LECTURES IN

THERMODYNAMICS
Claus Borgnakke
CHAPTER 6

For the 8th Edition of:

Fundamentals of Thermodynamics
Claus Borgnakke, Richard Sonntag
John Wiley & Sons, 2013
 Chapter 6

• The Inequality of Clausius

• Entropy
• Gibbs Property Relations
• Entropy Changes for Solids, Liquids and Ideal Gases
• The Polytropic Process in an Ideal Gas
• Entropy Generation and The Entropy Balance Equation
• Entropy Equation Applied to Heat Engines and Heat Pumps
• Entropy and Chaos

2
 The Inequality of Clausius

Previously we used net work and net heat transfer terms like ○ δQ for the cycle.
Consider a modification of this as ○ (1/T) δQ, that is we weigh the incremental heat
transfer with the factor (1/T) instead of factor 1.

Reversible heat engine:

Q Q
○ δQ = Q – Q ≥ 0 but ○ (1/T) δQ = H – L = 0
H L TH TL
Actual heat engine same QH:
Wac < Wrev  QL ac > QL
Q Q
○ δQ = QH – QL ac ≥ 0 but ○ (1/T) δQ = H – L ac < 0
TH TL

Reversible refrigeration cycle:

Q Q
○ δQ = QL – QH ≤ 0 but ○ (1/T) δQ = L – H = 0
TL TH
Actual refrigeration cycle same QL:
Wac > Wrev  QH ac > QH
Q Q
○ δQ = Q – Q ○ (1/T) δQ = L – H ac < 0
L H ac ≤ 0 but
TL TH
3
 The Inequality of Clausius

Conclusion from previous considerations:

All cycles:  δQ
○
T ≤ 0

= reversible processes; < irreversible processes

In the previous we considered Carnot cycles so the integrals could be evaluated, that is
not necessary for the general principle.

Example: Evaluate example 5.4 with the inequality of Clausius

. o . .
Heat engine: QH = 1000 kW in at 550 C, QL = 550 kW out at 300 K, W out is 450 kW

Solution ____________________________________________________
. . .
Q Q
Clausius:  δQ
○
T =
H
–
TH TL
L
=
1000 kW 550 kW
823 K – 300 K
kW kW
= (1.215 – 1.833) K = – 0.62 K Satisfied

4
 The Entropy

Consider a cycle composed of two processes, A + B moving a substance between states 1

and 2. Assume both of these are reversible then

 δQ
○
T
= 0 =

1
2 δQ
 T A + 
  
1 δQ
 
2  T B
Compare this to a reversible cycle with path C + B

 δQ
○
T = 0 = 2 δQ + 1 δQ
  T C   T B
1 2
Since the second integral is common we get by subtraction
2 δQ = 2 δQ = Fct(1,2)
  T A   T C
1 1
Integral is the same for all reversible paths, define a state function:

δQ δq
Entropy S: dS ≡  T rev or ds ≡  T rev [kJ/kg-K]
   

2 δq
s2 – s1 = 
  T rev
1

5
 The Entropy

Entropy of a pure substance.

Entropy for water, T-s diagram
Entropy is tabulated together with other
properties as (T, P, v, u, h, s) in the B section
of appendix. Properties (u or h) and s are
zero at a reference point that depends on
the substance.

In the two-phase region s relates to the

saturated liquid-vapor values as (v, u, h)

s = (1 – x)sf + x sg
= sf + x sfg

6
 The Entropy

T-s diagram from CATT3 for water. Enthalpy-Entropy for water,

Showing P = 1.55 MPa & v = 0.13 m^3/kg h-s diagram, Mollier diagram
curves with the plot option

Aqua, red separated by P = Pcritical

7
 The Entropy

Entropy changes in reversible processes.

In general
δq
ds =  rev and δqrev = T ds
T
Notice:
1. Change ds follows magnitude and sign of δq
2. For a given δq change ds is smaller for high T
3. For a reversible process we find heat transfer
2
δqrev = T ds  1 q2 =
 T ds = area
1
These points are illustrated in the figures.

8
 The Entropy

Entropy changes in reversible processes.

From the definition of the entropy there are two processes

for which we can evaluate the integral without further T-S diagram
developments.

Reversible adiabatic process: δq = 0 so

δq
ds =  rev = 0  s = constant
T
2
1 q2 =
 T ds = area = 0
1
This is called an isentropic process.

