The Chemistry of Natural Waters

Michael Martoglio
April 6, 2009 Chem 111 Section 104 TA: Shradda Surve Group: Jun Lee, Hayley Miller, Skyler Marzewski

I. Introduction In this lab, we were instructed to set out to explore different ways to test characteristics of a sample of water and its water hardness. Hard water is evaluated as the type of water that contains high concentrations of the divalent cations Ca2+ and Mg2+. These two cations enter streams, rivers, lakes and other water bodies by the dissolution of minerals as the water flows through rocks and soil.(2) The Calcium comes from sedimentary rocks such as limestone and dolomite, while Magnesium comes from rocks like olivine and pyroxenes. (11) A water sample with high concentrations of both of these are said to be hard, while lower concentrations are soft. Because hard water is natural, it can be found basically anywhere and its uses are endless. Hard water can be used in showers, garden hoses, and even drinking water. Although soft water is preferred as a drinking water, hard water will not harm you. (12) Hard water is important because of its use in industrial boilers and evaporators. Also untreated waters that are still hard are better in cleaning. When used with soaps and detergents, they help reduce the chemical bonds between dirt and the surface make it easier to be cleaned. (11) Water hardness is measured in units of parts per million (ppm). The higher the ppm, the harder the water is considered. (5) In this lab we explored two primary ways of testing water hardness, EDTA and AA. The EDTA is a titration can only be used when there are significant amounts of Ca2+ and Mg2+. The EDTA is an inexpensive lab experiment. To use this experiment you take a known amount of natural water and bring its pH to 10 by use of a buffer. Next you add EBT indicator which turns the solution blue because of the high pH. This indicator will soon turn a red wine color with the presence of Mg2+ but does not test for the presence of Ca2+.(11) Then a known concentration of EDTA solution is added which reacts first with Calcium and then the Magnesium. Once all of the Magnesium

has reacted to form a colorless chelate and is removed from the indicator, it will return to its blue color. The end of the titration comes when the color is now a definite sky blue.(11) The use of an Atomic Absorption Spectrophotometer is a large machine that although is easier to use it works in a more complicated manner. In region 1 of the machine, you select what you are testing for (Ca2+ or Mg2+). A beam of light leaves region 1 with the same energy level required to dissociate a molecule of what youre testing for. In region 2, about 10% of your sample is picked up and turned into an aerosol. The aerosol is then released in the form of a flame. The light passes through the flame and since it has the energy to dissociate the element youve been selected it is absorbed by the aerosol in the flame.(1) The light passes into region 3 through a slit which only allows the wavelength for the element you selected in region 1. Region 3 contains a photomultiplier tube (PMT) which reads and determines how much of Ca2+ and Mg2+ is in the light. This amount is proportional to the amount in your water sample. (11) These two methods differ because the titration is a very inexpensive experiment that takes a few minutes to perform. The use of AA is a very large, expensive machine which takes merely seconds. Also the AA is only capable of calculating the absorption of Ca2+ and Mg2+. The titration can calculate all polyatomics such as Chloride and Sodium. Water softening techniques work by using softeners such as sodium carbonate to reduce the dissolved calcium and magnesium ions in the water. Large scale softening techniques use negatively charged resin to attract the positive Ca and Mg ions. When the ions attach to the resin, potassium, hydrogen or sodium ions are released into the water. (5) I expect all of the water samples to, at some level, be considered hard. I think the water sample from Whitmore to be the hardest because it is tap water from the bathroom. The sample from the apartment on Pugh street is also tap water but because it is not on campus I think it will be

