WERABE UNIVERSITY

COLLEGE OF NATURAL AND COMPUTATIONAL SCIENCES

DEPARTMENT OF CHEMISTRY

Industrial Chemistry I (Chem 3111)

By: Tesfay Shebeto Araro (MSc)

2014 E.C
 Chapter One

Introduction to Industrial processes,

Unit Operations, Process Variables; and
Material Balances and Energy balances

2
 Industrial Processes

 Every industrial process is designed to produce a desired

product from a variety of starting raw materials using energy
through a series of treatment steps integrated in a rational
fashion.

 The treatment steps are either physical or chemical in nature.

Figure 1: A typical Industrial Process

3
o Energy is an input or output in chemical processes.

 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 are adjusted such as cooling

water and steam

4
 Units that make up a chemical process
 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, crystallization,
distillation and extraction.

 A chemical process is therefore any single processing unit or a

combination of processing units used for the conversion of
raw materials through any combination of chemical and
physical treatment changes into finished products.
5
 Unit processes
o Unit processes are the chemical transformations or
conversions that are performed in a process.
o Examples of some unit processes are given blow.
Acylation Causitization
Calcinations Electrolysis
Dehydrogenation Isomerization
Hydrolysis Amination
Alcoholysis Combustion
Carboxylation Esterification
Decomposition Neutralization
Ion Exchange Ammonolysis
Alkylation Condensation
Oxidation Fermentation
Aromatization Hydrogenation
Dehydration Pyrolysis…etc.
6
 Process Variables
 Figure 2 shows a process stream with several examples of
process variables of input and output. Meanwhile, the details
about process variables are stated in table 1.

Figure 2: Process streams with various process variables.

Table 1: Process variables
 Unit Operations
 There are many types of chemical processes that make up the
global chemical industry.

o However, each may be broken down into a series of steps

called unit operations.

o 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

9
Some common unit operations are given blow.
Agitation Classification
Dispersion Filtration
Heat transfer Pumping
Atomization Crushing
Distillation Flotation
Humidification Settling
Centrifuging Decanting
Evaporation Gas absorption
Mixing Size reduction…etc.

10
Introduction to Material Balance
and Energy Balance

11
 Process Classification
 Batch process
 No mass crosses system boundaries between the time feed
is charged and the time product is removed.
 Typically used for making small quantities.
Example: Rapidly add reactants to a tank and remove the
products and unconsumed reactants some time later when
the system has come to equilibrium.
 Continuous process
 Feeds and effluents continuously flow across the system
boundary through the duration of the process.
 Suited for the production of large quantities.
 Semibatch process
 Any process that is neither batch nor continuous.
12
 • Before writing a material balance (MB) you must first
identify the type of process in question.
 Batch – no material (mass) is transferred into or out of the
system over the time period of interest (e.g., heat a vessel of
water)
 Continuous – material (mass) is transferred into and out of the
system continuously (e.g., pump liquid into a distillation
column and remove the product streams from top and bottom
of column)
 Semi-batch= is when reactants are periodically added or
products are periodically removed.
– any process that is neither batch nor continuous (e.g., slowly
blend two liquids in a tank)
 Steady state

 There is no change in the value of all process variables

(temperature, pressure, flow rates, heat-transfer rates)
except for minor fluctuations about the mean value.

 Continuous processes may be steady-state.

 Transient (Unsteady-State)

 The values of process variables change with time.

 Batch and semi-batch process are transient by nature.

 Continuous processes may be transient.

14
 Pseudo Steady State

 A transient process for which the rate of change of particular

process variables is small may be considered to operate at close
to a steady state over short time periods.

 Classification is assumed in the development of mathematical

relationships that permit the design or describe the performance of
unit operations that involve fundamental phenomena such as heat
or mass transfer, heterogeneous catalysis, phase equilibrium, etc.

15
16
Filling an empty swimming pool with water.
Leave the milk on the counter.
 Cook pasta in boiling water in oven.

17
 The General Balance Equation
• Consider the following continuous process unit for
which methane is a component of both the input and
output, but the measured methane inlet and outlet
mass flow rates are not the same.

• Maybe methane is…

 consumed as a reactant, or generated as a product within
the process unit; or
 accumulating within or leaking from the unit; or
 the measurements are wrong (though we will assume they
are correct).
18
• A balance of a conserved quantity (mass, energy,
momentum) in a system may be written generally as:

input + generation – output – consumption = accumulation

 input: enters through system boundaries

 generation: produced within the system

 output: leaves through system boundaries

 consumption: consumed within the system

 accumulation: buildup within the system

19
Example: Each year, 50,000 people move into a city;
75,000 move out; 22,000 are born; 19,000 are die.
Perform a balance on the population of the city (system).

input + generation – output – consumption = accumulation

 input: 50,000 people/year

 generation: 22,000 people/year

 output: 75,000 people/year

 consumption: 19,000 people/year

 accumulation: unknown
20
input + generation – output – consumption = accumulation

50,000 P/yr + 22,000 P/yr - 75,000 P/yr - 19,000 P/yr = A

A = -22,000 P/yr

∴ The city’s (system) population is decreasing by 22,000

people each year.

21
 Balance Types
 Differential balances
 Indicate state of various rates occurring in a system at an
instant in time. Typically applied to a continuous process.

 Integral balances
 indicate total amounts of a balanced quantity between two
instants of time. Typically applied to a batch process.

22
 Rules of material balance simplification
• If the balanced quantity is total mass (law of conservation of
mass) :- set generation =0 and consumption = 0
Accumulation=In–Out

• If the balance substance is a non-reactive species:-

set generation =0 and consumption = 0

Accumulation=In–Out

• If a system is at steady state:- set accumulation = 0

In–Out+Generation–Consumption=0

23
 Continuous steady-state system
0
input + generation – output – consumption = accumulation

input + generation = output + consumption

• If the balance is for a non-reactive species or on total

mass, the generation and consumption terms equal
zero, and the balance reduces as:

input = output

24
• Benzene/Toluene distillation
 continuous process
 steady-state operation
 no reactions occurring

• General species balance

input + generation –0output – consumption0 = accumulation

0

input = output

25
 input = output
• Benzene balance
500 kg B/h = 450 kg B/h + m2
m2 = 50 kg B/h
• Toluene balance
500 kg T/h = m1 + 475 kg T/h
m1 = 25 kg T/h
• Total mass balance
1000 = 450 + m1 + m2 + 475 (all with units of kg/h)
1000 kg/h = 1000 kg/h ✓

26
Integral Balances on Batch Processes
consider the reaction N2 + H2 → NH3 in a batch reactor
 at t=0, there is n0 moles of NH3 in the reactor
 at t=tf, there is nf moles of NH3 in the reactor
 between 0 and tf, no NH3 crosses system boundary
 NH3 accumulation in system from 0 to tf is ∴ nf – n0.
• therefore, for a batch process,
accumulation = final output – initial input
= generation – consumption
⇒ initial input + generation = final output + consumption
 Identical to continuous steady-state balance except in/out terms denote
discrete amounts instead of flow rates

27
 Batch Mixing Process Balance
• Two methanol-water
mixtures are contained
in a flasks of amounts and
concentrations shown.
• If the flasks are mixed, what is the mass and
concentration of the resulting product?
 no reactions, ∴ generation = consumption = 0
 input = output

28
 • Total Mass Balance
 200 g + 150 g = m = 350 g
• Methanol balance
 
x g CH3OH
200g 
0.400 g CH3OH
g
150g 
0.700 g CH3OH
g

mg 
g
g CH3OH
x  0.529
g
• Water balance
200(0.6) + 150(0.3) = 350(1-0.529)

165 g H2O = 165 g H2O ✓

29
 Process Flowcharts
• A process flowchart is a method for organizing
information about a process in a format that permits
convenient and easy to understand.
• A process flowchart uses boxes and lines with arrows
to represent inputs and outputs of a process.

30
 Labeling Process Flowcharts
1. Write the values of all known stream variables on
the locations of the streams on the chart.
400 mol/h
0.21 mol O2/mol
0.79 mol N2/mol
320°C, 1.4 atm

2. Assign algebraic symbols to unknown stream

variables and write these variable names and their
associated units on the chart.
. 400 mol/h
n (mol/h) y (mol O2/mol)
0.21 mol O2/mol (1-y) (mol N2/mol)
0.79 mol N2/mol 320°C, 1.4 atm
320°C, 1.4 atm

31
 Basis of calculation
 Since a flowchart can always be scaled, material
balance calculations can be performed on the basis
of any convenient set of stream amounts or flow
rates and the results can subsequently be scaled to
any desired extent.
 A basis of calculation is an amount or flow (mass or
molar) of one stream or component in a process.

 The first step in balancing a process is to chose a

basis of calculation; all unknown quantities are then
determined to be consistent with this basis.

32
 If a stream amount or flow is given in a problem statement, it
is usually the most convenient basis to use.

 If no stream amounts or flows are known, assume a value of 1,

preferably for a stream of known composition.

 If mass fractions are known, set a total mass or flow of that

stream (i.e., 100 kg or 100 kg/h) as the basis.

 If mole fractions are known, choose a total number of

moles or molar flow rate.

33
 Balancing a Process
• Suppose 3.0 kg/min of benzene and 1.0 kg/min of
toluene are mixed.
• There are 2 unknown
quantities in this
process, mdot and x, thus 2 equations are needed to
solve for these unknowns.
• For non-reacting processes, the material balance
takes the form: INPUT = OUTPUT.
• 3 balances can be written: one for total mass, and one
for each component (benzene and toluene).

34
•Balances:

 total mass: 3.0 kg/min + 1.0 kg/min = mdot

mdot = 4.0 kg/min

 benzene:3.0 kg C6H6/min = mdot (kg/min) x (X kg C6H6/kg)

3.0 kg C6H6/min = 4.0 kg/min x (X kg C6H6/kg)
x = 0.75 kg C6H6/kg

35
3.0 kg C6H6/min = 4.0 (kg/min) x (0.75 kg C6H6/kg)
3.0 kg C6H6/min= 3.0 kg C6H6/min

 Toluene balance

1.0 Kg C7H8/min= 4.0 Kg/min(1-0.75)Kg C7H8/Kg

1.0 Kg C7H8/min= 1.0 Kg C7H8/min
 Balancing non-reactive processes
 The maximum number of independent equations that
can be derived by writing balances on a non-reactive
system equals the number of chemical species in the
input and output streams.
• In the benzene/toluene example, only two of the three
balance equations are independent, thus only two
unknowns can be found from these balances.

 Write balances first that involve the fewest unknown

variables.

37
Example: An aqueous solution of sodium hydroxide
contains 20.0% mass NaOH. It is desired to produce an
8.0% mass NaOH solution by diluting with pure water.
Calculate the ratios (liters H2O/kg feed solution) and
(kg product solution/kg feed solution).

38
 Balances on a mixing unit
1. Chose basis of calculation and draw/label flowchart.

39
2. Express what the problem asks you to determine in
terms of the labeled variables on the flowchart.
 V1/100 (liters H2O/kg feed solution)
 m2/100 (kg product solution/kg feed solution)

40
3. Count unknown variables and equations. If these
quantities are not equal, problem cannot be solved.
 3 unknowns: m1, m2, V1 (need 3 equations)
 equations:
• 2 species → 2 independent material balances
• density relates V1 to m1.

41
4. Outline solution procedure:

balances have the form INPUT = OUTPUT

1. NaOH balance contains 1 unknown: m2

2. total mass balance contains 2 unknowns: m1 and m2

3. water balance contains 2 unknowns: m1 and m2

4. density relation contains 2 unknowns: V1 and m1

only need 1 of Equations 2 and 3 above

42
5. NaOH balance (INPUT = OUTPUT):

(0.20 kg NaOH/kg)(100 kg) = (0.08 kg NaOH/kg)(m2)

m2 = 250 kg

= 250 kg NaOH

43
6. Total mass balance (INPUT = OUTPUT):

100 kg + m1 = m2 =250 kg

m1 = 150 kg

= 250 kg

= 150 kg

44
7. Diluent water volume:
Density=mass/volume
V1 = m1 / ρH2O = 150 kg /(1 kg/L)

V1 = 150 L

= 250 kg

= 150 kg
= 150 L

45
8. Ratios:

V1 /100 kg = 150 L / (100 kg) = 1.50 L H2O / kg feed solution

m2 /100 kg = 250 kg / 100 kg = 2.50 kg product solution/

kg feed solution

= 250 kg

= 150 kg
= 150 L

46
 Degree of Freedom Analysis
• Process used to determine if a material balance
problems has sufficient specifications to be solved.
a) draw and completely label the flowchart
b) count the unknown variables on the chart
c) count the independent equations relating these variables
d) calculate degrees of freedom by subtracting (c) from (b)

ndf = nunknowns – nindep_eqns

47
 ndf = nunknowns – nindep_eqns

o Possible outcomes of a DFA:

 ndf = 0, there are n independent equations and n unknowns.

The problem can be solved.

 ndf > 0, there are more unknowns than independent equations.

The problem is underspecified. ndf more independent
equations or specifications are needed to solve the problem.

 ndf < 0, there are more independent equations than unknowns.

The problem is over specified with redundant and possibly
inconsistent relations.
48
Sources of equations relating unknown process
stream variables include:
 Material balances. For a non-reactive process, no more
than nms (number of molecular species) independent
material balances may be written.
 Energy balance. An energy balance provides a
relationship between inlet and outlet material flows and
temperatures.
 Process specifications.
 Physical properties and laws.
 Physical constraints.
 Stoichiometric relations. (for reacting systems)

49
General Procedure – Single Unit Op
1.Choose as a basis of calculation an amount or flow rate
of one of the process streams.
 If an amount or flow of a stream is given, it is usually
convenient to use it as the basis of calculation. Subsequently
calculated quantities will be correctly scaled.
 If several stream amounts or flows are given, always use
them collectively as the basis.
 If no stream amount or flow rate is specified, take as a basis
an arbitrarily amount or flow rate of a stream with a known
composition. 50
2. Draw flowchart and fill in all variable values, including the
basis. Label unknown stream variables.
 Flowchart is completely labeled if you can express the
mass / mass flow rate (moles / molar flow rate) of each
component of each stream in terms of labeled quantities.
 Labeled variables for each stream should include 1 of:
a. total mass (or flow), and mass fractions of all stream
components
b. total moles (or flow), and mole fractions of all stream
components
c. mass, moles (or flow) of each component in each stream
• use (c) if no steam information is known
 incorporate given relationships into flowchart
 label volumetric quantities only if necessary
51
3. Express what the problem statement ask you to do in
terms of the labeled variables.

