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Some definitions
The mass of a mixture mm is the sum of the masses of the individual components, and the
mole number of the mixture Nm is the sum of the mole number of the individual
components:
k k
m m mi and Nm Ni
i 1 i 1
Mass fraction, mf: the ratio of the mass of a component to the mass of the mixture
mi
mf i
mm
Mole fraction, y: the ratio of the mole number of a component to the mole number of the
mixture
Ni
yi
Nm
Note that the sum of the mass fractions or mole fractions for a mixture is equal to 1.
The mass of a substance can be expressed as: m = NM.
Apparent molar mass:
Mm
mm
N M i i
y i M i or
Nm Nm
mm mm 1 1
Mm
Nm mi / M i mi / mm M i mf i / M i
Ru
Gas constant of a mixture can be written as: Rm ; and Ru = 8.314 kPa.m3/kmol.K
Mm
Mass and mole fractions of a mixture are related by:
mi NM M
mf i i i yi i
mm N m M m Mm
V, T V, T V, T
+ =
mA, NA, PA mB, NB, PB mm = mA + mB
Nm = NA + NB
Pm = PA + PB
P, T P, T P, T
+ =
mA, NA, VA mB, NB, VB mm = mA + mB
Nm = NA + NB
Vm = VA + VB
Real Gas Properties
Dalton’s law and Amagat’s law can also be used for real gases, often with reasonable
accuracy. However; the component pressure or volume should be calculated using
relationships that take into account the deviation of each component from ideal gas
behavior. One way of doing this is to use the compressibility factor:
PV = ZNRuT
The compressibility factor of the mixture Zm can be calculated from:
k
Z m yi Z i
i 1
where Zi is determined either at Tm and Vm (Dalton’s law) or at Tm and Pm (Amagat’s law)
for each individual gas. It should be noted that for real-gas mixtures, these two laws give
different results.
Kay’s Rule
Involves the use of a pseudo-critical pressure and pseudo-critical temperature for the
mixture, defined in terms of the critical pressures and temperatures of the mixtures
components as:
P ' cr ,m y i Pcr ,i and T ' cr ,m y i Tcr ,i
The compressibility factor of the mixture is then easily determined by using these
pseudo-critical properties. The result obtained by using Kay’s rule is accurate to within
10%.
Example 1
A rigid tank contains 2 kmol of N2 and 6 kmol of CO2 gases at 300 K and 15 MPa.
Estimate the volume of the tank on the basis of: a) the ideal-gas equation of state, b)
Kay’s rule, c) compressibility factors and Amagat’s law, and d) compressibility factors
and Dalton’s law.
Analysis:
a) Assuming ideal gas, the volume of the mixture is calculated from:
N m Ru Tm 8kmol 8.314kPa.m 3 / kmol. K 300 K
Vm 1.330m 3
Pm 15,000kPa
since
N m N N 2 N CO2 6 2 8kmol
The molar fractions are:
thus;
Vm
Z m N m Ru Tm 0.498kmol 8.314kPa.m 3 / kmol. K 300 K
0.652m 3
Pm 15,000kPa
c) Amagat’s law:
Tm 300 K
TR , N 2 2.38
Tcr , N 2 126.2 K
N2 :
Pm 15MPa Fig . A 15b Z N 2 1.02
PR , N 2 4.42
Pcr , N 2 3.39MPa
Tm 300 K
TR ,CO2 0.99
Tcr ,CO2 304.2 K
CO2 :
Pm 15MPa Fig . A 15b Z CO2 0.3
PR ,CO2 2.03
Pcr ,CO2 7.39MPa
Mixture:
Z m y i Z i y N 2 Z N 2 y CO2 Z CO2
0.251.02 0.750.3 0.48
Thus;
Vm
Z m N m Ru Tm 0.488kmol 8.314kPa.m 3 / kmol. K 300 K
0.638m 3
Pm 15,000kPa
Note that the compressibility factor in this case turned out to be almost the same as the
one determined by using Kay’s rule.
1.33m /2kmol 3
Similarly,
1.33m /6kmol 3
V R ,CO2
8.314kPa.m / kmol.K 304.2K /7390kPa 0.648
3
From Fig. A-15, we read ZN2 = 0.99 and ZCO2 = 0.56, thus,
Z m y N 2 Z N 2 y CO2 Z CO2 0.250.99 0.750.56 0.67
and,
Vm
Z m N m Ru Tm 0.67 8kmol 8.314kPa.m 3 / kmol. K 300 K
0.891m 3
Pm 15,000kPa
This is 33% lower than the assumed value. Therefore, we should repeat the calculations,
using the new value of Vm. When calculations are repeated we obtain 0.738 m3 after the
second iteration, 0.678 m3 after the third iteration, and 0.648 m3 after the fourth iteration.
This value does not change with more iteration. Therefore:
Vm = 0.648 m3
Note that the results obtained in parts (b), (c), and (d) are very close. But they are very
different from the ideal gas value. Therefore, treating a mixture of gases as an ideal gas
may yield unacceptable errors at high pressures.
Mixture Properties
Extensive properties such as U, H, cp, cv and S can be found by adding the contribution of
each component at the condition at which the component exists in the mixture.
k k k
U m U i mi u i N i u i kJ
i 1 i 1 i 1
k k k
H m H i mi hi N i hi kJ
i 1 i 1 i 1
k k k
S m S i mi s i N i s i kJ / K
i 1 i 1 i 1
Care should be exercised in evaluating the Δs of the components since the entropy of an
ideal gas depends on the pressure or volume of the component as well as on its
temperature.
k k Pi , 2
s 2 s1 m mf i s 2 s1 i mf i c p ,i ln T2 Ri ln
i 1 i 1 T 1 Pi ,1 i
Notes:
when ideal gases are mixed, a change in entropy occurs as a result of the increase in
disorder in the systems
if the initial temperature of all constituents are the same, the mixing process is
adiabatic; i.e., temperature does not change – but entropy does!
P P
S m m1 R1 ln 1 m2 R2 ln 2 ...
P P
k
P
mi Ri i
i 1 P