LECTURE NOTE

DEPARTMENT OF MECHANICAL ENGINEERING

FACULTY OF ENGINEERING, UNIVERSITY OF
JOS

COURSE: THERMOSCIENCE I (MEE 205)

CLASS: 200 LEVEL STUDENTS OF FACULTY OF
ENGINEERING

LECTURER:
ENGR. MAREN ISHAKU BOROK

1
 INTRODUCTION

There has been an exponential growth of population and material wealth since the Industrial
Revolution resulting to an ever increasing use of energy and machines. The energy resources
being used over the centuries, such as coal, petroleum, natural gas and uranium are limited,
exhaustible and environmentally unfriendly. Thus, there is a dire need to find ways of using our
energy resources more efficiently and also look for alternative sources of energy that are
sustainable and environmentally friendly.

Thermodynamics is a science that deals with the analysis of machines which convert energy
resources (chemical and nuclear energy) into useful work. It is the science of the relationship
between heat and work and the properties of a system. It is concerned with the means necessary
to convert heat energy (which is available in energy resources such as coal, petroleum, natural
gas and nuclear piles) into mechanical work. This is achieved through the engineering plants
such as combustion systems, rockets, turbojets, steam turbines, refrigerators, compressors,
boilers, condensers, cooling towers, heat exchangers and many others as they are concerned with
the transfer of heat and work, making use of the behavior of fluid when compressed or expanded,
heated or cooled. Therefore, thermodynamics is an essential study for those hoping to improve
the effectiveness with which we use our energy resources.

Thermodynamics is studied by physicists, chemists, and engineers. Physicists and chemists are
concerned with basic laws, properties of substances, and changes in the properties caused by the
interaction of different forms of energy. Engineers are interested not only in all these aspects, but
also in the application of thermodynamic principles to the design of machines that will convert
energy from one form into another. Mechanical engineers are frequently concerned with the
design of a system that will most efficiently convert thermal energy into mechanical energy, or
vice versa. Engineers use principles drawn from thermodynamics and other engineering sciences,
such as fluid mechanics and heat and mass transfer, to analyze and design things intended to
meet human needs. Engineers seek to achieve improved designs and better performance, as
measured by factors such as an increase in the output of some desired product, a reduced input of
a scarce resource, a reduction in total costs, or a lesser environmental impact. The principles of
engineering thermodynamics play an important part in achieving these goals.

BASIC THERMODYNAMICS CONCEPTS

A System is a region in space containing some quantity of matter whose behavior is under study.
A Boundary is a surface, imaginary or real, enclosing the system. Surrounding is everything
outside the boundary which might affect the behavior of the system. A Closed system is a
system of fixed mass as shown in fig.1 (b). There is no mass transfer across the system boundary.
There may be energy transfer into or out of the system. An example of a closed system is a gas
expanding in a cylinder by displacing a piston as shown in fig.1(c).

2
Fig. 1 (a) Thermodynamic system (b) a closed system (c) A gas in a piston- cylinder assembly
The Open system is one in which mass crosses the boundary of the system. There may be also
energy transfer across the boundary. An example of open system is water flowing through a
hydraulic turbine as shown in fig. 2 (a). An Isolated system is one in which there is no
interaction between the system and the surrounding. There is no mass or energy transfer across
the system boundary as shown in fig. 2 (b).

Fig. 2 (a) An open system (a hydraulic turbine) (b) an isolated system

A quantity of matter similar throughout in chemical composition and physical structure is called
a phase. Every substance can exist in any of the three phases, viz., solid, liquid and gas. A
system consisting of single phase is called homogeneous system, while a system consisting of
more than one phase is known as heterogeneous system.

Thermodynamic analysis is made of some devices such as compressors, turbines and pumps
through which mass flows. It is simpler to treat such devices as a given region of space through
which mass flows. With this approach, a region within a prescribed boundary is studied. The
region is called a control volume as shown in fig 3 (a) and (b). Mass may cross the boundary of
a control volume.

3
Fig. 3 (a) Automobile engine (b) Expressed as a control volume (open system).

To describe a system and predict its behavior requires knowledge of its properties and how those
properties are related. A property of a system is a macroscopic characteristic of a system such as
mass, volume, energy, pressure, and temperature to which a numerical value can be assigned at a
given time without knowledge of the previous behavior of the system.

For open system, in addition to the thermodynamic properties, there are mechanical properties
(for example, velocity relative to the fixed boundary of the system, position in the gravitational
field, which is height above some datum). Properties are the coordinates to describe the state of a
system.

Thermodynamic properties can be placed in two general classes: extensive and intensive.
Extensive properties depend on the size or extent of a system. They properties increase with the
increase in the mass of the system. Examples of extensive properties are mass, volume, enthalpy,
energy, internal energy and entropy. Intensive properties of a system are independent of the size
or extent of a system and may vary from place to place within the system at any moment. They
are independent of the mass of the system. Examples of such properties are temperature,
pressure, density, specific heat capacity and specific volume.

The state of a system refers to the condition of the properties of the system. Any operation
which results to the change of one or more of the properties of the system is called change of
state. For a change of state to occur in a system (for example, thermodynamic properties; p 1, v1,
T1, u1, s1 and h1 changing to p2, v2, T2, u2, s2 and h2) it has to undergo a process. Thus, a process is
an operation on matter in a system which could be either expansion or compression or the
conversion of water to steam. A system is said to be at steady state if its properties do not
change with time. Succession of states passed through during the change of state is called the
path of the change of state. When the path is completely specified, the change of state is called a
process.

The state of a matter in a system can change due to any of the following process.

4
 1. Constant temperature or Isothermal process-This is the process carried such that the
temperature of the system remains constant throughout the process. An example is the
process carried out according to Boyle’s law
2. Constant volume or Isometric process-This is the process carried out such that the
volume of the system remains constant throughout the process. An example of constant
volume process is the constant volume heat addition in Otto- cycle.
3. Constant pressure or Isobaric process-This is the process carried out such that the
pressure remains constant throughout the process. An example of such process is a gas
expanding in a cylinder under constant load.
4. Adiabatic process-This is a process carried out such that there is no heat transfer into or
out of the system. This is achieved if the system is sufficiently thermally insulated or if
the process is carried out with sufficient rapidity such that there will be little time for heat
transfer.
5. Polytrophic process-This is the process carried out according to the law PV  C where
n

C is a constant and n is a constant which depends only on the heat transferred and the
work done.
A system is said to exist in a state of thermodynamic equilibrium when no change in any
macroscopic property is registered, if the system is isolated from its surroundings. A system will
be in a state of thermodynamic equilibrium if the conditions for the following three types of
equilibrium are satisfied;

a) Mechanical equilibrium-is when there is absence of any unbalanced force within the
system itself and also between the system and the surroundings.
b) Chemical equilibrium-is when there is no chemical reaction or transfer of matter from
one part of the system to another, such as diffusion or solution.
c) Thermal equilibrium-when a system existing in mechanical and chemical equilibrium is
separated from its surroundings by a wall which allows heat to flow and there is no
spontaneous change in any property of the system, the system is said to exist in a state of
thermal equilibrium.
It is important to note that a process is said to be reversible when the change in state is in such a
way that at any instant during the process, the state point can be located on the diagram and in
such case, the matter in the system passes through a continuous series of equilibrium state. Thus
a reversible process between two states, for example states 1 and 2, can be drawn as a line on any
diagram of properties as shown in fig. 4(a).

In practice, the matter undergoing a process cannot be kept in equilibrium in its intermediate
states and a continuous path cannot be traced on a diagram of properties. Such real processes are
called irreversible processes. An irreversible process is represented by dotted lines joining the
end state to show that the intermediate states are indeterminate as shown in fig. 4(b).
5
Fig. 4(a) Reversible process (b) Irreversible process

The criteria for reversibility are:

i. The process must be frictionless, that is the fluid itself must have no internal friction and
there must be no mechanical friction (e.g. between cylinder and piston)
ii. The difference in pressure between the fluid and its surroundings during the process must
be infinitely small. This means that the process must take place infinitely slowly, since
the force to accelerate the boundaries of system is infinitely small.
iii. The difference in temperature between the fluid and its surroundings and during the
process must be infinitely small. This means that the heat supplied or rejected to or from
the fluid must be transferred infinitely slowly.
In practice, no process is reversible. However, in many practical processes a very close
approximation to an internally reversibility may be obtained. In an internally reversible process,
although the surroundings can never be restored to their original state, the fluid itself is at all
times in an equilibrium state and the path of the process can be exactly retraced to the initial
state. In general, processes in cylinders with a reciprocating piston are assumed to be
approximately internally reversible while rotary machinery such as turbines are known to be
highly irreversible due to high degree of turbulence and scrubbing of the fluid.

Pressure- The normal force exerted by a system on a unit area of its surroundings is called the
pressure (p) of the system. Since the pressure of a substance does not depend on its mass,
pressure is an intensive property. Pressure is a macroscopic property associated with
thermodynamic boundary work. Pressure is therefore called the driving force of thermodynamic
boundary work. Pressure is measurable and is one of the most important properties of a
thermodynamic system.

6
Two different pressures are common in engineering practice: gage pressure and absolute
pressure. Absolute pressure (Pab ) is the amount of force per unit area exerted by a system on
its boundaries.
Gage pressure (Pg) is the value measured by a pressure gauge, which indicates the pressure
difference between a system and its atmosphere. The atmospheric pressure (Patm ) is due to the
weight of the air per unit horizontal area in the earth’s gravitational field. Hence,
Pab  Pg  Patm
1 standard atmosphere 1atm=1.01325 x105 N/m2
The SI unit of pressure is the pascal. 1 pascal =1 N/m2
1 kPa=103N/m2
1 bar=105N/m2
1 MPa=106N/m2

Volume (V) - This is the physical space occupied by a body. The body itself can be in a solid,
liquid, or gaseous state. The volume of a body is proportional to the mass of the body, and
therefore volume is an extensive property. Volume can be easily measured. It is a macroscopic
property associated with thermodynamic boundary work. Volume is therefore called
displacement of thermodynamic boundary work. Volume is one of three basic measurable
thermodynamic properties that are commonly used to describe a substance. The SI unit of
volume is m3. The specific volume v is defined as the reciprocal of the density; it is the volume
per unit mass. The SI unit of specific volume is m3/kg.

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

is in thermal equilibrium with other system. Temperature is an indication of the thermal energy
stored in a thermodynamic system. In thermodynamics, temperature is defined to be the property
having equal magnitude in systems that are in thermal equilibrium. Temperature is a microscopic
property associated with heat. Temperature is therefore called the driving force of heat.
Temperature is measurable and is one of the most important properties of a thermodynamic
system.
The absolute temperature scale is defined such that a temperature of zero corresponds to a
theoretical state of no molecular movement of the substance. The SI unit of the absolute
temperature scale is the Kelvin (K). The Metric temperature scales are made by arbitrarily
selecting reference temperatures corresponding to reproducible state points (ice point and steam
point) and the SI unit SI of the metric temperature scales is the Celsius (ºC) scale.

EQUATION OF STATE

An equation showing the relation between the pressure (p), the specific volume (v) and the
temperature (T) for any gas is called the equation of state.
Ideal or Perfect Gas-is a gas that obeys the kinetic theory of gases which state that:
i. The gas molecules move randomly in straight lines, colliding with one another and with
the walls of the container. As a result, the speeds of the various molecules differ widely
and are constantly changing. The collision of the gas molecules on the walls of the
container constitute the gas pressure exerted in the container.

