FIRST LAW OF THERMODYNAMICS FIRST LAW OF THERMODYNAMICS (Part-1)

INTRODUCTION INTRODUCTION
The First Law of Thermodynamics is a particular statement based on the principles of law of
conservation of energy according to which the total amount of energy in any thermodynamic system
remains constant i.e. Energy cannot be created or destroyed. None of the energy is gained or expended
in the sense it is converted from one form to another. Initially the statement of conservation of energy
was quantitatively analyzed for thermodynamic systems by J.P. Joule during the period of eighteen
forties which has led to the statement of First law of thermodynamics.
Statement of First law of thermodynamics Statement of First law of thermodynamics
The transfer of heat and the performance of work may both cause the same effect in a system.
Energy which enters a system as heat may leave the system as work, or energy which enters the system
as work may leave as heat. Hence, by the law of conservation of energy, the net work done by the system
is equal to the net heat supplied to the system. The first law of thermodynamics can therefore be stated as
follows:
When a system undergoes a thermodynamic cyclic process, then the net heat supplied to the system
from the surroundings is equal to the net work done by the system on its surrounding.
Mathematically
i.e.,

Q =

W
where

represents the sum for a complete cycle.

The first law of thermodynamics can not be proved analytically, but experimental evidence has
repeatedly confirms its validity and since no phenomenon has been shown to contradict it, therefore the
first law is accepted as a law of nature.
Joules Experiment
The English scientist J.P.Joule conducted a series of experiments in 1840s, and these experiments led to
the first law of thermodynamics. The objective of joules experiment was to establish a relation between
amount of work spent to bring about the liberation of heat and the amount of heat liberated.
Fig-1: Joules Experiment
1
The experimental set up is shown in Fig-1(a). Work is done on the fluid(system) kept in an insulated
vessel by stirring of the paddle wheel. This work input to the fluid causes a rise in the temperature of the
fluid. The amount of work on the fluid is calculated by the product of the weight and the vertical
height(z) through which the weight descends. The system is then immersed in a water bath, as shown in
Fig-1(b), after removing the insulation. The heat is transferred from the fluid to the water bath till the
original temperature is reached, which will be indicated by the thermometer. Thus the system undergoes
a complete cycle with two energy interactions i.e. definite amount of adiabatic work transfer(W
1-2
) to the
system followed by an amount of heat transfer(Q
1-2
) from the system, shown in fig-1(c). The amount of
heat rejected by the fluid is equal to the increase of energy of the water bath.
y
x
W1-2
Q2-1
1
2
Fig-1(c): Cycle completed by a system with two energy interactions i.e., work transfer followed by heat transfer
Joule carried out many such experiments with different type of work interactions in a variety of systems,
he found that the net work input to the fluid system was always proportional to the net heat transferred
from the system regardless of work interaction. Based on this experimental evidence Joule stated that,
When a system (closed system) is undergoing a cyclic process, the net heat transfer to the system is
directly proportional to the net work done by the system. This statement is referred to as the first law
for a closed system undergoing a cyclic process.
i.e.,

W
J

Q =

W
Where J = Joules equivalent or Mechanical equivalent of heat
= 1Nm/J
If both heat transfer and work transfer are expressed in same units as in the S.I. units then the constant of
proportionality in the above equation will be unity and hence the mathematical form of first law for a
system undergoing a cyclic process can be written as
i.e.,

Q =

W
If the cycle involves many more heat and work quantities as shown in fig-1(d), the same result will be
found.
For this cyclic process the statement of first law can be written as

1 4 3 2 1 1 4 3 2 1
W Q
2
1
2
3 4
y
x
Fig-1(d): Cyclic Process on a Property Diagram
The cyclic integral in the above equation can be split into a series of non cyclic integral as
W W W W Q Q Q Q
1
4
4
3
3
2
2
1
1
4
4
3
3
2
2
1
+ + + + + +
or
1
Q
2
+
2
Q
3
+
3
Q
4
+
4
Q
1
=
1
W
2
+
2
W
3
+
3
W
4
+
4
W
1
i.e.,

Q =

W
or (Q)
cycle
= (W)
cycle
This is the first law for a closed system undergoing a cyclic process. i.e., it is stated as
When a closed system is undergoing a cyclic process the algebraic sum of heat transfers is equal to the
algebraic sum of the work transfers.
Equivalence of Heat and Work
Based on the results of a series of thoroughly conducted experiments J.P.Joule discovered a direct
proportionality between the spent work W and the quantity of heat obtained Q.
i.e., Q W
or Q = AW
where A is a Proportionality factor
Joule found that the proportionality factor A remains same irrespective of the method of heat
production, type of work, temperature of the body involved etc.
In other words, Joule established that when one and same amount of work is spent, one and same amount
of heat is liberated. Thus the amount of liberated heat was shown to be equivalent to the amount
equivalent of work spent; it is clear that this relation ship is true for the case when work is accomplished
with the expense of heat.
Using the results of these measurement. Joule calculated the magnitude of A which is known as
thermal equivalent of work and of J referred to as the mechanical equivalent of heat.
A = 0.002342 kcal/kgm
J = 426.99 kgm/kcal
It is obvious that J = 1/A
3
Note
J = 426.99 kgm/kcal
= 4.184 Nm/cal
= 1 Nm/J
First law for a closed system undergoing a non-cyclic process (i.e., for a change of state)
The expression (W)
cycle
= (Q)
cycle
applies only to the system undergoing cycles, and the algebraic
summation of all energy transfer across system boundaries is zero.
But if the system undergoes a change of states during which both heat and work transfer 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
shown in the fig-2 below,
The net energy transfer (Q-W) will be stored in the system.
Energy in storage is neither heat nor work and is given the
name internal energy or simply, the energy of the system.
Q-W = E
where E is the increase in the energy of the system
or Q = E + W
Here Q, W and E are all expressed in joules.
If there are more energy transfer involved in the process, as shown in the fig-3 below
Then the first law gives
(Q
2
+ Q
3
Q
1
) = E + (W
2
+ W
3
W
1
W
4
)
i.e., energy is thus conserved in the operation. Therefore the
first law is a particular formulation of the principle of the
conservation of energy. It can be shown that the energy has a
definite value at every state of a system and is therefore, a
property of a system.
4
Fig-2
Fig-3:
Energy- A Property of the system
Consider a system which changes its state from state from state-1
to state-2 by following the path L, and returns from state-2 to
state-1 by following the path M (fig-4). So the system undergoes
a cycle. Writing the first law for path L
Q
L
= E
L
+ W
L
----- (1)
And for path M
Q
M
= E
M
+ W
M
----- (2)
Fig-4: Energy-a property of system
The process L and M together constitute a cycle, for which

