UNIT-1

CHAPTER-1

Introduction

Areas of Application of Thermodynamics

Different Approaches in the study of Thermodynamics

SI Units

1.1 Introduction

The most of general sense of thermodynamics is the study of energy and its relationship to the
properties of matter. All activities in nature involve some interaction between energy and matter.
Thermodynamics is a science that governs the following:

Energy and its transformation

Feasibility of a process involving transformation of energy

Feasibility of a process involving transfer of energy

Equilibrium processes

More specifically, thermodynamics deals with energy conversion, energy exchange and the
direction of exchange.

1.2 Areas of Application of Thermodynamics:

All natural processes are governed by the principles of thermodynamics. However, the following
engineering devices are typically designed based on the principles of thermodynamics.

Automotive engines, Turbines, Compressors, Pumps, Fossil and Nuclear Power Plants,
Propulsion systems for the Aircrafts, Separation and Liquefication Plant, Refrigeration, Air-
conditioning and Heating Devices.

The principles of thermodynamics are summarized in the form of a set of axioms. These axioms
are known as four thermodynamic laws:

The zeroth law, the first law, the second law and the third law.
 • The Zeroth Law deals with thermal equilibrium and provides a means for measuring
temperatures.

• The First Law deals with the conservation of energy and introduces the concept of
internal energy.

• The Second Law of thermodynamics provides with the guidelines on the conversion of
internal energy of matter into work. It also introduces the concept of entropy.

• The Third Law of thermodynamics defines the absolute zero of entropy. The entropy of
a pure crystalline substance at absolute zero temperature is zero.

1.3 Different Approaches in the Study of Thermodynamics

Thermodynamics can be studied through two different approaches:

(a) Macroscopic Approach and

(b) Microscopic Approach

(a) Macroscopic Approach

Consider a certain amount of gas in a cylindrical container. The volume (V) can be measured by
measuring the diameter and the height of the cylinder. The pressure (P) of the gas can be
measured by a pressure gauge. The temperature (T) of the gas can be measured using a
thermometer. The state of the gas can be specified by the measured P, V and T . The values of
these variables are space averaged characteristics of the properties of the gas under
consideration. In classical thermodynamics, we often use this macroscopic approach. The
macroscopic approach has the following features.
 • The structure of the matter is not considered.
• A few variables are used to describe the state of the matter under consideration.
• The values of these variables are measurable following the available techniques of
experimental physics.

(b) Microscopic Approach

On the other hand, the gas can be considered as assemblage of a large number of particles
each of which moves randomly with independent velocity. The state of each particle can be
specified in terms of position coordinates ( xi , yi , zi ) and the momentum components ( pxi , pyi ,
pzi ). If we consider a gas occupying a volume of 1 cm3 at ambient temperature and pressure,
the number of particles present in it is of the order of 1020 . The same number of position
coordinates and momentum components are needed to specify the state of the gas. The
microscopic approach can be summarized as:

• Knowledge of the molecular structure of matter under consideration is essential.

• A large number of variables are needed for a complete specification of the state of the
matter.

1.4 SI Units

SI is the abbreviation of System International d' Unites. The SI units for mass, length, time and
force are kilogram, meter, second and Newton respectively. The unit of length is meter, m,
defined as 1 650 763.73 wavelengths in vacuum of the radiation corresponding to the orange-
red line of the spectrum of Krypton-86. The unit of time is second, s. The second is defined as
the duration of 9 192 631 770 cycles of the radiation associated with a specified transition of the
Cesium 133 atom. The unit of mass is kilogram, kg. It is equal to the mass of a particular
cylinder of platinum-iridium alloy kept at the International Bureau of Weights and Measures. The
amount of substance can also be expressed in terms of the mole (mol). One kilo mole of a
substance is the amount of that substance in kilograms numerically equal to its molecular
weight. The number of kilo moles of a substance, n , is obtained by dividing the mass (m) in
kilograms by the molecular weight (M), in kg/ kmol.

The unit for temperature is Kelvin, K . One K is the fraction 1/273.16 of the thermodynamic
temperature of the triple point of water. Quite often the Celsius, oC , is used to express the
temperature of a substance.
The SI unit of force, called the newton, N is a secondary unit. The, N , is the force required to
accelerate a mass of 1 kilogram at the rate of 1 meter per (second)2 .

1 N = (1kg) (1m/s2 )= 1kg m/s2

The smaller or bigger quantities are expressed using the following prefixes

Factor Prefix Symbol Factor Prefix Symbol

1012 tera T 10-2 centi c
109 giga G 10-3 milli m
106 mega M 10-6 micro µ
103 kilo k 10-9 nano n
102 hecto h 10-12 pico p

Pressure:

Pressure is the normal force exerted by a system against unit area of the boundary surface.

where δA approaches zero.