Reversible isothermal process: T = constant so The two processes and the

area below the process curve
1 q2 shows the heat transfer.
δq
s2 – s1 = 
2
  T rev = T
1  

2
1 q2 =
 T ds = area = T (s2 – s1)
1 9
 The Carnot Cycle in a T-s diagram

Entropy changes in the Carnot Cycle. Carnot Heat Engine

T-S diagram
The Carnot cycle consists of 2 adiabatic and 2 isothermal
processes so the cycle looks like a rectangle in a T-s
diagram as shown. Notice how the heat transfer is the area
below the process curve as in the heat engine

1 q2 = TH (s2 – s1) = qH
and
3 q4 = TL (s4 – s3) = – qL

The two isentropic processes (rev. and adiabatic) give

s2 = s3 and s4 = s 1
Carnot Heat Pump
so the entropy increase in 1-2 equals the decrease in the
3 – 4 process. The net work equals the net heat transfer so
the cycle efficiency is
wnet qH − qL area 1-2-3-4-1
η= q = q = area 1-2-b-a-1
H H

The reversed cycle is a refrigerator or heat pump and it has

opposite changes in entropy and all heat transfers. 10
 The Entropy Change in Evaporation

Entropy changes in reversible processes.

Consider a constant pressure process of boiling

saturated liquid to saturated vapor from state 1 to state 2
in the diagram. From the energy equation
1 q2 = u2 – u1 + 1w2 = h2 – h1 = hfg
Constant P process
The entropy change is
2 δq 1q2 hfg
s2 – s1 = sfg =   T rev = T = T
1  
relating the entropy of evaporation sfg to the enthalpy of
evaporation hfg. This is a consistency requirement for
the tables of thermodynamic properties.

hfg
sfg =
T

11
 TheCycle
The Carnot Work inTerm
a T-s diagram

Example 6.1
A Carnot heat pump with R-134a as the working fluid absorbs heat at 0oC changing from
a two-phase state to saturated vapor. Heat is rejected from the R-134a at 60oC as it moves
to a saturated liquid. Find the pressure after compression, before the heat rejection and
determine the COP for the cycle.

Solution _______________________________
We can identify the cycle from the end states of the two
heat transfer processes.
State 1 Table B.5.1: s1 = sg @0oC = 1.7262 kJ/kg-K,
State 3 Table B.5.1: s3 = sf @60oC = 1.2857 kJ/kg-K,
State 2: 60oC, s2 = s1 State 4: 0oC, s4 = s3
P after compression, before heat rejection is P2 @(T2, s2)
Interpolate in Table B.5.2 between 1400 kPa and 1600 kPa:
1.7262 − 1.736
P2 = 1400 + (1600 – 1400) = 1487.1 kPa
1.7135 − 1.736
From Carnot cycle COP is:
qH TH 60 + 273.15
βHP = = = = 5.55
win TH − TL 60 − 0 12
 Work and Heat Transfer in an Isothermal Process

Example 6.2
A piston/cylinder contains 1 L of R-410A at 20oC, x = 0. The piston expands reversibly
with T = C to a final pressure of 400 kPa. Find the work and heat transfer for the process.

Solution _____________________________________________________
C.V. R-410A is a control mass, for which we neglect kinetic and potential energies.
Continuity Eq.: m 2 – m1 = 0  m2 = m1 = m
Energy Eq.: m(u2 – u1) = 1Q2 – 1W2
Entropy Eq.: m(s2 – s1) = 
1 δQ/T
2

Process: T=C  
1 δQ/T = 1Q2 /T
2

State 1 (T, P) saturated Table B.4.1:

u1 = 87.94 kJ/kg, s1 = 0.3357 kJ/kg-K
State 2 (T, P) superheated vapor Table B.4.2:
u2 = 276.44 kJ/kg, s2 = 1.2108 kJ/kg-K

13
 Work and Heat Transfer in an Isothermal Process

Example 6.2 continued

From V1 = 1 L = 0.001 m3 and state 1:
m = V/v1 = 0.001 m3 / 0.000923 m3/kg = 1.083 kg
From the entropy and process equations
1Q2 = mT(s2 – s1) = 1.083 kg ×293.15 K × (1.2108 – 0.3357) kJ/kg-K = 277.8 kJ
Work from the energy equation
1W2 = 1Q2 – m(u2 – u1) = 277.8 kJ – 1.083 kg × (276.44 – 87.94) kJ/kg = 73.7 kJ

The work and heat transfers are the area in the P-V and the T-S diagrams respectively. The shape of the T = C
curve in the superheated vapor region makes area determination for work difficult. 14
The Entropy In-text Concept Questions

