REEERENC] 1 NAT'L INST. OF STAND & TECH AlllDb 33Mab3 N!ST jNBS Publi- cations NBS TECHNICAL NOTE 270-7 REFERENCE Selected Values of Chemical Thermodynamic Properties U.S. DEPARTMENT OF COMMERCE National |— QC— of 100 is ho.Z70-7 Tables for the Lanthanide (Rare Earth) Elements (Elements 62 through 76 in the Standard Order of Arrangement)
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REEERENC]1 NAT'L INST. OF STAND & TECH
AlllDb 33Mab3
N!ST
jNBSPubli-
cations
NBS TECHNICAL NOTE 270-7
REFERENCE
Selected Values of
Chemical Thermodynamic
Properties
U.S.
DEPARTMENTOF
COMMERCENational
|— QC— of
100 is
ho.Z70-7
Tables for the Lanthanide
(Rare Earth) Elements
(Elements 62 through 76 in the
Standard Order of Arrangement)
NATIONAL BUREAU OF STANDARDS
The National Bureau of Standards' was established by an act of Congress March 3,
1901. The Bureau's overall goal is to strengthen and advance the Nation's science andtechnology and facilitate their effective application for public benefit. To this end, theBureau conducts research and provides: (1) a basis for the Nation's physical mea.sure-
ment system, (2) scientific and technological services for industry and government, (3)
a technical basis for equity in trade, and (4) technical services to promote public safety.
The Bureau consists of the Institute for Basic Standards, the Institute for MaterialsResearch, the Institute for Applied Technology, the Center for Computer Sciences andTechnology, and the Office for Information Programs.
THE INSTITUTE FOR BASIC STANDARDS provides the central basis within theUnited States of a complete and consistent system of physical measurement; coordinatesthat system with measurement systems of other nations; and furnishes essential services
leading to accurate and uniform physical measurements throughout the Nation's scien-
tific community, industry, and commerce. The Institute consists of a Center for Radia-tion Research, an Office of Measurement Services and the following divisions:
THE INSTITUTE FOR MATERIALS RESEARCH conducts materials research lead-
ing to improved methods of measurement, standards, and data on the prop>erties of
well-characterized materials needed by industry, commerce, educational institutions, andGovernment; provides advisory and research services to other Government agencies;
and develops, produces, and distributes standard reference materials. The Institute con-
sists of the Office of Standard Reference Materials and the following divisions:
THE INSTITUTE FOR APPLIED TECHNOLOGY provides technical services to pro-
mote the use of available technology and to facilitate technological innovation in indus-
try and Government; cooperates with public and private organizations leading to the
development of technological standards (including mandatory safety standards), codes
and methods of test; and provides technical advice and services to Government agencies
upon request. The Institute also monitors NBS engineering standards activities and
provides liaison between NBS and national and international engineering standards
bodies. The Institute consists of a Center for Building Technology and the following
divisions and offices:
Engineering and Product Standards—Weights and Measures—-Invention andInnovation—Product Evaluation Technology—Electronic Technology—Techni-cal Analysis—Measurement Engineering—Building Standards and Code Serv-
ices-*—Housing Technology'—Federal Building Technology'—Structures, Mate-rials and Life Safety^—Building Environment'—Technical Evaluation andApplication'—Fire Technology.
THE INSTITUTE FOR COMPUTER SCIENCES AND TECHNOLOGY conducts re-
search and provides technical services designed to aid Government agencies in improv-ing cost effectiveness in the conduct of their programs through the selection, acquisition,
and effective utilization of automatic data processing equipment; and serves as the prin-
cipal focus within the executive branch for the development of Federal standards for
automatic data processing equipment, techniques, and computer languages. The Centerconsists of the following offices and divisions:
Information Processing Standards—Computer Information—Computer Services
Technical Note ZlO-7 is the seventh part of a series of Notes
containing the tables of numerical material prepared as a revision of
Series I of National Bureau of Standards Circular 500, Selected
Values of Chemical Thermodynamic Properties, by F. D. Rossini,
D. D. Wagman, W. H. Evans, S. Levine, and I. Jaffe. This Note
contains data for the compounds of 15 elements, numbered 62 through
76 in the Standard Order of Arrangement. In addition there is an
Appendix which contains a list of all the corrections and misprints
which have been detected in the previous Notes of this Series.
