Mizan Tepi University

College of Natural and Computational Science

Department of Chemistry

Course:- Industrial Chemistry I

Instructor : Debela Jufar (M.Sc.)
E-mail Address :- debelajuf2008@gmail.com
12/07/2023 +251984926308 1
 CHAPTER ONE
Introduction to industrial chemistry
What is the difference between Chemistry and Industrial Chemistry?

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 Difference between Chemistry and Industrial Chemistry
 Desired product is produced at
small scale in the lab
 The parameters such as
Temperature Pressure and
Concentration etc are set through
usual methods
 Different equipment and
instruments may not be required
to use
 Material balance and energy
balance may not be considered
 Cost of production may not be
considered
 Only chemist can perform the
chemical process(reaction)
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 Desired product is produced at large
scale in the industry
 The parameters such as Temperature
Pressure and Concentration etc are
monitored by sophisticated instrument
such as computers.
 Different equipment and instruments
are used in industrial process.
 Material balance and energy balance
must be considered.
 Cost effective production is to be
considered
 Along with Chemist, chemical,
electrical, mechanical engineers
experts required to carry out the
process. 3
 Definition:-
 Industry is a general term that refers to all economic activities that
deal with production of goods and services.
 Industrial Chemistry is the study of different chemical process
involved in the industry for the manufacture of synthetic products
like; Cement, Plastics, Glass, Paints, Medicines, Fertilizers, Food, and
other industrial products.
 Industrial chemistry as the branch of chemistry which applies
physical and chemical procedures towards the transformation of
natural raw materials and their derivatives to products that are
benefit to humanity.
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 Every industrial process is designed to produce a desired product

from a variety of starting raw materials using energy through a

succession of treatment steps integrated in a rational fashion.

 A chemical process consists of a combination of chemical reactions

such as synthesis, calcinations, ion exchange, electrolysis,

oxidation, hydration and operations based on physical phenomena

such as evaporation, filtration, crystallization, distillation and

extraction

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 It is combination of unit processes and Unit operation
 The layout of a chemical process indicates areas where:

 raw materials are pre-treated

 conversion takes place

 separation of products from by-products is carried out

 refining/purification of products takes place

 entry and exit points of services such as cooling water and steam

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Characteristics of the Chemical Industry
 Basic objective - make a profit
 Very competitive
 Highly dependent on science and technology
 Spends large amounts of money on designing of reactor
 Large capital requirements - to construct, expand and maintain
production facilities
 Low labor requirements - BUT needs highly qualified personnel
 Industry Growth - generally through integration rather than
diversification

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 Unit process and unit operations
 Unit processes: are the chemical transformations or conversions
that are performed in a process.
 involves principle chemical conversions leading to synthesis of
various useful product
 provide basic information regarding the reaction temperature and
pressure, extent of chemical conversions
 and yield of product of reaction nature of reaction whether
endothermic or exothermic, type of catalyst used

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Examples of
unit processes

 Unit operations
 Unit operations are the physical treatment steps applied in chemical
processes to transform raw materials and products into required
forms.
 These are the physical treatment steps, which are required to:
 put the raw materials in a form in which they can be reacted

chemically
 put the product in a form which is suitable for the market
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 Examples of unit operations

 Every chemical process can possess either batch process, semi

batch or continuous process
 Batch Processing is a manufacturing process in which components
or goods are produced in groups (batches) and not in a continuous
stream
 Therefore, Processing of subsequent batches must wait until the
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current batch is finished. Baked goods
 Characteristic of batch process

 Each batch is closed system

 The total mass of each batch is fixed

 The volume or density vary

 Residence time the same for all element

 The operation of rector is inherently un-steady

 Composition, temperature the same at any point

 Energy of the batch may be vary eg. Heat exchanger

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 Batch Production Examples
Clothing
Computer chips
Production of dye staffs
Computer software.
Electrical goods
Flat-pack furniture
 Semi batch process or semi continuous process is a process
containing both characteristic of batch and continuous process.
Example washing of machine, fermentation of purge etc.
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 Advantages of using batch production:
 Batch reactors are very versatile and are used for a variety for
different unit operations (batch distillation,
storage, crystallization, liquid-liquid extraction etc.) in addition to
chemical reactions.
 There is a large number of batch reactors within industry and their
method of use is well established.
 Batch reactors are excellent at handling difficult materials
like slurries or products with a tendency to foul.
 Batch reactors represent an effective and economic solution for
many types of slow reactions.
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 In continuous process raw materials are continuously feed into the
reactor and products continuously leave out the reactor.
 Continuous reactors are used for a wide variety
of chemical and biological processes within the food, chemical
and pharmaceutical industries.
 For most applications, continuous flow saves time, energy and costs.
 ones the reactor operates it stays several months
 the process is easy to clean the reactor

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 Benefits of continuous reactors
Continuous reactors are generally able to cope with much higher
reactant concentrations due to their superior heat transfer capacities.
The small size of continuous reactors makes higher mixing rates
possible.
The output from a continuous reactor can be altered by varying the run
time. This increases operating flexibility for manufacturers.
Reduces waste
Increases productivity-more units completed in less time.
Improves quality by making it easier to spot and correct errors.
• Examples,
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production of ammonia by Haber process, and sugar
15
 Figure : a continuous reactor
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  Process variables
 Process variables are parameters which determine the rate of
kinetics and mechanism of reaction in the unit process.
 These are reaction temperatures, pressures, Residence time, volume
of reactor, concentration of reacting species, and others.
 Variables can be either independent variable or dependent variable
based on relations each other.
 Example Fertilizer used to stimulate for the growth of plant.
 From this fertilizer is independent variable where as growth of plant
is dependent variable.

