An investigation of water hardness through AA and EDTA Daniel Lordan March 26th, 2014 In con unction with !

eff Li, "iang Li, and #age $reft %nder the direction of Ethel $hanis &he' 111(10) The *enns+lvania #tate %niversit+

Lordan 2

Introduction: ,ater hardness is a 'easure of dissolved divalent ions in -2., s/ecificall+ &a20 and Mg2011 ,hile it2s not a health /ro3le' to consu'e hard water 4so'e studies have even shown it to actuall+ reduce ris5 of cardiovascular disease26 there can 3e long ter' effects on water /i/es and 'ineral de/osits1) The Environ'ental *rotection Agenc+ 4E*A6 has set no standards on water hardness, 3ut counties and 'unici/alities create individual guidelines on what levels of individual ion concentration the+ will tolerate1) ,ater hardness can 3e found in two wa+s( EDTA titration and Ato'ic A3sor/tion #/ectrosco/+1 The first /rocess uses eth+lenedia''inetetraacetic acid, a solution that 3inds to cations and reveals dissolved Mg20 and &a20 ion concentration through titration14 E7T, an indicator, turns the water red in the /rocess of 3inding with 'etal ions, li5e &a20 and Mg201 At the end of the titration 4when all of the ions are chelated6 an+ e8tra E7T that is not 3onded a//ears 3lue, signaling the end of titration1 EDTA chelation 4the /rocess in which an EDTA agent is used to 3ond with 'etal ions6 is a techni9ue used co''erciall+ for food /reservation, soa/s and detergents, and 'edical reasons14,: Ato'ic A3sor/tion #/ectrosco/+, or AA, is another 'ethod of understanding ion content1 AA uses a fla'e that su/erheats a water sa'/le and then sends a light with a s/ecific wavelength across the su/erheated water1 Ele'ents that a3sor3 that /articular wavelength a3sor3 so'e of the light and the re'aining light can 3e 'easured on the other side1 The a'ount of light a3sor3ed is then 'easured and the concentration of the ele'ent can 3e calculated 3+ co'/aring values to chec5 standards, or /re'easured

Lordan ) a3sor/tions at s/ecific ion concentrations16 .ne other i'/ortant 'easure that is used in relation to dissolved ions in water is Total Dissolved #olids 4TD#61 TD# is a 'easure of chlorides, /hos/hides, nitrates and other /articles, as well as the &a20 and Mg20 ions that are 'easured in EDTA and AA1; TD# is 'easured 3+ weighing the re'aining solids after water has 3een eva/orated1; %nli5e hardness, the E*A has standards for a lot of the other dissolved solids found in TD#, so this 'easure is 'ore useful for overall water 9ualit+1 ) In this la3, however, the focus will 3e on water hardness and therefore on EDTA titration and AA #/ectrosco/+1 ,ater hardness is 'easured in /arts /er 'illion 4'illigra's /er liter6 of &a&.), or calciu' car3onate1< The calciu' car3onate 'easure includes the Mg20 and &a20 ions and there are general hardness =classifications,> as shown 3elow1

Table 1- Water Hardness Classifications, reproduced from http://continuingeducation.construction.com9

The water that is 3eing sa'/led in this re/ort is ta/ water fro' ?edifer Dining &o''ons in #tate &ollege, *enns+lvania, 16<021 Also reviewed are sa'/les fro' 'elted snowfall in #tate &ollege, seawater fro' .rlando, @L, and ta/ water fro' Aor5, *enns+lvania1 M+ h+/othesis is that the hardest water will 3e seawater 3ecause of the high ion content in saline water110 7ecause nor'al ta/ water is treated with softening agents11 the two ta/ water sa'/les will /ro3a3l+ 3e softer than salt water +et harder than

Lordan 4 the snow1 #o'e of these softening agents include a resin ion e8change in which 3eads /ull calciu' and 'agnesiu' ions in for sodiu' or h+drogen ions, 'uch li5e the one used in this la311) According to the #tate &ollege 7orough ,ater Authorit+, the hardness of their water ranges fro' 120(1B0 'gCL 4or //'6,1B so the water fro' ?edifer Dining &o''ons, #a'/le 1, should co'e in near that level1 #now will /ro3a3l+ 3e the softest, as the sus/ended snow did not run over the ground to /ic5 u/ salts so the levels of &a20 and Mg20 will 3e lower112

