A Non-Cubical Equation of State for Associating Compounds

M. Nori

Abstract

A non-cubical equation of state is proposed in order to represent the volumetric properties of associating
compounds (e.g. water, alcohols, acids ). Predictions are compared with the Peng Robinson Equation of State
and Statistical Associating Fluid Theory (SAFT) in terms of average absolute percentage deviations for liquid
density and vapor pressure. Analytical expressions for the fugacity coefficients of binary mixtures ( 1 associating
compound - 2 inert ) have been derived according to the mixing rules proposed by Brandani et al. (1997a).

Key words:

Equation of state, association, mixing rules

Introduction

The word association refers to the formation of molecular clusters due to interaction forces of “chemical” nature
among molecules. These chemical forces are short radius and strongly orientation dependent. They differ from
strict “physical” forces ( e.g. repulsion, dispersion and polar ) and the main difference between “chemical” and
“physical” forces is in the saturation criterion. The saturation is related to the high specificity of the chemical
forces, in fact once all the active sites on a molecule are occupied, it is not possible for other molecules to form a
bond with to that one, somehow analogously to intramolecular atomic interactions. Nonetheless the chemical
forces differ also from the covalent bond and the main difference is in the relative weakness of the chemical
forces with respect to the covalent bond. The energy for the chemical intermolecular bond is in typically in the
range 8-40 kJ/mol while for the covalent bond it is in the range 200-400 kJ/mol.
The most common of these forces is the hydrogen bond, however the donor-acceptor bond is also classified as
this type of forces. Currently the theory of the chemical bond is not developed enough, with few exceptions, to
establish quantitative relations between specific intermolecular forces and thermodynamics properties.
Associating compounds show a singular thermodynamic behavior. In the pure compounds, strong attractive
interactions among the molecules determine the formation of molecular clusters that have an important impact
on the thermodynamic properties. For instance, water, that have four associating sites to form hydrogen bond,
has a boiling point four times higher than neon, that has approximately the same volume and molecular weight.
Even more clarifying of the role of the chemical forces on the thermodynamic properties of the pure compounds
it is the comparison( Prausnitz et al, 1998) between the two isomers ethanol (Normal Boiling Point 78 °C) and
dimethyl ether (Normal Boiling Point -25 °C).
In the mixtures, chemical interactions could be established among molecules of the same type ( self-association )
or among different molecules ( solvation ). These interactions have a strong influence on the mixtures
properties. For instance, self-associating components exhibit liquid-liquid immiscibility with no associating
components.
Associating and polar species present a special problem with equations of state because in their equilibria
intervene both week reactions and phase’s equilibria. Until only some time ago, the only method to deal with
these mixtures was in fact based on activity coefficients models ( Prigogine et al., 1954 ) and equations of state
have been developed only lately by using two methods. The first method consists in refining the functional form
and/or the parameters of the equations of state developed for the non-associating fluids by the use of mixing
rules with more parameters. This method was used successfully for the correlation of VLE and LLE of binary
and multicomponent mixtures. However these models are only correlative, and there is no way to estimate a
priori the value of the requested binary parameters. Furthermore thermodynamic inconsistencies have been
highlighted. The second method is the development of an equation of state that includes chemical reaction and
association explicitly such that the resulting model is applicable to a wide range of temperatures and pressures
with only few adjustable parameters. Three types of theories have been developed in order to describe
associating systems with this method. The first theory is based on the assumption that associating molecules
react to form new species and consequently it is indicated as Chemical Theory ( Heidemann and Prausnitz, 1976
). The second theory is based on the lattice theory that is used to describe various types of specific interactions
and it is known as Quasi-Chemical Theory ( e.g. Sanchez and Lacombe, 1976 ). The third theory is based on the
resolution of integral equations by using a potential function that represents the hydrogen bond ( Perturbative
Theory, Huang and Radosz 1990 ). It was demonstrated that all these three approaches produce the similar
results ( Elliot and Suresh, 1992; Donohue and Economou, 1991 ).
The chemical theory was proposed initially by Dolezaleck in 1908. The basic idea is that the associating
molecules form in solution various chemical species that are in equilibrium. Those equilibria are determined by
the reaction constants, that are the models parameters. In his original formulation the chemical theory postulates
the ideal behavior of the formed chemical species and in the past it was mainly applied to model the
dimensionless excess Gibbs energy. The introduction of the chemical deviations determines the necessity to
solve simoultanesly the reactions and phase equilibria. The main problems connected with this type of theory
and with the development of a thermodynamic model are:
1) Arbitrary in deciding which chemical species are present in solution
2) Inadequacy to assign equilibrium constants for the postulated equilibria in absence of experimental data
for the considered solution
3) Huge difficulties to extend to the mixtures
Heidemann and Prausnitz ( 1976 ) have shown that it is possible to solve analytically the chemical equilibrium
within an equation of state so the phases equilibrium conditions could be solved straightly. Their approach has
been applied by other investigators, thought difficulties arise for the extension to mixtures and simplifying
assumptions must be made regarding the association’s model ( e.g. linear association model ) that limit the
applicability of model.
Wertheim ( 1984, 1986a and 1986b ) derived a Thermodynamic Perturbative Theory ( TPT ) for the hydrogen
bond using the hard-core repulsive potential as reference system, perturbing the hard-core with off-center
attractive sites. The key result of Wertheim theory is a relation between Helmholtz residual energy due to
association and the monomer density. This density of the monomer is related to a function that characterizes the
association force (𝐻 𝐴𝑖𝐵𝑗 ). Chapman et al. (1988) found a close match between molecular simulations and
Perturbative Theory and highlighted that the main effect due to the association energy is to enlarge the vapor
liquid coexistence region and to increase the critical temperature. The association theory of Wertheim, arrested
at the first order by Chapman ( 1988, 1990 ) has been applied in the Statistical Associating Fluid Theory ( SAFT
) equation by Huang and Radosz (1990), in the simplified SAFT by Fu and Sandler ( 1995 ) and in the Cubic
plus Association by Kontogeorgis et al ( 1996 ).
Theory/calculation

