Pure Substances

What is a Pure substance?

 A pure substance is a material whose properties are not a
blend and are always the same.
 It consists of a single substance (species)
 A pure substance can exists in three different states.
 Vapor and liquid mixture of water can be said as a
homogeneous mixture.
 It is chemically homogeneous but physically not.
 Air which is a mixture of 79% Nitrogen and 21% Oxygen is
a pure substance unless its composition does not change due
to cooling.
 All Materials

Heterogeneous Homogeneous
Materials Materials

Solutions Pure
(Homogeneous mixtures) substances
 Phases of Pure Substance
 Solid
 Liquid
 Gas
 Plasma

A phase is any homogeneous part of the system that is physically

distinctive
Each phase if the system is separated from other phases by phase
boundary.
Transition from one phase to other is called as change of phases
 Sensible heating: Process of heating a substance which
remains in a single phase all the way. Temperature rises.
 Latent Heating: It refers to a heating process that brings
about a phase change. No rise in temperature
 Boiling Point: Temperature at which vapor pressure of the
liquid equals the atmospheric pressure and phase change
takes place from a liquid to vapor state.
 Melting Point: It is the temperature at which a solid changes
into its liquid state when heat supplied is equal to the latent
heat.
 Freezing: Change from liquid phase to the solid phase.
 Saturation state: State at which phase transformation of a
substance takes place without any change in temperature or
pressure. There can be saturated solid state, liquid state and
vapor state.
 Saturation pressure: It is the pressure, for a given
temperature at which a substance undergoes a phase change
for example, the saturation pressure of water at 100oC (373
K) is 1.013 bar.
 Saturation temperature: Refers to the temperature, for a
given pressure at which a phase change of substance takes
place.
 Triple Point: Corresponds to the temperature at which a pure
substance can co-exist in solid, liquid and gaseous phases in
equilibrium. The corresponding temperature and pressure are
referred to as triple point temperature and triple point pressure
respectively. Triple point of water is 273.01 K (0.01oC)
 Critical point: Refers to a particular set of pressure and
temperature condition at which the density of vapor equals density
of liquid of a substance. Simply put, it is the highest temperature
and pressure condition at which a liquid co-exists with vapor for
the last time.
 The critical point of water is 22.12 MPa/647.15 K), vapor above
critical point is a gas.
2-2 Phase Change Process of Pure Substance
2-2-1 Constant Pressure Process of Water
 Definitions
 Compressed or Sub-Cooled liquid means that it is not
about to vapourize
 Saturated Liquid is a liquid that is about to vapourize
 SaturatedVapour is a vapour that is about to condense
 Saturated Liquid-Vapour Mixture is a condition where
liquid and vapour coexist in equilibrium
 Superheated Vapour is a vapour that is not about to
condense

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Influence of Pressure on Temperature

Water boils at 100oC at one

atmosphere pressure. (1 atm =
101.325 kPa)
When pressure is increased, say for
example 500 kPa by adding weights
water boils at 151.8oC
Temperature at which water boils
depends upon the pressure.
 At a given pressure, the
temperature at which a pure
substance changes phase is called as
saturation temperature (Tsat).
 Similar to Psat.
T-v Diagram at constant pressure heating
As pressure keeps on increasing water boils
at higher temperature.
At 1 Mpa it boils at 180oC
Specific volume of saturated liquid is larger
than that of vapor than when it was boiling at
1 atm pressure.
When pressure is increased further, the
saturation line continues to shrink.
There reaches a pressure of about 22.06
Mpa, called the critical pressure of water
where saturated liquid state and saturated
vapor states are identical. The temperature
pressure and specific volumes are critical
pressure, critical specific volume and critical
temperature respectively.
P-v diagram
•For the similar piston cylinder
arrangement for 1MPa, the system is
heated at constant temperatures
•The weights are removed slowly so
that the specific volume slightly
increases and the pressure decreases.
•When the saturation pressure value
0.4762 Mpa, the water starts to boil.
•During this vaporization the
pressure and temperature remains
constant whereas the specific volume
increases.
•This is repeated for other
temperatures and the values are
traced as per the p-v diagram.
Extending P-v diagrams to accommodate solid phase

