US03CICV01 Unit -2 Dr. N. K.

Patel

Natubhai V. Patel College of Pure & Applied Sciences

B.Sc. Semester III
Industrial chemistry (Vocational)
US03CICV01: Unit Process
UNIT – 2
Syllabus

Sulfonation: Introduction, sulfonating agents, chemical and physical factors in sulfonation,

Kinetics and mechanism of sulfonation reaction. Commercial sulfonation of benzene (Barbet
process) Batch v/s continuous sulfonation

Oxidation: Introduction, types of oxidation reaction, oxidizing reagents, kinetics and

mechanism of oxidation of organic compounds, liquid phase oxidation, vapour phase
oxidation. Commercial manufacturing of Benzoic acid, Phthalic anhydride and Acetic acid.

SULFONATION AND SULFATION

2.0 INTRODUCTION

Sulfonation may be defined as any chemical process by which the sulfonic acid
group (SO2OH) or the corresponding salt or sulfonyl halide group (e.g. –SO2CI) is introduced
into an organic compound. These groups may be situated on either a carbon or a nitrogen
atom. Sulfonates of the second type (e.g. RNHSO2ONa) are termed N-sulfonates or
sulfamates.
Particular types of sulfonation include sulfo-chlorination (introduction of an -SO2CI
group into an alkane using sulfur dioxide and chlorine), halo-sulfonation (reaction of
halosulfonic acid —CISO3H or —FSO3H with an aromatic or heterocyclic compound to
introduce an —SO2CI or an —SO2F group), sulfoxidation (use of sulfur dioxide and oxygen to
sulfonate an alkane), sulfo-alkylation, sulfo-acylation and sulfo-arylation (introduction of
sulfalkyl, sulfoacyl or sulfoaryl groups).
Sulfation involves placement of —OSO2OH group on carbon yielding an acid sulfate
(ROSO2OH) or of the -SO4- group between two carbons, forming the sulfate ROSO2OR
Sulfato-alkylation designate introduction of a sulfated alkyl group into an organic
compound.

2.1 CLASSIFICATION OF SULFONATES

 Aliphatic and alicyclic

 Aromatic
 Heterocyclic and
 N-sulfonates or sulfamates.
The first three types have the - SO2OH group on carbon, the chemical nature of which
determines the classification. Thus, C6H5OCH2SO2ONa (sodium-phenoxymethanesulfonate)
would be considered an aliphatic sulfonate.
For practical reasons, it is also useful to refer to three other types of sulfonates, namely
those derived from petroleum fractions, from lignin, and from fatty oils. These materials are
mixtures of indeterminate or variable composition, probably comprising one or more of the
main chemical types of sulfonates together with sulfates and other sulfur compounds, and
are made largely by empirical procedures. All three types are commercially important.

2.2 CLASSIFICATION OF SULFATES

Sulfates may be classified as sulfated alkenes, alcohol sulfates, cyclic sulfates,

sulfated carbohydrates and sulfated nitrogenous polysaccharides.

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2.3 GENERAL PROCEDURES FOR PREPARING SULFONATES

 Treatment of an organic compound with SO3 or a compound thereof

 Treatment with a compound of SO2
 Condensation and polymerization methods
 Oxidation of organic compound which already containing sulfur in a lower state of
oxidation such as RSH.
Condensation procedures refer to the reaction of organic sulfonates building blocks
(such as HOCH2CH2SO3Na) with other organic compounds (such as long-chain acid
chlorides) to form new sulfonates with altered properties; these methods include
sulfoalkylation, sulfoacylation and sulfoarylation.
For the preparation of sulfates, the first and third (i.e. sulfatoalkylation) methods only
are of interest.
2.4 SULFONATING AND SULFATING AGENTS AND THEIR PRINCIPAL APPLICATION