The unit for pressure in SI is pacsal, Pa

1 Pa = 1 N/m2

Two other units are widely used

1 bar = 105 Pa = 100 kPa = 0.1 MPa

and the standard atmosphere, where

1 atm = 101.325 kPa = 1.01325 bar = pressure exerted by a columan of 760 mm of Hg

Energy:

Energy is the capacity to exert a force through a distance. In SI, the unit of energy is Newton-
meter, N m or Joule, J.
Power:

The rate of energy transfer or storage is called power. The unit of power is watt, W.
1 W = 1 J/s = 1 N m/s and 1 kW = 1000 W.

Apart from these, the following units are used for various parameters of interest

Frequency, Hertz = Hz = s-1

Electric current, Ampere = A

Electric charge, Coulomb, C = As

Electric potential, Volt = V = W/A

Magnetic flux, Weber, Wb = Vs

Magnetic flux density, Tesla, T = Wb/m2

 CHAPTER-2

System

Surroundings

Types of Systems

Intensive and Extensive Properties

2.1 System

A thermodynamic system is defined as a definite quantity of matter or a region in space upon

which attention is focused in the analysis of a problem. We may want to study a quantity of
matter contained with in a closed rigid walled chambers, or we may want to consider something
such as gas pipeline through which the matter flows. The composition of the matter inside the
system may be fixed or may change through chemical and nuclear reactions. A system may be
arbitrarily defined. It becomes important when exchange of energy between the system and the
everything else outside the system is considered. The judgment on the energetic of this
exchange is very important.

2.2 Surroundings

Everything external to the system is surroundings. The system is distinguished from its
surroundings by a specified boundary which may be at rest or in motion. The interactions
between a system and its surroundings, which take place across the boundary, play an
important role in thermodynamics. A system and its surroundings together comprise a universe.

2.3 Types of systems

Two types of systems can be distinguished. These are referred to, respectively, as closed
systems and open systems or control volumes. A closed system or a control mass refers to a
fixed quantity of matter, whereas a control volume is a region in space through which mass may
flow. A special type of closed system that does not interact with its surroundings is called
an Isolated system.

Two types of exchange can occur between the system and its surroundings:

1. Energy exchange (heat or work) and

2. Exchange of matter (movement of molecules across the boundary of the system and
surroundings).
Based on the types of exchange, one can define

• isolated systems: no exchange of matter and energy

• closed systems: no exchange of matter but some exchange of energy
• open systems: exchange of both matter and energy

If the boundary does not allow heat (energy) exchange to take place it is called adiabatic
boundary otherwise it is diathermal boundary.

Property

To describe a system and predict its behaviour requires a knowledge of its properties and how
those properties are related. Properties are macroscopic characteristics of a system such as
mass, volume, energy, pressure and temperature to which numerical values can be assigned at
a given time without knowledge of the past history of the system. Many other properties are
considered during the course of our study.

• The value of a property of a system is independent of the process or the path followed
by the system in reaching a particular state.

• The change in the value of the property depends only on the initial and the final states.

The word state refers to the condition of a system as described by its properties.

Mathematically, if P is a property of the system, then the change in the property in going from
the initial state 1 to the final state 2 is given by

If P = P (x, y) then,

where,

If , then dP is said to be an exact differential, and P is a point function. A

thermodynamic property is a point function and not a path function. Pressure, temperature,
volume or molar volume are some of the quantities which satisfy these requirements.
2.4 Intensive and Extensive Properties

There are certain properties which depend on the size or extent of the system, and there are
certain properties which are independent of the size or extent of the system. The properties like
volume, which depend on the size of the system are called extensive properties. The properties,
like temperature and pressure which are independent of the mass of the system are
called intensive properties. The test for an intensive property is to observe how it is affected
when a given system is combined with some fraction of exact replica of itself to create a new
system differing only by size. Intensive properties are those which are unchanged by this
process, whereas those properties whose values are increased or decreased in proportion to
the enlargement or reduction of the system are called extensive properties.

Assume two identical systems S1 and S2 as shown in Figure 2.1 . Both the systems are in
identical states.
Let S3 be the combined system. Is the value of property for S3 same as that for S1 (and S2 )?

Figure 2.1

• If the answer is yes, then the property is intensive

• If the answer is no, then the property is extensive

The ratio of the extensive property to the mass is called the specific value of that property

specific volume, v = V/m = 1/ ρ ( ρ is the density)

specific internal energy, u = U/m

Similarly, the molar properties are defined as the ratios of the properties to the mole number (N)
of the substance

Molar volume = = V/N

Molar internal energy = = U/N

 CHAPTER-3

Energy

Macroscopic modes of Energy

Microscopic modes of Energy

Thermodynamic Equilibrium

Process

3.1 Energy

Energy is often defined as the capacity to produce work. However, this "capacity" has a special
significance. The capacity represents a combination of an effort and the change brought about
by the effort. However, the effort is exerted in overcoming resistance to a particular type of
change.

The effort involved is measured quantitatively as a "driving force" in thermodynamics. A driving

force is a property which causes and also controls the direction of change in another property.
The quantitative value of this change is called a "displacement". The product of a driving force
and its associated displacement represents a quantity of energy, but in thermodynamics this
quantity has meaning only in relation to a specifically defined system.

