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MIXTURES
A pure substance is defined as a substance having a constant and
uniform chemical composition (No chemical reaction taking place).
Properties of a mixture of gases can be determined as for a single gas,
e.g. the properties of air are considered as a single substance
1.1 Daltons Law and the Gibbs-Dalton Law
Consider;
(1.1)
By Daltons law:
P PA PB
(1.2)
or
(1.3)
or
P Pi
(1.4)
23.3
1 0.233kg
100
76.7
1 0.767 kg
100
Thus,
PO 2
PO 2
PCO
PAV
R AT
m m A m B m C m i
P PA PB PC Pi
n n A n B n C n i
Where
Figure
And referring to Figure 1.1
mA
PV A
R AT
R AT
R AT
i.e. PAV PV A
In general therefore,
Vi
i.e
Pi
V
P
(1.8)
Vi
Pi
V
V Pi
P
P
or
n A n B nC n
P Pi ,
therefore
V A V B VC V
or
n n i
(1.9)
(1.10)
(1.11)
Therefore,
( PiV ) ( ni T )
i.e.
VPi Tni
P Pi
PV Tni
n n i
therefore
PV nT
Thus, the mixture is acted as a perfect gas and obeys all the perfect gas laws.
To find the specific gas constant for the mixture in terms of the specific gas
constants of the constituents,
i.e. PV mRT
and
PiV mi Ri T
Then,
PiV mi Ri T
VPi Tmi Ri
or
P Pi ,
i.e.
mR mi Ri
where
mi
m
therefore;
or
PV mRT Tmi Ri
or
mi
Ri
m
(1.12)
PV
nT
Pi ni
P
n
or
(1.13)
P
n V
(1.14)
This means that the molar analysis is identical with the volumetric analysis.
Another method of determining the molar mass is as follows:
mi
PiV
Ri T
and
PV
RT
m m i ,
or
thus
P
P
i
R
Ri
Using equation of R
P
P
i i
i.e.
or
Pi
i
P
(1.15)
Vi
i
V
and
ni
i
n
(1.16)
Example 1.2
Consider a gas mixture that consists of 3kg of oxygen (O2), 5kg of nitrogen
(N2), and 12kg of methane (CH4). Determine:
(a) the mass fraction of each component
(b) the mole fraction of each component
(c) the average molar and gas constant of the mixture
Solution:
(a) Total mass = 3 + 5 + 12 = 20kg
Oxygen:
mO 2
3
0.15
20
Nitrogen:
mN 2
5
0.25
20
Methane:
m NH 4
12
0.6
20
3
0.094kmol
32
Nitrogen:
nN 2
5
0.179kmol
28
Methane:
n NH 4
12
0.75kmol
16
u C vT
. Hence,
m C
vi
Therefore,
mC v
m C
i
vi
or
m C
i
pi
Cv
mh mi hi
mi
C vi
m
, and
(1.18)
h C pT
, Therefore;
Therefore;
mC p mi C pi
Cp
or
mi
C pi
m
(1.19)
mi
m
m
C pi i C vi i (C pi C vi )
m
m
m
Ri C pi C vi
Using equation,
, therefore
C p Cv
mi
Ri ,
m
mi
Ri
m
C p Cv R
Cp
Cv
Cp
R
1
Cv
R
1
and
cv mCV
C p Cv R ,
(1.20)
therefore
c p c v mC p mC v mR
And
mR
c p cv
From equation
(1.21)
U mC v T
mC v cv
U ncv T
(1.22)
and
U 1 ( n A C vA n B C vB )T
n C
i
vi
and
Ti
Then
U1 = U2
i.e.
n C
i.e.
vi
U 2 T ni C v
Ti T ni C vi
n C T
n C
i
vi
vi
Another form of mixing is that which occurs when streams of fluid meet to
form a common stream in steady flow. The steady flow used in the mixing
section is
m A h A1 m B hB1 Q W m A h A 2 m B hB 2
m C
i
Pi
Ti T mi C Pi
m C T
m C
i
Pi
Since
Pi
cpi = mCP
Then
nc p mC P
Hence, T
n c T
n c
i
pi
pi
i ni
i 1
Where is the compressibility factor for the mixture and i is that for a
component. Further by experience it is established that Daltons law is more
appropriate for mixtures at low pressures.
1.7 Gas and Vapor Mixture