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Thermodynamic Properties of Minerals and Related Substances at 298.15°K (25.0°C) and One Atmosphere (1.013 Bars) Pressure and at Higher Temperatures

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Thermodynamic Properties of Minerals and Related Substances at 298.15°K (25.0°C) and One Atmosphere (1.013 Bars) Pressure and at Higher Temperatures Thermodynamic Properties of Minerals and Related ~ Substances at 298.15°K (25.0°C) o and One Atmosphere (1.013 Bars) hS O Pressure and at Higher Temperatures bd 82 GEOLOGICAL SURVEY BULLETIN 1259 ORTON MEMORIAL LIBRARY i: '£ OHIO STATE UWVEHSITY JUN 1 6 2000 CO a I to Or Thermodynamic Properties of Minerals and Related Substances at 298.15°K (25.0°C) and One Atmosphere (1.013 Bars) Pressure and at Higher Temperatures By RICHARD A. ROBIE ajid DAVID R. WALDBAUM GEOLOGICAL SURVEY BULLETIN 1259 A summary of the thermodynamic data for minerals at 298.15°K together with calculated values of the functions AH°f,T, AGI,T, ST, and (Gr H^.s/T) at temperatures up to 2,000°K ORTON MEMORIAL LIBRARY THE OHIO STATE UNIVERSITY 155 S. OVAL DRIVE UNITED STATES GOVERNMENT PRINTING OFFICE, WASHINGTON : 1968 UNITED STATES DEPARTMENT OF THE INTERIOR WALTER J. HICKEL, Secretary GEOLOGICAL SURVEY William T. Pecora, Director Library of Congress catalog-card No. OS 68-223 First printing 1968 Second printing 1970 For sale by the Superintendent of Documents, U.S. Government Printing OflBlce Washington, D.C. 20402 - Price $1.25 (paper cover) CONTENTS Page Abstract _____________________________________ 1 Introduction ___________________________________... 1 Acknowledgments ________________________________ 2 Physical constants and atomic weights ________________ 3 Reference states and transitions _________,______________ 5 Sources of data ___________,________________,______ 5 Methods of calculation ______________________________ 8 Thermodynamic properties at 298.15°K ___________________ 11 Thermodynamic properties at high temperatures ______________ 26 References and notes _______________________________ 238 Index of names ___________________________________ 249 Index of formulas ________________________________ 253 TABLES Page TABLE 1. Symbols and constants __________________ 3 2. Atomic weights for 1963 _____________________ 4 3. Chronological list of important critical summaries of thermodynamic data for inorganic substances _______. 6 THERMODYNAMIC PROPERTIES OF MINERALS AND RELATED SUBSTANCES AT 298.15°K (25.0°C) AND ONE ATMOSPHERE (1.013 BARS) PRESSURE AND AT HIGHER TEMPERATURES By RICHARD A. ROBIE and DAVID R. WALDBAUM ABSTRACT Critically selected values for the entropy (S°288.«), molar volume (VWw), and for the heat and Gibbs free energy of formation (AH 0f,z98.i5 and AG°f.288.is) are given for 50 reference elements and 285 minerals and related substances. For 211 materials for which high-temperature heat-capac­ ity or heat-content data are available AH°f,T, AG°f,T, S°T, logKf/r and (G°T H°298.i5/T) are tabulated at 100°K intervals for temperatures up to 2,000°K. For substances having solid-state phase changes or whose melt­ ing or boiling point is less than 2,000°K, we also have tabulated the prop­ erties listed above at the temperature of the phase change so that the heat or entropy changes associated with the transformation form an integral part of the high-temperature tables. INTRODUCTION The purpose of these tables is to present a critical summary of the available thermodynamic data for minerals and related sub­ stances in a convenient form for the use of earth scientists. To make the tables as useful as possible we have tried to include as much of the necessary auxiliary data as possible so that a single set of tables would suffice for most calculations, to insure internal consistency and to provide for the means of rapid revision and expansion as new data become available. This compilation is divided into two sections. In the first section we give values for the entropy (S°288.i5), molar volume (V°298.K), the heat (enthalpy, AH°f.298.i5) and Gibbs free energy (AG0f,288.15), and the logarithm of the equilibrium constant of formation (log Kf, 298.15) for the reference elements, minerals, a number of oxides, and other substances of geological interest. The data have been critically evaluated and uncertainties assigned to the 298.15°K properties. The sources of data are indicated numerically in the tables and listed in complete form following the tables. 