Contents

Specification for Water Hardness of Water

Types of Hardness Determination of hardness of water Units of Hardness and their Inter-relations

2 3
4 5 6

Boiler Feed Water

Scales Sludges Priming Foaming Boiler Corrosion Caustic Embrittlement Carry Over

8
9 12 13 14 15 16 17

Water Softening
Lime soda process Ion Exchange Process Internal treatment Colloidal condition Phosphate conditioning Calgon conditioning

18
18 22 25 25 25 26

Alkalinity of Water

27

Specification for Water

Different uses of water demand different specifications:

i) Textile Industry: Textile industry needs frequent dyeing of clothes and the water used by this industry should be soft and free from organic matter. Uniform dyeing is not possible with hard water as it decreases the solubility of acidic dyes. If water contains Fe, Mn, colour or turbidity, it causes uneven dyeing and leaves stains on fabrics. Hence, water should be free from these impurities.

ii) Laundries: Laundries require soft water free from colour, Mn and Fe because hardness increases the consumption of soaps. Salts of Fe and Mn impart a grey or yellow shade to the fabric.

iii) Boilers: Boilers require water of zero hardness otherwise; heat transfer is hindered by scale formation. Untreated water can also lead to corrosion of boiler materials.

iv) Paper Industry: Paper Industry require water free from SiO2 (as it produces cracks in the paper); Turbidity (Fe and Mn as they affect the brightness and colour of the paper); Alkalinity (consumes alum and increases the cost of production); Hardness (as Ca and Mg salts increase the ash content of the paper.)

v) Beverage: Beverages require which isn't alkaline as it destroys or modifies the taste as it tends to neutralize the fruit acids.

vi) Dairies and Pharmaceutical Industries: Such industries require ultra pure water which should be colourless, tasteless, odourless and free form pathogenic organisms.

Note: Water needs to be treated to remove all the undesirable impurities. Water treatment is the process by which all types of undesirable impurities are removed from water and making it fit for domestic or industrial purposes.

Hardness of Water
The soap consuming capacity of water is known as hardness of water. Hardness in water is due to the formation of soap by the cations of a soluble salt, when it dissolves in water. Generally, soap consists of sodium salts of oleic acid, palmitic acid and stearic acid. When these salts are dissolved in water, they do not allow lather to be formed due to insolubility. It is due to the reason that carbon dioxide present in water breaks sodium or potassium soaps into free fatty acids. Hardness of water is due to the presence of Ca2+ and Mg2+ contents of water.

2 C17H35COONa + CaCl2 Sodium stearate

(C17H35COO)2Ca + 2NaCl Calcium stearate (insoluble)

2C17H35COONa + Ca(HCO3)2

(C17H35COO)2Ca + NaHCO3

Types of Hardness
i) Temporary hardness ii) Permanent hardness

Temporary Hardness: It is due to the presence of soluble salts of bicarbonates of calcium and magnesium. Temporary hardness can be easily removed by boiling when the bicarbonates are decomposed into soluble carbonates.

Ca(HCO3)2

CaCO3 + H2O + CO2

The insoluble calcium and magnesium carbonates can be easily removed by filtration.

Permanent Hardness: This type of hardness is present due to the sulphides, chlorides and nitrates of calcium, magnesium and other metals. Permanent hardiness cannot be easily removed by boiling.

Another classification of hardness is based on alkalinity. The alkaline hardness is due to the presence of bicarbonates, carbonates and hydroxides of metals and non-alkaline hardness is due to the presence of chlorides, sulphides and nitrates of metals.

Determination of hardness of water

EDTA Method: EDTA method is the most accurate method for determination of hardness of water. EDTA (Ethylene diamine tetra acetic acid) has the following structure.

HOOCH2C NCH2CH2N HCOOCH2C

CH2COOH

CH2COOH

EDTA acts as a complexing agent. It forms complexes with Ca2+ and Mg2+ ions as well as with many other metals cations, in aqueous solutions. In hard water sample, the total hardness can be determine by titrating the Ca2+ and Mg2+ present in an aliquot sample with Na2 EDTA solution using NH4Cl-NH4OH buffer solution of pH10 and Eriochrome Black-T as the indicator. At the end point, the colour changes from wine red to blue.

Na2H2Y
Disodium EDTA in soln.

2Na+

H2Y2-

Mg2+ + HD2blue

MgD- + H+
wine red

Permanent hardness can be determined by precipitating the temporary hardness by boiling water for about 30 minutes followed by titration with EDTA solution. The difference in the titre values corresponds to the temporary hardness of the water solution.

