Engineering Chemistry

(CHY1701)
Text Book(s) Module -1
1. Sashi Chawla, A Text book of Engineering  Characteristics of hard water
Chemistry, Dhanpat Rai Publishing Co., Pvt.  Determination of water hardness
Ltd., Educational and Technical Publishers,  Numerical problems in hardness
New Delhi, 3rd Edition, 2015. determination by EDTA
2. O.G. Palanna, McGraw Hill Education  Determination of DO
 Determination of TDS in water
(India) Private Limited, 9th Reprint, 2015.
 Disadvantages of hard water in industries
3. B. Sivasankar, Engineering Chemistry 1st
 Modern techniques of water analysis for
Edition, Mc Graw Hill Education (India),
2008 industrial use.
Sources of Water

 Water has different physical, chemical and biological Impurities which can cause
problems in both domestic and industrial applications.
 Impurities in water

 Physical: - Inorganic such as clay, sand  Factors that control water characteristics
- Organic such as oil globules, vegetable/animal matter o Sedimentation
- Colloidal such as Fe(OH)3, Complex proteins, amines o Runoff/Erosion
o Dissolved oxygen (DO)
 Chemical: - Anions such as Cl-, SO42-, CO32-,HCO3-, NO3- o pH
- Cations such as Ca2+, Mg2+, Na+, K+, Fe3+, Al3+ o Temperature
- Dissolved gases such as O2, N2, CO2, H2S, NH3 o Decayed organic materials
o Toxic and hazardous substances
 Biological: - Microorganisms such as algae, fungi, bacteria o Oils, detergents, and other chemicals
(Pathogenic causing Malaria, diarrhoea, typhoid etc.) o Litter and rubbish
 Hardness of Water
 Symptoms of Hard Water include
 Hardness of water is the characteristic of
preventing lather formation of water  Stiff, dingy laundry
with soap.  Mineral deposits on dishes and glassware
 This is a common quality of water which  High energy costs, possibly due to scale
contains dissolved compounds of calcium build-up in pipes and on appliances
and magnesium and, sometimes, other  Scale build up in sinks, tubs, faucets etc.
divalent and trivalent metallic elements
 Hard water
 Hard water on treatment with soap (Stearic or palmitic acid salts
of sodium or potassium) causes white precipitate formation of
calcium or magnesium stearate or palmitate. Precipitation of the
soap prevents lathering at first.

 Types of Hardness
b) Permanent:
a) Temporary :
- Due to dissolved
- Due to dissolved bicarbonates of calcium and
chlorides and sulphates of
magnesium and carbonates of iron and other
calcium and magnesium.
heavy metals. Hence it is also called as carbonate
Also called as non-
hardness.
carbonate hardness.
- Can be easily removed by boiling where CO2
- Can be removed through
gas gets expelled removing the hardness.
zeolite, Lime-soda, ion-
exchange processes.
 Measurement of hardness of water
 Hardness of water is measured in parts per millions (ppm) as # Calculate the temporary
calcium carbonate equivalents. hardness in terms of calcium
 Reasons for expressing hardness in CaCO3 equivalents: carbonate equivalents in a water
- its molecular weight is 100; equivalent weight is 50. sample containing 12.2 mg
- it is the most common insoluble impurity in water. Ca(HCO3)2. Given that at. Wt. of
Ca=40 amu, O=16 amu, C=12
amu, H=1 amu. (Ans.: 7.53 mg)

# Calculate the temporary hardness and permanent hardness of a sample water containing Mg(HCO3)2 = 7.3
mg/L; Ca(HCO3)2 = 16.2 mg/L; MgCl2 = 9.5 mg/L; CaSO4 = 13.6 mg/L (atomic weight of Mg = 24, Ca = 40, Cl =
35.45 and S = 32). (Ans.: Temporary = 15 ppm, Permanent = 20 ppm)
Total Hardness= Temporary Water Hardness + Permanent Water Hardness
# Calculate the temporary hardness and total hardness of a sample water containing Mg(HCO3)2 = 73 mg/L ;
Ca(HCO3)2 = 162 mg/L ; MgCl2 = 95 mg/L; CaSO4 = 136 mg/L (atomic weight of Mg = 24, Ca = 40, Cl = 35.45
and S = 32) (Ans.: Temporary = 150 ppm, Total = 350 ppm)
# A sample hard water contains, 8.1 mg/L Ca(HCO3)2; 7.5 mg/L Mg(HCO3)2; 13.6 mg/L CaSO4; 12.0 mg/L
MgSO4 and 2.0 mg/L MgCl2. Calculate the hardness and express in CaCO3 equivalents. (Ans.: 5 ppm, 5.1
ppm, 10 ppm, 10 ppm, 2.1 ppm)
 Measurement of hardness of water
# Calculate the temporary hardness, permanent magnesium hardness, total permanent hardness & total
hardness in terms of calcium carbonate equivalents in a water sample containing calcium bicarbonate (12.2
mg), magnesium bicarbonate (8.2 mg), magnesium sulphate (5.6 mg), magnesium chloride (6.2 mg),
calcium sulphate (10.3 mg) & sodium sulphate (7.5 mg). Given that at. Wt. of Mg=24 amu, S=32 amu,
Cl=35.5 amu, Ca=40 amu, O=16 amu, C=12 amu, H=1 amu. (Ans.: temporary = 13.1 ppm, Permanent Mg =
11.2 ppm, Total permanent = 18.8 ppm, total = 31.9 ppm)
# How many grams of FeSO4 dissolved per liter gives 210.5 ppm of hardness? (Atomic weights: Fe = 56, S =
32, O = 16, Ca = 40, C = 12) (Ans.: 319.9 mg/L)

 Units of hardness
 Parts Per million (ppm)
Parts of CaCO3 eq./106 parts of water
 Milligrams per liter (mg/l)
mg of CaCO3 eq. present/ liter of water Relationship between units of water hardness
 Degree Clarke (oCl)  1 ppm = 1 mg/L = 0.1 °French = 0.07 °Clark
No. of geqv. of CaCO3/70000 parts of water
 Degree French (oFr)
No. of geqv. of CaCO3/105 parts of water
 Estimation of hardness of water
 O. Hehner’s method:
Permanent Hardness: Chloride and sulphates of Ca
 Temporary Hardness: Acid- and Mg are removed as insoluble CaCO3 and
base titration is performed MgCO3 by boiling the hard water with excess
before and after boiling the Na2CO3. Acid-base titration is performed before
hard water and after removal

 Soap titration method:

Hardness is estimated by adding a soap solution of known strength to a sample water solution until a
permanent lather is formed after shaking
 Estimation of hardness of water: EDTA method

 Water hardness can be readily determined by

complexo- metric titration with the chelating
agent EDTA
 EDTA is ethylene diamine tetraacetic acid.
 EDTA solution is colorless

 Corresponding disodium salt is used for the hardness estimation, as this slat forms
very strong and stable complex with Ca2+ and Mg2+.

 Initially, Ca2+ and Mg2+ or the

are treated with Eriochrome
black T (EBT) indicator using
ammonia buffer (to maintain
pH between 9-10) to get an
unstable Ca2+/Mg2+ complex
which imparts wine-red
colour to the solution
 EDTA method

 On addition of EDTA, EBT gets replaced by EDTA since EDTA forms a stronger complex with the metal ions

+ EBT
Steel blue

Wine red Ca2+/Mg2+ – EDTA complex (colorless)

 Overall process
 EDTA method: Procedure

 First EDTA Solution is standardized using standard hard water

(1 mg/mL of CaCO3 equivalents is prepared as standard hard water).
 For this, first known aliquot of Standard hard water is taken.
 10-15 mL of ammonia buffer is added to bring the pH between 9-10.
 Then a few drops of EBT solution is added to form the unstable complex giving wine red colour.
 This solution is titrated with the EDTA solution till the solution turns to steel blue indicating the formation
of stable EDTA-Metal ion complex.
 This volume of EDTA is noted as V1.
 The above procedure is repeated with sample hard water of unknown hardness.
 Volume of EDTA is noted as V2. (Total hardness)
 Then sample hard water of 250 mL is taken and evaporated to a volume of 50mL when the temporary hard
salts settle down.
 The solution is filtered and washed thoroughly and made up again to 250mL.
 From this solution, 50 mL is pipetted out and titrated in similar manner as done with standard hard water.
 Volume of EDTA is noted as V3 (Parmanent hardness)
 EDTA method: Calculation
 V1 mL of EDTA is consumed by 50 mL of standard hard water (1 mg/mL of CaCO3 )
V1 mL of EDTA = 50 mg of CaCO3
EDTA standardization
1 mL of EDTA = (50/V1)mg of CaCO3

 EDTA consumed by sample hard water = V2 mL

So, V2 mL of EDTA = [(50/V1)x V2] mg of CaCO3
Hence, 50 mL of sample hard water contains [(50/V1) x V2] mg of CaCO3
Total hardness
 1 mL of sample hard water contains = [(50/V1)x V2/50] mg of CaCO3
 1000 mL of sample hard water = [(50/V1)x V2/50 x 1000] mg/L
i.e. Total hardness of sample hard water = (V2/V1 x 1000) mg of CaCO3 (ppm)
 50 mL of sample hard water after removing temporary hardness consumed V3 mL of EDTA.
and, V3 mL of EDTA = [(50/V1) x V3]mg of CaCO3 equiv.
 50 mL of sample hard water after boiling contained [(50/V1) x V3] mg of CaCO3 equiv. Permanent
 1 mL of sample hard water after boiling contained = [(50/V1) x V3/50] mg of CaCO3 equiv. hardness
1000 mL of sample hard water after boiling contained = [(50/V1) x V3/50 x 1000] mg/L CaCO3 equiv.
= (V3/V1 x 1000) mg/L CaCO3 equiv
Temporary hardness = Total hardness – permanent hardness = (V2-V3)/V1 x 1000
 EDTA method
 A 100 ml sample of water require 15 ml of 0.02 M EDTA for titration using EBT as indicator. Another 100 ml of
water from the same source was boiled and precipitate removed by filtration, the filtrate requires 5 ml of
0.02 M EDTA for titration. Calculate the total hardness, permanent hardness & carbonate hardness of water
sample. [Ans.:Total=300ppm, Permanent =100ppm, Carbonate=200ppm] (Hint:1000 mL 1MEDTA ≡ 1000 mL
1M CaCO3 = 100 g of CaCO3]
 Calculate Total, Temporary and Permanent hardness of the given hard water sample with following data:
[i] 50 mL of standard hard water sample consume 42 mL of EDTA solution.
[ii] 50 mL of hard water sample consume 19.9 mL of EDTA solution before boiling.
[iii] 50 mL of hard water sample consume 8.9 mL of EDTA solution after boiling.
Standard hard water is prepared by dissolving 1.5 gram of CaCO3 per Litre.
[Ans.: 710.7 ppm, 392.9 ppm, 317.8 ppm]
 1 g CaCO3 was dissolved in 1 L solution. Then 100 mL of this solution was required to titrate 90 mL of EDTA
solution. A 200 mL of water sample required 72 mL of same EDTA solution. The water sample (200 mL) on
boiling was titrated against 36 mL of EDTA solution. Calculate the temporary hardness of the water sample.
 0.5 g of CaCO3 was dissolved in HCl and the solution made up to 500 ml with distilled water. 50 ml of the
solution required 48 ml of EDTA solution for titration. 50 ml of hard water sample requires 15 ml EDTA
and after boiling and filtering requires 10 ml of EDTA solution. Calculate the temporary hardness.
 10 mL of water sample required 20 mL of EDTA to titrate. Given that 20 mL of CaCl2 solution required 30
mL of EDTA solution and the strength of CaCl2 solution is equivalent to 1.5 g of CaCO3 per liter. Calculate
the hardness of the water sample.
 Dissolved Oxygen (DO)

 Dissolved oxygen (DO) is the

amount of oxygen dissolved in a
given quantity of water at a
particular temperature and
atmospheric pressure
 Dissolved oxygen gets into the
water by diffusion from the
atmosphere, aeration of the
water as it tumbles over falls
and rapids, and as a waste
product of photosynthesis
 It is an important parameter in
assessing water quality because
of its influence on the
organisms living within a body
of water
 Amount of oxygen dissolved is
expressed as mg/L or ppm
Types of Oxygen Demand
 Biochemical Oxygen Demand (BOD): Amount Causes of Low Dissolved Oxygen
of dissolved oxygen required by bacteria/other  Low dissolved oxygen (DO) primarily
microorganisms to break down organic material results from excessive algae growth
present in a given water sample at certain caused by Nitrogen/phosphorus which
temperature over a specific time period. generally originate from discharges from
̶ To determine BOD, a measured volume of municipal and private wastewater
waste water is taken and its DO is treatment, cropland and urban storm
measured. It is then incubated for 5 days water runoff, and natural decay of
at 20 °C and its DO is determined again. vegetation
 Chemical Oxygen Demand (COD): An indicative  After algae die, decompose process
measure of the amount of oxygen that can be consumes dissolved oxygen. This can
consumed by reactions in a measured solution. result in insufficient amounts of
̶ It is commonly expressed in mass of dissolved oxygen available for aquatic
oxygen consumed over volume of solution species.
which is milligrams per litre (mg/L).  Die-off and decomposition of submerged
̶ A COD test can be used to easily quantify plants also contributes to low dissolved
the amount of organics in water. oxygen.
 Factors affecting DO

 Aeration
# Estimation of DO by Winkler’s method
 Water temperature
 DO is important with respect
 Organic wastes
to the species of aquatic life, It
 Aquatic plant populations is also measure of its ability to
 Photosynthetic activity of the oxidize organic impurities in
water water
 Respiration of animals and  DO test is used to control the
plants amount of oxygen in boiler
 Speed of water flow feed water
 Altitude (atmospheric pressure)  DO test is helps to assess the
raw water quality and to keep a
 Human activities
check on stream pollution
 Salt concentration: The
solubility of oxygen decreases  It is one of the most useful
with increase in concentration titrations involving iodine
of the salt.  In order to avoid loss of oxygen
 Other dissolved gases from the water sample, it is
concentrations fixed by MnSO4
 DO estimation by Winkler’s method

Δ The principle involved in this methods of

determination of DO is to bring about the
oxidation of potassium iodide (KI) to iodine
with dissolved oxygen present in water sample
after adding MnSO4, KI and KOH
Δ The reaction with manganese(II) hydroxide
which is converted rapidly and quantitatively to
manganese(III) hydroxide. Here MnSO4 acts
oxygen carrier to enable the dissolved oxygen in
molecular form to take part into the reaction
Δ On acidification, the manganese reverts back to
the divalent state and an equivalent amount of
iodine is liberated form the KI present
Δ The liberated I2 is titrated against standard  Procedure:
sodium thiosulfate (hypo) solution, using starch
as indicator  Standardization of Na2S2O3
 Estimation of DO using standardized Na2S2O3
Δ This means that 4 mol thiosulphate is equivalent
to 1 mol dissolved oxygen
 DO estimation by Winkler’s method

 Procedure:

 Standardization of Na2S2O3
• The secondary standard solution of sodium thiosulphate
is standardized by titrating with a primary standard
potassium dichromate using starch as indicator
• Color change occurs from straw yellow to blue to
colorless
 Total Dissolved Solids (TDS)

# Total dissolved solids (TDS) is the amount of particles dissolved

in water
 They come from a) Organic sources (leaves), b) Silt, c) Industrial  Recommended TDS for drinking
wastage and sewage as well as runoff from urban sources, water is 25-250 mg/L
fertilizers and pesticides, d) Inorganic materials  At any cost drinking water TDS
 A constant level of minerals, eg. Phosphorous, nitrogen and should not exceed 500 mg/L
sulphur, is necessary for aquatic life.  TDS for distilled water will be 0.5-
 Concentration of dissolved solids should not be too high or too 1.5 mg/L
low which can affect the growth and leads to death of many  TDS ranges from 100-20,000 mg/L
aquatic organisms. in river water and will be generally
 High concentration of dissolved solids reduces the clarity of water higher in ground water
and can decrease the photosynthesis and raises the water  Sea water will have 3500 mg/L of
temperature. TDS
 It can be determined taking a known amount (say 100 mL) of  Lakes and streams will have a TDS
water and by evaporating the contents carefully to dryness. The of 20-250 mg/L
residue (W/g) left after evaporation of the filtered sample shows
the total dissolved solids present in that articular water sample.
 Hard Water: Problems
 For Domestic Use  For Industrial Use
a) Washing:  Paper Industry: Presence of Ca/Mg make impact on the
• Hard water, when used for washing properties and quality of paper and their products
purposes, does not lather freely  Textile industry: Hard water cause waste of soap. During
with soap. dyeing process, Ca/Mg salts present in water make the quality
• It produces sticky precipitates of of the shades very poor.
calcium and magnesium soaps.  Sugar industry: If nitrates, sulphates of Ca/Mg are present,
• Bathing – can cause skin problem they cause hindrance to crystallization of sugar
b) Cooking:  Concrete making: Water containing chlorides and sulphates, if
• Due to the presence of dissolved used for concrete making, affects the hydration of the cement
hardness producing salts the boiling and the final strength of the hardened concrete.
point of water is elevated & more  In steam generation in boilers: If the hard water fed directly to
fuel is and time are required. the boilers - lead many problems such as formation of scales
c) Drinking: which corrodes the boiler, wastage of fuel etc.
• Hard water causes bad effect on our
digestive system.
• The possibility of forming calcium
oxalate crystals in urinary tracks is
increased (Kidney stones).
 Boiler Troubles: Sludge

 These deposits may consist of  Prevention of sludge formation

minerals, oils, and other matter.
• By using well softened water
Sludge can stick to the boiler walls
and continue to grow in size over • Frequently ‘blow-down
time, causing clogs and other issues operation’, i.e., drawing off a
portion of the concentrated
 Sludge’s are formed by substances water.
which have greater solubility in hot
water than in cold water, e.g.,
MgCO3, MgCl2, CaCl2, MgSO4, etc
# Disadvantages of sludge formation
 Sludges are poor conductor of heat, so they tend to waste a
portion of heat generated.
 If sludges are formed along with scales, then former gets
entrapped in the latter and both get deposited as scales.
 Excessive sludge formation disturbs the working of the boiler.
It settles in the regions of poor water circulation such as pipe
connection, plug opening, gauge-glass connection, they even
choke the pipes. Blow-down vessel installation
 Boiler Troubles: Scale
 Decomposition of calcium bicarbonate
 Scales are hard deposits, which stick very firmly to
the inner surfaces of the boiler. Ca(HCO3)2 → CaCO3 ↓ + H2O + CO2 ↑
 Scales are difficult to remove, even with the help  However, scale composed chiefly of calcium
of hammer and chisel. carbonate is soft and is the main cause of scale
 These are the main source of troubles. formation in low-pressure boilers.
 Hard, adherent coating forms due to presence of  In high-pressure boilers, CaCO3 becomes soluble due
salts like Mg(HCO3)2, MgCl2, Mg(OH)2, Ca(HCO3)2, to the formation of Ca(OH)2
Fe2O3, CuO, CaSO4, Complex Silicates of CaCO3 + H2O → Ca(OH)2 + CO2 ↑
Magnesium, Iron, Sodium, and Aluminium
 Dissolved magnesium salts undergo hydrolysis (at
prevailing high temperature inside the boilers)
forming magnesium hydroxide precipitate, which
forms a soft type of scale
MgCl2 + 2 H2O → Mg(OH)2 ↓ + 2HCl ↑
 Presence of silica in small quantities deposits as
calcium silicate (CaSiO3) or magnesium silicate
(MgSiO3). These deposits stick very firmly on the
inner side of the boiler surface and are very difficult
to remove.
 Boiler Troubles: Scale
 Disadvantages of scale formation  Removal of Scales
# Wastage of fuel: # Decrease in efficiency:
Scales have a low thermal conductivity.  With the help of scraper or piece of
Scales may sometimes wood/wire brush, if they are
So rate of heat transfer from boiler to deposit in the valves and
inside water is greatly decreased. In loosely adhering.
condensers of the boiler
order to provide a steady supply of heat and choke them  If they are brittle, by giving thermal
to water, excessive or over heating is partially. This results in shocks –heating the boiler and
carried out and this causes increase in decrease in efficiency of then suddenly cooling with cold
fuel consumption. boiler. water.
# Lowering of boiler safety : # Danger of explosion:  By dissolving them by adding them
Due to scale formation, over-heating of When thick scales crack, chemicals, if they are adherent and
boiler is to be done in order to maintain due to uneven hard. Thus, CaCO3 scales can be
a constant supply of steam. The over- expansion, the water dissolved by using 5-10% HCl.
heating of the boiler tube makes the comes suddenly in CaSO4 scales can be dissolved by
boiler material softer and weaker. This contact with over-heated adding EDTA, with which they form
causes distortion of boiler tube and iron plates. This may soluble Ca-EDTA complexes.
makes the boiler unsafe to bear the even cause explosion of
pressure of the steam, especially in high- the boiler.  By frequent blow-down operation,
pressure boilers. if the scales are loosely adhering.
Sludge vs. Scale
 Prevention of scales formation
# External treatment: Softening of water by Soda-lime
process, Zeolite (permutit) process, Ion exchange
process
# Internal treatment (also called
sequestration): Changing original
character of the hardening
chemicals via
Precipitation of the scale forming
impurities/Converting them into
water soluble compounds
 Colloidal conditioning
 Carbonate conditioning
 Phosphate conditioning
 Calgon conditioning
 NaAlO2 treatment
 Electrical conditioning
 Radioactive conditioning
 Complex metric method
 Prevention of Scale Formation

