WATER TECHNOLOGY Characteristics alkalinity types of alkalinity and determination hardness types and estimation by EDTA method (problems),

ms), Domestic water treatment disinfection methods (chlorination, ozonation, UV treatment boiler feed water requirements disadvantages of using hard water in boilers internal conditioning (phosphate, calgon and carbonate conditioning methods) external conditioning demineralization process desalination and reverse osmosis. Water is the essential commodity for any engineering industry. The sources for water are of stationary type such as pond, lake etc. or of flowing type such as river. The purest source of water is rain but rain also during its travel through atmosphere contains trace levels of dissolved carbon dioxide. The impurities in any water sample influence its characteristics. The physical characteristics of water are colour, odour, taste etc. The chemical characteristics of water evolve from the dissolved gases, salts etc. Microorganisms such as bacteria, viruses etc present in any water sample impart biological characteristics such as pathogenic nature. Depending on the source, water sample may consist of impurities in soluble or dispersed or suspended form. The impurities in water sample impart some undesirable properties to water and hence render the sample ineffective for the particular engineering application. The important characteristics of water, which influence its utility in engineering industry, are alkalinity and hardness. The alkalinity of water (pH>7) is attributed to the presence of the following species: hydroxides (OH-), carbonates (CO32-) and bicarbonates (HCO3-) of alkali or alkaline earth metals. The alkalinity is of types namely hydroxide alkalinity and carbonate alkalinity. The alkalinity caused by the alkali metal ions Na+, K+ is termed as caustic alkalinity. It is obvious that the strength of alkalinity for the above anions is in the order OH- > CO32- > HCO3Worked Example 1: A water sample has the following composition: Sodium bicarbonate = 2.5 mg / lit Sodium Carbonate = 2.6 mg / lit; Potassium carbonate = 2.9 mg / lit Potassium bicarbonate = 1.7 mg / lit and carbon dioxide = 1.5 mg / lit. Identify the types of alkalinity present in the sample. Calculate the total alkalinity of the water sample. Solution: Alkalinity due to any species in terms of CaCO3 equivalent = = Weight of the species in water (mg / l) X 50 Equivalent weight of the species Weight of the species in water (mg / l) X 100 Molecular weight of the species (OR)

Alkalinity due to carbonate = [(2.5 / 84) + (1.7 / 100)] 50 Alkalinity due to bicarbonate = [(2.6 / 106) + (2.9 / 138)] 50 Alkalinity due to carbon dioxide = [(1.5 / 44) 50 Total alkalinity = alkalinity due to (CO32- + HCO3- - CO2) = 2.338 + 2.277 1.7045 = 2.9105 ppm CaCO3 equivalent Here it is to be noted that dissolved carbon dioxide tends to reduce the alkalinity of the water sample, as it amounts to the formation of carbonic acid (which reduces pH). Worked Example 2: A water sample has the following composition: Sodium hydroxide = 4 mg / lit and potassium hydroxide = 5.6 mg / lit. Identify the type of alkalinity present in the sample. Calculate the total alkalinity of the water sample. Ans: The type of alkalinity in the sample is caustic alkalinity. Total alkalinity = [ (4 / 40) + (5.6 / 56) ] 50 = 10 ppm CaCO3 equivalent. Determination of alkalinity: Principle / Theory: The alkalinity of water sample can be determined by titration against a standard (or previously standardized) acid using the indicators phenolphthalein and methyl orange. The reactions for the neutralization of various anionic species are as follows: OH- + H+ H2O CO32- + H+ HCO3HCO3- + H+ H2O + CO2 (i) (ii) (iii)

Phenolphthalein indicator can be used with stronger alkalinity only whereas the indicator methyl orange works well with any type of alkalinity. Thus, the titration of the water sample against a standard acid with phenolphthalein indicator (end point is termed as phenolphthalein end point) represents the completion of reactions (i) and (ii) only. On the other hand, the titration of the water sample against a standard acid with methyl orange indicator (end point is termed as methyl orange end point) represents the completion of all the reactions (i), (ii) and (iii). Hence, the amount of acid used for the phenolphthalein end point corresponds to all bicarbonates plus one half of normal carbonate while the total amount of acid used corresponds to the total alkalinity (caused by hydroxides, bicarbonates and carbonates). For practical purposes the alkalinity of water sample is expressed as types such as hydroxide alkalinity, carbonate alkalinity and bicarbonate alkalinity. Amongst the combinations of various ions causing alkalinity, the possibility of

