Three-parameter Cubic Equation of State for Pure Components of Heavy Oils

Ashutosh Kumar, Amr Henni*

University of Regina, 3737 Wascana Parkway, Regina, SK, S4S 0A2
*corresponding author: amr.henni@uregina.ca

A three-parameter cubic equation of state for pure hydrocarbons is proposed to model

PVT properties of heavy hydrocarbons found in heavy oils. Thirty hydrocarbons up to C40 and
some commonly found (associated) non-hydrocarbons in heavy oils have been used to regress
the parameters. Predicted results from the proposed equation for the liquid density, vapour
pressure, saturated liquid density, and saturated vapour density have been compared with the
widely used Peng-Robinson (PR), Soave-Redlich-Kwong (SRK) and Patel and Teja (PT)
equations of state. With the increase in carbon number in hydrocarbon, the average % absolute
errors in liquid density, vapour pressure and saturated liquid density prediction using PR, SRK
and PT equations of state were found to increase, whereas the proposed equation shows
consistency in the prediction, with a percentage average absolute error of 2.5 only.

Introduction:
Cubic equation of state is very important in process calculations particularly in the oil and
gas industries. Since the first cubic equation of state (EoS) in 1873 by van der Waals, many
improved versions of two-parameter equation of state have been proposed. The obvious
drawback of fixed critical compressibility factors and certain other problems led to development of
three-parameter cubic equation of state. The addition of one more parameter provides flexibility
and hence improves the performance, but its application to heavy hydrocarbons results in large
error. Particularly, the liquid density prediction for higher carbon number components with
available equations is challenging. The proposed three-parameter cubic equation of state for pure
non-hydrocarbons and hydrocarbons commonly found in heavy oils is the basic work aimed at
PVT modeling of heavy oils.
Commonly used equations such as Soave- Redlich- Kwong (SRK) and Peng- Robinson
(PR) suffer from limitations which make them unsuitable for heavy oils or heavy hydrocarbon
components. These two equations are often used with Peneloux volume shift (Peneloux et al.
1982) to predict liquid density. Equations of volume shift (Mathias et al., 1989, Monnery et al.,
1998, Sant Ana et al., 1999) require two or three additional parameters for each component,
which are often found experimentally. Also, application of volume shift does not improve the
phase behaviour prediction.
Inclusion of third parameter in cubic equation of state allows flexibility and hence provides
better results compared to two parameter equation of state. But not all the three parameter cubic
equations of state perform equally well. General form of three parameter cubic equation of state
is given as:
( ) 1
=
+
Major three-parameter cubic equations have and as functions of acentric factor and
both increase with increasing acentric factor. Harmens and Knapp, 1980 has two brackets for
( ) and has not been tried with heavy components. Application of this equation for heavy
hydrocarbon liquid density prediction results in increasing error with increase in carbon number.
Patel and Teja, 1981 (PT EoS) proposed three parameter cubic equation of state, formulation of
which is not simple but saturated liquid density and vapour pressure prediction for hydrocarbons
is good. Though, for lighter hydrocarbons (< n-Nonane), saturated liquid density prediction error
is around 4%, for heavier (upto n-Eicosane) the error is reported to be less than 1%. As, we will
see later that application of this equation for density prediction at pressure-temperature points
other than saturation area also results in increasing error with increase in carbon number.
Volume Translated Peng-Robinson (VTPR) equations are another form of three
parameter cubic equations of state. Equation proposed by Sheng et al. 1990 considers ( ) and
in general form of cubic EoS as function of reduced temperature and there are seven
component specific coefficients (A1, A2, A3, u0, u1, u2, and u3). Later work by Tsai and Chen
(1998) on VTPR is extensive, but it has added more complexity by making ( ) and transfer
parameter (t) a function of reduced temperature. Correlations for coefficients (M, K1, and K2)
used in this VTPR equations are of 4th degree and also other parameters (N, K3) are component
specific. Hence, VTPR equations are very complex and not user friendly.
In view of above review, our goal is to develop a three parameter cubic equation of state
having simplicity of PR EoS (except the addition of one more parameter), but predicts liquid
density with minimum error. In the proposed work, commonly found associated non-hydrocarbons
such as N2, CO2, H2S and 30 hydrocarbons (highest being C40H82) were used to model the
different parameters. The proposed equation has been developed in line with PR equation of
state, offering least complication unlike many other three-parameter equations of state. It is
observed that the proposed equation maintains consistency with an average absolute error of
2.5%. Similar trend is also observed in the prediction of the saturated liquid density and vapour
pressure prediction.

Formulation of the Equation:

All semi empirical cubic equations of state give pressure as the sum of two terms, a
repulsion pressure Pr and an attraction pressure Pa as follows:
= 2
The form of the pressure repulsion term has been kept intact like several other EoS, given as

= 3
( )

The attraction pressure terms can be expressed as:

 a( ) 4
=
( , )

In ( , ), is the molar volume and is a constant related to the size of the hard spheres. The
parameter a( ) takes into account the intermolecular attraction force. A common form of ( , )
is given as:
( , )= + 5
Here u is function of the acentric factor of the compound and w is the function of u. The
parameter a(T) is the product of ac and (T), where ac is value of a(T) at the critical point and
(T) is function of the reduced temperature, such that it is unity at critical point.
a( ) = ( ) 6

Derivation for and :

Imposing the critical point parameters ( , , and ) to equation 6 leads to:

= 7
( ) +

Taking the first partial derivative of with respect to , keeping constant, and imposing it at the
critical point gives:
[2 + ] 8
=
( ) [ + ]

Taking the second partial derivative of with respect to , keeping T constant, and imposing this
on critical point gives:
2 [2(2 + ) 2( + )] 9
=
( ) ( + )

Using equations 8 and 9, a relation between b and is obtained as b. is a function of u

and w. Using equations 7, 8 and 9, expressions for b and are obtained:

= 10

( ) 11
=

= 12
Parameters and are functions of u, w, and . Actual expressions (listed in
appendix) for , , and are complicated, however user friendly forms for these with negligible
weighted (with respect to u) % absolute deviation of 0.15, 0.05, and 0.013 respectively, are
presented in the following equations:
= 13
0.2294 + 0.15037 0.005211
= 14
2.2727+ 11.5807 6.5737
0.014728 15
= 0.006488 + + 0.423

Parameters and has been modelled keeping in view following two factors:

1. ( , ) increases with increasing acentric factor. Unlike many three parameter cubic
 equations of state where difference of parameters and is held constant, In the present
work this difference increases with increasing acentric factor, by making decrease with
increasing .
2. decreases with increasing acentric factor and remains almost equal to of PR EoS.
With the proposed equation average % absolute deviation for from of PR EoS (i.e.
0.45724) is 0.5%. However, decreases till acentric factor of 0.6 and after that there is
increase with small gradient.

