The basic principle for definition of the term “fine chemicals” is a three-tier

segmentation of the universe of chemicals into commodities, fine chemicals,

and specialty chemicals. Fine chemicals account for the smallest
part, about 4–5% of the total $1.8 trillion turnover of the chemical industry

Commodities are large-volume, low-price, homogeneous, and standardized chemicals

produced in dedicated plants and used for a large variety of applications. Prices are cyclic
and fully transparent. Petrochemicals, basic chemicals, heavy organic and inorganic
chemicals (large-volume) monomers, commodity fibers, and plastics are all part of
commodities. Typical examples of single products are ethylene, propylene, caprolactame,
methanol, BTX (benzene, toluene, xylenes), phthalic anhydride, poly (vinyl chloride), soda,
and sulfuric acid,

Fine chemicals are complex, single, pure chemical substances. They are produced in limited
quantities (<1000 metric tons per year) in multipurpose plants by multistep batch chemical
or biotech(nological) processes. They are sold for more than $10 per kilogram, based on
exacting specifi cations, for further processing within the chemical industry. The category is
further subdivided on the basis of either the added value (building blocks, advanced
intermediates, or active ingredients) or the type of business transaction (standard or
exclusive products).
Specialty chemicals are formulations of chemicals containing one or more fine
chemicals as active ingredients. They are identifi ed according to performance
properties. customers are trades outside the chemical industry and the public. Specialty
chemicals are usually sold under brand names.
Electronic chemicals

Merck KGaA produces a range of individual fi ne chemicals as active substances for liquid
crystals in a modern multipurpose plant in Darmstadt, Germany. An example is
(trans,trans)-4- [difl uoromethoxy)-3,5-difl uorophenyl]-4′-propyl-1,1′-bicyclohexyl…..Fine
Chemicals
Merck ships the active ingredients to its secondary plants in Japan, South Korea, and
Taiwan, where they are compounded into liquid crystal formulations. These specialties have
to comply with stringent use-related specifi cations (electrical and color properties, etc.)of
the Asian producers of consumer electronics such as cellular phones, DVD players,
and flat-screen TV sets

“Commoditized specialty” chemicals contain commodities as active ingredients

and are interchangeable. Thus, ethylene glycol “99%” is a commodity.
If it is diluted with water, enhanced with a colorant, and sold as “superantifreeze”
in a retail shop, it becomes a commoditized specialty.
 Before the nineteenth century, chemists
generally believed that compounds
obtained from living organisms were too
complex to be synthesized. According to
the concept of vitalism, organic matter
was endowed with a "vital force". They
named these compounds "organic" and
directed their investigations toward
inorganic materials that seemed more
easily studied.
Jöns Jacob Berzelius (1779–1848) Friedrich Wöhler

In 1828 Friedrich Wöhler produced the organic chemical urea (carbamide), a constituent
of urine, from the inorganic ammonium cyanate NH4CNO, in what is now called
the Wöhler synthesis. Although Wöhler was always cautious about claiming that he had
disproved the theory of vital force, this event has often been thought of as a turning
point.
Kolbe’s synthesis of acetic acid from its constituent elements in 1845 (Kobe, 1845).
First synthetic dye, mauveine (aniline purple) by Perkin in 1856 Perkin, 1856, 1862).

This is generally regarded as the first industrial organic synthesis.

 Catalysis
Catalysis is the key to chemical transformations. Most industrial syntheses and nearly all
biological reactions require catalysts. Furthermore, catalysis is the most important technology
in environmental protection, i. e., the prevention of emissions.

The term “catalysis” was introduced as early as 1836 by

Berzelius in order to explain various decomposition and
transformation reactions. He assumed that catalysts
possess special powers that can influence the affinity of
chemical substances.

A definition that is still valid today is due to Ostwald (1895):

“a catalyst accelerates a chemical reaction without affecting the position of the equilibrium.”
While it was formerly assumed that the catalyst remained unchanged in the course
of the reaction, it is now known that the catalyst is involved in chemical bonding
with the reactants during the catalytic process. Thus catalysis is a cyclic process:
the reactants are bound to one form of the catalyst, and the products are released
from another, regenerating the initial state.

In theory, an ideal catalyst would not be consumed, but this is not the case in
practice. Owing to competing reactions, the catalyst undergoes chemical changes,
and its activity becomes lower (catalyst deactivation). Thus catalysts must be regenerated
or eventually replaced.
another important property:
They can influence the selectivity of chemical
reactions.

Completely different products can be obtained

from a given starting material by using
different catalyst systems.

can be
gases, liquids, or solids
Mode of Action of Catalysts
The suitability of a catalyst for an industrial process depends mainly on the following
three properties:
– Activity
– Selectivity
– Stability (deactivation behavior)
The question which of these functions is the most important is generally difficult to
answer and depend on the demand.