hydroxide and bicarbonate ions existing together is ruled out, as these ions combine instantaneously to form carbonate ions. e.g. NaOH + NaHCO3 Na2CO3 + H2O. Similarly, all these three anions cannot exist together. The alkalinity due to these ions is expressed commonly in terms of CaCO3 equivalent. Procedure: 100 ml of the water sample is pipetted out into a clean conical flask. 2-3 drops of phenolphthalein indicator are added and titrated against N/50 sulphuric acid taken in the burette. End point is the disappearance of pink colour. Then to the same solution, 2-3 drops of methyl orange indicator are added and the titration continued for the reappearance of pink colour, which is the end point. Observations & Calculations: Let Vp and Vm be the volumes of acid used with phenolphthalein and methyl orange indicators respectively. (Obviously total volume Vt = Vp + Vm) Phenolphthalein alkalinity = (Vp X 50 X 106) / (50 X 100 X 1000) ppm CaCO3 equiv. Methyl Orange alkalinity = (Vm X 50 X 106) / (50 X 100 X 1000) ppm CaCO3 equiv. Total alkalinity = (Vt X 50 X 106) / (50 X 100 X 1000) ppm CaCO3 equiv. Following table enables the calculation of alkalinity due to various ions: (Let P = Vp & M = Vm) Alkalinity Titre Value P=0 P=M P>M P<M P=M OHPpm 0 0 2P M 0 M CO32ppm 0 2P 2 (M P) 2P 0 HCO3ppm M 0 0 M 2P 0

Alkalinity = (V X 50 X 106) / (50 X 100 X 1000) ppm CaCO3 equiv. Water is largely used in boilers (as feed) for the production of steam. High-pressure steam, in turn, is used much in mechanical engineering field. The presence of impurities in water sample renders it hard (and corrosive too in some cases). In turn, any water sample cannot be used as boiler feed as it may pose the problems of corrosion, embrittlement of the boiler vessel etc. Water with some specifications, used in boilers for steam generation is called boiler feed water. The requirements of boiler feed water are as follows: It should be free from (i) turbidity, oily / soapy matter and dissolved salts (ii)

hardness causing and scale forming materials (iii) dissolved oxygen and carbon dioxide (these cause boiler corrosion) and (iv) caustic alkali (it promotes boiler embrittlement). Hardness of Water: The hardness of a water sample means its resistance to lather forming tendency with soap. Lather forming capacity of the water sample with soap is hindered by the presence of cations Ca2+ and / or Mg2+ in water. The reason is that some amount of soap is consumed by these ions producing a precipitate / scum, as shown by the equation below: 2 RCOONa + M2+ (RCOO)2M + Na+, where M = Ca or Mg soap scum The hardness of water sample arises due to the presence of calcium and magnesium ions in the water sample. The hardness of any water sample is of two types namely temporary hardness and permanent hardness. Temporary hardness / Carbonate hardness of water is caused due to the presence of bicarbonates and carbonates of calcium and / or magnesium. It can be removed by boiling and filtration i.e. during boiling, carbonates / hydroxides are precipitated and retained on the filter bed on filtration. Ca(HCO3)2 CaCO3 + H2O + CO2 ; Mg(HCO3)2 Mg(OH)2 + 2 CO2

Permanent hardness / Non-carbonate hardness of water is caused due to the presence of chlorides and sulphates of calcium and / or magnesium and it cannot be removed by mere boiling and filtration. Permanent harness in water requires special methods for its removal. Total hardness of water is the sum of temporary and permanent hardness values. Since hardness of water may be due to one or more of the ions Ca 2+, Mg2+, CO32-, Cl-, SO42-, it is expressed commonly in terms of CaCO3 equivalent. The reason for CaCO3 reference is that it is the most insoluble form of all the salts causing hardness. Temporary hardness = Hardness due to (calcium bicarbonate + magnesium bicarbonate) Permanent hardness = Hardness due to (calcium chloride + calcium sulphate + magnesium chloride + magnesium sulphate) Hardness of a water sample in terms of CaCO3 equivalent = Weight of the substance (mg / l) X 100 Molecular weight of substance (OR) ppm ppm

where 100 is the molecular weight of calcium carbonate Hardness of a water sample

Weight of the substance (mg / l) X 50

in terms of CaCO3 equivalent =

Equivalent weight of substance

where 50 is the equivalent weight of calcium carbonate. Worked Example 3: A water sample has the following composition: Calcium bicarbonate = 4.3 mg / lit ; Magnesium bicarbonate = 3.4 mg / lit ; Calcium chloride = 2.3 mg/lit ; Magnesium chloride = 3.5 mg / lit ; Calcium sulphate = 2.3 mg/lit ; Magnesium sulphate = 3.5 mg / lit ; Sodium Chloride = 1.3 mg / lit ; Sodium bicarbonate = 2.5 mg / lit Sodium Carbonate = 2.6 mg / lit; Potassium carbonate = 2.9 mg / lit Potassium bicarbonate = 1.7 mg / lit and carbon dioxide = 1.5 mg / lit. Identify the types of hardness present in the sample. Calculate the total hardness of the water sample. Solution: Hardness due to any species in terms of CaCO3 equivalent = = Weight of the species in water (mg / l) X 50 Equivalent weight of the species Weight of the species in water (mg / l) X 100 Molecular weight of the species (OR)