7
 ii. The collisions of the gas molecules are perfectly elastic. When two molecules collide,
their individual energies may change, and one may move faster while the other slows
down, but their total kinetic energies remain the same, i.e. no kinetic energy is converted
to heat. When the molecules collide with the walls of the container, the re-bounce like
elastic balls without any loss of energy.
iii. The actual volume occupied by the gas molecules themselves is negligible relative to the
volume of the container. The gas molecules are also small in relation to the distance
between them.
iv. The cohesive forces between the gas molecules are negligible.
v. The temperature of the gas is a measure of the average kinetic energy of the gas
molecules.
In the case of an ideal or perfect gas, the equation of state is express by the relation

pv  RT (1)

Where, p is the pressure of the gas in N/m2, v is the specific volume of the gas in m3/kg, T is the
temperature of the gas in kelvin (K) and R is the gas constant. The units of R, are Nm / kgK or
kJ / kgK
Ro
But gas constant R  (1a)
M
Where, Ro is universal gas constant and has value 8314.3 Nm / moleK . M is the molar mas of the
gas.
For m kg of gas, occupying a volume of V m3, equation (1) becomes;
pV  mRT (1b)
Thus, we have
p1V1  m1 RT1 (1c)
p2V2  m2 RT2 (1d)
This equation holds exactly for real gas only as the pressure approaches zero. It holds for real gas
at high pressure when the gas is at high temperature.

Real Gas-is a gas that does not obey the kinetic theory of gases. This is because in reality,
whenever there is increase in pressure the specific volume decreases, the volume occupied by the
gas molecules themselves becomes increasingly important and intermolecular forces between
molecules becomes significant. Due to the finite size of the molecules the space available for free
motion of any molecule is decreased. Consequently, the rate of molecular collision and thereby
the pressure are increased over the ideal gas values. To take into account these effects, equations
of state for real gases are derived and one of such is:

 a
 p  2 v  b   RT (2)
 v 

8
This is called the van der Waals equation of state in which p is the pressure, T is the absolute
temperature, v is the specific volume, R is the universal gas constant, and a and b are the
constant for the gas.

EXAMPLES

1. 0.03 kg of a certain perfect gas occupies a volume of 0.01 m3 at a pressure of 8 bar and a
temperature of 176oC. Calculate the molecular weight of the gas. When the gas is allowed
to expand until the pressure is 2 bar the final volume is 0.03m3. Calculate the final
temperature.

SOLUTION

Given:
p1  8 bar ; V1  0.01 m 3 ; V2  0.03 m 3 ; m  0.03kg ; T1  176  273  449K ; p2  2 bar
Ro  8314.3 Nm / mole K ; M  ? ; T2  ?

From equation (1c) p1V1  mRT1

p1V1 8  10 5  0.01
Thus, R    593.9  594 Nm / kgK
mT1 0.03  449
Ro
From equation (1a) R  M
Ro 8314.3
Therefore, M    13.997  14
R 594
Molecular weight =14

From equation (1d) p1V2  mRT2

pV 2  10 5  0.03
T2  2 2   336.7  337 K
mR 0.03  594

Final temperature=337-273=640C

2. 0.2 m3 vessel contains nitrogen at 2 bar and 300C. If 0.3kg of nitrogen is now pumped
into the vessel, calculate the new pressure when the vessel has returned to its initial
temperature. The molecular weight of nitrogen is 28, and it may be assumed to be a
perfect gas.

SOLUTION

Given:
V1  0.2 m 3 ; p1  2 bar ; T1  30 0 C  273  303K ; Ro  8314.3 Nm / mole K ; M  28 kg

9
 Ro
From equation (1a), R  M
Ro 8314.3
Thus, R  M  28  296.9 Nm / kgK
From equation (1c) p1V1  m1 RT1

p1V1 2  10 5  0.2
, 1 RT  296.9  303  0.445kg
m 
1

0.3kg of nitrogen is added, hence m2  0.3  0.445  0.745 kg

Therefore from equation (1d) p1V2  m2 RT2
But V2  V1 and T2  T1
m2 RT2 0.745  296.9  303
Thus p 2  V2

0.2  10 5
 3.35 bar

ENERGY

The word energy refers to the ability to do work. Matter can store energy. Energy held within a
system is associated with the matter of the system. The amount of energy of a system is reflected
in properties such as temperature, velocity, or position in a gravitational field. As the amount of
stored energy changes, the values of these properties change. An important characteristic of
classical thermodynamics is that it deals with the changes in the amount of energy in a system
and not with the system’s absolute energy.

REVERSIBLE WORK

Work done (W) is defined as the product of a force and the distance moved in the direction of the
force. When the boundary of a closed system moves in the direction of the force acting on it,
then the system does work on its surroundings (i.e. positive work). When the boundary moves
inwards the work is done on the system by its surroundings (i.e. negative work). The SI unit of
work done is Nm or Joule (J) and kilojoule (kJ) for higher units.

Fig. 5 A reciprocating cylinder

10
Let’s consider an ideal frictionless fluid contained in a cylinder behind a piston as shown in fig.
5. Let’s assume that the pressure and temperature of the fluid are uniform and that there is no
friction between the piston and the cylinder walls. Let the cross-sectional area of the piston be A
and the pressure of the fluid at any instant be p. Let the restraining force exerted by the
surroundings on the piston be ( p  dp) A . Let the piston move under the action of the force
exerted by the fluid a distance dl to the right. Thus, the work done by the fluid on the piston is
given by force times the distance moved.

Work done by fluid (W )  ( pA)  dl  pdV

(Where, dV is a small increase in volume)

Considering unit mass, work done  pdv , where v is specific volume.

When the expansion of the fluid in the cylinder is reversible, between states 1 and 2, we have,

Work done (W)   pdv  v1 pdv

v2
(3)
1
The work done by the fluid during any reversible process is therefore given by the shaded area
under the line of the process plotted on p-v diagram as shown in fig. 6.
Equation (3) can be solved by expressing p in terms of v.

Fig. 6 (a) p-v diagram (b) Thermodynamic cycle

THERMODYNAMIC CYCLE
When a system containing fluid undergoes a series of processes and finally returns to its initial
state, then it is said to have undergone a thermodynamic cycle. A cycle which consists only of
reversible processes is a reversible cycle. A reversible cycle plotted on a p-v diagram forms a
closed figure and the shaded area of which represents the network of the cycle as shown in fig.
6(b). The rule is that, when the cycle is described in a clockwise manner, the enclosed area
represents work done by the system and when the cycle is described in an anticlockwise manner,
the enclosed area represents work done on the system.

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EXAMPLES

1. 1kg of fluid is compressed reversibly according to a law pv = 0.25 where p is in bar and v
1
is in m3/kg. The final volume is 4 of the initial volume. Calculate the work done on the
fluid and sketch the process on a p-v diagram.

SOLUTION

Fig. 8 A sketch of the p-v diagram

For a reversible compression, work done is calculated from equation (3)

i.e Work done W   pdv

1
Given:
0.25
pv  0.25 , thus, p   10 5 N / m 2
v
1
v1  1m 3 / kg ; v2  ( )m 3 / kg
4
Thus,
v2 0.25 0.25

 25000 lnv  25000 ln 0.25  ln(1)  25000  {(1.38629)  (0)}

dv dv
W  0.25  10 5
 25000 
v1
v 1
v 1

 34660 Nm

2. 0.09m3 of fluid at 0.7 bar are compressed reversibly to a pressure of 3.5 bar according to
a law pvn=constant. The fluid is then heated reversibly at a constant volume until the
pressure is 4 bar; the specific volume is then 0.5 m3/kg. A reversible expansion
according to a law pv2=constant restores the fluid to its initial state. Calculate the mass of

12
 fluid present, the value of n in the first process, and the net work done on or by the fluid
in the cycle. Sketch the cycle on a p-v diagram.

Fig. 9 A sketch of the p-v diagram

SOLUTION

Given:
p1  0.7 bar ; p2  3.5 bar ; p3  4.0 bar ; V  0.09 m 3 is the volume of the system
v2  v3  0.5 m 3 / kg ; v1  ? ; m  ?
Assuming the gas in the system is an ideal gas. Thus, the ideal gas equation holds for the system,
i.e. pv  RT
Hence, p3 v3  p1v1  C1 ,
2 2
(i)
where C1 is a constant.

C1 can be calculated from equation (i) as C1  p3 v3  4.0  0.5  1 bar

2 2

C1 1 bar
v1 can be calculated from equation (i) as v1    1.1952 m 3 / kg
p1 0.7
V 0.09
The mass of fluid present is calculated from m  v  1.1952  0.0753 kg
1
n
p 2 v1n  v1 
Rearranging gives p  v n   v  and taking the natural logarithm of both sides gives
1 2  2
p   3.5 
ln  2  ln  
ln 5
n
 p2   v1   v1   p1   0.7 
ln    ln    n ln   , and n     1.8468  1.85
 p1   v2   v2   v1   1.1952  ln 2.3904
ln   ln  
 2
v  0.5 

13
Similarly, from pv  C2 , we have, p1v1  p2 v2 , C2 is a constant and can be calculated as:
n n n

C2  p2 v2n  3.5 bar  0.5  3.5 bar  0.5  0.971 bar

n 1.85

The net work done by the system is given by the shaded area shown in fig.9 above.
Work done by the reversible expansion of the system according to the law pv  C1
2
(ii)
C1
From equation (ii), p  v 2 . Substituting for p into the equation for reversible work done W
gives:

1.1952
1 1
v1 v1 v v
1   1 1 
1 1
C1 dv
W   pdv   2 dv C1  2  C1    1 bar     1 bar   
v3 v3 v v3 v  v  v3  v1 v3  0.5 1.1952 0.5 
W  1 bar 0.8367  2  1  10 5   1.1633  116, 332 Nm
Thus W3 1  116, 332 Nm
Similarly, work done by reversible compression of the system according to the law
pv n  C2 (iii)
C2
From equation (iii), p 
v n , substituting for p into the equation for reversible work done W
gives:

     
v3 v2
C2 C2 C2 0.971 bar
W   pdv  v
v3 0.5
dv  v n1  v3n 1  v1n 1  0.5 1.851  1.1952 1.851
 n 1  n 1  1.85  1
n v1 1.1952
v1 v1

W
0.971 bar
1.8025  0.8590  1.1424 bar  0.9431  1.077  105  107700 Nm
 0.85
Thus, 1 2  107700 Nm
W

The net work done during the thermodynamic cycle is

W3 1  W1 2  116, 332  107700  8,632 Nm / kg
Thus, the net work done by 0.0753 kg of the fluid in the system is
WNet  8,632  0.0753  649.99 Nm

3. A fluid is heated reversibly at a constant pressure of 1.05 bar until it has a specific
volume of 0.1 m3/kg. It is then compressed reversibly according to a law pv=constant to a
pressure of 4.2 bar, then allowed to expand reversibly according to the law
pv1.3=constant, and is finally heated at constant volume back to the initial conditions. The
work done in the constant pressure process is 515 Nm and the mass of the fluid present is
0.2 kg. Calculate the net work done on or by the fluid in the cycle and sketch the cycle on
a p-v diagram.

14
SOLUTION

Work done by constant pressure expansion is given as W  p(v2  v1 ) (i)

Given:

W  515 Nm ; p1  p2  1.05 bar ; v2  0.1 m 3 / kg ; p3  4.2 bar ; v1  v4  ? ; v3  ?

