Fluid Phase Equilibria 356 (2013) 338–370

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Fluid Phase Equilibria

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Predictive correlations for ideal gas heat capacities of pure

hydrocarbons and petroleum fractions
Vaclav Lastovka 1 , John M. Shaw ∗
Department of Chemical Engineering, University of Alberta, Edmonton, Alberta T6G 2G6, Canada

a r t i c l e i n f o a b s t r a c t

Article history: The development of continuous predictive correlations for the temperature dependence of the ideal gas
Received 7 March 2013 heat capacity for hydrocarbons and substituted hydrocarbons valid over a wide range of elemental com-
Received in revised form 10 July 2013 positions (CHNOS), molecular structures, and temperatures (298.15–1500 K) is reported. The correlations
Accepted 11 July 2013
are functions of temperature, elemental composition, and 10 (naphthenic hydrocarbons) or 12 (aromatic
Available online 23 July 2013
and aliphatic hydrocarbons) universal coefficients. There are no compound specific coefficients. The vari-
ables are absolute temperature and a similarity variable, which possesses a value proportional to the
Keywords:
number of atoms in a molecule, irrespective of their nature, divided by molecular mass. Different data sets
Ideal gas
Heat capacity
obtained from the NIST TRC Ideal Gas Database 88 were used to evaluate parameters, and to test the pre-
g0
Prediction dictive nature of the correlations. Detailed comparisons between predicted ideal gas heat capacities (cp )
Correlation obtained in this work and values obtained using four Lee–Kesler correlations, and the Harrison–Seaton
Hydrocarbon correlation are presented. The present correlations are shown to be preferred over these other options on
the basis of accuracy and range of application for general-purpose calculations, unless the fluid assign-
g0
ment (naphthenic vs. aromatic/aliphatic) is unknown and cp values are only required at set temperatures
available for the Harrison–Seaton correlation. In this latter case, the Harrison–Seaton correlation is pre-
ferred. For large molecules, the universal correlations presented in this work approach the accuracy of
the benchmark Benson method. The universal correlations are well suited for the determination of ideal
gas heat capacities of large and complex molecules or mixtures, where more precise structure–property
group contribution correlations are difficult to apply or are inapplicable because groups present are not
defined in the correlations or are unknown.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction [1,3–6] over a wide range of temperatures. At low pressures the

Knowledge of thermal properties of petroleum fluids plays a
central role in the development, design and efficient operation
of heat transfer equipment, and on the energy requirements for
industrial processes more broadly. Ideal gas heat capacity is a ther-
modynamic property of particular importance as it is used as a
reference state in many thermodynamic calculations. For exam-
ple, Růžička and Majer [1–6] used thermodynamics relationships
between ideal gas heat capacity, related thermal properties and
vapor pressure to develop a methodology for multi-property cor-
relation. This method enabled thermodynamically consistent and
accurate extrapolations of vapor pressure and sublimation pressure
data beyond the experimental data range. Using this method, vapor
pressure and sublimation pressure data were recommended for
several groups of compounds in both liquid and crystalline states
∗ Corresponding author. Tel.: +1 780 492 8236.
E-mail address: jmshaw@ualberta.ca (J.M. Shaw).
1
Present address: Shell Canada, Calgary, Alberta, Canada.
thermal properties of ideal gases are useful approximations of the
properties of real gases. At higher pressures, departure functions
linked to equations of state are used to relate ideal gas properties,
including heat capacity, to properties of real gases and liquids.
Publications concerning direct determination of ideal gas heat
capacity for pure compounds are scarce. Experimental vapor heat
capacity data for petroleum fluids and their fractions is more
scarce mainly due to the unavailability of representative samples
and experimental difficulties related to generating thermally sta-
ble vapor of heavy petroleum cuts at constant compositions [7].
In-direct experimental determination of ideal gas heat capacities
over a wide temperature range has been provided by Chirico et
al. [8]. This thermodynamic approach requires accurate EOS rep-
resentation of gas and liquid densities along the saturation curve,
temperature dependence of vapor pressure data, constant pressure
heat capacities of solid state and saturated liquid, and enthalpy
of fusion. In this way, Chirico et al. [8] determined ideal gas
heat capacity values for naphthalene that deviate by less than 5%
from recommended data. This thermodynamic approach is labo-
rious and can only be applied to compounds where properties

0378-3812/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fluid.2013.07.023
 V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370 339

Nomenclature
a0,1. . .7 , a, b1 , c1 , b2 , c2 , A1,2. . .4 , B11 , B12 , B21 , B22 , C11 , C12 , C21 ,
cp Specific heat capacity at constant pressure, J K−1 g−1 C22 , A, c, d, , C1 , C2 , D1 , D2 Adjustable coefficients
Cp Molar heat capacity at constant pressure, of fitting equations
J K−1 mol−1 F Average standard deviation of the fit
cV or cv Specific heat capacity at constant volume, J K−1 g−1 ␴rel
F
Average standard relative deviation of the fit
CV or Cv Molar heat capacity at constant volume, J K−1 mol−1 ı Average relative deviation
g0
cp Specific heat capacity of ideal gas at constant pres- ε Average absolute deviation
sure, J K−1 g−1  Average standard deviation
g0
Cp Molar heat capacity of ideal gas at constant pressure,  rel Average standard relative deviation
J K−1 mol−1 ␴rel
i
Compound specific standard relative deviation
CVtranslation Contribution to the molar heat capacity at constant CF1 and CF2 Corrective factors in the Lee–Kesler correlations
volume from the translational motion of a molecule of ideal gas heat capacities
as a whole, J K−1 mol−1 SARA Solubility class based fractionation (saturates, aro-
CVrotation Contribution to the molar heat capacity at constant matics, resins, asphaltenes)
volume from the rotational motion of a molecule as DFT Density functional theory
a whole, J K−1 mol−1 B3LYP Hybrid density functional consisting of Becke’s
CVvibration Contribution to the molar heat capacity at con- three-parameter exchange functional and Lee, Yang,
stant volume from the intramolecular vibrations in and Parr’s correlation functional
a molecule, J K−1 mol−1 6-311G Polarized basis set for quantum–mechanical calcu-
P Pressure, Pa lations
V Volume, m3 QM Quantum–mechanical method
T Temperature, K RROH Rigid Rotor-Harmonic Oscillator approach
Tb Normal boiling point, K DSC Differential scanning calorimetry
Tc Critical temperature, K TG Thermogravimetry
Pc Critical pressure, Pa TMDSC Temperature modulated differential scanning
Vc Critical volume, m3 calorimetry
 Kinematic viscosity, m2 s−1 SAXS Small angle X-ray scattering
n Refractive index and number of elements in a com- EOS Equation of state
pound TRC Thermodynamic Research Center
SG Specific gravity, relative value ASTM American Society for Testing and Materials
M Molar mass, g mol−1 SRM Standard reference material
 Saturated densities of a compound, g cm−3 VMG Virtual Materials Group Inc.
p sat Saturated vapor pressure of a compound, Pa
CH Carbon-to-hydrogen ratio
ω Acentric factor are known with a great accuracy. Most ideal gas heat capacity
Kw Watson characterization factor data for pure compounds is currently determined from first prin-
D Debye temperature, K ciples using statistical thermodynamics, based on experimental or
D Debye frequency, Hz calculated fundamental vibrations. Vibrations can be determined
i Einstein temperature calculated from ith vibration using quantum–mechanical methods. Often, a simple Rigid Rotor-
mode as  i = hi /k, K Harmonic Oscillator model is used as a first-order approximation.
i Frequency of ith intramolecular vibration, Hz; Data of higher accuracy can be obtained through introduction of
R Universal gas constant, R = 8.314472 J K−1 mol−1 scaling factors for computed vibration frequencies and corrections
h Planck constant, h = 6.62606957 × 10−34 J s for rotational–vibrational coupling, internal rotation and centrifu-
kB or k Boltzmann constant, kB = 1.3806488 × 10−23 J K−1 gal distortion. For small molecules, the accuracy of computed
NA Avogadro constant, NA = 6.02214129 × 1023 mol−1 ideal gas heat capacities computed in this manner, exceeds the
N Number of atoms in a molecule g0
accuracy of experimentally determined values and computed cp
˚ Number of vibration modes per mass of a molecule, values are reported by TRC [9]. For large hydrocarbon molecules
g−1 a detailed treatment of internal degrees of freedom is compu-
f Total number of vibration modes in a molecule tationally intensive. For industrially relevant fluids that tend to
m Mass of a molecule, g and number of compounds in be ill-defined and multicomponent hydrocarbon mixtures, with
a dataset significant uncertainties in even average molecular structure, the
Mi Molar mass of chemical element i, g mol−1 quantum–mechanical approach is both uncertain and impractical,
xi Mole fraction of element i in a compound and their ideal gas heat capacities are particularly challenging to
wi Mass fraction of element i in a compound estimate.
˛ Similarity variable, mol g−1 Ideal gas heat capacity data and related thermal data can also be
p Number of fitted parameters predicted from structure–property correlation schemes. The sim-
i Stoichiometric coefficient for element i in a com- plest methods use contributions based on the atoms present in
pound molecules and are referred to as “Zero-Order Methods” e.g.: the
C Stoichiometric coefficient for element C in a com- g0
Harrison–Seaton method [10] which provides cp estimates at dis-
pound crete temperatures (298.15, 400, 500, 600, 800, 1000 and 1500 K)
H stoichiometric coefficient for element H in a com- using 15 temperature dependent coefficients. The next level of
pound methods assigns contributions to various chemical bonds. A rela-
S Objective function to be minimized tively easy to use method which assigns heat capacity contributions
in this way was developed by Benson [11]. More successful methods
340 V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370
involve assigning contributions to common molecular groupings of
elements e.g. CH3 , NH2 , COOH; which are then simply added
together. These are referred to as first-order methods. The zero and
first-order methods cannot describe unique structural fragments
such as saturated and aromatic rings and therefore corrections
must be incorporated. These group contributions do not capture
proximity effects or isomer differences. The Joback method [12,13]
employs first-order group contributions and the method also dis-
tinguishes non-ring, non-aromatic ring and aromatic ring groups as
well as different atoms and bonding. Benson and Buss [14] set up a
benchmark among estimation techniques and proposed an accu-
rate estimation scheme that includes contributions from atoms
or molecular groups, while an allowance is also made for inter-
actions with next nearest neighbors to the atom or group. These
methods are referred to as second-order methods. Values for the
Benson additivity scheme are only tabulated for discreet tempera-
tures (298.15, 400, 500, 600, 800, 1000 and 1500 K). Bureš et al.
[15] correlated the Benson values using three different types of
equations. However, the method has not been accepted because
prediction of some group contributions did not prove to be reliable
and group contributions for fused aromatic carbons in polyaromatic
compounds were omitted. Coniglio and Daridon [16] extended the
Bureš method especially to group contributions for polyaromatic
compounds which were omitted in the original work. They claim
that after this modification the method is in a good agreement
with the Benson method. It must be noted that the Benson–Buss
method applied to polynuclear aromatics shows poorer perfor-
mance than experimental data mainly due to the lack of group
contributions for fused aromatic carbons. Dorofeeva et al. [17] per-
formed quantum–mechanical calculations for heavy polynuclear
aromatics. Later, Moiseeva and Dorofeeva identified and developed
missing contribution groups for five [18] and six membered rings
[19] in heavy polycyclic aromatic hydrocarbons and improved the
Benson additivity scheme to cover all thermodynamic properties
over a wide range of temperatures. The Constantinou and Gani
[20] method is another example of a second-order method. In their
approach molecular structure is considered to be a collection of
two types of groups: simple functional groups, that is, the first-
order groups, and second-order groups which are functional groups
containing the first-order groups as building blocks. Domalski and
Hearing [21] proposed a group contribution technique based on the
Benson group additivity method for hydrocarbons in the gas, liq-
uid, and solid phases at 298.15 K. Later, the method was extended
to compounds containing the elements [22] carbon, hydrogen, oxy-
gen, nitrogen, sulfur, and halogens in the gas, liquid, and solid
phases at 298.15 K. These methods are only reliable above 298.15 K.
Coniglio and Daridon [16] developed a group contribution method
for both pure compounds and mixtures valid over a wider range
of temperatures (150–3000 K) based on group definitions of Con-
stantinou and Gani [20]. Unfortunately, contributions for groups
with heteroatoms were not included.
All of the above estimation techniques suffer from a lack of gen-
erality in the sense that certain bond contributions and molecular
grouping contributions are missing from the tables of available
parameters. When a calculation for a particular molecule is made,
occasionally a needed group contribution is missing. In such cases,
zero-order methods become very attractive. However, the accu-
racy of such predictions may be unfavorable although examples
where zero-order methods outperform more rigorous methods
are encountered. Harrison and Seaton [10] attempted to over-
come the limitation of missing group contributions by developing
a zero-order method for estimation of a heat capacity incre-
ment that may either refer to a grouping of elements within
a molecule (such as used by Benson’s method) or to an entire
molecule. This method was adopted in the CHETAH program [23].
The second-order structure–property correlations can be used for
accurate estimates of pure hydrocarbons. This approach was used
g0
for cp values reported by the TRC [9,24]. For heavy constituents
of petroleum fluids and/or their fractions (boiling fractions rep-
resented by pseudo-components), the molecular structures are
uncertain or unknown and none of these approaches can be applied.
The properties of fluids depend on intermolecular forces among
molecules. These forces depend on local charges and inter molecule
distances. For non-polar molecules, charges are induced by Lon-
don forces. The intermolecular forces are related to intermolecular
potentials, which are functions of the distance between molecules.
The main characteristic of a two-parameter potential energy func-
tion is the minimum value of potential energy and the distance
between molecules where the potential energy is zero. The second
characteristic is directly linked to the size of the molecule. These
characteristics gave rise to generalized correlations for many phys-
ical properties of petroleum fluids that have become popular in
the petroleum industry. Riazi [25] gives a broad overview of the-
oretically grounded correlations for critical properties (Tc , Pc , Vc )
as functions of mean boiling point (Tb ) and specific gravity (SG).
Tb represents the energy parameter and SG the size parameter.
Generalized correlations use readily available physical proper-
ties and constants, such as the mean boiling point (Tb ), molar
mass (M), and kinematic viscosity (), to represent the energy
parameter, while specific gravity (SG), refractive index (n), and
carbon-to-hydrogen weight ratio (CH) are used to represent a size
parameter. In general, correlations with two independent param-
eters are valid for light hydrocarbons and petroleum fractions
(M < 300 g mol−1 ). For heavier hydrocarbon fractions molecular
diversity and aromaticity naturally increase and the molecules pos-
sess more heteroatom/functional groups that lead to increased
polarity. Consequently, for these materials a third and a fourth
parameters are required. There have been numerous attempts to
correlate ideal gas heat capacity for petroleum fractions with the
Watson characterization factor [26] (a function of Tb and SG), acen-
tric factor, molecular weight, refractive index, etc. These include the
graphical methods of Watson and Nelson [26], API [27], and analyti-
cal correlations of Lee–Kesler [28], Cavett [29] and Twu–Black [30].
Despite the popularity of some of these methods, the two/three-
parameter approach is rather complicated and the quality of input
parameters directly affects the accuracy of predicted ideal gas heat
capacity values. Consequently, a similarity variable concept with a
track record for success with solids [31–33] and more recently with
liquids [34] is explored in this work.
2. Similarity variable concept for estimating isobaric heat
capacity of ideal gases
From quantum mechanics, it is well established that molecular
energy levels arise from molecular translation, rotation, vibration
and electronic excitation modes. Neglecting electronic excitation
and including internal rotations in the vibrational approximation,
the molar heat capacity of ideal gases is a function of contributions
from three degrees of freedom:
g0
Cp = R + CVtranlation + CVrotation + CVvibration (1)
The contribution from translation is
3
CVtrans = (2)
2R
For a linear molecule, the contribution from external rotations
(rigid rotor) is
CVrot = R (3)
 V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370 341

(a) 1000 (b) 3.0

900
800 2.5

Cp /(J·K ·mol )
-1

cp /(J·K ·g )
700

-1
2.0
600

-1
-1
500 1.5
400

g0
g0
300 1.0
200 0.5
100
0 0.0
0 250 500 750 1000 1250 1500 0 250 500 750 1000 1250 1500
T/K T/K

Fig. 1. TRC [9] recommended molar ideal gas heat capacities for aromatic compounds based on quantum–mechanical calculations: (a) mole basis, (b) mass basis.
blue line, Dicyclopenta[cd,fg]pyrene (C20 H10 , M = 250.3 g mol−1 , 84 vibration modes); green line, coronene (C24 H12 , M = 300.6 g mol−1 , 102 vibration modes);
red line, Phenanthro[1,10,9,8-opqra]perylene (C28 H14 , M = 350.4 g mol−1 , 120 vibration modes).(For interpretation of the references to color in this figure legend,
the reader is referred to the web version of the article.)

For a non-linear molecule, the contribution from external rota- approach provides an unbiased distribution of the relative devia-
tion is tions and a temperature dependence of the ideal gas heat capacities
3 that more closely approximates reference data.
CVrot = (4) Irrespective of the method of calculation, molecules comprising
2R
the same atoms are expected to possess comparable heat capaci-
In the simple Rigid Rotor-Harmonic Oscillator model (RRHO),
ties, irrespective of their arrangement. Further, molecules sharing
all internal vibration modes are treated as simple harmonic oscil-
the same atomic ratios but different molar masses are also expected
lations, with contributions from 3N − 5 internal vibration modes for
to possess comparable mass based heat capacities, particularly at
linear Eq. (5) and (3N) − 6 for non-linear molecules Eq. (6) respec-
higher temperatures where atomistic vibrations dominate. These
tively:
trends are illustrated in Figs. 1 and 2 for aromatic, and and lin-
g0
g0 3  (h /kB T ) exp(−h /kB T )
3N−5 2 ear hydrocarbons respectively. While the cp values scale with
i i
Cp,linear = R + +R+R 2
, (5) molar mass, Fig. 1a, the heat capacities for the same compounds
2R [1 − exp(−h /kB T )]
i=1 i fall within 2% on a mass basis – Fig. 1b. These compounds possess
the same elemental composition (C2n Hn ) and hence the same num-
ber of vibrations per unit mass. For saturated cyclic hydrocarbons
g0 3 3  (h /kB T ) exp(−h /kB T )
3N−6 2
Cp,non−linear = R + + +R i i
, (6) and linear unsaturated hydrocarbons possessing the same elemen-
2R 2R 2
[1 − exp(−h /kB T )] i tal composition (Cn H2n ), there is good agreement on a mass basis
i=1

where T is the temperature in Kelvin, i are the frequencies of vibra-

tions of the ith normal mode, kB is the Boltzmann constant, and h 4.5
is the Planck constant. At low temperatures, the contribution of
each normal vibration mode decreases with temperature and on 4.0
a molar basis, the ideal gas heat capacity approaches ∼3.5R for
liner molecules and ∼4R for non-linear molecules. At high tem-
3.5
cp /(J·K ·g )
-1

peratures, the contribution of the harmonic vibrations approaches

3.0
-1

1 and thus the upper limit for ideal gas heat capacity according
to the RRHO model is 3.5R + (3N − 5)R for linear molecules and 2.5
4R + (3N − 6)R for non-linear molecules. Thus the asymptotic dif-
g0

ferences between linear and non-linear molecules with the same 2.0
number of atoms (N) are −0.5R at low temperatures and +0.5R at
high temperatures and the relative differences ∼12.5% at low tem- 1.5
perature and ∼2% at high temperature for molecules comprising as
few as 10 atoms. At intermediate temperatures, differences are a 1.0
function of the details of molecular vibrations. Every solution of the
Schrödinger equation is approximate, resulting in uncertainties of
0.5
calculated vibrational frequencies. To compensate for this error, the
0 250 500 750 1000 1250 1500
computed frequencies are usually multiplied by empirical scaling T/K
factors. Scaling factors for fundamental vibrational frequencies and
for low-frequency vibrations can be found in the literature [35–38]. Fig. 2. TRC recommended specific ideal gas heat capacity data for aliphatic hydro-
Often, a single scaling factor for a given theory and basis set is corre- carbons. Solid lines – acyclic linear unsaturated hydrocarbons [9]: blue
line, 1-undecene (C11 H22 , M = 154.3 g mol−1 , 93 vibration modes); green
lated by comparison of experimental and calculated vibrations for
line, 1-octadecene (C18 H36 , M = 252.5 g mol−1 , 156 vibration modes);
a limited set of molecules. Variable scaling factors have also been red line, 1-eicosene (C20 H40 , M = 280.5 g mol−1 , 174 vibration modes). Dashed
proposed [35–37] to improve the agreement with a given experi- lines – cyclic saturated hydrocarbons [24]: blue dotted line,
mental thermal data. However, this later approach may break the 1,1-dimethylcyclohexadecane (C18 H36 , M = 252.5 g mol−1 , 156 vibration modes);
thermodynamic consistency of the thermodynamic properties [3]. green dotted line 1,1,4,4-tetramethylcyclohexadecane (C20 H40 ,
M = 280.5 g mol−1 , 174 vibration modes); red dotted line cycloocta-
Recently, Červinka et al. [39] proposed a new wavenumber and
cosane (C28 H56 , M = 392.7 g mol−1 , 246 vibration modes).(For interpretation of the
bond-dependent set of scaling factors that significantly improve references to color in this figure legend, the reader is referred to the web version of
the agreement between the theory and reference data. This new the article.)
342 V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370

g0
among cp values within each group, as shown in Fig. 2, but there are 3.5
differences between the two groups, particularly at high and low
temperature that link directly to their differing molecular struc- 3.0
tures as noted above. The heat capacity values for the saturated

cp /(J·K ·g )
-1
cyclic and unsaturated linear molecules cross, an effect anticipated
2.5
from theory, but the differences remain within 10% from ∼250 to

