Studies on the thermodynamics and conductances of molten salts and their mixtures. Part V. The density, change of volume on fusion, viscosity, and surface tension of sodium chlorate and of its mixtures with sodium nitrate

1968 ◽  
Vol 46 (8) ◽  
pp. 1279-1286 ◽  
Author(s):  
A. N. Campbell ◽  
E. T. van der Kouwe
Keyword(s):  
Activation Energy ◽  
Surface Tension ◽  
Sodium Nitrate ◽  
Molten Salts ◽  
Sodium Chlorate ◽  
Surface Heat ◽  
Lithium Nitrate ◽  
Positive Deviation ◽  
Molten Sodium ◽  
Salt Melts

The densities, viscosities, and surface tensions of molten sodium chlorate, and of molten mixtures of sodium chlorate and sodium nitrate, as well as the change of volume on fusion, have been determined.From the dependence of molar volume on temperature and composition, it appears that the mixing of sodium chlorate and sodium nitrate is a process of dilution rather than of interaction. The viscosity of sodium chlorate is found to be much lower than that of lithium chlorate, a possible indication of greater complexity in the lithium chlorate melt. The activation energy of viscous flow for sodium chlorate is less than that of lithium chlorate. For lithium chlorate – lithium nitrate mixtures, at constant temperature, there is pronounced positive deviation from linearity, when viscosity is plotted against molar composition. For sodium chlorate – sodium nitrate mixtures, the deviation is much less marked though still positive.The surface tension of sodium chlorate is almost identical with those of lithium and potassium chlorates. The surface heat of sodium chlorate is higher than that of lithium chlorate but it still indicates some degree of covalency. The Guggenheim formula and Sokolov's rule have been applied. In contrast to melts of mixtures of lithium chlorate and lithium nitrate, the sodium salt melts would appear to have simpler constituents and to be more ionic in character.

Studies on the thermodynamics and conductances of molten salts and their mixtures. Part VI. Calorimetric studies of sodium chlorate and its mixtures with sodium nitrate

1968 ◽  
Vol 46 (8) ◽  
pp. 1287-1291 ◽  
Author(s):  
A. N. Campbell ◽  
E. T. van der Kouwe
Keyword(s):  
Sodium Nitrate ◽  
Molten Salts ◽  
Sodium Chlorate ◽  
Heat Of Fusion ◽  
Heat Of Mixing ◽  
Lithium Nitrate ◽  
Entropy Of Fusion ◽  
Direct Experiment ◽  
Calorimetric Studies ◽  
Nitrate System

The following properties have been determined by direct experiment for pure sodium chlorate and its mixtures with sodium nitrate: heat capacity (both solid and liquid) and heat of fusion. From these experimental quantities, the following properties have been derived: entropy of fusion, heat of mixing, and free energy and entropy of mixing. The results have been compared with our previous results for the corresponding lithium chlorate – lithium nitrate system. On the whole, the conclusion is justified that the structure of melts containing lithium chlorate is more complex than that of melts involving sodium chlorate.

Studies on the thermodynamics and conductances of molten salts and their mixtures. Part VII. The electrical conductance of sodium chlorate and its mixtures with sodium nitrate

1968 ◽  
Vol 46 (8) ◽  
pp. 1293-1296 ◽  
Author(s):  
A. N. Campbell ◽  
E. T. van der Kouwe
Keyword(s):  
Constant Temperature ◽  
Sodium Nitrate ◽  
Molten Salts ◽  
Electrical Conductance ◽  
Sodium Chlorate ◽  
Activation Energies ◽  
Constant Composition ◽  
Temperature Range ◽  
Molten Sodium

The specific and equivalent conductances of molten sodium chlorate and of its mixtures with sodium nitrate have been determined over the temperature range 240–280 °C. The results are treated as temperature functions at constant composition and as composition functions at constant temperature. From these data, the activation energies of conductance have been derived. The results have been compared with various theoretical equations and the conclusion is made that, while melts containing lithium chlorate may be associated or complexed in some way, the sodium chlorate melts show less of such a structure and are more ionic.

