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Water liquid–vapor saturation
curve: During a phase-change
process, pressure and temperature
are obviously dependent properties,
and there is a definite relation
between them, that is, Tsat = f(Psat).
A plot of Tsat versus Psat, such as
the one given for water in Fig. 3–12,
is called a liquid–vapor saturation
curve. A curve of this kind is
characteristic of all pure substances.
Tsat increases with Psat. Thus, a substance at higher pressures boils at
higher temperatures.
Pressure Cooker: In the kitchen, higher boiling temperatures mean
shorter cooking times and energy savings. Meat , for example, may take 2
to 3 h to cook in a regular pan that operates at 1 atm pressure, but it may
take only 40 min in a pressure cooker operating at 3 atm absolute
pressure (corresponding boiling temperature: 134°C).
Boiling Temperature change with elevation:
The atmospheric pressure, and thus the boiling temperature of water,
decreases with elevation. Therefore, it takes longer to cook at higher
altitudes than it does at sea level (unless a pressure cooker is used). For
example, the standard atmospheric pressure at an elevation of 2000 m is
79.50 kPa, which corresponds to a boiling temperature of 93.3°C as
opposed to 100°C at sea level (zero elevation). The variation of the boiling
temperature of water with altitude at standard atmospheric conditions is
given in Table 3–2. For each 1000 m increase in elevation, the
boiling temperature drops by 3°C. Note that the atmospheric pressure
at a location, and thus the boiling temperature, changes slightly with the
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weather conditions. But the corresponding change in the boiling
temperature is no more than about 1°C.
T −ν Diagram
The phase-change process of water at 1 atm pressure was described in
detail
Now we repeat this process at different pressures to develop the T-v
diagram.
Let us add weights on top of the piston until the pressure inside the
cylinder reaches 1MPa. At this pressure, water has smaller specific
volume. The process has a path similar to 1atm, but boiling starts at
much higher temperature (180C). the specific volume of the saturated
liquid is larger, specific volume of saturated vapor is smaller than 1atm.
So the horizontal line is shorter.
Critical point:
As we increase the pressure, this line shrinks more and it becomes a point
when the pressure reaches 22.06 MPa. This point is called critical point.
At this point the saturated liquid and saturated vapor are
identical.
We call the temperature, pressure and specific volume, the critical
temperature, critical pressure and critical specific volume. For the water
these values are: (on the figure)
Supercritical pressures
At pressures above the critical pressure, there is not a distinct phase
change process. The specific volume of the material increases
continually, and at all times we have only one phase of material. At
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the end, it is a vapor, but we can never tell when the change has
happened.
Above the critical state, there is no line that separates the compressed
liquid region and the superheated vapor region. However, usually we call
the substance superheated vapor at temperatures above the critical
temperature and compressed liquid at temperatures below the critical
temperature.
T-V diagram of Pure Substance
The saturated liquid states in Fig. 3–16 can be connected by a line called
the saturated liquid line, and saturated vapor states in the same figure
can be connected by another line, called the saturated vapor line. These
two lines meet at the critical point, forming a dome as shown in Fig. 3–18.
All the compressed liquid states are located in the region to the left of
the saturated liquid line, called the compressed liquid region. All the
superheated vapor states are located to the right of the saturated
vapor line, called the superheated vapor region.
In these two regions, the substance exists in a single phase, a liquid or a
vapor.
All the states that involve both phases in equilibrium are located
under the dome, called the saturated liquid–vapor mixture region, or the
wet region .
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P-V diagram of Pure Substance
The general shape of the P-v diagram of a pure substance is very much
like the T-v diagram, but the T constant lines on this diagram have a
downward trend.
Consider again a piston–cylinder device that contains liquid water at 1
MPa and 150°C. Water at this state exists as a compressed liquid. Now the
weights on top of the piston are removed one by one so that the pressure
inside the cylinder decreases gradually.
The water is allowed to exchange heat with the surroundings so its
temperature remains constant. As the pressure decreases, the volume
of the water increases slightly.
When the pressure reaches the saturation-pressure value at the
specified temperature (0.4762 MPa), the water starts to boil.
During this vaporization process, both the temperature and the
pressure remain constant, but the specific volume increases.
Once the last drop of liquid is vaporized, further reduction in pressure
results in a further increase in specific volume.
Notice that during the phase-change process, we did not remove any
weights. Doing so would cause the pressure and therefore the
temperature to drop [since Tsat= f (Psat)], and the process would no
longer be isothermal.
When the process is repeated for other temperatures, similar paths are
obtained for the phase-change processes.