-1
2.0
∼850 K.
From the above, it is clear that the contributions of internal 1.5

g0
vibration modes to ideal gas heat capacity are weakly dependent
1.0
on the specific nature of the vibrations and these differences dimin-
ish through summation of internal vibration modes and increasing 0.5
mass of a molecule. Thus ideal gas heat capacity is primarily a
function of the number of vibrations per mass of a molecule: 0.0
f NA (3N − 5) 3N − 5 0 250 500 750 1000 1250 1500
˚linear = = = , (7)
m M m
T/K
f NA (3N − 6) 3N − 6
˚non−linear = = = , (8) g0
Fig. 3. Computed temperature dependences of cp values from 0 to 1500 K for
m M m
aromatic compounds with common molecular formula (Cn Hn ; ˛ = 0.1536 mol g−1 ).
where f is the number of vibration modes per molecule, m is the
blue line, benzene (C6 H6 , M = 78.1 g mol−1 , 30 vibration modes);
mass of a molecule, NA is the Avogadro number, N is the number of green line, 1-ethylnaphthalene (C12 H12 , M = 156.2 g mol−1 , 66 vibra-
atoms per molecule and M is the molar mass. For large molecules, tion modes); red line, 2-hexyltetracene (C24 H24 , M = 312.4 g mol−1 ,
the focus of this work, both Eqs. (7) and (8) reduce to: 138 vibration modes), — black line, 1,10-bis(6-ethylpyrenyl)decane (C46 H46 ,
M = 598.9 g mol−1 , 270 vibration modes).(For interpretation of the references to color
f ∼ NA 3N 3N
˚= = = . (9) in this figure legend, the reader is referred to the web version of the article.)
m M m
And convenient evaluation and further work, a similarity vari-
This convergent behavior is readily explained using statistical-
able ˛ is defined on the basis of the elemental composition as:
thermodynamic principles. For small molecules, low wavenumber
vibrations (whole body vibrations and torsional modes) dominate

n

n

n
at low temperatures. Skeletal vibration modes are among the first
i xi wi /Mi
to saturate as temperature is raised. However, with an increasing
N i=1 i=1 i=1 number of atoms (molecular weight) their significance vis-à-vis
˛= = = = , (10)
M  n

n

n
the mid and high wavenumber vibrations (symmetric and anti-
i Mi xi Mi wi symmetric stretching, scissoring, rocking, wagging and twisting)
i=1 i=1 i=1 diminishes. Mid and high wavenumber vibrations dominate at high
where i is the stoichiometric coefficient for element j in a com- temperatures and for larger molecules their contribution to specific
pound consisting of N atoms, n is the number of elements in heat capacity becomes significant even at low temperatures. The
a compound, and Mi is the atomic mass of element i (g mol−1 ). weak dependence of specific heat capacity on the specific nature
Variable xi is the mole fraction of element i in a compound, of the vibration modes within and among hydrocarbon classes and
and wi is the mass fraction of element i. The similarity vari- the secondary contributions from heteroatoms like oxygen, sulfur
able values for aromatic compounds typically range from 0.83 to and nitrogen present at low concentration is exemplified below.
0.16 mol g−1 . For cyclic and acyclic aliphatic compounds values typ- For rigid aromatic compounds (fluoranthene and pyrene)
ically range upward from 0.19 mol g−1 and possess an upper limit with the same elemental composition (C16 H10 , M = 202.3 g mol−1 ,
g0
of 0.2174 mol g−1 . The similarity variable for S, N, and O substituted ˛ = 0.1286 mol g−1 ), the computed cp curves, Fig. 4, are in a
hydrocarbons spans both ranges. good agreement with the recommended TRC data [9], and with
The roots and limitations of the similarity concept are best one another, Fig. 5a. The average relative deviation between the
explored on the basis of quantum–mechanical calculations. In this heat capacities of the two molecules evaluated in temperature
work, ideal gas heat capacities were evaluated using the RRHO range from 0 to 1500 K is 0.99% and the corresponding aver-
model. All intramolecular degrees of freedom were treated as vibra- age absolute deviation is 0.005 J K−1 g−1 , even though the first 10
tional modes. Quantum–mechanical calculations were performed or more vibration modes differ by more than 10%. For flexible
using the Density Functional Theory (DFT) in the Gaussian soft- alkyl substitute phenyl derivates 1,2-bis(4-pentylphenyl)ethane
ware package [40]. The ground state molecular structures were and 1,12-bis(phenyl)dodecane that possess the same elemental
determined by complete geometry optimization using the B3LYP composition: (C24 H34 , M = 322.5 g mol−1 , ˛ = 0.1798 mol g−1 ), the
g0
Hybrid Density Functional (Becke’s three-parameter exchange computed cp curves are also in good agreement with one another,
functional [41] and Lee, Yang, and Parr’s correlation functional Fig. 6. The average relative deviation between these two heat capac-
[42]) and the polarized 6-311G basis set. Frequency spectra cal- ities from 0 to 1500 K is 1.2% and the corresponding absolute
culations were performed for the optimized structures using the average absolute deviation is 0.01 J K−1 g−1 . This close agreement
B3LYP/6-311G basis set. This computational approach is in a good arises even though the relative deviation of the ith wavenumber of
agreement with experimental spectra [43–45]. Although small dif- 1,2-bis(4-pentylphenyl)ethane from the ith wavenumber of 1,12-
ferences between computed and experimentally obtained data bis(phenyl)dodecane is significant for first 58 vibration modes, of
were observed [44,45], no scaling factors for computed vibration 168, as shown in Fig. 7.
frequencies were used in this work. For alkyl substituted aromatics For compounds that include heteroatoms, the vibration spectra
that possess the same number of vibrations per mass of molecule differ both qualitatively and quantitatively from hydrocarbons and
(Cn Hn ; ˛ = 0.1536 mol g−1 ), Fig. 3, it is evident that they exhibit vary with molecular structure details. For example, organic com-
g0
a similar temperature dependence for cp and this consistency pounds that include hydroxyl groups possess infrared absorption
improves with increasing molar mass. Thus the asymptotic behav- wavenumbers in the range of 3640–3160 cm−1 while those with
ior of the similarity variable is convergent at high molar mass. carbonyl groups possess infrared absorption wavenumbers in
 V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370 343

3.0 4.0

2.5 3.5

/(J·K ·g )
-1
3.0
cp /(J·K ·g )
-1

2.0

-1
2.5
-1

1.5 2.0

g0,DFT
1.5
g0

1.0

cp
1.0
0.5
0.5
0.0
g0,TRC

0.0

g0,A
8
)/cp

)/cp
g0,DFT

4 2

g0,B
-cp
-cp

0 0

g0,A
g0,TRC

-4 -2

10 (cp
10 (cp

-8

2
-4
2

0 250 500 750 1000 1250 1500 0 250 500 750 1000 1250 1500
T/K T/K
g0 g0
Fig. 4. DFT RRHO computed temperature dependences of cp for fluoranthene Fig. 6. DFT RRHO computed temperature dependences of cp for:
( magenta line, this work) and pyrene ( green dotted line, magenta line, 1,2-bis(4-pentylphenyl)ethane; and green dotted
g0
this work). TRC recommended [9] temperature dependences of cp for: , fluoran- line, 1,12-bis(phenyl)dodecane. Lower insert: relative deviation of the computed
thene; , pyrene. Relative deviation of computed data from recommended TRC data cp
g0,DFT
values of 1,2-bis(4-pentylphenyl)ethane (A) from 1,12-bis(phenyl)dodecane
for: , Fluoranthene; 䊉, pyrene.(For interpretation of the references to color in this (B).(For interpretation of the references to color in this figure legend, the reader is
figure legend, the reader is referred to the web version of the article.) referred to the web version of the article.)

the range of 1760–1670 cm−1 . Significant differences are also
expected for low wavenumber vibration modes. The heat capac-
ity of compounds with carbonyl groups diverges from the heat
capacity of the compounds with hydroxyl groups because of
these spectral differences. However, if the mass fraction of
oxygen or other heteroatoms in a molecule is low, such differ-
ences are expected to fall within prediction error tolerances. For
g0
example computed cp values for N-methylcarbazole (C13 H11 N;
M = 181.2 g mol , ˛ = 0.1379 mol g−1 , 69 vibration modes) and
−1
1-pentylcoronene (C29 H22 , M = 370.5 g mol−1 , ˛ = 0.1377 mol g−1 ,
147 vibration modes) are presented in Fig. 8, and calcula-
tions for N,N -diphenylcarbodiimide (C13 H10 N2 , M = 194.2 g mol−1 ,
˛ = 0.1287 mol g−1 , 69 vibration modes) and fluoranthene (C16 H10 ,
M = 202.3 g mol−1 , ˛ = 0.1286 mol g−1 , 72 vibration modes) are
presented in Fig. 9. The mass percent of nitrogen in the N-
methylcarbazole is 7.7 wt%. The average relative deviation of the
g0
computed cp values from 0 to 1500 K is 6.7% and the average
deviation is 0.04 J K−1 g−1 . The mass percent of nitrogen in N,N -
diphenylcarbodiimide is 14.4 wt%. The average relative deviation
evaluated in the temperature range from 0 to 1500 K is 9.0% and
the corresponding average deviation is 0.05 J K−1 g−1 . Thus, het-
eroatoms are expected to impact the utility of the similarity concept
only at temperatures, below ∼300 K, and at high concentration.
g0
Thus, the contributions of internal vibration modes to cp are
only weakly dependent on the specific nature of the vibrations and
these differences diminish through summation of internal vibra-
g0
tion modes and increasing mass of a molecule. cp is primarily a
function of the number of vibrations per mass of a molecule and
over broad ranges of compounds, temperatures, elemental compo-
sitions and molar masses. Dependences on molecular structure and
heteroatom content are secondary. This is evident from a review of
data and is supported by computation.

(a) 8 (b) 30
g0,A

20
- cp )/cp

4
10 (νi - νi )/νi
g0,B

10
B

0
A

0
g0,A
10 (cp

-10
2

-4
-20

-8 -30
0 250 500 750 1000 1250 1500 0 10 20 30 40 50 60 70 80
T/K vibration i
g0,DFT
Fig. 5. Relative deviation of DFT RHHO computed (a) cp values and (b) vibration frequencies for fluoranthene (A) from pyrene (B).
344 V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370

30 3.0
20 2.5
A

/(J·K ·g )
10 (νi - νi )/νi

-1
10
B

2.0

-1
0
A

-10 1.5

g0,DFT
2

-20
1.0
-30

cp
-40 0.5
-50
0.0

g0,A
0 20 40 60 80 100 120 140 160 180

)/cp
vibration i 45
30

g0,B
Fig. 7. Relative deviation of computed vibration frequencies of 1,2-bis(4- 15

-cp
pentylphenyl)ethane (A) from 1,12-bis(phenyl)dodecane (B). 0

g0,A
-15
3. Development of a predictive correlation for isobaric heat -30

10 (cp
capacity of ideal gases -45
Many ideal gas state functions can be derived from cp values
g0 2 0 250 500 750 1000 1250 1500
using thermodynamic relations as long as the temperature depen- T/K
dence is internally consistent. An extensive overview of proposed
g0
mathematical functions can be found in the TRC compilation [9]. Fig. 9. DFT RRHO computed temperature dependences of cp for:
Most of the proposed expressions are polynomials that do not offer magenta line, N,N -diphenylcarbodiimide (C13 H10 N2 , M = 194.2 g mol−1 ,
˛ = 0.1287 mol g−1 ); green dotted line, fluoranthene (C16 H10 ,
safe extrapolation to high and more particularly toward low tem-
M = 202.3 g mol−1 , ˛ = 0.1286 mol g−1 ). Lower insert: relative deviation of the
peratures. Aly and Lee [46] proposed an expression for the molar computed cp
g0,DFT
values of N,N -diphenylcarbodiimide (A) from fluoranthene
(B).(For interpretation of the references to color in this figure legend, the reader is
referred to the web version of the article.)
3.0

2.5 ideal gas heat capacity that yields very accurate descriptions of heat
/(J·K ·g )
-1

capacity, as well as of the ideal gas enthalpy and entropy for many
2.0 compounds 300–1500 K. Coniglio et al. [47] proposed an expression
-1

rooted in statistical mechanics allowing the calculation of the ideal

1.5 gas heat capacity below 300 K. Frenkel et al. [9] developed an empir-
ical expression for molar ideal gas heat capacity that represents
g0,DFT

most of the available data, from 50 to 3000 K:

1.0  
Cp
g0 a   −a 
cp

1 2 a5
= a0 + exp + a3 y2 + a4 − · y8 ;
0.5 R T2 T (T − a7 )2
(11)
 T − a 2
7
0.0 where y = if T > a7 ; y = 0 if T ≤ a7
T + a6
g0,A

Eq. (11) includes eight adjustable parameters a0 –a7 . The value

)/cp

45
for a0 is equal to 3.5 for linear and 4 for non-linear molecules. There
30
g0,B

are three functional terms, each contributing to different temper-

15 ature ranges. This equation though accurate is thus not a suitable
-cp

0 base for generalization. As the similarity concept explored here is

g0,A

-15 less variable above ∼250 K as exemplified above through compar-

-30
10 (cp

isons among and between experimental and computed ideal gas

-45 heat capacity values and the majority of public domain data for
2

heavy compounds starts at 298.15 K, one of the Bureš et al. [15]

0 250 500 750 1000 1250 1500
equations, rooted in statistical mechanics and which provides accu-
T/K rate fits to experimental ideal gas heat capacities above 298.15 K:
   
Fig. 8. DFT RRHO computed temperature dependences of cp for:
g0  c1 2 exp −c1 /T  c2 2 exp −c2 /T
 
2  
2 , (12)
g0
cp = a + b1 + b2
magenta line, N-methylcarbazole (C13 H11 N; M = 181.2 g mol−1 , ˛ = 0.1379 mol g−1 ); T T
1 − exp −c1 /T 1 − exp −c2 /T
green dotted line, 1-pentylcoronene (C29 H22 , M = 370.5 g mol−1 ,
g0,DFT
˛ = 0.1377 mol g−1 ). Lower insert: relative deviation of the computed cp val-
was chosen as a basis for generalization in terms of the sim-
ues of N-methylcarbazole (A) from 1-pentylcoronene (B).(For interpretation of the
references to color in this figure legend, the reader is referred to the web version of ilarity variable ˛. There are only five adjustable parameters a,
the article.) b1 , c1 , b2 , c2 appearing in Eq. (12). The relative importance of
 V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370 345

A four parameter Boltzmann function provides an adequate fit for

4.0 parameter a:
3.5 A1 − A2
a = A2 +   (13)
1 + exp ˛ − A3 /A4
3.0
cp /(J·K ·g )
-1

Thus Eq. (12) is generalized as a correlation with 12 adjustable

2.5
-1

parameters, Eq. (14), for aromatic and acyclic hydrocarbons and

2.0 a correlation with 10 adjustable parameters, Eq. (15), for cyclic
 hydrocarbons:
aliphatic 
1.5
g0

A1 − A2
g0
cp = A2 +   +
1.0 1 + exp ˛ − A3 /A4
 2  
exp −(C11 + C12 ˛)/T
0.5 +(B11 + B12 ˛) −
(C11 + C12 ˛)
 
2 + (14)
T
1 − exp −(C11 + C12 ˛)/T
0.0
 2  
(C21 + C22 ˛) exp −(C21 + C22 ˛)/T
298 500 750 1000 1250 1500 +(B21 + B22 ˛) −
T  
2
1 − exp −(C21 + C22 ˛)/T
T/K g0
cp = (A1 + A2 ˛)

 2  
Fig. 10. Fitted temperature dependence of specific ideal gas heat capacity of n- (C11 + C12 ˛) exp −(C11 + C12 ˛)/T
hexadecylbenzene and contribution of each three terms of Eq. (12). —— black +(B11 + B12 ˛) −
T  
2 +
1 − exp −(C11 + C12 ˛)/T (15)
line (top), fitted curve; blue line: contribution from parameter a;
red line (second top): contribution from the second term;  2  
(C21 + C22 ˛) exp −(C21 + C22 ˛)/T
green line (bottom): contribution from the third term; ,TRC recommended data +(B21 + B22 ˛) −
T  
2
[9].(For interpretation of the references to color in this figure legend, the reader is 1 − exp −(C21 + C22 ˛)/T
referred to the web version of the article.)
The universal parameters of the rendered equations, Eqs. (14)
and (15), were regressed by minimizing the objective function
defined as:
⎡ ⎤
g0,calc 2
the three terms appearing in Eq. (12) is illustrated in Fig. 10 
m
n g0,Recommended
(cp − cp )j
for n-hexadecylbenzene. The function is dominated by the first S= ⎣ ⎦, (16)
n
and the second terms. The third term only contributes at high i=1 j=1
temperatures. g0
cp with the superscript “Recommended” is for data from Train-
The data used in the development of the universal correlations g0
reported in this work were culled from the NIST TRC Ideal Gas ing Set 1 or Training Set 2, whereas cp with the superscript “calc”
Database 88 [9] and NIST/TRC Web Thermo Tables [24]. Database are derived from Eq. (14) or Eq. (15); m denotes the number of
88 contains recommended data calculated using ab-initio meth- compounds, and n represents the number of data points.
ods and also data estimated using the Benson second-order group
contribution technique [11,48]. Where feasible ideal gas functions 4. Results and discussion
in these reference works were verified by comparison to experi-
mentally derived entropy or Cp values at a specific temperature. 4.1. Fitting the adjustable parameters using training data sets
Inherent limitations of any correlation, including the highly accu-
rate group contribution techniques are rooted in the size of the The optimized values for universal parameters of Eqs. (14) and
data pool and variety of compound classes available in the training (15) are indicated in Table 1. The quality of the fit of the correlation
data set. Four data sets were prepared and the list of compounds for both training sets is evaluated in terms of an average standard
with complete statistics can be found in Appendix A. Training Set deviation of the fit  F , average standard relative deviation of the fit
1 contains 123 aromatic and acyclic aliphatic hydrocarbons with a Frel , average relative deviation ı, and average absolute deviation ε.
total of 1734 data points [9]. Training Set 2 contains recommended These four measures provide useful statistics for different parts of
g0 the temperature ranges and are defined as:
estimated cp data for 10 cyclic aliphatic hydrocarbons with a total

of 160 data points [24]. Test Set 1 contains 323 compounds with a m 
 2
 n (cpRecommended − cpcalc )j
total of 3796 data points (mix of ab-initio and estimated data) [9]. F =
1  , (17)
Test Set 2 contains 17 cyclic hydrocarbons compounds with a total m (n − p)
i=1 j=1
of 160 data points [24].
In order to render Eq. (12) predictive, the dependence of the   2

1  
m n
adjustable parameters a, b1 , c1 , b2 , c2 on the similarity variable ˛ cpRecommended − cpcalc /cpRecommended
Frel =  j
, (18)
was evaluated by fitting the parameters for individual compounds m (n − p)
g0
to cp data. The parameter values, for compounds, drawn from i=1 j=1
Training Sets 1 and 2, which cover a wide range of similarity vari- ⎧  ⎫
m ⎪
Recommended calc Recommended
2 ⎪
able values, are reported in Fig. 11a–e. For each compound, the
 ⎨n
(c − c )/c ⎬
set of parameter values minimized the sum of the square deviation 1 p p p j
ı= , (19)
g0
between the experimental and estimated cp values. All five param- m ⎪
⎩ j=1 n ⎪
⎭
i=1
eters possess different values for cyclic aliphatic hydrocarbons
(naphthenic compounds) than for acyclic aliphatic and aromatic ⎡  ⎤
compounds and it was necessary to parse the data in this man- 
m
n Recommended − c calc )2
ner. For cyclic aliphatic hydrocarbons a, b1 , c1 , b2 , c2 can be fit as 1 ⎢ (cp p j ⎥
ε=
m
⎣ n
⎦, (20)
linear functions of the similarity variable, ˛. For aliphatic and aro- i=1 j
matic compounds only, a, possesses a non-linear dependence on ˛.
346 V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370

1.8 4
1.6 (a) (b)
1.4 3

b1/(J·K ·g )
a/(J·K ·g )
1.2

-1
-1

-1
1.0

-1
2
0.8
0.6
0.4 1
0.2
0.0 0
0.08 0.12 0.16 0.20 0.24 0.08 0.12 0.16 0.20 0.24
-1 -1
α/(mol.g ) α/(mol.g )
4 2500
(c) (d)
2000
3
b2/(J·K ·g )
-1

1500

c1/K
-1

2
1000

1 500

0 0
0.08 0.12 0.16 0.20 0.24 0.08 0.12 0.16 0.20 0.24
-1
α/(mol.g )
-1 α/(mol.g )

7000
6000 (e)
5000
4000
c2/K

3000
2000
1000
0
0.08 0.12 0.16 0.20 0.24
-1
α/(mol.g )

Fig. 11. Trends and fits for parameters appearing in Eq. (12) as functions of the similarity variable ˛: (a) a, (b) b1 , (c) b2 , (d) c1 , (e) c2 . TRC recommended data for aromatic
and acyclic aliphatic hydrocarbons [9]: , predicted data from the Benson additive scheme; , quantum–mechanical data; , TRC recommended data for cyclic aliphatic
hydrocarbons [24]; green line, fitted trend for aromatic and acyclic aliphatic hydrocarbons; blue line, fitted trend for cyclic aliphatic hydrocarbons.(For
interpretation of the references to color in this figure legend, the reader is referred to the web version of the article.)

where parameter p is the number of fitted parameters. The over-
all quality of the regression for both training sets is summarized
in Table 2. Absolute and relative deviations for the correlated
g0
cp values from Training Set 1 and Training Set 2 are shown
in Figs. 12 and 13 respectively. The quality of the fit for each
compound in the data set can be found in Appendix A where the
names of compounds, their formulae, molar masses, ˛ values, mass
based composition of heteroatoms, the temperature range of the
g0
data, the number of cp data points and the regression quality are
reported.

