Experiment 10- The Chemistry of Natural

Waters
Taylor Fellenz,
April 4, 2016
Chem 111-001
Group Members: Troy Garcia, Joey Grant,
and Paul Granados
TA: Andy Widstrom

Introduction
Water that contains large quantities of Ca2+ and Mg2+ are said to be hard. Water
hardness is important because it helps manufacturers that make fabric and dishwashing
detergents make their products. The ingredients used to make these products were made
to make it complicated for Ca2+ and Mg2+. 1 Hard water even leaves films. these films can
be left on hair, fabric and glassware. 2 Hard water is also important in industrial uses.
When water is heated to a specific temperature or evaporated it can leave rock like
deposits on surfaces of tubes, pipes, and evaporator walls. It is also important in
industrial uses because it forms scale in the heat exchange equipment. Scale is one of the
troubles of the industries. It can narrow pipes, block jets and tubes. Scale can also be very
expensive to remove. 1
We can measure water hardness in three different types of measurements, gallons
per gallon, milligrams per liter (mg/L), and parts per million (ppm). (Seen in Figure: 1)
Water can also be measured in different classifications. Water can be classified as soft,
slightly hard, moderately hard, hard, and very hard.3

Figure 1: Water hardness measured in ppm, mg/L, and grains per gallon 3
Classification
Soft

0-17.1

Grains/gal
0-1

Slightly hard

17.1-60

1-3.5

Moderately
hard
Hard

60-120

3.5-7.0

120-180

7.0-10.5

180 and over

10.5 and over

Very hard

Mg/l or ppm

To determine the water hardness of the samples used, three different types of
techniques were used. The first technique that was used was total dissolved solids (TDS).
TDS is the measurement of the volume of residue that is left after the water has
evaporated. TDS is used to determine the overall quality of the water. 1
The second technique that was used was EDTA Titration or
ethylenediaminetetracetic acid. EDTA Titration is used to determine the concentration of
divalent cations. It is used by adjusting the pH of the water sample to 10 by a buffer
(NH3/ NH4). Then EBTA indicator is added to the sample and at a high pH the indicator
turns blue. Mg2+ is then presented in the sample and reacts with the EBTA indicator to
form a red color. Calcium does not react with EBTA indicator. EDTA Titration is then
added to the sample and reacts with Ca2+ forming a colorless solution and then reacts with
Mg2+ where it is still colorless. Mg2+ is removed from the solution and the sample goes
back to its original blue color. 1
The last technique that was used to test the water sample was Atomic Absorption
Spectrophotometry (AA). A machine called atomic absorption spectrophotometer uses
AA to determine the amount of metals dissolved in the solution. The machine uses
monochromatic light that is projected through the water sample to be analyzed. The metal
concentration that is obtained in the sample is then calculated by using The Beer-Lambert
law. 1
AA and EDTA Titration are different by AA gives more accurate measurements of
Mg2+ and Ca2+. EDTA Titration is also sometimes hard but not impossible because if there
is no Mg2+ in the water sample it is impossible to do. EDTA Titration has to contain Mg2+
because Mg2+ needs to react with the indicator and get a red color in order for the reaction

to occur. If there is an absence of Mg2+ in the sample, the color of the solution will stay
blue during the whole reaction. Both AA and EDTA Titration give precise measurements
of the metal concentration in the sample. 1
Removing the calcium and magnesium ions in the solution can soften water that is
hard. You can also soften water by ion exchange. 4 The materials needed to soften water
in ion exchange are cation exchange resin. Cation exchange resins trades monovalent
cations for divalent cations. The exchange happens by moving water through the ion
exchange column. 1
My project is about the measuring the hardness of water. My partners and I
collected samples from different states and countries. In the experiment we tested which
of our samples was the hardest. The samples were from the salt marshes in Cattus Island,
NJ 5, tap water from Long Island, NY 6, water from a creek in South Brunswick, NJ 7, and
seawater in the New Providence island of Bahamas 8. My hypothesis for this experiment
is that the water sample from the beach in New Providence will be the hardest out of all
the samples because the Bahamas has a high water hardness of 250 parts per million
(ppm) which is considered very hard.9

