Physics-II

(PH 111)
Dr. Pawan Kumar Tiwari
Department of Physics
BIT Mesra, Ranchi
 Thermal Physics?
• Thermal Physics ≡ Thermodynamics
• Study of the effects of heat, work, energy on a system
• It deals with large scale observations such as propulsion systems
• Small scale gas interactions are described by the kinetic theory of gases
• It gives us a feeling that Thermodynamics is exclusively concerned
with the heat engines
• The learning about things like heat, temperature, and pressure hold
little appeal, consequently there is no glamorous concepts in
thermodynamics
• No one is very excited about heat engines and there is a mistaken
notion that thermodynamics is easy and trivial. True?
continues…..
 Thermal Physics?
• Thermodynamics has a wider applications when combined with basic
statistical mechanics
• Statistical mechanics interprets, for example, thermal energy as the energy of
atomic particles in disordered states and temperature as a quantitative
measure of how energy is shared among such particles
• Thermal Physics has applications in the multitude of areas such as
pharmaceutical industry, day-to-day life machines and devices, etc.
• Thermal Physics = Thermodynamics + Statistical Mechanics
• Thermal Physics introduces the ideas of Entropy and Free Energy
Principles
• This is the essential and underlying theme of thermal physics
Differentiating Thermodynamics and Statistical
Mechanics
• Thermodynamics
• Thermodynamics describes the processes during which heat is produced or absorbed
• Thermodynamics grows from the theory of temperature, heat, and entropy

• Statistical Mechanics
• It links macroscopic properties of matter in bulk in terms of microscopic properties of
its constitutive elements, and to learn about the latter through the former
• It is quite desirable to understand the Macroscopic and Microscopic point
of view in exploring physical systems
• By studying the system-surrounding diagram
 System and Surroundings
• In thermodynamics, attention is focused
on a particular part of the universe,
simply defined as the system
• The rest of the universe outside the
system is called the surroundings
• The system and the surroundings are
separated by a wall (boundary or
partition) and they may, in general,
exchange energy and matter, depending
on the nature of the partition. CF. Fig.1
• If no matter crosses the boundary, then
the system is closed Fig.1. A system is a fixed mass of compressible
• While, if there is an exchange of matter fluid, such as a gas, contained in a cylinder
between system and surroundings, then with a moveable piston
the system is open
 Macroscopic and Microscopic point of view

Macroscopic Microscopic
• In Layman’s term, it considers variables or • In Layman’s term, it considers variables or
characteristics of a system at characteristics of a system at approximately
approximately the human scale, or larger the molecular scale, or smaller
• They are few in number needed to • Many quantities must be specified to describe
describe the system, known as the system. The particles interact with one
macroscopic coordinates another by means of collisions, etc.
• For example, N number of particles in different
• For example, temperate, pressure, mass, states with energies 𝜖1 , 𝜖2 …, etc.
volume, composition
• It can’t be directly measured, however, must
• It can be directly measured, and no be calculated with assumptions and using
special assumptions are made. statistical techniques
• For example, In the laboratory, a pressure • For example, as per calculation, pressure is the
gauge may be used to measure and record average rate of change of linear momentum due
the changes of pressure as the engine to the large number of molecular collisions made
operates due to movement of piston on a unit of area.
 The Directly Measurable Variables
• The directly measureable variables are called state variables, or
thermodynamic variables, or thermodynamic coordinates
• The thermodynamic variables are classified into following three groups
1. The first group specifies amount of matter and includes the number of particles in
the system N and the mass of the system m
2. Variables which scales with the system size, like volume (V), internal energy (U),
and entropy (S), etc. are called extensive variables
3. The variables which are independent of the system size, like temperature (T), and
pressure (P), etc. are called intensive variables
• It is the purpose of thermodynamics to find, among the thermodynamic
coordinates, general relations that are consistent with the fundamental
laws of thermodynamics. However, attention is directed to the interior of
the system.
 Temperature
• The concept of temperature is fundamental to any study of
thermodynamics
• We have an intuitive sense of temperature, because we can feel if an
object is hot or cold; this it is not easy to give a precise definition of
temperature. Ambiguity !
• The temperature could be defined in an unambiguous way if we
understand some of the basics such as
• Equilibrium state
• Thermal Equilibrium, and
• Zeroth Law of Thermodynamics
 Equilibrium state
• Consider an isolated system (system in which neither mass nor energy can pass
through the wall) from its surrounding as shown in Fig.1. on slide number 5
• Also, there is not any mechanical interaction between the system and the
surroundings, i.e., no movement of the piston in the cylinder
• After a time, this gas system, tends to an equilibrium state in which no further
changes occur
• In particular, the pressure P becomes uniform throughout the gas and remains constant in
time, as does the volume V.
• We say that the gas is in the equilibrium state (P, V).
• The important point is that two variables are required to specify the equilibrium
state of a simple system
• An equilibrium state is one in which all the bulk physical properties of the system
are uniform throughout the system and do not change with time.

continues…..
 Equilibrium state
• Consider a system as shown in Fig.1. (slide
number 5) with its piston clamped, and
connected to a second cylinder via
intervening wall, fitted with a free piston,
containing the same gas with same mass,
volume, and pressure as the first (refer Fig.2.)
• Let piston of the second cylinder is pushed in,
there may or may not be changes in the
pressure of the gas system in the first cylinder
• If there is no change, the intervening wall is
said to be adiathermal or, more commonly,
adiabatic
• If there is a change, the wall is said to be Fig.2. Concept of Adiathermal (adiabatic) and
diathermal, and a thermal interaction has
taken place Diathermal wall
• Two systems in contact via a diathermal wall
are said to be in thermal contact.

continues…..
 Equilibrium state
• If two thermodynamic systems such as gases are put into thermal
contact, after a time no further changes in the pressures and volumes
will occur.
• When the gases pressures and volumes are no longer changing, each
gas is then considered to be in an equilibrium state, and the gases are
said to be in thermal equilibrium with each other, thereby leading to
the definition of temperature.
• Although, we have not yet introduced the concept of heat, it may be said that
a diathermic wall is a boundary through which heat is communicated from
one system to another system, yet remains closed to the transport of matter.
An ideal adiabatic wall does not communicate heat
 Thermal Equilibrium
• Refer Fig.3., which includes the systems
A, B, and C
• Each of the three is in an equilibrium
state, meaning that the state variables
have assumed constant and uniform
values
• Suppose that the states of the systems
are such that, when A and B are brought
together in thermal contact, thermal
equilibrium exists in that no changes
occur in the variables.
• Also suppose that the same is true for the
systems A and C. It is an experimental
observation that B and C would also be in
thermal equilibrium if they were similarly Fig.3. Concept of thermal equilibrium
brought together
 Zeroth Law of Thermodynamics &
Temperature
• Previous slide analysis lead us to conclude that

