Session 7:

Modelling Fluid-Phase equilibria of

Mixtures
Part II

Molecular Modelling of Fluids Session 7 – Slide 1 © Imperial College London

 Plan

• The solution of the phase equilibrium problem

• Understand the fundamental ideas used to
develop equations of state for mixtures
– Mixing rules
– Combining rules
– Understand the role of model parameters in the
development of models for mixtures
• Project 2: Use ASPEN to determine and study
unlike binary interaction parameters
– Hand in by email to a.galindo@imperial.ac.uk by 9am
Thurs 8th December.

Molecular Modelling of Fluids Session 7 – Slide 2 © 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 3 © 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 4 © 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 5 © 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 6 © 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 7 © 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 8 © Imperial College London

 Phase equilibrium

• What happened in the calculation of the

phase diagram with the Peng-Robinson
Equation?

• When we calculate phase diagrams of

mixtures and plot the phase boundaries, what
are we actually doing?

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

 Phase equilibrium in mixtures

Problem statement:
• Given:
1. A mixture of C components with mole numbers ni,
i=1,2,..C at a specified thermodynamic state (i.e.P,T)
2. A thermodynamic model, together with its parameter
values describing the C components and their
interactions
• Define:
1. The number np and type (vapour,liquid,solid) of stable
equilibrium phases, and
2. The number of moles of every component in each of
the np phases: nik, i=1,2,…C, k=1,2,…np
Molecular Modelling of Fluids Session 6 – Slide 10 © Imperial College London
 The 2nd law

• It is a consequence of the 2nd law of

thermodynamics that an isolated system will
approach equilibrium by increasing its
entropy,
∆Stotal ≥ 0
And that the equilibrium state is a stationary
point of maximum entropy (dS=0)
– Note: maximum

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

 Solving the phase equilibrium
problem

• Mathematical descriptions of the solution of the phase

equilibrium problem can then be derived following the
restrictions that must hold at every equilibrium state
(1) Material balances for all nc components must be preserved

(2) Pressure, temperature and chemical potential of each component

in the mixture must be equal in all phases

(3) The system should attain the global maximum in its entropy or
equivalently the global minimum of its free energy

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

 The necessary and sufficient
conditions
• Restrictions (1) and (3) are satisfied
– (2) is a consequence of (3) (see theory handout)
• It is a consequence of the 2nd law of thermodynamics that
an isolated system will approach equilibrium by increasing
its entropy, and that an equilibrium state is a stationary
point of entropy (dS=0)
– Restriction (2) can be derived from this statement (see notes)
• A stable equilibrium state is that corresponding to the
global maximum of entropy
– Or equivalently to the global minimum in its free energy
– Specifically, at specified P and T, the stable equilibrium state
corresponds to the global minimum in Gibbs free energy
– Restriction (3)

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

 A mathematical formulation

• For specified temperature Tspec , pressure Pspec , and

component mole numbers

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

 Necessary conditions

• Only restrictions (1) and (2) are satisfied

• Guarantee the conservation of mass in the system and the equality of
temperature, pressure and chemical potential of each component in
all phases

• May correspond to metastable or unstable equilibirum

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

 Necessary conditions in practice

• Often solved as a square system of non-linear equations using a

Newton-type method
– Sensitive to a good starting point sufficiently close to the answer
• Assume np=2 (vapour and liquid)
• Write in terms of mole fractions

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

 Stability analysis

• Ultimately, both global minimisation methods and methods

based on the necessary conditions lack a reliable way of
determining the number of equilibrium phases
• Step-wise approaches that combine the methods above with a
stability analysis check are often used
– The most common stability check is the tangent plane criterion, first
introduced by Gibbs (1873)
– Proved by Barker et al. (1981)
• At given T and P a phase is stable if the tangent plane to the
Gibbs free energy surface at the composition of the phase lies
on or below the Gibbs free energy surface for all possible values
of the composition

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

 The tangent plane criterion

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

 The tangent plane criterion

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

 Recall
• The solution of multicomponent, multiphase equilibria
is far from trivial
– Strictly, it requires finding the global minimum of the Gibbs free
energy (at P and T ).

