Unit 1: Water Chemistry

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 CO2

CO2

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 Types of Impurities present in the water or characteristics imparted by impurities in water

Three types:
1. Physical impurities
2. Chemical impurities
3. Biological impurities

1. Physical impurities:
a) Colour: The colour in water is caused by metallic substances like salts of iron, manganese, industrial effluents.
This is due to dissolved substances and substances present as fine colloids.
For example, the yellowish-red colour indicates the presence of iron.

b) Turbidity: is due to the colloidal, extremely fine suspensions such as insoluble substances like clay, slit, and
micro-organisms.
Turbidity in water can be eliminated by sedimentation, coagulation, filtration, etc.

c) Taste: The presence of dissolved minerals in water produces taste.

The bitter taste can be due to the presence of Fe, Al, Mn, Sulphates, and lime.
Soap taste can be due to the presence of large amount of sodium bicarbonate.

d) Odour: Disagreeable odor in water may be caused by the presence of living organisms, and decaying vegetation,
including algae, bacteria, and fungi.
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Types of Impurities present in the water or characteristics imparted by impurities in water

2. Chemical impurities: It includes:

 Inorganic and organic chemicals released from dyes, paints, vanishes, drugs,

insecticides, pesticides, etc. All these pollute water bodies.

 Acids discharged in water by DDT, high explosives, battery, industries, etc.

The use of this type of contaminated water cause harmful effects on health of human-beings.

3. Biological Impurities:
 Biological impurities are algae, pathogenic bacteria, fungi, viruses, pathogens,
parasite-worms, etc.
 The sources of these contamination is discharge of domestic and sewage wastes,
excreta (from man, animals and birds), etc.

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 Sludge is a soft, loose, and slimy precipitate formed within the boiler.
 It is formed at comparatively colder portions of the boiler and
collects in the area where flow rate is slow.
 Ex: MgCO3, MgCl2, CaCl2, MgSO4.

Reasons for formation of sludges:

 The dissolved salts whose solubility is more in hot water
and less in cold water produce sludges.

Fig. Scale and Sludge in boilers

Disadvantages of sludges:
 Sludges are bad conductors of heat and results in the wastage of heat and fuel.
 Excessive sludge formation leads to the settling of sludge in slow circulation areas such as pipe
connections, plug openings, gauge–glass connections, leading to the choking of the pipes.

Prevention of sludge formation:

 Using soft water, which is free from dissolved salts like MgCO3, MgCl2, CaCl2, and MgSO4, can prevent
sludge formation.
 By blow down operation carried out frequently can prevent sludge formation.
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 SCALES:
 Scales are hard, adhering precipitates formed on the inner walls of the boilers.
 Scales are stick very firmly on to the inner walls of the boiler.

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Disadvantages of Scales:
1. Wastage of heat and fuels: Scales have poor thermal conductivity, so the rate of heat transformation is reduced.
2. Lowering of boiler safety is due to overheating of the boiler material becoming softer and weaker, which causes
distortion of the boiler.
3. Decrease in efficiency of the boiler due to scales deposited in the values and condensers of the boiler cause
choking.
4. Danger of explosion, which happens with the formation of the scales, the boiler plate faces higher temperature
outside and lesser temperature inside due to uneven expansion.

Prevention of scales:
1. By giving thermal shocks, by sudden heating and sudden cooling which makes scale brittle and
removed by scrubbing with wire brush.
2. If the scale is very hard, that is formed by CaCO3 can be removed by washing with 5-10% HCl, and
CaSO4 can be removed with EDTA solution.

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Causes:
Priming is caused by:
1. The presence of large amount of dissolved salts
2. High steam velocities
3. Sudden boiling
4. Improper boiler design
5. Sudden increase in steam production rate.