softer. The samples from the HUB and the on-campus dorm are from water fountains. Because these are supposed to be suitable drinking waters, I think they should be softer. II. Procedure The procedure for this experiment came step-by-step from the PSU Chemtrek book. (1) In the first section we used the AA method to determine the level of hardness for our water samples. Because this is a machine that uses extremely advanced technology, the work on our part was limited and its process was mentioned above. The intensity of the light from region 3 in the spectrophotometer can be found using the Beer-Lambert Law. Our results will be discussed later. Next, we dissolved a small amount of our sample and compared it to a drop of distilled water and 1x10-3 M Ca2+. My water sample left a dark circle where it previously was while the distilled water left no trace behind and the Calcium left a light ring. This is because the white solids that remain are the original nonvolatile salts present in the water.(7) The amount of nonvolatile salts is known as the total dissolved solids (TDS). (11) We then performed a serial EDTA titration with Calcium, EBT indicator, buffer, and EDTA solution. After close observation to find the well where the color changed we used the formula MEDTA VEDTA = MCa2+ VCa2+. In this equation M is the molarity of the substances and V is the volume. For our experiment, the volume was represented by the number of drops in the well where the initial color change took place. This equation, when solved for MCa2+ will give us the concentration of the original Ca2+. (11) Again, our results will be discussed later. Using the same concept as before, we found the hardness of a mixture of 20 mg of a commercial conditioning product in our water sample. We then compared our results. III. Results Table 1 shows the absorbance rates for the water samples obtained by using the spectrophotometer.

Table 1- AA Absorption Rates (6,7,8,9) Sample Name Ca2+ Absorbance HUB Apartment (Pugh St) Dorm (Packer Hall) Whitmore Skyler Hayley Mike Jun 0.2926 0.2051 0.3186 0.4834 Mg2+ Absorbance 0.3214 0.1671 0.3222 0.5419 1:1 1:1 1:1 1:1 Dilution

Graph 1 shows the absorbance value versus the concentration of calcium. These numbers were presented to us when conducting the AA experiment.

Graph 1-

Graph 2 shows the absorbance value versus the magnesium of calcium. These numbers were presented to us when conducting the AA experiment. .

Also for section A, after producing these graphs and returning with our Calcium and MagGraph 2nesium data we are able to determine the hardness. By using the equations of

the trendline on the graphs and plugging in our values for Ca2+ and Mg2+ respectively we can find the light absorbance values. For Calcium, my trendline equation was: y = 0.0111x + 0.0513 Now when I plug in the Calcium concentration from the AA for the y value and solve the equation for x, I get x= 24.08 ppm Ca2+. I then use the following equation to convert to water hardness. (11) 1 ppm Ca2+ x 100 g CaCO3 1 mole _ = 2.5 ppm CaCO3 = 2.5 ppm hardness 2+ 40.0 g Ca 1 mole

For example my conversion would be: 24.08 ppm Ca2+ x 100 g CaCO3 1 mole _ = 60.2 ppm CaCO3 = 60.2 ppm hardness 2+ 40.0 g Ca 1 mole

Table 2 shows the results doing the same with my groups numbers. Table 2- AA Water Hardness (Ca2+ ) (6,7,8,9) Sample HUB Apartment (Pugh St) Dorm (Packer Hall) Whitmore Name Skyler Hayley Mike Jun Hardness (ppm) 54.3 34.6 60.2 97.3

We would do the same of the Magnesium value with the Magnesium trendline equation. My magnesium equation was: y = 0.0182x + 0.0635 Now when I plug in my Mg2+ concentration into the equation for y and solve for x I get

14.2 ppm Mg2+ . We then must convert this number into water hardness using the following equation: 1 ppm Mg x
2+

100 g CaCO3 1 mole _ = 4.12 ppm CaCO3 = 4.12 ppm hardness 24.3 g Mg2+ 1 mole

For example, my water hardness would be 14.2 ppm Mg2+ x 100 g CaCO3 1 mole = 58.4 ppm CaCO3 = 58.4 ppm hardness 2+ 24.3 g Mg 1 mole

Table 3 shows my groups data going through those same steps. Table 3- AA Water Hardness (Mg2+ ) (6,7,8,9) Sample HUB Apartment (Pugh St) Dorm (Packer Hall) Whitmore Name Skyler Hayley Mike Jun Hardness (ppm) 58.4 23.4 58.4 108.2

The total hardness is shown in Table 4.

