ME 321 Chapters 1-8, Review of Thermo I

1
1-8
Review of Thermo I
CHAPTERS CHAPTERS
Thermodynamics is a funny subject. The first time you
go through it, you dont understand it at all. The
second time you go through it, you think you
understand it, except for one or two points. The third
time you go through it, you know you dont understand
it, but by that time you are so used to the subject, it
doesnt bother you anymore.
-Arnold Sommerfield
ME 321 Chapters 1-8, Review of Thermo I
Systems
boundaries (control surface)
surroundings
closed systems (control mass)
e.g. balloons, tanks, cylinders
rigid systems
stationary systems
open systems (control volume)
e.g. nozzles, turbines, heat
exchangers
isolated systems
ME 321 Chapters 1-8, Review of Thermo I
2
V
ke ,
2
1
2
2
mV KE
gz mgz PE pe ,
Forms of Energy
Kinetic Energy
macroscopic motion
Potential Energy
change in elevation
Internal Energy
Sum of microscopic forms, U, u
Total Energy
E=U+KE+PE, e=u+ke+pe
Energy interactions
Heat (Temperature difference)
Work
ME 321 Chapters 1-8, Review of Thermo I
Any characteristic of a system
Not all properties are independent
e.g.
Specific gravity (/
H2O
)
Specific volume (1/)
Intensive properties- independent of system size
T, P, , v, u, ke, pe, e, MW, viscosity, conductivity, etc.
Extensive properties
m, Vol, Mol, E, KE, PE, U, heat capacity, etc.
The continuum hypothesis (no microscopic holes)
mixture saturated in T and P ,
V
m

Properties
ME 321 Chapters 1-8, Review of Thermo I
States, equilibrium, process, path,
state - the set of properties that
completely describe the
condition of the system
equilibrium - system experiences
no changes when isolated from
its surroundings (thermal,
mechanical, phase, chemical)
process - change in a system
from an initial to a final
equilibrium state
path - series of states through
which a system passes during the
process
ME 321 Chapters 1-8, Review of Thermo I
States, equilibrium, process, path, cycles
quasi-equilibrium process - all
states in process vary only
infinitesimally from
equilibrium states
cycle - when initial and final
state are identical
ME 321 Chapters 1-8, Review of Thermo I
Special processes
Isothermal
constant temperature
isobaric
constant pressure
isometric (isochoric)
constant specific volume
ME 321 Chapters 1-8, Review of Thermo I
The State Postulate
Simple compressible system
(electrical, magnetic,
gravitational, motion, and
surface effects are neglibible)
The state postulate - for a
simple compressible system
the state is completely
specified by two independent,
intensive properties
ME 321 Chapters 1-8, Review of Thermo I
Properties of Pure Substances
Pure substance - fixed chemical
composition throughout
3 types of phases - solid, liquid, gas
- related to molecular interactions
and distances
Transition between phases
evaporation/condensation
melting/fusion
sublimation
ME 321 Chapters 1-8, Review of Thermo I
Liquid-vapor phase transition
Subcooled liquid/compressed
liquid
Saturated liquid (about to
vaporize)
Saturated liquid-vapor mixture
Saturated vapor
Superheated vapor
ME 321 Chapters 1-8, Review of Thermo I
11
The P-v-T Solid
A P-v-T solid shows the
surface of equilibrium states
This P-v-T solid is for
substances which expand upon
freezing (water)
ME 321 Chapters 1-8, Review of Thermo I
12
The P-v Diagram Showing Phase Boundaries
ME 321 Chapters 1-8, Review of Thermo I
The T-v Diagram
ME 321 Chapters 1-8, Review of Thermo I
14
The P-T Diagram
The triple line becomes a
triple point
The critical point is at the
end of the liquid-vapor
line
This is also called the
phase diagram
ME 321 Chapters 1-8, Review of Thermo I
Vapor Pressure (in gas mixtures)
P
v
= P
sat@T
Relative humidity ranges from 0 to 1
The vapor pressure is the partial pressure of the
vapor in the mixture (P = P
dry

air
+ P
v
)
(If no air is present P
v
is simply P
sat
)
If is 1.0 the air is saturated
ME 321 Chapters 1-8, Review of Thermo I
Vapor Pressure (in gas mixtures)
Concentration differences in the gas will be the
driving force for mass transfer
At surface is 1.0 and vapor mass is transferred
away from the surface
Condensation and evaporation are the results
Evaporation is different than boiling
Saturation phenomena also exist in liquids
ME 321 Chapters 1-8, Review of Thermo I
17
The Saturation Tables
(A-4 and A-5)
A-4 is indexed by temperature,
A-5 is indexed by pressure
Notice only one equilibrium
pressure for a saturated liquid-
vapor mix at a given
temperature
The saturated liquid volume is
when there is only liquid at
saturated conditions
The saturated vapor volume is
when only vapor is present
ME 321 Chapters 1-8, Review of Thermo I
18
Graphical Representation of Specific Volume
By looking at the P-v diagram
we can see how the quality is
used to compute the specific
volume
A similar procedure is used
for T-v diagram
Note that graphically the
volume is not linear on the x-
axis
ME 321 Chapters 1-8, Review of Thermo I
The specific volume of the mixture is the weighted
average of the specific volume of saturated liquid
and saturated vapor
m
tot
v = m
f
v
f
+ m
g
v
g
or,
v = (m
tot
-m
g
)v
f
/m
tot
+ m
g
v
g
/m
tot
= (1-x)v
f
+ xv
g
Therefore v = vf + x(v
g
- v
f
)
Likewise, u = u
f
+ xu
fg
, and
h = h
f
+ xh
fg
Saturation tables (continued)
ME 321 Chapters 1-8, Review of Thermo I
20
Superheated Vapors
For superheated vapors
the properties are
indexed by both
temperature and
pressure
Double-interpolation
might be needed to get
more accurate values
ME 321 Chapters 1-8, Review of Thermo I
Compressed Liquid Tables
Use compressed liquid tables only for really
high pressures and when accuracy is needed
Generally evaluate properties as the saturated
liquid property at the given temperature
For enthalpy may need to compute as follows:
h = h
f@T
+ v
f
(P - P
sat
)
ME 321 Chapters 1-8, Review of Thermo I
An equation is better than a table
For gases experiments yielded the following:
at fixed T: P
2
/P
1
=v
1
/v
2
(or P
1
v
1
=P
2
v
2
=constant) (Boyles law, 1662)
at fixed P: T2/T1=v2/v1
(or T
1
/v
1
=T
2
/v
2
=const.) (Charles - Gay-Lussac law, 1802)
Combining these two ideas gives the Ideal gas law:
Pv=RT
R is an ideal gas constant which depends upon the gas
It turns out that R = Ru/M where Ru is the universal gas
constant
I deal Gas equation of state
ME 321 Chapters 1-8, Review of Thermo I
Pv RT
u

