LECTURE NOTE ON

THERMODYNAMICS (MCH 201)

Thermodynamics is the branch of science that treats the various phenomena of energy and
related properties of matter especially the relationship between heat, work and properties of
systems.

BASIC CONCEPTS AND DEFINITIONS

System: Any collection of matter contained within prescribed boundary, which is of interest for
a particular study or analysis, is referred to as a system. A boundary may be physical or
imaginary (either fixed or moving). The boundary separates the system from its surroundings or
environments. There are two kinds of system, closed and open system.

Closed System: A closed system is that which allows no exchange of matter with the
surroundings. A good example of a closed system is the gas contained within a cylinder that is
closed at one end and a movable piston as shown in Figure 1.1. The inner surface of the piston
and cylinder form the boundary of this system and the boundary is a moving one.

Fig. 1.1 Closed System

Open system: An open system is that which allows exchange of matter with the surroundings.
i.e there is flow of mass in addition to work and heat across its boundary. With open systems the
boundary is normally specified as a control surface and the volume encompassed by the surface
as the control volume. The mass of matter within the control volume may be constant ( though
not the same molecular matter at any given instant). An example of an open system with constant
mass is a water nozzle and that with varying mass is air in a rubber tube undergoing inflation.
 Fig. 1.2 Open System

State: At any instant or time a system is in a condition called state, which encompass all that can
be said about the result of any measurement and observation that can be performed on the system
at that time.

Process: That which changes the state of a system.

Path: path of a process is the series of state points passed through during process.

Cyclic process: is one in which the final state of the system is identical with its initial state. Such
a system is said to have undergone a cycle.

Property: any observable characteristics of a system is referred to as property of the system. The
thermodynamic properties are pressure, volume, temperature, internal energy, enthalpy and
entropy. Properties may be classified as intensive or extensive as they are independent or
dependent of mass of the system. For example, temperature, pressure, specific volume and
density are intensive properties, while total volume, total mass, total energy in a system, internal
energy, enthalpy and entropy are extensive properties. If a change in the value of a property
depends only on the initial and final states of the system, and is independent of the process
undergone by the system during a change of state, it is called a state/ point function. e.g
2
State functions are written as exact differentials e.g pressure ∫ 𝑑𝑝 = P2- P1 . Path functions
temperature, pressure and entropy.

1
have their values depend on the path followed during the process of changing their states i.e their
history is important in determining their values in the final equilibrium state. Examples are heat
and work written as inexact/partial differential as ∂Q and ∂w respectively. e.g heat ∫ 2∂𝑄 ≠ Q2 –
2 1
Q1 but ∫ ∂𝑄 = Q1-2
1

Specific properties: are those for a unit mass and are extensive by definition e.g. specific
volume.

Energy: The general term is the capacity to produce an effect. It appears in many forms which
are related to each other by the fact that the conversion can be defined with the precision.
Internal Energy: the sum of various forms of energy that a system has is the internal energy of
the system. It is a property of the system. The absolute amount of internal energy that a system
has is never known, but internal energy changes can be measured from any convenient datum.

Isolated System : is one that is completely impervious to its surrounding neither mass nor
energy cross its boundary.

PROCESSES AND CYCLE

Thermodynamic Processes: is the path of successive states through which a system passes in
changing its states. When the processes are performed on a system is such a way that the final
state is identical with the initial state, the closed system is said to have undergone a
thermodynamic cycle or cyclic process.

Fig. 1.3 Thermodynamic process Fig. 1.4 Thermodynamic Cycle

REVERSIBILITY

Reversible Process: May be defined as a process between two states during which the system
passes through a series of equilibrium states. A reversible process between two states can be
drawn as a line on any diagram of properties. When a fluid undergoes a reversible process, both
the fluid and its surroundings can always be restored to their original states. In practice, the fluid
undergoing a process cannot be kept in its intermediate states and a continuous path cannot be
traced on diagram of properties. Such a real process is called irreversible process and is usually
represented by a dotted line joining the end states to indicate the intermediate states are
indeterminate.

Fig. 1.5 Reversible process

Fig. 1.6 Irreversible process
The criteria for reversibility include:

(a) Absence of friction i.e no internal or mechanical friction

(b) No finite pressure difference between the fluid and its surroundings (i.e infinitely slow
process)

(c) No heat transfer across a finite temperature difference.

From the criteria stated above, it is apparent that no real process is reversible but a close
approximation to an internal reversibility may be obtained in many practical processes.

TEMPERATURE

Temperature is an intensive property, which determines the degree of hotness or the level of
heat intensity of a body. When a hot body and a cold body are brought in contact with each
other, heat energy is transferred from the hot body to the cold body until the two bodies are said
to have equal temperature if there is no change in any of their observable properties.
If a body A has the same temperature with body B when brought together and body B when in
contact with a third body C shows no change in any observable characteristics, then bodies A
and C when brought into contact will also show no change in their characteristics. That is, if two
bodies are each equal in temperature to a third body, they are equal in temperature to each other.
This principle of thermal equilibrium is often called the Zeroth law of Thermodynamics.

Scale of Temperature: A temperature scale is an arbitrary thing. The Fahrenheit and Celsius
(Centigrade) scales are based on melting and boiling points for water at 1 atmosphere. The
respective temperatures are 32 and 212 degrees in the former and 0 and 100 degrees in the latter.
The thermodynamic temperature scale which is measured from a point of absolute zero will be
discussed later.

Thermometer: is a system with a readily observable characteristics termed a thermometric

property. The systems are equal in temperature when there is no change in any property when
they are brought into contact.

