Review on Thermodynamics

Yun, ByongJo
School of Mechanical Engineering
Pusan National University

Contents
Thermodynamics Review on
-Systems and Control Volumes
-Energy
-The First Law of Thermodynamics
-The Second Law of Thermodynamics
-Entropy
-Reversible Work and Irreversibility
-Property Relations

Syllabus
Objectives
Review on the fundamental thermodynamics

Text Book
Y. A. Cengel,Introduction of classical thermodynamics for the engineer, 8th ed.,
McGraw Hill
Borgnakke, Sonntag Fundamentals of Thermodynamics, 8th ed.,

Systems and Control Volumes

Systems and Control Volumes

System, Surroundings, Boundary:

System: A quantity of matter or a region in space chosen for study.

Surroundings: The mass or region outside the system
Boundary: The real or imaginary surface that separates the system from its surroundings.

Isolated system: No mass and No energy can cross its boundary.

Closed system (Control mass): A fixed amount of mass, and no mass can cross its
boundary.
Open system (control volume): Mass and energy can across its boundary
Control surface: The boundaries of a control volume. It can be real or imaginary.

Energy

(1)

Energy
The ability to cause changes.
Energy can be categorized by macroscopic and microscopic forms energy.
Macroscopic Forms of Energy : Energy with respect to some outside reference
frame, such as kinetic and potential energies
Kinetic energy (KE)
V2
ke
(kJ / kg ),
2

V2
KE m
(kJ ),
2

V2
KE / V
(kJ / m 3 )
2

Potential energy (PE)

pe gz (kJ / kg ),

PE mgz (kJ ),

PE / V gz ( kJ / m 3 )

Electric, Magnetic, Surface Tension, etc.

Energy

(2)

Microscopic Forms of Energy ; Energy related to the molecular structure

of a system and the degree of the molecular activity (No relation with the
reference frame)

Internal Energy, U : Sum of all the microscopic forms of energy of a system

Sensible + Latent + Chemical + Nuclear energies
(Thermal(heat) Energy)

Sensible : Kinetic energy of molecules

Translation energy
Rotational kinetic energy
Vibrational kinetic energy

Changes in energy<=>changes in Temp.

Latent : associated with the phase change

Binding forces between molecules

If sufficient energy is provided -> phase

change (without change in chemical
composition)

Changes in energy<=>changes in phase

Energy

(3)

Thermal Energy : Sensible + Latent

Mechanical Energy : Form of energy that can be converted to mechanical
work completely and directly by an ideal mechanical device such as an
ideal turbine. (Thermal energy is not mechanical energy, since it cannot be
converted to work directly and completely )
Mechanical energy for flowing fluid

emech

P V2

gz (kJ / kg )
2

Emech

P V

m
gz (kJ )
2

E mech

P V2

m
gz (kW )
2

emech

E mech

P2 P1

P Pa N / m 2 N m / m 3 J / m 3
P

( J / kg ) : Flow Work

V V1
2
g ( z 2 z1 ) (kJ / kg )
2

P2 P1 V2 2 V12

g ( z 2 z1 ) (kW )
2

Energy

(4)

Flow Work (Flow Energy , Converted Energy or Transport Energy)

The work (or energy) required to push the mass into or out of the
control volume. This work is necessary for maintaining a continuous
flow through a control volume

W flow FL PAL PV (kJ )

w flow Pv (kJ / kg )

Energy

(4)

Flow work, or flow energy: The work (or energy)

required to push the mass into or out of the control
volume. This work is necessary for maintaining a
continuous flow through a control volume.

F PA

W flow FL PAL PV

(kJ )

w flow Pv (kJ / kg )
Flow work :
-Two properties: P,v
-Flow energy
,Converted energy
,Transport energy
PV represents energy for
flowing fluids only and does
not represents any form of
energy nonflow systems
->should be treated as Work.
9

The First Law of Thermodynamics (1)

The First Law of Thermodynamics

Qin Qout

The conservation of energy principle

Energy balance
Ein

Eout Esystem

PinAin

Total energy
Total energy
Change in the total

entering
the
system
leaving
the
system
energy
of
the
system

PoutAout

Control
Volume

Win,s

Wout,s

Energy transfer mechanism

Heat Transfer
Increase of the energy of molecules and thus the internal energy of the system

Work transfer
Energy transfer not caused by temperature difference between system and
surrounding

Mass flow
When mass enters a system, mass carries energy with it. (In fact, mass is energy)