also: P
1
v
1
/T
1
= P
2
v
2
/T
2
I deal Gas equation of state, other forms
Since the number of moles, n = m/M, and the
number of molecules, N, per mole is Avogadros
number, N
A
( n = N/N
A
):
PV = mRT
P = RT
PV = nR
u
T
PV = (N/N
A
)R
u
T
P = cR
u
T (c is concentration)
PV = Nk
B
T (kB is Boltzmanns const. = R
u
/N
A
)
ME 321 Chapters 1-8, Review of Thermo I
The Universal I deal Gas Constant
8.314 kJ /(kmol
.
K)
8.314 kPa
.
m
3
/(kmol
.
K)
0.08314 bar
.
m
3
/(kmol
.
K)
1.986 Btu/(lbmol
.o
R)
10.73 psia
.
ft
3
/(lbmol
.o
R)
1545 ft
.
lb
f
/(lbmol
.o
R)
1.987 cal/(mol
.
K)
0.08206 liter
.
atm/(mol
.
K)
0.7302 ft
3.
atm/(lbmol
.o
R)
ME 321 Chapters 1-8, Review of Thermo I
Notes on I deal Gas equation of state
Ideal gas is an imaginary substance
Most applicable to low density gases
H2, He, Ar, Ne, Air, O2, N2, CO2, CO, etc. can
generally be treated as an ideal gas
Water vapor and refrigerants typically not treated
as an ideal gas
How can I know if treating a gas as an ideal gas is
the right thing to do?
ME 321 Chapters 1-8, Review of Thermo I
The Compressibility Factor, Z
Z is defined by: Z = Pv/RT
If Z = 1, or close to 1, treat gas as an ideal gas
The behavior of gases can be generalized from
knowing their critical states (Fig. 2-57)
P
R
, the reduced pressure is P/P
c
T
R
, the reduced temperature is T/T
c
v
R
, the pseudo-reduced specific volume is v
act
P
c
/RT
c
ME 321 Chapters 1-8, Review of Thermo I
27
Regimes for using I deal Gas Law
This T-v diagram shows
the region where error in
using the ideal gas law is
less than 1%
Error is highest near the
critical point
This corresponds to
T
R
= 1 and P
R
= 1 on the
Z vs. P
R
diagram
ME 321 Chapters 1-8, Review of Thermo I
...
) ( ) ( ) ( ) (
5 4 3 2
+ + + + +
v
T d
v
T c
v
T b
v
T a
v
RT
P
Other Equations of State
van der Waals
Virial
( )
P
a
v
v b RT +

_
,

2
ME 321 Chapters 1-8, Review of Thermo I
29
Boundary Work
Boundary work can be
computed by integrating
This result comes from the
definition of work applied to a
simple compressible system
W P dV
b
V
V

1
2
W Fds P A ds Pd A s PdV
V
V


( ) ( )
1
2
ME 321 Chapters 1-8, Review of Thermo I
30
Work for Constant Pressure Processes
In terms of specific work
( )
W P dV P dV P V V
b
V
V
V
V


1
2
2 1
1
2
( ) w Pdv P dv P v v Pv Pv
b
v
v
v
v


1
2
2 1 2 1
1
2
ME 321 Chapters 1-8, Review of Thermo I
31
Work for I deal Gas Processes
( ) ( )
w P v v Pv Pv R T T
b

2 1 2 1 2 1
( ) ( )
W P V V PV PV mR T T
b

2 1 2 1 2 1
Constant Pressure
Constant Temperature
Constant volume
w Pdv
RT
v
dv RT
dv
v
RT v v RT
v
v
b
v
v
v
v
v
v

_
,

(ln ln ) ln
2 1
2
1
1
2
1
2
1
2
w
b
0
ME 321 Chapters 1-8, Review of Thermo I
32
Work for polytropic processes
A polytropic process is one given by
Work for a polytropic process is given by
PV C
n
(C is a constant)
w Pdv Cv dv C
v v
n
b
n
n n
v
v
v
v


+

+ +

2
1
1
1
2
1
1
2
1
( ) ( )
w
P v v Pv v
n
P v Pv
n
b
n n n n

+ +
2 2 2
1
1 1 1
1
2 2 1 1
1 1
ME 321 Chapters 1-8, Review of Thermo I
33
I deal gas and polytropic processes
Pv
n
=C and Pv = RT
n = 0 Constant pressure process
n = 1 Constant temperature process
n = Constant volume process
n = k = c
p
/c
v
= isentropic process