Parameters and are given as:

= 0.1794 + 1.7562 + 1.5061 16
where is the acentric factor.
1 17
=
1

Parameters and were obtained from best fit over a wide range of experimental data
in two steps. At step one, starting with initial assumption for (Equation 26), best value of was
obtained for each component giving minimum error for experimental PVT data, keeping the
critical compressibility close to experimental one. A correlation was thus obtained for , which
was used to obtain as function of acentric factor from experimental vapor pressure data at
second step. This was again used at step 1 to find suitable correlation for . This was
continued until optimum minimum % average absolute error was obtained for each component.

Equation 1 can be rewritten as cubic equation in Z-factor:

+( 1) +( ) +( + )=0 18
where Z, A, and B are given as:

= 19
a( ) 20
=
( )

= 21

Applying thermodynamic relationship for fugacity coefficient calculation to equation 1, an

expression for fugacity coefficient is given by the following equation:
2 + +4 22
log = ( 1) log( )+ log
+4 2 + + +4

The enthalpy departure is calculated using standard thermodynamic relation:

( ) 23
( ) 2 + + +4
= ( 1) + log
+4 2 + +4

with:
( ) ( ) 24
=
The expression for ( ) is same as used in SRK and PR EoS, and given as:
.
25
( )= 1+ 1

The vapour pressure calculation using the equation 1, was done for 27 components and
the value for m was tuned to give least deviation from experimental data. Optimum values were
then correlated with the acentric factor to give following relation (Figure 1):
= 0.3547 + 1.6296 0.2773 26

2
Octacosane
1.8 m = -0.2773 2 + 1.6296 + 0.3547 Docosane
R = 0.9998 Nonadecane Tetracosane
1.6
Eicosane
Hexadecane
1.4 Octadecane
Tetradecane
1.2 Dodecane
1 Decane
m

Pentane Nonane
Octane
0.8 Cyclo Hexane Heptane
Iso Butane Hexane
0.6 Propyelene CO2
Ethylene Butane Benzene
0.4 Propane
H2S
Nitrogen Ethane
0.2 Methane
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4
Acentric Factor,

Figure 1: Relationship between m and acentric factor,

Following simple mixing rules as in PR EoS are used in case of mixture:

= 27

.
= (1 , ) 28

29
=

30
=

+( 1) +( ) +( + )=0 31
( 1) 2 32
log = log( )+ , + , where
( +4 )
 = ( ) ( 2 ) 1
( )
+( ) (2 + ) 1
( )
2

2 + 2 +4
= log
2 +4 2 + + 2 +4

Proposed mixing rules for u and w (Equation 29 & 30) result in marginal improved result over the
linear mixing rule. However, these mixing rules are presented here as they have been used for
heavy oils and perform better than other mixing rules.

Comparison of Calculations:
The proposed equation of state is developed for hydrocarbon components and
associated non-hydrocarbons commonly found in oil and gas reservoirs. In this study, 34
compounds were considered among which 30 components were hydrocarbons. The highest
carbon number hydrocarbon investigated is n-Tetracontane (C40H82). Except for N2 and CO, liquid
density data for rest of the components were used. Vapour pressure, corresponding liquid and
vapour density predictions for 19 components were investigated considering two prominent two
parameter equation of state, SRK and PR EoS and one three parameter cubic equation of state
often used, Patel and Teja, 1981 (PT EoS). VTPR EoS was not included in the comparison as
they require several parameters which make them complex and also, some parameters are
component specific.

Liquid Density Calculation:

A total of 32 components were included to test the accuracy of proposed equation of
state to predict liquid density. In case of two components, N2 and CO, the pressure was predicted
from their temperature and molar volume data. Data from Doolittle, 1964, for components C11,
C17, C20, C30, and C40 are claimed to be accurate over 97% of the range to approximately
0.2%.There is possibility of more error than claimed, hence, only for all such data the deviation is
around 4%, whereas for other data deviation is close to 2%. The calculations results are
summarised in Table1. The deviation in liquid density prediction with the proposed equation of
state is consistently around 2.5 %, which is much less than that for SRK, and PR EoS and less
rd
than 1/3 of the error from PT EoS for heavier hydrocarbons. Though, for PT EoS error is
marginally higher than the proposed equation for lower hydrocarbons, for higher hydrocarbons
there is significant increase in the error with increase in carbon number.
Critical parameters for higher hydrocarbons (C20+) were obtained from correlations
(Appendix) developed for alkanes which fit quite well. Deviation in case of critical temperature
and acentric factor compared to other correlations may be negligible. However, in case of critical
pressure, deviation from other correlations is comparatively high (Table 2). The critical pressure
for higher alkanes calculated from some correlations available seem to be on the lower side (Nji
et al., 2008) and others on higher side (Lydersen,1955). It is recommended to use this correlation
to calculate critical pressure while using the proposed equation of state. A comparison of critical
pressures obtained from different correlations is given in Table 2. Critical parameters for other
hydrocarbons were taken from API Technical Data Book, by Daubert and Danner, 1997 and
http://www.cheric.org/.

