Unit Processes

PS02CICH29
Sem:2

Unit-2
1
 Syllabus
• Unit 2: Introduction, definition, agent, technologies
and applications of Esterification, Hydrolysis,
hydration.

2
 Esterification
• Introduction
• An ester is usually defined as a compound formed by substituting a group such
as ethyl (-C2H5) for the ioniable H of an acid.
• In many instances it is probably more accurate to regard it as an alcohol of which
the hydroxyl H has been replaced by the acyl group.
• Esterification by organic acids
• An ester is usually defines as a compound formed by substituting an organic
radical for an ionizable hydrogen of an acid.
• The mechanism by which this replacement occurs has been well established.
• If the direct esterification of an acid, such as acetic, by an alcohol, such as
ethanol, is considered, possibility of breaking either the carbonyl oxygen bond
or the alkyl-oxygen bond is evident.

3
• Evidence for the breaking of the carbonyl-oxygen bond was found in the
study of the following reaction.

• In which water was formed.

• If the alkyl-sulfur bond had broken, hydrogen sulfide would have been
formed.
• That the carbonyl-oxygen bond is the one broken was confirmed by the finding
that esterification of benzoic acid containing the normal oxygen isotope
distribution by methanol enriched with O18 produced methyl benzoate
containing the heavy oxygen isotope, while the water formed had only the
normal isotope distribution.
• A generalized explanation for the selectivity of the bond-breaking process is
found in the electronic structure of the reactants and products.
• Since oxygen is more electronegative than carbon, the carbonyl carbon is
more positive than the carbonyl oxygen. 4
5
• Any compound (B) containing a free pair of electrons,
whether due to ionization or not, can attack this positive center.
Thus,

• The transition state can lose the negative charge by loss either
of a hydroxyl ion or of the species, which originally attacked
the positive center.
• Equilibrium will be established between the starting materials
and the final products since the hydroxyl ion produced can
attack III to form the same transition state as that from I and II.
6
• The esterification reactions are reversible and that the extent
of reaction depended on the relative amounts of each
compound present.
• The equilibrium constant for the reaction is
Acid + Alcohol↔ Ester + Water

• Unless activities are used in this expression, the value of K

changes with the presence of salts.
• Menschutkin made a comparative study of the relative rates
of esterification and the equilibrium constant of a large
number of acids and alcohols.
• He concluded for primary, secondary, and tertiary alcohols as
follows: 7
• The primary alcohol ethyl, propyl, and butyl have
approximately the same initial rates.
• Allyl alcohol is much slower than propyl, the
saturated alcohol with the same number of carbon
atoms.
• The presence of the phenyl group in benzyl alcohol
has a retarding influence.
• The secondary alcohols are markedly lower than the
primary in both initial velocity and limit.
• The tertiary alcohols show little esterification in 1 hr
and hardly any more in 100. 8
• The tertiary alcohols get dehydrated easily to the
unsaturated hydrocarbon and the acid.
• It is frquent with esters of tertiary alcohols to find
less ester present after a long heating period than
after a short one.
• Phenol and thymol, which may be regarded as
tertiary alcohols from which water cannot be
split off, show low initial rated but comparatively
high limits.

9
• Catalytic esterification
• If samples are taken at intervals from a mixture
of acetic acid and ethyl alcohol at room
temperature and titrated, a slow decrease in
acidity can be observed, but days and even
months will elapse before the minimum value, or
limit, is reached.
• Like most other reactions, the speed of
esterification approximately doubles with 100C
rise in temperature.
10
• Hence, heat is used to speed up esterification
reactions.
• In most instances, heating alone does not speed up
esterification to a practical rate, except in the case of a
high-boiling alcohol, such as glycerol, with high
boiling acid such as stearic.
• Esterification cannot be affected at atmospheric
pressure in reasonable time without the use of catalyst.
• The process of esterification can be hastened by the
addition of a strong acid, such as sulfuric or
hydrochloric acid.
11
• The equilibrium point of the reaction is not altered by
the catalyst; only the rate of esterification is increased.
• Esterification proceeds by attack of an alcohol molecule
on the slightly positive carbonyl carbon of an acid.
• The larger this positive charge, the more rapid the
reaction will be.
• While the nature of the R group attached to the
carbonyl group will influence this charge.
• Catalysts can also be used to increase the positive
charge so that a given acid will esterifies more rapidly.

