
2 2 2

PART - IV : COMPREHENSION
Comprehension # 1
Enthalpy of neutralization is defined as the enthalpy change when 1 mole of acid/base is completely
neutralized by base/acid in dilute solution.
For strong acid and strong base neutralization net chemical change is
+ –
H (aq) + OH (aq)  H2O(); rHº = – 55.84 kJ/mol
Hºionization of aqueous solution of strong acid and strong base is zero.
When a dilute solution of a weak acid or base is neutralized, the enthalpy of neutralization is some what
less because of the absorption of heat in the ionization of the weak acid or base, for weak acid/base
Hºneutrilization = Hºionization + rHº (H+ + OH–  H2O)
1. If enthalpy of neutralization of CH3COOH by NaOH is –49.86 kJ/mol then enthalpy of ionzation of
CH3COOH is:
(A) 5.98 kJ/mol (B) –5.98 kJ/mol (C) 105.7 kJ/mol (D) None of these
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2. What is Hº for complete neutralization of strong diacidic base A(OH)2 by HNO3 ?
(A) –55.84 kJ (B) –111.68 kJ (C) 55.84 kJ/mol (D) None of these
3. Under the same condition how many mL of 0.1 M NaOH and 0.05 M H2A (strong diprotic acid) solution
should be mixed for a total volume of 100 mL produce the highest rise in temperature :
(A) 25 : 75 (B) 50 : 50 (C) 75 : 25 (D) 66.66 : 33.33
Comprehension # 2
Answer Q.4, Q.5 and Q.6 by appropriately matching the information given in the three columns
of the following table.
All the given reaction are carried out at constant pressure and temperature conditions. Assuming ideal
behavior of all the gases involved.
Column-1 Column-2 Column-3
Reaction is spontaneous at high
(I) 2Ag2O(s) 4Ag(s) + O2(g) (i) wrxn > 0 (P)
temperature.
(Q Reaction is spontaneous at all
(II) 2CO(g) + O2(g) 2CO2(g) (ii) wrxn < 0
temperatures.
(III) 2C(s) + O2(g) 2CO(g) (iii) rxnH > 0 (R) Reactant mixture is diamagnetic.
One of the reactant is used to reduce
(IV) N2(g) + 3H2(g) 2NH3(g) (iv) rxnS > 0 (S) metallic oxide in to metal.
4._ The only incorrect combination is –
(A) (I) (ii) (P) (B) (II) (iii) (P) (C) (IV) (ii) (R) (D) (III) (ii) (Q)
5._ The only correct combination is –
(A) (I) (iv) (Q) (B) (II) (ii) (S) (C) (II) (iii) (R) (D) (IV) (ii) (S)
6._ The only correct combination is –
(A) (III) (iv) (S) (B) (IV) (i) (Q) (C) (II) (iii) (S) (D) (I) (i) (P)

* Marked Questions may have more than one correct option.

PART - I : JEE (ADVANCED) / IIT-JEE PROBLEMS (PREVIOUS YEARS)
1. The species which by definition has ZERO standard molar enthalpy of formation at 298 K is :
[JEE 2010, 3/163]
(A) Br2(g) (B) Cl2(g) (C) H2O(g) (D) CH4(g)
2. The bond energy (in kcal mol–1) of a C–C single bond is approximately : [JEE 2010, 3/163]
(A) 1 (B) 10 (C) 100 (D) 1000
3. Match the transformation in column-I with appropriate options in column-II. [JEE 2011, 8/180]
Column-I Column-II
(A) CO2(s)  CO2(g) (p) phase transition
(B) CaCO3(s)  CaO(s) + CO2(g) (q) allotropic change
(C) 2H  H2(g) (r) H is positive
(D) P(white, solid)  P(red, solid) (s) S is positive
(t) S is negative

4. Using the data provided, calculate the multiple bond energy (kJ mol–1) of a CC bond C2H2. That
–1
energy is (take the bond energy of a C–H bond as 350 kJ mol ) [JEE 2012, 3/136]
2C(s) + H2(g)  C2H2(g) H = 225 kJ mol–1
2C(s)  2C (g) H = 1410 kJ mol–1
–1
H2(g)  2H(g)  H = 330 kJ mol
(A) 1165 (B) 837 (C) 865 (D) 815

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5. The standard enthalpies of formation of CO2(g), H2O(l) and glucose(s) at 25ºC are –400 kJ/mol, –300
kJ/mol and –1300 kJ/mol, respectively. The standard enthalpy of combustion per gram of glucose at
25ºC is [JEE (Advance)2013, 2/120]
(A) +2900 kJ (B) – 2900 kJ (C) –16.11 kJ (D) + 16.11 kJ

6. The standard state Gibbs free energies of formation of C(graphite) and C(diamond) at T = 298 K are
–1
fGº[C(graphite)] = 0 kJ mol
fGº[C(diamond)] = 2.9 kJ mol–1
The standard state means that the pressure should be 1 bar, and substance should be pure at a given
temperature. The conversion of graphite [C(graphite)] to diamond [C(diamond)] reduces its volume by
–6 3 –1
2 × 10 m mol . If C(graphite) is converted to C(diamond) isothermally at T = 298 K, the pressure at
which C(graphite) is in equilibrium with C(diamond), is : [JEE(Advanced) 2017, 3/122]
[Useful information: 1 J = 1 kg m2 s–2, 1 Pa = 1 kg m–1 s–2; 1 bar = 105 Pa]
(A) 58001 bar (B) 1450 bar (C) 14501 bar (D) 29001 bar

PART - II : JEE (MAIN) / AIEEE PROBLEMS (PREVIOUS YEARS)

1. (HU) for the formation of carbon monoxide (CO) from its elements at 298 K is [AIEEE 2006]
(R = 8.314 J K–1 mol–1) 
(1) 1238.78 J mol–1 (2) –2477.57 J mol–1 (3) 2477.57 J mol–1 (4) –1238.78 J mol–1
2. The standard enthalpy of formation (Hf°) at 398 K for methane, CH4(g) is 74.8 kJ mol–1. The additional
information required to determine the average energy for C–H bond formation would be :
[AIEEE 2007, 3/120]
(1) the dissociation energy of H2 and enthalpy of sublimation of carbon
(2) latent heat of vapourisation of methane
(3) the first four ionization energies of carbon and electron gain enthalpy of hydrogen
(4) the dissociation energy of hydrogen molecule, H2
3. On the basis of the following thermochemical data : (ƒGºH+(aq) = 0) [AIEEE 2009, 8/144]
+ –
H2O()  H (aq) + OH (aq.) ; H = 57.32 kJ
1
H2(g) + O2 (g) H2O () ; H = –286.20 kJ
2
–
The value of enthalpy of formation of OH ion at 25ºC is :
(1) –228.88 kJ (2) +228.88 kJ (3) –343.52 kJ (4) –22.88 kJ
4. In a fuel cell methanol is used as fuel and oxygen gas is used as an oxidizer. The reaction is
3
CH3OH() + O2 (g) CO2(g) + 2H2O()
2
At 298 K, standard Gibb’s energies of formation for CH3OH(), H2O() and CO2 (g) are –166.2, –237.2
–1 –1
and –394.4 kJ mol respectively. If standard enthalpy of combustion of methanol is –726kJ mol ,
efficiency of the fuel cell will be : [AIEEE 2009, 8/144]
(1) 87% (2) 90% (3) 97% (4) 80%
5. The standard enthalpy of formation of NH3 is – 46.0 kJ mol–1. If the enthalpy of formation of H2 from its
–1 –1
atoms is – 436 kJ mol and that of N2 is – 712 kJ mol , the average bond enthalpy of N – H bond in
NH3 is [AIEEE 2010, 4/144]
(1) – 964 kJ mol–1 (2) + 352 kJ mol–1 (3) + 1056 kJ mol–1 (4) – 1102 kJ mol–1
6. The value of enthalpy change (H) for the reaction, C2H5OH(l) + 3O2(g)  2CO2(g) + 3H2O(I) at 27°C is
–1
–1366.5 kJ mol . The value of internal energy change for the above reaction at this temperature will
be: [AIEEE 2011, 4/120]
(1) –1369.0 kJ (2) –1364.0 kJ (3) –1361.5 kJ (4) –1371.5 kJ

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7. Consider the reaction : 4NO2(g) + O2(g)  2N2O5(g), rH = –111 kJ.
If N2O5(s) is formed instead of N2O5(g) in the above reaction, the rH value will be:
–1
(given, H of sublimation for N2O5 is 54 kJ mol ) [AIEEE 2011, 4/120]
(1) + 54kJ (2) + 219 kJ (3) – 219 kJ (4) – 165 kJ
8. For complete combustion of ethanol, C2H5OH(l) + 3O2(g)  2CO2(g) + 3H2O(l), the amount of heat
–1
produced as measured in bomb calorimeter, is 1364.47 kJ mol at 25C. Assuming ideality the
–1
Enthalpy of combustion, CH, for the reaction will be : (R = 8.314 J mol ) [JEE(Main) 2014, 4/120]
–1 –1
(1) – 1366.95 kJ mol (2) – 1361.95 kJ mol
(3) – 1460.50 kJ mol–1 (4) – 1350.50 kJ mol–1
9. The heat of atomisation of methane and ethane are 360 kJ/mol and 620 kJ/mol, respectively. The
longest wavelength of light capable of breaking the C–C bond is :
23 –34
(Avogadro number = 6.02 × 10 , h = 6.62 × 10 J s) [JEE(Main, Online) 2015, 4/120]
3 3
(1) 2.48 × 10 nm (2) 1.49 × 10 nm (3) 2.49 × 104 nm (4) 2.48 × 104 nm
10. The heats of combustion of carbon and carbon monoxide are –393.5 and –283.5 kJ mol–1, respectively.
The heat of formation (in kJ) of carbon monoxide per mole is : [JEE(Main) 2016, 4/120]
(1) 676.5 (2) – 676.5 (3) –110.5 (4) 110.5
–1
11. Given : C(graphite) + O2(g)  CO2(g) ; rHº = – 393.5 kJ mol ;
1
H2(g) + O2(g)  H2O(l) ; rHº = – 285.8 kJ mol–1 ;
2
–1
CO2(g) + 2H2O(l)CH4(g) + 2O2(g) ; rHº = + 890.3 kJ mol
Based on the above thermochemical equations, the value of rHº at 298 K for the reaction :
C(graphite) + 2H2(g)  CH4(g) will be : [JEE(Main) 2017, 4/120]
–1 –1 –1 –1
(1) +144.0 kJ mol (2) –74.8 kJ mol (3) –144.0 kJ mol (4) +74.8 kJ mol

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Thermodynamics & Thermodynamics

EXERCISE – 1
PART – I
–1 –1
A-1. –1368 kJ mol A-2. –4.955 kJ B-1. – 2035 kJ mol
B-2. – 56.98 kJ mol–1 C-1. (–94.1 kcal) C-2. –102 kcal
–1
C-3. – 383 kJ mol C-4. 24 g D-1. 243.7 kJ mol–1
D-2. 1488 kJ mol–1. D-3. – 2573 kJ/mole D-4. –185 kJ
D-5. 309 kJ mol–1 E-1. – 65.3 kJ mol–1 E-2. – 28 kJ/mole
–1
E-3. 3890 kJmole F-1. 2a = b F-2. – 228 kJ/mole.
F-3. 11.2 Kcal

PART – II
A–1. (C) A-2. (A) A-3. (D) A-4. (D) A-5. (A)
B-1. (D) B-2. (A) B-3. (B) B-4. (D) C-1. (A)
C-2. (D) C-3. (D) C-4. (B) C-5. (A) C-6. (A)
C-7. (B) C-8. (A) D-1. (D) D-2. (B) D-3. (A)
E-1. (A) E-2. (A) E-3. (C) E-4. (C) E-5. (A)
F-1. (C) F-2. (A)
PART – III
1. (A)  (p, q) ; (B)  (q, r, s) ; (C)  (p) ; (D)  (r)

EXERCISE – 2
PART – I
1. (A) 2. (C) 3. (C) 4. (B) 5. (A)
6. (A) 7. (B) 8. (B) 9. (C) 10. (B)
11. (C)

PART – II
1. 9 2. 9 Kcal/mole 3. 3 4. 3 5. 5
6. 53 7. – 12 kJ 8. –87 9. 40 10. 78 Kcal

PART – III
1. (BCD) 2. (ABCD) 3. (ABC) 4. (AB) 5. (CD)
6. (ABC) 7. (BCD) 8. (BCD)

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Thermodynamics & Thermodynamics
PART – IV
1. (A) 2. (B) 3. (B) 4. (B) 5. (AD)
6. (A)

EXERCISE – 3
PART – I
1. (B) 2. (C) 3. (A – p, r, s) ; (B – r, s) ; (C – t) ; (D – p, q, t)
4. (D) 5. (C) 6. (C)

PART – II
1. (1) 2. (1) 3. (1) 4. (3) 5. (2)
6. (2) 7. (3) 8. (1) 9. (2) 10. (3)
11. (2)

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Thermodynamics & Thermodynamics

This Section is not meant for classroom discussion. It is being given to promote self-
study and self testing amongst the Resonance students.

PART - I : PRACTICE TEST-1 (IIT-JEE (MAIN Pattern))

Max. Time : 1 Hr. Max. Marks : 120
Important Instructions
1. The test is of 1 hour duration.
2. The Test Booklet consists of 30 questions. The maximum marks are 120.
3. Each question is allotted 4 (four) marks for correct response.
4. Candidates will be awarded marks as stated above in Instructions No. 3 for correct response of each
question.
¼ (one fourth) marks will be deducted for indicating incorrect response of each question. No deduction
from the total score will be made if no response is indicated for an item in the answer sheet.
5. There is only one correct response for each question. Filling up more than one response in any
question will be treated as wrong response and marks for wrong response will be deducted accordingly
as per instructions 4 above.
1. Among them intensive property is :
(1) Mass (2) Volume (3) Surface tension (4) Enthalpy
2. Which of the following is true for an adiabatic process :
(1) H = 0 (2) W = 0 (3) Q = 0 (4) V = 0
3. Which of the following is not a state function :
(1) S (2) G (3) H (4) Q
4. The relation between U and H at constant pressure is :
(1) H = U – PV (2) H = U + PV (3) U = V + H (4) U = H + PV
5. The work done in ergs for the reversible expansion of one mole of an ideal gas from a volume of 10
litres to 20 litres at 25ºC is :
(1) –2.303 × 298 × 0.082 log 2 (2) –298 × 107 × 8.31 × 2.303 log 2
(3) –2.303 × 298 × 0.082 log 0.5 (4) –8.31 × 107 × 298 – 2.303 log 0.5
6. A coffee cup calorimeter initially contains 125 g of water, at a temperature of 24.2ºC. 8 g of ammonium
nitrate (NH4NO3), also at 24.2ºC, is added to the water, and the final temperature is 18.2ºC. What is the
heat of solution of ammonium nitrate in kJ/mol ? The specific heat capacity of the solution is 4.2 J/ºC g.
(1) 33.51 kJ/mol (2) 39.5 kJ/mol (3) 32.2 kJ/mol (4) 37.3 kJ/mol
7. The molar heat capacities at constant pressure (assumed constant with respect to temperature) at A,B
and C are in ratio of 3 : 1.5 : 2.0 The enthalpy change for the exothermic reaction A + 2B  3C at
300 K and 310 K is H300 and H310 respectively then :
(1) H300 > H310 (2) H300 < H310 (3) H300 = H310
(4) if T2 > T1 then H310 > H300 and if T2 < T1 then H310 < H300
8. Heat of combustion of ethanol at constant pressure and at temperature T K (= 298 K) is found to be – q
J mol–1. Hence, heat of combustion (in J mol–1) of ethanol at the same temperature at constant volume
will be :
(1) RT – q (2) –(q + RT) (3) q – RT (4) q + RT
9. When 1.0 g of oxalic acid (H2C2O4) is burned in a bomb calorimeter whose heat capacity is 8.75 kJ/K,
the temperature increases by 0.312 K. The enthalpy of combustion of oxalic acid at 27ºC is :
(1) –245.7 kJ/mol (2) –244.452 kJ/mol (3) –246.947 kJ/mol (4) None of these

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Thermodynamics & Thermodynamics
–1 –1
10. Benzene burns according to the following equation at 300 K (R = 25/3 J mole K )
2C6H6() + 15 O2(g)  12 CO2(g) + 6H2O() Ho = – 6547.5 KJ
What is the Eo for the combustion of 1.5 mol of benzene
(1) –3271 kJ (2) –9813 kJ (3) –4905 kJ (4) –9810 kJ
11. Ethyl chloride(C2H5Cl), is prepared by reaction of ethylene with hydrogen chloride :
C2H4 (g) + HCl (g)  C2H5Cl (g) H = – 72.3 kJ/mol.
What is the value of E (in kJ), if 98 g of ethylene and 109.5 g of HCl are allowed to react at 300 K.
(1) – 64.81 (2) – 190.71 (3) – 209.41 (4) – 224.38
12. Which statement regarding entropy is correct ?
(1) A completely ordered deck of cards has more entropy than a shuffled deck in which cards are
arranged randomly.
(2) A perfect ordered crystal of solid nitrous oxide has more entropy than a disordered crystal in which
the molecules are oriented randomly.
(3) 1 mole N2 gas at STP has more entropy than 1 mole N2 gas at 273 K in a volume of 11.2 litre.
(4) 1 mole N2 gas at STP has more entropy than 1 mole N2 gas at 273 K and 0.25 atm.
13. One mole of solid Zn is placed in excess of dilute H2SO4 at 27ºC in a cylinder fitted with a piston. Find
2
the work done for the process if the area of piston is 500 cm and it moves out by 50 cm against a
pressure of 1 atm during the reaction.
Zn(s) + 2H+ (aq) Zn2+ (aq) + H2(g)
(1) – 1.53 KJ (2) – 2.53 KJ (3) Zero (4) 2.53 KJ
14. The enthalpy change for the reaction of 50 mL of ethylene with 50.0 mL of H2 at 1.5 atm pressure is 
H = –0.31 KJ. What is the E ?
(1) – 0.3024 (2) – 0.6048 (3) – 0.1.2 (4) None
15. When 0.1 mole of ice melt at 0ºC and at constant pressure of 1 atm 144 calories of heat are absorbed
by the system. Calculate H for the reaction.
(1) H = 720 J-mol–1 (2) H = 1440 Cal-mol–1 (3) H = 1.4 kCal-mol–1 (4) H = 0
16. One mole of ideal monoatomic gas is carried through the reversible cyclic B
process as shown in figure. Calculate net heat absorbed by the gas in the 3Pº
path BC. Pº C
1 7 A
(1) PºVº (2) PºVº
2 2 Vº 2Vº
5
(3) 2 PºVº (4) PºVº
2

17. 130 g of Zn is dissolved in dilute sulphuric acid in an open beaker at 27ºC. Find the work done in the
process assuming isothermal operation.
(1) – 1200 cal (2) – 1800 cal (3) + 1800 cal (4) +1200 cal
18. The enthalpy of combustion of propane (C3H8) gas in terms of given data is :
Bond energy (kJ/mol)
C—H O=O C=O O—H C—C
+x1 +x2 +x3 +x4 +x5
Resonance energy of CO2 is – zkJ/mol and Hvaporization [H2O()] is ykJ/mol.
(1) 8x1 + 2x5 + 5x2 – 6x3 – 8x4 – 4y – 3z (2) 6x1 + x5 + 5x2 – 3x3 – 4x4 – 4y – 3z
(3) 8x1 + 2x5 + 5x2 – 6x3 – 8x4 – y – z (4) 8x1 + x5 + 5x2 – 6x3 – 8x4 – 4y + 3z
19. If x1, x2 and x3 are enthalpies of H–H, O=O and O–H bonds respectively, and x4 is the enthalpy of
vaporisation of water, estimate the standard enthalpy of combustion of hydrogen.
x x x x
(1) x1  2  2x3  x 4 (2) x1  2  2x3  x 4 (3) x1  2  x3  x 4 (4) 2x 3  x1  2  x 4
2 2 2 2

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Thermodynamics & Thermodynamics
20. NH3(g) + 3Cl2(g)  NCl3(g) + 3HCl(g) ;  H1
N2(g) + 3H2(g)  2NH3(g) ;    H2
H2(g) + Cl2(g)  2HCl(g) ;    H3
The heat of formation of NCl3(g) in the terms of H1, H2 and H3 is
H2 3 H2 3
(1) Hf  H1   H3 (2) Hf  H1   H3
2 2 2 2
H2 3
(3) Hf  H1   H3 (4) None
2 2
21. Hof of water is – 285.5 kJ mol–1. if enthalpy of neutralisation of monoacidic strong base with strong acid
–1 o –
is – 57.3 kJ mol , Hf of OH ion will be
–1 –1 –1 –1
(1) – 228.5 kJ mol (2) 228.5 kJ mol (3) 114.5 kJ mol (4) –114.5 kJ mol
22. Ethanol can undergoes decomposition to form two sets of products.

