CHAPTER 1
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;
Figure 1.1 Gas mixture
By conservation of mass:
m m A mB
(1.1)
By Daltons law:
P PA PB
(1.2)
For the mixture of a number of gases;
m m A m B mC ...
m m i
or
(1.3)
Where mi is the mass of a constituent
Similarly for the pressure:
P PA PB PC ...
or
P Pi
(1.4)
Where Pi is the partial of a constituent
Example 1.1
A vessel of volume 0.4m3 contains 0.45kg of carbon monoxide (CO) and
1kg of air, at 15C. Calculate the partial pressure of each constituent and the
total pressure in the vessel. The gravimetric analysis of air is to be taken as
23.3% Oxygen and 76.7% Nitrogen. Take the masses of CO, O2, and N2 as
28, 32 and 28kg/kmol.
Solution:
Mass of oxygen=
Mass of nitrogen=
23.3
1 0.233kg
100
76.7
1 0.767kg
100
Thus,
PO 2
0.233 8.3145 288
43.59kN / m 2 0.4359bar
32 0.4
PO 2
0.767 8.3145 288
163.99kN / m 2 1.6399bar
28 0.4
PCO
0.45 8.3145 288
96.21kN / m 2 0.9621bar
28 0.4
Total pressure in the vessel:
P Pi 0.436 1.64 0.962 3.038bar
1.2 Volumetric Analysis of a Gas Mixture
Consider a volume V of a gaseous mixture at a temperature T, considering
of three constituents A, B and C. Let P is the total pressure and T is
temperature and remains constant.
Figure 1.2 Mass, pressure and mole of gas mixture
mA
PAV
R AT
m m A m B mC mi
P PA PB PC Pi
n n A n B nC ni
Where n
Figure
And referring to Figure 1.1
mA
PV A
R AT
Equating the two values for mA, we have
PAV PV A
R AT R AT
i.e. PAV PV A
In general therefore,
Vi
Pi
V
P
(1.8)
Vi
i.e
Pi
V
V Pi
P
P
Now equation 1.4, P Pi , therefore
Vi V
or
n A n B nC n
V A VB VC V
or
n n i
(1.9)
(1.10)
1.3 The Molar Mass and Specific Gas Constant
For any gas in a mixture,
PiV ni T
(1.11)
Therefore,
( PiV ) (ni T )
i.e.
VPi Tni
From equation 1.4, P Pi
PV Tni
Also from equation 1.10, n ni 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
or
VPi Tmi Ri
Now from equation 1.4, P Pi , therefore;
PV Tmi Ri
or
PV mRT Tmi Ri
i.e. mR mi Ri
or
where
mi
Ri
m
(1.12)
mi
is the mass fraction of a constituent.
m
From equation 1.11;
PiV ni T
PV nT
or
Pi ni
P n
(1.13)
This can be combined with equation 1.8, to give
Pi ni Vi
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 ,
From equation 1.3,
PV
PV
i
RT
Ri T
or
Using equation of R
P
P
i i
i.e.
or
thus
P
P
i
R
Ri
and substituting, we have
P Pi i
Pi
i
P
(1.15)
Also using equation 1.14,
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:
5
0.25
20
mN 2
Methane:
m NH 4
12
0.6
20
(b) The mole fraction for:
Oxygen:
nO 2
3
0.094kmol
32
Nitrogen:
nN 2
5
0.179kmol
28
Methane:
n NH 4
12
0.75kmol
16
Total molar fraction= 0.094 + 0.179 + 0.75 = 1.023kmol
(c) Average molar gas and gas constant of mixture:
Average molar gas, Mm= 20kg/1.023kmol = 19.6kg/kmol
Gas constant, Rm= 8.314/19.6 = 0.424kJ/kgK
1.4 Specific Heat Capacities of a Gas Mixture
Using the Gibbs-Dalton law the internal energy of mixture of gases;
mu mi ui
and for a perfect gas,
u C v T . Hence,
mCvT mi CviT
Therefore,
mCv mi Cvi
Cv
or
mi
C vi
m
Similarly form equation (1.6), mh mi hi , and
(1.18)
h C pT ,
Therefore;
mC pT mi C piT
Therefore;
mC p mi C pi
Cp
or
mi
C pi
m
(1.19)
From equation (1.18) and equation (1.19)
C p Cv
mi
m
m
C pi i Cvi i (C pi Cvi )
m
m
m
Using equation, Ri C pi C vi , therefore
C p Cv
Also from equation (1.12), R
mi
Ri
m
mi
Ri , therefore the mixture
m
C p Cv R
The equations below can be applied to a mixture of gases,
Cp
Cv
Cp
R
1
Cv
R
1
The molar heat capacities are defined as follows:
c p mC P
and
cv mC V
From the equation C p C v R , therefore
(1.20)
c p c v mC p mC v mR
And
mR
c p cv
(1.21)
From equation U mC vT
Also from equation m= nM and
mC v cv
U ncvT
(1.22)
1.5 Adiabatic Mixing of Perfect Gases
Consider two gases A and B separated from each other in a closed by a thin
diaphragm as shown in Figure 3.4. If the diaphragm is punctured, then the
gases mix as in Figure 3.4, and each then occupies the total volume.