4. If given mixed mass and mole units, convert.

5. Do a degree-of-freedom analysis.

6. If ndf = 0, write equations relating unknowns.

7. Solve the equations in (6).

8. Calculate requested quantities.

9. Scale results if necessary.

52
Example; Constituent balance of milk
Skim milk

53
54
 Recycle

 It is seldom cost effective to waste reactant fed that does not

react to product. More often, this material is separated
(recovered), and recycled (returned to its point of origin for
reuse).

55
56
 Reasons to recycle
 Recover catalyst
 typically most expensive chemical constituent
 Dilute a process stream
 reduce slurry concentration
 Control a process variable
 control heat produced by highly exothermic reaction
 Circulation of a working fluid
 refrigerant

57
 Reasons to recycle
 Recover catalyst
 typically most expensive chemical constituent
 Dilute a process stream
 reduce slurry concentration
 Control a process variable
 control heat produced by highly exothermic reaction
 Circulation of a working fluid
 refrigerant

58
Energy Balance
 Example; Dryer heat balance
A textile dryer is found to consume 4 m3/hr of natural gas with a calorific value
of 800 kJ/m ole. If the throughput of the dryer is 60 kg of wet cloth per hour,
drying it from 55% moisture to 10% moisture, estimate the overall thermal
efficiency of the dryer taking into account the latent heat of evaporation only.
60 kg of wet cloth contains: 60 x 0.55 kg water = 33 kg moisture and
60 x (1-0.55) = 27 kg bone dry cloth.
As the final product contains 10% moisture, the moisture in the product is 27/10
= 2.7 Kg = 3 kg
• And so Moisture removed / hr = 33 - 3 = 30 kg/hr
• Latent heat of evaporation = 2257 kJ/K
• Heat necessary to supply = 30 x 2257 = 6.8 x 104 kJ/hr
Assuming the natural gas to be at standard temperature and pressure at which 1
mole occupies 22.4 litres.
o Rate of flow of natural gas = 4 m3/hr = (4 x 1000)/22.4 = 179 moles/hr
o Heat available from combustion = 179 x 800 = 14.3 x 104 kJ/hr
o Approximate thermal efficiency of dryer = heat needed / heat used
= 6.8 x 104 / 14.3 x 104 = 0.4755 x 100= 48%.
 Chapter – Two
Water in Chemical Industry
 What is chemical Industry?
 refers to the manufacturing of chemical products from raw

materials (chemicals).

 These chemicals are primarily used for starting materials for

consumer goods (plastics, pharmaceuticals, etc), pulp & paper

industry, metallurgy, textiles, construction materials,
agriculture, …

163
 Water is used for the operation in a large number of industries
 as solvent

 Coolant

 for steam generation

 for air conditioning

 fire fighting

 Why is water useful for cooling?

 It is normally plentiful, readily available & inexpensive

 It is easily handled & safe to use

 It can carry large amount of heat per unit volume

 It does not expand or compress significantly within normally

encountered temperature range.

 It does not decompose 164

 Sources of water
-Rain water - purest form obtained as a result of evaporation
contains : dissolved gases ( CO2, SO2, NO etc.) & suspended solid
particles
River water-contains dissolved minerals of inorganic matter and
uprooted and decomposed plants as a result of its flowing in the
surface of the land.
Lake water- stagnant water which allows growth of algae and
aquatic animals which also contains large amount of organic mater
and less amount of dissolved salts.
Sea water: most impure form due to continuous evaporation of
water from the sea.
Underground water: the water which percolates down the earth till
meets the hard rock.
Spring water : after the percolated water level built up in the hard
rocks it starts to move upwards and comes out in the form of spring
water.
77
 Important water quality parameters
-Dissolved gases- very small and negligible amount
-Dissolved liquids-almost absent
-Dissolved solids-have the most reason for the impurities of natural
water which are present either in suspended or in dissolved form.

Determination of total solids: by evaporation of a known amount of

water sample by steam bath in porcelain dish
Total solids( TS) = residue obtained in mg / total volume of sample
water taken.
Determination of total suspended solids: by filtration and drying
technique . TSS=weight of suspended solids / total volume of water
sample ( mg/l)
Total dissolved solids ( TDS) =total solids – total suspended solids.
78
 Characteristics of water quality
 determined by its physical & chemical properties
Hardness of water
 the characteristics of preventing lather formation of water with
soap.
Generally salts like Cl-,HCO3- & SO42- of Ca2+, Mg 2+ & Fe2+ make
water hard.
2C17H35COONa + CaCl2 (C17H35COO)2Ca + 2NaCl
Sodium stearate Calcium stearate
Soap insoluble

Types of Hardness
i)Temporary hardness: due to the HCO3- of Ca+2 & Mg2+ & CO32- of
Fe2+
 can be easily removed by boiling.
heat
Ca(HCO3)2 CaCO3 ↓ + H2O + CO2
Insoluble 167
ii) Permanent Hardness: due to the presence of Cl- & SO42- of Ca2+,Mg2+,
Fe2+, etc
 can‟t be removed easily by boiling
Unit of Hardness
Hardness is usually reported as ppm of CaCO3 by weight.
1ppm=1mg/L
Hardness as CaCO3 = ml of EDTA x molarity of EDTA x 100 x 1000
ml of water sample
Where, 100 = molecular mass of calcium carbonate
1000 = conversion factor (i.e. to convert g to mg)

Ethylenediamine tetra acetic acid (EDTA)

168
 Disadvantages of Hard Water
a) In domestic uses.

 For washing & bathing, hard water creates difficulties. Since it

does not form lather freely with soap. It also creates sticky
precipitates that deposit on bath tub, body, clothes etc. until all the
Ca/Mg salts get precipitated. Thus a lot of soap get wasted also.
For cooking hard water creates similar difficulties by producing
scum on the bottom of the vessels. Due to the presence of hardness
producing salts in hard water, boiling point gets elevated & during
cooking a lot of fuel is wasted.
Drinking of hard water is also problematic since it affects the
digestive system & at the same time the possibility of deposition of
calcium oxalate crystals in the urinary tract is alarming. 169
b)In industrial uses
 For textile industry & dyeing industry- hard water causes the usual problem of
deposition of insoluble salts that interfere with the proper dyeing & printing of
the fabrics. The colors of iron salts also are undesirable on fabrics. Hard water
also hampers the economy by wastage of soap as it does not form good lather.
 For sugar industry- the salts responsible for hardness create difficulties in
sugar refining & crystallization of sugar & the sugar becomes deliquescent.
Deliquescence refers to the conversion of a solid substance into a liquid as a result of
absorption of moisture or water vapour from the air.

In the paper industry -Calcium & magnesium salts also interfere with the
smooth & glossy finish of the papers.
 Iron salts interfere with the colour of the paper.
In laundry- hard water causes wastage of costly soap & also interferes with
the coloration due to the staining of iron salts.
170
 In cement industry - The hydration of cement & final hardening of cement are
affected by use of hard water in concrete making.
 In pharmaceutical industry - Hard water is not suitable for preparing drug
solutions.
 For steam generation in boilers- hard water creates many problems like
 scale formation
 corrosion and
 caustic embrittlement ( a type of corrosion).

171
Sludge and Scale Formation in Boilers
When the salts present in the hard water precipitates are loose & slimy in nature, it
is called sludge whereas when these precipitates are hard & they adhere strongly to
the inner surface of the boilers, they are called scale.

 Sludge is formed by the presence of MgCO3, MgSO4, MgCl2, CaCl2 etc.

These salts are more soluble in hot water.
 Sludge can be easily removed by scrapping with a brush.
172
Disadvantages of sludge formation are
 Poor heat conduction due to the presence of sludge on the surface
 Difficulty in the operation of the boiler
 If sludge is formed along with the scale & is trapped within the scale
formed & so it is difficult to remove &
 It blocks the pipe lines & other connections to the vessel near the places
where water circulation rate is slow.
Removal of sludges.
Sludge formation can be prevented by
 using soft water for boiler operation &
 removing the concentrated salty water from time to time so that
deposition of sludge is prevented.

Scales are the hard deposits on the inner surface of the boilers which are
difficult to remove.
Disadvantages of scale formation are similar to sludge formation but the
severity is more, since its removal is more difficult. 173
Disadvantages include
 Poor heat transfer from boiler to water leading to increase in fuel consumption.
 Due to the overheating of the boiler, different parts of the boiler become weak
& distorted & so the operation of the boiler becomes unsafe.
 Valves & condensers of the boilers are chocked due to scale formation & boiler
efficiency decrease.
Removal of scales can be done by:
 Wooden scraper or wire brush, suitable for removing loose scales.
 Giving thermal shocks, which involve alternate heating & cooling to make the
scales brittle.
 Chemical treatment with 5-10% HCl for carbonates & EDTA treatment for Ca/Mg
salts forming complexes.

174
 Difference between sludges & scales

Is CaSO4 responsible for the formation of Scale at the colder portion of the boiler?
175
 Requisites of water for Industry
The principal requisites of water for some industries are as follows:-
i) Boiler feed water : should be soft & shouldn‟t contain organic matter
ii) Water for paper mills:
The presence of iron is injurious & any excess of lime & magnesia decomposes the
resin soups.
Ca & Mg salts also interfere with the smooth & glossy finish of the paper in the paper
industry.
iii) Water for dyeing & textile industry
Hard water causes the usual problem of deposition of insoluble salts that interfere
with the proper dyeing & printing of fabrics.
iv) Water for Sugar industry
The salts responsible for hardness create difficulties in sugar refining &
crystallization of sugar & the sugar become deliquescent
v) In laundry: hard water causes wastage of costly soap & also interfere with the
coloration due to the staining of iron salts. 176
vi) Pharmaceutical Industry: hard water is not suitable for preparing drug
solution in pharmaceutical industry

Treatment of water for Industrial use

Naturally occurring water which is used in steam raising boiler must undergo
the following treatment:-
 pptn of suspended & colloidal matter
Softening & desalination
Removal of O2, CO2 & other chemically reactive gases
As a principle, there are three important processes for treating water for
industrial use.
Distillation
Softening &
desalination
177
Softening of water
• the removal of Ca2+, Mg2+, Fe2+ salts & similar other metallic ions, which

would form insoluble metallic soaps.

Important industrial methods employed for softening of water are
i) cold & hot lime-soda process
ii) permutit or zeolite process
iiii) ion- exchange or demineralization process
i)Cold & hot lime-soda process
Soluble Ca2+ & Mg2+ salts are rendered insoluble by adding calculated
amount of lime & soda
The insoluble ppts of CaCO3 & Mg(OH)2 are removed by filtration
By this method, both temporary & permanent hardness are removed

178
For the removal of temporary hardness the rxns are:
Ca(HCO3)2 + Ca(OH)2 → 2CaCO3 ↓ + 2H2O
Mg(HCO3)2 + Ca(OH)2 → 2CaCO3↓ + MgCO3 + 2H2O
MgCO3 + Ca(OH)2 → Mg(OH)2↓ + CaCO3 ↓
For the removal of permanent hardness the rxns are:
CaSO4 + Na2CO3 → CaCO3↓ + Na2SO4
MgSO4 + Na2CO3 → MgCO3 + Na2SO4
MgCO3 + Ca(OH)2 → Mg(OH)2↓ + CaCO3 ↓
Hence, for the removal of permanent hardness due to Ca-salts, lime is not
necessary, but it is necessary for Mg-salts.

179
ii) Permutit or Zeolite process
Zeolite is hydrated sodium alumino silicate capable of exchanging reversibly
its Na+ for Ca2+ & Mg2+
General formula : Na2O.Al2O3.xSiO2.yH2O
Common zeolite : Na2O.Al2O3.3SiO2.2H2O & is known as Natrolith
Permutit is Artificial Zeolite used for softening purpose.
 Prepared by heating together with china clay, feldspar & soda ash.
Method of Softening
Hard water is passed through a bed of zeolite at a specific rate at ordinary
temperature; the hardness causing cations are exchanged for Na+ & it is
converted to CaZe & MgZe.

180
Reactions taking place are:
Na2Ze + Ca(HCO3)2 ↔ 2NaHCO3 + CaZe
Na2Ze + Mg(HCO3)2 ↔ 2NaHCO3 + MgZe
Na2Ze + CaSO4 ↔ Na2SO4 + CaZe
Na2Ze + CaCl2 ↔ 2NaCl + CaZe
Regeneration of Zeolite
Ca/Mg zeolites formed by passing hard water through the bed can be easily
regenerated into Na2Ze by passing brine through the bed of inactivated zeolite.

CaZe or MgZe + 2NaCl ↔ Na2Ze + CaCl2 (MgCl2)

The washings containing CaCl2 or MgCl2 are wasted. The water softened by
this process can be used for laundry purpose.

181
 Softening of hard water by zeolite
process

Advantages
Hardness of water can be removed
completely up to 10ppm
The equipment used is small & easy
to handle
It require less time for softening
There is no sludge formation
Easy to regenerate
Any hardness can be removed
without any adjustment of the
process
Disadvantages
Colored water or water containing
suspended impurities can‟t be used
before filtration.
Water containing acid can‟t be used
for softening
On removal of Ca2+ & Mg2+ the soft
water contains large amount of
NaHCO3 , this on heating liberates
CO2, which causes corrosion in
boilers & hence this soft water is not
suitable for boilers. 182
iii) Ion exchange or Demineralization
 Ion exchange resins are cross-linked high molecular weight organic polymers
having micro porous structure & the functional groups attached to the chains are
responsible for ion exchange properties.
a) Cation exchange resins (RH+) are phenol-sulfonic acid-formaldehyde resin,
styrenedivinyl benzene copolymers which exchange their H+ ions with the cations
present in the water. i.e., Ca2+ & Mg2+

183
Idealised image of water softening process, involving replacement of
calcium ions in water with sodium ions donated by a cation exchange resin.

184
185
 b) Anion exchange resins (ROH-): The styrene divinyl benzene or amine
formaldehyde copolymers contain quaternary ammonium tertiary sulphonium
or amino group in the resin. The resin on treatment with NaOH solution is capable
of exchanging the OH- with different anions of water. i.e., Cl-,SO42- etc..

Method: The hard water is passed through cation exchange resin whereby the cations
like Ca2+, Mg2+ are removed from the hard water & exchanged with H+ as follows:
2R-H + Ca2+/Mg2+ → R2Ca2+/R2Mg2+ + 2H+
186
 After this the hard water is again passed through anion exchange column, which
exchange all the anions like SO42-, Cl- present in the water with OH-.
R-OH + Cl- → R+Cl- + OH- ; 2R-OH + SO42- → R2SO4 + 2OH-
 Finally, H+ & OH- combine to form water molecule.
 Thus the water coming out finally from the two exchangers is ion free & called
deionized or demineralized.

