It deals with the study of interactions between heat and other forms of energy.

Thermodynamic System:

A collection of large numbers of molecules of matter (solid, liquid or gas) that are arranged in a manner
such that these possess particular values of pressure, volume and temperature forms a thermodynamic
system.

The parameters like pressure, volume, temperature, internal energy, etc., which determine the state or
condition of a system are termed thermodynamic state variables.

In thermodynamics, we consider the thermodynamic systems as a whole and learn the interaction of
heat and energy during the change of one thermodynamic state to another.

1.1 Thermal Equilibrium

The term ‘equilibrium’ in thermodynamics refers to the state when all the macroscopic variables
expressing the system (P, V, T

, mass etc.,) do not change with time.

Two systems when in contact with each other are said to be in thermal equilibrium when their
temperatures become the same.

Zeroth law of thermodynamics states that when the thermodynamics systems A and B are separately in
thermal equilibrium with a third thermodynamic system C, then the systems A and B are also in thermal
equilibrium with each other.
1.2 Heat, Work and Internal Energy

Internal Energy refers to the energy possessed by any system because of its molecular kinetic energy
and molecular potential energy. Both these energies are considered with respect to the center of mass
frame.

Internal energy is dependent entirely on the state and thus, it is a state variable. In the case of real
gases, internal energy is only by virtue of their molecular motion whereas for ideal gases, it is
mathematically given by

U=nfRT2

where,

n is the number of moles

f is the degree of freedom

R is the universal gas constant

T is the temperature in kelvin

Internal Energy can be altered either by providing heat energy or by performing some work.

Heat Energy refers to the energy transformed to or from the system due to the difference in
temperatures by conduction, convection or radiation.
The energy that gets transferred from one system to another by force moving its point of application in
its own direction is termed work.

Mathematically, work done by the system is given by

W=∫Fdx=∫PsAdx=∫PdV

where Ps is the pressure of the system on the piston.

This work done by the system is positive when the system is expanding and it is negative when the
system is contracting.

Work and heat are path functions while internal energy is a state function.

Heat and work are two different terminologies even though they might look similar.

1.3 Important Thermodynamics Terms

State Variables: P, V, T, moles

State variables can be extensive or intensive.

Equation of State: The equation that relates the pressure (P), the volume (V) and absolute temperature
(T) of a gas is known as the equation of state.
PV=constant

(Boyle’s Law)

VT=constant

(Charles’ Law)

⇒PV=nRT

Thermodynamic Process: A thermodynamic process happens when a few changes occur in the state of a
thermodynamic system, i.e., the thermodynamic parameters of the system get altered with time.
Thermodynamic process can be isothermal, adiabatic, isobaric or isochoric.

Quasi Static Process: A thermodynamic process that is infinitely slow is termed quasi-static process.

In a quasi static process, the system undergoes change with slow speed such that at every instant, the
system is in both thermal and mechanical equilibrium with the surroundings.

Quasi-static process is an ideal process. We generally consider all the processes to be quasi static unless
mentioned differently.

Indicator P-V Diagram: A graph

between pressure and volume of a gas
under thermodynamic operation is
known as a P-V diagram.
With respect to the diagram;

a → Isobaric

(Constant Pressure)

b → Isothermal

(Constant Temperature)

c →Adiabatic

(Q= Constant)

d →Isochoric

(Constant Volume)

Also, the area under the P-V diagram provides us the work done by a gas.

1.4 First Law of Thermodynamics

Suppose that

ΔQ=

Heat supplied to the system by the surroundings

ΔW=

Work done by the system on the surroundings

ΔU=

Change in internal energy of the system.

First law of thermodynamics suggests that energy can neither be created nor be destroyed. It can only
be transformed from one form to another. Thus, first law of thermodynamics states that the total
amount of heat supplied to the system by the surroundings will be equal to the sum of the Work done
by the system on the surroundings and the change in internal energy of the system.

Mathematically,

ΔQ=ΔU+ΔW

Sign Conventions:

When heat gets supplied to the system, then ΔQ

is taken positive and when heat gets withdrawn from the system, ΔQ

is taken negative.

