Chapter 4

THERMODYNAMICS

( 4.8,4.9,4.10,4.11,4.12)
Thermodynamics is the branch of physics that deals
with concept of heat and temperature and the inter
conversion of heat and other form of energy

Thermodynamic system
Thermodynamic variables
Thermodynamic processes
Thermodynamic laws
Application of thermodynamics
• Thermal equilibrium :
• Two systems in thermal contact with each other are
thermal equilibrium if they do not transfer heat between
them.

A B

• (At different temperature) (Heat flow) ( At same temperature)

• Suppose two bodies A and B in which A is hotter than B are

placed in contacts .
• The heat flows between them from A to B till their
temperature become equal .
• In this state the bodies A and B are said to be thermal
equilibrium with each other.
• Zeroth law of thermodynamics
( Concept of temperature)
It states that if two bodies A and B are separately in
thermal equilibrium with third body C , then A and B
are in thermal equilibrium with each other.

A A A
+ ⇒

B c B C B C

Bodies A , B and C are at same temperature.

• Zeroth law is used to measure the temperature of
body by thermometer.
• When thermometer and the body are in thermal
equilibrium , the thermometer indicates the
temperature of the object.
• Thermometry deals with different temperature scale
and methods of measurement of temperature.
• Temperature is the property of the body by which we
know whether the body is in thermal equilibrium with
other body or not.
• thermometer
 Heat , work and internal energy
• Heat and work are two different forms of
energy , which can be transferred to each
other.
• When energy is transferred from one body
to the other due to difference in
temperature, then transferred energy is
called heat.
• When the energy transfer does not depend
upon temperature difference between them
, the energy transfer between them is called
work
• Internal energy ( U ):
• Internal energy can be defined as the energy
associated with the random or disordered motion of
the molecules of the system.
• Every system consist of large no. of molecules. It may
be gas , liquid or solid.
• In gas it may be mono atomic, diatomic or poly atomic
which has translational , rotational and vibrational
kinetic energy.
• In liquid and solid due to strong intermolecular forces
along with kinetic energy it has also potential energy.
 Thermodynamic system:
It is a collection or a group of objects that can
form a unit which may have ability to exchange
energy with the surrounding.

• Any thing that is not part of system is surrounding .

• The boundary separate the system from surrounding.

• surrounding

• System boundary
 Thermodynamic system can be classified on the
basis of the possible transfer of heat and matter

•
• Heat matter Heat

• (Open system ) ( Closed system ) ( Isolated system )

 Heat and change in internal
energy of the system
• Let T S = temperature of the system
• T E = temperature of environment /surrounding
• Case – 1 :
• Energy flow into system

• Environment (T E)
TE>TS
•
• Q >0
System T s

•
• Case – 2 :
• Energy flows from the system
• Environment (T E )
TS>TE

• System (T S) Q< 0

• Q is negative (System loses heat energy)

• Case – 3 :
• There is no transfer of energy
• Environment (T E )
T S =T E

• System (T S)
• Q=0
• (No loss or gain in energy)

• System and surrounding (environment) are in thermal

equilibrium.
• The internal energy of the system can be changed by-
• 1. heating or cooling the system
• 2. work done on or by the system

• 1. heating or cooling the system:

• This can be done by supplying the heat to the system
or removing the heat from the system.

• T = 100 o C T =200 o C
• heat supplied to gas
•
• initial state final state
• burner
• 2.work done on or by the system:
• initial state work done on gas final state

• F→ o
T = 100 C T =200 o C

d
• When the piston is quickly pushed inside gas is
compressed , piston does some work on the system and
the energy of the system is increased , hence the internal
energy increased.
• When the gas pushes the piston outward , work done by
the system , volume increased and energy released .
Hence temperature decrease and the internal energy too
decreases.
 First law of thermodynamics
(relation between work and heat)
• When a quantity of heat is supplied to a system then the
quantity of heat absorbed by the system is equal to the
sum of increase in internal energy of the system and the
external work done by the system.