The continued encouragement and support of the Office of
Standard Reference Data of the National Bureau of Standards is
gratefully acknowledged.
IV
Contents
Preface iv
Introduction vii
Standard Order of Arrangements of the Elements^ Figure 1 . . xi
Table A. Conversion Factors for Units of Molecular Energy . xii
Table 62 Lutetium 1
Table 63 Ytterbium 4
Table 64 Thulium 9
Table 65 Erbium 13
Table 66 Holmium 16
Table 67 Dysprosium 21
Table 68 Terbium 25
Table 69 Gadolinium 29
Table 70 Europium ...» 33
Table 71 Samarium 37
Table 72 Promethium 42
Table 73 Neodymium 43
Table 74 Praseodymium 48
Table 75 Cerium 53
Table 76 Lanthanum 60
Appendix 69
Index of Contents c 73
SELECTED VALUES OF CHEMICAL THERMODYNAMIC PROPERTIES
INTRODUCTION
Substances and Properties Included in the Tables
The tables contain values where known of the enthalpy and Gibbs
energy of formation, enthalpy, entropy and heat capacity at 298.15 K(ZS^C), and the enthalpy of formation at K, for all inorganic substances
and organic molecules containing not more than two carbon atoms. In
some instances such as metal-organic compounds, data are given for
substances in which each organic radical contains one or two carbon
atoms
.
No values are given in these tables for metal alloys or other
solid solutions, fused salts, or for substances of undefined chemical
composition.
Physical States
The physical state of each substance is indicated in the column
headed "State" as crystalline solid (c), liquid (liq), glassy or amorphous
(amorp), or gaseous (g). Solutions in water are listed as aqueous (aq).
For non-aqueous systems the physical state is that normal for the
indicated solvent at 298.15 K.
Definition of Symbols
The symbols used in these tables are defined as follows: P =
pressure; V = volumie; T = absolute temperature; E = intrinsic or
internal energy; S = entropy; H = E + PV = enthalpy (heat content);
G = H - TS = Gibbs energy (formierly the ^ree energy); C = (dH/dT)-., =
heat capacity at constant pressure.
VI
Conventions Regarding Pure Substances
The values of the thermodynamic properties of the pure substances
given in these tables are for the substances in their standard states
(indicated by the superscript " on the thermodynamic symbol). Thesestandard states are defined as follows:
For a pure solid or liquid, the standard state is the substance
in the condensed phase under a pressure of one atmosphere.For a gas the standard state is the hypothetical ideal gas at unit
fugacity, in which state the enthalpy is that of the real gas at the sametemperature and at zero pressure.
The values of A Hf " and AGf" given in the tables represent the changein the appropriate thermodynamic quantity when one gram -formulaweight of the substance in its standard state is formed, isothermally at
the indicated temperature, from the elements, each in its appropriatestandard reference state. The standard reference state at 25 "C for
each element except' phosphorus has been chosen to be the standardstate that is thermodynamically stable at 25 "C and at one atmospherepressure. For phosphorus the standard reference state is the crystalline
white form; the more stable forms have not been well characterizedthermochemically. The same reference states have been maintained for
the elements at K except for the liqmd elements bromine and mercury,for which the reference states have been chosen as the stable crystalline
forms. The standard reference states are indicated in the tables by the
fact that the values of A Hi" and A Gf ° are exactly zero.
The values of H^q^ -Hq represent the enthalpy difference for the
given substance between 298.15 K and K. If the indicated standardstate at 25 °C is the gas, the corresponding state at K is the hypo-thetical ideal gas; if the state at 25 "C is solid or liqiiid, the corres-ponding state at K is the thermodynamically 'stable crystalline
solid, \anless otherwise specifically indicated.
The values of S° represent the virtual or "thermal" entropy of the
substance in the standard state at 298.15 K, omitting contributions fromnuclear spins. Isotope mixing effects, etc. , are also excluded exceptin the case of the hydrogen-deuterium ( H- H) system. Where data havebeen available only for a particular isotope, they have been correctedwhen possible to the normal isotopic composition.
