Ind. Eng. Chem. Res.

2010, 49, 11131–11141 11131

Industrial Requirements for Thermodynamics and Transport Properties

Eric Hendriks,*,† Georgios M. Kontogeorgis,‡ Ralf Dohrn,§ Jean-Charles de Hemptinne,|
Ioannis G. Economou,⊥ Ljudmila Fele Žilnik,# and Velisa Vesovic∇
Shell Global Solutions, Shell Technology Centre Amsterdam, Grasweg 3, 1031 HW Amsterdam, The
Netherlands, Centre for Energy Resources Engineering (CERE), Department of Chemical and Biochemical
Engineering, Technical UniVersity of Denmark, DK-2800, Lyngby, Denmark, Bayer Technology SerVices
GmbH, Process Technology, Kinetics, Properties & Modeling, Building B310, D-51368 LeVerkusen, Germany,
IFP, 1& 4 AVenue de Bois-Préau, 92852 Rueil-Malmaison Cedex, France, The Petroleum Institute, Department
of Chemical Engineering, P.O. Box 2533, Abu Dhabi, United Arab Emirates, National Institute of Chemistry,
Department of Catalysis and Reaction Engineering, P.O. Box 660, SI-1001 Ljubljana, SloVenia, and
Department of Earth Science and Engineering, Imperial College London, London SW7 2AZ, United Kingdom

This work reports the results of an investigation on industrial requirements for thermodynamic and transport
properties carried out by the Working Party on Thermodynamic and Transport properties (http://www.
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

wp-ttp.dk/) of the European Federation of Chemical Engineering, EFCE (http://www.efce.info/). A carefully

Downloaded via UNIV ESTADUAL DE CAMPINAS on September 9, 2019 at 02:28:46 (UTC).

designed questionnaire was sent to a number of key technical people in companies in the oil and gas, chemicals,
and pharmaceutical/biotechnology sectors. Twenty-eight companies have provided answers which formed
the basis for the analysis presented here. A number of previous reviews, specifically addressed to or written
by industrial colleagues, are discussed initially. This provides the context of the survey and material with
which the results of the survey can be compared. The results of the survey have been divided into the themes:
data, models, systems, properties, education, and collaboration. The main results are as follows. There is
(still) an acute need for accurate, reliable, and thermodynamically consistent experimental data. Quality is
more important than quantity. Similarly, there is a great need for reliable predictive, rather than correlative,
models covering a wide range of compositions, temperatures, and pressures and capable of predicting primary
(phase equilibrium) and secondary (enthalpy, heat capacity, etc.) properties. It is clear that the ideal of a
single model covering all requirements is not achievable, but there is a consensus that this ideal should still
provide the direction for future development. The use of new methods, such as SAFT, is increasing, but they
are not yet in position to replace traditional methods such as cubic equations of state (especially in oil and
gas industry) and the UNIFAC group contribution approach. A common problem with novel methods is lack
of standardization, reference data, and correct and transparent implementations, especially in commercially
available simulation programs. The survey indicates a great variety of systems where further work is required.
For instance, for electrolyte systems better models are needed, capable of describing all types of phase behavior
and mixtures with other types of components. There is also a lack of data and methods for larger complex
molecules. Compared with the previous reviews, complex mixtures containing carbon dioxide associated
with a wide range of applications, such as capture, transport, and storage are becoming interesting to a number
of survey participants. Despite the academic success of molecular simulation techniques, the survey does not
indicate great interest in it or its future development. Algorithms appear to be a neglected area, but improvements
are still needed especially for multiphase reactive systems (simultaneous chemical and physical equilibrium).
Education in thermodynamics is perceived as key, for the future application of thermodynamics in the industry.
A number of suggestions for improvement were made at all three levels (undergraduate, postgraduate, and
professional development) indicating that the education is correctly perceived as an ongoing process.

1. Introduction instance, for the design of separation processes the issue is

acute, as often more than 40% of the cost of the process is
Accurate knowledge of thermophysical properties of fluids
related to the separation units.1 As well as having impact in
plays an important role in cost-effective design and operation
of chemical and biochemical plants. Broadly speaking, the the design and operation of processes,1 the importance of
thermodynamic properties determine the feasibility of a given thermodynamics in product design,2-5 green and environ-
process, while the transport properties have a major impact mental engineering,6-8 applied nanotechnology/material
on sizing of the equipment. The requirement for accuracy science,9,10 and biotechnology11-14 was recently elucidated.
and reliability varies depending on the application. For Due to the diversity of products and applications, the need
for accurate and reliable thermodynamic and transport
* To whom correspondence should be addressed. E-mail: property data, over a wide range of mixtures and conditions,
eric.hendriks@shell.com.
†
Shell Technology Centre Amsterdam.
is apparent.
‡
Technical University of Denmark. These observations led in 2007 to the creation of a new
§
Bayer Technology Services GmbH. Working Party (WP) within the European Federation of Chemi-
|
IFP.
⊥
The Petroleum Institute.
cal Engineers (EFCE), with the following objectives:
#
National Institute of Chemistry. 1. To promote thermodynamic, transport, and physical
∇
Imperial College London. property measurements, correlations, predictions, and simula-
10.1021/ie101231b  2010 American Chemical Society
Published on Web 10/12/2010
11132 Ind. Eng. Chem. Res., Vol. 49, No. 22, 2010
tions in the academic and industrial chemical engineering
communities, the national societies, as well as among the
national and international funding agencies;
2. To promote concerted education activities to Chemical
Engineers in the areas of thermodynamics and transport
properties;
3. To offer a suitable forum to Chemical Engineers for
exchange of ideas, the development of new basic and applied
research projects, and collaboration through the organization
of conferences, workshops, and related activities;
4. To promote and coordinate research activities at the
European level by identifying chemical systems and conditions
that are important for novel chemical processes and for which
data and/or correlations are nonexistent or inaccurate;
5. To publish quarterly an electronic newsletter summarizing
recent developments in the field.
So far, the new Working Party (WP), entitled “Working Party
on Thermodynamics and Transport Properties” has published
a review on the role of thermodynamics in the chemical
engineering education in Europe and the USA.15 The objective
of the current paper is to report on a second activity that was
initiated by the WP, that is, to investigate the industrial needs
for thermodynamic and transport properties. For this purpose,
a WP task group on Industrial PerspectiVes prepared a
questionnaire that was sent to a number of key technical people
in major oil and gas, chemical, and pharmaceutical/biotechnol-
ogy companies. The responses received to this questionnaire
are analyzed and discussed in Section 3.
To put the analysis in its historical perspective, we briefly
summarize a number of previous reviews that have been
published in the last 20 years. Reviews emanating from both
academic and industrial sources are presented and analyzed.
2. Literature Studies on Industrial Needs
Some of the early review articles from industry including
those of Tsonopoulos and Heidman16 (Exxon) and Zeck17,18
(BASF) are almost 20 years old. They focus on the needs of
oil and gas and chemical industries, which have been tradition-
ally the first industries to make wide use of thermodynamic data
and models. Tsonopoulos and Heidman16 emphasized the then
very dominant role of cubic equations of state which they
consider to be largely adequate for the needs of the oil and gas
industry, due to their applicability to high pressures and
hydrocarbon-gas mixtures. The authors did not discourage the
use of higher-order equations of state (EoS), which were
appearing at the time (such as PHCT), but they were of the
opinion that the petroleum industry would still use cubic EoS
for years to come. Twenty-five years later, the cubic EoS remain
a ubiquitous working tool in the oil and gas industry. However,
association models such as SAFT and CPA are gaining ground,
as the evidence is growing that they are successful for many
petroleum engineering applications featuring water-hydrocarbon
mixtures, especially in the presence of (antihydrate) cosolvents
such as alcohols, as shown in the review of De Hemptinne et
al.19 (IFP).
In the early 90s, when interest in thermodynamics was
regenerated by the new industrial sectors (materials, nanotech-
nology, and biotechnology), Zeck17 wrote: “There is still
considerable potential for improVement for phase equilibrium
thermodynamics eVen in long-established areas of the chemical
industry. With all the enthusiasm about the possibilities of
thermodynamics in new areas, it is necessary first to concentrate
on performing the basic tasks”. The deficiencies of the
thermodynamic models, as Zeck saw them, were often related
to insufficient precision in the description of vapor-liquid
equilibria (VLE) and liquid-liquid equilibria (LLE), as well
as multicomponent LLE, using a single model with a single
parameter set. Many of the basic tasks noted by Zeck are related
to traditional, but still difficult, separation processes like complex
(azeotropic, extractive) distillations, adsorption, or extraction.
About the same time, Mathias and Klotz20 (Air Products) also
considered that main-stream traditional issues such as multi-
component liquid-liquid equilibria are far from solved. They
stated: “RelatiVe merits of these (classical, etc.) mixing rules
are uncertain at present because research is in progress, but it
is clear that the methods should be judged by whether they can
proVide good description of multi-component LLE e.g. for
water-alcohol-hydrocarbons”.
Almost ten years after Zeck’s review, Dohrn and Pfohl21
(Bayer) emphasized that the general needs for thermodynamic
data may differ substantially even within the same industrial
sector, in their case, the chemical industry. The answer to their
question about the availability of thermophysical data elicited
responses ranging from “we don’t haVe enough data” to “we
haVe enough data” including even “we haVe too many data”.
Each of these statements was “justified” based on the avail-
ability, or not, of relevant databases, of suitable models in
process simulators or on the level of difficulty of a particular
separation process. Data especially for multicomponent mixtures
can be scarce and costly even for well-defined mixtures of
industrial importance such as water-hydrocarbons-alcohols or
glycols. Dohrn and Pfohl21 illustrated moreover, via examples,
how similar models may yield different design when used in
process simulators even for rather simple mixtures. For this
purpose, they modeled a mixture of ethyl benzene-styrene with
the Soave-Redlich-Kwong (SRK) EoS. More examples were
given recently by Dohrn et al.22 showing that results may be
sensitive to the specific parametrization used in models. So the
evaluation of thermophysical property data should play an
increasingly important role in industrial thermodynamics.
Agarwal et al.23 (Virtual Materials Inc.) in their review
focused their attention on what they called “less attractive” (or
often neglected) properties such as heats of mixing, entropies,
excess volumes, and heat capacities. Such properties could be
used for additional validation and model development, and the
authors investigated how cubic EoS (using either classical or
advanced EoS/GE mixing rules) perform for these properties.
They conclude:
“Traditional actiVity coefficient models such as NRTL
haVe limitations on the magnitude of the excess enthalpies
they can predict. How these models behaVe inside cubic
EOS for the calculation of deriVed properties is not well
known and is disappointing sometimes. So, if you are
modeling a system with significant excess enthalpies using
a Gibbs free-energy-based EOS and you haVe a good VLE
fit, this does not automatically ensure you haVe a good
oVerall model from an energy balance point of View.”
About the same time, articles on industrial needs specifically
addressing polymer properties (from ASPEN24 and Bayer25)
appeared, illustrating that a large variety of models may be
required for designing polymer processes.
Simulator developers and providers have also frequently
published their opinions on thermodynamic requirements. Carl-
son26 (ASPEN) discusses the importance of using the so-called
decision or selection trees for selecting appropriate models
suitable for specific applications. He further discusses various
techniques, such as family plots, for estimating missing param-
eters. In general, commercial simulators offer a lot of versatility