Change of energy in the system

Changes in internal, kinetic and potential energies

1
Esystem E2 E1 U KE PE m(u2 u1 ) m(V22 V12 ) mg ( z 2 z1 )
2

10

The First Law of Thermodynamics (2)

Energy Balance Equation for Control Volume
Ein Eout (Qin Qout ) (Win Wout ) ( Emass ,in Emass ,out )
v22
v12
Esystem m2 (u2 gz 2 ) sys m1 (u1 gz1 ) sys
2
2
(Win Wout ) ( Pin Ain xin Pout Aout xout ) (Win Wout ) s ( PinVin PoutVout ) (Win Wout ) s
Flow work to move fluid

Pin

in

min

Pout

out

mout ) (Win Wout ) s

2
vin2
vout
( Emass ,in Emass ,out ) min (uin
gzin ) mout (uout
gzout )
2
2

Ein Eout

E in E out

2
vin2
vout
(Qin Qout ) (Win Wout ) s min ( Pin in uin
gzin ) mout ( Pout out uout
gzout )
2
2
hin
hout
2
2
v
v
Esystem m2 (u2 2 gz 2 ) sys m1 (u1 1 gz1 ) sys
2
2

2
2
v
v
in
out
(Q in Q out ) (Win Wout ) s m in (hin gzin ) m out (hout
gzout )
2
2

dEsystem
dt

v22
v12
m 2 (u2 gz 2 ) sys m 1 (u1 gz1 ) sys
2
2
11

The First Law of Thermodynamics (3)

Energy Conversion Efficiencies
Defined by using the first law of thermodynamics

Desired output
Re quired input

mech

Emech,loss
Mechanical energy output Emech,out

1
Mechanical energy input
Emech,in
Emech,in

turbine

W shaft ,out
Wturbine
Mechanical energy output

Mechanical energy decrease of the fluid Emech, fluid Wturbine,in

generator

Welect ,out
Electric power output

Mechanical power input W shaft ,in

turbine gen

Wturbine

Wturbine,in

Welect ,out
Welect ,out
turbine generator

Wshaft ,in
E mech, fluid

12

The First Law of Thermodynamics (4)

Enthalpy
Enthalpy for a constant-pressure expansion or compression process

Ein Eout (Qin Qout ) (Win Wout ) ( Emass ,in Emass ,out ) U KE PE
0

Q W U KE PE

(Q Q in Q out , W Wout Win )

Q Wother Wb U 2 U1

Boundary work
against atmosphere

Wb P0 (V2 V1 )

Q Wother Po (V2 V1 ) U 2 U1
Q Wother (U 2 PoV2 ) (U1 PoV1 )

Defining enthalpy energy : H U PV

Q Wother H 2 H1
13

The First Law of Thermodynamics (5)

Specific heat

(kJ/kgC or kJ/kgK)

Specific heat at constant volume, cv

The energy required to raise the temperature of
the unit mass of a substance by one degree as
the volume is maintained constant.

u
cv

T v

Specific heat at constant pressure, cp

The energy required to raise the temperature of
the unit mass of a substance by one degree as
the pressure is maintained constant

h
c p

T p

(values are for helium gas).

cp >cv : cp contains the energy for the expansion

work of system at constant pressure the system
14

The First Law of Thermodynamics (6)

Analysis of Some Steady-flow Engineering Devices
2
2
dEsystem

v
v

2
1
Ein Eout Esystem
m 2 (u 2 gz 2 ) sys m 1 (u1 gz1 ) sys

dt

2
2
v
v
in
out
(Q in Q out ) (Win Wout ) s m in (hin
gzin ) m out (hout
gzout ) 0
2
2
Nozzles and Diffusers
Turbines and Compressors
Pumps
2
Win m in hin m out hout 0
vin2
vout

Win m in hin Qout m out hout

)
m in (hin ) m out (hout
2
2
h u Pv

dh du dP v P dv 0

h u ( cavg T ) 0 P v
h vP

15

The Second Law of Thermodynamic (1)

The second law of thermodynamics
Processes occur in a certain direction, and not in
the reverse direction.
The second law also asserts that energy has quality
as well as quantity. The first law is concerned with
the quantity of energy and the transformations of
energy from one form to another with no regard
to its quality. The second law provides the
necessary means to determine the quality as well
as the degree of degradation of energy during a
process.
The second law of thermodynamics is also used in
determining the theoretical limits for the
performance of commonly used engineering
systems, such as heat engines and refrigerators, as
well as predicting the degree of completion of
chemical reactions.
16

The Second Law of Thermodynamic (2)

Heat engines
1. They receive heat from a high-temperature source
(solar energy, oil furnace, nuclear reactor, etc.).
2. They convert part of this heat to work (usually in
the form of a rotating shaft.)
3. They reject the remaining waste heat to a lowtemperature sink (the atmosphere, rivers, etc.).
4. They operate on a cycle.

