Properties of Pure

Substances
Pure Substance
• A pure substance is one that has a homogeneous and invariable
chemical composition even though there is a change of phase.
In other words, it is a system which is
(a) homogeneous in composition,
(b) homogeneous in chemical aggregation.
(c) invariable in chemical aggregation.
Examples : Liquid, water, mixture of liquid water and steam,
mixture of ice and water. The mixture of liquid air and gaseous
air is not a pure substance.
Pure Substance

a. comprising steam and water, is homogeneous in composition, since chemical

analysis would reveal that hydrogen and oxygen atoms are presents in the
ratio 2 : 1 whether the sample be taken from the steam or from the water.
b. containing uncombined hydrogen and oxygen gas in the atomic ratio 2 : 1 in
the upper part, and water in the lower part.
c. however, is not homogeneous in composition, for the hydrogen and oxygen are
present in the ratio 1 : 1 in the upper part, but in the ratio 2 : 1 (as water) in
the lower part.
 PHASE CHANGE OF A PURE SUBSTANCE
Let's consider the results of heating liquid water from 20 oC, 1 atm while
keeping the pressure constant. We will follow the constant pressure process shown
in figure below. First place liquid water in a piston-cylinder device where a fixed
weight is placed on the piston to keep the pressure of the water constant at all times.
As liquid water is heated while the pressure is held constant, the following events
occur.

Constant-pressure change from liquid to vapor phase for a pure substance

PHASE CHANGE OF A PURE SUBSTANCE
• Compressed liquid (subcooled liquid): A substance that it is not
about to vaporize
• Saturated liquid: A liquid that is about to vaporize
• Saturated vapor: A vapor that is about to condense.
• Saturated liquid–vapor mixture: The state at which the liquid and
vapor phases coexist in equilibrium
• Superheated vapor: A vapor that is not about to condense (i.e., not
a saturated vapor)
PHASE CHANGE OF A PURE SUBSTANCE

At 1 atm and 20°C, water exists in

the liquid phase (compressed
liquid)
PHASE CHANGE OF A PURE SUBSTANCE

At 1 atm pressure and 100°C, water

exists as a liquid that is ready to
vaporize (saturated liquid)
PHASE CHANGE OF A PURE SUBSTANCE

As more heat is transferred, part of the

saturated liquid vaporizes (saturated
liquid– vapor mixture).
PHASE CHANGE OF A PURE SUBSTANCE

At 1 atm pressure, the temperature

remains constant at 100°C until the
last drop of liquid is vaporized
(saturated vapor)
PHASE CHANGE OF A PURE SUBSTANCE

As more heat is transferred, the

temperature of the vapor starts
to rise (superheated vapor).
 PHASE CHANGE OF A PURE SUBSTANCE
If the entire process between state 1 and 5 described in the figure is reversed by cooling the
water while maintaining the pressure at the same value, the water will go back to state 1,
retracing the same path, and in so doing, the amount of heat released will exactly match the
amount of heat added during the heating process.

T-v diagram for the

heating process of
water at constant
pressure
Saturation Temperature and Saturation Pressure
The temperature at which water starts boiling depends on the pressure; therefore, if the pressure is fixed, so is the
boiling temperature.
• Water boils at 100oC at 1 atm pressure.
• Saturation temperature Tsat: The temperature at which a pure substance changes phase at a given pressure.
• Saturation pressure Psat: The pressure at which a pure substance changes phase at a given temperature.

The liquid–vapor saturation curve of a pure substance

(numerical values are for water).
Variation of the Standard Atmospheric Pressure
and the Boiling Saturation of Water Altitude
 Latent Heat
• Latent heat: The amount of energy absorbed or released during a phase change process.
• Latent heat of fusion: The amount of energy absorbed during melting. It is equivalent to the
amount of energy released during freezing.
• Latent heat of vaporization: The amount of energy absorbed during vaporization, and it is
equivalent to the energy released during condensation.
• The magnitudes of the latent heats depend on the temperature or pressure at which the phase
change occurs.
At 1 atm pressure, the latent heat of fusion of water is 333.7 kJ/kg and the latent heat of vaporization
is 2256.5 kJ/kg.

