Chemical Technology - I

Dr. Mohammad Kamruzzaman

Associate Professor

Dept of Applied Chemistry & Chemical Engineering

University of Dhaka

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Water Conditioning and Water Treatment

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 Introduction

Water is one of the abundantly available substances in nature.

Is an essential constituent of all animal and vegetable mater and forms about 75% of
the matter of earths crust.
Is an essential ingredient of animal and plant life.
Is absolute essential for all human activities- domestic, agricultural and industrial.
Four-fifth of the earths surface is covered by water
About 97.3% of the total sources is present in oceans which is too saline (3.5% salt
concentration) for any practical applications.
Considerable quantities are also locked up in polar ice caps and giant glaciers, rock
and crevices and minerals.
Less than 1% of the worlds water resources is available for ready use.
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 Sources of Water

The chief sources of water supply for industrial/house hold purposes are: Ground
water, Surface water, Sea water and Rain water.
Ground water may come from springs, shallow, wells and from deep wells
Surface water is flowing water (rivers, streams etc) and still water (lakes, ponds
etc.)
Sea water is not much used in industries because of great problems it creates in
chemical engineering.
Rain water is the purest form of naturally occurring water. It may be collected, e.g.
on roofs, but this water is also not used much for industrial use.

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 Quality of Natural Water
Water obtained from different sources is associated with a large number of
impurities.
For example, water gets impurities of various kinds from ground or soil with which it
comes into contact.
Water also gets contaminated with sewage and industrial wastes or effluents when
these are allowed to flow into running water through percolation through the ground.
The substances contained in natural or raw waters can be divided into the following
three groups:
1. Coarsely dispersed or suspended substances.
2. Colloids and molecular substances.
3. Ion dispersed substances.
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 Quality of Natural Water

Water from a water supply scheme may contain physical, chemical and biological
impurities.
Physical impurities impart color, taste, odor and turbidity to the water.
Chemical impurities cause hardness and water pollution.
Excess quantities of metals and dissolved gases cause corrosion of pipes and
fittings.
Bacteriological impurities are due to pathogenic bacteria which spread diseases such
as cholera, typhoid, diarrhea and dysentery.

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 Objectives of water Treatment

Objectives of the treatment of water are:

To remove color, objectionable odor and taste.
To remove dissolved gases, dissolved suspended impurities and harmful minerals.
To remove suspended as well as dissolved organic impurities
To remove pathogenic bacteria.
To make water safe for drinking and domestic purposes.

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 Water Treatment
Four Stages:
Preliminary treatment- involves screening for the removal of large objects and
skimming for removal of girt.
Primary treatment- suspended solids and colloidal matter are first allowed to
settle down and then removed.
Secondary treatment- organic pollutants both suspended and dissolved are
oxidized in the presence of microorganisms.
Tertiary treatment- involves the use of a number of techniques for removing non-
biodegradable pollutants, ionic constituents and trace impurities.

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 Wastewater Treatment Methods
Physical methods include processes where no gross chemical or biological changes
are carried out and strictly physical phenomena are used to improve or treat the
wastewater.
Common Physical Methods:
Sedimentation (Clarification): physical phenomena relating to the settling of
solids by gravity are allowed to operate.
Screening: to remove larger entraind objects.
Aeration: physically adding air, usually to provide oxygen to the wastewater.
Filtration: wastewater is passed through a filter medium to separate solids.

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 Wastewater Treatment Methods
Flotation and Skimming: Permitting greases or oils, for example, to float to the
surface and skimming or physically removing them from the wastewaters is often
carried out as part of the overall treatment process.
Degasification: Removal of gases.
Equalization: In certain industrial wastewater treatment processes strong or
undesirable wastes are sometimes produced over short periods of time. Since
such "slugs" or periodic inputs of such wastes would damage a biological
treatment process, these wastes are sometimes held, mixed with other
wastewaters, and gradually released, thus eliminating "shocks" to the treatment
plant. This is call equalization.

