1

Jill Bontrager
Lab Performed on: March 17, 2009
Experiment 10:
Exploring the Water Hardness of Bottled Waters
Chem. 111-103
Group Members: Kirsten Bickhart, Adam Brous,
Nick Bertsch, Jake Bezalel

TA: Ting-Hao Phan

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Introduction:
Water hardness is determined by concentration of metallic solids, such as magnesium and
calcium ions, dissolved in a water source. The degree of water hardness is determined by the
concentration of ions in a source; hard water contains a high concentration of metallic ions while
softer water contains a lower concentration. Since water is a universal solvent, it readily collects
ions and impurities when moving over rocks and soils. The most prevalent ions collected in a
1
water source are Ca2+and Mg2+.
The hardness level of water is important for a number of reasons. Although hard water is
not a health risk, it can negatively affect the performance of pipe efficiency, detergents in
laundry, and the use of shampoo and soap for bathing. Deposits of Ca2+and Mg2+ in hard water
can form limestone deposits that slow and block pipes, which is inefficient and costly. When
washing clothing with hard water, clothing may become scratchy and harsh as the ions damage
the cloth fibers. Hard water can create limestone film deposits in hair while bathing, as well as
causing soap to be less effective at removing dirt and bacteria from the skin. On a larger scale,
metallic ions in water can also cause metal corrosion and structural weakness of buildings and
bridges.2
Water hardness is measured either in grains per gallon or parts per million. The
Environmental Protection Agency (EPA) regulates the standards for drinking water based on
primary conditions, which evaluate health and safety, while the secondary conditions are based
on taste, color odor, and corrosivity. The following chart shows how the U.S. Department of the
Interior and Water Quality Association classifies water2:

Figure 1.1: Classification of Water

Classification mg/l or ppm grains/gal

Soft 0 - 17.1 0–1
Slightly hard 17.1 – 60 1 - 3.5
Moderately hard 60 – 120 3.5 - 7.0
Hard 120 – 180 7.0 - 10.5
Very Hard 180 & over 10.5 & over
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Water hardness can be tested in a variety of ways. One of the easiest ways of
determining the solutes present is to evaporate water from a sample and evaluate the remaining
solids. The method is called finding the Total Dissolved Solids (TDS) of a sample. This type of
analysis is good for determining the scale of how many ions are present in a sample, but is
unable to determine a more exact amount of cations present.
A more specific determinant of water hardness is determined through
ethylenediaminetetracetic, or EDTA. The EDTA method calculates how many divalent cations
(cations with a plus-two charge) are present in the sample of water through a complexation
reaction, as shown below:3
HD2- (blue) + Mg2+ + Ca2+ MgD-(red) + H+ + Ca2+ CaEDTA + MgEDTA + HD2- (last:blue)

To start the EDTA Titration, the pH of the water sample is adjusted by adding NH3/NH4
buffer. When EBT indicator is added, it is in the HD2- form, so the pH is high and the solution
turns blue. If Mg2+ is in the water sample, it will react with the indicator and turn a red wine
color. At this point, EDTA solution is added, which reacts with Ca2+ and the magnesium
indicator to produce colorless MgEDTA chelate. A chelate forms multiple bonds with metal
cations, inhibiting them from bonding with other elements or forming precipitates (or residue).
Once the magnesium chelate is formed, the color of the solution returns to blue. EDTA is used
in many commercial products like bathtub cleaners (dissolving limestone scum) and salad
dressing (preserving the oil).3

Another method of water softening is Atomic Absorption Spectroscopy (AA), which is

useful for determining dissolved metals in a solution. An AA Spectrometer has four main parts:
an aspirator (to collect the liquid sample), lamps that emit specific wavelengths, a flame or other
heat source, and a photon detector. Specific lamps are chosen according to what one wants to
test, such as calcium for example. After the aspirator suctions a sample of the liquid being
tested, any calcium ions in the flame will absorb light from the lamp before reaching the photon
detector. High levels of the cation, such as calcium, render high absorbance values. Once an
absorption level is determined (in nm), it can be used to calculate the concentration of the ion
through the use of a calibration graph.4

AA and EDTA methods of determining water hardness are fairly different. AA analysis
evaluates only one cation at a time with the use of a spectrometer machine. EDTA calculates the
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sum of all cations and cannot differentiate between them. EDTA involves titrating the sample
with indicators and the chelate-forming EDTA, while AA relies on a lamp source, a flame and a
detector. AA is more exact, since the machine calculates the absorbance level of one ion, which
limits chances to make both human and calculation error. EDTA, however, requires titrations of
different solutions, which leaves room for error in the precision of the experiment.5

