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ENGINEERING CHEMISTRY
For B.E. Ist YEAR (Common to all Branches)
[According to the latest Syllabus of
Rajiv Gandhi Proudyogiki Vishwavidyalaya, Bhopal]
(iii)
(iv)
PREFACE TO THE THIRD REVISED EDITION
The specular respone received by the earlier editions, both from teacher and students has
encouraged the authors to present this third revised editions.
The latest revised syllabus of RGPV Bhopal is fully covered in this new edition. Every aspect
written in this textbook is simple and presented in a lucid manner, so as to make students conversant
with the requirements of the subject. To enchance the understanding of problem, diagrams figures
and numebrical are included at required place. The authors believe that the book will largely meet
the requirements of students with simple understanding.
The authors received support and encouragement from many peoples. First, we wish to thank all
readers of our previous editions of this book who appreciate & compliments. We sincerly acknowledge
the encouragement moral support useful suggestions given by fellow teachers and students. Particularly
Dr. Namrata Jain Professor and HOD RKDFIST Bhopal.
We would like to extent our most sincere appreciation to all persons who have contributed his
valuable time in best possible way for the completion of this book.
Finally the author Dr. Abhilasha Asthana is particularly thankful to her parents Dr. K.K. Asthana,
Mrs. Usha Asthana and brothers Mr. Rajeev and Mr. Reetesh Asthana for being supportive in times
of stress and for assisting with the task of manuscript preparation. No major proffesional project can
be understand without the cooperation of one’s family.
Being a teacher, we appreciate the value of criticism. The quality of science improves through
critical discussion. Therefore constructive suggestions comments and criticism on the subject matter
of the book will be greatfully acknowledged as they will certainly help to improve the editions of
the book.
Disclaimer : While the authors of this book have made every effort to avoid any mistake or omission and have used their skill,
expertise and knowledge to the best of their capacity to provide accurate and updated information. The authors and S. Chand
does not give any representation or warranty with respect to the accuracy or completeness of the contents of this publication
and are selling this publication on the condition and understanding that they shall not be made liable in any manner whatsoever.
S.Chand and the authors expressly disclaim all and any liability/responsibility to any person, whether a purchaser or reader
of this publication or not, in respect of anything and everything forming part of the contents of this publication. S. Chand shall
not be responsible for any errors, omissions or damages arising out of the use of the information contained in this publication.
Further, the appearance of the personal name, location, place and incidence, if any; in the illustrations used herein is purely
coincidental and work of imagination. Thus the same should in no manner be termed as defamatory to any individual.
(v)
SYLLABUS
Unit I : WATER AND ITS INDUSTRIAL APPLICATIONS
Sources, Impurities, Hardness & its units, Industrial water characteristics, softening of
water by various methods (Exrernal & Internal treatment), Boiler trouble causes, effect
& remedies, Characteristics of municipal water & its treatment, Numerical problems
based on softening methods.
Unit IV : POLYMER
Introduction, types and classification of polymerization, Reaction Mechanism, Natural
& Synthetic Rubber; Vulcanization of Rubber, Preparation, Properties & uses of the
following- Polythene, PVC, PMA, PMMA, Teflon, Poly acrylonitrile, PVA, Nylon,
Nylon 6:6, Terylene, Phenol formaldehyde, Urea - Formaldehyde Resin, Glyptal,
Silicone Resin, Polyurethanes; Butyl Rubber, Neoprene, Buna N, Buna S. Flow sheet
manufacturing diagram of Nylon 6:6 & Decoran.
(vii)
(viii)
Water and Its Industrial
UNIT
1 Applications
1.1 INTRODUCTION
Water is the basic necessitiy of life. It is necessary for the survival of all livings. Approximately
80% of the earth surface is covered by water, but only 1% water is available for the uses of different
purposes such as domestic, agaricultural, municipal and industrial work.
(i) Surface water (ii) Underground (iii) Rain water (iv) Esutarine and
water sea water
1
2 BASIC ENGINEERING CHEMISTRY
1.3 TYPES OF IMPURITIES FOUND IN WATER
The impurities present in natural waters may be broadly classified as follows
(1) Dissolved impurities
(a) Inorganic salts e.g.,
(i) Cations : Ca2+, Mg2+, Na+, K+, Fe2+, Al3+ and sometimes traces of Zn2+ and Cu2+
(ii) Anions : Cl–, SO42–, NO3–, HCO3–, and sometimes F – and NO3–
(b) Gases e.g., CO2, O2, N2, oxides of N2 and sometimes NH3, H2S
(c) Organic salts
(2) Suspended impurities
(a) Inorganic e.g., clay and sand
(b) Organic e.g., oil globules, vegetable and animal matter.
(3) Dissolved impurities
Finely divided clay and silica, aluminium hydroxide, ferric hydroxide, organic waste products,
humic acids, colouring matter, complex protein, aminoacids, (which are generally classified as
albunoid ammonia).
(4) Bacterial impurities
Bacteria, other micro-organisms and other forms of animal and vegetable life.
Table– 1.1. Specifications of ater Used for Different Industries and Other Purposes
Other metal ions like Fe2+, Mn2+ and Al3+ also react with the soap in the same fashion, thus
contributing to hardness but generally these are present in natural waters only in traces. Further,
acids such as carbonic acid can also cause free fatty acid to separate from soap solution and thus
contribute to hardness. However, in practice, the hardness of a water sample is usually taken as a
measure of its Ca2+ and Mg2+ content.
1.4.1 Types of Hardness
It is of following two types:
(i) Temporary Hardness: Temporary hardness is mainly due to the presence of bicarbonate of
calcium and magnesium.
It is also known as carbonate hardness or alkaline hardness. It can be removed easily be boiling
the water. On boiling bicarbonates of calcium and magnesium get decomposed and formed insoluble
carbonates or hydroxides which can be removed in the form of precipitates
∆
Ca(HCO3)2 → CaCO3↓ + H2O + CO2↑
Mg(HCO3)2 ∆
→ Mg(OH)2↓ + 2CO2↑
(ii) Permanent Hardness: It is due to the presence of chlorides and sulphates of calcium,
magnesium, iron and other heavy metals such as Al2(SO4)3 etc. It is also known as non-carbonate
or non-alkaline hardness. It cannot be removed by simply boiling the water. However it can be
removed by using various chemical agents.
Total Hardness = Temporary Hardness + Permanent Hardness
Mg(HCO3)2 + 2Ca(OH)2
→ Mg(OH) ↓ + 2CaCO + 2H O
2 3 2
(ii) lime removes the permanent magnesium hardness:
MgCl2 + Ca(OH)2 → Mg(OH) ↓ + CaCl
2 2
MgSO4 + Ca(OH)2
→ Mg(OH) ↓ + CaSO
2 4
(iii) lime removes dissolved iron and aluminium salts:
FeSO4 + Ca(OH)2 → Fe(OH) ↓ + CaSO
2 4
2Fe(OH) + H O + O
2 2
→ 2Fe(OH) ↓
3
Al2(SO4)3 + 3Ca(OH)2
→ 2Al(OH) ↓ + 3CaSO
3 4
(iv) lime removes free mineral acids:
2HCl + Ca(OH)2
→ CaCl + 2H2O
2
H2SO4 + Ca(OH)2
→ CaSO + 2H2O
4
(v) lime removes dissolved CO2 and H2S
Ca(OH) + 2 CO 2
→ CaCO ↓
3 + H2O
Ca(OH)2 + H2S
→ CaS↓ + 2H2O
(vi) Soda removes all the soluble calcium permanent hardness (i.e., that which is originally pre-
sent as well as that which is introduced during the removal of Mg2+, Fe2+, Al3+, HCl, H2SO4
etc., by lime).
CaCl2 + Na2CO3 → CaCO3↓ + 2NaCl
CaSO4 + Na2CO3 → CaCO ↓
3 + Na2SO4
Since natural waters generally contain a large proportion of temporary hardness, it is often
convenient and economical to remove temporary hardness by lime treatment. Lime is rather cheap
and it removes temporary hardness efficiently without introducing any soluble salts in the water.
Magnesium hydroxide produced in the above reactions precipitates as an insoluble sludge. The
reaction of soda with the permanent calcium hardness produces insoluble CaCO3. Addition of a
coagulant such as sodium aluminate or alum helps in accelerating the coagulation of the carbonate
sludge, which is subsequently removed by filtration. Water softened by this process contains
appreciable concentrations of soluble salts, such as sodium sulphate, and cannot be used in high-
pressure boiler installations.
6 BASIC ENGINEERING CHEMISTRY
Types of cold lime-soda softeners
There are four basic types of cold lime soda softeners:
(1) The intermittent type (batch process)
(2) The conventional type
(3) The catalyst or spiractor type continous process
(4) The sludge blanket type
(1) Intermittent or batch process
The intermittent type of cold
lime-soda softener consists of a set
of two tanks which are used in turn
for softening of water. Each tank is
provided with inlets for raw water and
chemicals, outlets for softened water
and sludge, and a mechanical stirrer
(Fig. 1.1). Raw water and calculated
quantities of the chemicals are slowly
sent into the tank simultaneously under
agitation with the help of the stirrer. Fig.1.1. Intermittent cold lime-soda softener.
Some sludge from a previous operation
is also added which forms nucleus for
fresh precipitation and thus accelerates the process. Thus by the time the tank is full, the reaction
is more or less complete. Stirring is stopped and the sludge formed is allowed to settle. The clear
softened water is collected through a float pipe and sent to the filtering unit. The sludge formed in
the tank is removed through the sludge outlet. By employing a set of tanks planned for alternate
cycles of reaction and settling, continuous supply of softened water may be ensured.
(2) Conventional type
In this process, the raw water and
the chemicals in calculated quantities are Raw
water Chemicals
continuously fed from the top into an inner
chamber of vertical circular tank provided
with a paddle stirrer (Fig. 1.2). The raw water Softened
water
and the chemicals flowing down the chamber
come into close contact and the softening
reactions take place. The sludge formed settles Fibre filter
down to the bottom of the outer chamber from
Paddle stirrer
where it is periodically removed through the
sludge outlet. The softened water rising up
passes through the fibre filter where traces
Sludge
of sludge are removed and filtered soft water Sludge outlet
passes through the outlet provided.
Water treated by the cold lime-soda process Fig. 1.2. Conventional type of lime-soda
softner.
generally produces softened water containing
about 50 – 60 ppm of residual hardness.
WATER AND ITS INDUSTRIAL APPLICATIONS 7
(3) Catalyst or spiractor type
Air vent
The spiractor consists of a conical tank
which is about two-thirds filled with finely
divided granular catalyst (Fig. 1.3). The tank
used may be either open (for gravity operation) Softend
water
or closed (for operation under pressure). In
both the cases the raw water and the calculated Catalyst
quantities of chemicals enter the tank tangentially (crushed and graded
near the bottom of the cone and spiral upwards Raw calcite or green sand)
water
through the suspended catalyst bed. The catalyst Chemicals
employed is a finely granuled (0.3 to 0.6 mm
Draw-off valve
diameter) insoluble mineral substance such for enlarged catalyst
as graded calcite or sand or green sand. The Fig. 1.3. Catalyst or spiractor type cold lime-
retention time is about 8 to 12 minutes. The soda water softener.
sludge formed during the softening reactions
deposits on the catalyst grains in an adherent
form and hence the granules grow in size. The softened water rises to the top from where it is drawn
off.
The catalyst or spiractor type of continuous water softener is of interest as it gives a granular
sludge which drains and dries rapidly and can be handled easily.
(4) The sludge blanket type
The sludge blanket type of water treatment equipment is extensively used for coagulation
and settling as well as water softening by cold lime soda process. These softeners differ from the
conventional type in that the treated water is filtered upwardly through a suspended sludge blanket
composed of previously formed precipitates. Thus in a single unit, all the three processes namely
mixing, softening and clarification take place
In the conventional type of equipment, some of the added lime suspension is carried down in
the sludge formed by the precipitates, before it has time to dissolve and react with the hardness
causing impurities of the raw water and thus some of the lime is wasted. In the sludge blanket type,
this does not happen because the upward filtration through the suspended sludge blanket ensures
complete utilization of the added lime.
With the conventional type of equipment, it is generally observed that after precipitates or
after deposits form on the granules or filter media employed, and in pipe lines or distribution
systems carrying the filtered effluents. This usually necessitates recarbonation with CO2 to obviate
the formation of such deposits. However, in the sludge blanket type of equipment, the intimate
contact of the treated water with a large mass of solid phase mostly prevents super-saturation or
the formation of after deposits. This results in the production of the effluent which is clear enough
(turbidity usually less than 10 mg/l) for many industrial applications, so that subsequent filtration is
often unnecessary.
The retention period required with sludge blanket type equipment is one hour as against four
hours with the conventional units. Further, silica is removed better in sludge blanket units.
The sludge blanket type of water softening equipment, owing to its higher efficienc , shorter
detention period and smaller space requirements, is rapidly displacing the conventional type.
8 BASIC ENGINEERING CHEMISTRY
Hot lime-soda process
143.0
The reactions during water softening
take place in very dilute solutions (about 114.4
For instance, 136 parts by weight of CaSO4 would contain the same amount of Ca as that of 100
parts by weight of CaCO3. Hence, in order to convert the weight of CaSO4 as its CaCO3 equivalent,
100 50
the weight of CaSO4 should be multiplied by a factor of or .
136 68
Conversion factors for some of the impurities in water which commonly come across are given
in Table 1.2.
Table 1.2
Salt Multiplication factor to
convert into its CaCO3 equivalent
(1) (2)
Ca(HCO3)2 100/162
Mg(HCO3)2 100/146
CaSO4 100/136
CaCl2 100/111
MgSO4 100/120
MgCl2 100/95
Mg(NO3)2 100/148
Ca2+ 100/40
Mg2+ 100/24
100 100
HCO3– =
61 × 2 122
100 100
HCl =
36.5 × 2 73
H2SO4 100/98
CO2 100/44
100 100
Al2(SO4)2 =
342/3 114
FeSO4 . 7H2O 100/278
CaCO3 100/100
MgCO3 100/84
100 100
NaAlO2 =
82 × 2 164
Notes :
(a) If the impurities are given as CaCO3 or MgCO3, these should be considered to be due to
Ca(HCO3)2 or Mg(HCO3)2 respectively and they are only expressed in terms of CaCO3 and
MgCO3.
(b) The amount expressed as CaCO3 does not require any further convertion. However, the
amount expressed as MgCO3 should be converted into its CaCO3 equivalent by multiplying
with 100/84.
WATER AND ITS INDUSTRIAL APPLICATIONS 11
4. Calculate the lime and soda requirements as follows:
Temporary calcium hardness + (2 × Temporary magnesium
(A) Lime required
for softening
= } 74
×
hardness) + Perm. Mg hardness + CO 2 + HCl + H 2SO 4
- 2+ 3+
100 + HCO3 + salts of Fe , Al etc., - Na AlO 2 ; all expressed
in terms of their CaCO3 equivalents
× Volume of water × Purity
Fe(HCO3)2 + Na2Z
→ FeZ + 2NaHCO3
Mn(HCO3)2 + Na2 Z
→ MnZ + 2NaHCO3
(Note : Soluble iron and manganes are always present in the diva-
Softend
lent form in waters containing bicarbonate alkalinity). water
Fig. 1.6. Zeolite softener.
Regeneration: When the zeolite bad is exhausted (i.e., saturated
with Ca2+ and Mg2+), it can be regenerated by washing the zeolite
bed with concentrated sodium chloride (brine). Sodium nitrate, sodium sulphate potassium chloride
or potassium nitrate could also be used.
CaZ + 2NaCl → Na2Z + CaCl2
MgZ + 2NaCl → Na2Z + MgCl2
Hard Brine
water Cl
– –
Na+ Cl
Ca 2+ SO42–
Mg 2+
Ca Z Ca Z
Na2 Z and and Na2 Z
Mg Z Mg Z
Softening Exhausted Regenerated
–
Cl progresses
Na+ SO42–
9. This process adjusts itself to waters of 9. Reagent doses must be adjusted for waters
different hardness. of different hardness.
10. Salts causing temporary hardness are 10. Temporary hardness is completely re-
converted to NaHCO3 which will be moved in the form
present in the softened water. Such of
insoluble CaCO3 and Mg(OH)2. a wa-
ter creates problems when used as feed
water in boilers.
11. No problems of after precipitation. 11. There may be problems of after precipi-
tation in distribuion systems and even in
boilers when used as boiler feed water.
CH — CH2 — CH — CH2— CH
– –
SO3 H+ SO3 H+
Fig. 1.8. An Cation Exchanger Resin.
Resins having SO3H group are known as strongly acidic resins. While resins having COOH
group are known as weakly acidic resins.
(b) Anion Exchange Resins: Resing having basic functional groups like amine, substituted
amine or quaternary ammonium groups as their hydroxide salts are known as anion exchange
resins. They are styrene divinyl benzene complexes which are capable of exchanging their
basic functional groups with the anions of the solution.
WATER AND ITS INDUSTRIAL APPLICATIONS 15
— CH — CH2 — CH — CH2— CH
+ – + –
CH2NR3 OH CH2NR3 OH
H2C — CH— CH2
H2C — CH CH— CH2—
+ – + –
CH2NR3 OH CH2NR3 OH
Fig. 1.9. An Anion Exchanger Resin.
For effective water treatment, ion exchangers should possess the following properties.
1. They should be non-toxic.
2. They should not decolourise the water being treated.
3. They should possess a high ion-exchange capacity. (It depends upon the total number of ion
active groups per unit weight of the exchanger and is expressed as mill equivalents per gram
of the exchanger).
4. They should be physically durable.
5. They should be resistant to chemical attack.
6. They should be cheap and commonly available.
7. They must be capable of being regenerated and back-washed easily and economically.
8. They should have a large surface area since ion-exchange is a surface phenomenon. At the
same time, their resistance to flow must be compatible with hydraulic requirements
Process: The ion exchange unit consists of two tanks. Cation exchange resins are placed in first
tank and anion exchange resins are placed in second tank. At first hard water is passed through a
cation exchange resin. All the Ca2+ and Mg2+ ions are exchange by H+ ions of resin.
2RH+ + CaSO4 → R2Ca2+ + H2SO4
2RH+ + MgSO4 → R2Mg2+ + H2SO4
2RH+ + CaCl2 → R2Ca2+ + 2HCl
2RH+ + MgCl2 → R2Mg2+ + 2HCl
The effluent (from this step) is then passed through an anion exchanger tank. Here the anions
like SO42–, Cl– etc are present in water exchanged from OH– ions of the resin.
ROH– + Cl– → RCl– + OH–
2ROH– + SO42– → R2SO42– + 2OH–
2ROH– + CO32– → R2CO32– + 2OH–
The water coming out of the anion exchanger is completely free from cations and anions
responsible for hardness. It is known as deiomized or demineralized water.
H+ released from cation exchanger combine with OH– released from anion exchanger and
formed H2O
H+ + OH–
→ H2O
16 BASIC ENGINEERING CHEMISTRY
Raw
water
To vacuum
pump
steam
Cation Anion jacket
exchanger exchanger
Alkali for
regeneration
Acid for
regeneration Deionised
water
Fig. 1.10. Demineralization of water.
Regeneration. After some time the cation and the anion exchangers get exhausted and stop
working. The anion exchanger may be regenerated by treating it with NaOH solution.
R2SO42– + 2NaOH → 2ROH– + Na2SO4
R2Cl– + NaOH → ROH– + NaCl
The cation exchanger may be regenerated by passing a solution of HCl or H2SO4
R2Ca2+ + H2SO4 → 2RH+ + CaSO4
R2Mg2+ + H2SO4 → 2RH+ + MgSO4
or R2Ca2+ + 2HCl → 2RH+ + CaCl2
R2Mg2+ + 2HCl → 2RH+ + MgCl2
Mixed bed deionizer: Demineralisation of water can be better achieved by using a “mixed
bed” of cationic and anionic resins. This method produces an effluent which is far superior to that
produced by the two bed operation. When water is passed through a “mixed bed” consisting of
anion and cation exchange resins, each pair of contrasting resin particles functions as a stage in the
treatment and thus the total effect is that of a multiple cycle deionisation. Thus the process is highly
efficient
When the resins are exhausted the bed is backwashed when the two resins are separated in
different layers due to difference in their densities. Then the resins are separately regenerated,
washed and mixed again by injecting air and reused for a fresh cycle.
Advantages
(i) Highly acidic or alkaline water can be softened.
(ii) Water of very low hardness is produced (about 2 ppm)
(iii) Anions as well as cations are removed thereby problems like caustic embrittlement and cor-
rosion are reduced.
Disadvantage
(i) The process is costly.
(ii) Turbid water decreases the efficiency of the process
1.5.2 (b) Internal Treatment
Internal treatment consists of adding chemicals directly to the water in the boilers for removing
dangerous scale forming salts which were not completely removed in the external treatment for
water softening. This is mainly used as a corrective treatment to remove the slight residual hardness
and also sometimes to remove the corrosive tendencies in water. This treatment is not usually
WATER AND ITS INDUSTRIAL APPLICATIONS 17
applied to raw waters, except for small boilers, but it is usually practised in larger power stations. In
modern heavy-duty high pressure boilers, water of zero hardness is required, since even an egg-shell
thickness of scale may be extremely detrimental.
(A) Carbonate conditioning: In this, method we add sodium carbonate to boiler water, so that
salt like CaSO4 etc are converted into calcium carbonate and can be removed
CaSO4 + Na2CO3 → Na2SO4 + CaCO3
For a salt to be precipitate, sufficient amount of the ions forming the salt must be present, so
that the product of their ionic concentration is high from their solubility product. Thus, for a salt like
CaCO3 to be precipitated, the product of the concentration of Ca2+ and CO3– – must high from the
solubility product of CaCO3.
The above principles are used in the carbonate conditioning when sodium carbonate solution is
added to boiler water, the concentration of CO32– ion increased and when it becomes greater than the
solubility product of SO4– –(i.e. greater than K' × [SO4– –], only CaCO3 get precipitated and CaSO4
remains in solution. Thus the deposition of scale forming CaSO4 is prevented
Na2CO3 + CaSO4 → CaCO3↓ + Na2SO4
Carbonate conditioning is used only for low pressure boiler. In high pressure boiler the excess
Na2CO3 might be converted into NaOH due to hydrolysis as follows
Na2CO3 + 2H2O 2NaOH + H2CO3
H2O + CO2↑
H2CO3
NaOH causes caustic embrittlement in high pressure boilers.
(B) Phosphate conditioning: Phosphate conditioning is applicable to high pressure boilers. In
this method an excess of soluble phosphate is added to boiler water. It react with Ca and Mg salts
and form soft sludge of Ca and Mg phosphate which can be removed by blow down process
3MCl2 + 2Na3PO4 → M3(PO4)2↓ + 6NaCl
The three sodium orthophosphates viz., Na3PO4, Na2HPO4 and NaH2PO4 have been used for
phosphate conditioning. Sodium pyrophosphate (Na4P2O7) and sodium metaphosphate (NaPO3) are
also used for the same. The typical reactions of the various phosphates with the hardness represented
as CaCO3, may be summarized as follows:
2 Na3 PO4 + 3 CaCO3
→ Ca3(PO4)2 + 3 Na2CO3
2Na2HPO4 + 3 CaCO3
→ Ca3(PO4)2 + 2 Na2CO3 + CO2 + H2O
2 NaH2PO4 + 3 CaCO3
→ Ca3(PO4)2 + Na2CO3 + 2 CO2 + 2 H2O
2 NaPO3 + 3 CaCO3 → Ca3(PO4)2 + Na2CO3 + 2 CO2
The quality of the feed water decide the choice of a particular phosphate to be used. For instance,
if the feed water tends to produce an acidic condition in the boiler, the alkaline Na3PO4 should be
chosen. This treatment could be supplemented with NaOH if the required alkalinity could not be
maintained with Na3PO4 alone. If the feed water produces almost the right alkalinity desired in the
boiler, it is preferable to use Na2HPO4 which is practically neutral. If the boiler water becomes too
alkaline, the acidic NaH2PO4 would be selected.
Both sodium pyrophosphate and metaphosphate are rapidly hydrolysed under boiler water
temperatures to orthophosphate.
NaPO3 + H2O = NaH2PO4
Na4P2O7 + H2O = 2 Na2HPO4
Thus, their behaviour within the boiler is identical with that of orthophosphates mentioned
above. However, NaPO3 solutions are practically neutral, whereas NaH2PO4 solutions are acidic.
Hence the former would be preferred if the use of NaH2PO4 causes feedline corrosion.
18 BASIC ENGINEERING CHEMISTRY
The use of internal treatment combined with suitable blow down to remove sludge has
contributed largely to the operation of the modern high-pressure steam boilers without the formation
of hard scales. However, precaution should be taken to inspect them at least once in six months and
remove the scale and sludge accumulations.
(C) Colloidal conditioning : Scale formation can also be minimised by adding some colloidal
conditioning agents such as glue, agar agar, tannins, starches and sea-weed extract into the boiler
feed water. These substances act as protective colloids. They function by surrounding the minute
particles of CaCO3 and CaSO4 and prevent their coalescence and coagulation. Thus, the precipitated
scale-forming salts are maintained in loose suspended form which can easily be removed by blow-
down operation. Thus the scale formation is prevented.
(D) Calgon conditioning : Another approach for preventing scale formation is to convert the
scale forming salts into highly soluble complexes which are not easily precipitated under the boiler
conditions. In order to achieve this, sodium hexameta phosphate (Na PO3)6 or Na2 [Na4P6O18] (its
trade name is calgon) is generally employed. This substance interacts with the residual calcium ions
forming highly soluble calcium hexametaphosphate and thus prevents the precipitation of scale-
forming salts.
Na2 [Na4P6O18] 2 Na+ + [Na4P6O18]2–
2 Ca2+ + [Na4P6O18]2– → 4 Na+ + [Ca2P6O18]2–
Sludge Scales
1. They are soft, loose and slimy precipitate They are hard deposits
2. They are non-adherent deposits and can be They stick very firmly to the inner surface of
easily removed boiler and are very difficult to remov
3. Produced by salt like CaCl2, MgCl2, MgSO4, Produced by salt like CaSO4, Mg(OH)2 etc
MgCO3 etc.
4. It formed at comparatively colder portion of It formed generally at heated portion of the
the boiler boiler
5. They are less dangerous They are more dangerous as compare to sludge.
(ii) Corrosion of Boiler Metal. Boiler corrosion is disintegration of boiler body material either
due to chemical or electrochemical reaction with its environment. Boiler corrosion takes place due
to following factors:
(a) Presence of free acids in water.
(b) Acids generated as a result of hydrolysis of some salts in water.
(c) Acids formed by the hydrolysis of fatty lubricating oils.
(d) Presence of dissolved gases such as O2, CO2, H2S etc., in water.
WATER AND ITS INDUSTRIAL APPLICATIONS 21
(e) Presence of salts like MgCl2 which directly attack the boiler metal:
MgCl2 + Fe + 2H2O → Mg (OH)2 + FeCl2 + H2
(f) Presence of salts like MnS2 which may generate H2SO4 due to oxidation and hydrolysis.
(g) Formation of galvanic cells.
Some of these factors are discussed below:
(a) Dissolved oxygen. Dissolved oxygen is the main source of corrosion in boilers. The
concentration of oxygen in boiler waters should be below 0.05 ppm for low pressure boilers and less
than 0.01 ppm for high pressure boilers (~ 500 psi).
Oxygen enters the boilers through raw make up water and also through infiltration of air into the
condensate system. When the water containing dissolved oxygen is heated in the boiler, the free gas
is evolved which corrodes the metal parts under the conditions obtaining in the boiler.
Dissolved oxygen can be removed by:
Mechanical de-areation of water. The solubility
of a gas is directly proportional to pressure and inversly
proportional to temperature (Daltons law and Henry’s
law). These two principles are made use of in the design
of mechanical de-areratior. In mechanical dearators,
dissolved oxygen is removed by injecting hot feed-water
as a fine spray into a vacuum chamber heated externally
by steam.
Chemical Treatment
For complete removal of dissolved oxygen, chemical
methods of treatment are adopted.
Fig. 1.12. Mechanical de-areration of
Sodium sulfite is suitable for boilers operating below water.
650 psi. The sulphite reacts with the dissolved oxygen to
form sulphate.
1
Na2SO3 + O → Na2SO4
2 2
This method is very effective for removing oxygen in low pressure boilers but cannot be used
in high pressure boilers because (i) increasing dissolved salts’ concentrations produce foaming and
priming and (ii) sodium sulphate decomposes and liberates SO2 and/or H2S.
Ferrous sulphate is also used sometimes. It reacts with dissolved oxygen giving a precipitate of
Fe (OH)2 which is oxidized to Fe(OH)3.
FeSO4 + 2NaOH → Fe(OH)2 + Na2 SO4
2Fe (OH)2 + H2O + O → 2Fe(OH)3
Hydrazine, N2H4 is now extensively used to remove dissolved oxygen in high pressure boilers.
The pure compound is an explosive inflammable liquid (B.Pt. 113.5°C) but the 40% aqueous
solution used for water treatment is quite safe to handle. However, rubber gloves must be worn to
guard against the danger of dermatitis in some cases. One of the important advantage of hydrazine
treatment is that combination with oxygen does not produce any salts. Nitrogen and water are the
only reaction products obtained.
N2H4 + O2 → N2 + 2H2O
The molecular weight of hydrazine and oxygen are the same (viz. 32), so that complete
elimination of 1 ppm of oxygen would require only 1 ppm of hydrazine (which is 1/8 of the necessary
concentration of sodium sulphite). The residual hydrazine can be measured easily by a colorimeter.
22 BASIC ENGINEERING CHEMISTRY
The amount of hydrazine added must be closely controlled. Any excess reagent decomposes in
the boiler, liberating ammonia:
3N2H4 = 4NH3 + N2
Dissolved ammonia can bring about corrosion of some alloys, e.g., copper alloy condenser
tubes.
(b) Dissolved mineral acids
Most of the natural waters are alkaline excepting waters from mining areas or those polluted
from acidic industrial wastes or those in which wet oxidation of sulphide minerals occur.
Some inorganic salts like magnesium chloride and calcium chloride are also corrosive agents.
MgCl2 hydrolyzes completely at 200°C producing hydrochloric acid as follows:
MgCl2 + 2H2O → Mg (OH)2 + 2HCl
CaCl2 also undergoes hydrolysis but to a lesser extent. At 600°C, its hydrolysis is about 25%.
Silicic acid catalyzes the reaction so that in water containing silica, appreciable quantities of HCl
may be formed at lower temperatures. The HCl thus produced reacts with iron as follows:
Fe + 2HCl = FeCl2 + H2
FeCl2 + 2H2O = Fe(OH)2 + 2HCl
Hence, even a small amount of MgCl2 can cause considerable corrosion of the metal. If the
amount of HCl formed is small, it might get neutralized by the alkalinity present in the water, but
otherwise it should be neutralized by the addition of alkali.
(c) Dissolved carbon dioxide
Natural waters contain CO2. Water containing bicarbonates release CO2 on heating. If CO2 is
released inside the boiler, it will go along with the steam and as the steam condenses, the CO2 is
dissolved in water forming carbonic acid. This produces intense local corrosion called pitting.
CO2 along with oxygen in water, can be removed by mechanical deaeration.
CO2 in water can be removed by lime treatment. Another method of removing CO2 from water
is to filter it through lime stone
CaCO3 + CO2 + H2O → Ca (HCO3)2
but this reaction produces temporary hardness in the water.
CO2 can be converted into ammonium carbonate by the addition of ammonia.
CO2 + 2NH3 + H2O → (NH4)2 CO3
However, the excess ammonia added to the boiler feed water may go along with steam to the
condenser. If some O2 is also present in the condensate, the ammonia may attack the condenser tubes
made of copper. Hence, a safe limit of 10 mg of NH3/litre of the condensate is prescribed.
(d) Formation of galvanic cells
Corrosion can also occur because of galvanic cell formation between iron and other metals
present in the alloys used in boiler fittings. This may also lead to pitting corrosion. This can be
prevented by suspending zinc plates which act as sacrificial anodes
(iii) Caustic embrittlement : Caustic embrittlement is a form of corrosion caused by a high
concentration of sodium hydroxide in the boiler water. It is characterised by the formation of
irregular intergranular cracks on the boiler metal, particularly at places of high local stress, such as
riveted seams, bends and joints. It is caused by the high concentration of NaOH which is capable of
reacting with steels stressed beyond their yield point. It is most likely to occur in boilers operating
at higher pressures, where NaOH is produced in the boiler by the hydrolysis of Na2CO3 as follows:
Na2CO3 + H2O → 2NaOH + CO2
The extent of the hydrolysis increases with temperature and may reach even 90% of the
carbonate present. The rate and extent, of corrosion by caustic embrittlement increases with the
concentration of NaOH and temperature and hence with increasing operating pressure.
WATER AND ITS INDUSTRIAL APPLICATIONS 23
NaOH so formed along with the natural alkalinity of water make the boiler water caustic. The
NaOH travels to the minute hair cracks, bends and joints. Water evaporates and the concentration of
NaOH at these points keep on increasing with time due to poor circulation of water at these points.
This caustic soda attracks the surrounding areas and corroding the boiler material or dissolving the
iron of the boiler. This causes caustic embrittlement of the boiler parts.
The caustic embrittlement can be explained by the formation of the concentration cell as
Iron at Rivets Conc. NaOH Dil NaOH Iron at plane surfaces
The iron surrounded by concentrated NaOH act as anode while iron surrounded by diltue NaOH
act as cathode. The concentrated alkali dissolves the iron as sodium ferroate (Na2FeO2). Sodium
ferroate decomposes (a short distance away from its place of formation) as
3Na2FeO2 + 4H2O → 6NaOH + Fe3O4 + H2
Due to regeneration of NaOH further dissolution of iron takes place.
The caustic embrittlement occurs more rapily in following cases.
(i) Due to high concentration of NaOH
(ii) Presence of compounds such as sodium silicate etc.
(iii) Material subjected to great stresses beyond then yield point.
Prevention of Caustic Embrittlement
(a) By using sodium sulphate or sodium phosphate as softening agent in place of sodium
carbonate: It is observed that boiler water containing sodium sulphate or sodium phosphate
prevent the caustic embrittlement by blocking the capillaries, thereby preventing the
infiltration of caustic soda solution to these. The concentration of Na2SO4 : NaOH are
maintained at 1 : 1, 2 : 1 or 3 : 1 for operating pressure of 10, 20 and > 20 atmospheres
respectively to check the caustic embrittlement.
(b) By adding lignins or tannins which help in blocking the infiltration of NaOH through the
hair cracks.
(c) By adding NaNO3: It neutralize the excess amount of alkali and therefore help in preventing
the caustic embrittlment.
(iv) Carry over. As steam rises from the surface of the boiling water in the boiler, it may be
associated with small droplets of water. Such steam, containing liquid water, is called wet
steam. These droplets of water naturally carry with them some suspended and dissolved
impurities present in the boiler water. This phenomenon of carrying of water by steam along
with the impurities is called “carry over”. This is mainly due to priming and foaming.
Steam used for power production is usually superheated for achieving greater efficiencies in
the turbine or engine in which steam is used. Wet steam causes corrosion in the inlet ends of the
superheaters. If the steam contains high percentage of moisture, the extent of superheating will
decrease with the consequent reduction in efficiency of the turbine or engine. Further, the water
carried over with the steam contains salts and sludges, these are carried into the superheater where
they may deposit as the water evaporates. This will seriously restrict the flow of steam. Moreover,
due to the insulating effect of these deposits, the superheater tubes also may burn out. A part of the
dried salts may be carried along with the steam farther and deposit on the high-pressure turbine
blades or in engine valves. Even a small amount of deposit on the turbine blades decreases its
efficiency considerably. In order to eliminate the bad effects of moisture, mechanical steam purifiers
are often installed in the steam drums of the boiler or between the boiler and the superheater. These
devices force the steam to take curved paths whereby due to centrifugal action, the moisture is
thrown out of the steam.
24 BASIC ENGINEERING CHEMISTRY
(a) Foaming. Foaming is the formation of small but presistent bubbles at the water surface.
These bubbles are carried along with steam leading to excessive priming.
According to Bancroft, foams are formed when there is a difference in concentration of solute
or suspended matter between the surface film and the bulk of the liquid. Substances which increase
the viscosity of the film favour production of foam. The bubbles may also be protected by finely
divided solids forming a protective “shell” around each of them. Any material which lowers the
surface tension of the water will collect at the interface and thus increase the foaming tendency of
the liquid.
Pure water has no tendency to form foam but almost all impurities causes foaming, specially the
dissolved impurities like soap which reduces the surface tension of water.
Foaming can be avoided by :
(i) By the removal of the foaming and stabilizing agents from the water.
(ii) By controlling the concentration of salts and sludge in the boiler by intermittent or continu-
ous blow down process.
(iii) By adding antifoaming agents e.g., castor oil etc.
(iv) A foam may be destroyed by the addition of another good foaming agent. The foam is fi-
nally destroyed by mutual antagenistic effect of the difference in charge (Positive and nega-
tive) on the colloidal partical of the two foams. e.g., When foam obtained by a solution of
an anionic detergent (e.g., Aerosol OT) mix with foam obtained by a solution of an cationic
detergent (Ethyl cetab), they destroy each other.
(b) Priming. When the steam is generated rapidly in the boilers, some droplet of the liquid
water are carried along with steam. This process is known as wet steaming or priming.
Causes of priming: The main causes of priming are given below:
(i) It is due to the presence of suspended impurities and to some extent to dissolved impurities
in the water.
(ii) Due to alage and vegetable growth
(iii) Feed water containg even a small quantity of scale forming salts may causes priming
(iv) Due to sudden boiling
(v) Due to very high water level in the boiler.
(vi) Due to high velocity of steam which carries water droplets alongwith it in the steam pips.
Minimization of primining. It can be minimised by:
(i) By using a proper designed boiler
(ii) By maintaing low water level
(iii) By avoiding rapid changes in the steaming rate
(iv) By minimizing foaming
(v) By using only soft water
Water Water
Sand Sand
Gravel Gravel
germicidal properties. The OCl– ions are capable of rupturing the cell membranes of the disease
producing microbes.
