Thermodynamics - II

Lecture 21 & 22
Gas Mixtures (Ch-13)

Zia Ud Din

Objectives
Develop rules for determining nonreacting gas mixture
properties from knowledge of mixture composition and
the properties of the individual components.

Define the quantities used to describe the composition

of a mixture, such as mass fraction, mole fraction, and
volume fraction.
Apply the rules for determining mixture properties to
ideal-gas mixtures and real-gas mixtures.
Predict the P-v-T behavior of gas mixtures based on
Daltons law of additive pressures and Amagats law of
additive volumes.

COMPOSITION OF A GAS MIXTURE:

MASS AND MOLE FRACTIONS
To determine the properties of a mixture, we need to know the composition of
the mixture as well as the properties of the individual components. There are
two ways to describe the composition of a mixture:
Molar analysis: specifying
the number of moles of
each component
Gravimetric analysis:
specifying the mass of each
component
The mass of a mixture is equal to the
sum of the masses of its components.

Mass
fraction

The number of moles of a nonreacting mixture

is equal to the sum of the number of moles of
its components.

Mole
fraction
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Average molar mass

The sum of the mass and

mole fractions of a mixture
is equal to 1.

Gas constant

The molar mass of a mixture

Mass and mole fractions of a

mixture are related by

The sum of the mole

fractions of a mixture is
equal to 1.
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Properties of Air
Constituent

Chemical
Symbol

Analysis

Molar Mass

By Volume %

By Mass %

(Kg/kmol)

Oxygen

O2

20.95

23.14

31.999

Nitrogen

N2

78.09

75.53

28.013

Ar

0.93

1.28

39.948

CO2

0.03

0.05

44.010

Argon
Carbon
Diaoxide

Approximate Analysis of Air

Constituent

Chemical
Symbol

Analysis

Molar Mass

By Volume %

By Mass %

(Kg/kmol)

Oxygen

O2

21

23.3

32

Nitrogen

N2

79.0

76.7

28

Volumetric analysis is the analysis by volume

Gravimetric analysis is the analysis by mass

Example 13-1: Mass and Mole Fractions of a

Gas Mixtures

Example 13-1: Mass and Mole Fractions of a

Gas Mixtures

Example 13-1: Mass and Mole Fractions of a

Gas Mixtures

Daltons Law of Partial Pressures

Consider a closed vessel of volume V at temperature T, which contains a mixture
of ideal gases at a known pressure.
T

V= volume
of the container

T
pA

T
pB

Mixture of two
Ideal gases
A+B
Mixture A+B
Mass= m = mA + mB

Gas A
Mass= mA

Gas B
Mass= mB

When the individual gas is kept at the same Temperature and Volume as
that of the mixture then the pressure will be lowered.
The partial pressure of each constituent is that pressure which the gas
would exert if it occupied alone that volume occupied by the mixture at the
same temperature.

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Daltons Law of Partial Pressures

Daltons Law of Partial Pressures states that The pressure of a mixture of
gasses is equal to the sum of partial pressures of the constituents
T

pA

pB

pA

pB

Mixture of two
perfect gasses
A+B
Gas A
Mass= mA

Mixture A+B

Gas B
Mass= mB

By Daltons Law:

By Conservation of mass:

p
p

mA

mB

mA

mB

pA
pA

pB
pB

pi

pC

etc

mC

etc

mi
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P-v-T BEHAVIOR OF GAS

MIXTURES: IDEAL AND
REAL GASES

Daltons law of additive pressures for a mixture

of two ideal gases.

Amagats law of additive volumes for a mixture

of two ideal gases.

The prediction of the P-v-T

behavior of gas mixtures
is usually based on two
models:
Daltons law of additive
pressures: The pressure
of a gas mixture is equal
to the sum of the
pressures each gas would
exert if it existed alone at
the mixture temperature
and volume.
Amagats law of additive
volumes: The volume of a
gas mixture is equal to the
sum of the volumes each
gas would occupy if it
existed alone at the
mixture temperature and
pressure.
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Pi component pressure

Vi component volume

Pi /Pm pressure fraction

Vi /Vm volume fraction

For ideal gases, Daltons and Amagats

laws are identical and give identical results.

