Title;

Determination of Total Water Hardness and calcium content using EDTA Titration

Abstract:

This experiment aimed to determine the total hardness and calcium content of water using
ethylenediaminetetraacetic acid (EDTA) titration. Part A involved the standardization of EDTA
solution by titrating a o.3033g solution of calcium carbonate primary standard with an average
EDTA volume of 19.10 mL at pH 10 using eriochrome black T as an indicator. In Part B, total
hardness content was determined by titrating 100.0mL water sample with the standardized
EDTA solution and at the end point, an average EDTA volume of 4.4 mL was obtained. The
calculated molarity of EDTA solution was found to be 0.0082M which was used to calculate the
total hardness found to be 36 mg/L as CaCO₃, classifying the water as soft. The report also
discusses potential sources of errors in the experimental procedures and suggests remedies to
enhance accuracy and reliability in future analyses.

Introduction:

Water quality is a critical environmental factor evaluated through various parameters, one of
which is water hardness. Water hardness is primarily caused by the presence of polyvalent
cations, particularly calcium (Ca²⁺) and magnesium (Mg²⁺), which react with soap to form
precipitates and reduce soap effectiveness. Hard water also contributes to scale formation in
plumbing systems and household appliances. In natural water sources, hardness varies and is
commonly measured as the sum of calcium and magnesium concentrations, expressed in
milligrams of calcium carbonate (CaCO₃) per liter.

This experiment uses complexometric titration, specifically with ethylenediaminetetraacetic acid

(EDTA), to determine water hardness. EDTA is a chelating agent that forms stable complexes
with metal ions, such as Ca²⁺ and Mg²⁺, enabling their quantification. The process is conducted
 in two parts: total hardness determination at pH 10 and selective calcium determination at pH 12.
The difference between the two titrations provides the magnesium concentration.

The U.S. Geological Survey (USGS) classifies water hardness as follows: soft (0-60 mg/L),
moderately hard (61-120 mg/L), hard (121-180 mg/L), and very hard (>180 mg/L). The accurate
measurement of water hardness is essential for both environmental assessments and industrial
applications, making complexometric titration with EDTA a valuable technique.

This experiment introduces students to the preparation and standardization of an EDTA solution
and the determination of calcium and magnesium concentrations in water samples. The method
provides a comprehensive evaluation of water hardness, a key indicator of water quality.

Materials and Procedure:

1. 0.9005g of disodium EDTA was weighed and transferred into a 250 mL volumetric flask.
Deionized (DI) water was added to fill the flask halfway, followed by the addition of 3.00 mL of
3 M sodium hydroxide (NaOH) solution. The solution was gently swirled to dissolve the EDTA,
which took 15 minutes. The solution was then diluted to the mark with DI water and mixed
thoroughly.
2. A calcium carbonate (CaCO₃) primary standard solution was prepared by dissolving 0.3133g of
CaCO₃ in a 500 mL volumetric flask. A 25.00 mL aliquot of the standard solution was pipetted
into each of three 250 mL Erlenmeyer flasks. 1 mL of ammonia/ammonium chloride buffer was
added to adjust the pH to 10. Then, 2 drops of eriochrome black T indicator were added to each
flask. The solution was titrated with the prepared EDTA solution until the color changed from
violet to pale blue, indicating the endpoint. The endpoint volumes were recorded to the nearest
0.01 mL.
3. A 100.00 mL sample of water was taken and adjusted to pH 10 using ammonia/ammonium
chloride buffer. 3 drops of eriochrome black T indicator were added, turning the solution red.
The sample was titrated with EDTA until the color changed to blue. The total volume of EDTA
required to reach the endpoint was recorded. The titration was repeated two times for accuracy.
4. A blank titration was performed using 100 mL of DI water with the same buffer and indicator
reagents. This titration ensured no measurable amounts of calcium or magnesium ions were
present in the water used for dilutions.

FOR PART A
Table of results
Titre value 1 2 3
Final buret rdg( mL) 19.10 18.90 19.10
Initial buret rdg( mL) 0.00 0.00 0.00
Volume ofEDTA(mL) 19.10 18.90 19.10
Blank titration;
Volume of EDTA used = 0.00mL
Average volume of EDTA used = 19.10 mL

Calcium (Ca): 40.08 g/mol

Carbon (C): 12.01 g/mol

Oxygen (O): 16.00 g/mol (x3)

Molar mass of CaCO₃ = 40.08 + 12.01 + (16.00 × 3) = 100.09 g/mol

Mass of CaCO₃ used : 0.3133 g

mass 0.3033
Moles of CaCO₃= = ≈ 0.00313 moles
molecular mass 100.09

500 mL contain 0.00313 moles of CaCO₃

25× 0.00313
25.Oml contain = 0.0001565 mole of CaCO₃
500
According to the stoichiometry of the reaction between EDTA and calcium ions, one mole of
EDTA reacts with one mole of Ca²⁺. Thus, the moles of EDTA used will be equal to the moles
of CaCO₃:

Moles of EDTA=0.0001565 moles.