Table 1: Comparison of Liquid Density Prediction

Liq. Density/ Pressure (N2,CO)
%Average Absolute Error
Compo- No. of Temp. Press. PR SRK PT
References Model
nent Data Range (Tr) Range (Pr) EOS EOS EoS
N2 Deming and Shupe (1931) 168 1.61-7 0.6-35.8 2.0 8.3 2.5 3.9
Lewis and Fredrick (1968),
H2S 129 0.54-1.9 0.01-19 3.7 5.0 7.1 4.3
Perry and Green (2008)
CO Deming and Shupe (1931) 154 1.51-5 0.72-34.8 2.7 9.7 2.7 4.6
CO2 Klimeck et al. (2001) 101 0.79-1.55 0.68-4.2 3.7 3.3 9.2 4.0
Klimeck et al. (2001), 0.02-
CH4 176 0.52-3.15 1.7 3.1 2.4 1.5
Perry and Green (2008) 108.7
C2H6 Philips and Thodos (1962) 111 0.7-2 1-14 2.2 6.0 3.6 3.0
Claus et al. (2003),
C2H4 133 0.37-1.1 0.1-6 1.9 7.2 4.6 1.4
Nowak et al. (1996)
Glos et al. (2004),
C3H8 229 0.26-1.03 0.03-2.8 2.0 5.0 7.7 2.3
Kayukawa et al. (2005)
C3H6 Glos et al.(2004) 64 0.26-0.92 0.47-2.8 4.0 5.2 6.5 3.2
Glos et al.(2004), Kayukawa et al.
C4H10 222 0.33-0.89 0.01-3.2 1.4 4.2 7.9 1.6
(2005),Miyamoto and Uematsu (2007)
Glos et al.(2004),Kayukawa et al. (2005),
i-C4H10 210 0.29-0.93 0.01-3.3 1.9 5.0 7.3 2.1
Miyamoto et al. (2008)
C5H12 Lee and Ellington (1965) 164 0.66-0.91 0.2-16.4 3.0 4.4 7.3 2.8
C6H6 Straty et al. (1987) 314 0.75-1.3 0.18-7.3 4.8 4.1 11.3 5.3
C7H8 Franck et al. (1998) 90 0.55-0.97 1.22-73 1.9 2.0 9.9 1.9
C5H10 Harris et al. (2004) 183 0.5-0.58 0.02-84 1.8 4.2 6.7 1.7
Kelso and Felsing (1940),
C6H14 63 0.74-1.31 0.19-20 3.1 3.0 8.5 2.9
Abdulagatov (1996)
C7H16 Doolittle(1964),,Schilling et al. (2008) 214 0.43-1.06 0.4-182.5 2.3 1.8 11.6 1.9
Goodwin et al. (1996),
C8H18 34 0.52-1.06 0.04-40 2.6 3.2 13.1 1.9
Perry and Green (2008)
Perry and Green (2008),
C9H20 192 0.39-0.96 0.5-218 2.0 5.1 15.1 2.2
Schilling et al. (2008)
C11H24 Doolittle(1964) 70 0.47-0.9 2.53-253 3.1 7.2 16.7 3.8
C12H26 Elizalde-Solis et al. (2007) 150 0.48-0.55 0.56-13.6 1.5 9.6 19.2 2.7
C13H28 Elizalde-Solis et al. (2007) 150 0.45-0.55 0.6-14.9 1.7 12.2 21.5 4.9
C17H36 Doolittle(1964) 60 0.44-0.78 3.73-373 3.7 16.3 24.9 6.6
C18H38 Dutour et al. (2000) 103 0.42-0.51 7.87-118 2.4 18.9 27.2 8.3
C19H40 Dutour et al. (2000) 99 0.41-0.51 8.26-123 2.3 19.7 27.9 8.5
C20H42 Doolittle(1964) 50 0.49-0.75 4.31-431 3.8 17.9 26.3 6.1
C21H42 Dutour et al (2003) 128 0.38-0.47 0.08-118. 1.1 17.5 25.9 5.9
C23H48 Dutour et al. (2001) 90 0.42-0.49 9.91-148 2.7 23.1 30.9 10.0
C24H50 Dutour et al. (2001) 85 0.41-0.49 10.29-154 2.5 23.6 31.4 10.1
C25H50 Dutour et al (2003) 95 0.38-0.46 0.09-140 1.6 19.7 27.9 6.1
C28H58 Dutour et al. (2002) 81 0.42-0.48 11.7-176 1.8 25.1 32.7 10.3
C30H62 Doolittle(1964) 50 0.43-0.67 6.25-625 4.1 24.3 32.0 8.7
C36H74 Dutour et al. (2002) 64 0.4-0.45 0.15-220 1.2 27.0 34.4 10.3
C40H82 Doolittle(1964) 40 0.46-0.62 7.97-797 5.1 26.0 33.5 8.6

Table 2: Comparison of Critical Pressure Correlations

Critical Pressure (Bar)
Component Lydersen (1955) Developed Nji et al. (2008)
C23H48 10.636 10.12 9.603
C24H50 10.242 9.75 9.197
C28H58 8.921 8.52 7.846
C30H62 8.380 8.03 7.299
C36H74 7.090 6.88 6.021
C40H82 6.429 6.29 5.375

Vapour Pressure Calculation:

Vapour pressures for 27 components with 24 hydrocarbons (highest being C28H58) were
calculated. It can be seen that for light hydrocarbon components up to Heptane and for non
hydrocarbons, the average absolute deviation is similar to SRK and PR equations. However, with
the increase in carbon number, the error with proposed equation is less than SRK and PR
equations. Similarly, in case of PT EoS, vapour pressure prediction for light hydrocarbons is
good, but there is increasing trend of error for heavier hydrocarbons. For the proposed equation,
the error is not only around 2%, it is consistent as well.
Table 3 : Comparison of Vapor Pressure Prediction
Vapour Pressure,
% Abs. Avg. Error
Component No. of Data Reference Model PR EoS SRK EoS PT EoS
Nitrogen 28 Nowak et al. (1997) 1.24 0.51 1.64 0.65
H2S 18 Perry and Green (2008) 1.41 1.24 1.05 0.65
CO2 16 Perry and Green (2008) 1.14 0.81 0.38 0.60
Methane 18 Perry and Green (2008) 0.45 1.53 1.63 1.75
Ethane 20 Funke et al (2002) 0.66 1.25 1.61 1.39
Ethylene 31 Nowak et al (1997) 1.33 1.70 0.72 1.79
Propane 18 Miyamoto and Uematsu (2007), Perry and Green (2008) 1.25 1.44 1.39 1.31
Propylene 14 Perry and Green (2008) 2.27 2.46 1.38 2.27
Iso Butane 19 Miyamoto et al. (2008), Perry and Green (2008) 1.47 2.07 1.76 2.28
Butane 20 Miyamoto and Uematsu (2007), Perry and Green (2008) 1.40 1.99 1.72 2.13
Pentane 53 Ewing and Ochoa (2006), Beattie et al. (1951), Sage and Lacey (1942) 0.59 0.53 1.43 0.62
Hexane 67 Ewing and Ochoa (2006),Perry and Green (2008) 0.80 0.71 1.15 0.72
Cyclo Hexane 81 Ewing and Ochoa (2000), Perry and Green (2008) 1.70 1.48 1.43 1.25
Benzene 19 Perry and Green (2008) 2.03 2.18 0.85 1.78
Heptane 52 Ewing and Ochoa (2000),, Perry and Green (2008) 0.88 0.94 1.33 0.96
Octane 28 Gregorowicz et al. (1987), Perry and Green (2008) 0.96 1.09 0.82 1.02
Nonane 13 Perry and Green (2008) 1.09 1.90 1.81 1.47
Decane 30 Gregorowicz et al. (1987),,Perry and Green (2008) 1.23 2.86 1.51 1.08
Dodecane 16 Perry and Green (2008) 1.24 4.11 1.70 2.24
Tetradecane 16 Morgan and Kobayashi (1994) 1.45 3.97 0.81 2.87
Hexadecane 16 Morgan and Kobayashi (1994) 1.47 7.39 0.71 3.57
Octadecane 17 Morgan and Kobayashi (1994) 0.47 9.99 0.21 4.37
Nonadecane 16 Morgan and Kobayashi (1994) 0.86 11.14 1.49 5.07
Eicosane 16 Morgan and Kobayashi (1994) 1.18 11.72 3.80 4.87
Docosane 12 Morgan and Kobayashi (1994) 2.29 12.25 5.82 5.40
Tetracosane 13 Morgan and Kobayashi (1994) 1.06 17.43 6.16 10.89
Octacosane 14 Morgan and Kobayashi (1994) 1.21 24.20 7.75 19.14

Saturated Liquid Density Calculation:

Saturated liquid density calculations for 19 components considered for vapour pressure
prediction, were done with the proposed equation. In case of the proposed equation, the error is
consistently around 2.5%. Results are compared in Table 4.
Table 4: Comparison of Saturated Liquid Density Prediction
Saturated Liquid Density,
% Abs. Avg. Error
Component No. of Data Reference Model PR EoS SRK EoS PT EoS
Nitrogen 28 Nowak et al. (1997) 1.87 8.69 4.22 3.97
Hydrogen Sulfide 18 Perry and Green (2008) 1.14 6.58 5.90 2.07
Carbon Dioxide 16 Perry and Green (2008) 2.50 3.16 11.07 2.80
Methane 18 Perry and Green (2008) 3.01 8.92 3.87 3.19
Ethane 20 Funke et al. (2002) 2.08 6.13 6.92 3.35
Ethylene 31 Nowak et al. (1996) 2.76 6.14 7.24 3.41
Propane 18 Miyamoto and Uematsu (2007), Perry and Green (2008) 2.13 4.92 8.59 2.92
Propylene 15 Perry and Green (2008) 1.72 5.39 7.30 1.72
Iso Butane 24 Miyamoto et al. (2008), Perry and Green (2008) 1.96 4.49 8.36 2.28
Butane 25 Miyamoto and Uematsu (2007), Perry and Green (2008) 2.04 3.95 9.30 2.31
Pentane 9 Sage and Lacey (1942) 3.78 3.90 13.02 4.14
Hexane 33 Beg et al (1993), Perry and Green (2008) 2.22 2.19 12.62 2.20
Cyclo Hexane 36 Beg et al (1993), Perry and Green (2008) 2.39 4.43 8.58 2.54
Benzene 30 Beg et al (1993), Perry and Green (2008) 1.51 2.75 10.34 0.69
Heptane 14 Perry and Green (2008) 2.07 2.50 13.72 1.79
Octane 13 Perry and Green (2008) 2.67 4.42 15.47 2.07
Nonane 13 Perry and Green (2008) 2.02 4.79 15.77 1.31
Decane 15 Perry and Green (2008) 2.73 6.66 17.38 1.95
Dodecane 19 Perry and Green (2008) 2.37 9.12 19.42 2.23

It is obvious from the comparison that for all components, the predicted saturated liquid
density is much better than SRK and PR equations. For PT EoS for lighter components the error
is marginally higher than the proposed equation, for higher hydrocarbons it is almost equal.
Keeping in view the trends of error, the proposed equation should produce saturated liquid
density within 2.5% deviation even for higher hydrocarbons.
Saturated Vapour Density Calculation:
The saturated vapour density was calculated for all compounds considered for the vapour
pressure calculation. The comparison is presented in Table 5. Though, the SRK EoS appears
performing consistently well, on average the error for the proposed equation is a little higher than
that of the SRK and slightly better than that of the PR EoS. The proposed equation, on average
predicts better results compared to PT EoS.