The EOS is expressed in term of compressibility factor. The compressibility factor is the sum of the ideal,
repulsive, attractive term, and associative term:

𝑍 = 1 + 𝑍 𝑟𝑒𝑝 + 𝑍 𝑑𝑖𝑠𝑝 + 𝑍 𝑎𝑠𝑠 (1)

The reference contribution (1+Zrep) of the EOS represents the sum of ideal gas state and repulsion forces of
molecules according the hard spheres model.

4𝜂−2𝜂2
1 + 𝑍 𝑟𝑒𝑝 = 1 + (1−𝜂)3
(2)

𝜌𝑏
Where η is the reduced density ( 𝜂 = 4
).
For the attraction forces between non polar molecules ( dispersion ) it is proposed an expression similar to the
one of Dohrn and Prausnitz ( 1990 )

4𝜀
𝑍 𝑑𝑖𝑠𝑝 = − 𝑅𝑇 𝜂(1 + 𝑘1 𝜂 + 𝑘2 𝜂2 ) (3)

Where the constants k1 ( -1.40387 ) and k2 ( 4.53723) were obtained fitting density of the liquid and vapor
pressure for six nonpolar substances ( Argon, Xenon, Methane, Ethane, Propane and Butane ).The fitting has
been performed considering the percentage deviations existing between the experimental and calculated liquid
density and the vapor pressure, weighted respectively 5 and 1.
The parameters b ( excluded volume ) and ε ( energy parameter ) are dependent on the reduced temperature (Tr )
as per the following correlations:

1 𝛽 3
1− 𝑒𝑥𝑝(− )
3 𝑇𝑟
𝑏 = 𝑏𝑐 ( 1 ) (4)
1− 𝑒𝑥𝑝(−𝛽)
3

𝛼
1+
𝑇𝑟
𝜀 = 𝜀𝑐 ( 1+𝛼 ) (5)