WORK AND HEAT

For a closed system to undergo change of state, this must be accompanied by the appearance of
work and heat at the boundary. In mechanics, work is defined as the product of force and
distance (d) moved in the direction of the force.
Mathematically, work done W= F x d, where Force = pressure x area. The basic unit of work in
SI system is in Nm or Joule. Work is a transient quantity which only appears at the boundary
while a change of state is taking place within a system. Work can therefore be described in
thermodynamics as a form of energy transfer which appears at the boundary when a system
changes its state due to the movement of a part of the boundary under the action of a force.
By convention, work done by the system on the surroundings is taken to be positive i.e. Wout =
+ve e.g when a fluid expands within a cylinder pushing a piston outwards. Conversely, work
done on the system by the surroundings is taken to be negative i.e. W in = -ve e.g when a piston
compresses a fluid within a cylinder.
Heat can also be described in an analogous manner to work as a form of energy transfer that
appears at the boundary when a system changes its state due to a difference in temperature
between the system and its surroundings. Heat is transitory energy like work and can never be
contained or possessed by a body

By sign convention, heat flowing into a system from the surroundings is taken to be positive i.e
Qin = +ve while heat flowing from the system to the surroundings is taken to be negative.ie Qout =
-ve. It is worth noting that both heat and work are not thermodynamic properties and therefore
they are path path functions whose values depend on the particular path followed during the
process. Hence heat and work are written as inexact differentials in the forms ∂Q and ∂W
2 2
i.e ∫ ∂W = W1-2 and ∫ ∂𝑄 = Q1-2
respectively.
1 1

REVERSIBLE WORK

Consider an ideal frictionless fluid contained in a cylinder behind a piston. Assume 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 fluid pressure be p, let the pressure of the
surroundings be (p-dp). The restraining force exerted by the surroundings on the piston is (p-
dp)A. Let the piston move under the action of the force exerted by the fluid a distance dl to the
right. Then, the work done by the fluid on the piston is given by the force times the distance
moved. ie. Work done = pA x dl = pdv
Where dv is a small increase in volume.

Fig. 1.7 Fluid in a cylinder undergoing expansion

Or for a mass m, dW = mpdv, where v is the specific volume. This is only true when criteria (a)
and (b) for reversibility hold.
When a fluid undergoes a reversible process, a series state points can be joined up to form a line
on a diagram of properties. The workdone by the fluid during any reversible process is therefore
given by the area under the line of the process plotted on a p-v diagram as shown in Fig. 1.8.
Fig. 1.8 Reversible expansion process on a p-v diagram
Example 1.1
A fluid of unit mass at an initial pressure 6 bar and specific volume of 0.36 m 3/kg which is
enclosed in a cylinder behind a piston undergoes a reversible expansion process according to a
law pv2= constant. The final pressure is 1.2 bar. Calculate the work done during the expansion
process.
Solution
2

 2

Work done = shaded area = m where p  c / v2

1
pdv
2 1 
1
v2 1 1
W  mc  2  mc   v   mc   
1 v
d v v
v1  1 2 

But c  pv 2
c pv2
 6x105 N / m 22  m 3
/ kg 
2

1 1
0.36
 0.7776
105 N / m2 m 3
/ kg 
2

Also p v 2  c and v c
2 2 2 p2

0.7776  105 N / m2 m3

c / kg 
2
v2   1.2  105 N / m2
p2
v  0.805 m 3 / kg 
2

2
For unit mass m = 1
 1 1
 Nm 2 m3 / kg 
2
  1 1
 W  C     0.7776  103 
v
 1 v 2   0.36 0.805  m3 / kg
 119403.73 Nm / kg
 kJ / kg
119.404
Example 1.2
A fluid of unit mass which is enclosed in a cylinder at an initial pressure of 30 bar is allowed to
undergo a reversible expansion process behind a piston according to a law pv2 = constant until
the volume is doubled. The fluid is then cooled reversibly at constant pressure until the piston
regains its original position. With the piston firmly locked in position, heat is then supplied
reversibly until the pressure rises to the original value of 30 bar. Calculate the net work done the
fluid for an initial volume of 0.075 m3
Solution

pV2  pV2 C
1 1 2 2 2
v  20.075 30 x 105

p   1   30 x 10 
5
 
p 

2 1  0.15  4
v 2
 7.5 x 105 N / m 2
C
2
 p V  30 x 105  N / m2 m6
0.0752
1 1

 16875 N / m 2 m6

so, c  pv2 , p c
and
v2
2 2 c 2 1  1
v2

pdV  
w 12

v v
2 2
dV  c   
 V 
1
1 dV 1
1 1   1
 c   16875 1  v 1
 N / m2 m6
 0.07
5 0.015  m3
 
V V
  1 2 

 112500Nm
w 2  p 2 (v 3  v )  7.5 105 (0.075  0.15)N / m2  m3  56250Nm
3
 = -56250 Nm
W31 = 0 since the piston is locked in position dV= 0
Net work done = W12 + W23 +W31
= 112500-56250 + 0
= 56250Nm
Hence the net work done by the fluid is 56.25 kJ

PRACTICE QUESTIONS
1. A fluid at 10 bar is enclosed in a cylinder behind a piston, the initial volume being
0.05 m .Calculate the work done by the fluid when it expands reversibly according to a law pv 3=
C to a final volume of 0.06 m3 (7640 Nm)
2. 1 kg of a fluid is compressed reversibly according to a law pv = 0.25, where p is in bar and v is
in m3/kg. The final volume is one-fourth of the initial volume. Calculate the work done on the
fluid and sketch the process on a p-v diagram (3466 Nm)
3. 0.05 m3 of a gas at 6.9 bar expands reversibly in a cylinder behind a piston according to the
law pv1.2= Constant, until the volume is 0.08 m3. Calculate the work done by the gas and sketch
the process on a p-v diagram (15480 Nm)
4. A fluid is heated reversibly at a constant pressure of 1.05 bar until it has a specific volume of
0.1m3/kg. It is then compressed reversibly according to a law pv= Constant to pressure of 4.2bar,
then allowed to expand reversibly according to a law pv 1.7= Constant, and is finally heated at
constant volume back to the initial conditions. The work done in the constant pressure process is
1515Nm, and the mass of fluid present is 0.2 kg. Calculate the network of the cycle and sketch
the cycle on a p-v diagram (781 Nm)
2.0 THE FIRST LAW OF THERMODYNAMICS

The first law is concerned with the principle of conservation of energy as applied to
closed systems which undergo changes of state due to transfer of work and heat across the
boundary. It is in fact, a statement of the law of conservation of energy as applied to heat energy
and mechanical work that energy can neither be created nor destroyed though it can be
transformed from one form to another.
The law states that, when a closed system is taken through a thermodynamic cycle, the net heat
supplied to the system from its surroundings is equal to the net work done by the system on its
surroundings.
Mathematically,  ∂Q =  ∂W
Where  represents summation for a complete cycle. This implies that network done can never
be greater than the heat supplied. `

EXAMPLE 2.1
In a certain steam plant the turbine develops 2000 kW. The heat supplied to the steam in the
boiler is 3800 kJ/kg, the heat rejected by the steam to the cooling water in the condenser is 3100
kJ/kg and the feed-pump work required to pump the condensate back into the boiler is 10 kW.
Calculate the steam flow rate.

