Energy & Fuels 2006, 20, 609-619 609

Prediction of Chromatographic Retention Times for Aromatic

Hydrocarbons
Prasenjeet Ghosh,*,† Birbal Chawla,‡ Prasanna V. Joshi,§ and Stephen B. Jaffe†
ExxonMobil Process Research Laboratories, Paulsboro, New Jersey 08066, ExxonMobil Research and
Engineering, Paulsboro, New Jersey 08066, and ExxonMobil Process Research Laboratories,
Baton Rouge, Louisiana 70821
ReceiVed July 25, 2005. ReVised Manuscript ReceiVed NoVember 16, 2005

A quantitative model for predicting the retention times of various single- and multi-ring aromatic hydrocarbons
(AH) and heteroatom-containing molecules in high-performance liquid chromatography (HPLC) is presented.
The retention time behavior of 44 aromatic molecules containing one-, two-, and three-ring structures on a
[3-(2,4-dinitroanilino)]propyl-silica column was investigated under subambient separation conditions. Substituent
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effects (their number, type, and position on the ring) on the retention behavior of these aromatic ring structures
were also investigated. A quantitative structure-property relationship (QSPR) model elucidating the retention
behavior of AH molecules was developed based on the obtained experimental data. It was found that the
electronic properties of the molecule and its molecular geometry play a pivotal role in determining its retention
in the HPLC column. The important electronic and geometric descriptors were identified using partial least
squares analysis. The electronic properties of the molecule were quantified by its ionization potential and
electron affinity computed from the optimized solute geometry using the PM3 energy function. The molecular
geometry was characterized by the number of rings, molecular weight, and the valence connectivity indices.
The mathematical form of the QSPR model was derived using genetic algorithms, and a log-linear form of the
model was found to best correlate the HPLC retention time data with the solute molecular descriptors. The
QSPR model was also used to predict the retention behavior of many other AH molecules that are commonly
present in most heavy petroleum streams. The results obtained in this study enhance our understanding of the
AH retention behavior and are of significance in predicting the identity of chromatographic peaks and quantify
the extent of overlap based solely on parameters derived from solute structure.

1. Introduction The advent of advanced and inexpensive computational tools

Petroleum is a complex mixture of thousands of distinct
molecular species, containing many different hydrocarbon- and
heteroatom-containing molecules. The ability to analytically
identify and quantitatively measure these molecules is critical
for the successful design and the economic operation of
commercial refining processes. A key analytical technology that
enables this is the high-performance liquid chromatography
(HPLC) separation where the different molecules are retained
for different amounts of times in the chromatographic column
according to their molecular structures. The ease of operation,
versatility, and high separation capacity has made HPLC the
analytical method of preference for molecular identification,
particularly for the heavy petroleum streams. However, despite
its many advantages, it is often difficult to correctly identify
all the chromatographic peaks in the HPLC separation. This is
particularly true for the polyaromatic hydrocarbons (PAH),
where there might be significant chromatographic peak overlap
between the different molecules, possibly resulting in complete
molecular misidentification. We present in this article a better
understanding of the retention behavior of different AHs and
PAHs in the chromatographic column and the development of
a quantitative model that predicts their retention times, thereby
facilitating correct identification of the molecular structures.
* To whom all correspondence should be addressed. Email:
prasenjeet.ghosh@exxonmobil.com.
† ExxonMobil Process Research Laboratories, Paulsboro, New Jersey.
‡ ExxonMobil Research and Engineering, Paulsboro, New Jersey.
§ ExxonMobil Process Research Laboratories, Baton Rouge.
has brought a remarkable growth in the area of quantitative
structure-property relationships (QSPR). QSPR employs vari-
ous multivariate methods starting from simple regression models
to detailed nonlinear neural network models to correlate relevant
properties as a function of the molecular structure (also called
descriptors). These descriptors can be structural, topological,
electronic, and/or geometric, depending on the problem at hand.
There are many examples in the literature where a QSPR
methodology was used to develop a predictive model for the
retention behavior of different hydrocarbons in a chromato-
graphic column. Some of the relevant work includes the work
of Collantes et al.,1 Ledesma and Wormat,2 Ferreira,3 Forgacs
and Cserhati,4 and references therein who all used different
descriptors that encode specific aspects of the molecular
structure to correlate the retention time behavior to molecular
structure. The objective of the present work is similar to the
cited literature, that is, to develop a QSPR model correlating
the molecular descriptors derived from different AHs including
PAHs and heteroatom-containing molecules to their retention
(1) Collantes, E. R.; Tong, W.; Welsh, W. Use of Moment of Intertia in
Comparative Molecular Field Analysis To Model Chromatographic Reten-
tion of Nonpolar Solutes. Anal. Chem. 1996, 68, 2038.
(2) Ledesma, E. B.; Wormat, M. J. QSRR Prediction of Chromatographic
Retention of Ethynyl-Substituted PAH from Semiempirically Computed
Solute Descriptors. Anal. Chem. 2000, 72, 5437.
(3) Ferreira. M. C. M. Polycyclic aromatic hydrocarbons: a QSPR study.
Chemosphere 2001, 44, 125.
(4) Forgacs, E.; Cserhati T. Use of PCA for studying the separation of
pesticides on polyethylene-coated silica columns. J. Chromatogr., A 1998,
797, 33.