Q =

W
W
L
+ W
M
= Q
L
+ Q
M
or Q
L
W
L
= W
M
Q
M
----- (3)
from the equation (1), (2), and (3), it yields
E
L
= E
M
----- (4)
Similarly, had the system returned from the state-2 to sate-1 by following the path N instead of path M
E
L
= E
N
----- (5)
For the equation (4) and (5)
E
M
= E
N
Thus, it is seen that the change in energy between two states of a system is the same whatever the path
the system may fallow in undergoing that change of state. If some arbitrary value of energy is assigned
to the state-2, the value of energy at sate-1 is fixed independent of the path the system fallows.
Therefore, energy has definite value for every state of the system. Hence, it is a point function and a
property of the system.
Modes of Energy
Energy can exist in numerous forms such as thermal, mechanical, kinetic, potential, electric, magnetic,
chemical and nuclear and their sum constitutes the total energy E of a system.
i.e., E = kinetic energy (KE) + Potential Energy (PE) + remaining forms of energy.
5
The energy E is an extensive property and the specific energy e = E/m (J/kg) is an intensive property.
In thermodynamic analysis, it is often helpful to consider the various form of energy that make up the
total energy of a system in two groups
Macroscopic energy
Microscopic energy
The Macroscopic forms of energy are those a system possesses as a whole with respect to sum outside
reference frames which are related to motion and the influence of some external effects such as gravity,
magnetism, electricity and surface tension. Eg Kinetic energy and Potential energy
The Microscopic forms of energy are those related to the molecular structure of a system and the degree
of molecular activity, and they are independent of outside reference frames. The sum of all the
microscopic form of energy is called the internal energy (U).
Kinetic Energy
The energy that a system possesses as a result of its motion relative to reference frames is called kinetic
energy. When all parts of a system move with the same velocity, the kinetic energy(KE) is expressed as
KE = m V
2
/2 (kJ)
or, on a unit mass basis
ke = V
2
/2 (kJ/kg)

where V denotes the velocity of the system relative to some fixed reference frame
Potential energy
The energy that a system possesses as a result of its elevation in a gravitational field is called potential
energy(PE) and is expressed as
PE = mgz (kJ)
or, on a unit mass basis
pe = gz (kJ/kg)
where g is the gravitational acceleration and z is elevation of the center of gravity of a system to
some arbitrarily reference level
The magnetic, electric and surface tension effects are significant in some specialized cases only and
usually ignored. In the absences of such effects, the total energy of a system is expressed as
E = KE + PE + U =mV
2
/2 + mgz + U
or, on unit mass basis
e = ke + pe + u = V
2
/2 + gz + u
Since the terms comprising E are point functions, we can write
E or dE = d(KE) + d(PE) + dU
The first law of thermodynamics for a change of state of a system may therefore be written as
Q = E + W
Q = [dU + d(KE) + d(PE)] + W
6
In words this equation states that as a system undergoes a change of state, energy may cross the
boundary as either heat or work, and each may be positive or negative. The net change in the energy of
the system will be exactly equal to the net energy that crosses the boundary of the system. The energy of
the system may change in any of three ways, namely, by a change in IE, KE or P.E
Substituting for KE and PE in the above equation
Q = dU +
2
) d(mV
2
+ d (mgz) + W
In the integral form this equation is, assuming g is a constant
Q
1-2
= U
2
U
1
+
( )
2
V V m
2
1
2
2

+ mg (z
2
z
1
) + W
1-2
In most of the situations the changes in KE and PE are very small, when compared with the changes in
internal energies. Thus KE and PE changes can be neglected.
Q = dU + W
or Q
1-2
= U
2
U
1
+ W
1-2

