WATER TREATMENT NTRODUCTION ‘Wencr is nature's most wonderful, abundant and useful compound, Of the many essential fer the existence of human beings, animals and plants (wa ait, water, food, shelter, etc.), = is not only essential for the lives of animals and plants, but also occupies a unique = industries. Probably, its most important use as an engineering wuterial is 91 the ‘steam *- Water isalso used a coolant in power and chemical Plants. In addition to it, water is widely other lields such as production of steel, rayon, paper, atomic energy, textiles, chemicals, *r air-conditioning, drinking, bathing, sanitary, washing, irrigation, fire-fighting, etc. SOURCES OF WATER :(A) Surface waters :1. Rain water is probably the purest fori of atural acter, =sbtained asa result of evaporation from the surface water. However, during the joumey downwards PS Aimosphere, it dissolves a considerable amount of industrial gases (like CO,,S0,NO;, ete) an ‘wll particles, both of organic and inorganicorigin = aver Mater: Rivers are fed by rain and spring waters. Water from these sources flow over the = and. dissolves the soluble minerals of the soil and finally falls in rivers. fa general, the comer me aul hs with the sol. or the mare soluble the mineral of the soils with which it ee cme in cout sechacinbuii of dssoloed inpuriis th rier water. River water thus contains dissoled miemisot the cog sean ariiks sulphates, bicarbonates of sodiuna, calcium, magnesiuim and iron. River water alcocentorns ever vente cn tee ftom the decomposition of plants, and small particles of sand and yack in suspen to = nver wate contains considerable amounts of dissolved as well as sispended impurities 3 Lake water hasia more constant chemical composition. li, usually, conteins much lose ment nunerols then even svelssaler, but quantity of organic matter present in it ig quite high. 4. Sea water isthe most inure farm of natural water: Rivers join sea and throw in the impurities carried Shem: Moreiver, continuous evaporation of water fromthe surface of sen makes sea wher ernie cee =r in dissolved impurities, Sea water contains, on an average, about 3.5% of dissnived salts, outof which "ut 2.6% is sodium chloride. Other salts present are sulphate of sodium ; bicarbonates af potassium, p= presitum and calcium ; bromides of potassium and magnesium and a number of other compounds. Surface water, xenerally, contains suspended matter, which aften contains. the disease-procinciig. {ar Prthosenie) tacterias: Hence, such waters as such are not considered ti be safe for haman consumphion. {8) Underground voaters: A part of the rain water, which teaches the surface ofthe earth, Percolates mia the earth As this water journeys downwards it comes in contact with a number of mmannaleate present othe sbiland dissolves some of them; Water continues its downwards jaumey, till it meer e hea rock, when *retreads upwards and it may even come out in the form of ‘sprig’. Spring and well water (or underground water), in gene ds elerer In appearadce dic to te ih rig on Ofte soil, lit contains more of te dissolve salts. Thss;swater fron these saurees containg pire hardness Usually, underground! water is oF high orgartic pmrity, mouths a ———c= ENGINEERING CHEMISTR’ 2 CHARACTERISTICS IMPARTED BY IMPURITIES IN WATER ~The natural water is, usually, contaminated by different types of impurities. The charac! istic and consequent effects of impurities on the quality of water are discussed under the followi thr heads : (2) Physical impurities : (2) Colour in water is caused by metallic substances like salts of iron, mar nese, humus materials, tannins, peat, algae, weeds, protozoa, industrial effluents (from paper and pulp, text “tanneries, etc). Actually, colour in water is due to dissolved substances and substances present as fine colloid: The change in colour of water is not harmful, unless it is associated with any chemical of toxic natur Variations in colour of water from the same source (say a river) with time offen serves as indices of quali ‘of water. Usually, yellowish tinge indicates the presence chromium and appreciable amount of organic matter. ‘Yellowislt-red colour indicates the presence of iron ; while red-brow colour indicate the presence of peaty matter, (b) Turbidity is due to the colloidal, extremely fine suspension such as clay, slit, finely divided matters (organic and inorganic) micro-organisms like plankton, etc. Turbidity expresses the optical properties of water containidg insoluble substances, which scatter light rather than to transmit in straight lines, The turbidity tlepends not only on the quantity of insoluble substances, but also on their size, shape and reflective index, Turbidity in water can be eliminated by sedimentation, followed by coagulation, filtration, ete. | (© Taste is, usualy, interlinked directly with odour. However, in some waste water, taste is not accom panied by odour. Thus, presence of dissolved mineral in water produces taste, but not odour. For example ; (i) Bitter taste can be due to the presence of iron, aluminium, manganese, sulphate or-excess of lime. (ii) Sonpy taste can be due to the presence of large amount of sodium bicarbonate, (iti) Brackish taste is due to the presence of unusual amount of salts (iv) Polatable taste is due to the presence of dissolved gases (CO,) and minerals (like nitrates) in water, (@) Odour in water is undesirable for domestic as well as industrial purposes. Disagreeable odour is water may be caused by the presence of living organisms, decaying vegetation including algae, bacteria, fungi and weeds. The receiving water may be offensive where heavy pollution is caused by sewage/industrial effluents. The most common disagreeable odour in water bodies is due to presence of small quantity of sulphides. The causes of odour in polluted rivers are : (@ presence of inorganic and organic compounds of N, Sand P and the putrefaction of protiens ‘and other organic materials present in sewage ; (ii) industrial effluents containing organic substances stich as alcohols, aldehydes, phenols, esters, ketones, etc. flowing into the water bodies. Besides these : (i) presence of algae in water bodies impart a strong grassy odour, due to the liberation of traces of essential oils from their bodies, (i?) grow'th of iron and sulphur bacteria may produce offensive odours, (iii) presence of colloidal vegetable matter in surface-water evolves a faint flavour, called ‘penty’ odour, (i) clay and sand in finely divided state impart a faint earthy odour, (2) improper bituminous coating on east iron main pipes may give offa farry odour to water which passes through it, (ci) a faint odour is imparted to water passing through new iron or galvanized. This adour is due to the impure hydrogen. (2) Chemical impurities in water includes : (i) inorganic and orguie chemicals (some which are toxic immature) released from dyes, paints, and vanishes, drugs, insecticides, pesticides, detergent, pulp and textiles, industries, tanneries, etc. . All these pollute water bodies, (ii) acids discharged in water by DDT, high explosives, battery, industries, ete. The use of this type of contaminated water causes harmful effects on health of human-beings. (e) Acidity is not any specific pollutant and it simply determines the power to neutralise hydroxyl ions and is, usually, expressed in terms of ppm (or mg/L) af cilcium carbonate equivalent. Surface waters and ground waters attain acidity from industrial wastes like adid, mine, drainage, pickling liquors, etc. Usually, acidity is caused by the presence of free CO, mineral acids (¢., H;SO4) and weakly dissociated acids: Mineral acids are released when iron and aluminium salts hydrolyse.TREATMENT a ®) Gases : (i) All natural waters contain dissolved atmosphere CO;, Its solubility depends upon” ure, pressure and dissolved mineral content of water. Also polluted waters acquire CO, from the ‘oxiciation of organic matter: Its presence in water is of no significance. ©) Concentration of dissolved atmospheric O) in waters depends on temperature, pressure and salt @ in water. Dissolved O, in industrial waters is musance, since it induces corrosion reactions. On the band, dissolved O, in water is essential to the life of aquatic organisms such as fishes. i) Dissolved NHy in water arises from the decomposition (aerobic or anaerobic) of nitrogenous matter. Polluted waters and sewages contains nitrogen in the form of nitrogenous organiccompounds sea, which are partially converted into NH}. Mineral matters have origin from rocks and industrial effluents. These include mineral acids, Na’, KY, Be, CO", Mn, HCOx, Cr, $02", NOx, F™, SiO», ete. However, from industrial point alkalinity and hardness are important. These are discussed separately at a latter stage. (5) Biological impurities are algae, pathogenic bacteria, fungi, viruses, pathogens, parasite worms, etc. worce of these contamination is discharge of domestic and sewage wastes, excreta (from man, animals i), ete (9) Micro-organisms are, usually, abundant in surface waters, but their countis often quitelow or even = deep-well waters. The commonest type of micro-organisms from the point of treatment are algae, fungi Secteria, which often form ‘slinw’, thereby causing fouling as well as corrosion. The slime so-Formed clogs nozales and screens of the circulating pumps in air-conditioning and other industrial plants. The ch OF micro-organisms takes place at temperature between 20 ~ 35°C. In order to control the miiero-or- -ns, chemical treatment like chlorination is done. (b) Water bodies in water inchudes ; (i) bacteria, organisms inhabitating the bottom sludge, and (ii) isms and planktons developed at the water surface. These are inhabitated by different group of worms ‘Se Hat worms, hair worms tiny round worms, oligochetes, rotifers, ete. Usually, ost worms are parasite in _ setsre and these water bodies are nat only harmful to fishes, but also to human health. "3 HARDNESS OF WATER Hardness int water is thal characteristic, which “prevents the lnthering of seap”. This is due to ‘presence in water of certain salts of calcium, magnesium and other heavy metals dissolved in it. sample of hard water, when treated with soap (sodium or potassium salt of higher fatty acid Ske oleic, palmitic or stearic) does not produce lather, but on the other hand forms a white scuun or p=ipitate. This precipitate is formed, due to the formation of insoluble soaps of calcitn and