UNIT-III

PROPERTIES OF A PURE SUBSTANCE

A pure substance is one that has homogeneous and invariable chemical composition. It
may exist in more than one phase, but chemical composition is same for all the phases. Thus,
water, mixture of water and ice and water and steam are all examples of pure substance.
Sometimes a mixture of gases e.g. air is considered as pure substance. We have seen that two
independent properties are sufficient to determine thermodynamic state of a fluid when it is in
equilibrium. Any other thermodynamic property is a function of the chosen pair of independent
properties. We shall first consider the relation between the primary properties p, v and T, the
equation expressing this relation for any particular fluid being called the equation of state or
characteristic equation of the fluid.

The heat transferred to a substance while the temperature changes is sometimes referred
to as sensible heat. This constant pressure lines are called isobars. If the pressure is reduced,
there is a slight rise in the melting point and also there is a marked drop in the boiling point of
water and a marked increase in the change in volume, which accompanies evaporation. When the
pressure is reduced to 0.006113 bar (0.6113 kPa), the melting point and boiling point
temperatures become equal and change of phase, ice-water-steam, are represented by a single
line. The temperature at which this occurs has been accepted internationally as a fixed point for
the absolute temperature scale and is by definition 273.16 K. Only at this temperature and
pressure of 0.6112 kPa, can ice, water and steam coexists in thermodynamic equilibrium in a
closed vessel and is known as triple point. If the pressure is reduced further, the ice, instead of
melting, sublimes directly into steam. the phase diagram and properties are shown in the
following diagrams.
 Consider now the behaviour at pressure above atmospheric. The shape of the curve is
similar to that of the atmospheric isobar, but there is a marked reduction in the change in volume
accompanying vaporation. At a sufficiently high pressure, this change in volume falls to zero and
the horizontal portion of the curve reduces to a point of inflexion. This is referred to critical
point. The values pressure and temperature of water at which critical point reached are pc =
221.2 bar = 22.12 MPa ; Tc = 647.3 K ;vc = 0.00317 m3/kg.
 The pressure at which liquid vaporises or condenses is called saturation pressure
corresponding to a given temperature. Alternately, the temperature at which this phenomenon
occur is called saturation temperature corresponding to the given pressure. A vapour in a state
lying along the saturated vapour line is also called dry saturated vapour and the vapour lying
right of this line is called superheated vapour.

IMPORTANT POINTS TO BE REMEMBERED

Saturation temperature: Temperature at which a pure substance changes phase at a given

pressure.
Saturation pressure: Pressure at which a pure substance changes phase at a given temperature.
Latent heat: The amount of energy absorbed or released during a phase-change.
Melting /freezing: Latent heat of fusion.
Evaporation/condensation: Latent heat of vaporization.
Temperature at which water starts boiling depends on the pressure => if the pressure is fixed, so
is the boiling temperature.For a single phase we need to know only two independent properties
like (P, T), (T, v), etc.For a two-phase mixture, p and T are not independent. Hence, we require
defining “quality”.
Quality or Dryness fraction as shown in the following figure.
x= mv/(mv + ml)
Value of x varies from 0 to 1. For saturated water,
when water just starts boiling, x = 0 and
forSaturated vapour, when vaporisation is complete,
x = 1 and the vapour is called dry saturated.
Let
V be the total volume of a liquid vapour mixture of quality x.
Vf the volume of saturated liquid and
Vg the volume of saturated vapour, the corresponding masses are m, mf, and mg
respectively
 TWO MARKS
1. Define latent heat of ice?
Total amount of heat added during conversion of ice 0° C into water of 0°C.

2. What is pure substance?

Pure substance is a substance which has a fixed chemical composition throughout its
mass.
Example: Water, Nitrogen, Carbon dioxide, and helium.
A pure substance does not have to be of a single chemical element or compound .A
mixture of various chemical element or components is also called as pure substance as long as
the mixture is homogeneous.

3. What is saturation temperature and saturation pressure?

At a given pressure, the temperature at which a liquid boils is called saturation
temperature.
At the given temperature, the pressure at which the liquid boils is called saturation
pressure it is also called as vapour pressure.

4. Define latent heat of vaporizations.

The amount of heat added during heating of water from boiling point to dry saturated stage is
called as latent heat of vaporization or enthalpy of vaporization of latent heat of steam.

5. Define the terms ‘Boiling point ‘and ‘Melting point’ .

Boiling point:
It is the temperature at which the liquid starts to change its state from liquid to vapour.
Melting point:
It is the temperature at which the solid starts to change its state from solid to liquid
6. Explain the term: Degree of super heat, Degree of sub cooling.
Degree of super heat:
It is the difference between superheated temperature and saturated temperature at the same
pressure.
Degree of sub cooling.
It is the amount by which the water is cooled beyond the saturated temperature at the same
pressure.

7. Define triple point and critical point for pure substance.

Triple point:
Triple point is the state at where all the three phases ie solid, liquid and vapour to exist in
equilibrium.
Critical point:
It represents the highest pressure and temperature at which the liquid and vapour phases coexist
in equilibrium. At the critical point the liquid and the vapour phases are distinguishable ie Liquid
directly converted into vapour.