Corollaries of First Law
Corollary 1: System Executing a Process
For a system executing a process, change in stored energy of the system is given as
E = Q W
Where E = energy stored in the system
Corollary 2: Isolated system
For an isolated system,
Q = 0 and W = 0
Hence E = 0 or E = constant
Thus, the energy of an isolated system remains unchanged.
Therefore, the first law of thermodynamics may also be stated as follows, Heat and work are mutually
convertible but since energy can neither be created nor destroyed, the total energy associated with an
energy conversion remains constant.
Corollary 3: Perpetual Motion Machine of First Kind (PMM-1)
Definition: - It is an imaginary device which produces a continuous supply of work without absorbing
any energy from the surrounding or from the system. Such a machine in effect creates energy from
nothing and violates the first law of thermodynamics.
It is impossible to construct a perpetual motion machine of first kind. The PMM-1 violates the first law.
As per the law of conservation of energy, no engine can produce mechanical work continuously without
some other form of energy disappearing simultaneously.
7
The Pure Substance
The system encountered in thermodynamics is often quite less complex and consists of fluids that don
not change chemically, or exhibit significant electrical, magnetic or capillary effects. These relatively
simple systems are given the generic name the Pure Substance.
Definition
A system is set to be a pure substance if it is (i) homogeneous in chemical composition, (ii)
homogeneous in chemical aggregation and (iii) invariable in chemical aggregation.
Homogeneous in chemical composition means that the composition of each part of the system is same as
the composition of any other part. Homogeneous in chemical aggregation implies that the chemical
elements must be chemically combined in the same way in all parts of the system. Invariable in chemical
aggregation means that the chemical aggregation should not vary with respect to time.
Satisfies condition (i) Satisfies condition (i) Does not satisfies condition (i)
Satisfies condition (ii) Does not satisfies condition (ii)
Satisfies condition (iii)
Fig-5: Illustration of the definition of pure substance
In fig-5 three systems are shown. The system (a) shown in the figure is a mixture of steam and water. It
is homogeneous in chemical composition because in every part of the system we have, for every atom of
oxygen we have two atoms of hydrogen, whether the sample is taken from steam or water. The same is
true for system (b) consisting of water and uncombined mixture of hydrogen and oxygen. System (c)
however is not homogeneous in chemical composition because in the upper part of the system hydrogen
and oxygen are present in the ratio 1:1 where as in the bottom portion they are present in the ratio 2:1.
System (a) also satisfies condition (ii), because both hydrogen and oxygen have combined chemically in
every part of the system. System (b) on the other hand does not satisfies condition (ii) because the
bottom part of the system has two elements namely hydrogen and oxygen have chemically combined
where as in the upper part of the system the two elements appear as a mixture of two individual gases.
Invariable in chemical aggregation means that the state of chemical combination of the system should
not change with time. Thus the mixture of hydrogen and oxygen, if it is changing into steam during the
time the system was under consideration, then the systems chemical aggregation is varying with time
and hence this system is not a pure substance. Thus the system (a) is a pure substance whereas the
systems (b) and (c) are not pure substances.
8
The Two Property Rule for a Pure Substance
The two property rule states that,
The thermodynamics state of a pure substance of a given mass can be fixed by specifying two
independent properties provided (i) the substance is in equilibrium and (ii) the effects of gravity, motion,
capillarity, electricity and magnetism are negligible.
The above rule indicates that if the values of two properties of a pure substance are fixed then the values
for all other properties are fixed. This means that there is a definite relation between the two independent
properties and each of the other properties. Each of these relations is called Equation of state for a pure
substance. The equation of state for a pure substance can be in any one of the following forms:
(i) Algebraic equation (example: perfect gas equation),
(ii) Tables (example: steam tables) and
(iii) Charts (example: Mollier chart for steam).
Specific Heat (c)
Specific heat of a substance may be defined as the amount of heat required to raise the temperature of a
unit mass of the substance through one degree.
The SI unit of specific heat is
kg.K
J
The solids and liquids have only one specific heat whereas gases have two specific heats, which are
based on the type of the heating process. i.e., specific heat at constant volume (c
v
) and specific heat at
constant pressure (c
p
)
If Q is the amount of heat transferred to raise the temperature of 1 kg of substance by dT, then, specific
heat c = Q/dT
or, Q = c dT
the amount of treansferred to raise temperature of mass m of a substance by dT, is given as,
Q = m c dT
As we know, the specific heat of gas depends not only on the temperature but also upon the type of the
heating process. i.e., specific heat of a gas depends on whether the gas is heated under constant volume
or under constant pressure process.
We have Q = m c
v
dT for a rev. non-flow process at constant volume
and Q = m c
p
dT for a rev. non-flow process at constant pressure
For a perfect gas, c
p
& c
v
are constant for any one gas at all pressure and temperatures. Hence,
integrating above equations.
Flow of heat in a reversible constant pressure process Q
1-2
= m c
p
(T
2
T
1
)
Flow of heat in a reversible constant volume process Q
1-2
= m c
v
(T
2
T
1
)

9
Joules Law
Joules law states as follows:
The internal energy of a perfect gas is a function of the absolute temperature only.
i.e., u = f (T)
To evaluate this function let 1kg of a perfect gas be heated at constant volume.
According to non flow energy equation,
Q = du + W
W = 0, since the volume remains constant
Q = du
At constant volume the heat transferred for a perfect gas of 1 kg is given as,
Q = c
v
dT
Q = du = c
v
dT
and integrating
u = c
v
T + K (K = constant)
i.e., internal energy, u = c
v
dT for a perfect gas
or For mass m, of a perfect gas Internal energy, U = m c
v
T
For a perfect gas, in any process between state-1 and state-2, change in internal energy is given as
(U
2
U
1
) = m c
v
(T
2
T
1
)
Relation between Specific heats c
p
& c
v
:
Consider a perfect gas being heated at constant pressure from T
1
to T
2
.
According to non flow equation
Q
1-2
= (U
2
U
1
) + W
1-2
------ (1)
Also for perfect gas,
U
2
U
1
= m c
v
(T
2
T
1
)
In constant pressure process, the work done by the fluid,
W
1-2
= p (V
2
V
1
)
= m R (T
2
T
1
) [ pV = mRT, and p
1
= p
2
= p in this case]

Heat transferred in the constant pressure process is given as
Q
1-2
= m c
p
(T
2
T
1
)
By equating the three expressions in (1)
m c
p
(T
2
T
1
) = m c
v
(T
2
T
1
) + m R (T
2
T
1
)
m c
p
(T
2
T
1
) = (T
2
T
1
) (m c
v
+ m R)
m c
p
= m(c
v
+ R)
10
c
p
= c
v
+ R
or c
p
c
v
= R
Dividing both sides by c
v
, we get
v v
p
c
R
1
c
c