# Colloidal conditioning # Carbonate conditioning # Phosphate conditioning

 Colloidal conditioning is a  Performed in low-pressure  Performed in high-pressure boilers
mixture in which one substance boilers. Scale-formation is  Scale formation can be avoided by
of microscopically dispersed avoided by adding sodium adding sodium phosphate
insoluble particles is suspended carbonate to boiler water
 Mg2+ and Ca2+ salts are converted
throughout another substance  CaSO4 is converted into to non-adherent and easily
 In low-pressure boilers, scale calcium carbonate removable, soft sludge of calcium
formation can be avoided by CaSO4 + Na2CO3 → CaCO3 ↓+Na2SO4 and magnesium phosphates. The
adding organic substances like  Deposition of CaSO4 as sludge can be removed by blow -
kerosene, tannin, agar-agar (a scale does not take place down operation
gel), etc. These get coated over and calcium is precipitated 3 CaCl2 + 2 Na3PO4 →Ca3(PO4)2↓+ 6 NaCl
the forming precipitates, as loose sludge of CaCO3,  NaH2PO4 (acidic); Na2HPO4,
thereby yielding non-sticky and which can be removed by (weakly alkaline); Na3PO4,
loose deposits blow-down operation (alkaline) are used for this purpose
 These lose deposits can easily  Excessive Na2CO3 can result  Choice of the phosphate depends
be removed by pre-determined in caustic embrittlement of the alkalinity of the boiler feed
blow-down operations. water
 Prevention of Scale Formation
# Calgon conditioning # NaAlO2 treatment # Electrical conditioning:
 Involves in adding calgon [sodium  Sodium aluminates gets hydrolyzed Sealed glass bulbs,
hexametaphosphate (Na6P6O18) yielding NaOH and a gelatinous containing mercury
to boiler water. precipitate of aluminium hydroxide connected to a battery, are
set rotating in the boiler.
NaAlO2 + 2H2O → NaOH + Al(OH)3 When water boils, mercury
 The sodium hydroxide, so-formed, bulbs emit electrical
precipitates some of the magnesium discharges, which prevents
as Mg(OH)2 scale forming particles to
adhere /stick together to
MgCl2 + 2 NaOH → Mg(OH)2+ 2 NaCI
form scale
 The flocculent precipitate of # Radioactive conditioning:
 It prevents the scale and sludge Mg(OH) 2 plus Al(OH) 3, produced
formation by forming soluble complex inside the boiler, entraps finely Tablets containing
compound with CaSO4. Soluble complex suspended and colloidal impurities, radioactive salts are placed
Na2[Ca2P6O18] can be easily removed including oil drops and silica. inside the boiler water at a
few points. The energy
Na2[Na4(PO3)6] → 2 Na+ +[Na4P6O18]2-  The loose precipitate can be radiations emitted by these
removed by pre-determined salts prevent scale
2 CaSO4 + [Na4P6O18]2 − → [Ca2P6O18]2 −+ 2 Na2SO4 blow-down operation formation
 Prevention of Scale Formation
# Complexometric method  Caustic Embrittlement
 Prevention of Caustic
 Involves addition of alkaline # This type of boiler corrosion is caused by embrittlement
(pH = 8.5) solution of EDTA using highly alkaline water generated by
lime-soda process – free Na2CO3 is usually  by using sodium
to feed-water. The EDTA phosphate as softening
binds to the scale-forming present in small proportion in the softened
water. agent, instead of sodium
cations to form stable and carbonate
soluble complex. As a result, # In high pressure boilers, Na2CO3
the sludge and scale decomposes to NaOH and carbon dioxide  by adding tannin or lignin
formation in boiler is and this makes the boiler water alkaline to boiler water, since
prevented. these blocks the hair-
Na2CO3 + H2O → 2 NaOH + CO2 cracks, thereby preventing
 Moreover, this treatment : # The NaOH containing water flows into infiltration of caustic soda
(1) prevents the deposition of the minute hair-cracks present in the solution in these
iron oxides in the boiler, inner side of boiler and dissolving iron of  by adding sodium
(2) reduces the carryover of boiler as sodium ferroate (Na2FeO2) this sulphate to boiler water.
oxides with steam, and causes embrittlement of boiler parts, Na2SO4 also blocks hair-
particularly stressed parts (like bends, cracks, thereby preventing
(3) protects the boiler units
joints, rivets, etc.) infiltration of caustic soda
from corrosion by wet
steam Fe + NaOH → 2 Na2FeO2 + H2 solutions.
 Boiler Troubles: Dissolved gas

 It’s a decay of boiler material by  Removal of dissolved oxygen  Dissolved carbon dioxide
chemical or electro-chemical attack by  By adding calculated  CO2 is reacts with water to
its environment quantity of Sodium sulphite form carbonic acid (H2CO3)
 Main reasons for boiler corrosion are: or Hydrazine or Sodium which has a slow corrosive
Dissolved oxygen sulphide effect on the boiler
o Water usually contains about 8 ppm 2 Na2SO3 + O2 → 2 Na2SO4 material
of dissolved oxygen at room N2H4 + O2 → N2 + 2 H2O  CO2 is released inside the
temperature. boiler, if water used for
Na2S + 2 O2 → Na2SO4
o Dissolved oxygen in water, in steam generation contains
presence of prevailing high  By mechanical de-aeration bicarbonate
temperature, attacks boiler material: CO2 + H2O → H2CO3
2 Fe + 2 H2O + O2 → 2 Fe(OH)2 Mg(HCO3)2 → MgCO3 + H2O + CO2

4 Fe(OH)2 + O2 → 2 (Fe2O3.2H2O)  Removal of CO2

 By adding calculated
quantity of ammonia
2 NH4OH + CO2 → (NH4)2CO3 + H2O
 By mechanical-aeration process
 Boiler Troubles
 Acids from dissolved salts  Priming
 Water containing dissolved magnesium  When a boiler is
salts liberate acids on hydrolysis producing steam
MgCl2 + 2 H2O → Mg(OH)2 + 2 HCl rapidly, some particles
of the liquid water are
 The liberated acid reacts with iron of the carried along-with the
boiler in chain-like reactions producing HCl. steam. This process of
Fe + 2 HCI → FeCl2 + H2 'wet steam' formation
FeCl2 + 2 H2O → Fe(OH)2 + 2 HCl is called priming.
 As a result presence of even a small amount
of MgCl2 will cause corrosion of iron to a
 Priming is caused by:
large extent
o Presence of a large amount of dissolved solids
o high steam velocities
o sudden boiling
o improper boiler design
o sudden increase in steam-production rate
 Boiler Troubles: Priming & Foaming

 Foaming  Priming and Foaming are objectionable because:

 Production of persistent foam or  Dissolved salts in boiler water are carried by the wet
bubbles in boilers, which do not steam to super-heater and turbine blades, where they
break easily. Foaming is due to get deposited and the deposit reduces their efficiency
presence of substances like oils  Dissolved salts may enter the parts of other machinery,
(which greatly reduce the where steam is being used and decrease the life of the
surface tension of water) machinery
 Priming and foaming, usually,  Actual height of the water column cannot be judged
occur together properly, thereby making the maintenance of the boiler
 Priming can be avoided by: pressure becomes difficult.

 fitting mechanical steam purifiers

 Foaming can be avoided by:
 avoiding rapid changing steaming rate
 adding anti-foaming chemicals like castor oil
 maintaining low water levels in boilers,
 removing oil from boiler water by adding
and
compounds like sodium aluminates.
 efficient softening and filtration of the
boiler-feed water.
 Modern Methods of Water Analysis
 Importance of Water Analysis:
o to ensure its quality/to detect
pollutants that should be removed by
water treatment.
 For example, drinking water must be fit
for human consumption, while
industrial water should be free from
any contaminants that may
corrode/damage equipment.
 Limitations of Traditional Methods of
Water Analysis: The traditional analysis
includes chemical analysis,
colorimetry, spectrometry,
chromatography, and atomic
absorption. Although these techniques
differ in sensitivity and accuracy, most
of them are highly accurate.
 They require sampling, expensive devices, manpower & they are time-consuming and difficult to conduct onsite
 Lab-on-a-chip

 A lab-on-a-chip (LOC) is a device that integrates

one or several laboratory functions on a single
integrated circuit (commonly called a "chip") of  Advantages of LOC
only millimeters to a few square centimeters to  low fluid volumes consumption (less waste, lower
achieve automation and high-throughput reagents costs, and fewer sample volumes)
screening
 faster analysis and response time due to short
 Lab-on-a-chip devices are a subset of diffusion distance & high surface to volume ratio.
microelectromechanical systems (MEMS) devices Reduce manpower in the sampling process.
and sometimes called "micro total analysis
systems" (µTAS)  better process control because of compactness of
the systems due to the integration of much
 Lab-on-a-chip technology employs microfluidics, functionality and small volumes
which deals with very minute amounts of fluids in
microchannels, to perform the analysis. The lab-  safer platform for chemical, radioactive or biological
on-a-chip device is a chip that resembles studies
electronic chips, but with micro-channels instead  much less expensive and offers higher accuracy
of electrical circuits. It shrinks the lab to the chip because of the small volume analysis and the
size and can perform complete analysis or even possibility of eliminating the sampling process, which
series of analysis. reduces the human error
 Lab-on-a-chip
 The main components of a lab-on-a-chip system for water analysis
are – a liquid delivery system (injector and fluidic transporter),
mixer, reactor, separator, and power supply.
 The Injector – to deliver precise volumes into the chip.
(syringe pumps or robotic pipets); Transporters – to control
all aspects of the flow. They can be active (need an energy  LoC technology is rapidly developing and being
source) or passive (require manipulation the geometries of used in different industrial and research fields
the channels). The most preferred is electrochemical  Most biological LoC devices are commercialized,
pumping systems, such as microsyringe pumps. while More advanced LoCs for water analysis
 Mixers: to mix different fluids into the channels. It also are still developing.
could be passive (require design manipulation) and active  Some LoC applications in water analysis are
(require power). already established; such as pH testing,
detection of various chemicals (e.g., NO3-/NO2-,
 The Reactor: reaction takes place here. 3 types of reactors Mn+2, phosphates, and silicates).
– gas phase, liquid phase, and packed-bed reactors.  For example: the microfluidic pH analysis uses
 Controllers: used for controlling all types of activities in the sulfonaphthalein as the main indicator. It
chip as well as data acquisition and signal processing. includes the absorption cell, a static mixer, a
syringe pump and four valves attached to the
 Power supplies: essential to run the lab-on-a-chip systems. chip to regulate the flow.
 Engineering Chemistry
(CHY1701)
Module -2
 Water softening methods: - Lime-soda, Zeolite and ion exchange processes and their applications
 Specifications of water for domestic use (ICMR and WHO)
 Unit processes involved in water treatment for municipal supply: Sedimentation with coagulant,
Sand Filtration, Chlorination
 Domestic water purification: Candle filtration, Activated carbon filtration
 Disinfection methods: Ultrafiltration, UV treatment, Ozonolysis, Reverse Osmosis, Electrodialysis
 Water softening methods

 Softening of water by removing the  Basic principles of Lime-soda process

hardness producing substance from  All the soluble hardness-causing impurities are converted into
the water. In Industry three main insoluble precipitates which may be removed by setting and
methods are employed for filtration
softening of water.  Lime [Ca(OH)2] and soda [Na2CO3] are the reagents used to
 Lime-soda process: Lime [Ca(OH)2] precipitate the dissolved salts of Ca2+ and Mg2+ as CaCO3 and
and Soda [Na2CO3] is added - Mg(OH)2. The precipitates are filtered off.
residual hardness: 15-60 ppm  Lime reacts with temporary hardness producing substance, CO2,
 Zeolite (permutit) process: filtered acids, bicarbonates and alums.
through the zeolite - a natural  Lime cannot remove the calcium permanent hardness which should
substance – residual hardness ~ 10 be removed by soda.
ppm  The precipitation reactions with lime and soda are very slow & only
 Ion-exchange and Mixed bed ion- calculated amounts of lime and soda are to be added. Excess
exchange process: amount of lime & soda causes boiler troubles like caustic
embrittlement.
• Cation exchange resins (RH+)
• Anion exchange resins (R’OH-)  Cold lime-soda & Hot lime-soda process
• Mixed bed ion-exchange
Lime-soda process

 Cold lime soda process  Operated at room temperature.

 Precipitate formed are finely formed hence
do not settle down easily.
 It is essential to add small amount of
coagulant [aluminium sulphate, sodium
aluminate, Alum (K2SO4·Al2(SO4)3·24H2O)]
 Coagulant hydrolyse to form gelatinous
precipitates and entraps the fine
precipitate
2 NaAlO2 + 4 H2O → Al(OH)3 ↓ + 2 NaOH
Al2(SO4)3 + 3 Ca(HCO3)2 → 3 CaSO4 + 2 Al(OH)3 + 6 CO2
 The softened water passes through a
filtering media (wood fibre) for complete
removal of sludge
 It provides water with a residual hardness
of 50 to 60 ppm.
Lime-soda process
 Hot lime-soda process consists of three parts:
 Hot lime soda process
 a) Reaction tank to mix all ingredients
 b) Conical sedimentation vessel where the sludge settles down
 c) Sand filter where sludge is completely removed

 Calculated quantity of lime and soda are

mixed with water at 80-150 0C. Reaction
proceed faster, softening capacity is
increased many folds
 The precipitate and sludges formed settle
down rapidly; no coagulant needed
 Dissolved gases (CO2, O2) are driven out
easily
 Produces water contain the residual
hardness of 15 to 30 ppm
 Lime-soda process
Cold lime-soda process Hot lime-soda process
Done at room temp (25-30°C), Slow Process Elevated temperature, 80-150 °C, Rapid process
Use of Coagulants is must Coagulants are not required
Filtration is not easy Filtration is easy since the viscosity is low at high temperature
Residual hardness is around 60 ppm Residual hardness is 15-30ppm
Dissolved gases are not removed Dissolved gases like O2 and CO2 removed to some extent
Low softening capacity High softening capacity

# Advantages of lime soda process

# Disadvantages of lime soda process
 It is very economical. If the process is combined with
sedimentation/coagulation lesser amounts of coagulants shall be  For efficient and economical
needed. softening, careful operation and
skilled supervision is required.
 It increases the pH of the treated water - acidic corrosion reduced.
 Disposal of large amount of sludge
 Besides the removal of hardness, the quantities of minerals in the
poses a problem.
water are reduced.
 This can remove hardness up to 15
 Due to alkaline nature of treated water amount of pathogenic
ppm which is not good for boilers.
bacteria in water is considerably reduced.
 Lime-soda process - Reactions

 Lime can remove temporary hardness only  Soda removes all calcium permanent hardness
Ca(HCO3)2 + Ca(OH)2 → 2 CaCO3↓ + 2 H2O L CaCl2 + Na2CO3 → CaCO3 ↓+ 2 NaCl S

Mg(HCO3)2 + Ca(OH)2 → Ca(HCO3)2 + Mg(OH)2↓ CaSO4 + Na2CO3 → CaCO3 ↓+Na2SO4 S

Ca(HCO3)2 + Ca(OH)2 → 2 CaCO3 ↓ + 2 H2O  Mineral acid removal

Mg(HCO3)2 + 2 Ca(OH)2 → 2 CaCO3 ↓ + Mg(OH)2↓+ 2 H2O 2L 2 HCl + Ca(OH)2 → CaCl2 + 2 H2O L
CaCl2 + Na2CO3 → CaCO3 ↓+ 2 NaCl S
 Magnesium permanent hardness requires both L & S
2 HCl + Na2CO3 → 2 NaCl + CO2 + H2O S
MgCl2 + Ca(OH)2 → CaCl2 + Mg(OH)2 ↓ L
CO2 + Ca(OH)2 → CaCO3 ↓ + H2O L
CaCl2 + Na2CO3 → CaCO3 ↓+ 2 NaCl S
H2SO4 + Ca(OH)2 → CaSO4 + 2 H2O L

MgSO4 + Ca(OH)2 → CaSO4 + Mg(OH)2 ↓ L CaSO4 + Na2CO3 → CaCO3 ↓+ Na2SO4 S

CaSO4 + Na2CO3 → CaCO3 ↓+ Na2SO4 S

H2CO3 + Ca(OH)2 → CaCO3↓+ 2 H2O L
 Lime-soda process - Reactions
 Dissolved iron salts Substance Type of Requirement of Lime
FeSO4 + Ca(OH)2 → CaSO4 + Fe(OH)2 L hardness (L) and/or Soda (S)
CaSO4 + Na2CO3 → CaCO3 ↓ + Na2SO4 S Ca(HCO3)2 Temporary L
Mg(HCO3)2 Temporary 2L
4 Fe(OH)2 + 2 H2O + O2 → 4 Fe(OH)3 ↓
CaCl2 Permanent S
 Dissolved aluminum salts CaSO4 Permanent S
Al2(SO4)3 + 3 Ca(OH)2 → 3 CaSO4 + 2 Al(OH)3 ↓ 3L MgCl2 Permanent L+S
MgSO4 Permanent L+S
3 CaSO4 + 3 Na2CO3 → 3 CaCO3 ↓ + 3 Na2SO4 3S
FeSO4 Permanent L+S
 NaAlO2 + 2 H2O → Al(OH)3 ↓ + NaOH -L H2SO4 - L+S
HCl - L+S
 Reaction of HCO3- (Example: NaHCO3)
CO2 - L
2 HCO3- + Ca(OH)2 → CaCO3 ↓+ 2 H2O + CO32- L & -S
NaAlO2 - -L
 NaCl, KCl, Na2SO4, SiO2, Fe2O3: do not impart any Al2(SO4)3 Permanent 3L + 3S
hardness, do not consume any lime or soda, do not
HCO3- - L-S
account for calculating lime or soda requirement
 Lime-soda process - Numerical
 Lime required for softening * as CaCO3 equivalent
𝟕𝟒
[ Temp. Ca2+ + 2 × Temp. Mg2+ + Perm. (Mg2+ + Fe2+ + Al3+) + CO2 + H+ (HCl or H2SO4) + HCO3-] x Volume
𝟏𝟎𝟎

100 parts by mass of CaCO3 ≡ 74 parts of Ca(OH)2  1 part of CaCO3 ≡ 74/100 of Lime
 Soda required for softening
𝟏𝟎𝟔
[ Perm. (Ca2+ + Mg2+ + Fe2+ + Al3+) + CO2 + H+ (HCl or H2SO4) - HCO3-] x Volume
𝟏𝟎𝟎
100 parts by mass of CaCO3 ≡ 106 parts of Na2CO3  1 part of CaCO3 ≡ 106/100 of Lime

 Calculate the amount of lime  Hardness in CaCO3 equivalent due to Mg(HCO3)2 = 15.6*50/73 = 10.68
and soda required to soften ppm, Ca(HCO3)2 = 34.4*50/81 = 21.23 ppm, MgSO4 = 60*50/60 = 50 ppm
50000 L of the water sample mg/L; CaCl2 = 25*50/55.5 = 22.52 ppm, MgCl2 = 35*50/47.5 = 36.48
containing Mg(HCO3)2 = 15.6 ppm, SiO2 = 0 ppm, NaCl = 0 ppm
mg/L; Ca(HCO3)2 = 34.4 mg/L; 𝟕𝟒
MgSO4 = 60 mg/L; CaCl2 = 25  Required Lime = [ 21.23 + 2 × 10.68 + 50 + 36.48] x 50000 =
𝟏𝟎𝟎
mg/L; MgCl2 = 35 mg/L; SiO2 = 74*129.07*50000/100 = 4775590 mg = 4.77 Kg
25 mg/L; NaCl = 20mg/L. [Ca = 𝟏𝟎𝟔
 Required Soda = [ 22.52 + 50 + 36.48] x 50000
40; Mg = 24; H = 1; C = 12; O = 𝟏𝟎𝟎
16; Cl = 35.5, S = 32] = 106*109.36*50000/100 = 5777000 mg = 5.77 Kg
 Lime-soda process - Numerical
 Calculate the amount of lime (88.3% pure) and soda (99.2% pure) for treatment of 24,000 liters of water,
whose analysis is as follows: Ca(HCO3)2 = 18.5 ppm; Mg(HCO3)2 = 1.42 ppm; MgSO4 = 1.90 ppm; CaSO4 = 1.34
ppm; CaCl2 = 1.75 ppm. Also calculate the carbonate and non-carbonate hardness of the water sample.

# Hardness in CaCO3 equivalent due to

Ca(HCO3)2 = 18.5*50/81 = 11.42 ppm;
Mg(HCO3)2 = 1.42*50/73 = 0.97 ppm;
MgSO4 = 1.90*50/60 = 1.58 ppm;
CaSO4 = 1.34*50/60 = 1.12 ppm;
CaCl2 = 1.75*50/55.5 = 1.58 ppm
# Carbonate hardness = 11.42+ 0.97 = 12.39 ppm
# Non-carbonate hardness = 1.58+1.12+1.58 = 4.28 ppm
# Actual Lime req. = 74*[11.42+(2*0.97)+1.58]*24000/100 = 74*14.94*24000/100 = 265334.4 mg = 0.265 Kg

# Lime to be taken = 100*0.265/88.3 = 0.3 Kg

# Actual soda req. = 106*[1.58+1.12+1.58]*24000/100 = 106*4.28*24000/100 = 108883.2 mg = 0.109 Kg

# Soda to be taken = 0.109*100/99.2 = 0.11 Kg

 Lime-soda process - Numerical

 A sample water on analysis has been found to contain the following impurities in ppm: Ca(HCO3)2 = 48.6;
Mg(HCO3)2 = 29.2; MgCl2 = 3.8; CaCl2 = 33.3; CaSO4 = 54.4; NaCl = 659. Calculate the quantity of lime and
soda required for softening one million liters of water {Atomic weight: Ca = 40; Mg = 24; H = 1; C = 12; O =
16; Cl = 35.5, S = 32} (Ans: Lime = 54.8 Kg, Soda = 78.4 Kg)
 Calculate the amount of lime (85%) and soda (90%) required for softening 50,000 litres of hard water
containing following impurities (mg/L): CaSO4 = 40, MgCl2 = 46, Mg(HCO3)2 = 82 , Ca(HCO3)2 = 35, KCl = 10.
(Ans.: Lime = 7.94 kg, Soda = 4.58 kg)
 Explain with chemical equations and calculate the amount of lime and soda needed for softening
1,00,000 liters 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 purity of soda is 98%. 10% of Lime and Soda are to be used
in excess in order to complete the reaction quickly. (Ans.: Lime = 4.52 kg, Soda = 4.95 kg)
 Calculate the amount of lime and soda required for softening 50,000 liters of hard water containing
Ca(HCO3)2= 81 ppm, Mg(HCO3)2 = 73 ppm, CaCl2 = 222 ppm, MgSO4= 180 ppm, Na2SO4 = 15 ppm, NaCl =
165 ppm, and Fe2O3 = 25 ppm. (Ans.: Lime = 12.21 Kg, Soda = 18.55 Kg)
 Calculate the amount of lime and soda required for softening 50,000 liters of hard water containing
Ca(HCO3)2= 81 ppm, Mg(HCO3)2 = 73 ppm, CaCl2 = 222 ppm, MgSO4= 180 ppm, Na2SO4 = 15 ppm, NaCl =
165 ppm, and Fe2O3 = 25 ppm. Ans.: (Lime = 11.1 Kg, Soda = 18.55 Kg)
 Permutit or Zeolite Process

 Zeolite is hydrated
sodium aluminium
silicate having a general
formula,
Na2OAl2O3.xSiO2.yH2O.
(x = 2 to 10 & y = 2 to 6)
 Zeolites form with many different crystalline structures
having large open pores in a very regular arrangement and  Artificial zeolite used for water softening is
roughly the same size as small molecules. In the open Permutit, in Greek it means “boiling stone”.
pores it can trap other molecules/ions inside it.  These are porous, glassy particles having
 It exchanges Na+ ions for Ca2+ and Mg2+ ions of hard water higher softening capacity compared to green
 Common Zeolite is Na2OAl2O3.3SiO2.2H2O known sand.
as Natrolith  They are prepared by heating China clay (hydrated
 Other gluconites (Green sand – Iron potassium aluminium silicate), Feldspar (KAlSi3O8-NaAlSi3O8 –
phyllosilicate with characteristic green colour, a CaAl2Si2O8) are a group of rock-forming tectosilicate
mineral containing Glauconite) are used for
minerals which make up as much as 60 % of the earth’s
water softening.
 These are less porous, amorphous and durable crust) and soda ash (Na2CO3).
 Permutit or Zeolite Process

 For softening of water by zeolite process,

hard water is percolated at a specified
rate through a bed of zeolite, kept in a
cylinder. Zeolite holds sodium ions
loosely and can be represented as Na2Ze.
Where Ze = insoluble frame work.
 The hardness causing ions(Ca2+, Mg2+) are
retained by the zeolite as CaZe and MgZe
respectively, while the outgoing water
contains sodium salts. During this
process, the water becomes free from
Ca2+ and Mg2+ ions.