12
• Esterification catalysts are compounds, which are acidic in
nature.
• Acidic compounds in this case are those in which the central
atom has an incomplete external electron shell, so that besides
the hydrogen ion, compounds such as boron trifluoride,
aluminum chloride, or zinc chloride can be considered to be
acids.
• The neutralization reaction of such an acid is written as the
donation of an electron pair by a base to the acid.

13
• When an acid (HA) is added to an esterification
mixture, the oxygen present will act as bases
and coordinate with the acid.
• The mechanism may be written two ways,
depending on which oxygen of the carbonyl
group acts as the base.

14
• The alcohol oxygen also can act as a base
toward the acid.
• However, this reaction hinders esterification
and, may lead to dehydration of the alcohol /
dehydration is an especially important side
reaction with tertiary alcohols.
• In certain cases when the acid is sufficiently
strong, the esterification is self-catalyzed.
• Quite often the speed of the reaction is increased
by working under increased pressure so that
higher temperatures can be used.

15
 Esterification of carboxylic acid
derivatives
Alcoholysis
• In the alcoholysis or ester-interchange reaction;
• An alcohol reacts with a ester to give a new ester.

16
• Thermodynamics of Alcoholysis
• Alcoholysis may be regarded as a special case of
esterification.
• Equilibrium expression, which is similar to those for the
esterification of acids by alcohols, may be written for
alcoholysis reactions.

17
• The alcoholysis equilibrium (K) can be calculated
from the esterification constants (K 1 and K2) of
methanol and ethanol with benzoic acid

18
• This relationship between the esterification
constants is true in the absence of water and free
acid as it is in their presence.
• Thus, if 1 mole of methanol is added to 1 mole of
ethyl benzoate, 0.53 mole of the methyl ester will
be formed and like amount of ethyl alcohol set
free.

19
• The alcoholysis equilibrium is related to the
esterification constant of the alcohols with the acid.
• A tertiary alcohol will not replace a primary
alcohol in alcoholysis, and a secondary alcohol will
replace a primary alcohol to a small extent only.
• At room temperature in the absence of a catalyst,
equilibrium is established extremely slowly.
• The strong acids that are used as catalysts in ordinary
esterification serve equally well for alcoholysis.

20
• The most commonly used catalysts for alcoholysis are the
sodium alkoxides.
• They must be used in anhydrous systems since they are
hydrolyzed by water and the resulting hydroxides hydrolyze
the esters.
• Sodium alkoxides is prepared by dissolving a small amount
of sodium in the alcohol to be used and then to add the ester.
• Low concentrations of these catalysts cause the
transformation to take place rapidly even at room
temperature.
• Sodium ethoxide is about one thousand times as active as an
equivalent amount of hydrochloric acid.
21
• The increase in rate is observed due to the
basicity of the alcohol oxygen is increased.
• This increase in basicity facilitates attack on the
positive carbonyl carbon.

22
• The sodium methoxide-catalyzed methanolysis of
1-methyl benzoate is first order with respect to
both ester and methoxide ion and does not involve
fission of the alkyl-to-oxygen bond.
• The evidence indicates that the mechanisms of
basic ester interchange and basic ester hydrolysis
are similar.
• The mechanism of acid-catalyzed alcoholysis is
similar to that of acid-catalyzed esterification.

23
• The remarkable quality of alcoholysis in the presence
of sodium ethoxide as catalyst is the rapidity of
reaction as compared with esterification and
saponification.
• The saponification of phenyl benzoate in aqueous
alcohol ordinarily would be represented by equation 4