10.1021/ef0502305 CCC: $33.50 © 2006 American Chemical Society

Published on Web 01/07/2006
610 Energy & Fuels, Vol. 20, No. 2, 2006 Ghosh et al.

Table 1. Experimental HPLC Retention Time Data of Various Molecules Considered in This Studya

a The numbers in parentheses reflect the retention time in minutes for these molecules in the HPLC column run under subambient conditions.

time behavior in a chromatographic column. Specifically, our
objectives are threefold: first, to identify and rank the molecular
descriptors (in order of their relevance) that correlate to the
retention time of the AH molecule in the column; second, to
use these descriptors to develop a quantitative model to predict
the retention time; and third, to use this predictive model to
study the effect of various substituents (e.g., addition of alkyl
side chains, addition of naphthenic rings, increasing the length
of the biaryl bride between aromatic molecules, etc.) on the
retention behavior of AHs and PAHs.
2. Experimental Section
A number of different aromatic molecules containing one, two,
and three aromatic rings were eluted on a [3-(2,4-dinitroanilino)]-
propyl-silica (DNAP-silica) column (known to be aromatic ring-
class separation specific)5-11 under subambient temperature condi-
tions. The HPLC system consisted of a quaternary solvent delivery
system, a sample injector, and a photodiode-array detector. The
(5) Nondek, L.; Malek, J. Liquid Chromatography of Aromatic Hydro-
carbons on a Chemically Bonded Stationary Phase of the Charge-Transfer
Type. J. Chromatogr. 1978, 155, 187.
(6) Nondek, L.; Minarik, M.; Malek, J. Charge-Transfer Liquid Chro-
matography of Aromatic Hydrocarbons and Polyaryl Alkanes. J. Chro-
matogr. 1979, 178, 427.
(7) Nondek, L.; Ponec, R. Chemically Bonded Electron Acceptors as
Stationary Phases in High-Performance Liquid Chromatography. J. Chro-
matogr. 1984, 294, 175.
(8) Nondek, L.; Minarik, M. Chromatographic Selectivity in Liquid
Chromatography of Polycondensed Aromatic Hydrocarbons on 3-(2,4-
Dinitroanilino)propyl-Silica. J. Chromatogr. 1985, 324, 261.
Retention Times for Aromatic Hydrocarbons
Figure 1. Percentage correlation of different molecular descriptors with retention time based on PLS analysis.
Figure 2. Variation of valence connectivity index of orders 1 and 2 with molecular structure. Notice the different isomers (at carbon numbers 4
and 6) highlighting the difference between (1)χv and (2)χv.
commercially available HPLC grade mobile phases, n-pentane and
methylene chloride, were used after overnight drying over freshly
activated 4A molecular sieves (8-12 mesh). The photodiode-array
detector was set to measure the spectra in the range of 190-400
nm at intervals of 1.3 nm every 25 s. A 1-mm path length was
used for the UV/vis measurements. The chromatographic separation
details are subject of a separate publication.
The aromatic molecules were injected mostly as pure compound
solutions. However, in some cases, where the elution behavior was
well-known, mixtures of 2-4 compounds were injected (e.g., a
mixture of toulene, naphthalene, phenanthrene, and pyrene). Under
the subambient chromatographic separation conditions, the aromatic
molecules were eluted under increasing solvent polarity at a constant
flow rate. Molecules were classified into four different aromatic
ring compound (ARC)-classes, namely ARC-1, ARC-2, ARC-3,
(9) Nondek, L. Liquid Chromatography on Chemically Bonded Electron
Donors and Acceptors. J. Chromatogr. 1986, 373, 61.
(10) Grizzle, P. L.; Thomson, J. S. Liquid Chromatographic Separations
of Aromatic Hydrocarbons with Chemically Bonded (2,4-Dinitroanilino-
propyl)silica. Anal. Chem. 1982, 54, 1071.
(11) Thomson, J. S.; Reynolds, J. W. Separation of Aromatic Hydro-
carbons Using Bonded-Phase Charge-Transfer Liquid Chromatography.
Anal. Chem. 1984, 56, 2434.
Energy & Fuels, Vol. 20, No. 2, 2006 611
and ARC4+ depending upon the times for which they were retained
in the column. Specifically, a molecule was classified as ARC-1
(e.g., toulene with one aromatic ring) if its retention time was less
than 120 min, ARC-2 (e.g., naphthalene) if it was between 120
and 330 min, and ARC-3 (e.g., phenanthrene) if it was between
330 and 480 min. The chromatographic column was back-flushed
beyond 480 min, and consequently any molecule whose retention
time was greater than 480 min was lumped into ARC-4+. The
molecular basis for the ARC-class categorization of different
molecules is the number of aromatic rings fused together without
any methylene group(s) in the molecule, that is, molecules with
one ring usually elute in ARC-1, molecules with two rings in ARC-
2, and so on; however, there are some molecules with exceptional
shape and geometry that do not follow this grouping. The measured
chromatographic retention time data (in minutes) for the different
molecules considered in this study are summarized in Table 1.
3. Calculation of Molecular Descriptors
The development of any predictive model requires a postulate
of the underlying physical phenomenon and identification of
the key physical variables. Retention in the chromatographic
column is a molecular adsorption phenomenon where the
612 Energy & Fuels, Vol. 20, No. 2, 2006 Ghosh et al.