to the end user, but this comes at a price of sometimes
bewildering choice of models, model varieties, mixing rules,
and parameter selection.
Chen and Mathias,27 also from ASPEN, stated that in many
industrial systems polymers, electrolytes, sometimes surfactants,
and mixed solvents coexist, and this gives rise to multiple
simultaneous interactions. One of the major messages of their
investigation is that many existing models have been developed
for each subsystem independently (for example, only for
polymeric or electrolyte mixtures), and such independent
developments should be abandoned if future models are to have
wide applicability. They further emphasize that there is a great
demand for thermodynamic models for complex products, such
as consumer goods and bioprocesses. Another important issue
that is discussed is the industrial response to the developments
in the field. Chen and Mathias27 argue that industry rarely
updates or replaces its thermodynamic models with newer and
better correlations unless a clear advantage is evident. It often
takes a long time, of the order of 10 years or more, for a new
model to be conceived, developed, validated, and accepted by
the industry.
One of the most recent and extensive industrial articles on
thermodynamic requirements is that by Gupta and Olson28 (Dow
Chemical). In particular, they state:
“Most past work focused on extensions of cubic VdW-
type EoS ... This has occurred despite the now famous
recommendation of Henderson. No matter how sophis-
ticated a mixing rule, the use of Van der Waals-type cubic
equations of state force their inherent limitations on the
users. These are the ability to reasonably predict only
the Vapour pressure of a select series of components and
only an approximate modelling of the effect of liquid
density and compressibility. Van der Waals-type cubic
equations are unable to accurately model other liquid
phase properties, for example, enthalpy and heat capacity
also phase equilibria at high pressures, particularly the
mixture critical locus.”
Gupta and Olson illustrate, via examples (simultaneous VLE
and LLE of alcohol-alkanes), that SAFT-type models should
be preferred over cubic EoS for phase equilibria of polar
mixtures.
A report for the Eureka project written by Moorwood29
(InfoChem) discussed status and requirements for thermody-
namic data for a very broad range of applications including
metals and agrochemicals. In addition, Bruin30 (Unilever)
discussed some thermodynamic needs specifically related to food
industry.
In the most recent joint industrial-academic work, O’Connell
et al.31 analyzed in detail a number of specific cases from a
thermodynamic perspective. Special emphasis was given to the
need for simultaneous physical and chemical equilibria data,
for solvent selection for pharmaceuticals, and for formalde-
hyde-water and CO2-water-alkanolamine mixtures.
During the past decade, several articles have appeared from
industrial sources (Astra Zeneza, Mitsubishi, ASPEN, Merck,
etc.) on thermodynamic requirements of the pharmaceutical
sector,32-37 particularly the need for accurate and reliable models
for solvent screening. A variety of models have been tested,
ranging from modifications of UNIFAC and solubility param-
eters to modern versions of local composition models, such as
NRTL-SAC,38 and methods based on quantum chemistry like
COSMO-RS39,40 and COSMO-SAC.38 The use of quantum
chemistry methods in pharmaceutical industry has been also
Ind. Eng. Chem. Res., Vol. 49, No. 22, 2010 11133
highlighted in industrial lectures (for example, by Natori, 2001,
at the PPEPPD conference in Kurashiki, Japan).
A systematic investigation on industrial needs for both
thermodynamic and transport properties has been conducted
under the so-called Forum 2000 project, and the results are
documented in a detailed report41 and several publications.42,43
One important comment from Forum 2000, by Jim Olson
(Dow Chemical), focuses on the need for reliable experimental
data for families of compounds which have not been systemati-
cally studied:
“We can neVer conduct all the necessary experiments -
but many data measurements are missing. For instance,
multi-functional chemicals such as alkanolamines, glycol
ethers, excess properties like excess Volumes at Various
temperatures, amides, liquid phase heat capacities,
enVironmental phase equilibrium, safety data e.g. flash-
point and auto ignition temperatures, simultaneous physi-
cal and chemical equilibrium, ...”
The need for reliable experimental data is the message that
is also strongly supported by other industrial-oriented reviews,
e.g., by Rhodes44 (Union Carbide) and Richon.45
Other important comments from the Forum 2000 work are
related to the need for accurate data and models for transport
properties. For example, Bill Wakeham stated: “Thermal
diffusion, although an abstruse transport property, will turn out
to be extremely important in oil reserVoirs, due to the large
T-differences”. He later added:
“What’s the data in tissue engineering that we need? If
you look at the way cancer tumours are sometimes
remoVed, which is ultrasonic’s or microwaVes, this is all
done by heating. The thermal conductiVity of the tissue
you heat, the heat capacity of that tissue, matters and
they don’t know it. Sometimes it is measured in Vitro
neVer in ViVo.”
P. Mathias stated: “Transport properties are becoming
increasingly important, but little attention has been deVoted to
them”. He further made a point on solids: “When one actually
does modelling, with particle sizes, the issues of nucleation and
growth are important. An area I think chemical engineers did
many things 30 or 40 years ago, but there’s not been a lot
recently”.
So far, we have summarized some comments and opinions
based on the reviews of articles from industrial sources. Several
reviews emanating from academia have also been published.
In particular, the review by Prausnitz and Tavares46 and more
recently a book by Kontogeorgis and Folas38 review a large
number of thermodynamic models and present an outlook for
future developments. According to most of the academic
reviews, important advancements in thermodynamics are needed
to address issues related to “post-modernism”,47,48 life sciences/bio-
technology,11-14,49,50 and chemical product development.2-5,9,10
Moreover, there is a need to connect closely with other
disciplines of chemical engineering, such as mass and heat
transfer, nucleation, and chemical kinetics. One example where
such an interdisciplinary approach would pay great dividends
would be in the design of controlled drug release systems.
The postmodernism trends in chemical engineering encom-
pass the need for more “human aspects” in the curriculum. They
emphasize the role that chemical engineering plays in society
and provide ample opportunity for thermodynamics. The near-
future focus should be on addressing different environmental
and safety related aspects, for example, the use of supercritical
fluids, the optimization of processes related to CO2 capture and
storage, as well as modeling of loss-prevention scenarios.6-8,47,48
11134 Ind. Eng. Chem. Res., Vol. 49, No. 22, 2010
Many recent investigations39,40,51-53 point to the increasing
importance of quantum chemistry especially in the form of
models like COSMO-RS and COSMO-SAC for thermodynamic
calculations and especially screening purposes for a wide range
of situations, mostly at low pressures.
The role that the molecular description increasingly plays in
modern thermodynamics has been emphasized by Prausnitz:9
“Thermodynamics is often most useful when directed at
deVeloping model for new situations, where our quantita-
tiVe understanding is seriously inadequate. Pioneering
molecular thermodynamics is concerned not with im-
proVements where primary understanding has already
been achieVed, but with shedding light on situations where
as yet, we know little. For many practical problems, old
theories are sufficient proVided that they are used with
courage and imagination.”
3. Questionnaire and the Survey
The task group Industrial PerspectiVes appointed by the
EFCE Working Party on Thermodynamics and Transport
Properties (EFCE WP) prepared a questionnaire comprised of
seven questions that are presented in Appendix 1. The questions
ranged from simple yes/no answers to the ones that were open-
ended where any issue related to thermodynamic and transport
property requirements could be addressed.
The overall purpose of the survey was to:
• Review the situation in industry with respect to thermody-
namics and transport properties requirements. The emphasis was
primarily to collect information on European industry, although
some companies from the USA, Japan, Thailand, Brazil, and
South Africa were also included in the survey;
• Identify limitations in current approaches;
• Provide specific recommendations on R&D work (to be
initiated by the EFCE WP and individual researchers in this
area).
A list of possible companies that could take part in our survey
was created with the contact names collected by the coauthors
of this paper, and the invitations were sent out. Fifty-nine
companies in total from sixteen different countries were
contacted, and the reminders were sent out to increase the
number of responses. In total, 28 replies were received, which
represents a 47% response rate. Most responses were from
European but globally operating industries. Figure 1 illustrates
the industrial sectors of the companies that have responded to
the survey.
4. Results
Although it is rather difficult to categorize and summarize
an overwhelming number of answers received, an attempt is
made to summarize the essential features by means of Figure
2.
Figure 2 shows on the left the industrial requirements
regarding thermodynamics and transport properties, summarized
by a few keywords. The requirements are usually short-term,
and this is probably why there is a resistance in trying out
recently developed advanced tools, such as SAFT EoS and
molecular simulation (“first concentrating on basic tasks”). Yet,
the industrial requirements often relate to complex thermo-
physical systems, hence the reliance in some instances on simple
“rule of thumb” approaches, which are believed by industry to
give a good indication of trends. Finally, industrial needs require
either (i) the knowledge of thermophysical properties at given
operating conditions or (ii) in product design the ability to design
Figure 1. Responses to the questionnaire classified by industrial sector.
Some responders work in more than one category.
the right product with specific thermophysical properties (i.e.,
solvent design).
The “supply” from the thermodynamic community is pre-
sented in Figure 2 as a triangle that should respond to these
needs: the response is the “package” that includes models,
parameters, and algorithms. Ideally, this model should be unique,
independent of the type of system or operating conditions. To
construct this ideal package, the three vertices of the triangle
must be considered:

