The Wonder Liquid Water: Hard, Soft, or Softened

Alaina Weinheimer November 6, 2012 CHEM 111, Section 105 Group Members: Kyle Turner, Roxanne Umali, and Casey Watson TA: Matt Langston

Introduction: The purity of water can be measured in a variety of ways. One way to measure the amount of impurities in water is to measure the waters hardness. The hardness of water is the concentration of magnesium ions (Mg2+(aq)) and calcium ions (Ca2+(aq)) in the water. Water hardness results from the accumulation of these minerals in groundwater as the water passes through rocks and soil that contain these compounds with these ions in them. The water dissociates these compounds causing the hardness levels to increase1. Water hardness is commonly measured in grains per gallon2. Table 1. Concentration of Calcium ions and Magnesium ions Water Hardness Levels2 Concentration of Mg2+(aq) and Ca2+(aq) (gpg) Less than 1.0 gpg2 1.0 gpg 3.5 gpg2 3.6 gpg 10.5 gpg2 Greater than 10.5 gpg2 Hardness Level of Water Soft2 Slightly hard2 Hard2 Very hard2

Water hardness plays a large role industrial uses and cleanliness of items. Alone, Mg2+(aq) and Ca2+(aq) in water do not cause sickness or ills to a consumer. Water hardness is problematic in industrial uses and cleaning items because these ions often form insoluble compounds with other elements leaving behind solid deposits. A common problematic compound that results from the calcium ion is scale, CaCO3. Scale precipitates when the calcium ions in heated water combine with bicarbonate ions2. The buildup of scale causes problems in dishwasher, pipe, and heating system efficiency. In dishwashers, the solids accumulate on the dishes, making cleaning the dishes more difficult. Scale buildup in pipes lessens the amount of water able to flow through. Thus, pipes must be replaced every so often when the scale buildup becomes too obstructive3. In industrial boilers, scale buildup reduces heat transfer2. This phenomenon has

caused heating bills to rise up to 25%. Despite these issues hard water causes, the calcium ions and magnesium ions in hard water contribute, though minimally, to human daily nutrient intake3. There are several ways to measure the hardness of water. Three ways include a chemical indicator measurement , an instruments measurement, and a visual observation. The chemical indicator method involves the addition of ethylenediaminetetraacetic acid (EDTA) as a complexing agent and eriochrome black T (EBT) as the indicator. The equation for the addition
EDTA

of these chemicals is below: HD2 + Mg2+ + Ca2+

Blue

MgD + H+ + Ca2+
Red

CaEDTA + MgEDTA + HD2

(immediately) (immediately) (last) Blue

The addition of EBT turns the water sample solution a purple hue. EDTA is added to the solution until the water returns to a blue color. The amount of EDTA added is proportional to the hardness level of the water. The more EDTA needed to turn the water back to its original color, the more divalent ions are in the water4. An instrument that can be used to determine the hardness of water is an Atomic Absorption Spectroscope (AA). Sample water is sucked into the instrument and held to an extremely hot flame. This causes the atoms in the water sample to be separated. Meanwhile, a cathode lamp, which contains a source of light with a monochromatic wavelength that corresponds to the subject elements energy necessary to excite electrons to the next energy levels, is emitted across the instrument. This wavelength of light is only absorbed by that specific element in the atomized water sample because the energy of the wavelength only corresponds to that elements energy necessary to excite an electron. As the light beam passes through the sample, some of the light is absorbed and the rest of the light reaches a detector, which measures the difference between the initial amount of light and the amount of light that reached the detector. The amount of light absorbed is proportional to the concentration of the

