首页 | 本学科首页   官方微博 | 高级检索  
     检索      


Calculation of the UV-visible spectra and the stability of Mo and Re oxysulfides in aqueous solution
Authors:JA Tossell
Institution:Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742, USA
Abstract:Erickson and Helz (2000) established that molybdate, MoO4−2, is quickly and completely transformed to thiomolybdate, MoS4−2, by reaction with sulfide. They monitored the equilibria and kinetics of this process by measuring the UV-visible spectra of solutions containing the different oxythiomolybdate species. There is interest in the analogous reactions for the ReO4 species but little experimental data. We have therefore calculated quantum-chemically the equilibrium constants in solution for the sulfidation reactions of both MoO4−2 and ReO4, as well as recalculating their UV-visible charge-transfer spectra. Calculations using configuration interaction singles and time-dependent hybrid Hartree-Fock density functional methods give good absolute values and trends in UV-vis energies for both series. For MoO4−2 the calculated equilibrium constants for the various sulfidation steps match reasonably well against the experimental values (within two log K units). For the ReO4 sulfidation reaction the first two steps are considerably less favorable than for MoO4−2, suggesting that the “geochemical switch” of Erickson and Helz, a rapid transformation of oxyanion to thioanion highly dependent on sulfide concentration, will be less effective in the Re case. However, both our calculations and experiment indicate that ReO4 and ReS4 are both easier to reduce than their Mo analogs, so that reduction of these Re(VII) species will be the preferred mechanism for their removal from seawater. A previous suggestion that the neutral species MoO4H2 is actually the hydrated octahedral Mo(OH)6 species is found to be incorrect, but the MoO3(OH2)3 species, a highly distorted six-coordinate complex, is almost competitive in energy with MoO4H2 plus two H2O.
Keywords:
本文献已被 ScienceDirect 等数据库收录!
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号