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 Material and Energy balance

 Material balance is the application of the law of conservation of

mass in the form of equations to satisfy balances of total masses,
components and atomic species through a process

 One ton of total material input will only give one ton of total output,

i.e. total mass of input = total mass of output.

 They are used in industry to calculate mass flow rates of different

streams entering or leaving chemical or physical processes

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 Mass balance calculations serve the following purposes:

 They help us know the amount and composition of each stream

in the process.

 The calculations obtained in 1 form the basis for energy balances

through the application of the law of conservation of energy.

 We are able to make technical and economic evaluation of the

process and process units from the knowledge of material and

energy consumption and product yield obtained.

 We can quantitatively know the environmental emissions of the

process.
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In mass balance calculations, we begin with two assumptions

There is no transfer of mass to energy

Mass is conserved for each element or compound on
either molar or weight basis
During mass balance it is important to note the following:
 Mass and atoms are conserved
 Moles are conserved only when there is no reaction
 Volume is not conserved.

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 General mass balance equation
 Input (enters through system boundaries) + Generation (produced
within system boundaries)
− Output (leaves through system boundaries) − Consumption
(consumed within system) = accumulation (buildup within system)

Material balance for an element of volume of the reactor.

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  The concept of energy conservation as expressed by an energy
balance equation is central to chemical engineering calculations.
 Energy balances can be calculated on the basis of external energy
used per kilogram of product, or raw material processed, or on dry
solids or some key component.
 Non isothermal operations energy balances must be used in
conjunction with material balances.

Energy balance =

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 
Energy In = Energy Out + Energy Stored
ΣER= ΣEP+ ΣEW+ ΣEL+ ΣES

Where
ΣER= ER1+ ER2+ ER3+ ……. = Total Energy Entering
ΣEp= EP1+ EP2+ EP3+ ……. = Total Energy Leaving with
Products
ΣEW= EW1+ EW2+ EW3+ … = Total Energy Leaving with Waste
Materials
ΣEL= EL1+ EL2+ EL3+ ……. = Total Energy Lost to Surroundings

ΣES= ES1+ ES2+ ES3+ ……. = Total Energy Stored

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 general flow chart about Mass and Energy Balance
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 A “system” is an object or a collection of objects that an analysis is
done on
 The system has a definite boundary, called the system
boundary, that is chosen and Specified at the beginning of the
analysis
 Once a system is defined, through the choice of a system
boundary, everything external to it is called the surroundings.
 All energy and material that are transferred out of the system enter
the surroundings, and vice versa

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 system

An isolated If heat and work open system can

system is a system are exchanged
that does not exchange heat,
across a system’s work, and material
exchange heat, boundary, but
work, or material with the
material is not, it
with the is a closed system surroundings.
surroundings

 The accumulation term for steady-state continuous processes

is zero.
 The material balance equation becomes:
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The generation and consumption of material are the consequences
of chemical reactions.
If there is no chemical reaction, the production and consumption
terms are typically zero and
the balance equation for steady-state physical process will be simply
reduced to:

Input = Output

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 The general procedure for carrying out mass balance calculations is as
follows:

1. Make a block diagram (flow sheet) over the process

2. Put numbers on all the streams
3. List down all the components that participate in the
process.
4. Find the components that are in each stream and list them
adjacent to the stream in the block diagram
5. Decide on an appropriate basis for the calculations e.g.
100kg raw material A, 100kg/hr A, 1 ton of product, 100
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moles reactant B etc.
 6. Find out the total number of independent relations. This is
equivalent to the total number of stream components.
7. Put up different relations between stream components and
independent relations to calculate concentrations
8. Tabulate results.
Example1 A feed stream is flowing at a mass flow rate of
100 kg/min. The stream contains 20 kg/min NaOH and 80 kg/min
of water. The distillate flows at 40 kg/min and contains 5 kg/min
NaOH. Determine bottom stream mass flow rate and composition.

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Example 2. An aqueous solution of sodium hydroxide contains 20%
NaOH by mass. It is desired to produce an 8% NaOH solution by
diluting a stream of the 20% solution with a stream of pure water.

1. Calculate the ratios (g H2O/g feed solution) and (g product solution/g

feed solution).
2. Determine the feed rates of 20% solution and diluting water needed
to produce 2310 lbm/min of the 8% solution
Solution
 We could take a basis of 2310 lbm product/min, but for illustrative
purposes and to have neater numbers to work with let us choose a
different basis and scale the final results.
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Example 3

Calculate the unknown flow rate and composition of stream 1, 2, and 3

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 CHAPTER TWO
WATER IN CHEMICAL INDUSTRY

 Water is by far the most common liquid on the Earth’s surface, and
its unique properties enable life to exist.
 Water is usually regarded as a public resource a common good
because it is essential for human life and society.
 Water is an essential constituent of all animal and vegetable matter

 Industrially water used as in three categories process water,

cooling, and heating with a shifting emphasis important for each
industry.
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 Industrial water is used for fabricating, processing,
washing, diluting, cooling, or transporting a product.