•Water expands upon freezing. What would happen if in nature it

contracts on freezing?
•First diagram is for substances that contracts upon freezing and the
second one for substances that expand on freezing.
P-T diagram of a pure substance
•A critical point is the one
where all the three phases co-
exist.
•It appears as a point in P-T
diagrams.
•For water it is 0.01oC and
0.6117 kPa respectively.
•No substance can exist in the
liquid phase in stable
equilibrium at pressures
below triple point pressure.
•Substances at high pressures
can exist at liquid phase
below triple point
temperature.
P-v-T Surface

The P-v diagram is the projection of P-v-T surface on a P-v plane and T-v
diagram is the top (bird’s eye) view of the P-v-T surface.
Projections of P-v-T on different planes
Enthalpy as a combination property

Used mainly in power generation and Refrigeration

calculations
It combines Pressure volume and internal energy
H=u+pv in kJ/kg
Or H=U+PV in kJ
Suggested by [Link] Mollier, initially referred
it to heat content or total heat
But was later named as Enthalpy
Saturated Liquid and Saturated vapor states
• f denotes properties of
saturated liquid.
•g denotes properties of
saturated vapor
•fg denotes the difference
between saturated liquid and
vapor values for a given state
•hfg is called as enthalpy of
vaporization , it is the amount of
energy needed to vaporize a unit
mass of saturated liquid at given
temperature or pressure.
•It decreases as temperature or
pressure increases.
Saturated Liquid Vapor mixture

• Proportions of liquid vapor mix has

to be known
• Quality ‘x’ is the measure of the
mass of vapor mixture in a liquid
vapor mixture
• mtotal=mliquid+mvapor
• Value between 0 and 1
• Has no meaning in compressed
liquid and superheated region
• It stands 0 for saturated liquid and 1
for saturated vapor.
• The properties of saturated liquid is
same if it exists alone or with a liquid
vapor mixture
 Two phase system as a homogeneous mixture

u fg  ug  u f
The subscript fg refers to the difference between the
saturated vapor value and the saturated liquid value h fg  hg  h f
region. That is,
s fg  sg  s f
Super heated steam
• Superheated steam is steam at a temperature that is higher
than its vaporization (boiling) point at the absolute pressure where
the temperature measurement is taken.
• Steam can thus cool (lose internal energy) by some amount,
resulting in a lowering of its temperature without changing state.
• Continued heat input towards dry saturated steam will then
"super" heat, the dry saturated steam. This will occur if saturated
steam contacts a surface with a higher temperature. The steam is
then described as superheated by the number of degrees it has
been heated above saturation temperature.
• Superheated steam and liquid water cannot coexist under
thermodynamic equilibrium as any additional heat simply
evaporates more water and the steam will become saturated steam.
•Superheated steam’s greatest value lies in its tremendous internal
energy that can be used for kinetic reaction through mechanical
expansion against turbine blades and reciprocating pistons, that
produces rotary motion of a shaft.
•The value of superheated steam in these applications is its ability to
release tremendous quantities of internal energy yet remain above
the condensation temperature of water vapor; at the pressures at
which reaction turbines and reciprocating piston engines operate.
• Of prime importance in these applications is the fact that water
vapor containing entrained liquid droplets is incompressible. If steam
doing work in a reciprocating engine or turbine, cools to a
temperature at which liquid droplets form; the water droplets
entrained in the fluid flow will strike the mechanical parts of engines
or turbines, with enough force to bend, crack or fracture them.
 Characteristics of Superheated vapour
 Compared to saturated vapour, superheated vapour is
characterized by

Lower Pressures P  Psat at a given T 

Higher Temperatures T  Tsat at a given P 
Higher Specific Volumes v  v g at a given P or T 
Higher internal energies u  u g at a given P or T 
Higher Enthalpies h  h g at a given P or T 

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 Characteristics of Compressed Liquid
 A compressed liquid is characterized by

Higher Pressures P  Psat at a given T 

Lower Temperatures T  Tsat at a given P 
Lower Specific Volumes v  v f at a given P or T 
Lower internal energies u  u f at a given P or T 
Lower Enthalpies h  h f at a given P or T 
 However, the properties of compressed liquid are not much
different from the corresponding saturation liquid values

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