ME 321 Chapters 1-8, Review of Thermo I

34
Energy Change for a Cycle
In a cycle the beginning
and end states are the
same.
Therefore E is zero
The net heat must equal the
net work
ME 321 Chapters 1-8, Review of Thermo I
35
The First Law of
Thermodynamics takes on
several forms
Care must be taken to ensure
proper application and use of
signs
This is most easily learned
through doing examples
Closed-Systems, First-Law Closed-Systems, First-Law
ME 321 Chapters 1-8, Review of Thermo I
36
Formal Definitions of C
v
and C
p
Specific heat is the amount of
energy it takes to raise a
substances temperature one degree
If done as a constant volume
process:
If done as a constant pressure
process:
These are properties and do not
exist whether or not the actual
process is constant volume or
constant pressure
c
u
T
v
v

c
h
T
p
p

ME 321 Chapters 1-8, Review of Thermo I

37
Specific Heats for Some Gases
Inert gases have constant c
p
values
k (=c
p
/c
v
) is also constant at
around 5/3 for these gases
k for many diatomic gases is
around 7/5
These relate to degrees of
freedom of the molecules
ME 321 Chapters 1-8, Review of Thermo I
38
Three Ways to Calculate u
Table values are the simplest
method: u = u
2
- u
1
, but tables
are not available for all gases
If c
v
is known in functional form,
integration over the temp. range
gives u.
A good approximation can usually
be obtained by picking an average
value of c
v
or the c
v
at an average
temperature.
ME 321 Chapters 1-8, Review of Thermo I
39
Helpful Cp and Cv relations Applications
For ideal gases C
v
, and C
p
are related by:
The specific heat ratio k is defined as:
For incompressible substances (liquids and
solids), both the constant-pressure and constant-
volume specific heats are identical and denoted
by C:
ME 321 Chapters 1-8, Review of Thermo I
40
The volumetric flow rate divided
by the specific volume gives the
mass flow rate
Same as density times volumetric
flow rate
For steady flow, no mass
accumulates in the control volume
and the inlet mass flow rate equals
the exit mass flow rate
Continuity (Conservation of mass)
The McGraw-Hill Companies, Inc.,1998
Mass flow rate and Steady flow Mass flow rate and Steady flow
e
e
av e i
i
av i
e
e
av
e
i
i
av
i
e i
A V A V
A V
v
A V
v
m m

1 1
! !
ME 321 Chapters 1-8, Review of Thermo I
41
Flow Work Flow Work
The 1st law reduces to:
We rearrange the mass-related transfer terms to
the R.H.S. since they are measurable properties
and the enthalpy property becomes useful
( ) ( ) ( ) pe ke h h pe ke v P v P u u w q
i e i i e e i e out in
+ + + + +

For steady for dE

cv
/dt = 0
For single stream there is
one inlet and one outlet
m m m
e i
! ! !

( ) ( ) 0 + + + + + + +
e e e e e i i i i i out in
pe ke u v P m pe ke u v P m W Q
! !
! !
ME 321 Chapters 1-8, Review of Thermo I
42
Energy balance for Steady Flow Systems Energy balance for Steady Flow Systems
On a rate basis with steady mass flow rates the
energy equation becomes

1
1
1
]
1

,
_

+ +
1
1
1
]
1

,
_

+ +
i
i
i
av
i i
e
e
e
av
e e out in
gz
V
h m gz
V
h m W Q
2 2
2 2
! !
! !
.
.
.
.
.
ME 321 Chapters 1-8, Review of Thermo I
43
Steady-Flow Devices Operate
Steadily for Long Periods
Steady-Flow Devices Operate
Steadily for Long Periods
ME 321 Chapters 1-8, Review of Thermo I
44

,
_

+ +

,
_

+ +
i
i
av
i i e
e
av
e e out in
gz
V
h m gz
V
h m W Q
2 2
2 2
! !
! !
Nozzle and Diffuser Shapes Cause
Large Changes in Fluid Velocities
Nozzle and Diffuser Shapes Cause
Large Changes in Fluid Velocities
Nozzles increase fluid velocity
at the expense of pressure
Diffusers increase fluid pressure
by slowing it
Nozzles and Diffusers are shaped so
that they cause large changes in fluid
velocities and thus kinetic energies
0
0
0
Fluid spends little
time in C.V. so
no heat exchange
No work is done
by a nozzle or
diffuser
0
Small device so neglect
potential energy changes
2 2
,
2 2
2 2 2 2
i
av
e
av
i e
i
av
i
e
av
e
V V
h h
V
h
V
h + +
For single inlet single outlet the
constant mass flow rate cancels
0
0
ME 321 Chapters 1-8, Review of Thermo I
45

,
_

+ +

,
_

+ +
i
i
av
i i e
e
av
e e out in
gz
V
h m gz
V
h m W Q
2 2
2 2
! !
! !
Turbines and compressors convert
between thermal energy and work
Turbines and compressors convert
between thermal energy and work
Turbines output work from a
decrease in fluid enthalpy
Compressors and pumps
increase fluid enthalpy by doing
work on the fluid
0
0
0
No heat exchange if
sufficiently insulated
Kinetic energy change can often
(but not always) be ignored
0
Small device so neglect
potential energy changes
0
( )
1
1
]
1

,
_

+
2 2
2
2
,
e i
e i out turb
V V
h h m W
!
!
( )
1
1
]
1

,
_

+
2 2
2 2
,
i e
i e in comp
V V
h h m W
!
!
turb
W
!
out
comp
W
!
in
ME 321 Chapters 1-8, Review of Thermo I
46
Throttling Valve Devices Cause Large
Pressure Drops in Fluid
Throttling Valve Devices Cause Large
Pressure Drops in Fluid
Throttling processes are
regarded as constant enthalpy
processes
The temperature of an ideal gas
does not change during a throttling
(h =constant) process since h =h (T)

,
_

+ +

,
_

+ +
i
i
av
i i e
e
av
e e out in
gz
V
h m gz
V
h m W Q
2 2
2 2
! !
! !
0
No time for
significant heat
transfer
0
0
For incompressible flows density,
area and mass flow rate are
constant, hence no k.e. change
0
Small device so neglect
potential energy changes
0
0
No work is done
by or on
throttling device
ME 321 Chapters 1-8, Review of Thermo I
47
( )
( )
e
e
e
e
h h
h h
y
h y h y
m
m
h m m h m h m