When a gas expands, work done by the gas is taken positive whereas when a gas contracts, work is
taken negative.

ΔU

is taken positive when temperature increases while ΔU

is taken negative when temperature decreases.

It is to be noted here that we always take work done by the system. In chemistry, work done on the
system is considered. Hence there is another perspective to the first law of thermodynamics in
chemistry. Mathematically, this can be expressed as

ΔQ−ΔW=ΔU

where ΔQ

and ΔU

have the same meanings but W stands for the work done on the system.

1.5 Application of the First of Law of Thermodynamics

Here, we observe how the first law of thermodynamics is applied to different thermodynamic processes.

1.5.1 Isothermal Process

Description: A thermodynamic process in which the temperature remains constant.

Condition: The walls of the container should be perfectly conductive to allow free exchange of heat
between the gas and its surroundings.

The process of compression or expansion must be slow in order to provide time for exchange of heat.

Both these conditions are considered perfectly ideal.

Equation of State: T= Constant or Pv= Constant

Indicator Diagram:

Slope of P−V at any point is equal to −PV.

Change in internal energy, ΔU=0

(Temperature remains constant)

Work done is given by

W=∫v1v2PgdV

⇒W=∫v1v2(nRTV)dV Using$PV=nRT$

⇒W=nRTln(v2v1)

First Law of Thermodynamics:

Q=ΔU+W

⇒Q=nRTln(v2v1)

Remarks: All the heat supplied is utilized entirely to do work against external surroundings. When heat is
supplied, then the gas expands whereas when heat is withdrawn, then the gas contracts.
Practical Examples:

Melting of ice at 0∘C

Boiling of H2O at 100∘C

1.5.2 Adiabatic Process

Description: A thermodynamic process in which there is no heat exchange with surroundings.

Conditions: The walls of the container should be perfectly non-conducting in order to prevent any
exchange of heat between the gas and its surroundings.

The process of compression or expansion must be rapid so that there is no time for the exchange of
heat.

These conditions are ideal conditions and are difficult to achieve.

Equation of State:

PVr=constant
⇒TVr−1=constant

⇒PTr1−r=constant

Indicator Diagram

Slope of adiabatic curve =−rPV

As given in the graph, the adiabatic curve is steeper than the

isothermal curve. Change in internal energy, ΔU=nfRΔT2=nR(T2−T1)r−1=P2V2−P1V1r−1.

Work done by the gas when it adiabatically expands from V1 to V2 is given by

W=∫v1v2dVVr

⇒W=constant∫v1v2dVVr

∵PVr=constant

⇒P=constantVr

⇒W=constant×[V−r+11−r]v2v1
⇒W=constant1−r[1Vr−12−1Vr−11]

Also, it is known that

P1Vr1=P2Vr2=constant

⇒W=11−r[P2V2Vr−12−P1V1Vr−11]

⇒W=P2V2−P1V11−r=nR(T1−T2)r−1

First Law of Thermodynamics

Q=ΔU+W

Substituting the values

We get Q=0

, as expected

Remarks: When gas expands adiabatically, then its temp decreases and vice versa.

Practical Examples:
Propagation of sound waves in the form of compression and rarefaction.

Spontaneous bursting of a cycle tube.

1.5.3 Isochoric Process

Description: A thermodynamic process in which the volume remains constant.

Condition: A gas being heated or cooled inside a rigid container.

Equation of State: V=constant or PT=constant

Indicator Diagram:

Change in internal energy is given by

ΔU=nfRΔT2=nR(T2−T1)r−1

⇒ΔU=P2V2−P1V1r−1=nRΔTr−1

Work done is given by W=0 since the gas does not expand.
First Law of thermodynamics

Q=ΔU+W

⇒Q =nfRΔT2

Remarks: As we have learnt that when heat is supplied to any process, its temperature increases
according to relation:

Q=nCΔT

⇒C=QnΔT

Now, this C is dependent on external conditions for gases.

Here, it is referred to as ΔQnΔT∣∣vi.e., Molar heat capacity at constant volume.

Mathematically, it can be derived as

Cv= fR2

1.5.4 Isobaric Process

Description: A thermodynamic process in which the pressure remains constant.