Questions: What will happen if anion resin is located before cation resin?
This phenomenon would result in higher pH as the result hydroxide will also get precipitated and
will result in the blocking of the exchanger. This is why water is passed through cation exchanger first.
187
Demineralization of water showing the ion exchange
188
 Ion exchange chemical process.

Regeneration :
The inactivated or exhausted cation exchange resin is regenerated by
dil.H2SO4/HCl.
R2Ca2+ + 2H+ → 2RH+ + Ca2+
Similarly, the exhausted anion exchange resin is regenerated by dil.NaOH
R2SO42- + 2OH- → 2ROH- + SO42-
The columns are finally washed with deionized water & the washings are discarded.
189
Advantages of ion exchangers
Easy regeneration
Both acidic & alkaline water can be softened
Residual hardness is very low & hence the water is suitable for high pressure
boiler.
Disadvantages of ion exchangers
The equipment & the process is costly.
Turbid water can‟t be directly charged for softening. It needs prior filtration.

190
 Electrodialysis
 Dissolved inorganic salts in the water are in the form of
electrically charged ions.

 The process uses electric field to remove/pulled out the

electrically charged impurities from water.

 Positive ions move towards cathode and negative ions

move towards the anode.

 As a result of this ionic impurities are pulled out from the

central compartment as shown in figure below .

103
 Simple electrodialysis

Has three compartments using thin, rigid plastic membrane anode and cathode
placed at the two extreme ends of the cell and connected to positive and negative
terminals of the DC source
Draw backs
Concentrations of all cations and anions surround their respective electrode
and therefore, setting back emf and slow down the electrodialysis process.
Then, it can be overcome by using a cell with ion-selective membrane.
104
 Ion selective membrane

Cation selective membranes: −SO3‾H⁺, −COO‾H⁺ allows only the

cations to pass through.
Anion selective membranes: are like R4N⁺OH‾ allows only the anions to
pass through.

105 193
 Chapter- 3
Mineral acids manufacture: HCl, HF & H2SO4
HCl
Is the 26th rank highest volume chemically produced acid.
Qualities up to 28%, 31%, 35% and 37% sold as an acid solution of HCl gas in
water.
Manufacture of HCl: involves two steps
•Manufacture of HCl gas
•Absorption of HCl gas in water
A) Methods of manufacture of HCl gas:
From NaCl – is called salt cake method
0
The process is carried out in cylindrical shaped muffle furnace at elevated T
(150 0C) with H2SO4.
NaCl + H2SO4 → NaHSO4 + HCl↑
The temp. of the muffle furnace is increased to 550 0C and the NaHSO4
formed is allowed to react further with the remained NaCl
NaHSO4 + NaCl → Na2SO4 + HCl↑
Combustion of H2 with Cl2: carried out in pipe made of silica by filling
with H2 and then Cl2 is introduced through the pipe by a small nozzle .
H2 + Cl2 → 2HCl 106
 b) Absorption of HCl gas in water

 Its absorption is exothermic and its solubility decreases with

increasing temp. Due to this reason the process is carried out by cooling.
 Cooled HCl gas is admitted to bottom absorption tower which is
connected with scrub up absorber water is admitted into it from the top.
 Uses: metal surface cleaning, for manufacture of inorganic and organic
chlorides, activating oil wells etc.
HF acid manufacture
 It is the solution of HF gas in water.
 HF gas is made industrially by heating CaF2 with conc.H2SO4 then HF is
purified by successive washing, cooling and fractional distillation to remove the
SiO2 present still with HF b/se it interfere with quality of the acid.
SiO2 + 4HF → SiF4 +2H2O
SiF4 + 2HF → H2SiF6
 Absorption is similar as HCl but cu-alloy is used instead of fused silica as in
HCl for absorption tower purpose.
107
Sulfuric acid(H2SO4)

197
 What are sulfuric acids
• Highly caustic strong mineral acid.
• Colorless to slightly yellow
• Highly corrosive
• Soluble in water at all concentrations
• Historical name: Oil of Vitriol
• Diprotic acid which may show different
properties depending upon its concentration.

198
 Manufacture of Sulfuric acid (H2SO4)
Sulfuric acid (H2SO4) is a strong, heavy acid with a density of 1.84 g/cm3
& a marked tendency to absorb moisture from the air, generating
considerable heat.
Concentrated sulfuric acid (93–98 %) is used in the manufacture of
fertilizers, explosives, dyes, & petroleum products.
Sulfuric acid is formed during the Contact Process.
The Contact Process forms sulfur trioxide (SO3) gas from sulfur dioxide
(SO2) & oxygen in a catalyst tower, & sulfuric acid is formed when water
is added.
A mixture of H2SO4 & free SO3 is equivalent to a sulfuric acid
concentration of over 100 %. This mixture is called fuming sulfuric acid
or oleum.

199
Contact process

Sulfur trioxide cannot be mixed

with pure water as this is a highly
exothermic reaction, which would
produce a fine mist of sulfuric acid
that is difficult to condense and
could escape to pollute the air.

111
Chamber process Vs double contact process
Lead chamber process involves
i.S + O2 → SO2
ii.SO2 + NO2 → SO3
iii.SO3 + H2O → H2SO4
The process was modified by Gay-Lussac in 1827 & Glover in 1859.
 They include towers to recover excess nitrogen oxide & to increase
the final acid concentration from 65%(chamber acid) to 78%(tower
acid).
The contact process was invented by Phillips in England in 1831 but was
not used commercially until many years later.
Today 99% of all H2SO4 is manufactured by the contact process.
 use interpass absorption; also known as double absorption or
double catalysis.

201
The contact process for sulfuric acid
Almost all sulfuric acid is manufactured by the contact process.
Raw Materials
 SO2 or pyrite (FeS2)
 Air
Sources of raw material
The sources of sulfur & sulfur dioxide are as follows
Sulfur from mines
Sulfur or hydrogen sulfide recovered from petroleum desulfurization
Recovery of sulfur dioxide from coal or oil-burning public utility stack gases
Recovery of sulfur dioxide from the smelting of metal sulfide ores
2PbS + 3O2 → 2PbO + 2SO2
Isolation of SO2 from pyrite

202
Sources of SO2
 Sulfur burning
 Pyrites roasting
 Metal sulfide roasting and smelting
 Sulfuric acid regeneration
 Metal sulfate roasting
 Combustion of H2S or other sulfur-containing gases
 Other processes
Reactions
S + O2 → SO2 ΔH = - 71.2kcals
2SO2 + O2 2SO3 ΔH = - 46.3kcals
SO3 + H2O → H2SO4 ΔH = - 31.1kcals
203
Steps in the Contact Process
The steps in this process are as follow.
1. Burning of sulfur
2. Catalytic oxidation of SO2 to SO3
3. Hydration of SO3
1.Burning of sulfur
Burning of sulfur in presence of dry air is carried out in sulfur pyrite
burner.
As SO2 is needed for the catalytic oxidation & prevention of
corrosion, dry air is used in the combustion process.
If sulfur contains carbonaceous impurities, the molten material has
to be filtered to avoid poisoning the catalyst & forming water from
burning hydrogen.
204
2. Catalytic oxidation of SO2 to SO3
When using sulfur from mines or recovered from petroleum desulfurization,
purification of the SO2 gas is normally not needed.
Other sources of SO2 require wet scrubbing followed by treatment of the gas with
electrostatic precipitators to remove fine particles.
The catalyst used is V2O5 & K2O, in which the V2O5 is the active component.
& the pressure is 1.2-1.5 atmospheres.
The temperature has to be kept around 450oC. If it rises above 450oC, the
equilibrium is displaced away from SO3. Temperature should reach around
450oC for the catalyst to be activated. This process is strongly exothermic.
The catalytic reactor is designed as a four-stage fixed-bed unit. The gas has to
be cooled between each step. Four passes, together with "double absorption,
described below, are necessary for overall conversion of 99.5-99.8% (three passes,
97-98%).
The temperature rises to over 600oC with the passage of the gas through each
catalyst bed. 205
The doubled absorption consists of cooling the gases between
each bed back to the desired range by sending them through the heat
exchanger and then back through the succeeding beds.
Between the third and fourth beds, the gases are cooled and sent
to an absorption tower.
This is to shift the equilibrium to the right by absorbing SO3. The
gases are then sent to the heat exchanger to warm them to 410-
430oC and then on to the fourth catalyst bed.

206
CONTACT PROCESS FOR SULFURIC ACID MANUFACTURING
207
 3. Absorption (Hydration) of SO3 to give sulphuric acid

 After the catalytic oxidation process, the resulting SO3 is

hydrated by absorption in packed towers filled with 98-99%
sulfuric acid.
 The process of absorption is usually carried out in two
successive stages, of which the first produces 20-35% oleum &
the second 98% sulphuric acid.
 The remaining gas, which still contains 0.5 vol.% SO2 and 5-6
vol.% O2 is passed over a second catalyst (hence the term
"double contact process").
 In this process the total yield of SO3 exceeds 99.5%, & the
problems of dealing with the effluent gas are alleviated.
208
The acid strength can be adjusted by controlling the streams of H2SO4 to give
acid of 91 to 100% H2SO4 with various amounts of added SO3 and water.
The conversion of sulfur to acid is over 99.5%.

Kinetics and thermodynamics

The crucial step is the oxidation of SO2 to SO3. At normal conditions, the
equilibrium lies far to the left and the amount of SO3 formed is very small.
 To improve the yield of SO3, the reaction is carried out at around 450oC and
1.5-1.7atm pressure in presence of V2O5 or Pt as catalyst.
2SO2 + O2 2SO3 ΔH = - 46.98kcal
These conditions are chosen by applying Le Chatelier's principle.
 Effect of Temperature
 Effect of pressure
 Rate of contact reactions
209
Effect of temperature

Since the forward reaction is exothermic,

 at higher temperatures the backward reaction is more favored.
at very low temperature, the rate of combination of SO2 and O2 is very
slow and
 at higher temperature of about 4500C, the rate of formation of SO3 is
high & rate of decomposition of SO3 is minimum.

Hence, the temperature range which best meets kinetics and

thermodynamics requirements for high yield in the synthesis of SO3 is
located in between 4000C to 5000C, with optimum temperature at about
4500C.

210
 Effect of pressure
 The formation of SO3 takes place with decrease in volume & hence
increase in pressure is expected to increase the rate of formation of
SO3, i.e., rate of forward reaction.
 However, it has been observed that there is no appreciable change
in the yield at higher pressures.
 Also, higher pressure will increase the rate of corrosion of iron tower
used in the process.
 Hence pressure of 1.5-1.7atm is usually satisfactory.

211
 Uses of sulphuric acid
Sulphuric acid is the bulk commodity chemically used by almost
all the industries.
in organic chemistry for sulphonation, i.e. the introduction of the
functional group -SO3H
formation of alcohol from olefins in the presence of sulphuric acid.
as the catalyst in nitration.
in making fertilizers ,both superphosphate & (NH4)2SO4
in the manufacture of various chemical compounds.
in lead-acid accumulators(batteries).
for pickling metal prior to electroplating.
in the refining of petroleum.
212
 SUMMARY
Contact proces
S + O2 → SO2 + heat
SO2 + O2 V2O5Cat SO3 + heat
SO3 + H2SO4(conc.) → H2S2O7 (Oleum – fuming sulphuric acid)
H2S2O7 + H2O → 2H2SO4
Since the reaction is (exothermic) in oxidation of melted S and
SO2 , the heat obtained is used for melting of the sulphur.
If the concentration of the acid is less than 98%, it is sent to air
dryer where it flows in the counter current direction to inlet air.
The air takes away some heat of the acid and water. In that
way H2SO4 is cooled and concentrated. 124
 Chamber process

Uses impure H2SO4 containing oxides of nitrogen to

dissolve SO2 in glover tower.
Hot SO2 in contact with impure H2SO4 in counter current
direction , SO2 gets cooled and NOx’s (NO2 & NO) purged out.
2NO+O2→2NO2

SO2 + NO2 + H2O →H2SO4(impure dil.) + NO

Concentration and purification takes place in this part.
Some of the SO2 from lead chamber is absorbed in H2SO4
produced from glover tower in Gay-Lussac tower.

125
THANK YOU !!!
 Chapter 4.Common salts and the Chloro-alkali
Industry
4.1.Common salts and its sources
NaCl is a direct source of Cl2, Na metal, NaOH & Na2CO3
Indirectly-HCl,Na2SO4,Na3PO4,NaClO2 etc
Uses
preservative for meat, fish & hides
Animal/human being diet
For ice control
For soap makers to separate soap from glycerine
For the manufacture of various chemicals
Sources
i)From sea water-by solar evaporation
Pretreatment of the brine is necessary to attain sufficient purity
216
ii) From rock salt –by mining
Preliminary Crushing--- Crushing —Grinding—screening---saturation-evaporation
in the mining at the surface
Salt obtained by this method is 98.5-99.4% pure.
4.2. Chloro-alkali industry
 Includes the production of three main chemicals: NaOH, Cl2 & Na2CO3.
All the three chemicals are made from NaCl.
NaOH, & Cl2 are produced simultaneously by the electrolysis of NaCl (aq) soln.
the most important industrial chemicals.
NaOH, Cl2 & Na2CO3 are classified as “ heavy inorganic chemicals”
4.2.1.Leblanc process
Its chief use is for the regeneration of Cl2 for the manufacture of bleaching powder.
C.W. Sheel discovered Cl2 in 1774 by the following rxn:
4HCl + MnO2 → 2Cl2 + Mn2+ + 2H2O
HCl is a by-product of Leblanc-soda process. The process is now obsolete in use. The
process may represented by the equation:
217
 ∆
NaCl + conc.H2SO4 → NaHSO4 + 4HCl
NaHSO4 + NaCl → Na2SO4 + HCl
The HCl was then oxidized to give Cl2
4HCl + MnO2 → 2Cl2 + Mn2+ + 2H2O
Na2SO4 was used either to make glass, or to make Na2CO3 & NaOH.
Na2SO4 + C + CaCO3 → Na2CO3 + CaSO4
Na2SO4 + Ca(OH)2 → 2NaOH + CaCO3
In the Leblanc process the chemicals used are : H2SO4, NaCl,CaCO3 & C
The products are NaOH & Cl2.
In 1874 94% of NaOH was produced by the Leblanc process.
The Leblanc process become obsolete b/c cheaper methods were found. It was
replaced in turn by the Weldon process, the Deacon process and „
eventually by electrolysis.