+ +
+ +
1
2
2 1
2
1
2 1 2 2 1 1
1 yh ,
: rates flow mass inlet of ratio the find to
!
!
! ! ! !
T-Elbow Serves as Mixing Chamber for
Hot and Cold Water Steams
T-Elbow Serves as Mixing Chamber for
Hot and Cold Water Steams
Mixing devices have more
than one inlet mass flow rate
Work, Heat transfer, ke and pe
are usually neglected
The T-ebow of an
ordinary shower
serves as the mixing
chamber
for hot- and cold-
water streams.
{ }
e e
h m h m h m h m
! ! ! !
+ + ....
3 3 2 2 1 1
ME 321 Chapters 1-8, Review of Thermo I
48
Heat Transfer Via Heat Exchanger
Depends on System Selection
Heat Transfer Via Heat Exchanger
Depends on System Selection
The heat transfer associated with a heat exchanger may be zero or nonzero
depending on how the system is selected
ME 321 Chapters 1-8, Review of Thermo I
49
Steady Flow: Putting it into a system
Condenser
Boiler
High-P
Turbine
Pump
1
2
Low-P
Turbine
3
5
4
T
v
1
2
3
4
q
out
w
turb,out
q
in
w
pump, in
5
P
2,3
P
5,1
( )
2 3 ,
1 2 1 2 ,
1 5 ,
5 3 ,
h h q
P P v h h w
h h q
h h w
in boiler
in pump
out cond
out turb




A steam cycle is a good example
This is the Rankine cycle
ME 321 Chapters 1-8, Review of Thermo I
50
Steam Power Plants, a Common Heat Engine Steam Power Plants, a Common Heat Engine
Boiler and condenser
are two-phase
thermal energy
reservoirs
Some heat must be
rejected to condenser
Net work is given by
w
turb
-w
pump
ME 321 Chapters 1-8, Review of Thermo I
51
Thermal Efficiency Thermal Efficiency
Even the Most Efficient Heat
Engines Reject Most Heat as
Waste Heat
Performance measures are given
by:
Thermal efficiency is then
For this example
input Required
output Desired
P erformance
in
out
in
out net
th
Q
Q
Q
W
1
,

% 40 40 . 0
th

ME 321 Chapters 1-8, Review of Thermo I

52
The Kelvin-Plank Statement The Kelvin-Plank Statement
A heat-engine cycle cannot be completed without rejecting
some heat to a low-temperature sink
The Kelvin-Planck Statement of the 2nd Law
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
ME 321 Chapters 1-8, Review of Thermo I
53
Basic Components of a Refrigeration
System in Typical Conditions
Basic Components of a Refrigeration
System in Typical Conditions
ME 321 Chapters 1-8, Review of Thermo I
54
Refrigerators are designed to
remove heat from a cooler space
and push it into a warmer one
Work must be done to transfer heat
to a warmer reservoir
The efficiency for these kind of
devices is called a Coefficient of
Performance (COP)
In this case the low temperature
reservoir is the source and the high
temperature reservoir is the sink
Refrigerators Objective:
Remove Q
L
from the Cooled Space
1
1
,


L H in net
L
R
Q Q W
Q
COP
ME 321 Chapters 1-8, Review of Thermo I
55
Heat pump are used to heat
buildings by removing heat
from the cold outdoors
Work must be done to do this
This work typically requires
less energy than does resistive
heating
And thus
Heat Pumps Objective:
Supply Heat Q
H
into the Warmer Space
Heat Pumps Objective:
Supply Heat Q
H
into the Warmer Space
H L in net
H
HP
Q Q W
Q
COP

1
1
,
1 +
R HP
COP COP
ME 321 Chapters 1-8, Review of Thermo I
56
A Refrigerator That Violates Clausius
Statement of the Second Law
Not impossible to transfer heat
from cold to hot objects, it just
requires work
The Clausius Statement of the 2nd Law
It is impossible to construct a device that
operates in a cycle and produces no effect other
than the transfer of heat from a lower-
temperature body to a higher-temperature body.
ME 321 Chapters 1-8, Review of Thermo I
57
Execution of the Carnot Cycle
in a Closed System
Execution of the Carnot Cycle
in a Closed System
reversible isothermal heat addition
reversible adiabatic expansion
reversible isothermal heat rejection
reversible adiabatic compression
ME 321 Chapters 1-8, Review of Thermo I
58
P-v Diagram of the Carnot Cycle P-v Diagram of the Carnot Cycle
ME 321 Chapters 1-8, Review of Thermo I
59
Development of Clausius inequality
The first law gives:
C R C
dE Q W
Since the cyclic device is totally reversible the
following ratio rule holds
T
Q
T Q
T
Q
T
Q
T
T
Q
Q
R R
R
R R R

or , or ,
The combined system first law then is:
C R C
dE
T
Q
T W

For a complete cycle of the combined system

0 dE since ,
c
T
Q
T W
R C

Observing the combined system we see that
W
C
cannot be positive or Kelvin-Planck is
violated and T
R
must be positive so

Inequality Clausius the 0

T
Q
ME 321 Chapters 1-8, Review of Thermo I
60
Entropy change Entropy change
The entropy change between
two specific states is the same
whether the process is reversible
or irreversible

,
_

2
1
rev
T
Q
S S S

1 2
Integrating the definition of
entropy gives:
This integration must be done over
a reversible path, even if the actual
path is irreversible
Note that the change in entropy is
defined. A reference for entropy
must be established. (3rd law)
T
Q
dS

( ) 0
2 1
2
1
1
2
2
1
+ +

S S
T
Q
T
Q
T
Q
For 1-2 irreversible, 2-1 int. rev:
ME 321 Chapters 1-8, Review of Thermo I
61
The entropy change of an isolated
system is the sum of the entropy
changes of its components, and is
never less than zero
The Entropy Change of an I solated System
The inequality can be modeled as an equality
by adding an entropy generation term:
0
, 0
2
1
1 2