magne- Sem. Typical reactions of soap (sodium stearate) with calcium chloride and magnesium sulphate axe depicted as follows : 2CyHgCOONa + CaCl, ——+ (Ci7HgCOO), Ca b+ 2NaCl Sedumstcante —¢Handnes) ‘calcu stent (Sodium soap) Gaeeete 2CjH.gCOONa + MgSO, ——> (C\7HysCOO), Mg + + Na,SO, Magnesium stearate (Unsoluble) Thus, water which does not produce lather with soap solution readily, but forms awhile curd, is called hard water, On the other hand, water while fathers ensity on shaking with soap salution, is called soft swater. Such a water, consequently, does not contain dissolved calcium and magnesium salts in it, * Plumbosolvency : Lead is not attacked by piare ait-free water (except at the boiling point), Its readily corrided by water containing dissolved air, form Pb(OH)s, which is quite soluble in water, The dissolution action of water mead is called plunitosolcency. The reaction is, however, retarded by certain sats like carbonates and sulphates, since they form insoluble coating of PbCOsor PSO. on the surface ofthe metal, thereby protecting the metal from further-action. Consegivent!y, hard water lias no solvent action ont fend. In other wards, plumbosolvency problem is ‘maximuntinvease of transpartation of soft water through lead pipes:4 ENGINEERING CHEMISTR (2) Temporary or carbonate hardness is caused by the presence of dissolved bicarbonates calcium, magnesiunt and other hexoy metals and the carbonate of iron. Temporary hardness is mostly destroied by mere boiling of water, when bicarbonates are decomposed, yielding insoluble carbonal or hydroxides, which are deposited as a crust at the bottom of vessel. Thus : Hint Ca(HCO,), ——> CaCO, 1 +H,0+C0, T Calcio Calsivm bicrbonate corre insoluble) Heat Mg(HCO,), ——> Mg(OH), 4+ 2Co, T [ Magesien Magnesium bcarborate trond (2) Permanent or non-carbonate hardness i due to the presence of chlorides and sulphates calcium, magnesium, iron and other heavy metals. Unlike temporary hardness, permanent hardness not destroyed on boiling. : 4 EQUIVALENTS OF CALCIUM CARBONATE The concentration of hardness as well as non-hardness constituting ions are, usually, ex: pressed in terms of equivalent amount of CaCO, since this mode permits the multiplication and division of concentration, when required. The choice of CaCO, in particular is due to its molecular weight is 100 (equiznlent wight = 50) and moreover, it is the most insoluble salt that can be precipitated in water treatment, Table 1. Calculation of equivalents of calcium carbonate. | Dissolved Molar | Chemical | Multiplication factor for conveting into |__sattlion mass | equivalent equivalents of CaCO CalHCO), 12 8 100/162 Mg(HCO,), 146 ry 100/146 CaSO, 136 68 100/136 CaCl m 555 100/411 MgSO, 120 69 100/120 MgCl, 95 75 100/95 CaCO, 100 5 | 100/100 Mgco, 8 2 100/84 0, “ 2 100/48 Ca(NO,), 164 2 100/164 Mg«No,), 148 ” | 100/148 HCO; 61 a 100/122 on 7 7 100/38 | co? 60 30 100/60 NaalO, 2 82 100/164 AlySO4)s 32 3, 100/114 FeSO, 7H,0 278 is) 100/278, ut 1 pele ) 10/2 HL 365 af * 10073,7 TREATMENT The equivalents of CaCO, Mass of hardness], [Chemical equivalent producing substance of CaCO, © Chemical equivalent of hardness—producing substance = Mass of hard wroducing substance x 50 © Chemical equivalent of hardness producing substance UNITS OF HARDNESS (2) Parts per million (ppm) is the parts of calcium carbonate equivalent hardness per 10° parts of » ie, | ppm=1 part of CaCO, eq hardness in 10° parts of water. (2) Milligrams per litre (mg/L) is the number of milligrams of CaCO, equivalent hardness present Sire of water. Thus : 1 mg/L = 1 mg of CaCO, eq. hardness of 1 L of water But 1 L of water weighs = 1 kg = 1,000 g = 1,000 x 1,000 mg = 10° mg. 1 mg/L =1 mg of CaCO, eq per 10° mg of water. = 1 part of CaCO, eq per 10° parts of water = 1 ppm. (3) Clarke's degree (°C!) is number of grains (1/7000 Ib) of CaCO, equivalent hardness per gallon ©) ) of water. Or itis parts of CaCO, equivalent hardness per 70,000 parts of water. Thus : 1° Clarke = 1 grain of CaCO, eq hardiness per gallon of water. 1° C= 1 part of CaCO, eq hardness per 70,000 parts of water. (4) Degree French (°Fr) is the parts of CaCO, equivalent hardness per 10° parts of water. Thus : 1° Fr= 1 part of CaCO, hardness eq per 10° parts of water, (5) Milliequivalent per litre (smeq/L) is the numer of mili equivalents of hardness present per Se. Thu: Lmeq/L.= 1 meq of CaCO, per L of water =10°*x50 g of CaCO, eq per litre = 50 mg of CaCO, eq per litre =50 mg/L of CaCO, eq = 50 ppm. Relationship between various units of hardness : ppm =I mg/L =0.1° Fr mg/L =1 ppm =01° Fr 1Ch =1.433°Fr Fr = 10 ppm Tmeq/L = 50 mg/L 5 DISADVANTAGES OF HARD WATER (0) In domesticuse : (i) Washing : Harc water, when used for washing purposes, does not lather freely ‘with soap. On the other hand, it produces sticky precipitates of calcium and magnesium soaps. The formation of such insoluble, sticky precipitates continues, till all calcium and magnesium salts present in water are precipitated. After that, the soap (¢g., sodium stearate) gives lather with water. Thus :6 ENGINEERING CHEMISTRY: CigHgCOONA+HjO <2 Cyl gCOOH + NaOH Soap CyHgCOOH + CyzHysCOONa —> Lather. Stearic atid Soap ‘This causes a wastage of lot of soap being used. Moreover, the sticky precipitate (of calcium and magne- sium soaps) adheres on the fabric/cloth giving spots and streaks. Also presence of iron salts may cause staining of cloth, (i) Bathing : Hard water does not lather fresly with soap solution, but produces sticky scum on the bath-tub and body. Ths, the cleansing quality of soap is depressed and a lot of it is tasted. (ii) Cooking : Due to the presence of dissolved hardness-producing salts, the boiling point of water is elevated, Consequently, more fuel and time are required for cooking, Certain foods sueh as pulses, beans and [peas do not cook soft in hard water. Also tea or coffee, prepared in hard water, has an wrpleasant taste and nuiddy-looking extract. Moreover, the dissolved salts are deposited as carbonates on the inner walls of the water heating utensils: (fo) Drinking: Hard water causes bad effect on our digestive system. Moreover, the possibility of forming calcium oxalate crystals in urinary tracks is increased. (2) In industrial use ?()) Textile industry : Hard water causes much of the soap (used in washing yarn, fabric, ete) to go as waste, because hard water cannot produce goox! quality oF lather. Moreover, precipitates of calcium-and magnesium soaps adhere to the fabrics. These fabrics, when dyed latter on, do not produce exact Shadesof colour. ron and manganese alts-containing water may cause coloured spats on fabrics, thereby spoiling their beauty. (Wi) Sugar industry : Water containing sulphates, nitrates, alkali carbonates, etc, if used in sugar refining, causes difficities in the crystallization of suger. Moreover, the sugar so-produced may be deliquescet (ii) Dyeing industry : The dissolved calcium, magnesium and iron salts in hard water may react with costly dyes, forming undesirable precipitates, which yield inpure shades and give spots en the fabrics being dyed. (io) Paper industry : Calcium and magnesium salts tends to react with chemicals and other materials employed to provide a smoath and glossy (ie, shining) finish to paper. Moreover, iron salts may even affect the colour of the paper being, produced. (o) Laundry : Hard water, if used in laundry, causes much of the soap tised in Washing to go as ausie. Iron salts may even cause coloration of the clothes. (oi) Concrete making : Water containing chlorides and sulphates, if used for conerete making, affects the jydration of cement and the final strength of the hardened concrete (oii) Pharmaceutical industry : Hard water, if used for preparing pharmaceutical products (ike drugs, injections, ointments, ete, may produce certain sndesirable products in them. G) In steam generation in boilers : For steam generation, boilers are almost invariably employed. If the hard water is fed directly to the boilers, there arise many troubles such as :() scale and sludge formation, i) corrosion, (if) priming and foaming, and (io) caustic embrittlement 7 SCALE AND SLUDGE FORMATION IN BOILERS In boilers, water evaporates continuously and the concentration of the dissolved salts in- crease progressively. When their concentrations reach saturation point, they are throvon out of water in tie form: of precipitates on the innier walls of the boiler. Ifthe precipitation takes place in the form of loose and slimy precipitate it is called sludge. On the other hand, if the precipitated matter forms a hard, adhering crust/eoating on the inner walls of the boiler, itis called scale. Sludge is « soft, loose and slimy precipitate formed within the boiler, Sludge can easily be scrapped off with in wire brush, It is formed at comparatively, colder portions of he Loiter and callects in areas of the system, where. the flow rate 1sslow or at bends. Sludges are formed by substances which have greater solubilities in hot seater than in: cold tant, ¢§,, MgCOy, MgCl; Cah, MgSO, ete.TREATMENT % Fig. 1. Scale and sludge in boilers. Disadvantages of sludge formation : (1) Sludges are poor conductor of heat, so they tend to waste a © of heat generated, (2) If sludges are formed along-with scales, then former gets entrapped in the latter Seth get deposited as scales. (3) Excessive sludge formation disturbs the working of the boiler. It settles = wegions of poor water circulation such as pipe connection, plug opening, gauge-glass connection, Sy causing even choking of the pipes. Prevention of sludge formation : (1) By using well softened water. (2) By frequently ‘blow- = operation’, i.e,, drawing off a portion of the concentrated water. Scales are hard deposits, which stick very firmly to the inner surfaces of the boiler. Scales are Sault to remove, even with the help of hammer and chisel. Seales are the main source of boiler Sebles, Formation of scales may be due to: (1) Decomposition of calcium bicarbonate : Ca(HCO,), ——> CaCO, + +H,0+CO, T Seale However, scale composed chiefly of calcium carbonate is soft and is the main cause of scale seation in low-pressure boilers. But in high-pressure boilers, CaCO, is soluble. CaCO, + H,O ——> Ca(OH); (soluble) + CO, T (2) Deposition of calcium sulphate : The solubility of calcium sulphate in water decreases with == of temperature. Thus, solubility of CaSO, is 3,200 ppm at 15°C and it reduces to 55 ppm at SC and 27 ppm at 320°C. In other words, CaSO, is