Thermodynamic Properties

Copyright (c) 2005 by
John Wiley & Sons, Inc

ThermoNet
Thermodynamics: An Integrated Learning System
P.S. Schmidt, O.A. Ezekoye, J.R. Howell and D.K. Baker
Chapter 3: Thermodynamic Properties
of Pure Substances
A snowflake at high
magnification. The
solid phase of water
in one of its forms.

(Courtesy of Kenneth G.
Libbrecht, Cal Tech)
Chapter 3: Thermodynamic Properties of Pure Substances
3.1 STATE PRINCIPLE
Any two independent intensive thermodynamic
properties are sufficient to describe the state of a
system containing a single pure substance.
3.2 Intensive and Extensive Properties
The value of an extensive property is dependent of
the mass of the system.
The value of an intensive property is independent
of the mass of the system.
Partition box
P
o
, T
o
,
V
o
, m
o

P
1

T
1

V
1

m
1

P
2

T
2

V
2

m
2

P
0
= P
1
= P
2
Intensive Prop
T
0
= T
1
= T
2
Intensive Prop
V
0
= V
1
= V
2
Extensive Prop
m
0
= m
1
= m
2
Extensive Prop
Try specific volume:
v = V/m v
0
= v
1
= v
2
Intensive Property
3.2 Intensive and Extensive Properties
Property Extensive Intensive
Mass m -
Temperature - T
Pressure - P
Volume V v = V/m (specific volume)
Internal Energy U u = U/m (specific internal
energy)
Enthalpy H h = H/m (specific enthalpy)
Any extensive property can be made intensive
(specific) by dividing by mass.
3.3 Pure Substances
Are composed of a single
chemical species (e.g., either O
2

or CO
2
but not a mixture of O
2
and
CO
2
).
May exist in more than one phase
(e.g., solid and liquid)
A mixture of
snow, ice, liquid water
and water vapor is a
pure substance.
3.3.1 Phase Change and P-v-T Surface
Constant Pressure Heating in Piston-Cylinder at P = 1 atm
Constant Pressure Heating in Piston-Cylinder at P = 2 atm
Regions on T-v Diagram
Note directions of Isobars
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Regions on P-v Diagram
Note directions of Isotherms
Three-Dimensional P-v-T Surface
3.4 Liquid-Vapor Tables
For Ideal Gases (treated later):
Pv = RT
Very simple and accurate relation
No similar relation exists for liquids, saturated
liquid vapor mixtures or superheated vapors
Typically superheated vapors do not obey the
ideal gas law.
Use data tabulated based on T and P
Compressed Liquid Tables
Saturated Liquid-Vapor Tables
Superheated Vapor Tables
3.5 Saturation and Quality
Property Notation (Subscripts):
L = Saturated Liquid (e.g., v
L
and u
L
)
V = Saturated Vapor (e.g., v
V
and u
V
)
LV = Difference between saturated vapor and liquid
values (e.g., v
LV
= v
V
- v
L
)
SAT = Saturated Mixture (T
SAT
and P
SAT
)
Quality (x): Mass Fraction of Saturated Vapor
Specific Volume (v) of Saturated Liquid Vapor Mixture
with quality x
v = v
L
+ xv
V
Quality of Saturated Liquid Vapor Mixture with Specific
Volume (v)

L L
V L LV
v v v v
x
v v v

= =

Determine Phase if:
P = 100 kPa and v = 0.001000 m
3
/kg
P = 100 kPa and T = 100
0
C
P = 100 kPa and v = 1.0000 m
3
/kg
3.6 Compressed (Subcooled) Liquids
P = 1000 kPa & T = 105
0
C
P
SAT
(105
0
C) = 122.35 kPa
Since P > P
SAT
(T)
Compressed Liquid
T = 70
0
F & P = 14.7 psia
T
SAT
(14.7 psia) = 212
0
F
Since T < T
SAT
(P)
Subcooled Liquid
Subscript CL = Compressed Liquid: e.g., v
CL

