4/12/18
CHEM 113: Experimental Chemistry II
Section 004
TA Justin Munro
Group Members:
1) Sasha Neely, Seat 169
2) Lasair ni Chochlain, Seat 170
3) Mary Patterson, Seat 175
4) Selma Paul, Seat 176
INTRODUCTION
given sample. While numerous polyvalent cations can impart the specific chemical properties
associated with “hardness,” the most common contributing compounds are magnesium and
calcium. These elements are abundantly present in the natural mineral composition of soil and
rock. When water (the universal solvent) comes into contact with these inorganic substances, the
While the drinking of hard water is not associated with human health problems, it does
play a role in other social complications.2 On the individual level, hard water interferes with
daily cleansing routines by decreasing the effectiveness of synthetic soaps and detergents.
Operations of industry are also inhibited due to the buildup of scale, the precipitate of divalent
cation compounds that result from high-temperature usage in pipes. Scale increases blockages
while decreasing water flow efficiency, culminating in higher energy costs and shorter-lived
infrastructure.3 These problems, among others, warrant an examination of the ions that determine
water hardness.
There are two primary ways to determine the hardness of a water sample. The more cost-
effective method involves a titration process with the chelating agent ethylenediaminetetraacetic
acid, henceforth referred to as EDTA. In this procedure, a pH-adjusted water sample is combined
with the metal ion indicator Eriochrome black T, or EBT. In this buffered, basic environment of
1
The USGS Water Science School, USGS: Science for a Changing World. Water Properties
Home: Water Hardness. https://water.usgs.gov/edu/hardness.html (accessed Mar 22, 2018).
2
Cotruvo, J.; Bartram, J. eds. Calcium and Magnesium in Drinking Water: Public Health
Significance. Geneva, World Health Organization, 2009.
3
Drinking Water: Hard Water. City of Cambridge, MA [Online].
http://www2.cambridgema.gov/CityOfCambridge_Content/documents/Drinking%20WaterMy%
20edition.pdf (accessed Mar 30, 2018).
3
approximately pH 10, EBT is in its HD2- form and appears sky-blue in color. While Ca2+ will not
react with the indicator, Mg2+ ions in the sample will become MgD- and the beginning solution
thus becomes a characteristic wine-red. As EDTA is then added, the end point of the titration
will occur when all of the Ca2+ and Mg2+ ions have reacted with the EDTA to form colorless
chelates. The solution will return to a sky-blue color, indicative of the EBT indicator losing its
Mg2+ ions and returning to its HD2- structure.4 Using the end point of the titration, the total
divalent cation content can be found and converted into ppm CaCO3, a measure of water
hardness.
hardness of a given sample. AA is based on the chemical principle that each atom has its own
discrete electronic energy level. For any atom to absorb the energy of light that falls upon it, the
energy of the photons must equal the difference in energy between two of the atom’s electronic
energy levels.5 This concept led to the development of the atomic absorption spectrophotometer.
This instrument projects light of a single wavelength, matching the energy separation of the
atoms of interest, through the water sample. The amount of light absorbance will be proportional
to the concentration of that specific type of atom. If the absorbance measurement falls within the
standards of the instrument’s initial calibration used to check the accuracy/reproducibility of the
apparatus, the Beer-Lambert law can be used to calculate the unknown metal concentration in the
4
Community College of Rhode Island, Chemistry Courses: Labs, Calcium Analysis by EDTA
Titration.
http://www.ccri.edu/chemistry/courses/chem_1100/wirkkala/labs/Calcium_Analysis_by%20ED
TA_Titration.pdf (accessed April 10, 2018).
5
Sevostianova, Elena. New Mexico State University, Introduction: Atomic Absorption
Spectroscopy. https://web.nmsu.edu/~esevosti/report.htm (accessed Mar 30, 2018).
4
sample.6 If the absorbance measurement exceeds 1 absorbance unit, only a small amount of light
was successfully transmitted through the atoms. Dilution of the water sample will be necessary
In this project, both EDTA titration and AA Spectrophotometry were used to determine
the hardness of four distinct water samples. The water was obtained from different sources
throughout the state of Pennsylvania - river water from the Delaware River; pond water from
Bullfrog Valley Pond in Hummelstown, PA; tap water from a home in Macungie, PA; and well
water from a home in Zionsville, PA. The Delaware River water will be soft because the river is
fed by streams and creeks that flow through the high mountains of Appalachia. Due to the steep
slopes and thin soil cover on the ground, rain runoff quickly reaches the tributaries without
sinking into the earth and dissolving its rock.7 Because the Bullfrog Valley Pond water is
similarly supplied by a brook, it too will be classified as soft. In contrast, the Macungie tap water
and Zionsville well water will both be hard. These towns are located in the Lehigh Valley of
southeastern Pennsylvania, a region which contains the high-calcium limestones of the Kinzers,
Annville, Benner, and Keyser formations.8 The area also contains a high concentration of
6
Thompson, S. PSU Chemtrek: Small-Scale Experiments for General Chemistry. Keiser, J. Ed.;
Hayden-McNeil Publishing; Plymouth, MI 2017. pp. 10-1 to 10-24.