Enthalpy Departure Calculation:

Enthalpy departure calculation was done for five compounds. Though, not many suitable
enthalpy data are available, enthalpy calculation was done to see the range of deviation. The
comparison is presented in Table 6. It appears that the deviation in enthalpy departure calculation
is almost the same as for the PR EoS and PT EoS, but better than that of the SRK EoS. The
enthalpy departure and liquid are strong function of Z-factor and a(T). Since with the proposed
model, the liquid density prediction is much better, same is expected that even for higher
hydrocarbons.
Table 5: Comparison of Saturated Vapour Density Prediction
Saturated Vapour Density,
% Abs. Avg. Error
Component No. of Data Reference Model PR EoS SRK EoS PT EoS
Nitrogen 28 Nowak et al. (1997) 1.74 1.58 1.78 0.91
Hydrogen Sulfide 18 Perry and Green (2008) 1.67 1.38 1.80 0.79
Carbon Dioxide 16 Perry and Green (2008) 1.59 1.26 1.29 1.14
Methane 18 Perry and Green (2008) 0.83 2.19 1.55 1.62
Ethane 20 Funke et al. (2002) 1.13 1.72 1.33 1.30
Ethylene 31 Nowak et al. (1996) 1.68 2.30 0.57 1.70
Propane 14 Perry and Green (2008) 1.83 2.15 1.31 1.40
Propylene 14 Perry and Green (2008) 2.57 2.74 1.63 2.57
Iso Butane 13 Perry and Green (2008) 2.00 2.77 1.10 2.59
Butane 14 Perry and Green (2008) 1.60 2.35 0.84 2.11
Pentane 9 Sage and Lacey (1942) 1.17 1.16 0.47 1.07
Hexane 18 Perry and Green (2008) 1.71 2.10 1.49 1.75
Cyclo Hexane 26 Perry and Green (2008) 3.38 3.09 3.43 2.97
Benzene 19 Perry and Green (2008) 2.33 2.50 0.90 2.06
Heptane 14 Perry and Green (2008) 2.20 2.75 1.49 2.56
Octane 13 Perry and Green (2008) 1.19 1.30 1.01 1.45
Nonane 13 Perry and Green (2008) 1.43 1.66 1.36 1.89
Decane 15 Perry and Green (2008) 1.64 2.30 1.59 2.36
Dodecane 16 Perry and Green (2008) 2.21 3.76 1.74 3.38

Table 6: Comparison of Enthalpy Departure

Enthalpy Departure,
% Abs. Avg. Error
Component No. of Data Reference Model PR EOS SRK EOS PT EoS
Methane 42 Corcoran et al. (1945) 2.81 2.86 3.26 2.73
Pentane 160 Lenoir et al. (1970) 1.99 2.02 2.99 2.02
Benzene 169 Lenoir et al. (1971) 2.11 2.12 2.87 2.21
Cyclo Hexane 112 Lenoir et al. (1971) 3.15 3.13 3.86 3.23
Octane 106 Lenoir et al. (1970) 1.27 1.33 1.49 1.27

Mixture Density Calculation:

Mixture density calculation was done for hydrocarbons ranging from methane to
Tetracosane. In all calculation, the binary interaction parameter has been assumed to be zero to
have a better comparison. The results are listed in Table 7.
 It can be seen that error in liquid density prediction for hydrocarbons mixture for SRK and
PR EoS is like the pure components. In case of PT EoS the error is much smaller than the SRK
and PR EoS, however, the error keep on increasing with increase in carbon number. The
proposed equation, like pure component liquid density prediction, consistently predicts density
within error of 2.5%, which is around 1/3rd of error in case of PT EoS.

Table 7: Comparison of Mixture Density

Mixture Density,
%Avg. Abs. Error
Component No. of Reference Model PR EoS SRK EoS PT EoS
Data
Methane + Decane 104 Audonnet and Padua, (2004) 1.62 4.55 14.30 6.19
Pentane+ Hexane 11 Aucejo et al. (1995) 1.5 2.0 9.7 1.0
Pentane+ Heptane 11 Aucejo et al. (1995) 1.4 1.3 10.6 0.6
Pentane+ Octane 11 Aucejo et al. (1995) 1.1 1.9 11.8 0.6
Pentane+ Nonane 11 Aucejo et al. (1995) 0.8 2.9 12.9 1.2
Pentane+ Decane 11 Aucejo et al. (1995) 0.5 4.0 14.0 1.9
Pentane+ Undecane 11 Aucejo et al. (1995) 1.0 5.9 15.7 3.2
Pentane+ Dodecane 11 Aucejo et al. (1995) 0.9 6.4 16.2 3.4
Pentane+ Hexadecane 11 Aucejo et al. (1995) 3.1 11.8 20.9 7.3
Hexane+ Heptane 11 Aucejo et al. (1995) 1.2 0.6 11.4 0.4
Hexane+ Octane 11 Aucejo et al. (1995) 0.9 1.7 12.6 0.5
Hexane+ Nonane 11 Aucejo et al. (1995) 1.8 3.8 14.4 2.0
Hexane+ Decane 11 Aucejo et al. (1995) 0.5 4.1 14.6 1.7
Hexane+ Undecane 11 Aucejo et al. (1995) 0.6 5.4 15.7 2.5
Hexane+ Dodecane 11 Aucejo et al. (1995) 0.6 6.4 16.6 3.0
Hexane+ Hexadecane 11 Aucejo et al. (1995) 2.8 11.7 21.1 6.7
Heptane+ Octane 11 Aucejo et al. (1995) 1.1 2.3 13.2 0.4
Heptane+ Nonane 11 Aucejo et al. (1995) 0.9 3.4 14.1 0.8
Heptane + Decane 11 Aucejo et al. (1995) 0.6 4.6 15.1 1.5
Heptane + Undecane 11 Aucejo et al. (1995) 0.5 5.8 16.2 2.3
Heptane + Dodecane 10 Aucejo et al. (1995) 0.6 6.7 17.0 2.7
Heptane + Hexadecane 11 Aucejo et al. (1995) 2.6 11.9 21.5 6.3
Octane + Nonane 11 Aucejo et al. (1995) 0.7 4.5 15.1 1.3
Octane + Decane 11 Aucejo et al. (1995) 0.4 5.6 15.9 1.7
Octane + Undecane 11 Aucejo et al. (1995) 0.4 6.7 16.9 2.4
Octane + Dodecane 11 Aucejo et al. (1995) 0.6 7.8 17.8 3.0
Octane + Hexadecane 11 Aucejo et al. (1995) 2.6 12.5 22.0 6.3
Nonane + Decane 11 Aucejo et al. (1995) 0.4 6.3 16.6 1.9
Nonane + Undecane 11 Aucejo et al. (1995) 0.4 7.5 17.6 2.6
Nonane+ Dodecane 11 Aucejo et al. (1995) 0.4 8.3 18.3 2.9
Nonane + Hexadecane 11 Aucejo et al. (1995) 2.2 12.9 22.2 6.0
Decane + Undecane 11 Aucejo et al. (1995) 0.3 8.4 18.4 3.0
Decane + Dodecane 11 Aucejo et al. (1995) 0.4 9.2 19.1 3.3
Decane + Hexadecane 11 Aucejo et al. (1995) 2.2 13.4 22.7 6.0
Undecane + Dodecane 11 Aucejo et al. (1995) 0.7 10.1 19.9 3.8
Undecane + Hexadecane 11 Aucejo et al. (1995) 2.4 14.2 23.4 6.4
Dodecane + Hexadecane 11 Aucejo et al. (1995) 2.6 14.7 23.8 6.5
Decane + Eicosane 24 Queimada et al. (2005) 1.0 14.9 24.02 6.2
Decane + Docosane 20 Queimada et al. (2005) 2.4 16.97 25.82 8.0
Decane + Tetracosane 16 Queimada et al. (2005) 2.4 18.05 26.76 8.6
Decane + Docosane+ Tetracosane 23 Queimada et al. (2005) 1.8 17.17 26.0 7.6

