CHAPTER 1:

REVIEW OF FIRST AND SECOND LAW OF THERMODYNAMICS

1.1 THERMODYNAMICS REVISITED

Thermodynamics itself is a Greek technical term meaning heat (thermo) and

mechanical power (dynam-ics). We can define thermodynamics as the science and
technology that deals with the laws that govern the transformation of energy from one
form to another. There are 5 (five) basic laws governing the energy transformation. All
such laws are phenomenological. We can not prove these laws and at the same time
we can not violet them. These laws are given in Table-1.1.

Thermodynamic Laws Scientists/Researchers year

Zeroth Law Fowler & Guggenheim 1939
First Law Joule, Mayer, Thompson 1845
& Colding
Second Law Carnot 1824
Third Law Nernst 1907
Fourth Law Onnes 1957

Table 1.1: Different thermodynamic laws

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.

1.2 ABOUT THE FIRST LAW OF THERMODYNAMICS

Simple and most direct statement of the first law of thermodynamics is that energy is
conserved. Energy can neither be created nor destroyed.

First Law gives a quantative measure of energy

It can not distinguish the different types of energy
It fails to indicate the direction of flow of energy
It can not indicate whether the process is cyclic or not.
First law applied to a process gives rise to a property (internal energy, U for a
closed system and enthalpy, h for a open system)

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

Second law of thermodynamics provides the criterion as to the probability of various

processes. Sadi Carnot established this law in 1824. But it got importance from last
two decades (1980 onwards) in view of conservation of energy. First law dictates that
energy in a system is always conserved. There is no way to conserve energy by use
of first law of thermodynamics. However, it is the exergy, which is a consequence of
the second law that is never conserved. Unlike energy, exergy always decreases. So
minimization of exergy loss is nothing but the principle of energy conservation. The
net exergy output to the actual exergy input to the system is the second law efficiency.

Minimum exergy intake to perform a given task A 1.2

II = = min

Actual exergy intake to perform the same task A

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:

1.3.1 DIRECTIONAL FLOW OF ENERGY

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.

Table 1.2 Forces and fluxes

Sl No Force (Cause) Conjugate fluxes (Effect)

1 Temperature Gradient Heat Transfer
2 Concentration Gradient Mass Transfer
3 Electric Potential Gradient Flow of Electric Current

TRANSFER PROCESSES CAN NEVER SPONTANEOUSLY OCCUR FROM

A LOWER TO A HIGHER POTENTIAL. SECOND LAW OF
THERMODYNAMICS PUTS LIMITATION ON DIRECTION OF PROCESS
OCCURANCE.

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.

Table1.3 Different form of energy

High Grade Energy Low Grade Energy

Electrical energy Heat or thermal energy
Wind energy Nuclear fission
Hydropower Nuclear fusion
Kinetic energy of a water jet Heat derived from combustion of fossil
fuel
Mechanical work
Tidal power

Quality of energy can be ascertained by applying the second law of thermodynamics

to a process or a system.

1.4 RELATIONSHIP BETWEEN THE FIRST AND SECOND LAW OF

THERMODYNAMICS

Consider a power plant converting a fraction of available energy A or Wmax to useful

work W (Fig. 1.1)

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

I = Irreversibility = Wmax W 1.5

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:

Frictionless motion of solids

Slow frictionless adiabatic expansion/compression of a gas
Slow isothermal compression/expansion of a gas
Electrolysis of water
Flow of electric current through inductors and capacitors

4
Any process, which is not reversible, is irreversible. All natural (spontaneous)
processes are irreversible. Some of the irreversible processes are:

Irreversibility due to finite temperature differences between combustion gas and

working fluids in a boiler
Internal irreversibilities in pipe fittings, bends etc- viscous dissipation
Unrestrained expansion-Joule Thomson effect
Mixing of two different fluid streams
Magnetization of materials exhibiting hysteresis
Joulean heat production due to flow of current through a electric conductor

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.

1.6 THERMODYNAMIC PROPERTIES

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)

Fig. 1.2 (a)-(b) Thermodynamic system and surrounding

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

where, E is the increase in energy of the system.

