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PU8UCATIONS
NBSIR 81-2341
Chemical Thermodynamic Data Banks
U.S. DEPARTMENT OF COMMERCE
National Bureau of Standards
National Measurement Laboratory
Chemical Thermodynamics Division
Washington, DC 20234
August 1 981
Interim Report
f
Preoared for
QC
ice of Standard Reference Data
. r ional Bureau of Standards
shington, DC 20234
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NBSIR 81-2341
CHEMICAL THERMODYNAMIC DATA BANKS
David Garvin, Vivian B. Parker and Donald D. Wagman
U.S. DEPARTMENT OF COMMERCE
National Bureau of Standards
National Measurement Laboratory
Chemical Thermodynamics Division
Washington, DC 20234
August 1 981
Interim Report
Prepared for
Office of Standard Reference Data
National Bureau of Standards
Washington, DC 20234
U.S. DEPARTMENT OF COMMERCE, Malcolm Baldrige, Secretary
NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director
Table of Contents
Page
1 Introduction 1
2. Evolution of Data Evaluation in
in Chemical Thermodynamics 2
3. Description of Data Banks 5
3.1 Information Resources 5
3.2 Evaluation of Data 7
3.2.1 The Thermochemical Data System 7
3.2.2 Treatment of Individual Papers 9
3.2.3 Values for Chemical Thermodynamic
Properties 10
4. Thermodynamic Data Banks at the
Institute for High Temperatures 11
5 What of the Future? 14
References 15
Figures 18
Chemical Thermodynamic Data Banks* *
David Garvin, Vivian B. Parker and Donald D. Wagman
National Bureau of Standards
Washington, D.C. 20234
Abstract
A substantial critical evaluation of chemical thermodynamic measurements
on inorganic and C-j^ organic compounds has recently been completed. This provides
selected values for some 14300 substances, based on a collection of 250,000 measure-
ments. This work is placed in a historical context of three earlier comprehensive
evaluations of thermochemical data.
During the course of this work data banks of several types have been developed:
bibliography, extracted unevaluated data, evaluated measurements (catalogs of
reactions) and selected chemical thermodynamic properties for individual substances.
The design, structure and use of those data banks are described.
The course of modern data evaluation, based on these files, is discussed
briefly in terms of tests for inter-measurement consistency and automated
solutions of large networks of data.
A complementary thermodynamic data system developed at the Institute for High
Temperatures, Moscow, USSR is described briefly. Proposed international activities
are outlined.
Key words: chemical thermodynamics; data evaluation; data banks; information
systems; networks of data; standard reference data; thermochemistry.
★
Presented at the American Chemical Society Meeting, Atlanta, GA., March 1981
1 .
Introduction
The purpose of this paper is to describe several data banks that
have been developed as aids in providing compilations of evaluated chemical
thermodynamic data. They are also becoming available to the thermodynamics
community as information resources.
The first data resources to be described are those developed at the
Chemical Thermodynamics Data Center at the National Bureau of Standards. They
have been used primarily for the evaluation of thermochemical data.
Also to be described is a second set of data banks developed primarily
for use in the evaluation of thermophysical data. This set of data banks and
an associated data management system have been developed at the Institute for
High Temperatures of the USSR Academy of Science, Moscow.
These data banks reflect only part of the world wide activity in the
evaluation of chemical thermodynamic data. Some other major activities are
mentioned very briefly in the final section of this paper. There are also
data dissemination and calculation systems that are being developed to simplify
retrieval and use of thermodynamic data. This rapidly growing activity is not
reviewed here.
To begin with it is advisable to define the terms being used here.
"Thermochemical properties" are those that involve chemical reactions and
mixing processes such as enthalpies of reaction combustion, solution and dilu-
tion; Gibbs energies from equilibrium constants, electromotive cell measure-
ments, and mixing experiments; entropy and heat capacity changes. In all of
these chemical and physical (mixing) processes the chemical identity of the
substance in the system changes. "Thermophysical properties" are those that
pertain to single substances and mixtures that remain essentially unchanged
during a process. They include PVT properties, entropy, heat capacity, and
enthalpy changes accompanying changes of temperature and pressure, Gibbs en-
ergy functions, enthalpies of vaporization and transition, and all other as-
pects of phase changes.
1
These two types of properties are illustrated in figure 1. The
horizontal arrows for reactions apply to changes in thermochemical properties,
the vertical arrows to changes in thermophysical properties with temperature.
"Chemical thermodynamic properties" is the name given here to the
aggregation of thermochemical and thermophysical properties. It includes all
of those properties needed for a study of chemical equilibria and heat effects
of reactions as a function of temperature, pressure and composition (of mix-
tures.)
