ATD Unit 1

Engineering Thermodynamics 4
CHAPTER 1 Basic Concept & First law
What is Thermodynamics?
For a wide range of engineering plant like steam turbines, reciprocating engines, turbo-jets,
rockets, combustion systems etc., we are concerned with the transfer of heat and work. In many
cases the objective is to convert one form of energy to another. Thermodynamics is science of
energy and entropy. “Thermodynamics is the science that deals with heat and work and
those properties of substances that bear a relation to heat and work.”
Some keywords:
• Properties: density, temperature, pressure, …
• State: a collection of properties
• Process: a path between states
• Energy: heat, work, internal energy, enthalpy
• Entropy: degree of disorder
What will we learn?
• Identification of thermodynamic properties and states

• Basic laws
Zeroth law : equality of temperature (thermal equilibrium)
1st law : conservation of energy
2nd law : conservation of entropy
• System and control volume analysis

• Directionality of process
• Efficiency analysis
• Practical devices and cycles
All the above laws were derived from experience without mathematical proofs.
Before going into the analysis of such changes, it is necessary to introduce some basic
concepts.
System / Control Volume
For defining the object under study, we draw a boundary around what we wish to study.
A system is a region of space containing a quantity of matter whose behaviour is being

investigated. This quantity of matter is separated from the surroundings by a boundary, which
may be a physical boundary like walls of a vessel, or some imaginary surface enveloping the
region. The term surroundings is restricted to those portions of the matter external to the
system, which are affected by changes occurring within the system. Before any thermodynamic
analysis is attempted, it is necessary to define the boundary of the system because it is across
the boundary that work, heat and mass are said to be transferred.
Now let us see what is happening at the boundary? Can work, heat, mass cross the boundary?
This makes for different definitions of the systems:
Definition Work Heat Mass

Isolated system
No No No
Also called
Closed system Yes Yes No
Control Mass
Also called Yes Yes Yes
Open system
Control Volume
A closed system with moving boundary
Fig. Examples of Closed System
When the same matter remains within the region throughout the process under investigation it is
called closed system. In this case, only heat and work cross the boundary.
An open system is a region in space defined by a boundary across which the matter may flow
in addition to work and heat.
Fig. Examples of Open System

The isolated system is one in which there is no interaction

between the system and surroundings. There is no mass or
System energy transfer across the system boundary.
Examples of open system⇒ flow nozzles, steam turbine, boiler

Surroundings etc.
Fig. Isolated systems Examples of closed system⇒ mixer of water and steam in a
closed vessel, a gas expanding in a cylinder by displacing a
piston. Hence, for a closed system, boundary need not be fixed; it may contract or expand to
accommodate any change in volume undergone by a fixed quantity of fluid.
The processes undergone in a closed system ⇒ non-flow process.
The processes undergone in an open system ⇒ flow process.
State, Property, Path, Process
The idea of system is defined in the introduction. A closed system is fully defined when
the following details are known:
• The fluid, i.e. whether gas, water etc.
• The boundary between the fluid under consideration and its surroundings
• The mass of the fluid within the boundary.
Every system has certain characteristics by which its

physical condition may be described, e.g. volume,
temperature, pressure etc. Such characteristics are
called properties of the system. These are all
macroscopic in nature. When all the properties of a
system have definite values, the system is said to
exist at a definite state. Any operation in which one
or more properties of a system change is called a
change of state. The succession of states passed
through during a 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, e.g. a constant pressure process.
The value of property does not depend on process through which the fluid is passed. The
change in the value of property depends on the initial and final states of the system. Pressure,
specific volume and temperature are some examples of basic properties. Three more
properties- internal energy, enthalpy and entropy emerge as a consequence of First and
Second Laws of Thermodynamics. From these six properties, only two may be selected to
determine the state of a closed system in thermodynamic equilibrium and the remaining four
values are then fixed. Care must be taken to see that the two properties are independent of
each other, i.e. it must be possible to vary one of these properties without changing the other.
For example, when a liquid is in contact with its vapour in a closed vessel it is found that the
temperature at which the liquid and vapour in equilibrium is always associated with a particular
pressure and one cannot change one without the other. Pressure and temperature cannot be
used to determine the state of such systems. However, pressure and specific volume may be
used to define the state of such system. It follows that the initial and final states of any
closed system can be located as points on a diagram using two properties as
coordinates. Properties may be of two types. Intensive (Intrinsic) properties are independent
of mass of the system, e.g. pressure, temperature, etc. Extensive properties are related to the
mass of the system, e.g. volume, energy etc.
Equilibrium
By specifying the P, T, ρ and V, the state of the system is defined.
Two adjacent systems (or system and surroundings) left for a long time will reach
equilibrium.
A system is said to be in thermodynamic equilibrium if no further changes occur within it

when it is isolated from the surroundings in such a way that no heat and work can cross the
boundary. The properties must be uniform throughout the system when it is in equilibrium. Only
under conditions of equilibrium can a single values of pressure or temperature be ascribed to
the system, and thus be used to determine its state.
For a system to be in equilibrium, system must be in mechanical, thermal and chemical

