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6 April, 2017
Introduction:
In regards to water quality, the term hardness refers to the overall composition
of the water, including minerals that are comprised within a given sample through natural
dissolution. Water samples with low concentrations are considered soft while samples
with high concentrations are considered hard. More specifically, through the natural
the water passes over various rocks and soil 1 . The presence of these metallic ions varies
among regional samples, but frequently includes 2+ and 2+ , as these are two of the
common natural resource. Detergent and soap-making companies take into consideration
water hardness, as hard water is highly reactive with the fatty-acids of soap, causing the
soap-making companies must design products that are less reactive to these metal cations
among common water hardness 2 . In addition, industrial factories that incorporate boilers
must be aware of water hardness in an effort to avoid the clogging of pipes and jets from
For these reasons, the necessity for water softening is a prevalent element of
industrial services. A common method utilized for this process is cation exchange resin,
which entails the funneling of hard water through columns containing resin beads of
measured in units of grains per gallon, or ppm (parts per million), most commonly of
CaCO3 . These varying degrees of water hardness are often systematized through 5
primary categories: soft, slightly hard, moderately hard, hard, and very hard4 . Scientists
frequently utilize the methods of TDS, EDTA and AA analysis to categorize water
samples.
Perhaps the simplest method, TDS, or total dissolved solids method, as inferred
from its name, simply entails the evaporation of water and analysis of residue left behind.
This process is solely qualititative analysis. Any residue is categorized as remnants of the
polyvalent cations mentioned above. For obvious reasons, this method is highly generic
titration with water sample. By first adding an acid-base indicator (EBT) to the water, a
light blue color will appear, confirming a high pH of basic degree. Next, the magnesium
(2+ ) ions within the sample will react with the indicator, causing the formation of
ethylenediaminetetracetic acid, the solution will turn colorless as the EDTA reacts with
first the 2+ ions then the 2+ ions. A sudden final change in color of the solution
from red to blue will indicate the conclusion of the titration1 . By using an EDTA solution
of accepted concentration, one can easily calculate the calcium and magnesium ion
concentrations using the formula 1 1=2 2. Below is the formula for this reaction as
(EDTA)
2 2+ 2+ + 2+
+ + + + CaEDTA + MgEDTA +
process is conducted by burning a small liquid sample by the machine, which then
atomizes the water sample and using a cathode lamp, passes light through the sample and
concentrations, a calibration graph can be erected to create a trend line that estimates
Research of the two methods provides credibility for both techniques though each
has potential drawbacks. Due to the limited number of concentrations used, the titration
method is generally less precise to the exact concentration and generally fails for low
conducted to analyze and compare various samples of natural water. Using TDS, AA, and
ETDA, four unique water samples were obtained and tested from diverse regions,
including tap samples from Park City, Utah (6), Mineta San Jose International Airport in
San Jose, California (7), a local house in State College, Pennsylvania, (8), and a house in
The sample from Park City, Utah is expected to possess the highest magnesium and
calcium concentrations, based upon the locations and hardness values provided by the
expected to possess the lowest divalent ion concentration. Samples 3 and 4 are expected
to possess similar calcium and magnesium concentrations as they originate from similar
areas of Pennsylvania, though the State College water is expected to be slightly higher,
given data from the USGS. Therefore, using EDTA and AA analysis techniques, the
with samples 3 and 4 being roughly equivalent, as they are from similar areas.
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Procedure:
From PSU Chemtrek: Small Scale Experiments for General Chemistry written by
The following experiment consisted primarily of four sections: the use of TDS
calculate ion concentration, and water softening through ion exchange. All of the
processes used were derived from the PSU Chemtrek booklet guidelines and were
followed accordingly. The following graph identifies where each sample originated as
well as the name of the sample analyzer and specific sample type for both AA and EDTA
analysis. None of the samples were filtered, or underwent water conditioning prior to
experimentation.
piece of aluminum foil (4cm x 4cm) was placed on a hot plate set on low. Using
multiple pipets, a single drop of distilled water and a single drop of sample water was
place on the foil approximately 1cm apart from one another. In addition, two drops of
1103 M 2+ solution were also placed on the aluminum foil to create a secondary
reference. The drops were allowed to slowly dissolve and the residual from each sample
was analyzed.
Next, the samples were tested using Atomic Absorption spectroscopy. First
samples 1,2,3 and 4 were diluted with distilled water in a 10 mL graduated cylinder using
a 1:1 ratio. This was achieved by mixing 5mL of distilled water with 5mL of sample
water and then stirred thoroughly. Using two new pipets, each bulb was filled over
halfway with the sample water and then the samples were transferred to 24-well tray.
