Quantitative Determination of Total Hardness in Drinking Water
by Complexometric Titration
C. Inao
Institute of Chemistry, College of Science, University of the Philippines
Date Submitted: 9 September 2019
Instructor’s Name: M. Fajiculay
1. Question 1: What is the significance of
determining the hardness of water?
Answer to Question 1: Determining water hardness is
a useful method of analysis which gives a good
measure of the quality of water used in houdeholds
and industries by determining its components. An
example of its industrial significance is that heating
hard water precipitates out calcium carbonate which
causes pipes and boilers to clog, and in order to
prevent this, water hardness must be determined [1].
Reference:
[1] Skoog, D.A.; West, D.M.; Holler, F. J.; Crouch, S. R.
Fundamentals of Analytical Chemistry [Online]. 2004,
436
2. Question 2: What is the classification of
hardness of your water sample (why is it
expressed as ppm CaCO3)?
Answer to Question 2: The hardness of ewater is
equivalent to the concentration of calcium and
magnesium ions it contains. It is expressed in ppm of
CaCO3 because the total concentration of all
multivalent cations in the water is equal to the
concentration of calcium carbonate.
Reference:
[1] Skoog, D.A.; West, D.M.; Holler, F. J.; Crouch, S. R.
Fundamentals of Analytical Chemistry [Online]. 2004, ,
436
3. Question 3: Why is EDTA used as
complexing agent and titrant?
Answer to Question 3: EDTA is used as complexing
agent and titrant because it forms strong 1:1
complexes with metal ions which are Lewis acids. The
coordination complexes formed consist of a central
atom and ligands that bind to it. Ligands that attach
to the metal ion through more than one ligand atom
is called a multidentate of chelating ligand. The
chelating effect ersults to the ormation of more
stable metal complexes. EDTA is an important and
the most widely used chelator in analytical chemistry
by far as it is able to determine measurements for
almost all element[1].
Reference:
[1] Harris, D.C. Quantitative Chemical Analysis
[Online]. 2007. 237-240
4. Question 4: Why is EBT used as indicator?
Why are MgCl2∙6H2O crystals added to the
titrant?
Answer to Question 4: Usually, water hardness is
determined through EDTA titration after the sample
has buffered to pH 10. Magnesium forms the least
stable complex with EDTA among all the common
multivalent cations that are present in typical water
samples and is not titrated until all of the other
cations in the sample has formed complexes with the
addition of titrant. This makes it fit fot a magnesium
ion indicator such as EBT to be an indicator in
determining water hardness.
MgCl26H2O crystals were added in order to yield a
sharper end point. In the experiment, EDTA is used to
a determine the concentration of calcium ions,
however it is slow in binding these ions, so another
metal ion was added in the formof magnesium salt
to form a Mg-EDTA complex. Since Ca-EDTA is more
stable than Mg-EDTA, calcium ions will displace
magnesium ions[1]. Magnesium ions will be freed and
titrated since the concentration of free magnesium
ions is equal to that of calcium ions.
Reference:
[1] Harris, D.C. Quantitative Chemical Analysis
[Online]. 2007. 237-257
5. Question 5: What are the pertinent chemical
equations involved during titration?
Answer to Question 5: In making the standard, the
following equation was involved:
𝐶𝑎𝐶𝑂3 + 2𝐻𝐶𝑙 → 𝐶𝑎𝐶𝑙2 + 𝐶𝑂2 + 𝐻2 𝑂(1)
where calcium carbonate was dissolved, forming
calcium ions that will be the basis of determining the
exac concentration of EDTA.
In the sample analysis, the following reactions
occured during titration of water sample with EDTA:
𝐶𝑎2+ + 𝐸𝐷𝑇𝐴4− → 𝐶𝑎𝐸𝐷𝑇𝐴2− (2)
where the calcium ions present in the sample react
with the titrant to form a calcium-EDTA complex. The
end point of Equation 2 was determined by the
addition of EBT as seen in the equation below:
𝑀𝑔𝐼𝑛 + 𝐸𝐷𝑇𝐴4− → 𝑀𝑔𝐸𝐷𝑇𝐴2− + 𝐼𝑛2−(3)
where the solution shows a color change from wine
red to blue. Due to the lack of stability of calcium
complex with the presence of EBT indicator,
magnesium, which is stable with EBT, was used to
displace calcium and allow a Mg-EDTA complex to
form. Magnesium ions will late on be displaced and
its amount shall be the basis of the titration end
point. This is also known as displacement
titration .
