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WATER CHEMISTRY

We never know the worth of water till the well is dry English Proverb

The availability of water, both in quantity and quality, is one of the prime factor in deciding the growth of towns and cities as well as industries. For chemical industries, the available water must be as near as possible to the factory site and should also be soft. Otherwise the manufacturing cost will increase.

WATER PHASE DIAGRAM


A phase diagram is a convenient way of representing the phases of a substance as a function of temperature and pressure. The phase diagrams are the primary visualizing tools in material sciences because they help to predict and interpret changes of a composition of a material from phase to phase as a function of temperature and pressure. The phase diagram consists of following important headings: Phase Curves Phase Areas Triple Point Critical Point

i. ii. iii. iv.

i. Phase Curves
The phase diagram contains three curves, each indicating the equilibrium between two phases. Fusion/ Melting/ Freezing curve i,e Phase boundary line between Solid and Liquid phases show Melting Point/ Freezing Point.

Boiling curve/ vapour pressure curve of water i.e Phase boundary line between Liquid and Gaseous phases show Boiling Point/ liquefying point/ vapour pressure of water at that temperature.
Sublimation curve or vapour pressure curve of ice i.e phase boundary line between Solid and Gaseous phases show Sublimation Point/ Solidifying point/ vapour pressure of ice at that temperature.

ii. Phase Area


There are three phase areas each indicating range of set of conditions in terms of temperature and pressure at which that material is capable of stable existance in that particular single-phase state. Solid phase area is the area bounded by sublimation and fusion curves. Liquid phase area is the area bounded by fusion and boiling curves. Gaseous phase area is the area bounded by boiling and sublimation curves.

iii. Triple Point


The point in the phase diagram, where all three lines meet together, a unique combination of temperature and pressure exist, where all three phases are in dynamic equilibrium together

i.e solid is melting & sublimating, liquid is boiling & freezing and
gas is liquefying and solidifying. This point is called Triple Point. For water this point is at 0.00075oC and 4.58 mm pressure.

iv. Critical Point:


The point above which it is impossible to condense a gas into liquid, no matter how much pressure is applied. Temperature and pressure functions correspond to this point are called critical temperature and critical pressure respectively. So, Critical temperature is the temperature required to vaporize a liquid at its critical pressure. Beyond critical temperature it is not possible to distinguish between liquid and gaseous phases. CT of water is 374oC, NH3 132 degree, O2 119 degree & CO2 is 31.2 degree. Critical pressure is the pressure required to liquefy a gas at its critical temperature. CP of water is 217.7 atm, NH3 111.5 atm, O2 49.7 atm and CO2 is 73 atm.

SPECIAFICATION OF WATER FOR INDUSTRIAL PURPOSE


S. No
1.

Purpose
Boilers

specification
Hardness of water should be zero Soft and free from dissolved salts Should be noncorrosive and nonscale forming

Remarks
Untreated water may cause corrosion of boiler and scale formed Prevents the efficient heart transfer. Hard water produces unpleasant taste and it also requires more fuels. Corrosiveness cause damage to cooling lines & radiators while scale decrease cooling efficiency

2.

cooking

3.

coolant

4.

Beaverage

Should be free from Alkaline water neutralizes the fruit alkalinity acids which destroys or modified the taste.

5.

Dairies

Water should be colourless, tasteless, odourless and free from pathogens. Soft water In presence of hard water deliquescent sugar is formed which causes problem in crystallization. Turbidity in hard water causes uneven dying; hard water causes precipitation of basic dyes and decreases the solubility of acidic dyes. Organic matter imparts foul smell. Hard water consumes more soaps and detergents. Salts of iron and manganese impart undesirable colour to the fabric. It will destroy quality of paper pulp.

6.

Sugar industry Textile industry

7.

Water should be soft, free from turbidity, organic matter, colour, iron and manganese.

8.

laundry

Water should be soft and free from colour, iron and manganese Should not contain excess of lime and magnesia and should be free from iron salts.

9.

Paper mills

PARAMETERS OF WATER QUALITY:


1. Hardness: Hardness is the property of water which prevents the lather formation with soap.

Hardness in water is due to the presence of cations of


calcium, magnesium and other heavy metals. Other metal ions like Al3+, Mn3+, Fe2+ etc. also react with soap

but their contribution to hardness is very less because


these are present only in traces in natural water.

Soap action Soaps are generally sodium and potassium salts of higher fatty acids
like oleic acid, stearic acid, palmitic acid. When a sample of hard water is treated with soap it does not produce lather rather it forms insoluble white scum or precipitate which do not possess any cleansing action. This is because the Ca2+ and Mg2+ ions in water form insoluble salt of these fatty acids. 2 C17H35COONa + Ca2+
Soap (Sodium stearate) from hard water

(C17H35COO)2 Ca + 2Na+
Insoluble Calcium stearate

2 C17H35COONa + Mg2+
Soap (Sodium stearate) from hard water

(C17H35COO)2 Mg + 2Na+
Insoluble Magnesium stearate

Lather is not produced until the cations causing the precipitation of soap are completely removed and hence the need for a large quantity of soap to produce lather with hard water. Therefore hardness may be defined as soap consuming/wasting capacity of water. The present days detergent used in laundry work, contains a long hydrocarbon alkene of the type CnH2n where n is between 12 and 20. The alkene is first sulphonated with oleum and then converted into sodium salt. This sodium salt is the detergent. C15H30O + H2SO4 C15H31SO4H

C15H31SO4H + NaOH

C15H31SO4Na + H2O

They are better than soap as they are not affected by hardness in water.

