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Kgasu Mosa
[Email address]
 ABSTRACT

The purpose of the study was to determine the total hardness of

water using the concepts learned about the complexometric
EDTA titration. The hardness of water is defined in terms of its
content of calcium and magnesium ions, and by the
complexometric EDTA titration, which is the process of metal
ion titration until a product of complexes is obtained, hardness
can be determined. There total hardness of water was identified
to categorize the use a specific type of water —whether it is used
domestically or industrially. The determination of water
hardness is also a useful test that provides a measure of quality
of water for households, particularly for water potability. The
working standard CaCO3 solution was added with buffer
solution and Eirochrome Black T (EBT) indicator for the
standardization of the EDTA titrant solution. The analysis of
water sample involved the titration of a measured volume of
mineralized water of the brand Hidden Spring (plus buffer
solution and EBT indicator) with the EDTA solution. A color
change from wine red to clear blue indicates the titration
endpoint. The computed total hardness was 248.7 ppm (average
of the three trials), which is classified as very hard water. This
proves that Hidden Spring is a reliable source of mineral water.
However, possible errors during the experiment may have
caused by the intrinsic error of the method and typical random
errors including human errors.

Aim
The main objective of the experiment is to determine the “hardness” of a sample of water by
using EDTA to determine the concentration of calcium and magnesium ions.

Introduction
Water hardness is important to fish culture and is a commonly reported aspect of water quality. It
is a measure of the quantity of divalent ions such as calcium, magnesium and/or iron in water.
There are many different divalent salts; however, calcium and magnesium are the most common
sources of water hardness. Hardness is traditionally measured by chemical titration. The
hardness of a water sample is reported in milligrams per litre (same as parts per million, ppm) as
calcium carbonate (mg/l CaCO3). Calcium carbonate hardness is a general term that indicates
the total quantity of divalent salts present and does not specifically identify whether calcium,
magnesium and/or some other divalent salt is causing water hardness. Hardness can be a
mixture of divalent salts. In theory, it is possible to have water with high hardness that contains
no calcium. The determination of water hardness is a useful test that provides a measure of
quality of water for households and industrial uses. Originally, water hardness was defined as the
measure of the capacity of the water to precipitate soap. Hard water is not a health hazard.
People regularly take calcium supplements. Drinking hard water contributes a small amount of
calcium and magnesium toward the total human dietary needs of calcium and magnesium. The
National Academy of Science states that consuming extremely hard water could be a major
contributor of calcium and magnesium to the diet.

The ions involved in water hardness, i.e. Ca2+(aq) and Mg2+(aq), can be determined by titration
with a chelating agent, ethylenediaminetetraacetic acid (EDTA), usually in the form of disodium
salt (H2Y2-). The titration reaction is:

Eriochrome Black T is commonly used as indicator for the above titration. At pH 10, Ca2+(aq) ion
first complexes with the indicator as CaIn+(aq), which is wine red. As the stronger ligand EDTA is
added, the CaIn+(aq) complex is replaced by the CaY2-(aq) complex which is blue. The end
point of titration is indicated by a sharp color change from wine red to blue.

