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Natalie Cappelli

April 6, 2017

The Effect of Elevation on Water Hardness

CHEM 113

Section: 003

Matt Blau, Julia Classen, and Haley Clement

TA: Saehyun Choi

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Introduction:

Water hardness is defined as the amount of dissolved calcium and magnesium in water

samples. For water to be categorized as hard, it must be high in dissolved minerals, including

calcium and magnesium, so a sample with greater hardness will have a greater concentration of

these dissolved ions.1 The hardness of water is important due to the fact that it is a commonly

reported aspect of water quality. Additionally, hardness affects the amount of soap that is needed

to produce foam, thus hard water requires more soap because the calcium and magnesium ions

prevent the soap from lathering.2 Hard water often produces a noticeable deposit of precipitate in

containers and on surfaces, often resembling a ring, predominantly caused by the calcium and

magnesium cations.3 Generally, water hardness is measured by titration. Specifically, a buffer

and a color indicator are added to a volume of water, and then an acid, serving as the titrant, is

added to the sample. The acid reacts with the calcium and magnesium ions in the water;

therefore, the volume of acid needed for a color change to occur reflects the Ca2+ and Mg2+

concentration of the sample.2 Furthermore, a colorimeter can be used to test water hardness as

well. In order to do so, a white light beam is passed through an optical filter that transmits only

one band of wavelengths of light to the photodetector, where it is measured. The amount of

colored light absorbed is directly proportional to the concentration and is reported by the meter.4

Moving forward, EDTA titration can be used for direct determination of many metal

cations due to the fact that it reacts with metals on a 1:1 basis.5 This process is completed by first

taking a known volume of water and adding EBT indicator to the sample. If Mg2+ is present, it

will react with the indicator to form a wine red chelate, meaning the molecule binds at multiple

points in a complex.6 Then, EDTA is added to the solution, first reacting with Ca2+, to form a

colorless chelate. After enough EDTA is added to chelate all of the Ca2+, the EDTA will begin to
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react with the magnesium indicator chelate to produce a colorless MgEDTA chelate. At the end

point of the titration, there will be a definite change from a wine red to a sky-blue color,

corresponding to the complete reaction of all of the Ca2+ and Mg2+ with EDTA.7 On the other

hand, atomic absorption spectrophotometry (AA) is a technique used to determine the metals that

are dissolved in a solution. Atomic absorption methods measure the amount of energy, in the

form of photons of light, absorbed by a sample.8 The concentration of a metal in a sample is

determined by a calibration graph. In order to accomplish this, the operator of the AA first

prepares a set of metal solutions of known concentrations referred to as standard solutions, that

are analyzed by the AA so that the absorbance of each solution can be recorded. The values are

then used to construct a calibration graph.7 In addition, monochromatic light having energy that

corresponds to the change in energy of the atoms of interest is projected through the water

sample, and the atoms having electronic energy separation will absorb the light. As a result, the

amount of absorbance is proportional to the concentration of the metal atoms present, and then

the Beer-Lambert law is used to calculate the unknown metal concentrations in the water

sample.7 Therefore, EDTA and AA differ in a sense that EDTA is used to find the equivalence

point and the half equivalence point using titration methods, while AA spectrophotometry uses a

beam of light to find the concentration of a metal in a solution.8

When hard water is abundant, water softening techniques are often used that remove

calcium, magnesium, and other metal cations from the water, replacing them with sodium ions.

Hard water and soft water alike come with advantages and disadvantages, and, as a result, the

hardness of water varies from household to household.9 The purpose of this lab was to sample

water from three states of close proximity to test the hardness of the samples in order to focus

primarily on the effects of elevation on water hardness. Water was sampled from areas between
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western Pennsylvania and northern Delaware, including areas in between such as Huntingdon

Valley, Pennsylvania and Fredericktown, Maryland, respectively. Therefore, I hypothesized that

water from higher elevations would have a lower hardness, while water from lower elevations

would have a higher hardness value. This is because, as water travels down from a higher

elevation to a lower elevation it collects more ions, considering the sample starts as relatively

pure rainwater and then gains deposits of a variety of minerals as it travels down an elevation.1

To take that hypothesis a step further, I predict that the water sample from Middletown,