15
 Gibbs Relations
Gibbs Relations
Consider a mass element with an incremental reversible change of the thermodynamic state
in the absence of kinetic and potential energies.
Energy Eq.: du = δq – δw
Entropy Eq.: ds = δq /T
Simple compressible substance: δw = P dv
Substitute δq and δw into the energy equation
du = T ds – P dv (6.5)
The other relation is obtained when considering the variation in enthalpy
dh = d(u + Pv) = du + P dv + v dP
Solving Eq.6.5 for the entropy term using u or h we can get two expressions as

T ds = du + P dv
Gibbs relations:
T ds = dh – v dP

These expressions show the variation of one property when two other properties are varied.
This is consistent with a state being a function of two properties thus all other properties
must follow. 16
 Entropy Change for a Solid or Liquid

For a solid or liquid we have the behavior for an incompressible substance:

v ≈ constant; v also small; du = C dT
du P du C
ds = + dv ≈ = dT
T T T T
If specific heat is constant we can integrate

 2 C T2
s2 – s1 =  T dT = C ln T
1 1

Since v is constant u and s are functions of temperature only. Thus in an isentropic

process the temperature does not change, like pumping a liquid to higher pressure.

Example 6.3
Liquid water is heated from 20oC to 90oC. Find the change in entropy using constant
specific heat and by using the steam tables.
Solution _____________________________________________________
T2 363.15
Table A.4: s2 – s1 = C ln T = 4.18 kJ/kg-K ln 293.15 = 0.8951 kJ/kg-K
1

Table B.1.1: s2 – s1 = sf 90 – sf 20 = 1.1925 – 0.2966 = 0.8959 kJ/kg-K

17
 Entropy Change for an Ideal Gas
Now use the two Gibbs relations for an ideal gas
Ideal gas: Pv = RT ; du = Cv0 dT ; dh = Cp0 dT
RT
Gibbs: T ds = du + P dv = Cv0 dT + v dv

Cv0 R
ds = T dT + v dv

2 Cv0 v2
s2 – s1 =  T dT + R ln v (6.13)
1 1

RT
Gibbs: T ds = dh – v dP = Cp0 dT – dP
P
Cp0 R
ds = dT – dP
T P
2 Cp0 P2
s2 – s1 =  T dT – R ln P (6.15)
1 1

Conclusions:
Ideal gas: u(T), h(T) but s(T, P) or s(T, v)
Entropy increases with T, increases with v, but decreases with P
Model for specific heat (recall Cp0 = Cv0 + R) needed to evaluate the integrals 18
 Entropy Change for an Ideal Gas

Constant specific heat model:

Cp0 , Cv0 assumed constant and found in Table A.5, F.4
Integrals are done to give:
2 Cp0 P2 T2 P2
s2 – s1 =  T dT – R ln P  s2 – s1 = Cp0 ln T – R ln P (6.16)
1 1 1 1

2 Cv0 v2 T2 v2
s2 – s1 =  T dT + R ln v  s2 – s1 = Cv0 ln T + R ln v (6.17)
1 1 1 1

The expressions are alternatives and consistent. Use Cp0 = Cv0 + R and ideal gas law to
mathematically transform from one to the other equation.

Variable simple specific heat model:

Cp0(T) = Fct(T) polynomial, exponential or power functions
 Cv0(T) = Cp0(T) – RT also a function of T only
Table A.6 shows an example of polynomials used for function Cp0(T).
19
 Entropy Change using the Standard Entropy

Variable complex specific heat model:

0 T Cp0 0
Standard entropy tabulated: s(T, P0 ) = s T ≡  dT + s (6.18)
To T ref

0 0 P2
s2 – s1 = sT2 – sT1 – R ln (6.19)
P1
0 P
Absolute entropy: s(T, P) = sT – R ln
P0

Function is shown for air in A.7, F.5 and other gases in A.8, F.6 with an offset to make
0
the standard entropy a certain value at T0. For other Tables sref = s(T0, P0) may be set to
zero. Normally we need a difference so any offset will cancel out.
0 0 T2 Cp0 0 T1 Cp0 0
Notice: sT2 – sT1 =  dT + s –  dT – s
To T ref To T ref

T2 Cp0 To Cp0 2 Cp0

= dT +  dT =  T dT
To T T1 T 1

20
 Entropy Change Using Different Models
Example 6.4
Find the change in specific entropy of oxygen when state changes from 300 K, 200 kPa
to 1500 K, 150 kPa.
Solution _____________________________________________________
The most accurate result is using standard entropy from A.8 corrected for pressure as
0 0 P2 150
s2 – s1 = sT2 – sT1 – R ln P = 8.0649 – 6.4168 – 0.2598 ln 200 = 1.7228 kJ/kg-K
1

