Chapter 3

Gas Mixtures
Many important thermodynamics applications involve more than one pure substance rather than a single pure substance or gas mixtures
Current study of gas mixture are considered non-reacting.
Non-reacting gas mixtures can be treated as pure substance because its composition
is homogeneous.

3.1

Composition of a Gas Mixture: Mass and Mole Fraction

Properties of gas mixtures depend on:

1. composition of mixture.
2. properties of components.
Composition of gas mixtures can be described by:
1. Molar analysis = mole number of each component.
2. Gravimetric analysis = mass of each components.
Mass of mixture = the sum of masses of components:
mm =

k
X

mi

(3.1)

i=1

Mole number of mixture = sum of mole numbers of components:

Nm =

k
X
i=1

Ni

(3.2)

CHAPTER 3. GAS MIXTURES

Mass fraction, mfi = ratio of mass of component to the mass of mixture:

mfi =

mi
mm

(3.3)

Mole fraction, yi = ratio of mole of component to the mole of mixture:

yi =

Ni
Nm

(3.4)

The sum of mass fractions or mole fractions should equal to 1:

k
X

mfi =

i=1

k
X

yi = 1

(3.5)

i=1

Relation between mass, m and mole number, N :

m = MN

(3.6)

Apparent or average molar mass of mixture, Mm :

Mm =

k
X

yi Mi

(3.7)

i=1

Apparent of average gas constant of mixture, Rm :

Rm =

3.2

Ru
Mm

(3.8)

P-v-T Behaviour of Gas Mixtures: Ideal and Real

Gases

For ideal gases:

P v = RT

(3.9)

P v = ZRT

(3.10)

For real gases:

where Z is the compressibility factor.
For gas mixture P-v-T behaviour can be predicted using:
1. Daltons law of additive pressure.
2. Amagats law of additive volume.
3. Kays Rule.
HH

Updated: June 28, 2006

CHAPTER 3. GAS MIXTURES

For ideal gas, pressure fraction and volume fraction equals to the mole fraction:
Pi
Vi
Ni
=
=
= yi
Pm
Vm
Nm

(3.11)

For real gas,deviation from ideal gas can be approximated by incuding compressibility factor:
Pm Vm = Zm Nm Ru Tm
(3.12)
Zm =

k
X

yi Zi

(3.13)

i=1

3.2.1

Daltons Law of additive Pressure

Pressure of gas mixture equal to sum of pressures each gas would exert if it
existed alone at the mixture temperature and volume
Pm =

k
X

Pi (Tm , Vm )

(3.14)

i=1

The solution for equation 3.14 is exact for ideal gas and approximate for real gas.

3.2.2

Amagats Law of additive Volume

Volume of a gas mixture equal to the sum of volumes each gas would occupy
if it existed alone at the mixture temperature and pressure
Vm =

k
X

Vi (Tm , Vm )

(3.15)

i=1

The solution for equation 3.15 is exact for ideal gas and approximate for real gas.

3.2.3

Kays Rule

0 and pseudocritical temperature, T 0

Utilizing the pseudocritical pressure, Pcr
cr

Step by step procedures are as follows:

1. Create the pseudocritical pressure and temperature of the mixture:
0
Pcr,m
=

k
X

yi Pcr,i

(3.16)

yi Tcr,i

(3.17)

i=1

0
Tcr,m

k
X
i=1

HH

Updated: June 28, 2006

CHAPTER 3. GAS MIXTURES

2. From the pseudocritical pressure and temperature of the mixture, find reduced
pressure and temperature of the mixture (PR,m and TR,m ):
PR,m =

Pm
0
Pcr,m

(3.18)

TR,m =

Tm
0
Tcr,m

(3.19)

3. Using reduced pressure and temperature of the mixture, obtain compressibility factor of the mixture, Zm , from compressibility chart.
4. Substitute Zm into equation 3.12 for solution of pressure, temperature etc.

3.3

Properties Of Gas Mixture

Extensive property of gas mixture equal to sum of extensive property of
components of mixture
Um =

k
X

Ui =

i=1

Hm =

Sm =

k
X

k
X

mi ui =

i=1

Hi =

k
X

k
X

mi hi =

i=1

i=1

k
X

k
X

k
X

Si =

i=1

(3.20)

i
Ni h

(3.21)

Ni si

(3.22)

k
X

i=1

i=1

Ni u
i

i=1

mi si =

i=1

Intensive property of gas mixture equal to sum of intensive property of

components multiplied by mass fraction or mole fraction
um =

k
X

mfi ui

u
m =

k
X

i=1

sm =

k
X

mfi si

sm =

i=1

hm =

k
X

k
X

k
X
i=1

HH

(3.23)

yi si

(3.24)

i
yi h

(3.25)

i=1

mfi hi

m =
h

k
X

i=1

Cv,m =

yi u
i

i=1

mfi Cv,i

i=1

Cp,m =

k
X

mfi Cp,i

(3.26)

i=1

Updated: June 28, 2006