CHAPTER-| WATER QUALITY AND TREATMENT INTRODUCTION Water is nature's most wonderful, abundant and useful compound. Water is essential for the lives of animals and plants. Italso occupies a unique position in industries. Itis used as coolant in power and chemical plants. Itis used for steam generation in power plants. It is widely used in ice making, drinking, bathing, sanitary, washing, irrigation, fire-fighting, air-conditioning and also production of industrial materials. IMPURITIES IN WATER: ‘The natural water is usually contaminated by different types of impurities. They are mainly 3 types. 1. Physical impurities 2. Chemical impurities 3. Biological impurities 1. Physical Impurities: a. Suspended impurities: Sand, oll drops, vegetable and animal matter. They impart turbidity to water b. Colloidal impurities: Finely divided silica, clay, oil droplets and organic waste products. They impart turbidity, colour, odour and taste to water 2. Chemical Impurities: 2, Dissolved salts: Bicarbonates, chlorides, sulfates of Ca and Mg and carbonates of Na and K. They impart salty taste to water. b, Dissolved gases: COs, O2, HaS, S02 ete. They make water acidic, They accelerate corrosion. 3. Biological Impurities: Biological impurities are pathogenic bacteria, algae, fungi, viruses. They cause various diseases. HARDNESS OF WATER Hardness of water is defined as inability of water to produce lather (foam) with soap. This is due to presence of certain salts of Ca, Mg and other heavy metals dissolved in it. [Soaps are sodium or potassium salts of higher fatty acids like oleic acid or palmitic acid or stearic acids. e.g CapHssCOONa] 2C\7HssCOONA + CaCl, ——— (CyrHsC00),Ca + 2NaCl 2C\rHssCOONA + MgSO+ (CirHasCOO}.Mg + Na:SOx Hardness of water is mainly two types: 1. Temporary Hardness, 2. Permanent Hardness 1. Temporary Hardness: Itis also known as carbonate hardness Itis mainly caused by the presence of dissolved bicarbonates of calcium, magnesium and other heavy metals and the carbonate of iron. Temporary hardness of water mainly due to Ca(HCOs}2 and Mg(HCOs)2 When bicarbonates are decomposed, they give insoluble carbonates or hydroxides. Temporary Hardness can be removed by mere boiling of water. Heat Ca(HCOs} ——> CaCO + COs P40 Me(HCOsh "> MglOH)»v + 260, 2. Permanent harness: tis also known as non-carbonate Hardness. It is due to the presence of dissolved chlorides and sulphates of calcium, magnes metals. Permanent Hardness cannot be removed by boiling butt can be removed by the use of chemical agents im, iron and other heavy UNITS OF HARDNESS. Parts per million (ppm): It is the parts of CaCO: equivalent hardness per10® parts of water.i partothardness 10° parts of water itis the number of milligrams of CaCO. equivalent hardness present per litre of ppm = Milligram per litre (mg/I water. Imgf« agains Kg of water ,000 g of water = 1,000 x 1,000 mg of water = 10° mg of water mg/L 10° mg of water_ 1 ppm Clark’s degree (°Cl): It is the parts of CaCO: equivalent hardness per 70,000 parts of water ~~ 70,000 parts of water 1 Lof water 11°C 1 ppm Degree French (*Fr): Its the parts of CaCO; equivalent hardness per 10° parts of water ‘ofr = Lbartot hardness {oF parts of water partof hardness x 10 {oF parts of water x10 1 partofhardness x10, 10° parts of water 10 ppm Ippm =0.1°Fr Milliequivalent per litre (meq/t): It is the number of milliequivalents of CaCO; equivalent hardness present per litre. Ameg/t meq of CaCO: per Lof water 10° x 50 g of CaCO, eq per L of water 10 mg of CaCO: eq per L of water 0 mg/L of CaCOs eq = SO ppm. .02 meq/L. 1 ppm = 1 mg/L = 0.1 °Fr = 0.07 °Cl= 0.02 meq/L. ppm DISADVANTAGES OF HARDWATER: 1. In Domestic use: 2. Washing: hard water, when used for washing purposes, does not producing lather freely with soap. As 2 result cleansing quality of soap is decreased and a lot of soap is wasted. Hard water reacts with soap it produces sticky precipitates of calcium and magnesium soaps. These sticky precipitates adhere to the fabric/cloth giving spots and streaks. Presence of iron salts may cause staining of cloth. b. Bathing: hard water does not lather freely with soap solution, but produces sticky scum on the bath-tub and body. Thus, the cleansing quality of soap is depressed and a lot of soap is wasted. . Cooking: the boiling point of water is increased because of presence of salts. Hence more fuel and time are required for cooking. Salts are deposited on the inner walls of utensils. Tea/Coffee prepared from hard water has an unpleasant taste and muddy looking extract. d. Drinking: hard water causes bad effects on our digestive system. Moreover, the possibility of forming calcium oxalate crystals in urinary tracks increases. 2. In industrial use: a. Textile Industry: Hard water causes wastage of soap. Precipitates of calcium and magnesium soaps adhere to the fabrics and do not produce exact shades of colour. Fe and Mn salts may cause coloured spots on fabrics. b. Sugar Industry: water containing sulphates, nitrates, alkali carbonates ete. if used in sugar refining, causes difficulties in the crystallization of sugar. Moreover, the sugar so produced may be deliquescent. . Dyeing Industry: The dissolved salts in hard water may reacts with costly dyes forming undesirable precipitates which give impure shades and spots on fabric being dyed.d. Paper Industry: Calcium, magnesium, Iron salts in water may affect the quality of paper. e. Pharmaceutical Industry: Hard water may cause some undesirable products while preparation of pharmaceutical products. f. Concrete Making: Water containing chlorides and sulphates, if used for concrete making, affects the hydration of cement and the final strength of the hardened concrete. g. Laundry: Hard water, if used in laundry, causes much of the soap used in washing to go as waste Iron salts may even cause coloration of the clothes. 3. In steam generation in boilers: For steam generation, boilers are almost invariably employed. If the hard water is used in boilers, it causes ‘many troubles such as a, Scale and sludge formation, b. Corrosion, c. Priming and Foaming, d. Caustic embrittlement ESTIMATION OF HARDNESS BY EDTA METHOD: The anah done by complexometric titration using standard EDTA and EBT as ai EDTA is Ethylene diamine tetra acetic acid whose structural formula is HOOCH,C, (CHyCOOH HOOCH,C’ “Sesegaceae EDTA is insoluble water. Its disodium salt is soluble in water. Naoc,c, CH,COOH NH He ween HoocH,C’ \CH,COONa EDTA forms complexes with M’* Where M = Ca or Mg o Bw A) oocH,c~ H,;c———CH, cH,coo M-EDTA Complex is 1:1 complex. Itis soluble in water, Itis colourless, Itis stable. Principle: In this complexometric titration, the water sample is titrated with standard solution of di sodium salt of EDTA using EBT indicator. ‘The amount of EDTA consumed in the titration gives amount of hardness present in water. EBT indicator when added to hard water, it forms unstable wine-red M-EBT complex. The indicator is effective at pH of about 10. M+ EBT = ———»_[M~EBT] complex blue wine-red During titration with EDTA solution, EDTA combines with MP* (M = Ca or Mg), gives stable M-EDTA complex releasing the free indicator (blue). The colour changes from wine-red to blue at the endpoint. IM-eeT] + EDTA ————» [M-ETDA] + EBT Wine-red blueSolutions required: 1, Standard hard water: dissolve 1g of pure, dry CaCO; in minimum quantity of dil, HCI and then evaporate the solution to dryness. Dissolve the residue in distilled water to make 1 Litre solution. Each mL of this solution thus contains 1mg of CaCO3 equivalent hardness, 1 mLhard water solution = img of CaCO3 equalent hardness. 2. EDTA solution: Dissolve 4 g of pure EDTA crystals in 1 Litre of distilled water. 3. Indicator (EBT): Dissolve 0.5 g of Eriochrome Black-T in 100ml alcohol. 4 Buffer solution: add 67.58 of NHACI to 570 ml of Con. ammonia solution and then dilute with distilled water to 1 Litre, PROCEDURI Standardization of EDTA solution: Rinse and fill the burette with EDTA solution. Pipette out $0 mL of standard hard water in a conical flask. ‘Add 10-15 ml of buffer solution and 4 to 5 drops indicator. Titrate with EDTA solution tll wine-red colour changes to blue. Let volume used be V: ml. Estimation of Total hardness: Pipette out 50 mL of sample hard water in a conical flask, ‘Add 10-15 mL of buffer solution and 4 to 5 drops indicator. Titrate with EDTA solution till wine-red colour changes to blue. Let volume used be V2 ml. Estimation of Permanent hardness: Take 250 ml of the water sample in a large beaker. Bolt till the volume is reduced to about SO ml, filter it, wash the precipitate with distilled water, collecting filtrate and washing in a 250 ml. measuring flask. Finally make up the volume to 250 mL. with distilled water. Pipette out 50 ml of boiled water sample in a conical flask. ‘Add 10-15 mL of buffer solution and 4 to 5 drops indicator. Titrate with EDTA solution tll wine-red colour changes to blue. Let volume used be Vs ml. CALCULATIONS: Vi mL of EDTA is consumed by 50 mL standard hardwater. 50 mL of standard hard water VimLof EDTA 50 X 1mg of CaCOs = VamLof EDTA 1 mLof EDTA 50/V; mg of CaCOs eq Now 50 ml of sample hard water Va mLof EDTA Vx 50/Vs mg of CaCO: eq, 1(1000 mt) of sample hard water 1000 x Vi/Vs mg of CaCO; eg. Total hardness of water 1000 x V2/Vi mg/L 1000 x V2/V: ppm (Since 1 mg/| Now 50 ml of boiled water Vs mL of EDTA ‘Vax 50/Vs mg of CaCOs eq, 1000 mt of boiled water 1000 x Vs/Vi mg of CaCOs ea. = 1000xVs/Vi ppm Permanent hardness 1000 x Vs/Vi ppm Temporary hardness = Total hardness ~ Permanent hardness [1000 x Vo/Vs}- [1000 x Vs/Vi} . 1000[(V2-V3 /V;] ppm ‘Advantages of EDTA method: ‘This method is definitely preferable to the other methods, because of the 1. Greater accuracy 2. Convenience and 3. More rapid procedureDISSOLVED OXYGEN: Dissolved oxygen is estimated by Winkler’s method. It involves iodometric titration, Principle: Estimation of dissolved Oxygen in water is based on the oxidation of KI by dissolved Oxygen in to lodine. Liberated lodine is titrated with standard sodium thiosulphate solution using starch as indicator. The dissolved molecular Oxygen in water does not react with KI. So, an oxygen carrier is used to bring about the reaction between Oxygen and K Hence manganese hydroxide is produced as a result of the reaction of KOH and MnSOx. 2NaQH + MnSO, ———> Mn(OH) + Na:SOx 2Mn(OH)2 + O2 2MnO(OH). MnO(OH), + HS, ———> MnO, + 2H,0 + [0] 2KI + H2S0. + [0] K:SOx + H20 + I> 2Na,S,0, +l ———— 2Nal + Na,S,0. ‘Note: The presence of sulphites, nitrites, etc. in water gives wrong results. ‘These ions also liberate lodine from Kl In order to prevent the liberation of lodine from nitrite (If present in water), sodium azide (NaN) is added. ‘This reacts with nitrites. 