EG5099 Phase Behaviour and Physical Properties T.

Baxter

Phase Behaviour and Physical

Properties

1
EG5099 Phase Behaviour and Physical Properties T. Baxter

1 Introduction ............................................................................................................................. 3
2 Oil and Gas Components...................................................................................................... 3
2.1 Paraffins ........................................................................................................................ 3
2.2 Aromatics ...................................................................................................................... 3
2.3 Naphthenes .................................................................................................................... 4
2.4 Sulphur .......................................................................................................................... 4
2.5 Nitrogen ......................................................................................................................... 5
2.6 Carbon Dioxide ............................................................................................................. 5
2.7 Water ............................................................................................................................. 5
2.8 Mercury ......................................................................................................................... 5
3 Reservoir Oil and Gas .......................................................................................................... 6
3.1 Phase Diagrams ............................................................................................................. 7
3.1.1 Single Phase Fluid .................................................................................................. 7
3.1.2 Multicomponent Fluid ............................................................................................ 7
3.1.3 Phase Behaviour for differing Reservoir types ...................................................... 8
4 Fluid Sampling ................................................................................................................... 13
4.1 Drill Stem Test ............................................................................................................ 13
4.2 Extended Well Testing ................................................................................................ 13
5 Fluid Modelling .................................................................................................................. 14
5.1 Black Oil ..................................................................................................................... 14
5.2 Compositional ............................................................................................................. 14
5.2.1 Pseudo-Component .............................................................................................. 15
5.3 Equilibrium Ratios ...................................................................................................... 17
5.3.1 Bubble Point Calculation ..................................................................................... 18
5.3.2 Dew Point Calculation ......................................................................................... 18
5.3.3 Flash Calculation Procedure................................................................................. 18
5.4 Equations of State........................................................................................................ 24
5.4.1 Van der Waals ...................................................................................................... 24
5.4.2 Soave-Redlich-Kwong (SRK) .............................................................................. 25
5.4.3 Peng-Robinson ..................................................................................................... 28
5.5 Property Package Selection ......................................................................................... 30
5.5.1 BWRS................................................................................................................... 33
5.5.2 CPA Model – Polar Fluids ................................................................................... 34
5.5.3 Activity Models .................................................................................................... 35
5.5.4 Modelling Summary............................................................................................. 37
5.5.5 CO2 Modelling ..................................................................................................... 40
5.6 The Mollier Chart ........................................................................................................ 40
5.7 Crude Assay ................................................................................................................ 43
6 Physical Properties ............................................................................................................. 45
6.1 Critical and Reduced Temperature and Pressure ........................................................ 46
6.2 Liquid Density ............................................................................................................. 46
6.3 Gas Compressibility .................................................................................................... 50
6.4 Viscosity ...................................................................................................................... 53
6.4.1 Liquid ................................................................................................................... 53
6.4.2 Gas ........................................................................................................................ 54
6.5 Specific Heat Capacity ................................................................................................ 56
6.6 Thermal Conductivity ................................................................................................. 56
6.7 Surface Tension ........................................................................................................... 56
6.8 Vapour Pressure .......................................................................................................... 57
7 Key Learnings .................................................................................................................... 58
8 Reference books ................................................................................................................. 58

2
EG5099 Phase Behaviour and Physical Properties T. Baxter

1 Introduction
Accurate predicting of phase behaviour, and thermodynamic and physical properties is a pre-
requisite of process design and rating calculations. This module sets out a range of common
methods used in practice.

2 Oil and Gas Components

Naturally occurring oil and gas reservoirs contain a wide range of hydrocarbon compounds
and other species.

2.1 Paraffins
The paraffinic series of hydrocarbon compounds have the general formula CnH2n+2 and can be
either straight chains (normal) or branched chains (isomers) of carbon atoms. Paraffinic
hydrocarbons are commonly referred to as alkanes.

2.2 Aromatics
Aromatics are unsaturated ring-type (cyclic) compounds. All aromatics have at least one
benzene ring (a single-ring compound characterized by three double bonds alternating with
three single bonds between six carbon atoms) as part of their molecular structure.
Naphthalenes are fused double-ring aromatic compounds. The most complex aromatics are
the polycyclic aromatic hydrocarbons (PAH), also referred to as polynuclear hydrocarbons,
with three or more fused aromatic rings and they typically are found in the heavier fractions
of petroleum crude oil. PAH are generally toxic to most organisms.

3
EG5099 Phase Behaviour and Physical Properties T. Baxter

2.3 Naphthenes
Naphthenes are saturated hydrocarbon compounds having the general formula of CnH2n,
arranged in the form of closed rings. Naphthenes are also commonly referred to as
cycloparaffins or cycloalkanes.
Single-ring naphthenes (monocycloparaffins) with five and six carbon atoms predominate,
with two-ring naphthenes (dicycloparaffins) found in the heavier ends of the naphtha fraction
of petroleum crude oil.

2.4 Sulphur
Sulphur compounds occur to some extent in most naturally occurring oil and gases. They are
unwanted as sulphur compounds are poisons for many catalytic processes used within refinery
operations. In the presence of water they are corrosive. When burned/flared the sulphur
oxidises to sulphur dioxide – an atmospheric pollutant.
Typical sulphur species are shown below.

4
EG5099 Phase Behaviour and Physical Properties T. Baxter

2.5 Nitrogen
Nitrogen is present in many oil and gas fields. Note that nitrogen can significantly effect
phase behaviour characteristics with consequent impacts on processing requirements.

2.6 Carbon Dioxide

Like Nitrogen, carbon dioxide is a feature of most reservoirs. In combination with water it is
corrosive.

2.7 Water
Water is a ubiquitous component of almost oil naturally occurring hydrocarbon reservoirs. Its
presence and composition can significantly impact the process plant configuration as will be
discussed later.

2.8 Mercury
Mercury is found in many oil and gas fields. It is a concern for metallurgy particularly
Aluminium. It is also a health hazard.

5
EG5099 Phase Behaviour and Physical Properties T. Baxter

3 Reservoir Oil and Gas

Reservoir oil is conditioned to allow for pipeline transportation or as a suitable feedstock for a
refinery. The components of the unprocessed fluids and the refined products are shown.
CARBON DIOXIDE
HYDROGEN SULPHIDE

METHANE &
ETHANE
SUBSTANCE USES
LOWEST Propane and butane gas for lighter fuel
gases
& camping stoves
BOILING POINT
Chemicals for medicines, plastics, paints,
naphtha
cosmetics & clothing materials

gasoline Petrol for vehicles

kerosene Jet fuel and paraffin

diesel oils Diesel fuel

Lubricating
Machine oil, waxes and polishes
oils

Fuel oil Fuel for ships and central heating

HIGHEST
BOILING POINT Bitumen for road surfaces and roofing
residue
materials

WATER

SAND

Like oil, gas is conditioned into a form suitable for transportation and sale. It should be noted
that there is no typical oil or gas composition. Each field is different due to the geochemical
formation processes which produced the hydrocarbons.

6
EG5099 Phase Behaviour and Physical Properties T. Baxter

3.1 Phase Diagrams

An ability to predict the phase state of the fluids to be processed is an essential step in any
process design. Inaccurate prediction will lead to a flawed design of the associated process
equipment.

