Hardness - Multivalent metal ions which will form precipitates with soaps. e.g. Ca 2+ + (soap) Ca(soap) 2 (s)
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1 Water Softening (Precipitation Softening) (3 rd DC 178; 4 th DC 235) 1. Introduction Hardness - Multivalent metal ions which will form precipitates with soaps. e.g. Ca 2+ + (soap) Ca(soap) 2 (s) Complexation reaction a. Caused by ions of Ca 2+ and Mg 2+ - Hardness in water is caused by ions of Ca 2+ and Mg 2+ b. Other hardness constituents: Iron (Fe), manganese (Mn), strontium (Sr), aluminum (Al). - Iron (Fe), manganese (Mn), strontium (Sr), aluminum (Al) also produce hardness. c. Sources - Largely the result of geological formations of the water source. Precipitation : : : : : : : : /// /// Top organic soil - microbial activity /// /// CH 2 O + O 2 CO 2 + H 2 O organics Subsoil CO 2 + H 2 O H 2 CO Limestone formation weathering CaCO 3(s) + H 2 CO 3 Ca(HCO 3 ) 2 MgCO 3(s) + H 2 CO 3 Mg(HCO 3 ) 2 CaCO 3(s) + H + (aq) HCO 3 - (aq) + Ca 2+ (aq) 60 C 15 C 1
2 Types of Hardness with respect to cations (metallic ion) with respect to anions (nonmetallic ion) 1) With respect to cations (metallic ion; Ca 2+, Mg 2+ ) a. Calcium Hardness: Ca(HCO 3 ) 2, CaSO 4, CaCl 2 b. Magnesium Hardness: Mg(HCO 3 ) 2, MgSO 4, MgCl 2 Total Hardness (TH) = Calcium Hardness + Magnesium Hardness 2
3 2) With respect to anions (nonmetallic ion; HCO 3 -, SO4 2-, Cl - ) a. Carbonate Hardness (CH) b. Noncarbonate hardness (NCH) Carbonate Hardness (Temporary Hardness) - heating the water removes it. Calcium bicarbonate Ca(HCO 3 ) 2 Magnesium bicarbonate Mg(HCO 3 ) 2 Carbonate hardness = alkalinity, when alkalinity < TH Carbonate hardness = TH, when alkalinity > TH where TH = total hardness * Alkalinity - measured as the amount of acid required to titrate to PH 4.3. (e.g., HO -, CO 3 2-, HCO 3 - ) Noncarbonate hardness (Permanent hardness) - not removed when water is heated - will not precipitate when the water is boiled Calcium sulfates CaSO 4 Magnesium sulfates MgSO 4 Calcium chlorides CaCl 2 Magnesium chlorides MgCl 2 Total Hardness (TH) = Carbonate Hardness (CH) + Noncarbonate hardness (NCH) d. Expressed in mg/l as CaCO 3 - The sum of calcium and magnesium concentrations expressed in mg/l as CaCO 3. eq. wt of CaCO 3 Hardness (mg/l as CaCO 3 ) = (mg/l of M 2+ ) eq. wt of M 2+ Hardness (mg/l as CaCO 3 ) = (meq/l Ca 2+ + meq/l Mg 2+ ) (ew. wt of CaCO 3 ) (eq. wt of CaCO 3 = 50 mg/meq) Note: EW = equivalent weight, mg/meq meq mg mg = L meq L CaCO 3 Ca 2+ + CO 3 2- CO H + H 2 CO 3 (z = 2) 3
4 Example: Given Ca 2+ = 70 mg/l and Mg 2+ = 9.7 mg/l Determine calcium hardness, magnesium hardness, and total hardness as CaCO 3. (Solutions) EW of Ca 2+ = 20 mg/meq EW of Mg 2+ =12.2 mg/meq EW of CaCO 3 = 50 mg/meq 50 mg/meq CaCO 3 Calcium hardness = (70 mg/l Ca 2+ ) mg/meq Ca 2+ = 175 mg/l hardness as CaCO 3 50 mg/meq CaCO 3 Magnesium hardness = (9.7 mg/l Mg 2+ ) mg/meq Mg 2+ = 40 mg/l hardness as CaCO 3 Total hardness = ( ) = 215 mg/l as CaCO 3 Example: Given Ca 2+ = 3.5 meq/l and Mg 2+ = meq/l. Determine total hardness as CaCO 3. (Solution) Total hardness = (3.5 meq/l meq/l) (50 mg/meq CaCO 3 ) = 215 mg/l as CaCO 3 Hard Water Classification Table 3-13 (DC 179); Table 4-14 (4 th DC 236) Hardness Range Description mg/l as CaCO Soft Moderately hard Hard >300 Very Hard