 Regeneration:  At this stage, the supply of hard water is stopped and

the exhausted zeolite is reclaimed by treating the
• After some time, the zeolite is completely
bed with a brine solution. The washing (containing
converted into CaZe and MgZe and it ceases to
CaCl2 and MgCl2 ) are led to drain and the
soften water, i.e., it gets exhausted.
regenerated zeolite bed thus-obtained is used again
for softening purpose.
 Permutit or Zeolite Process

Na2Ze + Ca(HCO3)2 → 2 NaHCO3 + CaZe

Regeneration of Zeolite
Na2Ze + Mg(HCO3)2 → 2 NaHCO3 + MgZe
CaZe + 2 NaCl → CaCl2 + Na2Ze
Method of Na2Ze + CaSO4 → 2 Na2SO4 + CaZe
softening: MgZe + 2 NaCl → MgCl2 + Na2Ze
Na2Ze + MgSO4 → 2 Na2SO4 + MgZe
Na2Ze + CaCl2 → 2 NaCl + CaZe
Na2Ze + MgCl2 → 2 NaCl + MgZe
Advantages: Disadvantages:
 Residual hardness of water is about 10 ppm only > Coloured water or water
 Equipment is small and easy to handle containing suspended impurities
 Time required for softening of water is small cannot be used without filtration
 No sludge formation and the process is clean > Water containing acidic pH cannot
 Zeolite can be regenerated easily using brine solution be used for softening since acid
will destroy zeolite.
 Any type of hardness can be removed without any modifications
to the process
 Ion-exchange Process

 Ion exchange is a reversible chemical reactions for  Resins are natural/synthetic organic
removing dissolved ions from solution and compound
replacing them with other similarly charged ions  For water treatment purpose we
M-Ion(1) + Ion(2) → M-Ion(2) + Ion(1) use synthetic ion exchange resins,
 It is primarily used for softening where calcium which are insoluble in water, cross-
and magnesium ions are removed from water. it is linked & long chain polymers with
also used for the removal of other dissolved ionic micro-porous structure
species  The most widely used base-
materials are polystyrene and
 Cation-exchange Resins(RH ):+
polyacrylate
― Styrene divinyl  The functional groups attached to
benzene copolymers the polymer are responsible for
― Cation exchange the ion-exchanging properties
resins will exchange
cations with H+
― Common functional  2 R ̶ SO 3
̶ H+ + Ca2+ → [R ̶ SO ̶ ] Ca2+ + 2 H+
3 2

groups (X) are SO3H,  2 R ̶ SO3 ̶ H+ + Mg2+ → [R ̶ SO3 ̶ ]2Mg2+ + 2 H+

COOH, OH
 They are easily regenerated with mineral acids  [R ̶ SO3 ̶ ]2Ca2+/Mg2++ 2 H+ → 2 R ̶ SO3 ̶ H+ + Ca2+/Mg2+
 Ion-exchange Process
 Anion Exchange Resin
 An amino functional group is incorporated into the anion exchange resin
enabling the exchange of anions like the Cl- ion, SO42- ion.
 Common functional groups NMe3+, PR3+, SR2+
2 R ̶ OH + SO42 ̶ → R2 ̶ SO42 ̶ + 2 OH ̶
R ̶ OH + Cl ̶ → R ̶ Cl ̶ + OH ̶
 Regeneration: On alkali treatment they are capable of exchanging OH-
R2 ̶ SO42 ̶ / R ̶ Cl ̶ + n OH ̶ → n R ̶ OH + SO42 ̶ /Cl ̶

 After cation exchange column and anion

exchange column H+ + OH ̶ → H2O
de-ionized water
 Hard water should be first passed through
the Cation exchanger and then Anion
exchanger to avoid hydroxides of Ca2+ and
Mg2+ getting formed
 Ion-exchange Process
 Mixed bed ion-exchanger
 A mixed bed ion exchanger is a vessel
filled with a mixture of cation exchange
& anion exchange resin.
 When hard water flows through this
resin mixture cations dissolved in the
water are exchanged for H+ ions, while
anions dissolved in the water are
exchanged for OH- ions.
 The soft water from this method contains
less than 1 ppm of dissolved salts and
hence more suitable for boilers

 Regeneration:
 When the resin beds are exhausted, the
mixed bed is backwashed by using
compressed air or forcing the water from
the bottom in the upward direction.
Ion-exchange Process

NaOH

Mixed
Mixed ionizer Exhausted Anion
ionizer
bed mixed exchanger
bed ionizer bed (low
density)
H2SO4
Cation exchanger
(higher density)
Backwash
water
Comp.
Raw water Demineralized water air Washings to
sink
 The light weight anion exchanger move to the top and forms upper layer above the heavier cation
exchanger. The anion exchanger is regenerated by passing caustic soda (NaOH) from the top and
then rinsed with pure water. The lower cation exchanger bed is then washed with dilute H2SO4
solution and then rinsed.
 These two beds are then mixed again by forcing compressed air to mix both and the resins are now
ready to use.
 Ion-exchange Process
 Advantages:
 Can be used for highly acid and  Ion-exchange process vs. Zeolite process vs. Lime-soda process
highly alkaline water
 Residual hardness of water is as low
as 2 ppm
 Very good for treating water for
high pressure boilers

ꭓ Disadvantages:
 Expensive equipment and chemicals
 Turbidity of water should be < 10
ppm. Otherwise output will reduce;
turbidity needs to be coagulated
before treatment.
 Needs skilled labour
 Water for domestic use

 Drinking or potable water should be safe to drink and

should satisfy the following requirements:
 Clean and odourless, pleasant in taste, turbidity < 10
ppm, free from dissolved gases like H2S, free from
minerals like Pb, As, Cr and Mn salts, alkalinity should not
be too high (pH should be around 8.0), should be
reasonably soft, Total Dissolved Solids (TDS) < 500 ppm,
free from disease producing pathogenic micro-organisms.
 Water treatment for municipal supply
Lakes/Reservoirs/Rivers Storage tanks
Removes dirt/other particles suspended  Coagulation
in water. Alum/other chemicals are  Flocculation
added for coagulation through floc.  Clarification
 Sedimentation
Storage in
Disinfection
closed Filtration
containers for (Chlorination, Use
 Heavy particles settle to the bottom and clear water goes for filtration
distribution of Ozone, UV light)
 Filtration using Sand, Charcoal, Candle
 Steps involved in water purification
 Removal of suspended impurities:  Filtration: Filtration is the process of removing colloidal matter,
 Screening: Raw water is passed and most of the microorganisms, etc by passing water through a
through screens having large number bed of fine sand and other proper sized granular materials
of holes which retain the floating  The irregular pores in the Sand filter hold the sediment particles
particles thereby allowing the filtered water to pass through an
 Sedimentation: Removes suspended underground drain
particles
― stand undisturbed in big tanks where
most of the suspended matter settles
down due to gravity.
― Supernatant water is pumped off &
added coagulant to remove the
colloidal and fine clay particles – Alum
(K2SO4.Al2(SO4)3.24H2O), Sodium
Aluminate (NaAlO2) and Ferrous
sulphate (FeSO4.7H2O) used as
coagulant
 Filtration
 Advantages:  Activated Carbon Filtration
 Very effective removal of • Activated carbon filters are generally used in the process of removing
most contaminants organic compounds and/or extracting free chlorine from water.
 Simplicity in design, simple • Coconut shells and coal (anthracite or bituminous) are both organic
operation and maintenance, sources of activated carbon.
no electricity required,
construction with local Mechanism:
material and knowledge, No  Carbon formation: when an organic source is burned in an
chemicals involved anaerobic environment, about 30% of the organic mass remain
intact, driving off heavy organic molecules.
 Long lifespan (> 10 years)
 Activation: Prior to being used for water treatment, it must be
 Disadvantages: "activated by either Steam Activation (800°C-1000°C) or Chemical
Activation (a powerful dehydrating agent like phosphoric acid
 Minimal quality of initial
(P2O5) or zinc chloride (ZnCl2)."
fresh water or pre-
 The process of activation opens up the carbon’s massive number
treatment required
of pores and further drives off unwanted molecules. The open
 Majority of chemicals pores allow the carbon to capture contaminants through
and fluoride is not adsorption.
removed
 Sand Filtration & Disinfection
 Candle Filtration  Disinfection (Sterilization)
 The Candle Filters are pressure filters Removal of bacteria is sterilization or disinfection. There are several
– operating on a batch cycle. important sterilization methods
 By boiling:
 The Candle ― Kill only existing germs in water at the time of boiling
Filter consists ― Do not provide any protection against future possible contamination
of three major ― Costly & impossible to employ this in the large scale systems
components:  By adding bleaching powder
The vessel, ― The chemical action produces HOCl (Hypochlorous acid) –
filtering a powerful germicide)
elements &
cake discharge ― Introduces Calcium in water, thereby making it more hard
mechanism ― Excess of it gives a bad taste and smell to treated water
Ca(OCl)Cl + H2O → Ca(OH)2 + Cl2 Cl2 + H2O → HCl + HOCl
 Very well suited  By using chloramine
for handling  Mixing chlorine and ammonia in 2:1 leads to the formation of
flammable, toxic chloramine (ClNH2) which is more stable than chlorine. In water
and corrosive chloramine hydrolyzes and liberate HOCl
materials.
Cl2 + NH3 → HCl + ClNH2 ClNH2 + H2O → HOCl + NH3
 Disinfection
 Chloramine is more reactive and longer lasting than  Disinfection of Drinking Water with UV Light
chlorine and is a better bactericidal agent than chlorine.
 Excess of ClNH2 does not produce any bad smell but
imparts good taste to water
 By ozone
 Ozone gas is a very good disinfecting agent.
Produced by passing silent electric discharge
through cold and dry oxygen.
 Ozone is highly unstable and breaks down to give
nascent oxygen. It is a powerful disinfecting agent  Advantages of UV Disinfection
and kills all the microorganisms and oxidizes the √ Highly effective on broad range of pathogens &
organic matter present in the water. forms no harmful by-products
O3 → O2 + [O]
√ Inactivation independent of pH & temperature
 Advantages: Removal of colour, smell and taste in
√ No unpleasant taste/odor, no transportation,
water without giving any residue. Excess not harmful.
storage/handling of chemicals
ꭓ Disadvantage: Expensive than chlorine, not employed
for municipal water treatment. √ Easily installed within existing water treatment
facilities, simple to operate
 Water purification by Filtration process

 A microfiltration filter has a

pore size around 0.1 micron.
Through microfiltration, many
microorganisms are removed,
but viruses remain in the
water.
 An ultrafiltration filter has a
pore size around 0.01 micron.
Ultrafiltration remove larger
particles, and may remove
some viruses.
 Neither microfiltration nor
ultrafiltration can remove
Substances removed from water by membrane filtration process dissolved substances unless
they are first adsorbed (with
 The green arrow indicates that the particle is small enough to pass
activated carbon) or
through the filter, whereas the deflected orange arrow indicates
coagulated (with alum or iron
that the filter blocks the particle from passing through the filter.
salts).
Water purification by Filtration process
 A nanofiltration filter has a pore
size around 0.001 micron. It
removes most organic molecules,
nearly all viruses, most of the
natural organic matter and a
range of salts.
 Nanofiltration removes divalent
ionsso nanofiltration is often,
used to soften hard water.
 Reverse osmosis filters have a
pore size around 0.0001 micron.
 After water passes through a
reverse osmosis filter, it is
 RO gives 96-99 % NaCl rejection. >95 % inorganic salts and charged essentially pure water. In
organics are rejected by the RO membrane due to charge repulsion at addition to removing all organic
the membrane surface. molecules and viruses, reverse
 RO membranes are made of polymers, cellulosic acetate and osmosis also removes most
aromatic polyamides. minerals that are present in the
water.
 Water purification by RO

 Application:  When two solutions of unequal

 Potable water from sea water/brackish concentrations are separated by a
water Semipermeable membrane,
 Ultrapure water for food processing & solvent will flow from lower conc.
electronic industry to higher conc. due to osmotic
 Pharmaceutical grade water pressure
 Water for chemical, pulp, paper
industry
 The water gets forced through the
semipermeable membrane leaving
behind the dissolved solids.  This phenomenon can be
 Thus water is separated from the reversed by making the solvent
contaminants rather than removing to flow in the opposite direction
contaminants from water. by applying hydrostatic pressure
 Both ionic and non-ionic impurities on the concentrated side
as well as colloidal impurities are left (Reverse Osmosis)
behind.  Pressure of 15-40 kg/cm2 is
 This process is also called as “Super- applied on the contaminated
filtration” or “Hyper-filtration” water compartment.
 Water Purification
 Advantages of Reverse Osmosis  The process of removing common salt from water is desalination
 Advantage is in removing ionic, non-  Electrodialysis consists of a large container with two membrane
ionic, colloidal and high molecular wt. separators, one permeable to positive ions and the other
organic matter. permeable to negative ions.
 Only replacement cost of membranes  In the outer compartments anode and cathode are arranged to
(life is 2 years) pass DC Voltage. When DC voltage/current is passed through the
 Membrane replacement is fast and cell, Na+ will move towards cathode & Cl- will move towards
hence uninterrupted water supply can anode through the membrane.
be ensured
 Being adopted for converting sea
water into potable water and for high
pressure boilers

 The concentration of salt decreases in the middle

compartment and increases in the side
compartments. Water from the middle compartment
is collected and this water is desalinated water.
 For efficient separation, ion-selective membranes are
used which selectively allow cations or anions to
pass through them.
Water Purification

 Electrodialysis cell consists of Large number of pairs

of rigid Plastic membranes.
 Saline water at a pressure of 5-6 kg/cm2 is passed
through the membrane pairs.
 DC current is applied perpendicular to the direction
of water flow.

Advantages are:
 Unit is compact and installation is economical
 Best suited if electricity is available.
 Engineering Chemistry
(CHY1701)
Module -3: Corrosion
 Dry & Wet Corrosion – Detrimental effects to Buildings, Machines, Devices
 Decorative art forms emphasizing Differential Aeration, Pitting, Galvanic &
Stress Corrosion Cracking
 Factors that enhance corrosion and choice of parameters to mitigate
corrosion.
 Corrosion
Effects of corrosion
 Corrosion is termed as the (electro)chemical reaction  Loss of metal/metal
between a material and its environment that leads to thickness = Loss of
deterioration of the material and/or its properties efficiency = Loss of time
 It is a process through which metals in manufactured  Reduction in value: Loss
states return to their natural oxidation states of valuable materials such
as blockage of pipes,
mechanical damage of
underground water pipes
 This process is a reduction-oxidation reaction in which  Mechanical damage:
the metal is being oxidized by its surroundings, often Accidents due to
by oxygen in air mechanical loss of
metallic bridges, cars,
 The reaction is both spontaneous & electrochemically aircrafts
favoured.  Pollution: Causes
 Corrosion is essentially the creation of voltaic/ pollution due to escaping
galvanic cells where the metal in question acts as an products from corrosion
anode and generally deteriorates or loses functional (Contamination of fluids
stability. in vessels and pipes)
 Common Metals/Alloys
 Iron:  Steel:  Copper:
 Main corrosion product is rust  These contain Fe, C, Cr,  Main corrosion products are
or iron oxides Ni, Mo etc. CuCO3 + Cu(OH)2, patinas as Cu2O
 The most familiar form of rust  Main corrosion  Brass and Bronze:
is the reddish coating that product is iron oxides  Brass contains Cu, Zn
forms flakes on iron and steel – those similar to iron  Bronze contains mainly Cu, Sn
(Fe2O3)  Along with iron, other  Main corrosion products are
 Rust also comes in other alloying metals (Ni, Cr, similar to copper corrosion
colors, including Yellow, Mo) also get corroded products
Brown, Orange, and even due the formation of
Green! The different colors corresponding oxides
reflect various chemical
compositions of rust.
 Reason of corrosion

 In nature, most metals (except Au, Pt, etc) prefer Types of corrosion
existing as thermodynamically more stable  Corrosion is classified on the basis of nature of
compounds, such as, their oxides, carbonates, the Corrodent, Mechanism of corrosion, and
chlorides, silicates etc. Appearance of the corroded metal
 During the extraction process at high temperature, the  Dry corrosion (chemical corrosion):
metallic compounds are reduced to their pure metallic
state which is, thermodynamically unstable state. Classified depending on the corroding agent:
 The extracted/reduced pure metal will always have a (i) Corrosion by oxidation,
strong tendency to convert itself into the more stable (ii) Corrosion by gases other than oxygen
metallic compound oxidized state through corrosion. (iii) Corrosion by liquid metals.
 The Gibbs free energy changes of forming oxide and  Wet corrosion (electrochemical corrosion):
sulphides are negative, so oxidation reaction is usually (i) Evolution of hydrogen-type corrosion,
spontaneous.
(ii) Consumption of oxygen-type corrosion,
(iii) Galvanic or bimetallic corrosion,
(iv) Concentration cell corrosion (or water line
corrosion).
 Dry Corrosion
 This corrosion occurs due to the direct  Oxidation Corrosion
chemical attack of atmospheric gases such  Direct action of oxygen in the absence of moisture at high/low
as O2, halogens, H2S, SO2, N2 or anhydrous temp. leads to oxidation corrosion
inorganic liquids on the metal surface.  At high temp. all metals are attacked by oxygen – except noble
 Dry corrosion occurs when there is no metals like Ag, Au, Pt. At ambient temp. generally metals are
moisture or water to aid corrosion slightly attacked
 This process is very sensitive to  Alkali metals & alkaline earth metals get oxidized readily
temperature. Under hot conditions, dry
corrosion occurs at a much faster rate
 Corrosion is due to adsorption & the
corrosion products, generally, accumulate
in the same spot where corrosion occurs
 Main types of dry corrosion are
 Corrosion by oxygen/oxidation corrosion
 Corrosion by other gases like H2S, SO2, N2,
CO2, F2 etc.  When oxidation starts, a thin layer of oxide film will be
 Liquid metal corrosion/Erosion Corrosion formed on the surface and the nature of the film decides the
further action (Porous/non-porous film)
 Oxidation Corrosion
Mechanism
 For oxidation, either the metal must diffuse
outwards through the oxide layer to the
surface or the oxygen must diffuse inwards
through the oxide layer to the underlying
metal. Both transfers occur, but the outward
diffusion of the metal is generally much more
rapid than the inward diffusion of oxygen.
 This diffusion is driven by the size of metal
and oxide ion
 Types of oxide layers: Nature of the oxide formed
 Oxidation takes place first at the surface of the plays an important part in oxidation corrosion
metal process. As the oxide layer grows the rate of
electron transfer decreases. The corrosion can be
 Adsorption of oxygen on to the metal surface
stopped and the metal can be passive
 Loss of electron from the metal and gain of
 Stable: Oxides of Al, Cu, Pb, Sn
electron by oxygen
 Unstable: Ag, Pt, Au
 Dissociation of oxygen  Volatile: Molybdenum oxide
 Formation of oxide layer onto the metal surface  Porous: Oxide of Li, Na, Mg
 Oxide Layers
 Stable (protective) oxide layer  Porous oxide layer:
 It is a fine grain of oxide layer which is
non-porous and adheres strongly to the
metal. Oxides of Al, Pb, Cu, Ni and Cr
which form stable, non-porous & tightly
adhering impervious metal-oxide films (~
30 nm thick) to the pure metallic surface.
 Such layers prevents oxygen from
diffusing through the metal and further
attack is stopped. Further oxidation  These oxide layers have minute pores.
corrosion is stopped  Oxygen will diffuse through these pores and cracks
 Unstable oxide layer promoting further corrosion.
 Fe is a good example of this type of corrosion. Iron
 Oxide layers produced on noble metal surfaces
when attacked by H2S at high temperature forms
(Pt, Ag etc.) immediately decompose back into
porous FeS layer
the metal and oxygen, thereby preventing
oxidation corrosion
Metallic oxide Metal + Oxygen
 Oxide Layers
 Volatile oxide layer  Pilling – Bedworth rule
 The protective/non-protective nature of the
oxide film is determined by Pilling-Bedworth rule
 The ratio of the volume of the oxide formed to
the volume of the metal consumed is called as
Pilling-Bedworth ratio

