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Water Softening (Precipitation Softening) (3rd DC 178; 4th DC 235) 1. Introduction Hardness - Multivalent metal ions which will form precipitates with soaps. e.g. Ca2+ + (soap)

Ca(soap)2 (s)

Complexation reaction
2+ a. Caused by the ions of Ca2+ and Mg 2+ - Hardness in water is caused by the ions of Ca and Mg2+

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 /// /// CH2O + O2 CO2 + H2O organics -----------------------------------------------------------------Subsoil CO2 + H2O H2CO3 -----------------------------------------------------------------Limestone formation weathering CaCO3(s) + H2CO3 MgCO3(s) + H2CO3 Ca(HCO3)2 Mg(HCO3)2

CaCO3(s) + H+(aq)

HCO3-(aq) + Ca2+(aq)

60 C

15 C

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Types of Hardness with respect to cations (metallic ion) with respect to anions (nonmetallic ion) 1) With respect to cations (metallic ion; Ca2+, Mg2+) a. Calcium Hardness: b. Magnesium Hardness: Ca(HCO3)2, CaSO4, CaCl2 Mg(HCO3)2, MgSO4, MgCl2

Total Hardness (TH) = Calcium Hardness + Magnesium Hardness

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2) With respect to anions (nonmetallic ion; HCO3 , a. Carbonate Hardness (CH) b. Noncarbonate hardness (NCH)

SO42-,

Cl )

Carbonate Hardness (Temporary Hardness) - heating the water removes it. Calcium bicarbonate Magnesium bicarbonate Ca(HCO3)2 Mg(HCO3)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 Magnesium sulfates Calcium chlorides Magnesium chlorides CaSO4 MgSO4 CaCl2 MgCl2

Total Hardness (TH) = Carbonate Hardness (CH) + Noncarbonate hardness (NCH)

d. Expressed in mg/L as CaCO3.

- The sum of calcium and magnesium concentrations expressed in mg/L as CaCO3.

eq. wt of CaCO3 Hardness (mg/L as CaCO3) = (mg/L of M2+) -----------------------eq. wt of M2+ Hardness (mg/L as CaCO3) = (meq/L Ca2+ + meq/L Mg2+) (ew. wt of CaCO3) (eq. wt of CaCO3 = 50 mg/meq)
Note: CaCO3 Ca
2+

+ CO3

2-

CO3

2-

2H

H2CO3

(z = 2)

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Example: Given Ca2+ = 70 mg/L and Mg2+ = 9.7 mg/L Determine calcium hardness, magnesium hardness, and total hardness as CaCO3. (Solutions) EW = equivalent weight EW of Ca2+ = 20 mg/meq EW of Mg2+ =12.2 mg/meq EW of CaCO3 = 50 mg/meq 50 mg/meq CaCO3 Calcium hardness = (70 mg/L Ca2+) --------------------------20 mg/meq Ca2+ = 175 mg/L hardness as CaCO3 50 mg/meq CaCO3 Magnesium hardness = (9.7 mg/L Mg ) --------------------------12.2 mg/meq Mg2+
2+

= 40 mg/L hardness as CaCO3 Total hardness = (175 + 40) = 215 mg/L as CaCO3

Example: (Solution)

Given Ca2+ = 3.5 meq/L and Mg2+ = 0.795 meq/L. Determine total hardness as CaCO3.

Total hardness = (3.5 meq/L + 0.795 meq/L) (50 mg/meq CaCO3) = 215 mg/L as CaCO3

Hard Water Classification Table 3-13 (DC 179); Table 4-14 (4th DC 236) Hardness Range Description mg/L as CaCO3 -------------------------------------------------------------0 - 75 Soft 75 -100 Moderately hard 100 - 300 Hard >300 Very Hard -------------------------------------------------------------4

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Goal of water treatment is 75120 mg/L as CaCO3

(3rd DC, 179)

Hardness >300 mg/L as CaCO3 is considered excessive for public water supply - results in a. high soap consumption b. scale in heating vessels and pipes Mg2+ in excess of ~40 mg/L as CaCO3 forms scale on heat exchange elements in hot water heaters

From other literature -------------------------------------------------------------------------------------------a. High (excessive) hardness >300 mg/L as CaCO3 b. Hard c. Moderate hardness 150 - 300 mg/L as CaCO3 (100 - 300 mg/L as CaCO3) 60-120 mg/L as CaCO3 (75 -150 mg/L as CaCO3) - is considered moderately hard 0 - 75 mg/L as CaCO3 80-100 mg/L as CaCO3

d. Soft e. Acceptable

- acceptable for a public water supply - but magnesium content should not exceed 40 mg/L as CaCO3 --------------------------------------------------------------------------------------------

2. 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, Na2CO3 to precipitate hardness as: Calcium carbonate, CaCO3(s) Magnesium hydroxide, Mg(OH)2(s) b. Chemical reactions: a. CO2
- is not hardness but it consumes lime and must therefore be considered in calculating the amount required.