Upper left: what is the molecular system under inVestiga-
tion? There is a plethora of mixtures of industrial interest, and
it is more or less impossible to include every conceivable
combination. A reasonable approach would be to rely on good
description of thermophysical properties of pure species and
use modeling tools to obtain the properties of the mixtures. The
industrial interest changes with time, as a result of new
developments, new processes, and new products. Currently, there
is an emphasis on CO2, electrolytes, and polyfunctional mol-
ecules. Many molecular systems are compositionally well-
defined, but this is not always the case. For instance, for
reservoir fluids the detailed molecular composition is usually
not available, hence some additional characterization is needed.

Upper right: what is the property required? Although VLE
remains the most common, other types of phase equilibria (LLE,
SLE) are nowadays also in demand. Furthermore, there is an
increasing need for enthalpic properties (heat of mixing, heat
capacities, etc.) and transport properties. The traditional cubic
EoS is of limited use for this purpose,28 and one requires more
sophisticated models that are not necessarily available in every
package.

Lower corner: data. The most traditional approach is to
claim that there are not enough data or to use the available data
without any analysis of their accuracy or reliability. Although
it is true that for a large number of systems the data are scarce,
when the data are available one should ask the question
according to Dohrn and Pfohl:21 “do we have the correct data
(that means useful in view of the applications)?”
At the very right of Figure 2, the various state-of-the-art
predictive tools that the thermophysical property community
can use, to respond to the industrial needs, are illustrated.
Molecular simulation plays an essential role, as well as quantum
chemistry, as both have shown great advances in terms of both
development and applications. In the near future, other com-