Substituting the given values in equation (i), gives

515  1.05  105 (0.1  v1 )

515  1.05  10 4
Solving for v1 gives v1   1.05  10 5
 0.095 m 3 / kg

From reversible compression according to the law pv=constant, we have,

pv  C1

Hence, p2 v2  p3 v3  C1 (ii)

Thus from equation (ii), C1  p2 v2  1.05  10  0.1  1.05  10

5 4

p 2 v2 1.05  10 4  0.1
v
From equation (ii), 3    0.025 m 3 / kg
p3 4.2

From reversible expansion according to the law pv1.3=constant

pv1.3  C2

Thus, p3 v3  p4 v4  C2
1.3 1.3
(iii)
5

From equation (iii), C2  p3 v3  4.2  10 (0.025)  0.0347  10

1.3 5 1.3

p3 v31.3 4.2  10 5  (0.025)1.3

p
Similarly from equation (iii), 4    0.741  10 5  0.741 bar
v14.3 (0.095)1.3

Reversible compression work on the fluid is given as

v3

W2 3   pdv
v2
(iv)

15
 C1
But from reversible compression according to the law pv  C1 we have p  v and substituting
for p equation (iv) gives

 1.05  10 4 lnv0.1  1.05  10 4 ln(0.025)  ln(0.1)

v3 0.025 dv 0.025
dv
W2 3  C1   1.05  10 4  v
v2
v 0.1

W2 3  1.05  10 4 (3.6889  (2.3025))  14,556 Nm / kg

Reversible expansion work done by the fluid is given as

v4

W3 4   pdv
v3
(v)

C2
From reversible expansion according to the law pv 1.3
 C , we have p 
v1.3 and substituting
2

for p in equation (v) gives

dv 0.0347  10 5  1 
v4 0.095
 1 1 
W3 4  C 2    0.3 
 0.1157  10 5  
v3 v
1.3
 1.3  1  v  0.025  0.095
0.3
0.025 0.3 
W3 4  0.1157  10 5 2.026  3.024  11, 546.86 Nm / kg

The net work done by the system WNet  11, 546.86  515  14, 556  2,494.14 Nm / kg

Thus, the net work done by the system by 0.2kg of the fluid gives
WNet  2, 494.14  0.2  499 Nm

EXERCISE

4. 1 kg of a fluid expands reversibly according to a linear law from 4.2 bar to 1.4 bar. The
initial and final volumes are 0.004 m3 and 0.02m3 respectively. The fluid is then cooled
reversibly at constant pressure and finally compressed reversibly according to a law
pv=constant back to the initial conditions of 4.2 bar and 0.004m3. Calculate the work
done in each process stating whether it is done on or by the fluid and calculate the net
work of the cycle. Sketch the cycle on a p-v diagram.
HEAT

Heat is a form of energy which is transferred from one body to another at a lower temperature by
virtue of temperature difference between the bodies. In other word, heat is seen as a form of
energy transfer which appears at the boundary when a system changes its state due to a

16
difference in temperature between the system and its surroundings. It is denoted by the symbol
Q. It is conventionally accepted that heat received by system from its surroundings is positive
while heat rejected by system to its surroundings is negative. The SI unit for heat is Joules (J).

INTERNAL ENERGY

Joule carried out experiment on the nature of heat and work. He placed measured amount of
water in an insulated container and agitated the water with a rotated stirrer as shown in fig. 7.
The amount of work done on the water by the stirrer was measured and the temperature changes
of the water are noted. It was noticed that a definite amount of work was required per unit mass
of water for every degree of temperature rise caused by stirring. When water has its temperature
rose in this manner, it can be readily returned to its original condition by extracting heat from it.
The question arises as to what happens to this energy between the time it is added to the water as
work and extracted as heat. It is logical to conclude that this energy is contained within the water
in some form. This form of energy is defined as internal energy or in another word intrinsic
energy. A system stores energy within and between its constituent molecules. Microscopic
energy modes include molecular translation energy, molecular rotation energy, molecular
vibration energy, molecular binding energy, electron translation energy, electron spin energy,
etc. This deeply stored total energy, which is associated with all microscopic modes, is called
internal energy. The symbol U is used to represent internal energy, and u is used to represent
specific internal energy The SI unit for internal energy is Joule (J). Any change in molecular
velocity, vibration rate in the bonds and forces between molecules, or in the number and kind of
molecules, changes the internal energy. The change in internal energy is denoted by ΔU or ( Δu
change in specific internal energy). The internal energy is not directly measurable; however, it is
related to other measurable properties. The internal energy of a substance does not include
energy that it may possess as a result of its position or movement as a whole; rather it refers to
the energy of the molecules making up the substance.

Fig. 7 Joule’s experiment; paddling

17
THE FIRST LAW OF THERMODYNAMICS

This law is based on the principle of conservation of energy which says that energy can neither
be created nor destroyed. The law states that when a system undergoes a thermodynamic cycle
then the net heat supplied to the system from its surroundings is equal to the net work done
by the system on its surroundings.
Mathematically, it is written,
 dQ   dW (4)
Where  represents the sum for a complete cycle,

THE NON-FLOW EQUATION

As stated by the first law of thermodynamics, if a system possessing a certain intrinsic energy is
made to undergo a thermodynamic cycle by heat and work transfer, then the net heat supplied is
equal to net work output. This is true for a complete cycle when the final intrinsic energy of the
system is equal to its initial value. Let’s consider a process in which the intrinsic energy of the
system is finally greater than the initial intrinsic energy. The difference between the net heat
supplied and the net work output has increased the intrinsic energy of the system.

i.e, Gain in intrinsic energy =Net heat supplied - Net work output

When a fluid is not in motion then its intrinsic energy is known as the internal energy of the fluid
and is given the symbol u. The internal energy of mass, m, of a fluid is written as U=mu
Hence, the gain in internal energy in changing from state 1 to state 2 can be written as

2 2
U 2  U 1   dQ   dW (5)
1 1

In any one non-flow process there will be either heat supplied or heat rejected, but not both;
similarly there will be either work output or work input, but not both. Denoting heat which is
supplied to the system as positive and work which is done by the system as positive, equation (5)
becomes.

U 2  U1  Q  W (6)
Rearranging equation (6) gives

Q  (U 2  U1 )  W (7)

For unit mass of the fluid (1kg) equation (7) becomes

Q  (u 2  u1 )  W (8)
Equation (8) is known as the non-flow energy equation

18
For a small amount of heat supplied dQ , a small amount of work done by the fluid dW and a
small gain in internal energy du, the non-flow energy equation becomes

dQ  du  dW (9)

It is important to note that equations (4), (8) and (9) are applicable for non-reversible and
reversible process.
However, for non-flow reversible process, equation (3) is substituted in equations (8) and (9), i.e,
2
Q  (u 2  u1 )   pdv (10)
1

Thus for small amount of heat supplied dQ , a small amount of work done by the fluid dW , and a
small gain in internal energy du , then,
dQ  du  pdv (11)

STEADY FLOW ENERGY EQUATION

Fig. 8 (a) A steady flow through an apparatus (b) Enlarged view of the inlet section of apparatus

Let’s consider 1 kg of fluid flowing in steady flow through an open system pieces of apparatus
shown in fig.8 (a). The boundary is shown cutting the inlet pipe at section 1 and the outlet pipe at
section 2. This boundary is called a control surface, and the system a control volume.
Let’s assume that a steady flow of heat Q units per kg of fluid is supplied, and that each kg of
fluid does W units of work as it passes through the apparatus. Let the fluid at inlet has a velocity
C1 , internal energy u1 , pressure p1 and be at a height z1 from reference point. In order to
introduce 1 kg of fluid across the boundary an expenditure of energy is required; similarly in
order to push 1 kg of the fluid across the boundary at exit, an expenditure of energy is required.
An enlarged view of the inlet section is shown in fig. 8 (b). Let’s consider an element of fluid of
length l , and let the cross-sectional area of the inlet pipe be A1 , thus,
Energy required to push element across boundary  ( p1 A1 )  l  p1  (volume of fluid element )

19
Therefore the energy required for 1 kg of fluid  p1v1
(Where v1 is the specific volume of the fluid at section 1)
Similarly, it can be shown that,
Energy required at exit to push 1 kg of fluid across the boundary  p2 v2

Now, the total energy entering the system consists of the energy of the flowing fluid at inlet
section:
C2
(u1  1  Z1 g ) , the energy due to pressure, p1v1 , and the heat supplied Q .
2
Similarly, the energy leaving the system consists of the energy of the flowing fluid at the outlet
section:
C 22
(u1   Z 2 g ) , the energy due to pressure p 2 v 2 , and work done by the fluid, W .
2
Because there is steady flows of fluid into and out of the system and steady flows of heat and
work, then the energy entering must exactly equal the energy leaving.
C12 C 22
u1   Z1 g  p1v1  Q  u 2   Z 2 g  p2 v2  W (12)
2 2
In most of the applied thermodynamics system the changes in height are negligible; therefore the
potential energy tern can be omitted. Thus equation (12) becomes:
C2 C2
u1  1  p1v1  Q  u 2  2  p 2 v2  W (13)
2 2
The terms u and pv occur on both sides of equation (13) and the sum of u and pv is given the
symbol h and is called enthalpy
Enthalpy, h  u  pv (14)
Thus, h1  u1  p1v1 (14a)
h2  u 2  p2 v2 (14b)
Substituting equations (14a) and (14b) in equation (13) gives
C12 C 22
h1   Q  h2  W (15)
2 2
Equation (15) is known as the steady-flow energy equation
In steady flow the rate of mass flow of fluid at any section is the same as at any other section.
Consider any section of cross-section area A, where the final velocity is C, then the rate of
volume flow past the section is CA, Also, since mass flow is volume flow divided by the
specific volume,
* CA
Mass flow rate,  v
m (16)
(Where, v is specific volume)
Equation (16) is called continuity of mass equation
* CA C A
m 1 1  2 2 (17)
v1 v2

20
STEADY FLOW EQUATION APPLIED IN OPEN SYSTEMS

i. Boiler
A boiler is a system that converts liquid to vapour as shown in fig. 9 (a). Thus in a boiler, the
fluid enters as a liquid and leaves as a vapour at a constant rate. No work is done on or by the
fluid as it passes through the system, thus W  0 . Also, the velocities of low are usually quite
low, so that the difference between the kinetic energies at inlet and outlet is negligible compared
with the other terms of the steady flow equation. Thus the steady flow equation
C2 C2 C2 C2
h1  1  Q  h2  2  W reduces to Q  (h2  h1 )  2  1  (h2  h1 ) since C2  C1
2 2 2 2
For Boiler, steady state equation is Q  ( h2  h1 ) (18)

Fig. 9 (a) A boiler Fig. 9 (b) a condenser

EXAMPLE
2000kg of steam are to be produced per hour at a pressure of 20 bar, temperature 400 0C and
enthalpy 3248kJ/kg. The feed water is supplied to the boiler at a temperature of 500C and has
enthalpy of 209.3kJ/kg. Find the rate at which heat must be supplied, assuming typical values for
the velocity at inlet and outlet: 2 m/s in the feed pipe and 45 m/s in the steam main.

