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Chapter 3
Properties of Pure Substances

Sep. 25 Sep. 27, 2012
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3.1 Pure Substance () 3.1 Pure Substance ()
A substance that has a fixed chemical composition
is not.
A substance that has a fixed chemical composition
throughout is called a Pure Substance.
Pure Substance:
- N2, O2, gaseous Air
- A mixture of liquid and gaseous water is a pure
substance, but a mixture of liquid and gaseous Air is not.
3-1
3-2

2
Solid:
The attractive and repulsive forces between the molecules
Solid:
-The molecules in a solid are kept at their positions by the
large spring like intermolecular forces.
-The attractive and repulsive forces between the molecules
tend to maintain them at relatively constant distances
from each other.
Liquid: Groups of molecules move about each other.
Gas: Molecules move about at random.
3.2 Phases of a Pure Substance

3.2 Phases of a Pure Substance
()
3
3.2
3-3

3-4

4
(a) (b) (c)
3-5 (a)
(b)
(c)
5
Phase Rule (no chemical reaction) Phase Rule (no chemical reaction)
Remind:
: # of intensive (internal) properties need to fix the
Remind:
F=C-P+2
- F : # of intensive (internal) properties need to fix the
state of the system
- C: # of components
- P: # of phases
For pure liquid or gas (vapor) F =2 (C=1, P=1)
For un-saturated water F =1 (C=1, P=2)
For triple line (points) F =0 (C=1, P=3)
6
2
3.3 Phase-Change Processes of Pure Substance
()
1 atm
20

()
100

()

100

(
)

()
7
3-11 (1atm)
T-v
3-16
T- v
8
3.3 Phase Change Processes of Pure Substance

3.3 Phase-Change Processes of Pure Substance
- Terminologies ()
Compressed liquid () or a subcooled liquid ( Compressed liquid () or a subcooled liquid (
) : A liquid that is not about to vaporize.
Saturated liquid () : A liquid that is about to
vaporize.
Saturated vapor () : A vapor that is about to
condense.
Saturated liquid-vapor mixture () : the
liquid and vapor phases coexist in equilibrium.
Superheated vapor () : A vapor that is not about
to condense
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3.3 Phase-Change Processes of Pure Substance 3.3 Phase-Change Processes of Pure Substance
Saturated temperature (), T : At a given Saturated temperature (), Tsat: At a given
pressure, the temperature at which a pure substance
changes phase.
Saturated pressure (), Psat: At a given
temperature, the pressure at which a pure substance
changes phase.
Latent heat (): the amount of energy absorbed or
released during a phase-change process.
Latent heat of fusion (): the amount of energy
absorbed during melting.
Latent heat of vaporization (): the amount of
energy absorbed during vaporization.
10 11
Some Consequences of T
sat
and P
sat
Dependence
The temperature of liquid
nitrogen exposed to the
atmosphere remains constant
at 196C, and thus it
maintains the test chamber at
196C.
The variation of
the temperature of
fruits and
vegetables with
pressure during
vacuum cooling
from 25C to 0C.
In 1775, ice was
made by
evacuating the air
space in a water
tank.
3-1
()
3-12 -()
3-2
()
12
3
3-16, 17 (P > Pc )
()

(Critical Point), Tc (),
Pc ()
kg kJ u u
kg m v
MPa P
K C T
g f
c
c
c
/ 7 . 2015
/ 003106 . 0
064 . 22
647 95 . 373
3
= =
=
=
= =
13
3.4 Property Diagrams () for Phase-

3.4 Property Diagrams () for Phase-
Change Processes
The T-v diagram: The T-v diagram:
- Critical point: the point at which the saturated liquid
and saturated vapor states are identical.
- Saturated liquid line:
- Saturated vapor line:
- Compressed liquid region:
- Superheated vapor region:
- Saturated liquid-vapor mixture region:
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- P-v
P-v
T-v

15
3-20 (a) P-v , (b)() P-v
-
16
(triple point)

