UNIVERSITY OF MINES AND TECHNOLOGY (UMaT),

TARKWA
SCHOOL OF PETROLEUM STUDIES
(SPeTS)
DEPARTMENT OF CHEMICAL AND PETROCHEMICAL
ENGINEERING

A REPORT ON THE DETERMINATION OF WATER HARDNESS BY

COMPLEXOMETRIC TITRATION
(EXPERIMENT 3)
BY
ANIM POKUAH KAKARI WILHELMINA
(SPE.41.014.022.22)
RP 2
GROUP 4
COURSE NAME : CHEMISTRY LABORATORY PRACTICES
COURSE CODE: RP 273
COURSE LECTURER: DR. AMI JOHANNES
DATE: 15TH FEBRUARY, 2024
TABLE OF CONTENTS
INTRODUCTION 1
PURPOSE OF EXPERIMENT 3
APPARATUS FOR THE EXPERIMENT 4
USES OF APPARATUS 4
PRECAUTIONS 5
PROCEDURE 6
DATA TABLE 8
RESULTS AND DISCUSSION 11
RECOMMENDATIONS 13
CONCLUSION 14
REFERENCES 15
ANSWERS TO POST LAB 16

i
INTRODUCTION

Water hardness refers to the concentration of dissolved minerals, primarily calcium

and magnesium ions, in water. It is a crucial parameter in various industrial,
environmental, and domestic applications, as it can affect the performance of water
systems and the quality of products. Hard water can lead to scaling in pipes,
reduced effectiveness of detergents, and undesirable taste in drinking water.
Complexometric titration is a widely used analytical technique for the
determination of water hardness. In this method, a chelating agent, typically
ethylenediamminetetraacetic acid (EDTA), forms stable complexes with metal ions
present in water sample. The titration involves the gradual addition of a
standardized EDTA solution to the water sample until all the metal ions are
complexed, resulting in a sharp color change of the indicator.
This experiment utilized Complexometric titration as a method to determine the
endpoint of titration, indicated by the formation of a colored complex.
Complexometric titration stands out as a reliable technique for measuring total
water hardness. At a pH of approximately 10, EDTA readily reacts with both
calcium and magnesium ions in a 1:1 molar ratio. Calcium, having a slightly
higher stability constant for its complex, reacts before magnesium. The experiment
aimed to ascertain the water hardness, expressed in milligrams of calcium
carbonate(CaCO3 ) per litre of water.
Ethylenediamminetetraacetic acid (EDTA) serves as the chelating agent, binding
metal ions like calcium, magnesium, lead and iron, forming complex ions through
six bonds. These electron bonding groups within the complex are termed ligands.
Additionally, EDTA finds application in food preservation and color retention.
Eriochrome Black T indicator facilitated the identification of the endpoint,
indicating complete chelation of calcium ions by EDTA, evidenced by the solution
turning blue from the pink complex formed. The reaction equation is represented
as;
EDTA(aq) + Ca(aq) + 2H(aq) H2(aq) + CaEDTA(aq)
Ammonium chloride acted as a buffer to maintain calcium ions in the solution.
Water hardness is classified into two types: temporary and permanent. Temporary

1
hardness stems from the presence of bicarbonate ions(HCO3-) and can be alleviated
by boiling to remove the CO2 gas or through the use of water softeners, albeit
resulting in elevated sodium levels. Permanent hardness arises from yje presence
of calcium, magnesium, ferric, sulphate and bicarbonate ions presenting a lasting
challenge without feasible remedies.
In this report, we will outline the experimental procedure, including sample
preparation, titration technique and data analysis. Additionally, we will discuss the
principles behind Complexometric titration and significance of water hardness in
various applications. Finally, we will present our results and discuss their
implications.