 Water is distributed in nature in different forms such as:

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 Water molecule attracted to each other and to many solutes by
moderately strong “hydrogen bonds.
 The hydrogen bonds in ice and liquid water,∼21 kJ/mol,14 are much
weaker than the O-H bond of water (464 kJ/mol),
 but they are stronger than London-van der Waals forces (<4 kJ/mol).
Dissolved and suspended solid in water

Total dissolved solids (TDS) are inorganic salts and small amounts
of organic matter present in solution of water.

The principal constituents are usually calcium, magnesium, sodium,

and potassium cations and carbonate, hydrogen carbonate, chloride,
sulfate, and nitrate anions. 39
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 Generally their permissible limits has been up to 5 to 10 ppm (part

per million) or mg/ liter

TDS measures the solids remaining in a water sample filtered

through a 1.2 μm filter.

TDS is used to estimate the quality of drinking water, because

it represents the amount of ions in the water.

 Water with high TDS often has a bad taste and/or high water

hardness, and could result in a laxative effect.

TDS can be determined by evaporating a pre-filtered sample to

dryness, and then finding the mass of the dry residue per liter of
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A second method uses a Vernier Conductivity Probe to determine

the ability of the dissolved salts and their resulting ions in an unfiltered

sample to conduct an electrical current.

The conductivity is then converted to TDS
 The relationship of TDS and specific conductance of ground water
can be approximated by the following equation:
 TDS = keEC

where TDS is expressed in mg/L and EC is the electrical conductivity

in microsiemens per centimeter at 25 °C. The correlation factor ke

varies
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between 0.55 and 0.8. 41
 However, the tests described here will not tell you the specific ion
responsible for the increase or decrease in TDS (electrical
conductivity).

 Total Suspended Solids (TSS) are solids in water that can be

trapped by a filter.

 TSS include silt, stirred-up bottom sediment, decaying plant matter,

or sewage-treatment effluent.

 TSS will not pass through a filter, where as dissolved solids can pass

 The TSS test indicates whether it is likely that solids suspended in a

wastewater can be removed by settling, floating or filtering
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 Over load of TDS and TSS leads to hardness of water

Hard water contains dissolved salts of calcium and magnesium

present as bicarbonates, sulphate and chlorides.
These salts give insoluble precipitates with soap.
Sources of the inorganic species in natural waters can be divided into
two broad categories: natural and human derived.
In turn, natural sources can be divided into terrestrial and
atmospheric.
The former involve weathering reactions of rocks, minerals, and
soils in the catchment of a water body or solid matrix of an aquifer.

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 The latter represent a transport mechanism rather than an ultimate
source
The human source may be comes from effluent of inorganic
chemical industries, mining and other manufacturing sector.
 Weathering dissolution of mineral as Congruent and Incongruent
Congruent :- solid phase dissolves to form only soluble species, and
no new solid phase is formed. Dissolution of simple salts, including
metal sulfates and carbonates, behaves this way.
For example, limestone (impure calcium carbonate) dissolves to form
only calcium and bicarbonate ions:
CaCO3(s) + H2O+CO2 (aq) → Ca2+ (aq) +2HCO3- (aq)

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Incongruent:- Primary silicate minerals such as feldspars and secondary
alumino silicate clay minerals dissolve incongruently, forming a
secondary mineral phase, in addition to releasing ions to solution.
basic rocks/minerals +acidic rain → base cations + alkalinity +silica +
clay minerals
For example, albite, a sodium feldspar, reacts as follows:
NaAlSi3O8(s) + H2O+CO2 (aq) → Na+ +HCO3 +
2Si(OH)4(aq) + Al2Si2O5(OH)4(s) all in solution kaolinite

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 Hardness and alkalinity are usually closely correlated because they
are derived in large part from a common source dissolution of
limestone (CaCO3)
Hard waters tend to be high in total dissolved solids (TDS) and have
relatively high pH (>7).
Waters often are classified according to hardness as follows:
Hardness meq/L mg/L as CaCO3
Soft <1 <50
Moderately hard 1–3 50–150
Hard 3–6 150–300
Very Hard >6 >300
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 The process of removing divalent cations from water is called
softening of water

Alkalinity, which is defined as the sum of the “titratable bases in

water,” may be expressed in milli equivalents per liter (meq/L) or

micro equivalents per liter (µeq/L)

It is the capacity of base to neutralize an acid.

Alkalinity = [OH-] + [HCO3-] + [CO3-]- [H+]
Total inorganic carbon = [H2CO3] + [HCO3-] + [CO3-2]

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 Requisites of water for industry
The importance of suitably preparing water for chemical industry is
now well recognized and various processes for purification.
If free from mineral salts ,should be soft water

 Because hard water causes the formation CaCO3 on industrial

boilers which is an economic headache, because CaCO3 is a poor

heat conductor.
 Fuel efficiency is drastically cut and boilers have been put
completely out of action by local overheating due to boiler scale.
The fabric fibers adsorb calcium and magnesium salts and this
makes them brittle
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48
 Food loses its nutritional value when boiled in hard waters.
The intense corrosion of boilers and heat exchangers takes place
because of the hydrolysis of magnesium salts and the increased
concentration of H+ ions in the solution.

Mg2+ + H2O → Mg(OH)2 + 2H+

Scale deposits on the surfaces of heat exchangers (boilers,

condensers) reduce the efficiency of such equipment.
Scale has low heat conductivity and increases fuel consumption.

Water should be
It should not be turbid, Turbidity should be less than 10 ppm on silica
scale.
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49
 It should be colorless.