Procedure: The /rocedure was ta5en fro' the *enns+lvania #tate %niversit+ &he'tra51)1 EDTA readings were ta5en in la3 and AA #/ectrosco/+ readings were done using the AA #/ectrosco/e /rovided 3+ *enn #tate1 The EDTA was /erfor'ed in a 1 8 12 well stri/1 .ne dro/ of sa'/le water was added to each well along with a dro/ of E7T indicator and one of D-)CD-4&lCMgEDTA 3uffer 4one dro/ 3eing e9ual to 010160 'L 0C( 01000;4 'L611),21 Titration was considered co'/lete when a well turned co'/letel+ 3lue1 The AA #/ectrosco/+ was run at wavelengths of 4221; n' for &a20 concentration and 2021: n' for Mg201 E8cel was used to create gra/hs and lines of 3est fit1 The onl+ deviation fro' the la3 /rotocol ca'e fro' the EDTA set u/, in which so'e water sa'/les were diluted1 These dilutions were noted in the results and corrected for in the ta3les 4for e8a'/le #a'/le 1, the ta/ water fro' #tate &ollege was diluted at a 2E1 ratio so the final EDTA reading was 'ulti/lied 3+ three to correct for that61 In the results, sa'/le nu'3er refers to the four sa'/les discussed in the introduction with 1, the ta/ water fro' #tate &ollege, *A, 3eing the /ri'ar+ sa'/le

Lordan : 4anal+Fed 3+ Dan Lordan6114 #a'/le 2 is the 'elted ice fro' #tate &ollege, *A,1: ) is the sea water fro' .rlando, @L,16 and 4 is the ta/ water fro' Aor5, *A11;

Results:

Graph 1: Calibration of Ca ! Concentration b" ##

Lordan 6

Graph : Calibration of $g ! Concentration b" ##

AA Absorbance Data #a'/le Dilution 1 2 ) 4 Done Done :0E1 Done

&a20 A3sor3ance 011)46 010B)) 011426 011<))

&orrected for Dilution 011)46 4G6 010B)) 4G6 ;11) 011<)) 4G6

Mg20 A3sor3ance 0110B6 0102<B 0126B1 010<16

&orrected for Dilution 0110B6 4G6 0102<B 4G6 1)14:: 010<16 4G6

Table : ## absorbance data- gathered from readings from atomic absorption spectrophotometer. %eadings ta&en at the 'enns"l(ania )tate *ni(ersit" on $arch 1+, ,1-

AA Absorbance Data Conversion #a'/le &a20 &a20 &oncentration -ardness 4//'6 4//'6 1 1410; ):11< 2 B1:2 2)1<1 ) ;<21;B 1,B:61B< 4 1B142 4<1:4

Mg20 &oncentration 4//'6 <161 11;; 1,1)B1:; 6124

Mg20 -ardness 4//'6 ):14B ;12B 4,6<B161 2:16;

Total -ardness 4//'6 ;016: ))110 6,6461:B ;4121

Table .: ## absorbance data con(erted to ppm hardness using e/uations from Graphs 1 and . )ee calculations 0. . and 0... ## original data from 1Corrected for 2ilution3 columns of Table 1.

EDTA Titration Data #a'/le Dilution %nsoftened 1 2E1 4 2 Done : ) :0E1 6 4 2E1 6

&onv1 12 : 4G6 )00 1<

71#1 4 ) ) DCA

&onv1 12 ) 4G6 1:0 DCA

?esin DCA 1 2 DCA

&onv1 DCA 14G6 100 DCA

Table -: 02T# drop count from titration, Con(. is corrected for dilution, 4.). stands for 4a&ing )oda )oftened, and %esin is after %esin softening agent. 4a&ing soda 5as a commercial 5ater-softening agent, 5ith an acti(e ingredient of )odium Carbonate. 6# stands for not applicable, solution had too little of an ion count to return readings. %eadings ta&en at the 'enns"l(ania )tate *ni(ersit" on $arch 1+, ,1-

pH and TDS Data #a'/le /- 7efore 1 < 2 6 ) ; 4 6

/- After 4 4 1 )

TD# .3servation #light white resin, whiter than reference Light ring, si'ilar to reference Mil5+ white ring, interior si'ilar to reference More white than reference

Table 7: pH readings before and after resin softening agent. T2) 8bser(ation reference 5as one drop distilled 5ater. %eadings ta&en at the 'enns"l(ania )tate *ni(ersit" on $arch 1+, ,1-.