24
• Gibby and Water's estimated alcoholysis for above
equation and find to be one thousand times as rapid
as the saponification according to equation (1).
• Then the ethyl benzoate is saponified slowly.
• The greater rapidity of alcoholysis compared with
hydrolysis may be shown qualitatively by a simple
experiment with triacetin. 25
• Some triacetin C3H5(OCOCH3)3 which is odourless, is added
to a solution of sodium hydroxide in 50% alcohol the odor
of ethyl acetate is apparent at once and shows that the
immediate reaction is the information of ethyl acetate.
• On this account, it is necessary to use an efficient reflux
condenser when determining saponification numbers of
even high-boiling acetates.
• Besides the sodium alkoxides, various other catalysts for
this reaction have been recommended: ammonia, pyridine,
tetramethylammonium hydroxide, aluminum alkoxides,
lithium methoxide, sodium hydroxide and sodium
carbonate.
26
• In the alcoholysis of ethyl esters of alpha-halogenated
acids by allyl and methallyl alcohols, zinc is used as the
catalyst.
• An acid might polymerize the unsaturated alcohol, while
sodium methoxide would react with the halogen of the
acid.
• Titanium esters are excellent ester-exchange catalysts.
• They are effective in catalyzing interchange between two
esters as well as between an alcohol and an ester.
• They usually do not catalyze side reactions, and they are
especially useful with polymerizable standard ester-
exchange catalysts. 27
• Mechanism of esterification reaction

• In this step carboxylic acid is protonated which is

unstable so it is readily converted into carbocation.

• In this step, addition of alcohol to carbocation

and intramolecular hydrogen transfer will
produce oxonium ion. 28
• In this last step, the removal of water molecule
and intramolecular migration of proton (removal
of hydrogen) will produce ester.

29
 Ester by additions to unsaturated systems
• Addition of an Acid to an Olefin
• The addition of an organic acid to an unsaturated
hydrocarbon in the presence of a strong-acid
catalyst probably occurs through an Intermediate
carbonium ion

30
• The addition takes place according to Markownikoff's rule.
• The addition of carboxylic acids to the double bonds of
isobutylene and trimethyl ethylene gives tertiary esters.
• A true equilibrium independent of sulfuric acid
concentration is established in the exothermic reaction.
• The addition does not go well with ethylene, but goes well
with many of the higher alkenes, particularly with some of
the terpenes,
• To avoid the polymerizing effects of sulfuric acid, various
other catalysts, such as sulfonic acids, triethylamine,
hydrofluoric acid, boron trifluoride and cuprous chloride
have been used.
31
• The addition may take place at room temperature
or higher and is aided by pressure.
• The vapors of the acid and hydrocarbon may be
passed over catalysts, such as activated carbon,
heteropoly acids, or metal phosphates.
• The addition of formic acid to olefin is easily
controlled and gives high yields of esters.
• Since the formates are easily hydrolyzed, the
method provides a convenient way of
introducing hydroxyl groups into hydrocarbons.32
• Ester from Acetylene
• When acetylene and acetic acid are brought
together with a suitable catalyst, a vinyl ester
or an ester of ethylidene glycol is formed
according to reaction.

33
• By altering the reaction conditions, a preponderance of
either product may be produced as desired.
• Vinyl acetate, which is used for making polymers, and
ethylidene diacetate, which is an intermediate for the
manufacture of acetic anhydride, is produced on a
large scale.
• The reaction may be applied to other carboxylic acids
and acetylene derivatives.
• Strong acids, such as sulfuric, methane di-and
trisulfonic, and phosphoric acids are catalysts.
• They may be used in conjunction with mercury salts. 34
• Other catalysts, can be used for the reaction, include
boron trifluoride and the salts of various metals, such as
zinc silicate, zinc acetate, and mercuric phosphate.
• The addition may be effected in the vapor phase over a
solid catalyst at 200°C or above.
• Zinc salts of aliphatic acids on carbon carriers are
excellent catalysts for the vapor-phase reaction.
• Zinc acetate is widely used in the manufacture of vinyl
acetate.
• Zinc salts may be used also as catalysts for the preparation
of vinyl esters of higher carboxylic acids in the liquid
phase. 35
• Esterification by Ketene
• The reaction of ketene with alcohols to produce esters is attractive,
since all the ketene goes into the product and there are no by-products.