3.1.1 Single Phase Fluid

Consider the phase characteristics of water.

As can be seen the phase transition from all liquid to all vapour occurs at a single point. This
is not the case for a multicomponent mixture such as a naturally occurring oil or gas.

3.1.2 Multicomponent Fluid

7
EG5099 Phase Behaviour and Physical Properties T. Baxter

Here a different behaviour is seen – at a given pressure the transition from liquid to vapour
occurs across a temperature range as the heavier molecular weight components change phase
from liquid to vapour.
Key aspects of this phase behaviour plot are:
Bubble Point
The point at which the first infinitesimally small vapour bubble appears in a liquid system.
The bubble point curve on a phase diagram represents 0% vapour
Dew Point
The point at which the first infinitesimally small droplet of condensation forms in a gaseous
system. The dew point curve on a phase diagram represents 0% liquid
Phase Envelope
The area on a pressure-temperature phase diagram for a mixture enclosed by the bubble and
dew point curves. This area represents the set of conditions for the mixture where vapour and
liquid phases co-exist in equilibrium.
Cricondenbar
The maximum pressure at which vapour and liquid can co-exist in equilibrium
Cricondentherm
The maximum temperature at which vapour and liquid can co-exist in equilibrium.
Critical Point
At the critical point, liquid and vapour phases of a fluid have identical physical properties.
Quality Lines
Lines through the two-phase region showing a constant percentage of liquid and vapour.
Retrograde
The name given to phase behaviour where the slope of the quality line changes from negative
to positive.

3.1.3 Phase Behaviour for differing Reservoir types

Jargon used in the oilfield often categorises reservoirs into four types with a characteristic
phase behaviour as follows. There is no clear definition categorising the differing types –
black oil, volatile oil, condensate or gas. Typical compositions and phase characteristics are
shown.

8
EG5099 Phase Behaviour and Physical Properties T. Baxter

Black Oil
C o m p o ne nt Mol %
M e thane (C H 4 ) 4 8 .8 3
E thane (C 2 H 6 ) 2 .7 5
P ro p ane (C 3 H 8 ) 1 .9 3
B utane s (C 4 H 1 0 ) 1 .6
P e ntane s (C 5 H 1 2 ) 1 .1 5
H e xane (C 6 H 1 4 ) 1 .5 9
C7+ 4 2 .1 5
M o le c ular W e ig ht o f C 7 + 225
G O R (s c f /b b l) 625
O il G ravity (º A P I ) 3 4 .3
C o lo ur B lac k

C7+ is a pseudo/hypothetical component representing an average of all species C7 and

greater.
GOR – gas oil ratio, volume ratio of gas to liquid oil.
API – liquid density

9
EG5099 Phase Behaviour and Physical Properties T. Baxter

Volatile Oil
C o m p o ne nt Mol %
M e thane (C H 4 ) 6 4 .3 6
E thane (C 2 H 6 ) 7 .5 2
P ro p ane (C 3 H 8 ) 4 .7 4
B utane s (C 4 H 1 0 ) 4 .1 2
P e ntane s (C 5 H 1 2 ) 2 .9 7
H e xane (C 6 H 1 4 ) 1 .3 8
C7+ 1 4 .9 1
M o le c ular W e ig ht o f C 7 + 181
G O R (s c f /b b l) 2000
O il G ravity (º A P I ) 5 0 .1
C o lo ur B ro w n

Note the kick up in the envelope. This is a not a real situation; it is a function of the
determined mathematical solution. This is a useful reminder that not everything generated by
a computer is correct.

10
EG5099 Phase Behaviour and Physical Properties T. Baxter

Gas Condensate
C o m p o ne nt Mol %
M e thane (C H 4 ) 8 7 .0 7
E thane (C 2 H 6 ) 4 .3 9
P ro p ane (C 3 H 8 ) 2 .2 9
B utane s (C 4 H 1 0 ) 1 .7 4
P e ntane s (C 5 H 1 2 ) 0 .8 3
H e xane (C 6 H 1 4 ) 0 .6
C7+ 3 .8
M o le c ular W e ig ht o f C 7 + 112
G O R (s c f /b b l) 18200
O il G ravity (º A P I ) 6 0 .8
C o lo ur S traw

11
EG5099 Phase Behaviour and Physical Properties T. Baxter

Gas

Component Mol %
Methane (CH4) 95.85
Ethane (C2H6) 2.67
Propane (C3H8) 0.34
Butanes (C4H10) 0.52
Pentanes (C5H12) 0.08
Hexane (C6H14) 0.12
C7+ 0.42
Molecular Weight of C7+ 157
GOR (scf/bbl) 105000
Oil Gravity (º API) 125
Colour White

On inspection of the four phase envelopes the transition, temperature difference from the
bubble point to the dew point reduces from black oil to gas. The gas composition is
dominated by methane hence the system is behaving more like a single component. In the
extreme, if the gas were 100% methane the phase behaviour would be a single line.

12
EG5099 Phase Behaviour and Physical Properties T. Baxter

4 Fluid Sampling
Representative samples of the reservoir have to be obtained to allow for phase behaviour
modelling. This is generally facilitated by a Drill Stem Test.

4.1 Drill Stem Test

This is a procedure to determine the productive capacity, pressure, permeability or extent (or a
combination of these) of a hydrocarbon reservoir. A three phase separator is provided on the
test vessel which measures the quantity of each phase – generally oil and gas but sometimes
water too. Samples are taken of each phase and the composition determined by
chromatography at an onshore laboratory. Knowing the rate and composition of each phase a
recombined mass balance is used to determine the reservoir fluid composition.
This type of sampling may omit components which could deposit within the test well or react
with the iron in the well wall. For that reason downhole samples are taken – a fluid sample is
taken at reservoir rockface thus ensuring the fluid has all the compositional species.
A drill stem test may last for a day or two during which time the oil and gas are burned. The
longer the test the more informative is the data received. This has to be balanced against cost,
as the longer the vessel is on station the greater the expense.

4.2 Extended Well Testing

Contrary to the aforementioned, some oil fields may be subject to an extended test – many
months. This can arise where the field geology and reservoir flow characteristics are very
complex and a long duration test can provide additional information to offset potential risks
and uncertainties. Nowadays extended well tests are less common due to the environmental
impact of prolonged flaring/burning.

13
EG5099 Phase Behaviour and Physical Properties T. Baxter

5 Fluid Modelling
The choice of thermodynamic model is critical when evaluating phase behaviour. Fluid phase
behaviour and properties can be predicted using a either a ‘Black Oil’ model or a
‘Compositional’ model. Compositional models are now custom and practice in Process
Engineering.

