Heat & Thermodynamics

Heat (symbol: Q) is a kind of energy. It is the total amount of energy (both kinetic and potential) possessed by
the molecules in a piece of matter. Heat is measured in Joules.

Temperature (symbol: T) is not energy. It relates to the average (kinetic) energy of microscopic motions of a
single particle in the system per degree of freedom. It is measured in Kelvin (K), Celsius (C) or Fahrenheit (F).

𝐶 𝐹 − 32 𝐾 − 273 𝑅
= = =
5 9 5 4

When you heat a substance, either of two things can happen: the temperature of the substance can rise or the
state of substance can change.

Heat Temperature
Heat is energy that is transferred from Temperature is a measure of hotness or coldness
Definition one body to another as the result of a expressed in terms of any of several arbitrary scales like
difference in temperature. Celsius and Fahrenheit.
Symbol Q T
Unit Joules Kelvin, Celsius or Fahrenheit
SI unit Joule Kelvin
Temperature is related to how fast the atoms within a
Heat is a measure of how many atoms
substance are moving. The ‘temperature’ of an object is
Particles there are in a substance multiplied by
like the water level – it determines the direction in which
how much energy each atom possesses.
‘heat’ will flow.
Ability to Temperature can only be used to measure the degree of
Heat has the ability to do work.
do work heat.

The fundamental modes of heat transfer:

Conduction

The transfer of energy between objects that are in physical contact. Thermal conductivity is the property of a
material to conduct heat and evaluated heat conduction. On a microscopic scale, heat conduction occurs as hot,
rapidly moving or vibrating atoms and molecules interact with neighboring atoms and molecules, transferring
some of their energy (heat) to these neighboring particles. In other words, heat is transferred by conduction
when adjacent atoms vibrate against one another, or as electrons move from one atom to another. Conduction is
the most significant means of heat transfer within a solid or between solid objects in thermal contact.

Convection
Convection, is the transfer of heat from one place to another by the movement of fluids, a process that is
essentially the transfer of heat via mass transfer. Convection is usually the dominant form of heat transfer in
liquids and gases.

Radiation

The transfer of energy by the emission of electromagnetic radiation. Thermal radiation is a direct result of the
random movements of atoms and molecules in matter. Since these atoms and molecules are composed of
charged particles (protons and electrons), their movement results in the emission of electromagnetic radiation,
which carries energy away from the surface.
1
The Stefan-Boltzmann equation, which describes the rate of transfer of radiant energy, is as follows for an
object in a vacuum :

For radiative transfer between two objects, the equation is as follows:

where Q is the heat flux, ε is the emissivity (unity for a black body), σ is the Stefan-Boltzmann constant, and T
is the absolute temperature (in Kelvin or Rankine). Radiation is typically only important for very hot objects, or
for objects with a large temperature difference.

Thermal Conductivity

Thermal conductivity (K) is the intrinsic property of a material which relates its ability to conduct heat.
Thermal conductivity is defined as the quantity of heat (Q) transmitted through a unit thickness (L) in a
direction normal to a surface of unit area (A) due to a unit temperature gradient (ΔT) under steady state
conditions and when the heat transfer is dependent only on the temperature gradient. In equation form this
becomes the following:

Thermal Conductivity = heat × distance / (area × temperature gradient)

K = Q × L / (A × ΔT)

Exercise: A copper bar connects two beakers of water at different temperatures.One beaker is at 100°C and the
other is at 0°C. The bar has a cross section area of 0.0004 m2 and is one-half meter (0.5 m) long. How many
watts of heat are conducted through the bar from the hot beaker to the cold beaker? The thermal conductivity of
copper is 401 W/m°C.

Kinetic Theory of Gases

The kinetic theory of gases is a law that explains the behavior of a hypothetical ideal gas. According to this
theory, gases are made up of tiny particles in random, straight line motion. They move rapidly and continuously
and make collisions with each other and the walls. This was the first theory to describe gas pressure in terms of
collisions with the walls of the container, rather than from static forces that push the molecules apart. Kinetic
theory also explains how the different sizes of the particles in a gas can give them different, individual speeds.