Units of Hardness and their Interrelations

Parts per million (ppm) Milligram per litre (mg/l)

Units of hardness

Degree French (oFr)

Degree Clark (oCl)

i) Parts per million (ppm): It is defined as the number of parts by weight of calcium carbonate per million (106) parts by weight of water.

1 ppm = 1 part of CaCO3 equivalent hardness in 106 parts of water.

ii) Milligrams per litre (mg/L): It is defined as the number of milligrams of CaCO3 present in one litre of water.

iii) Degree Clarke (oCl): It is defined as the parts of CaCO3 equivalent hardness per 70,000 parts of water.

iv) Degree French (oFr): It is defined as the parts of CaCO3 equivalent hardness per 105 parts of water.

Relationship between various units of hardness: As, 1ppm = 1 part per 106 parts of water 1oFr = 1 part per 105 parts of water 1oCl = 1 part per 70,000 parts of water

Therefore, 106 ppm = 105 oFr = 70,000 oCl Hence, 1 ppm = 0.1 oFr = 0.007 oCl = 1 mg/L

Boiler Feed Water

Water is mainly used in boilers for the generation of steam for industries and power houses. For such water all the impurities lead to operational trouble in boilers are eliminated or kept within the tolerable limit.

Boiler-feed water should correspond with the following composition:

i) Its hardness should be below 0.2 ppm. ii) Its caustic alkalinity (due to OH-) should lie in between 0.15 and 0.45. iii) Its soda alkalinity (due to Na2CO3) should be 0.45-1ppm.

Excess of impurities, if present, in boiler feed water generally cause the problems such as scale and sludge formation, corrosion, priming and foaming, caustic embrittlement.

Scale & sludge Caustic embrittlement Priming

Boiler problems
Boiler corroison Carry over Foaming

Scales and Sludges

In a boiler, water is continuously evaporated to form steam. This increases the concentration of the dissolved salts. Finally a stage is reached when the ionic product of these salts exceeds their solubility product and hence they are thrown as precipitate. If the precipitate formed is soft, loose and slimy, these are known as sludges, while if the precipitate is hard and adhering on the inner wall, it is called as scale.

Scales
Scales are hard deposits firmly sticking to the inner surface of the boiler. They are difficult to remove, even with the help of hammer and chisel. Scales are major source of boiler troubles.

Scales may be formed inside the boiler due to: i) Decomposition of calcium bicarbonate Ca(HCO3)2 CaCO3 + H2 O + CO2

ii) Decomposition of calcium sulphate The solubility of CaSO4 in water decreases with increases in temperature. CaSO4 is soluble in cold water but almost

completely insoluble in super-heated water. This is due to increased ionization at high temperature. Consequently, CaSO4 gets precipitated as hard scale on the hotter parts of the boiler. This type of scale causes troubles mainly in high temperature boilers.

iii) Hydrolysis of magnesium salts Dissolved magnesium salt get hydrolysed (at prevailing high temperature inside the boiler) forming Magnesium Hydroxide precipitate, which forms a soft type of scale.

MgCl2

2H2O

Mg(OH)2

2HCl

iv) Presence of Silica Even if a small quantity of SiO2 is present, it may deposit as Calcium Silicate (CaSiO3) or Magnesium Silicate (MgSiO3). These deposits adhere very firmly on the inner side of the boiler surface and are very difficult to remove.

Disadvantages of Scale formation

i) Wastage of fuel: Scales have a poor thermal conductivity. So, the rate of heat transfer from the boiler to the inside water is reduced. In order to provide a steady supply of heat to water, excessive or over heating is done and this causes increase in fuel consumption.

ii) Decrease in efficiency: Deposition of scale in the valves and condensers of the boiler, choke them partially. This result is decreases in efficiency of the boiler.

iii) Danger in explosion: When thick scale crack due to uneven expansion, the water comes suddenly in contact with over-heated portion and large amount of steam is formed instantaneously this result in development of sudden high pressure which may cause explosion of the boiler.

Removal of Scale

Scales are removed by mechanical as well as chemical method.

i) If the scales are loosely adhering, they can be removed with the help of scraper or wire brush. ii) If the scales are brittle, it can be removed by giving thermal shocks. iii) If the scales are loosely adhering, they can also be removed by frequent blow down operation. (Blow down operation is a partial removal of hard water through a tap at the bottom of the boiler, when extent of hardness in the boiler becomes alarmingly high.)

iv) If the scales are adherent and hard, they can be removed by adding chemicals viz. HCl, EDTA etc.