2 THERMODYNAMIC PROPERTIES OF MINERALS The data are arranged in order of their conventional min- eralogical groups. Within each group (for example the oxides) the listing is by alphabetical order of the chemical symbol of the principal cation. The tables in the second section contain values for the high-temperature thermodynamic properties, H°T H°ns.u, (G°T -H°298.iS)/T, S°T, AG°f,T, AH°,,T, and log Kf,T at 100°K inter­ vals up to 2000°K. Heat-capacity data, as such, have been omitted from these tables in favor of the function H°T H0298.i5 which is the quantity actually measured in most high-temperature experi­ ments. Heat capacities, CP, derived from H°T H°298.i5 data are at best only approximate and their use should be avoided when possible. Approximate values for CP are readily obtained from the first differences of the tabulated H°T H 0298.i5 function. Thermodynamic properties of gases at high pressures have not been included in these tables. High pressure-high temperature functions of the geologically important gases H20 and C02 are given by Bain (1964), Hilsenrath and others (1955), and Robie (1966). These tables entirely supersede two earlier reports on the same subject matter by Robie (1959,1966)! ACKNOWLEDGMENTS Professor E. F. Westrum, Jr., University of Michigan, Profes­ sor 0. J. Kleppa, University of Chicago, and P. B. Barton, Jr., Priestley Toulmin, and D. R. Wones, U.S. Geological Survey, have kindly permitted us to use some of their unpublished data. We are particularly grateful to Keith Beardsley of the U.S. Geological Survey who wrote the computer routines for processing the 298.15°K tables and the bibliography. E-an Zen of the U.S. Geo­ logical Survey and Professor J. B. Thompson, Jr., of Harvard University offered many helpful suggestions for improving the clarity and usefulness of these tables. Computer facilities at the Massachusetts Institute of Technology were used initially to develop the program for compiling high- temperature thermodynamic functions. More recent revisions of the program and the present set of tables were prepared at the Harvard Computing Center, with computer costs supported by the Higgins Fund and the Committee on Experimental Geology and Geophysics of Harvard University. THERMODYNAMIC PROPERTIES OF MINERALS 3 PHYSICAL CONSTANTS AND ATOMIC WEIGHTS The symbols and constants adopted for this report are listed in table 1. Values for the physical constants used in the calculations were those recommended by the National Academy of Science- National Research Council (U.S. Natl. Bur. Standards Tech. News Bull., v. 47, p. 175-177, 1963). For convenience we also give values of the international atomic weights for 1963 (scale C12 = 12.0000) in alphabetical order by their chemical symbol in table 2. Elements for which no atomic weight is listed have no stable isotope. TABLE 1. Symbols and constants T Temperature in degrees Kelvin, (°K) gfw Gram formula weight H° -H° Enthalpy at temperature T relative to 298.15°K in cal gfw 1, T S° Entropy at temperature T in cal deg-gfw"1 G° -H° T SM.15 m Gibbs free energy function in cal deg-gfw"1 A^f° Heat of formation from reference state in cal gfw" 1 AG° Gibbs free energy of formation from reference state in cal gfw"1 Kr Equilibrium constant of formation Cp Heat capacity at constant pressure in cal deg-gfw" 1 0 Superscript indicates the substance is in its standard state » TTO meit Heat of melting at one atmosphere in cal gfw"1 AH° Heat of vaporization to ideal gas at one atmosphere at the "p normal boiling point in cal gfw"1 V° Volume of one gram formula weight at one atmosphere and "* " 298.15°K in cm8 R Gas constant, 1.98717 ±.00030 cal deg-gfw 1, 8.31469 joules deg-gfw"1 cal Calorie, unit of energy, 4.1840 absolute joules, 41.2929 cm* atmosphere A Avogadro's number, (6.02252 ±. 00028) xlO23 formula ' units gfw1 P Pressure, either in atmosphere or bars atm Atmosphere, 1,013,260 dynes cm"* bar Bar, 1,000,000 dynes cm"2 log Common logarithm, base 10 In Natural logarithm, base e= 2.71828. THERMODYNAMIC PROPERTIES OF MINERALS TABLE 2. Atomic weights for 1963 Atomic Atomic Element Symbol weight Element Symbol weight Ac _ N 14.0067 SllvPT* A<r 107.870 Sodium Na 22.9898 Aluminum _ Al 26.9815 Nb no onft Americium _ _ Am243 243.061 Neodymium Nd 144 94 Argon _ - Ar 39.948 Ne 9ft 1 8°. Arsenic As 74.9216 Ajlf»lfp1 Ni 58.71 Astatine At Np237 OQ7 ft/lQ Gold Au 196.967 Owcrpri _ 0 15 9994 Boron B 10.811 Osmium Os 1Qft 9 Barium Ba 137.34 _ _P on 0700 Beryllium __ Be Q 01 99 Protactinium _ Pa Bismuth Bi 208.980 Lead _ Pb 207.19 Br 7Q ana Palladium _ .. Pd 106.4 Carbon _ _ C 12.01115 Polonium __ Po Calcium _ _ Ca 40.08 Promethium _ _ Pm Cadmium _ Cd 112.40 Praseodymium __ Pr 140.907 Cerium . _Ce 140.12 Platinum _ Pt 195.09 Chlorine Cl 35.453 Plutonium Pu239 239.052 Cobalt Co 58.9332 Radium Ra Cr 51.996 Rubidium _ _ Rb 85.47 Cesium ._ Cs 132.905 Rhenium __ Re 186.2 Rhodium _ Rh Copper - Cu 63.54 102.905 Radon _ Rn Dysprosium _____Dy 162.50 _ Ru Erbium Er 167.26 Ruthenium 101.07 Sulfur _ S Europium Eu 151.96 32.064 Antimony _ Sb Fluorine F 18.9984 121.75 Scandium _ .Sc Iron Fe 55.847 44.956 Francium Fr Selenium - -Se 78.96 Silicon _ _Si Gallium Ga 69.72 28.086 Samarium Gadolinium 157.25 Sm 150.35 Tin .
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