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 THERMOPHYSICAL PROPERTIES OF
INDIVIDUAL HYDROCARBONS OF
PETROLEUM AND NATURAL GASES
Properties, Methods, and
Low-Carbon Technologies

BORIS A. GRIGORIEV
Department of the Study of Oil and Gas Reservoir Systems, Gubkin Russian State University of Oil and Gas,
Moscow, Russia

ANATOLY A. GERASIMOV
Department of Civil Engineering, Kaliningrad State Technical University, Kaliningrad, Russia

IGOR S. ALEXANDROV
Institute of Marine Technology, Energy and Construction, Kaliningrad State Technical University, Kaliningrad, Russia

BORIS V. NEMZER
FutureCeuticals, Inc.; University of Illinois at Urbana-Champaign, Urbana, IL, United States
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 About the authors
Boris A. Grigoriev, PhD, ScD, graduated
from the Grozny State Oil Technical Univer-
sity and is a member of the Russian Academy
of Sciences. Dr. Grigoriev is currently a profes-
sor at the department of the study of oil and
gas reservoir systems at Gubkin Russian State
University of Oil and Gas. He has authored
more than 400 scientific works, including a
very popular textbook on heat and mass trans-
fer and 6 books on thermophysical properties
of hydrocarbons, oils, petroleum products,
aqueous solutions, ordinary and heavy water,
sulfur hexafluoride, and other energy carriers.
He is a distinguished member of various
national and international societies and asso-
ciations such as Bureau of the National Com-
mittee on the Thermophysical Properties of
Substances, International Association for the
Properties of Water and Steam (IAPWS),
National Committee on Data for Science and
Technology (CODATA).
Anatoly A. Gerasimov, PhD, ScD, graduated
from the Grozny State Oil Technical Uni-
versity and is currently a professor in the
department of heat and gas supply and ven-
tilation at Kaliningrad State Technical
University. Dr. Gerasimov has authored
vii
more than 100 scientific works in the field of
thermophysical properties of substances,
including 3 monographs.
Igor S. Alexandrov, PhD, ScD, graduated
from Kaliningrad State Technical University
and is currently Director of the Institute of
Marine Technology, Energy and Construc-
tion at Kaliningrad State Technical Univer-
sity. Dr. Alexandrov has authored more
than 100 scientific works in the field of
thermophysical properties of substances.
Boris V. Nemzer, PhD, FRSC, is Vice Presi-
dent of R&D and Director of Research and
Analytical Center at FutureCeuticals, Inc.
(United States), and a professor at the Uni-
versity of Illinois at Urbana-Champaign
(United States). Dr. Nemzer is an author of
more than 180 scientific papers published
in peer-reviewed journals and 3 books in
the areas of thermophysical properties of
substances, physical and analytical chemis-
try, nutrition, and food sciences. He is a fel-
low and distinguished member of various
national and international scientific societies
and associates.
 Foreword
One of the most important priorities in sci-
entific and technological progress in energy
production is the increase in the efficiency
of recovery, processing, and transportation
of hydrocarbons. The problems associated
with the exploration of complex, offshore,
gas-hydrate fields and the extraction of
low-pressure gas from the fields that have
entered the final stages of operation require
the development of fundamental scientific
knowledge to create novel technologies for
the production and processing of hydrocar-
bons. Therefore, knowledge of the
thermophysical properties of fluids is essen-
tial for this development.
This reference monograph Thermophysical
Properties of Individual Hydrocarbons of Petro-
leum and Natural and Gases compiled by Boris
A. Grigoriev, a corresponding member of the
Russian Academy of Sciences, and his co-
workers summarizes the results of decades-
long experimental and theoretical studies
of thermophysical properties of main groups
of hydrocarbons, commonly existing in oil
and gas condensates under a wide range of
conditions (from the triple-point tempera-
tures to 700 K and pressures up to 100 MPa)
in the liquid and vapor phases, including
the critical region.
The monograph pays major attention to
the description of experimental methods, es-
timation of measurement uncertainties, and
reliability of experimental data. The authors
have decided to publish almost all the
ix
experimental data on the properties of hy-
drocarbons obtained in the thermophysical
laboratory of Grozny State Oil Technical Uni-
versity, as well as the detailed analysis of
these data.
This book also examines modern methods
for developing fundamental and local equa-
tions of state and methods for the prediction
of thermophysical properties, which are
used for modeling the production,
processing, and transportation of hydrocar-
bons. The main concept and principles of
hydrogen-based energy and the role of hy-
drocarbons in the process of transition to hy-
drogen energy are discussed. The
significance of the fundamental equations
of state of hydrocarbons and associated
gases in solving the problems of global
warming is emphasized.
We believe that the monograph will be in-
teresting and useful to a broad community of
engineers and researchers working in
this field.
Jan V. Sengersa and Mikhail A. Anisimovb
a
Distinguished University Professor Emeritus, Institute
of Physical Science & Technology, University
of Maryland, College Park, MD, United States
b
Distinguished University Professor, Department
of Chemical and Biomolecular Engineering,
and Institute of Physical Science & Technology,
University of Maryland, College Park, MD,
United States
 Dedicated to the staff of the Industrial Thermophysical
Laboratory of the Grozny State Oil Technical University
Preface
Oil and natural gas are the core elements
of the global economy and politics. Today,
the production, refining, and transportation
of oil and gas are becoming objects of inter-
national disputes and conflicts. They are in-
creasingly being used as tools to influence
countries and regions. Just a few decades
ago, the era of oil and gas seemed to be com-
ing to an end with the depletion of fossil fuel
reserves, as well as the obvious progress in
the development of alternative energy
sources. However, the end of the 20th cen-
tury and the beginning of the 21st century
were marked by a new turn in the develop-
ment of the oil and gas industry. Large
new deposits were discovered in the shelf
zones of the seas and oceans. New technolo-
gies for the development and production of
hydrocarbons from structurally complex
fields, such as shale oil and gas, have been
created; old fields operated dozens and even
hundreds of years ago have been turned on
due to new technologies, and intensive work
is being done to create technologies for pilot-
commercial production of natural gas from
gas hydrate deposits.
At the same time, due to climate change,
today, the issue of diversifying the energy in-
dustry as one of the main anthropogenic
“suppliers” of greenhouse gases is very
acute. A rational solution may be the develop-
ment of hydrogen energy, if technological
processes and capacities for the production
of hundreds of millions of tons of hydrogen
are created. Moreover, over the next
20–30years, the most competitive will be the
processes of hydrogen production from
xi
natural gas, oil, coal, biomass, and other or-
ganic sources.
A high-quality energy transition will re-
quire the development of efficient processes
for producing hydrogen with a low carbon
footprint (different levels: gray, blue, green);
capturing, transporting, storing, and effi-
ciently disposing of carbon dioxide; and re-
ducing man-made emissions of natural and
associated petroleum gases. All this will
require further improvement and develop-
ment of technologies for the production
and transport of carbon and hydrocarbon
raw materials, which are impossible without
the knowledge of the thermophysical prop-
erties of energy sources, intermediate and
