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super
= T
super
T
saturation
The other properties are calculated as v super = v
sat
* T
super
/ T
sat
h
super
= h
g
+ Cp (T
super
-T
sat
)
s
super
= s
g
+ Cp log(T
super
/T
sat
)
PHASE DIAGRAMS OF PURE SUBSTANCES
This page explains how to interpret the phase diagrams for simple pure substances -
including a look at the special cases of the phase diagrams of water and carbon
dioxide. This is going to be a long page, because I have tried to do the whole thing
as gently as possible.
The basic phase diagram
What is a phase?
At its simplest, a phase can be just another term for solid, liquid or gas. If you have
some ice floating in water, you have a solid phase present and a liquid phase. If
there is air above the mixture, then that is another phase.
But the term can be used more generally than this. For example, oil floating on water
also consists of two phases - in this case, two liquid phases. If the oil and water are
contained in a bucket, then the solid bucket is yet another phase. In fact, there might
be more than one solid phase if the handle is attached separately to the bucket
rather than molded as a part of the bucket.
You can recognize the presence of the different phases because there is an obvious
boundary between them - a boundary between the solid ice and the liquid water, for
example, or the boundary between the two liquids.
Phase diagrams
A phase diagram lets you work out exactly what phases are present at any given
temperature and pressure. In the cases well be looking at on this page, the phases
will simply be the solid, liquid or vapor (gas) states of a pure substance.
This is the phase diagram for a typical pure substance.
These diagrams (including this one) are nearly always drawn highly distorted in
order to see what is going on more easily. There are usually two major distortions.
Well discuss these when they become relevant.
If you look at the diagram, you will see that there are three lines, three areas marked
"solid", "liquid" and "vapour", and two special points marked "C" and "T".
The three areas
These are easy! Suppose you have a pure substance at three different sets of
conditions of temperature and pressure corresponding to 1, 2 and 3 in the next
diagram.
Under the set of conditions at 1 in the diagram, the substance would be a solid
because it falls into that area of the phase diagram. At 2, it would be a liquid; and at
3, it would be a vapour (a gas).
Moving from solid to liquid by changing the temperature:
Suppose you had a solid and increased the temperature while keeping the pressure
constant - as shown in the next diagram. As the temperature increases to the point
where it crosses the line, the solid will turn to liquid. In other words, it melts.
If you repeated this at a higher fixed pressure, the melting temperature would be
higher because the line between the solid and liquid areas slopes slightly forward.
So what actually is this line separating the solid and liquid areas of the diagram?
It simply shows the effect of pressure on melting point.
Anywhere on this line, there is an equilibrium between solid and liquid.
You can apply Le Chateliers Principle to this equilibrium just as if it was a chemical
equilibrium. If you increase the pressure, the equilibrium will move in such a way as
to counter the change you have just made.
If it converted from liquid to solid, the pressure would tend to decrease again
because the solid takes up slightly less space for most substances.
That means that increasing the pressure on the equilibrium mixture of solid and
liquid at its original melting point will convert the mixture back into the solid again. In
other words, it will no longer melt at this temperature.
To make it melt at this higher pressure, you will have to increase the temperature a
bit. Raising the pressure raises the melting point of most solids. Thats why the
melting point line slopes forward for most substances.
Moving from solid to liquid by changing the pressure:
Moving from liquid to vapor:
In the same sort of way, you can do this either by changing the temperature or the
pressure.
The liquid will change to a vapour - it boils - when it crosses the boundary line
between the two areas. If it is temperature that you are varying, you can easily read
off the boiling temperature from the phase diagram. In the diagram above, it is the
temperature where the red arrow crosses the boundary line.
So, again, what is the significance of this line separating the two areas?
Anywhere along this line, there will be an equilibrium between the liquid and the
vapour. The line is most easily seen as the effect of pressure on the boiling point of
the liquid.
As the pressure increases, so the boiling point increases.
The critical point
You will have noticed that this liquid-vapour equilibrium curve has a top limit that I
have labelled as C in the phase diagram.
This is known as the critical point. The temperature and pressure corresponding to
this are known as the critical temperature and critical pressure.
If you increase the pressure on a gas (vapor) at a temperature lower than the critical
temperature, you will eventually cross the liquid-vapor equilibrium line and the vapor
will condense to give a liquid.
This works fine as long as the gas is below the critical temperature. What, though, if
your temperature was above the critical temperature? There wouldnt be any line to
cross!
