Molten Salts Handbook

Molten Salts Handbook focuses on the features, properties, and structure of molten salts. This book presents several topics in annotated bibliographic table form, including phase equilibria, chemical syntheses, and molten salt electrolytes. Organized into six chapters, this book starts with a tabular presentation of data of the physical properties, thermodynamic properties, electrochemical properties, practical features, as well as spectroscopy and structure of molten salts. This text then illustrates the design features of different experimental assemblies and provides information on the technique through a liberally annotated bibliography. Other chapters provide a chemical index, which offers a ready guide to the status of data over the entire range of interests. This book presents as well the properties of viscosity, density, surface tension, refractive index, and electrical conductance for different compounds as single salt melts. This book is a valuable resource for scientists and researchers from diverse fields, including theoretical and applied electrochemistry, inorganic coordination chemistry, and transition metal chemistry.

Preface

I. Physical Properties

I. A. Atomic and Ionic Radii, Melting Points, and Boiling Points of Single Salts and Eutectics

Atomic and Ionic (Crystal) Radii

Solid State Interionic Separations

Volumes of Anions

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

The Effect of Pressure on Melting Points

Melting Points of some Quaternary Ammonium Salts R4N+X-

Selected Low Melting Binary Eutectics

Additional Low Melting Binary Eutectic Mixtures

Selected Ternary Eutectic Mixtures

Melting Points and the Law of Corresponding States

I. B. Density

Melt Densities - Single Salts

Density of Some Solid Halide Salts

Percentage Volume Change on Fusion for some Inorganic Halides

Volume Change of NaCl and KCl on Melting

Volume Changes Due to Melting and Molar Volumes of some Molten Nitrates

Densities of Cryolite with Additives

Melt Densities - Binary Systems

Melt Densities - Ternary and Quaternary Systems

Literature Values for the Densities of Molten NaCl and KCl

I. C. Viscosity

Viscosities of NaNO3 and KNO3 as Single Salt Melts

Viscosity - Single Salt Melts

Melt Viscosities - Binary Systems

Melt Viscosities - Ternary and Quaternary Mixtures

I. D. Vapor Pressure

Vapor Pressure Equations for Selected Molten Salts

Vapor Pressures - Additional Studies

Equilibrium Dissociation Pressures of Molten Carbonates

Corresponding State Vapor Pressures for Molten Alkali Halides

I. E. Surface Tension

Surface Tensions of Various Compounds as Single Salt Melts

Hole Size in Group IA Chlorides and Nitrates

Hole Size in Group IIΑ and IIΒ Halides

Surface Tensions of Molten Salt Mixtures

Surface Tensions — Additional Studies

Corresponding State Surface Tensions

I. F. Refractive Index

Refractive Index of Various Molten Salts as a Function of Temperature

Refractive Index of Various Molten Salts

Molar Refractivity of Various Molten Salts

Refractive Index — Molten Salt Mixtures

I. G. Critical Data

Critical Temperatures and Percent Dissociation of Several Alkali Halides

Critical Constants of NaCl and KCl

Boiling Points, Entropies of Vaporization, Reduced Temperatures, and Critical Temperatures of Alkali Halides

Saturated Vapor and Liquid Densities of NaCl and KCl above Their Normal Boiling Point

II. Thermodynamic Properties

II. A. Liquid- Liquid Immiscibility

Molten Salt Liquid-Liquid Immiscibility

II. B. Metal-Molten Salt Systems

Principal Data for Alkali Metal-Alkali Halide (MX-M) Phase Diagrams

Principal Data for some Alkaline Earth Metal-Halide Systems (MX2-M)

Solubility of some Transition and Post-Transition Metals in Their Molten Halides

Principal Data for some Rare Earth Metal-Halide Systems

Metal-Metal Chalcogenide Phase Relations

Metal-Molten Salt Equilibria

Metal-Fused Salt Systems - Additional Studies

II. C. Metal Oxide-Molten Salt Systems

Metal Oxide-Fused Salt Systems

II. D. Silver Salts-Molten Salt Systems

Binary Systems with One or More than One Component a Silver Salt

Foreign Cation Classification of Binary Systems with One Component a Silver Salt

II. E. Phase-Rule Studies

Phase Characteristics of Binary Salt Mixtures

Binary Salt Systems — Additional Phase-Rule Studies

Phase Relations - Ternary Salt Systems

Compounds in the Binary Phase Diagrams of the Monovalent Chlorides with Multivalent Chlorides

