Second Law of Thermodynamics

&
Entropy
Annexure

 A reversible engine operates between temperatures T1 and T (T1 > T). The
energy rejected from this engine is received by a second reversible engine

T1
Q1

at the same temperature T. The second engine rejects energy at

temperature T2 (T2 < T).

W1

Show that:

Q2

(a) Temperature T is the arithmetic mean of temperatures T1 and T2 if the

engines produce the same amount of work output

T
Q2

(b) Temperature T is the geometric mean of temperatures T1 and T2 if

the engines have the same cycle efficiencies

W2
Q3
T2

a.

If he produce the same amount of work

Then, W1 = W2

Or

Q1 = Q2a,
" "

"

(1 - " )( "#) Q2 = (1 - "$) Q2

#

"#
"$
- 1 = 1 - "
"
"#%"$
= 2
"
" % "
T = # $ $

T is geometric mean of T1 and T2

b. If their efficiency is same then

"

1 - " = 1 #

T = 12

"$
"

As T is positive, so negative sign neglected

We know that
Or

+#
"#

+#
"
Q1 = # Q2
"#
"

+$
"

Entropy Generation

Entropy generation Sgen is always a positive quantity or zero (reversible process)

Its value depends on the process, thus it is not a property of a system

The entropy of an isolated system during a process always increases, or in the limiting case of a
reversible process remains constant (it never decreases),this is known as the increase of entropy
principle.

The entropy change of a system or its surroundings can be negative; but entropy generation
cannot

6-9
Approximation of
Heat Absorbed

T2

T1

L
Q

S1

S2

The curve LM is obtained by heating ! Kg of gas from initial state L to final state M
Let the temperature during heating increases from T1 to T2.
Heat absorbed by the gas will be given by the area under curve LM
(T +T )
Heat absorbed = Area under the curve LM = (s1 s2) . 1 $ 2
Heat absorbed approximately equals the product of change in entropy and mean absolute temperature

ENTROPY CHANGES FOR A CLOSED SYSTEM

General Case for Change of Entropy of a Gas
- Let 1 kg of gas at a pressure p1, volume v1, absolute temperature T1 and entropy s1, be heated such that its
final pressure, volume, absolute temperature and entropy are p2, v2, T2 and s2 respectively

 Heating a Gas at Constant Volume

temperature be from s1 to s2 and T1 to T2

6-9absolute
- Let 1 kg of gas be heated at constant volume and let the change in entropy and

S2

T2

T1

S1
Q

S1

S2

Heating a Gas at Constant Pressure

6-9 changes from
- Let 1 kg of gas be heated at constant pressure, so that its absolute temperature

T1 to T2 and entropy s1 to s2

S2

T2

T1

S1
Q

S1

S2

Isothermal Process
- Entropy changes from s1 to s2 when gas absorbs heat during expansion
- The heat taken by the gas is given by the area under the line 1-2 which also represents the work
done during expansion.
- In other words, Q = W

T2

T = Constant

T1

S1

S2

An isothermal expansion at
constant temperature T

Adiabatic Process
- Entropy s1 = s2 when gas absorbs adiabatic process
- There is no change in entropy and hence it is known as isentropic process
- It is a vertical line (1-2) and therefore area under this line is nil ; hence heat supplied or
rejected and entropy change is zero
T

T2

T1

2
S1 = S2
Adiabatic Process

Polytropic Process
6-9

2
Q

S1

S2

Formulae for Change of Entropy for Different Processes for Closed Systems

Entropy Relations to Other Thermodynamic Properties

Consider a closed system undergoing a reversible process during which there are heat and work
interactions. Then applying the first law to the process, considering unit mass of the system, we can
write
dq = dw + du
Substituting dq = T.ds and dw = p.dv

we can write T.ds = p.dv + du

(1)

The enthalpy is given by h = u+pv

The differential enthalpy is dh = du + p.dv + v.dp
p.dv +du = dh v .dp
Substituting this value in equation T.ds = dh v. dp (2)
Equation 1 and 2 are know as fundamental thermodynamic relations combining first law and second
law of thermodynamics into single equation
Derived for a reversible process they are applicable to irreversible processes also, as they
express relation between the properties and therefore are independent of the path followed by
the process

Change of Entropy for an Open System

In an open system, as compared with closed system, there is additional change of entropy due to
the mass crossing the boundaries of the system

The net change of entropy of a system due to mass transport is equal to the difference between
the product of the mass and its specific entropy at the inlet and at the outlet of the system

Therefore, the total change of entropy of the system during a small interval is given by

+ 2 . 2 .

8+

General form " + .

9

To temperature of surroundings
Subscripts i and o refer to inlet and outlet conditions



+ 2 .

+ 2 .

# 8+
0 " 8<
9

8=
+ . 8<

1
+ 2 . 0

2 . 0
2 . = 0