2NaNs + H2SO; > 2HNs + NaSOx HNO; + HNs ———* NO + No + H20 Solutions Required: .MnSQ< Solution; It is prepared by dissolving 400g of MnSOx per L 2. Alkaline Azide lodide Solution: It is prepared by dissolving 150g KI + 500g NaOH + 20g NaN per L Procedure: Take 250 mL of water in bottle preventing it to contact with air. Add 2 mL of Manganous sulphate solution and also add 2 mL of alkaline azide iodine solution. Shake the bottle thoroughly, and repeat the process thrice. Allow the precipitate to settle half-way and mix again. ‘Then add conc, HsSOs'o dissolve precipitate and shake the bottle again. Allow the yellow solution to stand for 5 min. Withdraw 100 mL of solution and titrate it against N/100 solution (Na2S:0, solution) using freshiy prepared starch as indicator. The endpoint will be the disappearance of blue colour. When the volume of thiosuiphate Js V ml then dissolved oxygen content in water is 0.8 V ppm. Calculation: Let volume of N/100 Na,S:0; solution used 100x Normality of sample water Normality of sample water Strength of 0.0 in water vmt Vx IN/100] Vx IN/100)/100 1v/10000] x Eq [v/10000) x8 g/t v/10000) x 8 x 1000 mg/L 0.8 x ppm. lent weight of oxygen g/L ALKALINITY OF WATER: Alkalinity is a measure of ability of water to neutralize acids. It can be estimated by titration against standard acid ‘The alkalinity of water is attributed to the presence of the 1, Caustic alkalinity (due to hydroxide & carbonate ions) 2. Temporary hardness (due to Bicarbonate ions) The possible combinations in water are i. OW only li, CO} only ii, HCOr only iv, OH" and CO” together vv. COs* and HCOs together ‘The possibility of OH" and HCOs' ions is ruled out. Because they combine to form CO;*OH" + HCO; ————> C0;* +H,0 ‘On the basis of same reasoning, all the three (OH, HCOs, and COs”) cannot exist together. Alkalinity of water can be determined by titration against standard acid like N/SO H,SO, using first phenolphthalein and later methyl orange as indicators. The estimation is based on the following reactions (a). O# +" ——+ 20 iE (b). CO; +H” ——+HCO; [M (HCO +4" ——* H,c0s ‘The volume of the acid used up to phenolphthalein end point corresponds to the reactions (a) and (b) ie. complete neutralization of OH" ions and neutralization of COs” ions upto HCOs stage (half neutralization of CO;* ions) The volume of the acid used up to methyl orange end point corresponds to the reactions (a), (b) and (Jie. complete neutralization of OH’, CO;#and HCO; ions. Procedure: Rinse and fill the burette with N/50 H,S0, solution Pipette out 100 mL of the sample water in a clean titration flask. Ada to it2 to 3 drops of phenolphthalein indicator. Run in N/SO H.SO. from burette till the pink colour is just discharged, Add 2-3 drops of methy! orange indicator. Continue the titration against N/SO H,SOs solution till the pink colour reappears. Calculation Let volume of acid used to phenolphthalein endpoint = Vi mL Extra volume of acid used to methyl orange endpoint = Vz mL Phenolphthalein alkalinity: ‘Volume of N/SO H»SOx solution used Vimt 100.x Normality of sample water = Vax {N/50] Normality of sample water Vs x {N/S0]/100 Strength of alkalinity in terms of CaCOs {V:/5000] x 50 g/L. [4/100] x 1000 mg/L. = 10xVi ppm Phenolphthalein alkalinity Methyl orange alkalinity: Volume of N/50 H,SOs solution used [Mi Vel mt 100 x Normality of sample water IM # Val x IN/S0] Normality of sample water IMs + Val x [N/50]/100 Strength of alkalinity in terms of CaCO, [(Vs-+¥2}/5000} x 50 g/L {(Vs-+ V2}/100} x 1000 mg/L 10x (Vs + Valppm. 10.V: ppm Methyl orange alkalinity M = 10(V:+Va) ppm ACIDITY OF WATER. Acidity is a measure of ability of water to neutralize bases, It can be estimated by titration against standard base. Estimation of acidity is important because acidic water causes corrosion. Water may contain strong acids such as mineral acids and some other weak acids such as CO, Acidity of water can be determined by titration against standard base like N/50 NaOH using first methyl orange and later phenolphthalein as indicators. Procedure: Rinse and fill the burette with N/SO NaOH solution Pipette out 100 ml of the sample water in a clean titration flask. ‘Add to it2 to 3 drops of methyl orange indicator. Run in N/S0 H,SOx from burette till the colour changes from orange red to yellow. ‘Add 2-3 drops of phenalphthalein indicator.Continue the titration against N/50 NaOH solution tll the colour turns to pink, Calculation Let volume of acid used to methyl orange endpoint = V; mL Extra volume of acid used to phenolphthalein endpoint = V2 mL Mineral acidity: ‘Volume of N/SO NaOH solution used Va mt 100x Normality of sample water Vix 1N/50] Normality of sample water Va x (N/SO]/100 Strength of acidity in terms of CacOs [1/5000] x 50 g/L {[V,/100} x 1000 me/. 10x V; ppm. Mineral 10Vi ppm. Total acidity: Volume of N/SO NaOH solution used [Mi + Val mt. 100x Normality of sample water Normality of sample water Strength of acidity in terms of CaCO, IMs # Val x 1/50] [M1 + Va] x [N/50]/100 (i+ Ve}/5000] x50 g/t (Va + V2}/100] x 1000 mg/L 10x (Va + V2) ppm. Total acidity = 10(V.+V2) ppm ESTIMATION OF CHLORIDES IN WATER The chloride ions are present in water in the form of one or more of the compounds like CaCl, MgCl, NaCl ete. Principle: The estimation of chloride ions is generally made by titrating the water sample against a standard solution of silver nitrate using potassium chromate as indicator. The added silver nitrate precipitates chloride ions as white precipitate of silver chloride. NaCl + AgNOs ACI + NaNO When all the chiorine ions are removed as AgCl precipitate, the excess drop of silver nitrate reacts with potassium chromate forming silver chromate, which is red in colour. K,Cr0, + 2AgNOs, ‘AgiCrOs + 2KNOs Yellow Red ‘The endpoint is therefore the change in colour from yellow to red colour due to formation of AgiCrO, indicator. Procedu Rinse and fill the burette with N/SO AgNOs solution ‘Take 100 mL sample water into conical flask ‘Add 2:3 drops of potassium chromate indicator ‘Then titrate it against N/50 AgNO, solution til the colour changes from yellow to red. Calculations: Let volume of N/50 AgNO; used vimt 100x Normality of chioridesolution = Vx {N/S0) Normality of chloride solution Vx N/50]/100 Strength of chlorides in water = {V/5000] x 35.5 g/L {v/5000] x 35.5 x 1000 mg/L = 7.AxVppm. BOILER TROUBLE ‘The boiler troubles caused by the use of unsuitable water are 1. Priming and Foaming 2. Scale and sludge formation 3. Boller corrosion 4, Caustic embrittlementPRIMING AND FOAMING Priming: ‘The process of wet steam formation is called priming. When a boiler is producing steam rapidly, some particles of liquid water are carried along with the steam. Priming is Caused by: 1. the presence of large amount of dissolved solids, 2. high steam velocities, 3, sudden increase in steam production rate, 4, sudden boiling, and 5. improper boiler design, Foaming: Foaming is the formation of bubbles (which do not break easily) on the water surface. Foaming is due to the presence of oils (which reduce the surface tension). Priming and Foaming, usually, occur together. Disadvantages: They are objectionable because 1. salts get deposited on turbine blades, and reduces their efficiency. 2. salts decrease the life of the machinery. 3. actual height of water column cannot be judged properly. Priming can be avoided by 1. fitting mechanical steam purifiers, 2. proper boiler design, 3. avoiding rapid change in steam-rate, 4, maintaining low water level and 5. efficient softening and filtration of the boiler feed water. Foaming can be avoided by 1. adding anti-foaming chemicals like castor oil, 2. removing oil from boiler water by adding compounds like sodium aluminate. SCLAE AND SLUDGE FORMATION IN BOILERS: In boilers, because of continuous evaporation of water, the concentration of salts increases progressively. When their concentration reaches saturation point, they form precipitate on the inner walls of boiler. SLUDGE: Sludge is a soft, loose and slimy precipitate formed within the boiler. It is formed at comparatively colder portions of the boiler and collects in the area where flow rate is slow. These are formed by substances which have greater solubilities in hot water than in cold-water. e.g. MgCOs, MgCh, MgSOx, Cachete. Disadvantages: a. The sludges are poor conductor of heat, they cause wastage of heat. b. Sludge gets entrapped in scale and both get deposited as scale. «. Excessive sludge disturbs the working of the boiler by chocking pipes. Prevention: a, By using well softened water. bb. By frequent blow down operation (drawing off a portion of concentrated water). {itgey SCALES: Scales are hard, adhering precipitates formed on the inner walls of the boilers. They stick very firmly on to the inner wall surface and are difficult to remove with chisel and hammer.Causes of scale formation: 1, Decomposition of calcium bicarbonate: CalHHCOs), ————> CaCO; + H,0 + CO, In low pressure boilers, CaCO3 causes scale formation. In High pressure boilers, CaCO3 becomes soluble. ‘CaCOs + #20 ————* Ca(OH)2 + COz 2. Deposition of calcium sulphate: The solubility of CaSO. in water decreases with rise of temperature. In super heated water CaSO« is insoluble. This is the main cause of scale formation in high-pressure boilers. 3. Hydrolysis of Magnesium salts: Dissolved Magnesium salts undergo hydrolysis forming Mg(OH). precipitate. MgCl + 2H20 Mg(OH)2 + 2 HCl ‘Mg(OH}2 formed by hydrolysis of Magnesium salts isa soft scale. 4. Presence of Silica: Silica present in small quantities deposits as silicates like CaSiO; and MgSiOs. These are very difficult to remove. Disadvantages: 41. Wastage of fuel: The scale formation causes decreases of heat transfer. As a result over heating is required, this causes consumption of fuel. 2, Lowering of boiler safety: Over-heating of the boiler makes the boiler material softer and weaker. 3. Decrease in efficiency: Scales may deposit in the valves and condensers and choke them partially. This results in decrease in efficiency of boiler. 4, Danger of Explosion: The hot scale cracks due to uneven expansion and water suddenly comes in contact with overheated tron plates. This causes formation of large amount of steam suddenly. This results in high pressure causing explosion of boiler. Removal of scales: 1. With the help of seraper or piece of wood or wire brush. 2. By giving thermal shocks (Heating the boiler and sudden cooling with cold water) 3. By dissolving them by adding chemicals (Calcium carbonate scales can be dissolved by using 5-10% HCI, Calcium sulfate scale can be dissolved by adding EDTA) 4. By frequent blow-down operation Prevention: 1. External treatment: Efficient softening of water is to be carried out. 2. Internal treatment: Suitable chemicals are added to the boiler water either to precipitate as sludge or to convert the scale into soluble compounds. BOILER CORROSION: Decay of boiler material by a chemical or electrochemical attack by its environment in a boiler is known as boiler corrosion. The main reasons for this problem 1. Dissolved oxygen, 2. Dissolved carbon dioxide and 3. Acids from dissolved salts. 1. Dissolved oxygen: Water usually contains about 8 ml of dissolved oxygen per liter at room temperature. Dissolved oxygen in water, in presence of high temperature, attacks boilermaterial 2Fe + 2H,0+0, ——— 2Fe(OH) ‘4Fe(OH)2 +02 ————> 2 Fe20s.2H20] (rust) Removal of dissolved oxygen: i by adding calculated quantity of sodium sulphite or hydrazine or sodium sulphide, 2Na;S0; + 0; ————™ 2Na,S0. NoHe + 0; ——— Na + 24:0 Na,S + 20; ————* NaSO; Hydrazine is an ideal internal treatment chemical for the removal of dissolved oxygen. It reacts with oxygen, forming nitrogen and water. Nitrogen is harmless. li, by mechanical de-aeration process (water spraying in perforated plated-fitted tower, heated from sides and connected to vacuum pump. High temperature low pressure and large exposed surface removes the dissolved oxygen in water).2. Dissolved carbon dioxide: Carbon dioxide in water produces carbonic acid, which has a slow corrosive effect on the boiler material. (CO, + HO ———* HO Carbon dioxide is also released inside the boiler, if water used for steam generation contains bicarbonates. To vacuum pump ‘Steam jacket Mg(HHCOsj> => MglOH)ay +2C0, Removal of C02: i by adding calculated quantity of ammonia 2NH,OH + CO: ——— (NH4):CO3 + H:0 i by mechanical de-aeration process along with oxygen. 