If the molar ratio of C2H4 to CH3CHO is 8 : 1 in a set of product gases, then the energy involved in the
decomposition of 1 mole of ethanol is
(1) 65.98kJ (2) 48.137 kJ (3) 48.46 kJ (4) 57.22 kJ
23. Find the enthalpy of S–S bond from the following data.
(i) C2H5–S–C2H5(g) Hºf = –147.2 kJ/mol
(ii) C2H5–S–S–C2H5(g) Hºf = –201.9 kJ/mol
(iii) S (g) Hºf = 222.8 kJ/mol
(1) – 168.1 kJ/mol (2) + 168.1 kJ/mol (3) – 277.5 kJ/mol (4) + 277.5 kJ/mol
24. Given the following equations and Hº values, determine the enthalpy of reaction at 298 K for the
reaction :
C2H4(g) + 6F2(g)  2CF4(g) + 4HF(g)
H2(g) + F2(g)  2HF(g) ; Hº1 = –537 kJ
C(s) + 2F2(g)  CF4(g) ; Hº2 = –680 kJ
2C(s) + 2H2(g)  C2H4(g) ; Hº3 = 52 kJ
(1) –1165 (2) –2486 (3) +1165 (4) +2486
25. Animals operate under conditions of constant pressure and most of the process that maintain life are
isothermal (in a broad sense). How much energy is available for sustaining this type of muscular and
nervous activity from the combustion of 1 mol of glucose molecules under standard conditions at 37ºC
(blood temperature) ? The entropy change is + 182. 4 JK–1 for the reaction stated above.
Hcombustion [glucose] = –2808 KJ
(1) – 2754.4 KJ (2) – 2864.5 KJ (3) – 56.5 KJ (4) – 2808 KJ
26. From the given table answer the following question :
CO (g) CO2 (g) H2O(g) H2(g)
Hº 298(–Kcal/ mole ) – 26. 42 – 94.05 – 57 .8 0
Gº 298(–Kcal/ mole ) – 32 .79 – 94 .24 – 54 .64 0
Sº 298(– Cal/ K mol) 47.3 51.1 ? 31.2
Reaction : H2O(g) + CO(g) H2 (g) + CO2 (g)
Calculate So298 [H2O(g)]
(1) – 119.47 Cal/ K mole (2) + 119.47 Cal/ K mole
(3) – 45.13 Cal/ K mole (4) + 45.13 Cal/ K mole
27. Calculate the free energy change at 298 K for the reaction; Br2() + Cl2(g) 2BrCl(g). For the
reaction Hº = 29.3 kJ & the entropies of Br2(),Cl2(g) & BrCl(g) at the 298K are 152.3,223.0,239.7 J
mol–1K–1 respectively.
(1) – 1721.8 J (2) – 60321.8 J (3) + 60321.8 J (4) + 1721.8 J
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Thermodynamics & Thermodynamics
28. One gram sample of oxygen undergoes free expansion in insulated container from 0.75 L to 3.0 L at
298 K. Calculate S, q, w, H and E.
–1
(1) S = 0.36 JK , E = 0 (2) W = 227.97 J, E = 0
(3) q = – 227.97 J, E = 0 (4) W = 227.97 J, H = 0
29. Given that :  Gf° (CuO) = –30.4 kcal/mole
Gf° (Cu2O) = –34.98 kca/mole T = 298 K
Now on the basis of above data which of the following predictions will be most appropriate under the
standard conditions and reversible reaction.
(1) Finely divided form of CuO kept in excess O2 would be completely converted to Cu2O
(2) Finely divided form of Cu2O kept in excess O2 would be completely converted to CuO
(3) Finely divided form of CuO kept in excess O2 would be converted to a mixture of CuO and Cu2O
(having more of CuO)
(4) Finely divided form of CuO kept in excess O2 would be converted to a mixture of CuO and Cu2O
(having more of Cu2O)
30. Calculate fGº for (NH4CI, s) at 310 K.
Given : fHº (NH4CI, s)= –314.5 kJ/mol; rCp = 0
–1 –1 –1 –1
Sº= N2 (g) 192 JK mol ; Sº H2 (g) = 130.5 JK mol ;
–1 –1
SºCl2(g) = 233 JK mol ; Sº NH4 CI(s) = 99.5 JK mol/–1
–1

All given data are at 300 K.

(1) –198.56 kJ/mol (2) –426.7 kJ/mol (3) –202.3 kJ/mol (4) None of these

Practice Test-1 (IIT-JEE (Main Pattern))

OBJECTIVE RESPONSE SHEET (ORS)
Que. 1 2 3 4 5 6 7 8 9 10
Ans.
Que. 11 12 13 14 15 16 17 18 19 20
Ans.
Que. 21 22 23 24 25 26 27 28 29 30
Ans.

PART - II : NATIONAL STANDARD EXAMINATION IN CHEMISTRY (NSEC) STAGE-I

1. The enthalpy of hydrogenation for 1-pentene is +126 KJ/mol. The enthalpy of hydrogenation for 1 : 3-
pentadiene is + 230 KJ/mol. Hence estimate the resonance (delocalization) energy of 1 : 3-pentadiene?
[NSEC–2000]
(A) 22 KJ (B) 104 KJ (C) 252 KJ
(D) Cannot be calculated from this information.
2. The entropy change during an isothermal expansion of an ideal gas from V1 to V2 at temperature T is
given by [NSEC–2000]
(A) S = 0 (B) S = 2.303 R log10 V2 / V1
(C) S = 2.303 RT log10 V2 / V1 (D) S = 2.303 R log10 V1 / V2
3. An isothermal process is associated with [NSEC–2000]
(A) constant entropy (B) constant temperature
(C) constant enthalpy (D) large change in heat content

4. The heat change for the reaction, C(s) + 2S(s)  CS2() is known as [NSEC–2000]
(A) heat of transition (B) heat of fusion
(C) heat of vapourisation (D) heat of formation

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Thermodynamics & Thermodynamics
5. When a solid metls, there is : [NSEC–2001]
(A) decreases in enthalpy (B) increase in enthalpy
(C) no increase in enthalpy (D) decrease in entropy
6. The entropy change for the vapourisation of water at 100ºC (molar latent heat of vapourisation of water
–1
= 40.8 kJ mol ) is : [NSEC–2001]
(A) 109.4 JK mol–1
–1
(B) 0.1094 JK–1mol–1 (C) 0.408JK–1mol–1 (D) 40.8JK–1mol–1
7. The free energy change for an irreversible process is : [NSEC–2001]
(A) zero (B) negative (C) positive (D) very large positive
8. An isobaric process is associated with : [NSEC–2001]
(A) constant temperature (B) constant volume (C) constant pressure (D) small chagne in enthalpy
9. Lattice energy of ionic compound is calculated by using : [NSEC–2002]
(A) Hess’s law (B) Kirchoff’s equation (C) Born-Haber cycle (D) Carnot cycle.
10. According to second law of thermodynamics [NSEC–2002]
(A) total energy in the Universe remains constant
(B) total enthalpy in the Universe remains constant
(C) total entropy of the Universe always increases
(D) total entropy of the Unvierse always decreases.
11. For a spontaneous reaction, G and S should be [NSEC–2002]
(A) G = +ve and S = –ve (B) G = –ve and S = +ve
(C) G = 0 and S = +ve (D) G = +ve and S = 0
12. Which of the following expression is correct ? [NSEC–2002]
(A) E = H + PV (B) H = E + PV (C) H = E – PV (D) P = E + HV
13. The enthalpy change for the fusion of ice at 0oC (molar latent heat of fusion of ice = 6.025 kJ mol–1) is :
[NSEC–2002]
(A) 22.07 JK–1 mol–1 (B) 1.226 JK–1 mol–1 (C) 2.207 JK–1 mol–1 (D) 25.0 JK–1 mol–1
14. The correct figure representing isothermal and adiabatic expansions of an ideal gas from a particular
initial state is [NSEC–2003]

(A) (B)

(C) (D)

15. An ideal gas, on adiabatic expansion, gets cooled because [NSEC–2003]

(A) the average distance between the gas molecules increases and hence the intermolecular
interaction decreases
(B) the internal energy of the gas is used in doing the work of expansion
(C) the temperature of the gas is lower than the inversion temperature corresponding to Joule-
Thomson effect
(D) the pressure decreses and temperature is proportional to the pressure.

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Thermodynamics & Thermodynamics
16. Which energy diagram corresponds to exothermic reaction and highest value of the rate constant ?
[NSEC–2003]

(A) (B)

(C) (D)

17. The following equilibrium exists in a saturated solution of NH4 CI.

NH4CI(S) NH4+ (aq) + CI-(aq) ; H25°C = 3.5 kcal mol-1
A change that will shift the equilibrium to the right is [NSEC–2003]
(A) decrease in temperature
(B) increase in temperature
(C) addition of NH4CI crystals to the reaction mixture
(D) addition of NH4OH solution to the reaction mixture.
18. CCI4(g) + 2H2O(g)  CO2(g) + 4HCI(g). The standard enthalpies of formation at 298 K for CCI4(g), H2O(g),
CO2(g) and HCI (g) are –106.7, –241.8, –393.7 and –92.5 kJ mol-1 respectively. The value of Ho298 for
the above reaction is [NSEC–2004]
(A) –137.7kJ (B) 173.4 kJ (C) –173.4 kJ (D) 137.7 kJ.
19. The temperature of an ideal gas increases in an [NSEC–2004]
(A) adiabatic expansion (B) isothermal expansion
(C) adiabatic compression (D) isothermal compression.
20. The value of n for the combustion reaction of one mole of benzene in gaseous state when both the
reactants and products are at 298 K is [NSEC–2004]
(A) 1 (B) 0 (C) 1/2 (D) –1/2.
21. For two moles of an ideal gas [NSEC–2004]
(A) CV – CP = R (B) CP – CV = 2R (C) CP – CV = R (D) CV – CP = 2R.
22. Heat of combustion of ethanol at constant pressure and at 298 K is found to be –Q kJ mol–1. Hence,
heat of combustion of ethanol at the same temperature at constant volume will be [NSEC–2004]
(A) (–Q + RT) kJ mol-1 (B) (–Q – RT) kJ mol-1 (C) (+Q - RT) kJ mol-1 (D) (Q + RT) kJ mol-1.
23. NH3 (g)  NH2(g) + H (g)
NH2( g)  NH(g) + H(g)
NH (g)  N(g) + H(g)
The enthalpy changes for the above reactions [NSEC–2004]
(A) are the same (B) are in increasing order
(C) are in decreasing order (D) cannot be correlated.
24. How much heat is absorbed in the complete reaction of 3.00 grams of SiO2 with excess carbon in the
reaction below ? [NSEC–2005]
SiO2(g) + 3C(S)  SiC(S) + 2 CO (g) ; HO = +624.7 kJ
(A) 1.33 × 104 kJ (B) 1.13 × 105 kJ (C) 5.06 kJ (D) 31.2 kJ

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25. Estimate the temperature at which G = 0 for the following reaction:
(Given : H = –176 kJ and S = –284.5 J/K). Caution : Beware of units. [NSEC–2005]
NH(g) + HCI (g)  NH4CI(s)
(A) 582 K (B) 467 K (C) 634 K (D) 619 K.
26. A particular chemical reaction is characterised by Hrxn = +250 kJ/mol. Which of the floolwing
statements is/are true concerning this reaction ? [NSEC–2005]
I. Heat is liberated to the surroundings.
II. The reaction is endothermic.
III. The total heat content of the products is lower than that of the reactants.
(A) all are true (B) only II and III are true
(C) only I and II are true (D) only II is true.
27. Of the following composition for the mixture of H2(g) and N2(g) which gives rise to maximum entropy of
mixing? [NSEC–2006]
(A) 2 mols of H2 and 1 mol of N2 (B) 1 mol of H2 and 2 mols of N2
(C) 1.5 mols of H2 and 1.5 mols of N2 (D) 0.5 mol of H2 and 2.5 mols of N2.
28. The enthalpy change, H due to reversible adiabatic expansion of an ideal gas from P1,V1,T1, to P2, V2,
T2 is [NSEC–2006]
T2 T2 V2 P2
(A) CV ln (B) CP In (C) R In (D) R In .
T1 T1 V1 P1

29. Which of the following processes is/are accompanied by an increase in the entropy of the system?
(i) Water freezes
(ii) Iodine sublimes at room temperature
(iii) A building is constructed from bricks and mortar
(iv) A partition is removed to allow two gases to mix [NSEC–2006]
(A) (i) and (iv) (B) (i),(ii) and (iv) (C) (ii) and (iv) (D) only (iv).
30. A reference book lists the heat of formation of NH3(g) to be –46 kJ mol–1. The H (in kJ mol–1) of the
reaction: 2NH3(g)  N2(g) + 3H2(g) is [NSEC–2006]
(A) 46 (B) –46 (C) 92 (D) –92
31. Both the lattice energy (Uo) and hydration enthalpy (Hh) of a binary salt are negative quantities.
However, if Uo is more negative than Hh then [NSEC–2006]
(A) the salt will not dissolve in water (B) salt will dissolve in water
(C) dissolution of salt in water is exothermic (D) dissolution of salt in water is endothermic
32. Preferred conditions for spontaneity in nature are [NSEC–2006]
(A) low enthalpy and low entropy (B) high enthalpy and high entropy
(C) high enthalpy and low entropy (D) low enthalpy and high entropy.
33. The change in free energy accompanied by the isothermal reversible expansion of 1 mol of an ideal gas
when it doubles its volume is G1. The change in free energy accompanied by sudden isothermal
irreversible doubling of volume of 1 mol of the same gas is G2. Ratio of G1 to G2 is : [NSEC–2007]
(A) 1 (B) 1/2 (C) –1 (D) –1/2
34. The degress of freedom for NH4Cl(s) NH4Cl(g) NH3(g) + HCl(g) will be [NSEC–2008]
(A) 4 (B) 3 (C) 2 (D) 1
35. A reversible adiabatic expansion is an [NSEC–2008]
(A) isothermal process (B) isobaric process (C) isentropic process (D) isochoric process
36. If the bond energies are as follows [NSEC–2008]
(i) C–H = 413.8kJ (ii) Cl–Cl = 238.0 kJ (iii) C–Cl = 327.2 kJ (iv) H–Cl = 429.8 kJ
the enthalpy of the reaction: CH4 + 2Cl2  CH2Cl2 + 2HCl will be
(A) +202.6 kJ (B) –202.6 kJ (C) +220.1 kJ (D) +870 kJ

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37. For the isobaric gaseous reaction, the enthalpy change given by – [NSEC–2009]
(A) H = E + nRT (B) H = E + PV (C) H = E + nPV (D) H = E + VP
38. A reaction will never be spontaneous at any temperature and pressure if [NSEC–2010]
(A) S = +ve, H = +ve (B) S = +ve, H = –ve
(C) S = –ve, H = +ve (D) S = –ve, H = –ve
39. The internal energy change involved when a system goes from state A to state B is 40 kJ. If the system
goes from A to B by a reversible path and returns to A by an irreversible path, the net change in internal
energy is [NSEC–2010]
(A) 40 kJ (B) > 40 kJ (C) < 40 kJ (D) zero
40. The enthalpy of formation of carbon dioxide and water are –395kJ and –285kJ, respectively, and the
enthalpy of combustion of acetic acid is –869 kJ. Hence the enthalpy of formation of acetic acid is
[NSEC–2010]
(A) 235 kJ (B) –235 kJ (C) 420 kJ (D) 491 kJ
41. For the reaction N2(g) + 3H2(g)  2NH3(g)
Which of the following is correct ? [NSEC–2010]
(A) H = E (B) H > E (C) H < E (D) H = 2E
42. The enthalpies of decomposition of methane (CH4) (g) and ethane (C2H6)(g) are 400 and 670 kJ. mol–1,
respectively. The HC–C in kJmol–1 is [NSEC–2011]
(A) 270 (B) 70 (C) 200 (D) 240 mol

43. The degrees of freedom for the system CaCO3(s) CaO(s) + CO2(g) are [NSEC–2011]
(A) 1 (B) 2 (C) 3 (D) 4

44. Which of the following has a positive entropy change ? [NSEC–2012]

(A) H2O(g)  H2O(l) (B) BF3(g) + NH3(g)  F3B.NH3(s)
(C) 2SO2(g)+ O2(g)  2SO3(g) (D) 2NH4NO3(g)  2N2(g) + 4H2(O)(l) + O2(g)

45. The enthalpy changes for the following reactions are : [NSEC–2012]
Cdiamond + O2(g)  CO2(g) H = – 395.3 kJ mol–1
Cgraphite + O2(g)  CO2(g) H = – 393.4 kJ mol–1
The enthalpy change for the transition
Cdiamond  Cgraphite will be :
(A) – 3.8 kJ mol–1 (B) + 3.8 kJ mol–1 (C) – 1.9 kJ mol–1 (D) + 1.9 kJ mol–1

46. For a chemical reaction H is negative and S is positive. This reaction is [NSEC–2013]
(A) spontaneous at all temperatures (B) nonspontaneous at all temperature
(C) spontaneous only at high temperature (D) spontaneous only at low temperature

47. 6.24 g of ethanol are vaporized by supplying 5.89 kJ of heat energy. What is the enthalpy of
vapourisation of ethanol ? [NSEC–2013]
(A) 43.42 kJ (B) 47.0 kJ (C) 21.75 kJ (D) 435.0 kJ

48. Two sample A and B of an ideal gas, initially at same temperature and pressure, are compressed from
volume V to V/2, isothermally for A and adiabatically for B. The final pressure of A will be. [NSEC–2014]
(A) greater than that of B (B) less than that of B
(C) twice that of B (D) equal to that at B

49. The heat of formation of ethanol, from the following data is [NSEC–2014]
C2H2OH( )  3O2 (g)  2CO2 (g)  3H2O( ) 1368J
Hr CO2 (g)  393.5kJ / mol ; HrH2O( )  286kJ / mol
(A) – 277 kJ/mol (B) – 1260.5 kJ/mol (C) – 688.5 kJ/mol (D) – 3013 kJ/mol
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50. N2 gas stored in a cylinder, fixed with a movable piston, undergoes adiabatic expansion. The statement
that is true for the given situation is [NSEC–2014]
(A) q = W (B) U = W (C) U = 0 (D) U = q

51. The enthalpy of vaporization of benzene is +35.3 kJ/mol at its boiling point of 80ºC. The entropy change
in the transition of vapour of liquid at its boiling point is [NSEC–2014]
(A) –100 (B) +100 (C) +342 (D) –342
52. The process in which an ideal gas undergoes change from X to Y as shown in the
following diagram is [NSEC–2015]
(A) isothermal compression (B) adiabatic compression
(C) isothermal expansion (D) adiabatic expansion

53. Glucose when dissolved in water leads to cooling of the solution. Suppose you take 250 mL water at
room temperature in an open container (such as a bowl) made of thermally insulated material and
dissolve a spoonful’ of glucose in it. If you are able to accurately measure the heat absorbed by this
solution in reaching back to room temperature (assuming negligible changes in the composition and the
amount of solution during this process), you will be measuring [NSEC–2015]
(A) The enthalpy of dissolution of the glucose in water
(B) The Gibbs free energy of dissolution of the glucose in Water
(C) The work done by the atmosphere on the system during the dissolution process
(D) The heat capacity of the solution
54. An ideal gas taken in an insulated chamber is released into interstellar space. The statement that is
nearly true for this process is [NSEC–2015]
(A) Q = 0, W  0 (B) W = 0, Q  0 (C) U = 0, Q  0 (D) Q = W = U = 0
55. Standard molar enthalpy of formation of CO2(g) is equal to [NSEC–2016]
(A) Zero
(B) The standard molar enthalpy of combustion of carbon (graphite)
(C) The standard molar enthalpy of combustion of C(g)
(D) The standard molar enthalpy of combustion of CO(g)

