THERMODYNAMICS

Introduction

• Thermodynamics is a branch of physics,

which deals with the transformation of
heat into mechanical work.
• Thermo means heat and it is a form of
energy. The definition of heat is that
which is transferred between the system
and its surroundings by virtue of
temperature difference.
 Thermodynamic systems
• A system, which can be described in terms of
thermodynamic coordinates, is called a thermodynamic
system.
• The thermodynamic coordinates are pressure, volume,
temperature and entropy.
• Gas, steam vapour. mixture of gasoline and air etc. are
some of the thermodynamic systems.
• In Physics the thermodynamic systems also include
stretched wires, thermocouples, surface films, reversible
cells, magnetic materials, electrical condenser, electrical
cells etc.
 Thermal equilibrium
• A system is in thermal equilibrium if any two of its thermodynamic
coordinates remain constant so long as the external conditions are
unchanged.
• Consider a certain mass of a gas enclosed in cylinder with a gas tight
piston. If the pressure and volume of the enclosed gas are P and V at
the temperature of the surroundings, these values of P and V will
remain constant as long as the temperature and pressure of the
surroundings remain unaltered. Then the gas is said to be in thermal
equilibrium with the surroundings.
• In general thermal equilibrium is the state achieved by two or more
systems after they have been in thermal communication with each
other through diathermic walls.
• A diathermic wall allows thermal communication. The most common
experimental diathermic wall is a thin metallic sheet. An adiabatic wall
thermally isolates the system from the surroundings. Examples:- Thick
layers of wood, concrete, asbestoses etc.
 Zeroth law of thermodynamics
• The postulate of Ralph Fowler after the enunciation of first and
second laws of thermodynamics is known as the zeroth law of
thermodynamics. This law is established on the basis of temperature
• The zeroth law of thermodynamics states that two systems, in
thermal equilibrium with a third, are in thermal equilibrium with
each other.
• Consider three systems A, B and C. Let A and B are separately in
thermal equilibrium with C. Then A and B are also in thermal
equilibrium with each other.
 Concept of temperature

• Temperature is a measure of hotness of a body.

• The temperature of a system is a property that
determines whether or not a system is in thermal
equilibrium with other systems.
• The necessary and sufficient condition for thermal
equilibrium between two systems is that they
have the same temperature.
• If a number of systems are in thermal equilibrium,
the common property of the system can be
represented by a numerical value called the
temperature.
 Thermodynamic equilibrium
• A system is said to be in thermodynamic equilibrium if it is in
mechanical, chemical and thermal equilibrium. For a system to be
in mechanical equilibrium, there should not be any unbalanced
forces acting on any part of the system or the system as a whole.
• For a system to be in chemical equilibrium there should not be any
chemical reaction within the system and no movement of any
chemical constituent from one part of the system to the other.
• For a system to be in thermal equilibrium there should not be any
temperature difference between the system and the surroundings.
• Thus it is clear that if there is a finite unbalanced force it may cause
the system to pass through non equilibrium states.
 Quasi static process
• Once a system is in thermodynamic equilibrium and the surroundings are kept
unchanged, no motion will take place and no work will be done. But, if the sum of
the external forces is changed, there will be finite unbalanced force acting on the
system. Thus the condition for the mechanical equilibrium is not satisfied. Due to
this, unbalanced forces or torques may be created within the system, which may
result in setting up of turbulence or waves. So there may be some sort of
accelerated motion. As a result of the turbulence, acceleration etc. a non uniform
temperature distribution may occur thereby a finite difference of temperature
between the system and surroundings. Due to the change in the forces and
difference in temperature, chemical reaction or the motion of the chemical
constituent may take place.
• Thus a finite unbalanced force may cause the system to pass through non-
equilibrium states. We imagine an ideal situation in which the external forces
acting on a system are varied slightly so that the unbalanced force is infinitesimal
and the process proceeds infinitesimally slowly. A process performed in this ideal
way is said to be quasi-static.
• A quasi static process is defined as a process in which the deviations from the
thermodynamic equilibrium is infinitesimal and all the states through which the
system passes during the quasi static process can be considered as equilibrium
states.
• Consider a small amount of gas in an adiabatic
cylinder with a smooth moving airtight piston. Let
a small weight be placed on the piston so that the
pressure of the gas inside the cylinder is slightly
greater than outside the cylinder

If small weights are added

slowly one by one, the
compression of the gas can be
considered as quasi-static.
Since under these conditions
the piston moves in an
infinitesimal distance only
during compression.
 Intensive and extensive coordinates