CO2 + Ca(OH)2 CaCO 3(s) + H2O

(1)

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b. Carbonate hardness
- is precipitated by lime.

Ca(HCO3)2 + Ca (OH)2 2CaCO3 (s) + 2H2O Mg(HCO3)2 + Ca(OH)2 CaCO3 (s) MgCO3 + MgCO3 + 2H2O

(2) (3) (4)

+ Ca(OH)2 Mg (OH)2 (s) + CaCO 3 (s)

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) + CaSO4 CaSO4 + Na2CO3 CaCO 3(s) MgCl 2 + Ca(OH) 2 Mg(OH) 2(s) CaCl2 + Na2CO3 CaCO 3(s) Note: - 1 mole of lime Ca(OH)2 and 1 mole of soda ash Na2CO3 are needed to each mole of MgSO4 or MgCl 2 - 1 mole of soda ash Na2CO3 is needed to each mole of CaSO4 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 CaCO3(s) and Mg(OH)2 (s) = (0.6 meq/L of CaCO3)+(0.2 meq/L of Mg(OH)2) = (30 mg/L CaCO3) + (10 mg/L of Mg(OH) 2 as CaCO3) Total limiting hardness = 40 mg/L as CaCO3
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(5) (6) (7) (8)

+ Na2SO4 + CaCl2 + 2 NaCl

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- The minimum practical limits of precipitation softening = 30 mg/L of CaCO 3 and10 mg/L of Mg(OH)2 expressed as CaCO3 Goal is 75 120 mg/L hardness as CaCO3 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 is reduced - Lime also precipitates the soluble Fe and Mn - TDS (total dissolved solids) 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

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Excess Lime Treatment 1) Carbonate hardness associated with Ca2+ can be effectively removed to the practical limit of CaCO3 solubility (30 mg/L) by stoichiometric additions of lime. Ca(HCO3)2 + Ca(OH)2 2CaCO3(s) + 2H2O

2) Precipitation of Mg2+ 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 CaCO3 i.e., 30 mg/L of CaCO3 as CaCO3 10 mg/L of Mg(OH)2 as CaCO3 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) CO2 neutralizes excess lime as follows: Ca(OH) 2 + excess lime CO2 CaCO3(s) + H2O

- this reaction precipitates calcium hardness and reduces the pH from near 11 to about 10.2.

6) 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 + H2O Ca(HCO3) 2

- the final pH is in the range 9.5 to 8.5, depending on the desired carbonate to bicarbonate ratio.

Bar Diagram (Bar Graph) - purpose is to visualization of the chemical composition - data can be expressed in meq/L (milliequivalents per liter). a. Top row of the bar graph consists of major cations arranged in the order of Ca2+, Mg2+, Na+, K+. b. Bottom row of the aligned in the sequence of OH, CO32, HCO3 , SO42, Cl-, NO3-. c. The sum of the positive meq/L must equal the sum of the negative meq/L for a water in equilibrium.
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Ion Balance or I GCations - G Anions l Charge Balance = ---------------------------------- x 100 GCations + GAnions < 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: CO2 = 8.8 mg/L; Ca 2+ =70.0 mg/L; Mg2+ = 9.7 mg/L; Na+ = 6.9 mg/L; HCO3 =115.0 mg/L as CaCO3; SO42- = 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 1st stage recarbonation, d) softened water after 2nd 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 CO2 needed to provide finished water with of the alkalinity converted to bicarbonate ion.

