THERMODYNAMICS 1

The study of the relationship between mechanical work, heat and other forms of energy and energy transfer is known as
thermodynamics.
In thermodynamics, the main focus is on the macroscopic quantities of the system such as the pressure, volume,
temperature, internal energy, enthalpy etc., which have the impact on the internal state of the system. Thus,
thermodynamics provides a macroscopic description of the system.
Thermodynamic System
A collection of an extremely large number of atoms or molecules confined within certain boundaries such that it has a
certain values of pressure (P), volume (V) and temperature (T) is called a thermodynamic systems.
Anything outside the thermodynamic system to which energy or matter is exchanged is called its surroundings.
Taking into consideration the interaction between a systemand its surroundings, a system may be divided into three
classes.
(i) Open system
A system is said to be open if it can exchange both energy and matter with its surroundings.
(ii) Closed system
A system is said to be closed if it can exchange only energy and not matter with its surroundings.
(iii) Isolated system
A system is said to be isolated if it can neither exchange energy nor matter with its surroundings.
Thermodynamic variables
A thermodynamic systems can be described by specifying its pressure, volume, temperature, internal energy, entropy,
enthalpy and number of moles (n) . These variables are called thermodynamic variables.
Types of thermodynamic variables
(i) Intensive variables
The variables which are independent of the size of the system are called intensive variables.
Example: Temperature, pressure, specific heat capacity.
(ii) Extensive variables
The variables which are depends on the size or mass of the system are called extensive variables.
Example: Volume, energy, entropy, heat capacity and enthalpy
Thermal equilibrium
Two bodies (or) systems in contact are said to be thermal equilibrium if both are at the same temperature.
Zeroth law of Thermodynamics
Energy can be exchanged between the system A and C , so both
A and C are in thermal equilibrium. Similarly, energy can be
exchanged between the system B and C, so both B and C are in
thermal equilibrium.
When adiabatic wall between the systems A and B is removed, no
transfer of energy takes place between them. This shows that the
systems A and B are also in thermal equilibrium with each other.
Two systems A and B which are separately in thermal equilibrium with a third system C are also in thermal
equilibrium with each other.
Temperature of a system or a body is a physical quantity which determines whether the system is in thermal equilibrium
with another in its contact or not.
Heat
Energy that is transferred between a system and its surroundings whenever there is temperature difference between the
system and its surroundings is called heat.
Sign conventions for heat 2
(i) When energy is transferred to the system from its surroundings, then heat is taken as positive.(ii) When energy is
transferred to the surroundings from the system, then heat is taken as negative.
Work done
Consider a cylinder fitted with a frictionless piston of area of cross-section A. Let a gas be contained in the cylinder. The
walls of the cylinder are perfectly conducting one so that the gas in the cylinder is in thermal equilibrium at temperature T
with its surroundings.
If P be the pressure of the gas in the cylinder, then the force exerted by the gas on the piston of the cylinder is given by
F=PA
Let the piston moves through a small distance dx during the expansion of the
gas.
Therefore the work done by the gas dW = F . dx = P A dx
dW = P dV [ A dx = dV]
If the volume of the gas increases from initial volume Vi to final volume Vf , then
the total work by the system or gas,
V
∫ dW = Vi ∫ f P dv = P [Vf – Vi ]
Sign conventions for work done
(i) Work done on the system is taken as negative.
(ii) Work done by the system is taken as positive.
Internal Energy (U)
Internal energy of a system is defined as the sum of the kinetic energies of the constituent particles of the system plus the
sum of the potential energies of the constituent particles of the system.
Sign conventions for internal energy
(i) Increase in internal energy is taken as positive.
(ii) Decrease in internal energy is taken as negative.
First law of thermodynamics ( Law of conservation of energy)
Let a system absorbs Q amount of heat energy from the external source. As a result of this, let W be the work done by the
system on its surrounding and ΔU be the change in the internal energy of the system.
According to the law of conservation of energy, Q = ΔU + W
The energy entering the system in the form of heat is equal to the sum of the increase in the internal energy of the system
and the energy leaving the system in the form of work done by the system on its surrounding.
Definition of internal energy from first law of thermodynamics
We know ΔU = Q - W
Thus, the change in internal energy of a system is defined as the difference between the heat added to the system or
taken from the system and the work done by the system or work done on the system.
Thermodynamic process
Any process in which the thermodynamic variables of a thermodynamic system change is known as thermodynamic
process.
(i)Quasi-Static Process (Quasi-Static means nearly static)
A process in which the system departs only infinitesimally from the equilibrium state is known as quasi-static process.
In this process, the change in pressure or change in volume or change in temperature of the system is very very small.
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(ii) Isothermal Process – It is a thermodynamic process which occurs at a constant
temperature.