equilibrium.
If the system is imagined to pass through a continuous series of equilibrium states during the
process, the intermediate states could be located on the diagram, and a line representing the
path of the process could be drawn through all the points. Such a process is called a reversible
process or quasi-static process. However, in all real processes, the system is not in
equilibrium in any of the intermediate states. These states cannot be located on the coordinate
diagram because the properties do not have single unique values throughout the system. Such
processes are called irreversible processes.
1 1
2 2
Reversible Process Irreversible Process
Mechanical Equilibrium: Force Balance
For a system to be in mechanical equilibrium, summation of all the forces acting on the body
should be zero i.e. ΣF = 0 if acceleration is zero (Newton’s second law)
− Quasi-equilibrium versus non-equilibrium
Quasi-equilibrium: if the process is slow enough, the system is considered

approximately in equilibrium at each time.
For example, remove weights one by one. Each time the system reaches equilibrium
instantaneously. This process is called Quasi-Equilibrium Process.
If you remove weights all at once, Process is difficult to describe. Then it is Non equilibrium
process.
How slow is slow?
Relative to the relaxation time scales for pressure (speed of sound), temperature
(molecular collision), etc. These time scales are usually very short, so the quasi-
equilibrium approximation is valid (even for reciprocating engines).
Q: Can we define a path for a quasi-equilibrium process?
Q: Can we define a path for a non-equilibrium process?
Q: Can we calculate anything that happened during a non-equilibrium process?
Thermal equilibrium
The property, which distinguishes thermodynamics from other sciences, is temperature.
Temperature is associated with the ability to distinguish between hot from cold. When two
bodies at different temperature are brought into contact, after some time they attain a common
temperature and are said to be in thermal equilibrium. Two systems are said to have equal
temperatures if there is no change in any of their observable characteristics when they are
brought into contact with one another.
State 1 State 2
As
Process
show
Copper Steel Copper Steel n in
T1 T2 T3 T3 the
fig., if
a copper body at a temperature T1 is brought into contact of a steel body at temperature T2 such
that T1 > T2, then after some time both the bodies will be at a temperature T3. The temperature
T3 will be in between T1 and T2. Both the bodies then can be said to be in thermal equilibrium. If
two bodies (A and B) are each equal in temperature to a third body (C), they (A and B) are
equal in temperature to each other. This is the principle of thermal equilibrium and is known as
zeroth law of thermodynamics. In other words, the zeroth law of thermodynamics states that if
TA = TC and TB = TC, then TA = TB.
The possibility of measuring the temperature rests upon this principle.
Temperature scale:
C (Celsius) K (Kelvin) K = C + 273.15
F (Fahrenheit) R (Rankine) R = F + 459.67
F = 32 + (9/5)C
Summary:
We can say that the state of a system changes when heat and work cross the boundary.
Thermodynamics provides a means of relating the quantities of heat and work with the
change of state. The structure of thermodynamics rests on two important principles called
the First and Second Laws of Thermodynamics. These cannot be proved and are treated
as axioms.
WORK and HEAT

We can now:
1. Distinguish the system from its surroundings.
2. Find the properties of the system to identify its state.
Our objective now is to find out how we can use it to produce Work and Heat that are useful in
Work
Surroundings
Surroundings
Heat
our living.
Energy Transfer across the system boundary by Work and Heat
WORK
Work is said to be done when force acting upon a body moves through a distance in the
direction of the force. If part of the boundary of a system undergoes a displacement
under the action of a pressure, the work done, W, is the product of the force (pressure x
area), and the distance it moves in the direction of the force.
The basic unit of work is Newton metre (Nm), and also called the joule (J). Work is a quantity,
which is not a property of a system. It is a transient quantity, which only appears at the
boundary while a change of state taking place within a system.
Hence, work is ‘something’ which appears at the boundary when a system

changes its state due to movement of a part of the boundary under the action of
force. Another definition is: work is said to be done by a system if the sole effect on
things external to the system can be reduced to raising of weight.
Examples of Work
Work crossing the system boundary whose sole effect on the surroundings could be raising of a
weight
Various types of Work
(i) pdV- work or Displacement work

Let us consider a closed system where a part of the boundary is allowed to move under
such conditions that the external restraining force is infinitesimally smaller than the force
produced by the pressure of the system. The area of the piston is A and the pressure of
the fluid at any instant is p. If p is assumed to be constant during an infinitesimal
movement of the piston over a distance dl, the work done by the fluid in moving the
external force pA through this distance is pA dl. But A.dl is dV, the infinitesimal
change of volume, therefore
dW = pdV
If the expansion occurs from

pressure p1 to a pressure p2 in such
a way that the restraining force is
changed continuously, then the total
work done can be found out by
summing up all the increments of
work pdV, i.e.
2
W = ∫ p dV
1
(ii) Electrical work
When a current flows through a