• If each of two systems is in thermal equilibrium with a third, they are in

thermal equilibrium with one another

• The temperature of a system is a property that determines whether or not

that system is in thermal equilibrium with other systems. Systems in thermal
equilibrium with one another have the same temperature T
 Isotherms
• Consider again the gas system contained in a cylinder with a moveable piston, as in Fig.1.
(slide number 5)
• Suppose that the gas in the equilibrium state (P, V) and is in thermal equilibrium with
another reference system that surrounds the cylinder, so that the two systems have the
same temperature
• This state can be plotted as a point on a Pressure versus Volume plot, which is called an
indicator diagram or PV diagram (refer Fig.4., slide number 15)
• Let the gas system be separated from the reference system. If the piston is now pushed
in to take the gas to a new state (P′, V′), and if this new state is also in thermal
equilibrium with the unchanged reference system, then by the zeroth law the two states
(P, V) and (P′, V′) are themselves in thermal equilibrium and have the same temperature
• This really means that two identical systems in the states (P, V) and (P′, V′) would be in
thermal equilibrium.
• The locus of all such points with the same temperature is called an isotherm

continues…..
PV Diagram

Fig.4. PV Diagram
 State Functions
• The basic state variables P, V, and temperature T are used to define other functions,
which take unique values at each equilibrium state
• For example, the internal energy, the entropy, and the enthalpy.
• State property is an alternative and perhaps a more appropriate name for state function
• P, V, and T are functionally connected at each equilibrium state by the equation of state,

𝑓 𝑃, 𝑉, 𝑇 = 0 (1)
• It shows that, of the three directly measurable variables, P, V, and T, only two are independent
and any one may be expressed in terms of the other two, i.e., 𝑃, 𝑉 , 𝑃, 𝑇 , or 𝑉, 𝑇
• An example is the equation of state for an ideal gas,

𝑃𝑉 = 𝑛𝑅𝑇 (2)
where,
𝑛 → number of moles, 𝑅 → universal gas constant, 8.315 J mol. K , 𝑇 → temperature
 Temperature Scale
• In order to give numerical values to different temperatures, a
systematic and reproducible method for assigning such values is
required
• To choose a system and then to select a physical property of that
system (the thermometric variable or thermometric property) that
varies with temperature. For example
• Length of the column of mercury in a mercury-in-glass thermometer, or
• The resistance of a piece of platinum wire.
• We will discuss here two types of temperature scales
• Thermodynamic temperature scale
• The gas scale
 Thermodynamic temperature scale
• Let the thermometric variable is labeled X. The normal choice of X is
something that can easily be measured, e.g., length of column mercury or
resistance of platinum
• The general thermometric variable X is used to set up a scale of
temperature. Call 𝑇𝑋 the temperature on the X scale, where the subscript X
is a reminder that the temperature depends on the thermometric property
chosen
• The numerical value of temperature on this scale is defined so that the
thermometric property X varies with temperature in the simplest possible
way, according to the linear relation
𝑋 = 𝑐𝑇𝑋 (3)

where c is a constant
continues…..
 Thermodynamic temperature scale
• The value of c is fixed by choosing an easily reproducible 𝑇𝑋 (a fixed point) and
assigning to it a particular value
• The customarily chosen fixed point is the temperature at which ice, water, and
water vapor coexist in equilibrium; this is known as the triple point (TP) of water
• The value given to 𝑇𝑇𝑃 at this fixed point is 273.16
• Substituting the value for the temperature of the triple point, where the value of
X is 𝑋𝑇𝑃 , in Eq. (3) gives
𝑋
𝑇𝑋 = 273.15
𝑋𝑇𝑃 (4)
• While in the case of resistance based temperature scale, the expression is
𝑅
𝑇𝑅 = 273.15
𝑅𝑇𝑃 (5)
2
• Or, 𝑅 𝑇 = 𝑅𝑇𝑃 1 + 𝑎𝑇 + 𝑏𝑇 , where a and b are constants
 The gas scale

• The schematic diagram of a constant-volume

gas thermometer is shown in Fig.5.
• The volume of the gas is kept constant by
adjusting the height of the mercury column
until the mercury meniscus just touches the
marker at the end of the capillary tube
• The bulb of gas is immersed in a system
whose temperature is to be measured, and
the pressure of the gas is used as the
thermometric parameter
• The gas scale temperature is determined from
𝑃
𝑇𝑔𝑎𝑠 = 273.15
𝑃𝑇𝑃
• The ideal gas scale is defined as Fig.5. A constant-volume gas thermometer
𝑃
𝑇𝑔𝑎𝑠 = 273.15 lim
𝑃𝑇𝑃→0 𝑃𝑇𝑃
 To Think about?
• The choice of 273.15 K for the temperature of the fixed triple point
(TP)
• This value was chosen to make the size of the kelvin such that there would be
exactly 100 K between the experimentally determined temperatures of the ice
and steam points on the ideal gas scale.
• To the accuracy then available, these temperatures were measured to be
273.15 and 373.15 K, respectively.
• It should be noted that there is 0.01 K difference between the ice and triple
points.
 The Ideal Gas
• Kinetic theory assumes that a gas can
be modelled as a collection of
individual tiny particles which can
bounce off the walls of the container,
and each other
• The term “ideal” is due to the
following assumptions
• There are no intermolecular forces, so
that the molecules are not attracted to
each other
• Molecules are point-like and have zero
size
Fig.6. Gas as a collection of tiny
• The fundamental ideal gas equation is particles
explained in the next slide
continues…..
 The Ideal Gas Equation
• Experiments on the gases shows that the pressure P of a volume V of gas
depends on its temperature T. Refer the table below
Constraint Expression Law Combined Law
1. At Constant Pressure 𝑉∝𝑇 Charles’

2. At Constant Volume 𝑃∝𝑇 Gay-Lussac’s 𝑃𝑉 ∝ 𝑇

3. At Constant Temperature 𝑃∝1 𝑉 Boyle’s

• If there are N molecules in the gas, the above Combined Law can be expressed as
𝑃𝑉 = 𝑁𝑘𝐵 𝑇 (Ideal Gas Equation) (6)
• The Boltzmann constant, 𝑘𝐵 = 1.3807 × 10−23 𝐽𝐾 −1 .
• Eq.(2) and Eq. (6) are identical ?
 Question
1) Consider a gas contained in the cylinder-piston arrangement shown
in Fig.1. The gas is pure nitrogen (𝑁2 ) with a mass of 1.60 g and is in
equilibrium with its surroundings. The gas is initially at standard
temperature and pressure, with P = 101 kPa and T = 0°C. Find the
following
A. Find the gas’s volume.
B. The piston is now moved, slowly enough so that equilibrium with the
surroundings is maintained, until its pressure reaches 120 kPa. What is the
gas’s new volume?
C. Eq. (2) and Eq. (6) hold true, calculate the number of 𝑁2 molecules

continues…..
 Questions
2) The length of the mercury column in a mercury-in-glass thermometer is 5 cm
when the bulb is immersed in water at its triple point. What is the temperature
on the mercury-in-glass scale when the length of the column is 6.0 cm? What
will the length of the column be when the bulb is immersed in a liquid at 100°
above the ice point, as measured on the mercury-in-glass scale?