218
4.2.2.Weldon & Deacon processes
The Leblanc process used MnO2 to oxidize the HCl, but the MnCl2 formed
was wasted.
The weldon process recycled the MnCl2 and was therefore cheaper.
 In the Deacon process air was used to oxidize the HCl instead of using
MnO2.

Cat
4HCl + O2 ↔ 2Cl2 + 2H2O + heat (reversible)
440oC

Now a days about 90% of the world supply of Cl2 comes from the
electrolysis of an aqueous solution of brine.

219
 4.2.3. Solvay process
 The process produce soda ash and the overall reaction is from the
anions in calcium carbonate with cations of NaCl gets interchanged
in indirect manner .
Step1. ammonia gas is absorbed in concentrated brine.
Step2. lime stone is heated to give quick lime and CO2
Step3. ammoniated brine is passed from the top of solvay tower
and CO2 is flow upwards from the bottom of solvay tower.
NH3(aq) +H2O(l) +CO2 (g) → NH4HCO3(aq)
NH4HCO3(aq) + NaCl(aq) → NaHCO3(s) +NH4Cl(aq)

220
The Solvay process: Manufacture of Na2CO3

221
 Cont’d...
Step 4. filtration of suspension of NaHCO3(s) & NH4Cl(aq)

Step5. decomposition of NaHCO3(s) by heat in to soda ash.

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

Step 6. quick lime is slaked with excess H2O giving milk of lime.
CaO(s) + H2O(l) Ca(OH)2(aq/s)

Step7. Ammonia recovery:

2NH4Cl(aq) + Ca(OH)2(aq/s) CaCl2(aq) +2NH3(g) +2H2O(l)

222
4.2.4. Electrolytic processes
There are two competing processes for obtaining Cl2, NaOH & H2 by the
electrolysis of NaCl (aqu) solutions.
i) Mercury cell process & ii) Diaphragm process
i) Electrolysis in mercury cells
Chemistry of the process
The dissociation of NaCl (aqu) solution :
2NaCl → 2Na+ + 2 Cl
At the anode
The chloride ions are discharged , where they lose electrons to form chlorine,
which is evolved as a gas. 2Cl- → Cl2 + 2e
At the cathode
The sodium ions are discharged , where they take up electrons to form metallic
sodium, which dissolves in the mercury as an amalgam. 2Na+ + 2e → 2Na
223
The sodium amalgam thus formed, an alloy of sodium & mercury, flows together
with the liquid mercury into a separate decomposition chamber,„ where it reacts
catalytically with water to give caustic soda solution & hydrogen:
2Na + 2HOH → 2NaOH + ↑H2
Overall equation for the reaction:
0.232 kWh + 2 NaCI + H2O →. Cl2 + 2 NaOH + H2
The electrolysis of alkali metal chlorides is an endothermic reaction.

Process stages
The industrial process can be divided into five stages .
1.Dissolution
2. purification of solutions
3. electrolysis
4.decomposition of amalgam &
5. treatment of chlorine

224
225
1. Dissolution
Rock salt is mined & delivered by water.
Rock salt contains 98-99% NaCl.
 The main impurities are small quantities of sea sand, particles of shells,
CaSO4.H2O, KCl, MgCl2 & traces of iron.
 Dissolution is carried out at 60-80 oC & the concentration of the saturated
solution is about 315 g NaCl per litre .
2. Brine purification
A commonly used purification process is to precipitate the ions of the alkaline
earth metal (Ca2+ & Mg2+) & Fe3+ by adding caustic soda & soda solution. At the
same time a suspension of BaCO3 is added in order to precipitate the sulphate
ions, SO42-.
The precipitated impurities are filtered off, after which the purified solution is
acidified to pH 4-6 & fed into the electrolysis cells.

226
3. Electrolysis
The electrolysis cells consist of slightly sloping, long & narrow iron troughs,
whose sides are coated with rubber internally.
A thin layer of mercury, serving as the cathode flows over the uncoated iron
bottom of the trough. The anodes (positive poles) are held about 3 mm (0.118 in)
above the surface of the mercury in iron sheaths coated with rubber.
The anode material is either graphite or an activated metal (eg titanium)
coated with ruthenium oxide.
Application of a voltage of 4-5 volts per cell liberates chlorine at the anodes.
Metallic sodium is liberated at the cathode, where it dissolves in the mercury to
give sodium amalgam.
The depleted salt solution which runs out is dechlorinated by blowing through air or
by evacuating, after which it is made alkaline with caustic soda & re-saturated in
the dissolution vessels.

227
4. Decomposition of amalgam
The sodium amalgam is decomposed with softened water on a carbon or
graphite catalyst to give NaOH & H2.
The water supply is regulated so that a solution containing 50 wt.% of NaOH
leaves the decomposition vessel. It needs no further treatment, but is ready for
use.
The hydrogen formed is cooled with water & then cooled to a low temperature
in order to purify it. It is then distributed by pipelines for hydrogenations or
reductions.
The mercury leaving the decomposition vessels is returned to the electrolysis
cells.

228
5.Purification of chlorine
The chlorine produced by electrolysis is about 99% pure. In addition to entrained
droplets of solution it is contaminated with some hydrogen, carbon dioxide,
nitrogen and oxygen from air which has leaked in, and small quantities of
organic chlorine compounds formed by the chlorination of graphite.

The chlorine gas is purified by washing with water and by an electrostatic gas
purifier, and is finally dried by passing it through concentrated sulphuric acid.

The final purification of the chlorine is effected on the other side of the
compressors by means of filters containing chlorinated active carbon. The
chlorine is then passed to chlorinating units or is liquefied by cooling.

Very pure chlorine containing 99.99% Cl2 is obtained by evaporating liquid

chlorine.
229
Simple electrolysis: brine solution is taken in the electrolytic cell with
graphite electrode immersed in it.

Na+ move towards the cathode --- get reduced

Cl- move towards the anode- -----get oxidized
Cathode: Na+ + e- → Na
2Na + 2H2O → 2NaOH + H2
Anode : Cl- → Cl + e-
2Cl → Cl2
Disadvantage of simple electrolytic process is undesirable side reactions.
2NaOH + Cl2 → NaCl + NaOCl + H2O
2NaOH + Cl2 → 2NaOCl + H2
To overcome the above problem we have to use diaphragm
cell(asbestos), membrane cell ( with polymer film) that separates
the anode and cathode compartments.
230
 Diaphragm cell
The diaphragm process use inert electrodes – a titanium anode electrode to
withstand attack from the chlorine formed and an iron mesh cathode, which is
not affected by the hydroxide solution.
Advantage:
large quantities of NaOH can be produced at
reasonable costs and at quite acceptable levels
of purity.

Disadvantages:
-There is always a small amount of chloride in
the NaOH produced,
- There are health and env’tal problems with
small losses of asbestos,

-Hypochlorite, a strong oxidant, in the waste

brine solution and this needs to be removed
before the brine is discharged into the
environment.

231
A diaphragm cell consists of two separate compartments
cathode compartment with an iron cathode &
 anode compartment with a graphite anode.
The two compartments are separated by a porous semipermeable diaphragm.

Figure :Alkali-chlorine
electrolysis in diaphragm
cells
232
The diaphragm serves to
 keep apart the H2 produced at the cathode & the Cl2 produced at the anode.
 It also prevents the mixing of the electrolyte solutions produced at the
cathode & the anode, which would otherwise react with one another.
The diaphragms are constituted so that the OH- ions migrate in the opposite
direction to the flow of liquid.
The fresh solution of rock salt is introduced into the anode compartment.
At the anode the Cl- of NaCl are discharged to give Cl2.
2 NaCl → 2Na+ + 2Cl-
Process at the anode (+) : 2Cl- → Cl2 + 2e-

The Na+ migrate through the diaphragm into the cathode compartment, where
they meet the OH- which have been formed by the electrolysis of water; the
solution thus contains NaOH.
Process at the cathode (-): 2H2O + 2e → H2 + 2OH-
The Cl2 from the anode compartment & the H2 from the cathode compartment
are drawn off separately & purified. 233
The decisive advantage of the mercury process over the diaphragm process is
that it produces very pure caustic soda, completely free from sodium chloride.

By contrast, the diaphragm process produces a solution of caustic soda which still
contains some NaCl.

However, this process has the advantages of a lower capital investment, the
avoidance of mercury, and the fact that it can employ sodium chloride
solutions obtained by the subterranean dissolution of salt deposits.

234
Cont’d…

235
 Membrane cell
A membrane cell is a diaphragm cell with an improved diaphragm
called a ‘membrane’. This is made from polytetrafluoroethylene (PTFE),
making it a plastic membrane, which has been modified to include
anionic groups to act as an ion exchange membrane. This allows
sodium ions to pass through it but not chloride or hydroxide ions.
PTFE is very inert and so can withstand immersion in hydroxide
solutions.

236
 No by-product of NaCl due to the membrane preventing the
chloride and hydroxide ions to pass through.
 has negligible environmental impact. The advantages are
much more preferable to that of the mercury and diaphragm
process.

237
Cont’d…

238
 Castner- kellner process
Uses a flowing Hg as a cathode
Titanium anode immersed in brine electrolyte solution is used.
Contamination of NaOH by NaCl is overcome.
Cl- moves to the titanium anode where as Na+ moves to
wards the Hg cathode
Anode rxn: Cl- → Cl + e-
2Cl- → Cl2
Cathode rxn : Na+ + -e → Na
2Na(Hg) + 2H2O → 2NaOH (aq) + H2(g)

239
Advantage :

 it produces very pure sodium and it

avoids using asbestos.

Disadvantage:

 Hg is lost to the environment, the

Hg should just be recycled as it is

pumped back into the cell. However,

there is an unavoidable mechanical

transfer of Hg to the brine solution,

which is discharged into the

environment back to the ocean .

240
2.3. Manufacture of Soda-ash(Na2CO3)-The Solvay process

The Leblanc process for the manufacture of soda ash was discovered in 1773 &
was used universally for many years in Europe. Salt cake (sodium sulfate) reacts
with limestone to give soda ash & a troublesome side product gypsum (calcium
sulfate). The process is no longer used.

In 1864 Ernest Solvay, a Belgian chemist, invented his ammonia-soda process.
The Solvay process had completely replaced the LeBlanc method by 1915.
The Solvay method is still very popular worldwide.

241
Description
Soda ash is made from both limestone & salt, the two major raw materials.
 The brine (salt solution) is mixed with ammonia in a large ammonia absorber.
A lime kiln serves as the source of CO2, which is mixed with the salt & ammonia in
carbonation towers to form NH4HCO3 & finally NaHCO3 & NH4Cl.
Filtration separates the less soluble NaHCO3 from the NH4Cl in solution.

242
Manufacture of soda Ash
243
The NaHCO3 is heated to 1750C in rotary dryers to give light soda ash.
The CO2 is recycled. Light soda ash is less dense than the natural material b/c
holes are left in the crystals of NaHCO3 as the CO2 is liberated.
Dense soda ash, used by the glass industry, is manufactured from light ash by
adding water & drying.

The ammonium chloride solution goes to an ammonia still where the ammonia
is recovered & recycled.
The remaining calcium chloride solution is an important by-product of this
process, although in large amounts it is difficult to sell & causes a disposal
problem. 244
Uses of Soda Ash
Glass is the biggest industry using soda ash.
The 49% used by this industry is divided into 44% bottles & containers,
38% flat glass, 9% fiberglass, and 9% other.
 Glass 49%
 Chemical manufacture 27%
 Soaps/detergents 11%
 Flue gas desulfurization 3%
 Pulp & paper 2%
 Water treatment 2%
 Miscellaneous 6%

245
END OF CHAPTER-4!!!

246
 Chapter- 5
Industrial Derivatives of Nitrogen

 The derivatives are: ammonia, TNT,NC & NG

 Ammonia is most important derivative for making

fertilizers and nitric acid and in turn nitric acid is used to
manufacture the explosive chemicals like NG,TNT &
NC.

247
 History of nitric acid
 Nitric acid occurs in nature in the form of nitrate salts. Initially, large
scale production of nitric acid began with sodium nitrate as a feed stock.
 Near the beginning of the 20th century, world reserves of sodium nitrate
were low and processes were being developed to replace nitrate with
nitrogen.
 Nitric acid was needed for explosives and developing dyestuffs business
 Three techniques were used industrially:
1) Production of NO by reacting N2 and O2 at greater than 2000 oC,
abandoned because of poor energy efficiency.
2) Production of ammonia by hydrolysis of calcium cyanide, not widely
accepted.
3) Production of ammonia from N2 and H2. (Haber-Bosch Process)

N2 + 3H2 2NH3

248
 Cont’d.....
Ammonia synthesis:
a)Cyanide process – proper mixing of lime with carbon and heated at
high temp.

CaO + 3C CaC2 + CO

By grinding CaC2 , it is charged electrical furnace adjusted at 10000c.

And pure N2 is passed over the hot calcium carbide.

CaC2 + N2 Ca(CN)2 + C

Ca(CN)2 is treated with super heated steam

Ca(CN)2 + 3H2O (steam) CaCO3 + 2NH3

249
 b) Haber process
Ammonia synthesis through the mixture of nitrogen and hydrogen.
Involves two distinct operations.
1.Preparation of N2- H2 mix.
Nitrogen – from liquefactions of air and its separation from oxygen is through
cryogenic distillation
Hydrogen – from bosch system water gas producer
C + H2 O CO + H2 The water gas mix's. ( N2,H2 ,CO & CO2) are also
mixed with large excess steam and passed over
oxide of iron & chromium catalyst to bring the
water- gas shift reaction.
C O + H2 O CO2 + H2
2. PREPARATION OF AMMONIA: the purified N2 & H2 are charged to ammonia
tower in the ratio of 1:3 at the pressure of 200 atm. At 500 0c over iron oxide catalyst .
The product obtained is up to 15% NH3 is cooled at the same pressure to be liquefied
and stored under specially designed tanks.

250
Modern method of ammonia manufacturing
251
 Manufacture of HNO3
1. Soda nitric process:
NaNO3 + H2SO4 heated in retorts NaHSO4 + HNO3

The product HNO3 is distilled out of the retort and condensed up to

95% v/v. But this process suffers due to limited distribution of
raw material salt peter.

2. Arc process: air is passed through an electric arc which cause O2 &

N2 to combine to give nitric oxide(NO) , in turn the NO is cooled

and oxidized to NO2 which is absorbed in water to form HNO3 of
only 35% and also its investment and operation cost is very high.

