CLB 20703

Chemical Engineering
Thermodynamics
Properties of Pure Substances

Objective of Chapter 2
The objective of this chapter is to
introduce the concept of a pure
substance and apply the ideal-gas
equations to solve the problems in
engineering thermodynamics

Outline
Thermodynamic Properties Of Pure
Substances
PT, PV and PVT diagram
Ideal Gas Law
Compressibility Factor
Equation Of State
Other Equation Of States

Pure Substance

A substance that has a fixed chemical

composition throughout is called a pure
substance, e.g.: H2O, N2, CO2

A pure substance does not have to be of a

single chemical element or compound

A mixture of chemical elements/compounds

also qualifies as a pure substance as long
as the mixture is homogeneous, e.g. Air

Pure Substance (contd)

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

Example: a mixture of ice and liquid water

is a pure substance because both phases
have the same chemical composition

However, a mixture of liquid air and

gaseous air is not a pure substance since
their chemical compositions are not similar

Pure Substance (contd)

Water that exists in the liquid phase is called a

Compressed Liquid or Sub-cooled Liquid,
meaning that it is not about to vaporize

A liquid that is about to vaporize is called a

Saturated Liquid and a vapor that is about to
condense is called a Saturated Vapor

Liquid and vapor phases co-exist in a Saturated

Liquid-Vapor Mixture

A vapor that is not about to condense is called a

Superheated Vapor

Pure Substance (contd)

At a given P, T at which a pure substance changes

phase is called the Saturation Temperature

At a given T, P at which a pure substance changes

phase is called the Saturation Pressure

The amount of energy absorbed or released during

a phase-change process is called the Latent Heat

The amount of energy absorbed during melting is

called the Latent Heat Of Fusion

The amount of energy absorbed during vaporization

is called the Latent Heat Of Vaporization

PT Diagram

PT diagram illustrates:
Vapor

Pressure vs. Temperature curves

characterizing the equilibrium relationships of
different phases sublimation curve, fusion
curve, and vaporization curve

Three-phase

regions solid, liquid, vapor

Critical

point, C where highest P and T can exist

in vapor/liquid equilibrium

Triple

point, where 3 phases coexist in

equilibrium

PT Diagram (contd)

PV Diagram

PV diagrams displays:
Regions

of 2 phases coexist in equilibrium

Bounding
Triple

curves represent single phases

point becomes a horizontal line

A dome-shaped

curve with the left half represent

liquid phase and the right half represent vapor
phase

Horizontal

segment of isotherm represents the

mixtures of liquid and vapor phases

PV Diagram (contd)

PV Diagram (contd)

The Ideal Gas

Gas and Vapour are often used as
synonymous words.
a.)The Vapour phase of a substance is
customarily called a GAS when it is ABOVE
its Critical Temperature.
b.)VAPOUR usually implies a gas that is NOT
FAR from a state of Condensation i.e.
Saturated Vapour State.

The Ideal Gas

Introduction
-

Any equation that relates the

properties of Pressure ( P ),
Temperature ( T ) and Specific
Volume ( v ) of a substance is called
an Equation Of State.

The Ideal Gas

There are several Equations of State,
some are simple while others are very
complicated.
The simplest and the best known Equation
of State for substance in GAS phase is the
Ideal Gas Equation Of State.
The Equation of State predicts P, T and v
behaviour of a GAS quite accurately but

The Ideal Gas

within some properly selected region, i.e. it
has limitation.
Little Bit Of History :
a.) 1662
Robert Boyle, English scientist
observed/found out during his experiments
- In a Vacuum chamber, the Pressure of
gases is inversely proportional to their

The Ideal Gas

volume.
P 1/V ( Boyles Law )
b.) 1802
J. Charles and J. Guy-Lussac
experimentally determined that :
- Specifically at LOW pressures, the Volume
of a gas is proportional to its Temperature

The Ideal Gas

i.e.
V T ( Charles Law ).

Boyles Law and Charles Law can be

COMBINED into one equation which is
known as Ideal-Gas Equation of State or
Ideal-Gas Relation.

The Ideal Gas

Equation of State
PV=nRT PV=mRT

P=RT

Ru
R
MW

R = gas constant
Ru=universal gas constant, Ru=8.314 kJ/kmolK

MW=molecular weight of the gas

The Ideal Gas

Examples of Gas Constant, R value.