Essential conditions for an isothermal process to take place

(i) The walls of the container must be perfectly conducting to allow free exchange of heat between the system and the
surroundings.
(ii) The system should be compressed or allowed to expand very slowly so that there is a sufficient time for the exchange
of heat between the system and its surroundings.
(iii) Adiabatic Process – It is a thermodynamic process in which there is no exchange of
heat energy between system and surroundings..

Essential conditions for an adiabatic process to take place

(i) There should not be any exchange of heat between the system and its surroundings. All walls of the container and the
piston must be perfectly insulating.
(ii) The system should be compressed or allowed to expand suddenly so that there is no time for the exchange of heat
between the system and its surroundings.
(iv) Isobaric Process – It is a thermodynamic process which occurs at a constant pressure.
(v) Isochoric Process – It is a thermodynamic process which occurs at a constant volume.
(vi) Cyclic Process - A cyclic process consists of a series of changes which return the system back to its initial state.
P-V Diagram or Indicator Diagram
A graph representing the variation of pressure with the variation of volume is called P.V. diagram or Indicator diagram

Work done by the thermodynamic system is equal to the area under P-V diagram
Consider a gas in a cylinder fitted with frictionless piston. Let the gas expands from
the state A (P1, V1) to the state B (P2, V2)
Now consider two points a and b on P-V diagram. Points a and b are so close to each
other that the pressure (P) corresponding to these two points is same. Now work
done by the system against pressure is given by
dW = P dV = ad x dc = area of the strip abcd
Total work done by the system to change its state from A to B is given by
W= =
= Sum of areas of all strips like abcd within ABCD
.
W = Area under P-V diagram 4
Thus, work done by a thermodynamic process is equal to the area under P-V diagram
Applications of first law of thermodynamics
(i) Isothermal process
According to the first law of thermodynamics Q = ∆U + W
In an isothermal process, temperature is constant so change in internal energy, ∆U = 0
Q=W
Thus, during isothermal process, Heat added ( or removed) = work done by (or on ) the system
(ii) Adiabatic process
According to the first law of thermodynamics Q = ∆U + W
In an adiabatic process , Q = 0
∆U = - W
Hence, if work is done by the system during adiabatic process, then the internal energy of the system decreases by an
amount equal to the work done by it.
If work is done on the system , then ∆U = - (- W) = W
Thus, the internal energy of the system increases by an amount equal to the work done on it, during adiabatic process.
(iii) Isochoric process
In isochoric process, volume of the system remains constant. It means V = constant or dV = 0
Therefore, work done, W = P dV = 0. Hence, first law of thermodynamics Q = ∆U + W reduces to ∆U = Q
This shows that (i) if heat is added into the system or heat is absorbed by the system, then the internal energy of the
system increases and (ii) if heat is taken out from the system or the system loses heat energy then the internal energy of
the system deceases.
(iv) Isobaric process
When a liquid boils, it changes into vapours and its temperature and pressure remain constant till whole of liquid is
converted into vapours . The energy absorbed by the liquid is used in (i) increasing the internal energy of liquid molecules
and (ii) in doing external work during expansion of liquid at constant pressure (P)
dw = P ( Vf - Vi ) Vi - initial volume of the liquid
Vf - final volume of the vapours
Quality of heat given to the liquid to convert it into vapours Q = mL
Therefore, mL = ΔU + P ( Vf - Vi )
ΔU = mL- P ( Vf - Vi )
This is the change in internal energy of the liquid on vaporisation.
(v) Cyclic process
In a cyclic process , the initial and final states of a system are the
same . Since internal energy of a system depends upon its initial
and final states . So during cyclic process , there is no change in
internal energy of the system i.e ΔU=0
Therefore , Q= W for a cyclic process .
= area AEBFA
Work done per cycle is numerically equal to the area enclosed by
the loop representing the cycle.