soluble in cold water, but almost completely “soluble in super-heated water. Consequently, CaSQ, gets precipitated as hard scale on the heated «tions of the boiler. This is the main cause of scales in high-pressure boilers. Note : Calcium sulphate scale is quite adherent and difficult to remove, even with the help of hammer and feel (3) Hydrolysis of magnesium salts : Dissolved magnesium salts undergo hydrolysis (at prevail- ‘es high temperature inside the boiler) forming magnesium hydroxide precipitate, which forms a soft type of scale, eg, MgCl, + 2H,O ——> Mg(OH); 4+ 2HCIT Seale (4) Presence of silica : (SiO,), even present in small quantities, deposits as calcium silicate aSiO,) and / or magnesium silicate (MgSiO,). These deposits stick very firmly on the inner side % the boiler surface and are very difficult to rensove. One important source of silica in water is the sad filter.a ENGINEERING CHEMISTR| Disadvantages of scale formation : (1) Wastage of fuel : Scales have a low thermal conductivity, sot rate of heat transfer from boiler to inside water is greatly decreased. In order to provide a steady supply heat to water, excessive or over-Hteating is done and this causes ftcrease in fucl consumption. The wastage of fu slepends upon the thickness and the nature of scale : Thickness of sce (nto) 02257 | 0625 1.25 25 2 Wastage of fuel 10% 15% 50% 0% 150% (2) Lowering of boiler safety : Duc to scale formation, over-heating of boiler is to be done in order maintain a constant supply of steam. The over-heating of the boiler tube makes the boiler material softer an toeuker and this causes distortion of boiler tube and makes the boiler unsafe to bear the pressure of the stear especially in high-pressure boilers. (3) Decrease in efficiency ; Scalés may sometimes deposit in the valves and condensers of the boil and choke them partially, This results in decrease in efficiency of the boiter. (4) Danger of explosion : When thick scales crack, due to uneven expansion, the water comes sudden in cuntact with over-heated iron plates. This causes in formation of a large amount of steam suddenly, So sudd high-pressure is developed, which may even cause explosion of the boiler. Removal of scales : (i) With the help of scraper or piece of wood or wire brush, if they are loosel adhering, (7) By giving thermal shocks (.e, heating the boiler and then suddenly cooling with cold water), they are brittle. (if) By dissolving them by adding them chemicals if they are adherent and hard. Thus, calciun carbonate scales can be dissolved by using 510% HC1. Calcium sulphate scales can be dissolved by addi EDTA (ethylene diamine tetra acetic acid), with which they form soluble complexes. (iv) By frequent blow-dow operation, if the scales are loosely adhering. Prevention of scales formation : (1) External treatment incluctes efficient ‘softening of water” (ie, removing hardness-producing constituents of water). These will be discussed separately. 2) Internal treatment : In this process (also called sequestration), an ion is prohibited to exhibit its original character by ‘complexing’ or converting it into other more soluble salt by adding appropriate reagent. Ars internal treatment is accomplished by adding a proper chemcal to the boiler eater ither : (a) to precipitate the scale forming impuritivs in the form of sludges, which can be removed by blore-down operation, or (b) to concert them into compounds, which rill stay m dissolved form in rater and thts do not cause any harm. Notes :()) Blow down opention is partial removal of hard water through top at the bottom of boiler, when “extent of hardress in the boiler becomes alarmingly high. (Gi) “Make up’ woteris addition of fresh softened water to boiler after blow down operation. Internal treatments methods are, generally, followed by ‘blow-down operation’, so that accu- ‘mulated sludge is removed. Important internal conditioning /treatment methods are : (Colloidal conditioning : In low-pressure boilers, scale formation can be avoided by adding organic substances like kerosene, tannin, agar-agar (a gel), etc., which get coated over the scale forming precipitates, thereby yielding non-sticky and loose deposits, which can easily be removed by pre-determined blow-down operations. (@) Phosphate conditioning : In higl-pressure boilers, scale formation can be avoided by adding sodiun: phosphate, which reacts with hardness of water forming non-adherent and easily removable, soft sludge of calcium and magnesium phosphates, which can be removed by blow- clown operation, e4 3CaCh + 2NayPO, ——> CaPO,), 1+ 6NaCl The main phosphates employed are : (a) NaH,PO,, sodiwuin dihydrogen’ phosphate (acidie) : (0) NasHPO, disodium lrydrogen phosphate (coeakly alkaline) ; (c) NaxPO,, trisodium phosphate (alkaline),‘TREATMENT Note : The choice of salt depends upon the alalinily ofthe boiler-feed water. Calcium cannot be precipitated ly below @ pH of 9.5, so select a phosphate that adjusts pH to optimum valve (95-1055). Trisodium phosphate est suitable for treatment, when the alkalinity of boiler water is low, as it is most alkaline in nature. If boiler ‘alkalinity is sufficient, then disediumn phosphate is mare preferred. Buti the alkalinity of boiler water is too ond requires to be reduiced, then monosodium phosphate being acidic in nature, is preferred. (iii) Carbonate conditioning : In low-pressure boilers, scale-formation can be avoided by ing sodium! enrbonate to boiler water, when CaSO, is converted into calcium carbonate in librium. CaSO, +NajCO, =! CaCO; +Na,S0, Consequently, deposition of CaSO, as scale does not take place ani calcium is precipitated as loose ge of CaCO,, which can be removed by blow-down operation, (je) Calgon conditioning involves in adding calgon [sodium hexa meta phosphate (NaPO;), boiler water. It prevents the scale and sludge formation by forming soluble complex compound h CaSO,. Na,{NayPO,),]_ == 2Na’ + [Na,P,O) Gaon 2CaSO, + [NayP,Oyq]*> ——> [Ca,P,O,]?° + 2Na,S0, Slob complexion (v) Treatment with sodium aluminate (NaAIO,) : Sodium aluminate gets hydrolysed yield- 5 NaOH and a gelatinous precipitate of aluminium hydroxide. Thus : NaAlO, + 2H;0 —— NaOH + Al[OH}, J Sout. otorahomae (Gelato ppt) ‘The sodium hydroxide, so-formed, precipitates some of the magnesium as Mg(OH),, i MgCl, + 2NaOH ——> Mg(OH), J +2NaCI The flocculent precipitate of Mg(OH)s plus AI(OH),, produced inside the boiler, entraps finely suspended and colloidal impurities, including oil drops and silica. The loose precipitate can be smoved by pre-determined blow-down operation. Note : Sodium aluminate in thick solution form is available in plenty and at a cheap rate from bauxite sefining units and this can be used as such for boiler-water treatment. ~ (vi) Electrical conditioning : Scaled glass bulbs, containing mercury connected to a battery, are set sotating in the boiler. When water, boils, mercury bulbs emit electrical discharges, which prewnis scale forming perticles to aliderefstick together to form scale. (vii) Radioactive conditioning : Tablets containing radioactive salts are placed inside the boiler water at a few points. The energy mdiations emitted by these salts prevent saat formaticn. (vif) Complexometric method involves adding 1.5%alkaline (pH=8.5) solution of EDTA to feed-water The EDTA binds the scale-forming cations to form stable and soleble complex. As a result, the sludge and scale formation in boiler is prevented. Moreover, this treatment : (i) prevents the deposition of iron oxides in the boiler, (ji) reduces the carry over of oxides with steam, and (iii) protects the boiler units from corrosion by wet steam (steam containing liquid water), 8 CAUSTIC EMBRITTLEMENT Caustic embrittlement és a type of boiler corrosion, caused by using highly alkaline water in the ler. During softening process by lime-soda process, free Na;CO, is usually present in small proportion in the softened water. In high pressure builers, NasCO, decomposes to give sodium nydroxide and carbon dioxide, Na,CO, + H,0 ——> 2NaOH+CO,10 ENGINEERING CHEMISTRY and this makes the boiler water “caustic”. The NaOH containing water flows into the. minute hair-cracks, always present in the inner side of boiler, by capillary action. Here roter Conporctes anu! the dissoleed TAK sada cericentration increases progressively. This caustic soda attacks the surrounding area, thereby dissolving iron of boiler as sodium feroate. This causes embrittloners of boiler parts, Pan ularly stressed parts (tke bende, joints, rivets, etc), causing even failure of the boiler Caustic racking can be explained by considering the following concentration cell Tron at Concentrated Dilute "Tron at rivets, bends, ‘NaOH NaOH plane joints, etc. solution solution | surfaces aine,ton surrounded by the dilute NaOH becomes the cathodic side : while the iron in contact, ih rales concentrated NaOH becomes anodic part, which is consequently dissolved on ea Caustic embrittlement can be avoided : () by using sodium phosphate a softening reagent, ‘ustead of sodiura carbonate {() by adlng tenn or lignin to boiler sonter, since these blocks the hair-cracks, thereby prevent- ing infiltration of caustic soda solution in these ; AD in atin sot sulphate to boiler water: NagSO, also blocks hair-cracks, thereby prevent- 1g infiltration of caustic soda solutions in these: It has been observed that east cracking can be prevented, if Na,SO, is added to boiler water so that the ratio. : [Na,SO, concentration} INaOH concentration] S kept as 1:1:2:1 and 3:1 in boilers working respectively at pressures up to 10, 20 and above 20 atmospheres. 9 BOILER CORROSION Boiler corrosion is decay of boiler material bya chemical or electro-chemical atteck by its environ ‘ment. Main reasons for boiler corrosion are : {2) Dissolved oxygen : Water usually contains about 8 mL of dissolved oxygen per litre at boiler magaral ne Deselved oxygen in water, in presence of prevailing high tempenting atoke boiler material 28e+2H,0 + 0; —> 2FeOH), | 4Fe(OH), L + 0, ——, 2[Fe,0,.2H,0} 1 (Fetrous hydroxide) Rus Removal of dissolved oxygen : (1) By adding calculated quantity. of sodium sulphite or hydrazine or sodiunt stilphide. Thus 2Na,S0; + 0, ——> 2Na,S0, NH, + 0; —— N,+2H,0 (Hydrazine) Note “Huetasine ts an idea internal treatment chemical forthe removal of dissolved oxygen: It reacts with oxygen, frming iltrogen and water. Nitogen is harmless, Consently, ipiseoe roa axygen witiont increasing the caloha atin of tssolvot solide/salts. On the other hand, if sodium sulphite or sediang sulphide is used, the sodium Sulphate soformed is litble to decompose giving SO; , particularly in high-pressure boilers. The SO, enters the “tenot Pipes antl appears as sulphurous acid (H,SO3)in the steam condensate. So as. rule very low concentration AE 19 10}ppm of NazSO, in the boilers maintained rather adding it intermuttenly Recently developed, Azamina SOERD (a polyvalent organic compound) has been employed for degnssing tavern manna time.