Physical Properties of Benzene

1. Aromatic hydrocarbons like benzene are colorless and have characteristic odor.
2. Benzene is toxic and carcinogenic in nature.
3. It is a non-polar molecule and exists in the form of colorless liquid and highly
inflammable in nature.
4. That is the reason, the bottle of benzene are marketed with the warning of toxic and
flammable liquid.
5. Because of the high percentage of carbon atom compare to alkanes, Benzene burns with
sooty flame and less denser than water.
6. The density of benzene is 0.8765 g/cm 3 and melts at 278.7 K. The boiling point of
benzene is 353.3 K temperature.

Chemical Properties of Benzene

Benzene undergoes substitution reactions in spite of the high degree of unsaturation. This
behavior of benzene is called as aromaticity or aromatic character. Aromaticity of
benzene can be easily explained on the basis of resonance structure of benzene. During
additional reactions of benzene, it will lose its aromaticity, hence its preferred to undergo
substitution instead of additional reaction.
In benzene there are three pi bonds located in hexagonal ring in alternate manner. These
pi bonds get delocalized in ring and make molecule stable. The carbon atoms in benzene
are sp2 hybridized and each carbon atom has one unhybridized p-orbital. These six
unhybridized p-orbitals get delocalized above and below the plane of ring.

Since six pi electrons are delocalized over whole ring, therefore the cyclically conjugated
double bonds represents by a circle and the carbon-carbon bond length becomes
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equal. This structure of benzene is called as resonance hybrid of benzene and generally
used
to
represents
the
benzene
molecule.

Thus due to resonance and high electron density, benzene mainly undergoes electrophilic
substitution reaction. It can show additional and oxidation reactions also in the presence of
strong reagents. Some common chemical properties of benzene are as follows.

Electrophilic substitution reaction

The most common substitution with benzene is electrophilic substitution reaction which is a
multi-step reaction. The catalysts and co-reagents react to generate a strong electrophilic
species in initial step of the substitution. Electrophile interacts with benzene with to form a
cyclohexadienyl cation which is known as Wheland complex or the s complex or the arenium
ion. In second step, base involves in reaction and reacts with s complex to form substituted
product through deprotonation.

Arenium ion is a stable intermediate due to delocalization of positive charge on ring.

Electrophilic substitution reactions with electrophile, products and catalyst as follows.

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Since the intermediate formed during the substitution reaction is not aromatic in nature, therefore
reaction will continue until the aromaticity has been regained.

Nitration
1. A nitro group can be introduced into benzene by using a nitrating mixture to form nitro
benzene.
2. The nitrating mixture is a mixture of concentrated nitric acid and concentrated sulfuric
acid.
3. Here sulfuric acid acts as catalyst and responsible for the formation of electrophile that
is nitronium ion (NO2+).
4. When benzene is treated with this nitrating mixture at a temperature below 50C, it forms
nitrobenzene. Its an example of electrophilic substitution reaction of benzene and
completed through the formation of arenium ion as an intermediate.
Since sulfuric acid is a strong acid than nitric acid, it gets protonated the nitric acid which causes
the loss of a water molecule and form electrophile, nitronium ion. In the absence of sulfuric acid,
it is not possible to protonate the nitric acid due to its acidic properties.
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Nitration Mechanism
The reaction of benzene with concentrated nitric acid and sulfuric acid give nitro benzene. This
reaction is known as nitration of benzene. It follows electrophilic substitution mechanism and
completed in three steps.

The presence of concentrated sulfuric acid activates the nitric acid to form a
stronger electrophile; nitronium ion (NO2+). Since this is the reaction between two
acids, therefore one acts as Bronsted acid and another as Bronsted base. Out of
these two acids, sulfuric acid is a stronger one, hence acts as Bronsted acid and
protonated nitric acid. The protonation of nitric acid results loss of water molecule
and form nitronium ion.

In the second step, electrophile attacks on benzene ring to form intermediate and lose the
aromaticity.

