1

Sarea Recalde Phillips

9 November 2015
Experiment 10-The Chemistry of Natural Waters
Chem 111-104
Group Members: Noah Roberson, Tara Rogers, Andrew Phoebe, Zach Ripic
TA: Kriti Seth

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Introduction
Water hardness can best be defined as the amount of dissolved minerals present in a
volume of water. Magnesium and calcium are two of the most common minerals observed to
measure a waters hardness, but other substances such as zinc and aluminum attribute to the
hardness levels2. Water hardness is directly proportionate to the amount of magnesium and
calcium dissolved in the water; the higher the concentration of the two minerals causes the water
to become higher, and vice versa.
Water hardness is reported in terms of parts per million (ppm), and the degree of hardness
can be classified into five categories: soft, slightly hard, moderately hard, hard, or very hard1.
These classifications were determined and established by the U.S. Department of Interior and
continue to be a guideline for water quality departments in various state counties to report to
their inhabitants. Water with a concentration of 0-17ppm is classified as soft. Slightly hard water
contains 17-60ppm. Moderately hard water contains 60-120ppm. Hard water contains 120180ppm, and very hard water contains at least 180ppm. The hardness of water is usually
distributed in an annual report and displays the water hardness of that particular area to its
inhabitants5.
While water hardness can be classified with standards previously set by the U.S.
government, there are a range of factors that affect water and its hardness. Typically water that is
exposed to a higher amount of magnesium and calcium will have a higher likelihood of
dissolving, thus increasing its ppm. Both minerals, along with the many other substances that
account for water hardness, are acquired through water running past or through rock such as
limestone or other forms of sedimentary rock3. Water hardness also increases if it runs
underground as well1 2. Groundwater acquires dissolved particle in the same manner as water that

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simply runs through mineral rich rocks, but since the groundwater interacts and dissolves a more
concentrated amount of minerals, groundwater ppm will most likely be high than any other type
of water source.
The amount of minerals and ions present in water affects health and industry, with the
latter being more affected. Water hardness does not have a grave impact on an individuals
health. In, fact the health effects are moderately mild2. Ingestion of minerals, particularly
magnesium and calcium, present in water with a high amount of hardness may likelihood of
temporary diarrhea. Hard water also acts as an impromptu method of increasing mineral intake,
thus attributing positively towards aiding in increasing and individuals daily mineral intake.
Even if the mineral concentration is high, the body will flush out the excess particles from its
system.
The concern about hard water is more prevalent for industry and pipe systems. Minerals
contributing to water hardness deposit themselves within pipelines, and it can create a buildup
that renders the pipes inefficient8. Water with a high hardness can be costly to industries because
it can clog pipes and result in replacing machines altogether. The problem also transposes into an
individuals household1. Hard water leaves residue once the water is evaporated, and this then
can affect how efficient faucets and appliances that require water to work to perform in a subpar
way. Overall, hard water does not have many negative health effects, but efforts to reduce water
hardness are done in order to decrease the likelihood of inefficiency in devices and industrial
works.
While metal ions may be prevalent in water, methods have been used to decrease, or
soften, the amount of ions present in water. These include cation exchange resins4 8. The cation
exchange works by substituting an ion such as Na or H, strongly positive ions, with metal ions

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such as Mg or Ca. The exchanged ions then are separated from the water, thus decreasing its
presence and decreasing the water hardness.
Water hardness can be measured with devices such as the Atomic Absorption (AA)
Spectroscopy, and methods such as EDTA titration and a cation ion exchange8. The AA
spectroscopy was calibrated in order to provide an accurate representation of the specific
concentrations of Ca and Mg ions, as seen in Figure 1 and 2. In order to calibrate the device, a
known concentration of Ca and Mg were placed in two separate spectroscopy devices. Both
devices excited the atoms and raised the electrons to a higher state of energy. The electrons
would then stabilize and emit light specific to the element that would then calculate the
absorbance of the ions. From the two spectroscopy devices, two equations resulted that could
would be able to aid in finding the ppm of the respective ions. This method of calculating the
ppm is more specific in regards to Mg and Ca ions, and it provides more accurate results for the
specific amount of particles.
The EDTA titration and cation ion exchange were effective in calculating the ppm of the
water samples, but they have less accurate values for the Mg and Ca ions. Both titrations account
for all divalent ions and metal ions present in a water sample, while the AA spectroscopy
observes the specific amount of ppm of a specific ion. While the titrations give a more broad
number of ppm, it is effective in detecting the Mg and Ca ions and serves as a cheap alternative
to the AA1.
In this lab, the main objective was to observe and report the effect that the source of
water can have on the waters hardness. Five different water samples were obtained: Wichita, KS
tap water; Aquafina bottled water; State College, PA tap water; Lansdale, PA tap water; and
Buffalo, NY tap water. From these different water sources, the water obtained from Wichita, KS