2
PURPOSE OF EXPERIMENT

The objective of this experiment is to determine the hardness of water

samples using Complexometric titration with EDTA as the titrant. By titrating the
water sample with a known concentration of EDTA solution and monitoring the
color change using a suitable indicator that is Eriochrome Black T,the
concentration of calcium and magnesium ions can be quantified, thus determining
the total hardness of the water sample.

3
APPARATUS FOR THE EXPERIMENT

 Beaker
 Dropper
 Volumetric flask
 Erlenmeyer flask
 Well water
 River water
 Eriochrome Black T indicator
 Measuring cylinder
 Tap water
 Borehole water
 Analytical balance

USES OF APPARATUS

Beaker: Utilized for containing both liquid and solid samples during
experimentation.
Burette: Employed to precisely measure the volume of dispensed substances.
Dropper: Utilized for transferring small quantities of liquids with precision.
Erlenmeyer flask: Used for heating and storing liquids securely during
experiments.
Measuring cylinder: Employed for accurate volume measurement, with a
calibration error of 1% at full scale, enabling precision up to 0.1mL at the 10mL
mark.
Volumetric flask: Essential for the precise preparation of chemical solutions to the
specific concentrations.

4
PRECAUTIONS

 Wear lab coats, safety googles and gloves at all times to protect against
potential chemical splashes and spills.
 Exercise caution when handling chemicals like ethylenediamminetetraacetic
acid (EDTA) and indicator solutions. Avoid direct skin contact and inhalation
of vapors.
 Clean and dry all glassware thoroughly before use to prevent contamination of
water samples and titrant solutions.
 Dispose of chemical waste according to the laboratory guidelines and
regulations to prevent environmental contamination and ensure safety.
 Adhere to the experimental protocol outlined in the laboratory manual or
provided by the instructor, and seek clarification if unsure about any
procedures or precautions
 Verify the accuracy and precision of laboratory equipment, such as pH meters
and balances, before conducting experiments to obtain reliable results.

5
PROCEDURE

To conduct this experiment, gather the following materials:

0.01M EDTA solution and a pH 10.00 ammonia buffer.

PREPARATION OF 0.01M EDTA SOLUTION

Hardness of water is determined by titrating with a standard solution of
ethylenediamminetetraacetic acid(EDTA) which is a complexing agent. Since
EDTA is insoluble in water, the disodium salt of EDTA is taken for thus
experiment. Hence we calculate the molecular weight of the disodium salt of
EDTA using the chemical formula; Na2H2C10H12O8N2.2H2O.
Molecular weight = (2 x 23) + (2 x 1) + (10 x 12) + ( 12 x 1) + (8 x 16) + (2 x 14)
+ 2(2 x 1 + 16)
= 372.24g/mol
Determine the concentration of EDTA:
Concentration = 1mol/L = 0.01 mol/L
Concentration x molecular weight = 0.01 x 372.24 = 3.7224g/L. We adjust the
mass for the experiment based on the volume of the flask:
3.7224
Actual mass = 4
= 0.9306g

A pH 10 ammonia buffer was prepared by mixing ammonia solution with

water and adjusting the pH using hydrochloric acid. The pH was then verified
using a pH meter. The various water samples collected were well water, river water,
borehole and tap water. Each was collected into a clean container and labeled for
easy identification. Subsequently, 50mL of each water sample was measured using
a measuring cylinder was transferred into separate conical flasks. To each flask,
1.0mL of pH ammonia buffer and 4 drops of Eriochrome Black T indicator was
added.
For the titration process, the burette was filled with the 0.01M EDTA solution,
ensuring it was positioned above the 0.00mL mark. A clean and dry beaker was
placed under the burette, and the EDTA solution was allowed to flow slowly until
the bottom of the meniscus aligned precisely with the 0.00mL mark when viewed

6
at eye level. The solution in the conical flask was then titrated against the 0.01M
EDTA solution, with a drop-by-drop flow being permitted.
Observing the color change from pink-red to blue at equivalence point, the
endpoint values were recorded and tabulated accordingly for each water sample.
The water hardness in terms parts per million was also calculated for each water
sample.