Phase-Rule Studies — Quaternary Systems

II. F. Solubility

Henry's Law Constant for Noble Gases

Solubility of Argon in Molten Sodium Nitrate at 369ºC

Oxygen and Carbon Dioxide Solubilities in Molten Carbonates

Solubility of Water in Molten Salts

Solubility of HF in ZrF4 -NaF Molten Mixtures

Solubility of Various Solutes in (Li,K)NO3 Eutectic at 160ºC

Solubility of Metal Oxides in Fused Salts

Solubility of Metals - Effect of Added Halides

Solubility of Aluminum in Fused Salts

Solubilities in Molten Salts - Additional Studies

II. G. Thermal Data

Heats and Entropies of Fusion and Volume Changes upon Melting of the Halides and Nitrates of Group I and IIA Elements

Heats of Fusion - Selected Salts

Heats of Fusion - Recent Studies

Heats of Fusion - Selected Eutectic Mixtures

Entropies of Phase Transition and Fusion

Heat of Mixing — Binary Mixtures of Fused Salts

Heat of Mixing Data for Silver Chloride-Alkali Chloride and Silver Bromide-Alkali Bromide Systems

Heat of Mixing Data for Binary Alkali Halide Systems

Heats of Mixing of Halides, Perrhenates, and Perchlorates, with Nitrates, and Heats of Solution

Heats of Mixing - Additional Studies

Heat Conductance of Molten Salts

Temperature Dependence of the Thermal Conductivity of Molten NaOH

Thermal Conductivity of Pure Molten Nitrates and Nitrites

Thermal Conductivity of Molten Nitrate Mixtures

Heat Capacity of Selected Molten Salts

Increase of Molar Heat Capacity on Melting

Heat Capacity — Additional Studies

Heats of Formation

Heats of Sublimation and Vaporization of Alkali Halides at Their Melting Points

Partial Molar Heats of Solution

II. H. Cryoscopy and Related Thermodynamic Studies

Cryoscopic Constants — Selected Salts

Results of Some Cryoscopic Studies of Molten Salt Systems

Cryoscopy-Recent Studies

Cryoscopy - Additional Studies

Association Constants of Ionic Species in Fused Salt Solvents

Association Constants - Additional Studies

Thermodynamic Properties Calculated from emf Data

Thermodynamic Data from emf Studies

emf of Galvanic Jacobi-Daniell Cells

Activity Data from emf Studies

emf Cells - Additional Studies

Activity Data for PbCl2 in Molten Mixtures from Vapor Pressure Measurements (1003 ± 5ºK)

Thermodynamic Properties — Additional Studies

II. I. Expansivity, Compressibility, Ultrasonic, and High Pressure Studies

Molar Volumes and Coefficients of Expansion of NaCl and KCl

Molar Volumes and Expansivities of Molten Halides

Expansivities of Fused Salts at Τ = Tθ (°K)

Velocity of Sound in Molten Salts

Adiabatic and Isothermal Compressibilities for Group I Molten Salts

Isothermal and Adiabatic Compressibility of Group II Molten Halides

Free Volume for Molten Nitrates and Nitrites

Relation of Free Volume to Hole Volume and Heat of Activation of Viscous Flow of Some Group IIΒ Halides

Rao's Constant for Various Molten Salts and Organic Liquids

Values of ηB/ηS for Molten Salts, Associated and Nonassociated Liquids

Difference in Activation Energies for Shear and Structural Viscosity

Values of Parameters for Equations Relating to Shear and Structural Viscosity in Molten Salts

Viscosity, Density, and Absorption Data for Several Molten Salts

Viscosity and Absorption Data

Compressibility of Certain Molten Silicates and Borates

Density and Expansivity of Liquid Silicates

III. Electrochemical Properties

IIΙ. A. Reference Electrodes and emf Series

Reference Electrodes

Gaseous and Redox Electrodes

Various Metals Used as Electrode Systems in Fused Salts

Reference Electrodes - Additional Studies

Ep° in Pure Metal Fluorides at High Temperatures Compared with Ei° in Aqueous Solutions at 25°C

Ep° in Pure Metal Chlorides at High Temperatures Compared with Ei° in Aqueous Solutions at 25°C

Ep° in Pure Metal Bromides at High Temperatures Compared with Ei° in Aqueous Solutions at 25°C

Ep° in Pure Metal Iodides at High Temperatures Compared with Eiº in Aqueous Solutions at 25°C