Prevention:
1. By controlling the velocity of steam
2. Maintaining low water levels in boilers
3. Effective softening and filtration of boiler feed water
3. Using good boiler design

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 FOAMING:
The phenomenon of formation of persistent foam or bubbles on the surface of water inside the boiler,
which do not break easily.

Causes:
1. Water containing dissolved impurities and suspended matter has a greater tendency to produce
foam.
2. The presence of a large quantity of suspended impurities and oils lowers the surface tension,
producing foam.

Prevention:
1. Adding antifoaming chemicals like castor oil or polyamides.
2. Besides castor oil, Gallic acid and tannic acids, corn oil, cotton seed oil, sperm oil, bees wax, etc., are
also used as antifoaming agents.
3. Blow down operation of the boiler can prevent foaming.
4. Removing oil form boiler water by adding compounds like sodium aluminate.

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 3. CAUSTIC EMBRITTLEMENT

The formation of brittle and in crystalline cracks in the boiler shell is called caustic embrittlement.

 The main reason for this is the presence of alkali-metal carbonates and
bicarbonates in feed water.
 In lime-soda process, some residual Na2CO3 is still present in the softened water.
 This Na2CO3 decomposes to give NaOH and CO2, due to which the boiler water
becomes “Caustic Soda”.
Na2CO3+ H2O → 2NaOH + CO2

 The H2O evaporates, the concentration of NaOH increase progressively creating a concentration
cell as given below thus dissolving the iron of the boiler as sodium ferrate (Na2FeO2).
 Caustic attack on boiler parts can be represented as:

 The iron at plane surfaces surrounded by dilute NaOH becomes cathodic while the iron at bends and joints
surrounded by highly concentrated NaOH becomes anodic which consequently decayed or corroded.
 This causes embrittlement of boiler parts such as bends, joints, reverts etc, due to which the boiler gets fail.
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Caustic embrittlement can be prevented:
 By maintaining the pH value of water and neutralization of alkali.
 By using Sodium Phosphate as softening reagents, in the external treatment of boilers.
 It can also be prevented by adding Tannin or Lignin or Sodium sulphate which prevents the
infiltration of caustic-soda solution blocking the hair-cracks.

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 Boiler corrosion:
The decay of boiler material by chemical or electrochemical attack by its environment is known as
“Boiler corrosion”.

The main reasons for boiler corrosion are:

Removal of dissolved Oxygen:

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Suitable chemicals are added to the boiler water either to precipitate or to convert the scale
into compounds is called internal treatment of the boiler feed water.

1. Calgon conditioning

2. Phosphate conditioning

3. Colloidal conditioning

4. Carbonate conditioning

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1. Calgon conditioning:

 Involves in adding calgon to boiler water.

 Calgon = Sodium hexa meta phosphate = Na2 [Na4 (PO3)6]

 The addition of Calgon to hard water causes the calcium and magnesium ions of hard water to
displace sodium ions from the anion of Calgon.

 This results in the removal of calcium and magnesium ions from hard water in the form of a complex
with Calgon.

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 2. Phosphate conditioning:

 The addition of Trisodium phosphate (Na3PO4) in hard water.

 It reacts with the hardness causing agents and gives calcium and
magnesium phosphates which are soft and nonadhere and can be
removed easily by blow-down operation.

Three types of Phosphates are employed.

i. Tri sodium Phosphate (Na3PO4): is too alkaline used for treat to too acidic water.
ii. Di sodium Phosphate (Na2 HPO4): is weakly alkaline used for treat to weakly acidic water.
iii. Sodium dihydrogen Phosphate (Na H2PO4): is too acidic used for treat to too alkaline water.
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3. Colloidal conditioning:

 In low-pressure boilers, scale formation can be avoided by adding organic substances like kerosene, tannin,
agar-agar (a gel), etc.,
 These substances get coated over the scale forming precipitates, thereby yielding non-sticky and loose
deposits, which can easily be removed by using blow-down operation.

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4. Carbonate conditioning:

 Reagent added is sodium carbonate (Na2CO3).