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Further this intermediate reacts with base that is bisulphate ion (HSO 4- ion) produce in first step.
Base gets deprotonate the intermediate to form nitrobenzene and sulphuric acid which acts as a
catalyst for reaction.

Environmental Fate
Benzene is mainly found in crude oil, gasoline and cigarette smoke. Because of various
industrial processes like burning coal, tobacco smoke, gasoline leaks, it enters in air, water,
and soil. Many natural sources like crude oil seeps, volcanoes and forest fires are also
responsible for expose of benzene. Benzene is degradable substance up to a level by
volatilization, bio-degradation under aerobic conditions or photo oxidation with hydroxyl
radicals. In metropolitan areas, it found around 0.58 ppb in air sample and less than 5 ppb in
sediment sample. While the level of benzene found in surface water samples is around 100
g/L. The degradation of benzene in air, water and soil results the formation of other aromatic
compounds like nitro benzene, nitro phenols, dihydroxy benzene etc.

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Continuous reactors
An alternative to a batch process is to feed the reactants continuously into the reactor at one
point, allow the reaction to take place and withdraw the products at another point. There must
be an equal flow rate of reactants and products. While continuous reactors are rarely used in
the laboratory, a water-softener can be regarded as an example of a continuous process. Hard
water from the mains is passed through a tube containing an ion-exchange resin. Reaction
occurs down the tube and soft water pours out at the exit.

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Continuous reactors are normally installed when large quantities of a chemical are being
produced. It is important that the reactor can operate for several months without a shutdown.
The residence time in the reactor is controlled by the feed rate of reactants to the reactor. For
example, if a reactor has a volume of 20 m3 and the feed rate of reactants is 40 m3 h-1 the
residence time is 20 m3 /40 m3 h-1 = 0.5 h. It is simple to control accurately the flow rate of
reactants. The volume is fixed and therefore the residence time in the reactor is also well
controlled.
The product tends to be of a more consistent quality from a continuous reactor because the
reaction parameters (e.g. residence time, temperature and pressure) are better controlled than
in batch operations.
They also produce less waste and require much lower storage of both raw materials and
products resulting in a more efficient operation. Capital costs per tonne of product produced
are consequently lower. The main disadvantage is their lack of flexibility as once the reactor
has been built it is only in rare cases that it can be used to perform a different chemical
reaction.

Types of continuous reactors

Industry uses several types of continuous reactors.

(a) Tubular reactors

In a tubular reactor, fluids (gases and/or liquids) flow through it at high velocities. As the
reactants flow, for example along a heated pipe, they are converted to products (Figure 4). At
these high velocities, the products are unable to diffuse back and there is little or no back
mixing. The conditions are referred to as plug flow. This reduces the occurrence of side
reactions and increases the yield of the desired product.
With a constant flow rate, the conditions at any one point remain constant with time and
changes in time of the reaction are measured in terms of the position along the length of the
tube.
The reaction rate is faster at the pipe inlet because the concentration of reactants is at its
highest and the reaction rate reduces as the reactants flow through the pipe due to the decrease
in concentration of the reactant.

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Tubular reactors are used, for example, in the steam cracking of ethane, propane and butane and
naphtha to produce alkenes.

(b) Fixed bed reactors

A heterogeneous catalyst is used frequently in industry where gases flow through a solid
catalyst (which is often in the form of small pellets to increase the surface area). It is often
described as a fixed bed of catalyst (Figure 5).
Among the examples of their use are the manufacture of sulfuric acid (the Contact Process,
with vanadium(V) oxide as catalyst), the manufacture of nitric acid and the manufacture of
ammonia (the Haber Process, with iron as the catalyst).

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A further example of a fixed bed reactor is in catalytic reforming of naphtha to produce

branched chain alkanes, cycloalkanes and aromatic hydrocarbons using usually platinum or a
platinum-rhenium alloy on an alumina support.