final reaction products, reservoir fluids, oil-
and gas-saturated reservoirs, etc.
Successes and prospects for the develop-
ment of the oil and gas industry were made
possible thanks to numerous studies of the
properties of oil, natural gas, and their compo-
nents in research laboratories in different
countries and the support of these studies by
governments and businesses. The key point
of these studies is the study of the physico-
chemical and thermophysical properties of
the most important hydrocarbons of oil and
natural gas: alkanes, cycloalkanes, and arenes,
as well as gases associated with the extraction
of oil and natural gas, such as hydrogen,
helium, nitrogen, carbon dioxide, hydrogen
sulfide, water vapor, and others. The develop-
ment of new technologies for influencing the
reservoir and the bottom-hole zone to increase
oil and condensate recovery, improving
methods for modeling reservoir systems,
xii
supercritical technologies for oil production
and processing require knowledge of the
thermophysical properties of oil, natural gas,
and their components in a wide range of tem-
peratures and pressures.
Systematic studies of the physicochemical
properties of oil hydrocarbons were carried
out in the first half of the 20th century at the
American Petroleum Institute (API) by
F. Rossini and other employees. The study of
caloric properties at low temperatures in re-
search projects No. 6 and No. 44 was
conducted under the auspices of the US Na-
tional Bureau of Standards (NBS). The work
of the Thermodynamic Research Center of
the Texas A&M University System on the for-
mation of a data bank of the thermophysical
properties of hydrocarbons and other techni-
cally important substances was noteworthy.
Concurrently, active studies of hydrocarbon
properties were carried out at a number of uni-
versities in Germany, France, and England.
A significant contribution to the study of
the thermophysical properties of oil hydrocar-
bons was made by scientists from a number of
research centers in the USSR, such as the State
Service of Standard Reference Data (SSSRD),
the Grozny State Oil Technical University
(GSOTU), the Azerbaijan Oil and Gas Institute,
the Moscow State University, Moscow Power
Engineering Institute, Odessa Institute of
Marine Fleet Engineers, Dagestan Scientific
Center of the Russian Academy of Sciences
(RAS), the Institute of High Temperatures of
the RAS, Institutes of Thermophysics of the
Ural and Siberian Branches of the RAS.
At the beginning of the 1960s, large-scale
comprehensive studies of the thermophysical
properties of oils, oil products, gas conden-
sates and their fractions, as well as the main
groups of oil hydrocarbons, were started in
the Industrial Thermophysical Laboratory
(ITPL) at GSOTU.
Despite the large number of publications
on the properties of oil hydrocarbons, only
Preface
for some of them there was a set of data on
thermodynamic properties and transfer
coefficients, covering liquid and gaseous
states, phase transition lines, and critical
and supercritical regions over wide ranges
of temperatures and pressures. These
substances include light hydrocarbon
gases (methane, ethane, propane, and bu-
tane) as well as n-hexane, cyclohexane,
and toluene. These data are fragmentary
for most hydrocarbons, and information on
them is scattered over numerous literary
sources. Therefore, numerous consumers of
thermophysical information—scientific en-
gineers in universities, research and design
organizations—had to use the information
that was not sufficiently reliable in some
cases, which they found in the literature,
when conducting thermodynamic and
heat-mass transfer calculations. The situation
was constantly complicated because more and
more new substances and technologies and
multicomponent mixtures, for which knowl-
edge of properties was required, began to
appear. In this regard, new, expensive experi-
mental studies were carried out and forecast-
ing calculation methods were created. But
an increase in the volume of information and
its sources does not mean an increase in its
reliability. At the same time, in modern
publications (monographs, reference books,
study guides) on the development of oil and
gas condensate fields and transportation
and processing of hydrocarbons, the sections
devoted to the calculation of thermophysical
properties are based, with rare exceptions,
on nonsystematic information, the reliability
of which requires additional evaluation.
The same claims can be made for the
software products that were widely used for
calculating the thermophysical properties of
hydrocarbons. This results in the need for a
critical analysis of existing experimental data
and methods for calculating the thermo-
physical properties of oil hydrocarbons. Such
 Preface
an analysis has been carried out in the last
10–15years by several international groups
of scientists: in the United States (NIST) by
Lehmann, Eli et al.; in Germany (Ruhr Univer-
sity) by W. Wagner; in England (Imperial
College) by W. Weyham et al.; and in Australia
(University of Western Australia) by Eric May,
Ken Marsh et al. In Russia, such works were
carried out at the Kaliningrad State Technical
University, All-Russian Institute of Natural
Gases and Gas Technologies (VNIIGAZ),
SSSRD, Institute of Thermophysics of the
Siberian Branch of the RAS. Study groups
actively interact with each other and exchange
information on both experimental data and
studies and methods for constructing calcula-
tion equations.
All available experimental data and
methods for calculating the thermodynamic
properties and transfer coefficients of con-
sidered in this book hydrocarbons are ana-
lyzed in this reference monograph offered
to the reader. There were difficulties with
the design of the bibliographic references
due to the large number of publications. It
was considered appropriate to limit refer-
ences to publications with reliable evaluated
data. In addition, in cases where we had the
opportunity to work with theses and mono-
graphs, references were made to them, rather
than to the original articles. As a result, the
number of references has been reduced
significantly.
Information on the main groups of hydrocar-
bons of oil and gas condensates and their phys-
icochemical properties are presented in brief in
the first chapter. The reader is referred to the
monographs by F.D. Rossini, A. A. Petrova,
and others for additional information.
It should be noted our work in this mono-
graph differs significantly from that of our
foreign colleagues working on the equations
of state. Our analysis and development of
the equations of state and interpolation
dependences for n-alkanes, cyclohexane,
xiii
and aromatic hydrocarbons are based on
long-term, comprehensive, wide-range exper-
imental studies carried out in ITPL at GSOTU
(our own experimental data). Studies on hy-
drocarbon properties by domestic scientists
and scientists from the Commonwealth of In-
dependent States (CIS) countries were used to
the maximum extent in the analysis. Many of
these works are either inaccessible to Western
authors or, for some reason, they have been
ignored. At the same time, we have fully used
both experimental data and methodological
developments of our Western colleagues in
the analysis.
A correct, objective analysis of the experi-
mental data involved in the development of
calculation equations is impossible without
assessing the reliability and accuracy of the
experimental methods and experimental con-
ditions and considering various corrections re-
lated to disturbing factors, the correct use of
the applied measurement equipment and
instruments, the purity of the hydrocarbons
under study and their thermal stability in
the studied range of state parameters, etc.
We paid attention to all these features when
analyzing and processing data from studies
by various authors. However, it is not possible
to describe the many methods and facilities
based on which the experimental material
used in this work was obtained. At the same
