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The zeroth law and third law of thermodynamics are more definitional in nature. First
and second laws are more pragmatic and consequently most important to engineers.
Simple and most direct statement of the first law of thermodynamics is that energy is
conserved. Energy can neither be created nor destroyed.
From the definition of first law, it is obvious that energy is always conserved. First law
efficiency indicates conversion of energy in a cycle as given by Eq. (1.1)
Output 1.1
=
Input
The net output can be work or heat depending upon the application. In case of a heat
engine, the net output is in the form of work whereas in case of a solar water heating
system it can be the useful heat. The difference between the net output and input is
the energy unused. It is always the need from the first law of the thermodynamics to
reduce the energy waste from the system. First law efficiency can be improved to
limited extent with heavy insulation to the system.
1
1.3 ABOUT THE SECOND LAW OF THERMODYNAMICS
where, A = exergy
To improve a system, we always try to improve the second law efficiency. Exergy is a
tool to identify the loss of energy. In complicated systems, exergy loss at different
locations can give an estimation of such losses and measures can be taken up to
reduce the same. Exergy analysis will be discussed in Chapter 3.
Apart from the energy conservation, two important implications of second law of
thermodynamics are:
A spontaneous process occurs only in one direction. Heat always flows from a body
at high temperature to a body at lower temperature, water always flows downhill, time
always flows in forward direction. Reverse of these processes never happen
spontaneously. The spontaneous process is due to a finite driving potential called
FORCE or CAUSE. The outcome or result is called the FLUX, CURRENT or EFFECT.
2
1.3.2 QUALITATIVE MEASUREMENT OF ENERGY
The second law distinguishes energy in two different forms (1) High grade energy
and (2) Low grade energy. High grade energy is an orderly form of energy whereas
low grade energy is in random form. Some high and low grade energy forms are
given in Table 1.3.
T1 T1
Q1 Q1
H .E W net H .E W net
Q2 Q2
T2 To
(a) (b )
Fig. 1.1 A thermodynamic cycle (a) sink at temperature T2 and (b) sink at ambient
condition T0 .
3
For the desired output of W ,
Amin = W 1.3
A = Wmax 1.4
A W 1.6
II = min =
A Wmin
Now,
W W Wmax 1.7
I = = . = II .Carnot
Q1 Wmax Q1
where Carnot is the Carnot efficiency of an engine operating between two fixed
temperatures. Efficiency of any thermodynamic cycle cannot be more than the Carnot
cycle efficiency.
T T W 1.8
Carnot = 1 2
= 1 0
= max
T1 T1 Q1
Hence,
I 1.9
II =
Carnot
1.5 THERMODYNAMICS PROCESSES
Second law of thermodynamics enables us to divide all the processes into two
classes:
1. Reversible or ideal process
2. Irreversible or natural process
A process is reversible if, after the process has been completed, means can be found
to restore the system and its elements of its and the surroundings to their respective
initial states. Some of the reversible processes are:
4
Any process, which is not reversible, is irreversible. All natural (spontaneous)
processes are irreversible. Some of the irreversible processes are:
Various processes can be expressed mathematically. The first as well as the second
law can be combined together to analysis a thermodynamic system/process. Such
mathematical relationships are elaborately discussed in Chapter 2.
Both the first and second law of thermodynamics while applied to processes give rise
to some thermodynamic properties. First law of thermodynamics while applied to a
process for a closed system give rise to a property called internal energy U .
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 (Fig.1.2 (a)), the net energy transfer
( Q W ) will be stored in the system.
Q3 Q2
W
System Q1
System
W1
W4
Q
W2
W3
Surroundings Surroundings
(a) (b)
As both the heat and work are energies in transit, they can not be stored. Hence, the
quantity (Q W ) is not either heat or work, but it is entirely a new form of energy,
known as internal energy or simply the energy of the system.
5
Q - W = E 1.20
or,
Q = W + E 1.21
If there are more such energy transfer quantities involved in the process, as shown in
Fig.1.2(b), the first law gives,
Q2 + Q3 Q1 = E + (W2 + W3 W1 W4 ) 1.22
Consider a system, which changes from its state 1 to state 2 by following the path A ,
and returns from state 2 to state1 by following the path B (Fig.1.3). So the system
undergoes a cycle.
C
P
For path A:
QA = E A + WA 1.23
For path B:
QB = EB + WB 1.24
or,
WA + WB = QA + QB 1.26
6
or,
QA WA = (QB WB ) 1.27
Thus, it is seen that the change in energy between two states of a system is the same,
whatever path the system follow in undergoing the change of state. Therefore, energy
has a definite value for energy state of the system. Hence it is a point function and is a
property of the system. The energy is an extensive property. The specific energy
E
e= (J/kg) is an intensive property. The cyclic integral of any thermodynamic
m
property is zero ( v dE = 0 ) .
1.6.1 DIFFERENT FORMS OF STORED ENERGY
As discussed in section 1.6, total energy stored in a system is represented by E.
Basically there are two modes in which energy may be stored in a system.
mass velocity V (Fig.1.4). The macroscopic kinetic energy EK of the fluid element by
virtue of its motion is given by
_ 1.31
mV 2
EK =
2
7
Random Thermal
Motion of V
Molecules
Fluid
Mass
m z
motion with an average velocity v , constantly colliding with one another and with the
walls. Due to a collision, the molecules may be subjected to rotation as well as
vibration. They can have translational kinetic energy, rotational kinetic energy,
vibrational energy, electronic energy, chemical energy and nuclear energy (Fig.1.5).
