Chapter 3

The Energy Equation

The First Law of Thermodynamics
The Work in Simple Systems
The Heat Transfer
The Internal Energy
Control Volume Analysis and Problem Solution
Enthalpy, Specific Heats
Applications and Special Considerations

The Energy Equation

Fundamental laws of classical physics:
Mass, Momentum and Energy are conserved.
You cannot create or destroy mass (m), momentum (mV) or total energy (E ). They can
change form, but the total quantity remains constant.

Total energy:

E = me = U + KE + PE = m (u + ke + pe)
= m (u + 1/2 V2 + gZ)
simple kinetic energy, potential energy

For a given control volume any energy change is due to transfer in or out by work, heat
transfer or flow.
With no flow as in a control mass:
cv = = + in out
Figure dictates equation and sign
notation (your choice).
2

The Energy Equation

Summed over time t1 to t2 the changes are

E2 E1 = 1Q2 1W2
1Q2

E1 , E2

dt ;

1W2

dt

initial (state 1) and final (state 2) total energies so

E2 E1 = U2 U1 + m(V22 V12) + mg (Z2 Z1)

1Q2

, 1W2
followed.

accumulated transfer over the time period, a function of the path being

Both versions of the energy equation in words:

Change of storage = + in - out
Storage is within the CV, in/out are transfer terms across control surface.
3

The Energy Equation

Example 3.1
A tank containing a fluid is stirred by a paddle wheel with a work input of 5090 kJ. Heat
transfer is 1500 kJ out of the tank. Consider the tank and fluid as a control volume and
determine the change of its internal energy.

Solution __________________________________________________
For this control mass we assume:
No change in elevation, Z2 = Z1
No motion initially and motion has stopped at state 2.
The energy equation is
2

U2 U1 + m (V2 V1) + mg (Z2 Z1) = 1Q2 1W2

and with the assumptions reduces to
U2 U1 + m (0 0) + mg ( 0 ) = 1Q2 1W2
U2 U1 = 1500 kJ (5090 kJ) = 3590 kJ
Notice:
Both Q and W are negative (i.e. opposite direction from standard assumption)
We had to make some assumptions about the system
4

The Energy Equation

Exercise 3.1
Write the continuity and energy equations for the control
volume shown in the figure.

Solution ______________________________
From figure we recognize:
Three separate storage places (A, B, C),
No mass enters or leaves,
One work term out from B,
Two heat transfer terms in (A and C)
.
.
.
.
Continuity Eq.:
mcv = mA + mB + mC = in out = 0
.
.
.
.
.
.
.
Energy Eq.:
Ecv = EA + EB + EC = in out = QA + QC WB
When integrated in time the other form of the equations become
m2 m1 = (m2A + m2B + m2C) (m1A + m1B + m1C) = 0
E2 E1 = (E2A + E2B + E2C) (E1A + E1B + E1C) = 1Q2A + 1Q2C 1W2B

The First Law of Thermodynamics

Apply the energy equation to a complete cycle
= 0 = = Qnet Wnet
Giving the first law as
=
Typical real cycles have 4 processes involved so the meaning of the integrals are:
2

= 1 + 2 + 3 + 4
= (E2 E1) + (E3 E2) + (E4 E3) + (E1 E4) = 0
Notice they cancel pairwise.
=

+
+

= 1Q2 + 2Q3 + 3Q4 + 4Q1 = Qnet

= 1W2 + 2W3 + 3W4 + 4W1 = Wnet

Typically several of the 4 processes have = 0 or = 0.

6

The Work
Term
The First Law
of Thermodynamics
Example.
A window air-conditioner absorbs 1200 W as heat transfer from a room and requires an
electrical power of 500 W as input. Find the rate of energy leaving the unit to the outside.

