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The Chemistry of Natu- ral Waters

Michael Martoglio

April 6, 2009 Chem 111 Section 104 TA: Shradda Surve Group: Jun Lee, Hayley Miller, Skyler Marzews- ki

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 Ca 2+ and Mg 2+ . 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 Mag- nesium comes from rocks like olivine and pyroxenes. (11) A water sample with high concentra- tions 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 un- treated 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 Ca 2+ and Mg 2+. The EDTA is an inexpensive lab experiment. To use this experiment you take a known amount of natu- ral water and bring its pH to 10 by use of a buffer. Next you add EBT indicator which turns the so- lution blue because of the high pH. This indicator will soon turn a red wine color with the presence of Mg 2+ but does not test for the presence of Ca 2+ .(11) Then a known concentration of EDTA solu- tion 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 (Ca 2+ or Mg 2+ ). A beam of light leaves region 1 with the same energy level re- quired to dissociate a molecule of what you’re 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 you’ve 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 photo- multiplier tube (PMT) which reads and determines how much of Ca 2+ and Mg 2+ 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 sec- onds. Also the AA is only capable of calculating the absorption of Ca 2+ and Mg 2+ . 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 negative- ly charged resin to attract the positive Ca and Mg ions. When the ions attach to the resin, potassi- um, 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 lim- ited and it’s process was mentioned above. The intensity of the light from region 3 in the spec- trophotometer 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 Ca 2+ . 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

M EDTA V EDTA = M Ca 2+ V Ca 2+ . 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 ini- tial color change took place. This equation, when solved for M Ca 2+ will give us the concentration of the original Ca 2+ . (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 com- mercial 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

Ca 2+ Ab-

Mg 2+ Ab-

Dilution

sorbance

sorbance

HUB

Skyler

0.2926

  • 0.3214 1:1

 

Apartment (Pugh St)

Hayley

0.2051

  • 0.1671 1:1

 

Dorm (Packer

Mike

0.3186

  • 0.3222 1:1

 

Hall)

Whitmore

Jun

0.4834

  • 0.5419 1:1

 

Graph 1 shows the absorbance value versus the concentration of calcium. These numbers were pre-

sented to us when conducting the AA experiment.

Graph 1-

Graph 2 shows the absorbance value versus the magnesium of calcium. These numbers were pre-

sented to us when conducting the AA experiment.

.

Graph 2 shows the absorbance value versus the magnesium of calcium. These numbers were pre- sented

Also for section A, after producing these graphs and returning with our Calcium and Mag-

nesium data we are able to determine the hardness. By using the equations of

Graph 2-

Graph 2 shows the absorbance value versus the magnesium of calcium. These numbers were pre- sented

the trendline on the graphs and plugging in our values for Ca 2+ and Mg 2+ 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 Ca 2+ . I then use the following equation to convert to water hard-

ness. (11)

1 ppm Ca 2+ x

100 g CaCO 3 1 mole

_ = 2.5 ppm CaCO 3 = 2.5 ppm hardness

40.0 g Ca 2+ 1 mole

For example my conversion would be:

24.08 ppm Ca 2+ x

100 g CaCO 3 1 mole

_ = 60.2 ppm CaCO 3 = 60.2 ppm hardness

40.0 g Ca 2+ 1 mole

Table 2 shows the results doing the same with my group’s numbers.

Table 2- AA Water Hardness (Ca 2+ ) (6,7,8,9)

Sample

Name

Hardness (ppm)

HUB

Skyler

54.3

Apartment (Pugh St)

Hayley

34.6

Dorm (Packer Hall)

Mike

60.2

Whitmore

Jun

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 Mg 2+ concentration into the equation for y and solve for x I get

14.2

ppm Mg 2+ . We then must convert this number into water hardness using the following equa-

tion:

1 ppm Mg 2+ x

 

100 g CaCO 3 1 mole

_ = 4.12 ppm CaCO 3 = 4.12 ppm hardness

 

24.3 g Mg 2+ 1 mole

For example, my water hardness would be

 
 

100 g CaCO 3

14.2

ppm Mg 2+ x

1 mole

= 58.4 ppm CaCO 3 = 58.4 ppm hardness

 

24.3 g Mg 2+ 1 mole

Table 3 shows my groups data going through those same steps.

