MET 202 ENGINEERING

THERMODYNAMICS
MODULE 4 – Properties of Pure
Substance
 Pure Substance
• A pure substance is a substance of constant
chemical composition throughout its mass.
• It is a one-component system.
• It may exist in one or more phases.
• Water is a pure substance.
• Thermodynamic plots on p-V, p-T, T-s and h-s
coordinates is used to study the behaviour of
water in all the three phases
 P-V Diagram for a Pure Substance

Assume a unit mass of ice (solid water) at -10°C and 1 atm

contained in a cylinder and piston machine . Let the ice be
heated slowly so that its temperature is always uniform. The
changes which occur in the mass of water would be traced
as the temperature is increased while the pressure is held
constant.
P-V Diagram for a Pure Substance
 P-V Diagram for a Pure Substance
The distinct regimes of heating are
• 1-2 The temperature of ice increases from-10°C to 0°C. The
volume of ice would increase. At state 2, i.e., 0°C, the ice would
start melting.
• 2-3 Ice melts into water at a constant temperature of 0°C. At
state 3, the melting process ends. There is a decrease in volume,
which is a peculiarity of water.
• 3-4 The temperature of water increases, upon heating, from 0°C
to100°C. The volume of water increases because of thermal
expansion.
• 4-5 The water starts boiling at state 4 and boiling ends at state 5.
This phase change from liquid to vapour occurs at a constant
temperature of 100°C (the pressure being constant at I atm).
There is a large increase in volume.
• 5-6 The vapour is heated to, say, 250°C (state 6). The volume of
vapour increases from V5 to V6
• Water existed in the solid phase between 1 and 2,
in the liquid phase between 3 and 4, and in the
gas phase beyond 5.
• Between 2 and 3, the solid changed into the
liquid phase by absorbing the latent heat of
fusion.
• Between 4 and 5, the liquid changes into the
vapour phase by absorbing the latent heat of
vaporisation.
• The phase change occur at constant
temperature and pressure
• The states 2, 3, 4 and 5 are known as saturation states.
• A saturation state is state from which a change of
phase may occur without a change of pressure of
temperature.
• State 2 is a saturated solid state because a solid can
change into liquid at constant pressure and
temperature from state 2.
• States 3 and 4 are both saturated liquid states. In state
3, the liquid is saturated with respect to solidification,
where in state 4, the liquid is saturated with respect to
vaporisation.
• State 5 is a saturated vapour state, because from state
5, the vapour can condense into liquid without a
change of pressure or temperature.
• If the heating of ice at -10°C to steam at 250°C
were done at a constant pressure of 2 atm,
similar regimes of heating would have been
obtained with similar saturation states 2, 3, 4 and
5.
• All the state changes of the system can similarly
be plotted on the p-V coordinates, when it is
heated at different constant pressures.
• All the saturated solid states 2 at various pressures
are joined by a line called Saturated solid line
• Similarly, all the saturated liquid states 3 with
respect to solidification, all the saturated liquid
states 4 with respect to vaporisation are joined by a
line called Saturated liquid line
• And all the saturated vapour states 5 are joined
together to get the Saturated vapour line
• The saturated liquid line with respect to vaporisation
and the saturated vapour line incline towards each
other and form what is known as the vapour dome.
• The two lines meet at the critical state.
P-V diagram of a pure substance (water) whose
volume decreases on melting
P-V diagram of a pure substance whose volume
increases on melting
• To the left of the saturated solid line is the solid (S)
region.
• Between the saturated solid line and saturated
liquid line with respect to solidification there exists
the solid-liquid mixture (S+L) region.
• Between the two saturated liquid lines is the
compressed liquid region.
• The liquid-vapour mixture region (L+V) exists
within the vapour dome between the saturated
liquid and saturated vapour lines.
• To the right of the saturated vapour line is the
vapour region.
• The triple point is a line on the p-V diagram,
where all the three phases, solid, liquid, and gas,
exist in equilibrium
• At pressure below the triple point line, the
substance cannot exist in the liquid phase, and
the substance, when heated, transforms from
solid to vapour (known as sublimation) by
absorbing the latent heat of sublimation from
the surroundings.
• The region below the triple point line is,
therefore, the solid-vapour (S+V) mixture
region.
Liquid is, most often, the working fluid in power cycles, etc., and
interest is often confined to the liquid-vapour regions only.
• If the vapour at state A is compressed slowly and
isothermally, the pressure will rise until there is saturated
vapour at point B.
• If the compression is continued, condensation takes place,
the pressure remaining constant so long as the
temperature remains constant.
• At any point between B and C, the liquid and vapour are in
equilibrium.
• Since a very large increase in pressure is needed to
compress the liquid, line CD is almost vertical.
• ABCD is a typical isotherm of a pure substance on a p-V
diagram.
• As the temperature increases, the liquid-vapour transition,
as represented by BC, decreases, and becomes zero at the
critical point.
• Below the critical point only, there is a liquid-vapour
transition zone, where a saturated liquid, on heating, absorbs
the latent heat of vaporisation, and becomes saturated
vapour at a constant pressure and temperature.
• Above the critical point, however, a liquid, upon heating,
suddenly flashes into vapour, or a vapour, upon cooling,
suddenly condenses into liquid. There is no distinct
transition zone from liquid to vapour and vice versa.
• The isotherm passing through the critical point is called the
critical isotherm, and the corresponding temperature is
known as the critical temperature (tc). The pressure and
volume at the critical point are known as the critical pressure
(pc.) and the critical volume (vc) respectively.
For water
Pc = 221.2 bar, tc = 374.15°C, vc=0.00317 m³/kg
• Above the critical point, the isotherms are continuous curves
that at large volumes and low pressures approach equilateral
hyperbolas
 Saturation pressure and temperature