Sludges
Sludge is soft, loose and slimy precipitate formed within the boiler. These are formed by substances which have greater solubility in hot water than in cold water. Examples include MgCO3, MgCl2, CaCl2, MgSO4 etc. Sludges are formed at comparatively colder portions of the boilers and get collected at places, where the flow rate is slow; they can be easily removed (scrapped off) with a wire brush.

If sludges are formed along with scales, then sludges gets entrapped in the scale and both get deposited as scale.

Disadvantages of Sludge Formation

i) Sludges are poor conductors of heat, so they tend to waste a portion of heat generated and thus decreases the efficiency of boiler. ii) Excessive sludge formation disturbs the working of the boiler. It settles in the region of poor water circulation such as pipe connections, plug openings, thereby causing choking of the pipes.

Prevention of sludge formation

i) By using softened water. ii) By frequently 'blow down operation' (i.e. partial removal of concentrated water through a tap at the bottom of the boiler, when extent of hardness in boiler becomes alarmingly high.

Priming
When steam is produced rapidly in the boilers, some droplets of the liquid water are carried along with steam. This process of wet-steam formation is called priming.

Priming is caused by:

i) The presence of considerable quantities of dissolved solid (mainly due to suspended impurities and due to dissolved impurities in water). ii) Steam velocities high enough to carry droplet of water into the steam pipe. iii) Sudden boiling. iv) Faulty design of boiler.

Priming can be avoided by:

i) Controlling rapid change in steaming velocities. ii) The proper design of boilers. iii) Ensuring efficient softening. iv) Filtration of the boiler - Water carried over to the boiler and blowing off sludge or scale from time to time.

Foaming
It is the formation of small but persistent foam or bubbles at the water surface in boilers, which do not break easily. Foaming is caused by the presence of oil and alkalis in boiler feed water.

Foaming can be avoided by:

i) The addition of anti-foaming agent, which acts by counteracting the reduction in surface tension .For example, addition of castor oil, neutralises the surface tension reduction. ii) By removing the foaming agent from boiler water.

Boiler Corrosion
The decay of boiler material by is environment is known as corrosion.

The main causes for boiler corrosion:

i) Presence of dissolved oxygen, carbon dioxide, hydrogen sulphide etc. ii) Certain salts like magnesium chloride causes lot of corrosion. iii) Presence of free acids in water. iv) Formation of acids by dissolved salts. v) Acids formed by certain lubricating oil.

Prevention of corrosion:

Boils corrosion is prevented by introducing a calculated amount of an alkali in water to neutralise acidity or an to remove oxygen. Dissolved oxygen from the boiler must be eliminated as for as possible, by adding calculated quantity of sodium sulphate, hydrazine or sodium sulphide.

Na2SO3

O2

Na2SO4

The carbon dioxide can be removed from the boilers by mechanical deaeration process along with oxygen.

Caustic Embrittlement
It is the phenomenon during which the boiler material becomes brittle due to the accumulation of caustic substance. This type of boiler corrosion is caused by the use of highly alkaline water in the high pressure boiler.

Na2CO3

H2 O

2NaOH

CO2

This NaOH containing water flows into the small clacks of boiler by capillary action. The caustic dissolves the iron of surrounding area inside the boiler as sodium ferroate. At these areas corrosion takes place in such a manner that inter granular cracks occur in an irregular fashion. Such a phenomenon is known as caustic embrittlement.

Prevention of caustic embrittlement: i) During softening process, sodium phosphate is used in place of sodium carbonate.

ii) Tannin or lignin should be added in boiler water which blocks the hair cracks. iii) Sodium sulphate should be added in boiler water.

Carry Over
The phenomenon of carrying of water along with impurities by steam is called carry over. This is mainly due to priming and foaming.

Priming and foaming usually occur together. They are objectionable because:

i) Dissolved salts or suspended solids in boiler water decrease the efficiency of boiler. ii) Dissolved salts may enter the parts of other machines these by decreasing their life. iii) Maintenance of the boiler pressure becomes difficult because of improper judgement of actual height of water column.

Water Softening
The process whereby we remove or reduce the hardness of water irrespective of whether it is temporary or permanent is termed as softening of water. Water softening is very essential since hard water is unsuitable for domestic as well as industrial use. Water can be made soft by external as well internal treatment.

External treatment can be done by the following method:

i) Lime soda process ii) Ion-exchange method

Lime soda process

The basic principle of the process is to chemically convert all the soluble hardness causing impurities into insoluble precipitate which may be removed by settling and filtration. For this a suspension of milk of lime Ca(OH)2, together with a calculated amount of sodium carbonate, Na2Co3 (soda) is added in requisite amount. Proper mixing of chemicals and water is carried out. Calcium carbonate and magnesium hydroxide so precipitated are filtered off.

