THERMODYNAMICS

Thermodynamics

(1) Thermodynamics : It is a branch of science which deals with exchange of heat energy between bodies and
conversion of the heat energy into mechanical energy and vice versa.
(2) Thermodynamic system : A collection of an extremely large number of atoms or molecules confined within
certain boundaries such that it has a certain value of pressure, volume and temperature is called a thermodynamic
system. Anything outside the thermodynamic system to
which energy or matter is exchanged is called its surroundings.
Thermodynamic system may be of three types :
(i) Open system : It exchange both energy and matter with the surrounding.
(ii) Closed system : It exchange only energy (not matter) with the surroundings.
(iii) Isolated system : It exchange neither energy nor matter with the surrounding
Zeroth Law of Thermodynamics
If systems A and B are each in thermal equilibrium with a third system separately C, then A and B are in thermal
equilibrium with each other. The zeroth law leads to the concept of temperature.

First law of Thermodynamics :- It states that if an amount of heat dQ is added to a system , a part of heat is used in
increasing its internal energy while the remaining part of heat may be used up as the external work done dW by the
system
Mathematically dQ=dU+dW , dQ=dU+ PdV.
Quantities Involved in First Law of Thermodynamics
(1) Heat (ΔQ) : It is the energy that is transferred between a system and its environment. Heat is a form of energy so
it is a scalar quantity with dimension [ML2T-2].
(2) Work (ΔW) :
∴ Work done ΔW=

(i) Like heat, work is also a path dependent, scalar physical quantity with dimension [ML 2T-2]
(ii) ΔW = positive if Vf > Vi i.e., system expands ,ΔW = negative , if Vf < Vi i.e., system contracts
(iii) W = area under P – V diagram
It is positive if volume increases (for expansion)
It is negative if volume decreases (for compression)
It is positive if the cycle is clockwise.
It is negative if the cycle is anticlockwise

(3) Internal energy (U) :

(i) Internal energy of an ideal gas is totally kinetic U = Uk= 3/2 RT
(ii) Change in internal energy does not depends on the path. ΔU = Uf – Ui
(iii) Change in internal energy in a cyclic process is always zero.
Sign conventions

Types of thermodynamic Process:-

(1) Isothermal process – process taking place at constant temperature.
(2) Adiabatic process – process where there is no exchange of heat.
(3) Isochoric process – process taking place at constant volume
(4) Isobaric process –Process taking place at constant Pressure.
(5) Cyclic process:- Process where the system returns to its original state.

Example of Isothermal Process :

(i) Melting process [Ice melts at constant temperature 0ºC]

(ii) Boiling process [water boils at constant temperature 100ºC]

Work done for an isothermal process

Adiabatic Process: In this process P, V and T changes but ΔQ = 0.

(1) Essential conditions for adiabatic process :

(i) All wallls of the container and the piston must be perfectly insulating. (ii) The speed of process should be fast.
(2) Example of some adiabatic process :
(i) Sudden bursting of the tube of bicycle tyre. (ii) Propagation of sound waves in air and other gases.
(3) Energy in adiabatic process : For adiabatic process
ΔQ = 0, ∴ ΔU + ΔW = 0
If ΔW = positive then ΔU = negative i.e., adiabatic expansion produce cooling.
If ΔW = negative then ΔU = positive i.e., adiabatic compression produce heating.

(4) Equation of state :

Reversible and Irreversible Process

(1) Reversible process : A reversible process is one which can be reversed in such a way that all changes occuring
in the direct process are exactly repeated in the opposite order and inverse sense.The conditions for reversibility are:
(i) There must be complete absence of dissipative forces. (friction, viscosity etc.)
(ii) The speed of process should be infinitely slowly.
(iii) The temperature of the system must not differ appreciably form its surroundings.
Examples of reversible process are :
(a) All slow isothermal and quasistatic process are reversible.
(b) Very slow evaporation or condensation.
(2) Irreversible process : Any process which is not reversible exactly is an irreversible process. Examples of
irreversible processes are :
(i) Sudden expansion or contraction
(ii) Heat transfer between bodies
Cyclic and Non-cyclic Process
A cyclic process consists of a series of changes which return the system back to its initial state. In non-cyclic process
the series of changes involved do not return the system
back to its initial state.
(1) In cyclic process change in internal energy is zero and temperature of
system remains constant.
(2) Heat supplied is equal to the work done by the system.
(3) For cyclic process P–V graph is a closed curve and area enclosed by the closed path represents the work done.
If the cycle is clockwise work done is positive and if the cycle is anticlockwise work done is negative.
Heat Engine :The essential parts of a heat engine are :
Source : Working substance : Steam, petrol etc.
Sink : ‘‘efficiency’’ η is given by
A perfect heat engine η = 1. Practically efficiency is always less than 1.
Refrigerator or Heat Pump.
A refrigerator or heat pump is basically a heat engine run in reverse direction. It essentially consists of three same
parts. The performance of a refrigerator is expressed by means of ‘‘coefficient of performance’’ β which is defined
as the ratio of the heat extracted from the cold body to the work needed to transfer it to the hot body.