resistor taken as a system, there is
work transfer into the system. This is because current drives the motor, the motor can
drive a pulley and the pulley can raise the weight.
The current flow, I, in amperes is given by
dC
I=
dτ
where C is the charge in coulombs and τ is time in seconds. Thus dC is the charge
crossing a boundary during time dτ. If E is the voltage potential, the work is
dW = E. dC = EI. dτ
2
or W = ∫ E I dτ
1
The electrical power will be
W& = E I
(iii) Shaft work
If T is the torque applied to the shaft and dθ is the angular displacement, the shaft work
is
2
W = ∫ T dθ
1
and the shaft work is
& = T dθ = T ω
W ∫ dτ
where ω is the angular velocity.
HEAT
Heat is ‘something’ which appears at the boundary when a system changes its
state due to temperature difference between the system and surroundings. It is
denoted by Q and the unit of heat is joule (J).
Sign Convention for Heat and Work
Work done by the system on the
surroundings is positive; work done on the
system by the surroundings is negative.
Heat flow into the system from the surroundings is positive and heat flow from the
system to the surroundings is negative.
Hence,
Qin is taken as positive.
Wout is taken as positive.
PATH FUNCTION AND POINT FUNCTION
From Fig. it can be seen that a system can be taken from state 1 to state 2 along many
quasi-static paths, such as A, B or C. Since the area under each curve represents the
work for each process, the amount of work involved in each case is not a function of the
end states of the process, and it depends on the path of the system follows in going
from state 1 to state 2. For this reason, work is called a path function and dW is an
inexact or imperfect differential.
Thermodynamic properties are point

functions, since for a given state; there is a
definite value for each property. The
change in thermodynamic property of any
system in a change of state is independent
of path of the system follows during the
change of state, and only depends on the
initial and final states of the system. The
differentials of point functions are exact or
perfect differentials and integration is
simply
2
∫ dV = V
1
2 − V1
However,
∫ dW ≠ W
1
2 − W1
Rather
2
∫ dW =
1
W2 or W1-2
1
Work , heat and reversibility
Let us consider a closed system where

a part of the boundary is allowed to
move under such conditions that the
external restraining force is
infinitesimally smaller than the force
produced by the pressure of the
system. The area of the piston is A and
the pressure of the fluid at any instant
is p. If p is assumed to be constant
during an infinitesimal movement of the
piston over a distance dl, the work
done by the fluid in moving the external
force pA through this distance is pA dl.
But A dl is dV, the infinitesimal change
of volume, therefore
dW = pdV
If the expansion occurs from pressure p1 to a pressure p2 in such a way that the
restraining force is changed continuously, then the total work done can be found out by
summing up all the increments of work pdV, i.e.
2
W = ∫ p dV
1
The condition under which this expansion has been imagined to proceed is just those
necessary for the expansion to be reversible. There are no pressure gradients and the
properties are uniform throughout the system at all the times. The system passes
through a series of equilibrium states and the process may be represented by a full line
2
on the p-v diagram. The area under the curve is given by ∫ p dV and it represents the
1
work done per unit mass of fluid.
It may be noted that ∫pdV is not always equal to the work done per unit mass, and the
equality only holds when the system passes through a series of equilibrium states.
Consider a container divided

into two compartments by a
sliding partition. One part
contains a mass of gas at a
pressure p1 and specific (a) (b)
Free expansion
volume v1 and the other is
evacuated. When the partition is withdrawn, the gas undergoes free expansion and
settles down to a new equilibrium state with pressure p2 and specific volume v2.
The intermediate states are indeterminate

p1
because no single values of p and v can be
ascribed to the system as a whole. The end
p states could be located in the p-v diagram, but
p2 the process could be indicated only by dotted
dV
lines. By having several partitions, some
V1 V2
intermediate pressures and specific volumes
Irreversible process could be measured and the corresponding state
points plotted in the p-v diagram. If a dotted
curve is drawn through all such points, the area under the curve would be equal to
2
∫ p dV . Yet no work has been done by the system on the surroundings at all because
1
no external force has been moved through a distance.

Thus it implies that the reversible expansion or compression is an infinitely slow

process. Since any real process must occur within a finite time, it is clear that the
reversible process is an ideal process.
Similarly, it can be shown that the transfer of energy due to the temperature difference
can only be carried out reversibly if the temperature difference is infinitesimally small.
This implies that the rate at which the transfer can proceed is infinitely slow.
Similarities between Heat and Work
1. Heat & work are phenomena that occur at the system boundary.
2. The system does not possess heat & work; it only possesses energy.
3. The consequence of heat & work crossing the system boundary is to change the system
state or its energy content.
4. Both heat and work are path dependent phenomena
Summary
Neither heat nor work are properties of a system, but both are transient quantities, only
appearing at the boundary while a change in state occurs within the system. Although
they cannot be used to describe the state of a system, heat and work can be used to
describe the process undergone by the system during the change of state. Heat and
work are not only functions of the initial and final state of the system, but also of the
process undergone by the system.
First Law of Thermodynamics of a Closed System.
The structure of thermodynamics rests upon two fundamental laws. The First law, which
will be introduced here, is concerned with the principle of conservation of energy as
applied to a closed system, which undergo changes of state due to transfers of work
and heat across the boundary. The First law cannot be proved; its validity rests upon
the fact that neither it nor its consequences have ever been contradicted.
THE CYCLE
A closed system is said to undergo a cyclic

1
process, or cycle, when it passes through a
series of states in such a way that its final
1-2-1 A cycle
state is equal in all respect to its initial state.
This implies that all its properties have

