GUZMAN, Catherine Bernard Y.

April 5, 2019
IDOS, Gio Angelo G.

Group 6
Chem 26.1 CD

Experiment 7
Complexometric Determination of Calcium in Water Samples

ABSTRACT
Complexometric titration involves the determination of the concentration of ions
formed in a complex substance formed by a metal ion and a ligand. It is also
used to determine cations using complex-forming reagents. For this experiment,
the calcium determination of water samples, which came from the brand Refresh,
the researchers first prepared and standardized Ethylenediaminetetraacetic acid
(EDTA) solution using calcium solution. After the titration, the mean molarity of
the EDTA was determined to be 0.002340 ± 0.00028 M with a standard and
relative standard deviation of 9.156x10-5 and 3.913%, respectively. Since the
RSD is below 4%, then the results are reliable and precise. The CaCO3 titer in
mg/mL was also determined to be 0.2342 (mg/mL). The CaCO3 titer will be used
for the computation of the water hardness. Using the same methods for the
preparation and standardization of the EDTA solution, the water samples were
subjected to complexometric titration to determine their calcium content in mg/L
or ppm. After data gathering and analysis, the mean of the water samples’
hardness was determined to be 187.7 ppm, which is considered very hard based
on the water hardness scale. For the standard deviation and relative standard
deviation, the computed values were 0.4680 and 0.2494%, which is very low
signifying that the results and the measurements done are precise. However, the
computed water hardness, which is 187.7 ppm, was way too far compared to the
indicated calcium content in the bottle of the water sample, which is 25.0 mL.
This error may have caused by a lot of factor such as the misreading of the
researchers, the incorrect preparations of the monitors, or during the
manufacturing process itself of the bottled mineral waters as these factories and
companies use automated processes which can be left unseen by the quality
assurance.

Key words: complexometric titration, complex, ligand, water hardness

INTRODUCTION
Titration is a quantitative chemical method of analysis used to determine the unknown
concentration of solutions using known concentrations. Titration are often classified and
categorized into different types based on the components and chemicals used for the
determination (Helmenstine, 2019). Complexometric titration method is used when a metal ion
reacts with a suitable ligand which results to a complex ion, and the equivalence point of the
stoichiometric completion is determined using an indicator or an appropriate instrumental

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method (Skoog, West, Holler, & Crouch, 2014). Complexometric titrations are also useful for the
determination of the ions present in a solution (Kiruthiga, 2008).
Water in its pure molecular form does not exist in nature; it is a powerful solvent,
meaning a substance is more likely to be dissolved in it which forms a solution. Take for
example the rain, as it falls, it picks up gases and particulate matter in the air, and continues to
do this until it reaches the ground, wherein it picks up more soluble ions and other chemicals
(Byron, 2011). Due to this processes, natural water vary according to its “hardness”. Water
hardness is the amount of dissolved ions, calcium and magnesium to be specific, in water.
Water with a high amount of dissolved ions is considered “hard” and water with low amount of
these ions is termed as “soft” (Perlman, 2016).
The two cations mentioned are essential for the survival of organisms since they serve
many roles in several key processes. Since these ions are dissolved in water, the ion
concentration must be determined in order to monitor and control the intake of these two ions as
they may bring health effects these taking in large amounts.
The ligand used for this experiment was Ethylenediaminetetraacetic acid which is also
called (ethylenedinitrilo)tetraacetic acid, or simply EDTA. It is best known as a complexometric
titrant and chelating agent which contains both oxygen and nitrogen. The EDTA molecule has
six potential sites for bonding a metal ion: four carboxylic groups and two amino groups with an
unshared pair of electrons. Thus, EDTA is a hexadentate ligand (Skoog, West, Holler, &
Crouch, 2014).

