The Chemistry of Natural Waters Josh Hull 11/9/05 Experiment #10 Meredith Hudak Mike Hinman Tanner Gokec

Tyler Hall

I.

Introduction: Hard water is water that has a high mineral content (water that contains a low mineral content is said to be soft). This content usually consist of high levels of metal ions, mainly calcium (Ca2+) and magnesium (Mg2+) in the form of carbonates1. Other metals as well as bicarbonates and sulfates may also be included.2 Earlier generations coined the phrase hard water because it made cleaning extremely difficult. Hardness is caused by compounds of calcium and magnesium, and a variety of other metals. All freshwater sources of water contain calcium and magnesium in varying quantities. Water tends to suspend, dissolve, and exchange certain trace elements and compounds from many objects that it contacts on its travels.3 For example, lime will harden water and peat will soften it. Total water hardness which includes both Ca2+ and Mg2+ is reported in parts per million (ppm) of calcium carbonate (CaCO3). Water hardness usually measures the total concentration of calcium and magnesium, the two most prevalent divalent metal ions.4 In some geographical locations, iron, aluminum, and manganese may also be present at elevated levels. Calcium usually enters the water from either CaCO3, limestone or from mineral deposits of CaSO4.5 Magnesium predominantly comes from dolomite, CaMg(CO3)2.6 Temporary hardness pertains to hardness which can be removed by boiling or by the addition of lime (calcium hydroxide). It is caused by dissolved calcium bicarbonate in the water. Calcium bicarbonate is less soluble in hot water than in cold water, so boiling (which promotes the formation of

carbonate) will precipitate calcium carbonate out of the solution, leaving water that is less hard on cooling.7 On the other end of the spectrum, permanent hardness is mineral content that cannot be removed by boiling. It is usually caused by the presence of calcium and magnesium sulfates in the water, which are more soluble as the temperature rises. The mixture of minerals dissolved in the water, together with the waters acidity or alkalinity, as well as the temperature, will determine the behavior of the hardness.8 Descriptions of hardness correspond roughly with the ranges of mineral concentrations:9 Hardness Soft Moderately Soft Slightly Hard Moderately Hard Hard Very Hard Concentration of Calcium (mg/L Ca) 0-20 20-40 40-60 60-80 80-120 >120

Water hardness does not present a health hazard, however it can cause many potentially costly problems. Hard water also causes scaling, which is the precipitation of minerals to form a rock-hard deposit called lime scale.10 Scale has the potential of clogging pipes and decreasing the life of toilet flushing units by 70% and water faucets by 40%.11 It may also coat the insides of tea pots and coffee pots, and clog and destroy hot water heaters.

In the household environment, hard water requires more soap and synthetic detergents for laundry and washing. It takes half as much soap for cleaning with soft water. Hard water and soap often combine with one another to form soap scum which cannot be rinsed off. This scum forms bathtub rings and unwanted spots on your dishes. Using soap on your body in hard water can cause the formation of scum which is often referred to as curd.12 The formation of scum and curd is caused when calcium and magnesium form insoluble salts with anions.13 This curd remains on the skin even after rinsing. The curd may then clog pores and coat body hair. This can serve as the origin for bacterial growth, causing diaper rash, minor skin irritation and skin that constantly itches.14 In commercial industry, hard water contributes to scaling in boilers, cooling towers, and other industrial equipment. When hard water is heated or evaporated, rocklike deposits consisting mainly of calcite crystals form on the surface of pipes, boiler walls, tubes, and evaporator surfaces.15 Scale is one of the banes of industry. It blocks jets and tubes, and narrows pipes. The hard layer interferes with heat transfer in boilers, leading to gross energy inefficiencies, and can often lead to metal corrosion and structurally weakness. In these settings, water hardness must be under constant review to avoid costly breakdowns. Hardness is controlled by the addition of chemicals and by large scale softening with zeolite resins. A water softener works on the principle of cation or ion exchange in which ions of the hardness minerals are exchanged for sodium or potassium

