CHAPTER TWELVE

THERMODYNAMICS

12.1 INTRODUCTION
In previous chapter we have studied thermal properties of
matter. In this chapter we shall study laws that govern
thermal energy. We shall study the processes where work is
12.1 Introduction
converted into heat and vice versa. In winter, when we rub
12.2 Thermal equilibrium our palms together, we feel warmer; here work done in rubbing
12.3 Zeroth law of produces the ‘heat’. Conversely, in a steam engine, the ‘heat’
Thermodynamics of the steam is used to do useful work in moving the pistons,
12.4 Heat, internal energy and which in turn rotate the wheels of the train.
work In physics, we need to define the notions of heat,
12.5 First law of temperature, work, etc. more carefully. Historically, it took a
thermodynamics long time to arrive at the proper concept of ‘heat’. Before the
12.6 Specific heat capacity modern picture, heat was regarded as a fine invisible fluid
12.7 Thermodynamic state filling in the pores of a substance. On contact between a hot
variables and equation of body and a cold body, the fluid (called caloric) flowed from
state the colder to the hotter body ! This is similar to what happens
12.8 Thermodynamic processes when a horizontal pipe connects two tanks containing water
12.9 Heat engines up to different heights. The flow continues until the levels of
12.10 Refrigerators and heat water in the two tanks are the same. Likewise, in the ‘caloric’
pumps picture of heat, heat flows until the ‘caloric levels’ (i.e., the
12.11 Second law of temperatures) equalise.
thermodynamics In time, the picture of heat as a fluid was discarded in
12.12 Reversible and irreversible favour of the modern concept of heat as a form of energy. An
processes important experiment in this connection was due to Benjamin
12.13 Carnot engine Thomson (also known as Count Rumford) in 1798. He
observed that boring of a brass cannon generated a lot of
Summary
heat, indeed enough to boil water. More significantly, the
Points to ponder
amount of heat produced depended on the work done (by the
Exercises
horses employed for turning the drill) but not on the
sharpness of the drill. In the caloric picture, a sharper drill
would scoop out more heat fluid from the pores; but this
was not observed. A most natural explanation of the
observations was that heat was a form of energy and the
experiment demonstrated conversion of energy from one form
to another–from work to heat.
THERMODYNAMICS 299

Thermodynamics is the branch of physics that in a different context : we say the state of a system
deals with the concepts of heat and temperature is an equilibrium state if the macroscopic
and the inter-conversion of heat and other forms variables that characterise the system do not
of energy. Thermodynamics is a macroscopic change in time. For example, a gas inside a closed
science. It deals with bulk systems and does not rigid container, completely insulated from its
go into the molecular constitution of matter. In surroundings, with fixed values of pressure,
fact, its concepts and laws were formulated in the volume, temperature, mass and composition that
nineteenth century before the molecular picture do not change with time, is in a state of
of matter was firmly established. Thermodynamic thermodynamic equilibrium.
description involves relatively few macroscopic In general, whether or not a system is in a state
variables of the system, which are suggested by of equilibrium depends on the surroundings and
common sense and can be usually measured the nature of the wall that separates the system
directly. A microscopic description of a gas, for from the surroundings. Consider two gases A and
example, would involve specifying the co-ordinates B occupying two different containers. We know
and velocities of the huge number of molecules experimentally that pressure and volume of a
constituting the gas. The description in kinetic given mass of gas can be chosen to be its two
theory of gases is not so detailed but it does involve independent variables. Let the pressure and
molecular distribution of velocities. volume of the gases be (PA, VA) and (PB, VB)
Thermodynamic description of a gas, on the other respectively. Suppose first that the two systems
hand, avoids the molecular description altogether. are put in proximity but are separated by an
Instead, the state of a gas in thermodynamics is adiabatic wall – an insulating wall (can be
specified by macroscopic variables such as movable) that does not allow flow of energy (heat)
pressure, volume, temperature, mass and from one to another. The systems are insulated
composition that are felt by our sense perceptions from the rest of the surroundings also by similar
and are measurable*. adiabatic walls. The situation is shown
The distinction between mechanics and schematically in Fig. 12.1 (a). In this case, it is
thermodynamics is worth bearing in mind. In found that any possible pair of values (PA, VA) will
mechanics, our interest is in the motion of particles be in equilibrium with any possible pair of values
or bodies under the action of forces and torques. (PB, VB ). Next, suppose that the adiabatic wall is
Thermodynamics is not concerned with the replaced by a diathermic wall – a conducting wall
motion of the system as a whole. It is concerned that allows energy flow (heat) from one to another.
with the internal macroscopic state of the body. It is then found that the macroscopic variables of
When a bullet is fired from a gun, what changes the systems A and B change spontaneously until
is the mechanical state of the bullet (its kinetic both the systems attain equilibrium states. After
energy, in particular), not its temperature. When that there is no change in their states. The
the bullet pierces a wood and stops, the kinetic situation is shown in Fig. 12.1(b). The pressure
energy of the bullet gets converted into heat,
and volume variables of the two gases change to
changing the temperature of the bullet and the
(PB ′ , VB ′ ) and (PA ′ , VA ′ ) such that the new states
surrounding layers of wood. Temperature is
of A and B are in equilibrium with each other**.
related to the energy of the internal (disordered)
There is no more energy flow from one to another.
motion of the bullet, not to the motion of the bullet
We then say that the system A is in thermal
as a whole.
equilibrium with the system B.
12.2 THERMAL EQUILIBRIUM What characterises the situation of thermal
Equilibrium in mechanics means that the net equilibrium between two systems ? You can guess
external force and torque on a system are zero. the answer from your experience. In thermal
The term ‘equilibrium’ in thermodynamics appears equilibrium, the temperatures of the two systems

* Thermodynamics may also involve other variables that are not so obvious to our senses e.g. entropy, enthalpy,
etc., and they are all macroscopic variables.
** Both the variables need not change. It depends on the constraints. For instance, if the gases are in containers
of fixed volume, only the pressures of the gases would change to achieve thermal equilibrium.
300 PHYSICS

are equal. We shall see how does one arrive at The Zeroth Law clearly suggests that when two
the concept of temperature in thermodynamics? systems A and B, are in thermal equilibrium,
The Zeroth law of thermodynamics provides the there must be a physical quantity that has the
clue. same value for both. This thermodynamic
variable whose value is equal for two systems in
12.3 ZEROTH LAW OF THERMODYNAMICS
thermal equilibrium is called temperature (T ).
Imagine two systems A and B, separated by an Thus, if A and B are separately in equilibrium
adiabatic wall, while each is in contact with a third with C, TA = TC and TB = TC. This implies that
system C, via a conducting wall [Fig. 12.2(a)]. The TA = TB i.e. the systems A and B are also in
states of the systems (i.e., their macroscopic thermal equilibrium.
variables) will change until both A and B come to We have arrived at the concept of temperature
thermal equilibrium with C. After this is achieved, formally via the Zeroth Law. The next question
suppose that the adiabatic wall between A and B is : how to assign numerical values to
is replaced by a conducting wall and C is insulated temperatures of different bodies ? In other words,
from A and B by an adiabatic wall [Fig.12.2(b)]. It how do we construct a scale of temperature ?
is found that the states of A and B change no Thermometry deals with this basic question to
further i.e. they are found to be in thermal which we turn in the next section.
equilibrium with each other. This observation
forms the basis of the Zeroth Law of
Thermodynamics, which states that ‘two
systems in thermal equilibrium with a third
system separately are in thermal equilibrium
with each other’. R.H. Fowler formulated this
law in 1931 long after the first and second Laws
of thermodynamics were stated and so numbered.

