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An investigation of water hardness through AA and EDTA Daniel Lordan March 26 th , 2014 In conjunction with Jeff Li, Xiang Li, and Sage Kreft Under the direction of Ethel Khanis Chem 111-103 The Pennsylvania State University

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Introduction:

Water hardness is a measure of dissolved divalent ions in H 2 O, specifically Ca 2+ and Mg 2+ . 1 While it’s not a health problem to consume hard water (some studies have even shown it to actually reduce risk of cardiovascular disease 2 ) there can be long term effects on water pipes and mineral deposits. 3 The Environmental Protection Agency (EPA) has set no standards on water hardness, but counties and municipalities create individual guidelines on what levels of individual ion concentration they will tolerate. 3 Water hardness can be found in two ways- EDTA titration and Atomic Absorption Spectroscopy. The first process uses ethylenediamminetetraacetic acid, a solution that binds to cations and reveals dissolved Mg 2+ and Ca 2+ ion concentration through titration. 4 EBT, an indicator, turns the water red in the process of binding with metal ions, like Ca 2+ and Mg 2+ . At the end of the titration (when all of the ions are chelated) any extra EBT that is not bonded appears blue, signaling the end of titration. EDTA chelation (the process in which an EDTA agent is used to bond with metal ions) is a technique used commercially for food preservation, soaps and detergents, and medical reasons. 4,5 Atomic Absorption Spectroscopy, or AA, is another method of understanding ion content. AA uses a flame that superheats a water sample and then sends a light with a specific wavelength across the superheated water. Elements that absorb that particular wavelength absorb some of the light and the remaining light can be measured on the other side. The amount of light absorbed is then measured and the concentration of the element can be calculated by comparing values to check standards, or premeasured

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absorptions at specific ion concentrations. 6 One other important measure that is used in relation to dissolved ions in water is Total Dissolved Solids (TDS). TDS is a measure of chlorides, phosphides, nitrates and other particles, as well as the Ca 2+ and Mg 2+ ions that are measured in EDTA and AA. 7 TDS is measured by weighing the remaining solids after water has been evaporated. 7 Unlike hardness, the EPA has standards for a lot of the other dissolved solids found in TDS, so this measure is more useful for overall water quality. 3 In this lab, however, the focus will be on water hardness and therefore on EDTA titration and AA Spectroscopy. Water hardness is measured in parts per million (milligrams per liter) of CaCO 3 , or calcium carbonate. 8 The calcium carbonate measure includes the Mg 2+ and Ca 2+ ions and there are general hardness “classifications,” as shown below.

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Table 1- Water Hardness Classifications, reproduced from http://continuingeducation.construction.com 9

The water that is being sampled in this report is tap water from Redifer Dining Commons in State College, Pennsylvania, 16802. Also reviewed are samples from melted snowfall in State College, seawater from Orlando, FL, and tap water from York, Pennsylvania. My hypothesis is that the hardest water will be seawater because of the high ion content in saline water. 10 Because normal tap water is treated with softening agents 11 the two tap water samples will probably be softer than salt water yet harder than

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the snow. Some of these softening agents include a resin ion exchange in which beads pull calcium and magnesium ions in for sodium or hydrogen ions, much like the one used in this lab. 13 According to the State College Borough Water Authority, the hardness of their water ranges from 120-190 mg/L (or ppm), 19 so the water from Redifer Dining Commons, Sample 1, should come in near that level. Snow will probably be the softest, as the suspended snow did not run over the ground to pick up salts so the levels of Ca 2+ and Mg 2+ will be lower. 12

Procedure:

The procedure was taken from the Pennsylvania State University Chemtrak 13 . EDTA readings were taken in lab and AA Spectroscopy readings were done using the AA Spectroscope provided by Penn State. The EDTA was performed in a 1 x 12 well strip. One drop of sample water was added to each well along with a drop of EBT indicator and one of NH 3 /NH 4 Cl/MgEDTA buffer (one drop being equal to 0.0160 mL +/- 0.00074 mL). 13,21 Titration was considered complete when a well turned completely blue. The AA Spectroscopy was run at wavelengths of 422.7 nm for Ca 2+ concentration and 202.5 nm for Mg 2+ . Excel was used to create graphs and lines of best fit. The only deviation from the lab protocol came from the EDTA set up, in which some water samples were diluted. These dilutions were noted in the results and corrected for in the tables (for example Sample 1, the tap water from State College was diluted at a 2:1 ratio so the final EDTA reading was multiplied by three to correct for that). In the results, sample number refers to the four samples discussed in the introduction with 1, the tap water from State College, PA, being the primary sample

