Mixtures of Gases

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

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. The properties of
the mixture may be based on the mass of each component, called gravimetric
analysis, or on the moles of each component, called molar analysis.

k gases
T = Tm V = Vm
P = Pm m = mm

The total mass of the mixture mm and the total moles of mixture Nm are defined as
k k
mm   mi and N m   Ni
i 1 i 1

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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
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   Mi   yi Mi ( kg / kmol )
N m i 1 N m i 1

4
The apparent (or average) gas constant of a mixture is expressed as
Ru
Rm  ( kJ / kg  K )
Mm
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
yM
mf i  k i i
 yi Mii 1

To change from a mass fraction analysis to a mole fraction analysis, we can show that
mf / M i
yi  k i
 mf i / Mi
i 1

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 Volume fraction (Amagat model)
It describes the behaviour and properties of mixtures of ideal (as well as some cases of non-ideal)
gases. Of use in chemistry and thermodynamics, Amagat's law states that the extensive volume
V = N·v of a gas mixture is equal to the sum of volumes Vi of the K component gases, if the
temperature T and the pressure p remain the same. Divide the container into k sub containers, such
that each sub container 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
Vm  Vi (Tm , Pm )
Amagat's law: i 1

The volume fraction of the vfi of any component is

Vi ( Tm , Pm )
and vf i 
Vm
k

 vf
i 1
i =1 6
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)- This law stating that the pressure exerted by a
mixture of gases in a fixed volume is equal to the sum of the pressures that would be
exerted by each gas alone in the same volume

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

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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 N
  i  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.

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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

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 9
i 1 i 1
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 13-1

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

(b) What is the mass of 1 m3 of this gas when P = 1.5 MPa and T = 30oC?

(c)- Find the specific heats at 300 K.

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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 = 34.4

Ru
Rm  ( kJ / kg  K )
Mm
kJ
(B)- 8.314
 kmol  K  0.242 kJ
34.4
kg kg  K
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, 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 in  m (h2  h1 )
 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 15
kgm
(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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Then,
2
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

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