56. For the conversion CCl4()  CCl4(g) at 1 bar and 350 K, the correct set of thermodynamic parameters
is (Boiling point of CCl4 is 77ºC) [NSEC–2016]
(A) G = 0, S = +ve (B) G = 0, S = –ve (C) G = –ve, S = 0 (D) G = –ve, S = +ve
57. Which reaction is spontaneous at all temperatures at standard pressure and concentration ?
(A) exothermic reaction with a decrease in entropy [NSEC–2016]
(B) exothermic reaction with an increase in entropy
(C) endothermic reaction with a decrease in entropy
(D) endothermic reaction with an increase in entropy
–1 –1
58. Given rHº = –54.08kJ mol and rSº = 10.0 J mol at 25ºC, the value of log10K for the reaction
A B is [NSEC–2016]
(A) 3.4 (B) 10 (C) 0.53 (D) 113
59. Three samples of 100 g of water (samples I, II and III), initially kept at 1 atm pressure and 298 K were
given the following treatments.
Sample I was heated to 320 K and cooled to 298 K
Sample II was heated to 300 K, cooled to 273 K and heated to 298 K
Sample III was heated to 373 K and cooled to 298 K
At the end of these processes, the internal energy of [NSEC–2017]
(A) III is the highest (B) II is the highest
(C) I and III are the same, II is lower than that of I and III (D) I, II and III are the same

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60. For the following spontaneous process H2O(I) H2O(s) at 268 K, which of the following is true?
(A) Ssys < 0 (B) Ssys > 0 (C) Ssurr < 0 (D) Ssys = –Ssurr
61. At constant volume, 6.0 mol of H2 gas at 0ºC and 100 kPa was heated to 250 kPa. The molar heat of H2
at constant pressure (CP) = 28.9 J mol–1. (Assume that the heat capacity values do not change with
temperature). The final temperature of the H2 gas and the change in entropy of the process are
[NSEC–2017]
(A) 273ºC and 113 kJ mol–1 K–1 (B) 410ºC and 158.8 J mol–1 K–1
(C) 682.5ºC and 113 J mol–1 K–1 (D) 682.5 K and 113 J mol–1 K–1
59. Hydrazine used in rocket fuels can be obtained by the reaction of ammonia and hydrogen peroxide
according to the following equations
2NH3(g) + H2O2(l)  N2H4(l) + 2H2O(l) (Hºreaction = –241kJ/mol)
If Hº (formation) of NH3, H2O2 and H2O are –46.1, –187.8 and –285.8kJ/mol respectively, Hº for the
decomposition of hydrazine into N2 and H2 is [NSEC–2017]
(A) 50.6 kJ/mol (B) 241 kJ/mol (C) –50.6 kJ/mol (D) 120.5 kJ/mol

PART - III : HIGH LEVEL PROBLEMS (HLP)

SUBJECTIVE QUESTIONS
1. 6 moles of an ideal gas expand isothermally and reversibly from a volume of 1 litre to a volume of 10
litres at 270C. What is the maximum work done.
2. Calculate work done by 1 mole of Ideal gas expand isothermally and irreversibly from pressure of 5 atm
to 2 atm against a constant external pressure of 1 atm at 300 K temperature.
3. One mole of Ideal gas (CP, m = 15 JK–1 mole–1) follow the process as shown in
figure.

Predict the following :

(i) Nature of process

(ii) Calculate work done, Heat of process.

4. 1 mole of CO2 gas at 300 K is expanded under reversible adiabatic condition such that its volume
becomes 27 times.
(a) What is the final temperature ? (b) What is work done ?
Given  = 1.33 and CV = 25.08 Jmol–1K–1 for CO2.
5. (a) A certain mass of a gas initially at (1 L, 5 atm, 300 K) is expanded reversibly and isothermally to a
final volume of 5L, calculate work done by the gas and heat supplied in this process to the gas.
(b) Now, if the gas is restored to initial position by compressing it using an external constant pressure of
5 atm. Find work done on the gas in this process and heat rejected by gas
(c) In the above two processes, what is the net heat gained by surroundings?
[Note : From above question see that surroundings has done extra work on the system but system has
returned that work in the form of heat to surroundings and work is considered on organized form of
energy while heat as an unorganised form hence in the above process, there must be net increment in
randomness of universe which will be called Entropy, soon.]
6. The molar heat capacity, Cv of helium gas is 3/2 R and is independent of temperature. For hydrogen
gas, Cv approaches 3/2 R at very low temperatures, equal 5/2 R at moderate temperatures and is
higher than 5/2 R at high temperatures. Give a reason for the temperature dependence of Cv in case of
hydrogen, in not more than two or three sentences. [JEE 2003, 2/60]
7. There is 1 mol liquid (molar volume 100 ml) in an adiabatic container initial, pressure being 1 bar Now
the pressure is steeply increased to 100 bar, and the volume decreased by 1 ml under constant
5 2
pressure of 100 bar. Calculate H and E. [Given 1 bar = 10 N/m ] [JEE 2004, 2/60]
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8. One mole of monoatomic gas was taken through a cyclic process as shown in figure.

dqrev
Calculate . 
ABCA T

9. One mole of ideal monoatomic gas was taken through isochoric heating from 100 K to 1000 K.
Calculate Ssystem, Ssurr and Stotal in
(i) when the process carried out reversibly (ii) when the process carried out irreversibly (one step)
10. Comment on the following statements :
(a) An exothermic reaction is always thermodynamically spontaneous.
(b) Reaction with G° < 0 always have an equilibrium constant greater than 1.
11. Following reaction occurs at 25°C :
2NO (g, 1 × 10–5 atm) + Cl2 (g, 1 × 10–2 atm) 2NOCl (g, 1 × 10–2 atm) 
 Calculate G° [R = 8 J/mole K]
12. For the reaction : N2O4(g) 2NO2 (g)
(i) In a mixture of 5 mol NO2 and 5 mol N2O4 and pressure of 20 bar. Calculate the value of G
for the reaction. Given Gf° (NO2) = 50 kJ / mol, Gf° (N2O4) = 100 kJ / mol and T = 298 K.
(ii) Predict the direction in which the reaction will shift, in order to attain equilibrium
[Given at T = 298 K, 2.303 RT = 5.7 kJ / mol.] [JEE 2004, 2/60]
13. The difference between heats of reaction at constant presure and at costant volume for the reaction :
2C6H6 () + 15O2 (g)  12CO2 (g) + 6H2O () at 25ºC in kJ is :

14. Classify the following processes as exothermic or endothermic :

(A) Burning of a match stick (B) Melting of ice
(C) Molten metal solidifies (D) Reaction between Na and H2O
(E) Rubbing alcohol evaporates.
15. Why is the enthalpy of sublimation equal to the sum of enthalpy of fusion and enthalpy of vaporisation ?
16. For a chemical reaction, CP is negative (CP < 0).
The heat required to increase temperature of reactants of this reaction by a certain amount = q1 and
heat required to increase temperature of products of the same reaction by same amount = q2, Relate q1
and q2
17. The specific heats of iodine vapour and solid are 0.031 calg–1 ºC–1 and 0.055 calg–1 ºC–1 respectively. If
heat of sublimation of iodine is 24 cal/g at 200ºC, what is its value at 250ºC ?
18. Find out the heat evolved in combustion if 112 litres (at STP) of water gas (mixture of equal volume of
H2(g) and CO (g)).
H2(g) + 1/2 O2 (g)  H2O(g) H = – 241.8 kJ
CO (g) + 1/2 O2(g)  CO2(g) H = – 283 kJ
19. Substance A2B(g) can undergoes decomposition to form two set of products :

If the molar ratio of A2(g) to A(g) is 5 : 3 in a set of product gases, calculate the energy involved in the
decomposition of 1 mole of A2B ,

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0 –1 –1
20. The H f (KF,s) is – 563 kJ mol . The ionization enthalpy of K(g) is 419 kJ mol . and the enthalpy of
sublimation of potassium is 88 kJ mol–1. The electron affinity of F(g) is 322 kJ mol–1 and F–F bond
enthalpy is 158 kJ mol–1. Calculate the lattice enthalpy of KF(s).
The given data are as follows :
(i) K(s) + ½F2(g)  KF(s) H0f = – 563 kJ mol–1
+ – 0 –1
(ii) K(g)  K (g) + e  H Ioniz = 419 kJ mol
0 –1
(iii) K(s)  K(g) H sub = 88 kJ mol
(iv) F(g) + e–  F–(g) H0eg = – 322 kJ mol–1
0 –1
(v) F2(g) 2F(g) H diss = 158 kJ mol
+ – 0
(vi) K (g) + F (g)  KF(s) H L = ?

ONLY ONE OPTION CORRECT TYPE

21. In thermodynamics, a process is called reversible when -
(A) surroundings and system change into each other
(B) there is no boundary between system and surroundings
(C) the surroundings are always in equilibrium with the system
(D) the system changes into the surroundings spontaneously
22. Two moles of an ideal gas expand spontaneously in vacuum. The work done is :
(A) 2 Joule (B) 4 Joule (C) Zero (D) Infinite
23. Temperature of 1 mole of a gas is increased by 2°C at constant pressure, then wark done is :
(A) R (B) 2R (C) R/2 (D) Data insufficient
24. Mechanical work is specially important in system that contain
(A) Solid-liquid (B) Liquid-Liquid (C) Solid-Solid (D) Gases

25. Which of the following statements is/are correct regarding the following
process : A

(A) dW = – Pext.dv = 0; Only if the system is undergoing only P–V work.

(B) dW = – Pext.dv = 0; Irrespective of any type of work done by the system. P

(C) dU  dqv B
(D) dW  0
V

26. A piece of zinc at a temperature of 20°C weighing 65.38 g is dropped into 180 g of boiling water (T =
100°C). The specific heat of zinc is 0.4 J g–1 C–1 and that of water is 4.2 J g–1°C–1. What is the final
common temperature reached by both the zinc and water ?
(A) 97.3 °C (B) 33.4 °C (C) 80.1 °C (D) 60.0°C
27. Which has maximum internal energy at 290 K ?
(A) Neon gas (B) Nitrogen gas (C) Ozone gas (D) All have equal value
28. A sample of liquid in a thermally insulated container (a calorimeter) is stirred for 2 hr. by a mechanical
linkage to a motor in the surrounding, for this process :
(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
29. A balloon of 1 L volume is fill with O2 gas, kept in a spaceship at STP. Now this spaceship is send in
space & the balloon is released out of the spaceship. Then balloon expands upto bursting then
calculate work done by balloon.
(A) 0 (B) 1 (C) 2 (D) 3
30. 1 mole of an ideal diatomic gas undergoes a reversible polytropic process (PV2 = constant). The gas
expand from initial volume of 1 litre and temp 300 K to find volume 3 lit. Calculate change in internal
energy (approx.)
(A) –4.0 kJ (B) –4.2 kJ (C) –4.4 kJ (C) –4.6 kJ

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31. A system containing real gas changes it's state form state-1 to state-2.
State-1 (2 atm, 3L, 300 K)
State-2 (5 atm, 4L, 500 K)
If change in internal energy = 30 L atm then calculate change in enthalpy.
(A) 44 L atm (B) 35 L atm (C) 40 L atm (D) None of these

32. A container of volume 2L is separated into equal compartments.

In one compartment one mole of an ideal monoatomic gas is filled at 1 bar
pressure and the other compartment is completely evacuated. A pinhole is
made in the separator so gas expands to occupy full 2L and heat is supplied
to gas so that finally pressure of gas equals 1 bar. Then :
(A) U = H = 150 J (B) H = 250 J (C) U = 100 J (D) U = H = 0
33. Which one of the following statement is false :
(A) work is a state function
(B) temperature is a state function
(C) change in the state is completely defined when the initial and final states are specified
(D) work appears at the boundary of the system.
34. Identify the state function among the following
(A) q (B) q – w (C) q/w (D) q + w
35. Two moles of Helium gas undergo a reversible cyclic process as showin in
figure. Assuming gas to be ideal, what is the net work involved in the cyclic
process ?

(A) – 100 Rn4 (B) +100Rn4

(C) +200Rn4 (D) –200Rn4

36. Ice–Water mass ratio is mantained as 1 : 1 in a given system containing water in equilibrium with ice at
constant pressure. If CP(ice) = CP(water) = 4.18 J mol–1 K–1 molar heat capacity of such a system is
(A) Zero (B) Infinity (C) 4.182 JK–1 mol–1 (D) 75.48 JK–1 mol–1
37. Two mole of an ideal gas is heated at constant pressure of one atomosphere from 27ºC to 127ºC. If
Cv,m = 20 + 10–2 T JK–1 mol–1, then q and U for the process are respectively :
(A) 6362.8 J, 4700 J (B) 3037.2 J, 4700 J (C) 7062.8, 5400 J (D) 3181.4 J, 2350 J
38. The increase in internal energy of 1 kg of water at 100°C when it is converted into steam at the same
temperature and at 1 atm (100 k Pa) will be [The density of water and steam are 1000 kg/m 3 & 0.6
kg/m3 respectively. The latent heat of vapourisation of water is 2.25 × 106 J/kg.]
(A) 2.08 × 106 J (B) 4 × 107 J (C) 3.27 × 108 J (D) 5 × 109 J

39. Consider a classroom that is roughly 5 m × 10 m × 3 m. Initially t = 27°C and P = 1 atm. There are 50
people in an insulated class loosing energy to the room at the average rate of 150 watt per person. How
long can they remain in class if the body temperature is 42°C and person feels uncomfortable above
this temperature. Heat capacity of air = (7/2) R.
(A) 4.34 minutes (B) 5.91 minutes (C) 6.86 minutes (D) 7.79 minutes

40. A heat engine carries one mole of an ideal mono-atomic gas around the
cycle as shown in the figure, the amount of heat added in the process AB
and heat removed in the process CA are :
(A) qAB = 450 R and qCA = –450 R
(B) qAB = 450 R and qCA = –225 R
(C) qAB = 450 R and qCA = –375 R
(D) qAB = 375 R and qCA = –450 R
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41. There are two samples of same gas initially under similar initial state. Gases of both the samples are
expanded. st sample using reversible isothermal process and nd sample using reversible adiabatic
process till final pressures of both the samples becomes half of initial pressure. Then :
(A) Final volume of st sample < final volume of nd sample
(B) Final volume of nd sample < final volume of st sample
(C) Final volumes will be equal
(D) Information is insufficient
42. In the above problem :
(A) work done by gas in st sample > work done by gas in nd sample
(B) work done by gas in nd sample > work done by gas in st sample
st nd
(C) work done by gas in  sample = work done by gas in  sample
(D) none of these
43. A new flurocarbon of molar mass 102 g mol1 was placed in an electrically heated vessel. When the
0
pressure was 650 torr, the liquid boiled at 77 C. After the boiling point had been reached, it was found
that a current of 0.25 A from a 12.0 volt supply passed for 600 sec vaporises 1.8g of the sample. The
molar enthalpy & internal energy of vaporisation of new flourocarbon will be :
(A)H = 102 kJ/mol, E = 99.1 kJ/mol (B) H = 95 kJ/mol, E = 100.3 kJ/mol
(C) H = 107 kJ/mol, E = 105.1 kJ/mol (D) H = 92.7 kJ/mol, E = 97.4 kJ/mol
44. Internal pressure of a perfect gas (ideal gas) is :
(A) Zero (B) infinite
(C) Calculated by PV = nRT (D) Can not say directally
45. In a laboratory, liquid in a thermally insulated container is stirred for one hr, by a mechanical linkage to
a in surrounding, for this process :
(A) W < 0; q = 0 (B) W < 0; q > 0 (C) W < 0; q > 0 (D) W > 0 ; q = 0
46. If W 1; W 2 & W 3 are magnitude of work done of an ideal gas in isothermal, adiabatic & isobaric reversible
expansion process from same initial stage to same final volume. Then correct order will be :
(A) W 3 > W 1 > W 2 (B) W 3 > W 2 > W 1 (C) W 2 > W 1 > W 3 (D) W 1 > W 2 > W 3
47. A certain mass of gas is expanded from (1L, 10 atm) to (4L, 5 atm) against a constant external pressure
of 1 atm. If initial temperature of gas is 300 K and the heat capacity of process is
50 J/°C. Then the enthalpy change during the process is (1L atm ~ 100 J)
(A) H = 15 kJ (B) H = 15.7 kJ (C) H = 14.4 kJ (D) H = 14.7 kJ
48. 2 moles of ideal gas is expanded isothermally & reversibly from 1 litre to 10 litre. Find the enthalpy
change in kJ mol–1. [JEE 2004, 3/84]
(A) 0 (B) 11.7 (C) – 11.7 (D) 25
49. One mole of an ideal monoatomic gas at temperature T and volume 1L expands to 2L against a
constant external pressure of one atm under adiabatic conditions, then final temperature of gas will be :
[JEE 2005, 3/84]
2 2 T T
(A) T + (B) T – (C) 5 / 3 1 (D) 5 / 3 1
3  0.0821 3  0.0821 2 2
50. The ratio of P to V at any instant is constant and is equal to 1, for a monoatomic ideal gas under going
a process. What is the molar heat capacity of the gas. [JEE 2006, 3/184]
3R 4R 5R
(A) (B) (C) (D) 0
2 2 2
51. An ideal gas expands in volume from 1 × 10–3 m3 to 1 × 10–2 m3 at 300 K against a constant pressure
of 1 × 105 Nm–2 . The work is : [AIEEE 2004]
(A) – 900 J (B) – 900 kJ (C) 270 kJ (D) + 900 kJ
52. Consider the reaction, N2(g) + 3H2(g)  2NH3(g); carried out at constant temperature and pressure. If
H and U are enthalpy change and internal energy change respectively, which of the following
expressions is true ? [AIEEE 2005]
(A) H = 0 (B) H = U (C) H < U (D) H > U
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Thermodynamics & Thermodynamics
53. An ideal gas is allowed to expand both reversibly and irreversibly in an isolated system. If Ti is the initial
temperature and Tf is the final temperature, which of the following statements is correct ? [AIEEE 2006]
(A) Tf > Ti for reversible process but Tf = Ti for irreversible process
(B) (Tf)rev = (Tf)irrev
(C) Tf = Ti for both reversible and irreversible processes
(D) (Tf)irrev > (Tf)rev
54. When one mole of an ideal gas is comressed to half of its initial volume and simultaneously heated to
twice its initial temperature, the change in entropy of gas (S) is :
(A) Cp, m ln 2 (B) Cv, m ln 2 (C) R ln 2 (D) (Cv, m – R) ln 2
55. Two mole of an ideal gas is expanded irreversibly and isothermally at 37ºC until its volume is doubled
and 3.41 kJ heat is absorbed from surrounding. Stotal (system + surrounding) is :
(A) –0.52 J/K (B) 0.52 J/K (C) 22.52 J/K (D) 0
56. 1 mole of an ideal gas at 25°C is subjected to expand reversibly and adiabatically to ten times of its
–1 –1
initial volume. Calculate the change in entropy during expansion (in J k mol )
(A) 19.15 (B) – 19.15 (C) 4.7 (D) zero
57. What is the change in entropy when 2.5 mole of water is heated from 27ºC to 87ºC ? Assume that the
heat capacity is constant. (Cp,m (H2O) = 4.2 J/g-K ln (1.2) = 0.18)
(A) 16.6 J/K (B) 9 J/K (C) 34.02 J/K (D) 1.89 J/K
58. C2H6 (g) + 3.5 O2 (g)  2CO2 (g) + 3H2O (g)
Svap (H2O, ) = x1 cal K-1 (boiling point = T1)
Hf (H2O, ) = x2
Hf (CO2) = x3
Hf (C2H6) = x4
Hence, H for the reaction is -
(A) 2x3 + 3x2 – x4 (B) 2x3 + 3x2 – x4 + 3x1T1
(C) 2x3 + 3x2 – x4 – 3x1T1 (D) x1T1 + X2 + X3 – x4
59. Consider the Gºƒ and Hºƒ (kJ/mol) for the following oxides. Which oxide can be most easily
decomposed to form the metal and oxygen gas ?
(A) ZnO (Gº = –318.4, Hº = –348.3) (B) Cu2O (Gº = –146.0, Hº = –168.8)
(C) HgO (Gº = –58.5, Hº = –90.8) (D) PbO (Gº = –187.9, Hº = –217.3)
60. If a refrigerator's door is opened, then we get
(A) Room heated (B) Room cooled
(C) More amount of heat is passed out (D) No effect on room
61. Which of the following statement (s) is/are correct?
Statement (i) : The entropy of isolated system with P–V work only, is always maximized at equilibrium.
Statement (ii) : It is possible for the entropy of close system to decrease substantially in an irreversible
process.
Statement (iii) : Total entropy can be created but not destroyed.
Statement (iv) : Ssystem is zero for reversible process in an isolated system.
(A) Statement i, ii, iii, (B) Statement ii, iv (C) Statement i, ii, iv (D) All of these
62. During winters, moisture condenses in the form of dew and can be seen on plant leaves and grass. The
entropy of the system in such cases decreases as liquids possess lesser disorder as compared to
gases. With reference to the second law, which statement is correct, for the above process?
(A) The randomness of the universe decreases
(B) The randomness of the surroundings decreases
(C) Increase is randomness of surroundings equals to the decrease in randomness of system
(D) The increase in randomness of the surroundings is greater as compared to the decrease in
randomness of the system.