time, we consider it necessary and appropriate
to incorporate in the book descriptions of test
facilities and experimental methods for mea-
suring thermophysical properties—density,
isobaric heat capacity, surface tension, viscos-
ity, and thermal conductivity—developed or
improved in ITPL at GSOTU, as well as plants
where the study of isochoric heat capacity
(Dagestan Scientific Center of the RAS) and
sound velocity (Kursk State Pedagogical
University) were carried out.
In our opinion, the inclusion of this infor-
mation the second chapter is justified by the
fact that the reader and user of this reference
xiv
monograph will get an idea of the complex-
ity of a thermophysical experiment and the
value of a reliable experimental setup, as
well as the value of forecast calculation
methods based on reliable experimental data
and fundamental theory.
The expediency can be attributed to the
fact that for a thermophysical experiment a
large number of devices and plants are cur-
rently developed and produced by industry.
The plants are usually automated, equipped
with microprocessors, and have unified mea-
suring instruments, data transmission, and
processing channels. This allows increasing
the productivity and reducing the complex-
ity of the thermophysical experiment. But
there is also the flip side of the coin—the
uniqueness of test facilities is lost, the moti-
vation to develop new research methods is
reduced, and the experimentator, who has
obtained a ready-made device in his hands,
often does not know the methodological sub-
tleties, and it is difficult for him to assess the
presence and influence of disturbing factors
on the study subject and on the measurement
result.
Therefore, the book gives a description of
17 original test facilities that have been suc-
cessfully used to experimentally study the
thermophysical properties of hydrocarbons
and petroleum products for 25 years up to
the known events in Grozny. The research
method, its inherent amendments, the test fa-
cility design, the experimental technique,
and the assessment of the accuracy of mea-
surement results are described. Much atten-
tion is paid to the issues of thermostating,
pressure creation and measurement, and ac-
curacy of temperature changes. A fairly wide
range of the properties under study, such as
melting line; saturated vapor pressure; p-, V-,
T-dependence; Cp-, p-, T-dependence; Сv-, ρ-,
T-dependence; sound velocity; surface ten-
sion; thermal conductivity; and viscosity,
are covered.
Preface
The third chapter analyzes the state of the
research on the thermodynamic properties of
oil hydrocarbons in the phase equilibrium
lines: crystal-gas, crystal-liquid, and liquid-
gas. Using local and fundamental equations
of state, a database of hydrocarbon proper-
ties in the phase equilibrium lines was
formed; the temperatures and enthalpies of
phase transitions at the reference points were
calculated; and the individual and general-
ized equations for saturation pressure, the
corresponding densities and heat capacities
of the liquid and gas phases, as well as the
surface tension were proposed.
Chapter 5 devoted to the development of
multiparameter fundamental equations of
state will have an independent interest for
the reader. In writing this chapter, we were
guided by the work of Span, which will be
very interesting and useful for specialists
(Span R. Multiparameter Equations of State,
2000), especially because this work, in
which modern effective methods for
constructing the fundamental equations of
state are considered, is not accessible to a
wide circle of specialists. In addition to the
methods described in this specified publica-
tion and partially described by us, other
possibly more effective methods, which
we have experience in using, are also
considered.
To describe the thermodynamic proper-
ties of oil hydrocarbons in the liquid and
gas phases, including the critical state region
in the parameter range from the triple point
to 700 K at pressures of up to 100 MPa, we
used multiparameter fundamental equations
of state in the form of the reduced Helmholtz
free energy.
As already noted, several study groups
are working on the development of these
equations for technically important sub-
stances. Equations of state have already been
obtained for a number of substances. Based
on an analysis of previously published
 Preface
equations of state, we decided to take advan-
tage of the achievements of Wagner,
Lemmon et al. and include the equations of
state developed for light hydrocarbons
(gases such as CH4, C2H6, C3H8, n-C4H10,
isoC4H10) and cyclic liquid hydrocarbons
(namely cyclopentane, methylcyclohexane,
propylcyclohexane, benzene, and toluene)
in the book. We developed our own
multiparameter fundamental equations of
state for liquid n-alkanes from С5Н12 to
С13Н28; o-, m-, and p-xylenes; ethylbenzene;
and cyclohexane as well as generalized equa-
tions of state for n-alkanes (from С5Н12 to
С50Н102) and cyclic hydrocarbons. It should
be noted that almost all publications on the
thermodynamic properties of oil hydrocar-
bons were used during the development
and verification of these equations. Publica-
tions by researchers from Russia and the
countries of the former USSR will be of inter-
est to Western researchers.
The thermodynamic properties of hydro-
carbons in the critical region are described
by the crossover equations of state. The coef-
ficients of the crossover equation for Н2О and
СО2 (J. Sengers and his group), СН4 and
С2Н6 (A. Abbasi), alkanes from n-С5Н12 to
n-С8Н18, cyclohexane, benzene, and toluene,
as well as for the generalized crossover
equation of state are obtained.
Considerable attention is paid to the anal-
ysis and selection of experimental and calcu-
lated data on the transfer coefficients of oil
hydrocarbons. Chapters 8 and 10 consider
theoretical, semiempirical, and empirical
methods for calculating viscosity and ther-
mal conductivity, respectively. The basis of
the database to obtain individual and gener-
alized interpolation equations for calculating
transport coefficients was formed by in-
house research, as well as work performed
in Baku, at Azizbekov Azineftekhim; in
xv
Dagestan, at the Institute of Physics of the
Dagestan Scientific Center of the RAS; at
the Institute of High Temperatures of the
RAS; and at SSSRD. We have proposed indi-
vidual and generalized interpolation equa-
tions for thermal conductivity and viscosity
of the most important oil hydrocarbons.
In conclusion, we note that in this reference
monograph offered to the reader, the infor-
mation on the estimated accuracy of the ther-
modynamic and transport properties of the
most important oil hydrocarbons [n-alkanes
from СН4 to С13Н18; isoalkanes (isobutane,
isopentane, neopentane, isohexane); cyclanes
(cyclopentane, cyclohexane, methylcy-
clohexane, propylcyclohexane, benzene, tolu-
ene, ethylbenzene, and o-, m-, p-xylenes)] as
well as gases associated with oil and natural
gas extraction (hydrogen, helium, carbon
dioxide, hydrogen sulfide, nitrogen, water
vapor) is concentrated in the form of
multiparameter fundamental equations of
state and interpolation equations. The vast
majority of these equations and experimental
data used to create them were obtained by
the authors of this book or with their participa-
tion. The material concentrated in this mono-
graph can be used for software to simulate
reservoir oil and gas systems and heat and
mass transfer processes in hydrocarbon
processing, transportation, and use technolo-
gies, while developing forecasting methods
for calculating the properties of other
homologous series, as well as hydrocarbon
derivatives.
We are grateful to Professor J. Sengers and
Professor M. Anisimov from the University
of Maryland, United States, as well as Doctor
E. W. Lemmon from the US National Insti-
tute of Standards and Technology and Pro-
fessor W. Wagner from the Ruhr University
of Germany, for their continued attention
and support of our research.
 Contents