Where 𝛼 = 𝛼0 + 𝛼1 𝑇𝑟 + 𝛼2 𝑇𝑟2

The chemical association contributions to the equation of state is derived by the Thermodynamic Perturbation
Theory of Wertheim ( 1986a, 1986b ) approximated to the first order ( Chapman et al. (1988, 1990 ) ).
The resulting expressions for the “Two Equal Associating Sites” model and “The Single Associating Site”
model ( only dimerization ) are given by:

2𝜂+2𝜂2 −𝜂3 2𝜂+2𝜂2 −𝜂3

𝑍 𝑎𝑠𝑠 = −0.5𝐻 (1−𝜂)4
(𝑋 𝐴 )2 ( Two sites ) and 𝑍 𝑎𝑠𝑠 = −0.25𝐻 (1−𝜂)4
(𝑋 𝐴 )2 ( Single Site ) (6)

Where XA represent the fraction of molecules not bounded to site A:

2
𝑋𝐴 = (7)
1+√1+𝑍𝑟𝑒𝑝 𝐻

And H is the associating factor:

 𝜀
𝐻 = 𝑉𝐴𝐴 [𝑒𝑥𝑝 ( 𝐴𝐴 ) − 1] (8)
𝑇 𝑟

Where VAA and εAA are the associating volume and associating energy parameters respectively.
Overall the EOS has six adjustable parameters ( ao , a1 , a2 , β, εAA and VAA ), since εc and bc are obtained from the
zero curvature at the critical point. εc and bc : represent respectively the dispersion energy parameter and the
excluded volume parameter at the critical temperature.
ao , a1 , a2 : characterize the dependence on the temperature of the dispersion energy parameter.
β: characterize the dependence on the temperature of the excluded volume parameter.
The adjustable parameters ( Table 2 ) were determined by fitting vapor pressure and density of the liquid by
using a SIMPLEX algorithm. The vapor pressure and the density of the liquid are calculated solving iteratively
the system resulting from the equilibrium condition (Eq.9, equality of the chemical potential ) and the equation
of state (Eq.10 ):

𝜌𝐿 𝜌𝑉
𝑝 = (𝐴𝐿 − 𝐴𝑉 ) 𝜌𝐿 −𝜌𝑉 (9)

4𝑅𝑇 4𝜂−2𝜂2 4𝜀
𝑝− 𝑏
𝜂 (1 + (1−𝜂)3
− 𝑅𝑇 𝜂(1 + 𝑘1 𝜂 + 𝑘2 𝜂 2 ) + 𝑍 𝑎𝑠𝑠 ) (10)

The guess values are the vapor pressure obtained by Wagner Equation ( Wagner, 1973 ) and the reduced
densities ηv =0,01 and ηL=0.7. In the specified reduced densities range the Newton method is convergent, since
it is a monotonic function without horizontal tangent.

Compound ao a1 a2 β εAA/Tc VAA

Water 0.202813 -0.6893796 0.5161295 0.3048233 4.1544668 0.3782539
Ammonia 0.2859741 -0.60655 0.19107 0.0528436 5.527991 0.0379478
Hydrogen- 0.1334051 -0.999852 0.512685 1.9867647 4.5840738 0.1371466
sulfide
Methanol 0.1026779 -0.4105562 0.406340 0.64780 5.1998178 0.1456963
Ethanol 0.406655 -0.4369418 0.7942251 0.6295527 3.9684356 0.2835614
Propanol 0.561491 0.0987770 0.4067378 0.6253640 2.8707409 0.6511947
Butanol 0.4747883 -0.219685 0.2095012 0.017945 3.0783332 0.2360588
Acetic Acid -0.23421 0.13615 0.19370 1.60081 4.9837920 0.2131785
Propionic Acid 0.1813928 -0.4305559 0.4354635 1.3526437 4.6033954 0.1477996
Butyric Acid -0.015971 -0.1868766 0.6801355 2.2865651 4.3905361 0.0597331
Phenol 0.0899689 -0.0756728 -0.0945424 0.3547371 4.0600769 0.1384828