()
() (sublimation)
Note: , (triple point)(triple points line)
[T, P, fixed; need (x
v
,x
l
) or (v,x
l
) to
locate the point].
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3-24
P-v-T

3-25
P-v-T
3-23 P-T
P-v-T surface
P(v,T), T(P,v), v(T,P),
or z(x,y)
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4
19
3.5 Property Tables () 3.5 Property Tables ()
Table A-4: Table A-4:
Saturated water - Temperature table
Table A-5:
Saturated water - Pressure table
Table A-6:
Superheated water
Enthalpy, H
H= U + PV (kJ)
h= u + Pv (kJ/kg)
Entropy, S
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3.5
3-26
u + Pv
3-27 (P) (V)
kPa x m
3
= 10
3
N/m
2
x m
3

= 10
3
Nm= 10
3
J = 1 kJ
u
h = u + pv
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3-28 A-4
22 23 24
5
3-31 3-3 P-v
Example 3-3 Example 3-3
25 26
3-40 A-6
h
h
27
Liquid-vapor equilibrium
Liquid at P,T Liquid at P,T Surroundings
Vapor at P,T
Vapor at P,T Vapor at P,T
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3-32 x

quality ()
vapor liquid
vapor
total
vapor
m m
m
m
m
x
+
= =
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3-34 P-v T-v

3-35 v
TP vf vg
f g fg
f g g f t
g g f g f g f f g f
g g f f t
g f t g f
v v v
v v m v m
v m v m v m v m v m m
v m v m v m
m m m V V V
= + =
+ =
+ + = +
+ =
+ = + =
,
) (
) ( ) (
,
fg f xv v v
g f fg f
v v xv v v : Note + = + =
30
6
, xv v v
fg f
+ =
g f
g t g f t f
g g f f t
g f t g f
v x v x 1 v
v m m v m m v
v m v m v m
m m m V V V
+ =
+ =
+ =
+ = + =
) (
) / ( ) / (
,
Similar to U (u), H (h), S (s)
g f fg f
g f fg f
g f fg f
xs s x 1 xs s s
xh h x 1 xh h h
xu u x 1 xu u u
+ = + =
+ = + =
+ = + =
) (
) (
) (
a
g
> a
f
or a
fg
>0
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3-42 P T P>P
sat
@T T <T
sat
@P
(or v < vf , u < uf , h < or > hf at a given P or T)

32

For more accurate

) (
@ @ @ T sat T f T f
P P v h h + ~
) (
,
@ @ @
@
@ @ @ @
T sat T f T f
T f
T f T sat T f T f
P P v h h
v v
v P h u vP u h
+ ~
~
= + =
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3 - 41 3-8 T-u

~ 0.34% deviation
Example 3-8 Example 3-8
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3.6 The Ideal-Gas Equation of State

3.6 The Ideal-Gas Equation of State
()
Equation of state:

Equation of state:
Any equation that relates the pressure, temperature, and
specific volume of a substance.
Gas: The vapor phase of a substance
Vapor: A gas that is not far from a state of condensation
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Fluids and gases
Aliquid will take the
shape of its container
but exhibits a free
surface.
Aliquid will take the
shape of its container
but exhibits a free
surface.
Agas will fill its container
completely and does not
exhibit a free surface.
Agas will fill its container
completely and does not
exhibit a free surface.
gas gas
container gas
P T
V V
,
=
36
7
This implies:
(1) very little molecular interaction (p = 0),
(2) molecules are point masses, i.e.,
molecules occupy zero volume.
mRT PV
, T NR PV
u
=
=
N / V v , T R v P
m / V v , RT Pv
u
= =
= =
3.6 The Ideal-Gas Equation of State 3.6 The Ideal-Gas Equation of State
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R lbmol / lbf ft
K kmol / kJ . R
u
=
=
1545
314 8
The universal gas constant
3.6 The Ideal-Gas Equation of State 3.6 The Ideal-Gas Equation of State