That is because, above the critical temperature, it is impossible to condense a gas
into a liquid just by increasing the pressure. All you get is a highly compressed gas.
The particles have too much energy for the intermolecular attractions to hold them
together as a liquid.
The critical temperature obviously varies from substance to substance and depends
on the strength of the attractions between the particles. The stronger the
intermolecular attractions, the higher the critical temperature.
Moving from solid to vapour:
Theres just one more line to look at on the phase diagram. This is the line in the
bottom left-hand corner between the solid and vapour areas.
That line represents solid-vapour equilibrium. If the conditions of temperature and
pressure fell exactly on that line, there would be solid and vapour in equilibrium with
each other - the solid would be subliming. (Sublimation is the change directly from
solid to vapour or vice versa without going through the liquid phase.)
Once again, you can cross that line by either increasing the temperature of the solid,
or decreasing the pressure.
The diagram shows the effect of increasing the temperature of a solid at a (probably
very low) constant pressure. The pressure obviously has to be low enough that a
liquid cant form - in other words, it has to happen below the point labelled as T.
You could read the sublimation temperature off the diagram. It will be the
temperature at which the line is crossed.
The triple point
Point T on the diagram is called the triple point.
If you think about the three lines which meet at that point, they represent conditions
of:
solid-liquid equilibrium
liquid-vapour equilibrium
solid-vapour equilibrium
Where all three lines meet, you must have a unique combination of temperature and
pressure where all three phases are in equilibrium together. Thats why it is called a
triple point.
If you controlled the conditions of temperature and pressure in order to land on this
point, you would see an equilibrium, which involved the solid melting and subliming,
and the liquid in contact with it boiling to produce a vapor - and all the reverse
changes happening as well.
If you held the temperature and pressure at those values, and kept the system
closed so that nothing escaped, thats how it would stay. A strange set of affairs!
Normal melting and boiling points
The normal melting and boiling points are those when the pressure is 1 atmosphere.
These can be found from the phase diagram by drawing a line across at 1
atmosphere pressure.
The phase diagram for water
There is only one difference between this and the phase diagram that weve looked
at up to now. The solid-liquid equilibrium line (the melting point line) slopes
backwards rather than forwards.
In the case of water, the melting point gets lower at higher pressures. Why?
If you have this equilibrium and increase the pressure on it, according to Le
Chateliers Principle the equilibrium will move to reduce the pressure again. That
means that it will move to the side with the smaller volume. Liquid water is produced.
To make the liquid water freeze again at this higher pressure, you will have to
reduce the temperature. Higher pressures mean lower melting (freezing) points.
Now lets put some numbers on the diagram to show the exact positions of the
critical point and triple point for water.
Notice that the triple point for water occurs at a very low pressure. Notice also that
the critical temperature is 374C. It would be impossible to convert water from a gas
to a liquid by compressing it above this temperature.
The normal melting and boiling points of water are found in exactly the same way as
we have already discussed - by seeing where the 1 atmosphere pressure line
crosses the solid-liquid and then the liquid-vapour equilibrium lines
The phase diagram shows that the water would first freeze to form ice as it crossed
into the solid area. When the pressure fell low enough, the ice would then sublime to
give water vapour. In other words, the change is from liquid to solid to vapour. I find
that satisfyingly bizarre!
Measurement of Steam Quality:
The state of a pure substance gets fixed if two independent properties are given.
Thus the pure substance is said to have two degrees of freedom.
Fig 18: T s and h s diagram
Figure shows the values of pressure and temperature would fix up the state. But
when the substance is in the saturation state or two phase region the measured
values of pressure and temperature could apply equally well to saturated liquid point
f and saturated vapor point g. or two mixtures of any quality points x
1
, x
2
or x
3
. of the
two properties, P and T only one is independent; the other is a dependent property.
If the pressure is given the saturation temperature gets automatically fixed for the
substance. In order to fix up the state of the mixture one more property such as
specific volume, enthalpy or composition of mixture or internal energy is required to
be known. Since it is relatively difficult measure the specific volume of the mixture
devices such as calorimeters are used for determining the quality or the enthalpy of
the mixture.
In the measurement of quality, the object is always to bring the state of the
substance from the two phase region to the single phase region or superheated
region where, the pressure and temperature are independent and measured to fix
the state, either by adiabatic throttling or e3lectric heating.