Table 1 Eos parameters - Two associating sites

The extension of the EOS to mixtures could be obtained by mixing rules of the Huron and Vidal ( 1979 ) type.
The mixing rules are established relating equations of state and excess Gibbs energy models at a reference state.
It was highlighted ( Brandani and Brandani, 1996 ) that the infinite pressure reference state ( Huron and Vidal
(1979), Wong and Sandler, 1992 ) determined thermodynamic inconsistencies . In order to overcome these
limitations and based on the consideration that at a given reduced density, the free volume of a mixture is equal
to the free volume of its component in proportion to their own volume, Brandani et al (1997 a ) proposed a
reduced density reference state. The mixtures parameters ( εm and bm ) are evaluated imposing the following
conditions:
 1) Based on the consideration that at same reduced density, the free volume of a mixtures is the same of
their component in proportion to their own volume The attractive part of the Excess Free Helmholtz
Energy ( obtained by the EOS ) is equal to the Excess Free Gibbs Energy ( obtained by a Model for the
activity coefficients (e.g. NRTL ) ) at a reference state. The state of reference is at the reduced density of
10
𝜂= 0.74048, where 0.74048 is the reduced density in the closed packing limit, 12 the coordination
12
number, and 10 the coordination number applied in the GE models.

𝐴𝐸𝑎𝑡𝑡_𝜂𝑟𝑒𝑓 = 𝐺 𝐸 (11)

2) The quadratic dependence on the composition for the second virial coefficient of the mixtures as
imposed by the mechanical statistics.

𝐵𝑚𝑖𝑥 = ∑𝑖=1 ∑𝑗=1 𝑦𝑖 𝑦𝑗 𝐵𝑖𝑗 (12)

Furthermore the associating contribution for the mixtures ( Chapman et al. , 1988 ) is evaluated according the
following expression:

𝑋 𝑖 1 𝐴
𝐴̃ = ∑𝑖 𝑤𝑖 [∑𝐴𝑖 (𝑙𝑛𝑋𝐴𝑖 − 2 ) + 2 𝑀𝑖 ] (13)

Where 𝐴̃ is the difference between the Helmholtz free energy between the associating fluid and the reference
fluid.

𝑍 𝑟𝑒𝑝 −1
𝑋 𝐴 = (1 + ∑𝑗 ∑𝐵𝜖Γ(𝑗) 𝑤𝑗 𝑋𝐵𝑗 𝐻 𝐴𝑖𝐵𝑗 ) (14)
8

𝜀𝐴𝑖𝐵𝑗
𝐻 𝐴𝑖𝐵𝑗 = 𝑉 𝐴𝑖𝐵𝑗 [𝑒𝑥𝑝 ( ) − 1] (15)
𝑇𝑟

Based on the above conditions (Eqs. 14, Eqs. 15 ) the fugacity’s coefficients expression
for a binary mixture ( 1 associating compound - 2 inert) from the general thermodynamic relation:

𝜕(𝑛𝑇 𝐴̂)
ln(𝜙𝑖 ) = [( 𝜕𝑛𝑖
)] − 𝑙𝑛𝑍 (16)
𝑇,𝑉,𝑛 𝑗≠𝑖
𝑛 𝜕𝑏 4𝑛𝑇 𝜕𝜀𝑚 1 1
ln(𝜙1 ) = 𝐴̃ + (𝑍 − 1) + (𝑍 − 1) 𝑏 𝑇 ( 𝜕𝑛𝑚) − ( )
𝑅𝑇 𝜕𝑛1 𝑇,𝜂,𝑛
𝜂 (1 + 2 𝑘1 𝜂 + 3 𝑘2 𝜂2 ) +
𝑚 1 𝑇,𝑉,𝑛2 2
𝑤 2 𝜕𝑋 𝐴1
𝑛 𝑇 [𝑛 2 (2𝑙𝑛(𝑋𝐴1 ) − 𝑋𝐴1 + 1) + 𝑤1 (𝑋 𝐴1 − 1) ( 𝜕𝑛 ) ] − 𝑙𝑛𝑍
𝑇 1 𝑇,𝜂,𝑛
2
(17)