The gas constants, R = R R = R
uu
/M /M
M, M, molar molar mass, mass, the the mass mass of of 11 mole mole
of of substance substance in in grams, grams, or or 11 kmol kmol in in
kilograms kilograms.. [in [in SI SI
]]..
For For Air Air
MM == 28 28 kg/kmol kg/kmol == 28 28 g/mole g/mole
== 28 28 lbm/lbmol lbm/lbmol (definition) (definition)
mole / molecules .
23
10 023 6
38
The ideal gas state surface a 3 dimensional surface
Ideal Gas State Surface
pp
V TT
39
3-45

40
3-48 3-10
kg .
K ) )( K kg /( m N . (
m ) )(
m
N
(
K ) )( K kg /( kJ . (
m ) )( kPa (
RT
PV
m
mRT PV
3 140
273 25 10 287 0
6 5 4 10 100
273 25 287 0
6 5 4 100
3
3
2
3
3
=
+

=
+

= =
=
Example 3-10 Example 3-10
41
The perfect gas
R c c
t tan cons c
RT
Pv
v P
v
=
=
=1
1 =
RT
Pv The ideal gas
42
8
3-47
([(v

-v

)/v

]
100)1
3.7 Compressibility Factor- A Measure of

3.7 Compressibility Factor- A Measure of
Derivation from Ideal-Gas Behavior
43
3.7 Compressibility Factor- A Measure of

3.7 Compressibility Factor- A Measure of
Derivation from Ideal-Gas Behavior
Compressibility Factor () , Z Compressibility Factor () , Z
Z = Pv/RT
Z = v
actual
/v
ideal
Ideal gas: Z = 1
Real gases:
Z > 1
Z = 1
Z < 1
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Real Gases
P
1
Z
T
1

T
2

T
3

T
1
< T
2
< T
3

Ideal Gas
T R
v P
u
RT
Pv
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3.7 Compressibility Factor- A Measure of
Derivation from Ideal
3.7 Compressibility Factor- A Measure of
Derivation from Ideal-Gas Behavior
The normalization: The normalization:
- Reduced pressure, P
R

P
R
= P/ P
cr
- Reduced temperature, T
R

T
R
= T/ T
cr
The principle of corresponding states:
The Z factor for all gases is approximately the same at
the same reduced pressure and temperature.
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Reduced pressure and temperature
Generalized Compressibility Chart Generalized Compressibility Chart
T
R1
T
R2
Z
P
R
P
R
= P/P
critical
T
R
= T/T
critical
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Generalized Compressibility Chart

Reduced pressure and temperature
Corresponding State (PR, TR)
cr
R
P
P
P =
cr
R
T
T
T =
48
9
1.

2. (TR>2)

3.

49
Errors ; ideal gas ~ 20%

Errors ; ideal gas ~ 20%
charts ~ 2%
Example 3-11 Use of Generalized Charts determine v Example 3-11 Use of Generalized Charts determine v
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3-52 PR vR (A-15 figure)
cr
R
P
P
P =
cr
R
T
T
T =
cr
actural
cr cr
actural
R
v
v
,
P / RT
v
v
volume specific reduced pseudo
= =

, T = 350 C, v = 0.035262 m3/kg,

,
, T = 350 C, v = 0.035262 m3/kg,
P = ?
Sol. Exact 7.0 MPa, Z chart 6.84 MPa,
Ideal gas 8.15 MPa
Example 3-12 Use of Generalized Charts determine P Example 3-12 Use of Generalized Charts determine P
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3.8
3-55

Pages 141-144
RT b v
v
a
P = + ) )( (
2
van der Waals equation of state
a/v
2
: intermolecular force
b: volume occupied by the molecular
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3-56




0 = |
.
|

\
|
c
c
= cr T T
v
P
0
2
2
=
|
|
.
|

\
|
c
c
=
cr
T T
v
P
cr
cr
P
T R
a
64
27
2 2
=
cr
cr
P
RT
b
8
=
for van der Waals equation of state
53
3-57 P-v-T

54
10
3-58 (%)
= [(v

-v

)/v

] 100
55

11, 26, 35, 44, 56, 68, 77, 84, 93, 103, 112, 123

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