BIOINORGANIC

CHEMISTRY

Determination of the Hardness of Water

Sthandile Mehlo
School of Chemistry, University of the Witwatersrand, PO WITS 2050, Johannesburg, South Africa.
E-mail: [email protected]

Hardness EDTA as mg/L CaCO3 = (A*B*1000)/

Abstract:
(ml of sample)
Hardness is tendency of water not to react with
Where: A = ml EDTA solution used.
soap or tendency of water not to form a scale,
which is due to the presence of divalent cat-ions B = mg CaCO3 equivalent to 1 ml EDTA titrant.
mainly Ca+2 and Mg+2. In order to determine the Mg²⁺hardness as mg/L CaCO3 = Total hardness –
hardness some indicators will be used. Ca²⁺ hardness.
Hardness is most frequently measured through Objective:
application of the principle of chelation. Metals are
To introduce the concept of complex formation
capable of sharing electron pairs with a molecule and stability, and illustrate the analytical
or ion to form a coordination bond. These ions or application of these concepts to the measurement
molecule called chelating agents if it has more of calcium, magnesium and total hardness in
than one free electron pair to share. water.
As the number of these bonds increase the Apparatus:
stability of a chelate increase, one of the most
used chelating agents in analytical chemistry is
EDTA. This chelating agent is used to find the
concentration of calcium and magnesium ions.
Background
Introduction
Water that has high mineral content is known as
hard water. Hard water contains bicarbonate, Picture (1): Represent apparatus required, burette
chlorides and sulphates of calcium and (25 ml).
magnesium. Sample:
When treated hard water with soap, it gets
precipitated in the form of insoluble salts of
calcium and magnesium. Hardness of water is a
measure of the total concentration of the calcium
and magnesium ions expressed as calcium
carbonate.
Hardness of water is a measure of its capacity to Picture (2): Represent chemicals required
precipitate soap, and is caused by the presence of
divalent cations of mainly calcium and
magnesium.

1
 Table 2: Insert concise, descriptive table caption
Analysis

1 2 3
Trial
Initial burette 4.15 0.01 13.35 26.02
reading (mL)

Final burette 17.2 13.35 26.02 39.54

reading (mL) 5

Volume of EDTA 13.1 13.34 12.67 13.52

used (mL) 0
Picture (3): Shows the procedure followed when the
experiment was done. moles of (Ca) 6.47 6.590 6.259 6.679
1 ×10
−5
×10
−5
×10
−5
−5
Results ×10

Table 1: Insert concise, descriptive table caption

Analysis

1 2 3
Trial [Ca] mol L-1 25.9 26.41 25.08 26.77
Initial burette 0.00 11.75 22.20 32.73 aliquot 3
reading (mL)
Mean [Ca] mol L-1 Mean = 26.09 + 0.8902
Final burette 10.4 22.20 32.73 43.12 + stats
reading (mL) 0
Mean [Mg] mol L-1 Mean = 7.15 + 1.14
Volume of EDTA 10.4 10.45 10.53 10.39 + stats
used (mL) 0

moles of (Ca + 5.14 −5 −5 −5

5.16 ×105.20 ×105.13 ×10
Mg) −5 Table 3: Insert concise, descriptive table caption
×10 CaCO3 / mg.dm-3 Classification
0 – 50 Soft
-1
[Ca + Mg] mol L 33.1 33.20 33.50 33.00 50 – 100 Moderately soft
aliquot 0
100 – 150 Slightly hard
Mean [Ca + Mg] Mean = 33.23 + 0.2517 150 – 200 Moderately hard
mol L-1+ stats
200 – 300 Hard
> 300 Very hard