Table 2. Different Molecular Descriptors Considered for Characterizing the Electronic Structure and the Molecular Geometry of the Molecule

Table 3. Computation of Various Molecular Descriptors for the Different Molecules in This Study
ionization electron valence valence measured
potential affinity molecular ring connectivity connectivity retention
chemical sample (eV) (eV) weight count index (order 1) index (order 2) time (min)
1,3,5-tri-tert-butylbenzene 9.326 -0.508 246.435 1 6.982 8.549 21
1,4-di-tert-butylbenzene 9.283 -0.407 190.328 1 5.321 6.077 24
dioctylthiophene 9.124 0.08 308.564 1 10.363 7.201 25
neo-pentylbenzene 9.485 -0.364 148.247 1 4.118 4.223 32
p-dicyclohexylbenzene 9.323 -0.337 242.403 3 8.032 6.337 35
tetralin 9.248 -0.427 132.205 2 4.034 2.976 42
nC18-benzene 9.457 -0.354 330.596 1 10.971 7.539 42
n-hexylbenzene 9.41 -0.384 162.274 1 4.971 3.296 43
toulene 9.442 -0.376 92.14 1 2.411 1.655 44
mesitylene 9.281 -0.438 120.194 1 3.232 2.665 47
1,2,3,4-tetramethylbenzene 9.015 -0.423 134.221 1 3.661 2.949 110
durene 8.957 -0.382 134.221 1 3.655 3.021 129
1,3-diphenylpropane 9.473 -0.296 196.291 2 5.528 3.825 136
indene 8.971 0.077 116.162 2 3.211 2.305 140
dodecahydrotriphenylene 8.856 -0.509 240.388 4 8.121 6.493 145
phenylhexadecyl sulfide 8.557 -0.09 334.602 1 11.096 7.926 146
1,2-di-p-tolylethane 9.17 -0.231 210.318 2 5.85 4.471 147
6-benzyltetrahydronaphthalene 9.125 -0.268 222.329 3 6.563 4.973 149
biphenyl 9.145 0.142 154.211 2 4.071 2.732 149
4,4′-dimethylbiphenyl 8.867 0.131 182.265 2 4.893 3.732 164
naphthalene 8.836 0.408 128.173 2 3.405 2.347 174
hexamethylbenzene 8.865 -0.479 162.274 1 4.5 3.75 181
benzothiophene 8.797 0.467 134.195 2 3.769 2.906 195
1,2,3,6,7,8-hexahydropyrene 8.354 0.363 208.302 4 6.486 5.225 197
phenyl disulfide 9.234 2.154 218.331 2 6.546 5.069 199
2,2-biothiophene 8.977 1.016 166.255 2 4.8 3.85 203
2,6-dimethylnaphthalene 8.671 0.341 156.227 2 4.226 3.354 222
acenaphthene 8.59 0.352 154.211 3 4.445 3.432 245
dibenzofuran 9.019 0.476 168.195 3 4.313 3.094 256
fluorene 8.842 0.335 166.222 3 4.612 3.491 262
2(1-naphthylmethyl)-1,2,3,4- 8.763 0.454 272.389 4 7.934 6.22 334
tetrahydronaphthalene
1,2,3,4-tetrahydrophenanthrene 8.616 0.35 182.265 3 5.445 4.131 336
1,2,3,4-tetrahydro-1,2-binaphthyl 8.771 0.458 258.362 4 7.461 5.777 338
nC6-dibenzothiophene 8.511 0.596 268.416 3 8.101 6.323 339
2-benzylnaphthalene 8.79 0.404 218.298 3 5.933 4.344 340
acenaphthylene 9.056 1.062 152.195 3 4.149 3.126 348
2-phenylnaphthalene 8.743 0.525 204.271 3 5.476 3.928 358
dibenzothiophene 8.598 0.628 184.255 3 5.129 4.178 366
4,6-dimethyldibenzothiophene 8.46 0.609 212.309 3 5.963 5.082 377
phenanthrene 8.741 0.535 178.233 3 4.815 3.508 385
naphthothiophene 8.787 0.839 184.255 3 5.18 4.067 418
4H-cyclopentaphenanthrene 8.656 0.515 190.244 4 5.356 4.273 425
2,3-benzofluorene 8.585 0.612 216.282 4 6.017 4.69 432
benzonaphthothiophene 8.456 0.876 234.315 4 6.54 5.314 507

