WATERSOFTENING

HARDNESS Definedasthesumofallpolyvalentcations(i.e.,major:calciumand magnesium, and minor: iron, manganese, strontium and aluminium), however they are not present in significant quantities innaturalwater. Water hardness is largely the result of geological formation of the watersource.Thecommonunitsofexpressionaremg/LasCaCO3or meq/L. Many people object to water containing hardness more than 150 mg/L as CaCO3. A common water treatment goal is to provide water withhardnessintherangeof75to120mg/LasCaCO3. Hardness of 200500 mg/L as CaCO3 is considered excessive for a water supply and results in high soap consumption as well as objectionscaleinheatingvesselsandpipes. Theclassificationofwaterhardnessisasfollow: 075 =soft, 75150 =moderatelyhard, 150300 =hard, >300 =veryhard,allunitasmg/LasCaCO3.
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 The natural process by which water becomes hard is shown schematically in Figure 1. As rainwater enter the topsoil, the respiration of microorganisms increases the CO2 content of the water. The CO2 reacts with the water to form H2CO3. Limestone, which is madeupof solid CaCO3 andMgCO3,reactswiththecarbonicacidto form bicarbonates of Calcium and Magnesium [Ca(HCO3)2 and Mg(HCO3)2]respectively. While CaCO3 and MgCO3 are both insoluble in water, the bicarbonatesarequitesoluble. GypsumCaSO4and MgSO4mayalsogointosolution tocontributeto thehardness. Since Calcium and magnesium predominate, it is often convenient in performing softening calculations to define the total hardness (TH) ofawaterasthesumofelements TH=Ca2++Mg2+ Where the concentration of each elements in units of mg/L as CaCO3ormeq/L. Totalhardnessisoftenbrokendownintotwocomponents: 1. That associated with the HCO3 anion (called carbonate hardness (CH),and 2. That associated with other anions (called noncarbonate hardness(NCH).Totalhardnessmayalsobedefinedas

TH=CH+NCH

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 Carbonate hardness is defined as the amount of hardness equal to thetotalhardnessorthetotalalkalinity,whicheverisless. Carbonate hardness is often called temporary hardness because heatingthewaterremovesit. When pH is less than 8.3, HCO3 is the dominant form of alkalinity, andthealkalinityistakentobeequaltotheconcentrationofHCO3 Noncarbonate hardness is defined as the total hardness in excess ofthealkalinity. If the alkalinity is equal to or greater than the total hardness, then thereisnononcarbonatehardness. Noncarbonate hardness is called permanent hardness because it is notremovedwhenwaterisheated.
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Bar charts of water composition are often useful in understanding the process of softening. The bar is constructed with cation (i.e., Ca, Mg, Na andK)intheupperbarandanions(i.e.,HCO3,SO4andCl)inthelowerbar. Rain v v v v v v v Topsoil BacterialAction>CO2 Subsoil v v v v v CO2+H2O>H2CO3 v____v_____v_____v_____v____v____v Limestone CaCO3(s)+H2CO3Ca(HCO3)2

Example: Given the following analysis of a ground water, constructed a bar chartoftheconstituents,expressedasmg/LofCaCO3ormeq/L.
________________________________________________________________________ mg/L as Ca CO3 meq/L Ion mg/L as ion EW Ca CO3 /EW ion