Connecting the saturated liquid and the saturated vapor states by a curve,
we obtain the P-v diagram of a pure substance, as shown in Fig. 3–19.
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P-T Diagram
For example, lets consider we have a piston cylinder and we put some ice
in it. The pressure is 101 kPa , the temperature is 0 °F or -17.7 °C. I start
to heat it, temperature will increase, volume will increase, and the
pressure is constant since the mass of the piston is constant. we continue
to heat the system till we reach the 0°C. After this point if we continue
heating the system, the ice will start to melt. In this period of melting the
temperature will stay constant at 0°C, pressure is constant, volume will ?
decrease. In some materials when the melting happens, the volume
increases. Water is one example of these material. So the volume will
decrease. If I continue heating, the last particle of ice will convert to water.
We continue to heat the system, the temperature will increase, pressure is
constant and volume will decrease till 4 °C, after that volume will
increase.
Lets consider another experiment. We have ice in the cylinder and the
piston applies a pressure of 0.0505 psi or 348.2 Pascal. The temperature is
on 0 °F (or -18 °C). we start heating the system, till the temperature
reaches 20°F (-7°C). After this point heating the system, the ice will be
converted to vapor directly which is called Sublimation. At this point
pressure will be constant, temperature will be constant as well since the
phase change is happening.
Lets consider another condition for the experiment.
The mass of the piston selected in a way that the pressure inside the
system is 0.08854 psi or 610.4 Pa. The temperature is 0°F. We start
heating the system until we reach the 32.02° F temperature. When we
reach this temperature at this pressure, a portion of the the solid will
convert to liquid and some part to vapor. This point where we have all
three phases together is called the triple point.
On the EF line, first we have solid, at melting point temperature is
constant, volume is decreasing since we said it is water and pressure is
constant till the last part of the ice is melt. Then the temperature will
increase the pressure is constant and volume will increase after the 4°C.
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when we reach the saturation point, at this point the temperature is
constant, pressure is constant volume will increase until all of the liquid is
converted to vapor and then the temperature will start to increase.
The next line is starting from A it is heated till 20°F. then the solid is
converted to vapor. At this point temperature is constant. When all of the
solid is converted to vapor, the temperature of vapor will increase
The third test start with ice when we reach the triple point, some part of
solid is converted to liquid and some part to vapor. At this point the
temperature will stay constant until all of the material is changed to vapor.
Then heating the system temperature will increase.
The Figure shows the P-T diagram of a pure substance. This diagram is
often called the phase diagram since all three phases are separated from
each other by three lines. The sublimation line separates the solid and
vapor regions, the vaporization line separates the liquid and vapor
regions, and the melting (or fusion) line separates the solid and liquid
regions. These three lines meet at the triple point, where all three phases
exist in equilibrium. The vaporization line ends at the critical point
because no distinction can be made between liquid and vapor phases
above the critical point. Substances that expand and contract on freezing
have different trend only in the melting line on the P-T diagram.
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Equation of State
Property tables provide very accurate information about the properties,
but they are bulky and vulnerable to typographical errors. A more
practical and desirable approach would be to have some simple relations
among the properties that are sufficiently general and accurate. Any
equation that relates the pressure, temperature, and specific volume of a
substance is called an equation of state. Property relations that involve
other properties of a substance at equilibrium states are also referred to
as equations of state. There are several equations of state, some simple
and others very complex. The simplest and best-known equation of state
for substances in the gas phase is the ideal-gas equation of state. This
equation predicts the P-v-T behavior of a gas quite accurately within some
properly selected region.
Gas and vapor are often used as synonymous words. The vapor phase of a
substance is customarily called a gas when it is above the critical
temperature. Vapor usually implies a gas that is not far from a state of
condensation.
f R=1 J/mol/K , it means that for one mole of gas, increasing the
temperature by 1 Kelvin (K) will provide exactly 1 Joule (J) of energy to the
gas.
In other words: For every mole of gas, the energy required to raise the
temperature by 1 K is 1 Joule.
R: The gas constant R is different for each gas. But R is constant for all
gases.
M: The molar mass M can simply be defined as the mass of one mole
ν : Specific molar volume
ν=Mν N ν=NMν=mν=V
m=NM
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Ideal Gas:
A gas can be considered as ideal gas in low pressures and very high
temperatures.
In ideal gas, the molecules collisions and interactions are elastic. So they
do not loose energy in their collisions. So the molecular attraction should
be very low. So low pressure and high temperature is required. If we check
the P-v diagram of the water, so at lower pressure and far away from the
critical point. So it should be very superheated. The air in the condition we
are living at is considered to be superheated, because it is far from being
condensed.