The data banks developed at NBS are of several types:
° Data extracts of thermodynamic measurements
(substance/property index)
° Bulletin of Chemical Thermodynamics
(Inorganic chemistry section)
0 Catalogs of evaluated Chemical Thermodynamic
Measurements
° Selected Values of Chemical Thermodynamic
Properties (NBS Tech. Note 270)
From our point of view the first three are aids to the preparation of the
fourth: "Selected Values." This is a data bank that contains our recommen-
dations on the thermodynamic properties at 25 °C for inorganic compounds and
low molecular weight organics. It has just been completed and is the fourth
full-scale evaluation of chemical thermodynamic data with which NBS has been
associated in the past fifty five years. The data banks are best considered in
the context of this activity.
2. Evolution of Data Evaluation in Chemical Thermodynamics
The nature and scope of thermochemical data evaluation activities have
undergone a series of changes in the past 55 years, both in the collection and
storage of thermochemical data and in the actual data evaluation process itself.
A brief history of this evolution is in order.
2
The International Critical Tables under the editorship of E. Washburn at NBS
published a set of tables of heats of formation in 1929. These tables [1] were
compiled by F. Russell Bichowsky, Naval Research Laboratory, and represented
the first modern attempt to collate all the published data involving enthalpies
of reaction and to prepare self consistent tables of selected values of en-
thalpies of formation.
Approximately 3700 inorganic and C-j - organic compounds were listed, with
either an enthalpy of formation, of dilution, or of transition. Also included
was the measurement type, by code, and the reference: a shorthand documentation.
These 3700 total data items were obtained from a total of 1113 literature
references. These references were abstracted, indexed and coded by compound and
type of measurement. Bichowsky developed this as a hand written 3x5 card file.
This was the data bank. (Conservatively it must have had close to 12000 3x5
cards of pertinent information). The evaluation process itself was a completely
manual, sequential approach of making selections, one compound and value at a
time, building relationships and networks until a stable set of values for the
enthalpies had been developed.
This manual, sequential approach has dominated thermochemical data
evaluation and is still being used. Only during the past decade has the computer
based simultaneous solution approach become important. More on this later.
This early data bank was maintained and added to and in 1936 Bichowsky and
Rossini [2] published their "Thermochemistry of the Chemical Substances," which
updated the enthalpies of formation, reevaluating and reassembling a self-consistent
set of best values for approximately 6000 (inorganic and C-j - C 2 organic) sub-
stances. Phase transition enthalpies were included. The total number of data
items was 6600. The mesurements used were described tersely and compared in
the text. There were now 3750 references. The 3x5 card data bank had in-
3 _.
creased to 22000 items.
By 1940 it was quite obvious that the tables and maintenance of the data files
could no longer be a part-time "extracurricular" activity for one individual.
A formal program was undertaken at NBS headed by Frederick D. Rossini.
Donald D. Wagman joined the staff in 1940 and William H. Evans in 1947. It was
decided taht the scope of teh work must be enlarged, that evaluating only the
ArH's could be both misleading and incomplete, that both the Gibbs energy and
entropy should be included. When the volume "Selected Values of Chemical Thermo-
dynamic Properties," NBS Circular 500 [3] was published in 1952, a line entry
in Series I, on the formation properties, contained not only A^H°, but also
O
AfG°, log K.p, S°, Cp, and A^Hq. The phase transition properties (Series II)
covered were AH, T, AS, P, AC . The number of data items was 15000 based on
r
8500 references. The card bank expanded to 50000. The tables were documented
by reference citations only.
This expansion of the tables meant that the user now had data for the
prediction of equilibrium constants and also could correct them to temperatures
other than the reference point, 298.15 K.
The. expansion also had a major impact on the data evlauation process. Gibbs
energy and entropy data could be used to confirm enthalpy measurements and the
combined set could be used to predict values for which there was no direct reli-
able measurement. This meant that data evaluation became more complex and re-
quired more decision making.
It is now 1981 and NBS has just completed the fourth major evaluation of
chemical thermodynamic data. Originally conceived as a revision of Circular 500,
it is a greatly expanded, completely reevaluated self-consistent set of data.
It has been issued as NBS Technical Note 270 in eight parts over the past 16
years [4]. A combined volume will be issued later this year. It covers the
formation properties of 14,300 substances and has 26,000 data items, half of
which are enthalpies of formation. We estimate that 60,000 references were
4
used, and that these produced 180,000 cards in our compound/property index.
A sample page from the final section of NBS Tech. Note 270 is shown in Figure 2.
The documentation for this work has not been published. Our plans are des-
cribed later in this paper.
The growth and changing scope of compiled chemical thermodynamic data are
displayed in Figures 3 and 4.
It became increasingly clear by the later sixties that new methods must be
developed to cope with the explosion of the literature and the more complex
nature of the evaluation process. We turned to the computer for help in
(1) staying on top of the literature (simplify the abstracting of data)
(2) evaluating and intercomparing measurements (3) updating tables, and
(4) documenting and disseminating the information. The developments reported
in the next section reflect this change of procedure.