Bleaching powder has the limitations of being unstable during storage and also it increases the
calcium content of water rendering it more hard. Chlorine as a sterilizing agent has the advantages
of being economical, efficient, limited space requirement and convenience. Further, it does not
introduce any other impurities in the water. Both chlorine as well as bleaching power when used
in excess produce disagreeable odour in the water. Too much excess may cause irritation to the
mucous membranes. The unpleasant taste of this excess chlorine can be removed by treatment
with ammonia, which reacts with chlorine to form the tasteless compound chloramine (NH2.Cl).
Thus, the ammonia-chlorine treatment (chloramine process) is particularly useful where traces of
impurities are present (e.g., phenols) which produce unpleasant tastes when chlorine alone is used.
Further, chloramine provides a more lasting effect than that of chlorine.
Cl2 + NH3 → NH2Cl + HCl
Monochloramine
2Cl2 + NH3 → NHCl2 + 2HCl
Dichloramine
NH2Cl + Cl2 → NHCl2 + HCl
NH2Cl + H2O → HOCl + NH3
HOCl → HCl + [O]
nascent oxygen
The chloramine process consists of adding ammonia to water in the form of gas together
with chlorine resulting in the formation of dichloramine and monochloramine as shown above.
Dichloramine is a relatively stable compound and is perhaps not a sterilizing agent by itself.
However, it slowly decomposes with evolution of chlorine. Thus, the addition of ammonia stabilizes
the chlorine to provide a prolonged effect. This is particularly useful when the water is passed into
storage after treatment.
Chlorine, ammonia-chlorine, or sodium hypochlorite are used widely for the sterilization of
swimming-pool water.
A disadvantage of chlorination is the potential formation of trihalomethanes (such as chloroform,
bromodichloromethane, dibromochloromethane and bromoform) which are carcinogenic.
Trihalomethanes (THMs) may be formed when chlorine combines with natural organic substances,
such as decaying vegetation, etc., that may be present in water itself. One approach to tackle this
problem is to remove the organics completely before subjecting it to water chlorination.
In future, the actual removal of THMs from the treated water, perhaps by aeration or adsorption
on activated carbon, may become necessary.
Superchlorination
In superchlorination, a large excess of chlorine is added to the water, thereby destroying not
only the micro-organisms but also the other organic impurities present. This process ensures rapid
and complete sterilization and successfully used for waters derived from wells and rivers. This
process is usually followed by dechlorination by NH3 or SO2.
Break point chlorination
It is a more precisely controlled process in which just sufficient chlorine is added to oxidize
all the organic matter, destroy bacteria and react with any ammonia leaving a slight excess of free
chlorine. The amount of chlorine required for disinfecting water depends upon the inorganic and
organic impurities present in water. A relationship between the amount of chlorine added to water
and the free residual chlorine is shown in Fig. 1.16.
WATER AND ITS INDUSTRIAL APPLICATIONS 31
c
a Break-point
Sterilization by Ozone
Ozone is a powerful disinfectant and is readily absorbed by water. Ozone being unstable
decomposes as follows giving nascent oxygen which is capable of destroying the bacteria.
O3 → O2 + [O]
However, this process is relatively expensive but has the advantage of removing bacteria,
colour, odour and taste without leaving any harmful residual effects in the water being treated.
Sterilization by ultraviolet radiation
Ultraviolet radiation emanating from electric mercury vapour lamp is capable of sterilizing
water. This process is particularly useful for sterilizing swimming pool waters. However, this
process cannot be economical for water works. Irradiation of water by ultraviolet light is commonly
used for disinfection in food industries.
Water for domestic purposes on a smaller scale may be sterilized by boiling the filtered water
for about 20 minutes. Chemicals like potassium permanganate and tincture iodine are also used
occasionally but chlorine tablets and bleaching powder are more commonly employed.
100
Ca2+ → 40 × = 100 ppm
40
100
Mg2+ → 24 × = 100 ppm
24
100
Na+ → 8.05 × = 17.5 ppm
23 × 2
100
HCO3– → 183 × = 150 ppm
61 × 2
100
SO42– → 55.68 × = 58 ppm
96
100
Cl– → 6.74 × = 9.5 ppm
35.45 × 2
Hence,
Total alkalinity = 150 ppm
WATER AND ITS INDUSTRIAL APPLICATIONS 35
Calcium alkalinity = 100 ppm
Magnesium alkalinity = 50 ppm
Total hardness = 200 ppm
Calcium hardness = 100 ppm
Magnesium hardness = 100 ppm
Calcium temporary hardness = 100 ppm
(or calcium alkalinity)
Magnesium temporary hardness = 50 ppm
(or magnesium alkalinity)
Magnesium permament hardness = 50 ppm
(or magnesium non-carbonate hardness)
Hence the salts presents in terms of their CaCO3 equivalent may be expressed as follows:
Ca(HCO3)2 — 100 ppm
Mg(HCO3)2 — 50 ppm
MgSO4 — 50 ppm
Na2SO4 — 8 ppm
NaCl — 9.5 ppm
Rules:
1. Ca-alkalinity = Ca-hardness or total alkalinity, which ever is small.
2. (a) Mg-alkalinity = Mg-hardness, if total alkalinity is equal to or greater
than total hardness.
(b) Mg-alkalinity = Total alkalinity — Ca-hardness, if total alkalinity is
greater than Ca-hardness but less than total hardness.
3. Sodium alkalinity = Alkalinity — Total hardness.
4. Ca-non-carbonate hardness = Ca-harndess — Ca-alkalinity
5. Mg-non-carbonate hardness = Mg-hardness — Mg-alkalinity
6. Total non-carbonate hardness = Total hardness – Total alkalinity.
If any of the above computation gives negative or zero result, none of that substance is present.
Example 5. How many grams of FeSO4 dissolved per litre gives 210.5 ppm of hardness.
Solution.
FeSO4 ≡ CaCO3
56 + 16 + 64 100g
= 136 g
\ 100 ppm of hardness = 136 ppm of FeSO4
or 210.5 ppm of hardness
136 × 210.5
=
100
≡ 286.3 ppm of FeSO4
= 286.3 mg/L
or = 0.2863 g/L of FeSO4
Hence, 0.2863 g of FeSO4 dissolved per litre gives 210.5 ppm of hardness.
36 BASIC ENGINEERING CHEMISTRY
Example 6. A water sample contains 204 mg of CaSO4 per litre. Calculate the hardness in
terms of CaCO3 equivalent.
Solution.
CaSO4 ≡ CaCO3
136g mol 100g mol–1
–1
92% pure soda required for softening 20,000 litres of the water sample
106 100 20, 000
= [25 + 25 + 25] × ×
100 92 1, 000
CaSO4 CaCl2 MgSO4 Purity grams for
factor 2,000 litres
= 1728.26 g = 1.72826 kg
Example 2. A water sample has the analytical report as under:
MgCO3 — 84 mg/l
CaCO3 — 40 mg/l
CaCl2 — 55.5 mg/l
Mg(NO3)2 — 37 mg/l
KCl — 20 mg/l
Calculate the amount of lime (86% pure) and soda (83% pure) needed for the treatment of
80,000 litres of water.
Solution.
CaCO3 and MgCO3 should be regarded as being present in the form of their bicarbonates and
only their weights have been expressed in terms of CaCO3 and MgCO3. KCl does not react with
lime or soda and also it does not contribute to hardness.
On converting the weights of each constituent in terms of their CaCO3 equivalent, we get the
following:
Salt CaCO3 equivalent
100
MgCO3 — 84 × = 100 mg/l
84
100
CaCO3 — 40 × = 40 mg/l
100
100
CaCl2 — 55.5 × = 50 mg/l
111
100
Mg(NO3)2 — 37 × = 25 mg/l
148
KCl — Ignored
86% pure lime required for softening 80,000 litres of the water
74 100 80, 000
= [(2 × 100) + 40 + 25] × ×
100 86 1, 000
MgCO3 CaCO3 Mg(NO3)2 Purity grams for
factor 80,000 litres
= 18241.86 g. = 18.24186 kg
83% pure soda required for softening 80,000 litres of the water
106 100 80, 000
= [50 + 25] × ×
100 83 1, 000
CaCl2 Ca(NO3)2 Purity grams for
generated from reaction factor 80,000
of lime with Mg(NO3)2 litres
= 7662.65 g. = 7.6625 kg.
WATER AND ITS INDUSTRIAL APPLICATIONS 43
Example 3. A water sample, on analysis, gave the following data :
MgCl2 — 95 ppm
CaSO4 — 272 ppm
MgSO4 — 120 ppm
H2SO4 — 49 ppm
SiO2 — 4 ppm
Calculate the amount of lime (95% pure) and soda (97% pure) needed for treating 1 million
litres of water. If the costs of lime and soda are Rs. 40 and Rs. 2000 per 100 kg each respectively,
calculate the total cost of chemicals used for treating 1 million litres of the water.
Solution.
Impurity CaCO3 equivalent
100
MgCl2 95 × = 100 mg/l
95
100
CaSO4 272 × = 200 mg/l
136
100
MgSO4 120 × = 100 mg/l
120
100
H2SO4 49 × = 50 mg/l
98
SiO2 Ignored
Amount of 95% pure lime required for softening 1 million litres of the water
74 100 106
= [100 + 100 + 50] × ×
100 95 106
MgCl2 MgSO4 H2SO4 purity kg for
factor 106 litres
= 194.74 kg
... Cost of the lime required at the rate of Rs. 40 per 100 kg
194.74 × 40
= = Rs. 77.90
100
Similarly, amount of 97% pure soda needed for 1 million litres of the water
106 100 106
= [100 + 200 + 100 + 50] × ×
100 97 106
CaCl2 CaSO4 CaSO4 CaSO4 purity kg for
derived derived derived factor 106 litres
from from from
MgCl2 MgSO4 H2SO4
during during during
lime lime lime
treatment treatment treatment
= 491.75257 kg
... Cost of the soda required at the rate of Rs. 2000 per 100 kg
491.75257 × 2000
= = Rs. 9835.05
100
44 BASIC ENGINEERING CHEMISTRY
... Total cost of the chemicals needed for softening 1 million litres of the water
= Rs. (77.90 + Rs. 9835.05) = Rs. 9912.95
Example 4. A water sample, on analysis, gave the following constitutents in grains per gallon
MgCl2 — 9.5
CaSO4 — 3.4
CaCO3 — 5.0
Mg(HCO3)2 — 7.3
MgSO4 — 6.0
SiO2 — 2.4
Calculate the cost of the chemicals required for softening 20,000 gallons of water if the purities
of lime and soda are 95% and 90% respectively. The costs per 100 pounds each of lime and soda
are Rs. 28 and Rs. 96 respectively.
Solution.
Salt CaCO3 equivalent
100
MgCl2 9.5 × = 10 gpg
95
100
CaSO4 3.4 × = 2.5 gpg
136
100
CaCO3 5.0 × = 5.0 gpg
100
100
Mg(HCO3)2 7.3 × = 5.0 gpg
146
100
MgSO4 6.0 × = 5.0 gpg
120
SiO2 Ignored
Lime is required for [Temporary calcium hardness
+ (2 × Temporary magnesium hardness)
+ permanent magnesium hardness]
= 5 + (2 × 5) + 10 + 5 = 30 gpg
... Cost of 95% pure lime required for softening 20,000 gallons at the rate of Rs. 28 per 100 lbs
74 1 100 28
= × 30 × 20,000 × × ×
100 7000 95 100
lime required gallons 1 lb = 7000 purity cost per
per gallon treated grains factor 100 lb
= Rs. 18.69
Similarly, soda is required for [Ca permanent hardness + Mg permanent hardness which
generated equivalent quantity of Ca permanent hardness during lime treatment]
= 2.5 + (10 + 5) = 17.5 gpg
... Cost of 90% soda required for treating 20,000 gallons at the rate of Rs. 96 per 100 lbs
106 1 100 96
= × 17.5 × 20,000 × × ×
100 7000 90 100
Soda required gallons 1 lb = 7000 purity cost per
per gallon treated factor factor 100 lb
= Rs. 56.53.
WATER AND ITS INDUSTRIAL APPLICATIONS 45
Example 5. A water sample, using FeSO4 . 7H2O as a coagulant at the rate of 139 ppm, gave
the following results on analysis:
Ca2+ — 160 ppm; Mg2+ — 72 ppm
CO2 — 88 ppm; HCO3– — 488 ppm
Calculate the lime and soda required to soften 1,00,000 litres of water.
Solution.
Impurity Equivalents of CaCO3
100
Ca2+ 160 × = 400 ppm
40
100
Mg2+ 72 × = 300 ppm
24
100
CO2 88 × = 200 ppm
44
100
HCO3– 488 × = 400 ppm
61 × 2
100
FeSO4 . 7H2O 139 × = 50 ppm
278
74
Lime required = × [Mg2+ + CO2 + HCO3– + FeSO4 . 7H2O]
100
74
= × [300 + 200 + 400 + 50]
100
74
= × 950 = 703 ppm
100
= 703 mg/l
Lime required for softening 1,00,000 litres of water
105
= 703 × = 70.3 kg
105
Similarly, soda required
106
= × [Ca2+ + Mg2+ + FeSO4 . 7H2O – HCO3– ]
100
106
= × [400 + 300 + 50 – 400]
100
106
= × 350 = 371 ppm
100
= 371 mg/l
.. . Soda required for softening 105 litres of water
6
= 371 × 10 = 37.1 kg
106
Note 1 Mg2+ + Ca(OH)2 → Mg(OH)2 + Ca2+
Note 2 –
2HCO3 + Ca(OH)2 → CO3– – + CaCO3 + H2O
(Two (Two (Two
equivalents) equivalents) equivalents)
46 BASIC ENGINEERING CHEMISTRY
Example 6. Calculate the quantities of lime and soda required for cold softening of 2,00,000
litres of water using 16.4 ppm of sodium aluminate as a coagulant. The results of the analysis of raw
water and softened water are as follows:
Raw water Softened water
2+
Ca — 160 ppm 2–
CO3 — 30 ppm
Mg2+ — 72 ppm OH– — 17 ppm
HCO3 – — 732 ppm
Dissolved CO2 — 44 ppm
Solution.
Converting each of the constituents into their respective equivalents of CaCO3, we have
Raw Water
Ion or salt ppm CaCO3 equivalent Lime Soda
(ppm) required, required
(ppm) (ppm)
100
Ca2+ 160 160 × = 400 — 400
40
100
Mg2+ 72 72 × = 300 300 300
24
100
HCO3– 732 732 × = 600 600 – 600
61 × 2
100
CO2 44 44 × = 100 100 —
44
100
NaAlO2 16.4 16.4 × = 10 – 10 – 10
82 × 2
Softened Water
100
CO32– 30 30 × = 50 — + 50
60
100
OH– 17 17 × = 50 50 + 50
17 × 2
1040 190
74
Lime required = × 1040 mg/l
100
Lime required for 2,00,000 litres of water
74 2, 00, 000
= × 1040 × kg
100 106
= 153.93 kg
Similarly, soda required
106
= × 190 mg/l
102
... Soda required for 2,00,000 litres of water
106 2, 00, 000
= × 190 × kg
100 106
= 40.28 kg.
WATER AND ITS INDUSTRIAL APPLICATIONS 47
Notes:
1. 1 equivl. of Ca2+ requires 1 equiv. of soda.
Ca2+ + Na2CO3 → CaCO3 + 2Na+
2. 1 equiv. of Mg2+ requires 1 equiv. of lime and 1 equiv. of soda.
Mg2+ + Ca(OH)2 → Mg(OH)2 + 2Ca2+
Ca2+ + Na2CO3 → CaCO3 + 2Na+
3. 1 equiv. of HCO3– requires 1 equiv. of lime which simultaneously produces 1 equiv. of
CO32–, which may be considered to be equivalent to 1 equiv. of soda.
Ca (OH)2 + 2HCO3– → CaCO3 + CO32 – + H2O
2 equiv. 2 equiv. 2 equiv.
4. 1 equiv. of CO2 requires 1 equiv. of lime.
5. 1 equiv. of NaAlO2 requires neither lime nor soda. But, however, NaAlO2 produces 1 equiv.
of OH–, which may be imagined to be 1 equiv. of lime
Na AlO2 + 2H2O → NaOH + Al (OH)3
Hence the corresponding quantity of NaAlO2 in equivalents should be deducted both from
lime as well as soda requirements.
6. Since the treated water is shown to contain OH– and CO32–, the required amount of
OH– should have been supplied by its equivalent amount of Ca(OH)2. But, however, the
corresponding amount of Ca2+ so incorporated should have been removed by adding
equivalent amount of soda. The CO32– required to be present in the treated water must have
been supplied by its equivalent amount of Na2CO3.
Example 7. The analytical report of a raw water sample is as follows:
Mg Cl2 — 47.5 mg/l
Ca Cl2 — 55.5 mg/l
Ca SO4 — 4.06 mg/l
Turbidity — 120 mg/l
10 mg/l alum dose was found to be sufficient to remove the entire turbidity of the water sample.
Calculate the total weight of the dry sediment in a lime-soda softening plant for 20,000 litres of
water. Alum contains 7% Al.
Solution.
1. MgCl2 + Ca(OH)2 → Mg(OH)2↓ + CaCl2
95 58 111
CaCl2 + Na2CO3 → CaCO3↓ + 2NaCl
111 100
95 mg of MgCl2 yields 58 mg of Mg(OH)2
58 × 47.5
... 47.5 mg of MgCl2 yields mg
95
= 29 mg of Mg(OH)2 ...(1 a)
Again,
95 mg of MgCl2 will produce 111 mg of CaCl2 which gives 100 mg of CaCO3 on treatment
with soda,
100
... 29 mg of MgCl2 will produce 29 × mg of CaCO3
95
= 30.526 mg of CaCO3 ...(1 b)
48 BASIC ENGINEERING CHEMISTRY
Example 11. A water sample contains the following impurities, Ca2+ = 20 ppm, Mg2+ = 18
ppm, HCO3– = 183 ppm and SO42– = 24 ppm. Calculate the amount of lime and soad needed for
softening.
Solution. Calculation of CaCO3 equivalents
Salt CaCO3 equivalent
100
Ca2+ = 20 ppm 20 × 50 ppm
=
40
100
Mg2+ = 18 ppm 18 × = 75 ppm
24
100
HCO3– = 183 ppm 183 × = 150 ppm
122
Requirement of lime
74
= [Mg 2 + + HCO3- ]
100
74
= [75 + 150] ppm
100
= 166.5 ppm or mg/L.
WATER AND ITS INDUSTRIAL APPLICATIONS 51
Requirement of soda
106
= [Ca 2 + + Mg 2 + - HCO3- ]
100
106
= [50 + 75 - 150] ppm
100
= Nil.
Example 12. Calculate the amount of lime and soda needed for softening 1,00,000 litre of
water containing the following HCl = 7.3 mg/L, Al2(SO4)3 = 34.2 mg/L MgCl2 = 9.5 mg/L, NaCl =
29.25 mg/L
Purity of lime is 90% and that of soda is 98%. 10% of chemicals are to be used in excess in
order to comlete the reaction quickly.
Solution. Calculation of CaCO3 equivalent
Salt CaCO3 equivalent
100
HCl = 7.3 mg/L 7.3 × = 10 mg/L
73
100
Al2(SO4)3 = 34.2 mg/L 34.2 × = 30 mg/L
114
100
MgCl2 = 9.5 mg/L 95 × =10 mg/L
95
Requirement of lime
74
= [HCl + Al2 (SO 4 )3 + MgCl2 ] × Vol of water ×100/% purity
100
74 100
= [10 + 30 + 10] mg/L × 105 L ×
100 90
6
= 4.111 × 10 mg
= 4.111 kg
Lime required (using 10% excess)
110
= 4.111 kg ×
100
= 4.522 kg
Requirement of soda
106
= [HCl + Al2 (SO 4 )3 + MgCl2 ] × Vol of water ×100/% purity
100
= 106 [10 + 30 + 10] mg/L × 105 L × 100
100 98
= 5.488 × 106 mg = 5.408 kg
\ Soda requirement using 10% excess
110
= 5.408 × = 5.949 kg
100
= 5.949 kg.
Example 13. A water sample on analysis gave the following data
Ca2+ = 30 mg/L, Mg2+ = 24 mg/L, CO2 = 24 mg/L, HCl = 50 mg/L, K+ = 10 mg/L
Calculate the quantities of lime (90% pure) and soda (94% pure) required to soften one million
litres of water sample.
52 BASIC ENGINEERING CHEMISTRY
Solution. Calculation of CaCO3 equivalent
Salt CaCO3 equivalent
100
Ca2+ = 30 mg/L 30 × = 75.0 mg/L
40
100
Mg2+ = 24 mg/L 24 × = 100.0 mg/L
24
100
CO2 = 24 mg/L 24 × = 54.5 mg/L
44
HCl = 50 mg/L 100
50 × = 68.5 mg/L
74 73
Requirement of lime = [Mg 2 + + CO 2 + HCl] × Vol. of water × (100/% purity)
100
74 100
= [100 + 54.5 + 68.5 mg/L] × 106 L ×
100 90
= 1.834 × 108 mg = 1.834 × 102 kg
= 183.4 kg
106
Requirement of soda = [Ca2+ + Mg2+ + HCl] × Vol of water × 100% purity
100
106 100
= [75 + 100 + 68.5] mg/L × 106 L ×
100 94
106 100
= [243.5 mg/L] × 106 L ×
100 94
= 2.946 × 108 mg
= 2.946 × 102 kg = 294.6 kg
Example 14. Calculate the amount of lime and soda required per litre for the chemical
treatment of water containing:
Ca2+ = 80 ppm, Mg2+ = 36 ppm, K+ = 39 ppm, HCO3– = 244 ppm, FeSO4.7H2O added as
coagulant = 69.5 ppm.
Solution. Calculation of CaCO3 equivalent
Salt CaCO3 equivalent
100
Ca2+ = 80 ppm 80 ×= 200 mg/L or ppm
40
100
Mg2+ = 36 ppm 36 × = 150 mg/L or ppm
24
100
HCO3– = 224 ppm 224 × =200 mg/L or ppm
122
FeSO4.7H2O = 69.5 ppm 100
69.5 × = 25 mg/L or ppm
278
74
Requirement of lime = [Mg 2 + + HCO3- + FeSO 4 .7H 2 O] × Vol. of water
100
74
= [150 + 200 + 25 mgL-1 ] × 1L
100
= 277.5 mg
106
Requirement of soda = [200 + 150 - 200 + 25 mgL-1 ] × 1L
100
= 185.5 mg.
WATER AND ITS INDUSTRIAL APPLICATIONS 53
Example 15. Explain with equation and calculate the quantity of quick lime and soda ash
required to soften 10000 litres of water containing:
(i) 219 ppm of Mg(HCO3)2 and 234 ppm of NaCl
(ii) 36 ppm of Mg2+ and 18.3 ppm of HCO3–
(iii) 1.5 ppm of the free acids, 144 ppm of sulphate ions and 71 ppm of chloride ions.
Solution. Calculation of CaCO3 equivalent 65
Mg(HCO3)2 + 2Ca(OH)2 → 2CaCO3 + Mg(OH)2 + 2H2O (2L)
Mg2+ + Ca(OH)2
→ Mg(OH)2 + Ca2+
Then,
Ca2+ + Na2CO3 → CaCO3 + 2Na+ (L + S)
2HCO3– + Ca(OH)2
→ CaCO3 + H2O + CO32– (L–s)
2H+ + Ca(OH)2
→ Ca2+ + 2H2O
Then,
Ca2+ + Na2CO3 → CaCO3 + 2Na+ (L + S)
74 10000
Lime = [2Mg (HCO3 ) 2 + Mg 2 + + HCO3- + H + ] × kg
100 106
74 100 100 100 100 1
= 100 2 × 219 × 146 + 36 × 24 + 18.3 × 122 + 1.15 × 2 × 100
= 3.996 kg
106 2 + 10000
Soda = Mg - HCO3- + H + × kg
100 106
106 100 100 100 1
= 100 36 × 24 - 18.3 × 122 + 1.5 × 2 × 100
= 2.226 kg.
Example 16. Calculate the amount of lime and soda required to soften 24000 litres of water
per day for a year containing the following
CaCO3 = 1.85 mg/litres, CaSO4 = 0.34 mg/litre, MgCO3 = 0.42 mg/litre, MgCl2 = 0.76 mg/
litre, MgSO4 = 0.90 mg/litre, NaCl = 2.34 mg/litre, SiO2 = 2.32 mg/litre. The purity of lime is 88.3%
and that of soda is 99.2%.
Solution. Calculat of CaCO3 equivalent
Salt CaCO3 equivalent
100
CaCO3 1.85 × = 1.85 mg/litre
100
100
CaSO4 0.34 × = 0.25 mg/litre
136
100
MgCO3 0.42 × = 0.50 mg/litre
84
100
MgCl2 0.76 × = 0.80 mg/litre
95
MgSO4 100
0.90 × = 0.75 mg/litre
120
Note: NaCl, Fe2O3 and SiO2 do not require lime soda)
Amount of water to be softened per year = 24000 litres × 365 = 8760000 litres
54 BASIC ENGINEERING CHEMISTRY
74
[Temp Ca + 2 × temp Mg + Per Mg] × Vol of water
Requirement of lime =
100
74
= [1.85 + 2 × 0.50 + 0.80] mg/litre × 8760000
100
= 2.701 × 8760000 mg = 2.701 × 8.76 kg
= 23.66 kg.
106
[Temp + Per Mg] × Vol of water
Requirement of soda =
100
106
= 100 [0.80 + 0.75] × 8760000
= 1.643 × 8760000 mg
= 1.643 × 8.76 kg
= 14.39 kg.
Example 17. Calculate the amount of lime and soda ash required to soften a million litres of
water having the following composition by lime soda proces:
Free CO2 = 20 ppm, Ca(HCO3)2 as CaCO3 = 200 ppm, Mg(HCO3)2 as MgCO3 = 5 ppm,
CaSO4 as Ca2+ ions = 30 ppm, MgSO4 as Mg2+ ions = 10 ppm.
Solution. Calculat of CaCO3 equivalent
Salt CaCO3 equivalent
100
CO2 = 20 ppm 20 × =45.45 ppm
44
100
CaCO3 = 200 ppm 200 × =200 ppm
100
100
MgCO3 = 5 ppm 5× 5.95 ppm
=
84
100
Ca2+ = 30 ppm 30 × =75 ppm
40
100
Mg2+ = 10 ppm 10 × =41.67 ppm
24
74
Requirement of lime = [CO 2 + CaCO3 + 2 × MgCO3 + Mg 2 + ] × Vol of water
100
74
= [45.45 + 200 + 2 × 5.95 + 41.67] × 106 litre of water
100
= 221.27 × 106 mg
= 221.27 kg
106
[Ca 2 + + Mg 2 + ] × Volume of water
Requirement of soda =
100
106
= [75 + 41.67] × 106 mg
100
= 123.67 kg.
WATER AND ITS INDUSTRIAL APPLICATIONS 55
QUESTIONS
1. Match the following and write appropriate statements in each case:
Group A Group B
(i) Dissolved oxygen (a) Lime and soda
(ii) Sequestration (b) Carbonate alkalinity only
(iii) Calcium sulphate (c) Carbonate and bicarbonate alkalinity
(iv) Sodium fluorid (d) Carbonate and hydroxide alkalinity
(v) Turbidity (e) Degree Clark
(vi) Tannin (f) Silica scale
(vii) Milligrams per litre (g) Colloidal conditioning
(viii) Colour (h) Parts per million
(ix) Grains per gallon (i) Silica removal
(x) M = 2P (j) Sodium hexametaphosphate
(xi) M < 2P (k) Hydrazine
(xii) M > 2P (l) Hazen units
(m) Boiler scales
2. Complete the following statements with appropriate words:
(a) To control total dissolved solids in boiler water during boiler operation ....................
practice is adopted.
(b) Inter-crystalline cracking occurs in boiler due to presence of .................... .
(c) Sodium bicarbonate gives .................... colour with phenolphthalein.
(d) .................... is used as an indicator in the estimation of calcium hardness by EDTA
method.
(e) Principle involved in the zeolite process of water softening is .................... .
(f) Pulsating steam demand is believed to be the cause of .................... in a boiler.
(g) Sludges are formed by the substances which have .................... solubilities in hot water
than in cold water.
(h) Zeolite plant usually occupies .................... space than a lime soda plant softening same
volume of water.
(i) Exhausted cation exchanger bed is regenerated by passing a solution of ....................
while exhausted anion exchanger is regenerated by treating it with .................... .
(j) 1 ppm = .......................... degree clark.
(k) Temporary hardness is due to ...................... .
3. Answer the following as directed:
(a) “If hard water contains sufficient magnesium hardness, silica can be removed effectively
in lime soda softening process”. State whether the statement is true or false. Justify your
answer.
(b) “Phosphate conditioning is suitable at all-operating pressures”. Give reasons to support
this statement.
(c) Mention any two points of contrast in lime soda and zeolite water softening processes.
(d) Explain any two major drawbacks of scale formation.
(e) A water sample contains Ca++ – 20 mg/l, Mg++ – 12 mg/l. What is the total hardness of
the sample?
56 BASIC ENGINEERING CHEMISTRY
4. What are boiler troubles and what are their consequences? How can be boiler troubles be
minimized?
5. (a) What do you mean by hardness of water? How is it classified
(b) What process of water softening would you recommend for obtaining feed water for
the modern high pressure boilers, and why?
6. Compare the hot lime soda process and the zeolite process of water softening with respect
to the principles involved, advantages and limitations.
7. Compare carbonate conditioning and phosphate conditioning of boiler water with respect to
the principles involved, advantages and limitations.
8. (a) Establish the relation between ppm and mg/l.
(b) Calculate the lime and soda required to soften 10,000 litres of the water sample having
the following analysis:
Calcium hardness — 250 ppm as CaCO3
Magnesium hardness — 100 ppm as CaCO3
Total alkalinity present — 300 ppm as CaCO3
9. What are the problems expected by using untreated water in a boiler? How can they be
minimized?
10. A zeolite softener was 75% exhausted by removing the hardness completely when 7000
litres of a water sample are passed through it. The zeolite bed required 180 litres of 2.5%
NaCl solution for complete regeneration. Calculate the harndess of the water sample.
11. A water sample on analysis gave the following data:
Ca2+ — 20 ppm, Mg2+ — 24 ppm
CO2 — 30 ppm, –
HCO3 — 150 ppm
K+ — 10 ppm
Calculate the lime (87% pure) and soda (91% pure) required to soften 1 million litres of the
water sample.
12. Discuss the different types of cold lime soda softeners and their relative merits and
demerits.
13. Write short notes on the following:
(a) Sludge blanket type of lime soda softener
(b) Cold lime-soda process
(c) Sedimentation
(d) Coagulation
(e) Filtration of water
(f) Sterilization.
14. Write short notes on the following:
(a) Caustic embrittlement (RGPV Bhopal 2009)
(b) Boiler corrosion (RGPV Bhopal 2006)
(c) Internal treatment
(d) Blow-down
(e) Break-point chlorination (RGPV Bhopal 2006)
(f) Deep well water
(g) Impurities in water and their effects
(h) Slow sand filtratio
WATER AND ITS INDUSTRIAL APPLICATIONS 57
(i) Rapid pressure filtratio
(j) Scall and sludge formation (RGPV Bhopal 2009)
15. (a) Write the constituents responsible for the permanent hardness of water. Discuss one
treatment method.
(b) Why does hard water consume a lot of soap ?
(c) Why does magnesium bicarbonate required double amount of lime for softening.
(U.P. Technical University 2001)
16. (a) Describe the causes, harmful effects and control of scale and sludge formation in
boilers. (RGPV Bhopal 2009)
(b) A water sample using FeSO4.7H2O as coagulant at the rate of 278 ppm. gave the
following results on analysis :
Ca++ – 80 ppm, Mg++ – 48 ppm,
CO2 – 88 ppm; and HCO3– – 244 ppm
Calculate lime soda required for softening one million litres of the water sample.
or
(a) What are zeolites ? Discuss the chemistry involved in zeolite process of softening hard
waer. Also mention the limitations, advantages and disadvantages of this process.
(b) A zeolite softener was completely exhausted and was regenerated by passing 120
litres of sodium chloride solution containing 150 g/litre of NaCl. How many litres
of a sample of water of hardness 500 mg/liter can be softened by the softener before
regenerating it again ? (RGPV Bhopal 2001)
17. (a) The analytical results of raw water and treated water are as follows :
Ca2+ = 300 ppm
Mg 2+ = 150 ppm
HCO3– = 244 ppm
OH– = 65 ppm
2–
CO3 = 40 ppm
CO2 = 60 ppm
Calculate,
(i) The amount of lime (80% pure) and soda (90% pure) required to soften one million
litres of water using NaAlO2 as a coagulant at the rate of 41 mg/litre.
(ii) If 10,000 litres of the same water sample is softened through a zeolite softener, how
much NaCl will be required for its regeneration ? (Nagpur University, S-2001)
18. (a) What is meant by hardness of water ? Name the substances that cause permanent hard-
ness in water?
(b) Explain the importance of “phosphate conditioning ? in the “internal treatment” of
water.
(c) What is “demineralisation process” ? Point out its advantages and limitations ?
(Mumbai University, 1994)
19. (a) Explain the principle and process of lime-soda softening of water giving the different
chemical reactions involved in the process. Point out the advantages of hot lime-soda
process.
(b) A zeolite softener was completely exhausted and was regenerated by passing 100 liters
of sodium chloride solution containing 100 g/l of sodium chloride. How many litres of
sample of water of hardness of 500 ppm can be softened by the softener ?
58 BASIC ENGINEERING CHEMISTRY
20. (a) How does the formation of sludge and scales affect boiler performance ?
(b) What is meant by “Phosphate Conditioning” of water ?
21. (a) Explain the demineralisation of hard water, with a neat diagram and appropriate
equations. (RGPV Bhopal 2009)
(b) A sample of water was found to contain the following impurities.
Mg(HCO3)2 = 156 mg/1
H2SO4 = 4.9 mg/l
MgCl2 = 23.75 mg/1
NaCl = 5.6 mg/l
CaCl2 = 111 mg/1
SiO2 = 16.2 mg/l
Calculate the amount of lime (90% pure) and Soda (95% pure) required to soften
50,000 litres of the above water sample.
22. (a) Three water samples A, B and C were analyses for their salt contents. Sample A was
found to contain 168 gms of magnesium carbonate per liter. Sample B was found to
contain 82 gms of calcium nitrate and 2 mg of silica per litre, sample C was found to
contain 20 gms of potassium nitrate and 20 gms of calcium carbonate per 500 ml.
Determine the hardness in all the above three water samples.
(b) How does dissolved oxygen affect the quality of water used in boilers ? What are the
various methods employed in deaeration of water ?
23. (a) Describe lime-soda process of softening of water giving diagram and reaction
involved. (RGPV Bhopal 2009)
(b) When do you recommend only internal treatment for boiler water and completely
avoiding external treatment ?
(c) Write a brief note on “caustic embrittlement”.
24. (a) Why feed water conditioning is necessary in boilers ? What are the methods available
for the same ?
(b) Calculate the quantity of lime needed for softening of 5000 litres of water containing :
CaSO4 = 13.6 mg/l
MgCO3 = 8.4 Mg/l
CaCO3 = 5 mg/l
KNO3 = 20 mg/l (Mumbai University, 1998)
25. (a) Give only the equations involved in the lime-soda process. Describe the advantages of
hot-lime soda process over cold lime-soda process. (RGPV Bhopal 2006)
(b) The hardness of 10,000 litres of a sample of water (containing 341.9 ppm hardness)
was completely removed by passing it through a zeolite softener. The zeolite softener
was regenerated by passing sodium chloride solution containing 20 gms/l of sodium
chloride. How many litres of sodium chloride solution will be required to regenerate
zeolite softener ? (Mumbai University, 1998)
26. (a) What is the difference between scale and sludge ?
(b) What principle is applied to remove hardness of water. Explain giving chemical
reactions.
(c) Describe with the help of a neat labelled diagram ion-exchange process for purification
of water. (Mumbai University, 1999)
27. (a) Write notes on industrial uses of water.
WATER AND ITS INDUSTRIAL APPLICATIONS 59
(b) A zeolite softener was completely exhausted and was regenerated by passing 100 litres
of NaCl solution containing 60 gms/liter of NaCl. How many litres of a sample of
water of hardness 400 ppm can be softened by this softener ?
(Mumbai University, 1999)
28. (a) Describe with the help of a neat labelled diagram, the hot lime-soda process of softening
of water.
(b) The hardness of 10,000 litres of a hard water sample was completely removed by
passing it through a zeolite softener. The zeolite softener requires 5,000 litres of sodium
chloride solution containing 1170 mg of NaCl per litre for regeneration. Determine the
hardness of the water sample. (Mumbai University, 2000)
29. (a) Calculate the quantities of lime and soda required to soften 1 million litres of hard
water containing the following impurities.
CaCO3 – 10.0 ppm
Mg(HCO3)2 – 36.5 ppm
Al2(SO4)3 – 17.1 ppm
CaSO4 – 20.4 ppm
MgCl2 – 19.0 ppm
and SiO2 – 24.0 ppm
(b) State the limitations of the zeolite process of softening of water.
(Mumbai University, 2000)
30. (a) Explain with a neat sketch and all chemical reactions taking place, the zeolite permutit
process for softening water. What are the advantages and disadvantages of this process
(any two).
(b) Write a brief note on “Boiler Corrosion”.
(c) Calculate the quantity of lime and soda needed to soften 20,000 litres of hardwater
containing the following salts :
MgCl2 = 9.5 mgs/lit
CaCl2 = 22.2 mgs/lit
Ca(CHO3)2 = 81 mgs/lit
FeSO4 = 151.8 mgs/lit
Mg(HCO3)2 = 73 mgs/lit
MgSO4 = 120 mgs/lit
(d) Write brief notes on internal conditioning of boiler water. (Mumbai University, 2001)
(e) A totally exhausted zeolite softener required 50 litres of NaCl solution containing 351
g of NaCl/litre. How many litres of a hard water sample containing 70° clark hardners,
can be softened by this process.