Relative to a particular system there are generally two ways of locating a driving force and the
displacement it produces. In one way, the driving force and the displacement are properties of
the system and are located entirely within it. The energy calculated from their product
represents a change in the internal energy of the system. Similarly, both the driving force and its
displacement could be located entirely within the surroundings so that the calculated energy is
then a change in the total energy of the surroundings.

In another way, the displacement occurs within the system but the driving force is a property of
the surroundings and is applied externally at the system boundary. By definition, the boundary
of a system is a region of zero thickness containing no matter at all so that the energy
calculated in this way is not a property of matter either in the system or in its surroundings but
represents a quantity of energy in transition between the two. In any quantitative application of
thermodynamics it is always important to make a careful distinction between energy changes
within a system or within its surroundings and energy in transition between them.

3.2 Macroscopic modes of energy

Kinetic Energy (KE)

If a body is accelerated from its initial velocity to final velocity , the total work done on the
body is
The work done on a body in accelerating it from its initial velocity to a final velocity , is
equal to the change in the kinetic energy of the body. If the body is decelerated from a
velocity to a velocity by the application of resisting force, the work done by the body is
equal to decrease in its kinetic energy.

Potential Energy (PE)

A body of mass m is moved from an initial elevant Z1 to a final
elevation Z2(Fig 3.1)

Figure 3.1

The force on the body, F = mg

This force has moved a distance ( Z2 - Z1) . Therefore, the work done on
the body

The kinetic energy and potential energy are also called organized form of energy that can be
readily

3.3 Microscopic modes of energy

The microscopic modes of energy refer to the energy stored in the molecular and atomic
structure of the system.

The molecules are in random motion. A molecule possesses energy in several forms.

• Translational energy, Rotational energy, Vibrational energy.

• Electronic energy, Chemical energy, Nuclear energy.

If ε represents energy of one molecule, then

If N is the total number of molecules in the system, then the total amount of microscopic form of
energy

U=Nε

We may also call this as INTERNAL ENERGY of the system. The internal energy, U is due to
random motions or disorganized motions of molecules. The internal energy cannot be readily
converted into work. One of the major tasks involved in thermodynamics is devising means for
converting disorganized internal energy into useful or organized work.

3.4 Thermodynamic Equilibrium

Steady state

Under the steady state condition, the properties of the system at any location are independent
of time.

Equilibrium:-At the state of equilibrium, the properties of the system are uniform and only one
value can be assigned to it.

In thermodynamics, equilibrium refers to a state of equilibrium with respect to all possible

changes, thermal, mechanical and chemical.

(a). Thermal equilibrium:- A state of thermal equilibrium can be described as one in which the
temperature of the system is uniform.

(b). Mechanical equilibrium:- Mechanical equilibrium means there is no unbalanced force. In

other words, there is no pressure gradient within the system.

(c). Chemical equilibrium:- The criterion for chemical equilibrium is the equality of chemical
potential

Superscripts A and B refers to systems and subscript i refers to component

If Gibbs function is given by G, G = U + PV – TS

where ni is the number of moles of substance i . The composition of a system does not undergo
any change because of chemical reaction.
3.5 Process

In thermodynamics we are mainly concerned with the systems which are in a state of
equilibrium. Whenever a system undergoes a change in its condition, from one equilibrium state
to another equilibrium state, the system is said to undergo a process.

Consider a certain amount of gas enclosed in a piston-cylinder assembly as our system.

Suppose the piston moves under such a condition that the opposing force is always
infinitesimally smaller than the force exerted by the gas. The process followed by the system
is reversible .

A process is said to be reversible if the system and its surroundings are restored to their
respective initial states by reversing the direction of the process. A reversible process has to be
quasi-static, but a quasi - static process is not necessarily reversible.

Figure 3.2

The process is irreversible if it does not fulfill the criterion of reversibility. Many processes are
characterized by the fact that some property of the system remains constant. These processes
are:

A process in which the volume remains constant

constant volume process. Also called isochoric process / isometric process

A process in which the pressure of the system remains constant.

• constant pressure process. Also called isobaric process

A process in which the temperature of the system is constant.

constant temperature process. Also called isothermal process

A process in which the system is enclosed by adiabatic wall.

Adiabatic process.
 CHAPTER-4

Work

Thermodynamic Definition of Work

Heat

4.1 Work

Work is one of the basic modes of energy transfer. The work done by a system is a path
function, and not a point function. Therefore, work is not a property of the system, and it
cannot be said that the work is possessed by the system. It is an interaction across the
boundary. What is stored in the system is energy, but not work. A decrease in energy of the
system appears as work done. Therefore, work is energy in transit and it can be indentified
only when the system undergoes a process.