(a)

(a)

(b)

Fig. 12.2 (a) Systems A and B are separated by an

adiabatic wall, while each is in contact
with a third system C via a conducting
wall. (b) The adiabatic wall between A
(b) and B is replaced by a conducting wall,
while C is insulated from A and B by an
Fig. 12.1 (a) Systems A and B (two gases) separated
by an adiabatic wall – an insulating wall adiabatic wall.
that does not allow flow of heat. (b) The
same systems A and B separated by a 12.4 HEAT, INTERNAL ENERGY AND WORK
diathermic wall – a conducting wall that
allows heat to flow from one to another. In The Zeroth Law of Thermodynamics led us to
this case, thermal equilibrium is attained the concept of temperature that agrees with our
in due course. commonsense notion. Temperature is a marker
THERMODYNAMICS 301

of the ‘hotness’ of a body. It determines the volume of the container); it also includes
direction of flow of heat when two bodies are rotational and vibrational motion of the
placed in thermal contact. Heat flows from the molecules (Fig. 12.3).
body at a higher temperature to the one at lower What are the ways of changing internal
temperature. The flow stops when the energy of a system ? Consider again, for
temperatures equalise; the two bodies are then simplicity, the system to be a certain mass of
in thermal equilibrium. We saw in some detail gas contained in a cylinder with a movable
how to construct temperature scales to assign piston as shown in Fig. 12.4. Experience shows
temperatures to different bodies. We now there are two ways of changing the state of the
describe the concepts of heat and other relevant gas (and hence its internal energy). One way is
quantities like internal energy and work. to put the cylinder in contact with a body at a
The concept of internal energy of a system is higher temperature than that of the gas. The
not difficult to understand. We know that every temperature difference will cause a flow of
bulk system consists of a large number of energy (heat) from the hotter body to the gas,
molecules. Internal energy is simply the sum of thus increasing the internal energy of the gas.
the kinetic energies and potential energies of The other way is to push the piston down i.e. to
these molecules. We remarked earlier that in do work on the system, which again results in
thermodynamics, the kinetic energy of the increasing the internal energy of the gas. Of
system, as a whole, is not relevant. Internal course, both these things could happen in the
energy is thus, the sum of molecular kinetic and reverse direction. With surroundings at a lower
potential energies in the frame of reference temperature, heat would flow from the gas to
relative to which the centre of mass of the system the surroundings. Likewise, the gas could push
is at rest. Thus, it includes only the (disordered) the piston up and do work on the surroundings.
energy associated with the random motion of In short, heat and work are two different modes
molecules of the system. We denote the internal of altering the state of a thermodynamic system
energy of a system by U. and changing its internal energy.
Though we have invoked the molecular The notion of heat should be carefully
picture to understand the meaning of internal distinguished from the notion of internal energy.
energy, as far as thermodynamics is concerned, Heat is certainly energy, but it is the energy in
U is simply a macroscopic variable of the system. transit. This is not just a play of words. The
The important thing about internal energy is distinction is of basic significance. The state of
that it depends only on the state of the system, a thermodynamic system is characterised by its
not on how that state was achieved. Internal internal energy, not heat. A statement like ‘a
energy U of a system is an example of a gas in a given state has a certain amount of
thermodynamic ‘state variable’ – its value heat’ is as meaningless as the statement that
depends only on the given state of the system, ‘a gas in a given state has a certain amount
not on history i.e. not on the ‘path’ taken to arrive of work’. In contrast, ‘a gas in a given state
has a certain amount of internal energy’ is a
at that state. Thus, the internal energy of a given
perfectly meaningful statement. Similarly, the
mass of gas depends on its state described by
statements ‘a certain amount of heat is
specific values of pressure, volume and
supplied to the system’ or ‘a certain amount
temperature. It does not depend on how this
of work was done by the system’ are perfectly
state of the gas came about. Pressure, volume,
meaningful.
temperature, and internal energy are
thermodynamic state variables of the system To summarise, heat and work in
(gas) (see section 12.7). If we neglect the small thermodynamics are not state variables. They
intermolecular forces in a gas, the internal are modes of energy transfer to a system
energy of a gas is just the sum of kinetic energies resulting in change in its internal energy,
associated with various random motions of its which, as already mentioned, is a state variable.
molecules. We will see in the next chapter that In ordinary language, we often confuse heat
in a gas this motion is not only translational with internal energy. The distinction between
(i.e. motion from one point to another in the them is sometimes ignored in elementary
302 PHYSICS

physics books. For proper understanding of transfer : heat and work. Let
thermodynamics, however, the distinction is ΔQ = Heat supplied to the system by the
crucial. surroundings
ΔW = Work done by the system on the
surroundings
ΔU = Change in internal energy of the system
The general principle of conservation of
energy then implies that
ΔQ = ΔU + ΔW (12.1)
i.e. the energy (ΔQ) supplied to the system goes
Fig. 12.3 (a) Internal energy U of a gas is the sum in partly to increase the internal energy of the
of the kinetic and potential energies of its system (ΔU) and the rest in work on the
molecules when the box is at rest. Kinetic
environment (ΔW). Equation (12.1) is known as
energy due to various types of motion
(translational, rotational, vibrational) is to the First Law of Thermodynamics. It is simply
be included in U. (b) If the same box is the general law of conservation of energy applied
moving as a whole with some velocity, to any system in which the energy transfer from
the kinetic energy of the box is not to be or to the surroundings is taken into account.
included in U. Let us put Eq. (12.1) in the alternative form

ΔQ – ΔW = ΔU (12.2)