1
R
c
v

( where
v
p
c
c

)
Similarly, dividing both sides by c
p
, we get
1
R
c
p

Specific Heat of a Pure Substance

Specific heat at constant volume
Specific heat at constant volume, c
v
of a pure substance is defined as the ratio of change of the specific
internal energy of the substance with temperature, when the specific volume is held constant.
Symbolically it is written as,

v
v
t
u
c

,
_

Specific heat at constant pressure

Specific heat at constant pressure, c
p
of a pure substance is defined as the ratio of change of the specific
enthalpy of the substance with temperature, when the pressure of the substance is held constant.
Symbolically it is written as,

p
p
t
h
c

,
_

Enthalpy
One of the most important fundamental quantities which occur consistently in thermodynamics is the
internal energy (U) and pressure volume product (pV). This sum is called Enthalpy (H).

i.e. Enthalpy, H = U + pV
When the above is divided by the mass m of the system we have
i.e. H/m = h = u + pv
where h = specific enthalpy of the substance, u = specific internal energy and v = specific volume of the
substance.
11
The enthalpy of a fluid is a property of the fluid, since it consists of sum of a property and the product of
the two properties. Since enthalpy is property like internal energy, pressure, specific volume and
temperature, it can be introduced into any problem whether the process is a flow or a non flow process.
For a perfect gas referring the above equation
h = u + pv
h = c
v
T + RT [ from Joules law for a perfect gas inernal energy, u = c
v
T & pv = RT]
h = (c
v
+ R) T
h = c
p
T
and H = mc
p
T
Application of Application of First law of law of Thermodynamics to hermodynamics to Non-flow on-flow processes or or Closed system system
According to first law of thermodynamics, for a closed system, we have
Q
1-2
W
1-2
= (E)
system
Where (E)
system
= U
2
U
1
+
( )
2
V V m
2
1
2
2

+ mg (z
2
z
1
)
E or dE = dU+ d(KE) + d(PE)
If kinetic energy and potential energy are negligible, then
Q
1-2
W
1-2
= U
2
U
1
1. Constant Volume (Isometric or Isochoric Process)
In the Constant volume process the working substances is contained in the rigid vessel as shown in the
fig-6 below, let Q be the amount of heat supplied to the system. This results in increase of pressure and
temperature at constant volume as represented by the process 1-2 on the p-V diagram. Since boundaries
of the system are immovable and no work can done or by the system, it will be assumed that constant
volume implies zero work unless stated otherwise
Fig-6: Constant Volume process

Applying 1
st
law of thermodynamics to the process,
Note: The term pV is sometimes referred to as flow energy or flow work which will be evident when we
discuss first law for an open system,
The term U +pV is also called Total heat content in the system
12
Q
Q
1-2
= U
2
U
1
+ W
1-2
= U
2
U
1
+ 0
i.e., Q
1-2
= c
v
(T
2
T
1
)
For mass m of a substance, Q = mc
v
(T
2
T
1
)
2. Constant Pressure Process (or Isobaric Process)
Consider the cylinder with a piston carrying perfect gas shown in fig-7a. The gas pressure in the cylinder
is maintained constant by adding weight on the piston. When heat is supplied to the system, its
temperature will rise and it will expand forcing the piston to move upward. Thus the displacement work
is done by the system against a constant force. The above process is shown in fig-7b on the pV diagram.
Fig-7: Constant Pressure Process
Work done by the system, W = pdV
or W
1-2
=

2
1
pdV = p(V
2
V
1
)
From the first law of thermodynamics, we have
Q
1-2
= W
1-2
+ U
Q
1-2
= W
1-2
+ (U
2
U
1
)
= p(V
2
V
1
) + (U
2
U
1
)
= (U
2
+ pV
2
) (U
1
+ pV
1
)
Q
1-2
= H
2
H
1
= m c
p
(T
2
T
1
)
3. Constant Temperature Process (Isothermal Process)
A process at a constant temperature is called an isothermal process, or constant temperature process. In
this process the gas or vapour is heated at constant temperature and there shall be no change in internal
energy. The work done will be equal to the amount of heat supplied. For this case since the gas is
assumed an ideal gas and it implies that the gas follows Boyles law i.e. pV = C (T = Constant)
i.e pV = p
1
V
1
= p
2
V
2
= C or p =
V
C
Work done by the system W
1-2
=

2
1
pdV =

2
1
dV
V
C
=

,
_

1
2
1 1
V
V
ln V p
[since pV = C]
13
Q
From the first law of thermodynamics, we have
Q
1-2
= W
1-2
+ U

Q
1-2
= W
1-2
+ (U
2
U
1
)
Q
1-2
= W
1-2
+ m c
v
(T
2
T
1
)
Since T is constant, i.e. T
1
= T
2

Q
1-2
= W
1-2
+ 0
or Q
1-2
= W
1-2
=

,
_

1
2
1 1
V
V
ln V p
Q
1-2
= W
1-2
=

,
_

2
1
1 1
p
p
ln V p

1
]
1

2
1
1
2
p
p
V
V
4. Adiabatic process:
An adiabatic process is the thermodynamic process in which there is no heat interaction during the
process, i.e. during the process, Q = 0. In these processes the work interaction is there at the expense of
internal energy. The adiabatic process follows the law pV

= constant where is called adiabatic index

and is given by the ratio of two specific heats (c
p
/c
v
). Thus, it is obvious that adiabatic expansion shall be
accompanied by the fall in temperature while temperature will rise during adiabatic compression. The
adiabatic expansion process is shown on fig-9 below.
Fig-9: Adiabatic Process
Work done by the system W
1-2
=

