Engineering Thermodynamics

Chapter 3

PROPERTIES OF PURE SUBSTANCES

PURE SUBSTANCE
• Pure substance: A substance that has a fixed chemical
composition throughout.
• Air is a mixture of several gases, but it is considered
to be a pure substance.

Nitrogen and gaseous air are

pure substances A mixture of liquid and gaseous
water is a pure substance, but a
mixture of liquid and gaseous air
is not 2
PHASES OF A PURE SUBSTANCE
In a solid, the
The molecules attractive and
in a solid are repulsive forces
kept at their
between the
positions by the
large springlike
molecules tend
inter-molecular to maintain them
forces. at relatively
constant
distances from
each other.

The arrangement of atoms in different phases: (a) molecules are at

relatively fixed positions in a solid, (b) groups of molecules move
about each other in the liquid phase, and (c) molecules move about at
random in the gas phase. 3
FORMATION OF STEAM AT CONSTANT PRESSURE FROM
WATER AT 0°C
Frictionless Piston–Cylinder assembly is
taken.
1 kg water at 0°C is taken inside the
assembly.
The condition of water at various stages
is represented by Temp-Enthalpy (T-H)
chart.
Weight W is kept on piston to maintain
the intensity of pressure as constant at p.
Area of piston is 1 m2 & volume of water is
Vw.
FORMATION OF STEAM
Condition A: Water is at 0°C with volume Vw

W
Piston
T°C
p Vw A

Cylinder Water at 0°C Enthalpy

FORMATION OF STEAM
Because of heat addition Water
Condition B: temp. will gradually increase
from A and finally reach point B
-Enthalpy of water increases
-Negligible increase in volume of
water.

W Heating of water
Tsat ° B

p Vw+  T°C
A
Water at Tsat°C
FORMATION OF STEAM
Condition C: Now actual steam formation
starts at pt. B
-No change in temperature
-Piston moves upward with
increase in volume and enthalpy
of steam
W
Tsat° B C

p
T°C
A
Water & Steam
at Tsat°C Enthalpy
FORMATION OF STEAM
Steam formation is completed
Condition D: at point D
-No water particles are present
-Piston moves upward with
W volume of steam reaches to Vsat
-Temp. still at Tsat
Evaporation
B C D
Tsat°
p
Vsat
T°C
A

Steam at Tsat°C Enthalpy

FORMATION OF STEAM
Condition E: Further heating of steam
beyond D again increases the
W temp. of steam
-Temp will be Tsup with vol. Vsup
E
Tsup°
Super heating
p
B C D
Tsat°
Vsup

T°C A

Steam at Tsup°C
Enthalpy
FORMATION OF STEAM

A B C D E
E
B C
Tsat
D

T°C
A

Enthalpy
(kJ/kg)
IMPORTANT DEFINITIONS
Saturation temperature ( ts):
The temperature at which steam formation
starts at given pressure is called saturation
temperature or boiling point of water. In
figure at point B steam starts forming.
Temp. at B is Tsat.

-Each pressure has

unique saturation
temperature B
Tsat
e.g.
at 1 bar Tsat = 99.63ºC A
at 220.9 bar Tsat=374.14ºC
Enthalpy
(kJ/kg)
IMPORTANT DEFINITIONS
Enthalpy of water/Sensible heat of water (hf) :
The amount of heat absorbed by 1 kg of water to
change its temp. from the freezing point to the boiling
point Tsat, is known as the enthalpy of the saturated
water or sensible heat of water.
- It is also called liquid
enthalpy
hf = cpw x (Tsat - 0) kJ/kg
where,
cpw= sp. heat of water Tsat B
= 4.187 kJ/kg.K T°C
OR A
from steam table hf can
hf Enthalpy
be read at given pressure. (kJ/kg)
IMPORTANT DEFINITIONS
Enthalpy of Evaporation/Latent heat(L or hfg):
The enthalpy of evaporation or latent heat is defined as the
amount of heat required to convert 1 kg of water at a given
temperature Tsat and pressure p completely into steam at
the same temperature and pressure.

- In graph, heat required to

change water at B
completely into steam at
D is called latent heat. Tsat B C
- the value of hfg is T°C
directly obtained from hfg
A
steam table at given
pressure. Enthalpy
(kJ/kg)
IMPORTANT DEFINITIONS
Freezing point temperature :
The constant temperature at which phase
changes from liquid to solid at given
pressure, is called freezing point
temperature.
Evaporation/vaporisation :

The process during which the phase changes

from liquid to steam at constant pressure is
called Evaporation or vaporisation.
CONDITION OF STEAM
Saturated water :
At given pressure, the water at saturation
temperature is called saturated water.
Wet steam :
The mixture of saturated water & steam is
called wet steam.
Dryness fraction ( x ):
It is the measure of amount of saturated
water present in wet steam.
Mathematically it can be defined as the
ratio of mass of steam to the total mass of
mixture. msteam
mass of steam
x= = m
mass of steam + mass of water steam + mwater
CONDITION OF STEAM
Wetness of steam :
The quantity ( 1- x ) is called wetness of
steam.
Dry saturated steam :
If wet steam is heated till last water
particle get converted to steam, then such
steam is called dry saturated steam.
Super heated steam :
If dry saturated steam is heated its
temperature will increase. The steam
having temperature greater than saturation
temperature is called superheated steam.
Thus,
Tsup > Tsat at given pressure
CONDITION OF STEAM
Degree of superheat :
The difference of temperature of
superheated steam & saturation temperature
at given pressure is called degree of
superheat.
Mathematically,
degree of super heat = ( Tsup – Tsat )

e.g.
at 10 bar pressure & 250ºC temperature of steam,
degree of superheat = (250 – 179.91) = 70.09ºC
where Tsat = 179.91 at 10 bar from steam table
PROPERTY DIAGRAMS FOR CRITICAL PRESSURE
PHASE-CHANGE PROCESSES & TEMPERATURE
As the pressure increases,
latent heat decreases The pressure
At critical point, water & steam at which
co-exist. latent heat
p3> p2>p1 becomes 0 is
called critical
critical point pressure & The point
374.14° corresponding
p3=C temperature is at which
p2=C called critical latent heat
p1=C temperature is 0 is
T°C called
critical
from steam table, point
critical pr. = 220.9 bar
Enthalpy critical temp. = 374.14ºC
 PROPERTY DIAGRAMS FOR PHASE-CHANGE
PROCESSES

In T-V diagram constant pressure lines have upward In P-V diagram constant pressure lines have downward
trend trend
 The P-T Diagram
• This diagram is often called
the phase diagram since all
three phases are separated
from each other by three
lines.
• The sublimation line
separates the solid and
vapor regions,
• the vaporization line
separates the liquid and
vapor regions, and
• the melting (or fusion) line
separates the solid and
liquid regions.
• These three lines (sublimation, melting and vaporization
lines) meet at the triple point, where all three phases coexist
in equilibrium.
• The vaporization line ends at the critical point because no
distinction can be made between liquid and vapor phases
above the critical point.
• Substances that expand and contract on freezing differ only
in the melting line on the P-T diagram.

For water,
Subscript tp stands for triple point
Ttp = 0.01°C
Ptp = 0.6117 kPa