 These are oxide layers which

evaporate as soon as they are formed
and hence further corrosion is RPB = Pilling–Bedworth ratio, M = Atomic/Molecular mass, n = number
facilitated. of atoms of metal per 1 molecule of the oxide, ρ = density, V = volume.
 The underlying metal surface is  If Voxide > Vmetal: The oxide layer is protective and non-porous
exposed for further corrosion. After  Aluminium forms Aluminium oxide whose volume is greater
some time the metal itself will than the volume of the metal (Al). These do not undergo
disappear. corrosion rapidly. Other metals: Cu, In, Al, Ni, Cr
 Molybdenum (Mo) is an example of  If Voxide < Vmetal: The oxide layer is non protective and porous
volatile oxide layer corrosion. MoO3
is volatile (MoO2 is non-volatile).  Alkali and alkaline earth metals like Li, Na, K – these undergo
corrosion more rapidly
 Corrosion by other gases
 Main types of dry corrosion are  Liquid metal corrosion/Erosion Corrosion
 Corrosion by oxygen/oxidation corrosion
 Liquid metal (Hg, Zn, Sn, Pb, Cd etc.) flowing
 Corrosion by other gases like H2S, SO2, N2, CO2, F2 etc. at high temperature over the solid metal or
 Liquid metal corrosion/Erosion Corrosion alloy can result in
 In dry atmosphere CO2, Cl2, SO2, F2, NOx etc. are gases  dissolution of solid metal by liquid metal
which can attack the metal and corrode  internal penetration of the liquid metal into
 Extent of corrosion depends on the affinity of the metal the solid metal
to the gas. # This type of corrosion is experienced in
 These gases chemically react with the metal forming pipe lines used in oil and refineries. Liquid
either porous or non-porous layers of films mercury dissolves most metals by forming
 Protective/non-porous layer prevents from further attack, amalgams, thereby corroding them.
whereas non-protective/porous layer expose the # In devices used in nuclear power plants – it
underlying fresh metal surface for further attack. causes brittle failure of metal structure
 H2S gas attacks steel and make them brittle
2 Ag + Cl2 → 2 AgCl non-porous layer
Fe + H2S → FeS + H2 porous layer
Sn + 2 Cl2 → SnCl4 volatile layer
 Wet or Electrochemical Corrosion
Types of corrosion  In wet corrosion, a conducting liquid
(electrolyte) is in contact with a metal or two
 Dry corrosion (chemical corrosion) dissimilar metals or alloys are partially dipped in
 Wet corrosion (electrochemical corrosion) the electrolyte
 It occurs when electrons from metal surface are
 Criteria for Electrochemical Corrosion transferred to a suitable electron acceptor or
1. Formation of galvanic cells on the surface of metal depolarizer. Generally water is present to serve
generating anodic and cathodic areas. as a medium for the transport of ions
2. Presence of conducting liquid with the formation  The most common depolarizers are oxygen,
of electrochemical cells. acids, the cations of less active metals
3. At anode of metal surface, oxidation [Corrosion]  As the electrons flow through the metallic object
takes place by liberating electrons. itself, the anodic and cathodic regions can be at
widely separated locations
4. At cathode, reduction [No corrosion] takes place
 Generally, Anodic regions tend to develop at
# The rate of the electrochemical corrosion will locations where the metal is stressed
depend on the solubility of the corrosion product.  Contact with a different kind of metal, either
 If soluble: rate of corrosion will be high direct or indirect, can lead to corrosion of the
 If insoluble: rate of corrosion will be very low. more active one
 Mechanism of Wet Corrosion
 based on Nernst theory
 According to which all metals have a
tendency to pass into solution. If a
metal having higher electrode potential
comes into contact with another metal
having a lower electrode potential, a
galvanic cell is set up
 The metal having the Lower electrode (reduction) potential becomes Anodic
and goes into solution to a measurable extent. The other becomes Cathodic  General/Uniform corrosion
and does not enter solution. The extent of galvanic corrosion depends upon
the difference in the electrode potential of the two electrodes and their  Hydrogen evolution type
respective areas. corrosion
 The greater the difference in the potentials: the greater will be the corrosion.  Oxygen consumption type
corrosion
 Smaller the area of anode as compared to cathode: attack will be more
 Galvanic corrosion
# Oxidation and reduction steps occur at separate locations on the metal.
This is possible because metals are conductive & the electrons can flow  Concentration cell corrosion
through the metal from the anodic to the cathodic regions. The presence  Pitting corrosion
of water is necessary in order to transport ions to and from the metal  Stress corrosion
 Wet or Electrochemical Corrosion

 Uniform Electrochemical Corrosion  Hydrogen evolution type corrosion

 It occurs when metals are in contact with an acidic sol.
 The electrochemical reactions (in aqueous  All metals above hydrogen in electrochemical series can
or atmospheric media) proceed uniformly show this type of corrosion
over the entire exposed metal surface. ← Rusting of
 General corrosion represents the greatest iron metal
destruction of metal. But, general in acidic
corrosion is less dangerous than the other env. takes
corrosion forms because the life of place in this
equipment or structures can be accurately way
estimated from simple corrosion tests and  Metal ions
sometimes by visual inspection. produced at
the anode
dissolves in
the
 Hence, this type of corrosion causes electrolyte
“displacement of H+ ions from the acidic while
solution by metal ions” hydrogen
 Anodic areas are large & Cathodic areas evolves at the
are small. cathode.
 Wet or Electrochemical Corrosion
 Oxygen consumption type corrosion # The oxide of iron covers the surface of the iron.
 It occurs when metals are in contact with neutral # The small scratch on the surface creates small anodic
solutions like water with dissolved oxygen (DO) area and rest of the surface acts as cathodic area.
# Rusting of iron is an example of this type of corrosion @Anode Oxidation occurs
Fe → Fe2+ + 2 e– (These electrons move
from anode to cathode and react with the
electrolyte and oxygen giving)
@Cathode Reduction occurs
O2 + 2 H2O + 4 e– → 4 OH–
# The Fe2+ at the anode and OH – at the
cathode diffuse and react to produce
Fe(OH)2 which gets further oxidized to
Fe(OH)3 (rust).
Fe + 2 OH – → Fe(OH)2 (green)
4 Fe(OH)2 + O2 + 2 H2O → 4 Fe(OH)3
or 2 (Fe2O3.3H2O) Rust
 Wet or Electrochemical Corrosion

 The reactions involved with Fe are as  Galvanic corrosion or

follows: Differential metal corrosion/Bi-Metallic Corrosion
 Anodic reaction: Metal undergoes  Galvanic corrosion occurs when two different metals are
oxidation (corrosion) with positive release located together in a corrosive electrolyte
of electrons: Fe  Fe+2 + 2e ―  A galvanic couple forms between the two metals, where
 Cathodic reactions: These reactions are one metal becomes the anode and the other the
dependent on the constituents of the cathode
corrosion medium.  Metal with lower reduction potential (anode) undergoes
# If the solution is aerated and almost oxidation and the metal with higher reduction potential
neutral, oxygen is reduced in presence (cathode) undergoes reduction
of H2O to OH− ions.
O2 + 2 H2O + 4e―  4OH ―  The anode or sacrificial metal, corrodes and deteriorates
# If the solution is de-aerated and faster than it would alone, while the cathode
almost neutral, H2 is liberated along deteriorates more slowly than it would otherwise
with OH− ions.  Anodic area always undergoes corrosion and cathodic
2 H2O + 2e―  H2 + 2OH ― area remains unaffected
# If the solution is de-aerated and acidic,  Galvanic corrosion can only occur when there exists an
H+ ions are reduced to hydrogen gas. electric conducting path connecting the metals, eg., an
2 H+ + 2e―  H2 electrolyte
 Galvanic corrosion

 Three conditions must exist for # A metal placed low in Electrochemical series
galvanic corrosion to occur: the electrochemical
 Presence of series is said to be
electrochemically dissimilar anodic to the one Cathodic
metals placed above it (least active)
 The metals must be in
electrical contact, &
 The metals must be exposed
to an electrolyte

(most active)
Anodic
Galvanic corrosion
Electrochemical series

Cathodic
(least active)  Fe is anodic to Cu, Ni and Sn  Fe is cathodic to Zn, Mg

# When Zn is dipped in 1N H2SO4, the rate of corrosion is

quite slow. But, addition of Cu the rate of corrosion
increases significantly.
# In Zn-Cu, Zn acts as anode & Cu acts as cathode

Other examples of Galvanic corrosion:

1. Buried iron pipeline connected to zinc bar.
2. Steel pipe connected to copper plumbing.
3. Steel propeller shaft in bronze bearing.
(most active) 4. Zinc coating on mild steel.
Anodic 5. Lead–tin solder around copper wires.
 Form of Electrochemical Corrosion

Concentration cell corrosion Pitting corrosion

Uniform corrosion Galvanic corrosion
Metal surfaces are in contact Local corrosion occurs with
Generally occurs due An electrochemical action
with diff. concentration of pits at underneath surface
to direct attack that occurs between two
same solution formed due to corrosion
dissimilar metals
product accumulation

Filiform corrosion –
occurs on painted
surface due to
Crevice corrosion Intergranular corrosion penetration of coated
Generally occurs at the surface by moisture
Generally occurs when
grain boundary of a in the form of
metals are in contact
metal/alloy filaments
with non-metal
Form of Electrochemical Corrosion
 Corrosion
 Difference between chemical (dry) corrosion and electrochemical (wet) corrosion

Chemical (dry) corrosion Electrochemical (wet) corrosion

Chemical corrosion occurs in the dry state. It occurs the presence of moisture or electrolyte.
Corrosion products accumulate at the same spot It involves the setting up of a huge number of tiny
where corrosion occurs. galvanic cells.
Involves the direct chemical attack to the metal. Occurs only on heterogeneous metal surface.
It follows absorption mechanism. It follows mechanism electrochemical reactions.
Occurs on homogeneous & heterogeneous surfaces. Corrosion occurs at the anode surface
Uniform corrosion takes place. Pitting is more frequent if anode area is small.
It is slow process It is fast process
Nature of the metal Surface state of the metal
Primary Factors
Formation of protective
Electrode potential difference
 Factors Influencing films by metals
Rate of Corrosion pH Temperature Humidity
Secondary Factors Anodic & Cathodic
Conductance of the medium area effect
Factors Influencing Rate of Corrosion

 Nature of metal: having low  pH: Lower pH  Anodic and cathodic area:
reduction potential are high in mediumhigher Sizes of Anodic and cathodic
reactivity – leads to more corrosion area
corrosion(Li, Na, Mg, Zn). High  Temperature: Rate of
reduction potential metal reaction increases with
associates with less reactivity – increasing temp.
leads to less/no corrosion(Ag, Au,  Conductance of the
Pt,) medium: more
 Ele. Potential difference: Iron and conductance medium
silver = 1.04V (more corrosion) Vs. increases corrosion
Iron and Tin = -0.3V  Humidity: Low
 Surface state of metal- oil, dust, humidity low rate of
water leads corrosion corrosion and vice
 Formation of protective film- The versa
passive layer(Oxides) formation
around the metal. Unstable,
soluble, non-uniform, porous
oxides not able to control the
corrosion
Crevice Corrosion
 Differential aeration corrosion

 If a metal rod is dipped in an electrolyte, the portion dipped in water is poor in oxygen concentration
and works as anode which gets corroded and the portion above water acts as cathode which is
protected.
 The system will act as a concentration cell and the chemical
reactions for zinc dipped in water are given as:

Zn(OH)2 is the corrosion product here.

 Corrosion Resistance
 Selecting materials with similar electrode potentials [e.g., Joining Cu metal and Bronze]
 Breaking the electrical connection by insulating [Plastic washer, Paint] the two metals from each other.
Insulation is typically achieved by using polymer/elastomer-based bushings, washers, gaskets and coatings
 Applying coatings to both materials. The coating on the cathode is the most important and must be in good
condition, otherwise the galvanic corrosion could be worsened.
 Separating the two materials by inserting a suitably sized spacer.
 Installing a sacrificial anode that is anodic to both metals.
 Adding corrosion inhibitor to the environment. The inhibitor will adsorb on the metal surface there by
preventing the contacts of anode and cathode surface with electrolyte or aqueous medium.
 Minimizing the Area Ratio: During the preliminary design stages, it is worthwhile to ensure that the area of
the anodic metal is made as large as possible in relation to the cathode.
 Corrosion resistance methods can be classified as:
 Active corrosion protection: Development of corrosion-resistant alloys or addition of inhibitors
 Passive corrosion protection: Coating by protective layer, film
 Permanent corrosion protection: Tin plating, Galvanization, Coating, Copper plating
 Temporary corrosion protection: Protective coating
 Engineering Chemistry
(CHY1701)
Module -4: Corrosion Control
 Corrosion protection: Cathodic protection – Sacrificial anodic & Impressed
current protection methods, Advanced protective coatings: electroplating &
electroless plating, PVD & CVD.
 Alloying for corrosion protection: Basic concepts of Eutectic composition &
Eutectic mixtures, Selected examples, Ferrous & non-ferrous alloys.
 Module 3: Corrosion Resistance
 Selecting materials with similar electrode potentials [e.g., Joining Cu metal and Bronze]
 Breaking the electrical connection by insulating [Plastic washer, Paint] the two metals from each other.
Insulation is typically achieved by using polymer/elastomer-based bushings, washers, gaskets and coatings
 Applying coatings to both materials. The coating on the cathode is the most important and must be in good
condition, otherwise the galvanic corrosion could be worsened.
 Separating the two materials by inserting a suitably sized spacer.
 Installing a sacrificial anode that is anodic to both metals.
 Adding corrosion inhibitor to the environment. The inhibitor will adsorb on the metal surface there by
preventing the contacts of anode and cathode surface with electrolyte or aqueous medium.
 Minimizing the Area Ratio: During the preliminary design stages, it is worthwhile to ensure that the area of
the anodic metal is made as large as possible in relation to the cathode.
 Control of Corrosion
 Corrosion can be controlled by:
 Proper designing
 Proper selection of metal or alloy
 Cathodic protection
 Anodic protection
 Application of protective coatings
 Use of inhibitors
 Changing the environment
 Design Aspects for corrosion protection
 Avoid sharp corners and sharp edges
 Avoid contact between dissimilar metals
 While working with dissimilar metals – larger anodic area & lesser cathodic area are necessary
 Insulating materials (washers, spacers) can be used when two dissimilar metals required in a fabrication
 For two dissimilar metals – painting/electroplating the anodic metal help in reducing corrosion
 Weld rather than rivet
 Avoid excessive mechanical stress
 Cathodic Protection

 Principle is to make the Base metal to be protected as

Cathode by connecting to a highly anodic metallic plate.
 Two methods of cathodic protection known are
 i) Sacrificial anodic protection
 ii) Impressed current cathodic protection

 Sacrificial anodic protection

 The metallic structure to be protected is connected
through a metal wire to a more anodic metal. This will
induce corrosion at the anodic metal. Thus the anodic Zinc is attached
metal sacrifices itself and gets corroded protecting the to the steel hull
metallic structure. of the vessel
 Sacrificial anodes known are Zn, Mg, Al & their alloys.
 Application: Protection of underground pipelines,
ship hulls and other marine devices, water tanks.
 Sacrificial Anodic Protection

 Advantages:
 No external power is required
 Easy to install
 Anodes can be readily added
 Minimum of maintenance required
 Uniform distribution of current.
# Aluminium anodes mounted on a steel jacket  Disadvantages:
structure – using galvanic corrosion for corrosion  Limited driving potential
control!
 Poorly coated structures may require many anodes
Sacrificial Anode Cathodic Protection  Can be ineffective in high-resistivity environments
https://www.youtube.com/watch?v=cZg4bfEnLcU  Installation can be expensive, if installed after
construction.
 Cathodic Protection
 Impressed current cathodic protection:
 Using direct current larger than the corrosion current
Sacrificial anodic protection

# By imposing a voltage which

causes electrons to flow Vs.
towards the object to be
protected, we make it less
anodic and protect it from
corrosion damage.

Impressed current cathodic protection

https://www.youtube.com/watch?v=QYd9ENn1nP0
 Impressed Current Cathodic Protection
 Advantages:  Corrosion control: Changing the environment
 Enhanced lifespan of shafts, propellers and rudders and  Certain changes in the environment such as
other sea vessel parts involved in electrolysis reduction of acid, oxygen or humidity will
reduce corrosion
 Guarantees simple and dependable operation
 Oxygen can be removed by mechanical
 Maximum corrosion protection documentation at the agitation or by addition of hydrazine or sodium
least overall expense sulphite.
 Single installation needed for the structure or vessel 2 Na2SO3 + O2 → 2 Na2SO4 / N2H4 + O2 → N2 + 2H2O
 Designed to deliver more than 20 years of service.
 Disadvantages:  Dehumidification is carried out by introducing
certain substances like dehydrated aluminina,
 The method is expensive as it requires high current.
anhydrous silica gel etc. (suitable for closed
 Capital investment and maintenance costs are more. areas).
 It is difficult to maintain uniform current over the entire  Neutralization of acidic environment
surface containing H2S, SO2, HCl, CO2 etc., can be done
 The metal should not be over protected, ie, use of much by introducing alkaline neutralizers like
high potential is avoided otherwise problems related to ammonia gas, lime, naphthionic soaps, caustic
cathodic reactions like evolution of H2 and formation of soda etc. (Used in refinery to protect the
OH- Ions takes place leading to corrosion of base metal. equipment).
 Application of Protective Coatings

 Protective coating provide a physical  The most important step before protective coatings are applied
barrier between the metal and the to metals is Surface preparation.
environment.
# Surface preparation is a process to remove rust, oxide scales,
 They not only give corrosion oil, grease, dust etc. If these materials are not removed, the
protection but also add to the protective coating will not be smooth, uniform, cohesive and
decorative value of the article. will not adhere to the metallic surface.
 Coatings are broadly divided as
# Hence, mechanical and electrical methods are used to prepare
 Inorganic coatings: metallic and the surface of the metallic article to be coated clean and free of
chemical conversion coatings. these impurities. Mechanical cleaning, Sandblasting, Solvent
 Organic coatings: paints, varnishes, cleaning, Alkali cleaning, Acid pickling & Etching are normal
enamels, lacquers. processes followed for surface preparation of the article to be
 Protective coatings are classified as: coated.
 Metallic coatings  Mechanical cleaning:
 Chemical conversion coatings • Useful for removing loose scales and rust. Hammering, wire
 Organic coatings and linings brushing, grinding, pneumatic blasting, polishing are the
 Ceramic protective coatings. methods commonly used
 Protective Coatings: Surface Preparation
 Sandblasting:  Alkali cleaning:
• Fine sand or abrasive material along with air • Cleaning of the metal with sodium hydroxide,
stream at a pressure of 25-100 atm is impinged on trisodium phosphate, sodium silicate, soda ash etc.
the metal surface. This will produce enough is carried out to remove old paint coatings soluble
roughness for good adherence of the protective in alkaline medium.
coating. • After alkali cleaning, washing is done with 1%
• Though the method is expensive, it is quite fast chromic acid solution.
and useful
 Acid pickling & Etching:
 Solvent cleaning:
• Base metal is dipped inside the acid solution at
• Solvent cleaning is mainly used to remove oil, grease higher temperature for long periods of time.
and rust from the base metal.
• This treatment ensures cleaning of the metal
• Alcohols, xylene, toluene, chlorinated hydrocarbons surface free from all kinds of impurities
are used. including oils, greases, rust etc.,
• Hot water cleaning is followed after solvent cleaning • H SO , HCl, HF, H PO , HNO are the acids
2 4 3 4 3
is done. commonly used for pickling and etching.
 Application of Protective Coatings: Metallic Coatings
 Classified into Anodic and Cathodic coatings.
 Anodic coatings:  Cathodic coatings:
 Anodic coatings are given on cathodic  Cathodic coatings are given on anodic metals using
metals using metals which are more metals which are more cathodic.
anodic.
 Coating of tin, chromium, nickel on iron surface are
 Zinc, Aluminium, Cadmium coatings on
cathodic coatings. If there is a discontinuity in the
Iron are anodic coatings. If the coating
coating, then galvanic couple will form with base metal
breaks, then a galvanic couple is set up and
as anode and the coated metal as cathode.
corrosion rate gets enhanced.
 During this process, the anodic coating gets  Then the process of corrosion will start by the base
disintegrated but it protects the cathodic metal ions going into solution and the metal
base metal. Hence, the anodic metal deteriorating.
sacrifices itself to protect the base metal.  To avoid this, the article is checked and re-plated
 This type of coating is known as periodically so that there is no discontinuity in the
Galvanisation. coating.
 Metallic Coatings: Methods
I. Hot dipping:
I. Hot dipping  Hot dipping process is applicable to the metals (Base metal)
II. Electroplating having higher melting point than the coating metal.
III. Electrolessplating  It is carried out by immersing a well cleaned base metal in
IV. Physical Vapor Deposition (PVD) a bath containing molten coating metal and a flux layer.
V. Chemical Vapor Deposition (CVD) The flux cleans the surface of the base metal and prevents
the oxidation of the molten coating metal.
 Exmple: Coating of Zn, Pb, Al on iron and steel surfaces
B. Tinning  Two types: (A) Galvanization and (B) Tinning
 The process of coating tin metal over the
iron or steel A. Galvanization
 Uses: Tinning is widely used for coating  Galvanization is a process in which the iron
steel, Cu and brass sheets which are used article is protected from corrosion by coating it
for making containers for storing food stuff, with a thin layer of Zn. It is the anodic
oils, kerosene and packing of food protection offered by the zinc.
materials. Tinned Cu sheet are used for  Uses: Galvanization is used to protect Iron from
making cooking utensils and refrigeration corrosion for roofing sheets, buckets, bolts, nuts,
equipment. nails, pipes, wires, screws, rods etc.
I. Hot Dipping: Galvanizing vs. Tinning
 II. Electroplating

 It is the process by which the coating metal is

deposited on the base metal by passing a direct
current through an electrolytic solution containing
the soluble salt of the coating metal
 Electroplating is done for improving corrosion
resistance, wear resistance, chemical resistance,
surface hardness, appearance
 Both ferrous and non-ferrous metals are plated with
Ni, Cr, Cu, Zn, Pb, Al, Ag, Au, Sn etc.
 Electroplating is mainly used in automobile, aircraft,
refrigerator, chemical and electrical appliances etc.