‘TREATMENT " (2) By mechanical de-aeration, i.e, water spraying in a perforated plate-fitted tower, heated and connected to Vacuum pump (see Fig. 2). High temperature, low pressure and large surface (provided by perforated plates) reduces the dissolved oxygen in water. Fig. 2. Mechanical de-acration of water. 2) Dissolved carbon dioxide : (CO,) is carbonic acid, CO, +H,0 —> H,CO, ach has a slow corrosive effect on the boiler material, Carbon dioxide is also released inside the er, if water used for steam generation contains bicarbonate, ¢.¢.- a Mg(HCO,); ——> MgCO, + H,0 + Cy Removal of CO, : (1) By adding calculated quantity of ammonia. Thus : 2NH,OH + CO, ——> (NH,),CO,+H,0 (2) By mechanical-aeration process alongwith oxygen. (3) Acids from dissolved salts : Water containing dissolved magnesium salts liberate acids eo liudralysis, ‘MgCl, + 2H.O ——+ Mg(OR), 1 +2HCI ‘The liberated acid reacts with iron (of the boiler) in chain-like reactions producing HCl again ead again. Thus : Fe+2HCI —> FeCl, +H, ? FeCl, + 2H,O ——> Fe(OH); +2HCI Consequently, presence of evena small amount of MgCl; will cause corrosion of iron to a large extent, 10 PRIMING AND FOAMING When a boiler is steaming (ie., producing steam) rapidly, some particles of the liquid water are carried along-with the steam. This process of ‘wet steam’ formation, is called priming, Priming is caused by : (i) the presence of large amount of dissolved solids ; (ii) high steam velocities ; (ai) sudden boiling ; (io) improper boiler design, and (2) sudden increase in steam-production rate2 ENGINEERING CHEMISTR Foaming is the production of persistent foam or bubbles in boilers, which do not break easih Foaming is due to presence of substances like oils (which greatly reduce the surface tension water). Priming and foaming, usually, occur together. They are objectionable because : (2) dissolved salt in boiler water are carried by the wet steam to super-heater and turbine blades, where they deposited as water evaporates. This deposit reduces their efficiency ; (i) dissolved salts may ent the parts of other machinery, where steam is being used, thereby decreasing the life of the mi chinery ; (Hf) actual height of the water column cannot be judged properly, thereby making. th maintenance of the boiler pressure becomes difficult. Priming can be avoided by : (i) fitting mechanical steam purifiers ; (i) avoiding rapid in steaming rate ; (ii) maintaining low water levels in boilers, and (iv) eificient softening and filtration of the boiler-feed water. . Foaming can be avoided by : (i) adding anti-foaming chemicals like castor oil, or (i) remov- ing oil from boiler water by adding compounds like sodium aluminate. 11 SOFTENING METHODS ‘Water used for industrial purposes (such as for steam generation) should be sufficiently Pure, Itshould, therefore, be freed from hardness-producing salts before put to use. The process of removing hardiess:producing salts from water, is known as softening of water. In industry, main three methods employed for softening of water are : (@) Lime-soda process : In this method, the soluble calcium and magnesium salts in water are chemically converted into insoluble compounds, by adding calculated amounts of lime [Cx(OH),] and soda [Na,CO3}. Calcium carbonate [CaCO,] and magnesium hydroxide [Mg(OH)), so-precipitated, ate filtered off. Notes : (1) It may be pointed here that tie clemical reactions taking place during lime-soda treainacet are rather slow. Moreover, the precipitates formed, particularly of CaCO, and Mg(OH,, are fine and they tend to produce a supet saturated solution. This eventually results in "afer depnstion”, later inthe pipes and boiler tubes, producing shidges. These in-furm decrease the effective diameters of pipes, clog tubes and valves, cause their corosion, ote ‘Consequently, these drawbacks partly offsets the purpose of water softening, To overcome these drawbacks, the following arrangements are made (2 Thorough mixing of the chemicals and water is carried out, (i) Proper time for completion of reactions, these, {5 gicem Alternatively, means are adopted for accelerating the reaction (e,, by using hot lime-soda method), (Gi) Substances that bring, down the fine particles of precipitates called accelerators (lke activated charcoal) are added: (7) Substances that help in the formation of coarse precipitates are added, These are called coagulants or flocculents, ex, alutn, (0) Suitable sedimentation chamber is provided bofore final filtration. [2) IFCa(HCO,), and Mg(HCO,) are considered as ions (Ca’* + 2HICQ}) and (Mg + 2HCO5 ) respectively, then calculation results will be same. (3) Equivalent weight of NaAlO, is equal to its molar mass. (4) If eeatedl water contains OH and CO," fons, then these are formed from excess eq each of Ca(OH), pls Na;CO, and Na,CO, respectively. So these excess amounts should be added to the calculations. (5) When the impurities are given as CaCO, and/or MgCO,, these should be Gonsidered die to bicarbonates of calcium and/or magnesium respectively. (6) Substances like NaCl, KCI, Na,SOy SiO, Fe,O,, ete: donot impart any hardness and, therefore, these do ot coistime any lime oF soda, These should not be taken into consideration for calculating the lime and soda Feguirements.TREATUENT 2 Table 2. Calculation of time-soda requirement. . Reaction Need Ca®*+Na,CO,; —+ CaCO, + 2Na* s Mg” +Ca(OH), —> Mg(OH), +Ca?* Ca? +NagCO; —> CaCO5+2Na* | us | 2HCO; + Ca(OH), —+ CaCO, +H;0+CO?- L-S | NaHCO.) CA(HCO,), + CXOH), —+ 2CaCO, + 24,0 L Mg(HCO,), + 2Ca(OH), —> 2CaCO, + Mg(OH), +2H,0 pa CO} + CaO), —> CaCO, + H,0 he 4 2H" + Ca(OH), —> Ca” + 21,0 ack " 5, Les rey Cal*+NagCO, —> CaCO, + 2Na’ ‘Cosgulants : Fe** + Ca(OH), —> Fe(OH), +Ca”* Reo; 2Fe(OH), + H,0 +O, —> 2Fe(OH), ae Ca?" +Na,CO, —+ CaCO, +2Na" Al{SOy)s 2Al* +3Ca(OH), —> 2AI(OH)+3Ca?* ee 3Ca**+2Na,CO, —+ 3CaCO, + 6Na* NaAlO, NaAlO, +H,0 —> Al(OH), +NaOH -L 2NaOH is eg to CatOH)y Now 100 parts by mass of CaCO, are equivalent to: (i) 74 parts of Ca(OH), and (ii) 106 of Na;CO;. +. Lime requirement for softening 74 | Temp. Ca" +2. Temp. Mg” + Perm. (Mg”’ + Fe™ + Al") 700 | ¢CO2+H (HCI or H,S0,) + HCO; -NaAlO, all in terms of CaCO; eq + Soda requirement for softening 106 Perm. (Ca®* + Mg” + Al"* + Fe) + H” (HCI or H,S0,) - HCO; 100| all in terms of CaCO; eq () Cold lime-soda process : In this method, calculated quantity of chemical (lime and soda) =e mixed with water at room temperature. At room temperature, the precipitates formed are finely divided, so they do not settle down easily and cannot be filtered easily. Consequently, itis essential © add small amounts of coagulants (like alum, aluminium sulphate, sodium aluminate, etc.),14 ENGINEERING CHEMI which hydrolyse to flocculent, gelatinous precipitate of aluminium hydroxide, and entraps the fi precipitates. Use of sodium aluminate as coagulant also helps the removal of silica as well as if present in water. Cold L-S process provides water, containing a residual hardness of 50 to 60 pp NaAlO, + 2H,0 ——> NaOH + Al(OH), J Soctaluminie Al{SO.), + 3Ca(HCO;), —+ 2A1(OH), 1 +3CaSO, +6CO, 7 Coma) Cl Bante (Fins eaer) Method : Raw water and calculated quantities of chemicals (lime + soda + coagulant) a ted from the top into the inner vertical circular chamber, fitted with a vertical rotating shat caryin anunber of paddles. As the raw water and chemicals low down, there is a vigorous stirring an continucus mixing, whereby softening of water takes place. As the softened water comes ines outer co-axial chamber, it rises upwards. The heavy sludge (or precipitated floc) settles down fhe ter chamber by the tiie the softened water reaches up. The softened water then pass through a filtering miedia (usually made of wood fibres) to ensure complete removal of sludg Bitered soft water finally flows out continuously through the outlet atthe top (see Fig. 3) Sludgi selling at the bottoth of the outer chamber is drawn off occasionally. ‘Chemicals e Raw water {ses caguan ssi Fe cianea water Wocettye a ‘Outer chamber Sine paddes Inner chamber Fig. 3. Continuous cold ime-seda softener. ‘Steer ‘Secimenteg ‘slusge [6a005, MecOH),) (i®) Hot lime-soda process involves in treating water with softening chemicals at a temper- ature of 80 fo 150° C. Since hot process is operated at a temperature close to the boiling point of the solution, so :.(@) the reaction proceeds faster ; (b) the softening capacity of hot process is increased to many fold ; (c) the precipitate and sludge formed setile down rapidly and hence, no coagulants are needed ; (d) much of the dissolved gases (such as CO, and air) driven out of the water + (@) viscosity of softened water is lower, so filtation of water becomes much easier. This inctum increases the filtering capacity of filters, and (/) hot lime-soda process produces water of comparatively lower residual hardness of 15 to 30 ppm.TREATMENT 15 Sot lime-soda plant consists essentially (see Fig. 4) of three parts: (2) a ‘reaction tank’ in s=w water, chemicals and steam are thoroughly mixed ; (}) a “conical sedimentation vessel” sludge settles down, and (c) a “sand filter” which ensures complete removal of sludge Se softened water. Fig. 4. Continuous hot lime-soda er Advantages of L.S. process: (i) tis very economical. (i) If this process is combined with sedimentation sesgulation, lesser amounts of coagulants shall be needed, (iii) The process increases the pH value = treated-water, thereby corrosion of the distribution pipes is reduced. (jv) Besides the removal of ss, the quantity of minerals in the water are reduced. (0) To certain extent, iron and manganese are semoved from the water. (vi) Due to alkaline nature of treated-water, amount of pathogenic bacterias in is considerably reduced. Disadvantage of L-S process : (i) For efficient and economical softening, careful operation and skilled ‘sion in required. (it) Disposal of large amounts of sludge (insoluble precipitate) poses a problem. ever, the sludge