5 Hardness >300 mg/l as CaCO 3 is considered excessive for public water supply - results in a. high soap consumption b. scale in heating vessels and pipes Mg 2+ in excess of ~40 mg/l as CaCO 3 forms scale on heat exchange elements in hot water heaters Goal of water treatment (softening) is mg/l as CaCO 3 (3 rd DC, 179) From other literature a. High (excessive) hardness >300 mg/l as CaCO 3 b. Hard mg/l as CaCO 3 ( mg/l as CaCO 3) c. Moderate hardness mg/l as CaCO 3 ( mg/l as CaCO 3) - is considered moderately hard d. Soft 0-75 mg/l as CaCO 3 e. Acceptable mg/l as CaCO 3 - acceptable for a public water supply - but magnesium content should not exceed 40 mg/l as CaCO Chemistry of Water Softening Lime-soda ash processes a. The lime-soda ash water-softening process uses: Lime, Ca(OH) 2 (or CaO) and Soda ash, Na 2 CO 3 to precipitate hardness as: Calcium carbonate, CaCO 3(s) Magnesium hydroxide, Mg(OH) 2(s) b. Chemical reactions: a. CO 2 - is not hardness but it consumes lime and must therefore be considered in calculating the amount required. CO 2 + Ca(OH) 2 CaCO 3(s) + H 2 O (1) 5
6 b. Carbonate hardness - is precipitated by lime. Ca(HCO 3 ) 2 + Ca (OH) 2 2CaCO 3 (s) + 2H 2 O (2) Mg(HCO 3 ) 2 + Ca(OH) 2 CaCO 3 (s) + MgCO 3 + 2H 2 O (3) MgCO 3 + Ca(OH) 2 Mg (OH) 2 (s) + CaCO 3 (s) (4) Note: - 1 mole of lime is needed for each mole of calcium bicarbonate (Rxn 2) - 2 moles of lime are required for each mole of magnesium bicarbonate (Rxns 3 and 4). c. Noncarbonate hardness - requires the addition of soda ash for precipitation MgSO 4 + Ca(OH) 2 Mg(OH) 2(s) + CaSO 4 (5) CaSO 4 + Na 2 CO 3 CaCO 3(s) + Na 2 SO 4 (6) MgCl 2 + Ca(OH) 2 Mg(OH) 2(s) + CaCl 2 (7) CaCl 2 + Na 2 CO 3 CaCO 3(s) + 2 NaCl (8) Note: - 1 mole of lime Ca(OH) 2 and 1 mole of soda ash Na 2 CO 3 are needed to each mole of MgSO 4 or MgCl 2-1 mole of soda ash Na 2 CO 3 is needed to each mole of CaSO 4 or CaCl 2 Solubility of CaCO 3(s) and Mg(OH) 2(s) - Precipitation softening cannot produce water completely free of hardness because of: a. Solubility of CaCO 3(s) and Mg(OH) 2 (s) = (0.6 meq/l of CaCO 3 ) + (0.2 meq/l of Mg(OH) 2 ) = (30 mg/l CaCO 3 ) + (10 mg/l of Mg(OH) 2 as CaCO 3 ) Total limiting hardness = 40 mg/l as CaCO 3 6
7 - The minimum practical limits of precipitation softening = 30 mg/l of CaCO 3 and10 mg/l of Mg(OH) 2 expressed as CaCO 3 Goal is mg/l hardness as CaCO 3 Deviations from the theoretical hardness removal by the lime-soda ash treatment. - Limited completion of the chemical reactions by physical considerations; e.g., inadequate mixing, limited detention time in settling basins Advantages of Lime-Soda ash Softening a. Hardness is taken out of solution b. Lime added is also removed. - when soda ash is applied, Na + remains in the finished water. - noncarbonate hardness requiring soda ash is generally a small portion of the total hardness. c. TDS (total dissolved solids) is reduced - Lime also precipitates the soluble Fe and Mn - TDS may be significantly reduced. d. Disinfection - Excess lime treatment provides disinfection e. Aids in coagulation - Excess lime treatment provides aids in coagulation for removal of turbidity Schemes of lime-soda ash softening - three different basic schemes may be used to provide a finished water with the desired hardness. a. Excess lime treatment b. Selective calcium removal c. Split treatment 7