Table 1
Parameters appearing in Eqs. (14) and (15).

Eq. (14) – Aromatic and acyclic aliphatic hydrocarbons Eq. (15) – Cyclic aliphatic hydrocarbons

A1 0.58 A1 −0.1793547
A2 1.25 A2 3.86944439
A3 0.17338003
A4 0.014
B11 0.73917383 B11 −0.0805303
B12 8.88308889 B12 9.6997127
C11 1188.28051 C11 686.434198
C12 1813.04613 C12 1820.46648
B21 0.0483019 B21 −0.9996378
B22 4.35656721 B22 17.2624304
C21 2897.01927 C21 1532.25567
C22 5987.80407 C22 5974.87113
 V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370 347

(a) 15 (b) 0.2

)/(J·K ·g )
g0, TRC

-1
10

-1
0.1

)/cp
5

g0, corr

g0, corr
0.0

- cp
0

- cp
g0, TRC
-5

g0, TRC
-0.1
10 (cp
-10

(cp
2

-15 -0.2
298 500 750 1000 1250 1500 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
g0, TRC -1 -1
T/K cp /(J·K ·g )

g0
Fig. 12. Relative (a) and absolute (b) deviation of the correlated cp values from recommended values (Training Set 1 – aromatic and acyclic aliphatic hydrocarbons).

(a) 15 (b) 0.3

)/(J·K ·g )
-1
g0, TRC

10 0.2

-1
)/cp

5 0.1
g0, corr

g0, corr
0.0
- cp

- cp
g0, TRC

-5 -0.1
g0, TRC
10 (cp

-10 (cp -0.2

2

-15 -0.3
298 500 750 1000 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
g0, TRC -1 -1
T/K cp /(J·K ·g )

g0
Fig. 13. Relative (a) and absolute (b) deviation of the correlated cp values from recommended values (Training Set 2 – cyclic aliphatic hydrocarbons).

Table 2 standard deviation Eq. (21) and average standard relative deviation
Quality of Training Set 1 (aromatic and acyclic aliphatic hydrocarbons) and Training
Eq. (22):
Set 2 (cyclic aliphatic hydrocarbons) evaluated from 298.15 up to 1500 K. 

1  (cp m n Recommended 2
Parameter Training Set 1 Training Set 2 − cpcalc )j
=  , (21)
No. of compounds 1230.109–0.226 100.148–0.214 m (n − 1)
Range of ˛/mol g−1 i=1 j=1
Range of molar 116–420.5 1720 138–309 160
  2
mass/g mol−1 
1  
m n
g0
No. of cp values cpRecommended − cpcalc /cpRecommended
 F /J K−1 g−1 0.108 0.103  rel
=  j
. (22)
100Frel 5.31 4.51 m (n − 1)
i=1 j=1
ε/J K−1 g−1 0.038 0.054
100ı 1.84 2.31 The fit between the recommended (Test Set 1 and Test Set 2)
g0
and predicted cp values is shown in Figs. 14 and 15.
The quality of the fit for each compound in the Test Data Sets can
4.2. Testing the predictive character of the correlations also be found in Appendix A where again the names of compounds,
their formulae, molar masses, ˛ values, mass based composition of
g0
Statistical overviews of the data in Test Set 1 and Test Set 2 are heteroatoms, the temperature range of the data, the number of cp
presented in Table 3. Four statistical measures were used to demon- data points and the regression quality are reported.
strate the predictive character of the correlations: average relative
deviation Eq. (19), average absolute deviation Eq. (20), average 4.3. Comparison with other predictive methods

The predictive capability of the new correlations was com-

Table 3 pared with the popular Lee–Kesler [28] generalized correlation
Statistical overview of Test Set 1 (aromatic and acyclic aliphatic hydrocarbons) and
and with the Harrison–Seaton zero-order method [28]. The ref-
Test Set 2 (cyclic aliphatic hydrocarbons) evaluated from 298.15 up to 1500 K. g0
erence cp data for benchmark comparisons were culled from
Parameter Test Set 1 Test Set 2 the NIST/TRC Web Thermo Tables [24]. The Harrison and Seaton
No. of compounds 3230.108–0.226 170.192–0.214 [10] method was originally developed to predict missing Benson’s
Range of ˛/mol g−1 group contributions at discrete temperatures (300, 400, 500, 600,
Range of molar 118–444 3796 138.2–449 102 800, 1000 and 1500 K). The Harrison and Seaton method, which
mass/g mol−1
g0
No. of cp values
includes 15 temperature dependent coefficients, requires only ele-
/J K−1 g−1 0.079 0.059 mental composition and can be applied to petroleum fractions
100 rel 2.86 2.51 at these specific temperatures. Harrison and Seaton tested their
ε/J K−1 g−1 0.066 0.048 method for pure compounds and showed that the method com-
100ı 2.46 2.00
pares remarkably well with estimates of the more rigorous first
348 V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370

(a) 15 (b) 0.4

)/(J·K ·g )
g0, TRC

-1
0.3
10

-1
)/cp
0.2
5

g0, corr
0.1

g0, corr
0.0
- cp
0

- cp
-0.1
g0, TRC

-5

g0, TRC
-0.2
10 (cp

-10

(cp
-0.3
2

-15 -0.4
298 500 750 1000 1250 1500 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
g0, TRC -1 -1
T/K cp /(J·K ·g )

g0
Fig. 14. Relative (a) and absolute (b) deviation of the correlated cp values from recommended values (Test Set 1 – aromatic and acyclic aliphatic hydrocarbons).

(a) 15 (b) 0.3

)/(J·K ·g )
-1
g0, TRC

10 0.2

-1
)/cp

5 0.1
g0, corr

g0, corr
0.0
- cp

- cp
g0, TRC

-5
g0, TRC -0.1
10 (cp

-0.2
(cp

-10
2

-15 -0.3
298 500 750 1000 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
g0, TRC -1 -1
T/K cp /(J·K ·g )

g0
Fig. 15. Relative (a) and absolute (b) deviation of the correlated cp values from recommended values (Test Set 2 – cyclic aliphatic hydrocarbons).

and second-order methods. Lee and Kesler [28] developed two cor- where i and water are saturated densities of the questioned
relations for prediction of ideal gas heat capacities and enthalpies compound i and water at 15.6 ◦ C, respectively. The Waston charac-
of petroleum fractions. Both correlations require knowledge of the terization factor Kw has been used historically to indicate the nature
normal boiling point and specific gravity (two properties generally of the crude oil. It ranges from less than 10 for highly aromatic mate-
used for basic characterization of petroleum fractions) and provide rials to almost 15 for highly paraffinic compounds. Crude oils show
g0
estimates for temperature dependency of cp from 255 to 922 K a narrower range of Kw and vary from 10.5 for a highly naphthenic
(0–1200 F). crude to 12.9 for a paraffinic base crude (naphthenic 10.5–11.5,
The first and the less accurate correlation for temperature intermediate 11.5–12.2 and paraffinic 12.2–12.9). In addition, if the
g0
dependence of cp (in Btu lb−1 F−1 ) is defined as: characterization factor is above 12, the hydrocarbon liquid can be
g0 2 )10−4 T − 1.5393 × 10−7 T 2
cp = −0.32646 + 0.02678Kw − (1.3892 + 1.2122Kw + 0.03803Kw

(23)
−CF1 0.084773 − 0.080809SG − (2.1773 − 2.0826SG)10−4 T + (0.78649 − 0.70423SG)10−7 T 2

where CF1 is the corrective factor defined as

 12.8   10  2 expected to form waxy deposits [48,49] because of its paraffinic
CF1 = −1 − 1 × 100 nature. The second Kesler and Lee [28] correlation for direct calcu-
Kw Kw g0
lation of cp (in Btu lb−1 F−1 ) of petroleum fractions in terms of the
Watson factor and acentric factor:
g0 2 )10−4 T − 1.6658 × 10−7 T 2
cp = −0.33886 + 0.02827Kw − (0.9291 − 1.1543Kw + 0.0368 × Kw
, (26)
−CF2 [0.26105 − 0.59332ω − (4.56 − 9.48ω)10−4 T − (0.536 − 0.6828ω)10−7 T 2 ]
Kw is the Watson characterization factor that indicates chemical
where CF2 is the corrective factor defined as
character of the crude. The Watson factor is a relationship between
the boiling point and specific gravity defined as  (12.8 − K ) 2
w (10 − Kw )
CF2 = .
1/3 10ω
Tb
Kw = , (24)
SG Acentric factor ω was originally defined by Pitzer and is not a
where Tb is the average boiling point in degrees Rankine and SG is measurable quantity. It is directly linked to critical properties (Tc ,
the specific gravity at 15.6 ◦ C. Specific gravity is defined as follows: pc ) and vapor pressure:
!
psat
0.7T
◦ i ω = −log c
−1 (27)
SG (15.6 C) = , (25) pc
water
 V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370 349

Table 4
Statistical comparison with available methods.
g0
Method Temp. range (K) M range (g mol−1 ) No. of comp./cp values  (J K−1 g−1 ) ε (J K−1 g−1 )  rel (%) ı (%)

Comparison Set 1a: aromatic and acyclic aliphatic hydrocarbons; Kw < 10

This work Eq. (14) 300–1000 158.2–351.4 14/84 0.071 0.057 4.41 3.43
Lee–Kesler Eq. (23) 300–900 3.313 2.742 169.8 149.0
Truncated Eq. (23) 300–900 0.319 0.280 16.10 13.79
Lee–Kesler Eq. (26) 300–900 0.492 0.409 22.51 19.54
Truncated Eq. (26) 300–900 0.334 0.297 16.44 14.48
Harrison [10] 300–1000 0.051 0.039 3.34 2.33

Comparison Set 1b: aromatic and acyclic aliphatic hydrocarbons; 10 < Kw < 12.8
This work Eq. (14) 300–1000 162.3–346.7 14/84 0.072 0.060 3.70 2.91
Lee–Kesler Eq. (23) 300–900 0.210 0.172 8.75 7.43
Truncated Eq. (23) 300–900 0.215 0.173 8.92 7.47
Lee–Kesler Eq. (26) 300–900 0.164 0.141 7.07 6.20
Truncated Eq. (26) 300–900 0.167 0.142 7.21 6.26
Harrison [10] 300–1000 0.059 0.045 3.60 2.45

Comparison Set 1c: aromatic and acyclic aliphatic hydrocarbons; Kw > 12.8
This work Eq. (14) 300–1000 307.6–1264.4 10/60 0.032 0.024 1.43 1.03
Lee–Kesler Eq. (23) 300–900 0.592 0.517 21.65 19.55
Truncated Eq. (23) 300–900 0.410 0.356 14.87 13.50
Lee–Kesler Eq. (26) 300–900 0.321 0.249 12.50 9.84
Truncated Eq. (26) 300–900 0.310 0.277 12.02 10.90
Harrison [10] 300–1000 0.096 0.069 5.32 3.43

Comparison Set 2: cyclic aliphatic hydrocarbons Kw <10.7, 12.9>

This work Eq. (15) 300–1000 138.2–448.8 17/102 0.059 0.048 2.51 2.00
Lee-Kesler Eq. (23) 300–900 0.242 0.189 8.78 7.24
Truncated Eq. (23) 300–900 0.235 0.187 8.66 7.22
Lee-Kesler Eq. (26) 300–900 0.241 0.191 8.84 7.34
Truncated Eq. (26) 300–900 0.289 0.224 10.19 8.37
Harrison [10] 300–1000 0.124 0.090 4.43 3.44

(a) 1000 (b) 1000

100 100
rel
rel

10 10
i

σi
σ

1 1

0.1 0.1
7 8 10 12 14 16 100 200 300 400 500 600
Kw,i
-1 -1
Mi/(J·K ·g )

Fig. 16. Compound specific standard relative deviation as function of (a) Watson factor and (b) Molar mass (Comparison Set 1 – aromatic and acyclic aliphatic hydrocarbons
[9]). , Lee–Kesler Eq. (26); , Lee–Kesler – truncated Eq. (26); , Lee–Kesler Eq. (23); , Lee–Kesler – truncated Eq. (23); , Harrison–Seaton [10]; , this work Eq. (14).

Acentric factor for narrow boiling petroleum cuts (pseudo-
components) is a correlated parameter. Riazi’s monograph [25] lists
many predictive correlations for acentric factor developed specifi-
cally for petroleum fractions.
Lee and Kesler fitted parameters in Eqs. (23) and (26) by regress-
ing heat capacities of pure compounds and mixtures. The mixtures
contained about equal proportions of paraffinic, aromatic and
naphthenic components. The pure component data were taken
from the API Research Project 44 (the data are now part of the
NIST/TRC Web Thermo Tables [24]). Kesler and Lee published a
statistical analysis of results calculated from Eq. (26) for 24 hydro-
carbons, ranging from a carbon number C6 to C22 . Their analysis
g0
showed that Eq. (26) should predict cp of pure hydrocarbons with
errors of 1–4%. Riazi [25] re-evaluated this generalized equation
and claims that it may also be applied to pure hydrocarbons with a
carbon number greater than or equal to C5 . Tsonopoulos et al. [50]
g0
suggested using a truncated version of the Lee–Kesler cp correla-
tions where the terms CFi in the above equations are set equal to
zero when Kw is less than 10 or greater than 12.8. Riazi [25] refuted
this observation, however, the results of their statistical analysis
were not disclosed.
The Comparison Set 1 contains 35 aromatic and acyclic aliphatic
hydrocarbons. This data set was further divided into three sub-
groups (Comparison Set 1a: Kw < 10; Comparison Set 1b: Kw ∈ <10,
12.8>; Comparison Set 1c: Kw > 12.8). The Comparison Set 2 con-
tains 17 cyclic aliphatic hydrocarbons with Kw ∈ <10.7, 12.9>. Input
parameters required for both Lee–Kesler correlations (Tb , ω, i ,
water ) were culled from the VMGSim process simulator [51] whose
property data package are sourced from the TRC databases [24].
Results of the comparison are summarized in Table 4 and in
Figs. 16 and 17 for Comparision Data Sets 1 and 2 respectively,
where the compound specific standard deviation, defined as:

 n  Recommended calc 2
 cp − cp
 =
rel j
, (28)
i (n − 1)
j=1
350 V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370

(a) 20 (b) 20

15 15

rel
rel
10 10

σi
σi
5 5

0 0
10.5 11.0 11.5 12.0 12.5 13.0 100 200 300 400 500
-1 -1
Kw,i Mi/(J·K ·g )

Fig. 17. Compound specific standard relative deviation as function of (a) Watson factor and (b) molar mass (Comparison Set 2 – cyclic aliphatic hydrocarbons [24]). ,
Lee–Kesler Eq. (26); , Lee–Kesler – truncated Eq. (26); , Lee–Kesler Eq. (23); , Lee–Kesler – truncated Eq. (23); , Harrison–Seaton [10]; , this work Eq. (15).

4 3
(a) 3
(b)
2
1

cp /(J·K ·g )
0
cp /(J·K ·g )

-1
-1

-1
-1 2
-1

-2
-3
-4
-5
-6
-7
-8 1
-9
-10
-11
TRC
TRC

1000 35
10 (cp -cp )/cp
10 (cp -cp )/cp

30
100 25
corr
corr

20
10 15
TRC
TRC

10
1 5
0
2
2

0.1 -5
250 500 750 1000 250 500 750 1000
T/K T/K
g0
Fig. 18. Estimated cp for 1,5-diaminonaphthalene (C10 H10 N2 , M = 158.2 g mol−1 , ˛ = 0.1391 mol g−1 , Kw = 8.377) evaluated from 298.15 to 1000 K. (, TRC recommended data
[24]; , this work Eq. (14)); (a) , Lee–Kesler Eq. (23); 䊉, Lee–Kesler Eq. (26); (b) , Lee–Kesler – truncated Eq. (23); 䊉, Lee–Kesler – truncated Eq. (26). Lower
inserts: relative deviation of computed data from recommended TRC data for: , this work Eq. (14); (a) , Lee–Kesler Eq. (23); , Lee–Kesler Eq. (26); (b) , Lee–Kesler –
truncated Eq. (23); , Lee–Kesler – truncated Eq. (26).