Solution __________________________________________________
This is an example of a cyclic machine that requires some work input to drive two heat
transfers as shown in the figure. The working substance is R134a or R-410A going
through several processes inside the unit so the total system is in a steady state.
The energy equation becomes the first law of thermodynamics as in Eq.3.12:
.
.
.
.
Qnet in = Qroom - Qout = - Wel. in

ambient
.
Qout

so
.
.
.
Qout = Qroom + Wel. in
= 1200 W + 500 W = 1700 W

A/C

.
Wel. in = 500 W

.
Qroom = 1200 W
room

Work at a Moving Boundary of a Compressible Substance

Work from substance to piston
W = F dx = PA dx = P dV
2

=
P dV = area

1W2

To evaluate:

P = function of V
1W2

= Function(1, 2, path)

For example from figure

dV < 0

so

1W 2

is negative

Magnitudes:
1W2 A < 1W2 B < 1W2 C

The Internal Energy

Main characteristic:
u = uext molecule + utranslation + uint molecule
uint molecule = Potential + Rotation + Vibration + Atoms
uext molecule is sensitive to molecular distances and all parts are sensitive to T.
For liquid and solid phases this first part is significant (small distances) and it
diminishes for the vapor states going to zero for ideal gas states.
Information is in the B section tables for substances as fct(T, P).
For a two phase mixture of liquid and vapor
U = Uliq + Uvap = mliquf + mvapug
u = U/m = (mliq/m) uf + (mvap/m) ug
u = (1 x) uf + x ug
u = uf + x ufg

The Internal Energy

Example 3.9
A vessel with volume 5 m3 contains 0.05 m3 of saturated liquid water and 4.95 m3 of
saturated water vapor at 100 kPa. Heat is transferred to a final state of saturated vapor.
Find the heat transfer for this process.

Solution _________________________________
Control mass:
Process:
State 1:
State 2:

All the water.

Constant volume and mass, so v = C.
P1, V1liq and V1vap so we can get x1.
Saturated vapor so x2 = 1.
Process gives v2 = v1.

State 1 (P1, x1):

m1liq = V1liq /vf = 0.05 m3/ 0.001043 m3/kg = 47.939 kg
m1vap = V1vap /vg = 4.95 m3/ 1.6940 m3/kg = 2.922 kg
m1 = 47.939 + 2.922 = 50.861 kg,
x1 = m1vap / m1 = 0.05745
u1 = (1 x1) uf + x1 ug
= 0.94255 417.33 + 0.05745 2506.06 = 537.33 kJ/kg

10

The Internal Energy

Example 3.9 continued
State 2 (v2, x2): Table B.1.2 by interpolation (2000 kPa, 2250 kPa)
v2 = v1 = V/m = 5.0 m3 / 50.861 kg = 0.098 31 m3/kg
0.09831 0.09963
P2 = 2000 + (2250 2000) 0.088750 0.09963 = 2030 kPa
u2 = 2600.26 + 0.1213 (2601.98 2600.26) = 2600.5 kJ/kg
Since mass is enclosed kinetic energy is zero.
Small change in elevation is neglected, Z1 Z2.
Process:

v=C

1W2

P dV =

Energy equation becomes:

E2 E1 U2 U1 = 1Q2 1W2 = 1Q2
so
1Q2 = U2 U1 = m1 (u2 u1)
= 50.861 kg (2600.5 537.33) kJ/kg
= 104 935 kJ
11

The Enthalpy
Example: The constant P process
Recall the work for a constant pressure process
1W2

P dV

= P dV = P (V2 V1)

Assume changes in kinetic and potential energies are zero, the

energy equation gives the heat transfer as
1Q2

= m (u2 u1) + 1W2 = m (u2 u1) + P (V2 V1)

= m (u2 u1) + P m (v2 v1)
= m [(u2 + P2v2) (u1 + P1v1)]

Definition of enthalpy
H U + PV ;

h u + Pv

Enthalpy has same units as u [kJ/kg], and for a two-phase state

h = (1 x) hf + x hg = hf + x hfg
as the mass fraction [1 x and x] averaged property (same as for v, u).
Comment: Any combination of thermodynamic properties is another
property. Enthalpy is used because it appears often.

12

The Specific Heats

Specific heats
Previous cases (KE = 0 and PE = 0 ) give for an incremental process per unit mass:
dv = 0

w = 0

so

q = du

dP = 0

w = P dv

so

q = dh

We want to express this in terms of a property we can measure: T. Due to the above
processes we define the specific heats as:
u
Cv = T ;
v

h
CP = T
P

Thermodynamic properties, a function of the state. They simplify to be fct(T) only, as an

approximation, in the single phase regions: solid, liquid and ideal gas.
du
Cv dT ;

dh
CP dT

No phase change

Then
du = Cv dT

and

u2 u1 = Cv dT Cv (T2 T1)

dh = CP dT

and

h2 h1 = CP dT CP (T2 T1)

where the last expression assumes constant specific heats.