Volume of EDTA=19.1 mL= 0.0191 L
moles of solute
Molarity (M)=
volume of t h e solution∈litres
0.0001565
Molarity of EDTA= ≈0.0082 M
0.0191

FOR Part B

Table of results

Titre value 1 2 3
Final buret rdg( mL) 4.50 8.90 13.30
Initial buret rdg( mL) 0.00 4.50 8.90
Volume ofEDTA(mL) 4.50 4.40 4.40

Blank titration; volume of EDTA used = 0.00mL

Average volume of the EDTA used = 4.40mL

Moles of EDTA used =Molarity×Volume (L)

Moles of EDTA=0.0082M×0.0044L=0.000036moles

In the titration, each mole of EDTA reacts with one mole of Ca²⁺ and one mole of Mg²⁺. Thus,
the moles of total hardness (as CaCO₃) can be found as follows:

Moles of total hardness = Moles of EDTA=0.000036moles.

Using the molar mass of CaCO₃ (100.09 g/mol):

Mass of CaCO₃=Moles of total hardness×Molar mass of CaCO₃ Mass of CaCO₃=0.000036
mol×100.09 g/mol ≈ 0.0036 g

To express total hardness as mg/L, we consider that the volume of the water sample titrated was
100.00 mL (or 0.1 L):

mass(g)
Total hardness (mg/L)= ×1000
volume (L)
0.0036
Total hardness (mg/L)= × 1000 =36 mg/L
0.1

Discussion:

The experiment aimed to determine the total water hardness, calcium hardness, and magnesium
hardness in a water sample using complexometric titration with EDTA. The results obtained
from the titration volumes were converted to water hardness values expressed in milligrams per
liter (mg/L) of calcium carbonate (CaCO₃). The average volumes used in the titration for both
EDTA standardization (Part A) and total hardness (Part B) provided critical data to evaluate the
concentrations of calcium and magnesium ions in the water sample.

The total hardness, which includes both calcium and magnesium ions, was calculated to be 36
mg/L as CaCO₃. This value represents the combined effect of Ca²⁺ and Mg²⁺ ions present in
the water. According to the U.S. Geological Survey classification, water hardness is categorized
as follows:

Soft: 0-60 mg/L as CaCO₃

Moderately hard: 61-120 mg/L as CaCO₃

Hard: 121-180 mg/L as CaCO₃

Very hard: >180 mg/L as CaCO₃

Based on this classification, the total hardness of 36 mg/L indicates that the water sample can be
classified as soft. The low hardness suggests that the water sample contained low concentrations
of calcium and magnesium ions, and it may have come from a source like rainwater or water that
has undergone softening treatment.

The total hardness is an important water quality parameter, as hard water can cause scale
formation in plumbing and reduce the effectiveness of soaps and detergents. In this case, the
sample would likely not have these issues due to its relatively low hardness level.

The calcium content in the water sample can be determined by performing a selective titration at
a pH of 12. At this pH, magnesium ions precipitate as magnesium hydroxide (Mg(OH)₂),
leaving only calcium ions (Ca²⁺) in solution. The titration is carried out using EDTA, a chelating
agent that forms stable complexes with calcium ions. A few drops of Calcon indicator are added,
and the EDTA solution is titrated until the color changes from red to blue, indicating the
endpoint. The volume of EDTA used is then used to calculate the calcium concentration in the
sample.

Sources of Errors

Several sources of errors could affect the accuracy of the total hardness determination in this
procedure. Firstly, inaccurate measurements during the preparation of the EDTA solution, such
as weighing errors or improper dilution, could lead to incorrect molarity calculations.
Additionally, fluctuations in pH during titration could alter the binding efficiency of EDTA to
calcium and magnesium ions, affecting endpoint detection. Human errors, such as misreading the
burette or inconsistencies in adding the indicator, could further introduce variability in results.
Finally, the presence of interfering ions in the water sample could lead to erroneous color
changes and misinterpretation of the endpoint.

To minimize these errors, precise weighing and calibration of volumetric equipment should be
conducted to ensure accurate preparation of the EDTA solution. Regular pH monitoring during
the titration, using a calibrated pH meter, can help maintain the optimal pH range, enhancing the
accuracy of the endpoint detection. Careful training and practice in titration techniques will
reduce human errors, while conducting control experiments with known hardness standards can
help identify any interference from other ions. Additionally, running multiple trials and
 calculating average results will increase the reliability and validity of the findings, allowing for
more accurate conclusions regarding water hardness.

Conclusion:

The experiment successfully determined the total hardness of the water sample, which was found
to be 36 mg/L, falling within the soft water range. The calculated molarity of EDTA was 0.0082
M, and the titration results provide a reliable estimation of the calcium and magnesium content in
the water. Despite some experimental uncertainties, the methodology was effective in
quantifying water hardness, a key parameter for assessing water quality.
REFERENCES

1. Daniel C. Harris, Quantitative Chemical Analysis (8th Edition, or 7th Edition for older
resources), W.H. Freeman and Company.
2. U.S. Geological Survey (USGS), Water Hardness Classification and Its Effects on Water
Quality.
3. Christian, G.D., Analytical Chemistry (6th Edition), John Wiley & Sons..
4. Clesceri, L. S., Greenberg, A. E., & Eaton, A. D. (Eds.), Standard Methods for the
Examination of Water and Wastewater (22nd Edition), American Public Health Association.
5. Skoog, D. A., West, D. M., & Holler, F. J., Fundamentals of Analytical Chemistry (9th
Edition), Brooks Cole.