The free energy (Gibbs) of formation of
Li2C2
,
CaC2
, and
Li3N
and their activities in molten salt solutions at temperatures between 823° and 973°K have been determined by using the following galvanic cellsnormalFe,normalLi‐normalCa )(normalalloy|normalLiCl‐CaCl2 normaleut.CaC2|C)(normals,normalFe ][IandnormalFe,normalLi )(normalc|normalLiCl‐normalLiF eut.Li3N|N2 )(normalg,1 normalatm,normalFe ][IIThe nitrogen electrode used in cell (II) has been proved to have a Nernstian behavior by studying the dependence of emf on the partial pressure of nitrogen. The activity coefficients of
CaC2
and
Li3N
in molten salts have been found to decrease with increasing concentration.
Aus Löslichkeits‐ und elektrochemischen Untersuchungen geht hervor, daß AlN sich in Li3N‐ LiCl‐Schmelzen auflösen läßt und daß dieser Elektrolyttyp geeignete Zusammensetzungen und Eigenschaften f eine neuartige elektrolytische Al‐Gewinnung aufweist.
An exploratory study concerning the solubility and electrolysis of
normalAlN
in molten salts has been carried out in view of the development of a new process of electrowinning of aluminum with lower energy consumption than the Hall‐Herault process. Aluminum nitride appears soluble in molten
Li3N‐normalLiCl
and the existence of solubility is supported by thermal analysis, electrical conductivity, and galvanic cell measurements. Chemical analysis of the melt indicates the possibility of existence of aluminum chloride‐nitride complexes of the type
Li3N·3normalAlN·4normalLiCl
. Pre‐electrolysis or argon treatment of the bath could reduce
Li3N
content to about 0.1 w/o in the melt without observing decomposition of the solution. These melts with low
Li3N
content appear suitable for the electrowinning of aluminum. The Faradaic efficiency has been estimated to be about 83% from the amount of aluminum forming an alloy with the iron cathode. The cell voltage necessary for the electrolysis is in reasonable accord with the thermodynamic value.
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