• ΔQ=ΔU+ΔW
• Δ Q = heat supplied
• Δ U = change in internal energy
• Δ W = work done
• Case -1:
• When work done is zero (ΔW=0)
• Δ Q = ΔU
• The heat supplied results in increase in internal
energy only.
• Case- 2:
• When system does work and no heat is
supplied.(ΔQ=0)
• 0 = ΔU + ΔW
• ΔU = - ΔW
• The work done is positive and internal energy is
negative as energy lost to the surrounding.
• Case -3 :
• When heat supplied to the system and work done by
the system
• ΔQ=ΔU+ΔW
• Δ U =Δ Q - Δ W
• Case – 4 :
• When heat is supplied to the system and work done on
the system
• ΔQ=ΔU-ΔW
• Δ U =Δ Q + Δ W

• Work done by the system is positive

• Work done on the system is negative
 Thermodynamic work done
• Consider a thermodynamic system which consist of
some quantity of an ideal gas enclosed in a cylinder
with a movable mass less and friction less piston.
dx dx

• (compression) (expansion )
• Let P = pressure exerted
• A = area of piston
• Force F = P A
• d x = small displacement
• Let the small work done d W = F d x
• dW= PAdx =PdV
• A d x = d V = change in volume
• Total work done
• Vf Vf
• W = ∫ d W =∫ P d V = P ( V f - V i )
Vi Vi

• In compression V f < V i , V f – V i is negative

• Hence the work done is negative .

• In expansion V f > V i , V f – V i is positive.

• Hence the work done is positive
 Thermodynamic state variables
• When temperature of the system changes (it gains or
looses energy), it s other properties also changes.
• Any observable characteristic or property of the system
is called system variable.
• These are of two types:
• A ) Intensive variables : which does not depend upon
the size of the system.
• Example : pressure , temperature, density
• B) Extensive variable: which depend upon the size of
the system
• Example: mass , volume , internal energy
 Thermodynamic Equilibrium

• A system is in thermal equilibrium if the following

three conditions of equilibrium are satisfied
simultaneously.
• A) Mechanical equilibrium:
• When there are no unbalanced force with in the
system and between the system and surrounding .
• B) Chemical equilibrium:
• When the chemical composition of the system does
not change with time i.e. there is no chemical reaction
and there is no transfer of matter due to diffusion .
• C) Thermal equilibrium :
• When the temperature of the system remain constant
through out.
• Thermodynamic state variables:
• The pressure , volume, temperature and mass are the
state variables of the thermodynamic system. These
variables describe the equilibrium state of the system.
• The mathematical relation between the state variables
is called the equation of the state.
• The graphical representation of equation of state of a
system is called P – V diagram.
• The area under the P – V curve in graph represent the
work done in the process.
• Positive work:
• Negative work :
• Positive work at constant pressure:
 Thermodynamics Process

• It is a procedure by which the initial state of a system

changes to it’s final state.
• The process in which changes in the state variables of a
system occur infinitesimally slowly are called quasi static
systems.
• It is concluded that work done by a system depends not
only on the initial and the final states, but also on the
intermediate states i.e. on the paths along which the
change takes place.
• Heat transferred to a system also depends on the path.
 Reversible and irreversible process

• In thermodynamics, a reversible process is

a process whose direction can be returned to its
original position by inducing infinitesimal changes to
some property of the system via its surroundings.
• Throughout the entire reversible process, the system
is in thermodynamic equilibrium with its
surroundings.
• An irreversible process is a change that cannot be
retraced in reverse.
• The path is not same in the forward or the reverse
direction.
• There is some loss due to friction and dissipative
forces.
 • Assumption in thermodynamic
processes:
a) Majority of thermodynamic processes are reversible.
They are quasi static in nature . They are extremely
slow in nature and the system undergoes infinitesimal
change at every stage except adiabatic process. The
system is in thermodynamic equilibrium in every
stage.
b) The system has a movable , frictionless ,mass less
piston fitted to a cylinder containing ideal gas .
Depending on the requirement the wall of the cylinder
can be good conductor for isothermal process and good
insulator for adiabatic process.
c) The ideal gas equation is applicable to the system.
 Different types of thermodynamic process

• States of a thermodynamic system can be changed by

interacting with its surrounding through work and
heat. When this change occurs in a system, it is said
that the system is undergoing a process.

A. Isothermal process ( T = constant)

B. Isobaric process ( P = constant )
C. Isochoric process ( V = constant )
D. Adiabatic process ( Q = constant )
 Isothermal process
• The temperature of the system remains constant.
• At constant temperature PV = constant
• P i Vi = P f V f
• Consider an isothermal expansion of ideal gas .
• V i and V f are the initial and final volume of gas
• The work done in infinitesimally small expansion is
given by d W = P d V Vf
• The total work done is given by W = ∫ d W
• ∫dW=∫PdV Vi

• PV = n RT ⇒ P = n R T / V
Vf Vf Vf
• W = ∫ n R T (d V /V) = n R T ∫ d V /V = n R T [ l n V ]
Vi Vi
Vi
• W = n R T [ l n V f - l n V i] = n R T l n ( V f / V i )

W = 2.303 R T log ( V f / V i )

W = 2.303 R T log ( V f / V i )
• For an ideal gas the internal energy depends
upon the temperature.
• As the temperature is constant in isothermal
process Δ U = 0
• ΔQ=ΔW
• Here the heat supplied to the system results in
work done.
• During expansion the work done is positive .
• During compression the work done is negative.
• An isothermal change is very slow change . The
system exchanges heat with its environment
and is in thermal equilibrium through out the
change .
 Isobaric process
• It is a constant pressure process.
• Example: Boiling of water at atmospheric pressure.