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 Wastewater Treatment Methods
Chemical treatment consists of using some chemical reaction or reactions to
improve the water quality.
Chlorination: Probably the most commonly used chemical process is
chlorination. Chlorine, a strong oxidizing chemical, is used to kill bacteria and to
slow down the rate of decomposition of the wastewater.
Neutralization: A chemical process commonly used in many industrial wastewater
treatment operations is neutralization. Neutralization consists of the addition of
acid or base to adjust pH levels back to neutrality. Since lime is a base it is
sometimes used in the neutralization of acid wastes.

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 Wastewater Treatment Methods

Coagulation: Coagulation consists of the addition of a chemical that, through a

chemical reaction, forms an insoluble end product that serves to remove
substances from the wastewater. Polyvalent metals are commonly used as
coagulating chemicals in wastewater treatment and typical coagulants would
include lime, certain iron containing compounds (such as ferric chloride) and alum
(aluminum sulfate).
Adsorption: Certain processes may actually be physical and chemical in
nature. The use of activated carbon to "adsorb" or remove organics, for
example, involves both chemical and physical processes
Ion exchange: involves exchanging certain ions for others, are not used to any
great extent in wastewater treatment.
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 Wastewater Treatment Methods
Biological treatment methods use microorganisms, mostly bacteria, in the
biochemical decomposition of wastewaters to stable end products. More
microorganisms, or sledges, are formed and a portion of the waste is converted to
carbon dioxide, water and other end products. Biological treatment methods can be
divided into aerobic and anaerobic methods, based on availability of dissolved
oxygen.
Aerobic
1. Activated Sludge Treatment Methods 2. Aerobic Digestion
3. Trickling Filtration 4. Oxidation Ponds
5. Lagoons

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 Wastewater Treatment Methods
Anaerobic
Anaerobic Digestion
Septic Tanks
Lagoons

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 Hardness of Water

The total hardness in water (HT) is defined as the summary concentration of

calcium and magnesium cations expressed in milligrams equivalents per kilogram (mg-
equiv/kg) or microgram equivalents per kilogram (g-equiv/kg).
Hardness is related as HT = Hc + Hnc.
HT is total hardness
Hc is carbonate hardness and
Hnc is non-carbonate hardness.
The presence of Ca2+ (or of Mg2+ or Fe2+) in water is objectionable because of
formation of insoluble precipitates when such water is boiled or when soap is added.
Water that behaves in this way is called hard water.

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 Hardness of Water

The water is called hard as it is hard to get lather with soap (which is composed of
sodium salt of higher fatty acids such as stearic, oleic and palmitic acids) when it is
added to such a sample of water.
The sample of water is called soft when it leathers readily with the soap.
Types of hardness- hardness of water is of two types-
Temporary or carbonate hardness and Permanent hardness.
Carbonate or temporary hardness is caused by the bicarbonates of calcium and
magnesium in water and can be removed even by boiling.
The non-carbonate or permanent hardness is due to the presence of sulfates and
chlorides of calcium and magnesium and can not be removed by boiling etc. Its
removal requires the use of chemical agents and other methods.

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 Hardness of Water

The common units used in expressing water analyses are parts per million (ppm),
grains per gallon (gr/gal) and milligrams per liter (mg/L).
One grain per gallon is equivalent to 17.1 ppm and 17.1 mg/L.
Parts per million, ppm - is commonly used as a measure of small levels of pollutants
in air, water, body fluids, etc.
Parts per million (ppm) is the mass ratio between the pollutant component and the
solution and is defined as
ppm = 1,000,000 mc / ms
where,
mc = mass of component (kg, lbm)
ms = mass of solution (kg, lbm)
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 Softening of Water
Softening is the term applied to processes which remove or reduce the hardness of
water.
Water softening is the removal of calcium, magnesium, and certain other metal
cations in hard water.
The resulting soft water is more compatible with soap and extends the lifetime of
plumbing. Water softening is usually achieved using ion-exchange resins.
Purification, as distinguished from softening, usually refers to the removal of
organic matter and microorganism from water.