The atmospheric pressure, and thus the boiling temperature of water, decreases with elevation.
T-v diagram of constant-pressure phase-change
processes of a pure substance at various pressures

Critical Point is the point at which

the saturated liquid and saturated
vapor states are identical. At
pressures above the critical
pressure, there is not a distinct
phase change process.

*Numerical Values are for Water

T-v Diagram of a Pure Substance
Saturated liquid states can be
connected by a line called the
saturated liquid line.
Saturated vapor states 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
figure at the left.
T-v Diagram of a Pure Substance
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.
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.
The P-v Diagram of a 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.
During the vaporization process, both
the temperature and the pressure remain
constant, but the specific volume
increases.
 Pressure-Temperature (P-T) Diagram for Pure
Substances
The points representing the coexistence of
(i) solid and vapor lie on the ‘sublimation curve’,
(ii) liquid and vapor lie on the ‘vaporization curve’,
(iii) liquid and solid lie on the ‘fusion curve’.
In the particular case of water, the sublimation
curve is called the frost line, the vaporization curve is
called the steam line, and the fusion curve is called the ice
line.
The slopes of sublimation and the vaporization
curves for all substances are positive. The slope of the
fusion curve, however may be positive or negative. The
fusion curve of most substances have a positive slope.
Water is one of the important exceptions.
p-T diagram for a substance such as water
 Pressure-Temperature (P-T) Diagram for Pure
Substances
Triple point
The triple point is merely the point of intersection of
sublimation and vaporization curves. It must be understood that
only on p-T diagram is the triple point represented by a point.
On p-V diagram it is a line, and on a U-V diagram it is a triangle.
— The pressure and temperature at which all three phases of a
pure substance coexist may be measured with the apparatus that
is used to measure vapor pressure.
— Triple-point data for some interesting substances are given in
Table 1(found in next page)

p-T diagram for a substance such as water

P-V-T Surface
The P-V-T and T-V diagrams can be
combined into a single three-dimensional
surface as shown at the right for a
substance that contracts when it freezes.
In the diagram, the solid phase regions
are also represented. The regions where
only one phase exist are labeled solid,
liquid and vapor. The regions where two
phases exist the regions are labeled as
solid-liquid, solid-vapor, and liquid-vapor.
Along the triple line, a line constant
temperature and pressure, all three
phases coexists.
Phase Change Terminology and Definitions

Phase Change Name Process

1. Solid-Liquid Fusion Freezing, Melting
2. Solid-Vapor Sublimation Frosting, Defrosting
3. Liquid –Vapor Evaporation Evaporating, Condensing
Phase Change Terminology and Definitions
• Triple point—The only state at which the solid, liquid and vapor phases coexist
in equilibrium.
• Critical point (C.P.). The limit of distinction between a liquid and vapor.

• Critical pressure. The pressure at the critical point

• Critical temperature. The temperature at the critical point

• Gas—A vapor whose temperature is greater than the critical temperature.

Liquid-Vapor Terms
• Saturation temperature. The phase change temperature corresponding to the saturation
pressure. Sometimes called the boiling temperature.

• Saturation pressure. The phase change pressure.

• Compressed liquid. Liquid whose temperature is

lower than the saturation temperature. Sometimes called
a sub-cooled liquid
• Saturated liquid. Liquid at the saturation temperature corresponding to the saturation
pressure.

• Saturated vapor. A term including wet and dry vapor

• Dry (saturated) vapor. vapor which has just completed evaporation. The pressure and
temperature of the vapor are the saturation values.

• Wet vapor. The mixture of saturated liquid and dry vapor during the phase change.