Figure 2. Schematic illustration of the position of thermodynamic tools for the oil and gas, chemical, and process industries.
putational techniques might become available including, for
example, the ones dealing with nonequilibrium thermodynamics
or calculation of transport properties directly from intermolecular
potential. Industry is not yet fully aware of the applicability of
these computational techniques to address their requirements,
which is why very few industrial comments on this issue were
found in our survey. It is thus the role of the academic
community to introduce the use of advanced computational
techniques, by both further refining theoretical models and
showing that the results can be used as alternative, pseudoex-
perimental data, or parameter provider.
In the next set of subsections, we present and analyze the
results obtained in the current survey. For ease of use, the main
conclusions from the survey are presented in the bold font in
the first paragraph of each section.
4.1. Data. There is an acute need for high-quality experi-
mental data for both thermodynamic and transport proper-
ties, including the phase and chemical equilibrium data.
The high-quality data can only be obtained in a well-
characterized experimental apparatus with a well-defined un-
certainty level, which cannot be demonstrated to be inconsistent
with other data or with theory. Although such instruments do
exist, their use requires knowledge of their full-working
equation, and in some cases it requires a number of corrections,
to account for the nonideality of the apparatus, to be made to
experimental data. Thus, producing high-quality data is expen-
sive and time-consuming, and not surprisingly, such data are
scarce. It is important to emphasize that rather than focusing
on the amount of data available for a particular system one
should focus on gathering reliable data with well-defined
uncertainty levels that cover the phase space of interest. Such
sets of high-quality data, that are mutually consistent, can then
be used as a benchmark data set for a particular system essential
for validating or developing predictive models and tools.
More specific comments that were made in the survey were
as follows:
(i) For complicated molecules, containing multiple functional
groups (e.g., hyper-branched polymers, dendrimers, micelles)
that are used for fine chemicals, crop protection, and bioappli-
cations, very few phase equilibrium data exist in the open
literature. So group contribution methods are less accurate for
these molecules, as there are no data to fit the required
parameters.
(ii) For many traditional/bulk chemicals, a large number of
data sets exist that do not agree with each other. Most of the
data have been measured a long time ago in the apparatus whose
description does not allow for their proper levels of accuracy
to be established. There is a lack of high-quality reference data
to which model parameters can be fitted for process simulation.
Ind. Eng. Chem. Res., Vol. 49, No. 22, 2010 11135
Simple examples mentioned in the survey include the inorganic
acids, like sulfuric acid, hydrochloric acid, and nitrous acid.
(iii) The participants of the survey felt that the emphasis
should be given to more measurements on: (i) gas solubilities;
(ii) high-pressure and high-temperature phase equilibrium data
of nonideal mixtures; (iii) dilute conditions; (iv) solubilities and
diffusion in polymers; (v) reactive multiphase systems (CO2,
H2S-water-alkanolamines); and (vi) electrolytes. Essentially,
there is a need for high-quality data for a wide range of systems
and conditions.
(iv) Data are also lacking in petroleum-related applications
for: (i) gas hydrate systems, e.g., hydrate formation with CO2
and H2, with additives, and with loss of hydrate inhibitor such
as methanol and glycols; (ii) properties of heavy oils; (iii)
partition coefficient of gases in hydrotreatment conditions,
especially in the presence of oxygenated fuels; (iv) heats of
reaction and of adsorption; and (v) VLLE of complex natural
gas mixtures including water and electrolytes.
(v) There is an acute need for transport property data that
include viscosity, thermal conductivity, and diffusion coefficient
data. Especially, emphasis was put on the lack of data for
electrolytes and ionic liquids. It was noted that even when some
transport property data do exist they do not cover an extensive
temperature and pressure range.
(vi) The lack of data is made even more acute by the
observation that there are fewer research groups (at least in
Europe) that have well-equipped laboratories and have funding
to devote time to measurements. The disappearance over the
years of a number of research groups that were producing high-
quality data is a worrying trend, as without the high-quality
data the existing databases will become less useful as the
tendency to target quantity rather than quality will intensify.
(vii) A number of participants indicated that when the data
need is clearly identified in view of specific industrial require-
ment, companies do not hesitate to spend money to measure
the relevant properties. However, as these data are often
considered strategic, they are not always published. Note that
policy of expecting to find a laboratory, when a particular need
arises, that can perform the high-quality measurements is
relatively short sighted. Producing high-quality data requires
continuity in terms of both maintaining apparatus and even more
importantly maintaining research expertise, as the high-quality
measurements cannot be performed on a short-term basis by
inexperienced researchers.
(viii) The use of advanced computational tools, such as
molecular simulation or quantum chemistry, is sometimes
mentioned as an alternative to “producing” experimental data,
but this approach is currently not commonly accepted by
industry.
11136 Ind. Eng. Chem. Res., Vol. 49, No. 22, 2010
4.2. Models. 4.2.1. Scope of the Models. There is a need
for reliable thermodynamic and transport property models
for a Wery wide range of systems.
The participants of the survey put the special emphasis on:
(i) Need for models for phase equilibria and transport
properties, preferably within a single framework, that cover all
the components and conditions of interest and with good inter-
and extrapolation capabilities in temperature, pressure, and
composition.
(ii) The framework should be targeted toward making use of
generalized and simple equations of state for nonpolar, polar,
associating, and high boiling substances and their mixtures, with
sufficient accuracy for industrial purposes.
(iii) The number of available models in the literature should
be reduced by recommending either a unique model or a small
number of models. Today, specialists in industry are required
to recommend the best modeling approach for a specific
application, and the number of available models or versions of
the same model are sometimes bewildering.
More specifically, the survey results indicated:
(i) The models should cover the requirements of very diverse
industrial fields: (a) oil and gas including heavy oil, mercury
compounds, syngas, asphaltenes (currently poorly characterized),
and organic sulfur compounds; (b) chemicals including complex
oxygenated chemicals related to biofuels, ionic liquids, surfac-
tants, and polymers; (c) biotech including biopolymers, phar-
maceuticals, and building blocks; (d) colloids including emul-
sions, surfactants, food additives, emulsifiers, adhesives, and
gels; and (e) metal and mining. The applications were by and
large dependent on the industrial sector, but the following
processes were particularly emphasized as in need of good
models: flow assurance (gas hydrates, asphaltenes, and wax);
separation methods other than distillation/extraction, e.g.,
adsorption and chromatography; and crystallization.
(ii) As can be seen from the above list, requirements and
expectations for models are not only diverse but also very
extensive. Clearly current models cannot cover or meet all areas
of interest and expectations. However, an interesting issue is
that there is a feeling that models are incomplete or lacking
even in areas which might have been considered “mature”. For
instance, for bulk chemicals it was felt that a very important
system of ammonia-water-sulfuric acid is poorly addressed
by any of the available models. In the oil and gas area, the
presence of mercury and sulfur compounds was equally badly
catered for by the modeling community. There is a feeling that
an analysis of the different requirements and expectations carried
out for each industry sector would be useful.
(iii) A lack of high-precision EoS for a number of systems
was noted.
4.2.2. Theoretical Foundation of the Models. Traditional
and novel models are equally important, and developments
in both should continue.
Model approaches used in industry range from traditional
group-contribution (GC) models especially UNIFAC to modern
approaches such as COSMO-RS and SAFT. The general
consensus is that:
(i) The development of both UNIFAC and COSMO-RS
should continue as they are both very useful for industrial
applications. There was a suggestion that some work should be
carried out to combine them, by for instance making use of
group contributions for the sigma profiles of COSMO-RS. The
prediction of UNIFAC and COSMO-RS should be compared
as the actual range of applicability and accuracy appears to be
very system-dependent. Molecular modeling should be further
developed to gain better understanding, and molecular simula-
tions are suggested to improve the prediction of thermophysical
properties and phase equilibrium.
(ii) The GC models in general are used and are needed in
many contexts that do not necessarily involve predicting phase
behavior, for instance, for computer-aided product design,
properties of heavy compounds (even for pure species: melting
temperature, vapor pressures, etc.), solvent screening, emulsions,
and oxygenated compounds. Thus, the full phasing out of GC
models in favor of modern models is not yet imminent.
(iii) SAFT-based models are promising tools, but the requests
from the industrial community for these models are multiple:
• Characterization methods for oils, asphaltenes, and similar
complex mixtures;
• Speed must be improved for routine applications (see also
next point on standardization);
• Recommended pure-component and binary parameters
should be collected and made available;
• True improvements over classical cubic EoS should be
demonstrated, especially for multifunctional, complex, and
associating compounds like oxygenated compounds (biofuels);
• The model should be applied to truly important new areas
including polymers and electrolytes;
• Standardization is needed. This is further discussed in
section 4.2.3.
4.2.3. Availability of the Models. Standards are very
important for thermodynamic models.
The term “Standards” has been used and understood in
different (sometimes complementary) contexts, both in imple-
mentation and model validation:
(i) Models should be present in simulators for active use by
industry, otherwise, they may be forgotten. CAPE-OPEN is a
useful (and standard) tool for integrating user developed unit
operations and thermodynamics packages in commercial process
simulation programs, but it is still not fully developed and
supported. One of the comments in the survey was that the
analytical derivatives are needed. The tool should be improved
further, allowing exchange of thermodynamic packages belong-
ing to different process simulators.
(ii) The number of new models is enormous, even within the
same family. For instance, there are numerous versions of SAFT.
Sometimes different results are obtained with what should be
the same model. Proper coding and validation are extremely
important to ensure full reproducibility of the results. This should
also be performed by other researchers rather than just by those
involved in the model development.
The question arises how can this be accomplished? It is worth
investigating some process that would lead to a proper com-
parison of models. A first step in such a process could be the
agreement to use some standard well-accepted databases for
validation purposes. A second step would be the agreement on
criteria for model validation which could be used by all
developers. In particular, the model developers should try to
present, in a few comprehensive articles, all equations of their
models including a thorough evaluation. The codes can be made
publicly available, but a good accompanying documentation
would be necessary.
4.2.4. Algorithms. Implementation of the thermodynamic
models requires reliable flash and related algorithms, and
although significant developments have been made in the past
(e.g., Michelsen and Mollerup54), new challenges are appearing,
in particular, the need for very fast and robust calculations for
flashes, the presence of multiple phases, and reactive systems.
Further, there is a need to improve the stability test, the most

