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Research Question:
Using complexometric titration, how does the calcium and magnesium ion content in a range of
10 different bottled water and water types (Bel-Aqua, Evian, Awake, Voltic, distilled water, tap
water, Highland springs, Special Ice, Ocean Spring, Everpure) used in the school community
vary?
Subject: Chemistry
1.0 INTRODUCTION
The calcium and magnesium ion content of a solution contribute to a state of water,
described as “hardness”. This is the result of when water, in combination with carbon dioxide,
moves through rock and soil, dissolving small amounts of minerals and keeping them in this
solution. These water solutions contain cations usually with a charge of 2+ or larger. Ions with a
charge of 2+, which is typical of group 2 metals, include Ca2+ and Mg2+. The two cations in focus
are from the elements calcium and magnesium, two very common metals in nature that react to
form barely soluble products and sometimes complexes with water and other elements. These
products are often present in underground water systems and thus result in water being “hard”.
Some examples of such products are bicarbonate (HCO3) and calcium carbonate (CaCO3).
1.1 FOCUS
dissolved in water and so can be described as the concentration of multivalent cations (cations
with more than one valence electron, in this case the calcium and magnesium ions), dissolved in
the water.
Hard water has no adverse effects on health, and is in fact seen as healthy by individuals in
the school community based on its higher mineral ion concentration. It is, however, seen as a
hindrance to a number of cleaning tasks from laundry, to dishwashing, bathing and personal
grooming. In the school however, the primary use of most of these different water samples is
drinking. These brands of water have varying mineral ion content and are all perceived to be
beneficial due to these mineral ions. Hence, the aim of this experiment was to investigate the
hardness of water in a range of 10 different water samples, used by the many people on the
chelatometry, which is a form of volumetric analysis where the formation of a coloured complex
is used to determine the end point of a reaction and identification of metal ions in solution, This
used for measuring hardness in extremely soft water ( concentrations less than 4 mg/cm3). (Hach,
2017)
Research question: Using complexometric titration, how does the calcium and magnesium ion
content in a range of 10 different bottled water and water types (Bel-Aqua, Evian, Awake,
Voltic, distilled water, tap water, Highland springs, Special Ice, Ocean Spring, Everpure) used in
It is common knowledge to many people that metal ions such as calcium can be found in many
different sources of water, including drinking water, but as to the concentrations of mineral ions
present, many are unaware. Although still safe to drink (in high demand in fact), high
concentrations of multivalent metal ions (i.e. metal ions with a valence of more than one) can
result in water being “hard”, which can negatively impact some of the day to day tasks we
perform, from showering to washing other things. Well water can be hard because the high
calcium concentration in well water is a result of ground water passing through or over
limestone deposits or other calcium ore. Concentrations range from zero to several hundred
mg/dm. Like calcium, magnesium concentration is raised as a result of water passing over
magnesium ore formations. Calcium carbonate (CaCO3), magnesium hydroxide (Mg(OH)2), and
calcium sulphate (CaSO4) are a few of the deposits formed by the passage of water over ore
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formations of magnesium and calcium. Another example is the reaction of calcium with
bicarbonate;
CaCO3 (s) + CO2 (aq) + H2O (l) ⇋ Ca2+ (aq) + 2HCO3− (aq)
The sum of magnesium and calcium iron concentrations both expressed as calcium carbonate in
milligrams per litre is known as the total hardness. General guidelines for classification of water
in the United States are: 0 to 60 mg /dm3 (milligrams per litre) as calcium carbonate is classified
as soft; 61 to 120 mg/dm3 as moderately hard; 121 to 180 mg/dm3 as hard; and more than 180
mg/dm3 as very hard. (Heidekamp, Annelies J). Hardness was initially thought to be the
capacity of water needed to precipitate soap as water which is hard in nature would not allow
soap to form as much suds. Water with high concentrations of magnesium and calcium ions is
detrimental to plumbing and heaters, because at increased temperatures, scale of calcium and
magnesium ions is formed, which could possibly clog pipes or damage heaters.
1.3 JUSTIFICATION
Within the school community, the widespread usage of bottled water is as a result of the
preference of bottled water, thought to be high in metal ion concentration (especially calcium),
and therefore „purer‟ as compared to tap water. This investigation will aid in an informed
comparison and evaluation of this conception, as well as establishing the true calcium and
magnesium ion values in the samples of bottled water and tap water to be analysed.
2.0 METHOD
The method to be used was obtained from an online source (Canterbury). Some changes made to
the original method include metric systems (mL to cm3) and some volumes of reactants, such as
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halving the mass of ErioT indicator and the volume of ammonia and absolute ethanol needed to
turn it into a solution, in order to maintain the concentration specified in the referred literature
(Canterbury). This was done to avoid error and wastage, as advised not to store more than one or
two days before use, by the source the investigation was based on (Canterbury).