• Ketene is an effective acetylating agent as acetic anhydride. Salicylic

acid is acetylated by ketene.
• Esters are produced by the reaction of ketene with an acetal or ortho
ester.
• Boron trifluoride is an excellent catalyst for the addition.
• A catalyst is often necessary to complete the reaction.
• Even t-butyl alcohol reacts readily with ketene in the presence of
sulfuric acid. 36
• Products obtained by esterification process
• Ethyl acetate
• It is produced by esterification of ethanol with acetic acid.
• It is used as solvent.
CH3COOH + CH3CH2OH → CH3COOCH2CH3 +H2O
• Isopropyl acetate
• It is produced by esterification of isopropyl alcohol and acetic acid. It is
used as solvent.
CH3COOH + (CH3)2CHOH → CH3COOCH(CH3)2 + H2O
• Sec-butyl acetate
• It is produced by esterification of sec-butyl alcohol and acetic acid. It is
used as solvent.

37
• > Ester of phthalic acid
• It is important plasticizer and produced from phthalic
anhydride and alcohol containing 4-8 carbon atoms.

• > Methyl methacrylate

• MMA can be obtained by reaction of acetic acid with isopropyl
alcohol. It is used as monomer for the production of
polymethyl methacrylate.

38
• Ethylene terephthalate
• It is produced by reaction of dimethyl
terephthalte with ethylene glycol.

39
 Reactors used in esterifying process
Liquid-phase esterification process combined with
distillation of the azeotropic mixture

40
• Reactors, a), b) and c) are esterifying
reactors having sufficiently large volume.
• They are heated with the help of steam
continuously applied into the reactors.
• The units a), b) and c) are differ only in
separation techniques.
• In figure a, reactor equipped with
condenser, in figure b, reactor equipped
with dephlagmating column and in figure c,
reactor equipped with fractionating column
and boiler.
• The acid, alcohol and catalyst are entered from the upper side of the reactor
which is heated with the help of steam.
• The reaction mass contains vapors of ester, unreacted alcohol are condensed
in condenser and it is entered into the separator.
• In this separator water will be separated out. 41
• In figure d tray column is shown, which
is made up of single column with number
of horizontal trays.
• The distance between each two trays is
0.5 to 1.0m.
• The reactants are entered from the upper
side of the column where the reaction
mass is heated with the help of steam.
• After the reaction vapors of reactants and
products are condensed in condenser.
• Condensate is separated in separator unit
where water can be removed from the
condensate.
• Finally ester will come out from the
bottom of the column.
42
 VINYL ACETATE
• Raw materials:
• Acetylene, acetic acid, Zinc acetate as catalyst
• Reaction:

43
• The manufacture of vinyl acetate, to be used for preparing
polyvinyl acetate, is preferably carried out as a vapor-phase
reaction between acetylene and acetic acid.
• A flow sheet showing the major items of equipment for a vapor-
phase process is shown in figure.
• Zinc acetate is used commonly as the catalyst for these vapor-
phase processed.
• A suitable catalyst consists of 3-5 mm granules of a mixture of
42parts of zinc acetate to 100parts of activated charcoal.
• The catalyzers are steel boxes in which the catalyst is held
between vertical plates spaced 1 inch apart cooling of
exothermic reaction, is provided by horizontal steel tubes in the
catalyst bed through which water is passed. 44
• Purified acetylene, from which all traces of
hydrogen sulfide and phosphine have been removed
by scrubbing with sulfuric acid and passing over
potassium dichromate and kieselguhr is bubbles
through acetic acid heated to 60°C in the vaporizer.
• The rate of flow is adjusted so that the gas leaving
the vaporizer carries with it 23 %by weight of acetic
acid.
• The gas, which is heated to 1700C by passing
through a series of heat exchangers and heaters,
flows into the catalyzer in which the gas temperature
is held at 170°C. 45
• The conversion to vinyl acetate in the catalyzer
may be regulated either by adjusting the rate of gas
flow through the catalyzer or by varying the
reaction temperature.
• The best economic balance is obtained at a
conversion of 60%.
• A charge of catalyst has a life of about two months
when vinyl acetate is produced at a rate of 400-500
metric tons/month.
• The crude vinyl acetate vapor emerging from the
catalyzer passes through the heat exchanger and
then to a separator where carbon dusts is removed.
46
• The vapor is then passed through a series of three
condensers, as is illustrated in the flow diagram.
• Condensate from each of these units, plus the liquid from
the mist remover, is collected in a column line which
flows to the still.
• The condensate averages 60% of pure vinyl acetate and
40% of acetic acid.
• Resin formation during distillation is prevented by the
addition of thiodiphenylamine to the crude vinyl acetate in
the still.
• The yield of vinyl acetate varies from 92 - 95 % based on
acetylene and from 97 - 99 % based on acetic acid. 47
 ETHYL ACETATE
• Raw materials
• Acetic acid, ethanol
• Reaction