ion of interest. A calibration graph is made plotting known concentrations against absorbance values. An unknown concentration of an ion can then be solved after its absorbance value is measured by plugging that value into the calibration graph equation. In this experiment, a wavelength for calcium ions was sent through in one instrument, and magnesium ions in another. An additional method for measuring water hardness is the observation of total dissolved solids (TDS). A portion of the water sample is evaporated, and the amount of residue left behind indicates how impure the water is5. In summary, there are many ways to measure water hardness. The readings the two methods give differ slightly. The EDTA method tends to show higher results of water hardness than the AA reads. The EDTA method indicates the concentration of all divalent ions, more ions than calcium and magnesium ions. On the other hand, the AA measures for the concentrations of magnesium ions and calcium ions specifically. However, the AA reading is not completely accurate either. The AA that is being used may have inherent instrument error. Check standards are run to measure this level of inherent error. Known concentrations are run through the instrument to obtain a calibration curve. Then the new samples of the same known concentrations, or check standards, are run through the instrument again and solved for their concentration based on the new absorbance value using the calibration curve equation4. In the instrument used in this experiment, there was some error. A check standard for a concentration of 1ppm was ran through the instrument and came out to 1.27ppm6. The TDS observation does not lead to quantitative results and the solids in the residue may be other precipitates than those formed by magnesium ions and calcium ions. In short, the three methods of measuring water have their shortcomings, however, it is important to have to methods to compare readings to and ensure reasonable results.

Softening techniques include the addition of the lime or washing soda to the water and the ion exchange process. The chemical lime consists of calcium hydroxide. Calcium hydroxide dissociates in water and then magnesium ions form a precipitate of Mg(OH)2(s). Washing soda is sodium carbonate, which also dissociates in water. The carbonate forms a precipitate of CaCO3(s). These solids are then filtered out of the water, resulting in water with lower concentrations of magnesium ions and calcium ions2. In the ion exchange process, a resin, which is a bead of polystyrene coated in monovalent ions, is added to a sample of water7. In this experiment, the monovalent ion that coated the ion exchange resin was hydrogen ions. The presence of hydrogen ions as the coating ions was discovered by a pH test of the solution that remained after the ion exchange resin was added. All of the water samples displayed acidity6,9,10,11. The divalent magnesium and calcium ions replaced the monovalent hydrogen ions, on the resin, until the resin was saturated with magnesium and calcium ions, leaving the water sample virtually free of magnesium and calcium ions7. In summary, two common methods of softening water involve the addition of lime or washing soda to water and the ion exchange process. Regarding this experiment, many predictions can be made. In this experiment, sample of water were taken from stream water from Roarin Spring in Blair County, PA; stream water from Appalachian Springs in Blue Mountain, PA; pond water from the Alumni pond, and filtered drinking water from an Atherton Hall water fountain. It is predicted that the water from Roarin Springs or Appalachian Springs will have the softest water of the samples because it comes from a higher elevation than the other water sample sources. Water collects minerals that dissolve into the water as the water flows over rocks and soil. The less rock and soil the water has passed through, the less hard the water is7. Because the water from the springs originates from a higher

elevation than the other samples, it has travelled through less rocks and soil than the water in the other samples has. Therefore, the springs water will be softer than the other two water samples. These samples will leave less TDS behind when the sample is evaporated. It is expected that the Alumni pond water will be the hardest because it is at the lowest elevation and has not been processed at all, unlike the Atherton Hall water. The Alumni pond water will, predictably, have the most TDS remaining when the sample is evaporated. Regarding the water softening tests, it is expected that the springs waters will still be less hard than the other two water samples because the other two samples have a higher hardness initially. In short, it is predicted that the springs water samples will be softer than the other two water samples, and will remain softer even after water softening processes have been carried out.

Procedure: This experiment was carried out according to the steps within the PSU Chemtrek4. The water samples were measured for hardness using the AA first. A large pipette was filled with some of the water, and a diluted sample was prepared by adding 5mL of distilled to 5mL of sample water in a graduated cylinder. A large pipette was filled with this water. The diluted sample was prepared in case the concentration of either of the ions was too high for the AA to read. These samples were then taken to the AAs. The first AA measured calcium ion concentration and the second AA measured magnesium ion concentration. Prior to the use of the AAs, the AAs were calibrated. Next, the samples were tested for hardness by seeing how many total dissolved solids (TDS) the samples contained. Water sample drops were placed on individual pieces of aluminum foil, along with a drop of distilled water and a calcium ion solution for comparison4.

