Gas Mixture

Content:
Composition of gas mixture
P-v-T behavior of gas mixture
Properties of gas mixture: Ideal and real
gases

Composition of gas mixture

Gravimetric analysis

Molar analysis

Conservation of mass : mm = mi

Conservation of mass : N m =

therefore,

mfi =

mf

mi
mm

mole fraction :

=1

Mm =

mm mi
=
=
Nm
Nm

i =1

i =1

mass fraction:

therefore,

N M
i

Nm

yi =

Ni
Nm

=1

= yi M i
i =1

N= mole number, M = molar mass

Rm =

Ru
Mm

Ru=Universal gas const. = 8.313 kJ/kmolK

Example1 Consider a gas mixture which consists of 3 kg of O2,

5 kg of N2 , and 12 kg of CH4 . 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

a)The total mass of the mixture is

mm=mO2+mN2+mCH4= 3+5+12 kg

3 kg O2
5 kg N2
12 kg CH4

The mass fraction of each component becomes:

mf O 2 =

mO 2
3kg
=
= 0.15, mf N 2 = 0.25
mm 20kg

and

mf CH 4 = 0.60

b) To find the mole fractions,

NO2 =

mO 2
3kg
=
= 0.094kmol , N N 2 = 0.179kmol and N CH 4 = 0.750kmol
M O 2 32kg / kmol

b) To find the mole fractions,

N m = N O 2 + N N 2 + N CH 4 = 1.023kmol
yO 2 =

N O 2 0.094kmol
=
= 0.092, y N 2 = 0.175 and
N m 1.023kmol

yCH 4 = 0.733

(c) the average molar mass and gas constant of the mixture

Mm =

mm
20kg
=
= 19.6kg / kmol
N m 1.023kmol

then

R
8.314kJ / kmolK
Rm = u =
= 0.424kJ / kgK
Mm
19.6kg / kmol

3 kg O2
5 kg N2
12 kg CH4

P-v-T Behavior of Gas Mixture

Dalton
Daltons law of additive pressure :
The pressure of a gas mixture (P
(Pm) is equal to the sum
of the pressures each gas would exert if it existed alone
at the mixture temperature and volume.
k

Pm = Pi (Tm , Vm )
i =1

where Pi is component pressure of gas i

Pi
is pressure fraction of gas i
Pm

P-v-T Behavior of Gas Mixture

Amagat
Amagats law of additive volumes :
The volume of a gas mixture (Vm) is equal to the sum
of the volume each gas would occupy if it existed
alone at the mixture temperature and pressure.
k

Vm = Vi (Tm , Pm )
i =1

where Vi is component volume of gas i

Vi
is volume fraction of gas i
Vm

Ideal Gas Mixtures

Ideal Gas Eqn. of State PV = NRuT
PmVm = N m RuTm

(a)

for gas i (Dalton' s law); PiVm = N i RuTm

(b)

for the mixture;

Pi
N
= i = yi (mole fraction)
Pm N m

Then

for gas i (Amagat's law); PmVi = N i RuTm

(c)

Vi
N
= i = yi (mole fraction)
Vm N m

Then
Therefore,

Pi Vi
N
=
= i = yi
Pm Vm N m

(12.8)

Then partial pressure of gas i (Pi, Component pressure) = yiPm

partial volume of gas i (Vi, Component volume) = yiVm

Ideal Gas and Compressibility Factor

(Background from Thermo. I)
The deviation of actual gas from idealideal-gas behavior can
be corrected by the compressibility factor, Z

Z=
where

Z=

vactual
videal

Pv
or Pv = ZRT
RT

and videal = RT / P

The Z factor for all gases is approximate the same at the

same reduced pressure, PR and reduced temperature, TR

PR =

P
T
and TR =
Pcr
Tcr

Z, PR and TR can be found in Table AA-15 and Tcr and Pcr from
Table AA-1

Real Gas Mixtures

Ideal Gas Eqn. of State PV = ZNRuT
for the mixture;

PmVm = Z m N m RuTm

for gas i (Dalton' s law); PiVm = Z i N i RuTm

k

Pm = Pi

and

i =1
k

Therefore,

Z m = yi Z i
i =1

Vm = Vi
i =1

Zm can be determined from both Daltons and Amagats

Law.

Compressibility Factor of Gas Mixture (Zm)

Amagats law find Zi (table A-15) for each gas

from in the mixture from their TR and PR and
k

Z m = yi Z i
i =1

Daltons law find Zi (table A-15) for each gas in

k

the mixture from their VR and PR and Z m = yi Z i

i =1

Then Zm are different from different Laws. Amagats

law is more accurate because intermolecular forces
already consider.

Compressibility Factor Approached

Pcr,m =

K ey's R ule:

Tcr,m =

yP
i

i =1

(12.11a)

cr,i

yT
i =1

cr,i

(12.11b)

W here: Pcr,i and Tcr,i can be determ ined in T able A-1

Pcr,m = Pseudocritical Pressrue
Tcr,m = Pseudocritical T em perature
T hen, T R =

Tm
Tcr , m

and PR =

Pm
Pcr , m

Then, Zm is easily to determined by using these psueocritical

properties TR,m and PR,m (Table A-15).