31. (a) Mention the advantages of hot lime-soda process of softening of water.
(b) What are the different units for expressing hardness of water ?
32. (a) What are the natural sources of water ?
(b) How the presence of hardness of water affect the consumption of soap ?
(c) A Zeolite softener was 80% exhausted by removing the hardness completely when 800
litres of water are passed through it. The Zeolite bed required 200 litres of 3% NaCl
solution for complete regeneration. Calculate the hardness of water.
(d) Write short notes on:
(i) Sterilization
60 BASIC ENGINEERING CHEMISTRY
(ii) Regeneration of exhausted ion-exchange resins
(iii) Coagulation. (Nagpur University, 2002)
33. Calculate the quantities of lime and soda required to soften 1,25,000 litres of water having
the following analysis and using 50 mg/l of sodium aluminate as coagulant :
Ca2+ – 300 mg/l
Mg2+ – 96 mg/l
CO2 – 44 mg/l
HCO3– – 100 mg/l
(a) What do you understand by the terms priming and foaming ? How can they be
controlled ?
(b) What are the methods available for deaeration of boiler feed water ?
(Nagpur University, 2002)
34. Calculate the cost of lime and soda required for softening 1 million litres of water containing :
Mg(HCO3)2 = 73 mg/l
MgSO4 = 120 mg/l
CaSO4 = 68 mg/l
CaCl2 = 111 mg/l
The cost of lime of 80% purity is Rs. 200/MT and that of soda of 90% purity is Rs.
12000/M.T.
35. (a) What are the disadvantages of scale formation ? Explain briefly the various methods
adopted for prevention of scale formation.
(b) Describe a treatment method for municipal water supply. (Nagpur University, 1997)
36. (a) How is water softened by lime-soda process ? Describe the types and chemical reactions
involved.
(b) What are the external and internal treatment required for prevention of scale formation
in the boiler.
(c) Explain the functions of the following in water treatment :
(i) Coagulant (ii) Bleaching powder (iii) Calgon
37. A water sample has the analytical report as under:
MgCO3 = 84 ppm, CaCO3 = 80 ppm, MgSO4 = 30 ppm, CaSO4 = 34 ppm, NaCl = 10 ppm
Fe2O3 = 56 ppm.
Calculate the amount of lime and soda needed for the treatment of 80000 litres of water.
(RGPV Bhopal 2006)
UNIT
61
62 BASIC ENGINEERING CHEMISTRY
2.3.1 Units of Heat or Calorific alue
(i) Calorie : Calorie is the amount of heat required to increase the temperature of 1 gm of water
through one degree centigrade.
1 calorie = 4.185 Joules = 4.185 × 107 erg.
(ii) Kilocalorie or kilogram calorie or kilogram centigrade unit (Kcal or Kg cal or K.C.U.)
The amount of heat required to raise the temperature of 1 kg of water through 1°C (more
precisely from 15°C to 16°C) is known as kilocalorie
1 K cal = 1000 Cal
(iii) British thermal unit (B.Th.U. or B.T.U.)
The amount of heat required to rise the temperature of one pound (1 lb) of water through 1°F
(more precisely from 60°F to 61°F) is known as british thermal unit.
1 B.Th.U. = 1,054.6 Joules = 1,054.6 × 107 ergs.
(d) Centigrade heat unit (C.H.U.)
The amount of heat required to raise the temperature of one pound (1 lb) of water through 1°C
is known as centigrade heat unit.
Interconversion of the various units
These units can be interconverted as follows :
1 cal/g = 1K cal/kg = 1.8 B.Th.u/1b.
1 K cal/m3 = 0.1077 B.Th.u/1b
1 B.Th. u./ft3 = 9.3 K cals/m3
2.3.2 Gross and Net Calorific alues
The Gross Calorific Value or Higher Calorific Value is the total heat generated when a unit
quantity of fuel is completely burnt and the products of combustion are cooled down to 60°F or
room temperature i.e., ≈ 25°C.
When a fuel containing hydrogen is burnt, the hydrogen present undergoes combustion and will
be converted into steam. As the products of combustion are cooled to room temperature, the steam
gets condensed into water and the latent heat is evolved. Thus the latent heat of condensation of
steam so liberated is included in the gross calorific value
The calorific value determination by Bomb calorimeter gives the Gross or Higher Calorific
Value.
The Net Calorific Value or Low Calorific Value is the net heat produced when a unit quantity of
fuel is completely burnt and the products of combustion are allowed to escape. Thus,
Net Calorific Value = Gross Calorific Value — Latent heat of Condensation of the
water vapour produced.
= Gross Calorific Value — (Mass of Hydrogen per unit weight of the fuel burnt × 9 × latent
heat of vapourization of water).
1 part by weight of hydrogen gives 9 parts by weight of water as follows:
H2 + O → H2O
2g 16g 18g
1g 8g 9g
The latent heat of steam is 587 Cal/g (or Kcal/Kg) or 1060 B.Th.U./lb of water vapour produced.
FUELS AND COMBUSTION 63
H
Net C.V. = Gross C.V. – 9 × × 587
100
Net C.V. or L.C.V. = Gross C.V. – 0.09 × H × 587
where H = % of hydrogen in the fuel.
In actual practical use of a fuel, it is rarely feasible to cool the combustion products to the room
temperature to allow the condensation of water vapour formed and utilise that latent heat; hence the
water vapour formed also is allowed to escape along with the hot combustion gases.
2.3.3 Calorific value at constant pressur
The calorific value at constant pressure, C.P. can be calculated on the basis of the following:
QC.P. = QC.V. – (∆n). R.T.
where
QC.V. = Calorific value at constant volume (as determined in a Bomb Calorimeter).
∆n = increase in number of gaseous molecules after reaction.
R = gas constant
T = absolute temperature.
If there is a decrease in the number of gaseous molecules formed after the reaction, then ∆n will
have a negative value and consequently, QC.P. will be higher than QC.V.
2.3.4 Theoretical calculation of calorific value of a fue
Theoretically, the calorific value of a fuel can be calculated, if the percentages of the constituent
elements are known. According to Dulong, “the calorific value of a fuel is the sum of the calorific
values of its constituents”.
Constituent H C S
HCV (K cal/kg) 34500 8080 2240
If oxygen is present in the fuel it combines with hydrogen to form H2O. Thus the hydrogen in
the combined form is not available for combustion and is called fixed hyd ogen.
Amount of hydrogen available for combustion = Total mass of hydrogen-hydrogen combined
with oxygen.
Now, 8 parts of oxygen combine with one part of hydrogen to form water i.e., for every 8 parts
of oxygen 1 part of hydrogen gets fixed
\ Amount of hydrogen available for combustion = Total mass of hydrogen –1/8 mass of
oxygen, in fuel.
On the basis of above chemical composition of fuel Dulong’s gaves the following formula for
calculating the calorific value of fue
1 0
HCV =
100 8080C + 34,500 H − 8 + 22405 K cal/kg
and
LCV = [HCV – 0.09 H × 587] K cal/kg
where C, H O and S are the precentages of carbon, hydrogen, oxygen and sulphur in the fuel.
2.3.5 Determination of calorific valu
Bomb Calorimeter is an apparatus used for calculation of calorific value of solid and liquid
fuels.
A known mass of a fuel is burnt and the quantity of heat produced is absorbed in water and
measured. Now the quantity of heat generated by burning a unit mass of the fuel is calculated.
64 BASIC ENGINEERING CHEMISTRY
An steel vessel called the bomb. It is covered with a gas tight cover having three values. One for
oxygen inlet, second for pressure gauge and third for release of pressure. Two electrical leads made
up of platinum are fixed in the cover. A Silica crucible is kept inside the apparatus in which weighed
quantity of fuel is taken. A fuse wire of platinum is dipped in the fuel taken in the crucible and its
end are connected to the battery outside through a key.
The bomb is placed in the copper calorimeter, containing known quantity of water. The copper
calorimeter is surrounded by an air jacket, which is further inclosed in a vessel containing water.
One electric stirrer for stirring the water is provided in the calorimeter. Calorimeter also contains
one accurate thermometer for noting down the temperature.
Calculations
Let,
Weight of the fuel sample taken = m grams
Higher or Gross calorific value of the fuel = θ cals/gram
Weight of the water taken in the calorimeter = W grams
Water equivalent of the calorimeter, bomb, thermometer, stirrer, etc. } = w grams
Initial temperature = t1°C
Final temperature = t2°C
Heat liberated by the combustion of the fuel = mθ
Heat absorbed by the water, calorimeter, etc.
= (W + w) (t2 – t1)
Heat liberated = Heat absorbed
... mθ = (W + w ) (t2 – t1)
(W + w) (t2 − t1 )
... HCV or Gross CV (θ) =
m
However, for more accurate results, the following corrections will have to be incorporated in the
above equation : (i) Acids correction, tA, (ii) Fuse wire correction, tF, (iii) Cotton thread correction,
tT and (iv) Cooling correction, tC. Accordingly, the above equation will have to be modified as
[(W + w) (t2 − t1 + tc )] − [t A + t F + tT ]
HCV or Gross CV (θ) =
m
Calculation of net calorific valu
Net C.V. = Gross C.V. – Latent heat of water vapour, formed during the combustion of m grams
of the fuel
FUELS AND COMBUSTION 65
= Gross C.V. – 0.09 × H × 587
(where H is the percentage of hydrogen present in the fuel and latent heat of steam is 587
cals/g).
Determination of water equivalent of the apparatus
The water equivalent of the apparatus is best determined by burning a known weight (preferably
about 1.2g) of pure and dry benzoic acid (in a pellet form) in the bomb under identical conditions
as described above. The rise in temperature is noted. The standard calorific value of benzoic acid
is taken as 6324 calories per gram. Since all the other values in the formula are known, the water
equivalent of the apparatus can be calculated. Other substances suitable as standards are:
... Calorific alue
Naphthalene ... 9622 cals/g
Salicylic acid ... 5269 cals/g
Camphor ... 9292 cals/g
Corrrections:
For calculation of more correct values in the results, following three correction must be made,
while calculating the calorific value of a fuel
(i) Acids correction (tA). The sulfur present in the coal is converted into H2SO4 in the bomb.
S + O2 → SO2
2SO2 + O2 + 2H2O → 2H2SO4; ∆H = – 144,000
(4 × 49) calories
(Eq. Wt. of
H2SO4 = 49)
Similarly the nitrogen present in the coal and part of that in the air in the bomb are converted
into HNO3.
2N2 + 5O2 + 2H2O → 4HNO3; ∆H = – 57,160
(4 × 63) calories
(Eq. Wt. of
HNO3 = 63)
Since the above two reactions are exothermic and since the heat thus liberated is not obtainable
in practical use of coal (because SO2 and NO2 pass off into the atmosphere) correction must be made
for the heat liberated in the bomb by the formation of H2SO4 and HNO3, as follows:
(a) 3.6 calories should be subtracted for each ml of N/10, H2SO4 formed.
(b) 1.43 calories must be deducted for each ml of N/10 HNO3 formed
(as per the equations given above)
(ii) Fuse wire correction. The heat liberaled as measured above, include the heat given out by
ignition of the fuse wire used. Hence it has to be substracted from the total value. The amount to be
substracted are given in the instruction provided by the supplier of the fuse wire.
(iii) Cooling correction, (tC). If the time taken for the water in the calorimeter to cool from
the maximum temperature attained to the room temperature is x minutes and the rate of cooling
is dt°/minute, then the cooling correction = x × dt. This should be added to the observed raise in
temperature.
Hence,
[(W + w) (T2 − T1 + cooling correction)] − (Acid + Fuse correction)]
L=
Mass of the fuel ( x)
66 BASIC ENGINEERING CHEMISTRY
2.4. CRITERIA FOR SELECTING A FUEL
The following characteristics are taken into consideration for the selection of a fuel for a
particular purpose:
1. The fuel selected should be most suitable for the process. For instance, coke made out of
bituminous coal is most suitable for blast furnace and also as a foundry fuel.
2. The fuel should posses a high calorific value
3. The fuel should be cheap and readily available.
4. It should possess a moderate ignition temperature. Too high ignition temperatures cause dif-
ficulty in kindling while too low ignition temperatures may create safety problems during
storage, transport and use of the fuel.
5. The supply position of the fuel should be reliable.
6. The velocity of combustion should be moderate.
7. The fuel should have reasonable flexibility and control
8. The fuel should be such that a safe and clean operation is ensured. Too much smoke and
obnoxious (harmul) odours are not desirable.
9. It should be safe, convenient and economical for storage and transport.
10. It should have low moisture content.
11. In case of a solid fuel, the ash content should be less and the size should be more or less
uniform.
2.5. COAL
2.5.1. Origin of coal formation.
Coal is regarded as a fossil fuel produced from large accumulations of vegetable debris due to
partial decay and alteration by the action of heat and pressure over millions of years.
The formation of coal is explained by the following two theories:
(1) “In situ” theory states that coal seams are formed in the same area where vegetation grew
and accumulated. The great purity of many coal seams holds testimony to this theory.
(2) The “drift” or “transportation” theory contends that the coal seams are not formed where the
vegetation grew and accumulated originally. These materials were drifted or transported by rivers
to lakes or estuaries and got deposited there. The great thickness of coal seams support this theory.
Thus evidences are available in support of both the above theories.
The various agencies responsible for the conversion of plant tissues to coal include (i) Bacteria
(under water), (ii) Time (millions of years), (iii) Temperature (> 300°C) and (iv) Pressure.
The time required for the formation of young brown coals is of the order of 107 years while that
for the most mature coals is 3 × 108 years.
The vegetable matter fallen on the ground undergoes microbial degradation in presence of
air and eventually gets converted to carbon dioxide and water without leaving any organic
matter remaining. However, the course of decay when it is buried under water is different. The
transformation of the vegetable debris to coal takes place in two stages; (i) the biochemical or peat
stage and (ii) the metamorphic stage during which peat is transformed into coal.
The effect of temperature and pressure caused by the depth of burial on the rank of a coal is
brought out by Hilt’s law which states that in any vertical section the rank of the seams increases
with depth.
The formation of coal from decaying plant debris to bituminous stage is explained by two
alternative theories.
FUELS AND COMBUSTION 67
(i) Serial evolution. This is the commonly accepted theory according to which the evolution
of coals occurs through geochemical metamorphism of peat to anthracite as follows:
(peat → lignite → bituminous coal → anthracite)
(ii) Parallel evolution. This theory is based on the concept of entirely biochemical origin of
coals of various ranks. According to this theory, lignites, bituminous coals and anthracites
may not form a continuous series but may be the end-products resulting from the differ-
ences in the extent of the aerobic decomposition of peat, the subsequent composition of the
overlying strata and the depth of the burial. This theory may be represented as follows:
Vegetable Matter
Aerobic decay
Acid medium
H Peat stage prolonged 2 eliminated as CH4
continued elimination of H2
Peats
Burial under sedimentary rocks
2.6. CARBONIZATION
The process of converting coal into coke is called carbonization when the coking coal is heated
in absence of air, the porous hard and strong residue left is called coke. It is white lustrous, porous
and coherent mass.
When coal is heated in absence of air as per its behaviour it can be classified into the following
categories
(i) Non-coking coal
(ii) Coking coal
Non-coking coals. The coal which do not fuse at all when heated is known as non coking coals.
Anthracite, sub-bituminous, lignite coals are the example of non-coking coal.
Coking coals and caking coals. There are some coals which have a tendency to soften and
swell at higher temperature and form a solid coherent mass with porous structure, such coals are
FUELS AND COMBUSTION 71
called caking coals. While the coals which give porous, hard and strong residue after heating in the
absence of air, the residue is (used for metallurgical purpose) called coke. If the coke so produced
is hard, porous and strong, then the coal from which this coke is derived is called coking coals.
Obviously, all coking coals are caking coals but all caking coals are not coking coals.
2.6.1 Properties of good metallurgical coke
The quality requirements of a good metallurgical coke are given below.
1. High purity. The best metallurgical coke should contain lowest possible percentage of
moisture (< 4%), ash (< 6%), sulfur (< 0.5%) and phosphorous (< 0.1%). Mositure and ash reduce
the calorific value. Sulfur and phosphorous in the coke may contaminate the metal and adversely
affect its properties. They tend to make the metal brittle.
2. Porosity. The metallurgical coke should be porous to provide intimate contact between the
carbon and oxygen and to ensure efficient combustion of the fuel in the furnace
3. Strength. The coke should be strong enough to withstand the abrasion and over burden of
the ore, flux and the fuel itself in the furnace. If the coke breaks into fine particles during charging
of the furnace, they may hinder the flow of gases and choke the air passages
4. Uniformity. The coke should be uniform and medium in size. If the lumps are too big,
combustion is irregular. If they are too small, choking may result.
5. Calorific value The coke should possess a high calorific value
6. Cost. The coke should be cheaply available near the plant site.
7. Calorific intensity. The calorific intentisty of the fuel should be high enough to melt the
metal.
8. Combustibility. The coke should burn easily but at the same time should not be very
reactive.
9. Reactivity. Reactivity of coke refers to its ability to react with CO2, steam, air and O2.
The reactivity of the coke should not be very high. Coke of low reactivity gives a higher fuel bed
temperature than what is produced by a coke of high reactivity.
Coal cannot be used as a metallurgical fuel (excepting in reverberatory furnaces) because it
does not have the necessary purity, porosity and strength. During the process of carbonisation from
coking coals, much of the volatile matter and sulfur compounds are removed and a strong and
porous coke is produced.
2.6.2 Types of carbonization of coal
Carbonization is of two types:
(i) Low temperature carbonization. It is done at 500°–700°C and it produces mainly domestic
fuel. The yield of coke 75–80% calorific value 6500 to 9500 Kcal/m3 and percentage of volatile
matter is 5-15%.
(ii) High temperature carbonization. It is done at 900–1200°C and is mostly carried out
for the manufacture of metallurgical coke. The yield of coke is 65 to 75%, calorific value 5400 to
6000 °C Kcal/m3 and percentage of volatile matter 1 to 3%.
2.6.3 Manufacture of metallurgical coke
There are two methods of manufacture metallurgical coke
(i) Beehive oven method
(ii) Otto-Hoffman oves or chamber ovens or by product oven method
(i) Beehive oven. It is primitive method for the production of coke. A beehive oven is a fire
brick chamber having a dome shaped structure. It is called beehive oven because it resembles in
72 BASIC ENGINEERING CHEMISTRY
shap to that of a beehive. Its dimensions are 4 m wide and 2.5 m high. It has two doors, one charging
door for coal at top and other at the side for taking cut coke. It also acts as an inlet for air as and
when required.
Coal chaigina door
Refractory
lining
Zone of
combustion
2.5 m
Door for air
0.6 m supply or coke
discharging
4m
As the coal is heated in the coke oven, moisture is first expelled, then the decomposition of the
coal substance takes place at 300 to 450°C. At about 500°C, the coal passes through a plastic state
but at about 550° to 600°C, the plasticity ceases and semicoke is produced. This is black in colour
and is low in strength. As the temperature raises further above 600°C, the semicoke decomposes with
loss in volatile matter and gets transformed into steel grey hard coke. The process of carbonisation
takes place layer by layer in the coal charge starting from the two side walls of the oven and moving
towards the centre.
Each oven holds about 20 tonnes of coal charge and the time taken for carbonisation is about
12 to 20 hours. The temperature goes around 1100°C and the yield of the coke is about 70% of the
coal charged. Nearly 40% of the coke oven gas generated is sufficient to heat the ovens and the rest
is available for other uses in the steel plant or is sold out. This gas has high calorific value and can
be transported to distant places.
After the carbonisation is complete, the discharging doors are lifted by a crane and the red hot
coke is pushed out mechanically into a coke car. The car carries it to quenching station where the
coke comes into contact with a spray of cooling water. The excess water on the coke is allowed to
get evaporated and the coke is screened to different sizes. Then it is supplied for different uses in the
plant e.g., foundry and blast furnace and also for domestic purposes.
The gas coming out of the coke ovens contains ammonia, sulfur (as H2S) volatile hydrocarbons,
tar, etc. Important byproducts such as high calorific value gas, light oil, tar, ammonium sulfate,
finely divided sulfur and ammonium thiocyanate can be recovered from the byproduct-oven
gases.
(1) Recovery of tar. The gas from the coke ovens is passed through a tower where liquor
ammonia trickles from the top. Tar and dust are removed into a tar tank. Tar and ammonia are
recovered. Ammonia liquor is again sent to the top of the trickling tower.
(2) Recovery of ammonia. The gases now enter another tower when water is sprayed.
Ammonia goes into solution forming ammonium hydroxide. Sometimes, instead of water dilute
74 BASIC ENGINEERING CHEMISTRY
H2SO4 is sprayed when ammonium sulfate is recovered.
NH3 + H2O → NH4OH
2NH4OH + H2SO4 → (NH4)2SO4 + 2H2O
(3) Recovery of naphthalene. The gases then pass to a cooling tower where water at a low
temperature is sprayed. Condensation of some gases takes place and naphthalene is recovered.
(4) Recovery of benzene. The gases then pass through an oil (petroleum) scrubber where
benzene and its homologues are recovered.
(5) Recovery of H2S. The gases then enter a purifying chamber packed with moist Fe2O3
Fe2O3 + 3H2S → Fe2S3 + 3H2O
After all the Fe2O3 exhausted, it is exposed to atmospheric air to recover the sulfur (as SO2),
and regenerate the Fe2O3
Fe2S3 + 4O2 → 2FeO + 3SO2
4FeO + O2 → 2Fe2O3
(6) Recovery of gas. The gas after passing through the various scrubbers and condensers to
remove the various byproducts mentioned above is finally collected in a gas holder. The gas has the
calorific value of about 5000 Kcal/ 3.
2.7. CRACKING
In cracking process, higher saturated hydrocarbon molecules are converted into simpler
molecules such as paraffinic and olefinic hydrocarbons, as follow
cracking
C10 H 22 → C5 H12 + C5 H10
paraffin olefin
These simpler molecules may be still further decomposed until at very high temperatures, the
hydrocarbons may be cracked to completion, giving carbon and hydrogen only:
CH4 → C + 2H2
However, in actual practice, the cracking of heavy hydrocarbons results in the formation
of a complex mixture of saturated and unsaturated hydrocarbons in liquid and gaseous state. In
addition, hydrogen and carbon may be produced; and aromatic hydrocarbons may also be formed by
polymerisation. The higher the boiling range of petroleum fractions being cracked, (i.e., the larger
the molecules and their chain lengths), the lower the cracking temperatures.
Cracking is usually done by two methods:
1. Thermal cracking 2. Catalytic cracking
1. Thermal cracking
This is the oldest method and is being replaced by other methods. In this method, the heavy
oil is subjected to high temperature and pressure where the high molecular weight hydrocarbons
are decomposed to lower hydrocarbons of paraffinic and olefinic series. Some of the molecules
so formed may undergo polymerisation to yield larger molecules. The cracked products are then
separated by fractional distillation. Generally, the yields is from 7 to 30% but sometimes, higher
yields may be obtained. Some coke is also formed during this process along with other liquid and
gaseous products. There are two types of thermal cracking which are usually distinguished.
(a) Liquid-phase cracking. By this method, any type of oil (residues, fuel oil or gasolines)
can be cracked. In this method, the charge is kept in the liquid form by applying high pressures of
the range 15 to 100 kg/cm2. The temperature maintained is 420° to 550°C. The octane rating of the
product formed is 65 to 70.
(b) Vapour phase cracking. By this method, only those oils which can vaporize at low
temperatures can be cracked. The time required for cracking in this method is lesser, the stability
FUELS AND COMBUSTION 75
of the products poorer and the octane rating of the product higher, as compared to liquid-phase
cracking process. The temperature maintained is 600 to 650°C, while the pressure is 10 to 20 kg/cm2.
2. Catalytic cracking
In this method, cracking is brought about in presence of a catalyst at much lower temperatures
and pressures (300° to 450° and 1 to 5 kg/cm2 pressure). There are two main types of catalytic
cracking: (i) cracking carried out only in the presence of a catalyst (porous solid particles of definite
composition and structure); (ii) cracking carried out in presence of a catalyst, but in a hydrogen
atmosphere at a slightly reduced temperature but higher pressure. This type of cracking is known as
“hydro-cracking.”
The earliest cracking catalysts, were acid clays, but they were replaced by crystalline alumino-
silicates (zeolites). In these, alumina and silica are the major constituents, but they also contain
minor amounts of oxides of Ca, Mg, Na, Fe, Cr and rare earths.
Catalyst cracking is done by following two method.
(1) In fixed-bed cracking, the oil vapours, heated to cracking temperatures, are passed on to
the fixed catalyst bed. When the catalyst gets carbonised, it is reactivated by burning off the carbon
deposited.
(2) In Fluid-bed cracking, the catalyst in the form of a fine powder, is circulated through the
cracking reactor with the help of oil vapours or air. The catalyst accelerates and directs the cracking
and also acts as a heat transfer medium. The catalyst is continuously regenerated.
Fixed bed catalytic cracking
The essential features of this process are represented in Fig. 2.11.
Vapours Cooler
Cracked vapours
Hot air for Gases
reactivation
Charge
of heavy
oil heaters Heavy oil Gasoline
Preheater Fractionating Stabiliser
Catalyst towers Column condensed gasoline
+ dissolved gases
Fig. 2.5. Fixed-bed catalytic cracking.
The heavy oil charge is passed through a heater, where the oil is vaporized and heated to 400 to
500°C. The silica alumina gel (SiO2, Al2O3), or bauxite catalyst, is mixed with clay and zirconium
oxide and packed in catalyst towers. The hot vapours are passed over fixed bed of catalyst in the
catalyst towers maintained at 400 to 500°C and a pressure of 1 to 5 kg/cm2. Cracking of the oil
takes place in the reactor. About 30-40% of the charge is converted into low molecular weight
hydrocarbons, conforming to the composition of gasoline. About 4% of carbon is formed during
the cracking process which gets deposited on the catalyst bed. The cracked vapours now enter the
fractionating column where the gasoline vapours and other gaseous products are recovered from the
top while the heavy gas oil fractions are condensed at the bottom of the column. The vapours are
admitted into a cooler where the gasoline and some of the other gaseous products are condensed,
while the uncondensed gases move on further. The condensate is now sent into a stabilizer where the
dissolved gases are removed and gasoline is recovered. (The light gases produced in cracking are no
longer allowed to escape into air or burnt. They form valuable raw material for the synthesis of new
types of fuels and other materials such as antifreeze, plastics and synthetic rubber).
When substantial amount of carbon is deposited on the catalyst bed, the catalyst ceases to
function. It is reactivated by burning off the carbon deposited in a stream of hot air. This heat is
utilized for heating the reactor. During the reactivation of catalyst, the vapours are diverted through
a stand-by catalyst chamber. Thus, the reaction can proceed without interruption.
76 BASIC ENGINEERING CHEMISTRY
Fluid-bed catalytic cracking
The modern refineries employ fluid-bed of the catalyst in their huge and efficient “cat-crackers”.
These consist of a reactor and a regenerator, generally placed side by side, as in Fig. 2.6.
cooler
Smoke Cracked vapours Lighter
stock Reacter fractions
Catalyst
clean hot
catalyst
regenerator Uncondensed
gases
Fresh Gases
catalyst
Air Stabilizer
Heavy Gasoline
fuel + dissolved Gasoline
Heavy oil Spent catalyst Fractionating oil gases
charge column
Power output
40 ted HUCR
l c ula d Medium
30 Ca erve
20 obs
HUCR Low
10
0
0 1 2 3 4 5 6 7 8 9 10 3 4 5 6 7
Compression ratio Compression ratio
(i) (ii)
Fig. 2.8. Variation of (i) thermal efficiency (ii) and power output with compression ratio.
However, H.R. Ricardo, with the help of a variable compression engine showed that in actual
practice, the power increases to a maximum and then falls rapidly with further increase in the
compression ratio. The compression ratio, corresponding to the maximum power output, is known
as highest useful compression ratio (HUCR) at which a slight metallic “knock” or “pink” can be
heard. This becomes more pronounced and heavy as the compression ratio is further increased
above this optimum value and finally pre-ignition of the fuel will occur (i.e., the fuel ignites even
before the regular spark occurs). It was found that for a given engine, the HUCR largely depends
upon the type of the fuel used. For instance, aromatic fuels such as benzol can be used at higher
compression ratios without knocking than normal straight-run paraffinic petrol
Knocking is due to the spontaneous ignition of the last unburnt portion of the charge giving a
detonating shock wave. (Knock occurs after the passage of the firing spark, while pre-ignition is
the spontaneous combustion of the explosive mixture before the spark). The tendency to “knock”
depends not only on the fuel but also on the engine design, shape of head, location of plug, ports,
etc., and also upon the running conditions. The knocking tendency is increased by reducing the
engine speed, advancing the ignition etc.
2.9.1. Consequence of knocking
(i) Decreassed power output
(ii) Mechanical damage by overheating of cylinder parts
(iii) Huge loss of energy
FUELS AND COMBUSTION 79
2.9.2. Chemical structure and knocking
The knocking tendency decreases with increase in the compactness of the molecules, double-
bond and cyclic structure.
For straight chain hydrocarbon the knocking tendency increase with increasing the molecular
weight and boiling point.
e.g. n-hexane n-pentane n-butane
90 60 29
Branched chain paraffins have lower knock propertie than their normal isomers
The resistance to knock increase with the number of branches and their position. Thus 2-methyl
hexane has an octane number of 55 while 2 : 2 dimethy pentane has an octane number of 80.
Olefines have lower knocking properties than the corresponding paraffins. Further the knocking
tendency decreases as the position of the double bond approaches the centre of chain.
In general the knocking tendency is in the following order
Straight chain paraffins > Branched chain Paraffins > Olefins > Cyclo paraffins (naphthenes) >
Aromatic hydrocarbon.
2.10 OCTANE NUMBER
The resistance offered by gasoline to knocking can not be defined in absolute terms. It is
expressed on an arbitrary scale, known as octane rating or octane number. This scale is given by
Graham Edgar in 1926.
It was observed that n-heptane knocks very badly and hence it was assigned an antiknock value
of zero. On the other hand, iso octane (2, 2, 4 trimethyl pentane) has a high resistnce to knocking
and hence it was assigned an antiknocking value of 100.
H3C—CH2—CH2—CH2—CH2—CH2—CH3
n-heptane (Antinknock value = 0)
CH3 CH3
H3C—C—CH2—CH—CH3
CH3
Iso octane (2,2,4 trimethyl pentane) (Antinknock value = 100)
Thus “the percentage of iso octane in the n-heptane-isooctane blend which has the same knocking
characteristics as the gasoline sample, under the same set of conditions is called as octane number”.
The octane rating of some common hydrocarbons are given below.
Table 2.3
CH3
a-methyl naphthalene
Thus, the centane number of a disel oil may be defined as the percentage of centane in a mixture
of centane and a-methyl naphthalene which will have the same ignition characteristics as the fuel
under lest, under same set of conditions.
The centane number of high speed (1500-2000 rpm), medium speed (1500-500 rpm) and low
speed (150 to 500 rpm) diesel engines should be atleast 45, 35 and 25 respectively. Diesel engine
requires a fuel of cetane number greater than 45 Cetane no. of fuel primarily depends on the nature
and composition of its hydrocarbons.
For instance consider the following:
n-alkanes > naphthalene (cycloalkanes) > alkenes > branched alkanes > aeromatics (cyclo
alkanes)
(i) ignition delay increases from left to right,
(ii) ignition quality incrases from right to left,
(iii) cetane no. increases from right to left.
The straight chain hydrocarbons ignite easily (high ignition quality) but the aeromatics do not
ignite easily on compression. Cetane number fuels eliminate diesel knock.
The cetane number of diesel fuel may be raised by addition of pre ignition dopes. e.g., alkyl
nitrites, ethyl nitrite or amyl nitrite etc.
HMV (hepta methyl nomane) with cetane rating of 15 is now considered as the low quality
diesel in view of its easy availability and purity.
CH3 CH3 CH3 CH3
| | | |
CH3 C CH 2 C CH 2 C CH 2 C CH3
| | | |
CH3 CH3 CH3 CH3
On the revised scale (H.M.N.) the cetane number (C.N.) represents the % cetane in the blend
15
with H.M.N. plus of the % H.M.N.
100
Thus, a blend of 50% cetane and 50% H.M.N. has a cetane rating of
15
50 + × 50 =
57.5
100
FUELS AND COMBUSTION 81
Table 2.5. Difference Between Octane Number And Cetane Number.
Similarly, Equation (5) shows that 1 mol of CH4 reacts with 2 mols of O2 to give 1 mol of
CO2 and 2 mols of H2O. From this equation, we can calculate the air required for the complete
combustion of 1 mol of methane. Since 21 mols of oxygen come from 100 mols of air and also since
100
2 mols of oxygen are required to burn completely 1 mol of CH4, the air required = 2 × = 9.52
21
mols.
This also means that 1 cft of CH4 required 9.52 cft of air (since volume % = mol %).
Analyses
Analyses of solids are always reported on weight basis. In order to convert them into mol basis,
it is necessary to divide each constituent by its molecular weight. Thus a coal containing 72% C, 4%
72 4 6
H2 and 6% O2 would contain = 6 mols of C; = 2 mols of H2; and = 0.187 mol of O2
12 2 32
per 100 kg of the coal sample.
Analysis of gases is always reported on volume basis and hence directly gives the number of
mols of each constituent present per 100 mols of the mixture. Thus, the analyses of gases obtained
by the Orsat apparatus are always expressed as % by volume and also on dry basis. Hence, this gas
analysis gives molar composition directly since the mol is a volume unit. (A pound mol corresponds
to 359 cft at N.T.P.). For example, 100 mols of air (100 × 359 = 35900 cft) contains 21 mols of O2
(21 × 359 cft) and 79 mols of N2 (79 × 359 cft).
Excess air
Combustion seldom takes place efficiently with the theoretically minimum quantity of air.
Invariably, an excess of air is used in the furnace. Excess air is the amount of air used over and
above that required for complete combustion.
Sample problem
Let us consider the following data obtained with methane, CH4 as a fuel:
Fuel gas Flue gas
CH4 = 100% Constituent % Mols of C Mols of O2
CO2 5.5 5.5 5.5
O2 11.1 — 11.1
N2 83.4 — —
Total 100 5.5 16.6
(A) Ratio of Flue gas: Fuel gas
If we take 100 mols of dry flue gas as the basis for calculation, there are 5.5 mols of C, 16.6
mols of O2 and 83.4 mols of N2. It is obvious that the entire amount of carbon present in the fuel gas
must have been present in the flue gas. Since all the carbon came from the fuel gas, it is clear that
5.5 mols of CH4 (containing 5.5 mols of C) were used to form 100 mols of dry flue gas. Therefore,
Dry flue gas 100
= = 18.2
Fuel gas 5.5
i.e., 18.2 mols (or cft) of dry flue gas per mol (or cft) of fuel gas
(B) Dry flue gas: dry ai
We know that N2 in air is equal to N2 in flue gas. In the above example, there are 83.4 mols
of N2 per 100 mols of dry flue gas. In order to obtain 83.4 mols of N2, the air used must have been
100
83.4 × mols.
79
FUELS AND COMBUSTION 87
7.797 k mols
FUELS AND COMBUSTION 95
per100 kg of coal )
K mols of O 2 required = 7.797 Kmols.
(a) Hence, the theoretical quantity of O2 required for the combustion of 1 kg of coal
= 7.797 × 10–2 Kmols
= 7.797 × 10–2 × 32 kg.
Weight of air required for 100
... the complete combustion = 7.797 × 10–2 × 32 ×
kg.
of 1kg of coal 23
= 10.848 kg.
(b) Theoretical quantity of O2 required per kg. of coal = 7.797 × 10–2 K mols.
... Theoretical quantity of air required per kg. of coal
100
= 7.797 × 10–2 × = 0.3713 K mols
21
... Volume of air supplied at NTP for 1 kg of coal
= 0.3713 × 22.4 m3 = 8.3171 m3
(c) Composition of dry products of combustion by volume
The dry products formed by the combustion of 1 kg of coal are:
CO2 = 0.07 K mols
SO2 = 0.00016 K mols
79
N2 = 0.000178 + 0.3713 × = 0.2935 K mols
100
from fuel from air
... Total volume of the dry products of combustion = 0.3637 K mols
... Volumetric composition of the products of combustion is:
0.07 ×100
CO2 = = 19.25%
0.3637
0.00016 ×100
SO2 = = 0.04%
0.3637
0.2935 ×100
N2 = = 80.7%
0.3637
By weight
The dry products of combustion formed from 1 kg of coal are;
CO2 = 0.07 × 44 = 3.08 kg
SO2 = 0.00016 × 64 = 0.01024 kg
N2 = 0.2935 × 28 = 8.218 kg
Total weight = 11.3082 kg.
.. . Gravimetric composition of the dry products of combustion is:
3.08 ×100
CO2 = = 27.237%
11.3082
0.01024 ×100
SO2 = = 0.091%
11.3082
8.218 ×100
N2 = = 72.673%
11.3082
96 BASIC ENGINEERING CHEMISTRY
Method 2: (Stoichiometric method)
C + O2 → CO2
12 kg 32 kg 44 kg
1
H2 + O → H2O
2 2
2 kg 16 kg 18 kg
S + O2 → SO2
32 kg 32 kg 64 kg
Let 100 kg of the coal be the basis of calculation:
Constituent Weight Weight of O2 Weight of dry products, kg
in kg required, kg.
84 × 44
C 84.0 84 × 32/12 = 224 CO2 = = 308
12
16
H2 3.5 3.5 × = 28.0 —
2
O2 3.0 – 3.0 —
32 64
S 0.5 = 0.5 0.5 ×
SO2 = 0.5 × = 1.0
32 32
Moisture 3.5 — —
N2 0.5 — N2 = 0.5
Weight of O 2 required
for the combustion of = 249.5 kg.
100 kg coal
(a) Hence, the theoretical quantity of O2 required for the combustion of 1 kg of coal = 2.495 kg.
100
... The theoretical quantity of air required for the combustion of 1 kg. of coal = 2.495 × kg
23
= 10.848 kg.