2
1
pdV
But,

2 2

1 1

V p V p C pV
i.e

V
C
p

W
1-2
=
( )
( )
2
1
2
1
1

1
V
C
V
dV
C

1
]
1

+
=
( )
2
1
1
1) (
V pV
1
]
1

+
+
=
2
1
1
pV
1
]
1

+
14
Fig-8: Constant Temperature Process
=
1
V p V p
1 1 2 2
+

W
1-2
=
1
V p V p
2 2 1 1

or W
1-2
=
( )
1
T T mR
2 1

(since pV = mRT)
From the first law of thermodynamics, we have
Q
1-2
= W
1-2
+ U
Q
1-2
= W
1-2
+ (U
2
U
1
)
Since there is no heat interaction i.e. Q

= 0

0 = W
1-2
+ (U
2
U
1
)
W
1-2
= (U
1
U
2
)
W
1-2
= m c
v
(T
1
T
2
)
i.e
1
V p V p
2 2 1 1

= m c
v
(T
1
T
2
)
In an adiabatic expansion, the work done W
1-2
by the fluid is at the expense of a reduction in the internal
energy of the fluid. Similarly in an adiabatic composition process, all the work done on the fluid goes to
increase the internal energy of the fluid.
To derive pV

= C: For a reversible adiabatic process

To obtain the law relating p & V for a reversible adiabatic process, let us consider the non flow energy
equation in the differential from.
Q = dU + W
For the reversible process
W = pdV
Q = dU + pdV
For an adiabatic process Q = 0
dU + pdV = 0
Also for a perfect gas
pV = mRT or p =
V
mRT
Also U = m c
v
T (from Jouls law)
dU = m c
v
dT
15
Hence on substituting,
m c
v
dT +
V
dV mRT
= 0
c
v
dT +
V
dV RT
= 0
Dividing both sides by T, we get
c
v
T
dT
+
V
dV R
= 0
Integrating
c
v
log
e
T + R log
e
V = constant
Substituting T =
R
pV
c
v
log
e

R
pV
+ R log
e
V = constant
Dividing throughout both sides by c
v
c
v
log
e

R
pV
+
v
c
R
log
e
V = constant
Again
1
R
c
v

or
1
c
R
v

[from the relation between the two specific heats c
p
& c
v
]
Hence substituting
log
e

R
pV
+ ( 1) loge V = constant
log
e

R
pV
+ loge V
( 1)
= constant
log
e
R
V pV
1

= constant
i.e. log
e
R
pV

= constant
i.e. constant e
R
pV
constant

or pV

= constant
For unit mass, pv

= constant where v = specific volume

Relation between T & V, and T & p :
16
Now

2 2

1 1
V p V p or

2
1
1
2
V
V
p
p

,
_

or

1
2
1
1
2
p
p
V
V

,
_

For a perfect gas

2
2 2
1
1 1
T
V p
T
V p

1
2
1
1
2

2
1
1
2
1
2
1
2
V
V
V
V
.
V
V
V
V
.
p
p
T
T

,
_

,
_

or

1
1
2
1
2
p
p
T
T

,
_

5. Polytropic Process
Polytropic process is the most commonly used process in practice. In this case the
thermodynamic process is said to be governed by the law pV
n
= constant where n is the index which can
vary from to +. Fig 10 shows some typical cases in which the value of n is varied and the type of
process indicated for different values of n. Thus the various thermodynamics processes discussed above
are special cases of polytropic process.
n = 0
n = 1
n = 2
n =
p
V
n = 0, isobaric process
n =1, isothermal process
n =2, polytropic proces
n = , isochoric process
Fig-10: Polytropic process
Work interaction in case of polytropic process can be given as
W
1-2
=

2
1
pdV
But,
n
2 2
n
1 1
n
V p V p C pV
[ where n is called index of compression or expansion ]
i.e
n
V
C
p

W
1-2
=
( )
( )
2
1
2
1
1 n
n
1 n
V
C
V
dV
C

1
]
1

+
=
( )
2
1
1 n n
1) n (
V pV
1
]
1

+
+
=
2
1
1 n
pV
1
]
1

+
=
1 n
V p V p
1 1 2 2
+

17
W
1-2
=
1 n
V p V p
2 2 1 1

or W
1-2
=
( )
1 n
T T mR
2 1

(since pV = mRT)
From the first law of thermodynamics, we have
Q
1-2
= W
1-2
+ U

Q
1-2
= W
1-2
+ (U
2
U
1
)
Q
1-2
=
( )
1 n
T T mR
2 1

+ m c
v
(T
2
T
1
)

=
( )
1 n
T T mR
2 1

m c
v
(T
1
T
2
)
Since
1
R
c
v

[from the relation between the two specific heats c

p
c
v
]
Q
1-2
=
( )
1 n
T T mR
2 1

1
R m

(T
1
T
2
)

= ( )
2 1
T T mR
( ) ( )