Work must be regarded only as a type of energy in transition across a well defined, zero
thickness, boundary of a system. Consequently work, is never a property or any quantity
contained within a system. Work is energy driven across by differences in the driving forces on
either side of it. Various kinds of work are identified by the kind of driving force involved and the
characteristic extensive property change which accompanied it. Work is measured quantitatively
in the following way. Any driving force other than temperature, located outside the system on its
external boundary, is multiplied by a transported extensive property change within the system
which was transferred across the system boundary in response to this force. The result is the
numerical value of the work associated with this system and driving force. In static Equilibrium,
F=PA (Fig 4.1). The dX is small so that P does not change. The change in volume of the gas =
AdX. The elemental work,

dW=FdX=PAdX=PdV

Figure 4.1
4.2 Thermodynamic Definition of Work

In thermodynamics, work done by a system on its surroundings during a process is

defined as that interaction whose sole effect, external to the system, could be
reduced as the raising of a mass through a distance against gravitational force. Let
us consider the raising of mass m from an initial elevation z1 to final
elevation z2 against gravitational force. To raise this mass, the force acting on the
mass is given by F = mg . The work done on the body is W = mg( z2 - z1 )

An external agency is needed to act on the system

It can be seen that expansion of the gas gets reduced to raising a mass
against gravitational force (Figure 4.2)

dW = F dX = P A dX = P dV

Figure 4.2

During this expansion process, the external pressure is always infinitesimally smaller
than the gas pressure.

Figure 4.3

Compare two systems shown in the figure 4.3. Let the resistor be replaced by a
motor drawing the same amount of current as the resistor. The motor can wind a
string and thereby raise the mass which is suspended. As far as the battery is
concerned, the situations are identical. So, according to thermodynamic definition of
work, the interaction of a battery with a resistor is called work. By manipulating the
environment, that is external to the battery (system), the effect can be reduced to
raising of a mass against the gravitational force and that is the only effect on the
surroundings. We can see that the thermodynamic definition of work is more general
than that used in mechanics.
Situation in which W ≠ P dV

Figure 4.4

Let the initial volume be V1 and pressure P1

Let the final volume be V2 and pressure P2

What should be the work done in this case? Is it equal to ∫P dV ?

∫P dV = area under the curve indicating the process on P-V diagram.

The expansion process may be carried out in steps as shown in figure 4.4. It is
possible to draw a smooth curve passing through the points 1bcde2 . Does the area
under the curve (figure 4.5) represent work done by the system? The answer is no,
because the process is not reversible. The expansion of the gas is not restrained by
an equal and opposing force at the moving boundary.

W ≠ ∫ P dV

Figure 4.5

No external force has moved through any distance in this case, the work done is
zero. Therefore, we observe that

W = ∫ P dV only for reversible process

W ≠ ∫ P dV for an irreversible process
Another exceptional situation!

• The piston is held rigid using latches! (Figure 4.6)

• dV = 0
• Work done on the gas is equal to the decrease in the potential energy of
mass m
• A situation where dV = 0 and yet dW is not zero
• such work can be done in one direction only. Work is done on the system by
the surroundings

Figure 4.6

4.3 Heat

Heat is energy transfer which occurs by virtue of temperature difference across the
boundary. Heat like work, is energy in transit. It can be identified only at the
boundary of the system. Heat is not stored in the body but energy is stored in the
body. Heat like work, is not a property of the system and hence its differential is not
exact. Heat and work are two different ways of transferring energy across the
boundary of the system.

The displacement work is given by (figure 4.7)

Figure 4.7
It is valid for a quasi-static or reversible process. The work transfer is equal to the
integral of the product of the intensive property P and the differential change in the
extensive property, dV .

Just like displacement work, the heat transfer can also be written as

The quantity dQ is an inexact differential.

dQ = TdX

X is an extensive property and dX is an exact differential. The extensive property is

yet to be defined. We shall see later that X is nothing but the entropy, S of a system.

It is possible to write

or,

where is integrating factor.

 CHAPTER-5

Introduction to state postulate

Zeroth Law of Thermodynamics

Temperature Scale

Perfect Gas Scale

5.1 Introduction to state postulate

Since every thermodynamic system contains some matter with energy in its various
forms, the system can be completely described by specifying the following variables.

• The composition of the matter in terms of mole numbers of each constituent.

• The energy of the system.
• The volume of the system, and
• The measurable properties, such as pressure and temperature.

By specifying these quantities, the state of the system is defined. Once the system
is in a given state, it possesses a unique state of properties like pressure, P ,
temperature, T , density, etc. All the properties of a system cannot be varied
independently since they are interrelated through expressions of the following type

For example, the pressure, temperature and molar volume ( ) of an ideal gas are
related by the expression P = RT. Here R is a constant. Only two of the three
variables P , and T can be varied independently. Question is that for a given
thermodynamics system, how many variables can be varied independently.