• The coordinate due to that property of a system by

which it occupies space is called extensive coordinates.
Total mass, total volume, length, area etc. are examples
of extensive coordinates.
• The coordinates of a system that remains the same
irrespective of the properties are called intensive
coordinates. Pressure, temperature, surface tension, etc.
are intensive coordinates.
• The intensive coordinates of a system, such as
temperature and pressure, are independent of the mass;
the extensive properties are proportional to the mass.
 P-V Diagram and work done
• The volume of gas enclosed in a cylinder with a gas tight piston
changes with the motion of the piston in the cylinder. The position of
the piston at any moment is proportional to the volume.
• A convenient way to visualize these changes in the pressure
and volume is by using a Pressure Volume diagram or PV
diagram. Each point on a PV diagram corresponds to a
different state of the gas. The pressure is given on the vertical
axis and the volume is given on the horizontal axis.
• The area under the diagram gives the work done in that
thermodynamic process

dW = Fdx = Padx = PdV

• Area under the diagram = length x breadth
= (Vf – Vi) x P = ʃPdV = ʃdW =Total work done
The changes in pressure and volume of a gas during expansion are
indicated by the curve in fig 1.2(a). Here  PdV is the area under the
curve and work is done by the gas; dV is positive.
PV diagram during compression are indicated by fig 1.2(b). Here  PdV

is area under the curve and work is done on the gas; dV is negative.
The expansion and compression curves are drawn together so that they
constitute two processes that bring the gas back to its initial state. This is
shown in the fig1.2(c). Such a series of two or more processes represented
by a closed figure is called a cycle. The area within the closed figure in fig
1.2(c) represents the net work done in the cycle.
 State functions and path functions
• A property whose value doesn’t depend on the path taken
to reach that specific value is known to as state
functions or point functions.
Examples: Pressure, Temperature, Volume, Mass, Internal
energy
• In contrast, those functions which do depend on the path
from two points are known as path functions.
Examples:  heat, work
• State functions are the values which depend on the state
of the substance and do not depend on how the state was
reached or established..
 Heat – a path function
• When a system changes from one state
to another the quantity of heat
transferred will depend on the
intermediate stages through which the
system passes. That is, its path and
hence it is a path function
 Work - A path function
Consider a system, which is taken from an initial equilibrium state I to the final
equilibrium state 2 by two different paths A and B as in fig 1.3. We assume the
processes are quasi static. In the P-V diagram, the areas under these curves are
different and hence the work done are also different

2A

For the path A, the work done

WA   PdV
1A

2B

For the path B, the work done WB   PdV

1B

The values of WA and WB are not equal. Thus WA and WB depend

on the path. So the work is a path function. Hence work done in
taking a system from state 1 to state 2 will be different for
different paths
 First Law of Thermodynamics
• The first law of thermodynamics is the application of
the conservation of energy principle to heat and
thermodynamic processes:
• It states that when heat is given to a system, it is used for two
purposes. One is to increase the internal energy and the other
part of it to do external work.
• Let, ΔQ is the net heat transferred into the system of unit mass.
That is, ΔQ is the sum of all heat transfer into and out of the
system, ΔU be the change in internal energy of the system and
ΔW is the net work done on the system. Then
Q  U  W
Q  U  PV .......................(1)
Let C be the specific heat capacity of the substance. If ΔQ
amount of heat is given to the substance so that its
temperature changes by ΔT, at constant volume,

Q
C  CV 
T
Q  CV T
Substituting in equation (1)

CV T  U  PV V
But here since it is under constant volume, ΔV = 0 and hence
CV T  U Substituting this in equation (1), we get

Q  CV T  PV ..............................(2)
 Isothermal process
• A process in which pressure and volume changes at constant
temperature is known as an isothermal process
• In such a process there is always heat transfer between the
system and the surroundings so that the system must be in
very good thermal contact with the surroundings
• This means that the wall of the container is a perfect heat
conductor (diathermic)
• An isothermal process must be infinitely slow
Equation of state for an isothermal process
Consider 1 mole of an ideal gas. Then PV  RT
But, for an isothermal process T is a constant
 PV  k
Where k is a constant
 Adiabatic process (Isentropic process)
• In an adiabatic process the system is thermally isolated from the
surroundings so that heats neither enters and leaves the system.
• In this process pressure volume and temperature may change.
• This process is also called isentropic process, since the entropy of
the system remains constant throughout the process.
Equation of state of adiabatic process
Consider one mole of an ideal gas enclosed in a perfectly isolated
cylinder at a pressure P1, volume V1 and temperature T1. Then let
it be suddenly expanded so that pressure, volume and
temperature changes to P2, V2 and T2 . Then according to the first
law of thermodynamics

dQ  Cv dT  PdV ...........(1). But since it is an adiabatic process, dQ = 0

 0  Cv dT  PdV .........(2). Now, for an ideal gas, PV=RT. Differentiating
 PdV  VdP  RdT
PdV  VdP
 dT  .............(3)
R
From equation 2, PdV  Cv dT
PdV  VdP
 PdV  Cv
R
RPdV  Cv PdV  CvVdP
( R  Cv ) PdV  CvVdP
C p PdV  CvVdP
dV dP
 
V P
dV dP
 V  P
  

 ln V   ln P  k
ln V   ln P  k

ln PV  k
PV   k

PV  k Where k is a constant
Equation of state in terms of P & T Equation of state in terms of V & T

• We have PV   k PV   k
But PV = RT But PV = RT

RT RT
V  P 
P V
  RT  
 RT   V  k
P  k  V 
 P 
  1
P  1 
R T   k V RT  k
  1
P  1  
T k V T k

 1     1
P T  k & TV k
 Isochoric process Isobaric process
• An Isochoric process, also called • An isobaric process is a type of
an isovolumetric process, or an thermodynamic process in
isometric process, is a which the pressure of the
thermodynamic process during system stays constant: ΔP = 0.
which the volume of the closed
system undergoing such
a process remains constant.