3. Acids from dissolved salts: Water containing dissolved magnesium salts liberates acids on hydrolysis. MCh + 24:0 ————> Mg(O#) + 2HC! The liberated acid reacts with iron in chain-like reactions | producing HCl again and aga a Fe +2HCl ———» FeCin+ Ho a FeCl + 2H,0 ———* Fe(OH)1+ 2H) Mechanical dseration of water Consequently, presence of even a small amount of MgCl: will cause corrosion of iron toa large extent. CAUSTIC EMBRITTLEMENT: It is a type of boiler corrosion, caused by using highly alkaline water. During lime-soda process, some residual Na,COs is usually present in the softened water. This NasCOs decomposes to give NaOH and CO:, and this makes the boiler water “caustic”. Na;COs+ H:0 ————™ 2NaOH + CO; ‘This caustic water flows into minutes hair-cracks, by capillary action. Here water evaporates, the dissolved caustic soda concentration increases. This caustic soda attacks the surrounding area, thereby dissolving Iron of boiler as sodium ferroate. ‘This causes embrittlement of boiler parts such as bends, joints, rivets etc, causing failure of the boiler. Caustic cracking can be explained by considering the following concentration cel! : + Iron at bends, | Conc. Dil tron at joints, rivets | NaOH NaOH — | plane etc, solution | solution | surfaces At anode: Fe + 2NaQH NazFeO2 + Hx“t (Oxidation) Caustic embrittlement can be avoided: 1, by using sodium phosphate as softening reagents (instead of sodium carbonate). 2, by adding Tannin or Lignin to boiler water, since these block the hair-cracks 3. by adding sodium sulfate which blocks the hair-cracks 4, by maintaining the pH value of water and neutralization of alkali. INTERNAL TREATEMENT: Internal treatment of boiler water is carried out by adding proper chemicals 1. to precipitate the scale forming impurities in the form of sludge and 2. to convert the scale forming chemicals into compounds which will stay in dissolved form in water. Some of the internal treatment methods used for the removed of scale formation in boilers are 1. COLLODIAL CONDITIONING: The addition of organic substances such as Kerosene, tannin, agar-agar gel etc., to the surface in low pressure boilers may prevent the scale formation. These substances get coated over the scale forming precipitates and give a loose and non-sticky precipitates which can be removed by low-down operation. 2. CARBONATE CONDITIONING: In low-pressure boilers, scale-formation can be avoided by adding sodium carbonate to boiler water. e.g. CaSO; is converted into calcium carbonate. CaSOx+ NasCOs CaCOad + NaxSOxConsequently, deposition of CaSO, as scale does not take place and calcium is precipitated as loose sludge of CaCOs which can be removed by blow-down operation. 3. PHOSPHATE CONDITIONING: The addition of sodium phosphate to hard water reacts with the hardness causing agents and gives calcium and magnesium phosphates which are soft and non-adherent and can be removed easily by blow-down operation. In this way, scale formation is removed in high pressure boilers. 3CaClz + 2 NaPO, ———— Cas(POs)s + 6NaCl ‘The main phosphates employed are (a). NaHPOs (acidic), it is suitable if alkalinity of boiler water is too high. (6). NasHPO, (weakly alkaline), its suitable if alkalinity of boiler water is sufficient. (c). NasPOs (alkaline), itis suitable if alkalinity of boiler water is low. 4. CALGON CONDITIONING: Involves in addition calgon to boiler water. It prevents the scale and sludge formation by forming soluble complex. Calgon = Sodium hexa Meta phosphate = Na,[Na4(POs)] or (NaPOs)e 2CaS04 + Nas[Nas(POs}e] = Nas{Cax(POn}e] + 2NasSOx 5. TREATMENT WITH SODIUM ALUMINATE: Sodium aluminate gets hydrolyzed and gives NaOH and a gelatinous precipitate of aluminum hydroxide. Thus NaAlO; + 2H,0-———> NaOH + Al (OH) The sodium hydroxide, so-formed, precipitates some of the magnesium as Mg (OH); Le, MgCl, + 2NaoH ———» Mg (OH), J+ 2Nacl The flocculent precipitate of Mg (OH}z and Al (OH), produced inside the boiler, entraps finely suspended and colloidal impurities, including oil drops and silica. The loose precipitate can be removed by blow-down operation. EXTERNAL TREATMENT: ION EXCHANGE PROCESS lon exchange process also known as demineralization or de-ionization process. lon-Exchange resins are insoluble cross linked long chain organic polymers with a micro porous structure, and the functional groups attached to the chains are responsible for the ion-exchanging properties. In De-ionization process all the ions present in water are eliminated by using ion-exchange resins. Basically resins with acidic functional group are capable of exchanging H” ions with other cations. Resins with basic functional groups are capable of exchanging OH ions with other anions. Resins are classified as 1. Cation Exchange Resins 2. Anion Exchange Resins 1. Cation Exchange Resins: These are mainly styrene divinyl benzene co-polymers, which on sulphonation or carboxylation are capable of exchanging their hydrogen ions with cations in water. yt we te tee duutin, 4 dau, OH note He te é . boon boon basin, 4 bakin, On Cation exchange resin Anion exchange resin 2. Anion Exchange Resins: Anion exchange resins vinyl benzene or amineformaldehyde copolymers, which contains quaternary ammonium or quaternary phosphonium or tertiary sulphoniumgroups as an internal parts of the resin matrix. These after treatment with dilute NaOH solution become capable of exchanging their OH ions with anions in water. In fon-exchange process, hard water is passed through cation exchange resins, which remove Ca* and Mg* ions and exchange equivalent amount of H" ions, 2RH* + Ca* ———— R,Ca* + 2H* 2RH" + Mg* ———> R,Mg”" + 2H" (RH* = cation exchange resin) ‘After cation exchange column, the hard water is passed through anion exchange column. Anions exchange resins remove bicarbonates, chlorides and sulphates from water exchange equivalent amount of OH ions. R/OH' + Cr ——— R'C' + OH" 2R'OH + SO," ————™ R,S0,* + 20H 2R'OH + CO;* ————» R’2C0s"" + 20H (ROH = anion exchange resin) H’ and OH ions, thus released in water from respective cation and anion exchange columns, get combined to produce water molecules, H+ 0H ——— 0 ‘The water coming out from the exchanger is fon free (i.e, free from anions and cations). Thus water of zero hardness is obtained. Regeneration: When cation exchanger losses capacity of producing H* ions and exchanger losses capacity of producing OH" ions, they are said to be exhausted. The exhausted cation exchanger is regenerated by passing dilute HC! through it. R,Ca®* + 2H*———> 2H" + Ca R,Mg” + 2H* —————> 2RH* + Mg? ‘The exhausted anion exchanger is regenerated by passing a dilute solution of NaOH. R50," + 20H ————™ 2R'OH" + 50," R’C + OH” ————> R'OH'+ Cr Fig 8. Deminerazation of wat ‘Advantages: 1, The process can be used to soften highly acidic or alkaline water. 2. It produces water of very low hardness (2 ppm). So it is very good for treating water for use in high pressure boilers. Disadvantages: 1. The equipment is costly and more expensive chemicals are needed, 2. If water contains turbidity, the output of the process is reduced. The turbidity must be below 10pm; else it has to be removed by coagulation and filtration, ‘ZEOLITE (PERMUTIT) PROCESS Zeolite is also known as permutit. Zeolite is hydrated sodium alumino silicate. It is represented as Na,0.Al,03.xSiO;.yH2O where x= 2-10, y= 2-6Zeolites are mainly 2 types: 1, Natural zeolites are non-porous, eg. Natrolite- Naz0.Als0s.4SiO>,2H20. 2. Synthetic Zeolites are porous and possess gel structure. Sodium zeolites are generally used for softening of water and are simply represented as Na:Ze, where ‘Ze’ stands for insoluble zeolite, In the process, when hard water is passed through a bed of zeolite placed in a closed cylinder, the hardness causing ions like Ca®* and Mg’ ions are es taken up by the zeolite. Sodium salts are released during the reaction, as byproduct. Process: For softening of water by zeolite process, hard water is percolated at a specified rate through a bed of zeolite, kept in a cylinder. The hardness causing ions like Ca*, Mg” are retained by the zeolite as CaZe and MgZe, while the outgoing water contains sodium salts = | Te various eactions taking place may be : NasZe + Ca(HCOs}2 Caze + 2NaHCOs NazZe + Mg(HCOs)2 Mgze + 2NaHCOs NaoZe + MgCle Mgze + 2Nacl NaxZe + CaCl ——— Caze + 2NaCl Naxze + MgSO: Maze + 2Na:SOs Nazze + MgCl2 Meze + 2NaCl Hence zeolite process removes the hardness of water effectively. Regeneration: After some time, the Zeolite is completely converted into calcium and magnesium zeolites and it ceases to soften water, ie, it gets exhausted. At this stage, the supply of hard water is stopped and the exhausted zeolite is reclaimed by treating the bed with a concentrated Brine solution (10% NaCl). CaZe + 2NaCl ———* NaiZe + CaCle Meze + 2Nacl ——— Nazze + MgC Limitations: 1. Ifthe supply of water is turbid, the suspended matter must be removed, before the water is admitted to the zeolite bed. Otherwise the turbidity will cog the pores of zeolite bed, thereby making it ina 2. if water contains large quantities of coloured ions such as Mn** and Fe" they must be removed first, because these ions produce magnesium and Ferrous zeolites. This cannot be easily regenerated, 3. Mineral acids, if present in water, destroy the zeolite bed and therefore, they must be neutralized with soda, before admitting the water to the zeolite softening plant. Advantages: 1. Itremoves the hardness completely and water of about 10 ppm hardness is produced. 2, The equipment used is compact, occupying a small space. 3. No impurities are precipitated, so there is no danger of sludge formation in the treated water at later stage. 4, The process automatically adjusts itself for variation in hardness of incoming water. 5. Itis quite clean 6. Itrequires less time for softening 7. Itrequires less skill for maintenance as well as operation. Disadvantages: 1. The treated water contains more sodium salts than in lime-soda process. 2. Anions are not removed from water. CO: produces OH’, it causes caustic embrittlement. HCOs decomposes and produces CO;, it causes corrosion. 3. High turbidity water cannot be treated efficiently by this method. DESALINATION OF BRACKISH WATER: The process of removing common salt from the water is known as desalination. The water containing dissolved salts with a peculiar salty taste is called brackish water. Seawater, containing on an average about 3.5% salts, comes under this category. Brackish water is totally unfit for drinking purpose. Commonly used methods for the desalination of brackish water is: 1. Reverse Osmosis & 2. Electrodialysis. 1. REVERSE OSMOSIS: Osmosis: Flow of solvent takes place from a region of low concentration to high concentration when two solutions of different concentrations are separated by a semi-permeable membrane. The flow continues till the concentration is equal on both the sides, ‘The driving force for osmosis is osmotic pressure, However, if a hydrostatic pressure in excess of osmotic pressure is applied on the concentrated side, the flow of solvent reverses as itis forced to mave from concentrated side to dilute side across the membrane. Thisis the basis of reverse osmosis. For practical purposes, semi-permeable membrane based on thin Pressure films of cellulose acetate, polymethyl acrylate and polyamide | polymers are used. A pressure of the order of 15-40 kg/cm? is applied for separating the water from its contaminants. The process is also known as, — paton super filtration or hyper filtration. Advantages: 1. Itremoves ionic, non-ionic, colloidal impurities 2. Colloidal Sid, can be removed by reverse osmosis which even Stout som cannot be removed by demineralization. a 3. tis simple and reliable process. 4, Capital and operating costs are low. 5. Maintenance cost depends on the replacement of the semi- permeable membrane. The life time of membrane is quite high, about 2 years. 