time-consuming element of the multiphase calculations. Un-
fortunately, the field does not seem to be of active interest to
the thermodynamic community.
4.3. Systems. The most popular systems appear to be
electrolytes, CO2, and larger, polyfunctional molecules.
These systems appeared repeatedly in a survey in different
contexts from a number of companies belonging to different
sectors.
In particular:
(i) There is a need for improved description for electrolyte
systems that go beyond e-NRTL.38 The emphasis should be on
describing all types of phase behavior (VLE/LLE/SLE) covering
also electrolyte mixtures with water, other organic chemicals
(i.e., mixed solvents), and hydrocarbons (natural gas), over
extensive temperature and pressure ranges, up to high salt
concentrations. Electrolyte models are multiparameter models,
and modern e-EoS38 may be a way to go; however, much
remains to be done. There is a need to bring electrolyte
thermodynamic models to a level comparable to other fields.
The need for improved electrolyte models is common among a
wide range of industries.
(ii) There is a lack of data and models for larger molecules,
complex molecules, biomolecules (biopolymers, proteins, phar-
maceuticals, gels), or molecules that contain multiple functional
groups (polar and associating ones) that are used as food additives.
(iii) CO2 mixtures with water, polar chemicals (methanol,
glycols) including mixed solvents, H2S, N2O, O2, hydrocar-
bons, and (alkanol) amines appear of importance to a wide
range of applications (gas hydrates, oil and gas, CO2 capture,
transport, and storage). Of special importance to a number
of participants was that the description of the system covers
very extensive temperature and pressure ranges. The CO2-
containing systems also include electrolytes, as CO2-brine
(+ rock mineral) systems are of great interest in CCS (CO2
capture and storage) applications. A number of the systems
described are chemically reactive which further complicates
their thermophysical description.
4.4. Properties. Multiple thermodynamic properties are
of importance.
It was frequently stated in the survey that simultaneous
description of different thermodynamic properties and phase
equilibrium types is of great importance. Internal thermodynamic
consistency of the generated data by a given model is nowadays
as essential as accuracy and reliability. This is especially
important as the thermodynamic models are often used as part
of the simulator by a different set of software developers who
are not necessarily aware of all the nuances of a particular
thermodynamic model.
Hence, thermodynamic modelers should no longer be satisfied
with models that for instance give only good VLE results at
low pressures but are either untested or fail for other properties
and regions of the phase space.
In particular, the results of the survey indicated that for
equilibrium properties:
(i) Simultaneous description of VLE and LLE (+ VLLE) is
of interest with the same model and the same parameter set,
especially for complex multicomponent mixtures.
(ii) So is the simultaneous description of the phase behavior
and derivative properties (e.g., heats of mixing).
(iii) Special attention should be given to dilute systems
(infinite dilution), and the description of the system should be
mutually consistent with the description at higher concentra-
tions.
Ind. Eng. Chem. Res., Vol. 49, No. 22, 2010 11137
(iv) Extrapolations to high temperatures and pressures are
often needed, for instance, for gas solubilities in water-
hydrocarbon-CO2 mixtures that could involve salts and other
chemicals. The proposed correlations should have sensible
extrapolation behavior.
A number of other properties were mentioned as important
for specific applications:
(i) SLE is crucial for a variety of separation processes, e.g.,
crystallization, as well as for mineral stability and hydrate
formation in the oilfield.
(ii) Surface phenomena (adsorption) are typically equilibrium
phenomena that play an important role in a number of
applications.
(iii) Chemical reactions (formation properties).
None of these properties are currently well catered for by the
thermodynamic community.
Nonequilibrium properties: combined thermodynamic/
transport effects and appreciation of nonequilibrium effects
are important.
(i) There is a need for combined models for predicting
thermodynamic and transport properties, reaction rates, and
diffusivities. There is a need for a good procedure to disentangle
reaction kinetics and mass transfer where both processes
contribute.
(ii) Is it possible to predict transport properties from
thermodynamic data alone? Can we reliably estimate thermal
and transport properties from limited vapor pressure and density
data?
(iii) There is a need for models for predicting properties,
especially transport properties of complex products present
in many fields of process industry, such as viscosity index
of lubricant base oils from composition and octane/cetane
numbers.
(iv) What is the effect of nonequilibrium behavior? It is not
always clear whether a system is in thermodynamic equilibrium
or not.
(v) There are cases where thermodynamic predictions may
be quite misleading because of slow reaction kinetics, or poor
mass transfer, e.g., predicting inorganic scale deposition.
(vi) In many processes, the nonequilibrium part can be of
importance, e.g., nucleation in crystallization and gas hydrate
formation.
(vii) It would be of great industrial interest to develop
fundamental nonequilibrium thermodynamic approaches for
predicting transfer across boundaries (for replacing the empirical
“transfer efficiency” equations).
4.5. Education. What is the role of education in thermody-
namic modeling for process and product design? There is a clear
agreement among the participants in the survey that education
is the key for an appropriate use of thermodynamics in industry.
Three different levels of education are relevant in this context,
each with different requirements:
(i) Undergraduate education: it is essential that engineers in
operating companies know some basic thermodynamics but even
more importantly that they are aware of the limitations of their
understanding. This is especially relevant as black-box type
simulators are routinely used these days.
(ii) Professional development: with the advent of new
technologies (simulators) or as a result of job changes, people
may be confronted with new challenges after several years of
professional experience. The field of thermophysical properties
is evolving rapidly, and there is a need for industry professionals
to keep up with the latest developments.
11138 Ind. Eng. Chem. Res., Vol. 49, No. 22, 2010
(iii) Postgraduate education: the complexity and the wide
applicability of thermodynamics leads to a need for specialists
within a given company, typically educated to a PhD level, to
act as an internal expert on thermodynamic and transport
property issues.
4.6. Collaborations. Data collected revealed that:
(i) The R&D organization in the various companies is
generally rather strong: 25 out of 28 companies have a research
lab, and 9 of them have a research subsidiary.
(ii) Most of the companies that took part in the survey have
bilateral collaborations with universities. The average level of
collaboration fulfills close to 10% of the total research need.
Some companies rely quite heavily on it.
(iii) 25 out of 28 companies participate in consortia. Yet,
the willingness to participate in joint R&D programs is
surprisingly conservative with only 14 out of 28 indicating
a clear yes.
(iv) The area for joint collaboration is rather diverse: from
gathering new data to developing parameter tables (UNIFAC
consortium is often cited as an example).
5. Conclusion: Discussion and Comparison to Previous
Studies
A short discussion is provided in this section contrasting the
results of our industrial survey and those from the literature
that were presented in section 2.
An important common feature of current and previous
investigations (see for example a recent discussion45) is the
need for experimental work which will result in high-quality
measurements that are accurate, reliable, and thermodynami-
cally consistent. In many cases, the real accuracy of published
experimental data is far lower than the accuracy given by
the authors, as discussed by Peper et al.56 The importance
of practical expertise of the experimentalists in obtaining
high-quality data has been highlighted by Dohrn et al.55 in
their recent review on experimental methods for high-pressure
phase equilibria. Often, the qualification of the staff and their
familiarization with the technique have a stronger influence
on the accuracy of experimental results than the choice of
the experimental method or the equipment. Our survey shows
