UNIT PROCESSES

OXIDATION
• Oxidation is defined as the interaction between
oxygen molecules and all the different substances
they may contact, from metal to living tissue.

• Technically, however, with the discovery of

electrons, oxidation came to be more precisely
defined as the loss of at least one electron when
two or more substances interact. Those
substances may or may not include oxygen. 
In the organic chemical industry, oxidation constitutes one of the most powerful tools
used in the synthesis of chemical compounds. The oxidation processes are many and
varied and are manifested in a variety of net effects.

The principle types of oxidative reactions may be set forth as follows:

1. Dehydrogenation
Dehydration is illustrated in the transformation of a primary alcohol to aldehyde:
1
C 2 H 5OH  O2  CH 3CHO  H 2O
2
Or a secondary alcohol to a ketone:
1
CH 3 .CHOH.CH 3  O2  CH 3COCH3  H 2O
2
2. An atom of oxygen may be introduced into a
molecule, as Is illustrated by the oxidation of an aldehyde to an acid:
1
CH 3 .CHO  O2  CH 3COOH
2
Or of a hydrocarbon to an alcohol:
1
 C6 H 5  3 .CH  O2   C6 H 5  3 COH
2
3. A combination of dehydrogenation and
introduction of oxygen may occur, as in the preparation of
aldehydes from hydrocarbons
CH 4  O2  CH 2O  H 2O
Or the preparation of benzoic acid form benzyl alcohol:
C 6 H 5 .CH 3OH  O2  C 6 H 5 .COOH  H 2O

4. Dehydrogenation may also be accompanied

by molecular condensation , as is the case when two
molecules of benzene form diphenyl:
1
2C 6 H 6  O2  C 6 H 6  C 6 H 6  H 2O
2
5. Dehydrogenation, oxygen introduction and
destruction of carbon linkages may all occur in the same
process of oxidation, e.g. in the oxidation of naphthalene to phthalic anhydride:
C10 H 8  4.5O 2  C8 H 4 O 3  2H 2 O  2CO2

6. Oxidation may be accomplished indirectly through the use of

intermediate reaction.

C 6 H 5 .CH 3  C 6 H 5CCl3 H


2O
 C 6 H 5COOH
C 6 H 8  C6 H 5SO 3 H NaOH
 C 6 H 5OH
CH 3OH  CO 
 CH 3COOH
7. Olefin may be oxidized under mild conditions to hydroxyl derivatives and may be
converted to aldehydes and carboxylic acids of lower molecular weight when stronger
oxidizers are employed. Thus, oleic acid can be converted to dihydroxy stearic acid with
alkaline potassium permanganate.

CH 3 (CH 2 ) 7 CH = CH(CH2 ) 7 COOH KMnO

 4 
alkali
CH 3 (CH 2 ) 7 CHOH - CHOH(CH2 ) 7 - COOH

8. Peroxidation occurs readily under certain conditions. Thus some reaction

occur
directly with air when catalyzed by ultraviolet irradiation

Isopropyl benzene Air/UV

 isopropyl benzene peroxide
Others require the interaction of inorganic peroxide:

2C 6 H 5COCI + Na 2 O 2  C 6 H 5C - O - O - CC6 H 5 + 2 NaCI

Benzoyl chloride Benzoyl Peroxide

9. Amino compounds may be oxidized to azobenzene, p-aminophenol or

nitrobenzene under moderate conditions or the N-containing radical may be
completely removed under drastic conditions. In this way, quinone is derived from
aniline.
OXIDIZING AGENTS
The principal problem in oxidation reaction is the induction of the desired reaction
coupled with a satisfactory control of the extent of reaction.

1. Permanganates
The solid salts of permanganic acid are powerful oxidizing agent. Calcium
permanganate induces such rapid oxidation of ethanol that inflammation may result.
Aqueous solution of the permanganates also posses powerful oxidizing properties.

The calcium and barium salts have been

used for the oxidation of complex proteins. The
calcium salt has the advantage in that it forms
insoluble products. The calcium oxide
combines with the manganese dioxide to form
the insoluble CaO : MnO2, thus simplifying
recovery of products.

(a) Alkaline Solution (b) Neutral Solution (c) Acid

Solution.
2. Dichromates
The usual form of oxidation with dichromates is in the presence of sulfuric acid and
with the sodium or potassium salt. Although the dichromates exert an oxidizing
tendency in the absence of acid, the oxidation reaction can be made to occur more
quickly in the presence of acid and acid solutions are almost invariably used. Such
mixtures react to give oxygen as follows.:
K 2 Cr2 O 7 + 4H 2SO 4  K 2SO 4 + Cr2 (SO 4 ) 3 + 4H 2 O + 3O
2 moles of chromic acid (1 mole of dichromate) giving three atoms of oxygen. The
sodium salt is cheaper, much more soluble in water and is consequently more often
used.
3. Chromic Acid Solution
Chromic anhydride, CrO3, dissolves in glacial acetic acid is sometimes used as an
oxidizing agent.

4. Hypochlorous Acid and Salts

The lithium, sodium and calcium salts of hypochlorous acid are known in the solid
state. Although they decompose easily when wet, they are stable if thoroughly
dry.