Delaware will prove to be the hardest water if no softening agent is used, because the sample is

coming from the city with the lowest elevation out of all the samples collected. Once again, the

areas sampled have as high an elevation as 1,156 feet in Washington, PA, then Huntingdon

Valley, PA at 223 feet, Frederick, MD at 92 feet, and finally Middletown, DE at 66 feet.10

Procedure:

The procedure was followed according to PSU Chemtrek, outlined in Experiment 10: The

Chemistry of Natural Waters.7

Determination of Water Hardness by Atomic Absorption Spectroscopy (AA)

The water sample used to complete the study was collected from a tap. The water sample

was diluted according to a 1:1 factor, using distilled water. Two bulbs of cut pipets were filled so

that one sample could be used for the calcium analysis, while the other was for the magnesium

analysis. While using the AA, the aspirator was placed into the sample, and when it was run

through the machine, a value appeared on the screen that was recorded as the magnesium value

and the sample was run a second time for the calcium value.7

Total Dissolved Solids (TDS)

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Foil paper was placed onto a hot plate, and one drop of the undiluted water sample,

distilled water, and 1.00 x 10-3 M Ca2+ were placed 0.5 centimeters away from one another. After

the water evaporated, our observations were recorded so that the TDS of the water sample could

be compared to the others.7

EDTA Titration

First, a single drop of 1.00 x 10-3 M Ca2+ solution was added to each of the 12 wells of a

1x12 well strip, as well as one drop of EBT indicator and NH3/NH4Cl/MgEDTA. Titrating

serially with EDTA solution, 1 drop of 2.00 x 10-4 M EDTA was added to the first well, 2 drops

to the second well, continuing in such a manner. The first well to turn blue was considered the

endpoint. The titration was then repeated the same way, except one drop of 1.00 x 10-3 M Ca2+

and one drop of 1.00 x 10-3 M Mg2+ was added to each well.7

Determining Water Hardness by EDTA Titration

Using the undiluted water sample, one drop was added to each of the 12 wells of a 1x12

well strip, as well as one drop of EBT indicator and NH3/NH4Cl/MgEDTA. Titrating serially

with EDTA solution, 1 drop of 2.00 x 10-4 M EDTA was added to the first well, 2 drops to the

second well, continuing in such a manner. A duplicate analysis was carried out, and the average

of the two EDTA titrations was used to calculate the concentration of divalent cations in

molarity, and the hardness was then calculated in ppm.7

Divalent Cation Removal by Ion Exchange

Cation exchange resin was placed into a vial to cover the bottom, and then the undiluted

water sample was added to 1 centimeter in height. The vial was shaken and then was set down so

that the resin could settle. Liquid was removed from the vial and the pH, as well as the pH of the

original water sample for comparison purposes. Using the resin-treated water sample, one drop
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was added to each of the 12 wells of a 1x12 well strip, as well as one drop of EBT indicator and

NH3/NH4Cl/MgEDTA. Titrating serially with EDTA solution, 1 drop of 2.00 x 10-4 M EDTA

was added to the first well, 2 drops to the second well, continuing in such a manner. The average

of the two EDTA titrations was used to calculate the hardness of the resin-treated water sample,

and the percent change between the result of the titration where no softening agent was added to

the resin-treated titration was calculated.

Results:

Determination of Water Hardness by Atomic Absorption Spectroscopy (AA)

Table 1. Calcium Absorbance Standard Values

Calcium Concentration Absorbance Value Check Standard*
(ppm) (at 422.7 nm) (ppm)
1.000 0.00623 1.29
5.00 0.03953 5.15
10.00 0.07470 10.05
25.0 0.17207 24.53
50.0 0.32333 50.40

Graph 1. Light Absorbance vs. Ca2+ Concentration

Light Absorbance vs. Ca2+ Concentration

0.35
Light Absorbance (at 422.7 nm)

0.3
0.25
0.2
0.15
0.1
0.05 y = 0.0064x + 0.0066
0
0 10 20 30 40 50 60
Ca2+ Concentation (ppm)
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Table 2. Magnesium Absorbance Standard Values

Magnesium Concentration Absorbance Value Check Standard*
(ppm) (at 202.5 nm) (ppm)
1.000 0.02139 1.15
5.00 0.07399 4.84
10.00 0.14424 9.67
25.0 0.30530 25.63
30.0 0.38370 30.78