Solution

Steam Plant
 ∂Q = Qin- Qout = 3800-3100 =700 kJ/kg
Let the steam flow rate be 𝑚̇ kg/s
Then,  ∂Q = 𝑚̇ x 700 = 700 𝑚̇ kw
 ∂W = Wout-Win = 2000-10 =1990 kW
But  ∂Q =  ∂W
700 𝑚̇ =1990
𝑚̇ = 1990/700 = 2.84 kg/s
i.e. mass flow rate of steam required = 2.84 kg/s

COROLLARIES OF THE FIRST LAW

Corollaries are basic propositions or inferences about the behaviour of thermodynamic systems
deduced from the laws of thermodynamics. Corollaries of the first law of thermodynamics are
stated as follow:

COROLLARY 1
There exists a property of a closed system such that a change in its value is equal to the
difference between the heat supplied and the work done during any change of state.
Mathematically,  (∂Q - ∂W) = du
Where U denotes the property so discovered called internal energy of the system.
i.e. Q-W = (U2-U1) for a non-flow process.
This equation is called non-flow energy equation (NFEE)
Internal energy, which is the intrinsic energy of a body not in motion, being a property, can be
said to reside in the system and it can be increased or decreased by a change of state.
COROLLARY 2
The internal energy of a closed system remains unchanged if the system is isolated from its
surroundings.
COROLLARY 3
A perpetual motion machine of the first kind is impossible. That is, a system cannot produce
work continuously without absorbing heat-energy from the surroundings.

NON FLOW ENERGY EQUATION

From the first corollary of the first law, the following can be rightly deduced.
Gain in internal energy = Net heat supplied- Network done
 2 2
Mathematically, dU =  Q   W
1 1

For a single process between state 1 and state 2, we have, U2-U1 = Q-W for a non-flow process
or in differential form, dU= ∂Q - ∂W, where U is the specific internal energy in kJ/kg
This equation is true for both reversible and irreversible processes. For reversible non-flow
process dw = pdv = mpdv
But ∂Q = dU + ∂W = du + pdv for unit mass
2
Q = (u2-u1) +  1
pdv

The above equation is true for ideal reversible non-flow processes.

EXAMPLE 2.2
In the compression stroke of an internal combustion engine, the heat rejected to the cooling water
is 145 kJ/kg and the work input is 190 kJ/kg. Calculate the change in specific internal energy of
the working fluid stating whether it is a gain or loss.
SOLUTION
Qout = 145 kJ/kJ, Win = 190 kJ/kg
U 2  U1  Q  W
  145   190
 145  190
 45 kJ / kg
gain ininernal energy  45 kJ / kg
Example 2.3
In the cylinder of an air motor, the compressed air has a specific internal energy of 4200 kJ/kg at
the beginning of the expansion and a specific internal energy of 2050 kJ/kg after expansion.
Calculate the heat flow to or from the cylinder when the work done by the air during the
expansion is 1050 kJ/kg.
SOLUTION
U1 = 4200 kJ/kg, U2=2050 kJ/kg, Wout= +1050 kJ/kg
U 2  U1  Q  W
2050  4200  Q 1050
 2150  Q  1050
 Q = - 2150 + 1050
Q = -1100 kJ/kg
i.e. heat rejected by the air = 1100kJ/kg

PRACTICE QUESTIONS
1. An air compressor which compresses air at constant internal energy rejects 80 kJ of heat to
the cycling water for every kilogram of air. Calculate the work done during compression
stroke per kilogram of air (80 kJ/kg)
2. In the compression stroke of a gas engine the work done on the gas by the piston is 90
kJ/kg and the heat rejected to the cooling water is 52 kJ/kg. Calculate the change in
specific internal energy (38 kJ/kg)
3. The gases in the cylinder of an internal-combustion engine has a specific internal energy
of 950 kJ/kg and a specific volume of 0.08 m 3/kg at the beginning of expansion. The
expansion of the gases may be assumed to take place according to a reversible law pv 1.4 =
constant, from 50 bar to 1.6 bar. The specific internal energy after expansion is 180 kJ/kg.
Calculate the heat rejected to the cylinder cooling water per kilogram of gases during the
expansion stroke (-144 kJ/kg).

THE STEADY FLOW ENERGY EQUATION

The governing equation for an open system with mass transfer across its boundary is referred to
as steady flow energy equation (SFEE). This is analogous to non-flow energy equation for a
closed system.
For a flow to be regarded as steady, the mass flow must be constant and the same at inlet and
outlet and the fluid properties at any point in the open system must not vary with time.
Consider a unit mass of a fluid with specific internal energy u flowing steadily and moving with
velocity C through a seam power plant shown in Fig. 2.1 below
Fig. 2.1 Section of a steam power plant

The system above constitutes an open system with its boundary shown cutting the inlet pipe at
section 1 and outlet pipe at section 2.
This boundary is often referred to as a control surface and the system as a control volume.
Assuming a steady flow of heat Q per kg of fluid is supplied at the boiler and each kg of fluid
does work W at the turbine.

Also considering an element of fluid at the entry of the boiler shown below.