may be disposed off in raising low-lying areas of the city. (ii) This can remove hardness = upto 15 ppm, which is not good for boilers. __ ,, 2) Zeolite or permutit process : Chemical structure of sodium zeolite may be represented = Na,0.AL,O,. xSiO,, v,H,O where x=2~10 and y =2—6.. Zeolite is hydrated sodium alumino Sscate, capable of exchanging reversibly its sodium ions for hardness-producing ions in water. Ecolites are also known as permutits. Zeolites are of two types : (?) Natural zeolites are non-porous. = example, natrolite, Na,O.Al,0; 4SiO,,2H,O. (if) Synthetic zeolites are porous and possess el “vucture. They are prepared by heating together china clay, faldspar and soda ash. Such zeolites possess higher exchange capacity per unit weight than natural zeolites, Process : For softening of water by zeolite process, hard water is percolated at a specified ate through a bed of zeolite, kept in a cylinder (see Fig, 5). The hardness-causing ions Ca, Mg", etc.) are retained by the zeolite as CaZe and MgZe ; while the outgoing water contains dium salts. Reactions taking place during the softening process are : Na,Ze + Ca(HCO,), ——» CaZe + 2NaHCO, Na,Ze + Mg(HCO,), ——+ MgZe +2NaHCO,“n ENGINEERING CHEMIS' NayZe + CaCt, (or CaSO,) ——> CaZe + 2NaCl (or Na,SO,) Na,Ze + MgCl, (or MgSO,) ——> MgZe + 2NaCl (or Na,SO,) (Zeolite) (Hardness) Fig. 5. Zoolite softener. Regeneration : After some time, the zeolite is completely converted into calcium and mag- nesium zeolites and it ceases to soften water, ie., it gets exhausted, At this stage, the supply hard water is stopped and the exhausted zeolite is reclaimed by treating the bed with a concen- trated (10%) brine (NaCl) solution. CaZe (or MgZe) + 2NaCl ——> Na,Ze + CaCl, (or MgCl) (Exhausted zeolite) Brine) (Reclaimed (Washings) zeolite) ‘The washings (containing CaCl; and MgCl,) are led to drain and the regenerated zeolite bed thus-obtained is used again for softening purpose. Limitations of zeolite process : (1) If the supply of water is turbid, the suspended matter must be, removed (by coagulation, filtration, etc.), before the water is admitted to the zeolite bed ; otherwise the: turbidity will clog the pores of zeolite bed, thereby making it inactive. (2) If water contains large quantities of coloured ions such as Mn** and Fe™*, they must be removed first, because these ions produce maganese and iron zeolites, which cannot be easily regenerated. + G) Minefal acids, if present in water, destroy the zeolite bed and, therefore, they must be neutralised with soda, before admitting the water to the zeolite softening plant. “Advantages of zeolite pracess : (1) It removes the hardness almost compietely and water of about 10 ppm hardness is produced. (2) The equipment used is compact, occupying a small space. (3) No impurities dre precipitated, so there is no danger of sludge formation in the treated-water at a later stage. (4) The process hutomatically adjusts itself for variation in hardness of incoming water. (5) Its quite clean. (6) It requires less time for softening, (7) It requires less skill for maintenance as well as operation. Disadvantages of sealite process : (1) The treated-water contains more sodium salts than in lime-soda process. (2) The method only replaces Ca** and Mg’* ions by Na’ ions, but leaves all the acidic ions (like HCO; and COF) as such in the softened water. When such softened water (containing NaHCO, NazCOy, etc) is used in boilers for steam generation, sodium bicarbonate decomposes producing CO2, which causes corrosion ; and sodium carbonate hydrolysies to sodium hydroxide, which causes caustic embrittlement. (3) High turbidity water cannot be treated efficiently by this method, because fine im- purities get deposited on the zeolite bed, thereby creating problem for its working,Permutit method “©F 10-25 ppm residual hardness is obtained. ‘water contains larger amount of sodium Son in original raw water. ff plant and material is higher, son expenses are lower, 7 Table 3. Comparison of peruuntit process voit lime-soda process. Lime-soda method g Water of, generally, 15-50 ppm hardness wale] Treated-water contains lesser amount of sodium, | salts Operation expenses are higher. Capital cost is lower. | ot be used for trenting acidic water, becatise Permutit material undergoes disintegration. plant occupies less space. saw water to be softened must be free from ec matter ; otherwise the pores of permutit, serial are blocked and the bed loses its enge capacity. <= operate under pressure and can be made Satie automatic. & ssvolves no problem of settling, co-agulation, “Sttration and removal of the sludges and Precipitates. ‘Eestrol test comprises only in checking the Serdness of treated-water. There are no such limitations. Plant occupies more space. ‘There: are no such limitations. Itcannot operate under pressure. | | It involves difficulty in settling, co-agulation, filteration and removal of precipitates. In order to meet the changing hardness of incoming water, frequent control and adjustment ot reagents needed Tesated-water contains more dissolved solids. _| Treated-water contains lesser dissolved solids, >) Ton exchange or de-ionization or de-mineralization process : lon-exchange resins are © cross-linked, long chain organie polymers with a microporous structure, attd the “functional attached to the chains ave responsible for the ion-exchanging properties. Resins containing acidic i groups (-COOH, ~SO,H, etc.) are capable of exchanging their H” ions with other cations, comes in their contact; whereas those containing basic functional groups (NH; =NH as lloride) are capable of Sabai their anions with other anions, which comes in their The ion-exchange resins may be classified as : () Cation exchange resins (RH") are mainly styrenestivinyl benzene copolymers, which on nation or carboxylation, become capable to exchange their hydrogen ions with the cations she water. sw CHy-CH-CH,-CH-CH,-CH-CH,-., ° SOFH™ Fig. 6, Acidic or cation exchange resin (suiphenate form).18 ENGINEERING CHEMIS’ (i)Anion exchange resins (R’OH) ore styrenediviny!benamt orainineformaldelude capol mets, which coutain amino or quaternary anenoniun or quaternary phosphonium or tertiary sulphoniu groups es arintegral part ofthe resin matrix. These, after treatment with dil. NaOH solution, beco capable to exchange their OH” anions with anions in water. .-CH-CH —- CH, — CH-CH,-CH-CH,~.., @ 99 CH;NMe3OH~ CH,NMeOH™ esige .-CHy oe ee CH... oo CH,NMeOH~ — CH,NMejJOH™ Fig, 7. Basic of anion exchange resin (hydroxide form). Process : The hard water is passed first through cation exchange column, which removes all the cations like Ca’’.Mg™, etc from it, and equivalent amount of H” ions are released from this column to water. Thus : i 2RH* + Ca* ——s R,Ca™ + 2H" 2RH’ +Mg* ——> R,Mg™ +2H" Alter cation exchange column, the hard water is passed through anion exchange column, which removes all the anions like SO}, CI, etc. present in the water and equivalent amount of OH” ions are released from this column to water. Thus : ROH +Cl” —> RCI +OH™ 2K'OH™ +SO —— R’S0}"+20H™ 2ROH-+CO} —— RCO} +20H™ H* and OH “ions (released from cation exchange and anion exchange columns respectively) get combined to produce water molecule. H'+OH” ——> H,0 ‘Thus, the water coming out from the exchanger is free from cations as well as anions. fon-free water, is known as deionized or demineralised water. Regeneration : When capacities of cation and anion exchangers to exchange H” and OH™ ons respectively are lost, they are then said to be exhausted. The exlnusted cation exchange colunta is regenerated by passing a solution of dil. HCI or dil. H.SO,. The regeneration can be represented as : R.Ca**+2H* ——> 2RH"+ Ca*? (washing)Fig. 8. Demineralization of water. column is washed with deionised water and washing (which contains Ca®, Mg”, etc. @ SOF" ions) is passed to sink or drain. exhatisted dnion exchange column is regenerated by passing: solution of dil. NaOH. The on can be represented as « SO} +20H” ——s 2R'0H~+SO} (washing) column is washed with deionised water and washing (which contains Na” and SO? or is passed to sink or drain. regenerated ion exchange resins are then used again. vantages : (1) The process can be used to soften highly acidic or alkaline waters. (2) It produces very low hardness (say 2 ppm). So itis very good for treating water for-use in high-pressure boilers advantages : (1) The equipment is costly and more expensive chemicals are needed. (2) If water serbidity, then the output of the process is reduced. The turbidity must be below 10 ppm. If itis more, Se removed first by coagulation and filtration. t-bed deionizer consists essentially of « single cylinder containing an intimate mixtute of hydrogen -and strongly baste antion exchanger. When water i8 passed through this bed, it comes in contact, a Raw water NaH inet <- Fig. 9. Regeneration of mixed-bed lon exchanger,20 ENGINEERING CHEMI! number of times, with the two kinds of exchangers alternatively. Consequently, the net affect of mix exchangenisequivalent to passing water through a series of several cation and anion exchangers, The ou ‘water frp the mixed-bed contains even less than | ppm of dissolved salts Regeneration : When the resins are exhausted, the mixed-bed is backwashed (by forcing water tipward direction), when the lighter anion exchanger gets displaced to form an upper layer above the h gaiion exchanger (see Fig, 9.). Thereafter, the anion exchanger is regenerated by passing caustic soda s from the topand then rinses. The lower cation exchanger bed is then regenerated by HS0, solution trea ‘and then rinsed. The two beds are then mixed again by forcing compressed air, The bed is ready for se: Note It may be made clear that the mixed-bed exchangers cost nore and comparatively more exp. Fogenerate, but they are comparatively more convenient to use and afford much more efficient removal of di salts and silica. 