(a) 5 (b)
4
cp /(J·K ·g )

4
cp /(J·K ·g )

-1
-1

-1
-1

2 2

1
TRC
TRC

5
10 (cp -cp )/cp

30
10 (cp -cp )/cp

20 0
corr
corr

10 -5
0
-10
TRC
TRC

-10
-20 -15
2
2

-30 -20
250 500 750 1000 250 500 750 1000
T/K T/K
g0
Fig. 19. Estimated cp for n-octacontane (C80 H162 , M = 1124.1 g mol−1 , ˛ = 0.2153 mol g−1 , Kw = 14.585) evaluated from 298.15 to 1000 K. (a) Lee–Kesler equations, (b) truncated
Lee–Kesler equations. See Fig. 18 for explanation of symbols.
 V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370 351

g0 g0
Fig. 20. Estimated cp ( ) Eq. (14); ( ) Eq. (15)); (a) ˛ = 0.13; (b) ˛ = 0.15; (c) ˛ = 0.17; (d) ˛ = 0.22. Inserts: cp (differences between Eq. (14) and Eq. (15)).

is plotted against the Watson factor, Kw , and the molar mass of
the compounds in the Comparison Data Sets.
The universal correlations reported in this work (Eqs. (14) and
(15)) and the Harrison–Seaton method both provide reliable and
consistent performance over a wide range of Kw values (Figs. Fig.
1616a and Fig. 1717a) and molar masses, M (Figs. Fig. 1616b and
Fig. 1717b) respectively. The errors associated with the estimated
values approach experimental errors. By contrast, the performance
of the Lee–Kesler correlations, Eqs. (23) and (26) in either their
full or truncated forms, was variable and poor in many instances.
This family of correlations provides systematically poorer estimates
than the universal correlations proposed in this work for each of
the comparison sets and subsets, irrespective of Watson factor
and molar mass values. The universal correlations also out per-
formed the Harrison–Seaton method at the temperatures where it
is valid (300, 400, 500, 600, 800, 1000 and 1500 K) and the univer-
g0
sal correlations provide estimates of cp as a continuous function of
temperature. This is a distinct advantage over the limited number
of discrete temperature values available for the Harrison–Seaton
method.
Statistical analysis of the Lee–Kesler correlations performed
with Comparison Set 1 support Tsonopoulos observations [50].
For compounds with a Kw outside the region <10, 12.8>, both
Lee–Kesler methods give estimates with large qualitative and quan-
g0
titative errors. For example, cp values for 1,5-diaminonaphthalene
(Kw < 10) estimated using Eqs. (23) and (26) are shown in Fig. 18a
352 V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370
Fig. 21. Proposed molecular representations for asphaltenes: (a) C283 H337 N3 O4 S9 [56]; (b) C64 H52 S2 [64,65].
and for the truncated versions of Eqs. (23) and (26) in Fig. 18b.
Eqs. (23) and (26), Fig. 18a, both yield decreasing heat capacity val-
ues with increasing temperature and the truncated forms of Eqs.
(23) and (26), Fig. 18b, are clearly preferred. In general, for com-
pounds with Kw < 10 (Comparison Set 1a), the truncated forms of
Eqs. (23) and (26) provide correct trends with temperature. For
hydrocarbons with Kw > 12.8 (Comparison Set 1c) both Lee–Kesler
equations Eqs. (23) and (26) are unreliable, especially for large
molecules for which the input parameters are not available exper-
imentally. Estimates for n-octacontane are shown in Fig. 19. Again,
the truncated forms of Eqs. (23) and (26), Fig. 19b, are preferred
over the full versions, Fig. 19a. For compounds with Kw > 12.8, trun-
g0
cated forms of Eqs. (23) and (26) also provide comparable cp value
errors for Comparison Set 1c as noted in Table 4. For Kw values
between 10 and 12.8 (Comparison Set 1b), both Lee–Kesler corre-
lations predict correct temperature trends, but given the average
standard deviations 0.210 and 0.164 J K−1 g−1 and average stan-
dard relative deviations 8.75% and 7.07% for Eqs. (23) and (26) and
higher errors for the truncated forms even in this Kw region the
universal correlation, Eq. (14) and the Harrison–Seaton method are
preferred.
4.4. Application of the universal correlations for mixtures and
petroleum fractions
The universal correlations, Eqs. (14) and (15), are insensitive
to molecular structure and molecular size. Consequently, for well-
defined hydrocarbon mixtures, where the constituents are known
and fall into either the aromatic/paraffinic or naphthenic classes,
and the elemental composition is known or can be computed read-
ily from the composition, Eq. (14) or Eq. (15) can be applied for
g0
the calculation of cp . For crude oils or a crude oil fractions such
as a boiling range cuts or SARA fractions, where the nature of
the mixture (aromatic/paraffinic or naphthenic) and its elemen-
tal composition are known (measured or estimated), then either
Eq. (14) or Eq. (15) can also be applied directly for the calcula-
g0
tion of cp . For mixtures comprising both aromatic/paraffinic and
naphthenic lumped constituents, where the elemental analysis and
g0
mass fractions of these two constituents are known, then cp is
simply the mass fraction weighted value obtained using Eqs. (14)
and (15) separately for the lumped constituents. To obtain molar
heat capacities for mixtures, mean molar masses or estimates are
required.
Normally, the nature of an ill-defined hydrocarbon fluid is
known. One refers to waxy (paraffin-rich) and asphaltenic (typ-
ically aromatic-rich) crudes. Natural gas condensates are rarely
naphthenic. For such typical cases the selection of correlation is
apparent. However, for rare cases, the nature of the hydrocarbon
fluid is unknown, or indeterminate in the case of pure compounds
possessing both naphthenic and aromatic functionalities, and addi-
g0
tional uncertainty is introduced into the cp calculation for specific
values of the similarity variable ˛. Fortunately, the similarity vari-
able value for naphthenic constituents is bounded, 0.13 < ˛ < 0.22
and consequently the uncertainty introduced is also bounded. At
˛ = 0.13, Fig. 20a, the heat capacity of naphthenic constituents Eq.
(15) is systematically lower than those of other constituents Eq.
(14). The additional average absolute and average relative uncer-
tainty introduced, if the mean value obtained from Eqs. (14) and
(15) is used, is 0.094 J K−1 g−1 and 4.4% respectively from 300 to
g0
1500 K. At ˛ = 0.15, Fig. 20b, the predicted cp values from the two
correlations overlap, and the additional uncertainties are negligi-
ble (0.0084 J K−1 g−1 and 0.46% respectively). At ˛ = 0.175, Fig. 20c,
the heat capacity of naphthenic constituents Eq. (15) crosses the
heat capacity of the other constituents Eq. (14) but again the
additional uncertainties remain low (0.045 J K−1 g−1 and 1.74%
respectively). At ˛ = 0.22, Fig. 20d, the additional uncertainties are
larger (0.13 J K−1 g−1 and 3.6% respectively) but much of this addi-
tional uncertainty is introduced at high temperatures – greater than
800 K as is clear from Fig. 20d. Thus the additional uncertainty,
rarely introduced in practice, remains small and well-defined over
the relevant ranges of temperature and fluid composition. Even for
such cases, the average of the predictions from Eqs. (14) and (15)
is preferred over all four of the Lee–Kesler options Eqs. (23)–(26).
However, the averaged universal correlation does not remain pre-
ferred over the Harrison–Seaton correlation, at the temperatures
for which it is valid, and this method should be used to cross check
results.
The universal correlations are well suited for the prediction of
g0
cp values for non-distillable fractions of crude oils. Convention-
ally the properties of the non-distillable hydrocarbon residues are
derived from extrapolation of distillation curves or simulated dis-
tillation curves (SimDist) using generalized property correlations
[25]. For heavy oils and bitumen this fraction may comprise more
than 50 wt% of the fluid [52]. Additional fractionation such as deep
vacuum fractionation [53] and solubility class based fractionation
(SARA) have recently been applied to further characterize extra-
heavy oils [54]. SARA composition analysis yields four fractions:
saturates, aromatics, resins and asphaltenes. As part of this char-
acterization, the asphaltene boiling point curve was obtained by
extrapolation of the boiling point curve of the distillable portion
including deep vacuum cuts where two approaches were used to
represent the molecular weight distribution [54–56]. Extrapolation
combined with generalized property correlations leads to signifi-
g0 g0
cant uncertainty in cp values. cp is more certainly estimated for
 V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370
(a)
3.0
cp /(J·K ·g )
-1
2.5
-1
2.0
g0
1.5
g0,Benson
1.0
8 8
)/cp
g0,corr
4 4
-cp
0 0
g0,Benson
-4
-8
10 (cp
298 500
2
g0
Fig. 22. Estimated cp values for: (a) C283 H337 N3 O4 S9 (M = 4133.3 g mol−1 , ˛ = 0.1539 mol g−1 ), (b) C64 H52 S2 (M = 885.2 g mol−1 , ˛ = 0.1333 mol g−1 ) evaluated from 298.15 to
up to 1500 K. 䊉, Benson’s group contribution method;
each heavy fraction, however obtained, using elemental analysis,
which is frequently available, and the universal correlations pre-
sented in this work.
Molecule based representation of petroleum fractions is being
pursued in parallel and is expected to supplant current practice
over time. Currently, this approach remains at a formative stage
of development for non-distillable fractions [57], because different
molecular representations for the same fractions of the same flu-
ids based on the same or similar input data are proposed [58–60].
Despite this current limitation, successful phase behavior models
have begun to appear that are based on molecular representation
of non-distillable fractions [61,62]. These models are built upon
the Marrero-Gani group contribution equation of state and related
g0
structure property correlations [63]. While in principle, cp val-
ues for molecules appearing in such models can be obtained using
the Benson method augmented with group contributions specifi-
cally developed for polyaromatic compounds [18,19], the number,
nature, scale and complexity of the molecules proposed to rep-
resent non-distillable fractions underscores the need for simpler
computation approaches of equivalent or near equivalent accuracy.
The universal correlation Eq. (14) is expected to fulfill this role.
Two among many molecules proposed for representing the asphal-
g0
tene fraction are illustrated in Fig. 21a and b. cp values obtained
for these two compounds using the updated Benson method and
the universal correlation, Eq. (14), are compared in Fig. 22a and
b respectively. The agreement between the benchmark computa-
tional method and the universal correlation is excellent from 300
to 1500 K.
5. Conclusions
Generalized ideal gas heat capacity correlations, valid from
298.15 to 1500 K, for hydrocarbon and heteroatom substituted
compounds were developed that are based on the understanding
that ideal gas heat capacity is primarily a function of the number
of fundamental vibrations per mass of a molecule. This concept
embodied in the similarity variable, ˛, and its limitations were
explored. Molecular structure was found to play a secondary role
but it remained necessary to correlate aromatic + acylic aliphatic
compounds, and cyclic aliphatic compounds separately. Com-
pounds and mixtures comprising more than 15 wt% heteroatoms
353
(b) 3.0
2.5
cp /(J·K ·g )
-1
-1
2.0
g0
1.5
g0,Benson
1.0
)/cp
g0,corr
-cp
g0,Benson
-4
-8
10 (cp
750 1000 1250 1500 298 500 750 1000 1250 1500
2
T/K T/K
, this work Eq. (14);  and , relative deviations.
(NOSF) were excluded from both correlations. The correlation for
aromatic and acyclic aliphatic compounds was fit using a data set
comprising 123 compounds and 1720 heat capacity values and
tested using a data set comprising 323 compounds with 3796
specific heat capacity values. The average standard deviation of
the correlated values from recommended values for the test data
set is 0.079 J K−1 g−1 and the average standard relative deviation
is 2.86%. For cyclic aliphatic hydrocarbons, the correlation was fit
using a data set comprising 10 compounds and 160 heat capacity
values, and tested using a data set comprising 17 compounds with
102 data points. The average standard deviation of the correlation
from recommended values for the test data set is 0.059 J K−1 g−1 and
the average standard relative deviation is 2.51%. These zero-order
correlations provide ideal gas estimates with maximum errors
less than 10% and the values approach those calculated using the
benchmark Benson method for large molecules. The correlations
presented in this work are recommended over Lee–Kesler correla-
tions, and the Harrison–Seaton correlation on the basis of accuracy
and breadth of application for general-purpose calculations. If the
assignment of a hydrocarbon to the aromatic + acyclic or cyclic
aliphatic class is uncertain, then the Heaton–Seaton correlation is
preferred, if it can be applied. Otherwise, the average heat capac-
ity value obtained from Eqs. (14) and (15) is recommended. The
universal correlations presented in this work have already begun
to find industrial applications in oil characterization, and reservoir
and process simulation.
Acknowledgments
The authors acknowledge with thanks V. Lastovka’s PhD super-
visors K. Růžička and M. Fulem (ICT Prague) for their support,
guidance, and advice, as well as his managers Dr. L. Whale and
J. van Dorp (Shell, Canada) and Dr. V. Saubestre (Total SA) for
their encouragement and Ms. Sepideh Rajaeirad for her help with
the manuscript. This research received financial support from the
sponsors for the Industrial Research Chair in Petroleum Thermo-
dynamics: Alberta Innovates Energy and Environment Solutions,
British Petroleum, ConocoPhillips Inc., Halliburton, Imperial Oil
Resources, Kellogg Brown and Root (KBR), Nexen Inc., Shell Canada,
Total Canada, and the Natural Sciences and Engineering Research
Council of Canada (NSERC).
 354
Appendix A. Data used for fitting and testing Eqs. (14) and (15)

g0
Compound Formula Ref. Temperature Eqa Kw (VMGSIM) SG (VMGSIM) ω (VMGSIM) cp values εb Fc, d ıee (%)  rel  rel
F
range/K (J K−1 g−1 ) (J K−1 g−1 ) (%)f, g
Training
Set 1
Indene C9H8 [9] 298.15–1000 NA NA NA 16 0.04 0.08 2.19 4.45
Indane C9H10 [9] 298.15–1500 NA NA NA 14 0.05 0.15 2.11 6.35
o-Methylstyrene C9H10 [9] 298.15–1500 NA NA NA 14 0.01 0.05 0.71 2.62
m-Methylstyrene C9H10 [9] 298.15–1500 NA NA NA 14 0.02 0.05 0.79 3.06
p-Methylstyrene C9H10 [9] 298.15–1500 NA NA NA 14 0.01 0.04 0.54 1.62
A-Methylstyrene C9H10 [9] 298.15–1500 NA NA NA 14 0.04 0.11 1.79 4.98
Isopropylbenzene C9H12 [9] 298.15–1500 NA NA NA 14 0.01 0.04 0.57 2.07
1,2,3-Trimethylbenzene C9H12 [9] 298.15–1500 NA NA NA 14 0.05 0.15 2.03 5.99
1,2,4-Trimethylbenzene C9H12 [9] 298.15–1500 NA NA NA 14 0.06 0.17 2.70 8.90
1,3,5-Trimethylbenzene C9H12 [9] 298.15–1500 NA NA NA 14 0.09 0.26 4.19 12.71
n-Nonane C9H20 [9] 298.15–1500 NA NA NA 14 0.02 0.06 0.74 2.41
1-Fluoronaphthalene C10H7F [9] 298.15–1000 NA NA NA 16 0.03 0.08 1.95 4.37

V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370

2-Fluoronaphthalene C10H7F [9] 298.25–1000 NA NA NA 16 0.03 0.08 2.14 5.19
Naphthalene C10H8 [9] 298.15–1500 NA NA NA 14 0.03 0.08 1.50 4.15
1-Naphthalenol C10H8O [9] 298.15–1500 NA NA NA 14 0.03 0.09 1.78 6.05
1,2-Dihydronaphthalene C10H10 [9] 298.15–1500 NA NA NA 14 0.05 0.16 1.93 5.56
1,4-Dihydronaphthalene C10H10 [9] 298.15–1500 NA NA NA 14 0.06 0.16 2.18 5.98
Tetralin C10H12 [9] 298.15–1500 NA NA NA 14 0.06 0.17 2.52 8.13
1,2,3,4-Tetramethylbenzene C10H14 [9] 298.15–1500 NA NA NA 14 0.06 0.18 2.43 7.10
1,2,3,5-Tetramethylbenzene C10H14 [9] 298.15–1500 NA NA NA 14 0.07 0.21 2.82 8.51
n-Decane C10H22 [9] 298.15–1500 NA NA NA 14 0.01 0.04 0.55 2.06
3-Ethyloctane C10H22 [9] 298.15–1500 NA NA NA 14 0.04 0.11 1.24 3.67
4-Ethyloctane C10H22 [9] 298.15–1500 NA NA NA 14 0.04 0.12 1.41 4.11
2-Methylnonane C10H22 [9] 298.15–1500 NA NA NA 14 0.05 0.13 1.37 3.77
3-Methylnonane C10H22 [9] 298.15–1500 NA NA NA 14 0.04 0.12 1.16 3.24
4-Methylnonane C10H22 [9] 298.15–1500 NA NA NA 14 0.05 0.14 1.42 3.87
5-Methylnonane C10H22 [9] 298.15–1500 NA NA NA 14 0.04 0.13 1.30 3.60
4-Propylheptane C10H22 [9] 298.15–1500 NA NA NA 14 0.06 0.15 1.84 5.22
1-Methylnaphthalene C11H10 [9] 298.15–1500 NA NA NA 14 0.05 0.15 2.80 8.54
2-Methylnaphthalene C11H10 [9] 298.15–1500 NA NA NA 14 0.04 0.11 1.81 5.22
Acenaphthylene C12H8 [9] 298.15–1500 NA NA NA 14 0.01 0.04 0.83 3.79
Biphenylene C12H8 [9] 298.15–1500 NA NA NA 14 0.02 0.09 1.71 7.00
Dibenzo[1,4]dioxin C12H8O2 [9] 298.15–1500 NA NA NA 14 0.05 0.16 2.58 7.20
Acenaphthene C12H10 [9] 298.15–1500 NA NA NA 14 0.05 0.15 2.38 6.34
Biphenyl C12H10 [9] 298.15–1500 NA NA NA 14 0.06 0.15 2.87 8.33
Benz[e]indene C13H10 [9] 298.15–1500 NA NA NA 14 0.05 0.13 2.36 6.52
Benz[f]indene C13H10 [9] 298.15–1500 NA NA NA 14 0.05 0.12 2.21 5.99
Fluorene C13H10 [9] 298.15–1500 NA NA NA 14 0.05 0.14 2.50 6.78
Pyracyclene C14H8 [9] 298.15–1500 NA NA NA 14 0.02 0.07 1.10 3.05
Phenanthrene C14H10 [9] 298.15–1500 NA NA NA 14 0.04 0.11 2.21 6.64
1,2-Dihydroanthracene C14H12 [9] 298.15–1500 NA NA NA 14 0.06 0.18 2.75 7.31
1,4-Dihydroanthracene C14H12 [9] 298.15–1500 NA NA NA 14 0.07 0.18 2.92 7.81
9,10-Dihydroanthracene C14H12 [9] 298.15–1500 NA NA NA 14 0.07 0.19 3.00 7.99
1,2-Dihydrophenanthrene C14H12 [9] 298.15–1500 NA NA NA 14 0.06 0.18 2.87 7.67
1,4-Dihydrophenanthrene C14H12 [9] 298.15–1500 NA NA NA 14 0.07 0.18 3.01 8.09
3,4-Dihydrophenanthrene C14H12 [9] 298.15–1500 NA NA NA 14 0.06 0.18 2.87 7.67
9,10-Dihydrophenanthrene C14H12 [9] 298.15–1500 NA NA NA 14 0.07 0.19 3.15 8.41
1,2,5,6-Tetrahydro- C14H12 [9] 298.15–1500 NA NA NA 14 0.06 0.17 2.27 6.39
cyclopent[fg]acenaphthylene
1,2,3,4- C14H14 [9] 298.15–1500 NA NA NA 14 0.07 0.21 2.53 7.40
Tetrahydroanthracene
1,2,3,4- C14H14 [9] 298.15–1500 NA NA NA 14 0.07 0.22 2.65 7.55
Tetrahydrophenanthrene
1,2,3,5-Tetraethylbenzene C14H22 [9] 298.15–1000 NA NA NA 16 0.05 0.10 1.91 4.10
 g0
Compound Formula Ref. Temperature Eqa Kw (VMGSIM) SG (VMGSIM) ω (VMGSIM) cp values εb Fc, d ıed (%)  rel  rel
F
range/K (J K−1 g−1 ) (J K−1 g−1 ) (%)f , g
4H- C15H10 [9] 298.15–1500 NA NA NA 14 0.02 0.05 0.98 2.64
cyclopenta[def]phenanthrene
2,3-Benzo-1,6-methano(10)- C15H12 [9] 298.15–1000 NA NA NA 16 0.03 0.03 1.59 1.92
annulene
3,4-Benzo-1,6-methano(10)- C15H12 [9] 298.15–1000 NA NA NA 16 0.03 0.03 1.56 1.88
annulene
1-Pentadecene C15H30 [9] 298.15–1500 NA NA NA 14 0.06 0.20 1.72 5.35
Aceanthrylene C16H10 [9] 298.15–1500 NA NA NA 14 0.01 0.03 0.67 3.02
Acephenanthrylene C16H10 [9] 298.15–1500 NA NA NA 14 0.02 0.05 1.06 4.37
Fluoranthene C16H10 [9] 298.15–1500 NA NA NA 14 0.01 0.04 0.92 3.55
Pyrene C16H10 [9] 298.15–1500 NA NA NA 14 0.02 0.05 1.03 3.94
Aceanthrene C16H12 [9] 298.15–1500 NA NA NA 14 0.05 0.14 2.60 7.07
Acephenanthrene C16H12 [9] 298.15–1500 NA NA NA 14 0.05 0.14 2.41 6.48
17H- C17H12 [9] 298.15–1500 NA NA NA 14 0.04 0.11 2.19 6.15
cyclopenta[a]phenanthrene
1H- C17H12 [9] 298.15–1500 NA NA NA 14 0.04 0.11 2.17 6.13
cyclopenta[l]phenanthrene