+
+

isolated
gen total surr sys gen
gen sys
S
S S S S S
S
T
Q
S S S

Note that unlike S, S
gen
is not a
property, but totally dependent
upon the path between the two
states

2
1

T
Q
is treated as entropy transfer
due to heat transfer across
the boundary, some physics
texts consider it -S
surr
ME 321 Chapters 1-8, Review of Thermo I
62
The T-s diagram The T-s diagram
The T-s diagram is a useful
diagram.
For internally reversible
processes, integrating under it
yields q
rev
For non-quasi-equilibrium
processes we cannot integrate
directly over the process path
We will deal with non-quasi-
equilibrium process in some
cases with isentropic
efficiencies
( )
kg
kJ
K kg
kJ
q
s s T q
T
q
s
rev
rev
rev
770 5 - 6.7 K 453
) ( ,
1 2
2
1

1
2
ME 321 Chapters 1-8, Review of Thermo I
63
Heat Transfer for I nternally Reversible Processes Heat Transfer for I nternally Reversible Processes
Remember, the area under
the curve on a T-s diagram
is equal to the heat transfer
only for internally
reversible processes
For a complete cycle of
internally reversible
processes the enclosed area
is the net heat transfer (and
by 1st law argument, also
the net work)
Counter clockwise is
positive heat in or work out
d
T
S
Net heat (Q
in
-Q
out)
Heat in (Q
in
)
Heat out (Q
out
)
ME 321 Chapters 1-8, Review of Thermo I
64
System Entropy Constant During Reversible,
adiabatic (isentropic) Process
System Entropy Constant During Reversible,
adiabatic (isentropic) Process
Since there is no heat transfer the
entropy transferred by heat transfer
from the boundary is zero.
Since there are no irreversibilities,
the S
gen
term is also zero
Isentropic technically means
constant entropy, but is taken to
imply an adiabatic, internally
reversible process in engineering
applications

+
2
1
1 2 gen sys
S
T
Q
S S S

T
s
1
2
An isentropic
process
ME 321 Chapters 1-8, Review of Thermo I
65
Development of TdS equations Development of TdS equations
Consider a reversible piston-
cylinder device
An incremental amount of heat, Q
is added, while an incremental
amount of boundary work, W is
done by the piston
Q
W
or
since
or ,
,
int
int int
VdP, dH TdS
VdP PdV dU dH
PdV dU TdS
PdV W TdS Q
dU W Q
rev int rev
rev rev

+ +
+




The results deal with properties only and thus are valid as
differential equations for both reversible and irreversible processes
Pdv du Tds +
vdP dh Tds
ME 321 Chapters 1-8, Review of Thermo I
66
Use of TdS equations Use of TdS equations
These two equations are known as the first and second
Tds or Gibbs equations
They can be rearranged to give differential changes in
entropy
These will be useful in determining relationships when we know a
relationship between du or dh and T, or for ideal gases
Pdv du Tds +
vdP dh Tds
T
Pdv
T
du
ds +
T
vdP
T
dh
ds

+
2
1
2
1
T
Pdv
T
du
s
ME 321 Chapters 1-8, Review of Thermo I
67
I ncompressible liquids and solids I ncompressible liquids and solids
For incompressible liquids and solids the specific
volume is constant, hence dv=0
T
Pdv
T
du
ds +

,
_

2
1
v
that so
,
T
u
definition by since
T
dT c
s
dT c du c
v
v v
For many cases involving small temperature
differences c
v
= constant = c or c
avg
In these cases:

,
_

2
1
1
2
1 2
ln
T
T
c
T
dT
c s s
avg avg
ME 321 Chapters 1-8, Review of Thermo I
68
I deal gases I deal gases
For ideal gases
T
Pdv
T
du
ds +
T
vdP
T
dh
ds
1
2
2
1
1 2
ln ) (
v
v
R
T
dT
T c s s
v
+

1
2
2
1
1 2
ln ) (
P
P
R
T
dT
T c s s
P

v
dv
R
T
dT
T c ds
v
+ ) (
P
dP
R
T
dT
T c ds
P
) (
Integration gives
P
R
T
v
v
R
T
P
dT T c T dh dh
dT T c T du du
p
v




) ( ) (
) ( ) (
ME 321 Chapters 1-8, Review of Thermo I
69
Case 1: I deal gas w/ constant specific heats Case 1: I deal gas w/ constant specific heats
If C
v
and C
P
are constant over a temperature range (or an
average value is assigned for an approximation) the
integration is done easily
1
2
2
1
1 2
ln ) (
v
v
R
T
dT
T c s s
v
+

1
2
2
1
1 2
ln ) (
P
P
R
T
dT
T c s s
P

These can also be stated on molar (rather than mass) basis

1
2
1
2
, 1 2
ln ln
v
v
R
T
T
c s s
av v
+
1
2
1
2
, 1 2
ln ln
P
P
R
T
T
c s s
av p

1
2
1
2
, 1 2
ln ln
v
v
R
T
T
c s s
u av v
+
1
2
1
2
, 1 2
ln ln
P
P
R
T
T
c s s
u av p

ME 321 Chapters 1-8, Review of Thermo I
70
Case 2: I deal gas w/ variable specific heats Case 2: I deal gas w/ variable specific heats
Using the equation involving c
P
we develop an ideal gas
function that accounts for the first term on the R.H.S.
1
2
2
1
1 2
ln ) (
P
P
R
T
dT
T c s s
P

This function is not the entropy of the gas

It is used to easily tabulate the change of entropy of a gas
due to the change in temperature
Entropy is a function of two independent variables even
for an ideal gas
The resulting equation is:
1
2
1 2 1 2
ln ) (
P
P
R s s s s
o o

T
P
o
T
dT
T c s
0
) (
!
ME 321 Chapters 1-8, Review of Thermo I
71
Case 2: I deal gas w/ variable specific heats Case 2: I deal gas w/ variable specific heats
In a constant pressure process, the change in s
o
equates to
the change in entropy
Note that, except for
air, these values are
tabulated on a molar
basis
where
1
2
1 2 1 2
ln ) (
P
P
R s s s s
o o

