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Introduction
Nowadays the main concept of research in the petroleum and chemical industries is the
experience to identify the high-pressure phase equilibria, phase density and composition of
fluid mixtures and the existence changes respect to its pressure and temperature. One of the
most essential ways used by scientists in high-pressure phase equilibria observations is the
equation of state. An equation of state is a term which includes the pressure relationship to
temperature, volume of the fluid and its proper mixing rules. There are seven different
equation states below which represent their effects of pressure, temperature and its
composition.

Van
Vaals

der

Description
The van der Waals (VEOS) attraction is relatively very weak compared to the ionic bonding,
covalent bonding or hydrogen bonding (chemistry.tutorvista.com). Van der Waals attraction is
essential in understanding the forces of attraction between organic compounds. The solubility
of Van der Waals attraction is non -polar solvent component.
Above the critical temperature the van der Waals equation is an improvement of the ideal gas
law, and for lower temperatures the equation is also qualitatively reasonable for the liquid state
and the low-pressure gaseous state. (wikipedia) In the first-order phase transition the range of
(P, V, T), where the liquid phase and the gas phase are in equilibrium, it does not exhibit the
empirical fact that p is constant as a function of V for a given temperature.

1
a

Van der Vaals

reduced form

Description
Despite that a and b material constants in the usual form of the van der Waals equation differs
for every single fluid considered, the equation can be changed into an invariant form applicable
to all fluids. Defining the following reduced variables:

This invariance may also be understood in terms of the principle of corresponding states.
Suitable states are when two fluids have similar reduced pressure, reduced volume, and
reduced temperature. If the two fluids' states are corresponding, they exist in the same regime
of the reduced form equation of state. Therefore, they will affect to changes in almost the same
way, even though their measurable physical properties may differ significantly.

RedlichKwong

Desciption
Redlich-Kwong equation of state (RKEOS) could be used to estimate the vapour -liquid critical
properties of binary mixtures. The scientists Chueh and Prausnitz also demonstrated that the
RKEOS can be adapted to predict both phases which vapour and liquid properties. It is also the
most useful for vapour phase. RKEOS was designed largely to predict the properties of small,
non-polar molecules in the vapor phase, which it generally does well. For example, while the
Redlich and Kwong model does a positive effect showing the state of many gasses at low
temperatures and high pressures (wikipedia).

Soave Modification of
Redlich-Kwong

Description
The Soave-Redlich-Kwong (SRKEOS) equation was the first modification of the simple RedlichKwong (RK) equation where the parameter a, was presented as a temperature dependent in the
way that the vapour pressure curve can be reproduced. The additional factor is multiplied by
the attractive parameter a. The additional factor is a function of temperature and acentric
factor that represent the non sphericity of molecules.
From one experiment it is proved that the temperature coefficients of the a-parameter have
been regressed from vapour pressure data for methane to decane and many simple compounds
such as CO2. The b-parameter is assumed constant. Binary interaction parameters are available
to indicate for non-polar and weakly polar molecules. The liquid density is predicted as very
poor form.

Peng-Robinson

Description
A modification of the PengRobinson equation of state (PREOS) can be made that allows the
model to better capture vapor pressures of pure fluids. The main critical properties and the
acentric factor were expressed in the a and b parameters. Same as SRK but prediction of
liquid density is better than the SRK derivatives, none the less it is still poor for heavier
hydrocarbons (>C3). May be used for CO2 mixtures for a wide range of operating conditions,
though it is not applicable in the near-critical region.

ZudkevitchJoffe

Description
The Zudkevitch Joffee model (ZJEOS) is a modification of the Redlich-Kwong equation. This
model has been enhanced for better prediction of vapour liquid equilibrium for hydrocarbon
systems, and also the systems containing H2. The major advantage of this model over the
previous version of the RK equation is the improved capability of predicting pure component
equilibrium, and the simplification of the method for determining the required coefficients for
the equation. Zudkevitch Joffee equation is temperature dependent. The a and b values in the
a and b parameters for each pure substance at any temperature were observed by matching
the predicted liquid density data to the estimated value, and stabilizing of saturated liquid and

vapour phase behavior.