different solute molecules adsorb to varying extents on the
column depending upon the extent of interaction between the
solute and the column solid phase. We believe the nature of
this interaction to be a charged interaction where the electronic
structure of the solute would be expected to play a critical role.
Further, the strength of such an interaction is expected to be
shape-specific, implying that certain molecular geometries would
be more favored than others. Therefore, we assert that molecular
parameters that characterize the electronic structure, shape, and
geometry of the solute should be the most important parameters
that control the retention of different solutes on the chromato-
graphic column.
A number of molecular descriptors that characterize various
aspects of the electronic and molecular geometry of all the
different molecules considered in this study were computed.
The complete list of such descriptors is summarized in Table
2. Ionization potential (IP), electron affinity (EA), electron gap,
and the dipole moment were used to quantify the electronic
structure of each molecule, whereas molecular weight, physical
dimensions such as length, breadth, width, and volume, total
Retention Times for Aromatic Hydrocarbons
Figure 3. Comparison of predicted retention times against measured values. The molecules are categorized into different ARC-classes as indicated
by different symbols. The 15% error bands are indicated by the dotted lines. The inset shows the ARC-1 results in detail.
Table 4. Parameter Values for Eq 1
a0 a1 a2 a3 a4 a5 a6
5.1128 -0.5236 0.1461 0.0118 0.0916 -0.2232 -0.1868
number of rings, and various topological indices such as the
Wiener index and valence connectivity index of different orders
were used to quantify geometric effects. Although the chemical
formula of the molecule aids in calculating many geometrical
descriptors such as molecular weight, number of rings, and the
various topological indices, computation of the physical dimen-
sions of the molecule and its electronic descriptors requires a
more detailed quantum mechanical calculation. We used the
CAChe commercial software12 to compute these molecular
descriptors. The geometry of each molecule was optimized in
MOPAC using the semiempirical PM3 Hamiltonian function.12
The geometry calculations were performed multiple times with
small perturbations to the structure to ensure that the optimized
structures were indeed at their global minimum. (The term global
minimum is used loosely here and merely refers to the best
minimum found over multiple iterations. In general, it is not
possible to theoretically guarantee global minimum for nonlinear
functions unless under special circumstances such as convexity,
pseudoconvexity, etc.).
The descriptors listed in Table 2 convey information about
the electronic structure and the molecular geometry of the
molecule. However, not all of them are equally important to
predict the retention time. Partial Least Squares (PLS) was used
to identify the significant descriptors affecting retention time
behavior. PLS is a mathematical algorithm that identifies the
significant variables from a multidimensional independent
variable space that exhibit the most correlation with the
dependent variable space. It helps contract the dimensions of
the problem with minimal loss of information. The results of
the PLS analysis are presented in Figure 1, and only the most
significant descriptors are shown here along with their relative
contribution. The contribution from the other descriptors were
negligible, and consequently they are not addressed in this
figure. The PLS analysis identifies the following six descriptors
to be the most significant ones: (a) EA, (b) IP, (c) molecular
Energy & Fuels, Vol. 20, No. 2, 2006 613
weight (MW), (d) number of rings (Rc), (e) valence connectivity
index of order 1, (1)χv, and (f) valence connectivity index of
order 2, (2)χv. Further, the results also indicate that EA and IP
play the most dominant role, accounting for almost 60% of the
correlation of molecular descriptors with retention time, while
the molecular geometry plays a secondary role in controlling
the retention behavior of different molecules in the HPLC
column. These molecular descriptors are defined below:
(i) Ionization potential and electron affinity. IP is the energy
required to completely remove an electron from an atom. As
would be expected, this energy depends on the energy level of
the orbital in which the electron resides and also depends on
whether the energy level is full or half full. In contrast, the EA
is the energy released when an atom picks up an electron.
(ii) Molecular weight. The total mass of 1 mol of the molecule
(compound).
(iii) Total number of rings. The total number of rings, which
includes all polygonal rings in the molecule. For example, the
total number of rings in both naphthalene and tetralin is two,
whereas it is three for dibenzothiophene.
(iV) Valence connectiVity index of order 1 and 2.13 The
valence connectivity index, typically represented by χ, is a graph
theoretical index that characterizes the general topology and
shape of the molecule. Specifically, it quantifies the skeletal
makeup of the molecule and the degree and type of branching
in it based on the connectivity matrix of the molecule. It
distinguishes between the type of different atoms present in the
molecule by taking into account the electronic environment of
the valence shell of the different atoms. Depending on the exact
definitions of the connectivity measure of the molecule, various
valence connectivity indices of different orders may be defined.
The mathematical definition of valence connectivity index and
its different orders is summarized in the Appendix at the end
of the article. Some general observations of these indices are
(12) CAChe Modeling Software; Fujitsu Inc. http://
www.cachesoftware.com/cache/index.shtml.
(13) Hall, L. H.; Kier, L. B. Issues in representation of molecular
structure: The development of molecular connectivity. J. Mol. Graphics
Modell. 2001, 20, 4.
614 Energy & Fuels, Vol. 20, No. 2, 2006 Ghosh et al.