The next best evaluation is using the equation from Table A.6 to get
P2
s2 – s1 = ∫ CP0/T dT = ∫ CP0/θ dθ – R ln P
1
1 1 θ =1.5 P2
= [0.88 lnθ – 0.0001 θ + 2 0.54θ2 – 3 0.33 θ3 ]θ =0.3 – R ln P
1
= 1.7058 kJ/kg-K
Constant specific heat evaluation becomes
T2 P2 1500 150
s2 – s1 = Cp0 ln T – R ln P = 0.922 ln 300 – 0.2598 ln 200 = 1.5586 kJ/kg-K
1 1

This last evaluation is too low since Cp0 is taken at 300 K and it increases with T so in
21
Example 3.13 we found the average should be like Cp0 = 1.06 kJ/kg-K.
Entropy Change Using Different Models

22
 Process Equation Using Entropy

Process: Isentropic, s = constant.

A simple reversible adiabatic compression or expansion is an isentropic process. From
the previous expressions for changes in s we can get relations between P, v and T. A set
of explicit relations are obtained using constant specific heat.
Constant specific heat model:
T2 P2 T2 v2
0 = s2 – s1 = Cp0 ln T – R ln P = Cv0 ln T + R ln v
1 1 1 1

First one gives: ln (P2 / P1) = (Cp0/R) ln(T2 / T1) = ln[ (T2 / T1)Cp0 / R ]
Cp0 / R k/(k – 1)
P2 = P1 [T2 / T1] = P1 [T2 / T1]

Cv0 / R k–1
Second one gives: v2 = v1 [T1 / T2] = v1 [T1 / T2]

With the ratio of specific heats k as

Cp0 Cp0 k Cp0
= =
R Cp0 – Cv0 k – 1 and k=C
v0
23
 Process Equation Using Entropy

The Isentropic Process continued

The relations can be extended with specific volume by the ideal gas law Pv = RT
P2  T2 k/(k−1)  v1 k
P1 =  T1  =v 
 2
T2  P2 (k−1)/k  v1 k−1
T1 =  P1  =v 
 2
These relations are known as the power relations and are valid for an isentropic process
in an ideal gas with constant specific heats. If one of the ratios is known in an isentropic
compression or expansion (typically the P or v ratio) the other ratios can be found.
The pressure to volume relation can be rewritten to recognize
P vk = constant
as a polytropic process with polytropic exponent n = k. The different processes are:

The polytropic processes: P vn = constant

Isobaric: n = 0, P = constant Isentropic: n = k, s = constant
Isothermal: n = 1, T = constant Isochoric: n = ∞, v = constant
24
 Polytropic Process in P-v and T-s diagrams

The polytropic processes: P vn = constant

Isobaric: n = 0, P = constant Isentropic: n = k, s = constant
Isothermal: n = 1, T = constant Isochoric: n = ∞, v = constant

25
 An Isentropic Process
Example 6.6 Constant Specific Heat
Air is expanded from 400 kPa, 600 K to 150 kPa in a piston/cylinder in a reversible
adiabatic process. Find T2, the work done by the air and the expansion ratio v2/v1.

Solution ______________________________________________
CV air, a control mass.
Process: Reversible, Adiabatic  1q2 = 0 isentropic process
Energy Equation: u2 – u1 = 1q2 – 1w2 = – 1w2
Entropy Equation: s2 – s1 = ∫ δq /T = 0
State 1: T1, P1 State 2: P2, ? = s2 = s1
Properties A.5: k = 1.4, Cv0 = 0.717 kJ/kg-K
T2  P2 (k−1)/k
T1  P1 
Constant specific heat and s2 = s1: =

(k – 1)/k 0.2857
T2 = T1 ( P2/P1) = 600 K (150/400) = 453.37 K

1w2 = u1 – u2 = Cv0(T1 – T2) = 0.717 kJ/kg-K (600 – 453.37) = 105.1 kJ/kg

1/k 1/1.4
v2/v1 = (P1/P2) = (400/150) = 2.015 26
 Process Equation Using Entropy

Process: Isentropic, s = constant.