8
V Erot = 1
/W
2
2
2
Etan= 12 mV
(b)
(a)
2
E vib = 12 kx
n n
Vibrational Energy
p
(d)
(c )
(e)
Fig. 1.5 Various components of internal energy stored in a molecule (a) translational
kinetic energy, (b) rotational kinetic energy, (c) nuclear energy, (d) vibrational energy
and (e) electron spin
If N is the number of molecules in the system, then the total internal energy is
U = N 1.34
For an ideal gas there are no intermolecular forces of attraction and repulsion, and the
internal energy depends only on temperature. Thus, for an ideal gas
U= f T ( ) 1.35
9
Other forms of energy which can also be possessed by a system are magnetic
energy, electrical energy and surface tension energy. In absence of these forms, the
total energy E of a system is given by
E = ( EK + E p ) + U 1.36
For open system, the enthalpy H = U + pdV is a property. The specific enthalpy
h = u + pdv is an intensive property.
1.7 ENTROPY
Second law of thermodynamics while applied to a process give rise to a property,
called entropy. Absolute entropy ( S ) or entropy is a measure of molecular disorder in
a system. Following are basic features of entropy:
Entropy transfer is associated with heat transfer (direction of flow of entropy is
same as that of heat flow)
Entropy is proportional to mass flow in an open system
Entropy does not transfer with work
Besides flow, entropy may be generated in a system (Table1.4)
When work is dissipated, molecular disorder will increase. As a result entropy increases.
Consideration of entropy affords a more convenient and straightforward means of establishing
the reversibility and irreversibility of processes.
10
1.7.1 ENTROPY IN AN ISOLATED SYSTEM
No interaction of the system with surrounding.
No transfer of mass
and energy
System
Surroundings
dE = 0 1.42
Again,
T dS = dQ = 0 1.43
dS 0 1.44
Isolated system does not undergo any energy interaction with the surroundings
( dQ = 0 ) .
dSiso 0 1.45
or,
S=Constant 1.47
Hence, entropy of an isolated system can never decrease. It always increases and
remains constant only when the process is reversible. This is known as principle of
entropy increase or simply entropy principle.
11
For isolated system,
dSuniv 0 1.49
or,
dS sys + dS sur 0 1.50
S
max
Siso
Impossible
Xe
X
where,
12
Boundary
Surroundings
System
1---->2
dW
(Work Transfer)
dQ (Heat Transfer)
dQ/T (Entropy
Transfer)
dQ 1.52
= di S
T
dQ 1.53
dS
T
or,
dS di S 0 1.54
or,
de S 0 1.55
For any process executed by a system, energy is always conserved, but entropy is
produced internally. For any process between equilibrium states 1 and 2, the first law
can be written as,
2 2 1.57
dQ dW = E2 E1
1 1
or,
Q12 = E2 E1 + W12 1.58
2
dQ 1.59
S 2 S1
1 T
13
Now,
dQ2 1.60
( S2 S1 ) = S gen
1 T
where, (S 2
S1 ) = entropy change between two equilibrium states
2
dQ
1 = entropy transfer
T
S gen = entropy production between the two equilibrium states
S gen 0 1.61
me
Surroundings
Control Volume
mv
M
E
S
Surface Temperature
,T C.S.
Shaft work
Q
(Heat transfer rate)
Q/T (Entropy transfer rate)
1. Mass of fluid
2. Energy (heat and wok)
3. Entropy
For mass flow, continuity equation is
. .
M 1.62
mi me =
i e
14
M
where = rate of mass accumulation in the system
The energy equation gives
1.63
.
V2 .
V2 . .
E
i i
m h + + gz e e
m h + + gz + Q W =
i e
sh
2 2
E
where, = rate of energy accumulation in the system
Now, entropy principle gives
. 1.64
. .
Q s
i msi -e mse +
T
where
. .
msi =
i
rate of entropy transfer into the system (control volume) due to mass mi
. .
mse =
e
rate of entropy transfer out of the system (control volume) due to mass me
.
.
Q
.
Difference of entropy change of control volume and net rate of entropy transfer is the
entropy generated within the control volume due to irreversibility.
1.65
.
.
S Q
.
.
Sgen = mi si me se +
i e T
By second law of thermodynamics
. 1.66
S gen 0
15
From Eq. (1.64),
. 1.67
Q . .
S
- m i si + m e se +
T i e
From Eq. (1.63),
.
V2 .
.
V2 . E 1.68
Wsh = mi h + + gz me h + + gz + Q
i
2 e
2
1.69
.
.
.
.
V
2
V .
S E
2
Wsh mi h + + gz me h + + gz + T mi s + me s +
i
2 e 2 i e
1.70
.
.
+ gz + T0 mi s + me s +
2 2
. .
V .
V S
Wsh mi h + + gz me h +
i
2 e 2 i e
or,
V2 V2 1.71
+ gz ( E T0 s
. . .
Wsh max mi h T0 s + + gz me h T0 s +
i
2 e 2
Eq. (1.71) is the expression for the rate of shaft work in the system.
At steady state,
. . . 1.72
mi = me = m j
i e j
16
1.7.4 GOUY-STODOLA THEOREM
Expression for the lost work can be obtained from the Gouy-Stodola theorem.
According to this theorem rate of irreversibility or energy degradation is
. . 1.75
Wlost = I
( ) 1.76
. .
= Wsh Wsh
max
V2 V2 1.77
+ gz ( E T0 s )
. .
= mi h T0 s + + gz me h T0 s +
i
2 e 2
. V2 .
V2 . E
mi h + + gz me h + + gz + Q
i 2 e 2
V2 V2 1.78
+ gz ( E T0 s )
. .
= mi h T0 s + + gz me h T0 s +
i
2 e 2
. V2 .
V2 . E
mi h + + gz me h + + gz + Q
i 2 e 2
On simplification,
.
1.79
.
. .
.
s Q .
Wlost = I = T0 mi s + me s + = T0 S gen
i e T0
17
18