(b) 32 kg. of O2 occupies 22.4 m3 at N.T.P.
2.495 × 22.4
... 2.495 kg. of O2 occupies = 1.7465 m3
32
Now, 21 m3 of O2 are present in 100 m3 of air at N.T.P.
1.7465 ×100
... 1.7465 m3 are present in = 8.317 m3 of air.
21
... Volume of the air at N.T.P. = 8.317 m3.
(c) Composition of dry products of combustion.
By weight
The dry products of combustion formed from 1 kg of coal are:
CO2 = 3.08 kg
SO2 = 0.01 kg.
N2 = [0.005 + (10.848 – 2.495)] kg. = 8.358 kg.
from fuel from air
Total weight = 11.448 kg.
FUELS AND COMBUSTION 97
... Gravimetric composition of the dry products of combustion is
3.08 ×100
CO2 = = 26.90%
11.448
0.01×100
SO2 = = 0.087%
11.448
8.358 ×100
N2 = = 73.01%
11.448
By Volume
3.08
CO2 = = 0.07 Kmol
44
0.01
SO2 = = 0.0001563 Kmol
64
8.358
N2 = = 0.2985 Kmols
28
Total volume = 0.3687 Kmols
... Volumetric composition of the dry products of combustion is:
0.07 ×100
CO2 = = 18.986%
0.3687
0.001563 ×100
SO2 = = 0.0424%
0.3687
0.2985 ×100
N2 = = 80.96%
0.3687
Example 2. Find the volume of air required for complete combustion of 1 m3 of acetylene and
the weight of air necessary for the combustion of 1 kg of fuel.
Solution
2C2H2 + 5O2 = 4 CO2 + 2H2O
2 vols 5 vols 4 vols 2 vols
O2 required per m3 of C2H2 = 2.5 m3
100
... Air required per m3 of C2H2 = 2.5 × = 11.9 m3.
21
Further,
2 mols of C2H2 require 5 mols of O2
.. . (2 × 26) kg of C H requires (5 × 32) kg of O
2 2 2
(Since mol. wt. of C2H2 = 26 and Mol. wt. of O2 = 32)
160
O2 to be supplied per kg of fuel (C2H2) = kg
52
160 100
... Air to be supplied per kg of C2H2 = × = 13.378 kg.
52 23
Example 3. The % analysis by volume of producer gas is H2 – 18.3%, CH4 – 3.4%, CO –
25.4%, CO2 – 5.1%, N2 – 47.8%. Calculate the volume of air required m3 of the gas.
98 BASIC ENGINEERING CHEMISTRY
Solution.
100 mols of the producer gas contains:
Constituents % and Mols Mols of O2 required
H2 18.3 9.15
CH4 3.4 6.80
CO 25.4 12.70
CO2 5.1 —
N2 47.8 —
Total O2 required ... 28.65
100
... Air required for 100 mols of fuel gas = 28.65 × = 136.43 mols
21
136.43
... Air required per m3 of gas = = 1.3643 m3.
100
Example 4. A gas has the following composition by volume: H – 22%, CH4 – 4%, CO – 20%,
CO2 – 6%, O2 – 3% and N2 – 45%. If 25% excess air is used, find the weight of air actually supplied
per m3 of this gas.
Solution.
100 mols of the fuel gas contains
Constituents % and Mols Mols of O2 required
H2 22 11
CH4 4 8
CO 20 10
CO2 6 —
O2 3 –3
N2 45 —
Total O2 required ... 26
100
... Air required for 100 mols of fuel gas = 26 × = 123.8 mols
21
125
But air supplied actually (25% excess) for 100 mols of gas = 123.8 × = 154.75 mols.
100
154.75
... Air supplied for 1 mol of gas = = 1.5475 mols
100
1.5475 × 28.97
... Air supplied for 1 m3 of gas = 1.5475 m3 = = 2 kg.
22.4
(Since 22.4 m 3 of air i.e. 1 kg mol at N.T.P. weighs 28.95 kg).
Example 5. A sample of coal contained: C – 81%, H2 – 4%, O2 – 2% and N2 – 1%. Estimate
the minimum quantity of air required for complete combustion of 1 kg of the sample. Find the
composition of the dry flue gas by volume if 40% excess air is supplied
FUELS AND COMBUSTION 99
Solution.
Let the basis of calculation be 100 kg of coal.
Element Kg K Mols K mols of O2 Product
required
Notes
1. Air contains 21% by volume of O2 and 79% by volume of N2.
2. Average mol. wt. of air is 28.95.
3. H2O in flue gases is neglected for dry flue gas analysi
Example 6. A gas fi ed engine uses a fuel gas having the following composition:
CO2 – 9%, CO – 42%, H2 – 33%, N2 – 16%
The combustion takes places with the theoretical quantity of air. Calculate the volume of air
used per cubic meter of fuel gas burnt. Determine the dry flue gas analysis
Solution.
100 mols of fuel gas contains
% Mols Mols of O2 required Products and Mols
1
H 2 + O 2
→ H2O
2
... Hydrogen present in the fuel oil
= 6.38 k mols
The same quantity of fuel oil contains
= 10.2 k mols of C
... The fuel oil contains 10.2 k mols of C or (10.2 × 12) = 122.4 kg of C and (6.38 × 2) = 12.76
kg of H.
That means, the oil weighing (122.4 + 12.76) = 135.16 kg was burnt and it should be composed
of 122.4 kg of C and 12.76 kg of H.
Hence the composition of the fuel oil is:
122.4
C = × 100 = 90.5%
135.16
12.76
H = × 100 = 9.5%
135.16
(b) Total O2 supplied = 21.69 k mols
O2 needed for C = 10.20 k mols
O2 needed for H = 3.19 k mols
}
.. . O 2 actually needed for C and H = 13.39 k mols
present in100 mols of fuel oil
..
. Excess O2 = (21.69 – 13.39) = 8.30 k mols
8.30
... Excess O2 or air used = × 100 = 61.99%
13.39
(c) Total oil burnt = 135.16 kg
100
Total air supplied = 21.69 × = 103.29 k mols
21
= 103.29 × 22.4 = 2313.7 m3 at NTP
(Avogadro’s law)
2313.7
... Air used per kg of fuel oil = = 17.12 m3.
135.16
Example 8. A coal containing 62.4% C, 4.1% H, 6.9% O, 1.2% N, 0.8% S and 15.1 moisture
and 9.7% ash was burnt in such a way that the dry flue gases contained 12.9% CO2, 0.2% CO, 6.1%
O and 80.8% N. Calculate (a) the weight of air theoretically required per kg of coal, (b) the weight
of air actually used and (c) the weight of dry flue gas p oduced per kg of coal.
102 BASIC ENGINEERING CHEMISTRY
Solution.
(a) Basis of calculation. 100 kg of coal, which contains
Analysis Kg K mols K mols of O2 required K mols of product formed
Thus, O2 theoretically required for complete combustion of 100 kg of coal = 6.033 mols.
... Air theoretically required for complete combustion
100
= 6.033 × = 28.73 mols
21
= (28.73 × 28.95) = 831.7 kg
831.7
Wt. of air required per kg of coal = = 8.317 kg
100
(b) Actual air used:
Basis : 100 k mols of dry flue gas, which contain
Constituent % K Mols K Mols C K Mols of C K Mols of N
CO2 12.9 12.9 12.9 12.9 —
CO 0.2 0.2 0.2 0.1 —
O 6.1 6.1 — 6.1 —
N 80.8 80.8 — — 80.8
Total 13.1 19.1 80.8
13.1
13.1 k mols of C must have been supplied by × 100 kg of coal = 252 kg of coal containing
252 5.2
0.043 × = 0.108 k mols of N.
100
(Since 100 kg of coal contains 5.21 mols of C and 0.043 k mols of N).
... K Mols of N from air in 100 k mols of flue ga
= (80.800 – 0.108) = 80.692 k mols
... K Mols of air actually supplied to obtain 100 k mols of dry flue gas or to burn 252 kg of
coal would therefore be
100
= 80.692 × = 102.15 k mols
79
.. . Wt. of air supplied = (102.15 × 28.97) kg
= 2959.3 kg
... Weight of air supplied per kg of coal
= 2959.3 = 11.74 kg
252
FUELS AND COMBUSTION 103
(c) Wt. of dry flue gas obtained pe kg of coal:
100 kg mols of dry flue gas contains
Constituent % K Mols Weight in kg
CO2 12.9 12.9 × 44 = 567.6
CO 0.2 0.2 × 28 = 5.6
O2 6.1 6.1 × 32 = 195.2
N2 80.8 80.8 × 28 = 2262.4
Total = 3030.8 kg
100 k mols of dry flue gas contions 17.09 k mols of O2 and 82.91 k mols of N2 which must have
100
come out from the air supplied, i.e., 82.91 × = 104.95 k mols; and the O2 accompanying this air
79
21
= 104.95 × = 22.04 k mols.
100
Hence, the difference in quantity of O2 supplied and used in the formation of water vapour, which
is not appearing in dry flue gas analysis, will be (22.04 – 17.09) = 4.95, k mols
... The water vapour formed = 2 × 4.95 = 9.90 k mols.
... Mols of H2 present in the oil should also be = 9.90 k mols.
(2H2 + O2 → 2H2O)
The same quantity of the fuel oil contains 13.53 k mols, of C, (C + O2 → CO2).
... The fuel oil contains 13.53 mols of C ≡ 13.53 × 12 kg
= 162.36 kg of C and 9.9 × 2 = 19.8 kg of H2.
... The composition by weight of the hydrocarbon fuel is as follows:
162.36 ×100
C = 182.16 = 89.13%
19.8 ×100
H = = 10.87%
Now, 182.16
Total O2 supplied = 22.04 k mols,
O2 needed for C = 13.53 k mols,
O2 needed for H = 4.95 k mols.
104 BASIC ENGINEERING CHEMISTRY
... Total O2 actually needed} = (13.53 + 4.95) = 18.48 k mols
... Excess O2 = (22.04 – 18.48) mols = 3.56 k mols.
... % of Excess O2 (or air) used
3.56 ×100
= = 19.264%
Further, 18.48
Total fuel oil burnt = 182.16 kg
100
Total air supplied = 22.04 × kg mols
21
100
= 22.04 × × 22.4 m3
21
= 2319.4476 m3
.. . Air used per kg of fuel oil
2319.4476
= = 12.733 m3.
182.16
Example 10. A example gave the following analysis: C – 84%, H – 4%, O – 4%, ash – 8%. The
composition of the dry flue gas obtained by using the above coal is as follows
CO2 – 9%, CO – 1%, O2 – x% and N2 – (90 – x)%.
What will be the value of x?
Solution.
The problem can be solved by using the principle of oxygen balance.
100 kg of the coal sample contains:
Constituent Kg k Mols
84
C 84 =7
12
4
H 4 =2
2
4
O 4 = 0.125
32
100 mols of the flue gas contain
Constituent k Mols k Mols of C k Mols of O k Mols of N
CO2 9 9 9 —
CO 1 1 0.5 —
O2 x — x —
N2 (90 – x) — — (90 – x)
Total 100 10 (9.5 + x) (90 – x)
Let 100 mols of the petroleum gas be the basis for calculation:
Constituent Mols Mols O2 reqd. Products and Mols
C2H6 5 5 × 3.5 = 17.5 CO2 = 10; H2O = 15
C3H8 10 10 × 5 = 50 CO2 = 30; H2O = 40
C4H10 40 (Butane) 40 × 6.5 = 260 CO2 = 160; H2O = 200
30 (Isobutane) 30 × 6.5 = 195 CO2 = 120; H2O = 150
C4H8 10 10 × 6 = 60 CO2 = 40; H2O = 40
C3H6 5 5 × 4.5 = 22.5 CO2 = 15; H2O = 15
Total 605 mols 375 mols
Now,
O2 required for complete combustion of 100 mols of the petroleum gas = 605 mols.
106 BASIC ENGINEERING CHEMISTRY
100
... Air required for the complete combustion of 100 mols of the petroleum gas = 605 ×
21
mols = 2880.9524 mols.
.. . Air required for the complete combustion of 100 m3 of the petroleum gas = 2880.9524 m3.
40 21 3
O2 = 18.5 × × m = 1.554 m3
100 100
[from excess air)
79 3
N2 = 18.5 × + 0.06 m = 14.675 m
3
100
(from air + fuel)
Total volume of combustion products = 17.919 m3
Whence the volumetric composition of the flue gas i
1.69 ×100
CO2 = = 9.43%
17.919
1.554 ×100
O2 = = 8.67%
17.919
14.675 ×100
N2 = = 81.9%.
17.919
Example 15. A sample of coal contains C = 60%, H = 4%, O2 = 6%, N2 = 2% and ash = 28%.
Calculate the % age composition of the dry products of combustion, assuming that 40% excess air
is used.
Solution.
Constituents Amount percent in Combustion Amount of Amount of
1 kg of fuel Reaction O2 (in kg) dry pradud
Carbon 0.60 C + O2 → CO2 32/12 × 0.6 44/12 × 0.60
= 1.6 = 22
Hydrogen 0.40 H2 + 1/2O2 →H2O 16/2 × 0.4 —
= 0.32
Oxygen 0.60 — — —
Nitrogen 0.20 — — —
Amount of oxygen required = 1.6 + 0.32 – 0.06 = 1.86 kg
100
Amount of air = 1.86 × = 8.087 kg
23
140
Amount of air actually supplied = 8.087 × = 11.322 kg
100
Example 16. The percentage composition of coal was found to be as C = 54%, H = 6.5%, O
= 3.0%, N = 1.8%, moisture = 17.3% and remaining is ash. This coal on combustion with excess of
air gave 21.5 kg of dry flue gases per kg of coal burnt. Calculate the percentage of excess air used
for combustion.
Solution.
Constituents Amount/kg of Combustion Amount of Amount of
the fuel Reaction O2 (in kg) dry products (kg)
32 44
Carbon 0.54 C + O2 → CO2
0.54 × 0.54 ×
12 12
= 1.44 = 1.98
16
Hydrogen 0.065 H2 + 1/2O2 →H2 0.065 × —
12
= 0.52
Nitrogen 0.018 — — —
Oxygen 0.03 — — —
110 BASIC ENGINEERING CHEMISTRY
Amount of oxygen required = 1.44 + 0.52 – 0.3
= 1.93 kg
Amount of air required = 1.93 × 100
23
= 8.39 kg
Example 17. A gaseous fuel has the following composition by volume H2 = 20%, CH4 = 25%,
C2H6 = 16%, C2H4 = 9.5%, butene = 2.5%, CO = 4.0%, CO2 = 8%, O2 = 4% and N2 = 12%. Find
the air required for perfect combustion of 1m3 of this gas. If 50% of excess air is used, find the volume
analysis of the dry products of combustion.
Solution.
Constituent Amount in Combustion Vol of Vol of Dry
1m3 of fuel reaction Oxygen (m3) products (m3)
H2 0.20 H2 + 1/2O2 → H2O 0.20 × 0.50
= 0.1
CH4 0.25 CH4 + 2O2 →2CO2 0.25 × 2 CO2 =
+ 2H2O = 0.50 0.25 × 1 = 0.25
C2H6 0.16 C2H6 + 3.5O2→ 0.16 × 35 CO2 =
2CO2 + 3H2O = 0.56 16 × 2 = 0.32
C2H4 0.095 C2H4 + 3O2→ 0.095 × 3 CO2 =
2CO2 + 2H2O = 0.285 0.95 × 2 = 0.19
C4H8 0.025 C4H8 + 6O2→ 0.025 × 6 CO2 =
4CO2 + 4H2O = 0.15 0.25 × 4 = 0.1
CO 0.08 CO + 0.5O2→ 0.04 × 0.5 CO2 =
CO2 = 0.2 0.4 × 1 = 0.04
O2 0.04 — — —
N2 0.12 — — —
Example 18. A petrol sample contains 84% carbon and 16% hydrogen by weight. Its flue gas
compositional data by volume is as under
CO2 = 12.1%, CO = 1.1%, O2 = 1.3% and N2 = 85.5%
Calculate
(i) Minimum air for complete combustion of 10 kg of petrol
(ii) Calculate actual air supplied per kg of petrol
(iii) Calorific values of the pet ol sample
Solution. (i) 1 kg of petrol contain C = 840 g, H = 160 g
Constituent Amount Combustion Reaction Weight of O2 needed (g)
32
C 840 C + O2 → CO2 840 × = 2240
12
16
H 85.5 H + 0.5O2 → H2O 160 × = 1280
2
Total = 3520
Minimum wt. of air required for complete combustion of 1 kg of petrol
100
= 3520 × 15304.35 g = 15.30 kg
=
3
(ii) 1m of flue gas contain 23
CO2 = 0.121 m3, CO = 0.011m3, O2 = 0.013m3, N2 = 0.855 m3
FUELS AND COMBUSTION 111
Conversion :
Gas (V) Molecular mass (m) V × m Mass/kg of flue ga
CO2 = 0.121/m3 44 5.324 5.324/29.99 = CO2
= 0.1776 kg
CO = 0.011/m3 28 0.308 0.308/29.99 = CO
= 0.01027 kg
O2 = 0.013/m3 32 0.416 0.416/29.99 = O2
= 0.0139 kg
N2 = 0.855/m3 28 23.940 23.94/29.99 = N2
= 0.7983kg
E = 29.99 Total = 1.0000
Mass of excess O2 per kg of flue ga
= Mass of O2 (in flue gas – required to converte CO to C 2)
= [0.0139 – 0.01027 × (16/28)] kg
= [0.0139 – 0.0059] kg = 0.008 kg
12 12
Mass of C/kg of flue ga = Mass of CO 2 × + CO ×
44 28
12 12
= 0.1776 × kg − 0.0103 × kg
44 20
= 0.0440 kg
Weight of C/kg of petrol
=
Weight of C/kg of flue gas
0.84 kg
= = 19.09 kg
0.044 kg
\ Excess O2/kg of petrol burnt
100
= 0.153 × kg = 0.664 kg
23
Hence, actual air supplied per kg of petrol burnt
= Mass of air (For combustion + Excess in the gas)
= 15.30 + 0.664 kg
= 15.96 kg
1
(iii) HCV = [8080 × 8.4 + 34500 × 16] Kcal/kg
100
= 12307 Kcal/kg
Since the fuel does not contain hydrogen, so its
HCV = LCV.
Example 19. The percentage composition of petrol by weight was found to be C = 84% and
H = 16%. Calculate
(i) Minimum air required for complete combustion of 1 kg of petrol
(ii) % composition by weight of dry products of combustion corresponding to minimum air per
1 kg of petrol burnt
(iii) Calorific value of pet ol
112 BASIC ENGINEERING CHEMISTRY
Solution. (i) 1 kg of petrol contain C = 840 g, H = 160 g
Constituent Amount in (g) Combustion Reaction Weight of O2 required
32
C 840 C + O2 → CO2 840 × 2240g
=
12
16
H 85.5 H2 + 0.5O2 → H2O 160 × = 1280g
12
Total = 3520 g
Minimum weight of air required for complete combustion of 1 kg of petrol
100
= 3520 × = 15304.35 g = 15.30 kg
23
(ii) Weight of dry products of combustion
44
(i) CO2 = ×=840 3079.99 = g 3.08 kg
12
77
(ii) N2 = 77% of weight of air = × 15.30 = 11.78 kg
100
Total weight of dry products of combustion
3.08 + 11.78 = 14.86 kg
3.08 × 100
% of CO2 = = 20.73
14.86
11.78 × 100
% of N2 = = 79.27%
111.86
1
(iii) GCV = [(8080 × 84) + (34500 × 16)]
100
1
= [678720 + 552000] = 12307.2 Kcal
100
NCV = GCV – 0.09H × 587 Kcal/kg = 12307.2 – 0.09 × 16 × 587
= 12307.2 – 845.28 = 11461.92 Kcal.
Example 20. A gaseous fuel has the following composition by volume CH4 = 5%, H2 = 20%,
CO2 = 6%, CO = 25% and rest nitrogen. If 20% excess air is used for combustion, then calculate
volume of air per m3 of fuel and composition of dry fuel gas.
Solution. 1 m3 of gaseous fuel contains CH4 = 0.05 m3, H2 = 0.20 m2, CO = 0.25 m3, CO2 =
0.06 m3 and N2 = 0.46 m2 by difference)
Constituent Amount (m3) Combustion Volume of Vol of dry
Reaction O2 required product (m3)
CH4 0.05 CH4 + 2O2 0.05 × 2 = 0.10 CO2 = 0.005 × 1
→ CO2+ H2O = 0.5
H2 0.20 H2 + 0.5O2 0.20 × 0.5 = 0.100 —
→ H2O
CO 0.25 CO + 0.5O2 0.25 × 0.5 = 0.125 CO2 = 0.25 × 1
→ CO2 = 0.25
CO2 0.06 — — CO2 = 0.06 from
N2 0.46 — — N2 = 0.46 fuel
CO2 = 0.36
Total = 0.325 N2 = 0.46
FUELS AND COMBUSTION 113
Volume of air required per m3of gaseous fuel (using 20% excess air)
3 100 120
= 0.325m × × = 1.85% m3
21 100
Calculation of dry products of combustion CO2 = 0.36 m3, O2 = 20% of 0.325 m3
20 3
= × 0.325 m = 0.065 m3
100
N2 0.46 m3 (of gaseous fuel) + 1.857 m3 (77/100) of air
=
1.027 m3
=
Total volume of dry products (0.36 + 0.065 + 1.927) m3
=
2.352 m3
=
0.36 × 100
CO2 = = 15.306%
2.352
1.927 × 100
N2 = = 81.93%
2.352
0.065 × 100
O2 = = 2.764%
2.352
QUESTIONS
Percentage of excess air used and (c) the weight of the dry flue gas produced per kg of coal.
(Ans. : 8.3246 kg; 41.0984%; 12.0306 kg)
29. A gasoline sample contains 86% C and 14% H2. If the air supplied is only 95% of the
theoretically required value, calculate the dry flue gas analysis. Assume that all the H2
underwent complete combustion and no carbon is left free.
[Hint : For every 0.5 mol of O2 supplied less, 1 mol of C is converted into CO]
(Ans. : CO2 = 13.47%; CO = 2.36% and N2 = 84.17%)
30. Explain the following :
(a) The knocking tendency of petrol or diesel oil can be predicted on the basis of the nature
and molecular structure of its constituent compounds.
(b) All coking coals are caking but all caking coals are not coking.
31. A furnace utilises a mixture of blast furnace gas and coke oven gas as a fuel. The gas mixture
is fired along with air to obtain the required temperature. The analysis of the individual
gases used and the flue gas evolved due to the combustion of the above gas mixture
are given on dry basis and in volume percentage as below :
Constituent Coke oven gas Blast furnace gas Air Flue gas
3 Lubricants
3.1 INTRODUCTION
Friction and wear arise from the relative motion of two or more surface in contact. Friction
is a force of resistance to the relative motion of two contacting surfaces. Wear results when this
resistance is overcome by applied forces.
The substances which are used to remove friction between two or more moving surfaces is
known as Lubricant. The word ‘‘lubricant’’ derive from a latin word lubricus which means slippery.
Hence lubricants may be define as a substance which introduced between moving part of machinery
make the surface slippery and reduce friction, eliminates asperities and prevent cohesion. The
phenomeon is known as lubrication.
119
120 BASIC ENGINEERING CHEMISTRY
surfaces. Thus the expansion of metal by local frictional heat and the resultant deformation
and damage will be reduced.
3. In internal combustion engines, the lubricant also acts as fuel gasket between the piston and
cylinder wall at the compression rings and prevents the leakage of gases at high pressure in
the combustion chamber, thus minimizing the power loss.
4. It prevents the entry of moisture, dust and dirt between the moving parts.
5. It acts as a cleaning agent and as a scavenger to wash off and transport solid particles
produced in combustion or wear.
6. In aircraft, the lubricating oil may be used as a hydraulic fluid to change the pitch of the
propeller or to operate other mechanisms. The viscosity index of the oil is the important
property in such cases.
Coefficient of Friction f = F /W
where F = Force required to cause motion and
W = Applied load
Here the value of coefficient of friction is very lo . It ranges from 0.5 to 1.5.
In hydrodynamic lubrication (Fig. 3.2), a film of the lubricating oil covers the shaft as well
as the bearing surfaces. The oil film is sufficiently thick to cover the irregularities of the surfaces
and the metal surfaces do not come into contact with each other. Thus practically there is no wear.
The resistance to movement is only due to the resistance between the particles of the lubricant
moving over each other. Thus, in hydrodynamic lubrication, the lubricant chosen must have enough
viscosity so that the bearing force due to the rotation of the journal, will be sufficient to drag enough
oil between the journal and the bearing and at the same time, it should not be too much viscous to
offer resistance for the free motion of the lubricant particles over each other.
The efficiency of lubrication by this mechanism depends on the design of the bearing, the
loading, the rate of rotation of the shaft and on the viscosity of the lubricant. For a given load and
rate of rotation, the greater the lubricant viscosity, the greater the hydrodynamic pressure developed.
However, there is a practical limit to the viscosity which can be used, since a large amount of energy
would be needed to circulate and maintain a very viscous lubricant film
Hydrodynamic lubrication is maintained in case of delicate mechanical systems such as
watches, sewing machines and scientific instruments
The selection of a suitable fluid lubricant is complicated by changes of viscosity with
temperature. The viscosity of a typical hydrocarbon oil decreases as the temperature rises, so that
an oil which is satisfactory when an engine is cold may become too ‘thin’ to maintain an adequate
lubricant film at normal running temperatures. In order to maintain suitable viscosity of the oil for
A– LUBRICANTS 121
adequate lubrication in all seasons of a year, ordinary hydrocarbon lubricants are usually blended
with selected long chain polymers.
Hydrocarbon oils are considered to be satisfactory lubricants. Their viscosity increases with
increasing molecular weight. Suitable blends of appropriate fractions from petroleum refining
plants can be selected for different applications. However, these fractions generally contain small
quantities of unsaturated compounds which will oxidize under operating conditions, forming gums
or lacquers. Antioxidants, such as aminophenols, must therefore be blended with these oils. Further,
these oils may also undergo some decomposition in practice with the formation of solid carbon
particles. In order to keep these carbon particles in suspension in the lubricating oil, organometallic
“detergent” compounds are generally added.
B
2
R SOLIDS e.g. Graphite, Talc, Chalk, Molyhbdenum disulphide etc.
I 3
SEMI-SOLIDS e.g. Greases, Vaselines, waxes etc.
N
S
Furnace Dry
air
Coiled copper
tube
Hot
air
oil in
Platinum
tray
Gaseous fuel
57 mm
both from incomplete combustion of the fuel
as well as the carbonizing of the lubricating oil
1 mm
carried up past the piston rings into the combustion
chamber. Excessive build-up of carbon deposits
in the combustion chamber results in decreased Hemispherical
end
volume of the charge at the end of the compression
stroke giving increased compression ratio which 24.9 mm
eventually leads to detonation. Deposition of carbon ± 0.4 mm
residues by the lubricant may be objectionable in Fig. 3.9. Coking bulb used in Ramsbottom
other situations also. carbon residue test.
17. Flash and fi e point: The flash-point of an oil is defined as the minimum temperature at
which the oil gives off sufficient vapour to ignite momentarily when a flame of standard dimension
is brought near the surface of the oil (at a prescribed rate in an apparatus of specified dimensions) is
known as flash point. And the lowest temperature at which the vapours of the oil burn continuously
for at least 5 seconds when the standard flame is brought near the surface of the oil (which is heated
in a specified apparatus at a specified rate) is know as fire point. In a majority of the cases, the fire
point of an oil is about 5 to 40°F higher than its flash point
Determination: Flash point of an oil is determined by either open cup or closed cup apparatus.
In the open cup apparatus, the oil is heated with its upper surface exposed to the atmosphere. The open
cup apparatus commonly used is Cleveland’s apparatus. The closed cup apparatus in common use
are Abel’s apparatus and Pensky-Martens
apparatus. The closed cup apparatus gives
more reproducible results. The flash-point
obtained with an open cup apparatus is
generally about 10 to 30°F higher than that
obtained with a closed-cup apparatus.
of the lubricating oil. In addition, the flash point of an oil is often used as a means of identification
and also for detection of contamination of the lubricating oils.
17. Viscosity Viscosity is one of the most important properties of a lubricating oil. Viscosity is
a measure of the internal resistance to motion of a fluid and is mainly due to the forces of cohesion
between the fluid molecules. Absolute viscosity may be defined as the tangential force per unit area
required to maintain a unit velocity gradient between two parallel planes in the fluid unit distance
apart. The unit of absolute viscosity h (eta) in C.G.S. system are poise and centipoise (1/100th of a
poise). Poise is equal to one dyne per second per square centimeter. The viscosity of water at 20°C
is about 1 centipoise.
The ratio of absolute viscosity to density for any fluid is known as the absolute kinematic
viscosity. It is denoted by h and in C.G.S. system, its units are stokes and centistokes (1/100th of a
stoke).
h
v =
r
where
n = absolute kinematic viscosity
h = absolute dynamic viscosity
r = density of the fluid
The dimensions of dynamic viscosity are ML–1 T –1, and the dimensions of kinematic viscosity
are L2T–1.
For academic purposes, viscosity is usually expressed in centipoise or centistoke, but a more
common practical measure of the viscosity of an oil is the time in seconds for a given quantity of
the oil to flow through a standard orifice under the specified set of conditions. Thus, viscosities
are usually determined with Redwood Viscometer in the Commonwealth countries, with Engler’s
Viscometer in the Europe and with Seybolt’s viscometer in the U.S.A.
Measurement: Many types of viscometer are used to measure the viscosity of a lubricating
oil. Saybolt viscometer is used in United States of America and Redwood Viscometer is used in
England.
The Redwood viscometer no.1 consists of a standard cylindrical oil cup made up of brass and
silvered from inside. It has 90 mm height and 46.5 mm in diameter. It is fitted with an agate jet in
the base. The diameter of the orifice is 1.62 mm. The lid of the cup is provided with an arrangement
to fix a thermometer to indicate the temperature of oil. The oil cup is surrounded by water bath for
adjusting the temperature. A thermometer and stirrer are also provided in the water bath. A calibrated
receiving flask (known as Kohlraush flask) is provided for receiving the oil from the orifice. When
the sample reaches test temperature the time for 50 ml of the sample to flow through the orifice is
measured. Result are reported in redwood second.
Saybolt Viscometer
It was the first viscometer, which is based upon the principle of letting a known volume of
the liquid flow through a standard orifice. In the Saybolt Viscometer the fluid is contained in the
container. The container is surrounded by a water jacket in which water can be heated and stirred
electrically. The container is filled with the oil. After sometimes, the orifice at the bottom is opened
and the time taken for 60 cc of the liquid to pass through the standard orifice in the flask is noted and
the mean of the few reading recorded as viscosity.
Saybolt viscometer gives the viscosity of any liquid as the number of second required for 60cc.
of it to pass through the orifice under the given set of conditions
For very viscous fuels, a viscometer with a larger jet known as the Saybolt Furol Viscometer
is used. The Saybolt Universal viscometer can be used for oils having flow times of more than
32 seconds. There is no maximum limit, but in general, for liquids having flow times over 1000
seconds, Saybolt Furol Viscometer is better.
Viscosity Index
The viscosity of an oil decreases with increase of temperature as a result of decrease in
intermolecular attraction due to expansion. Hence it is always necessary to state the temperature at
which the viscosity was determined.
138 BASIC ENGINEERING CHEMISTRY
Viscosity index is the numerical expression of the average slope of the viscosity temperature
curve of a lubricating oil between 100°F to 210°F. The oil under examiantion is compared with two
standard oils having the same viscosity at 210°F as the oil under test. Oils of the Pennsylvanian type
crudes thin down the least with increase of temperature; whereas oils of Gulf coast origin thin down
the most as the temperature is increased. Hence the viscosity index of Pennsylvanian oil is taken as 100
and that of the Gulf oil as zero. Then the viscosity of the oil under investigation is deduced as follows:
VL – VX
Viscosity index = × 100
VL − VH
where
VL = Viscosity at 100°F of Gulf oil standard which has the same viscosity at
210°F as that of the oil under test
VX = Viscosity of the oil under test
VH = Viscosity at 100°F of Pennsylvanian standard oil which has the same
viscosity at 210°F as that of the oil under test.
Thus, the higher the viscosity index the lower the rate at which its viscosity decreases with increase
of temperature. Hence, oils of high viscosity index i.e., those having fl t viscosity temperature curves
are demanded for air-cooled internal combustion engines and aircrafts engines. In general, oils of
high specific gravity have steeper viscosity-temperature curves. However, all oils tend to attain the
same viscosity above 300°C.
By and large, light oils of low viscosity are used in plain bearings for high-speed equipment
such as turbines, spindles and centrifuges whereas high viscosity oils are used with plain bearings
of low speed equipment.
Conversion of Redwood, Engler and Saybolt viscosities into absolute units
Redwood, Engler and Saybolt viscosities can be converted to absolute units (centistokes).
However, since these instruments are not the ideal methods of determining the absolute viscosities,
the conversion values are only considered as good approximations and that too only when taken at
the same temperature. For instance, Redwood viscosities at 30°C cannot be converted into absolute
units at say 40°C, because, different fluids have di ferent viscosity temperature relationships.
The conversion of the above relative viscosities to absolute viscosities is done with the help of
the following equation:
v = Ct – b/t
where v = kinematic viscosity in centistokes, t = time of flow in seconds, and C and b are constants.
The following values are taken for the constants:
Instrument Value of C Value of b
Redwood No. 1 0.25 172
Redwood No. 2 2.72 1120
Saybolt Universal 0.22 180
Engler 0.147 374
Notes:
1. t = (Degrees Engler) × 52
2. Redwood Seconds No. 1 = 0.88 Saybolt Seconds Universal
3. Degrees Engler = 0.0328 Redwood Seconds No. 1
4. For accurate results, conversion constants should be determined experimentally at the
temperature under consideration.
19. Mechanical Tests. Several mechanical tests have been devised to test the performance of a
lubricating oil under a given set of conditions of temperature, load etc; one among them is the “four
ball extreme pressure lubricant test.” The working portion of such a machine consists three steel
balls held in a ring and an upper fourth ball in contact with them and this ball is held at the end of a
A– LUBRICANTS 139
vertical shaft which is rotated at a fix d speed by
an electric motor (Fig. 3.11). The three stationary
Ball chuck
balls are pressed upwards against the fourth ball
by a lever carrying an adjustable load. The torque Rotating ball
R
thus transmitted to the three fixed balls can be
measured and if required, the coefficient of S S S Stationery
balls
friction can be continuously recorded throughout
a test. The points of the balls are lubricated by
the test lubricant contained in a cup surrounding
the ball assembly. In a simple lubricant test, the
highest load that a ball can stand for 1 minute
without squeezing can be taken as a measure of Fig. 3.11. Four-ball extreme pressure testing
lubricant quality. machine.
L–U
Therefore V.I. = × 100
L–H
785 – 850
V.I. = × 100 = 19.4
785 – 450
QUESTIONS
1. Explain the following properties of lubricants and discuss their significance
(a) Viscosity and viscosity index (b) Flash Point
(c) Aniline Point (d) Saponification Value
2. Discuss the important properties of lubricating oils which are useful for their evaluation.
4. Distinguish between fluid film and boundary lubricatio
A– LUBRICANTS 143
5. A lubricating oil has the same viscosity as standard naphthenic and paraffinic type oils at
210°F. Their viscosities at 100°F are 320 S.U.S., 430 S.U.S. and 260 S.U.S. respectively.
Find the viscosity index of the oil.
6. What do you mean by viscosity index of a lubricating oil ?
A lubricating oil has a S.U.S. os 64 seconds at 210°F and of 600 seconds at 100°F. The high
viscosity index standard (i.e. Pennsylvanian) oil has S.U.V. of 64 seconds at 210°F and 400
seconds at 100°F. The low viscosity index standard (i.e. Gulf) oil has a S.U.V. of 64 seconds
at 210°F and 700 seconds at 100°F. Calculate the viscosity index of the oil.
(RGPV Bhopal 2006)
7. Write an essay on solid lubricants with emphasis on their classification, mechanism of action,
examples and applications.
8. How are semi-solid lubricants prepared ? In what situations a semisolid lubricant is preferred?
Mention some important tests for evaluating semisolid lubricants.
9. How are liquid lubricants classified ? Discuss the various methods available for refining
mineral oils.
10. What are the various types of synthetic lubricants available ? Discuss their merits and
demerits.
11. Discuss the use of lubricating emulsions.
12. Write informative notes on the following :
(a) Graphite (b) Cup greases (c) Neutralization number (d) Extreme pressure lubrication
(e) Oiliness (f) Carbon residue test (g) Pensky Martin’s apparatus (h) Redwood Viscometer.
13. Justify the following statements :
(a) Flash point determination by the closed cup apparatus gives a lower value than that
determined by an open cup apparatus.
(b) Closed cup apparatus gives a more reliable value than the open cup apparatus for the
determination of flash point
(c) The relative viscosity determined by Saybolt viscometer or Redwood viscometer can
be converted into absolute kinematic viscosity by calculations.
14. Define lubrication. Explain various types of lubrication and discuss any three important
properties of lubricants. (RGPV Bhopal 2001, 2006)
15. (a) How does viscosity determine the operating characteristics of a lubricant ?
(b) Suggest the suitable properties of the lubricating oil used for steam engines and
transformers.
(c) Describe with their significance the following
(i) Aniline Point
(ii) Cloud point and pour point (RGPV Bhopal 2009)
(iii) Steam emulsification numbe (Nagpur University, 2001)
(iv) Important function of lubricant.
16. (a) What are flash point and fire point of a lubricant. Point out their significan
(b) Explain the following properties of lubricants :
(i) Viscosity Index (ii) Aniline Point (iii) Neutralisation Number
(c) Write short note on Redwood Viscometer
17. (a) Define
(i) Acid Value (ii) Saponification iii) Pour Point
(b) What are different mechanisms of lubrication ? Explain the boundary lubrication.