About the authors vii 4. Thermodynamic functions of

Foreword ix hydrocarbons in the ideal gas state
Preface xi 4.1 Methods for determining the thermodynamic
properties in the ideal gas state 323
1. Hydrocarbons of petroleum and 4.2 Empirical correlations for calculating the ideal gas
functions 326
natural gases
4.3 Predictive methods for calculating ideal gas
1.1 The main groups of petroleum and natural gas functions of hydrocarbons 333
hydrocarbons 1 References 333
1.2 Basic physical and chemical properties of
hydrocarbons 5
References 12
5. Fundamental equations of state
of individual substances
2. Experimental methods, apparatuses 5.1 Overview of fundamental equations of
state 335
and results of experimental 5.2 Methods of constructing fundamental
measurements of the thermodynamic equations of state based on experimental data
properties of various types 355
2.1 Experimental uncertainties 15 5.3 Fundamental equations of state at the critical
2.2 Thermal properties 22 point 385
2.3 Isobaric heat capacity 124 5.4 Conclusions and recommendations 390
2.4 Isochoric heat capacity 188 References 391
2.5 Speed of sound 203
2.6 Surface tension 213 6. Modern fundamental equations of state
2.7 Conclusions and recommendations 232 for the most important hydrocarbons of oil,
References 233
gas condensates, and associated gases
6.1 Overview of the published equations of
3. Thermodynamic properties on the phase state 397
equilibrium lines 6.2 Critical region 502
3.1 Sublimation point line 251 6.3 Conclusions and recommendations 519
3.2 Melting point line 258 References 520
3.3 Thermal properties on the saturation line
liquid gas 261 7. Experimental apparatus and results
3.4 Surface tension 303
of measuring the viscosity of
3.5 Caloric properties on the liquid-gas saturation
curve 305 hydrocarbons
3.6 Conclusions and recommendations 310 7.1 Apparatus for measuring the viscosity of
References 310 hydrocarbons at the atmospheric pressure 541

