28 October 2023 19:41

1. Thermal equilibrium and definition of temperature

2. zeroth law of thermodynamics
3. heat, work and internal energy
4. First law of thermodynamics,
5. Second law of thermodynamics: gaseous state of matter,
6. change of condition of gaseous state -isothermal
7. adiabatic processes
8. reversible processes
9. irreversible processes
10. cyclic processes

Chapter 11- Thermodynamics Page 1

 THERMODYNAMICS

It is the branch of physics that deals with the concepts of heat and temperature and the inter-

conversion of heat and other forms of energy.

It mainly deals with the transformation of heat into mechanical work and vice versa

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 THERMODYNAMIC SYSTEM

An assembly of a very large number of particles having a certain value of pressure, volume

and temperature is called a thermodynamic system.

SURROUNDINGS

Everything outside a system which can have a direct effect on the system is called its

surroundings.

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 THERMODYNAMIC VARIABLES

The quantities like pressure (P), volume (V) and temperature (T) which help us to study the

behaviour of a thermodynamic system are called thermodynamic variables.

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 EQUATION OF STATE

The mathematical relation between the pressure, volume and temperature of a

thermodynamic system is called its equation of state.
PV = n RT,
P= pressure
V=volume
R = constant called universal gas constant
= 8.31 J mol-1 K-1
= 8.31 J mol-1 oC-1
T = temperature

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 THERMAL EQUILIBRIUM

Two systems are said to be in thermal equilibrium with each other if they have the same temperature.

ADIABATIC WALL

Wall that does not allow flow of heat.

DIATHERMIC WALL

Wall that allows flow of heat through it.

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 ZEROTH LAW OF THERMODYNAMICS

If TA = TC and TB = TC
Then TA = TB
If two systems A and B are separately in thermal equilibrium with a third system C, then A
and B are also in thermal equilibrium with each other. This is called zeroth law of
thermodynamics.

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 INTERNAL ENERGY

The internal energy of a system is the sum of molecular kinetic and potential energies.

➢ The intermolecular PE of a real gas is a function of its volume.

➢ The internal KE of a real gas is a function of its temperature.

➢ Internal energy of a system is a thermodynamic state variable.

➢ Internal energy of an ideal gas is purely kinetic in nature.

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 HEAT

Heat is a mode of energy transfer due to temperature difference between the system and the

surroundings.

WORK

Work is the mode of energy transfer brought about by means that do not involve temperature

difference.

N.B: Heat and work are not state variables.

Chapter 11- Thermodynamics Page 9

 SIGN CONVENTIONS USED

HEAT WORK INTERNAL ENERGY

1. Heat absorbed by a system → Positive 1. Work done by the system → Positive 1. Increase in internal energy → Positive

2. Heat given out by a system → Negative 2. Work done on the system → Negative 2. Decrease in internal energy → Negative

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 MOLAR SPECIFIC HEAT CAPACITY

Molar specific heat capacity =

SI unit of C =

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 TWO PRINCIPAL SPECIFIC HEATS OF GAS

Molar specific heat at Molar specific heat at

constant volume (CV) constant pressure (CP)

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 MOLAR SPECIFIC HEAT AT CONSTANT VOLUME (CV)

It is defined as the amount of heat required to raise the temperature of one mole of a gas

through 1oC at constant volume.

MOLAR SPECIFIC HEAT AT CONSTANT PRESSURE (CP)

It is defined as the amount of heat required to raise the temperature of one mole of a gas

through 1oC at constant pressure.

CP is greater than CV.

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SPECIFIC HEAT RELATION: MAYER'S FORMULA

CP - CV = R

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 FOR PROBLEM SOLVING

1. At constant volume: Q = n CV

2. At constant pressure: Q = n CP
3.

= constant which depends on the atomicity of the gas

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 FIRST LAW OF THERMODYNAMICS

If some heat is supplied to a system which is capable of doing work, then the quantity of
heat absorbed by the system will be equal to the sum of the increase in its internal energy and
the external work done by the system on the surroundings.
According to the first law of thermodynamics:
Q= u+ W

Q = heat supplied to the system by the surroundings

u = change is internal energy of the sytem

W = work done by the system on the surroundings.

=> Q = u + P V

Chapter 11- Thermodynamics Page 16

 THERMODYNAMIC PROCESS

A thermodynamic process is said to occur if the thermodynamic variables of a system

undergo a change with time.
1. ISOTHERMAL PROCESS 2. ADIABATIC PROCESS

It is thermodynamic process which occurs at a It is a thermodynamic process in which there is

constant temperature. no exchange of heat between the system and the
surroundings.