5.1 Black Oil

Not to be confused with the previous Black Oil Reservoir - Black Oil models are generally
used for simple, multiphase modelling in flowlines and wellbores. They predict phase
behaviour and bulk properties for varying conditions by relating the fluid volumetric
properties at the surface (e.g. GOR, Oil Gravity and Gas Gravity) to the system conditions.
No detailed knowledge of fluid composition is required. Black oil models are clearly not
recommended for preparing heat and mass balances.
With the development of equations of state (see later), black oil models are now seldom used
for Process Design. They are used for reservoir analysis where detailed compositional data is
not required.
Compositional models are used for rigorous heat and mass balance work. They use a property
package and a composition specified in terms of individual components which are available in
the package database or component library. If required, pseudo-components can be specified
for non-library components or for boiling point cuts. Binary interaction parameters for
components pairs are used to give improved VLE property predictions.
Modern simulation packages generally have several property packages available for selection
including both equations of state and activity models.

5.2 Compositional
Compositional fluid modelling is a method for describing a stream based upon its pure
components. An equation of state will be used to predict VLE (vapour liquid equilibria), gas
and liquid enthalpies, gas and liquid densities, gas and liquid viscosities, surface tension and
thermal properties - thermal conductivity.
It is not practical to model every component of a reservoir fluid due to the large numbers of
components that are present. Generally, for acceptable phase behaviour prediction, it is
sufficient to specify the mole fractions of the main light end paraffins, typically C1 to C10 for
black oils. If dealing with gas condensate systems, however, more rigorous compositional
data may be required, particularly if modelling retrograde behaviour. Heavier components are
handled as pseudo or hypothetical components.

14
EG5099 Phase Behaviour and Physical Properties T. Baxter

For the heavier components in a reservoir fluid mix one or more pseudo-components (or
hypothetical components) can be used. Pseudo-components are a mixture of many
components with different properties but modelled as one component with
generalised/average properties.

5.2.1 Pseudo-Component
Pseudo-Components are normally defined either by the critical properties or by average
molecular weight, specific gravity and normal boiling point. For most computer simulations a
minimum of two of these must be specified. Acentric factors and binary interaction
parameters can also be entered; most simulation packages will estimate these if not supplied
by the user.
Prediction of heavy end physical properties is important for accurate prediction of phase
behaviour; incomplete or inaccurate data can radically affect phase calculations, for example
the prediction of bubble and dew points.
Standard fractional distillation tests can be used to produce boiling point curves and physical
properties allowing the heavy ends to be split into a number of pseudo components.
Some simulation packages have the facility to take in distillation test data directly and to
produce the pseudo-components automatically. Some ‘tuning’ may be required to match the
properties of the modelled reservoir fluids to well test data.

15
EG5099 Phase Behaviour and Physical Properties T. Baxter

Commercial heat and mass balance simulators require an equation of state to be selected then
normal and hypothetical component properties are added as shown.

16
EG5099 Phase Behaviour and Physical Properties T. Baxter

5.3 Equilibrium Ratios

The vapour-liquid equilibrium constant (K) is defined as the mole fraction of any component
in the vapour phase divided by the mole fraction of the same component in the liquid phase:

Ki = yi / xi

Use of Equilibrium Ratios is key to the preparation of oil and gas processing heat and mass
balances. The application of K values allows for the calculation of dew points, bubble points
and the vapour-liquid behaviour inside the phase envelope (flash calculations).

17
EG5099 Phase Behaviour and Physical Properties T. Baxter

5.3.1 Bubble Point Calculation

The following criteria is met;

ΣKi xi = Σyi = 1.0

Assume a temperature for the known pressure (or assume pressure if temperature is known)
Find Ki at pressure and temperature known and assumed
Multiply Ki by the corresponding xi
If summation of values is 1.0, then pressure and temperature is correct, if not repeat until Σ Ki
xi = 1.0.

5.3.2 Dew Point Calculation

The following criteria is met;

Σ (yi/Ki) = Σ xi = 1.0
The steps involved in a dew point calculation are the same as for the bubble point calculation.
A dew point calculation is less exact than a bubble point calculation, especially for lean gases
containing a small amount of heavy ends.

5.3.3 Flash Calculation Procedure

By an overall and component mass balance the following is readily developed.

zi
 xi  
zi
 1.0 y  i
L
 1.0
( L  VKi) (V  )
Ki

 For a specific pressure and temperature Ki can be determined

 Flash calculation solution is iterative
 Guess V and calculate L
 Calculate all yi all xi
 Test Σxi or Σyi = 1.0 then a solution has been obtained
 If not re-initialse L or V

Using K value charts (available in many text books) the following are worked examples of the
three types of calculation.

18
EG5099 Phase Behaviour and Physical Properties T. Baxter

Bubble Point Estimate

19
EG5099 Phase Behaviour and Physical Properties T. Baxter

Dew Pont Estimate

20
EG5099 Phase Behaviour and Physical Properties T. Baxter

Flash Calculation

21
EG5099 Phase Behaviour and Physical Properties T. Baxter

22
EG5099 Phase Behaviour and Physical Properties T. Baxter

K values can be found from simulation packages as shown.

K values can also be estimated from the following – Wilson, A Modified Redlich-Kwong EOS,
AICHE National Meeting. The expression is a curve fit of the K value charts.
  Tci  
P 5.371i 1 T 
Ki  ci e  

P - absolute pressure
Pci – component i critical pressure in same units as P
T – absolute temperature
Tci – component i critical temperature in same units as T
wi - Acentric factor component i (discussed later)

23
EG5099 Phase Behaviour and Physical Properties T. Baxter

5.4 Equations of State

Whilst the K value method is useful and provide insight for the student, more accurate
calculations are provided by the use of Equations of State

5.4.1 Van der Waals

An equation of state is a thermodynamic equation describing the state of matter under a given
set of physical conditions. In 1873, J. D. van der Waals introduced the first equation of state
derived by the assumption of a finite volume occupied by the constituent molecules. His new
formula revolutionized the study of equations of state, and was most famously continued via
the Redlich–Kwong equation of state and the Soave modification of Redlich-Kwong.
The Van der Waals equation of state may be written:

where Vm is molar volume, and a and b are substance-specific constants.

a and b can be calculated from the critical properties pc,Tc and Vc as:
Also written as:

The van der Waals equation of state was one of the first to perform markedly better than the
ideal gas law. In this landmark equation a is the attraction parameter and b the repulsion
parameter or the effective molecular volume. While the equation is definitely superior to the
ideal gas law and does predict the formation of a liquid phase, the agreement with
experimental data is limited for conditions where liquid forms. While the van der Waals
equation is commonly referenced in text books and papers for historical reasons, it is now
obsolete. Other modern equations of only slightly greater complexity are much more accurate.
One such equation is SRK.

24
EG5099 Phase Behaviour and Physical Properties T. Baxter

5.4.2 Soave-Redlich-Kwong (SRK)

SRK is robust and well proven equation of state, ideal for use in oil & gas and refinery
applications. It is suitable for cryogenic conditions and pressures up to 300 bara. Binary
interaction parameters (BIP, symbol kij) for component pairs are used to improve accuracy
with correlations used to generate binary interaction parameters for pseudo-components. BIPs
are obtained from experimental data which is regressed for EOS use in simulators.
In common with many EOS, SRK is not considered suitable where accuracy is required for
systems with polar compounds.
Liquid compressibility predictions are sufficiently accurate for fugacity calculations but not
for accurate liquid densities (can be 10 - 20% low).
SRK can predict phase behaviour in the critical region although calculations are somewhat
unstable. Furthermore SRK is not considered to be particularly accurate for heavy end VLE
prediction and vacuum systems.
Redlich, O. and Kwong, J. N. S. (1949). On the Thermodynamics of Solutions. V: An Equation
of State. Fugacities of Gaseous Solutions. Chem. Rev., 44, 233-244.
Soave, G. (1972). Equilibrium Constants from a Modified Redlich-Kwong Equation of State.
Chem. Eng. Sci., 27 , 1197-1203.