1
2
1 2 1 2
ln ) (
P
P
R s s s s
u
o o

T
P
o
T
dT
T c s
0
) (
!
ME 321 Chapters 1-8, Review of Thermo I
72
I sentropic I deal Gas Relationships --
Case 1: Constant Specific Heats
I sentropic I deal Gas Relationships --
Case 1: Constant Specific Heats
For an isentropic process s
2
= s
1
Given this relationship we can come up with some shortcut formulas
for isentropic processes of ideal gases with constant specific heats
1
2
1
2
, 1 2
ln ln
v
v
R
T
T
c s s
av v
+
1
2
1
2
ln ln 0
v
v
R
T
T
c
v
+
Remember that for ideal gases c
v
and c
p
are functions of temperature
only, regardless of pressure or specific volume
( )
dT
du
T
u
c
dT
dh
T
h
c RT T u pv T u T h
v
v
p
p

,
_

,
_

+ + , , ) ( ) (
R c c or RdT dT c dT c
v p v p
+ + ,
ME 321 Chapters 1-8, Review of Thermo I
73
I sentropic I deal Gas Relationships --
Case 1: Constant Specific Heats
I sentropic I deal Gas Relationships --
Case 1: Constant Specific Heats
Introducing the specific heat ratio, k = c
p
/c
v
1
2
1
2
1
2
1
2
1
2
ln ln ln ln ln 0
v
v
c
c c
v
v
c
R
T
T
v
v
R
T
T
c
v
v p
v
v

+
( )
( ) 1
1
2
1
2
1
2
1
2
ln 1 ln

,
_

k
v
v
T
T
v
v
k
T
T
1
2
1
1
2

,
_

k
v
v
T
T
Using the const. specific heat relation based on the 2nd Tds equation:
1
2
1
2
1
2
1
2
1
2
ln ln ln ln ln 0
P
P
c
c c
P
P
c
R
T
T
P
P
R
T
T
c
p
v p
p
p

,
_

1
2
1
2
ln
1
ln
P
P
k
k
T
T
k
k
P
P
T
T
1
1
2
1
2

,
_

And equating
these two gives:
k
v
v
P
P

,
_

2
1
1
2
ME 321 Chapters 1-8, Review of Thermo I
74
The I sentropic Relations of I deal Gases The I sentropic Relations of I deal Gases
The isentropic relations of ideal gases
are valid for the isentropic processes of
ideal gases only
ME 321 Chapters 1-8, Review of Thermo I
75
I sentropic I deal Gas Relationships --
Case 2: Variable Specific Heats, Pressure ratio
I sentropic I deal Gas Relationships --
Case 2: Variable Specific Heats, Pressure ratio
For an isentropic
process s
2
= s
1
1
2
1 2 1 2
ln ) (
P
P
R s s s s
o o

( )
( ) R s
R s
e
P
P
R
s s
P
P
P
P
R s s
o
o
R
s s
o o
o o
o o
1
2
1
2
1 2
1
2
1
2
1 2
exp
exp
ln , ln ) ( 0
1 2

The quantity exp(s

o
/R) is called the pressure ratio, P
r
Do not confuse it with the Reduced Pressure P
R
{=P/P
c
}
This quantity is a function of temperature only and is
tabulated
It is only valid for isentropic processes
1
2
1
2
r
r
P
P
P
P

ME 321 Chapters 1-8, Review of Thermo I

76
I sentropic I deal Gas Relationships --
Case 2: Variable Specific Heats, Volume Ratio
I sentropic I deal Gas Relationships --
Case 2: Variable Specific Heats, Volume Ratio
1 2 1
2 1 2
1
2
2 1
1 2
1
2
,
r r r
r
P
T
P
T
v
v
v T
v T
P
P
P
P

The quantity T/P
r
is called the volume ratio, v
r
This quantity is a function of temperature only and is
tabulated
It is only valid for isentropic processes
Since volume and pressure are linked by
temperature in ideal gases a relationship
also exists for volume
1
2
1
2

r
r
v
v
v
v

ME 321 Chapters 1-8, Review of Thermo I

77
P-v Diagram for steady flow reversible processes P-v Diagram for steady flow reversible processes
Notice also that for
negligible changes in ke
and pe the reversible
steady flow work is the
area to the right of the
curve on the P-v diagram
w
rev

2
1
vdP w
rev
ME 321 Chapters 1-8, Review of Thermo I
78
P-v Diagrams of I sentropic, Polytropic, and
I sothermal Compression Processes
P-v Diagrams of I sentropic, Polytropic, and
I sothermal Compression Processes
By looking at the P-v diagrams
for isentropic, polytropic and
isothermal compression
processes, it is seen that the
isentropic process does not
require the least work
Consequently, when
compressors are discusses we
will have a different measure
for efficiency than for turbines
ME 321 Chapters 1-8, Review of Thermo I
79
The h-s (Mollier) Diagram for Water The h-s (Mollier) Diagram for Water
Valuable for analyzing
turbine performance
Critical point is not at
the vertical peak
Notice that lines of
constant temperature
become horizontal as
fluid behaves more like
an ideal gas
ME 321 Chapters 1-8, Review of Thermo I
80
I sentropic Turbine Efficiency I sentropic Turbine Efficiency
Actual turbines do less work
than isentropic turbines
operating between the same
two pressures
The ratio of the actual work
to the isentropic work is the
isentropic turbine efficiency
The isentropic efficiency is
easily seen on the Mollier
Diagram
s isentropic
act
T
h h
h h
w
w
2 1
2 1

ME 321 Chapters 1-8, Review of Thermo I
81
I sentropic Nozzle Efficiency I sentropic Nozzle Efficiency
A similar efficiency is
defined for nozzles operating
between to pressures
The ratio of the actual outlet
kinetic energy to that of an
isentropic nozzle is the
isentropic nozzle efficiency
This efficiency is also easily
seen on the Mollier Diagram
s s
T
h h
h h
V
V
2 1
2 1
2
2
2
2

