Chapter 16

Group 16 Elements

Physical Properties
The elements
Halides, oxohalides, oxides, salts of oxoacids
Metal sulfides, polysulfides, polyselenides,
polytellurides
Compounds of sulfur and selenium with nitrogen

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 • Dioxygen makes up 21% of the
Earth’s atmosphere and 47% of
the Earth’s crust is composed of
O-containing compounds (water,
limestone, silica, silicates).
• Sulfur occurs around volcanoes
and hot springs, iron pyrites
fool’s gold (FeS2), and other
minerals.
• Selenium and Tellurium are
relatively rare and occur in only
a few minerals
• Polonium is omitted because its
abundance is only 3 × 10−7 ppb,
giving a negative number on the
log scale.

Relative abundances of the group

16 elements in the Earth’s crust

Production of sulfur in the US from 1980 to 2008

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Uses of sulfur and sulfuric acid

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Given the ∆fHo(Na2O,s) = -414 kJ/mol, determine the
enthalpy change for the process: 2Na+(g) + O2-(g) Na2O(s)

Hint: Create an appropriate Born-Haber cycle and look up the

necessary values for each of the steps.

2∆aHo(Na)
2Na (s) + ½ O2(g) 2Na (g) + O (g)
∆aHo(O)

∆fHo(Na2O,s) ∆EAHo1(O)
2 IE1(Na)
∆EAHo2(O)

∆latticeHo(Na2O,s)
Na2O (s) 2Na+ (g) + O2-(g)

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 Chemistry of oxygen

MnO2 or Pt catalyst
2H2O2 O2 + 2H2O

∆, MnO2 catalyst
2KClO3 3O2 + 2KCl

Describe bonding in [O2]+, O2, [O2]-, [O2]2- using MO theory.

O2 + PtF6 [O2]+[PtF6]-

2O2F2 + 2BF3 2[O2]+[BF4]- + F2

Chemistry of ozone and ozonide

3/2 O2(g) → O3(g) ∆fHo(O3,g,298 K) = +142.7 kJ mol-1
O3(g) + 2H+(g) + 2e- ⇌ O2(g) + H2O(l) Eo = +2.07 V
The structures of O3 and [O3]−, and contributing resonance structures in O3.
• The O−O bond order in O3 is taken to be 3/2.

2KOH + 5O3 2KO3 + 5O2 + H2O

(Ozonide salts)

Phosphite ozonide

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 Sulfur: allotropes

S6 S7 S8

catena-S

S8 + 24F2 → 8SF6
S8 + 4Cl2 → 4S2Cl2
S8 + 4Br2 → 4S2Br2

SF6

structure of [S2I4]2+

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Polysulfides, [Sx]2-, and polythionates are formed from reaction of sulfur
with hot aqueous alkali

polythionate

Vulcanization – soft rubber is toughened by cross-linking polyisoprene

chains. Hydrocarbons are dehydrogenated when heated with sulfur and
further reaction with alkenes occur.

Other reactions of sulfur:

1/8 S8 + CO O=C=S 1/8 S8 + CN- N=C=S- ⇌ NΞC-S-

Na2SO3 + 1/8S8 –H2O, 373 K Na2S2O3

S8 + 3AsF5 –liquid SO2 [S8][AsF6]2 + AsF3

[S8]2+ is red and undergoes a change in ring conformation…

[S8]2+

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 [S19]2+

S82+

• transannular interactions
• Cross ring S-S separations
smaller than the sum of van
der Waals radii • Two 7-membered, puckered rings
• Delocalized bonding connected by a 5-atom chain
• Charge localized on the three-
coordinate S

Selenium
4SeCl2 + 4Ph3PSe Se8 + 4Ph3PCl2

Inorganic Chemistry By Egon Wiberg, Nils Wiberg, Arnold Frederick Holleman

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 tellurium

4+

2ReCl4 + 15Te + TeCl4 –heat in sealed tube→ 2[Te8][ReCl6]

Production of H2O2 BaO2 + H2SO4 → BaSO4 + H2O2

2[NH4][HSO4] – electrolytic oxidation, “-H2” [NH4]2[S2O8] 2[NH4][HSO4] + H2O2

H2O2 stabilizer

catalytic cycle used in the industrial

manufacture of hydrogen peroxide

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 H2O2

H2O2

H2O2 + 2H+ + 2e- ⇌ 2H2O Eo = +1.78 V

O2 + 2H+ + 2e- ⇌ H2O2 Eo = +0.70 V

Cl2 + H2O2 → 2HCl + O2

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Peroxo complexes

[V(O2)2(O)(bpy)]− [Mo2(O2)4(O)2(µ-OOH)2]2−

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 Polysulfanes: H2SX

n=2

2H2S + SnnCl2 H2Sn+2 + 2HCl

Polysulfides: [SX]2-

[S6]2- [Mn(S5)(S6)]2-
[Zn(S4)2]2-

[(S6)Cu(µ-S8)-Cu(S6)]4-
[AuS9]2-

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 Polyselenides and polytellurides: [Sex]2- and [Tex]2-

DMF*
3Se + K2Se2 K2[Se5] *DMF = Dimethylformamide =

4Se + K2Se2 + 2[Ph4P]Br [Ph4P]2[Se6] + 2KBr

DMF, 15-crown-5
3 Se + K2Se2 [K(15-crown-5)]2[Se5]
1,2-diaminoethane, crypt-222
2K + 3 Te [K(crypt-222)]2[Te3]

[Te5]2- [Te8]2-

O 141 pm
103°
F F

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Sulfur fluorides and oxofluorides

S2F10

SOF2

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 Sulfur chlorides and oxochlorides

206 pm
1/4S8(l) + Cl2(g) - S2Cl2
193 pm
Reaction Chemistry S2Cl2
2SO2 + S2Cl2 + 3Cl2 4SOCl2 Cl-S-S
108°
SO3 + SCl2 SOCl2 + SO2
Internal dihedral angle = 84°
2SCl2  S2Cl2 + Cl2

Reaction Chemistry of
SOCl2
RCO2H + SOCl2
RC(O)Cl + SO2 + HCl

SOCl2 SO2Cl2

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SeF4 TeF4 Se4Cl16

Tellurium halides

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 MO diagram for octahedral [ECl6]2− (E = Se or Te)

Oxides of Sulfur

SOCl2 + Ag2S -430 K S2O + 2AgCl

HS7H + SOCl2 → S8O

S8 ----CF3C(O)OOH → S8O

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[SO2N3]- [(SO2)3N3]-

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 Gas phase form of SO3 also
exists as a trimer of SO4 units.

Solid state form exists

as polymeric chains

Oxides of selenium and tellurium

[Te3O6F3]3- SeO3 tetramer

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 Oxoacids and their salts: S

H2S + HSO3Cl -low temp- H2S2O3 + HCl

ClSO3H ClSO3H
H2O2 -HCl H2SO5 -HCl H2S2O8

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[S2O6]2− H2SO4 (g)

H2SO4 (l)

Sulfur-Nitrogen Compounds

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Potential diagrams (values in V) for sulfur, selenium and tellurium at
pH = 0.

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