v
vi Contents

7.2 Experimental setup for measuring the viscosity 9.5 Conclusions and recommendations 813
of liquid hydrocarbons at pressures up to References 814
60 MPa 544
7.3 Experimental setup for measuring the viscosity of 10. Methods for calculating the thermal
hydrocarbons in the liquid and gas phases 561
7.4 Apparatus for measuring the dynamic viscosity
conductivity of hydrocarbons
of liquids and gases by the capillary method at a 10.1 Dilute gas thermal conductivity of
constant pressure drop 568 substances 825
7.5 The results of the experimental measurement 10.2 Methods for calculating thermal conductivities
of the hydrocarbon viscosities 589 in a wide range of state parameters 833
7.6 Conclusions and recommendations 602 10.3 Thermal conductivity in the critical
References 603 region 841
10.4 Correlation equations of thermal conductivities
8. Methods for calculating the viscosity of hydrocarbons 847
of hydrocarbons 10.5 Conclusions and recommendations 875
References 875
8.1 Dilute gas viscosity 607
8.2 Methods for calculating viscosities in a wide range
of state parameters 619 11. Thermophysical aspects of low-carbon
8.3 Viscosity in the critical region 641 technologies in the energy and oil
8.4 Correlation equations of viscosities of oils and and gas industry
natural gases hydrocarbons 644 11.1 General data about global climate change 881
8.5 Conclusions and recommendations 677 11.2 Hydrogen energy 889
References 678 11.3 Storage and disposal of carbon dioxide 894
11.4 Conclusions 897
9. Experimental apparatus and results References 898
of measuring the thermal conductivity
of hydrocarbons Appendix A 901
9.1 Stationary hot wire method 688 Appendix B 943
9.2 Stationary method of coaxial cylinders 720 Appendix C 969
9.3 The method of coaxial cylinders in the mode
Appendix D 973
of monotonous heating 743
9.4 Results of the experimental study of the thermal Appendix E 997
conductivity of hydrocarbons 757 Index 1051
 C H A P T E R

1
Hydrocarbons of petroleum
and natural gases
1.1 The main groups of petroleum and natural gas hydrocarbons

Petroleum and natural gases are complex mixtures of hydrocarbons and nonhydrocarbon
components—nitrogen, hydrogen, oxygen, sulfur, hydrogen sulfide, etc. Without going into
details, we note that the difference between a petroleum reservoir and a natural gas reservoir
is only in the phase behavior when the temperature and pressure of the formation change. The
hydrocarbon composition of petroleum and natural gases is diverse. Hundreds of hydrocar-
bons of various structures representing almost all homologous series, with the exception of
alkenes, which are not contained in petroleum and natural gases, were found in them. F.D.
Rossini et al. have been systematically studying the physicochemical and some thermody-
namic properties of petroleum hydrocarbons for several years. Sufficiently detailed informa-
tion on these studies is contained in Ref. [1].

1.1.1 Alkanes
Alkanes are saturated hydrocarbons with an open hydrocarbon chain. In natural hydro-
carbon mixtures, they are contained either in the form of normal structure aliphatic
hydrocarbons—n-alkanes: CH3–⋯ (–CH2–)n-2 ⋯–CH3, or in the form of isomers—isoalkanes.
The alkane formula has the form CnH2n+2, where n is the number of carbon atoms in the mol-
ecule. The first representative of this homologous range is methane (CH4). As an example, the
structure of three n-alkanes, methane, ethane, and butane, is shown in Fig. 1.1. The CdCdC
bond valence angle is 112°42’ and the distance between carbon atoms is 1.53 Å in normal
alkanes, judging by measurements based on electron diffraction. Detailed information on
the structure and chemical properties of alkanes is presented in Refs. [2, 3].
For simplicity of illustration, structures that are usually represented by the CH2 and
CH3 groups are not written but show only carbon bonds. For example, the structure for
n-heptadecane is shown in Fig. 1.2.
The first representative of isoalkanes is isobutane. Some examples of isomers are shown in
Figs. 1.3 and 1.4.

Thermophysical Properties of Individual Hydrocarbons 1

of Petroleum and Natural Gases Copyright # 2022 Elsevier Inc. All rights reserved.
https://doi.org/10.1016/B978-0-323-95217-0.00001-4
2 1. Hydrocarbons of petroleum and natural gases

FIG. 1.1 Structure of some normal alkanes.

FIG. 1.2 Structure of n-heptadecane (C17H36).

FIG. 1.3 Structure of isobutane and isopentane (methylbutane).

FIG. 1.4 Structure of isooctane (2-methylheptane).