48
Manufacture

49
• A continuous process for making ethyl acetate,
which is especially adapted to the utilization of
dilute acetic acid as shown in flow diagram.
• In the process residual acid water, exhausted of its
acid and the alcohol to as low a point of economical,
is promptly and continuously discharged from the
apparatus.
• The regulation of still is thus practically fixed.
• Another advantage is that the final purification and
work up of the wash water can be tied in with the
production of crude ester. 50
• The raw materials are first blended in a correct
proportions and feed from the feed tank in a
steady stream through a pre-heater into the
esterifying column.
• From the top of the column is taken off a
mixture of about 20% ester, 10% water and
70% alcohol, while a suitable amount of same
distillate is refluxed back to the column.

51
• The ternary mixture taken off passes to the separating
column, here it is rectified by closed steam in the
calandria.
• Part of the condensate is returned as reflux to the top of the
column, and the take-off goes to a proportional mixing
device, where it is blended with about an equal volume of
water, which causes a separation into two layers.
• These are setting out in the separator tank, the watery
portion overflowing back to the lower part of the separating
column, whence, blended with the alcohol and water
accumulating in the base of the column, the watery portion
is passed by pipe to in the esterification column.
52
53
• On the lower plates the column, the alcohol is exhausted and distills
upward as vapor, while the slop water goes to waste.
• The washed ester, containing a little dissolved water and alcohol,
overflows from the separator and enters the drying column in
which a sufficient amount is distilled off to came with it the water
and alcohol, which may go either to the separating column of back
to the mixer washer, and separator.
• The dry ethyl acetate that accumulates in the calandria of the drying
column is taken off through a cooler to the receiving tank.
• In general, this ester, although dry and holding very litter alcohol
and free acid, needs to be redistilled before it can be placed on the
market, because it may contain salts of copper and higher-boiling
esters formed from other acids present as impurities in the crude
acetic acid employed. 54
• The working up of crude ester made by the
batch process is very similar to that employed in
the continuous process, but in the former, a
special still must be provided for working up the
weak wash waters unless this is done in the main
batch still between esterification charges

55
 Hydrolysis
• Introduction
• The term hydrolysis is applied to the reaction in which water effects
a double decomposition with another compound, hydrogen goes to
one of the product, hydroxyl to the other.
• Breaking down of proteins, the saponification of fats and other esters
are the examples of hydrolysis.
• It is very difficult to carry out effective hydrolysis with water alone
even at high temperature and pressure.
• For completion and speedy hydrolysis an accelerating agent of some
kind is always added.
• The most important accelerating agents are alkali, acid and
hydrolyzing enzyme, although ion-exchange resins have also been
used. 56
 Hydrolysis
• The enzymes (organic catalyst) are of surpassing importance in vital
processes, both animal and plant.
• Different examples of hydrolysis reaction are as follows.
KCN + H2O → HCN + KOH
CH3COOC2H5 + NaOH → CH3COONa + C2H5OH

57
• Different hydrolyzing agent used for hydrolysis
• The important hydrolysis agents are
 Water
 Water - acid (acid hydrolysis)
 Water-alkali (alkali hydrolysis)
 Enzymes (enzymatic hydrolysis)
• Water:
• Although the word hydrolysis means decomposition by water, cases in which water
unaided brings about effective hydrolysis are rare, but are there few specific reaction
where water alone acting as effective hydrolysis agent.
• Hydrolysis of Grignard reagent takes place completely and quickly by water alone.
• The acid anhydrides, lactones, lactides and other internal anhydrides such as ethylene
oxide are readily hydrolyzed by water.
• Alkyl halide of complex composition reacts with water alone, e.g.

58
• Diazonium salt when heated with water hydrolyzed completely

• Ethyl hydrogen sulfate, sodium salt of acetoacetic ester can be completely

hydrolyzed by water.
• A slight degree of hydrolysis seems to occur with numerous materials such as
esters carbohydrates etc. but it should be noted that water by itself is able to
bring about complete and rapid hydrolysis of only very few substances.
• The use of steam rather that water has brought good result.
• Benzene sulfonic acid with steams yields benzene and sulfuric acid similarly
a-naphthalene sulfonic acid hydrolyzes to naphthalene.

