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THE PENNSYLVANIA STATE UNIVERSITY

Measuring and Comparing


Water Hardness in Three
Distinct Samples

















Kevin Brown
11/13/13
Chemistry 111-Experimental Chemistry
Section 105
Group Members: Derek Brady and Michael Brulo
Teaching Assistant: Ethel Khanis
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Introduction
In this lab report, I will explain the hardness analysis of three different samples
of water. Water described as hard contains high amounts of dissolved calcium and
magnesium. Hard water is not a health risk but is a nuisance because of mineral buildup
on plumbing fixtures and poor soap and/or detergent performance (Skipton). The three
samples I will examine in this report are the following:
1. A sample of sink water obtained from the bathroom on the third floor of
Sproul Hall, a Residence Hall in East Halls.
2. A sample of drinking water obtained from a water fountain on Penn States
Campus. My lab partner, Derek Brady, obtained this sample.
3. A sample of pond water from Hershey, Pennsylvania. My lab partner, Michael
Brulo, obtained this sample.
For each of these samples, my lab partners and I performed water hardness analysis
through the use of EDTA Titration and Atomic Absorption Spectrophotometry, two types
of analysis I will explain in greater detail further into this introduction.
Water hardness is a property that is attributed to water that has a large combined
concentration of Ca
2+
and Mg
2+
(Thompson 10-2). Conversely, waters that are not high in
concentration of these divalent cations are often described as soft (divalent merely
implies that the ions are missing two electrons in their valence shells compared to the
neutral form). The reason that water often picks up these impurities is because it is an
effective solvent. Water has the ability to dissolve and pick up small amounts of minerals
as it moves through terrain. Water hardness can be problematic because of its interference
with daily household cleaning. The quantity of soap or detergent needed to clean is
relative to the amount of hard minerals in the water being used. Hard water reacts with
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soap to create a sticky curd. Some synthetic detergents can be rendered ineffective by
hard water, because the active ingredient is partially inactivated by the hardness.
Laundering in hard water can be particularly troublesome, because these curds (which are
small and congealed solids) can form on fabric during washing. Repeatedly washing
clothes with hard water can ruin clothing. Other problems that can result from hard water
include curds forming on many household objects like dishes, bathtubs, and pipes. For
this reason, hard water can lead to inefficient and expensive utilization of water-using
appliances (Skipton).
Although hard water can be inconvenient, it is not considered a health risk.
Surprisingly, the National Research Council, also known as the National Academy of
Sciences, has said that hard drinking water can confer small amounts of calcium and
magnesium that are required in the human diet. Further studies have even suggested a
positive link between water hardness and reduced lower cardiovascular mortality.
Although some amount of correlation has been shown, there is no conclusive evidence
(Skipton).
Water hardness can be measured by a variety of methods. The two methods
utilized in this experiment were EDTA Titration and Atomic Absorption
Spectrophotometry. Titration, also known as volumetric analysis, is a laboratory
technique that is used in determining the concentration of substances in solution by
carefully adding certain amounts of a reactant until a visible reaction occurs; the quantity
of reactant needed to propel this reaction forward can be used to calculate concentration
of a substance, in this case Ca
2+
and Mg
2+
. For water, hardness can be determined by
titrating it with a standard solution of ethylene-diammine-tetra-acetic acid, otherwise
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known as EDTA. EDTA titration works by capturing metal ions through chelation.
EDTA is an effective chelating agent, which means it can form many bonds to a single
metal ion; EDTA can form somewhere between four to six bonds with a single metal ion.
Because EDTA captures these metal ions, it is in a sense a water softening process;
however, although the water is softer, the metal ions are not removed. EDTA merely
causes the metal ions to cling to itself in the solution rather than be dispersed throughout
the water. In order to observe this reaction between the EDTA and the metal cations,
Eriochrome Black T, or EBT, is used as an indicator. When EBT is added to a sample of
hard water, it forms a complex with calcium that is pink in color. As EDTA is
continuously added to this sample, it will steal these calcium atoms to form a complex
with them, returning the EBT to its original blue color. The amount of EDTA drops it
takes to return the solution to this blue color provides a way of quantifying the
concentration of calcium and magnesium (Spurlock). The reaction can be described by
the following chemical equation, where HD
2-
represents the indicator:
HD
2-
+ Mg
2+
+ Ca
2+
MgD
-
+ H
+
+ Ca
2+

