2.2 TECHNOLOGY OF WATER 2.2.1 Introduction Sources of water Surface water Underground water 2.2.2 Depletion of underground water 2.2.3 Rain water Harvesting Water is the most essential compound for all living matter on the earth. It plays an important role in human living and industries. The two important sources of water are (1) surface water and (2) underground water. The water available on the earth's surface is called as surface water. Surface water includes rainwater, river water, lake water and seawater. Underground water includes water present between the rocks in the earth crust, spring water, well water etc. The decrease in the quantum of underground water is depletion of water. Depletion of water is mainly caused by, 1. Modernization, industrialization and population growth 2. Global warming causing excess evaporation of surface water 3. Deforestation 4. Decrease in rainfall caused by seasonal changes and 5. Effluents from the industries spoiling the ground water source. To meet out this depletion of ground water sources, it is essential to find alternate plans using water management techniques to recharge the ground water sources. One of the techniques adopted is rainwater harvesting. Rainwater harvesting (RWH) is collection of rainwater for useful purposes . The methods employed are 1. Roof top harvesting 2. Open space harvesting 36 Roof top harvesting Open space Harvesting Types of impurities present in water 2.2.4 Types of water 2.2.5 Hardness of water Rainwater is directly used for recharging open wells and bore wells by directing them into it. It can also be stored in sumps or over head tanks and used directly. Open spaces around the buildings are used for rainwater harvesting as follows 1. With percolation/recharge pits 2. Recharge trenches 3. Recharge wells The recharge method used depends on the soil condition. There are three types of impurities present in water. They are (i) Suspended and colloidal impurities. (ii) Dissolved salts. (iii) Micro - organisms. There are two types of water. They are (i) soft water and (ii) hard water. (I) Soft water readily gives lather with soap. (ii) Hard water does not give lather with soap. There are two types of hardness in water. They are: (i) Temporary Hardness: (Carbonate hardness) It is due to the presence of calcium bicarbonate [Ca(HCO ) ] and magnesium bicarbonate [Mg (HCO ) ]. Temporary Hardness can be removed by boiling. (ii) Permanent Hardness: (Non-Carbonate hardness) It is due to the presence of chloride and sulphate salts of calcium and magnesium. (CaCl , CaSO , MgCl MgSO ).It cannot be removed by boiling. Hence it is known as permanent hardness. 3 2 3 2 2 4 2, 4 37 Disadvantages of a hard water sample 2.2.6 Degree of Hardness Units for measuring hardness Note        Hard water cannot be used for drinking purpose. It cannot be used for cooking purposes. It cannot be used for bathing and washing purposes as it does not give lather with soap. Hard water cannot be used in laboratories as it gives unwanted chemical reactions. Hard water cannot be used in boilers in steam raising. It cannot be used in sugar and paper industries. Hard water cannot be used in textile and leather industries. . 1.mg/litre of CaCO 2.parts per million of CaCO Usually ,the hardness of water is expressed in terms of calcium carbonate equivalents The formula used to convert the mass of hardness producing salt to mass of CaCO equivalents is given below Molecular masses of hardness producing salts are given below. CaSO 136 MgSO 120 CaCl 111 MgCl 95 Ca(HCO ) 162 Mg(HCO ) 146 CaCO 100 3 3 3 4 4 2 2 3 2 3 2 3 Hardness producing salt Molecular Mass 38 Mass of salt Molecular mass of CaCO3 Calcium carbonate equivalents Molecular mass of salt Problem - 1 2.2.7 Estimation Of Hardness Of Water - EDTAMethod PRINCIPLE PROCEDURE A water sample contains 