In the case of isooctane, if the CH3 group is attached to another carbon atom, then we will
get another substance—3-methylheptane. There are other options to attach a methyl group,
for example, 2,3-dimethylhexane and 2-methylheptane shown in a simplified form in Fig. 1.5.
In the name of the substances, the numbers indicate the carbon atom to which a methyl
group is attached. Accordingly, there are two isomers for butane, 3 ones—for pentane, 5
ones—for hexane, 9 ones—for heptane, 18 ones—for octane, 35 ones—for nonane, etc. The
number of isomers increases significantly with the number of carbon atoms in the molecule.
The number of isomers in C5–C12 paraffins exceeds 600, although only 200–400 of them are
found in petroleum mixtures.
Alkanes are gaseous, liquid, or solid substances under normal conditions. Gaseous com-
pounds contain from 1 to 4 carbon atoms (C1–C4) in the chain and are part of associated and
natural gases (methane, ethane, propane, butane, isobutane). Compounds containing from 5
to 15 carbon atoms (C5–C15) are liquid substances, and n-alkanes with carbon atoms over 16
are solids, which can be in a dissolved or crystalline state at the normal temperature in
petroleum, gas condensates, and high-boiling fractions.
 1.1 The main groups of petroleum and natural gas hydrocarbons 3

FIG. 1.5 Structure of 2-methylheptane and 2,3-dimethylhexane.

The total alkane content in petroleum is generally 25%–30% (not including dissolved gases).
Considering the dissolved-state hydrocarbons, the alkane content rises to 40%–50%, and in
some petroleum—to 50%–70%. However, there are petroleums in which the alkane content
is only 10%–15%, similar to gas condensates.

1.1.2 Cycloalkanes (naphthenes)

The cycloalkane molecule is a closed chain (ring). The cycloalkane series begin with cyclo-
propane C3H6, followed by cyclobutane, cyclopentane, etc. Detailed information on the struc-
ture and chemical properties of cycloalkanes is presented in Ref. [4]. The three main types of
naphthenes are shown in Fig. 1.6.
If only one paraffinic alkyl group (i.e., methyl-, ethyl-, propyl-, n-butyl, …) is attached to a
cyclopentane hydrocarbon, then the group is called n-alkylcyclopentanes. The first two hy-
drocarbons shown in Fig. 1.6 are in the above group. There is also a homologous series of
n-alkylcyclohexanes. One of the representatives of this series—ethylcyclohexane—is shown
in Fig. 1.6. Naphthenic hydrocarbons having only one ring are called monocycloparaffins or
mononaphthenes.
The cycloalkane content in petroleum and natural gas condensates is 25%–75%. Cycloalkanes
are present in all fractions. Their content usually increases as the fractions become heavier, and
decreases only in the highest boiling petroleum fractions due to an increase in the content of ar-
omatic structures.
Five- and six-membered rings are the most stable ones. They prevail in petroleum and gas
condensates—many homologues of cyclopentane and cyclohexane have been discovered.
Higher fractions of petroleum also contain bicyclic and tricyclic hydrocarbons of various

FIG. 1.6 Main types of naphthenic hydrocarbons.

4 1. Hydrocarbons of petroleum and natural gases

structures, mainly with two common carbon atoms. In addition, hydrocarbons, which are var-
ious combinations of five- and six-membered rings, often containing aromatic rings—the so-
called hybrid hydrocarbons, were found in petroleum.

1.1.3 Aromatic hydrocarbons (arenes)

A series of aromatic hydrocarbons are formed by benzene and its derivatives—toluene,
xylenes, ethylbenzene, propylbenzene, etc. In a broader sense, arenes are hydrocarbons,
whose molecular structure includes at least one benzene ring. Detailed information on the
structure and chemical properties of arenes is presented in Ref. [3]. Four different aromatic
hydrocarbons are shown in Figs. 1.7 and 1.8.
Each compound in the structures shown in Figs. 1.7 and 1.8 contains a CH group on the
benzene ring. A carbon atom is only contained at the sites of attachment of alkyl groups
(for example, in toluene). Although benzene has three carbon–carbon double bonds, it has
a unique electron arrangement that allows benzene to be relatively inactive (nonreacting).
The petroleum composition includes benzene and its derivatives with attached methyl, ethyl,
propyl, or higher alkyl groups. Such substances are called alkylbenzenes with the general for-
mula CnH2n-6 (where n
6). In general, aromatic series where one ring is present are called
monoaromatic. In turn, naphthalene and its derivatives having two rings are called

FIG. 1.7 Structure of benzene and toluene.

FIG. 1.8 Structure of o-xylene and naphthalene.

 1.2 Basic physical and chemical properties of hydrocarbons 5
diaromatic. Often, heavy petroleum fractions contain many benzene and naphthenic rings
connected to each other. Such structures are called polyaromatic.
The arene content in the petroleum of various fields varies widely and usually ranges from
15% to 50%. Arenes are represented in petroleum by benzene and its homologues, as well as
by derivatives of bi- and polycyclic hydrocarbons. The arene hydrocarbons content in gas
condensates also varies widely—from 1.5% to 50%.

1.2 Basic physical and chemical properties of hydrocarbons

The main physicochemical properties of hydrocarbons include molar mass, normal boiling
point, relative density, refractive index, and kinematic viscosity coefficient. These properties
are used in the identification of hydrocarbons and especially complex hydrocarbon mixtures
of natural and process origin.

1.2.1 Molar mass M (kg/kmol)

Unlike complex hydrocarbon mixtures of uncertain composition, the molar mass of indi-
vidual hydrocarbons is determined with high accuracy but can be calculated quite accurately
using the chemical formula of the substance, taking the mass of the hydrogen atom
mH ¼ 1.0079 kg/kmol and the mass of the carbon atom mC ¼ 12.011 kg/kmol.

