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EXPERIMENTAL DETERMINATION OF THE CONCENTRATION OF CALCIUM

AND MAGNESIUM IONS IN “SUPERMONT” MINERAL WATER.

INTRODUCTION:

Water is essential for life with each adult human being needing to drink an average of at least
2L of water per day to maintain optimum fitness and alertness. It is not only water that is
crucial but the minerals contained in it are vitally important for our wellbeing. These minerals
are the main constituents of all basic body fluids such as saliva, blood, synovial fluid, urine
and others. There are more than twenty mineral elements including calcium, magnesium,
sodium, potassium and other trace elements are known to be essential for humans. Some
important mineral elements for health include calcium for bones and teeth, magnesium for
healthy nervous system and bones, iron for producing haemoglobin, potassium to keep the
muscles and nervous system healthy, zinc for healthy immune system and sodium to maintain
balance of water around the cells. It has been observed that minerals are easily absorbed from
water than from food, because in water they are found in the form of ions and easily absorbed
by the intestines whereas in food they are food combined with other elements. Other anions
found in water are nitrates, chlorides and bicarbonates. The quantification of these mineral
ions can be done through many methods which could be instrumental or titrimetric. A reliable
and accurate titrimetric method to determine the amounts of these ions is by complexometry.

Since I was born my family has been consuming mineral water specifically Supermont. I used
to read the labels of supermont bottles and wonder how one could do to know those quantities
mentioned on the labels. In the book edited by Ingegerd, suggested ranges for Calcium and
Magnesium in water are from 20 to 80 mg/L and 10 to 50 mg/L respectively. For this reason I
wanted to determine the concentrations of these particular ions and compare with that on the
labels which are 30mg/L and 5.9mg/L for calcium and magnesium ions respectively. This will
also go to confirm the accuracy of complexometry in the determination of mineral ions in
solution.

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RESEARCH QUESTION:

To what extent does the concentration by mass of calcium and magnesium ions determined
through complexometric titration match the value on the label of the “ Supermont” mineral
water ?.

Background:

Titrimetry and especially complexometry is a good and reliable method which is used to
quantify a wide range of analytes. The high accuracy of the results and maturity of the
procedure have made it a routine method in various fields such as environmental monitoring,
bioanalytical chemistry and clinic analysis. When compared with quantitative instrumental
methods such as ion chromatography, Inductively coupled plasma spectroscopy coupled to a
mass spectrometer ( ICP-MS ) or Atomic Absorption spectroscopy (AAS), titrimetry and
especially complexometry is one of the simplest and most accurate because it relies on an
exhaustive consumption of the analyte at the end point. Today, titrimetry can be easily
adapted and commercially available standardized reagents provide more convenience to the
end users. Complexometric titration (complexometry or chelatometry) is one of the classical
titrimetric methods developed for the rapid and quantitative chemical analysis of metal ions.
The ions of interest are titrated with the chelator of choice through a coordination
complexation reaction and rapidly form stable monodentate or multidentate complexes. The
chelator is sometimes called the complexing reagent or more simply, titrant. The end point
can be identified by a metallochromic indicating dye, which shows a color change, or by other
instrumental indicators, such as ion-selective electrodes.

The use of complexometric titration method to quantify metal ions was formally introduced
in 1945 by Schwarzenbach, mainly using EDTA as chelator. Since then, complexometric
titration has been widely used, for example to measure water hardness. Murexide and
Eriochrome Black T were established as indicators for water hardness. A number of
researchers such Salvatore and coworkers have worked with EDTA which is the most widely
recognized chelator in complexometric titration. However good chelators and indicators as
well as new concepts have been continuously emerging. This work summarizes the use of
EDTA in the determination of mass concentration of Calcium and Magnesium ions on a given
mineral water “ Supermont” through complexometric titration, using Eriochrome Black T as
indicator.

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Principle: Metal complexes form stable complexes with complexing agents such as EDTA
and indicators such as Eriochrome Black T. The EDTA – Metal complex is very stable at a
pH of about 10, reason why Ammonia buffer of pH 10 is used.

Mg2+ +H2Y2- MgY2- + 2H+

Ca2+ +H2Y2- CaY2- + 2H+

Where, Y represents EDTA

At the end point colour of the indicator changes from red wine to blue.