• The line AB in p – V diagram is called isobar.

• The graphs issued by meteorological department are
the isobars representing the regions at same pressure.
• Consider an ideal gas undergoing volume expansion at
constant pressure . Δ P= 0
• Let V i and V f are the initial and final volume .
• T i and T f are the initial and final temperature .
• Then the thermodynamic work done is given by
• W = ∫ P d V = P ( V f – V i ) = n R (T f – T i )
• The change in internal energy of the system is given by
• ΔU=nCvΔT =nCv(Tf–Ti)
• Where C v = specific heat at constant volume .
• According to 1 st law of Thermodynamics
• Q=ΔU+W
• Q= n C v ( T f – T i ) + n R (T f – T i )
• = n ( T f – Ti) ( C v + R ) [Cp=Cv+R]
• Q= n C p ( T f – T i )
• In an isobaric process the internal energy changes due to change
in temperature.
• The heat exchanged is used to do work and change the internal
energy.
 Isochoric process
• It is a constant volume process.
• A system does no work on its environment during an
isochoric change .
• As work done W = P Δ V
• W=0 (Δ V = 0 )
• Q=ΔU+W
• Q=ΔU
• ΔU=nCvΔT
• Q=nCvΔT
 Adiabatic process
• It is a process during which there is no transfer of heat
from or to the system.
• For an adiabatic process Q = 0
• The heat flow is prevented by completely insulating the
system or by carrying out the process rapidly so that
there is no time for exchange of heat.
• Q=ΔU+W
• As Q = 0 , Δ U = - W
• For adiabatic expansion W is + v e , Δ U is – v e .
Internal energy decreases.
• For adiabatic compression W is – v e , Δ U is + v e .
Internal energy increases.
• For an adiabatic process
• P V ϒ = constant = C
• Where ϒ is called specific heat ratio or adiabatic ratio.
• ϒ=Cp/Cv
• ϒ = 5/3 for mono atomic gas
• ϒ = 7/5 for diatomic gas
• ϒ = 8/6 = 4/3 for poly atomic gas
• The change in internal energy Δ U = n C v Δ T
• For 1 mole of gas Δ U = C v Δ T

Vf
• The work done is given by W = ∫ P d V
Vi
 Vf Vf
-ϒ
• W=C∫dV/Vϒ =C∫V dV
Vi Vi

-ϒ+1 1 – ϒ Vf
• W=C[V / ]
Vi
• W = C / 1 – ϒ × [ 1/ V f (ϒ-1 ) - 1/ V i (ϒ-1 ) ]
• We know
• PV ϒ = constant
• Or
• P iViϒ=PfVfϒ=C
• W = 1/ 1 – ϒ × [ P f V f / V f (ϒ-1 ) - P i V i / V i (ϒ-1 ) ]
• W = (1 / 1 – ϒ) × ( P f V f – P i V i)
• W = P f V f – P i V i / 1- ϒ
• W = n R ( T f – T i ) / 1- ϒ = n R ( T i – T f ) / ϒ - 1
• When the gas expands Tf < Ti , The work done is
positive . The gas will cool down.
• When the gas is compressed Tf > Ti , The work done is
negative , the gas will warm up.
 Cyclic process
• A thermodynamic process that returns a system to its
initial state is a cyclic process.
• In this process the initial and final state are same .
• For a cyclic process the total change in internal energy
of the system is zero. (Δ U = 0 )
• According to 1 s t law of
Thermodynamics
Q=W
 Free expansion
I. These expansions are adiabatic expansions with no
work done on or by the system.
II. Q = W = 0 and according to First law of
thermodynamics Δ U = 0 .
III. It is an uncontrolled instantaneous change and the
system is not in thermal equilibrium.
IV. A free expansion cannot be plotted on a P – V diagram
, only initial and final state can be plotted .
V. Example : sudden rupture(break) of balloon, sudden
puncture of Tyre .