Studies of phase transformations in nitrates and nitrites I. Changes in ultra-violet absorption spectra on melting

Ultra-violet absorption spectra of ions in crystals are sensitive to their environment of neighbouring ions. This fact is utilized to study melting processes in nitrates and nitrites, with particular reference to changes in the average shell of nearest neighbours around any ion, on passing from crystal to melt. For the nitrates of sodium, potassium, rubidium, caesium, thallium and silver, for ammonium nitrate and for the nitrites of sodium and potassium this shell appears to contract on melting, which is attributed to the formation of association complexes in the melt. For the two crystal hydrates HNO3. H2O and HNO3. 3H2O, corresponding changes are observed, suggesting that the structure and absorption spectra correspond with the ions (OH3)+ and NO-3 in the crystals, likewise giving rise to tighter association complexes on melting. Pure nitric acid on the other hand behaves in a manner more closely similar to isopropyl nitrate.