Thermodynamics of the formation of some mercury(II) amine complexes in dimethyl sulfoxide

Add time:07/28/2019    Source:sciencedirect.com

The stabilities and the heats of formation of mercury(II) n-hexylamine, di-n-butylamine and piperidine complexes have been studied in dimethyl sulfoxide (DMSO) by means of potentiometric and calorimetric measurements. Three mononuclear complexes are formed with the secondary amines, and there the second complex is the strongest one;about ten times stronger than the first complex. This means that the first complex only reaches about 15% predominance. The two first complexes are formed in strongly exothermic reactions, while the entropy changes are negative. The third complexes are also formed in exothermic reactions, but the entropy terms are small and positive. In the mercury(II)— n-hexyl-amine system only the second complex has been established probably due to a very small K1/K2 ratio. The different trends in the stabilities of amine complexes of silver(I) and mercury(II) in water and DMSO are discussed and explained on basis of different structures of the complexes in aqueous and DMSO solutions.

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