Figure 4. Molecular structure of the different PAH cores considered in Table 5. Here, the number in parentheses refers to the index of the
molecule in Table 5, not the retention time. For example, (3) here refers to core-3 in Table 5.

Figure 5. Prediction of retention times for phenanthrene homologous series. The two dotted lines indicate the ARC-3 region. A molecule is
classified as ARC-3 if its retention time is between 330 min and 480 min.

presented in Figure 2, using benzene as the illustrative molecule.
The figure shows the valence connectivity indices of order 1,
(1)χ , and order 2, (2)χ , for benzene with its different substituents.
v v
Note that:
(a) Both (1)χv and (2)χv increase with increase in the length of
the alkyl substituent.
(b) For a fixed number of substituents, (1)χv decreases with
increased branching; in contrast, (2)χv increases with branching.
(c) For a fixed number of substituents and the same degree
of branching, (1)χv decreases with increased methylation on the
aromatic ring; in contrast, (2)χv increases.
Table 3 summarizes the computed values of these descriptors
for the different molecules that were studied in this work (refer
to Figure 1 for their structures). Also included in this table is
the measured retention time in minutes for these molecules in
the HPLC column. Using this data, a QSPR model between
the molecular descriptors and the retention time was developed,
which is shown in eq 1. Equation 1 is a log-linear relationship,
and although various other functional forms can also be
considered, we found that this functional form yielded the
highest correlation coefficient (i.e., R2 value) between the
molecular descriptors and the retention time. The log-linear
Retention Times for Aromatic Hydrocarbons Energy & Fuels, Vol. 20, No. 2, 2006 615