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will have the highest amount of metal ions like Mg and Ca. The softest water sample will be the
Aquafina bottled water, since this will have undergone filtration to get rid of any impurities or
excess metal ions. Wichita obtains a majority of its drinking water from the Cheney reservoir and
groundwater6, and groundwater contains more concentrations of metal ions than any other type
of water2. In fact, the average ppm for tap water in the Wichita area is around 107, according to
annual reports7 The other water samples, aside from the Aquafina, will have softer water than the
Wichita sample because most those areas receive their water from rivers. Buffalo, NY, for
example, is near Lake Erie, which is a large body of water that has a smaller concentration of
metal ions present5. Overall, the results should have the Wichita water sample as having the
hardest water, the Buffalo, Lansdale, and State College water samples as having similar
hardness, and the Aquafina water sample as having the lowest concentration of ions present.
Procedure
In order to determine the concentration of Mg and Ca within the waters samples, EDTA
titration, cation exchange, and AA spectroscopy were used. The procedures for conducting both
methods of finding the concentration were found in the PSU Chemtrek, but EDTA titration had
more explicit steps for the user to follow8. The EDTA titration is a method that calculates the
total amount of ions within a sample, but in order to visually see the amount of ions within a
sample, the sample must be have a pH level high enough to see titration reaction. This can be
achieved through the use of a NH3/NH4Cl buffer that is added to the sample. Along with the
adjusted pH level, eriochrome black T (EBT) is used a visual reactant with metal ions like Mg
which turns the sample blue, but after a while the solution becomes a purple as the EBT begins
to react with the Mg. The EDTA is then added to the solution until the solution returns to a blue

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color. This change occurs as a result of the interaction between the EDTA and the Mg indicator,
with the EDTA making the latter clearer as the interaction progresses.
With regards to the water sample experiment, the procedure was relatively similar to the
general guideline of the EDTA titration. A 1x12 well was filled with one drop of a 1:1 diluted
water sample per well. One drop of each the buffer (NH3/NH4Cl/MgEDTA) is dropped into each
well. After the three drops are placed into the wells, an EDTA solution of 2.00x10-4M is then
serially added into each well. Serially adding the EDTA meant adding one drop of solution into
one well and adding an extra drop per well following the preceding well. This procedure was
done twice, and with each EDTA procedure the solution was stirred in order to provide an
accurate representation where the solution changes color. After the two titrations were
performed, the point at which the color change occurred in each titration was averaged, and then
this result was then used to find the ion molarity, which would then be represented as a molarity
of CaCO3. The molarity would need to be multiplied by 2 in order to account for the 1:1 dilution
of the water sample. The molarity was found using the equation:
MEDTAVEDTA = Mdiluted sampleVdiluted sample
2*(2x10-4M)(3.5 drops) = (Mdiluted sample)(1 drop)
1.40x10-3 = Mdiluted sample
Once the molarity was calculated, the ppm of the water sample was found with this
equation:
(1.40x10-3mol CaCO3)
100.0g CaCO3 1000.0mg CaCO3
1 L of solution
1 mol CaCO3
1g CaCO3

140ppm

Another measurement of water hardness performed was the cation exchange. The cation
exchange substitutes divalent cations such as Mg and Ca with monovalent cations such as Na
and H, and this is done in order to soften the water sample by extracting the ions from the water
itself. To obtain the water hardness of the Wichita, KS tap water, an 8mL vial was prepared and

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cleansed with distilled water before a small amount of the cation exchange resin was placed in
the container. About a 1cm amount of the 1:1 diluted water sample and mixed with the resin.
Once the solution was fully mixed, a pipet was used to extract the excess liquid from the vial and
separate the formed resin beads. The resin water was then extracted with a small-drop pipet, and
one drop of the water was placed into each well of a 1x12 well. With the resin water, the same
dilution process used in the EDTA titration was followed, and the titration was done twice. The
average of the EDTA titrations were then used to calculate the concentration of the ions, and
subsequently of the water harness.
MEDTAVEDTA = Mdiluted sampleVdiluted sample
2*(2x10-4M)(2 drops) = (Mdiluted sample)(1 drop)
8.0x10-4 = Mdiluted sample