Procedure
The experiment started by preparing all the needed solutions for the study. The solutions
prepared were 500 mL 0.1000 M stock Ethylenediaminetetraacetic acid (EDTA) solution, 100 mL
0.0500 M stock Ca2+ solution, and a 250 mL 1.0 M NH3-NH4+ pH 10 buffer solution. To avoid
confusion, the solutions will be named solutions A, B, and C respectively.
Solution A was prepared by adding approximately 6,0009 grams of Na2H2EDTA * H2O to the
nearest 0.1 milligrams in a 500 mL beaker and adding 400 mL of distilled water. Then the entire
solution was quantitatively transferred in a 500 mL volumetric flask, filling to mark with distilled
water and mixing.
Next, solution B was prepared by adding approximately 0.791 grams of pure CaCO3 (with a
purity of 99.97%) to a 250 mL beaker and adding 40 mL distilled water. HCl was then added to
the solution as it was being heated and at the same time gently stirred. This was done to
dissolve the CaCO3 solids. Upon dissolution, the entire solution was transferred to a 100 mL
volumetric flask, diluted to mark with distilled water and mixed.
Finally, the solution C was prepared by mixing the specified values for NH3 and NH4Cl (in this
case, 57 mL of NH3 and 7.0116 grams of NH4Cl into a volumetric flask, diluted to the mark and
mixed. The pH was tested using a strip of pH paper and adjusted by either adding more acid or
base to attain a pH value of 10.
Additional solutions were also prepared; 250.0 ml .0100 M working EDTA solution from .1 M
EDTA and 50.0 ml .0050 M working standard Ca2+ from the .0500 M Ca2+ solution. These
solutions will be labelled as Solutions A1 and B1 respectively.
The solution A1 will be prepared by getting 25 ml from the .1000 M EDTA and diluting and
storing it to a specified 250 ml volumetric flask. The solution B1 was prepared by getting 5 ml of
the .0500 M Ca2+ solution diluting and storing it to a specified 50 ml volumetric flask.
Standardization of the .01 M EDTA solution started by getting three sets of 10 mL aliquots from
the .0050M CaCO3 solution. 75 mL of distilled water was also added to each of the flasks. Three
mL of the buffer solution was then added to the solution with 6 drops of the EBT indicator before
titration.
The volumes (initial and final) of the titrant were then recorded. The solution was titrated until a
change in color from wine red to a clear blue was observed. This part of the experiment was
done within 3 trials. After doing the standardization, a similar process was done for the analysis
of the blank titration with distilled water to which the same amount of hydroxylation blue indicator
and titrate with the EDTA solution were added. However, instead of 10 mL, 3 sets of 50 mL water
samples were added into 3 separate 250 mL Erlenmeyer flasks before adding 3 mL of the buffer
solution then titrating with the EDTA solution using the EBT as indicator. The color change
observed for both was from wine red to dark blue.

RESULTS AND DISCUSSION

During the preparation of EDTA solution, MgCl2 * 6H2O crystals were added to the dissolved salt
EDTA. It was added to the solution to increase its solubility via diverse ion effect.
The fact that Mg-EDTA has a higher formation constant hence a higher tendency to form
complexes than Ca-EDTA, Mg2+ from EDTA solution can easily displace Ca2+ ions and form
Mg-EDTA complex Since Ca-EDTA has a lower Kf, formation constant, Ca-EDTA is less stable
because there is a greater energy for the complex to form, so adding more Mg2+ ions will make
the endpoint sharper. On the other hand, EDTA is essentially insoluble in water, and will only
dissolve when pH is neutralized to 8. Addition of base, in this experiment NaOH pellets,
facilitates dissolution of acid form of EDTA.

Carbonate errors can cause discrepancies in pH readings so adding HCl while dissolving CaCO3
during the solution preparation is important for all reactions between metal ions and EDTA that
are pH dependent, and for divalent ions, solutions must be kept basic (and buffered) for the
reaction to go to completion [5]. Most ligands are basic and bind to H+ ions throughout a wide
range of pH. Some of these H+ ions are frequently displaced from the ligands (chelating agents)
by the metal during chelate formation, so a buffer was used to hold the pH constant. In this
experiment, NH3-NH4Cl buffer was used since EBT indicator only works when the pH is at 8 to
10, whereas the buffer has a pH equal to 10 [4].
Meanwhile NaOH was present to neutralize the carboxyl groups present in the EDTA crystals
and as such increases its solubility, therefore ensuring its complete dissociation into the solution
[5]
Equations (1), (2), and (3) below display the reaction process the various reactants and ions
undergo to display a color change from wine red to dark blue as well as to display a sharper
endpoint for the titration process.
H2Y2– + Ca2+ → CaY2– + 2H+ (1)
H2Y2– + Mg2+ → MgY2– + 2H+ (2)
H2Y2– + Mg-In → MgY2– + HIn2–+ H+ (3)
where Mg-In = wine red solution
and HIn2–+ = dark blue endpoint
Note how EDTA reacts to both calcium (equation (1)) and magnesium ions (equation (2)) before
the magnesium ions bind to the EBT indicator.
The concentration of the two most common hard water ions, Ca2+ and Mg2+ was then
determined by titrating the water sample with a known chelating agent, EDTA. It was
standardized with CaCO3 thrice and the resulting average concentration of EDTA is 0.0095 M.