(f) Melting process

When a solid melts into liquid, its internal energy increases, which can be calculated from first law of thermodynamics.
Amount of heat absorbed during the melting process dQ = mL
m – mass of a solid, L – latent heat of the solid.
When a substance melts, the change in its volume (dV) is very small and therefore, it can be neglected.
 5
dW = P (dV) = P x 0 = 0
According to first law of thermodynamics, dQ = dU + dW
Therefore mL = dU { dW = 0}
Hence, the internal energy during the melting process increases by (mL).
Note that increase in internal energy during melting process is at constant temperature. Therefore, it must be due to
increase in internal energy (Up). The internal kinetic energy (Uk) remains constant.
(g) Boiling process
In boiling , a liquid changes into vapours at constant temperature and process.
m – mass of a liquid at its boiling point, V1 – volume of the liquid
P – constant pressure at which boiling process occurs
V2 – Volume of the same liquid in the vapour from under the same pressure
L – Latent heat of vaporisation of the liquid.
Therefore, Work done in expansion , dW = P (dV) = P (V2 – V1)
Heat absorbed by the liquid in the boiling process dQ = mL
According to first law of thermodynamics , dQ = dU + dW
dU = dQ – dW
dU = mL - P (V2 – V1)
Increase in internal energy of the liquid in the boiling process.

Work done in an isothermal process

Suppose the gas expands isothermally from initial state (P1, V1) to the final state
(P2, V2) .
The total amount of work done will be W = = =
We know PV = RT ( one mole of gas)
P = RT/V
V2
Therefore, W = [ ] = / = RT [In V ] V1 = RT [ In V2 – In V1]
= RT In [V2/V1]
= 2.303 RT log [V2/V1]
Work done in an adiabatic process

W= =
ϑ
PV = K
ϑ
P=K/V
P = K / Vϑ
-ϑ
P=KV
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1) When work is done by the system i.e the system expands , then work done (w) is positive . Therefore T1 > T2 Thus ,
temperature of the system decreases when it expands adiabatically .
2) When work is done on the system i.e the system contracts , then work done (W) is negative . Therefore T2 > T1 Thus ,
temperature of the system increase when it is compressed adiabatically.
Comparison of the slopes of an isothermal and an
adiabatic curves
For an isothermal process PV= constant
Differentiating , we get PdV + VdP = 0
(dP/dV)iso= - (P/V) ----------(1)
ϑ
For an adiabatic process PV = constant
ϑ-1 ϑ
differentiating , we get P ϑ V dV + V dP = 0
ϑ
(dP/ dV)adi = - (P/V)
ϑ
( dP/ dV)adi = (dP/dV)iso
ϑ
Since ϑ > 1, ( dP/ dV)adi > (dP/dV)iso

Specific heat capacities relationship ( Cp - Cv = R )