The method to be used is known as complexometric titration, used for finding the total calcium
and magnesium content of a given sample or also to find the total hardness of water, as the total
concentration of magnesium and calcium ions in a sample are considered to be the hardness. This
method utilized EDTA (ethylenediaminetetraacetic acid) or Edetic Acid, which is the acid form
of edetate, a chelating agent with anti-hypercalcemic and anticoagulant properties. Edetic acid
bonds with calcium and heavy metal ions, forming soluble stable complexes with calcium and
magnesium ions. It made use of the azo dye, Eriochrome Black T or ErioT as an indicator, (due
to its chemical association with azo pigments which are insoluble in water and other solvents),
which is blue in colour. The indicator also formed a complex with the calcium, magnesium and
other metal ions, changing from blue to red (red being an indication of a higher concentration of
these metal ions and pink indicating a lower concentration) in the process. Ammonium chloride,
(NH4Cl), was used as a buffer for this titration because EDTA is insoluble in water at low pH.
This is because H4Y (The various EDTA species are often abbreviated H4Y, H3Y-, H2Y2-, HY3-
and Y4-), is predominant in environments of low pH (less than 2). By increasing the pH, each
hydrogen ion in the carboxyl groups of EDTA will start to dissociate, making it easier for metal
ions to bond to as they do not need to remove hydrogen ions first. Above pH 10, Y4- is
predominant. As Y4- is needed to react with the metal ions present in the titration solution, a
buffer with a pH of 10 or higher, such as ammonium chloride is used. The branded water
samples were obtained from a local shop, unrefrigerated (room temperature), and distilled and
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tap water samples were obtained within the school. Hydrated magnesium chloride (MgCl2⋅6H2O)
was used in back titration to complex the excess EDTA in solution until the endpoint, after
which the remaining calcium and magnesium ions complex with the Eriochrome black T
indicator. Hydrated magnesium chloride was also used due to its ability to produce a sharp
The set-up involved a titration setup, for the indicator reaction with the water samples. The
reagent preparations took place in a fume cupboard (as was the case with the preparation of the
ammonium chloride buffer due to the presence of concentrated ammonia) and away from naked
flame in the case of dissolving the Eriochrome Black T indicator in ethanol. The water samples
were covered during the time they were not in use to avoid contamination by any of the reagents.
The burette was filled to the (0.00 ±0.05) cm3 mark with the hydrated magnesium chloride
solution prepared, before being used to titrate each water sample, which had the specified
volumes of indicator, ammonium chloride and hydrated magnesium chloride in mixture, until the
colour change from blue to red occurred, at which point the burette tap was closed and the titre
value recorded. Prior to the actual experimentation, trial titrations were carried out, using
samples of tap water, to confirm that the experiment indeed was viable.
7. Kettle (1)*
*This equipment was used to remove reduce carbon dioxide levels in the distilled water samples via boiling, a
1. EDTA
2. Ammonium chloride
5. Water samples
1. EDTA (C10H16N2O8) was prepared by adding (9.310 ± 0.001) g of EDTA salt to (500.0 ±
0.001)g of ammonium chloride to (57.00 ± 0.05) cm3 concentrated ammonia and then
diluted to (100.00 ± 0.05) cm3 with distilled water in a volumetric flask (pH 10.5)
4. Hydrated magnesium chloride (MgCl2 .6H2 O(s) in a 0.025 moldm-3 solution was made
(500.00 ± 0.01) cm3 with distilled water in a volumetric flask (175.0 ± 0.1 cm3).
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In Fig. 3, the pink colour seen is as a result of the product formed by the indicator and the calcium ions in
the solution. At this point all reagents excluding EDTA have been added.
In Fig. 4, the blue colour change is seen after the endpoint of the titration has been reached- a sign of total
reaction of all Ca2+ and Mg2+ ions in solution.
2.4 VARIABLES:
Independent variables: Water samples used (Bel-Aqua, Evian, Awake, Voltic, distilled
water, tap water, Highland springs, Special Ice, Ocean Spring, Everpure).
Dependent variables: End point colour of each sample, varying from red (high concentration
of calcium and magnesium ions) to pink (lower concentration of calcium and magnesium ions),
Controlled variables: Volume of water (100.00 ± 0.05 cm3), EDTA and Ammonium chloride
buffer used (500 ± 17.5 cm3 and 157 ± 0.1 cm3 respectively).
Fig1: EDTA 2-D structure (Pubchem) Fig. 2: Eriochrome black T 2-D structure (Pubchem)
Fig. 3: Structural equation of reaction between EDTA and calcium ion (Penn State/ Behrend)
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Consider the indicator ion, In 2-, to be blue and the product, CaIn to be wine red
In this experiment, the end point will be indicated when the original red solution turns to blue, as
a result of all Ca2+ or Mg2+ ions forming complexes with EDTA ions.