Standard Potentials in Bromides and Iodides Compared with Chlorides at 700°C

emf Series in Alkali Chloride Solvents Compared with Ep°

emf Series in Fused MgCl2-NaCl-KCl Solvent at 475°C

emf Series in Various Fused Salt Electrolytes

emf Series-Additional Studies

III. B. Electrical Conductance

Equivalent Conductance — Single Salt Melts

Specific Conductance of Single Salt Melts

Temperature Dependence of Specific Conductivity of Molten Sulfides

Specific Conductivity of Cryolites

Specific Conductance of Molten KCl

Transport Parameters of Liquid BeF2, Typical Halides, and Network Oxides

Electrical Conductance of Low Melting Acid Sulfates

Effect of Additives on Electrical Conductance of LiClO3

Effect of p-Xylene on Conductance, Density, and Viscosity of (n-Amyl)4NCNS

Effect of Inert Gas Solubility and Pressure on Electrical Conductance of NaNO3

Effect of H2O on Conductance, Density, and Viscosity of NaOH-KOH

Effect of Additives on Electrical Conductance of Cryolite

Degree of "Ionic Dissociation" in Molten Compounds

Conductance Parameters for KNO3+Ba(NO3)2 Melts at 350°C

Melt Conductance - Binary Systems

Melt Conductance - Ternary and Quaternary Mixtures

Electrical Conductance - Metal-Molten Salt Systems

Molar Conductance A∞m of Na and Κ in Infinitely Dilute Solution in Their Molten Halides at 900°C

Electrical Conductivity of Metal-Molten Salt Systems — Additional Studies

IIΙ. C. Polarography, Chronopotentiometry, and Double Layer Capacity Studies

Polarographic Data for Fused Salts

Solid Electrodes for Molten Salt Voltammetry

Polarography-Additional Studies

Chronopotentiometric Data for Metal Ions in KCl-LiCl at 450°C

Chronopotentiometry - Diffusion Coefficients for Ag+ in Molten KNO3-NaNO3

Diffusion Data from Chronopotentiometric Studies

Chronopotentiometry - Formation Constants for Halide Complexes of Cd(II) in Molten NaNO3-KNO3 at 263°C

Chronopotentiometry - Additional Studies

Double Layer Capacities in Molten Salts

Comparison of the Potentials of Zero Charge and the Corresponding Standard Electrode Potentials

Exchange Currents and Kinetic Parameters in Molten Salt Electrode Processes

Exchange Currents and Double Layer Capacitance - Additional Studies

IIΙ. D. Electromigration: Transport Numbers and Diffusion

Movement of Inorganic Ions in Fused Anhydrous LiCl-KCl Eutectic at 450°C

Movement of Metal Ions in Fused Salts

Movement of Cd(II) and Pb(II) in Fused Salts When Employed as Different Salts

Electrophoresis - Additional Studies

Transport Numbers - Single Salt Melts

Comparison of Cation Transference Numbers Calculated with Those Measured Relative to Porous Plugs

Transport Numbers - Mixed Fused Salts

Transport Numbers - Additional Studies

Self-Diffusion Coefficients

Tracer Diffusion of Na22 in Molten NaNO3

Tracer Diffusion in Molten Carbonates

Interdiffusion Coefficients-Dilute Binary Systems

Diffusion-Additional Studies

Interionic Friction Coefficients for some Single Salt Melts

Transport Properties at Various Temperatures for Molten Nitrates

IIΙ. E. Dielectric and Thermoelectric Properties

Dielectric Constants of Molten Salts

Thermoelectric Properties

Thermoelectric Properties - Additional Studies

IV. Spectroscopy and Structure

IV. A. Vibrational Spectroscopy

Vibrational Spectra of Molten Nitrates

Assignments and Calculated Frequencies for In-Plane Vibrations of Molten Nitrates in C2V Symmetry

Urey-Bradley Force Constants of Coordinated Nitrate Ions in Nitrate Melts

Vibrational Spectra of Molten Hydroxides, Chlorates, Perchlorates, Sulfates, and Bisulfates

Vibrational Spectra of Molten Halides

Characteristic Vibrational Bands in Molten Halides

Raman Spectra of Gallium Dichloride and Dibromide

Raman Spectra of Molten and Aqueous Thiocyanates

Vibrational Spectra of Molten Nitrate Mixtures

Vibrational Spectroscopy — Additional Studies

IV. B. Visible and U. V. Spectroscopy

U. V. and Visible Absorption Spectra Studies

Coordination Numbers and Configurations of 3d Metal Ions in Molten Chlorides

Correlation of Results with Electrostatic and Crystal Field Stabilization Energies

