SLIDES 1&2

Course Outline---- Nitration • Esterification • Amination • Halogenation • Sulphonation • Oxidation •

Hydrogenation • Introduction to biochemical engineering……..Role of Thermodynamics in UP • Knowledge of
thermodynamics and kinetics is fundamental for complete understanding of UP . • Chemical thermodynamics can
be used to predict: Certain reaction takes place or not? – Extent of Conversion – Temperature and Pressure Effects
on Reaction behavior – Composition of Reactor effluents if Equilibrium is reached – Driving Force of Several
Competing Reactions – Amount of Heat Released……….Basic Concepts in Thermodynamics….>> 1-Energy balances
– Equilibrium Conversion – Heat requirements – Quantity of Catalyst • Energy balances are based upon 1st Law of
thermodynamics which is: • Energy cannot be created or destroyed during a process, although it may change from
one form to another. The total energy of system entering a process plus any addition during the process must be
equal to the total energy of the system leaving the process…………Basic Concepts in Thermodynamics …>>>>Energy
Classifications • Can be classified into two groups: 1) Related to the system – Internal Energy – Flow or Pressure
energy – Kinetic Energy – Potential Energy 2) Associated with the process – Heat – Work……….Basic Concepts in
Thermodynamics::: Energy Balance over a Flow System • The first law of thermodynamics when applied to two
points in a flow system can be expressed as:

• For chemical processes, changes in kinetic and potential energy are negligible and also if system performs no work,
above equation reduces to:

Basic Concepts in Thermodynamics Standard States • To fix the properties of a component in a system, a standard
state must be defined which specifies: – Temperature – Pressure – Physical State Heat of Reaction • The change in
enthalpy of a system when a reaction occurs is usually called heat of reaction, it is also called enthalpy change on
reaction.

Thermodynamics and Unit Processes • Thermal Effects – Heat of reaction and effect of temperature on heat of
reaction – Sensible heat transfer in preheating and cooling – Heat effects in phase transformations • Chemical
Equilibrium Calculations – Equilibrium constant – Effect of Temperature on equilibrium constant – Extent (how far) of
reaction – Concentration of desired product in reactor effluent
Topics to be covered • Chemical Kinetics – Order of Reaction – Mechanism of Reaction – Effect of Temperature on
Reaction Rate – Types of Chemical Reactions
• Chemical Process Kinetics – Types of Reactors
Chemical Kinetics • It is a study of the rates of chemical reaction and the effect that process conditions (temperature,
pressure and reactant concentration) have on these rates. • Application of kinetics is important in selection and
design of reactors. …… Order of Reaction • Can be calculated by the sum of exponents of the concentration terms
in the rate equation.

• The order of reaction is a+b

Chemical Kinetics ….Mechanism of Reaction • A reaction usually does not occur in a single step but rather in a series
of steps. These steps are called the mechanism of the reaction. • For example,
Chemical Kinetics ….Effect of Temperature on Reaction Rate • The rate equation only defined by concentration of
reactants while the effect of temperature appears in rate constant k. • The relationship between reaction rate
constant (k) and temperature is given by Arrhenius law as follows:
𝑘 = 𝐴𝑒^(−𝐸 𝑅𝑇)
Chemical Kinetics Types of Chemical Reactions • Number of phases involved during reaction (Heterogeneous or
Homogenous) • Mechanism of reaction (Chain, Photochemical, etc.) • Presence of Catalyst (Catalytic or Noncatalytic)
• Operation (Adiabatic, Isothermal)
Chemical Process Kinetics • Study of the influence of the physical factors that affect chemical reactions – Type and
shape of reactor – Method of operation (batch, continuous, recycle) – Temperature control (isothermal, adiabatic)
– Back mixing (Diffusion or mixing of products back to reactants) – Fixed or fluidized bed (important in case of
catalytic reactions)……. Chemical Process Kinetics Types of Reactors • Batch Reactors – Most common type – Used
at small scale to obtain kinetic data – Reactants are charged at the beginning with no mass transfer until the reaction
is complete. • Semi-batch Reactors – Continuous addition of one reactant or continuous removal of product during
reaction……….Chemical Process Kinetics Types of Reactors • Continuous Reactors 1) Tubular reactors – No diffusion
or mixing of product with reactants (no back-mixing) 2) Stirred-tank continuous reactors (CSTR) – Complete back-
mixing 3) Tower – Provide large volumes – Back-mixing occurs
Topics to be covered ……..• Introduction • Nitrating Agents • Mechanism of Nitration • Aromatic and Paraffinic
Nitration • Kinetics of Aromatic Nitration • Thermodynamics of Nitration • Equipment For Nitration Processes •
Industrial Applications……….Introduction • The reaction between nitrating agent and another reacting compound
that results in one or more nitro (--NO2) groups chemically bonded to an atom in this compound. • The nitro group
(--NO2) may become chemically attached to a carbon (nitroaromatic or nitroparaffinic), oxygen (nitrate ester), or
nitrogen (nitramine) . • A hydrogen atom is often replaced by the nitro group and this is of great technical
importance.
Introduction (Contd.) • Three general reactions summarize nitration chemistry: 1. Carbon nitration:

2. Oxygen nitration:

3. Nitrogen nitration:
Nitrating Agents • A variety of reagents can be used for nitration. • These include: Concentrated and aqueous
nitric acid. Mixtures of nitric acid with sulfuric acid, acetic anhydride, acetic acid, phosphoric acid and chloroform.
Nitrogen Pentoxide (N2O5) and nitrogen tetroxide (N2O4). • For selecting suitable nitrating agent it is desirable to
know: Species present in the system for reaction. Mechanism of the reaction with the selected nitrating agent
Nitryl Ion • Mixture of nitric acid and sulfuric acid (mixed acid) is the most important nitrating medium. • Nitric
acid exists in strong sulfuric acid as the nitryl ion NO2+.

• In weaker solutions of sulfuric acid, ionization of nitric acid is very slight but rapidly increases as the sulfuric acid
becomes more concentrated………Mechanism of Nitration • The mechanism of nitration depends on the reactants
and the operating conditions. • The nitration reactions usually follow two types of mechanism: 1. Ionic 2. Free-
radical……. • Ionic nitration is commonly used for aromatics, heterocyclic compounds, hydroxyl compounds and
amines. • Nitration of paraffins, cycloparaffins and olefins frequently involves free-radical mechanism………Ionic
Nitration of Aromatics • Most ionic nitrations are performed at 0-120°C. For nitrations of most aromatics, there are
two liquid phases: an organic and an acid phase. • Sufficient pressure is provided to maintain the liquid phases. A
large interfacial area between the two phases is needed to accelerate transfer of the reactants to the interface and
of the products from the interface. • The nitration agent is an electrophilic reactant, therefore the substitution will
be electrophilic aromatic substitution………Electrophilic Aromatic Substitution • The characteristic reaction of
benzene is electrophilic aromatic substitution, a hydrogen atom replaced by an electrophile (E+). • Benzene has six
π electrons and these loosely bound π electrons make the benzene ring electron rich and so reacts with electrophiles.
 • Unlike addition reactions, substitution of hydrogen keeps the aromatic ring intact
Mechanism of Substitution Reaction • Regardless of the electrophile used, all electrophilic aromatic substitution
reactions occur by the same two-step mechanism: …….1. Addition of electrophile (E+) to form a resonance-stabilized
carbocation. 2. Deprotonation with base,…….. Formation of Electrophile

Electrophilic Aromatic Substitution

Ionic Nitration of Aromatics …….• NO2+ attacks an aromatic compound (ArH) as follows:

Substitution of Substituted Benzenes • Many substituted benzene rings undergo electrophilic aromatic substitution.
• Already present substituent either increases or decreases the electron density in the benzene ring.

Substitution of Substituted Benzenes • A substituent affects two aspects of the electrophilic aromatic substitution
reaction: ……1. The rate of reaction: A substituted benzene reacts faster or slower than benzene itself. 2. The
orientation: location of new group with respect to the existing substituent.
How large interfacial area can be practically provided between two phases during nitration of aromatics???? • Which
factors decide the position of substitution (ortho, para or meta) in the substituted benzene???? • What are the
benefits of using sulfuric acid with nitric acid during nitration reaction????
Kinetics of Aromatic Nitration
• The rate of nitration reaction can be written as:

• So, the kinetics of aromatic

nitrations are functions of temperature, which affects the kinetic rate constant, and also of the concentration of
both the acid and hydrocarbon phases. • In addition, a larger interfacial area between the two phases increases the
rate of nitration since the main reactions occur at or near the interface.
Kinetics of Aromatic Nitration • The reaction rate also depends on sulfuric acid concentration. • Reaction rate rises
sharply with increasing sulfuric acid concentration and reaches a maximum value at 90% H2SO4. • This increase in
reaction rate is due to the increase in concentration of nitryl ion (electrophile). • But the rate start to decrease at
concentration higher than 90%.
Why rate of reaction decreases with sulfuric acid concentration higher than 90%?????
Kinetics of Aromatic Nitration • The viscosities and densities of the two phases and the interfacial tension between
the phases are important physical properties affecting the interfacial area.
• Such properties are, of course, dependent on both temperature and the respective compositions of the phases.
How density, viscosity and interfacial tension will effect the interfacial area??? How these parameters should be
changed to increase interfacial area?????
Nitration of Paraffins • Both gas-phase and liquid-phase processes are employed to nitrate paraffins, using either
HNO3 or NO2. • The nitration occurs by means of freeradical mechanism. • Sufficiently high temperatures are
required to produce free radicals to initiate the reaction steps
Gas-phase Nitration • Temperature range for gas-phase nitration is 350450°C. • Gas-phase nitrations occur at
atmospheric pressure, but pressures of 0.8 -1.2 MPa (8-12 atm) are frequently employed in industrial units. • The
higher pressures facilitate the condensation and recovery of the nitroparaffin products when cooling water is
employed to cool the product gas stream leaving the reactor.
Liquid-phase Nitration • This reaction is of less importance than the gas-phase because of low yields, lower
conversion and occurrence of side products. • Temperatures of about 150-200°C are usually required. • Sufficient
pressures are needed for the liquid-phase processes to maintain the reactants and products as liquids.
Free Radical Mechanism • In case of HNO3 as a nitrating agent:

 In case of NO2 as a nitrating agent

• Why aromatic compounds follow ionic reaction mechanism and paraffins follow free radical
mechanism?????
Thermodynamics of Nitration • The nitration reaction is highly exothermic. The heat released, for example, in
nitration of 1 lb of benzene is comparable to that released on condensation of 1 lb of steam. • Study of thermal
properties of nitrating acids is essential for adequate understanding of the process. • To design nitrating equipment
and providing safe and efficient operations knowledge of thermodynamic data (heat of nitration, heats of solution,
heats of dilution) is essential. • The nitration reaction must be controlled by systematic cooling designed to remove
the heat released. • The heat released or the enthalpy change due to the process equals the heat lost to the cooling
mechanism as follows: Q = - H
Process Equipment for Nitration • Two types of operation can be used for nitration: 1. Batch Nitration 2. Continuous
Nitration
Pros and Cons of Batch Process Pros • Simple and ideal for small scale experimental studies on reaction kinetics •
Easy cleaning in case of fouling • Lower capital investment • Easier to start up and shut down Cons • High labor
costs • Dead time • Can be difficult to control highly exothermic reactions
Pros and Cons of Continuous Process Pros • Ideal for industrial purposes when large quantities of material are to
be processed • Facilitates good quality control for the product through the provision of greater constancy in reaction
conditions • Minimizes the labor costs • No dead time involved …Cons • High capital costs
Batch Nitration • Nitration is usually done in closed cast iron or steel vessels. Modern practice is to use mild carbon
steel. • Nitrator consists of a cylindrical vessel containing some kind of cooling surface, a means of agitation, feed
inlets and product outlet lines. • They are also equipped with a large diameter quick dumping line for emergency
use if the reaction gets out of control. • The contents of the nitrator are dumped rapidly into a large volume of water
contained in a drowning tub. A common accessory for the nitrator is a suction line in the vapor space above the
liquid charge to remove the acid fumes and oxides of nitrogen which may be liberated. • Two factors which are of
prime importance in the design of nitrators are: • Degree of agitation • Control of temperature. • Temperature
control is generally accomplished by coils of tubes through which cold water for cooling or hot water and steam for
heating may be circulated. • A wall jacket is usually not sufficient enough for nitration reaction except in the case of
vessels of very small capacity. Advantages of coils: • High coolant velocity is possible • More compact so can be
installed anywhere in the tank. Disadvantages of coils: • Fouling and scaling problem • Cleaning is not easy .. • The
most common type of agitating system used in nitrators consists of a vertical shaft with one or more propellers
mounted on it.
Continuous Nitration • Same type of vessel as used for batch nitration, with the exception that an overflow pipe is
provided for the continuous withdrawal of product and that continuous feed of reactants is provided. • Atomization
is there in continuous process. Two typical nitrators for continuous operation are: • Schmid Nitrator • Biazzi Nitrator