Indicator reaction:
2.6 PROCEDURE
1. A (10.00 ± 0.01) cm3 sample of the EDTA solution was pipetted into a (100.00 ± 0.05
cm3) conical flask.
2. (10 ± 0.01) cm3 of ammonia buffer solution and 1.00 ± 0.01 cm3 of Eriochrome Black T
indicator solution were added to the EDTA solution.
3. Using a (50.00 ± 0.05 cm3) burette, the EDTA was titrated with the magnesium chloride
solution until the endpoint was reached; a permanent colour change from blue to pink.
Titration method for water samples
1. (100.00 ± 0.01) cm3 of the water sample was poured into a (250.00 ± 0.01) cm3 conical
flask.
2. A 0.005 moldm-3 EDTA solution was made by adding (100.00 ± 0.01) cm3 of water to
the 0.05 moldm-3 solution of EDTA.
3. (20.00 ± 0.01) cm3 of the 0.005 moldm3 EDTA solution was added to the water sample.
4. (10.00 ± 0.01) cm3 of the ammonia buffer and (1.00 ± 0.01) cm3 of Eriochrome Black T
indicator solution were added to the water sample.
5. A 0.0025 moldm-3 magnesium chloride solution was prepared by adding (100.00 ± 0.01)
cm3 of water to the 0.025 moldm-3 magnesium chloride solution.
6. The water samples were titrated with this 0.0025 moldm-3 magnesium chloride solution
until the solution changed from blue to a permanent pink colour.
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7. The prior steps were followed with other samples, keeping the volume and concentration
of reactants the same until concordant results (titres agreeing within 0.10 ± 0.01 cm3)
were obtained.
2.7 SAFETY AND ETHICAL CONCERNS:
1. Ammonia, a highly corrosive substance with a pungent smell. As such parts of the
gloves and an apron were used to protect my skin and eyes. In the event of contact with
my skin, the affected area was thoroughly washed and neutralized with water. Disposal of
chemicals were carried out by pouring the ammonia down a designated drain and pouring
2. Ethanol, a highly flammable liquid with a sharp smell. Parts of my experiment involving
ethanol were carried out away from naked flame and heat to avoid combustion. Safety
The water samples were colourless. They remained colourless upon the addition of the EDTA
and buffer (both also colourless), but changed upon the addition of the indicator, from colourless
to blue (a sign of succesful reaction and complexing with calcium and magnesium ions in
solution.
Samples such as Evian, Ocean Spring, Highland Spring and Awake resulted in light red (pink)
solutions when EDTA, ammonium chloride and eriot T were added to the water samples, and a
blue solution after the titration was completed. The Bel-Aqua and Voltic samples however
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resulted in a dark red solution, much like a red wine, though very clear, and a dark blue, at the
end point. This difference is likely due to the highly basic nature of the water samples (both
companies boast of pH values above 7 (citifmonline.com). With this in mind high metal ion
Initial ( ± 0.05 cm3) Final ( ± 0.05 cm3) Volume used ( ± 0.1 cm3)
Initial volume ( ± 0.05 cm3) Final volume ( ± 0.05 cm3) Volume used ( ± 0.1 cm3)
Initial volume ( ± 0.05 cm3) Final volume ( ± 0.05 cm3) Volume used ( ± 0.1 cm3)
Initial volume ( ± 0.05 cm3) Final volume ( ± 0.05 cm3) Volume used ( ± 0.1 cm3)
Initial volume ( ± 0.05 cm3) Final volume ( ± 0.05 cm3) Volume used ( ± 0.1 cm3)
Initial ( ± 0.05 cm3) Final ( ± 0.05 cm3) Volume used ( ± 0.1 cm3)
Initial ( ± 0.05 cm3) Final ( ± 0.05 cm3) Volume used ( ± 0.1 cm3)
Initial ( ± 0.05 cm3) Final ( ± 0.05 cm3) Volume used ( ± 0.1 cm3)
Initial ( ± 0.05 cm3) Final ( ± 0.05 cm3) Volume used ( ± 0.1 cm3)
Initial ( ± 0.05 cm3) Final ( ± 0.05 cm3) Volume used ( ± 0.1 cm3)
Initial ( ± 0.05 cm3) Final ( ± 0.05 cm3) Volume used ( ± 0.1 cm3)
3.3 GRAPHS
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20
15
10
5
0
The data above was calculated to 2 decimal places (initial and final volumes) while volume
differences were calculated to 1 decimal place. The measurement was carried out with a 50 ±
0.05 cm3 burette, which is accurate to up to ± 0.05 cm3 meaning the titre differences for each
The first two titrations for each water samples was to gain a general idea of how much of the
EDTA would be required and so were performed much slower than the rest in order to do so,
In order to calculate the total moles of EDTA added to the sample solution:
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The moles of the magnesium chloride solution used in the back titration from concordant
results were calculated. From the equation of the titration below, the moles of Mg2+ are
Given that the ratio of Ca2+ + Mg2+ : EDTA = 1 : 1, the moles of Ca2+ and Mg2+ that must have
been complexed with EDTA were calculated by subtracting the moles of excess EDTA from the