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The Tables
ν fg =ν g−ν f
Lets consider we have both liquid and vapor both in the system. The
specific volume of liquid is a small value and the specific volume of the
vapor is very high.
Sometimes we need to talk about the specific volume of the whole
system. So we have to divide the whole volume to the whole mass.
V =V f +V g
V sys
ν sys= ν m =mf ν f + mg ν g msys=mν sys=ν
msys sys sys
mf mg m−m g mg
ν= νf + νg= νf + νg
m m m m
(
ν= 1−
mg
m ) m m
ν f + g ν g x= g ν= ( 1−x ) ν f + x ν g
m m
ν=ν f + x ν fg
ν=ν g−( 1−x ) ν fg
These equations relates the specific volume of the system to the specific
volume of the material and quality. If I have the saturated temperature, I
can find the saturated pressure then we can know specific volumes of the
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liquid and vapor. These values are the properties of the material and they
do not depend on the how much of material I have in the system. If I have
the quality, which is the property of the system, then using one of above
three equations we can find the specific volume of the whole system.
The B-1-2 is a similar table. Only difference is : the first column is
pressure. So if the pressure is given you should check the table 1 for each
material. If the pressure is given you will use the 2 table.
B1-3 Superheated vapor
In the state of saturated liquid-vapor, the temperature and pressure are
dependent parameters. How they are dependent? By the vapor pressure
curve we had for the saturation pressure and saturation temperature. But
in the region of superheated vapor, P and T are independent parameters.
So in table -3 we have to define the table for each pressure separately. It
starts from 10kPa. In this pressure different temperatures and
corresponding specific volume is written next to temperature.
For each pressure the temperature starts from the saturation
temperature. For example 45.81 for 50 kPa. The specific volume for the
first row is the vg.
As I said the first temperature for any pressure is the saturation
temperature. How about the last value of the temperature? What do you
think?
We do not have any limit for this, but after a specific temperature the
vapor is ionized (ayonayzd) so we will not have a compressible fluid
anymore. So we can consider the temperature till a point that the vapor is
not ionized.
B 1-4 : Compressed Liquid
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The table is for compressed liquid. Similarly to the B1-3, you can see
different sections for different pressures. Because similar to the in this
region pressure and temperature are independent properties. But it starts
with high pressures like 500 kPa. While it was starting from 10 kPa for
superheated vapor.
Why the pressures are started from very high values here? Since the
liquids are not compressible fluids. So the volume and specific volume
change with small pressures are not very significant to be listed in the
table. But when the pressures are very high the volume variation can be
important.
B1-5:
It is related to the sublimation line, below the triple point where we have
the solid-vapor phase changes.
The first column is temperature, the second is pressure ( they are
dependent), vi is the specific volume of solid, vg is the specific volume of
the vapor, and the vig is the difference between the vi and vg.
We can write the equations we had for vf,vg and x . just we can replace
the f with I which is for solid. x the quality is the same and it is the mass of
gas divided by the total mass.
Question?
What if the pressure and temperature that is given is not in the table. For
example 10kPa (superheated vapor) and 62 degree Celsius? Any idea?
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Extending the Diagrams to Include the Solid Phase
The two equilibrium diagrams developed so far represent the equilibrium
states involving the liquid and the vapor phases only. However, these
diagrams can easily be extended to include the solid phase as well as the
solid–liquid and the solid–vapor saturation regions. The basic principles
discussed in conjunction with the liquid–vapor phase-change process
apply equally to the solid–liquid and solid–vapor phase-change processes.
Most substances contract during a solidification (i.e., freezing) process.
Others, like water, expand as they freeze. The P-v diagrams for both
groups of substances are given in Figs. 3–21 and 3–22. These two
diagrams differ only in the solid–liquid saturation region. The T-v diagrams
look very much like the P-v diagrams, especially for substances that
contract on freezing.
The fact that water expands upon freezing has vital consequences in
nature. If water contracted on freezing as most other substances do, the
ice formed would be heavier than the liquid water, and it would settle to
the bottom of rivers, lakes, and oceans instead of floating at the top. The
sun’s rays would never reach these ice layers, and the bottoms of many
rivers, lakes, and oceans would be covered with ice at times, seriously
disrupting marine life.
We are all familiar with two phases being in equilibrium, but under some
conditions all three phases of a pure substance coexist in equilibrium (Fig.