59
• Acid hydrolysis
• The use of acid in hydrolysis is rapidly extended to organic materials
such as esters, sugar, amide etc.
• it was found that acid accelerates the reaction.
• It also initiates the reaction where water alone fails to complete the
hydrolysis.
• This effect is due to hydrogen ion content of acid.
• Hydrochloric and sulfuric acids are the most commonly used.
• Formic acid and trichloro acetic acid appears to be lower in activity
whereas oxalic and benzene sulfonic acid are more active.
• Sulfuric acid is particularly useful because it forms, with many types of
organic substances, intermediate compound that themselves readily
undergo hydrolysis; sulfuric acid exhibits a specific action, distinct from
its hydrogen ion concentration, and cannot be replaced by other acids.60
• Organic esters of all kinds, including the esters
of carbohydrates are quite subject to hydrolysis
with acid.

61
• Alkali hydrolysis
• Sodium hydroxide is most commonly used, but alkali carbonates and bicarbonates
as well as the alkaline earth hydroxides all find occasional application.
• Potassium hydroxide shows no advantage over other hydroxides except in some case
permits the use of a lower temperature.
• Ammonium hydroxide and ammonium salts are rarely used.
• Hydroxyl ion catalyzes the hydrolysis.
• Acid is one of the products of hydrolysis that immediately reacts with hydroxyl ion.
• Alkali hydrolysis is distinguished into three cases.
• > The use of low concentration of alkali in the hydrolysis of esters and similar
material.

62
• The use of sufficient caustic under pressure and in high
concentrations to unite with all the acid produced

• The fusion of organic material with caustic soda or

potash.

63
• Enzymatic hydrolysis
• Very few enzymes are used for hydrolysis on
large scale.
• Molasses is converted by invertase in the
manufacture of industrial alcohol.
• Conversion of starch into glucose and maltose by
amylase enzyme.
• Carbohydrate to cellobiose by enzyme cellulose
are the few examples of enzymatic hydrolysis
where enzymes are used.

64
• Thermodynamic of hydrolysis
• The extent to which a chemical reaction may proceed
under a given set of condition is given by the equilibrium
state.
• The driving force of the reaction is the change in free
energy, which is related to the equilibrium constant (K) by
ΔF° = - RT In K
• Where, superscript o indicates that all reactant and products
are in the same standard state.
• Thermodynamics relations relates the change in free
energy to the heat of reaction Also:
ΔF° = ΔH° - TΔS° 65
• Where, ΔH° is the heat of the reaction ΔS° is the entropy
change.
• If free energy change (ΔF°) is -ve, the reaction is
spontaneous and favorable and if free energy change is
+ve and greater than 10 kcal/mole then the reaction is not
suitable for practical application. E.g. Hydration of
Ethyne
C2H4(g) + H2O → C2H5OH(g) ΔH296 = -1.1 kcal/mole
• It is seen that log k and thus ΔF° becomes zero at
approximately 70°C (experimental) or 90°C (calculated).
• At temperature below these value the formation of alcohol
is favored (k>1) and at higher temperature the dehydration
to ethylene takes place (k<1). 66
• Kinetics of hydrolysis
• In commercial processes, it is very important whether
reactions goes fast or slow, if the reaction is
thermodynamically possible but proceeds with slow rate
then for desirable result, it is modified by:
 Changing temperature,
 Pressure and
 Concentration ratios,
 A catalyst may be employed
• The data obtained on reaction rates may be interpreted
through either the collision theory or the theory of
absolute reaction rate. 67
• The collision theory emphasis on the energy of
activation as the rate-determining factor, which
may be related to temperature (T) and the rate
constant (k) by Arrehenius equation
k = pze(-Ea /RT)
• Where,
 Ea = Activation energy
 Z = frequency of collision at unit concentration of
reactant
 R = Gas constant
 P = probability factor 68
• The newer theory, called transition state theory,
places emphasis on the free energy of activation and
is concern with thermodynamic probability of
attaining an activated complex, one form of rate
constant expression is

