Properties of Pure Substances

The pure substance is any mixture or compound having a uniform composition through it e.g CO2,
H2, and gaseous air are pure substance. The mixture of two or more pure substance is considered
to be pure.
Condensed/Saturated liquid, Saturated /Super-heated vapors:
Say at some pressure “P” the liquid at temperature lower than its boiling point is condensed liquid,
at the same pressure the liquid at the temperature equal to its boiling point is saturated liquid i.e.
Its phase transition is about to happen. At this point the vaporization process continues and the
system contains the mixture of vapors and saturated liquid until all the liquid is vaporized to vapors
and the temperature remains constant. At the same pressure the vapor so produced that are about
to condense are saturated vapors. The vapor that is heated to a very higher temperature after the
transition has completed is superheated vapor.
Saturation temperature and Pressure, Latent heats:
At a given pressure the temperature at which the substance changes its phase is saturation
temperature Tsat. Similarly at a given temperature the pressure at which the substance changes its
phase is its saturation pressure Psat.
The amount of heat exchanged during a phase transition is latent heat. For melting
we have latent heat of fusion and for vaporization we have latent heat of vaporization.
What is a vapor:
Vapor is an intermediate state between the liquid state and gaseous state. It can be condensed to
the liquid form by just applying high pressure. However gas can’t be converted to liquid state
without cooling. Any substance above its critical temperature behaves like a gas. It should be kept
in mind that the laws valid for the gases are not valid for the vapor state. Thus vapors are studied
separately.

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Water Vapors:
Take a look at the T-V graph for the water vapor as follows:
P constant= 101.325 kPa

100
f (x=0,mg=0 ) g (x=1,mf=0)

Ice 1kg
Anomalous
behavior of -10 C
water

heat

4
e
vfg= vg- vf
c
0 d For other
-10
vf
substances
V
vx vg

We start heating a kilogram of ice at -10˚C in a closed piston cylinder system. The temperature
rises with the increase in the volume as shown in the figure curve b-c till the temperature becomes
equal to 0˚C. Further heating the system does not cause any temperature change in the system
instead the volume of the system decreases from point c-d. This is only manifested in case of water
called the anomalous behavior of the water and not manifested by other substance. The temperature
of the water remains the same throughout the transition from the ice phase to liquid phase. The
transition temperature is always constant. It is the temperature at which the phases of the substance
changes to other phase. At this temperature which is also called the melting point of the water there
is a decrease in the volume of the water. As a consequence the density of the water increases to a
maximum level. At 4˚C the density of the water is maximum. This anomalous behavior of water
is responsible for the lives of countless number of marine species which exist in the subzero
temperature. The ice remains at the top and the dense water stays below thus insulating it from the
outside effects.
Again when the heat is given the temperature increase and the volume also increase from
point e to f till we reach the boiling point of the water i.e. 100 C at 101.325 kPa. We should bear
in mind that this boiling point is relative to the applied pressure. It means that the boiling point of
the water or any substance can be increased or decreased by increasing or decreasing the pressure.
Effect of pressure changes is only present in case of gaseous substance.
Heating the system further does not change the temperature as transition from liquid to
gaseous phase is taking place. This is depicted in curve f-g. We have a volume increase but no
temperature changes. Further heating the system improves the quality of steam as shown in the
curve g-s. Now,

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  At ‘f’ the substance is called the saturated liquid.
 At ‘g’ it is called the saturated vapor or dry vapors.
 The curve f-g is a mixture of the two called wet vapors.
 At the points beyond ‘g’ such as‘s’ the substance is called super-heated steam.

There are three kinds of vapors:

1. Wet Vapors
2. Dry Vapors
3. Super-Heated Vapors

Heat required between the phase (state) d-f =hf = enthalpy of a saturated liquid
(Sensible heat because of temperature variations)

Heat required between the phase (state) d-g =hg = enthalpy of dry saturated vapor
Heat required between the phase (state) f-g = hfg = hg-h f = latent heat of vaporization
Heat required to change the phase from d-s= hg+h s = hf + hfg+ h s= Enthalpy of Super-heated
vapors
What is a Wet Vapor?
It is a partially evaporated liquid and is the homogenous mixture of saturated vapor and saturated
liquid droplets. The familiar cloud of steam is due to the water droplets it contains. It is therefore
wet steam. The wet steam is the only visible steam others are invisible.
Dryness Fraction:
It is the measure of the quality of the wet steam. Mathematically’

0 x1

m
x g
m m
g s
where mg , ms are mass of saturated vapors in the sample and mass of saturated liquid droplets
respectively.
At the point f in the figure x=0 and mg=0
At the point g, x=1 and mf =0 Thus 0  x 1
If the water content in the steam is 5% by mass, then the steam is said to be 95% dry with a
dryness fraction 0.95.

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Volumes, Enthalpy and other properties of wet vapors:
The volume of the wet vapors = v =vx = vf +x vfg
The enthalpy of the wet vapors = h =hx = hf +x hfg
The internal energy of the wet vapors = u =ux = uf +x ufg
Similarly all the other properties can be expressed. In case of dry vapors we have v=vg, h=hg and
u = ug
Triple Point
It is the state point at which the solid, liquid and vapor phases can coexist in equilibrium.