,
_

1
1
1 n
1
=
( ) ( )
( ) ( ) 1 n . 1
1 n 1 . T T mR
2 1

+
=
( ) ( )
( ) ( ) 1 n . 1
n . T T mR
2 1


=
( )
( ) 1
n

.
( )
( ) 1 n
T T mR
2 1

Q
1-2
=
( )
( ) 1
n

. W
1-2
18
19

Application of First law of Thermodynamics to Application of First law of Thermodynamics to Open system or system or Flow processes w processes
Flow Process
20
In the case of closed system there is only energy transfer across the system boundary. In most of the
engineering applications, we come across equipment through which there a continuous flow of material
in and out along with energy transfer. Such processes are called flow processes.
For example consider a portion of power plant is in fig-11, high pressure steam enters the turbine at
section-1, expands while doing work on the rotor, and then leaves at low pressure at section-2.
Moving System
Steam
Supply
Pipe
Turbine
Control
Surface
Exhaust Pipe
Q
W
Control
Volume
Fig-11 Turbine Plant: A Flow Process
The flow process are generally analyzed by the concept of control volume and a control surface, in this
approach, we focus attention upon the fixed region in space through which fluid flow takes place. This
fixed region is called the control volume and its surface is called the control surface. (Shown in fig-11)
The method of analysis is to select a control volume and then account for all quantities of energy
entering and leaving this volume. Note that in addition to flow of matter across the control surface, heat
and work transfer also take place.
Like a closed system the control volume is also defined by a boundary ( the control surface ). There is
however differences are
The closed system boundary may change shape, position and orientation, the control volume
boundary usually does not.
The matter flows across the control volume boundary but not across the closed system boundary.
The control volume is also called an open system.
The advantage and simplification resulting from the control volume concept can be understood by the
turbine plant shown above (in fig-10). The average change of state of steam from entrance to exit can be
related to the shaft work delivered by the turbine and heat transfer from the turbine across the control
volume boundary. Thus we need not to bother about the numerous changes of state and heat & work
interactions experienced by the steam during its passage through different parts of the turbine.
Flow Work or Flow Energy
21
Unlike closed systems, control volumes involve mass flow across their boundaries, and some work
is required to push the mass into or out of the control volume. This work is known as the flow
work, or flow energy, and is necessary for maintaining a continuous flow through a control volume.
V
p
m
Control Volume
(CV)
F
L
imaginary
piston
A
Fluid Element
Fig-12: Flow Work
To obtain a relation for flue work, consider a fluid element of volume V, as shown in fig-12. The
fluid immediately upstream will force this fluid element to enter the control plume; thus, it can be
regarded as an imaginary piston. The fluid element can be chosen to be sufficiently small so that it
has uniform properties throughout.
If the fluid pressure is p and the cross-sectional area of the fluid element is A, the force applied on
the fluid element by the imaginary
F = p .A
To push the entire fluid element into the control volume, this force must act through a distance L.
Thus, the work done in pushing the fluid element across the boundary (i.e., the flow work) is
W
flow
= F.L = p. A. L = p. V (kJ)
The total work per unit mass is obtained by dividing both sides of the above equation by the mass of
the fluid element:
w
flow
= p.v (kJ/kg) (where v = specific volume)
The flow work relation is same whether the fluid is pushed into or out of control volume.
(The source of this flow energy is a pump located somewhere in the surroundings.)
Energy accompanying mass in a flow process
22
In a flow process the energy contained within the control volume is influenced by the following energy
transfers across the control surface:
a) Heat transfer
b) Work transfer
c) Energy flow accompanying mass flow at entrance and exit of the control volume
It is, therefore, necessary to determine the energy flow per unit mass flowing at various positions
coordinates of the control volume. The energy accompanying unit mass consists of the following parts:
1) Internal energy: Each kg of matter has the internal energy u and as the matter crosses the
system boundary the energy of the system changes by u for every kg mass of the matter
that crosses the system boundary.
2) Kinetic energy: Since the matter that crosses the system boundary will have some velocity
say C each kg of matter carries a K.E. 2 /
2
C thus causing the energy of the system to
change by this amount for every kg of matter entering the system boundary.
3) Potential energy: P.E. is measured with reference to some base. Thus z is the elevation of
the matter that is crossing the system boundary, then each kg of matter will possess a P.E.
of gz.
4) Flow energy or Flow work: It is defined as the work required either to push a certain
quantity of fluid into or out of the system. The flow work per unit mass of a fluid is given
by the product of pressure and specific volume (i.e. p.v); Thus external to the system there
must be some force which forces the matter across the system boundary and the energy
associated with this is called flow energy.
Thus energy accompanying a unit mass flow is given by
e
flow
= u +
2
C
2
+ gz + pv [ where e
flow
is energy accompanying a unit mass flow ]
= ( u + pv ) +
2
C
2
+ gz
= h +
2
C
2
+ gz

The total energy accompanying the mass flow is
E
flow
= m

,
_

gz +
2
C
+ h
2
where m is the mass flow rate in the system ( kg/sec)
Steady Flow Process
23
The processes occurring in an open system which permits the transfer of mass as well as energy across
its boundaries are known as flow processes. A process is said to be steady flow process if the conditions
in the control volume remain unchanged with time, i.e. which the mass flow rate into the system is equal
to mass flow rate out of the system. The common examples of steady flow processes are: nozzles, open
system turbines, compressors, pumps
The following conditions exist in a steady flow process: (assumptions)
The mass flow rate remains constant within the system.
The fluid is uniform in composition.
The only interaction between the system and the surrounding are work and heat.
The state of the fluid at any point remains constant with the time.
In the analysis only potential, kinetic and flow energies are considered.
Consider a control volume of a thermodynamic open system as shown in a fig-13, through which a
working fluid is passing at a steady rate.
p
1
, v
1
, T
1
u
1
, C
1
p
2
, v
2
, T
2
u
2
, C
2
z
1
z
2
Datum
Control
Volume
Control
Surface
Q
W
Fig-13: Steady flow open system
Let
m = mass flow rate, kg/s
p = pressure, Pa
v = specific volume, m
3
/kg
C = velocity of fluid, m/s
u = specific internal energy, J/kg
z = height from datum, m
h = specific enthalpy of fluid, J/kg
Q = heat supplied, J
q = heat supplied per unit mass, J/kg
W = work transferred, J
w = work transferred per unit mass, J/kg
A = area of flow, m
2
1, 2 = subscripts for inlet and outlet respectively.
a. Steady flow Mass Balance
24
For the conservation of mass, if there is no accumulation of mass within the control volume, the mass
flow rate for a single stream entering must equal the mass flow rate leaving or
2 1
m m or
2
2 2
1
1 1
v
C A
v
C A

This equation is called as the equation of continuity.

