Derivation of Entropy from Second Law

Consider the following combined system consisting of a

Carnot heat engine and a piston cylinder system
ΤR
δQrev δQrev

E δWrev
δWC =δWsys +δWrev
δQ
Τ
Combined
system System δWsys

First Law applied to the combined system

dEC = δQrev − δWC

δWC = δQrev − dEC

For a Carnot Engine (reversible cycle)

δQrev TR TR
= → δQrev = δQ ⋅
δQ T T

δQ
substituting δWC = ⋅ TR − dEC
T

130
Let the system undergo a cycle while the Carnot cycle
undergoes one or more cycles. Integrate over entire cycle
(recall system energy is a state property)

δQ
∫ δWC = ∫ ⋅ TR − ∫ dEC
T

The net work for one cycle is

 δQ 
=
WC TR ∫  
 T  boundary

The integral must be evaluated at the system boundary

The combined system (cycle) draws heat from a single

reservoir while involving work WC

Based on K-P statement the combined system cannot

produce net work output Æ WC ≤ 0

 δQ 
∫  ≤0
 T  boundary

This is the Clausius Inequality which is valid for all

thermodynamic cycles, reversible or irreversible.

131
For a reversible cycle (no irreversibilities in the system)

 δQ 
∫  Int = 0
 T  rev

Since the cycle integral of (δQ/T) is 0, the quantity δQ/T

is a state property, it does not depend on the path (similar
∫ dE = 0 ).

We call this new property entropy, S,

 δQ 
dS =   units : kJ/K
 T  int
rev

For a process where the system goes from state 1 to 2

2  δQ 
S 2 − S1 = ∫1  
 T  int
rev

Specific entropy s= S/M

2  δQ / M  2  δq 
s 2 − s1 = ∫1  =
 int ∫1   int
 T  rev  T  rev

132
The entropy change between two specified states is the
same whether the process is reversible or irreversible

Irreversible 2
T process

Internally
reversible process
1

To calculate S2-S1 evaluate ∫ δQ / T for the reversible path

Consider a cycle made up of an irreversible process

followed by a reversible process
Irreversible 2
T process

Internally
1 Reversible process

Applying Clausius Inequality to the cycle

δQ 2  δQ  1  δQ 
∫ = ∫1   ∫2   int ≤ 0
+
T  T b  T  rev

133
  δQ 
∫   +(S1 − S 2 ) ≤ 0
2
1
 T b
2  δQ 
S 2 − S1 ≥ ∫1  
 T b

Remove inequality sign to get the entropy balance

equation for a closed system

2  δQ 
S 2 − S1 = ∫1   + S gen
 T b

Change in entropy Entropy transfer Entropy generated in

of the system to the system by the system due to
heat transfer irreversibilities

> 0 irreversible process


S gen = 0 reversible process
< 0 impossible process


Note: Moran and Shapiro uses symbol σ instead of Sgen

134
For an isolated system (adiabatic closed system)

δQ
∆Sisol = ∫1
2
+ S gen
T

Since Sgen ≥ 0 Æ ∆Sisol ≥ 0

This is the Increase in Entropy Principle which simply

stated says that for an isolated system the entropy always
increases or remains the same

surroundings
Isolated
system
W,Q

system W,Q

∆S total = ∆Ssystem + ∆Ssurr ≥ 0

135
The increase of entropy principle does not say that the
entropy of a system cannot decrease

Isolated ∆Ssurr= +3 kJ/kg

system

∆Ssys=
-2 kJ/kg

A process that is both adiabatic and reversible is referred

to as isentropic, and for a closed system

2 δQ
∆S isentropic = ∫1 + S gen = 0
T

entropy is constant, S1=S2.

Microscopic Point of View:

Entropy is the measure of molecular disorder or
randomness. As a system becomes more disordered, the
position of the molecules becomes less predictable and
the entropy increases. Entropy is the lowest in a solid
because molecules are held in place and simply vibrate
and highest in a gas where the molecules are free to move
136
in any direction. Entropy of a pure crystalline substance
at absolute zero temperature is zero since the state of each
molecule is known Æ Third Law of Thermodynamics

Disorganized energy does not have potential to do useful

work,

M
M

Organize the KE of the molecules (on average moving in

one direction) by expanding through a nozzle increases
the ability to do useful work. Some of the IE of the
molecules is converted in to KE resulting in a temperature
drop and corresponding drop in entropy.