 In low pressure boilers scale formation can be avoided by adding sodium carbonate to boiler water.

 Deposition of CaSO4 as scale doesn’t takes place and calcium is precipitated as loose sludge
of CaCO3 which can be removed by blow down operation.

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In industry, four external methods are mainly employed for softening of water.

1. ZEOLITE OR PERMUTIT PROCESS

2. LIME-SODA PROCESS

3. ION EXCHANGE/DEMINERALIZATION PROCESS

4. DESALINATION OF BRACKISH WATER–REVERSE OSMOSIS (RO)

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 Zeolites are hydrated sodium aluminum silicates Na2O.Al2O3 xSiO2.yH2O. (x=2-10 and y=2-6) (inorganic salts).

 They work as water softeners by replacing the calcium and magnesium ions in water with the Sodium ions in
the zeolite.

1. Natural zeolites: Non-porous, amorphous and durable

e.g. Na2O. Al2O3.3SiO2.2H2O

2. Synthetic zeolites: Gel like structures, generally porous Na2CO3, Al2O3 and
SiO2 heated together Na2O.Al2O3 xSiO2.yH2O. (x=2-10 and y=2-6)
e.g. Silicalite-1 and ZSM-5 (MFI)

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 In this process hard water is allowed to pass through a bed of zeolite at a specified rate.
 Then the sodium ions present in the zeolite bed continuously replace the calcium and magnesium ions present in water
and hence the water becomes soft.

Regeneration:
 When the zeolite bed becomes exhausted it requires
regeneration.
 This is achieved by passing 10% NaCl solution through it.

CaZe + 2NaCl → Na2Ze + CaCl2

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 Advantages:
1. Almost complete removal of hardness (10ppm)

2. It is compact

3. Requires only less time for softening

4. No sludge formation since no precipitate is formed

5. Can work under pressure.

Disadvantages:
1. More sodium salt concentration in softened water.

2. Turbidity containing water cannot be used

3. Process exchange only Ca2+ and Mg2+ ions but cannot exchange HCO3- and CO32- ions. So, it cannot be used in boilers.

4. If Fe2+ and Mn2+ are present in large quantities. They form respective zeolites, so zeolites cannot be regenerated

5. Water consisting of high alkalinity or acidity cannot be used because zeolite is decomposed
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 Numerical Problems based on Zeolite Process

Regeneration of NaCl Solution

 Concentration of NaCl (Strength, Normality, W/V %)
 Volume of NaCl Solution

Hard Water
 Hardness
 Volume of Water

Q1. Determination of Hardness

Q2. Determine the volume of water
Q3. Determine the volume of NaCl solution required for regeneration
Q4. Determine the concentration of NaCl solution.

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Principle: The lime soda process involves the chemical conversion of all the soluble
hardness causing salts by the addition of soda (Na2CO3) and lime [Ca(OH)2] into
insoluble precipitates which could easily be removed by settling and filtration.

Functions of lime Removes:

1. Temporary hardness
2. Permanent Mg hardness
3. Dissolved Fe, Al salts
4. Dissolved CO2 and H2S gases
5. Free mineral acids Present in water

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Lime:
The temporary hardness of water can be removed by hydrated lime. It react with Ca(HCO3)2 &
Mg(HCO3)2 to form insoluble precipitate of calcium carbonate and magnesium hydroxide respectively.

Hydrated lime is also used to remove permanent hardness (magnesium salt impurities only) from
water. It reacts with MgSO4 & MgCl2 to form insoluble precipitate of magnesium hydroxide.

In above reaction calcium based impurities like CaCl2 & CaSO4 also form, which are soluble in
water. Therefore calcium based impurities (CaCl2 & CaSO4) are not removed by lime treatment.

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Soda:
Sodium carbonate (Na2CO3) is used to remove permanent hardness of water which
caused
By MgSO4 & MgCl2 or CaCl2 & CaSO4.