2
 changes. To minimize errors, experiments should
use controlled lighting, well-buffered solutions,
Discussion freshly prepared indicators, and ideally, digital
A water sample is adjusted to pH 10.1 and placed detection in place of visual interpretation for critical
in a conical flask. When an indicator like EBT analyses.
(Eriochrome Black T) is added to a solution
containing calcium and magnesium ions, the
solution appears wine red. EDTA, the titrant, binds Declarations
with calcium and magnesium ions, pulling them All the work I wrote is the work of my own, I used
away from the indicator. Once all the Mg²⁺ and an Ai to formalize my report.
Ca²⁺ ions have reacted with EDTA, the indicator
changes color to blue, signaling the titration
endpoint.
Carbonate hardness can be removed simply by
boiling the water. In contrast, non-carbonate
hardness requires chemical treatment. This
process of measuring hardness relies on chelation References
reactions. 1. Skoog, D. A., West, D. M., Holler, F. J., &
To measure only calcium hardness, a Murexide Crouch, S. R. (2013). Fundamentals of
indicator is used, which shifts color from purple to Analytical Chemistry (9th ed.). Cengage
violet. For total hardness, EBT is used, which Learning.
changes from wine red to blue during the titration. – This textbook provides a comprehensive
Hard water is characterized by high levels of explanation of complexometric titrations and
calcium, magnesium, and other divalent ions. the use of indicators like EBT and Murexide.
While Ca²⁺ and Mg²⁺ are not harmful to health,
they can interfere with everyday water uses, such 2. Harris, D. C. (2015). Quantitative Chemical
as cleaning. Analysis (9th ed.). W. H. Freeman and
Permanent (non-carbonate) hardness, which Company.
cannot be eliminated by boiling, can be treated – A reliable source for titration methods,
using chemicals like calcium oxide (CaO) or soda including EDTA titrations for hardness
ash. In contrast, temporary (carbonate) hardness determination.
is removed by boiling.
3. World Health Organization (WHO). (2011).
This experiment showed good precision with low
%RSD, and assuming a known concentration, Hardness in Drinking Water: Background
percentage error could be assessed to judge Document for Development of WHO
accuracy. While the method is reliable, small Guidelines for Drinking-water Quality.
systematic errors like endpoint subjectivity can be Retrieved from: https://www.who.int/
improved through the use of digital tools and – This document discusses the implications of
automation. Repeating trials and carefully water hardness and acceptable ranges.
controlling experimental conditions will ensure
more accurate and reproducible results in future 4. U.S. Environmental Protection Agency (EPA).
work.
(2009). National Secondary Drinking Water
Both EBT and Murexide are vital in determining Regulations.
water hardness through complexometric titration. – Useful for hardness classifications and
EBT is preferred for total hardness, while
understanding water quality standards.
Murexide is specific to calcium hardness. Accurate
results depend heavily on proper handling, correct 5. Standard Methods for the Examination of
pH, good technique, and clear recognition of color
Water and Wastewater. (2017). 23rd ed.,
3
 American Public Health Association (APHA), m
Number of moles (EDTA) =
American Water Works Association (AWWA), Mr
Water Environment Federation (WEF).
0.46 g
– The definitive source for lab methods =
372.24 g/mol
including EDTA titration of water samples.
= 0.001236 mol EDTA
6. Rieman, W. & Walton, H. (1970). Ion
Exchange in Analytical Chemistry.
International Series of Monographs in n
Concentration (EDTA) =
Analytical Chemistry. Pergamon Press. V
0.001236 mol
=
0.250 L
Supplementary Information = 0.00494 M of EDTA
Part B: Total hardness of (Ca²⁺ and Mg²⁺):
In this section, you need to include any raw data,
Average volume (mL) =
all calculations, Excel statistical analysis printouts 10.45+10.53+10.39
etc. Results and statistical analyses must be 3
= 10.46 mL
calculated using Excel spreadsheets. Use
appropriate headings to compile this section. Only
summarised findings should appear in the Total moles of EDTA = moles of (Ca²⁺ and
“Results” section. Mg²⁺)
= ( 0.00494) × (
10.46 mL
Volume of EDTA used per Trial )
1000
15 =5,167×10 -5 mol EDTA used
∴ moles of (Ca²⁺ and Mg²⁺) in 100 mL sample
Volume (ml)

10

= 5,167×10-5 mol
5
0
1 2 3
Trial number

Trials Volume of EDTA (ml)

(2) Convert to ppm as CaCO3:
1 mg/L = 1 ppm
Picture (4): A Bar graph showing the volume
used per trial. Mass of CaCO3 = moles (EDTA) × (Mr
CaCO3×1000)

= 5.579×10 -5 × (100.09×1000)
Calculations:
= 5.584 mg in 100 mL sample
(1) Concentration of the EDTA
100 mL of tape water = 0.100 L
∴ The amount of CaCO3 found in 0.1 L = 5.584 mg
Data:
Mass of EDTA = 0.46g
m
Volume = 250 mL Concentration (CaCO3) =
V
= 0.250 L
5.584 mg
Molecular weight = 372.24 g/mol ¿
0.100 L
4
 = 55.84 mg/L m
Concentration (CaCO3) =
= 55.84 ppm Mr
∴ From table 3: 50 – 100 ppm indicates that the
6.517 mg
=
0.100 L
water hardness is moderately soft.
= 65.17 mg/L = 65.17
(3) %RSD for part B ppm
S = ∴ From table 3: 50 – 100 ppm indicates that the

√
2 2
( 10.45−10.46 ) + ( 10.53−10.46 ) + ( 10.39−10.46 ) 2 water hardness is moderately soft.
3−1
= 0.0704 mL %RSD for part B
x = 10.46 mL S =

%RSD = ×100 √ ( 13.34−13.18 ) + ( 12.67−13.18 ) + ( 13.52−13.18 )2

2 2
S
x 3−1
0.0704 =0.4479 mL
= ×100
10.46 x = 13.18 mL
=0.67% > 2%
×100
S
%RSD =
x
Part C: Ca²⁺ titration with EDTA 0.4479
Ca²⁺ Determination
= ×100
13.18
=3.40% > 2%
Average volume (mL) =
13.34+12.67+13.52
3
= 13.18 mL Mg²⁺ Determination by subtraction

Moles of EDTA used n (Ca²⁺ and Mg²⁺) = 5,167×10-5 mol

n(EDTA) = c(EDTA) × V(EDTA) n (Ca²⁺) = 6.511×10-5 mol

∴ n (Mg²⁺) = n (Ca²⁺ and Mg²⁺) - n (Ca²⁺)
= (0.00494) × (
13.18 mL
)
1000 = 5,167×10-5 mol - 6.511×10-5 mol

= 6.511×10-5 mol of EDTA used = 1.344×10-5 mol of Mg²⁺

∴ moles of EDTA = moles of Ca²⁺

Convert to ppm as CaCO3
1 mg/L = 1 ppm
Moles of Ca²⁺ = 6.511×10 mol -5
m (CaCO3) = n (Mg²⁺) × (Mr CaCO3 ×1000)
= 1.345 mg
1 mg/L = 1 ppm (CaCO3) = moles (EDTA) × (Mr
(2) Convert to ppm of CaCO3

CaCO3×1000)
Concentration (CaCO3) =
n
V
= (6.511×10-5 mol) × (100.09 ×1000)
g
= 13.45 ppm
mol
= 6.517 mg in 100 mL Sample