3. Description of Data Banks
The NBS data banks mentioned at the beginning of this paper were developed
in the course of the evaluation of chemical therodynamic measurements for the
NBS tables "Selected Values of Chemical Thermodynamic Properties." The data
banks are of two types:
° information resources
° evaluated data
3.1. Information Resources These are of three types: bibl iography , microform
copies of papers and extracts of data. The last, the "card file" mentioned
earlier, is the principal resource. It contains many types of information, all
needed for the evaluation of data:
° Experimentally measured enthalpies of reaction, fusion,
vaporization, sublimation, transition, solution
and dilution.
5
° Vapor pressures, solubilities, chemical equilibria and
EMF measurements.
° Heat capacities, experimental and statistically calculated
entropies .
° Molecular structure and energy level data.
0 PVT data and correlations of properties with structure.
All of this information is organized by compound and then by the property
measured. In order to keep this data bank current, staff members of the Chemical
Thermodynamic Data Center scan the primary literature and Chemical Abstracts
each month, select articles, and abstract them. A typical data extract (on one
measurement on one compound) is shown in Figure 5.
This index is now in two parts. Up to 1969 each information unit was
written by hand on a 3 x 5" card. Since then the abstracts have been keyboarded
into a computer file and the hard copies of them have been produced by a complex
report-writing program. This has reduced sharply the routine labor required of
the data abstractors and at the same time has created an archival file of raw
data.
The hand-written file covering chemical thermodynamics up to 1969 has been
microfilmed and is being sold by the NBS Office of Standard Rererence Data. It
contains images of 156,000 cards covering about 40,000 articles.
The computer based file, covering chemical thermodynamics since 1969, is
available on site at NBS-Gai thersburg (as a card file) and has been distributed,
in part, but only for special cooperative projects. Distribution of the entire
file to the public is being considered in connection with the development of an
on-line retrieval system. In the meantime, the limited version that appears in
the Bulletin of Chemical Thermodynamics should serve as an effective guide to
the literature [5].
The Bulletin is an annual current awareness service. It contains indexes to
published thermodynamic and related studes on: organic substances and mixtures.
6
inorganic substances, biological and macromolecular systems, and reports on current
research throughout the world. It is issued under the auspices of IUPAC, edited by
Prof. R.D. Freeman, Oklahoma State University, and published by Thermochemistry ,
Inc., Stillwater, Oklahoma. A typical section of a page from the Bulletin is
shown in Figure 6.
3.2. Evaluation of Data The development of machine-readable evaluated chemical
thermodynamic data is a result of the automation of parts of the final stage of
the evaluation process in the Chemical Thermodynamics Data Center. "Machine
readable" must be emphasized. Data banks similar to the ones to be described
here existed in the pre-computer era. The evaluation process itself has two
major parts:
* evaluation of each set of measurements reported in an
individual paper
° combining the acceptable measurements from the
various sources to obtain selected, reliable values
of properties.
The process has been discussed in detail elsewhere [6, 7, 8]. It is
described briefly here starting with a brief discussion of the interconnected
nature of thermodynamic data.
3.2.1. The Thermochemical Data System
All thermochemical measurements are relative, yielding changes in properties
for processes. Thermochemical properties of a system also are functions only of
the initial and final states and are independent of the path between the reactants
and the products. These facts and what it is possible to measure control the
structure of the thermochemical data system. There are two features that become
apparent when a large number of such measurements are examined. First there is
7
usually a very limited number of replicate measurements for any particular
reaction. Intercomparison of many supposedly identical measurements is not a
major part of the evaluation process.
Second, there often are several chemically distinct experiments or sets
of experiments that lead from a particular reactant to a particular product.
We call each of these distinct sets a "measurement pathway." The phenomenon
is illustrated in Figure 7 for a few compounds of beryllium. It shows six
pathways leading from Be to BeO. They involve measurements on six other com-
pounds, each of which may be part of other networks. Because changes of thermo-
chemical properties are independent of the path, all six paths from Be to BeO
must lead to the same result, in the absence of experimental error.
The multiple measurement path phenomenon adds a dimension to the evaluation
of chemical thermodynamic data that is absent from many other evaluation efforts
extensive quantitative cross checks. This multiple path phenomenon is a major
feature. The extensive crosslinking in the thermochemistry of lithium compounds
is displayed in Figure 8. The many possible intercomparisons make it possible
to select a highly consistent data set.
The large data networks, such as Figure 8, are maps for linear algebra
problems. Thermochemical measurements can be reduced, formally, to equations
involving only the addition and subtraction of properties of compounds, and
these appear only to the first power. An example is given in Figure 9 in which
the measurement for a hydration process is decomposed into three terms, the
enthalpies of formation of each substance from its chemical elements. Given an
interconnected set of such equations, the enthalpies of formation can be solved
for and then the "best values" for the processes reconstructed. For many years
the solution of such networks has been done by hand, but now computer assisted
solutions are becoming important.
