Oxides of the Halogens

In compounds such as the oxides and oxyacids the halogens (except F) occur in
high oxidation states. Some properties of oxides are shown below:

Property OF2 O2F2 Cl2O ClO2 I2O5

Physical Colourless Yellow Brownish Yellowish gas white
appearanc gas; (very solid below yellow gas; or liquid; crystalline
e pale yellow) 119 K; solid
gas;
General explosive decompose explosive at explosive hygroscop
characteris and toxic s above high above 15% ic s
tics 223 K concentration volume in air
s
Melting 49 119 153 213 573
point /K decomp
Boiling 128 210 275 284 -
point /K
ΔHf°(298 24.7 18 80.3 102.6 -158.1
K) / kJ mol-
1

Dipole 0.3 1.44 0.78 1.78 -

moment /D
O-X bond 141 157.5 170.0 147.3 180 (term)
length /pm 195
(bridging)

Oxygen difluoride was first prepared in 1929; it was obtained by the

electrolysis of slightly moist molten potassium fluoride and hydrofluoric acid.
More recently it has been prepared by the reaction of difluorine with 2%
aqueous NaOH solution:

2F2 + 2NaOH → OF2 + 2NaF + H2O

Although OF2 is the most stable of the oxygen fluorides, conditions must be
controlled so as to minimise losses due to decomposition via the secondary
reaction.
OF2 + 2 OH- → O2 + 2F- + H2O
This reaction occurs slowly with water at room temperature, more rapidly with
base and explosively with steam.
The shape of the OF2 molecule has been compared with HOF and H2O and the
three give bent structures where the bond angles range from 97 to 104.5 °.

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 The shape of the OF2 molecule

The basic shape of O2F2 resembles that of H2O2 except that the internal
dihedral angle is smaller (87° cf. to 111°). The very long O-F bonds (157.5 pm)
probably explains why the molecule is able to easily dissociate.

There are at least 10 oxides of chlorine known, of which only 2 will be

discussed.

Cl2O is best prepared by treating fresh yellow mercuric oxide with Cl 2 gas:
2 Cl2 + 2 HgO → Cl2O + HgCl2·HgO

It can also be prepared by reaction of Cl2 gas with moist sodium carbonate,
Na2CO3.
2Cl2 + 2Na2CO3 + H2O → Cl2O + 2NaCl + 2NaHCO3

Dichlorine monoxide is very water soluble (a saturated solution at -9.4 °C

contains 143.6 g Cl2O per 100 g H2O) and it hydrolyses to hypochlorous acid.
Cl2O + H2O → 2HOCl

Dichlorine monoxide

Much of the Cl2O is used to prepare hypochlorites, especially Ca(OCl)2 that is

used for water treatment of swimming pools.

Chlorine dioxide (ClO2) was mentioned in the first lecture as being an

important industrial chemical for bleaching flour and wood pulp and for water
treatment. Over 95% of the chlorine dioxide produced in the world today is
made from sodium chlorate:
2NaClO3 + 2NaCl + 2H2SO4 → 2ClO2 + Cl2 + 2Na2SO4 + 2H2O

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ClO2 was first discovered by Humphry Davy (1778-1829) in 1811 and was the
first of the chlorine oxides to have been isolated. The yellow paramagnetic gas
explosively decomposes into chlorine and oxygen and the decomposition is
initiated by light. Thus, it is never handled in concentrated form, but is almost
always used as a dissolved gas in water in a concentration range of 0.5 to 10
grams per liter. Its solubility increases at lower temperatures: it is thus
common to use chilled water (5 °C) when storing at concentrations above 3
grams per liter. In many countries, such as the USA, chlorine dioxide gas may
not be transported at any concentration and is almost always produced at the
application site using a chlorine dioxide generator. Chlorine dioxide is less
corrosive than chlorine and superior for the control of legionella bacteria. It is
more effective as a disinfectant than chlorine in most circumstances against
water borne pathogenic microbes such as viruses, bacteria and protozoa.

The oxidation number of the Cl is considered to be +3 and Pauling originally

proposed that resonance structures be used to account for this. An alternative
explanation by Brockway extended this to resonance between 3 electron 2
centre bonds. For many years it was claimed that a dimer was not formed and
considering that ClO2 is a radical this might have been one mechanism to
provide some stability by using up the odd electron in a 2 electron 2 centre
bond. In 1992, Rehr and Jansen conducted magnetic susceptibility and single
crystal studies at various temperatures and it was found that below about 170
K the sample became diamagnetic and did indeed form a dimer. They noted
that to avoid explosions all equipment had to be scrupulously cleaned with
aqua regia prior to use and temperatures kept low.

The Shape of ClO2 molecule

The oxides of bromine are less numerous than for chlorine and they are
generally unstable at room temperature decomposing to the elements.