48 mg of MgSO per 200ml of water. Calculate the hardness in terms of CaCO equivalent in mg/litre of CaCO Mass of MgSO = 48mg Molecular mass of MgSO = 120 Mass of CaCO present in200 ml of water = 40mg Therefore, mass of CaCO present in 1000ml of water = 200mg Hardness of water = 200mg/litre of CaCO EDTA method is used to determine the hardness of a sample of water. EDTA refers to Ethylene diamine tetra acetic acid. This method is also called as Modern method. This is a volumetric method based on the principle of formation of complexes. Ethylene diamine tetraacetic acid (E.D.T.A.) forms colourless complexes with Ca and Mg ions present in water. Similarly Eriochrome Black-T, another dye, also forms wine red coloured complexes with Ca and Mg ions. Pure Eriochrome Black-T is blue in colour. At the pH range of 9 to 10, the Eriochrome complexes are less stable when compared to E.D.T.A. complexes. Thus when E.D.T.A. solution is added to Eriochrome-Ca or Mg complexes it displaces pure Eriochrome to form E.D.T.A-Ca or Mg complexes. Thus at the end point E.D.T.A. frees the total Eriochrome Black-T to change the colour of the solution from wine red to steel blue. Eriochrome-Ca +E.D.T.A.---------> .D.T.A-Ca + Eriochrome Black-T The burette is filled with the standard E.D.T.A. solution. A 50-ml pipette is washed with distilled water and rinsed with the sample of hard- 4 3 3. 4 4 3 3 3 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ 2+ E WineRed Steel Blue 39 40mg 120 48 100 Molecular Mass of MgSO Mass of MgSO Massof CaCO Calcium carbonate equivalents 4 4 3 water. Exactly 50 ml of hard-water is pipetted out into a conical flask and 5 ml of NH Cl - NH OH buffer solution is added. A pinch of Eriochrome Black-T indicator is added. The colour of the conical flask solution changes into wine red. The water sample is titrated against the E.D.T.A. solution taken in the burette. The colour changes from wine red to steel blue. This is the end point of the titration. The burette reading is noted. Titrations are repeated until two consecutive values agree. From the volume of E.D.T.A. the hardness of the sample of water is calculated. In the estimation of hardness of water, a standard data relating the mass of CaCO and volume of 0.01M EDTAsolution .is given below Let,the Volume of water taken =50ml volume of E.D.T.A. consumed =Vml 1ml of 0.01 M E.D.T.A. 1 mg of CaCO V ml of 0.01 M E.D.T.A.= V mg of CaCO V ml of 0.01 M E.D.T.A. 50 ml of Hard water. Mass of CaCO present in 50 ml of Hard water = V mg = 20 V mg A sample of 100 ml of hard water consumes 25 ml of 0.01M EDTA solution. Calculate the hardness of the sample of water. 25ml of 0.01M EDTAsolution 25 mg of CaCO 25ml of 0.01M EDTAsolution 100 ml of hard water Mass of CaCO present in 100 ml of hard water = 25 mg Mass of CaCO present in 1000ml of hard water = 250mg Hardness of water = 250mg/litre of CaCO 4 4 3 3 3 3 3 3 3 3 Note: CALCULATION HARDNESS OF WATER = 20V mg /litre of CaCO Problem- 1 ≡ ≡ ≡ ≡ Mass of CaCO present 3 3 mg 50 V 1000 Mass of CaCO present in1000ml of Hard water 3 1ml of 0.01M EDTA solution 1mg of CaCO ≡ 3 1ml of 0.01M EDTA solution 1mg of CaCO ≡ 3 40 g 100 25 10 10 Mass of CaCO present in 10 g of hard water -3 6 6 3 To express in ppm Mass of CaCO present in 100 ml of hard water = 25 mg Mass of CaCO present in 100g of hard water = 25×10 g = 250g Hence, hardness of water = 250 ppm of CaCO A sample of 100 ml of water consumed 12.5 ml of 0.01 M EDTA solution. In another titration 100 ml of the same sample, after boiling for half an hour consumed 8.2 ml of the same EDTA solution. Calculate the carbonate and non-carbonate hardness of the sample of water. 