(RGPV Bhopal 2009)
(c) Write a note on determination of flash point by Pensky Martin Method. What is the
significance of flash poin (RGPV Bhopal 2009)
18. (a) Define grease. Under what situations it is used as a lubricant (RGPV Bhopal 2006)
144 BASIC ENGINEERING CHEMISTRY
(b) How are lubricants obtained and refined from crude petroleum
(c) Write notes on boundary lubrication. (Mumbai University, 1998)
19. (a) What is the purpose of dewaxing a lubricant ? How is it carried out ?
(b) Explain the following :
(i) Flash point and fire poin (ii) Pour point and cloud point
(c) Write notes on :
(i) Solid lubricants
(ii) Working of Redwood Viscometer. (Mumbai University, 1998)
20. (a) Define lubrication. Explain the mechanism of boundary lubrication
(b) Explain the following properties of lubricants and give their significance
(i) Emulsification ii) Aniline Point (iii) Cloud Point and Pour Point
(c) Describe the conditions under which solid lubricants are used.
(Mumbai University, 1999)
21. (a) How would you determine viscosity of a lubricating oil using Redwood Viscometer ?
(b) Describe how do you determine neutralisation number and saponification value of a
lubricant.
(c) State essential properties of a lubricant. (Mumbai University, 2000)
22. (a) What are the essential properties of a lubricant ?
(b) How would you determine flash and fire points of a lubricant
(c) Explain the extraction and purification of mineral oil (Mumbai University, 2001)
23. Explain the following :
(a) Synthetic lubricants (b) Boundary lubrication
24. Write informative notes on any two of the following :
(a) Lubricating Emulsions (b) Solid Lubricants
(c) Synthetic Lubricants
25. Write informative notes on any two of the following :
(a) Extreme Pressure Lubricants. (b) Lubricating Emulsions
(c) Blended Oils.
26. What do you mean by viscosity index ? Discuss the importance of oxidation stability and
iodine value of a lubricant.
27. What are the factors to be considered while selecting a lubricant for a particular purpose.
28. How can we obtain lubricating oil from crude oil. What is the importance of dewaxing of
oil fractions?
29. (a) “Closed cup apparatus gives a more reliable flash point than that given by the open cup
apparatus”. Justify the statement.
(b) Describe how relative viscosity of a lubricating oil is determined by Redwood viscometer.
What is the difference between Redwood No.1. and Redwood No. 2 viscometers ?
(c) What considerations should be made while selecting a lubricant for cutting oils.
(Nagpur University, 2002)
30. (A) Explain the following properties of liquid lubricants emphasizing their significance
(a) Neutralization number (b) Aniline point (c) steam emulsification numbe
(B) Write short notes on graphite as a lubricant
(C) Suggest suitable lubricants for the following with proper justification
(i) Steam turbines (ii) I.C. engines (Nagpur University, 2002)
31. How viscosity index of a lubricating oil is determined by Redwood viscometer? Write the
significance of the test (RGPV Bhopal 2009)
32. What are the characteristic features of lubricats? Write the criteria for selection of lubricants
for specific purpose (RGPV Bhopal 2009)
PART–B
UNIT
CEMENT
3.11 Introduction
Cement is a material which possesses adhesive and cohesive properties and capable of bonding
materials like bricks, stones, building block etc.
Properties
(i) It possess hydrolic properties
(ii) It is a quite setting cement
(iii) It has low strength
Applications
(a) Combination of sand with natural cement (Known as Mortors) is used for laying bricks and
setting stones.
(b) It is also used in large masses of concretes e.g. dams and foundation
(ii) Pozzolana cement: It is the oldest cement which was invented by Romans and was used
for construction of dams etc. It is prepared by mixing and grinding pozzolana and slaked
time. Natural pozzolana is deposit of volcanic ash produced by rapid cooling lava. Lava is
a molten mixture of silicates of calcium, iron and alminium.
Properties. They posses hydrolic properties.
Application Their mixture with Portland cement is used for different applications
(iii) Slag cement: It is prepared from blast furnace slag and hydrated lime. At first a mixture of
calcium, aluminium silicates (blast furnace slag) is granulated by pouring it into the streams
of cold water. Now dried the mixture and mix it with hydrated lime. Now pulvarized the
mixture. Sometimes acceleratory like clay, salt or caustic soda are added to accelerate the
hardening process.
Properties. (i) They are low setting
(ii) They are poor in abrasion resistance.
(iii) They have low strength.
145
146 BASIC ENGINEERING CHEMISTRY
Applications
(a) It is used for making concrete in bulk construction.
(iv) Portland Cement: It is made by calcining (at 1500 °C) an intimate mixture of clay and
lime containing raw material in correct proportion. After calcinations, retarder like gypsum
is added.
Other Types of Cements
Some other types of cements are also used in special types of construction work, and these are
not portland cements or their derivatives.
(1) High alumina cement. It is manufactured by heating, until molten, a mixture of limestone
and bauxite to produce essentially calcium aluminates (CA and C12A7) and quickly cooling the product.
The finely ground product is quite dark in colour. It gains strength very quickly and is particularly
useful under extremely low temperature conditions where ordinary Portland cement does not gain
strength. This kind of cement is known as “Ciment Fondu” in western countries. Another remarkable
feature about this cement is that it can be used as refractory material at 1000°C and is used for making
castable refractories and for making ‘in situ’ castings.
(2) Magnesium oxychloride cement. This is also called Sorel cement. It is prepared by the
reaction of magnesia and a solution of MgCl2. The reaction is exothermic. The composition of the
product formed is roughly 3 MgO.MgCl2.11 H2O. This kind of cement is generally prepared ‘in
situ’ or in moulds. It can be used as flooring material with coloured pigments and other inert fillers
producing very pleasing surfaces. However, it is rapidly eroded by water and hence is limited in its use.
(3) Strontium and Barium Cements. These cements are extensively used in concrete shielding
for atomic piles where resistance to penetration of radioactive emanations is essential. These are
manufactured by employing strontium and barium salts instead of calcium salts during the cement
manufacture.
3.13 PORTLAND CEMENT
At first Joseph Aspidin in 1824 find out that the hard clinkers when ground and mixed with
water, produced a highly superior hydraulic cement. Which are similar in colour with a natural stone
Portland therefore it is known as Portland cement.
Raw Materials
The raw materials used in the manufacture of Portland cement are:
(a) Calcareous materials (which supply lime) e.g., lime stone, cement rock (a soft argillaceous
lime stone), chalk, marl or marine shells, and waste calcium carbonate from industrial processes.
A lime stone high in magnesia cannot be used unless its magnesia content is reduced by some
means, as by flotation, or dilution with low-magnesia rock so that the product will not contain more
than 5% MgO. Similarly, chalk containing flint has to be freed from that impurity, and seams of
gypsum or other materials such as pyrite may require selective handling before use.
(b) Argillaceous materials (which supply silica, alumina and iron oxide) e.g., clay, shale, blast-
furnace slag, ashes and cement rock. Clay or shale are most commonly used. Cement rock was
sometimes used as such without any further addition, since it contains both limestone and clay
minerals. The modern demands, however, have made necessary more precise control of composition
and hence, such a simple procedure is rarely employed today.
The compounds then combine together to form small, hard, greyish pellets called cement clinkers.
148 BASIC ENGINEERING CHEMISTRY
6. Grinding the clinker with gypsum. The cooled clinker is then finely pulverised together
with 2 to 6% gypsum (which acts as a setting time retarder of cement water paste) in long tube mills.
The finer the cement, the greater is the strength of the concrete made from it
B– CEMENT AND REFRACTORIES 149
7. Storage and packing. The cement coming out of the grinding mills is stored in concrete
storage silos. Moisture free compressed air is used to agitate the cement and to keep it free from
compaction by its own weight. In India, cement is usually packed in jute bags each holding 50 kg
nett of cement.
Dry process. In this process, the calcareous and argillaceous materials are crushed in gyratory
crushers to small pieces, dried and mixed in proper proportion, pulverised in tube mills and
homogenised in a mixing mill with the help of compressed air. This “raw meal” is introduced into
the upper end of the rotary kiln while a blast of burning coal dust is blown from the other end. The
reactions taking place and the rest of the process is same as described under wet process.
Semi dry process. In this process, the raw materials are initially ground dry, but instead of
feeding as a powder the ‘raw meal’ is nodulised with 10–14% water in a pan or drum type noduliser.
The nodules are fed on a travelling grate where they get dried and preheated before entering a short
rotary kiln where they are burnt to form cement clinker.
Dry Process Vs Wet Process
Dry Process Wet Process
1. It is slow and costly process. It is comparatively faster and cheaper process.
2. Cost of production of cement is less, as the
Cost of production higher become of the higher
fuel consumption is low. fuel consumption.
3. The quality of cement produced is inferior.
The quality of cement produced is somewhat
superior.
4. This process is adopted when the raw This process is preferred when the raw materials
materials are quite hard. are soft.
5 A shorter kiln is sufficien Longer kiln needed to drive off the excess water.
* KJ/Kg = Kilo joules per kilogram. This is the unit of heat in MKS system. 1 cal/g = 4.185 Joules/g = 4.185 KJ/Kg.
** The rate on hydration is the percentage of hydration over 7 days using Type I cement at water to cement ratio of 0.4. It
is followed by X-ray diffraction studies.
150 BASIC ENGINEERING CHEMISTRY
(2) Tricalcium silicate (C3S): It develops very high strength quite early and the ultimate strength
is also the highest. Its rate of hydration is medium (73.5%). Its heat of hydration is about 120 cals/
gram (502 KJ/Kg).
(3) Tetracalcium aluminoferrite (C4AF): It does not contribute much to the strength of
cement because both its early strength and the ultimate strength are poor and the lowest among the
constitutional compounds. Its rate of hydration is slow (57%) and hence it is slow setting. Its heat of
hydration is about 100 cals/gram (418.4 KJ/Kg).
(4) Dicalcium silicate (C2S): This hydrates very slowly. Its rate of hydration is 37.5%. Its heat
of hydration is the lowest among all the constitutional compounds of cement and is about 60 cals/
gram (251 KJ/Kg).
Its early strength is quite low but develops ultimate strength almost of the same order as C3S.
* The term “Pozzolanic” comes from “Pouzzoles”, a city near Naples where volcanic silico-aluminate calcium ash is found.
152 BASIC ENGINEERING CHEMISTRY
These gels shrink with passage of time and leave some capillaries for the water to come in contact
with C3S and C2S to undergo further hydration and hydrolysis reactions enabling the development
of greater strength over a length of time.
3 CaO . SiO2 + x H2O → 2 CaO . SiO2 (x – 1) H2O + Ca (OH)2
gels crystals
2 CaO . SiO2 + x H2O → 2 CaO . SiO2 . x H2O
gels
The setting and hardening of cement may be summarized diagrammatically as follows:
Unhydrated cement
Hydration
↓
Stable Gel → Crystalline products
An abnormal type of set is sometimes encountered where the cement paste stiffens quickly, but
without the evolution of considerable heat and may again be rendered fluid by remixing. This condition
is called false set. This is due to (1) the dehydration of the gypsum during grinding process brought
about by excessive temperature in the mills. The resulting cement then contains anhydrite, CaSO4
which quickly sets by hydrating to gypsum, CaSO4, 2H2O, and (2) presence of alkali carbonates in
the cement, which may form during storage of alkali containing cements. The alkali carbonate could
then react with Ca(OH)2 produced by the rapid hydrolysis of C3S, thus generating CaCO3 which
brings about some rigidity of set.
Cement
+
Water
↓
Plastic mass
Physical requirements
1. Setting time:
Initial : Not less than 30 minutes
Final: Not more than 600 minutes
2. Compressive strength:
(1 : 3 cement mortar cubes cement and blended Ennore sand)
3 days Not less than 1.6 Kgf/mm2
7 days Not less than 2.2 Kgf/mm2
(Kgf = Kilogram force = 9.807 Newtons).
3. Soundness:
By Autoclave method : Expansion not more than 0.8%
By Le Chatiler method : Unaerated cement : max 10 mm
Aerated cement : max 5 mm
4. Fineness:
As specific surface b Not less than
Blain permeability method 215 m2/Kg
154 BASIC ENGINEERING CHEMISTRY
Table 3.3 General Composition of Ordinary Portland Cement:
Reactions taking place during burning of the raw materials in the rotary kiln:
< 800°C — Formation of CA, C2 F and C2S starts
800 – 900°C — Formation of starts
900 – 1100°C — Formation and decomposition of C2AS; Formation of C3A and C4AF
starts; Full decomposition of CaCO3 takes place and formation of
free CaO reaches a maximum.
1100 – 1200°C — Maximum formation of the constitutional compounds viz., C3A,
C4AF, and C2S
1200 – 1450°C — Formation of C3S with gradual disappearance of free CaO takes place.
REFRACTORIES
3.18 REFRACTORIES
Refractories are such inorganic materials which can withstand very high temperatures without
softening, melting or deformation. The essential function of a refractory is to serve as structural
material and maintain its mechanical functions at high temperatures under the service conditions.
The PCE test is also used to check the uniformity of composition of refractory raw material
and finished products, to classify fire clay refractories, and to determine the contamination of the
refractories from the fluxes and other material encountered in serice conditions
162 BASIC ENGINEERING CHEMISTRY
(ii) Refractoriness Under Load (Strength): The Commercial refractories which are used for
lining high temperature furnace are expected to withstand varying load of the charge. Therefore, the
refractory should have high strength and good temperature resistance.
Refractoriness under load is an important consideration because usually a refractory fails at a
lower temperature when subjected to load e.g. alumina brick and fire clay refractory they collapse
for below their fusion temperature. This is supposed to be due to the fact that some crystals which
have become fluidic act as a lubricant and deformation becomes easier when subjected to load.
Some other refractory material like silica bricks when exert good bearing charactecteristics up to
their fusion temperature. Thus for good results, refractoriness under load (R.U.L) test is performed
by applying a load (3.5 or 1.75 Kg/cm2) to the refractory specimen (of size 5cm2 and 75 cm high).
The sample is then kept in carbon resistance furnace and heating is started at the rate of 10 °C/
minute. The height of the specimen is plotted against temperature and R.U.L. is expressed as the
temperature at which 10% deformation take place.
(iii) Porosity: Porosity of a material is given by the ratio of its pores volume to that of its bulk
volume. The higher the porosity of a refractory brick, the more easily it is penetrated by gases and
molten fluxes. For a particular class of refractory brick, the one with the lowest porosity may be
taken as the best because it will have the greatest strength, heat capacity, and thermal conductivity.
Further, it will have greater resistance to abrasion and corrosion although the resistance to thermal
spalling decreases with the decrease in porosity. Thus, porosity is an important property of a
refractory material as it is related directly to many other physical properties.
(iv) Thermal spalling: Rapid change in temperature, cause uneven expansion and contraction
of refractory material. Due to which internal stresses and strains develops, which lead cracking,
breaking or fracturing of refractory bricks under high temperature, this whole process is known
as thermal spalling. Spalling may also occur due to penetration of molten slag into the pores of
refractory brick which leads to cracking due to the differences in their coefficient of expansion and
contraction. A good refractory must show a good resistance to thermal spalling. It can be minimized
by
(a) Using a refractory bricks having low coefficient of expansion, good thermal conductivity
and high porosity
(b) By avoiding sudden change in temperature.
(c) By over firing the refractory bricks during manufacture
(d) By improving furnace design to minimize the stresses and strain.
(v) Thermal Conductivity: Thermal conductivity is an important property of a refractory
because it determines the amount of heat that flows through a furnace wall under given service
conditions. Insulating refractories with low thermal conductivity will not allow much loss of the
furnace heat and hence they are used in blast furnace, open hearth furnace, etc. On the other hand,
refractories with high thermal conductivity are used in the construction of muffle walls, retorts
and recuperators where efficient heat transfer from the outer surface to the charge is needed. The
densest and least porous bricks possess the highest thermal conductivity due to the absence of air
in the voids. If the brick is porous, the air entrapped in the voids (or pores) provides an insulating
effect. Porous bricks can be prepared by mixing copious amount of a carbonaceous material with
the refractory mix before moulding. When the moulds are burnt, the carbonaceous material burns
off leaving behind minute voids which provide the insulating effect.
B– CEMENT AND REFRACTORIES 163
(vi) Heat Capacity: The heat capacity of a furnace depends upon the following three factors:
(i) the thermal conductivity (ii) the specific heat and iii) the specific gravity of the refractor .
Lightweight refractory bricks have low heat capacity and hence are suitable for intermittently
operated furnaces because the working temperature of the furnace can be achieved in lesser time
and with lesser consumption of fuel. Conversely, the dense and heavy fire clay bricks have higher
heat capacity and as such are best suited for regenerative checkerwork systems used in coke ovens,
stoves for blast furnaces, glass furnaces etc.
(vii) Electrical Conductivity: Refractories are poor conductors of electricity with the exception
of graphite. Refractories used for lining of electric furnaces should also have low electrical
conductivity.
(viii) Bulk Density: This influences many other important properties. A high bulk density will
improve strength, volume stability, heat capacity and spalling resistance. However, for insulating
refractories, a porous structure is needed which is provided by a low density of the refractory.
(ix) Dimension Stability: It is resistance of a material to any change in volume when the
refractory is exposed to high temperature, over a prolonged period of time.
1. Acid Refractories
(A) Fire Clay Refractories. Fire clays are the most widely used refractory materials and are
well suited for a variety of applications. These contain 25 to 44% of Al2O3 and upto 70% SiO2. The
164 BASIC ENGINEERING CHEMISTRY
chief raw materials used for the manufacture of this type of refractory are calcined fire clays, and
since these clays can withstand high temperatures, these are called fire clay refractories. Calcined
fire clay, known as the “Grog”, accounts for 50% or more of the batch mix. Grog is prepared by
calcining fire clay at about 1450°C in rotary kilns, followed by crushing, sieving and grading. The
graded fractions are suitably blended. Plastic clay is the usual bonding material used. For high
grog bricks, additional bonding material like molasses, dextrin or sulphite may also be required.
Addition of water may vary from 3 to 30% depending upon the method of forming proposed to
be used subsequently. Moulding is done by hand or by machine. Hand moulding is done for non
standard sizes and shapes. In this the mixture containing 15 to 20% water is rammed and beaten
into mould taking care to see that air pockets, voids etc., are absent. Bricks of low porosity and high
slag resistance are generally produced by dry pressing the mix containing 3 to 74 water in de-airing
type mechanical or hydraulic toggle presses at a pressure of 75 to 150 MN/m2. Hollow bricks like
sleeves, pipes and tuyers are prepared in specially designed vertical auger machines using semi-
plastic mixes having 10 to 12% water.
Properties
1. The fire clay refractories are pale bu f to light brown in colour.
2. Their hardness depends upon the firing conditions.
3. Properly fired bricks are as hard as steel.
4. Their porosity varies from 8 to 30%.
5. At high temperatures, the fire clay refractories combine with soda, potash, lime, MgO, FeO,
sulphates, chlorides and carbonates to form fusible salts.
6. Their crushing strength in cold is about 950 kg/cm2 which goes down with increasing tem-
perature.
7. Their refractoriness depends upon the softening point of the fire clay used. Their safe work-
ing temperature is about 1545°C.
8. They have softening point of 1350°C under a load of 50 lbs sq.in.
9. Their spalling tendency can be decreased by using a coarse grog, by increasing the porosity,
and decreasing the coefficient of expansion.
10. The specific heat of fire clay brick is as low as 0.25 which increases with temperature and
reaches 0.264 at 1300°C.
11. Its thermal conductivity varies from 0.8 to 0.95 (in CGS units) from 300°C to 1100°C.
12. Though they are bad conductors of heat, their radiation power is high and hence fire cham-
bers made of fire clay can be heated to very high temperature compared to silica bricks.
13. Their spalling resistance makes them particularly suitable for making checker work of re-
generating furnaces which are susceptible to temperature fluctuations.
14. Fire clay refractories are classified as high duty (> 40% Al2O3), moderate heat duty ‘A’ (>
30% Al2O3 and < 65% SiO2) and moderate heat duty ‘B’ (> 25% Al2O3 and < 70% SiO2)
types.
Uses
1. The steel industries are the largest consumers of fire clay refractories.
2. They are used for lining of blast furnaces, open hearths, stoves, ovens, flues, crucible
furnaces etc.
3. Fire clay refractories are also widely used in foundries, lime kilns, regenerators, pottery
kilns, continuous ceramic and metallurgical kilns, glass furnaces, cupolas, brass and copper
furnaces, boiler settings, gas-generators, etc.
B– CEMENT AND REFRACTORIES 165
(B) Silica Refractories. The raw material used for the manufacture of silica bricks are quartz,
quartzites, sand stone, gannister etc. The rock is first crushed and ground with 2% lime and water
(binding material). The thick paste is then made into bricks by machine pressing. Bricks are then
dried slowly and than they are fired in the kiln for 24 hours. The temperature is slowly raised to
1500°C. This temperature is kept constant for twelve hours. During this period the quartzite is
converted into crystobalite. Careful cooling is then taken in 1 to2 weeks. Cristobalite is slowly
changed into tridymite and final brick is the mixture of the two form
Properties
1. Silica bricks have homogeneous texture, free from air pockets and moulding defects.
2. They possess a low porosity (17 to 25%).
3. These are the properties desirable for resistance to slag penetration for a refractory used in
furnaces.
4. The silica bricks can withstand a load of about 3.5 kg/cm2 upto about 1600°C.
5. They are resistant to thermal spalling below 800°C.
6. They possess low permeability to gases.
7. Their physical strength when heated is much higher than that of fire clay bricks.
8. Furnaces using silica bricks must be heated and cooled gradually to minimize spalling and
cracking.
Uses
(i) The largest consumer of silica is the iron and steel industry.
(ii) Due to their high Physical strength, they are used for arches in large furnace.
(iii) They are used for side walls, port arches, and built-heads of open health furnaces, coproduct
cake ovens, gas retorts, glass furnaces, electric furnace, roofs, copper stove, domes, acid
converter linings etc.
(C) High-alumina Refractories When the alumina content in fire clay brick reaches above
47.5%, then it is called high alumina refractory brick. These are made from clays rich in bauxite and
diaspore. The refractoriness and the temperature of incipient vitrification increase with the alumina
content.
BASIC REFRACTORIES
(A) Magnesite Refractories:
It is made from dead burnt magnesite grain, which are properly crushed into powder form of
proper size. Molasses or sulphite lye is used as a binder. 2 to 6% of alumina is added to impart
thermal shock resistance of the refractory. Now add sufficient amount of water into it and ingredients
are blended. The mix is aged for 1 to 10 days to ensure complete hydration of any free lime present.
The mix is then moulded into bricks and temperature is slowly increased to 1500°C. The bricks are
kept at this temperature for about 8 hrs and then slowly cooled.
Fire bonded magnesite bricks are susceptible to spalling. This drawback is removed by chemical
bonding or by metal casing. For preparing chemically bonded magnesite refractories, the mechanical
strength is developed by adding a chemical bonding agent e.g., oxychloride or oxysulphate, instead
of by firing. In this case, higher forming pressures are needed to minimize voids. Curing and drying
are carried out in specially designed tunnel dryers.
Properties
1. Magnesite bricks have low resistance to acid slag but high resistance to basic slag.
2. They have high thermal conductivity and low permeability.
166 BASIC ENGINEERING CHEMISTRY
3. Their resistance to spalling for normal bricks is very poor.
4. However, chemically bonded and metal cased bricks have better spalling resistance.
5. Magnesite bricks can be used upto 2000°C without load and upto 1,500°C under load of 3.5
kg/cm2. Their abrasion resistance is poor.
6. They have a tendency to combine with water and CO2.
Uses
1. Magnesite refractories are preferred where basic materials in molten state are to be heated
at high temperatures.
2. These refractories are used in open hearth and electric furnace walls in the roofs of non-
ferrous reverberatory furnaces e.g., those used for Cu, Pb and Sb.
3. They are also used for lining of basic converters in steel industry, hot mixer linings, copper
converters, refining furnaces for Ag, Au and Pt. etc.
(B) Dolomite Refractories
Dolomite is a mixed carbonate of calcium and magnesium CaMg (CO3)2.For preparing dolomite
bricks, the mineral is washed, crushed and calcined. Due to which dolomite decomposed and form
CaO and MgO. Now mix it with binder (e.g. silicate) and water. The mixture is allowed to stand
for sometime and then moulded into bricks. The dried bricks are then fired at 1500°C in a kiln for
about 24 hours.
Properties:
(i) They posses less strength and low resistance to thermal shocks.
(ii) They are more soft, more hygroscopic, more porous and possess less strength as compared
to magnesia bricks.
(iii) They have greater shrinkage and lesser resistance to thermal shock.
The properties of dolomite bricks can be improved by mixing the dolomite with MgO SiO2
and calcining the mixture. Which brings about the formation of di and tri-calcium silicate.
Now blend the mixture with silicate binder. Mould the mixture into bricks followed by fi -
ing at 1500°C for a day or two to give stabilized dolomite bricks. These bricks are more
stable towards basic slags.
Uses
Dolomite refractories are quite cheap and used in granular form to pitch the bottom of open-
hearth furnace and for repairing works. Stabilized dolomite bricks are used in Bessemer convertors,
ladle linings and for basic electric furnace lining.
Such materials are called super-refractories which possess high melting point, good volume
stability and stability against transformations during heating. Their preparation does not require
calcining.
Uses
Forsterite is used in glass tank super-structures and checkers because they possess high chemical
resistance to the fluxes used and good strength at high temperatures allow increased tank output.
These refractories are also used in open-hearth end walls and copper refining furnaces
NEUTRAL REFRACTORIES
(A) Carbon Refractories
For preparing carbon refractories low ash content (0.15%) carbon (e.g. coke derived from coal)
are used. At first crushed the coke and dried it in a rotary dryer. Now mix it with 15% tar or pitch
in a dry pal mill. The mixing or blending carried out when the mixer is hot at 58 to 80°C. Moulding
is carried out by dry pressing of the hot mixture at a pressure of 30 to 40 MN/m2. Hardening takes
place within 1 to 6 days, depending upon the size. Firing is carried out in a reducing atmosphere at
800 to 1000°C packing the shapes in carbon.
Properties
(i) Carbon refractories have high refractoriness, high resistance to acid slag, high resistance to
thermal shock and spalling and high load bearing capacity at high temperatures.
(ii) They have low resistance to basic slag, low resistance to oxidising atmosphere and possess
low thermal expansion.
(iii) Their thermal and electrical conductivity is wide ranging.
(iv) They react with water above 600°C and CO2 above 700°C.
(v) Carbon refractories are practically infusible, close textured and can withstand temperature
fluctuations and chemical attack in neutral or reducing condition .
Uses
Carbon refractories are used for making electrodes and for linings in chemically reactive
equipments.
Properties
1. Silicon carbide super-refractories are characterised by their chemical resistance, high re-
fractoriness and ability to withstand sudden temperature fluctuations.
2. The bricks are extremely refractory and possess high resistance to spalling and abrasion.
3. They have a high thermal conductivity, low thermal expansion, high mechanical strength
and can withstand loads in furnaces even at 1650°C and higher.
4. Their resistance to acid slag and to reducing atmosphere is high, whereas their resistance to
oxidising atmosphere is medium and their resistance to basic slag is low.
5. Self-bonded silicon carbide refractory bricks have superior properties than silicon nitride-
bonded bricks which in turn are superior to the clay bonded bricks. Silicon carbide bricks
have a tendency to oxidize to silicon in oxidizing atmosphere around 950°C.
6. This tendency can be counteracted by coating with a thin layer of zirconium.
Uses
1. Silicon carbide refractories on account of their good thermal conductivity, are mainly used
in muffles.
2. Their ability to absorb and release heat rapidly and their resistance to spalling under repeated
temperature fluctuations make them an ideal choice for recuperators.
3. Silicon carbide bricks are also used for partition walls of chamber kilns, coke ovens and
furnace floors.
4. Owing to their high electrical conductivity, they are used as heating elements in furnaces in
the form of rods and bars known as globars.
5. Silicon carbide bonded with tar are excellent for making high conductivity crucibles.
6. Clay bonded bricks are preferred for high conductivity bricks while lime-bonded bricks are
used for muffle and electric furnace lining
B– CEMENT AND REFRACTORIES 169
(D) Chromite Refractories
Chromite is a mineral of spinel group which is chemically a double oxide of chromium and
iron, FeO.Cr2O3. The general term spinel indicates any mineral given by the general composition
M,O,M2O3 where M = Ca, Fe and Mg and M' = Cr and Al respectively.
Preparation: At first chromite (Cr2O3. FeO) is blended with clay and then firing is done at
temperature of 1500°C to 1700°C.
Due to firing process oxidation of Fe ii) to Fe (iii) takes place.
Fe2 Cr2 O4 + O2 —→ Fe2O3 + Cr2O3
Properties
(i) They are neutral refractory having good resistance for slag
(ii) Their spalling resistance is average.
(iii) They have high density and have moderate thermal conductivity
(iv) They are used at 1800°C
(v) They have refractoriness under load and have excellent crushing strength
Uses
These bricks are used in
(i) Furnace lining
(ii) Sodium carbonate recovery furnace
(iii) Bottom of soaking pits.
SPECIAL REFRACTORIES
(A) Single or Pure Oxide Refractories
The refractory industry has been constantly facing demands for products having very high
refractoriness and which can withstand very severe operating conditions. Pure oxide refractories are
developed to meet these demands. Refractory oxides of interest under this category in the increasing
cost per unit volume are: alumina, magnesia, zirconia, beryllia and thoria. All these have been
developed commercially for light refractory products. The pure zirconia refractories are used in kilns
needed for firing barium titanate resistors
(i) Pure Alumina Refractories
These are made from calcined or fused alumina having a purity greater than 97%. The usual
additions are 2% of Kaolin (which reduces the sintering temperatures and improves pressing
characteristics) and 2% of talc or magnesite (which controls the grain size and improves pressing
characteristics). The binding agent used depends upon the method adapted for forming. For dry
pressing, organic binders e.g., cellulose or polyvinyl alcohol are used. Firing temperatures are in
the range of 1700-1800°C depending upon the purity of alumina. Forming can also be done by hot
pressing in graphite moulds. Pure alumina refractories belong to neutral type having good resistance
to oxidising and reducing atmospheres even upto 1900°C. High temperature kilns furnish alumina
bricks which approach pure corundum in properties which have high slag resistances. Such refractories
are used where severe slagging occurs.
(ii) Magnesia Refractories
These are prepared from fused magnesia grains. Cellulose is normally used as binder. Firing
temperatures are in the range 1900-1950°C. Care must be taken in their setting to ensure that they
do not react with the kiln material at this high temperature. Forming by hot pressing is similar as in
the case of pure alumina refractories. This is a basic type of refractory having refractoriness of the
order of 2300°C.
170 BASIC ENGINEERING CHEMISTRY
(B) Mixed Oxide Refractories
QUESTIONS
1. Match the following and write appropriate statements in each case:
Group A Group B
(1) Tricalcium silicate (a) Flash set
(2) Dicalcium silicate (b) High ultimate strength
(3) Tricalcium aluminate (c) Lowest heat of hydrogen
(4) Tetracalcium aluminaferrite (d) Retarder
(5) Gypsum (e) Lowest ultimate strength
(6) Argillaceous material (f) Chalk
(7) Setting of cement (g) Shale
(8) Calcareous material (h) Hydration and hydrolysis reactions
(9) Mortar (i) Cement + Sand + Fine aggregates
(10) Concrete (j) Cement + Sand + Coarse aggregates
(11) High alumina cement (k) Superior chemical resistance to sea water
(12) Barium and strontium cement (l) Concrete shield for atomic piles
Answers : 1b, 2c, 3a, 4c, 5d, 6g, 7h, 8f, 9i, 10j, 11k, 12l.
2. Draw a labelled diagram of a rotary kiln used for the manufacture of Portland cement by wet
process and discuss the various reactions taking place in the furnace.
3. What are the microscopic constituents (or constitutional compounds) present in Portland cement?
How do they contribute towards the properties of the cement?
4. What do you mean by setting and hardening of cement? Discuss the various reactions involved
with the help of equations.
5. “The properties of Portland cement depend upon the relative proportions of its constitutional
compounds”. Justify this statement.
6. What are the different methods of manufacturing cement? Discuss their relative merits and
demerits.
7. Write informative notes on the following:
(a) Important process parameters for the manufacture of good cement clinker
(b) Sequence of operations in the manufacture of Portland cement
(c) Reactions taking place in the rotary kiln
(d) Constitutional compounds in cement and their properties
(e) Additives for cement
(f) Important properties of cement
8. Discuss the different types of Portland cement and its derivatives.
9. Write short notes on the following:
(a) Setting and hardening of cements (b) Soundness of cements
(c) Cement additives (d) Mortar and concrete
10. Write short notes on the following :
(a) Curing (b) High alumina cement
(c) Magnesium oxychloride cement (d) Strontium and barium cements
11. Discuss the significance of the following with respect to the manufacture and properties of
Portland Cement:
(a) Lime saturation factor (b) Silica modulus
(c) Cooling of clinker (d) Heat of hydration (e) Soundness
172 BASIC ENGINEERING CHEMISTRY
12. (a) Explain the role of gypsum in setting and hardening of cement :
(b) Which type of cement will you recommend for the follwing and why :
(i) construction of a dam.
(ii) Lining of fire bricks in a blast furnace
(iii) Oil and gas wells.
(d) State the various reactions taking place in the rotary kiln during the manufacture of Portland
Cement.
13. (a) What is the percentage of composition of the constitutional compounds of portland
cement ?
(b) Explain the reactions involved in setting and hardening of cement.
(RGPV Bhopal 2001)
14. Explain briefly
(a) Hardening and setting of cement
(b) Constitutional compounds of portland cement and their role. (RGPV Bhopal 2003)
15. What are the requisites of a good refractory material ?
16. What are refractories ? How are they classified ? State some important industrial applications
of refractories.
17. Discuss the important properties of refractories which have a direct bearing on their industrial
use.
18. Write informative notes on
(a) Fire clay refractories (b) Silica refractories (c) Magnesite refractories
(d) Silicon carbide refractories (RGPV Bhopal 2009)
19. (a) Define the term “refractory”. How are refractories classified ? Give two examples of each
type.
(b) What are the causes for failure of a refractory?
20. Write short notes on the following :
(a) Pyrometric Cone Equivalent (b) Thermal spalling
(c) Graphite refractories.
21. (a) Discuss the essential characteristics of a good refractory.
(b) What type of refractories are used for each of the following and why?
(i) Bessemer converter (ii) Regenerative furnace
(iii) Blast furnace (iv) Open-hearth furnace.
22. Give an important of the preparation, properties and uses of the following:
(a) High alumina refractories (b) Dolomite refractories
(c) Fire clay refractories
23. Write informative notes on:
(a) Single oxide refractories (b) Mixed oxide refractories
(c) Non-oxide refractories.
24. (a) What are the raw materials for refractories ?
(b) What are the different steps in the manufacture of refractories ?
(c) What do you mean by super-refractories ?
25. Discuss the significance of the following properties in the evaluation of a refractory brick
(a) Refractoriness (b) Dimensional stability
(c) Spalling (d) Thermal conductivity (RGPV Bhopal 2009)
26. Discuss the various physical and chemical factors which affect the industrial uses of refractories.
27. Write briefly on the preparation, properties and uses of the following
(a) Carborundum bricks (b) Zirconia bricks (c) Chromite bricks
B– CEMENT AND REFRACTORIES 173
28. Write short notes on :
(a) Insulating refractories (b) Monolithic refractories
(c) Silica refractories
29. Fill up the blanks in the following:
(a) Refractoriness of a material is def nes as ..................
(b) Acid refractories should not be used in contact with .................. whereas basic refractories
should not be used in contact with ..................
(c) Porosity of a refractory material is given by the ratio of ..................
(d) Thermal spalling means ..................
(e) The heat capacity of a furnace depends upon the following three factors namely ..................
(f) Dimensional stability of a refractory indicates ..................
30. Def ne and classify refractories and discuss any two important properties of refractories.
(RGPV Bhopal 2001, 2006)
31. (a) Mentional different raw materials used in the manufacture of silica refractories. Discuss
its manufacture giving the various steps involved in the process. Give their important
properties and used.
(b) Explain the following properties of refractory materials :
(i) Refractoriness
(ii) Thermal conductivity
(iii) Spalling
32. (a) Def ne : (i) Refractoriness
(ii) Refractoriness under food
(iii) Porosity
(b) With the neat f ow diagram, explain the manufacture of silica bricks. State their properties
and uses.
33. (a) What are the essential constituents of a good refractory ?
(b) Give the manufacture, properties and uses of silica refractories.
34. (a) Discuss with a neat f ow diagram the various steps involved in the manufacture of chrome
magnestite refractory bricks. Describe their properties and uses.
(b) Mention different causes that lead to the failure of refractories.
35. (a) Explain the term “refractoriness” of the refractories.
(b) What are the refractories ? Give the classif cation of refractoriness with examples.
36. (a) What are the essential qualities of good refractory ?
(b) Discuss, with the help of a f ow diagram, the manufacture of chrome magnesite bricks.
What are their uses ?
(c) State the causes that lead to the failure of refractories.
36. (a) Describe the manufacture of chrome magnesite refractories. Give f ow sheet. Give any
two properties and industrial uses.
(b) Write a brief note on failure of refractories.
37. Write informative notes on the following :
(a) Types of lime and their properties
(b) Setting and hardening of lime mortors
(c) Gypsum plasters
(d) Weathering and deterioration of cement concrete.
38. Explain brief y –
(a) Silica refractories
(b) Thermal spalling and thermal conductivity (RGPV Bhopal 2003)
174 BASIC ENGINEERING CHEMISTRY
UNIT
4 Polymers
4·1 INTRODUCTION
The word “polymer” is derived from two Greek words, Poly (= many) and meros (= parts or
units). A polymer is a large molecule which is formed by repeated linking of small molecules called
“monomers”. For example, the polymer polyethylene is formed by repeated linkages of simple
ethylene molecules.
n CH=
2 CH 2 → ( −CH 2 − CH 2 − ) n
ethylene polyethylene
CH2 = CH2 →
Epoxy polymers … O R O CH 2 CH CH 2 …
Polyurethane … C NH ( CH 2 ) x NH C O ( CH 2 ) y O …
O O
… R (S) z R ' (S) z …
Polysulfides
starch, cellulose, etc.