5. Sodium Chlorite and Chlorine Dioxide

Sodium chlorite, NaCIO2 is marketed as 80% dry powder for use in bleaching. When
reacted with chlorine, sodium chlorite releases chlorine dioxide, CIO2, a gas at
normal temperatures and soluble in water. Chlorine dioxide is a powerful oxidizing
and bleaching agent; but because of its instability, it cannot be produced and stored.
The aqueous solution is decomposed by light to perchloric acid and chloric acid,
oxygen and water.
6. Chlorates
Chloric acid, HCIO3 is a powerful oxidizing agent. It may
be obtained in aqueous solutions at concentrations up
to about 40% and is stable at temperature up to 40°C.

Potassium chlorate is a powerful oxidizing agent.

However its solubility in water is limited, being only
3.3gm/100gm of water at 0°C and 56.5 gm/100gm of
water at 100°C. It has been widely used in the dry, finely
divided state as an oxidizing agent and in the laboratory
as a source of pure oxygen.

7. Peroxides
The principal peroxides used as oxidizing agents are those of lead, manganese
and hydrogen.
(a) PbO2 (b) MnO2 (c) H2O2 (d) Na2O2 (e) Silver Oxides

8. Nitirc acid and nitrogen tetroxide

The principle disadvantages of nitric acid as a partial oxidizing agent arises from the
tendency to act as a nitrating agent. Even then dilute solutions are used; the products
of oxidation may contain nitro derivatives.
9. Copper Salts
Copper is capable of existing in two states of oxidation and of passing readily from one
to the other of these states by oxidation or reduction. In its higher state of oxidation, it
is capable of acting as an oxidizing agent and in its lower state, as reducing agent. This
property makes the metal a useful material as an oxygen carrier or oxidation catalyst.

10. Alkali Fusion

Fusion with alkali in the presence of air (oxygen) often accomplishes oxidation
impossible to obtain otherwise.

11. Fuming Sulfuric Acid (Oleum)

Fuming sulfuric acid, H2SO4 + SO3, in the presence of mercury salts is a powerful
oxidizing agent.
12. Ozone
The powerful oxidizing potential of ozone has been made use of in textile
bleaching, paper bleaching, for destruction of phenolic bodies in coke-oven
waste liquors, and in limited ways for water purification.

Ozone in oxygen mixtures reacts slowly with lower-molecular weight paraffinic

hydrocarbons at room temperatures. At temperature above 260°C the ozone
reaction merges with normal slow combustion.
Acetic acid from Acetaldehyde
Figure shows the general type of apparatus used and flow diagram of the
manufacturing process. The reaction vessel consists principally of
aluminum-lines steel vessel fitted with air distributor. Aluminum coils for
heating and cooling, inlet and outlet opening and an air distributor.

In operation, 4,500kg (10,000lb) of 99.00-99.8%

acetaldehyde previously cooled to 0-5°C is
introduced, and then 18-22kg (39.6-48.4lb) of
manganese acetate is added in the form of saturated
acetic acid solution or as a powder ground to pass a
200 mesh sieve. Air is introduced through the
distributor head and at same time, steam is passed
through the aluminum coils to raise the temperature
gradually to the operating point. When the reaction
starts oxygen absorption from the incoming air is
almost complete and the heat of reaction must be
removed by cooling water, which is substituted for
the initial steam. The temperature is so controlled
that after 1 hr it approximates 27°C, after 2 hr. 28-
30°C and after 4 hr. 60°C.
The most satisfactory operating temperature is about 60°C. The reaction is complete in
about 12-14 hr. The pressure is not allowed to exceed 5 kg/cm2 (65.3 psi). The nitrogen
being vented through a series of condensers attached to the dome. Condensed aldehyde
is returned to the kettle. Before being released, the nitrogen is passed through water
scrubbers to remove the last of the aldehyde, which is later recovered.
 A concentrated acetic acid, exceeding 96% in strength, results Distillation is used for
final concentration and purification of acid. The yield varied from 88-95% of the
theoretical.
A retort of this size will produce about 60 tones of 99% acid per month when operated
normally or about 80-100 tons per month when forced.

Through study of the mechanism by which the catalyzed liquid phase oxidation of
acetaldehyde to acetic acid proceeds, it has been found that at temperatures below 15°C
and in suitable solvents the acetaldehyde forms an unstable compound, acetaldehyde
monoperacetate. At controlled low temperatures this compound can be made to yield
peracetic acid and acetaldehyde, salts of the metal cobalt, copper and iron catalyze the
first-stage reaction in a manner used in acetic acid manufacture.

This process is significant in that it is now in pilot-plant operation and commercial

production of peracetic acid is being planned. Previously, in situ use of this peracetic
oxidation of unsaturated natural fatty acid to epoxy derivatives. Commercial availability
of low cost peracetic acid will open new areas of epoxidaton reaction since almost any
olfinic double bond is capable of epoxidaton by peracetic acid. Because of the resulting
co-production acetic acid, it is possible that custom epoxidaton by user of acetic acid
might be a logical result or that an added incentive will be given for product
diversification by acetic acid user.
Oxidations of fatty oils by peracetic, acid results in products, which are epoxidized,
hydroxylated and acetylated and have properties of value for use in vinyl plasticizers and
greases.
In the presence of catalysts, such as the acetates of the eighth group of metals,
particularly cobalt, oxidation of acetaldehyde by air to acetic anhydride is claimed to occur
directly at temperatures of 30-35 °C and to result in 85-95 percent conversion per pass