• Consider the known types of phase diagram to help

assess the validity of results

• An equation of state for mixtures is required

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

 Break

• 10 min

Molecular Modelling of Fluids Session 7 – Slide 21 © Imperial College London

 Mixing rules

• The extension of an equation of state to treat

mixtures requires a number of composition-
dependent expressions; these are the so-
called “mixing rules”
• Consider the van der Waals equation of state for a pure fluid
– Consider it at a molecular level and identify parameters
• Consider now a mixture of van der Waals molecules
– Draw its molecules
– Characterise parameters
– Attempt to write a pressure equation

Molecular Modelling of Fluids Session 7 – Slide 22 © Imperial College London

 Van der Waals one-fluid mixing rule

• Mixture treated as a hypothetical “pure” fluid

• Defined by averaged parameters
– weighted averages (by composition) of the parameters
of each pure
• For the van der Waals equation

∑∑ x x a
nc nc

amix = i j ij
i =1 j =1

∑∑ x x b
nc nc

bmix = i j ij
i =1 j =1

Molecular Modelling of Fluids Session 7 – Slide 23 © Imperial College London

 A one-fluid SW model
• Consider now a square-well potential

• The integrated energy is used to define the parameters of the mixture

∑∑
nc nc

σ mix
3
= xi x jσ ij3
i =1 j =1

∑∑
nc nc

ε mixσ mix
3
(λ3mix − 1) = xi x jε ijσ ij3 (λij3 − 1)
i =1 j =1

• A mixing rule for the range needs to be defined

∑∑
nc nc

σ mix
3
(λ3mix − 1) = xi x jσ ij3 (λij3 − 1)
i =1 j =1

Molecular Modelling of Fluids Session 7 – Slide 24 © Imperial College London

 Combining rules

– commonly used combining rules

• SW potential:
(Lorentz rule)

(adjusted “Berthelot” rule)

• van der Waals’ a and b:

(Lorentz rule)
(adjusted Berthelot rule)
– (try not to confuse mixing rules and combining rules!)
Molecular Modelling of Fluids Session 4 – Slide 25 © Imperial College London
 Improving Cubic EOS for mixtures

• EOS/GE mixing rules

from
Kontogeorgis & Folas
Thermodynamic Models
for Industrial Applications
(Wiley, 2010)

Molecular Modelling of Fluids Session 7 – Slide 26 © Imperial College London

 Improving Cubic EOS

• Predictive cubics: EoS/GE mixing rules

– relate the (molar) excess Gibbs energy obtained with a
given cubic EOS (SRK, PR) at a given pressure
– to that obtained from a liquid-phase activity-coefficient
model (at the same specified reference pressure)
• NRTL, UNIQUAC or UNIFAC often used to obtain gE, the molar
excess Gibbs free energy at a specified pressure
– The result are some of the most successful cubic-
based models for the prediction of properties of fluid
mixtures
• Predictive Soave-Redlich-Kwong (PSRK)
• Predictive Peng-Robinson (PPR)

Molecular Modelling of Fluids Session 7 – Slide 27 © Imperial College London

 Improving Cubic EOS

• Predictive SRK (PSRK) mixing rules

from UNIFAC

Molecular Modelling of Fluids Session 7 – Slide 28 © Imperial College London

 Project 2
• Modelling the phase equilibria of a carbon dioxide +
methane + ethane mixture with the PR EOS using
Aspen properties
– Use the Peng-Robinson equation of state in Aspen-properties to
study the phase behaviour of a three-component mixture
containing carbon dioxide, methane and ethane at fixed
temperature T=220K and pressure P=20 bar.
– Investigate in some detail each of the binary mixtures in order to
confirm that the equation of state chosen and the Aspen
calculations are adequate
– Correlate binary parameters for one of the mixtures
– Obtain the phase diagram of the three-component mixture.
• Hand in by Friday 9th Dec at 4.30pm via BB

Molecular Modelling of Fluids Session 7 – Slide 29 © Imperial College London

 Feedback

• Feedback of Project 1

Molecular Modelling of Fluids Session 7 – Slide 30 © Imperial College London