5.4.2.1 Fugacity
Fugacity is key to the understanding of the solution of an equation state and the principles of
equilibrium. To recap earlier thermodynamic lectures, fugacity is a conceptual term which is
related to Gibb’s free energy, temperature, volume and pressure. The units of fugacity are the
same as pressure. Although fugacity has the same units as pressure it will only be equal to
pressure under ideal conditions.
For a system of phases to be in equilibrium there must be no mechanical, thermal or chemical
driving force. At constant temperature and pressure the chemical potential of every species
must be equal. Thus there is no driving force to for species to move from one phase to
another. Fugacity is directly related chemical potential hence at equilibrium species fugacity
will be equal.
The fugacity coefficient for a pure component is defined as:

fi
Fi =
P

For a component in a gas and liquid mixture, the fugacity coefficient is:

25
EG5099 Phase Behaviour and Physical Properties T. Baxter

fi
Fi =
yi P
fi
Fi =
xi P
Where yi and xi is the mole fraction of component y in the vapour and liquid phase.
Classical thermodynamics shows;

é z -1ù p
lnFi = ò ê i údP
0
ë P û
Each equation of state provides a related solution to the above integral as will be shown in the
following information on SRK.
Properties and parameters used;
a Attraction parameter
b Residual volume parameter
W SRK Parameter (numerical co-efficient)
A Derived parameter
B Derived parameter
z = PV/RT, compressibility factor
^
fi Partial fugacity of species i
kij Binary Interaction Parameter
F = fi/P, Fugacity Coefficient
w Acentric Factor
ρ Molar Density
Subscripts
c Value of any variable at the critical point
r Reduced Value
pc Pseudo-critical value
Superscripts
0 property of a standard state

26
EG5099 Phase Behaviour and Physical Properties T. Baxter

SRK Standard Form

RT aα
P 
(V  b) V(V  b)
The variables ‘a’ and ‘b’ are derived from the Van-der-Waals equation, which was based on a
model where molecules were represented by hard spheres which behaved in a classical and
predictable fashion
The parameter ‘b’ represents the hard-sphere volume of the molecules
The parameter ‘a’ represents the intermolecular attraction

Polynomial Compressibility Form – (the cubic equation)

z3 - z2 + (A - B- B2) z - AB = 0
Parameters
A = (aP)/(R2T2) = 0.42748Pr/Tr2
B = (b P)/(RT) = 0.08664Pr/Tr
a = WaR2Tc2/Pc = 0.42748R2Tc2/Pc
b = WbRTc/Pc = 0.08664RTc/Pc

α  1  m(1  Tr 0.5 ) where

m  0.48  1.574  0.172 2

Fugacity Coefficient
ln F = z - 1 - ln (z - B) - A/B ln (1 + B/z)
Mixtures
aα = Σ Σ yiyj(aa)ij
b = Σ yibi
A = Σ Σ yiyjAij
B = Σ yiBi
(aα)ij = (1 - kij)[(aαi)(aα)j]0.5

The system in equilibrium if the phase

fugacities at roots are equal.

27
EG5099 Phase Behaviour and Physical Properties T. Baxter

5.4.3 Peng-Robinson
Peng-Robinson is robust and well proven, generally ideal for use in oil & gas and refinery
applications. It is similar to SRK in performance however it is generally accurate over a wider
range of conditions. Specifically;
– It is more accurate around the critical point.
– Liquid phase density prediction is more accurate.
Adapted PR packages can be used for heavy end VLE prediction, vacuum distillation and
glycol dehydration.
Peng, D. Y. and Robinson, D. B., (1976). A New Two-Constant Equation of State. Ind.
Eng. Chem. Fundam., 15, 59-64.
PR Standard Form
RT aα
P  2
(V  b) (V  2bV - b2)
Polynomial Compressibility Form
z3 - (1- B)z2 + (A - 3B2 - 2B)z - (AB - B2 - B3) = 0
Parameters
a= 0.45724 [(R2Tc2)/Pc]
b = 0.07780 RTc/Pc
α = [1 + (0.37464 + 1.54226ɷ - 0.26992 ɷ 2) (1-Tr0.5)]2
A = (aαP)/(R2T2) = 0.45724αPr/Tr2
B = (bP)/(RT) = 0.0778Pr/Tr
Fugacity Coefficient
ln ɸ = z - 1 - ln (z - B) - [A/2(2B)0.5] ln [(z+2.414B)/(z-0.414B)]
Mixtures
aα = Σ Σ yiyj (aα)ij
b = Σ yibi
(aα)ij = (1 - kij) [(aα )i(aα )j]0.5
A = Σ Σ yiyjAij
B = Σ yiBi
Aij = (1 - kij)(AiAj)0.5

Acentric Factor
The acentric factor (ω) describes the change in the intermolecular attraction component, a
with temperature.

28
EG5099 Phase Behaviour and Physical Properties T. Baxter

The table shows typical acentric factors, the value increases with the size of the molecule and
polarity.
Compound Acentric Factor
Nitrogen 0.039
Carbon Dioxide 0.224
Methane 0.011
Ethane 0.099
Butane 0.119
Hexane 0.299
Octane 0.398
Decane 0.489

Acentric factors can also be found in simulation packages.

SRK worked example

Calculation of the saturation pressure (boiling point) of n-Pentane at 100 ºC using SRK.
The experimentally determined vapour pressure is 5.86 atm
Critical properties of n-Pentane are:
Tc = 469.7 K, Pc = 33.25 bar, w = 0.251

Using S-R-K :
  1  m(1  Tr ) where m  0.48  1.574  0.172 2

 373 
  1  0.48  1.574  0.251  0.172  0.2512 1    1.094
 469.6 

Calculate A & B
A  0.42747 P / Pc Tc / T   0.0224P
2

29
EG5099 Phase Behaviour and Physical Properties T. Baxter

B  0.08664P / Pc Tc / T   0.0033P

Substitute values of A & B into the polynomial compressibility equation:

Z 3  Z 2  ( A  B  B 2 )Z  AB  0
Solve to find Z for liquid and vapour phases

Calculate the fugacity of the vapour and liquid phases:

ln f = z - 1 - ln (z - B) - A/B ln (1 + B/z)
fV = fV/PV and fL = fL/PV
At equilibrium, fV = fL therefore fV = fL

z f
P Vapour Liquid Vapour Liquid Ratio
4 0.8943 0.0184 3.665 5.196
5 0.8647 0.0229 4.4774 5.2287 0.8563
6 0.831 0.0275 5.2482 5.2512 0.9994
7 0.7955 0.0321 5.9775 5.2807 1.132

At equilibrium, the fugacity of the liquid and vapour phases is equal.