6. Semi-permeable membrane can be easily replaced within a few minutes, thereby uninterrupted water supply can be provided. ee water out Reverse osmosis cell 2. ELECTRODIALYSIS: In this method, ions are pulled out of the salt water by passing direct current. When direct current is passed through saline Seawater Sea water Sea water water, the Na” ions move towards negative pole (cathode) and Cl’ ions move towards positive pole (anode) through membranes. As a result the concentration of brine decreases in the central compartment. Desalinated water is removed from central compartment from time to time, while concentrated water in side compartments is replaced by fresh sea water. sereare | | tents | @ Cathode For more efficient separation, ion selective membranes are employed. Anion-selective membrane has permeability for only one kind of ions with specific charge. Pu Concerted wat ‘rine Line diagram of electrodialysis. Cation-selective membrane is permeable to cations only. It has negatively charged fixed functional groups such as RSOrH" or RCOOH'. Anion-selective membrane is permeable to anions only. It has positively charged fixed functional groups such as RaN‘CI An electrodialysis cell consists of a large number of paired sets of plastic membranes. Cation-selective membrane is placed near cathode.Anion-selective membrane is placed near anode, Saline water is passed under a pressure of about 5-6 Ke/m? between membrane pairs and an electric field is applied perpendicular to the direction of water flow. Cation-selective_ membrane repels anions and Seanad allows cations to pass through. Anion-selective membrane repels cations and allows anions to pass through.Therefore water in sstne || one compartment of the cell deprived of salts, while the salt concentration in adjacent compartments is increased, Thus, we get alternative streams of pure water and concentrated brine ‘Advantages: 1. The unit is compact, 2. Cost of installation and operation is econo! 3. If electricity is easily available, it is best suited“ method. — ‘TREATMENT OF WATER FOR DOMESTIC PURPOSES: Sereening: Raw water is passed through screens, having large number of holes. Floating matter Is stopped by the screen. Sedimentation: In this process water is allowed to stand undisturbed in big tanks, about Sm deep. Most of the suspended particles settle down at the bottom, due to the force of gravity. The clear supernatant water is then drawn from tank with the help of pumps. The retention period in a sedimentation tank ranges from 2-6 hours. Sedimentation by coagulation In order to carry out the sedimentation process successfully, some of the chemicals are added to water before sedimentation. These chemicals are called coagulants. The coagulants when added to water form an insoluble gelatinous, flocculent precipitates, which descends through the water and adsorbs very fine suspended impurities forming bigger flocs, which settle down. Some of the coagulants used for sedimentation process are alum, ferrous sulphate, sodium aluminate etc. Chemical coagulants: ‘Alum: KaSOs, Al(SOs)3. 24H:0 ‘Alum is the most widely used in water treatment plants. ‘Als(SOx)2 + Ca(HCOs]2 ———> 2AI(OH}2 + 3CaSO« + 6COz NaAlO; + 2H.0 ————» Al(OH); + NaOH FeSO. + Mg(HCO:)2 ————= Fe(OH): + MgSO: + 2CO: Filtration: It is the process of removing colloidal matter and most of the bacteria, microorganisms etc, by passing water through a bed of fine sand and other proper-sized granular materials. Filtration is carried out by using sand-filter. A sand filter consists of a thick layer of fine sand placed over coarse sand and gravel. The impurities are unable to pass through the gaps in the sand bed, because of their size. ig 10. Sone. Removal of microorganisms (Disinfection or Ster Water after passing through Sedimentation, Coagulation and Filtration operations still contains a small quantity of Pathogenic bacteria. Disinfection: The process of destroying/killing the disease producing bacteria, micro-organisms, etc. from the water and making it safe for use, is called disinfection, Disinfectants: the chemicals or substances which are added to water for killing the bacteria.“The disinfection of water can be carried out by following methods: A. Boiling water for 10-15 minutes, all the disease-producing bacteria are killed and water becomes safe for use. This method is very costly. B. Bleaching Power: In small water works, about 1 kg of bleaching powder in 1000 kilolitres of is mixes and water is allowed to stand for several hours, The chemical reaction produces a powerful germicide called hypochlorous acid. ‘The disinfection action of bleaching powder is due to the chlorine made available by it. Ca0Ch + #0 ————» Ca(OH). + Cle H,0 + Cl, ————> HCI + Hocl HOC! + Germs ————» Germs are killed Drawbacks: 1. Bleaching powder introduces calcium in water, and increases its hardness. 2. Bleaching powder deteriorates due to decomposition during storage. 3. Excess of bleaching powder gives a bad taste and smell to treated water. €. Chlorine: Chlorine (either gas or in conc. Solution form) produces hypochlorous acid which is a powerful germicide, H,0 + Cl, ————> HOCI + Hcl HOC! + Germs ———— Germs are killed Death of micro-organisms results due to inactivation of enzymes (in the cells of organisms) by hypochiorous acid, It produces OCI’ which cannot combine with enzymes. Hocl HW’ +0cr So, chlorine is found to be more effective disinfectant at lower pH values (below 6.5). ‘Apparatus used for chlorination process is known as Raw vaier —» =< Goneanated chlorinator, which is a high tower having number of baffle “ cai plates. Water and chlorine solution are introduced at its top. During their passage through the tower, they get — ‘thoroughly mixed. The treated water is taken out from the 2 bottom. For filtered water, about 0.3-0.5 ppm of chlorine SAF sat lates is sufficient Sid ‘Advantages of Chlorine: 2 1 Itis effective and economical Se High tower 2. Itrequires very little space for storage. Sa 3. Itis stable and does not deteriorate on keeping. 4. tan be used at low and high temperatures. 5. It leaves no salt impurities in the treated water. I. 6, Itis most ideal disinfectant. =p rte eer Disadvantages: oaiet 1. Excess of chlorine produces unpleasant taste and odour Chlorinator 2. The quantity of free chlorine in treated water should not exceed 0.1-0.2 ppm Break-Point Chlorination (Free-residual chlorination): It involves addition of sufficient amount of chlorine to kill all the bacteria, to oxidize the entire (a). organic matter, (b). reducing substances and (c. free ammonia present in water. When chlorine is added to water, first oxidation of reducing substances, then formation of chloro-organic compounds and chloramines and then destruction of chloro-organic compounds and chloramines occur. ‘The point at which free residual chlorine begins to appear is termed as “Break-point”. Addition of chlorine at the break point is called ‘Break-Point Chlorination’ or ‘Free-residual chlorination’. Advantages: 1. Itoxidizes organic compounds, ammonia and reducing compounds completely. 2, It removes colour in water (due to the presence of organic matter) 3. It destroys pathogens completely4, Itremoves both odour and taste from water 5. It prevents growth of any weeds in water ‘Sexton! ' Disinfection by ozone: Ozone is an excellent £ sngen | ogameand|, sige} isinfectant. It is produced by passing silent electric | |"Ordalor" Tal choram Fg residual discharge through cold and dry oxygen. | | reste ltmeteacccetinast = TS 0) 30 205 3 | Jeompounds| ana BL enoranine Oxygen Ozone lorie | eompounss Ozone is highly unstable and breaks down, liberating —CH,—CH,— 1. In case of bifunctional monomer two reactive cain oration by groups attach side by side to each other, gives oot rear (or) straight-chain polymer. Chain : movements possible in one direction | | secondary van de waa ctor tbce of meer rcton en 2, When a small amount of trfunctional monomer Main chain (backbone) is mixed with a bifunctional monomer, a branched : chain polymer results. The movement in branched chain molecules is more restricted than that of straight chain 3. In case of polyfunctional monomers, a three dimensional polymer network is formed. The movement of individual molecules is prevented by strong cross-links. Tacticrry The orientation of monomeric units in a macromolecule can take an orderly or disorderly fashion with respect to the chain. The difference in configuration (tacticity) affects their physical properties On the basis of the configuration (stereochemistry), polymers can be classified into three categories viz., isotactic (cis-arrangement), syndiotactic _(trans- arrangement) and atactic. Isotactic polymer: If all the side groups are present on the same side of the chain (cis arrangement), itis called an isotactic polymer. Syndiotactic polymer: If the arrangement of side groups is in alternating fashion (trans arrangement), it is called 2 syndiotactic polymer. Atactic Polymer: If the arrangement of side groups is, random around the main chain, it is termed as atactic polymer. | 4 NERA. | | [re R R f R Atactic Polymer‘TYPES OF POLYMERIZATION: Polymers can be synthesized by the following polymerization processes. |. Addition (chain growth) polymerization I. Condensation (step growth) polymerization Ill. Copolymerization 1) Addition polymerization: ‘This reaction gives a product, which is an exact multiple of the original monomeric molecule. No molecule is evolved during polymerization. ‘Monomer usually contains one or more double bonds. Intermolecular rearrangement may make the molecule bifunctional. ‘The reaction must be initiated by heat, light, pressure, or a catalyst. ‘The reaction is taking place by successive addition of monomer uni polymerization. e.g. Ethylene on addition polymeriza n gives polythene Rearrangement Polymerization He Ha o Hjo—or, Remamssmen, fgg}. Pobmeiaign _/ Oe _& Te (& & ( Ethylene Pressure or Catalyst functional molecules Polythene 1!) Condensation polymerization: ‘The reaction occurs with the elimination of small molecules like HO, HCI, CHsOH, NH; etc. ‘The products not exact multiple of the original monomeric molecule. ‘This reaction occurs between polar group containing monomers. ‘Monomers having ~ COOH and ~ OH or, COOH and -NH2 undergo condensation polymerization. ‘The product is formed through a series of independent reactions. It is also called step growth polymerization. e.g. Nylon-6,6': Condensation accurs between adipic acid and hexamethylene diamine 9 9° ia g 24 8 HANICHe NH «9 HO-E-ICHae—E-OM | > {H-(CHle NHC (0Hle€ Hexamethylene diamine Adipic acid on Ill) Copolymerization: Joint polymerization of two or more monomer species is known as copolymerization. The polymer is known as copolymer. e.g. Copolymerization of butadiene and styrene gives styrene-butadiene copolymer. {He He\ He alae mend «fu | Be ‘ ley ae Poly butadiene-co-styrene MECHANISM OF ADDITION POLYMERIZATION FREE RADICAL MECHANISM Chain initiation Initiation involves two reactions. 