It should be noted that the indicators colour (Eriochrome Black T) is red-wine when
complexed with the metal and blue when free.

Mez+ + lny- Meln(y-z)

At the start of the complexometric titration, because of the excess of metal ions (Me z+ ) in the
titrated solution, we see the colour of the metal-indicator complex (MeIn (y-z)) , which is red
wine. As the titration advances, Mez+ progressively disappears from the solution because of
the formation of the complex EDTA-metal, until a point is reached when the MeIn (y-z)
complex is decomposed to the free indicator. At this point, the colour of the solution changes
from that of MeIn(y-z) to that of the free indicator lny- which is blue

Hypothesis:

Mass concentrations of calcium and magnesium ions determined by complexometric titration

should closely match that on the label of our Supermont mineral water. This is so because
complexometric titration is a reliable and accurate method in quantitative analysis of metal
ions in solution.

AIM:

To determine the mass concentrations of Ca2+ and Mg2+ ions in Supermont mineral water and
compare with the values on the labels.

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Requirements:

Sample of EDTA
Quantity: 10.00g

Pipette and pipette filler

Number: 2 of 25cm3 +/- (1/300cm3)
Burette
Number: 1 of 50cm3 +/- (0.05cm3)
Conical Flask
Number: 3 of 250cm3
Beaker
Number: 2 of 100cm3 and 2 of 250 cm3
Volumetric Flask
Number: 2 of 250cm3 and 2 of 1000cm3 (1L)
Distilled Water
Quantity: 01 Gallon of 5L
Clamp and stand
Number: 1
Filter Funnel
Number: 1
Spatula
Number: 1
Electronic Balance
Number: 01 +/- (0.01g)
Glass Rod
Number: 1
Sodium hydroxide
Quantity: 200cm3 of 2M NaOH (80g NaOH in 1L volumetric flask)
Dropper
Number: 04
Ammonia buffer (pH = 10)
Quantity: 100 mL ( dissolve 7g of NH 4Cl in 57cm3 of conc. NH3 solution , complete with distilled
water to 100 mL)
Eriochrome Black T indicator.
Quantity: 100mL solution ( 0.5g in 100mL absolute methanol)
Mineral water
Quantity: 01 bottle of 1.5L
Table 1: Requirements for experiment

Controlled variables Method of control of Reason for controlling

variable variable

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1. Temperature KEPT CONSTANT (room Temperature affects the rate

temperature; approximately of a reaction. When
25°C ± 1) increased it speeds it up and
when decreased might slow
it down. All reactions taking
place at the same
temperature, will therefore
ease data analysis.
2. Pressure KEPT CONSTANT Pressure of atmospheric
gases such as CO2 affect the
pH of solutions. It is
therefore kept constant in all
reactions to avoid its effects.
Table 2: Controlled variables

Procedure:

- Weigh accurately 0.425g of EDTA (M.W = 292.25 g/mol) using an analytical balance
use it to prepare a standard solution in 1L volumetric flask.
Number of moles of EDTA = (0.425/ 292.25)
= 0.00145 mol
Concentration of EDTA in 1L = 0.00145 mol/dm3.

- Fill a burette with the EDTA solution prepared earlier.

- Pipette 25mL of the mixture of calcium and magnesium ions from the Supermont
mineral water into a 250 mL conical flask.
- Add 5ml of the Ammonia buffer using a measuring cylinder and then two to three
drops of Eriochrome black T indicator using the dropper. The solution turns to a red
wine colour.
- Start titration by pouring the EDTA solution from the burette into the flask into the
conical flask and swirl until a permanent blue colour is obtained. This is the
approximate titration and record in table 1.
- Record the results of two accurate titrations too in table 3
- The volume of EDTA here is that used to react with the mixture of calcium and
magnesium ions.

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To determine the concentration of Magnesium ions only

- Fill the burette with the EDTA solution and pipette 25 mL of the solution containing
both ions into the conical flask.
- Add 2 mL of 2M NaOH into the conical flask to precipitate out the calcium ions in the
form of calcium hydroxide. Then add 3mL of ammonia buffer and titrate with solution
from the burette.
- Record the results of an approximate and two accurate titrations in table 4

Data collection and Processing

i) Table 3: Determination of total concentration of Calcium and Magnesium

ions.