Types of Hardness
i) ii) A. On the basis of sustain ability hardness is of two types Temporary hardness. Permanent hardness.

i) ii)

B. On the basis of alkaline character hardness is of two types Alkaline hardness Non-alkaline hardness

(i) Temporary hardness: Temporary hardness of water is due to the presence of bicarbonates of calcium, magnesium and other heavy metals and carbonate of iron. Temporary hardness is removed by mere boiling of water, which converts bicarbonates into insoluble carbonates or hydroxides which are deposited as crust at the bottom of the vessel. It needs only physical treatment.
Ca(HCO3)2 Calcium Bicarbonate
T

CaCO3 + H2O + CO2 Calcium carbonate (Insoluble) Mg(OH)2 + 2CO2 Magnesium hydroxide (Insoluble)

Mg(HCO3)2 Magnesium bicarbonate

ii)

Permanent hardness: Permanent hardness is due to the presence of chlorides and sulphates of calcium magnesium, iron and other heavy metals. Permanent hardness cant be removed by boiling and need chemical treatment.

These are removed by special chemical methods like


Lime-soda process Zeolite process Ion exchange process

i)

Alkaline hardness
Alkaline hardness is defined as the hardness due to Alkaline anions as bicarbonates, carbonates and hydroxides of the hardness producing cations.

OH+ H+ CO3-2 + H+ HCO3- + H+

H2O HCO3H2O + CO2

ii) Non-alkaline hardness

Non-alkaline hardness is due to non-alkaline anions like Cl- and SO42- of hardness producing cations. The non alkaline hardness is obtained by substracting the alkaline hardness from the total hardness.
Ca(HCO3)2 Mg(HCO3)2 FeCO3 Ca(OH)2 CaCl2 MgCl2 FeCl2 FeCl3 CaSO4 MgSO4 FeSO4 Fe2(SO4)3

Temporary Hardness

Alkaline Hardness

Total Hardness

Permanent Hardness

Non-Alkaline Hardness

Units of Hardness: Hardness usually measured in terms of CaCO3 due to its round figure molecular weight i.e 100 a.m.u and its abudance in hard water after treatment. a) Parts Per Million (ppm): Number of parts by weight of CaCO3 equivalent hardness present per million (106) parts by weight of H2O.
Hence X ppm = X part CaCO3 equivalent hardness in 106 parts of H2O

b) Milligrams Per Liter: Number of milligrams of CaCO3 equivalent hardness present per liter of H2O is known as mg/liter hardness.
Hence X mg/liter = X mg CaCO3 equivalent hardness per liter of H2O

d = m/v = 1 gm/cm3 for water so m = v for water 1 Kg H2O = 1 L of H2O 103 x 103 mg = 1 Kg H2O 106 mg = 1 L of H2O X mg/liter = X mg of CaCO3 equivalent per 106 mg of water X mg/liter = X parts of CaCO3 equivalent per 106 parts of water X mg/liter = X ppm

c) Degree French: Number of parts by weight of CaCO3 equivalent hardness present per lakh (105) parts of water is called degree French. It is denoted by Fr. X oFr = X Parts of CaCO3 equivalent hardness per 105 parts of H2O d) Degree Clarks: Number of parts by weight of CaCO3 equivalent hardness present per 70,000 parts of water or It may also be defined as the number of grams of CaCO3 equivalent hardness present per gallon or in 10 lb of water. It is denoted by oCl.

Relation Between Various Units X ppm = X parts CaCO3 equi hardness per106 parts of H2O X mg/L = X ppm X oFr = X parts CaCO3 equi hardness per105 parts of H2O X oCl = X parts CaCO3 equi hardness per 70,000 parts of H2O From above equations the inter-relation of various units can be written as 106 ppm = 106 mg/L = 105 oFr = 70,000 oCl 1 ppm = 1 mg/L = 0.1 oFr = 0.07 oCl 1 oCl = 14.3 ppm (approximately) = 1.43 oFr (approximately) 1 oFr = 10 ppm = 0.7 oCl

Water hardness scale


Parts per Gallon Less than 1.0 1.0 - 3.5 3.5 - 7.0 7.0 - 10.5 More than 10.5 Parts per Million(ppm) Less than 17.1 17.1 60.0 60.0 120.0 120.0 180.0 More than 180.0 soft Slightly hard Moderately hard Hard Very hard Classification

2. Alkalinity:
Alkalinity of water may be defined as its capacity to neutralize acids.

The alkalinity of water may be attributed to the presence of OH- ions CO3 -2 ions HCO3 - ions
The determination is based on the following reactions (i) OH- + H+ H2O P (ii) CO3-2 + H+ HCO3M (iii) HCO3- + H+ H2O + CO2

The titration of water sample against a standard acid up to phenolphthalein end point (P) marks the completion of reactions (i) and (ii) only. The amount of acid used upto phenolphthalein end point thus corresponds to neutralization of whole OH- and one half of the normal carbonate present. While the titration of water sample against the standard acid upto methyl orange end point (M) marks the completion of reactions (i), (ii) and (iii). Therefore the additional acid used after phenolphthalein end point corresponds to one half of normal carbonate and all the bicarbonate present. The total amount of acid used represents the total alkalinity (due to OH-, CO3-2 and HCO3-). Therefore, P = OH- + CO3-2 M = OH- + CO3-2 + HCO3-

The possible combination of ions causing alkalinity in water are: OH- only CO3-2 only HCO3- only OH- and CO3-2 only CO3-2 and HCO3- only The possibility of OH- and HCO3- together is not possible since they combine together to form CO3-2 and H2O OH- + HCO3CO3-2 + H2O Similarly, all the three (OH-, CO3-2 and HCO3-) can not exist together.

