Session 6:

Modelling Fluid-Phase Equilibria of Mixtures

Part I

• Prof Amparo Galindo

• ACEX 310
• a.galindo@imperial.ac.uk

Molecular Modelling of Fluids Session 6– Slide 1 © Imperial College London

 Objectives

• Review basic knowledge of phase diagrams

• Interpret any type of binary fluid-phase diagram in the

classification of Scott and van Konynenburg

• Class work
o Use ASPEN to calculate a binary phase diagram with a given
thermodynamic model and interpret the results

Molecular Modelling of Fluids Session 6 – Slide 2 © Imperial College London

 At this point you know

• From earlier sessions in this course

– How the most popular engineering
thermodynamic models (equations of state)
came about
• Van der Waals, Redlich-Kwong and SRK, and Peng-
Robinson equations
– The statistical associating fluid theory: SAFT
• From other courses
– Activity coefficient models
• Wilson, NRTL, UNIQUAC, UNIFAC
Molecular Modelling of Fluids Session 6 – Slide 3 © Imperial College London
 At this point you know

• “Molecular models” are those based on an understanding of the

interactions between molecules (intermolecular interactions)
• By “understanding” here we mean
– We can characterise the interactions between molecules mathematically
• The intermolecular pair potential u(r)
– Lennard-Jones, Mie, square-well
• Molecular parameters
– a and b in van der Waals, SRK, PR
– σ, λ, ε, m in SAFT

• So that:
– Given thermodynamic conditions (p,T,n)
– A model: an equation of state and its model parameters
– Any thermodynamic property can be determined
• Psat, H, µ, cp….

Molecular Modelling of Fluids Session 6 – Slide 4 © Imperial College London

 Pure fluid: determining model
parameters

• Assuming an equation of state model is

chosen (e.g. SAFT, van der Waals)
– Phase behaviour data is used to determine the model
parameters
• Tc, Pc traditionally
• Nowadays Psat and ρsat
– Solve the coexistence conditions
– (You did this in a previous session)

• Our question now is, what happens in

mixtures?

Molecular Modelling of Fluids Session 6 – Slide 5 © Imperial College London

 Mixtures: general considerations
• The addition of components adds to the degrees of
freedom of the system
– Recall the Gibbs phase rule
• F = C – np + 2
• F (degrees of freedom): the number of intensive variables that can be
changed independently without inducing a change in the number of
phases np observed
– Meaning that defining a thermodynamic state requires more
independent variables when more components are present (P,T,n)
• More phases and types of phase equilibrium
– Representation of thermodynamic states in phase diagrams is
more complex
• The solution of phase equilibria is also more complex
– Recall that phase boundaries are the most frequently used data to
develop thermodynamic models

Molecular Modelling of Fluids Session 6 – Slide 6 © Imperial College London

 Pure component phase diagram

Molecular Modelling of Fluids Session 6 – Slide 7 © Imperial College London

 Fluid phase behaviour: pure
substance
• While the phase diagram of a pure substance reasonably simple
– If we concentrate only the fluid phases a P,T diagram presents only the vapour
pressure (saturation) curve
• The critical point is of interest

Molecular Modelling of Fluids Session 6 – Slide 8 © Imperial College London

 Fluid phase behaviour: binary
mixture
• The diagram of a mixture requires one more variable, usually x
(mole fraction) is used
– Occasionally w (weight fraction) when the MWs of the two components
are very different

Molecular Modelling of Fluids Session 6 – Slide 9 © Imperial College London

 Types of binary phase diagram
• Review the constant-temperature Px and constant
pressure Tx phase diagrams:
– Ideal solution/mixture phase diagram
• Mixtures that follow Raoult’s law

Molecular Modelling of Fluids Session 6 – Slide 10 © Imperial College London

 Types of binary phase diagram

– Azeotropic mixtures: Negative azeotropes

• Mixture is less volatile than the pure components
• Often due to strong hydrogen bonding between components

Water + HF @1bar

Molecular Modelling of Fluids Session 6 – Slide 11 © Imperial College London

 Types of binary phase diagram

– Azeotropic mixtures: Positive azeotropes; mixture is more volatile

than the pure components
• Often leads to liquid-liquid separation at low temperature
• Weak interactions between components