Schmid Nitrator • Material to be nitrated is fed at the top of the nitrator and is immediately drawn down and
thoroughly mixed with the acid. • In the bottom of the nitrator, fresh mixed acid is fed in and mixed with the other
reactant by means of agitator provided. • The reacting material then pass upwards through the tubes surrounded
by refrigerated brine. Product and spent acid are withdrawn continuously from the nitrator through the overflow

line.
In this apparatus the turbine type agitator provides intensive agitation. A vortex is formed in the center about the
agitator shaft. The reactants (acid and hydrocarbon) fed from the top are immediately drawn into the vortex
thoroughly mixed and circulated down through the center of the bank of cooling coils and back up through and
around the coils. • The high velocity imparted to the nitrator contents makes efficient mixing and heat transfer.

Health and Safety Factors • The danger of explosion of a nitrated product generally increases as the degree of
nitration increases, e.g., trinitroaromatics are more hazardous as compared to dinitroaromatics or
mononitroaromatics. • Nitroaromatics and some polynitrated paraffins are highly toxic when inhaled or when
contacted with the skin. All nitrated compounds tend to be highly flammable.
INDUSTRIAL APPLICATIONS…1- Nitrobenzene Manufacturing • Nitrobenzene, C6H5NO2, is a pale yellow liquid with
an odor that resembles bitter almonds. • Nitrobenzene is slightly soluble in water and is readily soluble in most
organic solvents. • It is a good organic solvent. • Nitrobenzene is made by direct nitration of benzene using a mixture
of nitric acid and sulfuric acid.
 • This process may be carried out by a Batch operation Continuous operation • The continuous process is more
effective for large amount of production.
Steps of Nitrobenzene Manufacturing • Both batch and continuous processes involve following steps: Nitration
reaction Washing of crude nitrobenzene Distillation to separate water‚ benzene and dinitrobenzene.
Batch Nitration Process • Composition of mixed acid used is: HNO3 27 to 32 wt % H2SO4 56to
60 wt % H2O 8 to 17 wt %
• Cast-iron nitrating vessels are used. • The temperature of the mixture is maintained at 50-55°C by adjusting the
amount of cooling. • The process requires lot of agitation due to the required mass and heat exchange. • The batch
reaction time generally is 2-4 hours. After that nitrobenzene is separated‚ washed and distilled. • The selectivity
reaches 98 to 99%.
Continuous Nitration Process • Continuous nitration process generally offers more efficient labor usage than a batch
process, most of the nitrobenzene producers use continuous processes. • Composition of mixed acid used is:: HNO3
20 to 26 wt % H2SO4 56 to 65 wt % H2O 15 to 18 wt %
• Benzene and nitrating acid are fed into the nitrator, which can be a stirred cylindrical reactor with internal cooling
coils. • The nitrator also can be designed as a tubular reactor, e.g., a tube-and-shell heat exchanger with appropriate
cooling. • A slight excess of benzene is usually fed into the nitrator to ensure that the nitric acid is consumed to the
maximum possible extent.
Economic Aspects • The main parameter affecting the economic aspects for nitrobenzene production is process
related cost including raw material costs, energy requirements, waste treatment, etc. • The most significant cost
related to the production process is the raw material cost. These typically are at least 85% of the production costs
for nitrobenzene.
Health and Safety Factors • Nitrobenzene is a very toxic substance; the maximum allowable concentration for
nitrobenzene is 5 mg/m3. • It is readily absorbed by contact with skin and by inhalation of vapor. • Exposure to
nitrobenzene may irritate the skin and eyes. • Nitrobenzene affects the central nervous system and produces
fatigue, headache, vomiting, general weakness, and in some cases unconsciousness and coma. • In areas of high
vapor concentrations (>1 ppm), full face masks or air-supplied respirators should be used. • Clean work clothing
should be worn daily and showering after each shift should be mandatory. • With respect to the hazards of fire and
explosion, nitrobenzene is classified as a moderate hazard when exposed to heat or flame.
Uses of Nitrobenzene • The largest end use for nitrobenzene is in the production of aniline. Approximately 95-98%
of nitrobenzene is converted to aniline; the demand for nitrobenzene fluctuates with the demand for aniline. • The
other uses are in p-aminophenol‚ dyes, pigments, as a chemical intermediate and solvent.
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