RELATIONSHIP B/W P & M ALKALINITY


P = OH- + CO32, M = OH- + CO32- + HCO3-

Case-I : When only OH- is present in water P = OH- + CO32, M = OH- + CO32- + HCO3P = OH, M = OHP=M Case-II : When only CO32- is present in water P = OH- + CO32, M = OH- + CO32- + HCO3P = CO32, M = CO32P=M M = 2P Case-III : When only HCO3- is present in water P = OH- + CO32, M = OH- + CO32- + HCO3P= 0 , M = HCO3-

Case-IV : When only OH- & CO32- are present in water (i). P = OH- + CO32, M = OH- + CO32- + HCO3P = OH- + CO32, M = OH- + CO32P = OH- + OH- + CO32P = OH- + (OH- + CO32-) P = OH- + M P = M + OHP > M
(ii). P = M + OHP = (M + OH-) 2P = M + OHOH- = 2P M (iii). P = OH- + CO32-

M = OH- + CO32M = OH- + CO32- + CO32M = P + CO32M - P = CO322(M P) = CO32-

Case-V : When only CO32- & HCO3- are present in water

P = OH- + CO32P = CO322P = CO32M = 2P + HCO32P = M - HCO3P = M HCO3P<M

, , ,

M = OH- + CO32- + HCO3M = CO32- + HCO3M = CO32- + HCO3-

BOILER TROUBLES BY FEEDING WATER

Water absorbs more heat for a given temperature rises than any other common inorganic substance and expands 1600 times as it evaporates to form steam at atmospheric pressure. The steam is capable of carrying large quantities of heat. If hard water is directly fed into the boilers it may lead to the following problems: (I) Scale and sludge formation. (II) Boiler corrosion. (III) Caustic embrittlement. (IV) Priming and foaming.

(I) Scale and Sludge


In boilers steam is generated continuously by the evaporation of

water. As the water evaporates continuously, the concentration of dissolved salts increases, finally the solution becomes saturated. The point at which ionic product exceeds the solubility product, they are thrown out as precipitates. A) Scale: Scales are the hard deposits firmly sticking on the inner wall of the boiler and cant be removed easily by scrapping.
B) Sludge: If the precipitate formed is soft, loose and floats in boiler water it is called sludge.

Why scale formation takes place?


Scaling is mainly due to the presence of calcium and magnesium salts (carbonates or sulphates), which are less soluble in hot than

cold water, or due to presence of too high concentration of silica


in relation to the alkalinity of the water in the boiler. They may be formed in boilers due to following reasons:
Hydrolysis of magnesium slats:
MgCl2 + 2H2O Mg(OH)2 + 2HCl scale Decomposition of calcium bicarbonate:

Ca(HCO3)2

CaCO3 + CO2 + H2O


scale

Calcium carbonate scale is soft and can be easily removed by wire brush. In high pressure boilers CaCO3 is soluble because it undergoes hydrolysis to form calcium hydroxide and carbon dioxide. CaCO3 + H2O Ca(OH)2 + CO2

On continuous heating CaSO4 present in hard water also gets precipitated as hard scale. (A sulphate deposit is much harder and denser than a carbonate deposit because the crystals are smaller and cemented together more tightly). A sulphate deposit is brittle, does not pulverize easily, and does not show any effervescence when dropped into acid. If silica is present in small amount in water it may form calcium silicate (CaSiO3) and magnesium silicate (MgSiO3) scales which adhere very firmly to the inner walls of the boiler. Scales are generally removed by chemical reactions.

A high silica deposit is very hard, resembling porcelain. The crystals of silica are extremely small, forming a very dense and impervious scale. This scale is extremely brittle and very difficult to pulverize. It is not soluble in hydrochloric acid and is usually very light colored. Iron deposits, either due to corrosion or iron contamination in the water, are very dark coloured. Iron deposits in boilers are most often magnetic. They are soluble in hot acid giving a dark brown colored solution. Iron oxide scales consist of ferric and ferrous compounds such as iron silicates, ferrous phosphate Fe3(PO4)2, sodium ferrophosphate (NaFePO4) and iron oxides (Fe2O3, Fe3O4).

Disadvantages of scale formation:


Wastage of fuel: Scales are bad conductor of heat, which considerably reduces the heat transfer from boiler to inside water. The values corresponding to the thermal conductivity of these salts are: Steel= 15 kcal/m2.h/oC, CaSO4 = 1-2 kcal/m2.h/oC, CaCO3 = 0.5-1 kcal/m2.h/oC and SiO2 = 0.2-0.5 kcal/m2.h/oC. Decrease in efficiency: Sometime scales are deposited in the valves and condensers of the boiler and reduces water circulation. Lowering of boiler safety: Hence boiler has to be overheated in order to maintain a constant supply of steam. The overheating makes the boiler material softer and weaker, and boiler becomes unsafe to bear the pressure of steam particularly at high pressure.

Danger of explosion: On overheating thick scales crack due to uneven expansion. Water comes suddenly in contact with overheated metal and large quantity of steam is formed instantaneously leads to development of very high pressure which may cause explosion of boiler.

Removal of scale formation:


Brittle scales can be removed by giving thermal shocks, i.e, boiler is heated and then suddenly cooled with cold water. Hard and adherent scales can be removed by adding chemicals. The added chemical dissolves the scale and hence removes it, e.g., (i) Silicate and calcium sulphates scales are removed by dissolving them with EDTA solution. (ii) CaCO3 scale can be dissolved by using 10% HCl solution. Loose and adherent scale can be removed with the help of scrapper and frequently blow down operation.

Prevention of scale formation:


Scale formation can be prevented by - External treatment

- Internal treatment

External treatment:
In this process water is externally treated before feeding it into the boiler and hence the name external treatment. The various external treatment methods are:

Lime soda process.


Zeolite process. Ion-exchange process.

Internal treatment:
The treatment of raw water inside the boiler is known as internal treatment. This is also known as internal conditioning or sequestration. In internal treatment suitable chemicals are added to the boiler water either To precipitate the scale forming impurities in the form of Sludges which can be removed by blow down operation or To convert them into compounds which will stay in dissolved form in water.

Internal treatment methods


(i) Phosphate conditioning:
In phosphate conditioning scale formation is prevented by addition of sodium phosphate which reacts with magnesium and calcium salts giving non-adherent and soft sludge of magnesium and calcium phosphate respectively. This process is effective in between the pH range 9.5 to 10.5. 3MgCl2 + 2Na3PO4 3CaCl2 + 2Na3PO4 Mg3(PO4)2 + 6NaCl Ca3(PO4)2 + 6NaCl

The phosphates employed are NaH2PO4, Na2HPO4 and Na3PO4. The precipitate formed is then removed by blow down operation.