5.2 Zeroth Law of Thermodynamics

Statement: If a body 1 is in thermal equilibrium with body 2 and body 3, then the
body 2 and body 3 are also in thermal equilibrium with each other

Figure 5.2
Two systems 1 and 2 with independent variables ( U1 , V1 , N1 ) and (U2 , V2 ,
N2 ) are brought into contact with each other through a diathermal wall (figure 5.2).
Let the system 1 be hot and system 2 be cold. Because of interaction, the energies
of both the systems, as well as their independent properties undergo a change. The
hot body becomes cold and the cold body becomes hot. After sometime, the states
of the two systems do not undergo any further change and they assume fixed values
of all thermodynamic properties. These two systems are then said to be in a state of
thermal equilibrium with each other. The two bodies which are in thermal equilibrium
with each other have a common characteristic called temperature. Therefore
temperature is a property which has the same value for all the bodies in thermal
equilibrium.

Suppose we have three systems 1, 2 and 3 placed in an adiabatic enclosure as

shown in figure 5.3.

Figure 5.3

The systems 1 and 2 do not interact with each other but they interact separately with
systems 3 through a diathermal wall. Then system 1 is in thermal equilibrium with
system 3 and system 2 is also in thermal equilibrium with system 3. By intuition we
can say that though system 1 and 2 are not interacting, they are in thermal
equilibrium with each other.

Suppose system 1 and 2 are brought into contact with each other by replacing the
adiabatic wall by a diathermal wall as shown in figure 5.3 (B). Further they are
isolated from system 3 by an adiabatic wall. Then one observes no change in the
state of the systems 1 and 2.

5.3 Temperature Scale

Based on zeroth law of thermodynamics, the temperature of a group of bodies can

be compared by bringing a particular body (a thermometer) into contact with each of
them in turn. To quantify the measurement, the instrument should have thermometric
properties. These properties include: The length of a mercury column in a capillary
tube, the resistance (electrical) of a wire, the pressure of a gas in a closed vessel,
the emf generated at the junction of two dissimilar metal wires etc. are commonly
used thermometric properties.
To assign numerical values to the thermal state of a system, it is necessary to
establish a temperature scale on which temperature of a system can be read.
Therefore, the temperature scale is read by assigning numerical values to certain
easily reproducible states. For this purpose, it is customary to use

a. Ice Point: The equilibrium temperature of ice with air saturated water
at standard atmospheric pressure which is assigned a value of 0oC.
b. Steam Point: The equilibrium temperature of pure water with its own
vapor at standard atmospheric pressure, which is assigned a value of
100oC.

This scale is called the Celsius Scale named after Anders Celsius.

5.4 Perfect Gas Scale

An ideal gas obeys the relation

P =RT

where R is the Universal Gas Constant ( R = 8.314 J/mol K). This equation is only an
approximation to the actual behavior of the gases. The behavior of all gases
approaches the ideal gas limit at sufficiently low pressure (in the limit P 0). The
perfect gas temperature scale is based on the observation that the
temperature of a gas at constant volume increases monotonically with
pressure. If the gas pressure is made to approach zero, the gas behavior follows
therelation
P =RT

Figure 5.4 shows a constant volume gas thermometer.

The bulb is placed in the system whose temperature is to be measured. The mercury
column is so adjusted that the level of mercury stands at the reference mark S . This
ensures that the volume of the gas is held at a constant value. Let the pressure of
the gas be read as P. Let a similar measurement be made when the gas bulb is
maintained at the triple point of water, Ptp. We can obtain triple point by putting water
and ice in an insulated chamber and evacuating air ( which is then replaced by water
vapour).

Figure 5.4
The temperature of the triple point of water has been assigned a value of 273.16 K.
Since for an ideal gas T varies as P ,

or,

where Ttp is the triple point temperature of water.

Suppose a series of measurements with different amounts of gas in the bulb are
made. The measured pressures at the triple point as well as at the system
temperature change depending on the amount of gas in the bulb. A plot of the
temperature Tcal , calculated from the expression T = 273.16 ( P/ P tp ) as a function
of the pressure at the triple point, results in a curve as shown in figure 5.5.

Figure 5.5

When these curves are extrapolated to zero pressure, all of them yield the same
intercept. This behaviour can be expected since all gases behave like ideal gas
when their pressure approaches zero. The correct temperature of the system can be
obtained only when the gas behaves like an ideal gas, and hence the value is to be
calculated in limit Ptp 0. Therefore

, as

A constant pressure thermometer also can be used to measure the temperature. In

that case,

; when

Here Vtp is the volume of the gas at the triple point of water and V is the volume of
the gas at the system temperature.
 CHAPTER-6

First Law of Thermodynamics

Heat is a Path Function

Energy is a Property of the System

A Perpetual Motion Machine of First Kind

Analysis of Closed Systems

6.1 First Law of Thermodynamics

A series of Experiments carried out by Joule between 1843 and 1848 from the basis
for the First Law of Thermodynamics

The following are the observations during the Paddle Wheel experiment shown in
Fig. 6.1.

Figure 6.1

Work done on the system by lowering the mass m through =

change in PE of m

Temperature of the system was found to increase

System was brought into contact with a water bath

System was allowed to come back to initial state

Energy is transferred as heat from the system to the bath

The system thus executes a cycle which consists of work input to the system
followed by the transfer of heat from the system.
 (6.1)

Whenever a system undergoes a cyclic change, however complex the cycle may be,
the algebraic sum of the work transfer is equal to the algebraic sum of the energy
transfer as heat (FIRST LAW OF THERMODYNAMICS).