12 DRINKING WATER OR MUNICIPAL WATER Municipalities have to supply potable water, iv., water which is sate to drink, Drinki potable water, fit for human consumption, should satisfy the following essential requirem« (4) It should be sparking clear and odourless. (2) It should be pleasant in taste. (3) It sho perfectly cool. (4) Its turbidity should not exceed 10 ppm. (6) It should be free from objection dissolved gases like hydrogen sulphide. (6) It should be free from objectionable minerals sux ead, arsenic, chromium and manganese salts. (7) Its alkalinity should not be high. Its pH be about 8.0, (8) It should be reasonably soft. (9) Its total dissolved solid>-should be less 300 ppm. (10) It should be free from disease-producing micro-organisms. Purification of water for domestic use : Natural water from rivers, canals, etc., does confirm toaall the required specifications of drinking water. For removing various types of i ies, the following treatment processes are employed : Note. Municipal water treatment does not sim at removing the dissolved salts present. Consequ municipalities do not, generally, supply softened water. = (A) Removal of suspended impurities : (1) Screening : The raw water is passed throt screens, having large number of holes, when floating matters are retained by them. (2) Sedimentation is « process of allowing water to stand undisturbed in big tanks, about 5 mde when most of the suspended particles settle down at the bottont, due to the force of gravity. The supernatant water is then drawn from tank with the help of pumps. The retention period i sedimentation tank ranges from 2-6 hours. When water contains fine lay particles and colloidal matter, it becomes necessary to aj sedimentation with coagulation for removing such impurities. Sedimentation with coagulatis tHe process of removing fine suspended and colloidal impurities by the addition of requisite amount cheiticals (called coagulants) to.svater before sedimentation. Coagulant, when added to-toater, forms insollble gelatinous, flocculant precipitate, which descent through the water, adsorbs and entangles very, suspended inpurities forming bigger flocs, which settle down easily. Coagulants like alum or ferro! sulphate provide Al orFe™ ions, which neutralise the negative charge on the colloidal particles. After losing their charge, the tiny clay particles come nearer to one another and combis to fotm bigger particles, which settle down, due to the force of gravity. Thus, coagulant forces evi colloidal particles to settle down. The coagulants (or flocculanis) are, generally, added in soluti form. For proper mixing of coagulants with water, mixers are employed. Properly mixed water then seginrented icoagulants : The following are the most commonly used coagulant: BKSO, - A1,(04); .24H30] is the most widely used in water treatment plants. Alum reacts Presence of alkalinity of water. Ifnatural alkalinity is not present, sufficient time is also added Al{SOph + CalHCO,)) —+ 2AOH)y 4 +3Ca50; +6CO} (Congalant) Cal, bicarbonate Aluminjuum went in water) hydroxide og losculant ppt) aluminate (Na AIO) is obtained from bauxite refineries in the form of a thick solution, This Be used for treating water having no alkalinity (i, pH less than 7). pil range for best resulls NaAlO,+2H.O —— AIOH), | + NaOH Gelatinous floc ‘of alumniniam, hydroxide Seminium hydroxide floc eauses sedimeniation. The sodium hydnixide thus-preduced, precipi- vam salts as Mg(OH)s. MgSO, +2 NaQH ——+ Mg(OH), 1 +Na;S0, poras or ferrous suiphiate [FeSO, . 7 HO] isalso commonly used for coagulation purposes. It gives abovepH valuesof6.5, (ie, slightlyalkaline), Copperas reacts in water in the presence of alkalinity. & not present, sufficient line is also added. FeSO, + Mg(HCOq), ——> Fe(OH), 44 MeCOy+CO;+H,0 (Coagulant) Mag. bicabonate (Present in ter 4FeOH, 1+ O02 #2H;0 —+ 4Fe OH), | (Dissolved Ferric hydronice oxygen) (Hoy foo) SOF); |S in the form of feazy floc, which causes quick sedimentation. ) Filtration és the process of removing colloidal matter and most of the bacterins, micro-organisms, posing water through a bed of fine sand and other proper-sized granular materials. Filtration is ‘out by using send filter, N N N N N N y N N N N N NY N NY N N N N N N N Fig. 10. Sand filer. Operation of sand filter : A sand filter consists ofa thick top layer of fine sand placed ver coarse sand and gravels. Its provided withan inlet for water and an wnderdrain channel at the bottom forexitof filtered22 ENGINEERING CHE! ltt aint water entering the sand filters uniformly distributed over the entire find sand bed. filtration, the sand pores get clogged, due to retention ot impurities in the pores. Wien. the rte of coun slow, the working of filler stopped and abort 2-3 om of tn ‘0p fie sond layer is scrapped off and ‘oth lean sand and the filters put back into use again. The scrapped sand is washed with water, dried and: for refuse at the time of next scrapping operation, {B) Removal of micro-organisms : Water after Passing through sedimentation, coag anu filtration operations still contains small percentage of Pathogenic bacteria (disease-prod Consequently, water used, patticulaly for drinking er ‘municipal purposes, must be freed roducing bacteria, micro-organisms, etc. The provess of destroving/killing the subataneee sts et. from the woater and making it safe for use, Realled disinfe The chemicals or substances, zich are added to water for Killing the bacteria, etc., are known as di {ants The disinfection of water can be cartied out by following methods : (2) By boiling water for 10-15 minutes, all the disease-producing bacterias are kill water becomes safe for use. Note: This process can il ony the existing germs in wntee at th ‘usuis furs possible contamivatian, Moreover, this methaat Particularly during the break tip of epidemics in the Water-wworks, Lone of oan, at does not provide ay ‘ery costly and can be used onty-in individ eal {own or city, and itis impossible to employ it in min ‘orks, about 1 kg of bleaching po per 1.00 kilolitres Of water is mixed and water allowed te atea undisturbed for several h The chemical action produce: (powerful germicide), Ca0Cl, +H,0 ——, CxOF D+ Cl, Ch+H,O — Ha + HOC Hypochlorous acid Germs + HOC! —> Germs are killed. The disinfecting action of bleachin, is Drawbacks (1) Bleaching; powder introdhices ealcium in Water, theteby making it more ha Bleaching powdler deteriomtcs, due to its continunus Secomposition during storage. So, whenever iti added. ithas to be analysed for its effective chlorine content, (G) Only-calculated quantity ofbleaching pe should be used, since an excess of it gives aid laste and contin treated-water. lnm, citorination : Chlorine (either gas or in concentrated solution form) prod: ‘typochiorous acid, which is a po werful germicice, Ch+HO —+ Hod + HC after long experimentation, ‘sported that the death of micro-organisms, bacteria, etc,, results f Cental reaction of hypocklorous acid (HOC) with the enzymes in the cells of the organism. Since enzyme is essential for the metabolic Processes of the micto-oganisms, so death of micr SMUAIS TUTE due to inactiiation of enzyme (te cells of organism) by hypochlorous acid, HOC! = H+0CcI- Proctucing OCI (hypochlorite ions), which eannot combine with enzymes in the cells of micro anisms, This explains the fact that chlotineis found to be mone effective disinfectant at lower Nalues (below 6.5) This is due tothe fact that HOC! is abeur en times more destructive to bacteri than OCT ions,snc is most efectice, when applied to filtered water at such a point zohere adequate mixing & the most widely used disinfectant throughout the world. Apparatus used for {= Known as cllorinator (see Fig; 11), which is a high tower, having a number of baffle and proper quantity of concentrated chlorine solution are introduced at its top. poscoge through the tower, they get thoroughly mixed. The treated-water is taken out etom For filtered-water, about 0.3 to 0.5 ppm of chlorine is sufficient. q Baw co an + chine ‘niet soluion Fig. 11. Chlorinator. AE in water cutlot Factors affecting efficiency of chlorine : (i) Time of contact : Ithas been experimentally shown ber of micro-organisms destroyed by chlorine per unit time is proportional to the number organisms remaining alive. Consequently, the death rate is maximum to start with andl on decreasing with time. (ii) Temperature of water : The rate of reaction with enzymes with temperature, Consequently, death rate of micro-organisms by chlorine increases ese in water temperature, (jif) pH malue of water : It has been found that at lower pH values 5-655), a small contact period is required to kill same percentage of organisms. “Advantages ofcilorine: (0) Itiseffectiveand economical. (if) It requires very little space for storage. (ii) It land does not deteriorate on keeping. (i0) It can be used at lo as well as hgh: temperatures. (0) Te Soces no salt impurities in the treated-water. (0) Itis most idea disinfectant. sivantages : (1) Excess of chlorine, if added, produces a characteristic wnplensan! taste and odour. aver, tsexcess produces an irtation on muscus membrane. The quantity of free chlorinein treated-water J mmf exceed 0.1 to 02 ppm. (2) Itis more effective below 6.5 pH and less effective at higher pH values. Break-point chlorination (or free-residual chlorination) involves in addition of sufficient set of clforine towxidise -(a) organic matter, (b) reducing substances, and (c) free ammonia is raw ronter cing behind mainly free chlorine, whieliypossesses disinfecting action against disease-producing (patho- se) bacterias. When the dosage of applied chlorine to water rich in organic compound or ammonia is dually increased, the results obtained can be depicted graphically in Fig: 12, in which apper- © of following four stages occurs : Theaddition of chlorine at the dip or break, is called “break-point” chlorination. This indicates 'Se point at which free residual chlorine begins to appear. Usually, all tastes, odours (chlorinous ‘ecci others) disappear at break-point, resulting in appeazance of water, free from bad tastes and ‘odours. Moreover, because of the highly persistent and powerful disinfection possessed by avail- ble free chlorine, any type of pathogenic organisms present in water are destroyed, thereby snaking disinfection highly efficient.ENGINEERING CHEMIS’ Fig. 12. Break point ‘chlorination curve, ‘Aopled chiorine coso——p Advantages of break-point chlorination : (1) It oviises completely organic compounds, ammonia ar other reducing compounds, 2) It removes calour in water, due to the presence of ‘Organic matters. (3) It destroy completely (100%) all the disease-prodicing bacteria. (4) It removes both odour atid taste from, the water. (5) Prevents the growth of any weeds in water. De-chlorination : Qver-chlorination after the ‘break-point produces unpleasant taste and dou i ‘iar. These objectionable qualities may be removed by filtering the over-chlorinated wate through a bed of molecular carbon. Altematively, a small percentage of activuled carbon may be added directly to the water and afte: allowing a short reaction period, it is then removen by filtration. Objectionable qualities resulting from over-chlorination may also be remedied by the adéition ofa small percentage of sulphur dioside or sadn suiphite or sodium thiosulphate, eke, SO, +Cl,+2H,0 — H,S0,+2HCI NaSO;+ Cl, +H,O ——+ Na,SO,+2 HCl (S) By using chloramine (CINH,) : When chlorine and ammonia are mixed in the ratio 2: U by volume, a compotind chloramine is formed, Cl,+NH, ——5 CINH, + HCI (Chloramine) Chloramine is much more tasting than chlorine alone and consequently, it isa better bactericidal than chlorine alone. CINH,+H,O —— HOCL + NH, (Disinfeciann etre tea chlormine is used for disinfection of water, because its exces dos not produce aay irritating odour. Moreover, it imparts a yoo fst to treated-water. {S) Disinfection by ozone : Ozone (g) is an excellent disinfectant, which is produced by Passing silent electric discharge through cold and dry oxygen. Silent eletrc 30, ———, 20, (Orygen) discharge (zone Ozone is highly unstable and breaks down, liberating nascent oxygen. 