Measuring the water hardness by the EDTA method involved a serial dilution of EDTA. The number of drops of EDTA required to turn the purple water blue corresponded to the concentration of divalent ions in the water4. Next, the water samples tested for the ability to soften with two techniques. A commercial water-conditioning agent was added to the water sample. Then that solution was tested for hardness via the EDTA serial dilution test. The next softening technique used was the ion exchange resin. An ion exchange resin was added to the water sample. Then the water sample was tested for harness, using the EDTA serial dilution test. Once these tests were completed, calculations were made to find the hardness of the water4. Results: Atomic Absorption Spectroscopy Data Table 1. Calibration of Calcium Ion Concentration in the AA6. Caption: This table shows the absorbance values of the different known concentrations of calcium ions and the check standards. The values of the calcium ion concentrations and absorbances in this table are used to create a calibration curve seen in Graph 14. The check standards show the level of error in the instrument. The instrument has higher error in low concentration values and less error in higher concentration values6.

Calcium ion Concentration 0 1 5 10

Standard

Check

0.01082 0.05310 0.10000

1.27 5.09 9.81

25 50

0.23103 0.43298

24.08 50.45

Graph 1. Calcium ion Absorbance Values vs. Calcium ion Concentration6 Caption: The known calcium ion concentrations from Table 2 were plotted against their respective absorbance values from Table 2 to find a line of best fit. This line of best fit equation allows concentrations of calcium ions to be calculated based on the absorbance reading from the AA4. The trendline equation in this graph is y = 0.0085x + 0.016.

Absorption Value vs. Calcium Concentration

Absorption Value 0.6 0.4 0.2 0 0 10 20 30 40 50 60 Concentration (ppm) y = 0.0085x + 0.01 R = 0.9987

Table 2. Calibration of Magnesium Ion Concentration in the AA6 Caption: This table shows the absorbance values of the different known concentrations of magnesium ions and the check standards. The values of the magnesium ion concentrations and absorbances in this table are used to create a calibration curve seen in Graph 14. The check standards show the level of error in the instrument. The instrument has higher error in low concentration values and less error in higher concentration values6. Magnesium ion Concentration 0 Standard Check

1 5 10 25 30

0.01517 0.08718 0.18376 0.39579 0.48868

1.48 5.62 10.53 24.72 29.02

Graph 2. Magnesium ion Absorption Values vs. Magnesium ion Concentration6 Caption: The known magnesium ion concentrations from Table 2 were plotted against their respective absorbance values from Table 2 to find a line of best fit. This trendline allows concentration of magnesium ions to be calculated from the absorbance reading from the AA4. The line of best fit equation in this calibration graph is y = 0.0159x + 0.00836.

Absobrance Value vs. Magnesium Concentration (ppm)

Absorbance Value 0.6 0.4 0.2 0 0 5 10 15 20 25 30 35 Concentration (ppm) y = 0.0159x + 0.0083 R = 0.9972

Table 3. Concentration of Calcium ions and Magnesium ion in Samples Measured by the AA Caption: Table 3 displays the calcium ion and magnesium ion concentrations of each water sample measured by the AA and calculated using the equations from the graphs of the corresponding ion.

Calculation: Ion Concentration from Absorbance Value4 The concentration of calcium ions and magnesium ions in water samples were calculated plugging the absorbance reading from the AA in the calibration graph equation from Graph 1 and Graph 2 for the respective ions. Example calculation of ion concentration6: Absorbance value of calcium from the Atherton Hall water sample: 0.4216 y is the absorbance value that the AA measured. x is the concentration that is being solved for. y = 0.0085x + 0.01 In this example calculation, the absorbance value (y) being used is 0.4216. 0.4216 = 0.0085x + 0.01 Algebraic manipulation is used to isolate the x value by subtracting the 0.01 from 0.4216 and dividing that value by the slope of the trendline of 0.0085. Because x represents the ion concentration, the value x equals, once x is isolated using the trendline equation, is the ion concentration. 0.4116 = 0.0085x 48.42ppm = x Calculation: Concentration of Diluted Sample6 The diluted water sample contains half of the original concentration of the water sample. In this experiment, the only water sample that was diluted in order for the AA to be able to read the absorbance value was in the magnesium ion sample of the Atherton Hall water. In order to calculate to the undiluted concentration, the concentration that the calibration graph read in the diluted sample must be doubled, because this concentration represents only half of the original concentration.