  Trial 1 Trial 2 Trial 3

Initial burette 0.0 0.0 0.0

reading / cm3
(±0.05 cm3)

Final burette 24.0 22.4 23.2

reading / cm3
(±0.05 cm3)

Titre / cm3 (±0.1 cm3) 24.0 22.4 23.2

22.4 +23.2
¿
Average titre 2
¿ (22.8 ± 0.1 ) cm3

Mg2+ +H2Y2- MgY2- + 2H+

Ca2+ +H2Y2- CaY2- + 2H+

From the equation of the complexation:

MEDTA VEDTA = M(Mg2++ Ca2+) V(Mg2++ Ca2+)

[Mg2++ Ca2+ ] = ([H2Y2- ] x Vol H2Y2-)/ vol of mixture

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[Mg2++ Ca2+ ] = (0.00145M x 22.8 cm3)/25 cm3

= 0.00132 M

Uncertainty calculation on concentration of mixture.

∆[Mg2++ Ca2+ ] = [Mg2++ Ca2+]x [ (∆Vol H2Y2-/ Vol H2Y2-) + (∆vol of mixture/ vol of
mixture)]

∆[Mg2++ Ca2+ ] = 0.00132x[(0.1/22.8) + (1/300)]

[Mg2++ Ca2+ ] = (0.00132000 ± 0.00000002) mol/dm3

ii) Table 4: Determination of total concentration of Magnesium ions.

  Trial 1 Trial 2 Trial 3

Initial burette 0.0 0.0 0.0

reading / cm3
(±0.05 cm3)

Final burette 5.0 4.2 4.6

reading / cm3
(±0.05 cm3)

Titre / cm3 (±0.1 cm3) 5.0 4.2 4.6

4.2+4.6
¿
Average titre 2
¿ ( 4.4 ± 0.1 ) cm3

Data processing

i) Calculation of concentration Magnesium ions in solution.

Equation: Mg2+ +H2Y2- MgY2- + 2H+

From the equation of the complexation:

MEDTA VEDTA = M(Mg2+) V(Mg2+)

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Concentration of Mg2+ [Mg2+ ] = ([H2Y2- ] x Vol H2Y2-)/ vol Mg 2+

= ( 0.00145M x 4.4 cm3)/25 cm3

= 0.0002552M

Uncertainty calculation on concentration of magnesium ions.

∆[Mg2+ ] = [Mg2+]x [∆ (Vol H2Y2-/ Vol H2Y2-) + (∆vol of Mg2+/vol of Mg2+)]

∆[Mg2+] = 0.0002552x[(0.1/4.4) + (1/300)]

[Mg2+ ] = (0.00025520 ± 0.00000002) mol/dm3

Concentration of Mg2+ (P) in mg/L = 0.0002552mol/L x (24.3 x 1000) mg/mol

= 6.23 mg/L

uncertainty calculation on mass concentration P

∆PMg2+ = PMg2+ x (∆ [Mg2+ ] / [Mg2+ ])

= 6.23x( 0.00000002/0.00025520)

Concentration of Mg2+ (P) in mg/L = (6.230 ± 0.001 ) mg/L

Calculation of concentration of Calcium ions

Number of moles of calcium ions = number of moles of mixture – number of moles of Mg 2+

ions

= ( [Mg2++ Ca2+ ] - [Mg2+]) x vol in dm3

= [( 0.00145 x 22.8) – (0.00145 x 4.4)] / 1000

= 0.0008265 -0.00000638

= 0.000820 mol/L

Concentration of Ca2+ (P) in mg/L = 40,000 mg/mol x 0.00082mol/L

= 32.8 mg/L

uncertainty calculation on mass concentration P

∆PCa2+ = PCa2+ x (∆ [Ca2+ ] / [Ca2+ ])

= 32.8 x (0.00000002/ 0.00132)

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= ( 32.80 ± 0.001) mg/L

Calculation of percentage error of values.

The table below compares values obtained by titration to values on label of Supermont
mineral water.