Table 5. Computation of Various Molecular Descriptors for the Different Core Structures and ARC-Class Prediction by the Model
ionization electron valence valence retention
chemical potential affinity molecular ring count connectivity connectivity time predicted ARC-class
sample (eV) (eV) weight (all rings) index (order 1) index (order 2) (min) predicteda
core-1 9.249 -0.432 186.296 3 6.028 4.889 53.69 1
core-2 9.248 -0.427 132.205 2 4.034 2.976 63.29 1
core-3 9.751 -0.396 78.113 1 2 1.155 40.21 1
core-4 8.602 0.26 234.34 4 7.152 5.594 280.46 2
core-5 9.125 -0.268 222.329 3 6.563 4.973 128.97 2
core-6 9.002 -0.462 294.479 5 10.061 8.581 53.65 1
core-7 9.298 -0.413 240.388 4 8.011 6.794 43.74 1
core-8 8.646 0.395 242.378 4 7.796 6.647 158.24 2
core-9 8.609 0.398 188.287 3 5.809 4.69 197.67 2
core-10 8.797 0.467 134.195 2 3.769 2.906 183.61 2
core-11 8.75 0.475 204.271 3 5.482 3.893 441.11 3
core-12 8.434 0.298 290.447 5 9.479 7.829 229.42 2
core-13 8.633 0.351 236.356 4 7.438 6.044 209.37 2
core-14 9.145 0.142 154.211 2 4.071 2.732 172.33 2
core-15 8.616 0.35 182.265 3 5.445 4.131 250.96 2
core-16 8.836 0.408 128.173 2 3.405 2.347 223.46 2
core-17 8.342 0.706 256.346 5 7.571 6.074 658.00 4
core-18 8.493 0.436 286.416 5 8.89 7.12 368.18 3
core-19 8.725 1.044 202.255 4 5.565 4.255 527.63 4
core-20 8.622 0.486 232.324 4 6.856 5.292 370.70 3
core-21 8.651 0.511 204.271 4 5.856 4.596 378.83 3
core-22 8.741 0.535 178.233 3 4.815 3.508 371.90 3
core-23 8.652 0.504 374.558 6 11.702 9.712 338.43 3
core-24 8.842 0.335 166.222 3 4.612 3.491 248.06 2
core-25 8.377 0.507 292.438 5 9.21 7.725 334.24 3
core-26 8.627 0.924 320.466 5 9.549 8.224 414.14 3
core-27 8.439 0.569 238.347 4 7.17 5.965 356.87 3
core-28 8.663 1.192 266.375 4 7.509 6.465 488.78 3
core-29 8.598 0.628 184.255 3 5.129 4.178 342.75 3
a A molecule is classified as ARC-1 if retention time is less than 120 min, ARC-2 if it is between 120 and 330 min, ARC-3 if it is between 330 and 480

min, and ARC-4 if it is greater than 480 min.

Table 6. Effect of the Length of Biaryl Bridge on the Retention Timea

a The numbers correspond to the retention time in minutes.

functional form was identified using genetic algorithms (specif-
ically genetic function approximations), a stochastic search
algorithm run to identify the most appropriate mathematical
structure among the various other alternative mathematical
structures.
the solute would be [L/ux]. Furthermore, if u denotes the
interstitial velocity in the column, that is, the velocity with which
a nonadsorbing solute molecule will move within the interstices
of the column bed and us the velocity of an adsorbed solute in
the bed, mass balance yields

[]
tr nsus + nmu nmu
log10 ) a0 + a1(IP) + a2(EA) + a3(MW) + a4(Rc) + ux ) ) (2)
to n s + nm ns + nm
a5((1)χv) + a6((2)χv) (1) Since an adsorbed solute is stationary, us ) 0. Therefore, eq 2
may be rearranged as
In eq 1, tr is the retention time of the solute molecule, to is
the retention time of a nonadsorbing solute molecule (i.e., a
solute that does not have any measurable interaction with the
column, e.g., olefins), and ai (i ) 0-6) are the fitting parameters
tr )
L
ux ( ) ( )
) 1+
ns L
nm u
) 1+
ns
t
nm o
(3)

of the model to be regressed from the experimental data.
Interestingly, the ratio [tr/to] used in eq 1 can be related to the
partition coefficient of the solute molecule between the station-
ary and mobile phases on the chromatographic column. The
partition coefficient is defined as the ratio of the number of
moles of a solute molecule in the stationary adsorbed phase to
the number of moles in the mobile phase and represents a widely
used quantitative measure of separation. To see this, assume
that ns and nm are the moles of a particular solute molecule in
the stationary and mobile phase, respectively. Further, let us
assume that ux denotes the average velocity with which the
solute band moves in the column so that if L were the length of
the chromatographic column, the observed retention time for
Equation 3 shows that the ratio [tr/to] is related to the number
of moles of the solute in the stationary phase to mobile phase,
that is, the partition coefficient of the solute.
4. Results and Discussion
To obtain the different ai parameters in eq 1, a least squares
error minimization problem was solved, and the final optimized
values are tabulated in Table 4. To ensure that the regressed
parameters were adequately reliable and robust for the model
to be used in an extrapolative predictive mode, the dataset was
partitioned into a training set (90% of the samples) and a testing
set (10% of the samples), and the errors were compared against
many such partitions (total partitions considered ) 200). Figure
616 Energy & Fuels, Vol. 20, No. 2, 2006 Ghosh et al.