12.5ml of 0.01M EDTAsolution 12.5 mg of CaCO 12.5ml of 0.01M EDTAsolution 100 ml of hard water Mass of CaCO present in 100 ml of hard water = 12.5 mg Mass of CaCO present in 1000ml of hard water = 125mg Hence, Total hardness of water = 125 mg/litre of CaCO 8.2ml of 0.01M EDTAsolution 8.2 mg of CaCO 8.2ml of 0.01M EDTAsolution 100 ml of hard water Mass of CaCO present in 100 ml of hard water = 8.2 mg Mass of CaCO present in 1000ml of hard water = 82 mg Hence, Non-carbonate hardness of water = 82 mg/litre of CaCO Therefore, Carbonate Hardness =Total hardness – Non-carbonate hardness =(125 – 82) = 43 mg/litre of CaCO 3 3 3 3 3 3 3 3 3 3 3 3 -3 Problem- 2 Total hardness Non-carbonate Hardness ≡ ≡ ≡ ≡ 41 2.2.8 Methods of softening hard water (1) Ion exchange method Softening Process In this method the hard water is first passed through an acidic resin (RH ) to remove the cations [Ca , Mg ] and then it is passed through a basic resin [R'(OH) ] to remove the anions. Thus both types of ions are totally removed. Acidic resin is represented by RH . Basic resin is represented by R'(OH) When the hard water sample is passed through the I-Cylinder (acidic resin) calcium and magnesium ions are replaced by hydrogen ions of the acidic resin. RH + Ca RCa + 2H RH + Mg ----------> RMg + 2H When this water is passed through the II-Cylinder (basic resin) chloride, bicarbonate and sulphate ions are replaced by the hydroxide ions of the basic resins. R'(OH) + 2Cl ---------->R'Cl + 2OH¯ R'(OH) + 2HCO ¯---------> R'(HCO ) + 2OH¯ R'(OH) + SO ----------> R'SO + 2OH¯ Thus all the ions responsible for hardness are removed from water. The H and OH ¯ ions combine together to form water. H + OH ----------> H O The quality of water obtained by this method is equivalent to distilled water. 2 2 2 2. 2 2 2 2 2 3 32 24 4 2 2+ 2+ 2+ + 2+ + 2– + + – ----------> Acidic resin Acidic resin 42 Diagram Regeneration ofAcid Resin and Basic Resin Advantages (2) Reverse Osmosis Method Osmosis : After a long use, the acidic resin can be regenerated by the addition of a strong solution of Hydrochloric acid. RCa + 2HCl -----------> RH +CaCl The basic resin after a long use, can be regenerated by the addition of a strong solution of NaOH. R'Cl + 2OH¯ -----------> R' (OH) + 2Cl ¯ R' (HCO ) + 2OH¯ -----------> R'(OH) + 2HCO ¯ R'SO + 2OH¯ ----------> R'(OH) + SO 1) In this method, both types of hardness are removed. 2) The quality of water obtained is equivalent to distilled water. 3) There is no wastage of water When a semi-permeable membrane separates two solutions of different concentrations, solvent molecules move from side to side until the two concentrations become equal. This process is called osmosis. The pressure gradient produced due to osmosis is called osmotic pressure. 2 2 2 2 32 2 3 4 24 2– dilute concentrated 43 Hard water Acid resin Basic resin Soft water Cation exchanger Anion exchanger Reverse Osmosis Method When a hydrostatic pressure greater than the osmotic pressure is applied on the concentrated side, solvent molecules move from concentrated side to the dilute side across the membrane. This is called reverse osmosis. This principle is used in Reverse Osmosis plants to soften hard water. In this method hard water and soft water are taken in two different chambers separated by a semi permeable membrane. When a hydrostatic pressure greater than the osmotic pressure is applied on the hard waterside, the water molecules move from hard waterside to soft waterside leaving the impurities on the membrane due to reverse osmosis. Thus hard water is converted to soft water by Super filtration or hyper filtration. The semi permeable membrane is made of polysulphone or cellulose acetate or polyamide. Diagram Hard water Soft water Pressure Piston Semi-permeable membrane 44 Advantages 2.2.9 Municipal water supply Water for Drinking purpose ( Potable water ) 1) In this method ionic, non-ionic, colloidal, and organic particles are removed from water. 2) The semi permeable membrane can be replaced and reused. 