SOLUTION
GIVEN:
Feed water into boiler at 500C, h1  209.3 kJ / kg


Superheated steam at 20 bar at 400 C, h2  3248 kJ / kg ; Steam production rate m  2000 kg / h

0

C1  2 m / s ; C2  45 m / s

21
From steady flow energy equation, since C1  C2 the heat required per kg of steam is given as:

C 22 C12 (45 2  2 2 )
Q  (h2  h1 )    (3248  209.3)   3038.7  1.0105  3039.7 kJ / kg
2 2 2  10 3
* 2000
Thus, the rate of heat supplied is Q  3600  3039.7  1688.7 kJ / s
m

ii. Condenser
A condenser is a system that changes vapour to liquid as shown in fig. 9 (b). The vapour passes
over a bank of tubes and is condensed as it comes in contact with the surface of the tubes. The
tubes are maintained at a lower temperature than the vapour by a flow of cooling water. The
cooling water is not part of the fluid of this open system, but acts as a sink of heat in the
surroundings.
C12 C 22
Thus for condenser, the steady flow equation h1  2  Q  h2  2  W reduces to
Q  h2  h1 (19)
Where, h1  h2 thus, Q is negative.

EXAMPLE
A steady flow of steam enters a condenser with enthalpy of 3500 kJ/kg and a velocity of 370
m/s. The condensate leaves the condenser with an enthalpy of 200 kJ/kg and velocity of 100 m/s.
Find the heat transfer to the cooling fluid per kg of steam condensed.

SOLUTION
GIVEN:
h1  3500 kJ / kg ; h2  200 kJ / kg ; C1  370 m / s ; C2  100 m / s

From steady flow energy equation, since C1  C2 , the heat transferred to the cooling fluid per kg
of steam condensed is:
C 22 C12 (100 2  370 2 )
Q  (h2  h1 )    (200  3500)   3300  (63.45)  3236.55 kJ / kg
2 2 2  10 3
Thus the heat transferred to cooling water is Q  3236.55 kJ / kg

iii. Nozzles

A nozzle is a duct of varying cross-sectional area so designed that a drop in pressure from inlet to
outlet accelerates the flow as shown in fig. 10 (a). The flow through a nozzle occurs at a very
high speed and there is little time for the fluid to gain or loss energy by flow of heat through the
walls of the nozzle as the fluid passes through it. The process is thus assumed to be adiabatic.
Also, no work crosses the boundary during the process. Thus the steady- flow equation
C2 C2
h1  1  Q  h2  2  W becomes;
2 2

22
 C 22 C12
(  )  h1  h2 (20)
2 2
Since Q  0 and W  0
Nozzles are found applicable in steam and gas turbines, jet engines, rockets motors and fluid
measurements.

Fig. 10 (a) Nozzle (b) Diffuser

EXAMPLE
A nozzle is a device for increasing the velocity of a steady flowing stream of fluid. At the inlet to
a certain nozzle the enthalpy of the fluid is 3025kJ/kg and the velocity is 60m/s. At the exit from
the nozzle the enthalpy is 2790kJ/kg. The nozzle is horizontal and there is negligible heat loss
from it.
(a) Find the velocity at the nozzle exit.
(b) If the inlet area is 0.1 m3 and the specific volume at inlet is 0.19 m3/kg, find the rate of
flow of fluid.
(c) If the specific volume at the nozzle exit is 0.5 m3/kg, find the exit area of the nozzle.

SOLUTION
GIVEN:
C1  60 m / s ; h1  3025 kJ / kg ; h2  2790 kJ / kg ; A1  0.1 m 2 ; v1  0.19 m 3 / kg
v2  0.5 m 3 / kg ; C 2  ? ; A2  ?

C 22 C12
From steady flow energy equation (20), ( 2  2 )  h1  h2 and solving for C 2 gives
C2  2  103  (h1  h2 )  C12  2  103  (3025  2790)  60 2  473600  688.2 m / s

 C1 A1 60  0.1
(b) Rate of flow m    31.6 kg / s
v1 0.19
C1 A1 C 2 A2
(c) From continuity equation v  v solving for A2 gives;
1 2

C Av 60  0.1  0.5
A2  1 1 2   0.232 m 2
v1C 2 0.19  688.2

23
Thus A2  0.232 m
3

iv. Diffuser
A diffuser is a duct of smoothly varying increasing cross-sectional area in which a steadily
flowing fluid is made to decelerate thereby causing a rise in pressure along the stream in a duct
as shown in fig.10 (b). Areas of application are centrifugal compressor and ramjet.
v. Turbine
This is a system as shown in fig. 11, by means of which work is extracted from a flow of fluid
expanding from high pressure to a low pressure. In turbine, the fluid is accelerated in a set of
fixed nozzles, and the resulting high speed jets of fluid then change their direction as they pass
over a row of curved blades attached to a rotor. A force is exerted on the blades equal to the rate
of change of momentum of the fluid and thus produces a torque at the rotor shaft. At the same
time the velocity of the fluid is reduced to near the value it possessed before entering the nozzle.
Thus the velocity flow at the inlet and outlet can be assumed to be equal. Since the average
velocity of flow through a turbine is very high, the process can be assumed to be adiabatic. Thus
C12 C 22
the steady flow equation h1  2  Q  h2  2  W
becomes, W  (h1  h2 ) (21)
Since Q  0

Fig. 11 Turbine

EXAMPLE
A turbine operating under steady flow condition receives steam at the following state;
Pressure 13.8 bar; specific volume 0.143 m3/kg; internal energy 2590kJ/kg; velocity 30m/s. The
state of the steam leaving the turbine is; Pressure 0.35 bar; specific volume 4.37 m3/kg; internal
energy 2360 kJ/kg; velocity 70m/s. Heat is lost to the surroundings at the rate of 0.25kJ/s. If the
rate of steam flow is 0.38kg/s. What is the power developed by the turbine?

24
SOLUTION
GIVEN:
p1  13.8 bar ; p2  0.35 bar ; v1  0.143 m 3 / kg ; v2  4.37 m 3 / kg ; u1  2590 kJ / kg

u 2  2360 kJ / kg ; C1  30 m / s ; C2  90 m / s ; m  0.38 kg / s

C12 C 22
u 
From steady flow energy equation (13) 1 2  p v
1 1  Q  u 2   p 2 v2  W , solving for
2
W gives;
C12  C 22
W  (u1  u 2 )  ( p1v1  p 2 v 2 )  ( )Q
2
30 2  90 2
W  (2590  2360)  (13.8  0.143  0.35  4.37)  10 2  ( )  0.25
2  10 3
W  230  (0.444)  10 2  3.600  0.25
W  271.05 kJ / kg


Thus the total work done is given as WTotal  W  m  271.05  0.38  103 k W
vi. Rotary Compressor
A rotary compressor is a reverse of a turbine, where work done on the fluid to raise its pressure.
Work is done on the fluid by a bladed rotor driven from an external source. This increases the
velocity of the fluid. The velocity is then reduced in a set of fixed diffusers to some value
approximately to that at inlet of the compressor, and the pressure is increased. Thus from
C12 C 22
h 
equation of steady flow, 1 2  Q  h2   W becomes,
2
W  (h1  h2 ) (22)
Where h2  h1 and Q  0

EXAMPLE
Air flows steadily at the rate of 0.4kg/s through an air compressor, entering at 6m/s with a
pressure of 1 bar and a specific volume of 0.85 m3/kg and leaving at 4.5m/s with a pressure of
6.9 bar and a specific volume of 0.16 m3/kg. The internal energy of the air leaving is 88kJ/kg.
greater than that of the air entering. Cooling water in a jacket at the rate of 59kJ/s. Calculate the
power required to drive the compressor and the inlet and outlet pipe cross-sectional areas.

SOLUTION

GIVEN:
C1  6 m / s ; p1  1 bar ; v1  0.85 m 3 / kg ; (u 2  u1 )  88 kJ / kg ; C2  4.5 m / s ; p2  6.9 bar
*
v2  0.16 m 3 / kg ; Q  59 kJ / s ; m  0.4 kg / s
From steady flow energy equation (13)

25
 C12 C 22
u1   p1v1  Q  u 2   p 2 v2  W , solving for W gives;
2 2
C 2  C 22
W  (u1  u 2 )  ( p1v1  p 2 v 2 )  ( 1 )Q
2
6 2  4.5 2 59
W  (88)  (1  0.85  6.9  0.16)  10 2  ( )
2  10 3
0.4
W  88  (0.254)  10  0.00788  147.5
2

W  259.99 kJ / kg

Thus the total work done WTotal  W  m  259.99  0.4  104 kW

 C1 A1  C 2 A2
From continuity equation m  and m  A1 gives;
v1 v2 solving for

m v1 0.4  0.85
A1    0.0567 m 2
C1 6

m v2 0.4  0.16
Similarly, solving for A2    0.0142 m 2
C2 4.5

vii. Reciprocating Compressor

Like the rotary compressor, the reciprocating compressor is a reversed turbine. It does work on
fluid to raise its pressure as shown in fig.12. However, some heat transfer does occur in a
relatively low speed, and the surface area of the cylinder walls is appreciable.

Fig. 12 Rotary compressor

The difference between the kinetic energies at inlet and outlet can be neglected. Thus the steady
C12 C 22
h
flow equation 1 2  Q  h2  W
2 becomes;

26
Q  W  (h2  h1 ) (23)

viii. Throttling
A flow of fluid is said to be throttled when some restriction is placed in the flow as shown in in
fig.13. A partially closed valve in a pipe line is a simple example. The term throttling is usually
applied to relatively low-speed flow, i.e low enough for any difference between the kinetic
energy at inlet and outlet to be negligible. Any heat transfer across the boundary can be
neglected; because throttling takes place in such a short length of pipe that the surface area
across which heat can flow is very small.

Fig. 13. Throttling process

There is no work across the boundary. Therefore, the steady flow energy equation
C2 C2
h1  1  Q  h2  2  W
2 2 becomes
h1  h2 (24)

Since W  0 , Q  0 and C1  C2
We thus say that throttling process is an adiabatic steady flow process such that the enthalpy is
the same at inlet and outlet.

SPECIFIC HEAT CAPACITIES

The specific heat of a solid or liquid is usually defined as the heat required to raise unit mass
through one degree temperature rise, mathematically expressed as:
dQ  mcdT (25)

Where, m is the mass, dT is the increase in temperature and c is the specific heat capacity. It is
important to note that the definition must be restricted to reversible non-flow processes, since
irreversibilities can cause temperature changes which are indistinguishable from those due to
reversible heat work quantities. There are many number of ways in which heat may be added to
gas between any two temperatures, hence gas could have an infinite number of specific heats.
For example, heat can be added at constant volume and constant pressure. Thus, we have specific
heat capacity at constant volume, c v and specific heat at constant pressure, c p .

27
We have,
dQ  mc p dT (26)
For reversible non-flow process at constant pressure

dQ  mcv dT (27)
For reversible non-flow process at constant volume

The values of c p and c v for perfect gas are constant for any one gas at all pressures and
temperatures. Hence integrating equations (26) and (27) will give,
2
Q  mc p  dT  mc p T2  T1  (28)
1

2
Q  mcv  dT  mcv T2  T1  (29)
1

For real gases, c p and c v vary with temperature, but for most practical purposes a suitable
average value may be used.

