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Elemental Allotropes: Sulfur, Selenium, and Polonium Characteristics

Explore the properties and applications of sulfur, selenium, and polonium allotropes, including their structures, reactivity, and unique features. Learn about their diverse forms and use in various chemical processes.

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Elemental Allotropes: Sulfur, Selenium, and Polonium Characteristics

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  1. Ch 16. Group 16

  2. O allotropes O2: Ground state is a paramagnetic gas BP = -183 C (blue liquid) 3/2 O2 (g)  O3(g) ΔGf = +163 kJ/mol Ozone is a strong oxidant!

  3. S allotropes S: ring structures S6 to S20 with S8 most common S8 --> Sn (a red, viscous, elastomeric helical polymer) Sn is metastable at RT, reverts to S8 application: Na/S battery uses a molten S anode Na (liq) + Sn(liq)  NaSn

  4. HSO3F S8 + 3AsF5 (S8)(AsF6)2 + AsF3 bright red solution 4 Se + S2O6F2 (Se4)(SO3F)2 Se42+ is a square planar ring Elemental forms S-S ~ 0.19-0.21 nm transannular bond ~ 0.28 nm Se Te Po increasing metallic character Se (m) is a semiconductor, photoconductor, bandgap ~ 1.8 eV Po is metallic, primitive cubic structure, radioactive with max body burden = 7x1012g (20 trillion atoms) S82+

  5. S halides C2

  6. S halides C2v C2v

  7. S halides Oh kinetically stable against hydrolysis

  8. Frost diagrams

  9. S oxides generally mild oxidants or mild reducing agents, i.e. they are readily oxidized or reduced “+2” S2O32 thiosulfate +4 SO2 weak LA C2v H2SO3 sulfurous acid SO32- (sulfite) C3v +6 SO3 strong LA D3n H2SO4 sulfuric acid SO42 (sulfate) Td Add BF3 to SO3 to prevent oligomerization

  10. S oxides +6 S2O82 peroxydisulfate S2O82 2 SO4- . 2 SO42- 2e- , ~+2V

  11. Pourbaix diagrams

  12. SN compounds (28 pp in Greenwood and Earnshaw, Chemistry of the Elements) S2N2 almost sq. planar S4N4 S4N4  (SN)x polysulfurnitride, zig-zag chain, metallic conduction in chain direction Δ, Ag SN compounds

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