A simple reversible adiabatic compression or expansion is an isentropic process. From
the previous expressions for changes in s we can get relations between P, v and T.
Using standard entropy variable specific heat model:
0 0 P2 P2 0 0
0 = s2 – s1 = sT2 – sT1 – R ln P  ln P = (sT2 – sT1) / R
1 1
0 0
Solve for P2: P2 = P1 exp [(sT2 – sT1) / R ]
0 0
Solve for T2: sT2 = sT1 + R ln (P2 / P1)
This gives the relation between P2 and T2 implicitly using the standard entropy. Using
the ideal gas law the specific volume change can also be found as
0
T2 P1 exp(sT1/R) T2
v2/v1 = T P = T1 0
1 2 exp(sT2/R)

Since T is implicit in the standard entropy a solution for T given the v’s becomes trial and
error.
27
 An Isentropic Process
Example 6.6 Variable Specific Heat
Air is expanded from 400 kPa, 600 K to 150 kPa in a piston/cylinder in a reversible
adiabatic process. Find T2, the work done by the air and the expansion ratio v2/v1.

Solution ______________________________________________
CV air, a control mass.
Process: Reversible, Adiabatic  1q2 = 0 isentropic process
Energy Equation: u2 – u1 = 1q2 – 1w2 = – 1w2
Entropy Equation: s2 – s1 = ∫ δq /T = 0
State 1: T1, P1 State 2: P2, ? = s2 = s1
0
Properties A.7: u = 435.1 kJ/kg, sT1 = 7.5764 kJ/kg-K
Process: : s2 = s1 
0 0
sT2 = sT1 + R ln (P2 / P1) = 7.5764 + 0.287 ln(150/400) = 7.2949 kJ/kg-K
A.7: Interpolate for standard entropy T2 = 457 K, u2 = 328.14 kJ/kg

1w2 = u1 – u2 = 435.1 – 328.14 = 106.96 kJ/kg

v2/v1 = (T2/T1) (P1/P2) = (457/600) (400/150) = 2.03 28
 Process Equation Using the Pr , vr Functions

The relations obtained with the standard entropy for the process s2 = s1 are
0 0 0 0
P2 = P1 exp [(sT2 – sT1) / R ] = P1 exp (sT2/R) / exp (sT1/R)
0
T2 P1 exp(sT1/R) T2
v2/v1 = = 0
T1 P2 T1 exp(sT2/R)

These relations suggest using functions called the relative pressure and relative volume
defined as
0
Pr ≡ exp ( sT / R ), vr ≡ T / Pr
The above relations can be written as
0
P2 Pr2 exp(sT2/R) T2Cp0 / R v2 vr2 T2Cv0 / R
s2 = s1 : P1 = Pr1 = exp(s0 /R) ≈ T  ; v1 = vr1 ≈ T 
 1  1
T1

The near equality shows the constant specific heat approximation. These are tabulated in
Table A.7.2 for air.

29
 Process Equation Using Entropy

Example 6.6 Variable Specific Heat, Pr Function

Air is expanded from 400 kPa, 600 K to 150 kPa in a piston/cylinder in a reversible
adiabatic process. Find T2, the work done by the air and the expansion ratio v2/v1.

Solution ______________________________________________
CV air, a control mass.
Process: Reversible, Adiabatic  1q2 = 0 isentropic process
Energy Equation: u2 – u1 = 1q2 – 1w2 = – 1w2
Entropy Equation: s2 – s1 = ∫ δq /T = 0
State 1: T1, P1 State 2: P2, ? = s2 = s1
Properties A.7: u1 = 435.1 kJ/kg, Pr1 = 13.092
Process: : s2 = s1  Pr2 = Pr1 (P2/P1) = 13.092 (150/400) = 4.9095
A.7.2: Interpolate for Pr2: T2 = 456.9 K, u2 = 328.04 kJ/kg

1w2 = u1 – u2 = 435.1 – 328.04 = 107.06 kJ/kg

v2/v1 = (T2/T1) (P1/P2) = (456.9/600) (400/150) = 2.03

30
 Work in a Polytropic Process

Polytropic process definition: Pv n = constant = C

Indicated work ( n ≠ 1):

2 2
−n C 1−n C 1−n 1−n
1 2 
w =  P dv = 
 C v dv = (v )│2
= (v − v )
1−n 1 1−n 2 1
1 1
1 n 1−n n 1−n
= (P 2v2 v 2 − P1v1 v1 )
1−n
1 R
= (P2v2 − P1v1) = (T – T1)
1−n 1−n 2

Indicated work ( n = 1):

2 2
−
v2 v2
 P dv =  C v dv = C ln v│1 = P1v1 ln v = RT1 ln v
 2
1 w2 = 
1 1 1
1

Last equality in both work expressions is for ideal gas only. The heat transfer is
2
1 q2 =
 T ds = e2 – e1 + 1w2
1
but the polytropic process does not directly relate to T and s, so we can get it from the
energy equation as indicated.
31
 Work and Heat Transfer in a Polytropic Process