For example, BrO2 is a pale yellow crystalline solid formed quantitatively by

low-temperature ozonolysis of dibromine.
Br2 + 4O3 → 2BrO2 + 4O2

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The oxides of iodine are the most stable of the halogens and the first of these to
be prepared was I2O5 which was independently discovered by Joseph Louis
Gay-Lussac (1778-1850) and H. Davy in 1813 although the structure was not
determined until 1970. The white hygroscopic crystals are very soluble in
water and commercial I2O5 has been found to consist of HI3O8 or I2O5.HIO3.
Likewise crystals of commercial iodic(V) acid, HIO3, were investigated using
single-crystal and powder X-ray diffraction and the crystals turned out again to
be HI3O8 or HIO3·I2O5.

Partially staggered conformation of I2O5

I2O5 is one of only a few chemicals that is capable of oxidising carbon monoxide
rapidly and completely at room temperature:
I2O5 + 5 CO → I2 + 5 CO2
This reaction has been used as the basis of an analytical method for sampling
CO in the atmosphere. I2O5 can be used for the oxidation of a number of other
small molecules including: NO, C2H4, SO3, H2S.

Oxoacids and their salts

Numerous oxoacids of the halogens exist and chlorine is able to form a

complete series of such acids ranging from HOCl to HClO4where the formal
oxidation state is +1,+3,+5 and +7. [1]

Oxoacids of chlorine Oxoacids of bromine Oxoacids of iodine

Hypochlorous acid HOCl, Hypobromous acid Hypoiodous acid HOI,
pKa=7.53 HOBr, pKa=8.69 pKa=10.64
Chlorous acid HOClO
(HClO2), pKa=2.0
Chloric acid Bromic acid Iodic acid HOIO2 (HIO3)
HOClO2 (HClO3), pKa=-1.0 HOBrO2 (HBrO3)
Perchloric acid Perbromic acid Periodic acid
HOClO3 (HClO4), pka = ~- HOBrO3(HBrO4) HOIO3 (HIO4)
8

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 Orthoperiodic acid
(HO)5IO (H5IO6)

HOF has been isolated by reaction of difluorine gas with ice at 230 K but it
does not ionise in water or give stable salts and on warming to room
temperature it decomposes to HF.
2HOF → 2 HF + O2

The hypohalous acids (X=Cl, Br, I) are conveniently prepared by the reaction of
the dihalogen with mercury oxide:
2X2 + 3 HgO + H2O → 2 HOX + Hg3O2X2

The hypohalous salts formed from the heavier halogens are all weak acids with
the hypochlorites being important industrial reagents.
Bleaching powder is a mixture of CaCl2, Ca(OH)2 and Ca(OCl)2 and is
manufactured by the reaction of dichlorine on Ca(OH)2. The sodium salt is a
well known disinfectant and bleaching agent

Each of these hypohalites are unstable and disproportionate at room

temperature to the halates and halide ion:
3[OX]- → [XO3]- + 2X-
The equilibrium constants for these reactions vary with X such that for Cl,
K=1027 for Br, K=1015 and for I, K=1020. The reaction speed increases down the
group so that for OI- the decomposition is very fast.

Chlorous acid, chloric acid and bromic acid cannot be isolated as pure
compounds but exist in aqueous solution and are prepared from the barium
salts.
Ba(ClO2)2 + H2SO4(aq) → 2 HClO2(aq) + BaSO4(s)
and Ba(XO3)2 + H2SO4 → 2 HXO3 + BaSO4 (X= Cl, Br)

Iodic acid (HIO3) is a stable white solid at room temperature and is prepared
from I2 and nitric acid or from I2O5 in water.
I2O5 + H2O → 2HIO3

The structure below shows trigonal pyramidal HIO3 units and these are
connected by extensive H-bonding. In aqueous solution it is a reasonably
strong acid with pKa ~ 0.77.

Potassium chlorate is a white crystalline substance that is used:

as a pesticide. In Finland it was sold under the trade name Fegabit.

 as an oxidizing agent,
 to prepare oxygen,

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  as a disinfectant,
 in safety matches, and
 in explosives and fireworks.

