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Published on: May 1, 2016
A universal chemical potential for sulfur vapours
Adam J Jackson1, Davide Tiana1, Aron Walsh1,2
1Centre for Sustainable Chemical Technologies , Dept. of Chemistry , University of Bath , Claverton Down , Bath BA2 7AY , UK .
Abstract:
The unusual chemistry of sulfur is illustrated by the tendency for catenation. Sulfur forms a range of open and closed S n species in the gas phase, which has led to speculation on the composition of sulfur vapours as a function of temperature and pressure for over a century. Unlike elemental gases such as O2 and N2, there is no widely accepted thermodynamic potential for sulfur. Here we combine a first-principles global structure search for the low energy clusters from S2 to S8 with a thermodynamic model for the mixed-allotrope system, including the Gibbs free energy for all gas-phase sulfur on an atomic basis. A strongly pressure-dependent transition from a mixture dominant in S2 to S8 is identified. A universal chemical potential function, microS(T,P), is proposed with wide utility in modelling sulfurisation processes including the formation and annealing of metal chalcogenide semiconductors.
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