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 Softening of Water
The major question is how to soften hard water effectively and economically.
One way is to add sufficient quantities of soap. Thus enough stearate ions are added
to precipitate all the objectionable Ca2+ ions, leaving the excess soap to carry on the
cleansing action.
Another way is to boil the water. The temporary hardness, which is attributed to
the presence of bicarbonates of calcium and magnesium can be removed simply by
boiling the water or by adding lime to the hard water. The soluble bicarbonates of
calcium and magnesium decompose on boiling and are precipitated as insoluble
carbonates which are allowed to settle and water is filtered off.

Ca(HCO3)2 CaCO3 + CO2 + H2O

Mg(HCO3)2 MgCO3 + CO2 + H2O
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 Softening of Water
Ca(HCO3)2 CaCO3 + CO2 + H2O
Mg(HCO3)2 MgCO3 + CO2 + H2O

The reactions are reversible, but the forward reaction can be made dominant by
boiling off the CO2. Boiling , however, is not practical for large scale softening.
In the Clarks process, calculated amount of lime is added to the hard water,
whereby the bicarbonates are converted into insoluble carbonates and are removed
as above.

Ca(HCO3)2 + Ca(OH)2 2CaCO3 + H2O

Mg(HCO3)2 + Ca(OH)2 MgCO3 + CaCO3 + H2O

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 Softening of Water
Permanent hardness can not be removed by merely boiling or adding lime. Special
methods are used for the removal of permanent hardness.
So the third way to soften water is to precipitate Ca2+ by adding washing soda,
Na2CO3. the added CO32- ions react with Ca2+ ion to give insoluble CaCO3. If
bicarbonate ion is present, the water may be softened by adding a base such as
ammonia. The base de-protonates HCO3- to give CO32-, which then precipitates the
Ca2+.
The fourth way to soften water is to tie up the Ca2+ ion so that it becomes harmless.
One way to do this is to form a complex containing Ca2+. Certain phosphates, such as
sodium phosphates (Na3PO4) act as sequestering agents by forming complexes in
which Ca2+ is trapped by the phosphates.
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 Softening of Water
The fifth and most clever method of softening water is to replace the offending
calcium ion by another ion such as Na+.
This is done by the process called ion exchange. The ion exchangers originally used
for softening water were naturally occurring silicate materials, called zeolites.
The giant silicate network of a zeolite is negatively charged and is composed of
covalently bound silicon, oxygen, and aluminum atoms.
Zeolites are very closely related in structure to clays, which also show ion exchange.
The mobile Na+ ions in the pores can be readily exchanged for Ca2+ ions.

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 Lime-Soda Processes

In this process, the lime treatment is followed by the addition of soda ash (Na2CO3)
as a result of which calcium ions in the hard water are removed as CaCO3, and
magnesium ions as Mg(OH)2.
This process is used for the removal of temporary as well as permanet hardness and
has been divided into-
The cold lime process and The hot lime process.
The cold lime process is used for partial softening of water, say 100 ppm to 35 ppm
of hardness.
The hot lime process is employed almost entirely for conditioning the boiler feed
water.

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 Lime-Soda Processes
The reactions involved are:
For Carbonate Hardness
Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O
Mg(HCO3)2 + Ca(OH)2 MgCO3 + CaCO3 + 2H2O

Since MgCO3 is fairly soluble, further addtion of lime is nesseary, causing

MgCO3 + Ca(OH)2 Mg(OH)2 + CaCO3

For non-carbonate soluble calcium and magnesium salts

MgCl2 + Ca(OH)2 Mg(OH)2 + CaCl2
CaCl2 + Na2CO3 CaCO3 + 2NaCl
CaSO4 + Na2CO3 CaCO3 + Na2SO4
MgSO4 + Na2CO3 + Ca(OH)2 Mg(OH)2 + CaCO3 + NaSO4

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 Lime-Soda Processes
If there is excess of lime in the softened water, the water will be made hard due to
the presence of soluble Ca(OH)2
So it is most essential to add requisite amounts of Ca(OH)2 and Na2CO3 to the hard
water.
For removing 10 ppm of hardness from one million gallon of water, the following
quantities have been proposed:
1) Ca(HCO3)2 hardness (expressed as CaCO3) 521 lbs of lime.
2) Mg(HCO3)2 hardness (expressed as CaCO3) 1040 lbs of lime.
3) Calcium non-carbonate hardness (expressed as CaCO3) 900 lbs of soda ash
4) Magnesium non-carbonate hardness (expressed as CaCO3) 900 lbs of soda ash and
520 lbs of lime.
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 Lime-Soda Processes