Procedure:
During this experiment students followed the PSU Chemtrek in order to conduct
the experiment. Taylor Fellenz ran the sample and her sample was seawater from the salt
marshes in Cattus island NJ. The sample was from the Mosquito cove part of the island.
The water was first diluted to 4:1 and then to a 24:1 ratio.
The first step of the experiment was to determine the water hardness by using
atomic absorption spectroscopy (AA). Every student took either their diluted or undiluted

sample and put them into two extra large pipets. The pipets were placed on 24-well trays
and carried to the instrument analysis room. In the instrument analysis room, a small tube
from the atomic absorption spectrophotometer was placed in the sample. The instrument
absorbed a proportion of the sample and tested the Ca2+. Another atomic absorption
spectrophotometer was right next to the first one except, this machine tested for the Mg2+
in the sample. The same procedure done for Ca2+ was followed for Mg2+. The sample
from a creek in South Brunswick, NJ 7 and tap water from Long Island, NY 6 were not
diluted for AA, while the sample from New Providence, Bahamas 8 was diluted at a 1:9
ratio for Ca2+ and 1:49 ratio for Mg2+. 1
After measuring the Ca2+ and Mg2+ in AA, the next step of the experiment was to
observe the total dissolved solids (TDS). In this section of the experiment one drop of
the undiluted sample of water, a drop of distilled water, and 1.00 X 10-3 M Ca2+ were
dropped onto a piece of aluminum foil. The aluminum foil was placed on a hot plate and
students waited to see their sample amounts of nonvolatile salts. 1
In the following step EDTA Titration was carried out. Using a small pipet one
drop of the water sample was added to each of the 12 wells in a 1 X 12 well strip. Next,
one drop of EBT indicator was added and NH3/NH4Cl/MgEDTA buffer was added to
each well. Then, the next step was to titrate serially with a 2.00 X 10 -4 M EDTA
solution. This analysis was done twice. The first well that turns blue is used to calculate
the concentration of divalent cations in molarity. The sample from Long Island, NY was
not diluted in this section while the samples from Cattus Island, NJ 5, South Brunswick,
NJ 7, and New Providence, Bahamas 8 were diluted. The sample from Cattus Island, NJ 5

was diluted to a 4:1 ratio. South Brunswick, NJ 7 sample was diluted to a 1:1 ratio and the
sample from New Providence, Bahamas 8 was diluted to 1:4 ratio.1
The last step in the experiment was to measure the use of cation exchange resin in
the dismissal of Ca2+ and Mg2+ from samples with hard water. A small proportion of the
water sample and cation exchange resin were added to a 8 mL vial. The vial was shaken
gently for a about a minute and then placed down to allow the resin to settle. Liquid from
the vial was removed and placed in a pipet. One drop from the pipet was tested using a
wide range pH paper. Then one drop from the pipet was dropped into each well of a 1 X
12 well tray with one drop of EBT indicator, and NH3/NH4Cl/MgEDTA buffer. The
sample was then titrated serially with the 2.00 X 10-4 M EDTA solution to calculate
hardness of the resin- treated water sample. 1

Results
Figure 2: Comparison of TDS residue after water samples evaporated
Sample
Distilled Water
1.00 X 10 -3 M Ca 2+
Cattus Island, NJ 5
Long Island, NY 6
South Brunswick, NJ 7
New Providence, Bahamas 8

Observation
Brown circle residue
Faint white ring
White heavy circle
Faint ring
White full circle
White full circle

Figure 3: AA Standards for Ca2+ and Mg2+

Ca Absorbance
(at 422.7 nm)

Mg Absorbance
(at 202.5 nm)

Concentration
(ppm)
1.000
5.00
10.00
25.0
30.0
1.000
5.00
10.00
25.0
30.0

Absorbance
value
0.01102
0.04709
0.09459
0.22065
0.41029
0.2257
0.07114
0.15377
0.31633
0.38552

Figure 4: Calibration graph of Ca2+ for AA analysis

Note: graphs based off of information from figure 3

Calibration Graph Ca2+

f(x) = 0.01x + 0.01
R = 1

Figure 5:Calibration graph of Mg2+ for AA analysis

Calibration Graph Mg2+

f(x) = 0.01x + 0.02
R = 1

Calculations of Ca2+ and Mg2+ in water sample using linear trend line (in molarity) 5