Fig. 2.2 section at inlet of boiler

Energy required to push fluid element across the boundary
= p1A1 x l = p1A1l = p1 x volume of fluid element
 Energy required to move fluid element across the boundary at the eating = p1v1; v1=specific
volume at inlet.
Similarly,
Energy required to move fluid element across the boundary at the exit = p2v2; v2 = specific
volume at exit.
Total energy entering the system consists of the energy of the flowing fluid at inlet, energy term
p1v1 and the heat supplied Q i.e.
E  u  1 c 2  gz  p v  Q
in 1
2 1 1 1 1

Total energy leaving the system consists of energy of the flowing fluid at the exit, energy term
p2v2 and the output work W

Eout  u 1 c2  gz p2 v2  W
2 2
 
2 2

Since the flow of fluid into and out of the system with heat and work crossing the boundary are
steady, then Ein = Eout. Thus
u  1 c 2  gz  p v  Q  u 1 c 2  gz  p v  W
1
2 1 1 1 1 2
2 2 2 2 2

The sum of specific internal energy and pv term is given the symbol h and is called specific
enthalpy i.e. h = u + pv
By writing h for (u+pv), the equation reduces to
h2  1 1
2 c 2  gz  Q  h2 2 c 2  gz 2  W

1 1 1 2
QW
 h 
1
c  c   2 z 1
2 2 21
h
gz
2

where Q and W are the heat and work transfers per unit mass flow through the system.
The above equation is called the steady flow energy equation (SFEE) and provides the basic
means for studying most open systems of importance in engineering. In nearly all problems in
practice, the potential energy term g(z2-z1) is either zero or negligible compared with other terms.
It has been included in the equation for the sake of completeness and hence can be omitted in
analysis.
For steady flow, the mass flow rate over a cross section of the flow at inlet is constant and equal
to the mass flow rate at exist.
i.e. 𝑚̇ in = 𝑚̇ out = 𝑚̇
and mass flow rate is the ratio of volume flow rate (AC) and specific volume (v) hence, mass

flow rate 𝑚̇
A1C
  AC
1 A2C2
=
v1 v2
This equation which expresses the principle of conservation of mass in steady flow is known as
continuity equation.
EXAMPLE 2.4
In a steam turbine unit, the mass flow rate of stream through the turbine is 17 kg/s and the power
developed by the turbine is 14000 kw. The specific enthalpies of the steam at inlet and exit of the
turbine are 1200 kJ/kg and 360 kJ/kg while the velocities are 60 m/s and 150 m/s respectively.
Calculate the rate at which heat is rejected from the turbine. Also find the area of the inlet pipe
given that the specific volume of the steam at inlet is 0.5 m3/kg.
SOLUTION

Given
In = 17 kg/s, W = 14000 kw, h1= 1200 kJ/kg, h2 = 360 kJ/kg
C1 = 60 m/s, C2 = 150 m/s, v1=0.5 m3/kg
To determine Q
From SFEE, neglecting the potential energy term
Q-W = in (h2-h1) + ½ in ( c2  c2)
2 1


Q  14,000  17360  1200  1/ 2 17 1502  602 
 14280  160.65   14119.35kW
Q   14119.35  1400   119.35kW
i.e. heat rejected = 119.35 kW
To determine inlet area A1
From the continuity equation,
 
m1C
A and A  mv1
1 1
C1
v1
17 0.5
mv1
A 1
 60
C1
 0.142 m 2

i.e. inlet A 1 0.142 m2

area

EXAMPLE 2.5
At the inlet to a nozzle employed for increasing the velocity of a steadily flowing fluid, the
specific enthalpy and the velocity of the fluid are 3025 kJ/kg and 60 m/s respectively. The
specific enthalpy of the fluid at the exit is 760 kJ/kg. The nozzle is horizontal and there is a
negligible heat loss from it. Calculate the fluid velocity at the exit, and also find the mass flow
rate of the fluid when the inlet area is 0.1m 2 and inlet specific is 0.19 m3/kg. If the specific
volume at the nozzle exit is 0.5m3. Determine the exit area of the nozzle.

SOLUTION

Solution
Given
h1  3025 kJ / kg, C1  60 m / s, h2  2790 kJ / kg
A1  0.1m2 ,  0.19 m3 / kg, v  0.5m3 / kg
1 2
v
Determine C2
From SFEE, neglecting the potential energy term
Once the nozzle is horizontal i.e. z1 = z2

2 1

Q W  h  h   1/ 2 C2 C 2
2 1

But no heat and work cross the boundary
i.e. Q = 0 and W = 0
 h  1/ 2 C 2  h  1/ 2 C 2
1 1 2 2
3025 10 3  1/ 2 60  2790  1/ 2 C 2
2

103
2
3026.8 103  2790  103  1/ 2 C
2 2

 2 236.8 x103 
2
C2
 473.6  103
C2  4736  103
C2  688.19 m / s`
i.e. fluid velocity at exit = 688.19 m/s
From continuity equation,

𝑚̇ = 0.1  60
A1C1  0.19
v1
Inlet mass flow rate= 31.59 kg/s

Also, 𝑚̇
A1C A 2 C2

=
1
v2
v1

mv2
A 31.59 .5
 688.19
2
C2
 0.02295m2
i.e. the exit area A2 = 0.02295 m2

PRACTICE QUESTIONS
1. A steady flow of steam enters a condenser with a specific enthalpy of 2300 kJ/kg and a
velocity of 350m/s. The condensate leaves the condenser with a specific enthalpy of 160
kJ/kg and a velocity of 70 m/s. calculate the heat transfer to the cooling fluid per
kilogram of steam condensed (02199 kJ/kg)
2. A steam turbine receives a steam flow of 4.35 kg/s and the power output is 500 kw. The
heat loss from the casing is negligible. Calculate the change in specific enthalpy across
the turbine when the velocity at entrance is 60 m/s, the velocity at exist s 360 NS, and the
inlet pipe is 3m above the exhaust pipe. (433 kJ/kg)
3. A turbine operating under steady-flow conditions receives steam at the following state:
pressure 13.8 bar, specific volume 0.143 m 3/kg, specific internal energy 2590 kJ/kg,
velocity 30 m/s. The state of the steam leaving the turbine is as follows: pressure 0.35bar,
 specific volume 4.37 m3/kg, specific internal energy 2360 kJ/kg, velocity 90 m/s
Heat is rejected to the surroundings at the rate of 0.25 kW and the rate of steam
flow through the turbine is 0.38 kg/s.
Calculate the power developed by the turbine (102.7 kW)

REVERSIBLE NON-FLOW PROCESS

CONSTANT VOLUME PROCESS (ISOCHORIC PROCESS)
In a constant volume process, he working substance is contained in a rigid vessel, hence the
boundaries of the system are immovable, so work cannot be done on or by the system other than
parallel which work input which is negative and this can be carried out in practice by some
method of during the fluid. It will be assumed that constant volume indies zero work unless
otherwise stated.
From the non-flow energy equation for unit mass, since no work is done, i.e. W = 0, we therefore
have Q = u2-u1
Or for mass m, of the working substance
Q= U2 – U1
That is, all the heat supplied in a constant volume process goes to increasing the internal energy.
This equation can be written in differential form as ∂Q = dU
For a perfect gas, Q = mcv (T2-T1)
The figures below show the p-v diagrams of constant volume process for a vapour and a perfect
gas
 CONSTANT PRESSURE PROCESS (ISOBARIC PROCESS)
A closed system undergoing a process at constant pressure is illustrated in the figure below

The fluid is enclosed in a cylinder by a piston on which rests a constant, weight. If heat is
supplied, the fluid expands and work is done by the system in overcoming the constant force.
Heat is extracted, the fluid contracts and work is done on the system by the constant force .