As discussed before, water hardness can be a hindrance at industrial, economic and

residential levels. Cation exchange resins are therefore very useful in softening water. In both
the commercial softening agent and the resin, cation exchange was the means to which the water
samples did soften. The resin takes up calcium and magnesium ions (divalent cations) and
releases sodium and hydrogen ions (monovalent cations), which makes water ―softer‖.
Therefore, both of the softening techniques worked to lower hardness (in ppm) significantly.6
In this experiment, five bottled water brands were tested: Evian, Fiji, Kirkland, Aquafina,
and Deer Park. The market for bottled water has dramatically increased over the last twenty
years, due to its portability and ―purer‖ taste. Bottled water regulations and governed by a
different set of rules than municiple water that are usually more lenient. The chemical treatment
used to keep municipal water hardness at the correct level can have an unpleasant taste, so
bottled water manufacturers try to avoid such stipulations.7 Within bottled water, there is mineral
water, such as Evian and Fiji, which contain a hardness level of at least 250ppm. Spring water,
on the other hand, is usually softened through cation exchange, so it has a lower hardness level.
The hypothesis of this experiment is that the Evian and Fiji waters will have the highest hardness
levels, due to the more natural process of filtering. As for Evian, the water spends 15 years
filtering through an aquifier on a mountain, and should therefore have a stronger mineral
composition than the spring waters, Deer Park, Aquafina, and Kirkland. Spring waters differ in
hardness depending on their geological location but are treated chemically for hardness before
being marketed, so are softer than mineral waters.8

Procedure:

The full explanation of the procedure for Experiment 10: The Chemistry of Natural
Waters, can be found in chapter 10 of PSU Chemtrek.3 In this experiment, each of the five
bottled water samples—Evian, Fiji, Kirkland, Aquafina and Deer Park—was tested for hardness
through a number of methods including TDS, AA, and EDTA.
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The first method measures the Total Dissolved Solids (TDS) of an evaporated water
sample. By placing a drop of each sample (as well as two references) on aluminum foil and
heating the source with a hot plate, the water evaporated, leaving white solid residue. The white
solids remaining are the salts of the original water sample, which helped determine the hardness
of the samples. High TDS results correlated with the harder water samples. The salts that are
likely to be present in the remaining residue are ions like Ca2+and Mg2+.
The second method is Atomic Absorption (AA) Spectroscopy. In the AA analysis, the
samples were tested by a machine that measures calcium and magnesium levels separately. By
inserting the aspirator into each water sample, the absorption level (in nanometers) of Ca2+ and
Mg2+ was calculated. Using the absorption level, as well as the calibrated equations for both
ions, the hardness (in ppm) of the samples was calculated. These ppm values were then
converted into their ―equivalent concentration‖ of CaCO3, and then added together for a resulting
total hardness.
The third method used was EDTA titration used, in which a series of dilutions was
performed. EDTA is used in a complexation reaction with the water samples in order to
determine the concentration of ions such as Ca2+ and Mg2+ , as well as other resulting minerals
and ions. The first well that changes to a blue color is considered the volume of EDTA
necessary in the titration. Results are subject to human error in this method of testing
specifically, due to the titration. In addition to the hardness calculated in the initial EDTA
method, the samples were observed by EDTA titration with a commercial softening agent and
with resin.
Results:
The results and information gathered is from the lab notebooks of group members as follows:
Jill Bontrager9, Jake Bezalel10, Kirsten Bickhart11, Adam Brous12, and Nick Bertsch.13
Total Dissolved Salts (TDS) Results:
By using TDS as a means of investigating water hardness, we obtained the following results:
Figure 1.2: Total Dissolved Salts (TDS) of Each Water Sample:
Water Sample: Observations:
Distilled Water No residue
1 x 10-3 M Ca2+ - reference White residue
Evian Heavier residue than reference
Fiji Lighter residue than reference
Kirkland Heavier residue than reference
Aquafina No residue
Deer Park Lighter residue than reference
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By comparing the residue results as compared to the reference, Aquafina showed no residue, Fiji
and Deer Park showed lighter residue, and Evian and Kirkland showed a heavier residue. This
loosely follows the TDS analysis of the softer waters having lighter residue and hard waters
having heavier residues.
Atomic Absorption (AA) Results:
Each group member sampled a different bottled water brand for the experiment. After running
the samples through the AA water device, the following results were obtained:

Figure 1.3: Bottled Water Samples and Absorption rates according to AA

Sample Name Ca2+Absorbance (@ Mg2+ Absorbance
422.7nm) (@202.5nm)
Evian 0.1390nm 0.1131nm
Fiji 0.4060nm 0.1943nm
Kirkland 0.0378nm 0.0336nm
Aquafina 0.0004nm 0.0038nm
Deer Park 0.0738nm 0.0873nm

The AA device, run by the Penn State Chemistry Department, obtained the standard values of
calibration of Ca2+ and Mg2+ concentrations:
Figure 1.4: AA Standards of Ca2+ concentration
Ca2+ Concentration (ppm) Ca2+Absorbance (@ Check Standard for Ca2+
422.7nm) (ppm)
0 -- --
1.000 0.01609 0.99
5.000 0.08087 4.82
10.000 0.16286 10.16
25.000 0.32177 23.37
50.000 0.57016 50.89

Figure 1.5: AA Standards of Mg2+ concentration

Mg2+ Concentration (ppm) Mg2+Absorbance (@ Check Standard for Mg2+
202.5nm) (ppm)
0 -- --
1.000 0.03229 1.27
5.000 0.12431 4.99
10.000 0.23623 9.84
25.000 0.54136 25.25
30.000 0.61989 30.53
The absorbance standards from the AA device were used to calculate the calibration curve shown
on the following graphs. These linear equations are used to calculate hardness (in ppm) for both
Ca2+ and Mg2+.
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Figure 2.1: Calibration of Ca2+Concentration by AA

Calibration of Ca2+ Concentration by AA
y = 0.011x + 0.020

y = 0.0113x + 0.0206
Absorbance Value (at 422.7 nm)

R² = 0.9911

Series1
Linear (Series1)
Linear (Series1)

Calcium Ion Concentration (ppm)

This graph, like the one below, shows that as concentration (in ppm) increases, absorbance value
(in nm) increases. This direct relationship between concentration and absorbance provides a
linear equation that can be used to determine the hardness value of the Ca2+ and Mg2+
Figure 2.2: Calibration of Mg2+Concentration by AA
Calibration of Mg2+ Concentration by AA

y = 0.020x + 0.014
Absorbance Value (at 202.5 nm)

Series1
Linear (Series1)

Magnesium Concentration (ppm)

Example equations for calibration graphs:

y-value=absorbance (nm)
x-value=concentration (ppm)
For Ca2+: y = 0.011x + 0.020
(0.1390nm)=0.011x+0.020
0.119=0.011x
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x=10.818 ppm
For Mg2+: y=0.020x+0.014
(0.1131nm)=0.020x+0.014
0.0991=0.020x
x=4.955ppm

In the Evian sample, it was necessary to dilute by 50 drops of distilled water due to its hardness.
Therefore, in order to obtain an accurate concentration, one has to multiply the ppm value
calculated by 50. The resulting hardness for the Evian sample is then:
For Ca2+: 10.818 x 50=540.9ppm
For Mg2+: 4.995 x 50=249.75ppm
For the other water samples, it was not necessary to dilute with distilled water, so the resulting
ppm values are the same as the calculated calibrations.

The next step is converting the concentration values into their ―equivalent concentration of
calcium carbonate,‖ which determines the hardness of the sample. A sample calculation of
calculating hardness is as follows:
Ca2+ hardness:
100g CaCO3 / 1 mole
540.9 ppm Ca2+ x ---------------------------- = 1352.25 ppm hardness
40.0g Ca2+ / 1 mole
Mg2+ hardness:
100g CaCO3 / 1 mole
249.75 ppm Mg2+ x ---------------------------- = 624.375 ppm hardness
24.3g Ca2+ / 1 mole

The Ca2+ and Mg2+ hardness must be added together for the total hardness value from AA
analysis.