8
That such large thermochemical networks should be and are being solved using
computer programs is due to the imagination and foresight of two groups of thermo-
chemists. In the early 1960's Daniel Stull, Dow Chemical Co. proposed a system
in which all thermochemical measurements would be put into computer files and the
entire set for all inorganic chemistry could be solved at one time. This concept
was developed by A. N. Syverud [9]. Shortly thereafter J. Brian Pedley,
University of Sussex, proposed a computerized system designed for rapid updating
of tables and for coordinating the work of several groups of data evaluators [10].
He has used it to produce the CATCH Tables [11] and the Sussex - N.P.L. tables
on organic compounds [12]. These computerized approaches have been merged by us,
expanded in a cooperative program between NBS and the University of Sussex, and
used on large networks.
3.2.2. Treatment of Individual Papers
The first step in solving a data network, by computer or not, is the
preparation of the input data. This is the most difficult step. The data evaluator
must verify the work reported in each paper, develop an exact statement
describing the chemistry for each process, and reduce the measured value to a
consistent set of conditions (temperature, pressure, atomic masses etc.). The
overall accuracy must be estimated. All of these acts require the evaluator
to have a broad knowledge of chemical thermodynamics. This preparation of the
input is the most time consuming part of the entire evaluation process. It is
over 80% of the work.
The results of each of these reanalyses can be summarized succinctly as
shown in Figure 10: chemical reaction, property, value, uncertainty, reference
and comments. They can be used directly as input to a machine solution of a
thermochemical network problem. These reanalyses are also accumulated to form
a catalog of evaluated thermochemical measurements that can be used to document
the data evaluation.
9
We expect to produce the documentation of the NBS Tables "Selected Values of
Chemical Thermodynamic Properties" in the form of such catalogs, supplemented by
commentary concerning special problems and tables of thermal functions used in the
process. This is instant documentation in a detail that has not been practical
previously.
One such catalog has been published. It covers the thermodynamics of compounds
of thorium and is an experiment in highly structured, detailed documentation with
the minimum of prose [13].
3.2.3. Values for Chemical Thermodynamic Properties
The second part of the evaluation process is the simultaneous solution of the
network of thermodynamic equations to get the formation properties of the compounds.
This is, in effect, the reconciliation of data from many laboratories. The network
is an overdetermined set and has been solved by a robust procedure involving
both least sums and least squares treatments. [6] Several iterations may be
necessary because this is the first point in the process at which estimates of
interlaboratory agreement and accuracy of methods can be made reliably.
The output from a network solution is a set of selected values for the
AfH°, A^G° and S°’s of the compounds being studied. This solution has a property
that is not well recognized. Because the measurements are all linked together,
a change in one part of the network will cause changes in most of the A^H's , etc.,
while the best values for most of the individual processes will remain almost the
same. This situation is the basis of pleas by evaluators that the user avoid
mixing property values from several tables. It also explains why tables of
thermochemical data are constructed to cover the full range of chemical compounds.
Because the totality of inorganic thermochemistry is still too large for one
solution to be practical, a series of solutions has been made, usually for com-
pounds of one element at a time, group by group across the periodic table from
right to left. (As the results of each solution are entered into the data bank
they become available as fixed data for later solutions. This keeps all solutions
10
consistent with each other.) Solutions for compounds of eight elements: Th,
U, Li, Na, K, Rb, B, and Cs, have been made by machine. Earlier solutions
were made by hand, using a sequential technique.
The computer file of selected values is being used to produce the forthcoming
NBS Tech. Note 270-8, the last in the series, and will be used to produce the com-
bined volume for the entire series. With this computerized data bank it will be
very easy to convert all values to SI units (from calories at 1 atmosphere to
joules at 10 pascal.) This data bank will also become part of the thermodynamics
module of the Chemical Information System sponsored by NIH and EPA.
Let us return for a moment to the catalog of evaluated thermodynamic
measurements. This catalog will outlive our "Selected Values" because new measure-
ments will force modification of the selections. The catalog, supplemented with
new data, and operated on by existing programs will permit an instant update.
This would have been impractical using the older, manual, sequential methods.
4. Thermodynamic Data Banks at the Institute for High Temperatures
A very active thermodynamic data evaluation group at the Institute for
High Temperatures of the USSR Academy of Sciences, Moscow (IVTAN), headed by
L.V. Gurvich, publishes two sets of tables. They are "Thermodynamic Properties
of Individual Substances" [14] and "Thermal Constants of Substances," [15] The
former is analogous to the JANAF Thermochemical Tables [16] and the latter [15]
is similar to NBS Technical Note 270, but also includes transition properties.
In recent years the preparation of these volumes has been supported by a specialized
data base management system that contains extensive data banks. Professor Gurvich
has provided a description of this very attractive, flexible data system, which
is given below in a slightly modified form.