2
regained their initial values. The system is
then in a position to be put through the same
A cycle
cycles of events again, and the procedure
may be repeated indefinitely.
FIRST LAW OF THERMODYNAMICS FOR A CLOSED SYSTEM
When any closed system is taken through a cycle, the net work delivered to the
surroundings is proportional to the net heat taken from the surroundings. This may be
expressed as
(ΣδQ)cycle ∝ (ΣδW)cycle
or
(ΣδQ)cycle = J (ΣδW)cycle
J is called the mechanical equivalent of heat or Joule’s equivalent; it expresses the

number of work units, which are equivalent to one unit. For SI unit the value of J is unity.
If kJ and kcal are chosen as the units of work and heat respectively, then the value of J
is 4.19 kJ/kcal. Hence, J can be dropped from above equation, which now can be
written as
(ΣδQ)cycle - (ΣδW)cycle = 0
FIRST LAW OF THERMODYNAMICS FOR A CHANGE OF STATE

The expression (ΣδQ)cycle = (ΣδW)cycle applies to a system undergoing a cycle. But if the
system undergoes a change of state during which both heat and work transfers are
involved, the net energy transfer will be stored or accumulated within the system. If Q is
the amount of heat transferred to the system and W is the amount of work transferred
from the system during the process, the net energy transfer (Q-W) will be stored in the
system. This stored energy is known as internal energy or simply energy of the system.
Hence, the First Law for a change of state is the net energy transfer during a process
involving heat and work transfers is equal to the change in increase in energy of the
system.
That is
Q – W = ΔE
ENERGY IS A PROPERTY OF THE SYSTEM
Proof: Consider a system which changes its state from state 1 to state 2., following the
path A and returns from state 2 to state
1 following path B. So the system
undergoes a cycle.
Hence,
QA = WA +ΔEA
and QB = WB +ΔEB
The process A and B together forms a cycle and hence
QA + QB = WA + WB
or QA - WA = WB - QB = - (QB - WB)
or ΔEA = -ΔEB
Similarly if the system returns from state 2 to state 1 following path C instead of path B
then
ΔEA = -ΔEC
Hence, ΔEB = ΔEC

That is the change in energy between the two states of a system is same and
independent of path followed by the system. Therefore energy has a definite value for
every state of the system. Hence, it is a point function and a property of the system.
Different forms of energy
The symbol E refers to the total energy of the system. Basically there are two modes in
which the energy may be stored in the system:
• Macroscopic energy mode;
• Microscope energy mode.
Macroscopic energy mode includes kinetic energy and potential energy of the system.
m V2
Kinetic energy, EK =
2
Potential energy, EP = mgZ
Where, m is the mass, V is the velocity and Z is the elevation of the system.
Microscopic energy mode refers to the energy stored in the molecular and atomic
structure of the system, which is called internal energy, denoted by U.
Hence, E = EK + EP + U
For a closed system EK = 0 and EP also can be assumed to be zero.
Hence, for a closed system E=U
and Q – W = ΔU = U2 – U1
or dQ – dW = dU
COROLLARIES OF THE FIRST LAW
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.
If the property is denoted by U, the corollary can be expressed as

2
∑ (δQ − δW ) = U2 − U1
1
or Q – W = U2 – U1
where Q and W are the net quantities of heat and work crossing the boundary during
the change of state. The property U is called the internal energy of the system and
equation is called the non-flow energy equation.
The internal energy, U, is sum of microscopic energy due to
• Molecular level – translation, rotation, vibration
• Chemical reaction – bond energy (heat of formation)
• Dissociation – ion energy
• Atomic – nuclear energy
Internal energy is a thermodynamic property and hence it is a State function and independent of
process. If two independent properties are given, U is uniquely determined.
Corollary 2. The internal energy of a closed system remains unchanged if the system is
isolated from its surroundings.
Boundary If the system is isolated from the surroundings,

Hot Q and W are both zero and hence, ΔU must be
zero. The system represented in Fig. below is
Cold an example of an isolated system. All that
happens in this case is a spontaneous
redistribution of energy between parts of the
Isolated system system, which continues until a state of
equilibrium is reached; there is no change in the
total quantity of energy within the system during the process. Corollary 2 is often called
the Law of Conservation of Energy.
Corollary 3. A perpetual motion machine of the first kind (PMM I) is impossible.

Definition: PMM1 is a device which delivers work continuously without any energy
input.
The perpetual machine was originally conceived Q

as a purely mechanical contrivance which, when
once set in motion, would continue to run forever.
Existence of such a machine is impossible W
Engine
because of the presence of friction. What would be
immense value is a machine producing a PMM I
continuous supply of work without absorbing energy from the surroundings.
It is always possible to devise a machine to deliver a limited quantity of work without a