When more than one stream of fluid enters the control volume, then
4 3 2 1
m m m m + +
4
4 4
3
3 3
2
2 2
1
1 1
v
C A
v
C A
v
C A
v
C A
+ +
b. Steady Flow Energy Equation
The total energy entering the system,
m E
1

2 1 1
2
1 1 1 1
Q gz C
2
1
v p u

+

,
_

+ + +

The total energy leaving the system,
m E
2

2 1 2
2
2 2 2 2
W gz C
2
1
v p u

+

,
_

+ + +

According to the first law of thermodynamics,
E
1
= E
2
m
2 1 1
2
1 1 1 1
Q gz C
2
1
v p u

+

,
_

+ + +

= m
2 1 2
2
2 2 2 2
W gz C
2
1
v p u

+

,
_

+ + +

If we consider the flow of a fluid through a pipe of cross-sectional area A, having specific volume, v
and the fluid velocity C then mass flow rate m is given as follows,
mass flow rate, m = Volume flow rate density
= (Area velocity) density
= A C
or, m = AC =
v
AC
(kg/sec)
25
Now h = u + pv

m
2 1 1
2
1 1
Q gz C
2
1
h

+

,
_

+ +

= m
2 1 2
2
2 2
W gz C
2
1
h

+

,
_

+ +

2 1
Q

2 1
W

= m
1
]
1

,
_

+ +

,
_

+ +
1
2
1 1 2
2
2 2
gz C
2
1
h gz C
2
1
h
The above equation is called the Steady Flow Energy Equation (SFEE),
For a unit mass, we have
( ) ( ) ( )
1 2
2
1
2
2 1 2 2 1 2 1
z z g C C
2
1
h h w q + +

In differential form, SFEE can be written as:
g.dz C.dC dh w q
2 1 2 1
+ +

When more than one stream of fluid enters the control volume, then
W gz .C
2
1
h m gz .C
2
1
h m Q gz .C
2
1
h m gz .C
2
1
h m
4
2
4 4 4 3
2
3 3 3 2
2
2 2 2 1
2
1 1 1

,
_

+ + +

,
_

+ + +

,
_

+ + +

,
_

+ +
Mechanical work in a Steady flow process
The steady flow process energy equation per unit mass is:
w gz C
2
1
h q gz C
2
1
h
2
2
2 2 1
2
1 1
+ + + + + +
In differential form, it can be written as:
( ) gz d C
2
1
d dh w q
2
+

,
_

+
=
( ) ( ) gz d C
2
1
d pv u d
2
+

,
_

+ +

w q

( ) gz d C
2
1
d v.dp p.dv du
2
+

,
_

+ + +
For a closed system, according to first law of thermodynamics, we have
p.dv du q +
Hence the substituting the above equation in the differential form of SFEE
( ) gz d C
2
1
d v.dp w
2
+

,
_

+
If kinetic and potential energies are neglected, then
v.dp w
26
p
1
p
2
1
2

2
1
v.dp W
p
v
Fig-14: Work done in a steady flow process
Or
v.dp w
Integrating, we get


2
1
2
1
v.dp w
The work done in a steady flow process is shown in fig-14, where the area under the curve (1-2) on the
ordinate represent the work

2
1
v.dp
Applications of Steady Flow Energy Equation
1. Nozzle & Diffuser
Fig-15
A nozzle (fig-15) is a passage of varying cross-section by means of which the pressure energy of the
flowing fluid is converted into kinetic energy. The main use of the nozzle is to produce a jet of high
velocity to derive turbine and to produce thrust. From the SFEE per unit mass, we have
w gz C
2
1
h q gz C
2
1
h
2
2
2 2 1
2
1 1
+ + + + + +
Here w = 0 and q = 0. Also z
1
= z
2
. Hence
2
2 2
2
1 1
C
2
1
h C
2
1
h + +

( )
2
1
2
2 2 1
C C
2
1
h h
i.e., the gain in KE during the process is equal to the decrease in enthalpy of the fluid
Diffuser: A diffuser is a passage of varying cross section by means of which the kinetic energy of the
flowing fluid is changed into pressure energy. The energy equation for a steady flow can be applied and
similar results as for the nozzle may be obtained.
2. Boiler
27
Control volume
Control surface
Fig-16: Boiler
A boiler is a device to generate steam from feed water by heating due to burning of fuel. The steam can
be used to derive steam engine or a stem turbine. For the boiler shown in the fig-16, applying SFEE per
unit mass, we have
w gz C
2
1
h q gz C
2
1
h
2
2
2 2 1
2
1 1
+ + + + + +
Since no work is done in a boiler, therefore, w = 0. also changes in potential and kinetic energies are
zero. Thus