 Theory of Electroplating  If the anode is made of coating metal itself in the

electrolytic cell, during electrolysis, the concentration
 The base metal to be plated is made cathode of an of electrolytic bath remains unaltered. If the anode is
electrolytic cell, whereas the anode is either made made of an inert material like graphite, electrolyte
of the coating metal itself or an inert material of should be added continuously to maintain the
good electrical conductivity. concentration of the coating metal ions in the bath.
 Important Factors of Electroplating
 Cleaning of the article is essential  Thickness of the deposition
 pH of the bath: For a good
for strong adherence of the should be optimised to get a
electrodeposit, the pH of the
electroplating. strong & adherent deposition.
bath must be properly
 Scraping, grinding, sand blasting,  For corrosion protection multiple maintained (ranges from 4 – 8)
wire brushing, solvent cleaning and coatings are given without any
 Method of Electroplating:
acid pickling are used for surface discontinuity. Thin coating is for
Depends upon the type of
cleaning. decorative purpose.
metal, the size and type of
 A well cleaned and properly pre  Current density is the current per article to be electro-plated.
treated surface of any material to unit area of the article being Besides, main objectives &
be electroplated is necessary for plated (amps cm-2). It should be economics are also
obtaining the coating of long life. maintained at optimal level to get considered.
uniform & adherent deposition.
 Concentration of the electrolyte is  Throwing power is the ability
another important factor.  Additives to electrolytic bath: of electrolytic cell to give a
Added in small quantities to get deposit of uniform thickness
 Low concentration of metal ions will
strong adherent deposition. over the entire cathode area.
give uniform coherent deposition.
Commonly used additives are
 To maintain low conc. of metal ions,  Maximum throwing power can
gelatin, glue, glycine, boric acid
complexing agents are added to the be attained when cathode has
etc. & brighteners for bright
electrolyte. regular shape.
plating.
 Electroplating: Plating Bath Solution
 It is a highly conducting salt solution of the Electroplating with Nickel on Copper
metal which is to be plated. However, non-
participating electrolytes are added to the bath
solution to increase the conductivity and the
throwing power.
 For sufficient throwing power, mixture of two
or more electrolytes are used for electrolytic
bath.
Copper
 It should be good conductor and highly soluble. Cathode is Nickel
It should not undergo hydrolysis, oxidation, reduced Anode is
reduction and other chemical changes. (accepts oxidized
 The level of the plating bath should cover electrons) (gives
completely the cathode and sufficient area of electrons)
anode. Ni2+ ions within solution
 Heating (if required) can be provided. become attracted to
 Air sparger or nitrogen sparger is employed to Copper cathode
introduce convection current in the plating bath
solution.
 III. Electrolessplating
 Electrolessplating is the controlled  Copper electrolessplating
autocatalytic deposition of a metal on a
substrate (conductor/Nonconductor)
from its salt solution on a catalytically
active surface by a suitable reducing
agent without using electrical energy.
This process is also called autocatalytic
plating, since it takes place on catalytic
surface.
 The metallic ions (M+) are reduced to the
metal with the help of reducing agents
(R-). When the metal (M) is formed, it
gets plated over a catalytic surface.
 The electrolessplating involving a nickel sulfate bath
M+ + R- →M+R
 Typically, sodium hypophosphite is used
as a reducing agent. Also, formaldehyde,
hydrazine, borohydride, amine boranes,
and their derivatives could be utilized
 III. Electrolessplating
 Advantages of electrolessplating:  Differences
 Electrical energy is not required. Electroplating Electrolessplating
 Even intricate parts (of irregular Driving force Electric current Autocatalytic reduction
shapes) can be plated uniformly. reaction
 There is flexibility in plating volume Electrodes Separate anode and Catalytically active
and thickness. The process can plate cathode surface
recesses and blind holes with stable
thickness. Applicability Deposition can’t be made Deposition can be
 Chemical replenishment can be on non-conductors such as made on non-
monitored automatically. plastics, ceramics etc. conductors such as
 Plating on articles made of plastics, ceramics etc.
insulators (like plastics) and Throwing power Low High
semiconductors can easily be
carried out. Nature of Pure metal Metal contaminated
deposit with reducing agents
 It is a pore free coatings with very and oxidizing agents
high hardness, corrosion resistance
and wear resistance values. Additives Levelers are added. Levelers are not
required.
 IV. Physical Vapour Deposition (PVD)
 Physical Vapour Deposition (PVD)
 Thin Film Coatings or Industrial Coatings
 PVD is a process used to produce a metal
 Technology of applying a very thin film of material vapour that can be deposited on electrically
between a few nanometers to about 100 μm. conductive materials as a thin, highly adhered
 Thin film deposition is usually divided into two pure metal or alloy coating. This coating process
broad categories produces coating thickness in the range 1 to 10
 Physical Vapour Deposition (PVD) µm.
 Chemical vapour Deposition (CVD)  It involves physically deposition atoms, ions or
molecules of a coating species on to a substrate.
 The process of thin film coating by means of
PVD is to apply electric current and voltage or
bombardment of inert gas to ionize the desired
material. Once the material is ionized into vapor
form it is the deposited on the desired
substrate. PVD methods use clean and dry
vacuum deposition.
 Coating is deposited over the entire object
simultaneously, rather than in localized areas
 IV. Physical Vapor Deposition (PVD)
 There are three main types of PVD: a. Thermal evaporation
 It uses the heating of a material to form a vapour
a. Thermal evaporation (vacuum thermal evaporation) which condenses on a substrate to form the coating.
b. Sputtering and  Heating is achieved by
c. Ion plating various methods including
hot filament, electrical
 All these three processes are resistance, laser beam,
performed under vacuum. electric arc, electron beam
Vacuum evaporation is also
known as vacuum deposition  The surface to be coated
needs to have a higher
 Material used for coating is
melting temperature than
thermally vaporized and then
the coating metal and this
proceeds by potential
limits the choice and make
differences to the substrate
more complicated to mix
with little or no collisions with
the components
gas molecules.
 Normal vacuum levels are in  no chemical bonding between the coatings & substrates is established.
the medium to high vacuum  When the coating materials hit the substrate, it is physically deposited as
range of 10-5 to 10-9 Torr. layers or atom by atom or molecules by molecules.
 IV. Physical Vapor Deposition (PVD)
b. Sputtering Method
 Sputtering is a process whereby particles are ejected from a solid
target material due to bombardment of the target by
energetic particles.
 Sputtering involves the electrical generation of a plasma between
the coating species and the substrate.
 Plasma is a “state of matter similar to gas in which a certain
portion of the particles are ionized”
 In this method a controlled gas, usually chemically
inert argon, is introduced into a vacuum chamber
and electrically energized to establish a self
sustaining plasma.
 The argon ion (Ar+) will move toward to cathode with high
speed and sputter the target material.
 The target atom or molecular will be hit to substrate
surface and condense as a film.
# Instead of heat melting in evaporation method, the plasma Ar+ ion hit and
sputter the target is the main mechanism in plasma sputtering method.
 PVD: Sputtering Method
 The target atom is knocked out by Ar+ ion. The knock force is so big
 Types of Sputtering:
that it can accelerate target atom a high speed. With such velocity, the
 DC sputtering.
target atom can hit and attach to substrate surface deeply.
 Magnetron sputtering.
 The film density is good compared to thermal evaporation
 Radio frequency (RF) sputtering.
 For efficient momentum transfer, the atomic weight of the sputtering
 Reactive gas sputtering.
gas should be close to the atomic weight of the target. For sputtering
 Ion beam sputtering.
light elements neon is preferable, while for heavy elements krypton or
 Pulse DC/AC sputtering.
xenon are used.
 Applications of Sputtering method:
 This method is used in VLSI fabrication (Very-large-scale integration: process of creating an integrated
circuit (IC) by combining hundreds of thousands of transistors or devices into a single chip)
 Sputtering is used extensively in the semiconductor industry to deposit thin films of various materials in
integrated circuit processing.
 Thin antireflection coatings (MgF2 and Fluoropolymers; mesoporous silica materials; titanium nitride and
niobium nitride) on glass for optical applications are also deposited by sputtering.
 An important advantage of sputter deposition is that even materials with very high melting points are easily
sputtered while evaporation of these materials in a resistance evaporator or Knudsen cell is problematic or
impossible. Sputter deposited films have a composition close to that of the source material.
PVD: Sputtering Method
 Sputtering offers the following advantages
over other PVD methods used in VLSI  Disadvantages of Sputtering:
fabrication:
 High capital expenses are required
I. Sputtering can be achieved from large-size
targets, simplifying the deposition of thins  The rates of deposition of some materials
with unifrom thickness over large wafers (such as SiO2) are relatively low
II. Film thickness is easily controlled by fixing
 Some materials such as organic solids are
the operating parameters and simply
easily degraded by ionic bombardment
adjusting the deposition time
III. Control of the alloy composition, as well as  Sputtering has a greater tendency to introduce
other film properties such as step coverage impurities in the substrate than deposition by
and grain structure, is more easily evaporation because the former operates
accomplished than by deposition through under a lesser vacuum range than the latter.
evaporation
 The coatings are having very poor crystallinity
IV. Sputter-cleaning of the substrate in vacuum
prior to film deposition can be done  Formation of holes inside the coating matrix
V. Device damage from X-rays generated by due to very energetic hitting of target atoms.
electron beam evaporation is avoided.
 IV. Physical Vapor Deposition (PVD)
c. Ion plating
 Ion plating is the combination of thermal
evaporation and sputtering methods. sometimes
called ion assisted deposition (IAD) or ion vapor
deposition (IVD).
 Metal is evaporated thermally and plasma is established to
ionize the evaporated species.
 Evaporated metal ions bombard the substrate with high energy.
 They physically implant into the substrate to produce an
extremely strong coating bond.
 Sputter and ion plated coatings are used in design for very thin films for
electrical, optical and wear-resistant applications.
 The wear properties of tools are greatly enhanced by hard thin film coatings.
 Sputtered coating processes produce microscopic modules of diameter of several micrometers and they are
called macros.
 IV. Physical Vapor Deposition (PVD)
 Advantages of PVD coating:  Disadvantages of PVD coating:
 Materials can be deposited with improved ≠ It is extremely difficult to coat undercuts and
properties compared to the substrate complicated surface features.
material. ≠ High capital cost.
 Almost any type of inorganic material can be ≠ Some processes operate at high vacuums and
used as well as some kinds of organic temperatures requiring skilled operators.
materials.
≠ Process emit large amounts of heat and hence require a
 The process is more environmentally friendly cooling system.
than processes such as electroplating.
≠ The rate of coating deposition is usually quite slow.
 Applications of PVD methods
 This process is widely used to produce decorative coatings on plastic parts those are
resembling shiny metal.
 Many automobile parts are plastic with a PVD coating of aluminium.
 A polish coating is applied over the decorative coating to provide corrosion protection.
 This process is also used to apply relatively thick (1 mm) coatings of heat resistant
materials on jet engine parts
 PVD coating is widely used for artificial medical implants.
 V. Chemical Vapor Deposition (CVD)
 CVD is one of the most common processes used to coat almost
any metallic/ceramic compound, including elements, metals
and their alloys and inter-metallic compounds.
 The CVD process involves depositing a solid material from a
gaseous phase
 Coating process uses thermally induced chemical reactions
at the surface of a heated substrate, with reagents
supplied in gaseous form
 Precursor gases are delivered into the reaction chamber.
As they pass over or come into contact with a heated
substrate, they react or decompose forming a solid phase
which are deposited onto the substrate.
 The substrate temperature is critical and can influence what reactions will take place
 A CVD apparatus will consist of following basic components
o Vacuum system,
o Gas delivery system,
o Exhaust system,
o Reactor chamber,
o Exhaust treatment systems,
o Substrate loading mechanism,
o Process control equipment
o Energy source,
 V. Chemical Vapor Deposition (CVD)
 Gas delivery system: For the supply of precursors  Applications of CVD
to the reactor chamber  Coatings: Coatings for a variety of applications such as
 Reactor chamber: Chamber within which wear resistance, corrosion resistance, high temperature
deposition takes place protection, etc.
 Substrate loading mechanism: A system for
introducing and removing substrates, mandrels etc  Semiconductors and related devices: Integrated circuits,
 Energy source: Provide the energy/heat that is sensors and optoelectronic devices
required to get the precursors to  Optical Fibers: For telecommunications.
react/decompose.  Dense structural parts: To produce components that are
 Vacuum system: A system for removal of all other difficult/uneconomical to produce using conventional
gaseous species other than those required for the fabrication techniques.
reaction/deposition.  Composites: Preforms can be infiltrated using CVD
 Exhaust system: System for removal of volatile by- techniques to produce ceramic matrix composites such
products from the reaction chamber. as carbon-carbon, carbon-silicon carbide and silicon
 Exhaust treatment systems: In case exhaust gases carbide-silicon carbide composites.
may require treatment or conversion to  Powder production: Production of novel powders and
safe/harmless compounds. fibres
 Process control equipment: Gauges, controls etc to
 Nanomachines
monitor process parameters such as pressure,
temperature and time.  CVD is also used to produce synthetic diamonds
 V. Chemical Vapor Deposition (CVD)
 Advantages:
 CVD coatings are typically fine grained
and of high purity.
 Harder than similar materials produced
using conventional ceramic fabrication
processes. CVD coatings are used to
make explosion or shatter resistant
glasses.
 The main advantage of CVD process
over PVD is that it is not line of sight.
All surfaces in the reaction chamber get
coated.
 Disadvantages:
≠ Separate process and reaction must be
developed for each coating.
≠ Some of the gases are toxic and dangerous.
≠ Greatest disadvantage is temperature of the substrate should be very high at 700°C. At this temperature,
many metals (substrates) soften.
 Alloying for Corrosion Protection
 Alloy is a homogeneous substance formed by mixing two or
more elements, at least one of them being a metal
 Types: Alloys are of three types.
 Formed by two or more metals; eg. Cu-Zn (Brass)
 Formed between a metal & a non-metal; eg. WC
 Formed between mercury & another metal; eg. Zinc amalgam
 Characteristics of alloys:
 Chemical Properties are modified
 Hardness and tensile strength of the alloy is higher
⃝ Dissolution of alloy in HCl is lower
⃝ Tensile strength of Fe 10 fold increases by alloying with 1% Carbon compared to its constituent metals
 Melting points of alloys is generally lower  Corrosion resistances: Generally
⃝ Solder melts at 183°C; while Pb melts at 327°C and Sn melts at 232°C alloys are more resistant to
corrosion than pure metals.
 Alloys are less conductive than pure metals
⃝ Stainless steel (alloy of Fe, C, Ni &
⃝ Small quantity of impurities in copper will reduce its conductivity Cr) is not corroded by atmospheric
 Colour of alloy gets modified conditions though pure Fe
⃝ Red coloured copper & Silver white Zinc provide Yellowish brown brass corrodes heavily in moist
environment.
 Alloying for Corrosion Protection
 Significance of Alloying  Basic concepts of Eutectic composition
 The alloy coatings bring quality, reliability and durability  Phase
for process vessel linings and pipe linings along with the
surface protection of components and equipment
against extreme conditions such as high temperature,
higher abrasion or high acidity surroundings.
 Alloying Increases mechanical strength, reduce chemical
reactivity, change electrical conductivity, increase
corrosion protection
 Examples
 Lead-Tin alloys – for soldering purpose
 Nickel alloys – for resistance to extreme corrosion &
high temperature requirements.
 Copper-nickel alloys – for anti-fouling resistance.  When a phase in one form is altered to another form, a
phase change is said to have occurred. Phase change
 Iron-nickel alloys – for low thermal expansion
generally occurs by addition/removal of thermal energy
 A heterogeneous system is defined as a system consisting
of a number of phases in equilibrium
 Basic Concepts of Eutectic Composition
 A phase diagram is a type of chart used to  Generally the phases at equilibrium are studied under
show conditions (pressure, temperature, the conditions considering following variables
volume) at which thermodynamically distinct  Temperature & Pressure or Temperature & Composition
phases (such as solid, liquid or gaseous states)
occur and coexist at equilibrium  Phase diagram is one of the most succinct ways of
presenting the physical changes of state that a
substance can undergo.
 For two component systems
 Temperature, pressure and composition are
Water required to define the system
 This leads to 3-dimensional figures which cannot
Ice be explained on a paper. Hence one of the three
variable to be kept constant.
 The composition variable zB is the mole fraction
of component B in the system as a whole.
Vapour  The measurement is carried out in an open vessel
to keep the system under constant atmospheric
pressure
 Basic Concepts of Eutectic Composition
• Tf,A* = freezing point of A • The curve Tf,A* = FP of B to which A is being added
• Tf,B* = freezing point of B • The curve Tf,B* = FP of A to which B is being added
• These two curves represent condition of temperature
at which the liquid mixture is in equilibrium with solid
A and solid B
Point ‘a’ = meeting point of the curves Tf,A* &
Tf,B*. At this point three phases, solid A, solid B
and the liquid mixture, are in equilibrium.
The point ‘a’ correspond to a temperature below
which any liquid mixture of A and B will freeze as
a whole. This is known as the Eutectic Point.
The composition at this point is the eutectic
composition, and the temperature here (denoted
Te ) is the eutectic temperature

 Composition of any point, say d, can be obtained by

drawing a horizontal line passing through the
particular point to find where it cuts the curves Tf,A*
& Tf,B*
 Eutectic System
 The line connecting the composition of  Examples:
the solid and liquid phases in These mixtures typically have useful properties that are not
equilibrium is called the tie line possessed by any single constituent substance.
 Eutectic system is a homogeneous, solid  Sodium chloride and water form a eutectoid (23.3% salt by
mixture of two or more substances that mass with a eutectic point at -21.2 °C. The system is used to
form a super-lattice; the mixture either make ice cream and to melt ice and snow.
melts or solidifies at a lower
temperature than the melting point of  Eutectic alloys are used for many purposes:
any of the individual substances.  Pb (FCC) and Sn (tetragonal) - solder systems
 Eutectic point: Minimum freezing point  Fe (BCC) and C (graphite - hexagonal) - cast irons
attainable corresponding to the eutectic  Al (FCC) and Si (diamond cubic) - cast aluminum alloys
mixture is called eutectic point.  Cu(FCC) and Ag(FCC) – high temperature solder
 A eutectic system contains two solid  Eutectoid glassy metals exhibit extreme corrosion resistance
phases at low temperature. These and strength.
phases may have different crystal
structures, or the same crystal structure  Inkjet printer ink is a eutectic mixture
with different lattice parameters.  Galinstan is a liquid metal alloy (composed of gallium, indium,
and tin) used as a low-toxicity replacement for mercury
Eutectic System

 Solidification starts @ nucleation sites

 Nucleation sites grow
 Entire alloy becomes solid
Basic Concepts of Eutectic Composition

 Isomorphous phase diagrams

 In crystallography crystals are described as isomorphous if

they are closely similar in shape.
 Cu-Ni Alloys follow Hume-Rothery rules
Hume-Rothery rules for solid solutions
1. The atomic radius of the solute and solvent atoms must
differ by no more than 15%.
2. The crystal structures of solute and solvent must be similar.
3. Complete solubility occurs when the solvent and solute
have the same valency. (A metal of higher valency is more
likely to dissolve in a metal with lower valency).
4. The solute and solvent should have similar electronegativity
(If the electronegativity difference is too great, the metals
tend to form intermetallic compounds instead of solid
solutions).
Metals and Alloys
 Applications of Ferrous alloys
 Ferrous steel is produced as
sheet for automobiles,
appliances, and containers
 As plates for ships, boilers
and bridges
 Bar products for leaf springs,
gears axles, crank shaft and
railroad rails
 As wire and fasteners such as
bolts, rivets and nuts
 Ferrous materials comprise
70% to 85% by weight of
virtually all structural
members and mechanical
components.
 Carbon steels are least
expensive.
Ferrous Alloy
 The Iron ‐Iron Carbide (Fe‐Fe3C)
Phase Diagram
 C: an interstitial impurity in Fe
 It forms a solid solution with α,
γ, δ phases of iron
 maximum solubility in BCC
α‐ferriteis 0.022 wt % @ 727 °C.
 Maximum solubility in FCC
austenite is 2.14 wt% at 1147 °C
 Mechanical properties:
Cementite (Fe3C) is hard and
brittle: strengthens steels
 Mechanical properties also
depend on microstructure: how
ferrite and cementite are mixed
 Magnetic properties: α‐ferrite is
magnetic below 768 °C
 Austenite is non‐magnetic
Non-ferrous Alloys
 Some applications of non-ferrous alloys
 Copper Alloys:
• One of the largest usea of Cu is probably in coins.
• Euro coins are made of Cu-Ni, Cu-Zn-Ni or Cu-Al-Zn-Sn alloys.
• Brasses and Bronzes are most commonly used alloys of Cu.
• Brass is an alloy with Zn.
• Bronzes contain tin, aluminum, silicon or beryllium.
• More than 400 copper-base alloys are recognized.
 Magnesium Alloys:
• Aerospace industry,
• High speed machinery
• Transportation and materials handling equipments
 Nickel Alloys:
• Corrosion resistant parts: Valves, pumps, vanes Heat exchangers, shafts, impellers
• Heat treatment equipments, Gas turbines, Chemical reactor, etc
Non-ferrous Alloys
 Lead-Tin Phase Diagram
 The curves AO & BO meet at the point
A O is called eutectic point. Here, solid
Sn, Solid Pb and solution of Sn & Pb
are in equilibrium. The point O (183
°C) represents a fixed composition of
Eutectic point (O) B 61.9 % Sn and 38.1 % Ag, and is called
eutectic composition.
 Area above AOB: Ag and Pb exist as
Eutectic solution
temperature  Although lead-tin alloys are too weak
for use as structural materials, they
are widely used as solders for
everything from joining copper
plumbing to soldering electrical
circuits. However, there is an
international effort to develop lead-
free solders because of the health
concerns associated with lead.
 Engineering Chemistry
(CHY1701)
Module -5: Electrochemical Energy Systems
 Brief introduction to conventional primary & secondary batteries
 High energy electrochemical energy systems: Lithium batteries – Primary and secondary,
its Chemistry, advantages and applications.
 Fuel cells – Polymer membrane fuel cells, Solid-oxide fuel cells: working principles,
advantages, applications.
 Solar cells – Types, Importance of silicon single crystal, polycrystalline & amorphous silicon
solar cells, dye sensitized solar cells: working principles, characteristics & applications
 Electrochemical Cell

 An electrochemical cell is a device in which a redox

reaction is utilized to get electrical energy.
Commonly referred to as voltaic or galvanic cell.
 The electrode where oxidation occurs is called
anode while the electrode where Reduction occurs
is called CAthode.
 An electrolytic cell is one in which the electrical
energy is converted to chemical energy and resulting
in a chemical reaction
 Battery: A device that consists of one or more
electrochemical cells connected in series or
parallel or both and converts the chemical
energy by means of an electrochemical
oxidation-reduction reaction depending on
their desired output voltage and capacity  Zn Electrode dipped in ZnSO4 solution: Oxidation
 Cu Electrode dipped in CuSO4 solution: Reduction
 Each electrode is referred to as half cell which are
connected through a salt bridge
 Cell/Battery
 The cell consists of three major components:  Basic Concepts of Cells and Batteries
A. The anode or negative electrode: It gives up  When two dissimilar metals are immersed in an
electrons to the external circuit and is oxidized electrolyte, there will be a potential difference
during the electrochemical reaction. produced between these metals
B. The cathode or positive electrode: It accepts  If they are immersed in same electrolyte solution,
electrons from the external circuit and is reduced one of them will gain electrons and the other will
during the electrochemical reaction release electrons. As a result, there will be a
C. The electrolyte: It is the ionic conductor which difference in electron concentration between these
provides the medium for transfer of charge, as two metals.
ions, inside the cell between the anode and  This difference of electron concentration causes an
cathode electrical potential difference to develop between
the metals or compounds.
 This electrical potential difference or emf can be
utilized as a source of voltage in any electronics or
electrical circuit.
 All battery cells are based only on this basic
principle.
 Cell/Battery
 Representation of galvanic cell
 Primary battery (Primary cells): The cell reaction is
 Anode is written on the left-hand side
not reversible. When all the reactants have been
 Electrode on the left, Metal| Electrolyte (conc.) converted to product, no more electricity is
produced and the battery is dead.
# Zn|ZnSO4 (1M)
# Example: Lechlanche Cell (Dry Cell), Alkaline Cell and
 Cathode is written on the right hand side Lithium batteries.
 Electrode on the right, Electrolyte (conc.)| Metal  Secondary battery (secondary cells): Cell reactions
can be reversed by passing electric current in the
# CuSO4 (1M)|Cu
opposite direction. Thus it can be used for a large
 A salt bridge is indicated by two vertical lines, number of cycles.
separating the two half cells # Example: Lead acid batteries, Ni-Cd batteries, Ni-
Zn|Zn2+ (1M) ║ Cu2+ (1M)|Cu Metal Hydride batteries, Lithium ion batteries.
 Important applications: It has wide variety of  Flow battery and fuel cell: Materials (reactants,
applications & there market is very potential products, electrolytes) pass through the battery,
 Car batteries – Pb/acid cell which is simply an electrochemical cell that converts
 Portable electronics – secondary battery chemical to electrical energy.
 Low power applications – primary battery # Example: Hydrogen-oxygen fuel cell (HOFC), Alkaline
 From military applications to medical applications fuel cell (AFC), Solid oxide fuel cell(SOFC), etc.
 Lithium Primary Batteries