Thermal efficiency

17

The Second Law of Thermodynamic (3)

The Second Law of Thermodynamics
Clausius Statement

KelvinPlanck Statement
It is impossible for any device that
operates on a cycle to receive heat
from a single reservoir and produce
a net amount of work.

It is impossible to construct a device that

operates in a cycle and produces no effect
other than the transfer of heat from a lowertemperature body to a higher-temperature
body.

Impossibility of
having a 100%
efficient heat.

-Direction of
heat flow.
-Reversed
heat flow
requires
work input

18

The Second Law of Thermodynamic (4)

Reversible and Irreversible Processes
Reversible process: A process that can be reversed without leaving any trace on
the surroundings.
Irreversible process: A process that is not reversible.
friction, unrestrained expansion, mixing of two fluids, heat transfer across a
finite temperature difference, electric resistance, inelastic deformation of
solids, and chemical reactions.

Two familiar reversible processes.

Friction renders a
process irreversible.

(a) Heat transfer

through a
temperature
difference is
irreversible
(b) the reverse
process is
impossible.
19

The Second Law of Thermodynamics (5)

The Carnot Cycle
Idealized reversible cycle->the most efficient cycle
between two specified temperature limit

Isothermal
expansion
by heat addition (Work Output)

Isothermal
compression
by heat rejection (Work
Input)

20

The Second Law of Thermodynamic (6)

Efficiency of heat engine
Any heat
engine

Carnot heat
engine

QL
th 1
QH

th,rev 1

th ,rev

th th,rev

th , rev

TL
TH

irrevsrsible heat engine

revsrsible heat engine
impossible heat engine

Energy has a quality as well as a quantity.

More of the high-temperature thermal energy can be converted to work
->Therefore, the higher the temperature, the higher the quality of the energy.
21

The Second Law of Thermodynamics (7)

Entropy

Qin
Tin

Clausius Inequality & Definition of Entropy

Clausius
inequality

Q
Entropy is an extensive
ds

T int,rev property of a system.

Increase of Entropy Principle

Qout
Tout

Clausius inequality

Q
0

2
T
T int,rev

Q
T

ds 0
2

S S 2 S1

Q
T

S sys S 2 S1

Q
T

Increase of
entropy principle

S gen

0 irrevsrsible heat engine

S gen 0 revsrsible heat engine

0 impossible heat engine

22

The Second Law of Thermodynamics (8)

Remark on the Entropy
Processes can occur in a certain direction only, not in any direction. A process
must proceed in the direction that complies with the increase of entropy
principle, that is, Sgen 0.

Entropy is a nonconserved property, and there is no such thing as the

conservation of entropy principle. Entropy is conserved during the idealized
reversible processes only and increases during all actual processes.

The performance of engineering systems is degraded by the presence of

irreversibility, and entropy generation is a measure of the magnitudes of the
irreversibility during that process.

Isentropic process
Entropy of fixed mass can be changed by
(1) heat transfer (2) irreversibility
-> No change of entropy if (1) adiabatic (2)reversible
A process during which the entropy remains constant is
called an isentropic process
23

The Second Law of Thermodynamics (9)

Ex) Entropy generation according to temperature difference during heat transfer
S source

Ssin k

Qsource
Tsource
2000kJ
2.5kJ / K
800K

2000 kJ

Qsin k

Tsin k

Source
800 K

S gen S source Ssin k

Sink
500 K

Qsource
Tsource
2000kJ
2.5kJ / K
800 K

2000 kJ
Ssin k

2000kJ
4kJ / K
500K

1.5kJ / K

Source
800 K

S source

Sink
750 K

Qsin k
Tsin k

2000kJ
2.7kJ / K
750K

S gen S source Ssin k

0.2kJ / K

Higher temperature difference, more irreversibility!

24

The Second Law of Thermodynamics (10)

What is Entropy?
-A measure of molecular, disorder or molecular randomness.
-> As a system becomes more disorder, the positions of the molecules
becomes less predictable and the entropy increases
-> Associated with the molecular chaos.
-> Level of entropy according to phases of a substance : solid< liquid < gas
-The entropy of a system is related to the total number of
possible microscopic states of that system, called
thermodynamic probability p, by the Boltzmann relation,
Boltzmann relation :
->Entropy increases whenever the molecular randomness or
uncertainty (molecular probability) of a system increases.