ions.16 The most economical way to soften household water is with an ion exchange water softener. This unit uses sodium chloride (table salt) to recharge beads made of ion exchange resin the exchanges hardness minerals for sodium17. Artificial or natural zeolites can also be used. As the hard water passes through and around the beads, the hardness minerals attach themselves to it, dislodging the sodium ions. This process is called ion exchange18. When the beads or sodium zeolite has no sodium ions left, it is exhausted and can no longer soften the water. The resin is recharged by flushing with saltwater. The excess of sodium ions force the hardness ions off the resin beads. The excess sodium is rinsed away and the resin is ready to start the process all over again. According to the US Geologic survey, 85% of US homes have hard water.19 The softest water occurs in parts of New England, South AtlanticGulf, Pacific Northwest, and Hawaii regions.20 Moderately hard waters are common in many of the rivers of Tennessee, Great lakes, Pacific Northwest, and Alaska regions.21 Hard and very hard waters are found in some of the streams in most of the regions throughout the country22. Hardest waters are found in the streams of Texas, New Mexico, Kansas, Arizona and Southern California23. EDTA titration is used to determine the concentration of divalent cations (hardness) in water (for example the concentration of calcium and magnesium).24 1. A known volume of water is taken and the pH is adjusted to 10 by a NH3/NH4 buffer. 2. EBT indicator is added to the solution. At the

high pH the indicator is in the HD2- form, which is blue. 3. If magnesium is present in the water sample then it will react with the indicator to form a wine red chelate. Calcium does not react with the indicator. Therefore, at the start of the titration, the solution is wine red in color. 4. EDTA solution is now added to the solution from a microburet. It first reacts with calcium and forms a colorless chelate. As soon as enough EDTA has been added, it begins to react with the magnesium indicator chelate to produce a MgEDTA chelate. When the magnesium is removed from the indicator, it returns to its blue form. 5. The end point of titration is a definite change from a wine red color to a blue sky color.25 Titration is difficult to do if there is little or no magnesium in the water sample. If there is no magnesium in the sample, then the color of the solution at the beginning would be the same at the end of the titration, in other words there would be no end point. In order to ensure that the sample contains enough magnesium, it is usually spiked with a solution which contains the MgEDTA chelate.26 After the titrations were complete in the experiment, the following equation was used to determine the concentration of the calcium solution. Moles of EDTA=moles of Ca2+ MEDTAVEDTA=MCa2+VCa2+

Atomic absorption spectrophotometry (AA) is a technique which is used to determine metals that are dissolved or suspended in a solution.27 These metals can consist of alkalis, alkaline earth, and even transition metals. In order for the atom of interest to be excited, the energy of light falling on the atom must match the energy separation between two electronic energy levels.28 This principle is used in the operation of AA. Monochromatic light having the energy corresponding to the change in energy of the atoms of interest is shined through the sample which is to be analyzed.29 Atoms which have electronic energy separation will absorb the light. The amount of absorbance is proportional to the concentration of the metal atoms in the sample. The Beer-Lambert law is used to calculate the unknown metal concentration in the sample30. A typical atomic absorption spectrophotometer functions in a systematic way. Voltage across the electrodes excites the calcium and magnesium inside the lamp. When the excited Mg or Ca atoms relax, a monochromatic light is produced which equals the energy separation of the two electronic levels. The emitted monochromatic light will then be absorbed by Mg or Ca atoms in the water sample.31 The liquid water sample is then aspirated into the sample chamber where it is converted from a liquid to a fine aerosol which is introduced into a flame. The flame is composed of air-acetylene mixture which reaches 2300 degrees Celsius. This temperature is capable of atomizing everything in the liquid sample. The light from the hallow cathode lamp passes through the flame where the sample is atomized. The light will

only be absorbed if there is a matching energy separation of energy levels.32 A grating in the monochrometer is adjusted so that only the wavelength of light corresponding to the energy change of the metal of interest is allowed to pass through a narrow slit. This light then falls on the detector which is a photomultiplier tube (PMT). Since the metal atoms absorb some light passing through the flame from the lamp, a decrease in initial signal is detected by the PMT. This decrease is proportional to the concentration of metal in the sample.33 The concentration of a metal sample is determined by a calibration graph that is based on the light absorbance of known concentrations of the metal of interest. The goal of this experiment is to determine the hardness of five different water samples: Aquafina, Dasani, Poland Springs, Evian, and tap water from Millheim, PA. These values will then be compared to each other as well as to the state average of hardness for the location in which each bottled water is produced. After these values are obtained it will be possible to determine whether each company prefers to sell water which is softer or harder than that which is found within the state. Millheim town water will be tested due to the curiosity of how it will compare to the expensive bottled water which is sold at the store. After all of the samples are tested, the degree of hardness chart found on page 718 in Chemistry- The Molecular Science, will be used to classify the samples as soft, slightly hard, moderately hard, hard, or very hard.34 My hypothesis for this investigation is that the hardness of each bottled water sample is going to be different than the state value for hardness