13

Chapter 5

Heat Engines and Refrigerators

The Second Law of Thermodynamics
The Reversible and Irreversible Process
The Carnot Cycle
The Temperature Scales
The Ideal and Real Machines
Typical Devices and Applications

14

Heat Engines and Refrigerators

Historical development of the second law.
Possibility of running heat engines and refrigerators.

Cyclic Machines-Energy Conversion Devices

Heat engines:
To produce work from an energy input of heat.
Steam power plant
Engine (gasoline, diesel)
Gas Turbine
Heat Pumps:
To move energy as heat from lower T to higher T
Refrigerator/Freezer (purpose cooling)
Heat pump (purpose heating)
Air-conditioner (cooling or heating)

15

Heat Engines
Heat Engines
Closed loop between components (flow)
Steps giving a cycle repeated in time (piston/cyl. type)
Details are inside the CV only net W and Qs cross the
CV surface, shown in schematic at bottom.
.
.
.
Energy Eq.: 0 = QH QL WHE
.
.
.
WHE = QH QL
Conversion efficiency:

WHE

thermal = =
QH

QH QL

QH

QL

Q H from combustion

WP, in

WT
.
Q L to ambient

Work is net WHE = WT - WP

=1
QH

.
.
Only part of the heat QH is converted to work WHE, the
remaining part is rejected, typically to the ambient.

16

Heat Engines
Example 5.1
A car engine delivers 136 hp to the drive shaft with
a thermal efficiency of 30%. The fuel it burns
releases 35 000 kJ/kg of energy. Find the total rate
of heat rejected to the ambient and the rate of fuel
consumption in kg/s.

Solution _______________________
Thermal efficiency and conversion of hp from Table A.1 we get
.
.
W = thermal QH = 136 hp 0.7355 kW/hp = 100 kW
.
.
QH = W / thermal = 100 / 0.3 = 333 kW
Energy equation gives
.
.
.
.
QL = QH W = (1 0.3) QH = 233 kW

Energy release, QH = m
qH so
.

m
= QH / qH =

333 kW
= 0.0095 kg/s
35 000 kJ/kg
17

The Refrigerator
Refrigerators/Heat Pumps
Nearly all are closed loop flow between components
Details are inside the CV only net W and Qs cross the
CV surface, shown in schematic at the bottom.
.
.
.
Energy Eq.:
0 = QL QH + W
.
.
.
W = QH QL
Conversion ratio:

QL

QL

COP = ref = =

W QH QL

QH

QH

COP = HP = =

W QH QL
.
.
.
Since QH = QL + W then we have
HP = 1 + ref
Coefficient Of Performance gives the heat transfer that
can be pushed by the engine like a locomotive pulls a coal train.

Room
QH
REF
cb

Win

QL
TL
18

The Refrigerator
Example 5.2
A refrigerator in a kitchen has a power input of 150 W and
it rejects 400 W to the kitchen air. Find the rate of heat
taken from the cold space and the COP of the refrigerator.

Solution ________________________________
.
.
CV refrigerator with WREF = 150 W and QH = 400 W so
the energy equation gives
.
.
.
QL = QH WREF = 400 150 = 250 W
and

QL

250 W
COP = ref =
= 150 W = 1.67
WREF
Comment: The QL is removed since energy transfers into
the cold space from the warmer kitchen and air is
exchanged when the refrigerator door is opened.

19

The Second Law of Thermodynamics

The statements of Kelvin-Planck

and

Clausius

A heat engine cannot convert QH to W 100%

Heat cannot be moved from TL to TH with W = 0

Conclusion:
There must be a QL rejected so
W = QH QL

Conclusion:
There must be some Win > 0
QH = Win + QL

= W / QH < 1

so

= QH /Win <

Notice energy equation does not say these are impossible

20

The Equivalence of Kelvin-Planck to Clausius

Assume a refrigerator can run with W = 0 which is a violation of Clausius, then run a heat engine to
have the same QL. The combination shown as a CV is a heat engine exchanging heat with only one
reservoir (QL net = 0) and some work output, which is a violation of Kelvin Planck.