Table 7. Prediction of Retention Times and ARC-Classes of the Different Alkylated Structures Resulting from the PAH Cores Shown in
Figure 4a
Retention Times for Aromatic Hydrocarbons Energy & Fuels, Vol. 20, No. 2, 2006 617

Table 7. (Continued)

a The numbers correspond to the retention time in minutes. The elution ARC-class is shown in parentheses.
618 Energy & Fuels, Vol. 20, No. 2, 2006
Table 8. Effect of Naphthenes for the Various Ring Structuresa
a The numbers correspond to the retention time in minutes. The elution ARC-class is shown in parentheses.
3 compares the results of the model predictions against the
experimental data set. The figure reveals a good quantitative
agreement between the model-predicted and experimentally
observed retention times with a correlation coefficient (R2) of
0.905 in the training set and 0.831 in the cross-validation set.
The average error of the model is about 10% for ARC-1
molecules and about 15% for both ARC-2 and ARC-3 mol-
ecules. These results reveal that simple molecular descriptors
that are computationally inexpensive to calculate easily describe
a complex phenomenon such as retention behavior.
The ability to quantitatively predict the retention time of
different AHs and PAHs is certainly the most desirable
requirement of the predictive model. However, more frequently,
the question of interest is not so much the actual retention time
for the AH or PAH molecule, rather just which ARC-class the
molecule will elute in. Therefore, the model was used to predict
the ARC-class of typical PAH molecules present in heavy
petroleum fractions. These molecules include most of the
aromatic cores that are analytically measurable in the heavy
petroleum fractions. Further, the effect of substituents on the
PAH retention time behavior was also investigated using the
QSPR model (e.g., addition of alkylated side chains, introduction
of branching, or addition of naphthenic rings, etc.).
Figure 4 shows the 29 different PAH cores considered for
this purpose, which includes one- to five-membered rings
including many heteroatom-containing molecules. Many of these
PAH cores can be seldom obtained in large quantities to
experimentally measure their retention time in the column, and
hence a predictive model is required to quantify their retention
behavior. Table 5 summarizes the computed molecular descrip-
tors along with the predicted retention times for these PAH
cores. On the basis of the retention times, the ARC-class
assignments of these cores are also shown in the table. The
actual molecular structure corresponding to each PAH core can
be read from Figure 4 where its index is represented in
parentheses. For example, Core-2 represents tetralin, Core-3
represents benzene, and so on.
The table shows that each PAH core is assigned to a unique
ARC-class. However, interesting deviations from these class
assignments can happen as different substituents are added to
the basic PAH core. For instance, increasing the length of the
biaryl bridge for core-5 (which is assigned to ARC-class 2; see
Table 5) decreases the retention time. Table 6 shows this effect.
For the biaryl bridge length containing one and two carbon
atoms, the molecules elute in ARC-2. However, as the bridge
becomes longer (e.g., four carbon atoms), the molecules elute
Ghosh et al.
Table 9. Effect of the Position of Naphthenic Substitution on
Naphthalenea
a The numbers correspond to the retention time in minutes. The elution
ARC-class is shown in parentheses.
in ARC-1, indicating that the two aromatic rings tend to behave
independently of each other as the rings get separated by longer
alkyl chains.
Next, we use the model to investigate the effect of side chains
on the retention behavior of the different PAH cores by adding
different alkyl side chains to each PAH core. A typical result
for the phenanthrene core is presented in Figure 5. The figure
shows the variation in the retention time of phenanthrene with
increase in alkyl chain length. The retention time increases for
the first few molecules containing methyl substituents and then
drops as the length of the alkyl substitution increases. This
suggests that alkylation with methyl groups increases the
retention time of the molecule, while alkylation with longer
chain groups such as propyl, butyl, pentyl, and so on progres-
sively decreases it. Also, the initial steep decrease in the
retention behavior with increasing alkylation eventually plateaus
out as the alkyl chains grow longer. The effect may be
rationalized as follows: The methyl group is an electron-
donating group; consequently, alkylation with methyl groups
leads to increased electron density on the aromatic ring, resulting
in increased aromatic character of the ring and hence the longer
retention time. In contrast, as the number of carbon atoms in
the alkyl group increases (i.e., going from methyl to ethyl,
propyl, butyl, and so on), the electron-donating ability of the
group progressively decreases. In other words, increasing
paraffinic character reduces electron donation, and hence the
decrease in retention time with alkylation. Further, since the
incremental decrease in electron-donating ability with the
addition of each CH2 group in the alkyl chain decreases steeply
initially, eventually leading to a plateau, a similar trend is
observed in the retention behavior. The increase or decrease in
retention time with alkylation can have important consequences
as it suggests that the entire homologous series may not elute
Retention Times for Aromatic Hydrocarbons Energy & Fuels, Vol. 20, No. 2, 2006 619

Table 10. Prediction of Retention Times for Some Other Important Moleculesa

a The numbers correspond to the retention time in minutes. The elution ARC-class is shown in parentheses.