Kinetic theory makes many assumptions in order to explain the reasons gases act the way they do. According to
kinetic theory:

1. Gases consist of particles in constant, random motion. They continue in a straight line until they collide
with something—usually each other or the walls of their container.
2. Particles are point masses with no volume. The particles are so small compared to the space between
them, that we do not consider their size in ideal gases.
3. No molecular forces are at work. This means that there is no attraction or repulsion between the
particles.
 4. Gas pressure is due to the molecules colliding with the walls of the container. All of these collisions are
perfectly elastic, meaning that there is no change in energy of either the particles or the wall upon
collision. No energy is lost or gained from collisions.
5. The time it takes to collide is negligible compared with the time between collisions.
6. The kinetic energy of a gas is a measure of its Kelvin temperature. Individual gas molecules have
different speeds, but the temperature and kinetic energy of the gas refer to the average of these speeds.
7. The average kinetic energy of a gas particle is directly proportional to the temperature. An increase in
temperature increases the speed in which the gas molecules move.
8. All gases at a given temperature have the same average kinetic energy.
9. Lighter gas molecules move faster than heavier molecules.

Mean free path: The mean free path is the mean path length that a molecule traverses between two successive
impacts with other molecules. It depends upon molecular diameter dm and temperature T.
Explanation: Imagine a ball traveling in a box (Figure 1) where the ball represents a moving molecule. Each
time it hits the wall, a collision occurs and the direction of the ball changes. In figure 1, the ball hits the wall
five times, causing five collisions. Between every two consecutive collisions, the ball travels an individual
path. It travels a total of four paths between the five collisions; each path has a specific distance, d. The mean
free path of this ball is the average distance of all four paths.

Figure 1. This figure shows a ball traveling in a box.

Every time it hits the wall, a collision occurs and the ball changes direction. The ball travels an individual path
between every two consecutive collisions. Each path traveled by the ball has a distance, d.

Mean Free Path ( ) = [d(1) + d(2) + d(3) + d(4)] / 4

Mean Free Path calculation:

The mean free path or average distance between collisions for a gas molecule may be estimated from kinetic
theory. Serway's approach is a good visualization - if the molecules have diameter d, then the effective cross-
section for collision can be modeled by

using a circle of diameter 2d to represent a molecule's effective collision area while treating the "target"
molecules as point masses. In time t, the circle would sweep out the volume shown and the number of
collisions can be estimated from the number of gas molecules that were in that volume.

The mean free path could then be taken as the length of the path divided by the number of collisions.

Prob-1: A gas has a density of 10 particles m-3 and a molecular diameter of 0.1 m. What is its mean free
path?

1
Solution: We know, mean free path,   =1/(3.14 x 0.12 x 10) = 3.18 m.
d 2 nv

Self assessment-1: The mean free path of the molecules of a gas is 6 x 10-8 m and the diameter of a
molecule is 2.5 x 10-10 m. Find the number of molecules per m3. (Ans: 8.5 x 1025 )
 Van der Waals Equation
The Van der Waals equation was derived by Johannes Diderik van der Waals in the year 1873. The
equation is basically a modified version of the Ideal Gas Law which states that gases consist of point masses
that undergo perfectly elastic collisions. However, this law fails to explain the behaviour of real gases.
Therefore, the Van der Waals equation was devised, and it helps us define the physical state of a real gas.
More significantly, the Van der Waals equation takes into consideration the molecular size and molecular
interaction forces (attractive and repulsive forces). Sometimes, it is also referred to as the Van der Waals
equation of state.

What Is Van der Waals Equation?

The Van der Waals equation is an equation relating the relationship between the pressure, volume, temperature,
and amount of real gases. For a real gas containing ‘n’ moles, the equation is written as;
𝑎𝑛
𝑃+ × (𝑉 − 𝑛𝑏) = 𝑛𝑅𝑇
𝑉
Where P, V, T, and n are the pressure, volume, temperature and moles of the gas, respectively, and ‘a’ and ‘b’
constants specific to each gas.
Units of Van der Waals Constants
 Unit of “a” and is atm lit² mol⁻²
 Unit of “b” litre mol⁻¹

Van der Waals Equation Derivation

Van der Waals equation derivation is based on correcting the pressure and volume of the ideal gases
given by the Kinetic Theory of Gases. Another derivation is also used, which is based on the potentials of the
particles. Nonetheless, both derivations help us establish the same relationship.

Van der Waals Equation of State for Real Gases-

The kinetic theory of ideal gases assumes the gaseous particles as –
 Point masses without any volume
 Independent having no interactions
 Undergo perfectly elastic collisions
In practice, Van der Waals assumed that gaseous particles –
1. Are hard spheres.
2. Have definite volume, and hence cannot be compressed beyond a limit.
3. Two particles at close range interact and have an exclusive spherical volume around them.