CaEDTA + MgEDTA + HD
2-
(Thompson 10-6)
The HD
2-
will make the solution blue first. When it combines with magnesium it will turn
red. Finally, when enough EDTA is added to complex with calcium, and then the
magnesium, the solution will return to its blue color. It is important to note that before
this titration can be carried out, the pH of the solution has to be buffered to a pH of 10 so
that the blue color can be observed at the start (Thompson 10-5).
Atomic Absorption analysis can be utilized through a machine called an Atomic
Absorption Spectrophotometer. This device works by creating voltage that excites the
magnesium or calcium atoms within the lamp. When these excited atoms relax, they emit
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monochromatic light that is proportional to the difference between two electronic energy
levels (Thompson 10-8). The magnesium and calcium atoms in the water sample then
absorb this emitted light; the amount of this absorbance, which is proportional to the
concentration of calcium and magnesium, is then measured and quantified by the
machine (Thompson 10-7).
There are some apparent differences when conducting both of these types of
analysis. Atomic Absorption Spectrophotometry can be used to assess the distinct
concentrations of either calcium or magnesium, whereas EDTA titration will only sum up
the concentration of these and other sources of water hardness. EDTA will also create
more chances for error in the experiment, whereas Atomic Absorption
Spectrophotometry is a more exact and mechanical measurement process. Therefore,
there are benefits and drawbacks to either type of analysis. Since the Spectrophotometer
leaves less room for error however, and allows one to measure concentrations for
individual ions, I personally see it as the better form of analysis.
A common way of softening water is through an ion exchange unit. Most
household water softeners use this process. This process works by moving the water
through a resin, which is a solid. The negative charge of these anion groups are balanced
by a monovalent cation, such as Na
+
. When the hard water passes through a device such
as this, the divalent cations, due to their stronger attraction, will exchange places with the
monovalent cations; this will reduce the hardness due to divalent cations such as calcium
and magnesium. However, the unit cannot soften water forever; eventually there will be
no monovalent cations left in the resin to switch with either calcium or magnesium. In
order to soften water again, the unit must undergo regeneration, which involves
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backwashing the resin with a salt solution, which will remove the divalent cations and
replace them with Na
+
.
I hypothesize that water samples taken from sources that are considered less
consumable should contain the greatest level of hardness. In this case, I suspect the pond
water to be the hardest, followed by the bathroom sink water, and then the drinking
fountain water. I have formed this hypothesis based on the information I have compiled
from the sources above; it appears that the only places where water hardness is seen is
where there has been no steps to reduce it, such as in natural water sources or household
appliances.
Procedure
The following procedure was taken from 2013-2014 edition of the PSU
Chemtrek, written by Stephen Thompson, and edited by Dr. Joseph T. Keiser. Although
this procedure was mapped out in a specific order of completion, it was not followed in
this specific order due to constraints of time and use of the AA machine. I will describe
the procedure in the fashion that I completed it.
First, I completed a TDS determination, which was a qualitative determination of
the amount of Total Dissolved Solids in my sample. To perform the TDS determination
required a small piece of aluminum foil and a hot plate. The procedure required me to
place the aluminum foil on the hot plate and then put one drop of my undiluted water
sample onto the foil. After the drop of the undiluted sample was added, I added one drop
of distilled water and then another drop of 1 x 10
-3
M Ca
2+
. After the water evaporated, I
removed the foil from the hot plate so I could observe what remained on the foil.
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Next, I proceeded to do a Divalent Cation Analysis by EDTA Titration, which
allowed me to observe the chemistry involved in complexation reactions of EDTA with
calcium and magnesium standard solutions. Before I carried out the titration I completed
some preliminary steps. First, I placed one drop of EBT into the first three wells of a 1 x
12 well, and then added NH
3
(also called NH
4
Cl) buffer to well two and three. Wells two
and three turned a dark blue color. Then I added Mg
2+
to well three, and observed the
color turn a pinkish-red. What I was observing was the beginning of an EDTA titration.
Now that I had familiarized myself with the process, I continued by cleaning out a
separate 1 x 12 well strip with distilled water so I could perform a serial titration. In each
well, I added one drop each of Ca
2+
solution, EBT, and NH
3
/NH
4
Cl/MgEDTA buffer.
Then I completed a serial titration by adding one drop to the first well, two drops to the
second well, and so forth.
` In the next section of titrations, I completed another titration, except this time
using my own water sample rather than the standard solutions of calcium and
magnesium. Although the book instructed me to do another serial titration, I had to do a
well titration to adequately meet reach the equivalence point of my titration; there simply
was not enough room in the 1 x 12 wells to accommodate the titration of my water
sample.
After I had carried out my titration analysis, I used the Spectrophotometer to
determine the specific concentrations of both calcium and magnesium in my water
sample. Before doing this however, I had to dilute my sample because of its expected
high level of hardness. I diluted it by two parts distilled water for every one part of
sample water; basically, I combined ten milliliters of my sample with twenty milliliters of
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distilled water to achieve adequate dilution for analysis. I filled two large pipets with this
diluted sample so that they could each be analyzed by the Spectrophotometer for the
concentrations of calcium and magnesium.
In the next section I softened my water sample with a commercial water-
conditioning agent. I did this by pouring some of my sample into a small vial and then
adding approximately twenty milligrams of the baking soda. I did notice that it took less
drops of EDTA to reach a titration equivalence point when I tested the softened sample.
Finally, I used a cation exchange resin to remove calcium and magnesium ions
from my water sample. I did this by combining a small amount of cation exchange resin
and my sample in a small vial. Then I tested the pH of the vial and observed that it was
highly acidic. The pH of my water on the other hand was fairly neutral. The new sample
in the vial was significantly less hard as determined by my EDTA titration.
Results
The following results can be found in the lab notebooks of Kevin Brown (pages
44 to 51), Derek Brady (pages 35 to 42), and Michael Brulo (pages unknown). The first
results I would like to present are those obtained from the Atomic Absorption analysis.
Table 1. Description of Sample and AA Analysis
Sample Diluted Calcium Absorbance Magnesium Absorbance
Bathroom Sink Yes. 1 to 2. 0.2525 0.2152
PSU Drinking Fountain
(Brady)
Yes. 1 to 2. 0.2524 0.2057
Pond in Hershey, PA
(Brulo)
No. 0.1977 0.1191
Table 1: Describes where sample was obtained, whether or not it was diluted, and the
calcium/magnesium absorbance values recorded by AA machine.
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Below, I have also included the AA calibration graphs for magnesium and calcium.
These graphs describe what concentration, in parts per million (ppm), of either
magnesium or calcium that corresponds to a specific absorbance. I have also included a
table of the points used to make these graphs. These points represent the way the AA
machine was calibrated to read certain concentrations and absorptions.
Table 2. AA Standards for Calcium
Calcium Concentration (ppm) Absorbance Value (at 422.7 nm) Check Standard (ppm)
0
1.000 0.01507 1.27
5.00 0.05970 5.08
10.00 0.10965 9.87
25.0 0.25829 24.79
50.0 0.47564 50.40
Table 2: Describes the standards that the AA machine utilizes in its evaluation of calcium.
Table 3. AA Standards for Magnesium
Magnesium Concentration (ppm) Absorbance Value (202.5 nm) Check Standard (ppm)
0
1.000 0.07085 1.08
5.00 0.08723 4.81
10.00 0.14790 9.24
25.0 0.33728 25.70
30.0 0.38734 30.40
Table 3: Describes the standards that the AA machine utilizes in its evaluation of magnesium.
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Figure 1: Calibration Curve for Magnesium Concentration by AA measured at 202.5 nm.