• Where, ΔH° = heat of the reaction

• ΔS° =entropy change
69
• Mechanism of hydrolysis
• Hydrolysis of Ester
• Extensive study of the hydrolysis of ester has shown that reaction is
reversible and catalyzed by both H3O+and OH- ions.
• The addition of acid speeds up the reaction but scarcely shift the
equilibrium position, where, the addition of sufficient base not only
increase the rate but also causes the reaction to go completion by
neutralization of the acid product.
• Ingold has proposed eight possible mechanisms for ester hydrolysis
BAC1, BAC2, BAL1, BAL2, AAC1, AAC2, AAL1 and AAL2

B =Basic hydrolysis AL=Alkyl oxygen fission

A =Acidic hydrolysis 1=Unimolecular process
AC= Acyl oxygen fission 2=Bimolecular process 70
• The most common case of basic hydrolysis
follows BAC2 mechanism, which is represented
as follows:

• or considering the intermediate to be transition

state of nucleophilic substitution.

71
 HYDRATION
• The addition of water molecule to olefinic double bond will produce
alcohol.
• Such reaction is known as hydration.
• Protic acid i.e. HCl, H2SO4, HNO3 and H3PO4 are used as a catalyst in
hydration process.
• The role of catalyst in hydration process is formation of 6-π complex.
• Isopropyl is produced from propylene:
H2C=CH2 + H2O → CH3CH2OH

72
• Hydration across the triple bonds of acetylene
and nitriles give aldehyde and amide
respectively.

73
• Products obtained by hydration process
• Ethanol
 Ethanol is a liquid which having 78oC boiling point. It is used as solvent and it
is also used in food and drug industries.
• Diethyl ether
 Its boiling point is 34oC, it is highly flammable.
 It is used as solvent in drug industries.
• Isopropyl alcohol
 Its boiling point is 82.5oC, miscible in water.
 Its vapor produces explosive mixture with air within the concentration limit (2-
12%).
 It can be used as solvent in place of ethanol.
• Secondary and tertiary butyl alcohol
 Both solvents are colorless liquid having 99.5oC and 82oC boiling point
respectively.
 They are used for manufacture of methyl ethyl ketone.
74
 Equipment used in hydration process
Horizontal absorber with disk mixer

• This type of reactor is made of horizontal column containing stirrer.

• The olefins and H2SO4 has to be charge from upper side of the reactor.
• Water is circulated continuously through jacket which absorbs the heat,
producing during the reaction.
• Products like alcohol coming out from the bottom of the reactor.
75
• Continuous column type tray
absorber
• It is made up of single vertical
column containing number of
horizontal trays.
• Between each two horizontal trays,
one cooling system is installed.
• Sulfuric acid and olefins are passed
counter currently in the reactor.
• Water is circulated continuously
through cooling system which
absorbs the heat, producing during
the reaction.
• 90% pure product is coming out
from the bottom of the reactor.
76
• Direct hydration
• Generally in hydration process sulfuric acid is used
as catalyst with water.
• Because of water concentration of sulfuric acid will
decreases up to 45% to overcome this problem
direct hydration is used where addition is carried out
across the double bond of olefins.
• It is a single step process where sulfuric acid is not
used so no need to regenerate the sulfuric acid and
so corrosion problem can be removed.
• The yield of alcohol is about 95%.

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 Ethanol
• Raw materials Ethylene
• Water
• Reaction
• H2C=CH2 + H2O→ CH3CH2OH

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• Compressed ethylene is first passed from heat
exchanger where it is slightly heated with flash
water and recycled water.
• Now this heated reaction mixture is heated in
tubular furnace up to 2500C.
• After that reaction mixture is neutralized with the
help of caustic soda.
• Followed by the cooling mass is separated in
separator in liquid and gas phase.

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• Gaseous vapor containing ethanol is absorbs in
absorber by water and unreacted ethylene is recycled
through compressor.
• Liquid phase from separator is send to another gas
liquid separator where dissolved gas in liquid can be
separated out.
• While liquid phase is charged in to separating column
where diethyl ether is vaporized and remaining phase
is fractionated in next column where ethanol is
distilled out from the top of the column and water is
finally recycled through ion exchange unit.
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