7
McCarthy, L. T.; Keighton, W. B.; Quality of Delaware River Water at Trenton, New Jersey.
Geological Survey Water-Supply Paper 1779-X. [Online] 1964.
https://pubs.usgs.gov/wsp/1779x/report.pdf (accessed April 5, 2018).
8
Limestone and Dolomite Distribution in Pennsylvania. Bureau of Topographic and Geologic
Survey, Fourth Edition, 1990; Third Printing. [Online] Revised, 2000. http://www.water-
research.net/Waterlibrary/geologicdata/map15.pdf (accessed April 8, 2018).
9
Geologic Map of Pennsylvania. Commonwealth of Pennsylvania Department of Conservation
and Natural Resources. Bureau of Topographic and Geologic Survey, Third Edition, 1990;
Fourth Printing. [Online] Revised, 2007.
http://www.docs.dcnr.pa.gov/cs/groups/public/documents/document/dcnr_016205.pdf (accessed
April 8, 2018).
5
PROCEDURE
Four water samples were analyzed using the procedure outlined in Experiment 10: The
Chemistry of Natural Waters.6 The table on the following page identifies and describes these
samples.
The water samples were first examined using Atomic Absorption spectroscopy. Two
instruments were used – one for the Ca2+ analysis, the other for the Mg2+ analysis. The pond
water and river water were measured without dilution, while the tap water and well water were
10
Neely, S. Seat 169, pp. 34-37. Pond water sample, Bullfrog Valley Pond, PA.
11
Paul, S. Seat 176, pp. 31-33. River water sample, Delaware River, PA.
12
Chochlain, L. Seat 170, pp. 40-56. Tap water sample, Macungie, PA.
13
Patterson, M. Seat 175, pp. 51-53. Well water sample, Zionsville, PA.
6
both diluted at a 1:1 ratio with distilled water. Droplets of the undiluted samples were then
evaporated to determine the concentration of total dissolved solids in the water. To do this, three
distinct droplets were placed on the shiny side of a piece of aluminum foil. One drop was the
undiluted water sample, the other drop was distilled water, and the final drop was 1.00 X 10-3 M
Ca2+. Placing the foil on a hot plate, the droplets were allowed to evaporate. The white solids that
remained were the nonvolatile salts that were originally in the solutions. These were observed,
The next procedures involved divalent cation analysis by EDTA titration. Before
analyzing the water samples directly, a practice serial titration with a known amount of Ca2+ (aq)
was carried out. One drop of 1.00 X 10-3 M Ca2+ solution was added to each of the 12 wells in a
clean 1 X 12 well strip along with one drop of the EBT indicator and one drop of the
NH3/NH4Cl/MgEDTA buffer. From there, a serial titration was done with the EDTA solution (1
drop of the 2.00 X 10-4 M EDTA to the first well, 2 drops to the second, and so on). The end
point (the first sky-blue well) was noted and the concentration of the original solution was
calculated. This process was repeated in another titration, the only change being the addition of
one drop of a 1.00 X 10-3 M Mg2+ solution to the one drop of the 1.00 X 10-3 M Ca2+ solution.