V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370

1H-cyclopent[b]anthracene C17H12 [9] 298.15–1500 NA NA NA 14 0.04 0.11 1.96 5.34
Benzo[ghi]fluoranthene C18H10 [9] 298.15–1500 NA NA NA 14 0.02 0.06 1.02 2.73
Cyclopenta[cd]pyrene C18H10 [9] 298.15–1500 NA NA NA 14 0.02 0.05 0.85 2.35
Cyclopent[fg]aceanthrylene C18H10 [9] 298.15–1500 NA NA NA 14 0.02 0.05 0.98 3.05
Benz[a]anthracene C18H12 [9] 298.15–1500 NA NA NA 14 0.04 0.09 1.96 5.87
Benzo[c]phenanthrene C18H12 [9] 298.15–1500 NA NA NA 14 0.04 0.10 2.07 6.29
Chrysene C18H12 [9] 298.15–1500 NA NA NA 14 0.04 0.10 2.07 6.29
Naphthacene C18H12 [9] 298.15–1500 NA NA NA 14 0.03 0.09 1.86 5.48
Triphenylene C18H12 [9] 298.15–1500 NA NA NA 14 0.04 0.10 2.19 6.79
1-Nonadecene C19H38 [9] 298.15–1500 NA NA NA 14 0.06 0.19 1.55 5.12
Dicyclopenta[cd,fg]pyrene C20H10 [9] 298.15–1500 NA NA NA 14 0.04 0.11 1.88 5.07
Dicyclopenta[cd,jk]pyrene C20H10 [9] 298.15–1500 NA NA NA 14 0.04 0.10 1.67 4.64
Dicyclopenta[cd,mn]pyrene C20H10 [9] 298.15–1500 NA NA NA 14 0.04 0.11 1.85 4.99
Corannulene C20H10 [9] 298.15–1500 NA NA NA 14 0.03 0.10 1.83 4.94
Benz[j]aceanthrylene C20H12 [9] 298.15–1500 NA NA NA 14 0.01 0.04 0.84 3.41
Benzo[a]pyrene C20H12 [9] 298.15–1500 NA NA NA 14 0.02 0.06 1.19 4.42
Benzo[e]pyrene C20H12 [9] 298.15–1500 NA NA NA 14 0.02 0.06 1.24 4.65
Benzo[k]fluoranthene C20H12 [9] 298.15–1500 NA NA NA 14 0.01 0.04 0.92 3.39
Perylene C20H12 [9] 298.15–1500 NA NA NA 14 0.02 0.06 1.24 4.65
Cholanthrene C20H14 [9] 298.15–1500 NA NA NA 14 0.05 0.13 2.33 6.34
1H-cyclopenta[a]chrysene C21H14 [9] 298.15–1500 NA NA NA 14 0.04 0.10 2.00 5.71
Dicyclopenta[ghi,pqr]perylene C22H10 [9] 298.15–1500 NA NA NA 14 0.07 0.17 3.62 9.79
Tricyclopenta[cd,fg,jk]pyrene C22H10 [9] 298.15–1500 NA NA NA 14 0.06 0.16 2.89 7.67
Benzo[ghi]perylene C22H12 [9] 298.15–1500 NA NA NA 14 0.01 0.04 0.66 2.06
Dibenzo[def,mno]chrysene C22H12 [9] 298.15–1500 NA NA NA 14 0.01 0.04 0.63 1.92
Indeno[1,2,3- C22H12 [9] 298.15–1500 NA NA NA 14 0.02 0.05 0.99 2.67
cd]fluorenthene
Benzo[a]naphthacene C22H14 [9] 298.15–1500 NA NA NA 14 0.03 0.08 1.76 5.26
Benzo[b]chrysene C22H14 [9] 298.15–1500 NA NA NA 14 0.03 0.09 1.85 5.61
1,2:3,4-Dibenzanthracene C22H14 [9] 298.15–1500 NA NA NA 14 0.03 0.09 1.95 6.01
Benzo[c]chrysene C22H14 [9] 298.15–1500 NA NA NA 14 0.03 0.09 1.94 5.95
Benzo[g]chrysene C22H14 [9] 298.15–1500 NA NA NA 14 0.04 0.10 2.04 6.37
Dibenz[a,h]anthracene C22H14 [9] 298.15–1500 NA NA NA 14 0.03 0.09 1.85 5.60
Dibenz[a,j]anthracene C22H14 [9] 298.15–1500 NA NA NA 14 0.03 0.09 1.85 5.61
Naphth[1,2-a]anthracene C22H14 [9] 298.15–1500 NA NA NA 14 0.03 0.09 1.85 5.62
Pentacene C22H14 [9] 298.15–1500 NA NA NA 14 0.03 0.08 1.67 4.93
Pentaphene C22H14 [9] 298.15–1500 NA NA NA 14 0.03 0.08 1.76 5.26
Picene C22H14 [9] 298.15–1500 NA NA NA 14 0.03 0.09 1.93 5.93
Tetracyclopenta[cd,fg,jk,mn]pyrene C24H10 [9] 298.15–1500 NA NA NA 14 0.08 0.21 4.24 11.27
Benz[m,n,o]indeno[1,7,6,5- C24H12 [9] 298.15–1500 NA NA NA 14 0.03 0.09 1.51 4.03
cdef]chrysene
Benz[m,n,o]indeno[5,6,7,1- C24H12 [9] 298.15–1500 NA NA NA 14 0.03 0.08 1.20 3.49
defg]chrysene

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Compound Formula Ref. Temperature Eqa Kw (VMGSIM) SG (VMGSIM) ω (VMGSIM) cp values εb Fc, d ıed (%)  rel  rel
F
range/K (J K−1 g−1 ) (J K−1 g−1 ) (%)f , g
Benzo[ghi]cyclopenta[cd]perylene C24H12 [9] 298.15–1500 NA NA NA 14 0.03 0.08 1.21 3.50
Coronene C24H12 [9] 298.15–1500 NA NA NA 14 0.03 0.08 1.37 3.72
Dibenzo[def,mno]cyclo- C24H12 [9] 298.15–1500 NA NA NA 14 0.03 0.08 1.23 3.54
penta[hi]chrysene
Dicyclopenta[cd,lm]perylene C24H12 [9] 298.15–1500 NA NA NA 14 0.03 0.08 1.16 3.27
Indeno[5,6,7,1- C24H12 [9] 298.15–1500 NA NA NA 14 0.03 0.09 1.47 3.96
pqra]perylene
Dibenzo[b,def]chrysene C24H14 [9] 298.15–1500 NA NA NA 14 0.01 0.04 0.96 3.59
Dibenzo[de,mn]naphthacene C24H14 [9] 298.15–1500 NA NA NA 14 0.01 0.04 0.96 3.57
Dibenzo[de,qr]naphthacene C24H14 [9] 298.15–1500 NA NA NA 14 0.01 0.04 0.96 3.59
Dibenzo[fg,op]naphthacene C24H14 [9] 298.15–1500 NA NA NA 14 0.02 0.05 1.10 4.19
Cyclopenta[bc]coronene C26H12 [9] 298.15–1500 NA NA NA 14 0.05 0.13 2.32 6.16
Rubicene C26H14 [9] 298.15–1500 NA NA NA 14 0.01 0.04 0.75 2.96
Dicyclopenta[bc,hi]coronene C28H12 [9] 298.15-1500 NA NA NA 14 0.06 0.17 3.43 9.13
Benzo[pqr]naphtho[8,1,2- C28H14 [9] 298.15-1500 NA NA NA 14 0.02 0.06 0.97 2.75

V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370

bcd]perylene
Phenanthro[1,10,9,8- C28H14 [9] 298.15–1500 NA NA NA 14 0.02 0.06 0.98 2.75
opqra]perylene
Tricyclopenta[bc,hi,no]coronene C30H12 [9] 298.15–1500 NA NA NA 14 0.07 0.19 3.71 9.83
Dibenzo[bc,ef]coronene C30H14 [9] 298.15–1500 NA NA NA 14 0.04 0.10 1.86 4.96
Dibenzo[bc,kl]coronene C30H14 [9] 298.15–1500 NA NA NA 14 0.04 0.11 1.90 5.04
Pyranthrene C30H16 [9] 298.15–1500 NA NA NA 14 0.01 0.03 0.49 1.66
Ovalene C32H14 [9] 298.15–1500 NA NA NA 14 0.05 0.14 2.78 7.37
Pentacyclo- C34H12 [9] 298.15–1500 NA NA NA 14 0.09 0.25 4.87 12.88
penta[bc,ef,hi,kl,no]coronene

Test Set 1
(E)-1-Phenyl-1-propene C9H10 [9] 298.15–1500 NA NA NA 14 0.03 0.03 1.45 2.25
(Z)-1-Phenyl-1-propene C9H10 [9] 298.15–1500 NA NA NA 14 0.01 0.02 0.50 0.62
4-Indanol C9H10O [9] 298.15–1500 NA NA NA 14 0.03 0.04 1.73 2.10
5-Indanol C9H10O [9] 298.15–1500 NA NA NA 14 0.04 0.04 1.69 1.88
1-Ethyl-2-methylbenzene C9H12 [9] 298.15–1500 NA NA NA 14 0.06 0.07 2.37 2.85
1-Ethyl-3-methylbenzene C9H12 [9] 298.15–1500 NA NA NA 14 0.07 0.08 3.46 4.21
1-Ethyl-4-methylbenzene C9H12 [9] 298.15–1500 NA NA NA 14 0.06 0.07 3.09 3.83
Propylbenzene C9H12 [9] 298.15–1500 NA NA NA 14 0.06 0.06 2.34 2.56
1-Nonyne C9H16 [9] 298.15–1500 NA NA NA 14 0.11 0.13 3.42 3.85
Nonanenitrile C9H17N [9] 298.15–1500 NA NA NA 14 0.06 0.07 2.16 2.44
1-Nonene C9H18 [9] 298.15–1500 NA NA NA 14 0.08 0.09 2.32 2.49
2-Nonanone C9H18O [9] 298.15–1000 NA NA NA 9 0.10 0.13 3.80 4.58
3-Nonanone C9H18O [9] 298.15–1000 NA NA NA 9 0.10 0.12 3.81 4.34
4-Nonanone C9H18O [9] 298.15–1000 NA NA NA 9 0.10 0.12 3.81 4.34
Nonanal C9H18O [9] 298.15–1500 NA NA NA 14 0.07 0.08 2.42 2.75
(3RS,4RS)-Dimethylheptane C9H20 [9] 298.15–1500 NA NA NA 14 0.08 0.10 2.09 2.44
(3RS,4SR)-Dimethylheptane C9H20 [9] 298.15–1500 NA NA NA 14 0.08 0.10 2.09 2.47
(3RS,5RS)-Dimethylheptane C9H20 [9] 298.15–1500 NA NA NA 14 0.10 0.11 2.92 3.13
(3RS,5SR)-Dimethylheptane C9H20 [9] 298.15–1500 NA NA NA 14 0.10 0.11 2.88 3.07
2,(3RS,4RS)- C9H20 [9] 298.15–1500 NA NA NA 14 0.12 0.14 3.39 3.69
Trimethylhexane
2,(3RS,4SR)- C9H20 [9] 298.15–1500 NA NA NA 14 0.12 0.14 3.49 3.77
Trimethylhexane
1-Nonanol C9H20O [9] 298.15–1500 NA NA NA 14 0.11 0.12 3.57 3.74
1-Nonanethiol C9H20S [9] 298.15–1000 NA NA NA 9 0.07 0.09 2.86 3.44
2-Nonanethiol C9H20S [9] 298.15–1000 NA NA NA 9 0.08 0.10 3.15 3.76
2-Thiadecane C9H20S [9] 298.15–1000 NA NA NA 9 0.11 0.14 4.38 5.16
3-Thiadecane C9H20S [9] 298.15–1000 NA NA NA 9 0.11 0.13 4.08 4.72
4-Thiadecane C9H20S [9] 298.15–1000 NA NA NA 9 0.11 0.13 4.08 4.72
5-Thiadecane C9H20S [9] 298.15–1000 NA NA NA 9 0.11 0.13 4.08 4.72
 g0
Compound Formula Ref. Temperature Eqa Kw (VMGSIM) SG (VMGSIM) ω (VMGSIM) cp values εb Fc, d ıed (%)  rel  rel
F
range/K (J K−1 g−1 ) (J K−1 g−1 ) (%)f ,g
1,2,4,5-Tetramethylbenzene C10H14 [9] 298.15–1000 NA NA NA 9 0.06 0.07 2.66 3.00
1,2-Diethylbenzene C10H14 [9] 298.15–1000 NA NA NA 9 0.05 0.06 2.05 2.46
1,3-Diethylbenzene C10H14 [9] 298.15–1000 NA NA NA 9 0.07 0.08 3.19 3.44
1,4-Diethylbenzene C10H14 [9] 298.15–1000 NA NA NA 9 0.08 0.09 3.60 3.89
Butylbenzene C10H14 [9] 298.15–1500 NA NA NA 14 0.04 0.05 2.12 2.84
1-Decyne C10H18 [9] 298.15–1500 NA NA NA 14 0.10 0.13 3.21 3.64
Decanenitrile C10H19N [9] 298.15–1500 NA NA NA 14 0.06 0.06 1.88 2.16
1-Decene C10H20 [9] 298.15–1500 NA NA NA 14 0.07 0.08 2.15 2.36
Decanal C10H20O [9] 298.15–1500 NA NA NA 13 0.07 0.08 2.42 2.72
2-Decanone C10H20O [9] 298.15–1000 NA NA NA 9 0.10 0.12 3.54 4.26
3-Decanone C10H20O [9] 298.15–1000 NA NA NA 9 0.10 0.12 3.51 4.01
4-Decanone C10H20O [9] 298.15–1000 NA NA NA 9 0.10 0.12 3.51 4.01
(3R,6S)-Dimethyloctane C10H22 [9] 298.15–1500 NA NA NA 14 0.06 0.08 1.57 1.92
(3RS)-Ethyl-2,(4RS)- C10H22 [9] 298.15–1500 NA NA NA 14 0.09 0.11 2.22 2.74
dimethylhexane
(3RS)-Ethyl-2,(4SR)- C10H22 [9] 298.15–1500 NA NA NA 14 0.09 0.11 2.30 2.75
dimethylhexane

V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370

(3RS,5RS)-Dimethyloctane C10H22 [9] 298.15–1500 NA NA NA 14 0.09 0.10 2.85 3.04
(4R,5S)-Dimethyloctane C10H22 [9] 298.15–1500 NA NA NA 14 0.07 0.08 1.86 2.12
(4RS)-Ethyl-3- C10H22 [9] 298.15–1500 NA NA NA 14 0.07 0.08 2.17 2.41
methylheptane
(4RS,5SR)-Dimethyloctane C10H22 [9] 298.15–1500 NA NA NA 14 0.07 0.09 1.90 2.19
2,(3RS,4RS)- C10H22 [9] 298.15–1500 NA NA NA 14 0.11 0.13 3.21 3.44
Trimethylheptane
2,(3RS,4SR),5- C10H22 [9] 298.15–1500 NA NA NA 14 0.14 0.17 4.19 4.47
Tetramethylhexane
2,(3RS,4SR)- C10H22 [9] 298.15–1500 NA NA NA 14 0.11 0.13 3.35 3.57
Trimethylheptane
2,(3RS,5RS)- C10H22 [9] 298.15–1500 NA NA NA 14 0.10 0.12 2.94 3.19
Trimethylheptane
2,(3RS,5SR)- C10H22 [9] 298.15–1500 NA NA NA 14 0.10 0.12 2.76 3.10
Trimethylheptane
2,(4RS,5RS)- C10H22 [9] 298.15–1500 NA NA NA 14 0.11 0.13 3.05 3.34
Trimethylheptane
2,(4RS,5SR)- C10H22 [9] 298.15–1500 NA NA NA 14 0.11 0.13 3.17 3.42
Trimethylheptane
2,2,(3RS,4RS)- C10H22 [9] 298.15–1500 NA NA NA 14 0.16 0.21 4.00 4.85
Tetramethylhexane
2,2,(3RS,4SR)- C10H22 [9] 298.15–1500 NA NA NA 14 0.16 0.21 4.00 4.85
Tetramethylhexane
3-Isopropyl-2-methylhexane C10H22 [9] 298.15–1000 NA NA NA 9 0.02 0.02 0.49 0.68
r-(3R),4,(5S)- C10H22 [9] 298.15–1500 NA NA NA 14 0.10 0.12 2.71 3.04
Trimethylheptane
s-(3R),4,(5S)- C10H22 [9] 298.15–1500 NA NA NA 14 0.11 0.12 3.14 3.38
Trimethylheptane
1-Decanol C10H22O [9] 298.15–1500 NA NA NA 14 0.10 0.12 3.33 3.52
1-Decanethiol C10H22S [9] 298.15–1000 NA NA NA 9 0.08 0.09 2.92 3.40
2-Decanethiol C10H22S [9] 298.15–1000 NA NA NA 9 0.08 0.10 3.05 3.69
2-Thiaundecane C10H22S [9] 298.15–1000 NA NA NA 9 0.11 0.14 4.29 4.98
3-Thiaundecane C10H22S [9] 298.15–1000 NA NA NA 9 0.10 0.13 4.04 4.59
4-Thiaundecane C10H22S [9] 298.15–1000 NA NA NA 9 0.10 0.13 4.04 4.59
5-Thiaundecane C10H22S [9] 298.15–1000 NA NA NA 9 0.10 0.13 4.04 4.59
6-Thiaundecane C10H22S [9] 298.15–1000 NA NA NA 9 0.10 0.13 4.04 4.59
6,7-Dithiadodecane C10H22S2 [9] 298.15–1000 NA NA NA 9 0.08 0.10 4.45 6.18
2-Naphthalenol C10H8O [9] 298.15–1500 NA NA NA 14 0.03 0.03 1.44 1.92
1-Methylnaphthalene C11H10 [9] 298.15–1000 NA NA NA 9 0.06 0.06 3.38 4.08
2-Methylnaphthalene C11H10 [9] 298.15–1000 NA NA NA 9 0.05 0.05 3.00 3.88
Pentylbenzene C11H16 [9] 298.15–1500 NA NA NA 14 0.05 0.06 2.52 3.17
Pentamethylbenzene C11H16 [9] 298.15–1500 NA NA NA 9 0.05 0.06 2.39 2.81
1-Undecyne C11H20 [9] 298.15–1500 NA NA NA 14 0.10 0.12 3.05 3.48

357
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Compound Formula Ref. Temperature Eqa Kw (VMGSIM) SG (VMGSIM) ω (VMGSIM) cp values εb Fc, d ıed (%)  rel  rel
F
range/K (J K−1 g−1 ) (J K−1 g−1 ) (%)f , g
Undecanenitrile C11H21N [9] 298.15–1500 NA NA NA 14 0.05 0.06 1.63 1.92
1-Undecene C11H22 [9] 298.15–1500 NA NA NA 14 0.07 0.08 2.02 2.26
n-Hexylcyclopentane C11H22 [9] 298.15–1500 NA NA NA 14 0.05 0.05 1.64 2.00
2-Undecanone C11H22O [9] 298.15–1000 NA NA NA 9 0.09 0.12 3.29 3.97
3-Undecanone C11H22O [9] 298.15–1000 NA NA NA 9 0.09 0.11 3.22 3.70
4-Undecanone C11H22O [9] 298.15–1000 NA NA NA 9 0.09 0.11 3.23 3.71
2,3-Dimethylnonane C11H24 [9] 298.15–1500 NA NA NA 14 0.05 0.07 1.41 1.65
2,4-Dimethylnonane C11H24 [9] 298.15–1500 NA NA NA 14 0.08 0.09 2.67 2.85
2,2-Dimethylnonane C11H24 [9] 298.15–1500 NA NA NA 14 0.10 0.12 2.88 3.12
2-Methyldecane C11H24 [9] 298.15–1500 NA NA NA 9 0.03 0.03 1.12 1.22
3-Methyldecane C11H24 [9] 298.15–1500 NA NA NA 14 0.03 0.04 1.01 1.10
n-Undecane C11H24 [9] 298.15–1000 NA NA NA 9 0.01 0.02 0.68 0.97
1-Undecanol C11H24O [9] 298.15–1500 NA NA NA 14 0.10 0.11 3.11 3.31
1-Undecanethiol C11H24S [9] 298.15–1000 NA NA NA 9 0.08 0.09 2.92 3.34
2-Undecanethiol C11H24S [9] 298.15–1000 NA NA NA 9 0.08 0.10 3.04 3.60
2-Thiadodecane C11H24S [9] 298.15–1000 NA NA NA 9 0.11 0.13 4.19 4.80