(8.0x10-4mol CaCO3) 100.0g CaCO3 1000.0mg CaCO3

1 L of solution
1 mol CaCO3
1g CaCO3

80ppm

The last method used to evaluate the hardness of the water sample was the AA
spectroscopy. The spectroscopy enables the specific concentrations of Mg and Ca ions to be
calculated precisely without any of the extra divalent ions that may be accounted for in the two
previous water hardness methods stated previously. Before the 1:1 diluted water sample was
placed in the AA spectroscopy, the water sample was used to fill two thirds of two large bulbs of
two large pipets. The stems were then cut off and placed into a sample holder until the water was
analyzed with the AA spectroscopy. The concentration levels found from the device were then
recorded and later used to find the ppm of the water human in regards to the waters specific Mg
and Ca concentrations.

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Once the equations were found, the ppm could then be found. The water samples from
Wichita, KS and State College, PA were multiplied by two in order to account for their 1:1
dilution factor. The results would then be multiplied by 100g CaCO3 per mole and divided by the
grams of Mg or Ca per mole. The following results for Ca and Mg ions were added together to
create the total water hardness. The results for all the water samples can be seen in Table 1.
CaWichita, KS tap water: y = 0.0063 + 0.006
0.1019 = 0.0063x + 0.006
(0.1019-0.006)/0.0063 = x
2*(15.22)ppm = x
30.44ppm = x

MgWichita, KS tap water: y = 0.014x + 0.0144

0.1410 = 0.014x + 0.0144
(0.1410-0.0144)/0.014 = x
2*(9.043)ppm = x
18.09ppm = x

The ppm values of the Ca and Mg ions were then treated as if they were a concentration
of CaCO3, and the two ppm values were then added together to form the total water hardness of
the sample.
100.09g CaCO3
1 mole ac
30.44ppm Ca x
40.08g Ca s
1 mole

= 76.016ppm CaCO3
= 76.016ppm hardness

100.09g CaCO3
1 mole ac
18.09ppm Mg x
24.31g Mg
1 mole

= 74.48ppm CaCO3
= 74.48ppm

hardness
Valuetotal hardness = HardnessMg + HardnessCa
= (74.48 + 76.016)ppm
= 150.50ppm
RESULTS
The graphs and data tables were created from a compilation of five peoples data9 10 11 12.
The members of this groups included: Sarea Recalde-Phillips, Noah Roberson, Tara Rogers,
Andrew Phoebe, and Zach Ripic. Figure 1 and 2 are line graphs of the calibrated AA
spectroscopies for Ca and Mg ions. The tables to the right of the graphs are the ion

9
concentrations with respect to the absorbance value. The slope equation for both figures are
located in the top left of the graphs, and below the equation is the R2 value. The AAs were
calibrated before the waters samples were evaluated in order to establish a relation for the water
samples to be based off of. The r-value is used to indicate the accuracy of the calibrating; the
closer the r-value was to zero, the more accurate the results were.

Ca
Concentration
(ppm)
Ca
Concentration
(ppm)
1
5
10
25
50

Absorbance Value (at 422.7nm)

Figure 1: AA spectroscopy light

absorbance vs. Ca metal ion concentration
0.35
0.3 y = 0.0063x + 0.006
R = 0.9992
0.25
0.2
0.15
0.1
0.05

Absorbance
Value (at
422.7nm)
Absorbance
Value (at
422.7nm)
0.00822
0.03787
0.07041
0.16875
0.3186

0
0

10

20

30

40

50

60

Ca Concentration (ppm)

Mg
Absorbance
Concentration Value (at
(ppm)
202.5nm)
1
0.01999
5
0.08804
10
0.16386
25
0.3614
30
0.43598

Absorbance Value (at 202.5nm)

Figure 2: AA Spectroscopy light

absorbance vs. Mg metal concentration)
0.5
0.4

y = 0.014x + 0.0144
R = 0.9986

0.3
0.2
0.1
0
0

10

15

20

25

30

35

Mg Concentration (ppm)

Table 1: Ca and Mg Concentrations Based on AA

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copy Calibrations
Table 1: Ca and Mg Concentrations Based on AA Spectroscopy Calibrations
Ca Concentration (in
Type of Water
ppm)
Mg Concentration (in ppm)
Wichita, KS Tap Water
30.444
18.086
Aquafina (Bottled
Water)
-0.95238
-0.779
State College, PA Tap
56.920
27.071
Water
Lansdale, PA Tap
Water
20.5238
7.564
Buffalo, NY Tap Water
24.095
10.243