3) The resistance of a wire is given by

𝑅 = 𝑅0 1 + 𝛼𝑡 + 𝛽𝑡 2
where t is the temperature in degrees Celsius measured on the ideal gas scale
and so 𝑅0 is the resistance at the ice point. The constants α and β are
3.8 × 10−3 𝐾 −1 and −3.0 × 10−3 𝐾 −1 , respectively.
• Calculate the temperature on the resistance scale at a temperature of 70°C on the ideal gas
scale.

continues…..
 To Think !
• Are Thermal and Thermodynamic Equilibrium identical?
 Thermal and Thermodynamic Equilibrium
• If two systems have the same temperature so that they are in thermal
equilibrium, this does not necessarily mean that they are in complete
or thermodynamic equilibrium
• For this condition to hold, in addition to being in thermal equilibrium,
they also have to be in
• Mechanical equilibrium, with no unbalanced forces acting
• Chemical equilibrium, with no chemical reactions occurring
• Diffusive equilibrium, with no flow of matter from one system to another
• Much of thermodynamics concerns the changes that occur to both
systems when one or more of these three kinds of equilibrium do not
exist
 Mathematical Theorem
• Let 𝑓 𝑥, 𝑦, 𝑧 = 0, then 𝑥 can be imagined as a function of 𝑦 and 𝑧, then we can write,

𝜕𝑥 𝜕𝑥
𝑑𝑥 = 𝑑𝑦 + 𝑑𝑧 (6)
𝜕𝑦 𝑧
𝜕𝑧 𝑦
• If 𝑦 is imagined as a function of z and 𝑥, then

𝜕𝑦 𝜕𝑦 (7)
𝑑𝑦 = 𝑑𝑧 + 𝑑𝑥
𝜕𝑧 𝑥
𝜕𝑥 𝑧
• Substituting Eq. (7) in Eq. (6) and rearranging the term, we obtain

𝜕𝑥 𝜕𝑦 𝜕𝑥 𝜕𝑦 𝜕𝑥 (8)
𝑑𝑥 = 𝑑𝑥 + + 𝑑𝑧
𝜕𝑦 𝑧
𝜕𝑥 𝑧
𝜕𝑦 𝑧
𝜕𝑧 𝑥
𝜕𝑧 𝑦

continues…..
 Mathematical Theorem
• Of the three coordinates, only two are independent, and choosing 𝑥 and z as independent
coordinates, Eq. (8) must be true for all values of 𝑑𝑥 and 𝑑𝑧. If 𝑑𝑧 = 0, and 𝑑𝑥 ≠ 0, then
𝜕𝑥 𝜕𝑦 𝜕𝑥 𝜕𝑦
= 1, or =1 (9)
𝜕𝑦 𝑧 𝜕𝑥 𝑧 𝜕𝑦 𝑧 𝜕𝑥 𝑧
• If 𝑑𝑧 ≠ 0, and 𝑑𝑥 = 0, then from Eq. (8), we obtain
𝜕𝑥 𝜕𝑦 𝜕𝑥
=− , or
𝜕𝑦 𝑧 𝜕𝑧 𝑥 𝜕𝑧 𝑦
𝜕𝑥 𝜕𝑦 𝜕𝑧 (10)
= −1
𝜕𝑦 𝑧 𝜕𝑧 𝜕𝑥 𝑦
𝑥
• Eq. (9) and Eq.(10) are widely used expressions in the thermodynamics, and 𝑓(𝑃, 𝑉, 𝑇) can
similarly be expressed as
𝜕𝑃 𝜕𝑉 𝜕𝑇
= −1
𝜕𝑉 𝑇 𝜕𝑇 𝜕𝑃 𝑉
𝑃
 The Two Important Coefficients
• From the general Physics, the following two coefficients play
important roles in thermodynamics
1. Coefficient of volume expansion (at constant pressure, P) = β =
𝑐ℎ𝑎𝑛𝑔𝑒 𝑜𝑓 𝑣𝑜𝑙𝑢𝑚𝑒 𝑝𝑒𝑟 𝑢𝑛𝑖𝑡 𝑣𝑜𝑙𝑢𝑚𝑒 ∆𝑉 𝑉
=
𝑐ℎ𝑎𝑛𝑔𝑒 𝑜𝑓 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 ∆𝑇
• For a small change or infinitesimal change, the above equation in differential coefficient
of volume expansion, or volume expansivity can be expressed as,

1 𝜕𝑉 (11)
𝛽=
𝑉 𝜕𝑇 𝑃
• 𝛽 is expressed in the unit of reciprocal kelvin (𝐾 −1 )

continues…..
 The Two Important Coefficients
2. Bulk modulus (at constant Temperature, T) =𝐵=
𝑐ℎ𝑎𝑛𝑔𝑒 𝑜𝑓 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 ∆𝑃
− =−
𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑣𝑜𝑙𝑢𝑚𝑒 𝑝𝑒𝑟 𝑢𝑛𝑖𝑡 𝑣𝑜𝑙𝑢𝑚𝑒 ∆𝑉 𝑉
• For a small change or infinitesimal change, the above equation in differential bulk
modulus, or isothermal bulk modulus is expressed as
𝜕𝑃 (12)
𝐵 = −𝑉
𝜕𝑉 𝑇
• In thermodynamics, the reciprocal of B is called isothermal compressibility, and it is
written as
1 𝜕𝑉
𝜅=− (13)
𝑉 𝜕𝑃 𝑇
• The unit of isothermal compressibility is reciprocal Pressure (𝑃𝑎−1 )
 Relation between 𝜷 and 𝛋
• Dividing Eq. (11) by Eq. (13), we would obtain
𝛽 𝜕𝑉 𝜕𝑉
=− (14)
𝜅 𝜕𝑇 𝑃
𝜕𝑃 𝑇

𝛽 𝜕𝑉 𝜕𝑃
≡ =− , 𝑢𝑡𝑖𝑙𝑖𝑧𝑖𝑛𝑔 𝐸𝑞. (9)
𝜅 𝜕𝑇 𝑃
𝜕𝑉 𝑇

• Besides, using Eq. (10), Eq. (14) can be expressed as

𝛽 𝜕𝑇
=1 , or by utilizing Eq. 9 similarly
𝜅 𝜕𝑃 𝑉

𝛽 𝜕𝑃
= (15)
𝜅 𝜕𝑇 𝑉
 Questions
5) The equation of a state of an ideal gas is 𝑃𝑉 = 𝑛𝑅𝑇, where 𝑛 and 𝑅 are
constant, show that the
• Volume expansivity 𝛽 is equal to 1 𝑇
• Isothermal compressibility 𝜅 is equal to 1 𝑃

6) The equation of state of a non-ideal gas (unimolar gas) is given as

𝑃 + 𝑎 𝑉 2 𝑉 − 𝑏 = 𝑅𝑇
where 𝑎, 𝑏, and 𝑅 are constants. Calculate the following quantities
𝜕𝑃
•
𝜕𝑉 𝑇
𝜕P
•
𝜕T V
𝜕𝑉
• From above two relations calculate
𝜕𝑇 𝑃
 Questions
7) The equilibrium states of a superheated steam are represented by
Callendar’s equation
𝑟𝑇 𝑎
𝑉−𝑏 = − 𝑚
𝑃 𝑇
where 𝑏, 𝑟, 𝑎 and 𝑚 are constants.
• Calculate the volume expansivity 𝛽 as a function of T and P