Consider 1 mole of an ideal gas at a pressure P and temperature T
From the first law of thermodynamics
dQ = dU + dW = dU + PdV ------------------ (1)
Let dq be the heat energy given to the gas at constant volume. Dt be the rise in temperature of the gas .
dQ = 1 x CV dT ------------------- (2) ( dW = PdV , dV = 0, Therefore dW= 0)
From (1) and (2) we get, Cv = specific heat of the gas at constant volume
Therefore , dU= Cv dT. -----------------(3)
Now , let the gas be heated at constant pressure P. If the change in volume of the gas is dV and rise in temperature is in
temperature is dT , then dW = PdV , dQ = Cp dT
CP dT = dU + P dV Therefore dU= CV dT
7
or, CP dT = CV dT + P dV
( Cp – CV ) dT = PdV--------------------(4)
For an ideal gas PV= RT , where R is gas constant
Differentiating , keeping P constant ,
PdV = R dT ------------------(5)
Substituting (5) in (4) we get
(CP - CV) dT = R dT
CP – CV = R
This relation is known as Mayer ‘s Formula.
Isothermal Equation of an ideal gas
-1 -1
For an ideal gas PV= RT R=8.31 } mol k
In isothermal process , T= constant
Therefore PV= constant which is isothermal equation of an ideal gas
Adiabatic Equation of an ideal gas (Pv ϑ = K )
 Consider 1 mole of an ideal gas in a vessel which is thermally insulated from its surroundings.
Let it expands adiabatically so that change in its volume = dV
Therefore, workdone by the gas , dW = PdV ----------------(1) P- pressure of the gas
Since work is done by the gas at the cost of in own internal energy , so there shall be fall in its temperature (say dT)
dU= 1X CV dT = Cv dT ---------------(2)
Applying the first law of thermodynamics
dQ= dU + PdV = Cv dT-------------(3)
In an adiabatic process , dQ = 0
Therefore CV dT + PdV = 0 ---------(4)
For an ideal gas , PV= RT
Differentiating both sides ,we get
PdV + VdP= R dT
dT= (PdV+ VdP) / R
CV( PdV + VdP ) / R + PdV = 0
Cv(PdV + VdP ) + R PdV = 0
Cv ( PdV + VdP ) + CpPdV – CvPdV =0 [ CP – CV = R ]
CvVdP + CpPdV= 0
Dividing by CvPV
dP/P + (Cp/Cv) ( dV/V) = 0
dP/P + ϑ (dV/ V) = 0
Integrating
log P+ ϑ log V= constant
ϑ
log( PV ) = constant
ϑ
PV = constant
Other forms of equation
ϑ
P (RT/P) = constant PV = RT
1- ϑ ϑ
P T = constant V= RT /P
(RT/V) V ϑ = constant PV = RT
ϑ-1
TV = constant P= RT/V

Reversible process
. A process is said to be reversible when the various steps of an operation to which it is subjected can be traversed back
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in opposite direction in such a way that the substance passes through exactly the same conditions at every step in the
reverse process as in the direct process.
Thus, if in a particular step in a direct process, heat is absorbed by the substance , then in the same step in the reverse
process the same amount of heat will be given out by the substance.
The basic requirements for a reversible process :
1. The pressure difference between working substance and surrounding at any steps of operation of cycle should be very
small.
2) The process should take place very slowly .
3) The various parts of the system must be free from friction
4) There should be no loss of energy due to conduction , convection and radiation during the operation

Since all the conditions stated above are not possible to obtain in actual practice, therefore, completely reversible
process cannot be realized in actual practice
Irreversible Process
 A process in which the system cannot be retraced to its original state is called an irreversible process. Following are the
examples of irreversible processes :
i) Heat generation during the flow of current through a resistor
ii) Work done against force of friction
iii) Diffusion of two gases
iv) Exchange of heat between bodies at different temperature

Limitations of First Law of Thermodynamics

It tells us that heat and mechanical work are interconvertible . However, this law fails to explain the following points :
i) It does not tell us about the direction of transfer of heat. We know this heat flows from a hot body to a cold body , but
this law does not give any reason as to why heat cannot flow from a cold to a hot body
ii) It does not tell us how much of a given quantity of heat is converted into work.
iii) It does not tell us about the conditions under which heat energy is converted into work . When a bullet strikes a target ,
its kinetic energy is converted into heat energy . This law does not tell us as to why heat energy produced in the target
cannot be converted back into kinetic energy of the bullet to make it fly back into the gun.
Heat Engine
Heat energy is a device which converts heat energy into mechanical energy. For example, steam engine , diesel engine ,
petrol engine etc .
Principle
A fact that a system whose different parts are at different temperatures tends to change towards the state of thermal
equilibrium is used as the principle of heat engine.
Construction
Any heat engine consists of the following parts :
1. Source – A hot body maintained at very high temperature T1 which
supplies heat energy is called source or reservoir
2. Sink – A cold body maintained at low temperature T2 which absorbs
the rejected heat is called sink.
3. Working substance – A material which absorbs heat energy from the
source and converts it into mechanical energy by rejecting some of the
heat too the sink is called Working substance.
4. Mechanical parts - The mechanical parts of the engine are requires
for containing working substance and for transfer of mechanical energy to
the appropriate parts of the machine.

