The classification of phase behaviour according

to van Konynenburg and Scott

Bjørn Tore Løvfall

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
ζ=
a + a22
 11 
a11 − 2a12 + a22
Λ=
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 , Xe–HCl
and H2 O–phenol

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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 O–diethylether,
H2 O–propane and
H2 O–1-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 O–diethylether,
H2 O–propane and
H2 O–1-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:
He–Xe, Ne–Kr,
methane–n-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:
He–Xe, Ne–Kr,
methane–n-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:
methane–1-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:
methane–1-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:
ethane–ethanol,
CO2 –nitrobenzene
and
methane–n-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:
ethane–ethanol,
CO2 –nitrobenzene
and
methane–n-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 O–HCl

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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 O–HCl

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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):1139–1148, 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):4225–4231, 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):495–540, 1980.
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