Ca(OH)2

+ Na2CO3 + H2o

CaCO3

2NaOH

(Soluble impurities)

(Insoluble ppt.)

At room temperature, the precipitates formed are very fine. They do not settle down easily and causes difficulty in filtration. If small amount of coagulants like alum K2SO4.Al2(SO4)3.24H2O and aluminium sulphate are added, they hydrolyse to precipitate of aluminium hydroxide which entraps the fine precipitate of CaCO3 and Mg(OH)2. Thus coagulant helps in the formation of coarse precipitates.

Lime soda processes are of two types:

i) Cold lime soda process ii) Hot lime soda process

Cold lime soda process: In this process, calculated quantities of lime and soda are mixed with water at room temperature. The precipitate formed at room temperature is finely divided and does not settle down easily. They cannot be easily filtered so, it is essential to add a small quantity of coagulant which hydrolysis to give flocculent and gelatinous precipitate of aluminium hydroxide, thus it entraps the fine precipitate. There are two kind of softeners used for softening water by this process.

i) Intermittent type softeners, where the softening is done by batch process. ii) Continuous type softeners.

Hot lime soda process: In this process, water is treated with chemicals at a temperature of 94-1000C. The softeners used are of intermittent type or continuous type.

Advantages of Hot lime soda process:

i) They are more rapid in operation. The time taken for completion is 15 minutes and several hours for hot and cold lime soda processes respectively. ii) Elevated temperature accelerates the actual chemical reaction and reduces the viscosity of the water. This increases the rate of aggregation of the particle. Hence, both the setting rates and filtration rates are increased. Thus the softening capacity of the hot process is several times higher than the cold process. iii) The sludge and the precipitate formed settle down rapidly and hence no coagulant is needed. iv) Quantity of chemical required for softening is low. v) At the higher temperature, the dissolved gases such as CO2 are driven out of the solution to some extent.

Advantages of Lime-soda Process:

i) It is very economical. ii) Treated water is alkaline and hence has less corrosion tendencies. iii) It removes not only hardness causing salt but also minerals. iv) Due to alkaline nature of treated water, amount of pathogenic bacteria in water is considerably reduced. v) Iron and manganese are also removed from the water to some extent.

Disadvantages of Lime-soda process:

i) It requires careful operation and skilled supervision for economical and efficient softening. ii) Sludge disposal is a problem. iii) Water softened by this process contains appreciable concentration of soluble salts, such as sodium sulphate and cannot be used in high pressure boiler.

Ion Exchange Process

Ion exchange is a process by which ions held on a porous, essentially soluble solid are exchanged for ions in solution that are brought in contact with it.

Ion exchange resins are insoluble, cross linked, high molecular weight; organic polymers with a porous structure and the functional group attached to the chains are responsible for the ion-exchange properties.

There are two types of ion-exchange resins:

i) Cation Exchange Resin: They are mainly styrene-diamine s benzene co-polymers, which on sulphonation or carboxylation become capable to exchange their hydrogen ions with the cautions in the water. Such resins have acidic functional groups like SO3H, COOH or OH group capable of exchanging the cationic portion of minerals by their hydrogen ions, hens they are termed as cation exchange. For example: Ambalite IR-20 and Dowex-50 are commercially available cation exchange resins.

ii) Anion Exchange Resin: They are styrene divinyl benzene or amino formaldehyde copolymers, which contain basic

function group such as amino as integral part of region matrix. These after treatment with dilute NaOH, become capable to exchange their OH anions with anions in water and therefore they are known as anion exchanges. For example: Amberlite-400 and Dowex-3 are commercially available anion exchange resins.

Process

The hard water is first passed through cation exchange column, where all the cautions like Ca2+, Mg2+ are removed from it, and equivalent amount of H+ ions are released from this column to water.

xRSO3-H+ + solid solution

M+

(RSO3-)x Mx+ solution

xH+ solid

After passing through cation exchange column, the hard water is passed though anion exchange column, where all the anions like SO2-, Cl- etc. present in water are removed and equivalent amount of OH- ions are released from this column to water.

x[RN(CH3)3+ ]OH- + A+ solid solid

[RN(CH3)3+]xAx- + xOHsolution solution

H+ and OH- ions, released from cation and anion exchange respectively, get combined to produce water molecules.

H+

OH-

H2O

Thus the water coming out from the exchanges is free from cations as well as anions. Ion free water is known as deionised or demineralised water. Thus it is known as pure as distilled water.