(b) Elemento organic or hetero organic polymers:
These include :
(a) Compounds whose chains are composed of carbon atoms and hetero atoms (excepting N,
S and O).
(b) Compounds with organic chains if they contain side groups with C atoms connected
directly to the chain.
(c) Compounds whose main chains consist of carbon atoms and whose side groups contain
hetero atoms (excepting N. S, O and halogen atoms) connected directly to the C atoms in the chain.
Examples. :—Polysiloxanes Polytitoxanes
R R R R
| | | |
... — Si — O — Si — O — ... ... — Ti — O — Ti — O — ...
| | | |
R R R R
(c) Inorganic Polymers:
These are polymers containing no carbon atoms. The chains of these polymers are composed of
different atoms joined by chemical bonds, while weaker intermolecular forces act between the chains.
Examples :—
(c) Cross-linked polymer: The contain monomers molecules connected to each other by only
covalent bond. These monomers units are connected to each other by cross links.
Due to presence of cross links, they are hard, rigid, brittle and do not melt, but burn on
heating.
(iv) On the Basic of Physical State
(i) Amorphous: The polymer formed are amorphous in nature.
(ii) Crystalline: The polymer formed are crystalline in nature.
POLYMERS 177
(v) On the Basic of synthesis
(a) Addition polymer: In addition polymerization, the polymer is formed from the monomer,
without the loss of any material, and the product is an exact multiple of the original mono-
meric molecule.
e.g. n
(d) Co-ordination Polymer: Polymerization reaction taking place in the presence of organe
metallic compounds as catalyst, are known as co-ordination polymerization and the
polymer formed is know as co-ordinate polymer.
Karl Triegler in Germany developed a steriochemical process to polymerize ethylene at much
lower temperature and pressure than what were required for free-radical polymerization by
using Zeigler-Natta catalyst. The product thus formed had fewer branches and possess a
higher degree of crystallinity than that of LDPE and hence is called high density polyethylene
(HDPE). Zeigler and Natta were awarded the Nobel prize in 1963 for this work. Ziegler-
Natta catalysts are a novel type of transition metal catalysts, which exhibit a co-ordination
or insertion-type of mechanism during the polymerization. A Ziegler-Natta catalyst, in
general, comprises of a metal-organic complex of a metal cation from I to III Group of the
periodic table [e.g. triethyl aluminium, Al(C2H5)3] and a transition metal compound from
IV to VIII Group [e.g., titanium tetrachloride, TiCl4].
178 BASIC ENGINEERING CHEMISTRY
For example, HDPE can be produced by bubbling ethylene into a suspension of Al(C2H5)3 and
TiCl4, in hexane at ambient temperature. Similarly, polypropylene of about 90% isotacticity
can be prepared by polymerising propylene in presence of TiCl3 and diethylaluminium
chloride, Al (C2H5)2 Cl, at 50°C. It is postulated that the growing polymer-chain is bound
to the metal atom of the catalyst and that monomer insertion involves a coordination of the
monomer with the atom. Thus, it is this coordination of the monomer which is responsible
for steriospecificity of the polymerization. Coordination polymerisation processes can
be terminated by the introduction of hydrogen, water, metals, such as Zinc and aromatic
alcohols.
(b) Syndiotic: If the arrangement of side group is in alternating fashion (i.e. trans arrangement)
it is called an syndiotic arrangement.
(c) Atactic: If the monomers have entered the chain in a random fashion it is called an atatic
polymer.
POLYMERS 179
(v) On the Basis of Intermolecular Force of Attraction
(a) Elastomers: The polymers which are capable of being stretched rapidly atleast 150% of
their original length without breaking and return to their original shape on release of stress
are known as elastomers.
(b) Fibres: They are thin, long threadlike materials which have great tensile strength in the
direction of fibres. they posses strong intermolecular forces
(c) Thermoplastic: Thermoplastic resins soften on heating and become plastic so that it
can be converted to any shape by moulding. On cooling, they become hard and rigid. On
re-heating, they soften again and the material can be remoulded to any desired shape. Thus,
their softness and hardness are temporary phenomena which are attainable by heating
or cooling. The resins that are formed by addition polymerization are thermoplastic and
have linear long chain polymeric structure without any cross linkings. In thermoplastic
resins, the chemical structure or the molecular weight are not changed during the heating or
moulding operations. Only the secondary bonds between the individual molecular chains
are broken on heating which results in their softening and flow properties. On cooling, these
secondary bonds are re-established as a result of which they become hard again. Obviously,
thermoplastic resins are weaker, softer and less brittle as compared to thermosetting resins.
The molecular weights of thermoplastic resins are smaller than those of thermosetting
resins. Also their inter-molecular forces are weaker than in thermosetting plastics. That is
why thermoplastics swell or dissolve in some solvents.
(d) Thermosetting resins. Thermosetting resins are those which set upon heating and cannot be
reformed when once they are set. In general, those resins which are formed by condensation
are thermosetting. The thermosetting resins have three dimensional network structure and
have very high molecular weights. These resins have predominant covalent cross links
between the long chain molecules which are responsible for the three dimensional network
structure. When these materials are moulded, additional cross linkings are formed between
the long chains leading to further increase in molecular weight. When cross linkings are
formed, the thermosetting resins acquire some of their characteristic properties such as
hardness, toughness, non-swelling and non-softening properties, brittleness, etc. The strength
of these bonds are retained even on heating and hence they cannot be softened or remoulded
or reclaimed when once they are cured as can be done in the case of thermoplastic resins.
(vi) On the Basis of Polarity
(i) Ionic
(ii) Non-ionic
(vii) On the Basis of Miscellaneous
(i) Steriospecific polymerization. Steriospecific polymerization is one which results in the
production of sterioregular polymers. Sterioregular polymers are those in which all units
and substituents are arranged in space in some definite order. It may proceed by an ionic or
a radical mechanism.
A polymer lacking a regular order of its units and substituents is called sterioirregular.
These differences in spatial arrangement of units or substituents give rise to configurational
isomerism (e.g., cis-trans and D—L isomerism) of polymers.
The term coordination polymerisation is sometimes used to the processes that yield
polymers with ordered structure (steriopolymers) because the coordination complex
between the monomer and the organometallic compound regulates the polymer structure
through coordination.
180 BASIC ENGINEERING CHEMISTRY
(ii) Step polymerization. Step polymerization involves the combination of several molecules
(b) By disproportionation: In some cases one hydrogen atom from one growing chain is ab-
sorbed by the other growing chain. Due to which one saturate and one unsaturate polymer
molecules are formed.
—→
Dead polymer
(c) Thus the product so formed do not contain any reactive sites known as dead polymer,
because these cannot grow further.
In addition to the above two method of chain termination, chain transfer by hydrogen
abstraction from solvent molecule, may also terminate the growing chain.
R—[ CH2 — CH2— ]n CH2 — CH2 + SH —→ R—[ CH2 — CH2— ]n CH2 — CH2 + S
Solvent
Ionic polymerization
In ionic polymerization, the active centres initiating the chain reaction are “ions”. Ionic
polymerization proceeds due to the presence of catalysts and hence it is called catalytic polymerization.
Depending upon the charge of the ion formed, the polymerization may be cationic or anionic.
(a) Cationic polymerization: Cationic polymerization (or carbonium polymerization) takes
place with the formation of a carbonium ion, which is a polar compound with a tricovalent carbon
atom having a positive charge :
+
R — CH
|
R'
The catalysts used in carbonium polymerization (or cationic polymerization) are compounds
with pronounced electron acceptor properties e.g., AlCl3, SnCl2, TiCl4 boron fluoride etc. The
polymerizing monomer is an electron donor such as styrene in the presence of SnCl4.
A carbonium ion interacts with a monomeric molecule, and the reaction of the chain growth is
accompanied with the communication of a positive charge along the chain. Thus, the growing chain
itself is a cation and the molecular mass increases in the course of polymerization.
Cationic polymerization completed in following three steps.
(i) Initiation: This step involves the formation of a carbonium ion by the attack of a proton
on the monomer. Any strong lewis acid like BF3, AlCl3 etc can be used as a catalyst. In this
case a cocatalyst like water is required to provide the proton source.
POLYMERS 183
Here H+ act as a initiator and [F3BOH]– anion faces the growing chain end
+
CH2 = CH2 + [F3BOH] H+ —→ CH2 — CH2 [BF3OH] –
(ii) Propagation: The Propagation reaction involves the addition of monomer units. More and
more units are added up and the chain keeps on growing. The electron pair of the adding
monomer units are pulled in a direction opposite to the growth of the chain and the positive
charge keeps on moving in the direction of the chain growth. The counter ion [BF3OH]–
moves along the positive charge all the time.
+ +
–
CH2 – CH2 [BF3OH] + CH2 = CH2 —→ – CH2 – CH2 – CH2 – CH2 [F3BOH] –
(iii) Termination: In this step the growing polymer chain having C + collides with an anion,
which may be added deliberately or with the counter ion. The termination takes place–
(a) By the donation of a proton to the counter ion by the growing polymer chain
+ –
CH2 – CH2 – CH2 – CH2 [F3BOH] – —→ CH2 – CH2 – CH = CH2 + [F3BOH] — H+
(b) By the formation of covalent bond between the carbonium ion and the counterion
(coupling)
+
CH2 – CH2 – CH2 – CH2 [F3BOH] – —→ CH2 – CH2 – CH2 – CH2 – OH + BF3
In this case also the regeneration of the initiator takes place.
(b) Anionic Polymerization: Anionic or carbanion polymerization involves the formation
of a carbanion, a compound with a trivalent carbon atom carrying a negative charge. Naturally,
anionic polymerization occurs in the presence of catalysts which readily yield electrons. e.g.
electron donors such as sodium or potassium amide, triphenyl methyl sodium, alkali metals and
alkyl alkalis. Carbanion polymerization takes place in case of monomers such as acrylonitrile
and methyl methacrylate which contain electronegative substituents at one of the carbon atoms
connected by a double bond.
Anionic polymerization involves the following steps :
(i) Initiation: In anionic polymerization initiators are strong base such as organo alkali com-
pounds (alky) or aryl derivatives of alkali metals) like n-butyl lithium, ethyl, sodium, alkali
metal amides, hydroxide etc.
The electron pair in the case is pushed to the end of the molecule forming the carbanion Li+
is the counter ion.
Propagation: The carbanion formed propagates the chain growth by attacking the second
monomer unit, pushing its p electron pair further away to the end and forming a sigma bond
with the new monomer unit.
184 BASIC ENGINEERING CHEMISTRY
In the case of anionic polymerization the movement of the p electrons is towards the direction
of the chain growth.
Termination: The termination in anionic polymerization is not a spontaneous process. If the
starting reagents are pure and no impurities are present, propagation can proceed indefinitely or until
all the monomer is consumed. Thus anionic polymerization is also known as “living polymerization”,
because the carbanions at the chain ends remain potentially active. If a fresh quantity of monomer is
added, polymerization again goes on until the added monomer is consumed.
Termination is generally carried out by the transfer of negative charge to a species which is not
directly involved in the reaction. E.g. CO2, methanol,water etc.
It may be noted that like free radical polymerization, the initating specie (BU) has been in
corporated as the end group of the terminated polymer. Thus Butyl-lithium is an initiator rather than
a catalyst.
Table 4.1. Difference between Addition and Condenstion Polymer
Addition Polymer/Polymerization Condensation Polymer/Polymerization
1. In addition polymerization, the In condensation polymerization, the chain growth is
polymer is formed by the addition of accompained by elimination of small molecules, such as H2O,
monomer unit, without the loss of any SO2 etc.
material.
2 It requires the presence of double It requires two reactive functional group to be present at both
bond in the monomer. end of the monomer. There should be atleast two different
monomers having functional groups with affinity for each other.
3. No byproduct is formed Generally a byproduct is formed.
4. They are Homochain polymer, They are Heterochain polymer either thermoplastic or thermoset
generally a thermoplastic is obtained. can be obtained.
5. The growth of chain is at one active The growth of chain occurs at minimum of two active centre.
centre
6. Example: Polystrene PVC etc. Example: Nylon 6 : 6, Bakelite etc.
Properties
(i) Cellucose nitrate plastics are transparent, flexible, strong and touch.
(ii) The specific gravity is 1.35 to 1.40. Its dimensional stability is poor as it slowly shrinks due
to slow loss of plasticizer and hence is not used for precision parts.
(iii) It is inflammable.
(iv) It is resistant to water but is attacked by strong acids and alkalis.
(v) It tends to discolour with age.
(vi) It becomes brittle at low temperatures.
Uses
(i) Nitrocellulose containing 10.5 to 11.5% N is used for moulded extruded articles; that con-
taining 11.5 to 12.1% N is used in lacquers, and that with 12.1 to 13.8% N is used for ex-
plosive gun cotton.
(ii) Cellulose nitrate plastics are used for tool handles, spectacle frames, drawing instruments,
pens, toothbrush handles, table tennis balls, radio dials, picture films and many fancy article .
(iii) The first ‘‘artificial leather’’ was made by coating fabric with nitrocellulose suitably covered
and embossed, which is still used in coverings for books, luggage and upholstery.
(ii) Cellulose Acetate
It is obtained by treating cellulose with concentrated acetic acid or acetic anhydride in presence
of a catalyst such as H2SO4
n [ C6 H 7 O 2 .(OH)3 ] + 3n.CH3COOH → n [ C6 H 7 O 2 .(OCOCH3 )3 ] + 3n.H 2 O
H 2SO4
The resulting cellulose triacetate is partially hydrolysed to render it soluble in organic solvents
such as acetone.
Properties
(i) It has high dielectric strength
(ii) It has good clarity, stability, toughness, impact strength and resistance to U.V. radiation
(iii) It also has high tensile strength
(iv) It shows resistance to mineral acid
(v) It has good film and plastic strength
186 BASIC ENGINEERING CHEMISTRY
Uses
(i) It is used for preparing fibres for textiles on one hand and for preparing transparent sheets
on the other.
(ii) Thick sheets are made from blocks and polishing.
(iii) Thinner films can be cast from solution on to polished metal surfaces.
(iv) The films are also widely used in photography, for wrapping, and for making small enve-
lopes, bags and boxes for packaging.
(v) It is also used for combs, goggles, handles, radio-appliances, steering wheels, etc.
(vi) Since cellulose acetate is much less inflammable than cellulose nitrate it has replaced the
latter in the manufacture of photographic films
(iii) Cellulose acetate butyrate
It is a copolymer having lower water absorption that the cellulose acetate alone. It is prepared
by treating cellulose with a mixture of acetic acid and butyric acid in presence of H2SO4 (catalyst).
Its thermal stability and other properties are similar to that of cellulose acetate plastics but has
better chemical and moisture stability, better dimensional stability and impact strength. It is used for
toothbrush handles, combs, buttons, pens automobile hardware, etc.
O C O O C O
H H
C C C C
OH H + NaOH H H
H C C H C C
O O
H OH ONa ONa
1 1
2
Cellulose unit 2
Soda Cellulose unit
CH2OC2H5
+ C2H5Cl
O C O Pressure
H
H
C C
OC2H5 H
H C C
O
H OC2H5
Triethyl Cellulose
Fig. 4.3. Triethyl cellulose.
POLYMERS 187
Properties
(i) It is the toughest cellulose derivative among all the cellulose plastics
(ii) Soluble in many cheap solvents
(iii) It shows good chemical resistance
(iv) Stable to heat and light
(v) It shows good electrical properties
Uses
(i) In the formation of chisel handles mallet heads etc.
(ii) As electrical insulators
(iii) In the preparation of raincoats, surgical tapes, laminated glass sheet and straw etc.
4.7 POLYETHYLENE
Polyethylene or polythene is a versatile plastic made from the polymerization of ethylene
molecule.
n CH2 = CH2 —→ (—CH2 —CH2)n
Ethylene Polyethylene
Polyethylene was first produced in the laboratories of Imperial chemical Industries Ltd.
(England) in a fortuitous experiment in which ethylene was subjected to 1400 atmospheres of
pressure at 70°C. Traces of oxygen caused the polymerization to take place.
There are two variety of polyethylene
(i) High Density Polyethylene (H.D.P)
(ii) Low Density Polyethylene (L.D.P)
Properties
(i) It shows higher melting point (145-150°C), higher density (0.941 to 9.65) and higher tensile
strength
(ii) It is much stiffer than LDPE and has high hardness
(iii) Chemically resistant
(iv) It shows lower gas permeability
Uses
(i) It is used in the manufacture of toys, housewares
(ii) For wrapping material for food products
188 BASIC ENGINEERING CHEMISTRY
(iii) Due to low gas permeability it is used in the formation of domestic gas pipes.
(iv) It is used in the manufacture of overhead tanks for water storage.
(v) It is also used for manufacturing bottles for milk, household chemicals and drug packing.
(ii) Low Density Polyethylene L.D.P.E
It is prepared by polymerizing ethylene at high pressure (1000 to 3000 atm) at a temperature of
250°C in the presence of oxygen as a free radical initiator.
Properties:
(i) It is a white, waxy translucent material
(ii) It has low density (0.91 g/cm3)
(iii) Chemically inert, slightly flexible and poor electrical conducto
(iv) It shows moderate tensile strength and high toughness
(v) Moisture resistant
(vi) Its elasticity is preserved even at lower temperature
Uses
(i) It is used as films and sheet for packaging applications, including bags and wrappings,
drapes, table cloth etc.
(ii) It is also used for insulation for electric wires and cables.
(iii) In the manufacture of ‘‘squeeze bottles’’
(iv) It is used for production of industrial containers, pipes for water supply etc.
4.8 TEFLON OR POLYTETRAFLUORO ETHYLENE
Polytetrafluoro ethylene (Teflon) is prepared by polymerization of tetrafluoroethylene (CF2 =
CF2) at elevated pressures in presence of water using initiators (catalysts) such as benzoyl peroxide,
persulfates, H2O2, etc.
F F F F
| | | |
= nC C → C C
| | | |
R F F F n
Tetrafluroethylene PTFE (Teflon)
Polymerization can lead to reactions of explosive violence. Since the heat of polymerization is
high, precautions must be taken to prevent local overheating leading to explosive disproportionation
the monomer into carbon and carbon tetrafluoride
It is a highly crystalline and orientable polymer. It has many remarkable properties.
(1) It is extremely resistant to attack by corrosive reagents and solvents. Of several hundreds
of reagents tested upto their boiling points, only alkali metals either molten or dissolved in
liquid ammonia attack the polymer, probably by removing fluorine from the chain. Fluorine
itself can degrade the polymer under pressure on prolonged contact.
(2) It is totally unaffected by water.
POLYMERS 189
(3) It has an excellent thermal stability even at 250°C. Its mechanical and electrical properties
do not change for months together. It decomposes at still higher temperatures.
(4) Its melting point is so high that techniques similar to those employed in powder metallurgy
have to be used in forming sheets and moulding articles.
(5) Moulded polytetrafluoroethylene articles have high impact strength but are easily strained
beyond the point of elastic recovery.
(6) Its density is unusually high (2.1 to 2.3).
(7) Its refractive index is unusually low (1.375).
(8) It is not hard, but is slippery and waxy to the touch.
(9) It has a very low coefficient of friction
(10) It has extremely good electrical properties. Its dielectric constant is low (2.0), and its loss
factor for all frequencies tested, including radar and T.V., is one of the lowest known for
solids.
(11) Its mechanical properties including resistance to wear and deformation under load, stiffness
and compressive strength can enhanced by the use of additives or fillers such as asbestos,
glass fibre, graphite, bronze powde , zirconium oxide etc.
(12) It can be machined, punched and drilled.
Uses
Teflon is widely used because of its excellent toughness, chemical and heat resistance, electrical
properties and low frictional coefficient
(1) Its electrical applications include wire and cable insulation, insulation for motors, generators,
coils transformers and capacitors and high frequency electronic uses.
(2) Its low friction and antistick applications include its use a solid lubricant film on ammunition,
gun mechanisms and as a bearing surface for light loads.
(3) It is also used in non-lubricated bearings, linings for trays in bakeries, etc.
(4) It is used in mould release devices, package machines, etc.
(5) It does not stick to other materials and is hence called an abhesive.
(6) It is accordingly used for making non-sticking stopcocks for burettes and as a thin tape for
severing pipe threads.
(7) Low molecular-weight PTFE can be dispersed as aerosols for effective dry lubrication.
(8) It is used in chemical equipment e.g., gaskets, pumps, valve packing, and pump and valve
parts.
(9) Its use as fibre include gasketing, belting, pump and valve picking, filter cloths and for
various industrial functions where absolute chemical and thermal resistance upto 250°C is
required.
4.9 POLYSTYRENE
It is prepared by the polymerization of styrene monomer in presence of a peroxide (e.g.benzoyl
peroxide). Here peroxide act as a initiator.
190 BASIC ENGINEERING CHEMISTRY
Properties
(i) Polystyrene is a linear polymer which is relatively inert chemically.
(ii) It is quite resistant to alkalis, halide acids and oxidizing an reducing agents.
(iii) It can be nitrated by fuming HNO3 and sulfonated by con. H2SO4 at 100°C to a water-
soluble resin.
(iv) Polystyrene is transparent and its high refractive index (1.60) renders it useful for plastic
optical components.
(v) It is a good electrical insulator and has a low dielectric loss factor at moderate freequencies.
Its tensile strength reaches about 8000 psi.
(vi) On the other hand, polystyrene is readily attacked by a number of solvents including dry-
cleaning agents.
(vii) It has a poor stability for outdoor weathering.
(viii) It turns yellow and crazes on exposure.
(ix) Its two major mechanical defects are its brittleness and low heat distortion temperature
(softening temperature) which is only about 82—100°C. Hence polystyrene articles cannot
be sterilized.
Uses
(i) Polystyrene is used for injection moulding of articles such a combs, buttons, toys, buckles,
high frequency electric insulators, lenses, radio, T.V. and refrigerator parts, indoor lighting
panels, etc.
(ii) High impact strength polystyrene made by compounding polystyrene with styrene butadi-
ene synthetic rubber is used as an injection moulding material for producing all the above
mentioned articles.
4.10 POLYMETHYL METHACRYLATE
It is prepared by the polymerization of methyl methacrylate in presence of acetyl oxide.
Properties
(i) Polymethyl metacrylate is a clear, colourless transparent plastic with a higher softening
point, better weatherability and better impact strength than polystyrene.
(ii) It transmits 98% of the sunlight including the ultraviolet.
(iii) Owing to internal reflection, light entering one end of a spiral or bent rod of this plastic will
emerge from the opposite end with almost the same intensity.
(iv) Hence it is used to pipe light behind opaque objects through bundle of fibers and appropriate
lenses.
Uses
(i) It is mostly used for automotive applications such as in tail and signal light lenses, dials,
medallions, etc.
(ii) It is also used for brush backs, jewellery, lenses and small signs. Its sheets are used for signs,
glazing skylights and decorative purposes.
(iii) It is also used in aircraft light fixtures, bone splints, paints, adhesives, etc
POLYMERS 191
4.11 POLYVINYL ACETATE
Polyvinyl acetate. It is the most widely used polymer. It is used as a plastic and also for the
preparation of polyvinyl alcohol as well as polyvinyl acetals, both of which cannot be prepared by
direct polymerization.
The monomer, vinyl acetate is prepared (1) by bubbling acetylene through hot glacial acetic
acid in presence of a catalyst (such as mercuric salts plus H2SO4), or (2) by passing the mixed gases
of acetylene and acetic acid at about 200°C over a catalyst containing Zn or Cd salts on charcoal
(vapour phase synthesis).
CH ≡ CH + CH 3 COOH
→ CH 3 COOCH = CH 2
acetylene acetic Vinyl acetate
acid
Polyvinyl acetate is prepared from vinyl acetate by heating in presence of a small quantity of
benzoyl peroxide or acetyl chloride as catalyst. Emulsion or suspension polymerization is most
commonly used although bulk or solution polymerization can also be used.
Properties
(i) This polymer is atactic and hence amorphous.
(ii) Its glass transition temperature is only 28°C as a result of which the polymer although tough
and stable at room temperature (below 28°C), becomes sticky and undergoes severe cold
flow at slightly higher temperatures. Hence the articles formed from polyvinylacetate are
distorted even at room temperature under the influence of compressive and tensile forces.
(iii) Lower molecular weight polymers are brittle but become gum like when masticated, and
hence are used in chewing gums.
(iv) Polyvinyl acetate is a clear, colourless and transparent material.
(v) It has got water and heat resistance.
(vi) It is fairly soluble in organic solvents.
Uses
(i) It is used for the manufacture of polyvinyl alcohol.
(ii) Its major use is in the production of water based emulsion paints, lacquers and adhesives
(iii) It is used for making chewing gums, surgical dressings, for coating on wrapping paper and
cardboard for packing purposes, for the finishing of textile and other fabrics and for bonding
papers, textiles, leather, metals, etc.
4.12 POLYVINYL CHLORIDE (PVC)
It is one of the cheapest and most widely used plastic globally. Polyvinyl chloride (PVC) is
prepared by the polymerisation of vinyl chloride by heating its water emulsion in presence of a small
quantity of benzoyl peroxide or H2O in an autoclave under pressure.
192 BASIC ENGINEERING CHEMISTRY
It is prepared from the monomer, vinyl chloride. The vinyl chloride is a gas, boiling at —14°C
and is commercially produced by the catalytic addition of dry hydrogen chloride to acetylene. The
two gases are passed together at 100 to 250°C over charcoal catalysts containing mercuric or other
heavy metal salts. An alternative source is vapour phase cracking.
PVC is available in two grade:
(i) Rigid PVC
(ii) Plasticized PVC: For the preparation of plasticized PVC plasticizer are added .e.g. tricresly
phosphate.
Properties
(i) Commercial PVC is a hard and stiff amorphous plastic
(ii) Soluble in cyclohexanone and tetrahydrofuran
(iii) Its glass transition temperature is 81 °C.
(iv) Its shows flame resistanc
Uses
Plasticized PVC
(i) For wire coating
(ii) As electrical insulator
(iii) As tool handles, toys etc.
Rigid or unplasticized PVC
(i) For tanks, linings, display and light fitting
(ii) In safety helmets
(iii) In refrigerator components
(iv) Mudguards of cycle and motor cycle.
4.13 POLYAMIDE
Polyamides are a group of polymers which contain the amide (—CONH—) linkage in the main
polymer chain. Polymers of this type are the synthetic linear aliphatic polyamides which are capable
of fibre formatio
Nylon is a generic term for synthetic polyamides capables of forming fibres.Aminoacid polymers
are designated by a single number, as Nylon : 6 for poly (w-amino-caproic acid) or polycaprolactum.
Nylons from diamines and dibasic acids are designated by two numbers, the first representing the
diamine, and second representing acid as Nylon 6 : 6 for the polymer of hexamethylene diamine and
adipic acid and Nylon 6 : 10 for that of hexamethylene diamine and sebacic acid.
Nylon 6:6
POLYMERS 193
It is known as Nylon 6:6, because both the monomer (i.e. hexamethylene diamine and adipic
acid) contain six, six carbon atom.
Properties
(i) It has high strength, elasticity toughness and abrasion resistance.
(ii) Its solvent resistance is good, only formic acid, phenols and cresols dissolve the polymer at
room temperature. Strong acids degrade it somewhat.
(iii) It shows good mechanical properties upto 125 °C.
(iv) Its m.p. is 264 °C and specific gravity is 1.14
(v) Resistant to moisture.
(vi) Hydro carbons resistant.
Uses
(i) It is used as a plastic as well as fibres. Its most important fibre applications include automo-
bile tire cords, ropes, threads, cords having high tenacity and good elasticity.
(ii) It is also used to make textile fibres for use in dresses, unde garments, socks etc.
(iii) Being a tough plastic it is used as a substitute for metals in gears and bearing etc.
(iv) It is used in making rollers, slides and door latches.
(v) It is also used in making thread guide in textile machinery
(vi) It is used for jacketing electrical ware to provide a tough, abrasion resistant outer cover
to protect the primary electrical ware to provide a tough, abrasion resistant outer cover to
protect the primary electrical insulation.
(ii) Nylon 6
It is prepared by the self condensation of a-amino carporic acid
(iv) Ring opening polymerization of caprolactum to give amino carproic acid, which on self
polymerization formed Nylon 6
Selt
nNH 2 (CH 2 )5 COOH [ NH 2 (CH 2 )5 CO
polymerization → ]n
Nylon 6
Properties
Its properties are similar to those of nylon 6:6 but its m.p. is 225 °C and it is less stiff and
softer than Nylon 6:6.
Uses
It is mainly used for making tyre cords.
(iii) Nylon 6:10
Nylon 6:10 (Poly hexamethylene sebacamide) is prepared by the condensation between
hexamethylene diamine and sebacic acid.
Nylon 6:10 is generally not used as a fibre, but it is suitable for mono filaments, which are used
for bristles, brushes etc.
(iv) Nylon 11
Nylon 11 or poly w-aminoundecanoic acid is prepared by self condensation of w-amino
undecanaic acid
(b) Novolac
In the presence of acid catalyst when the P/F ratio is greater than one, the methylol derivative
condenses with phenol and form a liner polymer with little methylo groups. The product is
thermosetting in nature and known as novolac.
196 BASIC ENGINEERING CHEMISTRY
Resole Formation
In the presence of alkaline catalyst and when the P/F ratio is less than 1, the methylol phenols
condenses and formed a linear structure called resole. The resoles are soluble in the reaction mixture
and have excess of methylol group, which are capable of further reaction during continued heating.
Cross linking of resoles can be done by heating in either neutral or just acidic conditions. Cross
linked product from resole is called Resite.
POLYMERS 197
Properties
(i) They have excellent heat resistance
(ii) They have good dielectric property
(iii) They have good chemical resistance
(iv) They have good abrasion resistance
(v) They are hard, rigid and scratch resistant
(vi) They have remarkable adhesive properties and bonding strength
(vii) They are hard rigid and strong materials
(viii) They are resistance to cold flo
Uses
(i) Because of their good dielectric properties, they are widely used in electrical, automotive,
radio and TV parts.
(ii) Due to their excellent adhesive properties and bonding strength, they are used for producing
brake linings, abrasive wheels and sand paper, and sand filled foundry moulds
(iii) Phenolic resins are widely used in varnishes, electrical insulation and protective coating
(iv) They are also widely used in the production of ion exchange resins with a variety of func-
tional groups such as amine, sulfonic acid, hydroxyl, phosphoric acid etc.
4.15 AMINO RESINS
Amino resins or amino plasts are prepared by the reactions of formaldehyde with nitrogen
compounds such as urea, melamine and other amino compounds. Because of their attractive light
colours, these resins have great commercial importance.
Now dimethylol urea undergoes condensation polymerization and formed cross linked
polymer.
198 BASIC ENGINEERING CHEMISTRY
Thermosetting of the resin takes place during the moulding process. For moulding, the methylol
derivative are compound with fillers plasticizer, pigments etc and then are subjected to heat and
pressure. The resulting product is hard and infusible substance.
Properties
(i) They are clear and colourless.
(ii) They have better hardness and tensile strength than phenol formaldehyde resins.
(iii) They have good electrical insulating properties.
(iv) They have good adhesive property.
(v) They are resistant to oxidation to oil, grease and weak acids.
(vi) Their heat and moisture resistance are lower than those of phenolic resins.
Uses
(i) They are used for the production of light or pastel coloured object.
(ii) They are widely used for moulding articles.
(iii) They are also used to impregnate wood to prevent cracking.
(iv) They are used for the manufacture of coated abrasive paper and binder for foundry cores.
(v) They are used for the manufacture of cation exchange resins.
(vi) They are used for making buttons, vaccum flask cups and jugs, colored toilet seats etc
(vii) They are also used for the finishing of cotton textiles (for crease resistance, shrinkage con-
trol, water repellency and fire-retardation)
(viii) They are used as an adhesive for plywood and furniture.
(ix) They are widely used for making cosmetic container closures.
4.17 POLYESTERS
(i) Decron or Terylene; It is most important polyester
It is prepared by the action of terephthalic acid with ethyleneglycol.
Terephthalic acid is first react with methyl alcohol and formed dimethyl terephthalate. Now this
dimethyl terephthalate react with ethylene glycol and formed diethylene glycol terephthalate. Which
on polymerization formed ethylene terephthalate polymer, commonly known as decron or terylene.
200 BASIC ENGINEERING CHEMISTRY
Properties
(i) Its glass transition temperature is 80°C
(ii) M.P. 265°C
(iii) Chemical and solvent resistance
(iv) Its retains its good mechanical properties up to 150-175°C
(v) Crease resistance
Uses:
(i) The polyester fibres are generally blended with cotton or wool to make summer and me-
dium weight suiting and other goods.
(ii) In making magnetie tapes.
(iii) In bypass surgery, decron tubes are good substitutes for human blood vessel
(iv) In the preparation of films and for packing frozen food
4.18 SILICONES
They are the very high molecular weight polymers in which the siloxane unit –si-o-si, is the
continuing framework. Each silicon atom is attached to one or two organic groups.
They are prepared by following 3 methods.
(i) Direct Method: In this method methyl chloride is passed through a mixer of powdered
silicon and powdered copper (act as catalyst). Heating is carried out about 230-290°C
2 CH3Cl + Si ——→ (CH3)2 SiCl2
Methyl Chlorosilane
The exist gases are condensed and methyl chlorosilace can be separated by fractional
distillation.
Note: Silver catalyst is used in the preparation of phenyl chlorosilane.
(ii) Grignard Method: In the Grignard method, a solution of silicon tetrachloride in dry ether
is allowed to react with the Grignard reagent which is pumped slowly into the reactor :
2CH3MgCl + SiC4 ——→ (CH3)2 SiCl2 + 2MgCl2
Depending on the amount of Grignard reagent added, 1 to 4 organic groups may be added to
silicon. After filtering the MgCl2, the mixture of products formed is separated by fractional
distillation.
(iii) Olefin Hydrocarbon Method: In this method an olefin hydrocarbon is added to a
chlorasilane in a bomb uder pressure and at a temperature of 400 °C without a catalysl or at
a temperature of 45 °C using a peroxide catalyst.
CH2=CH2 + HSiCl3 ——→ CH3CH2SiCl3
POLYMERS 201
Properties
(i) They shows remarkable stability over wide range of temperature (from-70° to 250 °C)
(ii) They shows chemically and physiological inertness
(iii) They are good water repellent
(iv) They are resistance to the effect of weathering
All these properties of silioxanes are due to (a) their molecular size(b) the number and type
or organic groups attached to silicon (c) configuration of the molecules
Classification of silico
On the basis of their physical state and appearance at room temperature silicon are classified
into following classes.
(i) Silicone Fluid
(ii) Silicon Resins
(iii) Silicon Greases
(iv) Silicon Rubber
Silicon Resins
They contain ring structure. They have a much higher cross link density than silicon elastomer.
Resins. The preparations of silicone resins is as much an art as a science. The resins are
prepared by hydrolyzing and condensing (or polymerizing) mixtures of bifunctional or trifunctional
alkyl chlorosilanes under carefully controlled conditions. The properties of the resins can be varied
by controlling the relative amounts of bifunctional and trifunctional units, the type of organic units
attached to silicon, the polymer size or configuration, and the addition of other organic resins. It is
202 BASIC ENGINEERING CHEMISTRY
usually necessary to cure the silicone resin at a temperature somewhat higher than that at which it
is likely to be used.
The silicone resins can be broadly classified into six categories, although there is overlapping
because some can be applied in more than one way.
Coating resins. These have got distinctive properties of heat resistance, water repellency and
resistance to most of the aqueous chemicals and corrosive gases. The pure silicone (unmodified)
films are useful on hot stocks, exhausts, electric motors and turbines, stoves, boilers, steam pipes
and other places where conditions are too severe for the usual type of protective coatings. Silicone
coating resin formulations with aluminium flakes or zinc dust and with or without the addition
of organic resin can withstand temperatures of the order of 500°C and can be applied on high
temperature processing equipments.
Silicone modified alkyd resins have got the additional advantages of giving finishes with greater
flexibility and hardness, stability at elevated temperatures, better colour retention and toughness.
They are recommended for application to refrigerators, washing machines, stoves and similar
household equipments.
Laminating resins. They possess high temperature stability and good electrical properties
and can be prepared in the form of sheets or tubes. Resin laminated structures are widely used in
electrical industry in the form of insulated board, coil former, rods, tubes and slotwedges in motors
operating at high temperature. They can be used in aircraft instruments such as radomes.
Release resins. The release characteristics of the silicone fluids and compounds are incorporated
into the resins. The release resins are widely applied to bread pans, waffle irons, cooky sheets candy
pans as well as to ‘‘smoke sticks’’ used in smoking of meats.
Water repellent resins. These resins applied as dilute solution coat the pores (but do not fill
them) in masonry and concrete. They do not allow water to enter the pores because of their water
repellent character and as a result keep the masonry dry.
Electrical resins. Silicone electrical insulations possess greater heat resistance, water repellency
and resistance to combustion. They can be used with advantage where conditions are too severe for
conventional insulators. Impregnating silicone resin compositions are also used in the treatment of
capacitor insulations, transformer coils, motor windings and similar equipment demanding excellent
chemical, mechanical and dielectric stability.
Foamed resins. Silicone resins may be foamed in situ or may be foamed and then moulded
to the desired shape by the use of blowing agents. They can be advantageously used for thermal
and electrical insulation, firewall structures, buoyancy applications and high temperature vibration
dampers.
Uses:
Silicon resins are used:
(i) as electrical insulators
(ii) for coating on metal and for coating cooking pans
(iii) for lamination purpose.
4.19 ALKYD RESINS
Alkyd or Glyptal resins are synthesized from polybasic acids or anhydrides with polyhydric
alcohols (such as glycerol) by condensation polymerisation at elevated temperatures in presence of
a catalyst.
POLYMERS 203
Since the above polymer is synthesized from glycerol and phthalic anhydride, the alkyd resin
thus prepared is called “glyptal resin’’.
