Chemical Engineering 317 2016: Additional Notes

Extension of PVT models to mixtures

General mixing rules

Mixing rules are necessary to combine pure component properties or parameters

to obtain the mixture property or parameter
Only the Virial equation has a 100% theoretical basis for developing mixing rules
Mixing rules are often developed as much for mathematical convenience, as by any
theory
In some case for some EOS, the mixing rule can be related to the physical origin of
the terms involved (e.g. Van der Waals).

Van der Waals EOS mixing Rules

Van der Waals EOS =

Replace a and b parameters with mixture parameters and :

Need some kind of mathematical relationship for and

Qualitatively:
o indicates the attractive energy of the mixture
o parameter the mixture hard sphere volume
Similar (like) molecules:
o a1= a11: Van der Waals attractive interactions between like molecules of
molecule type 1
o Similarly for a2 or a22.
o This implies that molecule of type 1 must find another molecule of type
1 - Probability is proportional to concentration of type 1 vs. concentration
of type 1, i.e. y12.
o Similar for 2-2 interaction probability is y22.
Dissimilar (unlike) molecules
o a12: Van der Waals attractive interactions between unlike molecules of
molecule type 1 and type 2.
o Similarly a21
o This implies that molecule of type 1 must find a molecule of type 2 probability is proportional to concentration of type 1 vs. concentration of
type 2, i.e. y1y2.
o Similar for 2-1 interaction probability is y2 y1
o However a21 and a12 interactions are equivalent thus a21= a12
Mathematically amix:
o = 1 2 11 + 1 2 12 + 2 1 21 + 2 2 22 but 12 = 21 therefore
= 1 2 11 + 21 2 12 + 2 2 22
o a12 we normally estimate from the pure component parameters: 12 =
2
1 2
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If a binary interaction parameter is incorporated: 12 = 21 = 21 2 (1

12 )
The binary interaction parameter can be used to improve the fit of
the model to the mixture data.
Usually by minimizing model error by changing k12
May minimize one or more property e.g. P, T and/or x,y
Remember to consider the phase rule and inputs vs. outputs
Mathematically bmix:
o Remember b is a volume term = 1 1 + 2 2
Generally for multicomponent mixtures: = and =
The van der Waals mixing rules can be applied to all the other cubic EOS (e.g. RK,
SRK, PR)
o The b-value for the mixture is calculated in exactly the same way as for Van
der Waals.
o In the case of the attractive forces in SRK and PR, there is also a parameter, (included in the -value), so instead of a mixture a-value, rather
a mixture a.(T) is calculated along similar lines as for the mixture a, i.e.:
() = () Principle of Corresponding States
o

Mixing Rules

Virial EOS mixing rules

Second order virial coefficient:

Three types of 2-body interactions influencing the second Virial coefficient:

o U11 resulting in B11
o U22 resulting in B22
o U12 resulting in B12
The three second-order Virial coefficients depend only on intermolecular potential
(Uij)
They are independent of composition or density / molar volume.
For a mixture is proportional to number of possible binary interactions weighted
by the amount of species present, i.e.: Bmix = y12B11 + 2y1y2B12 + y22B22
Need values/expression for B12
o Rough approximation: 12 = 11 12
o If possible, use published values for B12
For multiple components: =

Third order virial coefficients

General: = with = 3
For a binary mixture: = 1 3 111 + 31 2 2 112 + 31 2 2 122 + 2 3 222 where
112 = 121 = 211
The virial EOS is the only EOS for which there are rigorous fundamental mixing
rules available

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Corresponding states mixing rules

Mixture pseudo properties are developed using a mole fraction weighted average of the
property (Kays Rule) i.e.

, = , = ,
, = , = ,
= , =

NB! There is no good basis for the mixing rules used in generalized compressibility charts
other than mathematical convenience!
Remember adjustments for quantum gases e.g. hydrogen and helium

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