Volume Correction in Van der Waals Equation

As the particles have a definite volume, the volume available for their movement is not the entire container
volume but less. Volume in the ideal gas is hence an overestimation and has to be reduced for real gases.

The volume of the real gas VR = Volume of the container or ideal gas (VI) – Correction factor (b)
VR = VI – b.
If the particles are independent, then,
Total volume of the particle = number of particle x volume of one particle = 𝑛 ( 𝜋𝑟 )
But, the particles are not independent, and they do interact.
Van der Waals considered two hard-sphere particles can come as close as to touch each other, and they will not
allow any other particle to enter into that volume, as shown in the diagram.

5
The two-sphere model has a total radius of ‘2r’ (r is the radius of the sphere particle) and volume of
= [ 𝜋(2𝑟) )= 8× 𝜋𝑟 = 8 × volume of a single particle.
Then, each of the two particles has a sphere of influence of 4 times the volume of the particles.
Volume correction for each particle is not the volume of the particle but four times of it
b = 4×( 𝜋𝑟 )
Volume correction for ‘n’ particles = nb = 4𝑛 × ( 𝜋𝑟 )
Volume (V) of the real gas = Vi – nb

Pressure Correction in Van der Waals Equation

Gaseous particles do interact. For inside particles, the interactions cancel each other. But, the particles
on the surface and near the walls of the container do not have particles above the surface and on the walls. So,
there will be net interactions or pulling of the bulk molecules towards the bulk that is away from the walls and
surface. The molecules experiencing a net interaction away from the walls and will hit the walls with less force
and pressure. Hence, in real gases, the particles exhibit lower pressure than shown by ideal gases.

The reduction in pressure α (particle density/volume)2

𝑛
𝑃 =𝑎×
𝑉
where, a is the proportionality constant.
Pressure of the real gas,
𝑛
𝑃 = 𝑃 +𝑎×
𝑉
Substituting the pressure and volume correction in the ideal gas equation, we get the Van der Waals equation
for real gases as:
𝑛
[𝑃 + 𝑎 × ](V – nb) = 𝑛𝑅𝑇
𝑉
For 1 mole gas,
𝑎
(𝑃 + )(V – b) = 𝑅𝑇
𝑉
Here, ‘a’ and ‘b’ are Van der Waals constants and contain positive values. The constants are characteristic of
the individual gas. When gas is ideal, or it behaves ideally, then both the constants will be zero. Generally, a
constant helps in the correction of the intermolecular forces, while the b constant helps in making adjustments
for the volume occupied by the gas particles.
Ideal Gas Equation and Van der Waals Equation
Ideal gas equation is given as PV = nRT
Van der Waals equation is

𝑎
(𝑃 + )(V – b) = 𝑅𝑇
𝑉
At constant temperature, a decrease in pressure increases the volume (V). Hence at low pressures, the volume
will be larger. So, the correction factor in pressure becomes very small and negligible.
Again, the volume of the gas will be larger compared to the volume of the molecules (n, b). Hence, the volume
correction also will be small and negligible.
As the correction factor becomes negligible, the pressure and volume of the real gases will be equal to that of
ideal gases. Interestingly, all real gases behave like ideal gases at low pressures and high temperatures.

Merits of Van der Waals Equation of State

1. Able to predict the behaviour of gases better than the ideal gas equation
2. Applicable not only to gases but to all fluids
3. The arrangement of the equation in a cubic equation in volume. The cubic equation gives three volumes
that are useful for calculating the volume at and below critical temperatures.
�3−(�+���)�2+���−���=0
4. Able to calculate the critical conditions of liquefaction and derive an expression of the Principle of
Corresponding States.
(�+3�2)(3�−1)=8�:�ℎ���,�=���,�=�������=���
Demerits of Van der Waals Equation
1. The equation gives more accurate results for all real gases only above the critical temperature.
2. The results are acceptable below the critical temperature.
3. The equation completely fails in the transition phase of gas to the liquid below a critical temperature.
In any case, Van der Waals theory helps us to develop an approximation for real gases at high pressures and
also predict the behaviour of non-ideal gases.