• Superheated vapor. vapor whose temperature is greater than the saturation temperature
corresponding to the pressure of the vapor.
• Degree of superheat. The term used for the numerical amount by which the temperature
of a superheated vapor exceeds the saturation temperature.
PROPERTY DIAGRAMS IN COMMON USE
Besides p-V diagram which is useful because
pressure and volume are easily visualized and the T-s
chart which is used in general thermodynamic work,
there are other charts which are of practical use for
particular applications. The specific enthalpy-specific
entropy chart is used for steam plant work and the
pressure-specific enthalpy chart is used in refrigeration
work. Sketches of these charts are shown at the left. These
charts are drawn for H2O (water and steam) and represent
the correct shape of the curves for this substance.
IMPOTANT TERMS RELATING STEAM FORMATION

Enthalpy of wet steam (h). It is defined as the quantity of heat required to

convert 1 kg of water at 0°C into wet steam at constant pressure. It is the sum of total
heat of water and the latent heat and this sum is also called enthalpy.
In other words

If Steam is dry and saturated, then and

where
IMPOTANT TERMS RELATING STEAM FORMATION

Sensible heat of water (hf ). It is defined as the quantity of heat

absorbed by 1 kg of water when it is heated from 0°C (freezing point)
to boiling point .

Cp=specific heat of water, 4.187

t- temperature of water

Latent heat or hidden heat (hfg). It is the amount of heat required to

convert water at a given temperature and pressure into steam at the
same temperature and pressure.
IMPOTANT TERMS RELATING STEAM FORMATION

Dryness fraction (x). The term dryness fraction is related with

wet steam. It is defined as the ratio of the mass of actual dry steam to
the mass of steam containing it. It is usually expressed by the symbol ‘x’.
If
ms=Mass of dry steam contained in steam considered
mw = mass of water particles in suspension in the steam considered

Then,
Wetness fraction. Ratio of mass of moisture to the total mass of
steam considered. It is denoted by y and expressed

(1-x)-Priming-wetness fraction in percent.

Enthalpy of Superheated Steam. The specific enthalpy of
superheated steam can be calculated from

where
- enthalpy of superheated steam (kJ/kg)
- specific enthalpy of saturated steam (kJ/kg)
- specific heat of steam at constant pressure
- 1.8860 at standard atmosphere. Take note that
varies with temperature.
- Saturation temperature
- Superheated Steam temperature
Enthalpy of Saturated Water (). Enthalpy of Saturated water is
designated as , in the steam tables and can directly be obtained from
steam tables. It is defined as an amount of heat energy absorbed by 1 kg
of water during its heating from 0°C to the saturation temperature () at
a given pressure.

Enthalpy of Saturated Steam (). It is the sum of enthalpy of saturated

water and enthalpy of vaporization. It may be defined as the amount of
heat required to convert 1 kg of water at 0°C into dry and saturated
steam at a given pressure
IMPOTANT TERMS RELATING STEAM FORMATION
Superheated steam. When steam is heated after it has become dry and
saturated, it is called superheated steam and the process of heating is called
superheating. Superheating is always carried out at constant pressure. The
additional amount of heat supplied to the steam during superheating is called
as ‘Heat of superheat’ and can be calculated by using the specific heat of
superheated steam at constant pressure (cps), the value of which varies from 2.0
to 2.1 kJ/ kg K depending upon pressure and temperature.
If Tsup., Ts are the temperatures of superheated steam in K and wet or dry
steam, then (Tsup – Ts) is called ‘degree of superheat’.
The total heat of superheated steam is given by
The advantages obtained by using ‘superheated’ steam are as follows

(i) By superheating steam, its heat content and hence its capacity to do work is
increased without having to increase its pressure.

(ii) Superheating is done in a superheater which obtains its heat from waste furnace
gases which would have otherwise passed uselessly up the chimney.

(iii) High temperature of superheated steam results in an increase in thermal

efficiency.