of where it is produced. This conclusion has been derived on the basis that pure water from each state is not just being bottled and sold. Companies use methods such as chemical and mechanical water softeners, water filters and magnetic water conditioners to adjust the hardness of water. The hardness of drinking water does not affect your life as much as the hardness of the water which is used for household appliances. It is important to get the water at your own household tested for hardness. The information that is produced from this test is essential to saving money that will be needed to repair industrial malfunctions due to water hardness. The addition of a water softening machine can prevent the clogging of pipes, bath tub rings, dripping faucets, and the need to replace hot water heaters. II. Procedure: The procedure for this investigation is found in the PSU Chemtrek manual. Each water sample is visually examined for particles. If the sample is not clean it will need to be filtered before the AA process can take place. Two bulbs must be filled with the sample water (one for Ca analysis and one for the Mg analysis). Each sample must then be taken to the instrumental analysis room where the AA process will take place. An experienced chemist will assist you in operating the AA machine. A series of buttons are pressed and a thin straw is placed in your water sample. The machine begins its complicated process (explained in intro) and another button is pressed which provides you with the absorbance value for your sample. This process must be done twice, once for calcium concentration and one for magnesium concentration. Once the absorbance values have been

obtained, a calibration graph of light absorbance vs. metal ion concentration must be made. Determine the equation of the best fit line for the data. The absorbance value can then be plugged into the equation in order to produce a value for the metal ion concentration. This value will then need to be converted to its equivalent concentration of CaCO3. Finally, the hardness due to calcium and magnesium must be added together to give a total hardness value. A qualitative measurement of the total dissolved solids (TDS) will be determined. A TDS value is related to hardness, but it is not identical to the hardness of a sample. Water with a high TDS will most likely be hard. But, if all of the dissolved solids were NaCl then the sample would have a hardness of zero. A small piece of aluminum is obtained and placed shiny side up on a bunsen burner. Two drops of water, one of the designated sample and one of distilled water are placed on the foil. Allow the water to evaporate and remove the foil from the burner. The white solids that remain are nonvolatile salts that were originally in the water sample. This information provides you with some insight about what your hardness value is comparable to (a lot of white solid usually means a high hardness). Divalent Cation Analysis by EDTA titration will take place. This section requires a quantitative volumetric analysis. One drop of calcium solution, EBT indicator and buffer is added to each of the wells in a 1x12 well strip. The strip will now be serially titrated with EDTA solution. The first blue well

is the point where excess EDTA is present. Concentration based on volume can now be determined using the following equation:

Moles of EDTA=moles of Ca2+ MEDTAVEDTA=MCa2+VCa2+ The same titration must also be done for magnesium, the sample of interest, water which contains a water conditioning agent, and water which has had divalent cation removal by ion exchange.

III. Results: Fig. 1 Calibration graph of light absorbance vs. metal ion concentration for Ca

Absorbance vs. Concentration for Cay = 0.018x + 0.017300.10.20.30.40.50.60.70.

Fig. 2 Calibration graph of light absorbance vs. metal ion concentration for Mg

Absorbance vs. Concentration for Mgy = 0.0152x + 0.003500.050.10.150.20.250.30.350.4

Calibration graphs were derived from data supplied by the instrument operator. Known absorbance values were graphed vs. known concentration values. A best fit line supplied an equation which will be used in order to determine the concentration of the test sample.