The data bank on thermodynamic properties was created in the chemical
thermodynamic department of the Institute of High Temperatures of the USSR
Academy of Sciences (IVTAN). Unlike most other data banks, the IVTAN data bank
does not accumulate the data recommended in various reference books. It contains
11
or generates the thermodynamic properties data for a wide temperature range
on the basis of critical analysis of all primary literature sources. This data
bank is used in the conversational mode using the "Image" subsystem on an
Hewlett-Packard 3000 computer system. It contains a number of disc files, one
file for each compound. Data for different isomers and also gaseous and con-
densed phases of the same substance are stored in separate files.
The system consists of a set of programs and data bases. The data bases now
include the following:
A) Auxiliary data such as fundamental constants, atomic masses etc.
B) Input data used for the calculation of thermal functions: These
data include molecular constants for gases and values of heat
capacity enthalpy change and phase transition characteristics
for condensed substances. All the data are selected by expert
analysis of the primary literature.
C) Experimental data on equilibrium constants of chemical reactions
and vapor pressures of substances.
D) Intermediate constants obtained by statistical treatment and
critical analysis of data (B) and (C), e.g. reduction of high
temperature data.
E) Thermochemical constants (enthalpies of formation, enthalpies of
sublimation, dissociation energies, ionization potentials, etc.)
based on analysis of the primary literature and data from base (D).
F) Tables of thermodynamic properties, e.g. thermal functions, and
related data for each substances.
The program set includes tens of programs and program modules providing for:
A) Treatment of primary experimental and theoretical data accumulated
in bases (B) and (C).
12
B) Calculation of thermal functions of substances in gaseous and
condensed phases over a wide temperature interval using different
approaches in order to get the best possible accuracy for each
compound.
C) Estimation of uncertainties of the thermal functions taking into
account the reliabilities of the selected values of constants
and method of calculation.
D) Statistical treatment of primary experimental data contained in
base (C) using the calculated thermal functions.
E) Calculation of a consistent set of thermochemical constants for
all compounds of a given element using data from base (E).
F) Calculation of the final table of thermodynamic properties for a
given compound including equations fitting the tabulated thermal
functions and equilibrium constants for the reaction of atomization
(or evaporation) .
G) Management of all parts of the data bank.
The data for more than 1000 substances have been accumulated in the IVTAN
data bank up to the present. They cover all substances considered in the first
three volumes of "Thermodynamic Properties of Individual Substances" and some
substances from the last, fourth volume of this series.
In the continuation of this work, IVTAN plan to enlarge the list of elements
and compounds, to introduce a bibliography and short descriptions, and to create
a data base on direct results of experimental measurements of the enthalpy and
free energy of chemical reactions. A number of new programs will be written
also for more accurate calculation of the thermal functions of simple polyatomic
gases, for obtaining an interconsi stent set of thermochemical values for a given
number of chemical substances from primary experimental data, etc.
13
5. What of the Future? Where is chemical thermodynamic data evaluation going?
The problem for the future is the rapid updating and effective delivery of
thermodynamic data. Already, the major compilations of evaluated data are aging.
Suppose that a new set of tables of evaluated data is to be issued in 1985.
At least 25,000 new measurements will have to be considered and added to the
catalogs. This is the bottleneck. The assessment of the individual paper has
not been automated successfully although the process can be aided by calculational
programs and graphical displays. Thus the answer must be to use all evaluative
resources throughout the world in a cooperative program.
CODATA, the Committee on Data for Science and Technology, is developing such
a program. The first phase is the highly successful international Task Group on
Key Values for Thermodynamics which provided new recommendations for one hundred
fifty substances that are base points for many thermochemical measurements. [17].
The second phase is a plan for a much larger multinational thermodynamic data
^yaluation consortium that might produce the next round of thermochemical and
thermophysical tables. This is being developed by the CODATA Task Group on
Internationalization and Systematization of Thermodynamic Tables.
An example of what this might mean is shown in Figure 11. Here we have
a series of independent groups (on the left) each contributing its output to
an international system that would, in turn, serve the individual users.
The cooperative scheme would reduce the overlap in services that exists at
present, and provide the users with a single set of reconmendations and do this
more rapidly. By splitting up the work, by exchange of data, and by common
development of computer procedures the evaluation groups would greatly simplify
their presents tasks.
If all this can be done, the future will indeed be bright for the user of
thermodynamic data.
14
References
1. Bichowsky, F.R., "Thermochemistry: Heats of Formation under Constant
Pressure (Heats of Solution, Heats of Transition)" in Washburn, E. W.,
editor, International Critical Tables of Numerical Data, Physics,
Chemistry and Technology" McGraw Hill Book Co., N.Y. 1929, vol . V pg 169-213.
2. Bichowsky, F.R. and Rossini, F.D., The Thermochemistry of the Chemical
Substances , Reinhold Publ . Co., N.Y., 1936, 460 pp.