O
Phthalic anhydride
Properties
(i) Alkyd resins are hard (ii) Dimensionally stable
(iii) It is infusible, insoluble and resistant to chemical and corrosion
Uses
Alkyd resins are used:
(i) In paints, lacquers, varnishes, and enamels (ii) In switches and gears
(iii) As binder in asbestor (iv) In cement and automobile parts
(v) In circuit breaker insulation
4.20 ELASTOMERS
An elastomer is a linear polymer which exhibits elasticity and other rubber like properties. The
main source of natural rubber is the species of tree known as “Hevea Brasiliensis”, although it is
found in several other plants. Today, more than 95% of the rubber is obtained from the rubber tree.
‘‘Hevea Brasiliensis’’, grown on plantation mostly in Ceylon and the Malay peninsula. Small
quantities of the rubber are produced in Brazil from the uncultivated wild rubber trees and from the
‘‘guayule’’ shrub in Mexico and southwestern United States.
204 BASIC ENGINEERING CHEMISTRY
Natural rubber is a polymerized form of isoprene (2 methyl-1, 3-butadiene) :
CH 2 = C − CH = CH 2
|
CH3
The polyhydrocarbon chain consists of 2000 to 3000 monomer links. The polymerization
occurs by a biochemical reaction in which a particular type of enzyme acts as a catalytic agent.
For obtaining rubber from rubber plant a cut is made halfway through the bark, expending about
2/3rds around the tree. The liquid is collected in the containers. This liquid is known as latex. Latex
is milky collidal emulsion which contain 25 to 45% of rubber.
The flow of latex from the cut diminishes with time, necessitating the removal of another thin
layer of bark. This process, called tapping, is continued at intervals throughout the life of the tree. A
plantation grown tree continues to yield for as long as 40 years and gives latex to the extent that 3 to
6 lb of rubber can be obtained every year.
Latex is treated in two ways to obtain rubber goods : (1) the crude rubber is coagulated from
it by acids or heat, and then processed (2) the latex itself is mixed with appropriate compounding
materials and then precipitated directly from solution in the shape to be used, e.g., rubber gloves.
This is a new and important technique.
Generally, a small amount of ammonia is added as a preservative to the latex collected. The
latex is then coagulated by the addition of 5% solution of acetic acid or formic acid of 90% strength.
Ammonium or potassium alum are also used as coagulants. The coagulum is washed and dried.
Then it is subjected to any of the following processes :
1. Crepe rubber is prepared by adding a small amount of sodium bisulfite to bleach the rubber
and the coagulum is then rolled out into sheets of about 1 mm thickness and dried in air at about
50°C.
2. Smoked rubber is made by eliminating the bleaching with sodium sulfite and rolling the
coagulum into somewhat thicker sheets. These are then dried in smokehouses at about 50°C in the
smoke from burning wood or coconut shells.
4.20.1 Vulcanization
The process of vulcanization is
discovered by Charles Goodyear in 1839.
He observed that when rubber is heated
with sulfur, its tensile strength, elasticity
and resistance to swelling are increased
tremendously. This process is named
as vulcanization. The sulfur combines
chemically at the double bonds in the
rubber molecule bringing about excellent
changes in its properties e.g., resistance
to changes in temperature, increased
elasticity and tensile strength, durability
and chemical resistance.
Vulcanization brings about a
stiffening of the rubber by anchoring and Fig. 4.5. Unvulcanized and vulcanized rubber.
restricting the intermolecular movement
of the rubber springs. This is due to the chemical combination of the sulfur at the double bonds of
different rubber and providing cross linking between the chains.
POLYMERS 205
The vulcanization (or the curing as it is some times called) can be carried out in several ways :
1. The articles to be vulcanized are heated with steam under pressure.
2. The article is immersed in hot water under pressure.
3. By heating the article in air or in carbon dioxide.
4. By passing steam directly into the article such as fire hose
5. By vulcanizing the article in the mould in which it is shaped.
The temperature used in 110 to 140°C. The curing time may vary from a few minutes to 3 hours;
overcured stock decreases stretch and tensile strength whereas undercured stock is too soft with
excessive stretch but lower tensile strength. The amount of sulfur used for ordinary soft vulcanized
rubber is 1 to 5% whereas for hard rubber, it is 40 to 45% of the rubber.
Vulcanization of very thin sheets of rubber can be accomplished by either dipping the articles
in S2Cl2 or exposing them to vapours of S2Cl2. Other vulcanizing agents used include Se, Te, ZnO,
benzoyl chloride, trinitrobenzene, alkyl phenol sulfides, 2S, MgO, benzoyl peroxide etc.
Advantage of Vulcanization
(i) Due to vulcanization the tensile strength of vulcanized rubber is 10 time more as compared
to raw rubber.
(ii) Vulcanized rubber shows resistant to organic solvent like CCl, benzene etc but it swell in
them.
(iii) It has only slight tackiness.
(iv) It has excellent resilience (After the removal of deforming force, the articles made from
vulcanized rubber regains their original shape.
(v) It has useful temperature range -40 to 100°C.
(vi) It has better resistant to moisture, oxidation and abrasion.
4.20.2 Mastication
In 1824, Hancock discovered that rubber becomes a soft and gummy mass when subjected to
severe mechanical working. This process is called mastication or plasticization.
In 1824, Hancock discovered that rubber becomes a soft and gummy mass when subjected to
severe mechanical working. This process is called mastication. This process greatly facilitated the
addition of compounding agents to rubber, which is usually carried out on roll mills or in internal
mixers or Banbury mixer or plasticators which are similar to extruders. Mastication is accompanied
by a marked decrease in the molecular weight of the rubber. Oxidative degradation is an important
factor in mastication, since the decrease in viscosity and the other changes in properties do not
take place if the rubber is masticated in the absence of oxygen. After mastication is complete,
compounding ingredients are added and the rubber mix is prepared for vulcanization process.
9. When rubber is extended, heat is evolved and this is called Joule’s effect. When it is stretched
to 82%. 680 calories of heat/g are liberated.
10. When rubber is cooled to low temperatures, it becomes stiff.
11. When it is frozen it attains a fibrous structure
12. When rubber is heated with about 1% organic sulfonyl chloride or an organic sulfonic acid
at about 130°C, it is converted into a tough, thermoplastic resin which resembles Gutta-
percha.
13. Such products are known as thermoprenes.
14. Rubber reacts with chlorine giving chlorinated ruber.
15. With HCl, rubber forms rubber hydrochloride.
16. Rubber is oxidized by oxidizing agents such as HNO3, peroxybenzoic acid, peroxide and
KMnO4.
17. The oxidation reactions are catalyzed by Cu and Mn.
18. During the normal oxidation of rubber, an unstable peroxide of rubber is first formed
followed by transformation into a stable oxide.
4.20.5 Uses of Rubber
1. Rubber is used for the manufacture of gaskets used for sealing refrigerator cabinet doors,
etc.
2. Rubber is mainly used for the manufacture of tyres.
3. It is used for preparing V-belts for the power transmission and conveyor belts for conveying
several types of materials. These products are compact, non-slipping, clean and shock-
absorbing.
4. Rubber lined tanks (steel, Al, etc.) are widely used in chemical plants where protection from
corrosive chemicals is required.
5. Rubber mountings are prepared from sandwiching the rubber between two metal plates.
They reduce machine vibrations and prolong the life of the machines besides reducing
noise.
6. Rubber is used for manufacturing hoses.
7. Rubber threads and sponge rubber have good shock absorbing and thermal insulation
properties. Rubber threads are used in shock absorber cords, heat bands for goggles and
helmets, golf balls, etc.
8. Rubber is used for various related products like chlorinated rubber, oxidized rubber, rubber
hydrochloride, cyclized rubber and ebonites. All these substances have many industrial
uses.
9. Foam rubber is used in the manufacture of cushions, mattresses, paddings, etc.
10. Rubber is also used for manufacturing toys, sports items, etc.
11. Rubbers when blended with plastics give improved strength, hardness, flexibility and
chemical and thermal resistance.
4.20.6 Manufacture of rubber articles directly from latex
Manufacture of rubber goods directly from latex is a recent technique and has several advantages :
(1) There is no need of expensive machinery.
(2) Mastication of rubber is not required in this process and hence higher tensile strength can
be obtained.
208 BASIC ENGINEERING CHEMISTRY
(3) Time required for vulcanization is much less.
In this process, the compounding ingredients are first emulsified in water and then added to
the latex. Then, the finished articles are made in any of the following ways
(1) Insulated wires may be made by passing the wire through the latex compound.
(2) Cords and fabrics can be impregnated by dipping.
(3) Sponge rubbers can be prepared by forcing air into the latex compound mechanically,
followed by adding a coagulant.
(4) Rubber thread can be prepared by extruding the latex into a coagulating bath.
Several other techniques are also available and in all these cases, the forming process should
invariably be followed by vulcanization.
4.20.7 Polymers Related to Natural Rubber
1. Chlorinated rubber. Chlorinated rubber was traditionally prepared by allowing chlorine gas
to react with a solution of masticated rubber in a chlorinated solvent. The newer methods of preparing
chlorinated rubber involve the direct chlorination of the latex or passing of Cl2 over thin sheets of
rubber swollen with a solvent like CCl4.
The mechanism of chlorination involves substitution, addition as well as cyclization.
Chlorinated rubber is mainly used for preparing thermal and chemical resistant paints, varnishes
and lacquers. Films, impregnating solutions and adhesives also can be prepared from chlorinated
rubber.
2. Oxidized rubber: This is prepared by controlled oxidation of rubber by mastication in air in
presence of a catalyst. This is used for impregnating paper and cardboard and for protective coatings.
Varnishes prepared with oxidized rubber have outstanding electrical insulating properties.
3. Rubber hydrochloride: When HCl gas is passed into a solution of previously milled rubber
in benzene, rubber hydrochloride is produced, due to the addition of HCl to the double bonds of
rubber as follows :
CH 3
|
— CH 2 — C — CH 2 — CH 2 —
|
Cl
The presence of chlorine atom on the tertiary carbon has been confirmed by X-ray studies and
is also in accordance with Markownikoff’s rule.
Stretched and plasticized films of rubber hydrochloride have good mechanical properties,
including high tear resistance. Rubber hydrochloride is highly resistant to chemical attack but it is
susceptible to thermal and photochemical decomposition, stabilizers are helpful in retarding this
decomposition.
Rubber hydrochloride is extensively used for wrapping precision machines, machine parts, food
materials, etc.
4. Cyclized rubber: Cyclized rubbers are commercially prepared by treating rubber with either
H2SO4 or various sulfonic acids or sulfonyl chlorides, or chlorostannic acid. The products are non-
elastic and are primarily used as compounding ingredients in shoe soles and heels and for rubber to
metal bonding adhesives.
5. Hard rubber (ebonite): Ebonite was discovered in 1840 and the commercial production
started since about 1860.
If rubber reacts with excess of sulfur, the final product is a hard, inextensable solid, called ebonite.
It contains about 32% combined sulfur.
POLYMERS 209
Fillers are usually used in the production of ebonite to reduce the difficulties in handling the
rubber sulfur mix before vulcanization. Since reinforcement is not needed, only inert fillers and carbon
black are added. Accelerators reduce the curing time from several hours to minutes. The commonly
used ebonite dust is prepared by grinding the scrap ebonite. Ebonite stocks for vulcanization are
prepared by calendering or extrusion.
Ebonite can be machined well and is usually produced in bar, tube or stock for this purpose.
Its main uses are dependent upon its chemical inertness, corrosion resistance, thermal and electrical
insulating properties. However, it is not suitable for high temperature applications.
6. Guayule Rubber: It is obtained from Guayule shrub and is a source of natural rubber in
North America. Rubber latex from Hevea tree exists in a canal system but the rubber Guayule is
enclosed in the cells. Rubber obtained from the Guayule bush is recovered by cutting the shrub
(after removing the leaves) into small pieces and then milling them in pebble mills in presence of
water. The material is then sent to flotation tanks. The rubber floats to the top which is collected.
This rubber material contains 70% rubber hydrocarbon, 20% resin and 10% cellulose, lignin and
other insolubles.
Hevea rubber and Guayule rubber are chemically identical and both exist in the form of cis-
polymer of isoprene. However, the molecular weight of Guayule rubber is lower than that of Hevea
rubber.
Fig. 4.17. Hevea rubber and Guayule rubber (cis polymer of isoprene)
7. Gutta Percha and Balata: This is obtained from the mature leaves of the trees known as
Dichopsis gutta and palaqium gutta belonging to Sapotaceae family, which are found mostly in
Sumatra, Borneo and Malaya. The mature leaves are carefully ground in mills and treated with water
at 70°C for about half an hour and then dropped into cold water. Gutta-percha floating on the surface
is collected. Very pure Gutta percha can be recovered by solvent extraction, so that insoluble gums
and resins are separated.
Gutta-percha is tough and horny at room temperature but turns soft and tacky at about 100°C. It
is soluble in chlorinated and aromatic hydrocarbons but not in aliphatic hydrocarbons. Gutta percha is
used in the manufacture of submarine cables, golf ball covers, tissue for adhesive and surgical purposes.
Balata is obtained from wild trees in Central and South America and the processing and uses are
to Gutta percha. Both are the trans-polymers of isoprene.
Properties
It is resembles to natural rubber in processing characteristics, however, it gets readily oxidized
especially in oils and solvents. It requires less amount of sulphur for vulcanization.
Uses
It is used for lighter duty tires, hoses, molded goods. Unvulcanized sheet, are used for floaring,
rubber shoe soles and for electrical insulation.
Properties
1. Thiokols have outstanding resistance to swelling and disintegration by organic solvents.
2. Fuel oils, lubricating oils, gasoline and kerosene have no effect on Thiokols. However,
benezene and its derivatives cause some swelling.
3. Thiokol films have low permeability to gases. However, it has some limitations such as (1).
It tends to flow or lose shape under continuous pressure (2). Its tensile strength is lesser than
that of natural rubber. Recent developments of Thiokols have made up for these deficiencies
to some extent.
4. It has lower tensile strength and modulus than natural rubber. Under continuous pressure, it
tends to lose shape
5. It has offensive mercaptan like odour, which restricts it use.
Uses
(i) Fabrics coated with Thiokol are used for barrage balloons, life rafts and jackets which are
inflated by C 2.
(ii) Thiokols are also used for lining hoses for conveying gasoline and oil, in paints, for gaskets,
diaphragms and seals in contact with solvents and for printing rolls.
(iii) It is also used in the making of containers for transporting solvents and solid propellant
fuels for rockets etc.
3. Polyurethane
They are prepared by the rearrangement polymerization of di (or poly) isocyanate with di (or
poly) hydric alcohol. They contain the characteristic urethane linkages.
212 BASIC ENGINEERING CHEMISTRY
e.g. Reaction between ethylene di-isocyanate and polyalcohols (e.g. ethylene glycol) gives
polyurethane rubber.
Properties
(i) Because of their saturated character, they are highly resistant to oxidation.
(ii) They have good resistance to many organic solvents, but are attacked by concentrated and
hot acids and alkalis.
(iii) In comparison with Nylons, polyurethanes are less stable at elevated temperature.
Uses
(i) For the coating of gymnasium and dance floors
(ii) Resilient polyurethane fibres (spandex) are use for making swim suits and foundation gar-
ments.
(iii) Elastomeric polyurethanes are used for enhancing the life of tyre treads. They are also used
for making small industrial wheels and shoe soles.
(iv) Flexible formed polyurethanes are used for making car and furniture cushions. They are
also very good leather substitute and well known in market as car foams, used for making
pillow, mattresses etc.
4. Nitrile Rubbers
It is a polymers of butadiene and acrylonitrile.
Properties
(i) These rubber have low swelling and low solubility.
(ii) They are abrasion resistance even after immersion in gasoline or oils
(iii) The rubbers have good heat resistance
(iv) They are inherently less resilient than naturel rubber
(v) They are good heat resistance
POLYMERS 213
Uses
(i) Nitrile rubbers are extensively used for fuel tanks, gasoline hoses, creamery equipment etc.
(ii) In adhesive
(iii) In the form of latex, for impregnating paper, leather and textile.
5. Polyisobutylene and Butyl Rubber
Butyl rubbers are copolymers of isobutylene with a small amount of isoprene added in order to
render them vulcanizable.
It is manufactured by mixing isobutylene with 1.5 to 4.5% isoprene and methyl chloride as
solvent. The mixture is fed to stirred reactors cooled to —95°C by liquid ethylene. Catalyst solution
made by dissolving anhydrous AlCl3 in methyl chloride is added. The polymer forms at once as fi ely
divided product suspended in the reaction mixture.
Properties
(i) Under normal conditions these rubber are amorphous but crystallize on stretching.
(ii) Unstabilized polyisobutylene are degraded by light or heat.
(iii) It is resistance to heat, abrasion, ageing, chemicals and ozone.
(iv) It has good electrical insulating properties.
Uses
(i) Due to its superior impermeability to gases, butyl rubber is used as inner tubes.
(ii) It is used for wire and cable insulation.
(iii) It is also used in the production of tyres.
6. Neoprene
Neoprene is copolymers of chloroprene (2-Chloro-1, 3-butadiene).
Properties
(i) Its oil resistance is inferior to nitrile rubber but superior to natural rubber.
(ii) It have good weathering resistance and ozone resistance properties.
(iii) It possess high tensile strength.
(iv) It has excellent resistance to petroleum oils and gas oline.
Uses
(i) It is excellent rubber for tyres, but more expensive than other rubbers
(ii) It is mainly used in wire and cable coatings, industrial hoses and belts, shoe heels and solid
tyres.
(iii) Gloves and coated fabrics can be prepared from neoprene latex.
214 BASIC ENGINEERING CHEMISTRY
4.21 POLYACRYLATES
Polyacrylates are the esters of acrylic acid or its anhydride, halide, amide methyl or nitril
derivatives. Among them, esters and nitriles are commercially important.
(i) Polyacrylic Acid
It is prepared by the polymerization of acrylic acid.
Properties
It shows high viscosity in solution.
Uses
It is used as a thickener in adhesive.
(ii) Polymethyl Acrylate (PMA)
It is obtained by the polymerization of methyl acrylate.
Properties
(i) It is stable to light and moderate heat.
(ii) It has good adhesive property.
Application
It is used in making emulsion, paints, adhesive and other substances.
Properties
(i) It is amorphous, colourless, transparent thermoplastic with high optical transparency.
(ii) Due to presence of intermolecular dipole forces, it has high softening point (about
130-140° C).
(iii) It shows excellent weather ability.
(iv) Scratches resistened.
POLYMERS 215
Uses
(i) In making display signs.
(ii) It used for making dome shaped covers of solar collectors (i.e. solar heater) and optical
fibers
(iii) It is also used in the making of motor cycle windscreen.
(iv) It is used for light fittings for street lamp housing, ceiling lighting for school rooms, railway
stations, factories and offices and automobile rear lamp housing
(iv) Polyacrylonitrile or Orlan or Acrilon
It is prepared by the polymerization of acrylonitrile. Produced by vapour phase reaction
between propylene, ammonia and excess of air in presence of a fluidised catalyst (BiO3 + MoO3) or
Biophosphomolybdate on SiO2.
500°C
CH3CH = CH2 + NH3 + O2
Catalyst
→ CH2 =CH – CN + H2O + heat
Polymerization
n CH 2 = CH CH [ CH 2 CH CN]
→ n
Properties
(i) It is hard and has a high melting point
(ii) It is chemical resistant
(iii) It is also resistant to weathering
(iv) It has good mechanical properties
(v) Resistance to heat upto about 220° C
Uses
(i) In the form of latex, it is used for impregnating leather, paper and textiles.
(ii) In the production of fibers
(iii) The copolymer of acrylonitrile with butadiene (Known as nitrile rubber) has many indus-
trial uses such as in fuel tanks, gasoline hoses, adhesives etc.
216 BASIC ENGINEERING CHEMISTRY
4.22 CHART FOR THE MANUFACTURE OF SOME IMPORTANT POLYMER
5. H H H
| | |
CH3 – C = 0 + HCN ––→ CH3 – C – OH H·OH CH3 – C – OH
| |
Acetaldehyde CN COOH
cyanohydrin hydroxy acid
– HOH On heating
4.19. Flow-sheet for the manufacture of Butadiene styrene (SBR) rubber process.
226 BASIC ENGINEERING CHEMISTRY
QUESTIONS
5.1 INTRODUCTION
The variation of the colour of a system with change in concentration is the basis of colorimetry.
In colorimetry, the concentration of a substance is determined by measurement of the relative
absorption of light with respect to a known concentration of the substance. In visual colorimetry,
natural or artificial white light is generally used as a source of light, and determinations are made
with the help of a simple instrument called a calorimeter or colour comparator. If the eye is replaced
by a photoelectric cell, the instrument is called a photoelectric colorimeter. Colorimeter analysis is
specially useful for systems in which substances or their solutions are colored. When a substance
is colourless, then a suitable complexing agent is added to the solution so that a coloured complex
is obtained. The later than absorbs light in the visible region. For instance, for the estimation of
cuprous ions, complexing agent, ammonium hydroxide is used to get blue coloured solution.
5.1.1 Theoretical principles
Lambert’s Law: If a monochromatic light passes through a transparent medium, the rate of
decrease in intensity with the thickness of medium is proportional to the intensity of the incident
light. In other words, the intensity of the emitted light decreases exponentially as the thickness of the
absorbing medium increases arithmetically. The law may be expressed in the form of a differential
equation;
−d I
= K I
d1
where I is the intensity of the incident light of wavelength l, l is the thickness of the medium,
and K is proportionality factor. On integration, and equating I with I0 if l = 0, we get
−d
ln 0 = K l …(1)
dt
or It = I0.e–Kl …(2)
where It is the intensity of transmitted light, I0 is the intensity of the incident light, l is the
thickness of the absorbing medium and K is the constant for the wavelength and the absorbing
medium used. By changing from natural to common logarithms, we get
It = I0 . 10–2.303 kl = I0 . 10–Kl …(3)
where K = k / 2.3026 , which is known as the absorption coefficient
The ratio It / I0 is called transmittance, T.
log I0/It = A, the absorbance of the medium or optical density, D or the extinction, E.
229
230 BASIC ENGINEERING CHEMISTRY
Beer’s Law: If a monochromatic light passes through a transparent medium, the rate of decrease
in intensity is directly proportional to the concentration of the media or the intensity of a beam
of monochromatic light decreases exponentially as the concentration of the absorbing substance
increases arithmetically. This may be expressed in the form
It = I0 . e–K'c
= I0 . 10–2.303K'c
= I0 . 10–k'c …(4)
where c is the concentration, and K' and k' are constants.
Combining equations 3 and 4, we get
It = I0 . 10–a c l …(5)
or logI0/I = a c l …(6)
This expression is known as Beer-Lambert’s Law, which is the fundamental equation for
colorimetry and sprectrophotometry.
If c is expressed in mole L–1 and l in cm, ‘a’ is given a symbol ‘e’, which is known as the molar
absorption coefficient or molar absorptivit .
Since I0/It is called absorbance, A, we arrive at the following inter-relationship:
A = e c l = log I0 /It = log l / T = –log T
If l is constant (as in the case of matched cells used in a colorimeter or spectrophotometer), the
Beer-Lambert’s may be written as
c ∝ log I0 / It
c ∝ log l / T
or c ∝ A
Hence, by plotting A or log l/T as ordinate, against concentration as abscissa, straight line will
be obtained and this will pass through a point (c = 0, A = 0 i.e., T = 100%). This calibration line can
be used for determining unknown concentrations of the same material by measuring their respective
absorbances, and obtaining their corresponding concentrations from the calibration line.
Deviations from or exceptions to the Beer-Lambert’s Law
The law does not hold when coloured solute ionises, associates, dissociates, or undergoes
complexation, because the nature of the coloured species will vary with concentration.
Additivity of absorbances
According to Beer’s law, the absorbance at any particular wavelength is directly proportional to
the number of absorbing molecules. If a solution contains more than one type of absorbing species,
the total absorbance will be the sum of the absorbances of all the species, provided they do not
interact chemically.
5.1.2. Instrumentation
1. Radiation Source: Tungsten filament lamp is most widely used for producing visible light
in the wavelength range 400–750 nm. If colorimetric analysis is carried out in the UV range, (i.e.,
down to 200 nm) hydrogen discharge lamp or deuterium is used as radiation source, whereas for
work in IR region, Nernst Glower is used.
2. Dispersing Device: The selection of a narrow band of wavelength, which is required
for colorimetry and spectrophotometry, is accomplished with the help of a monochromator.
Monochromators used in various spectral regions are:
(a) filters b) prisms, and (c) gratings
A– INSTRUMENTAL TECHNIQUES IN CHEMICAL ANALYSIS 231
Plates of coloured glass can be used as filters in the visible region. From the stability point of
view, gelatin filters are better. i.e., Glass prisms are used for work in the visual range, quartz prisms
are used for UV and alkali halide prisms are generally used for IR range.
Gratings are of two types: (a) Transmission gratings (b) Reflection gratings. A transmission
grating comprises of a series of closely spaced parallel grooves ruled on a piece of glass or other
transparent material. The greater the number of lines per square inch, shorter will be the wavelength
dispersed by the grating and greater will be the dispersing power. A grating suitable for visible and
UV work should have 15,000–30,000 lines per square inch.
3. Slits: A slit system is used for selecting the desired wavelengths from the light dispersed by
a monochromator. An entrance slit and an exit slit are placed each side of the prism or grating. The
slit jaws are made of metal in the shape of knife-edges, and they can be moved with respect to each
other to control the width. The entrance slit chooses a small parallel beam of incident light, while
preventing stray radiations entering the optical path. The light, after being dispersed (by the prism or
grating) goes through the exit slit and travels through the sample or reference cell and finally reaches
the detector system.
4. Sample holders: To hold the sample solution to be analysed and the reference solution,
optically matched colour corrected fused glass cells are used in the wavelength range 300–2500 nm.
Corex glass or quartz cells are used in the wavelength range 210–300 nm, and fused silica cells are
used for measurements at somewhat lower wavelengths.
5. Detector: Generally we use following type of detectors.
(i) Photovoltaic or barrier layer cells
(ii) Photoemissive cells or phototube
(iii) Photo multiplier tube
(iv) Silicon diode or photodiode
5.1.3 Colorimetric method
The fundamental principal for colorimetric analysis is to compare, under well designed
conditions, the colour produced by the substance in unknown amount with the same colour produced
by a known amount of material being determined. The following methods are available for the
quantitative comparison of colours of known and unknown solutions:
(i) Methods using visual comparators
(a) Standard series method: In this method, Nessler tubes are used, which are colourless glass
tubes of uniform cross section and flat bottoms. The solution of the substance being determined is
made up to a known volume, and the colour is compared with that of a series of standards in the
same way starting from known amounts of the substance being determined. 100 ml of the solutions
of the unknown and each of the standard solutions are placed in Nessler tubes, and the solutions
are viewed vertically through the length of the liquid columns. The concentration of the unknown
solution is equal to that of the standard solution having the same colour. LOVIBOND–2000
comparator works on this principle.
(b) Duplication method: In this method, a known volume (say x ml) of the test solution is
treated in Nessler cylinder with a measured volume (say y ml) of appropriate reagent so as to develop
a colour. Now, x ml of distilled water is placed in a second Nessler cylinder together with y ml of
the reagent. A concentrated standard solution of the substance under test is now added to the second
Nessler cylinder from a micro burette until the colour thus developed exactly matches the colour in
the first Nessler cylinder already developed with unknown solution
(c) Dilution method: In this method, a colour developed from the sample and standard solution
are taken in two identical glass tubes of same diameter and are observed horizontally through the
232 BASIC ENGINEERING CHEMISTRY
tubes. The more concentrated solution is diluted until the colours in the tubes are of identical intensity
when observed horizontally through the same thickness of solutions. The relative concentrations of
the two original solutions (known and unknown) are then proportional to the heights of the matched
solutions in the tubes.
(d) Balancing method: In this method, comparison is made in two tubes, and the height of
the liquid in one tube is so adjusted that when both the tubes are observed vertically, the colour
intensities in the tubes are equal. If the concentration of solution in one of the tubes is known then
the concentration in the other can be calculated from the relation
c1 l1 = c2 l2
where c1 and c2 are the known and unknown concentrations and l1 and l2 are their respective
lengths of the two liquid columns.
Hence, c2 = c1 l1 / l2
Duboscq colorimeter works on this principle.
(e) Photoelectric photometer method: In this method, the human eye is replaced by a
photoelectric cell. Instruments which incorporate photoelectric cells measure the light absorption
and not the colour of the substance, hence the term ‘photoelectric colorimeters’ is a misnomer.
They may be better called as photoelectric photometers or photoelectric comparators or
absorptiometers.
These instruments essentially Source
consist of a light source, a suitable light
filter to provide nearly monochromatic
light, a glass cell for the sample/
standard solution, a photoelectric cell Collimating lens
to receive the radiation transmitted
by the solution, and a measuring
device to determine the response of
the photoelectric cell. The various
types of each of these components Filter
A
F
M
E D C G H
Fig. 5.2. Essential features of a single-beam spectrophotometer.
A - Light source, B - dondensing mirror, C - diagonal mirror, D - entrance slit,
F - quartz prism, G - absorption cell, H - photocell, M - meter
An image of the light source, A is focussed by the condensing mirror, B and the diagonal mirror,
C on the entrance slit, D. The light beam falls on the collimating mirror, E where it is rendered
parallel and reflected to the quartz prism, F. The back surface of the prism is aluminised, so that
the light refracted at the first surface is reflected back through the prism. This light beam undergoes
further refraction as it emerges from the prism. The collimating mirror focuses the spectrum in the
plane of the slit system, D. The light of the wavelength for which the prism is set then passes out of
the monochromator through the exit slit, through the absorption cell, G and finally to the photocell,
H. The response of the photocell is amplified and registered on the meter. In modern versions of the
instrument, the prism is replaced by a diffraction grating.
Double beam spectrometers are the most modern general purpose UV-visible instruments
covering the spectral region from 200-800 mm by a continuous automatic scanning process and
producing the absorption spectrum as a pen trace on calibrated chart paper.
Salient features of colorimetric analysis:
(a) It gives accurate results at low concentrations.
(b) It enables the analysis of such substances for which gravimetric and titrimetric procedures
are not available (e.g. In case of some biological substances).
(c) It is ideal for quick and routine analysis of components of a number of similar samples.
When once the calibration curve is plotted, a large number of samples of the same compo-
nent in different concentrations can be rapidly analysed.
234 BASIC ENGINEERING CHEMISTRY
Criteria of a satisfactory colorimetric analysis:
(a) The colour reaction should be specific or atleast selective for the particular substance being
analysed under the chosen experimental conditions.
(b) Beer’s law should be obeyed in the desired concentration range. In other words, the colour
should be proportional to concentration.
(c) The colour should be sufficiently stable to enable accurate analysis
(d) The colorimetric procedure should give reproducible results under the specific experimental
conditions.
(e) The colour reaction should be highly sensitive and the reaction product should strongly
absorb in the visible region.
(f) The coloured solution should be clear and free from turbidity.
5.2. SPECTROSCOPY
Spectroscopy deals with the transitions that a molecule undergoes between its energy levels
upon absorption of suitable radiation determined by quantum mechanical selection rules.
Spectrophotometer is an instrument used for absorption measurements. It can be made to
operate in the ultraviolet, visible and infrared regions, using suitable source of radiant energy.
5.2.1. Ultraviolet spectroscopy
It involves the transition of electrons within a molecule or ion from a lower electronic energy
level to a higher electronic energy level by the absorption or emission of radiations falling in the
UV-visible range of electromagnetic spectrum i.e., When a molecule absorbs U.V. radiation of
frequency V sec–1, the electron in that molecule undergoes transition from a lower to a higher energy
level. The difference in energy in given by
E = hv erg
The actual amount of energy required depends on the difference in energy between the ground
state (E0) and the excited state (E1) of the electrons.
E1 – E0 = hv
The total energy of a molecule is the sum of electronic energy (Eelec), vibrational energy (Evib)
and rotational energy (Erot), Also
Eelc > Evib > Erot
When UV energy is quantised, the absorption spectrum arising from a single electronic
transition is expected to consist of a single discrete line. But this does not happen because electronic
absorption is superimposed upon vibrational and rotational subenergy levels.
Due to which formation of bands in the electronic spectra of simple molecules in the gaseous
phase take place.
Classification of electronic transitio
Electronic transition in molecules can be broadly classified into
(i) s-s* transition. Such transitions occur in case of saturated hydrocarbons, which do not
contain lone pairs of electrons. The energy required for this type of transitions is very large and the
absorption band occurs in the far ultraviolet region (126 to 135 nm). For example, methane has λmax
at 121.9 nm and ethane at 135 nm correspond to this transition. These transitions cannot be observed
in commercial spectrophotometers which generally do not operate at wavelengths below 180 nm.
(ii) p-p* transition. These type of transitions are related to the promotion of an electron from
a bonding p orbital to an antibonding p* orbital.
A– INSTRUMENTAL TECHNIQUES IN CHEMICAL ANALYSIS 235
(iii) n-s* transition. The energy required for n → σ*
transition is generally less than that
required for σ → σ* transition and their corresponding absorption bands appear at longer wavelengths
in the near untraviolet region (180 to 200 nm). Saturated compounds with lone pair (non-bonding)
electrons undergo n → π* transitions apart from σ − σ* transitions.
(iv) n-π* transition. These transitions are shown by unsaturated molecules which contain atoms
like N, O and S. These transtions show a weak band in their absorption spectrum. In aldehydes and
ketones (having no C º C or C = C bonds), the band due to n → π* transition generally occurs in the
range 270-300 nm. On the other hand, carbonyl compounds having double bonds separated by 2 or
more single bonds exhibit the bands in the range 300 to 350 nm due to n → π* transitions.
Instrumentation for UV spectroscopy
The following are the important component of a UV spectrometer.
(i) Source of radiation: The following are the most common radiation sources used in UV
spectrometers:
(a) Hydrogen discharge lamps (b) Deuterium lamps (c) Xenon discharge lamps (d) Mercury arcs.
(ii) Monochromators: Monochromators are used to disperse the radiation according to the
wavelength. The essential components of a monochromator are an entrance slit, a dispersing
element (eg., a prism or a grating) and an exit slit. The prisms are generally of quartz or fused silica.
The dispersing element disperses the heterochromatic radiation into its component wavelengths,
whereas the exit slit allows the nominal wavelength to pass through.
(iii) Detectors: The following three type of detectors are commonly used
(a) Photovoltaic or Barrier-layer cell
(b) Photocell or photoemissive cell
(c) Photomultiplier cell
(iv) Recorders: The signal from the detector is received by the recording system provided with
a recorder pen.
(v) Sample and reference cells: Matched pair of cells made of quartz or fused silica are used.
Single-beam and double-beam UV-spectrophotometers are available commercially.
Working of double-beam UV-Spectrophotometer
The lay-out of a double-beam UV spectrophotometer is shown in Fig. 5.3.
Attenuators
Sample
Prism
Photomultiplier
M1
Reference
Rotating
Lamp sector
Source Monochromator Beam spliter Sample chamber Detector
m1 × m 2 A r1 × A r2
µ= = kg
( m1+ m2 ) ( A r1 + A r2 ) × L × 1000
Where m1 and m2 are masses of the individual atoms, and Ar1 and Ar2 are the relative atomic
masses, L is Avogadro’s constant.
The absorption bands are usually quoted in units of wave numbers ( n ) which are expressed in
reciprocal centimeters, cm–1. In some cases, wavelengths (l) measured in micrometers (nm) are also
used. The inter-relationship between these units is given by.
1 V
n= =
l C
1
× ( f / µ ) cm −1
1/ 2
Therefore, = n
2pC
Usually, reasonably good agreement is found between calculated and experimental values for
wave numbers.
However, this simple calculation has not taken into consideration any possible effects arising
from other atoms in the molecule. More sophisticated methods of calculation have been developed
to take these interactions into account.
Vibrational Spectra of Polyatomic molecules
A diatomic molecule has only one vibrational mode and hence it yields a rather simple system.
But for a polyatomic molecule, several vibrational modes are possible and, therefore, it gives a
complicated IR spectrum. The vibration of atoms in a polyatmoic molecule may be visualised from
a mechanical model of the system. The atoms in a molecule can be seen as resembling a system of
balls by varying masses and arranged in accordance with actual space geometry of the molecule.
These balls are connected with the mechanical springs whose forces are proportional to the bending
forces of the chemical bonds. These forces keep the balls in position of balance. From such a model,
it can be visualised that a molecule has two types of fundamental vibrations; (i) in one type of
vibrations, the distance between two atoms increases or decreases but the atoms remain in the same
bond axis. This is known as stretching vibration. When the stretching and compressing occurs
in a symmetric fashion, it is called symmetric stretching. On the other hand, when one bond is
compressing while the other is stretching, then it is called asymmetric stretching (ii) The other type
of vibration is known as bending or deformation in which the position of the atom changes relative
to the original bond axis. This bending involves oscillation of the atoms perpendicular to its bond
axis. Four types of deformations may be distinguished:
(a) Scissoring: When the two atoms joined to a central atom deformation produced is known as
scissoring.
(b) Rocking: When the two atoms joining a central atom move back and forth in the plane of
the molecule, the resulting deformation is called rocking.
(c) Wagging: In this type of deformation, the structural unit moves back and forth, out of the
plane of the molecule.
(d) Twisting: In this type of deformation, the structural unit rotates about the bond which joins
the rest of the molecule.
Types of Vibration
(a) symmetric (b) asymmetric (a) scissoring (b) rocking (c) wagging (d) twisting
A– INSTRUMENTAL TECHNIQUES IN CHEMICAL ANALYSIS 239
Table 5.1 Approximate Group Positions of Some Infrared Absorption Bands
Detector
Exit slit
Source
Sample Entrance
Chopper slit
In this system, the radiation emitted from the source passes through the sample entrance slit,
collimating mirror and then through a fixed prism and a littrow mirror. The prism and the littrow
mirror select the desired wavelength and allows it to pass on to the detector, with the help of the
collimating mirror. The detector measures the intensity of radiation. On comparing this with the
original intensity of radiation, one can measure the fraction of radiation that has been absorbed
by the sample. The absorption spectrum can be obtained by measuring the degree of absorption of
radiation at different wavelengths in the desired range.
The single beam instruments have the following disadvantages.
