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 Answer to Question 3: EDTA is used as complexing

determining the hardness of water? agent and titrant because it forms strong 1:1
complexes with metal ions which are Lewis acids. The
Answer to Question 1: Determining water hardness is
coordination complexes formed consist of a central
a useful method of analysis which gives a good
atom and ligands that bind to it. Ligands that attach
measure of the quality of water used in houdeholds
to the metal ion through more than one ligand atom
and industries by determining its components. An
is called a multidentate of chelating ligand. The
example of its industrial significance is that heating
chelating effect ersults to the ormation of more
hard water precipitates out calcium carbonate which
stable metal complexes. EDTA is an important and
causes pipes and boilers to clog, and in order to
the most widely used chelator in analytical chemistry
prevent this, water hardness must be determined [1].
by far as it is able to determine measurements for
Reference: almost all element[1].

[1] Skoog, D.A.; West, D.M.; Holler, F. J.; Crouch, S. R. Reference:

Fundamentals of Analytical Chemistry [Online]. 2004,
[1] Harris, D.C. Quantitative Chemical Analysis
436
[Online]. 2007. 237-240

2. Question 2: What is the classification of

hardness of your water sample (why is it
4. Question 4: Why is EBT used as indicator?
expressed as ppm CaCO3)?
Why are MgCl2∙6H2O crystals added to the
Answer to Question 2: The hardness of ewater is titrant?
equivalent to the concentration of calcium and
Answer to Question 4: Usually, water hardness is
magnesium ions it contains. It is expressed in ppm of
determined through EDTA titration after the sample
CaCO3 because the total concentration of all has buffered to pH 10. Magnesium forms the least
multivalent cations in the water is equal to the stable complex with EDTA among all the common
concentration of calcium carbonate. multivalent cations that are present in typical water
samples and is not titrated until all of the other
Reference: cations in the sample has formed complexes with the
addition of titrant. This makes it fit fot a magnesium
[1] Skoog, D.A.; West, D.M.; Holler, F. J.; Crouch, S. R. ion indicator such as EBT to be an indicator in
Fundamentals of Analytical Chemistry [Online]. 2004, , determining water hardness.
436
MgCl26H2O crystals were added in order to yield a
sharper end point. In the experiment, EDTA is used to
3. Question 3: Why is EDTA used as a determine the concentration of calcium ions,
complexing agent and titrant? 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 6. Question 6: What is the relationship of pH
stable than Mg-EDTA, calcium ions will displace and feasibility of titration using EDTA for
magnesium ions[1]. Magnesium ions will be freed and cation analysis?
titrated since the concentration of free magnesium
ions is equal to that of calcium ions. Answer to Question 6: The desired form of EDTA that
will form a complex with metal ions is produced at
Reference: high pH levels. This form is the most deproptonated
form of EDTA since as pH is increased, the hydrogens
[1] Harris, D.C. Quantitative Chemical Analysis
bound to its carboxyl groups are freed. At low pH
[Online]. 2007. 237-257
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
5. Question 5: What are the pertinent chemical complexes with metal cations for analysis.
equations involved during titration?
Reference:
Answer to Question 5: In making the standard, the
following equation was involved: [1] Skoog, D.A.; West, D.M.; Holler, F. J.; Crouch, S. R.
Fundamentals of Analytical Chemistry [Online]. 2004,
𝐶𝑎𝐶𝑂3 + 2𝐻𝐶𝑙 → 𝐶𝑎𝐶𝑙2 + 𝐶𝑂2 + 𝐻2 𝑂(1) 237-257
where calcium carbonate was dissolved, forming
calcium ions that will be the basis of determining the
exac concentration of EDTA. 7. Question 7: What are other applications of
EDTA complexation?
In the sample analysis, the following reactions
occured during titration of water sample with EDTA:
Answer to Question 7: EDTA complexation is also
𝐶𝑎2+ + 𝐸𝐷𝑇𝐴4− → 𝐶𝑎𝐸𝐷𝑇𝐴2− (2) important in other industries such as cosmetics.
where the calcium ions present in the sample react EDTA is often found in cosmetic and personal care
with the titrant to form a calcium-EDTA complex. The produts such as mositurizers, cleansing products,
end point of Equation 2 was determined by the shampoo and conditioners. EDTA binds to metal
addition of EBT as seen in the equation below: ions and inactivates them, preventing them from
deteriorating the said products[1]. Moreover, EDTA is
𝑀𝑔𝐼𝑛 + 𝐸𝐷𝑇𝐴4− → 𝑀𝑔𝐸𝐷𝑇𝐴2− + 𝐼𝑛2−(3) used in agriculture as micronutrient fertilizers. This
where the solution shows a color change from wine metallic chelate allows for the supplication of
red to blue. Due to the lack of stability of calcium metallic ions which are mineral needed by plants for
complex with the presence of EBT indicator, their growth[2].
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 Reference:
its amount shall be the basis of the titration end
[1] Cosmetics Info. Disodium EDTA.
point. This is also known as displacement
https://cosmeticsinfo.org/ingredient/disodium-edta
titration .
[1]
(4) (accessed Sept. 7, 2019).
𝐶𝑎𝐼𝑛 + 𝑀𝑔2− → 𝐶𝑎𝑌 2− + 𝑀𝑔𝐼𝑛−
[2] SMART Fertilizer Management. Chelated
Fertilizers and their Use.
https://www.smart-fertilizer.com/articles/chelate-fert
ilizers (accessed Sept. 7, 2019).
Reference:

[1] Harris, D.C. Quantitative Chemical Analysis

[Online]. 2007. 237-257
8. Question 8: What is the difference between 10. What is the effect of using too much buffer
the experimental and the stated value in in the analysis of Ca and Mg during EDTA
your water sample? titration?

Answer to Question 8: The experimental value for the

hardness of the water sample turned out to be Answer to Question 10: Too much buffer in the
145.83 ppm. However the theoretical value was at analysis will result to a stronger resistance to
176.2 ppm. This gave a relative percent error of changes in pH. In this case, a weaker endpoint will be
about 17%. observed. The addition of buffer must be of
appropriate amounts to acheive a sharp end point [1].

Reference:
9. Question 9: What is the rationale behind
[1] Harris, D.C. Quantitative Chemical Analysis
doing the analysis of Ca and Mg at pH 10?
[Online]. 2007. 237-257

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 11. What is the correlation between the stability
not react with the metal ions. Divalent ions have to of MgY2-, CaY2-, MgIn-, and CaIn
be kept basic (pH 10) to drive the reaction into corresponding Kf values?
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. 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
Figure 1. Ladder Diagram of EDTA
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
Reference:
data may have more precision than accuracy.
[1] Harris, D.C. Quantitative Chemical Analysis
[Online]. 2007. 237-257