Total hardness:
1352.25ppm + 624.38ppm = 1976.63 ppm

The following chart compiles all group results of the hardness results from AA analysis:
Figure 1.6: Hardness calculated from AA Analysis:

Sample Ca2+ hardness (ppm) Mg2+ hardness Total Hardness—

(ppm) converted to CaCO3
Evian 540.9ppm 249.75ppm 1976.63 ppm
Fiji 34.10ppm 8.69ppm 121.01ppm
Kirkland 3.8ppm 3.79ppm 25.1ppm
Aquafina N/A (too soft) N/A (too soft) N/A (too soft)
Deer Park 4.80ppm 3.54ppm 26.57ppm
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EDTA Results:
In addition to the AA analysis, divalent cation analysis was conducted through EDTA Titration.
The following results were obtained and samples are given for each unique calculation:
Ppm calculated through titration:
(2.0x10^-4 M)(2 drops EDTA)=(sample concentration)(1 drop)
4.40x10-4M x 50*=2.0x10-2=2000ppm
*=sample diluted by 50 drops

Molarity of water sample:

(2.0x10-2M) (100g CaCO3) (1000mgCaCO3) 2000mg CaCO3
------------- x ------------------ x ------------------- = -------------------
( 1 L) (1 MCaCO3) (1g CaCO3) 1 L Solution

Grains per gallon of water sample:

(2000mg CaCO3) (1 grain) (3.785 L) 117.0 grain
---------------- x --------------- x ------------------- = -------------------
( 1 L) (64.7g) (1 gallon) 1 gallon
Ppm of water sample:
(117.0 grain) (17.1ppm)
---------------- x --------------- = 2000.7ppm
(1 gallon) (1 grain/gal)

Figure 1.7: Compiled EDTA Results

Sample VolumeEDTA EDTA initial Molarity Grains per
(drops) (ppm) (mg/L) gallon
Evian 2 drops 2000.7 ppm* 2000mgCaCO3 117.0 grains
------------------ -------------
1 L Solution 1 gallon
Fiji 4 drops 80.0ppm 80mgCaCO3 4.68 grains
------------------ --------------
1 L Solution 1 gallon
Kirkland 2 drops 40.0ppm 40mgCaCO3 2.34 grains
------------------ --------------
1 L Solution 1 gallon
Aquafina N/A N/A N/A N/A
Deer Park 2 drops 40.0ppm 40mgCaCO3 2.34 grains
------------------ ---------------
1 L Solution 1 gallon
*Dilution: multiplied by 50 distilled water drops due to extreme hardness

Using a commercial water-conditioning agent, hardness levels were calculated as follows:

Softening Agent (Arm + Hammer) results:

(Evian sample changed after 6 drops at 12.0x10-4 M, determined by EDTA titration)
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Molarity of water sample with softening agent:

(12.0x10-4 M) (100g CaCO3) (1000mg CaCO3) 120mg CaCO3
---------------- x --------------- -- x ------------------- = -------------------
(1 L) (1 M CaCO3) (1g CaCO3) 1 L Solution

Grains per gallon:

(120mg CaCO3) (1grain) (3.785 L) 7.02 grain
---------------- x --------------- -- x ------------------- = -------------------
(1 L) (64.7mg) (1 gallon) 1 gallon
Ppm:
17.1ppm
7.02 grain/gal x -------------- = 120.04ppm
1 grain/gal.
To determine how much softer the Evian sample became, keeping in mind the dilution, the
following calculation gives a percentage of the change in water softness:

Figure 1.8: Water Softening Agent EDTA titration results:

Sample Volume Water Water Water

(drops) of Softening Softening Softening
Softening Molarity Grains/gallon Hardness
Agent (mg/L) (ppm)
Evian 6 drops 120mgCaCO3 7.02 grains 120.04ppm
---------------- ---------------
1 L Solution 1 gallon
Fiji 3 drops 60mgCaCO3 3.51 grains 60.0ppm
--------------- ----------------
1 L Solution 1 gallon
Kirkland 1 drop 20mgCaCO3 1.17 grains 20ppm
--------------- ---------------
1 L Solution 1 gallon
Aquafina N/A N/A N/A N/A
Deer Park 1 drop 20mgCaCO3 1.17 grains 20ppm
--------------- ---------------
1 L Solution 1 gallon
From the softening agent results, show that the hardness (in ppm) is reduced by the initial EDTA
titrations.

By using the cation exchange resin in the removal of Ca2+ and Mg2+ to investigate the softening
effect on the hard water samples, the following results were obtained:
Resin:
(Evian sample changed after 4 drops at 8.0x10-4 M, determined by EDTA titration)
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Molarity of water sample with resin:

(8.0x10-4 M) (100g CaCO3) (1000mg CaCO3) 80mg CaCO3
---------------- x --------------- -- x ------------------- = -------------------
(1 L) (1 M CaCO3) (1g CaCO3) 1 L Solution

Grains per gallon:

(80mg CaCO3) (1grain) (3.785 L) 4.68 grain
---------------- x --------------- -- x ------------------- = -------------------
(1 L) (64.7mg) (1 gallon) 1 gallon

Ppm:
17.1ppm
4.68 grain/gal x -------------- = 80.03ppm
1 grain/gal.