252
 3/Ammonia oxidation process: conversion of ammonia to nitric acid.
Ammonia is mixed with hot air and passed through Pt-Rh alloy acting as a catalyst
as seen the rxn below.
a) 4NH3(g) + O2(g) 4NO(g) + 6H2O(l) (Catalytic Combustion)
b) 2NO(g) +O2(g) 2NO2(g) N2 O 4 (oxidation of NO)
c) 3NO2(g) + H2O(l) 2HNO3(aq.) + NO(g) (absorption)
Other reactions : N2O4 +H2O → HNO2 + HNO3,
2HNO2 → HNO3 + H2O + 2NO
.
 Absorption of NO2 in H2O produce 60% HNO3 and sent to
a bleacher to purge away unnecessary oxides of nitrogen and
unreacted NO to be oxidized.
 The biggest issue with this method is the loss of precious
metal at the reactor temperatures.
 Recovery gauze is typically used to absorb platinum oxide
vapor and form an alloy. This gauze can periodically be
removed and platinum recovered.
253
254
 Markets and Uses of Nitric Acid

Markets and use of nitric acid

 The largest use of nitric acid is in the fertilizer industry,
74-78%

 The second largest use is for manufacture of chemicals.

Some examples are dinitrotoluene and nitrobenzene

 Finally for explosives, metal nitrates, nitrocellulose,

nitrochlorobenzene, a metal treatment solvent, rocket
propellants, and nuclear fuel processing.

255
 explosives

In general, an explosives basic characteristics are:

 Upon ignition, it decomposes rapidly in a detonation;
 rapid release of heat and large quantities of high-pressure
gases that expand rapidly with sufficient force to overcome
confining forces; and
 The energy released by the detonation of explosives produces
 rock fragmentation
 rock displacement
 ground vibration
 air blast
256
Alfred Nobel, Sweden

Nitro-glycerine (dynamite)-
used for rock fragmentation

257
 A general theory of explosives is that the detonation of the explosives
charge causes a high-velocity shock wave and a tremendous release of gas.
The shock wave cracks and crushes the rock near the
explosives and creates thousands of cracks in the rock.

Classification of explosives

Low Explosives: Deflagrate rather than detonate. Their

reaction velocities are 2000 to less than 3000 feet per
second. Black powder is a good example.
Black powder is mixture of potassium nitrate, charcoal and sulphur
Smokeless powder is nitrocellulose and perhaps nitro-glycerine
These materials normally have little water resistance, are highly
flammable
 Generally do not fragment rocks
258
 Black Powder (Low Explosive)
 Black powder contains:
• 75% Potassium Nitrate (KNO3)
• 15% Charcoal (C)
• 10% Sulfur (S)

The KNO3 is the oxidizing agent.

– When heat is applied to the powder, the oxygen from KNO3 is
liberated.
– It combines with the carbon (fuel) and sulfur (for stable
combustion).
– The combustion of charcoal and sulfur produces 2 gases – CO2 and
N2.
– The buildup of gases in the cartridge, propels the bullet forward in
bullet cartridges.

259
 Cont’d…
High Explosive: any chemical mixture that detonates with a
reaction velocity over 5000 feet per second.

Straight Dynamite - Nitroglycerin in an absorbent, with

velocities between 10,000 and 20,000 feet per second.
This dynamite is the most sensitive of all commercial explosives.
has poor fumes, good water resistance, and poor cohesion.

Ammonia Dynamite - This is similar to straight dynamite except

that ammonium and/or sodium nitrate and various carbonaceous
fuels are substituted for a portion of the nitroglycerin.
-blast agent

260
 Cont’d……

 Combustion (or decomposition) of explosives occurs

so rapidly, that there isn’t enough time for the oxygen
in the surrounding atmosphere to combine with the
fuel.

 Therefore, many explosives must have their own

source of oxygen – or oxidizing agents.

261
 Manufacture of TNT,NG & NC
TNT:- by nitrating toluene with nitrating mixture.
 The product is washed with ammoniacal solution of Na2SO3 and
cold water.
 The crystal of TNT is filtered and purified by melting.

NG: it is the class of explosives which is known as dynamite.

 prepared by adding glycerol to a cooled mix of H2SO4(60%) and
HNO3(40%) at 10oc with constant stirring.
 They form NG top layer and acid bottom layer so that we add
dilute Na2CO3 to neutralize the acid completely.
NC:- mild explosive.
[C6H7O2(OH)3 ] n + 3nHNO3 conc. H2SO4 [C6H7O2(NO3)3 ]n
+ 3nH2O
262
END OF CHAPTER -5 !!!

263
 Chapter 6. Fertilizers and phosphoric acid
Manufacture of H3PO4
1. FROM PHOSPHATE ROCKS:
- Phosphate rocks is digested with conc. H2SO4
Ca3(PO4)2 + 3H2SO4 + 6H2O 2H3PO4 + 3(CaSO4.2H2O)
-This product is mostly used to manufacture the phosphatic fertilizers because
essential nutrients like Mg, Al, Fe etc. Resides as impurities with phosphate
rocks.
-Side rxns: CaF2 + H2SO4 2HF + CaSO4 during digestion with the acid.

2. FROM PHOSPHORUS:
-Burning of phosphorus with excess air (O2) and absorbing the resultant oxide
in water form pure H3PO4.
P4 + 5O2 P4O10 absorbing in H2O 3H3PO4

264
176
Polyphosphoric acids: formed by heating two or more molecules of ortho-
phosphoric acids which undergo condensation form linear structure.
Eg. H4P2O7,H5P3O10....

Meta-phosphoric acids- heating of ortho-phosphoric acid at high temp. Form a

series of ring structures to general formula (HPO3)n
Eg. (HPO3)3 , (HPO3)4

Essential and trace elements for plant growth

From 35 elements of the plant nutrients 17 of them are essential
C,H,O – Natural nutrients since they are supplied by air & water
N, P ,K - primary nutrients which are consumed in large amounts and
supplied by soil.
Ca, Mg &S -occurring only in limited extent in soil – secondary nutrients
All these nutrients are called major nutrients and the remaining 8 elements
are considered as trace.

266
 Manufacture of nitrogenous fertilizers
1. ammonium nitrate
It is produced on conjugation with the NH3 & HNO3 plant.
a)Neutralization – it is exothermic ,heat is utilized for
concentration of the solution.
b)Evaporation – the solution is heated with steam and passed to
vacuum evaporator.
c)Prilling- solidification of the concentrated solution in the Prilling
tower.
d)Drying and finishing
NH4NO3 is an explosive and sensitive to heat . To reduce its
explosive nature it is mixed with (masked by) CaCO3.
It is also hygroscopic & prevented by packing in plastic bags.

267
 Urea manufacture
o
1 ) Carbamate formation in silver lined autoclave at 350-400 c
Rxn : 2NH3(l) + CO2(l) → NH2COONH4
2) Carbamate decomposition in high pressure decomposer and heated in steam
NH2COONH4 → NH2CONH2 + H2O
3) Concentration by vacuum evaporator
4) Prilling –solidification of the concentrated solution in to prills.

Potash fertilizers
 Containing the fertilities KCl,K2SO4 & KNO3
NPK – FERTILIZERS: it is a modern approach.
 known as mixed fertilizer containing N,P &K fertilizer combination.
 Raw materials : anhydrous liquid ammonia, phosphoric acid(25-30%),
H2SO4(80-93%) and potash(KCl).

Uses 3 neutralization tanks as the rxns equation seen below.

NH3 + H3PO4 → NH4H2PO4
NH3 + NH4H2PO4 → (NH4)2HPO4
2NH3 +H2SO4 → (NH4)2SO4
Then the product from the 3rd neutralizer is mixed with the calculated amount of
potash
268
 Phosphatic fertilizer
Simple and triple phosphates are the two most commonly used
phosphatic fertilizer.
Simple superphosphate : it is the mix. of mono-calcium
phosphate and crystalline calcium sulphate obtained by treating
phosphate rock with H2SO4.
Ca3(PO4)2 + 2H2SO4 + 2H2O → Ca(H2PO4)2 + 2CaSO4.2H2O
Due to fluorite present in the phosphate rock there is undesirable side
reaction.
CaF2 + H2SO4 → 2HF + CaSO4
Triple supper phosphate: contain 44-47% P2O5.

Action 78% phosphoric acid in phosphate rock

instead of H2SO4
Ca3(PO4)2 + 4H3PO4 → 3Ca(H2PO4)2
269
Cont’d…

181 270
271
 CHAPTER 7
SILICATE INDUSTRY

(Ceramics, Glass and Cement)

272
7.1. Introduction
Silicates are chemical compounds of silicon & oxygen with metals.
 Silicates are common raw materials for
•Ceramic industries
•Glass industries
•Cement industries
•Refractories
For that reason the technologies of these industries fall under the common
name silicate industry.
Generally, silicate materials are bad conductors of heat & electricity.
Now a days, some new types of ceramics are discovered with electrical &
magnetic properties. These ceramics are called high performance ceramics.

266
 7.1.1. Glass
Definition of Glass
“….an inorganic product of fusion that has cooled to a rigid condition
without crystallization”

Other Definitions:
―Glass is an inorganic product of melting, which when cooled
without crystallization, assumes a solid state‖

―Glass includes all materials which are structurally similar to a liquid

but which have a viscosity so great at normal ambient temperatures
that they can be considered as solids‖
Glasses are ceramics materials that are rigid like solids but which
are not crystalline. It may be considered as super cooled liquid of
infinitely high viscosity.
267
7.1.1.1 Properties of glass
Properties of Glass
Physical:
 transparent
 hard & brittle
 no fixed melting point
 bad conductors of heat & Electricity &
 can incorporate colour maintaining transparency.
 Its conductivity improves at high temperature while the opposite is
true for metals.
Chemical: not attacked by air, water, oxidizing agents, acids.
 Only attacked by HF readily.
Na2O.SiO2 + 6HF → 2NaF + SiF4 + 3H2O
CaO.SiO2 + 6HF → CaF2 + SiF4 + 3H2O
 Ordinary glass attacked by alkali solutions. 268
The two essential features on which glass formation depends are:
i) There should be a temperature range in which the viscosity of the
liquid increases very rapidly with decrease in Temperature.
ii) The liquids temperature must lie in or preferentially below this range.
If the viscosity of a liquid is already very high at the liquids temperature, the
rate of crystal growth will be negligible and the resultant super cooled liquid is
glass.
6.1.1.2. Composition of glass
 Glass is not a single compound. It is difficult to write any chemical formula
for it.
Generally the formula for glass may be represented thus, xR2O.yMO.6SiO2
Where R=alkali metals ; M=bivalent metals ; x and y =number of
molecules.
269
 7.1.1.3. Manufacture of glass
 Glass is made by melting one or more oxides in a furnace.
 Most glass is made from silica mixed with other oxides that melt at a
lower temperature than glass made from pure silica.
Raw materials
 The raw material in manufacture of glass may be selected from the
following.
Sand, soda ash, calcium oxide, fledspar, borax, magnesia, zinc,
alumina, lead oxide, manganese oxide, selenium metal, broken glass,
fluxes, colouring agent, reducing agent, oxidizing agent etc.
 Glasses are made of naturally occurring inorganic oxides.
 Silica in the form of sand is the main raw material.

270
 The raw material employed in the manufacture of glass
can be classified under three heads:
 Substances of an acid character, like SiO2,B2O3.
 basic “ CaO,Na2O,K2O,BaO,ZnO,PbO,etc.
 Various decolorizing & opalizing agents like
MnO2,Pb3O4,SnO2 etc.

271
 The oxides used for glass manufacture are classified into following
groups:
a) Network former
These are oxides of elements which are surrounded by four oxygen
atoms in the tetrahedral chain forming glass. Eg. SiO2, B2O3

b) Network modifier
These are large diameter elements having higher co-ordination number &
necessary to reduce the melting & working temperature.
The important network modifiers are oxides of alkali metal, alkaline earth
metals, lead, zinc etc.
The common modifiers are:
Na2O,K2O,MgO,BaO,CaO,B2O3,Al2O3,PbO,ZnO etc.

172
c) Intermediate glass formers
They do not give glass on melting but in presence of some network
formers using their co-ordination number they start giving glass.
Eg. Al2O3, ZrO2

d) Decolorizing/Oxidizing agent
 used to neutralize an undesired colour or reduce the colour of impurities
like iron oxides and manganese oxide.
Decolorant: MnO2,CeO2,SeO
e) Fining/Refining agent
 Added to promote the removal of bubbles from the glass melt.
 To reduce or to eliminate quantity of air bubbles from molten glass.
 The most commonly used fining agents include: Sb2O3,As2O3, SnO2,
CaSO4 , NaCl, Na2SO4 (salt cake) or small amount of feldspar

173
f) Colouring agent
 Small quantities of metal oxide is added as colourant during manufacture
of a definite coloured glasses.
Eg. Colourizing agents: CuO-blue, Cr2O3-green colour glass,
CoO-deep blue,Cu2O-red colour etc.
g) Cullet
 Waste or broken glass species.
 In normal glass production 33% of charge is broken glasses.
 Recycling of cullet increases the rate of production.

h) Opalizing agents: gives an opalescent appearance to the finished glass.

Eg.CaF2 & Ca3(PO4)2 274
 The manufacturing process of glass consisting of the following
four steps:
1. Melting the charge
2. Homogenization & refining
3. Fabrication of the article--------- shaping
4. Annealing the article formed
5. Finishing treatments
1. Melting of the charge
Amount of raw materials for the batch are calculated from the chemical
composition of individual components. After proper mixing of ingredient
it is charged into the furnace.
 From the batch to the melt
Chemical reactions
Sand dissolution
275
Two types furnaces are used for glass melting
a) Pot furnace b) Tank furnace
a) Pot furnace
In pot furnace, glass is melted in open or covered pots (closed pots) of fire clay
placed inside the combustion chambers of the furnace fired directly with coal or
producer gas.
Pot furnaces are generally used for small scale melting & fabrication by hand, for
the production of glass, table wares, lamp wares, thermos-flask etc.

b)Tank furnace: manufacturing large quantities of a particular type of

glass for bottle making & large sheets of glasses.
2) Homogenization & refining: for removal of bubbles, essential in order
to obtain a glass without fine bubbles.

 Dissolved gases
 Removal of bubbles
276
 Degassing the glass melt and removing all bubbles including also all
very small bubbles (seeds) from the molten glass.

Besides formation of the desired silicate melt phases, a large amount of

gases is produced:

From carbonates: CO2 gas is formed

From carbonates and cokes: CO gas
Hydrated ingredients give water vapor
From nitrates: O2 gas, N2/NOx gases;
Sulfates & sulfides can give sulfur gases, such as SO2, H2S.