Condition: When in a container, the piston can move freely and it is not connected by any agent.

Equation of State:

P=constant

or VT=constant

Change in internal energy, ΔU=nfRΔT2 is the same as always.

Work done is given by

W=∫PdV=PΔV

(since pressure is constant)

⇒W=PV2−PV=nRΔT

First Law of Thermodynamics

Q=ΔU+W

⇒Q =nfRΔT2 +nRΔT
⇒Q=[fR2+R]ΔT

Remarks: Just like CV, we may define molar heat capacity at constant pressure as CP=QnΔT ∣∣P.

Mathematically, it can be derived as:

CP=fR2+R

Replacing fR2 by CV, we get CP+CV=R

, which known as Mayer’s Relation.

Notes:

Just like molar specific heat at constant pressure and molar specific heat at constant volume, we may
define molar specific heat for any process.

For example:

Cadiabatic=0

Cisothermal=∞

Basically, gases do not possess unique specific heats though we have CP and CV

mainly.
Specific Heat at Constant Volume: It refers to the amount of heat needed to raise the temperature of 1g
of a gas through 1∘C, when its volume is kept constant. It is denoted by cV

Specific Heat at Constant Pressure: It refers to the amount of heat needed to raise the temperature of
1g of a gas through 1∘C keeping its pressure constant. It is denoted by cP.

Here, it is to be noted that CP,CV

refer to molar heat capacity while cP, cV

refer to specific heat capacity.

CV=McV and CP =McP

where M stands for molar mass of any sample.

⇒cP−cV=CP−CVM=RM

1.5.5 Melting Process

In any case, the first law is always applicable.

During the melting process,

Internal energy, Q=mLf

, as studied earlier and where Lf

is the latent heat of fusion.

Work done, W=0

(In the change of state from solid to liquid, we do not consider any expansion or contraction as it is very
small)

With respect to the first law of thermodynamics,

ΔU=Q−W

⇒ΔU=mLf

Remark: The heat provided during melting is utilized in increasing the internal energy of any substance.

1.5.6 Boiling Process

During the boiling process,

Internal energy, Q=mLV

, where LV

is the latent heat of vaporization.

Work done, W=P[V2V1]

.
(Pressure is constant during boiling and it is equal to atmospheric pressure)

With respect to the first law of thermodynamics,

ΔU=Q−W

⇒ΔU=mLf−P(V2−V1)

1.5.7 Cyclic Process

A cyclic process refers to the process wherein the system returns to its initial stage after undergoing a
series of change.

Example Indicator Diagram

Here, change in internal energy, ΔU=mLV=0.

Work done, W= Area under the loop.

⇒Q=W according to the first law of thermodynamics.

Also, W is positive when the cycle is clockwise whereas it is negative when the cyclic is anti-clockwise.

1.6 Limitations of the First Law of Thermodynamics

The first law does not provide the direction in which the change can occur.

The first law provides no idea on the extent of change.

The first law of thermodynamics provides no information about the source of heat. i.e., whether it is a
hot or a cold body.

1.7 Heat Engines

Heat engine is a device which converts heat energy into mechanical energy.

Key Elements

A source of heat at higher temperature

A working substance

A sink of heat at lower temperature

Working

The working substance follows a cycle consisting of several processes.

In some processes, it absorbs a total amount of heat Q1

from the source at temperature T1.

In some other processes, it rejects a total amount of heat Q2

to the sink at a lower temperature T2

The work done by the system in a cycle gets transferred to the environment with the help of an
arrangement.

Schematic Diagram

First Law of Thermodynamics

Since energy is always conserved,

Q1=W+Q2

Thermal Efficiency of a heat engine refers to the ratio of net work done per cycle by the engine to the
total amount of heat absorbed per cycle by the working substance from the source. It is represented by
η. Mathematically,

η=WQ1

Substituting for Q1, we get

⇒η=1−Q2Q1
Ideally, engines must have efficiency η=1.

Remarks: The mechanism of conversion of heat into work varies for various heat engines:

The system which gets heated by an external furnace similar to a steam engine. These engines are called
external combustion engines.

The system wherein heat is produced by burning the fuel inside the main body of the engine. These
engines are called internal combustion engines.