In cold lime soda process, the reactions take place at room temperature as a result
of which partial softening of water takes place and all hardness forming salts are
not precipitated completely.
Cold lime soda process is not used now a days for softening of boiler feed water,
because of the following reasons.
a) Water treated in lime soda process does not have zero hardness.
b) The residual hardness is harmful for water tube boilers.

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 Lime-Soda Processes
The hot soda lime process is similar to cold process
except that the mixture of raw water, softening
chemicals and seed-sludge is heated near about the
boiling point of water.
The reactions are much more faster and the
precipitation becomes almost complete, because of
the fact that reactions are carried out near about the
boiling point.
The precipitation also takes place much more quickly,
and hence only one tank is sufficient.
Fig.: Continuous type of hot lime
Moreover, most of the dissolved gases, such as air or soda softener

carbon dioxide are removed or driven off.

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 Lime-Soda Processes
The most important advantages of hot lime soda process are:
a) The reaction is completed within a short period.
b) Silica in water also gets precipitated. Silica is precipitated by adding magnesium
oxide and lime at about 50C.
The most important disadvantages of lime soda process are that
a) It cannot be used for household use because it is difficult to know how much of
Ca(OH)2 and Na2CO3 should be added and then how to filter off the precipitates,
b) It is not suitable for many industrial purposes, because it usually leaves water
super saturated with CaCO3. this can be very serious in a laundry, where CaCO3
may end up on the customers clothing.

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 Permutit or Zeolite Process
In this process, water is softened through a natural or artificial zeolite.
Permutit is an artificial zeolite, called as hydrate of sodium aliminum orthosilicate and can
be obtained in the form of a coarse sand by fusing together sodium carbonate (Na2CO3),
alumina (Al2O3) and silica (SiO2).
Zeolites, known as green sand are used for water softening, but artificial zeolite known as
permutit is more common and it has a general formula Na2O.Al2O3.nSiO2.xH2O (n = 5-13, x
= 3-4).
Permutit or zeolite is insoluble in water, but can act as base exchanger when brought in
contact with water containing cations.
The zeolite or permutit is placed in a suitable column as shown in Fig. and hard water
containing Ca2+ and Mg2+ ions is allowed to percolate through it. This process removes both
temporary and permanent hardness.
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 Permutit or Zeolite Process
In this process, water is softened through a natural or artificial zeolite.
Permutit is an artificial zeolite, called as hydrate of sodium aliminum orthosilicate and can be
obtained in the form of a coarse sand by fusing together sodium carbonate (Na2CO3), alumina
(Al2O3) and silica (SiO2).
Zeolites, known as green sand are used for water softening, but artificial zeolite known as permutit
is more common and it has a general formula Na2O.Al2O3.nSiO2.xH2O (n = 5-13, x = 3-4).

Fig.: Structure of o naturally occurring zeolite,

NaAlSiO4. The sodium ions are loosely held in
holes in the lattice

The mobile Na+ ions in the pores can be readily exchanged

for Ca2+ ions.
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 Permutit or Zeolite Process

Permutit or zeolite is insoluble in water, but

can act as base exchanger when brought in
contact with water containing cations.
The zeolite or permutit is placed in a
suitable column as shown in Fig. and hard
water containing Ca2+ and Mg2+ ions is allowed
to percolate through it.
This process removes both temporary and
permanent hardness.

Fig.: Permutit Process

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 Permutit or Zeolite Process
The permutit or zeolite is represented as Na2Z and after base exchange it is
converted into CaZ and MgZ.
Sodium present in the zeolite is replaced by divalent Ca2+ and Mg2+ ions present in
the hard water. Water is thus softened as sodium salts do not cause hardness.