Where the last equality hold if
inlet velocity is small
ME 321 Chapters 1-8, Review of Thermo I
82
I sentropic Compressor Efficiency I sentropic Compressor Efficiency
Actual compressors require
more work input than
isentropic turbines operating
between the same two
pressures
The ratio of the isentropic
work requirement to the
actual work the isentropic
compressor efficiency
This efficiency is also easily
seen on the Mollier Diagram
1 2
1 2
h h
h h
w
w
s
actual
isentropic
Cs

ME 321 Chapters 1-8, Review of Thermo I
83
I sothermal Compressor Efficiency I sothermal Compressor Efficiency
A reduced work input can
actually be required for
isothermal compressors
The ratio of the isothermal
work requirement to the
actual work the isothermal
compressor efficiency
This efficiency can not be
clearly shown on the Mollier
Diagram
( )
1 2
1 2
1 2
ln
h h
P P RT
h h
q
w
w
isoth
actual
isothermal
Ct

ME 321 Chapters 1-8, Review of Thermo I
84
Entropy Generation During Heat Transfer Entropy Generation During Heat Transfer
Graphical representation of entropy generation during a heat
transfer process through a finite temperature difference
ME 321 Chapters 1-8, Review of Thermo I
85
Work depends upon the final state, the initial state
and the process path
Consider the case where
The initial state is given
The process is reversible
The final state is in equilibrium with the surroundings
This case results in the maximum possible work
output from the initial state
The state at which the system is in equilibrium
with the surroundings is the dead state
The McGraw-Hill Companies, Inc.,1998
Maximum Work Available and the Dead State Maximum Work Available and the Dead State
ME 321 Chapters 1-8, Review of Thermo I
86
The dead state provides a convenient reference
from which to analyze the usefulness of a quantity
of energy
(Thermo-mechanical) dead state is assumed to be:
z = 0 (sea level)
V = 0 (at rest with respect to Earths surface)
P = P
0
= 101.325 kPa = 1 atm
T = T
0
= 25
o
C = 77
o
F = 298 K
u
0
= u(T
0
, P
0
), h
0
= h(T
0
, P
0
), s
0
= s(T
0
, P
0
)
Chemical availability - models standard sea level
atmosphere constituents (O
2
, CO
2
, N
2
, H
2
O) at
normal concentrations
The McGraw-Hill Companies, Inc.,1998
- The Dead State -
A State of Equilibrium with the Surroundings
- The Dead State -
A State of Equilibrium with the Surroundings
ME 321 Chapters 1-8, Review of Thermo I
87
Exergy represents
maximum useful work a
system will deliver while
going from a given state to
the dead state
Surroundings work
Not all boundary work is
useful
Work loss in pushing the
environment
Other work forms are
considered 100% useful
The McGraw-Hill Companies, Inc.,1998
Useful Work and Surrounding Work Useful Work and Surrounding Work
P
0
V
2
-V
1
( )
1 2 0
V V P W
surr

surr u
W W W
ME 321 Chapters 1-8, Review of Thermo I
88
Reversible work is the maximum
useful work between two states
Exergy represents maximum
useful work a system will deliver
while going from a given state to
the dead state
If an object delivers less than the
maximum work the remaining
work potential is exergy destroyed,
or irreversibility, I
Exergy has same units as work and
energy
Exergy is always positive, even for
states below the dead state
The McGraw-Hill Companies, Inc.,1998
Reversible work, Exergy, I rreversibility Reversible work, Exergy, I rreversibility
For systems with a moving
boundary:
W
u,out
=W
act,total
- W
surr
- I
If final state is dead state, then
X =W
act,rev
- W
surr
=W
u,act
+I
ME 321 Chapters 1-8, Review of Thermo I
89
Derivation of Exergy Definition
Consider a combined system of
closed system and its
environment
Only work leaves the combined
system
First TdS eq. for combined
system gives
W
C
W
Q
u
e
, v
e
, s
e
, T
e
(=T
0
) , P
e
(=P
0
) fixed
U
e
, V
e
, S
e
vary due to
interactions with closed system,
but are governed by 1st TdS eq.
e e e
V P S T U
0 0
( ) V V V
V V V
e
cm e C

+
0
0
The final system state is the
dead state 0
W
C
is then given by
( ) [ ] ( ) ( ) [ ]
e e e C C
V P S T E U U E U E W + +
0 0 0 0
ME 321 Chapters 1-8, Review of Thermo I
90
Derivation of Exergy Definition
Continuing with the equation for combined system work:
W
C
W
Q
The entropy change for the combined system equals the
entropy generation
( ) ( ) [ ]
e C
S T V V P U E W +
0 0 0 0
( )
e gen C
S S S S S +
0
( ) ( ) ( ) [ ]
gen C
S T S S T V V P U E W
0 0 0 0 0 0
+
If process is reversible the S
gen
is zero
and work is maximized. It is this
maximum work that we call exergy
( ) ( ) ( )
0 0 0 0 0
S S T V V P U E X +
ME 321 Chapters 1-8, Review of Thermo I
91
Types of Exergy Types of Exergy
Exergy is a property that depends upon two
independent intensive properties and the
definition of the dead state
Specific exergy may be better explained by
combining exergy due to component energies
( ) ( ) ( )
( )
( ) ( )
0 0 0
0 0
0 0 0 0 0
e
2
ke
x : enthalpy of Exergy
x : energy flow of Exergy
x : energy internal of Exergy
x : energy potential of Exergy
2
x : energy kinetic of Exergy
s s T h h
v P P v P Pv
s s T v v P u u
gz pe
V
ke
h
pv
u
p