There are four types of calorimeter are common in use namely
1) Separating Calorimeter
2) Throttling Calorimeter
3) Combined separating and throttling calorimeter.
4) Electrical calorimeter.
Separating Calorimeter: the steam whose dryness fraction is to be determined
is very wet then separating calorimeter gives the quality of the steam. A known
quantity of steam is passed through a separating calorimeter as shown. The steam
is made to change direction suddenly, the water being denser than the dry steam is
separated out. The quantity of water, which is separated out, is measured at the
separator. The dry steam coming out of the separator is sent through a condenser
where it is condensed separately.
The dryness fraction of the steam is calculated by weighing the mass of the water
and mass of dry steam after condensation separately.
Throttling Calorimeter: sample of wet steam of mass m at pressure p1 is taken
from the steam main through a perforated sampling tube as shown in the figure.
Fig 19: Throttling calorimeter
Then it is throttled by the partially opened valve to a pressure p
2
measured by a
mercury manometer and temperature T
2
so that after throttling the steam is in the
superheated region. The process is shown on T-s and H-s diagram.
The steady flow energy equation gives the enthalpy after throttling as equal to
enthalpy before throttling. It is a irreversible process hence joined by a dotted line.
Thus the initial state of the steam is p
1
, t1 and its dryness fraction is x1 and the final
state of the superheated steam is p
2
x
2
.
Fig 20: T s and h s diagram for throttling calorimeter
Now h
1
=h
2
h
f1
+x
1
h
fg1
= h
2
x
1
=( h
2
h
f1
) / h
fg1
With P
2
and T
2
being known, h
2
can be found out from the superheated steam table.
The values of h
f
, h
fg
are taken from saturated steam table., thus quality of the wet
steam x
1
can be calculated.
Combined separating and throttling calorimeter:
When the steam is very wet and the pressure after throttling is not low enough to
take the steam to the superheated region then a combined separating and throttling
calorimeter is used for the measurement of quality. Steam from the main is first
passed through a separator as shown in the figure, where some part of the moisture
separates due to sudden change in direction and falls by gravity and partially dry
vapor is then throttled and taken to the superheated region.
Fig 21: Schematic diagram for separating and throttling calorimeter.
As shown in the figure process 1-2 represents moisture separation from the wet
sample of steam at constant pressure P1 and process 2-3 represents throttling to
pressure P
2
withP
2
and T
3
being measured, h
3
can be found out from the
superheated steam table.
h
3
= h
2
= h
f1
+ x
2
h
fg1
Therefore x
2
, the quality of the steam after partial moisture separation can be
evaluated. If m kg of steam is taken through the sampling tube in y seconds, m
1
kg is
separated and m
2
kg is throttled and then condensed to water and collected, we
have
m=m
1
+m
2
.
The mass of dry vapor will be at state2 is x
2
m
2
.
Therefore the quality of the sample of the steam at state1 which ids x1 is given by
x
1
= x
2
m
2
/ (m
1
+ m
2
)
There is one more method of measurement of quality of wet steam by using electric
calorimeter as shown in the figure. The sample of steam is passed in steady flow
through an electric heater. Electrical energy input Q should be sufficient to taken the
steam to the superheated region where pressure P
2
and temperature T
2
are
measured. If I is the current flowing through the heater in amperes and V the
voltage across the coil at steady state Q=VI. If m is the mass of steam taken in t
seconds under steady flow condition then the steady flow energy equation for heater
is given by m
1
h
1
+ Q = m1h
2
Fig 22: Electric calorimeter
Hence h
1
+ Q / m
1
= h
2
. With h
2
,Q and m
1
=being known h1 can be computed. Thus
h
1
= h
f1
+ x1 h
fg1
.
Hence x
1
can be calculated.
1) A steam boiler initially contains 5 m3 of steam and 5 m3 of water at 1 MPa.
Steam is taken out at constant pressure until 4 m3 of water is left. What is the
heat transferred during the process?
Solution:
Fig 23: Steam drum.