Reactions
Na2Z + Ca(HCO3)2 2NaHCO3 + CaZ
Na2Z + Mg(HCO3)2 2NaHCO3 + MgZ
Na2Z + CaSO4 Na2SO4 + CaZ
Na2Z + MgSO4 Na2SO4 + MgZ
Na2Z + CaCl2 2NaCl + CaZ
Na2Z + MgCl2 2NaCl + MgZ
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 Permutit or Zeolite Process
After some time of use, the whole of zeolite gets exhausted.
The zeolite may be regenerated by treatment for some hours with 10% solution of sodium
chloride, when the sodium salt of zeolite is formed.
The soluble chloride of Ca and Mg passing into the solution can thus be washed away.

CaZ + 2NaCl CaCl2 + Na2Z

The permutit or zeolite process has become a commercial success, because calcium and
magnesium zeolite formed by passing hard water through the bed of sodium zeolite can be
easily recovered into sodium zeolite.
Soft water obtained by this method is used mostly for laundry purpose. Water softened
by this process can not be used for boiler purpose.

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 Ion Exchange

Ion exchange has become a valuable chemical conversion process.

Its utilization on a large industrial scale is widespread, including the commercial

production of demineralized water having low electrical conductivity.

A variety of synthetic organic resins have been developed which can exchange cation and
anion present in water.

The process enables the removal of all soluble minerals of water without subjecting it to
the costly distillation process.

Two types of Ion Exchangers-

Cation exchange resins

Anion exchange resins

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 Ion Exchange

A cation exchanger may be defined as a high molecular weight, cross linked polymer
containing sulphonic, carboxylic, phenolic etc. groups as integral part of the resin and
eqiuvalent amount of cations.
In other words, a cation exchanger consists of a polymeric anion and active cations.
Cation exchange occurs when the mobile, positively charged cation fixed to the negatively
charged fixed group of the ion exchanger, exchanges for another cation in the solution.
An anion exchange resin is a polymer containing amine or quarternary ammonium groups as
integral parts of the resin and equivalent amount of anions, such as Cl-, SO42-, OH- ions etc.
Anion exchange occurs when the mobile, negatively charged anion attached to the positively
charged fixed group on the ion exchange resin is exchanged for another anion in the solution.

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 Ion Exchange

The first products used industrially for ion exchange were naturally occurring
inorganic zeolites, such as aluminum silicates, which have very low exchange capacity
per cubic meter of the material. The next improvement was the introduction of
organic ion exchangers which have very high exchange capacity per cubic meter of
material.
The next improvement was the introduction of organic ion exchangers made from
sulfonated natural products such as coal, lignite, and peat.
However, most high-capacity ion-exchange resins are based upon poly-styrene-
divinylbenzene (SDVB). Over 80 percent of ion-exchange resins are used for the
treatment of water.

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 Ion Exchange
Sodium-cation-exchange process is the most widely employed method for softening water.
During the softening process, calcium and magnesium ions are removed from hard water by
cation exchange for sodium ions.

When the exchange resin has essentially removed the

calcium and magnesium ions to the limit of its
capacity, the resin is regenerated to the sodium form
with a salt solution in the pH range of 6 to 8.
This type is exceptionally stable at high temperature
(up to 150C) and over the wide pH range of 0 to 14.

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 Ion Exchange
The symbol R represents the cation-exchanger radical in the following reactions for softening:

Ca (HCO3)2 Ca (HCO3)2
SO4 + 2NaR R2 + Na2 SO4
Mg Cl2 Mg
Sodium cation Cl2
exchanger Calcium and/or
magnesium cation
exchanger
(soluble) (insoluble) (insoluble) (soluble)

When the ability of the cation-exchange bed to produce completely softened water is exhausted, the softener
unit is temporarily taken out of service, backwashed to cleanse and hydraulically reclassify the resin particles
in the bed; regenerated with a solution of common salt (sodium chloride), which removes the calcium and
magnesium in the form of their soluble chlorides.