 Lithium batteries have high charge density and long life  Lithium-Manganese Dioxide Cell
 The electrolyte in this system is a solid
 Lithium cells can produce voltages from 1.5 V – 3.7 V
(comparable to a Zn-C or alkaline battery)  The active cathode material consists of a specially
prepared [treated @ 300 °C] mixture of
 Lithium cells are primary cells in which lithium acts as electrolytic MnO2 and other specific components.
anode and the cathode may differ. It yields an outstanding volume/capacity ratio.
 The main attractions of lithium as an anode material is  Anode: Lithium metal
● Most electropositive metal @ electrochemical series  Cathode: Carbon in contact with MnO2
● It has very low density  Electrolyte: LiBF4 salt in a mixture of propylene
● Largest amount of electrical energy per unit weight carbonate and dimethoxy ethane.
 Li can’t be used with traditional aqueous electrolytes  Voltage: 3 V
o Very vigorous corrosive reaction between Li and water  Li|Li + (nonaqueous)/nonaqueous Li salt
o Flammable hydrogen as the product. paste|MnO2-|MnO2, C
or, Li/Li+(nonaqueous)|MnO2
 Reactions: @ Anode: Li → Li+ + e- , @ Cathode: MnO2 + e- → MnO2-
 Net reaction: Li+ + MnO2 → LiMnO2
 Lithium Primary Batteries

 Lithium-Manganese Dioxide Cell: Alkaline medium  Li-SOCl2 Cell

 The cell is represented as  It consists of high
Li|Li+(nonaqueous)|KOH(paste)|MnO2,Mn(OH)2,C surface area carbon
cathode, a non-woven
 The electrolyte is a paste of aqueous KOH. glass separator.
@ anode: Li → Li+ + e-  Thionyl chloride acts
as an electrolyte & as
@cathode: MnO2 + 2H2O + e- → Mn(OH)2 + OH-
a cathode.
Net reaction: Li + MnO2 + 2H2O → Li+ + Mn(OH)2 + OH-
 Sometimes LiGaCl4 is added to avoid its decomposition

 Applications  Cell reaction: @ Anode: Li → Li+ + e

@Cathode: 4Li+ + 4e- + 2 SOCl2 → 4 LiCl + SO2 + S
 The coin type cells are used in watches and
calculators. Net reaction: 4 Li+ + 2 SOCl2 → 4 LiCl + SO2 + S
 Cylindrical cells are used in fully automatic cameras  Li-SOCl2 Cell is an example of liquid cathode. The
co-solvents used are acrylonitrile or propylene
carbonate (or) mixture of the two with SO2 in
50% by volume. 2 Li + 2 SO2 → Li2S2O4
 Lithium Secondary Batteries
 Use of Li-SOCl2 Cell  Secondary Lithium Batteries or Lithium ion (Li ion) battery
 They are used for  Lithium-ion battery is a secondary battery, also known as rocking chair battery
military and space
 It does not contain metallic lithium as anode.
applications.
 The movement of lithium ions are responsible for charging & discharging.
 In medicinal devices
such as neuro-  Lithium-ion cell has the following three components:
stimulators, drug
• Cathode: Layers of lithium-
delivery system, metal oxide (LiCoO2, LiNiO2
lithium batteries are and LiMn2O4)
widely used.
• Anode: Layers of porous
 They are also used in carbon (graphite, usually
electric circuit boards with composition Li0.5C6
for supplying fixed • Electrolyte: Polymer gel,
voltage for memory organic liquid, gel, polymer
protection and and ceramic-solid
standby functions. electrolytes
 Lithium Secondary Batteries

 Advantages/Characteristics:
 Lithium-ion batteries are high voltage
and light weight batteries.
 It is smaller in size & produces three
time the voltage of Ni-Cd batteries.
 Uses: It is used in cell phone, note PC,
portable LCD TV, semiconductor driven
audio, etc.

 Charging Reaction:  Disharging Reaction:

 During charging, Li+ ions flow from the positive  Li+ ions flow back through the electrolyte form
electrode (LiCoO2) to the negative electrode (graphite) negative electrode to the positive electrode.
through the electrolyte. Electrons flow from the negative electrode to the
 Electrons also flow from the positive electrode to the positive electrode.
negative electrode. The electrons and Li+ ions combine  The Li+ ions and electrons combine at the positive
at the negative electrode and deposit there as Li. electrode and deposit there as Li
Lithium Secondary Batteries
 Lithium polymer (Poly-Carbon Monofluoride) batteries
 Polycarbon monofluoride cells have an output of 2.8 V
and moderately high energy density.
 Commercial Li/CFx battery:
 Cathode: Composite of CFx, conductive additive and
a polymeric binder
 Anode: Lithium
 Polypropylene separator and a non-aqueous
electrolyte (such as LiBF4 in γ-butyrolactone).
 Discharge reaction: CFx + xLi + xS → C(Li+SF-)x
C(Li+SF-)x → C + xLiF + xS
 Lithium Polymer batteries are better than
Lithium ion batteries
 Li-ion batteries use organic solvents as
dispersing medium. In situations where the
structure of the battery is compromised, that
solvent can ignite and vent from the
pressurized battery. The result is a dangerous
explosion
 Fuel Cells
 Operation Principle:
 It uses hydrogen (or hydrogen-rich fuel) and oxygen to create
electricity by an electrochemical process
 Hydrogen and oxygen (air) are supplied to anode & cathode.
 When hydrogen is led to anode,
the hydrogen molecules are split
into proton & electron [oxidation].
 It is a device that converts chemical
 Protons migrate through the
potential energy (energy stored in
electrolyte to cathode for reacting
molecular bonds) into electrical
with oxygen to form water
energy
[Reduction].
 Electricity is generated by combining
 At the same time, the electrons
hydrogen & oxygen (without
are forced to travel around the
combustion) to produce water & heat
electrolyte to the cathode side –
 They offer higher electrical efficiency This movement of electrons thus
(≥40%) compared to conventional creates an electrical current
power generation systems.
 Fuel Cells

 There are eight main types of fuel cells –  Hydrogen – Oxygen Fuel Cells
based mainly on the type of electrolyte  This cell is a common type of fuel cell. Similar to a galvanic
a) PEMFCs: Proton Exchange cell, fuel cell also have two half cells.
Membrane/Polymer Electrolyte  Both half cells have porous graphite electrode with a
Membrane Fuel Cells catalyst (platinum, silver or a metal oxide).
b) AFCs: Alkaline Fuel Cells  The electrodes are placed in the aqueous solution of NaOH
or KOH (alkaline fuel cells-AFC) or H2SO4 (acidic fuel cell)
c) PAFCs: Phosphoric Acid Fuel Cells
which acts as an electrolyte.
d) MCFCs: Molten Carbonate Fuel Cells  Hydrogen and oxygen are supplied at anode and cathode
e) SOFCs: Solid Oxide Fuel Cells respectively at about 50 atmospheric pressure, the gases
f) DMFCs: Direct Methanol Fuel Cells diffuse at respective electrodes.
g) DAFCs: Direct Ammonia Fuel Cells  The overall chemical reaction in a hydrogen fuel
electrochemical cell involves the oxidation of hydrogen by
h) DCFCs: Direct Carbon Fuel Cells oxygen to produce only water. 2 H2 + O2 → 2 H 2 O
 Apart from DAFCs, DMFCs, and DCFCs other
types of fuel cells are fed with hydrogen
 AFCs
 Alkaline fuel cells (AFCs)
 Alkaline fuel cells consume hydrogen and pure
oxygen producing potable water, heat & electricity.
 Structure:
 Anode & Cathode: Inert and porous graphite
electrode impregnated with finely divided
platinum catalyst or alloy of Pd, Ag & Ni serves the
purpose.
 Hydrogen (through anode) and oxygen (through
cathode) gases are bubbled through the respective
compartments.
 Electrolyte: 25 % KOH hot solution (alkaline).
 OH- ions migrate from the cathode to the anode.
 At the anode, hydrogen gas reacts with the OH-
ions to produce water and release electrons.

@anode: 2 H2 (g) + 4 OH- (aq) → 4 H2O (I) + 4 e- [E ˚Anode = -0.83 V]  Released electrons supply electrical power
@cathode: O2 (g) + 2 H2O (I) + 4 e- → OH- (aq) [E ˚Cathode = 0.40 V] to an external circuit then return to the
 Net reaction: O2 (g) + 2 H2 (g) → 2 H2O (I) [E ˚Cell= 1.23 V] cathode where electrons react with oxygen
and water to produce more hydroxyl ions
 AFCs
 Sulphuric acid fuel cell  Advantages  Application:
• Energy conversion is very high (75-82%). • The most
 Phosphoric acid fuel cell (PAFC)
• It has high reliability in electricity generation. important
• The by-products are environmentally acceptable. application of a
• Maintenance cost is low for these fuels. fuel cell is its use
in space
• They save fossil fuels. vehicles,
• Noise and thermal pollution are very low submarine or
 Disadvantages: military vehicles.
• The major disadvantage of the fuel cell is • The product H2O
the high cost and the problems of durability is valuable
and storage of large amount of H2. source of fresh
water for the
• The accurate life time
astronauts.
• It cannot store electricity
• Fuel cell
 At anode: H2 (g) → 2 H + 2 e
+ - • Electrodes are expensive and short lived. batteries for
 At cathode: O2 (g) + 4 H+ + 4 e- → 2 H2O • Storage and handling of H2 gas is dangerous automotive will
because it is inflammable be a great boon
 Net reaction: O2 (g) + 2 H2 (g) → 2 H2O (I) for the future.
 PEMFC

 Proton exchange membrane fuel cell (PEMFC) or

Polymer electrolyte membrane fuel cells (PEMFC)

 This type of fuel cell utilize water-based, acidic polymer

electrolyte membranes (PEMs), such as Nafion, to conduct
protons for ion exchange purposes
 PEMFC cells operate at relatively low temperatures (< 80°C)
 Due to the relatively low temperatures and the use of
precious metal-based electrodes, these cells must operate
on pure hydrogen.

Nafion

 Hydrogen fuel is processed at the anode where electrons are separated from protons on the surface of a
platinum-based catalyst.
 The protons pass through the membrane to the cathode side of the cell while the electrons travel in an
external circuit, generating the electrical output of the cell.
 On the cathode side, another Pt electrode combines the protons and electrons with oxygen to produce water.
 PEMFC

@ anode: H2 (g) → 2 H+ + 2 e-  SOFCs: Solid Oxide Fuel Cells

@ cathode: O2 (g) + 4 H+ + 4 e- → 2 H2O  SOFC (also known as ceramic FC) is a high-
temperature FC that utilizes solid ceramic
Net reaction: O2 (g) + 2 H2 (g) → 2 H2O (I) inorganic oxide as an electrolyte. SOFCs
E ˚Cell= 1.23 V work at very high temperatures (around 800
°C to 1,000 °C)
 Advanced PEMFC:
 e.g., zirconium oxide stabilized with yttrium
• A variant of the PEMFC which operates at elevated oxide, instead of a liquid or membrane. Also
temperatures is known as the high temperature–PEMFC known as Yttria-stabilized Zirconia (YSZ)
• By changing the electrolyte from being water-based to a  Both H2 & CO are used as fuels
mineral acid-based system, these can operate up to 200 °C.
 Efficiency is over 60% when converting fuel
• This overcomes some of the current limitations with regard to electricity
to fuel purity
 This cell relatively resistant to small
• Electrolyte in HT-PEMFC is phosphoric acid. quantities of sulphur in the fuel, compared
• Membrane is polybenzimidazole (PBI) or pyridine based to other types of fuel cell, and hence can be
used with coal gas

PBI
 PEMFC

@ anode: H2 (g) → 2 H+ + 2 e-
 SOFCs: Solid Oxide Fuel Cells
@ cathode: O2 (g) + 4 H+ + 4 e- → 2 H2O  SOFC (also known as ceramic FC) is a high-
Net reaction: O2 (g) + 2 H2 (g) → 2 H2O (I) temperature FC that utilizes solid ceramic
inorganic oxide as an electrolyte. SOFCs
E ˚Cell= 1.23 V work at very high temperatures (around 800
 Advanced PEMFC: °C to 1,000 °C)
• A variant of the PEMFC which operates at elevated  e.g., zirconium oxide stabilized with yttrium
temperatures is known as the high temperature–PEMFC oxide, instead of a liquid or membrane. Also
known as Yttria-stabilized Zirconia (YSZ)
• By changing the electrolyte from being water-based to a
mineral acid-based system, these can operate up to 200 °C.  Both H2 & CO are used as fuels
• This overcomes some of the current limitations with regard  Efficiency is over 60% when converting fuel
to fuel purity to electricity
• Electrolyte in HT-PEMFC is phosphoric acid.  This cell relatively resistant to small
quantities of sulphur in the fuel, compared
• Membrane is polybenzimidazole (PBI) or pyridine based to other types of fuel cell, and hence can be
used with coal gas

PBI
 SOFC
 Structure of SOFC
 Anode (or fuel) electrode:
 Nickel mixed with YSZ (yttria stabilized zirconia) –
called Nickel-YSZ cermet (Ceramic + metal).
 It is a porous ceramic layer to allow the fuel to flow
towards electrolyte
 Cathode (or air) electrode:
 The cathode is usually a mixed ion-conducting and
electronically conducting ceramic material.
 It is a thin porous ceramic layer coated over the
solid electrolyte where oxygen reduction takes  At anode (oxidation):
place. Example: Strontium doped lanthanum H2 (g) + CO (g) + 2 O2- → H2O (g) + CO2 (g) + 4e-
manganite  At cathode (reduction):
 Electrolyte: O2 (g) + 4e- → 2 O2-
 Oxide ion (O2-) conducting ceramic
 Net reaction:
 The most popular electrolyte material is a bilayer
composite electrolyte (YSZ layer + gadolinium H2 (g) + CO (g) + O2 (g) → H2O (g) + CO2 (g)
doped CeO2) or a mixture of ZrO and CaO.
 SOFC
 Advantages of SOFC:  Applications:
 SOFCs have high operating temperature.  SOFCs are being considered for a wide range of
 Since all the components are solid, applications – working as power systems for trains, ships
there is no need for electrolyte loss- and vehicles; supplying electrical power for residential or
related maintenance and electrode industrial utility.
corrosion is eliminated.  Stationary power generation
 Because of high-temperature operation,  By product gases are channeled to turbines to generate
the SOFC has a better ability to tolerate more electricity: cogeneration of heat and power and
the presence of impurities resulting improves overall efficiency
higher lifetime  Auxiliary power units in vehicles
 High efficiencies: Due to high-quality
waste heat for cogeneration  Disadvantages:
applications and low activation losses,  High operating temperature (500 to 1000 °C) which
the efficiency for electricity production results in longer start up times and
is great. mechanical/chemical compatibility issues.
 Low emissions. Releasing negligible  The cost and complex fabrication are also significant
pollution. It is the cleanest among all problems that need to be solved
fuel cells.
Differences Between Primary, Secondary & Fuel cells
Solar Cells

 Solar energy conversion devices: Methods of

tapping solar energy

A. Photosynthesis plants (Visible light )

B. Water heaters etc. (IR radiation)
C. Photovoltaic cells (Visible light)
D. Chemical routes

Biomimetic Mimicking Photoelectrochemical

photosynthesis using (PEC) Cell
chemicals

Liquid Junction Photoelectrosynthesis

Solar Cell (LJSC) (PES) cells
i. Photoassisted electrolysis cells
ii. Photoassisted electrosynthesis
cells
 Photovoltaic Cells
 It’s a device that converts the energy of sunlight
directly into electricity by the photovoltaic effect
 The photovoltaic effect involves creation of a voltage
(or a corresponding electric current) in a material
upon exposure to electro-magnetic radiation.
 Though the photovoltaic effect is directly related to
the photoelectric effect, the two processes are
different. In the photoelectric effect electrons are
ejected from a material's surface upon exposure to
radiation of sufficient energy.
 System converts light energy to electricity
 Applications in Aerospace & Satellite etc

# Silicon is a very common element abundant in nature. It is the main element in sand and quartz.
Silicon is considered as the most suitable material for solar energy conversion because of
 Most abundance (~ 28 % by mass) after oxygen
Why  Optimum band gap of 1.23 eV at 300 K
Silicon?  Cost effectiveness
 Interestingly, silicon has a greater density in a liquid state than a solid state.
 Silicon
 Structure of Silicon : The crystal
structure, or atomic
arrangement, of any material
has a great deal to do with its
electrical properties.

 Different types of silicon:

 Single crystal silicon: In its crystalline form, a material is characterized by an ordered array of component
atoms. This array is repetitive with displacement through the material sample.
 Polycrystalline silicon: The object is composed of a number of sub-sections, each of which is crystalline in
form. These subsections are independently oriented and at their interfaces the atomic order & regularity
undergo sharp discontinuities.
 Amorphous silicon (non-crystalline for higher light absorption): The amorphous material displays no
atomic regularity of arrangement on any macroscopic scale.
 Band gap (Eg) should be optimum
 Conditions for
 Doping level should be optimum, so that there will be a good spatial separation
Efficient Solar
of the photo-generated carriers and high quantum efficiency.
Energy Conversion –
 Having large values of absorption co-efficient (α), which is usually found for
Electrode materials
direct band gap SC’s.
 Dye Sensitization: Grätzel Cell

 Sunlight energy (photon of light) passes through the titanium

dioxide layer and strikes electrons within the adsorbed dye
molecules. Electrons gain this energy and become excited. The
excited electrons escape the dye molecules and become free
electrons. These free electrons move through the titanium
dioxide and accumulate at the dyed TiO2 plate.
 The free electrons then start to flow through the external
circuit to produce an electric current. This electric current
powers the light bulb.
 To complete the circuit, the dye is regenerated. The dye
regains its lost electrons from the iodide electrolyte. Iodide (I-) ions are oxidised (loss of 2 electrons) to tri-
iodide (I3-). The free electrons on the graphite plate then reduce the tri-iodide molecules back to their iodide
state. The dye molecules are then ready for the next excitation/oxid/red cycle.
 Dye Sensitization: Grätzel Cell
 In Grätzel cell a range of organic dyes are used.
 Examples: Ruthenium-Polypyridine, Indoline dye & metal Upper Plate : Dye coated TiO2
free organic dye. These dyes are extractable from simple
foods such as hibiscus tea, tinned summer fruits,
blackberries.

 Construction:
 Two transparent glass plates are perforated on one side with
a transparent thin layer of a conducting material.
 Onto the conducting sides, one plate is coated with graphite
and the other plate is coated with titanium dioxide (TiO2).
 A dye is adsorbed onto the TiO2 layer by immersing the plate
into a dye solution of 10-4 M in alcohol for 10 min. (approx.)
 The plates are then carefully sandwiched together and
secured using a paper clip.
 To complete the cell a drop of iodide electrolyte is added
between the plates. Lower Plate : Graphite coated
 Figure shows a Grätzel cell prepared from hibiscus tea.
 Engineering Chemistry
(CHY1701)
Module -6: Fuels and Combustion
● Calorific value: Significance, Comparison between LCV & HCV. Measurement of
calorific value using Bomb calorimeter and Boy’s calorimeter with numerical problems.
● Controlled combustion of fuels, Air fuel ratio, Minimum quantity of air by volume and
by weight, Numerical problems. Catalytic converter (Three ways), Selective catalytic
reduction of NOX.
● Knocking in IC engines: Octane & Cetane number, Anti-knocking agents
 Fuel

 A fuel is any compound which has stored energy.

 Characteristics of a good fuel
These are the combustible substances, which on
 High Calorific Value
combustion produces a large amount of heat,
which can be used for various domestic and  Moderate Ignition Temperature – should be
industrial purposes higher than room temperature
 The process of combustion involves oxidation of  Should not undergo spontaneous combustion
carbon, hydrogen etc. of the fuels to CO2, H2O, and  Low Moisture Content
the difference in the energy of reactants and the  Low non-combustible matter content
products are liberated as large amount of heat
 Moderate velocity of combustion
energy which is utilized
 Products of combustion should not be harmful
Fuel + O2 → Products + Heat  Low Cost
 The primary or main source of fuels are coal and  Easy to transport
petroleum oils, the amounts of which are  Combustion should be easily controllable
dwindling day by day. These are stored fuels  Storage cost in bulk should be low
available in earth's crust and are generally called
 Size should be uniform (solid fuel) –
"fossil fuels"
Combustion is regular
Fuel
 Calorific Value of Fuel
 The calorific value is defined as the amount of heat produced upon  Fuels are generally composed of
complete combustion of a unit amount or volume of substance. hydrocarbons (HC) and carbon. They
 The most important property of fuel to be taken into account is its also contain some amount of H2
calorific value or the capacity to supply heat  Upon combustion the constituents
undergo following reactions

C + O2 → CO2 (g) + Heat

HC + O2 → CO2 (g) + H2O (l) + Heat
H2 + O2 → H2O (l) + Heat

 During combustion process the water

gets converted into water vapour
 The latent heat of evaporation is taken
from the heat liberated due to burning
of fuel
 Calorific Value of Fuel
 Higher or Gross Calorific Value (HCV/GCV)  Lower or Net Calorific Value (LCV/NCV)
 It is defined as “Total amount of heat liberated  In actual use of fuel, the water vapour and moisture
when one unit mass/volume of the fuel has been etc. are not condensed and escapes as such along
burnt completely and the products of combustion with hot combustion gases. Hence a lesser amount
have been cooled to room temperature” of heat is available. So, net or lower calorific value
may be defined as "the net heat produced when
 Usually all fuels contain some H2 and when the unit mass / volume of the fuel is burnt completely
calorific value of hydrogen containing fuel is and the products are permitted to escape".
determined experimentally, the hydrogen is
converted to water vapour.  LCV/NCV can be found from HCV/GCV value
 To get back the heat lost due to evaporation, the NCV = GCV - Latent heat of water vapour formed
products of combustion are condensed by cooling = GCV - Mass of hydrogen × 9 × latent heat of steam
to room temperature = GCV - % of hydrogen × 0.09 × latent heat of steam
 The latent heat of condensation of steam also gets  The latent heat of steam is 587 kcal/kg or 1060
included in the measured heat, which is then called B.Th.U./lb of water vapour formed at room
"higher or gross calorific value". temperature
 Formation and the release of water vapour reduce  For gaseous combustion products both HCV & LCV
the amount of thermal energy available in the are same
system.
 Determination of Calorific Value

Bomb calorimeter

 The Bomb Calorimeter is used to measure the Boys calorimeter:

calorific value of the solid and liquid samples  To measure calorific value of gaseous and
 It is a constant-volume type calorimeter that volatile liquid fuels
measures the heat of a particular reaction or  Designed by Sir Charles Vernon Boys
measures the calorific value of the fuels
 Bomb Calorimeter
 Bomb calorimeters are built in such a
way that they can withstand the large
pressure produced within the
calorimeter
 The essential parts of any bomb
calorimeter are:
 An insulating jacket to protect the
copper calorimeter from transient
thermal stresses during the combustion
process
 A copper calorimeter for holding the
bomb in a measured quantity of water,
together with a stirring mechanism
 A steel bomb in which the combustible charges can
be burnt
 A stainless steel crucible
 A thermometer/other sensor for measuring  Electrical fuse wire to ignite the
temperature changes within the calorimeter combustible charge or fuel
 Bomb Calorimeter

 Working principle:
 In the bomb calorimeter, measured
amount (generally 1 g) of the sample is
taken in the crucible & the bomb is
pressurized (25-30 atm) with pure O2
 The charge is then electrically ignited to burn
in the high-pressure oxygen atmosphere.