source of energy in the surroundings. For example, a gas compressed behind a piston
will expand and do the work at the expense of internal energy of the gas. Such a device
cannot produce work continuously and for this to happen the machine must be capable
of undergoing a succession of cyclic process. But as per First Law no net amount of
work can be delivered by the system if a net amount of heat is not supplied by the
surroundings during a cycle. Thus the First law implies that a perpetual machine of first
kind is impossible.
THE ENERGY EQUATION AND REVERSIBILITY
The energy equation for the non-flow process can be written as
Q – W = U2 – U1
When the system is in equilibrium all the properties are uniform throughout the system
and each unit mass of the system will have same internal energy. Thus if u represents
the internal energy per unit mass of the system, then it is possible to write U = mu. u is
termed as specific internal energy. It is often convenient to work with the specific
quantities throughout an analysis and then multiply the final result by the mass of the
system. Thus the non-flow energy equation is usually written as
Q – W = u2 – u1
implying that Q and W are the quantities of heat and work per unit mass.
For a reversible process, the system is imagined to pass through a continuous series of
equilibrium states. In such cases the equation may be applied to any infinitesimal part of
the process between the end state, and the energy equation can be written as
dQ – dW = du
For irreversible process the system does not pass through a series of equilibrium states.
Hence, it is not possible to write mu for the internal energy of the system in any
intermediate state. Each elemental mass δm may have a different specific internal
energy e, which may include kinetic and potential energy of the mass δm. When
considering the irreversible processes, the energy equation can only be used in the
integrated form and it is then sufficient to be able to assign the values of u to the end
states.
CONSTANT VOLUME PROCESS
For a constant volume process, work can only be done by some method of churning
the liquid. There cannot be any ∫pdV work as no external force has been moved through
a distance. Hence, W must be zero or negative. For a constant volume process, unless
otherwise stated, work done is taken as zero. Thus energy equation for a constant
volume process is usually written as
Q = u2 – u1
If, in addition to work being zero, it is stipulated that the heat is transferred by virtue of
an infinitesimally small temperature difference, then the process is reversible and the
equation can be written in differential form as
dQ = du
CONSTANT PRESSURE PROCESS
A closed system undergoing at constant process is shown in Fig. The fluid is enclosed
in a cylinder by a piston on which rests a constant weight. If heat
W
is supplied, the fluid expands and work is being done by the
system in overcoming the constant force; if the heat is extracted,
Q
the fluid contracts and work is done on the system by the constant force. In the general
case
Q – W = (u2 – u1)
If no paddle work is done on the system, and the process is reversible,
dQ – p dv = du
Since p is constant, this can be integrated to give
Q – p (v2 – v1) = (u2 – u1)
A further simplification is for constant pressure process if a new property is introduced.

Since p is constant, p dv is identical to d(pv). Thus energy equation becomes
dQ – d(pv) = du
or dQ = d(u + pv) = dh
where h = u + pv, known as enthalpy. Since enthalpy is a combination of properties u, p

and v, it itself is a property. Hence
h = u + pv
and for any mass of fluid m, in a state of equilibrium
H = U + pV
Using this derived property, the energy equation for a reversible constant pressure
process becomes
dQ = dh
or in the integrated form
Q = (h2 – h1)
Thus heat added in a reversible constant pressure process is equal to increase of

enthalpy, whereas it is equal to increase of internal energy in the reversible constant
volume process.
SPECIFIC HEAT
The specific heat at constant volume CV is defined as the rate of change of specific
internal energy with respect to temperature when volume is held constant, i.e.
⎛ ∂u ⎞
CV = ⎜ ⎟
⎝ ∂T ⎠ V
For constant volume process
Δu = CV ΔT
For a closed system with constant volume process
Q = Δu = CV ΔT
The specific heat at constant pressure CP is defined as the rate of change of specific
enthalpy with respect to temperature when pressure is held constant, i.e.
⎛ ∂h ⎞
CP = ⎜ ⎟
⎝ ∂T ⎠P
For constant pressure process
Δh = Cp ΔT
For a closed system with constant pressure process
Q = Δh = CP ΔT
For a perfect gas u = f(T)
Hence, du = CV dT or u2 – u1 = CV (T2 – T1)
h = u + pv
= u + RT
or dh = du + R dT = CV dT + R dT = (CV + R) dT
Now, dh = CP dT ( this is true only for a perfect gas)
Hence, CP = Cv + R
CP
Also, =γ
CV
For air: CP = 1.005 kJ/kg K
Cv = 0.718 kJ/kg K
R = 0.287 kJ/kg K
γ = 1.4
PROCESS IN WHICH p v = constant

2
W1− 2 = ∫ p dV
1
p1v1
Now pv = p1v1 = c or p=
v
2 2
p1 v 1 dv v
∴ 1W2 = ∫ dv = p1 v 1 ∫ = p1 v1 ln 2
1
v 1
v v1
v2 p
∴ 1W2 = p1 v1 ln = p1 v 1 ln 1
v1 p2
POLYTROPIC PROCESS
The constant volume and constant pressure processes can be regarded as limiting
cases of a more general type of processes in which both volume and pressure change
in a certain specified way. In many real processes, it is found that the states during
expansion or compression can be expressed as pvn = 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. This is called Polytropic process. When
n=0 the relation reduce to p = constant and when n = ∞ it reduces to v = constant.
For the reversible Polytropic