+


"
ME 321 Chapters 1-8, Review of Thermo I
92
Kinetic and Potential Exergy Kinetic and Potential Exergy
Mechanical forms of energy are equivalent to
exergy since work is 100% recoverable
2
2
1
V m
"
mgz
W
shaft
2
x
2
ke
V
ke
"
gz pe
p

e
x
ME 321 Chapters 1-8, Review of Thermo I
93
The Exergy of I nternal Energy The Exergy of I nternal Energy
Consider a stationary closed
system reversibly transferring
work and heat, ending at the
dead state
Heat transfer energy is captured
by a reversible heat engine
The exergy of a specified mass at a
specified state is the useful work
that can be produced as it
undergoes a reversible process to
the state of the environment
( ) Q dV P W Q W dU
u b
+
0 ,
dS T Q W
T
Q
Q
T
T
W
0 HE HE
+

,
_

, dS , 1
0
dS T dV P dU W W
0 u b, HE
+ +
0

( ) ( ) ( )
0 0 0 0 0 ,
s s T v v P u u x w
u u tot
+
ME 321 Chapters 1-8, Review of Thermo I
94
The Exergy of Flow Work The Exergy of Flow Work
Flow work is the work
done pushing fluid into
and out of an open
system
Not all flow work is
useful. Some is pushing
against at atmosphere
The exergy of flow of work is
the useful work that would be
delivered by an imaginary
piston in the flow section
( )v P P v P Pv x
Pv 0 0

ME 321 Chapters 1-8, Review of Thermo I
95
The Exergy of Enthalpy The Exergy of Enthalpy
The exergy associated with a fluids enthalpy is the
combination of the exergies associated with
internal energy and flow work
For a point in a flow system, enthalpy combines
internal energy with flow work
( ) ( ) ( ) ( )v P P s s T v v P u u x x x
Pv u h 0 0 0 0 0 0
+ + +
( ) ( )
0 0 0
s s T h h x
h

Pv u h +
ME 321 Chapters 1-8, Review of Thermo I
96
The Energy and Exergy contents of
(a) a Fixed Mass and (b) a Fluid System
The Energy and Exergy contents of
(a) a Fixed Mass and (b) a Fluid System
J ust as energy terms can be
combined into a single
property, e, so can exergy
For flow systems we
include flow work exergy
( is called methalpy)
These shorten future
equations by using or ,
which are symbols for the
intensive property exergy
at a state or a point in the
flow
gz
V
u e + +
2
2
"
( ) ( ) ( ) gz
V
s s T v v P u u + + +
2
2
0 0 0 0 0
"

gz
V
h + +
2
2
"

( ) ( ) gz
V
s s T h h + +
2
2
0 0 0
"

ME 321 Chapters 1-8, Review of Thermo I

97
Exergy Transfers Exergy Transfers
In order to get a exergy balance equation
we must consider exergy transfer from the
system to the surroundings
For exergy transfer by heat, assume heat is
transferred into reversible heat engine

,
_

Q
T
T
X
heat

0
1
If objects temperature remains constant:
Q
T
T
X
heat

,
_

0
1
Exergy transfers by work and mass follow simply

'

forms) k (other wor

work) (boundary
W
W W
X
surr
work
m X
trans. mass
ME 321 Chapters 1-8, Review of Thermo I
98
The Exergy of a Cold Medium The Exergy of a Cold Medium
Exergy of a cold medium is
still positive even though it is
below T
0
Consider ideal gas at constant
P
0
but below T
0
(Baggie of
cold air).
The exergy of a cold
medium is also a positive
quantity since work can
be produced by
transferring heat to it
( ) ( )

,
_

+
0
0 0 0
ln
T
T
c T T T R T T c x
p v
( )
1
1
]
1

,
_

0
0 0
ln
T
T
T T T c x
p

'

<
>
1
]
1

,
_

0
0
0
T T for negative
T T for positive
1
T
T
c
dT
dx
p
( ) ( ) ( )
0 0 0 0 0
s s T v v P u u x
u
+
ME 321 Chapters 1-8, Review of Thermo I
99
The Transfer and Destruction of Exergy
During Heat Transfer
The Transfer and Destruction of Exergy
During Heat Transfer
The same amount of heat
leaves a boundary as enters it
More entropy leaves a
boundary than enters during
heat transfer across a finite
temp. difference
Exergy is destroyed during
heat transfer
The transfer and destruction of exergy
during a heat transfer process through
a finite temperature difference
ME 321 Chapters 1-8, Review of Thermo I
100
The Exergy Balance The Exergy Balance
General:
Exergy balance for any system undergoing any process
can be expressed as
General, rate form:
ME 321 Chapters 1-8, Review of Thermo I
101
Exergy Transference Exergy Transference
Exergy is transferred into or out of a
control volume by mass as well as by
heat and work transfer
The explicit statement for the energy
balance equation for control volumes
is given by:
ME 321 Chapters 1-8, Review of Thermo I
102
Exergy Transference Exergy Transference
Exergy transfer for a closed system can be determined as well.
The explicit statement for the energy balance equation for
closed systems is given by:
( ) [ ] ( )
1 0 1 2 0
0
1

,
_

2 gen
k
k
k
X S T V V P W Q
T
T
dt
dX
S T
dt
dV
P W Q
T
T
sys
gen
sys
k
k
k

1
]
1

,
_

! ! !
0 0
0
1
Note that
destroyed exergy ility irreversib
0
I S T
gen
ME 321 Chapters 1-8, Review of Thermo I
103
Second Law of Efficiency Second Law of Efficiency
The second law of efficiency is a measure of the performance of a device
relative to its performance under reversible conditions
( )

'

all
supplied Exergy
destroyed Exergy
1
supplied Exergy
recovered Exergy
pumps) heat and tors (refrigera
devices) consuming (work
engines) (heat W W
rev u
rev
u rev
rev th, th
II COP COP
W W

ME 321 Chapters 1-8, Review of Thermo I

104
The Second-Law Efficiency of All Reversible
Devices is 100%
The Second-Law Efficiency of All Reversible
Devices is 100%