7
DATA TABLE

FIRST SAMPLE: RIVER WATER

Trial # 1 2 3
Final volume (mL) 4.50 4.50 4.70
Initial volume 0.00 0.00 0.00
(mL)

4.50 + 4.50+ 4.70

Average volume of EDTA = 3

= 4.56mol
����� �� ��2+ �������� �� ���� × ������ �� ����
1�
= 50�� �� �����
0.01� × 4.56��
= 50���

= 9.12 x 10-4M
(��� ��2+ ) × (1��� ����3) × ( 100.1 ����3 ) × (103 )
Hardness of river water in ppm = (1�) × (1 ��� ��2+ ) × (1 ��� ����3 ) × 1�

9.12 × 10−4 ��� � 1 × 100.1 × 103

= 1 × 1× 1 × 1

= 91.2912ppm

SECOND SAMPLE: TAP WATER

Trial # 1 2 3
Final volume (mL) 5.40 5.50 5.70
Initial volume 0.00 0.00 0.00
(mL)

5.40 + 5.50 + 5.70

Average volume of EDTA = 3

= 5.53mL
����� �� ��2+ �������� �� ���� × ������ �� ����
1�
= 50�� �� �����
0.01� × 5.53��
= 50��

= 1.106 x 10-3M

8
Hardness of tap water in ppm;
(��� ��2+ ) × (1 ��� ����3 ) × (100.1����3 ) × (103)
Ppm CaCO3 = (1�) × (1�����2+ ) × (1 ��� ����3 ) × 1�

1.106 × 10−3 × 1 × 100.1 ×103

= 1 × 1 ×1 × 1

= 110.7106ppm

THIRD SAMPLE: WELL WATER

Trial # 1 2 3
Final volume (mg) 5.00 5.20 5.40
Initial volume 0.00 0.00 0.00
(mg)

5.00 + 5.20 + 5.40

Average volume of EDTA used = 3

= 5.20mL
����� �� ��2+ �������� �� ���� × ������ �� ����
1�
= 50�� �� �����

����� �� ��2+ 0.01 × 5.20

1�
= 50

= 1.04 x 10-3M
Hardness of well water in ppm;
( ��� ��2+ ) × (1 ��� ����3 ) × (100.1 ����3) × (103 )��
Ppm CaCO3 = (1�) × (1 ��� ��2+ ) × ( 1 ��� ����3 ) × (1�)

1.04 × 10−3 × 1 × 100.1 × 103

= 1 × 1 × 1 ×1

= 104.104ppm

FOURTH SAMPLE: BOREHOLE WATER

Trial # 1 2 3
Final volume (mL) 5.90 6.00 6.20
Initial volume 0.00 0.00 0.00
(mL)

5.90 + 6.00 + 6.20

Average volume of EDTA used = 3

= 6.03mL

9
 ����� �� ��2+ �������� �� ���� � ������ �� ����
1�
= 50�� �� �����

����� �� ��2+ 0.01 × 6.03

1�
= 50

= 1.206 x 10-3 M
Hardness of borehole water in ppm;
(��� ��2+ ) × (1 ��� ����3 ) × ( 100.1 ����3 ) × (103)
Ppm CaCO3 = (1�) × (1 ��� ��2+ ) × (1 ��� ����3 ) × (1�)