8. When saturation pressure increases, what happens to saturation temperature and freezing
point?
When saturation pressure increases, then the saturation temperature is increasing and the
freezing point decreasing.

9. What is meant by steam power cycles?

Thermodynamics cycle which use steam as the working fluid is called steam power cycle.

10. What are the effects of condenser pressure on the rankine cycle?
By lowering the condenser pressure, we can increase the cycle efficiency. the main
disadvantage is lowering the back pressure increase the wetness of steam. isentropic comparison
of a very wet vapour is very difficult.

\11. Why carnot cycle cannot be realized in practical for vapour power?
The main difficult to attain the cycle in practice is that isothermal condensation is stopped
before it reaches to saturated liquid conditions .There fore the compressors has to deal with a non
–homogeneous mixture of water and steam .Because of the large specific volume of liquid
vapour mixture before compression ,the compressor size and work input have to be large. The
higher power requirement reduces the plant efficiency as well as work ratio.

12. Mension the improvement made to increase the ideal efficiency of Rankine Cycle.
1. Lowering the condenser pressure.
2. Superheated steam is supplied to the turbine.
3. Increasing the boiler pressure to certain limits.

13. What are the disadvantages of reheating?

The cost of the plant increases due to the reheater and its long connections It also
increases the condenser capacity due to increased dryness fraction.
14. List the advantages of reheat cycle.
1. Marginal increase in thermal efficiency.
2. Increses in work done per kg of steam which results in reduced size of boiler and
auxiliaries for same output.
3. We can prevent the turbine from erosion.

15. What is the function of feed water heaters in the regenerative cycle with bleeding?
The main function of feed water heater is to increase the temperature of feed water to the
saturation temperature corresponding to the boiler pressure before it enters into the boiler.

12 MARKS
1. Find the enthalpy and entropy of steam when the pressure is 2MPa and the specific volume is
0.09 m3/kg

Solution:
When P= 2MPa,
Vf = 0.001177 m3/kg and Vg=0.09963 m3/kg.
Since the given volume lies between Vf and Vg, the substance will be a mixture of
liquid and vapour, and state will be within the vapour dome. When in two phase region, the
composition of the mixture or its quality has to be evaluated first. Now

2. A vessel of volume 0.04m3 contains a mixture of saturated water and saturated steam at a
temperature of 2500C. The mass of the liquid present is 9kg. Find the pressure, the mass, the
specific volume, the enthalpy, the entropy and the internal energy.

Solution:
For temperature 2500C
Psat=3.973MPa
3. Steam at 20 bar, 3600C is expanded in a steam turbine at 0.08 bar. It then enters a condenser,
where it is condensed to saturatedliquid to water. The pump feeds back the water in to the boiler.
(a) Assuming ideal processes, find per kg of steam the net work and the cycle efficiency. (b) If
the turbine and the pump have each 80% efficiency, find the percentage reduction in the net work
and cycle efficiency.

Solution: The property values at different state points (as shown in fig) found from steam tables
are given below.
4. A steam turbine gets its supply of steam at 70 bar and 4500C. After expanding to 25bar in high
pressure stages, it is reheated to 4200C at the constant pressure. Next, it is expanded in
intermediate pressure stage to an appropriate minimum pressure such that part of the steam bled
at this pressureheats the feedwater to a temperature of 180 0C. The remaining steam expands from
this pressure to a condenser pressure of 0.07 bar in the low pressure stage. The isentropic
efficiency of the h.p. stage is 78.5 % while that of the intermediate and l.p. stage is 83% each.
From the above data (a) determine the minimum pressure at which bleeding is necessary , and
sketch a line diagram of the arrangement of the plant. (b) Sketch on the T-S diagram all the
process, (c) determine the quantity of steam bled per kg of flow at the turbine inlet, and (d)
calculate the cycle fficiency. Neglect the pump work.

Solution:
Fig. gives the flow and T-S diagrams of the plant. It would be assumed that the
feed water heater is an open heater. Feedwater is heated to 1800C. So Psat at 1800C =10bar is the
pressure at which the heater operates.
5. A certain chemical plant requires heat from process steam at 120 0C at the rate of 5.83 MJ/s and
power at the rate of 1000kW from the generator terminals. Both the heat and power requirements
are met by a back pressure turbine of 80% brake and 85% internal energy, which exhausts steam
at 1200C dry saturated. All the latent heat released during condensation is utilized in the process
heater. Find the pressure and temperature of steam at the inlet to the turbine. Assume 90%
efficiency for the generator.

Solution: At 1200C, hfg=2202.6 kJ/kg = h2-h3

6. In a single heater regenerative cycle the steam enters the turbine at 30 bar, 4000C and the
exhaust pressure is 0.10 bar. The feedwater heater is a direct contact type which operates at 5 bar.
Find (a) the efficiency and the steam rate of the cycle and (b) the increase in main temperature of
heat addition, efficiency and steam rate, as compared to the rankine cycle (without regeneration).
Neglect pump work.

Solution: Fig. gives the flow, T-S and h-S diagrams. From the steam tables, the property values
at various states have been obtained