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Thermodynamics I CH - 3 - Pure-Substance
Thermodynamics I CH - 3 - Pure-Substance
Pure Substances
3.1 Pure Substances
Pure Substance
In Chemistry you defined a pure substance as an Air
element or a compound
Something that can not be separated N2
Pure substance
Example of Non-Pure Substance Air Gas
Piston cylinder
device –
Liquid Water maintains
constant
pressure
T Phase Change
Processes on a
5 T-v diagram
3
2 4
1
v
Phase Change Processes on a T-v diagram
Consider a piston-cylinder device with water
inside at 20oC and 1 atm pressure .
At this P and T, water is called compressed
(or subcooled) liquid state.
Compressed liquid means that it is not about
to vaporize.
The system is heated and the piston is allowed A liquid that is about
to float and thus the pressure will be constant. to vaporize is called
Saturated Liquid.
T and v will increase until the system reaches
1000 C at which any addition of heat will
cause some of the liquid to vaporize
The temperature at which a pure substance
changes phase is called the saturation
temperature, Tsat.
At Tsat, Liquid and vapor phases are in
equilibrium.
A substance between
saturated liquid (state 2) and
Adding more heat will cause saturated vapor (state 4) is
called saturated liquid-vapor
boiling to start. Liquid gradually mixture.
evaporates (state 3) but
temperature will remain constant.
The only change is the increase in
the specific volume (v) until it
reaches state 4 (saturated vapor).
A vapor that is about to
Heating the system further, will condense is called
Saturated vapor.
increase both the temperature and
specific volume (state 5). This
single-phase state is called
“Superheated vapor”
Repeat this experiment for higher
pressures.
Similar curves will be obtained but
at higher sat. temperature.
Note that the sat. liquid specific
volume (vsat,l ) will increase while
the sat. vapor specific volume
(vsat,g ) will decrease
Saturation Temperature and Pressure
Water at a pressure of 101.325 kPa, Tsat is
100oC. Conversely, at a temperature of
100oC, Psat is 101.325 kPa.
Latent heat: fusion and vaporization.
The magnitude of the latent heats depend
on the temperature or pressure at which
the phase change occur.
Saturation Temperature and Pressure
At a given pressure, the temperature at which a
pure substance changes phase is called the
saturation temperature. Likewise the pressure.
vsat,l and vsat,g will be the same and we
Critical Point speak of Pcrit, Tcrt, and vcrit.
liquid
Solid
3.3. Property Diagrams
P-T diagram
(or Phase diagram)
The P-T diagram is often called
phase diagram since all three
phases are separated by three lines,
namely the sublimation line
(between solid and vapor regions),
the vaporization line (between
liquid and vapor regions), and the
melting line (between solid and
liquid).
T
P-v-T surfaces
You can plot P, T, V on a
three dimensional graph
Top view
v
P iew P
v
v P
P Tv
iew
v T
3.4. Thermodynamic
Tables
Thermodynamics Tables
The relationship among thermodynamic properties are too complex to be
expressed in simple equations and thus, properties are measured and/or
calculated and then presented in a tabulated form.
In single-phase regions, any
Compresse Liquid
two properties will fix the
Table A7
state.
In two phase regions, any
(o ea 6
ap d
two properties (except P and
er rh A
)
r v te
or
at pe le
w Su T ab
T) will fix the state. P and T
Saturated liquid-
are dependent on each other. vapor region
Table A4 T entry
Table A5 P entry
Table A8
Saturated ice-vapor
Enthalpy − A Combination Property
In the analysis of certain types of processes, particularly in power
generation and refrigeration, we frequently encounter the combination of
internal energy U, and pressure-volume product PV. That is
H U PV h u pυ
Before 1930, h was referred to as heat content or total heat.
After 1930, it is referred to as enthalpy (from the Greek word enthalpien
which means to heat)
Saturated Liquid and Saturated Vapor States
Table A-4
Saturated liquid-vapor
mixture falls under the P-v
(or T-v) dome.
Its properties can be obtained
from Water Tables A-4 and
A-5
T
t.
ns
co
=
P
vf vg
Saturated Liquid and Saturated Vapor States
Table A-5
Pressure is listed in the left
column as the independent
variable.