3-Parameter

RT
a
2
v b v cbv (c 1)b 2

Descrition
Hydrocarbons which have the range of Zc varying from 0.2 to 0.3 with the two parameter EOS
where the same critical compressibility factor prediction, Z, of 0.307 PREOS and 0.333 SRKEOS
(et al. Ibrahim Ashour, 2011). Although the inaccuracy of predicted volume at the critical point,
not necessarily leads to unreliable volumetric data at all conditions, it demonstrates the
easement of two-parameter EOS for matching both the vapor pressure and volume. The
inclusion of a third parameter relaxes the above limitation. The third parameter is generally
identified by managing the volumetric data. 3-parameter EOS has temperature dependent
coefficients which are a and b and they are often more accurate to predict systems containing
polar molecules.

Schmidt-Wenzel
modification to Van der
Vaals

RT
a
2
v b v ubv wb2

Description
Liquid density prediction by SRK and PR for pure substances is related with noticeable deviation
from strong values (et al. Ibrahim Ashour, 2011). Take into account that SRK is more reliable for
substances with small acentric factors, while PR shows reliable data for composition with
acentric factors around (1/3). Based on the above observation, Schmidt and Wenzel included
the acentric factor as the third parameter in the attractive term. Schmidt and Wenzel selected
the same form of as proposed by Soave, but the same, m, with the acentric factor and
reduced temperature by representing the vapor pressure data of pure compounds. Adding the
in EOS as the third parameter by Schmidt and Wenzel followed by variable estimated critical
compressibility, corresponding to the value of acentric factor.

Mixing Rules
After the statistical and mechanical theory of the Van der Vaals mixing rules, the new idea for
cubic equations of state developed. Widely using cubic equations of state are still in practise
for estimation and identifying the properties of fluids and fluid mixtures. The prediction of
solubility of heavy solids in supercritical fluids is resulted by using the mixing rules for the
Redlich-Kwong and the Peng-Robinson equations of state. The table below shows the different
types of mixing rules and their functions.

Mixing Rules
Van der Waals one-fluid Model

Quadratic Main Rule

Composition-Dependent Combining Rule

Function
It is applied on the main assumption
that the EOS for a substance is similar
to the hypothetical pure fluid
Composition of the mixture is essential
in EOS parameters
Only non-polar compounds can be used
in the mixtures
Virial coefficients which is derived from
statistical thermodynamics is described
as the temperature dependence
Can be correlated by non-ideal
mixtures
containing
strong
polar

compounds
For having CH4, N2 and CO2
Used for highly non ideal fluids
Vidal for use with Redlich-Kwong
Huron-Vidal for use with van der
Waals, Soave-Redlich-Kwong and PengRobinson.
Mollerup for use with van der Waals
Modified Huron-Vidal for use with the
Soave-Redlich-Kwong.

Gibbs Energy (gE)

Question 1
i.

Consider which equations of state would be more relevant for a nonIsothermal case containing <90% hydrocarbons (assume 10% CO2).
-

ii.

The only non isothermal conditions is existing in the Zudkevitch- Joffe which is the
best represent the vapour liquid equilibrium in special hydrocarbon system. It is
temperature dependent due to the a and b parameters in each pure mixture at any
temperature that observed by matching the predicted liquid density. So, one of the
common quadratic mixing rule is used from statistical thermodynamics. This condition
is predicted that it contains the non - polar molecules. Although the content of nonisothermal <90% hydrocarbons and 10% of CO2 with temperature dependent, the
Three Parameter is not applicable as a result of containing polar systems.

Consider which equations

temperatures (T > 300C)
-

iii.

of

state

would

be

more

relevant

at

high

According to the details of each EOS, the critical temperature which is more than 300C
meets in Redlich Kwong (RKEOS), Soave Modification (SRKEOS) and Peng-Robinson
(PREOS). However, the most preferable equation of state is SRK where the term a/T 0.5 is
changed to a more temperature term a(T) when the vapour pressure curve could be
reproduced well. So, in this case it is extrapolated for the supecritical temperatures.
Which equation of state would be preferable for of non-polar substances,
with 5%mole/mole of carbon dioxide?

There are two appropriate EOS which is Redlich Kwong and Peng Robinson which are
the non-polar molecules consistent. In reason of the modification over Redlich- Kwong,
the Peng-Robinson is more applicable EOS for non-polar substances with 5% mole/mole of
carbon dioxide

iv.

Given a super-critical gas condition, what equations of state would you

consider using and why?
-

v.

