Molten Salts Handbook

MOLTEN SALTS HANDBOOK

George J. Janz

Rensselaer Polytechnic Institute, Troy, New York

Table of Contents

Cover image

Title page

Copyright

PREFACE

ACKNOWLEDGMENTS

I: PHYSICAL PROPERTIES

I.A: ATOMIC AND IONIC RADII, MELTING POINTS, AND BOILING POINTS OF SINGLE SALTS AND EUTECTICS

I.B: DENSITY

I.C: VISCOSITY

I.D: VAPOR PRESSURE

I.E: SURFACE TENSION

I.F: REFRACTIVE INDEX

I.G: CRITICAL DATA

II: THERMODYNAMIC PROPERTIES

II.A: LIQUID-LIQUID IMMISCIBILITY

II.B: METAL-MOLTEN SALT SYSTEMS

II.C: METAL OXIDE-MOLTEN SALT SYSTEMS

II.D: SILVER SALTS-MOLTEN SALT SYSTEMS

II.E: PHASE-RULE STUDIES

II.F: SOLUBILITY

II.G: THERMAL DATA

II.H: CRYOSCOPY AND RELATED THERMODYNAMIC STUDIES

II.I: EXPANSIVITY, COMPRESSIBILITY, ULTRASONIC, AND HIGH PRESSURE STUDIES

III: ELECTROCHEMICAL PROPERTIES

III.A: REFERENCE ELECTRODES AND EMF SERIES

III.B: ELECTRICAL CONDUCTANCE

III.C: POLAROGRAPHY, CHRONOPOTENTIOMETRY, AND DOUBLE LAYER CAPACITY STUDIES

III.D: ELECTROMIGRATION: TRANSPORT NUMBERS AND DIFFUSION

III.E: DIELECTRIC AND THERMOELECTRIC PROPERTIES

IV: SPECTROSCOPY AND STRUCTURE

IV.A: VIBRATIONAL SPECTROSCOPY

IV.B: VISIBLE AND U. V. SPECTROSCOPY

IV.C: NUCLEAR MAGNETIC AND ELECTRON PARAMAGNETIC RESONANCE SPECTROSCOPY

IV.D: X-RAY AND NEUTRON DIFFRACTION

IV.E: FUSED SALT ELECTROLYTES

V: PRACTICAL FEATURES

V.A: MELT PREPARATION AND PURIFICATION

Principles of Electrolyte Purificationa, b

V.B: CONTAINMENT AND CORROSION

V.C: CHROMATOGRAPHIC ANALYSIS

V.D: ELECTROLYSIS

V.E: CHEMICAL PROCESSES

V.F: FUEL CELLS, BATTERIES, NUCLEAR TECHNOLOGY

VI: EXPERIMENTAL TECHNIQUES

VI.A: ILLUSTRATIONS OF EXPERIMENTAL ASSEMBLIES

VI.B.1: Additional References and Data Sources

CHEMICAL FORMULA INDEX

Copyright

COPYRIGHT © 1967, BY ACADEMIC PRESS INC.

ALL RIGHTS RESERVED.

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PRINTED IN THE UNITED STATES OF AMERICA

PREFACE

The field of molten salts has been the subject of renewed interest over the past 25 years and has attracted the attention of scientists in research and technology from such diverse fields as: theoretical and applied electrochemistry, inorganic coordination chemistry, transition metal chemistry, preparative and process chemistry having melts as catalysts or as reaction media, nonaqueous solvents, thermochemistry, fuel cells and batteries, nuclear technology, analytical principles of chromatography and liquid-liquid solvent extraction, corrosion science, and the principles of liquid structure, theoretical chemistry, and physics.

The presentation of data for a topic as complex as the entire field of molten salts in a convenient yet concise and orderly format is difficult without some measure of compromise. The information contained in Molten Salts Handbook has been organized into five well-defined areas: Physical Properties, Thermodynamic Properties, Electrochemical Properties, Spectroscopy and Structure, and Practical Features. A sixth section, that of Experimental Techniques, is included to illustrate design features of various experimental assemblies and to provide information on points of technique through a liberally annotated bibliography. The chemical index offers a ready guide to the status of data over the entire range of interests.

For the greatest part, the numerical values in this handbook are exactly those in the original source material. Differing values arise for derived propperties (for example, cryoscopic constants) of the same compound since the investigators’ results do not agree as to melting point temperatures, heats of fusion, and other properties. Molten Salts Handbook will fulfill part of its purpose if it focuses attention on such problem areas. A need exists for data evaluation studies in order to recommend best values from a critical assessment of the experimental problems and the precision and accuracy of the measurements. The results of such studies in the author’s laboratory are summarized in this handbook for the properties of density, viscosity, surface tension, refractive index, and electrical conductance for various compounds as single salt melts.