Trial 1 2 3
Volume of working 10 10 10
Ca(II) standard, mL

Net volume EDTA, 8 8.5 8.3

mL

M EDTA .0098 .0093 .0095

Average M EDTA .0095

Titer .9566187928

𝑔 𝐶𝑎𝐶𝑂3 (100.09𝑔/𝑚𝑜𝑙)(%𝑝𝑢𝑟𝑖𝑡𝑦)
𝑀 𝑠𝑡𝑜𝑐𝑘 𝐶𝑎2+ =
𝐿𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
(𝑀𝑠𝑡𝑜𝑐𝑘 𝐶𝑎 )(𝑉𝑠𝑡𝑜𝑐𝑘 𝐶𝑎 )
𝑀𝑤𝑜𝑟𝑘𝑖𝑛𝑔 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 =
𝑉𝑤𝑜𝑟𝑘𝑖𝑛𝑔 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑

(𝑀𝑤𝑜𝑟𝑘𝑖𝑛𝑔 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 )(𝑉𝑤𝑜𝑟𝑘𝑖𝑛𝑔 𝑠𝑡𝑎𝑛𝑑𝑎𝑟𝑑 )

𝑀𝐸𝐷𝑇𝐴 =
𝑉𝐸𝐷𝑇𝐴
𝑇 = 𝑀(𝐹𝑊)
During standardization, purple color appeared upon addition of EBT indicator compared to the
expected wine-red color of the solution. This may happen since there are no Mg2+ ions in the
solution, and the indicator only exists as wine-red complex due to the magnesium ions.
On the other hand, the water sample (Hidden Spring) was titrated with the standardized EDTA.
The starting color sample upon addition of EBT indicator was wine red due to the existence of
Mg2+ ions and upon titrating with EDTA, the color gradually changes from wine red to clear blue,
indication that the endpoint is reached, which occurs when Ca2+ ions complexes with EDTA, the
same time the Mg2+ complexes with it sequentially and the Mg-EBT complex breaks as
illustrated in the equation.

When comparing the obtained values above with the theoretical values obtained from the labels
indicated in the water bottle, it can be concluded that errors were still present in the experiment,
however, the objective of the experiment was still achieved, that is to determine the total
hardness of a water sample.
Theoretically, the water sample contained 25 ppm and 35 ppm of both Ca2+ and Mg2+ ions
respectively; and the calculated water hardness (CaCO3 ppm) based on these theoretical values
are 62.44 ppm (from ppm Ca) and 144.10 ppm (from ppm Mg) for a total hardness of 206.54
ppm. Experimentally, the total hardness of water was 248.70 ppm, which according to Table 1,
falls under the very hard category. This fully supports the theoretical category of the Hidden
Spring water sample to fall to the very hard category.
As mentioned, certain errors could have been committed while performing the experiment that
may have affected the overall result, primarily the ppm value of calcium carbonate. Such errors
committed that could have affected the ppm value of CaCO3 are over titration (increase in
VEDTA = increase in ppm CaCO3), the negligence to allow for EDTA to pass through the burette
pre-titration (increase in ppm CaCO3 due to a most likely diluted EDTA titrant), too much EBT
indicator added (indeterminate ppm CaCO3 due to a vague shift in color), too little EBT indicator
added (increase ppm CaCO3 as the time for a color shift will be delayed), actual pH of the
solution is less than 10 (decrease ppm CaCO3 due to the possible precipitation of metal
hydroxides.) The addition of indicator before the 3 mL buffer solution to the analyte may also
affect the overall process as some of the indicator may react with the solution before the buffer
can work for an ideal set-up.

CALCULATIONS

-3
{ 9.878915223x10 M + 9.297802562x10-3M + 9.521845998x10-3M )
AVERAGE M =
𝟑
-3
= 9.566187928𝑥 10 M
CONCLUSIONS
Complexometric titration was utilized to determine the hardness of the 50 mL Hidden Spring
water sample. Water hardness is basically a set of standards used to determine whether a water
sample is suitable for domestic or industrial use. Generally, very hard water is mostly suitable for
drinking and not for industrial use for hard water can; clog pipes due to formation of precipitates
called “scales /mineral deposits” when heated, reduce the life of clothes due to the slimy
film/yellow coating the “scales” form in clothes, and it can further deteriorate the performance of
appliances due to excess mineral deposits. EDTA was used as the titrant because of its
efficiency and stability in forming metal-ion complexes, specifically with the Mg2+ and Ca2+ ions
found in the water sample. Because of various disassociations and formations among the
reactants and ions involved as expressed in equations (1), (2), and (3), a color change from wine
red to dark blue may be observed to determine the MEDTA as well as the ppm CaCO3. Various
errors such as over titration, addition of indicator before buffer (for the analyte), addition of too
much or too little indicator, have influenced the accuracy of the data. Lastly, after determining the
total hardness of the water sample, and after comparing the results from the theoretical values, it
can be concluded that the Hidden Spring water sample is classified with a total hardness that
falls to the category of “very hard” which signifies its high-mineral content and potability as a type
of drinking water.