Finally, the demineralised water is passed through a degasifier, a tower whose sides are heated and which is connected to a vacuum pump. High temperature and low pressure reduces the amount of dissolved gases like CO2 and O2 in water.

Regeneration: When capacities of caution and anion exchange H+ and OH- ions respectively are lost, they are said to be exhausted.

The exhausted caution exchange column is regenerated by passing a solution of dilute HCl or HNO3/H2SO4.the exhausted anion exchange column can be regenerated by passing a solution of dilute NaOH.

Internal treatment
In this water softening is done by treating raw water inside the boiler. This method is known as sequestration. Internal treatment methods are followed by blow down operation, so that the accumulated sludge is removed.

Some of the important internal treatment methods are:

i) Colloidal condition: Scale formation can be avoided in low pressure boilers by adding substances like kerosene, tin, agaragar etc, which get absorbed over the scale forming precipitates thus giving us non- sticky and loose deposits, which can be easily removed by blow-down operation.

ii) Phosphate conditioning: In low pressure boilers, the carbonate conditioning by adding Na2CO3 is applicable but at high pressure, the CO32- undergoes hydrolysis to form OH-

CO32- + HCO3+

H2 O

HCO3H2 O

OH-

H2O

+ CO2 + OH-

Thus, the concentration of CO32- is decreased and CaCO3 is not precipitated out. This causes caustic embrittlement. In this case, it is preferable to precipitated Ca as the most insoluble

compounds of Ca i.e. calcium phosphate; Ca3(PO4)2. This is done by adding NaS3PO4.

CaSO4

Na3PO4

Ca(PO4)2

Na2SO4

The Ca3(PO4)2 so formed can be removed by blow down operation.

iii) Calgon conditioning: Calgon is the commercial name of sodium hexa-metaphosphate. The process involves the addition of sodium hexa-metaphosphate to boiler water to prevent the scale and sludge formation. Calgon converts the scale forming impurity like CaSO4 into soluble complex compound, which are harmless to the boiler.

Na2[Na4(PO3)6] Calgon

2Na+

[Na4(PO3)6]2-

CaSO4 + [Na4(PO3)6]2Soluble complex

[Ca2(PO3)6]2- + Na2SO4

Addition of 0.5-5 of Calgon prevents scale formation in one of the following ways:

i) At low temperature and pressure, it forms quit stable and soluble complexes with calcium salts

ii) At high temperature and pressure, calgon is converted into sodium orthophosphate which reacts with calcium salts to form calcium orthophosphates. Calcium orthophosphate appears as loose sludge and this can be removed by blow down operation.

Alkalinity of Water
Alkalinity is a measure of the ability of water to neutralize the acids. The alkalinity of water is normally due to the presence of bicarbonates and hydroxides of sodium, potassium, Ca and Mg. Presence of borates, silicates phosphates can also contribute to the total alkalinity to some extent.

Depending upon the anion present, the alkalinity can be classified as:

i) Caustic alkalinity (due to OH- and CO32-ions) ii) Bicarbonate alkalinity (due to HCO3- ions) iii) Hydroxide only (OH-)

iv) Carbonates only (CO32-) v) Bicarbonates only (HCO3-) vi) Hydroxides & carbonates (OH- + CO32-) vii) Carbonates and bicarbonates (Co32- + HCO3-)

Rules for Calculation of Lime and Soda

1. Equivalent of Ca(HCO3)2 or ca temporary hardness requires one equivalent of lime.

Thus,

Ca(HCO3)2 162

= =

Ca(OH)2 74

Lime requirement = 74/100xXx100/162

2. One equivalent of magnesium temporary hardness requires two equivalents of lime.

Thus,

Ca(OH)2

2 x Mg(HCO3)2

Lime equivalent = 74/100x (2xMg(HCo3)2 in terms of CaCO3 equivalent

3. One equivalent of calcium permanent hardness requires one equivalent of soda. CaSO4 = Na2CO3

Soda requirement = 106/100xCaSo4 in terns of CaCO3 equivalent

4. One equivalent of magnesium permanent hardness requires one equivalent of lime & soda.

Thus, lime requirement will be: = 74/100(MgSO4 + MgCl2 in terms of CaCO3 equivalent.

and, soda requirement will be = 106/100x(MgSo4 + MgCl2 in terms of CaCo3 equivalent.

5. Al2(So4)3 and FeSo4 require equivalent amount of and soda.

Thus, lime requirement = 74/100[Al2(SO4)3 + FeSO4 in terms of CaCO3 equivalent and, soda requirement = 106/100[(Al2(SO4)3 + FeSO4 in terms of CaCO3 equivalent