Table 3- AA Water Hardness (Mg 2+ ) (6,7,8,9)

Sample

Name

Hardness (ppm)

HUB

Skyler

58.4

Apartment (Pugh St)

Hayley

23.4

Dorm (Packer Hall)

Mike

58.4

Whitmore

Jun

108.2

The total hardness is shown in Table 4.

Table 4- Total Hardness (6,7,8,9)

Sample

Name

Hardness (ppm)

HUB

Skyler

112.7

Apartment (Pugh St)

Hayley

58.0

Sample

Name

Hardness (ppm)

Dorm (Packer Hall)

Mike

118.6

Whitmore

Jun

205.5

Table 5 shows the absorption rates for my group’s water samples obtained by using the EDTA titra-

tion

Table 5- EDTA Titration (6,7,8,9)

Sample

Name

Drops of Sam- ple

Drops of EDTA

Dilution

HUB

Skyler

1

 
  • 39 none

Apartment (Pugh St)

Hayley

1

 
  • 24 none

Dorm (Packer

Mike

1

 
  • 23 none

Hall)

Whitmore

Jun

1

 
  • 12 none

In section D, we had to determine the hardness of our water samples by counting the num-

ber of drops of EDTA it took to change the color of the well. We use the following equation with

the

following variables:

“M EDTA ”: (2.0x10 -4 M)

M EDTA V EDTA = M Ca 2+ V Ca

2+

“V EDTA ”: number of drops of EDTA (differs for each sample)

“M Ca 2+ ”: What we are solving the equation for

“V Ca 2+ ”: 1

For example, the equation for my water sample would be:

(2.0x10 -4 M) (23) = (M Ca 2+ ) (1)

M Ca 2+ = 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)

Sample

Name

Concentration

HUB

Skyler

7.8x10 -3 M

Apartment (Pugh St)

Hayley

4.8x10 -3 M

Dorm (Packer Hall)

Mike

4.6x10 -3 M

Whitmore

Jun

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 CaCO 3 1 mole CaCO 3

x

1000 mg CaCO 3 1 g CaCO 3

100 mg CaCO 3 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

Name

Concentration (ppm)

HUB

Skyler

780

Apartment (Pugh St)

Hayley

480

Dorm (Packer Hall)

Mike

460

Whitmore

Jun

240

We then took the concentration in ppm and converted to grams/gallon. This was done by the fol-

lowing:

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

Name

Concentration (grains/gal- lon)

HUB

Skyler

45.6

Apartment (Pugh St)

Hayley

28.1

Dorm (Packer Hall)

Mike

26.9

Whitmore

Jun

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

Name

Concentration (ppm)

HUB

Skyler

380

Apartment (Pugh St)

Hayley

240

Dorm (Packer Hall)

Mike

230

Whitmore

Jun

120

The concentration of everyone’s 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 Ca 2+ and Mg 2+

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

Name

Concentration (ppm)

HUB

Skyler

580

Apartment (Pugh St)

Hayley

360

Dorm (Packer Hall)

Mike

340

Whitmore

Jun

180

IV.

Discussion

The AA method resulted in Jun’s sample from the Whitmore lab having the highest level of

water hardness. Haley’s 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 Whit-

more 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 hard-

ness. Table 11 shows these values.

Table 11- Typical Hardness Guidelines (5)

Grains Per

Miligrams

Rating

 

Gallon

Per Liter (mg/l) or Parts Per Million (ppm)

less than 1.0

less than 17.1

Soft

1.0

- 3.5

17.1 - 60

Slightly Hard

3.5

- 7.0

60 - 120

Moderately Hard

7.0

- 10.5

120 - 180

Hard

over 10.5

over 180

Very Hard

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 condi-

tioning 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 hard-

ness 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 recommend-

ed 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 apart-

ment 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 pro-

vides 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 rank-

ings in which we predicted in the beginning indicating we had done something right.

VI.

References

1) “A Microscale Spectrophotometric Determination of Water Hardness” http://

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.

(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)