Use whichever table is
convenient.
v fg v g v f
h fg hg h f
Enthalpy of vaporization or
latent heat
the amount of energy needed
to vaporize a unite mass of
saturated liquid at a given
temperature or pressure
Example 3-1:
Saturated Liquid and Saturated Vapor
A rigid tank contains 50 kg of saturated liquid water at 90 oC. Determine
the pressure in the tank and the volume of the tank.
m m m
f g total
Derivation: Gas
V V f Vg P or T mg vg
mv m f v f mg v g Liquid
mf v f
( m m g )v f m g v g
v (1 x)v f xvg
v v f x (v g v f )
v v f xv fg
where v fg v g v f f f g g
Average Properties
In the saturated mixture region, the average value of any intensive property
y is given as:
y y f x( yg y f )
y f x y fg
where f stands for saturated liquid and g for saturated vapor. For example:
Average Properties
In the saturated mixture region, the average value of any intensive property y is
given as:
y y f x( yg y f )
01
yf x y fg = yg
where f stands for saturated liquid and g for saturated vapor. For example:
The average properties of the mixtures are always between the values of the
saturated liquid and the saturated vapor properties. That is
y f yavg y g
X=0 X=1
Saturated Liquid-Vapor Mixture
T
co
t.
ns T Tsat at given P
P=
T
Tsat
P Psat at given T
vg v v
v f v v g at given P or T
vf
P u f u u f at given P or T
Psat h f h h f at given P or T
T=
co
ns
t.
P saturated mixture
vg v v
Quality is an intensive property
Example 3- 3:
Saturated Liquid-vapor mixture (continued)
A rigid tank contains 10 kg of water at 90oC. If 8 kg of water is in the
liquid form and the rest is in the vapor form, determine (a) the pressure in
the tank and (b) the volume of the tank.
T=
co
ns
t.
vg v v
Superheated Vapor
T
t. T Tsat at given P
ns
co
P=
P Psat at given T
Tsat
vf vg v v
v v g at given P or T
P u u g at given P or T
Psat T=
co
h h g at given P or T
P
ns
t.
superheated vapor
vg v v
Compressed liquid Table A-7
In the region to the left of the saturated liquid line, a substance exists as
compressed liquid.
v
Compressed Liquid
T
t.
ns
T Tsat at given P
co
P=
T
Tsat
P Psat at given T
vf vg v v v v f at given P or T
u u f at given P or T
h h f at given P or T
compressed liquid
A general approximation
In the absence of compressed liquid data, a general approximation is to treat
compressed liquid as saturated liquid at the given temperature. Such that
T Acceptable P Wrong
.
pa
5M 5 Mpa T=2
P=
64
264
80
T=
80
v vf v v vf v
Approximate value Wrong value
Precise value Precise value
y y f @T
If the compression is moderate, the properties do not vary significantly with
pressure. But they do vary with temperature
Linear Interpolation
A B
100 5
130 y
200 10
130 100 y 5
200 100 10 5
Linear Interpolation (Continued)
Now
T (0C) Psat(MPa)
y y1 x x1
X1= 140 y1= 0.3615
X = 143 y=? y 2 y1 x 2 x1
X2= 145 y2= 0.4154
x x1
y y1 ( y2 y1 )
x2 x1
143 140
Psat 0.3615 ( 0.4154 0.3615)
145 140
Example 3-6:
Determine the internal energy of
compressed liquid water at 80oC
and 5 MPa using (a) data from the
pa
5M
compressed liquid table and (b)
saturated liquid data. What is the 263.99
error involved in the second case? 80
80
(Answers: 333.82 kJ/kg, 334.97 kJ/kg, 0.34%)
Reference State and Reference Values
The values of u, h, and s cannot be measured directly, and they are
calculated from measurable properties using the relations between
thermodynamic properties. However, those relations give the changes in
properties, not the values of properties at specified state.
For water, the state saturated liquid at 0.01oC is taken as the reference
state, and the internal energy and entropy are assigned zero values at that
sate.
For refrigerant 134a, the state saturated liquid at -40oC is taken as the
reference state, and the enthalpy and entropy are assigned zero values at
that state.
In thermodynamics we are concerned with the changes in properties, and
the reference chosen has no consequences in the calculations.
Examples
Example 3-7 (optional)
Example 3-8
Example 3-9 (Homework)