It consists of
 a reaction tank
 a conical sedimentation vessel and
 a sand filter. Fig. Continuous hot lime-soda softner

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 Process
 The lime-soda process can be carried out both at room temperature as well as at higher temperatures.

 The process carried out at room temperature is called cold lime–soda process and that carried out at
80°-150°C is called hot lime-soda process.

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 Hot Lime-Soda Process

 Water is treated with the softening chemicals at a temperature of 80°-150°C.

 Since the process is carried out at a temperature close to the boiling point of the
solution, the reaction proceeds faster and the softening capacity of the process
increases several times.

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Cold Lime Soda Process:
 Water to be softened is treated with calculated quantities of lime and soda at room temperature.
 Precipitates formed are finely divided.
 Small amounts of a coagulant such as alum, aluminium sulphate, sodium aluminate etc., are also added
to flocculate.

Sodium aluminate also helps in the removal of silica and oil present in Fig. Continuous cold lime-soda
water. softner
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 Advantages:
1. Economical
2. Hot lime soda process is much faster than the cold lime soda process
3. During this process pH value of water is increased hence the corrosion of
pipe is reduced
4. Besides the removal of hardness, the quantity of minerals in water is also
reduced
5. Due to alkaline nature of water, amount of pathogenic bacteria in water are also
removed
6. Requires less amount of coagulants

Disadvantages:
1. The softened water is not completely free from hardness (15-30ppm of
hardness still remains)
2. Disposal of large amount of sludge is a problem
3. Careful operation and skilled supervision is required for efficient treatment
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Difference between cold and hot lime soda process

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Numerical Problems Based on Lime-Soda Method

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= 1.17 Kg

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 Cross linked long chain organic polymers with a microporous structure, and the
“functional Groups” attached to the chains are responsible for the ion-exchanging
properties.
 Resins with acidic functional groups are capable of exchanging H+ ions with other
cations.
 Resins with basic functional groups are capable of exchanging OH−ions with other
anions.
 Resins are classified as:
i. Cation Exchange Resins ii. Anion Exchange Resins.

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i. Cation Exchange Resins (RH+) :
 Cation exchange resins are styrene divinyl benzene co-polymers.
 on sulphonation (or) carboxylation, which contains –COOH, –SO3H functional groups (FG)
 These FG responsible for exchanging their hydrogen ions with cations in water.

(Exhausted
Resin)
(RH+ = Cation exchange)

Fig. Acidic or cation exchange resin (sulphonate form)

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ii. Anion Exchange Resins (OH-):
 Anion exchange resins are Phenol formaldehyde (or) amine formaldehyde copolymers
 It contains amino or basic functional groups which responsible for exchanging their OH− ions with anions
in water.

Fig. Basic or anion exchange resin (hydroxide form)

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 Cation exchange resins, which remove Ca+2 and Mg+2 ions and exchange an equivalent amount
of H+ ions.
 Anions exchange resins remove bicarbonates, chlorides and sulphates from water exchange
equivalent amount of OH- ions.
 Thus by passing hard water through cation hardness is observed by the following reactions.
 H+ and OH ions, thus released in water from respective cation and anion exchange columns, get
−

combined to produce water molecules.

H+ + OH− → H2O

 Softened water ion free from anions and cations low

(2ppm) or zero hardness is obtained.

Softening Cycle:
1. Cation Exchange Resin:

2. Anion Exchange Resin: Fig. Ion Exchange Process

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 2. Regeneration Cycle:
 When cation exchanger losses capacity of producing H+ ions and exchanger losses capacity of producing
OH- ions, they are said to be exhausted.

 The exhausted cation exchanger is regenerated by passing it through dilute sulphuric acid.

 The exhausted anion exchanger is regenerated by passing a dilute solution of NaOH.

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Merits of the Ion exchange process:
 The process can be used to soften highly acidic or alkaline water.