Ca2+ 103 Mg2+ 5.5 Na+ 16 HCO3255 SO4249 Cl 37

2.50 4.12 2.18 0.82 1.04 1.41

258 23 35 209 51 52

5.15 0.45 0.70 4.18 1.02 1.03

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Solution: 0.0 Ca2+ HCO3 0.0

4.18

5.15 5.60 Mg2+ Na+ SO42 5.20

6.30 Cl 6.23

The concentration of the ions has been converted to CaCO3 equivalent and theresultsareplottedinabovefigure. The total cat ions 316 mg/L as CaCO3, of which 281 mg/L as CaCO3 is hardness, the total anions 312 mg/L (i.e. less than 316 mg/L due to other ions which were not analyzed.) of which the carbonate hardness is 209 mg/L as CaCO3. Therefore the non carbonate hardness should be 72 mg/L asCaCO3(NCH=THCHor281209=72). The relationship between the total hardness, carbonate hardness and non carbonate hardness are illustrated in Figure 3.14. In Figure 3.14a, the total hardness is 250 mg/L as CaCO3, the carbonate hardness equal to the alkalinity (HCO3 = 200mg/L as CaCO3), and the noncarbonate hardness equal to the difference between the total harness and the carbonate hardness(NCH=THCH=250200=50mg/LasCaCO3). In Figure 3.14b, the total harness is again 250 mg/L as CaCO3. However, since the alkalinity (HCO3) is greater than the total hardness, and since the carbonate hardness cannot be greater than the total hardness, the carbonate hardness is equal to the total hardness that is 250 mg/L as CaCO3. Therefore there is no noncarbonate hardness. Note that in both cases it may be assumed that the pH is less than 8.3 because HCO3 is the onlyformofalkalinitypresent.
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TableEquilibriumofsolidanddissolvedspeciesofcommonions Mineral Formula Solubility mg/LCaCO3 Calciumbicarbonate Ca(HCO3)2 1,620 CalciumCarbonate CaCO3 15 336,000 CalciumChloride CaCl2 1,290 Calciumsulfate CaSO4 2,390 Calciumhydroxide Ca(OH)2 37,100 Magnesium Mg(HCO3)2 bicarbonate 101 MagnesiumCarbonate MgCO3 362,000 MagnesiumChloride MgCl2 17 Magnesiumhydroxide Mg(OH)2 170,000 Magnesiumsulfate MgSO4 38,700 Sodiumbicarbonate NaHCO3 61,400 SodiumCarbonate Na2CO3 SodiumChloride Na Cl 225,000 Sodiumhydroxide Na OH 370,000 Sodiumsulfate Na2SO4 33,600
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Example: Waterhasanalkalinityof200mg/LasCaCO3.TheCa2+concentrationis160 mg/Lastheion,andtheMg2+concentrationis40mg/Lastheion.ThepHis 8.1.Findthetotal,carbonate,andnoncarbonatehardness. Solution: TheMWofCaandMgare40and24respectively,withbothhaveavalency of2andthustheEWofCaandMgare20and12mg/meqrespectively.EW forCaCO3is50mg/meq. TH=160mg/L(50mg/meq)+40mg/L(50mg/meq)=567mg/LasCaCO3 (20mg/meq)(12mg/meq) In this case, the alkalinity is less than the total hardness; the carbonate hardness (CH) is equal to 200 mg/L as CaCO3. The noncarbonate hardness (NCH)isequaltothedifference NCH=THCH =567200=367mg/LasCaCO3 NotethatwecanaddorsubtractconcentrationofCa2+orMg2+ifthereare inequivalentunit,forexample,moles/L,mg/Lormillequivalents/L.
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LIMESODASOFTENING The limesoda water softening process uses lime, Ca (OH)2 and soda ash,Na2CO3,toprecipitatehardnessfromsolution. Carbon dioxide and carbonate hardness (calcium and Magnesium bicarbonate)arecomplexedbylime. Noncarbonate hardness (Calcium and magnesium sulfates, chlorides andnitrates)requiresadditionofsodaashforprecipitation. In order to precipitate CaCO3, the pH of the water must be raised to about 10.3. To precipitate magnesium, the pH must be raised to about11.0 Mg is more expensive to remove, so we leave as much Mg 2+ in the wateraspossible. Similarly,thereismoreexpensivetoremovenoncarbonatehardness because we must add another chemical (soda ash). Therefore, we leaveasmuchnoncarbonatehardnessinthewateraspossible. Thecommonsourceofhydroxylioniscalciumhydroxide[Ca(OH)2].It is cheaper to use quicklime (CaO), commonly called lime, than hydratedlime[Ca(OH)2]. The quicklime is converted to hydrated lime in the water treatment plant by mixing CaO and water to produce a slurry of [Ca (OH)2]. The conversionprocessiscalledslaking.
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 i. 1. In order to raise the pH, we must first neutralize any free acids that may be presented in the water. CO2 is the principal acid present in unpolluted,naturallyoccurringwater. Notedthatnohardnessisremovedinthisstep. In order to precipitate CaCO3 we have to raise the pH to about 10.3. Toachievethiswemustconvertallofthebicarbonateto carbonate. 3. Precipitationofcarbonatehardnessduetomagnesium Inordertoremove carbonatehardness dueto magnesium, we must addmorelimetoincreasethepHtoabout11. Thereactionmaybeconsideredtooccurintwostages Note that the hardness of the water did not change because MgCO3issoluble.
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CHEMICALREACTIONSINTHELIMESODAPROCESSARE:

CO2+Ca(OH)2=CaCO3v+H2O

2. Precipitationofcarbonatehardnessduetocalcium

Ca(HCO3)2+Ca(OH)2=2CaCO3v+2H2O

Mg(HCO3)2+Ca(OH)2=CaCO3v+MgCO3+H2O

 With the addition of more lime the hardness due to magnesiumisremoved. MgCO3+Ca(OH)2=Mg(OH)2v+CaCO3v

4. Removalofnoncarbonatehardnessduetocalcium If we need to remove noncarbonate hardness due to calcium, nofurtherincreaseinpHisrequired. We must provide additional carbonate in the form of soda ash (Na2CO3). Ca2+(SO4,ClandNO3)+Na2CO3=CaCO3v+2Na+(SO4,ClandNO3) 5. RemovalofnoncarbonatehardnessduetoMagnesium If we need to remove noncarbonate hardness due to Magnesium,wewillhavetoaddbothlimeandsodaash. MgSO4[Cl,(NO3)]+Ca(OH)2=Mg(OH)2v+CaSO4[Cl,(NO3)] Note that although the magnesium is removed, there is no changeinhardnessbecausecalciumisstillinthesolution. Toremovethecalciumwemustaddsoda CaSO4[Cl,(NO3)]+Na2CO3=CaCO3v+Na2SO4[Cl,(NO3)] Note that is the same as the one to remove noncarbonate hardnessduetocalcium.
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ii.

PROCESSLIMITATION(EXCESSLIMEAPPROACH) Lime soda softening cannot produce a water at completely free of hardnessbecauseofthesolubility(little)ofCaCO3andMg(OH)2.Thus the minimum calcium hardness can be achieved is about 30 mg/L as CaCO3, and the magnesium hardness is about 10 mg/L as CaCO3. we normally tolerate a final total hardness on the order of 75 to 120 mg/L as CaCO3, but the magnesium content should not exceed 40 mg/L as CaCO3 ( because a greater hardness of magnesium forms scalesonheatexchangeelements).

Notes: a) For Mg removal less than 20 mg/L as CaCO3, the basic excess lime (20mg/LasCaCO3)issufficient. b) For Mg removal of 20 to 40 mg/L as CaCO3, we must add excess limeequaltotheMgtoberemoved(e.g.25.8mg/LofMg2+,thus theexcesslimeshouldbe25.8mg/L). c) For Mg removal of more than 40 mg/L as CaCO3, we need to add excesslimeof40mg/LasCaCO3). In order to achieve reasonable removal of hardness in a reasonable time period, an excess of Ca(OH)2 beyond the stoichiometric limit usually implemented. Based on empirical experience, a minimum excessof20mg/LofCa(OH)2expressedasCaCO3mustbeprovided. There are several advantages of lime softening in water treatment: the total dissolved solids are dramatically reduced, hardness is taken out of solution, and the lime added also removed. Lime also precipitates soluble iron (i.e., Fe 2+) and manganese often found in ground water. In processing surface waters, excess lime treatment providesdisinfectionandaidsincoagulationforremovalofturbidity.
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Example:ExcessLime Water defined by the following analysis is to be softened by excess lime treatment. Assume that the practical limit of hardness removal forCaCO3is30mg/L,andthatofMg(OH)2is10mg/LasCaCO3. Parameter(cations) CO2=8.8mg/L Ca2+=40.0mg/L Mg2+=14.7mg/L Na+=13.7mg/L a) Sketch a meq/L bar graph, and list the hypothetical combinations ofchemicalscompoundinsolution. b) Determine the calcium, magnesium and total hardness as CaCO3. Carbonateandnoncarbonatehardness. c) Calculate the chemicals softening required, expressing lime dosageasCaOandsodaashasNa2CO3. d) Draw a bar graph for the softened water before and after carbonation.Assume that half the alkalinity in the softened water isthebicarbonateform. Solution: Component Concentration Equivalent Meq/L mg/L Weight CO2 8.8mg/L 22.0 0.40 2+ Ca 40.0mg/L 20.0 2.00 2+ Mg 14.7mg/L 12.2 1.21 + Na 13.7mg/L 23.0 0.60 Totalcations 3.81 Alk(HCO3 ) 135.0mg/L 50.0 2.70 2 SO4 29.0mg/L 48.0 0.60 Cl 17.8mg/L 35.0 0.51 Totalanions 3.81
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Parameter(anions) Alk(HCO3)=135mg/LasCaCO3 SO42 =29.0mg/L Cl =17.8mg/L