8) Show that for small thermal expansions of a solid object the linear
and volume coefficients of expansion are related by β ≈ 3α
 Process in Thermodynamics
• Thermodynamics is concerned with changes in the different state
functions that occur when a system changes from one equilibrium
state to another
• A process is the mechanism of bringing about such a change. These
initial and final equilibrium states are called the end points of the
process
• For example, Pushing in a piston (Fig.1, slide number 5) and
compressing the gas in a cylinder from an equilibrium state (𝑃1 , 𝑉1 ) to
a new equilibrium state (𝑃2 , 𝑉2 ) is an example of a process

continues…..
 Processes

Reversible Irreversible
• Reversible processes are quasistatic processes • In contrast, it is possible to bring about the
• A process that can be thought of as a succession same change between the same two end
of equilibrium states is called a quasistatic points by pushing in the piston suddenly from
process. For example, pushing in piston to bring volume 𝑉1 to volume 𝑉2 .
changes in the equilibrium states, i.e., initial • Then there would be turbulence, with finite
( 𝑃1 , 𝑉1 ) to a new equilibrium state ( 𝑃2 , 𝑉2 ) temperature and pressure gradients both within
through series of intermediate states the gas and between it and the surroundings
• The equation of state 𝑃𝑉 = 𝑛𝑅𝑇 holds for • The equation of state 𝑃𝑉 = 𝑛𝑅𝑇 does not
each point in the process. hold for the intermediate stages in an
• Thermal expansion is an example of a irreversible process
reversible process, because cooling a • Mixing of two different substances which
substance by an amount ∆𝑇 results in a cannot be separated as the process of
volume decrease equal to the volume intermixing is again spontaneous in nature,
increase that occurs when the temperature is the reverse of which is not feasible
increased by ∆𝑇.

continues…..
 Processes

Fig.7. A reversible process may be shown as a continuous line on a PV diagram. The one
shown here is an isothermal process. An irreversible process cannot be shown in this way.
continues…..
 Concept of Work
• If a system undergoes a displacement under the action of force, work is
said to be done, the amount of work being equal to the product of the
force and the component of the displacement parallel to the force
work = force × displacement
• The work done either by the system or on the system is called external
work
• For example, a gas confined in a cylinder and at uniform pressure, while expanding
and imparting motion to a piston does external work on the surrounding
• The work done, however, by one part of a system on another part is called
internal work
• For example, the interactions of molecules, atoms, or electrons on one another
constitute internal work
• Unless otherwise indicated, the word work, will mean external work
 Sign Convention for work
• Old Books
• When the force exerted on a mechanical system is in same direction as the
displacement of the system, the work of the force is positive, work is said to
be done on the system
• Conversely, when the work is done by the system, the work is regarded as
negative
New Books
• Negative work is done on the system
• Positive work is done by the system

 Regardless of which convention is chosen, it makes no difference to the

fundamental thermodynamic relations
 Interpretation of Work
• If the force is increased infinitesimally
so that the piston moves in by 𝑑𝑥, the
work done on the gas by the
surroundings applying the force 𝐹 is
𝑑𝑊 = 𝑃𝐴𝑑𝑥 = −𝑃𝑑𝑉 (16)
• Negative sign is necessary because during
compression, the volume is decreased,
but the work done on the gas is positive
• The total work performed on the gas
in the process is
𝑉2
𝑊=− 𝑃𝑑𝑉 (17)
𝑉1 Fig.8. The work done on a gas when it is compressed
reversibly through an infinitesimal volume change dV is
−P dV
 Work and Path
(curve 1-2)
• Suppose a gas undergoes isothermal
expansion, from ( 𝑃1 , 𝑉1 ) to (𝑃2 , 𝑉2 ). Refer
Fig.9.
• The path is represented by upper curve 1-2
• The absolute value of the work done in a
reversible process is the area under the curve
or path for the process
• Using ideal gas equation, i.e., Eq. (2) in Eq.
(17), we obtain
𝑉2 𝑉2
1
𝑊=− 𝑃𝑑𝑉 = −𝑛𝑅𝑇 𝑑𝑉
𝑉1 𝑉1 𝑉
𝑉2 (18)
= −𝑛𝑅𝑇𝑙𝑛
𝑉1
• The result in Eq. (18) works equally well for
compression and expansion Fig.9. Work depends on the path

continues…..
 Work and Path
(curve 1-2)

Compression Expansion
• If the gas is compressed from • If the gas is expanded from
volume 𝑉1 to volume 𝑉2 , then volume 𝑉1 to volume 𝑉2 , then

𝑉2 < 𝑉1 , and 𝑉2 > 𝑉1 , and

𝑙𝑛 𝑉2 𝑉1 < 0 𝑙𝑛 𝑉2 𝑉1 > 0
• The work done on the gas is • The work done by the gas is
positive negative
continues…..
 Work and Path
(curve 1-3-2)
• The path 1-3-2 (cf. Fig.9) consists of an
• isochoric (constant volume) decrease of pressure 1-3, followed by an
• Isobaric (constant pressure) expansion 3–2
• The work done on the gas is simply
(19)
𝑊 = −𝑃2 𝑉2 − 𝑉1
• The work represented by Eq. (19) is different from that for the
isothermal expansion, i.e., Eq. (18)
• The relationship between work done and area on a PV diagram is
especially useful for a reversible cycle that begins and ends at the
same point.
continues…..
 Work and Path
Path 1-3-2-1 Path 1-2-3-1
• The work done in the path 1-3 • The work done in the path 3-1
𝑊 = −𝑃𝑑𝑉 = 0 𝑊 = −𝑃𝑑𝑉 = 0
• The work done in the path 3-2 • The work done in the path 2-3
𝑊 = −𝑃𝑑𝑉 = −𝑃2 𝑉2 − 𝑉1 𝑊 = −𝑃𝑑𝑉 = −𝑃2 𝑉1 − 𝑉2
= 𝑛𝑒𝑔𝑎𝑡𝑖𝑣𝑒 𝑤𝑜𝑟𝑘 = 𝑝𝑜𝑠𝑖𝑡𝑖𝑣𝑒 𝑤𝑜𝑟𝑘
• The work done in the path 2-1 • The work done in the path 1-2
𝑉1 𝑉2
1 𝑉1 1 𝑉2
𝑊 = −𝑛𝑅𝑇 𝑑𝑉 = −𝑛𝑅𝑇𝑙𝑛 𝑊 = −𝑛𝑅𝑇 𝑑𝑉 = −𝑛𝑅𝑇𝑙𝑛
𝑉2 𝑉 𝑉2 𝑉1 𝑉 𝑉1
= 𝑝𝑜𝑠𝑖𝑡𝑖𝑣𝑒 𝑤𝑜𝑟𝑘 = 𝑛𝑒𝑔𝑎𝑡𝑖𝑣𝑒 𝑤𝑜𝑟𝑘
• Because the positive work is greater, the • Because the negative work is greater, the
net work for the entire cycle is positive. net work for the entire cycle is negative.