1, Production of free radicals by hemolytic dissociation of initiator, R-R—— 2K 2. Initiation involves addition of free radicals to the monomer to produce a chain initiating species R noe RL H,0—6u be : Chain propagation Itinvolves growth of chain by the successive addition of large no of monomers.vi \ noe Fao pH aft one —¢'—CH R R \ e/a oR Chain termination Termination of the growing chain occurs either by coupling or disproportionation Combination (Coupling) He W\ He /Hy ji sn BBB 64 16 Bon Bin — af Be hfe R R \R dy \ok Rody Disproportionation fA LO elon Pha on, «wot f “e beth * a se aft on gis + Het fon ee \ ba toe), CATION MECHANISM This mechanism occurs when electron donating groups like CHs, CsHs etc. are present in monomer. These groups stabilize carbocation formed. Chain initiation The catalyst initiates polymerization by the addition of H* to the monomer to form a chain initiating species AICl, + HCl —— H* AIC; Hac: a. ww R Chain propagation It involves growth of chain by the successive addition of large number of monomers. R ham oN \ 4. HOCH + ntocH + yf? oul oe By \ R \ a ok Chain termination ‘set RT WW ANION MECHANISM Chain initiation This mechanism occurs when electron withdrawing groups like COOH, CN, COOR etc. are present in monomer. These groups stabilize carbanion formed. KNH, ——» Kv 4 NHy ‘The catalyst initiates polymerization by the addition of NH; ion to the monomer to form a chain initiating species, NHy 4, bo Hal BL HN-C—CH R R Chain propagation Itinvolves growth of chain by the successive addition of large number of monomers.He a ite He H\ He HN-C—CH + 0 H,C—=CH — nNfe “ye eH R R \ r/o oR Chain termination Terineoncl roving chance bye anf aa gest pt # oa (te wnf BSB Bee wl \ dA \ dA } CO-ORDINATION POLYMERIZATION MECHANISM Tiegler-Natta catalyst is a combination of transition metal halide (TiCle, TiCls, ZrBrs, TiCl2, halides of V, Zr, Cr, Mo and W) and an organo metallic compounds (like AIR). Stereo specific polymerization can be carried out Using Zegler-Natta catalyst Polymerization occurs due to Insertion of alkene monomers between TIC bond cl cl Ziegler-Natta catalyst from TiCls- AIR: R > Cat—R' ne re No OR Chain initiation car’ HOCH cote R Chain propagation HoH cae’ tr yong R Heo / He H\ HX, Heo / He PLASTICS: Organic materials of high molecular weight which can be moulded into desired form by the application of heat and pressure in the presence of a catalyst. Resins are the basic binding materials. They form major part of plastics and they actually undergo polymerization and condensation during their moulding operation. Properties of plastics: 1. lightness in weight 14. low melting points 2. Good thermal and electrical insulation 15, high refractive index 3. Corrosion resistance 16, Ability to take variety of colours and shades 4, Easy workability 17. Goad shock absorption capacity 5. Adhesiveness 18, High resistance to abrasion 6. Low fabrication cost 19, Dimensional stability 7. Decorative surface effects 20, Impermeable to water 8. Easy moulding 21 capacity of being made to order 9. Insect resistance 22, Good strength 10. Low thermal expansion coefficient 23, Toughness, 11, Chemical inertness 24, Absorbent of vibration and sound 12, Transparency 25, Excellent in finish 13. Low maintenance costDisadvantages of plastics over metals, 1. High cost 5. Deformation under load 2. Combustibility 6. Embrittlement at low temperatures 3. poor ductility 7. low heat resistance 4, Softness Uses of plastics 1. For making electrical goods 9. For making hoses, water tubings, electrical cables 2. For making furniture 10 For preparing decorative laminates and mouldings 3. For making handles for tools LLL. For making overhead tanks and pipes 4. For making paints 12. For making household articles 5. For making floor and wall linings 13. For making synthetic fibres 6. For making electrical appliances 14. For making adhesives 7. For making bearings and propeller shafts 15. As water softening agent 8, For heat and sound insulation CLASSIFICATION OF PLASTICS (TYPES OF PLASTICS) ‘Thermoplastics: ‘Thermo plastics are the plastics which can be softened on heating and hardened on cooling reversibly. Their hardness is a temporary property. 1. They are formed by addition polymerization 2. They consist of linear polymer chains with negligible cross-linking, 3. They are soft and less brittle. 4, They are soluble in organic solvents. 5. They soften on heating, because secondary forces between individual chains can break easily. 6. They can be reshaped and reused. 7. They can be reclaimed from wastes. Examples: Polythene (PE), polypropylene (PP), polyvinyl chloride(PVC), polytetrafiuoroethylene (PTFE or Teflon}, polystyrene (PS), nylons. ‘Thermosetting plastics: ‘Thermo plastics are the plastics which get hardened during moulding process, and once they have solidified they cannot be softened. Their hardness is a permanent property. —v—————— a a a M. ‘M—M- 1. They are mostly formed by condensation polymerization. 2. They have three-dimensional network structure, joined by strong covalent bonds. 3. They are hard and rigid (They become hard on heating during moulding process). 4, They are not soluble in organic solvents. 5. They do not soften on heating due to cross links (Strong covalent bonds between chains). 6. They cannot be reshaped once they are set, cannot be reused. 7. They cannot be reclaimed from wastes. Examples: Phenol-formaldehyde resins, urea-formaldehyde resin, epoxy resins (araldite), Bakelite.POLY VINYL CHLORIDE (PVC): Preparation: PVC is obtained by heating 2 water emulsion of vinyl chloride in presence of a small amount of benzoyl peroxide in an autoclave under pressure. Polymerization H oe a. Properties: PVC is colourless, odourless and non-inflammable and chemically inert powder. Itis resistant to light, atmospheric oxygen, inorganic acids and alkalis. Itis soluble in chiorinated hydrocarbons such as ethyl chloride. It possesses high softening point (148°C) thas greater stiffness and rigidity than polyethylene, but is brittle. ‘Applications: Rigid PVC (Unplasticized PVC) thas superior chemical resistance and high rigidity, but is brit. It is used for making sheets, which are used for tank-linings, light fittings, safety helmets, refrigerator components, tyres, mudguards of cycle and motor cycie. Itis also used in strip or tube form for use in place of non-ferrous metals. Plasticized Pvc: Itis obtained by adding plasticizers such as diocty! phthalate, dibutyl phthalate, tricresyl phosphate etc, to rigid PVC. It is used for making continuous sheets employed for rain-coats, table-cloths and curtains, electrical insulations like cable covering. Itis used for making toys, tool handles, radio components, plastic coated cloth, chemical containers, thermal insulating foam, conveyor belts etc. a He ‘TEFLON (PTFE or FLUON) Preparation: Teflon is usually obtained by polymerization of emulsion of tetrafluroethylene, under pressure in presence of benzoyl peroxide as catalyst. Properties: Strong attractive forces exist between chains due to highly electronegative fluorine atoms and the regular configuration Strong attractive forces give extreme toughness, high softening point (350°C), high resistance to chemicals (except hot alkali metal and hot fluorine), high density, waxy touch, very low coefficient of friction, good electrical and mechanical properties tt can be machined, punched and drilled It cannot be dissolved and cannot exist in true molten state. Around 350°C it forms viscous opaque mass which can be moulded into desired shape. Applications: Teflon is used as insulating material (for motors, transformers, cables wires etc.) It is used for making gaskets for packings, pump parts, tank linings, chemical carrying pipes, tubings, and tanks. Itis used for coating and impregnating glass fibre, asbestos fibres, cloth ete. Itis used in non-lubricating bearings. Itis used in non-sticking coatings. Itis used in burette stop-cocks.BAKELITE: Preparation: Its prepared by condensing phenol with formaldehyde in presence of acidic /alkaline catalyst. Initial reaction results in the formation of o- and p- hydroxymethyl phenols, which react to form linear polymer, novolac. o# OQ _HCHO | a C HOH O-Methylol Phenol P-Methylol Phenol OH OH OH OH OH OH nom H oe se rv “ wy — C Novolac During moulding, hexamethylene tetramine is added. It provides formaldehyde and converts novolac into crosslinked structure called bakelite. SES Ss LCHIN Gy sid ga BEd OH Properties: It is hard, rigid, scratch resi It is resistant to non-oxidi presence of -OH groups). Ithas excellent electrical insulating character. Application: Bakelite is used for making electrical insulator parts like switches, plugs, switch boards, heater handles etc. It is used for making telephone parts, cabinets for radio and television. It is used for impregnating fibre, wood and paper. It is used as adhesives for grinding wheels. It is used in paints and varnishes. It is used as cation exchange resin water softening. Its used for making bearings and propeller shafts and rolling mills. fant, water resistant, infusible, insoluble solid. agents, salts many organic solvents but is attacked by alkalis (due to the NYLON: Nylons are synthetic fibres which have recurring amide groups. Preparation: Nylon 6,6: Nylon 6,6 is prepared by the condensation polymerisation of hexamethylene diamine and adipic acid. ny ne oO © HANC(CHDe-NHy 5 9 HO-G-(CHale-G-OH Horii wt& ron. 8} Hexamethylene diamine Adipic acid ‘ °Nylon-6: Nylon-6 can be synthesized from cyclohexane. The steps involved are 1. Conversion of cyclohexane to cyclohexanone by oxidation. 2. Treatment of cyclohexanone with hydroxyl amine to form an oxime. 3. Conversion of cyclohexanone oxime into caprolactam by Beckmann rearrangement in the presence of +250. Nylon-6 can be prepared by ring opening polymerisation of caprolactam. -OH 9 Beckmann] NioH Rearrangement “NH Cr few tf Nylon-6 can be prepared by self-condensation of e-amino caproic acid. g 3 HaN—(CHz)s—C-OH Nylon=11: Nylon-11 can be prepared by the self-condensation of w amino undecanoic acid. oO H 1 enn 8 Properti ‘They are translucent, whitish, horny, high melting (160-264°C) polymers. ‘They possess high temperature stability and good abrasion resistance. ‘They are insoluble in common organic solvents (like methylated spirit, benzene, and acetone) and soluble in phenol and formic acid ‘Their mouldings and extrusions have good physical strengths and self lubricating properties. Applications: Nylon 6,6 is primarily used for fibres, used in making socks, ladies hoses, undergarments, dresses, carpets etc, Nylon-6 and nylon-L1 are mainly used for gears and bearings (work without any lubrication). ‘They are also used for making filaments for ropes, brustles for tooth brushes and films, tyre-cords etc. 9 RHaN-(CH;)ig—C-OH RUBBERS (ELASTOMERS): Rubbers are high polymers which have elastic properties in H excess, I Rubber can be stretched to 4-10 times of its original length e en Nd and as soon as the stretching force is released, it returns to N— tN its original length. aan ~~ \ Elster malecle ot staght chained, butin te form "SN / ot of a coil and it can be stretched like a spring, Tf dig The unstretched rubber is amorphous wee As stretching is done, the rubber chains get partially get b US aligned with respect to another, thereby causing ‘ crystallization and stiffening of material Coiled rubber chain of natural rubber On releasing the deformation stress, the chains get reverted to their original coiled state and the material becomes amorphous. NATURAL RUBBER: Natural rubber consists of basic material called latex. It is a dispersion of isoprene. During the treatment, these isoprene molecules polymerize to form, long chains of cis-polyisoprene.Polyisoprene exists in two geometric isomers Cis- and Trans-forms. Natural rubber is soft and has cis- configuration while ‘Guttapercha’ has trans configauration. a ma 2 bon pcr J { \ ad Ne CHe HSC isoprene ix polsinoprene Molecular weight of raw rubber is about 100,000-150,000. Natural rubber is made from saps of a wide range of plants like Hevea brasiliensis and guayule, found in tropical and semi tropical countries (such as Indonesia, Malaysia, Thailand, Ceylon, India, South America etc. ‘The rubber latex is obtained by making incisions in the bark of the rubber trees allowing the saps to flow in ‘to small vessels. The latex is emptied into buckets and transferred to a factory for treatment. PROCESSING OF LATEX ‘The latex is diluted to contain 15-20% of rubber and filtered, Acetic acid or formic acid (1Kg per 200 Kg) is added, rubber is coagulated to soft mass. Coagulated mass (coagulum) is washed. The coagulum is treated as follows. Crepe Rubber: The coagulum is allowed to drain for two hours. It is passed through a creping machine, which consists of two rollers (3 mm apart and 50 cm wide) with longitudinal grooves. ‘The coagulum is converted into a sheet. It possesses uneven surface and resembles crepe paper. Smoked Rubber: Coagulation is carried out in long tanks (1 m wide and 30 cm deep) having sides with vertical grooves (about 4cm apart), fitted with metal plates. Diluted latex is poured into the tanks, acetic acid or formic acid is added, and the mixture is stirred. The partition plates are inserted into grooves. ‘The tanks are kept undisturbed for 16 hours. The slabs of coagulum are removed. ‘The