Newest Thermodynamic and Thermophysical Databases of the 1997 Era
Edgar F. WESTRUM, Jr. Department of Chemistry, University of Michigan, Ann
Arbor, MI 48109-1055
Abstract:
Because of the broad utilization of thermodynamics by many scientific disciplines,
thermal data of many sorts are crucial to scientific progress. The Survey of
Thermodynamic...Databases [OECD's Nuclear Energy Agency] is a good initial
focus for the more quantitative aspects of the field. In the overall correlation of
measured and predictive values, the vibrational ("lattice") contribution of the
crystalline lattice needs resolution to ascertain "excess" magnetic and electronic
contributions. To this end, lanthanide series (Ln2O 3, Ln 2S 3, LnB 6, LnF 6, etc.)
provide opportunities for resolution with runs of several members of the same
crystallization providing opportunities for development of schemes for resolution of
lattice contributions (e.g., the Komada-Westrum approach). The extension of these
phonon dispersion evaluations has proven fruitful�even for the vitreous state
(Westrum et al.). Finally, the increasing availability of better descriptions of the
trends in electronic contribution to electrical conductivity are enabling the resolution
of data to the much higher temperatures useful in modern technology.
1. Historical Prelude
Because thermodynamics is a discipline widely used throughout the gamut of
sciences�physical, earth, biological, cosmological, etc. (and because few of its
present practitioners are designated "thermodynamicists") and moreover because it is
widely claimed that the data needed by user scientists can't be found, it seems
important to ask about the data-available-situation today in thermodynamics. What
new printed and electronic data bases have become available today?
From the very beginning of CODATA several decades ago, thermodynamical data
have been a continuing problem and several task groups have struggled to facilitate
data recovery in thermochemistry and thermophysics. Thermodynamics has never
been easy going and developments on databases in this area were often tackled with
the motto: "if you can do it for thermodynamics you can do it for any science."
Thermodynamics is hard because of the many interlocking intellectual relationships
and because of the need of having tables created from self-consistent data, involving a
unique set of standard values of fundamental constants. Utter chaos ensues when data
gleaned from several tables are combined haphazardly without attention to overall
consistency, particularly because networks involving many substances and their
thermal properties are solved by computer in search of the most coherent values.
2. CODATA'S Thermodynamic Involvements
CODATA early in its history (1968) established a Thermodynamic Key Values Task
Group which published a table for several hundred substances in 1989 (1). In 1976
on becoming Secretary General of CODATA, I created a Task Group on the
Internationalization and Systematization of Chemical Thermodynamic Data which,
while claiming to rebel at a long and little understood name (but really trying to
extend the term of a Task Group Chairman by changing the name of the Task Group!),
became the Task Group on Chemical Thermodynamic Tables. They published the
prototype Calcium Tables (2) to show how their plan for insuring the self-consistency
of a CODATA scheme based on the key values and a master computer program
extension.
As Ward Hubbard at Argonne National Laboratory used to emote: "All
thermodynamic tables ought to fit on the same shelf!"
The Task Group pushed the completion of a book on "iron" to parallel the "calcium"
volume, but voted themselves out of existence before its publication (3). (I'm
attempting to salvage the main features of that CODATA book�and may succeed.)
The kaleidoscopic Task Group has now reappeared as a Key Values Task
Group�but no output has ensued.
The CODATA Geothermodynamics group has tried to tackle the properties of glasses,
magmas, and minerals, but also has stumbled before publication.
3. Databases and All That
But what about thermodynamic databases today? Well, the CODATA Newsletter (5)
does provide a current awareness service whenever possible.
Fortunately, the OECD has put out a neat Survey (4) that is available on the Internet
and in hard copy from OECD and which supplements my thrice yearly compilations
in the CODATA Newsletter. After a few comments on its contents and assessments, we
can turn to things it either missed or which were published subsequently to its closure
of its academic process.
4. Types of Thermodynamic Databases
Broadly, three groups of thermo databases exist:
(1) Pure substance databases. Typically 1000's of species, wide Trange�NO solution phases.