After this preparation, the EDTA titration was done on the four water samples. The same
serial titration process was used, however, one drop of the water sample replaced the known
concentrations of Ca2+ and Mg2+ that were used in the previous titrations. It should be noted that
the pond and river water samples remained undiluted, while the 1:1 dilutions of the tap and well
water samples (mentioned previously in the evaporation test of the procedure) were used. After a
duplicate analysis was carried out and the average of the two EDTA titrations was determined,
7
the concentration of the divalent cations was calculated and converted into the typical
Finally, the divalent cations of the water samples were removed through the process of
ion exchange. A small amount of the water sample was added to a vial containing cation
exchange resin. The vial was secured and then shaken vigorously for approximately a minute. A
serial titration was then carried out with one droplet of the resulting supernatant liquid. After a
duplicate analysis was done, the average of the two EDTA titrations was used to calculate the
RESULTS
Table 2: Comparison of TDS Residue after Water Evaporation from 1 Drop of Sample
Sample Observation
Bullfrog Valley Pond Water11 Visible white ring, slightly more than reference
Macungie Tap Water13 Fully opaque white ring, more than reference
Date: 3/15/2018
Time: 6:20 PM
AA Operator: K. Brown
Ca2+ Concentration (ppm) Absorbance Value (at 422.7 nm) Check Standard (ppm)
0.25
0.2
0.15
y = 0.005x + 0.0027
0.1
0.05
0
0 10 20 30 40 50 60
Concentration of Ca2+ (ppm)
9
Date: 3/15/2018
Time: 6:20 PM
AA Operator: K. Brown
Mg2+ Concentration (ppm) Absorbance Value (at 202.5 nm) Check Standard (ppm)
0.35
0.3
0.25
y = 0.0063x + 0.0536
0.2
0.15
0.1
0.05
0
0 10 20 30 40 50 60
Concentration of Mg2+ (ppm)
10
! = 0.005& + 0.0027
! − 0.0027
&=
0.005
0.1278 − 0.0027
&= = 25.02 ../
0.005
* Note: 1:1 diluted samples were multiplied by 2 to get the concentration of the original sample
! = 0.0063& + 0.0536
! − 0.0536
& =
0.0063
0.1705 − 0.0536
&= = 18.56 ../
0.0063
12
* Note: 1:1 diluted samples were multiplied by 2 to get the concentration of the original sample
Pond Water total hardness value = 62.48 ppm CaCO3 + 76.42 ppm CaCO3
= 138.9 ppm CaCO3
Table 11: EDTA Serial Titration Results for the Water Samples
Table 13: Divalent Cation Removal by Ion Exchange EDTA Serial Titration
DISCUSSION
Geological Survey, is as follows: 0-60 mg/L CaCO3 is soft, 61-120 mg/L is moderately hard,
121-180 mg/L is hard, and more than 180 mg/L is very hard.14 According to these guidelines and
the ranges calculated through the AA and EDTA experiments, the relative hardness of the four
water samples can be determined. The results illuminated that the river water was soft, the well
water was hard, the pond water was harder, and the tap water was very hard/hardest.
This scale was not exactly what was expected. The main difference from the original
hypothesis was that the pond water came back as being harder than the well water. There are a
few possible explanations for this development. On the qualitative level, the Bullfrog Valley
Pond where the water was collected is located in Dauphin County, Pennsylvania. The same
limestone and dolomite deposits that run below the ground of the Lehigh Valley are present in
the soil of the Dauphin region.9 While the pond is fed by a very small creek, it is largely made up
of standing water. It thus has more time in contact with the surrounding soil and rock, dissolving
Conversely, the well water could be softer than expected because of its construction.
Private wells such as the one from which the Zionsville sample was taken are cased within the
ground. This casing prevents groundwater contaminants from entering the well and mixing with
the drinking water.15 Due to this structural component, the well water has a set number of
14
USGS Water-Quality Information, USGS: Science for a Changing World. Water Hardness and
Alkalinity: Water Hardness. https://water.usgs.gov/owq/hardness-alkalinity.html
(accessed Mar 22, 2018).
15
Private Wells, United States Environmental Protection Agency. Learn About Private Water
Wells: Well Components. https://www.epa.gov/privatewells/learn-about-private-water-wells
(accessed April 3, 2018).
18
dissolved solids in the water system. The water does not continuously dissolve the surrounding
ground minerals because it does not come into contact with them after a certain time.
The Delaware River water was the softest, as was expected. This conclusion was
bolstered by the timing of the water sample collection. The water sample was taken from the
river in early spring (March) after a particularly bad winter storm brought an accumulation of
10+ inches of snow to central and southeast Pennsylvania.16 This snow was in the process of
melting and inundating the tributaries that lead to the Delaware River. The higher flow rate
The Macungie tap water was the hardest, also the result that was expected. According to
the Borough of Macungie water parameters, its water has a Ca2+ hardness of 13.3 grains per
gallon.17 When converted to ppm, this is a hardness of approximately 228 ppm CaCO3. This
measurement is a little more than the range which was calculated for the tap water (160 – 218
ppm CaCO3). This brings up the quantitative differences of the experiments that were carried
out.
The EDTA serial titration naturally resulted in a higher CaCO3 ppm measurement
because it is a technique used to find out the total divalent cation concentration in a solution. It
does not discriminate between polyvalent ions and takes into account all of them, not just the
Ca2+ and Mg2+ ions that are responsible for water hardness. Pennsylvania geologic records
include sandstone and shale formation, which contributed to the polyvalent cation content of the
16
Lehigh Valley Live, Lehigh Valley Weather. Lehigh Valley is in ‘Jackpot’ Area for
03/07/2018 Snowstorm.
http://www.lehighvalleylive.com/weather/index.ssf/2018/03/lehigh_valley_is_jackpot_area_for_
03072018_snowsto.html (accessed Mar 25, 2018).