Conclusion:
From the comparison, it is evident that the proposed equation can predict liquid density in
general, and the saturated liquid density with an average absolute error less than 2.5%, whereas
with other equations of state, the error in prediction keeps on increasing with increasing carbon
number. Deviation in vapour pressure prediction with the proposed equation is also better than
other equation. Vapour density prediction is slightly better than PR EoS and close to SRK
equation. Enthalpy departure prediction is better than SRK, and close to PR and PT EoS. Given
a significantly better liquid density prediction, better enthalpy departure prediction for higher
hydrocarbons is also expected.
 It is important to note that error with the proposed equation for all predicted
thermodynamic parameters is consistent and very low, whereas for the other equations, there is
an increasing trend and for higher hydrocarbon, errors can be very high. This makes the
proposed equation suitable for PVT prediction for pure and mixed hydrocarbons and non-
hydrocarbons associated with crude oil.

Acknowledgement: The authors thank Petroleum Technology Research Centre, Regina, SK,
Canada, for the financial support provided for this project.

Appendix
Actual expression for , , :

( 1) 4 + ( 2 + ( )+ + 2) ( 1)
= + + +1
2 2
( 1) 4 + ( 2 + ( )+ + 2)
+
2 2

( 2 + )
=
(2 + )( 1)

( 2 + )[ + ]
=
[(2 + )( 1) ]

Correlation used for critical pressure (Pc):

M is molecular weight and Pc is in Bar.

2.0736 + 0.000655
=
298.02
1 + 0.0006867

Correlation used for critical temperature (Tc):

M is molecular weight and Tc is in Kelvin.

. .
61.7269 + 2099.44

Correlation used for acentric factor ( ):