The paddle-wheel work done on a

gas increases the level of disorder
(entropy) of the gas and thus the
energy is degraded during this process M T increases

Heat is a form of “disorganized energy”

Q
and some entropy will flow with it

137
Evaluation of Entropy Change in a Closed System

System
Q W

Apply First Law neglecting KE and PE effects, no shaft

work

In differential form du = δq − δw = δq − Pdv

δq = du + Pdv
δq
For an internally reversible process ds = so
T

Tds = du + Pdv

recall h = u + Pv → du = d (h − Pv) = dh − Pdv − vdP

substitute du into the above equation

Tds = ( dh − Pdv − vdP) + Pdv

Tds = dh − vdP

These are the Gibb’s equations (or simply Tds equations)

138
For a system undergoing a process from state 1 to state 2

du 2 P
s 2 − s1 = ∫12 ds = ∫12 + ∫1 dv
T T
dh v
s 2 − s1 = ∫12 ds = ∫12 − ∫12 dP
T T

Note the terms on the RHS are state properties, so the

terms on the LHS, i.e., entropy, must also be a state
property

Although we derived the Tds equations for a reversible

process since entropy is a state property we can integrate
these equations to get the change in entropy between any
two states for any process

c ( P, T ) dT 2 P
s 2 − s1 = ∫1
2 V
+ ∫1 dv
T T
c ( P, T ) dT 2 v
s 2 − s1 = ∫12 P − ∫1 dP
T T

The above integration is not straight forward, so entropy

is tabulated along with u and h in the steam tables and
plotted on T-s and h-s (Mollier) diagrams.

139
Entropy tabulated in steam tables is relative to an
arbitrary reference state

The value of entropy at a given state is determined just

like for the other state properties u and h

Liquid Vapor
P,TÆs P,TÆs

Liqud-vapor
S=(1-x)sf + xsg

s
140
 δQ
Recall for an internally reversible process dS =
T
Therefore, δQint = TdS
rev

Heat added in process from 1Æ2 is Qint = ∫12 TdS

rev

= Area under curve

For an isentropic process S is constant

2
T

No heat transfer Æ area under the curve is zero

141
Entropy Change for an Ideal Gas

For an ideal gas du = cV (T )dT , dh = c P (T )dT , Pv = RT

du 2 P c (T )dT dv
s 2 − s1 = ∫12 + ∫1 dv = ∫12 V + R ∫12
T T T v
c (T ) dT v 
s 2 (T2 , v2 ) − s1 (T1 , v1 ) = ∫12 V + R ln 2 
T  v1 
and
dh 2 v c (T )dT dP
s 2 − s1 = ∫12 − ∫1 dP = ∫12 P − R ∫12
T T T P
c (T ) dT P 
s 2 (T2 , P2 ) − s1 (T1 , P1 ) = ∫12 P − R ln 2 
T  P1 

The value of the specific entropy is set to zero at 0K and 1

atm, e.g., s(0K, 1 atm)= 0

The specific entropy at temperature T and 1 atm is

c P (T )dT  1 atm 
s (T ,1 atm) − s (0K,1 atm) = ∫0T − R ln 
T  1 atm 

dT
s o = s (T ,1atm) = ∫0T c p (T )
T

142
Values of s o are tabulated as a function of T for air in
Table A-22

dT dT 1 dT
so 2
∫1 c p (T ) = ∫02c p (T ) − ∫0 c p (T ) = s 2o − s1o
T T T

 P2 
Therefore, s 2 − s1 = (s − s ) − R ln 
o
2
o
1
 P1 

If the specific heats cP and cV are taken as constant

dT v 
s 2 − s1 = cV ∫12 + R ln 2 
T  v1 
 T2   v2 
s 2 − s1 = cV ln  + R ln 
 T1   v1 

dT P 
s 2 − s1 = c P ∫12 − R ln 2 
T  P1 
 T2   P2 
s 2 − s1 = c P ln  − R ln 
 T1   P1 

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