Now, the system may go from an initial state

to the final state in a number of ways. For
example, to change the state of a gas from
(P1, V 1) to (P2, V 2), we can first change the
volume of the gas from V 1 to V2, keeping its
pressure constant i.e. we can first go the state
(P1, V2) and then change the pressure of the
gas from P1 to P2, keeping volume constant, to
take the gas to (P2, V 2). Alternatively, we can
first keep the volume constant and then keep
the pressure constant. Since U is a state
variable, ΔU depends only on the initial and
final states and not on the path taken by the
gas to go from one to the other. However, ΔQ
and ΔW will, in general, depend on the path
taken to go from the initial to final states. From
the First Law of Thermodynamics, Eq. (12.2),
Fig. 12.4 Heat and work are two distinct modes of it is clear that the combination ΔQ – ΔW, is
energy transfer to a system that results in however, path independent. This shows that
change in its internal energy. (a) Heat is if a system is taken through a process in which
energy transfer due to temperature ΔU = 0 (for example, isothermal expansion of
difference between the system and the an ideal gas, see section 12.8),
surroundings. (b) Work is energy transfer
brought about by means (e.g. moving the ΔQ = ΔW
piston by raising or lowering some weight
connected to it) that do not involve such a i.e., heat supplied to the system is used up
temperature difference. entirely by the system in doing work on the
12.5 FIRST LAW OF THERMODYNAMICS environment.
We have seen that the internal energy U of a If the system is a gas in a cylinder with a
system can change through two modes of energy movable piston, the gas in moving the piston
THERMODYNAMICS 303

does work. Since force is pressure times area, If the amount of substance is specified in
and area times displacement is volume, work terms of moles μ (instead of mass m in kg ), we
done by the system against a constant pressure can define heat capacity per mole of the
P is substance by

ΔW = P ΔV S 1 Q
C (12.6)
T
where ΔV is the change in volume of the gas.
Thus, for this case, Eq. (12.1) gives C is known as molar specific heat capacity of
the substance. Like s, C is independent of the
ΔQ = ΔU + P ΔV (12.3) amount of substance. C depends on the nature
of the substance, its temperature and the
As an application of Eq. (12.3), consider the conditions under which heat is supplied. The
change in internal energy for 1 g of water when unit of C is J mo1–1 K–1. As we shall see later (in
we go from its liquid to vapour phase. The connection with specific heat capacity of gases),
measured latent heat of water is 2256 J/g. i.e., additional conditions may be needed to define
for 1 g of water ΔQ = 2256 J. At atmospheric C or s. The idea in defining C is that simple
pressure, 1 g of water has a volume 1 cm3 in predictions can be made in regard to molar
liquid phase and 1671 cm3 in vapour phase. specific heat capacities.
Table 12.1 lists measured specific and molar
Therefore, heat capacities of solids at atmospheric pressure
ΔW =P (Vg –Vl ) = 1.013 ×105 ×(1670)×10–6 =169.2 J and ordinary room temperature.
We will see in Chapter 13 that predictions of
Equation (12.3) then gives specific heats of gases generally agree with
ΔU = 2256 – 169.2 = 2086.8 J experiment. We can use the same law of
equipartition of energy that we use there to
We see that most of the heat goes to increase predict molar specific heat capacities of solids.
the internal energy of water in transition from Consider a solid of N atoms, each vibrating
the liquid to the vapour phase. about its mean position. An oscillator in one
dimension has average energy of 2 × ½ kBT
12.6 SPECIFIC HEAT CAPACITY
= kBT. In three dimensions, the average energy
Suppose an amount of heat ΔQ supplied to a is 3 kBT. For a mole of a solid, the total energy is
substance changes its temperature from T to
U = 3 kBT × NA = 3 RT
T + ΔT. We define heat capacity of a substance
(see Chapter 11) to be Now, at constant pressure, ΔQ = ΔU + P ΔV ≅
ΔU, since for a solid ΔV is negligible. Therefore,
ΔQ
S= (12.4) ΔQ ΔU
ΔT C= = = 3R (12.7)
ΔT ΔT
We expect ΔQ and, therefore, heat capacity S
Table 12.1 Specific and molar heat capacities
to be proportional to the mass of the substance.
of some solids at room
Further, it could also depend on the temperature and atmospheric
temperature, i.e., a different amount of heat may pressure
be needed for a unit rise in temperature at
different temperatures. To define a constant
characteristic of the substance and
independent of its amount, we divide S by the
mass of the substance m in kg :
S 1 Q
s (12.5)
m m T
s is known as the specific heat capacity of the
substance. It depends on the nature of the
substance and its temperature. The unit of As Table 12.1 shows, the experimentally
specific heat capacity is J kg–1 K–1. measured values which generally agrees with
304 PHYSICS

predicted value 3R at ordinary temperatures. ideal gas, we have a simple relation.

(Carbon is an exception.) The agreement is
known to break down at low temperatures. Cp – Cv = R (12.8)
Specific heat capacity of water where C p and C v are molar specific heat
capacities of an ideal gas at constant pressure
The old unit of heat was calorie. One calorie
was earlier defined to be the amount of heat and volume respectively and R is the universal
required to raise the temperature of 1g of water gas constant. To prove the relation, we begin
by 1°C. With more precise measurements, it was with Eq. (12.3) for 1 mole of the gas :
found that the specific heat of water varies ΔQ = ΔU + P ΔV
slightly with temperature. Figure 12.5 shows
this variation in the temperature range 0 to If ΔQ is absorbed at constant volume, ΔV = 0
100 °C.
Q U U
Cv (12.9)
T v T v T

where the subscript v is dropped in the last

step, since U of an ideal gas depends only on
temperature. (The subscript denotes the
quantity kept fixed.) If, on the other hand, ΔQ
is absorbed at constant pressure,

Q U V
Cp P (12.10)
T p T p T p

Fig. 12.5 Variation of specific heat capacity of water The subscript p can be dropped from the
with temperature. first term since U of an ideal gas depends only
on T. Now, for a mole of an ideal gas
For a precise definition of calorie, it was,
therefore, necessary to specify the unit PV = RT
temperature interval. One calorie is defined
which gives
to be the amount of heat required to raise the
temperature of 1g of water from 14.5 °C to V
15.5 °C. Since heat is just a form of energy, P R (12.11)
T p
it is preferable to use the unit joule, J.
In SI units, the specific heat capacity of water Equations (12.9) to (12.11) give the desired
is 4186 J kg–1 K–1 i.e. 4.186 J g–1 K–1. The so relation, Eq. (12.8).
called mechanical equivalent of heat defined
as the amount of work needed to produce 12.7 THERMODYNAMIC STATE VARIABLES
1 cal of heat is in fact just a conversion factor AND EQUATION OF STATE
between two different units of energy : calorie Every equilibrium state of a thermodynamic
to joule. Since in SI units, we use the unit joule system is completely described by specific
for heat, work or any other form of energy, the values of some macroscopic variables, also
term mechanical equivalent is now called state variables. For example, an
superfluous and need not be used. equilibrium state of a gas is completely
As already remarked, the specific heat specified by the values of pressure, volume,
capacity depends on the process or the temperature, and mass (and composition if
conditions under which heat capacity transfer there is a mixture of gases). A thermodynamic
takes place. For gases, for example, we can system is not always in equilibrium. For example,
define two specific heats : specific heat a gas allowed to expand freely against vacuum
capacity at constant volume and specific is not an equilibrium state [Fig. 12.6(a)]. During
heat capacity at constant pressure. For an the rapid expansion, pressure of the gas may
THERMODYNAMICS 305

not be uniform throughout. Similarly, a mixture temperature do not. To decide which variable is
of gases undergoing an explosive chemical extensive and which intensive, think of a
reaction (e.g. a mixture of petrol vapour and relevant system in equilibrium, and imagine that
air when ignited by a spark) is not an it is divided into two equal parts. The variables
equilibrium state; again its temperature and that remain unchanged for each part are
pressure are not uniform [Fig. 12.6(b)]. intensive. The variables whose values get halved
Eventually, the gas attains a uniform in each part are extensive. It is easily seen, for
example, that internal energy U, volume V, total
temperature and pressure and comes to
mass M are extensive variables. Pressure P,
thermal and mechanical equilibrium with its
temperature T, and density ρ are intensive
surroundings.
variables. It is a good practice to check the
consistency of thermodynamic equations using
this classification of variables. For example, in
the equation
ΔQ = ΔU + P ΔV
quantities on both sides are extensive*. (The
product of an intensive variable like P and an
extensive quantity ΔV is extensive.)