Figure 1. The Ethylenediaminetetraacetic acid (EDTA) molecule

In this experiment, water hardness was measured using complexometric titration where
in amount on calcium in milligrams (mg) per liter of solution. Also, a more complex and deeper
understanding of titration was also introduced as the terms and concepts such as ligand, titer,
and chelating agents were used in the actual experimentation process.

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MATERIALS AND METHODS
In the complexometric determination of calcium in water, different chemicals and
instruments were used. The chemicals used are AR-grade disodium dihydrogen EDTA hydrate,
AR-grade CaCO3, concentrated HCl, NH3·NH4Cl buffer solution, and MgCl2·6H2O. The indicator,
Eriochrome black T (EBT) indicator, was already prepared prior to the standardization by
dissolving 0.5 g solid into 100 mL of alcohol. The water sample was obtained in a mineral water
Refresh. The laboratory apparatuses that were used was three 250-mL Erlenmeyer flasks, 250-
mL volumetric flask, 100-mL volumetric flask, buret, pipet & aspirator, small beaker, graduated
cylinder, and analytical balance. The complexometric determination is divided into two parts, the
preparation and standardization of EDTA solution which is presented by Figure 2 and the
analysis of calcium in water sample which is shown in Figure 3.
A. Preparation and Standardization of EDTA Solution
For the preparation of EDTA solution, 0.5 g disodium hydrogen EDTA dehydrate and
about 0.02 g of MgCl2·6H2O was dissolved using distilled water in a small beaker. Afterwards,
the solution was transferred into a 250-mL volumetric flask and was filled to mark. The solution
was then mixed thoroughly and was transferred to a clean labeled reagent bottle. The calcium
solution was prepared by weighing 0.05 g of previously dried CaCO3 and was put into a small
beaker. It was dissolved using a small amount of distilled water and was transferred to a 100-
mL volumetric flask. The effervescence and the solution were cleared by adding 1:1 drop-wise
concentrated hydrochloric acid. The solution was then diluted to mark and was mixed
thoroughly. The molarity of Ca2+ was then calculated.
The standardization of EDTA was done by pipetting out three preparations of 25.00 mL
of the calcium solution into three different 250-mL Erlenmeyer flasks. Each set-up was then
added 5.00 mL of ammonia-ammonium chloride buffer solution. Five drops of Eriochrome Black
T indicator was then added to each set up. The solution will turn wine red at this point of the
experiment. The three set-ups of the solution were then carefully titrated using the prepared
EDTA solution until the wine red color changes into pure blue. The molarity of the EDTA
solution and the calcium carbonate titer was then calculated.
B. Analysis of Water Samples
Three samples of 25.00 mL portion from the mineral water were pipetted out into three
250-mL Erlenmeyer flask. The samples were then added 1.0 mL of the ammonia-ammonium
chloride buffer solution. Afterwards, five drops of Eriochrome Black T indicator was added to
each sample which will turn them into wine red. The three set-ups were titrated using the
standardized EDTA solution until the wine red color turned pure blue, which indicated the

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stoichiometric completion of the reaction. The volume at which the color change/ end point was
observed was noted and was used for the calculation of the calcium ion concentration and the
water hardness.

Weigh 0.5 disodium dihydrogen Weigh 0.05 g primary standard

EDTA dihydrate and about 0.02 g CaCO3.
of MgCl2·6H2O.
Transfer to a 100-mL volumetric
Dissolve in a small beaker using flask using a small amount of
distilled water then transfer to a water
250-mL volumetric flask.
Add 1:1 hydrochloric acid until
solution is clear. Dilute to mark
Dilute to mark then mix the
solution. Transfer to a clean
labeled bottle. Calculate the
molarity of Ca2+

Pippette out 25.0 mL portion into

a 250 mL Erlenmeyer flask.