(ii) Calgon conditioning:


Calgon is sodium hexametaphosphate Na2[Na4(PO3)6]. It is extensively used in internal treatment and prevents the scale and sludge formation by converting scale forming impurity like CaSO4 to highly soluble complex.
Na2[Na4(PO3)6] 2CaSO4 + Na2[Na4P6O18] Na2[Na4P6O18] Na2[Ca2P6O18] + 2Na2SO4 Soluble complex

Why sludge formation takes place?


Salts like MgCl2, MgCO3, CaCl2 & MgSO4 having greater solubility in

hot water than in cold water are responsible for the formation of
Sludges and hence are generally formed at comparatively colder parts/portions of the boilers. They get collected at places where the rate of flow is slow. Sludge can easily be removed with a wire brush. They may lead to chocking of pipes. Sludges are usually sparingly soluble compound while scales are highly insoluble compounds.

Disadvantages of sludge formation:


Sludges are bad conductor of heat and hence a portion of heat generated is wasted which decreases the efficiency of boiler.

Excessive sludge may cause chocking of pipe in the region where there is less water circulation.

Prevention of sludge formation


Formation of Sludge can be prevented by

Frequently blow down operation Using soft water Coagulation and dispersion are two general approaches When the total amount of sludge is high (as the result of high feedwater hardness) it is better to coagulate the sludge to form large flocculent particles. When the amount of sludge is not high (low feed water hardness) it is preferable to use a higher percentage of phosphates in the treatment. The materials used for conditioning sludge include various organic materials of the tannin, lignin or alginate classes.

(II) Boiler corrosion


Loss of boiler body material or its useful properties by chemical or electrochemical interaction with its environment is known as boiler corrosion. Corrosion may occur in the feed-water system as a result of low pH water presence of dissolved oxygen and carbon dioxide.

Dissolved carbon dioxide:


CO2 gas dissolved in water, forms carbonic acid which has a corrosive effect on boiler material like any other acid. CO2 is also produced in water by the decomposition of bicarbonates. Mg (HCO3)2 Ca (HCO3)2 CO2 + H2O Removal: Carbon dioxide can be removed (a) By addition of calculated amount of ammonium hydroxide (NH4OH) CO2 + 2NH4OH (NH4)2CO3 + H2O (b) By mechanical de-aeration along with oxygen (sonication). MgCO3 + CO2 + H2O CaCO3 + CO2 + H2O H2CO3

(ii) Dissolved oxygen:


Dissolved oxygen is the most important factor causing boiler corrosion. Water usually contains about 8 ppm dissolved oxygen at room temperature. Dissolved oxygen present in water attacks the boiler material according to the reactions: Fe Fe2+ + 2e-] x 2 at anode

O2 + 2H2O + 4e2Fe + O2 + 2H2O

4OH2Fe2+ + 4OH2Fe(OH)2

at cathode

4Fe(OH)2 + 2H2O + O2

4Fe(OH)3

Fe2O3.XH2O (Rust)

Removal:
(a) O2 is removed by adding oxygen scavengers like Na2SO3, hydrazine etc.
2Na2SO3 + O2 Sodium Sulfite N 2H 4 + O2 (b) 2Na2SO4 Sodium Sulfate N2 + 2H2O

it is also removed by mechanical de-aeration.

(III). Caustic Embrittlement


Caustic embrittlement is a type of boiler corrosion due to which boiler material becomes brittle in presence of high conc of caustic and static tensile stress (thermal stress). It is characterized by the formation of inter-granular cracks on the boiler metal particularly at places of high stress like bends, joints, riveted seams etc. During softening by lime-soda process, residual sodium carbonate is usually present in softened water. Under the condition of high pressure in boiler sodium carbonate decomposes to form sodium hydroxide and CO2. Na2CO3 + H2O 2NaOH + CO2

Prevention:
Caustic embrittlement can be prevented by:

Using sodium phosphate as softening agent instead of sodium carbonate (soda) in external treatment. By adding sodium sulphate or sodium phosphate to boiler water which clogs the hair cracks opening, reducing the chance of caustic embrittlement. Tannin or lignin addition to boiler water which blocks the hair cracks preventing the infilteration of caustic soda. All these substances fill hairline cracks in boiler to avoid caustic embrittlement.

(IV) Priming and Foaming


As steam rises from the surface of boiling water in boiler it may be associated with small droplets of water. Steam containing liquid water is called wet steam. The process of wet steam formation is known as priming. Priming is the carryover of varying amounts of droplets of water in the steam (foam and mist). Which lowers the energy efficiency of the steam and leads to the deposit of salt crystals on the super heaters and in the turbines. Steam-carried solids produce turbine blade deposits. These conditions often lead to super heater tube failures as well. Priming is related to the viscosity of the water and its tendency to foam. These properties are governed by alkalinity, the presence of certain organic substances and by total salinity or TDS. The degree of priming also depends on the design of the boiler and its steaming rate.

Priming is mainly attributed to the presence of Suspended impurities and to some extent to dissolve some impurities in water. Sudden boiling (bumping). High steam velocity. Faulty boiler design.

Priming can be minimized by:


Proper designing (i.e dimensions). Maintaining low water levels. Controlled rate of steam velocity. Efficient softening.

Foaming:
The formation of persistent bubbles in boiler which do not break easily is known as foaming.

Foaming is generally caused by the presence of oils and alkalis in water. Clay or organic matter in raw water, oil and grease in condensed make up water and finely divided particles of sludge may also cause foaming. Foaming also increase priming.
Foaming can be minimized by Removal of foaming agent like oil, grease from boiler water. Addition of castor oil and antifoaming chemicals like 2-Octanol, sulfonated oils, Organic phosphate, silicon fluids etc.

Water Softening Methods


The process of removing or reducing the hardness (temporary or permanent) from water is known as softening of water. The important method employed for the softening of water are: Zeolite process lime-Soda process Ion exchange process All these three are external treatments.