277
3)Shaping or forming; either manually or by machine.
 Shaping is generally done while the glass is still molten, and the
processes of shaping are the following: blowing, casting, bending &
pressing.
4) Annealing; the process of heating glass, metals or other materials & then
cooling them slowly.
- It is a controlled cooling process.
 The purpose is to reduce strains.
5) Finishing: all types of glass articles must undergo certain finishing
operations.
These includes cleaning, grinding, polishing, cutting, enameling etc.

278
Enameled glass

Polished glass

279
280
281
Flow diagram mentioning manufacturing sequences of glass

282
7.1.1.4. Different verities of glass
a) Vitreous silica (Quartz glass)
Made by fusing pure silica without a flux.
Very resistant thermally & chemically
Used beyond the temperature ranges of other glasses.Clear quartz glass Tube
Transparent to UV- radiation
Used primarily for the manufacture of prisms & windows in optical
instruments
b) Alkali silicates (Na2O.SiO2.K2O.SiO2)
•Used for preservation of eggs &
in the manufacture of artificial stones

283
c) Lime glass
i) Soda-lime glass (Na2O.CaO.6SiO2)
 By far the greatest number of industrially produced glasses
 Main constitute–silica(60-75% SiO2) along with two major modifying
oxides
(12%-16% Soda, 10%-15% Lime).
 Easily fusible & low softening temperature.
 Use: Laboratory apparatus, Bottles, Jars, Drinking Glasses & Window
Glass, automobile glass , plate glass, electric lamp glass etc.
 It accounts for about 90% of manufactured glass.
ii) Potash-lime glass (K2O.CaO.6SiO2)
 High fusion temperature.
 Used for chemical apparatus which with stand high temperatures
especially combustion tubes. 284
d) Lead glass (K2O.PbO.6SiO2)
 54%-65% SiO2, 18%-38% Lead Oxide (PbO), 13%-15% Soda ash or
potash
 Higher refractive index than that of common glass, suited for decorative
purposes
 Used for decoration items, Vases, Bowls, Drinking Glasses, manufacture
of lens, prism, artificial gems and electrical bulbs.

285
e) Borosilicate glass
Made by replacing part of SiO2 by B2O3 in glass formulation
Usually contains 70%-80% SiO2, 7%-13% B2O3, 4%-8% Na2O, 2%-7%
Al2O3
Posses a high resistance to chemical corrosion & temperature change.
Low expansion coefficients
Superior resistance to shock
Excellent chemical stability
High electrical resistance
Widely used for Cooking Wear, laboratory glassware. Eg.Pyrex.

286
Special glasses
•colored glass
•Opal or translucent glass
•Safety or laminated glass
•Fibre glass
•Phosphate glass
•High silica glass

287
7.1.2. Cement
Cement was 1st used by Egyptians in constructing the pyramids.
 A cement is a binder, a substance which sets & hardens independently, &
can bind other materials together.
 The most important use of cement is the production of mortar & concrete.
Cements used in construction are characterized as hydraulic or non-
hydraulic.
Hydraulic cement is the cement that will set under water.
Non-hydraulic cement is the cement that must be kept dry in order to gain
strength.
Eg. lime & gypsum plasters.
Most construction cements today‟s are hydraulic, & most of these are based
on Portland cement.
Since Portland cements sets & hardens by reaction with water, it is
considered a hydraulic cement. 288
The raw materials for Portland cement production are a mixture of mineral
containing CaO,SiO2,Al2O3 & Fe2O3.
The main ingredient of cement are:
 Lime stone
 Clay (as a source of alumino-silicate) &
 Sand(SiO2)

7.1.2.1.Manufacturing procedure
It involves the following steps
1. Mixing of raw material
2. Burning
3. Grinding
4. Storage and packaging

1.Mixing can be done by any one of the following two processes:

Wet process: grinding & mixing of the raw materials in the
existence of water.
Dry process: grinding & mixing of the raw materials in the dry
state. 289
3
290
 Raw materials are crushed, powdered
and stored in silos. The clay is washed
with water in wash mills to remove
adhering organic matter

291
The wet process was the original one. For a time it was gradually
displaced by the dry process. But the wet process is now being adopted
largely for new plants for more accurate control & mixing of the raw mixture.
The three fundamental stages in the production of Portland cement are:
•Mixing/Preparation of the raw material
•Production of clinker (Burning process)
•Preparation of the cement ( grinding, storage & packaging)

2. Burning is carried out in rotary kiln which rotating at 1-2 rpm at its
longitudinal axis.
 Rotary kiln is steel tubes having diameter in between 2.5-3.0 meter
and length varies from 90-120 meter.
 The inner side of kiln is lined with refractory bricks.

292
The raw materials are mixed, ground & calcined together in a rotary
kiln at about 1400-1500oC.

Due to inclined position & slow rotation of the kiln, the material charged from upper
end is moving towards lower end. As gradually descends the temperature is rises.
293
Main part of the kiln :
1. The Upper part (dry zone) : water or moisture in the raw material is evaporated at
400oC, so it is known as drying zone
2.The Central part (calcination zone): decomposition of lime stone takes place
around 1000oC
CaCO3 → CaO + CO2
3.The Lower part (Clinkering zone): have To in b/n 1500-1700oC where lime & clay
reacts to yield calcium aluminates & calcium silicates.
These two compounds fused together to form small & hard stones known are as
Clinkers. The size of the clinker is varies from 5-10 mm.

A molten phase is formed by the alumina & ferric oxide in which the lime &
silica can dissolve & react together to give di-and tri-calcium silicate,
which then crystallize out.
The fused particles coming from the kiln are known as Clinker. The clinker is
cooled by a counter current flow of air in a rotary kiln type of cooler.
294
 2CaO + SiO2 → Ca2SiO4 (dicalcium silicate (C2S))
3CaO + SiO2 → Ca3SiO5 (tricalcium silicate (C3S))
3CaO + Al2O3 → Ca3Al2O6 (tricalcium aluminate (C3A))
4CaO + Al2O3 + Fe2O3 → Ca4Al2Fe2O10 (tetracalcium aluminoferrite(C4AF))

 As clinkers are coming from burning zone, they are very hot.
 The clinkers are cooled down by air admitting counter current
direction at the base of rotary kiln.
 Resulting hot air is used for burning powdered coal or oil and cooled
clinkers are collected in small trolleys or in small rotary kiln.

295
3. Grinding
 Cooled clinker is ground to fine powder in mill.
 2-3% powdered gypsum is added as retarding agent during final grinding.
So that, resulting cement does not settle quickly, when comes in contact with water.
 After initial set, cement-water paste becomes stiff, but gypsum retards the
dissolution of C3A by forming tricalcium sulfoaluminate which is insoluble &
prevents too early further rxns of setting & hardening.
3CaO.Al2O3 + xCaSO4.7H2O→3CaO.Al3O3.xCaSO4.7H2O

During fine grinding the following materials are added to the finished cement:
retarders, dispersing agents & waterproofing agents.

4. Storage and packaging

The ground cement is stored in silos, from which it is marketed either in
container load or 50kg bags.

296
Retarders: Glue, saw dust, organic substances, borax and
acetic acid. But they will not exceed 2 percent.
Accelerators: Common salt, alum, sodium carbonate.

297
Production Steps of Portland Cement
The basic steps in the manufacture of Portland Cement include:
- Crushing, screwing, and stockpiling the raw materials
- Calculating the proportions of raw materials
- Preparing the raw mix by blending
- Feeding the raw mix into rotary kiln
• 100oC: Free water is evaporated.
• 150-300oC: Loosely bound water is evaporated.
• 500oC: More firmly bound water is evaporated.
• 600oC: MgCO3 → MgO + CO2
• 900oC: CaCO3 → CaO + CO2

298
Reaction between lime and clay starts
• 1300oC: Major compound formation starts.
• 1400-1600oC: Output temperature.
(Around 1600oC clinker forms C3A, C2S, C3S, C4AF)
- Clinker cooled and stored.
- Clinker is ground with gypsum
. - Storing and marketing

299
Reactions at various Temperatures in the kiln

300
 Portland cement is a mixture of the following compounds:
Compounds Formula Abbrevation
Tricalcium aluminate 3CaO.Al2O3 C 3A
5-14%
Tricalcium silicate 3CaO.SiO2 C 3S
42-60%
Dicalcium silicate 2CaO.SiO2 C 2S
15-35%
Tetracalcium alumino ferrate 4CaO.Al2O3.Fe2O3 C4AF
10-16%

The composition of cement is usually given in terms of the oxides:

CaO(70%),SiO2(20%),Al2O3(5%),Fe2O3(3%),CaSO4.H2O(2%).
301
 The raw materials used in the manufacture of Portland cement consist
mainly of lime, silica, alumina and iron oxide.
 The oxides account for over 90% of the cement.
 The oxide composition of (ordinary) Portland cement may be expressed
as follows:

These materials (oxides) interact with each other in the kiln to form a
series of more complex products (compounds). 302
 Tricalcium Silicate (C3S): Hardens rapidly & is largely responsible for initial
set & early strength. In general, the early strength of Portland cement concrete is
higher with increased percentages of C3S.
 Dicalcium Silicate (C2S): Hardens slowly & contributes largely to strength
increases at ages beyond 7 days.
 Tricalcium Aluminate (C3A): Contributes to strength development in the first few
days because it is the first compound to hydrate.
Liberates a large amount of heat during the first few days of hardening & together
with C3S & C2S may somewhat increase the early strength of the hardening cement.
It affects setting time.
 Cements made with low C3A contents usually generate less heat, develop
higher strengths, and show greater resistance to sulfate attacks.
Tetracalcium Aluminoferrite (C4AF): contributes very little to strength of concrete
even though it hydrates very rapidly.
However, acts as a flux during manufacturing (allowing lower clinkering
temperature). Contributes to the colour effects that makes cement gray.
303
 C3S and C2S are the most stable compounds of cement. They are
together form from 70 to 80 percent of the constituents in the cement.

 When cement comes into contact with water, C3S begins to hydrate
rapidly, generating a considerable amount of heat and making a
significant contribution to the development of the early strength
particularly in the first 14 days.

 In contrast C2S which hydrates slowly & is mainly responsible for the
development in strength after about 7 days.

 The cement rich in C2S result in a greater resistance to chemical

attack & a smaller drying shrinkage than the other Portland cements.

304
 The hydration of C3A is extremely exothermic & takes place very
quickly. It contributes to high early strength but produces little strength
after about 24 hours.

 C3A is the least stable & cements containing more than 10 percent of
this compound produces concretes, which are susceptible to
sulphate attack.

 The use of iron oxide in the kiln feed contributes to lower C3A, but
leads to the formation of C4AF a product that is almost nothing but a
filler that should be kept at a minimum.

305
 Types of Cement
1. ASTM (American Society for Testing and Materials) Types
Type I: Normal (ordinary) Portland Cement
Type I-A: Air-entrained type-I Cement
Type II: Modified Portland Cement
Type II-A: Air-entrained
type-II Cement
Type III: High Early strength Portland Cement
Type III-A: Air-entrained
type-III Cement
Type IV: Low heat Portland Cement
Type V: Sulfate Resistant Portland Cement
2. Other Types
White Portland Cement
High Alumina Cement
Portland Pozzolan Cement
Portland Blast Furnace Slag Cement
Masonry Cement
Natural Cement
Expansive Cement

306
Type I (Ordinary Portland cement):
 It is used for general construction work when the special properties of
the other types are not required.
 It is normally used for reinforced concrete buildings, bridges,
pavements & sidewalks when the soil conditions are normal, for
concrete masonry units, & for all uses where the concrete is not
subjected to special sulfate hazard, heat of hydration is not
objectionable, where freezing-thawing is not expected.

 The regular Portland cement contains medium amount of

CaO.

307
Type II (Modified Portland Cement):
 It has better resistance to the action of sulfates than normal
(ordinary) Portland cement & used where sulfate concentrations in
groundwater are higher than normal but not very severe.

Type III: (High Early Strength Cement)

 High early strength cement is made from a raw material

with a high lime to silica ratio. It contains a higher
proportions of C3S than regular Portland cement & hence
hardens much more quickly.
 It is used where high early strengths are required at early
periods, usually a week or less.

308
 It is particularly useful where it is required to remove forms as soon
as possible or when the structure must be brought into service
quickly.
 High-early strength makes it possible to reduce the period of
protection for concrete during cold weather.

Type V (Sulfate Resistant Portland Cement):

 It is used in structures subject to sulfate attack, chemical plants,
etc.
 It is also resistant to the action of sea water.

309
OTHER CEMENTS
White Portland Cement (WPC):
 It is made from raw materials containing very little iron oxide & manganese
oxide. China clay is generally used together with chalk or limestone free
from specified impurities (iron oxide, manganese oxide).
 To avoid contamination by coal ash, oil is used as fuel in the kiln.
 The cost of grinding is higher & this completed with the more expensive
raw materials makes White Cement rather expensive (about 2 times).
 Specific gravity & strength of White Portland Cement are less than those of
OPC.
 WPC is used for architectural purposes.

„„White cement” is a Portland cement manufactured from particularly

pure raw materials with very low iron oxide contents.
310
High Alumina Cement (HAC):
 The raw materials of HAC are limestone or chalk & bauxite (a residual
deposit formed by weathering under tropical conditions of rock containing
Al2O3, Fe2O3, FeO, TiO2) which are interground & calcined at 1600oC in the
kiln. Its color is dark grey.

Properties are;
 It has high resistance to the action of sulfate waters (due to absence of
Ca(OH)2).
 Extremely high early strength (suitable for emergency repairs). 80% of the
ultimate strength is achieved in 24 hours or even at 6-8 hours.
 With special aggregates such as firebrick, it can be used to make refractory
concrete that can stand high furnace temperature (T> 1300oC)
 It is expensive.

311
Made by fusing a mixture of limestone & bauxite with small
amounts of SiO2 & TiO2 at 1500-1600oC in a rotary kiln.
It sets much quicker & develops high strength within one day
More expensive than Portland cement.
Used to make beams for bridges & buildings.
It withstands temperatures up to 1500oC.
A typical analysis of high alumina cement is CaO(40%),
Al2O3(40%), SiO2(10%), and Fe2O3(10%).

312
 Portland Pozzolan Cement:

 All pozzolans contain silica & siliceous or aluminous minerals.

 Fly ash, slag (blast-furnace), silica fume are artificial pozzolans.