Second Law of Thermodynamics

(1) Clausius statement : It is impossible for a self acting machine to transfer heat from a colder body to a hotter one
without the aid of an external agency.
(2) Kelvin’s statement : It is impossible for a body or system to perform continuous work by cooling it to a
temperature lower than the temperature of the coldest one of its surroundings.
(3) Kelvin-Planck’s statement : It is impossible to design an engine that extracts heat and fully utilises into work
without producing any other effect.
Carnot Engine
Carnot designed a theoretical engine. This engine cannot be realized in actual practice.
(1) Carnot cycle : The working substance of the engine undergoes a cycle known as Carnot cycle. It consists of the
following four strokes.
(i) Isothermal expansion :
(ii) Adiabatic expansion :
(iii) Isothermal compression :
(iv) Adiabatic compression :
Efficiency of Carnot cycle :
(i) Efficiency of a heat engine depends only on temperatures.
(ii) Efficiency of a heat engine is always lesser than unity, i.e., whole ofheat can never be converted into work which
is in accordance with second law.

1 Mark Questions

1. Which Thermo dynamical variable is defined by the first law of thermodynamics?

2. What is the amount of work done in the Cyclic process?
3. Out of the parameters- temperature, pressure, work and volume, which parameter does not Characterize the
thermodynamics state of matter?
4. What is the nature of P-V diagram for isobaric and isochoric process?
5. On what factors does the efficiency of Carnot engine depends?
6. Can we increase the temperature of gas without supplying heat to it?
7. Which thermodynamic variable is defined by Zeroth law of thermodynamics?
8. Under what ideal condition the efficiency of a Carnot engine be 100%.
9. What is the efficiency of Carnot engine working between ice point and steam point ?
10. Heat cannot flow itself from a body at lower temperature to a body at higher temperature is a statement or
consequence of which law of thermodynamics

2 and 3 Mark Questions

1. Write two limitation of the first law of thermodynamics.
2. Write the expressions for Cv and Cp of a gas in terms of gas constant R and

γ where

3. No real engine can have an efficiency greater that of a carnot engine working between the same low
temperatures. Why ?
4. Give two statements for the second law of thermodynamics
 5. An ideal monatomic gas is taken round the cycle ABCDA as shown. Calculate the work done during the
cycle.

6. Explain what is meant by isothermal and adiabatic operations.

7. Two bodies at different temperatures T1 and T2, if brought in thermal contact do not necessarily settle to the
mean temperature (T1 + T2)/2 Explain
8. Obtain an expression for work done in an isothermal process
9. Identify and name the Thermodynamic processes 1, 2, 3 as shown in figure.

10. Explain briefly the principle of refrigerator . What is meant by coefficient of performance ?
11. (a) Why a gas has two principal specific heat capacities ?
(b) Which one is greater and why ?
(c) Of what significance is the difference between these two specific heat capacities and their ratio ?
12. State first law of thermodynamics. On its basis establish the relation between two molar specific heat for a gas.
13. State zeroth law of thermodynamics. How does it lead to the concept of temperature ?
14. What is a cyclic process ? Show that the net work done during a cycle process
is numerically equal to the area of the loop representing the cycle.