 During the combustion, heat is liberated by

the combustion is absorbed in water present
inside the calorimeter

 The increase of water temperature change is

recorded
 The heat of combustion of the sample is then calculated by multiplying the temperature rise in the
calorimeter by a previously determined energy equivalent or heat capacity determined from
previous tests with a standardizing material
 Bomb Calorimeter
 Calculation of HCV  Calculation of NCV
NCV = HCV – (0.09 × H × latent heat of steam) cal/g
Let, H = % of hydrogen in fuel
W = mass of water in the calorimeter (g)  then, 1 g fuel will have (H/100) g of hydrogen
w = water equivalent of calorimeter (g) Now, upon combustion, hydrogen is converted into steam as
m = mass of the fuel (g) H2 (g)+ ½ O2(g) → H2O (l)
t1 = initial temperature of calorimeter  2 g of hydrogen produces 18 g of water
t2 = final temperature of calorimeter  1 g of hydrogen produces 18/2 = 9 g of water
HCV = gross calorific value of fuel  (H/100) g of hydrogen produces = 9 × (H/100) g of water
 To get HCV in Joule/g, multiply above = (0.09 × H) g of water
equation by 4.2
Latent heat of stem = 587 cal/g
 Water Equivalent of the calorimeter is
determined by burning a fuel of known  Heat taken by water to form steam or the latent
calorific value heat of water vapor formed = (0.09 x H x 587) cal
 Benzoic acid (HCV = 6,325 kcal/kg) Now, NCV = HCV - Latent heat of water vapour formed
 Naphthalene (HCV = 9,688 kcal/kg)  NCV = HCV – (0.09 × H × 587) cal/g
 Determination of Calorific Value: Bomb Calorimeter
 0.72 gram of a fuel containing 80% carbon, when  On burning 0.83 g of a solid fuel in a bomb calorimeter,
burnt in a bomb calorimeter, increased the the temperature of 3500 g of water increased from 26.5
temperature of water from 27.3o to 29.1oC. If the oC to 29.2 oC. Water equivalent of calorimeter and

calorimeter contains 250 grams of water and its water latent heat of steam are 385.0 g of and 587.0 cal/g
equivalents is 150 grams, calculate the HCV of the fuel. respectively. If the fuel contains 0.7 % hydrogen,
Give your answer in KJ/Kg. calculate its gross and net calorific value.
W = mass of water in the calorimeter = 250 g W = mass of water in the calorimeter = 3500 g
w = water equivalent of calorimeter = 150 g w = water equivalent of calorimeter = 385 g
m = mass of the fuel = 0.72 g m = mass of the fuel = 0.83 g
t1 = initial temperature of calorimeter = 27.3 °C t1 = initial temperature of calorimeter = 26.5 °C
t2 = final temperature of calorimeter = 29.1 °C t2 = final temperature of calorimeter = 29.2 °C
H = 0.7 %
(𝟑𝟓𝟎𝟎+𝟑𝟖𝟓) 𝟐𝟗.𝟐−𝟐𝟔.𝟓
HCV= = 12638 cal/g
𝟎.𝟖𝟑
= (1000 × 4.2) kJ/kg = 4200 kJ/kg NCV = HCV – (0.09 × 0.7 × 587) = 12638 - 37 =
12601 cal/g
 On burning 0.83 g of a solid fuel in a bomb calorimeter, the temperature of 3,500 g of water increased from
26.5 oC to 29.2 oC. In another experiment in the same calorimeter 0.5 g of naphthalene (HCV = 9,688 kcal/kg)
was burnt and temperature was increased form 25.5 oC to 29.2 oC. Latent heat of evaporation of water is
587.0 cal/g and the fuel contains 0.7 % hydrogen, calculate its gross and net calorific value.
 Bomb Calorimetric Corrections

 Fuse wire correction

 Precision in bomb calorimetry is dependent
upon a repeatable set of operating conditions.  Together with the sample, part of the ignition or
fuse wire is also burned. The heat generated by
 Those factors which cannot be held constant
burning of the fuse wire is also gets included in the
will require corrections to compensate for their
gross calorific value and this value must be
effects. Any differences between the
subtracted from observed value to get correct HCV
combustion as it takes place in the bomb in
relation to the process in a power plant or other  A correction term, ∆Qwire, the heat released by the
application must also be taken into account combustion of the wire must be introduced
 ∆Qwire is obtained by measuring the length of the
fuse wire before and after combustion and
 There are three major corrections: multiplying the difference by a conversion factor
● Fuse wire correction qwire, valid at standard temperature
● Acid correction ∆Qwire = qwire × (L0 – L)
● Cooling correction L0 = fuse wire length before combustion
L = fuse wire length after combustion
 Bomb Calorimetric Corrections
 Acid correction  For 1 ml of 0.1 N H2SO4 formed: 3.6 calories should be
 Combustion in the bomb takes place in an subtracted
atmosphere of pure oxygen at high temperature
 For 1 ml of 0.1 N HNO3 formed: 1.43 calories should be
and pressure. Fuels containing S and N gets
subtracted
oxidized under high pressure & temperature of
 When H2SO4 is determined by precipitation as BaSO4:
ignition producing H2SO4 & HNO3
For 1 mg of S is 2.25 cal should be subtracted
S + O2 → SO2
2 SO2 + O2 + 2 H2O → 2 H2SO4 ΔH = - 144 kcal/mol
 Cooling correction
2 N2 + 5 O2 + 2 H2O → 4 HNO3 ΔH = - 57.2 kcal/mol
 For an adiabatic calorimeter, the heat loss to the water
 These side reactions, being exothermic, generate jacket is negligible. Cooling correction isn’t necessary
an appreciable amount of heat which can’t be  For an isothermal/static calorimeter, the heat loss occurs
credited to the sample due to the radiation through the dewar. Highest
 This heat liberated gets included into the overall temperature recorded be slightly less than the actual.
HCV. Hence, the heats of formation of H2SO4 and  This loss is corrected with an empirical radiative
HNO3 should be subtracted from the heat correction (RC). The rate of cooling of the calorimeter
liberated from maximum temperature to room temperature is
 The correction term for the formation of noted. From this rate of cooling (i.e., dt/min) and the
sulphuric and nitric acid is obtained by titrating actual time taken for cooling (X min), correction (dt × X) is
the aqueous residues in the bomb with a called cooling correction and is added to the (t2 - t1) term.
standardized NaOH solution
 Bomb Calorimetric Corrections

(𝑾 + 𝒘)(𝒕𝟐 − 𝒕𝟏 + 𝒕𝒆𝒎𝒑. 𝒄𝒐𝒓𝒓𝒆𝒄𝒕𝒊𝒐𝒏) − (𝑨𝒄𝒊𝒅 + 𝒇𝒖𝒆𝒍 𝒄𝒐𝒓𝒓𝒆𝒄𝒕𝒊𝒐𝒏)

𝑯𝑪𝑽 =
𝑴𝒂𝒔𝒔 𝒐𝒇𝒕𝒉𝒆 𝒇𝒖𝒆𝒍 (𝒎)

NCV = HCV – (0.09 × H × latent heat of steam) cal/g

 A sample of coal contains C = 93 %; H = 6 % and ash = 1 %. The following data were obtained when the above
coal was tested in bomb calorimeter. wt. of coal burnt = 0.92 g, Wt. of water taken = 550 g, water equivalent of
calorimeter = 2200 g, rise in temperature = 2.42 °C, fuse wire correction = 10.0 cal, acid correction = 50.0 cal.
Calculate gross and net calorific value of the coal. The latent heat of condensation of steam is 580 cal/g.

• Wt. of coal sample (m) = 0.92 g; GCV/HCV = (W + w) (t1 - t2) – [ acid + fuse corrections]
• wt. of water (W) =550 g; m
• water equivalent of calorimeter (w) = 2,200 g;  {(550 + 2,200) × 2.42} – [50 + 10] cal = 7168.5 cal/g.
• temperature rise (t2-t1) = 2.42 oC; 0.92g
• acid correction = 50.0 cal;
• fuse wire correction = 10.0 cal;  NCV = [HCV – 0.09 H × latent heat steam]
• latent heat of steam = 580 cal/g; = (7168.5 – 0.09 × 6 × 580) cal/g = 6855.3 cal/g
• percentage of H =6%
 Determination of Calorific Value: Bomb Calorimeter

Problem 1:
 The temperature of 950 g of water increased from
25.5 °C to 28.5 °C on burning 0.75 g of solid fuel in a  Problem 2:
bomb calorimeter. Water equivalent of the  A sample of coal contains C = 92%; H = 5% and
calorimeter and the latent heat of steam are 400 g ash = 3%. The following data were obtained
and 587 cal/g. If the fuel contains 0.65% of when the above coal was tested in bomb
hydrogen, calculate its net calorific value. calorimeter.
Wt. of coal burnt = 0.95 g,
Wt. of water taken = 700 g,
 Problem 3: Water equivalent of calorimeter = 2000 g,
 A sample of coal contains C = 90 %, H = 8.9 % and Rise in temperature = 2.48 °C,
ash = 3 %. On burning 1 g of coal in a bomb Fuse wire correction = 10.0 cal,
calorimeter, the temperature of 2500 g water Acid correction = 60.0 cal and
increased 2.5 °C. Mean specific heat of the Cooling correction = 0.02 °C.
apparatus is 0.098. Acid and fuse-wire corrections Calculate gross and net calorific value of the coal,
are 50 cal and 10 cal respectively. Calculate gross assuming the latent heat of condensation of
and net calorific value of coal sample. Given the steam as 580 cal/g.
latent heat of water is 587 cal/g.
Home Work
 Boys Calorimeter

 It is to measure calorific value of gaseous and volatile liquid fuels.

It has designed by Sir Charles Vernon Boys
 Construction
 Boys calorimeter consists of a combustion chamber
surrounded by water tube with two thermometers T1 and
T2 attached. There is a burner in the chamber, which is
connected to a gas tube.
 Principle:
 A known volume of gaseous fuel sample is burnt in the
combustion chamber of a Boys calorimeter.
 The released heat is quantitatively absorbed by cooling
water, circulated through copper coils surrounding the
combustion chamber.
 The mass of cooling water & its rise in temperature are
noted.
 The mass of water produced by condensation of steam is calculated.
 The calorific value of the fuel sample is then calculated from these data.
 Boys Calorimeter
 Working method:  Calculation
 A known volume of water is passed through the tubes.
 The initial temperature is noted when the two
thermometers show the same constant temperature.
 A known volume of the gas (measured using a meter) is W = mass of cooling water passed through the
passed through the tube and burnt in the combustion cooling coil (g)
chamber. S = Specific heat of water = 1 cal g-1 ℃-1
 The heat liberated is absorbed by the water in the tubes.
V = Volume of the fuel burnt (mL)
 The final temperature of water is noted.
 The gaseous products are cooled and condensed into a T1 = Temperature inlet water
measuring jar. T2 = Temperature outlet water
 The following data were obtained in a Boys gas calorimeter HCV = gross calorific value of fuel
experiment:
Volume of gas (V) = 0.5 m3 at STP, Weight of water heated (W) =
125 kg
Inlet water temperature (T1) = 20 °C,
Outlet water temperature (T2) = 40 °C m = mass of water condensed (g)
Weight of steam condensed (m) = 0.125 kg. L = Latent heat (cal g-1 ℃-1)
Calculate the HCV and LCV
 Calorific Value: Theoretical Calculation
 Dulong’s Formula
 Calculate HCV and NCV of a coal sample
 Theoretical estimation of the higher calorific value (HCV) of
having the following composition: C =
a fossil fuel based upon the weighted heats of combustion
80 %, H = 7.5 %, O = 3 %, S = 3.5 %, N =
of the constituent element, such as, C, H, S and O
2.1 % and ash = 4.4 %.
 The HCVs of the constituent elements are used here 𝟏
 HCV = 𝟖𝟎𝟖𝟎 ∗ 𝟖𝟎 +
𝟏𝟎𝟎
H = 34500 kcal/kg, C = 8080 kcal/kg, S = 2240 kcal/kg
 Oxygen present in the fuel is assumed to be present as water
(fixed hydrogen).
Available Hydrogen = Total hydrogen – Fixed hydrogen
= Total hydrogen - 1/8 mass of oxygen in fuel.
 Dulongs formula for calorific value from the chemical  NCV = HCV – 0.09*H*latent heat of steam
composition of fuel is, = 9000.5 – 0.09*7.5*587
= 9000.5 – 396.2
= 8604.3 kcal/g
 Combustion

 Combustion is a chemical reaction  Air-Fuel Ratio (AFR)

between substances, usually including  To guarantee the combustion process, certain quantities
oxygen and usually accompanied by the of fuel and air need to be supplied in the combustion
generation of heat and light in the form chamber.
of flame.  A complete combustion takes place when all the fuel is
 During combustion process the carbon, burned, in the exhaust gas there will be no quantities of
hydrogen, etc., combine with oxygen unburned fuel.
with simultaneous liberation of heat  Air-fuel ratio (AF or AFR) is the ratio between the mass of
 During combustion, lower energy air and mass fuel, used by the engine when running
molecules are formed from a higher
energy molecule.  The ideal (theoretical) air-fuel ratio, for a complete
 The energy difference between the combustion, is called stoichiometric air-fuel ratio.
reactants and products appear as heat For a gasoline (petrol) engine, the stoichiometric air-
fuel ratio is around 14.7:1
 The lowest temperature at which a
combustible substance when heated (as  The AFR is necessary for controlling emission and
in a bath of molten metal) takes fire in performance-tuning reasons
air and continues to burn is called the  The AFR is important measure for anti-pollution and
Ignition Temperature performance tuning reasons.
 Calculation of Air Quantities
 Following chemical principles are applied to find out the  Common combustion reactions are:
amount of oxygen/air is required for complete combustion
 Substances always combine in definite proportions which
are determined by their molecular weights. Writing a
balanced stoichiometric equation is necessary, eg
C (s) + O2 (g) → CO2 (g)
12 32 44
 At 0 ℃ and 760 mm pressure 1 mole gas will occupy 22.4 L
 At STP 22.4 L of O2 will have a mass of 32.
 Molar mass of air = 28.94 g mol-1
 Air contains 21% oxygen by volume and 23% oxygen by mass
 1 kg of oxygen can be obtained from 100/23 = 4.35 kg
of air
 1 m3 oxygen can be obtained from 100/21 = 4.76 m3 of
air
 We consider all gases behave ideally and follow: PV = nRT
 Calculation: Combustion

Problem 1: How much air will be required to

Wt of Oxygen Vol. Of burn 1 kg carbon?
needed Oxygen  Burning of carbon involves following reaction:
needed
C (s) + O2 (g) → CO2 (g)
C + O2 → CO2 x * 1 * 32/12 x*1
12 32 44
x g or m3
to burn 12 g C we need = 32 g oxygen
H2 + 0.5 O2 → H2O x * 0.5 * 32/2 x * 0.5
x g or m3 For 1000 g C, oxygen required is = (32 x 1000)/12 g
CO + 0.5 O2 → CO2 x * 0.5 * 32/28 x * 0.5 = 2667 g = 2.667 kg oxygen
x g or m3  Now, air contains 23 % oxygen by mass
S + O2 → SO2 x * 1 * 32/32 x*1 So, amount of air will be = (100 x 2.667)/23 kg
x g or m3 = 11.59 kg
CH4 + 2 O2 → CO2 + 2H2O x * 2 * 32/16 x*2
Problem 2: A coal sample having the following
x g or m3
composition: C = 80%, H = 4%, O = 3%, S = 2%.
C2H6 + 3.5 O2 → CO2 + 3H2O x * 3.5 * 32/30 x * 3.5 Calculate the quantity of air needed for the
x g or m3 complete combustion of 1 kg of coal.
 Catalytic Converter
 A catalytic converter is a device used to reduce the  Component
toxicity of emissions from an internal combustion  The current three-way catalyst is generally a multi
engine component material, containing the precious
 Catalytic converters are used on spark ignition metals rhodium, platinum and (to a lesser extent)
(petrol, liquefied petroleum gas (LPG), compressed palladium, ceria (CeO2), γ-alumina (Al2O3), and
natural gas (CNG)) engines; and compression ignition other metal oxides.
(diesel) engines
 In the three-way catalyst, reactions between CO, HC,
and NOx result in the simultaneous removal of all three
major exhaust pollutants
 A three-way catalytic converter has three
simultaneous tasks:
a. Reduction of nitrogen oxides to nitrogen and
oxygen
b. Oxidation of carbon monoxide to carbon dioxide
c. Oxidation of unburnt non-methane hydrocarbons
(HC) to carbon dioxide and Water
 Catalytic Converter
 It typically consists of a ceramic monolith of  Working of 3-way Catalytic Converter
cordierite (2Mg.2Al2O3. 5SiO2) with strong porous  A three-way catalytic converter makes use of two
walls enclosing an array of parallel channels. catalysts to convert harmful gases to harmless gases.
 For example, Cordierite is used  They are Reduction Catalyst & Oxidation Catalyst
because it can withstand the
high temperatures in the
exhaust, and the high rate of
thermal expansion encountered
when the engine first starts –
typically, the exhaust gas
temperature can reach several
hundred degrees in less than a
minute.
 The reduction catalyst is made of
platinum and rhodium while the
oxidation catalyst is made of
platinum and palladium. Both the
catalysts have a ceramic
honeycomb structure.
 Catalytic Converter

 Stage 1 – Reduction Catalyst:

 The exhaust gases are first sent over the reduction
catalyst (which is made of Pt and Rh). It converts
oxides of nitrogen (NOx) to nitrogen and oxygen
2 NO → N2 + O2
2 NO2 → N2 + 2 O2

 Stage 2 – Oxidation Catalyst:

 Exhaust gases that are free of oxides of nitrogen
(NOx) are then sent over the oxidation catalyst
(made of Pd & Pt). The oxidation catalyst coverts
carbon-monoxide (CO) and hydrocarbons (HC) in the
gases into carbon-di-oxide and water
2 CO + O2 → 2 CO2
HC + O2 → CO2 + H2O
 Internal Combustion Engine
 An internal combustion engine (ICE) is a heat engine in which
the combustion of a fuel occurs with an oxidizer (usually air) in
a combustion chamber that is an integral part of the working
fluid flow circuit.
 ICEs are the most common form of heat engines as they are
used in vehicles, boats, ships, airplanes, and trains.
 Most of the ICEs are four-stroke cycle engines, meaning four
piston strokes are needed to complete a cycle.
 Intake stroke: The piston moves downward to the bottom,
this increases the volume to allow a fuel-air mixture to
enter the chamber.
 Compression stroke: The intake valve is closed, and the piston
moves up the chamber to the top. This compresses the fuel-
air mixture. At the end of this stroke, a spark plug provides the
compressed fuel to begin combustion.
 Power Stroke: As the fuel reaches the end of it’s  Exhaust stroke: As the piston reaches the
combustion, the heat released from combusting bottom, the exhaust valve opens. The
hydrocarbons increases the pressure which causes the gas remaining exhaust gas is pushed out by the
to push down on the piston and create the power output. piston as it moves back upwards
 Compression Ratio (CR)

 In an internal combustion engine, a mixture of  Knocking

gasoline vapour and air is used as a fuel  In IC engine, sharp sounds caused by premature
 After the initiation of the combustion, the flame combustion of compressed air-fuel mixture in the
should spread rapidly and smoothly through the cylinder is called knocking
gaseous mixture, thereby the expanding gas drives  In a properly functioning engine, the charge burns with
the piston down the cylinder the flame front progressing smoothly from the point of
 The ratio of the gaseous volume in the cylinder at ignition across the combustion chamber.
the end of the intake-stroke to the volume at the  In certain circumstances, at high compression ratio, the
end of compression-stroke of the piston is known rate of oxidation becomes so great that the last portion
as the 'compression ratio (CR)' of the fuel-air mixture gets ignited instantaneously
 Compression ratio (CR): ratio of the cylinder producing an explosive violence, known as 'knocking'.
volume (V1) at the end of the intake stroke to the  Some reasons are:
volume (V2) at the end of the compression stroke  Under high pressure of compression cycle certain
of the piston portion might get over heated leading to uneven
 The efficiency of an internal combustion engine combustion
increases with the compression ratio. Successful  Presence of some constituents, such as, deposited
high compression ratio is dependent on the nature carbon particle in the gasoline used, the rate of
of the constituents present in the gasoline used. oxidation becomes uncontrolled
 Knocking

 Effect of knocking in IC engine

 The knocking results in loss of efficiency,
since this ultimately decreases the
compression ratio
 Knocking can cause overheating of the
spark-plug points
 Erosion of the combustion chamber surface
& rough, inefficient operation
 Engine pistons get severely damaged when
subjected to prolonged operation under
knocking
 In a properly functioning  Fuel may spontaneously ignite
engine, fuel burning ahead of the flame front and
occurs smoothly from burn in an uncontrolled
the point of ignition manner, producing intense
across the combustion high-frequency pressure
chamber. waves
 Factors Affecting Knocking

 Engine design  Octane number or Octane rating or Antiknock Rating

 Octane number is the measure of the ability of a fuel
 Running conditions and cleanliness
to resist knocking when ignited in a mixture with air
 Chemical structure of fuel hydrocarbons: in the cylinder of an internal-combustion engine.
 The tendency of fuel constituents to  The most common way of expressing the knocking
knock is in the following order. characteristics of a combustion engine fuel
Straight – Chain paraffins > Branched -  The higher the number, the better the fuel burns
Chain paraffins (Isoparaffin) > Olefins > within the engine of a vehicle. Higher performance
Cyclo Paraffins (Naphthenes) > vehicles require fuels with a higher octane rating.
Aromatics  The octane number is determined by comparing,
 For the straight chain hydrocarbons the under standard conditions, the knock intensity of
tendency to knock increases with the fuel with that of blends of two reference fuels:
molecular weights and boiling points: iso-octane, which resists knocking, and heptane,
n-hexane > n-pentane > n-butane which knocks readily.
 Aromatic hydrocarbons have higher
H H H H H H H CH 3
anti-knocking properties than paraffins
H C C C C C C C H CH 3 C CH 2 CH CH 3

H H H H H H H CH 3 CH 3
 Improvement of Anti-knock Characteristics of a Fuel
 The octane number of many otherwise poor fuels  There are three major groups of anti-knocking agents :
can be raised by the addition of tetra ethyl lead 1. Aromatics: Toluene and Xylene (non-carcinogenic) - A
(C2H5)4Pb/ TEL and diethyl telluride (C2H5)2Te.
mixture of Benzene, Toluene and Xylene is used as an
 TEL is converted into a cloud of finely divided anti-knocking agent [Benzole (BTEX)]
lead and lead oxide particles in the cylinder and
these particles react with any hydrocarbon 2. Oxygenates: MTBE (methyl tertiary butyl ether)
peroxide molecules formed, thereby slowing and ETBE (ethyl tertiary butyl ether)
down the chain oxidation reaction and thus 3. Organometallic compounds: MMT (methyl
decreasing the chances of any early detonation. cyclopentadieny manganese tri-carbonyl), Ferrocene
 But the usage of this is associated with Environmental (dicyclopentadienyl iron), nickel carbonyl, TEL (tetra
& Health issues of Lead.
 However deposit of lead oxide is harmful to ethyl lead) or TML (tetra methyl lead). They are all toxic
the engine life. In order to help the in nature. But Ferrocene is safer than TEL/ TML.
simultaneous elimination of lead oxide formed
from the engine, a small amount of ethylene  Other additives
dibromide (or ethylene dichloride) is also  Oxidation inhibitors: 2,4-ditertiary butyl-4-methyl
added to petrol. phenol.
 The added ethylene dibromide removes lead  Rust inhibitors: Organic compounds of phosphorus or
oxide as volatile lead bromide along with the antimony.
exhaust gases. The presence of sulphur  Ignition control additives: Tricresyl phosphate which
compounds in petrol reduces the effectiveness
of the TEL. TEL is more effective on saturated suppresses pre-ignition of the fuel due to glowing
hydrocarbons than on unsaturated ones. deposits on spark plug or a hot spot on the cylinder wall.
 Diesel Engine Fuels

 Characteristics of an ideal diesel oil

 It should have low spontaneous ignition temperature.
 It should have very little sulphur, aromatic and ash content.
 The ignition lag should be as short as possible.