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(SOLUTIONS) 1. Express the concentrations in meq/L

a. Sketch a meq/L bar graph for the raw water. Species Conc. MW z MW/z = eq.wt (mg/L) (g/mol) (mg/meq) CO2 Cations Ca 2+ Mg2+ Na
+

mg/L ------------ = meq/L G(meq/L) mg/meq 0.4 3.5 0.795 0.3 2.3 2.0 0.3 4.6 4.595 0.4

8.8 70.0 9.7 6.9 115 96.0 10.6

44 40.1 24.3 23.0 100 96.0 35.5

2 2 2 1 2 2 1

22.0 20.0 12.2 23.0 50.0 48.0 35.3

Anions HCO3 (as Ca CO3) SO4 2 Cl

b. Check ion balance Ion Balance or I GCations - G Anions l Charge Balance = --------------------------------- x 100 GCations + GAnions I 4.595 - 4.6 l = ----------------------- x 100 = 0.05 % < 5% 4.595 + 4.6 Ion Balance is OK

2. 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 CO2 Ca(HCO3)2 CaSO4 MgSO 4 NaCl (meq/L) 0.4 2.3 1.2 0.8 0.3

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Lime Required CO2: CO2 0.4 + Ca(OH)2 0.4 CaCO 3(s) + H2O (1)

Ca(HCO3)2: Ca(HCO3)2 + Ca (OH)2 2.3 2.3 MgSO 4:

2CaCO3 (s) + 2H2O (2)

MgSO 4 + Ca(OH) 2 Mg(OH) 2(s) + CaSO4 (5) 0.8 0.8 0.8 -------------------------------------------------------------------------------(meq/L) 3.5 3.5

Soda Ash Required CaSO4: CaSO4 + Na2CO3 CaCO 3(s) + Na2SO4 Raw water 1.2 1.2 Produced w/Lime 0.8 0.8 ______________________________________________ (meq/L) 2.0 2.0 (6)

Calculate eq.wt of lime and soda ash MW Quick Lime Soda Ash CaO Na2CO3 106 z eq.wt (mg/meq) 28.0 53.0 2

56.1 2

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 Na2CO3 = (106 mg/L)(8.34 lb/MG per mg/L) = 884 lb/MG

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(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 CaCO3 as Ca CO3 Mg(OH)2 as Ca CO3 30 10 50 50 0.6 0.2

After the addition of softening chemicals

CATIONS Ca
2+ 2+

(meq/L) Excess lime Solubility of Ca CO3 Solubility of Mg(OH) 2 Present in raw water From Na2CO3 added 3M+, not including excess lime Excess lime Solubility of Mg(OH) 2 Solubility of Ca CO3 Present in raw water Present in raw water 3M , not including excess lime 1.25 0.6 0.2 0.3 2.0 3.1 (meq/L) 1.25 0.2 0.6 2.0 0.3 3.1

Ca Mg2+ Na+ Na
+

ANIONS OH OHCO32SO4 2Cl-

Recarbonation 1) converts the excess OH to CO32 Ca(OH)2 + CO2 CaCO3(s) + H2O

Excess OH = OH from excess lime + OH from Mg(OH) 2 = 1.25 meq/L + 0.2 meq/L = 1.45 meq/L 1.45 meq 22 mg = --------------- (---------- CO2 ) = 31.9 mg/L of CO2 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.
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2) After second-stage processing, final recarbonation convert of remaining CO32 to HCO3CaCO 3 + CO 2 + H2O 0.6 0.6 MgCO 3 + CO 2 + H2O 0.2 0.2 Ca(HCO3) 2 Mg(HCO3) 2

22 mg ()(0.8 meq/L)(--------- CO2 ) = 8.8 mg/L of CO2 meq Total CO2 Reacted = 31.9 + 8.8 = 40.7 mg/L = 40.7 mg/L (8.34 lb/MG per mg/L) = 340 lb CO2 / MG

(d) Draw a bar graph for the softened water after recarbonation and filtration.
CATIONS Ca 2+ Mg2+ Na+ Solubility of Ca CO3 Solubility of Mg(OH) 2 Present in raw water + From Na2CO3 added + 3M , not including excess lime (meq/L) 0.6 0.2 2.3 3.1 (meq/L) 0.4 0.4 2.0 0.3 3.1

ANIONS CO32HCO3SO4 2ClSolubility of Ca CO3 From Ca(HCO3) 2 and Mg(HCO3) 2 Present in raw water Present in raw water 3M-, not including excess lime

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A single-stage calcium carbonate softening plant

A two-stage excess lime softening plant

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A split-treatment softening plant

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