5 Mark Questions

1. When a system is taken from state A to state B along the path ACB, 80 kcal of heat flows into the system
and 30 k cal of work is done.
(a) How much heat flows into the system along path ADB if the work done is 10 kcal ?
(b) When the system is returned from B to A along the curved path the work done is 20 k cal. Does
the system absorb or liberate heat.
(c) If UA= 0 and UD = 40 k cal, find the heat absorbed in the process AD ?
2. 0.5 mole of helium is contained in a container at S.T.P. How much heat energy is needed to double the
pressure of the gas, keeping the volume constant ?
Heat capacity of gas is 3 J g–1 K–1.

3. A thermodynamic system is taken from an original state to an intermediate state by the linear process
shown in Fig. Its volume is then reduced to the original value from E to F by an isobaric process.
Calculate the total work done by the gas from D to E to F.

4. What is the coefficient of performance (β) of a carnot refrigerator working between 30ºC and 0ºC ?
5. Calculate the fall in temperature when a gas initially at 72ºC is expanded suddenly to eight times its
original volume. (γ = 5/3)
6. Refrigerator is to maintain eatables kept inside at 9ºC. If room temperature is 36ºC calculate the
coefficient of performance.
7. A perfect carnot engine utilizes an ideal gas the source temperature is 500 K and sink temperature is 375
K. If the engine takes 600 k cal per cycle from the source, calculate
(i) The efficiency of engine
(ii) Work done per cycle
(iii) Heat rejected to sink per cycle
8. Two Carnot engines A and B are operated in series. The first one A receives heat at 900 K and reject to a
reservoir at temperature T K. The second engine B receives the heat rejected by the first engine and in
turn rejects to a heat reservoir at 400 K calculate the temperature T when
(a) The efficiencies of the two engines are equal
(b)The work output of the two engines are equal
 9. Ten mole of hydrogen at NTP is compressed adiabatically so that its temperature become 400ºC. How
much work is done on the gas ? What is the increase in the internal energy of the gas? R = 8.4 J mol–1
K–1, γ = 1.4

10. The temperature T1 and T2 of the two heat reservoirs in an ideal Carnot engine be 1500ºC and 500ºC
respectively. Which of these increasing T1 by 100ºC or decreasing T2 by 100ºC would result in a greater
improvement in the efficiency of the engine.

11. Describe briefly Carnot engine and obtain an expression for its efficiency.

12. Define adiabatic process. Derive an expression for work done during adiabatic process.

CASE STUDY BASED QUESTIONS

(1) In a quasi-static process, at every stage, the difference in the pressure of the system and the external pressure is
infinitesimally small. The same is true of the temperature difference between the system and its surroundings . To
take a gas from the state (P, T ) to another state (P', T ' ) via a quasi-static process, we change the external pressure
by a very small amount, allow the system to equalize its pressure with that of the surroundings and continue the
process infinitely slowly until the system achieves the pressure P ¢. Similarly, to change the temperature, we
introduce an infinitesimal temperature difference between the system and the surrounding reservoirs and by
choosing reservoirs of progressively different temperatures T to T', the system achieves the temperature T'

(a) An ideal gas undergoes four different process from the same initial state. (Fig.). Four process are adiabatic ,
isothermal, isobaric & isochoric. Out of 1, 2, 3 & 4 which one is adiabatic

(a) 4 (b)3 (c)2 (d)1

(b) An ideal gas undergoes cyclic process ACBC as shown is given PV diagram
The amount of work done by the gas is
(a) 6 Po Vo (b) –2 Po Vo (c) + 2Po Vo (d) + 4 Po Vo

(C) Consider two containers A and B containing identical gases at the same pressure, volume and temperature. The
gas in container A is compressed to half of its original volume isothermally while the gas in container B is
compressed to half of its original value adiabatically. The ratio of final pressure of gas in B that of gas in A is

(d) Which of the process described below are irreversible?

(a) The increase in temperature of an iron rod by hammering it

(b) A gas in a small container at a temperature T1 is brought in contact with a big reservoir at a higher Temperature.
T2 which inverses the temperature of the gas
(c) A quasi - state isothermal expansion of an ideal gas in cylinder fitted with a frictionless piston
(d) An ideal gas is enclosed in a piston cylinder arrangement with adiabatic Walls. A weight W is added to the
piston, resulting in compression of a gas

(2) Adiabatic Process

In an adiabatic process, the system is insulated from the surroundings and heat absorbed or
released is zero. for an adiabatic process of an ideal gas.P Vγ = constant
where γ is the ratio of specific heats (ordinary or molar) at constant pressure and at constant volume.