STUDIES ON THE THERMODYNAMICS AND CONDUCTANCES OF MOLTEN SALTS AND THEIR MIXTURES: PART III. DENSITIES, MOLAR VOLUMES, VISCOSITIES, AND SURFACE TENSIONS OF MOLTEN LITHIUM CHLORATE, WITH SMALL ADDITIONS OF WATER, AND OTHER SUBSTANCES

1964 ◽  
Vol 42 (8) ◽  
pp. 1778-1787 ◽  
Author(s):  
A. N. Campbell ◽  
D. F. Williams
Keyword(s):  
Surface Tension ◽  
Melting Point ◽  
Temperature Dependence ◽  
Temperature Change ◽  
Molten Salts ◽  
Surface Heat ◽  
Lithium Nitrate ◽  
Molar Volumes ◽  
Other Substances ◽  
Molten Lithium

The density (2.088 g ce−1) at 131.8 °C and viscosity (0.35 P at 131.8 °C) and their temperature dependence, of molten lithium chlorate, have been determined. Similar results have been obtained for lithium chlorate melts containing small quantities of water. The surface tension and its temperature dependence have been determined for lithium chlorate and for several lithium chlorate – water and lithium chlorate – lithium nitrate mixtures. From these measurements the surface heat has been calculated.The results for pure lithium chlorate indicate that the melt is complex, this complexity probably caused by association of some kind. This is especially evident just above the melting point, since there the temperature change in properties is greatest.Addition of water to the lithium chlorate melt causes the melt properties, especially the viscosity, to alter considerably. These changes are in part caused by a breakdown of the structural entities in the melt.

STUDIES ON THE THERMODYNAMICS AND CONDUCTANCES OF MOLTEN SALTS AND THEIR MIXTURES: PART IV. THE ELECTRICAL CONDUCTANCES OF MOLTEN LITHIUM CHLORATE AND OF ITS MIXTURES WITH PROPYL ALCOHOL, LITHIUM NITRATE, WATER, METHYL ALCOHOL, AND LITHIUM HYDROXIDE

1964 ◽  
Vol 42 (8) ◽  
pp. 1984-1995 ◽  
Author(s):  
A. N. Campbell ◽  
D. F. Williams
Keyword(s):  
Activation Energy ◽  
Melting Point ◽  
Methyl Alcohol ◽  
Molten Salts ◽  
Electrical Conductance ◽  
Lithium Hydroxide ◽  
Lithium Nitrate ◽  
Propyl Alcohol ◽  
Electrical Conductances ◽  
Molten Lithium

The electrical conductance and its temperature dependence of molten lithium chlorate have been determined. Similar results have been obtained for lithium chlorate melts containing small quantities of methyl alcohol, propyl alcohol, lithium nitrate, lithium hydroxide, and water.The results obtained, taken in conjunction with the results of previous work, all indicate that the melt is complex. There is probably considerable association and this is especially evident slightly above the melting point: at temperatures in this region the temperature change of the properties of the lithium chlorate melt is greatest.The activation energy of conductance is approximately the same as the activation energy of viscous flow, for pure lithium chlorate melt and for mixtures of lithium chlorate with lithium nitrate. From this it appears that the melt constituents are not principally the simple ions, but that some form of cohesion exists between the simple constituents of the melt.The addition of water to the lithium chlorate melt causes the melt properties to alter considerably, especially the transport properties, viscosity and conductance. It is suggested that these changes may in part be due to a breakup of the structural entities of the pure melt, though the increase in electrical conductance cannot be completely explained in this way. A cryoscopic investigation seems to indicate that water is •not present as such in the melt.

THE BINARY (ANHYDROUS) SYSTEMS NaNO3–LiNO3, LiClO3–NaClO3, LiClO3–LiNO3, NaNO3–NaClO3 AND THE QUATERNARY SYSTEM NaNO3–LiNO3–LiClO3–NaClO3

1962 ◽  
Vol 40 (7) ◽  
pp. 1258-1265 ◽  
Author(s):  
A. N. Campbell ◽  
E. M. Kartzmark ◽  
M. K. Nagarajan
Keyword(s):  
Thermal Analysis ◽  
Sodium Nitrate ◽  
Binary Systems ◽  
Quaternary System ◽  
Sodium Chlorate ◽  
Eutectic Type ◽  
Lithium Nitrate ◽  
Allotropic Transformation ◽  
X Ray ◽  
Invariant Points

The equilibrium diagrams of the systems NaNO3–LiNO3, LiClO3–NaClO3, LiClO3–LiNO3, NaNO3–NaClO3, and NaNO3–LiNO3–LiClO3–NaClO3 have been investigated by thermal analysis and, to some extent, by X-ray powder photography. All the binary systems are of the simple eutectic type, accompanied, in one instance, by considerable solid solubility. The allotropic transformation of sodium nitrate complicates the equilibria involving sodium nitrate somewhat, especially when there is solid solution.The quaternary diagram shows that in the (fused) reaction[Formula: see text]lithium nitrate and sodium chlorate constitute the stable solid pair. The two invariant points of this system are both congruent.

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