Trial and error is conducted from 4 to 7 atm. By interpolation of the above table, the predicted
saturation pressure is 6.01 atm

5.5 Property Package Selection

Selection of the property package must take into account the components and the operating
conditions. For most purposes, Peng Robinson (PR), Soave-Redlich-Kwong (SRK), or a
modified version of these methods, will provide sufficiently accurate modelling for oil and
gas equipment applications.
The PR and SRK equations of state give accurate modelling for systems containing up to 5%
N2, CO2 or H2S. For systems with greater than 5% N2, CO2 or H2S these equations of state are
still recommended if the system does not include free water. It may be advisable, however, to
utilise user defined binary interaction parameters if available. This will depend upon the
simulation/flash package being used and the quality of the data in its components library. It is
recommended to consult the user guide for the particular simulation package being used.
Polar compounds can be problematic for EOS methods - methanol, glycol and water -
empirical correction factors are often required to improve accuracy. Most simulation packages
offer specialised property packages to handle such systems. These utilise a combination of an
EOS to predict vapour phase fugacity coefficients and an activity coefficient model for the
liquid phase.

30
EG5099 Phase Behaviour and Physical Properties T. Baxter

The following is the modelling output for a simple system where the gas rate to compressors
is a key issue. Two EOS are used – Peng-Robinson and Zudevitch Joffe. As can be seen
similar gas from the higher pressure separator are predicted by both EOS. However for the
lower pressure separator a difference of around 30% is shown. This difference could be very
significant when considering the design of the low pressure compressor. The question is what
is correct? That is a key skill for the engineer – the selection of the most accurate EOS for the
particular application.

31
EG5099 Phase Behaviour and Physical Properties T. Baxter

32
EG5099 Phase Behaviour and Physical Properties T. Baxter

5.5.1 BWRS
This is the Benedict-Webb-Rubin equation of state modified by Professor Kenneth E. Starling
of the University of Oklahoma:

ρ = the molar density.

Values of the various parameters for 15 substances can be found in K.E. Starling, Fluid
Properties for Light Petroleum Systems. Gulf Publishing Company (1973).
The BWRS is favoured by some gas pipeline designers. The following phase envelope shows
BWRS, PR and SRK results with measured values of cricondentherm and cricondenbar for a
specific gas. As can be seen PR and SRK are very accurate whereas BWRS is significantly
different. If BWRS were assumed to be accurate for this application significantly more
process plant would be required to achieve the pipeline cricondenbar. Once again reinforcing
the requirement for appropriate package selection.

Application ofGullfaks
BWRS erroneous – Pipeline two-phase
Fluid from SOW

130

120
Minimum
110
Pipeline
100 Operating
Pressure
90

80
Pressure (bar)

BWRS
70 PR
RKS
60 Cricondentherm
Cricondenbar
50

40

30

20

10

0
-40 -35 -30 -25 -20 -15 -10 -5 0 5 10 15 20 25 30 35
Temperature (C)

33
EG5099 Phase Behaviour and Physical Properties T. Baxter

5.5.1.1 Limitations of Phase Behaviour Prediction

All phase behaviour methods assume an equilibrium is reached. Phase behaviour prediction
deals with mass transfer effects and therefore does not take into account bulk fluid flow. In
practice there is almost inevitably some bulk transfer of fluids between the phases: emulsions
may be formed due to high fluid shear rates which disperses water in the oil phase, water will
carry over into the oil phase. Also liquid droplets may be entrained into the gas phase.
EOS do not accurately predict phase behaviour at the critical point.

5.5.2 CPA Model – Polar Fluids

The cubic equation of state is the most widely used thermodynamic models for phase
equilibrium calculation and physical property estimation in the petroleum industry. As stated
earlier, Peng-Robinson was developed originally for hydrocarbon mixtures and can have
limitations when there are associating molecules present e.g. water, methanol, glycol. The
Cubic Plus Association model is gaining interest as a useful EOS for handling associating
molecules. It is a modified SRK model introducing an association term.

Kontogeorgis GM, Voutsas EC, Yakoumis IV, Tassios DP. An equationof state for associating
fluids. Ind Eng Chem Res.1996

34
EG5099 Phase Behaviour and Physical Properties T. Baxter

Within simulators the available property packages are generally grouped under the types
detailed;
Property Package Type Typical Application
Equations of State, Ideal hydrocarbon systems
Activity Models, Polar or non-ideal systems
Chao Seader Models Systems containing mainly liquid or vapour H2O or high H2 contents
Heavy hydrocarbon systems at low pressures (increasing light hydrocarbons
Vapour Pressure Models
results in decreasing accuracy)
Acid gas systems, steam systems, non-volatile oils, aqueous electrolyte
Miscellaneous Type
systems

Non-ideal components include alcohols, acids, glycols and other non-ideal or polar chemicals.
The more non-ideal components present, the less ideal the mixture.

5.5.3 Activity Models

As previously stated, although equation of state models have proven to be very reliable in
predicting properties of most hydrocarbon based fluids over a large range of operating
conditions, their application has been limited to primarily non-polar or slightly polar
components.
Polar or non-ideal chemical systems have traditionally been handled using dual model
approaches. In this approach, an equation of state is used for predicting the vapour fugacity
coefficients and an activity coefficient model is used for the liquid phase. Although there is
considerable research being conducted to extend equation of state applications into the
chemical arena (e.g., the PRSV equation), the state of the art of property predictions for
chemical systems is still governed mainly by activity models.
Activity Models are much more empirical in nature when compared to an EOS for property
predictions. For example, they cannot be used as reliably as the equations of state for
generalised application or extrapolating into untested operating conditions. Their tuning
parameters should be fitted against a representative sample of experimental data and their
application should be limited to moderate pressures. Consequently, more caution should be
exercised when selecting these models for simulation.
The phase separation or equilibrium ratio Ki for component i, defined in terms of the vapour
phase fugacity coefficient and the liquid phase activity coefficient, is calculated from the
following expression:

35
EG5099 Phase Behaviour and Physical Properties T. Baxter

5.5.3.1 NRTL
The NRTL (Non-Random-Two-Liquid) equation was proposed by Renon and Prausnitz in
1968, is an extension of the original Wilson equation. It uses statistical mechanics and the
liquid cell theory to represent the liquid structure.
The NRTL equation in contains five adjustable parameters (temperature dependent and
independent) for fitting per binary pair.
The NRTL equation has the form shown.

