SCHOOL OF NATURAL AND PHYSICAL SCIENCE

CHEMISTRY DEPARTMENT

ANALYTICAL CHEMISTRY 1

EXPERIMENT #9- CHELOMETRIC TITRATION

TITLE: Chelometric titration also known as complexometric titration

NAME: Roselyn NORM

ID#:202110102

LECTURER: MR. V BAU

Analytical Prac#9

Title: Chelometric titration also known as complexometric titration

Aim: Formation of complex ions, they combine with chelating agents mainly using EDTA, Unrelating
agents have sites which can donate electrons. Hence, this experiment is to determine the hardness of
water using tap water and the second part is to determine of salt in solution via ion exchange procedure
and EDTA titration.

Introduction

A versatile chelating agent is EDTA. It can create four or six bonds with a metal ion and chelates with
main-group and transition-metal ions. Due to its propensity to form complexes with calcium and
magnesium ions, EDTA is commonly employed in soaps and detergents. The poly- amino carboxylic acid
EDTA has six sites with a single pair of electrons and can bind to metals via four carboxyl and two amine
groups. As a polydentate ligand, CA can attach to metals using three carboxyl groups, each of which has
a single electron.

arrow indicating donating sites(ligand sites).

Organic dyes that create a colorful complex with the metal ion being titrated are the most used
indicators in complexometric titrations. When the reaction is complete, the color changes because the
indicator is replaced by EDTA, which creates a more stable complex with the metal.

From this practical there will be two part, where the first being the determination of the hardness of
water, by titration using the chelating agent EDTA acid. Thus, EDTA (Ethylenediaminetetraacetic acid) is
a common molecule used in complexometric titrations to determine the hardness of water. When
Eriochrome Black T dye is added to the hard water at pH around 10, it gives a wine-red coloured
unstable complex with Ca+2 and Mg+2 ions of the sample water. By titrating with a standard solution of
the complexing agent ethylene diamine tetra acetic acid (EDTA), the hardness of water is ascertained.
We'll measure the overall hardness as well as the distinct calcium and magnesium hardnesses.
Complexometric titration is used to estimate hardness. Metal ions contribute to the hardness of water.

Method
Part a; Determination of water hardness

i. In this part 100ml of tap water was added with 5ml of NH4Cl/NH4OH buffer at pH 10, then a few
crystals of KCN was added with few crystals of hydroxyammonium chloride followed by eriochrome black
T indicator. Then titrated with 0.01M EDTA till endpoint for pink red color to blue color.

ii. For temporary hardness 100ml tap water was added with 1ml of 5M NaOH and 0.2g of murexide
indicator and stir. The solution obtained was then titrated with EDTA this will then have a small value
than the previous titration.

The effect of heavy metal impurities with repeat from (i) but without crystals of KCN was added with few
crystals of hydroxyammonium chlorid.

Part b; Total dissolved salts in solution

There was 50ml of 5M hydrochloric acid prepared in a cation exchanges column which was flowed
through slowly. There were salt solutions provided Mg2+,Zn2+,Cd2+with total number of moles yet to be
determined.

In the Ion Exchange Procedure 20ml of the aliquot metal salt solution was passed through a column
collection effluent in a clean 500ml flask. This was then followed through with 100ml distilled water and
collected the washing in the same flask. This liberated acid is then titrated with standard alkali solution.

For the EDTA Titration a transfer of 20ml aliquots of the salt solution was added with NH4Cl/NH4OH
buffer followed by 3-4drops of eriochrome black T indicator in a 250ml flask. This was titrated with
0.01M EDTA solution till 0.1M.

Results

1. M + EBT → M −EBT

2. M −EDTA + EDTA → M −EDTA+ EBT

∴For Ca-EDTA and Mg-EDTA

A) Total hardness of water

Volume of EDTA added to endpoint

1. 6.72ml
2. 6.70ml
3.6.74ml
Average =6.72ml
Q: Calculate the hardness in ppm of CaCO3 .
Water sample= 100ml
Titration volume of EDTA= 38.73ml
Molarity of EDTA= 0.01mol/L
2−¿¿
4−¿¿ ¿
EDTA +Ca2+¿ →CaEDTA

Calculate moles of Ca2+

Water hardness ( ppm)=(Volume of EDTA used x Concentrationof EDTA x 1000)/Volume of water sample

0.01 mol
6.72 mL × ×1000
L g
∴ =0.672
100 m L mol

0.672 mol 100.09 g 1000 mg

× × =67260.48 mg/ L
l mol 1g

b) Temporary hardness

Volume of EDTA
3.75ml
3.85ml
Average = 3.8ml
Calculate temporary Hardness as ppm CaCO3

TH=(C×2.497)+(M×4.118)

Where TH is the temporary hardness in ppm of CaCO3, C is the concentration of calcium bicarbonate in
ppm, and M is the concentration of magnesium bicarbonate in ppm.