𝑛 𝜕𝑏 4𝑛𝑇 𝜕𝜀𝑚 1 1
ln(𝜙2 ) = 𝐴̃ + (𝑍 − 1) + (𝑍 − 1) 𝑏 𝑇 ( 𝜕𝑛𝑚) − ( )
𝑅𝑇 𝜕𝑛2 𝑇,𝜂,𝑛
𝜂 (1 + 2 𝑘1 𝜂 + 3 𝑘2 𝜂 2 ) +
𝑚 2 𝑇,𝑉,𝑛1 1
𝑤 2 𝜕𝑋 𝐴1
𝑛 𝑇 [− 𝑛 1 (2𝑙𝑛(𝑋𝐴1 ) − 𝑋𝐴1 + 1) + 𝑤1 (𝑋 𝐴1 − 1) ( 𝜕𝑛 ) ] − 𝑙𝑛𝑍
𝑇 2 𝑇,𝜂,𝑛
1
(18)

Where the dimensionless residual Helmholtz free energy is given by:

 4𝜂−3𝜂 4𝜀2 1 1
𝐴̃ = (1−𝜂)2 − 𝑅𝑇𝑚 𝜂 (1 + 2 𝑘1 𝜂 + 3 𝑘2 𝜂2 ) + 𝑤1 (2𝑙𝑛𝑋𝐴1 − 𝑋 𝐴1 + 1) (19)

𝐴1 2
𝑋 = (20)
𝑟𝑒𝑝
1+√1+𝑤1 𝑍 𝐻 𝐴1 𝐴1

𝐴1 𝐴1 𝜀𝐴1𝐴1
𝐻 𝐴1 𝐴1 = 𝑉 [𝑒𝑥𝑝 ( 𝑇𝑟
) − 1] (21)

The proposed mixing rules ( in Table 3) have a clear physical meaning corresponding to a reference state where
the fluid properties are measurable and they verify the quadratic dependence on the second virial coefficient :

Parameter Expression
𝜀𝑚 𝐴
𝑤1 + 𝑤2 𝐺̃ 𝐸 𝑤1 𝑋𝑟𝑒𝑓 𝐴0 𝐴
𝑅𝑇 − + (2𝑙𝑛 𝐴 + 𝑋𝑟𝑒𝑓 − 𝑋𝑟𝑒𝑓 )
𝑅𝑇 𝑅𝑇 4𝛿 𝑋 0
𝑟𝑒𝑓

𝛿 1 1 2
𝜂 𝑟𝑒𝑓 (1 + 𝑘1 𝜂 𝑟𝑒𝑓 + 𝑘2 (𝜂 𝑟𝑒𝑓 ) )
2 3
𝐴 2
𝑋𝑟𝑒𝑓
𝑟𝑒𝑝
1+√1+𝑤1 𝑍𝑟𝑒𝑓 𝐻 𝐴1 𝐴1

0𝐴 2
𝑋𝑟𝑒𝑓
𝑟𝑒𝑝
1+√1+𝑍𝑟𝑒𝑓 𝐻 𝐴1 𝐴1

𝑏𝑚 𝑤12 𝐵11 + 2𝑤1 𝑤2 𝐵12 + 𝑤22 𝐵22

𝜀 𝑤 2 𝐻 𝐴1 𝐴1
1− 𝑚 − 1
𝑅𝑇 4

𝐵11 𝜀1 𝐻 𝐴1 𝐴1
𝑏1 (1 − − )
𝑅𝑇 4

𝐵22 𝜀2
𝑏2 (1 − )
𝑅𝑇

𝐵12 𝐵11 + 𝐵22

(1 − 𝑘12 )
2

Table 2 Mixtures Parameters

Results and Discussion

In the following table are reported the results obtained with the EOS for water, Ammonia , some common
alcohols and acids.