3. Rossini, F.D., Wagman, D.D., Evans, W.H., Levine, S. and Jaffe, I.,
"Selected Values of Chemical Thermodynamic Properties", NBS Circular 500
(1952), 1268 pp.
4. Wagman, D.D., W.H. Evans, V.B. Parker, I. Halow, S.M. Bailey, and
R.H. Schumm, "Selected Values of Chemical Thermodynamic Properties",
U.S. Nat. Bur. Standards Tech. Note 270-3 (1968); idem, Tech. Note 270-4
(1969); Wagman, D.D., W.H. Evans, V.B. Parker, I Halow, S.M. Bailey,
R. H. Schumm, and K.L. Churney, Tech. Note 270-5 (1971); Parker, V.B.,
D.D. Wagman, and W.H. Evans, Tech. Note 270-6 (1971); Schumm, R.H., D.D. Wagman,
S. M. Bailey, W.H. Evans, V.B. Parker, Tech. Note 270-7 (1973); Wagman, D.D.,
W.H. Evans, V.B. Parker, R.H. Schumm and R.L. Nuttall, Tech. Note 270- 8
(1981), U.S. Govt. Printing Office, Washington, D.C.
5. Freeman, R.D., editor, Bull. Chem. Thermodynamics (Thermochemistry , Inc.
Stillwater, Oklahoma) vol. 22 (1979).
6. Garvin, D. , V.B. Parker, D.D. Wagman and W.H. Evans, "A Combined Least
Sums and Least Squares Approach to the Solution of Thermodynamic Data
Networks" in B. Dreyfus, editor, Proc. Fifth Biennial Int. CODATA Conf . ,
Pergamon, N.Y. 1977, pg 567.
15
7 .
Wagman, D.C., D. Garvin, V.B. Parker, W.H. Evans, J.B. Pedley and
P.M. Burkinshaw, "Handling and Evaluation of Large Networks of
Thermochemical Data", Seventh Int. CODATA Conf . , Kyoto, Japan, Oct. 8-11, 1980.
8. Wagman, D.D., D. Garvin, V.B. Parker, R.H. Schumm and J.B. Pedley.
"New development in the evaluation of thermochemical data". In National
Measurement Laboratory 1979 Technical Highlights. U.S. Nat. Bur. Stand.,
Spec. Publ . 572, U.S. Govt. Printing Office, Washington, D.C. 91980),
pp 53-55.
9. Syverud, A.N. and Klein, M. (Periodic Reports on USDC-NBS Contract
CST 1165), Dow Chemical Co., Midland, Mich., 1964-65.
10. Guest, M.F., Pedley, J.B. and Horn, M., "Analysis by computer of
thermochemical data on boron compounds", J. Chem. Thermodynamics, (1969),
1, 345.
11. Pedley, J.B. (ed.). Computer Analysis of Thermochemical Data (CATCH Tables) ,
University of Sussex, Brighton. Data selectors and tables issued:
Cox, J.G., "Halogen Compounds" (1972); Pilcher, G., "Nitrogen Compounds"
(1972); Pedley, J.B. and Iseard, B.S., "Silicon Compounds" (1972);
Head, A.J., "Phosphorus Compounds" (1972); Barnes, D.S., "Cr, Mo and W
Compounds" (1974).
12. Pedley, J.B., and J. Rylance, Sussex-N. P.L. Computer Analyzed Thermochemical
Data: Organic and Organometal 1 ic Compounds." University of Sussex,
Brighton, England (1977).
13. Wagman, D.D., R.H. Schumm, and V.B. Parker. A Computer-Assisted
Evaluation of the Thermochemical Data of the Compounds of Thorium .
NBSIR 77-1300. U.S. Nat. Bur. Standards, Washington, D.C. (1977).
16
14. Glushko, V.P., L.V. Gurvich, G.A. Bergman, I.V. Veits, V.A. Medvedev,
G.A. Khachkuruzov, and V.S. Yungman, eds. "Thermodinamicheskie
Svoistva Individual 'nykh Veschestv", vol . 1, parts 1 and 2 (1978),
vol . 2, parts 1 and 2 (1979), Izdatel'stvo "Nauka" Moscow.
15. Glushko, V.P., V.A. Medvedev, G.A. Bergman, L.V. Gurvich, V.S. Yungman,
A.F. Vorob'ev, V.P. Kolesov, L.A. Reznitskii, G.L. Gal'chenko, and for
various volumes, V.V. Mikhilov, M. Kh. Karapet 'yants , V.P. Vasilev,
V.N. Kostryukov, N.T. Ioffe, G.G. Malenkov, N.L. Smirnova, V.F. Baibuz,
V.I. Alekseev, I.L. Khodakovskii , K.B. Yatsimirski i , and B.P. Biryukov,
editors, "Termicheskii Konstanty Veshchestv", Vol. 1 (1965), Vol. 2 (1966),
Vol. 3 (1968), Vol. 4, part 1 (1970), part 2 (1971), vol. 5 (1971),
Vol. 6, part 1 (1972), part 2 (1973), Vol. 7 in 2 parts (1974), vol. 8 in
2 parts (1978), Vol. 9 (1979); Viniti, Moscow.