Sulfonating and sulfating agents are of two types (1) inorganic and (2) organic. The
latter type is employed in the condensation procedures.
2.4.1 Principal sulfonating and sulfating agents
Sulfur trioxide and compounds thereof
 Sulfur trioxide, oleum, concentrated sulfuric acid (SO3 plus water)
 Chlorosulfonic acid (SO3 plus HCl)
 Sulfur trioxide adducts with organic compounds
 Sulfamic acid
The sulfur dioxide group
 Sulfurous acid, metallic sulfites
 Sulfur dioxides with chlorine
 Sulfur dioxide with oxygen
Sulfoalkylating agents
 Sulfo-methylating agents (hydroxy and aminomethanesulfonates)
 Sulfo-ethylating agents (hydroxy-chloro and methylaminoethanesulfonates,
ethylenesulfonic acid)
 Miscellaneous sulfo-alkylating agents, sulfo-acylation, sulfo-arylation,
sulfato-alkylation
2.4.2 Uses and application of sulfonate and sulfates
Millions of tons of sulfonates are manufactured annually lignin sulfonates obtains as a
by-product of paper manufacture constitutes the major single product. These compounds
have achieved a wide variety of interesting and important uses. Most of them are employed
as such in acid or salt form for application where the strongly polar hydrophilic - SO2OH group
confers needed properties on a comparatively hydrophobic non-polar organic molecule. A
few sulfonates are both marketed and used in acid form, including methane and
toluenesulfonic acids as catalysts and phenolsufonic acid as an electroplating additive. A
considerably larger group is marked in salt form and used in acid form; such compounds
include mothproofing agents, and synthetic tanning agents. In these cases, the salts are
applied in acid medium, thereby liberating the free -SO2OH group, which firmly attaches the
organic molecule to the textile fiber or leather. The major quantity of sulfonates and sulfates is
both marketed and used in salt form. This category includes detergents, emulsifying,
deemulsifying, penetrating, wetting and solubilising agents, lubricant additives, and rust
inhibitors. Polymeric sulfonates include dispersing agents, elastomers, water-soluble synthetic
gums and thickening agents and ion exchange resins which function as strong acids with
complete water insolubility and unusual combination of properties leading to many
important applications.
Aromatic sulfonyl chlorides -RSO2CI are useful for preparing sulfonamides (including
sulfa drugs, dyes, tanning agents, plasticizers and the sweetening agents (saccharin) and
sulfonate ester (insecticides).
Sulfamates include herbicide, sweetening agent and blood anticoagulant.

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Sulfonates and sulfates find use as intermediates for preparing organic compounds
not containing sulfur, notably phenols (prepared by caustic fusion of various sulfonates) and
alcohols (made by hydrolysis of sulfated alkenes). Phenol, resorcinol, the naphthols, hydroxy-
anthraquinones and 8-hydroxyquinoline are phenols so produced while ethanol and
isopropanol are examples of alcohols made from the sulfates.

2.5 BENZENE SULFONIC ACID OR MONOSULFONATION OF BENZENE

2.5.1 Raw materials

Under optimum condition, the reaction time for this process has been calculated at
1.5hr. at 180°C using a seven-stage reactor, continuous process10 moles of benzene per
mole of sulfuric acid required. In contrast, the same process operated in batches at 160-
180°C would require 14 hr. and 6-8 moles of benzene per mole sulfuric acid. Thus the
continuous method increases by nearly ten times the capacity of the batch method. It is
further estimated that the ratio of benzene used, to benzene reacted could be reduced as
low as 3 :1 by doubling the time of reaction. The efficiency of the process can be further
increased by using 10% oleum instead of sulfuric acid, thereby reducing the required water
removal without substantially raising by product sulfone formation.
2.5.2 Reaction

2.5.3 Manufacture
Benzene can be monosulfonated efficiently and on a continuous basic by the partial
pressure distillation method. A typical operating procedure based on the flow diagram shown
in figure is as follow.
Sulfuric acid is continuously pumped from storage tank (1) by means of pump (2)
through pressure regulator (3) and meter (4) to the sulfonator (5) Liquid benzene from storage
tank (6 or 14) is continuously fed by pump (7) through meter (8) to the direct vaporizer super
heater (9) and hence to the sulfonator (5) and the Sulfonation tower (10) In the Sulfonation,

1. H2SO4 storage tank

2. Pump
3. Pressure regulator
4. Flow-meter
5. Sulfonator
6. Liquid benzene
storage tank
7. Pump
8. Meter
9. Vaporizer
10. Sulfonation tower
11. Condensor
12. Separator
13. Neutralizing drier
14. Liquid benzene
storage tank

Sulfuric acid reacts with benzene, and the reaction mass containing 30% un-reacted
sulfuric acid flows out continuously to the top of the Sulfonation tower (10) which is arranged
like a plate column, the reaction mass flows downward through the tower while further
reacting with a countercurrent stream of benzene vapour.