Sign convention followed in this text:

• Work done by a system on its surroundings is treated as a positive

quantity.

• Energy transfer as heat to a system from its surroundings is treated as

a positive quantity

(6.2)

or,

6.2 Heat is Path Function

Lets us consider following two cycles: 1a2b1 and la2cl and apply the first law of
thermodynamics Eq (6.2) to get

Figure 6.2

(6.3)

or,
 (6.4)

Subtracting Eq. (6.4) from Eq. (6.3)

(6.5)

Since, work depends on the path

(6.6)

Therefore,

(6.7)

Energy transfer as heat is not a point function, neither is it a property of the system.

Heat interaction is a path function.

6.3 Energy is a Property of the System

Refer to Figure 6.2 again and consider Eq. (6.5)

(6.8)

and depend on path function followed by the system. The

quantity is the same for both the processes and connecting

the states 2 and 1. The quantity does not depend on path followed by
the system, depends on the initial and final states. Hence is an exact
differential.

Differential of property of the system

This property is the internal energy of system, E

(6.9)
Energy of an Isolated System

An isolated system is one in which there is no interaction of the system with the
surroundings. For an isolated system

(6.10)

6.4 A Perpetual Motion Machine of First Kind

Thermodynamics originated as a result of man's endeavour to convert the

disorganized form of energy (internal energy) into organized form of energy (work).

(6.11)

An imaginary device which would produce work continuously without absorbing any
energy from its surroundings is called a Perpetual Motion Machine of the First
kind, (PMMFK). A PMMFK is a device which violates the first law of
thermodynamics. It is impossible to devise a PMMFK (Figure 6.3)

Figure 6.3

The converse of the above statement is also true, i.e., there can be no machine
which would continuously consume work without some other form of energy
appearing simultaneously.

6.5 Analysis of Closed System

Let us consider a system that refers to a definite quantity of matter which remains
constant while the system undergoes a change of state. We shall discuss the
following elementary processes involving the closed systems.Constant Volume
Process

Our system is a gas confined in a rigid container of volume V (Refer to Figure 6.4)
 Figure 6.4

Let the system be brought into contact with a heat source.

The energy is exchanged reversibly. The expansion work done (PdV) by the
system is zero.

Applying the first law of thermodynamics, we get

(6.12)

or,

(6.13)

• Hence the heat interaction is equal to the change in the internal energy of the
system.

Constant Volume Adiabatic Process

Refer to Figure 6.5 where a change in the state of the system is brought about by
performing paddle wheel work on the system.

Figure 6.5
The process is irreversible. However, the first law gives

(6.14)

or

(6.14)

Interaction of heat and irreversible work with the system is same in nature. (-W)
represents the work done on the system by the surroundings

Specific Heat at Constant Volume

By definition it is the amount of energy required to change the temperature of a unit

mass of the substance by one degree.

(6.16)

While the volume is held constant. For a constant volume process, first law of
thermodynamics gives

(6.17)

Therefore,

(6.18)

Where is the specific internal energy of the system. If varies with temperature,
one can use mean specific heat at constant volume

(6.19)

The total quantity of energy transferred during a constant volume process when the

system temperature changes from

(6.20)

The unit for is kJ/kgK. The unit of molar specific heat is kJ/kmolK.
 CHAPTER-7

Constant Pressure Process 1

Constant Pressure Process 2

Specific Heat at Constant Pressure

Constant Temperature Process

Adiabatic Process

7.1 Constant Pressure Process-1

A gas in the piston-cylinder assembly is considered as the system of interest (figure

7.1)

Figure 7.1

• The pressure is maintained at a constant value by loading the system with a

mass.

• The cylinder is brought into contact with a heat source.

Energy transfer as heat takes place reversibly. The work is done by system when it
changes from the initial state (1) to the final state (2).

(7.1)

Applying the first law, we get

(7.2)
or

(7.3)

or

(7.4)

The quantity is known as enthalpy, H (a property) of the system. The

specific enthalpy his defined as

(7.5)

The molar enthalpy is , where N is the mole number of the substance.

7.2 Constant Pressure Process-2

Let us assume paddle wheel work is done on the system figure 7.2. Also, consider
adiabatic walls, so that

Figure 7.2

Now the application of first law enables us to write

(7.6)

or

(7.7)

or
 (7.8)

Therefore, the increase in the enthalpy of the system is equal to the amount of shaft
work done on the system.

7.3 Specific Heat at Constant Pressure

Let us focus on Figure 7.3

Figure 7.3

• System changes its state from 1 to 2 following a constant pressure process.

• There will be an accompanying change in temperature.

Specific heat at constant pressure is defined as the quantity of energy required to

change the temperature of a unit mass of the substance by one degree during a
constant pressure process.