From the non-flow energy equation,

Q = (u2-u1) + W
Work might also be done in the system simultaneously by turning the fluid with a paddle, and
this negative quantity of work must be included in the term W if no paddle work is done on the
system and the process is reversible i.e. W = ∫pdv = pdv, we have
∂Q = du + pdv Or
∂Q – pdv = du
Since p is constant, this can be integrated to give
Q  pv2  v1   u 2 u 1 
A further implication of the energy equation is possible if a new property is introduced. Since p is
constant, pdv is identical with d(pv)
Thus the energy equation can be written as
Q  d pv  du
Q  d u  pv
But specific enthalpy h = u+pv
i.e. ∂Q = dh
or in the integrated form
Q = h2-h1
or for mass m, of a fluid
 Q = H2-H1 (reversible process only)
That is the heat added in a reversible constant pressure process is equal to the increase in
enthalpy. The above equation does not apply if the process is irreversible.
For a perfect gas, Q = mcp (T2-T1)

The figures above show the p-v diagrams of constant pressure process for a vapour and a perfect
gas
NB: The areas shaded represent the work done by the fluid i.e. (v2-v1)

CONSTANT TEMPERATURE PROCESS (ISOTHERMAL PROCESS)

When the quantities of heat and work are so proportioned during an expansion or compression
that the temperature of the fluid remains constant the process is said to be isothermal when a fluid
in a cylinder behind a piston expands from a high pressure to a low pressure, there is tendency for
the temperature to fall. In isothermal expansion heat must be added continuously in order to keep
the temperature at the initial value.
Similarly in an isothermal compression heat must be removed from the fluid continuously during
the process. It is possible to show that for a reversible isothermal process, a certain definite
relationship must exist between p and v, and consequently, the work done has a definite value
that can be predited.
For any reversible process the energy equation is ∂Q – pdv = du
Or
2
Q-  pdv  2
 u1 
u
1

The figures below show the p-v diagrams of isothermal process for a vapour and a perfect gas
For isothermal process of a perfect gas which is assumed to have an equation of state.
pv = RT=constant, since T = constant
i.e pv = constant
or
p1v1 = p2v2
The work done by a perfect gas which undergoes a reversible isothermal expansion from state 1
to state 2 as shown in the figure above is given by the shaded area and can be evaluated as:
2
W = 1 pdv

In this case pv = c or p = c/v

2𝑐 2
∴ W=∫ 𝑑𝑣 = 𝑐∫
1
𝑑𝑣
1 𝑣 1 𝑣
𝑣2
= c [ln 𝑣]𝑣2 = c ln( )
𝑣1 𝑣1

Since c = 𝑝1𝑣1 =
𝑝2𝑣2
W = 𝑝 𝑣 ln ) = 𝑝 𝑣 ln
𝑣 ) per unit mass of gas
( 2 𝑣
( 2
1 1
𝑣1 2
𝑣1
2

For mass, m, of the gas

W = 𝑝 𝑣 ln
) = 𝑝 𝑣 ln ( 2)
𝑣
𝑣2
( 2 2 𝑣
1 1 1
𝑣1

From 𝑝1𝑣1 = 𝑝2𝑣2 , we have

−𝑝2
𝑣2 𝑝1
𝑣1
∴ W = 𝑝 𝑣 ln ( ) =
𝑝 𝑝1
1 1 1 𝑝2𝑣2 ln (2 )
𝑝 𝑝
2

Also 𝑝1 𝑣1 = 𝑅𝑇
Hence W =
 𝑝1
ln ( )
𝑝2
And for mass, m, of the gas
𝑝1
W = mRT ln ( )
𝑝2
From Joule’s law for perfect gas,
du = cvdT
For isothermal process dT = 0
i.e du = 0
That is the internal energy remains constant in an isothermal process for a perfect gas
From non-flow energy equation, we have
∂Q = dU + ∂W
Since dU = 0
∴ ∂Q = ∂W
or
Q=W
That is, the quantity of heat supplied is equal to the work done in an isothermal process for a
perfect gas only.

ADIABATIC PROCESS
An adiabatic process is the one in which heat is prevented from crossing the boundary of the
system. i.e. no heat is transferred to or from the fluid during the process. That is, an adiabatic
process is one undergone by a system which is thermally insulated from its surroundings.
From the non-flow energy equation
Q = u2-u1 + W
For an adiabatic process Q = 0, we have
-W = (u2-u1)
or
W= (u1-u2)
This equation is true for an adiabatic non-flow process whether or not the process is reversible.
In an adiabatic compression process all the work done on the fluid goes to increasing the internal
energy of the fluid. Similarly in an adiabatic expansion process, the work done by the fluid is at
the expense of a reduction in the internal energy of the fluid.
A reversible adiabatic process is called isentropic (constant entropy) process.
For a vapour undergoing a reversible adiabatic process the work done can be found from equation
given above by evaluating u1 and u2 from tables. For a perfect gas, a law relating p and v has been
obtained for a reversible adiabatic process as pv  = constant
Each perfect gas undergoing a reversible adiabatic process have its own value of 