 In general, work is path dependent and cannot be expressed simply as the difference
between the two end point values of some state function
 Example of the Calculation of Work
• As an example of a reversible process, consider changing the state of a compressible fluid from
(𝑃1 , 𝑇1 ) to (𝑃2 , 𝑇2 ). Calculate the work done in this process
• The infinitesimal work done in part of the process is –P dV , so it is necessary to find dV.
• Referring slide number 16, we can write 𝑉 = 𝑓 𝑃, 𝑇 , and by chain rule, we can write
𝜕𝑉 𝜕𝑉
𝑑𝑉 = 𝑑𝑃 + 𝑑𝑇 (20)
𝜕𝑃 𝑇 𝜕𝑇 𝑃
• Using Eq. (11) and Eq. (12), Eq. (20) can be expressed as
𝑉
𝑑𝑉 = − 𝑑𝑃 + 𝛽𝑉𝑑𝑇
𝐵
• The work done can be expressed as
𝑃𝑉
𝑑𝑊 = −𝑃𝑑𝑉 = 𝑑𝑃 − 𝑃𝛽𝑉𝑑𝑇, and
𝑃2 𝐵 𝑇2
𝑃𝑉
𝑊= 𝑑𝑃 − 𝑃𝛽𝑉𝑑𝑇
𝑃1 𝐵 𝑇1
 Questions
9) 10 moles of an ideal gas are compressed isothermally and reversibly
from a pressure of 1 atm to 10 atm at 300 K.
• (a) How much work is done on the gas?
• (b) How much work is done on the gas in the reverse process?
10) An ideal gas undergoes the following reversible cycle:
(i) an isobaric expansion from the state (P1,V1) to the state (P1,V2)
(ii) an isochoric reduction in pressure to the state (P2,V2)
(iii) an isobaric reduction in volume to the state (P2,V1)
(iv) an isochoric increase in pressure back to the original state (P1,V1)
• (a) What work is done on the gas in this cycle?
• (b) If 𝑃1 = 3.0 atm, 𝑃2 = 1.0 atm, 𝑉1 = 1.0 L and 𝑉2 = 2.0 L, how much work is done on
the gas in traversing the cycle 100 times?

continues…..
 Questions
11) During a reversible adiabatic expansion of an ideal gas, the pressure and
volume at any moment are related by 𝑃𝑉 𝛾 = 𝑐 where c and 𝛾 are constants.
Show that the work done by the gas in expanding from a state (𝑃1 , 𝑉1 ) to a state
(𝑃2 , 𝑉2 ) is
𝑃1 𝑉1 − 𝑃2 𝑉2
𝑊=
𝛾−1
12) Show that the work done by an ideal gas during the quasi-static, isothermal
expansion from the initial pressure 𝑃𝑖 a final pressure 𝑃𝑓 is given by
𝑃𝑓
𝑊 = 𝑛𝑅𝑇𝑙𝑛
𝑃𝑖
• Calculate the work done when the pressure of 1 mol of an ideal gas is decreased quasi-
statically from 20 to 1 atm, the temperature remaining constant at 20𝑜 C (𝑅 =
8.31 𝐽 𝑚𝑜𝑙 ∙ deg)
 First Law of Thermodynamics
• The first law of thermodynamics is a statement of conservation of
energy

• It gives the precise relationship between

• concept of work and,
• the new concepts of internal energy and heat

• Let us begin by approaching the first law historically

• The theory of Thompson and Joule that,
• Led the definition of the First Law of Thermodynamics
 Benjamin Thompson Theory
• Benjamin Thompson worked in the arsenal in Munich supervising the
boring of cannons when he noticed that great heat was produced in that
process, as measured by the temperature rise in the cooling water
• Further, when he used a blunt boring tool, he found that he could even boil
the water, with the supply of heat being apparently inexhaustible
• He concluded that there is a direct relation between the work done and
the heat produced
• He founded the Royal Institution of Great Britain
• The precise relation between work and heat was established by James Joule some 50
years later in a series of experiments between 1840 and 1849
 James Joule Theory
• James Joule, a Manchester brewer,
constructed a tub containing a paddle
wheel that could be rotated by the
action of weights falling outside the
tub (cf.Fig.10)
• Water inside the tub could be stirred
(irreversibly because of turbulence),
raising its temperature between two
equilibrium states
• The walls of the tub were insulating,
so the work was performed under
adiabatic conditions Fig.10. A schematic representation of Joule’s
• This kind of work is called adiabatic work apparatus

continues…..
 James Joule Theory: Findings
• 4.2 kJ of work is required to raise the temperature of 1 kg of water through
1°Celsius
• This is known as the mechanical equivalent of heat J
• No matter how the adiabatic work was performed, it always required the
same amount of work to take the water system between the same two
equilibrium states
• Joule varied his adiabatic work by changing the weights and the number of drops
• The experimental findings are in the following statement of the first law of
thermodynamics:
• If a thermally isolated system is brought from one equilibrium state to another (by
adiabatic means only), the work necessary to achieve this change is independent of
the process used
 Work and Process
• There are infinite number of paths
(processes) by which system may
be transferred from an initial state
to a final state by the performance
of adiabatic work only
• The adiabatic work is same along
all such paths
• Although in general, work is path
dependent, there is a class of
processes where the work is path
Fig.11. Changing the state of a system from the initial state
independent-adiabatic work i to the final state f along three different adiabatic paths
 Internal Energy
• The adiabatic work expended in a process is path independent, depending only
on the end equilibrium points; this is true whether or not the process is reversible
• Therefore, there must exist a state function whose difference between the two
end points 2 and 1 is equal to the adiabatic work
• This state function is called the internal energy U
𝑊𝑎𝑑𝑖𝑎𝑏𝑎𝑡𝑖𝑐 = 𝑈2 − 𝑈1 (21)
• From a molecular viewpoint, the external work goes into increasing kinetic and potential
energies
• —those of the individual molecules that have kinetic energy because of their random motion
and potential energy because of their mutual attraction
• It is these molecular motions and relative positions that constitute the internal energy U
• In general, the internal energy will be a function of temperature and volume, so that we can
write 𝑈 = 𝑓 𝑇, 𝑉
 Heat
• If the system is not thermally isolated, then the work W done in taking the
system between a pair of equilibrium points depends on the path
• For a given change, ∆𝑈 = 𝑈2 − 𝑈1 is fixed, but W is not now equal to ΔU
• The difference between ΔU and W is called the heat Q
• Heat is exchange of energy between the system and the surroundings
because of their temperature difference
• There is a sign convention for heat, just as there is for work
• Heat Q is defined to be positive when it enters the system
• The direction of heat flow is always from higher to lower temperature
• An alternative definition of heat is the energy that flows spontaneously from an
object with higher temperature to an object with lower temperature.
 First Law of Thermodynamics
• The generalization of Eq. (21) is the important mathematical
statement of the first law:
(22)
∆𝑈 = 𝑊 + 𝑄
• The first law says that the internal energy can be increased either by
doing work on the system or by supplying heat to it
• It is true for all processes whether reversible or irreversible
• In differential form, the first law takes the form (23)
d𝑈 = 𝑑𝑊 + 𝑑𝑄
• For a reversible process, 𝑑𝑊 = −𝑃𝑑𝑉, then from Eq. (23), we get
𝑑𝑄 = 𝑑𝑈 + 𝑃𝑑𝑉 (24)
 Heat Capacity
• Suppose there is a process that allows heat Q
to flow into a system, changing it from one
equilibrium state to another with a
temperature difference ΔT, cf. Fig.12
• The heat capacity C of a system is defined as
the limiting ratio of the heat introduced
reversibly into the system divided by the
temperature rise
𝑄 𝑑𝑄
𝐶 = lim = (25)
∆𝑇→0 ∆𝑇 𝑑𝑇
• The specific heat c is the heat capacity per
unit mass
1 𝑑𝑄 (26)
𝑐=
𝑚 𝑑𝑇 𝑄
• Lower case c is used consistently for specific Fig.12. The heat capacity is lim
∆𝑇→0 ∆𝑇
heat, whether per unit mass, per mole, or
another definite quantity
 Heat capacity at constant volume, 𝑪𝑽
• Suppose the system is heated under conditions of constant volume,
such as a gas in a closed container
• For an infinitesimal isochoric reversible process, Eq. (24) gives