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(analyzed by Dan Lordan). 14 Sample 2 is the melted ice from State College, PA, 15 3 is the sea water from Orlando, FL, 16 and 4 is the tap water from York, PA. 17

Results:

Lordan 5 (analyzed by Dan Lordan). Sample 2 is the melted ice from State College, PA,

Graph 1: Calibration of Ca 2+ Concentration by AA

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Graph 2: Calibration of Mg 2+ Concentration by AA

AA Absorbance Data

Sample

Dilution

Ca 2+

Corrected

Mg 2+

Corrected

 

Absorbance

for Dilution

Absorbance

for Dilution

  • 1 None

0.1346

0.1346 (=)

0.1096

0.1096 (=)

  • 2 None

0.0933

0.0933 (=)

0.0289

0.0289 (=)

  • 3 50:1

0.1426

7.13

0.2691

13.455

  • 4 None

0.1833

0.1833 (=)

0.0816

0.0816 (=)

Table 2: AA absorbance data- gathered from readings from atomic absorption spectrophotometer. Readings taken at the Pennsylvania State University on March 18, 2014

AA Absorbance Data Conversion

Sample

Ca 2+

Ca 2+

Mg 2+

Mg 2+

Total

Concentration

Hardness

Concentration

Hardness

Hardness

(ppm)

(ppm)

(ppm)

(ppm)

(ppm)

  • 1 14.07

35.18

8.61

35.49

70.65

  • 2 9.52

23.81

1.77

7.29

33.10

  • 3 782.79

1,956.98

1,139.57

4,689.61

6,646.59

  • 4 19.42

48.54

6.24

25.67

74.21

Table 3: AA absorbance data converted to ppm hardness using equations from Graphs 1 and 2. See calculations E.2. and E.3. AA original data from “Corrected for Dilution” columns of Table 1.

EDTA Titration Data

Sample

Dilution

Unsoftened

Conv.

B.S.

Conv.

Resin

Conv.

2:1

  • 1 4

 

12

4

12

N/A

N/A

  • 2 5

None

 

5 (=)

3

3 (=)

1

1(=)

50:1

  • 3 6

 

300

3

150

2

100

  • 4 6

2:1

 

18

N/A

N/A

N/A

N/A

Table 4: EDTA drop count from titration, Conv. is corrected for dilution, B.S. stands for Baking Soda Softened, and Resin is after Resin softening agent. Baking soda was a commercial water-softening agent, with an active ingredient of Sodium Carbonate. NA stands for not applicable, solution had too little of an ion count to return readings. Readings taken at the Pennsylvania State University on March 18, 2014

pH and TDS Data

Sample

pH Before

pH After

TDS Observation

8

  • 1 4

 

Slight white resin, whiter than reference

  • 2 4

6

 

Light ring, similar to reference

  • 3 1

7

 

Milky white ring, interior similar to reference

  • 4 3

6

 

More white than reference

Table 5: pH readings before and after resin softening agent. TDS Observation reference was one drop distilled water. Readings taken at the Pennsylvania State University on March 18, 2014.

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Ca 2+ Conc. (ppm)

Absorbance Value (at 422.7

Check Standard (ppm)

nm)

0

1.000

0.01196

0.68

5.00

0.05509

4.89

10.00

0.09912

10,20

  • 25.0 0.23146

24.73

  • 50.0 0.45972

49.29

Table 6: AA Standards for AA Spectroscopy. AA Operator- White. Readings taken at 1:15 pm at the Pennsylvania State University on March 18, 2014

AA Check Standards for Mg 2+

Mg 2+ Conc. (ppm)

0

1.000

0.01093

1.04

5.00

0.06838

5.21

10.00

0.13690

9.11

  • 25.0 0.30405

24.57

  • 30.0 0.35777

29.30

Table 7: AA Standards for AA Spectroscopy. AA Operator- White. Readings taken at 1:15 pm at the Pennsylvania State University on March 18, 2014

Calculations:

  • A. EDTA titration molarity calculation:

M EDTA *V EDTA = M SAMPLE * V SAMPLE

(2 *10 -4 M SAMPLE ) *(4 drops)*3 (dilution correction)= M SAMPLE *(1 drop)

0.0024 = M SAMPLE

  • B. Molarity to ppm conversion (as per Section G, Chemtrak procedure 13 ):

0.0024 mol * 100g CaCO 3 * 1000mg CaCO 3 = 240 mg CaCO3 (240 ppm)

1 liter

1 mol CaCO 3

1 g CaCO 3

1 liter of solution

  • C. Ppm to grains per gallon conversion (as per Section G, Chemtrak procedure 13 ):

