Gas Mixtures

Nurkholis Hamidi
The discussions in this chapter are restricted to nonreactive ideal-gas mixtures.
Those interested in real-gas mixtures are encouraged to study carefully the material
presented in Chapter 12.

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
2
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. 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.

H2 O2 H2 + O2
＋
6 kg 32 kg 38 kg

H2 O2 H2 + O2
＋
3 kmol 1 kmol 4 kmol

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

3
Consider a gas mixture composed of k components. 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 = H2 + O 2
mm Nm
yH2 = 0.75
Note that yO2 = 0.25
k k

 mf
i =1
i =1 and y
i =1
i =1 1.00

The mass and mole number for a given component are related through the molar
mass (or molecular weight).
mi = Ni Mi
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

5
EXAMPLE
Consider a gas mixture which consist of 3 kg of O2, 5 kg of N2, and 12 kg of CH4. Determine
(a) Mass fraction of each component, (b) mole fraction of each component, and (c) the average
of molar mass and gas constant of the mixture

solution

(a) The total mass of the mixture

mm = mO2 + mN2 + mCH4 = (3 + 5 + 12) = 20 kg

The mass fraction of each component

mO2 3 kg
mf o2 = = = 0.15
mm 20 kg
mN 2 5 kg
mf N 2 = = = 0.25
mm 20 kg
mCH 4 12 kg
mfCH 4 = = = 0.60
mm 20 kg

6
(b) To find the mol fraction of each component, we need to determine the mole
numbers of each component

mO2 3 kg
NO2 = = = 0.094 kmol
M O2 32 kg / kmol
mN 2 5 kg
N N2 = = = 0.179 kmol Nm = 0.94 + 0.179 + 0.750 = 1.023 kmol
M N2 28 kg / kmol
mCH 4 12 kg
NCH 4 = = = 0.750 kmol
M CH 4 16 kg / kmol

The mol fraction of each component

N O2 0.094 kmol
yO2 = = = 0.092
Nm 1.023kmol
N N2 0.179 kmol
yN2 = = = 0.175
Nm 1.023kmol
N CH 4 0.750 kmol
yCH 4 = = = 0.733
Nm 1.023kmol
7
(c) the average of molar mass and gas constant of the mixture

mm 20 kg
Mm = = = 19.6 kg / kmol
N m 1.023kmol
or
Mm = y M i i = yO2 M O2 + y N 2 M N 2 + yCH 4 M CH 4
= (0.092)(32) + (0.175)(28) + (0.733)(16)
= 19.6 kg / kmol
Ru 8.314 kJ /(kmol.K )
Rm = = = 0.424 kJ /(kg.K )
Mm 19.6 kg / kmol

8
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.

Gas A Gas B Gas mixture

P, T ＋ P, T
 A+B
P, T
VA VB VA+ VB

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

Vi is called the component volume.

Vi (Tm , Pm )
The volume fraction of the vfi of any component is vf i =
Vm
and
k

 vf
i =1
i =1
9
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.

10
Partial pressure (Dalton model)

Dalton's law of additive pressure states that the volume of a gas mixture is equal to
the sum of the pressure each gas would exert if it existed alone at the mixture
temperature and volume.

Gas A Gas B Gas


mixture
T, V ＋ T, V A+B
T, V
PA PB PA+ PB

k
Dalton’s law: Pm =  Pi (Tm ,Vm )
i =1

Pi is called the component pressure.

11
For ideal Gas

Ni RuTm
Pi (Tm ,Vm ) Vm Ni
= = = yi
Pm N R T
m u m Nm
Vm
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.

Therefore Pi = yi Pm
Pi V N
= i = i = yi Vi = yi Vm
Pm Vm N m
Ni = yi N m

yi Pm is called the partial pressure (identical to the component pressure for ideal gases).
yi Vm is called the partial volume (identical to the component pressure for ideal gases)

12
Real Gas
Dalton’s law and Amagat’s law can also be used for real gas. This time, however, the
component pressure or component volume should be evaluated from relations that take
into account the deviation of each component from ideal gas behavior. One way doing
that is use more exact equations of state (van der Walls, Beattie-Bridgeman, etc).
Another way is to use the compressibility factor as :

PV = ZNRuT

The Zm can be expressed in terms of the compressibility factor of individual gases Zi

k
Zm = y Z
i =1
i i

Where Zi is determined either at Tm and Vm (Dalton’s law) or at Tm and Pm (Amagat’s

law) for each individual gas.
The compressibility factor approach, in general, gives more accurate results when the
Zi ‘s are evaluated using Amagat’s law.

13
Another approach for predicting the P-v-T behavior of a gas mixture is to treat the gas
mixture as pseudo-pure substance. One such method, proposed by W.B Kay and Kay
rule，involves the use of pseudocritical pressure P’cr,m and pseudocritical temperature
T’cr,m. k k
P 'cr , m = y P
i =1
i cr ,i and T 'cr , m = yT i =1
i cr ,i

The Zm can be determined easily using these pseudocritical properties

Another way of treating gas mixture as pseudopure substance is to use more exact
equations of state (van der Walls, Beattie-Bridgeman, etc). In the van der Walls
equation, for example, the two constants can be determined from

 k  k
am = 
  yi ai1/ 2  2

and bm = yb i i
 i =1  i =1

14
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
k k
and 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 15
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

16
The entropy change of the mixture per mass of mixture is

The entropy change of the mixture per mole of mixture is

17
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

18
 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

(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
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

19
(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

20
(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 21
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.

22
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,

23
 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.

24
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

25
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,

26
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
If the process is adiabatic, why did the entropy increase?

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 500oC. 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 Mixture
NOZZLE C = 500 m/s
T = 500oC
N2 and CO2

Answer: yN2 = 0.589, yCO2 = 0.411 27