When the sequence of events in the formation of vapors is followed through at low pressures
firstly there is a slight rise at in the melting point and there is a marked drop in the boiling point.
When the pressure is reduced to 0.6113 kPa the melting point and the boiling point becomes
equal. At this point of concurrency the solid liquid and gaseous phases coexist in equilibrium.
If the pressure is reduced still further the ice instead of melting sublimes directly into steam. The
melting point increases and the boiling point decreases with the pressure decrease. The horizontal
lines come close as pressure decreases. At 0.6113 kPa the boiling and the melting points become
coincident. At this point the temperature is 0.01 C called the triple point. The lower most line
is the sublimation line. On the P-T diagram it appears as a point and hence triple point. On the T-
V and P-V diagram it appears as a line and hence triple line. For substances having triple point
pressure higher than the atmospheric pressure like CO2, sublimation is the only way to change
from the solid to vapor phase.

The importance of the triple point is that it is taken as the reference point for most of the vapors.
In case of gases we take 0 K as the reference temperature.

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Critical Point
At the critical point the saturated liquid phase and saturated vapor phase are identical.

The saturated liquid states are connected and we have a saturated liquid line. Similarly when the
saturated vapor states are connected we have the saturated vapor line. These two lines meet at the
critical point and form a dome as shown above. There are three regions of the dome. The
Compressed liquid, Saturated liquid and saturated vapor mix (wet region) region, superheated
region as shown.

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C.P#20-Find the volume of 1.5 kg of steam 70% dry at 1 MPa.

We have been provided with the fo We have been provided with the follwing data:
Mass  m  1.5 kg
Pressure  P  1 MPa
Dryness fraction  x  0.7
State  wet steam as the dryness fraction has been provided
We have to find the following:
specific volume  v  ?
We have v  v f  xv fg
where v fg  vg  v f
Using the steam table we have,
v f  0.001127 m3
v fg  0.193313 m3
Then
v  v f  xv fg
v  0.001127  (0.7)(0.193313)
v  0.1364 m3 / kg
V  1.5(0.1364)  0.2046 m3
(Variation between the two rows of steam table properties is not linear
so no mean can be taken. All the values are for unit mass)
In case when v f is not given we can use the relation :
v f  xvg
and approximation can be used.

C.P#21-

Solution

54
C.P#22-

55
C.P#23-A rigid vessel of volume 1 m³ contains steam at 20bars and 400 ˚C. The vessel is cooled
until the steam is just dry saturated. Calculate the mass of the steam in the vessel the final
pressure of the steam and the heat removed during the process.

We have been provided with the following data:

Volume  1 m3
Initial Pressure  20 bars
Initial Temperature  T1  400 C o
We have to calculate the following:
Final Pressure  P2  ?
Heat exchanged  Q  ?
As it is about the processes we have the followin two stages:
Stage 1:
Nature of the steam is Super heated steam as T1  Tboil (using the steam table read
boiling point at 20 bars Tboil  212.4 C o )

Stage 2:
Dry saturated as stated
At 20 bars and 400 C from the superheated portion of the steam table we have
v1  0.1512 m3 / kg and u1  2945.2 kJ / kg
V 1.0
Thus m    6.61 kg
v 0.1512
To find the pressure P2 we have v1  v2  vg  0.1512 m3 / kg search for the vg
value in the column for P2  1.3MPa.
Similarly u2  u g  2589.9 at P2  1.3MPa using the steam table.
Thus we have
At constant volume Q  U 2  U1  m(u2  u1 )  6.61(2589.9  2945.2)  2348.5 kj

C.P#24- Steam at 7 bars with dryness fraction of 0.9 expands in a piston cylinder assembly
at constant pressure until the temperature is 200˚C. Calculate he work done and the specific
heat supplied of the steam during the process.

56
We have been provided with the following data:
Pressure  P1  P2  7 bars
Dryness Fraction  x  0.9
Initial temperature  T1  200 C o
Mass  m  1 kg
we have to calculate the following:
Work Done  W  ?
Heat Supplied  Q  ?
We have the case of isobaric expansion which involves two states.
State 1:
Wet steam as the x has been given to us in the problem.

State 2:
Using the data P2  7 bars T2  200 C o we find the boiling point of the
steam at 7 bars which on the steam table is given to be 165 C o . Now as the
T2  Tboil so the steam is super-heated steam.

Now at constant pressure as m  1 kg we have

W  P (V2  V1 )  P (v2  v1 ) also
Q  H 2  H1  h2  h1
and from the steam table we can find v1 and h1 as follows:
v1  v f  x(v fg )  v f  x (vg  v f )  0.001108  0.9(0.2718)  0.2457 m3 / kg
h1  h f  x(h fg )  697  0.9(2065.9)  2556 kJ / kg
At the state 2 we have
P2  7 bars  0.7 MPa
T2  200 C o

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from the super heated steam table we have the following data:
v2  vg  0.2999 m3 / kg
h2  hg  2845 kJ / kg
Thus using the relation above we have the folowing results:
W  P(V2  V1 )  P(v2  v1 )  700(0.2999  0.2457)  37.94 kJ / kg
Q  H 2  H1  h2  h1  2845  2556  289 kJ / kg

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