36
EG5099 Phase Behaviour and Physical Properties T. Baxter

The five adjustable parameters for the NRTL equation are the aij, aji, bij, bji, and αij terms. The
equation uses parameter values stored in the simulator or user supplied value for further
fitting the equation to a given set of data.
The best results are produced when an activity model is applied in the operating region for
which the parameters apply.
The table below shows when the different Activity Models can be used
Application Margules van Laar Wilson NRTL UNIQUAC
Binary Systems A A A A A
Multicomponent Systems LA LA A A A
Azeotropic Systems A A A A A
Liquid-Liquid Equilibria A A N/A A A
Dilute Systems ? ? A A A
Self-Associating Systems ? ? A A A
Polymers N/A N/A N/A N/A A
Extrapolation ? ? G G G

A = Applicable; N/A = Not Applicable;? = Questionable; G = Good; LA = Limited Application

5.5.4 Modelling Summary

The table below summarises recommended property packages for various systems commonly
encountered in oil and gas/ petrochemical simulations.
Type of System Recommended Property Methods
TEG Dehydration PR
Sour Water Sour PR
Cryogenic Gas Processing PR, PRSV, TST
Air Separation PR, PRSV, TST
Atm Crude Towers PR, PR Options, GS, TST
PR, PR Options, GS (<10 mm Hg), Braun K10,
Vacuum Towers
Esso K, TST
Ethylene Towers Lee Kesler Plocker
High H2 Systems PR, ZJ, GS, TST
Reservoir Systems PR, PR Options, TST
Steam Systems Steam Package, CS or GS
Hydrate Inhibition PR
Chemical systems Activity Models, PRSV
HF Alkylation PRSV, NRTL*
TEG Dehydration with Aromatics PR*
Hydrocarbon systems where H2O solubility in HC is
Kabadi Danner
important
Systems with select gases and light hydrocarbons MBWR
*Recommended that Hyprotech is consulted for details of accuracy

Validation of simulation against real data should be carried out where appropriate to check
that the most appropriate property package has been selected.
In summary for oil, gas and petrochemical applications, the Peng-Robinson EOS is generally
the recommended property package. Enhancements to this equation of state enable it to be
accurate for a variety of systems over a wide range of conditions. It rigorously solves most

37
EG5099 Phase Behaviour and Physical Properties T. Baxter

single, two-phase or three-phase system with a high degree of efficiency and reliability, and is
applicable over a wide range of conditions.
The PR equation of state is enhanced to yield accurate phase equilibrium calculations for
systems ranging from low temperature cryogenic systems to high temperature, high pressure
reservoir systems. The same equation of state predicts component distributions for heavy oil,
aqueous glycol, and CH3OH systems.
PR equation of state recommendation is largely due to the preferential attention that is given
to it by modelling packages. Although the Soave-Redlich-Kwong (SRK) equation also
provides comparable results to the PR in many cases, it is known that its range of application
is significantly limited and it is not as reliable for non-ideal systems. For example, it should
not be used for systems with CH3OH or glycols.
As an alternate, the CPA or PRSV equation of state should also be considered. It can handle
the same systems as the PR equation with equivalent, or better accuracy, plus it is more
suitable for handling moderately non-ideal systems.
Activity Models, which handle highly non-ideal systems, are much more empirical in nature
when compared to the property predictions in the hydrocarbon industry. Polar or non-ideal
chemical systems are traditionally handled using dual model approaches. In this type of
approach, an equation of state is used for predicting the vapor fugacity coefficients and an
activity coefficient model is used for the liquid phase. Since the experimental data for activity
model parameters are fitted for a specific range, these property methods cannot be used as
reliably for generalized application.
The CS and GS methods, though limited in scope, may be preferred in some instances. For
example, they are recommended for problems containing mainly steam/water systems because
they include special correlations that accurately represent the steam tables. The Grayson-
Streed correlation is recommended for use with systems having a high concentration of H2
because of the special treatment given to H2 in the development of the model. This correlation
may also be slightly more accurate in the simulation of vacuum towers.
The vapor Pressure K models, Antoine, BraunK10 and EssoK models, are designed to handle
heavier hydrocarbon systems at lower pressures. These equations are traditionally applied for
heavier hydrocarbon fractionation systems and consequently provide a good means of
comparison against rigorous models. They should not be considered for VLE predictions for
systems operating at high pressures or systems with significant quantities of light
hydrocarbons.
Typical simulator default combinations are as indicated;

38
EG5099 Phase Behaviour and Physical Properties T. Baxter

39
EG5099 Phase Behaviour and Physical Properties T. Baxter

5.5.5 CO2 Modelling

Interest in Carbon Capture and Storage has focussed
attention on accurate CO2 modelling. The EOS of Span and Wagner is recommended.

5.6 The Mollier Chart

The Mollier Chart is a convenient representation of the phase behaviour and thermodynamics
of a fluid. The charts are very useful for preliminary calculations. Key features are shown.

40
EG5099 Phase Behaviour and Physical Properties T. Baxter

Isotherms

Bubble Point, Constant

Saturation, Entropy
Vapour Density
Pressure at
60 DegC
-40 DegC

41
EG5099 Phase Behaviour and Physical Properties T. Baxter

Constant entropy Constant enthalpy

42
EG5099 Phase Behaviour and Physical Properties T. Baxter

The Mollier chart can be used for as a first approximation gas expansion across a
valve follows an isenthalpic path. Gas expansion can result in downstream
temperatures considerably below the ambient temperature. Low temperatures can
result in ice and hydrate formation furthermore; materials have to be designed to
handle low temperatures where appropriate. A typical application is the opening of a
closed well. Here the formed gas cap expands isenthalpically.

5.7 Crude Assay

An Assay is a detailed fluid analysis of crude oil, sampled under strictly controlled
conditions
Assay reports include the quantities and properties of distillates used for crude
valuation purposes, the quantity of waxes, heavy metals, salt and sulphur and physical
properties of the fluid such as viscosity
Assay samples are taken periodically for the purposes of crude valuation purposes and
annually for crudes being exported via a pipeline shared with other fields

43
EG5099 Phase Behaviour and Physical Properties T. Baxter

SPR CRUDE OIL COMPREHENSIVE ANALYSIS

Sample ID BAYOU CHOCTAW SWEET Date of Assay 18/09/2000

Crude

Specific Gravity, 60/60° F 0.8447 Ni, ppm 3.50 RVP, psi @ 100° F 4.62
API Gravity 36.0 V, ppm 5.49 Acid number, mg KOH/g 0.084
Sulfur, Wt. % 0.36 Fe, ppm 0.844 Mercaptan Sulfur, ppm 7.021
Nitrogen, Wt. % 0.114 H2S Sulfur, ppm 0
Micro Car. Res., Wt. % 2.22 Org. Cl, ppm 0.3 Viscosity: 77° F 6.874 cSt
Pour Point, °F 31 UOP "K" 11.94 100° F 4.623 cSt