POLYTROPIC PROCESS
The constant volume and constant pressure processes can be regarded as limiting cases of a more
general type of process in which both the volume and pressure change, but in a certain specified
manner.
In many real processes it is found that the states during an expansion or compression can be
described approximately by a relation of the form pv n = constant where n is a constant called the
index of expansion or compression, and p and v are average values of pressure and specific
volume for the system.
Compressions and expansion of the form pvn = constant are called polytropic processes. When n
= 0, the relation reduces to p = constant (isobaric process) and when n = ∞ , it can be seen to

reduce to v = constant by writing it in the form 𝑝𝑛 v = constant

1

For any reversible process, W =  pdv

c
For a process in which pvn = constant, we have p 
vn
Where c is a constant
c
Thus, W 2 dv  v2 dv  c v n1  v2

 v cn n 
1
v1 v v1 v   n  1v

 v n1  v 1n1   1n 1n


c 2   c  v2  v 1 
  n  1   n1 
  
 1n 1n
  1n 1n

 c  (v 1  v 2 )   c  v1  v 2

  n 1 


 n1 

 p 1v 1nv 1n
1  p v
n
2 2v 2
1n

 
 n1 
Since constant c = p1 v1n = p 2 v2n
 p1v1  p2 v2
W n 1
This equation is true for any working substance undergoing a reversible polytropic process. It
follows also that for any polytropic process, we can write
n
p v 
1
 2
p2  v1 
The integrated form of the energy equation for a reversible polytropic process can therefore be
written as
p v
 p1v1  2 1   u 
Q u
  2 1
 n 1 
In a polytropic process the index ‘n’ depends on in the heat and work quantities during the
process. The various processes considered previously are special cases of the polytropic process.

When n = ∞, 𝑝𝑣∞ = c or 𝑝∞ v = constant (isobaric process)

1

When n =  , pv = c or pv1/∞ = C i.e. v = constant (isochoric)

When n = 1, pv = c i.e. T= constant (isothermal process
Since pv/T=constant for a perfect gas
When n= 𝛾, 𝑝𝑣𝛾 = constant i.e. reversible adiabatic
process This is illustrated on a p-v diagram shown below

State 1 to A is constant pressure cooling (n = 0)

State 1 to B is isothermal compression (n = 1)
State 1 to C is reversible adiabatic compression (n = 𝛾)
State 1 to D is constant volume heating (n=  )
Similarly,
State 1 to A1 is isobaric heating State
1 to B1 is isothermal expansion
State 1 to C1 is reversible adiabatic expansion
State 1 to D1 is isochoric cooling

THE SECOND LAW OF THERMODYNAMICS

THE HEAT ENGINE
A heat engine is a thermodynamic system operating in a cycle and across the boundaries
of which flows only heat and work.

Fig. 3.1 Symbolic representation or Heat Engine

Example of Heat Engine

The Steam Turbine Plant: Represented diagrammatically in Fig. 3.2.
Applying the first law
dW  dQ
Wx  Wp   Q2
Q1
Fig. 3.2 Steam Turbine Plant
3.1.2 Closed system gas Turbine plant: Represented diagrammatically by Fig. 3.3.

Fig 3.3 Close System Gas Turbine Plant

Wx  Wc  Q1  Q2

The open system gas turbine plant and the reciprocating types of internal combustion engine
have fuel and air mixture crossing their boundaries and so are not heat engine.

HEAT ENGINE PERFORMANCE

The greater the proportion of heat supplied that is converted to work the better is the

engine.
net work output 
The ratio is termed the cycle efficiency denoted by
heat sup plied 
W x  Wp
  Q1 where
Q1 is heat supplied per mass of the system
Wx is work done per mass by the system
Wp is work done per mass on the system.
If Q2 is heat rejected per mass by the system, by the first law
Q1 - Q2 = Wx - Wp

 Q1  Q2
Q2 Q1  1 

Q1
This shows that the cycle efficiency will be unity (i.e. 100%) if Q 2 = 0. That is, Q2 = 0 there will
be 100% conversion of heat into work.

Heat Reservoir: Heat Source and Heat Sink

The term heat reservoir (or reservoir) is used in thermodynamics to mean a heat source or heat
sink of uniform temperature and of infinite capacity such that unlimited quality of heat can flow
across its boundary without changing its temperature.
When heat flow is at a high temperature, it is referred to a hot reservoir and when heat flow is at
a low temperature, it is referred to as a cold reservoir.

STATEMENT OF THE SECOND LAW OF THERMODYNAMTICS

It is impossible to construct an engine which will work in a complete cycle and produce no
effect, except to raise a weight and exchange heat with a single reservoir.
The first law of thermodynamics shows that net work cannot be produced during a cycle without
some supply of heat. The second law emphasizes the fact that some heat must always be rejected
during the cycle, i.e. the net work must be less than the heat supplied.

PERPETUAL MOTION MACHINES

Any machine which creates its own energy is called a perpetual motion machine of the
first kind (PMM 1). Such a machine contradicts the first law since the first law rejects the
possibility of creating or destroying energy. Similarly, any machine which produces work
continuously while exchanging heat with only a single reservoir is know as perpetual motion
machine of the second kind (PMM 2). This machine contradicts the second law. From the
foregoing both propositions are impossible.
If the second law were not true it would have been possible
a. To drive a ship across the ocean by taking heat from the ocean.
b. To run a power station by extracting heat from the surrounding air.
There is nothing in the first law to say that the above projects are not possible (interchange
between heat and work). The projects are, however, impossible and so the second law must be
true. There is not natural sink of heat at a lower temperature than the atmosphere or ocean.
 DIRECT AND REVERSED HEAT ENGINES:

Direct heat engine Reversed heat engine

Produces net out-put of Directions of work and
Work and heat from net heat flow is reversed
Input of heat. (Heat pump refrigerator)
Fig. 3.6 (A) Fig 3.6 (B)

Refrigerator withdraws heat at a lower temperature since its principal purpose is the
extraction of heat from a cold space.
Heat pump. The principal purpose of the heat pump is to supply heat to the hot space.
The Coefficient o performance of Refrigerators and Heat Pumps:
The coefficient of performance of a refrigerator (known as the performance energy ratio ref is
defined as
Hea Transfer at Lower Temperature
t Work sup ply

ref Q where Q2 = heat extracted

 W2

The coefficient of performance of a heat pump (performance energy ratio)

hp is defined as

Heat Transfer at Higher Temperature

Work Supply

hp 
Q
1
W
The relation between these two coefficients of performance can be established by applying the
first law.
Q1  Q2 W
Q1  W  Q2

hp Q W  1    ref
 W1 
Q2 Q2 1
W
W
hp  ref

1

PRACTICE QUESTIONS
1. The work done on a reversed heat engine is 100kg whilst the heat transfer to the engine
from the low temperature is 300kJ. Determine the heat transfer to the high temperature reservoir
and the COP as a refrigerator and as a heat pump.(400kJ, 3, 4)
2. A heat pump picks up 1000kJ of heat from well water at 10 0C and discharges 3000kJ of
heat to a building to maintain it at 200C. What is the COP of the heat pump? What is the
minimum required cycle net work? (1.5, 2000kJ)
4.0 ENTROPY
q1
From thermo temp. Scale
numerically
T1 
q2
T2

q1 q2 Algebraically
T1 
q2 T2
q1  =
 T
1 0
T2
i.e. summation of ratio of heat transfer to absolute temp. in reversible cycle = 0
two property diagram for any Reversible cycle may be replaced by elemental Carnot cycle