16.67ppm = Magnesium ions concentration in the Atherton Hall water sample 33.35ppm = Magnesium ion concentration in the Atherton Hall water sample Calculation: Total Hardness of Water Calcium ion concentration (ppm) + Magnesium ion concentration (ppm) = Hardness (ppm) 48.42ppm + 33.35ppm = 81.77ppm Sample Absorbance in Calcium ion Calcium ion concentration Absorbance in Magnesium ion Magnesium ion concentration Hardness in ppm Atherton Hall6 0.4216 48.42ppm 0.2734 (diluted) 33.35ppm 81.77ppm Roarin Springs9 0.2720 30.82ppm 0.1258 Alumni Pond10 0.3073 34.98ppm 0.4012 Appalachian Springs11 0.3281 37.42ppm 0.3281

7.390ppm 38.21ppm

24.71ppm 59.69ppm

18.15ppm 55.57ppm

Table 4. Water Hardness in of Samples Determined by the EDTA Serial Dilution Caption: This table shows the hardness of the water samples based on the EDTA serial dilution. Calculation: Hardness in ppm by EDTA Serial Dilution To find the concentration of calcium ions and magnesium ions in the water samples based on the amount of EDTA added to the water sample, the molarity and volume of the EDTA were set equal to the molarity and volume of the calcium and magnesium ions since the amount of EDTA added is proportional to the ions concentration. The molarity of the EDTA was known to be 2.0 X 10-4M. The volume of the EDTA is the number of drops added to the water sample. Only one drop of water sample was in each well. The unknown variable, then, is the molarity of calcium

ions and magnesium ions in the water. Algebraic manipulation is then used to find the molarity, by dividing the product of the EDTA molarity and volume by the 1 drop of sample water. MEDTAVEDTA = MCa2+Mg2+ V Ca2+Mg2+ Molarity EDTA = 2.0 X 10-4 M Volume of EDTA = number of drops added to well Volume of Calcium ions and Magnesium ions: 1 drop Example: Atherton Hall water sample6 (2.0 X 10-4M)(12 drops EDTA) = MCa2+Mg2+(1 drop water sample) 2.4 X 10-3Mdrops = MCa2+Mg2+(1 drop water sample) 2.4 X 10-3M = MCa2+Mg2+ Calculation: Convert Molarity to ppm4 Water hardness is often measured in the amount of calcium carbonate (CaCO3(s)) in the solution necessary to have the same results as the EDTA titration. In this case, the moles in the molarity of the water sample are converted to grams of CaCO3(s) using the molar mass of CaCO3(s). Those grams are then converted to milligrams to result in parts per million (ppm)4. Example Calculation6: MCa2+Mg2+ X the grams in one mole of CaCO3(s) X the number of milligrams in one gram = ppm MCa2+Mg2+ = 2.4 X 10-3M 2.4 X 10-3M X Sample # of EDTA drops Hardness X = 240ppm Roarin Springs9 6 120ppm Alumni Pond10 50 1000ppm Appalachian Springs11 9 180ppm
4

Atherton Hall8 12 240ppm

Table 5. Comparison of Hardness Results from the Three Techniques in the Water Samples This table shows the difference in hardness levels that each method gave. Hardness Measurement Technique AA reading EDTA titration TDS Observation Atherton Hall8 81.77ppm 240ppm Faint thin white ring Roarin Springs9 38.21ppm 120ppm Distinct thin ring Alumni Pond10 59.69ppm 1000ppm Distinct thick ring Appalachian Springs11 55.57ppm 180ppm Thick white ring

Sample

Table 6. Hardness of Water Samples after Application of Water Softener Techniques Calculation: Hardness of Water in ppm after Water Softeners Added After the water softeners were added, an EDTA titration followed to find the hardness of the water samples. The calculation for this is the same as the calculations done for the hardness of water in Table 4. Water Softening Technique Baking Soda Addition Resin Addition Name and Sample Drops EDTA added Hardness ppm Drops EDTA added Hardness ppm Alaina Atherton Hall8 12 240ppm 3 60ppm Kyle Roarin Springs9 6 120ppm 1 10ppm Roxanne Alumni Pond10 12 240ppm 5 100ppm Casey Appalachian Springs11 9 180ppm 1 10ppm