that there is a clear need for qualified laboratories with
experienced staff to provide experimental measurements. As
many companies seek to reduce in-house facilities for routine,
nonexploratory type of measurements, this need will likely
increase. Universities have also reduced their experimental
activities. The key problem is that performing high-quality
measurements requires accumulation of many years of
experience for which funding has to be secured. The different
funding bodies in many instances do not see this type of
activity as leading edge research and in the present climate
decline to fund it. Furthermore, the pain-staking effort leads
to a rather limited publication output. Nevertheless, data are
lacking for a wide range of systems from “simple” common
mixtures up to multifunctional chemicals, complex com-
pounds originating from biomass, ionic liquids, polymers,
and pharmaceuticals. Surprisingly, the data are still very
scarce for solubility of water in CO2 at high pressures and
for mixtures that involve inorganic acids or ammonia.
Another common feature of the current survey and the
previous ones is that reliable models are needed and that
the predictive character is essential, but many existing models
are essentially correlative. Thus, SAFT, COSMO-RS, and
UNIFAC (GC) approaches should be further developed, and
it appears unlikely that a single tool will be sufficient in all
cases. Most models have serious problems when applied to
(poly)electrolyte systems, mixed solvents relevant for gas
treatment using amines, and new solvents like ionic liquids.
The simultaneous presence of polymers, electrolytes, and
biomolecules is also an area where none of the models
perform adequately. These are areas where important revi-
sions and improvements are needed. It is particularly interest-
ing that deficiencies in current electrolyte models are apparent
even for models used in commercial simulators, as illustrated
in a recent joint academia-industry project.57 Emphasis on
electrolytes and polymers is found in both previous and the
current investigation. New in our survey is the special interest
in predicting the thermophysical properties of mixtures
containing CO2. This is a direct result of climate change
concerns and the development of sustainable technologies,
in particular, the CCS.
Regarding the capabilities of thermodynamic models, we can
state that the advent of SAFT-family models has certainly
contributed to better representation of a wide range of systems
(nonpolar, polar, associating, polymers, etc.) and the simulta-
neous representation of various phase equilibrium types, e.g.,
VLE and LLE. On the other hand, there is a clear impression
from the survey that certain important issues, also emphasized
in the earlier industrial studies, have been overlooked. Good
examples are the multicomponent multiphase equilibria espe-
cially for prediction purposes and the accurate description of
derivative properties (e.g., heat capacity, speed of sound,
enthalpy of mixing) together with phase behavior. Clearly, these
issues need to be considered and included in future develop-
ment-model validations.
Some of the previously published industrial reviews empha-
sized molecular simulation techniques as enabling technology
which can supplement the experimental data or act as pseu-
doexperimental data at temperatures and pressures where
experiments are difficult. However, the participants of the current
survey were not particularly encouraging the further develop-
ments of molecular simulation, which is a rather disappointing
state of affairs.
Algorithms appear to be a neglected area in many of the
previous publications, but the results of the current survey
illustrate that the improvements are clearly needed, especially
for multiphase and/or reacting systems (simultaneous physical
and chemical equilibria).
According to the current survey, implementation is an
important issue to the industrial users. In the previously
published reviews, this aspect was not emphasized greatly,
although the importance of CAPE-OPEN58 standard has been
mentioned. The issue of having standardized and validated
models is particularly highlighted in the current survey. The
new models are published very frequently, but unfortunately
most, if not all, of these models are tested against only a
few data sets. A large, standardized set of data against which
all models may be tested will be of great benefit, as it will
allow models to be compared on equal footing. It will also
be of benefit to those developing the models, as the validation
against agreed industry benchmarks could lead to the
reduction of cycle time from development to industrial use.
A final original issue raised by the current survey is the need
for education and the possible role the EFCE WP can play in
this. A number of suggestions of improving the undergraduate
level courses were made. Thermodynamics of process simulation
should be taught with the emphasis on how generic simulators
work, without necessarily going into peculiarities of a particular
simulator, unless a particular simulator is used in class. It is
 Ind. Eng. Chem. Res., Vol. 49, No. 22, 2010 11139
important to get across how to distinguish between reliable and Acknowledgment
unreliable thermodynamic data and practices. However, the main
We acknowledge the contribution from all industry experts
issue raised is how to make engineers more aware of the
who replied to the survey and thank them for their effort, without
practical consequences of “right and wrong” thermodynamics. which this paper could not have been written.
In particular what type of problems require initiation of proactive
research and under what circumstances would quick empirical
fixes suffice. Appendix 1. The Survey Questionnaire
Overall, the gap between the industrial requirements and the Below are listed the questions asked in the EFCE Working Party
data availability has not appreciably shrunk over the years. It Task group on Industrial Perspectives Questionnaire. All ques-
is not immediately clear how this gap can be closed especially tions are to be considered in relation to physical properties,
in the present economic climate. The first step is to once again thermodynamics, and transport properties.
try to bring the relevant stakeholders closer together.
As an example of possible actions, the French working party Question 1. Your company’s business
Thermodynamique des procédés organizes small scale one-day
meetings on specific topics such as education, molecular What are the main businesses of your company? (Put Yes or
thermodynamics, and use of databases. The objective is to create No)
learning and exchange opportunities between the academic and Exploration and production
Refining
the industrial communities. Specific potential actions from these
Bulk chemicals
meetings are the installation of a Web site for exchange between
Fine chemicals
educators and a Web-based information system for molecular
Natural gas
thermodynamics issues.
Power generation
Other examples include the organization of workshops such Pharmaceuticals
as the one recently organized between our working party and Agrochemicals
the German ProcesNet working party. Such workshops should
be tailored so that they address some of the numerous
questions raised above. At the same time, they can act as a Question 2. Limitations in thermodynamics and transport
properties
forward looking forum where the industry can articulate their
medium- and long-term needs and open a dialogue with data What do you consider as the limitations in thermodynamics
and model generators. and transport properties in addressing your company’s chal-
The issue of having large, standardized set of data against lenges?
which all models may be tested is also a very pertinent one Products
that needs addressing. Although, there are databases (NIST- Processes
TRC, Dechema-Detherm, Danner and Gess59) that are used by Data
individuals, their use is still not widespread enough. Models
Process simulation
Of equal importance is the definition and availability of Reservoir simulation
standardized models. In our view, this requires for each such CO2 sequestration
model the publication of a paper, perhaps in a dedicated Enhanced oil recovery
journal, containing all that is needed to perform the calcula- Extraction and processing of discounted (opportunity) crudes
tions and reproduce results. This includes all the equations (heavy oil, high sulfur crudes, high acid crudes...)
and parameter values needed to achieve this and results for Gas processing
a number of defined input cases. However, discussions on Long-range transport
the merits of the model and comparison to experimental data Add as many as you wish
should be left out. The model can then receive a unique