Fraction Gas 1 2 3 4 5 6 Residuum Residuum

C2 - C5 - 175° - 250° - 375° - 530° - 650° -
Cut Temp. C4 175° F 250° F 375° F 530° F 650° F 1050° F 650° F+ 1050° F+
Vol. % 1.7 7.3 8.1 14.2 16.3 10.0 31.8 42.4 10.7
Vol. Sum % 1.7 9.0 17.1 31.3 47.6 57.6 89.3 100.0 100.0
Wt. % 1.2 5.8 7.1 13.1 15.9 10.1 34.3 47.0 12.7
Wt. Sum % 1.2 7.0 14.1 27.1 43.0 53.1 87.4 100.0 100.0
Specific Gravity, 60/60° F 0.6730 0.7396 0.7763 0.8240 0.8526 0.9116 0.9349 1.004
API Gravity 78.8 59.8 50.8 40.2 34.5 23.7 19.9 9.4
Sulfur, Wt. % 0.0043 0.0040 0.0123 0.07 0.21 0.57 0.69 1.04
Molecular Weight 97 111 136 184 246 425
Hydrogen, Wt. % 15.89 14.65 na 12.99 10.61
Mercaptan Sulfur, ppm 14.6 10.1 22.5 17.4
H2S Sulfur, ppm 0.03 0.8 0.7 0.02
Organic Cl, ppm 2.1 0.5 0.5 0.6
Research Octane Number* 68.4 61.1 42.3
Motor Octane Number* 66.5 58.6 40.0
Flash Point, ° F 77 171 246 303
Aniline Point, ° F 122.4 144.1 164.3 193.3
Acid Number, mg KOH/g 0.03 0.10
Cetane Index 47.1 53.2
Diesel Index 62.2 58.0 56.6
Naphthalenes, Vol. % 4.42 8.20
Smoke point, mm 20.3 16.8
Nitrogen, Wt. % 0.0015 0.006 0.108 0.240 0.603
Viscosity, cSt 77° F 2.473
100° F 1.951 4.795
130° F 3.312 37.03 95.3
180° F 14.22 28.28 5671
210° F 1722
275° F 249.3
Freezing Point, °F -28.54
Cloud Point, °F 24.0 106
Pour Point, °F 19.9 102 75
Ni, ppm 7.539 26.2
V, ppm 11.81 41.0
Fe, ppm 3.856 13.87
Micro Car. Res., Wt. % 5.07 18.17

* = calculated from gas chromatographic data

44
EG5099 Phase Behaviour and Physical Properties T. Baxter

6 Physical Properties
Accurate physical properties are required for system and equipment design. They
underpin Chemical Engineering calculations and errors here will result in a flawed
design or perhaps an unsafe design. The student should not blindly assume that the
physical property output from a simulation is accurate and verification should be
undertaken.
A typical heat exchanger data sheet follows, as can be seen key physical properties are
essential for the design to proceed.

45
EG5099 Phase Behaviour and Physical Properties T. Baxter

6.1 Critical and Reduced Temperature and Pressure

Critical and reduced pressure and temperature are often used as correlating parameters.
As the critical temperature is approached, the properties of gas and liquid phases
approach one another, resulting in only one phase at the critical point: a homogeneous
supercritical fluid. The heat of vaporization is zero at and beyond this critical point,
hence there is no distinction between the two phases. Above the critical temperature a
liquid cannot be formed by an increase in pressure, but with enough pressure a solid
may be formed. The critical pressure is the vapour pressure at the critical temperature.
Critical properties vary from material to material, just as is the case for the melting
point and boiling point. Critical properties for many pure substances are readily
available in the literature. Obtaining critical properties for mixtures is somewhat more
problematic.
The critical point for a multicomponent mixture is referred to as the state of pressure
and temperature at which all intensive properties of the gas and liquid phases are
equal.
Reduced Properties
Like critical properties, reduced properties are often used as correlating parameters
and properties in thermodynamics. Reduced properties are temperature and pressure
divided by their respective critical property.

6.2 Liquid Density

Liquid density is required for the design of numerous items of process plant. Common
liquid densities are as shown.

Compound Density @ 15 oC
(kg/m3)
Water 1000
Ethyl alcohol 785
Butane 563.2
Octane 706.7
Heavy Crude 903
Medium Crude 859
Light Gas Condensate 734
Steel Approx. 7800
Concrete Approx. 2300

One of the simplest calculation methods is the API corresponding states method which
uses a correlation to obtain a correction factor that adjusts the density at standard
conditions to the actual conditions.

46
EG5099 Phase Behaviour and Physical Properties T. Baxter

M i xi
m  
i
M m   xi M i
 C1 
 actual   s tan dard. 
 C2 
Where:
3
 - Molar Volume (m /kmol)
3
 - density (kg/m )
M - Molecular weight (kg/kmol)
x - Mole fraction
C1 & C2 - Correlation factors for density correction
m - mixed compound

Example:
Calculate the liquid density of a saturated mixture of 70% ethane, 20% propane and
10 %butane at 100 bara and 25oC.

47
EG5099 Phase Behaviour and Physical Properties T. Baxter

Obtain the density of components at standard conditions , here data is given relative to water.
C2    0.3581    358.1 kg/m 3 , M  30.07 

C3    0.5083    508.3 kg/m 3 , M  44.097 

C4    0.5637    563.7 kg/m 3 , M  58.124

Using volume mixing equation

30.07  0.7 44.097  0.2 58.124  0.1
m     0.0865 m 3 / kmol
358.1 508.3 563.7
M m  (30.07  0.8)  (44.097  0.2)  (58.124  0.1)  35.68 kg/kmol

Mm 38.69
 m standard    412.6 kg/m 3 @Standard Conditions
m 0.0864
Now find the correlatio n factors to adjust the standard density to the actual conditions .
Taking Critical Properties from standard databooks

Pcm   xi Pci  (0.7  48.8)  (0.2  42.49)  (0.1 36.49)  46.31 bara

Tcm   xiTci  (0.7  305.43)  (0.2  369.82)  (0.1 408.13)  328.6 K

@ Standard Conditions ( 15 C & 1 bara)

288
Pr standard  Saturated Liquid Tr standard   0.876
328.6
From Correlatio n chart C1  0.745

@ Actual Conditions (25 C & 100 barg)

100 298
Pr actual   2.16 Tr actual   0.907
46.31 328.6
From Correlatio n Chart C2  0.764

 C2   0.764 
So  actual   s tan dard    412.6   423.11 kg/m
3

 C1   0.745 

48
EG5099 Phase Behaviour and Physical Properties T. Baxter

API Correction Factor Chart

Comparing the above with the simulation Unisim. Equation of State generally use the
Hawkinson, Brombst & Thomson method - referred to as COSTALD because it uses
Corresponding Standard Liquid Tables.

Vs
*
 VR0 [1  SRKVR ]
V

VR0  1  a(1  Tr )1 3  b(1  Tr ) 2 3  c(1  Tr )  d (1  Tr ) 4 3 0.25  Tr  0.95

VR  [e  fTr  gTr2  hTr3 ] /(Tr  1.00001) 0.25  Tr  1.0

Where

49
EG5099 Phase Behaviour and Physical Properties T. Baxter

a = -1.52816 b = 1.43907
c = -0.81446 d = 0.190454
e = -0.296123 f = 0.386914
g = -0.0427258 h = -0.0480645

The mixing rules for the variables in the previous equations are as follows:

n n

 x x V
i 1 j 1
i j
*
T
ij cij

Tcm 
Vm*

Vm* 
1
4
 x V  3 x V  x V 
i i
*
i i
*2 3
i i
*1 3

 V T V T 
12
Vij*Tcij i
*
ci
*
j cj

 SRK   xi SRK Acentric Factor (shape sensitive)

0.291  0.80 RT
m i

Pcm 
SRK m cm
*
V m

This is a much more complicated method and is not suitable for hand calculations.
Using the liquid density calculation in Unisim returns a density of 456.5. kg/m3.
Using the API method a value of 423.11 kg/m3 was calculated.