 Volcanic ash is natural pozzolan.
 Portland Pozzolan Cement produces less heat of hydration & offers
greater resistance to the sulfate attack than OPC (useful for marine &
hydraulic construction & mass concrete).
 However, most pozzolans do not contribute to the strength at early ages,
so strength gain of these cements is slow. Therefore they require larger
curing period, but the ultimate strength is the same as OPC.

313
 Pozzolans are silica-containing natural or synthetic
materials, which can form calcium silicate hydrates with
lime & water even at low temperatures. Their addition to
Portland cement clinkers can therefore improve the
strength of the cement, but their slower hardening is a
drawback.
 The pozzolans are ground together with cement clinkers
& gypsum to form pozzolan cement.
 Pozzolan cements exhibit good chemical resistance.

314
Portland Blast-Furnace Slag Cement:
 Is made by intergrinding OPC clinker and 25-60% granulated blast-
furnace slag
 Granulated blast-furnace slag is a waste product of the
manufacture of iron.
A proper slag is a mixture of;
 Lime = 40%
 Silica = 30%
 Alumina = 20%
 Magnesia = 5% &
 Alkali Oxides = 1%

315
 The slag can also be used together with limestone as a raw material for

the conventional manufacture of PC clinker. This cement is less

reactive than OPC and gains strength at a slower rate during first 28

days, so adequate curing is essential.

 Properties are;

- suitable for mass concrete

- unsuitable for cold weather

- has high sulfate resistance(suitable for use in sea-water construction)

316
“Expanding cement” (shrinkage-compensated cement)
do not shrink upon hardening. Addition of 10 to 15% of
calcium sulfate or aluminate even effects an expansion
(“managed gypsum bursting”).

317
7.1.3. Ceramics

318
INTRODUCTION
Ceramic is an inorganic, nonmetallic solid prepared by the action of heat &
subsequent cooling.
Ceramic materials may have a crystalline or partially crystalline structure, or may be
amorphous (e.g. glass).
 Because most common ceramics are crystalline, the definition of ceramic is often
restricted to inorganic crystalline materials, as opposed to the non-crystalline glasses.
The earliest ceramics were pottery objects made from clay, either by itself or mixed
with other materials, hardened in fire. Later ceramics were glazed & fired to create a
coloured & smooth surface.
Ceramics now include domestic, industrial & building products & art objects.
 In the 20th century, new ceramic materials were developed for use in advanced
ceramic engineering; e.g., in semiconductors.
.

319
The word "ceramic" comes from the Greek word Keramos means burnt stuff.
Earlier the term ceramic was applied to products made from natural earth material
that was not exposed to heat. But nowadays the silicate mainly used in the
construction industries and prepared by burning the clay products are called as
ceramics.
Ceramics can be considered as the materials made from naturally occurring
clay.
In modern application, the term ceramics is extended to a wide range of
inorganic & non-metallic materials processed or used at high temperature.
Ceramics are usually hard & brittle in nature & exist in the form of amorphous or
glassy solid.
Ceramics materials include a wide range of silicates, oxides & combination of
silicates & oxides.

320
CLASSIFICATION
 A broad sense classification divides the ceramic products in to two
classes
1. Heavy clay products e.g. bricks, roofing tiles, drain tiles, hollow tiles,
stoneware & refractories.
2. Pottery products e.g. chinaware, wall tiles, electric insulation
 Ceramic may also be classified as porous & non-porous.
 Further, ceramic may be classified based on the method of production &
its uses into following classes.
1. White ware
2. Structural clay products
3. Refractory material
4. Special ceramic products
5. Vitreous enamel Red stoneware
321
7.1.3.1.Raw materials

The raw materials for ceramics are divided into the following groups:

 Plastic materials such as Clay (kaolinite) - Al2O3.2SiO2.2H2O

 Fluxes such as Feldspare - K2O.Al2O3.SiO2 &

 Non-plastics materials such as Silica (Sand)

Besides the three main raw materials, a large variety of inorganic

materials used for fluxing agents & special refractory.

 Common fluxing agents borax, cryolite, boric acid, Na2CO3, etc.

 Common special refractory ingredients are acidic, basic & neutral.

322
a) Clay

Clay gives the main body to the ceramics.

The advantage of using clay are it is plastic when mixed with water becomes
hard after drying & finally it becomes irreversibly solid after firing.
The use of clay in ceramics depends up on its following important
properties:
It is plastic enough to be moulded when it is wet.
It retain its shape when dried &
When the moulded mass is heated to high temperature, it sinters
together forming a hard, coherent mass without losing its original
color.

323
Impurities in common clay incorporate specific qualities as follows.
Iron oxide in common clay gives red color to the burnt material.
Lime, magnesia, iron oxide & alkali oxides act as flux which lowers the
fusion point of clay.
Silica increases its porosity & refractory nature, while decreases
shrinkage.
Clay containing very little & good deals of silica known as fire clays.

324
b) Feldspar
Feldspar is general name given to the group of minerals.
Flux materials like feldspar (Na2O.Al2O3.6SiO2) which is easily melting material
decreases the melting point of sand or quartz present in the ceramic body. So,
that after firing glass like material is obtained called as vitrified material, which is
highly impervious and stable to the environment.
Fluxes are used for adding verifications, reducing porosity, to increase the
strength of cold articles & for bonding.
Feldspar is used as fluxing constituent in ceramic formulations along with clay.
The common fluxing agents which lower the temperature are borax, boric acid,
soda ash, sodium nitrate, potassium carbonate, calcined bones, lead
oxides, lithium & barium minerals.
Type of feldspar
Potash feldspar K2O.Al2O3.6SiO2
Soda feldspar Na2O.Al2O3.6SiO2
Lime feldspar CaO.Al2O3.6SiO2
325
 c) Silica or quartz

The non-plastic or leading admixture like sand or quartz gives strength to

the body.
It is incorporated in ceramic formulation to reduce shrinkage & cracking
which is occurs during drying & firing.

7.1.3.2. The manufacturing procedure

The various steps involved in making the clay products are:
Compounding
Shaping
Drying
glazing &
firing.
Glazing is the process of covering articles made of clay with a glaze to give a
hard shiny surface & produce a wear resistance non-porous surface.
Wear resistance refers to a material's ability to resist
material loss by some mechanical action. 326
 Glazed ceramics

Handmade glazed ceramic pottery pieces

327
The glazing agents are: aqueous suspension of a heavy metal oxide such
as SnO2,PbO2 & a mixture of powdered feldspare,SiO2,Borax etc.
Glazing is done on various clay products such as
•sanitary goods
•floor & wall tiles
•electric insulators
•pots, dishes
•dinner & tea sets
•Crucible, etc.
Lead glazed

The dark red-brown ceramic electrical

insulators 328
7.1.3.3. Properties of ceramic materials
The ceramics find wide applications in various fields due to their many
favorable properties such as
Chemical resistance
electrical resistivity
thermal resistivity
compressive strength etc.

329
PROPERTIES
The physical & chemical properties of ceramic depend upon component
present in it.
The strength is mainly controlled by the factors like temperature, size &
shape, composition, surface condition & microstructure
Mechanically they are brittle & highly resistant to compression
Oxides & carbides which give high chemical & physical stability
Electrical & magnetic properties are due to composition itself.
E.g. oxides are generally bad conductors where the non-oxides are
semiconductors & ceramics with transition metal ions shows the magnetic
properties.
Transparency depends upon the crystal lattice of ceramic which in turn is
dependent of composition, crystal structure, extent of polarization etc.
330
USES
Ceramic is one of the oldest materials used in construction with the time
quality & decoration has been added to its property & therefore they are
at present used in following
Construction & decoration as bricks & tiles
Metallurgy as construction material of furnace
Chemical products as stoneware & porcelain
In drainage of water
In sanitation

The small uses includes pottery work, specialty ceramic like peuzo
electric and insulation material in electrical connections

331
332
 Chapter 8

Metallurgical Processes

251
 Introduction
Metals occur in nature in two different forms.
1.Native state:
The metals occur in native or free or uncombined
state are non-reactive with the environment. They
are noble metals, exist as such in the earth’s crust.
Example: Au, Pt, Ag
2.Combined state :
They exists in the form of stable compounds.
These cpds are associated with impurities such as
sand, clay, rocks etc.
Example: Fe2O3, ZnO, PbS, CaCO3 etc.
252
 8.1. Minerals and Ores
 Mineral is a naturally occurring materials present in
the earth’s crust, which contains metal in the native or
in the combined state.

 All minerals are not suitable for the extraction of

metals commercially.

 Ore is a mineral from which a metal can be extracted

profitably. Thus, “all ores are minerals, but all minerals
are not ores”.
253
Examples: clay (Al2O3, SiO2, 2H2O) and bauxite (Al2O3, 2H2O) are two minerals of
aluminum. But Al can be extracted only from bauxite and not from clay.
Therefore, bauxite is an ore of Al and Clay is a mineral.

Classification of ores:

1.Oxide ores ( bauxite, cuprite, haematite etc)

2.Sulphide ores (cinnabar, zinc blende, etc.)

3.Carbonate ores (dolomite=CaMg(CO3)2, limestone, etc. )

4. halide ores ( rock salt, cryolite etc)

5. sulphate ores ( epsom salt, gypsum etc)

6. silicate ores ( feldspar, asbestos etc )

7. nitrate ores ( chile salt, peter etc.)

8. phosphate ores ( phosphorite )

254
 8.2. Metallurgy
Process of extracting metal from ores is called
metallurgy which involves the following steps.
1. size reduction of ores

2. concentration of ores

3. extraction process

4. refining of impure metal

255
 Cont’d…
8.2.1. size reduction of ores
In order to process the ore to the metal, the ore must be reduced
to the appropriate size first by crushing and then by grinding.
a) Crushing
1.Jaw crushers
2. roll crushers

256
 b) Grinding
Grinding is mainly carried out in ball mills, tube mills,
hammer mills etc.
 Hammer mill

Screening
The ground particles are to be screened for their size and any
over size particles are to be recycled back to grinding.
There are two types of equipment's of commonly used for
screening.
1. reels or trammels
2. flat screen
257
 8.2.2. concentration of ores
The concentration of ores involves removal of rock impurities (i.e.
gangue or matrix) from the powdered ore.
The concentration of ore can be brought by any of the
following methods.

1. Gravity flotation process or hydraulic washing process

2. Froth flotation process

3. Electromagnetic separation process

4. Chemical methods

258
 1. Gravity separation or hydraulic washing process
This method is suitable especially for heavy “oxide” ores.
The concentration of ores is based on the difference in
the specific gravity (density) of the ore and the gangue
particles.
Principle: the powdered ore is treated with a stream of
running water, during which the lighter gangue
particles are washed away and heavier ore particles
settle down.
Gravity separation is carried out by two methods:
i. wilfely table method
ii.Hydraulic classifier method

259
 2. froth flotation process
This process is based on the difference in wetting
characteristics of the ore and gangue with oil and water.

 Used for sulphide ores in which the impure ore (ore with
gangue) is mixed with water and pine oil to make a suspension.
The suspension is violently agitated by the rotating
paddle/stirrer which draws in air, causing frothing.

 Due to this the ore particles which are wetted by oil come to
the surface with the froth, which can easily be separated to
get pure ore.

260
Cont’d...

261
 Cont’d...

 Sometimes it is possible to separate two sulphide

ores by adjusting proportion of oil to water or by
using 'depressants'.

Example: In case of an ore containing ZnS and PbS,

the depressant used is NaCN. It selectively prevents
ZnS from coming to the froth but allows PbS to come
with the froth.
262
 Cont’d...

Foaming agents- pine oils

Collectors (floating agents)- ethyl xanthates, amyl xanthates

Activators or depressants (NaCN) For frothing sulphide ores to

be concentrated 263
 3. Electromagnetic separation process
If any one part of the impure ore is magnetic in nature (either
ore or gangue), electromagnetic method can be used in which the
impure ore is dropped over a conveyer belt moving around two
rollers, one of which is an electromagnet. The magnetic parts will
be attracted by the electromagnet and collect as a separate heap
from the non-magnetic part.

264
 Cont’d…

 Tin stone ore is non magnetic. It contains wolframite as

impurity. The wolframite (FeWO4) is magnetic.

 Haematite (or) Magnetite ore is magnetic. It contains

silica as impurity. The silica is non magnetic.

265
 4. Chemical Methods
Chemical properties are utilized in concentration or purification
of the ore.

Example: Crude bauxite ( Al2O3.2H2O), impurities are

TiO2 and SiO2.

Al2O3 + 2NaOH 2NaAlO2 + 3H2O

NaAlO2 + 2NaOH Al(OH)3 + NaOH

2Al(OH)3 Al2O3 + 3H2O

266
 8.3. Extraction Process
 It is an essential process of reduction ( it uses a Chemical Reduction

method).

 For chemical reduction, the concentrated ore is converted in to oxide by

roasting or calcination followed by reduction.

6.3.1. Calcination

Calcination is the process of heating the ore strongly in the absence of

blast of air. Carbonates and oxides are generally calcined. This method

removes moisture, CO2 and other volatile impurities.

267
 Calcination (cont’d…)
Examples:
1.Calcination of limestone (CaCO3) to lime (CaO)
CaCO3 CaO + CO2
2.When bauxite is calcined, water is removed and only
anhydrous alumina is obtained.
Al2O3. 2H2O Al2O3 + 2H2O

The following changes occurs during calcinations.

a) the moisture is removed
b) gases are expelled
c) volatile impurities are removed
d) The mass becomes porous
e) thermal decomposition of the ore takes place 268
 8.3.2. Roasting
This is the process of heating the ore strongly in excess
of air. Sulfide ores are generally roasted.

 During roasting, sulfide ores are converted in to oxide

ores and volatile impurities are removed.

Example:

2ZnS + 3O2 2ZnO + 2SO2

269
Cont’d…

270
 8.3.3. Smelting
Smelting is the process of heating the roasted or
calcined ore along with a reducing agent and a flux
to high temperature.
Commonly used reducing agents in metallurgy: H2(g), CO(g), water
gas, Al, Mg, Ca metals, coke(C)

Example:

Fe2O3 + 3C (reducing agent) 2Fe + 3CO

271
272
 8.4. Refining of impure metal
8.4.1. Electrolytic refining
The impure metal to be refined is taken as anode and pure metal is taken
as the cathode and soluble salt of the metal dissolved in water is the
electrolytic bath.

At anode:

M Mn+ + ne-

At cathode:

Mn+ + ne- M
273
 Cont’d…
The pure metal from the electrolyte gets deposited
on the cathode and the equivalent amount of metal
from the anode pass in to the solution or are
deposited down the anode forms an anode mud.