Graph 2. Light Absorbance vs. Mg2+ Concentration

Light Absorbance vs. Mg2+ Concentration

0.5
Light Absorbance (at 202.5 nm)

0.4

0.3

0.2

0.1
y = 0.0129x + 0.0119
0
0 5 10 15 20 25 30 35
Mg2+ Concentration (ppm)

Table 3. Atomic Absorption Values

Sample Ca2+ AA Value Mg2+ AA Value
Tap Water from Washington, PA 0.1086 0.0703
Tap Water from Huntingdon, 0.1701 0.1602
PA11
Tap Water from Frederick, MD12 0.1600 0.0012
Softened Tap Water from -0.0008 0.2098
Middletown, DE13
All samples diluted on a 1:1 ratio

Using the absorbance value for calcium, 0.1806, and for magnesium, 0.0703, the

concentration of calcium and magnesium was found using the equations provided in Graph 1 and

Graph 2. From that point, the hardness could be calculated by converting the Ca2+ and Mg2+
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concentration values into their equivalent concentrations of CaCO3 in ppm. Total hardness was

then found by combining the Ca2+ and Mg2+ values.

1:1 dilution:
Ca = .1806
y = 0.0064x + 0.0066
.1806 = 0.0064x + 0.0066
x = 27 ppm x 2.0 = 54 ppm

54 ppm Ca2+ x 100.09 g CaCO3/1mole = 130 ppm CaCO3 = 130 ppm hardness
40.08 g Ca 2+/1mole

Mg = .0703
y = 0.0129x + 0.0119
.0703 = 0.0129x + 0.0119
x = 4.53 ppm x 2.0 = 9.06ppm

9.06 ppm Mg2+ x 100.09 g CaCO3/1mole = 37.3 ppm CaCO3 = 37.3 ppm hardness
24.31 g Mg2+/1 mole

Total hardness:
130 ppm hardness + 37.3 ppm hardness = 167.3 ppm hardness = 167 ppm hardness

Table 4. Hardness Calculated from AA Analysis

Sample Ca2+ Hardness Mg2+ Hardness Total Hardness
(ppm) (ppm) (ppm)
Tap Water from Washington, PA 130.0 37.30 167.0
Tap Water from Huntingdon, 133.8 63.02 196.8
11
PA
Tap Water from Frederick, MD12 59.78 66.63 126.4
Softened Tap Water from 7.540 -5.090 2.450
Middletown, DE13

Total Dissolve Solids (TDS)

Table 5. Total Dissolved Solids Observations

Sample Observation
Distilled Water No white residue
Ca2+* Slight white ring
Tap Water from Washington, PA Dark white circle
Tap Water from Huntingdon, PA11 Dark with defined white ring
Tap Water from Frederick, MD12 Thicker white ring
Softened Tap Water from Middletown, DE13 Faint white ring
*Reference Value
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Determining Water Hardness by EDTA Titration

Table 6. Amount of EDTA Needed for Titration

Sample Number of Drops of EDTA Needed for
Titration
Tap Water from Washington, PA 4.0
Tap Water from Huntingdon, PA11 9.5
Tap Water from Frederick, MD12* 4.5
Softened Tap Water from Middletown, DE13 9.0
*Diluted on a 1:1 ratio

Using the number of drops of EDTA needed for titration, the concentration of divalent

cations in molarity was found. The molarity was then used to find the hardness value of the

various water samples in ppm.

Concentration of divalent cations in molarity:

(2.00 x 10-4 M)(4.0 drops EDTA) = M(1.0 drop tap water from Washington, PA)
M = 8.00 x 10-4 M

Hardness Value in ppm:

8.00 x 10-4 mol CaCO3 x 100.0 g CaCO3 x 1000 mg CaCO3 = 80.0 ppm
1 L solution 1 mole CaCO3 1 g CaCO3

Table 7. Hardness Calculated from EDTA Titration

Sample Hardness Value (ppm)
Tap Water from Washington, PA 80.0
Tap Water from Huntingdon, PA11 190.
Tap Water from Frederick, MD12* 180.
Softened Tap Water from Middletown, DE13 19.0
*Diluted on a 1:1 ratio

Divalent Cation Removal by Ion Exchange

Table 8. Amount of EDTA Needed for Titration

Sample Number of Drops of EDTA Needed for
Titration
Tap Water from Washington, PA 1.0
Tap Water from Huntingdon, PA11 1.0
Tap Water from Frederick, MD12* < 1.0
Softened Tap Water from Middletown, DE13 1.0
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Using the number of drops of EDTA needed for titration, the concentration of divalent

cations in molarity was found in the resin treated water sample. The molarity was then used to

find the hardness value of the various water samples in ppm.