Ca2+
0.0618= 0.0081x+0.0088
x= 6.543ppm(2)= 13.086 ppm
13.086 mg/ L * (1g/ 1000) * (1 mol/40.078 g) = 0.00032651
=3.27 X 10 -4 mol/ L

Mg2+
0.2566= 0.0123x+ 0.0151
x= 19.634ppm(2)= 39.268ppm
39.268mg/ L *(1g/1000) * (1 mol/24.31) = 0.00161530
=1.68 X 10-3 mol/ L
Conversions of Ca2+ and Mg2+ Concentrations Into Their Equivalent Concentrations
of CaCO3 5
2+
13.086 ppm Ca x abs. (100.09 g CaCO3)/(1 mole) / (40.08g Ca2+)/ (1 mole) = 32.68
ppm hardness
39.268 ppm Mg2+ x abs. (100.09 g CaCO3)/ (1 mole)/ (24.31g Mg2+)/ (1 mole) =
161.676 ppm hardness
Total Hardness of Water Sample 5
32.68 ppm hardness + 161.676 ppm hardness= 194.356 ppm hardness
Figure 6: Comparison of Groups AA results
Cattus Island, NJ water
sample 5
Long Island, NY water
sample 6

Ca2+
0.618

Mg2+
0.2566

0.2286

0.2926

South Brunswick, NJ water

sample 7

0.1932

0.1402

New Providence, Bahamas

water sample 8

1.1304

0.3737

Figure 7: Comparison of Groups EDTA Titration Results From Water Sample

Cattus Island, NJ water

sample 5
Long Island, NY water
sample 6
South Brunswick, NJ water
sample 7
New Providence, Bahamas
water sample 8

Concentration of
Unsoftened (ppm)
100 ppm

Concentration of Rein
Softened (ppm)
160 ppm

50 ppm

40 ppm

80 ppm

40 ppm

600 ppm

100 ppm

Calculations for EDTA Titration:

Calculation of divalent cations in molarity: 5

Moles of EDTA = Moles of Ca2+

MEDTA VEDTA = MCa2+ VCa2+
1 drops * 2.00 x 10-4 M * 1 dilution= 0.0002 M
Hardness of Water Sample in ppm: 5
2 x 10-3 M CaCO3
1 liter of solution
=

100.0 g CaCO3
1 mole CaCO3

1000 mg CaCO3
1 g CaCO3

100 mg CaCO3
1 liter of solution

=100ppm CaCO3
Precision of Measurements in ppm: 5
(2.00 x 10-4 mole CaCO3)(2)=4.00 x 10-4 CaCO3 = 0.0004 moles CaCO3
4.00 x 10 -4 moles CaCo3 x 100.0g CaCO3 x 1000mg CaCO3 =40 ppm

1liter of solution

1 mole CaCO3

1 g CaCO3

100ppm 40ppm= 60 ppm

Calculation for Hardness of Resin Treated Sample in ppm: 5
M1V1=M2V2 M1V1/ V2=M2
(2.00x10-4) (8)= M2 (8)
=8 * 2.00 x10-4 M (100) (1000) = 160 ppm
% Change after softening: 5
% Change= (ppm CaCO3 of original water sample) (ppm CaCO3 of softened water sample) X 100
ppm CaCO3 of original water sample
100ppm-160ppm = 60% error
100

% Error for EDTA Titration: 5

Original- Experimental x 100 =194.356 ppm CaCO3 100ppm CaCO3 =48% error
Original
194.356 ppm CaCO3

Discussion
My results for my groups comparisons of TDS residue (figure 2) suggests
that the water samples from New Providence, Bahamas 8, South Brunswick, NJ 7, and
Cattus Island, NJ 5 had the hardest water. They all had the same large amounts of residue.
The sample from Long Island, NY6 looked to be the softest because it left almost no
residue. The water only left a faint residue.
The results from the AA test indicated that the water sample from New
Providence, Bahamas8 was the hardest water. It had a Ca2+ absorbance of 1.1304 and a
Mg 2+ absorbance of 0.3737. These absorbance levels were notably higher than the Ca2+
levels from Cattus Island, NJ5 and higher levels in Mg2+ than the sample from South