 It produces water of very low hardness (2ppm)

 Very good for treating water for use in high-pressure boilers.

Demerits of Ion-exchange process:

 The equipment is costly and more expensive chemicals are needed.

 If water contains turbidity, the output of the process is reduced. (Turbidity must be below
10ppm; otherwise, it has to be removed by coagulation and filtration.)

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 Numerical Problems based on Ion Exchange Process:

Example 1: After treating 104 L of water by ion exchange, the cationic resin required 200 L of 0.1 N HCl &
anionic resin required 200 L of 0.1 N NaOH solutions. Find hardness of the above sample of water.

Sol.
• In an ion exchanger, all hardness causing cations are removed by cation exchanger; while anion exchanger
removes anions of the constituents present in water.
• Consequently, the amount of acid used for generation of cation resin refers hardness of water.

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Example 2:
1000 L water was softened by Ion Exchange method. For regeneration 150 L of 0.1 N each of HCl and
NaOH was needed by respective exhaustive resins. Calculate the hardness of water.

Sol.
• In an ion exchanger, all hardness causing cations are removed by cation exchanger; while anion exchanger
removes anions of the constituents present in water.
• Consequently, the amount of acid used for generation of cation resin refers hardness of water.

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Example 3:

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 The process of removing common salt (Sodium Chloride) from the water is known as desalination.

Depending upon the quantity of dissolved salts, water is graded as:

i. Sea water is about 35 parts per thousand,ppt (35 parts in 10³)
ii. Brackish water is between 0.5 and 30 parts per thousand.
iii. Fresh water is less than 0.001 parts per thousand.

 Sea water and brackish water can be made available as drinking water through the desalination
process.

Desalination

Reverse Osmosis Electrodialysis

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Electrodialysis Process
Components
 Power Source
 Cathode and Anode
 Ion Exchange Membranes

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Osmosis:

 When two solutions of unequal concentrations are separated by a semi permeable membrane, flow
of solvent takes place from dilute to concentrate sides, due to osmosis.

 A solution that is less concentrated will have a

natural tendency to migrate to a solution with a
higher concentration
 A semi-permeable membrane is a membrane that
will allow some atoms or molecules to pass but not
others.

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 If, however a hydrostatic pressure in excess to osmotic pressure is applied on the concentrated side,
the solvent flow is reversed, i.e, solvent is forced to move from concentrated side to dilute side across the
membrane. This is the principle of reverse osmosis (RO).

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 How does Reverse Osmosis work?
 RO: In this method, pure solvent is separated from its contaminants, rather than removing contaminants from the
water.
 The membrane filtration is sometimes also called super-filtration or hyper-filtration.

Method:
 In this process, pressure is applied to the sea water or
impure water to force the pure water content of it out the
semipermeable membrane, leaving behind the dissolve
solids.

 The membrane consists of very thin film of cellulose

acetate, affixed to either side of a perforated tube.

 However, more recently superior membranes made of

polymethacrylate and polyamide polymers have come into
use.

Fig: Reverse Osmosis Cell

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Advantages:

1. RO possesses distinct advantages of removing ionic and non-ionic, colloidal, and high
molecular weight organic matter.

2. It removes colloidal silica, which is not removed by demineralization.

3. The maintenance cost is almost entirely on the replacement of the semi-permeable

membrane.

4. The lifetime of membrane is quite high, about 2 years

5. The membrane can be replaced within a few minutes, thereby providing nearly
uninterrupted water supply.

6. Due to low capital cost, simplicity, low operating cost and high reliability, the RO is
gaining grounds at present for converting sea water into drinking water and for obtaining
water for very HP boilers.

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 Disadvantages:

Reverse Osmosis wastes a lot of water

Reverse Osmosis removes all minerals

Dependency on electricity

The High Pressure Pump is required to extract Clear water from the membrane element.

Water taste altered

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