Add 5 mL buffer soluton and 5

drops of EBT indicator

Titrate using the prepared EDTA solution until wine-red color changes into blue

Repeat three times then calculate for the molarity of the EDTA solution and the
calcium carbonate titer

Proceed to Analysis of Water Samples

Figure 2. Procedure for the preparation and standardization of EDTA solution

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 Obtain water from Pipette out 25.0 mL Add 1.0 mL buffer
commercially available portion into 250-mL solution and 5 drops of
drinking water Erlenmeyer flask EBT indicator

Titrate with
Calculate water
standardized EDTA
hardness in mg/ L or Repeat three times.
solution until wine-red
ppm.
color changes to blue

Figure 3. Procedure for the water analysis and calcium determination

RESULTS
The following data measurements below are obtained by performing and following the
methods stated in this laboratory experiment.
Table 1. Mass of CaCO3 and Molarity of Ca2+
Mass of CaCO3 0.05192 g
Molarity of Ca2+ 0.01284 M

The table above shows the mass of the weighed CaCO3 used for the calcium solution,
which is 0.05192 g, with its corresponding molarity of the Ca2+, which is 0.01284 M.

Table 2. Volume of Ca2+ solution, Volume of EDTA used, and the computed Molarity of EDTA
Volume of Ca2+ Volume of EDTA
Trial Molarity of EDTA (mol/L)
solution (± 0.1 mL) used (mL)
1 25.00 mL 99.6 mL 0.001289 M
2 25.00 mL 57.1 mL 0.002248 M
3 25.00 mL 52.8 mL 0.002432 M

The table above shows the three samples of the calcium solution with the corresponding
EDTA used in the complexometric titration and the computed molarity. For trial 1, 99.6 mL of
EDTA was used which ended up to a molarity of 0.00189 M. Trial 2 used 57.10 mL of EDTA
resulting to an EDTA solution with a molarity of 0.002248 M. Lastly, 52.8 mL of EDTA was used
in trial 3 which resulted to a computed molarity of 0.002432 M. Depicted in the table above, trial
1 can be considered as an outlier as it used way too much EDTA compared to the two other
trials. Therefore, trial 1 is neglected and will not be used for further computations of the mean,
standard deviation, and relative standard deviation.
Table 3. Statistical Analysis of the Molarity of EDTA
Mean Molarity of EDTA (mol/L) 0.002340 ± 0.00028 M

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 Standard Deviation 9.156x10-5
Relative Standard Deviation 3.913%

Table 3 shows the statistical analysis and computation for the molarity of the EDTA.
Using only trial 1 & 2, the molarity of EDTA was found to be 0.002340 ± 0.00028 M. The
standard deviation was computed and determined to be 9.156x10-5. The relative standard
deviation, which is 3.913%, is below 4% which depicts that the measurements are precise and
accurate and that the results of the standardization are reliable.
Table 4. CaCO3 titer in each trial and their mean
Trial CaCO3 titer (mg/mL) Mean CaCO3 titer (mg/mL)
1 0.1290 (mg/mL)
2 0.2250 (mg/mL) 0.2342 (mg/mL)
3 0.2434 (mg/mL)

The CaCO3 titer in each trial and the mean is presented by table 4 above. For trial 1, the
resulting CaCO3 titer is 0.1290 (mg/mL). Trial 2 resulted to 0.2250 (mg/mL) while trial 3 has
0.2434 (mg/mL). Since the CaCO3 titer in trial 1 was determined by computation using the
volume of EDTA used in trial 1 on table 3, the resulting CaCO3 titer is still far compared to the
two other trials. With that being said, trial 1 is still considered as an outlier and was not used to
determine the mean CaCO3 titer, which is 0.2342 (mg/mL).
Table 5. Volume of water sample, Volume of EDTA consumed, and Water hardness
Volume of sample Volume of EDTA Hardness
Trial
(± 0.1 mL) used (mL) (mg CaCO3/L sample) in ppm
1 25.00 mL 15.10 mL 141.3 ppm
2 25.00 mL 20.00 mL 187.2 ppm
3 25.00 mL 20.10 mL 188.1 ppm