Example 2 A rigid tank contains 2 kmol of N2 and 6 kmol

of CO2 gases at 300 K and 15 MPa.
MPa. Estimate the volume
of the tank on the basis of (a) the ideal gas equation of
state, (b) Key
Keys Rule, (c) Compressibility factor and
Amagat
Amagats law, and (d) compressibility factor and
Dalton
Daltons law.
Solution
(a) the ideal gas ,

1.330 m3

(b) Keys Rule,

0.652 m3

(c) Z and Amagats law 0.638 m3

(d) Z and Daltons law. 0.648 m3

Properties of Ideal Gas Mixtures

Extensive properties of gas mixtures
_

U m = U i = mi u i = N i u i
_

H m = H i = mi h i = N i h i
_

S m = Si = mi s i = N i s i
Heat capacities of gas mixtures

cv ,m = cv ,i = mi cv ,i = N i cv ,i

c p ,m = c p ,i = mi c p ,i = N i c p ,i

Properties Change of Ideal Gas Mixtures

_

U m = U i = mi u i = N i u i
T2

or (U 2 U1 ) m = mi (u2 u1 ) i = C v ,m dT
i

T1

H m = H i = mi h i = N i h i
T2

or ( H 2 H1 ) m = mi (h2 h1 ) i = C p ,m dT
i

T1

S m = Si = mi s i = N i s i

or ( S 2 S1 ) m = mi ( s2 s1 ) i
i

T2

= mi C p ,i d (ln T ) mi Ri ln
i

T1

pi ,1
pi , 2

Example 3 An insulated rigid tank is devided into two

compartments by a partition. One compartment contains 7 kg of
oxygen gas at 40oC and 100 kPa, and the other component
contains 4 kg of nitrogen gas at 20oC and 150 kPa. Now the
partition is removed, and the two gases are allowed to mix.
Determine, (a) the mixture temperature, and (b) the mixture
pressure after equilibrium has been established.
Solution

a) The energy balance for the system

(no heat transferred to/from the tank):

Ein Eout = Esystem

0 = U = U N 2 + U O 2

[mcv (Tm T1 )]N 2 + [mcv (Tm T1 )]O 2 = 0

Tm = 32.2 o C

(b) the mixture pressure can be calculated

from ideal-gas relation:

PmVm = N m RuTm
NO2 =

mO 2
7 kg
=
= 0.219kmol
M O 2 32kg / kmol

NN2 =

mN 2
4kg
=
= 0.143kmol
M N 2 28kg / kmol

N m = N O 2 + N N 2 = 0.362kmol
VO 2

NR T
(0.219)(8.314)(313)
= u 1 =
= 5.70m 3
100
P
1 O 2

Then,

Pm =

N m RuTm
= 114.4kPa
Vm

NR T
(0.143)(8.314)(293)
= 2.32m 3
VN 2 = u 1 =
150
P
1 N 2
Vm = VO 2 + VN 2 = 8.02m 3

Example 4 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 = vi / vm
Component
N2
CO2

yi

Mi
yiMi
kg/kmol kg/kmol
0.60 28
16.8
0.40 44
17.6
Mm = yi Mi = 34.4

mfi = yiMi /Mm

kgi/kgm
0.488
0.512

(b) What is the mass of 1 m3 of this gas when P = 1.5 MPa

and T = 30oC?
Rm =

mm =

Ru
Mm

( kJ / kg K )

kJ
kmol K = 0.242 kJ
kg
kg K
34.4
kmol

8.314

PmVm
RmTm

15
103 kJ
. MPa (1m3 )
(0.242 kJ / ( kg K ))(30 + 273) K m3 MPa
= 20.45 kg
=

(c) Find the specific heats at 300 K.

Using Table A-2, Cp N2 = 1.039 kJ/kgK and Cp CO2 = 0.846 kJ/kgK
2

C p , m = mf i C p ,i = (0.488)(1039
. ) + (0.512)(0.846)
1

= 0.940

kJ
kgm K

Cv , m = C p , m Rm = ( 0.940 0.242)
= 0.698

kJ
kgm K

kJ
kgm K

(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

& p , m (T2 T1 )
= mC

The heat transfer per unit mass flow is

Q& in
= C p , m (T2 T1 )
m&
kJ
= 0.940
(120 K )
kgm K

qin =

= 112.8

kJ
kgm

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(e) This mixture undergoes an isentropic process from 0.1 MPa, 30oC,
to 0.2 MPa. Find T2.
C

0.940

.
The ratio of specific heats for the mixture is k = Cp,m = 0.698 = 1347
v ,m
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.

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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sm = mfi si
i =1

.
= (0488

kgN2

.
= 0167

kJ
kgm K

kgm

)(0206
.

kgCO2
kJ
kJ
) + (0512
.
)(0131
.
)
kgN2 K
kgm
kgCO2 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
The entropy change becomes

Pi = yi Pm

But here the components are not mixed initially. So,

y N 2 ,1 = 1

and in the mixture state 3,

Then,

yCO2 , 2 = 1
y N 2 , 3 = 0.6
yCO2 , 3 = 0.4

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Then,
2

sm = mf i si
i =1

= (0.488
= 0163
.

kg N 2
kgm

)(0152
.

kJ
kg N 2 K

) + (0.512

kgCO2
kgm

)(0173
.

kJ
kgCO2 K

kJ
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 500C. 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
N2 and CO2

NOZZLE

C = 500 m/s
T = 500oC

Answer: yN2 = 0.589, yCO2 = 0.411

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