(2) Model solution databases. Relevant to metal-metal, metal-oxide, and
oxide-oxide systems. Typically very specific in applications, small number of
basic compounds.
(3) Aqueous solution databases. Usually contain data for solid and gaseous
phases as well as aqueous ions and complexes.
When using (1) and (3) together, care must be taken to use a common reference state
to avoid incorrect results.
5. The NEA-OECD Survey
Between 1994 and 1996 the Nuclear Science Committee of the OECD's Nuclear
Energy Agency produced a 50-page survey (4) of existing databases for chemical
thermodynamic data, relevant to nuclear systems reviewing their contents and quality
vis a vis nuclear fuel cycles and to identify important gaps. The existence of this
survey is relevant to my presentation and makes an excellent point of departure for us.
The work was done by a substantially competent Task Force (cf. Table 1). They
surveyed about 40 databases, approximately ten of them integrated within computer
codes (cf. Table 2). In addition, an index of geochemical modeling computer
programs is incorporated. A (partial) sample entry to one of the entries is shown in
Table 3.
Solution databases are more complicated to express and require evaluation of Gmix
and Gex and usually involve only binary and ternary solutions data, but
multicomponent systems can usually be adequately modeled by representations for the
lower order systems.
Waterbased processes are founded on the ability to model quantitatively speciation,
and the interaction of the aqueous phase with solid phases and/or a vapor provides a
key step towards the understanding and, in some cases, control of processes. This
could lead to an increase in the efficiency of industrial processes, in particular
complex applications using concentrated solutions at elevated temperatures. Methods
based on thermodynamics can be very useful for understanding the various processes,
for example dissolution and precipitation, oxidation and reduction, acid-base and
coordinative interactions, which govern the chemical composition of aqueous
chemical
systems. Typically, these models require the computation of equilibrium compositions
for systems containing numerous species distributed among an aqueous phase, a gas
phase, and several solid phases. For this reason, when modeling applications for
aqueous systems, data are required for both aqueous species and for pure substance
compounds. Most aqueous databases do include a small sub-set of pure substance
data. However, high-temperature solution data particularly are still scarce.
As noted in Table 2 "stand alone" aqueous solution databases can be used in
connection with a number of computer codes; those in the next category have their
own computer codes.
6. What's Newer?
Although the forty-odd thermo data bases tend to be good standby products, I would
like now to discuss briefly the even more recent databases (using the four OECD
categories in order as a framework).
Let's begin with pure substance databases in Table 4: The first is the Properties of
Organic Compounds on CD-ROM (Personal Edition) by D. R. Lide and G. W. Milne
(6). Lide is a long-standing CODATA hand who recently finished a term as Secretary
General. (He claimed in the 1970's that 90% of scientific data in the literature was so
lacking in metadata that it could not be compiled!)
This electronic database focuses on 27,500 of the most commonly used organic
compounds. The disk can be used to locate additional data and references for a
known compound or to identify an unknown compound that meets a given search
extensive help
-compatible word
processors. While the data compilation is the core of POC PE, the accessibility of the
data including simple and combined query capabilities proves the user with enhanced
features unavailable in the previous version. ISBN:0849304083, 9/96 (Price: $129.00)
CRC Press LLC, Boca Raton, FL 33431. Unfortunately, little thermodynamic data are
offered, but it does supplement nicely the following two books (the first of which also
has an electronic diskette) (7,8).
Although the Lide and Kehiaian volume on Thermophysical and Thermochemical
Data (7) dates back to 1994, it was not included in the Survey, which reasonably
enough focused primarily on inorganic materials. This volume covers a broad
spectrum of materials and indeed also includes thermodynamic properties of mixtures
(our following category).
Another cumulative work on organic compounds is the NIST (U.S. National Institute
of Science and Technology) Volume III compilation on Heat Capacities and
Entropies of Organic Compounds (8). This covers 2503 discrete organic compounds
in condensed phases through 1993.