process, single values of p and v can truly define the state of a system, and dW = pdv.
For any intermediate state
p1 v1n = p2 v n2 = p v n
Therefore
2 2
( )
dv p1v1n v12−n − v11−n p2 v n2 v12−n − p1 v1n v11−n
W = ∫ p dv = p v ∫ n =
n
=
1 1
1 1
v 1− n 1− n
⎡ n −1
⎤
p2 v 2 − p1 v1 p1 v1 ⎢ ⎛ p2 ⎞ n ⎥
= = 1 − ⎜⎜ ⎟⎟
1− n n − 1 ⎢ ⎝ p1 ⎠ ⎥
⎣ ⎦
The integrated form of energy equation for a reversible polytropic process may therefore
be written as
p2 v 2 − p1 v1
Q− = (u2 − u1 )
1− n
Relation between p,v,T
pv = RT
p1 v1 p2 v 2 T2 p2 v 2
= or =
T1 T2 T1 p1 v1
1
−
v 2 ⎛ p2 ⎞ n
Now p1 v1n = p2 v 2n or =⎜ ⎟
v1 ⎜⎝ p1 ⎟⎠
n −1
1− n
T ⎛p ⎞ n ⎛v ⎞
∴ 2 = ⎜⎜ 2 ⎟⎟ = ⎜⎜ 2 ⎟⎟
T1 ⎝ p1 ⎠ ⎝ v1 ⎠
Reversible Adiabatic Process (Isentropic Process)
The term adiabatic is used to describe any process during which heat is prevented
from crossing the boundary of the system. That is, an adiabatic process is one
undergone by a system, which is thermally insulated from its surroundings. For
adiabatic non-flow processes, the energy equation reduces to
- W = (u2 – u1)
From First Law
Q = du + W
For adiabatic process, this becomes
0 = CV dT + pdv
Also pv = RT (equation of state)
or pdv + vdp = R dT
CV ⎛ CV ⎞ C
Hence, (p dv + v dp) + pdv = 0 or ⎜ + 1⎟ p dv + V v dp = 0
R ⎝ R ⎠ R
Now CP = CV +R
CP C
∴ pdv + V vdp = 0
R R
CP dv dp
or + =0
CV v p
Integrating we get
γ ln v + ln p = const
or pvγ = const.
ISOTHERMAL PROCESS
When the quantities of heat and work are so proportioned during a process such that
the temperature of the fluid remains constant, the process is said to be isothermal.
Since temperature gradients are excluded by definition, the reversibility of the
isothermal process is implied.
Recommended Solution Procedure
STEP 1
Sketch the diagram including all mass, heat and work flows, and direction of forces (e.g.
external pressures and gravitation).
STEP 2
Define a system. Identify the initial and final states (label them 1 and 2), and write down all the
known conditions.
STEP 3
Write the applicable laws for the system.
STEP 4
Determine if the substance can be handled as an ideal gas or by the table.
STEP 5
What do you know about the process? Anything constant or zero? Relationships
between properties?
STEP 6
Find which quantities are known and which are unknown. Determine which two independent
properties should be found for any given state. Diagrams are helpful.
STEP 7
Determine the unknown quantities.

First Law applied to Flow Processes

STEADY FLOW ENERGY EQUATION
For any system and in any process, the first law can be written as
Q = ΔE + W
Where E represents all forms of stored energy in the system.
For a pure substance

E = EK + EP + U
Where
m C2
EK= Kinetic energy = ; where C is the velocity of fluid.
2
EP = Potential energy = mgz
U is the residual energy (internal energy) stored in the molecular structure of the
substance. Hence,
Q = ΔEK + ΔEP + ΔU + W
δQ
e
Ce
Steady flow device

i Shaft
Ci δW ze
zi
Steady-flow process
Let
Ai, Ae ⎯ Cross sectional area , m2
Wi, we ⎯ mass flow rate, kg/s
pi, pe ⎯ absolute pressure, N/m2
vi, ve ⎯ specific volume, m3/kg
ui, ue ⎯ specific internal energy, J/kg

Ci, Ce ⎯ velocity, m/s
zi, ze ⎯ elevation from an arbitrary datum level, m
Subscript i and e refers to the inlet and exit sections.
The total energy of mass δm at the inlet is
1 ⎛ C2 ⎞
Ui + δm Ci2 + δm g zi or δm ⎜⎜ ui + i + gzi ⎟⎟
2 ⎝ 2 ⎠
Similarly, the total energy of mass δm at the outlet is
⎛ C2 ⎞
δm ⎜⎜ ue + e + gz e ⎟⎟
⎝ 2 ⎠
Lastly we must consider how the system changes its state from i to e. We may assume
that δQ units of energy are transferred to the system as heat and that δW units of
energy are transferred to the surroundings as work via. a turbine shaft. δW is not only
work done so far as the system is concerned
because parts of its boundary move at
sections i and e. For the element δm to enter
the open system, the system must be
compressed, its volume decreasing by δm vi.
This is accompanied by a force piA moving a
distance l = δm v1/A, where A is the cross-
sectional area of the element. The work done by the surroundings on the system is
therefore δm pi vi. Similarly it can be shown that the work done by the system to the
surroundings is δm pe ve. The net work done by the system during the change is
therefore
δW + δm (pe ve – pi vi)
We may now write the energy equation for the open system as
⎛ C2e ⎞ ⎛ C2 ⎞
⎜
δQ – {δW + δm (pe ve – pi vi)} = δm ⎜ ue + + gz e ⎟⎟ - δm ⎜⎜ ui + i + gzi ⎟⎟
⎝ 2 ⎠ ⎝ 2 ⎠
By writing h for (u + pv), the equation becomes
⎛ C2 ⎞ ⎛ C2 ⎞
δQ − δW = δm ⎜⎜ he + e + z e ⎟⎟ − δm ⎜⎜ hi + i + zi ⎟⎟
⎝ 2 ⎠ ⎝ 2 ⎠
The continuous steady-flow process consists of the sum total of all the elemental mass
transfers across sections 1 and 2. It may therefore be represented as
⎛ C2e ⎞ ⎛ Ci2 ⎞
∑ δQ − ∑ δW = ∑ δm ⎜ he + 2 + ze ⎟ − ∑ δm ⎜ hi + 2 + zi ⎟⎟
⎜ ⎟ ⎜
⎝ ⎠ ⎝ ⎠
If we consider the properties to be uniform over the cross-section of flow at inlet and
outlet and write m for Σδm then the above equation becomes after simplifying
Q − W = (he − hi ) +
2
(
1 2
)
Ce − Ci2 + g (z e − zi )
where Q and W are the heat and work transfers per unit mass flowing through the
system. The assumptions upon which the equation is based may be summarised as
follows:
1. The mass flow at the inlet is constant with
respect to time, and equal to mass flow at
outlet.
2. The properties at any point within the open
system do not vary with time.
3. The properties are constant over the cross-
section of the flow at inlet and outlet.
4. Any heat or work crossing the boundary does
so at a uniform rate.
Finally we must note an important equation which
follows directly from assumptions (1) and (3). It is known as the continuity equation
and expresses the principle of conservation of mass in steady flow. If m is the rate of
mass flow, we have
A i Ci A e Ce
m = = = ρi Ci A i = ρ e Ce A e
vi ve
FIRST LAW AS A RATE EQUATION