12.8 THERMODYNAMIC PROCESSES

12.8.1 Quasi-static process
Consider a gas in thermal and mechanical
equilibrium with its surroundings. The pressure
of the gas in that case equals the external
Fig. 12.6 (a) The partition in the box is suddenly pressure and its temperature is the same as
removed leading to free expansion of the that of its surroundings. Suppose that the
gas. (b) A mixture of gases undergoing an external pressure is suddenly reduced (say by
explosive chemical reaction. In both lifting the weight on the movable piston in the
situations, the gas is not in equilibrium and
container). The piston will accelerate outward.
cannot be described by state variables.
During the process, the gas passes through
In short, thermodynamic state variables states that are not equilibrium states. The non-
describe equilibrium states of systems. The equilibrium states do not have well-defined
various state variables are not necessarily pressure and temperature. In the same way, if
independent. The connection between the state a finite temperature difference exists between
variables is called the equation of state. For the gas and its surroundings, there will be a
example, for an ideal gas, the equation of state rapid exchange of heat during which the gas
is the ideal gas relation will pass through non-equilibrium states. In
due course, the gas will settle to an equilibrium
P V = μR T state with well-defined temperature and
For a fixed amount of the gas i.e. given μ, there pressure equal to those of the surroundings. The
are thus, only two independent variables, say P free expansion of a gas in vacuum and a mixture
and V or T and V. The pressure-volume curve of gases undergoing an explosive chemical
for a fixed temperature is called an isotherm. reaction, mentioned in section 12.7 are also
Real gases may have more complicated examples where the system goes through non-
equations of state. equilibrium states.
The thermodynamic state variables are of two Non-equilibrium states of a system are difficult
kinds: extensive and intensive. Extensive to deal with. It is, therefore, convenient to
variables indicate the ‘size’ of the system. imagine an idealised process in which at every
Intensive variables such as pressure and stage the system is an equilibrium state. Such a

* As emphasised earlier, Q is not a state variable. However, ΔQ is clearly proportional to the total mass of
system and hence is extensive.
306 PHYSICS

process is, in principle, infinitely slow-hence the A process in which the temperature of the
name quasi-static (meaning nearly static). The system is kept fixed throughout is called an
system changes its variables (P, T, V ) so slowly isothermal process. The expansion of a gas in
that it remains in thermal and mechanical a metallic cylinder placed in a large reservoir of
equilibrium with its surroundings throughout. fixed temperature is an example of an isothermal
In a quasi-static process, at every stage, the process. (Heat transferred from the reservoir to
difference in the pressure of the system and the the system does not materially affect the
external pressure is infinitesimally small. The temperature of the reservoir, because of its very
same is true of the temperature difference large heat capacity.) In isobaric processes the
between the system and its surroundings. To pressure is constant while in isochoric
take a gas from the state (P, T ) to another state processes the volume is constant. Finally, if
(P ′ , T ′ ) via a quasi-static process, we change the system is insulated from the surroundings
the external pressure by a very small amount, and no heat flows between the system and the
surroundings, the process is adiabatic. The
allow the system to equalise its pressure with
definitions of these special processes are
that of the surroundings and continue the
summarised in Table. 12.2
process infinitely slowly until the system
achieves the pressure P ′ . Similarly, to change Table 12.2 Some special thermodynamic
the temperature, we introduce an infinitesimal processes
temperature difference between the system and
the surrounding reservoirs and by choosing
reservoirs of progressively different temperatures
T to T ′ , the system achieves the temperature T ′ .

We now consider these processes in some detail :

Isothermal process
For an isothermal process (T fixed), the ideal gas
equation gives
PV = constant
i.e., pressure of a given mass of gas varies inversely
as its volume. This is nothing but Boyle’s Law.
Suppose an ideal gas goes isothermally (at
temperature T ) from its initial state (P1, V1) to
Fig. 12.7 In a quasi-static process, the temperature the final state (P2, V 2). At any intermediate stage
of the surrounding reservoir and the with pressure P and volume change from V to
external pressure differ only infinitesimally V + ΔV (ΔV small)
from the temperature and pressure of the
system. ΔW = P Δ V
A quasi-static process is obviously a Taking (ΔV →0) and summing the quantity
hypothetical construct. In practice, processes ΔW over the entire process,
that are sufficiently slow and do not involve V2
accelerated motion of the piston, large W= P dV
temperature gradient, etc. are reasonably V1
approximation to an ideal quasi-static process.
V2
We shall from now on deal with quasi-static dV V2
= RT RT In
processes only, except when stated otherwise. V V1 (12.12)
V1
THERMODYNAMICS 307

where in the second step we have made use of We can calculate, as before, the work done in
the ideal gas equation PV = μ RT and taken the an adiabatic change of an ideal gas from the
constants out of the integral. For an ideal gas, state (P1, V1, T1) to the state (P2, V2, T2).
internal energy depends only on temperature.
V2
Thus, there is no change in the internal energy
W= P dV
of an ideal gas in an isothermal process. The
V1
First Law of Thermodynamics then implies that
heat supplied to the gas equals the work done
V2 – +1 V2
by the gas : Q = W. Note from Eq. (12.12) that dV V
= constant constant
for V2 > V1, W > 0; and for V2 < V1, W < 0. That V 1 V1
V1
is, in an isothermal expansion, the gas absorbs
heat and does work while in an isothermal
cons tant ⎡ 1 1 ⎤
compression, work is done on the gas by the = ×⎢ – ⎥ (12.15)
environment and heat is released. (1 – γ ) ⎢ V γ –1 V γ –1 ⎥
⎣ 2 1 ⎦
Adiabatic process From Eq. (12.34), the constant is P1V1γ or P2V2γ
In an adiabatic process, the system is insulated 1 P2V2 P1V1
from the surroundings and heat absorbed or W = 1 1
1– V2 V1
released is zero. From Eq. (12.1), we see that
work done by the gas results in decrease in its
1 R(T1 – T2 )
internal energy (and hence its temperature for = P2V2 P1V1 (12.16)
an ideal gas). We quote without proof (the result 1– –
that you will learn in higher courses) that for As expected, if work is done by the gas in an
an adiabatic process of an ideal gas. adiabatic process (W > 0), from Eq. (12.16),
P V γ = const (12.13) T2 < T1. On the other hand, if work is done on
where γ is the ratio of specific heats (ordinary the gas (W < 0), we get T 2 > T 1 i.e., the
or molar) at constant pressure and at constant temperature of the gas rises.
volume. Isochoric process
Cp
γ = In an isochoric process, V is constant. No work
Cv is done on or by the gas. From Eq. (12.1), the
Thus if an ideal gas undergoes a change in heat absorbed by the gas goes entirely to change
its state adiabatically from (P1, V1) to (P2, V2) : its internal energy and its temperature. The
γ γ change in temperature for a given amount of
P1 V1 = P2 V2 (12.14) heat is determined by the specific heat of the
Figure12.8 shows the P-V curves of an ideal gas at constant volume.
gas for two adiabatic processes connecting two
Isobaric process
isotherms.
In an isobaric process, P is fixed. Work done by
the gas is
W = P (V2 – V1) = μ R (T2 – T1) (12.17)
Since temperature changes, so does internal
energy. The heat absorbed goes partly to
increase internal energy and partly to do work.
The change in temperature for a given amount
of heat is determined by the specific heat of the
gas at constant pressure.
Cyclic process
In a cyclic process, the system returns to its
Fig. 12.8 P-V curves for isothermal and adiabatic initial state. Since internal energy is a state
processes of an ideal gas. variable, ΔU = 0 for a cyclic process. From
308 PHYSICS