Figure 2: Calibration Curve for Calcium Concentration by AA measured at 422.7 nm
Using the equations that these linear trend lines produce, an approximate
concentration of either Mg
2+
or Ca
2+
can

be calculated. Here are two sample calculations,
y = 0.0115x + 0.0426
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0 5 10 15 20 25 30 35
A
b
s
o
r
b
a
n
c
e

V
a
l
u
e

(
2
0
2
.
5

n
m
)

Magnesium Concentration (ppm)
Graph 1. Magnesium Atomic Absorption Calibration Line
y = 0.0093x + 0.0166
0
0.1
0.2
0.3
0.4
0.5
0.6
0 10 20 30 40 50 60
A
b
s
o
r
b
a
m
c
e

V
a
l
u
e

(
4
2
2
.
7

n
m
)

Calcium Concentration (ppm)
Graph 2. Calcium Atomic Absorption Calibration Line
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using my absorbance values, of the concentrations of both calcium and magnesium using
their respective linear equations.
Sample Calculation 1. Magnesium Concentration Calculation
1. y=0.0115x+0.0426
y is the known variable. Solve for x to find magnesium concentration.
2. 0.2525=0.0115x+0.0426
3. 0.2525-0.0426=0.0115x
4. 0.2099=0.0115x
5. x=0.2099/0.0115=18.25 ppm
Sample Calculation 2. Calcium Concentration Calculation
1. y=0.0093x+0.0166
y is the known variable. Solve for x to find calcium concentration.
2. 0.2152=0.0093x+0.0166
3. 0.2152-0.0166=0.0093x
4. 0.1986=0.0093x
5. x=0.1986/0.0093= 21.35 ppm
I have also produced a table containing all of the calculated concentrations of my partners
and myself. The concentration produced by these equations for myself and Dereks
samples will only show the concentration of the diluted sample. In order to obtain the
concentration of the original solution, the concentration calculated must be multiplied by
a factor of three. This is because only 1/3 of the diluted sample actually contains our
water sample; the rest is distilled water.