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 Ion Exchange
The regeneration reactions may be indicated as follows, using salt (or H2SO4 on a hydrogen cycle):

Ca Ca
R2 + 2NaCl 2NaR + Cl2
Mg Mg
(soluble) (insoluble) (insoluble) (soluble)
The hydrogen-cation-exchange process closely resembles the sodium cation procedure, except that all
exchange resins contain an exchangeable hydrogen ion and can be employed to remove all cations.
The symbol R represents the complex radical for the hydrogen-cation exchanger in the following reactions for
exchanges with bicarbonates:

Ca Ca
Mg (HCO3)2 + 2HR Mg R2 + 2H2O + 2CO2
Na2 Hydrogen Na2
cation
exchanger
(soluble) (insoluble) (insoluble) (soluble)
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 Ion Exchange
The reactions with sulfates and chlorides, using the symbol R to represent the organic radical of the
exchanger, may be indicated as follows:
Ca Ca
SO4 Mg SO4
Mg + 2HR R2 + H2
Cl2 Na2 Cl2
Na2 Hydrogen
cation
exchanger
(soluble) (insoluble) (insoluble) (soluble)

Regeneration with sulfuric acid is the most widely used and most commercial method of regeneration.
The reactions, in condensed form, may be indicated as follows:

Ca Ca
Mg R2 + H2SO4 Mg SO4 + 2HR
Na2 Na2

(Insoluble) (Soluble) (Soluble) (Insoluble)

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 Ion Exchange
Anion exchangers are either highly basic or weakly basic.
Both types remove strongly ionized acids, but weakly ionized acids such as silicic acid and
carbonic acids can only be removed by highly basic anion exchangers.
For the anion exchange of strongly ionized acid (HCl, H2SO4, HNO3, etc.), where R4N
represents the complex anion exchanger radical, the following reaction takes place:

H2SO4 + 2R4NOH (R4N)2SO4 + 2H2O

Soluble insoluble insoluble soluble
Regeneration
(R4N)2SO4 + 2NaOH 2R4NOH + Na2SO4
inoluble soluble insoluble soluble
Highly basic anion exchangers are regenerated with caustic soda, while weakly basic anion
exchangers may be regenerated with caustic soda, soda ash, or ammonium hydroxide.

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 Ion Exchange Process

Fig.: Ion Exchange Method

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 Book References
1. Shreves Chemical Process Industries
By George T. Austtin
2. Industrial Chemistry
By B. K. Sharma.
3. Outlines of Technology
By M. Gopala Rao.
4. Environment: An Introduction to Fresh & Wastewater Treatment Process.
By Prof. A. H. M. Mahbubar Rahman.

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Ca (HCO3)2 Ca (HCO3)2
SO4 + 2NaR R2 + Na2 SO4
Mg Cl2 Mg
Sodium cation Cl2
exchanger Calcium and/or
magnesium cation
exchanger
(soluble) (insoluble) (insoluble) (soluble)

Ca Ca
R2 + 2NaCl 2NaR + Cl2
Mg Mg
(soluble) (insoluble) (insoluble) (soluble)

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Ca Ca
Mg (HCO3)2 + 2HR Mg R2 + 2H2O + 2CO2
Na2 Hydrogen Na2
cation
exchanger
(soluble) (insoluble) (insoluble) (soluble)

Ca(HCO3)2 CaCO3 + CO2 + H2O

Mg(HCO3)2 MgCO3 + CO2 + H2O

Ca Ca
R2 + 2NaCl Ca
Mg R2
Mg Mg

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Ca (HCO3)2 Ca (HCO3)2
SO4 + 2NaR R2 + Na2 SO4
Mg Cl2 Mg
Sodium cation Cl2
exchanger Calcium and/or
magnesium cation
exchanger
(soluble) (insoluble) (insoluble) (soluble)

Ca Ca
Mg (HCO3)2 + 2HR Mg R2 + 2H2O + 2CO2
Na2 Na2

Ca Ca
R2 + 2NaCl Ca
Mg R2
Mg Mg

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Ca Ca
Mg R2 + H2SO4 Mg SO4 + 2HR
Na2 Na2

(Insoluble) (Soluble) (Soluble) (Insoluble)