3.6 Incompressible Liquid Approx (ICL)
v
CL
(70
0
C, 5000 kPa) = 0.001020 m
3
/kg
v
L
(70
0
C) = 0.00102 m
3
/kg
v
L
(5000 kPa) = 0.00129 m
3
/kg
v
CL
(T,P) ~ v
L
(T) ICL
3.6 Incompressible Liquid Approx (ICL)
v
CL
(T,P) ~ v
L
(T)
u
CL
(T,P) ~ u
L
(T)
h
CL
(T,P) ~ h
L
(T) + v
L
(T) [P P
SAT
(T)]
Recall h = u + Pv h sensitive to P
If P ~ P
SAT
(T)
h
L
(T) >> v
L
(T) [P P
SAT
(T)]
h
CL
(T,P) ~ h
L
(T)
3.7 Superheated Vapor
T = 400
0
C & P = 3000 kPa
T
SAT
(3000 kPa) = 233.9
0
C
Since T > T
SAT
(P) Superheated Vapor
3.7 Superheated Vapor
3.8 Gases
Molecules are relatively far apart
Do not feel one anothers presence except
during collisions
Have a low density
Are highly compressible
In next two slides, compare
Liquid-Vapor working fluid in steam engine
Gas working fluid in gas turbine
3.8 Gases
3.8 Gases
3.9 Ideal Gas Law
Universal Gas Constant ( ): All gases have same
value.
Particular Gas Constant (R): Each gas has a
unique value.
R
3.10 Compressibility Factor
R
CR
R
CR
Pv
Z
RT
P
P
P
T
T
P
=
=
=
Use if not IGL and vapor tables not available
3.11 Other Equations of State
Van der Waals equation

Redlich-Kwong Equation

Benedict-Webb-Rubin Equation of State

Virial Equation of State
2
v
a
b v
RT
P
=
( )
RK
1/2
RK
RK
a RT
P
v b
v v b T
=
+
2
0
0 0
2 2 3 6 3 2 2
C RT 1 (bRT a) a 1 / v
P (B RT A ) c exp
v
T v v v v T v
o +
| | | |
= + + + +
| |
\ . \ .
2
RT B C
P 1 ......
v v
v
| |
= + + +
|
\ .
3.12 Internal Energy and Enthalpy
Internal Energy
If not an ideal gas, u = u(T,P)
If ideal gas, u = u(T) = u(P)
Enthalpy
Recall h = u + Pv
For an Ideal Gas, Pv = RT h = u(T) + RT
Therefore for ideal gas, h = h(T) = h(P)
T, u and h are dependent properties for ideal
gases
3.13 Heat Capacities and Specific Heats
Approximately,

Heat capacity (C
V
) and specific heat capacity
(c
V
) for constant volume process

Heat capacity (C
P
) and specific heat capacity
(c
P
) for constant pressure process

Energy
C
T
A
=
A
v v
v v
U u
C and c
T T
c c
| | | |
= =
| |
c c
\ . \ .
P P
P P
H h
C and c
T T
c c
| | | |
= =
| |
c c
\ . \ .
3.13 Specific Heats for Ideal Gases
For an ideal gas, h = h(T) = h(P) and

Similarly, for ideal gas u = u(T) = u(V) and
2
1
T
P
P
P
T
h dh
c
T dT
h c dT Always
c
| |
= = =
c
A
|
\ .
}
2
1
T
V
V
V
T
u du
c
T dT
u c dT Always
c
| |
= = =
c
A
|
\ .
}
R = c
P
c
V
For monatomic gases (e.g., He, Ar, Ne)
c
V
= 3R/2 = Constant
c
P
= 5R/2 = Constant

Au = c
V
AT only if c
V
= constant
Ah = c
P
AT only if c
P
= constant
2 2
1 1
T T
V P
T T
u c dT h c dT A = A =
} }
3.13 Specific Heats for Solids and Liquids
For incompressible solids and liquids,
c
P
= c
V

Sometimes denoted as c
2
1
T
T
u h cdT A = A =
}
3.14 Ideal Gas Tables
Unlike steam tables, pressure not tabulated
Use Pv = RT to relate P, v and T
Use tables to relate T, u and h
3.15 Some Other Thermodynamic Properties
Isothermal Compressibility (k)

Coefficient of Thermal Expansion (|)

Joule Thompson Coefficient ()
T
1 v
v P
c
| |
k =
|
c
\ .
P
1 v
v T
c
| |
| =
|
c
\ .
dV
dT dP
V
= | k
h
T
P
c
| |
=
|
c
\ .

Thermodynamic Properties

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Thermodynamic Properties

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Copyright (c) 2005 by

John Wiley & Sons, Inc

Chapter 3: Thermodynamic Properties of Pure Substances

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