The values of the enthalpies of formation of gaseous ionic speciesare computed on the convention that the value of AHf ° for the electronis zero. Conversions between and 298.15 K are calculated usingthe value of H2Q8-Hq = 1. 481 kcal per mole of electrons, and assumingthat the values of H2Q0-H0 for the ionized and vui-ionized molecules are
the same.
VII
Conventions Regarding Solutions
Solutions in water are designated as aqueous (aq); other solventsare designated by name or chemical formula. The concentration of the
solution is expressed in terms of the number of moles of solvent asso-ciated with one mole of the solute. If no concentration is indicated, the
solution is assumed to be "dilute".
The standard state for a non-dissociated solute in aqueous solution
is taken as the hypothetical ideal solution of unit molality, which has beendesignated as "std. state, m = 1". For strong electrolytes in aqueoussolution the conventional standard state is the ideal solution of unit
activity (unit mean molality). For nonaqueous solutions the standardstate of the solute is the hypothetical ideal solution of unit molefraction of solute (std. state, X2 = 1).
The value of IHl" given the tables for a solute in its standardstate is the apparent molal enthalpy of formation of the substance in
the infinitely dilute real solution. At this dilution the partial molalenthalpy is equal to the apparent molal quantity. At concentrations
other than the standard state, the value of A Hf° represents the apparententhalpy of the reaction of formation of the solution from the elennents
comprising the solute, each in its standard reference state, and the
appropriate total number of moles of solvent. In this representation
the value of AHf° for the solvent is not required. The experimental value
for a heat of dilution is obtained directly as the difference between the
two values of A Hf° at the corresponding concentrations.
The values of the thermodynainic properties tabulated for the
individual ions in aqueous solution are based on the usual conventionthat the values of AHf°, AGf°, S° and Cp° for H+ (aq, std. state, m = 1)
are zero. The properties of a neutral electrolyte in aqueous solution
in the standard state are equal to the algebraic sum of these values for
the appropriate kinds and number of individual ions assumed to constitute
the molecule of the given electrolyte. When the undissociated species,
rather than the s\im of the ions, is meant, the notation "undissociated"
or "\in-ionized" is used. For an ionic species the properties tabulated
refer to that undissociated ion. By adopting the above convention with
respect to aqueous H , it follows that the thermodynamic relation A Gf°
= A Hf° - T ASf° will not hold for an individual ionic species. Howeverno problem arises when neutral chemical systems are considered.
Vlll
Unit of Energy and Fundamental Constants
All of the energy values given in these tables are expressed in termsof the thermochemical calorie. This unit, defined as equal to 4.1840
joules, is generally accepted for the presentation of chemical thermo-dynamic data. Values reported in other units have been converted to
calories by means of the conversion factors for molecular energy given
in Table A.The following values of the fundamental physical constants have
been used in these calculations:
R = gas constant = 8. 3143 + 0. 0012 J/deg mol = 1.98717 + 0. 00029
Z = Nhc = 11.96258 + 0.00107 J/cm"^ mol = 2.85912 -k 0.00026 cal/cm"^ molC2 = second radiation constant = hc/k = 1.43879 ± 0.00015 cm degO'C = 273.15 K
These constants are consistent with those given in the Table of GeneralPhysical Constants, recommended by the National Academy of Sciences -
National Research Council . The formula weights in the tables havebeen calculated for the molecular formula given in the Formula andDescription column using the 1961 Table of Relative Atomic Weights basedon the atomic mass of ^ C = 12 exactly .
Internal Consistency of the Tables
All of the values given in these tables have been calculated fromthe original articles, using consistent values for all subsidiary anda\ixiliary quantities. The original data were corrected where possible
for differences in energy units, molecular weights, temperature scales,
etc. Thus we have sought to maintain a vmiform scale of energies for
all the substances in the tables. In addition the tabulated values of the
properties of a substance satisfy all the known physical and thermodynamicrelationships among these properties. The quantities A Hf ", A Gf °, andS" at 298.15 K satisfy the relation:
A Gf = A Hf° - T ASf".
NBS Technical News Bulletin, October 1963.
2A. E. Cameron and E. Wichers, J. Am. Chem, Soc. 84, 4192 (1962).
IX
Furthermore the calculated value of any thermodynamic quantity for a
reaction is independent of the path chosen for the evaluation.
