Inorganic anti-oxidants

1. Sulfur dioxide (SO2)

Production
(i)Sulfur dioxide is a gas primarily produced for sulfuric acid
manufacture. Most sulfur dioxide is produced by the combustion of
elemental sulfur. Sulfur dioxide is the product of the burning of
sulfur or of burning materials that contain sulfur:
S + O2 → SO2, ΔH = -297 kJ/mol

The combustion of hydrogen sulfide and organosulfur compounds

proceeds similarly.
For example: 2 H2S + 3 O2 → 2 H2O + 2 SO2

(ii) On a laboratory scale, the action of hot sulfuric acid on copper

turnings produces sulfur dioxide. Cu + 2 H2SO4 → CuSO4 + SO2 +
2 H 2O

(iii) Acidification of sodium metabisulfite produces sulfur dioxide:

H2SO4 + Na2S2O5 → 2 SO2 + Na2SO4 + H2O
 Reactions (Chemical properties)

• Industrial reactions
Treatment of basic solutions with sulfur dioxide affords
sulfite salts:
SO2 + 2 NaOH → Na2SO3 + H2O
Featuring sulfur in the +4 oxidation state, sulfur dioxide is
a reducing agent. It is oxidized by halogens to give the
sulfuryl halides, such as sulfuryl chloride:
SO2 + Cl2 → SO2Cl2
Sulfur dioxide is the oxidizing agent which is reduced by
hydrogen sulfide to give elemental sulfur:
SO2 + 2 H2S → 3 S + 2 H2O
The sequential oxidation of sulfur dioxide followed by its
hydration is used in the production of sulfuric acid.
2 SO2 + 2 H2O + O2 → 2 H2SO4
 Uses / Pharmaceutical Uses
• Precursor to sulfuric acid
Sulfur dioxide is an intermediate in the production of sulfuric acid. Sulfur dioxide for
this purpose is made when sulfur combines with oxygen. Several billion kilograms are
produced annually for this purpose.
 
• As a preservative
Sulfur dioxide is sometimes used as a preservative for dried fruits owing to its
antimicrobial properties. As a preservative, it maintains the colorful appearance of the
fruit and prevents rotting.

• In winemaking

Sulfur dioxide is an important compound in winemaking. It serves as an antibiotic

and antioxidant, protecting wine from spoilage by bacteria and oxidation. Its
antimicrobial action also helps to minimize volatile acidity.
SO2 is also a very important compound in winery sanitation. Wineries and equipment
must be kept clean, and because bleach cannot be used in a winery due the risk of
cork taint, a mixture of SO2, water, and citric acid is commonly used to clean and
sanitize equipment. Compounds of ozone (O3) are now used extensively as cleaning
products in wineries due to their efficiency, and because these compounds do not
affect the wine or equipment.
• As a reducing agent
Sulfur dioxide is also a good reductant. In the presence of water,
sulfur dioxide is able to decolorize substances. Specifically it is a
useful reducing bleach for papers and delicate materials such as
clothes. In municipal wastewater treatment, sulfur dioxide is used to
treat chlorinated wastewater prior to release.

• As a refrigerant
Being easily condensed and possessing a high heat of evaporation,
sulfur dioxide is a candidate material for refrigerants. Prior to the
development of CFCs, sulfur dioxide was used as a refrigerant in
home refrigerators.

• As a reagent and solvent in the laboratory

Sulfur dioxide is a versatile inert solvent that has been widely used
for dissolving highly oxidizing salts. It is also used occasionally as a
source of the sulfonyl group in organic synthesis. Treatment of aryl
diazonium salts with sulfur dioxide and cuprous chloride affords the
corresponding aryl sulfonyl chloride, for example:
2. Sodium metabisulfite (Na2S2O5):

Sodium metabisulfite is an inorganic compound of

chemical formula Na2S2O5. It is used as a disinfectant,
antioxidant and preservative agent.

Preparation: Sodium metabisulfite can be prepared by

evaporating a solution of sodium bisulfite saturated with
sulfur dioxide:
2 HSO3- ⇌ H2O + S2O52- , which leaves solid Na2S2O5
behind.
Uses / Pharmaceutical uses:
I. Food additive
It is used as a preservative and antioxidant in food. It may
cause allergic reactions in those who are sensitive to sulfites,
including respiratory reactions in asthmatics, anaphylaxis and
other allergic reactions in sensitive individuals. Sodium
metabisulfite and potassium metabisulfite are the primary
ingredients used for wine and beer making.
The acceptable daily intake is up to 0.7 mg per kg of body
weight. Sodium metabisulfite has no side effects; it is oxidised
in the liver to harmless sulfate and excreted in urine.

II. Sanitization and cleaning agent

It is commonly used in home brewing and winemaking to
sanitize equipment. It is used as a cleaning agent for potable
water. It is also used to remove chloramines from drinking
water after treatment.
III. Other uses

Added to local anesthetic (lidocaine etc.) solutions to prevent

oxidation of vasoconstrictor adrenaline and thus improve the shelf
life of the solution.

It is used in photography for film development.

It is also used as an excipient in some tablets, such as

paracetamol. .