17
Borough of Macungie, Borough Water Parameters, Borough Test Results: Calcium Hardness.
http://macungie.pa.us/drinkingwater.htm (accessed April 15, 2018).
19
water samples.18 In contrast, the Atomic Absorption Spectrophotometry technique only measured
the concentration of one type of cation at a time and was thus a smaller, more specific hardness.
EDTA as a whole is relatively precise. In three of the four sample titrations, the duplicate
analysis matched the original. However, in the pond water sample, one endpoint occurred at well
7 while the other occurred at well 9. Because each drop of EDTA corresponded to a change of
20.0 ppm CaCO3, the hardness value would change by that number if there were a one well
difference. By EDTA, the pond water consequently had a range of 139 – 180. ppm CaCO3.
EDTA was not only precise, it was also quite accurate in this experiment. When determining the
concentration of the known Ca2+ and Mg2+ solution, it only had a percent error of 20%. For a
general overview of the water sample composition, EDTA offered a scientifically sound, cost-
Atomic Absorption Spectrometry also had a high degree of accuracy in this project. The
percent errors of the check standards are outlined in the tables on the next page. In summary, the
percent error of the AA spectrophotometer did not exceed 43% for any of the standards. For
most of the standards, the percent error was much lower. The AA instrument can thus be trusted
to be accurate in the analysis of the four water samples that were tested.
18
Barnes, J. H.; Sevon, W. D. The Geological Story of Pennsylvania. Commonwealth of
Pennsylvania Department of Conservation and Natural Resources. Bureau of Topographic and
Geologic Survey. [Online] Educational Series 4, 2014.
http://www.docs.dcnr.pa.gov/cs/groups/public/documents/document/dcnr_014597.pdf
(accessed April 11, 2018).
20
CONCLUSION
Of the four water samples that were tested, the Delaware River water was the softest, the
Zionsville well water was the next softest, the Bullfrog Valley Pond water was hard, and the tap
water from Macungie was the hardest. These results were not what was expected, but can be
explained due to the geologic trends of the state of Pennsylvania, the specific construction of
well water pipes, and recent meteorological events to the sampling period.
22
REFERENCES
In numerical order:
1. The USGS Water Science School, USGS: Science for a Changing World. Water Properties
Home: Water Hardness. https://water.usgs.gov/edu/hardness.html (accessed Mar 22, 2018).
2. Cotruvo, J.; Bartram, J. eds. Calcium and Magnesium in Drinking Water: Public Health
Significance. Geneva, World Health Organization, 2009.
4. Community College of Rhode Island, Chemistry Courses: Labs, Calcium Analysis by EDTA
Titration.
http://www.ccri.edu/chemistry/courses/chem_1100/wirkkala/labs/Calcium_Analysis_by%20ED
TA_Titration.pdf (accessed April 10, 2018).
6. Thompson, S. PSU Chemtrek: Small-Scale Experiments for General Chemistry. Keiser, J. Ed.;
Hayden-McNeil Publishing; Plymouth, MI 2017. pp. 10-1 to 10-24.
7. McCarthy, L. T.; Keighton, W. B.; Quality of Delaware River Water at Trenton, New Jersey.
Geological Survey Water-Supply Paper 1779-X. [Online] 1964.
https://pubs.usgs.gov/wsp/1779x/report.pdf (accessed April 5, 2018).
10. Neely, S. Seat 169, pp. 34-37. Pond water sample, Bullfrog Valley Pond, PA.
11. Paul, S. Seat 176, pp. 31-33. River water sample, Delaware River, PA.
12. Chochlain, L. Seat 170, pp. 40-56. Tap water sample, Macungie, PA.
13. Patterson, M. Seat 175, pp. 51-53. Well water sample, Zionsville, PA.
23
14. USGS Water-Quality Information, USGS: Science for a Changing World. Water Hardness
and Alkalinity: Water Hardness. https://water.usgs.gov/owq/hardness-alkalinity.html
(accessed Mar 22, 2018).
15. Private Wells, United States Environmental Protection Agency. Learn About Private Water
Wells: Well Components. https://www.epa.gov/privatewells/learn-about-private-water-wells
(accessed April 3, 2018).
16. Lehigh Valley Live, Lehigh Valley Weather. Lehigh Valley is in ‘Jackpot’ Area for
03/07/2018 Snowstorm.
http://www.lehighvalleylive.com/weather/index.ssf/2018/03/lehigh_valley_is_jackpot_area_for_
03072018_snowsto.html (accessed Mar 25, 2018).
17. Borough of Macungie, Borough Water Parameters, Borough Test Results: Calcium
Hardness. http://macungie.pa.us/drinkingwater.htm (accessed April 15, 2018).