The process is equivalent to a free expansion and assumed adiabatic. From
equation (1.22):
U 1 n A C vAT A n B C vBTB
and
U 1 (n A C vA n B C vB )T
Extending this results to any number of gases,
U1 ni CviTi
and
Then
U1 = U2
i.e.
n C T
i.e.
U 2 T ni Cv
T ni Cvi
vi i
n C T
n C
i
vi i
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 hA1 mB hB1 Q W m A hA2 mB hB 2
For adiabatic flow, Q= 0, and also W= 0,
m A hA1 mB hB1 m A hA2 mB hB 2
From the equation, h= CpT
m AC PATA mB C PBTB m AC PAT mB C PBT
For any other gases this becomes
m C
i
T T mi CPi
Pi i
m C T
m C
i
Pi i
Pi
Since cpi = mCP
Then
nc p mC P
Hence, T
ni c piTi
n c
i
pi
1.6 Real-Gas Mixture
Daltons law can also be used for real gases. For this case, the component
pressures or component volumes should be evaluated from relations which
account for real gas effects. This is done either by using more exact
solutions of state like van der Waals equation or by using the compressibility
factor as
PV nT
It can be shown that,
k
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
Consider a vessel of fixed volume that maintained at a constant temperature,
Figure 1.3 Mixture of gas and vapor
In Figure 1.3(a), the vessel is evacuated and the absolute pressure is
zero. When a small quantity of water introduced, it evaporates and
occupy the whole volume. The pressure in the vessel is less than the
saturation pressure corresponding to the vessel temperature.
Until, the additional water will not evaporate and the vapor in contact
with its liquid.
If the heat supplied to the vessel, more vapor will evaporate, the
temperature and pressure of vessel will increase.
When a mixture contains a saturated vapor, the partial pressure of
vapor can be found in the table and obeys the Gibbs-Dalton law. This
is only valid for low values of the total pressure.
1.8 The Steam Condenser
Figure 3.4 Air extractions in a condenser
Condenser is used in the steam power plant. The condensation occurs
at 25C to 40C corresponding at Psat= 0.03166 and 0.07375bar
respectively.
There is some leakage of air into condenser and dissolved in the feed
water causes reduction in performance.
The condenser contains a mixture of steam, air and water. The air is
pumped out continually from the condenser to maintain the vacuum
and the air moved out carries some of the steam. Thus, a loss of feed
water to the boiler.
The pressure in the condenser approximately constant at steady
condition. The steam is condensed due to the partial pressure of steam
decreases and the partial pressure of air increases to maintain the same
total pressure.
Example 1.3
A rigid tank contains 0.35kg of steam of quality 0.2 and 0.1kg of nitrogen
gas. If the temperature of the mixture is 90C, determine the volume of the
tank and the pressure of the mixture.
Solution:
The mixture consists of steam, N2, and H2O in liquid phase;
The quality of steam, x
mg
mT
0.2
m g 0.2 0.35 0.07 kg
The mass of liquid H2O,
m f 0.35 0.07 0.28 kg
From the steam table, Ts = 90o
Psat = Pg = 70.14kPa
f = 0.001036m3/kg
g = 2.361m3/kg
Total volume, V
V m f f mg g (0.28 0.001036) (0.07 2.361) 0.166m3
The partial pressure of N2:
PN 2
m N 2 RT 0.1(8.314 / 28 )(363 .15 )
65 .24 kPa
VN 2
0.07 2.361
Since VN2= Vg = 0.07 x 2.361
Thus, Pm = Pg + PN2 = 70.14 + 65.24 = 135.38kPa