Working and efficiency of Heat Engine 9

The working substance of the engine absorbs heat energy from the source . A part of this absorbed heat energy is
converted into mechanical energy and the remaining heat energy is rejected to the sink . Thus , the temperature of the
working substance remains as it was before the absorption of heat energy . Therefore , the working substance is now
again ready to absorb the heat energy from the source and to repeat the process continuously . This process continues
and we get the continuously. This process continues and we get the continuous amount of mechanical energy.

Let Q1= Amount of heat absorbed by working substance from the source .
Q2 = Amount of heat rejected o the sink.
W = Mechanical energy or work performed in each cycle .
Since there is no change in the temperature of the working substance at the end of the each cycle, therefore the change
in internal energy of the working substance is zero.
i.e dU = Uf – Ui = 0
According to first law of thermodynamics ,
dQ = dU + W
dQ = W
or W = Q1 –Q2 = dQ (therefore, dU= 0)
The efficiency of heat engine is defined as the ratio of the mechanical work done to the heat absorbed
i.e Efficiency , ɳ = W/ Q1 = (Q1 – Q2 )/Q1 or ɳ = 1 – ( Q2/ Q1) ------------(1)
From eqn. (1) , it is clear that efficiency of heat engine is less than one

Carnot’s reversible engine

Sadi Carnot introduce the concept of an ideal heat engine. He made important thermodynamic studies using an ideal,
reversible heat engine, which operated through sequence of isothermal and adiabatic processes known as Carnot Cycle.
Construction
The essential parts of an ideal heat engine or Carnot engine are:
1. Source: A hot body maintained at a fixed high temperature T1 is called source or reservoir. It has infinite thermal
capacity and any amount of heat can be withdrawn from it without changing its temperature T1.
2. Sink : A cold body maintained at a fixed high temperature T2 is called sink. It has also infinite thermal capacity and any
amount of heat can be rejected from it without changing its temperature.
3. Working substance: A cylinder with insulated sides and conducting base contains perfect gas as the working
substance. A perfectly insulated and frictionless piston is fitted into the cylinder.
4. Insulated stand: A perfectly non-conducting platform serving as a stand for the cylinder is also provided so that the
working substance can undergo adiabatic operation.

Carnot cycle
Operation 1 : Isothermal expansion
Let the cylinder be placed on the source and the gas be allowed to expand by slow outward motion of the piston. Since it
10
absorbs the requisite amount of heat from the source through the conducting base of the cylinder , therefore, temperature
of the gas remains constant. This operation is called isothermal expansion and is represented by the isothermal curve AB.
Let the amount of heat energy absorbed in the process be Q1 and W 1 be the corresponding amount of work done by the
gas in expanding isothermally from A ( P1, V1) to B (P2, V2).
Q1 = W 1 = = RT1 loge [V2/V1]
= area ABRPA
Operation 2: Adiabatic expansion
The cylinder is now removed from the source and is placed on the perfectly insulating pad. The gas is allowed to expand
further from B (P2, V2) to C ( P3, V3). Since, the gas is thermally insulated from all sides, so heat can be gained from the
surroundings. Temperature of gas falls to T2 the expansion is adiabatic and is represented by the adiabatic curve BC.
Let W 2 be the work done by the gas in expanding adiabatically from B (P2, V2) to C ( P3, V3)
W2 = = [ R (T2-T1)]/ (1-γ)
= area BCSRB
Operation 3 : Isothermal compression
The cylinder is now removed from the insulating pad and is placed on the sink at a temperature T2. The piston is moved
inwards slowly so that gas is compressed until its pressure P4 and volume is V4. This state is represented bythe point D.
Since, the base of cylinder is conducting, heat produced in compression will pass to the sink so that the temperature of
the gas remains constant at T2. This process is, therefore, isothermal and is represented by an isothermal curve, CD.
Let Q2 be the amount of heat energy rejected to the sink and W3 be the amount of work done on the gas in
compressing is isothermally from state C (P3, V3) to D ( P4, V4).
Q2 = W 3 = − = - RT2 loge [V4/V3] = RT2 loge [V3/V4]
= - area CSQDC
Operation 4: Adiabatic compression
The cylinder is again placed on the insulating pad. The piston is further moved downwards so that the gas is compressed
to its initial volume V1 and pressure P1. As the gas is insulated from all sides, heat produced raises the temperature of the
gas to T1. This change is adiabatic and is represented by the adiabatic curve DA.