Fig. 3 Chart of Mg/Ca hardness determined by AA analysis (best fit line) Water type Millheim tap water Evian Dasani Poland Springs Aquafina Mg2+ hardness (ppm) 5.88 25.7 .656 1.06 9.3 Ca2+ hardness (ppm) 30 42.35 4.63 3.15 9.13

The equation that was produced by the calibration curve was used to determine the hardness values in Fig. 3. Fig. 4 Chart of concentration of CaCO3 AA analysis Water type Mg2+ CaCO3 concentration (ppm) Millheim tap water Evian Dasani Poland Springs Aquafina 23.87 105.76 2.67 4.36 38.27 Ca2+ CaCO3 concentration (ppm) 75 105.88 11.6 7.875 22.825

The hardness values in Fig. 3 were converted to CaCO3 concentration values in Fig. 4. This method of determination will be compared to the EDTA method.

Fig. 5 Chart of hardness EDTA analysis Water type Hardness (ppm) Hardness (grains/gal) Millheim tap water Evian Dasani Poland Springs Aquafina 120 120 0 4.21 20 7.0 7.0 0 4.68 1.17

A series of titrations where conducted in order to obtain the hardness of the sample waters. This method of determination will be compared to the AA analysis method. Fig. 6 Chart of Total Hardness Value (THV) AA analysis Water type Millheim tap water Evian Dasani Poland Springs Aquafina THV (ppm) 98.8 211.64 14.27 12.24 61.10

The THV was determined by adding both the concentration of calcium and magnesium together. These values will then be compared to the THV determined by EDTA analysis. Fig. 7 Chart of Total Hardness Value (THV) EDTA analysis Water type Millheim tap water Evian Dasani Poland Springs Aquafina THV (ppm) 120 120 0 4.21 20

The THV was determined by adding both the concentration of calcium and magnesium together. These values will then be compared to the THV determined by AA analysis.

Fig. 8 Classification of Water Hardness Hardness Soft Moderately Soft Slightly Hard Moderately Hard Hard Very Hard Concentration of Calcium (mg/L Ca) 0-20 20-40 40-60 60-80 80-120 >120

This chart will be used to classify the hardness due to concentration of calcium for the five different samples.

Fig. 9 Chart of Average Water Hardness for Various States/Countries State/Country and type of water Hardness due to Ca2+ CaCO3 concentration (ppm) 9 65 122 130 59

Maine (Poland Springs) New York (Aquafina) Pennsylvania (Millheim tap water) France (Evian) Vermont (Dasani)

A comparison will be made between the hardness values of the sample waters and the state in which they are produced in based on the information presented in Fig. 9. Fig. 10 Classification of Hardness Water Type Poland Springs Aquafina Millheim tap water Evian Dasani Classification of Hardness Soft Moderately Soft Moderately Hard Hard Soft

Sample Calculations: 1. Determination of Ca2+ and Mg2+ hardness by best fit line (absorbance value to ppm) Ca2+ y=.018x+.0173 .5562=.018x+.0173 .5389=.018x x=29.93 ppm y=.0152x+.0035 .0771=.0152x+.0035 .0736=.0125x x=5.88 ppm

Mg2+

2. Converting a metal ion concentration in ppm, to a hardness value in ppm Ca2+ ppm Ca2+ x[100g CaCO3 per mole/40.0 g Ca2+ per mole] 30x[100g CaCO3 per mole/40.0 g Ca2+ per mole]= 75 ppm CaCO3=75 ppm hardness Mg2+ ppm Mg2+ x[100g CaCO3 per mole/24.3 g Mg2+ per mole] 5.88x[100g CaCO3 per mole/24.3 g Ca2+ per mole]= 23.87 ppm CaCO3=23.87 ppm hardness 3. Calculation of Total Hardness Value AA Analysis Total hardness value=Ca2+ ppm+Mg2+ ppm Total hardness value=75+23.8 Total hardness value=98.8ppm Ca2+ and Mg2+

4. Calculation of Hardness in molarity EDTA Analysis MEDTAVEDTA=MSAMPLEVSAMPLE (2.0x10-4)(6)= MSAMPLE(1) MSAMPLE=1.2x10-3 M

5. Converting a molar concentration of divalent cations into a hardness value in ppm EDTA Analysis Hardness=1.2x10-3 mol CaCO3/ 1 liter Hardness=(1.2x10-3 mol CaCO3/ 1 liter) x (100g CaCO3/ 1 mol CaCO3) x (1000mg CaCO3/ 1 g CaCO3) Hardness= 120mg/ liter Hardness=120 mg CaCO3/ 1000g H20 Now: 1mg CaCO3/1000g H20 Therefore: 120mg CaCO3/ 1000g H20= 120 ppm hardness