Compound Number of Number of AAPD Vapor AAPD Bibliographic

data Vapor Data Liquid Pressure Liquid References
Pressure Density Density
Water 29 29 0.62 0.34 NIST
Ammonia 15 15 0.86 0.82 NIST
Hydrogen- 8 8 0.27 0.51 API
sulfide
Methanol 15 11 0.17 0.94 TRC
Ethanol 15 11 0.09 1.35 TRC
Propanol 15 9 0.18 0.77 TRC
Butanol 15 4 0.10 0.34 TRC
Acetic Acid 18 23 0.32 0.82 TRC
Propionic Acid 7 22 0.15 0.12 TRC
Butyric Acid 7 22 0.2 0.16 TRC
Phenol 27 16 0.94 0.88 TRC

Table 3 Pure Compounds Results

The correlative properties of the equation are better than cubic equation ( Peng Robinson EOS ) and the order
of magnitude of SAFT ( Table 5 ).

Compound AAPD AAPD AAPD AAPD

Vapor Liquid Vapor Liquid
Pressure Density Pressure Density
Peng- Peng- SAFT SAFT
Robinson Robinson
Water 5.42 15.96 1.3 3.2
Ammonia 0.77 12.93 1.6 3.2
Hydrogen- 1.99 3.51 0.69 1.4
sulfide
Methanol 3.57 16.59 0.83 0.88
Ethanol 1.2 8.46 0.86 0.83
Propanol 2.57 3.27 0.16 0.12
Butanol 4.0 2.29 0.23 1.0
Acetic Acid 5.3 22.7 1.6 0.69
Propionic Acid 6.14 6.44 0.25 0.1
Butyric Acid 5.4 11.65 0.3 0.84
Phenol 3.31 12.13 0.24 0.02

Table 4 Pure Compounds Results – Comparison with Peng Robinson and SAFT

Acids are known to dimerize. This could be represent by the 1-site model. From a computational pint of view,
the 1-site model is equivalent to the two-sites model for the acids ( Tables 3 and 5 ).

Compound AAPD AAPD

Vapor Liquid
 Pressure Density
Peng- Peng-
Robinson Robinson
Acetic Acid 0.19 0.47
Propionic Acid 0.16 0.61
Butyric Acid 0.21 0.14

Table 5 1-site model ( acid dimerization )

Conclusions

The proposed EOS includes the repulsion contribution of Caharnan-Starling and it could be applied to represent
the volumetric properties of associating pure fluids ( water, alcohols, acids ) with good accuracy in a wide range
of experimental conditions . Future work could be aimed to verify the predictions for high pressure binary
mixtures (1 associating, 2 inert ) by means of the proposed mixing rules.

Acknowledgements

This work was extracted from my thesis laurea degree developed under the guidance of the late Professor
Vincenzo Brandani at Università degli Studi dell’Aquila.

Nomenclature
a – parameter of equation of state
A – associating site over molecule A
𝐴̃ – reduced dimensionless Helmholtz energy
B – associating site over molecule B
b – size parameter, m3 mol–1
bc – size parameter at the critical point, m3 mol–1
~
G – reduced Gibbs energy
H – associating factor
k – constants dispersive force
k12 – binary parameter for the virial cross-coefficient
AAPD – absolute average percent deviation, %
M – number of sites
N – number of moles
P – pressure, Pa
Pc – critical pressure, Pa
R – ideal gas constant, J mol–1 K–1
T – temperature, K
Tc – critical temperature, K
V – volume
VAB – association’s volume
w – mole fraction
Z – compressibility factor

Greekletters
α – parameter in equation
β – parameter in equation
γ – activity’s coefficient
ε – dispersion energy parameter
εAB – association energy parameter
η – reduced density
μ – chemical potential
ρ – molar density
ϕ – intermolecular potential
ω – acentric factor

Superscript
attr – attractive contribution
E – excess function
rep – repulsive contribution
ass – associative contribution
(i) – i phase
0 – reference state

Subscript
calc. – calculated quantity
exp. – experimental quantity
k – index
i, j – components
m – mixture
T – total
ref – reference

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