Discussion: Overall, the results show that none of the water samples are considered very hard. The water samples all have hardness levels below 5.0 grains per gallon, the equivalent of 85.5ppm, using the values given in the AA readings, which is considered very hard2. On the whole, the hardness levels of the different water samples resulted as predicted. The water from the springs had the lowest levels of hardness. Roarin Springs water had the lowest hardness of 38.21ppm, given by the AA reading, and Appalachian Springs water was on the lower half with a hardness

level of 55.57ppm, from the AA reading6. The highest hardness level was found in the Atherton Hall water, with a hardness of 81.77ppm, from the AA reading, while the Alumni pond water had a lower hardness level of 59.69ppm, from the AA reading6. In short, the water samples had hardness levels from the AA readings that matched the hypothesis. The EDTA measurement gave very different results. As expected, the EDTA titration analysis of the water samples hardness did exceed the AA analysis, because the EDTA titration measures the concentration of all of the divalent ions in the water, not just calcium ions and magnesium ions as the AA does, making the AA reading more accurate than the EDTA measurement in regards to water hardness. For instance, in the Atherton Hall water, the EDTA titration reading of hardness of 240ppm, was roughly triple that of the AA reading of 81.77ppm. This significant difference in EDTA titration hardness readings and AA hardness readings may explain why the Alumni pond water had a lower hardness level of 55.57ppm than the Atherton Hall water 81.77ppm of according to the AA reading, and a hardness level, 1000ppm, significantly higher than that of the Atherton Hall water, 240ppm, according to the EDTA titration. The Alumni pond must contain additional polyvalent ions that the Atherton Hall water does not contain in order for the EDTA reading to be higher in the Alumni pond water while having a lower hardness level in the AA reading. In short, the EDTA measurements are less accurate than the AA readings. The TDS observation displayed results that conflicted with the other hardness reading methods. It appeared as though Appalachian spring water had the most total dissolved solids left after the water had evaporated even though the Appalachian spring water had a relatively low water hardness level of 59.69ppm. Meanwhile, the water sample with the highest hardness level of 81.77ppm had the least total dissolved solids. In short, apart from the TDS test, the hardness

levels of water in the water samples followed the hypothesis that the springs waters would have lower hardness levels. After water softeners were added to the water samples, similar pattern was seen. The lowest hardness levels were in the springs water and the higher levels were in the other two samples. As seen in Table 6, for the most part, the addition of the washing soda to the water samples did not decrease the hardness of the water samples. Only in the Alumni pond water and the Appalachian springs water did the hardness level decrease. However, as seen in Table 6, the ion exchange softening method caused water hardness levels to decrease dramatically across the board. For instance, after the ion resin was added to the Atherton Hall water decrease from a hardness of 240ppm to 60ppm, one-fourth of the original hardness. Generally speaking, the ion exchange resin is a more effective water softener than the commercial water softening agent. Throughout the experiment, there was plenty of room for error. To start, the AA instrument did not give completely accurate results. As seen in Table 1 and Table 2, the check standards deviated from the original concentrations. The original known concentrations were even concentrations of 1ppm, 5ppm, etc. They were run through the AA to find their absorbance values. The absorbance values were then plotted against the known concentrations to make a best fit line equation that could be used to find unknown concentrations based on absorbance values. When new samples of the same known concentrations, such as 1ppm, were run through the AA, the AA read different absorbance values, causing the concentration calculated based on the best fit line to not result in the same concentration, calculating to 1.27ppm instead of 1ppm in the calcium ions check standards. Lower known concentrations resulted in greater deviancies from the actual concentration. For instance, the calcium ion check standard for 1ppm was 1.27ppm, almost a 1/3 of a difference, while the calcium ion check standard for 50ppm was