1.8 Refrigerator and Heat Pumps

A refrigerator or heat pump is a device utilized for cooling things.

Key Elements

A cold reservoir at temperature T2

A working substance

A hot reservoir at temperature T1

Working

The working substance follows a cycle consisting of several processes.

A sudden expansion of the gas from high to low pressure cools it and converts it into a vapor-liquid
mixture.

Absorption by the cold fluid of heat from the region to be cooled converts it into vapor.

The vapor gets heated up due to external work done on the working substance.

The heat gets released by the vapor to the surroundings bringing it to the initial state and completing
the cycle.

Schematic Diagram

First Law of Thermodynamics

Q2+W=Q1

Coefficient of performance of refrigerator (β) refers to the ratio of quantity of heat removed per cycle
from contents of the refrigerator (Q2) to the energy spent per cycle (W) to remove this heat.
Mathematically,

β=Q2W

Substituting for W, we get

⇒β=Q2Q1−Q2

Ideally, heat pumps must have β=∞.

1.9 Second Law of Thermodynamics

There are a lot of ways in which this law can be stated.

Even though all the statements are the same with respect to their contents, the following two are the
most significant.

Kelvin Planck Statement: No process is possible whose sole result is the absorption of heat from a
reservoir and the complete conversion of the heat into work.

Clausius Statement: No process is possible whose sole result is the transfer of heat from a colder object
to a hotter object.

Significance: 100 efficiency in heat engines or infinite CoP in refrigerators is not possible.

1.10 Reversible and Irreversible Process

Reversible Process: A thermodynamic process taking a system from initial state i to final state f is
considered reversible if the process can be reversed back such that both the system and the
surroundings return to their original states with no other change anywhere else in the universe.

Conditions for reversibility:

Process must proceed at an extremely slow rate, i.e., process is quasi-static so that the system is in
equilibrium with surroundings at every stage.

The system must be free from dissipative forces like friction, inelasticity, viscosity, etc.

Examples: No process can be considered perfectly reversible though a slow expansion of an ideal gas is
approximately reversible.

Irreversible Process: A process that does not satisfy any of the conditions of a reversible process is
known as an irreversible process.

Causes:

Spontaneous process

Presence of friction, viscosity and other dissipative forces

Significance of Reversibility:

Major concern of thermodynamics is the efficiency with which the heat is converted into mechanical
energy.

Second law of thermodynamics opts out the possibility of a perfect heat engine with 100 efficiency.

It is found that heat engines based on idealized reversible processes attain the highest possible
efficiency.
2.11 Carnot Engine

Sadi Carnot devised an ideal cycle of operation for a heat engine termed the Carnot cycle.

The engine used for realizing this ideal cycle is known as the Carnot heat engine.

Construction

The essential sections of an ideal heat engine or Carnot heat engine are shown in the diagram below.

Source of heat: The source is maintained at a fixed higher temperature T1, from which the working
substance takes heat. The source is supposed to possess infinite thermal capacity and as such any
amount of heat can be taken from it without altering its
temperature.

Sink of heat: The sink is maintained at a fixed lower temperature T2,

to which any amount of heat can be emitted by the working substance. It also has infinite thermal
capacity and as such its temperature remains constant at T2 , even when any amount of heat is emitted
to it.

Working substance: A perfect gas plays the role of a working substance. It is contained in a cylinder with
non-conducting sides but having a perfectly conducting-base. This cylinder is fixed with a perfectly non-
conducting and frictionless piston.
Apart from these essential parts, there is also a perfectly insulating stand or pad on which the cylinder
can be positioned. It provides complete isolation to the working substance from the surroundings so
that the gas can undergo adiabatic changes.

Working

The Carnot cycle consists of the following four stages:

Isothermal expansion

Adiabatic expansion

Isothermal compression

Adiabatic compression

The cycle is carried out by making use of the Carnot engine as detailed below:

Consider one gram mole of an ideal gas enclosed in the cylinder.