Solving Van der Waals Equation Problems

1. At 250 K, the activation energy for a gas-phase reaction was determined to be 6.500 kJ mol -1. What
percentage of gaseous molecules would be expected to have less than this energy at 250 K?
The expression in terms of moles for the distribution of molecular energies, n E = ne-E/RT, the fraction of the total
moles, (n), that have energy E or greater, (nE), as = nE/n = e-E/RT
At T = 250 K and for E = 6.500 kJ mol-1 = 6500 J mol-1, so, nE/n = e-6500/(8.314 x 250) = 0.044 or 4.4%.
Therefore, the percentage of molecules that have less than 6.500 kJ mol -1 energy = 100.0 – 4.4 = 95.6%.
2. Choose the correct option.
a) Increasing temperature increases the distribution of molecular velocities.
b) Larger the mass lesser the distribution of velocities.
c) Most probable velocity is the velocity that most of the molecules have at that temperature.
d) All the above
All the options are correct, and hence, ‘d’ is the correct option.
3. What is the compressibility factor?
The compressibility factor is a measure of the deviation of the real gas from ideal gas behaviour.
It is given by
�=�����;
, where P is the pressure, and Vm is the molar volume of the gas.
R is the gas constant, and T is the temperature.
4. How are the real gases classified in terms of compressibility?
�=�����
Real gases can be classified into three types on the magnitude of the compressibility factor.
i) For an ideal gas, PVm = RT, so that Z = 1 at all temperatures and pressure. But, there is no ideal gas.
ii) Z > 1. PVm > RT. The gases having compressibility greater than 1 have a positive deviation from the ideal
gases at all temperatures and pressures. Hydrogen and noble gases, except krypton, are examples.
They have low ‘a’ values.
iii) Z < 1. PVm < RT. The gases having compressibility lesser than 1 show negative deviation from the ideal
gases at all temperatures and pressures. Hydrogen and Helium are examples.
They have larger ‘a’ values.
Most of the gases show a compressibility factor of less than one at low pressures and greater than one at high
pressures.

7
5. What is the Boyle temperature? Give an example.
The compressibility factor depends on the temperature also.

The compressibility factor is inversely proportional to temperature. So, an increase in temperature decreases the
deviation from ideal behaviour. Every real gas has a certain temperature, where the compressibility factor
shows little changes and comes close to one. Some gases obey ideal gas laws at high pressures at a certain
temperature.
The temperature at which a real gas behaves like an ideal gas over a long range of pressure is Boyle’s
temperature for the gas. For example, nitrogen has a Boyle temperature of 323 K.
 Laws of thermodynamics
The four laws of thermodynamics define fundamental physical quantities (temperature, energy, and entropy)
that characterize thermodynamic systems. The laws describe how these quantities behave under various
circumstances, and forbid certain phenomena (such as perpetual motion).
The four laws of thermodynamics are
Zeroth law of thermodynamics: If two systems are both in thermal equilibrium with a third system then they
are in thermal equilibrium with each other. This law helps define the notion of temperature.
First law of thermodynamics: Famous scientist Joule first established the relation between heat and work and
expressed the relation in terms of law. The law is stated below:
Law: “When work is transformed into heat or heat is transformed into work, then work and heat is directly
proportional to each other”
Explanation: If Q be the amount of heat produced due to transformation of W amount of work, then according
to first law of thermodynamics, W  Q  W  JQ , Here J is a proportionality constant. It is called mechanical
equivalent of heat or Joule’s equivalent. This law is a special form of the principle of conservation of energy.
General form of first law of thermodynamics: Clausius expressed the first law of thermodynamics in a
general form. He expressed the law in the following way.
Law: “If some heat is supplied to a system which can do work, then the quantity of heat absorbed by the
system is equal to the sum of the increase in internal energy of the system and the external work done by the
system”.
Explanation: If dQ be the amount of heat absorbed by a system and dU be the change in the internal energy
and dW be the work done by the system due to absorption of heat, according to the first law of
thermodynamics, dQ = dU + dW. This is the special form of the principle of conservation of energy. It is valid
for any system. In above equation, dQ,dU and dW may be positive or negative.
(i) dQ is positive when the system absorbs heat and is negative when it loses heat,
(ii) dU is positive when the internal energy of the system increases and is negative when it decreases,
(iii) dW is positive when the system does work on the environment and is negative when the
surrounding does work on the system.
Significance of the 1st law of thermodynamics:
1. It establishes the relation between heat and work,
2. Heat and work are equivalent to each other,
3. It is nothing but the principle of conservation of energy,
4. Work or heat cannot be obtained from noting,
5. It is impossible to design a machine of perpetual motion without spending energy.
Prob-2: A system absorbs 800 J heat energy from the environment and its internal energy increases by 500
J. Find the work done by the system on the environment.
Solution: We know, dQ = dU + dW or, dW = dQ – dU = 800 J-500 J = 300 J.
Prob-3: A quantity of gas inside a cylinder while doing work of 200 J on the environment absorbs heat of
500 J. What is the change in internal energy of the gas? Will it increase or decrease?
Solution: We know, dU = dQ – dQ = 500 J – 200 J = 300 J.
Since dU is positive so the internal energy will increase.
Self assessment-2: A system receives 1800 J heat and does work of 400 J. Calculate the change in internal
energy of the system. [Ans: 1450 J]
Self assessment-3: A quantity of gas inside a cylinder while doing work of 500 J on the environment absorbs
heat of 300 J. What is the change in internal energy of the gas? Will it increase or decrease?
Second law of thermodynamics:
(1) Clausius’s statement: It is impossible to make heat flow from a body at a lower temperature to a
body at a higher temperature without doing external work on the substance.
(2) Kelvin’s statement: Continuous flow of energy cannot be obtained from an object cooling it
from its surrounding.
(3) Plank’s statement: It is impossible to construct an engine which can extract heat continuously
from a heat source and completely transforms into work.
(4) Carnot’s statement: No engine can be built which can extract a fixed amount of heat and will
convert totally into work.