50.45ppm, a 0.9% deviance6. The EDTA titration had ample room for error. When adding EDTA to the water sample solutions in the serial dilution, being one well off in determining which well shows the endpoint is a difference of 20ppm. The TDS observation has similar error factors as the EDTA, regarding a qualitative analysis. The TDS remaining on the aluminum foil may have appeared different to different eyes in the group. Also, as stated previously, the drop used to measure the TDS may have had a concentration of dissolved solids that misrepresents the entire what sample since the solution is not completely homogeneous. In all, there is ample room for experimental and human error in this experiment. Overall, the water hardness of each water sample was under or matched typical levels. The Atherton Hall water fountain water had a lower hardness level of 81.77ppm compared to average State College water of 120ppm-190ppm. Similarly, the Alumni Pond water, which is also in State College, had a hardness level of 59.69ppm, also within the State College water range of 120ppm-190ppm12. The spring water sample from Roarin springs had a water hardness level of 38.21ppm within the average range of Blair Countys water of 34ppm-85ppm13. The spring water sample from Appalachian springs had a hardness level of 55.57ppm, within the typical range of Blue Mountain areas water hardness levels of 5ppm-88ppm14. On the whole, the water hardness levels of each water sample either were under or matched typical levels. Conclusion: This experiment revealed the hardness of different water samples using different techniques, as well as tested the effectiveness of water softening techniques. The techniques to measure water hardness included AA, EDTA titration, and TDS observation. The water softening techniques included adding a washing soda to the water samples and the ion exchange process. The results of the experiment coincided with the hypotheses. The spring waters did

have the lower levels of hardness. In Roarin Springs, the water hardness, according to the AA reading, was 38.21ppm. The water hardness in the Appalachian Springs was 55.57ppm. Both of these values are higher than the hardness of the Alumni pond water, 59.69ppm, and the Atherton Hall water, 81.77ppm. The EDTA titration readings were higher than the AA readings, as expected. Overall, the experiment met predictions.

References: (Print sources are bolded.) 1. "Hard Water." The Water Quality Association. Water Quality Association. Web. 1 Nov 2012. <http://www.wqa.org/sitelogic.cfm?ID=207>. 2. Casiday, Rachel, and Regina Frey. "Water Hardness." The Department of Chemistry, Washington University. Washington University, n.d. Web. 1 Nov 2012. <http://www.chemistry.wustl.edu/~edudev/LabTutorials/Water/FreshWater/hardn ess.html>. 3. . "Hard Water Problems." Hard Water.org.uk. Guides Network. Web. 1 Nov 2012. <http://www.hardwater.org/hard_water_problems.html>. 4. Keiser, Joseph. PSU ChemTREK. Hayden McNeil. (2012-2013): 10-1 10-22. 5. Campbell, Jarryd, and Dan Peterson. "Concordia College Journal of Analytical Chemistry ." Concordia College Journal of Analytical Chemistry . 1. (2010): 48. Web. 1 Nov. 2012. 6. Weinheimer, Alaina. Chemistry 111 Notebook. 7. Skipton, Sharon O., Bruce I. Dvorak, and Shirley M. Niemeyer. "NEB Guide." NEB Guide. (2008): n. page. Web. 5 Nov. 2012.*

8. "Hardness in Drinking Water." wellcare. Water Systems Council. Web. 6 Nov 2012. <http://www.watersystemscouncil.org/VAiWebDocs/WSCDocs/1683274HARD NESS.PDF>. 9. Turner, Kyle. Chemistry 111 Laboratory Notebook. 10. Umali, Roxanne. Chemistry 111 Laboratory Notebook. 11. Watson, Casey. Chemistry 111 Laboratory Notebook. 12. . "FAQ." State College Borough Water Authority. State College Borough Water Authority. Web. 13 Nov 2012. <http://www.scbwa.org/pages/faq>. 13. "Frequently Asked Questions." Altoona Water Authority. Altoona Water Authority. Web. 13 Nov 2012. <http://www.altoonawater.com/index.php?page=faq>. 14. "Typical Water Quality Information: Blue Mountain System." Pennsylvania American Water. Pennsylvania American Water. Web. 13 Nov 2012. <http://www.amwater.com/paaw/customer-service/water-quality-reports.html>. * This source was a brochure I viewed online. The page numbers were not on the brochure. It was from the University of Nebraskas website.