Concentration of divalent cations in molarity:

(2.00 x 10-4 M)(1.0 drops EDTA) = M(1.0 drop tap water from Washington, PA)
M = 2.00 x 10-4 M

Hardness Value in ppm:

2.00 x 10-4 mol CaCO3 x 100.0 g CaCO3 x 1000 mg CaCO3 = 20.0 ppm
1 L solution 1 mole CaCO3 1 g CaCO3

Table 9. Hardness after Resin Treatment

Sample Hardness Value after Resin Treatment (ppm)
Tap Water from Washington, PA 20.0
Tap Water from Huntingdon, PA11 20.0
Tap Water from Frederick, MD12* 40.0
Softened Tap Water from Middletown, DE13 2.00
*Diluted on a 1:1 ratio

Analysis of Elevations

Table 10. Comparison of Elevation10

Sample Elevation of Source (ft.)
Tap Water from Washington, PA 1,156
Tap Water from Huntingdon, PA11 223
Tap Water from Frederick, MD12 92
Softened Tap Water from Middletown, DE13 66

Summary of Calculated Data

Table 11. Calculated Results

Sample Elevation of Source AA Hardness EDTA Hardness
(ft.) (ppm) (ppm)
Tap Water from 1,156 167.0 80.0
Washington, PA
Tap Water from 223 196.8 190.
Huntingdon, PA11
Tap Water from 92 126.4 180.
Frederick, MD12*
Softened Tap Water 66 2.450 19.0
from Middletown, DE13
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Graph 3. AA Hardness vs. Elevation

Elevation vs. AA Hardness

250

Hardness (ppm) 200

150

100

50

0
0 200 400 600 800 1,000 1,200 1,400
Elevation (ft.)

Graph 4. EDTA Hardness vs. Elevation

Elevation vs. EDTA Hardness

200
180
160
Hardness (ppm)

140
120
100
80
60
40
20
0
0 200 400 600 800 1000 1200 1400
Elevation

Discussion:

After analyzing the results for trend on how elevation affected water hardness, it was

apparent that the tap water from Huntingdon, Pennsylvania was the hardest, coming from an

elevation of 223 feet, with an AA hardness value of 196.8 ppm and an EDTA hardness value of

190 ppm. However, the data collected showed that there was no relationship between the
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hardness of water and the elevation from which it was collected. The water sample from

Middletown, Delaware was found to be the softest, coming from an elevation of 66 feet, with an

AA hardness value of 2.450 ppm and an EDTA hardness value of 19.0 ppm. Then, the tap water

from Frederick, Maryland, 92 feet above sea level, was the next softest sample with an AA

hardness of 126.4 ppm and EDTA hardness value of 180 ppm. The tap water that came from

Washington, Pennsylvania at 1,156 feet was calculated to have an AA hardness value of 167.0

ppm and an EDTA hardness value of 80.0 ppm, while the water from Huntingdon, PA was the

hardest. The sample from Washington, PA broke the trend that appeared as water hardness

increased as elevation increased for the samples collected from Delaware and Maryland. If that

trend was to be accurate, the tap water from Washington, PA should have been the hardest but it

was not. In either case, the results proved my hypothesis to be wrong because I originally

predicted that water from lower elevation would be the hardest and that the water sample from

Middletown, Delaware would be the hardest, but it was found to be the softest. In fact, we saw

the opposite trend in our data as areas of lower elevations appeared to have the softest water.

However, the water collected from Middletown, Delaware went through a softening agent, and

that could have altered the data. That is because, as the water flowed through a residential

softening unit, resin released sodium ions and traded them for the calcium and magnesium ions.9

Therefore, the water that poured out of the spigot was softened.