Let V1

, P1

and T1

be the initial volume, pressure and temperature of the gas respectively. The initial state of the gas is
demonstrated by point A in the above P-V diagram. We may assume that all the four processes are
quasi-static and non-dissipative in nature, which are the two conditions for reversibility.
Steps

1. Isothermal Expansion:

The cylinder is positioned on the source and the gas is allowed to expand from A(V1,P1) to B(V2,P2) by
slow outward motion of piston. As the base is perfectly conducting, the process is isothermal.

Now,

ΔU1=0;

⇒Q1=W1=RT1ln(V2V1)=Area ABMKA

where,

Q1→Heat absorbed by gasin this process

W1→Work done by gas in this process

2. Adiabatic Expansion:

The cylinder is now removed from the source and is positioned on the perfectly insulating pad. The gas
is allowed to expand further from B(P2,V2) to C(P3,V3). As the gas is thermally insulated from all sides,
the process is adiabatic.

Here,
Q2=0;

⇒ΔU2=W2=R(T2−T1)r−1=Area BCNMB

3. Isothermal Compression:

The cylinder is now removed from the insulating pad and is positioned on the sink at a temperature T2.
The piston is moved slowly so that the gas is compressed until the pressure is P4

and the volume is V4.

Here,

ΔU3=0

W3=Q3=RT2ln(V4V3)=−Area CDLNC

where,

Q3=Heat absorbed in this process

W3=Work done by gas in this process

4. Adiabatic Compression:
The cylinder is again positioned on the insulating pad such that the process remains adiabatic. Here, the
gas is further compressed to its initial pressure and volume. i.e., P1 and V1.

Here,

Q4=0;

W4=ΔU4=R(T1−T2)r−1=−Area DAKLD

Analysis:

Total work done by the engine per cycle is derived as:

W=W1+W2+W3+W4

⇒W=W1+W3

⇒W=RT1ln(V2V1)+RT2ln(V4V3)

Q1=Total heat absorbed=RT1ln(V2V1)

Q2=Total heat released=−RT2ln(V4V3)

Clearly, it is seen that for a heat engine,

W=Q1−Q2=Area under ABCDA

Efficiency of Carnot Engine

Mathematically, efficiency of a Carnot engine is given by

η=WQ1=1−Q2Q1

Now, considering all the adiabatic processes, we have

T1Vr−12=T2Vr−13 and T1Vr−11=T2Vr−14

⇒V2V1=V3V4

Clearly,

⇒Q1Q2=T1T2

⇒ηCarnot=1−T2T1

Division

ηCarnot

is dependent only on source temperature and sink temperature.

ηCarnot=1

only when T2=0 K or T1=∞, which is not possible to achieve.

If T2=T1⇒η=0, heat cannot be converted to mechanical energy unless there is equal difference between
the temperature of source as well as sink.

1.12 Carnot Theorem

Statement

Working between two given temperatures, T1 of hot reservoir (the source) and T2 of cold reservoir (the
sink), no engine can have efficiency more than that of the Carnot engine.

The efficiency of the Carnot engine is not dependent on the nature of the working substance.

Proof

Step - 1: Consider a reversible engine R and an irreversible engine I working between the source (hot
reservoir at T1) and sink (cold reservoir at T2).

Step - 2: Pair up two engines in such a manner that I act like a heat
engine and R acts like a refrigerator.

Step - 3: Suppose that the engine I absorbs Q1 heat from the source; deliver a work W1 and release the
balance Q1−W1

to the sink in a single cycle.

Step - 4: Setup R such that it returns the same heat to the source, taking Q2 from the sink and requiring
a work W=Q1−Q2 to be done on it.

Step - 5: Suppose ηR<ηI i.e., When R were to act as an engine, it would give less work output than that
of I.

⇒W<W1 for a given Q1 and Q1−W>Q1−W1

Step - 6: In totality, the I-R system extracts heat (r1−W)−(Q1−W1)=W1−W and delivers the same amount
of work in a single cycle without any change in source or anywhere else. This contradicts the second law
of thermodynamics. (Kelvin - Planck statement)

Clearly, the assumption q1>qR is incorrect.

A similar argument can be set up for the second statement of the Carnot theorem, i.e., Carnot efficiency
is independent of the working substance.

Thus, Q1Q2=T1T2 will always hold true for any working substance used in a Carnot engine.