C4H10+C4F10

Pratas de Melo et al., Fluid Phase Equilibria, 242, 210 (2006)

Molecular Modelling of Fluids Session 6 – Slide 12 © Imperial College London

 Vapour-liquid-liquid

• In mixtures with weak unlike interactions, those that exhibit liquid-

liquid separation at low T, 3-phase coexistence (vapur-liquid-liquid) is
seen at low P.
• Draw the corresponding Tx phase diagram at constant pressure

Molecular Modelling of Fluids Session 6 – Slide 13 © Imperial College London

 Quick break

• 5 min

Molecular Modelling of Fluids Session 6 – Slide 14 © Imperial College London

 Binary fluid phase behaviour
• Study the complete pressure, temperature, composition space
– Six types of binary phase diagram have been observed
experimentally

Molecular Modelling of Fluids Session 6 – Slide 15 © Imperial College London

 Classification

• Scott and Van Konynenburg

– R.L. Scott, P.H. van Konynenburg, “Static properties of solutions: Van der
Waals and related models for hydrocarbon mixtures”, Discussions of the
Faraday Society 49 (1970) 87–97

Molecular Modelling of Fluids Session 6 – Slide 16 © Imperial College London

 The PT projection
• The classification follows the topology of the critical
lines in the PT projection of the diagram
Type I Type II Type III
P
U

1 1 U 1
2 2 2
Type IV Type V Type VI

U U

1 U
1 L 1
2 L 2 2
U L
T
17

Molecular Modelling of Fluids Session 6 – Slide 17 © Imperial College London

 Type I
• Mixture exhibits a continuous gas-liquid critical line
– The liquid phase is homogeneous throughout
– Components of similar size and polarity (CH4+CO2, H2O+Methanol)

Type I
P
1 2

Molecular Modelling of Fluids Session 6 – Slide 18 © Imperial College London

 Type II

• Mixture exhibits a liquid-liquid critical line ending at an upper critical end point,
in addition to the gas-liquid critical line of type I
– Liquid-liquid demixing is seen at low temperature
– A three-phase line appears
– Components similar vapour pressure but immiscible, or components of very different volatility

Type II

1 U 2

Molecular Modelling of Fluids Session 6 – Slide 19 © Imperial College London

 Type VI

• Similar to type II, but where the liquid-liquid immiscibility disappears at low T
– An additional liquid-liquid critical line is seen
– The three-phase line is limited by an upper and a lower critical end point
– Mixtures with unlike hydrogen bonding (water + C4E1, water + PEG)

Type VI

U
1 L
2

Molecular Modelling of Fluids Session 6 – Slide 20 © Imperial College London

 Type III

• No continuous gas-liquid critical line is seen

– One critical line starts at C2 and continues towards high pressures
– A second shorter critical line starts at C1 and ends at an UCEP
– Components with extreme immiscibility: water + hydrophobic molecules

Type III

U
1 2

Molecular Modelling of Fluids Session 6 – Slide 21 © Imperial College London

 Type V
• As type IV, but with no demixing in the low T liquid region
• Two gas-liquid critical lines:
– One “gas-liquid” critical line starts at C2 and continues towards lower T to end at a LCEP
– A second shorter gas-liquid critical line starts at C1 and ends at an UCEP
• Components with large size difference or critical point, C1+C6, C2+C19, gas+polymer, C2+C2OH

Type V

1
L 2

Molecular Modelling of Fluids Session 6 – Slide 22 © Imperial College London

 Type IV
• Two gas-liquid critical lines + one liquid-liquid critical line are seen
– One “gas-liquid” critical line starts at C2 and continues towards lower T to end at a LCEP
– A second shorter gas-liquid critical line starts at C1 and ends at an UCEP
– A liquid-liquid critical line is also seen at low T
• Components with large size difference or critical point, C1+1-C6=, CO2+C13,
cC6+Polystyrene

U
2
1 L
U

Molecular Modelling of Fluids Session 6 – Slide 23 © Imperial College London

 Break

• 10min
• Grab a quick coffee!