Example 6.7 Constant Specific Heat

Nitrogen at 100 kPa, 20oC is compressed to 500 kPa by a piston/cylinder in a reversible
polytropic process with exponent n = 1.3. Find the specific work and heat transfer.
Solution _______________________________________
CV nitrogen, a control mass.
Process: Reversible, polytropic Pv n = C, n = 1.3
Energy Equation: u 2 – u1 = 1 q2 – 1 w 2
State 1: T1, P1 State 2: P2, ? = on process curve
Properties A.5: R = 0.2968 kJ/kg-K, Cv0 = 0.745 kJ/kg-K
Polytropic process:
(n – 1)/n 0.3/1.3
T2 = T1 (P2/P1) = 293.15 K (500/100) = 425.0 K
R R
1 w2 = (T2 – T1) = (425 – 293.15) = –130.4 kJ/kg
1−n 1−n
1 q2 = u2 – u1 + 1w2 = Cv0(T2 – T1) + 1w2
= 0.745 kJ/kg-K (425 – 293.15) – 130.4 = –32.2 kJ/kg
32
 Work and Heat Transfer in a Polytropic Process
Example 6.7 Variable Specific Heat
Nitrogen at 100 kPa, 20oC is compressed to 500 kPa by a piston/cylinder in a reversible
polytropic process with exponent n = 1.3. Find the specific work and heat transfer.
Solution _________________________________________
CV nitrogen, a control mass.
Process: Reversible, polytropic Pv n = C, n = 1.3
Energy Equation: u 2 – u1 = 1 q2 – 1 w 2
State 1: T1, P1 State 2: P2, ? = on process curve
Polytropic process and R = 0.2968 kJ/kg-K from A.5:
(n – 1)/n 0.3/1.3
T2 = T1 (P2/P1) = 293.15 K (500/100) = 425.0 K
R R
1 w2 = (T2 – T1) = (425 – 293.15) = –130.4 kJ/kg
1−n 1−n
Properties A.8: u1 = 217.54 kJ/kg, u2 = 315.83 kJ/kg

1 q2 = u2 – u1 + 1w2 = 315.83 – 217.54 – 130.4 = –32.11 kJ/kg

33
 The Entropy Change in an Irreversible Process
Entropy Change in an Actual Process.

Consider a cycle composed of two processes, A + B moving

a substance between states 1 and 2, then from Clausius

 δQ
2 δQ 1 δQ ≤ 0
○ =
   + 
T 1  T  A  2  T  B
Assume path B is reversible then
1 δQ
  T  B = S1 – S2
2  

2 δQ 2 δQ
  T  A + S1 – S2 ≤ 0  S2 – S1 ≥ 
  T A
1   1
If path A is reversible equal sign applies and if it is irreversible greater than sign applies.
So entropy change is larger than the integral of δQ/T,

δQ δq
dS ≥   or ds ≥  
T T

Reversible path = Irreversible path >

Notice this holds even if δQ is negative so entropy decreases in which case the decrease
is smaller than for a reversible path. 34
 The Entropy Change in an Irreversible Process

Entropy Change in an Actual Process.

The previous conclusion was that entropy increase by more than δQ/T so

δQ
dS =  T  + δSgen ; δSgen ≥ 0 (= for reversible process)
 

Sgen is the generation of entropy due to the irreversibilities in the system (CV). For
reversible processes the Sgen is zero and the integral of δQ/T is the sole explanation for
changes in entropy.

Two reasons for increase in entropy:

Heat Transfer in Q>0
Irreversible process Sgen > 0
One reason for decrease in entropy:
Heat Transfer out Q<0

Change in S, T can go up or down

35
 The Effect of Entropy Generation on Process Work

An Actual Process
Irreversible process: dS = δQ/T + δSgen so δQ = T dS – T δSgen
Energy Eq.: dE = δQ – δW = dU + dKE + dPE
Gibbs relation: T dS = dU + P dV (property relation)

Substitute δQ and T dS into the energy equation to give

dE = T dS – T δSgen – δW = dU + P dV – T δSgen – δW
= dU + dKE + dPE
Now solve for work
δW = P dV – T δSgen – dKE – dPE

work is reduced by T δSgen compared to a reversible process.

Lost work = T δSgen

36
 The Entropy Balance Equation

The previous entropy equation gives the rate form of the Entropy Balance Equation
.
dSCM Q . .
dt = TCS + Sgen ; Sgen ≥ 0

or integrate in time to get

δQ
S2 – S1 = 
2
  T CS + 1S2 gen ; 1S2 gen ≥0
1  

This is the modern version of the second law for a control mass (CM). This follows the
equations for mass, momentum and energy with one extra term

Change of Entropy = + in – out + gen

stating that we can generate but not destroy entropy.