Substance

R, kJ/kgK

Air

0.2870

Helium

2.0769

Argon

0.2081

Nitrogen

0.2968

The Ideal Gas

Limitations of Ideal-Gas Equation of State:
a.)It has been experimentally observed that
Ideal-Gas relation closely approximates the Pv-T behaviour of Ideal-Gas at LOW densities.
b.)At LOW Pressures and HIGH Temperatures,
the density of a gas DECREASES and
therefore the gas behaves

The Ideal Gas

like an Ideal-Gas at LOW densities.
This is especially concerning the CRITICAL
VALUES of Pressure and Temperature.
c.)Many FAMILIAR gases such as Air,
Nitrogen, Oxygen, Hydrogen, Helium,
Argon, Neon, Krypton and even heavier
gases such as Carbon Dioxide CAN be
treated as Ideal-Gas with negligible error
( often less than 1%).

The Ideal Gas

Dense gases such as Water Vapour in

Steam Power Plants and Refrigerant
Vapour in Refrigerators should NOT be
treated as Ideal-Gas. Instead, the
Property Tables should be used.

The Compressibility Factor, Z

The ideal gas is a model fluid described by

simple property relations, which are good
approximations for actual gases

Gases at pressures up to a few bars may be

considered ideal and simple equations
apply.
However, gases deviate from Ideal Gas
behaviour significantly at states near the
Saturation Region and the Critical Point.

The Compressibility Factor, Z

This deviation from Ideal-Gas behaviour at

a given Temperature and Pressure can
accurately be accounted for by the
introduction of a Correction Factor called
the Compressibility Factor, Z.
PV
Z
RT

For ideal gas, Z = 1, thus PV = RT.

The Compressibility Factor, Z

For Real Gases i.e. gas that deviates from
Ideal Gas behaviour, Z can be greater than
or less than unity.
The farther away Z is from unity, the more
the gas deviates from Ideal Gas behaviour.
Compressibility Factor, Z can also be
expressed as
Z = VActual / Videal

The Compressibility Factor, Z

Gases behave differently at given Temperature and
Pressure, but behave very much the same at
Temperatures and Pressures normalized with respect
to their Critical Temperatures and Pressures.
The normalization is done as
PR = P/Pcr and TR = T/Tcr

PR = Reduced Pressure, TR = Reduced

Temperature

The Compressibility Factor, Z

These correlations can be found using a
Generalized Compressibility Chart.
According to the Principle of
Corresponding States, the Compressibility
Factor, Z for all gases is approximately the
SAME at the same reduced Pressure and
Temperature.

The Compressibility Factor, Z

From the Generalized Compressibility

Chart, the following observation can be
made :
1.) At VERY LOW Pressures (PR << 1),
gases behave as an Ideal Gas regardless
of Temperature.
2.) At HIGH Temperatures (TR > 2), Ideal
Gas behaviour can be assumed with good
accuracy regardless of Pressure except

The Compressibility Factor, Z

when PR>>1.
3.) The deviation of a gas from Ideal Gas
behaviour is GREATEST in the vicinity of the
Critical Point.
When P and v or T and v are given instead of P
and T, the Generalized Compressibility Chart
can still be used. However, one more reduced
property need to be used.

The Compressibility Factor, Z

This reduced property is called Pseudo-Reduced
Specific Volume, vR
vR = vactual / (RTcr/Pcr)

Lines of vR are also added to the Compressibility Chart

which enables to determine T or P without having to
resort to time-consuming iterations.

Other Equation Of State

Other Equation Of State are :

1.) Van der Waals Equation Of State.
2.) Beattie-Bridgemann Equation Of
State.
3.) Benedict-Webb-Rubin Equation Of
State.
4.) Virial Equation Of State.

Other Equation Of State

Van der Waals Equation Of State.
Was proposed in 1873.
Has 2 constants determined from the
behaviour of a substance at the Critical Point.
( P + a/v2 ) ( v b ) = RT
a = ( 27R2T2cr / 64Pcr ) and b = RTcr/8Pcr

Include 2 effects which are Intermolecular

Attraction Forces and Molecular Volume.

Other Equation Of State

Beattie-Bridgemann Equation Of State.
Was proposed in 1928.
Based on 5 experimentally determined
constants.

where
and

Other Equation Of State

Benedict-Webb-Rubin Equation Of
State
Was extended by Benedict, Webb and
Rubin in 1940 by raising the number of
constants to 8.
This equation can handle substances at
densities up to about 2.5cr

Other Equation Of State

Virial Equation Of State
This is the Equation Of State expressed in
a series with the coefficients are functions
of Temperature and are called Virial
Coefficients.

Other Equation Of State

Equation Of State

Number Of Constants

Description

Van der Waals

Accurate over a limited

range.

Beattie-Bridgeman

Accurate for 0.8cr

Benedict-Webb-Rubin

Accurate for 2.5cr

Strobridge

16

More suitable for

computer calculation

May vary

Accuracy depends on
the number of terms
used.

Virial