Temporary hardness (Carbonate) = [(4.3 / 162) + (3.4 / 146)] 100 = 4.983 ppm Permanent hardness = [(2.3 / 136) + (2.3 / 111) +(3.5 / 95) +(3.5 / 120)] = 10.364 ppm Total hardness = Temporary hardness + Permanent hardness = 10.364 + 4.983 = 15.347 ppm CaCO3 equivalent Estimation of Hardness by EDTA Method: Three methods available for the estimation of hardness of water are (i) soap titration method (ii) alkali titration method and (iii) EDTA method. Soap titration is based on the volume of soap solution required for lather formation. Alkali titration is based on the alkalinity created by the temporary hardness causing ions. Of these three methods, EDTA method is the most accurate method of estimation of hardness of water. Principle / Theory: EDTA method is a based on the complexometric reaction between the hardness causing cations Ca2+ and Mg2+ and EDTA (Ethylene Diamine Tetra-acetic Acid). EDTA acts as the ligand (with amino nitrogen atom having lone electron pair for donation) and chelates with the metal ions Ca2+ and Mg2+. The resulting chelate complex anion is more stable so that this reaction excludes the ordinary reactions of the metal ions. EDTA is used as its

disodium salt. Hence the hardness of water can be determined by EDTA method with special indicator.
+ _ Na OOCH2C NCH2-CH2N CH2COOH EDTA HOOCH2C

HOOCH2C NCH2-CH2N HOOCH2C

CH2COOH

CH2COOH _ + CH2COO Na

Disodium salt of EDTA

OH + _ Na O3S N=N

ON Structure of EBT EDTA or its disodium salt forms stable complex ions with Ca 2+ and Mg2+ ions in water. The indicator used is Eriochrome Black T (EBT - alcoholic solution of a blue dye). EBT is sodium-1-(1-hydroxy-2-naphthylazo)-6-nitro-2-naphthol-4-sulphonate. The indicator forms a weak, wine-red coloured complexes with Ca2+ and Mg2+ ions at a pH of about 10. Ca2+ + EBT Mg
2+

Ca EBT Mg

This unstable complex is quickly replaced by the titrant EDTA, to form more stable metal-EDTA complex, thereby releasing the free indicator molecules. Ca2+ + EDTA Mg
2+

Ca EDTA Mg

Thus the end point of the titration is the change of colour from wine red to distinct blue. Procedure: Standard hard water is prepared by dissolving 1 g of CaCO3 in minimum amount of dil. HCl, evaporating the solution to dryness on a water bath, dissolving the residue in distilled water and making up to 1 lit. Each ml of the resultant solution contains 1 mg of CaCO3 equivalent hardness. 4 g of pure EDTA crystals is dissolved in 1 lit of distilled water. 0.5 g of EBT is dissolved in 100 ml of alcohol. Buffer soln (to maintain a pH of 10) is prepared by dissolving 67.5 g of NH4Cl in 570 ml of concentrated ammonia solution and making to 1 lit with distilled water.

Standardization of EDTA: The burette is rinsed and filled with EDTA solution. 50 ml of std. hard water is pipetted out into a clean conical flask and added 10-15 ml of buffer solution and 4-5 drops of indicator. The solution is titrated against EDTA solution in the bureete for the change of colour from wine red to clear blue, which is the end point. Let the titre value be V1 ml. Estimation of total hardness of water sample: 50 ml of sample water is similarly titrated and the titre value is noted as V2. Estimation of permanent hardness of water sample: 250 ml of the water sample is taken in a 500 ml beaker and boiled till the volume is reduced to 50 ml. [Now, all the bicarbonates are decomposed to insoluble CaCO3 and Mg (OH)2 ]. Then it is filtered and the precipitate washed with distilled water. The washings are collected in 250 ml standard flask and made up to the mark with distilled water. 50 ml of the boiled water is titrated in a similar and the titre value noted as V3. Calculations: 50 ml of std. hard water V1 ml of EDTA i.e. 50 X 1 mg of CaCO3 V1 ml of EDTA 1 ml of EDTA (50 / V1) mg of CaCO3 equivalent hardness 50 ml of sample hard water V2 ml of EDTA (V2 X 50 / V1) mg of CaCO3 equivalent hardness 1lit (1000 ml) of water sample (V2 X 50 X 1000 / V1 X 50) mg of CaCO3 equivalent hardness Total hardness of water = (1000 V2 / V1) mg/lit (or) ppm 50 ml of boiled water V3 ml of EDTA (V3 X 50 / V1) mg of CaCO3 equivalent hardness 1lit (1000 ml) of water sample (1000 V3 / V1) mg of CaCO3 equivalent hardness Permanent hardness = (1000 V3 / V1) mg/lit (or) ppm Temporary hardness = Total hardness minus permanent hardness = 1000 (V2-V3) / V1 mg/lit (or) ppm Worked Example 4: 1 ml of a standard hard water contains 1 mg of CaCO3. 20 ml of this standard hard water requires 19 ml of EDTA for titration. 50 ml of a water sample consumes 21.5 ml of EDTA for titration. 50 ml of the same water sample after boiling and filtration consumed 9 ml of EDTA for titration. Calculate the temporary, permanent and total hardness values of the water sample. Solution:

20 ml Std. hard water 20 mg CaCO3 19 ml of EDTA 1ml of EDTA 20 / 19 = 1.053 mg CaCO3 21.5 ml of EDTA (20 X 21.5 / 19) = 22.6316 mg CaCO3 i.e. 50 ml of water sample 22.6316 mg CaCO3 1000 ml (or) 1 lit of water sample contains ( 22.6316 X 1000 / 50) ppm Total hardness = 452.63 ppm CaCO3 equivalent