V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370

3-Thiadodecane C11H24S [9] 298.15–1000 NA NA NA 9 0.10 0.12 3.94 4.44
4-Thiadodecane C11H24S [9] 298.15–1000 NA NA NA 9 0.10 0.12 3.94 4.44
5-Thiadodecane C11H24S [9] 298.15–1000 NA NA NA 9 0.10 0.12 3.94 4.44
2,7-Dimethylnaphthalene C12H12 [9] 298.15–1000 NA NA NA 9 0.06 0.07 3.81 5.14
1,3-Dimethylnaphthalene C12H12 [9] 298.15–1000 NA NA NA 9 0.07 0.07 3.87 4.85
1,6-Dimethylnaphthalene C12H12 [9] 298.15–1000 NA NA NA 9 0.07 0.07 3.87 4.85
1,7-Dimethylnaphthalene C12H12 [9] 298.15–1000 NA NA NA 9 0.07 0.07 3.87 4.85
2,6-Dimethylnaphthalene C12H12 [9] 298.15–1000 NA NA NA 9 0.06 0.07 3.79 5.11
1,2-Dimethylnaphthalene C12H12 [9] 298.15–1000 NA NA NA 9 0.07 0.08 4.20 5.04
1,4-Dimethylnaphthalene C12H12 [9] 298.15–1000 NA NA NA 9 0.07 0.08 4.20 5.04
1,5-Dimethylnaphthalene C12H12 [9] 298.15–1000 NA NA NA 9 0.07 0.08 4.20 5.04
2,3-Dimethylnaphthalene C12H12 [9] 298.15–1000 NA NA NA 9 0.05 0.06 3.23 4.66
1-Ethylnaphthalene C12H12 [9] 298.15–1000 NA NA NA 9 0.07 0.08 4.11 4.89
2-Ethylnaphthalene C12H12 [9] 298.15–1000 NA NA NA 9 0.06 0.07 3.78 4.70
1,3,5-Triethylbenzene C12H18 [9] 298.15–1000 NA NA NA 9 0.08 0.09 3.61 3.90
n-Hexylbenzene C12H18 [9] 298.15–1500 NA NA NA 14 0.07 0.07 2.83 3.35
1-Dodecyne C12H22 [9] 298.15–1500 NA NA NA 14 0.10 0.12 2.92 3.35
Dodecanenitrile C12H23N [9] 298.15–1500 NA NA NA 14 0.04 0.05 1.41 1.71
n-Heptylcyclopentane C12H24 [9] 298.15–1500 NA NA NA 14 0.04 0.05 1.28 1.44
n-Hexylcyclohexane C12H24 [9] 298.15–1500 NA NA NA 14 0.04 0.04 1.58 2.21
1-Dodecene C12H24 [9] 298.15–1500 NA NA NA 14 0.07 0.08 1.91 2.19
2-Dodecanone C12H24O [9] 298.15–1000 NA NA NA 9 0.09 0.11 3.13 3.80
3-Dodecanone C12H24O [9] 298.15–1000 NA NA NA 9 0.08 0.10 3.00 3.46
4-Dodecanone C12H24O [9] 298.15–1000 NA NA NA 9 0.08 0.10 3.00 3.46
2,3-Dimethyldecane C12H26 [9] 298.15–1500 NA NA NA 14 0.04 0.05 1.22 1.40
2,4-Dimethyldecane C12H26 [9] 298.15–1500 NA NA NA 14 0.07 0.08 2.39 2.57
2-Methylundecane C12H26 [9] 298.15–1000 NA NA NA 9 0.03 0.03 1.05 1.17
3-Methylundecane C12H26 [9] 298.15–1500 NA NA NA 14 0.03 0.03 0.84 0.91
2,2-Dimethyldecane C12H26 [9] 298.15–1500 NA NA NA 14 0.09 0.10 2.58 2.76
n-Dodecane C12H26 [9] 298.15–1000 NA NA NA 9 0.01 0.02 0.67 0.95
1-Dodecanol C12H26O [9] 298.15–1500 NA NA NA 14 0.09 0.11 2.94 3.16
1-Dodecanethiol C12H26S [9] 298.15–1000 NA NA NA 9 0.07 0.09 2.88 3.25
2-Dodecanethiol C12H26S [9] 298.15–1000 NA NA NA 9 0.08 0.10 2.99 3.49
2-Thiatridecane C12H26S [9] 298.15–1000 NA NA NA 9 0.11 0.13 4.05 4.61
3-Thiatridecane C12H26S [9] 298.15–1000 NA NA NA 9 0.10 0.12 3.82 4.28
4-Thiatridecane C12H26S [9] 298.15–1000 NA NA NA 9 0.10 0.12 3.82 4.28
5-Thiatridecane C12H26S [9] 298.15–1000 NA NA NA 9 0.10 0.12 3.82 4.28
7-Thiatridecane C12H26S [9] 298.15–1000 NA NA NA 9 0.10 0.12 3.82 4.28
7,8-Dithiatetradecane C12H26S2 [9] 298.15–1000 NA NA NA 9 0.07 0.09 3.80 4.91
3-Methylbiphenyl C13H12 [9] 298.15–1500 NA NA NA 14 0.05 0.05 2.28 2.73
4-Methylbiphenyl C13H12 [9] 298.15–1500 NA NA NA 14 0.05 0.05 2.28 2.73
2-Methylbiphenyl C13H12 [9] 298.15–1500 NA NA NA 14 0.07 0.07 3.30 3.76
 g0
Compound Formula Ref. Temperature Eqa Kw (VMGSIM) SG (VMGSIM) ω (VMGSIM) cp values εb Fc, d ıed (%)  rel  rel
F
range/K (J K−1 g−1 ) (J K−1 g−1 ) (%)f, g
2-Methyl-6- C13H14 [9] 298.15–1000 NA NA NA 9 0.04 0.05 2.54 3.69
ethylnaphthalene
2-Methyl-7- C13H14 [9] 298.15–1000 NA NA NA 9 0.04 0.05 2.54 3.69
ethylnaphthalene
n-Heptylbenzene C13H20 [9] 298.15–1500 NA NA NA 14 0.07 0.08 3.01 3.45
1-Tridecyne C13H24 [9] 298.15–1500 NA NA NA 14 0.09 0.11 2.80 3.24
Tridecanenitrile C13H25N [9] 298.15–1500 NA NA NA 14 0.04 0.04 1.22 1.52
n-Heptylcyclohexane C13H26 [9] 298.15–1500 NA NA NA 14 0.03 0.04 1.31 1.93
n-Octylcyclopentane C13H26 [9] 298.15–1500 NA NA NA 14 0.04 0.05 1.00 1.19
1-Tridecene C13H26 [9] 298.15–1500 NA NA NA 14 0.06 0.08 1.82 2.14
3-Tridecanone C13H26O [9] 298.15–1000 NA NA NA 9 0.08 0.10 2.80 3.24
4-Tridecanone C13H26O [9] 298.15–1000 NA NA NA 9 0.08 0.10 2.80 3.24
2,2-Dimethylundecane C13H28 [9] 298.15–1500 NA NA NA 14 0.08 0.09 2.32 2.46
2,3-Dimethylundecane C13H28 [9] 298.15–1500 NA NA NA 14 0.04 0.05 1.08 1.19
2,4-Dimethylundecane C13H28 [9] 298.15–1500 NA NA NA 14 0.07 0.07 2.15 2.34

V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370

2-Methyldodecane C13H28 [9] 298.15–1000 NA NA NA 9 0.02 0.03 1.00 1.12
3-Methyldodecane C13H28 [9] 298.15–1500 NA NA NA 14 0.02 0.02 0.73 0.80
n-Tridecane C13H28 [9] 298.15–1000 NA NA NA 9 0.01 0.02 0.68 0.95
1-Tridecanol C13H28O [9] 298.15–1500 NA NA NA 14 0.09 0.11 2.78 3.02
1-Tridecanethiol C13H28S [9] 298.15–1000 NA NA NA 9 0.07 0.09 2.81 3.15
2-Tridecanethiol C13H28S [9] 298.15–1000 NA NA NA 9 0.08 0.10 2.92 3.38
2-Thiatetradecane C13H28S [9] 298.15–1000 NA NA NA 9 0.10 0.12 3.90 4.42
3-Thiatetradecane C13H28S [9] 298.15–1000 NA NA NA 9 0.10 0.12 3.69 4.12
4-Thiatetradecane C13H28S [9] 298.15–1000 NA NA NA 9 0.10 0.12 3.69 4.12
5-Thiatetradecane C13H28S [9] 298.15–1000 NA NA NA 9 0.10 0.12 3.69 4.12
2,2 -Dimethylbiphenyl C14H14 [9] 298.15–1500 NA NA NA 14 0.07 0.07 3.18 3.87
2,3 -Dimethylbiphenyl C14H14 [9] 298.15–1500 NA NA NA 14 0.06 0.07 2.93 3.42
2,4 -Dimethylbiphenyl C14H14 [9] 298.15–1500 NA NA NA 14 0.06 0.07 2.93 3.42
3,3 -Dimethylbiphenyl C14H14 [9] 298.15–1500 NA NA NA 14 0.04 0.05 2.01 2.51
3,4 -Dimethylbiphenyl C14H14 [9] 298.15–1500 NA NA NA 14 0.04 0.05 2.01 2.51
4,4 -Dimethylbiphenyl C14H14 [9] 298.15–1500 NA NA NA 14 0.04 0.05 2.01 2.51
2,3-Dimethylbiphenyl C14H14 [9] 298.15–1500 NA NA NA 14 0.07 0.07 3.18 3.87
2,5-Dimethylbiphenyl C14H14 [9] 298.15–1500 NA NA NA 14 0.06 0.07 2.93 3.42
2,6-Dimethylbiphenyl C14H14 [9] 298.15–1500 NA NA NA 14 0.07 0.07 3.18 3.87
3,5-Dimethylbiphenyl C14H14 [9] 298.15–1500 NA NA NA 14 0.04 0.05 2.01 2.51
2,4-Dimethylbiphenyl C14H14 [9] 298.15–1500 NA NA NA 14 0.06 0.07 2.93 3.42
3,4-Dimethylbiphenyl C14H14 [9] 298.15–1500 NA NA NA 14 0.05 0.06 2.53 3.51
2-Ethylbiphenyl C14H14 [9] 298.15–1500 NA NA NA 14 0.08 0.08 3.55 3.98
3-Ethylbiphenyl C14H14 [9] 298.15–1500 NA NA NA 14 0.06 0.06 2.64 3.05
4-Ethylbiphenyl C14H14 [9] 298.15–1500 NA NA NA 14 0.06 0.06 2.64 3.05
1,2,4,5-Tetraethylbenzene C14H22 [9] 298.15–1000 NA NA NA 9 0.13 0.15 5.08 5.73
n-Octylbenzene C14H22 [9] 298.15–1500 NA NA NA 14 0.08 0.08 3.12 3.48
1-Tetradecyne C14H26 [9] 298.15–1500 NA NA NA 14 0.09 0.11 2.69 3.14
Tetradecanenitrile C14H27N [9] 298.15–1500 NA NA NA 14 0.03 0.04 1.05 1.36
n-Nonylcyclopentane C14H28 [9] 298.15–1500 NA NA NA 14 0.04 0.05 1.00 1.23
n-Octylcyclohexane C14H28 [9] 298.15–1500 NA NA NA 14 0.02 0.03 1.09 1.68
1-Tetradecene C14H28 [9] 298.15–1500 NA NA NA 14 0.06 0.08 1.74 2.10
3-Tetradecanone C14H28O [9] 298.15–1000 NA NA NA 9 0.07 0.09 2.64 3.07
4-Tetradecanone C14H28O [9] 298.15–1000 NA NA NA 9 0.07 0.09 2.64 3.07
2,2-Dimethyldodecane C14H30 [9] 298.15–1500 NA NA NA 14 0.07 0.08 2.10 2.21
2,4-Dimethyldodecane C14H30 [9] 298.15–1500 NA NA NA 14 0.06 0.06 1.95 2.15
2,3-Dimethyldodecane C14H30 [9] 298.15–1500 NA NA NA 14 0.03 0.04 0.94 1.03
3-Methyltridecane C14H30 [9] 298.15–1500 NA NA NA 14 0.02 0.02 0.63 0.72
2-Methyltridecane C14H30 [9] 298.15–1000 NA NA NA 9 0.02 0.02 0.95 1.09
n-Tetradecane C14H30 [9] 298.15–1000 NA NA NA 9 0.02 0.03 0.85 1.04
1-Tetradecanol C14H30O [9] 298.15–1500 NA NA NA 14 0.09 0.10 2.64 2.91
2-Tetradecanethiol C14H30S [9] 298.15–1000 NA NA NA 9 0.08 0.09 2.83 3.26

359
 360
g0
Compound Formula Ref. Temperature Eqa Kw (VMGSIM) SG (VMGSIM) ω (VMGSIM) cp values εb Fc, d ıed (%)  rel  rel
F
range/K (J K−1 g−1 ) (J K−1 g−1 ) (%)f , g
1-Tetradecanethiol C14H30S [9] 298.15–1000 NA NA NA 9 0.07 0.08 2.73 3.05
2-Thiapentadecane C14H30S [9] 298.15–1000 NA NA NA 9 0.10 0.12 3.74 4.24
3-Thiapentadecane C14H30S [9] 298.15–1000 NA NA NA 9 0.09 0.11 3.55 3.96
4-Thiapentadecane C14H30S [9] 298.15–1000 NA NA NA 9 0.09 0.11 3.55 3.96
5-Thiapentadecane C14H30S [9] 298.15–1000 NA NA NA 9 0.09 0.11 3.55 3.96
8-Thiapentadecane C14H30S [9] 298.15–1000 NA NA NA 9 0.09 0.11 3.55 3.96
8,9-Dithiahexadecane C14H30S2 [9] 298.15–1000 NA NA NA 9 0.07 0.09 3.42 4.09
1-Pentylnaphthalene C15H18 [9] 298.15–1000 NA NA NA 9 0.05 0.05 2.49 3.14
n-Nonylbenzene C15H24 [9] 298.15–1500 NA NA NA 14 0.08 0.08 3.16 3.48
1-Pentadecyne C15H28 [9] 298.15–1500 NA NA NA 14 0.09 0.11 2.60 3.05
Pentadecanenitrile C15H29N [9] 298.15–1500 NA NA NA 14 0.03 0.03 0.93 1.22
n-Decylcyclopentane C15H30 [9] 298.15–1500 NA NA NA 14 0.04 0.05 1.21 1.42
n-Nonylcyclohexane C15H30 [9] 298.15–1500 NA NA NA 14 0.02 0.03 0.96 1.50

V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370

4-Pentadecanone C15H30O [9] 298.15–1000 NA NA NA 9 0.07 0.09 2.49 2.90
2,4-Dimethyltridecane C15H32 [9] 298.15–1500 NA NA NA 14 0.05 0.05 1.77 1.99
2,2-Dimethyltridecane C15H32 [9] 298.15–1500 NA NA NA 14 0.06 0.07 1.91 1.99
2,3-Dimethyltridecane C15H32 [9] 298.15–1500 NA NA NA 14 0.03 0.03 0.83 0.89
3-Methyltetradecane C15H32 [9] 298.15–1500 NA NA NA 14 0.01 0.02 0.55 0.69
2-Methyltetradecane C15H32 [9] 298.15–1000 NA NA NA 9 0.02 0.02 0.92 1.07
n-Pentadecane C15H32 [9] 298.15–1000 NA NA NA 9 0.02 0.02 0.71 0.95
1-Pentadecanol C15H32O [9] 298.15–1500 NA NA NA 14 0.08 0.10 2.52 2.82
1-Pentadecanethiol C15H32S [9] 298.15–1000 NA NA NA 9 0.07 0.08 2.64 2.94
2-Pentadecanethiol C15H32S [9] 298.15–1000 NA NA NA 9 0.07 0.09 2.74 3.15
2-Thiahexadecane C15H32S [9] 298.15–1000 NA NA NA 9 0.10 0.12 3.59 4.06
3-Thiahexadecane C15H32S [9] 298.15–1000 NA NA NA 9 0.09 0.11 3.41 3.80
4-Thiahexadecane C15H32S [9] 298.15–1000 NA NA NA 9 0.09 0.11 3.41 3.80
5-Thiahexadecane C15H32S [9] 298.15–1000 NA NA NA 9 0.09 0.11 3.41 3.80
Pentaethylbenzene C16H26 [9] 298.15–1000 NA NA NA 9 0.12 0.14 4.34 5.12
n-Decylbenzene C16H26 [9] 298.15–1500 NA NA NA 14 0.08 0.09 3.17 3.44
1-Hexadecyne C16H30 [9] 298.15–1500 NA NA NA 14 0.08 0.11 2.52 2.97
Hexadecanenitrile C16H31N [9] 298.15–1500 NA NA NA 14 0.02 0.03 0.84 1.09
n-Undecylcyclopentane C16H32 [9] 298.15–1500 NA NA NA 14 0.05 0.05 1.47 1.67
n-Decylcyclohexane C16H32 [9] 298.15–1500 NA NA NA 14 0.02 0.03 0.90 1.35
1-Hexadecene C16H32 [9] 298.15–1500 NA NA NA 14 0.06 0.08 1.61 2.05
4-Hexadecanone C16H32O [9] 298.15–1500 NA NA NA 14 0.11 0.13 3.23 3.69
2,4-Dimethyltetradecane C16H34 [9] 298.15–1500 NA NA NA 14 0.05 0.05 1.62 1.87
2,2-Dimethyltetradecane C16H34 [9] 298.15–1500 NA NA NA 14 0.06 0.06 1.74 1.81
2,3-Dimethyltetradecane C16H34 [9] 298.15–1500 NA NA NA 14 0.02 0.03 0.73 0.79
3-Methylpentadecane C16H34 [9] 298.15–1500 NA NA NA 14 0.01 0.02 0.49 0.67
2-Methylpentadecane C16H34 [9] 298.15–1000 NA NA NA 9 0.02 0.02 0.88 1.05
n-Hexadecane C16H34 [9] 298.15–1000 NA NA NA 9 0.01 0.02 0.58 0.89
1-Hexadecanol C16H34O [9] 298.15–1500 NA NA NA 14 0.08 0.10 2.42 2.74
1-Hexadecanethiol C16H34S [9] 298.15–1000 NA NA NA 9 0.07 0.08 2.55 2.84
2-Hexadecanethiol C16H34S [9] 298.15–1000 NA NA NA 9 0.07 0.09 2.64 3.03
2-Thiaheptadecane C16H34S [9] 298.15–1000 NA NA NA 9 0.09 0.11 3.44 3.89
3-Thiaheptadecane C16H34S [9] 298.15–1000 NA NA NA 9 0.09 0.10 3.27 3.65
4-Thiaheptadecane C16H34S [9] 298.15–1000 NA NA NA 9 0.09 0.10 3.27 3.65
5-Thiaheptadecane C16H34S [9] 298.15–1000 NA NA NA 9 0.09 0.10 3.27 3.65
9-Thiaheptadecane C16H34S [9] 298.15–1000 NA NA NA 9 0.09 0.10 3.27 3.65
9,10-Dithiaoctadecane C16H34S2 [9] 298.15–1000 NA NA NA 9 0.07 0.09 3.16 3.65
n-Undecylbenzene C17H28 [9] 298.15–1500 NA NA NA 14 0.08 0.09 3.16 3.40
1-Heptadecyne C17H32 [9] 298.15–1500 NA NA NA 14 0.08 0.10 2.46 2.92
Heptadecanenitrile C17H33N [9] 298.15–1500 NA NA NA 14 0.02 0.03 0.79 1.00
 g0
Compound Formula Ref. Temperature Eqa Kw (VMGSIM) SG (VMGSIM) ω (VMGSIM) cp values εb Fc, d ıed (%)  rel  rel
F
range/K (J K−1 g−1 ) (J K−1 g−1 ) (%)f , g
n-Dodecylcyclopentane C17H34 [9] 298.15–1500 NA NA NA 14 0.05 0.06 1.71 1.93
n-Undecylcyclohexane C17H34 [9] 298.15–1500 NA NA NA 14 0.02 0.03 0.86 1.24
1-Heptadecene C17H34 [9] 298.15–1500 NA NA NA 14 0.06 0.08 1.58 2.03
2,2-Dimethylpentadecane C17H36 [9] 298.15–1500 NA NA NA 14 0.05 0.05 1.59 1.66
2,3-Dimethylpentadecane C17H36 [9] 298.15–1500 NA NA NA 14 0.02 0.02 0.65 0.72
2,4-Dimethylpentadecane C17H36 [9] 298.15–1500 NA NA NA 14 0.04 0.04 1.48 1.76
3-Methylhexadecane C17H36 [9] 298.15–1500 NA NA NA 14 0.01 0.02 0.52 0.68
2-Methylhexadecane C17H36 [9] 298.15–1000 NA NA NA 9 0.02 0.02 0.86 1.04
n-Heptadecane C17H36 [9] 298.15–1000 NA NA NA 9 0.02 0.02 0.75 0.96
Heptadecanol C17H36O [9] 298.15–1500 NA NA NA 14 0.08 0.10 2.32 2.66
1-Heptadecanethiol C17H36S [9] 298.15–1000 NA NA NA 9 0.07 0.08 2.46 2.73
2-Heptadecanethiol C17H36S [9] 298.15–1000 NA NA NA 9 0.07 0.09 2.54 2.93
2-Thiaoctadecane C17H36S [9] 298.15–1000 NA NA NA 9 0.09 0.11 3.30 3.74
3-Thiaoctadecane C17H36S [9] 298.15–1000 NA NA NA 9 0.08 0.10 3.14 3.51
4-Thiaoctadecane C17H36S [9] 298.15–1000 NA NA NA 9 0.08 0.10 3.14 3.51
5-Thiaoctadecane C17H36S [9] 298.15–1000 NA NA NA 9 0.08 0.10 3.14 3.51
Dodecylbenzene C18H30 [9] 298.15-1500 NA NA NA 14 0.08 0.09 3.12 3.34
1-Octadecyne C18H34 [9] 298.15–1500 NA NA NA 14 0.08 0.10 2.40 2.86