slabs are passed through a series of smooth rollers. ‘The sheets are then hung for about 4 days in a smoke house, in which temperature between 40 to 50°C. Drawbacks of raw rubber: Natural rubber as such has no practical utility value. Its because of many inherent deficiencies. Itis plastic in nature [It is hard at low temperature and soft at high temperature (10 to 60°C)] Itis weak (Its tensile strength is only 200 Kg/em?) thas high water absorption tendency. Itis not resistant to non-polar solvents and oils Itis attacked by oxidizing agents. Itperishes due to oxidation in air. thas marked tackiness (two pieces when pressed together, the unite to form a single piece) It swells in organic solvents and gradually disintegrates. Ithas little durability. It suffers permanent deformation, when its stretched to a greater extent. Vulcanization: Discovered by charles Goodyear in 1838. To improve the properties, rubber is compounded with some chemicals like sulfur, hydrofgen sulfide, benzoyl chioride ete. Most important additive is sulfur. Vulcanization is a process of heating the raw rubber at 100 ~ 140°C with sulfur. The sulfur combines chemically at the double bonds of different rubber molecules and provides cross-linking between the chains. Vulcanization gives stiffness to rubber. The extent of stiffness depends on the amount of sulfur used e.g. Tyre rubber contains 3 ~ 5% sulfur. The battery case rubber contains 30% sulfur. Vuleanite or ebonite or hard rubber contains about 32% sulfurRaw Rubber chains ‘Vuleanized Rubber Advantages of vuleanization: Vulcanized rubber has good tensile strength (2000 Ke/cm’. It has excellent resilience ice, articles made from it returns to the original shape when the deforming load is removed, It has low water absorption tendency. thas better resistance to oxidation, and abrasion It has much higher resistance to wear and tear compared to raw rubber. thas broader useful temperature range (-40 to 100°C) compared to raw rubber. It is a better electrical insulator. e.g. Ebonite Itis resistant to organic solvents like petrol, benzene, CCls, fats and oils, but it swells in them. thas only slight tackiness, It has low elasticity. They property depends on the extent of vulcanization, Ebonite has practically no elasticity, COMPOUNDING OF RUBBER Mixing of raw rubber with other substances to give specific properties to the product and make it suitable for particular job. ‘The following materials are added to raw rubber. Softeners and plasticizers: They gives greater tenacity and adhesion. e.g. vegetable oils, waxes, stearic acid, rosin etc. ‘Vuleanizing agents: They give stiffness to rubber e.g. sulfur, sulfur monochloride, hydrogen sulfide, benzoyl chloride, trinitro benzene and alkyl phenyl sulfides ete ‘Accelerators : They shorten the time required for vulcanization e.g. 2-mercaptol, benzothiozole, and zinc alkyl zanthate. Antioxidants: They prevent oxidation on rubber. e.g. complex amines (such as phenyl naphthyl amines) and phosp! Reinforcing fillers: They give strength and rigidity to rubber. e.g. carbon black, zinc oxide, calcium carbonate, magnesium carbonate. Colouring matters: They give desired colour to rubber. e.g. Titanium dioxide White Chromium oxide Green Antimony sulfide Crimson Ferric oxide Red Lead chromate Yellow Process: Properly weighed amounts of ingredients are mixed and kneaded or masticated. During mastication, the ‘material is softened by continuous ‘break down’, The process is carried out in hallow roll mills through which cold and hot water can be passed to maintain temperature. SYNTHETIC RUBBERS. ‘The term synthetic rubber is a misnomer, because itis not chemically identical with natural rubber. Its more appropriate to use the term artificial rubber, instead of synthetic rubber.Buna-S Rubber (Styrene Rubber) Preparation: It is produced by copolymerization of butadiene and styrene (about 75% and 25% respectively). te) He onic —e oy — QO, 1,3-butadiene © Styrene butadiene rubber (SBR) Poly btaioe-co-yrene Properties It resembles natural rubber thas high abrasion resistance, high load bearing capacity and resilience. It gets readily oxidized especially in presence of Ozone It swells in olls and solvents. It can be vulcanized in the same way as natural rubber (either by sulfur or by sulfur monochloride}{it requires less sulfur, but more accelerator) Applications It is mainly used for the manufacture of motor tyres. Other uses are floor tiles, Shoe soles, Foot ware components, wire and cable insulations, carpet backing, Gaskets, Adhesives, Tank linings. BUNA-N RUBBER (NITRILE RUBBER) Preparation: Its produced by copolymerization of butadiene and acrylonitrile. [ea —ame + hemp] 7 1.3-butadiene Acrylo nitrile Poly butadiene-co-acrylonitrile Properties It has excellent resistance to heat, sunlight, rubber (due to presence of ~CN groups). As the acrylonitrile proportion is increased, the resistance to heat, sunlight, oils, solvents, acids, salts et., increases, but the low temperature resilience suffers. It can be vulcanized in the same way as natural rubber ‘Vulcanized rubber is more resistant to heat than natural rubber. Applications It is used for making conveyor belts, air craft components, automobile parts, oil resistant foams, printing rollers, hoses, gaskets, adhesives, tank linings. 's, acids and salts, but less resistant to alkali than natural POLYURETHANE RUBBER Preparation: It is prepared by the reaction of a polyalcohol with a di-isocyanate. j 9 ° 9 He He I | te te nce =e | — AH He Hy KO—c'—c'—OH| 5» oe eg ll gs Be Ethylene glyco Eylene diisocyanate * Polyurethane rubber (Iscyanate aber) Properties ‘They are highly resistant to oxidation (because of saturated character) ‘They also show good resistance to many organic solvents, but are attacked by acids and alkalis (especially concentrated and hot). Polyurethane foams are light, tough and resistant to heat, abrasion, chemicals and weathering.Applications Its used for surface coatings, for the manufacture of foams and spandex rubber. POLYSULPHIDE RUBBER [THIOCOL (THIOKOL) RUBBER]: Polysulphide rubber is also known as Thiokol rubber. Preparation Itis prepared by the reaction between sodium polysulphide (Na2S,) and ethylene dichloride (CHC|—CH,Cl). He He $8 [te He & $)\ nega «ana —$—$—na > L688 Properties It has extremely good resistance to mineral oils, fuel oxygen, ozone and sunlight. It is impermeable to gases. It cannot be vulcanized and hence does not form hard rubber. Ithas poor strength and abrasion resistance. Applications Polysulphide rubbers are mainly used to make sealants, gaskets, balloons, fabric coatings and gasoline hoses, oil tank linings, cable coverings. Polysulphide rubber is used as a solid propellant fuel for rockets. CONDUCTING POLYMERS Most of the polymeric materials are poor conductors of electricity because of non availability of large no. of free electrons in the conduction process. Polymeric materials which possess electrical conductivities on a par with metallic conductors are called conducting polymers ‘The conductivities of as high as 1.5 X 10” Ohm’* m*are attained in these polymeric materials. Different types of conducting polymers 1. Intrinsically conducting polymers 2. Doped conducting polymers 3. Extrinsically conducting polymers 4. Coordination conducting polymers 1. intrinsically conducting polymers (Conjugated n-electrons conducting polymers) itis a polymer whose backbones or associated groups consist of delocalized electron pair or residual charge. In an electric field conjugated m-electrons of polymer get excited there by electricity passes through solid polymeric material. Presence of conjugated m-electrons in polymer increases its conductivity to larger extent. eg. IOS IIR a K ow M8 Rk VO mt TTT 7 VY pia — i \ S OO Oe O- Pipe OHO OL Polyaniine2. Doped conducting polymers: It is obtained by exposing a polymer to a charge transfer agent either in gas phase or in solution. 1. Intrinsically Conducting polymers have low conductivity (~10"" Ohm" m*) 2. These posses low ionization potential and high electron affinities. So these can be easily oxidized or reduced 3. Conductivity of ICP can be increased by creating either positive or negative charge on the polymer backbone by oxidation or reduction. This technique is called doping (an analog with semiconductor). It is of ‘two types p-doping involves treating an intrinsically conducting polymer with a Lewis acid. There by oxidation takes place and positive charges on the polymer back bone are created, Some of the common p-dopants used are l:, Bra, ASFs, PFs, FeCl, etc., ‘n-doping involves treating an intrinsically conducting polymer with a Lewis base. There by reduction takes place and negative charges on the polymer back bone are created. Some of the common n-dopants used are Li, Na, Ca, Naphthyl amine ete. (CoH )y + 2FeCl; = ——— (GH), FeCl, + FeCh (GH), + 3h ——— (GH), 2 3. Extrinsically conducting polymers The conductivity is due to the presence of external ingredients in polymer. ‘These are two types Conductive element-filled polymer It is a polymer filled with conducting elements such as carbon black, metallic fibres, metal oxides etc., They are low in cost, light in weight, mechanically durable, strong and easily processable. i. Blended conducting polymer A product obtained by mixing a conventional polymer with a conducting polymer either by physical or chemical change. These can be easily processed and possess better physical, chemical and mechanical properties. 4, Coordination conducting polymers It is a charge transfer complex obtained by combining a metal atom with polydentate ligand. Their degree of polymerization is small (less than 18). ‘Applications of conducting polymers 1. In rechargeable light weight batteries. 2. In optical display devices. 3. In wiring in aircrafts and aerospace components. 4, In telecommunication systems. 5. In antistatic coatings for clothing, 6 7. 8 9. In electromagnetic screening materials. In electronic devices such as transistors and diodes. In solar cells, drug delivery system for human body etc., In photo voltaic devices e.g., Al / polymer / Au Photo voltaic cells. 10. In non linear optical materials. 11, In molecular wires, molecular switches. POLYACETYLENE Synthesis: It is prepared by addition polymerization of acetylene. Acetylene gas is passed over Ziegler-Natta catalyst to get polyacetylene. 2 H-C=c-H ———>Mechanism of p-doping Mechanism of n-doping a a a i ee ee fs I Polaron |» b Me i "6 ARK AA AEE SIS Ne Bipotazon 15 Bipolaron | | 2 PBrAy = POLYANILINE Synthesis: Its prepared by the reaction of aniline with ammonium perdisulfate at low temperature (0-5 °C). 2 Opn (NHD:S,05 - wh Mechanism of doping a ar) OOP OREO SE OO O-O- Conductivity Ohm! cm™ eat ie %y GQ OF04-07-O- —-Ob0H0F0- ci A h i Conductivity = 10 Oba em"! lc INORGANIC POLYMERS Inorganic polymers are giant molecules composed of atoms except carbon. Atoms in these polymers are Inte ‘wee mai by covalent bonds. e.g. {he} on (SN) note Silicone Polyphosphazine Polysulfur nitride Characteristic 1. They do not burn, They only soften at high temperatures. 2. They possess cross-linked structures. They are stiffer, harder, and more brittle than organic polymers. 3. The chain segments between cross links are usually short, but stiff, They are not flexible enough to allow intercalation of solvent molecules, so they do not swell in solvents.4, They contain polar repeating units, so they only dissolve in polar solvents. But, most of the polymers undergo reaction with solvent. 