M is molecular weight
0.003784 0.01474
=
1 + 0.0004109 + 7.4913 10
References:
Abdulagatov, I. M., Bazaev, A. R., Gasanov, R. K. Measurements of the (p, , T) properties and
virial coefficients of pure water, methane, n-hexane, n-Octane, Benzene, and of their aqueous
mixtures in the supercritical regions, Journal of Chemical Thermodynamics, 28, 1037-1057
(1996)
Audonnet, F., Padua, A. A. H, Viscosity and Density of Mixture of Methane and n-Decane from
298 to 393 K and upto 75 MPa, Fluid Phase Equilibria, 216, 235-244(2004)
Aucejo, A., Burguet, M. C., Muoz, R.,Marques, J. L., Densities, Viscosities, and Refractive
Indices of Some n-Alkane Binary Liquid System at 298.15K, Journal of Chemical and
Engineering Data, 40, 141-147(1995)
Beattie, J. A., Levine, S. W., Douslin, D. R., The Vapour Pressure and Critical Constants of
Normal Pentane, Journal of American Chemical Society, 73(9), 4431-4432 (1951)
Beg, S. A., Tukur, N. M., Al-Harbi, D. K., Hamad, E. Z., Saturated Liquid Densities of Benzene,
Cyclohexane, and Hexane from 298.15 to 473.15 K, Journal of Chemical and Engineering Data,
38, 461-464 (1993)
Claus, P., Kleinrahm, R., Wagner, W., Measurements of the (p, , T) Relation of Ethylene,
Ethane, and Sulphur Hexafluoride in the Temperature Range from 235K to 520K at Pressure upto
30MPa Using and Accurate Single Sinker Densimeter, Journal of Chemical Thermodynamics,
35, 159-175(2003)
Corcoran, W. H., Bowles, R. R., Sage, B. H., Lacey, W. N., Thermodynamic Properties of
Methane at Low Temperature, Industrial and Engineering Chemistry, 37(9), 825-828(1945)
Deming, W. E., Shupe, L.E., Some Physical Properties of Compressed Gases I. Nitrogen,
Physical Review, 37,638-654(1931)
Daubert, T. E., Danner, R. P., API Technical Data Book-Petroleum Refining, 6th Edition, American
Petroleum Institute, Washington D.C., 1997
Deming, W. E., Shupe, L.E., Some Physical Properties of Compressed Gases II. Carbon
Monoxide, Physical Review, 38, 2245-2264(1931)
Doolittle, A. K., Specific Volumes of n-Alkanes, Journal of Chemical and Engineering Data, 9(2),
275-279 (1964)
Dutour, S., Carier, H., Daridon, J. L., Compressibilities of Liquid Pentadecylcyclohexane and
Nonadecylcyclohexane from High Pressure Speed of Sound and Density Measurements,
Journal of Chemical Thermodynamics, 35, 1613-1622 (2003)
Dutour, S., Daridon, J. L., Lagourette, B., Pressure and Temperature Dependence of the Speed
of Sound and Related Properties in Normal Octadecane and Nonadeane, International Journal of
Thermophysics, 21(1), 173-184(2000)
Dutour, S., Lagourette, B., Daridon, J. L., High Pressure Speed of Sound and Compressibilities
in Heavy Normal Hydrocarbons: n-C23H48 and n-C24H50, Journal of Chemical Thermodynamics,
33,765-774(2001)
Dutour, S., Lagourette, B., Daridon, J. L., High Pressure Speed of Sound and Compressibilities
in Heavy Normal Paraffins: n-C28H58 and n-C36H74, Journal of Chemical Thermodynamics,
34,475-484(2002)
Elizalde-Solis, O., Galicia-Luna, L. A., Camacho-Camacho, L. E., High Pressure Vapor Liquid
Equilibria for CO2 + Alkanol Systems and Densities of n-Dodecane and n-Tridecane, Fluid
Phase Equilibria, 259, 23-32 (2007)
Ewing, M. B., Ochoa, J. C. S., The Vapour Pressures of Cyclohexane Over the Whole Fluid
Range Determined Using Comparative Ebulliometry, Journal of Chemical Thermodynamics, 32,
1157-1167(2000)
Ewing, M. B., Ochoa, J. C. S., Vapour Pressure of n-Pentane Determined by Comparative
Ebulliometry, Journal of Chemical Thermodynamics, 38, 289-295 (2006)
Ewing, M. B., Ochoa, J. C. S., Vapour Pressures of n-Heptane Determined by Comparative
Ebulliometry, Journal of Chemical Thermodynamics, 50, 1543-1547(2000)
Ewing, M. B., Ochoa, J. C. S., Vapour Pressures of n-Hexane Determined by Comparative
Ebulliometry, Journal of Chemical Thermodynamics, 38, 283-288(2006)
Franck, E. U., Kerschbaum, S., Wiegand, G., The Density of Toluene at High Pressure to 673K
and 300 MPa, Ber. Bunsenges. Phy. Chem. 102(12), 1794-1797 (1998)
Funke, M., Kleinrahm, R., Wagner, W., Measurement and Correlation of the (p, , T) Relation of
Ethane II. Saturated Liquid and Satuarted Vapour Densities and Vapour Pressure along the
Entire Coexistence Curve, Journal of Chemical Thermodynamics, 34, 2017-2039 (2002)
Glos, S., Kleinrahm, R., Wagner, W., Measurements of the (p, , T) Relation of Propane,
Propylene, n-Butane, and Isobutane in the Temperature Range from (95 to 340) K at Pressure up
to 12 MPa Using an Accurate Two Sinker Densimeter, Journal of Chemical Thermodynamics,
36, 1037-1059(2004)
Goodwin, A. R. H., Bradsell, C. H., Toczylkin, (p, , T) of Liquid n-Octane Obtained with a
Spherical Pycnometer at Temperature of 298.03K and 313.15K and Pressures in the Range of
0.7 MPa to 32 MPa, Journal of Chemical Thermodynamics, 28, 637-646 (1996)
Gregorowicz, J., Kiciak, K., Malanowski, S., Vapour Pressure Data for 1-Butanol, Cumene, n-
Octane and n-Decane and Their Statistically Consistent Reduction with the Antoine Equation,
Fluid Phase Equilibria, 38, 97-107 (1987)
Harmens, A., Knapp, H., Three Parameter Cubic Equation of State for Normal Substances,Ind.
Eng. Chem. Fundamen.,19(3),291-294(1980)
Harris, K. R., Newitt, P. J., Woolf, L. A., Temperature and Density Dependence of the Viscosity
of Cyclopentane, Journal of Chemical and Engineering Data, 49, 138-142(2004)
Kayukawa, Y., Hasumoto, M., Kano, Y., Watanabe, K., Liquid Phase Thermodynamic Properties
for Propane (1), n-Butane (2), and Isobutane (3), Journal of Chemical & Engineering Data, 50,
556-564(2005)
Kelso, E. A., Felsing, W. A., The Pressure Volume Temperature Relation of n-Hexane and of
2-Methylpentane, Journal of American Chemical Society, 62(11), 3132-3134 (1940)
Klimeck, J., Kleinrahm, R., Wagner, W., Measurements of (p, , T) Relation of Methane and