6. Converting ppm value to grains/gallon EDTA Analysis 1 grain=64.7 mg 1 gallon=3.785L 1 grain CaCO3/gal H20= 17.1ppm 120ppm x (1grain/gal)/ 17.1 ppm= 7.0 grains per gallon IV. Discussion: At the conclusion of the experiment, all goals were met. Water samples from five different sources: Aquafina, Dasani, Poland Springs, Evian, and tap water from Millheim, were successfully analyzed and a hardness value was produced for each. Fig 4 shows the break down of Mg2+ CaCO3 concentration and Ca2+ CaCO3 concentration in parts per million for each sample of water determined by AA analysis. Referring to the Mg2+ CaCO3 concentration, Evian water produced the highest hardness value of 105.76ppm, Aquafina yielded 38.27ppm, Millheim tap water 23.87ppm, Poland Springs 4.36ppm and Dasani was the softest at 2.67ppm. Analyzing the Ca2+ CaCO3 concentration, Evian once again produced the highest hardness value of 105.88ppm, Millheim tap water followed with 75ppm, Aquafina 22.825, Dasani 11.6ppm and Poland Springs was the softest at 7.875ppm. All of the bottled water samples seem to contain a

balance between Ca2+ CaCO3 concentration and Mg2+ CaCO3 concentration. The largest difference between both concentrations is 15.445ppm. This difference was produced from Aquafina water. Millheim tap water did not contain a balance between the two concentrations. The concentration difference was 51.13ppm. This may be due to the fact that tap water is treated in a different manner than bottled water. Unlike the bottled water companies, the Millheim water treatment center does not try to produce a balance between calcium and magnesium concentrations. In order to obtain a reasonable comparison between the water samples, the total hardness value determined by AA analysis must be reviewed. Fig. 6 categorizes the THV for each type of water. Out of five water samples, Evian yielded the highest total hardness value of 211.64ppm, Millheim tap water was second with 98.8ppm, Aquafina 61.10ppm, Dasani 14.67ppm, and Poland Springs was the softest at 12.24ppm. With the AA determination of Ca2+ CaCO3 concentration in each sample, a comparison between the state averages of Ca2+ CaCO3 concentration in the state in which the bottled water was produced can be made with the AA value. This comparison is being made in order to determine whether the bottled water companies prefer to produce water higher or lower than the state average of Ca2+ CaCO3 concentration. Fig. 9 shows the average calcium carbonate concentration for each state. Of the five water samples tested, all of them contained a hardness value less than the state averaged of where they are produced. This provides evidence that the bottled water manufactures prefer to sell their

products lower than the state average. This data also suggest that the bottled water companies are not simply bottling tap water and selling it. Methods such as chemical and mechanical water softeners, water filters, and magnetic water conditioners are being used to create softer water for sale. The fact that Millheim tap water is below the state average simply means that the Millheim region produces water slightly softer than the state average. The difference in hardness was only 47ppm. Fig. 10 was used to classify the hardness of the water samples by concentration of calcium. Poland Springs and Dasani both fell under the category of soft. Aquafina was moderately soft, Millheim tap water was moderately hard, and Evian was ranked as hard. The hypothesis for this investigation was experimentally proven to be correct. The hardness of each water sample was different than the state average value for hardness for the state in which it was produced. In fact, the hardness value for each sample was less than the state averages, once again supporting the idea that manufactures are using methods such as: chemical and mechanical water softeners, water filters, and magnetic water conditioners to produce softer water. EDTA titration and AA analysis were used to determine the hardness of the water samples. After reviewing data, AA analysis proved to be the more accurate of the two methods. The AA machine has been calibrated and fine tuned to produce precise as well as accurate information. EDTA titration is only precise to one drop due to the fact that half and quarter drops of titration solution can not be produced. The use of AA analysis