Colors Produced by Transition Metal Ions in Molten Salts

Frequencies of Absorption Maxima Ε(2) for Alkali Nitrates

Spectra of Ni2+ and CO2+ in Molten Sulfates

Spectra of Pt2+ and Pd2+ in Molten LiCl-KCl

Calculated Parameters for Ni2+ in Various Media

IV. C. Nuclear Magnetic and Electron Paramagnetic Resonance Spectroscopy

NMR Chemical Shift on Fusion of Thallium Salts

Chemical Shift in Solid and Molten Thallium Salts

Chemical Shift of 205Tl+ in Solutions of RbCl and AgCl

NMR Spectroscopy - Additional Studies

Electron Spin Resonance Spectroscopy

Magnetic Susceptibility of Some Molten Metals, Molten Salts, and Their Solutions

Magnetic Susceptibility — Additional Studies

IV. D. X-Ray and Neutron Diffraction

Structural Parameters from the First Peaks of Alkali Halide Radial Distributions

Cation-Cation or Anion-Anion Distances and Coordination in Molten and Crystalline Alkali Halides

X-Ray and Neutron Diffraction - Additional Studies

IV. E. Fused Salt Electrolytes

Current Viewpoints

V. Practical Features

V. A. Melt Preparation and Purification

Principles of Electrolyte Purification

Electrolyte Purification - Recent Studies

Crystal Growth from Melts

V. B. Containment and Corrosion

Containment of Fused Salts

Containment of Molten Metals

Containment of Molten Oxides

Molten Salt Corrosion Data

Corrosion Processes in Melts

V. C. Chromatographic Analysis

Chromatographic Behavior of Inorganic Ions in Molten LiCl-KCl Eutectic at 450°C under Various Conditions

Chromatography on Various Supports with Different Eluants (160°C)

Comparison between Adsorption, Oxide Solubility, and Ionic Potentials

Electromigration in Fused Salts

Chromatography - Additional Studies

V.D. Electrolysis

Metal Formation

Electroplating from Fused Salts

Electrolysis - Additional Studies

Inorganic Compound Formation by Fused Salt Electrolysis

Alloy Formation by Fused Salt Electrolysis

Isotope Enrichment - Single Salts, Binary Mixtures

Polarization Potentials - Fused Salt Electrolysis

Decomposition Potentials in Fused Salt Electrolysis

Decomposition Potential Studies

Electrode Discharge Potentials of Anions (700°C)

V. E. Chemical Processes

Chemical Synthesis with Molten Salts as Reaction Media

Acid-Base Concepts in Molten Salts

Molten Salts as Reaction Media — Additional Studies

V. F. Fuel Cells, Batteries, Nuclear Technology

Fuel Cells

Molten Salts in Voltaic Cells

Vapor Pressure Data of some Molten Fluoride Systems Used in Nuclear Reactor Fuels

Thermochemical Data for Some Molten Fluoride Systems Used in Nuclear Reactor Fuels

Density and Viscosity Data of Some Molten Fluoride Systems Used in Nuclear Reactor Fuels

Thermal Conductivity and Equilibrium Data for Some Molten Fluoride Systems Used in Nuclear Reactor Fuel

Effect of Temperature on Corrosion and Corrosion Reactions of Some Molten Fluoride Systems Used in Nuclear Reactor Fuels

Radiation Stability of Some Molten Fluoride Systems Used in Nuclear Reactor Fuels

Some Molten Fluoride Systems Used in Nuclear Reactor Fuels - Additional Studies

VI. Experimental Techniques

VI. A. Illustrations of Experimental Assemblies

Conductance Cells

d. c. Conductance Cell and Transformer Circuit for Electrode Cells

Cell for Potentiometric Measurements and Electrode Assemblies

Electrodes for Polarography

U.V. Spectroscopy Assembly

Molten Salt Infrared Cells

Molten Salt Raman Cells

Molten Salt NMR Assemblies

Transport Number Electrolysis Cells

Electromigration (Electrophoresus) Assembly

Viscometers

Heat of Mixing and Heating Fusion Calorimeters

Cryoscopic Assemblies

Density and Surface Tension Assemblies

Ultrasonic Velocity Assembly

Refractive Index Apparatus

Molten Salt Chromatography Apparatus

Reaction Vessel for Chemical Synthesis Using Melts as Reaction Media

VI. B. Experimental Techniques - Annotated Bibliography

Additional References and Data Sources

Preparation and Purification of Melts

Container Materials

Furnace and Temperature

Electrochemical Techniques

Electrolysis

Conductance

Potentiometry

Polarography

Chronopotentiometry

Electrode Polarization Methods

Visible and Ultraviolet Spectroscopy

Infrared and Raman Spectra

NMR and ESR Spectra

X-Ray and Neutron Diffraction

Electrical Transport

Diffusion

Viscosity

Calorimetry

Phase Equilibria

Cryoscopy

Thermoelectric Properties

Surface Tension

Density and Compressibility

Refractive Index

Magnetic Susceptibility

Adsorption and Chromatography

Chemical Reactions

Chemical Formula Index