0, —— 0, + 19) Ozone Nascent oxygen‘Sheer & very powertul oxidising agent and kills all the bacterias as'well as matter present in water. out the disinfection by ozone, ozone is released /injected into the water and the ‘Se come in contact ina sterilizing tank (see Fig. 13). The disinfected water is removed ‘Be contact period is about 10-15 minutes and the usual dose strength is 2-3 ppm. Fig. 13. Ozone sterilizer. 7 stage : This method is quite expensive and hence, not employed for disinfection of municipal tages: Disinfection by ozone is coastlier than ehiorine, but it simultaneously removes colour, adour and peng any residue. Its excess is not harmful, since it i uustable and decomposes ftto oxygen. = municipal water treatment in short may be illustrated by flow diagram show in Fig. 14. Fig. 14. Flow diagram of drinking _ water treatment plant. DESALINATION OF BRACKISH WATER ‘Te process of removing common salt (sodittn chloride) from the water, és known as desalination. eer containing dissolved salts with a peculiar salty (or brackish) taste, is called brackish water. Sea containing on an average about 3.5% salts, comes under this category. Brackish water is totally Ser drinking purpose. Commonly used methods for the desalination of brackish water are : {2) Electrodialysis is a method in which the ions (of the salts present) arc puted out of the salt Sy passing direct eurrent, using electrodes and thin rigid plastic membrane pair (natural or synthetic) 5. illustrates the method of desalination by electrodialysis. When direct electric current is ed through saline water, the sodium ions (Na* ) start moving towards negative pole (cathode) ;26 ENGINEERING CHEMI while the chloride ions (CI”) start moving towards ‘the positive pole (anode), through the brane. Asa result, the concentration of brine decreases inn the central compartment ; while it incre ‘oo side compartments. Desalinated brine (or pure water) is removed from the central compa {com time to time; while concentrated brine (in the side compartments) is replaced by fresh brine! water. ‘Sea water ‘Sea water ‘Seawater Lo Sree Fig. 15. Line diagram elactirodialysis. Pure bene water For sone efficient separation, nsially, ions-selective membranes are employed. An ion-selective mem has permeability for only one hind of ions wit specific charge. Bor example, a cntion-selective membrane is peri ‘ations only, because of the presence of charged fixed (inside the membrane) functional groups (suc RSO}, or RCOO™ ), reject anions (having the same charge as that of fixed functional groups). Simi fix anion-selective menibrate lias posit functional groups such as RyN*CT- An electrodialysis cell (sce Fig. 16), consists of a large number of paired sets of rigid pk membranes. Saline water is passed under a pressure (of about 5-6 kgm”) between membi ly ch y charge Fig. 16. ElectrodialysisWSTER TREATMENT Ses and an electric field is applied perpendicular to the direction of water flow. Just as magnets _ like charges repel each other, the fixed positive charges inside the membrane repel positively | Sarged ions (Na’ ), yet permit negatively charged ions (CI) to pass through. Similatly, the fixed ‘sezative charges inside the other type of membrane repel negatively charged ions (CI), yet permit Peitively charged ions (Na’ ) to pass through. Therefore, water in one compartment of the cell is eerived of its salts: while the salt concentration in adjacent compartments is increased. Thus, we ernate streemis of pure water and concentrated brine, Advantages : (1) Its most compact unit. 2) The cost of installation of the plant and its operation is _Semomical. (3) If electricity is easily available, it is best suited. (2) Reverse osmosis : When two solutions of unequal concentrations are separated by a “Ssipermeable membrane (which selectively does not permit the passage of dissolved solute particles, = molecules, ions, etc.), flow of solvent takes place from dilute to concentrated sides, due to -mmosis. If however, a hydrostatic pressure in excéss of osmotic pressure is applied on the concen wei side, the solvent flow reverses, ix., solvent is forced to move from concentrated side to dilute ‘Sse across the membrane. This is the principle of reverse osmosis, Thus, iT FEVEFSE OSMOSIS (RO) | Sethods, pure solvent (water) is separated from its contaminates, rather than removing contaminants from "© water, This membrane filtration is sometimes also called “super-filtration” or “hyper- ‘Sitration”. Method : In this process, pressure (of the order 15 to 40 kg cm *) is applied to the sea- Sater/impure water (to be treated) to foree its pure water out through the semi-permeable ment- ‘brane ; leaving behind the dissolved solids (both ionic as well as non-ionic). The principle of reverse ‘ssmosis, a8 applied for treating saline/sea water, is illustrated in Fig. 17. The membrane consists ef very tluin films of cellulose acetate, affixed to either side of a perforated tube. However, more secently superior membranes made of polyntvthaerylate and polyamide polymers have come into use. Fig. 17. Reverse osmosis cell Advantages: (i) Rewrse osmosis possessesa distitict adountage of renioving ionic tis well as non-ionic, colloidal snd Irgh molecular soeight organic matter. (i) ft removes colloidal silica, whichis not removed by demineralization, (Gi The maintenance cost is almost entirely on the replacement of the semipermeable membrane. (iv) The life time uf membrane is quite high, about 2 years, (c) The membrane can be replaced within a few minutes, thereby providing nearly uninterrupted water supply. (ci) Due to low capital cost, simpheity, low operating cost and high reliablility, the reverse csmosiss gaining ground at present for converting sea water into drinking water and for obtaining water for very high-pressure boilers.28 ENGINEERING CHEMIST 14 CHEMICAL ANALYSIS OF WATER (1) Estimation of free chlorine : Free chlorine in water, if present beyond a certain limi makes the municipal water unfit for drinking purposes, because chlorine gas is finjurious to Inu nitabolismt. The estimation of free chlorine in water is based on the oxidation of potassium iodide free chlorine. Thus, when the water sample is treated with an excess of potassium iodide solution the free chlorine, present in water, oxidizes potassium iodide and liberates an equivalent amon ‘of iodine, which dissolves in excess potassium iodide forming a deep-violet coloured complex. Cl,+2Ki ——> 2KCl+1, kis Ry (Violet coloured complex) ‘The amount of liberated “iodine” can be estimated by titrating the resulting solution again: standard sodium thiosulphate solution using starch as final indicator. 1,+2NaS,0, —> 2Nal + . NaS,O, (God. teteathionatey I, +Starch ——> Deep blue complex. Procedure : Take about 10 mL. of 10% KI solution in a stoppered 250 mL conical flask. Add to it 50 mL of water sample, holding the point of the pipette just above the iodide solution. Put on the stopper and shake the flask vigorously. Remove the stopper and wash the adhering solution into flask, with about 5-10 mL of distilled water. Then, titrate the solution against N/50 sodium thigsulphate solution, using starch as final indicator. The end-point is the change of colour from. devp-blue to jtist colourless. Calculations : Let 50 mL of water sample mL N/50 Na,S,0, soln. 50 x Normality of free chlorine = Vx (N/50) Normality of free chlorine 72,500 Vx355 Vx 355% 10° and strength of free chlorine ="3500 8/ “= g50051.000 PP™ =142 V ppm. (2) Alkalinity : The alkalinity of water is attributed to the presence of the : ()) caustic alkalinity (due to OH” and COS ions), and (i) temporary hardness (due to HCO; ions). These can be estimated separately by titration against standard acid, using phenolphthalein and methyl orange as indica- tors. The determination is based on the following reactions : (@) (OH”]+[e}] —— H,0 iy (COP) +E] —— [HCO] M (iii), [HCOs}+[H"] ——> H,0+C0, ‘The titration of the water sample against a standard acid upto pireolptthalein end-ponst marks the completion of reactions (i) and (ii) only. This amount of acid used thus corresponds to liydroxide plus one-half of the normal carbonate present, On the other hand, titration of the water sample against a standard acid to methy! orange end-point marks the completion of reactions (i), (ii)-and (iti). Hence, the amount of acid used after the phenalplithalein end-point corresponds to one-half of normal carbonate plusall the bicarbonates; while the total ammount of acid used represents the total alkalinity (due to hydroxide, bicarbonate end carbonate ions).STMENT 29 pestle combinations of ions causing alkalinity in water are :() OH™ only or ‘ely or (fi) HCOF only or (iv) OH” and CO together or (v) CO} and HCO; together. ef OH and HCO; ions together is ruled out, because they combine instantaneously. OH~+HCO; ——3 CO*+H,0 NaOH +NaHCO, — Na,CO,+ 1,0 0H and HCO, ions cannot exist together in water. On the basis of stine reasoning, all the OF ant HCO) cannot exist together. Procedure : Pipette out 100 mL of the water sample in a clean titration flask. Add to it 2 to ‘ef a phenolphthalein indicator. Run in N/50 H,SO, (from a burette), till the pink colour is {Then to the same solution, add 2 or3 drops of methyl orange. Continue the titration, colour reappears, ‘Calculations : Let volume of acid used to phenolphthalein end-point = V, ml, and extra ‘of acid used to methyl orange end-point = V; mL. = Phenolphthalein alkalinity (in terms of CaCO, equivalents), |, __.