Using the atomic absorption spectrometer, the liquid samples were burnt from within the
tray. Each of the samples was divided into two separate samples with one being tested for
2+ absorption and the other being tested for 2+ absorption. These absorption
values were then recorded. Using the AA standard values provided, a calibration graph
was constructed for each sample by plotting light absorbance vs. metal ion concentration
into Microsoft Excel. Next, a trend line equation was generated for both 2+ and 2+ ,
which was then used to calculate the concentrations of both ions individually. These
values (in ppm) were added together to provide a final hardness estimation using this
technique. Below is a table depicting dilution factors used for each sample.
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Following AA, a divalent cation analysis was conducted through EDTA titration
3 /4 /Mg buffer solution was also added to each well. Finally, the wells were
titrated in succession using 2104 M EDTA, as well 1 received 1 drop of solution and
each well after received an additional drop as the one prior. The well in which the color
of the solution shifted to blue represented a complete titration, or the equivalence point.
Once completed, this process was repeated using the water samples listed above. The
experiment was conducted twice and the number of drops required to complete the
titration was averaged. Below is a chart depicting the dilution factors used for each
Finally, the samples were softened through ion exchange processes. Using the
sample dilution factor from the initial EDTA method, the samples were placed into 8mL
vial. Enough monovalent cation exchange resin was then added to each vial to cover the
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bottom. These vials were then shaken up for 2-3 minutes each, and the remaining liquid
from each vial was sucked up using small-drop pipets. A pH test of the liquid then
validated evidence of successful water softening. Finally, these softened samples were
Results:
Below are the results of the TDS analysis from the evaporated water samples. The
distilled water served as a standard for clean water containing no ions while the
divalent cations. As stated above in the procedure section, with the exception 1103 M
2+ solution (2 drops), a single drop of each sample was added to the aluminum foil.
Below are the AA-operator calibration standards for 2+ and 2+ concentrations (in
ppm) along with the absorbance values at (422.7 nm). These were used to construct the
value as the corresponding standard. This value serves as a measure of accuracy of the AA instrument.
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Tables 6 and 7 display the AA 2+ and 2+ , absorbance values determined for each
sample. As noted prior, all samples were diluted for this measurement using a 1:1 dilution
factor.
(ppm)
4 PA Ta9 0.0896
(ppm)
4 PA Ta9 0.0620
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Tables 8 and 9 show the calculated concentrations values of 2+ and 2+ (in ppm) in
each sample. These values were calculated using the equation of best-fit lines given
x= 25.5 ppm
3. If a dilution factor was used, then multiply by a factor of 2 to account for 1:1 s
p ratio
(25.5 ppm) *2= 51.0 ppm 2+
Tables 9 and 10 display the overall combined hardness of each sample in ppm
CaCO3 . These values are be calculated by converting ppm of Mg 2+ and Ca2+ (from
Table 8 and Table 9) into ppm of CaCO3 , then adding both values together.
3. Finally, add the values calculated from step 1 and step 2 together to
calculate total hardness value.
250.0 ppm CaCO3 + 210.0 ppm CaCO3 = 460 ppm CaCO3
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Below are the results of the EDTA titrations for both the unsoftened water samples
(Table 10) and monovalent resin treated water samples (Table 11). The dilution
factors used in each scenario are also listed. Note: the number of drops listed in each
= 1 x 1
( )/( 1 )= 1
((2.00 4 M)(7 drops))/(1 drop) = 0.0014 M
Note: If dilution factor of 1:1 is used, multiply final molarity by 2.
(2*0.0014 M CaCO3 ) = 0.0028 M CaCO3
Discussion:
Once synthesized, the data collected for both AA and TDS methods revealed
interesting results. In regards to overall water hardness, the PA tap sample from Jamison,
Pennsylvania, possessed the lowest values. Samples 2 and 3 from California and State
College possessed similar hardness values. In support of the original hypothesis, the Park
City, Utah sample yielded the highest overall hardness values. However, the
Pennsylvania samples greatly varied in hardness value ranges, contrary to the hypothesis.
consistently failed to provide a smaller hardness value than EDTA analysis in each
sample. AA analysis is limited in scope to search for specifically Mg 2+ and Ca2+ ions in
each sample while EDTA expands the analysis of each sample to search for the presence
of other additional divalent cations, including Iron, Strontium, and Barium. However, the
results of AA testing fail to validate this logic, suggesting potential errors in the
experiment. The most probable explanation of this consistent anomaly is the potential
contamination of the EDTA solution with the given molarity of 2.00104 M. As many
students rely on using the same bottles, it is feasible to expect that contamination
occurred, which in turn generated lower than expected values. Consequently, the
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EDTA data is largely invalid for analysis as clear fallacies are present within the data.