Thus, for any reversible cycle;

Tq r
 0
q R
But
 0 is a property = entropy = S

T

Note: Non  property = property

property

For a reversible process,

qr
T  S

In any adiabatic process, q  0

ad

In any reversible adiabatic process

 q R
( ) 0
ad
T
 Isentroppic
QR =Tds = area under T-S curve

For an irreversible cycle, 1  R

 q2   T2 
1  q   1 T 
 1   1 

q2
Hence q2 and numerically
T2 
q1 T1 T1
Algebraically,
q1 q2
T   0
1 T2
q
  0
T
[= 0 reversible ] Clausius
[< 0 irreversible] Inequality.
2
q
Path 132
T 1  0
1
2
q
Path 241 
R
 S1  S2
1
T
 q1
Path 13241 
1 T
 2

  1 1 R
q
1 T
 q
2 T

 0  S1  S2   0
 S2  S1

Note: If part of a cycle is irreversible, the whole cycle must be irreversible.

Irreversible adiabatic process incurs rise in entropy.
All Reversible adiabatic process incurs no rise in Entropy. Rise in S. if non – adiabatic, heat flow
across boundary, and rise in S for system + environment e.g. heat flow q from system at T 1 to
environment at lower To.

q
System: entropy loss,  
T1
q
Environment entropy gain
T0
Since T1 > To, gain > loss.
 s positive
A decrease in entropy can only be temporary and local with a greater increase elsewhere.
There is no process that cannot be reversed if we accept a greater irreversibility elsewhere.
Since entropy is a property (extensive) s . Same irrespective of path (rev. and irrev.) but
 qR
s 
T
q
 actual
T only in reversible case
One spontaneous tendency in nature is towards minimum energy.
Another spontaneous tendency in nature is towards maximum disorder (of motion or position) as
in changes from solid to liquid, to gas, to gas at lower pressure to a larger number of molecules,
mixing of different fluids, dissipation of energy by friction or viscosity
Entropy is a measure of disorder
In an adiabatic device, reversible (Reversible adiabatic) process is most efficient. Hence,
isentropic efficiency s can be devised.
(N.B. a process efficiency not cycle effy.)
For work absorber (compressor or pump)
Isentropic Efficiency ( ) = isentropic work W
s  s
actual work W

For work producer (turbine)

W
s =
WS
For a flow device (nozzle)
actual outlet E
s = isentropic outlet kE
k

E 2  Kinetic Energy 
c.f. in a slow moving device (large piston compressor) time for heat transfer
 isothermal
ideal
T  WT
W
4.1 Third law states that “the entropy of a pure substance in its most stable/state approaches
zero as the temperature approaches zero i.e. lim S = 0
Practice Questions
1. A system consists of a pure dissipative element and a pure thermal element with a heat
capacity of 50kJ/K. It experiences an irreversible work transfer interaction which takes the
system from state 1 at a temperature of 300K to state 2 at a temperature of 310K. If no heat is
transferred during this irreversible process, calculate the change in entropy of the system for this
process (1.6395kJ/kgK).
2. A carnot heat engine rejects 230kJ of heat at 25 0C. The net cycle work is 375kJ. Determine
the thermal efficiency and the cycle high temperature.

Availability
Available energy is the maximum portion of energy which could be converted into useful work
by ideal processes which reduces the system to a dead state (state equilibrium with the earth and
its atmosphere)
If a system within the surroundings is in equilibrium with the surroundings and itself is in an
equilibrium state, then there can be no interaction between the two. This is called the “dead
state”.
If the system is in some states other than the dead state, it will change spontaneously toward the
dead state. The work done by the system in changing to the dead state. The work done by the
system in changing to the dead state will never be less than zero i.e. W max  O , where W max
is the maximum useful work that can be produced by the system as it interact with the
surroundings in achieving the dead state.

Availability (Exergy): Availability is a measure of the maximum amount of useful work that
can be obtained from a system interacting with the surroundings at any state P 1 and T1 when
operating with a reservoir at constant pressure and temperature Po and To.
Note: Anergy and Exergy  Energy
Max Work Max useful work – Exergy
Unusable work
Q = A.E + U.E
Or Wmax = A.E = Q – U.E

From  circle T  To

To
Efficeincy
max
T T
Reversible heat transfer from a system
 w
From  max
  Q
w 
 Q
max
 T  To 
   Q
 T 
 To  T 
   dQ
 T 
During change in volume (dv) which is resisted by the pressure of the surroundings, Po
 Network =  w  Po dV
 Note : The network is the sum of all the individual work
T 
i.e.    Po    o  1
wnet w dV Q T 
To
 w  Po   Q
Q
dV T
T o Q
 w  P dV  Q 
o
T

w  Q  Po Q ......................1
dV  To
T
From the first law of thermodynamics for a closed system undergoing a reversible
process,
Q  du  w
 du  w  Q
Substitute (-du) in equation 1
w
ce  du  Podv  Tods sin  dQ 
net
ds  
 T rev
 dwnet   du  Po dv  To ds
W   du  P dv  T ds (Max work that can be accomplished by any system at
max o
1 o o

state 1 to state 0 can be represented by the decrease in this function


  Uo  U1   oP oV  1V  To So  S1  
  U  U  P V  P V T S  T S 
o 1 o o o 1 o o o 1

 Uo  U1  Po Vo  Po V1  To So  To S1
  U  P V T S   U  P V  T S 
1 o 1 o 1 o o o o o