3) There is no wastage of water. Municipal water is mainly used for drinking purposes and for cleaning, washing and other domestic purposes. The water that is fit for drinking purposes is called potable water (1)Characteristics of Potable water 1.It should be colourless, odourless and tasteless. 2.It should be free from turbidity and other suspended Impurities. 3.It should be free from germs and bacteria. 4.It should not contain toxic dissolved impurities. 5. It should be moderately soft. 6. It should not be corrosive to the pipe lines. 7. It should not stain clothes. (2)Standards of drinking water as recommended by WHO Parameters WHO standards pH BOD COD Arsenic Calcium Cadmium Chromium Ammonia Copper Iron Lead Mercury Magnesium Manganese Chloride Cyanide Nitrate + Nitrite 6.5 - 9.2 6 10 0.05ppm 100ppm 0.01ppm 0.05ppm 0.5ppm 1.5ppm 1.0ppm 0.001ppm 0.1ppm 150ppm 0.5ppm 250ppm 0.05ppm 45ppm 45 (3)Water quality standards in india The three stages involved in purifying a water sample for drinking purpose are 1. Sedimentation 2. Filtration 3. Sterilisation Water from river or lake is taken in the big tank called sedimentation tank. Here the insoluble matter settles down at the bottom of the tank as sediments. In this tank the colloidal impurities are converted into precipitate by adding Alum. The clear water from the top layer is sent to the next tank, called Filtration tank. In filtration tank, the suspended impurities and the microorganisms are removed. In all types of filtration, the filter bed used is constructed as follows. Sedimentation Filtration 46 Parameters Standard pH Total Hardness Turbidity Chlorides Cyanide Fluoride Nitrate Sulphate Manganese Mercury Iron Copper Cadmiun Chromium Lead Arsenic Zinc Magnesium 6.3 - 9.2 600 ppm 25 ppm 1000 ppm 0.05 ppm 1.5 ppm 45 ppm 400 ppm 0.5 ppm 0.001 ppm 1 ppm 1.5 ppm 0.01 ppm 0.05 ppm 0.15 ppm 0.05 ppm 15 ppm 150 ppm The filter bed consists of a layer of fine sand, followed by a layer of coarse sand, which is then followed, by a layer of gravel. There is a drain at the bottom to remove the filtered water. The layer of fine sand acts as the filtering unit and the other two beds support the fine sand layer. Generally filtration is done due to the gravitational force. The filtered water is then taken to the sterilization tank. In industrial areas where large amount of drinking water is required in short period, Pressure filters are used in which water is sent through filter beds using external pressure.) Sterilization is destroying of bacteria. It is done by Chlorination. Chlorination is addition of chlorine. Chlorine is added to water in the pH range of 6.5 to 7. When chlorine is added to water, it forms HCl and HOCl. The hypochlorous acid enters into the living cells of bacteria and destroy them. H O + Cl ---------- >HCl + HOCl Hypochlorous acid Other sterilizing agents used are chloramines, bleaching powder etc. The advantage of using chloramines is that it does not evaporate out easily and can be carried over to a longer distance along with the water. Diagram (Note: Sterilization Chlorination 2 2 Drain Drain Water Water from sedimentation tank Fire sand Coarse sand 47 Ultra-violet rays can also be used for sterilizing purpose. Water is used in boilers, steam engines etc., to raise steam. When a sample of hard water is used in boiler to prepare steam, the following problems will occur. 1. Scale formation 2. Corrosion of boiler metal 3. Caustic Embrittlement and 4. Priming and foaming. When hard water is used in boilers to get steam, the impurities that are present in the hard water will settle down on the sides of the boiler. This residue in due course will adhere to the boiler vessel surface in the form of a sludge or scale. This is called as boiler scale. The following calcium salts are responsible for the formation of boiler scale. CaSO , CaCO CaSiO , Ca (OH) Mg (OH) ,etc 1. The salt deposit formed is a poor conductor of heat. Therefore, fuel is wasted in raising the temperature of the boiler. 