Let W 4 be the work done on the gas is compressing it adiabatically from a state D ( P4, V4) to the initial state A ( P1, V1).
W4 = − = -[ R (T2-T1)]/ (1-γ)
= - area DQPAD
The total work done during the complete cycle
W = W 1 + W 2 – W 3 – W4
W2 = W4
W = W1 – W3
= area ABCDA
Efficiency of Carnot engine
ɳ = [ work done (output)]/ [Heat absorbed from source (input)]
ɳ = W/Q1 = [W1-W3]/ W1 = [Q1- Q2]/Q1
ɳ = 1- [W3/W1] = 1- [Q2/Q1]
ɳ = 1- [RT2 loge [V3/V4]/ [RT1 loge [V2/V1]--------- (1)
Note
1. The efficiency of Carnot’s engine depends upon the temperatures of source and sink.
2. The efficiency of Carnot’s is independent of the nature of the working substance.
3. The efficiency of Carnot’s is 100% if temperature of the sink is 0 K. Since, we cannot have a sink at absolute zero., so a
heat engine with 100% efficiency is not possible to realize in practice.
Second law of Thermodynamics 12
The law specifying the condition of transformation of heat into work is called second law of thermodynamics.
Second law of thermodynamics has been stated in two forms :
Kelvin statement of the second law- It states that : “ It is impossible to get a continuous supply of work by cooling a body
to a temperature lower than that of the coldest of its surroundings “.
Kelvin statement of second law of thermodynamics is supported by the working of heat engine.
Claussius statement of second law : It states that : “ It is impossible for a self acting machine, unaided by any external
agency to transfer heat from one body at lower temperature to another body at a higher temperature.”
Refrigerator or Heat Pump
The process of removing heat from bodies colder than their
surroundings is called refrigeration and the device doing so is called a
refrigerator .
In refrigerator , heat is absorbed at low temperature and rejected at
higher temperature with the help of external mechanical work . Thus ,
refrigerator is a heat engine working backward and hence it is also
called heat pump. The working substance used in a refrigerator is
called refrigerant . The commonly used refrigerants are ammonia and
Freon.
Let heat Q2 from a cold body at temperature T2 is transferred to a hot
body at temperature T1 with the help of external mechanical work W
Let Q1 be the heat rejected to the hot body.
According to the law of conservation of energy,
Q1= Q2 + W ----------(1)
Instead of efficiency , we use the quantity coefficient of performance
(β )in the refrigerator , which is defined as
β= Desired output / Required input = Heat extracted from
cold body/ work done on the refrigerant = Q2/W
Using eqn.(1),we have β=Q2/(Q1–Q2) --------------------(2)
Since Q2/Q1 = T2/T1 Therefore β = Q2 /(Q1–Q2 ) = T2/(T1–T1) ----(3)
If ɳ is efficiency of carnot cycle, then
1 – [T2/T1] = ɳ
1 - ɳ = T2/T1
β = (1-ɳ)/ɳ
The coefficient of performance is large for small temperature difference ( T1 – T2 ) between hot body and cold body .
When temperature of two bodies becomes equal i.e T1 = T2 , then coefficient of performance becomes infinite .
i) To have large coefficient of performance , the object to be cooled.
must have temperature close to the temperature of the surroundings , before placing it in the refrigerator .
ii) The room can be warmed by keeping the door of a refrigerator open.