(c) Fluid bed reactors

A fluid bed reactor is sometimes used whereby the catalyst particles, which are very fine, sit
on a distributor plate. When the gaseous reactants pass through the distributor plate, the
particles are carried with the gases forming a fluid (Figure 6). This ensures very good mixing
of the reactants with the catalyst, with very high contact between the gaseous molecules and
the catalyst and a good heat transfer. This results in a rapid reaction and a uniform mixture,
reducing the variability of the process conditions.
One example of the use of fluid bed reactors is in the oxychlorination of ethene to
chloroethene (vinyl chloride), the feedstock for the polymer poly(chloroethene) (PVC). The
catalyst is copper(II) chloride and potassium chloride deposited on the surface of alumina.
This support is so fine, it acts as a fluid when gases pass through it.

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(d) Continuous stirred tank reactors, CSTR

In a CSTR, one or more reactants, for example in solution or as a slurry, are introduced into a
reactor equipped with an impeller (stirrer) and the products are removed continuously. The
impeller stirs the reagents vigorously to ensure good mixing so that there is a uniform
composition throughout. The composition at the outlet is the same as in the bulk in the
reactor. These are exactly the opposite conditions to those in a tubular flow reactor where
there is virtually no mixing of the reactants and the products.

A steady state must be reached where the flow rate into the reactor equals the flow rate out, for
otherwise the tank would empty or overflow. The residence time is calculated by dividing the
volume of the tank by the average volumetric flow rate. For example, if the flow of reactants
is 10 m3 h-1 and the tank volume is 1 m3, the residence time is 1/10 h, i.e. 6 minutes.

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A variation of the CSTR is the loop reactor which is relatively simple and cheap to construct
(Figure 11). In the diagram only one loop is shown. However, the residence time in the
reactor is adjusted by altering the length or number of the loops in the reactor.
Loop reactors are used, for example, in the manufacture of poly(ethene) and the manufacture
of poly(propene). Ethene (or propene) and the catalyst are mixed, under pressure, with a
diluent, usually a hydrocarbon. A slurry is produced which is heated and circulated around the
loops. Particles of the polymer gather at the bottom of one of the loop legs and, with some
hydrocarbon diluent, are continuously released from the system. The diluent evaporates,
leaving the solid polymer, and is then cooled to reform a liquid and passed back into the loop
system, thus recirculating the hydrocarbon.

Nitration reactions are among the basic reactions used in chemical synthesis, and
have remained indispensable for the synthesis of pharmaceuticals, agricultural
chemicals,
pigments,
explosives
and
precursors
for
polymers.
The majority of nitrations give off considerable amounts of heat. The highly
exothermic nature of these reactions sometimes with explosive potential along
with the acidic corrosivity of the nitrating agent, makes nitration processes potentially
very hazardous. Marked warming can also cause large numbers of secondary,
consecutive and decomposition reactions to accompany nitration processes. The
occasional result is the formation of unwanted by products such as higher nitrated
compounds or oxidation products. As a consequence, exothermic nitrations exhibit
restrictions
with
respect
to
yield
and
purity
of
target
products.
Nitrations of aromatic compounds are usually electrophilic substitution reactions
which require the acid-catalyzed formation of nitronium ions (NO 2+) as reactive
species, typically realized by employing a mixture of sulfuric acid and nitric acid.
The purpose of using sulfuric acid is not only to donate protons to the nitric acid, thus
forming nitronium ions, but also to bind water that is formed during the reaction.
The use of microreactors for performing aromatic nitration reactions has been
described by several authors. The main drivers in most cases were to find
routes to overcome restrictions in heat and mass transfer resulting in improved
process performance and safety. For example, the nitration of benzene and Other aromatic
compounds is often strongly limited by the mass transfer performance within the reactor that
is used. In particular in the case of biphasic nitration reactions, a good mass transfer
performance is essential to suppress the formation of unwanted by-products such as
higher nitrated compounds (e.g. dinitro and trinitro compounds) or oxidation products.
Therefore, the use Of microreactors offers a good possibility to overcome common
restrictions in mass transport and thus achieve higher yields and selectivities in
nitration reactions. Burns and Ramshaw (12) were among the first to describe the use of
microreactors for the isothermal nitration Of aromatic compounds (Scheme 4.5). They chose
the nitration of benzene as a first test reaction to study the concept Of enhancing diffusion
in a capillary slug flow micro reactor applied for the reaction Of two immiscible liquid
phases (in this case benzene and aqueous nitrating acid (H2S04 + HNO3)). A high
sulfuric acid concentration was used to ensure fast nitration kinetics and promote a
mass transfer-limited regime. The reaction was performed in stainless-steel capillaries
Of different width (127 and 254 um) at temperatures between 60 and 90C (in later
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studies, PTFE capillary microreactors were used to avoid corrosion problems within
the setup). Relative high conversion rates achieving up to 50% nitrobenzene were
obtained for residence times Of only a seconds: 94% conversion was obtained in
24s while maintaining low by-product levels. As expected, the narrower capillary reactor
yielded significantly higher conversion than the broader reactor due to
smaller diffusion lengths 1214. An enhancement of reaction rate was also observed
when higher flow rates were applied, leading to increased mixing. Results for the benzene
nitration indicated reaction rates in the range 18 min-1 that can be provided from a capillary
slug-flow reactor depending on the process conditions applied. Consequently, residence times
for complete conversion were estimated to be in the range 10-60s.

