Chapter 13

Gas Mixtures

Study Guide in PowerPoint

to accompany

Thermodynamics: An Engineering Approach, 7th edition

by Yunus A. Çengel and Michael A. Boles

Prof. Dr. Abdullah Marashli

AL-HUSSEIN BIN TALAL UNIVERSITY
The discussions in this chapter are restricted to nonreactive ideal-gas mixtures.

Many thermodynamic applications involve mixtures of ideal gases. That is, each of
the gases in the mixture individually behaves as an ideal gas. In this section, we
assume that the gases in the mixture do not react with one another to any
significant degree.

We restrict ourselves to a study of only ideal-gas mixtures. An ideal gas is one in

which the equation of state is given by

PV  mRT or PV  NRu T
Air is an example of an ideal gas mixture and has the following approximate
composition.

Component % by Volume
N2 78.10
O2 20.95
Argon 0.92
CO2 + trace elements 0.03

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Definitions
Consider a container having a volume V that is filled with a mixture of k different
gases at a pressure P and a temperature T.

A mixture of two or more gases of fixed chemical composition is called a nonreacting

gas mixture. Consider k gases in a rigid container as shown here.
There are two ways to describe the composition of a
mixture: either by specifying the number of moles of each k gases
component, called molar analysis, or by specifying the T = Tm V = Vm
mass of each component, called gravimetric analysis. P = Pm m = mm
*Throughout this chapter, the subscript m denotes the gas mixture and the subscript i
denotes any single component of the mixture.
The total mass of the mixture mm and the total moles of mixture Nm are defined as

k k
mm  m
i 1
i and Nm  N
i 1
i

mm=m1+m2+m3+…….+mi Nm=N1+N2+N3+…….+Ni

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The composition of a gas mixture is described by specifying either the mass fraction
mfi or the mole fraction yi of each component i.
mi Ni
mf1=m1/mm mf i  and yi 
mm Nm
Note that k k

 mf
i 1
i =1 and y
i 1
i 1

The mass and mole number for a given component are related through the molar
mass (or molecular weight).
mi  N i M i
To find the average molar mass for the mixture Mm , note
k k
mm   mi   N i M i  N m M m
i 1 i 1
Solving for the average or apparent molar mass Mm
k k
mm Ni
Mm   M i   yi M i ( kg / kmol )
N m i 1 N m i 1

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The apparent (or average) gas constant of a mixture is expressed as
R Ru=8.314 kJ/kmol K
Rm  u ( kJ / kg  K )
Mm Mair 29 kmol/ kg
Can you show that Rm is given as
k
Rm   mf i Ri
i 1
To change from a mole fraction analysis to a mass fraction analysis , we
can show that
yi M i
mf i  k

y M
i 1
i i

To change from a mass fraction analysis to a mole fraction analysis , we can

show that
mf i / M i
yi  k

 mf
i 1
i / Mi

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Volume fraction (Amagat model)

Divide the container into k subcontainers, such that each subcontainer has only one
of the gases in the mixture at the original mixture temperature and pressure.

Amagat's law of additive vol­umes states that 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.
k
Amagat's law: Vm   Vi (Tm , Pm )
i 1
The volume fraction of the vfi of any component is

Vi (Tm , Pm )
vf i 
and Vm
k

 vf
i 1
i =1
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For an ideal gas mixture
N i Ru Tm N m Ru Tm
Vi  and Vm 
Pm Pm
Taking the ratio of these two equations gives
Vi Ni
vf i    yi
Vm N m
The volume fraction and the mole fraction of a component in an ideal gas mixture are
the same.

Partial pressure (Dalton model)

The partial pressure of component i is defined as the product of the mole fraction and
the mixture pressure according to Dalton’s law. For the component i
Pi  yi Pm
k
Dalton’s law: Pm   Pi (Tm ,Vm )
i 1

exact for ideal gases, but approximate for real gases

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 Now, consider placing each of the k gases in a separate container having the volume
of the mixture at the temperature of the mixture. The pressure that results is called
the component pressure, Pi' .