(i) The intensity of the emission of radiation source may change with wavelength from time
to time during the analysis, which results in sloping of the base-line and deformation of the spectra
(ii) When the sample is analysed in solution, the bands of the solvent appear in the spectrum.
This may lead to problems in interpreting the bands.
These difficulties can be overcome by double beam spectrophotometers
Double beam spectrophotometers
These are constructed in such a way that the radiation emitted by the source is split into two
identical beams having equal intensity, one of the beams passes through the sample, whereas the
other passes through the reference (air or pure solvent) for compensation. The two half beams
are recombined on to a common axis, and are alternately focussed on to the entrance slit of the
monochromator.
When there is no sample in the sample cell, the half-beam travelling along the sample cell is
equal to that travelling through the reference cell, when these two identical half beams recombine,
a steady signal reaches the detector.
However, when the sample is present in the sample cell, the half-beam travelling through it
becomes less intense (depending on the nature of the sample). When the two half beams (one coming
from the reference and the other from the sample) recombine, an oscillating signal is produced,
which is measured by the detector. The signal from the detector then passes through a servomotor
to the recorder.
Applications of Infrared spectrophotometry
The important applications of infrared spectrophotometry are:
(i) It is used for the identification of an unknown compound. This is generally done by
finger print technique which involves matching the spectrum (IR) of unknown compound with that
of known compound.
242 BASIC ENGINEERING CHEMISTRY
(ii) Identification of functional groups in organic molecules: The different functional groups
in organic compounds will absorb at characteristic frequencies in the IR spectrum. Thus, from the
IR spectrum of a compound, the presence and absence of certain functional groups in the compound
is know.
(iii) Elucidation of structure: Structure elucidation is possible by IR spectroscopy because
it gives valuable information regarding molecular symmetry, dipole moments, bond lengths, bond
strength etc.
(iv) Identification of an unknown compound: It is done by finger print technique which
involves matching the spectrum (IR) of unknown compound with that of a unknown compound with
that of a known compound.
(v) To distinguish between intra and inter molecular hydrogen bonding: It is based on the
fact that as the concentration is increased, the absorption band, due to intermolecular hydrogen
bonding increase, while that due to intra-molecular Hydrogen bonding remains unchanged.
(vi) IR spectroscopy is used in conformational studies of some compounds by studying the
C-X stretching frequency present in equitorial and axial positions. It is also used in determining
conformational equilibrium constant, k which is given by
k = Ce / Ca
Where Ce and Ca are the integrated intensities of the C – X stretching peaks in the equitorial
and axial positions.
(vii) IR spectroscopy can be used for studying the progress, of a chemical reaction. For instance
during the oxidation of a secondary alcohol to a ketone, by examining the IR spectrum of aliquots
withdrawn from the reaction mixture from time to time. As the reaction proceeds the O-H stretching
band (at 3570 cm–1 ) of secondary alcohol slowly disappears and the C = O stretching band (at 1725
cm–1) due to the formation of ketone appears.
(viii) IR spectroscopy is useful to study the progress of chromatographic separations.
(ix) Determination of aromaticity: The difference in the wavelengths of overtones of C–H
bands in different environments can be used to determine the relative proportions of unsaturated and
saturated rings present in hydrocarbons and also to determine the percentage of aromatics or olefines
present in the mixture.
(x) In determining the shape or symmetry of a molecule such as NO2, which shows 3 peaks as
per (3n-6) formula whereby it is confirmed that it is not a linear molecule
(xi) In calculation of force constants of molecules. The force constant is a measure of the force
(in dynes/cm) required to deform a bond.
(xii) In studying tautomeric equilibria such as Keto-enol, lactum-lactum and mercaptothioamide
tautomerism by examining the characteristic frequencies of groups such as C = O; O–H, H–H or
C = S in the respective IR spectra.
(xiii) Industrial Applications: (a) IR spectroscopy is used to determine bulk structure and
incidental structure of industrial polymers. Bulk structure results from the normal polymerisation
of the monomers, whereas the incidental structures arise from impurities in the monomers, side
reactions, etc. IR studies helped in assigning bulk structure of ploymers such as butadiene polymers
and incidental structures of polythylene, etc.
(b) The degree of crystallinity of nylon-66 has been studied by IR spectra. Absorption band
at 934 cm–1 is a measure of crystallinity while the band at 1238 cm–1 is used as a measure of the
amorphous content.
(c) IR spectroscopy has been used to determine molecular weight of polymers by measuring
end group concentrations.
A– INSTRUMENTAL TECHNIQUES IN CHEMICAL ANALYSIS 243
5.3 NUCLEAR MAGNETIC RESONANCE (NMR) SPECTROSCOPY
It is a branch of spectroscopy in which radio frequency waves induce transitions between
magnetic energy levels of nuclei of a molecule, which are created by keeping the nuclei in a
magnetic field
For a nucleus to be magnetic, it must possess spin angular moment, whose magnitude is
(h / 2p) I ( I + 1), where I is the spin quantum number of the particular nucleus and “h” is planck’s
constant. Nuclei with I = 0 are non-magnetic and hence is not important from NMR point of view.
Nuclei with I = 1/2 give the best resolved NMR spectra. Important examples are 1H, 13C, 19F, and
31P nuclei. Nuclei with I > ½, which are of interest from NMR point of view, include 2H (I = 1),
14N(I = 1) and 11B (I = 3/2). The magnetic axis of the nucleus can assume (2I + 1) orientations with
respect to the external magnetic field. Each orientation corresponds to a discrete energy level, given
by the following relationship:
mµ
=E × βH o
I
Where E is the energy of transition, m is the magnetic number, µ is the magnetic moment
of nucleus expressed in nuclear magnetons, I is the spin quantum number, and Ho is the external
magnetic field strength in gauss. The spectrum of allowed values, in terms of spin quantum number,
is I, (I – 1),…., - (I – 1), –I. Each value corresponds to a discrete orientation (or energy level).
Therefore, a nucleus with spin 1 has three
orientations, and so on.
When a nucleus is placed in a system
where it absorbs energy, it gets excited. It then
loses energy and reverts to the unexcited state.
It absorbs energy again and enters the excited
state. Such a nucleus, which becomes excited
and unexcited alternately, is said to be in a state
of resonance. For determining the resonance
frequency, the energy absorbed by the nuclei is
measured while the magnetic field is varied. As
the magnetic field is increased, the processional
frequency of the nucleus increases. When this
frequency becomes equal to the frequency of
the oscillation field, transitions occur between
the nuclear energy states. The energy absorbed
in this process produces a signal at the detector,
which after amplification is recorded as a band
in the spectrum.
An NMR spectrum is then plotted between
absorption signal at the detector and the strength Fig. 5.5. Schematic diagram of NMR spectrometer.
of the magnetic field
Instrumentation
Two types of NMR spectrometers are in use :
(1) Wide line NMR spectrometers.
(2) High resolution NMR spectrometers.
The essential components of an NMR spectrometer are:
244 BASIC ENGINEERING CHEMISTRY
(a) A strong magnet to provide the principal part of the magnetic field, Ho
(b) A sweep circuit consisting of a set of Helmholtz coils superimposing the main magnetic
field, to provide the additional field required to bring the total field to the resonance condi-
tion.
(c) A transmitter to supply the desired radio frequency (r.f.) energy.
(d) A detector amplifier circuit to pick up and amplify the resonance signal
(e) A probe which serves to hold the sample between the pole pieces.
(f) A device to receive and record the signal.
For recording NMR spectra, the sample is placed between the poles of the strong magnet. The
sample is then irradiated with radiowaves. At certain value of the magnetic field, absorption of r.f.
energy occurs. A sensitive detector monitors the absorption energy which is recorded as a peak on
the graph. The spectra can be plotted at low resolution or high resolution as desired. The peak areas
are measured automatically by the modern NMR spectrometers.
NMR spectra can be described in terms of chemical shifts and coupling constants.
Chemical shifts: Chemical shift is an important feature of high resolution NMR spectra. In
different chemical environments, the same type of nucleus will be shielded slightly from the applied
field surrounding electrons. For a fixed external field, Ho, different screening factors cause slightly
different frequencies.
The magnitude of the effective field experienced by each group of nuclei can be expressed a
Heff = Ho (1 – s)
Where s is a non-dimensional shielding constant, which may be a positive or negative number.
The value of the shielding constant depends on factors such as hybridization and electronegativity
of the groups attached to the atom containing the nucleus. Thus, the shielding constant for protons
in a methyl group is larger than that for protons in methylene, and it is zero for an isolated hydrogen
molecule. For ethanol, the field applied must be always greater than the field for the resonance of
an isolated protein, in order that the various protons may resonate. Since the value of shielding
constant for protons in different functional groups is different, the required applied field would also
be different for different groups. Thus, least shielded (i.e., low shield constant) proton of hydroxyl
group resonates at the lowest field and of methyl group at the highest field. The areas under the peaks
are in direct ratio to the numbers of protons, e.g., 1:2:3 on hydroxyl, methylene and methyl groups.
Experimental Calibration: Since commercial NMR spectrometers employ different field
strengths, it is desirable to express the position of resonance, in field independent units and with
respect to the resonance of a reference compound.
For proton spectra in non aqueous media, tetramethyl silica, (CH3)4 Si (abbreviated at TMS) is
used as reference material. Its position is assigned as 0.0 on the δ scale. TMS contains 12 protons
but these are all chemically equivalent and hence give rise to a sharp signal. The magnitude of the
chemical shift is expressed in ppm as follows:
Hsample − H TMS
δ= ppm
v1
Where Hsample and HTMS are the positions of the absorption lines for the sample and reference
respectively, expressed in frequency units (hertz) and ν is the operating frequency of the spectrometer.
A positive δ value represents a greater degree of shielding in the sample than in the frequency.
Chemical shifts are also expressed tau (τ ) units, with t = 10 – δ.
Values for the chemical shifts (δ) of protons (hydrogen atoms) in some chemical groups are
given in Table 5.2 given below.
A– INSTRUMENTAL TECHNIQUES IN CHEMICAL ANALYSIS 245
Table 5.2. Chemical shifts for protons in ppm relative to TMS = 0
5.3. CHROMATOGRAPHY
Chromatography is a techniques used for the separation of a mixture of solutes brought about
by the dynamic partition or distribution of dissolved or dispersed materials between two immiscible
phases, one of which is moving past the other.
Chromatographic processes may be conveniently classified broadly as follows
(i) Partition chromatography; (ii) Adsorption chromatography.
Chromatographic process may also be classified under Liquid chromatography and Gas
chromatography.
246 BASIC ENGINEERING CHEMISTRY
5.3.1 Gas Chromatography (G.C.)
This is a process by which a mixture is separated into its constituents by a moving gaseous
phase passing over a stationary sorbent. Gas chromatography may be of the following two types :
(i) Gas Liquid Chromatography (GLC), in which the separation takes place by partitioning
a sample between a mobile gas phase and a thin layer of a non-volatile liquid coated on an inert
support. This is more important technique than GSC.
(ii) Gas Solid Chromatograophy (GSC), in which a suitable solid material with a large surface
area such as granular silica, alumina or carbon is used as a stationary phase, while employing a
mobile gas phase.
Gas chromatography technique was originally developed in 1941 by A.J.P. Martin and R.L.M.
Synge for which they were awarded Nobel prize in 1952. Today this technique is the most important
and extensively used analytical tool for the determination of number of components in a mixture,
the presence of impurities in a substance, and identification of a compound. This technique is also
becoming important for process control in chemical industries and refineries
Although gas chromatography is limited to volatile materials, the applicability of this technique
has been further extended because of
(i) availability of column temperatures upto 450°C
(ii) availability of pyrolytic techniques, and
(iii) the possibility of converting non-volatile materials into volatile derivatives.
Theoretical Principles
Gas chromatography process is controlled by three physical transport phenomena namely,
flo , diffusion and more importantly, the partition of the solutes between the stationary phase and
the mobile phase. As the solute is introduced into the column, the molecules are distributed (or
partitioned) between the stationary phase and the mobile phase (the carrier gas) and a dynamic
equilibrium is soon established. The process of distribution of the solutes between the two phases
continues further as the fresh mobile phase (carrier gas) passes over the column, thereby establishing
a fresh dynamic equilibrium.
The process goes on and on until a final equilibrium is established and at this stage, the
concentration of molecules of each solute in the two phases is constant.
Partition ratio,
Concentration of solute molecules in the stationary phase K = Concentration of the solute
molecules in the mobile phase
Partition ratio depends upon
(a) the nature of the solute
(b) the nature of the solvent (i.e., the stationary liquid phase)
(c) the concentration of the liquid phase, and
(d) temperature.
The solute components of the sample mixture travel down the column at their own rate depending
upon their respective partition ratios and the extent of their band spreading, thereby allowing a clear
and clean separation of the components and their subsequent detection and determination.
Sequence of Gas Chromatographic process steps: A sample mixture containing different
solutes is injected into a heating block where it is immediately vaporized and swept by the mobile
phase (carrier gas) stream into the column inlet. The solutes are absorbed at the head of the column
by the stationary phase and then desorbed by fresh carrier gas. This sorption-desorption process
occurs repeatedly as the sample is moved by the carrier gas down towards the column outlet. Each
A– INSTRUMENTAL TECHNIQUES IN CHEMICAL ANALYSIS 247
solute band will travel at its own rate through the column. Their bands will separate to a degree
that is determined by partition ratios of the individual solutes present in the sample, and the extent
of their band spreading. The solutes are then eluted sequentially in the increasing order of their
partition ratios and enter a detector attached to the column exit. If a recorder is used, the signals
appear on the chart as a plot of time versus the composition of the carrier gas stream. The time
of emergence of a peak is characteristic of each component. The peak area is proportional to the
concentration of the component in the sample mixture.
Equipment: A schematic representation of a typical laboratory gas chromatographic apparatus
is shown in Fig. 5.6.
Pressure
control Flow regulator
Flow meter
Drying tube
Detector
Pure Sample Sample
carrier gas injection collector
(H2, He, N2
Ar, CO, etc.)
Bridge
Amplifier
Cylinder containing
carrier gas Thermostated Recorder
column
QUESTIONS
PART–B
UNIT
5.4 ALKALINITY
Alkalinity. By alkalinity of water we mean the total content of those substances in water that
cause an increased concentration of OH– ions upon dissociation or due to hydrolysis. The alkalinity
of natural waters is generally due to the presence in them of HCO3–, SiO32 –, HSiO3 – , and sometimes
CO32 – ions and also due to the presence of salts of some weak organic acids, known as humates, that
bind H+ ions as a result of hydrolysis, thereby increasing the concentration of OH– ions. In addition
to the above, the alkalinity of boiler water is also conditioned by the presence of PO43– and OH–
ions. Also, the presence of salts of weak acids such as silicates and borates induces buffer capacity
in water and resists the lowering of pH. Surface waters containing algae and also water treated by
lime-soda process may contain considerable quantities of alkalinity due to CO32 – and OH–.
Depending on the anion that is present in water (HCO3 –, CO32 – or OH–), alkalinity is classified
respectively as bicarbonate alkalinity, carbonate alkalinity or hydroxide alkalinity.
Highly alkaline waters may lead to caustic embrittlement and also may cause deposition of
precipitates and sludges in boiler tubes and pipes.
With respect to the constituents causing alkalinity in natural waters, the following situations
may arise :
1. Hydroxides only
2. Carbonates only
3. Bicarbonates only
4. Hydroxides and carbonates
5. Carbonates and bicarbonates
(Notes. The possibility of hydroxides and bicarbonates existing together is ruled out because of
the fact that they combine with each other as follows forming the carbonates:
OH– + HCO3– → CO3– – + H2O
The types and extent of alkalinity present in a water sample may be conveniently determined by
titrating an aliquot of the sample with a standard acid to phenolphthalein end-point, P, and continuing
the titration to methyl orange end point M. The reactions taking place may be represented by the
following equations:
OH– + H+ → H O
2 ...(1)
– –
CO3 + H + → HCO – P
M ...(2)
3
HCO3– + H+
→ H CO
2 3
→ H2O + CO2 ...(3)
251
252 BASIC ENGINEERING CHEMISTRY
The volume of acid run down upto phenolphthalein end point P corresponds to the completion
of equations (1) and (2) given above, while the volume of acid run down after P corresponds to the
completion of equation (3). The total amount of acid used from beginning of the experiment, i.e.,
the methyl orange end point M, corresponds to the total alkalinity present which represents the
completion of reactions (1) to (3).
Table 5.1.
5. P< 1M Nil 2P M – 2P
2
(or V1 < V2)
Indicator
Eriochrome Black T (EBT) is used as a indicator: It is a typical metal ion indicator chemically it
is sodium 1-(1-hydroxy-2-naphthylazo)-6-nitro-2-naphthol-4-sulphonate. The indicator Eriochrome
Black T (a dye stuff) is effective between the pH (8 - II). It is therefore, essential while performing
the titration of hard water with EDTA solution, the pH of the solution must be made (pH = 10) by
adding a suitable buffer solution.
254 BASIC ENGINEERING CHEMISTRY
OH
OH
NaO3S N N
NO2
Ca/Mg
NO2
O
O
Eriochrome Black T
NaO3S N N
+ 2H+
NO2
Weak complex wine red in colour
B– WATER ANALYSIS TECHNIQUES 255
(ii)
At last thus releases Eriochrome Black T in free state. At this stage wine red colour of the
solution changes into sky blue colour (End point)
Permanent hardness can be determined by precipitating the temporary hardness by prolonged
boiling for about 30 minutes followed by titration with the EDTA solution as above. The difference
in the titre values corresponds to the temporary hardness of the water sample.
Calculation
Let volume of the water taken for each titration = 50 ml
Volume of EDTA used when titrated against standard hard water = V1 ml
Volume of EDTA used when titrated against sample hard water = V2 ml
Volume of EDTA used when titrated against water having permanent hardness = V3ml
(a) Strength of EDTA solution
1 ml of standard hard water (SHW) contains = 1 mg of CaCO3
50 ml of SHW contains = 50 mg of CaCO3
Volume of EDTA consumed for 50 ml of SHW = V1ml
\ V1ml of EDTA is used for = 50 mg of CaCO3
50
Or strength of EDTA solution = mg/ml of EDTA.
V1
(b) Total hardness
Volume of EDTA used for 50 ml of sample hard water = V2 ml
50
Since 1 ml of EDTA consume = mg of CaCO3
V1
50
V2 ml of EDTA will consume = × V2 mg of CaCO3
V1
256 BASIC ENGINEERING CHEMISTRY
50 × V2 1000
1000 ml of sample water = × mg of CaCO3
V1 50
V2 × 1000
= mg
V1
V × 1000
\ Total hardness = 2 ppm.
V1
(c) Permanent hardness
Volume of EDTA used for 50 ml of water, containing permanent hardness = V3 ml
50
V2 ml of EDTA will consume = × V3 mg of CaCO3
V1
Hence, 50 ml of water contains permanent hardness
50 V3
= × × 1000 mg of CaCO3
V1 50
V × 1000
= 3 mg
V1
V3
Permanent hardness = × 1000 ppm
V1
(d) Temporary hardness
Temporary hardness = total hardness – permanent hardness.
Report
The given water sample contains:
CO3– – alkalinity = 94 ppm
HCO3– alkalinity = 58 ppm
Total alkalinity = 152 ppm
Example 4. 100 ml of a water sample, on titration with N/50 H2SO4, gave a titre value of
5.8 ml to phenolphthalein end-point and 11.6 ml to methyl orange end point. Calculate the alkalinity
of the water sample in terms of CaCO3 and comment on the type of alkalinity present.
Solution.
P = 5.8 ml; M = 11.6 ml.
1
Since P = M, it means that all the alkalinity present in the water sample is due to CO3– – only:
2
while OH– and HCO3– are absent.
Further, the volume of N/50 H2SO4 equivalent to CO3– – present in 100 ml of the water sample
= 2P = 2 × 5.8 = 11.6 ml
Since 1 ml of 1N HCl ≡ 50 mg of CaCO3
11.6 1
11.6 ml of N/50 HCl ≡ 50 × × = 11.6 mg of CaCO3
1 50
This is the CO3– – present in 100 ml of the sample
... Strength of CO3– – in terms of CaCO3
1000
= 11.6 × = 116 mg/l
100
= 116 ppm
Report
The alkalinity of the water sample is 116 ppm, which is only due to CO3– –.
Example 5. 100 ml of a water sample, on titration with N/50 H2SO4, using phenolphthalein
as indicator, gave the end point when 5.0 ml of acid were run down. Another aliquot of 100 ml of
the sample also required 5.0 ml of the acid to obtain methyl orange end-point. What is the type of
alkalinity present in the sample and what is its magnitude?
Solution.
P = 5.0 ml; M = 5.0 ml.
Since P = M, it is obvious that the water sample contains only hydroxide alkalinity and it is not
a natural water sample. Further, since 1 ml of 1N H2SO4 ≡ 50 mg of CaCO3
B– WATER ANALYSIS TECHNIQUES 263
5 1
5 ml of N/50 H2SO4 ≡ 50 × ×
1 50
= 5 mg of CaCO3
This corresponds to 100 ml of the sample only.
... The amount of OH– present in 1 litre of the water sample
1000
= 5× = 50 mg of CaCO3
100
... Alkalinity of the water sample = 50 mg/l or 50 ppm
Example 6. A sample of water was found to contain the following species, on analysis:
Ca2+ = 40 mg/l Mg2+ = 24 mg/l
Na+ = 8.05 mg/l HCO3– = 18.3 mg/l
SO42– = 55.68 mg/l Cl– = 6.74 mg/l
Express the results in terms of salts present as their CaCO3 equivalents.
Solution.
Impurity CaCO3 equivalents
100
Ca2+ → 40 × = 100 ppm
40
100
Mg2+ → 24 × = 100 ppm
24
100
Na+ → 8.05 × = 17.5 ppm
23 × 2
100
HCO3– → 183 × 61× 2 = 150 ppm
100
SO42– → 55.68 × = 58 ppm
96
100
Cl– → 6.74 × = 9.5 ppm
35.45 × 2
Hence,
Total alkalinity = 150 ppm
Calcium alkalinity = 100 ppm
Magnesium alkalinity = 50 ppm
Total hardness = 200 ppm
Calcium hardness = 100 ppm
Magnesium hardness = 100 ppm
Calcium temporary hardness = 100 ppm
(or calcium alkalinity)
Magnesium temporary hardness = 50 ppm
(or magnesium alkalinity)
Magnesium permament hardness = 50 ppm
(or magnesium non-carbonate hardness)
Hence the salts presents in terms of their CaCO3 equivalent may be expressed as follows:
Ca(HCO3)2 — 100 ppm
Mg(HCO3)2 — 50 ppm
MgSO4 — 50 ppm
264 BASIC ENGINEERING CHEMISTRY
Na2SO4 — 8 ppm
NaCl — 9.5 ppm.
Example 7. 50 ml of a sample of water required 5 ml of N/50 H2SO4 using methyl orange as
indicator but did not give any colouration with phenolphthalein. What type of alkalinity is present?
Express the same in ppm.
Solution. As the water sample does not give any colouration with phenolphthalein (P = 0) hence
only HCO3– ions are present.
Now, 50 ml of water sample upto methyl orange end point = 5 ml of N/50 H2SO4
\ 50 mL × NM = 5 mL × N/50
Normality,
N 1 1
NM = 5mL × × = N
50 50mL 500
Now, strength of alkalinity upto methyl orange end point (in terms of CaCO3 equivalents)
= (NM × 50) g/L
1
M = × 50g/L × 1000 mg/L
500
M = 100 mg/L = 100 ppm
Hence, alkalinity due to HCO3– = M = 100 ppm.
Example 7. 500 ml of a water sample, on titration with N/50 H2SO4 gave a titre value of
20 ml to phenolphthalein end point and another 500 mL sample on titration with same acid gave a
titre value of 58 ml to methyl orange end point. Calculate the alkalinity of water sample in terms of
CaCO3 and comment on the type of alkalinity present.
Solution. 500 ml of water upto phenolphthalein end point
N
= 29 mL of H 2SO 4
50
N
\ 500 mL × NP = 29 mL of 50
29 mL 1
or Normality, NP = × N
500 mL 50
Now, strength of alkalinity upto phenolphthalein end point in terms of CaCO3 equivalent
= NP × 50 × 1000 ppm
= P = 58 ppm ...(i)
Give, 500 ml of water upto methyl orange end point
N
= 58 mL of H 2SO 4
50
N
\ 50 mL × NM = 58 mL ×
50
58 mL 1
Normality, NM = × N
500 mL 50
Now, strength (in terms of CaCO3 equivalents)
= M = NM × 50 × 1000 ppm
= M 116 ppm ...(ii)
From equation (i) and (ii)
1
P = M
2
B– WATER ANALYSIS TECHNIQUES 265
Hence only CO32– ions are present and alkalinity of water sample is due to CO32– = 2P =
M = 116 ppm.
Example 9. Acid solution Elucidate on the type and extent of alkalinity present in the water.
Solution. 200 ml of water upto phenolphthalein end point
= 9.4 ml of N/50 HCl
\ 200 ml × NP = 9.4 ml × N
50
9.4 ml 1
or Normality, NP = × N
200 ml 50
Now, strength of alkalinity upto phenolphthalein end point in terms CaCO3 equivalent
= P = NP × 50 × 1000 ppm
P = 47 ppm
As, 200 ml of water upto methyl orange end point
N
= 9.4 + 21 = 30.4 ml of HCl
50
30.4 ml 1
\ 200 ml × NM = × N
200 ml 50
30.4 ml 1
or N M = × N
200 ml 50
Hence, strength of alkalinity upto methyl orange end-point in of CaCO3 equivalent hardness
M = NM × 50 × 1000
M = 152 ppm
1
Since P < M , Hence CO32– and HCO3– ion re present in terms the given sample of water.
2
The alkalinity due to CO32– = 2P
= 2 × 47 = 94 ppm
and the alkalinity due to HCO3–
= M – 2P
= 152 –94
= 58 ppm
Hence, the given water sample contains CO32– alkalinity = 94 ppm
and HCO3– alkalinity = 58 ppm.
QUESTIONS
1. How does dissolved oxygen affect the quality of water used in boilers ? What are the vari-
ous methods employed in deaeration of water ? (RGPV Bhopal 2006)
2. Give the principle involved in the estimation of hardness by EDTA method.
3. Calculate the hardness of a water sample, whose 20 ml required 30 ml of EDTA. 10 ml of
calcium chloride solution, whose strength is equivalent to 300 mg of calcium carbonate per
200 ml, required 20 ml of EDTA solution. (Mumbai University, 1998)
4. Describe briefly the methods used for the analysis of the following parameters in water or
wartewater and discuss their significance
(a) Alkalinity (b) Hardness
(c) DO (d) BOD
(e) COD
5. How are the following determined in a water sample ?
(a) Chlorides (b) Sulfates
(c) Dissolved CO2 (d) Residual Chlorine
(e) TDS
6. �������������������������������������������������������������������������������������������
Evluate the type and extent of alkalinity due to various anions in the presence of phenolp-
thalein and methyl orange indicator in a titration (RGPV Bhopal 2009)
7. 0.5 gm of CaCO3 was dissolved in dilute HCl and diluted to 500 ml. 50 ml of this solution
required 48 ml of EDTA solution. For titration 50 ml of given hard water sample require 15
ml of EDTA solution for titration. Calculate total hardness of water sample in ppm.
(RGPV Bhopal 2006)
B– WATER ANALYSIS TECHNIQUES 271
2– –.
8. A sample of water contains 32 mg/l. of CO3 and 56 mg./L of HCO3 If the pH of the water
sample is 10.0, what is the alkalinity of the water sample in mg/L as CaCO3.
(Ans : 104.2 mg/L as CaCO3)
9. (a) How is the harness of water determined by the complexometric method using EDTA ?
(b) 50 ml of a water sample when directly titrated with 0.01 m EDTA solution using the standard
procedure gave 21 ml titre value at the end-point. Calculate the total hardness of the water
sample in PPm as CaCO3. (Ans : 420 PPm)
10. (a) How is the alkalinity of a water sample determined ?
(b) 100 ml of a water sample on titration with N/50 H Cl required 8.0 ml of the acid to phenol-
phthalein end-point and 9.0 ml of the acid to methyl orange end-point. Calculate the type
and extent of alkalinity present in the water sample.
(Ans. OH– alkalinity = 70 PPm as CaCO3 CO32–- alkalinity = 20 PPm as CaCO3).
11. Discuss briefly the principles involved in the determination of DO, BOD and COD in waste
water and their significance from the point of view of environmental pollution.
6. How are the following parameters determined in a water sample ?
(a) Chloride, Sulphate and TDS.
(b) Briefly discuss their significance
272 BASIC ENGINEERING CHEMISTRY
QUESTION BANK
Water And Its Industrial Application
1. (a) Explain the significance of the following types of chlorination :
(i) Break Point chlorination (ii) super chlorination
(b) Distinguish between disinfection and sterilization of water.
2. (a) How can you determine the residual chlorine in a water sample ?
(b) Discuss the importance of the following processes with reference to the treatment of water
for domestic and industrial purposes :
(a) sedimentation (b) coagulation (c) filtration (d) sterilization
3. Compare the lime-soda process and zeolite process of water softening with respect to the
principles involved, merits and demerits.
4. (a) Discuss the ion-exchange process of water softening.
(b) Why does the mixed bed ion exchange resin column provide very efficient demineralisation
of water ?
5. State some important specifications of the water used for the following industries.
(a) Thermal power generation (b) Paper (c) Textile (d) Dairy
6. (a) State the reasons as to why water used in boilers should be softened.
(b) Discuss the ion-exchange method of softening water.
7. (a) Explain the following :
(i) Priming (ii) Foaming (iii) Blow down (iv) Units of hardness
(b) What are the factors responsible for caustic embrittlement in boilers ? How can this be
prevented ?
8. (a) What are boiler troubles ?
(b) Why are they caused ?
(c) How can they be prevented ?
9. (a) Why are scales formed in boilers ? What are they made up of ? Why are they undesirable ?
(b) How can the scale formation in boilers be minimised ?
10. Discuss the various methods used for internal treatment of boiler feed water.
11. (a) Explain the zeolite process of water softening ?
(b) An exhausted zeolite softener was regenerated by passing 200 liters of NaCl solution
containing 0.2 g per liter of NaCl. How many liters of hard water sample having hardness
of 500 ppm can be softened using this softener ? (Ans : 68,376 lit)
12. A water sample gave the following analytical results : Ca (HCO3)2 – 162 ppm, Mg (HCO3)2
– 7.3 ppm, CaCl2 – 111 ppm, MgCl2 - 9.5 ppm, Mg SO4 - 60 ppm, NaCl - 60 ppm, CO2 - 44
ppm, HCl - 36.5 ppm. Calculate the quantities of lime (80% pure) and soda (85 % pure required
for softening 1012 litres of such a water sample. (Ans: 684.5 kgs lime ; 648..5 kg soda)
13. Write informative notes on any two of the following :
(a) Phosphate conditioning
(b) Boilder corrosion
(c) Internal treatment
(d) Sludge blanket type of lime - soda water softener
(e) Temporary and permanent hardness
(f) Colloidal conditioning.
272
QUESTION BANK 273
14. What are the requirements of feed water quality for modern high pressure boilers ? How can
they be achieved ?
15. Write short notes on the following:
(a) Caustic embrittlement (RGPV Bhopal 2009)
(b) Boiler corrosion (RGPV Bhopal 2006)
(c) Internal treatment
(d) Blow-down
(e) Break-point chlorination (RGPV Bhopal 2006)
(f) Impurities in water and their effects
(g) Slow sand filtratio
(h) Rapid pressure filtratio
(i) Scale and sludge formation (RGPV Bhopal 2009)
(j) Priming and foaming.
16. (a) Write the constituents responsible for the permanent hardness of water. Discuss one
treatment method.
(b) Why does hard water consume a lot of soap ?
(c) Why does magnesium bicarbonate required double amount of lime for softening.
(U.P. Technical University 2001)
17. (a) Describe the causes, harmful effects and control of scale and sludge formation in
boilers. (RGPV Bhopal 2009)
(b) A water sample using FeSO4.7H2O as coagulant at the rate of 278 ppm. gave the
following results on analysis :
Ca++ – 80 ppm, Mg++ – 48 ppm,
CO2 – 88 ppm; and HCO3– – 244 ppm
Calculate lime soda required for softening one million litres of the water sample.
or
(a) What are zeolites ? Discuss the chemistry involved in zeolite process of softening hard
waer. Also mention the limitations, advantages and disadvantages of this process.
(b) A zeolite softener was completely exhausted and was regenerated by passing 120
litres of sodium chloride solution containing 150 g/litre of NaCl. How many litres
of a sample of water of hardness 500 mg/liter can be softened by the softener before
regenerating it again ? (RGPV Bhopal 2001)
18. (a) The analytical results of raw water and treated water are as follows :
Ca2+ = 300 ppm
Mg2+ = 150 ppm
HCO3– = 244 ppm
OH– = 65 ppm
CO32– = 40 ppm
CO2 = 60 ppm
Calculate,
(i) The amount of lime (80% pure) and soda (90% pure) required to soften one million
litres of water using NaAlO2 as a coagulant at the rate of 41 mg/litre.
(ii) If 10,000 litres of the same water sample is softened through a zeolite softener, how
much NaCl will be required for its regeneration ? (Nagpur University, S-2001)
274 BASIC ENGINEERING CHEMISTRY
19. (a) What is meant by hardness of water ? Name the substances that cause permanent hard-
ness in water?
(b) Explain the importance of “phosphate conditioning ? in the “internal treatment” of
water.
(c) What is “demineralisation process” ? Point out its advantages and limitations ?
(Mumbai University, 1994)
Lubricants
1. (a) What are the functions of a lubricant ?
(b) What are the important properties that an efficient lubricant should possess ?
2. How are lubricants classified ? Give examples of each type.
3. (a) Discuss the various mechanisms of lubrication ?
(b) What type of lubricants are used in situations wher such mechanisms are in operation ?
276 BASIC ENGINEERING CHEMISTRY
4. (a) What are greases ? Under what service conditions they are used ?
(b) What are cup greases ? How are they manufactured ?
(c) What are the important tests for evaluating greases and what is their significance ?
5. Write informative notes on any two of the following :
(a) Extreme pressure lubrication.
(b) Blended or compounded oils
(c) Lubricating emulsions
(d) Synthetic lubricants
6. (a) What are the characteristics of a good solid lubricant ?
(b) How do the following act as lubricants ?
(i) Graphite (ii) Molybdenum disulphide
7. Discuss the various additives used for lubricants and their functions.
8. What are the various factors that determine the choice of a lubricant for a given application ?
9. (a) What do you understand by viscosity index and why it is an important property for lubricant ?
(b) A lubricating oil has the same viscosity as standard naphthenic and paraffinic type of oils
at 210° F. Their viscosities at 100° F are 320 S U respectively. Find the viscosity index of
the lubricating oil.
10. Write the significance of the following in evgluating a libricating oil :
(a) Flash point (b) Pour point
(c) Aniline pint (d) Oiliness
11. Write short note:
(a) saponification value (b) Acid value
(c) Iodine value (d) Carbon residue test
12. Describe with their significanc the following :
(i) Aniline Point
(ii) Cloud point and pour point (RGPV Bhopal 2009)
(iii) Steam emulsificatio number (Nagpur University, 2001)
(iv) Important function of lubricant.
13. (a) What are flas point and fir point of a lubricant. Point out their significance
(b) Explain the following properties of lubricants :
(i) Viscosity Index (ii) Aniline Point (iii) Neutralisation Number
(c) Write short note on Redwood Viscometer
14. (a) Defin :
(i) Acid Value (ii) Saponificatio (iii) Pour Point
(b) What are different mechanisms of lubrication ? Explain the boundary lubrication.
(RGPV Bhopal 2009)
(c) Write a note on determination of flas point by Pensky Martin Method. What is the
significanc of flas point. (RGPV Bhopal 2009)
Polymers
1. What are polymers? How are they classified ? Give examples of each type.
2. Mention any three important high polymers and their important uses.
3. How are polymerization reactions classified on the basis of their mechanism ? Discuss with
examples.
4. What are addition and condensation polymerization processes ? Give examples.
278 BASIC ENGINEERING CHEMISTRY
5. (a) Discuss the mechanism of chain polymerization.
(b) Degree of polymerization
(c) Homopolymer
(d) Copolymer.
6. Describe the major manufacturing processes employed for polymerization. Give examples.
7. What are the basic differences between thermoplastics and thermosetting plastics ? Give
examples.
8. What is Bakelite ? How is it manufactured ? State some of its important applications.
9. What are nylons ? How is nylon : 6 : 6 manufactured ? Give flow sheet, state some important
uses.
10. How is terylene prepared ? State some important uses.
11. What are silicones ? How are they manufactured ? Give flow sheet diagram ? State some
important applications of some important silicone products.
12. Discuss the preparation, properties and uses of any three of the following :
(a) PVC (b) Teflon
(c) High density polyethylene (d) Polyacrylates
(e) Glyptals (f) Urea formaldehyde
(g) Terylene (h) Polyurethanes
(i) Thiokols (j) Neoprene
13. Discuss the various stages of processing of rubber ? Give some important uses of rubbers.
14. What are elastomers ? What type of structural features are necessary for a polymer to behave
like an elastomer ? Give some important applications of elastomers.
15. Mention 3 important types of synthetic rubbers and discuss their synthesis, properties and
applications. How do synthetic rubbers compare with natural rubbers with respect to their
properties and service conditions ?
16. Write informative notes on any two of the following :
(a) Vulcanization of rubber (b) Compounding of rubber
(c) Reclamation of rubber (d) Fabrication of plastics
17. Describe the preparation, properties and uses of any three of the following :
(a) Cellulose acetate (b) Phenol-formaldehyde resins
(c) Polyethylene (d) Polystyrene
(e) Melamine formaldehyde resins (f) Decaron
(g) Silicone resins (h) Butyl rubber
(i) Buna-s (j) Nitrile rubbers
(k) Orlan (l) PMMA or lucite
18. Discuss the preparation properties and uses of various polymers related to synthetic rubber.
19. Draw the flow sheet for Nylon 6:6 and decron.