240 ppm * 1grain per gallon = 14.0 grains per gallon 17.1 ppm

  • D. Error Calculations:

If the EDTA well count was one off, the calculation from part A would be:

M EDTA *V EDTA = M SAMPLE * V SAMPLE

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(2 *10 -4 M SAMPLE ) *(3 or 5 drops)*3 (dilution correction)= M SAMPLE *(1 drop)

0.003 or 0.0018 = M SAMPLE

D.2. Percent Error:

Abs. Value (Observed-Expected) *100 Expected

Abs. Value (0.0018M -0.0024M) *100 = 25%

D.3. Precision:

0.0024M

Observed (one off) – Expected

0.0024M – 0.0018M = +/- 0.0006M

E. AA Calculations:

For concentration from absorbance value, use line of best fit (found in Excel)

y=mx + b

where (y) is absorbance value and (x) is Ca 2+ concentration in parts per million, rewritten as:

x = y – b

m

E.2. ppm Ca 2+ to ppm CaCO 3 :

ppm Ca 2+

*

100g CaCo 3 /mol = ppm CaCO 3 = ppm hardness 40g Ca 2+ /mol

E.3. ppm Mg 2+ to ppm CaCO 3 :

ppm Mg 2+

*

Discussion:

100g CaCo 3 /mol = ppm CaCO 3 = ppm hardness 24.3g Mg 2+ /mol

According to the AA data, Table 3, the softest water was the melted snow

(Sample 3) with a total hardness reading of 33.1 ppm CaCO 3 . The two tap water AA

readings were remarkably similar (at 70.7 and 74.2 ppm for Samples 1 and 4

respectively). The hardest water from the AA readings was seawater at over 6,600 ppm.

This seems a little high for salt water, which usually has a Ca 2+ content of around 420

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ppm and Mg 2+ levels around 1280 ppm. 18 Using the same calculations from E.2. and E.3.,

the total hardness that would result from the accepted values of seawater hardness 18

would come out to about 6,317. This is relatively close, with a percent error (calculated

like D.2) of 5.2%.

For Sample 1, the water from State College, there were two different hardness

results. According to the AA Spectroscopy, the hardness of Sample 1 was 70.7 ppm but

EDTA titration gave a result of 240 ppm. In order to reconcile this, the EDTA titration

reading was divided by the dilution factor (of 3) resulting in 80 ppm. These two results

are still quite different but can be understood by looking at the precision of the two

measurements. From D.3, which gives a precision of +/- 0.0006M, the ppm can be

calculated as in B. The ppm precision would be +/- 60 ppm, which is a much greater

range than that of the check standards from the AA Spectroscopy (Tables 6 and 7). The

check standards in the AA Spectroscopy experiment do not differ from the actual values

by more than one ppm. Therefore it can be concluded that the AA Spectroscopy results

are both more precise (because the readings are extremely close to what they should be in

the check standards, signifying repeatability) and more accurate (because the actual

values center around the real results as shown by the high R 2 values of Graphs 1 and 2. R 2

is a measure of the amount of data approximated by the graph).

EDTA titration confirmed the readings of the AA Spectroscopy in that more drops

of EDTA were needed to titrate seawater than the other three (see Table 2 Column 4).

Once again the two tap water readings were 2 nd and 3 rd hardest, but the order of the two

was switched (Sample 1, the State College water, needed 12 drops to turn the solution to

blue whereas the York water, Sample 4, needed 18). Considering the difference between

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Samples 1 and 4 in AA Spectroscopy readings was less than four ppm, it is not surprising

that the EDTA was consistent with AA in this case. The calculated margin of error, as

noted previously, is +/- 60 ppm, so a difference of 4 ppm could easily be mistaken. The

titration did confirm that the snow was once again the softest, because it took only five

drops to finish the reaction. Using the A and B calculations again, five drops is equal to

100 ppm, which is about three times the AA result. In the case of the snow, however,

there was no dilution, so there must have been some error in the calculation.

Some possible sources of error in this project come from a couple important

things. First of all, both tap water measurements come from taps and not straight from the

municipality. This means that the water that is being measured has passed through pipes

and possibly softening agents installed from the manufacturers. Therefore, it is not

surprising that the State College tap water might not match up exactly with the borough

water data provided (it was about 60 ppm under according to AA). 19 Also, the plastic

containers in which we used to keep the water and their sterility might have had some

impact on the ion concentration by adding extra electrolytes (Sample 1, for example, was

contained in a Gatorade bottle). 20

Conclusion:

The data is consistent with my hypothesis. The hardest water, according to AA

Spectroscopy, was the seawater (6,649.59 ppm CaCO 3 ), followed by State College and

York tap water (70.65, 74.21 ppm), and finally the melted State College snow (33.10

ppm). The EDTA titration confirmed that the two tap water measurements were in the

middle of the data collected, but the margin of error showed the ordering of the two to be

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statistically insignificant (error of +/- 60 ppm). The AA Spectroscopy should be used in

this situation, as its check standards prove it to be both more precise and more accurate.