5. Their tensile strength is lesser than that of organic polymers. POLYPHOSPHAZINES: Polyphosphazines are inorganic polymers containing phosphorus atoms. Their general formula is = Clin polyphosphonitrle chlorides (Re \ we R= OCH in polydietiony phosphine a /n R = OCHS in polydiethoxy phosphazine Preparation of polyphosphonitrile chlorides: nPCls + nNHCI + (PCLN)s + (PCLN)s -(4n-1) HCL 250°C, Vacuum A (PChN)s + Py 4 2Np + 3Ch Properties: ‘They exhibit high elasticity and can be stretched many times reversibly. They are called inorganic rubbers. They are soluble in chloroform, but not in petroleum ether. They become brittle in presence of moisture due to formation oxide bridges. cl $l cl a q Gl ‘They form cross-linked polymers with ammonia. oI ¢ cl a @ 9 cl a a ] q a Polydimethoxy phosphazine and Polydiethoxy phosphazine are prepared by treating polyphosphonitrile chloride with sodium methoxide and sodium ethoxide respectively. / 9CHs\ cl \ 9CaHs \ pw cuona fT \ :ONa se \ Oc /n \d Js \ deat / Polydimethoxy phosphazine Phosphonitrile chloride Polydiethoxy phosphazineProperties: They are colourless, transparent and film-forming thermoplastics. ‘On heating above 100 °C, they form cyclic polymers (trimers or tetramers). Applications: 1. These are used as rigid plastics, expanded foams and fibres. 2. The inorganic backbone gives flexibility, fire resistance and stability to oxidation. 3. They form flexible plastics which are useful for fuel hoses and gaskets. 4. Thin films of poly (amino phosphazine) are used in hospitals to cover burns and wounds (They prevent body fluids and keep germs out). 5. [PN(OR)2], is a water repellent polymer and used where water proof thermoplasts are required. 6. Poiyditrfuoroethoxy)phosphazine is used for the construction of artificial blood vessels and organs 7. Polyphosphazines are used where good bio-stability and bio-compatibility are necessary, such as in the encapsulation of pancreatic cll. 8. Poly (organophosphazines) exhibit high permeability for fixed gases and organic liquids and may find use in membrane applications. 9. The polyphosphazines having alkyl ether side chain are used as solid solvents for salt such as lithium (These ion conducting materials can be fabricated into light weight, thin-film rechargeable lithium batteries). 10. They are also used in membranes, hydro-gels and bone replacement materials. SILICONES Silicones contain alternative silicon-oxygen structure and organic groups are attached to silicon atoms, Their structure is: R \ (ts si \d Preparation: Reaction of silicon with alky/ halide gives a mixture of products CHCl + Si CHSiCly : (CH,),SiCl, + (CHg);SiC1 3 (CH3),Si Reaction of silicon halide with Grignard reagent (alkyl magnesium halide) gives a mixture of products. SiC, + CHjMgCl ———* CH,SiCl; : (CH3)2SiCl, + (CH)3SiCl } (CH5),Si ‘The mixture is separated by fractional distillation to get different organo-silicon chlorides. These are polymerized by controlled hydrolysis. 1. Dimethy| silicon dichloride is ‘bifunctional’ and gives linear polymeric chains. CH CH CH, I Hydrolysis I Polymerization | | soms—cl S| Host $0 #H,0 ;-HCI CH, CHs CH, 2. Trimethy| silicon chloride is ‘monofunctional’ and can be used as a ‘chain stopper’. It can also be used in proportions to limit the chain-length. CHs CHs CHy CH I Hydrolysis I cl 2 |Hyc—Si-OH —Si—O—Si—CH 28,0 ; 281 I CHs CHs CH; CHs Minomethyl-silicon chloride is ‘trifunctional’ and gives cross-linked polymer. Its proportion determines the amount of cross-lin 2 HyC—Hs CH 40 o-& q OH ] oO ° CHy oO Hyolis Polymtiztion oo a nego » Hjo-$--H ne—d-o—$-0-d-0— l +H, ; HC] } } } 4 on | $9 6 { -0- $0080 CH; CHy 0 (Cross linked polymer Characteristics of silicones: 1. Silicones may be liquids, viscous liquids, semi-solids (like greases), rubber like and solids, depending on the proportion of various alky! silicon chlorides used during their preparation. 2. Because of Si-O links, they exhibit outstanding stability at high temperatures, good water resistance, good oxidation stability, but their chemical resistance is generally lower than that of other plastics. 3. Their specific gravity ranges from 1.03-2.1 g/cm*, 4, Their physical properties are much less affected by variations in temperature. 5. They are non-toxic in nature. Different types of silicones and their applications. Liquid silicones or silicone oils: ‘They are relatively iow molecular weight silicones. ‘They possess wetting power for metal. ‘They have surface tension. ‘They show small changes in viscosity with temperature. Applications: ‘They are used as high temperature lubricants, antifoaming agents, water repellent finishes, for leather and textiles, heat transfer media, as damping and hydraulic fluids. They are also used in cosmetics and polishes, Silicone greases: ‘They are modified si Applications: ‘They are used as lubricants at high and low temperatures. Silicone rubbers: ‘They are obtained by cross-linking the linear chains of silicones using peroxide. HC CH; | | CH CHs o- licone oils. They are obtained by adding fillers like silica, carbon black, lithium soap ete. HCH Cl 0 © of organic peroxide § ———~ cH, HCH CHy be cH; CH, cH, Vulcanized silicone rubber Raw silicone rubber Properties: ‘They are resistant to prolonged exposure to sunlight, weathering, most common oils, boiling water, dilute acids and alkalis.‘They remain flexible in temperature range of 90-250 °C (So used for making tyres of fighter aircrafts). Silicone rubber at very high temperature decomposes, gives SiO2 instead of carbon tar. Applications: Its used as a sealing material in search search-lights and in aircraft engines. Its used for insulating the electrical wiring in ships. It is used in making lubricants, paints and protective coatings for fabric and water proofing. Its used as adhesive in electronics industry. It is used for making insulations for washing machines. Its used for making artificial heart valves, transfusion tubes and padding for plastic surgery. Its used for making boots for use at very low temperature. Solid silicone resins: ‘They are highly cross-linked silicones obtained by condensing bi-functional tri-functional silicon halides. Properties They are thermosetting plastics. ‘They possess good electrical insulation properties and outstanding heat resistance (up to 200 °C). ‘The resins are good water repellents and have chemically high thermal stability. Applications: ‘They are used for making high voltage insulators, high temperature insulating foams and in mouldings requiring high thermal stability.CHAPTER-III ELECTROCHEMISTRY GALVANIC CELLS An electrochemical cells a device in which a redox reaction is utilized to get electrical energy. Itis also called voltaic cell or galvanic cell. The electrode where oxidation occurs a is called anode. - A The electrode where reduction occurs is called cathode Zrerod | An example of galvanic cell is Daniel (anode) cell. It consists of zinc electrode dippe: ZnSO, solution, copper electrode dipped in CuSO: solution. Each electrode is regarded as a half cell. The two solutions are separated | aso, bya salt bridge. soution The solutions can seep through salt bridge, and come into contact with each other automaticaly. Beecrochonical The salt bridge completes the circuit and maintains electical neutrality The electrode reactions in Danie! cell are: =—Cuent Copper rod (cathoce) cuso, souten 2s) + Zn" (ag) +20 xiation Gu (aa) * 26° > Cus) reduction (Daniel catty At anode (-ve electrode): Zn ———— Zn" +2e (Oxidation) At Cathode (+ve electrode) Cu" 42° ————> cu (Reduction! Cell reaction’ Zn+Cu® ———> Zn" + Cu The tendency of Zn to form Zn** is greater than the tendency of Zn’* to get deposited as Zn and hence, Zn electrode acquires a negative charge. The tendency of copper to go into solution is less than the tendency of Cu to get deposited as Cu and hence, copper electrode becomes positively charged. The e.m, ofthe cellis 1.1 volts Representation of a galvanic cell: ‘Agalvanic cell is represented by keeping in view the following points: 1. Anode is written on the left-hand side, while the cathode is written on the right-hand side. 2. The electrode on the left (i.e., anode) is represented by writing the metal (ar solid phase) first and then the electrolyte. The two are separated by vertical line or a semicolon. The electrolyte may be represented by the formula of the compound or ionic species. Additional information regarding concentration may also be mentioned in bracket. [Pt, H2 (1atm.); H* (1M)] ZnjZn*(1M) or — Zn /2n*(1M) or Zn; ZnSOs (1M) 3. The electrode on the right (i.e., cathode) is represented by writing the electrolyte first and the metal (or solid phase) thereafter. The two are separated by vertical line or a semicolon. cu (IM) ;Cu or Cu" (1M) /Cu or —CuSO4(1M) /Cu 4, Asalt bridge is indicated by two vertical lines, separating the two half cells. ‘Thus, Daniel cell may be represented as: Zn / Zn™* (1M) | Cu* (AM) /Cu NERNST EQUATION For a reversible reaction, the free energy change (AG) and its equilibrium constant (K) are inter-related as: [Products] AG =-RTInK + RT In eases We know that, AG° = -RT In K (Van’t Hoff isotherm) 4G 16° + RT In Peeductsl . (2) iReactants}Where, AG = Standard free energy change. R jas constant (8.314 J/Mol.K) T __=Temperature on Kelvin scale For a reversible reaction involving n electrons, the decrease in free energy (-AG) will produce electrical energy (E) of F coulombs and is given by and -AG*= nFE® = Standard free energy change. jumber of electrons (2) F = Faraday (96,500 coulombs of electricity) & standard electrode potential. Substituting equation (2) in equation (1), we get, © 4 RT in LProduets] FE = -nFE*+ RT In roe cee. RU jp (Products| M+ ne ———> M fea = rein he En Eres peat En [M"*] For an electrode oxidation reaction, M———> +ne Fox (Concentration of metal, [M] is unity) Fo, = Boe Zin [Mt] (a) Equations (3] and 4) are known as Nernst equations for single electrode potential From the above equations, itis clear that (i) concentration solution is increased, electrode potential increases and vice versa. (i 1 temperature is increased, electrode potential increases and vice versa, NUMERICAL CALCULATIONS (Concentration of metal, [MJ is unity) wel)Example 1. Calculate the standard potential of Cu*®/Cu if the electrode potential at 25° is 0.296 V when [Cu*®] = 0.015 M. Sol. ” og (M*") 0.0592 106 (Cu"?] 2 log 0.015 = [0.296 — 0.0296 x (- 1.8239)] V (0.296 + 0.05398] V = 0.34998 V. Example 2. Calculate the single electrode potential of copper metal in contact with 0.15 (M) Cu® solution. €° for copper = + 0.34 V (R= 8.314 J. K' mot, T = 298 K). Sol. e=ert PE nies) nF 2,803 x 8.314 x 208 2x 96500 4 2303x8314 298 2 96500 = 034+ 1g [Cu] 34 log 0.15 = 0.3156 V. BATTERIES: A reaction for which AG < Qis capable of doing work. Electricity can be generated by doing this work. ‘The reactants in a galvanic cell are containing stored energy and that can be released as electricity. A battery is an electrochemical cell, or a group of several electrochemical cells connected in as series, that can be used as a source of direct electric current at a constant voltage. Batteries are of three types: (i) Primary battery in which cell reaction is not reversible. (i) Secondary battery in which cell reaction can be reversed by passing direct electric current in opposite direction. Thus, a secondary battery may be used through a large number of cycles of discharging and charging. (ii) Flow battery (Fuel cell) which coverts chemical energy of fuels directly to electricity. NICKEL-CADMIUM BATTERY Its commonly abbreviated Ni-Cd or NiCad battery. It consists of cadmium as anode and nickel oxide as cathode. ‘The electrode reactions during discharging are: Atanode: Cd + 20H" ————» Cd(OH)2 +e" (Oxidation) AtCathode: NiO; +2H,0 + 2e° ———» Ni(OH) + 20H" (Reduction) Cell reaction: Cd + NiO; + 2H,O —————> CdOH), + Ni(OH)2 The reaction can be readily reversed, because the reaction products, Ni(OH)2 and Cd(OH): adhere to the electrode surfaces. Its a portable, rechargeable cell and its cell voltage is fairly constant (about 1.4 V). Itcan be packed in a sealed container. No gases are produced during discharging (or charging), it can be left for long period of time without deterioration. Uses: It is used in electronic