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The exit benzene-water vapour are continuously discharged from top of tower (10) to
condenser (11) and stratified in separator (12) and the benzene storage (14) while the
benzenesulfonic acid, containing 2.5-3.5% of sulfone and 3-4% of sulfuric acid is continuously
drawn off at the bottom of the tower.

2.6 NAPHTHALINE β - SULFONIC ACID

2.6.1 Raw materials

Naphthalene, sulfuric acid, water, steam etc
2.6.2 Reaction

2.7.3 Manufacture
The hydrocarbon is reacted with sulfuric acid; in addition to the desired isomer, about
15% of the alpha isomer is also formed.
Naphthalene (3,350 1b - 26.2 1b moles) is charged to a cast iron sulfonation kettle, 500
gal capacity, equipped with propeller or anchor agitator and heated either directly with
generator gas or by high-pressure (100 1b) jacket steam. It is melted by heating to 90-110 °C.
Sulfuric acid (3,350 lb of 96% strength - 32.8 lb moles) is then added with agitation, the
temperature being allowed to rise to about 160 °C. The batch is held at 160 -165°C for about
2hrs to complete reaction, during which time water (approx. 400 lb-22.2 lb moles) and
naphthalene (approx. 350 lb -2.7 lb moles) distill off and are collected by condensation. The
reaction products contains mainly monosulfonic acids (85 % beta and 15% alphas) plus some
sulfone,free sulfuric acid, disulfonic acids and tar. The undesired α- sulfonate is now removed
by blowing dry steam into the charge to effect hydrolytic desulfonation, the liberated
naphthalene being distilled and recovered. It is essential to employ dry steam to avoid
foaming and to maintain a temperature in the range 160-165°C to ensure rapid reaction.
About 16% or 540 lb of the original naphthalene employed is recovered, leaving the
β-sulfonate contaminated with only about 0.1% alpha isomer.
The hydrolyzed sulfonation mixture is discharged into the water with good agitation
and the resulting solution is run into the brine to form the sodium sulfonate salt. The slurry so
obtained is agitated for 10 hr as it cooled to 30 °C this yields an easily filterable precipitate.
The filtration is accomplished by pumping or blowing the sodium sulfonate suspension into a
pressure filter containing wooden plate filters and rubber-coated frames. The shell of the filter
is coated with tar to minimize corrosion. The filtrate is permit to stand and more salt added if
necessary and then it is refiltered to collect any additional sulfonate that has crystallized out.
The second crop of sodium sulfonate is not as pure as the first. The filter cakes are
washed with a minimum of water and these washings are employed to advantage as part of
the liquor in the sulfonation dilution tank. The filter cake of sodium sulfonate containing about
70 % water is pressed hydraulically to a water content of about 30%. The press cakes are
dried to moisture content of about 5%, disintegrated and delivered to the caustic fusion
kettles for conversion to β -naphthol. The yield is about 90% of theory on the basis of
naphthalene consumed.
Factors ensure rapid and complete sulfonation
 use of about 25% excess acid, corresponding to about 40% excess over that actually
converted to sulfonate
 Distillation of a quantity of water (22.2 moles) only slightly less than the amount of
naphthalene (23.5 moles) sulfonated
 Use of an elevated reaction temperature. At this temperature, water will distill from
dilute acid until it has increased to 68% in concentration, which is above the
concentration (64%) required to sulfonate naphthalene at this temperature.