It is used as the source of SO2 in wine and acts as an important

anti-oxidant and bactericide.

It is used in waste treatment to chemically reduce hexavalent

chromium to trivalent chromium which can then be precipitated
and removed from an aqueous waste stream.
Chemical properties

• When mixed with water, sodium metabisulfite releases sulfur dioxide (SO2),
a pungent, unpleasant smelling gas that can also cause breathing difficulties
in some people. For this reason, sodium metabisulfite has fallen from
common use in recent times, with agents such as hydrogen peroxide
becoming more popular for effective and odorless sterilization of equipment.
Released sulfur dioxide however makes the water a strong reducing agent.
• Sodium metabisulfite releases sulfur dioxide in contact with strong acids:

Na2S2O5 + 2 HCl → 2 NaCl + H2O + 2 SO2

• On heating to high temperature, it releases sulfur dioxide, leaving sodium

sulfite behind:

Na2S2O5 → Na2SO3 + SO2

3. Sodium nitrite (NaNO2)

Sodium nitrite is the inorganic compound with the chemical

formula NaNO2. It is a white to slightly yellowish crystalline
powder that is very soluble in water and is hygroscopic. It is a
useful precursor to a variety of organic compounds, such as
pharmaceuticals, dyes, and pesticides, but it is probably best
known as a food additive to prevent botulism.

Botulism is a rare and potentially fatal paralytic illness

caused by a toxin produced by the bacteria Clostridium
botulinum. The disease begins with weakness, trouble seeing;
feeling tired, and trouble speaking. This may then be followed
by weakness of the arms, chest muscles and legs. The
disease does not usually affect consciousness or cause a
fever.
Production

The salt is prepared by treating sodium hydroxide with

mixtures of nitrogen dioxide and nitric oxide:

2 NaOH + NO2 + NO → 2 NaNO2 + H2O

The conversion is sensitive to the presence of oxygen,

which can lead to varying amounts of sodium nitrate. In
former times, sodium nitrite was prepared by reduction
of sodium nitrate with various metals.
Chemical reactions

I. In the laboratory, sodium nitrite can be used to destroy excess sodium

azide.
2 NaN3 + 2 Na NO2 + 2 H+ → 3 N2 + 2 NO + 2 Na+ + 2 H2O
II. Above 330 °C sodium nitrite decomposes (in air) to sodium oxide,
nitrogen (II) oxide and nitrogen monoxide.
2 NaNO2 → Na2O + NO + NO2
III. Sodium nitrite can also be used in the production of nitrous acid via
sulfuric acid. This reaction first yields nitrous acid and sodium
sulfate:
2NaNO2 + H2SO4 → 2HNO2 + Na2SO4
IV. The nitrous acid then, under normal conditions, decomposes:
2HNO2 → NO2 + NO + H2O
V. The nitrogen dioxide of the prior decomposition is then routed
through a condenser or fractional distillation apparatus to react with
water and yield nitric acid:
2NO2 + H2O → HNO3 + HNO2
Uses / Pharmaceutical uses

I. Industrial chemistry
The main use of sodium nitrite is for the industrial production of
organonitrogen compounds. It is a reagent for conversion of amines into
diazo compounds, which are key precursors to many dyes, such as diazo
dyes. Nitroso compounds are produced from nitrites which are used in the
rubber industry.
Other applications include uses in photography. It may also be used as an
electrolyte in electrochemical grinding manufacturing processes, typically
diluted to about 10% concentration in water.
Sodium nitrite is an effective corrosion inhibitor and is used as an additive in
industrial greases, as an aqueous solution in closed loop cooling systems,
and in a molten state as a heat transfer medium.

II. Medicine
Sodium nitrite can be used as part of an intravenous mixture with sodium
thiosulfate to treat cyanide poisoning. There is also research to investigate
its applicability towards treatments for heart attacks, pulmonary
hypertension in infants, and Pseudomonas aeruginosa infections.
 III. Food additive
• Sodium nitrite has been found to inhibit growth of disease-causing
microorganisms; give taste and color to the meat; and inhibit lipid oxidation that
leads to rancidity. The ability of sodium nitrite to address the above mentioned
issues has led to production of meat with improved food safety, extended
storage life and improving desirable color/taste. In the European Union it may
be used only as a mixture with salt containing at most 0.6% sodium nitrite. It is
approved for usage in the EU, USA and Australia and New Zealand.
Iv. Inhibition of microbial growth
• Sodium nitrite is well known for its role in inhibiting the growth of Clostridium
botulinum spores in refrigerated meats. The mechanism for this activity results
from the inhibition of iron-sulfur clusters essential to energy metabolism of
Clostridium botulinum. However, sodium nitrite has had varying degrees of
effectiveness for controlling growth of other spoilage or disease causing
microorganisms. Even though the inhibitory mechanisms for sodium nitrite are
not well known, its effectiveness depends on several factors including residual
nitrite level, pH, salt concentration, reductants present and iron content.
Furthermore, the type of bacteria also affects sodium nitrites effectiveness. It is
generally agreed upon that sodium nitrite is not considered effective for
controlling gram-negative enteric pathogens such as Salmonella and Escherichia
coli.