Topics such as phase equilibria, molten salt electrolytes, and chemical syntheses are presented in annotated bibliographic table form. This format was also chosen to direct attention to further contributions and these are listed as tables of additional studies. While it was recognized that certain data relate quite aptly to two or more areas of classification, the detailed list of tables and the chemical index should compensate, in part, for the arbitrary classification adopted in such instances. The original references with each table will prove useful to those undertaking further studies or calculations.

The author is indebted to his research co-workers for assistance with proofreading; in particular, thanks are due to G. R. Lakshminarayanan (Bapu) for his constant attention and care in all phases of the production of Molten Salts Handbook.

July, 1967

GEORGE J. JANZ,     Rensselaer Polytechnic Institute

ACKNOWLEDGMENTS

The author is pleased to acknowledge the permission granted to reproduce, in part or in total, the tabulations of data from the various scientific research journals and books. Without this very generous gesture from authors and publishers, this volume would not have been realized.

It is a pleasure to acknowledge the financial support for basic research in molten salts in the author’s laboratory at Rensselaer Polytechnic Institute for the past two decades from: National Science Foundation; Office of Naval Research, U. S. Navy; Air Force Office of Scientific Research; Office of Standard Reference Data, U. S. Bureau of Standards; and the Rensselaer Trustees Research Committee.

The source material for this handbook is a cumulative file to which the pre-doctoral and post-doctoral researchers in molten salts have contributed on a continuing basis over a number of years. The author wishes to take this opportunity to thank the following members of this team for their very material assistance in this respect:

I. Ahmad, E. J. Andalaft, C. M. Baddiel, C. T. Brown, T. G. Coker, F. Colom, A. Conte, F. W. Dampier, Chr. G. M. Dijkhuis, L. Friedman, H. J. Gardner, J. Goodkin, B. B. Hardman, M. D. Ingram, D. W. James, F. J. Kelly, T. R. Koslowski, G. R. Lakshminarayanan (Bapu), M. R. Lorenz, P. Lorenz, G. E. Mayer, Y. Mikawa, J. D. E. McIntyre, E. Neuenschwander, J. Perano, D. J. Perettie, R. D. Reeves, F. Saegusa, H. Taniguchi, A. Timidei, R. J. Tofte, R. P. T. Tomkins, A. T. Ward, and J. Wong.

I

PHYSICAL PROPERTIES

I.A

ATOMIC AND IONIC RADII, MELTING POINTS, AND BOILING POINTS OF SINGLE SALTS AND EUTECTICS

TABLE I.A. 1a

Atomic and Ionic (Crystal) Radii a

aIonic crystal radii are the Pauling values; see L. Pauling, The Nature of the Chemical Bond. Cornell Univ. Press, Ithaca, New York, 1948.

bThe number in parentheses indicates the valency of each element as the ion

TABLE I.A. 1b

Solid State Interionic Separations (Å) a,b

aAt room temperature.

bJ. Lumsden, Discussions Faraday Soc. 32, 138 (1961); from R. W. G. Wyckoff,Crystal Structures. Wiley (Interscience), New York, 1948.

TABLE I.A. 1c

Volumes of Anions

TABLE I.A. 2a

Formula Weights, Melting Points, and Boiling Points for Some Inorganic Compounds a,b

aThroughout Table I. A. 2a, the values enclosed in parentheses represent estimates (as reported in Ref. 2).

bThe mp is taken under pressure.

¹10.1 mm 400, 1 atm 540.

²0.21 mm 500, 1 atm 900.

³1 atm 1289.

⁴0.2 mm 900,1 atm 1360.

⁵1atm 282.

¹11 mm 900.

²2mm 900.

³2mm 900.

¹1atm O2 474.

²1 atm O2 525.

³1 atm O2 533.

⁴1 atm O2 548.

⁵1 atm O2 584.

¹Explodes at 800°C.

TABLE I.A. 2b

The Effect of Pressure on Melting Points a

aJ. Lumsden, The Thermodynamics of Molten-Salt Mixtures, p. 10. Academic Press, New York, 1966. See also, S. P. Clark, J. Chem. Phys. 31, 1526 (1959).