Table 4- Total Hardness (6,7,8,9) Sample HUB Apartment (Pugh St) Name Skyler Hayley Hardness (ppm) 112.7 58.0

Sample Dorm (Packer Hall) Whitmore

Name Mike Jun

Hardness (ppm) 118.6 205.5

Table 5 shows the absorption rates for my groups water samples obtained by using the EDTA titration Table 5- EDTA Titration (6,7,8,9) Sample HUB Apartment (Pugh St) Dorm (Packer Hall) Whitmore Name Skyler Hayley Mike Jun Drops of Sample 1 1 1 1 Drops of EDTA 39 24 23 12 Dilution none none none none

In section D, we had to determine the hardness of our water samples by counting the number of drops of EDTA it took to change the color of the well. We use the following equation with the following variables: MEDTA: (2.0x10-4 M) VEDTA: number of drops of EDTA (differs for each sample) MCa2+: What we are solving the equation for VCa2+: 1 For example, the equation for my water sample would be: (2.0x10-4 M) (23) = (MCa2+) (1) MCa2+ = 4.6x10-3 M Table 6 shows the concentration of the samples after plugging the number of drops in. Table 6- Calcium Concentration (6,7,8,9) MEDTA VEDTA = MCa2+ VCa2+

Sample HUB Apartment (Pugh St) Dorm (Packer Hall) Whitmore

Name Skyler Hayley Mike Jun

Concentration 7.8x10-3 M 4.8x10-3 M 4.6x10-3 M 2.4x10-3 M

Instead of expressing the concentrations in molarity, we then had to convert it to ppm. 1x10-3 M 1 liter of solution x 100.0 g CaCO3 1 mole CaCO3 1000 mg CaCO3 100 mg CaCO3 x 1 g CaCO3 = 1 liter of solution

The final number of this equation is equal to ppm Table 7 shows the concentration of the water samples using the above equation to convert to ppm. Table 7- Calcium Concentration in Parts per Million (ppm) (6,7,8,9) Sample HUB Apartment (Pugh St) Dorm (Packer Hall) Whitmore Name Skyler Hayley Mike Jun Concentration (ppm) 780 480 460 240

We then took the concentration in ppm and converted to grams/gallon. This was done by the following: 100 ppm x 1 grain per gallon = 5.8 grain per gallon 17.1 ppm For example my conversion would be: 460 ppm x 1 grain per gallon = 26.9 grain per gallon 17.1 ppm Table 8 shows the Calcium concentrations in grain per gallon. Table 8- Calcium Concentrations in grain/gallon (6,7,8,9)

Sample HUB Apartment (Pugh St) Dorm (Packer Hall) Whitmore

Name Skyler Hayley Mike Jun

Concentration (grains/gallon) 45.6 28.1 26.9 14.0

In Section E we experimented water softening with our water sample and a commercial water-conditioning agent. This commercial product was designed to make water softer. We mixed in 20 mg of the product and then completed an EDTA titration with our water samples. Our results are displayed in Table 9. The conversions into ppm have already been completed. (11)

Table 9- Concentration with Commercial Water-Conditioning Agent (6,7,8,9) Sample HUB Apartment (Pugh St) Dorm (Packer Hall) Whitmore Name Skyler Hayley Mike Jun Concentration (ppm) 380 240 230 120

The concentration of everyones water sample went down with the use of the water softener. In Section F, we explored the use of cation exchange resins in the removal of Ca2+ and Mg2+ from our water samples. Again using the EDTA titration we determined the hardness of our treated water sample. Table 10 shows the concentrations of the samples after they were treated. Table 10- Concentration after Ion Exchange (6,7,8,9)

Sample HUB Apartment (Pugh St) Dorm (Packer Hall) Whitmore

Name Skyler Hayley Mike Jun

Concentration (ppm) 580 360 340 180

IV.

Discussion The AA method resulted in Juns sample from the Whitmore lab having the highest level of water hardness. Haleys sample from an off-campus apartment had the softest water. The samples from the HUB and the dorm were similar in numbers. When doing the EDTA Titration, the Whitmore sample took the least number of drops to change colors. Because of this, it resulted in the lowest concentration of calcium. The sample from the HUB required the most drops and therefore had the highest concentration. The two methods clearly do not agree with each other. They almost show exact opposites. However the AA method somewhat agreed with my hypothesis whereas the titration did not. It is most likely possible that while doing our titrations we made significant errors at some point. I would trust the results from the AA because it is a machine that does the work and there is little room for error. Because the machine is so expensive and complex, I trust the data more than my own do-it-yourself experiment. During the titration, several things could have gone wrong. The number of drops could have been counted wrong, not enough sample was used, or my judging of where the color changed could have been wrong. During my research, I came across this table of typical values that determine water hardness. Table 11 shows these values.