This error was not discovered during the experiment; so further testing would be required
As stated prior, EDTA analysis identifies the presence of all (in theory) divalent
cations present in each sample. To the contrary, AA only identified Mg 2+ and Ca2+ ions
present in each sample. Consequently, the AA data should be less than or equal to the
hardness values obtained through EDTA. This trend was not true for all samples, which
largely invalidates the results of the data. Theoretically, the slight variance in hardness
values between the two methods would suggests a minimal presence of additional
divalent cations in each sample, though this conclusion cannot be drawn. These could
potentially include, Iron, Strontium, and Barium, which are frequently present, yet less
common. Ultimately, these values are within the bounds of natural water, with an overall
CaCO3 hardness value of 450 ppm, creating an ideal balance for life, according to UK
State College region as an area possessing very hard water potentially greater than
250ppm. This assertion can be justified by the existence of a carbonate rock aquifer
located beneath the Centre County area11 .This notion is supported by the data provided
by the EDTA and AA titrations of the PSU sample given the value of 230 ppm. The
United States Geological Survey (USGS) identifies the states of northern California and
121-180ppm and 60-121ppm, respectively12 . This data roughly aligns with the results of
AA for the PA Tap9 (96.9 ppm) and California tap7 (220 ppm), given a variance of 40
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areas possessing mountain ranges like that of San Jose, California, where rain water runs
down mountains and mixes with rivers, causing increased divalent ion
concentrations12,13 . This justifies the slightly higher than anticipated concentrations from
In comparison to the other methods, TDS would be the least accurate as it is based
solely upon physical observations and generalities. However, due to the atomic
likely the most accurate of methods. In accordance with this assessment, the check
standard values reveal accuracy in the respective divalent cation concentrations, but
suggest a lack in precision as the concentrations are rounded to the nearest ones value. In
addition, if the sample is not mixed evenly, the AA readings could lack precision. A
single trial analysis of each divalent cation concentration may have facilitated a lack of
absorption value. Similarly, the EDTA method is more precise than accurate. The lack of
assessing the overall water hardness of each sample. However, when repeated
consistently, the titration methods as well as pipettes used should yield consistent relative
data. If a more specific unit of volume were used, rather than the whole number unit of
Furthermore, during the procedure of EDTA, the equivalence point was achieved
with 7 drops in both trials, suggesting relative precision. This could be further tested with
multiple trials, though two consistent trials do provide evidence of precision. However,
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particular consideration for the variance of a single drop in regards to calculations should
be accounted for as well. An increase by a factor of a single drop during the titration
undiluted. This being recognized, none of the samples varied in number of drops
3 M 2+ solution prior to sample testing provided insight into the methods used. With
respective percent errors of 0% and 20% for this section, Section C in PSU Chemtre1
provided credibility to the practicality and accuracy of EDTA as used in this section. This
process suggests a potential error of approximately 20% for data using this method,
which translates to a 20% error when calculating water hardness among samples.
However, in reference with the AA results, the EDTA results suggest greater error.
The accuracy of AA data can be easily calculated through percent error between
the check standard values and divalent ion concentrations provided in Table 4 and Table
()
5. By plugging the values from the tables into the formula: %error=
100 ,
the percent errors for Table 4 (Ca2+ Concentrations) are 29%, 3.0%, 0.5%, 1.9%, and
0.8% in order of increasing concentration. In the same order, the Mg 2+ percent errors
from Table 5 are 15%, 3.2%, 3.3%, 2.5%, and 2.6%. From these values, one can
conclude that AA is generally more accurate than EDTA, as all but one of these values is
less than 20%. In addition, the AA values generally agree more with outside data
Conclusion:
including Park City, Utah (6), Mineta San Jose International Airport in San Jose,
California (7), a local house in State College, Pennsylvania, (8), and a house in Jamison,
Pennsylvania (9). It was hypothesized that the Utah sample would possess the highest
hardness values while the two PA samples would produce roughly equivalent hardness
values, and the California sample would possess the lowest values.
spectroscopy, and EDTA titration, the overall hardness values were calculated and
assessed. The experimental steps used were a direct following of the PSU Chemtrek
booklet. While the TDS yielded very similar qualitative data, the AA and EDTA methods
largely invalidated the hypothesis, but failed to fall within similar ranges. Ultimately, the
Utah sample yielded the highest concentration values, while the California sample and
the State College sample came in second with the other PA sample coming last while
possessing very soft water. The likely causation of these particularly hard samples is the
carbonate rock aquifer beneath the State College area as well as the mountains of
California and Utah. The California sample yielded hardness values much higher than
anticipated, but this can likely be justified by the presence of water run-off from
References:
10. Professor William Wurt, PHD. Understanding Water Hardness Web. April
4, 2017
12. Water Hardness. The United States Geological Survey. Web. April 4, 2017