calculators, electronic flash units, cordless electronic shavers, transistors and other battery powered small tools.LEAD-ACID BATTERY A storage cell can operate both as an electrochemical cell and as an electrolytic cell When operating as a electrochemical cell, it supplies electrical energy. When being recharged, the cell operates as an electrolytic cell ‘The common example of storage cell is the lead- acid storage cell. One of its electrodes is made of lead (Pb). The other is made of lead dioxide (PbO:] A number of lead plates are connected in parallel @ Anode and a number of lead dioxide plates are also connected in parallel 4 - ‘The lead plates fit in between the lead dioxide plates. ‘The plates are separated from the adjacent ones by the insulators. The entire combination is immersed in approximately 20-21% dil. H:SOs, corresponding to a density of 1.2-1.3 Discharging: When a storage cell is operating as an electrochemical cell ‘The electrode reactions during discharging are: Atanode: Ph ————> Pb*+2e (Oxidation) Pb* + SO,» PbSO. At Cathode: PbO: +4H*+2e° ————> Pb" +2H.0 (Reduction) Pbi* + SO,*————» PbO. Cell reaction: Pb + PbO: + 4H" + 2S0,> > 2 PSO. + 2,0 + Eneray Lead sulphate is precipitated at both electrodes. ‘The voltage of each cell is about 2.0 volts at 2 concentration of 21% of H2SOs at 25 °C. In general, itis a combination of six cells in series to form a battery with e.m.f of 12 volts. Charging: When both anode and cathode become covered with PbSO., the cell ceases to function as an. electrochemical cell. To recharge a lead storage, the reactions are reversed by passing an external e.m.f greater than 2 volts from a generator. Cell reaction during charging: 2 PbS, + 2H0 + Energy ————> Pb + PbO, + 4H* + 250, During discharging operation, the concentration of acid decreases, while it increases during charging. Uses: It is used for many purposes such as to supply current for electrical vehicles, gas engine ignition, in telephone exchanges, railway trains, mines, laboratories, hospitals, broadcasting stations, automobiles, power stations and distribution works. 2 cathode plates PbO,plates Aqueous H.SO, | its said to be discharging. UTHIUM ION CELLS: Lithium ion battery is a secondary battery. It does not contain metallic lithium. It contains lithium salt. ‘The movement of lithium ions is responsible for charging and discharging. Lithium ion cell has the following three components. Anode (-ve electrode): Layers of porous carbon Cathode (+ve electrode]: Layers of lithium ~metal oxide Electrolyte: Polymer gel Construction: The positive electrode is typically made from layers of lithium cobalt oxide (LiCoO.) ‘The negative electrode is made from layers of porous carbon (Graphite) Both the electrodes are dipped in a polymer gel electrolyte (organic solvent) and separated by a separator which is a perforated plastic and allows the Li" ions to pass through. Working:Charging: During charging, Lit ions flow from LUthium ton electrolyte: the positive electrode (LiCoO,) to negative Festive Charge —> electrode (graphite) through the electrolyte. “°° The electrons and lithium ions combine and t deposit there as UiCoO2 + C ———— Li. xCoOz + Clix Sor Discharging: During discharging, Li" ions flow — —» back through the electrolyte from negative electrode (graphite) to the positive electrode + —— (LiCoO,). The Li* ions and electrons combine at positive electrode and deposit there as Li UiaCo02 + CLig ———= LiCoO, + Advantages: 1. It is a high voltage and light weight battery. 2. tis small in size 3. Its voltage is three times to that of Ni-Cd battery. Uses: It is used in cell phones, note PC, portable LCD TV, semiconductor driven audio etc. agate Daciage | UC FUEL CELLS: An electrochemical cell that converts chemical energy of a fuel to electrical energy without combustion. A fuel cell converts the chemical energy of the fuels directly to electricity, ‘The essential process in a fuel cell is: Fuel + Oxygen ————> Oxidation products + Electricity Fuel cells do not store chemical energy. Reactants are supplied continuously and products are removed constantly. HYDROGEN-OXYGEN FUEL CELL: It is one of the simplest and most successful fuel cells. It consists of an electrolyte solution such as 25% KOH solution and two inert porous electrodes. Hydrogen and oxygen gases are bubbled through the anode and cathode compartments respectively. ‘The electrode reactions are: Atanode: 2H, +4OH’ ———— 4H.0+4e (Oxidation) AtCathode: Or +2H:0+4e" > 40H" _ (Reduction) Cell reaction: 2H; +0; ————= 2H,0 + Electricity ‘The standard e.m.Fof the cell, E° = E°ox + E°ya= 0.83 V+0.40V= 1.23 VIn actual practice, the e.m-f of the cell is 0.8-1.0V. ‘ome ‘The only product discharged by the cell is water. Usually, a large number of these cells are stacked S in series to make a battery, called fuel cell battery. wee ttt The electrodes must meet the stringent Sen requirement. Electrodes must = i. be good conductors. “rn i be good sources or sinks. iM, not be consumed by electrode reactions. =e iv, be excellent catalysts for the reactions takes place on their surfaces. The electrodes are made of either graphite impregnated with platinum or 75/25 alloy of Pd i and Ag. :] ‘The success of fuel cell lies in the development of Lat tH inexpensive electrodes that are powerful catalysts. )}—fhek Applications: HO; fuel cell is used as auxiliary energy source in space vehicles, submarines or other military vehicles. ‘The product water is a valuable source of fresh water for astronauts. METHANOL-OXYGEN FUEL CELL: In this fuel cell, CHsOH is used as a fuel, O2 as oxidant to generate electricity It consists of an electrolyte solution such as 25% KOH or NaOH solution and two inert porous electrodes. Anode is made of porous nickel plate coated with platinum / palladium catalyst. Cathode is made of porous nickel plate coated with Silver catalyst. Methanol vapour is passed through the anode, where it is oxidised Oxygen gas is bubbled through the cathode, where it is reduced. The electrical energy is produced with continuous supply of CHsOH at the anode. When the cell operates, the water vapour and carbon dioxide are liberated at around electrodes. The electrode reactions are: Atanode: CHsOH+H:0 > CO,+6H"+6e" (Oxidation) At Cathode: 20, +6H"+6e'————> 3H.0 _ (Reduction) Calleacton: —CHOH+20, COs 24:0 Bectrity Applications: The power produced in methanol oxygen fuel cell is enough to run a simple transistor radio. SOLID OXIDE FUEL CELL (SOFC): It differs in many respects from other fuel cells. i. It is composed of all solid-state materials. The anode, cathode and electrolyte are made from ceramic substances. Because of all ceramic make up, the cell operates at high temperatures (1,000 °C). The cell can be configured either as rolled tubes or flat plates.For solid oxide electrolyte, the most common ceramic material used is a mixture of zirconium oxide and calcium oxide. ‘The ceramic electrolyte is coated on both sides with specialized porous electrode materials. At the high operating temperatures, oxygen ions are formed at cathode. When the fuel gas is passed over the anode, the oxygen ions migrate through the crystal lattice to oxidize the fuel. Electrons generated at the anode move out through an external circuit, creating electricity In such 2 fuel cell, water gas (Hz + CO) is used as a fuel and oxygen as the oxidant. The electrode reactions are Atanode: x H+ CO+ (x+y) O™ XH: + COr+ 2(xty)e (Oxidation) At Cathode: + (x+y) 02+ 2(xty] ee ———= [x+y] 0" _(Reduction) Cellreaction: x Hy CO +5 (x+y) O; ———™ x H.0 + y CO» + Electricity The reaction rate at the operating temperature is quite high, so, no noble metal catalyst is needed. ‘The fuel-to-electrcity efficiency in SOFC is expected to be around 50 percent. If the hot exhaust of the cell is used for rotating turbines, the efficiency is likely to approach 60%. If waste heat is also used, the overall fuel efficiency could top 80-85%. ELECTROPLATING: It is the process of depositing the coating metal on the base metal by passing a direct current through an electrolytic solution containing the soluble salt of the coating metal ‘The base metal is the metal to be plated, Base metal is made cathode of the D.C power source electrolytic cell. o Anode is either made of the coating ‘metal itself or an inert metal of good electrical conductivity ike graphite. Electrolytic solution contains the soluble salt of the coating metal In order to geta strong, adherent and smooth deposit, certain additives are added to the electrolytic bath. sank In order to improve the brightness of the deposit, brightening agents are added to the electrolytic bath. ‘Schematic representation of the principle of electroplating For bright and smooth deposits, favourable conditions such as optimum temperature and optimum pH and ‘optimum current density (Current per unit surface area of cathode) are employed. For uniform deposition, slow electrolysis should be followed. Objectives of electroplating: (On metals: i. To increasing the resistance to corrosion of the plated metal li, To increase to chemical attack and wear resistance. i, To improve physical appearance and hardness, iv, To improve the surface properties. \. To improve the decorative and commercial values of metal On non-metals: i. For increasing strength. i. For preservation and decoration of the surfaces of non-metal (like plastics, wood, glass etc.) ii, For making the surface conductive. node lectoplaing bath Process of electroplating:The article to be plated first treated with an i ier agety organic solvent (trichloro ethylene, methylene if chloride etc.) or hot alkali to remove oils and o ieee greases. Then the article is treated with dil. acid to remove scale or rust. Electrolytic solution is taken in an electroplating bath, aE ‘Anode and cathode are dipped in the electrolytic Boater solution and direct current is passed | When direct current is passed from a battery, =— coating metal ions migrate to the cathode and get ad deposited there as metal atoms. Thus, a thin layer con coating metal is obtained on the cathode (base UJ Copper sutate metal), — ELECTROPLATING OF COPPER: Plating bath composition: 200-250 g CuSOs + 50-75 g H:S0s and rest water (Per L) Additives, : Gelatin or dextrin, sulfur-containing brightener, sulfonic ac. Temperature 20-40°C Current density 2 20-50mA/em? Anode 1 Pcontaining rolled Cu. Currentefficiency : 95-98% Throwing power :_—_~Low (Ability of electrolytic cell to give a deposit of uniform thickness) Applications In printed circuit boards. ELECTROPLATING OF NICKEL: Plating bath composition: 250 gNISO.+45 g NIC + 30g Bore acd and rest water (Per) Additives + Coumarin, saccharin, benzene sulfonamide Temperature : 40-70" Current density : 20-50mA/em? Anode Ni pieces in titanium mesh basket Currentefficiency 95% Throwing power Medium Applications Under coat for Cr plating, ELECTROPLATING OF CHROMIUM: Plating bath composition: 100 parts CrOs +1 part sulfuric acid Current density 100-200 ma/em? Temperature 45-60% ‘Anode + Pb-Snor Pb-Snalloy coated with PbO:. Currentefficiency : 812% Applications corrosion resistant and decorative finish on iron objects ELECTROLESS PLATING: It is a technique of depositing a noble metal on a catalytically active surface of less noble metal by employing a suitable reducing agent without using electrical energy. Reducing agent causes reduction of metal ions to metal which gets plated over the catalytically active surface, Metal ions + Reducing agent Metal + Oxidized products ‘The driving force is autocatalytic redox reaction on a pretreated catalytic surface. Preparation of active surface (of the object to be plated): ‘This step is most important in this technique. ‘This is achieved by using one of the following methods . Etching (by acid treatment). i, Electroplating a thin layer of the metal or any other suitable metal. This is usually followed by heat treatment.