total moles of EDTA added to the sample, using titre values. This result is the moles of Ca2+ and
Ppm(CaCO3) = × 1000ppm
<61 Soft
121-180 Hard
= = 8.3 cm3
= = cm3
% Uncertainty = = 1.204%
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m(EDTA): 9.31 g
= ×
Table 14: Water hardness, ppm value and number of calcium and magnesium ions present in
each sample
Water sample Parts per million (ppm) and Number of Ca2+ and Mg2+
water
4.0 ANALYSIS
These results show an interesting pattern: as expected, the most basic water samples had the
highest values per parts per million (ppm) and hardness levels at 186.9 ppm, 194 ppm and 205.9
ppm (Voltic, Bel-Aqua, distilled water respectively), however the number of moles of calcium
and magnesium ions for these water samples are not the highest and in fact low compared to the
other water samples (0.026897 mol, 0.026903 mol, 0.026907 as compared to the 0.026992 mol
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content of the Everpure water sample or the 0.026977mol content of the Highland Springs water
sample). This could be as a result of the presence of other metal ions being present in the water
samples which provided, for example copper, nickel, zinc, manganese, explaining how this
might have affected the calculation for the moles of the metal ions in the water samples. These
results reflect in the graph, showing the uncertainty for the average volume of EDTA used in
titrating each water sample in the error bars of accuracy (from the calculation) ± 0.1 cm3. The
graph illustrates the Ocean Spring sample, the tap water sample, the Special Ice sample and the
Everpure sample are the samples that recorded the least amounts of EDTA required for titration
(to form complexes with the calcium and magnesium ions present in the solution). The Evian and
Highland Springs samples reported moderately higher volumes of EDTA needed to complex,
while the Awake, distilled water, Bel-Aqua and Voltic samples required the most volumes of
5.0 CONCLUSION
Based from calculations and visual representation from the chart, the water samples tested
for hardness can be ranked according to their hardness (calcium and magnesium ion content) in
With these results, it is possible to predict the most popular water brands, based on hardness,
the most popular in that regard being Voltic mineral water, and the least predicted to be Ocean
6.0 EVALUATION
Though the experiment went as planned, one limitation was the presence of other ions in varying
concentrations in each of the water samples, which was beyond control, as they were added in
solution in the original packaging of the bottles. This did not nullify the results found in the
experiment, as the values of calcium and magnesium ions in parts per million of each of the
water samples were calculated and directly factored into the comparison and formation of the
conclusion, tackling the requirements of the research question. In terms of methodology, the
procedure used was sourced from a paper published by the University of Canterbury
(Canterbury), and so was considered credible. Titration was opted for as opposed to
spectrophotometry because it offered a broader range of detection for magnesium and calcium
ion concentrations. For data collection, ten readings were taken for each water sample, which
was deemed suitable enough for concrete data. For data processing and conclusion, parts per
million values (ppm) were calculated, as well as using the hardness scale, to determine the
hardest water samples. Controlled variables such as volume of water samples and reagents used
were adhered to strictly, however the distilled water sample required boiling to remove excess
carbon dioxide.
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7.0 IMPROVEMENTS
In order to improve upon the experiment, one could delve deeper to investigate the effect of
temperature, if any, on the ion contents of the different water samples, as well as the effect of
mineral ions or metal ions, other than the calcium and magnesium ions, present in the solution,
which was a condition beyond my control. Additional readings could be recorded to further
8.0 REFERENCES
Websites
www.hach.com/hardnessguide.
Webmaster. “Bel-Aqua Emerges Water Brand of the Year Again.” Citifmonline.com, 17 May
2017, citifmonline.com/2017/05/17/bel-aqua-emerges-water-brand-of-the-year-again/.
Edetic Acid.” National Center for Biotechnology Information. PubChem Compound Database,
Journals
Canterbury,www.canterbury.ac.nz/media/documents/science-outreach/magnesium_calcium.pdf
en.wikipedia.org/wiki/Eriochrome_Black_T.
waterquality.cce.cornell.edu/publications/CCEWQ-50-HardWater.pdf
Nov. 2018.
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