𝑑𝑄𝑉 = 𝑑𝑈, thus

𝑑𝑄𝑉 𝜕𝑈
𝐶𝑉 = = (27)
𝑑𝑇 𝜕𝑇 𝑉
 Heat capacity at constant Pressure, 𝑪𝑷
• Now suppose the system is heated at constant pressure. The heat
capacity at constant pressure is
𝑑𝑄𝑃 𝜕𝑄 (28)
𝐶𝑃 = =
𝑑𝑇 𝜕𝑇 𝑃
• where 𝑑𝑄𝑃 is the heat added reversibly and isobarically to produce the
temperature rise 𝑑𝑇
Or
𝑑𝑄𝑃 𝜕𝐻
𝐶𝑃 = = , how? (29)
𝑑𝑇 𝜕𝑇 𝑃
 Enthalpy
• Analogous to the result 𝑑𝑄𝑉 = 𝑑𝑈 for constant volume, one can obtain a
similar result for 𝑑𝑄𝑃 by defining a new state function, the enthalpy H, as
𝐻 = 𝑈 + 𝑃𝑉
• For infinitesimal change, Eq. (30) can be written as (30)
𝑑𝐻 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 = 𝑑𝑄 + 𝑉𝑑𝑃
• For isobaric process, 𝑑𝑃 = 0, which implies
(31)
𝑑𝐻 = 𝑑𝑄𝑃
• Using Eq. (28) and Eq. (31), we get
𝜕𝐻 (32)
𝐶𝑃 =
𝜕𝑇 𝑃
 Relationship between 𝑪𝑽 and 𝑪𝑷
• Adding heat can change the internal energy of gas. In general, the internal energy will be a function of
temperature and volume, so that we can write,
𝑈 = 𝑓 𝑇, 𝑉
Hence a small change in U can be related to changes in T and V by
𝜕𝑈 𝜕𝑈
𝑑𝑈 = 𝑑𝑇 + 𝑑𝑉 (33)
𝜕𝑇 𝑉
𝜕𝑉 𝑇
• Using Eq. (24) and Eq. (33), and dividing by 𝑑𝑇, we obtain
𝑑𝑄 𝜕𝑈 𝜕𝑈 𝑑𝑉
= + +𝑃 (34)
𝑑𝑇 𝜕𝑇 𝑉 𝜕𝑉 𝑇
𝑑𝑇
• At constant Pressure, Eq. (34) can be written as,
𝜕𝑄 𝜕𝑈 𝜕𝑈 𝜕𝑉 (35)
= + +𝑃
𝜕𝑇 𝑃 𝜕𝑇 𝑉
𝜕𝑉 𝑇
𝜕𝑇 𝑃
𝜕𝑈 𝜕𝑉
𝐶𝑃 = 𝐶𝑉 + +𝑃 (36)
𝜕𝑉 𝑇
𝜕𝑇 𝑃
 𝐶𝑃 − 𝐶𝑉
• Consider n moles of an ideal gas, and using first law of
thermodynamics, we get
(36)
𝑑𝑄 = 𝑑𝑈 + 𝑃𝑑𝑉 = 𝐶𝑉 𝑑𝑇 + 𝑃𝑑𝑉
• Dividing Eq. (36) by 𝑑𝑇, and partial derivative at constant P could be
written as
𝜕𝑄 𝜕𝑉 (37)
= 𝐶𝑉 + 𝑃
𝜕𝑇 𝑃 𝜕𝑇 𝑃
𝜕𝑉
• Calculating using the relation 𝑃𝑉 = 𝑛𝑅𝑇, we would obtain
𝜕𝑇 𝑃
(38)
𝐶𝑃 = 𝐶𝑉 + 𝑛𝑅
 The Equation of Adiabatic Process
• Since for a reversible adiabatic process, the expression of first law of
thermodynamics can be written as
𝑛𝑅𝑇
𝑑𝑄 = 𝑑𝑈 + 𝑃𝑑𝑉 = 𝐶𝑉 𝑑𝑇 + 𝑃𝑑𝑉 = 0 = 𝐶𝑉 𝑑𝑇 + 𝑑𝑉, Or
𝑉
𝑑𝑇 𝑛𝑅
0 = 𝐶𝑉 + 𝑑𝑉 (39)
𝑇 𝑉
Integrating Eq.(39), and rearranging the terms, we would obtain
𝑛𝑅
𝑙𝑛𝑇 + 𝑙𝑛𝑉 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 (40)
𝐶𝑉
𝑛𝑅
• Utilizing Eq. (38), = 𝛾 − 1, 𝐶𝑃 𝐶𝑉 = 𝛾 , and 𝛾 is called 𝑎𝑑𝑖𝑎𝑏𝑎𝑡𝑖𝑐 𝑒𝑥𝑝𝑜𝑛𝑒𝑛𝑡,
𝐶𝑉
Eq. (40) can be written as,
𝑇𝑉 𝛾−1 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡, Or (41)
𝑃𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
 Adiabat Vs. Isotherm
• An adiabat is the curve that
describes an adiabatic process
• The adiabat for an ideal gas has
a slope 𝛾 times that for the
isotherm at each point on the PV
diagram
• The result of the slide 64, Eq.
(38) shows that 𝛾 > 1, because
𝑛𝑅 is a positive number, and so
the adiabat has the steeper
slope. This is shown in Fig.13.
Fig.13. The adiabat for an ideal gas
 Second Law of Thermodynamics
• The first law of thermodynamics says that, in any process, energy is
conserved. Energy may be converted from one form to another, but the
total amount of energy is unchanged
• The second law of thermodynamics imposes limits on the efficiency of
processes that convert heat into work, such as in a steam engine or internal
combustion engine
• It allows for the definition of a thermodynamic temperature scale, which is
independent of the nature of the thermometric substance.
• The second law also leads to the concept of entropy, which is related both
to bulk processes and to the microscopic arrangements within a system
• Before considering the second law, it is useful to discuss Carnot cycles,
which are central to the discussion.
 Carnot Cycles
• French Engineer Sadi Carnot was a French Engineer, who in 1824
published an influential paper on how work could be produced from
sources of heat
• Carnot realized, since any return to thermal equilibrium could be used
to produce work, any return to equilibrium without the production of
this work must be considered a loss
• Thus, any temperature difference may be utilized in the production of work,
or it may be dissipated wastefully in a spontaneous flow of heat
 Carnot Engine cycle
• The ideal gas is taken through the four-
step reversible cycle abcda (2 isotherms
and 2 adiabats), as shown in Fig.14
• The first step ab is an isotherm at
temperature 𝑇1 , and to maintain constant
temperature heat 𝑄1 enters from a heat
reservoir at 𝑇1
• Step cd is an isotherm at a lower
temperature 𝑇2 , where heat 𝑄1 is
rejected to another reservoir at that
temperature.
• The second and fourth steps (bc and da)
are adiabats
• The net work W done in the cycle is the
area enclosed by abcda Fig.14. Carnot cycle for an ideal gas