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63. When CH3OH () is mixed in water :
(A) Degree of Randomness (entropy) decreases due to formation of Hydrogen bond.
(B) Entropy of surrounding decreases
(C) Mixing is spontaoneous and reversible process
(D) All of the above are correct
64. Although graphite is thermodynamically most stable allotrope of Carbon but it has more entropy than
diamond. Because :
(A) It has layer structure which slides on each other.
(B) In diamond Carbon is bonded with covalent bond.
(C) In graphite covalent bond only present within sheet and weak vanderwaal froce present between
sheets which allow sliding easliy.
(D) Two types of bond lengths are present in graphite.
65. By how much does the entropy of universe change if 3 mole of an ideal gas is going from a pressure of
2 bar to a pressure of 1 bar without any change in temperature. If the surrounding is at 1 bar and 300 K.
(Expansion is again of the constant external pressure of surrounding).
(A) + 7.29 J-K–1 (B) + 4.82 J-K–1 (C) – 5.29 J-K–1 (D) – 8.35 J-K–1
66. For a perfectly crystalline solid Cp,m = aT3 + bT, where a and b constant. If Cp,m is 0.40 J/K mol at 10 K
and 0.92 J/K mol at 20 K, then molar entropy at 20 K is :
(A) 0.92 J/K mol (B) 8.66 J/K mol (C) 0.813 J/K mol (D) None of these
67. For the hypothetical reaction A2(g) + B2(g) 2AB(g)
If rGº and rSº are 20 kJ/mol and –20 JK–1 mol–1 respectively at 200 K.
rCp is 20 JK–1 mol–1 then rHº at 400 K is :
(A) 20 kJ/mol (B) 7.98 kJ/mol (C) 28 kJ/mol (D) None of these
68. Given rSº = –266 and the listed [Sºm values].
Calculate Sº for Fe3O4(s) :
4Fe3O4 (s) [..............] + O2 (g) [205]  6Fe2O3 (s) [87]
(A) +111.1 (B) +122.4 (C) 145.75 (D) 248.25
–1
69. The enthalpy change for a given reaction at 298 K is – x J mol (x being positive). If the reaction occurs
spontaneously at 298 K, the entropy change at that temperature
(A) can be negative but numerically larger than x/298
(B) can be negative but numerically smaller than x/298
(C) cannot be negative
(D) cannot be positive
70. Select the correct statement(s) :
S1 : AlCl3 when dissolve in H2O its entropy decreases therefore it is a non-spontaneous process.
S2 : When H2 gas adsrobed at the surfce of Pd, some amount of heat is released.
S3 : Entropy of D2 gas is greater than H2 gas.
(A) S1, S2 & S3 (B) S1 & S3 (C) S2 & S3 (D) S1 & S2
71. One mole of an ideal diatomic gas (Cv = 5 cal) was transformed from initial 25°C and 1 L to the state
when temperature is 100°C and volume 10 L. The entropy change of the process can be expressed as
(R = 2 calories/mol/K)
298 373
(A) 3 ln + 2 ln 10 (B) 5 ln + 2 ln 10
373 298
373 1 373 1
(C) 7 ln + 2 ln (D) 5 ln + 2 ln
298 10 298 10
72. Combustion of sucrose is used by aerobic organisms for providing energy for the life sustaining
processes. If all the capturing of energy from the reaction is done through electrical process (non P–V
work) then calculate maximum available energy which can be captured by combustion of 34.2 g of
sucrose.
–1
Given : Hcombustion (sucrose) = – 6000 kJ mol
Scombustion = 180 J/K-mol and body temperature is 300 K
(A) 600 kJ (B) 594.6 kJ (C) 5.4 kJ (D) 605.4 kJ
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Thermodynamics & Thermodynamics
73. Given the following data :
Substance H° (kJ/mol) S°(J/mol K) G° (kJ/mol)
FeO(s) – 266.3 57.49 – 245.12
C (Graphite) 0 5.74 0
Fe(s) 0 27.28 0
CO(g) – 110.5 197.6 – 137.15
Determine at what temperature the following reaction is spontaneous ?
FeO(s) + C (Graphite)  Fe(s) + CO(g)
(A) 298 K (B) 668 K (C) 964 K
(D) G° is +ve, hence the reaction will never be spontaneous
–1
74. H = 30 kJ mol , S = 75 J / k / mol. Find boiling temperature at 1 atm. [JEE 2004, 3/84]
(A) 400 K (B) 300 K (C) 150 K (D) 425 K
75. Spontaneous adsorption of a gas on a solid surface is exothermic process because [JEE 2004, 3/84]
(A) enthalpy of the system increases. (B) entropy increases.
(C) entropy decreases. (D) free energy change increases.
76. For a spontaneous reaction the G, equilibrium constant (K) and E°cell will be respectively
[AIEEE 2005]
(A) – ve, > 1, + ve (B) + ve, > 1, – ve (C) – ve, < 1, –ve (D) – ve, > 1, – ve
77. If H is the change in enthalpy and U the change in internal energy accompanying a gaseous reaction
(A) H is always greater than U
(B)H < U only if the number of moles of the products is greater than the number of the reactants
(C) H is always less than U
(D)H < U only if the number of moles of the products is less than the number of moles of the
reactants

78. In the reaction CS2 () + 3O2 (g) CO2 (g) + 2SO2 (g), H = – 265 kcal
The enthalpies of formation of CO2 and SO2 are both negative and are in the ratio 4 : 3. The enthalpy of
formation of CS2 is +26kcal/mol. Calculate the enthalpy of formation of SO2.
(A) – 90 kcal/mol (B) – 52 kcal/mol (C) – 78 kcal/mol (D) – 71.7 kcal/mol
79. Heat of hydrogenation of ethene is x1 and that of benzene is x2. Hence, resonance energy is :
(A) x1 – x2 (B) x1 + x2 (C) 3x1 – x2 (D) x1 – 3x2
80. Calculate the resonance energy of gaseous benzene from the given data
HC–H = 416 ; HC–C = 331; HC=C = 591; Hsub (C, graphite) = 718
Hdiss (H2 , g) = 436 and Hf (benzene, g) = 83 (all unit in kJ mole–1)
(A) 354 (B) 271 (C) 437 (D) 83
81. Born-Haber cycle is used to determine :
(A) Lattice energy (B) Electron affinity (C) Crystal energy (D) All of these
82. Heat of neutralization of strong acid by a strong base is a constant value due to :
(A) salt formed does not hydrolysis
(B) only H+ and OH– ions react
(C) The strong base and strong acid react completely
(D) The strong base and strong acid react in aqueous solution
Heat of neutralization of strong acid by a strong base is a constant value due to :
83. If CH3COOH + OH–  CH3COO– + H2O + q1
H+ + OH–  H2O + q2
then the enthalpy change for the reaction CH3COOH  CH3COO– + H+ is equal to:
(A) (q1 + q2) (B) (q1 – q2) (C) (q2 – q1) (D) – (q1 + q2)
84. Enthalpy of neutralization of H3PO3 acid is – 106.68 kJ/mol using NaOH. If enthalpy of neutralization of
HCl by NaOH is –55.84 kJ/mol. Calculate Hionization of H3PO3 into its ions :
(A) 50.84 kJ/mol (B) 5 kJ/mol (C) 2.5 kJ/mol (D) None of these
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85. The difference between H and E (on a molar basis) for the combustion of n-octane () at 25°C would
be :
(A) – 13.6 kJ (B) – 1.14 kJ (C) – 11.15 kJ (D) + 11.15 kJ
86. The heat of formation of HCl at 348 K from the following data, will be
0.5 H2(g) + 0.5 Cl2 (g)  HCl H°298 = – 22060 cal
The mean heat capacities over this temperature range are,
–1 –1 –1 –1 –1 –1
H2(g), CP = 6.82 cal mol K ; Cl2 (g), Cp = 7.71 cal mol K ; HCl (g), CP = 6.81 cal mol K
(A) – 20095 cal (B) – 32758 cal (C) – 37725 cal (D) – 22083 cal

87. From the following data of H, of the following reactions,

1
C(s) + O2 (g)  CO (g)   H = – 110 kJ
2
C(s) + H2O (g)  CO (g) + H2(g)  H = 132 kJ
What is the mole composition of the mixture of steam and oxygen on being passed over coke at 1273
K, to maintain constant temperature :
(A) 0.5 : 1 (B) 1 : 0.6 (C) 0.8 : 1 (D) 1 : 1
88. When 12.0 g of carbon reacted with limited quantity of oxygen, 57.5 kcal of heat was produced,
Calculate the number of moles of CO produced (fH (CO2) = – 94.05 kcal, fH (CO) = – 21.41 kcal.
(A) 0.5 mol (B) 0.46 mol (C) 0.64 mol (D) 0.74 mol
89. The standard enthalpy of formation of FeO & Fe2O3 is  65 kcal mol1 and 197kcalmol1 respectively. A
mixture of two oxides contains FeO & Fe2O3 in the mole ratio 2 : 1. If by oxidation, it is changed into a
1 : 2 mole ratio mixture, how much of thermal energy will be released per mole of the initial mixture ?
(A) 13.4 kcal/mole (B) 14.6 kcal/mole (C) 15.7 kcal/mole (D) 16.8 kcal/mole
90. Reactions involving gold have been of particular interest to alchemists. Consider the following
reactions,
Au(OH)3 + 4 HCl  HAuCl4 + 3 H2O, H =  28 kcal
Au(OH)3 + 4 HBr  HAuBr4 + 3 H2O, H =  36.8 kcal
In an experiment, there was an absorption of 0.44 kcal when one mole of HAuBr4 was mixed with 4
moles of HCl. Then, the fraction of HAuBr4 converted into HAuCl4 (percentage conversion)
(A) 5% (B) 6 % (C) 7% (D) 8%
91. The average XeF bond energy is 34 kcal/mol, first I.E. of Xe is 279 kcal/mol, electron affinity of F is
85 kcal/mol & bond dissociation energy of F2 is 38 kcal/mol. Then, the enthalpy change for the reaction
XeF4  Xe+ + F + F2 + F will be
(A) 367 kcal/mole (B) 425 kcal/mole (C) 292 kcal/mole (D) 392 kcal/mole
92. Equal volumes of molar hydrochloric acid and sulphuric acid are neutralized by dil. NaOH solution and x
kcal and y kcal of heat are liberated respectively. Which of the following is true ?
1
(A) x = y (B) x = y (C) x = 2y (D) None of these
2
93. A solution is 500 ml of 2 M KOH is added to 500 ml of 2 M HCl and the mixture is well shaken. The rise
in temperature T1 is noted. The experiment is then repeated using 250 ml of each solution and rise in
temperature T2 is again noted. Assume all heat is taken by the solution
(A) T1 = T2 (B) T1 is 2 times as large as T2
(C) T2 is twice of T1 (D) T1 is 4 times as large as T2
94. 50.0 mL of 0.10 M HCl is mixed with 50.0 mL of 0.10 M NaOH. The solution's temperature rises by
3.0ºC. Calculate the enthalpy of neutralization per mole of HCl. (Assuming density of sol. = 1 g/ml &
specifice heat of water is 4.2 J/g-K) is
2 2 1 1
(A) – 2.5×10 kJ/mole (B) –1.3×10 kJ/mole (C) – 8.4×10 kJ/mole (D) – 6.3×10 kJ/mole

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95. A piece of NH4Cl is kept inside a ballon filled with Insulated expandable
some air, having thermally insulated walls. The balloon
temperature is kept just above sublimation
temperature of NH4Cl.
sub lim e
NH4Cl (s)   NH3 (g) + HCl (g). NH4Cl
Which of the following is correct regarding this :
(A) qsystem = positive Temperature just above sublimation
(B) U = negative Temperature of NH4Cl
(C) w = zero
(D) U = positive

96. Equal volume of HCOOH and NaOH are mixed. If x is the heat of formation of water from strong acid &
strong base, then heat evolved of neutralization is :
(A) more than x (B) equal to x (C) twice of x (D) less than x
97. Which of the following equation gives the values of heat of formation (Hf0) [JEE 2003, 3/84]
1 1
(A) C (diamond) + O2(g)  CO2 (g) (B) H2(g) + F2(g)  HF(g)
2 2
(C) N2(g) + 3H2(g)  2NH3(g) (D) H2(g) + F2(g)  2HF(g)
98. The enthalpies of combustion of carbon and carbon monoxide are – 393.5 and – 283 kJ mol–1
respectively. The enthalpy of formation of carbon monoxide per mole is [AIEEE 2004]
(A) 110.5 kJ (B) 676.5 kJ (C) – 676.5 kJ (D) – 110.5 kJ
99. If the bond dissociation energies of XY, X2 and Y2 (all diatomic molecules) are in the ratio of 1 : 1 : 0.5
and Hf for the formation of XY is - 200 KJ mol–1. The bond dissociation energy of X2 will be
[AIEEE 2005]
(A) 100 KJ mol–1 (B) 200 KJ mol–1 (C) 300 KJ mol–1 (D) 800 KJ mol–1
100. The enthalpy changes for the following processes are listed below: [AIEEE 2006]
Cl2(g)  2Cl(g); 242.3 kJ mol–1 ; I2(g)  2I(g); 151.0 kJ mol–1
ICl(g)  I(g) + Cl(g); 211.3 kJ mol–1 ; I2(s)  I2(g); 62.76 kJ mol–1
Given that the standard state for iodine and chlorine are I2(s) and Cl2(g), the standard enthalpy of
formation for ICl(g) is
(A) –16.8 kJ mol–1 (B) +16.8 kJ mol–1 (C) +244.8 kJ mol–1 (D) –14.6 kJ mol–1

MATCH THE COLUMN

101. Match column-I to column-II standard entropy in J/K-molar at 298 K
Column-I Column-II
(A) C (s, diamond) (p) 5.7
(B) C (s, graphite) (q) 2.37
(C) H2 (g) (r) 117.6
(D) H (g) (s) 130.6

SINGLE AND DOUBLE VALUE INTEGER TYPE

20
102. A gas expands against a variable pressure given by P = bar-lt. During expainsion from volume of 1
V
litre to 10 litre, the gas undergoes a change in internal energy of 400 J. Heat absorbed by the gas
during expansion (in kJ) :
103. A sample of 4 mole He is originally confined in 20 L at 270 K and then undergoes adiabatic expansion
against a constant pressure of 125 mbar until the volume has increased by a factor of 3. calculate T
during process:

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104. The molar enthalpy of vaporization of benzene at its boiling point (353K) is 29.7 KJ/mole. For how long
(minute) would a 11.4 Volt source need to supply a 0.5 A current in order to vaporise 7.8 g of the
sample at its boiling point ? (Round off to nearest integer)
105. At 5 ×105 bar pressure, density of diamond and graphite are 3 g/cc and 2 g/cc respectively, at certain
 U – H 
temperature T. Find the value of   for the conversion of 1 mole of graphite to 1 mole of
 20 
diamond (in KJ) at temperature T. (1L.atm = 100 J)
 3 
106. 1 mole of an idal gas A (C v,m = 3R) and 2 mole of an ideal gas B are  Cv,m  R  taken in a container
 2 
and expanded reversible and adiabatically from 1 litre to 4 litre starting from initial temperature of 320 K.
Find the magnitude value of U/10R for the process is :
107. 10 litres of a monoatomic ideal gas at 0°C and 10 atm pressure is suddenly released to 1 atm pressure
and the gas expands adiabatically against this constant pressure. The final volume (L) of the gas.
108. A system is provided 50 joule of heat and the change in internal energy during the process is 60 J.
Magnitude of work done on the system is :
109. A system works in a cylic process. It absorbs 20 calories of heat and rejects 60 J of heat during the
process. The magnitude of work done (J) is [1 calorie = 4.2 J] :
110. Two moles of an ideal gas is expanded isothermally and irreversibly at 27ºC from volume V1 to 7.5 V1
and 4.17 kJ heat is absorbed from surroundings. Determine Ssys ? (Approximate integer in Cal)
111. The vapour pressure of liquid Hg at 433 K is 5 mm Hg. Calculate the free energy change accompanying
the expansion of one mole of Hg vapour in equilibrium with liquid at 433 K to a pressure of 750 mm Hg
at the same temperature assuming the vapour behaves like an ideal monoatomic gas in kJ mole–1.
(Approximate integer and e5 = 150)
112. Two mole of an ideal gas originally at a volume of 8 L. at 1000 K, is allowed to expand adiabatically
until final volume is 24 L. For the gas CV = 1.5 R. Calculate values of S for the process when :
(i) The expansion takes place reversibly.
(ii) The change in volume involves a free expansion.
Sum of S of these two case is______ . (Used : e1.09 = 3 and 1.09 × 8.314 = 9)
113. One litre sample of a mixture of CH4 and O2 measured at 32ºC and 760 torr, was allowed to react at
constant pressure in a calorimeter. The complete combustion of CH4 to CO2 and water caused a
temperature rise in calorimeter of 1 K. Calculate mole % of CH4 in original mixture.
[Given : Heat of combustion of CH4 is – 210.8 Kcal/mol. Total heat capacity of the calorimeter = 2108
cal/K]
114. 150 mL of 0.5 N HCl solution at 25ºC was mixed with 150 mL of 0.5 N NaOH solution at same
temperature. Calculate heat of neutralization of HCl with NaOH, if find temperature was recorded to be
29ºC. (H2O = 1g/mL) (Give your answer magnitude wise).
115. Calculate the resonance energy of isoprene (C5H8) from the data given.
–1 –1 –1 –1
Given that HC=C = 615 kJmole ; Hc–C = 348 kJ mole ; HC–H = 413 kJmole ; HH–H = 435 kJmole
–1
The standard heat of sublimation of graphite is 718 kJmole and heat of formation of C5H8(g) is 79
kJmole–1
(Give your answer in kcal mole–1 ; approximate integer).
116. Calculate the amount of heat evolved during the complete combustion of 100 ml of liquid benzene from
H
the following data. Predict your answer as (in KJ/mole).
100
(i) 18 g of graphite on complete combustion evolve 585 KJ heat
(ii) 15540 KJ heat is required to dissociate all the molecules of 1 litre water into H2 and O2.
(iii) The heat of formation of liquid benzene is 48 kJ/mol
(iv) Density of C6H6 () = 0.87 g/m
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–1
117. The enthalpy of neutralisation of a weak acid in 1 M solution with a strong base is – 56.1 kJ mol . If
the enthalpy of ionization of the acid is 1.5 kJ mol–1 and enthalpy of neutralization of the strong acid with
a strong base is – 57.3 kJ equiv –1, what is the % ionization of the weak acid in molar solution (assume
the acid to be monobasic)?