AA Check Standards for Ca2

Lordan ; &a20 &onc1 4//'6 0 11000 :100 10100 2:10 :010 A3sor3ance Halue 4at 4221; n'6 01011B6 010::0B 010BB12 012)146 014:B;2 &hec5 #tandard 4//'6 016< 41<B 10,20 241;) 4B12B

Table 9: ## )tandards for ## )pectroscop". ## 8perator- White. %eadings ta&en at 1:17 pm at the 'enns"l(ania )tate *ni(ersit" on $arch 1+, ,1-

AA Check Standards for !"2 Mg20 &onc1 4//'6 0 11000 01010B) :100 0106<)< 10100 011)6B0 2:10 01)040: )010 01):;;;

1104 :121 B111 241:; 2B1)0

Table :: ## )tandards for ## )pectroscop". ## 8perator- White. %eadings ta&en at 1:17 pm at the 'enns"l(ania )tate *ni(ersit" on $arch 1+, ,1-

&alculationsE A1 EDTA titration 'olarit+ calculationE MEDTAIHEDTA G M#AM*LE I H#AM*LE 42 I10(4 M#AM*LE6 I44 dro/s6I) 4dilution correction6G M#AM*LEI41 dro/6 010024 G M#AM*LE 71 Molarit+ to //' conversion 4as /er #ection J, &he'tra5 /rocedure1)6E 010024 'ol I 100g &a&.) I 1000'g &a&.) G 240 'g &a&.) 4240 //'6 1 liter 1 'ol &a&.) 1 g &a&.) 1 liter of solution &1 */' to grains /er gallon conversion 4as /er #ection J, &he'tra5 /rocedure1)6E 240 //' I 1grain /er gallon G 1410 grains /er gallon 1;11 //' D1 Error &alculationsE If the EDTA well count was one off, the calculation fro' /art A would 3eE MEDTAIHEDTA G M#AM*LE I H#AM*LE

Lordan < 42 I10(4 M#AM*LE6 I4) or : dro/s6I) 4dilution correction6G M#AM*LEI41 dro/6 0100) or 01001< G M#AM*LE D121 *ercent ErrorE A3s1 Halue 4.3served(E8/ected6 I100 E8/ected A3s1 Halue 401001<M (010024M6 I100 G 2:K 010024M D1)1 *recisionE .3served 4one off6 L E8/ected 010024M L 01001<M G 0C( 010006M E1 AA &alculationsE @or concentration fro' a3sor3ance value, use line of 3est fit 4found in E8cel6 "G'; 0 3 where 4"6 is a3sor3ance value and 4;6 is &a20 concentration in /arts /er 'illion, rewritten asE ;G"L3 ' E121 //' &a20 to //' &a&.)E //' &a20 I 100g &a&o)C'ol G //' &a&.) G //' hardness 40g &a20C'ol E1)1 //' Mg20 to //' &a&.)E //' Mg20 I 100g &a&o)C'ol G //' &a&.) G //' hardness 241)g Mg20C'ol Discussion: According to the AA data, Ta3le ), the softest water was the 'elted snow 4#a'/le )6 with a total hardness reading of ))11 //' &a&.)1 The two ta/ water AA readings were re'ar5a3l+ si'ilar 4at ;01; and ;412 //' for #a'/les 1 and 4 res/ectivel+61 The hardest water fro' the AA readings was seawater at over 6,600 //'1 This see's a little high for salt water, which usuall+ has a &a20 content of around 420