16. Stull, D.R. and H. Prophet, JANAF Thermochemical Tables, 2d Ed.,
Nat. Stand. Ref. Data Ser., Nat. Bur. Stand. (U.S.), (1971) 37.
Chase, M.W., J.L. Curnutt, A.T. Hu, H. Prophet, A.N. Syverud and
L.C. Walker, - 1974 Supplement, J. Phys. Chem. Ref. Data (1974) .3,
311-480. Chase, M.W., J.L. Curnutt, H. Prophet, R.A. McDonald, A.N. Syverud,
- 1975 Supplement, J. Phys. Chem. Ref. Data (1975) 4., 1-175.
Chase, M.W., Curnutt, J.L., R.A. McDonald, A.N. Syverud, J. Phys. Chem.
Ref. Data (1978) 7, 793-940.
17. CODATA Task Group on Key Values for Thermodynamics J.D. Cox. Chairman (1978).
"CODATA Recommended Key Values for Thermodynamics 1977." CODATA Bulletin 28.
CODATA, Paris, Idem (1980). "Tentative Set of Key Values for Thermodynamics.
Part VIII". CODATA Special Report No. 8. CODATA, Paris.
17
FIGURE CAPTIONS
Figure
Figure
Figure
Figure
Figure
Figure
Figure
Figure
Figure
Figure
Figure
1. A thermodynamic cycle involving a chemical reaction at two temperatures
2. Sample entries from the table on compounds of sodium from NBS Tech.
Note 270-8. The highlighted items are new material, showing expansion
from NBS Circular 500. All properties values (highlighted or not)
are the result of new evaluations.
3. Chemical thermodynamic properties included in the International
Critical Tables, Bichowsky and Rossini, NBS Circular 500 and
NBS Tech. Note 270.
4. Growth of compiled chemical thermodynamic data over a fifty year period
5. Extract of Data. The contents summarize one set of measurements of a
property of a single compound. This is the useful information unit in
chemical thermodynamics.
6. Section of a page from the Bulletin of Chemical Thermodynamics showing
the substance, property measured (two letter code) and reference.
7. A Thermochemical network showing the measurement paths leading from
elemental beryllium to beryllium oxide.
8. Lithium Thermochemical Network. Each node (box) is a compound and
each line is a measurement. The common starting point at the left
is Li(^) and the top two compounds in the next column are Li ( g )
and Li (aq, std. state). Rectangles are enthalpies, diamonds are
Gibbs energies and hexagons are entropies.
9. Thermochemical process showing relationship of the measured enthalpy
to enthalpies of formation.
10. Reaction Catalog. Examples of the stylized summary of evaluated data.
The form actually used is machine readable.
1 1 . International Cooperation in Thermodynamic Data Evaluation. A
possible organization of a consortium.
18
c
T 2
+ B
+ B
THERMOPHYSICAL
H 2' H 1
(G 2 - HjJ/Tj
THERMOCHEMICAL
AH, AG, AS
FIGURE 1
19
0)
.2
'C
03
CO co
I ®
1 r*»
to ^
03 a;
~ o
S.f
2 ra
0- .2
•2J
£ o
S*
■o I
2 w
l-E
03 (0
£ T3
I- C
_ (0
o </5
So
5 =>
o g
■ ■ u.
o =
</>“
I!
(0 O
> ••=
_ ra
13 z
03 " C -
O
_03
03
(0
o
<8
a
a
O
cs
a>
X
■o
c
£8
a
o
w
C
LU
C
o
to
s
o
LL
>.
O)
w
03
C
LU
eft
n
n
5
"D
C
>»
a
ez
£
C
LU
20
FIGURE 2
a f H
a f G
s
4 f H 0
H-H 0
ICT B&R C500 TN 270
X X X X
X
X
X
X
X
X
X
X
X
4H tr
4S tr
P T
r TR' 1 TR
X
X
X
X
X
FIGURE 3
21
ICT
B&R
C500
TN 270
PUBLi YEAR
1929
1936
1952
1981
Substances
3720
6000
7000
14300
2840 CTR)
Data Items
3720
6600
10,500
26,000
4,200 CTR)
References
1113
3750
8500
60,000
Document-
ReF,+
Ref.+
Ref,
Reaction
ation
Meas,
TEXT
ONLY
catalog
code
(Planned)
FIGURE 4
22
0
BaCl 2 taq ,B00H 2 O)
Sobol, L.G., and Selivanonva, N . M . , t Zhur. F i z . K h i m .
43, 2937-2938 (1969)
Heas. heat of reaction of N a H S 0 4 and NaHSO^.HgO with
BaClg(aq), plus heats of solution, at 25 C in isothermaL-
jacket calorimeter.