JOULE’S LAW

According to Joule’s law, the internal energy of a perfect gas is a function of the absolute
temperature only expressed as u  f (T ) .
Let’s consider 1kg of a perfect gas be heated at a constant volume. Since the volume is constant,
then no work is done, i.e. dW  0
Thus, the non-flow energy equation (9) dQ  du  dW becomes;
dQ  du (i)
Similarly, at constant volume for 1 kg of a perfect gas, equation (27) becomes
dQ  cv dT (ii)
Equating equations (i) and (ii) gives dQ  du  cv dT (iii)
Integrating equation (iii) gives  du  cv  dT  u  cvT  K (iv)
Where K is a constant
It follows from equation (iv) that the internal energy varies linearly with absolute temperature.
For a perfect gas it can be assumed that u  0 when T  0 , hence the constant K  0 .
Therefore, for 1 kg of perfect gas u  cvT (v)
And for m mass of perfect gas, U  mcvT (vi)
For a perfect gas that undergoes process between states 1 and 2, the gain in internal energy can
be obtained from equation (vi) as;
Gain in internal energy, U 2  U1  mcv (T2  T1 ) (30)
Equation (30) is applicable to both reversible and irreversible processes.

28
Relationship between the specific heat capacities

Let’s consider a perfect gas heated at constant pressure from T1 to T2 . Now from the non-flow
equation, (7) Q  (U 2  U1 )  W (i)
U
Also for perfect gas from equation (30) 2  U 1  mc v (T2  T1 ) (ii)
Thus substituting equation (ii) in (i) gives;
Q  mcv (T2  T1 )  W (iii)
Similarly, in a constant pressure process the work done by the fluid is given by the pressure
times the change in volume, i.e. W  p(V2  V1 ) (iv)
Also, from equations (1c) and (1d), we have;
p1V1  m1 RT1 (v)

p2V2  m2 RT2 (vi)

But for constant pressure process p1  p2  p
Thus, substituting equations (v) and (vi) in equation (iv) gives;
. W  mR(T2  T1 ) (vii)

Substituting equation (vii) in equation (iii) gives;

Q  mcv (T2  T1 )  mR(T2  T1 )  m(cv  R)(T2  T1 ) (viii)

However, for constant pressure process from equation (28) Q  mc p (T2  T1 ) (ix)

Substituting equation (ix) in (viii) gives;

m(cv  R)(T2  T1 )  mc p (T2  T1 ) (x)

Simplifying equation (x) gives cv  R  c p

Or c p  cv  R (31)

Enthalpy of a perfect gas

From equation (14), enthalpy, h  u  pv (i)

For a perfect gas, from equation (1) gives pv  RT (ii)

Similarly, for perfect gas from Joule’s law, u  cvT (iii)

Hence, substituting equations (ii), (iii) in (i) gives;

29
h  cvT  RT  (cv  R)T (iv)

But from equation (31), cv  R  c p and substituting in equation (iv) gives;

h  cvT  RT  (cv  R)T  c pT

Thus, h  c pT (32)

For mass, m , of a perfect gas

H  mc pT (33)

Ratio of specific heat capacity

The ratio of the specific heat at constant pressure to the specific heat at constant volume is given
cp
as;   (34)
c v

From equation (31) c p  cv  R (i)

c p cv R cp R
Dividing equation (i) by c v gives c  c  c . Simplifying gives c 1  c (ii)
v v v v v

R
Substituting equation (34) in (ii) gives  1  c . Rearranging gives
v

R
cv 
(  1) (35)

EXAMPLES

1. The molecular weight of carbon dioxide, CO2 is 44. In an experiment the value of  for
CO2 was found to be 1.3. Assuming that CO2 is a perfect gas, calculate the gas constant,

R, and the specific heats at constant pressure, c p and constant volume, c v .

SOLUTION

GIVEN:

Ro  8314.3 Nm / mole K ; M  44kg ;   1.3 ; R  ? ; cv  ? ; c p  ?

30
 Ro 8314.3
From R  M  44  189 Nm / kgK  0.189kJ / kgK

R 0.189
c    0.63 kJ / kgK
Also, from (  1) (1.3  1)
v

From c p  R  cv  0.189  0.63  0.819 kJ / kgK

2. Calculate the internal energy and enthalpy of 1 kg of air occupying 0.05 m 3 at 20 bar. If
the internal energy is increased by 120kJ/kg as the air is compressed to 50 bar, calculate
the new volume occupied by 1 kg of the air. For air take, cv  0.718 kJ / kgK ;
c p  1.005 kJ / kgK and R  0.287 kJ / kg / K
SOLUTION

GIVEN:

R  0.287 kJ / kg / K ; cv  0.718 kJ / kgK ; V1  0.05 m 3 ; (u 2  u1 )  120 kJ / kgK ;

c p  1.005 kJ / kgK ; p1  20 bar ; p2  50 bar ; m  1kg

p1V1 20  10 2  0.05
p V
From 1 1  mRT1 we have, T1    348 K
R 0.287

Similarly, from (u 2  u1 )  cv (T2  T1 ) and solving for

(u  u1 )  cvT1 120  0.718  348
T2  2   515.13 K
cv 0.718

p1V1 p 2V2
From p1V1  mRT1 and p2V2  mRT2 we have T  T . Thus, solving for V2 gives;
1 2

From u 2  cvT2  0.718  515.13  369.89 kJ / kg , however, the internal energy of the system is
increased by 120 kJ / kg . Thus, the internal energy of the system is
u1  369.89  120  249.86  250 kJ / kg

Similarly, enthalpy of the system can be calculated from:

h1  c pT1  1.005  348  349.74  350 kJ / kg

3. When a certain perfect gas is heated at constant pressure from 150C to 950C, the heat
required is 1136kJ/kg. When the same gas is heated at constant volume between the same

31
 temperatures the heat required is 808kJ/kg. Calculate c p , c v  , R and the molecular
weight of the gas.
SOLUTION

GIVEN:

T1  150 C  15  273  288 K ; T2  950 C  95  273  368 K ; Q p  1136 kJ / kg ;

Qv  808 kJ / kg

Qp 1136
From Q  c (T  T ) , solving for c    14.2 kJ / kgK
(T2  T1 ) (368  288)
p p 2 1 p

Qv 808
Similarly, from Qv  cv (T2  T1 ) , solving for cv  (T  T )  (368  288)  10.1 kJ / kgK
2 1

From R  c p  cv  14.2  10.1  4.1 kJ / kgK

R 4.1
Also, from   c  1  10.1  1  1.405 kJ / kgK
v

Ro 8.3144
M   2.08 kg / Kmol.
Molecular mass R 4.1

4. In an air compressor the pressures at inlet and outlet are 1 bar and 5 bar respectively. The
temperature of the air at inlet is 150C and the volume at the beginning of compression is
three times that at the end of compression. Calculate the temperature of the air at outlet
and the increase of internal energy per kg of air.
SOLUTION

GIVEN:

p1  1 bar ; p2  5 bar ; T1  150 C  15  273  288 K ; v1  3v2 ; T2  ? (u 2  u1 )  ?

p1V1 p 2V2
From p1V1  mRT1 and p2V2  mRT2 we have T  T and solving for T2 gives;
1 2

p 2V2T1 5  V1  288
T2    480 K  480  273  207 0 C
p1V1 1  3  V1

Increase in internal energy (u 2  u1 )  mcv (T2  T1 )  0.718(480  288)  138 kJ / kg

32
EXERCISE

5. A quantity of a certain perfect gas is compressed from an initial state of 0.085 m3, 1 bar
to a final state of 0.034 m3, 3.9 bar. The specific heat at constant volume is 0.724kJ/kgK,
and the specific heat at constant pressure is 1.02kJ/kgK. The observed temperature rise is
146K. Calculate the gas constant, R, the mass of gas present, and the increase of the
internal energy of the gas.

REVERSIBLE NON-FLOW PROCESSES

A. Constant volume process

As earlier explained, the constant volume process has the working substance contained in a rigid
vessel, hence the boundaries of the system is immovable and no work can be done by or on the
system, other than paddle-wheel work input. Thus, it can be assumed that for constant work
process, there is zero work unless stated otherwise.

Fig.14. A constant volume process on a p-v diagram

From non-flow energy equation (8), Q  (u 2  u1 )  W , and since there is no work done, we
have,

Q  (u 2  u1 ) (36)

For m , mass of the working fluid, equation (36) becomes;

Q  (U 2  U1 ) (i)

This implies that for constant volume process, the heat supplied goes to increase the internal
energy of the working fluid in the system.

33
For a perfect gas, the change in internal energy of a system for a constant volume process as
given by equation (30) is;

U 2  U1  mcv (T2  T1 ) (ii).

And substituting equation (ii) in equation (i) gives;

Q  mcv (T2  T1 ) (37)

B. Constant pressure process

This is explained as the process carried out such that the pressure remains constant throughout
the process. In constant pressure process the boundary must move against an external resistance
as heat is supplied; for example a fluid in a cylinder behind a piston can be made to undergo a
constant pressure process. Since the piston is pushed through a certain distance by the force
exerted by the fluid, then the work is done by the fluid on the surroundings. The constant
pressure process is as given in fig.15 on the p-v diagram. The shaded area under the p-v diagram
represents the total work done.

Fig.15. A constant pressure process on a p-v diagram

2
v2
From equation (3), for any reversible work done, we have, W   pdv  v1 pdv (i)
1

Since p is constant, integrating equation (i) with respect to v gives;

2
W   pdv   pdv  p(v2  v1 )
v2

v1 (ii)
1

But for the non-flow energy equation for unit mass;

Q  (u 2  u1 )  W (iii)

Substituting equation (ii) in equation (iii) gives;

34
Q  (u 2  u1 )  p(v2  v1 )  (u2  pv2 )  (u1  pv1 ) (iv)

Thus, rearranging equation (iv) gives Q  h2  h1 (38)

For m , mass of a fluid, Q  H 2  H1

Similarly, for a perfect gas, at constant pressure process, the heat supplied is given in equation
(28) as;

Q  mc p (T2  T1 )

C. Constant temperature process

In this process, the temperature of the system remains constant throughout the process. An
example is the process carried out according to Boyle’s law. When a fluid in a cylinder behind a
piston expands from a high pressure to a low pressure there is tendency for the temperature of
the system to fall. Thus, for a constant temperature expansion process, heat must be added
continuously in order to keep the temperature constant. Similarly, for constant temperature
compression process, heat must be removed from the fluid continuously during the process to
keep the temperature constant.

Fig.16. A constant temperature process on a p-v diagram

For perfect gas, constant temperature process is guide by the law;

pv  RT  C (39)

Where C is a constant

35
This implies that, applying equation (39), for constant temperature reversible process for states 1,
and 2 gives;

p1v1  p2 v2  C (40)

The work done by a perfect gas in expanding from state 1 to state 2 at constant temperature and
reversibly corresponding to the area under the p-v diagram in fig.16, is given as;
2
W   pdv   pdv
v2

v1 (i)
1

C
But from equation (39), p  v (ii)

Substituting equation (ii) in equation (i) and integrating with respect to v gives;
2
 Cln vv12  C ln 2
v2 v2 Cdv v
W   pdv   pdv  
v

1
v1 v1 v v1

v2
W  C ln (iii)
v1

Substituting for C  p1v1  p2 v2 in equation (iii) gives;

v2
W  p1v1 ln (41)
v1

v2
Or W  p 2 v 2 ln v (42)
1

v2
For m , mass of the gas, W  p1V1 ln v (43)
1

v2 p1
Also, since p1v1  p2 v2 , we have v  p (iv)
1 2

Substituting equation (iv) in equation (41) gives;

p1
W  p1v1 ln (44)
p2

36
 p1
For m , mass of the gas, W  p1V1 ln p (45)
2

Similarly, from equation (39), pv  RT , implies that, p1v1  RT (v)

Substituting (v) in equation (44) gives

p1
W  RT ln (46)
p2

p1
For m , mass of gas, we have W  mRT ln p (47)
2

It is also important to note that for a perfect gas from Joule’s law, equation (30) gives;

U 2  U1  mcv (T2  T1 )
(vi)

But for a constant temperature process, for a perfect gas, T1  T2 , thus, equation (vi) becomes

U 2 U1  0 , that is, the internal energy remains constant in a constant temperature process for a
perfect gas.