Eg. Cu is refined in this manner

274
 Refining of metals by Liquation
This method is used if the ore contains high melting
gangue and easily fusible mineral particles

Refining of metal by liquation

275
 8.4.2. Poling
Impure metals extracted are refined by bringing them to molten
state in a furnace and then treating with oxygen (air).

276
 8.4.3. Fractional Distillation

Impure metals containing other volatile impurities

can be refined by fractional distillation.

Eg. Zn is separated from Pb & Cd by fractional

distillation using a separate column for each impurity.

277
 8.4.4. Zone refining method
 Purification is employed when the impurities are more soluble in the
molten metal than the solid metal , and the molten metal on re-solidification
crystallizes out as pure metal.

Used to refine elements like Si, Ge, Ga etc.

Used to produce ultra pure elements based on the difference in
solubility of impurities in the molten and solid states of the metal
It is applied by a movable heater around the rod of impure metal
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N.B.

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Diagram Showing Extraction of Uranium
from Pitchblende Ore

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 Chapter-9
High Temperature Materials

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 9.1. Refractories
 Refractories are materials which are used to withstand high temperature,
chemical & physical effects without softening or suffering a deformation in shape.

 The main objective of a refractory is to confine heat (i.e.,to resist the heat loss) &
at the same time to resist the abrasive & corrosive action of molten metals,
slags & gases at high operating temperatures.

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Thus refractories are those materials which are used for the construction of
furnaces, kilns, ovens, crucibles, retorts, converters etc.

crucibles

9.1.1.Classification of refractories
(i) Acid refractories:
 made of clay, clay-silica mixtures & pure silica.
 not attacked by acidic materials.
Examples

silica bricks
fire clay bricks.
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ii) Basic refractories:
 made up of large proportion of lime or magnesia or a mixture of these
bases or other metal oxides.
Examples-

Magnesite bricks (magnesia) bauxite bricks

(iii) Neutral refractories:
 made up of weakly acidic or basic materials like carbon, chromite (FeO,
CrO,), zirconia (ZrO2) etc.
Examples-Chromite bricks, silicon carbide & graphite

silicon carbide

graphite
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9.1.2.Properties of refractories
Refractories should possess the following general properties:
 They must be able to withstand high temperature.
 The fusion temperatures of the usual refractories in use vary from 1600°C
to 2700 °C.
 They should be chemically inert towards the corrosive action of gases,
liquid metal & slags produced in its immediate contact in furnaces.
 They should be able to withstand sudden change of temperature.
 They should be able to withstand spalling, i.e.. cracking & flaking of the
bricks due to uniform expansion or contraction. Annealed bricks can better
withstand spalling.
 They must be able to withstand abrasion or erosion of the furnace charge
& also the pressure of the load.

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9.1.3. Manufacturing of refractories
The steps can be displayed schematically as follows:

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9.1.4. Common Refractory Bricks
i) Silica bricks: It contain 92-95% silica, 2% lime, the main raw materials are
quartz, quartzite, sandstone etc.
Uses
Main applications of silica bricks are:
 In open hearth furnaces
 In coke-oven walls
 Glass-furnaces
ii) Fire clay-bricks: Raw material is fire clay (clay-Al2O3.2SiO2.2H2O)
Generally fire clay bricks contain 55% silica. 35% alumina.
This is acidic fire clay brick.
Basic fire clay bricks contain 55% alumina & 40% silica, rest consists of K2O,
FeO. CaO, MgO.
 The acidic slag contains high amounts of SiO2, Al2O3 which can make the
slag thinner. A basic slag contains oxides like MgO and CaO, which
makes the slag thicker. FeO is the most important part of the slag in that it
causes lime to dissolve at lower temperatures which is called 'fluxing'.

o a slag low in silica and high in base-forming

oxides that is used in the basic process of
steelmaking and that is subsequently useful as
a fertilizer. 371
 Properties
 Light yellow-reddish brown in colour Uses
 Low porosity & lower refractoriness . In blast furnaces
than silica bricks . . In kilns
 Fusion temperature 1350°C
 Better resistance to thermal spalling
than silica bricks.
 Cheaper than silica bricks.
iii) High alumina bricks: Composition-50% or more alumina.
Properties
 Low coefficient of expansion
 High porosity
 Little tendency to spall
 Excellent wear resistance & stability.
Uses
 For linings for Portland cement rotary kilns
 Furnace hearths & walls
 In reverberatory furnaces
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iv) Magnesite bricks: Magnesite is naturally occurring magnesium carbonate
(MgCO3) & is the raw material for the magnesite refractories.
Preparation method
Calcined magnesite (at 1600°C) i.e.. MgO is powdered to a proper size & then
mixed with caustic magnesia or iron oxide as binding material & then ground.
The prepared powder is pressed into bricks in hydraulic presses. The bricks are then
slowly heated to 1500oC & kept for about eight hours at this temperature & cooled
then slowly.

Properties
 They are generally grey or brown in colour
 They can be used up to 1500 oC
 They possess good crushing strength, good resistance to basic slags &
very little shrinkage
 Their resistance to abrasion is poor.
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Uses
 For the lining of basic converters & open hearth furnaces in steel industry
 They are used in hot mixer linings, copper convertors
 In reverberatory furnaces for smelting lead, copper
 In refining furnaces for gold, silver & platinum etc.0994240959
v) Dolomite bricks: made by mixing calcined dolomite (i.e., mixture CaO + MgO) in
equimolar proportion with silica as binding material. Other binding materials used for
the same are tar, quick lime, iron oxide. clays etc. They are then fired at 1500°C for
about 24 hours.
Properties
 They are less strong, more porous & have more softness & shrinkage than
magnesite bricks
 They are not very much resistant to thermal shock
 They are more resistant to slags & spalling than magnesia bricks
 They wear out quickly.
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Uses: For repairing materials, In Bassemer converters, open-hearth furnaces. etc.
vi) Chromite bricks: is a neutral refractory.
The crushed chromite ore (FeO.Cr2O3) is fired at 1500°C-1700°C after mixing
with a little clay as binding material.
Properties
 They are neutral in colour
 They possess high density, resistance to acidic as well as basic slags
 They can withstand up to 1800°C
 They possess good crushing strength
 They have moderate thermal conductivities.
vii) Carborundum or silicon carbide bricks
Composition : Silicon = 65%, Carbon = 30% & Impurities = 5%
Properties
 dark grey to black colour
 High Hardness
 Fusion point is 2500°C
 Coefficient of thermal expansion is very low
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  High resistance to abrasion
 silica bricks tend to oxidise to silica in presence of air at 1000°C
2SiC + 3O2 = 2SiO2 + 2CO
 very high mechanical strength
Preparation Method
They are prepared from coke & sand. Sand (60%) & coke (40%) are properly
mixed & is followed by addition of some sawdust & a little salt. The mixture is then
fired at 1500°C in an electric furnace. Sawdust when burned evolves gases,
which by circulation increases the porosity of the charge. Salt reacts with iron &
similar impurities present in the raw materials to form volatile chlorides. These
volatile chlorides make the final products porous. The silicon carbides obtained
from the furnace are interlocked tridiscent crystals. Bonding agents like clay, silicon
nitride are mixed. The mixture is then shaped, dried & fired. The firing temperature
is 2000°C. At this temperature interlaced crystals are formed.
Reaction :SiO2 + 3C → SiC + 2CO
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Uses
 Owing to its high thermal conductivity they are used in muffle furnaces.
 Owing to their high electrical conductivity, they are used in electric arc furnaces.
.

muffle furnaces Structure of electric arc furnaces

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viii) Zirconia bricks: fall under pure oxide refractories.
Refractory oxides of common use are alumina (Al2O3), magnesia (MgO), zirconia
(ZrO2) & thoria (ThO2).
Preparation method
Zirconia brick is prepared by heating zirconite (ZrO2).
First zirconia is calcined & powdered. The powdered zirconia is kept under water
for sometime & the wet zirconia is mixed with binding material, viz. colloidal
zirconia or alumina in a mill. The materials are then molded into bricks by hand
molding or pressing. The molded bricks are dried & fired at about 1750°C.

Properties
 Zirconia refractories fall under neutral refractories
 They can withstand a temperature up to 2600°C.
 They are resistant to basic slags.
 Zirconia bricks are very costly

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Uses
 Specially used when high temperature is used
ix) Beryllia bricks: Beryllia minerals are used to prepare the bricks which are fired at
2000°C.
Properties
 High melting point (2550°C)
 Low electrical conductivity
 High thermal conductivity
 Good resistance to thermal shocks
 Inertness to carbon dioxide & carbon monoxide up to 2000°C.

Uses
 Beryllia is used in making crucibles to melt uranium & thorium, owing to
its low neutron absorption capacity.

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x) Cermets: are hot pressed or sintered materials comprising ceramic & metallic
components.
A cermet is a composite material composed of ceramic (cer) & metallic (met)
materials.

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Methods to Manufacture Cermets

381
Properties
 They are the combination of ceramics & metals
 They have high refractoriness of ceramics
 They have high thermal conductivity of metals
 They have high thermal shock resistance of metals etc.
 Refractory ceramics used in the manufacture of cermets are zirconium carbide,
molybdenum carbide & tungsten carbide.
 Most cermets contain about 80% of ceramic materials & 20% of the metal. They
are usually fabricated by the techniques of powder metallurgy.
Uses : In rocket and jet engine parts & Spinning tools for hot metals.

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 Chapter -10
Miscellaneous Materials

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 10.1. Abrasives and Classification
Abrasives are materials characterized by higher hardness.
Used to wear down softer surfaces by cutting, grinding and
polishing.
Hardness is important quality of an abrasives and is measured
on Moh’s scale.
Based on occurrence abrasives classified into two ( Natural
and artificial abrasives)
Natural abrasives
Diamond
 Crystalline form of carbon ranks 1st hardness.
 Chemically inactive and not attacked by acids & alkalis.
 Used in operation where a great hardness is required.

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 Corundum
 Is crystalline aluminum oxide.
 Used as abrasives for glass, lenses, metals and metal cutting.
Emery- fine grained, opaque and massive mineral.
 55-75% crystalline alumina.
 20-40% magnetite(Fe3O4)
 12% others, eg. Tourmaline
 Its grinding power depends on proportion of alumina.
 Used for as tips of bits of cutting and drilling tool.
Garnets
 Tri-silicate of alumina, magnesia and ferrous oxide: (Ca3Al2(SiO4)3,
Ca3Fe2(SiO4)3, Fe3Al2(SiO4)3)
 Used for glass grinding & polishing metals
Quartz:
 crystalline silica cemented with feldspars, clays, carbonates and
other minerals
 Used for grinding of flour, pigments and ores ,etc.
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 Artificial Abrasives
 Silicon carbide (carborundum)
 bluish-black crystalline artificial mineral with
hardness B/n corundum and diamond
 Made by Mixing silica with carbon(coke or coal) in
electric furnace at 1650-2200oc
SiO2 +3C SiC+2CO
 Is Chemically inert, withstand high T0 without
damage, is not tough but brittle.
Use:
 As a Cutting wheel, abrasive paper and clothes
 Extensively used for grinding low tensile strength
materials like cast iron, brass, bronze, porclain, glass
and optical lenses.
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 Alundum(Al2O3)
 Mixture of Calcined bauxite and carbon in 4000oc electric arc
furnace.
 Used for grinding hard steel and less brittle, high tensile
strength.
Boron carbide or Norbide(B4C)
Inert and hardest of all artificial abrasives.
made by heating boron oxide with coke in electric furnace at 27000C
2B2O3 + 7C → B4C + 6CO↑
USES
 For making grinding dies and for cutting and sharpening hard high
speed tools.

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10.2. Grinding Wheel
Abrasives are widely used for grinding of different
materials such as metal ,stone, wood etc. in the
form of wheels.
For preparing Grinding Wheel:
 Abrasive materials crushed in jaw crusher and
roller mill.
 Graded according to grain size.
 Mixing with binding materials.
 Moulded into wheel.

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308
 Factors governed production of grinding wheel
 Type of abrasive:
(mostly artificial abrasives are used like carborundum, fused alumina or silica b/c
of their uniformity in chemical composition and hardness).
 Grain size(4,8,20,12,64,96,180,&220)- mesh numbers
The grits(size of the grain obtained by crushing and grinding) are separated by
screens, coarser grains cut quickly and fine sized grains cut slowly but give
better and smooth finishes.
 Type of binding materials- used for cementing together the grains of abrasive
materials.
 Five of bonds are used.
1. ceramic bond- abrasive grains mixed with powdered feldspar and clay along with
water. The material is shaped by moulding, dried in hot air chambers and fired in
kiln at 1300-15000c
-very strong, Highly chemical resistant & resistant to To changes
2. Silicate bond - abrasive grains mixed with jelly of Na- silicate, the mixture is
moulded, dried and baked at 400-500oc
3. Shallac bond- abrasive grains mixed with molten shallac
4. rubber bond
5. synthetic resin bond

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311
10.3.Abrasive papers and abrasive cloth

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 10.4.Electrical Insulators or Dielectrics

 Electrical Insulators or Dielectrics are materials used to

prevent lose of electricity.

 Main function of dielectrics is electrical storage

 Main function of insulators is to prevent passage of current

and thereby insulate conducting materials.

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Characteristic of an Insulator or Dielectric
 Low Electrical conductivity i.e high resistivity

 High dielectric strength(Measure of voltage at which

the material undergoes electrical breakdown)

 Low/High Dielectric constant respectively (measure of

materials ability restore electric charge)

Less porosity

Chemically inert.

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 Important insulating materials
Gaseous insulators

1. Air- provides insulation b/n overhead transmission lines

2. Nitrogen : chemically inert, used in transformers.

3. Sulfur hexafluoride(SF6):good cooling effect than air and N2.

Liquid insulating materials

1. mineral oil: presence of organic Cpd,O,N,S increases dielectric loss.

2. silicon fluids: excellent insulating material and stability at high

T0besides their viscosity.

3. Synthetic Hydrocarbons

4. Vegetable Oil
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 Solid Electrical Insulators

 Organic fibrous materials like cotton, silk, nylon, paper etc.

 Inorganic materials like mica, asbestos glass ceramics

10.5. Thermal Insulators

Thermal Insulators are materials having low conductivity.
used when:
 To stop heat flow from the surrounding to the system
 To stop heat flow from the system to the surrounding
prevent heat transfer by conduction, convection and
radiation
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 Characteristics of Thermal Insulator
1. Low thermal conductivity
2. must be fire proof
3. chemically stable at high temperature
4. strong
5. odorless during use
6. low cost
Classification of Thermal Insulator
1. Organic Insulator
2. inorganic Insulator

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