8 Excess Lime Treatment 1) Carbonate hardness associated with Ca 2+ can be effectively removed to the practical limit of CaCO 3 solubility (30 mg/l) by stoichiometric additions of lime. Ca(HCO 3 ) 2 + Ca(OH) 2 2CaCO 3(s) + 2H 2 O 2) Precipitation of Mg 2+ calls for a surplus of approximately 1.25 meq/l (30 mg/l) of CaO above stoichiometric requirements. 3) The practice of excess-lime treatment reduces the total hardness to about 40 mg/l as CaCO 3 i.e., 30 mg/l of CaCO 3 as CaCO 3 10 mg/l of Mg(OH) 2 as CaCO 3 4) After excess-lime treatment, the water is scale forming and must be neutralized to remove caustic alkalinity (OH - ). - Recarbonation and soda ash are regularly used to stabilize the water 5) CO 2 neutralizes excess lime as follows: Ca(OH) 2 + CO 2 CaCO 3(s) + H 2 O excess lime - this reaction precipitates calcium hardness and reduces the ph from near 11 to about ) Further recarbonation of the clarified water converts a portion (say 1/2) of the remaining carbonate ions to bicarbonate by the reaction. CaCO 3(s) + CO 2 + H 2 O Ca(HCO 3 ) 2 - the final ph is in the range 9.5 to 8.5, depending on the desired carbonate to bicarbonate ratio. 8
9 Bar Diagram (Bar Graph) - purpose is to visualization of the chemical composition - data may be expressed in meq/l (milliequivalents per liter). a) Top row of the bar graph consists of major cations arranged in the order of Ca 2+, Mg 2+, Na +, K +. b) Bottom row of the aligned in the sequence of OH, CO 3 2, HCO 3, SO 4 2, Cl -, NO 3 -. c) The sum of the positive meq/l must equal the sum of the negative meq/l for a given water sample in equilibrium. Ion Balance or I Cations - Anions l Charge Balance = x 100 Cations + ΣAnions < 5% OK Example: WATER SOFTENING - Excess Lime Treatment The water defined by the analysis given below is to be softened by excess lime treatment in a two-stage system. Given chemical Analysis Data: CO 2 = 8.8 mg/l; Ca 2+ =70.0 mg/l; Mg 2+ = 9.7 mg/l; Na + = 6.9 mg/l; HCO 3 =115.0 mg/l as CaCO 3 ; SO 4 2- = 96.0 mg/l; Cl = 10.6 mg/l 1. Sketch a bar graph for: a) the raw water, b) softened water after chemical addition and settling, but before recarbonation and filtration, c) softened water after 1 st stage recarbonation, d) softened water after 2 nd stage recarbonation and filtration assuming that one-half of the alkalinity is in the bicarbonate form. 2. List the hypothetical combinations of chemical compounds in the raw water. 3. Calculate the quantity of softening chemicals required in lb/mg of water. 4. Calculate the theoretical quantity of CO 2 needed to provide finished water with ½ of the alkalinity converted to bicarbonate ion. 9