From non-flow energy equation,

Q  (u 2  u1 )  W , and since u1  u 2 , then;

Q W (48)

D. Reversible Adiabatic process

An adiabatic process is one in which no heat is transferred to or from the fluid during the
process. Such process can be reversible or irreversible. We are considering a reversible process.

From non-flow energy equation, Q  (u 2  u1 )  W , and for adiabatic process, Q  0

Thus, we have, W  (u1  u 2 ) (49)

Equation (49) is applicable to all adiabatic process whether reversible or not. In an adiabatic
expansion, the work done by the fluid is at the expense of a reduction in the internal energy of
the fluid. Similarly, in an adiabatic compression process all the work done on the fluid goes to
increasing the internal energy of the fluid. For an adiabatic process to take place, perfect thermal
insulation for the system must be available.

37
The law relating pressure, p and specific volume, v for a perfect gas may be obtained for a
reversible adiabatic process, considering the non-floe energy equation in differential form.

From equation (9);

dQ  du  dW (i)

Also for reversible process, W   pdv and differentiating with respect to v , gives

dW  pdv (ii)

Substituting equation (ii) in equation (i) for reversible adiabatic process, we have

Q  du  pdv  0 (iii)

Now, for a perfect gas, from equation (1) pv  RT , from which,

RT
p (iv)
v

Also, from u  cvT and du  cv dT (v)

Substituting equations (iv) and (v) in equation (iii) gives;

RTdv
cv dT   0 , Dividing through by T gives;
v

cv dT Rdv
  0 Integrating both sides gives;
T v

cv ln T  R ln v  Cons tan t . (vi)

pv
Similarly, from pv  RT , we have T  R (vii)

Substituting equation (vii) in equation (vi) gives;

pv
cv ln  R ln v  Cons tan t . (viii)
R

Dividing equation (viii) by c v gives;

pv R
ln  ln v  Cons tan t . (ix)
R cv

38
 R
Also, from  1  c and substituting in equation (ix) gives;
v

pv
ln  (  1) ln v  Cons tan t .. Simplifying gives
R

pv
ln  ln v  1  Cons tan t
R

pvv 1
ln  Cons tan nt
R

pv 
ln  Cons tan nt
R

pv   e cons tan t  Cons tan t (50)

From equation (50), the relationship between equation p , v and T may derived using the perfect
gas equation pv  RT (i)

RT
From equation (i) p  v (ii)

Substituting equation (ii) in equation (50) gives;

RTv 
 Cons tan t
v

Tv 1  Cons tan t (51)

RT
Also, from pv  RT , we have, v  p .And substituting in equation (50) and simplifying gives;


 RT 
p   Cons tan t
 p 

T
 Cons tan t
p  1

T
( 1) / 
 Cons tan t (52)
p

39
Thus for a perfect gas undergoing reversible adiabatic process from states 1 and 2, we have;

From equation (50);


  p1  v 2 
p1v1  p2 v2 or p   v  (53)
2  1

From equation (51);

 1
 1  1 T1  v 2 
T1v1  T2 v or T   v  (54)
2  1

From equation (52);

( 1) / 
T1 T2 T1  p1 
p1( 1) / 

p 2( 1) /  or T   p  (55)
2  2 

From equation (49) the work done in an adiabatic reversible process is given as;

W  (u1  u 2 ) (i)

Also, the gain in internal energy for a unit mass of a perfect gas is given as;

u 2  u1  cv (T2  T1 ) (ii)

Substituting equation (ii) in equation (i) gives;

W c v (T1  T2 ) (iii)

R
But cv  (  1) (iv)

Substituting equation (iv) in equation (iii) gives;

R(T1  T2 ) RT1  RT2

W 
(  1) (  1) (56)

Substituting from pv  RT ,in equation (56) gives;

p1v1  p 2 v 2
W
(  1) (57)

40
 E. Polytropic process
There are many thermodynamic processes in practice that approximate to reversible law of the
form pv  Cons tan t , where n is a constant. Both vapours and perfect gas obey this law
n

closely in many non-flow processes.

For any reversible process,

W   pdv (i)

C
And for a process in which pv  C, we have p  v n ,
n
(ii)

where C is a constant;
n
Also from equation (ii), p  Cv , thus, for states 1 and 2, we have;

p1  Cv1 n (iii)

p2  Cv2 n (iv)
v2
v2 dv  v n 1   v2n 1  v1n 1   Cv 2n  v2  Cv1n  v1 
Thus, W  C v1 vn
 C 
 
  C 
 
  
 
 (v)
 n 1  v1  n 1   n 1 

Substituting equations (iii) and (iv) in equation (v) gives;

p 2 v2  p1v1
W
 n  1 , Multiplying and dividing by (-1) gives;

p1v1  p 2 v2
W (58)
n 1

For perfect gas, of mass m gives pV  mRT ,

Thus, p1V1  RT1 (i)

p2V2  RT2 (ii)

Substituting equations (i) and (ii) in equation (58) gives;

mR(T1  T2 )
W (iii)
n 1

41
Applying the non-flow energy equation for m mass of gas, we have,

Q  (U 2  U1 )  W , (iv)

But U 2  U1  mcv (T2  T1 ) (v)

Substituting equation (iii) and (v) in equation (iv) gives;

mR(T1  T2 )
Q  mcv (T2  T1 )  (59)
n 1

Le t’s consider a polytropic process in which the state changes from 1 to 2

Thus, p1v1  p2 v2
n n
(i)

p1v1 p 2 v 2
From characteristic gas equation, T  T (ii)
1 2

n
p1  v 2 
From equation (i), p   v  (iii)
2  1 

T1  p1  v1 
Also, from equation (ii), T   p  v  (iv)
2  2  2 

Substituting equation (iii) in equation (iv) gives;

n n 1 n 1
T1  v2   v1   v2   v2  v 
           2 
T2  v1   v2   v1   v1   v1 
(v)

1/ n 1/ n
v 2  p1  v1  p 2 
From equation (iii), v   p  or v   p  (vi)
1  2  2  1 
1 n 1
T1 p1  p1  n  p1  n

Substituting (vi) in (iii) gives; T      

2 p 2  p2   p2  (vii)

Equating equation (v) and (vii) gives;

n 1
n 1
T1  p1  n v 
    2 
T2  p 2   v1 
(viii)

42
 n
Raising equation (viii) to the power of n  1 gives;

n n 1 n n
 n 1
 T1  n 1  p1  n n 1 v  n 1
       2  (ix)
 T2   p2   v1 
n
n
 T1  n 1 p v 
   1   2  (x)
 T2  p 2  v1 

1
Also raising equation (viii) to the power of n  1 , gives;

1 n i 1 1
 n 1
 T1  n 1 p  n n 1 v  n 1
    1    2  (xi)
 T2   p2   v1 
1 1
 T1  n 1  p1  n v 2
      (xi)
 T2   p2  v1

It is sometimes more convenient to express the work done in terms of the temperatures at the end
of state for a perfect gas expanding polytropically.

p1v1  p 2 v2
Thus from equation (58) W  n 1 and substituting p1V1  RT1 and p2V2  RT2 , into
the equation gives;

R(T1  T2 )
W
n 1

mR(T1  T2 )
For m , mass of gas, W  n 1

From the non-flow energy equation, the heat flow during the process is given as

R(T1  T2 )
Q  (u 2  u1 )  W  cv (T2  T1 ) 
(n  1)

Rearranging gives

R(T1  T2 )
Q  cv (T1  T2 ) (i)
(n  1)

43
 R
c 
From (  1) and substituting in (i) gives
v

R R
Q (T1  T2 )  (T1  T2 ) rearranging gives
(n  1) (  1)

 1 1  R(T1  T2 )(  1  n  1)
Q  R(T1  T2 )   
 n 1  1 (  1)(n  1)

   n  R(T1  T2 )
Q   
   1  (n  1)
Thus, (ii)

R(T1  T2 )
However, from W  n 1 for unit mass of perfect gas and substituting in (ii) gives

  n
Q    W
  1 
(60)

The index n depends exclusively on the work and heat quantities during the process for a
polytrophic process.

In summary, the various polytrophic process for a perfect gas are as shown below.

Figure 17. Special cases of polytrophic processes of perfect gas.

44
When n  0 we have pv  constant, i.e. p  constant
0

When n   we have pv  constant or p v  constant, i.e. v  constant .

 

When n  1 we have pv  constant, i.e. T  constant

pv
(since T  constant for perfect gas)


When n   we have pv  constant, i.e. reversible adiabatic process.

The p  v diagram shown in figure 17 gives an illustration of the summary of the polytrophic
process.

State 1 to state A is a constant pressure cooling (n  0) ;

State 1 to state B is isothermal compression (n  1) ;

State 1 to state C is reversible adiabatic compression (n   ) ;

State 1 to D is a constant volume heating (n  ) .

, , ,
Likewise, 1 to A is constant pressure heating; 1 to B is isothermal expansion; 1 to C is
,
reversible adiabatic expansion; 1 to D is constant volume cooling. It is important to note that
since  is always greater than unity, then the process 1 to C must lie between process 1 to B and
, , ,
1 to D; similarly, process 1 to C must lie between processes 1 to B and 1 to D .

However , for vapour it is not possible to make a generalization such as above. A vapour may
undergo a process according to a law pv  constant. Now since the characteristic equation state
pv  RT does not apply to a vapour, then the process is not isothermal. The steam table must be

used to find the properties at the end of state, making use of the fact that p1v1  p2 v2 .

EXAMPLES:

1. Air at 2 bar, 27 0 C initially occupying a cylinder volume of 0.030 m3 is compressed

reversibly and adiabatically by a piston to a pressure of 10 bar. Calculate the final
temperature, the final volume and the work done on the mass of the air in the cylinder.

45
SOLUTION
GIVEN:
T1  273  27 0  300 K ;   1.4 and cv  0.718 kJ / kgK
( 1) /  ( 1) / 
T1  p1  p 
From equation (55) we have T   p  T2  T1   2 
2  2  , and  p1 

1.4 1
 10  1.4
T2  300     475.145 K
Substituting gives 2

Therefore the final temperature is 475.145 -273=202.1450 C.

1 1

p1  v 2  v1  p 2    p 
 
p 2  v1  and v   p  v 2  v1   1 
From equation (53), we have 2  1 . Thus,  p2 

and substituting gives

1
 2  1.4
v 2  0.03     0.0095 m 3
 10 

The final volume is 0.0095 m3.

R(T1  T2 )
W  cv (T1  T2 ) and
(  1) substituting gives
For adiabatic process, work done is
W  0.718(399  475.145)  125.75 kJ / kg

Thus, the work done on the mass of air in the cylinder is 125.75 kJ/kg.

p1v1
The mass of air in the cylinder can be determined from pv  mRT where, m  RT
1

46
 2  10 5  0.03
m  0.0696864 kg
0.287  10 3  300
Substituting gives

WT  m  W  0.0696864  125.75  8.76 kJ

The total work done is

2. 1 kg of Oxygen gas (molecular weight 32) is compressed reversibly and isothermally from
1.5 bar, 350 C to 7.5 bar. Calculate the work done and the heat flow during the process.
Assume Oxygen is a perfect gas.