Table 5 above shows the results of the actual calcium determination in water sample
using complexometric titration. The volume used for each aliquot is 15.10 mL, 20.00 mL, and
20.10, respectively. For trial 1, the resulting water hardness in ppm is 141.3 ppm. For trials 2 &
3, both water samples contained above 180 ppm of ions, which is 187.2 ppm and 188.1 ppm,
respectively. Since trial 1, again, used much different volume of EDTA during the
experimentation process, the resulting water hardness is too far to consider compared to the
two other trials. With that, the computations for the mean, standard deviation, and relative
standard deviation, which is shown in table 7, neglected and did not use the result of trial 1.
Table 6. Statistical Analysis of the water hardness
Mean Hardness (mg CaCO3/L sample) in ppm 187.7 ppm
Standard Deviation 0.4680
Relative Standard Deviation 0.2494%

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 After the complexometric titration and data collection, the data gathered which is
presented in the tables above, were used for the computation of the mean hardness of the
water in ppm, which is 187.7 ppm. The resulting standard deviation is 0.4680 and the relative
standard deviation as 0.2494%, which is a very good value since it is way below 4%. It depicts
that the measurements and the experimentation process was precisely and accurately done
result to a very reliable result.

DISCUSSION
In complexometric titrations, a complex forms from a ligand an a metal ion caused by the
Lewis acid-base interactions wherein the positively charge metal ion acts as the Lewis acid and
the lone pair of electrons of the ligand acts as the Lewis base (Averill & Eldredge, 2016). A
complex is any chemical species which involves the coordination of ligands to a metal center.
The metal center can be of an atom or an ion and the complex formed may be a cation, an
anion, or a neutral molecule. In a chemical formula, a complex is denoted by the use of brackets
“[]”. Compound containing complex ions or complex themselves are also known as coordination
compounds (Petrucci, Herring, Madura, & Bissonnette, 2011).
In this experiment, the calcium determination of water, the ligand used to bind with a
metal ion is Ethylenediaminetetraacetic acid (EDTA), which is a aminocarboxylic acid with six
binding sites. According to Harvey (2010), the resulting metal-ligand complex from this
experiment is very stable. The chelate effect, or the stability of the complex, resulted from the
several complexing sites with the molecule which gives rise to a cage like structure wherein the
cation is surrounded by solvent molecules (Skoog, West, Holler, & Crouch, 2014).
Ethylenediaminetetraacetic acid is a hexadentate chelating ligand, which means it binds
in six points on to a metal central metal ion. The EDTA tends to react with a metal ion on a 1:1
stoichiometric ratio. Having able to bind four oxygen atoms and two nitrogen atoms, the EDTA
can form a strong 1:1 complexes with most metal ions (Harris, 2007). It also produces a sharp
endpoint upon the stoichiometric completion. With these characteristics, EDTA is preferred as a
ligand to react with a cation. In this experiment, EDTA can readily bind the metal ions into itself
with several bonds which increase its stability and reducing the hardness of water.
At the chosen pH, EDTA titrations should prevent metal hydroxide precipitation. An
auxiliary complexing agent was used to permit titration of metal in alkaline conditions with
EDTA. This was aided by the NH3·NH4Cl buffer solution which maintained the pH of the Ca2+
solution of more than 10 throughout the titration while EDTA acted as the titer (Skoog, West,
Holler, & Crouch, 2014).

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 In the first part of the experiment, the standardization of EDTA solution, the EDTA
solution, which was prepared with accordance to the steps indicated in the methodology, was
used as the titrant. Afterwards, the standard calcium solution was also prepared was was used
as he analyte of the titration. A complexation reaction occurred during the titration process
caused by the Mg2+ ions present in the granules which produced and isolated the Ca2+ ions. The
molarity of the Ca2+ was computed and was determined to be 0.01284 M.
After the preparation of the standard solution, the calcium solution was then subjected to
analysis by preparing three set-ups. Using a pipet, three 25.00 mL aliquot was transferred into
three Erlenmeyer flasks. These were then added 5 mL of NH3·NH4Cl buffer solution and 5 drops
of the Eriochrome Black T indicator. Since both EDTA and Eriochrome Black T indicator are
polyprotic, the NH3·NH4Cl buffer solution aided the solution to have constant pH. The
Eriochrome Black T indicator allowed the addition of EDTA to be quantifiable at a certain pH
level (Harris, 2007). Upon the addition of the Eriochrome Black T indicator, the Ca2+ and Mg2+
ions bonded with H2In-.