1.206 × 10−3 × 1 × 100.1 × 103

= 1×1×1×1

= 120. 7206ppm

10
RESULTS AND DISCUSSION

The results obtained in this experiment were quite satisfactory. The results
obtained from the Complexometric titration indicate that both borehole water and
tap water exhibit significant levels of water hardness compared to river and well
water, as evidenced by the amount of EDTA solution required to reach the end
point. Water hardness is typically categorized within a numerical range, with soft
water falling between 0 and 75 ppm, moderately hard between 75 and 150ppm,
hard between 150 and 300ppm and anything exceeding 300ppm considered very
hard. In this experiment, our fell within the moderately hard range of the scale.
The titration of river water yielded a water hardness of 91.2912ppm CaC03.
This level of hardness may be attributed to the geological composition of the
surrounding area, with minerals leaching into the water from the rocks and soil.
The water hardness of well water was measured to be 104.104ppm CaCO3.
The lower hardness could be due to differences in groundwater sources and aquifer
characteristics.
Titration of tap water resulted in a water hardness of 110.7106ppm CaCO3.
This value falls within the range of moderately hard water, which may be
influenced by the treatment process and the distribution system of the municipal
water supply.
Borehole water exhibited the highest water hardness among the samples
tested, with a value of 120.706ppm CaCO3. this elevated hardness may be
attributed to the deeper groundwater source and the presence of dissolved minerals
in the aquifer.
Reflecting on the experiment, it became evident that adding more indicator
at the beginning of the titration process woukd have been beneficial as in some
trials less than the required 4-5 drops were used. In one trial, the solution did not
turn blue initially, indicating that the endpoint had already been surpassed. By
adding additional indicator, the color changed promptly to blue, leading to more
accurate results in subsequent trials.
Additionally, distinguishing between violet and blue color chanes proved
challenging at times, highlighting the importance of a more distinct color transition
to ensure precise endpoint determination in future experiments.

11
 Overall, the results highlight the variability of water hardness among
different water sources, which can have implications for various applications such
as household water use, industrial purposes, and agricultural practices.
Understanding the water quality characteristics of each source is essential for
effective water management and treatment strategies.

12
RECOMMENDATIONS

In light of the findings and experiences gained from the Complexometric

titration experiment for the determination of water hardness, several
recommendations emerge to enhance the robustness and efficacy of future
experiments in this area.
Firstly, it is imperative to establish a standardized protocol encompassing all
aspects of the experiment, including the preparation of reagents, titration
procedures, and data analysis techniques. This protocol should be meticulously
documented and adhered to by all laboratory personnel to ensure consistency and
reproducibility across experiments. By implementing a standardized protocol,
variations in experimental procedures can be minimized.
Furthermore, careful consideration should be given to the selection of
indicators used in the titration process. While Eriochrome Black T is commonly
employed for the determination of water hardness, alternative indicators may offer
improved sensitivity and specificity, particularly in cases where subtle color
changes are difficult to discern.
Moreover the importance of conducting multiple trials for each water sample
cannot be overstated. By replicating the titration process several times and
calculating the average water hardness, the impact of random errors and variability
in experimental conditions can be mitigated.
Lastly, efforts should be directed towards optimizing the endpoint detection
process. This may involve exploring alternative endpoint detection techniques,
such as spectrophotometric analysis to improve the accuracy and efficiency of
endpoint determination.
The recommendations outlined above aim to enhance the methadological
rigor, accuracy and reliability of future experiments on the determination of water
hardness by Complexometric titration. By incorporating these, researchers can
advance our understanding of water quality and contribute to the development of
effective strategies for water resource management and conservation.

13
CONCLUSION

The Complexometric titration experiment conducted to determine water

hardness has provided valuable insights into the mineral composition and quality
of various water sources. Through meticulous titration procedures and careful
analysis of endpoint data, important conclusions can be drawn regarding the
hardness levels of the tested water samples.
Overall, the experiment revealed that water hardness varies significantly
among different sources, with borehole water exhibiting higher hardness levels
compared to well, tap and borehole water. The observed variations in water
hardness can be attributed to geological factors, groundwater sources, and human
activities that influence the mineral content of each water source. The results
obtained from the experiment underscore the importance of water quality
monitoring and management strategies to ensure access to safe water for
consumption. High levels of water hardness can adverse effects on industrial
processes, household appliances and aquatic ecosystems, highlighting the need for
the effective treatment and mitigation measures.
The Complexometric titration experiment provided valuable data on water
hardness levels in various water sources, highlighting the variability and
significance of this parameter. Moving forward, the further research and
monitoring efforts are warranted to address emerging water quality challenges and
ensure the sustainable management.