Eq. (12.1), the total heat absorbed equals the and W is the work done on the environment in
work done by the system. a cycle. In a cycle, a certain amount of heat (Q2)
may also be rejected to the environment. Then,
12.9 HEAT ENGINES
according to the First Law of Thermodynamics,
Heat engine is a device by which a system is over one complete cycle,
made to undergo a cyclic process that results
W = Q1 – Q2 (12.19)
in conversion of heat to work.
(1) It consists of a working substance–the i.e.,
system. For example, a mixture of fuel Q
vapour and air in a gasoline or diesel engine η =1 − 2 (12.20)
Q1
or steam in a steam engine are the working For Q2 = 0, η = 1, i.e., the engine will have
substances. 100% efficiency in converting heat into work.
(2) The working substance goes through a cycle Note that the First Law of Thermodynamics i.e.,
consisting of several processes. In some of the energy conservation law does not rule out
these processes, it absorbs a total amount such an engine. But experience shows that
of heat Q1 from an external reservoir at some such an ideal engine with η= 1 is never possible,
high temperature T1. even if we can eliminate various kinds of losses
(3) In some other processes of the cycle, the associated with actual heat engines. It turns
working substance releases a total amount out that there is a fundamental limit on the
of heat Q2 to an external reservoir at some efficiency of a heat engine set by an independent
lower temperature T2. principle of nature, called the Second Law of
(4) The work done (W ) by the system in a cycle Thermodynamics (section 12.11).
is transferred to the environment via some The mechanism of conversion of heat into
arrangement (e.g. the working substance work varies for different heat engines. Basically,
may be in a cylinder with a moving piston
there are two ways : the system (say a gas or a
that transfers mechanical energy to the
mixture of gases) is heated by an external
wheels of a vehicle via a shaft).
furnace, as in a steam engine; or it is heated
The basic features of a heat engine are
internally by an exothermic chemical reaction
schematically represented in Fig. 12.9.
as in an internal combustion engine. The
various steps involved in a cycle also differ from
one engine to another. For the purpose of general
analysis, it is useful to conceptualise a heat
engine as having the following essential
ingredients.

Fig. 12.9 Schematic representation of a heat engine. 12.10 REFRIGERATORS AND HEAT PUMPS
The engine takes heat Q1 from a hot
A refrigerator is the reverse of a heat engine.
reservoir at temperature T1, releases heat
Q2 to a cold reservoir at temperature T2 Here the working substance extracts heat Q2
and delivers work W to the surroundings. from the cold reservoir at temperature T2, some
external work W is done on it and heat Q1 is
The cycle is repeated again and again to get released to the hot reservoir at temperature T1
useful work for some purpose. The discipline of (Fig. 12.10).
thermodynamics has its roots in the study of heat
engines. A basic question relates to the efficiency
of a heat engine. The efficiency (η) of a heat
engine is defined by
W
η= (12.18)
Q1
Fig. 12.10 Schematic representation of a refrigerator
where Q 1 is the heat input i.e., the heat or a heat pump, the reverse of a heat
absorbed by the system in one complete cycle engine.
THERMODYNAMICS 309

Pioneers of Thermodynamics

Lord Kelvin (William Thomson) (1824-1907), born in Belfast, Ireland, is

among the foremost British scientists of the nineteenth century. Thomson
played a key role in the development of the law of conservation of energy
suggested by the work of James Joule (1818-1889), Julius Mayer (1814-
1878) and Hermann Helmholtz (1821-1894). He collaborated with Joule
on the so-called Joule-Thomson effect : cooling of a gas when it expands
into vacuum. He introduced the notion of the absolute zero of temperature
and proposed the absolute temperature scale, now called the Kelvin scale
in his honour. From the work of Sadi Carnot (1796-1832), Thomson arrived
at a form of the Second Law of Thermodynamics. Thomson was a versatile
physicist, with notable contributions to electromagnetic theory and
hydrodynamics.
Rudolf Clausius (1822-1888), born in Poland, is generally regarded as
the discoverer of the Second Law of Thermodynamics. Based on the work
of Carnot and Thomson, Clausius arrived at the important notion of entropy
that led him to a fundamental version of the Second Law of
Thermodynamics that states that the entropy of an isolated system can
never decrease. Clausius also worked on the kinetic theory of gases and
obtained the first reliable estimates of molecular size, speed, mean free
path, etc.

A heat pump is the same as a refrigerator. where Q2 is the heat extracted from the cold
What term we use depends on the purpose of reservoir and W is the work done on the
the device. If the purpose is to cool a portion of system–the refrigerant. ( α for heat pump is
space, like the inside of a chamber, and higher defined as Q1/W) Note that while ηby definition
temperature reservoir is surrounding, we call can never exceed 1, α can be greater than 1.
the device a refrigerator; if the idea is to pump By energy conservation, the heat released to the
heat into a portion of space (the room in a hot reservoir is
building when the outside environment is cold),
Q1 = W + Q2
the device is called a heat pump.
In a refrigerator the working substance Q2
(usually, in gaseous form) goes through the i.e., Q1 – Q2 (12.22)
following steps : (a) sudden expansion of the gas In a heat engine, heat cannot be fully
from high to low pressure which cools it and converted to work; likewise a refrigerator cannot
converts it into a vapour-liquid mixture, (b) work without some external work done on the
absorption by the cold fluid of heat from the system, i.e., the coefficient of performance in Eq.
region to be cooled converting it into vapour, (c) (12.21) cannot be infinite.
heating up of the vapour due to external work
12.11 SECOND LAW OF THERMODYNAMICS
done on the system, and (d) release of heat by
the vapour to the surroundings, bringing it to The First Law of Thermodynamics is the principle
the initial state and completing the cycle. of conservation of energy. Common experience
The coefficient of performance ( α) of a shows that there are many conceivable
refrigerator is given by processes that are perfectly allowed by the First
Law and yet are never observed. For example,
Q2 nobody has ever seen a book lying on a table
(12.21)
W jumping to a height by itself. But such a thing
310 PHYSICS