2H2In- + Ca2+ + Mg2+ → MgIn- + CaIn- + 4H+

Figure 4. Reaction between the calcium and magnesium ions and the EBT indicator before the
equivalence point

As shown in the chemical equation above, two complexes were formed as a product
between the reaction of the metal ions and the indicator; these are CaIn- and MgIn-. These two
metal complexes are wine-red in color due to the fact that a complex between a metal ion and
EBT is wine-red (Harris, 2007). At this point, before the equivalence point, excess Ca2+ ions
are still present in the solution
After the solution turned red, titration with EDTA was then performed. The metal ions
from the wine-red complex (In) gave up its metal ions and the excess Ca2+ bonded with EDTA
forming a more stable complex. At the equivalence point, the concentration of the calcium ions
and the indicator were now equal. The metal ions bonded with the EDTA assumed the colorless
CaEDTA2- ion form leaving the displaced In ions from the wine-red complex in the solution.
These In ions contributed to the blue color of the solution at the end point.
CaIn- + EDTA4- ↔ CaEDTA2- + In2-
(wine-red) (colorless) (blue)
Figure 5. Reaction between the wine-red complex and the EDTA isolating the colorless
CaEDTA2- and blue In2-

Page 8 of 14
 Figure 6. CaEDTA2- complex formed by calcium ions and EDTA

With the following reactions and methods above, the molarity of the EDTA solution was
0.002340 ± 0.00028 M. The mean of the EDTA solution only used trials 2 and 3 as trial one was
far from the other to be considered. This made the measurement from trial 1 to be negligible
and considered as an outlier. The reason for this was the prepared indicator of the monitors
were not concentrated enough and the stoichiometric completion was taking so long which led
to the large volume of EDTA needed for the solution change color from wine-red to blue. The
problem was then solved by adding more solid EBT indicator and no more problems was
encountered during trial 2 until the end of the experiment. The standard deviation of 9.156x10-5
is considered small therefore the result is not that scattered and the measurements were
precise and accurate, as also depicted by a relative standard deviation of 3.913%

% 𝑝𝑢𝑟𝑖𝑡𝑦 𝑜𝑓 1 𝑉 𝐶𝑎𝐶𝑂3 𝑎𝑙𝑖𝑞𝑢𝑜𝑡

( ) (𝑔 𝐶𝑎𝐶𝑂3 ) ( )( )
𝐶𝑎𝐶𝑂3 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓𝐶𝑎𝐶𝑂3 𝑉 𝐶𝑎𝐶𝑂3 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑀𝑜𝑙𝑎𝑟𝑖𝑡𝑦 𝑜𝑓 𝐸𝐷𝑇𝐴 =
𝑉 𝐸𝐷𝑇𝐴 𝑢𝑠𝑒𝑑 𝑖𝑛 𝐿
Figure 7. Equation for the computation of EDTA molarity