21

Perpetual Motion Machines

A perpetual-motion machine of the first kind:
Creates work from nothing or creates energy, violating the energy equation (1 st Law)

A perpetual-motion machine of the second kind:

The machine makes an energy conversion that violates the second law.
A perpetual-motion machine of the third kind:
The machine has no friction and produces no work. (Example: Vibrations in a molecule)

A perpetual-motion machine of the second kind:

22

Effects Making Processes Irreversible

We illustrate what a reversible process is by showing processes that are not
reversible. These are called irreversible processes and common in most
practical processes.
Friction:
Sliding something against a surface requires a
work input to overcome friction. Work is converted to
internal energy leading to a warmer surface.
Example: brake pads on a car.

In-elastic deformation:
Bending a piece of metal giving a permanent
deformation turns work into internal energy. This is
internal friction called plastic deformation (unlike a
spring action which is elastic, the work input is stored
as potential energy in the spring).
Current through an Ohmic resistor:
A current through a resistance dissipates power
which heats the resistor. You cannot recover the
electrical energy 100%.
23

Effects Making Processes Irreversible

We illustrate what a reversible process is by showing processes that are not reversible.
These are called irreversible processes and common in most practical processes.
Unrestrained Expansion:
A process can happen and be reversed as shown.
However the surroundings in this case must
supply the work and absorb the heat transfer.
Those two terms are not equivalent. Flow through
a valve is similar, there a pressure is lost.
Heat Transfer over a finite temperature
difference:
Heat transferred from a higher T to a lower T
domain cannot be brought back to the higher T
domain without work input (a heat pump). In the
limit of a differential dT the heat transfer
approaches a reversible process. This becomes a
very slow process, recall
= CA T

T + T

.
Q

Mixing:
After mixing two gases a complicated process with
work input is required to separate the gases again.
24

The Carnot Cycle

The Carnot Cycle
The most efficient heat engine between two constant T
reservoirs. If thermal < 1 then how much less?

Heat engine in reverse is a refrigerator,

Qs and Ws change sign.

Reversible heat transfer: T 0 i.e. T = Treservoir

Two such processes: TL and TH
Practical devices: P = C, heat exchangers
Process where T changes: adiabatic, Q = 0
Two such processes: Expansion / Compression
Practical devices: Turbine Compressor/Pump
Four processes in Carnot cycle:
1.
2.
3.
4.

Reversible isothermal process,

Reversible adiabatic process
Reversible isothermal process,
Reversible adiabatic process

QH at TH
T TL
QL at TL
T TH

Heat engine: 1-2-3-4-1 . QH in, QL out

Refrigerator: 1-2-3-4-1 . QH out, QL in

25

Two Propositions Regarding Carnot Cycle Efficiency

Proposition I:

any rev

Proposition II: rev 1 = rev 2

Proof of both starts assuming they are not true.
Let the better machine be a heat engine and the
other work as a refrigerator (since reversible) with
same QL. The combination is an impossible heat
engine as stated by Kelvin Planck.
This implies the initial assumption is wrong.
These statements are alternative statements to
Kelvin-Planck and Clausius

26

The Thermodynamic Temperature Scale

Since TH and TL are the only common features when two reversible heat engines are
compared it follows:
QL
Proposition II: rev 1 = rev 2 = (TH, TL) = 1
= 1 (TL, TH)
QH
where is a function. Further consideration puts some restrictions on the functional form
to be like (TL, TH) = f(TL)/f(TH). The thermodynamic temperature scale is selected
to have f(T) = T.
TL QL
(TL, TH) = T = Q
H
H
This gives the Carnot heat engine efficiency as
QL
TL
Carnot = 1 Q = 1 T
H
H
This particular choice was done by Lord Kelvin defining the Kelvin scale [K]. The
corresponding English unit scale is Rankine [R].
Ideal Gas Temperature:

Pv = RT

By considering a Carnot cycle it can be proved that this T equals the thermodynamic
temperature scale.
27

The Ideal Versus Real Machines

Real efficiency will be less than the Ideal Carnot cycle
value. The ideal values can still provide some insight
to the real device trend with a variation in T.

TL = 293 K

Heat engines with TH and TL

QL
TL
real thermal = 1 Q 1 T
H
H
First = is from energy eq. and definition,
the last term is Carnot value (max possible).