In Sonne cases new^er data may have become available on certain
substances after the values were selected for these tables. Becauseof the need to maintain the internal consistency of the tables, it is not
always possible to incorporate these newer data into the tables without
a detailed analysis of the effect of such a change. Unless great care is
used, relatively significant errors in calculated values of A H° or A G"for specific reactions may result from the introduction of such data.
Uncertainties
The uncertainty in any value in the tables depends on the uncertain-
ties of all the determinations in the total chain of reactions used to
establish the value.
A discussion of the uncertainties will be included in the final
publication of these tables in the National Standard Reference DataSystem. However we have followed certain rules with respect to
significant figures to indicate these ixncertainties. Values are tabulated
in general such that the overall uncertainty lies between 2 and 20 units
of the last figure. On the other hand, values are given so that the
experimental data from which they are derived may be recovered with
an accuracy equal to that of the original quantities. Thus the numberof significant figures for any one value in the tables need not representthe absolute accuracy of that value. For solutions of varying connposition
values are frequently tabulated to more figures to make possible the
recovery of enthalpies of solution and dilution. Similarly values of
A Hfrt and AHflqo ic may be given to different numbers of significant
figures. In this instance the quantity with the lesser number of figures
is used to represent the uncertainty estimate. The larger number of
figures is used for the other quantity to retain the significance of the
temperature correction term.
Arrangement of the Tables
The compounds in the tables are entered according to the StandardOrder of Arrangement, (see Figure 1), by the principle of latest position.
In this scheme, a compound is listed \ander the element occurring latest
in the list; water of hydration is neglected. Within a given element-table will be found all of the compoonds of that element with elementsoccurring earlier in the order; the arrangement within a table follows
the same ordering. An exception occurs in the carbon tables (Table 23),
which is divided into subgroups consisting of all compounds with onecarbon atom, then all with two carbon atoms, etc.
X
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TABLES OF SELECTED VALUES OF PROPERTIES
SERIES I
Enthalpy of Formation at K
Enthalpy of Formation at 298. 15 K
Gibbs Energy of Formation at 298. 15 K
Enthalpy at 298. 15 K
Entropy at 298. 15 K
Heat Capacity at 298. 15 K
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75
FORM NBS-114A (1-71)
2. Gov't AccessionNo.
U.S. DEPT. OF COMM.BIBLIOGRAPHIC DATA
SHEET
PUBLICATION OR REPORT NO.
NBS-TN-270-73. Recipient's Accession No.
4. TITLE AND SUBTITLESelected Values of Chemical Thermodynamic PropertiesTables for the Lanthanide (Rare Earth) Elements(Elements 6Z through 76 in the Standard Order of Arrangement)
5. Publication Date
April 1973
6. Performing Organization Code
7. AUTHOR(S) R. H. Schumm, D. D. Wagman, S. Bailey,W. H. Evans, and V. B. Parker
8. Performing Organization
10. Project/Task/Work Unit No.
316-01159. PERFORMING ORGANIZATION NAME AND ADDRESS
NATIONAL BUREAU OF STANDARDSDEPARTMENT OF COMMERCEWASHINGTON, D.C. 20234
11. Contract/Grant No.
12. Sponsoring Organization Name and Address
Same as 9.
13. Type of Report & PeriodCovered
Final
14. Sponsoring Agency Code
15. SUPPLEMENTARY NOTES
16. ABSTRACT (A 200-word or less factual summary of most significant information. If document includes a significantbibliography or literature survey, mention it here.)
Contains tables of values for the standard heats and Gibbs (free)
energies of formation, entropies and enthalpies at 298.15 K and heatsof formation at K for compounds of the rare-earth elements ( thelanthanides ; lutetium through lanthanum; elements 62 through 76 in theStandard Order of Arrangement). These tables are a continuation of
17. KEY WORDS (Alphabetical order, separated by semicolons)
S ee above
18. AVAILABILITY STATEMENT
[3 UNLIMITED.
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19. SECURITY CLASS(THIS REPORT)
UNCLASSIFIED
20. SECURITY CLASS(THIS PAGE)
UNCLASSIFIED
21. NO. OF PAGES
93
22. Price
S1.25 Domestic Postpaid
Sl.OO GPO Bookstore
USCOMM-DC 66244.P7t
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Selected Values of Chemical Thermodynamic Properties
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