Chapter 17

Group 17 Elements

Physical Properties
The elements
Hydrogen Halides
Interhalogen compounds and polyhalogen ions
Oxoacids and salts

1
 Bromine resources
and commercial
demand

2NaClO3 + 2NaCl + 2H2SO4  2ClO2 + Cl2 + 2Na2SO4 + 2H2O

5NaClO2 + 4HCl  4ClO2 + 5NaCl + 2H2O

2
Fluorine has several differences in properties
from later halogens:
• Only exists in -1 formal oxidation state (unlike
HClO4, HClO3 etc.)
• Small size
• Low dissociation energy for F2, bond breaks
easily.
• High oxidation power (+2.87 V)
• High electronegativity (highest element)

The A-F bond is stronger than A-Cl bond

• Small size and good overlap of atomic orbitals
strengthens bonds

Fluorocarbons are volatile, have weak London

forces.
• Nonpolarizable F

Small size also leads to large lattice energies in

solids
• Born-Lande equation. (melting point: NaF 993
°C; NaCl 801 °C)

3
 [I(py)2]

Although anions are the most commonly observed ion form a group 17
elements, cations can be stabilized by complexation or solvation.

Fluorine-19 NMR

19Fis (spin I =1/2, 100%) is valuable in structure elucidation and investigating

reaction mechanisms.

Neutron Activation Analysis

Naturally occurring 19F is converted to 20F by neutron bombardment, the

radioactive decay is monitored, allowing the original amount of 19F in the sample
to be determined.

Fluoride ion-selective electrode

An electrode that is sensitive to the concentration of a specific ion is called an

ion sensitive electrode. (a pH meter electrode is sensitive to H+ ions.)

4
 Difluorine

Difluorine is a pale yellow gas, but is difficult to store since it is highly reactive
and extremely corrosive.

Glass can be used* if the gas is freed of HF

NaF + HF  NaHF2

SiO2 + 2F2  SiF4 + O2 *Reaction is slow unless SiO2 is powdered

SiO2 + 4HF  SiF4 + 2H2O
2H2O + 2F2  4HF + O2

Typical F2 source is gas cylinders, but F2 may be

produced by decomposition:
K2MnF6 + 2SbF5 ---420 K 2KSbF6 + MnF2 + F2

Diiodine, dibromine, and dichlorine

Cl2 may be purchased for laboratory use, but also

may be prepared in the lab scale by:
MnO2 + 4HCl  MnCl2 + Cl2 + 2H2O

Layered solid

Solid State Structures

van der Waals radius, rv
Cl 180 pm
Br 195 pm
I 215 pm

5
 Charge transfer complexes

A charge transfer complex is one in which a donor and acceptor interact

weakly together with some transfer of electronic charge, usually facilitated by
the acceptor.
•HOMO-LUMO gap decreases in
the order F2 > Cl2 > Br2 > I2
•Shift in the absorption maximum
from the near UV to the red region
of the visible spectrum.
•When combined with donor atoms
(e.g. ethers, ketones, pyridine), Br2
and I2 form charge transfer
complexes with the halogen s* MO
acting as the acceptor orbital.
•Solutions of I2 in donor solvents
are typically brown or yellow.
•Electronic spectrum contains an
intense absorption in the UV (230-
330 nm) region arising a charge
transfer band.

Example charge transfer complexes

charge transfer complexes involving Br2-
2MeCN•Br

chain structure of C6H6•Br2

1,2,4,5-(EtS)4C6H2•(Br2)2

Ph3P•Br2

6
. Proposed bonding scheme for [(AgI2)n]n illustrating the ability of I2 to act
as both a charge donor and a charge acceptor.

Physical Properties of hydrogen halides

7
IBr

-ICl

ClF

8
 Cation-anion interaction

[I2F12]2- dimer
[BrF4] [Sb2F11]- dimer

9
 Bonding in [XY2]- ions

Review Chapter 5 – MO theory

Polyhalogen Cations

Homonuclear cations are known:

[Br2]+, [I2]+, [Cl3]+, [Br3]+, [I3]+, [Br5]+, [I5]+, [I4]2+

Br2 + SbF5 –--BrF5 [Br2]+[Sb3F16]-

(unbalanced)
2I2 + S2O6F2 ---HSO3F 2[I2]+[SO3F]-
Using MO theory, predict the change in X-X bond length on going from X2 to [X2]+
[Br2]+[Sb3F16]- Br-Br stretching is 368 cm-1
Br2 Br-Br stretching is 320 cm-1
2+
I

[I2]+ dimerizes at 193 K to give [I4]2+ I

I
2I2 + 3AsF5 –liq SO2 [I4][AsF6]2 + AsF3 I

3Br2 + 2[O2]+[AsF6]-  2[Br3]+[AsF6]- + 2O2

3I2 + 3AsF5 –liq SO2 2[I3]+[AsF6]- + AsF3

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 Polyhalide anions

Homonuclear polyhalide anions are known:

[I3]-, [I4]2-, [I5]-, [I7]-, [I8]2-, [I9]-, [I10]4-, [I12]2-, [I16]2-, [I16]4-,
[I22]4- , [I26]3-, [I29]3-

[I5]- [I7]- [I8]-

Oxides of chlorine, bromine, and iodine

Iodine is the only halogen to form an oxide which is thermodynamically

stable with respect to decomposition into its elements.

I2 + 5/2 O2  I2O5 DfHo(298 K) = -151.1 kJ mol-1

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 O3, 195 K O3, 195 K
Br2 Br2O3 Br2O5
Brown Orange Colorless

Charge separated species

for coordination numbers
greater than 4 and still
obey the octet rule.

CCl3F, 195 K
H2O + 2BrOTeF5 Br2O + 2HOTeF5

2Cl2 + 3HgO Cl2O + Hg3O2Cl2

2Cl2 + 2Na2CO3 + H2O 2NaHCO3+2NaCl+Cl2O

Cl2O + H2O 2HOCl

2KClO3 + 2H2C2O4 K2C2O4 + 2ClO2 + 2CO2 + 2H2O

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ClO2F + HClO4  Cl2O6 + HF

May decompose by:

Cl2O6 + H2O - HClO4 + HClO3

Cl2O7 – anhydride of perchloric acid

Oxofluorides of chlorine, bromine, and iodine

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 trans-[F2BrO3]- [F5IO2]2-

H5IO6

HIO3

HIO4
HClO4 ClO4-

14
Aqueous solution chemistry

Potential diagrams

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