It should be odorless and must have an agreeable taste

Water should be obtained from a source that is free from pollution.

All kinds of bacteria and microorganisms should be absent.

Water supply system should be free from health hazards and

sanitary defects.

pH should be in the neutral region

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 The various important factors which are responsible for
color, odor and taste are :
 Presence of iron and maganese in appreciable concentration impart
colour to water.
 Presence of algae in water during collection, which multiply during
storage.
 Electrolytic corrosion of the metal of the water pipe.
 Presence of bacteria in water being stored. These bacteria reduce
sulphates to sulphides which produce H2S by hydrolysis.

 Presence of organic matter in water.

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  Water treatment
Water treatment transforms raw surface and groundwater into safe
drinking water and for industrial applications.
Water treatment involves two major processes:
physical removal of solids and
chemical disinfection.

Surface Water Treatment Plant

Ozonation Coagulant, pH Adjustment Disinfectant (Cl2, NaOCl)

Raw Water Mixing Flocculation Filtration

Storage Sedimentation
Clear Well

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Distribution
  Sedimentation
 The simplest way to clarify muddy water is to allow the suspended
material in it to settle.
 This process, known as sedimentation, takes place when water is
allowed to stand in a reservoir or to flow through a series of settling
tanks.
 Removal of coarse, dispersed and colloidal impurities from water is
known as clarification.
 The suspended and colloidal impurities are separated in
sedimentation tanks by gravitation.

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 The main principle of sedimentation is to allow water to rest or flow
at a very slow velocity so that heavier particles settle down due to
gravity.
Sedimentation takes a long time, requires large capacity settling
tanks and can not ensure complete removal of coarse dispersed
impurities from water
 Filtration of water is done in order to remove colloidal and
suspended matter remaining after sedimentation and to remove
bacterial load.
 The process of filtration usually consists in allowing the water to
pass through thick layers of sand, called media which act as
strainers.
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 The chemical characteristics of water get altered and the number of
bacteria present in water is considerably reduced.
 Types of Filtration
 Rapid filtration - uses gravity (faster flow).
 Slow filtration - uses gravity [slower flow].
 Pressure sand filters-use water pressure.
 Micro straining - uses fine steel fabric (sometimes used prior to other
filtrations).

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Filter media should be:

 coarse enough to retain large quantities of flock

 sufficiently fine to prevent passage of suspended solids
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  deep enough to allow relative long filter runs
 May be mesh screens, cartridges with fibrous elements, or media
(sand or carbon or both)
 Removes particles that are too small to be removed in
sedimentation basins

 Coagulation of water
 Sedimentation alone is not sufficient to remove all the suspended
mater.
 The process of coagulation is used to remove colloidal particles
from water.

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  The process of consolidation of colloidal particles, terminating in
precipitation of the substance removed from the treated water by
settling or filtration is called coagulation.
 Use reagents so as to remove colloidal and coarse dispersed
impurities.
 Since, colloidal particles of a given substance carry same charges,
they are very stable and cannot be easily coagulated or consolidated
into coarse formations.
 In water treatment technology ferrous sulphate (FeSO 4.7H2O),

aluminum sulphate (Al2(SO4)3.18H2O) and ferric chloride (FeCl3)

are used as coagulants.
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 When a coagulant such as aluminiumsulphate is added to water,
it undergoes hydrolysis according to the equation.
Al2(SO4)3 + 6H2O ⇌ 2Al(OH)3 + 3H2SO4
The hydrolysis of aluminiumsulphate gives complex ions whose
charge depends on the pH of the medium. The hydrolysis product
[Al2(OH)5Cl] promote coagulation of natural water.
 Ferric chloride is the most important in the iron containing
coagulants.

 Ferrous iron is used as a coagulant when it is added to chlorine

(Cl2 + FeSO4.7H2O), in the ratio by weight of 1:8.

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 6FeSO4 + 3Cl2→2Fe2(SO4)3 + 2FeCl3

 Coagulation is especially effective with subsequent liming.

FeSO4.7H2O + Ca(OH)2→ Fe(OH)2 + CaSO4 + 7H2O

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 Flocculants
 The process of coagulation can be intensified by adding
special reagents known as flocculants.
 These are the substances, forming colloidal dispersed systems with
water.
 Flocculants work by neutralizing the charge on the colloidal
particles of the coagulant and by destroying the protective
properties of some colloids.
 Flocculants are used to coagulate fine dispersed particles and reduce
the consumption of coagulant 2-3 times.

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  Starch, sodium polyalginate, polyacrylamide, a copolymer of
vinyl acetate and maleic anhydride, activated silica etc are used as
flocculants.
 Polyacrylamide has widely been used as a flocculants. Small
quantities of this additive (up to 1mg/litre) accelerate 10-20 times
coagulation by aluminumsulphate.

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Membrane process
 In a membrane separation process, a feed consisting of a mixture of
two or more components is partially separated by means of a semi
permeable barrier through which one or more species move faster
than the other species. Used as:
Desalting seawater
Holding back seawater intrusion
Treating brackish groundwater
Water softening
Waste water recovery
Removing color, odor, and other organic contaminants
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 Reverse osmosis and electro dialysis
 In osmosis, if a semi-permeable membrane separates two solutions,
solvent from the lower concentration passes to the higher
concentration to equalize the concentration of both.
 But in the reverse osmosis, pressure higher than osmotic pressure is
applied from the higher concentration side so that the path of the
solvent is reversed, i.e. from higher concentration to lower
concentration.