Lordan B //' and Mg20 levels around 12<0 //'11< %sing the sa'e calculations fro' E121 and E1)1, the total hardness that would result fro' the acce/ted values of seawater hardness1< would co'e out to a3out 6,)1;1 This is relativel+ close, with a /ercent error 4calculated li5e D126 of :12K1 @or #a'/le 1, the water fro' #tate &ollege, there were two different hardness results1 According to the AA #/ectrosco/+, the hardness of #a'/le 1 was ;01; //' 3ut EDTA titration gave a result of 240 //'1 In order to reconcile this, the EDTA titration reading was divided 3+ the dilution factor 4of )6 resulting in <0 //'1 These two results are still 9uite different 3ut can 3e understood 3+ loo5ing at the /recision of the two 'easure'ents1 @ro' D1), which gives a /recision of 0C( 010006M, the //' can 3e calculated as in 71 The //' /recision would 3e 0C( 60 //', which is a 'uch greater range than that of the chec5 standards fro' the AA #/ectrosco/+ 4Ta3les 6 and ;61 The chec5 standards in the AA #/ectrosco/+ e8/eri'ent do not differ fro' the actual values 3+ 'ore than one //'1 Therefore it can 3e concluded that the AA #/ectrosco/+ results are 3oth 'ore /recise 43ecause the readings are e8tre'el+ close to what the+ should 3e in the chec5 standards, signif+ing re/eata3ilit+6 and 'ore accurate 43ecause the actual values center around the real results as shown 3+ the high ?2 values of Jra/hs 1 and 21 ?2 is a 'easure of the a'ount of data a//ro8i'ated 3+ the gra/h61 EDTA titration confir'ed the readings of the AA #/ectrosco/+ in that 'ore dro/s of EDTA were needed to titrate seawater than the other three 4see Ta3le 2 &olu'n 461 .nce again the two ta/ water readings were 2nd and )rd hardest, 3ut the order of the two was switched 4#a'/le 1, the #tate &ollege water, needed 12 dro/s to turn the solution to 3lue whereas the Aor5 water, #a'/le 4, needed 1<61 &onsidering the difference 3etween

Lordan 10 #a'/les 1 and 4 in AA #/ectrosco/+ readings was less than four //', it is not sur/rising that the EDTA was consistent with AA in this case1 The calculated 'argin of error, as noted /reviousl+, is 0C( 60 //', so a difference of 4 //' could easil+ 3e 'ista5en1 The titration did confir' that the snow was once again the softest, 3ecause it too5 onl+ five dro/s to finish the reaction1 %sing the A and 7 calculations again, five dro/s is e9ual to 100 //', which is a3out three ti'es the AA result1 In the case of the snow, however, there was no dilution, so there 'ust have 3een so'e error in the calculation1 #o'e /ossi3le sources of error in this /ro ect co'e fro' a cou/le i'/ortant things1 @irst of all, 3oth ta/ water 'easure'ents co'e fro' ta/s and not straight fro' the 'unici/alit+1 This 'eans that the water that is 3eing 'easured has /assed through /i/es and /ossi3l+ softening agents installed fro' the 'anufacturers1 Therefore, it is not sur/rising that the #tate &ollege ta/ water 'ight not 'atch u/ e8actl+ with the 3orough water data /rovided 4it was a3out 60 //' under according to AA611B Also, the /lastic containers in which we used to 5ee/ the water and their sterilit+ 'ight have had so'e i'/act on the ion concentration 3+ adding e8tra electrol+tes 4#a'/le 1, for e8a'/le, was contained in a Jatorade 3ottle6120

Conclusion: The data is consistent with '+ h+/othesis1 The hardest water, according to AA #/ectrosco/+, was the seawater 46,64B1:B //' &a&.)6, followed 3+ #tate &ollege and Aor5 ta/ water 4;016:, ;4121 //'6, and finall+ the 'elted #tate &ollege snow 4))110 //'61 The EDTA titration confir'ed that the two ta/ water 'easure'ents were in the 'iddle of the data collected, 3ut the 'argin of error showed the ordering of the two to 3e

Lordan 11 statisticall+ insignificant 4error of 0C( 60 //'61 The AA #/ectrosco/+ should 3e used in this situation, as its chec5 standards /rove it to 3e 3oth 'ore /recise and 'ore accurate1