¥, 50% 1,000,000 P= "50% 100% 1000 = 10¥s Ppm. wl orange zlkalinty (in terms of CaCO, equivalents), = Wack Va)» 50 1,000,000 ~ 50% 100% 1000 |, both OH” and CO} are absent and alkalinity in that case is due to HCO; = 10(V, + V2) ppm. P@) when P= 2) When P=1M, only CO} is present, since half of carbonate neuralization reaction (i.c., =H” ——> HCO}) takes place with phenolphthalein indicator; while complete carbonate tion reaction (ie., CO} +H* ——> HCO;; HCO; + H* ——> H,O+CO,) occurs methyl orange indicator is used. Thus, alkalinity due to CO? =2 P. (3) When P = M, onily OH” is present, because neither CO} nor HCOJ ions are present. Thus, ity due to OH" =P=M, (4) When P > 2M. In this case, besides CO}, OH™ ions are also present. Now half of CO? HCO; +H” — CO,+H,0) equal to (M-P). So, alkalinity due to complete CO?" =2(M=P) Alkalinity due to OH“ =M—2(M—P) =(2P-M). (5) When P< $M, In this case, besides COs", HCO; ions are also present Now alkalinity due to CO-=2P Alkalinity due to. HCO; =(M-2P).30 ENGINEERING CHEMIS" Table 4 : Calculation of alkalinity of water Alakinity | OH pm CO} ppm | —_-HCOS (ypm, | | a 0 M. | | 0 | 2p 0 | 0 | 2P ep-m | 201-7) o | | | | p=M | 0 0 Note : If alkalinity is to be expressed in terms of individual components, then their chemical equiva shouldl be used instead oF 50 (for CaCO). (3) Hardness : The estimation of water hardness as applied to boiler water and other wat is of great interest for the chemical industry in general. Determination of hardness of water can done by using any of the following methods : (i) O. Helmer’s method : (a) Temporary hardness is determined by finding the alkalinity of water before boiling and that left after boiling. This is because temporary hardness is removed on boiling, Boiling Ca(HCO,), os CaCO, $+ Hj0+CO, T Boiling Mg(HCO,),; ——> Mg(OH), 1 + 200, T Procedure ; Pipetie out 50 mi. of water sample in a conical flask. Add 2-3 drops of methyl orange indicator. Titrate against N/50 HICI. Note the volume of acid used (say V, mL). Now take 100 mL. of water sample in a pyrex beakerand evaporate it to dryness, Add about 50 mL of distilled water, warm, stir to dissolve the soluble portions left. Filter the solution and wash the residue with distilled water. Make up the volume to 100 mL in a measuring flask, by adding distilled water. ‘Take 50 ml. of this filtrate in a conical flask and titrate against N/50 HCI using methyl orange as indicator. Let the volume of acid used be V; mL. ~ Volume of N/50 HCl used by temporary harciness present in 50 mL of water =(V,- V2) mL Alkalinity due to temporary hardness in 50 mL of water sample = (V,-V,) mL of N/S0 HCI Alkanlinity due to temporary hardness in terms of CaCO, eq (Vy= V2) * 1x 50 a 50x 50 g/L =(V, - V,)/50 g of CaCO, eq L (y= V5) 10° = ape ior Pm =[20(¥)— Vo ppm (0) Determination of permanent hardness is based on the fact that it can be removed by boiling with a known excess of standard sodium carbonate. The chloride and sulphates of calcium andat ssoluble carbonates. The residual sodium carbonate is then determined by standard acid. The reduction in the amount of soda added is equivalent to CaCl, + NaxCO; ——> CaCO, 1+2NaCl MgSO, +Na,CO, ——+ MgCO, | +Na,SO, + Take 50 mL of given water sample in a beaker. Add it to 50 mL. of N/50 Boil for 15 minutes. Cool the solution. Filter the precipitate, collecting the filtrate Wash the precipitate on filter paper with distilled water, collecting all the conical flask. Then, titrate the unused NajCO, present in the flask against N/50 ts spl orange as indicator. Let the litre value be V mL. of N/50 Na;CO, used for removing permanent hardiess in water sample =(60-V) mL of permanent hardness in terms of CaCO; eq 50 — V) x 50 50% gofCaco, eq= 4) goF CaCO, eq ppm=|2060-V) ppm| fitration method is based on the fact that zolien soluble soap (sodium or potassium salt secid) is added to hard water, it does not give lather, until a sufficient quantity ins been added ll the hardness-praducing metal ions. When all hardness-causing ions have been precipitated, of soap gives lather. 2. CysHyyCOONa + Ca(HCO;), ——> (CyyHagCOO),Ca | +2 NaHCO, Soci stearate (sp) Insoluble cal stearate 2.CyHyCOONa +MgCl, ——> (CiHygCOO), Mg 4-+2NaCl 2 CypHgCOONa + CaSO, ——+ (CyzFygCOO),Ca | +Na,SO, ture : 1, Preparation of standard hard water ; Dissolve 1.0 g of pure, dry CaCO, is ‘quantity of dilute HCI, Boil to dryness to expel excess of acid andl CO3, Dissolve the [M-EDTA] complex + EBT Wine-red (Blue) 7 M* + EBT ————> [M-EBT] complex (Ca? or Mg still present) (Blue) Wine-red34 ENGINEERING CHEMIS} However, when nearly all M™ (Ca** or Mg”) ions have formed [M-EDTA] complex, tH | next'drop of EDTA added displaces the EBT indicator form [M-EBT] complex and the wi colour changes to blue colour (due to EBT). Thus, at equivalence point, {M-EBT] complex + EDTA ——> [M-EDTA] complex + EBT (blue) Titus, change of wine-red colour to distinct blue marks the end-poin! of titration. Various involved in this method are : 1. Preparation of standard hard water : Dissolve 1.0 of pure, dry CaCO, in minimum of dilute HCI and then evaporate the solution to dryness on a water bath. Dissolve the resid distilled water to make 1 L solution. Each mL of this solution thus contains 1 mg of CaCO, hardness. 2. Preparation of EDTA solution : Dissolve 4 g of pure EDTA crystals +0.1 g MgCl in 11. distilled water. 3. Preparation of indicator : Dissolve 0.5 g of Briochrome black-T in 100 mL. of alcohol, 4. Preparation of buffer solution : Add 67.5 g of NH,CI to 570 mL of concentrated amm solution and then dilute with distilled water to 1 L. 5, Standardization of EDTA solution ; Rinse and fill the burette with EDTA solution. Pij out 50 mL of standard hard water ina conical flask. Add 10-15 mL. of buffer solution and 4 t drops indicator. Titrate with EDTA solution, till wine-red colour changes to clear blue. Let vol used by V, mL. 6. Titration of unknotun hand mater: Titrate 50 mL of water sample just in step (5). Let vol used be V, mL. 7. Titration of permanertt hardness’: Take 250 ml. of the water sample in a large beaker. Boil i till the volume is reduced to about 50 mL [when all the bicarbonates are decomposed *0 insoli CaCO, +Mg(OH))|. Filter, wash the precipitate with distilled water, collecting filtrate and w: ings in a.250 mL. measuring flask. Finally make up the volume to 250 mL. with distilled wat ‘Then, titrate 50 ml. of boiled water sample just as in step (5). Let volume used by V3 mL. Calculations : 50 ml. of standard hard water = VymL of EDTA 50x 1 mg of CaCO, V, mL of EDTA 1 ml of EDTA =50/V, mg of CaCO, eq Now 50 mL of given hard water =V,mL of EDTA x50 FMB of CaCOs eq 1 1 L (1,000 mL) of given hard water =1,000 V-/V, mg of CaCO, €4 Vimg/L =| 1,000 V/V, pppal @ Total hardness of waterof boiled water =V, mL of EDTA. V4x50 = am mg of CaCO, eq 1 ‘2800 mL (= 1 L) of boiled water = 1,000 V,/V, mg of CaCO, eq Peet hardness = 1,000 V3/V; ppm ii) Reeperary hardness = [Total — Permanent] hardness iil) of EDTA method : This method is definitely preferable to the other methods, because of -sccaracy : (ii) convenience, and, (ii) more rapid procedure. wed oxygen determination is based on the oxidation of potassium iodide by dissolved ated iodine is titrated against a standard sodium thiosulphate solution using starch However, dissolved molecular oxygen in water is not capable of reacting with carrier (such as manganese hydroxide) is used to bring about the reaction between Manganese hydroxide is produce by the action of potassium hydroxide and man: 2KOH + MnSO, ——> Mn(OH), + K, SO, 2MnQH), + O; ——> 2MnQ(OH); (Oxygen career) Basie manganic oxide MnO(OH), + H,S0, ——+ MnSO,+2H,0+[0] [Nascent oxygen] 2K1+H,S0,+ [0] —> KS0}+H,0 +} 2.Na,$,0, +1, —— 2Nal +Na,S,0,, Starch +1; ——> Starch iodine (blue). ies, water (like rain water) contains substances like nitrites, sulphites, etc. and of dissolved oxygen in their presence will give wroitg results, since these fons also from KI. Therefore, sodium azide (NaN,) is used in alkaline iodide solution to take ny nitrite, if present in water, does not liberate iodine from K I. Sodium azide reacts with decompose it as follows : 2NaN,+H,S0, ——> 2HN,+Na,SO, HNO, +HN, —— > N,OT+N;7+H,0 Procedure : Collect 250 mL of water in a bottle aovidinig as for as possible contact with aur ly add 2 mL of manganous sulphate solution (prepared by dissolving 400 g MnSO, per of pipette, dipping the end well-below the water surface. Add 2.0 mi. of alkaline iodide {prepared by dissolving 150 g K 1 +500 g NaOH and 20 g sodium azide, NaN; per L) in manner. Stopper the bottle and shake it thoroughly. Allow the precipitate to settleeo ENGINEERING G} Tale way and mix again. Repeat this process of shaking and settling at least three times. toyit 20 mL of conc."H,SO,, Insert the stopper and shake the bottle again. Allow the yellow sok stand for 5 minutes. Withdraw 100 mL. of the solution and titrate it against N/100 thiosulphate solution (prepared by dissolving 2.48 g of sodium thiosulphate per L) using Prepared starch as indicator. End-point is disappearance of blue colour. If mt. is vol thiosulphate used then, dissolved oxygen content in water =8 Vppm. Cal GO 4 EG — CaCO, . 1,0 (Ofwater) (Oxalate ions) (Cal. oxalate) The precipitate is filtered through a weighed Whatman 40 filter paper. Wash the P Lunt the washings are free from oxalate ions. Then, dry the filter paper (containing precipi an oven at 105°C for 1 hour. Finally, weigh the precipitate along-with filter. Diffccence weighings gives the amount of calcium oxalate formed. Caleutations : Let volume of water sample taken = 250 mL. Initial weight of Whatman paper ‘We of dry ppt. along-with Whatman paper Wt of dry precipitate (of cal. oxalate) Now CaC,0,.H,0 =Ca M6 “0 146 g of cal. oxalate contains Ca = 40g _40xw “146 & "250 ml. of water sample contains Ca=x g (say) oF 1,000 mL of water sample contains Ca =4 xg.Ca or calcium in water sample =4 x g/litre = 4,000 x mg/litre w § of cal. oxalate contains Ca Hence, amount of calcium in water =[4,000x ppm 18 — LANGELIER INDEX (L.1,) whete =[PKiy~ PKL} +P [Ca? "| +p (bicarbonate alkalinity) a= schubiity product of CaCO =[Cs**}{CO}T Gssociation constant for: HCO; = HY +CO}~ J =

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