10 (SOLUTIONS) 1. Express the concentrations in meq/l a. Sketch a meq/l bar graph for the raw water. b. Species Conc. (mg/l) MW (g/mol) z MW/z = eq.wt (mg/meq) mg/l = meq/l mg/meq Total (meq/l) CO Cations Ca Mg Na Anions HCO 3 (as Ca CO 3 ) SO Cl b. Check ion balance Ion Balance or I ΣCations - ΣAnions l Charge Balance = x 100 ΣCations + ΣAnions I l = x 100 = 0.05 % < 5% Ion Balance is OK Sketch a bar graph for the raw water. - See the bar graph below: 1) Raw water 3. Calculate the softening chemicals required. 1) List the combination and concentration (meq/l) of chemical compounds from the bar graph (Raw water) Compound (meq/l) CO Ca(HCO 3 ) CaSO MgSO NaCl
11 Lime Required CO 2 : CO 2 + Ca(OH) 2 CaCO 3(s) + H 2 O (1) Ca(HCO 3 ) 2 : Ca(HCO 3 ) 2 + Ca (OH) 2 2CaCO 3 (s) + 2H 2 O (2) MgSO 4: MgSO 4 + Ca(OH) 2 Mg(OH) 2(s) + CaSO 4 (5) (meq/l) Soda Ash Required CaSO 4 : CaSO 4 + Na 2 CO 3 CaCO 3(s) + Na 2 SO 4 (6) Raw water Produced w/lime (meq/l) Calculate eq.wt of lime and soda ash MW z eq.wt (mg/meq) Quick Lime CaO Soda Ash Na 2 CO Lime (as CaO) required = stoichiometric requirement + excess lime = (3.5 meq/l)(28 mg/meq) + (1.25 meq/l)(28 mg/meq) = 133 mg/l CaO = (133 mg/l)(8.34 lb/mg per mg/l) = 1100 lb/mg Soda ash required = (2.0 meq/l)(53 mg/meq) = 106 mg/l Na 2 CO 3 = (106 mg/l)(8.34 lb/mg per mg/l) = 884 lb/mg 11
12 (c) Sketch an meq/l bar graph for the water after lime and soda ash additions and settling, but before recarbonation 1) Calculate solubilities (in meq/l) mg/l eq.wt (mg/meq) meq/l CaCO 3 as Ca CO Mg(OH) 2 as Ca CO After the addition of softening chemicals CATIONS (meq/l) Ca 2+ Excess lime, Ca(OH) Ca 2+ Solubility of Ca CO Mg 2+ Solubility of Mg(OH) Na + Present in raw water 0.3 Na + From Na 2 CO 3 added 2.0 M +, not including excess lime 3.1 ANIONS (meq/l) OH - Excess lime, Ca(OH) OH - Solubility of Mg(OH) CO 3 2- SO 4 Solubility of Ca CO Present in raw water 2.0 Cl - Present in raw water 0.3 M -, not including excess lime 3.1 See the bar graph (2) Recarbonation 1) converts the excess OH to CO 3 2 Ca(OH) 2 + CO 2 CaCO 3(s) + H 2 O Excess OH = OH from excess lime + OH from Mg(OH) 2 = 1.25 meq/l meq/l = 1.45 meq/l 1.45 meq 22 mg = ( CO 2 ) = 31.9 mg/l of CO 2 L meq - Draw a bar graph for the softened water after recarbonation and filtration assuming that one-half of the alkalinity is in the bicarbonate form. See the bar graph (3) 12
13 2) After second-stage processing, final recarbonation convert ½ of remaining CO 3 2 to HCO 3 - CaCO 3 + CO 2 + H 2 O Ca(HCO 3 ) MgCO 3 + CO 2 + H 2 O Mg(HCO 3 ) mg (½)(0.8 meq/l)( CO 2 ) = 8.8 mg/l of CO 2 meq Total CO 2 Reacted = = 40.7 mg/l = 40.7 mg/l (8.34 lb/mg per mg/l) = 340 lb CO 2 / MG (d) Draw a bar graph for the softened water after recarbonation and filtration. CATIONS (meq/l) Ca 2+ Solubility of Ca CO Mg 2+ Solubility of Mg(OH) Na + Present in raw water + From Na 2 CO added ΣM +, not including excess lime 3.1 ANIONS (meq/l) 2- CO 3 Solubility of Ca CO HCO 3 - From Ca(HCO 3 ) 2 and Mg(HCO 3 ) SO 4 Present in raw water 2.0 Cl - Present in raw water 0.3 ΣM -, not including excess lime
14 14 9-Softning_F12
15 A single-stage calcium carbonate softening plant A two-stage excess lime softening plant 15
16 A split-treatment softening plant CO 2 Homework #7 is due one week from today! 16
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