1. Zeolite Process or permutit Process


Zeolites are hydrated sodium alumino silicates capable of exchanging its sodium ions reversibly with the hardness producing cations in water. The formula of sodium zeolite is Na2OAl2O3.xSiO2.yH2O Where x = 2 to 10 and y = 2 to 6. They are also known as permutit. Zeolite are of two types: Natural Zeolites Synthetic Zeolites

(i) Natural Zeolites: They are amorphous and non-porous in nature. They are derived from green sands by washing, heating and treating with NaOH. The exchange value of green sand is 7000 to 9000 gm of hardness per m3 of zeolite. e.g. Natrolite Na2O.Al2O3.4SiO2.2H2O (ii) Synthetic Zeolites: They are porous and gel structured synthetic zeolites are prepared by heating together solutions of Sodium silicate, aluminium sulphate and sodium aluminate. China clay, feldspar and soda ash. The most common artificial zeolite is the permutit. The permutit is white in colour and its chemical formula is 2SiO2Al2O3.Na2O. The exchange value of permutit is 35000 to 41000 gm of hardness per m3 of zeolite.

A. Principle:
Zeolites can be simply represented as Na2Z where Z represents insoluble radical frame work. They hold sodium ion loosely. When hard water is passed through a bed of Zeolite, the hardness causing ions are retained by zeolite as CaZ and MgZ. Therefore water becomes free from the main hardness producing cations but gets more concentrated with respect to sodium salts and eventually zeolite gets exhausted. Ca(HCO3)2 + Na2Z Mg(HCO3)2 + Na2Z MgCl2 + Na2Z CaCl2 + Na2Z CaSO4 + Na2Z MgSO4 + Na2Z CaZ + 2NaHCO3 MgZ + 2NaHCO3 MgZ + 2NaCl CaZ + 2NaCl CaZ + Na2SO4 MgZ + Na2SO4

B. Regeneration
During softening, Zeolites exchange its sodium ions with magnesium and calcium ions and after some time they are completely converted into calcium and magnesium zeolites and the zeolite bed cease to soften water, i.e gets exhausted The process by which the exhausted zeolite is reclaimed by treating it with 10% brine solution is known as regeneration CaZ MgZ + + 2NaCl 2NaCl
Brine solution

Na2Z + CaCl2 Na2Z + MgCl2


reclaimed zeolite (Washings)

exhausted Zeolie

Process:
Hard water is percolated (filtered/passthrough) at a definite rate through

the bed of zeolite housed in a cylindrical unit. The hardness causing


Ca+2 and Mg+2 ions are retained by zeolite as CaZ and MgZ respectively. The outgoing water contains sodium salts. After some time the bed gets exhausted. At this stage the supply of hard water is stopped and regeneration is carried out. Thus softening by Zeolite involves alternate cycles of softening run and regeneration. The regeneration step comprises of (1) backwashing (2) brining (3) rinsing before reuse. The soft water thus obtained has hardness less than 30 ppm.

Advantages of zeolite process softener


Hardness is almost completely removed and water of about 10 ppm hardness is produced. It automatically adjust itself to the water of different hardness. The equipment used is compact and occupies less space. It required less time for softening. Less skill is required for maintenance as well as operation. There is no danger of sludge formation because impurities are not precipitated.

Disadvantages of zeolite process


Only cations (Ca+2, Mg+2) are replaced by sodium ion sand not the acidic ions. Treated water contains more sodium salts than in lime-soda process.

Limitations:
If water is turbid, it will cause the clogging of pores of zeolite bed, thereby making it inactive. Acid radicals are not removed by this process. Such waters used in boilers causes highly alkaline condition which leads to Caustic embrittlement Boiler corrosion.

NaHCO3
CO2 + H2O

NaOH + CO2
H2CO3 (Carbonic acid)

If large quantities of Fe+2 and Mn+2 are present in water the zeolite bed is converted into iron and manganese zeolites which cant be regenerated. Zeolite process gives good results only with cold water in terms of hardness removal.

2. Lime-soda process
Principle: Lime-soda process is based upon the precipitation of soluble calcium and Magnesium salts by addition of calculated amount of lime and soda. Function of lime: The lime used in this process may be quick lime or hydrated lime. Calcium ion is precipitated as calcium carbonate (CaCO3) and magnesium as magnesium hydroxide [Mg(OH)2] which then filtered off. At room temperature precipitates formed are very fine and they do not settle down easily, causing difficulty in filtration. Hence a

small amount of coagulant like alum, aluminium sulphate or sodium


aluminate are added for the coarsening of precipitates.

The following reactions take place during this process: 1) Lime removes any free acid present: 2HCl + Ca(OH)2 H2SO4 + Ca(OH)2 Al2(SO4)3 + 3Ca(OH)2 FeSO4 + Ca(OH)2 2Fe(OH)2 + H2O + O2 CO2 + Ca(OH)2 Ca(HCO3)2 + Ca(OH)2 CaCl2 + 2H2O CaSO4 + 2H2O 2Al(OH)3 + 3CaSO4 Fe(OH)2 + CaSO4 2Fe(OH)3 CaCO3 + H2O 2CaCO3 + 2H2O

2) Lime precipitates iron and aluminium salts as hydroxides:

3) Lime dissolves carbon dioxide as calcium carbonate: 4) Lime precipitates bicarbonate of calcium as calcium carbonate: 5) Lime precipitates magnesium salts as hydroxides:

Mg(HCO3)2 + 2Ca(OH)2
MgCl2(or MgSO4) + Ca(OH)2

2CaCO3 + Mg(OH)2 + 2H2O


Mg(OH)2 + CaCl2(or CaSO4)

6)

Lime converts bicarbonate ions (like NaHCO3, KHCO3, etc) into carbonates: 2NaHCO3 + Ca(OH)2 Na2CO3 + CaCO3 + 2H2O

7) Soda coverts all soluble calcium permanent hardness: Na2CO3 + CaCl2 CaCO3 + 2NaCl
Na2CO3 + CaSO4 CaCO3 + Na2SO4

Function of soda:
The added ingredient soda ash reacts with calcium permanent hardness including calcium hardness introduced during the reaction of lime with HCl (equations in point vii above). Bicarbonate ions (NaHCO3, KHCO3), if present in the hard water, produced carbonate ions (as Na2CO3 or K2CO3) during their reaction with lime and this may be imagined to be equivalent to production of Na2CO3. Hence, the amount of carbonate ions thus produced from bicarbonate ions are to be subtracted from the total requirement of soda for softening.

