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CHAPTER

Properties of a
Pure Substance
Outlines
• Definition of a pure substance
• Phase Changes
• P-T diagrams
• T-v diagrams
• P-v diagrams
• Property Tables
• The Ideal Gas Law
• Equations Of State (EOS)

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 Thermodynamics
HEAT POWER
Dr. Elsa Maalouf CHEN 214 Thermodynamics 1 3
What is an engine?

An engine or motor is a machine designed to convert one

form of energy into mechanical energy. Heat engines, like
the internal combustion engine, burn a fuel to create heat
which is then used to do work (motion).

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 Pure Substances

Dr. Elsa Maalouf Thermodynamics 1 5

Why do we study the properties of substances?
We need a substance to allow an engine to function.

We must know the properties of the substance in the liquid

and vapour state (e.g. temperature and specific volume for
a given pressure) to properly size the equipment (e.g., heat
exchangers, pumps, turbine) for the desired transfer of
matter and energy.

If the system is not properly sized, (e.g. too small) this can
lead to increased friction, which reduces the efficiency (so
more losses).

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 What is a pure substance?

 A pure substance has homogeneous and invariable

chemical composition. i.e., it has a fixed chemical
composition throughout.

 Is Nitrogen a pure substance? Is water a pure

substance?

 A pure substance does not have to be of a single

chemical element. So water, H2O, is a pure substance.

 Is a mixture of water and oil a pure substance?

No, because oil is not soluble in water and the mixture
will separate into two chemically distinct phases.
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Phases of a Pure Substance

Substances exist in different phases. At room

T and P, copper is a solid, mercury is a liquid, and
nitrogen is a gas. Under different conditions,
each may appear in a different phase.

A mixture of two or more phases of a pure

substance is still a pure substance as long as the
chemical composition of all phases is the same.

Is ice water a pure substance?

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 Phases of a Pure Substance

SOLID: The molecules are arranged in a 3D pattern that is

repeated. Molecules are close and the attractive forces of
molecules on each other are large and keep the molecules in
fixed positions. The molecules cannot move relative to each
other, but they continually oscillate about their equilibrium
positions.

LIQUID: At high T, the velocity of the molecules increase

and the intermolecular forces are partially overcome and
groups of molecules break away. This is the beginning of the
melting process.
The molecular spacing in liquid is not much different from
solid, except the molecules are no longer at fixed positions
relative to each other and they can rotate and translate
freely. The distances between molecules generally experience
a slight increase as a solid turns liquid, with water being a
notable exception
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 Phases of a Pure Substance
.
GAS: The molecules are far apart from each other, and
a molecular order is nonexistent. Gas molecules move
randomly, colliding with each other and the walls of the
container.
The inter molecular forces are very small, and
collisions are the only mode of interaction between
molecules.
In the gas phase molecules are at a considerably higher
energy level than they are in the liquid or solid phases.
The gas must release a large amount of its energy
before it can condense or freeze.

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 Phase Changes

Dr. Elsa Maalouf Thermodynamics 1 11

 Phase Changes
Assume a container filled with water with a piston on top.
(a) Water at 1 atm (101 kPa), room temperature.
Heat the water, gas forms, state moves from (a) towards (b).
At (b) it is boiling with co-existing liquid and vapor.
Continue heating: more vapor, less liquid until no more liquid.

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 Phase Changes
P atmospheric P atmospheric

Water is still a liquid, but
Water is in the heat addition causes some of
liquid phase, a the liquid to vaporize. That
compressed liquid, is, a phase-change process
or a subcooled from liquid to vapor is about
liquid, meaning to take place. A liquid that is
that it is not about to vaporize is called a
about to vaporize. saturated liquid.
Once boiling starts, T stops rising until the liquid is
completely vaporized. T = constant during the
entire phase-change process if P is held constant.
During a boiling process, the only change we will
observe is a large increase in the volume and a
steady decline in the liquid level. State 3 is midway
about the vaporization line i.e., the cylinder
contains equal amounts of liquid and vapor.
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Phase Changes

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 Phase Changes
Continue transferring heat, the vaporization
process continues until the last drop of
liquid is vaporized (state 4). The entire
cylinder is filled with vapor that is on the
borderline of the liquid phase. Any heat loss
from this vapor will cause some of the vapor
to condense (phase change from vapor to
liquid). A vapor that is about to condense is
called a saturated vapor (state 4).
Once the phase-change process is completed, we
have a a single phase vapor. Transfer of heat
results in an increase in T and the v.
If we transfer some heat from the vapor, the T
may drop somewhat but no condensation will take
place as long as T > 100°C (for P = 1 atm). A vapor
that is not about to condense (i.e., not a
saturated vapor) is called a superheated vapor.
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Phase Changes
Does water boil at 100 C?

The statement “water boils at

100°C” is incorrect.

The correct statement is “water

boils at 100°C at 1 atm pressure.”