Additional CFD calculations indicated that the enhancement of mass transfer is a result of
an internal circulation flow within the plugs (Figure 4.1). As a consequence, mixing inside
the plug is also enhanced. yielding decreasing amounts of sequential by-products.

This is actually the mass transfer added process because this is increased microreactor that is
why we used it.

Decanter
A decanter is used to separate the organic and acid phases.
The term 'decant' is usually associated with wine. Decanting is also a chemical laboratory
process used to separate mixtures.
Answer: Decanting is a process to separate mixtures. Decanting is just allowing a mixture
of solid and liquid or two immiscible liquids to settle and separate by gravity. This process can
be slow and tedious without the aid of a centrifuge. Once the mixture components have
separated, the lighter liquid is poured off leaving the heavier liquid or solid behind. Typically, a
small amount of the lighter liquid is left behind. In laboratory conditions, small volumes of
mixtures are decanted in test tubes. If time is not a concern, the test tube is kept at a 45 angle in
a test tube rack. This allows the heavier particles to slide down the side of the test tube while
allowing the lighter liquid a path to rise to the top. If the test tube were held vertically, the
heavier mixture component could block the test tube and not allow the lighter liquid to pass as it
rises.
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Nitrobenzene
C6H5NO2, very poisonous, flammable, pale yellow, liquid aromatic compound with an odor like
that of bitteralmonds. It is sometimes called oil of mirbane or nitrobenzol. Nitrobenzene melts at
5.85C;, boils at 210.9C;, is only slightly soluble inwater, but is very soluble in ethanol, ether, a
nd benzene.

Plug Flow Hydrogenation Reactor

Plug Flow Reactor employed in industrial application where high exothermic or

explosive energy involved in carrying the chemical reaction.
It ensures safe heat transfer between the instrument and the surrounding.
It is commonly used to ensure static mixing of the components.

Works effectively under condition

Constant density
Balanced conditions
A single reaction
Plug flow

Features

Uniform distribution
Short residence time
Advanced technique
Smooth appearance
Quality design
Ensure safe heat transfer
Static mixing of components

Flow Capacity of Tubular Reactors

Very wide range of flows are possible, subject to pump range and pressure drop across
reactor.
Gas and liquid flow rate determines:
the "pattern" of flow
Gas/liquid mixing and contact with catalyst
Conversion
'Ease of scale up
Flows rates widely selected to favour that "trickle bed" mode.

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