(iv) Since the superheated steam is at a temperature above that corresponding to its
pressure, it can be considerably cooled during expansion in an engine before its
temperature falls below that at which it will condense and thereby become wet. Hence,
heat losses due to condensation of steam on cylinder walls etc. are avoided to a great extent
Specific Volume of Wet Steam. The wet steam is a mixture of dry
vapor and moisture. The specific volume of wet steam is the sum of
moisture volume and a fraction of volume during evaporation.

where

= specific volume of dry and saturated steam

=specific volume of moisture (water)
specific volume change of steam during evaporation =
Specific Volume of superheated steam. As superheated steam behaves like a
perfect gas its volume can be found out in the same way as the gases. If,
vg=Specific volume of dry steam at pressure p
Ts=Saturation temperature in K
Tsup-Temperature of superheated steam in K, and
vsup = Volume of 1 kg of superheated steam at pressure p,
Then,
STEAM TABLES
Internal Energy of Steam
Internal energy is the energy associated with the random, disordered motion of molecules or it
refers to energy contained within the system. Internal energy also refers to the invisible microscopic energy
on the atomic and molecular scale having a property whose value is the sum of all the microscopic forms of
energy. Internal energy also accounts of the gains and losses of energy of the system.
There are two ways internal energy can be changed:
(1) by heating the system, and
(2) by doing work on the system. The total heat is given by,

or

where:
u = internal energy of steam at pressure p (kJ/kg)
h = specific enthalpy of steam (kJ/kg)
p = saturation pressure (kPa)
v = specific volume of saturated steam (m3/kg)
Internal Energy of Steam
Internal energy of wet steam can be found using,

where
u = internal energy (kJ/kg)
uf= internal energy of saturated liquid (kJ/kg)
ug = internal energy of saturated vapor (kJ/kg
ufg = internal energy change of vaporization (kJ/kg)
Internal Energy of superheated steam can be found using

u = internal energy of superheated steam (kJ/kg)

hsup = enthalpy of superheated steam (kJ/kg)
= hg+ Cps(ts-tf)
hg = specific enthalpy of saturated steam, kJ/kg
Cps= specific heat of steam at constant pressure
= 1.860 (kJ/kg-°C) at std. atmosphere
(Take note that Cps varies with pressure).
tr = saturation temperature (°C)
ts = superheated steam temperature (°C)
p = saturation pressure. kPa
vsup = specific volume of superheated steam (m3/kg)
Entropy of Pure Substances
Entropy of Dry or Saturated Steam. It is the sum of entropy of
saturated water sf, and the entropy of evaporation sfg. It can be
directly determined in the in the steam table.
Entropy of Wet Steam. It is the sum of entropy of
saturated water sf and the entropy of partial
evaporation.
Entropy of Superheating Steam. The entropy change during
superheating of 1 kg of dry steam from Tsat to Tsup at constant
pressure.

The total entropy of superheated steam above the freezing point

temperature of water
where:
Cps = specific heat of steam at constant pressure
= 1.860 (kJ/kg-°K) at std. atmosphere
(Take note that Cps varies with pressure).
Tsat = saturation temperature (°K)
Tsup= superheated steam temperature (°K)
Entropy Change During Heating of Water. Let 1 kg of water be
heated from temperature T1 to T2 at constant pressure. The change
in entropy is calculated by:

where:
s = change in entropy (kJ/kg-°K)
Cpw = specific heat of water, 4.187 kJ/kg-°K
T = -absolute temperature (°K)
T2 = final temperature (°K)
T1 = initial temperature (°K)
The entropy of saturated water, sf from 273 K to Tsat can
be obtained directly from the steam tables or it can be
calculated as
Entropy Change During Evaporation. The specific entropy change
during evaporation is denoted by Sfg for saturated steam and
obtained from steam tables. For saturated steam, entropy
during evaporation can be calculated as:
Mollier Diagram (H-S Chart)
Also known as the Enthalpy-Entropy
diagram or the H-S diagram
It Plots the total heat against entropy,
describing the enthalpy of thermodynamic
system.
It is a graphical representation of functional
relationship between enthalpy, entropy,
temperature, pressure and quality of steam

Mollier Chart is used only for superheated steam

and when the quality of the steam is greater than 50%