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 As in every important sulfonation, several modified procedures have been suggested

to reduce the acid factor more closely to theoretical, including the use of excess
naphthalene or operation under vacuum. Continuous operation has also been
studied. None of these expedients has been adopted commercially. Variations in the
working up procedure have however sometimes proved advantageous.

OXIDATION

2.8 TYPES OF OXIDATIVE REACTIONS

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 principal types of oxidative reactions may
be set forth as follows:
1. Dehydrogenation is illustrated in the transformation of a primary alcohol to an aldehyde:
C2H5OH + ½ O2 CH3CHO + H2O
Or a secondary alcohol to a ketone:
CH3CHOH.CH3 + ½ O2 CH3COCH3 + H2O
2. An atom of oxygen may be introduced into a molecule, as is illustrated by the
oxidation of an aldehyde to an acid:
CH3CHO + ½ O2 CH3COOH
Or of a hydrocarbon to an alcohol:
(C6H5)3CH + 1/2O2 (C6H5)3COH
3. A combination of dehydrogenation and introduction of oxygen may occur, as in the
preparation of aldehyde from hydrocarbons:
CH4+O2 CH2O + H2O
Or the preparation of benzoic acid from benzyl alcohol
C6H5CH2CH.OH + O2 C6H5COOH + H2O
4. Dehydrogenation may also be accompanied by molecular condensation, as is the
case when two molecules of benzene from diphenyl or two molecules of toluene
from stilbene or when methyl, anthraquinone is converted to anthracene yellow C.
2C6H5 + ½ O2 C6H5 - C6H5 + H2O
2C6H5.CH3 + O2 C6H5.CH = CH.C6H5 + 2H2O
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:
C10H8+4.5O2 C8H4O3 + 2H2O + 2CO2
6. Oxidation may be accomplished indirectly through the use of intermediate reaction.
H 2O
C6H5.CH3 C6H5CCI3 C6H5COOH
NaOH
C6H6 C6H5SO3H C6H5OH
CH3OH + CO CH3COOH
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.
KMNO4
CH3(CH2)7CH= CH(CH2)7COOH CH3(CH2)7CHOH-CHOH(CH2)7- COOH
Alkali
When sodium dichromate in acid solution is employed, fission as well as oxidation
occur and pelargonic and azelain acids are produced

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8. Peroxidation occurs readily under certain conditions. Thus some reaction occur
directly with air when catalyzed by ultraviolet irradiation
Air
Isopropyl benzene isopropyl benzene peroxide
UV
Others require the interaction of inorganic peroxide:
2C6H5COCI + Na2O2 C6H5C-O-O-CC6H5 + 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.
10. Sulfur compounds may be oxidized by acid permanganate, as in the
preparation of sulfonate, trionals and tetranals from (CH 3)2C(S.C2H5)2 or
(CH3)(C2H5)C(SC2H5)2 or (C2H5)2C(SC2H5)2 In which the sulfide sulfur is oxidized to sulfonic
groups. It should be noted that the mercaptans behave differently toward oxidizing
agents from the alcohols in that the action of strong oxidizing agents increases the
valence of the sulfur atom instead of removing hydrogen as in the case of alcohols. Thus;
Oxidation
CH3CH2OH CH3CHO + H2O
Ethyl alcohol Acetaldehyde
CH3CH2SH CH3CH2SO2OH
Ethyl Mercaptan Ethane sulfonic Acid
On the other hand, mild oxidation of mercaptans may result in the formation of disulfides
2CH3CH2SH C2H5S--SC2H5 + H2O
Ethyl mercaptan Diethyl Disulfide

2.9 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.
K2Cr2O7 + 4H2SO4 K2SO4 + Cr2(SO4)3 + 4H2O + 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.

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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. Alkaii 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.