118. For reduction of ferric oxide by hydrogen, Fe2O3(s) + 3 H2(g)  2 Fe(s) + 3 H2O() ;
Hº300 =  26.72 kJ. The reaction was found to be too exothermic. To be convenient, it is desirable that
Hº should be at the most  26 kJ . At what temperature difference it is possible ?
CP[Fe2O3] = 105, CP[Fe(s)] = 25, CP[H2O()] = 75, CP[H2(g)] = 30 (all are in J/mol)

119. Calculate the enthalpy change of 1 mole of NaBr

1
Na(s) + Br2(g)  NaBr(s) in kcal
2
Given : Hsub (Na) = 137 kJ mole–1 ; Hbond dissociation (Br2(g)) = 144 kJ mole–1
–1 –1
H1st ionisation(Na(g) = 496 kJ mole ; H1st electron affinity(Br(g) = –325 kJ mole
HLattice energy (NaBr) = +742 kJ mole–1
120. In a constant volume calorimeter, 3.5 g of a gas with molecular weight 28 was burnt in excess oxygen
at 298.0 K. The temperature of the calorimeter was found to increases 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, the numerical
value for the enthalpy of combustion of the gas in kJ mol–1 is : [JEE 2009, 4/160]
121. One mole of an ideal gas is expanded isothermally at 300 K until its volume is tripled. Find the values of
Stotal under the condition.
Expansion is carried out irreversibly where 900 J of heat is less absrobed than expansion is carried out
reversibly. (Approximate integer value, Used e1.09 = 3 & 8.314 × 1.09 = 9)

ONE OR MORE THAN ONE OPTIONS CORRECT TYPE

122. Which of the following are incorrect : 
 (A) Work done by the surrounding in case of infinite stage expansion is more than single stage
expansion
(B) Irreversible work is always greater than reversible work. (with sign)
(C) On an ideal gas in case of single stage expansion and compression system as well as surrounding
are restored back to their original states
(D) If a gas in thermodynamic equilibrium is taken from state A to state B, by four successive single
stage expansions. Then we can plot 4 points on the P-V indicator diagram.
123. Identify the following processes in which non P-V work is involved :
(A) Transfer of electron through a resistor.
(B) Stirring of liquid through mechanical agitator.
(C) Falling of an apple on Newton's head.
(D) Attraction of iron filings towards a magnet.

 5 
124. 0.5 mole each of two ideal gases A and B  Cv, m  R  (Cv,m = 3R) are taken in a container and
 2 
expanded reversibly and adiabatically, during this process temperature of gaseous mixture decreased
from 350 K and 250 K. Then for the process :
(A) U = – 100 R (B) U = – 275 R (C) H = – 375 R (D) H = – 300 R
125. 4 KJ of heat is absorbed when 1 mol of ice melts at 0ºC and at constant pressure 1 atm. If molar
volume of ice and water are 19 ml and 18 ml respectively, then [Take 1 atm = 105 Pa]
(A) H > U (B) U > H (C) U = 4.1 KJ (D) U = 4.0001 KJ

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126. 5 moles of a liquid L are converted into its vapour at its boiling point (273°C) and at a pressure of 1 atm. If
the value of latent heat of vapourisation of liquid L is 273 L atm/mole, then which of the following statements
is/are correct: Assume volume of liquid to be negligible and vapour of the liquid to behave ideally.
(A) Work done by the system in the above process is 224 L atm.
(B) The enthalpy change (H) for the above process is 1365 L atm (with respect to magnitude only)
(C) The internal energy of the system increases in the above process.
(D) The value of U for the above process is 1589 L atm.
127. Three moles of an ideal diatomic gas undergoes a change in state from A
to B reversibly as follows :
Which of the following statements is/are correct regarding the above
process :
(A) Work done on the gas is 2700 R
(B) In the above process, pressure varies inversely with square of volume.
(C) Heat supplied to the gas is 4050 R
(D) Data insufficient for the calculation of work and heat supplied.
128. Following graph is constructed for the fixed amount of the gas.
(A) From 1 - 2 pressure will increase
(B) From 2 - 3 pressure remains constant
(C) Gas pressure at (3) is greater at state (1)
(D) From 1 - 2 pressure will decrease

129. Which of the following option show more entropy of first compound than second :
(A) (i) 1-hexene at 273 K and 1 atm (ii) Cyclohexane at 273 K and 1 atm
(B) (i) at NTP (ii) at NTP
(C) (i) SO2 (g) at 300 K and 0.1 atm (ii) SO2 (g) at 300ºC and 0.1 atm
(D) (i) C2H5OH () at 46ºC and 1 atm (ii) CH3OH () at 46ºC and 1 atm
130. Choose the correct statement (s) :
(A) Temperature, enthalpy and entropy are state functions
(B) For reversible and irreversible both isothermal expansion of an ideal gas, change in internal energy
and enthalpy is zero
(C) for a reaction in which ngas = 0, entropy change is not always zero
(D) The entropy change associated with reversible isothermal expansion of an ideal gas is equal to
P
2.303 R log10 1
P2
131. One mole of an ideal diatomic gas (Cv = 5 cal) was transformed from initial 25°C and 1 L to the state
when temperature is 100°C and volume 10 L. Then for this process(R = 2 calories/mol/K) (take calories
as unit of energy and kelvin for temp)
(A) H = 525
373
(B) S = 5 ln + 2 ln 10
298
(C) E = 525
(D) G of the process can not be calculated using given information.
132. Select the correct statements :
(A) All combustion reactions are exothermic (B) Heat of combusiton are always exothermic
1
(C) N2 + O2  2NO ; H = + ve (D) F2 + O2  F2O ; H = + ve
2
133. Consider the reactions
(i) S (rhombic) + 3/2 O2(g)  SO3(g), H1 (ii) S (monoclinic) + 3/2O2(g)  SO3(g), H2
(iii) S (rhombic) + O3(g)  SO3(g), H3 (iv) S (monoclinic) + O3(g)  SO3(g), H4
(A) H1 < H2 < H4 (magnitude only) (B) H1 < H3 < H4 (magnitude only)
(C) H1 < H2 = H4 (magnitude only) (D) H1 + H4 = H3

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134. In an insulated rigid chamber some CO2, CO and carbon is placed and O2 is passed in the chamber.
The mixture is ignited and combustion takes place. Which of the following is/are correct :
(A) T for system > 0 (B) T for system < 0 (C) q system = zero (D) U = zero
135. Which of the following is/are correct. (Consider all gases are ideal & reaction occure at const.
tempreture & pressure.
(A) CaCO3(s)  CaO(s) + CO2(g) (–ve P-V work)
(B) H2(g) + Cl2(g)  2HCl(g) (–ve P-V work)
+2 2+
(C) Zn(s) + Cu (aq)  Zn (aq) + Cu(s) (Non zero non P-V work)
(D) NaCl(s)  Na (aq) + Cl–(aq) (Non zero non P-V work)
+

136. If Hof(C2H6 ) (g) = – 85 kJ mol–1, Hof(C3H8 ) (g) = – 104 kJmol–1, Hº for C (s)  C (g) is 718 kJmol–1 and
heat of formation of H-atom is 218 kJmol–1 then :
(A) HC–C = 345 kJ (B) HC–H = 414 kJ (C) HH–H = 436 kJ (D) HH–H = 218 kJ

COMPREHENSION
Comprehension # 1
A gaseous sample is generally allowed to do only expansion/compression type of work against its
surroundings. The work done in case of an irreversible expansion (in the intermediate stages of
expansion/compression the states of gases are not defined). The work done can be calculated using
dw = – Pext dV
while in case of reversible process the work done can be calculated using
dw = – PdV where P is pressure of gas at some intermediate stages. Like for an
nRT
isothermal reversible process. Since P = , so
V
vf
nRT V 
w =  dw = –  . dV = –nRT ln  f 
vi V  Vi 
Since dw = – PdV so magnitude of work done can also be calculated by calculating the area under the
PV curve of the reversible process in PV diagram.
137. An ideal gaseous sample at initial state i (P0 , V0,T0) is allowed to expand to volume 2V0 using two
different process; in the first process the equation of process is PV2 = K1 and in second process the
equation of the process is PV = K2. Then,
(A) work done in first process will be greater than work in second process (magnitude wise)
(B) The order of values of work done can not be compared unless we know the value of K1 and K2.
(C) value of work done (magnitude) in second process is greater in above expansion irrespective of the
value of K1 and K2.
(D) st process is not possible
138. There are two samples of same gas initially under similar initial state. Gases of both the samples are
st nd
expanded.  sample using reversible isothermal process and  sample using reversible adiabatic
process till final pressures of both the samples becomes half of initial pressure, then
(A) Final volume of st sample < final volume of nd sample
(B) Final volume of nd sample < final volume of st sample
(C) final volumes will be equal
(D) Information is insufficient

139. In the above problem

st nd
(A) work done by gas in  sample > work done by gas in  sample
nd st
(B) work done by gas in  sample > work done by gas in  sample
st nd
(C) work done by gas in  sample = work done by gas in  sample
(D) none of these

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140. If four identical samples of an ideal gas initially at similar state (P0, V0,
T0) are allowed to expand to double their volumes by four different
process.
 : by isothermal irreversible process
 : by reversible process having equation P2 V = constant
 : by reversible adiabatic process
V : by irreversible adiabatic expansion against constant external
pressure.
Then, in the graph shown the final state is represented by four
different points then, the correct match can be
(A) 1 –  , 2 - , 3 – , 4 - V (B) 1 –  , 2 - , 3 – V, 4 - 
(C) 2 –  , 3 - , 4 – , 1 - V (D) 3 –  , 1 - , 3 – V, 4 - 

141. Two samples (initially under same states) of an ideal gas are first
allowed to expand to double their volume using irreversible
isothermal expansion against constant external pressure, then
samples are returned back to their original volume first by
reversible adiabatic process and second by reversible process
having equation PV2 = constant then
(A) final temperature of both samples will be equal
(B) final temperature of first sample will be greater than of second
sample
(C) final temperature of second sample will be greater than of first
sample
(D) none of these.

Comprehension # 2
Phase transitions are ubiquitous in nature. We are all familiar with the different phase of water (vapour,
liquid and ice) and with the change from one to another, the change of phase are called phase
transitions. There are six ways a substance can change between these three phase ; melting, freezing,
evaporating, condensing ; sublimination and decomposition.
At 1 atm pressure vaporisation of 1 mole of water from liquid (75ºC) to vapour (120ºC).
Cv(H2O, ) = 75 J mole–1 K–1 ; Cp (H2O, g) = 33.3 J mole–1 K–1
Hvap at 100ºC = 40.7 kJ/mole.
Calculate change in internal energy when
142. Liquid water is heated from 75°C to 100ºC ?
(A) 1875 J (B) 13125 J (C) – 1875 J (D) – 13125 J
143. Liquid water at 100°C is converted to vapour at 100ºC ?
(A) 40700 J (B) 37598.878 J (C) 43801.1 J (D) 3101.2 J
144. Water vapour at heated from 100ºC to 120ºC ?
(A) 666 J (B) 2998 J (C) 499.72 J (D) 166.28 J
Comprehension # 3
A gaseous mixture of propane, acetylene and CO2 is burnt in excess of air. Total 4800 kJ heat is
evolved. The total volume of CO2 (g) after combustion is 224 liters at NTP.
The total evolved heat is used to perform two separate process :
(i) Vapourising 87.5% of water (liquid) obtained in the process of burning the original mixture.
(ii) Forming 3808 liters ethylene measured at STP from its elements.
HH–H = 435 kJ/mol HC–H = 416 kJ/mol HC–C = 347 kJ/mol
HC=C = 615 kJ/mol, HCC = 812 kJ/mol Hsublimation of (C,s) = 718 kJ/mol
Hºf (CO2, g) = –394 kJ/mol Hºf (H2O, ) = – 286 kJ/mol. Hºf (H2O, g) = – 246 kJ/mol.

145. Horxn for C2H2(g) + H2(g)  C2H4(g)

(A) –220 kJ/mol (B) –180 kJ/mol (C) –250 kJ/mol (D) – 200 kJ/mol

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146. Sum of enthalpies of combustion of C3H8(g) and C2H2(g) is :
(A) –2198 kJ/mol (B) – 3499 kJ/mol (C) –2798 kJ/mol (D) –3099 kJ/mol
147. Total moles of hydrocarbon gases taken in the initial mixture
(A) 3 (B) 4 (C) 2 (D) 5

PART - IV : PRACTICE TEST-2 (IIT-JEE (ADVANCED Pattern))

Max. Time : 1 Hr. Max. Marks : 81
Important Instructions
A. General %
1. The test is of 1 hour duration.
2. The Test Booklet consists of 27 questions. The maximum marks are 81.
B. Question Paper Format
3. Each part consists of five sections.
4. Section-1 contains 8 multiple choice questions. Each question has four choices (A), (B), (C) and (D) out
of which ONE is correct.
5. Section-2 contains 6 multiple choice questions. Each question has four choices (A), (B), (C) and (D) out
of which ONE OR MORE THAN ONE are correct.
6. Section 3 contains 6 questions. The answer to each of the questions is a single–digit integer, ranging
from 0 to 9 (both inclusive).
7. Section 4 contains 2 paragraphs each describing theory, experiment and data etc. 6 questions relate to
paragraph. Each question pertaining to a partcular passage should have only one correct answer
among the four given choices (A), (B), (C) and (D).
8. Section 5 contains 1 multiple choice questions. Question has two lists (list-1 : P, Q, R and S; List-2 : 1,
2, 3 and 4). The options for the correct match are provided as (A), (B), (C) and (D) out of which ONLY
ONE is correct.
C. Marking Scheme
9. For each question in Section 1, 4 and 5 you will be awarded 3 marks if you darken the bubble
corresponding to the correct answer and zero mark if no bubble is darkened. In all other cases, minus
one (– 1) mark will be awarded.
10. For each question in Section 2, you will be awarded 3 marks. If you darken all the bubble(s)
corresponding to the correct answer(s) and zero mark. If no bubbles are darkened. No negative marks
will be answered for incorrect answer in this section.
11. For each question in Section 3, you will be awarded 3 marks if you darken only the bubble
corresponding to the correct answer and zero mark if no bubble is darkened. No negative marks will be
awarded for incorrect answer in this section.

SECTION-1 : (Only One option correct Type)

This section contains 8 multiple choice questions. Each questions has four choices (A), (B), (C)
and (D) out of which Only ONE option is correct.

1. One mole of ideal monoatomic gas is carried through the reversible cyclic process as shown in figure.
Calculate the max. temperature attained by the gas during the cycle.

25  Po V o  25  Po V o  35  Po V o  35  Po V o 
(A)   (B) –   (C)   (D) –  
8  R  8  R  8  R  8  R 

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2. Determine Uº at 300 K for the following reaction using the listed enthalpies of reaction :
4CO(g) + 8H2(g) —— 3CH4 (g) + CO2(g) + 2H2O()
C(graphite) + 1/ 2O2(g) —— CO(g); H1º = – 110.5 kJ
CO(g) + 1/ 2O2(g) —— CO2(g); H2º = –282.9 kJ
H2(g) + 1/ 2O2(g) —— H2O(l); H3º = –285.8 kJ
C (graphite) + 2H2(g) —— CH4(g); H4º = –74.8 kJ
(A) –653.5 kJ (B) –686.2 kJ (C) –747.4 kJ (D) None of these
3. Determine enthalpy of formation for H2O2(), using the listed enthalpies of reactions :
N2H4() + 2H2O2()—— N2(g) + 4H2O(); rHº1 = –818 kJ/mol
N2H4() + O2(g) —— N2(g) + 2H2O();  rHº2 = –622 kJ/mol
1
H2(g) + O2(g) —— H2O();  rHº3 = –285 kJ/mol
2
(A) –383 kJ/mol (B) –187 kJ/mol (C) –498 kJ/mol (D) None of these
4. The enthalpy of neutralization of a weak monoprotic acid (HA) in 1M solution with a strong base is –
55.95 kJ/mol. If acid HA requires 1.4 kJ/mol heat for it’s complete ionization and enthalpy of
neutralization of the strong monobasic acid with a strong monoacidic base is –57.3 kJ/mol. What is the
% ionization of the weak acid in molar solution ?
(A) 1% (B) 3.57% (C) 35.7% (D) 10%
5. Calculate fGº for (NH4CI, s) at 310 K.
Given : fHº (NH4CI, s)= –314.5 kJ/mol; rCp = 0
Sº N2 (g) = 192 JK–1 mol–1; Sº H2 (g) = 130.5 JK–1 mol–1;
SºCl2(g) = 233 JK–1 mol–1; Sº NH4 CI(s) = 99.5 JK–1 mol/–1
All given data are at 300 K.
(A) –198.56 kJ/mol (B) –426.7 kJ/mol (C) –202.3 kJ/mol (D) None of these
3
6. For a perfectly crystalline solid Cp.m. = aT , where a is constant. If Cp.m. is 0.42 J/K–mol at 10 K, molar
entropy at 10 K is
(A) 0.42 J/K–mol (B) 0.14 J/K–mol (C) 4.2 J/K–mol (D) zero

7. The molar entropy content of 1 mole of oxygen (O2) gas at 300 K and 1 atm is 250 J mole–1 K–1.
Calculate G when 1 mole of oxgyen is expanded reversibily and isothermally from 300 K, 1 atm to
double its volume (Take R = 8.314 J mole–1 K–1, log e = 2.303)
–1 –1
(A) 1.728 KJ mole K (B) 0
(C) –1.728 KJ mole–1 K–1 (D) 0.75 KJ mole–1K–1
8. Fixed amount of an ideal mono atomic gas contained in a sealed rigid vessel (V = 24.6 litre) at 1.0 bar
is heated reversibly form 27oC to 127oC. Determine change in Gibb's energy (in Joule) if entropy of gas
S = 10 + 10–2 T (J/K)
(A) 530 J (B) –530 J (C) 1778.5 J (D) 3778.5 J
Section-2 : (One or More than one options correct Type)
This section contains 6 multipole choice questions. Each questions has four choices (A), (B),
(C) and (D) out of which ONE or MORE THAN ONE are correct.

9. Which of the following statement(s) is/are ture?

(A) E = 0 for combustion of C2H6(g) in a sealed rigid adiabatic container
(B) fHº (S, monoclinic)  0
(C) If dissociation energy of CH4 (g) is 1656 kJ/mol and C2H6(g) is 2812 kJ/mol, then value of C—C
bond energy will be 328 kJ/mol
(D) If Hf(H2O,g) = – 242 kJ/mol; Hvap (H2O, l) = 44 kJ/mol then fHº (OH– ,aq.) will be – 142 kJ/mol
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10. From the following data, mark the option(s) where H is correctly written for the given reaction.
+ –
Given : H (aq) + OH (aq) — H2O(); H = – 57.3 kJ
Hsolution of HA(g) = –70.7 kJ/mol
Hsolution of BOH(g) = 20 kJ/mol
Hionization of HA = 15 kJ/mol and BOH is a strong base.
Reaction Hr (kJ/mol)
(A) HA(aq) + BOH(aq) — BA(aq) + H2O –42.3
(B) HA(g) + BOH(g) — BA(aq) + H2O –93
+ –
(C) HA(g) — H (aq) + A (aq) –55.7
(D) B+(aq) + OH–(aq) — BOH(aq) –20
11. The value of Htransition of C (graphite) — C (diamond) is 1.9 kJ/mol at 25ºC entropy of graphite is
higher than entropy of diamond. This implies that :
(A) C (diamond) is more thermodynamically stable then C (graphite) at 25ºC
(B) C (graphite) is more thermodynamically stable than C (diamond) at 25ºC
(C) diamond will provide more heat on complete combustion at 25ºC
(D) Gtransition of C (diamond) — C (graphite) is –ve
12. Which of the following statement(s) is/are false ?
(A) All adiabatic processes are isoentropic (or isentropic) processes
(B) When (Gsystem) T,P < 0; the reaction must be exothermic
(C) dG = VdP – SdT is applicable for closed system, both PV and non–PV work
(D) the heat of vaporisation of water at 100ºC is 40.6 kJ/mol. When 9 g of water vapour condenses to
liquid at 100ºC of 1 atm, then Ssystem = 54.42 J/K
13. For the reaction 2Ag2O (s)  4Ag(s) + O2 (g), H is 61.17 kJ mol–1 and S is 132 J K–1 mol–1.
Compute the temperature above which the given reaction will be spontaneous.
(A) T > 463.4 K (B) T > 190.250 C (C) T < 190.250 C (D) T < 463.4 K
14. Select the correct enthalpy at corresponding temperature using following datas
(i) Heat capacity of solid from 0 K to normal melting point 200 K
CP,m(s) = 0.035 T JK–1 mol–1.
–1
(ii) Enthalpy of fusion = 7.5 KJ mol ,
(iii) Enthalpy of vaporisation = 30 KJ mol–1.
(iv) Heat capacity of liquid form 200 K to normal boiling point 300 K
CP,m() = 60 + 0.016 T JK–1 mol–1.
(v) Heat capacity of gas from 300 K to 600 K at 1 atm
CP,m (g) = 50.0 JK–1 mol–1.
(A) S200 (s) = 7 (B) S300 () = 70.43 (C) S300 (g) = 170.43 (D) S600 (g) = 205.09

Section-3 : (One Integer Value Correct Type.)