24

Molecular Modelling of Fluids Session 6 – Slide 24 © Imperial College London

 Using ASPEN properties

• Use Aspen to calculate the phase diagram of

water + ethanol @ 1 bar for three
thermodynamic models
– Ideal
– Peng-Robinson
– Predictive SRK

• Identify all phases

• Comment on the accuracy and differences of
the models
Molecular Modelling of Fluids Session 6 – Slide 25 © Imperial College London
 Work in your own time

Molecular Modelling of Fluids Session 6 – Slide 26 © Imperial College London

 Water + ethanol: P=1bar
T-xy diagram for WATER/ETHANOL
376
375
x Ideal
374
y Ideal
373 x PR
372 y PR
371 x PSRK

370 y PSRK

369
368
367
366
365
364
363
Temperature, K

362
361
360
359
358
357
356
355
354
353
352
351
350
349
348
347
346
0.000 0.025 0.050 0.075 0.100 0.125 0.150 0.175 0.200 0.225 0.250 0.275 0.300 0.325 0.350 0.375 0.400 0.425 0.450 0.475 0.500 0.525 0.550 0.575 0.600 0.625 0.650 0.675 0.700 0.725 0.750 0.775 0.800 0.825 0.850 0.875 0.900 0.925 0.950 0.975 1.000
Liqu id/vapor mo le fraction, WATER

Molecular Modelling of Fluids Session 6 – Slide 27 © Imperial College London

 Water + ethanol: P=1bar
T-xy diagram for WATER/ETHANOL
376
375
x Ideal
374
y Ideal
373 x PR
372 y PR
371 x PSRK

370 y PSRK
Exp . y D-1
369
Exp . x D-1
368
367
366
365
364
363
Temperature, K

362
361
360
359
358
357
356
355
354
353
352
351
350
349
348
347
346
0.000 0.025 0.050 0.075 0.100 0.125 0.150 0.175 0.200 0.225 0.250 0.275 0.300 0.325 0.350 0.375 0.400 0.425 0.450 0.475 0.500 0.525 0.550 0.575 0.600 0.625 0.650 0.675 0.700 0.725 0.750 0.775 0.800 0.825 0.850 0.875 0.900 0.925 0.950 0.975 1.000
Liqu id/vapor mo le fraction, WATER

Molecular Modelling of Fluids Session 6 – Slide 28 © Imperial College London

 Water + ethanol P=1bar: PSRK EoS

T-xy diagram for WATER/ETHANOL

100

x 1.0133 b ar
98 y 1.0133 b ar

96

94

92

90
Temperature, C

88

86

84

82

80

78

76
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00
Liqu id/vapor mo le fraction, WATER

Molecular Modelling of Fluids Session 6 – Slide 29 © Imperial College London

 Water + ethanol P=1bar: PR EoS
T-xy diagram for WATER/ETHANOL
102
101
x 1.0133 b ar
100 y 1.0133 b ar
99
98
97
96
95
94
93
92
91

90
89
Temperature, C

88
87
86
85
84
83
82
81
80
79
78
77
76
75
74
73
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00
Liqu id/vapor mo le fraction, WATER

• Result when selecting vapour, liquid, liquid

phases
Molecular Modelling of Fluids Session 6 – Slide 30 © Imperial College London
 Water + ethanol P=1bar: PR EoS
T-xy diagram for WATER/ETHANOL
105

x 1.0133 b ar
100 y 1.0133 b ar

95

90

85

80

75
Temperature, C

70

65

60

55

50

45

40

35
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85 0.90 0.95 1.00
Liqu id/vapor mo le fraction, WATER

• Result when selecting only vapour and liquid phases

Molecular Modelling of Fluids Session 6 – Slide 31 © Imperial College London

 Summary

• There are six types of binary fluid phase behaviour

– Classified by Scott & van Konynenburg
• Review these and make sure you can draw them and identify phases

• Choosing the right thermodynamic model can be

difficult
– Consider the underlying physical assumptions and approximations
of the model chosen
– If possible, comparison with experimental data is recommended

Molecular Modelling of Fluids Session 6 – Slide 32 © Imperial College London