continues…..
 Carnot Engine cycle: Important Points
• A Carnot engine operates between only two reservoirs and that it is
reversible
• Also, if a working substance is chosen other than an ideal gas, then
the shape of the Carnot cycle is different than the one depicted in
Fig.13., because
• the equations for the adiabats and isotherms are no longer 𝑃𝑉 𝛾 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
and 𝑃𝑉 = 𝑛𝑅𝑇, respectively
• The Carnot engine cycles described is a specific example of a general
class of engines called heat engines
• A heat engine is an engine that uses the flow of heat from a higher-
temperature reservoir 𝑇1 to a lower-temperature reservoir 𝑇2 to do work.
 Efficiency of Carnot Engine
• Any heat engine E may be represented by the
schematic diagram in Fig.15., where the heat
supplied is 𝑄1 and the heat rejected is 𝑄2 , and
• W is the work done by the engine
• The arrow around the edge of the block
depicting the engine indicates that the engine
works in a cycle
• To quantify the notion of engine efficiency,
consider it to be a ratio of
• “what you get out to what you put in”
• Therefore, the efficiency 𝜂 is expressed as
𝑊
𝜂= (42)
𝑄1
• Note that efficiency 𝜂 is a dimensionless
quantity that must be less than 1, because
the heat 𝑄2 expelled to the cold reservoir is Fig.15. Schematic representation
not available to do work, and therefore
𝑊 < 𝑄1 , efficiency below 100% of an engine working in a cycle

continues…..
 Efficiency of Carnot Engine
• Applying the first law to the working substance in the engine
∆𝑈 = 𝑄1 − 𝑄2 − 𝑊
(43)
• Because the process is cyclic, the change of internal energy (a state function) in going
round the cycle is zero, i.e., ∆𝑈 = 0, implying
𝑊 = 𝑄1 − 𝑄2 (44)
• Therefore, the engine efficiency is
𝑊 𝑄1 − 𝑄2 𝑄2
𝜂= = = 1 − , 𝑂𝑟 (45)
𝑄1 𝑄1 𝑄1
𝑇2 (46)
𝜂 =1− how?
𝑇1
• It appears that the strategy for making a more efficient engine is to make the ratio
𝑄2 𝑄1 as small as possible
• The subscript 1 and 2 in Q and T are also read as h and l, respectively, i.e., ℎ →
high 𝑎𝑛𝑑 𝑙 → low in some of the text books
 Statements of Thermodynamics
• There are two statements of the second law of thermodynamics that are
both based on general experience and observations about how real
engines work
• They were each formulated in the 1850s by Clausius (Rudolf Clausius) and
Kelvin (William Thomson), but the latter was subsequently modified by
Planck
• Clausius’ statement of the second law of thermodynamics: “No process is possible
whose sole result is the transfer of heat from a colder to a hotter body.”
• Kelvin-Plank’s or simply Kelvin’s statement of the second law of thermodynamics:
“No process is possible whose sole result is the complete conversion of heat into
work.”
• Besides, the two statements are equivalent
Schematic Kelvin–Planck and Clausius
statement

Fig.16. Schematic representation of (a) Kelvin–Planck statement and (b) Clausius statement
Equivalence of Kelvin and Clausius statements
• The two statements of the second law of thermodynamics are shown
to be equivalent by showing that the falsity of each implies the falsity
of the other. This can be done in two ways:
• We first prove the proposition that if a system violates Kelvin’s statement of
the second law of thermodynamics, it violates Clausius’ statement of the
second law of thermodynamics
• If a system violates Clausius’ statement of the second law of thermodynamics,
it violates Kelvin’ statement of the second law of thermodynamics.

continues…..
 The Kelvin statement is untrue
• This means that one can have an engine E
that takes 𝑄1 from a hot body and delivers
work 𝑊 = 𝑄1 in one cycle
• Let this engine drive a refrigerator R as shown in
Fig.17(a)
• Suppose the refrigerator extracts heat 𝑄2 from
the cold body
• Then the heat delivered by it to the hot body is
𝑄2 + 𝑊 or 𝑄1 + 𝑄2
• It is useful to regard the engine and the
refrigerator as the composite engine enclosed
by the dashed line as shown in Fig.17(b)
• This composite engine (strictly a refrigerator)
extracts 𝑄2 from the cold body and delivers a net
amount of heat 𝑄2 + 𝑄1 − 𝑄1 = 𝑄2 to the hot
body, but no work is done
• Hence, there is a violation of the Clausius Fig.17. If the Kelvin statement of the second law is false,
statement this implies that the Clausius statement is also false

continues…..
 The Clausius statement is untrue
• This means that you can have a refrigerator
that extracts heat 𝑄2 from a cold body and
delivers the same heat 𝑄2 to a hot body in
one cycle, with no work having to be done
• Let an engine operate between the same two
bodies
• Adjust the size of its working cycle so that in one
cycle it extracts heat 𝑄1 from the hot body, gives
up the same heat 𝑄2 to the cold body as was
extracted by the refrigerator, and so delivers the
work 𝑊 = 𝑄1 − 𝑄2 , refer Fig.18(a)
• The engine and the refrigerator may be
regarded as the composite engine enclosed
by the dashed line, as shown in Fig.18(b)
• which takes in heat 𝑄1 − 𝑄2 from the hot body
and delivers the same amount of work Fig.18. If the Clausius statement of the second law is false,
• Hence, there is a violation of the Kelvin this implies that the Kelvin statement is also false
statement
 Carnot’s Theorem
• No engine operating between two reservoirs can be more efficient
than a Carnot engine operating between those same two reservoirs
Or
• Of all the heat engines working between two given temperatures,
none is more efficient than a Carnot engine
 Proof of Carnot’s theorem
• To prove this, imagine that such a
hypothetical′ engine E′ does exist with an
efficiency 𝜂 larger than the Carnot efficiency
𝜂𝑐
• Refer Fig.19(a), this engine extracts heat 𝑄1′
from the hot reservoir,
′
performs
′ ′
work W′, and
delivers heat 𝑄2 = 𝑄1 − 𝑊 to the cold
reservoir
• Now operate a Carnot engine, denoted by C
and with efficiency 𝜂𝑐 , between the same two
reservoirs
• The Carnot engine extracts heat 𝑄1 , expels
heat 𝑄2 , and delivers work 𝑊
• Adjust the size of the cycle to make the Fig.19. Arrangement used to prove Carnot’s theorem
Carnot engine perform the same amount of
work as the hypothetical engine E′, implying
𝑊 ′ = 𝑊 = 𝑄1′ − 𝑄2′ = 𝑄1 − 𝑄2 (47)

continues…..
 Proof of Carnot’s theorem
• Because the hypothetical engine is assumed to be more efficient than the Carnot engine,
𝑊′ 𝑊
>
𝑄1′ 𝑄1
Since 𝑊 ′ = 𝑊, we would get (47)
′
𝑄1 > 𝑄1
• A Carnot engine is a reversible engine, so it may be driven backward as a refrigerator as shown in
Fig.19(b)
• The hypothetical engine and the Carnot refrigerator together act as a composite device, shown by
the dashed line, which extracts positive heat
𝑄2 − 𝑄2′ = 𝑄1 − 𝑊 − 𝑄1′ − 𝑊 = 𝑄1 − 𝑄1′
from the cold reservoir and delivers the same heat to the hot reservoir with no external work being required (48)
• This means that there is a violation of the Clausius statement
• Therefore the engine 𝐸 ′ cannot exist, and the original assumption 𝜂′ > 𝜂𝑐 is incorrect
• It is concluded that, for any real engine 𝜂𝑐 ≥ 𝜂
 Corollary to Carnot’s Theorem
 All Carnot engines operating between the
same two reservoirs have the same
efficiency
• To prove this statement, imagine two Carnot
engines C and C′ operating between the same
two reservoirs, and let the size of the working
cycles be adjusted so that they each deliver
the same amount of work
• Let C run C′ backward as in as shown in Fig.20,
then from Carnot’s Theorem
𝜂𝐶 ′ > 𝜂𝐶 (49)
• If C′ now runs C backward, then
𝜂𝐶 > 𝜂𝐶 ′ (50)
Fig.20. Arrangement used to prove that all Carnot
• Therefore, engines operating between the same two reservoirs
𝜂𝐶 = 𝜂𝐶 ′ (51)
have the same efficiency
which proves the assertion
 The Thermodynamic Temperature Scale
• The efficiency of a Carnot engine operating between the two
reservoirs is independent of the nature of the working substance and
can depend only on the temperatures of the reservoirs
• This gives a means of defining a temperature scale that is
independent of any particular material
• Let us discuss this scale through
• Carnot Engine
• Ideal gas scale