This section contains 6 questions. Each question, when worked out will result in one integer
from 0 to 9 (both inclusive)

15. Two moles of a perfect gas undergo the following processes :

(a) a reversible isobaric expansion from (1.0 atm, 20.0 L) 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, 40.0 L) to (1.0 atm, 20.0 L)
Calculate the magnitude of work (W) done in L.atm [JEE 2002, 5/60]
16. The enthalpy of combustion of mol. wt. 180 glucose is – 2808 KJmol–1 at 25ºC. X and Y grams of
glucose do you need to consume respectively cases [Assume wt = 62.5 Kg].
(a) to climb a flight of stairs rising through 3M. (b) to climb a mountain of altitude 6000 M ?
Assume that 25% of enthalpy can be converted to useful work.
X and Y are related as Y = mX; then find m/1000.

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17. A sample of certain mass of an ideal polyatomic gas is expanded against constant pressure of
1 atm adiabatically from volume 2 L, pressure 6 atm and temperature 300 K to state where its final
volume is 8L. Then calculate entropy change (in J / K ) in the process. (Neglect vibrational degrees of
freedom) [1L atm = 100 J, log 2 = 0.3, log 3 = 0.48, log e = 2.3] (aproximate integer)
18. The heat of combustion of acetylene is 312 kcal. If heat of formation of CO2 & H2O are –94 & –68 kcal
respectively. Given that heat of atomisation of C(s) & H2(g) are 150 & 100 kcal respectively and C–H
HCC
bond energy is 95 kcal. Calculate .
22
19. Boron exist in different allotropic forms. All allotropic form contains icosahedral units (icosahedral is a
regular shape with 12 corners & 20 faces) with boron atoms at all 12 corners and all bonds are
equivalent. [M]

B (g)  (g)

Calculate heat evolved at constant pressure (in kJ) per mole of boron atoms undergoing above change
if HBE(B–B) = 200 kJ/mol. Report you Answer after dividing by 100
20. 1 mole of an ideal gas is allowed to expand isothermally at 27ºC till its volume is tripled . If the
expansion is carried out reversibly then the Suniverse will be ?

SECTION-4 : Comprehension Type (Only One options correct)

This section contains 1 paragraphs, each describing theory, experiments, data etc. 3 questions
relate to the paragraph. Each question has only one correct answer among the four given
options (A), (B), (C) and (D)

Paragraph for Questions 21 to 23

Concerete is produced from a mixture of cement, water, sand and small stones. It consists primarily of
calcium silicates and calcium aluminates formed by heating and grinding of clay and limestone. In later
steps of cement production a small amount of gypsum, CaSO4.2H2O is added to improve subsequent
hardening of concrete. The use of elevated temperatures during the final production may lead to
formation of unwanted hemihydrate, CaSO4.1/2H2O. Consider the following reaction :
CaSO4.2H2O(s) CaSO4.H2O(s) + H2O (g)
The following thermodynamic data apply at 27ºC, standard pressure : 1 bar
Compound Hºf(kJ / mol) Sº (JK 1mol1 )
CaSO4 .2H2O (s) 2021.0 194.0
1
CaSO4 . H2 O(s) 1575.0 119.5
2
H2 O(g) 242.8 188
–1 –1
R = 8.314 JK mol
1
21. Hº for the formation of 1.45 kg of CaSO4. H2O(s) from CaSO4.2H2O(s) is
2
(A) +446 kJ (B) –830 kJ (C) –446 kJ (D) +818 kJ
1
22. Equilibrium pressure (in bar) of water vapour in closed vessel containing CaSO4. 2H2O(s),
2
CaSO4.H2O(s), H2O(g) at 27ºC : (2.303R × 300 × 1.5 = 8645.83, log 5.5 = 0.74)
(A) 15 × 10–4 bar (B) 2 × 10–4 bar (C) 5.5 × 10–3 bar (D) 7.00 × 10–4 bar
23. Approximate temperature at which the equilibrium water vapour pressure is 1.00 bar
(A) 121°C (B) 400ºC (C) 200ºC (D) 240ºC

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Paragraph for Questions 24 to 26
The accompanying diagram represents a reversible cannot cycle for an ideal gas :

24. How many heat is rejected at the lower temperature, 200 K, during the isothermal compression ?
(A) 150 kJ (B) 30 kJ (C) 120 kJ
(D) data are not sufficient to calculate exact value
25. What is the entropy increase during isothermal expansion at 1000 K ?
(A) 0.15 JK–1 (B) 150 kJ K–1 (C) 150 JK–1 (D) 750 JK–1
26. What is the Gibbs free energy change during the process A  B ?
(A) 150 kJ (B) –150kJ (C) 30kJ (D) Data are not sufficient

SECTION-5 : Matching List Type (Only One options correct)

This section contains 1 questions, each having two matching lists. Choices for the correct
combination of elements from List-I and List-II are given as options (A), (B), (C) and (D) out of
which one is correct

27. Match column-I to column-II standard entropy in kJ/K-molar at 25ºC

Column-I Column-II
1. HC–C (p) 733.48
2. HC–H (q) 97.81
3. HC=C (r) 434.3
4. HCC (s) 454.64
5. HC=O (t) 804.22
Using the data (all values are in kJ/mol at 25ºC) given below :
Hºcombustion (ethane) = –1559.8 ; Hºcombustion (ethene) = –1410.9
Hºcombustion (acetylene) = –1299.7 ; Hºcombustion (acetaldehyde) = –1192.3
 Hºf CO2(g) = –393.5 ; Hºf of H2O () = –285.8
Hº for C(s) (graphite)  C(g) = 716.68 ; Bond energy of H–H = 435.94
Bond energy of O=O = 498.94
1 2 3 4 5 1 2 3 4 5
(A) q s r p t (B) r p t q s
(C) q p s r t (D) p s q r t

Practice Test-2 ( (IIT-JEE (ADVANCED Pattern))

OBJECTIVE RESPONSE SHEET (ORS)
Que. 1 2 3 4 5 6 7 8 9 10
Ans.
Que. 11 12 13 14 15 16 17 18 19 20
Ans.
Que. 21 22 23 24 25 26 27
Ans.

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

PART – II
1. (A) 2. (B) 3. (B) 4. (D) 5. (B)
6. (A) 7. (B) 8. (C) 9. (C) 10. (B)
11. (B) 12. (B) 13. (A) 14. (A) 15. (B)
16. (A) 17. (B) 18. (C) 19. (C) 20. (C)
21. (C) 22. (B) 23. (D) 24. (D) 25. (D)
26. (D) 27. (C) 28. (B) 29. (C) 30. (C)
31. (D) 32. (D) 33. (A) 34. (D) 35. (C)
36. (B) 37. (B) 38. (C) 39. (D) 40. (D)
41. (C) 42. (B) 43. (A) 44. (D) 45. (C)
46. (A) 47. (A) 48. (B) 49. (A) 50. (B)
51. (A) 52. (B) 53. (A) 54. (D) 55. (B)
56. (A) 57. (B) 58. (B) 59. (D) 60. (A)
61. (D) 59. (C)
PART – III
1. –34.465 kJ 2. –0.7478 kJ
3. (i) Isobaric (ii) w = 830.865 J, q = –150 J
4. T2 = 100 K, w = – 5.016 KJ 5. (a) – 816 J (b) + 2026 J (c) 1210 J
6. Hydrogen is diatomic so at high temperature rotational and vibrational motion also counts.
7. H = 990 J, E = 10 J 8. Zero
3 3
9. (i) Rev. Process Ssystem = R In 10; Ssurr = – R In 10 ; STotal = 0
2 2
3 3 3
(ii) Irr. Process Ssystem = R In 10; Ssurr = – R (0.9); Stotal = R (1.403)
2 2 2
10. (a) When H = – ve and TS = – ve, also TS > H then G = + ve in such case, the reaction will not
be spontaneous.
(b) – Gº = 2.303 RT log Kc.
If Gº is negative (not to say that G < 0) then Kc will be +ve and will have value greater than one.

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11. –43.92 KJ
12. (i) G = 5.7 kJ/mol (ii) backward shifting 13. –7.432 kJ
14. Exothermic A, C, D; endothermic : B, E

S V
15. Since, sublimation involves

L
According to Hess’s law, H(f) + H(v) = H(s)

16. q1 > q2 17. 22.8 cal/g. 18. 1312 kJ 19. 43.73 kJ/mol
–1
20. –827 kJ mol 21. (C) 22. (C) 23. (B) 24. (D)
25. (A) 26. (A) 27. (C) 28. (D) 29. (A)
30. (B) 31. (A) 32. (B) 33. (A) 34. (D)
35. (A) 36. (B) 37. (A) 38. (A) 39. (B)
40. (C) 41. (B) 42. (A) 43. (A) 44. (A)
45. (D) 46. (A) 47. (B) 48. (A) 49. (B)
50. (B) 51. (A) 52. (C) 53. (D) 54. (D)
55. (B) 56. (D) 57. (C) 58. (B) 59. (C)
60. (A) 61. (D) 62. (D) 63. (B) 64. (C)
65. (B) 66. (D) 67. (A) 68. (C) 69. (B)
70. (C) 71. (B) 72. (D) 73. (C) 74. (A)
75. (C) 76. (A) 77. (D) 78. (D) 79. (C)
80. (B) 81. (D) 82. (B) 83. (C) 84. (B)
85. (C) 86. (D) 87. (B) 88. (A) 89. (A)
90. (A) 91. (C) 92. (B) 93. (A) 94. (A)
95. (B) 96. (D) 97. (B) 98. (D) 99. (D)
100. (B) 101. (A - q), (B - p), (C - s), (D - r) 102. 5 103. 6
104. 9 105. 5 106. 96 107. 64 L 108. 10
109. 24 110. Ssystem = 8 Cal   111. 18 112. 18
113. 25%. 114. –16 Kcal. 115. 5 116. 36 kJ 117. 20 %
–1 –1
118. 9 119. –362 kJ mole 120. 9 121. Stotal = 3 J K
22. (ACD) 123. (ABCD) 124. (BC) 125. (BD) 126. (ABC)
127. (ABC) 128. (ABC) 129. (AD) 130. (ABCD) 131. (ABD)
132. (ABCD) 133. (ABD) 134. (ACD) 135. (ACD) 136. (ABC)
137. (C) 138. (B) 139. (A) 140. (B) 141. (C)
142. (A) 143. (B) 144. (C) 145. (A) 146. (B)
147. (A)

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PART – IV
1. (A) 2. (D) 3. (B) 4. (B) 5. (A)
6. (B) 7. (C) 8. (B) 9. (ABC) 10. (ABC)
11. (BCD) 12. (ABCD) 13. (AB) 14. (ABCD)
15. (– 20 + 0 + 14) = – 6 L atm 16. 2 17. 3 18. 7
19. 5 20. 0 21. (D) 22. (C) 23. (A)
24. (B) 25. (C) 26. (B) 27. (A)

PART – I
(125  8)  4.2  6
6. Hsolution = × 80 = 33516 J/mol or 33.51 kJ/mol.
8
7. rC p = 0,  H300 = H310

8. C2H5OH () + 3O2 (g) 2CO2 (g) + 3H2O

ng = 2 – 3 = –1
so U = H – ng RT
= –q + RT
1
9. H2C2O4() + O2(g)  H2O() + 2CO2(g);
2
ng = 3/2
0.312  8.75
Uc = – × 90 = – 245.7 kJ/mol
1
H = U + ngRT
3 8.314  300
= – 245.7 + × = – 241.947 kJ/mol.
2 1000
10. From given reaction ng = 12 – 15 = – 3
so E° = H° – ng RT = – 6542 + 3RT
1.5
for 1.5 mole, E° = { –6542 + 3RT} = 4900.9 kJ
2
11. ng = 1–2 = –1
–3
E = H – ng RT = H – RT = – 72.3 + 8.314  300  10 = – 69.806 kJ/mole
so for 3 mole we will get E = – 69.806  3 kJ/mole = 209.42 kJ/mole
12. For same amount of gas at constant temperature, lesser is the volume, lower will be the entropy.
–3
13. W = – Pext(V) = –(1 atm)  500  50  10 L
–3
= – 25 L atm = – 25  101.3  10 kJ = –2.53 kJ
14. C2H4 + H2  C2H6
50 ml 50 ml 0
X X 50 ml
H = U + P (V)
– 0.31 = U + 1.5 × 1.01 × 105 (– 50 × 10–6).
U = – 0.3024 kJ.

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15. H2O (s)  H2O (l), H = 1440 cal.
16. E = q + w
1
W BC = (2Vº – Vº) (Pº – 3Pº) + (2Vº – Vº) (0 – Pº) = – 2PºVº
2
3  P 2V 3P V  3
E = nCVT = 1  R        = – PºVº
2  R R  2
3 1
qBC = E – W = – PºVº + 2PºVº = PºVº
2 2
17. Beaker is open and in open beaker external pressure remains constant.
Zn + H2SO4  ZnSO4 + H2 (g)
130
= 2 mole
65
PV = nRT
PV = ngRT
W = – ngRT = 2 × 2 × 300 = – 1200 cal.

18. C3H8(g) + 5O2  3CO2(g) + 4H2O()

 6  B.E. (C  O) 
8  B.E. (C — H)   8  B.E.(O — H) 
CH =  2  B.E. (C — C) –  
 3 | R.E. | of CO2 
 5  B.E. (O  O)   
 4   vap H(H2O) 

1
19. H2 (g) + O2 (g)  H2O (l) ; Hcomb H
2
1 x
Hcomb = HH — H + H O = O – 2HO — H – Hvap = x1  2  2x3  x 4
2 2
1 3 H2 3
20. N2(g) + Cl2(g)  NCl3(g) ; H = H1 + – H3
2 2 2 2

21. H+(aq) + OH–(aq)  H2O()

so H° = – 57.3 = – 285.5 – Hf° (H+, aq) – Hf° (OH–, aq)
so Hf° (OH–, aq) =– 228.5 kJ/mole (as Hf° (H+, aq) = 0)
8 1
22. r H = × 45.54 + × 68.91 = 48.137 kJ.
9 9
23. C2H5–S–C2H5 + S  C2H5–S–S–C2H5
Hºƒ (C2H5–S–C2H5) Hºf (C2H5–S–S–C2H5) – HS – S + Hsub S.
– 201.9 = – 147.2 – HS – S + 222.8
HS – S = 277.5 kJ/mol
24. Hº = 2 × H 1º + 2 × H º2 – H 3º

25. G = H – TS = – 2808 – 310 × 182.4 × 10–3 = – 2864.5 kJ

26. S = 10.13 = 31.2 + 51.1 – 47.3 – SH2O
SH2O = 45.13 cal/k mole.
3
27. G = 29.3 × 10 – (2 × 239.7 – 152.3 – 223) × 298 = – 1721.8 Joule.

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28. Since, expansion occurred at constant temperature,
V 1 3.0
S = nR ln 2  × 8.314 ln = 0.36 JK–1
V1 32 0.75
Since, this is case of free expansion, Pext = 0.  – W = Pext V = 0, q = 0
Also, since, T = 0  H = E = 0.
1
29. (2) Cu2O(s) + O2(g) 2CuO (s)
2
 Gºreaction = [2 × (–30.4)] – [–34.98] = – 25.82 kcal
and – 25.82 × 103 = 2.303 × 2 × 298 logK
 K 1019, a very high value, hence reaction will be almost complete with a trace of Cu2O.
30. fSº(NH4CI,s) at 300 K
1 1 º 
= S oNH4 CI(s) –  SNº 2  2SHº 2  SCI2 
= – 374 JK–1 mol–1
2 2 
fC P = 0
 f So310 = f So300
–1 –1
= – 374 JK mol
o o
f H310 = f H300 = – 314.5
f Go310 = fHº – 310
310(–374)
Sº = – 314.5 – = – 198.56 kJ/mol.
1000

PART - III
V2 10
1. W = –2.303 nRT log  2.303  6  8.314  300log = –34464.8 Joule = 34.465 kJ
V1 1

2.  dW = –  Pext d
 nRT nRT   1 1
W irr = –Pext [V2 – V1] = –Pext    = –Pext × nRT   
 2P P1   P2 P1 
 1 1 3
= –1 × 1 × .082 × 300    = –1 × .082 × 300 × = –7.38 L.atm = –747.8 J
 2 5  10
W irr = –0.7478 KJ
 Pv   Pv 
3. (i)   =  
 nRT  A  nRT B
PA  4 PB  3 P P
= = A = B  PA = PB Hence process is isobaric.
nR  400 nR  300 100 100
 nRTA   1 .082  300 
(ii) W = –Pext (V2 – V1) = –   (VB – VA) = –   (3 – 4) × 101.325 J = 830.865 J
V
 A   3 
qAB = nCP (T2 – T1) = 1 × 15 × (300 – 400) = –150 J
4. (a) T1V1 – 1 = T2V2 – 1
1/3 1/3
300 × V = T2 × (27 V)  T2 = 100 K
(b) E = q + W
For reversible adiabatic process,
q=0
U = W
 W = n CV T
 W = 1 × 25.08 × (100 – 300) = – 5.016 kJ
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5. PV = nRT  5 × 1 = n × 0.082 × 300  n = 0.203.
Initial Final
(a) V = 1 L. V2 = 5 L.
P = 5atm
T = 300 K T = 300 K
V2
w = –2.303 nRT log = – 2.303 ×0.203 × 8.314 × 300 log 5 = –816 J
V1
w = – 816 J and q = –w = 816 J
So, work done by the gas = 816 J.
(b) w = – Pext (V2 – V1) = –5 [1–5] = +20 ×101.325
w = 2026 J.
(c) q1 = – w1 = +816 J
q2 = – w2 = –2026 J
q1 + q2 = –1210 J
So, Net heat released by the system = –1210
Net Heat gained by the surroundings = 1210
6. Helium (He) gas is monoatomic and it has three translational degree of freedom. Hence, the
contribution of each translational degree of freedom towards Cv being R/2, so the total contribution
towards Cv = 3 × R / 2. Hydrogen molecule is diatomic. At low temperature, rotational and vibrational
contribution for H2 are zero. So, Cv for H2 at low temperature continues to be 3R/2. At moderate
temperature, rotational contribution (= 2 × R / 2) also becomes dominant and hence total contribution
3R 5R
towards CV = +R= . At even high temprature, vibrational contribution (= 1 × R) also becoms
2 2
3R 7R
significant. Hence total contribution towards CV = +R+R=
2 2
7. U = q + W
for adiabatic process q = 0, hence U = W and W = – p(V) = – P (V2 – V1)
so, U = – 100 (99 – 100) = – 100 (–1) = 100 bar mL = 10 J
Now H = U +  (PV)
Here U already calculated above and
PV = (P2V2 – P1V1)
So, H = 100 + (100 × 99 – 1 × 100) = 9900 bar mL = 990 J
dqrev. dq
8. dS =
T
  Trev. = S
As 'S' being a state function, S = 0 in a cyclic process.
dq
  Trev. = 0.
T2 3
9. (i) Ssystem = nCV ln = R In 10 and
T1 2
T2
dqsys nCv dT T 3
Ssurr = – = – = –nCVln 2 = – Rln 10
T T1 T T1 2
(ii) Entropy is a state function.
3
Ssystem = R In 10.
2
q nCV (T2  T1 ) 3
Ssurr = =– = – R (0.9).
T T2 2
3 3 3
STotal = Rln 10 – R(0.9) = R(1.403)
2 2 2