9 ml of EDTA (20 X 9 / 19) = 9.474 mg CaCO3 i.e. 50 ml of water sample 9.474 mg CaCO3 1000 ml (or) 1 lit of water sample contains ( 9.474 X 1000 / 50) ppm Permanent hardness = 189.474 ppm CaCO3 equivalent

Temporary hardness = Total hardness minus Permanent hardness = 452.63 189.474 = 263.156 ppm CaCO3 Domestic water treatment: The requisites of water for domestic / drinking purposes, called potable or domestic water are: (i) sparkling clarity and odourless nature (ii) pleasant taste (iii) chillness (iv) turbidity content less than 10 ppm (mg/l) (v) to be free from objectionable dissolved gases such as H2S, objectionable minerals such as lead, arsenic, chromium and manganese salts and disease causing organisms (vi) only slight alkalinity (with pH8) (vii) reasonable softness and (viii) low TDS (total dissolved salt) content ( 500 ppm). Domestic water treatment mainly aims at the removal of suspended impurities and microorganisms (with desalination also). The main steps involved in domestic water treatment are (i) screening (ii) sedimentation (iii) filtration and (iv) disinfection. Screening is the process of removal of coarse impurities such as floating matter, leaves, wood pieces etc. by passing through mesh screens with large number holes, which retain these impurities. Sedimentation is the process of removal of suspended impurities. It is effected by allowing some retention time for the water sample in a storage tank, when the suspended impurities settle at the bottom under the influence of gravity. The clear supernatant water can be drawn from the tank using pumps. This process is called plain sedimentation and it removes almost 70-75% of the suspended matter with a retention time of 2-6 hours. Plain sedimentation is a spontaneous process; sedimentation characteristics can also be improved by coagulation. By sedimentation aided by coagulation, colloidal impurities in the water sample are removed. The method involves the addition of coagulants such as alums (potash or ferric alum), sodium aluminate,

ferrous sulphate to the water sample. The role of coagulant is the formation of gelatinous iron / aluminium hydroxide precipitates called flocs, which entrap the finer impurity particles, enhance the sedimentation and enable their removal. The phenomenon is called flocculation. The flocs are formed by the hydrolysis of the coagulant material. Alum salts possess the advantage that a proper combination of aluminium sulphate and sodium aluminate can be used for any pH of the water sample. Al2(SO4)3 + 6 H2O 2 Al(OH)3+ 3 H2SO4 ; NaAlO2 + 2 H2O NaOH + Al(OH)3 Filtration removes (bacteria and other) microorganisms, taste and colour; renders the water sample sparkling clear. In the filtration process, water sample is passed through beds of fine sand, coarse sand and large granular material such as gravel. Water sample is allowed to percolate through the filter beds. This type of filtering arrangement is called slow sand filter as it possesses low filtering rates (volume of water filtered per unit area of filter bed and unit time - lit/m 2/hr) and uses sand as filtering medium. Rapid sand filters and pressure filters are also in use. Filtration can take place either under gravity or be forced with pressure.

Fine sand

Coarse sand Gravels Filtered water Disinfection is the removal of pathogenic (disease causing) organisms from the water sample. It is carefully distinguished from the sterilization process, which is the ultimate removal (killing) of any microorganism, irrespective of whether it is pathogenic or not. E.g. hospital campus is disinfected whereas surgical instruments are sterilized. The methods available for disinfection are (i) boiling (ii) addition of bleaching powder (iii) chlorination (iv) ultraviolet (UV) irradiation and (v) ozone treatment. Boiling the water sample for 10-15 minutes removes the pathogenic bacteria by killing them and renders water safe for use. Chlorination: Chlorine can be used directly as a gas or in concentrated solution form. On passing chlorine to water sample, hydrochloric acid (HCl) and hypochlorous acid (HOCl) are produced. HOCl is a good germicide. HOCl is also supposed to inactivate the enzymes responsible for metabolic activity of bacteria. Cl2 + H2O HCl + HOCl

HOCl HCl + [O] (or) H+ + OClBacteria + HOCl killing of bacteria Chlorine is widely used as a disinfectant and decolorizer for water. It is a chiefly available powerful oxidizing agent. The amount of chlorine has to be maintained at an optimal level because insufficient chlorine affects disinfection whereas excess Cl2 renders water not suitable for drinking and injurious for human metabolism. The concept of break point chlorination is important in this context. Break point Chlorination: Chlorine is generally applied as Cl2 / NH3 mixture. The applied chlorine dosage is first utilized for the formation of compounds called chloramines (chlorine derivatives of ammonia). Chloramines act as chlorine sources and used for killing micro-organisms such as bacteria and also for the oxidation of organic substances present in the water sample. On completion of all these processes, the excess chlorine appears as free chlorine, which causes unpleasant odour in water. This critical value of chlorine dose is called break point chlorination. The amount of chlorine required to effect these processes is termed as chlorine demand. Break point chlorination is a critical value deciding the chlorine demand or free chlorine for the water sample. These salient points are shown in fig. below:

Residual chlorine

Oxidation of Organic sub.& Germicidal action

Formation of Chloramine s

Break point chlorination

Cl2 applied dosage

Disinfection by ozone: Ozone is a very good disinfectant. It is produced by passing silent electric discharge through cold and dry oxygen. 3 O2 silent elec. dch. 2 O3

oxygen

ozone

Ozone is readily absorbed by water. Ozone is unstable and decomposes readily, liberating nascent oxygen. O3 O2 + [ O ] Nascent oxygen is a very powerful oxidizing agent. It kills all the bacteria and also oxidizes the organic matter present in water. raw water inlet ozone inlet disinfected water outlet

contact tank

For disinfection by ozone, ozone is injected into the water when the two come in contact with each other in a sterilizing tank (Fig. below). The disinfected water is removed from the tap. The contact period is about 10-15 minutes with the usual dosage of 2-3 ppm. Disinfection by ozone is very effective in terms of removal of colour, odour and taste from the water sample without the formation of any residue and harmless but the process is expensive. Disinfection by UV light: Ultraviolet light (invisible with wavelength range 100-400nm) is obtained by passing electric current through mercury vapour lamp, enclosed in quartz tube. UV light is known for its effective bactericidal action but renders the water sample tasteless and odourless. For this reason, swimming pools are disinfected by ozone treatment. The limitation with disinfection by UV light is that this process is expensive and requires technical skill. Boiler feed water: Boilers use water for steam production. Any water sample cannot be used in boilers, as the impurities present in water sample may affect the performance of the boiler. Water with proper specifications, used as a feed for boiler (for steam production) is termed as boiler feed water. Requisites of boiler feed water: (i) Boiler feed water should be free from suspended solids and dissolved corrosive gases such as CO2, SOx, NOx, halogens, hydrogen halide etc. (ii) hardness should be less than 0.1 ppm (iii) alkalinity (soda and caustic alkalinity values) should be in the range 0.1 1 ppm; less than 0.5 ppm alkalinity is preferable (iii) it should be free from dissolved salts and oily / soapy matter that reduces the surface tension of water.

Disadvantages of using hard water in boiler: The main detrimental effects of using hard water in boilers are (i) formation of scales and sludges (ii) boiler corrosion (iii) caustic embrittlement and (iv) priming and foaming. Formation of scales and sludges is the main disadvantage of using hard water in boiler. When the water sample is heated to temperatures exceeding 100oC for steam production, the dissolved salts such as the hardness causing ones are deposited on the boiler vessel. Initially they are deposited as loose, spongy masses called sludges but with time, they are deposited as tight, adherent, not easily removable, insulating undesirable masses called scales. Sludge in boiler (cross sectional views) scale in boiler are represented in fig. below: Water ----------Boiler wall scale The scale formation in boilers, in turn, poses a variety of problems, such as wastage of fuel, overheating of the boiler leading to explosion etc., which will be discussed in due course. These scales and sludges in turn pose various problems as detailed below: 1. Wastage of fuel: Scales are poor conductors (almost insulators) of heat and result in a low heat transfer rates. To main steady heat supply to water, greater heat energy has to be supplied. This results in over-heating of the boiler and also increased fuel consumption. The extent of fuel wastage depends on the thickness and nature of the scale, as evidenced from the following table: Scale thickness (mm) Fuel wastage (%) 0.325 10 0.625 15 1.5 50 2.5 80 12 150 ------------------

2. Decrease in efficiency: Scales, if deposited in the boiler components such as valves, condensers etc., choke in fluid paths and hence lead to decreased efficiency of the boiler. 3. Lowering of boiler safety: Scale formation demands over-heating of the boiler for maintaining a constant supply of steam. Boiler plates, initially maintained at a temperature of 180oC in the absence of scales has to be heated to a temperature of 370oC to maintain the steam supply, if covered with 12 mm thick scale. The overheating of the boiler tubes renders the boiler material softer and weaker and hence the boiler becomes unsafe at high steam pressures.

4. Danger of explosion: when scales undergo cracking due to uneven expansion, water comes in contact with overheated boilerplates suddenly. This results in sudden formation of large amount of steam and hence the development of high pressure of steam, which may cause the boiler explosion. II: Boiler corrosion: It is a serious problem experienced in boiler operation, if proper water sample is not used in boilers. Boiler corrosion is the deterioration / decay / loss of boiler material by the chemical or electrochemical attack by its environment. Boiler corrosion is due to the presence of dissolved corrosive gases such as oxygen, carbon dioxide or corrosive acids formed from the dissolved salts. Dissolved Oxygen (DO) is the main corrosion causing impurity in water. The normal DO content of water is 8 ml / lit at room temperature. The DO attacks the boiler at the prevailing high temperature, forming metal oxide as the corrosion product. 2 Fe + 2 H2O + O2 2 Fe(OH)2 ; 4 Fe(OH)2 + O2 2 Fe2O3. 2 H2O (Rust)

Thus the elemental (metallic) content of the boiler material is lost in the form of metallic compounds. Boiler corrosion due to the DO can be controlled by the removal of the DO content of water i.e. by using substances such as sodium sulphite, sodium sulphide, hydrazine etc. these substances react with DO, as mentioned below and reduce its level in water. 2 Na2SO3 + O2 2 Na2SO4 N2H4 + (hydrazine) O2 N2 + H2O