9
Third law of thermodynamics: The entropy of a system approaches a constant value as the temperature
approaches zero. The entropy of a system at absolute zero is typically zero, and in all cases is determined only
by the number of different ground states it has. Specifically, the entropy of a pure crystalline substance at
absolute zero temperature is zero.
Isothermal process: An isothermal process is a thermodynamic process in which the temperature of the
system remains constant. The heat transfer into or out of the system typically must happen at such a slow rate
that the thermal equilibrium is maintained.
A practical example of this is some heat engines which work on the basis of the carnot cycle. The carnot cycle
works on the basis of isothermal.
Adiabatic process: An adiabatic process is a thermodynamic process in which there is no heat transfer (Q)
into or out of the system. In other words Q = 0. An adiabatic process is generally obtained by surrounding the
entire system with a strongly insulating material or by carrying out the process so quickly that there is no time
for a significant heat transfer to take place.
The compression and expansion strokes in an internal-combustion engine are both approximately adiabatic
processes. What little heat transfers outside of the system is negligible and virtually all of the energy change
goes into moving the piston.
Air is made up of a mixture of gases that is subject to adiabatic heating when it is compressed and adiabatic
cooling when it is expanded.

Difference between isothermal and adiabatic change

Sl. No. Isothermal change Adiabatic change
1 The change of pressure and volume of a gas The change of pressure and volume of a gas by
at constant temperature is called isothermal keeping the total heat content of the gas fixed is called
change. adiabatic change.
2 In this change necessary heat is taken or Change of temperature takes place in this process.
rejected to keep the temperature constant.
3 It is very slow process. It is very fast process.
4 The container of the gas should be good The container of the gas should be non-conducting.
conductor of heat.
5 It follows Boyle’s law. It does not follow Boyle’s law.

Specific Heat of Gas

Specific heat of any material is defined as the amount of heat required to increase the temperature of unit mass
of the material by one degree.
dq
C
mdT
The unit of C is JKg 1 K 1
Specific Heat at Constant Volume: The amount of heat required to raise the temperature by one degree of unit
mass of a gas at constant volume, is known as specific heat at constant volume.
dq
Cv  ( )v
mdT
10
Specific Heat at Constant Pressure: The amount of heat required to raise the temperature by one degree of
unit mass of a gas at constant pressure, is known as specific heat at constant pressure.
dq
Cp  ( )p
mdT

Relation between pressure and volume of a gas in a adiabatic change:

Let dQ amount of heat is supplied in one mole of an ideal gas. Due to this heat the temperature of the gas will
increase and the gas will do some work. Let the change in volume and temperature be dV and dT respectively.
From 1st law of thermodynamics, we have
dQ = dU + dW = CvdT + PdV…………(1) where Cv is the specific heat of the gas at constant pressure.
In adiabatic process, dQ = 0, so eq. (1) gives, CvdT + PdV = 0……………………(2)
For ideal gas, PV=RT, here R is molar gas constant.
Differentiating the above equation we get, PdV + VdP = RdT or, dT = (PdV + VdP)/R. Using this in eq.
(2), we get,
PdV  VdP
Cv ( )  PdV  0  C v PdV  C vVdP  RPdV  0
R
 C v PdV  C vVdP  (C p  C v ) PdV  0 [ R  (C p  C v ) ]

 C v PdV  C vVdP  C p PdV  C v PdV  0  C vVdP  C p PdV  0

Cp
 VdP  PdV  0 [Dividing both side by Cv]
Cv

Cp dP dV
 VdP  PdV  0 [   ]   0 [Dividing both side by PV]
Cv P V
Now integrating the above equation, we get,
Log e P  Log eV  Cons tan t  Log e K , [Here K = constant]

Log e P  Log eV   Log e K  Log e PV   Log e K  PV   K  cons tan t

This is the relation between pressure and volume of a gas in a adiabatic change.
Relation between temperature and volume of a gas in a adiabatic change:
We know for ideal gas, PV=RT, here R is molar gas constant. So, P = RT/V
Again, we know, PV   K  cons tan t ………(1), Putting the value of P in eq. (1), we have
RT
XV   cons tan t  RTV  1  cons tan t  TV  1  cons tan t
V
This is the relation between temperature and volume of a gas in a adiabatic change.

Prob-1: The volume of air is made three times the original volume by adiabatic expansion. If the initial
pressure is 1 atmosphere, what is the final pressure? [γ = 1.4]

11
   V2  P 3V 1.013 X 10 5 1.013 X 10 5
Solution: P1V1  P2V2  ( )  ( 1 )  ( 1 )1.4  ( )  P2   P2  2.176 X 10 4 Pa
V1 P2 V1 P2 (3)1.4
Prob-2: A fixed amount of gas at NTP is suddenly compressed to 1/3 th of its volume. What is the final
temperature? [γ = 1.4]
 1  1 V1  1 V
Solution: T1V1  T2V2  T2  ( ) XT1  ( 1 )  1 XT  (3)1.41 X 273  428.33K  155.330 C
V2 1
V1
3
Prob-3: For an ideal gas γ = 1.4, calculate the values of molar specific heats of the gas.
[R = 8.31 Jmol-1K-1]
Cp R
Solution:    C p  C v Again, C p  C v  R  C v  C v  R  C v (  1)  R  C v 
Cv  1

R 8.31
 Cv    20.8 Jmol-1K-1 So, C p  R  C v  8.31  20.8  29.11 Jmol-1K-1
  1 1.4  1
Reversible Process:
A reversible process is one which can be retraced in the opposite direction so that the working substance
passes through exactly the same state in all respects as in the direct process.
Example: A given mass of ice changes to water when a certain amount of heat is absorbed by it and the same
mass of water changes to ice when the same quantity of heat is removed from it.
Irreversible Process:
An irreversible process is one which can not be retraced in the opposite direction by reversing the controlling
factor. All changes which occur suddenly like the explosion etc may be considered as irreversible.
Some examples of irreversible process are:
(a) Sudden unbalanced explosion of a gas either isothermal or adiabatic.
(b) Heat produced by friction.
(c) Heat generated when a current flows through an electrical resistance.

The Carnet’s Ideal Engine:

The ideal engine consists of the following parts.
(i) A cylinder with perfectly non-conducting wall but with a perfectly conducting bottom containing a
perfect gas instead of steam as working substance and fitted with a perfectly non- conducting and
frictionless piston.
(ii) A source of heat called a heat reservoir H of unlimited heat capacity, always kept at higher
temperature T10 absolute.
(iii) A perfectly non-conducting stage N.
(iv) A refrigerating or cold body R of unlimited heat receiving capacity, which is kept at a constant
temperature T20 absolute to serve as the sink.
12
Efficiency of Heat Engine

Each heat engine has a source and a sink. While working it absorbs an amount of heat from the source at higher
temperature and a part of the absorbed heat is used up in doing external work and the residual heat is given out
to the (sink) or to the environment at lower temperature.

Let us consider an engine absorbs Q1 amount of heat from the source at higher temperature T1 .

After doing some external work at the cost of a part of heat Q1 and release heat Q2 to the sink at temperature T2 ,

where T2 < T1 .