References:

  • 1. Frey, Regina. "Water Hardness." Water Hardness. Washington University Dept. of Chemistry, n.d. Web. 30 Mar.

2014. http://www.chemistry.wustl.edu/~edudev/LabTutorials/Water/FreshWater/hardness.html

  • 2. "Hardness in Drinking Water." Agency of Human Services. Vermont Department of Health, n.d. Web. 30 Mar. 2014.

<http://healthvermont.gov/enviro/water/hardness.aspx>.

  • 3. "Explanation of Water Hardness." Explanation of Water Hardness. Fairfax County Water, n.d. Web. 30 Mar. 2014.

<https://www.fcwa.org/water/hardness.htm>.

  • 4. Spurlock, D. "Determination of Water Hardness By Complexometric Titration." IU Southeast. Indiana University, 12

Nov. 2013. Web. 30 Mar. 2014. <http://homepages.ius.edu/DSPURLOC/c121/week13.htm>.

  • 5. "Ethylenediaminetetraacetic Acid." University of Maryland Medical Center. UMMC, n.d. Web. 30 Mar. 2014.

<http://umm.edu/health/medical/altmed/supplement/ethylenediaminetetraacetic-acid>.

  • 6. Campbell, Jarryd. "Determination of Water Hardness from Common Sources Using Flame Atomic Absorption

Spectrometry." Concordia Journal of Experimental Chemistry 4.8 (2010): 2. Web. 30 Mar. 2014.

<http://wwwp.cord.edu/dept/chemistry/CCJAC/2010_Vol_1/2010_1_4.pdf>.

  • 7. "5.8 Total Solids." Water Monitoring and Assets. EPA, n.d. Web. 30 Mar. 2014.

<http://water.epa.gov/type/rsl/monitoring/vms58.cfm>.

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alkalinity.html>.

9. "Template Assisted Crystallization- A Sustainable Solution to Hard Water Scale." Continuing Education Center. Architectural Record, Mar. 2012. Web. 30 Mar. 2014. <http://continuingeducation.construction.com/article.php?

L=291&C=881&P=4>.

  • 10. "What Is in Seawater?" Ocean Chemistry. Duke, n.d. Web. 30 Mar. 2014.

<http://people.chem.duke.edu/~jds/cruise_chem/oceans/seawater1.html>.

  • 11. "Water Quality Association." Water Quality Association. N.p., 2 May 200. Web. 29 Mar. 2014.

<http://www.wqa.org/sitelogic.cfm?ID=477>.

  • 12. "Water News & Articles." Salt Institute. Salt Institute, 13 July 2013. Web. 30 Mar. 2014.

<http://www.saltinstitute.org/news-articles/hard-water/>.

  • 13. PSU Chemtrak 2013-2014 written by Stephen Thompson, edited by Joseph T. Kaiser by Hayden- McNeil pgs.

10.1-10.22

  • 14. Lordan, Daniel, Chem 111-103 Laboratory Notebook, spring 2014, pp. 23-26.

  • 15. Li, Jeff, Chem 111-103 Laboratory Notebook, spring 2014, pp. 24-28.

  • 16. Li, Xiang, Chem 111-103 Laboratory Notebook, spring 2014, pp. 21-22.

  • 17. Kreft, Sage, Chem 111-103 Laboratory Notebook, spring 2014, pp. 27-29.

  • 18. "Calcium, Alkalinity and Magnesium." Captive Reef Ecosystems. N.p., n.d. Web. 31 Mar. 2014.

<http://www.reefecosystems.com/reef-facts/water-chemistry-and-parameters/calcium-alkalinity-and-magnesium/>.

  • 19. "Frequently Asked Questions." State College Borough Water Authority. SCBWA, n.d. Web. 31 Mar. 2014.

<http://www.scbwa.org/faq.php>.

  • 20. Budge, Julia, and Jason Overbuy. "9.1 General Properties of Aqueous Solutions." Chemistry: Atoms First. Boston:

McGraw-Hill Learning Solutions, 2012. 307-11. Print.

  • 21. Lordan, Daniel, Chem 111-103 Laboratory Notebook, spring 2014, pg. 6.