 0.4 0.0 CO2 0.4 a) From the meq/L bar graph the hypotheticals combination are Ca (HCO3)2 2.0 meq/L, Mg (HCO3)2 0.70, Mg SO4 0.51, Na2SO4 0.09, andNaCl,0.51meq/L. b) Calcium hardness 2.0 x 50 = 100 mg/L as CaCO3 and magnesium hardness = 1.21 x 50 = 60.5 mg/L as CaCO3 or Total hardness = 160.5mg/LasCaCO3.Carbonatehardness2.7x50=135.0 mg/L. Noncarbonatehardness=0.51x50=25.5mg/L. c) Chemical required: The required lime dosage equals the amount needed for the softening reactions 1.25 meq/L (35 mg/L) CaO of excesslimetoparticipatethemagnesium. Dosageoflime =4.31x28+35=156mg/LCaO. Dosageofsodaash =0.51x53=27mg/LNa2CO3. Component CO2 Ca(HCO3)2 Mg(HCO3)2 MgSO4 Totalrequired d) The hypothetical bar graph after excess lime treatment is shown below: The dashed box to the left of zero is the excess lime (1.25 meq/L CaO) added to increase the pH high enough to precipitate the Mg (OH)2. The practical limit of 0.6 meq/L Ca 2+ (30 mg/L as CaCO3and0.2meq/LMg2+(10mg/LasCaCO3).
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2.0 Ca HCO3
2+

0.0

3.21 3.81 Mg Na+ SO42 Cl 2.7 3.3 3.81

2+

Meq/L 0.4 2.0 0.7 0.51

LimeCaOmeq/L 0.4 2.0 2x0.7=1.4 0.51 4.31

Sodaashmeq/L 0 0 0 0.51 0.51

Recarbonation converts the excess lime to calcium carbonate precipitate. Further carbondioxide addition converts CO32 to HCO3, and finish water with a total hardness of 40 mg/L. The amount CO2 required is (1.25 + 0.2 + 0.4) meq/L x 22 mg/meq = 40.7mg/LofCO2. 1.25 Ca OH
2+

0.0 Ca OH
2+

0.6 Mg CO32

0.8
2+

1.91 Na SO42
+

Cl 1.4 1.91

0.0 0.2

0.8

0.0

0.6 0.8 2+ Mg Na+ Ca HCO3 CO32 SO42 0.0 0.4 0.8 1.4
2+

1.91 Cl 1.91

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SELECTIVECALCIUMREMOVAL Waters with a magnesium hardness of less than 40 mg/L as CaCO3 can be soften by removing only a portion of the calcium hardness. The processing can be a singlestage system of mixing, sedimentation, recarbonation and filtration. Enough lime is added to the raw water to precipitate calcium hardness without providing any excess for magnesium removal. Soda ash mayberequireddependingonthenoncarbonatehardness.Recarbonation isusuallypractised toreduce scaling ofthefilter sand and producea stable effluent.(seeexampleproblem10.5and10.4pp433437). Example:SelectiveCalciumRemoval Considerselectivecalciumcarbonateremovalsofteningofarawwaterwith a bar graph as shown below: Calculate the lime dosage as CaO, and sketch thesoftenwaterbargraphafterrecarbonationandfiltration. Solution The only hypothetical combination involving calcium is 2.0 meq/L of Ca (HCO3)2 ; therefore, no soda ash is needed and the lime required is 2.0 meq/L which equal to 28 mg/meq x 2 meq/L = 56 mg/L of CaO. The soften waterbargraphhas0.6meq/Lofcalciumhardness(thepracticallimitof30 mg/L) and the total alkalinity is 0.8 meq/L, which is 0.6 meq/L from the practical limit and 0.2 meq/L associated with magnesium in the raw water bar graph. The degree of recarbonation determines the relative amount of carbonate and bicarbonate anions. The other ions in the soften water are thesameasintherawwater. 0.0 2.0 2.6 2.9 2+ 2+ Ca Mg Na+ HCO3 SO42 Cl 0.0 2.2 2.7 2.9 0.0
2+

0.6 Ca CO32 HCO3 Mg SO42 0.8

2+

0.0

1.2 1.5 Na+ Cl 1.3 1.5

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