Table 2: Group Data

Members

Method
Distilled Water
Total
Ca2+
Dissolved
Salts
(TDS)
Water Sample

AA

EDTA

Sarea
RecaldePhillips

Andrew
Phoebe

Zach
Ripic

Tara Rogers

Noah
Roberson

Wichita,
KS Tap
Water

Aquafina
Bottled
Water

State
College,
PA Tap
Water

Lansdale, PA Tap
Water

Buffalo,
NY Tap
Water

no residue

no residue

no residue no residue

some
residue

faint ring

white ring

small
amount of
residue

strong
white ring

slightly darker
ring than Ca2+

small, thin
white ring
of residue
heavy
amount of
white
residue

very faint
residue
heavier ring
than
distilled
heavier ring
compared
to Ca2+

Ca Absorbance

0.1019

0.0000

0.1853

0.1353

0.2200

Mg Absorbance
Unsoftened
Water
concentration
(M)
Resin Softened
Water
Concentration
(M)

0.1410

0.0035

0.2039

0.1203

0.1578

1.4x10-3

2.0x10-4

1.3x10-3

1.0x10-3

2.0x10-3

8.0x10-4

6.0x10-4

4.0x10-4

2.0x10-4

4.0x10-4

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Table 3: Group Data of ppm Results Using AA Spectroscopy and EDTA

Methods
Sarea
Andrew Zach
Tara
Noah
Members
RecaldePhoebe
Ripic
Rogers
Roberson
Phillips
State
Wichita, Aquafina
Lansdale, Buffalo,
College,
Method
KS Tap
Bottled
PA Tap
NY Tap
PA Tap
Water
Water
Water
Water
Water
Ca (ppm)
76.01646 -2.37834 142.1438 51.27565 60.17137
AA
Mg (ppm) 74.46432 -3.20733 111.4577 31.14277 42.17285
Unsoftened
Water
(ppm)
140
20
130
100
200
EDTA Resin
Softened
Water
(ppm)
80
60
40
20
40

Discussion
After accumulating the data results from the five water sources, the results concluded that
the State College, PA tap water had the highest Mg and Ca concentrations and ppm hardness,
and the Wichita, KS tap water had the second highest concentrations and ppm hardness. This
went against the preconceived hypothesis that the Wichita, KS tap water would have the highest
of all results. Although the first part of the hypothesis was incorrect, the second part stating that
Aquafina would be the softest water sample was correct, as seen by the first EDTA row
calculation in Table 3. The first EDTA water harness row was the largest for all samples except
the Wichita, KS tap water and State College, PA tap water. The second highest total water
hardness was obtained from the AA spectroscopy calculations, and the softened EDTA water
hardness had the smallest amount of ppm present for each water sample except the Aquafina
water sample.

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The order in which water total water hardness was present the most in each type of
method is plausible and makes sense. As it was previously stated in earlier sections, EDTA
titrations take into account all forms of divalent ions present in the sample, so when observing
the data, the reader must take into account that the data presented in Table 3s EDTA rows
include other substance besides the dominating Mg and Ca ions. The EDTA samples had a
relatively significant change among all samples. For example, the Lansdale sample experienced
an 80% decrease in its hardness once it was softened, while the Wichita sample experienced a
43% decrease in its hardness. The change in ppm was within that range of percentage of
increase, but the Aquafina sample had an anomalous change in its ppm hardness. Unlike the
other that experienced a decrease in their hardness, the bottled water sample had a 200%
increase, which is very unrealistic result.
Throughout the data there were some inconsistencies when compared to other water
sample results. For example, in the AA the total ppm hardness of the Ca and Mg ions were
higher than the total water hardness found in the EDTA titration. It is also a point to raise that
these water samples were also the only samples that had a 1:1 dilution, so any type of error that
might have occurred in these samples could be due to improper calculations or misinterpreted or
incorrect data. Along with that anomaly, the Aquafina water sample presented a negative
concentration of Ca and Mg concentration in Table 2, and subsequently a negative ppm for both
ions in Table 3. These negative result may be because the sample underwent a filtration process
that omitted a majority of ions that would have been present had it not been filtered.
Some of these inconsistencies may have been caused by a number of factors, particularly
in the procedure for the EDTA titrations. The EDTA titrations had multiple steps that required
placing drops into wells, and the angle at which a substance was placed into the well could affect

