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Concept
Sulfur trioxide
Summary
Sulfur trioxide (alternative spelling sulphur trioxide, also known as nisso sulfan) is the chemical compound with the formula SO3. It has been described as "unquestionably the most important economically" sulfur oxide. It is prepared on an industrial scale as a precursor to sulfuric acid.
Sulfur trioxide exists in several forms - gaseous monomer, crystalline trimer, and solid polymer. Sulfur trioxide is a solid at just below room temperature with a relatively narrow liquid range. Gaseous SO3 is the primary precursor to acid rain.
The molecule SO3 is trigonal planar. As predicted by VSEPR theory, its structure belongs to the D3h point group. The sulfur atom has an oxidation state of +6 and may be assigned a formal charge value as low as 0 (if all three sulfur-oxygen bonds are assumed to be double bonds) or as high as +2 (if the Octet Rule is assumed). When the formal charge is non-zero, the S-O bonding is assumed to be delocalized. In any case the three S-O bond lengths are equal to one another, at 1.42 Å. The electrical dipole moment of gaseous sulfur trioxide is zero.
Both liquid and gaseous SO3 exists in an equilibrium between the monomer and the cyclic trimer. The nature of solid SO3 is complex and at least 3 polymorphs are known, with conversion between them being dependent on traces of water.
Absolutely pure SO3 freezes at 16.8 °C to give the γ-SO3 form, which adopts the cyclic trimer configuration [S(=O)2(μ-O)]3.
If SO3 is condensed above 27 °C, then α-SO3 forms, which has a melting point of 62.3 °C. α-SO3 is fibrous in appearance. Structurally, it is the polymer [S(=O)2(μ-O)]n. Each end of the polymer is terminated with OH groups. β-SO3, like the alpha form, is fibrous but of different molecular weight, consisting of an hydroxyl-capped polymer, but melts at 32.5 °C. Both the gamma and the beta forms are metastable, eventually converting to the stable alpha form if left standing for sufficient time. This conversion is caused by traces of water.
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