2. Due to the increase in the temperature, the plates may melt. This may lead to explosion of boiler. 3. At higher temperature, more oxygen may be absorbed by the boiler metal, which causes corrosion of boiler metal. 4. The sudden spalling of the boiler scale exposes the hot metal suddenly to super-heated steam, which causes corrosion of boiler. The two types of methods employed to prevent scale formation are, 1. Internal conditioning method 2. External conditioning methods. 1. Internal conditioning methods involve addition of complexing agents like Calgon to boiler feed water. Another method of internal conditioning method is Phosphate conditioning. In this method sodium phosphate is added to boiler feed water which forms non-sticky Calcium 2.2.10 Boiler feed water (1) Boiler scale formation Disadvantages of Boiler scale 4 3, 3 2, 2 . 48 and Magnesium Phosphate which can be removed by blow down operation. 2. In external conditioning methods water is purified either by Zeolite process or by ion-exchange method before being fed into boilers. The impurities such as dissolved oxygen, dissolved Carbon di oxide, mineral acids, dissolved salts of calcium and magnesium, organic matter etc.are responsible for the corrosion of boilers. The dissolved matter undergoes hydrolysis and forms acids. The acid slowly attacks the inner part of the boiler. The dissolved oxygen attacks iron at high temperature. The CO and H O form carbonic acid (H CO ), which slowly attacks the metal. 1. By using proper water treatment procedures. 2. By degasification to remove the dissolved gases like oxygen, CO , etc., 3. The dissolved CO can be removed by the addition of limewater. 4. Adding calculated amount of base could neutralize the mineral acids. Sometimes cracks appear inside the boiler parts, particularly at the places, which are under stress. Metal becomes brittle at these places. It is due to the high concentration of caustic soda (NaOH) and a little amount of silica in water. This is called as caustic embrittlement. Caustic soda is formed by the hydrolysis of Na CO . Na CO + H O ----------> 2NaOH + CO Removal of Na CO present in water can prevent caustic embrittlement. This can be done by the following methods. 1. By adding sulphuric acid. 2. By adding CaSO and CaCl to boiler water 3. By adding Na SO 4. By adding trisodium phosphate. (2) Corrosion of Boiler metal Prevention of Boiler Corrosion (3) Caustic Embrittlement: 2 2 23 2 2 2 3 232 2 2 3 4 2 2 4. 49 Foaming is nothing but the formation of foam. Bubbles of water will enter the surface of water inside the boilers and results in the formation of foam. Foam comes out of the boiler along with the steam. Hence the steam becomes wet and the heat content of the steam is reduced considerably. This type of wet steam spoils the machine parts where it is used. The main cause for foaming is the presence of dissolved salts in water. Hence soft water should be used in boilers to avoid foaming. Priming is violent and rapid boiling of water inside the boiler. Due to priming the water particles mix up with the steam when it comes out of the boiler. Like foaming, priming also reduces the heat content of the steam and reduces the efficiency of the steam. Main reasons for Priming a) Defective design of the boiler. b) Presence of large quantities of dissolved salts, oily matter, alkaline and suspended matter. 1. Priming can be controlled by proper design of the boiler 2. By uniformly heating the water in the boiler. 3. By using a better sample of water. Students have learnt about rain water harvesting, estimation of hardness, methods of softening and bad effects of hard water in boilers.