TH

Typical values from some common heat engines:

TL
Coal fired power plant: TH = 800 K, TL = 325 K so 1 T = 0.60, real 45%
H
Nuclear power plant:

TL
TH = 550 K, TL = 325 K so 1 T = 0.40, real 30%
H

TL
Gas turbine natural gas: TH = 800 K, TL = 325 K so 1 T = 0.60, real 50%
H
Car gasoline engine:

TL
TH = 2000 K, TL = 900 K so 1
= 0.55, real 35%
TH

28

The Ideal Versus Real Machines

Real coefficient of performance efficiency or COP will
be less than the Ideal Carnot cycle value. The ideal values
can still provide some insight to the real device trend with
a variation in T.

ref

HP

Refrigerators/heat pumps with T

QL
TL
real ref =

QH QL
TH TL
TH = 293 K
Ref: TL

TL = 293 K
HP: TH

First = is from energy eq. and definition,

the last term is Carnot value (max possible).
Typical values from some common refrigerators/heat pumps:
Refrigerator: TH = 325 K, TL = 270 K so

TL

= 4.9,
TH TL

real 3.5

TL
Deep Freezer: TH = 325 K, TL = 250 K so
= 3.3,
TH TL

real 2

TL

= 7,
TH TL

real 4

Air conditioner: TH = 320 K, TL = 280 K so

29

The Ideal Versus Real Machines

Example 5.4
A heat engine receives 1 MW at 550oC and rejects heat to the ambient at 300 K while it
produces a rate of work as 450 kW. We want to know the rate of heat discarded to the
ambient and the thermal efficiency and compare both to a Carnot heat engine operating
between the same two reservoirs.

Solution ________________________________
CV Heat engine.
.
.
.
QL = QH W = 1000 450 = 550 kW
. .
Efficiency:
thermal = W / QH = 450/1000 = 0.45
TL
. .
300
Carnot:
Carnot = 1 QL/QH = 1 T = 1 550 + 273 = 0.635
H
For same source the work becomes
.
.
W = Carnot QH = 0.635 1000 kW = 635 kW
.
.
.
Energy Eq.:
QL = QH W = 1000 635 = 365 kW
Energy Eq.:

30

The Ideal Versus Real Machines

Example 5.5
An air conditioner operates like a refrigerator as shown. It should remove 4 kW from a
room at 24oC to the outside atmosphere at 35oC. We want an estimated for the required
work but we will not analyze the details of the cycle, which is deferred to Chapter 9, but
use a lower estimate assuming a Carnot cycle.

Solution ________________________
CV refrigeration cycle, COP for the cycle is

A/C in cooling mode

QL

TL
273 + 24
ref = =
=
= 27
T

T
35

24
H
L
W
so the work will be
.
.
W = QL / ref = 4 kW / 27 = 0.15 kW

Comments: The ref is too optimistic a real A/C has maybe 5. The heat transfers do
require a T to function. Cycle should have TH = 45oC and TL = 18oC to be realistic.

31

The Ideal Versus Real Machines

Example 5.5 extended
An air conditioner operates by removing 4 kW from a room at 24oC to the outside
atmosphere at 35oC. The actual COP is assumed to be a fraction (1/4.5) of the
corresponding Carnot cycle COP. How much power does it require?
If the thermostat is lowered from 24oC to 20oC find the new power requirement.

Solution __________________________
CV refrigeration cycle, COP for the cycle is

QL

ref = = Carnot ref /4.5

W
TL
1
1 273 + 24
= 4.5
= 4.5
=6
TH TL
35 24
so the work will be
.
.
W = QL / ref = 4 kW / 6 = 0.667 kW
When the thermostat is lowered then:

QL

TL
1
1 273 + 20
ref = = Carnot ref /4.5 = 4.5
= 4.5
= 4.34
T

T
35

20
H
L
W
and we can redo the work, but is that enough?

What are we missing?

32

The Ideal Versus Real Machines

Example 5.5 extended continued
As
First condition:

TL ref and Tleak = ( TH TL )

.
Q leak = Cleak Tleak so 4 kW = Cleak (35 24) K
Cleak = 4 kW / 11 K = (4/11) kW/K

Assume Cleak does not change (construction, insulation, wind, ) then

.
Q leak new = Cleak Tleak new = (4/11) kW/K (35 20) K = 5.455 kW
.
.
For steady state ( QL = Q leak new ) so the new power requirement becomes
.
.
W = QL / ref = 5.455 kW / 4.34 = 1.257 kW
Significantly higher, it is very sensitive to TL.

33

Processes limited by first law (energy eq.)