1.2.2 Normal boiling point temperature Tb

It is determined experimentally at normal barometric pressure p ¼ 101,325 Pa (760 mmHg).
The normal boiling point determination accuracy mainly depends on the temperature
maintaining accuracy of a test specimen and the temperature and pressure measuring accu-
racy. Contributing factors—temperature range, thermal stability, and purity of the test sub-
stance—are equally important. In general, we can conclude that the higher the normal boiling
point of a hydrocarbon, the less accurately it is determined. For a series of complex high mo-
lecular weight hydrocarbons, there are no experimental data on Tb and calculation methods
are used. These are usually methods of structural-group components [5,6] or empirical cor-
relations; for example, the following simple formula is proposed in Ref. [7].
Tb ¼ 49:5C0:2791
frac M
0:5039
(1.1)

where Cfrac is the fraction of carbon atoms in the molecule: Cfrac ¼ nCn+CnH ; nC is the number of
carbon atoms in the molecule; nH is the number of hydrogen atoms; and M is the molar mass
(mass of kilomole) (kg/kmol).
The accuracy of the calculation is difficult to evaluate, but it is not high, and these methods
can only be recommended for evaluative calculations.
6 1. Hydrocarbons of petroleum and natural gases

1.2.3 Relative density ρtt12

It is the ratio of the density of a substance at a temperature t2 to the density of water at a
temperature t1. In domestic practice [8,9], t1 ¼ 4 °C, t2 ¼ 20 °C are taken for substances with a
melting point below 20 °С and t2 ¼ 70 °C—for substances with a higher melting point. In the
United States and England, the relative density is determined at a temperature of 60 °F, i.e.,
t1 ¼ t2 ¼ 15.56 °C. In domestic literature, this density is indicated as ρ1515. To recalculate the
values ρt4 in ρ15
15, the literature recommends various formulas and tables [9,10]. The author’s
methodology, according to which the recalculation is carried out practically without loss of
accuracy, is presented here [11].
 t 
15 ¼ 1:0009 ρ4 + γðt  15:56Þ
ρ15 (1.2)

where ρt4 is the relative density at a temperature t2 ¼ t and γ is the temperature correction of
density determined by the formula [11].

1
γ¼ (1.3)
43:65
1:706 
MRE
where RE is the specific Eijkman refraction, which does not depend on temperature and is
determined by the formula [12].

2
ntD  1
RE ¼ t
(1.4)
nD + 0:4 ρt4

where ntD and ρt4 are the refractive index and relative density at the t temperature, respectively.
The relative density is generally determined by the pycnometric method [9] with an error
of 0.02%. The accuracy for well-studied hydrocarbons, the density of which was determined
by other instrumental methods, can be increased to 0.01%.

1.2.4 Optical properties

In practice, to identify hydrocarbons, optical properties such as refractive index, molecular
refraction, and dispersion are used.
It is known that the less the refractive index ntD of hydrocarbons, the greater the relative hy-
drogen content in them. The refractive index of cyclic compounds is greater than that of aliphatic
ones. Cycloalkanes occupy an intermediate position between arenes and alkanes. The refractive
index in a homologous series increases with chain elongation. The most noticeable changes are
observed in the first members of the homologous series and then the changes are gradually
smoothed out. However, there are exceptions to this rule. The refractive index for cycloalkanes
(cyclopentane, cyclohexane, cycloheptane) and arenes (benzene and its homologues) is firstly
decreased and then increased as the length or number of alkyl substituents is growing.
 1.2 Basic physical and chemical properties of hydrocarbons 7
A linear relationship in the homological series of hydrocarbons is observed between the
density and the refractive index.
In addition to the refractive index, some of its derivatives are also very important charac-
teristics, for example, specific refraction:
– Gladstone-Dahl formula

nD  1
RGD ¼ (1.5)
ρ
– Lorentz-Lorenz formula

nD  1
RLL ¼
(1.6)
n2D + 2 ρ

where ρ is the hydrocarbon density measured at the same temperature as the refractive index.
The product of the specific refraction by the molar mass M is called a molecular refraction:
ðnD  1ÞM
RGDM ¼ (1.7)
ρ
ðnD  1Þ
RLLM ¼
(1.8)
n2D + 2 ρ
The molecular refraction is additive for mixtures. In addition, molecular refraction is equal
to the sum of atomic refractions, i.e., the group contribution method can be used to calculate it.
The refractive index of a test substance depends on the incident light wavelength. The re-
fractive index is the most important for light with a shorter wavelength and vice versa. The
dependence between the refractive index of light and its wavelength for a given substance is
characterized by the dispersion (scattering) of light.
In laboratory practice, a light source with a yellow sodium line D (wavelength λ ¼ 589.3 nm),
as well as hydrogen lines F (λ ¼ 486.1 nm) and G (λ ¼ 434.1 nm), is most often used.
The difference (nF  nG) is called an average dispersion, and the ratio

nF  nG 3
10
nD  1
a relative dispersion. Finally, the ratio
nF  nG 4
10
ρ
is called a specific dispersion. The specific dispersions of arenes are much higher than those of
saturated alkanes and cycloalkanes.
In the identification of hydrocarbons, one more characteristic that is derived from the re-
fractive index—a RI refractometric difference—is widely used.