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 Reverse osmosis

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 Reverse osmosis removes the ionic and non-ionic substances in the

water. It also can remove suspended colloidal particles

 Both size and charge are effective

 Single charged H ions pass readily

 Large metallic ions with higher + charge cannot pass easily (Ni, Zn,

Cu, Cd)

 Lower + charges ions can pass (Na, K)

 Dialysis is a process in which diffusion of smaller particles takes

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  Dialysis (DIA) is driving force is a trans membrane concentration
difference Selective passage of ions and low molecular weight
solutes and rejection of larger colloidal and high-molecular-weight
solutes
 In electro dialysis, two electrodes (anode and cathode) are dipped in
brine, separated by semi permeable membrane.
 When current is passed through electrodes, oppositely charged ions
present in sea water pass through membrane towards electrodes.
Chloride ions pass towards anode while sodium ions pass through
cathode.

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 After some time, the water in middle chamber become pure and is
taken out. When outer chambers become more concentrated with
brine, they are also changed.

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Ion exchange process
 Ion exchangers are two types. Anionic & Cationic.
 These are co-polymers of styrene & divinylbenzene.i.e., long chain
organic polymers with a micro porous structure
 Cation exchange resins: containing acidic functional groups such
as -COOH,-SO3H etc. are capable of exchanging their H+ ions with
other cations are called cation exchange resins, represented as RH+
Anion exchange resins: The resins containing amino or quaternary
ammonium or quaternary phosphonium or tertiary sulphonium groups,
treated with “NaOH solution becomes capable of exchanging their OH -
ions with other anions. These are called as Anion exchange resins,
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 Sterilization and Disinfection of Water
 Coagulation and filtration of water through sand purify it from
suspended solids and partly decrease its bacteriological
contamination.
 Complete disinfection is attained by chemical reagents which kill
pathogenic bacteria or microorganisms.
 Chlorine gas and chlorine compounds, such as chlorinated lime,
chloramines, chlorine dioxide, hypochlorite's, as well as ozone, and
salts of heavy metals are effective against microorganisms.
 Ultraviolet radiation, ultrasound and other physical factors also
kill pathogenic organisms.
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 But, the most important and common disinfecting agent used to
treat water is chlorine and chlorine compounds
 For chlorination, chlorine may be used directly in the liquid
form or as bleaching powder.
 The chemical action of chlorine is that it reacts with water to
form hypochlorous acid and nascent oxygen. Both these are
powerful germicides.
 Cl2 + H2O → HOCl (Hypochlorous acid)+HCl
 HOCl→HCl + [Nascent oxygen]

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 Chapter 3
Manufacture of Hydrochloric acid ,
Hydrofluoric acid and Sulphuric acid
 Hydrochloric acid

 hydrochloric acid is the aqueous (water-based) solution of

Hydrogen chloride gas (HCl).
 It is a strong acid, the major component of gastric acid

 It must be handled with appropriate safety precautions because

it is a highly corrosive liquid.
 Also known as muriatic acid (muriatic means "pertaining to
brine
12/07/2023or salt) by its historical but still occasionally used name
77
 Manufacturing of HCl

 Hydrochloric Acid can be manufactured either purposely or as a by-

product
 However, the volume of hydrochloric acid manufactured as a by-
product is so important that hydrochloric acid is not often produced
purposely
 Main process:-

 Burner Process (inorganic direct synthesis),

 Organic By-product Synthesis,
 Waste Incineration

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 Burner Process
Chlorine and hydrogen react exothermally to form hydrogen chloride
gas as follows:
Cl2(g) + H2 (g)  2HCl (g)
Both gases pass through a burner nozzle, and are ignited inside a
graphite combustion chamber, which is cooled by water.
The hydrogen chloride gas produced is cooled, and absorbed into
water to give hydrochloric acid at the desired concentration.

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 Organic By-product Synthesis
 Hydrochloric acid is made during chlorination of organic products as
follows:

 RH + Cl2  RCl + HCl

 where R stands for organic products and RCl stands for chlorinated
organic products such as methyl chloride, methylene chloride, alkyl
chloride, etc.

 HCl is also made during fluorination of chlorinated organic

products to manufacture (hydro) chlorofluorocarbons as follows:

 RCl + HF  RF + HCl
12/07/2023 80
 where RCl stands for chloroform, trichloroethane, etc and RF

stands for (hydro)chlorofluorocarbons such as HCFC etc.

 Organic Waste Incineration
 It is made during Incineration, at high temperatures, of chlorinated
wastes as follows:

 RCl + O2  CO2+ H2O + HCl

Where R2HCl are unusable by-products, chlorinated solvents such as

vinyl chloride monomer, etc

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 Cont..
•Reaction of metallic chlorides, particularly sodium chloride (NaCl),
with sulfuric acid(H2SO4) or a hydrogen sulfate

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 Thermal decomposition of the hydrated heavy-metal chlorides
from spent picklen Liquor in metal treatment

 Characteristic of HCl
 HCl is a non-flammable transparent and colorless or light
yellow liquid
 It reacts with a chromate, permanganate, or per sulfate to
generate chlorine; and
 reacts
12/07/2023
with a metal peroxide to form its chloride and chlorine
83
 It has a strong pungent odor, and is highly corrosive.
 It is harmful to humans and animals. The inhalation of a large
quantity of hydrochloric acid will cause intoxication and result in
death

 The shipping containers used for hydrochloric acid are those rail

tanks be tightly sealed, such as acid-resistant bottles (including

polyethylene containers, etc.),and steel drums tank trucks, tank cars,

and tankers with corrosion resistant linings.