SOLUTION
GIVEN:
R0  8.314 kJ / kmol K T1  273  35  310 K
The universal gas constant ; ; Molecular weight of
Oxygen gas M= 32 kg; P1=1.5 bar and p2=7.5 bar
R 8.314
R O   0.2598123 kJ / kgK
M 32
From
When a process takes place from left to right on a p-v diagram, then work is done on the fluid
p 1.5
W  RT ln 1 we have W  0.2598  300  ln
p2 7.5
and is negative. Thus, from

W  129.62 kJ / kg  130 kJ / kg
Q  W  130 kJ / kg
For isothermal process, fro perfect gas,

47
 pv1.3  c
3. 1 kg of air at 1.02 bar, 200 C is compressed reversibly according to a law ,
where c is a constant., to a pressure of 5.5 bar. Calculate the work done on the air and the
heat flow to or from the cylinder walls during the compression.

SOLUTION
GIVEN:
p1  1.02 bar p2  5.5 bar T1  273  20  293 K R  0.2871 kJ / kg / K n  1.3
; ; ; ;
n 1 n 1
T1  p1  n p  n
  T2  T1  2 
T2  p 2   p1 
From we have,
1.31
 5.5  1.3
T2  293   432.25 K
Substituting gives  1.02 

R(T1  T2 )
W
n 1 , the work done on the air is
From

R(T1  T2 ) 0.2871  (293  432.25)

W   133.26 kJ / kg
n 1 1.3  1

R(T1  T2 )
Q  (u 2  u1 )  W  cv (T2  T1 ) 
The heat transfer is n 1

0.2871(293  432.25)
Q  0.71715(432.25  293)   99.8  133.26  33.45 kJ / kg
1.3  1

48
SECOND LAW OF THERMODYNAMICS

The first law of thermodynamics states that when a system undergoes a thermodynamics cycle
then the net heat supplied to the system from its surrounding is equal to the net workdone by the
system on its surrounding. The first law obeys the principle of conservation of energy.

Energy is a conserved property, and no process is known to have taken place in violation of the
first law of thermodynamics. Therefore, it is reasonable to conclude that a process must satisfy
the first law to occur. However, satisfying the first law alone does not ensure that the process
will actually take place. Let look consider the following processes:
If a cup of hot coffee left in a cooler room it eventually cools off. This process satisfies the first
law of thermodynamics since the amount of energy lost by the coffee is equal to the amount
gained by the surrounding air. Now let us consider the reverse process—the hot coffee getting
even hotter in a cooler room as a result of heat transfer from the room air. We all know that this
process never takes place. Yet, doing so would not violate the first law as long as the amount of
energy lost by the air is equal to the amount gained by the coffee.
Also, let’s consider a paddle-wheel mechanism that is operated by the fall of a mass. The paddle
wheel rotates as the mass falls and stirs a fluid within an insulated container. As a result, the
potential energy of the mass decreases, and the internal energy of the fluid increases in
accordance with the conservation of energy principle. However, the reverse process, raising the
mass by transferring heat from the fluid to the paddle wheel, does not occur in nature, although
doing so would not violate the first law of thermodynamics.

Figure: 18 Transferring heat to a paddle wheel will not cause it to rotate.

49
It is clear from the arguments above that processes proceed in a certain direction and not in the
reverse direction. The first law places no restriction on the direction of a process, but satisfying
the first law does not ensure that the process can actually occur. This inadequacy of the first law
to identify whether a process can take place is remedied by introducing another general principle,
the Second law of thermodynamics.
The use of the second law of thermodynamics is not limited to identifying the direction of
processes. The second law also asserts that energy has quality as well as quantity. The first law
is concerned with the quantity of energy and the transformations of energy from one form to
another with no regard to its quality. Preserving the quality of energy is a major concern to
engineers, and the second law provides the necessary means to determine the quality as well as
the degree of degradation of energy during a process.

THERMAL ENERGY RESERVOIRS

In the development of the second law of thermodynamics, it is very convenient to have a
hypothetical body with a relatively large thermal energy capacity (mass _ specific heat) that can
supply or absorb finite amounts of heat without undergoing any change in temperature. Such a
body is called a thermal energy reservoir, or just a reservoir. In practice, large bodies of water
such as oceans, lakes, and rivers as well as the atmospheric air can be modeled accurately as
thermal energy reservoirs because of their large thermal energy storage capabilities or thermal
masses. The atmosphere, for example, does not warm up as a result of heat losses from
residential buildings in winter. Likewise, mega joules of waste energy dumped in large rivers by
power plants do not cause any significant change in water temperature.
A two-phase system can be modeled as a reservoir also since it can absorb and release large
quantities of heat while remaining at constant temperature.
Another familiar example of a thermal energy reservoir is the industrial furnace. The
temperatures of most furnaces are carefully controlled, and they are capable of supplying large
quantities of thermal energy as heat in an essentially isothermal manner. Therefore, they can be
modeled as reservoirs.
A body does not actually have to be very large to be considered a reservoir. Any physical body
whose thermal energy capacity is large relative to the amount of energy it supplies or absorbs can

50
be modeled as one. The air in a room, for example, can be treated as a reservoir in the analysis of
the heat dissipation from a TV set in the room, since the amount of heat transfer from the TV set
to the room air is not large enough to have a noticeable effect on the room air temperature.
A reservoir that supplies energy in the form of heat is called a source, and one that absorbs
energy in the form of heat is called a sink. Thermal energy reservoirs are often referred to as
heat reservoirs since they supply or absorb energy in the form of heat.

HEAT ENGINE

Heat engine is a system operating in a complete cycle and developing net work from a supply of
heat. The work-producing device that best fits into the definition of a heat engine is the steam
power plant, which is an external-combustion engine. That is, combustion takes place outside the
engine, and the thermal energy released during this process is transferred to the steam as heat.
The schematic of a basic steam power plant is shown in figure 19.
The various quantities shown on this figure are as follows:
Qin - amount of heat supplied to steam in boiler from a high-temperature source (furnace)
Qout - amount of heat rejected from steam in condenser to a low temperature sink (the
atmosphere, a river, etc.)
Wnet –net work done

According to the first law of thermodynamics, net heat supplied =net work done
Qin  Qout  Wnet

51
Figure: 19 Part of the heat received by a heat engine is converted to work, while the rest is
rejected to a sink.

Thermal efficiency of a heat engine is defined as the ratio of the net work done in the cycle to the
gross heat supplied in the cycle.

Wnet Qin  Qout Q

Thermal efficiency   Q  Qin
 1  out
Qin
in

There are numerous valid statements of the second law of thermodynamics. However, two of
such statements are mostly considered.

(i) Kelvin-Planck’s Statement- states that it is impossible for any device that operates
on a cycle to receive heat from a single receiver and produce net amount of work.

This implies that, a heat engine must exchange heat with a low-temperature sink as well as a
high-temperature source to keep operating. The Kelvin–Planck statement can also be expressed
as no heat engine can have a thermal efficiency of 100 percent, or as for a power plant to
operate, the working fluid must exchange heat with the environment as well as the furnace.

52
 (ii) Clausius Statement- states that it is impossible to construct a device that operates in
a cycle and produces no effect other than the transfer of heat from a lower-
temperature body to a higher-temperature body.

It is common knowledge that heat does not, of its own volition, transfer from a cold medium to a
warmer one. The Clausius statement does not imply that a cyclic device that transfers heat from a
cold medium to a warmer one is impossible to construct. In fact, this is precisely what a common
household refrigerator does. It simply states that a refrigerator cannot operate unless its
compressor is driven by an external power source, such as an electric motor. This way, the net
effect on the surroundings involves the consumption of some energy in the form of work, in
addition to the transfer of heat from a colder body to a warmer one. That is, it leaves a trace in
the surroundings. Therefore, a household refrigerator is in complete compliance with the
Clausius statement of the second law.
The second law of thermodynamics is based on experimental observations. No experiments has
been conducted to contradict the second law, thus, taken as a proof for its validity. However,
both Kelvin-Planck and Clausius statements of the second law of thermodynamics are negative
statements and negative statement cannot be proved.

PERPETUAL MOTION MACHINES

A perpetual machine is any machine that violates the first and the second law of
thermodynamics. No perpetual motion machine is known to have worked.
A system that violates the first law of thermodynamics (i.e. creates energy) is perpetual motion
machine of the first kind (PMM 1)

53
Figure: 20 A perpetual-motion machine that violates the first law of thermodynamics (PMM1).

Let’s consider the steam power plant shown in figure 20. It is proposed to heat the steam by
resistance heaters placed inside the boiler, instead of by the energy supplied from fossil or
nuclear fuels. Part of the electricity generated by the plant is to be used to power the resistors as
well as the pump. The rest of the electric energy is to be supplied to the electric network as the
net work output. The inventor claims that once the system is started, this power plant will
produce electricity indefinitely without requiring any energy input from the outside.
A careful examination of this invention reveals that the system enclosed by the shaded area is

continuously supplying energy to the outside at a rate of Qout  Wnet,out without receiving any

energy. That is, this system is creating energy at a rate of Qout  Wnet,out , which is clearly a
violation of the first law. Therefore, this wonderful device is nothing more than a PMM1.
Similarly, a device that violates the second law of thermodynamics is called a perpetual motion
machine of the second kind (PMM2).
Let’s consider an inventor who decides to discard the condenser and decided to send the steam to
the pump as soon as it leaves the turbine as shown in figure 21. In this way, there is no heat
wasted and all the heat transferred to the steam in the boiler will be converted to work, and thus
the power plant will have a theoretical efficiency of 100 percent. Since the system works on a
cycle and does a net amount of work while exchanging heat with a single reservoir (the furnace)
only. It satisfies the first law but violates the second law, and therefore it will
not work. It is therefore considered as a perpetual motion machine of the second kind (PMM2)

54
Figure: 21 A perpetual-motion machine that violates the second law of thermodynamics
(PMM2).

ENTROPY
Clausius in 1865 realized that he had discovered a new thermodynamic property and he chose to
 dQ 
name the property entropy designated S and defined as ds   
 T  int er .rev . Entropy is an extensive
property of a system also referred as total entropy, S and has unit kJ/K. However, entropy per

unit mass designated s is an intensive property and has the unit kJ/kgK. Thus, S  ms where m is
the mass of the fluid.

 dQ 
2

The change in entropy ds  s 2  s1    T 

1 int er .rev

Entropy can be viewed as a measure of molecular disorder, or molecular randomness. As a

system becomes more disordered, the positions of the molecules become less predictable and the
entropy increases. Thus, it is not surprising that the entropy of a substance is lowest in the solid
phase and highest in the gas phase. In the solid phase, the molecules of a substance continually
oscillate about their equilibrium positions, but they cannot move relative to each other, and their

55
position at any instant can be predicted with good certainty. In the gas phase, however, the
molecules move about at random, collide with each other, and change direction, making it
extremely difficult to predict accurately the microscopic state of a system at any instant.
Associated with this molecular chaos is a high value of entropy. The quantity of energy is always
preserved during an actual process (the first law), but the quality is bound to decrease (the
second law). This decrease in quality is always accompanied by an increase in entropy.

T-S DAIGRAM FOR PERFECT GAS

The area under the P-V diagram for a reversible process represents the workdone. Similarly, the
area under the T-S diagram for a reversible process represents the heat flow in the system.
2

On the P-V diagram, the reversible work is W   pdv

1

Similarly on the T-S diagram, the reversible heat flow is Q   Tds

1

(a) (b)
Figure 22: (a) P-V diagram (b) T-S diagram
As shown in figure 22 (b) above, the shaded area represent the heat supplied during the process.