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Table 4. Calculated Concentrations Using Calibration Line Equations
Diluted Ca
2+

Concentration
Diluted Mg
2+
Concentration
Original Ca
2+
Concentration
Original Mg
2+

Concentration
Bathroom Sink 18.25 ppm 21.35 ppm 54.75 ppm 64.05 ppm
PSU Fountain
(Brady)
14.18 ppm 25.35 ppm 42.5 ppm 76.05 ppm
Hershey Pond
(Brulo)
Not Diluted Not Diluted 19.47 ppm 6.65 ppm
Table 4: Describes the concentrations of calcium and magnesium calculated through the use of the
calibration lines.
For the EDTA Titrations used to measure hardness of the samples, no samples were
diluted. Below is a table describing the number of drops it took to titrate each sample to
the equivalence point.
Table 5. Number of Drops Required in Different EDTA Titrations
Bathroom Sink PSU Fountain (Brady) Hershey Pond (Brulo)
Unsoftened EDTA 29 drops 29 drops 7 drops
Baking Soda EDTA 23 drops 23 drops 5 drops
Resin EDTA 7 drops 6 drops 2 drops
Table 5: Describes the number of drops of EDTA required to reach the equivalence point of titration with
all three samples before they were softened, after they were softened with Baking Soda, and after they
were softened with a Ion Exchange Resin.
The next table describes the pH levels recorded before an ion exchange resin was used
and after.
Table 6. pH of Unsoftened and Softened Water Samples
pH Before Softening pH After Softening
Bathroom Sink 8 14
PSU Drinking Fountain (Brady) 4 8
Hershey Pond (Brulo) 7 4
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Table 6: Describes the pH levels of water samples before being softened, and after being softened by an
Ion Exchange Resin.
The table below describes the observations made on the aluminum foil after evaporating
the water sample.
Table 7. Total Dissolved Solids Observations of Residue
Sample Observation
Distilled Water No visible residue.
1 x 10
-3
M CaCl
2
Slightly visible white ring.
Bathroom Sink Sample White ring. Most visible of all.
PSU Drinking Fountain Sample (Brady) White Ring. Most visible of all.
Hershey Pond Sample (Brulo) White Ring. Most visible of all.
Table 7: Describes the observed residue of distilled water, CaCl2, and the three water samples.
The next calculation describes how to determine the total hardness of a sample through
the use of EDTA Titration.
Sample Calculation 3. Total Hardness Calculation
Total hardness can be calculated using the relationship M
1
V
1
=M
2
V
2
, where M
1
is the
concentration of EDTA, M
2
is the concentration of divalent cations, V
1
is the volume of
EDTA, and V
2
is the volume of the water sample. In this case, the objective is to solve
for M
2
, which is the concentration that will describe the hardness.
1. M
2
= M
1
V
1
/V
2
.
2. M
2
= (2.00 x 10
-4
M EDTA)(29 drops)/(1 drop)=5.8 x 10
-3
M CaCO
3

3. 5.8 x 10
-3
M CaCO
3
x (100 g CaCO
3
/1 mol CaCO
3
) x (1000 mg CaCO
3
/1 g CaCO
3
)
4. 580 mg CaCO
3
/1 L or 580 ppm.
The final table lists the calculated total hardness of the water samples according to
the EDTA titrations.
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Table 8. Calculated Total Hardness from EDTA Titration