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Use of HCl
It is a strong inorganic acid that is used in many industrial processes
Pickling of steel
To remove rust or iron oxide scale from iron or steel before
subsequent processing, such as extrusion, rolling, galvanizing, and
other techniques
 The steel pickling industry has developed hydrochloric acid
regeneration processes, such as the spray roaster or the fluidized
bed HCl regeneration process
Production of organic compounds
 2CH2=CH2 + 4HCl + O2 → 2 ClCH2CH2Cl + 2 H2O (dichloroethane
by oxychlorination)
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 Wood + HCl + heat → activated carbon (chemical activation)
 Production of inorganic compounds
 eg. Fe2O3 + 6HCl → 2 FeCl3 + 3 H2O (iron (III) chloride from
magnetite)
CaCO3 + 2HCl → CaCl2 + CO2 + H2O (calcium chloride from
limestone)
pH Control and neutralization
OH− + HCl → H2O + Cl−
 Regeneration of ion exchangers
HCl is used to rinse the cations from the resins. Na + is replaced with
H+ and Ca2+ with 2 H+
12/07/2023 86
Other
such as leather processing,
purification of common salt,
 household cleaning, and building construction.
 Hydrofluoric acid
HF is a weak inorganic acid used primarily in industrial processes:
glass etching, metal cleaning, electronics manufacturing, laboratory
reagent, etc
Anhydrous hydrogen fluoride is manufactured by the action of
sulfuric acid on calcium fluoride.
The gaseous hydrogen fluoride that leaves the reactor is condensed
and12/07/2023
purified by distillation 87
 CaF2 + H2SO4 CaSO4 +2HF

It can be produced as a byproduct during manufacture of

superphosphate from fluoroapatite.

 Ca5(PO4)3F (s) + 5H2SO4(l) +10H2O 3H3PO4.H2O (aq) +

5CaSO4.2H2O (s) + HF(g)

12/07/2023 88
Some Feature of HF

Colorless liquid with a pungent, irritating, penetrating odour.

Concentrations above 40% fume in air. Will not burn.

Cylinders or tanks may rupture and explode if heated.

Highly reactive Contact with metals, such as iron or steel, slowly

releases flammable and potentially explosive hydrogen gas.

very toxic. May be fatal if inhaled, absorbed through the skin or

swallowed. Corrosive to the nose, throat and respiratory tract.

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 Causes lung injury-effects may be delayed. corrosive to the eyes
and skin.
May cause blindness and permanent scarring.
Absorbed fluoride can cause metabolic imbalances with irregular
heartbeat, nausea, dizziness, and vomiting.
Long-term exposure may cause skeletal fluorosis (weakened bone
structure)
HF etches glass by forming strong bonds between the fluoride
anions and the silicon molecules in glass
HF is reactive with concrete, enamels, glazes, rubber and many
organic compounds
12/07/2023 90
Use of HF
It used for the production of fluorine and hydrogen gas.
 Fluorine is produced commercially by electrolyzing anhydrous HF
containing dissolved potassium fluoride to achieve adequate
conductivity.
 Potassium fluoride and hydrogen fluoride form potassium bifluoride
(KHF2 or KF·HF).

 Fluoride is oxidized at the anode, producing fluorine, and the

hydrogen ion is reduced at the cathode, producing hydrogen gas
 It used in stainless steel pickling, glass etching, metal coatings,
exotic
12/07/2023
metal extraction, and quartz purification. 91
 It use of hydrogen fluoride is in the production of fluorocarbon
chemicals, including
o hydro fluorocarbons,
60% of production is used
o Hydrofluorochlorocarbons, and for this purpose
o fluoropolymers;

12/07/2023 92
  Sulphuric acid (H2SO4)
 Sulfuric acid (H2SO4) is a highly corrosive strong mineral acid.
 It is a colorless to slightly yellow viscous liquid which is soluble in
water at all concentrations
Manufacturing of sulfuric acid
The commonly used raw materials are:
 Elemental sulphur
 Sulphides such as pyrites
 Hydrogen sulphide from petroleum refineries

12/07/2023 93
 Chamber Process and Contact Process of
Manufacturing of H2SO4
 Lead chamber process:
 This process employs as reaction vessels large lead-sheathed brick
towers.
 In these towers, sulphur-dioxide gas, air, steam, and oxides of
nitrogen react to yield sulphuric acid as fine droplets that fall to the
bottom of the chamber

 SO2 + NO2 —> SO3 + NO ; 2NO + O2 —> 2NO2

 SO3 + H2O —> H2SO4

12/07/2023 94
 Sulphuric acid produced in this way is only about 62 to 70 percent
H2SO4
 The chamber process has become obsolete and has been replaced by
the contact process due to the following reasons:
i. An increased demand for strong, pure acid and oleum.
ii. Contact process plants are cheaper and more compact.

 Contact process:
 The contact process, which came into commercial use about 1900,
depends on oxidation of sulphur dioxide to sulphur trioxide, SO3,
under the accelerating influence of a catalyst.
 The first contact plants (before 1920) were built using platinum
12/07/2023 95
catalysts.
 This platinum catalysts has two Limitation
 it is very expensive, and
 it is deactivated by certain impurities in ordinary sulphur dioxide.
 In the middle of 1920s, vanadium catalysts started being used and
have since then replaced platinum.
 By 1930, the contact process could compete with the chamber
process and Because it produces high strength acid, it has almost
replaced the chamber process.