It expresses the instantaneous or average rate at which energy crosses the system
boundary as heat and work and the rate at which the energy of the system changes.
Conservation of Mass
Mass flow in – mass flow out = accumulation in the
control volume.
i.e. δmcv = mi - me
Dividing by δt we get
δm cv m i m e
= −
δt δt δ t
dm cv
or = mi − m e
dt
δm i δm e
where = mi and = me
δt δt
Conservation of Energy
Consider a time interval δt during which an amount
of heat δQ crosses the system boundary, an
amount of work δW is done by the system, the
internal energy change is ΔU, the kinetic energy
change is ΔK and potential energy change is ΔPE.
Since the mass flow rates at the inlet m i and outlet
m e are not same, there will be a change of energy
stored in the system. If the change in energy stored

in the system is ΔEcv, then
First Law states
δQ = ΔU + ΔKE + ΔPE + δW + ΔEcv
Dividing by δt we get
δQ ΔU ΔKE ΔPE δW ΔE cv
= + + + +
δt δt δt δt δt δt
dU d (KE ) d (PE ) dE cv
or Q= + + +W+
dt dt dt dt
δQ δW
where =Q and =W
δt δt
Hence, the First Law becomes
⎛ C2 ⎞ ⎛ C2 ⎞ dE cv
Q + ∑ mi ⎜⎜ h i + i + g z i ⎟⎟ = ∑ m e ⎜⎜ h e + e + g z e ⎟⎟ + W +
⎝ 2 ⎠ ⎝ 2 ⎠ dt
dE cv ⎛ C i2 ⎞ ⎛ C 2e ⎞
i.e. = Q − W + ∑ mi ⎜ hi +
⎜ + g zi ⎟ − ∑ me ⎜ he +
⎟ ⎜ + g z e ⎟⎟
dt ⎝ 2 ⎠ ⎝ 2 ⎠
Simplifications
1. Steady State Flow
Fluid properties may vary in space but are constant at each location.
mi ≠ m e ; hi ≠ h e
dEcv
=0
dt
Hence,
⎛ C i2 ⎞ ⎛ C 2e ⎞
0 = Q − W + ∑ mi ⎜ hi +
⎜ + g zi ⎟ − ∑ me ⎜ he +
⎟ ⎜ + g z e ⎟⎟
⎝ 2 ⎠ ⎝ 2 ⎠
2. Steady state flow with uniform mass flow rate
Continuity equation becomes
mi = m e = m
∴ Q − W = m (h e − hi1 ) +
m 2
2
( )
C e − C i2 + m g (z e − z i )
3. Negligible KE and PE
& −W
Q & (h e − h i1 )
& =m
4. No heat loss, work with negligible KE and PE
hi = he
Examples of Steady State Devices
OPEN SYSTEM WITH STEADY FLOW
Boiler
In the boiler, the fluid entering as liquid, leaves as a vapour at a constant rate. In this
case no work is done on or by the fluid as it passes through the system. The velocities
are usually quite low, so that the difference between kinetic energies at the inlet and
outlet is negligible compared to the other terms of the equation.
Assumptions
• Steady (dECV/dt = 0)
• Single inlet/exit
• No shaft work
• KE, PE change negligible (usually)
Hence, Steady Flow Energy Equation (SFEE)

becomes
Q = he – hi kJ/kg
Nozzles and Diffusers
A nozzle is a duct of varying cross-sectional area so designed that a drop in pressure from inlet
to outlet accelerates the flow. The flow through a nozzle usually occurs at a very high speed,
and there is little time for the fluid to gain or lose energy by a flow of heat through the walls of
the nozzle as the fluid passes through it. The process is therefore always assumed to be
adiabatic. Also, no work crosses the boundary during the process. The function of diffuser is the
reverse of that of nozzle.
Nozzle – A device to increase velocity at the expense of