TABLE I.A. 3

Melting Points of Some Quaternary Ammonium Salts R4N+X−

TABLE I.A. 4

Selected Low Melting Binary Eutectics a

aW. R. Grimes and D. R. Cuneo, in Reactor Handbook (C. R. Tipton, Jr., ed.), Vol. I., Chap. 17, 2nd ed. rev. Wiley (Interscience), New York, 1960. See also, R. A. Bailey and G. J. Janz, in The Chemistry of Non- Aqueous Solvents (J. J. Lagowski, ed.), Vol. I, p. 291. Academic Press, New York, 1966. See also reference to P. V. Clark in Section VLB. 1, p. 514.

bH. W. Otto and R. P. Seward, J. Chem. Eng. Data 9, 507 (1964).

cW. D. Powers and G. C. Blalock, U. S. At. Energy Comm. Rept. ONRL-1653, Jan. 20 (1954).

TABLE I.A. 5

Additional Low Melting Binary Eutectic Mixtures a

aSee also reference to P. V. Clark in Section VLB. 1, p. 514.

TABLE I.A. 6

Selected Ternary Eutectic Mixtures a

aW. R. Grimes and D. R. Cuneo, in Reactor Handbook (C. R. Tipton, Jr., ed.), Vol. I, Chap. 17, 2nd ed. rev. Wiley (Interscience), New York, 1960. See also, R. A. Bailey and G. J. Janz, in The Chemistry of Non- Aqueous Solvents (J. J. Lagowski, ed.), Vol. I, p. 297. Academic Press, New York, 1966. See also P. V. Clark (full reference given in Section VI.B. 1, P. 514).

TABLE I.A. 7

Melting Points and the Law of Corresponding Statesa

aH. Reiss, S. W. Mayer, and J. L. Katz, J. Chem. Phys. 35, 820 (1961).

bMelting point data from O. Kubaschewski and E. L. Evans, Metallurgical Thermochemistry, 3rd ed. rev. Pergamon, Oxford, 1958.

cSee Table I.A.1, this volume.

dτ m is the reduced variable corresponding to Tm. This is defined τ=k λ T/Z², where λ is the sum of the radii, Z is the valence of the compound, and k is the dielectric constant (k is assumed equal to unity in the above calculation).

REFERENCES

1. Janz, G.J., James, D.W. Electrochim. Acta 7. 1962; 427.

2. Zarzycki, J. Discussions Faraday. Soc. 32. 1961; 38.

REFERENCES

1. Rossini, F.D., Wagman, D.D., Evans, W.H., Levine, S., Jaffe, I. Selected values of chemical thermodynamic properties. Natl. Bur. Std. (U.S.) Circ. 1952; 500.

2. A. Glassner, The thermochemical properties of oxides, fluorides, and chlorides to 2500°K. ANL Rept. 5750(1959).

3. Janz, G.J., Ward, A.T., Reeves, R.Molten salt data: conductance, density, and viscosity. Tech. Bull. Ser. Troy, New York: Rensselaer Polytechnic Inst., 1964.

4. Schneider, S.J. Compilation of the melting points of the metal oxides. Natl. Bur. Std. (U.S.) Monograph. 1963; 68.

5. Hodgman C.D., et al, eds. Handbook of Chemistry and Physics, 45th. ed., Cleveland, Ohio: Chemical Rubber Co., 1964–65.