Furthermore, the data collected from the two-different hardness-determination methods

showed the same trend, although the actual values varied between the AA method and the EDTA

titration. The water samples from Middletown, Delaware and Frederick, Maryland had EDTA

hardness values that were larger than the AA hardness values, while the tap water from

Huntingdon, PA and Washington, PA had AA hardness values than the EDTA hardness values.
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Both techniques showed that the water from Middletown, Delaware was the softest, but the

EDTA titration method found the tap water from Washington, Pennsylvania to be the next

softest, while the AA method found the water from Frederick, Maryland to be the softest after

Delaware. The AA hardness values are more accurate considering that the concentration of the

calcium and magnesium ions in water samples had a percent error of twenty percent.

Additionally, the EDTA hardness values had a plus or minus value of 20.0 ppm. This is because

if we were off one well in the EDTA titration process, the hardness value was altered 20.0 ppm,

proving that the EDTA titration method shows hardness in multiples of twenty.6 Moreover, the

results of our experiment could have been altered by possible sources of error. As for the AA

method, there could have been an error in the calibration graph that affected the number provided

from the machine for the concentration of magnesium and calcium in the water samples.14 As a

result, the AA hardness values would be off, and our data would be altered. Also, the water

samples used in the lab could have been softened before pouring out of the spigot without our

knowledge, and that would have changed the results we collected.

When comparing the results of the water hardness from the locations from which we

collected the tap water samples with the local water authorities, the Huntingdon Water Authority

expressed how hard water was common in Huntingdon, PA, showing the accuracy of the

hardness value calculated.15 Similarly, the Middletown, DE Water Quality report showed that, on

average, the water had a total hardness of 24.5 ppm, and we found the AA hardness to be 2.450

ppm and EDTA hardness to be 19.0 ppm.16 Considering the use of a softening agent and the plus

or minus 20.0 ppm for EDTA titration, the accuracy of the softest water is also confirmed.
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Conclusion:

Overall, our experiment found that the tap water sample from Huntingdon, Pennsylvania

had the largest AA hardness value of 196.8 ppm and an EDTA hardness value of 190 ppm. On

the other hand, the softened tap water from Middletown, Delaware was the softest sample with

an AA hardness value of 2.450 ppm and an EDTA hardness value of 19.0 ppm. The results

proved my hypothesis to be wrong because I originally believed that the tap water from

Washington, Pennsylvania would be the hardest, and then found that the water from Huntingdon,

PA was the hardest despite having a lower elevation. Ultimately, our data showed that there was

no relationship between the hardness of water and the elevation from which it was collected.
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References:

1. Water Hardness https://water.usgs.gov/edu/hardness.html (accessed April 2017)

2. General Information on Hardness

http://bcn.boulder.co.us/basin/data/NEW/info/Hard.html (accessed April 2017)

3. Hardness in Drinking-water

http://www.who.int/water_sanitation_health/dwq/chemicals/hardness.pdf (accessed April

2017)

4. Measuring Water Hardness http://www.lamotte.com/en/blog/test-factors/75-measuring-

water-hardness (accessed April 2017)

5. Complexometric titration EDTA http://www.titrations.info/EDTA-titration (accessed

April 2017)

6. EDTA

https://chem.libretexts.org/Core/Inorganic_Chemistry/Coordination_Chemistry/Propertie

s_of_Coordination_Compounds/Ligands/EDTA (accessed April 2017)

7. Thompson, Stephen. PSU Chemtrek; Hayden-McNeil: Plymouth, MI, 2016-2017; pp 10-

16-10-23.

8. Atomic Absorption Spectroscopy https://web.nmsu.edu/~esevosti/report.htm (accessed

April 2017)

9. Water Quality http://extension.psu.edu/natural-resources/water/drinking-water/water-

testing/water-treatment/water-softening (accessed April 2017)

10. 50 State Elevations http://www.netstate.com/states/tables/state_elevation_mean.htm

(accessed April 2017)

11. Blau, Matt, Chem 113 Laboratory Notebook, spring 2017, pp. 45-50.
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12. Clement, Haley, Chem 113 Laboratory Notebook, spring 2017, pp. 31-34.

13. Classen, Julia, Chem 113 Laboratory Notebook, spring 2017, pp. 37-41.

14. Lehr, Jay H.; Keeley, J Water Encyclopedia. John Wiley & Sons, Inc., Hoboken, NJ,

2005, pages 96-123.

15. Water Testing http://certifiedwaterservices.com/services.html#water_testing (accessed

April 2017)

16. Middletown Water Department https://imageserv10.team-

logic.com/mediaLibrary/254/Middletown_CCR-2011.pdf (accessed April 2017)