For the CaCO3 titer of each trial the equation in figure 8 was used. Note that the computed
CaCO3 titer in trial 1 used the outlier volume which makes it also an outlier. The CaCO3 titer
mean was determined to be 0.2342 (mg/mL).
𝑉 𝐶𝑎𝐶𝑂3 𝑎𝑙𝑖𝑞𝑢𝑜𝑡
𝑚𝑔 (% 𝑝𝑢𝑟𝑖𝑡𝑦 𝑜𝑓 𝐶𝑎𝐶𝑂3 )(𝑚𝑔 𝐶𝑎𝐶𝑂3 ) ( )
𝑉 𝐶𝑎𝐶𝑂3 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝐶𝑎𝐶𝑂3 𝑡𝑖𝑡𝑒𝑟 ( ) =
𝑚𝐿 𝑉 𝐸𝐷𝑇𝐴 𝑢𝑠𝑒𝑑 𝑖𝑛 𝑚𝐿
Figure 8. Equation for the computation of CaCO3 titer

Page 9 of 14
 The second part of the experiment involves the determination of calcium in water
samples. The determination followed the same method applied in the standardization of EDTA
solution using the calcium solution. The water sample was obtained in a mineral water with the
brand Refresh. The amount of calcium in water analyzed determines the water hardness. Water
hardness is determined by the total concentration of alkaline earth ions, whch are mainly Ca2+
and Mg2+ in water (Gass, n.d.). Water hardness is usually expressed as equivalent number of
CaCO3 per liter of water. It can also be expressed as parts per million, or ppm.
Table 7. Water hardness scale
Total Hardness (mg/L as CaCO3)
Soft Water 0-30 mg/L
Moderately soft water 31-60 mg/L
Moderately hard water 61-120 mg/L
Hard water 121-180 mg/L
Very hard water >180 mg/L

For the three trials, trial 1 contained 141.3 ppm, which is hard water based on the water
hardness scale. Both trial 2 & 3 contained above 180 ppm of calcium ion, 187.2 ppm and 188.1
ppm, respectively, which is considered very hard water. Note that the water in trial 1 only
consumed 15.1 mL of EDTA, which is far compared to the volume of EDTA used in trials 2 and
3, which is 20.0 mL and 20.1 mL, respectively, with that being said, the results in trial 1 was
considered as an outlier and was not used in the calculation of the mean of the water hardness,
which is 187.7 ppm, which is still very hard with accordance to the water hardness scale. The
standard deviation and the relative standard deviation, which is 0.4680 and 0.2494% depicted
that the results are near to each other. However, the amount of calcium indicated at the
packaging of the mineral water was 25.0 ppm, which is way too far from the the water hardness
mean. This possibly resulted from the error of the researchers such as misreading, inaccurate
weighing and other factors which resulted to discrepancies. Also the monitors may have also
contributed errors due to the fact that if they did not prepare the indicator properly, we would not
know if they also prepared the other solutions, such as the buffer solution correctly and
accurately. Also, the company may have also misstated the calcium content as the water
production where the sample was made is mostly automated and errors during the production
have may gotten through quality inspection. The bulk production of the bottled water may have
also contributed to the different calcium content indicated from the calcium content computed by
the researchers.

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CONCLUSION
This experiment made use of the complexometric titration wherein complex substances
are formed by a metal ion and a ligand reacted with each other. EDTA was used as the ligand
which reacted with the calcium ions present in the water sample. This method helped the
researchers determine the hardness of water depending on the amount of calcium ions present
which is indicated by an endpoint, a color change from wine-red to blue, to be specific. The
resulting water hardness of the water samples contained 187.7 ppm of calcium which is far from
the indicated 25.0 mL in the bottle of the water sample. This is due to the numerous errors the
researchers may have been encountered during the process. Water hardness is one important
property of water which is being used in industrial and domestic uses however, it do not pose
any significant effect on human consumption. According to the National Research Council,
drinking hard water significantly contribute very small amount of the total calcium and
magnesium human dietary needs.

ANSWERS TO POST LAB QUESTIONS

1. Explain the advantage/disadvantage of using Eriochrome Black T over calmagite as indicator.
Eriochrome Black T indicator or EBT indicator is the most widely used indicator in
complexometric titrations. Solutions which used EBT as an indicator decompose slower unlike
calmagite. It is alaso cheaper than calmagite. However, some of its disadvantages is that it is
very unstable so it is prepared as a solid solution. Also EBT indicator has a very short shelf life
when using it as a fresh indicator. EBT indicator can only last two months while calmagite can
be kept for a year (Brooks, 2015).

