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

Gas Mixtures 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 The composition of a gas mixture is described by specifying either the mass fraction
mfi or the mole fraction yi of each component i.
Consider a container having a volume V that is filled with a mixture of k different mi Ni
gases at a pressure P and a temperature T. mf i = and yi =
mm Nm
A mixture of two or more gases of fixed chemical composition is called a nonreacting Note that
gas mixture. Consider k gases in a rigid container as shown here. The properties of k k
the mixture may be based on the mass of each component, called gravimetric ∑ mf
i =1
i =1 and ∑y
i =1
i =1
analysis, or on the moles of each component, called molar analysis.

k gases
The mass and mole number for a given component are related through the molar
T = Tm V = Vm mass (or molecular weight).
P = Pm m = mm
mi = N i M i
The total mass of the mixture mm and the total moles of mixture Nm are defined as To find the average molar mass for the mixture Mm , note
k k
k
mm = ∑ mi and
k
N m = ∑ Ni
mm = ∑ mi = ∑ N i M i = N m M m
i =1 i =1
i =1 i =1

Solving for the average or apparent molar mass Mm

k k
mm N
Mm = = ∑ i M i = ∑ yi M i ( kg / kmol )
N m i =1 N m i =1

3 4
The apparent (or average) gas constant of a mixture is expressed as Volume fraction (Amagat model)
Ru
Rm = ( kJ / kg ⋅ K ) Divide the container into k subcontainers, such that each subcontainer has only one
Mm of the gases in the mixture at the original mixture temperature and pressure.
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 Amagat's law of additive vol-umes states that the volume of a gas mixture is equal to
mf i = k i i the sum of the volumes each gas would occupy if it existed alone at the mixture
∑ yi Mi i =1
temperature and pressure.
k
Amagat's law: Vm = ∑ Vi (Tm , Pm )
To change from a mass fraction analysis to a mole fraction analysis, we can show that i =1

mf / M i The volume fraction of the vfi of any component is

yi = k i
∑ mf i / Mi
i =1 vf i =
Vi ( Tm , Pm )
Vm
and
k

∑ vf
i =1
i =1
5 6

For an ideal gas mixture Now, consider placing each of the k gases in a separate container having the volume
NRT N RT of the mixture at the temperature of the mixture. The pressure that results is called
Vi = i u m and Vm = m u m
Pm Pm the component pressure, Pi' .
Taking the ratio of these two equations gives
Vi N
vf i = = i = yi
Vm N m
The volume fraction and the mole fraction of a component in an ideal gas mixture are N i Ru Tm N m Ru Tm
Pi ' = and Pm =
the same. Vm Vm
Note that the ratio of Pi' to Pm is
Partial pressure (Dalton model)
Pi ' Vi N
= = i = yi
The partial pressure of component i is defined as the product of the mole fraction and Pm Vm N m
the mixture pressure according to Dalton’s law. For the component i
For ideal-gas mixtures, the partial pressure and the component pressure are the
Pi = yi Pm same and are equal to the product of the mole fraction and the mixture pressure.
k
Dalton’s law: Pm = ∑ Pi ( Tm ,Vm )
i =1

7 8
 Other properties of ideal-gas mixtures 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
The extensive properties of a gas mixture, in general, can be determined by summing real-gas relations developed in earlier chapters.
the contributions of each component of the mixture. The evalu-ation of intensive
properties of a gas mixture, however, involves averaging in terms of mass or mole Ratio of specific heats k is given as
fractions: C p ,m C p ,m
km = =
k k k
U m = ∑ U i = ∑ mi ui = ∑ N i ui (kJ)
i =1 i =1 i =1
Cv ,m Cv ,m
k k k
Hm = ∑ Hi = ∑ mi hi = ∑ N i hi (kJ) The entropy of a mixture of ideal gases is equal to the sum of the entropies of the
i =1 i =1 i =1 component gases as they exist in the mixture. We employ the Gibbs-Dalton law that
k k k says each gas behaves as if it alone occupies the volume of the system at the
Sm = ∑ Si = ∑ mi si = ∑ N i si (kJ / K) mixture temperature. That is, the pressure of each component is the partial pressure.
i =1 i =1 i =1

and k k
For constant specific heats, the entropy change of any component is
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 10
i =1 i =1

The entropy change of the mixture per mass of mixture is 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

The entropy change of the mixture per mole of mixture is
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