[1]
(4)
𝐶𝑎𝐼𝑛 + 𝑀𝑔2− → 𝐶𝑎𝑌 2− + 𝑀𝑔𝐼𝑛−
Reference:
[1] Harris, D.C. Quantitative Chemical Analysis
[Online]. 2007. 237-257
6. Question 6: What is the relationship of pH
and feasibility of titration using EDTA for
cation analysis?
Answer to Question 6: The desired form of EDTA that
will form a complex with metal ions is produced at
high pH levels. This form is the most deproptonated
form of EDTA since as pH is increased, the hydrogens
bound to its carboxyl groups are freed. At low pH
levels, carboxyl groups are not dissociated, making
EDTA insoluble in water[1]. Therefore, increasing the
pH also increases its solubility and allows it to form
complexes with metal cations for analysis.
Reference:
[1] Skoog, D.A.; West, D.M.; Holler, F. J.; Crouch, S. R.
Fundamentals of Analytical Chemistry [Online]. 2004,
237-257
7. Question 7: What are other applications of
EDTA complexation?
Answer to Question 7: EDTA complexation is also
important in other industries such as cosmetics.
EDTA is often found in cosmetic and personal care
produts such as mositurizers, cleansing products,
shampoo and conditioners. EDTA binds to metal
ions and inactivates them, preventing them from
deteriorating the said products[1]. Moreover, EDTA is
used in agriculture as micronutrient fertilizers. This
metallic chelate allows for the supplication of
metallic ions which are mineral needed by plants for
their growth[2].
Reference:
[1] Cosmetics Info. Disodium EDTA.
https://cosmeticsinfo.org/ingredient/disodium-edta
(accessed Sept. 7, 2019).
[2] SMART Fertilizer Management. Chelated
Fertilizers and their Use.
https://www.smart-fertilizer.com/articles/chelate-fert
ilizers (accessed Sept. 7, 2019).
8. Question 8: What is the difference between
the experimental and the stated value in
your water sample?
Answer to Question 8: The experimental value for the
hardness of the water sample turned out to be
145.83 ppm. However the theoretical value was at
176.2 ppm. This gave a relative percent error of
about 17%.
9. Question 9: What is the rationale behind
doing the analysis of Ca and Mg at pH 10?
Answer to Question 9: Reaction between metal ions
and EDTA are dependent on pH. Carboxyl groups in
EDTA do not dissociate at low pH, and will therefore
not react with the metal ions. Divalent ions have to
be kept basic (pH 10) to drive the reaction into
completion.The certain form of EDTA, Y4-, needed to
react with the metal ions is only present in high pH
levels[1], hence the pH for analysis must be kept at 10.
Figure 1. Ladder Diagram of EDTA
Reference:
[1] Harris, D.C. Quantitative Chemical Analysis
[Online]. 2007. 237-257
10. What is the effect of using too much buffer
in the analysis of Ca and Mg during EDTA
titration?
Answer to Question 10: Too much buffer in the
analysis will result to a stronger resistance to
changes in pH. In this case, a weaker endpoint will be
observed. The addition of buffer must be of
appropriate amounts to acheive a sharp end point [1].
Reference:
[1] Harris, D.C. Quantitative Chemical Analysis
[Online]. 2007. 237-257
11. What is the correlation between the stability
of MgY2-, CaY2-, MgIn-, and CaIn
corresponding Kf values?
12. Why is NaOH added to the EDTA solution if
the disodium-EDTA crystals do not dissolve?
Answer to Question 12: NaOH is a base and adding it
to the EDTA solution allows for the rise in pH
resulting to dissociated carboxyl groups, releasing
H+ into the solution. This makes the crystals more
soluble[1].
Reference:
[1] Harris, D.C. Quantitative Chemical Analysis
[Online]. 2007. 237-257
13. How do the results of your group correlate
to those obtained by the other groups?
Answer to Question 13: The values obtained by other
groups for the hardness of water in 2 to 3 trials were
not far from our group at the value of around 144
ppm on average. The data points were relatively
close to each other, which is why the experimental
data may have more precision than accuracy.