1 2
h h q kJ/kg
or,
( )
1 2 s
h h m Q
kJ/s or kW
where
s
m
= mass flow rate of steam, kg/s
3. Turbine and Compressors
Turbine:
A turbine converts the heat energy of steam or gas into useful work. In this a steam or gas is passed
through the turbine and part of its energy is converted into work in the turbine. This output of the turbine
runs a generator to produce electricity as shown in fig-17. The steam or gas leaves the turbine at low
pressure and temperature and the changes in potential energy, kinetic energy & heat transfer are
negligible. Applying SFEE per unit mass, we have
Generator
Turbine
Control volume
Gas or Steam in
Gas or Steam out
Control surface
W
Q = 0
Fig-17: Steam or Gas Turbine
28
w gz C
2
1
h q gz C
2
1
h
2
2
2 2 1
2
1 1
+ + + + + +
Since z
1
= z
2
and q = 0
w C
2
1
h C
2
1
h
2
2 2
2
1 1
+ + +
( ) ( )
2
1
2
2 2 1
C C
2
1
h h w kJ/kg
and ( ) ( )
2
1
2
2 s 2 1 s
C C m
2
1
h h m W
kJ/s or kW
where
s
m
= mass flow rate of steam or gas, kg/s
Compressor
The function of the compressor is to compress air or gas from low pressure to high pressure with the
help of work input, which is accompanied by increase in temperature. There are two types of compressor
based on the type of compression
a. Rotary or Centrifugal Compressor
b. Reciprocating Compressor
a. Rotary or Centrifugal compressor
A rotary compressor can be regarded as a reversed turbine (fig-18). The function of rotary compressor is
to compressor is to compress the air or gas with the help of a rotating element called rotor followed by a
stationary element called stator. This increases the energy level of the working fluid.
Electric
Motor
Centrifugal
Compressor
Control volume
Air out
Air in
Control surface
W
Q
Fig-18: Centrifugal compressor
Applying SFEE per unit mass, we have
w gz C
2
1
h q gz C
2
1
h
2
2
2 2 1
2
1 1
+ + + + + +
Since z
1
= z
2
w C
2
1
h q C
2
1
h
2
2 2
2
1 1
+ + + +
The q is taken as negative since heat is lost from the system and w is taken as negative since work is
supplied to the system.
29
w C
2
1
h q C
2
1
h
2
2 2
2
1 1
+ +
or,
,
_

,
_

+
2
2 2
2
1 1
C
2
1
h C
2
1
h w q
kJ/kg
or,
1
]
1

,
_

,
_

+
2
2 2
2
1 1
C
2
1
h C
2
1
h m W Q
kJ/s or kW
where
a
m
= mass flow rate of air, kg/s
b. Reciprocating Compressor
The reciprocating compressor (fig-19) draws in air from atmosphere and supplies at considerable higher
pressure in small quantities (compared with centrifugal compressor). The reciprocating compressor can
be considered as steady flow system provided the control volume includes the receiver which reduces
the fluctuations of the flow considerably.
Compressor
Fig-19: Reciprocating Compressor
Applying SFEE per unit mass, we have
w gz C
2
1
h q gz C
2
1
h
2
2
2 2 1
2
1 1
+ + + + + +
PE = 0 and KE = 0 since these changes are negligible compared with other energies
The q is taken as negative since heat is lost from the system and w is taken as negative since
work is supplied to the system.

w h q h
2 1


2 1
h h w q kJ/kg
or,
( )
2 1 a
h h m W Q
kJ/s or kW
where
a
m
= mass flow rate of air, kg/s
4. Heat Exchanger:
30
A heat exchanger is a device in which heat is transferred from one fluid to another. It is used to add or
reduced heat energy of the fluid flowing through the device. Radiator in an automobile, condenser in a
steam power and refrigeration plants, evaporator in a refrigerator are examples of heat exchangers. There
will be no work interaction during the flow of the fluid through any heat exchanger.
a. Steam Condenser
The condenser is used to condense the steam in case of steam power plant and condense the refrigerant
vapour in the refrigeration system using water or air as cooling medium. In the condenser shown in the
fig-20, there is negligible change in potential and kinetic energies. The q is taken as negative since heat
is lost from the steam (system) and the work done is zero. Therefore, z
1
= z
2,
C
1
= C
2
, and w = 0.
Water in
Water out
Steam in
Condensate out
( )
1 w
T
( )
2 w
T
Fig-20: Condenser
Hence, applying steady flow energy equation we have
2 1
h q h
or,
2 1
h h q kJ/kg
or
( )
2 1 s
h h m Q
kJ/s or kW
where
s
m
= mass flow rate of steam or gas, kg/s
h
1
& h
2
= enthalpy of steam at entry & exit
Assuming there is no other interaction except the heat transfer between steam and water, then

Q = heat gained by water passing through condenser
=
( ) ) T (T c m h h m
1 2
w w w w w1 w2 w

Substituting the value of Q in the above equation, we have

( )
2 1 s
h h m
=
) T (T c m
1 2
w w w w

Where
w
m
= mass flow rate of the cooling water
c
w
= specific heat of water
h
w1
& h
w2
= enthalpy of water at entry & exit

2 1
w w
T & T
= temperature of the water at entry & exit
b. Evaporator
31
An evaporator is a device used in refrigeration system to take away heat from the refrigerator to maintain
low temperature. In the evaporator shown in fig-21, there is no change in potential and kinetic energies.
The work done is also zero. Therefore, z
1
= z
2,
C
1
= C
2
, and w = 0.
Fig-20: Evaporator
Hence, applying steady flow energy equation we have
2 1
h q h +
or,
1 2
h h q kJ/kg
or, ( )
1 2 r
h h m Q
kJ/s or kW
where
r
m
= mass flow rate of refrigerant, kg/s
h
1
& h
2
= enthalpy of refrigerant at entry & exit
5. Throttling Process
Throttling process is an irreversible process in which a fluid flows across a restriction in such a manner
that there is drop of pressure without any change in enthalpy of the fluid, kinetic energy, potential
energy, and there is no work or heat transfer. Such a process occurs in flow through porous plug, a
partially closed valve or a small orifice. (Fig-21).
Restriction
F-g-21: Throttling Process
Applying SFEE per unit mass, we have
w gz C
2
1
h q gz C
2
1
h
2
2
2 2 1
2
1 1
+ + + + + +
Since, q = 0; w = 0; z
1
= z
2
, & C
1
C
2
0 0 = h
2
h
1
+ 0 + 0
i.e., h
1
= h
2
In a throttling process, the enthalpy remains constant.
32
This process has wide application in engineering practice, on typical application of the throttling process
is when fluid pass in a pipe line through a partially opened valve.
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