11 12
 Comp. yi Mi yiMi mfi = yiMi /Mm (c) Find the specific heats at 300 K.
kg/kmol kg/kmol kgi/kgm
N2 0.60 28 16.8 0.488 Using Table A-2, Cp N2 = 1.039 kJ/kg⋅K and Cp CO2 = 0.846 kJ/kg⋅K
CO2 0.40 44 17.6 0.512 2
Mm = ΣyiMi = 34.4 C p , m = ∑ mf i C p ,i = (0.488)(1039
. ) + (0.512)(0.846)
1
(b) What is the mass of 1 m3 of this gas when P = 1.5 MPa and T = 30oC? kJ
= 0.940
R
Rm = u ( kJ / kg ⋅ K ) kgm ⋅ K
Mm
kJ
kJ Cv , m = C p , m − Rm = (0.940 − 0.242)
8.314
kmol ⋅ K = 0.242 kJ kgm ⋅ K
=
34.4
kg kg ⋅ K kJ
kmol = 0.698
kgm ⋅ K
PmVm
mm =
RmTm
. MPa (1m3 )
15 103 kJ
=
(0.242 kJ / ( kg ⋅ K ))(30 + 273) K m3 MPa
= 20.45 kg

13 14

(d) This gas is heated in a steady-flow process such that the temperature is (e) This mixture undergoes an isentropic process from 0.1 MPa, 30oC, to 0.2 MPa.
increased by 120oC. Find the required heat transfer. The conservation of mass and Find T2.
energy for steady-flow are
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

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 (f) Find ΔSm per kg of mixture when the mixture is compressed isothermally from 0.1
qin = = C p , m (T2 − T1 ) MPa to 0.2 MPa.
m&
kJ
= 0.940 (120 K )
kgm ⋅ K
kJ
= 112.8 15 16
kgm
 2
But, the compression process is isothermal, T2 = T1. The partial pressures are given Δsm = ∑ mf i Δsi
by i =1

Pi = yi Pm = (0.488
kg N 2
)( −0.206
kJ
) + (0.512
kgCO2
)( −0131
.
kJ
)
kgm kg N 2 ⋅ K kgm kgCO2 ⋅ K
The entropy change becomes
kJ
= −0167
.
kgm ⋅ K
Why is Δsm negative for this problem? Find the entropy change using the average
For this problem the components are already mixed before the compression process. specific heats of the mixture. Is your result the same as that above? Should it be?
So,
(g) Both the N2 and CO2 are supplied in separate lines at 0.2 MPa and 300 K to a
yi , 2 = yi ,1
mixing chamber and are mixed adiabatically. The resulting mixture has the
Then, composition as given in part (a). Determine the entropy change due to the mixing
process per unit mass of mixture.

17 18

Take the time to apply the steady-flow conservation of energy and mass to show that But here the components are not mixed initially. So,
the temperature of the mixture at state 3 is 300 K.
y N 2 ,1 = 1
yCO2 , 2 = 1
and in the mixture state 3,
y N 2 , 3 = 0.6
But the mixing process is isothermal, T3 = T2 = T1. The partial pressures are given by yCO2 , 3 = 0.4
Pi = yi Pm Then,

The entropy change becomes

19 20
Then,
2
Δsm = ∑ mf i Δsi
i =1

kg N 2 kJ kgCO2 kJ
= (0.488 )(0152
. ) + (0.512 )(0173
. )
kgm kg N 2 ⋅ K kgm kgCO2 ⋅ K
z Q9-18 (b) 0.422kJ (c) 20.4%
kJ z Q9-19 (b) 0.39kJ (c) 20.9%
= 0163
.
kgm ⋅ K z Q9-23 (a) 46.1 kPa (b) 87.5 kJ/kg (c) 0.533 (d) 0.578
z Q9-32 Given in text book
If the process is adiabatic, why did the entropy increase?
z Q9-35 Given in text book
z Q9-47 (a) 1.848 (b) 158.87 Btu/lbm (c) 59.1%
Extra Assignment
z Q9-57 Given in text book
z Q9-76 (a) 52.7% (b) 27.0%
Nitrogen and carbon dioxide are to be mixed and allowed to flow through a
z Q9-80 Given in text book
convergent nozzle. The exit velocity to the nozzle is to be the speed of sound for the
z Q9-92 Given in text book
mixture and have a value of 500 m/s when the nozzle exit temperature of the mixture
z Q9-94 Given in text book
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

21 22
Answer: yN2 = 0.589, yCO2 = 0.411