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10. (a) When H = – ve and TS = – ve, also TS > H then G = + ve in such case, the reaction will not
be spontaneous.
(b) – Gº = 2.303 RT log Kc.
If Gº is negative (not to say that G < 0) then Kc will be +ve and will have value greater than one.
11. 2NO (9, 1 × 10–5 atm) + Cl2 (9, 1 × 10–2) 2NOCl (9, 1 × 10–2)
 (1 102 )2   1 102 
G° = – 2.303 RT  log  = – 2.303 RT log 10 
 (1 105 )2 (1 102 )   1 10 
= – 2.303 RT [log 1 × 108] = – 2.303 × 8 × 298  8 = – 43.92 KJ.
12. (a) (i) Gº for the reaction
Gºreac. = 2Gº (NO2) – Gº (N2O4)
100 – 100 = 0
Now, G = 2.303 RT log QP + Gº
2
PNO 100
Here QP = 2
= = 10 atm
PN2O4 10
So, G = 2.303 RT log QP + 0 = 2.303 RT log QP = 2.303 RT log10 10= 2.303 RT = 5.7 kJ/mole
(ii) Since QP is more than KP
(Calculate KP by putting the value of Gº in the equation Gº = 2.303 RT log KP as Gº = 0 that’s why
KP comes as 1.)
Hence, the reaction will proceed in backward direction.
13. H = U + nRT
H – U = – 3RT
= – 3 × 8.314 × 298 = – 7432 J = – 7.432 kJ
16. Cp = –ve ; Cp (products) < Cp (Reactants) so q2 < q1
17.  H2 – 24 = – 0.024 × (523 – 473) cal/g.  H2 = 22.8 cal/g.
18. Equal volume of H2(g) & CO(g)
Total volume = 112 L
So, volume of CO = volume of H2 = 56 L
Mole of CO = Mole of H2 = 2.5 mole
1
H2(g) + O2(g)  H2O(g) H = – 241.8 kJ
2
For 1 mole H = – 241.8 kJ
For 2.5 mole H = – 241.8 × 2.5
1
Similarly, CO(g) + O2(g)  CO2(g) H = –283 kJ
2
H = –283 × 2.5 kJ
Total Heat evolved = [–241.8 + (–283] 2.5 = – 1312 kJ
5 3
19.  rH = × 40 + × 50 = 43.75 kJ/mol
8 8
20. Equation (vi) can be generated by the following manipulations.
Eq. (i) – Eq. (ii) – Eq. (iii) – Eq. (iv) – ½ Eq. (v)
Carrying out the corresponding manipulations on H0L, we get
H0L = (– 563 – 419 – 88 + 322 – 79) kJ mol–1 = – 827 kJ/mole
21. In a reversible process, the driving and the opposite forces are nearly equal, hence the system and the
surroundings always remain in equilibrium with each other.
22. (C) An ideal gas under going expansion in vacuum shows, E = 0, W = 0 and q = 0.
23. W 2 – P(V2 – V1) = nRT = 1 × R × 2 = 2R.
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24. Mechanical work is important only in gases as they undergo appreciable change in volume.
26 Let final common temperature is Tf.
Heat gained by Zinc piece = Heat lost by water
0.4 (Tf – 20) × 65.38 = 4.2 (100 –Tf) × 180  Tf = 97.3 °C
f
27. Internal energy of a gas = nRT
2
Internal energy of a gas  f
28. Mechanical work is done on the system and internal energy increases.

29.  The process is of free expansion then W = 0.

30. For polydropic process (n = 2)

PV2 = C
TV = C
T1V1 = T2V2
300 × 1 = T2 × 3  T2 = 100 K
U = nCv,m T
fR 5R 1 5  R
=1× (T2 – T1) = 1 × × (100 – 300) = × 200 = –500 R = –4.2 kJ
2 2 2
32. Final temperature of gas must be double of the initial temperature
H = U +  (PV) = nCV T + (PV) (T = Tf – Ti = 2Ti)
nR 3
= Ti + (PV) = × 100 + 100 = 250 J.
(   1) 2
33. Work is not a state function becuase it depends upon the path followed.
34. q + w = U is a state function.

35. W Total = area enclosed

nRT
V=
P
2R  300 600 R
VA = 
1 1
2R  300 300 R 2 R  400 400 R
VB =  ; Vc = 
2 1 2 1
800 R
VD =
1
V 1
W AB = –nRT TAln B = –2R (300)ln = 600 Rln2
VA 2
W BC = –2(400 –300) R= – 200 R
V
W CD = – 2 R(400)ln D = – 800 Rln2
VC
W AD = –1(600 R – 800 R) = 200 R
W Total = W AB + W BC + W CD + W AD =– 200 Rln2 = – 100 Rln4
36. Since ice-water ratio is maintained as 1 : 1. So, T = 0.
37. (A) w = – nR T = –2 × 8.314 × 100 = –1662.8 J
400 400
 10 2 
U = n C V, m dT = 2 ×  (20 + 10–2 T) dT = 2 20  100 
2
 4002 – 3002   = 4700 J
300 300  
4700 = q – 1662.8
 q = 6362.8 J.
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38. latent heat of vaporisation of water = 2.25 × 106 J/kg
H = 2.25 × 106 J/kg.
work done = – Pext (V2 – V1)
H = 2.25 × 106 J/kg
H = U + PV
m 1
(a) Now, volume of water V =   = M3 = 1 L
d 1000
1000
(b) volume of steam = = 1666.67 L
0.6
6
2.25 × 10 = U + 1 [1666.67 – 1] 101.325
U = 22.5 × 105 – 1.68 × 105 = 20.8 × 105 = 2.08 × 106 J
39. Volume = 5 × 10 × 3 = 150 m3 = 150 × 103 L ; T = 27°C = 300 K ; P = 1 atm
PV = nRT  1 × 150 × 103 = n × 0.082 × 300  n = 6097.6
Total energy released per second = 150  50 = 7500 J/sec.
Amount of energy released by persons = energy gained by air  [7500] tsec = n C[dT]
7 354.87
 7500 tsec = 6097.6 × × 8.312 × 15  tsec = 354.87 sec. = = 5.91 minutes.
2 60

3
40. At constant volume U = qv = nCvm T = R × 300 = 450 R
2
5
At constant pressure H = qp = nCp,m T = R (–150) = –375 R
2
41. FACTUAL
42. FACTUAL
43. Molar mass = 102 gram/mole
P = 650 torr ; T = 77 + 273 = 350 K
Q = i × t = 0.25 × 600 = 150
E = Q × V = 150 × 12 = 1800 J
This heat is supplied to the system at constant pressure that’s why this is used for change in enthalpy
 For vaporisation of 1.8 gram, amount of heat required q = 1800 J
1800
 For vaporisation of 102 gram, amount of heat required q = × 102 J
1.8
3
= 102 × 10 J = 102 KJ/mole
H = U + PV
H = U + ngRT
For determination of U per mol (ng = 1)
–3
102 (KJ/mol) = U + (1 × 8.3 × 350) × 10 U = 102 – 2.9 = 99.1 KJ/mole
44. In a perfect gas is no energy of interaction between the molecules of the gas, so change the distance
between the molecular by changing the volume of the gas cannot affect the internal energy of the gas.
U is independent of V. Hence internal pressure is zero.
45. W = +ve because work done on system.
W = 0 because thermally insulated container.
47. State 1  State 2
(1 L, 10 atm, 300 K) (4L, 5 atm, 600 K)
Heat given, q = 50 ´ (600 – 300) = 15000 J
W = – Pext (V2 – V1) = – 1 (4–1) = – 3 L atm = – 300 J
E = q + W = 15000 – 300 = 14700 J
H = E + P2V2 – P1V1 = 14700 J + (20 – 10)  100 J = 15.7 KJ

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48.  H = E + PV and H = E + PV
PV = nRT.
 H = E + nRT
For isothermal and reversible process
T = 0.
 H = E + 0.
 E = 0.  H is also equal to zero.

49. U = W
nCv (T2 – T ) = – P × (V2 – V1)
3 2
R (T2 – T) = – 1   T2 = T –
2 3  0.0821
50. From first law of Thermodynamics, E = q + w nCvdT = nCdT – PdV .....(1)
Now according to process, P = V and according to ideal gas equation, PV = nRT
2
We have , V = nRT
n R dT
On differentiating, 2VdV = nRdT and PdV = VdV =
2
n R dT
So, from first equation we have, nCvdT = nCdT –
2
R 4R
So, Cv = C – Hence, C =
2 2
51. W = – PV = – 1 × 105 (1 × 10–2 – 1 × 10–3) = – 1 × 105 × 9 × 10–3 = – 900 J.
52. N2 + 3H2  2NH3 n = 2 – 4 = – 2
H = U + nRT = U – 2RT.  H < U.
53. In isolated system, the expansion of gas is carried out adiabatically. Since heat exchange between
system and surrounding is not possible i.e. q = 0 and secondary wrev is always greater than wirr
therefore for reversible process there must be comparatively higher decreases in internal energy i.e. U
for reversible process will be more negative. Hence, final temperature in reversible process will be
smaller than irreversible process.
 (Tf)irrev > (Tf)rev
T2 V  1
54. S = nC v, m In + nR In 2 = C v, m In 2 + R In   = (C v, m – R) In 2
T1 V1  2
V
55. Ssystem = nR In 2 = 2 × R × In 2 = 11.52 J/K
V1
3.41 1000
Ssurrounding = – = – 11 J/K
310
Stotal = + 11.52 – 11 = + 0.52 J/K
T2 V
56. S = nCv n + nR n 2
T1 V1
For adiabatic process (Q = 0)
T2 V
E = W  nCv n = – nR n 2  S = 0.
T1 V1

T2  360 
57. S = nC p, m In = 2.5 × 18 × 4.2 In   = 34.02 J/K
T1  300 

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58. H2O (l)  H2O (g) Hvap = SvapTB.P. = x1T1
Hf (H2O,g) = Hf(H2O,l) + Hvap = x2 + x1T1
Hreaction = 2Hf, (CO2, g) + 3Hf(H2O, g) – Hf(C2H6,g)
= 2x3 + 3 (x2 + x1T1) – x4 = 2x3 + 3x2 + 3x1T1 – x4.
59. Lesser the Gºf, lesser its stability & easily it can decompose.
60. The compressor has to run for longer time releasing more heat to the surroundings.
61. All these are statements of second law of thermodynamics.
62. As dew formation is spontaneous process, therefore, entropy or randomness of the universe will
increase. As randomeness of the system has decreased but randomness of the surrounding will
increase larger so that change is positive.
P1
65. S (gas) = nR ln = 3 × 8.314 × ln2 = 17.29 J/K
P2
Since T = 0, therefore U = 0,
So, q = – W
 P 
= nRT 1– 2 
 P1 
q = T × 12.47 J/K
q
Ssurr = – = – 12.47 J/K
T
Change in S = + 4.82 J/K
66. 0.40 = aT 13 + bT1  0.40 = a × (1000) + b × 10  0.4 = 1000a + 10b ....(1)
0.92 = aT + bT2   0.92 = a × 8000 + 20b ....(2)
from Eqs. (1) and (2)
a = 2 × 10–5, b = 0.038
aT 3  bT a[T23 – T13 ]
Sm =  . dT = + b[T2 – T1] = 0.427 J/K-mol
T 3

67. (A) G º200 = H º200 – T S º200

H º200 = 20 – 4 = 16 kJ/mol
H ºT2 = H + Cp[T2 – T1]
20  200
H º400 = H º200 + kJ/ mol = 16 + 4 = 20 kJ/mol.
1000
68. Sreaction = 6(87) – 4X – 205  x = 145.75 J/mole K
69. It is because of the fact that for spontaneity, the value of G = (H – TS) should be < 0. If S is – ve,
H x
the value of TS shall have to be less than H or the value of S has to be less than i.e., .
T 298

T  V  5 373
71. S = nCV ln  f  + nR ln  f  = × 2 ln + 2 ln 10
T
 i V
 i 2 298

34.2
72. (D) No. of moles of sucrose = = 0.1
342
– (G)T.P = useful work done by the system
180  0.1 300
–G = – H + T.S = + (6000 × 0.1) + = 605.4 kJ.
1000

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73. G = H – TS
H =  HP   HR
H = – 110.5 + 266.3 = 155.8 KJ
S =  SP   SR
S = 197.6 + 27.28 – (57.5 + 5.74) = 161.64 J/mole K
For reaction to be spontaneous, G < 0
H 155800
H – TS < 0  T > = = 964 K
S 161.64
3
74. Given that, Hvaps = 30 kJ/mol = 30 × 10 J/mol.
Svaps = 75 J/mol.
Hvap
We know that, S =
TB.P
  H = TS  30×103 = T × 75.
T = 400 K.
75. In adsorption there is bond formation between the gases and solid surface which decrease the entropy.
76. For spontaneous process, G = – ve, K > 1 and E0cell = + ve.
77. If n = – ve than H < U.

78. CS2 () + 3O2 (g) CO2 (g) + 2SO2 (g)  H = –256 Kcal
Let Hf (CO2 , g) = –4 x and Hf (SO2 , g) = –3x
Hreaction = Hf (CO2 ,g) + 2 Hf (SO2 .g) – Hf (CS2, )
– 265 = –4 x – 6x –26
x = + 23.9
Hf (SO2,g)= 3x = –71.7 Kcal / mol.
79. CH2 = CH2 + H2 CH3–CH3 H = X1
So, Hydrogenation energy of benzene sholud be 3x1
H calculated = 3x1
So, Resonance energy = [3x1 – x2]
80. Required reaction  6C(graphite) + 3H2(g)  C6H6(g)
1. 6C(g) + 6H(g)  C6H6(g)
–1
H1 = –(6 × HC–H + 3HC=C + 3HC–C ) = –(6 × 416 + 3 × 591 + 3 × 331) = –5262 kJ mole
2. 6C(graphite)  6C(g) H2 = 6 × 718 = 4308
3. 3H2(g)  6H(g) H3= 3 × 436 = 1308
Adding (1) + (2) + (3)
6C(graphite) + 3H2(g)  C6H6(g)
H = H°f(C6H6,(g)) = H1 + H2 +H3 = 354 kJ mole–1
–1
Hence resonance energy = Hf (cal.) – H°f(theo) = 354 – 83 = 271 kJ mole
82. In neutralization of strong acid and base only H+ and OH– ions react in every case. So, heat of
neutralization is remain constant and equal to – 13.7 kcal (approximate).
83. Eqn. (ii) is for heat of neutralisation of strong acid with strong base. Eqn. (i) for weak acid with strong
base. The difference q2 – q1 is heat of dissociation of weak acid.
84. H3PO3  2H+ + HPO 32– ; rH = ?
+ –
2H + 2OH 2H2O;
rH = – 55.84 × 2 = – 111.68
–106.68 = ionH – 55.84 × 2
ion H = 5 kJ/mol.

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25
85. C8H18() + O2 (g)  8CO2(g) + 9H2O ()
2
25 16 – 25 9
ng = 8 – = = – = – 4.5
2 2 2
4.5  8.314  298
H – E = ngRT = – = –11.15 kJ
1000

1 1 1 1
86. CP = CP (HCl) – CP (H2) – Cp (Cl2) = 6.81 – × 6.82 – × 7.71
2 2 2 2
= 6.81 – 3.41 – 3.855 = – 0.45
H348 = H298 + (CP) (T) = – 22060 + (– 0.45) × 50 = – 22082.5 cal

87. Let mixture contain x mole of steam & y mole oxygen then,
Here, temperature is constant. So, amount of heat released = amount of heat gain
x 220 1.66
x × 132 = y(220)  = =  y : x = 1 : 0.6
y 132 1

88. 12g C = 1 mole, suppose CO produced = x moles.

Then CO2 produced = (1 – x) mole
 x (– 21.41) + (1 – x) (– 94. 05) = – 57.5.
This on solving gives x = 0.54 mole.
89. FeO + Fe2O3
2x x
1
Fe + O2  FeO Hof = – 65 Kcal/mole
2
3
2Fe + O2  Fe2O3 Hof = – 197 Kcal/mole
2
1
2FeO + O2  Fe2O3 
2
H = –197 + 65 × 2  H = – 67 Kcal/mole
1
2FeO + O2 Fe2O3 
2
1 2
3 3
2 1
– 2x +x
3 3
2
 2x
3 1 1
  x=
1 2 5
x
3
1
So, energy released = × 67 = 13.4 kcal/mole
5
90. Au(OH)3 + 4 HCl  HAuCl4 + 3 H2O, H =  28 kcal
HAuBr4 + 3 H2O  Au(OH)3 + 4 HBr, H =  36.8 kcal
_________________________________________________________
HAuBr4 + 4 HCl  HAuCl4 + 3 H2O, H =  8.8 kcal

When 100% conversion, heat absorbed = 8.8 Kcal

0.44
% conversion =  100 = 5%
8.8

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Au(OH)3 + 4 HCl  HAuCl4 + 3 H2O, H =  28 kcal
HAuBr4 + 3 H2O  Au(OH)3 + 4 HBr, H =  36.8 kcal
_________________________________________________________
HAuBr4 + 4 HCl  HAuCl4 + 3 H2O, H =  8.8 kcal

91.

+ –
H = 4EXe–F + Hloni [Xe  Xe ] – EF–F – Heg [F  F ]
= 4 × 34 + 279 – 85 – 38 = 136 + 279 – 123 = 415 – 213 = 292 kcal/ mole.

92. 1 M H2SO4 = 2g eq. of H2SO4

1
hence, y = 2x or x = y.
2
QR m
93. Q = m S T1   S T1  So, T1 = T2
2 2
94. Assuming density of solution is 1g/cc
and specipic heat is 4.2 J/g-K
q = msT = 100 × 4.2 × 3
millimoles of acid nuetralized = 5
1000
H = – 100 × 4.2 × 3 × = – 2.52 × 102 kJ/mole.
5
96. HCOOH is a weak acid so heat of neutralization is less than x.
97. The amount of heat either evolved or absorbed when one gram mole of a substance is formed from its
constituent elements, is known as the standard heat of formation (H°f ).
Standard state temperature is 25C° or 298K and pressure of gaseous substance is one atmosphere.
Thus in given thermochemical equation ‘(B)’ represents the standard heat of formation of HF.
1 1
H2(g) + F2(g)  HF(g) , H°f = ? (Standard heat of formation of HF(g))
2 2
98. C(s) + O2(g)  CO2(g) ;H = – 393.5 kJ mol–1 .... (1)
1
CO(g) + O2(g)  CO2(g) ; H = – 283 kJ mol–1 .... (2)
2
On subraction equation (2) from equation (1), we get C(s) + O2(g)  CO(g) ; H = – 110.5 kJ mol–1.
The enthalpy of formation of carbon monoxide per mole = – 110.5 kJ mol–1.
x
99. Let the bond dissociation energy of XY, X2 and Y2 be x,x and x, KJ/mol respectively,
2
1 1 –1
X2  Y2  XY; H = – 200 KJ mol .
2 2
H reaction = [(sum of bond dissociation energy of all reactants) – (sum of bond dissociation energy of
all product)]
1 1  x 0.5x
=  HX2  HY2  HXY  =  – x = – 200
2 2  2 2
200
 x= = 800 KJ mol–1.
0.25

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1 1 1 1 1 
100. I2(s) + CI2(g)  ICI(g) Hf, ICI(g) =  HI2 (s)I2 (g)  HI – I  HCI CI  –  HI CI 
2 2 2 2 2 
 1 1 1 
=   62.76  151.0   242.3  –  211.3  = 16.73 kJ/mol.
2 2 2 
10 10
dv
102. W =  Pdv  –20  = –20[n(V)]110 = –20 ln(10) = – 4605 J
1 1 V
q = U – W
= 400–(–4605) = 5005 J  5 kJ.
103. n=4
V1 = 20 lit. V2 = 60 lit
W = –Pext (V2 – V1)
125
=– × (60– 20) × 100 = – 500 J.
1000
In case of adiabatic process q = 0
U = 0 +W
nCpT = W
5
4× × RT = – 500
2
T = – 6 K
7.8
104. mole = = 0.1
78
H = n × Hvap
= 0.1 × 29.7 KJ = 2.97 KJ = 2970 J
H = vaporization
H 2970
t= =
v.i 11.4  .5
t = 540 second
t = 9 minute
105. C(graphite) C(diamond)
1 mole 1 mole
 = 2 g/cm3  = 3 g/cm3
12 12
V= ml V= ml
2 3
H = U + PV
U – H = –PV
5  12 12  –3 5 12 –1 4
= –5×10  –  × 10 L.atm = – 5× 10 × ×10 J= 100 KJ/mole = 10×10 J = 100KJ/mole
 3 2  6
U – H 100
 = 5 Ans.
20 20
3
n1CV, m1  n2 CV, m2 1 3R  2  R
106. Avg. CV, m = = 2 =2 R
n1  n2 3
3
–1
3/2–1
T1V1–1 = T2V2–1  320 × 12 = T2 ×(4)  T2 =160 K
U = (n1 + n2) CV,avg T = 3 × 2R × (160 – 320) = –960 R
|(U/10R)| = |–960 R/10R| = 96

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107. This is adiabatic irreversible process so, for this process
PV  = Constant, is not applicable
W = – Pext (V2 – V1)
But for adiabatic process
 P V  P1V1 
W = dU =  2 2 
  1 
PV = nRT  10 × 10 = n × 0.082 × 273 n = 4.47 moles
 P V  P1V1  1 V2  10  10
– Pext (V2 – V1) =  2 2   – 1 × (V2 – 10) =
  1  1.67  1
V2  100
 (10 – V2) =  6.7 – 0.67 V2 = V2 – 100  106.7 = 1.67 V2  V2 = 64
0.67
108. E = q + w 60 = 50 + w w = 10 J
109. E = 0   20 × 4.2 – 60 + W = 0
W = –24 J.
V2 T
110. Ssys = nRln + nCvln 2 
V1 T1
V2
 Ssystem = nR In = 2 × 8.314 In 7.5 = 33.6 J = 8 Cal.
V1

111. Hg () Hg (g) at 433 K and 4.19 mm of Hg is reversible and G = 0 but

G for Hg (g) (4.19 mm of Hg)  Hg (g) (760 mm of Hg)
P
with G = nRT ln 2 G = 18 J/mol.
P1

112. (i) In case of adiabatic reversible expansion, dqrev = 0  S = 0.