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 ISOTHERMAL PROCESS

1) ESSENTIAL CONDITIONS FOR AN ISOTHERMAL PROCESS TO TAKE PLACE:

i) The walls of the container must be properly conducting to allow free exchange of
heat between the system and the surroundings.
ii) The process of compression or expansion should be slow so as to provide
sufficient time for the exchange of heat.

2) EQUATION OF ISOTHERMAL PROCESS

PV = n R T
=> PV = constant, ∵ T = constant
=> P1V1 = P2V2

3) Work done in an isothermal process

Wiso = n R T ln

=> Wiso = n R T ln , ∵ P1V1 = P2V2

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4) FIRST LAW OF THERMODYNAMICS APPLIED TO ISOTHERMAL PROCESS

Q= u+P V
=> Q = P V , ∵ T=constant,
∴ u=0

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 ADIABATIC PROCESS

ESSENTIAL CONDITIONS FOR AN ADIABATIC PROCESS TO TAKE PLACE

1) The walls of the container must be perfectly insulated.

2) The process of compression or expansion should be sudden.

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 EQUATION OF ADIABATIC PROCESS

1) ADIABATIC RELATION BETWEEN P AND V

P = constant
=> P1 = P2

2) ADIABATIC RELATION BETWEEN P AND T

3) ADIABATIC RELATION BETWEEN V AND T

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FIRST LAW OF THERMODYNAMICS APPLIED TO ADIABATIC PROCESS

Chapter 11- Thermodynamics Page 22

WORK DONE IN AN ADIABATIC PROCESS

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 HEAT ENGINE

It is a device which converts continuously heat energy into mechanical energy in

a cyclic process.

EFFICIENCY OF THE HEAT ENGINE ( )

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 SECOND LAW OF THERMODYNAMICS

1. KELVIN-PLANCK STATEMENT

It is impossible to construct an engine, which will produce no effect other than

extracting heat from a reservoir and performing an equivalent amount of work.

It indicates that a working substance (the gas which we are using in the heat engine

to do work) operating in a cycle, cannot convert all the heat extracted from the
source into mechanical work. It must reject some heat to the sink at a lower
temperature.

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 2. CLAUSIUS STATEMENT

It is impossible for a self-acting machine, unaided by any external agency to

transfer heat from a body at a lower temperature to another body at a higher
temperature.

This is applicable to a refrigerator. The working substance can absorb heat

from a cold body only if work is done on it. The work is done by an electric
compressor.

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 REVERSIBLE PROCESS

Any process which can be made to proceed in the reverse direction by variation
in its conditions such that any change occurring in any part of the direct process
is exactly reversed in the corresponding part of reverse process is called a
reversible process.
At the end of the reversible process, both the system and surroundings must
return to their original states.

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 NECESSARY CONDITIONS FOR A REVERSIBLE PROCESS

1) The process must be quasi-static.

2) The dissipative forces such as viscosity, friction, inelasticity etc. should be

absent.

EXAMPLES OF REVERSIBLE PROCESS

1) An infinitesimally slow compression and expansion of an ideal gas at constant

temperature.
2) The process of gradual compression and extension of an elastic spring.
3) The process of electrolysis is reversible if the resistance offered by the

electrolyte is negligibly small.

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 IRREVERSIBLE PROCESS

Any process which cannot be retraced in the reverse direction exactly is

called an irreversible process.
Most of the process occurring in nature are reversible processes.

EXAMPLES OF REVERSIBLE PROCESS

1) Dissolution of salt in water.
2) Resting of iron.
3) Diffusion of gases.
4) Sudden expansion or contraction of a gas.

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 CYCLIC PROCESS

Any process in which the system returns to its initial state after undergoing a series of changes is known as a cyclic
process.

Work done during a cyclic process

➢ Work done during expansion or compression of a gas is equal to the area enclosed between the P-V curve and the
volume axis.
➢ Work done per cycle = area of the loop representing the cycle.
➢ If the loop is traced clockwise, the work done is positive and work is done by the system.
➢ If the loop is traced anticlockwise, the work done is negative and work is done on the system.

First law of thermodynamics applied to cyclic process

Q= u+ W
=> Q = W , as internal energy is a state function,
∴ u=0
Hence, in a cyclic process, the total heat absorbed by a system is equal to the work done by the system.

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 PROBLEMS

1. An ideal gas is taken round the cycle ABCDA as shown in the P-V

diagram.

The work done during the cycle is

a) PV
b) 2PV
c) PV/2
d) Zero

Chapter 11- Thermodynamics Page 31

1. An ideal gas is taken through the cycle A→B→C→A as shown in the

figure.
If the net heat supplied to the gas in the cycle is 5 J, the work done by the
gas in the process C→A is
a) -5 J
b) -10 J
c) -15 J
d) -20 J

Chapter 11- Thermodynamics Page 32