The level of molecular

disorder (entropy) of a
substance increases as it
melts or evaporates.

A pure crystalline substance at absolute

zero temperature is in perfect order, and its
entropy is zero -> Absolute entropy
(the third law of thermodynamics).
25

The Second Law of Thermodynamics (11)

Disorganized energy does not create much

useful effect, no matter how large it is.

In the absence of
friction, raising a
weight by a rotating
shaft does not
create any disorder
(entropy), and thus
energy is not degraded
during this
process.

The paddle-wheel work done on a gas

increases the level of disorder (entropy)
of the gas, and thus the provided work
energy is degraded during this process.

During a heat transfer process, the net entropy increases.

(The increase in the entropy of the cold body more than
offsets the decrease in the entropy of the hot body.)
26

The Second Law of Thermodynamics (12)

Isentropic efficiency
Defined based on the 2nd law of Thermodynamics.
Ideal steady flow devices such as turbines, compressors, and nozzles, etc.
->Adiabatic and Isentropic
->Defining Isentropic or adiabatic efficiencies.
Turbine

Turbine

h h
Actual work
1 2a
Isentropic work h1 h2 s

27

The Second Law of Thermodynamics (13)

Compressor and Pump

Compressor

Isentropic work
Actual work

Compressor

h2 s h1
h2 a h1

Pump

Nozzles

Compressor

V22a
Actual KE at nozzl exit

2
Isentropic KE at nozzl exit V2 s

dh vdP
vP2 P1

ds

T
T
h2 a h1

28

The Second Law of Thermodynamics (14)

Entropy balance
Change in the
Total entropy Total entropy

Total entropy
total entropy
entering
leaving

generated
of the system
the system the system

Sin

S out S gen S system

S system S final

Sinitial S 2

S1

S system sm sV

Entropy transfer by heat transfer

Entropy transfer by mass flow

29

The Second Law of Thermodynamics (15)

Entropy generation, Sgen

for closed system

30

The Second Law of Thermodynamics (16)

Control volume

31

The Second Law of Thermodynamics (17)

32

The Second Law of Thermodynamics (18)

33

Property Relations (1)

Property Tables
Properties in the form of tables.
The state of a simple compressible system is completely specified by
two independent, intensive properties=> State postulate
Thermodynamic properties for
Compressed liquid
Saturated liquid
Two-phase-mixture
Saturated vapor
Superheated vapor

34

Property Relations (2)

Phase Change Process
Quality, x : The ratio of the mass of
vapor to the total mass of the mixture
mvapor
x
mtotal
v2 v f xv fg

u2 u f xu fg

h2 h f xh fg

s2 s f sh fg

35

Property Relations (3)

Ideal (Perfect) Gases
Equation of state: Any equation that relates the pressure, temperature,
and specific volume of a substance.
An ideal gas is a theoretical gas composed of a set of randomly-moving,
non-interacting point particles. (()
.
, .)

V
Pv P RT
m

Ru
R
(kJ / kg K )
M

PV mRT

R: gas constant
M: molar mass (kg/kmol)

PV m

Ru
T nRuT
M

Ru: universal gas constant

N (m/M) : number of moles

36

Property Relations (4)

Actual (Imperfect) Gases
Compressibility factor Z is introduced in the ideal gas equation of state.
A factor that accounts for the deviation of real gases from ideal-gas behavior
at a given temperature and pressure.

Pv vactual

Pv ZRT , Z
RT videal

Z factor for various gases

P
PR
Pcr

Reduced
pressure

TR

T
Tcr

vR

vactual
v
actual
vcr
RTcr / Pcr

Reduced
temperature
Pseudo-reduced
specific volume

37

Property Relations (5)

Tds relations
From energy eq. for a closed stationary system containing a simple compressible
substance and an internally reversible process;

the first T ds, or Gibbs equation

The T ds relations are valid for

both reversible and irreversible
processes and for both closed
and open systems.

the second T ds equation

Differential changes
in entropy in terms
of other properties

38

Property Relations (6)

ENTROPY change of liquids and solids

For an isentropic process of an incompressible substance

ENTROPY change of ideal gas

From the first T ds relation

From the second T ds relation

39

Property Relations (7)

Constant Specific Heats

Isentropic Processes of Ideal Gases

40

Property Relations (8)

Variable Specific Heats

Relative Pressure and Specific Volume for Isentropic Process

exp(s/R) is
the relative
pressure Pr.

41