When a liquid or solid is in equilibrium with its vapour at a

given temperature, the vapour exerts a pressure that
depends only on the temperature. In general, the greater the
temperature, the higher is the vapour pressure. The
temperature at which the vapour pressure is equal 760 mm
Hg is called the Normal Boiling Point (N.B.P).
 Phase change occurs at constant pressure and
temperature.

• A pure liquid at a given pressure will transform

into vapour only at a particular temperature,
known as saturation temperature ,which is a
function of pressure.

• Similarly, if the temperature is fixed, the liquid

will boil (or condense) only at a particular
pressure, called the saturation pressure, which is
a function of temperature.
• At point A the liquid starts boiling
and at point B, the boiling gets
completed. At A it is all liquid
(saturated) and there is no vapour,
while at B, it is all vapour
(saturated) and there is no liquid.
Vapour content progressively
increases as the liquid changes its
state from A towards B.
If vf is the specific volume of the
saturated liquid at a given
pressure, and vg the specific
volume of the saturated vapour,
then (vg-vf) or vfg is the change in
specific volume during phase
transition (boiling or
condensation) at the pressure. As
pressure increases, vfg decreases,
and at the critical point vfg
becomes zero.
P-T Diagram for a pure substance
• Heating of ice from -100C to 2500C at the constant
pressure of 1 atm is considered.
• 1-2 is the solid(ice) heating
• 2-3 is the melting of ice at 00C
• 3-4 is the liquid heating
• 4-5 is the vaporization of water at 1000C
• 5-6 is the heating in the vapour phase.
• The state changes at different constant pressures are
considered.
• The curve passing through the 2,3 points is called the
fusion curve.
• The curve passing through the 4,5 points is called the
vaporization curve.
• Sublimation curve is obtained by plotting the vapour
pressure of solid at different temperature.
• The fusion curve, the vaporization curve and the
sublimation curve meet at the triple point.
• The slopes of the sublimation and vaporization
curves for all substances are positive.
• The slope of the fusion curve for most substance
is positive, but for water it is negative.
• The triple point of water is at 4.58 mm Hg and
273.16K
P-T diagram for a substance that contracts on freezing
 P-v-T surface
P-v-T surface and projections for a
substance that expands on freezing
 P-v-T surface
P-v-T surface and projections for a
substance that contracts on freezing
T-S Diagram for a pure substance
h-s diagram or Mollier diagram for a pure
substance
 Quality or dryness fraction

• Quality is the mass fraction of vapour in a liquid vapour

mixture.
• Consider 1kg of liquid vapour mixture in which x kg of
vapour and (1-x)kg of liquid are present. Then ‘x’ is the
quality or dryness fraction of the liquid vapour mixture.
• If mv and ml are the mass of vapour and mass of liquid in
the mixture, then the quality (dryness fraction) of the
mixture is given by
• The value of x varies from 0 to 1
• For saturated water, when water just starts boiling,
x=0 and for saturated vapour, when vaporization is
complete, x=1
• When x=1 the vapour is called dry saturated vapour.
Constant quality lines on P-v, T-s, and h-s diagram
Steam Tables
Saturation states
Liquid vapour mixture
Superheated vapour
Compressed liquid
• Find the enthalpy , entropy and volume of steam at 1.4 MPa, 3800C
• Find the enthalpy and entropy of steam when the pressure is 2MPa
and the specific volume is 0.09 m3/kg
• Steam at 25 bar and 300⁰C expands isentropically to 5 bar. Calculate
the change in enthalpy, volume and temperature of unit mass of
steam during this process using steam tables and Mollier chart and
compare the values
• Determine the change in specific volume, specific enthalpy and
quality of steam as saturated steam at 15 bar expands isentropically
to 1 bar. Use steam tables
• Steam is throttled from 3 MPa and 600˚C to 2.5 MPa. Determine
the temperature of the steam at the end of the throttling process.
• 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.