34

Processes limited by second law

35

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

36

The Inequality of Clausius

Conclusion from previous considerations:
All cycles:
= reversible processes;

Q
T 0
< 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 ____________________________________________________
Clausius:

.
.
.
Q
Q
1000 kW 550 kW
H
L

Q
=

=
T
TH TL
823 K 300 K
kW
kW
= (1.215 1.833) K = 0.62 K

Satisfied
37

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
2

Q
=
0
=

T
1

1 Q
Q
T A +

2 T B

Compare this to a reversible cycle with path C + B

2 Q + 1 Q

Q
=
0
=
T C T B
T
1
2
Since the second integral is common we get by subtraction
2 Q = 2 Q = Fct(1,2)
T A
T C
1
1
Integral is the same for all reversible paths, define a state function:
Entropy S:

Q
dS T rev

or

q
ds T rev

[kJ/kg-K]

2 q
s2 s1 =
T rev
1
38

The Entropy
Entropy changes in reversible processes.
In general
q
ds = T rev

and

qrev = T ds

Notice:
1. Change ds follows magnitude and sign of q
2. For a given q change ds is smaller for high T
3. For a reversible process we find heat transfer
2

qrev = T ds

1q2

=
T ds = area
1

These points are illustrated in the figures.

39

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
developments.
Reversible adiabatic process:
q
ds = rev = 0
T

q = 0

T-S diagram

so

s = constant

2
1q2

=
T ds = area = 0
1

This is called an isentropic process.

Reversible isothermal process:
2
s2 s1 =

T = constant so

1q2
q
T rev = T

The two processes and the

area below the process curve
shows the heat transfer.

2
1q2

=
T ds = area = T (s2 s1)
1

40

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
1q2

= TH (s2 s1) = qH

3q4

= TL (s4 s3) = qL

and
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
= 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.

41

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
1q2

= u2 u1 + 1w2 = h2 h1 = hfg

Constant P process

The entropy change is

2 q
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

42

TheCycle
Work
The Carnot
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:
State 3 Table B.5.1:

s1 = sg @0oC = 1.7262 kJ/kg-K,

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:
P2 = 1400 + (1600 1400)

1.7262 1.736
= 1487.1 kPa
1.7135 1.736

From Carnot cycle COP is:

qH
TH
60 + 273.15
HP =
=
=
= 5.55
win TH TL
60 0

43

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.:

2
m(s2 s1) =
1 Q/T

Process:

T=C

2

1 Q/T = 1Q2 /T

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

44

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.

45

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 = q w

Entropy Eq.:

ds = q /T

Simple compressible substance: w = P dv

Substitute q and w 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

Gibbs relations:

T ds = du + P dv
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.

46

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 = T + T dv T = T dT
If specific heat is constant we can integrate
T2
2 C

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 _____________________________________________________
Table A.4:

T2
363.15
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

47

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:
P2
2 Cp0
s2 s1 = T dT R ln P
1
1
v2
2 Cv0
s2 s1 = T dT + R ln v
1
1

T2
P2
s2 s1 = Cp0 ln T R ln P
1
1

(6.16)

T2
v2
s2 s1 = Cv0 ln T + R ln v
1
1

(6.17)

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).

48

Entropy Change using the Standard Entropy

Variable complex specific heat model:
Standard entropy tabulated:

Absolute entropy:

T Cp0
0

dT
+
s
ref
To T

(6.18)

P2
R ln
P1

(6.19)

s(T,

0
P0) = s T

s2

0
0
s1 = sT2 sT1

P
0
s(T, P) = sT R ln P

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
ref
ref
To T
To T

T2 Cp0
To Cp0
2 Cp0
=
dT +
dT = T dT
To T
T1 T
1
49

Entropy Change Using Different Models

50

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 = q /T = 0
State 1:

T1, P1

Properties A.5:

State 2: P2, ? = s2 = s1
k = 1.4, Cv0 = 0.717 kJ/kg-K

Constant specific heat and s2 = s1:

(k 1)/k

T2 = T1 ( P2/P1)
1w2

T2 P2 (k1)/k
T1 = P1
0.2857

= 600 K (150/400)

= 453.37 K

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

v2/v1 = (P1/P2)

1/k

1/1.4

= (400/150)

= 2.015

51

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 = s2

0
0
s1 = sT2 sT1

P2
R ln P
1
0

Solve for P2:

P2 = P1 exp [(sT2 sT1) / R ]

Solve for T2:

sT2 = sT1 + R ln (P2 / P1)

P2
0
0
ln P = (sT2 sT1) / R
1

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 =
0
T1
1 2
exp(sT2/R)
Since T is implicit in the standard entropy a solution for T given the vs becomes trial and
error.
52

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 = q /T = 0
State 1:

T1, P1

Properties A.7:

State 2: P2, ? = s2 = s1
0

u = 435.1 kJ/kg, sT1 = 7.5764 kJ/kg-K

Process: : s2 = s1
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

1w2

T2 = 457 K, u2 = 328.14 kJ/kg

= u1 u2 = 435.1 328.14 = 106.96 kJ/kg

v2/v1 = (T2/T1) (P1/P2) = (457/600) (400/150) = 2.03

53

Process Equation Using the Pr , vr Functions

The relations obtained with the standard entropy for the process s2 = s1 are
0

P2 = P1 exp [(sT2 sT1) / R ] = P1 exp (sT2/R) / exp (sT1/R)

v2/v1 =

T2
T1

P1 exp(sT1/R)
T2
=
0
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

s2 = s1 :

P2 Pr2 exp(sT2/R)
P1 = Pr1 = exp(s0 /R)
T1

T2Cp0 / R
;
T
1

v2 vr2
v1 = vr1

T2Cv0 / R
T
1

The near equality shows the constant specific heat approximation. These are tabulated in
Table A.7.2 for air.
54

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
u2 u1 = 1q2 1w2

Energy Equation:
State 1:

T1, P1

Properties A.5:

State 2: P2, ? = on process curve

R = 0.2968 kJ/kg-K, Cv0 = 0.745 kJ/kg-K

Polytropic process:
(n 1)/n

T2 = T1 (P2/P1)
1 w2 =
1q2

= 293.15 K (500/100)

0.3/1.3

= 425.0 K

R
R
(T2 T1) =
(425 293.15) = 130.4 kJ/kg
1n
1n

= u2 u1 + 1w2 = Cv0(T2 T1) + 1w2

= 0.745 kJ/kg-K (425 293.15) 130.4 = 32.2 kJ/kg
55

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:
State 1:

T1, P1

u2 u1 = 1q2 1w2
State 2: P2, ? = on process curve

Polytropic process and R = 0.2968 kJ/kg-K from A.5:

(n 1)/n

T2 = T1 (P2/P1)
1 w2 =

0.3/1.3

= 425.0 K

R
R
(T2 T1) =
(425 293.15) = 130.4 kJ/kg
1n
1n

Properties A.8:
1q2

= 293.15 K (500/100)

u1 = 217.54 kJ/kg, u2 = 315.83 kJ/kg

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

56

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
2 Q + 1 Q 0

Q
=
T A T B
T
1
2
Assume path B is reversible then
1

2
2

Q
T B = S1 S2

Q
T A + S1 S2 0

2 Q
S2 S1
T A
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 Q/T,
Q
dS T

Reversible path =

or

q
ds T

Irreversible path >

Notice this holds even if Q is negative so entropy decreases in which case the decrease
is smaller than for a reversible path.

57

The Entropy Change in an Irreversible Process

Entropy Change in an Actual Process.
The previous conclusion was that entropy increase by more than Q/T so
Q
dS = + Sgen ;
T

Sgen 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 Q/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

58

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

2
S2 S1 =

Q
T CS + 1S2 gen ;

1S2 gen

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.

59

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 CVs 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

60

The Statement of Heat Engines From Entropy

CV Heat engine, steady state
.
.
.
0 = QH QL WHE
.
.
QH QL .
0 = T T + Sgen
H
L
.
Solve for QL using the entropy equation as
TL .
.
.
QL = T QH + TL Sgen
H
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 T ) QH TL Sgen
H

(6.45)

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

.
.
.
WHE = HE carnot QH loss = HE actual QH

(6.46)
61

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 = T QL + TH Sgen
L
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)

62

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.

63

The Statement of Clausius by Entropy Equation

If the entropy equation is used for a steady state cyclic machine as CM then
.
.
dSCM
.
.
Q
Q

=
0
=
+
S

[
+
S
gen
gen] = 0
dt
TCS
TCS
and
.
.
Q

TCS = Sgen 0
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.

64