Ca Ca
R2 + 2NaCl Ca
Mg R2
Mg Mg

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 Ca (HCO3)2 Ca (HCO3)2
SO4 + 2NaR R2 + Na2 SO4
Mg Cl2 Mg
Sodium cation Cl2
exchanger Calcium and/or
magnesium cation
exchanger
(soluble) (insoluble) (insoluble) (soluble)

+ 2NaR
Ca
R2 + 2NaCl Ca Ca
Mg R2
Mg
Mg
(HCO3)2
Bicarbonate, SO4
Calcium sulfate, Cl2
and/or and/or
Magnesium chloride

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 Silica Removal
Silica is not removed by hydrogen-cation exchange or sodium zeolite exchange.
Is only partially removed in cold- or hot-lime-soda processes.
It may be a very objectionable impurity, since it can form a tenacious scale.
Silica may be removed from feedwater by the use of dolomite lime or activated magnesia in
the softener.
If preliminary coagulation and settling are carried out, the use of a ferric coagulate will
remove some silica.
These are especially suitable when the silica concentration of makeup water is high.
Such methods do not entirely remove the dissolved silica, but they do lower its
concentration to a point where adequate blowdown will eliminate the danger of scale in a
boiler. The most commonly used method of producing water with only a trace of silica is
demineralization.
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 Silica Removal
Silica is not removed by hydrogen-cation exchange or sodium zeolite exchange and
usually is only partially removed in cold- or hot-lime-soda processes.
It may be a very objectionable impurity, since it can form a tenacious scale. Silica may
be removed from feedwater by the use of dolomite lime or activated magnesia in the
softener. If preliminary coagulation and settling are carried out, the use of a ferric
coagulate will remove some silica. These are especially suitable when the silica
concentration of makeup water is high. Such methods do not entirly remove the
dissolved silica, but they do lower its concentration to a point where adequate blowdown
will eliminate the danger of scale in a boiler. The most commonly used method of
producing water with only a trace of silica is demineralization.

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 Deaeration

Deaeration of water is often necessary to condition water properly for industrial boiler
use, although this is unnecessary for municipal waters.
Dissolved oxygen hastens corrosion by a number of reactions depending on conditions.
The following is a typical outline of an important phase of iron water corrosion
accelerated by oxygen under alkaline or neutral conditions.
Iron in contact with water exerts a certain solution pressure and sets up the anodic half
reaction:
Fe(s) Fe2+(aq) + 2e
This ceases after a certain potential is reached. However, oxygen can react with water
to give OH ions at the cathode:
O2(g) + 2H2O(l) + 4e 4OH-(aq)

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 Deaeration
The Fe2+ and the OH- ions react, and the electrons are neutralized by the flow of current between the
adjacent anode and cathode:
Fe2+(aq) + 2OH-(aq) Fe(OH)2(s)
The initial reactions then proceed further. This electrochemical corrosion can be summarized:

2Fe(s) + O2(g) + 2H2O(l) 2Fe(OH)2(s)

Naturally, air and water can change ferrous hydroxide to ferric hydroxide. Anything that stops the foregoing
sequences will stop the corrosion. This may be accomplished by removal of the dissolved oxygen, by
electrode polarization, by organic inhibitors, or by protective salts. Such protective salts are chromates,
silicates, phosphates, and alkalies, which probably act as anodic inhibitors by forming a film over the anodic
or active areas and thus interrupt the electrochemical sequence.

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 Deaeration
Water ordinarily saturated with air at 10 C contains about 8 ml of oxygen per liter. In preheating boiler
feedwater, oxygen is removed by spraying or cascading the water down over a series of trays contained in a
pressurized vessel. During the downward flow, the water is scrubbed by steam rising upward. Closed
deaerating heaters of this type, operating at approximately 105 C, will generally lower the dissolved oxygen
content to below 10-2 ppm. Any remaining traces of oxygen can then be chemically combined by using an
oxygen scavenger such as sodium sulfite or hydrazine hydrate.

O2 + 2Na2SO3 2Na2SO4
O2 + N2H4.H2O 3H2O + N2
Such complete deoxygenation is desirable to minimize corrosion in the modern high-temperature high-
pressure boiler.

University of Dhaka
University of Dhaka
University of Dhaka
University of Dhaka