Then let's take a look at Texas A&M which has a long-standing reputation for
thermodynamic data compilation. Another 1994 Thermodynamics Research Center
(TRC) book (apparently not included in the Survey because it was organic in nature)
is Pedley's Thermochemical Data and Structures of Organic Compounds [9],
focuses on enthalpies of formation
and bond energies for gaseous and/or
condensed phases and explains the Pedley Method.
Two massive TRC books, Thermodynamics in the Gas State Vol. I and II, cover (in
Vol. I [10]) the introductory material and data on C1 through C4 compounds and (in
Vol II [11]) C5 through C36 compounds and a comparison of the functions used for
temperature dependence. Special coefficients, etc. are provided on diskettes for both
volumes.
For minerals and related substances, the Robie and Hemingway U.S. Geological
Suvery Bulletin (12) provides the most recent heat capacities, entropies, and
formation data.
The peer reviewed draft of OECD Nuclear Energy Agency Chemical
Thermodynamics of Americium (13) has an appendix on the chemistry of uranium.
The DIPPR Data Compilation of Pure Compound Properties boasts not only a
Windows version (14) and a full version ASCII source files (15) and an STM on-line
access (16) but a hard copy version (17) in five loose leaf volumes. All cover about
1500 chemicals.
Then, among the Solution Database Category: The four mammoth (total mass ca. 10
kg) volumes already produced by TRC of the Transport Properties and Related
Thermodynamic Data of Binary Mixtures (1993-97) (18-22) represent the endeavor
of DIPPR (The Design Institute for Physical Property Data). The properties included
are: density, diffusion coefficient, solubility, surface tension, thermal conductivity,
viscosity, and critical properties.
The ongoing DECHEMA Chemistry Data System boasts two additional volumes, the
Electrolyte Data Collection, dealing with aqueous electrolyte solutions (23) and
another with transference numbers and limiting ionic conductivities (24).
Finally, I want to close on a rather specialized Vapor Liquid Equilibriium
Bibliographic Database (25) to emphasize a somewhat unique electronic approach to
a broad spread of thermodynamic data on diskettes with long term summary
calculations both on diskette and on books deceivingly thin because they are printed
on the very thin Bible paper. This innovation is largely due to Dr. Henry Kehiaian
(26).
Well, with all the new databases is it easy to find a particular datum? One of my
colleagues came by as I was proofreading this paper urgently asking for help in
locating the
search!
H for SeF6. Despite the new databases, it is still a difficult
LIPIDAT (31) is a database of literature data on the mesomorphic and polymorphic
phases and phase transition temperatures and enthalpy changes for synthetic and
biologically-derived complex polar lipids. The database, current through January,
1993, contains approximately 15,000 records. The project's second phase, compiling
data regarding the miscibility properties of lipids, is underway. Approximately 1,300
evaluated isobaric and isothermal phase diagrams have been collected. Currently,
LIPIDAT is available in handbook form and as an electronic database through the
National Institute of Standards and Technology. A World Wide Web relational
database version has recently been implemented. It incorporates the ability to display
and search for molecular structures. Electronic data submission by the individual(s)
responsible for making the thermodynamic measurements is being developed and
search capabilities, particularly for lipid mixtures, are being enhanced. In parallel,
the database is being brought up to date from 1993.
7. "Quo Vadis"
New thermophysical and thermochemical data are not popular research objectives
this biennium and new estimated schemes leave much to be desired. Neither
correlations nor comparisons nor interpretations are commonplace. The phonon
dispersion models seem to be flourishing (27-29) and should enhance the resolution
of cryogenic calorimetric data. The interest in the amorphous vitreous phases can
now be treated in the same idiom as the crystalline phases. Gradually, the
development of electronic conductivity is enabling extension of data interpretation to
much higher temperatures than formerly.
Referencesfont
1. CODATA Key Values for Thermodynamics. Cox, J. D.; Wagman, D. D.;
Medvedev, V. A.: editors. Hemisphere Publishing Corp.: New York. 1989, 279
pp.