(7.9)

The total heat interaction for a change in temperature from T1to T2 can be calculated
from

(7.10)

The molar specific heat at constant pressure can be defined as

(7.11)
7.4 Constant Temperature process

Let us refer to figure 7.4

Figure 7.4

The system is allowed to undergo an expansion process while in contact with

constant temperature bath. During the expansion process, the opposing force is
continuously reduced. System is in equilibrium at all times. Applying the first law, one
can write

(7.12)

For an ideal gas, the desired property relations are

and (7.13)

Since the temperature is held constant, du=0 and Q=W . We can also write

(7.14)

7.5 Adiabatic Process

1-Irreversible Adiabatic Process

A process in which there is no energy transfer as heat across the boundaries of the
system, is called an adiabatic process. For an adiabatic process, Q=0. Paddle wheel
work is performed on the system (Figure 7.5).
 Figure 7.5

Application of first law gives

(7.15)

or

(7.16)

2-Reversible Adiabatic (ISENTROPIC) Process

Consider a gas contained in the cylinder piston assembly as the system. The
cylinder wall and the piston act as adiabatic walls. Suppose the gas is allowed to
expand from the initial pressure P1 to the final pressure P2 and the opposing
pressure is so adjusted that it is equal to inside gas pressure. For such a process,
dW=PdV

The first-law of thermodynamics will give

Let us consider the system as an ideal gas which satisfies the relation
and . Also, we know that .

or

(7.17)

or,

(7.18)
or

(7.19)

Or

For an ideal gas,

Therefore,

(7.20)

The ratio of specific heats is given by

(7.21)

or,

(7.22)

Thus,

(7.23)

Therefore when an ideal gas expands reversibly and adiabatically from the initial
state to final state , the work done per mole of the gas is
given by the above expression.
 CHAPTER-8

Limitations of First Law of Thermodynamics

Heat Engine

Heat Pump

Refrigerator

KELVIN PLANCK STATEMENT

8.1 Limitations of First Law of Thermodynamics

The first law of thermodynamics is a law of conservation of energy. It does not

specify the direction of the process. All spontaneous processes processed in one
direction only. The first law of thermodynamics does not deny the feasibility of a
process reversing itself. The first law of thermodynamics does not provide answers
to the following questions.

IS A PARTICULAR PROCESS / REACTION FEASIBLE?

TO WHAT EXTENT DOES THE PROCESS / REACTION PROCEED?

IS COMPLETE CONVERSION OF INTERNAL ENERGY INTO WORK POSSIBLE?

There exists a law which determines the direction in which a spontaneous process
proceeds. The law, known as the second law of thermodynamics, is a principle of
wide generality and provides answer to the above questions.

It is essential to understand the meaning of the following terms in order to discuss

the second law of thermodynamics:

• Thermal reservoir is a large body from which a finite quantity of energy can
be extracted or to which a finite quantity of energy can be added as heat
without changing its temperature.

• A source is a thermal reservoir at high temperature from which a heat engine

receives the energy as heat.

• A sink is a low temperature thermal reservoir to which a heat engine rejects

energy as heat.

8.2 Heat Engine

A heat engine is a device which converts the energy it receives at heat, into
work.

It is a cyclically operating device.


It receives energy as heat form a high temperature body, converts part of it
into work and rejects the rest to a low temperature body.

A thermal power plant is an example of a heat engine.

Figure 16.1

Figure 16.1 describes a basic arrangement of a thermal power plant

• In the boiler, the working fluid receives a certain amount of heat from
the hot combustion products.

• The superheated steam enters a turbine where it undergoes expansion

performing the shaft work .

• The low pressure steam enters a condenser where it exchange energy as

heat at constant pressure with the cooling water and emerges as the
condensate. The condensate rejects a certain amount of heat to the
cooling water.

• The low pressure condensate from the condenser enters the pump.
Work is done on the pump to elevate the condensate to the boiler
pressure and return it to the boiler.

In the above example,

Work done by the system

Energy absorbed as heat by the system

Energy rejected as heat by the system

According to first law of thermodynamics, the heat and work interaction are related
by the equation.

(16.1)

Finally, the thermal efficiency of a heat engine can be expressed as

or,

(16.2)

8.3 Heat Pump

Heat Pump is cyclically operating device which absorbs energy form a low
temperature reservoir and reject energy as heat to a high temperature reservoir
when work is performed on the device. Its objective is to reject energy as heat to a
high temperature body (space heating in winter). The atmosphere acts as the low
temperature reservoir

8.4 Refrigerator

A refrigerator is a cyclically operating device which absorbs energy as heat from a

low temperature body and rejects energy as heat to a high temperature body when
work is performed on the device. The objective of this device is to refrigerate a body
at low temperature. Usually it uses atmosphere as the high temperature reservoir.
 Figure 16.2

Refer to figure 16.2. Let and represents the amount of energy absorbed as
heat from the low temperature reservoir and the energy rejected as heat to the high
temperature reservoir respectively, Let W be the work done on the device to
accomplish the task.