would be possible if the principle of conservation bring both the system and surroundings to their
of energy were the only restriction. The table initial states with no other effect anywhere ?
could cool spontaneously, converting some of its Experience suggests that for most processes in
internal energy into an equal amount of nature this is not possible. The spontaneous
mechanical energy of the book, which would processes of nature are irreversible. Several
then hop to a height with potential energy equal examples can be cited. The base of a vessel on
to the mechanical energy it acquired. But this an oven is hotter than its other parts. When
never happens. Clearly, some additional basic the vessel is removed, heat is transferred from
principle of nature forbids the above, even the base to the other parts, bringing the vessel
though it satisfies the energy conservation to a uniform temperature (which in due course
principle. This principle, which disallows many cools to the temperature of the surroundings).
phenomena consistent with the First Law of The process cannot be reversed; a part of the
Thermodynamics is known as the Second Law vessel will not get cooler spontaneously and
of Thermodynamics. warm up the base. It will violate the Second Law
The Second Law of Thermodynamics gives a of Thermodynamics, if it did. The free expansion
fundamental limitation to the efficiency of a heat of a gas is irreversible. The combustion reaction
engine and the co-efficient of performance of a of a mixture of petrol and air ignited by a spark
refrigerator. In simple terms, it says that cannot be reversed. Cooking gas leaking from a
efficiency of a heat engine can never be unity. gas cylinder in the kitchen diffuses to the
According to Eq. (12.20), this implies that heat entire room. The diffusion process will not
released to the cold reservoir can never be made spontaneously reverse and bring the gas back
zero. For a refrigerator, the Second Law says that to the cylinder. The stirring of a liquid in thermal
the co-efficient of performance can never be contact with a reservoir will convert the work
infinite. According to Eq. (12.21), this implies done into heat, increasing the internal energy
that external work (W ) can never be zero. The of the reservoir. The process cannot be reversed
following two statements, one due to Kelvin and exactly; otherwise it would amount to conversion
Planck denying the possibility of a perfect heat of heat entirely into work, violating the Second
engine, and another due to Clausius denying Law of Thermodynamics. Irreversibility is a rule
the possibility of a perfect refrigerator or heat rather an exception in nature.
pump, are a concise summary of these Irreversibility arises mainly from two causes:
observations. one, many processes (like a free expansion, or
Second Law of Thermodynamics an explosive chemical reaction) take the system
to non-equilibrium states; two, most processes
Kelvin-Planck statement
involve friction, viscosity and other dissipative
No process is possible whose sole result is the effects (e.g., a moving body coming to a stop and
absorption of heat from a reservoir and the losing its mechanical energy as heat to the floor
complete conversion of the heat into work. and the body; a rotating blade in a liquid coming
Clausius statement to a stop due to viscosity and losing its
No process is possible whose sole result is the mechanical energy with corresponding gain in
transfer of heat from a colder object to a hotter the internal energy of the liquid). Since
object. dissipative effects are present everywhere and
It can be proved that the two statements can be minimised but not fully eliminated, most
above are completely equivalent. processes that we deal with are irreversible.
A thermodynamic process (state i →state f )
12.12 REVERSIBLE AND IRREVERSIBLE is reversible if the process can be turned back
PROCESSES such that both the system and the surroundings
Imagine some process in which a thermodynamic return to their original states, with no other
system goes from an initial state i to a final change anywhere else in the universe. From the
state f. During the process the system absorbs preceding discussion, a reversible process is an
heat Q from the surroundings and performs idealised notion. A process is reversible only if
work W on it. Can we reverse this process and it is quasi-static (system in equilibrium with the
THERMODYNAMICS 311

surroundings at every stage) and there are no complete a cycle, we need to take the system
dissipative effects. For example, a quasi-static from temperature T1 to T2 and then back from
isothermal expansion of an ideal gas in a temperature T2 to T1. Which processes should
cylinder fitted with a frictionless movable piston we employ for this purpose that are reversible?
is a reversible process. A little reflection shows that we can only adopt
Why is reversibility such a basic concept in reversible adiabatic processes for these
thermodynamics ? As we have seen, one of the purposes, which involve no heat flow from any
concerns of thermodynamics is the efficiency reservoir. If we employ any other process that is
with which heat can be converted into work. not adiabatic, say an isochoric process, to take
The Second Law of Thermodynamics rules out the system from one temperature to another, we
the possibility of a perfect heat engine with 100% shall need a series of reservoirs in the
efficiency. But what is the highest efficiency temperature range T2 to T1 to ensure that at each
possible for a heat engine working between two stage the process is quasi-static. (Remember
reservoirs at temperatures T1 and T2 ? It turns again that for a process to be quasi-static and
out that a heat engine based on idealised reversible, there should be no finite temperature
reversible processes achieves the highest difference between the system and the reservoir.)
efficiency possible. All other engines involving But we are considering a reversible engine that
irreversibility in any way (as would be the case operates between only two temperatures. Thus
for practical engines) have lower than this adiabatic processes must bring about the
limiting efficiency. temperature change in the system from T1 to T2
and T2 to T1 in this engine.
12.13 CARNOT ENGINE
Suppose we have a hot reservoir at temperature
T1 and a cold reservoir at temperature T2. What
is the maximum efficiency possible for a heat
engine operating between the two reservoirs and
what cycle of processes should be adopted to
achieve the maximum efficiency ? Sadi Carnot,
a French engineer, first considered this question
in 1824. Interestingly, Carnot arrived at the
correct answer, even though the basic concepts
of heat and thermodynamics had yet to be firmly
established.
We expect the ideal engine operating between
two temperatures to be a reversible engine.
Irreversibility is associated with dissipative Fig. 12.11 Carnot cycle for a heat engine with an
effects, as remarked in the preceding section, ideal gas as the working substance.
and lowers efficiency. A process is reversible if
it is quasi-static and non-dissipative. We have A reversible heat engine operating between
seen that a process is not quasi-static if it two temperatures is called a Carnot engine. We
involves finite temperature difference between have just argued that such an engine must have
the system and the reservoir. This implies that the following sequence of steps constituting one
in a reversible heat engine operating between cycle, called the Carnot cycle, shown in Fig.
two temperatures, heat should be absorbed 12.11. We have taken the working substance of
(from the hot reservoir) isothermally and the Carnot engine to be an ideal gas.
released (to the cold reservoir) isothermally. We (a) Step 1 →2 Isothermal expansion of the gas
thus have identified two steps of the reversible taking its state from (P1, V1, T1) to
heat engine : isothermal process at temperature (P2, V2, T1).
T1 absorbing heat Q1 from the hot reservoir, and
another isothermal process at temperature T2 The heat absorbed by the gas (Q1) from the
releasing heat Q2 to the cold reservoir. To reservoir at temperature T 1 is given by
312 PHYSICS