3–23). On P-v or T-v diagrams, these triple-phase states form a line called
the triple line. The states on the triple line of a substance have the same
pressure and temperature but different specific volumes. The triple line
appears as a point on the P-T diagrams and, therefore, is often called the
triple point. The triple-point temperatures and pressures of various
substances are given in Table 3–3. For water, the triple-point temperature
and pressure are 0.01°C and 0.6117 kPa, respectively. That is, all three
phases of water coexist in equilibrium only if the temperature and
pressure have precisely these values. No substance can exist in the liquid
phase in stable equilibrium at pressures below the triple-point pressure.
The same can be said for temperature for substances that contract on
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freezing. However substances at high pressures can exist in the liquid
phase at temperatures below the triple-point temperature. For example,
water cannot exist in liquid form in equilibrium at atmospheric pressure at
temperatures below 0°C, but it can exist as a liquid at -20°C at 200 MPa
pressure. Also, ice exists at seven different solid phases at pressures
above 100 MPa.
There are two ways a substance can pass from the solid to vapor phase:
either it melts first into a liquid and subsequently evaporates, or it
evaporates directly without melting first. The latter occurs at pressures
below the triplepoint value, since a pure substance cannot exist in the
liquid phase at those pressures (Fig. 3–24). Passing from the solid phase
directly into the vapor phase is called sublimation. For substances that
have a triple-point pressure above the atmospheric pressure such as solid
CO2 (dry ice), sublimation is the only way to change from the solid to
vapor phase at atmospheric conditions.
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Example 6:
A tank with volume of 0.4 m2contains m=2 kg of saturated water. The
pressure inside the tank is measured to be 6 ¯¿. Find the mass and
volume for the water and vapor.
ν=ν g−( 1−x ) ν fg
v is the specific volume of the system. vf , vg and vfg are the specific
volume of liquid, vapor and their difference respectively. These values
are dependent on the pressure and temperature.
The pressure is given in the question so we can use the B1-2 table. If the
temperature were given we would use the B1-1.
P= 600 kPa
and ν fg =0.3146
3 3 3
m m m
ν f =0.001101 ν g=0.3157
kg kg kg
We have the volume and mass of the system. So we can calculate the ν of
the system:
3
V 0.4 m
ν= = =0.2
m 2 kg
ν=ν g−( 1−x ) ν fg
and
0.3157−0.2
0.2=0.3157− (1−x ) 0.3146 1−x= =0.3678 x=0.6322
0.3146
mg m−mf mf
x= = =1−
m m m
mf =( 1−x ) m=0.3678∗2=0.7356 kg
mg =x∗m=0.6322∗2=1.2644 kg
Vf 3
νf = V =ν f ∗mf =0.001101∗0.7356=0.000809 m
mf f
Vg 3
ν g= V g =ν g∗mg =0.3157∗1.2644=0.3992 m
mg
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Example 7:
A rigid tank contains saturated water at 100 kPa. Determine the
volume percentage of liquid when the system is heated and
reaches the critical point.
In the saturated condition the temperature and pressure is dependent
properties. It is the same for the critical point and the critical pressure and
critical temperature are dependent. So for each liquid we have a specific
critical pressure and critical temperature pair.
The tank is rigid so it does not deform and we do not have volume change
during the process. So the pressure will increase instead and it will reach
the critical point that we know its temperature and pressure. As we
discussed at the critical point, we do not have evaporation at a constant
temperature. So at one point the liquid is evaporated. So at this point we
have a homogeneous fluid inside the tank. we can say that the specific
volume of the vapor and liquid are the same at critical point since . If you
check this in B1-1 or B1-2 tables you can see that the ν f is equal to ν g and
the ν fg is equal to zero. So the specific volume of the system will be equal
to ν g or ν f which is 0.003155 kg/m3.
In addition the volume and mass of the system is constant. So the specific
volume at 100kPa is also 0.003155.
kg
v=v f =v g =0.003155 3
m
kg kg
@ P=100 kPa ν f =0.001043 3
ν g=1.69400 3
m m
ν=ν f + x ν fg 0.003155=0.001043+ x (1.69400−0.001043 )
x=0.0012475 1−x=0.998752
X is the percentage of mass of vapor. But we want to find the percentage
of volume
V f ( 1−x )∗V
mf =( 1−x ) m =
νf ν
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V f ( 1−x )∗ν f 0.998752∗0.001043
= = =0.33=33 %
V ν 0.003155
So at 100kPa pressure 1/3 of the tank was liquid and the remaining was
filled with gas.