The accurate prediction of the phase behaviour in the critical region in Soave
modification (SRKEOS) and Peng-Robinson (PREOS) gives us the super critical gas
conditions.

Which equation of state is most valid for high water content (>30% mole
fraction) and why?
-

For high H20 content (>30% mole fraction) case the most appropriate EOS is Three
Parameter. As a result of the polar component of water substance in Three Parameter
equation of state. As it written in details of each equation of state that 3-parameter
EOS has temperature dependent which are a and b and they are often more
accurate to predict systems containing polar molecules.

Question 2
In the case where none of the above equations of state hold valid, what would you
do to predict state for a known composition at a temperature and pressure above
the data sample condition?
-

The complex structure of hydrocarbon molecules introduces significant Van der Vaals
forces. Provided composition at reservoir temperature and pressure and SG (Specific
Gravity) is given, also Z factor indicated from Standing and Kats correlation chart (for
95% hydrocarbon components). With all that known data we can estimate the
pseudocritical pressure (Ppc) and pseudocritical temperature( T pc), where after we can
calculate the values of pseudoreduced pressure (P pr) and pseudoreduced temperature
( Tpr) in order to predict the state.

Question 3
Which of the above equations of state would you use to predict vapour-liquid
equilibrium for a reservoir containing > 98% Hydrocarbons and at a temperature
and pressure of less than 50 barg and 200C. Provide justification as to your
choice of Equations of State.
-

It is obvious that 98 % of hydrocarbons in the reservoir will be non-polar systems

content. Left 2 percent can replace such substances like water or gas (for example
CO2). So, dependently the remained small substance plays role in choosing the right
equation of state. On one hand if the small component is going to be considered as
polar systems, we will use the three parameter EOS. On the other hand if it is nonpolar, there are three equation of states with 2 parametres of a and b which

SRKEOS, PREOS or ZJEOS. Those are the most widely used in thermodynamics.
Generally, for hydrocarbon systems and their mixtures SRKEOS and PREOS have been
widely acceped in oil industry. Also acentric factors are calculated through critical
properties. Therefore, for heavy compounds where critical properties should be
estimated, errors in critical properties will be contributed to acentric factor.

Question 4
Where no laboratory data exists, how would you predict the viscosity and
gas solubility of API30 (exactly) oil at 110C for a known composition?
Viscosity
The viscosity can be found by using the Lohrenz-Bray-Clarks correlation (shown below) which
received great acceptance in oil industry. It is also the most used engineering equation to
predict fluid viscosity in the reservoir:

Where:
=fluid viscosity (cp)
* = viscosity at atmospheric pressure (cp)
m= mixture viscosity parameter (cp-1)
r= reduced liquid density (unitless)
Gas solubility
Using the Vasques-Beggs correlation (shown below) we can predict the gas solubility it API30
oil at 110C without knowing the laboratory data. Table below shows the separation of

two groups, one for oil gravity over 30 API and one at and below 30 API:

Coefficient
C1

o 30 API
0.0362

o >30 API
0.0178

C2

1.0937

1.1870

C3

25.7240

23.9310

Reference

Website: http://en.wikipedia.org/wiki/Van_der_Waals_equation

Website:
http://chemistry.tutorvista.com/physical-chemistry/van-der-waalsequation.html#

Applications of Equations of State in the Oil and Gas Industry, pubished 2011,
By Ibrahim Ashour, Nabeel Al- Rawahi, Amin Fatemi and Gholamreza VakiliNezhaad

Van Der Waals Mixing Rules For Cubic Equations of State, Applications For
Supercritical Fluid Extraction Modelling; 11 January 1985; by T.Y. Kwak and G.A
Mansoori

Reservoir Fluid Property Correlations State of the Art by W.D. McCain Jr., SPE,
Cawley, Gillespie and Assosc.Inc

The Viscosity and Gas Solubility from Fludi properties of petroleum

Journal review the Equations of State for the Calculation of Fluid-Phase

Equilibria by Ya Song Wei and Richard J. Sadus

Schmidt-Wenzel and Peng-Robinson Equations of State for COdHydrocarbon

Mixtures:
Binary Interaction Parameters and Volume 'Translation Factors by Milind D. Deo,
University of Utah; Ram Nutakki, Computer Modelling Group; and Franklin M.
Orr, Jr., Stanford University