Table 5: Calculation of percentage error of values

Value on label ( Plab) Value from Titration (Ptit) Difference in values % Difference

PMg2+ = 5.9 mg/L 6.23 mg/L 0.33 5.6%

PCa2+ = 30mg/ L 32.8 mg/L 2.80 9.3%

Ptit −Plab
% Difference ¿ × 100
Plab

6.23−5.9
% difference on concentration of Mg2+ = × 100
5.9
= 5.6%

32.8−30.0
% difference on concentration of Ca2+ = ×100
30
= 9.3%

Below is a graphical representation of the values of the concentrations of magnesium

and calcium ions respectively

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concentration of mineral ions

35
30 30 32.8
mass conc P /mg/L

25
20
15 5.9
10
5 0 6.23
0
0
1
2
3
4
mineral ions 5

Figure 1: graph of comparism of mass concentration Of Ca and Mg ions on bottle label

and through titration

Conclusion

The values of mass concentration of Calcium and Magnesium ions obtained by

complexometric Titration are slightly higher than those presented on the label of the
supermont mineral water bottle. Though they are higher the difference gotten is less than 10%
for both Mg2+ and Ca2+ ions. The difference in these values can be attributed to various
sources of errors which could be due to the experimenter or the techniques and apparatus
employed in carrying out the different steps of the experiment. Nevertheless it can be said the
complexometric technique can be said to be accurate because the percentage accuracy is less
than 10% and can be recommended as a reliable and important quantitative analytical
technique. The quantity of calcium and magnesium ions in solution gives of an idea of the
hardness of the water. In this case we can say the water is medium in hardness. Finally it can
rightly be concluded that are aim which was to determine the concentrations of calcium and
magnesium ions in a given mineral water has been attained for Calcium ions and this value
fall below maximum recommended values for mineral water by Ingegerd. On the other hand
that of Magnesium ions are below the recommended values but this does not have any serious
effect because only very large concentrations can be of health concern;

Evaluation

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The methodology of this experiment did not prevent many sources of error from influencing
the results.

Source 1: the distilled water used might still have contained some traces of calcium and
magnesium ions which might influenced the final concentrations obtained

Effect: This might have gone a long way to increase the amounts of these calcium and
magnesium ions in the solutions prepared and hence much standard solution from the burette
had to be used than expected and this might increase the total amount of ions obtained.

Improvement: in future it would be advised to use distilled water (distill the water twice) to
ensure that all traces of calcium and magnesium ions would be greatly reduced

Source 2: The detection of the end point with the naked eyes might not have been very
accurate given the weak concentrations involved and the sensitivity in the the colour change
involved.

Effect: This might have increased the time taken to detect the end point of the titration and
might have allowed for more standard from the burette to be poured than hence more standard
was poured than expected .

Improvement: a more accurate way of detecting the end point could be used such as uv-
visible spectrometric techniques which could easily detect sharp changes in colour and give
more accurate volumes of standard from burette.

Source 3: The pH of the reaction mixture was supposed to be at 10 because the stability of the
metal- EDTA complex formed is stable at that pH and unstable at higher or lower pH values.

Effect: This might have greatly interfered with the equilibrium taking place for a more
accurate end point to be attained and also in the total amount of EDTA that actually reacted,
since its availability in solution and its reaction with the metal ions is pH dependent.

Improvement: In addition to the use of a buffer solution, not only should it well prepared but
its pH has to tested after preparation to ensure it is actually at the required pH. A pH meter
could be used even after the buffer has been added to ensure the amount added is able to
maintain the pH at the required value. For further research it could be advised to determine
the composition of other ions such as bicarbonate and nitrate ions and compare the obtained
values with internationally accepted standards.

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References

1. World Health Organization (2020). Retrieved 14 April 2020, from

https://apps.who.int/iris/bitstream/handle/10665/254637/9789241549950-
eng.pdf;jsessionid=A8214C97889BCDB050D280CD66154B56?sequence=1
2. World Journal of chemical Education (2015). Retrieved 14 April 2020, from
https://www.iris.unina.it/retrieve/handle/11588/616522/26513/wjce-3-1-2%20%283%29.pdf
3. Rosborg, I. Retrieved 14 April 2020, from https://link.springer.com/content/pdf/bfm%3A978-3-
319-09593-6%2F1.pdf
4.

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