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where Ws and WL represent the number of independent ways of realizing the arrangements of solid and melt respectively and Sf is the entropy of fusion. Each new kind of disorder which occurs on passing from the crystal to the melt involves a new mechanism of randomization on melting. Ubbelohde! has summarized the different ways of randomization in the transition from the solid to the melt as positional, orientational, vibrational and configurational randomization. Other terms, which in certain cases can make large contributions to the entropy of fusion, are those due to the presence of mesomorphic states and the formation of association complexes in the melt2. Treating these increases of disorder as independent and additive, Sf becomes to a first approximation: Sf = SpOSitiOnal + Sorientational + Svibrational + SCOnflgUrational + Sassociation + Generally, in an ideal case the melting point is sharp and it is assumed that the free-energy curves for the liquid and solid phases are completely independent. In certain cases, however, this is not strictly true and there are changes in slope of the free energy curve of the solid state before the two curves intersect". This phenomenon is known as "homophase pre­ melting" and occurs whenever the structures of the two phases are very similar (e.g. the crystalline paraffins)2. This paper is concerned with the melting mechanism of the alkali thio­ cyanates which are a group of low melting ionic salts such as:

The melting mechanism of the alkali thiocyanates