Sample Total Hardness of Sample
Bathroom Sink Sample 580 ppm CaCO
3
PSU Drinking Fountain Sample (Brady) 580 ppm CaCO
3
Hershey Pond Sample (Brulo) 140 ppm CaCO
3
Table 8: Contains the calculated total hardness of the three samples of water.
Discussion
In the beginning of this report, I hypothesized that the pond water would be the
hardest sample, followed by the bathroom sink sample, and then the drinking fountain
sample. This hypothesis turned out to be not only wrong, but also backwards. The pond
sample turned out to be the least hard of all the samples. The reasoning for my hypothesis
turned out to be misplaced because I disregarded some other important details concerning
water hardness and the samples obtained.
I reasoned that the water hardness of the pond sample would be the most high
because it was from a natural water source, and therefore in close contact with natural
minerals and terrain. However, I ignored the probable fact that the water was taken from
the surface of the pondthis dramatically changes the way any such minerals would
have affected the sample. Since my lab partner Michael Brulo most likely took his
sample from the top of the pond, his sample would be less hard than a water sample taken
at the bottom, which has more contact with the terrain on which the natural water source
settles. Another possibility worth entertaining is that it rained before this sample was
taken, which would dramatically reduce the water hardness. Rainwater is very soft, and
could potentially reduce a harder sample to a much softer one (Hardness of Rainwater).
Since Derek Bradys samples and mine were both taken from the State College
area, it seems reasonable that both also have similar levels of hardness. Most of the water
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in State College is groundwater, which means that it is obtained from wells. State
College water typically contains between 120-190 mg of calcium/magnesium per liter.
Water that has a concentration of 100 milligrams per liter or above is considered hard
(Frequently Asked Questions). Therefore, water in State College is reputable for being
hard, so the State College water samples were well aligned with this reputation.
In my opinion, the data retrieved from the AA analysis is much more useful than
that retrieved from the EDTA titration. The EDTA titrations could have major errors
from inconsistency in drop size and careless observation. The AA machine eliminates the
chance for human errors such as these and allows users to at least reasonably approximate
the magnesium and calcium concentration through the use of a calibration line and
equation.
Water is typically classified as soft between 0-17.1 ppm, slightly hard between
17.1-60 ppm, and moderately hard between 60-120 ppm (Skipton). The pond water could
be safely classified as slightly hard, whereas the sink water and drinking fountain samples
could be classified as either moderately hard or simply hard.
My misplaced reasoning led me to conjecture that the water used in appliances
such as a sink or a drinking fountain would have a reduced hardness compared to natural
sources; it turns out that the appliances in State College have a high level of water
hardness because it is sourced from wells in the ground. I still think that the water at the
very bottom of the pond might be harder than either State College water sample, but I
have also come to the conclusion that surface water on natural water forms may not
always be that hard.

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Conclusion
In this experiment, I have discovered that water hardness can manifest itself in
many different everyday appliances. Although many people associate impurity with
natural water sources, I have come to the conclusion that many natural water sources can
actually be less impure in terms of hardness. My initial hypothesis has turned out to be
wrong because I failed to consider the fact that the appliances we use are initially
obtained from natural water sources and other types of sources that are in close contact
with soil, and therefore minerals such as calcium and magnesium. State College is one
place where the water is obtained from such sources, and this is the reason why the State
College samples turned out to be much harder than I would have initially expected.














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References
Brady, Derek. PSU Lab Notebook, pages 35-42. 12 Nov. 2013.
Brulo, Michael. PSU Lab Notebook. 12 Nov. 2013.
Burdge, Julia R. Chemistry: Atoms First. New York, NY: McGraw-Hill, 2012. Print.
"Frequently Asked Questions." State College Borough Water Authority Customer
Questions. N.p., n.d. Web. 13 Nov. 2013. <http://www.scbwa.org/faq.php>.
"Hardness of Rainwater." Hardness of Rainwater. N.p., n.d. Web. 13 Nov. 2013.
<http://www.newton.dep.anl.gov/askasci/env99/env99413.htm>.
Robillard, Paul, William Sharpe, and Bryan Swistock. "Water Softening." Agricultural
and Biological Engineering. N.p., n.d. Web. 12 Nov. 2013.
<http://resources.cas.psu.edu/WaterResources/pdfs/watersoftening.pdf>.
Skipton, Sharon, and Bruce Dvorak. "Drinking Water: Hard Water (Calcium and
Magnesium)." University of Nebraska-Lincoln. N.p., n.d. Web. 12 Nov. 2013.
<http://www.ianrpubs.unl.edu/epublic/live/g1274/build/g1274.pdf>.
Spurlock, Deborah. "Determination of Water Hardness By Complexometric Titration
Class Notes." Determination of Water Hardness By Complexometric Titration
Class Notes. N.p., n.d. Web. 12 Nov. 2013.
<http://homepages.ius.edu/DSPURLOC/c121/week13.htm>.
Thompson, Stephen. Chemtrek: Small-Scale Experiments for General Chemistry. PSU
Chemtrek ed. Boston: Hayden-McNeil Publishing, 2013. Print.




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