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Higher sulfur oxides

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Higher sulfur oxides are a group of chemical compounds with the formula SO3+x where x lies between 0 and 1. They contain peroxo (O−O) groups, and the oxidation state of sulfur is +6 as in SO3.

Monomeric SO4 can be isolated at low temperatures (below 78 K) following the reaction of SO3 and atomic oxygen or photolysis of SO3ozone mixtures. The favoured structure is:

sulfur tetroxide

Colourless polymeric condensates are formed in the reaction of gaseous SO3 or SO2 with O2 in a silent electric discharge. The structure of the polymers is based on β-SO3 (one of the three forms of solid SO3) with oxide bridges (−O−) replaced randomly by peroxide bridges (−O−O−). As such these compounds are non-stoichiometric.

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