(16.3)

Therefore,

(16.4)

and

(16.5)

Heat engine and the refrigerator (/heat pump) can be represented as shown in
Figure 16.2.The efficiency of a heat engine is given by

(16.6)

since (heat) transferred to the system cannot be completely

converted to work in a cycle. Therefore is less than unity. A heat engine can
never be 100 efficient. Therefore i.e., there has always to be a heat
rejection. Thus a heat engine has to exchange heat with two reservoirs, the source
and the sink. This experience leads to the proposition of the second law of
thermodynamics which has been stated in several different ways.
8.5 KELVIN PLANCK STATEMENT

It is impossible to construct a cyclically operating device such that it produces no

other effect than the absorption of energy as heat from a single thermal reservoir
and performs an equivalent amount of work.The only option then is that the engine
converts part of the energy it receives as heat into work and rejects the rest to
another thermal reservoir the temperature of which is less than the temperature of
the source. Two thermal reservoirs, one of high temperature (source), from which the
working fluid receives energy as heat, and the other of low temperature (sink), to
which the working fluid rejects energy as heat, are needed for a heat engine. Once
the heat engine rejects a part of the energy it receives, its efficiency becomes less
than one. Thus the Kelvin Planck statement further implies that no heat engine can
have a thermal efficiency of one (hundred percent). This does not violate the first law
of thermodynamics either.
 CHAPTER-9

Kelvin - Planck Statement (Continued)

Clausius Statement of the Second Law

9.1 Kelvin - Planck Statement (continued)

Second law restricts the thermal efficiency of a heat engine to less than one. It
stipulates that some portion of the energy absorbed as heat from a source must
always be rejected to a low temperature sink.

Wilhelm Ostwald introduced the concept of perpetual motion machine of the second
kind (PMMSK or PMM2), that is, of a device which would perform work solely by
absorbing energy as heat from a body. Such a device does not violate the first law of
thermodynamics.

Figure 17.1

A PMMSK is a hypothetical device (Figure 17.1) which working cyclically, receives

energy as heat from a single thermal reservoir, and delivers as equivalent amount of
work. The Kelvin-Planck statement of the second law tells us that it is impossible
to constructs a perpetual motion machine of the second kind.

9.2 Clausius Statement of the Second Law

Heat always flows from a body at higher temperature to a body at a lower

temperature. The reverse process never occurs spontaneously. Clausius' statement
of the second law gives: It is impossible to construct a device which, operating in a
cycle, will produce no effect other than the transfer of heat from a low-temperature
body to a high temperature body.

This statement tells us that it is impossible for any device, unaided by an external
agency, to transfer energy as heat from a cooler body to a hotter body. Consider the
case of a refrigerator or a heat pump (Figure 17.2)
 Figure 17.2

When

and

It is impossible to construct a refrigerator or a heat pump whose COP is infinity.

Consider a domestic refrigerator, this device extracts energy as heat from the
substance to be coded and transfers it to the surroundings. The refrigerator is
supplied with electric power. Energy transfer as heat from a high temperature body
to a low temperature body is a spontaneous process. The Clausius statement of the
second law of thermodynamics tells that this spontaneous process cannot proceed
in the reverse direction.

Apparently, the Kelvin Planck statement and the Clausius statement of the second
law of thermodynamics are altogether different. They are not ! Instead, they are
equivalent. A violation of Kelvin Planck statement leads to a violation of the Clausis
statement too and vice-versa.

Clausius Statement of the Second Law (contd...)

Let us suppose that the Kelven Planck statement is incorrect.

Figure 17.3
Refer to Figure 17.3 that is, it is possible to construct a device I which, working
cyclically, absorbs energy a heat from a source at temperature and
performs an equivalent amount of work . Next consider a device II which
absorbs amount of energy from a low temperature body at and delivers
energy as heat to a high temperature reservoir at . To accomplish this,
work is done on the device. The device II does not violate the Clausius
statement. For device II, we can write . Now combine I and II. The
work delivered by device I is used by device, II.

Then

(17.1)

(17.2)

This combined device (which is no more aided by any external agency) working
cyclically, is not producing any effect other than the transfer of energy as heat
from the low temperature reservoir to the high temperature reservoir. This is in
violation of the Clausius statement.

Figure 17.4

To prove that violation of the Clausius' statement leads to violation of Kelvin Planck
statement, let us assume that the Clausius' statement is incorrect. That is, it is
possible to constructs a device I (refer to Figure 17.4) such that it transfers energy
as heat from a body at lower temperature to a body at higher temperature
unaided by any external agency. Consider another device II which receives energy
as heat from a body at higher temperature, delivers work and rejects
energy as heat to the body at a low temperature. Device II does not violent
Kelvin Planck statement. Application of the first law of thermodynamics to device II
gives,

(17.3)
Now consider the combination of devices I and II as a single device. This combined
device, working cyclically, absorbs amount of energy as heat from the
thermal reservoir at temperature and delivers work , leaving the
thermal reservoir at temperature unaffected. That is, the resulting device is a
PMMSK, which is in violation of the Kelvin Planck statement. Thus the Kelvin Planck
statement and the Clausius' statement are equivalent.