Eq. (12.12). This is also the work done (W1 →2) 1/( 1)
by the gas on the environment. V2 T2
i.e. = (12.29)
V3 T1
⎛ V2 ⎞
W1 →2 = Q1 = μ R T1 ln ⎜ V ⎟ (12.23)
⎝ 1⎠
Similarly, since step 4 → 1 is an adiabatic
(b) Step 2 →3 Adiabatic expansion of the gas process
from (P2, V2, T1) to (P3, V3, T2) 1 1
Work done by the gas, using T2 V4 T1 V1
Eq. (12.16), is
1/ 1
V1 T2
R T1 T2 i.e. = (12.30)
W2 (12.24) V4 T1
3
1
From Eqs. (12.29) and (12.30),
(c) Step 3 →4 Isothermal compression of the
gas from (P3, V3, T2) to (P4, V4, T2). V3 V2
= (12.31)
V4 V1
Heat released (Q2) by the gas to the reservoir
at temperature T2 is given by Eq. (12.12). This
Using Eq. (12.31) in Eq. (12.28), we get
is also the work done (W3 →4) on the gas by the
environment. T2
1- (Carnot engine) (12.32)
T1
V
W3 4 Q2 RT2 ln 3 (12.25)
V4 We have already seen that a Carnot engine
(d) Step 4 →1 Adiabatic compression of the is a reversible engine. Indeed it is the only
gas from (P4, V4, T2) to (P1,V1, T1). reversible engine possible that works between
two reservoirs at different temperatures. Each
Work done on the gas, [using Eq.(12.16)], is step of the Carnot cycle given in Fig. 12.11 can
be reversed. This will amount to taking heat Q2
T1 T2 from the cold reservoir at T2, doing work W on
W4 1 R (12.26)
-1 the system, and transferring heat Q1 to the hot
reservoir. This will be a reversible refrigerator.
From Eqs. (12.23) to (12.26) total work done
by the gas in one complete cycle is We next establish the important result
(sometimes called Carnot’s theorem) that
W = W1 →2 + W2 →3 – W3 →4 – W4 →1 (a) working between two given temperatures T1
and T2 of the hot and cold reservoirs respectively,
2 ⎛V ⎞
3 ⎛V ⎞ no engine can have efficiency more than that of
= μ RT1 ln ⎜ V ⎟ – μ RT2 ln ⎜ V ⎟ (12.27)
⎝ 1⎠ ⎝ 4⎠ the Carnot engine and (b) the efficiency of the
The efficiency η of the Carnot engine is Carnot engine is independent of the nature of
the working substance.
W Q2
1 To prove the result (a), imagine a reversible
Q1 Q1
(Carnot) engine R and an irreversible engine I
working between the same source (hot reservoir)
In V3 and sink (cold reservoir). Let us couple the
T2 V4 engines, I and R, in such a way so that I acts
1 (12.28)
T1 V2 like a heat engine and R acts as a refrigerator.
In V Let I absorb heat Q1 from the source, deliver
1
work W ′ and release the heat Q1- W′ to the sink.
Now since step 2 →3 is an adiabatic process, We arrange so that R returns the same heat Q1
1 1 to the source, taking heat Q2 from the sink and
T1 V2 T2 V3 requiring work W = Q1 – Q2 to be done on it.
THERMODYNAMICS 313

Now suppose ηR < ηI i.e. if R were to act than that of the Carnot engine. A similar
as an engine it would give less work output argument can be constructed to show that a
than that of I i.e. W < W ′ for a given Q1. With R reversible engine with one particular substance
acting like a refrigerator, this would mean cannot be more efficient than the one using
Q2 = Q1 – W > Q1 – W ′ . Thus on the whole, another substance. The maximum efficiency of
the coupled I-R system extracts heat a Carnot engine given by Eq. (12.32) is
(Q1 – W) – (Q1 – W ′ ) = (W ′ – W ) from the cold independent of the nature of the system
reservoir and delivers the same amount of work performing the Carnot cycle of operations. Thus
in one cycle, without any change in the source we are justified in using an ideal gas as a system
or anywhere else. This is clearly against the in the calculation of efficiency η of a Carnot
Kelvin-Planck statement of the Second Law of engine. The ideal gas has a simple equation of
Thermodynamics. Hence the assertion ηI > ηR state, which allows us to readily calculate η, but
is wrong. No engine can have efficiency greater the final result for η, [Eq. (12.32)], is true for
any Carnot engine.
This final remark shows that in a Carnot
cycle,
I Q1 T1
= (12.33)
Q 2 T2
is a universal relation independent of the nature
R of the system. Here Q1 and Q2 are respectively,
the heat absorbed and released isothermally
(from the hot and to the cold reservoirs) in a
W Carnot engine. Equation (12.33), can, therefore,
be used as a relation to define a truly universal
Fig. 12.12 An irreversible engine (I) coupled to a thermodynamic temperature scale that is
reversible refrigerator (R). If W ′ > W, this independent of any particular properties of the
would amount to extraction of heat system used in the Carnot cycle. Of course, for
W ′ – W from the sink and its full an ideal gas as a working substance, this
conversion to work, in contradiction with universal temperature is the same as the ideal
the Second Law of Thermodynamics. gas temperature introduced in section 12.11.

SUMMARY

1. The zeroth law of thermodynamics states that ‘two systems in thermal equilibrium with a
third system are in thermal equilibrium with each other’. The Zeroth Law leads to the
concept of temperature.
2. Internal energy of a system is the sum of kinetic energies and potential energies of the
molecular constituents of the system. It does not include the over-all kinetic energy of
the system. Heat and work are two modes of energy transfer to the system. Heat is the
energy transfer arising due to temperature difference between the system and the
surroundings. Work is energy transfer brought about by other means, such as moving
the piston of a cylinder containing the gas, by raising or lowering some weight connected
to it.
3. The first law of thermodynamics is the general law of conservation of energy applied to
any system in which energy transfer from or to the surroundings (through heat and
work) is taken into account. It states that
ΔQ = ΔU + ΔW
where ΔQ is the heat supplied to the system, ΔW is the work done by the system and ΔU
is the change in internal energy of the system.
314 PHYSICS

4. The specific heat capacity of a substance is defined by

1 ΔQ
s=
m ΔT
where m is the mass of the substance and ΔQ is the heat required to change its
temperature by ΔT. The molar specific heat capacity of a substance is defined by

