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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
1
• 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.
2
Uses of sulfur and sulfuric acid
3
Given the ∆fHo(Na2O,s) = -414 kJ/mol, determine the
enthalpy change for the process: 2Na+(g) + O2-(g) Na2O(s)
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)
4
Chemistry of oxygen
MnO2 or Pt catalyst
2H2O2 O2 + 2H2O
∆, MnO2 catalyst
2KClO3 3O2 + 2KCl
O2 + PtF6 [O2]+[PtF6]-
Phosphite ozonide
5
Sulfur: allotropes
S6 S7 S8
catena-S
S8 + 24F2 → 8SF6
S8 + 4Cl2 → 4S2Cl2
S8 + 4Br2 → 4S2Br2
SF6
structure of [S2I4]2+
6
Polysulfides, [Sx]2-, and polythionates are formed from reaction of sulfur
with hot aqueous alkali
polythionate
[S8]2+
7
[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
8
tellurium
4+
H2O2 stabilizer
9
H2O2
H2O2
10
Peroxo complexes
[V(O2)2(O)(bpy)]− [Mo2(O2)4(O)2(µ-OOH)2]2−
11
Polysulfanes: H2SX
n=2
Polysulfides: [SX]2-
[S6]2- [Mn(S5)(S6)]2-
[Zn(S4)2]2-
[(S6)Cu(µ-S8)-Cu(S6)]4-
[AuS9]2-
12
Polyselenides and polytellurides: [Sex]2- and [Tex]2-
DMF*
3Se + K2Se2 K2[Se5] *DMF = Dimethylformamide =
[Te5]2- [Te8]2-
O 141 pm
103°
F F
13
Sulfur fluorides and oxofluorides
S2F10
SOF2
14
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
15
SeF4 TeF4 Se4Cl16
Tellurium halides
16
MO diagram for octahedral [ECl6]2− (E = Se or Te)
Oxides of Sulfur
17
[SO2N3]- [(SO2)3N3]-
18
Gas phase form of SO3 also
exists as a trimer of SO4 units.
19
Oxoacids and their salts: S
ClSO3H ClSO3H
H2O2 -HCl H2SO5 -HCl H2S2O8
20
[S2O6]2− H2SO4 (g)
H2SO4 (l)
Sulfur-Nitrogen Compounds
21
Potential diagrams (values in V) for sulfur, selenium and tellurium at
pH = 0.
22