(ii) In case of free expansion (Adiabatically)
W = 0, q = 0, U = 0  nCV (T2 – T1) = 0  T2 = T1
V 
S = nR In  2  = 2R In (3) = 18 J/K.
 V1 

113. Heat generated = CTT = 1260 × 0.667 cal.

2.108  1
 nCH4 = = 0.01
210.8
PV 0.01
ntotal = = 0.04  mol% = × 100 = 25% Ans.
RT 0.04
114. Total mass of solution = (150 + 150) = 300 g {H2O = 1 g/mL}
Qtotal = mST = 300 × 1 × (29 – 25) = 1200 Cal
Since heat is liberated.
Q 1 1200 1
Heat of neutralization = × 1000 × = × 1000 × = 16 kcal
150 0.5 150 0.5
Hence Heat of neutralization = –16 kcal
115. 2C(s)  5C(g)  H1 = 5 × 718 = 3590
4H2(g)  8H(g)  H2 = 4 × 435 = 1740
5C(g) + 8H(g) — C5H8(g) H3 = –(8 × 913 + 2 × 348 + 2 × 615) = –5230
(1) + (2) + (3)
5C(s) + 4H2(g)  C5H8(g) Hr×n = Hf(C5H8) = H1 + H2 + H3 = 100
so resonance energy = 79 – 100 = –21 kJ mole–1
Hence resonance energy in Kcalmole–1 = 5

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585
116. (i) C(s) + O2(g)  CO2(g) ; Hºf = – 390 KJ/mol ; Hºf = × 12
18
1 15540
(ii) H2(g) + O2(g)  H2O () ; Hºf = – 280 KJ/mol ; Hºf =
2 55.5
15
(iii) C6H6() + O2(g)  6CO2 (g) + 3H2O () ; Hºf = –48
2
 Hº = [6(–390) + 3 (–280)] – 48= –3228 KJ/ mol
Mass of benzene is = 0.87  100 = 87 g
 Heat evolved from 87 g benzene = 3600 KJ.
H
Hence, = 36 kJ.
100

117. Hionization = Hneutralization of WA + SB – Hneutralization of SA + SB

= – 56.1 – (–57.3) = 1.2 KJ eq–1
–1
Enthalpy of ionization for making 100% ionization when there is no ionization at all = 1.5 KJ eq
1.5  1.2
 % of ionization =  100 = 20%
1.5

118. Fe2O3(s) + 3 H2(g)  2 Fe(s) + 3 H2O(l)

H°300 K = –35 kJ
H° = – 26 KJ
CP = 2CP (Fe, s) + 3CP (H2O, ) – CP (Fe2O3, s) – 3CP (H2, g)
CP = 80
– 26 × 103 = – 80 × 26720 + 80 (T)
T = 9
119.

so, Hr×n = Hf(NaBr) = Hsub + H1st ionisation (Na) + Hdiss. (Br2(g)) + H1st e–affinity –HL.E.
= 137 + 496 + 144 – 325 – 742 = 294
for .1 mole   Hr×n = 29.4 kJ mole–1
29.4
so, in kcal mole–1 Hr×n = = 7 kcal mole–1
4.2
3.5
120. n=
28
T = T2 – T1 = 298.45 – 298 = 0.45
CV = 2.5 kJ k–1 = 2500 JK–1 ; CP = CV + R = 2500 + 8.314 = 2508.314 JK–1
QP = CPT = 1128.74 J
Qp 1128.74 –1 –1 –1
H =   9030 J mol = 9.030 KJ mol = 9 KJ mol .
n 3.5 / 28
V2
121. q = –w = nRT ln = 2700 J
V1
V2 –1
Sgas = nR ln = 8.314 × 2.303 × log 3 = 9 JK
V1
q = 2700 – 900 = 1800 J
As entropy is a state function and S of system will be same as above one.
–1
Sgas = 9 J K
1800
Ssurr = – = – 6 J K–1 ; Stotal = 3 J K–1
300
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122.  – Work done by the system in case of infinite stage expansion is more than single stage expansion.
– Single stage process is a irreversible process.
V– We have 5 points on PV diagram.
 7 
124. H = (n1Cp,m1 + n2Cp,m2 )T =  0.5  R  0.5  4 R  (– 100) = – 375 R
 2 
5
and U = (0.5  R + 0.5  3R) (–100) = – 275 R.
2
125. H = 4 KJ
H = U + (PV)
U = 4 – P (V2 – V1)
105 (18  19)  10 –6 –4
=4– 3
= 4 + 1 × 10 = 4.0001 KJ
10
126. 1 × Vf = 5 × R × 546 = 224 L
W = – Pext (V) = – 1 atm (224 L) = – 224 L atm
 work done by system = 224 L atm
Enthalpy change (H) = q = 273 × 5 = 1365 L atm
U = q + W = 1365 – 224 = 1141 L atm.
127. From graph, slope = –1
 eq = log10V + log10T = constant
 VT = constant or PV2 = constant
R 5R R 3R
C = CV + C= + =
1 n 2 1 2 2
3R
 q = nCT = 3   (1000-100) = 4050 R
2
5R
U = nCVT = 3   (1000 – 100) = 6750 R
2
 W = U – q = 6750 R – 4050 R = 2700 R
128. V–T curve for a given mass of the gas is given

 nR 
PV = nRT ; V =  T
 P 

T  V  373
131. S = nCV ln  f  + nR ln  f  = 5 ln + 2 ln 10
 Ti   Vi  298
H = nCP T = n (CV+ R) T = 1 × 7  75 = 525 cal
136. 2C + 3H2  C2H6
Also, Hof(C2H6 ) (g) = 2 × 718 + 3 × 436 – a – 6b (HC–C = a, HC–H = b)
a + 6b = 2829 .....(i)
3C + 4H2  C2H8
Hof(C3H8 ) (g) = 3 × 718 + 4 × 436 – 2a – 8b
2a + 8b = 4002 .....(ii)
a = 345 & b = 414 kJ.

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137. Work done in isothermal process will be more than PV2 = const, process whatever be the value of K1
and K2 as is shown in the diagram.

138. Clearly (Vf )isothermal > (Vf )adiabatic

139. Work done in isothermal process is more than in adiabatic process as shown in the diagram above.

irreversible P
141. P°,V°   2V°,
isothermal 2

For reversible adiabatic,

P
(2V°)= P1V0  P1 = P°2–1
2
For reversible PV2 = K
P
(2V°)2 = P2V02  P2 = 2P°
2
So, P2 > P1
Since final volume is same
P  T
So, T2 > T1 
(142 to 144)
U3
H2O(, 75ºC) 
U1
H2O (, 100ºC) 
U2
H2O(g, 100ºC)  H2O(g), 100ºC
U1 = nCV, m() , T = 1 × 75 × (100 – 75) = 1875 J
U2 = n × Hvap – ngRT = 1 × 40700 – 1 × 8.314 × 373 = 37598.878 J
U3 = nCV, m()T = n(Cp,m(g) – R) T
= 1 × (33.3 – 8314) × (120 – 100) = 24.986 × 20 = 499.72 J
(145 to 147)
Let moles of C3H8 = x, moles of C2H2 = y & moles of CO2 = z.
Calculation of Hof of C3H8(g)
3C(s) + 4H2 (g)  C3H8(g)
.

Hof of C3H8(g) = [3(718) + 4(435)] – [2(347) + 8 (416)]

= 3894 – 4022 = –128 kJ / mol.

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Calculations of Hºf of C2H2.(g)
2C (s) + H2(g)  C2H2(g)
Hofof C2H2(g) = [2(718) + (435)] – [(812) + 2(416)]
= (1436 + 435) – [1644]
= 227 kJ/mol.
Calculations of Hof of C2H4(g)
2C (s) + 2H2(g)C2H4(g)
Hof of C2H4 (g) = 2 (718) + 2 (435) – [615 + 4(416)]
= 2306 – 2279 = 27 kJ/mol.
Calculation of Hocomb of C3H8(g)
C3H8(g) + 5O2(g)  3CO2(g) + 4H2O ()
Hocomb of C3H8 = [3 Hof (CO2) + 4 Hof (H2O, )] – Hof (C3H8, g)
= [3 (–394) + 4 (–286)] – (–128) = –2198 kJ/mol.
Calculation of Hocomb of C2H2(g)
C2H2(g) + 2.5O2(g)  2CO2(g) + H2O ()
Hocomb of C2H2 = [2 Hof (CO2) + Hof (H2O,)] – Hof (C.H.)
= [2 (–394) + (–286)] – 227 = –1301 kJ/mol.
Now total heat released during combustion
2198 x + 1301 y = 4800 (i)
Combustion = 3x + 2y + z = 10 (ii)
Total moles of H.O () formed = 4x + y.
3808
moles of C.H.(g) to be prepared = = 170.
22.4
Total heat absorbed during evaporation of water formation of 170 moles C.H. = 4800.
[(4x + y) × 0.875 x 40] + (170 x 27) = 4800
4x + y = 6 (iii)
on solvent (i), (ii) and (iii)
we get x = 1, y = 2, and z = 3

PART - IV
1. BC is a straight line & equation can be obtained by using
y  y1
(y – y1) = 2 (x – x1)
x 2  x1
P  3P 2P
(P – 3P°) = (V – V°)  (P – 3P°) = – (V – V°) ..... (1)
2V   V V
RT
Replacing P by T by using P = in equation (1)
V
 RT  2P 2PV(V  V) 3PV
  3P  = – (V – V°)  T = +
 V  V  V R R
For T to be maximum
dT
=0
dV
dT 2P(2V  V) 3P 5
=– + = 0  V = V°
dV VR R 4
5 5 
2P  V  V  V   3P 5 V
4 4 + 4 25  P V 
Tmax = – =  
VR R 8  R 

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Thermodynamics & Thermodynamics
2. Hº = – 3H 1º + H º2 + 2H 3º + 3H º4
= – 747.4 kJ
Hº = Uº + ng RT; where ng = – 8
8  8.314  300
– 747.4 = Uº –
1000
Uº = – 727.44 kJ.

3. For H2(g) + O2(g) — H2O2()

rHº2 rH1º
fHº (H2O2,) = rH3º + –
2 2
4. HA — H+ + A –; rH = 1.4 kJ/mol
+ –
Hneutralization = Hionization + rH of (H + OH  
– 55.95 = Hionization – 57.3 
 Hionization for 1 M HA = 1.35 kJ/mol
1.35
% heat utilized by 1 M acid for ionization = × 100 = 96.43%
1.4
So, acid is 100 – 96.43 = 3.57% ionized.
5. fSº(NH4CI,s) at 300 K
º 1 1 º 
= S NH 4 CI(s)
–  SNº 2  2SHº 2  SCI2 
 2 2 
–1 –1
= – 374 JK mol
fC P = 0
 f Sº310 = f Sº300
= – 374 JK–1 mol–1
º º
 H310 f = f H300 = – 314.5

º 310(–374)
f G310 = fHº – 310 Sº = – 314.5 – = – 198.56 kJ/mol.
1000
6. 0.42 = a(10)3  a = 0.42 × 10–3
10 10
Cp.m. a 0.42
Sm =  dT =  aT 2  [103  0]   0.14 J / K  mol
0 T 0 3 3

7. G = H – (TS)
= H – TS (isothermal)
 dq 
= 0 – TS = – T   rev 
 T 
= –  dqrev = – qrev = W rev
as process is isothermal so E = 0 = qrev + W rev
V 
so G = – nRT ln  f 
 Vi 
= – RT ln 2 = – 8.314 × 300 × 0.693 × 10–3 KJ mol–1 K–1
= – 1.728 KJ mol–1 K–1
P2 T2
4 
8. G =  V dP – S dT = 24.6   1 × 100 –  (10  102 T) dT

P1 T
3 
1

2 2
 10 2 (T22  T12 )   2 [(400)  (300) ]

= 820 – 10 (T2  T1 )   = 820 –  10 (400  300)  10 
 2   2 
= 820 – 1000 – 350 = –530 J
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Thermodynamics & Thermodynamics
9. (A) E will be – ve for combustion reactions
(B) Hf° (S, rhombic) = 0
(C) CH4(g) — C(g) + 4H (g) H = 1656 kJ/mole = 4 HC–H
C2H6(g) — 2C(g) + 6H (g) H = 2812 kJ/mole = 6 HC–H + HC–C
6
so HC–C = (2812 –  1656) kJ/mole = 328 kJ/mole
4
(D) Can not be concluded from given data.
10. (D) BOH (g) + aqueous — B+ (aq) + OH–(aq) H = –20 kJ/mole
11. More heat is evolved due to combustion of less stable form.
12. (A) Reversible adiabatic process is isoentropic
(B) Reaction is spontaneous, need not be exothermic.
(C) Only when PV work is innvolved
Hsystem 40600
(D) Ssystem = =– = – 54.42 J/K
Tb 373  2

13. The given reaction will be spontaneous when G would be negative when H – TS is negative. That
is,
H – TS < 0 or TS > H
or T> or T> or T > 463.4 K
200
CP dT
14. S200 (B) =  = 7 J mol–1 K–1
0 T
7500
S200 () = 7 + = 44.5 J mol–1 K–1
200
300
CP dT 300
S300 () = 44.5 +  = 44.5 + 60 ln + 1.6 = 70.43 J mol–1 K–1
200 T 200
30000
S300 (g) = 70.43 + = 170.43 J mol–1 K–1
300
600
S600 (g) = 170.43 + 50 ln = 205.09 JK–1 mol–1
300
15. (a) State A to state B (Isobasric expansion)
Wrok done by the gas = W 1 = – p(VB – VA) = – 1(40 – 20) = – 20L atm
(b) State B to state C (isochoric process)
Work done by the gas = W 2 = 0. ( V = 0)
(c) State C to state A (Isothermal compression)
V
Work done on the gas = W 3 = – 2.303 nRT log A
VC
VA
= – 2.303 pV log (pV = pAVA = pBVB = nRT = 20) = –20 n(½) = 20 × n(2) = 14
VC
 total work done by the gas = W 1 + W 2 + W 3 = – 20 + 0 + 14 = – 6 L atm
x
16. (a) 0.25 × 2808 × × 103 = 62.5 × 9.81 × 3.
180
x = 0.47 g.
3 y
(b) 0.25 × 2808 × 10 × = 62.5 × 9.81 × 6000.
180
Y = 940 g.
Y = mX   940 = m × 0.47   m = 2000

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Thermodynamics & Thermodynamics
17. W = – Pext (Vf – Vi) = – (1 atm) (8 – 2) L = – 6 L atm
as q = 0 so
E = W   3 (8 Pf – 12) = – 6
6 5
8 Pf = 12 – = 10  Pf = atm
3 4
5
3
Tf 10
so, = 4 =
Ti 62 12
T  V  12  10  12
so S = nCV, m n  f  + nR n  f  = 3 × ln   + ln 4
T
 i V
 i 300 12
  300
= 3.312 J/K
Ans. 3 J/K
5
18. H–CC–H+ O2  2CO2 + H2O, – 312 Kcal.
2
– 312 = [2(– 94) + (– 68)] – Hf(C2H2 ) .
Hf(C2H2 ) = 56 Kcal.
2C (s) + H2 (g) C2H2 (g), 56
2×150 100

2C (g) + 2H (g) H' = 0 – 2 × 95 – x

56 = [(2 × 150) + 100] – [(2 × 95) + x].
x = 154 Kcal.
HCC
=7
22
5
19. Heat evolved per mol of 'B' atoms = × 200 = 500 kJ
2
20. In isothermal reversible process.
qrev
S =
T
V2
q = –w = 2.303 RT log
V1
= 2740.6 J/mole
qrev 2740.6
Ssurr. =  = 9.135 J/K mole
T 300
Ssurr. = –Ssystem = –9.135 JK–1 mole–1
Suniverse = 0
1 3 –1
21.  Hº = Hfº of CaSO4 . H2 O(s) + Hfº of H2O(g) –Hfº of CaSO4.2H2O(s) = +83 kJ mol
2 2

22. Sº = 119.5 + (188 × 1.5) – 194 = 207.5 J/K mol 

–1
 Gº = Hº – TSº = 19550 J mol
Gº = –2.303 RT log Kp = – 2.303 R × 300 log (PH2O )3 / 2
19550 –3
log PH2 O =  = – 2.26 ; PH2 O = 4 × 10 atm
8645.83

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Thermodynamics & Thermodynamics
23. PH2 O = 1, Kp = 1
Gº = 0 at eqm.
Hº 83000
Hº – TSº  T = = = 400 K = 127ºC
Sº 207.5
(24 to 26)
T  200
1. –qc = qh  c  = 150 × Heat rejected = 30 kJ
T
 h 1000
q q 150  103 –1
2. S = rev = h = = 150 JK
T Th 1000
3. G = H – TS ; H = 0; S = 150 JK–1 ; G = –150 kJ
7
27. C2H6 (g) + O2(g)  2CO2 + 3H2O (l), – 1559.8.
2
– 15559.8 = 2 × (– 393.5) + 3 × (– 285.8) – Hf (C2H6 ) .
 Hf (C2H6 ) = – 84.6.

H' = 0 – 6 × BEC – H – BEC – C.

2 × 716.68 + 3 × 435.94 – 6BEC – H – BE C – C = – 84.6.
6BEC – H + BEC – C = 2741.18 kJ. ......(i)
5
CH3CHO + O2  2CO2 + 2H2O, – 1192.3.
2
– 1192.3 = 2 × (– 393.5) + 2 × (– 285.8) – Hf (CH3CHO)
Hf (CH3CHO) = – 116.3 kJ.

H' = 0 – 4 × BEC – H – BEC = O.

1
– 166.3 = 2 × 716.68 + 2 × 435.94 + × 498.94 – 4BEC – H – BEC = O .....(ii)
2

H' = 0 – 2 × BEC = O.
716.68 + 498.94 – 2 × BEC = O = – 393.5.
BEC = O = 804.56 kJ. .....(iii)
Now we can find all bond energies.

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