pressure.
Diffuser – A device to increase pressure at the Ci Ce

expense of velocity.
Nozzle, Ci < Ce
Assumptions
• Single inlet/exit Ci Ce
• No heat transfer (assuming adiabatic)
• No shaft work
• PE change negligible Diffuser, Ci > Ce
Hence, SFEE becomes
Ci2 C2e
hi + = he +
2 2
If Ce > Ci (nozzle) ⇒ he < hi (cools down)
If Ce < Ci (diffuser) ⇒ he > hi (warms up)
Turbine/Compressor
A turbine is a means of extracting work from a flow of fluid expanding from a high
pressure to a low pressure. 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 the rotor. As first approximation, the velocity at the inlet and
outlet of the turbine can be assumed equal. Since the velocity of flow through the
turbine is very high, the process can be assumed to
be adiabatic. The rotary compressor can be
regarded as a reverse turbine, work being done on
the fluid to raise the pressure.
Assumptions
• No heat transfer (usually, but not always)
• KE, PE change negligible (usually)
Hence, SFFF becomes
W = hi - he kJ/kg
Throttling Valves
A flow-restricting device that causes a significant pressure drop accompanied by a large

drop in Temperature (valves, porous plug, capillary tubes in refrigerators). The term
throttling is usually applied to relatively low-speed flow, i.e. low enough for any
difference between the kinetic energy at the inlet and outlet to be negligible. Any heat
transfer across the boundary can be neglected. Also no work crosses the boundary.
Assumptions
• No heat transfer and shaft work
• KE, PE change negligible
Hence, SFFF becomes
hi = he kJ/kg
ui + pivi = ue +peve
Hence, pv increases at the expense of u (temperature drops)
For real gases, h = h (T) only, i.e. Ti = Te
Heat Exchangers
Consider a double-tube type heat exchanger (tube and shell). In heat exchanger, the
change in potential energy and kinetic energy terms are very small and can be
neglected. Also, there is no external work.
Assumptions
• Multiple inlets/exits
• No heat transfer and shaft work
• KE, PE change negligible
Hence, SFEE becomes
∑m h = ∑m
i
i i
e
e he
or m 1 h1 + m 3 h 3 = m 2 h 2 + m 4 h 4
Power Plant
Boiler: Q b = 1Q 2 = m (h1 − h 5 ) = m (h 2 − h 5 ), sin ce h1 = h 2
Turbine: WT = − 2W3 = m (h 3 − h 2 )
Condenser: − Q C = 3 Q 4 = m (h 4 − h 3 )
Pump: − WP = − 4W5 = m (h 5 − h 4 )
Adding we have
1 Q2 + 3 Q4 − 2W3 − 4W5 = 0
or ∑ δQ − ∑ δW = 0

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Engineering Thermodynamics 4

CHAPTER 1 Basic Concept & First law

• Properties: density, temperature, pressure, …

• State: a collection of properties

• Process: a path between states

• Energy: heat, work, internal energy, enthalpy

• Entropy: degree of disorder

What will we learn?

• Identification of thermodynamic properties and states

1st law : conservation of energy

2nd law : conservation of entropy

• System and control volume analysis

A system is a region of space containing a quantity of matter whose behaviour is being

Definition Work Heat Mass

A closed system with moving boundary

Fig. Examples of Closed System

Fig. Examples of Open System

The isolated system is one in which there is no interaction

Examples of open system⇒ flow nozzles, steam turbine, boiler

The processes undergone in a closed system ⇒ non-flow process.

The processes undergone in an open system ⇒ flow process.

State, Property, Path, Process

• The fluid, i.e. whether gas, water etc.

• The mass of the fluid within the boundary.

Every system has certain characteristics by which its

A system is said to be in thermodynamic equilibrium if no further changes occur within it

For a system to be in equilibrium, system must be in mechanical, thermal and chemical

Reversible Process Irreversible Process

Mechanical Equilibrium: Force Balance

should be zero i.e. ΣF = 0 if acceleration is zero (Newton’s second law)

− Quasi-equilibrium versus non-equilibrium

Quasi-equilibrium: if the process is slow enough, the system is considered

How slow is slow?

Q: Can we define a path for a quasi-equilibrium process?

Q: Can we define a path for a non-equilibrium process?

Q: Can we calculate anything that happened during a non-equilibrium process?

The possibility of measuring the temperature rests upon this principle.

C (Celsius) K (Kelvin) K = C + 273.15

F (Fahrenheit) R (Rankine) R = F + 459.67

WORK and HEAT

2. Find the properties of the system to identify its state.

Energy Transfer across the system boundary by Work and Heat

Hence, work is ‘something’ which appears at the boundary when a system

Various types of Work

(i) pdV- work or Displacement work

If the expansion occurs from

(ii) Electrical work

When a current flows through a

The current flow, I, in amperes is given by

The electrical power will be

(iii) Shaft work

and the shaft work is

where ω is the angular velocity.

Wout is taken as positive.

PATH FUNCTION AND POINT FUNCTION

Thermodynamic properties are point

Work , heat and reversibility

Let us consider a closed system where

work done per unit mass of fluid.