Abstract
The effect of temperature on the octahedral equilibria which occur in solutions of thiocyanate and cobalt(II) ions in dimethyl sulphoxide at various thiocyanate/cobalt mole ratios has been studied spectrophotometrically. With increasing temperature, or thiocyanate/cobalt mole ratio, the equilibrium between [Co(SCN)(DMSO) 5] + and [Co(NCS) 4] 2− favours the latter species, but at temperatures in excess of around 100°C [Co(NCS) 3DMSO] − appears. This was established by conventional arguments and confirmed by computing the fourth derivative function of the spectra recorded at a thiocyanate/cobalt mole ratio of two. Trace amounts of [Co(NCS) 3DMSO] −1 where also thereby identified at temperatures where it could not normally be detected. Details of the various digitizing procedures and computer programmes are given. It is concluded that computer calculations on selected spectra can yield the same, and often more, chemical information than that obtainable from an extensive experimental study.
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