identifier which together with this definition paper can serve
as the reference. It would also be very useful to publish the Question 3. R&D in thermodynamics and transport
implementation of this model including the parameters as properties
open source code, preferably together with the definition. The How is the R&D organized in your company?
vendors of commercial software should refer to these standard
Do you have your own research laboratories?
models in their documentation and clearly state when and
where they deviate from them. The same holds for authors Do you have a research subsidiary?
discussing a comparison of their results against those obtained Do you subcontract your research?
with standard models. What proportion of the work is subcontracted to academic
We see this paper as the first step in reinitiating the teams?
dialogue between the interested parties which can lead to a
more effective collaboration that can close the current gap Question 4. Collaboration
between the requirements and the availability of thermody-
namic and transport property data and models. We feel that Consortia or other collaborative work in thermodynamics and
the EFCE WP should play an important role in this process, transport properties.
acting as a conduit between the academia, industry, and Do you participate in consortia?
decision makers. If so, in which areas?
11140 Ind. Eng. Chem. Res., Vol. 49, No. 22, 2010
Is your company willing to sponsor research work that is to
be shared with the rest of the thermodynamic community?
If so, in which areas?
Question 5. Benefit
Can you provide examples of achievements in Thermody-
namic R&D where you can give an estimate of potential
business or avoided risk?
Question 6. Areas
What are your ideas and opinions concerning the development
in the following areas?
Suggestions:
Try to be concrete, so refer explicitly to elements such as
components (carbon dioxide, sulfur), models (SAFT), phenom-
ena (gas hydrates), experimental quantities (SLE, speed of
sound), standards (CAPE OPEN), algorithms (multiphase flash,
speed improvement), conditions (T > 500 K), applications (heavy
oil, reinjection of hydrogen sulfide), procedures (characterization
of well fluids), and so on wherever this is possible.
Look at competing or complementary approaches, such as
Group Contribution methods versus CosmoLogic. Is there a need
for both? Do we have a preference?
Look at the need for standardization versus flexibility. For
example, do we want yet another equation of state, or should
we devote all effort to extending the traditional ones now present
in most process simulation programs? And if the latter holds
true, which ones would we single out in this stage?
Physical Data
Phenomena
Conditions and environments
Models
Algorithms
Procedures
Implementation
Applications
Process simulation
Standards
Add your own item(s)
Question 7. Other thoughts
Do you have any other thoughts on thermodynamics and
transport properties that could be relevant to us?
Literature Cited
(1) Prausnitz, J. M.; Lichtenthaler, R. N.; de Azevedo, E. G. Molecular
Thermodynamics of Fluid-Phase Equilibria, 3rd ed.; Prentice Hall Inc.:
Englewood Cliffs, NJ, 1999.
(2) Kontogeorgis, G. M.; Gani, R. Introduction to Computer Aided
Product Design. In: Computer-Aided Property Estimation for Process and
Product Design; Kontogeorgis, G. M., Gani, R., Eds.; Elsevier: Amsterdam,
The Netherlands, 2004.
(3) Abildskov, J.; Kontogeorgis, G. M. Chemical product design - A
new challenge of applied thermodynamics. Chem. Eng. Res. Des. 2004, 82
(11), 1505–1510.
(4) Villadsen, J. Putting structure into chemical engineering - Proceedings
of an industry/university conference. Chem. Eng. Sci. 1997, 52, 2857–2864.
(5) Favre, E.; Kind, M. Formulation engineering: towards a multidis-
ciplinary and integrated approach of the training of chemical engineers.
Paper presented in the 2nd European Congress of Chemical Engineering
(Montpellier), 1999.
(6) Sandler, S. I. Infinite dilution activity coefficients in chemical,
environmental and biochemical engineering. Fluid Phase Equilib. 1996,
116, 343–353.
(7) Sandler, S. I. Unusual chemical thermodynamics. J. Chem. Ther-
modyn. 1999, 31, 3–25.
(8) Sandler, S. I.; Orbey, H. The thermodynamics of long-lived organic
pollutants. Fluid Phase Equilib. 1993, 82, 63–69.
(9) Prausnitz, J. M. Thermodynamics and the other chemical engineering
sciences: old models for new chemical products and processes. Fluid Phase
Equilib. 1999, 158-160, 95–111.
(10) Prausnitz, J. M. Some new frontiers in chemical-engineering
thermodynamics. Fluid Phase Equilib. 1995, 104, 1–20.
(11) Prausnitz, J. M. Biotechnology: A new frontier for molecular
thermodynamics. Fluid Phase Equilib. 1989, 53, 439–451.
(12) Prausnitz, J. M. Molecular thermodynamics for some applications
in biotechnology. J. Chem. Thermodyn. 2003, 35, 21–39.
(13) Prausnitz, J. M. Molecular thermodynamics: Opportunities and
responsibilities. Fluid Phase Equilib. 1996, 116, 12–26.
(14) Prausnitz, J. M.; Foose, L. Three frontiers in the thermodynamics
of protein solutions. Pure Appl. Chem. 2007, 79, 1435–1444.
(15) Ahlström, P.; Aim, K.; Dohrn, R.; Elliott, J. R.; Jackson, G.; Jaubert,
J.-N.; Macedo, E. A.; Pokki, J.-P.; Reczey, K.; Victorov, A.; Fele Žilnik,
L.; Economou, I. G. A Survey on the Role of Thermodynamics and
Transport Properties in ChE Education in Europe and the USA. Chem. Eng.
Ed. 2010, 44, 35–43.
(16) Tsonopoulos, C.; Heidman, J. L. High-pressure vapour-liquid
equilibria with cubic equations of state. Fluid Phase Equilib. 1986, 29, 391–
414.
(17) Zeck, S. Thermodynamics in process development in the chemical
industry - importance, benefits, current state and future development. Fluid
Phase Equilib. 1991, 70, 125–140.
(18) Zeck, S.; Wolf, D. Requirements of thermodynamic data in the
chemical industry. Fluid Phase Equilib. 1993, 82, 27–38.
(19) de Hemptinne, J. C.; Mougin, P.; Barreau, A.; Ruffine, L.; Tamouza,
S.; Inchekel, R. Application to Petroleum Engineering of Statistical
Thermodynamics - Based Equations of State. Oil Gas Sci. Technol. - ReV.
IFP 2006, 61, 363–386.
(20) Mathias, P. M.; Klotz, H. C. Take a Closer Look at Thermodynamic
Property Models. Chem. Eng. Prog. 1994, 90, 67–75.
(21) Dohrn, R.; Pfohl, O. Thermo-physical properties - Industrial
directions. Fluid Phase Equilib. 2002, 194-197, 15–29.
(22) Dohrn, R.; Leiberich, R.; Fele Žilnik, L. Solubility related to
Reaction and Process Design. In: DeVelopments and Applications in
Solubility; Letcher, T., Ed.; Royal Society of Chemistry: Cambridge (UK),
2007; pp 273-291.
(23) Agarwal, R.; Li, Y.-K.; Santollani, O.; Satyro, M. A.; Vieler, A.
Uncovering the Realities of Simulation. Chem. Eng. Prog. 2001, 97, 64–
72.
(24) Bokis, C. P.; Orbey, H.; Chen, C. C. Properly Model Polymer
Processes. Chem. Eng. Prog. 1999, 95, 39–52.
(25) Pfohl, O.; Dohrn, R. Provision of thermodynamic properties of
polymer systems for industrial applications. Fluid Phase Equilib. 2004, 217,
189–199.
(26) Carlson, E. C. Don’t Gamble with Physical Properties for Simula-
tions. Chem. Eng. Prog. 1996, 92, 35–46.
(27) Chen, C. C.; Mathias, P. M. Applied Thermodynamics for Process
Modeling. AIChE J. 2002, 48, 194–200.
(28) Gupta, S.; Olson, J. D. Industrial Needs in Physical Properties. Ind.
Eng. Chem. Res. 2003, 42, 6359–6374.
(29) Moorwood, T. CAPE Tools and Techniques for the 21st Century.
Properties of Materials and Mixtures - Where do we need to be 10 years
from now? Report for Eureka Project 3211, 2001.
(30) Bruin, S. Phase equilibria for food product and process design. Fluid
Phase Equilib. 1999, 158-160, 657–671.
(31) O’Connell, J. P.; Gani, R.; Mathias, P. M.; Maurer, G.; Olson, J. D.;
Crafts, P. A. Thermodynamic Property Modeling for Chemical Process and
Product Engineering: Some Perspectives. Ind. Eng. Chem. Res. 2009, 48,
4619–4637.
(32) Frank, T. C.; Downey, J. R.; Gupta, S. K. Quick screen solvents
for organic solids. Chem. Eng. Prog. 1999, 95, 41–61.
(33) Kolar, P.; Shen, J.-W.; Tsuboi, A.; Ishikawa, T. Solvent selection
for pharmaceuticals. Fluid Phase Equilib. 2002, 194, 771–782.
(34) Crafts, P. The role of solubility modeling and crystallization in the
design of active pharmaceutical ingredients. In Chemical Product Design:
toward a perspectiVe through case studies; Ng, N. M., Gani, R., Dam-
Johansen, K., Eds.; Elsevier: New York, 2007.
(35) Chen, C. C.; Crafts, P. A. Correlation and prediction of drug
molecule solubility in mixed solvent systems with the Nonrandom Two-
Liquid Segment Activity Coefficient (NRTL-SAC) model. Ind. Eng. Chem.
Res. 2006, 45, 4816–4824.
(36) Modarresi, H.; Conte, E.; Abildskov, J.; Gani, R.; Crafts, P. Model-
based calculation of solid solubility for solvent selection - A review. Ind.
Eng. Chem. Res. 2008, 47, 5234–5242.