Wmax = A1 - Ao
The function A = U  PoV To ds is known as the non-flow availability function which is a
composite property in that it is not only a function of the system but also of its surroundings.
Availability in Steady Flow
  
W
U   PV 2
Z g U  P  T S 
1
C 1 1 o V
S
max
 1 1
2 
o o o 1 o


 P1V1  Uo  PoVo  To S1  To S0 (Neglect Kinetic / Potential Energy
U1
  P1V1 To S1   U o  PoVo  To S0 
 U1  Go 

G1
The concept of availability may be expressed in terms of another thermodynamics
function. The Gibbs function or free energy, G, which is defined as G=H-TS
dG   Tds  SdT 
dH
  Tds  SdT
dH
Also,
H = U + PV
dH = du + PdV + Vdp
dG = du +Pdv + Vdp – Tds – SdT
Conditions of constant temperature and pressure where the temperature is To and the
pressure is Po, yields for the Gibbs function
dG = du + Podv – Tods
dG = G1 – Go

AVAILABLE ENERGY FOR SYSTEMS WITH HEAT TRANSFER

From Q1 = A.E + U.E
But Wmax = A.E
= Q1 – U.E
However, wmax
 ( A.E)
 A.E  
 To 
Q 1  
 T 
T
 Q  Q o
T
By integrating from state 1 to state 2
 d A.E 
2

2
Q 
T 2 dQ
 1 o  1 T

TA.E 
1
 Q  ds
2
12  1 o

Availability Energy  A.E   T S 2  S 1 

12 Q12 o
Also,
A.E  2
dQ To 2 Q

12
1
 1 T
2 2 Mc p dT
  dQ To 
1 1 T
2 dT
  1
dQ TMc p 

T
T2

2
dQ In
1
T1
ToMc p

 A.E T2
  To Mc ln
12 p T
Q12  T2 
1

 U .A12  To S 2  S1  p o
 T Mc ln  T 
 1
Again from gas equation
P1V
PV
1
 T2 2
T1 2

V2 T

P1 V x T21
1

P2
V
2
Putting the value of
V1 in equation 1

S S
  Cv T2 R
 log
e P1
x
T2
log
2 1 e
T1 P2 T1

 Cv log P2 T
T2  R log e 2
R
e
T loge P1
1
T1
  P
C v  R log  R loge
2P1
T2
e
T1
 Cp log P
T2 e
 R loge
T 2P1

Examples 4.1
If 300KJ of heat are reversibly added to 0.2kg of air at constant pressure and initial temperature
is 300oC, find the available and unavailable energies of the heat added. The temperature of the
surroundings is 30oC.
SOLUTION
Given: Q=300KJ, Mar = 0.2kg, T1 = 300oC = 300 + 273 = 573K
To = 300oC = 30 + 273 = 303K Cpar = 2005KJ kgk
Required: A.E = ?, U.E.=? T2 =?
To determine T2
Q = AH = Mcp (T2-T1)
T2 = Q + T1 = 300 + 573 = 2066k
 T2 
(A.E) 1-2 = Q1-2 – To mcp In  T 
 1
 2066 
 300  303 0.2 1005 In
   
573
 300  78.111  221.89 J
U .E   A.E  12  78.11KJ
 12
Q 12

EXAMPLE
4.2
It is required to remove 500KJ of heat from or construct temperature reservoir of 835K. The heat
is received by a system at constant temperature of 720k. The temperature of the surroundings,
the lowest available temperature is 280k. Find the net loss of available energy as a result of the
irreversible heat transfer.
SOLUTION
Given: Q = 500KJ, To = 280K, T1-2 = 835K, T3-4 = 720K
Required: (A.E)net = ?

A T-S diagram illustrating the processes

The total heat is the same in both the heat reservoir or
system (A.E)1-2 = Q1-2 – To (S2-S1 )

= Q1-2 –To Q
T12
   500 
  500  280
 
 835 
  332.34 KJ
 A.E   T S 4  S 3 
34 o
Q34

 A..I  TodQ
34  T34
Q34
  500 
  500  280
 
 720 
  305.55KJ
 A.E net    A.E 
  305.55  332.34KJ
  26.78KJ
There is a net loss of available energy the heat transfer process, and this is equal to the net gain
in unavailable energy
U .E 1  2  To S 2
 S 1   To dQ
 500
 _ 280  107.66KJ
 
 835 

U .E dQ
 To  S3   To
34 S4 500  To
  280  194.44KJ
 
720 
U .E net   1 U .E 
 194.44  167.66KJ
  26.78KJ
The use of a T-S diagram is very useful in visualizing heat, available energy, and unavailable
energy.
It is primetimes easier to find the net gain of unavailable energy (U.E)net = To ASnet) than the net
less of available energy.
  A.E   To dQ
54 Q34
  500 
  500  280

 
720
  305.55KJ
 A.E net   i  A.E 
  305.55  332.34KJ
  26.78KJ
There is a net loss of available energy in the heat transfer process, and this is equal to the net
gain in unavailable energy.

U .E  To  S1  To dQ
12 S 2 500  T12
  280   107.66KJ
 
835 
dQ
U .E  To  S3 
T12
34 S 4 
  500
To
  280   194.44KJ
 
720 
U.E net  iU .E 
 194.44  167.66KJ
  26.78KJ
The use of a T-S diagram is very useful in visualizing heat, available energy, and unavailable
energy.
It is sometimes easier to find the net gain of unavailable energy (U.E)net = To ∆Snet) than the less
of available energy.

PRACTICE QUESTIONS
1. Determine the available energy of finance gas SP 046KJ/kg. K when is seized from
1260K. i.e. 480k at constant pressure. The surroundings is at 295k
2. A carnot engine receives heat from a constant temperature reservoir. The engine has a
maximum temperature of 820k. For each 1100KJ of heat transferred, compute the net
change of entropy when the high-temperature reservoir is at the following temperatures:
(a) 1700K; (b) 1425K (c) 875K.
3. At constant pressure, 138Pa, 5kg air is cooled from 500K to 300K. The temperature of the
surroundings is 277k. Determine the available portion of the heal removed and the entropy
increase of the universe
4. Steam is contained in constant pressure closed system at 200kPa and 202oC and is allowed
to reach thermal equilibrium with the surroundings which is at 260C. Find the loss of
available energy per kilogram of steam