The amount of heat used to do external work  Q1  Q2

The efficiency of the heat engine is defined as the ratio of heat used to do work to the heat supplied or absorbed
by the machine. It is denoted by  .

Heat used to do work Q  Q2

  1
Heat sup plied or absorved Q1
Q  Q2
  1 ............................................(1)
Q1
The efficiency is expressed in percentage
Q  Q2
  1  100%..................................(2)
Q1
It is known that the amount of heat absorbed from a source of an engine is proportional to its temperature, i.e.
Q T
Q
Or ,  Cons tan t
T
Q Q
Therefore, 1  2
T1 T2
Q T
Or, 2  2 ....................................(3)
Q1 T1
Q  Q2 Q
From equation   1 1  2
Q1 Q1

T2
Or,   1  .....................................(4)
T1
In percentage,
T T
  1 2  100%...........................(5)
T1
If Q2  0 then 100 %
Practically, an engine of efficiency 100 % can not be constructed. Only mathematically or theoretically, an
engine with 100% efficiency can be made.
The Carnot Cycle:

13
A simple cyclic process is one in which a working substance starting from a given initial condition of
temperature, pressure and volume is made to undergo two successive expansions (one isothermal and another
adiabatic) and then two successive compression and then brought back finally to its original condition.

Exercise-1: A reversible engine is working between 273k and 373k . Find its maximum efficiency.
Solution: Given, Temperature of the source, T1  373K
Temperature of the sink, T2  273K
Efficiency of the engine,   ?
T  T2 373  273 100
We know,   1  100%   100%   100%
T1 273 372
Or ,  0.268  100 %  27 %

Exercise-2: The efficiency of a Carnot’s engine is 80%. If the temperature of the source is 500k . what is the
temperature of the sink of the engine?
Solution: Let T2 is the temperature of the engine.
Given,
80
Efficiency of the engine,   80% 
100
Temperature of the source, T1  500K
Temperature of the sink, T2  ?
T  T2
We know that,   1
T1
80 500  T2
Or , 
100 500
Or, T2  100K
Exercise-3: The temperature of source and sink of a Carnot;s engine are 700k and 400k respectively. If the
engine absorbs 350  10 4 J heat per cycle of operation. Find (a) efficiency of the engine (b) amount of work
done per cycle and (c) amount of heat rejected to the sink.
Solution: Given, Temperature of the source, T1  700K
Temperature of the sink, T2  400K
Heat absorbed by the engine, Q1  350  10 4 J
T  T2 700  400 300
(a) Efficiency,   1  100%   100%   100%  42.85%
T1 400 400
(b) Let W is the amount of work done per cycle.
W  Q1  Q2
T Q
But 1  1
T2 Q2
700k 350  10 4 J
Or , 
400k Q2
Or , Q2  200  10 4 J
 W  350  10 4 J  200  10 4 J  150  10 4 J
(d) The amount of heat rejected to the sink, Q2  200  10 4 J
14
Entropy: Entropy is the quantitative measure of disorder in a system. The concept comes out of
thermodynamics, which deals with the transfer of heat energy within a system. Instead of talking about
some form of "absolute entropy," physicists generally talk about the change in entropy that takes place in a
specific thermodynamic process.
Entropy is measured by the rate of change of heat absorbed or rejected with respect to temperature of the
system.
Let the temperature of the system be T and it absorb or reject dQ amount of heat. So, the
change of entropy of the system is given by, dS = dQ/T. Its SI unit is J/K.

Change of entropy in an irreversible process

Let an irreversible engine take up Q1 amount of heat from a source at temperature T1 and reject Q2 amount
Q1  Q2
of heat to the sink at temperature T2. So, the efficiency,  / 
Q1

T1  T2
But the efficiency of a reversible cycle working within the above temperature limit is,  
T1
Now, according to Carnot’s theorem, η > η/
T1  T2 Q1  Q2 T Q Q T Q Q Q Q
So, >  1 2  1 2  2  2  2  1  2 - 1  0
T1 Q1 T1 Q1 Q1 T1 T2 T1 T2 T1

Q1
So, if the working system is considered as a whole, we find that the heat source loses entropy and the
T1

Q2 Q Q
heat sink gains entropy . Hence, the net gain of entropy = 2 - 1 , the value of which is positive.
T2 T2 T1
So, entropy increases in case of irreversible process.

15