2.10 ACETIC ACID

The formation of acetic acid furnishes an excellent example of liquid-phase oxidation

with molecular oxygen. Acetic acid may be obtained by the direct oxidation of ethanol, but
the concentrated acid is generally obtained by oxidation methods from acetaldehyde that
may have been formed by the hydration of acetylene or the oxidation of ethanol. The
oxidation usually occurs in acetic acid solution in the presence of a catalyst and at
atmospheric or elevated pressures.
Temperatures may range, up to 100°C, depending upon conditions, but are usually
lower.
2.10.1 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

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added either 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

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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

2.11 PHTHALIC ANHYDRIDE

2.11.1 Raw materials

O- xylene, Air, Vanadium pentoxide as catalyst
2.11.2 Reaction

2.11.3 Manufacture
O-xylene oxidation in presence of a catalyst like vanadium pentoxide at 5500C yields
phthalic anhydride.

As shown in figure preheated o-xylene is sent into a hot stream of air which is kept at
140–1500C and under a pressure of 2 bars. Air is enriched with vapours of o-xylene and care
should be taken that the mixture is outside to combustion, where the catalyst packed in
tubes.
Exothermic heat is absorbed by circulating molten salt in the space between tubes
and shell. The hot vapours are allowed to exchange heat to waste heat boiler. By cooling

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further phthalic anhydride is sub lined and is a deposit on the surface of switch condenser.
The deposited film of phthalic anhydride is melted by means of circulation of steam.
The molten anhydride is again distilled under vacuum for purification. Along with
phthalic anhydride a small amount of benzoic acid and maleic anhydride are also there.
Phthalic anhydride is converted into phthalic acid through potassium phthalates. By
hydrolyzing potassium terephthalic acid can be obtained.

2.12 BENZOIC ACID

The use of manganese dioxide for the oxidation of toluene to benzaldehyde and
benzoic acid was formerly extensive. With manganese dioxide the principle product is
benzaldehyde, for high yield to benzoic acid, a stronger oxidizing agent such as chromic
acid is required.
Considerable benzoic acid is manufactured by decarboxylation of phthalic acid, a
process that yields a chlorine free product. The development of this process has served to
restrict the investigation of air oxidation method.
The products of toluene oxidation, chiefly benzadehyde, benzoic acid, maleic acid
and anthraquinone are obtain in proportions that depend upon catalyst, temperature,
oxygen ratio and time of contact. High oxygen ratios and long time of contact are in general
conductive to Benzoic acid formation. At temperature of 280 – 3000C, reaction begins in
presence of vanadium oxide catalyst, but reaction slow, long time of contact are required
and benzoic acid tend to be the major product.
Oxidation of toluene with large excess of air over an alumina- supported vanadium
oxide catalyst has been claimed to be an effective method for benzoic acid production.
Thus the use of air: toluene weight ratios of 39 – 49: 1, temperature on the order of 410–4300C
and contact time of 0.25 – 0.75 sec. are claimed to result in yields of benzoic acid of about
34% with corresponding maleic acid yields of 7–11% based on toluene consumed in the
process.
2.13 EXERCISE

Sr. Question Marks Exam/year

No.
1. Explain sulfonation and sulfation. State the principle sulfonating 03 SPU 2005
and sulphating agents
2. Give an account of different type of oxidising agents and 08 SPU 2005
oxidative reaction
3. With the help of flow diagram describe the manufacture of vinyl 05 SPU 2006
acetate
4. Write manufacture of acetic acid from acetaldehyde 05 SPU 2006,
2007
5. Explain the term sulphonation and sulfation giving suitable 03 SPU 2006
examples
6. Write note on various oxidative reactions 06 SPU 2006
7. Write manufacture of benzoic acid 04 SPU 2006
8. Write note on different hydrolysing agents used for hydrolysis 03 SPU 2006
9. With the help of flow diagram describe the continuous partial 05 SPU 2007
sulfonation of benzene
10. Describe manufacture of benzoic acid from toluene 04 SPU 2007
11. Define the term hydrolysis. Write note on alkali hydrolysis 04 SPU 2007
12. Using neat flow diagram describe the manufacture of ethyl 05 SPU 2007
acetate
13. Define term sulfonation and sulfation giving suitable examples. 04 SPU 2007
Also write various sulfonating and sulphating agents used for
sulfonation and sulfation
2.26 FURTHER READING
1. Unit Processes in Organic Synthesis by P. H. Grogins.

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