Determination of Water
Hardness by EDTA Titrimetric
Method
Dr. Connie Cheng
Medical applications of Inorganic elements/ compounds
Objective:
• To determine the concentration of permanent hardness in
water by titration with a standard solution of
ethylenediaminetetraacetic acid (EDTA)
• To understand complexometric titration
What is water hardness?
• Water itself that contains certain dissolved minerals in relatively large
amount is called hard water.
• Ground and surface water dissolves Ca2+, Mg2+ containing ores/
minerals from surrounding soil and rock.
• Hardness is commonly expressed as mg of CaCO3 eq./L
• Amount of hardness causing chemicals:
Ø 60mg/L = soft water
Ø 60 -120 mg/L = moderately hard water
Ø 120 -180 mg/L = hard water
Ø > 180 mg/L = very hard water
• Bicarbonate ion, HCO 3-, is classified as temporary hard because the
water may be “softened” by boiling.
• Water that contains ions that are not removed by heating, such as
Ca2+, Mg2+, Fe 3+, and SO4 2-, is said to be permanently hard.
Principle:
• EDTA forms complexes with large number of cations including Ca 2+
and Mg2+ ions.
• Since EDTA is insoluble in water, the disodium salt of EDTA is used.
• The resulting metal-ligand complex, in which EDTA forms a cage-like
structure around the metal ion, is very stable at specific pH.
Ligand:
EDTA 1. The molecules or ions that surround the metal
in a complex ion.
2. has at least one unshared pair of valence electrons
donated by the donor atom (an atom
which is electron rich)
a polydentate ligand – as EDTA4- ion
Disodium salt of EDTA
EDTA:
+ Ca2+(aq)
EDTA-metal
2 Na+
complex
EDTA: Ca = 1:1 moles
EDTA-metal 2+
complex
- Crystal Field Theory
- Octahedral in geometry
M = Ca2+
MYn-4
Color change
1. Ca2+ + calmagite ⇌ Ca(calmagite)2+
2. Ca(calmagite)2+ + EDTA ⇌ Ca-EDTA + calmagite
Wine-red blue
weak complex strong complex
colorless
Structure of Calmagite, an indicator
Azo compound
Used as an indicator in the titration of calcium (Ca) or
magnesium (Mg) with EDTA
Titration set up
EDTA
What is the expected color change?
Calcium solution
https:/ /www.youtube.com/watch?v=akRcLMQUxm4
Ca
Ca2+ ion
Consider the stability of the complexes,
explain the color change in the lab report.
Ca(calmagite)2+ + + EDTA ⇌ Ca-EDTA + calmagite
Concentration of Solution
1. Percentage notation
2. Parts-per notation
3. Mole-based notation
4. Molarity and Molality
15
1. Percentage notation
16
Weight/weight is the same meaning as Mass Percent.
17
2. Parts-per notation
• ppm, parts per million (mg/g, mg/L)
- 1mg of solute dissolved in 1L (1000g) of water
- Concentration = 1 10-3 g solute / 103 g solution
= 1 g solute / 106 g solution = 1 ppm
• ppb, parts per billion (ng/g, mg/L)
- 1 mg of solute dissolved in 1L (1000g) of water
- Concentration = 1 10-6 g solute / 103 g solution
= 1 g solute / 109 g solution = 1 ppb
18
Mole – a counting unit in chemistry to represent the amount of substance, like a dozen
mole =
( )
Concentration of EDTA
Molarity of EDTA = (Molarity of Ca 2+) (vol. of Ca2+ used)
vol. of EDTA used
Hardness calculation
• Molarity of Ca2+ = (Molarity of EDTA) (vol. of EDTA used)
vol. of water sample used
= mol / L (unit)
• 1 ppm CaCO 3 = 1mg CaCO 3 / L
• ppm CaCO 3 = molarity of Ca2+ ion ´ 100 g CaCO3 / 1 mol ´ 103 mg/g
100 3 1000
= Ca2+ ion ´ ´
1
Cautions:
• None of the reagents in this procedure is particularly dangerous.
• The normal safety precautions should be followed.
• Wear eye protection.
• Never pipet by mouth. Always use a suction device when drawing a
solution into a pipette.
Experimental Procedures
A) Preparation of standard calcium ion solution
• Measure 0.25 g of calcium chloride, CaCl2 and prepare a 250 mL
standard calcium ion solution
B) Standardization of EDTA Solution
• Titrate the standard Ca2+ solution with EDTA solution
Observation:
• wine-red color of the Ca indicator complex changes from purple-red
to the pure blue color of the free form of the indicator.
C) Determination of permanent hardness of a water sample (as ppm
CaCO3)
• Determine the hardness of a water sample by EDTA complexometric
titration
Lab Report – 12 July 2024 (Fri) @ 23:59
1. Title
2. Objectives
3. Introduction
4. List of glassware and reagents
5. Results (p.6, result table)
6. Discussion - the theory to explain the formation of the colour complex, advantages and disadvantages of
the complexometric titration experiment, possible sources of error etc.
7. answer to the Questions (p.7 of the lab manual)
8. Conclusion
9. Reference - if applicable