Table 11- Typical Hardness Guidelines (5) Grains Per Gallon Miligrams Per Liter (mg/l) or Parts Per Million (ppm) less than 17.1 17.1 - 60 60 - 120 120 - 180 over 180 Soft Slightly Hard Moderately Hard Hard Very Hard Rating

less than 1.0 1.0 - 3.5 3.5 - 7.0 7.0 - 10.5 over 10.5

Looking back, my numbers from the EDTA Titration are very high. The lowest is 240 and the highest is 780. Judging by my research it tells me that these water samples all fall in the very hard category. A justified conclusion cannot be made from these numbers. The AA hardness levels fall more into the ranges of the rating system I found. The HUB sample and the sample from the dorm appear to be moderately hard. The sample from Whitmore lab falls into the very hard category and the apartment sample is slightly hard. I predicted the Whitmore sample to be the hardest, but thought the drinking waters from the HUB and the dorm would be softer. Perhaps the apartment water is so soft because it is a very large apartment building and would want to decrease the chance of buildup in pipes as much as possible. From my tables we also determined that the hardness levels after the commercial conditioning agent was added dropped by half. After the Ion Exchange section, the hardness levels were decreased by a factor of about 3/4ths. V. Conclusion The purpose of this experiment was to gather different water samples and test their hardness levels. Hard water is a type of water that has high concentrations of salts, specifically Calcium

and Magnesium. Hard water is not necessarily damaging to your health however it is recommended to use softer water if possible. My group gathered four samples each from different places located around our campus. The samples came from the HUB, an on-campus dorm, Whitmore Lab, and an off-campus apartment on Pugh Street. Prior to the experiment, we hypothesized which sources of water would be the hardest. We then underwent two tedious experiments to test our hypothesis. We concluded that the use of a very expensive, complex machine was the most reliable and effective way to determine water hardness. Using an atomic absorption spectrophotometer gave us values that we were able to apply to previous experiments and judge their hardness by. The method that we found did not work as well was the EDTA Titration. This is a very tedious, experiment where many things can go wrong. However if done correctly and successfully, the titration provides data which can lead to the same conclusions. After careful calculations, we received our water hardness values in parts per million (ppm) and were able to rank them according to previous standings. Our values corresponded to the rankings in which we predicted in the beginning indicating we had done something right. VI. References 1) A Microscale Spectrophotometric Determination of Water Hardness http:// www.centralmethodist.edu/employee/jgordon/J%20Chem%20Ed%20-%20Spectro%20 Water%20Hardness.pdf (accessed April 2009) 2) Boyd, Claude E. Water Quality An Introduction; Kluwer Academic Publishers: Norwell, 2000; pp126-128. 3) Guidelines for Chem 111 Formal Report. Chemistry Lecture Text. pp 58-60

4) Drinking Water: Hard Water. http://www.ianrpubs.unl.edu/epublic/live/g1274/build/ g1274.pdf (accessed April 2009) 5) Household Water Quality- Water Hardness http://www.ext.vt.edu/pubshousing356-4903 56-490.html (accessed April 2009) 6) Lee, Jun, Chem 111 Laboratory Notebook, pp 18-22 7) Martoglio, Michael, Chem 111 Laboratory Notebook, pp 25-30 8) Marzewski, Skyler, Chem 111 Laboratory Notebook, pp 34-38 9) Miller, Hayley, Chem 111 Laboratory Notebook, pp 31-36. 10) Natural Water. http://www.science.uwaterloo.ca/~cchieh/cact/applychem/waternatural.html (accessed April 2009) 11) Thompson, Stephen. PSU Chemtrek; Hayden-McNeil Publishing Inc.: Plymouth, 2006-2007; pp 10-1 to 10-22 12) Water Quality and Waste Management. http://www.bae.ncsu.edu/programs/extension publicat/wqwm/tc1.html (accessed April 2009)