1 Q
C
T
where μ is the number of moles of the substance. For a solid, the law of equipartition
of energy gives
C = 3R
which generally agrees with experiment at ordinary temperatures.
Calorie is the old unit of heat. 1 calorie is the amount of heat required to raise the
temperature of 1 g of water from 14.5 °C to 15.5 °C. 1 cal = 4.186 J.
5. For an ideal gas, the molar specific heat capacities at constant pressure and volume
satisfy the relation
Cp – Cv = R
where R is the universal gas constant.
6. Equilibrium states of a thermodynamic system are described by state variables. The
value of a state variable depends only on the particular state, not on the path used to
arrive at that state. Examples of state variables are pressure (P ), volume (V ), temperature
(T ), and mass (m ). Heat and work are not state variables. An Equation of State (like
the ideal gas equation PV = μ RT ) is a relation connecting different state variables.
7. A quasi-static process is an infinitely slow process such that the system remains in
thermal and mechanical equilibrium with the surroundings throughout. In a
quasi-static process, the pressure and temperature of the environment can differ from
those of the system only infinitesimally.
8. In an isothermal expansion of an ideal gas from volume V1 to V2 at temperature T the
heat absorbed (Q) equals the work done (W ) by the gas, each given by

⎛ V2 ⎞
Q = W = μRT ln ⎜⎜ V ⎟⎟
⎝ 1⎠
9. In an adiabatic process of an ideal gas
γ
PV = constant

Cp
where
Cv

Work done by an ideal gas in an adiabatic change of state from (P1, V1, T1) to (P2, V2, T2)
is

R T1 T2
W
–1

10. Heat engine is a device in which a system undergoes a cyclic process resulting in
conversion of heat into work. If Q1 is the heat absorbed from the source, Q2 is the heat
released to the sink, and the work output in one cycle is W, the efficiency ηof the engine
is:

W Q2
1
Q1 Q1
THERMODYNAMICS 315

11. In a refrigerator or a heat pump, the system extracts heat Q2 from the cold reservoir and
releases Q1 amount of heat to the hot reservoir, with work W done on the system. The
co-efficient of performance of a refrigerator is given by

Q2 Q2
α= =
W Q1 − Q2

12. The second law of thermodynamics disallows some processes consistent with the First
Law of Thermodynamics. It states
Kelvin-Planck statement

No process is possible whose sole result is the absorption of heat from a reservoir and
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.
Put simply, the Second Law implies that no heat engine can have efficiency η equal to
1 or no refrigerator can have co-efficient of performance α equal to infinity.
13. A process is reversible if it can be reversed such that both the system and the surroundings
return to their original states, with no other change anywhere else in the universe.
Spontaneous processes of nature are irreversible. The idealised reversible process is a
quasi-static process with no dissipative factors such as friction, viscosity, etc.
14. Carnot engine is a reversible engine operating between two temperatures T1 (source) and
T2 (sink). The Carnot cycle consists of two isothermal processes connected by two
adiabatic processes. The efficiency of a Carnot engine is given by

T2
η =1 − (Carnot engine)
T1
No engine operating between two temperatures can have efficiency greater than that of
the Carnot engine.
15. If Q > 0, heat is added to the system
If Q < 0, heat is removed to the system
If W > 0, Work is done by the system
If W < 0, Work is done on the system

Quantity Symbol Dimensions Unit Remark

Co-efficienty of volume αv [K–1] K–1 αv = 3 α1

expansion

Heat supplied to a system ΔQ [ML2 T–2] J Q is not a state

variable

Specific heat s [L2 T–2 K–1] J kg–1 K–1

dt
Thermal Conductivity K [MLT–3 K–1] J s–1 K–1 H = – KA
dx
316 PHYSICS

POINTS TO PONDER
1. Temperature of a body is related to its average internal energy, not to the kinetic energy
of motion of its centre of mass. A bullet fired from a gun is not at a higher temperature
because of its high speed.
2. Equilibrium in thermodynamics refers to the situation when macroscopic variables
describing the thermodynamic state of a system do not depend on time. Equilibrium of
a system in mechanics means the net external force and torque on the system are zero.
3. In a state of thermodynamic equilibrium, the microscopic constituents of a system are
not in equilibrium (in the sense of mechanics).
4. Heat capacity, in general, depends on the process the system goes through when heat is
supplied.
5. In isothermal quasi-static processes, heat is absorbed or given out by the system even
though at every stage the gas has the same temperature as that of the surrounding
reservoir. This is possible because of the infinitesimal difference in temperature between
the system and the reservoir.

EXERCISES

12.1 A geyser heats water flowing at the rate of 3.0 litres per minute from 27 °C to 77 °C.
If the geyser operates on a gas burner, what is the rate of consumption of the fuel if
its heat of combustion is 4.0 × 104 J/g ?
12.2 What amount of heat must be supplied to 2.0 × 10–2 kg of nitrogen (at room
temperature) to raise its temperature by 45 °C at constant pressure ? (Molecular
mass of N2 = 28; R = 8.3 J mol–1 K–1.)
12.3 Explain why
(a) Two bodies at different temperatures T1 and T2 if brought in thermal contact do
not necessarily settle to the mean temperature (T1 + T2 )/2.
(b) The coolant in a chemical or a nuclear plant (i.e., the liquid used to prevent
the different parts of a plant from getting too hot) should have high specific
heat.
(c) Air pressure in a car tyre increases during driving.
(d) The climate of a harbour town is more temperate than that of a town in a desert
at the same latitude.
12.4 A cylinder with a movable piston contains 3 moles of hydrogen at standard temperature
and pressure. The walls of the cylinder are made of a heat insulator, and the piston
is insulated by having a pile of sand on it. By what factor does the pressure of the
gas increase if the gas is compressed to half its original volume ?
12.5 In changing the state of a gas adiabatically from an equilibrium state A to another
equilibrium state B, an amount of work equal to 22.3 J is done on the system. If the
gas is taken from state A to B via a process in which the net heat absorbed by the
system is 9.35 cal, how much is the net work done by the system in the latter case ?
(Take 1 cal = 4.19 J)
12.6 Two cylinders A and B of equal capacity are connected to each other via a stopcock.
A contains a gas at standard temperature and pressure. B is completely evacuated.
The entire system is thermally insulated. The stopcock is suddenly opened. Answer
the following :
(a) What is the final pressure of the gas in A and B ?
(b) What is the change in internal energy of the gas ?
(c) What is the change in the temperature of the gas ?
(d) Do the intermediate states of the system (before settling to the final equilibrium
state) lie on its P-V-T surface ?
THERMODYNAMICS 317

12.7 A steam engine delivers 5.4×108J of work per minute and services 3.6 × 109J of heat
per minute from its boiler. What is the efficiency of the engine? How much heat is
wasted per minute?
12.8 An electric heater supplies heat to a system at a rate of 100W. If system performs
work at a rate of 75 joules per second. At what rate is the internal energy increasing?
12.9 A thermodynamic system is taken from an original state to an intermediate state by
the linear process shown in Fig. (12.13)

Fig. 12.13
Its volume is then reduced to the original value from E to F by an isobaric process.
Calculate the total work done by the gas from D to E to F
12.10 A refrigerator is to maintain eatables kept inside at 90C. If room temperature is 360C,
calculate the coefficient of performance.