At 1 MPa vf = 0.001127 and vg= 0.1944 m3 / kg.
hg=2778.1 kJ/kg uf = 761.68 , ufg = 1822 , ug = 2583.6 kJ/kg
The initial mass of saturated water and steam in the boiler = (Vf /vf) + (Vg / vg) =
[(5/0.001127) + (5/0.1944) ] = [(4.45 * 10
3
) + (25.7) ] kg
Final mass of saturated water and steam = (4/0.001127) +(6/0.1944) = [ (3.55 *
10
3
) + 30.8] kg
Mass of steam taken out of the boiler, ms = [4.45 * 10
3
+ 24.7] - [ (3.55 * 10
3
) + 30.8]
= 894.9 kg
Making an energy balance we have initial energy stored in saturated water and
steam + heat transfer from external source = final energy stored in saturated water
and steam + energy leaving the steam or
U1 + Q =U1 + ms*hg
Assuming that the steam taken out is dry.
Hence 4.45 * 10
3
* 761.68+27.7*2583.6+ Q = 3.55 * 103 *761.68 +30.8 *2583.6
+894.9 * 2778.1
Q = 2425000-685500+13176
Q = 1752676 kJ.
2) Steam flows in a pipeline at 1.5Mpa. After expanding to 0.1MPa in a
throttling calorimeter, the temperature is found to be 120
o
C. Find the quality
of steam in the pipe line. What is the maximum moisture at1.5 MPa that can be
determined with this set-up if least 5
o
C of superheat is required after
throttling for accurate readings?
Fig 24 : h s Diagram
Solution.
At state 2 when p = 0.1 MPa and t = 120
o
C by interpolation,
h
2
= 2716.2 kJ/kg and
p = 1.5 MPa h
f
= 844.89 and h
fg
= 1947.3 kJ/kg
and h
1
= h
2
h
f1
+ x1 h
fg1
= h
2
844.89 + x
1
*1947.3 = 2716.2
x
1
= 1871.3 / 1947.3 = 0.963 Ans.
When p = 0.1MPa and t = 99.63 + 5 = 104.63
o
C,
h
3
=2685.5 kJ/kg
Since h
3
=h
4
2685.5 = 844.89 + x
4
*1947.3
x
4
= 1840.6 / 1947.3 = 0.948
The maximum moisture that can be determined with this set up is only 5.2% Ans
3) The following data were obtained with a separating and throttling
calorimeter:
Pressure in pipeline :1.5 MPa
Condition after throttling:0.1 MPa.110
o
C
During 5 min moisture collected in the separator:0.150 litre at 70
o
C,
Steam condensed after throttling during 5 min
Find the quality of steam in the pipeline
Fig 25: h s Diagram
Solution :
AT 0.1 MPa, 110
o
C, h3 = 2696.2 kJ/kg
Now h
3
=h
2
= h
f2
+ x
2
h
fg2
2696.2=844.89 + x2 1947.3
x
2
= 1851.31/1947.3 = 0.955
If m
1
= mass of moisture collected in the separator in 5 min and
m
2
= mass of steam condensed after throttling in 5 min then
x
1
= (x
2
m
2
) / (m
1
+ m
2
)
at 70
o
C v
f
= 0.001023 m
3
/kg
m
1
= 0.1462 kg and m
2
= 3.24 kg
Hence x
1
= 0.955*3.24 / (0.1462 +3.24) = 0.915 Ans.
4) A vessel having a volume of .4 m
3
contains 2.0 kg of liquid water and vapor
mixture in equilibrium at a pressure of 600 kPa. Calculate a) The volume and
mass of liquid b) The volume and mass of vapor.
Solution: The specific Volume is calculated first.
v =(0.4/2 ) = 0.2 m
3
/kg
The quality of steam can now be calculated
0.2 = 0.001101 + x * 0.3146, x = 0.6322
Therefore mass of liquid is 2.0*(1 - 0.6322) = 0.7356 kg
Mass of vapor is 2.0(0.6322) = 1.2644 kg
Volume of liquid is m
l
v
f
= 0.7356(0.001101) =0.0008m
3
Volume of vapor is m
v
v
g
= 1.2644(0.3157)=0.3992 kg
5) Steam at 1 bar and a dryness fraction of 0.523 is heated in a rigid vessel
until it becomes saturated vapor. Calculate the heat transferred per kg steam.