Thus if an ideal gas undergoes a change in its state adiabatically from (P1, V1) to (P2, V2) :

(a).A mono-atomic gas at a pressure P, having a volume V expand isothermally to a volume 2V and then
adiabatically to a volume 16V. The final pressure of the gas is (Y = 5/3)
(a) 64 P (b) 32 P (c) P/64 (d) 16 P
(b). One mole of an ideal diatomic gas undergoes a transition from A to B along a path AB as shown in fig. The
change in internal energy of the gas during the transition is (γ =3/5)
(a) –20 KJ (b) 20 J (c) –12 KJ (d) 20 KJ
(c). At 27°C two moles of an ideal mono-atomic gas occupy a volume V. The gas expands adiabatically to a volume
2V. The final temperature of the gas is (γ=5/3)
(a) 179 K (b) 189 K (c) 213 K (d) 219 K
(d). P–V plots for two gases during adiabatic process are shown in fig. Plots 1 & 2 should correspond respectively to

(a) He and O2 (b) O2 and He (c) He and Ar (d) O2 and N2

(3) Heat engine is a device in which a system undergoes a cyclic process resulting in conversion of heat into work. If
Q1 is the heat absorbed from the source, Q2 is the heat released to the sink, and the work output in one cycle is W, the

efficiency η of the engine is

In a refrigerator or a heat pump, the system extracts heat Q2 from the cold reservoir and releases Q1 amount of heat
to the hot reservoir, with work W done on the system. The co-efficient of performance of a refrigerator is given by,

(a) The efficiency of engine is 1 is η1 at T1= 200 C

ͦ and T2= 0 ͦC and η2 at T1 = 0°C and T2 –200 K. Find the ratio of
η1/η2
(a) 1.00 (b) 0.721 (c) 0.577 (d) 0.34
(b) A Carnot engine, having an efficiency of η =1/10 as heat engine is used as a refrigerator. If the work done on the
system is 10J the amount of energy absorbed from the reservoir at lower temperature is
(a) 99 J (b) 90 J (c) 1 J (d) 100 J
(c) The door of a running refrigerator inside a room is left open. The correct statement out of the following ones is
(a) The room will be cooled slightly
(b) The room will be warmed up gradually
(c) The room will be cooled to the temperature inside the refrigerator
(d) The temperature of the room will remain unaffected.
(d) If an engine takes 5J of heat energy from a reservoir and rejects 3J to the surroundings, what is its efficiency?
a) 2/5 b) 3/5 c) 1/5 d) 0

ASSERTION- REASON BASED QUESTIONS

Q.1. Assertion : When a bottle of cold carbonated drink is opened, a slight fog forms around the opening.
Reason : Adiabatic expansion of the gas causes lowering of temperature and condensation of water vapours.

Q.2. Assertion : The heat supplied to a system is always equal to the increase in its internal energy.Reason : When a
system changes from one thermal equilibrium to another, some heat is absorbed by it

Q.3. Assertion : In adiabatic compression, the internal energy and temperature of the system get decreased.
Reason : The adiabatic compression is a slow process

Q.4. Assertion : In isothermal process whole of the heat energy supplied to the body is converted into internal
energy.
Reason : According to the first law of thermodynamics ΔQ = ΔU.

Q.5. Assertion : We cannot change the temperature of a body without giving (or taking) heat to (or from) it.
Reason : According to principle of conservation of energy, total energy of a system should remains conserved.

Q.6. Assertion : The specific heat of a gas is an adiabatic process is zero and in an isothermal process is infinite.
Reason : Specific heat of a gas in directly proportional to change of heat in system and inversely proportional to
change in temperature.

Q.7. Assertion : Reversible systems are difficult to find in real world.

Reason : Most processes are dissipative in nature

Q.8. Assertion : Air quickly leaking out of a balloon becomes coolers

Reason : The leaking air undergoes adiabatic expansion.

Q.9. Assertion : Thermodynamic process in nature are irreversible.

Reason : Dissipative effects cannot be eliminated.

Q.10. Assertion : Work and heat are two equivalent form of energy.
Reason : Work is the transfer of mechanical energy irrespective of temperature difference, whereas heat is the
transfer of thermal energy because of temperature difference only.