Carbon Dioxide in the Temperature Range of 240K to 520K at Pressure upto 30MPa Using a
New Accurate Single Sinker Densimeter, Journal of Chemical Thermodynamics, 33, 251-
267(2001)
Lee, A. L., Ellington, R. T., Viscosity of n-Pentane, Journal of Chemical and Engineering Data,
10(2), 101-103 (1965)
Lenoir, J. M., Hayworth, K. E., Hipkin, H. G., Enthalpy of Benzene and Mixtures of Benzene with
n-Octane, Journal of Chemical and Engineering Data, 16(3), 280-285(1971)
Lenoir, J. M., Robinson, D. R., Hipkin, H. G., Enthalpies of Mixture of n-Octane and n-Pentane,
Journal of Chemical and Engineering Data, 15(1), 26-31(1970)
Lenoir, J. M., Robinson, D. R., Hipkin, H. G., Flow Calorimeter and Measurement of the Enthalpy
of n-Pentane, Journal of Chemical and Engineering Data, 15(1), 23-26(1970)
Lenoir, J. M.,Kuravila, G. K., Hipkin, H. G., Enthalpies of Cyclohexane and Mixtures of n-Pentane
and Cyclohexane, Journal of Chemical and Engineering Data, 16(3), 271-276(1971)
Lewis, L.C., Fredericks, W.J., Volumetric Properties of Supercritical Hydrogen Sulfide, Journal
of Chemical and Engineering Data, 13(4), 482-485(1968)
Lydersen, A. L.,Estimation of Critical Properties of Organic Compounds, University of
Wisconsin, Engineering Experimental Station Report 3, Madison, Wisconsin, April, 1955
Mathias, P. M., Naheiri, T., Oh, E. M., A Density Correction for the Peng-Robinson Equation of
State, Fluid Phase Equilibria, 47, 77-87(1989)
Miyamoto, H., Koshi, T., Uematsu, M., Measurements of Saturated Liquid Densities for
Isobutane at T = (280 to 407) K, Journal of Chemical Thermodynamics, 40, 1222-1225 (2008)
Miyamoto, H., Uematsu, M., Measurements of Vapour Pressures and Saturated Liquid
Densities for n-Butane at T=(280 to 424) K, Journal of Chemical Thermodynamics, 39, 827-832
(2007)
Miyamoto, H., Uematsu, M., Measurements of Vapour Pressures and Saturated Liquid
Densities for n-Butane at T = (280 to 424) K, Journal of Chemical Thermodynamics, 39, 827-
832(2007)
Miyamoto, H., Uematsu, M., Saturated Liquid Densities of Propane at T= (280 to 365 ) K,
Journal of Chemical Thermodynamics, 39, 225-229(2007)
Miyamoto, Koshi, T., H., Uematsu, M., Measurements of Saturated Liquid Densities for
Isobutane at T = (280 to 407) K, Journal of Chemical Thermodynamics, 40, 1222-1225(2008)
Monnery, W. D., Svrcek, W. Y., Satyro, M. A., Gaussian Like Volume Shifts for Peng Robinson
Equation of State, Ind. Eng. Chem. Res. 37,1663-1672(1998)
Morgan, D.L., Kobayashi, R., Direct Vapour Pressure Measurements of Ten n-Alkanes in the
C10-C28 Range, Fluid Phase Equilibria, 97, 211-242(1994)
Nji, G. N., Svrcek, W. Y., Yarranton, H. W., Characterization of Heavy Oils and Bitumens. 1.
Vapor Pressure and Critical Constants Prediction Method for Heavy Hydrocarbons, Energy &
Fuels, 22, 455-462 (2008)
Nowak, P., Kleinrahm, R., Wagner, W., Measurement and Correlation of (p, , T) Relation of
Ethylene, I. The Homogeneous Gaseous and Liquid Regions in the Temperature Range from
105K to 340K at Pressure upto 12 MPa, Journal of Chemical Thermodynamics, 28, 1423-1439
(1996).
Nowak, P., Kleinrahm, R., Wagner, W., Measurement and Correlation of the (p, , T) Relation of
Nitrogen II. Saturated Liquid and Saturated- Vapour Pressures along the Entire Coexistence
Curve, Journal of Chemical Thermodynamics, 29, 1157-1174(1997)
Nowak, P., Kleinrahm, R., Wagner, W., Measurements and Correlation of the (p, , T) Relation
of Ethylene II. Saturated Liquid and Saturated Vapour Densities and Vapour Pressure along
the Entire Coexistence Curve, Journal of Chemical Thermodynamics, 28, 1441-1460 (1996)
Patel, N.C., Teja, A. S., A New Cubic Equation of State for Fluids and Fluid Mixture, Chemical
Engineering Science, 37(3), 463-473(1982)
Peneloux, A., Rauzy, E., Freze, R., A Consistent Correction for Redlich-Kwong-Soave Volumes,
Fluid Phase Equilibria, 8, 7-27(1982)
Peng, D. B., Robinson, D.B., A New Two Constant Equation of State, Industrial and Engineering
Chemistry Fundamentals, 15(1), 59-64(1976)
th
Perry, R.H., Green, D. W., Perrys Chemical Engineers Handbook, 8 Edition, The McGraw Hill
Companies, Inc., New York, USA (2008)
Phillips, E. M., Thodos, G., The PVT-Behavior of Ethane in the Gaseous and Liquid States,
Society of Petroleum Engineers Journal, SPE 1632-G,83-86 (1962)
Queimada, A. J., Marrucho, I. M., Coutinho, J. A. P.,Stenby, E. H., Viscosity and Liquid Density
of Asymmetric n-Alkane Mixture: Measurement and Modeling, International Journal of
Thermophysics, 26(1), 47-61(2005)
Sage, B. H., Lacey, W. N., Thermodynamic Properties of n-Pentane, Industrial and Engineering
Chemistry, 34(6), 730-737 (1942)
Sant Ana, H. B., Ungerer, P., de Hemptinne, J. C., Evaluation of an Improved Volume
Translation for the Prediction of Hydrocarbon Volumetric Properties, Fluid Phase Equilibria, 154,
193-204(1999)
Schilling, G., Kleinrahm, R., Wagner, W., Measurement and Correlation of the (p, , T) relation of
liquid n-Heptane, n-Nonane, 2,4-Dichlorotoluene and Bromobenzene in the Temperature Range
from (233.15 to 473.15) K at Pressures upto 30 MPa for Use as Density Reference Liquids,
Journal of Chemical Thermodynamics, 40, 1095-1105(2008)
Soave, G., Equilibrium Constants from a Modified Redlich-Kwong Equation of State, Chemical
Engineering Science, 27(6), 1197-1203 (1972)
Sheng, W., Lu, B. C. Y., A Modified Volume Translated Peng-Robinson Equation with
Temperature Dependent Parameters, Fluid Phase Equilibria, 56, 71-80(1990)
Straty, G. C., Ball, M. J., Bruno, T. J., PVT Measurements on Benzene at Temperatures to
723K, Journal of Chemical and Engineering Data, 32(2), 163-166 (1987)
Tsi, J., Chen, Y., Application of a volume-translated Peng-Robinson Equation of State on Vapor-
Liquid Equilibrium Calculation, Fluid Phase Equilibria,145, 193-215(1998)