Notice the T is at the control surface (CS) where the Q enters (or leaves) the control
.
volume. The term Q/TCS is a flux of S (entropy per unit time) into the control volume.

37
 The Entropy Balance Equation

Energy Entropy
. .
Storage in CV Ecv Scv
.
Generation in CV - Sgen
. . .
Flux across CS Q, W Q/Tcs

The fluxes across CS are summed over the area,

generally an integral, so then TCS is the local value
Entropy generation: Done by all the irreversible processes inside CV
Friction, Throttling (flow through valve or restriction),
Plastic deformation, Mixing of fluids at two different states,
Unrestrained expansion, Heat Transfer over a finite ΔT
Current through resistor, Mixing of different substances (O2, N2)
Combustion ect…….
Flux is a rate of transport not associated with a mass flow (generic name for many types)
and its value depends on where the control surface is located.
Storage effect, generation are inside CV so they depend on precisely what CV includes.

38
 The Entropy Generation, Heat Transfer over ΔT
Steady state heat transfer through a window

Consider a thermo-pane window separating inside room air from outside ambient air.
When the inside and outside temperatures are different a rate of heat transfer through the
window occurs. Let us examine this with the energy and entropy equations.

CV Window: two glass plates and some gas.

. . . . .
Energy Eq.: 0 = Q1 − Q2  Q1 = Q2 = Q
. . .
Entropy Eq.: 0 = Q1/T1 − Q2/T2 + Sgen
. . . . 1 1
Sgen = Q2/T2 − Q1/T1 = Q ( − ) ≥0
T2 T1
. .
Case 1: T1 > T2 then Sgen ≥ 0 if Q ≥ 0
. .
Case 2: T1 < T2 then Sgen ≥ 0 if Q ≤ 0
.
The entropy equation says it is only possible that Q moves energy from the higher
towards the lower temperature domain. That matches with our experimental observations
and the standard models for heat transfer
.
Q = CA (T1 − T2)
39
The Entropy In-text Concept Questions

40
 The Entropy Generation, Heat Transfer over ΔT
Example 6.8 modified
Saturated water vapor at 100oC is condensed to saturated liquid in an isobaric process by
heat transfer to the ambient which is at 25oC. Find the entropy generation for the process.
Solution ________________________________
CV water out to ambient at 25oC, a control mass.
Energy eq.: u2 – u 1 = 1 q2 – 1 w 2
Entropy Eq.: s2 – s1 = 1q2/TCS + 1s2 gen
Process: P = C  1w2 = P1 (v2 – v1)
State 1: T1, x1 = 1 ; State 2: P1, x2 = 0
From work term and energy equation we get
1 q2 = h2 – h1 = –hfg = – 2257 kJ/kg

1s2 gen = s2 – s1 – 1q2/TCS = – sfg – 1q2/Tamb

= – 6.048 kJ/kg-K – (– 2257 kJ/kg)/298.15 K = 1.522 kJ/kg-K
Notice if CV was water only then TCS = 100oC, same 1q2 and we get

1s2 gen = – sfg – 1q2/TCS = – 6.048 kJ/kg-K –(– 2257 kJ/kg)/393.15 K = 0 kJ/kg-K
This should match, sfg = hfg/T. Process is internally reversible, externally irreversible. 41
 The Entropy Generation, Conversion of W to Q
Example 6.9
In an electric space heater 1 kW of electric power is converted into a heat flux of 1 kW
delivered at 600 K from the hot wire surface. Find the rate of entropy generation for the
wire.
Solution ______________________________________
CV1 Wire in steady state, this is a control mass.
. . . . .
Energy Eq.: Ecv = 0 = Wel. in – Qout  Qout = Wel. in
. . .
Entropy Eq.: Scv = 0 = – Qout / Twire surface + Sgen wire
. .
Sgen wire = Qout / Twire surface = 1 kW/ 600 K = 0.001 67 kW/K

Comment: If we want the total entropy generation then we must include the part of space
where heat is transferred from 600 K to ambient T, i.e. take CV1 + CV2. By taking the
two CV’s separately we can get the two individual entropy generation terms. The total is
the sum of the two individual terms.
. . .
Entropy Eq. CV2: 0 = Qout / Twire surface – Qout / Tamb + Sgen CV2
. . .
Sgen CV2 = Qout / Tamb – Qout / Twire surface