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the concentration evaluation at the end. For example, holding the small-drop pipet perpendicular
to the well yielded a more voluptuous drop of a substance, so more of it would be present.
Conversely, if the pipet was held at a 45 degree angle, the substance that came out would have a
lower volume when dropped in the well. Besides the pipet technique, the EDTA titration
required an individual to observe a color change during the serial titrations. If the solutions were
not properly stirred, the color change could be inaccurate, thus making the concentration levels
wrong later on in calculating the ppm hardness of the water samples.
Along with these factors that may have contributed to the inaccuracies found in the water
samples, improper washing techniques may have added impurities to the samples. In the AA
method, the pipet in which the water samples were held should have be cleaned out with distilled
water. The same should have been done for the EDTA titrations pipets and wells used in the
procedures. Besides the manual sources that could have contributed to the results inaccuracies,
computational errors could have attributed to the samples inaccurate reports. Not accounting for
dilution factors or improperly using a dilution factor in regards to the concentrations could have
resulted in concentrations that were too low or too high. Using the wrong equations with the
wrong data could have resulted with improper yields of ppm hardness for Mg and Ca ions in a
water sample as well.
Conclusion
Based on the experiment, the initial hypothesis was incorrect. The sample water obtained
from State College, PA had the highest Ca and Mg concentrations. Wichita, KS, however had the
second highest concentration of the Ca and Mg ions, so although the initial hypothesis stated that
Wichita would have the hardest water, it still had a rather high amount of ions present. The AA
spectroscopy calculations should be focused on if a person wanted to know the amount of Ca and

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Mg ppm hardness. The AA provides more accurate and specific amounts of a particular ion
placed within the device. The EDTA titration takes into account the presence of all ions in the
sample, so EDTA provides a higher hardness for the water because of its broadness in
interpretation. The EDTA softening method aids in establishing a more precise number in other
divalent ions present in a water sample since the cation exchange process used in the titration
removes Mg and Ca ions out of the water.
The AA spectroscopy and EDTA titrations enabled water hardness to be calculated, but
EDTA is more applicable for real life applications. Water hardness is a problem in industry and
pipeline systems because harder water leaves residue in devices and pipes. This then creates an
inefficiency in the devices use and could lead to costly consequences with regards to replacing a
system or removing a system or fixture completely.
References
1

Oram, Brian. "Drinking Water Hardwater Hardness Calcium Magnesium Scale Stained

Laundry." Water Research Center. Water Research Watershed Center, n.d. Web. 2 Nov. 2015.
<http://www.water-research.net/index.php/water-treatment/tools/hard-water-hardness>.
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Sengupta, Pallav. "Potential Health Impacts of Hard Water." International Journal of

Preventive Medicine. Medknow Publications & Media Pvt Ltd, 4 Mar. 2013. Web. 02 Nov.
2015. <http://www.ncbi.nlm.nih.gov/pmc/articles/PMC3775162/>.
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"Hardness in Drinking-water." Guidelines for Drinking-water Quality, 2nd ed. Vol. 2. (1996): 1-

4. Who.int. The World Health Organization, 4 Mar. 2006. Web. 2 Nov. 2015.
<http://www.who.int/water_sanitation_health/dwq/chemicals/en/hardness.pdf>.
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"Consumer Guide to Water Filters." Nrdc.org. Natural Resources Defense Council, 9 Jan. 2006.

Web. 02 Nov. 2015. <http://www.nrdc.org/water/drinking/gfilters.asp>.

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5

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Protection Agency, n.d. Web. 29 Oct. 2015.

<http://ofmpub.epa.gov/apex/safewater/f?p=136%3A102%3A>.
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"Where Does Your Water Come From?" Nature Conservancy: Protecting Nature, Preserving

Life. The Nature Conservancy, 2015. Web. 29 Oct. 2015.

<http://www.nature.org/ourinitiatives/habitats/riverslakes/placesweprotect/where-does-yourwater-come-from.xml>.
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Boyd, Claude E. "2015 Water Quality Report: Delivering High Quality Water to Your Tap."

2015 Water Quality Report (2015): n. pag. Water Services Department-City of Kansas City. KC
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Thompson S. PSU Chemtrek Small-Scale Experiments for General Chemistry. Plymouth, MI:

Hayden-McNeil, 2015. 10-2-0-11. Print.

9

Roberson, Noah, Fall 2015, Chem 111-104.

10

Rogers, Tara, Fall 2015, Chem 111-104, pp.46-51.

11

Phoebe, Andrew, Fall 2015, Chem 111-104.

12

Ripic, Zach, Fall 2015, Chem 111-104.