Lime-soda process are of two types: Cold lime-soda process. Hot lime-soda process.

Advantages of Lime-soda process:


Economical. cost effective. Lesser amount of coagulants are required. Iron and manganese could be removed. Minerals are also removed Reduce corrosion tendency. The alkaline nature of water reduces the amount of pathogenic bacteria. Suitable for turbid and acidic water.

Disadvantages of Lime-soda process:


Disposal of large amount of sludge is a problem. Skilled supervision and careful operation are required for efficient and economical softening.

3.

Ion Exchange or de-ionization or Mineralization process.

The process used for removal of all dissolved salts from water is referred to

as deionization
Deionization requires the flow of water through two ion exchange materials in order to effect the removal of all salt content. The terms demineralization and deionization are used somewhat interchangeably by the industry. While the term demineralization is generally better understood, deionization is especially apt. The word soft water means it does not have hardness producing Ca2+ and Mg2+ ions but it may contain other ions like Na+, Cl-, K+ etc. Alternatively, demineralized water does not have any ion including hardness producing ones. Thus, it should be noted that every soft water is not de-mineralized water; whereas every demineralized water is soft water

Polished/Intrinsic water

The extremely pure water used for washing in the manufacturing of delicate electronic equipments like TV tubes, calculators, watches, transistors etc is known as polished water or intrinsic water which is usually obtained by passing water through several ion exchange resin columns.

Ion exchange resins


They are insoluble cross-linked long chain organic polymers with a

micro porous structure. The functional groups attached to the


chains are responsible for the ion exchanging properties.

Resins containing carboxylic (-COOH) or sulphonic acid (-SO3H) functional groups are able to replace their H+ ions with other cations, which comes in their contact whereas those containing basic amino (-NH2OH) or substituted amino (quaternary ammonium

salts) functional group are able to replace their anions with other
anions, which comes in their contact.

CLASSIFICATION OF RESINS i) Cation exchange resins:

Cations exchange resins are mainly styrene-divinyl benzene copolymers, which on sulphonation or caboxylation become capable to exchange their hydrogen ions with the cations in the water. For example, AmberliteIR 120, Dowex-50, Nalcite-HCR. These can be represented as R-H+. Their exchange reactions with cations (for example, Ca2+, Mg2+) are shown below: 2R-H+ + Ca2+ R22-Ca2+ + 2H+

2R-H+ + Mg2+

R22-Mg2+ + 2H+

CH2

CH

CH2

CH

CH2

CH

CH2

CH2

CH2

SO3-H+ M+ M
++

SO3-H+ M+ M+ M++

SO3-H+ M++ M
+

SO3 H M++

M+

M+

CH2

CH

CH2

CH

CH2

CH2

CH2

CH2

CH2

SO3 M M+ M
++

SO3-M+ M+ H+ ++ M

H+

SO3 O 3S M++ H+ H+ + M++ M

M+

ii) Anion exchange resins:


They are styrene-divinyl benzene or amine formaldehyde copolymers, which contain amino or quaternary ammonium or quaternary phosphine

or tertiary sulphonium groups as an integral part of the resin medium.


After treatment with dilute NaOH solution the above groups are able to exchange their OH- anions with the anions in the water. For example, Amberlite-400, Dowex-3, and Zeolite-F. These can be represented as R+OH-, their exchange reactions with anions (for example, SO42-, Cl-, CO32-, etc,) are shown as below: R+OH- + Cl2R+OH- + SO422R+OH- + CO32R-Cl- + OHR22+SO42- + 2OHR22+CO32- + 2OH-

CH2

CH

CH2

CH

CH2

CH

CH2

CH

CH2

NMe2 OH X2 X CH2
-

X-

NMe2 OH X-

NMe2+OH X
2-

X-

X-

2-

NMe2 OH X
-

X2 -

CH

CH2

CH

CH2

CH

CH2

CH

CH2

NMe2+X X2 X
-

NMe2+X X
-

OH -

OH 2X

+ NMe2+ Me2N X2 X2 OH - OH X X

The process:
The raw water is passed first through the cation exchange material to remove the Ca2+ and Mg2+ ions just as in the normal softening process. The metallic ions in the water get attached to the ion exchange material, which releases its hydrogen ions on a chemically equivalent basis. At this point the deionization process is just half complete. While the positive metallic ions have been removed, the water now contains positive hydrogen ion and the anions originally in the raw water. The partially treated water then is passed through a second unit containing an anion exchange material normally consists of replaceable hydroxyl anions and fixed irreplaceable cations. Now the negative ions in solution (the anions) are absorbed into the anion exchange material and hydroxyl anions are released in their place. All that emerges from such two-unit system is ion-free water.

Regeneration:
The ion exchange capability of these resins towards the exchange of ions from the water is based upon their ion exchange potential. These resins are said to be exhausted when ion exchange potential is lost/decreased. These exhausted Cation exchange resins can be regenerated by passing a solution of dil.HCl or dil. H2SO4 through the Cation exchange column. The renewal is represented as: R22-Ca2+ + 2H+ Ca2+ + 2R-H+ The column is washed with de-ionized water and washing (contains Ca2+ Mg2+ and Cl- or SO42- ions) is passed to a sink or drain. The exhausted anion exchange column can be regenerated by passing a solution of dil. NaOH, the regeneration can be represented as: R22+SO42- + 2OH2R+OH- + SO42-

Advantages of the ion exchange process:


Highly efficient process, >99.9% removal of desired ions. Predictable performance. The process can be used to soften highly acidic or alkaline water. Produces water of very low hardness (say 2ppm).

Disadvantages of the ion exchange process:


The equipment is costly and more expensive chemicals are needed. If water contains turbidity, then the output of the process is reduced. The turbidity must be below 10 ppm. If it is more, it has to be removed first by co adulation and filtration. This water softening does not remove bacteria, sand, pesticides, and many other organic and inorganic compounds.