 In general the contact process, SO2 obtained by burning of S or iron

pyrites is catalytically oxidized to SO3 in presence of finely

divided
12/07/2023 Pt or V2O5 as catalyst. 96
 S + O2 --------- SO2 or

 4FeS2 + 11O2 —> 2Fe2O3 + 8SO2

pt/V2O5
 So2 + O2 2SO3.
 The favorable conditions for maximum yield of SO3 are,

 High concentration of SO2 and O2.

 Low temperature of 673 to 723 K,

 High pressure about 2 atmospheres.

 SO3 thus obtained is absorbed in 98% H2SO4 to form oleum which on

dilution with water gives H2SO4 of desired concentration.

 SO3 + H2SO4 —> H2S2O7;

12/07/2023 97
 H S O + H O —> 2H SO
 Oleum
 Contact process is preferred over lead chamber process (gives 98%
pure H2SO4) since it gives H2SO4 of greater purity (100%).

12/07/2023 98
12/07/2023 99
 The efficiency of the absorption step of is SO3 related to:-

 The H2SO4 concentration of the absorbing liquid (98.5-99.5%) .

 The range of temperature of the liquid (normally 70°C-120°C).

 The technique of the distribution of acid
 The raw gas humidity (mist passes the absorption equipment)
 The mist filter
 The temperature of incoming gas

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  Application of H2SO4

 Most of its uses are actually indirect in that the sulphuric acid is
used as a reagent rather than an ingredient.
 The largest single sulphuric acid consumer by far is the fertilizer
industry
 Substantial quantities are used as an acidic dehydrating agent in
organic chemical and petrochemical processes, as well as in oil
refining
 used for pickling and desaling steel; for the extraction of copper,
uranium and vanadium from ores; and in non-ferrous metal
purification and plating.
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 In the inorganic chemical industry, it is used most notably in the

production of titanium dioxide.

 Certain wood pulping processes for paper also require sulphuric

acid, as do some textile and fibers processes (such as rayon and

cellulose manufacture) and leather tanning

 Other end uses for sulphuric acid include: effluent/water treatment,

plasticizers, dyestuffs, explosives,, adhesives, rubbers, edible oils,

lubricants and the manufacture of food acids such as citric acid and
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lactic acid
12/07/2023 103
 Environmental impact

 Sulfuric acid is a constituent of acid rain, being formed by

atmospheric oxidation of sulfur dioxide in the presence of water - i.e.
oxidation of sulfurous acid.
 Sulfur dioxide is the main product when the sulphur in sulfur-
containing fuels such as coal or oil is burned.
 Acid rain can:
 cause deforestation
 acidify waterways to the detriment of aquatic life
 corrode building materials and paints.
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 Sulfuric acid is formed naturally by the oxidation of sulfide minerals,

such as iron sulfide.

 The resulting water can be highly acidic and is called Acid Rock

Drainage (ARD).

 The acidic water so formed can dissolve metals present in sulfide

ores, resulting in brightly colored and toxic streams.

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 Chapter 4
The Common Salts and Chlor-alkali Industries
• Common salts and its resource
 Salt is most widely distributed inorganic compound throughout the
world.
 Sodium chloride (NaCl), also known as salt, common salt, table salt
or halite, is an ionic compound.
 It is a part of human food and life without salt is impossible
 It is responsible for the salinity of the ocean and the
extracellular fluid of many multi-cellular organisms
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 Salt is the basic raw material for the production of caustic soda,
chlorine, soda ash (sodium carbonate), sodium sulfate, hydrochloric
acid etc
 It can be formed by the reaction of hydrochloric acid and sodium
hydroxide
HCl + NaOH → H2O + NaCl
As a solid, sodium chloride is crystalline and forms a cubic lattice
The bonding of the sodium and chlorine atoms is one of the classic
examples of ionic bonding.
Lattice structure of
sodium chloride

12/07/2023 107
 SOURCES OF SODIUM CHLORIDE
 The main source of sodium chloride salt is:
 Sea Water, Salt Lakes, Sub Soil Water, and Rock Salt

 Manufacture table salt

Three main process used
Solar Evaporation
Artificial Evaporation
Freezing method
 Solar Evaporation is the cheapest and best method manufacturing
of salt from the brines.
This method has widely been used in India.
12/07/2023 108
 process
 Sea brine (3-3.5°Be) is first conveyed to a reservoir through
channels to store brine,
 remove suspended impurities and to concentrate the brine from
original, 3-3.5°Be to about 10°Be by solar energy.
The reservoir is usually kept at a certain height, where brine flows
under gravity.
10°Be brine is again concentrated to 25°Be brine by solar
evaporation by passing it to condensers through the channels.

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12/07/2023 110
Due to evaporation of water from brine the solution gradually

concentrates and different impurities separate out at different

concentration as follows

At 7.5°Be ferrous iron present separates out as ferric oxide

At 10°Be, calcium carbonate precipitates out

At12-25°Be, calcium sulfate precipitated out

At the 25 °Be brine from the condensers is now passed on to the

crystallizes, where salt crystallizes from 25.4°Be to 30°Be and other

impurities
12/07/2023 also start separating. 111
 Artificial evaporator

12/07/2023 112
Artificial evaporation was carried out in open pans but it is now

carried out in vacuum pans, known as vacuum evaporation methods.