N i Ru Tm N m Ru Tm
Pi '  and Pm 
Vm Vm
Note that the ratio of Pi' to Pm is

Pi ' Vi Ni
   yi
Pm Vm N m

For ideal-gas mixtures, the partial pressure and the component pressure are the same
and are equal to the product of the mole fraction and the mixture pressure.
P`i=Pi
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Other properties of ideal-gas mixtures

The extensive properties of a gas mixture, in general, can be determined by

summing the contributions of each component of the mixture. The evalu­ation of
intensive properties of a gas mixture, however, involves averaging in terms of
mass or mole fractions:

k k k
U m   U i   mi ui   N i ui (kJ)
i 1 i 1 i 1
k k k
Hm   Hi   mi hi   N i hi (kJ)
i 1 i 1 i 1
k k k
Sm   Si   mi si   N i si (kJ / K)
i 1 i 1 i 1

CAN WE Add new properties ?

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and
k k
um   mf i ui and um   yi ui (kJ / kg or kJ / kmol)
i 1 i 1
k k
hm   mf i hi and hm   yi hi (kJ / kg or kJ / kmol)
i 1 i 1
k k
sm   mf i si and sm   yi si (kJ / kg  K or kJ / kmol  K)
i 1 i 1

k k
Cv , m   mf i Cv , i and Cv , m   yi Cv , i
i 1 i 1
k k
C p , m   mf i C p , i and C p , m   yi C p , i
i 1 i 1

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 These relations are applicable to both ideal- and real-gas mixtures. The prop­erties or
property changes of individual components can be determined by using ideal-gas or
real-gas relations developed in earlier chapters.

Ratio of specific heats k is given as

C p ,m C p ,m
km  
Cv ,m Cv ,m
The entropy of a mixture of ideal gases is equal to the sum of the entropies of the
component gases as they exist in the mixture. We employ the Gibbs-Dalton law that
says each gas behaves as if it alone occupies the volume of the system at the
mixture temperature. That is, the pressure of each component is the partial pressure.

For constant specific heats, the entropy change of any component is

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The entropy change of the mixture per mass of mixture is

The entropy change of the mixture per mole of mixture is

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In these last two equations, recall that

Pi , 1  yi , 1 Pm, 1
Pi , 2  yi , 2 Pm, 2
Example 1

An ideal-gas mixture has the following volumetric analysis

Component % by Volume
N2 60
CO2 40

(a)Find the analysis on a mass basis.

For ideal-gas mixtures, the percent by volume is the volume fraction. Recall

yi  vf i

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 Comp. yi Mi yiMi mfi = yiMi /Mm
kg/kmol kg/kmol kgi/kgm
N2 0.60 28 16.8 0.488
CO2 0.40 44 17.6 0.512
Mm = yiMi = ( 16.8+17.6)=34.4

(b) What is the mass of 1 m3 of this gas when P = 1.5 MPa and T = 30oC?
Ru
Rm  ( kJ / kg  K )
Mm
kJ
8.314
 kmol  K  0.242 kJ
kg kg  K
34.4
kmol
PmVm
mm 
RmTm
15. MPa (1m3 ) 103 kJ

(0.242 kJ / ( kg  K ))(30  273) K m3 MPa
 20.45 kg
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(c) Find the specific heats at 300 K.

Using Table A-2 (CENGEL), Cp N2 = 1.039 kJ/kgK and Cp CO2 = 0.846 kJ/kgK
2
C p , m   mf i C p ,i  (0.488)(1039
. )  (0.512)(0.846)
1

kJ
 0.940
kgm  K
kJ
Cv , m  C p , m  Rm  (0.940  0.242)
kgm  K
kJ
 0.698
kgm  K

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(d) This gas is heated in a steady-flow process such that the temperature is increased
by 120oC. Find the required heat transfer. The conservation of mass and energy for
steady-flow are

m 1  m 2  m
m 1h1  Q in  m 2 h2
Q  m (h  h )
in 2 1

 mC
 p , m (T2  T1 )
The heat transfer per unit mass flow is
Q in
qin   C p , m (T2  T1 )
m
kJ
 0.940 (120 K )
kgm  K
kJ
 112.8
kgm 16
(e) This mixture undergoes an isentropic process from 0.1 MPa, 30oC, to 0.2 MPa.
Find T2.