Both cases: Entropy generation is the difference in flux of S as out minus in 42

 The Entropy Generation in an A/C Unit
Example 6.10
Consider an air-conditioner using R-410A working in heat pump mode. It has a COP of 4
with 10 kW of power input. The cold side is buried underground where it is 8oC and the
hot side is a house kept at 21oC. The cycle has T high of 50oC and T low of –10oC, recall
section 5.10. Find where entropy is generated assuming the heat pump is in steady state.
Solution ____________________________________________________
First take CVHP as the heat pump itself. From coefficient of performance
. .
QH = HP  W = 4  10 kW = 40 kW
. . .
Energy Eq. : QL = QH – W = 40 kW – 10 kW = 30 kW
. .
QL QH .
Entropy Eq.: 0= T – T + SgenHP
low high
. .
. QH QL 40 kW 30 kW
SgenHP = T – = – = 9.8 W/K
high Tlow 323 K 263 K

Notice this CV excludes the ∆T in the heat exchangers those are in CV1 and CV2.

43
 The Entropy Generation in an A/C Unit

Example 6.10 continued

Now consider CV1 from the underground 8oC to the cycle –10oC
. .
QL QL .
TL – Tlow + SgenCV1
Entropy Eq.: 0 =
.
. . W
. QL QL 30 kW 30 kW
Tlow – TL = 263 K – 281 K = 7.3 W/K
SgenCV1 =

And finally CV2 from the heat pump at 50oC to the house at 21oC
. .
QH QH .
Thigh – TH + SgenCV2
Entropy Eq.: 0 =
. .
. Q H Q H 40 kW 40 kW
SgenCV2 = – = – = 12.2 W/K
TH Thigh 294 K 323 K

44
 The Entropy Generation in an A/C Unit
Example 6.10 continued

The total entropy generation rate becomes

. . . .
SgenTOT = SgenCV1 + SgenCV2 + SgenHP
. . . . . .
QL QL QH QH QH QL
=T – + – + –
low TL TH Thigh Thigh Tlow
. .
QH QL 40 kW 30 kW
= T – T = 294 K – 281 K = 29.3 W/K
H L

CV Total = CVHP + CV1 + CV2

Using this analysis we cannot specify where the entropy is made,

only the more detailed smaller control volumes can provide this
information.

Bonus question: This misses one effect not shown on the figure.
What is it?

45
 The Statement of Heat Engines From Entropy

CV Heat engine, steady state

. . .
0 = QH – QL – WHE
. .
QH QL .
0= – + Sgen
TH TL
.
Solve for QL using the entropy equation as
. TL . .
QL = Q + T S
TH H L gen

Substitute this into the energy equation from which we get the work term as
. . . . TL . .
WHE = QH – QL = QH – Q – TL Sgen
TH H
. TL . .
WHE = ( 1 –
TH ) QH – TL Sgen (6.45)

The result can be expressed as and related to the actual efficiency

. . .
WHE = ηHE carnot QH – loss = ηHE actual QH (6.46)

46
 The Statement of Refrigerators From Entropy

CV Refrigerator, steady state

. . .
0 = QL – QH + Wref.
. .
QL QH .
0 = T – T + Sgen
L H
.
Solve for QH using the entropy equation as
. TH . .
QH = QL + TH Sgen
TL
and substitute it into the energy equation
. TH . . .
[ ]
0 = QL – T QL + TH Sgen + Wref.
L
.
Now solve for QL to give
. TL . TH TL .
QL = W – S
TH – TL ref. TH – TL gen
. . .
QL = carnot Wref. – loss = actual Wref. (6.50)

47
 Heat Engines, Refrigerators & Entropy: Conclusions

From the results of the analysis of the heat engine and the refrigerator we can conclude:

.
1. We get maximum benefit for a reversible process, Sgen = 0,
. .
Heat Engine: Max WHE for a given QH input
. .
Refrigerator: Max QL for a given Wref. input

2. For a reversible device the analysis predicted

Carnot heat engine efficiency

Carnot refrigerator coefficient of performance

3. For an actual device the analysis shows the decrease in performance

is directly proportional to the entropy generation.

48
 The Statement of Clausius by Entropy Equation

If the entropy equation is used for a steady state cyclic machine as CM then
. .
dSCM . .
dt = 0 =
Q
TCS + S gen  
○ [ Q
TCS + S gen] = 0

and
.
.
 TCS = −  Sgen ≤ 0
○ Q ○

which is the statement of Clausius.

The entropy equation is the modern version of the second law and this is used in an
engineering analysis of systems, devices and processes.

49