Na2S + 2 O2 Na2SO4 Hydrazine is preferable among these three substances, as its oxidation products are harmless (sulphite or sulphide is oxidized to sulphate, which may decompose to corrosive SO2 in high pressure boilers). The DO content of water used in boilers can also be removed by mechanical de-aeration the process of spraying water in a tower fitted with perforated plates, which is heated from sides and connected to a vacuum pump. High temperature, low pressure and low surface area provided by the perforated plates reduce the DO content of water. Dissolved CO 2 in water is carbonic acid, which has a slow corrosive effect on the boiler material. CO2 may also be released inside the boiler if the boiler feed water contains bicarbonates. Mg(HCO3)2 MgCO3 + H2O + CO2

Dissolved CO2 in boiler feed water can be removed by mechanical de-aeration or by the addition of ammonia (reaction below).

2 NH4OH + CO2 (NH4)2CO3 + H2O If the boiler feed water contains dissolved magnesium salts, they liberate acids on hydrolysis. The liberated acid reacts with iron content of the boiler in a chain process. MgCl2 + 2 H2O Mg(OH)2 + 2 HCl The liberated acid causes boiler corrosion to a larger extent. Fe + 2 HCl FeCl2 + H2 ; FeCl2 + 2 H2O Fe(OH)2 + 2 HCl Boiler corrosion by acids can be avoided by the introduced alkalinity to water before supply to boiler. III: Caustic embrittlement: This is also a type of boiler corrosion experienced if highly alkaline water is used as boiler feed. Caustic embrittlement is generally experienced in high-pressure boilers, using carbonate conditioning in internal treatment. In high pressure boilers, Na2CO3 decomposes to give sodium hydroxide and carbon dioxide. Na2CO3 + H2O 2 NaOH + CO2 The formed caustic soda (NaOH) renders the water sample alkaline; the water containing NaOH flows into the minute hair-cracks (generally present in the inner parts of the boiler) by capillary action. Here, water evaporates and the concentration of the dissolved caustic soda increases progressively. This caustic soda attacks / dissolves the surrounding areas / iron content of the boiler, forming sodium ferroate. This causes embrittlement of the boiler parts (particularly the stressed parts like bends, joints, rivets etc.) causing even the failure of the boiler. Caustic cracking generally proceeds by a concentration cell mechanism, as represented below: Iron at Stressed ( + ) Parts Concentrated NaOH solution Dilute NaOH solution Iron at (-) plane surfaces

The iron atoms surrounded by dilute NaOH become cathodic whereas the iron atoms in contact wit concentrated NaOH become anodic. The parts becoming anodic are more readily corroded or dissolved. Caustic embrittlement can be prevented by using phosphate conditioning instead of carbonate conditioning for internal treatment or by using tannin or sodium sulphate which may choke / block the hair-cracks or by keeping the pH of the boiler feed water carefully in the range 8-9. IV & V: Priming and foaming: Priming is the phenomenon of wet steam formation i.e. carrying water particles along with steam. The causes of priming are higher dissolved salt content, high steam velocities, sudden boiling / high steam production rate, improper

boiler design. Foaming is the formation of persistent foam or bubbles (which do not break easily) in boilers. The foaming is due to the presence of oily substances, which tend to reduce the surface tension of water. The phenomenon of priming and foaming (the two processes generally occur together) is undesirable as it (i) reduces the boiler efficiency by the deposition of dissolved matter on super-heater / turbine blades (ii) lowers the life of the machinery due to the entry of dissolved matter to other parts of the machinery and (iii) makes boilermaintenance difficult as the height of the water column is to be decided properly. Priming can be avoided by (i) using mechanical steam purifiers (ii) avoiding sudden changes in steaming rates (iii) maintaining low water levels in boilers and (iv) effective softening and filtration for boiler feed water. Foaming can be avoided by the use of anti-foaming agents such as castor oil or by the removal of oily matter from the water sample by the addition of compounds such as sodium aluminate. (The function of this type of compounds is discussed under domestic water treatment sedimentation improved by coagulation). The process of removal of harness of water is termed as conditioning or softening or treatment of water sample. Conditioning of water is of two types namely internal conditioning and external conditioning methods. Internal conditioning: Three important types of internal conditioning methods in use are phosphate conditioning, calgon conditioning and carbonate conditioning. Phosphate and carbonate conditioning methods work on the principle of precipitation of hardness causing cations whereas in calgon conditioning, hardness-causing cations are prevented from their action even in the soluble state. Phosphate Conditioning: In high-pressure boilers, scale formation can be avoided by the addition of sodium phosphate to the water sample. Here, calcium (and also magnesium) ions (responsible for hardness) are precipitated as their phosphates (sludges) and can be removed easily by filtration. Three types of phosphates mono, di and trisodium phosphates are employed in phosphate conditioning. The advantages of phosphate conditioning over carbonate conditioning are (i) it can be applied to high-pressure boilers and (ii) it can be used for softening / conditioning acidic, neutral or alkaline water sample. Ca2+ + 2 Na3PO4 Ca3(PO4)2 If acidic water is to be conditioned, trisodium phosphate can be used. For neutral and alkaline water samples disodium phosphate and monosodium phosphate can be used used respectively. Calgon conditioning: It is the process of addition of calgon or sodium hexametaphosphate to boiler feed water. The calcium ions (responsible for scale / sludge