References:
11 @re+, ?egina1 M,ater -ardness1M Water Hardness1 ,ashington %niversit+ De/t1 of &he'istr+, n1d1 ,e31 )0 Mar1 20141 htt/ECCwww1che'istr+1wustl1eduCNedudevCLa3TutorialsC,aterC@resh,aterChardness1ht'l 21 M-ardness in Drin5ing ,ater1M #genc" of Human )er(ices1 Her'ont De/art'ent of -ealth, n1d1 ,e31 )0 Mar1 20141 Ohtt/ECChealthver'ont1govCenviroCwaterChardness1as/8P1 )1 "Explanation of Water Hardness." Explanation of Water Hardness. Fairfax County Water, n.d. Web. 30 Mar. 2014. !ttps"##$$$.f%$a.or&#$ater#!ardness.!t'(. 4. )purlo%*, +. "+eter'ination of Water Hardness ,y Co'plexo'etri% -itration." IU Southeast. .ndiana /ni0ersity, 12 1o0. 2013. Web. 30 Mar. 2014. !ttp"##!o'epa&es.ius.edu#+)2/345C#%121#$ee*13.!t'(. 6. "Et!ylenedia'inetetraa%eti% 7%id." University of Maryland Medical Center. /MMC, n.d. Web. 30 Mar. 2014. !ttp"##u''.edu#!ealt!#'edi%al#alt'ed#supple'ent#et!ylenedia'inetetraa%eti%8a%id(. 9. Ca'pbell, :arryd. "+eter'ination of Water Hardness fro' Co''on )our%es /sin& Fla'e 7to'i% 7bsorption )pe%tro'etry." Concordia Journal of Experimental Chemistry 4.; <2010=" 2. Web. 30 Mar. 2014. !ttp"##$$$p.%ord.edu#dept#%!e'istry#CC:7C#2010>?ol>1#2010>1>4.pdf(. @. "6.; -otal )olids." Water Monitoring and Assets. E27, n.d. Web. 30 Mar. 2014. !ttp"##$ater.epa.&o0#type#rsl#'onitorin&#0's6;.%f'(. ;. "Water Hardness and 7l*alinity." US S. /)A), n.d. Web. 2@ Mar. 2014. !ttps"##$ater.us&s.&o0#o$B#!ardness8

Lordan 12
al*alinity.!t'l(. C. "-e'plate 7ssisted CrystalliDation8 7 )ustainable )olution to Hard Water )%ale." Continuing Education Center. 7r%!ite%tural 3e%ord, Mar. 2012. Web. 30 Mar. 2014. !ttp"##%ontinuin&edu%ation.%onstru%tion.%o'#arti%le.p!pE 4F2C1GCF;;1G2F4(. 10. "W!at .s in )ea$aterE" !cean Chemistry. +u*e, n.d. Web. 30 Mar. 2014. !ttp"##people.%!e'.du*e.edu#HIds#%ruise>%!e'#o%eans#sea$ater1.!t'l(. 11. "Water Juality 7sso%iation." Water "uality Association. 1.p., 2 May 200. Web. 2C Mar. 2014. !ttp"##$$$.$Ba.or&#sitelo&i%.%f'E.+F4@@(. 12. "Water 1e$s G 7rti%les." Salt Institute. )alt .nstitute, 13 :uly 2013. Web. 30 Mar. 2014. !ttp"##$$$.saltinstitute.or&#ne$s8arti%les#!ard8$ater#(. 13. 2)/ C!e'tra* 201382014 $ritten by )tep!en -!o'pson, edited by :osep! -. Kaiser by Hayden8 M%1eil p&s. 10.1810.22 14. 4ordan, +aniel, C!e' 1118103 4aboratory 1oteboo*, sprin& 2014, pp. 23829. 16. 4i, :eff, C!e' 1118103 4aboratory 1oteboo*, sprin& 2014, pp. 2482;. 19. 4i, Lian&, C!e' 1118103 4aboratory 1oteboo*, sprin& 2014, pp. 21822. 1@. Kreft, )a&e, C!e' 1118103 4aboratory 1oteboo*, sprin& 2014, pp. 2@82C. 1;. "Cal%iu', 7l*alinity and Ma&nesiu'." Captive #eef Ecosystems. 1.p., n.d. Web. 31 Mar. 2014. !ttp"##$$$.reefe%osyste's.%o'#reef8fa%ts#$ater8%!e'istry8and8para'eters#%al%iu'8al*alinity8and8'a&nesiu'#(. 1C. "FreBuently 7s*ed Juestions." State College $orough Water Authority. )C,W7, n.d. Web. 31 Mar. 2014. !ttp"##$$$.s%b$a.or&#faB.p!p(. 20. ,ud&e, :ulia, and :ason 50erbuy. "C.1 Aeneral 2roperties of 7Bueous )olutions." Chemistry% Atoms &irst. ,oston" M%Ara$8Hill 4earnin& )olutions, 2012. 30@811. 2rint. 21. 4ordan, +aniel, C!e' 1118103 4aboratory 1oteboo*, sprin& 2014, p&. 9.