continues…..
 Temperature scale from Carnot Engines
• It defines the thermodynamic temperature 𝑇 so that 𝑇1 and 𝑇2 for the
two reservoirs in a Carnot engine are related as
𝑇1 − 𝑇2 𝑇2
𝜂𝑐 = =1− (52)
𝑇1 𝑇1
• Comparing Eq. (52) with Eq. (45), we would obtain
𝑇2 𝑄2
= (53)
𝑇1 𝑄1
• Eq. (53)gives a sensible definition for a scale of temperature
• Let us explore how?

continues…..
 Temperature scale from Carnot Engines
• Refer Fig.21, Carnot Engine 𝐶12 and 𝐶23 operate
between the temperatures 𝑇1 − 𝑇2 and 𝑇2 − 𝑇3 ,
respectively
• Thus we can write
𝑇1 𝑄1
= (54)
𝑇2 𝑄2
𝑇2 𝑄2
= (55)
𝑇3 𝑄3
• Multiplying Eq. (53) and Eq. (55) we can deduce
𝑇1 𝑄1
= (56)
𝑇3 𝑄3
• Eq. (56) infers that 𝐶12 and 𝐶23 are working
together as Engine 𝐶13
• It follows that, by taking a whole series of Carnot
engines, any range of temperatures may be
defined in a self-consistent way
• The thermodynamic scale of temperature will now be
shown to be identical to the familiar ideal gas scale

Fig.21. Thermodynamic temperature scale illustration

 Equivalence of Thermodynamic and Ideal gas
Scales
• Let 𝑇𝑔 and 𝑇 refers to the gas scale and
thermodynamic temperature scale, respectively
• The isotherms are represented as 𝑇𝑔1 and 𝑇𝑔2
• According to first law of thermodynamics for an
isothermal reversible process
𝑑𝑈 = 𝑑𝑄 − 𝑃𝑑𝑉 = 0, 𝑤ℎ𝑖𝑐ℎ 𝑖𝑚𝑝𝑙𝑖𝑒𝑠
𝑐
𝑑𝑉 𝑉𝑐
𝑄1 = 𝑛𝑅𝑇𝑔1 = 𝑛𝑅 𝑇𝑔1 𝑙𝑛 (57)
𝑏 𝑉 𝑉𝑏
and, 𝑄1 is positive for 𝑉𝑏 > 𝑉𝑐 , heat flowing “in”
• Similarly, 𝑄2 is expressed as,
𝑉𝑎 (58)
𝑄2 = −𝑛𝑅𝑇𝑔2 𝑙𝑛
𝑉𝑑
Fig.22. A Carnot cycle with an ideal gas
and, 𝑄2 is negative for 𝑉𝑑 > 𝑉𝑎 , heat flowing “out” as the working substance. This figure is
used to show that the ideal gas scale
temperature is identical to the
thermodynamic temperature T continues…..
 Equivalence of Thermodynamic and Ideal gas
Scales
• Dividing Eq. (57) by Eq. (58), we get
𝑄1 𝑇1 𝑇𝑔1 𝑉𝑐 𝑉𝑑
= = 𝑙𝑛 𝑙𝑛 (59)
𝑄2 𝑇2 𝑇𝑔2 𝑉𝑏 𝑉𝑎
• But ab and cd are adiabats where 𝑇𝑔 𝑉 𝛾−1 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡, so
𝛾−1 𝛾−1
𝑇𝑔1 𝑉𝑐 = 𝑇𝑔2 𝑉𝑑 (𝑐𝑑 adiabat) (60)
𝛾−1 𝛾−1
𝑇𝑔2 𝑉𝑎 = 𝑇𝑔1 𝑉𝑏 (𝑎𝑏 adiabat) (61)
• Dividing Eq. (60) by Eq. (61), we obtain
𝑉𝑐 𝑉𝑑
= (62)
𝑉𝑏 𝑉𝑎
• From Eq. (59) and Eq.(62), we can deduce
𝑇1 𝑇𝑔1
= (63)
𝑇2 𝑇𝑔2
And Eq. (63) implies
𝑇𝑔 ≡ 𝑇 (64)
 For Carnot’s Engine Efficiency to be 100%?
• It is interesting to note that the Carnot engine’s efficiency would be 100%
were it possible to obtain a lower temperature reservoir at absolute zero.
However, this is forbidden by the third law
• One might argue then that a good strategy for increasing efficiency would
be to use a refrigeration system to create a low-temperature reservoir with
much less than ambient temperature, say 100 K or lower
• The counter-argument against this strategy is that there is an energy cost
to refrigerate, a cost that increases as refrigeration temperature gets lower
• This offsets any gain obtained by increasing a heat engine’s theoretical
efficiency
• Let us investigate the Refrigerator concept
 Refrigerator and Coefficient of Performance
(COP)
• Carnot engine working in backward direction acts as a refrigerator
• In keeping with the concept of efficiency as a ratio of effective output
to input, the “efficiency” 𝜂𝐶𝑅 of a refrigerator is the heat extracted
from the cold reservoir divided by the work input
• So as not to confuse this with the efficiency of a heat engine, it is
customary to drop the word efficiency and instead refer to 𝜂𝐶𝑅 as the
coefficient of performance, or simply COP
• The COP is simply a measure of how effectively the input energy W
moves thermal energy from the cold reservoir at 𝑇2 to the hot
reservoir at 𝑇1
 Refrigerator and Coefficient of Performance
(COP)
• For a Carnot refrigerator
𝑅
𝑄2 𝑄2 𝑇2
𝜂𝐶 = = = (65)
𝑊 𝑄1 − 𝑄2 𝑇1 − 𝑇2
• In this case W is the energy
input into the device, normally
electrical energy for a household
refrigerator or air conditioner
• Commercially produced
refrigerators now typically come
with a COP rating posted in their
specifications
Fig.23. A Carnot refrigerator
continues…..
 COP Value
• A household refrigerator in a 20°C room (293 K) might maintain a
refrigerator compartment at 3°C (276 K)
• For this system the Carnot model predicts a maximum COP 𝜂𝐶𝑅 of
about 16
• However, for the freezer compartment maintained at −18°C (255 K),
the maximum COP is only about 6.7
• Real household refrigerators have coefficients of performance of
about 4 or 5, which as expected is less than the theoretical maximum
• Notice that the theoretical COP of any refrigerator drops as the
temperature difference increases