formation) are complexed by calgon to form a soluble complex and hence prevented from their scale forming action. Ca2+ + Na2[Na4(PO3)6] Na2[Ca2(PO3)6] + 2 Na+ This phenomenon of complexing of the ions is called sequestration. Calgon is the sequestering agent used. Carbonate conditioning: Formation of scales and sludges is avoided by the addition of sodium carbonate to the water sample. Here, calcium (and also magnesium) ions (responsible for hardness) are precipitated as calcium carbonate, that can be removed easily by filtration. Ca2+ + Na2CO3 CaCO3 + 2 Na+ Carbonate conditioning can be very well adopted for low-pressure boilers. But in high (hydrostatic) pressure boilers, since water is available in large excess, sodium carbonate is easily hydrolyzed to sodium hydroxide. The formation of caustic soda (NaOH) causes boiler corrosion. Also, caustic soda formation is not uniform over the entire sirface of the boiler metal exposed. There is a differential concentration of caustic soda on various parts of the boiler metal surface. The boiler metal / alloy atoms exposed to concentrated NaOH solution are more readily corroded than those exposed to dilute NaOH solution. Thus, (corrosion of boiler metal / alloy by) caustic soda renders the boiler metal / alloy brittle and this phenomenon of rendering the boiler metal / ally brittle by the caustic soda formed is called caustic embrittlement. So, the limitation with carbonate conditioning is that it cannot be adopted for high-pressure boilers as it may cause boiler corrosion and / or caustic embrittlement.. External conditioning is the process of removal of harness of water before supply to the boiler as feed for steam production. Internal conditioning is the process of removal of harness of water when it is inside the boiler. Boiler feed water is obtained after subjecting the water sample to external conditioning. Since any process is not 100% efficient (second law of thermodynamics), external conditioning leaves the water sample with very little hardness. The hardness of water sample after external conditioning is called residual hardness. The purpose of internal conditioning is to remove the residual hardness and also avoid the formation of scales and sludges. Three types of external conditioning methods in use are (i) Lime-soda process (ii) Permutit or zeolite process and (iii) Demineralization process. The first process is based the precipitation of hardness causing ions by the addition of soda (Na2CO3) and lime (Ca(OH)2) whereas the second and third process is based on some ion exchage mechanism (ion exchange process). In ion exchange process, troublesome ions are exchanged by resins called ion exchange resins (IER). IE resins are insoluble, crosslinked long chain organic polymers with micro-porous structure. The functional groups attached to the polymeric chain have the tendency to exchange the (hardness causing) ions. Acidic functional groups such as carboxyl (-COOH), sulphonic acid (-SO3H) have

the capacity to exchange cations whereas basic functional groups such as amines (-NH2), hydroxyl (-OH) have the capacity to exchange anions. Ion exchange resins are generally synthesized such as styrene-divinyl benzene copolymers; some of them are also naturally available as different clays having silica composition (that is why clay / sand is used as natural filtering medium / bed). Demineralization Process: It is the process of removal of any mineral (cation or anion) from the water sample. Water sample is first passed through a column called cation exchanger, which is packed with cation exchange resins. This causes the removal of cations by ion exchange process, but renders the water sample acidic, explained as follows: The cation exchange resins are synthesized by the carboxylation or sulphonation of styrene-divinyl benzene copolymers. The structure of these resins is given below:

H H2C=C

H C=CH2

H H2C=C-C6H5 (styrene)

(para divinyl benzene) The copolymer has the structure of alternate styrene and divinyl benzene units with the aromatic rings bearing the substituents of acidic / basic functional groups such as sulphonic acid, carboxylic acid, (substituted) amines etc. Cation exchange resin is generally represented as RH+ ; the ion exchange process is represented as 2 RH+ + Ca2+ R2Ca + 2 H+ ; 2 RH+ + Mg2+ R2Mg + 2 H+ The exchange of any metallic cation (Mn+) can be written as n RH+ + M2+ RnM + n H+ The acidic water water coming out of the cation exchanger is then fed to a column called anion exchanger, which is packed with anion exchange resins. This causes the removal of anions by ion exchange process and also neutralizes the acidity of the water sample, explained as follows. The anion exchange resins are synthesized by the hydroxylation or amination of styrene-divinyl benzene copolymers. Anion exchange resin is generally represented as ROH- ; the ion exchange process is represented as 2 ROH- + SO42- R2SO4 + 2 OH- ; 2 ROH- + CO32- R2CO3 + 2 OH- ; ROH- + X- RX + OHThe ultimate reaction taking place on passing the water sample through the cation and anion exchanger systems is

H+ + OH- H2O The sketch of a typical de-ionizer is in fig.