D  0:5ρ4
RI ¼ n20 20
(1.9)
8 1. Hydrocarbons of petroleum and natural gases

This value is almost constant for hydrocarbons of the same homologous series.
The refractive index in laboratory conditions is usually determined on refractometers for
the D line with an accuracy of (2 ∙ 104–1.5∙ 105) depending on the type of refractometer.

1.2.5 Kinematic viscosity

Viscosity is one of the most important thermophysical characteristics of a substance; it
varies over a wide range depending on the temperature, pressure, and structure of hydrocar-
bons. The kinematic viscosity ν (m2/s) which is equal to the ratio of dynamic viscosity to liq-
uid density at the same temperature and pressure, is widely used as a physicochemical
characteristic of a substance in technological practice. Kinematic viscosity as a physicochem-
ical characteristic is measured under laboratory conditions at an atmospheric pressure in the
liquid phase. Measurements are usually taken using capillary viscometers. In domestic prac-
tice, Pinkevich viscometers (GOST 33-66) and VPZh-type viscometers (GOST∗ 10028-62) are
used. The measurement error is generally 0.5%–1.0%. More accurate results can be obtained
in special viscosity studies by various methods, some of which will be discussed in Chapter 7.
The kinematic viscosity of the liquid phase is characterized by a strong temperature depen-
dence, especially near the melting point. Various empirical formulas are used to interpolate
the kinematic viscosity, but there is no generally accepted formula, since viscosity, as already
noted, has a strong dependence not only on temperature but also on the structure of the
hydrocarbon.

1.2.6 Critical properties

Critical properties—critical temperature Tc, critical pressure pc, and critical density
ρc—are important thermophysical characteristics of a substance; they are widely used as
parameters for reducing to a dimensionless form in various equations of state and forecast
methods for calculating thermophysical characteristics based on the principle of
corresponding states. Critical properties are usually determined experimentally, using both
direct and indirect methods in the process of studying any thermodynamic properties in the
critical region. A lot of works published in special periodicals have been devoted to the
methods for the determination of critical properties, data analysis, and generalization
(see, for example, Refs. [13–16]). This book does not address these issues. However, given
the importance of critical properties and the fact that they are used in the development of
equations and calculation methods, Table. 1.1 provides the main physicochemical proper-
ties, including critical, of hydrocarbons of various homologous series, which were studied
in the ITPL and are discussed in this publication. The critical properties of hydrocarbons, for
which the authors developed fundamental or interpolation equations, are also discussed in
more detail in Chapter 3.
TABLE 1.1 Main physicochemical properties of the studied hydrocarbons.
Hydrocarbons Formula Purity (%) M (kg/kmol) ρ20
4 n20
D Tm (K) Tb (K) Tc (K) pc (MPa) ρc (kg/m3)
n-Pentane C5H12 99.90 72.151 0.6219 1.3574 143.47 309.22 469.5 3.357 232
n-Hexane C6H14 99.88 86.172 0.6594 1.3749 177.83 341.89 507.4 3.025 234

n-Heptane C7H16 99.96 100.205 0.6838 1.3876 182.55 371.58 540.1 2.7361 234
n-Octane C8H18 99.95 114.232 0.7025 1.3974 216.38 398.82 568.7 2.485 232
Isooctane C8H18 99.02 114.232 0.69190 1.3914 165.800 372.40 543.96 2.485 237
n-Nonane C9H20 99.60 128.259 0.7176 1.4054 219.65 423.95 594.4 2.290 231
2,3,5-Trimethylhexane C9H20 99.90 128.259 0.72191 1.4060 145.25 404.52 579.25 2.324 290

n-Decane C10H22 99.42 142.285 0.7301 1.4119 243.50 447.37 617.6 2.149 228
n-Undecane C11H24 99.37 156.313 0.7402 1.4173 247.58 469.04 638.8 2.004 227
n-Dodecane C12H26 99.64 170.340 0.7488 1.4215 263.58 489.43 658.1 1.859 226
n-Tridecane C13H28 99.09 184.367 0.7565 1.4254 267.78 508.58 675.2 1.756 224
n-Tetradecane C14H30 99.12 198.388 0.7630 1.4269 279.02 526.7 693.0 1.623 222
n-Pentadecane C15H32 98.89 212.419 0.7682 1.4318 283.0 543.8 708.0 1.480 220

n-Hexadecane C16H34 99.04 226.446 0.7734 1.4345 291.0 560.0 723.0 1.400 219
n-Heptadecane C17H36 96.14 240.473 0.7434a
1.4167a
295.0 575.2 736.0 1.340 218
n-Octadecane C18H38 96.00 254.500 0.7480a
1.4189a
301.3 589.5 747.0 1.290 214
n-Nonadecane C19H40 95.00 268.527 0.7521a
1.4211a
305.0 603.1 759.8 1.289 231
а а
n-Eicosane C20H42 97.30 282.553 0.7557 1.4231 310.0 617.0 770.7 1.236 231
а а
n-Heneicosane C21H44 90.64 296.580 0.7539 1.4244 312.7 631.5 781.0 1.186 230
а а
n-Docosane C22H46 92.66 310.607 0.7620 1.4256 317.1 643.9 790.6 1.140 230
а а
n-Tricosane C23H48 92.14 324.634 0.7647 1.4271 320.6 655.0 799.7 1.096 229
а
n-Tetracosane C24H50 90.10 338.661 0.7672a
1.4204 323.3 667.7 808.2 1.056 229
Hexene-1 C6H12 99.30 84.162 0.67317 1.3070 133.32 336.63 504.03 3.142 233

Continued
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