Brunswick, NJ7. Cattus Island, NJ 5 had a Ca2+ value at .0618 and South Brunswick, NJ 7
had a Mg2+ value .1402.
The outcome from my EDTA Titration followed along the same lines as the
results from my TDS and AA results. The sample from New Providence, Bahamas8 had
the highest concentration for unsoftened ppm. The samples unsoftened concentration
was 600ppm .The sample from Cattus Island, NJ 5 had the highest softened resin of 100
ppm. The samples from South Brunswick, NJ 7 and Long Island, NY 6 had similar
concentrations and were one of the softest. South Brunswick, NJ 7 water sample had a
unsoftened concentration of 80 ppm and softened resin concentration of 40ppm. Long
Island, NY6 water sample had a unsoftened concentration of 50 ppm and softened resin
concentration of 40 ppm.
These results relate to my hypothesis by I predicted that the water sample
from New Providence, Bahamas8 was the hardest water and I was right. New Providence,
Bahamas 8 had the highest unsoftened concentration and highest absorbance levels for
both Ca2+ and Mg2+. The sample was also one of the water samples that left the most
residue. I also did not predict that the sample from Cattus Island, NJ 5 would be the
softest water since it left one of the most residue during the TDS part of the experiment.
Cattus Island, NJ 5 water sample also had one of the lowest absorbance values of Mg2+
and Ca2+ in the AA part of the experiment.
The most accurate technique was AA. During the EDTA Titration the
endpoint was not the same each time a duplicate analysis was formed. I was off by
20ppm. If I was off by 1 drop the value would have been 120 ppm instead of 100ppm. If
the ppm was 120ppm instead of 100ppm all of my calculations would have been off. My

accuracy of EDTA was good; my percent errors for questions two and three were low. For
question two my percent error was 0% and for question three my percent error was 20%.
After calculating the percent error for each check standard, my AA readings were close to
the actual concentration for both my Ca2+ and Mg2+ concentrations.
In the Bahamas most of the seawater is from runoffs on the island.10 When
rainwater falls it is naturally soft. However, once it makes its way through the ground it
picks up different kinds of minerals like magnesium and calcium that makes the water
hard. 11 Salt marshes are coastal wetlands that are filled by seawater from the overflow of
the ocean.12 Since the ocean gets most of its water from rainwater there is no wonder
why the Cattus Island, NJ 5 water sample is soft. 11

Conclusion
Water hardness is due to the large amounts of dissolved calcium and
magnesium concentrations in water. Water with low concentrations of magnesium and
calcium are soft. The AA part of the experiment turned out to be the most accurate
technique because after calculating the percent error for each check standard, the AA
readings were close to the actual concentration for both the Ca2+ and Mg2+ concentrations.
The water sample from New Providence, Bahamas 8 turned out to be the hardest water out
of all four water samples. The water sample from Cattus Island, NJ 5 turned out to be the
softest according to the AA analysis and EDTA.

References
1

Thompson, Stephen. PSU Chemtrek Small Scale Experiments for General Chemistry.
2015-2016, Hayden-McNeil Publishing MI, USA 2015 Exp. 10
2

http://bcn.boulder.co.us/basin/data/NEW/info/Hard.html

http://www.water-research.net/index.php/water-treatment/tools/hard-water-hardness

https://www3.epa.gov/watersense/products/watersofteners.html

Fellenz, Taylor, Chem 111 Laboratory Notebook pp. 37-41

Garcia, Troy, Chem 111 Laboratory Notebook pp.19-21

Grant, Joey, Chem 111 Laboratory Notebook pp.21-24

Granados, Paul, Chem 111 Laboratory Notebook pp. 27-30

http://www.sam.usace.army.mil/Portals/46/docs/military/engineering/docs/WRA/Baham
as/BAHAMAS1WRA.pdf
10

https://books.google.com/books?
id=iGMhBQAAQBAJ&pg=PA90&lpg=PA90&dq=water+ppm+new+providence+baham
as&source=bl&ots=jAoTnAf1yJ&sig=wWHNqpXIk6J7S1KWp_xnN4l_SE&hl=en&sa=X&ved=0ahUKEwiY8rPvlvTLAhVE1x4KHRuFDCQQ6AEIR
TAJ#v=onepage&q=water%20ppm%20new%20providence%20bahamas&f=false
11

12

http://www.freedrinkingwater.com/water-education/quality-water-hard.htm
http://oceanservice.noaa.gov/facts/saltmarsh.html