BaCl 2 (800H 2 0) + NaHS0 4 . HgO ( c ) = BaS0 4 (c)
+ NaCl(800H 2 0) + HCl(800H 2 0] + HgOtliq)
iAH = -6.7 + 0.10 kcal/mol
BaC l 2 691442
FIGURE 5
47. OSMIUM Os
Os/Zr(c/!iq)
Px
5623-79
OsOj(g)
Md
5209-79
OsO,(g)
Md
5672-79
OsO,F,(g)
Md
5672-79
48. MANGANESE
Mn
Mn(aq)
Px
6811-79
Mn(c) + FeSlc) — MnS(c) + Fdc)
Kk
6525-79
Mn(liq) - H ; (g>
Px
6580-79
Mn - Fe - O(liq)
Px
6672-79
Mn/O/S/Fe/Ti
DmPx
AUSOOIK
Mn/D,
Hm
GFR023P
Mn/D.
Pv
GFR023P
FIGURE 6
Al (c)
FIGURE 7
See next page for Figure 8.
NaBr(c) + 2H 2 0(C) = NaBr-2H 2 0 (c)
AH = -19.24 + 0.05 kJ/mol
= A f H (NaBr-2H 2 0) -A f H(NaBr) -2A f H (HO)
Y + u = (-19.24 + 0.05) kJ/mol = X 3 - X ] - 2x 2
FIGURE 9
24
cmiiDi:
25
Li Thermochemical Network
REACTION CATALOG INPUT
REFERENCE: 66 ARO/AUS
* PROPERTY MEASURED: H (OR G OR S ) ; UNIT: C (OR J OR V)
OBSERVED VALUE +- UNCERT.: 37.0 +-4.5
REACTION: TH'3N4(C) = 3 TH'N(C) + 0.5 N2(GS')
COMMENT: AUTHORS ' 2N0-LAW VALUE 36 .35 AT APPROX. 1923 K
ADJ'D BY 0.65 USING ESTD. CPITH3N4] = 39.33 +
0.00624T - 533000/T2 .
BIBLIOGRAPHY: ARONSON, S.; AUSKERN, A.B.; J. PHYS.CHEM.
70, 3937 (1966) .
FIGURE 10
Coordinated Projects
Shared Expertise
Shared Work Load
Common, Consistent Wortd Wide
Data Bank Use
FIGURE 11
26
NBS-114A (REV. 2-80
U.S. DEPT. OF COMM.
1. PUBLICATION OR
2. Performing Organ. Report No.
3. Publication Date
BIBLIOGRAPHIC DATA
REPORT NO.
August 1981
SHEET (See instructions)
NBSIR 81-2341
4. TITLE AND SUBTITLE
Chemical Thermodynamic Data Banks
5. AUTHOR(S)
David Garvin, Vivian B. Parker, Donald D. Wagman
6. PERFORMING ORGANIZATION (If joint or other than NBS, see instructions )
NATIONAL BUREAU OF STANDARDS
DEPARTMENT OF COMMERCE
WASHINGTON, D.C. 20234
7. Con tract/ Grant No.
8. Type of Report & Period Covered
9. SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS (Street. City. State. ZIP)
10. SUPPLEMENTARY NOTES
1 | Document describes a computer program; SF-185, FIPS Software Summary, is attached.
11. ABSTRACT (A 200-word or less factual summary of most significant information. If document includes a significant
bibliography or literature survey, mention it here)
A substantial critical evaluation of chemical thermodynamic measurements on
inorganic and C-. -Cp organic compounds has recently been completed. This provides
selected values for some 14300 substances, based on a collection of 250,000 measurements
This work is placed in a historical context of three earlier comprehensive evaluations
of thermochemi cal data.
During the course of this work data banks of several types have been developed:
bibliography, extracted unevaluated data, evaluated measurements (catalogs of reaction:.)
and selected chemical thermodynamic properties for individual substances. The design
structure and use of those data banks are described.
The course of modern data evaluation, based on these files, is discussed briefly
in terms of tests for inter-measurement consistency and autmoated solutions of large
networks of data.
A complementary thermodynamic data system developed at the Institute for High
Temperatures , Moscow, USSR is described briefly. Proposed international activities
are outlined.
12. KEY WORDS (Six to twelve entries; alphabetical order; capitalize only proper names; and separate key words by semicolons)
chemical thermodynamics; data evaluation; data banks; inforamtion systems; networks of
data; standard reference data; thermochemistry.
13. AVAILABILITY
[X 1 Unlimited
| 1 For Official Distribution. Do Not Release to NTIS
f | Order From Superintendent of Documents, U.S. Government Printing Office, Washington, D.C.
20402.
|A | Order From National Technical Information Service (NTIS), Springfield, VA. 22161
14. NO. OF
PRINTED PAGES
30
15. Price
$6 . 50
USCOMM-DC 6043-P 90
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