Since Ca2+ : Mg2+ is 1:1

(
Hardness of Ca is => 3.8 mL ×
0.01mol
L )
×1000 ÷ 100 ml=0.38 M
 (
Hardness of Mg =hardness of Ca 3.8 mL ×
0.01mol
L )
×1000 ÷ 100 ml=0.38 M

2.5137 mol
Temporary Hardness= ( 0.38 M ×2.497 ) + ( 0.38 M × 4.118 )=
L

mol mg 2.5137 mol 100.09 g 1000 mg

¿ CaC O3 change ¿ =¿ × × =251370 mg /L
l l l mol 1g

Effect of heavy metal impurities

Volume of EDTA
1. 40.0ml
2.34.0ml
3.42.2ml
Average= 38.73ml
Calculate the Hardness as ppm of CaCO3

Water sample= 100ml

Titration volume of EDTA= 38.73ml
Molarity of EDTA= 0.01mol/L

(3 8 .73 mL × 0.01Lmol ×1000) ÷100 ml=3.873 mol / L

Part B: Total ion in solution

 Ion Exchange procedure

Volume of salt= 20.0mL

Volume of distilled H2O=100mL
Conc of Alkalide solution= 0.1M
Amount of alkali required to reach end point=20.5mL
Calculate moles of M2+ present /L of salt solution (conc)
0.1 mol 1L −3
moles of alkalide= × 20.0 l× =2.00 ×10 mol
L 1000 ml
−3 20 ml −4
2 +¿=2.00 ×10 mol× =4.00 ×10 mol¿
100ml
moles of M
 EDTA Titration

1. 10.4mL
2. 10.4mL
3. 10.3mL
Average= 10.37mL
Calculate moles of M2+ present /L of salt solution (conc)
 0.1 mol 1L −3
moles of alkalide= × 20.0 l× =2.00 ×10 mol
L 1000 ml
−3 10.37 ml −4
2 +¿=2.00 ×10 mol ÷ =2.074 ×10 mol¿
100 ml
mole of M

∴ total moles equal=4.00 ×10−4 mol+2.074 × 10−4 mol=6 .074 × 10−4 mol
Discussion

A water sample is placed in a conical flask after being buffered to pH 10.1. A solution containing calcium
and magnesium ions changes to a wine-red color when an indicator dye, such as EBT, is added. The
titrant, EDTA, forms compounds with calcium and magnesium ions to prevent their association with the
indicator. The indicator will become blue once all of the Mg+2 and Ca+2 have been complexed with
EDTA. This marks the titration's conclusion. On the other hand, carbonate hardness may be easily
removed by boiling while non-carbonate hardness must be removed using chemical processes. The
concept of chelation provides the foundation for determining hardness. EBT moves from red wine to
blue and is used to assess total hardness, while Murexide indicator changes from purple to violent and is
used to evaluate Ca+2 hardness. Hard water is defined as having a comparatively high content of and
other divalent contaminants. Although the presence of Ca+2 and Mg+2 normally poses no health risk,
they can render water unfit for use in certain domestic applications. Permanent non-carbonate
hardness, which cannot be eliminated by boiling water as in carbonate hardness (Temporary), can be
eliminated with CaO and soda ash.

Water's hardness, which results in the formation of an insoluble precipitate with soap, is mostly caused
by the presence of calcium and magnesium ions in the water. Hard waters may taste better than soft
fluids and have no known negative health effects. The main reasons why hard water is a problem are
that it makes cleaning more difficult, makes clothes yellow, toughens vegetables cooked in it, and
develops scales in boilers, water heaters, pipes, and cooking utensils. Water of acceptable quality
shouldn't have a hardness greater than 250 mg/L, expressed as calcium carbonate equivalents.
Depending on the pH, alkalinity, and dissolved oxygen levels in the water, water that is softer than 30 to
50 mg/L may corrode pipework. Ca2+, Mg2+, and other divalent ions are primarily to blame for the water's
hardness. Water's ability to precipitate soap and other substances used in industry is measured by its
hardness.

For this experiment the hardness of water is more than safe due to it having a value greater than
250mg/L at 67260.48mg/L, with its temporary hardness at 251370mg/L for the water hardness part.
Thus tap water is safer for human uses.

For part b it is the determination of dissolved salt in solution, where the amount of all inorganic and
organic compounds present in a liquid in molecular, ionized, or micro-granular (colloidal sol) suspended
form is known as total dissolved solids (TDS). Since some of the ions that make up the definition of TDS
are also present in salinity, total dissolved solids are often exclusively mentioned for freshwater systems.
The total amount is calculated at 6.074×10-4 moles as the question asked to calculate the amount of
moles only.
Reference
Anon., n.d. [Online]
Available at: https://www.byjus.com
[Accessed 22 July 2022].
Johnson, A., September 6, 2022. What are the donor sites of EDTA?. [Online]
Available at: https://scienceoxygen.com/what-are-the-donor-sites-of-edta/
[Accessed 21 September 2023].