in the same ARC-class. For example, Figure 5 shows that
although phenanthrene elutes in ARC-3, some molecules in the
phenanthrene homologous series (specifically molecules 4, 5,
and 6) are very close to the boundary of ARC-3 and ARC-4
and might elute in ARC-4, while the rest elute in ARC-3. Similar
computations were performed for all the other PAH cores shown
in Figure 4, and the results are summarized in Table 7. Each
row in this table corresponds to a particular core structure and
its homologous series. The numbers below each structure
represent the predicted retention time (in minutes) and the
corresponding ARC-class (in parentheses) assignments. Al-
though most of the PAH cores and their homologous series tend
to elute in the same ARC-class, there are a few cores for which
some of the molecules in the homologous series elute in a class
different from the core. This happens for cores 8, 14, 20, 22,
25, and 27. These structures may be termed as “overlapping
structures” since they overlap across the different ARC-classes.
The effect of naphthenic rings on the retention time was also
studied, and some typical results for a few PAH cores are
illustrated in Table 8. Analogous to alkylation, the retention
time initially increases and then gradually decreases with the
addition of naphthenic rings. The position of the naphthenic
ring attachment also has an effect on the final retention time.
This is shown in Table 9 for naphtheno-naphthalene where the
retention times are quite different (i.e., 214.85 and 288.03 min,
respectively), depending on whether the second naphthenic ring
is attached to the aromatic ring or the first naphthenic ring.
Finally, the effect of a replacing a paraffinic bond with an
olefinic bond in the PAH core was also studied, and the results
are illustrated in Table 10. The results show that the presence
of an olefinic bond may migrate the molecule to the next ARC-
class. For example, indene (with a retention time of 138 min)
will elute in ARC-2, although indane (with a retention time of
68 min) will elute in ARC-1. Likewise, ethylbenzene (65 min)
is ARC-1, whereas styrene (124 min) is ARC-2. Acenaphthylene
(348 min) is at the border of ARC-2 and ARC-3, whereas its
paraffinic equivalent acenaphthene (273 min) is strictly ARC-
2.
the effect of different substituents on the bare PAH cores. It
was found that alkylation with methyl groups increased the
retention time, while alkylation with longer chains (gtwo
carbons) decreased it. Addition of naphthenic rings initially
increased the retention time, followed by a gradual reduction
of the retention time as more rings were added. The position of
the naphthenic ring also affected the retention time of the
molecule. Finally, addition of an olefinic bond always increased
the retention time.
Acknowledgment. We wish to thank Clint Kennedy, Roland
Saeger, and Larry Green for many useful discussions during the
development of the model.
Appendix: Definition of Valence Connectivity Index
The valence connectivity index (vχ) is a topological index
that encodes the skeletal geometry of the molecule using a graph
theoretic approach with explicit accounting for the valence state
of the different atoms. (A graph theoretic representation of a
molecule is an abstraction where each atom is considered a node
and each bond is considered an edge.)
To compute vχ, we need to first define the valence δv value
given by
Zv - h
δv ) (A.1)
Z - Zv - 1
Zv ) σ + π + n (A.2)
where σ, π, and n are the number of valence sigma, pi, and
lone pair electrons in the atom, h is the count of bonded
hydrogens, and Z is the atomic number. Thus, for instance, in
alkanes where each carbon is sp3 hybridized, the vδ value of
all the carbon atoms is 4 - h where h ) 3, 2, 1, or 0 depending
on whether the carbon is primary, secondary, tertiary, or
quaternary. The following table shows the computed vδ values
for a few selected examples.
-CH3 -CH2- dCH2- -NH2 >N- dO -F -Cl -S-

5. Conclusions δV 1 2 2 3 5 6 7 0.78 0.56

Once the vδ
values are computed, the valence connectivity
The retention time behavior of various AH and PAH
molecules was studied in this work. QSPR analysis was used of order 1 may be computed as
to investigate relationships between the AH and PAH molecular
structure and its chromatographic retention behavior. It was
χ )
1 v
∑k (δvi δvj )k-1/2 (A.3)
found that the electronic structure of the molecule and its
molecular geometry controlled its retention on the column. A where the vδ values are taken pairwise for all subgraphs having
predictive quantitative model was developed based on the one edge and in general of order t as
molecular descriptors that characterized the molecule’s elec-
tronic structure and its geometry. The model was used to predict
χ )
t v
∑1 ∏i (δvi )1-1/2 (A.4)
the retention time and investigate the ARC-class assignment
where the vδ are taken t-tuplewise for all subgraphs with t edges.
for the various AHs and PAHs typically encountered in heavy
petroleum streams. The model was also employed to investigate EF0502305