Thus, Q  T (s2  s1 )

56
Reversible Isothermal Process for a Perfect Gas on a T-S Diagram

Figure 23: Isothermal process on a T-S diagram

From the non-flow equation for reversible process, we have

dQ  du  pdv (i)
Also for perfect gas from Joule’s law
du  cv dT (ii)
Putting equation (ii) in equation (i) gives
dQ  cv dT  pdv (iv)

But for isothermal process, dT  0 , hence

dQ  pdv (v)

For perfect gas, pv  RT

dv
Thus, dQ  pdv  RT (vi)
v
2 2 2 2
dQ dv dv
From  ds   T  RT  Tv  R  v
1 1 1 1

v  p 
s 2  s1  R ln  2   R ln  1 
 v1   p2 

57
Reversible Constant Pressure and Constant Volume Process for a Perfect Gas on a T-S
Diagram
A plot of the lines of constant pressure and constant volume on the T-S diagram for perfect gas
shows that a line of constant pressure slopes less steeply than a line of constant volume.

Figure 24: Plot of constant volume and constant pressure on a T-S diagram

(A) Reversible Constant Pressure Process for Perfect Gas

From dQ  du  pdv  dh
2 2
dQ dh
But ds   T   T
1 1

For perfect gas dQ  dh  c p dT

2 2
c p dT T 
 ds  s2  s1  
1 1
T
c p ln  2 
 T1 

 T2 
Thus, s 2  s1  c p ln  T 
 1 

(B) Reversible Constant Volume Process for a Perfect Gas

From perfect gas, dQ  du  cv dT

58
 2 2
dQ
2
cv dT T 
Also,  ds  s 2  s1      cv ln  2 
1 1
T 1
T  T1 
 T2 
Thus, s 2  s1  c v ln  
 T1 

Reversible Polytropic Process for a Perfect Gas on a T-S Diagram

Figure 25: Polytropic process on a T-S diagram

The change in entropy for any polytropic process can be determined from the T-S diagram in two
stages:

First stage is to find the change in entropy in an isothermal process from v1 to v 2 which is given
as:
v 
s A  s1  R ln  2 
 v1 

Second stage is to find the change in entropy in a constant volume process from T1 to T2 where
T1  T2 which is given as:

T 
s A  s 2  cv ln  1 
 T2 

59
Thus, the change in entropy from state 1 to 2 is replaced by two simpler processes, i.e. from 1 to
A and from A to 2:
v  T 
s 2  s1  s A  s1   s B  s 2   R ln  2   cv ln  1 
 v1   T2 
Also from figure 25, the change in entropy can be determined when considering the process
changing from 1 to B and from B to 2.

First stage is a change in entropy at constant temperature between p1 to p 2 given as:

p 
s B  s1  R ln  1 
 p2 

Second stage is a change in entropy in a constant pressure process from T1 to T2 where T1  T2

which is given as:
T 
s B  s 2  c p ln  1 
 T2 
Hence, the change in entropy is:
p  T 
s 2  s1  s B  s1   s B  s 2   R ln  2   c p ln  1 
 p1   T2 

Reversible adiabatic (isentropic) Process for a Perfect Gas on a T-S Diagram

A process during which the entropy remains constant is called an isentropic process. It is

characterized by s  0 or s1  s 2 That is, a substance will have the same entropy value at the
end of the process as it does at the beginning if the process is carried out in an isentropic manner.
Many engineering systems or devices such as pumps, turbines, nozzles, and diffusers are
essentially adiabatic in their operation, and they perform best when the irreversibilities, such as
the friction associated with the process, are minimized. Therefore, an isentropic process can
serve as an appropriate model for actual processes. Also, isentropic processes enable us to define
efficiencies for processes to compare the actual performance of these devices to the performance
under idealized conditions. It should be recognized that a reversible adiabatic process is

necessarily isentropic s 2  s1 , but an isentropic process is not necessarily a reversible adiabatic

process. (The entropy increase of a substance during a process as a result of irreversibilities may

60
be offset by a decrease in entropy as a result of heat losses, for example.) However, the term
isentropic process is customarily used in thermodynamics to imply an internally reversible,
adiabatic process.

Figure 26: Isentropic process on a T-S diagram

CARNOT CYCLE
A reversible process is defined as a process that can be reversed without leaving any trace on
the surroundings. That is, both the system and the surroundings are returned to their initial states
at the end of the reverse process. This is possible only if the net heat and net work exchange
between the system and the surroundings is zero for the combined (original and reverse) process.
Processes that are not reversible are called irreversible processes.
Reversible processes actually do not occur in nature. They are merely idealizations of actual
processes. Reversible processes can be approximated by actual devices, but they can never be
achieved. That is, all the processes occurring in nature are irreversible. You may be wondering, then, why we
are bothering with such fictitious processes. There are two reasons. First, they are easy to analyze, since a

61
system passes through a series of equilibrium states during a reversible process; second, they
serve as idealized models to which actual processes can be compared.
The factors that cause a process to be irreversible are called irreversibilities. They include
friction, unrestrained expansion, mixing of two fluids, heat transfer across a finite temperature
difference, electric resistance, inelastic deformation of solids, and chemical reactions.
Engineers are interested in reversible processes because work-producing devices such as car
engines and gas or steam turbines deliver the most work, and work-consuming devices such as
compressors, fans, and pumps consume the least work when reversible processes are used instead
of irreversible ones.
Reversible cycles cannot be achieved in practice because the irreversibilities associated with
each process cannot be eliminated. However, reversible cycles provide upper limits on the
performance of real cycles. Heat engines and refrigerators that work on reversible cycles serve as
models to which actual heat engines and refrigerators can be compared. Reversible cycles also
serve as starting points in the development of actual cycles and are modified as needed to meet
certain requirements.
The most efficient possible cycle is one in which all the heat supplied is at one fixed temperature,
and all the heat rejected is at a lower fixed temperature. It is a reversible cycle known as the
Carnot cycle, first proposed in 1824 by French engineer Sadi Carnot. The theoretical heat
engine that operates on the Carnot cycle is called the Carnot heat engine. The Carnot cycle is
composed of four reversible processes—two isothermal and two adiabatic—and it can be
executed either in a closed or a steady-flow system.

62
Figure 27: Carnot cycle
The Carnot cycle is conveniently represented on a T-S diagram as shown in figure 27.
Process 1 to 2 is isentropic expansion from T1 to T2.
Process 2 to 3 is isothermal heat rejection
Process 3 to 4 is isentropic compression from T2 to T1.
Process 4 to 1 is isothermal heat supply.

Similarly, from the Carnot cycle it will be seen that the heat supplied , Q1 is given by the area

41BA4, i.e. Q1  T1 (s B  s A )

Heat rejected Q2 is given by the area 23AB2, i.e. . Q2  T2 (s B  s A )

Q2
The thermal efficiency of heat engine is given as:   1  Q
1

Q2 T2 ( s B  s A ) T2
Hence the thermal efficiency of Carnot cycle,  Carnot  1  Q  1  T ( s  s )  1  T
1 1 B A 1

T2
 Carnot  1 
T1
It can be seen that if a sink for heat rejection is available at a fixed temperature T 2 (for example a
T2
large supply of cooling water), then the ratio T will decrease as the temperature of the source
1

T1 is increased. Also, for a fixed lower temperature for heat rejection, the upper temperature at

which heat is supplied must be made as high as possible. The maximum possible thermal
efficiency between any two temperatures is that of the Carnot cycle.
The work output of the Carnot cycle can be found very simply from the T-S diagram.

From first law,  dQ   dW

Thus, the work output of the cycle is given by
W  Q1  Q2
Hence from the Carnot cycle,
WCarnot  Area 12341  T1 (s B  s A )  T2 (s B  s A )  (T1  T2 )(s B  s A )

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EXAMPLES

1. Air at 25oC and 1.05 bar occupies 0.04m3. The air is heated at constant volume until the
pressure is 5.0bar, and then cooled at constant pressure back to the original temperature.
Calculate the net heat flow to or from the air and the net entropy change. Sketch the
process on a T-S diagram.
SOLUTION
GIVEN:
T1=25oC=25+273=298K; P1=1.05bar=1.05 x105N/m2; 0.04m3; P2=5.0 bar=5.0 x105N/m2

The processes are as shown in figure above.

First, let’s calculate the mass of the gas from pV  mRT

pV 1.05  10 5  0.04
i.e. m    0.0491kg
RT 0.287  10 3  298
p1 p 2
For perfect gas at constant volume, . T  T , hence
1 2

p 2  T1 5.0  298
T2    1419 K
p1 1.05

Hence for constant volume, Q12  mcv T2  T1   0.0491 0.7181419  298  39.52kJ

Similarly for constant pressure, Q23  mc p T3  T2   0.0491 1.005298  1419  55.32kJ

Net heat flow = Q12  Q23  39.52  55.32  15.80kJ

Heat received = -15.80kJ

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Net decrease in entropy = ms1  s3   ms2  s3   ms2  s1 

But at constant pressure dQ  mc p dT

 1419 
1419
mc p dT
Hence, ms 2  s3    T
 0.0491  1.005  ln 
 298 
  0.077kJ / kgK
298

Similarly for constant volume, dQ  mcv dT

 1419 
1419
mcv dT
Therefore, ms 2  s1    T
 0.0491  0.718  ln 
 298 
  0.055kJ / kgK
298

Thus, ms1  s3   ms2  s3   ms2  s1   0.77  0.55  0.022kJ / kgK

Decrease in entropy of air=0.22kJ/kgK.

2. 0.025m3 of nitrogen (molecular weight 28kg/kmol.) contained in a cylinder behind a

piston is initially at 1.05bar and 20oC. The gas is compressed isothermally and reversibly
until the pressure is 5.5 bar. Calculate the change of entropy, the heat flow, and the work
done, and sketch the process on a P-V and T-S diagram. Assume nitrogen to be a perfect
gas. Take Ro=8.314kJ/kgkmol.K
SOLUTION
GIVEN:
V1=0.025m3; M=28kg/kmol.; P1=1.05 bar=1.05 x105N/m2; T1=20oC=20+273=293K; P2=5.5
bar=5.5 x105N/m2; Ro=8314J/kgkmol.

(a) (b)

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The shaded area on figure (a) represent the work input and the shaded area on figure (b)
represent the heat rejected.
Ro 8314
R   297 J / kgK
M 28
pV 1.05  10 5  0.025
From pV  mRT , we have m    0.0302kg
RT 297  293
 p1   1.05 
Change in entropy S 2  S1  mR ln  p   0.0302  297 ln  5.5   14.85 J / kgK
 2

Therefore the decrease in entropy S1  S 2  0.01485kJ / kgK

Heat rejected =shaded area on figure (b) = T S1  S 2   2930.01485  4.35kJ

For isothermal process for perfect gas W  Q  4.35kJ

Thus, Work input W  4.35kJ

3. What is the highest possible theoretical efficiency of a heat engine operating with a hot
reservoir of furnace gases at 2000oC when the cooling water available is at 100C?
SOLUTION
GIVEN:
T1=2000oC+273=2273K; T2=10oC+273=283K

T2 283
 Carnot  1   1  1  0.1245  0.8754
T1 2273
Thus, the maximum possibly efficiency is 87.54%

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