Solution:
From the steam table at 1 bar pressure, t
s
= 99.62
o
C,
v
f
=0.001043m
3
/kg,v
fg
=1.69296m
3
/kg,
u
f
=417.33 kJ/kg, u
fg
=2088.72kJ/kg,
Volume of one kg of given state of vapor = v
f
+ x v
fg
= 0.001043 + 0.523 * 1.69296 = 0.8864 m
3
/kg
Enthalpy correspond to the state of steam,
u= u
f
+ x u
fg
= 417.33 + 0.523 * 2088.72 =1509.73kJ/kg
v (0.8864 m
3
/kg ) correspond to the saturated condition of the steam, from steam
table, which is vg,
The pressure found to be 2 bar and u
g
=2529.49kJ/kg
Heat added = 2529.49 1509.73 = 1019.76 kJ/kg Ans
.
6) A rigid vessel contains one kg of mixture of saturated water and saturated
steam at a pressure of 0.15MPa. When mixture is heated the state passes
trough the critical point. Determine,
a) Volume of the vessel
b) The mass of the liquid and vapor
c) The temperature of the mixture when the pressure rises to 3 MPa.
d) The heat transfer required to produce the final state.
Solution. V
c
: Critical volume = 0.003155 m
3
/kg (From the steam table.)
v = v
f
+ x X v
fg
0.003155 = 0.001035 + x
1
* 1.15828 , x
1
= 0.00183
Hence, mass of vapor = x = 0.00183 kg
Mass of liquid = (1-x
1
) = 0.998 kg.
u
1
= u
f
+ x
1
X u
fg ;
u
1
= 466.92 + 0.00183 X 2052072 = 470.68 kJ/kg
Saturation temperature correspond to 3 MPa, is 233.9
O
C, the temperature of the
mixture
x
2
= (0.003155 0.001216)/0.06546 = 0.02962
Heat transfer in constant volume process = u
2
u
1
,
u
2
= 1004.76 + 0.02962 X 1599.34 = 1052.13 kJ/kg
Heat transfer = 1052.13 470.68 = 581.45 kJ/kg.
7) Steam initially at 0.3MPa, 250
O
C is cooled at constant volume. Find
i) At what temperature will the steam become saturated vapor?
ii) What is the quality at 80
O
C? What is the heat transferred per kg of steam in
cooling from 250
O
C to 80
O
C?
Solution:
At 300kPa, 250
O
C, from the steam table , it is a superheated condition.
v = 0.79636 m
3
/kg , u = 2728.69 kJ/kg
v
g
= 0.79636 m
3
/kg , P
s
= 225 kPa, t
s
= 124
O
C
at 80
O
C
0.79636 = 0.001029 + x 3.45612
x = (0.79636 - 0.001029) /3.45612 = 0.23
u
2
= 520.45+0.23(2013.1) = 483.463 kJ/kg
Heat transfer = change in internal energy as the process is const. volume,
Heat transfer = u
1
u
2
= 2728.69 983.463 = 1745.227 kJ/kg
8) State whether the following samples of steam are wet, dry or superheated:
Justify your answer.
I) Pressure = 1 MPa absolute enthalpy = 2880 kJ/kg
II) Pressure=500kPa absolute, volume =0.35m
3
/kg
III) Temperature = 200
o
C Pressure = 1.2 MPa.
IV) Temperature = 100
o
C, entropy =6.88kJ/kg K.
V) Pressure= 10 kPa, enthalpy = 2584 kJ/kg.
Try as homework.
Problems for practice:
1) A vacuum pump is used to evacuate a chamber where some specimens are
dried at 50
0
C. the pump rate of volume displacement is 0.5 m
3
/s with an inlet
pressure of 0.1 kPa and temperature 323K. How much water vapor has been
removed over 30 minutes period?
2) A sample of steam from a boiler drum at 3 MPa is put through a throttling
calorimeter in which the pressure and temperature are found to be 0.1 MPa,
393K. Find the quality of the sample taken from the boiler.
3) Two streams of steam, one at 2MPa, 573K and the other at 2MPa, 673K
mixed in a steady flow adiabatic process. The rate of flow of two streams are
3 kg/min and 2 kg/min respectively. Evaluate the final temperature of the
emerging stream, if there is no pressure drop due to the mixing process.
What would be the rate of increase in the entropy of the universe?
4) Steam enters an engine at a pressure of 10 bar absolute and 523 K. it is
exhausted at 2 bar. The steam at exhaust is 0.9 dry. Find drop in enthalpy
and change in entropy.
5) Calculate the internal energy per kg of superheated steam at a pressure of 10
bar absolute and a temperature of 573 K. also find the change of internal
energy if this steam is expanded to 1.4 bar absolute and dryness fraction 0.8