SALT WATER DESALINATION METHODS


Water is indisputably the most essential resource of the earth has to
offer to the human race. As already explained oceans contribute about 97% of the total water on earth. The ocean (sea) water contains about 2.5% salt and it has a peculiar salty (brackish) taste and is also known as brackish water (If the water contains 1000 to 35,000 mg/lit of dissolve salts, it is called brackish water). This brackish water is totally unfit for drinking purposes.

The process of removing common salt (NaCl) from sea (brackish)


water is called desalination

The most commonly used methods for desalination of water are:

Electrodialysis, Reverse osmosis Distillation.

1) Electro-dialysis
It is a process by which oppositely charged ions (Na+ and Cl- ) are pulled out of the salt water by passing direct current using electrodes and ion selective natural or synthetic membranes. When current is passed sodium ions start moving towards cathode whereas chloride ions move towards anode through the ion selective membranes [which allows only one kind of ion with specific charge to pass through it, for example, As a result of movement of Na+ and Cl- ions, the concentration of brine decreases in the central compartment. Desalinated (pure) water in the central compartment is removed from time to time and replaced with fresh seawater and the process continues. The advantage of electro-dialysis is that the cost of the plant installation is economical.

2) Reverse Osmosis
When a semipermeable membrane separates two solutions of different concentrations, the flow of solvent takes place from dilute solution to concentrated solution and the process is called osmosis. However, on application of a hydrostatic pressure in excess of osmotic pressure, the solvent flow can be reversed, that is, the flow of solvent takes place from concentrated solution to dilute solution and the process is called as reverse osmosis. So, in Reverse Osmosis (RO) process, the pure solvent (water) is separated from its contaminants (in case of brackish water contaminant is NaCl). In this process the pressure (20-100 atm ) is applied to seawater (higher conc.) to force pure water (lower conc.) out through semipermeable membrane. The most commonly used polymeric RO membranes are made from cellulose acetate or Polymethamethaacrylate or polyamides.

The advantages of reverse osmosis include: It significantly reduces salt, most other inorganic material present in the water, and some organic compounds. It usually removes microscopic parasites (including viruses), but any defect in the membrane would allow these organisms to flow undetected into the filtered water. The process is less expensive to operate and maintain.

The disadvantages of reverse osmosis include:


The process makes only a few gallons of treated water a day for drinking or cooking. Wastage of water is more. 2-4 gallons of waste water are flushed down the drain for each gallon of filtered water produced. Some pesticides, solvents and other volatile organic chemicals are not completely removed by reverse osmosis systems. The efficiency of RO membrane is dependent on many factors [the contaminant concentrations, chemical properties of the contaminants, the membrane type and condition, and operating conditions (like pH, water temperature, and water pressure)] in reducing the amount of contaminant in the water. These systems require periodic maintenance. The pre and post filters and the reverse osmosis membranes must be changed according to the manufacturers recommendation, and the storage tank must be cleaned periodically. Damaged membranes are not easily detected, so it is hard to tell if the system is functioning normally and safely.

Potable Water

Water which is safe and palatable for drinking

purposes is known as potable water

Characteristics of potable water


It must possess the following characteristics: It should be colourless, odourless and sparkling clear. Potable water should be perfectly cool. It should have pleasant taste. It should be free from objectionable gases (CO2, NH3,H2S etc) and minerals such as Pb, Mn, Cr, As salts. pH should be about 8.0. It should be reasonably soft. Turbidity should be less than 10 ppm. Free chlorine should be less than 0.1-0.2 ppm. Dissolved solid less than 500 ppm is desirable. It should be free from pathogens. Water obtained from most of the natural sources is generally impure and is thus not fit for drinking purposes.

Water treatment plant:


There are two types of water treatment for potability 1) 2) POE water treatment POU water treatment

1. POE water treatment

Schematic diagram of a POE water treatment plant

In point of Entry (POE) water treatment, the following steps are taken for purification of the water before domestic supply: (i) Screens: The untreated water is passed through screens having large number of holes of different sizes to retain the floating material in the water. (ii) Pre-chlorination: Pre-chlorination is utilized mainly in situations where the inflow is taken from a surface waste source such as a river, lake, or reservoir. (iii) Sedimentations with coagulation and flocculation: Sedimentation is a process in which the water is allowed to stand undisturbed in big tanks for 2-6 hours. During sedimentation most of the suspended particles settle down at the bottom of the tank due to force of gravity. Coagulants are added before sedimentation to remove impurities like fine clay particles or colloidal matter.

The various chemical reactions involved in the coagulation/flocculation


are given below: a) Alum [K2SO4.Al2(SO4)3.24H2O] is the most widely used coagulant in water treatment. Alum reacts with the natural alkalinity present in the water as follows: Al2(SO4)3+ Ca(HCO3)2 (coagulant) 2Al(OH)3 + 3CaSO4 + 6CO2 (Flocculant ppt)

b) Sodium Aluminate (NaAlO2) is used as coagulant when the water undergoing treatment have pH less than 7 (no alkalinity). It gives best results in the pH range of 5.5-7.0. NaAlO2 + 2H2O Al(OH)3 + NaOH The sodium hydroxide formed reacts with magnesium salts present in the water to form magnesium hydroxide flocculants as given below.

MgCl2(or MgSO4) + 2NaOH

Mg(OH)2 + 2NaCl(or Na2SO4)

c)

Ferrous sulphate [FeSO4.7H2O] is commonly used as flocculant above pH 8.5. The chemical reactions involved are given below
Fe(OH)2 + MgCO3 + CO2 + H2SO4

FeSO4 + Mg(HCO3)2 + H2O

(coagulant)
4Fe(OH)2 + O2 + 2H2O (coagulant)

(Flocculant ppt.)
4Fe(OH)3 (heavy Flocculant ppt.)

Fe(OH)3 is a heavy flocculant which quickly settles down during sedimentation process.