 At this method, brine is boiled under reduced pressure in vacuum

pan in order to get cubical grains of salt

Addition of chloride removes the last traces of H2S and oxidize

ferrous ion to ferric ion.

Then brine sent to settling tank and it is treated with dilute solution

of caustic soda and soda ash to remove most of calcium, magnesium

and12/07/2023
ferric ions. 113
 Freezing Method
 In some countries, salt is also manufactured by freezing the brine, but
it is not a common method.
 Salt water usually takes short time to freeze as compare to free water.
 This is due to freezing point depurations than pure solvent.
4.2. Chlor-alkali industry introduction

The caustics chain begins with sodium chloride (NaCl) and forms the

basis for what is often referred to as the chlor-alkali industry.

Major products of the chlor-alkali industry include chlorine,

sodium hydroxide (caustic soda), soda ash (sodium carbonate), sodium

12/07/2023 114
bicarbonate, potassium hydroxide, and potassium carbonate.
12/07/2023 115
12/07/2023 116
Manufacture of sodium Carbonate
Soda ash (sodium carbonate) and potash (potassium carbonate),
collectively termed as alkali.
 they are vital chemicals in the glass, textile, soap, and paper
industries.
The traditional source of alkali in Western Europe had been
potash obtained from wood ashes.
Manufacture process
Leblanc process
Deacon process
Solvay process
12/07/2023 117
12/07/2023 118
  Pollution issues of Leblanc process

The Leblanc process plants were quite damaging to the local

environment.

The process of generating salt cake from salt and sulfuric acid

released hydrochloric acid gas.

 because this acid was industrially useless in the early 19th century, it

was simply vented into the atmosphere.

Also, an insoluble, smelly solid waste CaS was produced.

For every 8 tons of soda ash, the process produced 5.5 tons of
12/07/2023 119
This solid waste had no economic value, and was piled in heaps.

where it weathered to release hydrogen sulfide, the toxic gas

responsible for the odor of rotten eggs.

By the 1880s, methods for converting the hydrochloric acid to

chlorine gas for the manufacture of bleaching powder and for

reclaiming the sulfur in the calcium sulfide waste had been discovered,

by Henry Deacon.

but the Leblanc process remained more wasteful and more polluting

than12/07/2023
the Solvay process 120
  Deacon process
 The Deacon process was a secondary process used during the
manufacture of alkalis (the initial end product was sodium carbonate)
by the Leblanc process.
Hydrogen chloride gas was converted to chlorine gas which was
then used to manufacture a commercially valuable bleaching powder,
and
 At the same time the emission of waste hydrochloric acid was
reduced.
Invented by Henry Deacon in 1874. The process was based on the
oxidation of Hydrogen Chloride:
4HCl(g)+
12/07/2023
O2(g) → 2Cl2(g) + 2H2O (aq) 121
 The reaction takes place at about 400 to 450 °C in the presence of a
copper chloride (CuCl2) catalyst.
Three companies developed commercial processes for producing
chlorine based on the Deacon reaction:
 The Kel-Chlor process developed by the M.W. Kellogg Company in
the United States.
The Shell-Chlor process developed by the Shell Oil Company in the
Netherlands.
The MT-Chlor process developed by the Mitsui Toatsu Company in
Japan

12/07/2023 122
  Solvay process

The Solvay process or ammonia-soda process is the major

industrial process for the production of sodium carbonate (soda

ash, Na2CO3).

The ammonia-soda process was developed into its modern form

by Ernest Solvay during the 1860s

The ingredients for this are readily available and inexpensive: salt

brine (from inland sources or from the sea) and limestone (from

quarries)
12/07/2023 123
 Main steps
 Ammonia absorption. NH3 in the recycled gases is dissolved

in brine until a 6 mol L-1NH3 solution is obtained.

 Since this is an exothermic process, cooling is necessary.
 Carbonation. Carbon dioxide from an on-site lime kiln is absorbed
in the ammoniated brine:
NaC1 + NH3 + CO2 + H2O (aq) NaHCO3 + NH4C1.

The precipitated NaHCO3 is filtered.

 The reaction is stopped at about 75% completion, otherwise
NH4HCO3 is also precipitated.

12/07/2023 124
 Calcination. The NaHCO3 product is heated at approximately 150 ~

to form soda ash:

2NaHCO3(s) Na2CO3(s) + H2O(g) + CO2(g).

 Ammonia recovery. The solution phase ("mother liquor") is heated

to expel excess CO2, and then lime from the kiln is added to

regenerate the ammonia for recycling:

2NH4Cl(aq) + Ca(OH)2 CaC12(aq) + 2NH3(g) + 2H2O(1)

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12/07/2023 126
 Applications
A large part of the sodium carbonate consumed is utilized in the
glass industry, of which ca. 40% is used in the manufacture of bottle
12/07/2023 127
glass.
It serves both as a raw material and as a flux for the glass melt to
dissolve the sand. A further 19% is utilized in the manufacture of
chemicals, of which ca. 10% is for the production of :
sodium phosphates, mainly Penta sodium triphosphate, in addition to
silicates (sodium meta silicate pentahydrate and sodium orthosilicate),
chromate, sodium dichromate, sodium hydrogen carbonate, sodium
nitrate etc.
13.5% is utilized in the soap and detergent industry and 2.5% in the
paper and pulp industry

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