(37) Mathias, P. M. Applied thermodynamics in chemical technology:
current practice and future challenges. Fluid Phase Equilib. 2005, 228, 49–
57.
(38) Kontogeorgis, G. M.; Folas, G. K. Thermodynamic models for
industrial applications. From Classical and AdVanced mixing rules to
association theories; John Wiley & Sons: New York, 2010.
(39) Klamt, A.; Eckert, F.; Hornig, M. COSMO-RS: A novel view to
physiological solvation and partition Questions. J. Comput.-Aided Mol. Des
2001, 15, 355–365.
(40) Klamt, A.; Eckert, F.; Hornig, M.; Beck, M. E.; Burger, T.
Prediction of aqueous solubility of drugs and pesticides with COSMO-RS.
J. Comput. Chem. 2002, 23 (2), 275–281.
(41) NIST Special Publication 975 (Rainwater et al., 2001). Report on
Forum 2000: Fluid Properties for new technologies - connecting Virtual
design with physical reality (http://Forum2000.Boulder.NIST.Gov/
NISTSP975.pdf).
(42) Harvey, A. H.; Laesecke, A. Fluid properties and new technologies:
Connecting design with reality. Chem. Eng. Prog. 2002, 98, 34–41.
(43) Rainwater, J. C.; Friend, D. G.; Hanley, H. J. M.; Harvey, A. H.;
Holcomb, C. D.; Laesecke, A.; Magee, J. W.; Muzny, C. Forum 2000: Fluid
properties for new technologies, connecting virtual design with physical
reality. J. Chem. Eng. Data 2001, 46, 1002–1006.
(44) Rhodes, C. L. The process simulation revolution: Thermo-
physical property needs and concerns. J. Chem. Eng. Data 1996, 41,
947–950.
(45) Richon, D. The essential importance of experimental research and
the use of experimental thermodynamics to the benefit of industry, internal
document - discussions during round table during Colloquium to promote
experimental work in Thermophysical Properties for Scientific Research
and Industry in honour of the 60th birthday of Prof. Dominique Richon,
September 2009.
(46) Prausnitz, J. M.; Tavares, F. W. Thermodynamics of fluid-phase
equilibria for standard chemical engineering operations. AIChE J. 2004,
50 (4), 739–761.
(47) Prausnitz, J. M. Chemical engineering and the postmodern world.
Chem. Eng. Sci. 2001, 56, 3627–3639.
Ind. Eng. Chem. Res., Vol. 49, No. 22, 2010 11141
(48) Prausnitz, J. M. Athena, Hercules and Nausica: Three dimensions
of chemical engineering in the twenty-first century. Fluid Phase Equilib.
2007, 261, 3–17.
(49) von Stockar, U.; van der Wielen, L. A. M. Thermodynamics in
biochemical engineering. J. Biotechnol. 1997, 59, 25–37.
(50) von Stockar, U.; van der Wielen, L. A. M. Process integration in
biochemical engineering. AdV. Biochem. Eng./Biotechnol. 2003, 80, 1.
(51) Arlt, W.; Spuhl, O.; Klamt, A. Challenges in thermodynamics.
Chem. Eng. Process. 2004, 43, 221–238.
(52) Sandler, S. I. Quantum mechanics: a new tool for engineering
thermodynamics. Fluid Phase Equilib. 2003, 210, 147–160.
(53) Sandler, S. I.; Castier, M. Computational quantum mechanics: An
underutilized tool in thermodynamics. Pure Appl. Chem. 2007, 79 (8), 1345–
1359.
(54) Michelsen, M. L.; Mollerup, J. Thermodynamic Models: Funda-
mental and Computational Aspects, 2nd ed.; Tie-Line Publications: Holte,
Denmark, 2007.
(55) Dohrn, R.; Peper, S.; Fonseca, J. M. S. High-pressure fluid-phase
equilibria: Experimental methods and systems investigated (2000-2004).
Fluid Phase Equilib. 2010, 288, 1–54.
(56) Peper, S.; Haverkamp, V.; Dohrn, R. Measurement of Phase
Equilibria of the Systems CO2 + Styrene and CO2 + Vinyl Acetate Using
different Experimental Methods. J. Supercrit. Fluids 2010, doi: 10.1016/
j.supflu.2010.09.014, in press.
(57) Lin, Y.; ten Kate, A.; Mooijer, M.; Delgado, J.; Fosbøl, P. L.;
Thomsen, K. Comparison of activity coefficient models for electrolyte
systems. AIChE J. 2010, 56 (5), 1334–1351.
(58) CAPE/OPEN laboratories network, http://www.colan.org/.
(59) Danner, R. P.; Gess, M. A. A data base standard for the evaluation
of vapor-liquid-equilibrium models. Fluid Phase Equilib. 1990, 56, 285–
301.
ReceiVed for reView June 6, 2010
ReVised manuscript receiVed September 17, 2010
Accepted September 20, 2010
IE101231B