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

The following explanation can be given to justify internal energy as a thermodynamic

property:

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

Fig. 1.3 Thermodynamic processes

For path A:
QA = E A + WA 1.23

For path B:
QB = EB + WB 1.24

The processes A and B , together constitute a cycle for which

Wcycle = Qcycle 1.25

or,
WA + WB = QA + QB 1.26

6
or,

QA WA = (QB WB ) 1.27

From Eqs. (1.23) and (1.24), it yields

E A = EB 1.28
similarly, had the system returned from state 2 to state 1 by following the path C
instead of path B ,
E A = EC 1.29

From Eqs. (1.28) and (1.29),

EB = EC 1.30

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.

(a) Macroscopic energy mode

(b) Microscopic energy mode
The macroscopic energy mode includes the macroscopic kinetic energy and potential
energy of a system. Let us consider a fluid element of mass m having the centre of
_

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

Fig. 1.4 Macroscopic and microscopic energy

If the elevation of the fluid element from an arbitrary datum is z , then the macroscopic
potential energy E p by virtue of its position is given by
E p = mgz 1.32
The microscopic energy mode refers to the energy stored in the molecular and atomic
structure of the system, which is called the molecular internal energy or simply internal
energy U . Matter is composed of molecules. Molecules are in random thermal
_

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 )

Electron spin and rotation

X

(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 represents the energy of one molecule, then

= trans + rot + vib + chem + electronic + nuclear 1.33

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

where, EK + E p = Macro energy and U = Micro energy.

In absence of motion and gravity,
EK = 0, E p = 0 1.37
Hence,
E =U 1.38

Hence, Eq. (1.21) becomes

Q = U + W 1.39

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)

Table 1.4 Entropy linked with energy

Heat Work Entropy transfers
Work Work No entropy transfer
Work Heat No entropy transfers,
Entropy generates

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

Fig.1.6 An isolated system

For a given system,
Q W = dE 1.40

For isolated system

Q = W = 0 1.41

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

For a reversible process,

dSiso = 0 1.46

or,
S=Constant 1.47

For irreversible or natural process

dSiso > 0 1.48

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

Fig. 1.7 Equilibrium state of an isolated system

1.7.2 CLOSED SYSTEM

Entropy of any closed system can increase in two different ways

1. By heat interaction
2. By internal irreversibility or dissipative effects in which work or kinetic energy is
dissipated into internal energy increase.
If dQ is the infinitesimal amount of heat transferred to the system through its
boundary at temperature T , being same as that of surroundings, the entropy increase
dS of the system can be expressed as,
dS = d S + d Se i
1.51

where,

d e S entropy increase due to external heat interaction

d i S entropy increase due to internal irreversibility ( also called entropy production
or entropy generation, S gen )

Entropy change=entropy transfer+ entropy generation

12
 Boundary

Surroundings

System
1---->2
dW
(Work Transfer)

dQ (Heat Transfer)

dQ/T (Entropy
Transfer)

Fig. 1.8 A closed system

dQ 1.52
= di S
T
dQ 1.53
dS
T
or,
dS di S 0 1.54

or,
de S 0 1.55

S sys = Strans + S gen 1.56

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

By second law of thermodynamics,

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

Second law of thermodynamics states that, in general, any thermodynamic process is

accompanied by entropy generation.

1.7.3 OPEN SYSTEM

me
Surroundings

Control Volume
mv
M
E
S

Surface Temperature
,T C.S.

Shaft work
Q
(Heat transfer rate)
Q/T (Entropy transfer rate)

Fig. 1.9 An open system

In an open system, there are transfer of three quantities:

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
.

i msi -e mse + = net rate of entropy transfer

T
s
= rate of change of entropy of control volume

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

Hence, energy equation becomes

.

.
V2 .
V2 1.73
Wsh = Q + m j h + + gz h + + gz
j
2 i 2 e
Entropy equation is
. 1.74
. .
Q .
S gen = me se mi si
T

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

Hence, lost work is proportional to the entropy generation rate.

17
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