6. Russell, H., Rundle, R.E., Yost, D.M. J. Am. Chem. Soc. 1941; 63:2825.

7. Phipps, T.E., Sears, G.W., Seifert, R.L., Simpson, O.C. J. Chem. Phys. 1950; 18:713.

8. Kolditz, L. Z. Anorg. Allgem. Chem. 1957; 289:118.

9. Cook, C.M., Dunn, W.E. J. Phys. Chem. 1961; 65:1505.

10. Germann, F.E.E., Metz, C.F. J. Phys. Chem. 1931; 35:1944.

11. Baker, E.H. J. Chem. Soc. 1962; 699.

12. Markowitz, M.M. J. Phys. Chem. 1958; 62:827.

13. Schmitz-Dumont, O., Weeg, A. Z. Anorg. Allgem. Chem. 1951; 265:139.

14. Smith, W.T., Long, S.H. J. Am. Chem. Soc. 1948; 70:354.

15. Wyllie, P.J., Tuttle, O.F. J. Petrol. 1960; 1:1.

REFERENCES

1. Wedekind, E. Ber. Deut. Chem. Ges. 1902; 35:766.

2. Sugden, S., Wilkins, H. J. Chem. Soc. 1929; 1291.

3. Deno, N.C., Berkheimer, H.E. J. Org. Chem. 1963; 28:2143.

4. Tucker, L.M., Kraus, C.A. J. Am. Chem. Soc. 1947; 69:454.

5. Walden, P., Ulich, H., Birr, E.J. Z. Physik. Chem. 1927; 130:495.

6. Vernon, A.A., Masterson, J.P. J. Am. Chem. Soc. 1942; 64:2822.

7. Reynolds, M.B., Kraus, C.A. J. Am. Chem. Soc. 1943; 70:1709.

8. Inami, Y.H., Ramsey, J.B. J. Chem. Phys. 1959; 31:1297.

9. Copenhafer, D.T., Kraus, C.A. J. Chem. Phys. 1951; 73:4557.

10. Gordon, J.E. J. Org. Chem. 1966; [in press].

11. Kenausis, L.C., Evers, E.C., Kraus, C.A. Proc. Natl. Acad. Sci. U.S. 1962; 48:121.

12. Ostwald, W., Roederer, H. Kolloid Z. 1938; 82:174.

13. Walden, P., Gloy, H. Z. Physik. Chem. 1929; 144:395.

14. Lind, J.E., Jr., Abdel-Rehim, H.A.A., Rudich, S.W. J. Phys. Chem. 1966; 70:3610. [For additional data, see also:].

REFERENCES

1. Sinistri, C., Franzosini, P. Ric. Sci. Rend. Sez. 1963; A3(4):419.

2. Franzosini, P., Sinistri, C. Ric. Sci. Rend. Sez. 1963; A3(4):439.

3. Sinistri, C., Franzosini, P. Ric. Sci. Rend. Sez. 1963; A3(4):449.

4. Sinistri, C., Franzosini, P., Rolla, M. Ric. Sci. Rend. Sez. 1965; A8(4):681.

5. Franzosini, P., Riccardi, R. Ann. Chim. (Rome). 1963; 53:558.

I.B

DENSITY

TABLE I.B. 1

Melt Densities – Single Saltsa

aG. J. Janz, A. T. Ward, and R. D. Reeves, Molten salt data: conductance, density, and viscosity. Tech. Bull. Ser., Rensselaer Polytechnic Inst., Troy, New York (1964); data in Table I.B.I revised by F. Dampier and G. J. Janz, 1966.

bThe underscored references contain data which were weighted in this assessment of the densities of single salt melts.

TABLE I.B. 2

Density of Some Solid Halide Saltsa

aJ. O’M. Bockris, A. Pilla, and J. L. Barton, Rev. Chim. Acad. Rep. Populaire Roumaine 7, 59 (1962).

TABLE I.B. 3a

Percentage Volume Change on Fusion for Some Inorganic Halidesa

aJ. O’M. Bockris, A. Pilla, and J. L. Barton, Rev. Chim. Acad. Rep. Populaire Roumaine 7, 59 (1962).

bVs is the solid volume at the melting point.

TABLE I.B. 3b

Volume Change of NaCl and KCl on Melting

aVs is the solid volume at the melting point.

TABLE I.B. 3c

Volume Changes Due to Melting and Molar Volumes of Some Molten Saltsa

aM. Shimoji, Discussions Faraday Soc. 32, 128 (1961). ΔV(%) denotes the ratio of the volume change to the molar volume of the solid state; V1 is the molar volume of the liquid at melting temperature.

TABLE I.B. 4

Densities of Cryolite with Additivesa

aJ. D. Edwards, C. S. Taylor, L. A. Cosgrove, and A. S. Russell, J. Electrochem. Soc. 100, 508 (1953).

TABLE I.B. 5

Melt Densities – Binary Systems

aSee also Table II. I. 13, this volume.

TABLE I.B. 6

Melt Densities – Ternary and Quaternary Systems

aJ. Lasek, Collection Czech. Chem. Commun. 29, 1958 (1964). bG. W. MellorsandS. Senderoff, J. Electrochem. Soc. 111, 1355 (1964). cI. A. Semerikova and A. F. Alabyshev, Zh. Fiz. Khim. 37, 207 (1963). d E. F. Riebling, J. Chem. Phys. 43, 499, 1772 (1965).e E. F. Riebling, J. Chem. Phys. 41, 451 (1964).f E. F. Riebling, Can. J. Chem. 42, 2811 (1964).g P. I. Protsenkv and O. N. Shokina, Zh. Fiz. Khim. 36, 474 (1962).

TABLE I.B. 7

Literature Values for the Densities of Molten NaCl and KCl

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