Equation of state is Equation of state is

P V
k k
T T
 Work done during isothermal process
V2

Consider a system in a state W   PdV

presented by (P1,V1,T) be V1

undergoing an isothermal RT
change to a state (P2,V2,T) PV  RT  P 
V
which can be represented V2 V
RT 2
dV
 dV  RT 
by using the PV diagram as W
shown. work done for the V1
V V1
V
small change of volume dV
is dW=PdV and the total W  RT  ln V2  ln V1 
work done is V2
W  RT ln
V1
V2
W  2.303RT log
V1
but
V2 P1
1 1  PV
PV 2 2  
V1 P2
P1
W  2.303RT log
P2
 Work done during adiabatic process

Consider a system in a state V2

presented by (P1,V1,T1) be
undergoing an adiabatic
W   PdV
change to a state (P2,V2,T2) V1
which can be represented
 k
by using the PV diagram as
shown. work done for the PV  k  P  
small change of volume dV V
is dW=PdV and the total V2 V2
k dV
work done is
W    dV  k  
V1
V V1
V
V2   1 V2
V 
 k  V dV  k   1 


V1  V1
k 1 1
W 
V2  V1 
1 
 1
W   kV21  kV11 
1 
but
 
PV
1 1  2 2 k
PV
1
W  PV  1
V  PV  1
1 1 V1

1 
2 2 2

1
W  PV 1 1
2 2  PV
1 
but
PV  RT
1
W  RT2  RT1 
1 
R
W  T2  T1 
1 
 Work done during isochoric process
For an isochoric process, dV=0
Hence work done = 0
Also we have the equation dQ  dU  PdV
Since dV = 0 here, dQ  dU
Hence the increase in internal energy of a
system is equal to the heat absorbed by the
system
Work done during isobaric process
V2

W   PdV Let Q be the heat absorbed by the

V1
system at constant pressure P and
suppose its volume increases from V1 to
V2
V2. Then from first law, we have
W  P  dV
V1
Q   U 2  U1   P  V2  V1 
Q   U 2  PV2    U1  PV1 
W  P  V2  V1 
Q  H 2  H1
Where H  U  PV
So when heat is given to a system at constant pressure, it is used
to change the quantity (U+PV) associated with the system. This
quantity (U+PV) is called enthalpy of the system. Enthalpy is the
heat function at constant pressure
 Cyclic process
From first law we have Ñ
 dQ  Ñ
 dU  Ñ
 PdV
For a cyclic process Ñ
 dQ  Ñ
 dU  Ñ
 PdV
For a cyclic process dU = 0
Ñ
 dQ  Ñ
 PdV  Ñ dW
Hence the heat supplied to the system is equal to the work
done by the system. No heat supply means no work done
in a cyclic process. Also in a cyclic process, work done is
equal to the area enclosed in the P-V diagram
 Significance of first law of
thermodynamics
1. It is applicable to any process by which a
system undergoes a physical or chemical
change
2. It introduces the concept of internal energy
ie, U2 - U1 = Q - W
3. It provides a method for determining the
change in the internal energy
 Limitations of first law
1. This law does not specify the
condition under which the system can
use its heat energy to produce a suppy
of mechanical work
2. It also does not say how much of the
heat energy can be converted into
work
 Application of first law of
thermodynamics
Relation between Cp & Cv
dQ  dU  PdV .............(1)
U  U (V , T )
 U   U 
dU    dV    dT ............(2)
 V T  T V
 U   U 
dQ    dV    dT  PdV
 V T  T V
 U    U 
dQ     P  dV    dT
 V T   T V
dQ  U   dV  U  dT
    P  
dT  V T  dT  T V dT
 dQ  U   dV  U 
    P   ........(3)
dT  V T  dT  T V
 dQ 
CV   
 dT V
From equation (3)
 dU 
CV    ..............(4)
 dT V
 dQ 
CP   
 dT  P
 dQ   U    dV 
(3)        P   CV
 dT  P  V T   dT  P
 U    dV 
CP     P   CV ..............(5)
 V T   dT  P
 Since internal energy is a function of temperature only
U
0
V
 dV 
(5)  CP  P    CV ............(6)
 dT  P
dV dP
P V R
dT dT
 dV   dP 
 V   R
At constant pressure P
 dT  p  dT  p
 dV 
P  R
 dT  p

CP  R  CV
Equation (6) becomes
or
CP  CV  R