Sunday, January 24, 2010

Chemistry

Ozone is a powerful oxidizing agent, far better than dioxygen. It is also unstable at high concentrations, decaying to ordinary diatomic oxygen (in about half an hour in atmospheric conditions):[9]

2 O3 → 3 O2

This reaction proceeds more rapidly with increasing temperature and decreasing pressure. Deflagration of ozone can be triggered by a spark, and can occur in ozone concentrations of 10 wt% or higher.[10]

Metals

Ozone will oxidize metals (except gold, platinum, and iridium) to oxides of the metals in their highest oxidation state. For example:

2 Cu+ (aq) + 2 H3O+ (aq) + O3 (g) → 2 Cu2+ (aq) + 3 H2O (l) + O2 (g)

Non-metals

Ozone also increases the oxidation number of oxides, such as the oxidation of nitric oxide to nitrogen dioxide:

NO + O3 → NO2 + O2

This reaction is accompanied by chemiluminescence. The NO2 can be further oxidized:

NO2 + O3 → NO3 + O2

The NO3 formed can react with NO2 to form N2O5:

NO2 + NO3 → N2O5

Ozone reacts with carbon to form carbon dioxide, even at room temperature:

C + 2 O3 → CO2 + 2 O2

Ozone does not react with ammonium salts but it reacts with ammonia to form ammonium nitrate:

2 NH3 + 4 O3 → NH4NO3 + 4 O2 + H2O

Ozone reacts with sulfides to make sulfates. For example, lead(II) sulfide is oxidised to lead(II) sulfate:

PbS + 4 O3 → PbSO4 + 4 O2

Sulfuric acid can be produced from ozone, starting either from elemental sulfur or from sulfur dioxide:

S + H2O + O3 → H2SO4
3 SO2 + 3 H2O + O3 → 3 H2SO4

All three atoms of ozone may also react, as in the reaction of tin(II) chloride with hydrochloric acid and NaCl:

3 SnCl2 + 6 HCl + O3 → 3 SnCl4 + 3 H2O

In the gas phase, ozone reacts with hydrogen sulfide to form sulfur dioxide:

H2S + O3 → SO2 + H2O

In an aqueous solution, however, two competing simultaneous reactions occur, one to produce elemental sulfur, and one to produce sulfuric acid:

H2S + O3 → S + O2 + H2O
3 H2S + 4 O3 → 3 H2SO4

Iodine perchlorate can be made by treating iodine dissolved in cold anhydrous perchloric acid with ozone:

I2 + 6 HClO4 + O3 → 2 I(ClO4)3 + 3 H2O

Solid nitryl perchlorate can be made from NO2, ClO2, and O3 gases:

2 NO2 + 2 ClO2 + 2 O3 → 2 NO2ClO4 + O2

Combustion

Ozone can be used for combustion reactions and combusting gases; ozone provides higher temperatures than combusting in dioxygen (O2). The following is a reaction for the combustion of carbon subnitride which can also cause lower temperatures:

3 C4N2 + 4 O3 → 12 CO + 3 N2

Ozone can react at cryogenic temperatures. At 77 K (-196 °C), atomic hydrogen reacts with liquid ozone to form a hydrogen superoxide radical, which dimerizes:[11]

H + O3 → HO2 + O
2 HO2 → H2O4

Ozonides

Ozonides can be formed, which contain the ozonide anion, O3. These compounds are explosive and must be stored at cryogenic temperatures. Ozonides for all the alkali metals are known. KO3, RbO3, and CsO3 can be prepared from their respective superoxides:

KO2 + O3 → KO3 + O2

Although KO3 can be formed as above, it can also be formed from potassium hydroxide and ozone:[12]

2 KOH + 5 O3 → 2 KO3 + 5 O2 + H2O

NaO3 and LiO3 must be prepared by action of CsO3 in liquid NH3 on an ion exchange resin containing Na+ or Li+ ions:[13]

CsO3 + Na+ → Cs+ + NaO3

Treatment with ozone of calcium dissolved in ammonia leads to ammonium ozonide and not calcium ozonide:[11]

3 Ca + 10 NH3 + 6 O3 → Ca·6NH3 + Ca(OH)2 + Ca(NO3)2 + 2 NH4O3 + 2 O2 + H2

Applications

Ozone can be used to remove manganese from water, forming a precipitate which can be filtered:

2 Mn2+ + 2 O3 + 4 H2O → 2 MnO(OH)2 (s) + 2 O2 + 4 H+

Ozone will also turn cyanides to the one thousand times less toxic cyanates:

CN- + O3CNO + O2

Finally, ozone will also completely decompose urea:[14]

(NH2)2CO + O3 → N2 + CO2 + 2 H2O

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