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Centre for Energy

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Advanced Thermodynamics
Phase Behaviour of Fluid Mixtures
Lecture 1, 26
th
February 2014
Advanced Thermodynamics
Centre for Energy
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Outline
1. Course Administration
Introduction, Expectations & Outline
2. Phase Behaviour of Pure Substances
3. Phase Behaviour of Fluid Mixtures
4. Solving the Standard Flash Problem
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Introduction & Expectations
About the lecturers
Goal of Education:
The creation of independent, autonomous students
who assume responsibility for their own learning
Why is this unit relevant?
Need to know about:
How fluids behave
Why they behave that way
How we predict that behaviour
Advanced Thermodynamics
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Unit Outline
CHPR4404 Advanced Thermodynami cs
Outl i ne Week Date Tutori al
Topi c Ti tl e Lectures
Wed
11:00 -
12:30
17:30 -
18:15
18:25 -
19:10
19:20 -
20:05
A Phase behaviour & thermodynamics 3 1 26-Feb-14 1-A 2-A 3-A
B Fundamentals of Statistical Mechanics 2 2 5-Mar-14 MultiFlash 4-B 5-B 6-C
C The Perfect Molecular Gas 2 3 12-Mar-14 A,B 7-C 8-D 9-D
D Intermolecular Potential and Virial EOS 3 4 19-Mar-14 C,D 10-D 11-E 12-E
E Corresponding States 2 5 26-Mar-14 D,E Qui z 13-F 14-F
F Equations of State 4 6 2-Apr-14 E,F 15-F 16-F 17-G
G Flash Calculations 3 7 9-Apr-14 F 18-G 19-G 20-H
H Activity Coefficients & Liquid Solutions 2 8 16-Apr-14 G Qui z 21-H 22-I
I Solubility of Solids in Liquids 2 NT 23-Apr-14 Non teach
J Gas Hydrates 2 9 30-Apr-14 H 23-I 24-J 25-J
K Interfaces & Petroleum Fluid Characterisation 2 10 7-May-14 I,J Qui z 26-K 27-K
L Introduction to Transport Properties 2 11 14-May-14 J ,K 28-L 29-L 30-M
M Viscosity Models 2 12 21-May-14 L,M 31-M Mock Exam
31 13 28-May-14 Review Qui z Mock Exam
Semester 1 2014 - Ti mel i ne summary
Lecture/Qui z
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Unit Assessment & Contacts
3 hour final exam: 60 % or 70 %
4 quizzes based on tutorials & lectures: 40% or 30%
Exam weighting adjusted to give student best result
Lecturer & Co-ordinator
Prof Eric F May
Rm 2.50
Eric.May@uwa.edu.au
On sabbatical until April 21st
Lecturers
Dr Thomas Hughes
Rm 2.47B
thomas.hughes@uwa.edu.au
Dr Zachary Aman
Rm 2.49B
zachary.aman@uwa.edu.au
Consultation by appointment (arrange
through email) or during tutorials.
Recommended texts (short-hand author reference in bold)
1) Assael, Trusler & Tsolakis. "Thermophysical Properties
of Fluids: An Introduction to their Prediction"
2) Prausnitz, Lichtenthaler, de Azevedo. "Molecular
Thermodynamics of Fluid-Phase Equilibria"
3) Kyle. "Chemical and Process Thermodynamics"
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1. Choose your response from the
keypad buttons.
2. The light will go GREEN to confirm
your response has been received.
3. You can change your answer by
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NOTE:
Please DO NOT press the GO button, this is
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What is a Phase?
A phase is a homogenous region in space where
the intensive properties are the same.
i.e. uniform properties throughout
A heterogenous system is made up of two or
more phases (homogenous systems).
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PVT Surface for a Pure Substance
a b c d e
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Terminology
Triple Line
Triple Point
Sublimation line
Saturation curve
Dew-point curve
Phase Envelope
What would be the shape of the
PVT surface for an ideal gas?
Critical Point
Melting line
Vapour-pressure curve
Bubble-point curve
Two-phase region
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A non-simple
substance: H
2
O
Clapeyron Equation
T v
L
T v v
h h
dT
dP
o|
o|
| o
| o
A
=

=
) (
For ALL pure substances:
i.e. Slope in P-T plane of
boundary between phases
o and| in terms of latent
heat and change in volume
(per unit mole or mass).
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Phase Behaviour of Fluid Mixture
2 or more components
2 phase region of
PVT surface not flat
(Quality lines)
Exercise: P-V
projection for a
fluid mixture?
Upper dew point (for isotherm)
Lower dew point
(for isotherm)
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Retrograde Behaviour
At point d, there are 2 competing processes
1. Molecules compressed together, start to
associate & form liquid phase
Normal behaviour: P |, liquid volume |
2. Small molecules remaining in gas phase
behave as a solvent for the large molecules
in condensate phase
Retrograde behaviour: P |, liquid volume +
Can be thought of in terms of a supercritical solvent
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Typical Hydrocarbon Mixtures
C
n
notation & plus fraction
Phase envelope completely determined by
composition. Why?
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Phase Envelopes for Reservoir Fluids
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Issues for Engineers
Evaluate reserves & production strategy
Facilities Sizing
Gas-Oil Ratio GOR & CGR
Condensate drop-out and Gas Recycling
Pipeline specifications: HC dew point
Location of dew point curve VERY
sensitive to (small) amounts of heavy HCs
Dew points key parameter for measurement
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N components, 2 phases:
Compositions: Bulk - z
i
, Vap - y
i
, Liq - x
i
, i =1 to N
Molar Flow Rates or Quality Specification:
F
feed
, F
vap
, F
liq
amounts of substance
Phase Behaviour Problem
Vectors length N
The Standard Flash Problem
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Specify F
feed
, z
i
, and two of {T, P, F
liq
}
2N+2 unknowns: x
i
, y
i
, F
vap
& one of {T, P, F
liq
}
N+2 material balance equations:
1
1
=

=
N
i
i
x 1
1
=

=
N
i
i
y
2 normalisation eqns
feed vap liq
F F F = +
feed i vap i liq i
F z F y F x = +
N eqns
Solving the Standard Flash Problem
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Remaining Equations?
Where do we get the remaining N equations?
ANSWER:
Chemical Thermodynamics gives us N equations
in algebraic form:
i
(v)
=
i
(l)
Models of microscopic nature of matter gives us
the numerical values needed to solve them
So we must start with the armoury of
Classical Thermodynamics
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Lecture 1: Core Ideas
1. Phase Behaviour of Pure Substances
PVT Surface, PT & PV Planar Projections, Terminology,
ClapeyronEquation
2. Phase Behaviour of Fluid Mixtures
2-phase AREA in PT plane, Terminology
Retrograde Condensation
3. Typical Reservoir Fluids
Compositions, Phase Behaviour, Critical Points, Issues for
Engineers
4. Solving the Standard Flash Problem
Material balance +Thermodynamics +Model of microscopic world