The ratio of specific heats for the mixture is

Cp,m 0.940
k   1347
.
Cv , m 0.698
Assuming constant properties for the isentropic process

(f) Find Sm per kg of mixture when the mixture is compressed isothermally from 0.1
MPa to 0.2 MPa.

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But, the compression process is isothermal, T2 = T1. The partial pressures are given
by
Pi  yi Pm
The entropy change becomes

For this problem the components are already mixed before the compression process.
So,
yi , 2  yi ,1
Then,

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 2
sm   mf i si
i 1

kg N 2 kJ kgCO2 kJ
 (0.488 )( 0.206 )  (0.512 )( 0131
. )
kgm kg N 2  K kgm kgCO2  K
kJ
 0167
.
kgm  K
Why is sm negative for this problem? Find the entropy change using the average
specific heats of the mixture. Is your result the same as that above? Should it be?

(g) Both the N2 and CO2 are supplied in separate lines at 0.2 MPa and 300 K to a
mixing chamber and are mixed adiabatically. The resulting mixture has the
composition as given in part (a). Determine the entropy change due to the mixing
process per unit mass of mixture.

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 Take the time to apply the steady-flow conservation of energy and mass to show that
the temperature of the mixture at state 3 is 300 K.

But the mixing process is isothermal, T3 = T2 = T1. The partial pressures are given by

Pi  yi Pm
The entropy change becomes

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But here the components are not mixed initially. So,

y N 2 ,1  1
yCO2 , 2  1
and in the mixture state 3,
y N 2 , 3  0.6
yCO2 , 3  0.4
Then,

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 2
Then,
sm   mf i si
i 1

kg N 2 kJ kgCO2 kJ
 (0.488 )(0152
. )  (0.512 )(0173
. )
kgm kg N 2  K kgm kgCO2  K
kJ
 0163
.
kgm  K
If the process is adiabatic, why did the entropy increase?

Real-Gas Mixtures:
Dalton’s law of additive pressures and Amagat’s law of additive volumes can also be
used for real gases, often with reasonable accuracy.

Van der Waals or Beattie–Bridgeman, Benedict–Webb–

Rubin equations

compressibility factor Z

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Another approach for predicting the P-v-T behavior of a gas mixture is to treat the gas
mixture as a pseudopure substance. One such method, proposed by W. B. Kay in 1936
and called Kay’s rule, involves the use of a pseudocritical pressure P `cr,m and
pseudocritical temperature T`cr,m for the mixture

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Extra Assignment

Nitrogen and carbon dioxide are to be mixed and allowed to flow through a
convergent nozzle. The exit velocity to the nozzle is to be the speed of sound for the
mixture and have a value of 500 m/s when the nozzle exit temperature of the mixture
is 500°C. Determine the required mole fractions of the nitrogen and carbon dioxide to
produce this mixture. From Chapter 17, the speed of sound is given by

C  kRT NOZZLE C = 500 m/s

Mixture T = 500oC
N2 and CO2

Answer: yN2 = 0.589, yCO2 = 0.411

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 Example: Consider a gas mixture that consists of 3 kg of O 2, 5 kg of N2, and 12 kg of
CH4, as shown in Fig. Determine (a) the mass fraction of each component,
(b) the mole fraction of each component, and (c) the average molar mass and gas
constant of the mixture.
Solution: The masses of components of a gas mixture are given.
The mass fractions, the mole fractions, the molar mass, and the gas
constant of the mixture are to be determined.
Analysis :(a) The total mass of the mixture is

Then the mass fraction of each component becomes

(b) To find the mole fractions, we need to determine the mole numbers of each
component first:

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(c) The average molar mass and gas constant of the mixture are determined
from their definitions,

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