(iv)

Filtration: Slow filtration through a fine sand filter to remove any remaining small particles, microorganisms, bacteria etc.

(v)

Aeration: of water to oxidize small quantities of organic material to carbon dioxide and water. The BOD (biological oxygen demand) value is the amount of oxygen required, with the assistance of bacteria, to oxidize the oxidizable organic materials present in 1 liter of water to carbon dioxide and water.

Therefore, BOD is a measure of the degree of pollution of water and is


expressed in mg of oxygen /L.

The COD value (chemical oxygen demand) indicates how much oxygen, measured in mg/L is required to oxidize most of the organic material in 1 liter of dirty water by oxidizing agent. This test method oxidized more organic material than the BOD test and therefore the COD value is always higher than the BOD value. Despite this, measurement of the COD value is often preferred because the results can be obtained more quickly. (vi) Disinfection: Disinfection with either ozone or chlorine to render the remaining bacteria harmless and to reduce the growth of algae in water pipes. 3-6 mg of chlorine per liter are added to the water with which it reacts to form hypochlorous acid, which is a more efficient disinfectant than the hypochlorous anion.

A. Chlorination
Water for drinking purposes, the potable water, is treated to make it acceptable and free from harmful bacteria. This is most often accomplished by adding chlorine to the water, which forms the strong oxidizing hypochlorous acid, HOCl. Cl2 + H2O HOCl + H+ + ClHOCl H+ + OClDepending on pH and products formed, the effective residual concentration of chlorine [free available chlorine (FAC)], HOCl or OCl(hypochlorite ion) is 0.1 0.2 mg/l. Higher concentrations of chlorine (or products of chlorination) tend to give water a definite taste. The hypochlorous acid produced by the reaction of chlorine with water is responsible for the death of microorganisms and bacteria, etc. present in water.

The advantages of using chlorine as disinfectant are:


Chlorine provides a strong residual in the distribution system. Chlorine can be easily converted to chloramines, which also provide a strong residual and do not produce by-products. Chlorine is easy to apply. Chlorine is relatively inexpensive. Chlorine is effective even at low concentrations.

The disadvantages of using chlorine are:

When chlorine reacts with organic material its concentration is reduced and trihalomethanes (THMs) are formed which are carcinogenic.
Chlorine provides poor cryptosporidium and Giardia control. Both of these disease cause gastrointestinal problems, which in severe instances can cause death.

B. Ozonation
A mixture of ozone and air can be bubbled through water to oxidize impurities. Ozone is toxic, and can be detected by its odour at about 0.01 ppm whereas its total limit value (TLV) is 0.1 ppm. Unlike chlorine, ozone does not produce known carcinogens as a byproduct of its water treatment and, therefore, is gaining increased use for domestic as well as industrial water supplies. Chlorination must follow ozonation in public water supply because ozone decomposes rapidly, and chlorine residual may be carried throughout a distribution system. For domestic water purifiers, ozone is often combined with activated carbon filtration to achieve a more complete water treatment.

The advantages of using ozone include:


Ozone is primarily a disinfectant that effectively kills biological contaminants. It oxidizes and precipitates iron, sulphur, and manganese which can be filtered out from solution. It oxidizes and breaks down many organic chemicals including many that cause odour and taste problems. Ozonation produces no taste or odour in the water. Since ozone is made of oxygen and reverts to pure oxygen, it vanishes without trace once it has been used.

The disadvantages of using ozone include:


Ozone treatment can produce undesirable by-products that can be harmful to health (for example, formaldehyde and bromate). The process requires electricity and hence, it cannot be used in an emergency. Ozone is not effective in removing dissolved minerals and salts.

2. POU water treatment:


Point of use (POU) methods treat water at the point where it is used frequently (at the kitchen sink). Only the water that is actually used for drinking, cooking, beverage preparation, etc. is treated. This has the advantage of economy only a few hundred gallons of water need to be treated per year instead of many thousands if all of the water entering the home were to be treated. POU generally include following three processes A) Filtration by filter B) Adsorption by activated carbon C) UV irradiation by UV lamp

(a) Filtration by filter


Fiber filters:
These filters contain cellulose, rayon or some other material spun into a mesh with small pores. Suspended sediment (or turbidity) is removed as water pressure forces water through tightly wrapped fibers. Some small organic particles that cause disagreeable odour and taste may also be removed. The finer the filter, the more particles are trapped and the more often the filter

must be changed. Fiber filters are often used as pre-filters to reduce the
suspended contaminants that could clog carbon or RO filters. The main drawback of fiber filters is that these can not remove contaminants that are dissolved in the water, like chlorine, lead, mercury, trihalomethanes or other

organic compounds.

(b) Adsorption by activated carbon Granular activated carbon (GAC): In this types of filter, water flows through a bed of activated carbon granules which trap some particulate matter and remove organic contaminants causing undesirable taste and odour.

(c) Ultra-violet light irradiation:


Water passes through a clear chamber where it is

exposed to Ultra-violet (UV) light. UV light effectively destroys bacteria and viruses. However, how well the UV system work depends on the energy dose that the organism absorbs. If the energy dose is not high enough, the organisms genetic material may only be damaged rather than disrupted.

The advantages of using UV include: (i) it does not produce any toxic or significant nontoxic by products during the process. (iii) it leaves no smell or taste in the treated water. (iv) It requires very little contact time (seconds versus minutes for chemical disinfection). (v) It improves the taste of water because microorganisms are destroyed. (vi) Many pathogenic microorganisms are killed or rendered inactive by UV radiations. (vii) It does not affect minerals in water.

The disadvantages of using UV include:


(i) UV radiation is not suitable for water with high level of suspended solids, turbidity, colour, or soluble organic matter. These materials can react with UV radiation, and reduce disinfection performance. Turbidity makes it difficult for radiation to penetrate water and pathogens can be shadowed, protecting them from the light. (ii) UV light is not effective against many non-living contaminant, lead, asbestos, many organic chemicals, chlorine, etc. (iii) It requires electricity to operate so can not be used in an emergency situation when the power is out.