6.3 Gas Compressibility

The term "compressibility" is also used in thermodynamics to describe the deviance in

the thermodynamic properties of a real gas from those expected from an ideal gas. The
compressibility factor is defined by the familiar expression as;

PVm
z=
RT

where
P is the pressure of the gas
T is its temperature
Vm is molar volume. In the case of an ideal gas

50
EG5099 Phase Behaviour and Physical Properties T. Baxter

Note, Z can be either greater or less than unity for a real gas.
The deviation from ideal gas behavior tends to become particularly significant near the
critical point, or in the case of high pressure or low temperature. In these cases, a
generalized compressibility chart or an alternative equation of state better suited to the
problem can be utilised to produce accurate results.

Methane

Ethane

Typical gas densities at 15 C and 1 bara

51
EG5099 Phase Behaviour and Physical Properties T. Baxter

Compound Vapour Density

3
(kg/m )
Air 1.21
Oxygen 1.335
Carbon dioxide 1.873
Methane 0.6784
Propane 1.865

The main parameter in calculating vapour density is the compressibility. This can be
calculated by either the appropriate equation of state or activity model, or by
generalised compressibility charts.

Example calculation using compressibility charts;

Calculate the density of the following vapour at 15 bara pressure and 25 C

temperature. At these conditions the mixture is single phase gas. Watch units MPa.

Component Yi Tci (K) YTci Pci (MPa) YPci M Myi

C2 0.7 305 213.5 4.88 3.416 30.07 21.049
C3 0.2 370 74 4.25 0.85 44.097 8.8194
C4 0.1 408 40.8 3.65 0.365 58.124 5.8124
Sum 328.3 4.631 35.681

We have the mixtures critical properties, next calculate

the reduced properties
P
Pr 
Pc
T
Tr 
Tc

Pr  15 / 46.3  0.324
Tr  298.15 / 328.3  0.907
52
EG5099 Phase Behaviour and Physical Properties T. Baxter

6.4 Viscosity

6.4.1 Liquid
Component viscosities can be found by using viscosity charts. The charts are in many
data books along with co-ordinates which relate to different compounds. There are
separate charts for gases and liquids.

Example:
Using the viscosity chart estimate the viscosity of a mixture of 30% Pentane and 70%
Octane at 25 oC and 1 bar.
Find the co-ordinates for Pentane and Octane to be used with the chart.

Pentane - X=14.9, Y=5.2

Octane - X=13.7, Y=10
from the chart

53
EG5099 Phase Behaviour and Physical Properties T. Baxter

 (mPa)= 0.23 for pentane and 0.54 for octane (note: cP = mPas)

Viscosity of Liquid
Component X Y
Water 10.2 13
Pentane 14.9 5.2
Hexane 14.7 7
Heptane 14.1 8.4
Octane 13.7 10

Note Unisim returns a liquid viscosity of 0.416 cP

6.4.2 Gas

Viscosities are found from viscosity charts. The charts give the viscosity at
1atmosphere and the required temperature. Correction for pressure and temperature

54
EG5099 Phase Behaviour and Physical Properties T. Baxter

can be made by using a viscosity correction chart. This requires the reduced P & T
from Kay’s rule.
Example:
Estimate the viscosity of a gas with composition 40% methane & 60% propane
at 25oC and 5 bara pressure.
Calculated the viscosity of the gas at 1 atmosphere and the required temperature
Using co-ordinates: Methane - X= 9.9, Y= 15.5: Propane - X= 9.7, Y= 12.9
From chart  (mPa) = 0.011 for methane
= 0.0084 for propane
Viscosity of Gases

Component X Y
Air 11 20
Carbon Dioxide 9.5 18.7
Methane 9.9 15.5
Ethane 9.1 14.5
Propane 9.7 12.9

55
EG5099 Phase Behaviour and Physical Properties T. Baxter

6.5 Specific Heat Capacity

Typical values are given. Note the high heat capacity of water compared to
hydrocarbons.

The AIChemE method can be applied for both gases and liquids. A correction factor is
used to adjust the ideal value.
A simple weight fraction average can be used as a first approximation

6.6 Thermal Conductivity

Typical values are given for some common fluids and solids.

Most simulators use the general guidelines of Reid, Prausnitz & Poling to determine
which model best suits each class of component.
– Hydrocarbon systems use the corresponding states method of Ely & Hanley
– Glycols & Acids are calculated by Sato-Reidel method
– Esters, alcohols and light hydrocarbons by Latini

6.7 Surface Tension

A molecule on the surface of a liquid is subject to an inward force as a result of the
attraction between molecules. This surface molecule tends to adjust itself to a

56
EG5099 Phase Behaviour and Physical Properties T. Baxter

minimum surface area causing the droplet to assume a spherical shape. Work is
required to extend this surface or to bring molecules from the bulk of the liquid into
the surface.
The units of surface tension are therefore force/unit length – N/m. However, most
surface tension values are presented as dyne/cm – where 1 dyne – 10-5 Newton.

6.8 Vapour Pressure

The vapor pressure of a liquid, is the pressure exerted by its vapor when the liquid and
vapor are in dynamic equilibrium. Vapor pressure is the pressure of a vapor in
equilibrium with its non-vapor phases All solids and liquids have a tendency to
evaporate to a gaseous form, and all gases have a tendency to condense back. At any
given temperature, for a particular substance, there is a partial pressure at which the
gas of that substance is in dynamic equilibrium with its liquid or solid forms. This is
the vapor pressure of that substance at that temperature. In meteorology, the term
vapor pressure is used to mean the partial pressure of water vapor in the atmosphere,
even if it is not equilibrium, and the equilibrium vapor pressure is specified as such.
Vapor pressure is an indication of a liquid's evaporation rate. It relates to the tendency
of molecules and atoms to escape from a liquid or a solid. A substance with a high
vapor pressure at normal temperatures is often referred to as volatile. The higher the
vapor pressure of a material at a given temperature, the lower the boiling point.

57
EG5099 Phase Behaviour and Physical Properties T. Baxter

The vapor pressure of any substance increases non-linearly with temperature

according to the Clausius-Clapeyron relation. The boiling point of a liquid is the
temperature where the vapor pressure equals the ambient atmospheric pressure. At the
boiling temperature, the
vapor pressure becomes
sufficient to overcome
atmospheric pressure and
the liquid forms bubbles
inside the bulk of the
substance.
Vapour pressure of
common liquids. Note
bubble point and
saturation pressure are commonly utilised to describe vapour pressure.

7 Key Learnings

Features of mixed hydrocarbon Phase Envelope – dew point etc.

Pseudo/hypothetical components
Concept of fugacity
Application of K values
Application of Peng-Robinson/SRK EOSs
Application of Activity Models
Importance of EOS selection
Importance of physical property prediction
Vapour pressure

8 Reference books

1. GPSA Engineering Data Book (Gas Processors Association)

2. Phase Equilibria in Chemical Engineering, Stanley M Walas
3. Chemical and Engineering Thermodynamics, S.I Sandler

58
EG5099 Phase Behaviour and Physical Properties T. Baxter

59