 Knocking in Diesel Engines

 In a diesel engine, the fuel is exploded not by a spark, but by the application of heat and pressure. In the
cycle of operations of a diesel engine, air is first drawn into the cylinder and compressed.
 Towards the end of the compression stroke, the fuel (diesel oil) is injected as a finely-divided spray into air
in the cylinder heated to about 500 C by compression.
 The oil absorbs the heat from the air and if it attains its ignition temperature the oil ignites spontaneously.
The pressure of the gases is further increased by the heat accompanying the ignition of the oil.
 The piston is pushed by the expanding gases and this constitutes the power stroke.
 Fuel feed and ignition continue during this down stroke. The fuel injection stops at the exhaust stroke.
 Diesel engine fuels consist of longer chain hydrocarbons than internal combustion engine fuels.
 Diesel Engine Fuels
 The main characteristic of diesel engine fuel CH3
 It should easily ignite below compression temperature.
 There should be as short an induction lag as possible.
This means that it is essential that the hydrocarbon
 n-Hexadecane  2-Methyl naphthalene
molecules in a diesel fuel should be as far as possible (Cetane No. = 100) (Cetane No. = 0)
the straight-chain ones with a minimum admixture of
aromatic and side-chain hydrocarbon molecules.  Ignition quality decreases among hydrocarbons is
as follows
 The suitability of a diesel fuel is determined by its
cetane value, which is the percentage of hexadecane in # n-alkanes > naphthalenes > alkenes >
branches alkanes > aromatics
a mixture of hexadecane and 2-methyl naphthalene,
which has the same ignition characteristics as the ● Cetane number & Ignition quality decreases
diesel fuel sample, under the same set of conditions. ● Ignition delay increases
 The cetane number of a diesel fuel can be raised by
the addition of small quantity of certain "pre-ignition
dopes" like alkyl nitrites such as ethyl nitrite, iso-amyl
nitrite, acetone peroxide.
 Engineering Chemistry
(CHY1701)
Module -7: Polymer
● Difference between thermoplastics & thermosetting plastics, Engineering applications of
plastics - ABS, PVC, PTFE and Bakelite
● Different moulding processes: Injection moulding (Car parts/Bottle caps), Extrusion
moulding (Pipes/Hoses), Compression moulding (Mobile Phone Cases/Battery Trays),
Transfer moulding (Fibre reinforced polymer matrix composites) & blow moulding (PET
bottles)
● Conducting polymers, Polyacetylene, Mechanism of conduction, Applications (Polymers in
sensors, Self-cleaning windows)
 Polymer
 What is a Polymer?
 A polymer is a large molecule composed of
repeating structural units connected by covalent
chemical bonds. These large molecules also
known as macromolecules
 Polymers make up many of the materials in living
organisms, for example, proteins, cellulose, DNA, RNA,
nucleic acids and such man-made materials as Proteins
paper, plastics, and rubbers. Starch, Rubber,
 Polymers exist since the dawn of life mostly in Resin
the form of bio-polymer
☻ Polymer: Polymers are complex and giant
molecules which are made from joining a
large number of small and simple molecules
by primary valency linkage.
☻ Monomer: The individual small & simple molecules from which the polymer is formed are known as monomer.
☻ Polymerization: The process by which the monomer molecules are linked to form a big polymer molecule is
called polymerization.
 Polymer
 Depending on number of active functionality monomers can be classified as
☻ Functionality: The
● Bifunctional: a monomer with functionality
functionality of a molecule
2, can link to two other molecules under
is the number of sites it
suitable conditions
has for bonding to other Styrene, ethylene,
molecules under the given ● Polyfunctional: react with more than ethylene glycol, diamines,
conditions of the two molecules under the conditions of dicarboxylic acids, etc
polymerization reaction the polymerization reaction

☻ Degree of polymerization: The number (n) of

monomers forming the polymer chain are
Glycerol, Phenol
called its degree of polymerization
Nylon-6:
☻ Monomer and repeating units are coincident:
 “n” could be in the range of hundreds to
thousands – they are high polymers.
 n < 10, they are oligomers.
 Classification
 Polymers are classified in a number of ways 1. On the basis of source or origin
1. On the basis of source or origin  Natural Polymers: Polymers that occur in Nature and are
2. On the basis of structure existing in natural sources like plants, animals
3. On the basis of mode of synthesis
◙ Polysaccharides: Starch and cellulose are the polymers of
4. On the basis of molecular forces
glucose or monosaccharides. Starch is a chief food reserve of
 Semi-Synthetic Polymers: Polymers that plants while cellulose is chief structural material of plants.
obtained by making modification in natural
polymers artificially in a lab

Cellulose
◙ Proteins: Polymers of α-amino acids. They are building
blocks of animal cells. They constitute indispensable part of
our food. Natural protein, wool, leather, etc. are proteins.
◙ Cellulose acetate
(rayon)
Silk fibroin ←
 Polymer Classification
Example of Semi-Synthetic Polymers: 2. On the basis of structure
◙ Vulcanized Rubber  This classification of polymers is based
upon how the monomeric units are linked
together

Linear
Branched
Well packed, high
Irregularly packed,
density, high tensile
low density, lower
strength& high
tensile strength &
melting points
 Synthetic Polymers: Polymers that can be lower melting points.
e.g.; polyethylene,
artificially created/synthesized in the lab. e.g.; Amylopectin,
nylon, polyester
glycogen

Hard, rigid & brittle because of their

network structure
e.g.; Bakelite, formaldehyde resin,
Crosslinked melamine
 Polymer Classification
 Tacticity: The spatial arrangement of  Homopolymers: The polymers which formed from the same
pendent groups of successive type of monomers are called homopolymers.
stereocenters (asymmetric carbon) in
the main chain is called its tacticity

☻ Syndiotactic Polymer

 Copolymers: When
two or more
☻ Isotactic Polymer different types of
monomer make up
the polymer, it is
known as
copolymer.
☻ Atactic Polymer
 Polymer Classification
3. On the basis of mode of synthesis 4. On the basis of molecular forces
 The mechanical properties of
 Addition Polymers: These type of polymers are formed by the
polymers such as elasticity,
repeated addition of monomer molecules.
tensile strength, toughness, etc.
● The polymer is formed by
depend upon intermolecular
polymerization of monomers with
forces like Vanderwaal's force
double or triple bonds (unsaturated
and hydrogen bonding existing in
compounds). No elimination of small
the macromolecules
molecules like water or alcohol
 On the basis of the magnitude
 Polyethylene, polystyrene, polyacrylonitrile, PVC of intermolecular forces, the
 Condensation Polymers: Formed by the combination of monomers, polymers have been classified
with the elimination of small molecules like water, alcohol etc. into the following four
● The monomers in these types of condensation reactions are bi- categories:
functional or tri-functional in nature a) Elastomers
 Nylon – 66, PET, polyester, polyureathane b) Fibers
c) Thermoplastics
d) Thermosetting Polymers
 Polymer Classification
a) Elastomers b) Fibers
 Elastomers are rubbery materials composed of long chainlike  These are the polymers which have quite
molecules, or polymers, that are capable of recovering their strong inter-particle forces such as hydrogen-
original shape after being stretched to great extents bonds.
 Strong inter-molecules forces between the
chains giving them less elasticity and high
tensile strength.
 These are thread-like polymers and can be
woven into fabrics. Silk, terylene, nylon, etc.

 Polymer chains are held up by weakest attractive forces

 They are amorphous polymers having high degree of elasticity
with a glass transition temperature well below room temperature
 The weak forces permit the stretched polymer to be retracted
when the stretching forces is withdrawn
 Classification of Elastomers
● Diene/Unsaturated rubbers: polyisoprene, polybutadiene, polychloroprene
● Non-diene or Saturated rubbers: butyl rubber, polysiloxanes, polyurethane
● Thermoplastic elastomers: Elastomers have no double bonds in the structure Hydrogen bonding
 Polymer Classification
c) Thermoplastics d) Thermosetting Polymers
 A thermoplastic is a polymer that softens and hardens  These are the polymers which become hard
reversibly on changing the temperature. and infusible on heating.
 Inter-particle forces of attraction are in between those of  They are normally made from semi-fluid
elastomers and fibres. substances with low molecular masses, by
 The polymers can heating in mould. Heating results in excessive
be easily moulded cross-linking between the chains forming
into desired shapes three dimensional network of bonds
by heating and  Thermosetting material undergoes a
subsequent cooling permanent change upon melting and
to room thereafter sets to a solid which can not be
temperature remelted
 There is no cross-  Bakelite, Vulcanized rubber, Melamine, epoxy
linking between resin etc.
the polymer chains
 Examples of
thermoplastics are:
polyethylene, PVC,
polystyrene, etc
 Polymer Classification

Thermoplastic Thermosetting
They are formed by addition polymerization only. They are formed by condensation polymerization.
They consist of long chain linear polymers with They have three dimensional network structures, joined
negligible cross-links. by strong covalent bonds.
They soften on heating readily because secondary The cross-links and bonds retain their strength on
forces between the individual chain can break heating and hence, they do not soften on heating on
easily by heat or pressure. prolonged heating charring of polymers is caused.
By re-heating to a suitable temperature, they They retain their shape and structure even on
can be softened, reshaped and thus reversed. heating. They cannot be reshaped & reversed.
They are usually soft, weak and less brittle. They are usually, hand, strong and more brittle.

These can be reclaimed from wastes. They cannot be reclaimed from wastes.
They are usually soluble in some organic solvents. Due to storing bonds and crosslinking they
are insoluble in almost all organic solvents.
Engineering Applications of Polymers
 ABS (Acrylonitrile-Butadine-Styrene)
 Disadvantages &
Limitations:
● Poor solvent resistance
● Low dielectric strength
● Only low elongations
available
● Low continuous service
temperature
 Advantages:
● Good impact resistance with toughness & rigidity
● Metal coatings have excellent adhesion to ABS
● Formed by conventional thermoplastic methods
● A light-weight plastic
 Typical Engineering Applications:
Automotive hardware (used in electroplated metal coatings for decorative
hardware), appliance cases, pipe, plated items.
 Engineering Applications of Polymers
 PVC (Polyvinyl Chloride)  PTFE (Polytetrafluoroethylene) or TEFLON

Polymerisation

vinyl Chloride Polyvinyl Chloride  Properties

● Highly crystalline
 Properties: ● High melting point, high temp.
● PVC is colourless, odourless & chemically inert powder stability, low temp. flexibility
● Insoluble in inorganic acids and alkalis, but soluble in ● Low friction, remain slippery
hot chlorinated hydrocarbons. ● Insoluble in any solvent
● It undergoes degradation in presence of heat (or) light. ● Electrical insulate
 Applications  Applications
☻ Building & construction ☻ Insulation of motor, generator,
☻ Pipes, flooring & vinyl siding wires, cable
☻ Wire, cable insulation ☻ Coating in food processing units
☻ Packaging ☻ Anti corrosive coat in weapons
☻ Flexible films, pool lining ☻ Gasket, industrial filters, belts,
☻ Artificial leather, wall covering non lubricated bearing
☻ Electrical outlet boxes, automotive bumpers ☻ Cardiovascular grafts, heart patches, knee ligament
Engineering Applications of Polymers

 Bakelite (Phenol Formaldehyde Resin)

● Condensation polymerization
using phenol & formaldehyde
via base/acid catalyst
● Product depends upon conc. of
reactant & type of catalyst used

 Application:
● used as an adhesive in plywood
laminations, grinding wheels etc.
 Properties ● used in paints, varnishes,
● Bakelite is rigid, hard, scratch resistant decorative articles like plates,
● Electrically insulative drinking glasses, dishes etc.
● Thermal stability up to 200 0C ● used for making electrical
Cooker with Bakelite insulator parts like plugs,
● Resistant to water, low flammability Handles switches, heater handles etc.,
 Polymer: Moulding Processes
 Different molding processes:
 This process involves fabrication of
 Compression moulding (Mobile Phone Cases/ Battery Trays)
plastic material into desired shape under
the influence of heat and pressure in a  Injection moulding (Car parts/Bottle caps)
closed chamber.  Extrusion moulding (Pipes/Hoses)
 Transfer moulding (Fibre reinforced polymer matrix composites)
 Blow moulding (PET bottles)
 Compression Moulding
 Applied to both thermoplastics and thermosetting plastics
 Compression moulding is one of the oldest and most widely used technique
 Moulding process:
☻ The mould is made up of two halves.
The lower half usually contains a cavity
in the shape of the article to be
moulded and the upper half has a
projection, which fits into the cavity
when the mould is closed
 Polymer: Moulding Processes
 Compression moulding process:  Compression moulding products
☻ The material to be moulded is placed in the cavity of the • Car tyres/rubber tyres
mould and then the mould is closed carefully under low • Rubber gaskets or seals
pressure • Handles
• Electrical components
☻ Finally the mould is heated to 100-200 °C & • Automotive parts
simultaneously high pressure (100-500 kg/cm2) is applied • Bottle caps, etc.
☻ The mould is left for some time so that polymerization
can take place, converting the raw material into the solid
final product.
☻ The mould is opened and the part is removed.

 Advantages:
o Low material waste
 Disadvantages:
o Little or no post processing required
 Limited materials can be used
o Good surface finish
with this process
o Minimum internal stresses
 Limited producible geometry.
 Polymer: Moulding Processes
 Injection Moulding:
 This method is mainly applicable to
thermoplastics
 The method is suitable for the mass
production of products with complicated
shapes
 Injection moulding process:
• The powdered plastics material is fed into
a heated cylinder through the hopper
• The plastic material melts under the
influence of heat and becomes fluid.
• The hot fluid is injected at a controlled
rate into a tightly locked mould by means
of a screw arrangement or by a piston
• The mould is kept cold to allow the hot  Injection moulding products
plastic to cure and becomes rigid. ● Telephones
● Buckets etc.
 Polymer: Moulding Processes
 Extrusion Moulding
 This method is mainly used for
continuous moulding of thermoplastic
materials into articles of uniform cross
section like rods, tubes etc.
 Extrusion moulding process:
☻ In this method, the powdered plastic
material is fed into the heated cylinder
through the hopper.
☻ The molten plastic material is then
pushed by means of a revolving screw
conveyor into a dice having the required
shape of the object to be manufactured.
The finished product that extrudes out is
cooled by atmospheric air. A long
conveyor carries away the cooled product.  Extrusion moulding products
● Pipes
● Hoses etc.
 Polymer: Moulding Processes
 Transfer moulding
 This method is used for thermosetting plastics
 The principle is same as that of the injection
moulding
 The powdered moulding materials is taken in a
heated chamber, while low temperature is
maintained at which the material just begins to
become plastic.
 This plastic is then injected through an orifice into the
mould by a plunger working at high pressure
 Due to the great friction developed at the
orifice during ejection, the temperature of
the material rises to such an extent that the
moulding powder becomes almost liquid.  Advantages of Transfer Moulding
So that it flows quickly and easily into the ● More complicated shapes can be fabricated by this method
mould. ● Less expensive
 Then the mould is heated up to the curing ● Blisters can be eliminated
temperature required for setting. Finally the ● Shrinkage and distortion are minimum
moulded article is ejected from the mould. ● Very delicate articles can be made by this method
 Polymer: Moulding Processes
 Blow moulding
 Blow moulding is the process of forming a
molten tube (preform) of thermoplastic
material (polymer or resin) and placing
the preform within a mould cavity and
inflating the tube with compressed air, to
take the shape of the cavity and cool the
part before removing from the mould.
 The major difference between injection
moulding and blow moulding is the kind
of product produced. Typically, blow
moulding is designed to produce hollow,
singular containers, such as bottles. On
the other hand, injection moulding is used
to produce solid pieces.
☻ Advantages: Because of lower pressure,
the mold costs in this blow molding are
lower as compared to injection molding
and the machinery costs are low as well.
 Conducting Polymers
 A conducting polymer is an organic based polymer that
can act as a semiconductor or a conductor.

 The most widely studied organic polymers are

Polyacetylene, Polyaniline (PANI), Polypyrroles,
Polythiophenes, Polyphenylene vinylenes.

◙ Conducting polymers (CPs) are extensively conjugated molecules.

They have alternating single and double bonds. In these molecules,
electrons are able to move from one end of the polymer to the other
through the extended π-orbital system.
◙ Hence CPs are known to be either semiconductors or  Factors that affect the conductivity
conductors giving them unique optical and electrical  Density of charge carriers
properties.  Their mobility
◙ Most polymers are poor conductors due to non-availability  The direction
of large number of free electrons in the conduction process.  Presence of doping materials
◙ However, conducting polymers are synthesized which (additives that facilitate the polymer
possess electrical Conductivity similar to metal conductors. conductivity in a better way)
 Temperature
 Conducting Polymers
I. Intrinsically Conducting Polymers (ICP)
 Different Types:
 Polymer consisting of alternating single and double bonds
I. Intrinsically conducting polymers (ICP) is called conjugated double bonds.
II. Doped Conducting polymers  In conjugation, the bonds between the carbon atoms are
III. Extrinsically conducting polymers (ECP) alternately single and double. Every bond contains a
localised “sigma” (σ) bond which forms a strong chemical
II. Doped Conducting Polymers bond. In addition, every double bond also contains a less
● It is obtained by exposing a polymer to a strongly localised “pi” (π) bond which is weaker.
charge transfer agent in either gas phase or  Conjugation of sigma and pi-electrons over the entire
in solution. backbone, forms valence bands and conduction bands.
 ICPs possess low conductivity (10-10  Example: Poly-acetylene polymers like poly-p-phenylene,
/Ohm.cm), but they possess low ionisation polyaniline, polypyrrole
potential/high electron affinity. So they can
be easily oxidised or reduced.
 The conductivity of ICP can be increased by
creating positive charges (oxidation) or by
negative charges (reduction) on the polymer
backbone. This technique is called DOPING .
 Conducting Polymers

 Doping: It is a process in which the polymer i. p-Doping:

structure can be disturbed - either by removing  It involves treating an intrinsically conducting polymer
electrons from (oxidation), or inserting them (ICP) with a Lewis acid which leads to oxidation
into (reduction), the material. process and positive charges on the polymer
backbone.
 There are two types of doping:  Some of the p-dopants are I2, Br2, AsF5, PF5 etc.
i. Oxidation with halogen (or p-doping).
ii. Reduction with alkali metal (called n-doping). 2(C2H2)n + 3I2 2[(C2H2)n+ I3-
polyacetylene
 Conductivity Mechanism in Polyacetylene ii. n-Doping:
 It involves treating an ICP with a Lewis base which
 The mechanism followed by polyacetylene for
leads to reduction process and negative charges on
the transfer of charge from one chain to
the polymer backbone.
another is called inter-soliton hopping.
 Some of the n-dopants are Li, Na, Ca, FeCl3,
 What is a soliton? naphthylamine etc.
 The soliton is a charged or a neutral defect in the
polyacetylene chain that propagates down the polyacetylene
chain, thereby reducing the barrier for
interconversion.
naphthylamine
 Conducting Polymers
 Conductivity in Polyacetylene
 In n-type doping (This can be done by dipping the film in
THF solution of an alkali metal) soliton is a resonance-
stabilized polyenyl anion of approximately 29-31 CH units in
length, with highest amplitude at the center of the defect.
 The solitons (anions) transfer electrons to a neutral soliton
(radical) in a neighboring chain through an isoenergetic
process.
 The charged solitons are responsible for making
polyacetylene a conductor.
 In p-type doping, The dopant (Iodine, I2) attracts an electron
from the polyacetylene chain to form (I3-) leaving a positive
soliton (carbenium ion) in the polymer chain that can move
along its length.
 The lonely electron of the double bond, from which an
electron was removed, can move easily.
 As a consequence, the double bond successively moves along the molecule, and the polymer is stabilized
by having the charge spread over the polymer chain.
 Conducting Polymers
III. Extrinsically conducting polymers (ECP)  Applications of conducting polymers
 These are those polymers whose conductivity is  As sensors into clothing:
due to the presence of externally added  Conducting polymer textiles as a camouflage for defense
ingredients in them. machinery. Since the textiles have no sharp edges they
 These are two types: absorb > 50% of the incident microwave radiation.
a) Conductive element filled polymer:  In LEDs
 It is a resin/polymer filled with carbon black,  In controlled drug release applications etc.
metallic fibres, metal oxides etc. Polymer acts Group 1 Group 2
as a binder to those elements. • Electrostatic materials o Molecular electronics
 These have good bulk conductivity and are low • Conducting adhesives o Electrical displays
• Electromagnetic shielding o Chemical, biochemical and
in cost, light weight, strong and durable. They
can be in different forms, shapes and sizes. • Printed circuit boards thermal sensors
• Artificial nerves o Rechargeable batteries
b) Blended Conducting Polymers:
• Antistatic clothing and solid electrolytes
 It is product obtained by blending a
• Piezoceramics Artificial nerves
conventional polymer with a conducting
• Active electronics o Drug release systems
polymer either by physical/by chemical change.
• Aircraft structures o Ion exchange membranes
 Such polymers can be processed and possess
better physical, chemical and mechanical  The first group utilizes their conductivity as its main property.
strength.  The second group utilizes their electroactivity.