2. Explain why Mg (II) must be added when EDTA is standardized using calcium carbonate as a
primary standard and Eriochrome Black T as indicator.
Mg2+ was added so that there would be a reacting agent to the EBT indicator. When
EDTA was added, the MgIn- formed from the reaction of Mg2+ and EBT dissociated and the
Mg2+ associated with the EDTA which gives a sharp end point. Also, Since EDTA has four
acidic protons, the formation of complexes depends on the pH, thus, the addition of Mg(II)
buffered the solution and the complex formation would be quantitative (Harris, 2007).

3. A 20.00 mL volume of EDTA titrant is required to titrate 25.00 mL of standard 0.0100 M

CaCO3. A 75.00 mL sample solution of chalk requires 30.00 mL of this EDTA titrant in the
analysis of calcium content. Calculate both the ppm Ca and ppm CaCO3 in the sample solution

Page 11 of 14
of chalk. If the 75.00 mL sample solution is withdrawn from a stock solution of 500.00 mL which
contains 2.1345 grams of chalk, what is the %Ca in the solid sample?
Given: 20.00 mL EDTA used in titrating CaCO3
25.00 mL of 0.0100 M CaCO3
30.00 mL EDTA used in titrating chalk solution
75.00 mL chalk solution from 500.00 mL containing 2.1345 g solid chalk
CaCO3 molar mass=100.08 mg/mmol
Ca molar mass=40.08 mg/mmol
Find: CaCO3 content in chalk solution (ppm)
Ca content in chalk solution (ppm)
%Ca in in solid chalk sample
Solution:
MOLARITY OF EDTA
𝑀𝐶𝑎𝐶𝑂3 𝑥 𝑉𝐶𝑎𝐶𝑂3 1𝑚𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 0.0100 𝑀 𝑥 25.00 𝑚𝐿 1 𝑚𝑚𝑜𝑙 𝐸𝐷𝑇𝐴
𝑀𝐸𝐷𝑇𝐴 = ( ) = 𝑥 ( ) = 0.0125 𝑀
𝑉𝐸𝐷𝑇𝐴 1 𝑚𝑚𝑜𝑙 𝐶𝑎2+ 20.00 𝑚𝐿 1 𝑚𝑚𝑜𝑙 𝐶𝑎2+

MOLARITY OF CaCO3
𝑀𝐸𝐷𝑇𝐴 𝑥 𝑉𝐸𝐷𝑇𝐴 0.0125 𝑀 𝑥 30.00 𝑚𝐿
𝑀𝐶𝑎𝐶𝑂3 = = = 0.00500 𝑀
𝑉𝐶𝑎𝐶𝑂3 75.00 𝑚𝐿

ppm Ca2+
𝑀𝐶𝑎𝐶𝑂3 𝑥 𝐹𝑊𝐶𝑎2+
𝑝𝑝𝑚 𝐶𝑎2+ =
𝐿𝑠𝑎𝑚𝑝𝑙𝑒
0.00500𝑚𝑚𝑜𝑙 1𝑚𝑚𝑜𝑙 𝐶𝑎2+ 40.078𝑚𝑔 2+
𝐶𝑎𝐶𝑂3 𝑥 𝑥 𝐶𝑎 𝑥 1000 𝑚𝐿
𝑚𝐿 1𝑚𝑚𝑜𝑙 𝐶𝑎𝐶𝑂3 𝑚𝑚𝑜𝑙
=
1𝐿
𝑝𝑝𝑚 𝐶𝑎2+ = 200𝑝𝑝𝑚