To determine how much softer the Evian sample became, keeping in mind the dilution, the
following calculation gives a percentage of the change in water softness:

The following chart compiles all of the information for EDTA titrations for resin:

Figure 1.9: Resin EDTA Titration Results:

Sample Volume Resin Resin Resin
(drops) of Molarity Grains/gallon Hardness
Resin (mg/L) (ppm)
Evian 4 drops 80mgCaCO3 4.68 grains 80 ppm
---------------- --------------
1 L Solution 1 gallon
Fiji 3 drops 60mgCaCO3 3.51 grains 60ppm
---------------- ---------------
1 L Solution 1 gallon
Kirkland Less than 1 Less than Less than Less than 20
drop 20mgCaCO3 1.17 grains ppm
---------------- ----------------
1 L Solution 1 gallon
Aquafina N/A N/A N/A N/A
Deer Park Less than 1 Less than Less than Less than 20
drop 20mgCaCO3 1.17 grains ppm
----------------- -----------------
1 L Solution 1 gallon
Overall, the resin softened the water even more than the commercial softening agent, according
to the results above.
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Discussion:

Each water sample was tested for hardness with the AA and EDTA methods. For the
Evian sample, the AA value was 1973.63ppm and the EDTA value was 2000.7ppm.9 For the Fiji
sample, the AA value was121 ppm and the EDTA value was 80ppm.10 The Kirkland sample has
an AA value of 25.1ppm and an EDTA value of 40 ppm.11 The Aquafina sample was too soft to
retrieve hardness data for either AA or EDTA, so the values are obviously 0.0ppm for both. For
the Deer Park sample, the AA value was 23.57ppm and the EDTA value was 40.0ppm.
The initial hardness values for both AA and EDTA for the five samples support my
hypothesis for the most part. Evian and Fiji have the highest hardness values, as Evian would be
considered very hard and Fiji would be considered hard, according to the U.S. Department of the
Interior and Water Quality Association classifies water (see Figure 1.1). The Evian sample was
initially so hard that it had to be diluted with 50 drops of distilled water before titrating the well
samples with EDTA. Due to the dilution, all the hardness calculations for both AA and EDTA
had to be multiplied by 50, making the hardness levels significantly higher than the other
samples, including Fiji. According to the Evian website, the mineral water goes through a 15
year filtering process, but the aquifier has glacial sand content and other minerals which gives it
such a high hardness value.8
In comparing the data between AA and EDTA methods, all of the AA values were less
than the EDTA values. These results make sense, because the AA Spectrometer measures the
absorbance of one cation at a time, white EDTA accounts for the hardness value of all cations at
once. AA is more accurate because it gives machine-calculated results that leave less room for
human error, in addition to calculating a much more specific absorbance rate, such as one cation
at a time. EDTA involves a lot of human calculation from counting the titrating drops, to hand-
dropping into the 1x12 well. The precision of the results can be skewed even if just one drop is
miscalculated. Also, the EDTA results account for all impurities and salts in the sample, making
it harder to distinguish the key cations present in the sample. In our experiment with bottled
waters, the AA calculations were both more accurate and precise than the EDTA titrations.
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6
―Ion Exchange Resins.‖ http://www.nzic.org.nz/ChemProcesses/water/13D.pdf (accessed April
2008)

7
Technology of bottled water, 2nd edition. Edited by Dorothy Senior and Nicholas Dege.
Oxford, UK: Blackwell Publishing Ltd. 2004. Pp 1-5.

8
―Bottled Water of the World.‖ http://www.finewaters.com/Bottled_Water/France/Evian.asp
(accessed April 2008)

9
Bontrager, Jill, Chem 111 Laboratory Notebook, pp.35-41

10
Bezalel, Jake, Chem 111 Laboratory Notebook, pp.38-42

11
Bickhart, Kirsten, Chem 111 Laboratory Notebook, pp. 35-41

12
Brous, Adam, Chem 111 Laboratory Notebook, pp.27-31

13
Bertsch, Nick, Chem 111 Laboratory Notebook, pp. 25-27