The classification of phase behaviour according

to van Konynenburg and Scott

Bjrn Tore Lvfall

December 18. 2008

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Outline

Background
Important terminology
Classification of phase behaviour
Summary

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Background
Why is a classification system needed?
van der Waals equation of state
RT a
p= Vm b vm2

a = (1 x)2 a11 + 2(1 x)xa12 + x 2 a22

b = (1 x)2 b11 + 2(1 x)xb12 + x 2 b22

Assumes all molecules are the same size

Change of parameters
Only fluid phases
Binary systems

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Global phase diagram

 
a22 a11
=
a + a22
 11 
a11 2a12 + a22
=
a11 + a22

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Important terminology

Phase behaviour
Critical points
Upper critical end point (UCEP)
Lower critical end point (LCEP)
Upper critical solution temperature (UCST)
Lower critical solution temperature (LCST)

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Important terminology (Azeotropes)

Negative azeotrope

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Important terminology (Azeotropes)

Positive azeotrope

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Important terminology (Azeotropes)

Heteroazeotrope

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Global phase diagram

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Type I systems

One critical line from

C1 to C2
Simplest type of
systems
Typical systems:
CO2 -O2 ,Ar-Kr, N2 -O2

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Type I systems

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Global phase diagram

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Type I-A systems

One critical line from

C1 to C2
Negative azeotrope
Typical systems: HCl
dimethylether

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Type I-A systems

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Global phase diagram

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Type II systems

Two critical lines from

C1 to C2 and from Cm
to UCEP
Three phase line
always between the
two vapour pressure
curves.
Typical systems:
CO2 n-octane,
CO2 n-decane and
n-pentane
nitrobenzene

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Type II systems

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Global phase diagram

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Type II-A systems

Two critical lines from

C1 to C2 and from Cm
to UCEP
Positive azeotrope
Typical systems:
CO2 C2 H6 , XeHCl
and H2 Ophenol

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Type II-A systems

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Type II-A systems

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Global phase diagram

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Type III-HA systems

Two critical lines from
C1 to UCEP and from
Cm to C2
Heteroazeotrope
Three phase line
always to the left of
the two vapour
pressure curves.
Typical systems:
H2 Odiethylether,
H2 Opropane and
H2 O1-butene

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Type III-HAm systems

Two critical lines from
C1 to UCEP and from
Cm to C2
Heteroazeotrope
Three phase line
always to the left of
the two vapour
pressure curves.
Typical systems:
H2 Odiethylether,
H2 Opropane and
H2 O1-butene

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Type III-HA systems

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Global phase diagram

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Type III systems

Two critical lines from
C1 to UCEP and from
Cm to C2
Three phase line
always between the
two vapour pressure
curves.
UCEP at higher
temperature and
pressure than C1
Typical systems:
HeXe, NeKr,
methanen-heptane

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Type IIIm systems

Two critical lines from
C1 to UCEP and from
Cm to C2
Three phase line
always between the
two vapour pressure
curves.
UCEP at higher
temperature and
pressure than C1
Typical systems:
HeXe, NeKr,
methanen-heptane

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Type IIIm systems

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Global phase diagram

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Type IV systems
Three critical lines
from C1 to UCEP,
LCEP to C2 and Cm to
UCEP
Two three phase
regions
Typical systems:
methane1-hexene,
benzene
polyisobutene and
cyclohexane
polystyrene

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Type IV systems
Three critical lines
from C1 to UCEP,
LCEP to C2 and Cm to
UCEP
Two three phase
regions
Typical systems:
methane1-hexene,
benzene
polyisobutene and
cyclohexane
polystyrene

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Type IV systems

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Type IV systems

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Type IV systems

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Global phase diagram

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Type V systems

Two critical lines from

C1 to UCEP and
LCEP to C2
Three-phase region,
but not at low
temperature
Typical systems:
ethaneethanol,
CO2 nitrobenzene
and
methanen-hexane

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Type V systems

Two critical lines from

C1 to UCEP and
LCEP to C2
Three-phase region,
but not at low
temperature
Typical systems:
ethaneethanol,
CO2 nitrobenzene
and
methanen-hexane

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Global phase diagram

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Type V-A systems

Two critical lines C1 to

UCEP and LCEP to
C2
Negative azeotrope
Three phase region
but not at low
temperature
Typical systems:
H2 OHCl

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Type V-A systems

Two critical lines C1 to

UCEP and LCEP to
C2
Negative azeotrope
Three phase region
but not at low
temperature
Typical systems:
H2 OHCl

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Type V-A systems

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Extensions of the classification system

Five main types, cover most real systems

Type VI
Type VII
Type VIII
Type II*-IV*

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Summary

van der Waals equation of state

Nine different types of systems
Qualitatively correct, but quantitatively not
Cover most real systems
More advanced approaches gives limited new information

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References
D. Furman and R. B. Griffiths.
Global phase-diagram for a van der waals model of a binary
mixture.
Physical Review a, 17(3):11391148, 1978.
J. S. Rowlinson and F. L. Swinton.
Liquids and Liquid Mixtures.
Butterwoth & Co Ltd, 1982.
R. L. Scott.
Van der waals-like global phase diagrams.
Physical Chemistry Chemical Physics, 1(18):42254231, 1999.
P. H. van Konynenburg and R. L. Scott.
Critical lines and phase equilibria in binary van der Waals
mixtures.
Philos. Trans. R. Soc. London, Ser. A, 298(1442):495540, 1980.
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