also eliminates a large portion of human error that could occur while performing calculations like those that are required for EDTA. Human error could occur while graphing the calibration curve and converting the absorbance value to concentration. However, this process only counts for a portion of the calculation. The absorbance value produced by the AA machine is not affected in any way by calculations that contain human error. The entire EDTA process requires human computations. This fact allows for a large margin of error due to mistakes made by the chemist. Due to the possibility of human error, all EDTA values were reviewed. After comparing THV for AA analysis to EDTA titration, it was determined that the calculations for EDTA must be repeated for all bottled water samples. Referring to Fig. 6 and Fig. 7, it is obvious that the values do not agree with each other. For instance, Millheim tap water produced a THV of 98.8ppm (AA analysis) and 120ppm (EDTA). This two values are reasonable due to the fact that the calculations were repeated several times. On the other hand, Evian water yielded a THV of 211.64ppm (AA analysis) and 120ppm (EDTA). Duet to the fact that the EDTA values of Millheim tap water and Evian water are the same and the AA analysis determination is different, an error was obviously made. Due to the fact that the other EDTA values for the bottled waters dont agree with the data, the EDTA values were not taken into consideration when comparing the hardness values of the water samples. For better results, EDTA titration must be preformed again.

Referring to fig. 7, it may appear as though an error occurred while calculating the THV for Aquafina water while using the EDTA method. This assumption is incorrect. Due to very low calcium and magnesium concentrations in Aquafina water, the EDTA method is insufficient when trying to determine the hardness value. V. Conclusion: The hardness values for Aquafina, Dasani, Poland Springs, Evian, and tap water from Millheim, PA were successfully determined. After comparing these values to the state average values, it was concluded that they all fell below the average state hardness values. This suggest that water manufactures are using methods to soften the water before it is sold. In conjunction, these manufactures prefer to sell the water at a hardness below the state average. The hypothesis for this investigation stated that: the hardness of each bottled water sample is going to be different than the state value for hardness of where it is produced. Data produced by this experiment supported and proved the hypothesis to be correct. However, for a better comparison between AA analysis and EDTA titration, all EDTA titrations should be repeated due to human error. VII. References: 1. Water Treatment Methods. http://www.hardwater.org/water_treatment.html. (Oct. 22, 2005). 2. Water Hardness. www.chemistry.wustl.edu/~edudev/LabTutorial/Water/FreshWater/hardness.html. (Nov. 1, 2005).

3. Explanation of Water Hardness. http://water.usgs.gov/owq/Explanation.html. (Oct 28, 2005) 4. Leeden, Frits van der; Troise, Fred L.; Todd, David Keith The Water Encyclopedia. Lewis Publishers, Second Edition: Chelsea, MI, 1990 pages 449-453. 5. Moore, John W.; Stanitski, Conrad L.; Jurs, Peter C. Chemistry-The molecular science. Harcourt College Publishers, First Edition: Philadelphia, 2002, page 718. 6. Thompson S. PSU Chemtrek 2005-06, Haydem McNeil Publishing pages 10-15 - 1022. 7. Chem 14 Student packet, section 101-106, Fall 2005, Joseph T. Keiser. pages 49-54. 8. Mike Hinman, Chem 14, Lab Notebook, pg. 17 9. Meredith Hudak, Chem 14, Lab Notebook, pgs. 37-40 10. Tanner Gokec, Chem 14, Lab Notebook, pg. 30 11. Tyler Hall, Chem 14, Lab Notebook, pgs. 27-29 12. Holt, Jack. Water Properties. W.W. Norton and Co. Publishing, First Edition: New York, NY, 1998, pages 38-45. Endnotes to references 1. http://water.usgs.gov/owq/Explanation.html 2. Ibid 3. Ibid 4. www.chemistry.wustl.edu/~edudev/LabTutorial/Water/FreshWater/hardness.html 5. Ibid

6. Ibid 7. Ibid 8. Ibid 9. http://water.usgs.gov/owq/Explanation.html 10. Ibid 11. Water Properties 12. Ibid 13. Ibid 14.. http://www.hardwater.org/water_treatment.html 15. http://water.usgs.gov/owq/Explanation.html 16. http://www.hardwater.org/water_treatment.html 17. Ibid 18. Ibid 19. Water Encyclopedia 20. Ibid 21. Ibid 22. Ibid 23. Water Encyclopedia 24. Water Properties 25. Steps 1-5 PSU CHEMTREK 26. Ibid 27. Ibid 28. Ibid 29. Ibid 30. Ibid 31. Ibid 32. Ibid 33. Ibid

34. Chemistry-The molecular Science