The only reason water started

boiling at 100°C was because we held
the pressure constant at 1 atm
(101.325 kPa).

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 Phase Changes

P-T diagram

Dr. Elsa Maalouf Thermodynamics 1 17

Saturation P and T
At a given pressure, the temperature at which
a pure substance changes phase is called the
saturation temperature Tsat.

At a given temperature, the pressure at which

a pure substance changes phase is called the
saturation pressure Psat.

The table indicates that the pressure of

water changing phase (boiling or condensing)
at 25°C must be 3.17 kPa, and the pressure of
water must be maintained at 3973 kPa (about
40 atm) to have it boil at 250°C.

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Phase Changes

Where does the saturation

temperature fall on this
curve where P = 1 atm?

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 Phase Boundaries – Liquid Vapor

• During a phase-change process,

P and T are dependent
properties, i.e., Tsat = f (Psat).

• A plot of Tsat versus Psat, for Liquid

water is shown on the right; this
is called a liquid–vapour
saturation curve or a vapour-
pressure curve.
Vapour

• A curve of this kind is

characteristic of all pure
substances. The liquid–vapor saturation curve of a
pure substance (numerical values are for water).
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 Phase Changes

T-v diagram

Dr. Elsa Maalouf Thermodynamics 1 21

Phase Changes – T-v P = 1 atm P = 1 atm

(Liquid vapor)

P = 1 atm

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Phase Changes – The T-v diagram
the point at which the Let’s add weight to the piston (or
saturated liquid and increase the surrounding pressure)
saturated vapor
states are identical
1- Water starts boiling at
a much higher
temperature

2- The specific volume

of the saturated liquid is
larger and the specific
volume of the saturated
vapor is smaller

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Phase Changes – The T-v diagram – Critical Point

• At pressures above the critical

pressure, there is not a distinct phase
change process.
• There is only one phase present that
resembles a vapor
• Above the critical state, there is no
line that separates the compressed
liquid region and the superheated
vapor region.
• It is customary to refer to the
substance as superheated vapor at
temperatures above the critical
temperature and as compressed liquid
at temperatures below the critical
temperature.

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Phase Changes – The T-v diagram – Connect the dots

Saturated
Saturated Vapor Line
Liquid Line
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 Phase Changes

P-v diagram

Dr. Elsa Maalouf Thermodynamics 1 26

 Phase Changes – The P-v diagram

• Remove weights one by one so that the

pressure decreases.
• The water is allowed to exchange heat
with the surroundings; T = cst.
Compressed liquid

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 Phase Changes – The P-v diagram

Draw the Pv diagram for a constant T • As P decreases, V increases. When

P=Psat, the water starts to boil.
• During this vaporization process, T and
P are constant, but v increases.
• Once the last drop of liquid is
vaporized, further reduction in
pressure (by removing pistons) results
in a further increase in specific volume.
• Notice that during the phase-change
process, we did not remove any weights.
Doing so would cause the P and
therefore T to drop [since Tsat = f
(Psat)], and the process would no longer
be isothermal. 28
Phase Changes – The P-v diagram

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Phase Changes – The P-v diagram with solids

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 Phase Diagram – Triple Point

 All three phases of a pure substance coexist in equilibrium.

 On P-v or T-v diagrams, these triple-phase states form a line called the
triple line.
 On the triple line the phases of the substance have the same pressure and
temperature but different specific volumes.
 The triple line appears as a point on the P-T diagrams and, therefore, is
often called the triple point.

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 Phase Changes

P-v diagram

Dr. Elsa Maalouf Thermodynamics 1 32

 Phase Diagram
 All three phases are separated from
each other by three lines.

 At the triple point, all three phases

coexist in equilibrium. b

a
 State (a):
 Superheated vapor (T >Tsat for same P)
 Expanded vapor (P < Psat for same T)

 State (b):
 Compressed liquid (P > Psat for same T)
 Subcooled liquid (T < Tsat for same P)

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 Phase Diagram – CO2

 CO2 (dry ice) has a triple-point

pressure above the atmospheric
pressure.

 Sublimation is the only way to Sublimation

change from the solid to vapor

phase at atmospheric conditions.

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 Concept – Why do we care?
Why do we care about the fluid properties?
Because we are using these phase changes and volume changes
for energy transformations.

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Phase Changes – The T-P diagram

The Phase Diagram for Water The Phase Diagram for CO2

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Phase Changes – The P-T diagram

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 The P-v-T surfaces
• All the points on the surface represent
equilibrium states.

• All states along the path of a quasi-

equilibrium process lie on the P-v-T surface
since such a process must pass through
equilibrium states.

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The P-v-T surface for water
• The total P-v-T surface shows all the different regions
• Small v's are liquid or solid
• Large v's are vapor (gas)
• Look at this diagram from the right along the volume axis. You see
the P-T phase diagram.
• Look from the left along the T axis you see a P-v diagram partly
obscured by the solid surface.
• We will use these 2-D figures/projections (for simplicity)

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