Water to be Acid demineralized

Cation exhanger

Anion exchanger

Demineralized water

De-ionizer Thus all the ions are removed from the water sample and it is called de-ionized water. Demineralization is a softening process but not the reverse (?). Desalination: Water sample is of three types namely fresh water, brackish water and seawater depending upon the total dissolved salt (TDS) content. Water type Fresh water Brackish water Sea water TDS content (g / l) 1-10 10-35 35

A water sample is said to be saline if it has much of dissolved salt content. Desalination is the process of removal of salinity dissolved content from a water sample. Four methods of desalination are distillation, freezing, reverse osmosis and electrodialysis. Somewhat economical method of these four methods is Reverse Osomosis (RO). Reverse Osomosis (RO): Principle: Osmosis can be defined as the phenomenon of spontaneous flow of solvent molecules from dilute solution side to concentrated solution side, when they are separated by a semi-permeable membrane. The driving force for the osmosis phenomenon is the hydrostatic pressure called osmotic pressure. Osmotic pressure is a

critical value. If the hydrostatic pressure (of the solution) is less than the osmotic pressure, osmosis takes place spontaneously. On the other hand, if a hydrostatic pressure in excess of osmotic pressure is applied on the concentrated solution side, the direction of solvent flow can be reversed and the process is called reverse osmosis. This is the principle of Reverse Osomosis (RO). The dilute solution can be re replaced by fresh water to get fresh water effectively. Thus in Reverse Osomosis (RO), the solvent / water is separated from the contaminants (solution). The schematic of reverse osmosis process is mentioned below: Semi-permeable membrane ---------------------------Dilute solution ------------------- - - - - - - - - -Osmosis ------------------Concentrated solution - - - - - - - - - -Reverse - - - - - - - - - - Osmosis

----------------------Sea water--------------------------------------------------------------Pure water-------------------------------RO Process Problems for practice: 1. 100 ml of a water sample on titration against N/50 HCl required 8.0 ml of acid for phenolphthalein end point and another 5.0 ml of the acid for methyl orange end point. Calculate the hydroxyl and carbonate alkalinities in terms of CaCO3 equivalent. (30, 100 ppm) 2. 100 ml of a water sample on titration against N/20 acid required 12.3 ml of acid for phenolphthalein end point. The same sample required 18.6 ml of the acid for methyl orange end point. Calculate the alkalinities in terms of CaCO3 equivalent. (150, 315 ppm) 3. 100 ml of a water sample required 20 ml of N/40 H2SO4 for complete neutralization. Calculate the temporary hardness. (250 ppm) 4. 0.5 g of CaCO3 was dissolved in dil. HCl and diluted to 500 ml. 50 ml of this solution required 48.0 ml of EDTA solution for titration. 50 ml of a hard water sample required 15 ml of EDTA solution for titration. 50 ml of same water sample on boiling and filtration required 10 ml EDTA for titration. Calculate the hardness. (Total=312.5; Permanent = 208.3 ; Temporary = 104.2)

5. 50 ml of a standard hard water containing 1 mg of pure CaCO3 per ml consumed 20 ml of EDTA. 50 ml of a water sample consumed 25 ml of same EDTA solution using EBT indicator. Calculate the total hardness (1250 ppm) 6. Calculate the hardness of a water sample whose 10 ml required 20 ml of EDTA. 20 ml of calcium chloride solution , whose strength is equivalent to 1.5 g CaCO3 per litre, required 30 ml of EDTA solution. (200 ppm) Question Bank Part A 1. Define alkalinity / hardness. 2. What are the sources for alkalinity / hardness in water sample? 3. What are the types of alkalinity / hardness in water sample? 4. What is meant by boiler feed water? State its requirements. 5. What are the disadvantages of using hard water in boiler? 6. What are meant by scales and sludges? 7. Differentiate between scale and sludge. 8. What is meant by conditioning of water? 9. What are the types of water conditioning methods? 10. Why is phosphate conditioning preferable to carbonate conditioning? 11. What is calgon conditioning? How is it preferred to carbonate conditioning? 12. Outline the steps in domestic water treatment. 13. Define desalination. 14. What is reverse osmosis? 15. What is disinfection? 16. Outline the methods of desalination. 1. 2. 3. 4. 5. 6. 7. 8. Part B Explain the determination of hardness by EDTA method. Explain the process of domestic water treatment. Explain in detail the disadvantages of using hard water in boilers. Explain in detail, the internal conditioning methods. Explain the disinfection methods by chlorine, ozone and UV treatment. Explain in detail the demineralization process. Explain with sketch, the R.O. process of desalination. Explain the determination of alkalinity.

Addition of bleaching powder is adopted for smaller storage tanks. On addition bleaching powder (CaOCl2) to water, chlorine and hence hypochlorous acid (HOCl) are produced, HOCl is a good germicide. HOCl is also supposed to inactivate the enzymes responsible for metabolic activity of bacteria. CaOCl2 + H2O Ca(OH)2 + Cl2 ; Cl2 + H2O HCl + HOCl HOCl HCl + [O] (or) H+ + OCl-

Nascent oxygen and hypochlorite anion also possess germicidal activity. Use of bleaching powder is convenient on smaller storage tanks. In case of high chlorine requirement, chlorine gas can be directly passed into the water sample (direct chlorination) but at optimum levels neither to cause objectionable odour nor causing incomplete disinfection.