%Ca
0.0125 𝑚𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 1 𝑚𝑚𝑜𝑙 𝐶𝑎2+ 40.078𝑚𝑔 𝐶𝑎2+
%𝐶𝑎 = 30.0 𝑚𝐿 𝐸𝐷𝑇𝐴 𝑥 𝑥 𝑥
1 𝑚𝐿 𝐸𝐷𝑇𝐴 1𝑚𝑚𝑜𝑙 𝐸𝐷𝑇𝐴 1𝑚𝑚𝑜𝑙 𝐶𝑎2+

500𝑚𝐿 𝑠𝑡𝑜𝑐𝑘 𝑠𝑎𝑚𝑝𝑙𝑒 1 1𝑔 𝐶𝑎𝐶𝑂3

𝑥 𝑥 𝑥 𝑥 100% = 𝟒. 𝟔𝟗% 𝑪𝒂
75.000 𝑚𝐿 𝑠𝑎𝑚𝑝𝑙𝑒 2.1345 𝐶𝑎𝐶𝑂3 1000𝑚𝑔 𝐶𝑎𝐶𝑂3

Page 12 of 14
4. The titration of a 50.00 mL water sample for total hardness required 4.08 mL of 0.0100 M
EDTA. Calculate the hardness of the water as ppm CaCO3.
𝑚𝑔 0.0100𝑚𝑚𝑜𝑙 100.09𝑚𝑔 𝐶𝑎𝐶𝑂3
𝐶𝑎𝐶𝑂3 𝑥 𝑚𝐿 𝐸𝐷𝑇𝐴 𝑚𝐿 𝑥 𝑥 4.08 𝑚𝐿
𝑚𝑚𝑜𝑙 𝐶𝑎𝐶𝑂3
𝒑𝒑𝒎 𝑪𝒂𝑪𝑶𝟑 = 𝑚𝐿 = = 𝟖𝟏. 𝟕 𝒑𝒑𝒎
𝐿 𝑤𝑎𝑡𝑒𝑟 𝑠𝑎𝑚𝑝𝑙𝑒 0.0500𝐿

REFERENCES
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Chemistry_(Averill_and_Eldredge)/17:_Solubility_and_Complexation_Equilibria/17.3:_Th
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Brooks, D. (2015, April 20). Determining the Hardness of Water. Retrieved April 22, 2019, from
http://dwb5.unl.edu/chem/smallscale/SmallScale-051.html
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20, 2019, from https://www.tropicalfishkeeping.com/member-submitted-articles/water-
hardness-ph-freshwater-aquarium-73276/
De la Camp, U., & Seely, O. (n. d.). Complexometric Ca Determination. Retrieved 21 April 2019,
from http://www.csudh.edu/oliver/che230/labmanual/calcium.htm
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Gass, D. (n.d). “What is water hardness”. Study.com. Retrieved 21 April 2019, from
http://study.com/academy/lesson/what-is-water-hardness-definition-measurement.html
Harris, D. (2007). Quantitative Chemical Analysis. (7th ed.). USA: W.H. and Freeman Company.
Helmenstine, A. M. (2019, January 30). What Is Titration? Retrieved April 20, 2019, from
https://www.thoughtco.com/titration-definition-602128
Kiruthiga, B. (2008). Complexometric Titration. India: Department of Pharmaceutical Chemistry,
SRM
Perlman, H. (2016). Hardness in Water, USGS Water Science School. U.S. Geological Survey.
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Petrucci, R. H., Herring, F., Madura, J. D., & Bissonnette, C. (2011). General Chemistry:
Principles and Modern Applications (10th ed.). Toronto: Pearson Canada.
Sinex, S. A. (2004, March). EDTA - A Molecule with a Complex Story. Retrieved April 21, 2019,
from http://www.chm.bris.ac.uk/motm/edta/edtah.htm

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Skoog, D. A., West, D. M., Holler, F. J., & Crouch, S. R. (2014). Fundamentals of Analytical
Chemistry (9th ed.). Belmont, CA.: Brooks/Cole, Cengage Learning. University.

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