V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370

Octadecanenitrile C18H35N [9] 298.15–1500 NA NA NA 14 0.02 0.03 0.72 0.91
n-Dodecylcyclohexane C18H36 [9] 298.15–1500 NA NA NA 14 0.02 0.03 0.83 1.15
Tridecylcyclopentane C18H36 [9] 298.15–1500 NA NA NA 14 0.06 0.06 1.91 2.18
1-Octadecene C18H36 [9] 298.15–1500 NA NA NA 14 0.06 0.08 1.56 2.02
2,3-Dimethylhexadecane C18H38 [9] 298.15–1500 NA NA NA 14 0.02 0.02 0.57 0.67
2,4-Dimethylhexadecane C18H38 [9] 298.15–1500 NA NA NA 14 0.04 0.04 1.36 1.68
2,2-Dimethylhexadecane C18H38 [9] 298.15–1500 NA NA NA 14 0.04 0.05 1.45 1.53
3-Methylheptadecane C18H38 [9] 298.15–1500 NA NA NA 14 0.02 0.02 0.58 0.70
2-Methylheptadecane C18H38 [9] 298.15–1000 NA NA NA 9 0.02 0.02 0.85 1.03
n-Octadecane C18H38 [9] 298.15–1000 NA NA NA 9 0.02 0.02 0.76 0.97
1-Octadecanol C18H38O [9] 298.15–1500 NA NA NA 14 0.08 0.10 2.26 2.63
1-Octadecanethiol C18H38S [9] 298.15–1000 NA NA NA 9 0.06 0.08 2.37 2.63
2-Octadecanethiol C18H38S [9] 298.15–1000 NA NA NA 9 0.07 0.08 2.45 2.82
2-Thianonadecane C18H38S [9] 298.15–1000 NA NA NA 9 0.09 0.10 3.17 3.59
3-Thianonadecane C18H38S [9] 298.15–1000 NA NA NA 9 0.08 0.10 3.02 3.37
4-Thianonadecane C18H38S [9] 298.15–1000 NA NA NA 9 0.08 0.10 3.02 3.37
5-Thianonadecane C18H38S [9] 298.15–1000 NA NA NA 9 0.08 0.10 3.02 3.37
10-Thianonadecane C18H38S [9] 298.15–1000 NA NA NA 9 0.08 0.10 3.02 3.37
10,11-Dithiaeicosane C18H38S2 [9] 298.15–1000 NA NA NA 9 0.07 0.09 2.95 3.45
Tridecylbenzene C19H32 [9] 298.15–1500 NA NA NA 14 0.08 0.09 3.08 3.28
1-Nonadecyne C19H36 [9] 298.15–1500 NA NA NA 14 0.08 0.10 2.34 2.81
Nonadecanenitrile C19H37N [9] 298.15–1500 NA NA NA 14 0.02 0.02 0.67 0.84
Tetradecylcyclopentane C19H38 [9] 298.15–1500 NA NA NA 14 0.06 0.07 2.09 2.40
Tridecylcyclohexane C19H38 [9] 298.15–1500 NA NA NA 14 0.02 0.03 0.81 1.10
2,2-Dimethylheptadecane C19H40 [9] 298.15–1500 NA NA NA 14 0.04 0.04 1.34 1.43
2,3-Dimethylheptadecane C19H40 [9] 298.15–1500 NA NA NA 14 0.01 0.02 0.50 0.65
2,4-Dimethylheptadecane C19H40 [9] 298.15–1500 NA NA NA 14 0.03 0.04 1.25 1.61
2-Methyloctadecane C19H40 [9] 298.15–1000 NA NA NA 9 0.02 0.02 0.84 1.03
3-Methyloctadecane C19H40 [9] 298.15–1500 NA NA NA 14 0.02 0.02 0.62 0.74
n-Nonadecane C19H40 [9] 298.15–1000 NA NA NA 9 0.02 0.02 0.77 0.96
1-Nonadecanol C19H40O [9] 298.15–1500 NA NA NA 14 0.07 0.09 2.17 2.56
1-Nonadecanethiol C19H40S [9] 298.15–1000 NA NA NA 9 0.06 0.07 2.28 2.54
2-Nonadecanethiol C19H40S [9] 298.15–1000 NA NA NA 9 0.07 0.08 2.35 2.72
2-Thiaicosane C19H40S [9] 298.15–1000 NA NA NA 9 0.08 0.10 3.04 3.45
3-Thiaicosane C19H40S [9] 298.15–1000 NA NA NA 9 0.08 0.09 2.90 3.25
4-Thiaicosane C19H40S [9] 298.15–1000 NA NA NA 9 0.08 0.09 2.90 3.25
5-Thiaicosane C19H40S [9] 298.15–1000 NA NA NA 9 0.08 0.09 2.90 3.25
Tetradecylbenzene C20H34 [9] 298.15–1500 NA NA NA 14 0.08 0.09 3.03 3.21
1-Eicosyne C20H38 [9] 298.15–1500 NA NA NA 14 0.08 0.10 2.29 2.77
Icosanenitrile C20H39N [9] 298.15–1500 NA NA NA 14 0.02 0.02 0.64 0.79
1-Eicosene C20H40 [9] 298.15–1500 NA NA NA 14 0.06 0.08 1.54 2.00
Pentadecylcyclopentane C20H40 [9] 298.15–1500 NA NA NA 14 0.07 0.07 2.24 2.61
Tetradecylcyclohexane C20H40 [9] 298.15–1500 NA NA NA 14 0.02 0.03 0.81 1.07

361
2,2-Dimethyloctadecane C20H42 [9] 298.15–1500 NA NA NA 14 0.04 0.04 1.22 1.34
 362
g0
Compound Formula Ref. Temperature Eqa Kw (VMGSIM) SG (VMGSIM) ω (VMGSIM) cp values εb Fc, d ıed (%)  rel  rel
F
range/K (J K−1 g−1 ) (J K−1 g−1 ) (%)f, g
2,3-Dimethyloctadecane C20H42 [9] 298.15–1500 NA NA NA 14 0.01 0.02 0.48 0.64
2,4-Dimethyloctadecane C20H42 [9] 298.15–1500 NA NA NA 14 0.03 0.04 1.15 1.55
2-Methylnonadecane C20H42 [9] 298.15–1000 NA NA NA 9 0.02 0.02 0.84 1.03
3-Methylnonadecane C20H42 [9] 298.15–1500 NA NA NA 14 0.02 0.02 0.67 0.78
n-Eicosane C20H42 [9] 298.15–1000 NA NA NA 9 0.02 0.02 0.78 0.98
1-Eicosanol C20H42O [9] 298.15–1500 NA NA NA 14 0.07 0.10 2.14 2.58
1-Eicosanethiol C20H42S [9] 298.15–1000 NA NA NA 9 0.06 0.07 2.20 2.45
2-Thiahenicosane C20H42S [9] 298.15–1000 NA NA NA 9 0.08 0.10 2.92 3.32
3-Thiahenicosane C20H42S [9] 298.15–1000 NA NA NA 9 0.08 0.09 2.78 3.13
4-Thiahenicosane C20H42S [9] 298.15–1000 NA NA NA 9 0.08 0.09 2.78 3.13
5-Thiahenicosane C20H42S [9] 298.15–1000 NA NA NA 9 0.08 0.09 2.78 3.13
11-Thiahenicosane C20H42S [9] 298.15–1000 NA NA NA 9 0.08 0.09 2.78 3.13
11,12-Dithiadocosane C20H42S2 [9] 298.15–1000 NA NA NA 9 0.07 0.09 2.86 3.36
n-Pentadecylbenzene C21H36 [9] 298.15–1500 NA NA NA 14 0.08 0.09 2.98 3.15
Henicosanenitrile C21H41N [9] 298.15–1500 NA NA NA 14 0.02 0.02 0.61 0.75
Hexadecylcyclopentane C21H42 [9] 298.15–1500 NA NA NA 14 0.07 0.07 2.39 2.80
Pentadecylcyclohexane C21H42 [9] 298.15–1500 NA NA NA 14 0.02 0.03 0.81 1.06

V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370

Dibenzo[c,g]phenanthrene C22H14 [9] 298.15–1500 NA NA NA 14 0.05 0.05 2.70 3.38
Hexadecylbenzene C22H38 [9] 298.15–1500 NA NA NA 14 0.08 0.09 2.93 3.09
Hexadecylcyclohexane C22H44 [9] 298.15–1500 NA NA NA 14 0.02 0.03 0.80 1.05
Hexacyclo- C36H12 [9] 298.15–1500 NA NA NA 14 0.10 0.11 5.37 6.45
penta[bc,ef,hi,kl,no,qr]coronene

Training Set 2
Bicyclo[530]decane C10H18 [24] 298.15–1000 NA NA NA 16 0.080 0.132 3.43 5.84
1,5-Methano(10)-annulene C11H10 [24] 298.15–1000 NA NA NA 16 0.014 0.025 0.88 1.75
1,6-Methano(10)-annulene C11H10 [24] 298.15–1000 NA NA NA 16 0.006 0.014 0.43 1.12
Tricyclo[33113,7]decane, C13H22 [24] 298.15–1000 NA NA NA 16 0.067 0.142 2.34 4.58
1-ethyl-3-methyl-
(E,E)-2,6,6,9-Tetramethyl- C15H26 [24] 298.15–1000 NA NA NA 16 0.045 0.080 2.18 4.59
1,4-cycloundecadiene
Perhydropyrene C16H26 [24] 298.15–1000 NA NA NA 16 0.053 0.091 2.40 4.43
Thiacycloeicosane C19H38S [24] 298.15–1000 NA NA NA 16 0.054 0.099 2.72 5.76
10,10,13,13- C20H32 [24] 298.15–1000 NA NA NA 16 0.099 0.168 4.57 8.87
Tetramethylcyclohexadeca-
1,5-diyne
1,11-Cycloeicosanedione C20H36O2 [24] 298.15–1000 NA NA NA 16 0.078 0.176 2.60 5.36
Cyclodocosane C22H44 [24] 298.15–1000 NA NA NA 16 0.047 0.099 1.51 2.86

Test Set 2, Comparison Set 2

cis,cis-7- C10H18 [24] 300–1000 This work 10.820 0.8614 0.306 6 0.07 0.09 2.95 3.31
Methylbicyclo[430]nonane
300–900 LK1 6 0.13 0.19 4.73 6.08
300–900 CF1 = 0 6 0.16 0.20 5.67 6.93
300–900 LK2 6 0.06 0.08 2.24 2.67
300–900 CF2 = 0 6 0.22 0.29 7.80 9.63
300–1000 HS 6 0.08 0.10 4.11 5.38

Propylcyclooctane C11H22 [24] 300–1000 This work 10.850 0.8717 0.471 6 0.04 0.06 1.37 1.75
300–900 LK1 6 0.28 0.35 10.49 11.75
300–900 CF1 = 0 6 0.30 0.36 11.24 12.49
300–900 LK2 6 0.33 0.41 12.16 13.72
300–900 CF2 = 0 6 0.36 0.44 13.26 14.91
300–1000 HS 6 0.07 0.09 2.78 3.32
Cyclododecyne C12H20 [24] 300–1000 This work 11.133 0.8810 0.279 6 0.02 0.02 0.82 1.18
300–900 LK1 6 0.07 0.12 2.57 3.65
300–900 CF1 = 0 6 0.07 0.12 2.52 3.59
300–900 LK2 6 0.15 0.18 6.15 6.90
300–900 CF2 = 0 6 0.13 0.20 4.42 6.30
300–1000 HS 6 0.08 0.12 3.08 3.98

Perhydrophenanthrene C14H24 [24] 300–1000 This work 10.766 0.9302 0.409 6 0.05 0.05 2.20 2.65
 g0
Compound Formula Ref. Temperature Eqa Kw (VMGSIM) SG (VMGSIM) ω (VMGSIM) cp values εb Fc, d ıed (%)  rel  rel
F
range/K (J K−1 g−1 ) (J K−1 g−1 ) (%)f , g
300–900 LK1 6 0.15 0.21 5.37 6.85
300–900 CF1 = 0 6 0.15 0.19 5.32 6.55
300–900 LK2 6 0.16 0.21 5.72 7.08
300–900 CF2 = 0 6 0.20 0.28 7.33 9.25
300–1000 HS 6 0.09 0.10 4.16 5.33

1,1 -Bicycloheptyl C14H26 [24] 300–1000 This work 11.362 0.8863 0.363 6 0.02 0.03 1.25 1.67
300–900 LK1 6 0.11 0.16 3.97 5.26
300–900 CF1 = 0 6 0.12 0.16 4.17 5.26
300–900 LK2 6 0.08 0.10 3.30 4.19
300–900 CF2 = 0 6 0.17 0.25 5.85 7.74
300–1000 HS 6 0.10 0.13 4.22 5.16

Hexadecahydrofluoranthene C16H26 [24] 300–1000 This work 10.684 0.9603 0.457 6 0.05 0.06 2.45 3.08
300–900 LK1 6 0.13 0.17 4.95 5.99
300–900 CF1 = 0 6 0.12 0.15 4.55 5.33
300–900 LK2 6 0.15 0.20 5.83 7.02
300–900 CF2 = 0 6 0.17 0.23 6.59 8.01

V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370

300–1000 HS 6 0.08 0.09 4.07 5.53

1,1 -Bicyclooctyl C16H30 [24] 300–1000 This work 11.458 0.9062 0.397 6 0.02 0.02 0.93 1.12
300–900 LK1 6 0.12 0.18 4.19 5.57
300–900 CF1 = 0 6 0.12 0.17 4.22 5.35
300–900 LK2 6 0.11 0.15 4.02 5.17
300–900 CF2 = 0 6 0.18 0.26 5.90 7.83
300–1000 HS 6 0.10 0.14 3.96 4.92

Cycloheptadecanone C17H32O [24] 300–1000 This work 11.014 0.9252 0.482 6 0.05 0.08 1.49 2.18
300–900 LK1 6 0.16 0.25 5.01 7.54
300–900 CF1 = 0 6 0.15 0.24 4.96 7.11
300–900 LK2 6 0.19 0.29 6.21 8.77
300–900 CF2 = 0 6 0.22 0.32 7.07 9.77
300–1000 HS 6 0.12 0.18 4.49 5.74

Octadecahydrotriphenylene C18H30 [24] 300–1000 This work 11.464 0.9214 0.487 6 0.03 0.03 1.27 1.68
300–900 LK1 6 0.08 0.10 4.43 6.27
300–900 CF1 = 0 6 0.06 0.09 3.86 6.06
300–900 LK2 6 0.09 0.11 4.67 6.72
300–900 CF2 = 0 6 0.09 0.12 4.47 6.13
300–1000 HS 6 0.08 0.09 3.53 4.46

1,1- C18H36 [24] 300–1000 This work 10.894 0.9072 0.393 6 0.03 0.04 0.90 1.18
Dimethylcyclohexadecane
300–900 LK1 6 0.35 0.44 12.19 13.89
300–900 CF1 = 0 6 0.35 0.43 12.41 14.01
300–900 LK2 6 0.34 0.42 11.82 13.49
300–900 CF2 = 0 6 0.41 0.52 14.38 16.42
300–1000 HS 6 0.11 0.16 3.39 4.54

3-Decylbicyclo[440]decane C20H38 [24] 300–1000 This work 12.665 0.8457 0.698 6 0.08 0.10 3.12 3.96
300–900 LK1 6 0.18 0.20 7.58 8.51
300–900 CF1 = 0 6 0.18 0.20 7.55 8.48
300–900 LK2 6 0.11 0.12 5.08 6.52
300–900 CF2 = 0 6 0.11 0.12 5.10 6.52
300–1000 HS 6 0.03 0.04 1.19 1.51

1,1,4,4- C20H40 [24] 300–1000 This work 10.948 0.9122 0.416 6 0.05 0.05 2.02 2.50
Tetramethylcyclohexadecane
300–900 LK1 6 0.36 0.44 12.72 14.27
300–900 CF1 = 0 6 0.36 0.43 12.87 14.32
300–900 LK2 6 0.36 0.44 12.69 14.25
300–900 CF2 = 0 6 0.42 0.52 14.84 16.69
300–1000 HS 6 0.09 0.16 2.73 4.20

363
 364
g0
Compound Formula Ref. Temperature Eqa Kw (VMGSIM) SG (VMGSIM) ω (VMGSIM) cp values εb Fc, d ıed (%)  rel  rel
F
range/K (J K−1 g−1 ) (J K−1 g−1 ) (%)f, g
1,2-Bis(decahydro-1- C22H38 [24] 300–1000 This work 11.787 0.9398 0.595 6 0.02 0.02 0.98 1.25
naphthyl)ethane
300–900 LK1 6 0.07 0.09 3.60 5.10
300–900 CF1 = 0 6 0.07 0.08 3.56 5.10
300–900 LK2 6 0.09 0.11 4.13 5.55
300–900 CF2 = 0 6 0.08 0.10 3.68 4.95
300–1000 HS 6 0.06 0.08 2.00 2.64

Cyclooctacosane C28H56 [24] 300–1000 This work 12.855 0.8247 0.511 6 0.05 0.08 1.42 2.04
300–900 LK1 6 0.16 0.20 7.93 11.11
300–900 CF1 = 0 6 0.16 0.20 7.93 11.11
300–900 LK2 6 0.18 0.21 8.25 10.70
300–900 CF2 = 0 6 0.18 0.21 8.25 10.69
300–1000 HS 6 0.13 0.20 4.37 5.65

5,5,8,8,16,16,19,19- C30H56O2 [24] 300–1000 This work 11.008 0.9756 0.635 6 0.11 0.12 4.71 5.56
Octamethylcyclodocosane-
1,12-dione
300–900 LK1 6 0.24 0.30 9.12 10.32

V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370

300–900 CF1 = 0 6 0.21 0.26 8.16 9.13
300–900 LK2 6 0.28 0.36 10.41 11.98
300–900 CF2 = 0 6 0.28 0.35 10.25 11.65
300–1000 HS 6 0.13 0.19 4.74 5.85

1,1,4,4,12,12,15,15- C30H60 [24] 300–1000 This work 11.084 0.9533 0.487 6 0.08 0.09 3.45 4.21
Octamethylcyclodocosane
300–900 LK1 6 0.37 0.45 13.27 14.80
300–900 CF1 = 0 6 0.35 0.42 12.72 14.09
300–900 LK2 6 0.39 0.47 13.62 15.29
300–900 CF2 = 0 6 0.42 0.51 14.70 16.45
300–1000 HS 6 0.12 0.17 3.83 4.90