ACTIVITY
The reaction rate r is calculated as the rate of change of the amount of substance
nA of reactant A with time relative to the reaction volume or the mass of catalyst:
Empirical rate equations are obtained by measuring reaction rates at various concentrations
and temperatures.

If, however, different catalysts are to be compared for a given reaction, the use of constant
concentration and temperature conditions is often difficult because each catalyst requires it
own optimal conditions. In this case it is appropriate to use the initial reaction rates r0
obtained by extrapolation to the start of the reaction.

Another measure of catalyst activity is the turnover number TON, which originates
from the field of enzymatic catalysis.
space–time yield STY
The chemical, thermal, and mechanical stability of a catalyst determines its lifetime
in industrial reactors. Catalyst stability is influenced by numerous factors, including
decomposition, coking, and poisoning. Catalyst deactivation can be followed by
measuring activity or selectivity as a function of time.
HETEROGENIOUS CATALYSIS

Processes Involved
Homogeneous Catalysis

Steps involved: complexation

Decomplexation
In homogeneous catalysis using transition metals the catalytic centre comprises a metal
atom surrounded by ligands.

Transition metals are very versatile catalysts, mainly as a result of their variability of
oxidation state and co-ordination number.

Of great importance is their ability to readily interchange between oxidation states and to
rapidly change between co-ordination numbers.
catalytic cycle starts with the so-called oxidative addition

After the creation of vacant site by loosing a PPh3 ligand, ethylene interacts with Rh by
co-ordination,

Then insertion of the ethylene takes place to form an ethyl group

The hydride ion then combines with the ethyl to form ethane, which leaves the co-
ordination sphere of the metal

This process is called reductive

elimination which is
essentially the
reverse of oxidative addition

Some principles of homogeneous transition-metal catalysis" L = PPh3 c.n. = coordination

number; o.s. = oxidation state
HETEROGENEOUS CATALYSTS- TYPES AND PREPARATION

Catalysts can be divided in classes in several ways. Based on their appearance catalysts can
be subdivided into:

1. soluble catalysts (homogeneous),

2. bio-catalysts (enzymatic),
3. solid catalysts (heterogeneous).
Composition
Catalyst Production

Raney Nickel: It is prepared by the reaction of a powdered nickel-aluminium alloy with

aqueous sodium hydroxide to selectively remove a large fraction of the
aluminium component. The product consists of porous nickel with a high
surface area. The remaining aluminium probably has an essential function in
stabilizing the small nickel particles.
Raney Nickel

Very useful catalyst for hydrogenation

Disadvantages
a) Sensitive to poisoning
b) Not very effective at high temperature
c) Regeneration is not cost effective
d) Sensitive to air and thus needs to be stored in water
e) Can not store for longer period
Catalyst supports
Most of these supports have surface area in the range of 100-700 m2/g

Choice of support depends on the following parameters

a) Surface area
b) Pore size
c) Heat transfer capacity
d) Regenerability
Alumina
Zeolites
From X-ray Diffraction patterns it is clear that the material shows only weak broad
lines, characteristic of non-crystalline materials. Silica and alumina are typical
examples. Zeolites are an exception: they are crystalline materials but nevertheless
exhibit high (micro) porosity.

belong to the class of molecular sieves, which are porous solids with pores of
molecular dimensions, i.e., typically the pore diameter ranges from 0.3 to 10 nm.
Examples of molecular sieves are carbons, oxides and zeolites.
Zeolites Preparation
First an amorphous alumino-silicate gel is formed. This process is completely
analogous to the production of alumina and silica gels described before.
Subsequently this gel is crystallized into zeolite.
Activated carbons can be prepared from a wide variety of carbonaceous materials such as
wood, coal, lignite, and sugar. Usually, the manufacturing process consists of pyrolysis
followed by 'activation' (partial gasification). The specific surface area of activated carbon
can be quite high, up to 1500 - 2000 mZ/g, and the surface can be highly functionalized.
 PHASE-TRANSFER CATALYSIS

In the mid-1960s a series of papers by Makosza and Serafinowa (1965, 1966) appeared
under the common title "Reactions of Organic Anions", in which the catalytic alkylation of
phenylacetonitrile and its derivatives carried out in the presence of concentrated NaOH and
the catalyst triethylbenzylammonium chloride (TEBA) was described. This was the beginning
of phase-transfer catalysis (PTC), and since then thousands of papers haven been published on
the subject.
 Suitable catalysts for PTC are those which have a highly lipophilic cation (i.e. have strong
affinity for an organic solvent

Catalysts used most extensively are quaternary ammonium or

phosphonium salts (quats). Examples are tetra-n-butylammonium bromide (TBAB),
triethylbenzylammonium chloride (TEBA) and methyltrioctylammonium chloride (Aliquat
336 or Adogen 464).
Neutral complexants for organic cations, e.g. crown ethers, poly(ethylene glycol)s (PEGs),
cryptands, etc., are also suitable catalysts. Open chain PEGs (e.g. PEG 400) are the least
expensive catalysts and may be preferable to quats in some processes.