14
REFERENCES

Sorg, Thomas J.; Schock, Michael R.; Lytle, Darren A. (August 1999). "Ion
Exchange Softening: Effects on Metal Concentrations". Journal AWWA. 91 (8):
85–97. doi:10.1002/j.1551-8833.1999.tb08685.x. ISSN 1551-
8833. S2CID 94253149. Archived from the original on 2011-07-26.
Retrieved 2010-11-23.

Stephen Lower (July 2007). "Hard water and water softening". Retrieved 2007-10-
08.

Rice, EW, Baird RB, Eaton AD, Clesceri LS (eds) (2012) Standard methods for
the examination of water and wastewater, 22st edn, Method 2340. American Public
Health Association, American Water Works Association, Water Environment
Federation, Washington, DC, pp. 2–37 to 2–39

Ryznar, John W.; Langelier, W. F. (April 1944). "A New Index for Determining
Amount of Calcium Carbonate Scale Formed by a Water". Journal of the
American Water Works Association. 36 (4): 472–486. doi:10.1002/j.1551-
8833.1944.tb20016.x. JSTOR 23345279.

Pocock SJ, Shaper AG, Packham RF (April 1981). "Studies of water quality and
cardiovascular disease in the United Kingdom". Sci. Total Environ. 18: 25–
34. Bibcode:1981ScTEn..18...25P. doi:10.1016/S0048-9697(81)80047-
2. PMID 7233165.

Reid, Robert N. (2003). Water Quality Systems: Guide For Facility Managers.
CRC Press. pp. 66–. ISBN 978-0-8247-4010-8.

^ Langelier, W. F. (October 1936). "The Analytical Control of Anti-Corrosion

Water Treatment". Journal of the American Water Works Association. 28 (10):
1500–1521. doi:10.1002/j.1551-8833.1936.tb13785.x. JSTOR 41226418.

15
ANSWERS TO POST LAB QUESTIONS

FIRST SAMPLE (RIVER WATER)

Hardness of river water sample in ppm;
(��� ��2+ ) × (1 ��� ����3) ×(100.1 ����3) × (103 ��)
Ppm Ca��3 = (1�) × (1 ��� ��2+ ) × (1 ��� ����3 ) × (1�)

9.12 × 10−3 ×100.1 × 103 × 1

Ppm CaCO3 = 1 × 1 ×1 × 1
= 91.2912 ppm

SECOND WATER SAMPLES (TAP WATER)

Hardness of tap water sample in ppm;
(��� ��2+ ) × (1 ��� ����3 ) × (100.1 ����3) × (103 ��)
Ppm CaCO3 = (1�) × (1 ��� ��2+ ) × (1 ��� ����3) × (1�)

1.106 × 10−3 × 1 × 100.1 × 103

Ppm Ca��3 = 1×1×1×1
= 110.7106 ppm

THIRD WATER SAMPLE (WELL WATER)

Hardness of well water sample in ppm;
(��� ��2+ ) × (1 ��� ����3 ) × (100.1 ����3 ) × (103 ��)
ppm Ca��3 = (1�) × (1 ��� ��2+ ) × (1 ��� ����3) × (1�)

1.04 × 10−3 × 1 × 100.1 × 103

ppm CaC03 =
1×1×1×1
= 104.104 ppm

FOURTH WATER SAMPLE (BOREHOLE WATER)

Hardness of tap water sample in ppm;
( ��� ��2+ ) × (1 ��� ����3 ) × (100.1 ����3 ) × (103��)
Ppm Ca��3 = (1�) × (1 ��� ��2+ ) × (1 ��� ����3 ) × (1�)

(1.206 × 10−3 ) × 1 ×100.1 × 103

ppm Ca��3 = 1×1×1×1
= 120.7206���

16