1,1-Bis(decahydro-1- C31H56 [24] 300–1000 This work 12.877 0.9320 0.700 6 0.06 0.07 2.70 3.42
naphthyl)undecane
300–900 LK1 6 0.26 0.28 10.97 12.38
300–900 CF1 = 0 6 0.26 0.28 10.97 12.38
300–900 LK2 6 0.18 0.20 8.45 10.30
300–900 CF2 = 0 6 0.18 0.20 8.45 10.30
300–1000 HS 6 0.05 0.06 1.77 2.14

Comparison Set 1
1,5-Diaminonaphthalene C10H10N2 [24] 300–1000 This work 8.377 1.2409 0.807 6 0.05 0.07 3.74 5.80
300–900 LK1 6 7.54 9.17 382.3 436.5
300–900 CF1 = 0 6 0.39 0.43 22.68 25.61
300–900 LK2 6 0.79 0.99 39.50 45.97
300–900 CF2 = 0 6 0.43 0.48 24.46 27.24
300–1000 HS 6 0.01 0.02 0.76 1.26

2-Decanethiol C10H22S [24] 300–1000 This work 11.804 0.8187 0.506 6 0.09 0.11 3.59 4.39
300–900 LK1 6 0.22 0.28 8.44 10.17
300–900 CF1 = 0 6 0.18 0.24 7.01 8.70
300–900 LK2 6 0.14 0.17 5.38 6.32
300–900 CF2 = 0 6 0.12 0.15 4.50 5.47
300–1000 HS 6 0.05 0.07 3.00 4.51

6,7-Dithiadodecane C10H22S2 [24] 300–1000 This work 10.983 0.9003 0.614 6 0.05 0.08 3.04 5.29
300–900 LK1 6 0.21 0.27 8.96 11.01
300–900 CF1 = 0 6 0.20 0.27 8.53 10.75
300–900 LK2 6 0.13 0.17 5.66 7.01
300–900 CF2 = 0 6 0.14 0.18 6.09 7.47
300–1000 HS 6 0.08 0.09 4.31 5.70

2-(p-Nitrophenyl)pyridine C11H8N2O2 [24] 300–1000 This work 8.510 1.2779 0.689 6 0.07 0.08 4.03 4.65
300–900 LK1 6 6.01 7.31 353.3 403.6
300–900 CF1 = 0 6 0.09 0.12 7.16 10.25
 g0
Compound Formula Ref. Temperature Eqa Kw (VMGSIM) SG (VMGSIM) ω (VMGSIM) cp values εb Fc, d ıed (%)  rel  rel
F
range/K (J K−1 g−1 ) (J K−1 g−1 ) (%)f ,g
300–900 LK2 6 0.32 0.43 17.31 22.01
300–900 CF2 = 0 6 0.13 0.15 9.29 11.40
300–1000 HS 6 0.02 0.02 1.23 1.42

Dibenzothiophene C12H8S [24] 300–1000 This work 8.947 1.1496 0.398 6 0.13 0.15 8.98 10.13
300–900 LK1 6 1.13 1.40 68.48 78.95
300–900 CF1 = 0 6 0.13 0.17 8.03 9.56
300–900 LK2 6 0.48 0.61 29.27 33.83
300–900 CF2 = 0 6 0.09 0.11 5.56 6.43
300–1000 HS 6 0.05 0.06 3.97 5.94

1,3,5-Triethylbenzene C12H18 [24] 300–1000 This work 11.012 0.8703 0.479 6 0.08 0.10 3.72 4.16
300–900 LK1 6 0.06 0.08 2.61 3.16
300–900 CF1 = 0 6 0.05 0.07 2.31 2.90
300–900 LK2 6 0.02 0.03 1.16 1.56
300–900 CF2 = 0 6 0.04 0.04 1.97 2.51
300–1000 HS 6 0.03 0.04 1.47 2.19

1,1-Difluorododecane C12H24F2 [24] 300–1000 This work 11.119 0.8638 0.557 6 0.07 0.09 2.89 3.37

V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370

300–900 LK1 6 0.10 0.12 4.11 4.98
300–900 CF1 = 0 6 0.08 0.11 3.60 4.57
300–900 LK2 6 0.03 0.05 1.86 2.73
300–900 CF2 = 0 6 0.04 0.06 2.28 3.35
300–1000 HS 6 0.04 0.06 2.43 3.92

N,N-Dimethylundecanamide C13H27NO [24] 300–1000 This work 10.788 0.9389 0.765 6 0.04 0.05 1.58 1.87
300–900 LK1 6 0.23 0.26 10.31 11.89
300–900 CF1 = 0 6 0.22 0.25 10.02 11.71
300–900 LK2 6 0.30 0.33 12.63 13.97
300–900 CF2 = 0 6 0.28 0.31 12.14 13.56
300–1000 HS 6 0.08 0.10 3.90 5.34

9,10-Phenanthrenedione C14H8O2 [24] 300–1000 This work 8.307 1.3159 0.733 6 0.03 0.04 2.09 2.57
300–900 LK1 6 10.41 12.66 594.2 678.8
300–900 CF1 = 0 6 0.21 0.23 14.28 16.84
300–900 LK2 6 0.58 0.78 30.85 38.84
300–900 CF2 = 0 6 0.25 0.27 16.23 18.46
300–1000 HS 6 0.04 0.05 2.06 2.84

1-Pentylnaphthalene C15H18 [24] 300–1000 This work 10.760 0.9429 0.575 6 0.04 0.05 2.43 3.10
300–900 LK1 6 0.08 0.12 3.40 4.52
300–900 CF1 = 0 6 0.10 0.14 3.76 5.19
300–900 LK2 6 0.04 0.05 1.49 1.97
300–900 CF2 = 0 6 0.04 0.06 1.43 2.07
300–1000 HS 6 0.03 0.04 1.77 2.64

Naphtho[1,2- C16H10S [24] 300–1000 This work 8.589 1.2495 0.534 6 0.07 0.10 4.10 5.08
b]thianaphthene
300–900 LK1 6 4.61 5.61 271.6 310.6
300–900 CF1 = 0 6 0.09 0.11 6.78 9.44
300–900 LK2 6 0.03 0.04 1.41 1.85
300–900 CF2 = 0 6 0.10 0.12 7.58 10.06
300–1000 HS 6 0.02 0.03 1.31 1.78

2-Ethyl-9,10- C16H12O2 [24] 300–1000 This work 8.749 1.2781 0.830 6 0.04 0.06 3.09 4.70
anthracenedione
300–900 LK1 6 3.51 4.25 187.5 212.8
300–900 CF1 = 0 6 0.17 0.19 11.19 13.54
300–900 LK2 6 0.40 0.50 21.46 24.51
300–900 CF2 = 0 6 0.22 0.24 13.24 15.17
300–1000 HS 6 0.04 0.06 2.57 3.40

5-(2- C16H18 [24] 300–1000 This work 10.017 1.0396 0.634 6 0.03 0.03 1.68 2.10
Methylpropyl)acenaphthene
300–900 LK1 6 0.05 0.06 3.02 4.14

365
300–900 CF1 = 0 6 0.05 0.06 3.02 4.14
 366
g0
Compound Formula Ref. Temperature Eqa Kw (VMGSIM) SG (VMGSIM) ω (VMGSIM) cp values εb Fc, d ıed (%)  rel  rel
F
range/K (J K−1 g−1 ) (J K−1 g−1 ) (%)f , g
300–900 LK2 6 0.10 0.11 5.08 5.69
300–900 CF2 = 0 6 0.10 0.11 5.08 5.69
300–1000 HS 6 0.01 0.02 0.65 0.76

1,4,5- C17H16 [24] 300–1000 This work 10.267 1.0337 0.572 6 0.08 0.09 4.66 5.80
Trimethylphenanthrene
300–900 LK1 6 0.11 0.15 4.86 6.26
300–900 CF1 = 0 6 0.12 0.16 5.33 6.82
300–900 LK2 6 0.06 0.09 2.91 3.64
300–900 CF2 = 0 6 0.06 0.09 2.88 3.65
300–1000 HS 6 0.02 0.03 1.16 2.08

1-[2-Methyl-1-(1- C17H20 [24] 300–1000 This work 10.963 0.9501 0.595 6 0.06 0.07 2.99 3.80
methylethyl)-1-
propenyl]naphthalene
300–900 LK1 6 0.14 0.17 6.40 7.26
300–900 CF1 = 0 6 0.16 0.20 7.01 8.02
300–900 LK2 6 0.10 0.11 4.57 5.03
300–900 CF2 = 0 6 0.10 0.11 4.52 5.02

V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370

300–1000 HS 6 0.03 0.05 1.90 2.86

4-Cyano-2-fluorophenyl-4- C19H18FNO2 [24] 300–1000 This work 9.058 1.2782 1.030 6 0.07 0.09 4.81 7.46
pentylbenzoate
300–900 LK1 6 1.53 1.81 80.42 90.12
300–900 CF1 = 0 6 0.12 0.15 8.15 11.52
300–900 LK2 6 0.27 0.31 15.09 16.65
300–900 CF2 = 0 6 0.17 0.19 10.31 12.69
300–1000 HS 6 0.05 0.06 3.31 4.87

1-Nonadecanethiol C19H40S [24] 300–1000 This work 9.774 1.0754 0.807 6 0.05 0.07 2.14 2.66
300–900 LK1 6 0.55 0.61 23.24 25.78
300–900 CF1 = 0 6 0.53 0.59 22.61 25.13
300–900 LK2 6 0.59 0.65 24.52 27.03
300–900 CF2 = 0 6 0.58 0.65 24.42 26.93
300–1000 HS 6 0.07 0.09 3.47 5.16

Benz[a]anthracene, C20H16 [24] 300–1000 This work 9.900 1.1094 0.650 6 0.07 0.08 4.54 5.79
9,10-dimethyl-
300–900 LK1 6 0.10 0.14 4.54 6.00
300–900 CF1 = 0 6 0.10 0.14 4.68 6.18
300–900 LK2 6 0.05 0.07 2.46 3.10
300–900 CF2 = 0 6 0.05 0.07 2.48 3.13
300–1000 HS 6 0.01 0.03 1.14 2.21

Pyrene, 4,5-Diethyl- C20H18 [24] 300–1000 This work 10.490 1.0483 0.681 6 0.07 0.08 4.08 5.48
300–900 LK1 6 0.20 0.25 9.54 11.00
300–900 CF1 = 0 6 0.23 0.28 10.94 12.67
300–900 LK2 6 0.16 0.20 8.15 9.12
300–900 CF2 = 0 6 0.17 0.21 8.34 9.41
300–1000 HS 6 0.03 0.03 1.55 2.17

Sulfide, butyl hexadecyl C20H42S [24] 300–1000 This work 9.172 1.1612 0.795 6 0.05 0.07 2.16 2.68
300–900 LK1 1.40 1.61 55.46 60.98
300–900 CF1 = 0 0.74 0.82 30.82 34.03
300–900 LK2 0.84 0.96 34.33 37.64
300–900 CF2 = 0 0.78 0.87 32.43 35.67
300–1000 HS 0.07 0.09 3.38 4.88

11,12-Dithiadocosane C20H42S2 [24] 300–1000 This work 12.225 0.8677 0.830 6 0.05 0.07 2.30 2.69
300–900 LK1 0.31 0.37 12.41 14.09
300–900 CF1 = 0 0.30 0.36 12.09 13.76
300–900 LK2 0.22 0.25 9.06 10.03
300–900 CF2 = 0 0.23 0.27 9.46 10.55
300–1000 HS 0.07 0.10 3.97 5.76

6-(1-Methylethyl)chrysene C21H18 [24] 300–1000 This work 9.826 1.1171 0.622 6 0.09 0.10 5.10 6.19
 g0
Compound Formula Ref. Temperature Eqa Kw (VMGSIM) SG (VMGSIM) ω (VMGSIM) cp values εb Fc, d ıed (%)  rel  rel
F
range/K (J K−1 g−1 ) (J K−1 g−1 ) (%)f, g
300–900 LK1 0.06 0.07 3.02 3.74
300–900 CF1 = 0 0.06 0.08 3.20 4.01
300–900 LK2 0.03 0.04 2.13 2.99
300–900 CF2 = 0 0.03 0.04 2.17 3.03
300–1000 HS 0.02 0.03 1.42 2.25

Henicosanenitrile C21H41N [24] 300–1000 This work 13.065 0.8148 0.812 6 0.04 0.05 1.56 1.86
300–900 LK1 0.28 0.33 10.39 11.65
300–900 CF1 = 0 0.27 0.33 10.21 11.46
300–900 LK2 0.19 0.22 7.50 8.24
300–900 CF2 = 0 0.20 0.23 7.65 8.41
300–1000 HS 0.07 0.09 3.40 5.32

(S)-(+)-2-Methylbutyl C22H25NO3 [24] 300–1000 This work 9.977 1.1892 0.951 6 0.02 0.03 1.20 1.72
3-[4-[(4-methoxyphenyl)
methylene]amino]phenyl-
2-propenoate
300–900 LK1 0.13 0.16 6.61 7.45
300–900 CF1 = 0 0.13 0.16 6.62 7.47

V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370

300–900 LK2 0.08 0.09 4.17 4.57
300–900 CF2 = 0 0.08 0.09 4.17 4.57
300–1000 HS 0.03 0.04 2.07 2.65

Hexadecylbenzene C22H38 [24] 300–1000 This work 11.766 0.8961 0.964 6 0.07 0.08 2.86 3.22
300–900 LK1 0.07 0.09 2.38 3.08
300–900 CF1 = 0 0.06 0.09 2.10 3.02
300–900 LK2 0.04 0.05 1.46 1.69
300–900 CF2 = 0 0.01 0.02 0.70 0.90
300–1000 HS 0.04 0.06 2.34 3.66

Hexadecylcyclohexane C22H44 [24] 300–1000 This work 9.377 1.1250 0.741 6 0.03 0.04 1.15 1.42
300–900 LK1 1.08 1.23 41.01 44.93
300–900 CF1 = 0 0.82 0.91 31.90 35.05
300–900 LK2 0.89 1.01 34.21 37.48
300–900 CF2 = 0 0.86 0.97 33.47 36.71
300–1000 HS 0.06 0.07 2.83 3.67

1,1-Dimethylethyl C22H44O2 [24] 300–1000 This work 10.348 1.0108 1.050 6 0.05 0.06 1.79 2.16
octadecanoate
300–900 LK1 0.38 0.42 16.31 18.30
300–900 CF1 = 0 0.37 0.40 15.85 17.86
300–900 LK2 0.43 0.48 18.03 19.94
300–900 CF2 = 0 0.43 0.47 17.83 19.74
300–1000 HS 0.07 0.09 3.51 5.36

1-Decylpyrene C26H30 [24] 300–1000 This work 11.352 1.0017 0.825 6 0.05 0.07 3.11 4.25
300–900 LK1 0.25 0.30 11.26 12.58
300–900 CF1 = 0 0.29 0.35 13.05 14.73
300–900 LK2 0.20 0.23 9.38 10.31
300–900 CF2 = 0 0.23 0.27 10.40 11.53
300–1000 HS 0.04 0.05 2.30 3.44

4-Tetradecyl-1,1 -biphenyl C26H38 [24] 300–1000 This work 9.969 1.1026 1.605 6 0.01 0.02 0.66 0.90
300–900 LK1 0.33 0.36 14.94 16.76
300–900 CF1 = 0 0.33 0.36 14.93 16.74
300–900 LK2 0.38 0.42 16.92 18.67
300–900 CF2 = 0 0.38 0.42 16.91 18.67
300–1000 HS 0.06 0.07 3.01 4.40

1-Octadecylnaphthalene C28H44 [24] 300–1000 This work 12.908 0.8777 0.833 6 0.04 0.04 1.52 1.77
300–900 LK1 0.39 0.45 15.90 17.53
300–900 CF1 = 0 0.39 0.45 15.89 17.52
300–900 LK2 0.31 0.35 13.18 14.46
300–900 CF2 = 0 0.31 0.35 13.20 14.49

367
300–1000 HS 0.06 0.08 3.10 4.67
 368
g0
Compound Formula Ref. Temperature Eqa Kw (VMGSIM) SG (VMGSIM) ω (VMGSIM) cp values εb Fc, d ıed (%)  rel  rel
F
range/K (J K−1 g−1 ) (J K−1 g−1 ) (%)f, g
n-Octacosane C28H58 [24] 300–1000 This work 13.713 0.7894 1.1446 6 0.02 0.03 0.91 1.33
300–900 LK1 0.36 0.41 13.28 14.62
300–900 CF1 = 0 0.27 0.32 10.12 11.16
300–900 LK2 0.10 0.12 4.52 6.37
300–900 CF2 = 0 0.20 0.22 7.59 8.37
300–1000 HS 0.07 0.09 3.26 5.06

n-Triacontane C30H62 [24] 300–1000 This work 13.783 0.7920 1.184 6 0.02 0.03 0.91 1.33
300–900 LK1 0.39 0.44 14.32 15.77
300–900 CF1 = 0 0.29 0.33 10.67 11.76
300–900 LK2 0.10 0.13 4.67 6.74
300–900 CF2 = 0 0.21 0.23 8.13 8.97
300–1000 HS 0.07 0.09 3.30 5.12

n-Pentatriacontane C35H72 [24] 300–1000 This work 13.942 0.7973 1.248 6 0.02 0.03 0.91 1.34
300–900 LK1 6 0.45 0.51 16.77 18.48
300–900 CF1 = 0 6 0.32 0.37 11.88 13.06
300–900 LK2 6 0.12 0.15 5.60 7.78
300–900 CF2 = 0 6 0.24 0.27 9.31 10.27

V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370

300–1000 HS 6 0.07 0.10 3.38 5.25

n-Tetracontane C40H82 [24] 300–1000 This work 14.082 0.8013 1.279 6 0.02 0.03 0.91 1.34
300–900 LK1 6 0.51 0.58 19.05 21.01
300–900 CF1 = 0 6 0.34 0.40 12.90 14.18
300–900 LK2 6 0.16 0.19 6.70 9.13
300–900 CF2 = 0 6 0.27 0.30 10.32 11.38
300–1000 HS 6 0.07 0.10 3.44 5.34

n-Pentacontane C50H102 [24] 300–1000 This work 14.276 0.8069 1.296 6 0.02 0.03 0.88 1.31
300–900 LK1 6 0.60 0.68 22.35 24.71
300–900 CF1 = 0 6 0.38 0.43 14.28 15.68
300–900 LK2 6 0.23 0.30 9.31 12.13
300–900 CF2 = 0 6 0.30 0.33 11.67 12.89
300–1000 HS 6 0.07 0.10 3.51 5.44

n-Heptacontane C70H142 [24] 300–1000 This work 14.510 0.8134 1.2989 6 0.02 0.03 0.93 1.36
300–900 LK1 6 0.70 0.80 26.55 29.45
300–900 CF1 = 0 6 0.42 0.48 15.90 17.45
300–900 LK2 6 0.37 0.50 13.65 17.75
300–900 CF2 = 0 6 0.34 0.38 13.26 14.64
300–1000 HS 6 0.07 0.10 3.63 5.63

n-Octacontane C80H162 [24] 300–1000 This work 14.585 0.8155 1.2990 6 0.02 0.03 0.89 1.32
300–900 LK1 6 0.74 0.84 27.93 31.02
300–900 CF1 = 0 6 0.43 0.49 16.40 18.00
300–900 LK2 6 0.43 0.58 15.77 20.18
300–900 CF2 = 0 6 0.35 0.39 13.75 15.19
300–1000 HS 6 0.07 0.10 3.64 5.64

n-Nonacontane C90H182 [24] 300–1000 This work 14.643 0.8171 1.2990 6 0.02 0.03 0.90 1.33
300–900 LK1 6 0.77 0.87 28.99 32.24
300–900 CF1 = 0 6 0.44 0.50 16.78 18.42
300–900 LK2 6 0.48 0.65 17.45 22.20
300–900 CF2 = 0 6 0.36 0.40 14.13 15.61
300–1000 HS 6 0.07 0.10 3.66 5.68
VMGSIM Kw , SG and ω were culled VMGSim Version 6.5.
a
Abbreviations of the equations used: LK1 – first Lee–Kesler correlation Eq. (23), CF1 = 0 represents its truncated form; LK2 – second Lee–Kesler correlation Eq. (26), CF2 = 0 represents its truncated form; HS – Harrison–Seaton
correlation.
b
ε is the average absolute deviation.
c
 F is the average standard deviation of the fit.
d
 is the average standard deviation.
e
ı is the relative deviation.
f
 F rel is the average standard relative deviation of the fit.
g
 rel is the average standard relative deviation.
 V. Lastovka, J.M. Shaw / Fluid Phase Equilibria 356 (2013) 338–370
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