2. CODATA Thermodynamic Tables. Selections for Some Compounds of
Calcium and Related Mixtures: A Prototype Set of Tables. Garvin, D.; Parker,
V. B.; White, H. J., Jr.: editors. Hemisphere Publishing Corp.: New York.
1987, 376 pp.
3. Iron Tables (expected 1998)
4. Nuclear Science Committee. Survey of Thermodynamic and Kinetic
Databases. Nuclear Energy Agency Organisation for Economic Co-Operation
and Development: France. 1996, 48 pp.
5. CODATA Newsletter . 1997. (ca. 18 pp. per annum), Ann Arbor, MI.
6. Lide, D. R.; Milne, G. W. Properties of Organic Compounds on CD-ROM
(Personal Edition). CRC: Boca Raton. 1996.
7. Lide, D. R.; Kehiaian, H. V. CRC Handbook of Thermophysical and
Thermochemical Data (with diskette). CRC: Boca Raton. 1994, 528 pp. ISBN
0-8493-0197-1.
8. Domalski, E. S.; Hearing, E. D. Journal of Physical and Chemical
Reference Data 1996, 25, 1-525.
9. Pedley, J. B. Thermochemical Data and Structures of Organic Compounds,
Vol. I. Thermodynamics Research Center: College Station, Texas. 1994, 579
pp. ISBN 1-883400-01-5.
10. Frenkel, M.; Kabo, G. J.; Marsh, K. N.; Roganov, G. N.; Wilhoit, R. C.
Thermodynamics of Organic Compounds in the Gas State, Vol. I.
Thermodynamics Research Cener: College Station, Texas. 1994, 803 pp. ISBN
1-883400-03-1.
11. Frenkel, M.; Kabo, G. J.; Marsh, K. N.; Roganov, G. N.; Wilhoit, R. C.
Thermodynamics of Organic Compounds in the Gas State, Vol. II.
Thermodynamics Research Cener: College Station, Texas. 1994, 1009 pp.
ISBN 1-883400-04-x.
12. Robie, R. A.; Hemingway, B. S. Thermodynamic Properties of Minerals
and Related Substances at 298.15 K and 1 Bar (105 Pascals) Pressure and at
Higher Temperatures. U.S. Geological Survey Bulletin 2131. U.S. Govt.
Printing Office: Washington, D.C. 1995, 461 pp.
13. Silva, R. J.; Bidoglio, G.; Rand, M. H.; Robouch, P. B.; Wanner, H.;
Puigdomenech, I. Chemical Thermodynamics of Americium. Nuclear Energy
Agency Organisation for Economic Co-Operation and Development: France.
(Preprint draft). 1995, 374 pp.
14-17. DIPPR
Data Compilation of Pure Compound Properties.
Daubert, T. E.; Danner, R. P.; Sibul, H. M.; Stebbins, C. C.: editors.
Technical Database Services: New York (14); book format, Taylor and
Francis: Bristol, PA (15); STN Intl.: Columbus, OH (16); NIST: Gaithersburg,
MD (17). 1996.
18. Transport Properties and Related Thermodynamic Data of Binary
Mixtures. Part 1. Gammon, B.E.; Marsh, K. N.; Dewan, A. K. R.: editors.
American Institute of Chemical Engineers: New York. 1993, 994 pp. ISBN 08169-0580-0.
19. Transport Properties and Related Thermodynamic Data of Binary
Mixtures. Part 2. Gammon, B.E.; Marsh, K. N.; Dewan, A. K. R.: editors.
American Institute of Chemical Engineers: New York. 1994, 584 pp. ISBN 08169-0622-x.
20. Transport Properties and Related Thermodynamic Data of Binary
Mixtures. Part 3. Dong, Q.; Marsh, K. N.; Gammon, B.E.; Dewan, A. K. R.:
editors. American Institute of Chemical Engineers: New York. 1996, 626 pp.
ISBN 0-8169-0699-8.
