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Thermodynamics
Lecture 7
Gaseous Mixtures (Non-Reacting)
Sections 13.1 to 13.3 (Cengel & Boles)
Mass fraction
The total mass of a mixture is the sum of the constituents:
m mi
i
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Mole
The mole is the amount of substance of a system containing as many
elementary entities as there are atoms in 0.012 kg of C.
Example of a mole
One mole of O2 is a mass of 0.032 kg since O has a molar mass of 32.
(compared to 12 for Carbon-12)
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Avogrado's hypothesis
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Mole fraction
The total number of moles, n for a mixture is the sum of the moles
of the constituents.
The ratio, ni/n is termed the mole fraction, xi.
xi 1 for a mixture
i
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1
ni M i i xi M i
n i
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n n1 n2 ...... ni ni
PV PV
PV
PV
PV
1 2 ...... i i
RT RT RT
RT
i RT
P P1 P2 ...... Pi Pi
i
Also x i
ni PV
RT Pi
i
n PV RT P
n n1 n2 ...... ni ni
PV
PV
PV PV1 PV2
...... i i
RT RT RT
RT
i RT
V V1 V2 ......Vi Vi
Also x i
ni PVi RT Vi
n
PV RT V
Pi
P
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Internal energy
For a constituent,
U U 1 U 2 ......U i U i
i
U
U
n
U
i
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n u
i i
xi ui
i
Enthalpy
Total mixture enthalpy:
H U PV
The enthalpy per mole of mixture may be calculated:
H U
V Pi 1
1
U i PiV ni ui PiV
n
n i
n i
i.e. H xi hi
i
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Specific heats
For ideal gases, the specific heat quantities per mole:
CV
dU
xi CV , i
dT
i
CP
dH
xi C P , i
dT
i
R C P CV xi R
i
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Entropy
Total mixture entropy:
S S i ni S i
i
1
S i xi S i
n i
i
s mf i si
i
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Entropy of Mixing
C P dTi R
dPi where Ti temperature of component
Ti
Pi
dT
dP
dS xi C P i xi Ri i
Ti i
Pi
i
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ni mi
n Mi
m
M
ds
mi Ri dPi
dS 1 mi C P i dTi
M m i M i Ti i M i Pi
ds
dPi
dTi
1
mi C P i
mi Ri
Pi
Ti i
m i
The entropy change resulting from mixing may be calculated from the
temperature and partial pressure changes and constituent masses!
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Example 1
The percentage volumetric composition of air is as follows: nitrogen (N ) 78.09,
oxygen (O ) 20.95, argon (Ar) 0.96. Given that the molar masses of the
constitutients are 28, 32 and 40, respectively, calculate the % gravimetric
composition. If the mixture is maintained at 150 kPa and 25C, determine the
partial pressure of the oxygen.
Solution:
The mass per kmole of mixture for each constituent, and hence the %
gravimetric composition may be calculated as shown in the following table:
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Example 1 (contd)
Constituent
Volume
fraction
Molar
mass
Mass per
kmole
% grav comp.
(a)
(b)
(c)
(d)=(b)x(c)
(e)=(d)/(d)
N2
0.7809
28
21.87
75.55
O2
0.2095
32
6.70
23.14
Ar
0.0096
40
0.38
1.31
TOTAL
28.95
100.0
Partial pressure of O2
= vol fraction of O2 x total pressure
= 0.2095 x 150 = 31.44 kPa
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Example 2
Two containers, each of volume 0.7 m3, are isolated from each other by a
partition. One contains O2, the other N2, each at 7 bar and 90C. The partition
is removed and mixing occurs. Calculate the end state of the mixture and the
entropy change.
Solution:
Assuming adiabatic conditions, there will be no changes of pressure, P and
temperature, T of the mixture.
Considering Avogrado's Law,
no. of moles of O2, nO2 = no. of moles of N2 , nN2
Therefore mole fraction of both O2 and N2 ,
x O2 = x N2 = 0.5 after removal of partition
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Example 2 (contd.)
C P dT R
dP
T
P
PV nR T
dT = 0
P
S nO2 R ln
PO2
P
n N 2 R ln
PN 2
=1.87 kJ/K
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Assignment 5
Please attempt:
Problem Set 3:
Q 1 (problem-solving class)
Q 2 (Imparo online tutorial)
(Please attempt problems before referring to the Outline Solutions
for maximum benefit in learning)
Enjoy!!
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