The volume a component would occupy if it existed alone

at the mixture T and P is called the component volume (for
ideal gases, it is equal to the partial volume yiVm).

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Ideal-Gas Mixtures

This equation is only valid for ideal-gas mixtures as it is derived by assuming

ideal-gas behavior for the gas mixture and each of its components.

The quantity yiPm is called the partial pressure (identical to the component
pressure for ideal gases), and the quantity yiVm is called the partial volume
(identical to the component volume for ideal gases).
Note that for an ideal-gas mixture, the mole fraction, the pressure fraction,
and the volume fraction of a component are identical.

The composition of an ideal-gas mixture (such as the exhaust gases leaving

a combustion chamber) is frequently determined by a volumetric analysis
(Orsat Analysis)
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Compressibility factor

Real-Gas
Mixtures

Kays rule

Zi is determined either at Tm and Vm

Daltons law) or at Tm and Pm (Amagats
law) for each individual gas. Using
Daltons law gives more accurate
results.

One way of predicting the P-v-T

behavior of a real-gas mixture is to
use compressibility factor.

Another way of predicting the

P-v-T behavior of a real-gas
mixture is to treat it as a
pseudopure substance with
critical properties.
Zm is determined by using these
pseudocritical properties.
The result by Kays rule is
accurate to within about 10%
over a wide range of
temperatures and pressures.
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PROPERTIES OF GAS MIXTURES:

IDEAL AND REAL GASES
Extensive properties of a gas mixture
The extensive
properties of a
mixture are
determined by
simply adding the
properties of the
components.
Changes in properties of a gas mixture

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Extensive properties of a gas mixture

Properties per unit mass involve

mass fractions (mfi) and
properties per unit mole involve
mole fractions (yi).
The relations are exact for idealgas mixtures, and approximate for
real-gas mixtures.

The intensive
properties of a
mixture are
determined by
weighted
averaging.
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Ideal-Gas Mixtures
GibbsDalton law: Under the ideal-gas
approximation, the properties of a gas are
not influenced by the presence of other
gases, and each gas component in the
mixture behaves as if it exists alone at
the mixture temperature Tm and mixture
volume Vm.
Also, the h, u, cv, and cp of an ideal gas
depend on temperature only and are
independent of the pressure or the
volume of the ideal-gas mixture.
Partial pressures (not
the mixture pressure)
are used in the
evaluation of entropy
changes of ideal-gas
mixtures.

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Expansion of an Ideal Gas Mixture in a

Turbine
A mixture of oxygen (O2), carbon dioxide (CO2) and
helium (He) gases with mass fractions of 0.0625, 0.625
and 0.3125 respectively, enter an adiabatic turbine at
1000 kPa and 600 K steadily and expand to 100 kPa
pressure. The isentropic efficiency of the turbine is 90 %.
For gas components assuming constant specific heats at
room temperature, determine
(a) The work output per unit mass of mixture

Real-Gas Mixtures
T ds relation for a gas mixture

This equation suggests that the generalized property

relations and charts for real gases developed in
Chap. 12 can also be used for the components of
real-gas mixtures. But TR and PR for each
component should be evaluated using Tm and Pm.
If the Vm and Tm are specified instead of Pm and Tm,
evaluate Pm using Daltons law of additive pressures.
Another way is to treat the mixture as a pseudopure
substance having pseudocritical properties,
determined in terms of the critical properties of the
component gases by using Kays rule.

It is difficult to predict the

behavior of nonideal-gas
mixtures because of the
influence of dissimilar
molecules on each other.
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Summary
Composition of a gas mixture: Mass and mole
fractions

P-v-T behavior of gas mixtures

Ideal-gas mixtures
Real-gas mixtures

Properties of gas mixtures

Ideal-gas mixtures
Real-gas mixtures

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