21. Transport Properties and Related Thermodynamic Data of Binary
Mixtures. Part 4. Marsh, K. N.; Dong, Q.; Gammon, B.E.; Dewan, A. K. R.:
editors. American Institute of Chemical Engineers: New York. 1997, 746 pp.
ISBN 0-8169-0725-0.
22. Transport Properties and Related Thermodynamic Data of Binary
Mixtures. Part 5. Marsh, K. N.; Dong, Q.; Dewan, A. K. R.: editors. American
Institute of Chemical Engineers: New York. Expected 1998. (A cross reference
& guide to 2140 mixture property tables involving 361 binary mixture classes.)
23. Barthel, J.; Buchner, R.; M�nsterer, M. DECHEMA Chemistry Data
Series. Vol. XII, Part 2. Electrolyte Data Collection. Part 2: Dielectric
Properties of Water and Aqueous Electrolyte Solutions. DECHEMA:
Frankfurt am Main, Germany. 1994, 375 pp.
24. Barthel, J.; Neueder, R.; Schr�der, P. DECHEMA Chemistry Data
Series. Vol. XII, Part 1c. Electrolyte Data Collection. Part 1C: Conductivities,
Transference Numbers, and Limiting Ionic Conductivities of Solutions of
Aprotic, Protophobic Solvents. I: Nitriles DECHEMA: Frankfurt am Main,
Germany. 1996, 576 pp.
25. Wichterle, I.; Linek, J.; Wagner, Z.; Kehiaian, H. V. Vapor-Liquid
Equilibrium Bibliographic Database (Integrated Electronic Chemical
Databases, Vol. 1). ELDATA SARL: Montreuil, France. 1993, 766 pp.
26. CODATA Newsletter #76, February 1997 (for more information).
27. Komada, N.; Westrum, E. F. Jr. J. Chem. Thermodynamics 1997, 29, 311336.
28. Kieffer, S. W. Rev. Geophys. Space Phys. 1979, 17, 1-19; ibid. 20-34; ibid.
35-59; ibid. 1980, 18, 862-886; ibid. 1982, 20, 827-849.
29. Kieffer, S. W. Reviews in Mineralogy. Vol. 14: Microscopic to
Macroscopic. Kieffer, S. W.; Navrotsky, A.: editors. Mineralogy Society of
America 1985, 65-126.
30. Westrum, E. F., Jr. Thermochimica Acta 1997, 320, 0-15.
31. Caffrey, M.; Kerr, D. S.; Kuo, E.; Feng, L.; Koynova, R.; Ding, L.
LIPIDAT: A Database of Thermodynamic Data and Associated Information
on Lipid Mesomorphic and Polymorphic Transitions. CRC Press: Boca Raton.
1993, 305 pp. Electronic database available as NIST Standard Reference
Database 34. On World Wide Web: http://www.lipidat.chemistry.ohiostate.edu.
Note Added in Proof, 17 December 1997:
Through the kind offices of Ted Selover, I have become aware of the International
Workshop on Thermophysical Properties and Databases held at Sogang University,
Seoul, Korea, 2 October 1997 by the Thermodynamics Division of the Korea Institute
of Chemical Engineers in response to demands from Korean processing engineering
technology. The Ministry of Trade is funding a three year database project leading to
the collection of data and the construction, continuation and enhancement of a
thermodynamic database.
Experts from U.S.A., Korea, Japan, and Germany made seminal presentations
apparently available in a Proceedings volume. Only that of Pennsylvania State
University Professor Ronald P. Danner on "Development of Databases for Process
Design in the USA " is available to me at this time. He quotes Wilhoit and Marsh
(1997) that the total global collection of data doubles on a 10 year basis. Thinking
futuristically, they argue that production of databases in advance is becoming
prohibitively expensive (except for a few systems of major economic importance) and
a method of producing compilation-to-order is needed (e.g., a computer software
driven program to locate needed data from large archives to carry out appropriate
interpretation and conversions to compare and select best values, and to generate an
output to user specifications). It is especially pertinent to the thrust of my dataoriented presentation and delves into the management of the DIPPR Pure component
Database and that of others.