Potassium chlorate will readily decompose if heated in contact with a catalyst,

typically manganese (IV) dioxide (MnO2). Thus, it may be simply placed in a
test tube and heated over a burner and this can provide a convenient source of
dioxygen for school laboratories. The reaction is as follows:
2 KClO3(s) + heat → 3 O2(g) + 2 KCl(s)

The materials used need to be of high purity since even small amounts of
impurities can lead to explosions and it is considered good practice to test a
new batch of potassium chlorate with a small reaction first (less than 1 g!)
Even commercial oxygen generators have been known to explode and cause
problems such as at least one plane crash and a fire on the space station MIR.
[10]

Both potassium bromate and iodate are used in volumetric analysis and in
particular the iodate is a primary standard being available in high purity and
with excellent stablity. In the standardisation of thiosulfate for example
potassium iodate is used a source of diiodine.
[IO3]- + 5 I- + 6 H+ → 2 I2 + 3 H2O

HIO H5IO6 orthoperiodi

3 c acid

Several different I(VII) oxyacids are known including periodic acid (HIO 4) and
orthoperiodic acid (H5IO6). In the latter case there is extensive H-bonding
present in the solid state resulting in a 3D network. Wherease perchloric acid
exists as discrete monomeric units HIO4 is again extensively H-bonded
through cis- edge-sharing octahedra.

The reactions involving the various oxyacids in aqueous solution is

complicated, as seen by the following equilibria:
[H3IO6]2- + H+ → [IO4]- + 2H2O
2[H3IO6]2- → 2[HIO5]2- + 2H2O
2[HIO5]2- → [H2I2O10]4- → [I2O9]4- + H2O

Perchlorates

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Count Friederich von Stadion is credited with the preparation of the first perchlorate
compound in 1816 which he obtained by mixing potassium chlorate with concentrated
sulfuric acid and allowing it to stand for 24 hours with frequent agitation. The water-
insoluble residue was potassium perchlorate. Perchloric acid is the only oxoacid of
chlorine that can be isolated and in the vapour phase the Cl-O bonds are not
equivalent unless deprotonated when they become the same length.

The structure of HClO4

Pure perchloric acid is a colourless mobile, shock-sensitive liquid and at least 6

different hydrates are known and the monohydrate forms an H-bonded
crystalline lattice [H3O]+ [ClO4]-

The perchlorate anion is not a good ligand and it is sometimes used for the
isolation of metal complexes. Perchlorate salts are often soluble in acetone
which can provide a very useful solvent system for reactions. Unfortunately
though the solids are often unstable and can lead to violent explosions. I know
someone who lost the tip of their finger when attempting to grind up 1 or 2 mg
of complex for an IR spectrum!

Aqueous Solution Chemistry

The diagrams below show the variation of redox potentials with acid and base,
It should be noted that the couples ½X2/X- are independent of pH and together
with the estimated value for F2 indicate a steady decrease in oxidising strength
moving down the group.
F2 (+2.866 V) > Cl2 (+1.358 V) > Br2 (+1.066 V) > I2 (+0.536 V)

The reason the potential for difluorine must be estimated is that it is too strong
an oxidant and will oxidise water to O2 so the potential can not be easily
measured!

Given that the value listed for dichlorine is also greater than what is needed to
oxidise water (+1.229 V) this should happen as well however this is not the
case since there is a slow kinetic step in the oxidation of water. Note as well

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that this is the same reason why aqueous solutions of potassium permanganate
can be prepared, although they are not stable over time.

We already mentioned the variation of acid strength of the HX acids and in a

similar way the magnitudes of the E° for the half-reactions
½X2 + e- → X-

are best described in terms of bond-energies, electron affinities and hydration

energies.
½X2 → X(g) → X-(g) → X-(aq)

Overall this causes Cl2 to be a more powerful oxidant than Br2 or I2, partly
because of a more negative enthalpy of formation of the anion but by taking
into consideration the strong interaction with the small Cl - ion with water.

The majority of the couples are pH dependent so that an increase in pH causes

a dramatic lowering of the E° value. This is expected since if we consider an
example where BrO3- is converted to ½Br2 by the reaction:
BrO3- + 6H+ + 5e- → ½Br2 + 3 H2O (E° = +1.495 V)

the equilibrium constant includes a term with [H+]6 so that if the pH is changed
from pH=1 to pH=14 then H+ effectively changes by 10-14 and the estimated
difference can be seen in E° as:
ΔG° = - RTln(K)
ΔG° = - nE°F

from which just looking at the effect of pH is ~(RT/nF)ln([H +]6) or roughly

(0.0592/5) * 14 * 6 that is an effect of ~+0.99 V. Experimentally the measured
E° for

BrO3- + 3H2O + 5e- → ½Br2 + 6 OH- (E° = +0.519 V)

so estimated value is +1.495 - 0.99 = +0.51 V and found is +0.519 V showing

excellent agreement.

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 Redox processes in acid solutions

Redox processes in basic solutions

These diagrams indicate that in acid, periodate and perbromate are more
powerful oxidising agents than perchlorate when being reduced to halate ions
(I +1.653, Br +1.74, Cl +1.189 V) and that iodate and iodine are much weaker
oxidants compared to the other halates (I +1.34, Br +1.470, Cl +1.214 V) or
halogens (I +0.535, Br +1.066, Cl +1.358 V).

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