DEPARTMENT OF CHEMICAL AND FORENSIC SCIENCES

CHEM 301 LAB TWO: EDTA DETERMINATION OF TOTAL WATER

HARDNESS AND CALCIUM
STUDENT NAME: KEALEBOGA AMIE PHIRI
STUDENT NUMBER: 18000352
PROGRAMME: PURE AND APLLIED CHEMISTRY
1. AIM
The main objective of this experiment is to determine the total hardness and calcium
of water using EDTA.

2. INTRODUCTION
Water hardness is the measure of cations in water. Hard water contains cations such
as calcium, magnesium, iron, zinc and iron. Calcium and magnesium are easily
measured by titration with the complexing agent ethylene-diamine tetraacetate
(EDTA). The Y4- ion that forms a 1:1 complex with the metal ion is the completely
deprotonated anion of ethylenediaminetetraacetic acid (“H4Y”). At pH=10, the EDTA
is present in solution primarily as its monoprotonated form, HY3-. The endpoint of an
EDTA titration is determined with a metallochromic indicator. These indicators are
themselves complexing agents that change colour as they combine with a metal ion.
Two popular indicators for titrating Ca2+ or Mg2+ are eriochrome black T and
calmagite. In a titration, EDTA, a stronger complexing agent than the indicator,
displaces the indicator form the metal ion allowing the indicator to return (through
shades of violet) to a pure blue color, indicating the end of the reaction, (Bellomo et
al, 2000).

According to (Bellomo et al,2018), EDTA forms a more stable complex with calcium
(log Kf = 10.65) than with magnesium (log Kf = 8.79). Thus, in solutions (such as
natural water samples) that contain both metals, EDTA reacts first with Ca2+ , and,
when all the Ca2+ ions have been complexed, with Mg2+ . When all the free Mg2+
has been complexed by EDTA, the remaining free (uncomplexed) EDTA displaces
the Calmagite from the red MgIn– complex. At the endpoint, just enough EDTA has
been added to displace all the calmagite and the solution turns blue because of the
presence of HIn2– in solution. The EDTA at first will only react with Ca+2 creating a
colourless chelate, but once enough EDTA is added it will use up all the Ca+2 and
will begin reacting with the Mg+2. The Mg+2 will eventually be used all up and the
EBT will go back to its original blue colour. The less EDTA needed to turn blue, the
softer the sample is.

3. EXPERIMENTAL
i. Apparatus and chemicals
 250- volumetric flasks
 50 mL burette
 250-mL Erlenmeyer flasks
 10-mL graduated cylinder
 volumetric pipette
 250-mL plastic bottle
 plastic bottle
 50ml Beakers
 Droppers
 Disodium salt of EDTA or disodium EDTA dihydrate
 Tap water
 50% w/v NaOH solution (50g in 100cm3 solution
  5cm3 measuring cylinder
ii. Procedure
Part A: Determination of total hardness
25cm3 tap water was pipetted into a conical flask. Afterwards 2cm 3 buffer
solution was added followed by 3 drops of Eriochrome Black T indicator
solution. The solution was then titrated with 0.01 M EDTA until the solution
turned from wine red to sky blue with no hint of red (the solution was then for
colour comparison). The titration was then repeated to obtain two concordant
results.

Part B: Determination of concentration of Ca" (aq) ions

Into the next part of the experiment 50 cm3 of tap water was pipetted into a
conical flask. 30 drops of 50% w/v NaOH solution were added, the solution
swirled and waited for a couple of minutes to completely precipitate the
magnesium ions as Mg (OH)2. A pinch of hydroxy naphthol blue (exact
amount to be decided by the intensity of the resulting-coloured solution) was
added and titrated with 0.01 M EDTA until it changed to sky blue (the
solution was saved for colour comparison). Lastly, the titration was repeated
to obtain two concordant results.
4. RESULTS

A. PART A: DETERMINATION OF TOTAL HARDNESS

Trial 1 2
Final burette 3.22 6.18 9.12
reading / cm3
Initial burette 0.22 3.22 6.18
reading/ cm3
Volume used/ cm3 3.00 2.96 2.94
 
Average volume = 2.95

B. PART B: DETERMINATION OF THE CONCENTRATION OF Ca2+(aq) ions

Trial 1 2
Final burette 2.90 5.88 8.80
reading/cm3
Initial burette 0.02 2.90 5.88
reading/cm3
Volume/cm3 2.88 2.98 2.93
 
Average 2.96
volume=

SAMPLE CALCULATIONS
1.PART A
Average volume used = 0.00295 L
Concentration of EDTA= 0.01M
Moles of EDTA= concentration x volume
Moles of EDTA = 0.01M x 0.00295L
Moles of EDTA = 0.0000295 moles
Moles of Ca2+ in 25ml tap water used
Moles of EDTA: Moles of Ca2+
1 : 1
0.0000295 mol: x
Moles of Ca2+= 0.0000295 mols
Concentration of Ca2+ = n / v
                                     = 0.0000295mols / 0.025L
                                     = 0.00118 mol/L
1L = 1 dm3
Hence concentration = 0.00118mol/dm3
Moles of EDTA: Moles of Mg2+
Mole ratio = 1:1
Moles of EDTA: Moles of Mg2+
Moles of Mg2+ = 0.0000295 moles
Concentration of Mg2+=0.0000295mols/0.025L
                              =0.00118mol/L
Concentration of Mg2+= 0.00118 mol/dm3

2.PART B
  Ca2+ + H2EDTA2- → CaEDTA2- + 2H+
Average volume of EDTA used= 2.96mL
2.96mL = 0.00296L
Concentration of EDTA = 0.01 M
Moles of EDTA = concentration x volume
Moles of EDTA = 0.01M x 0.00296L
 Moles of EDTA = 0.0000296 mols
Moles of Ca2+ in 50mL tap water used
Moles of EDTA: Moles of Ca2+
1 : 1
0.0000296 : x
Moles of Ca2+ = 0.0000296 mols
Concentration of Ca2+ = n /v
               = 0.0000296 mols /0.05L
                                 = 0.000592mol/L
1L of water contains 0.000592mols Ca2+
Mass of Ca2+ = moles x molar mass
 Mass of Ca2+ = 0.000592mol x 40.078g/mol
Mass of Ca2+ =0.023726176g
Mass of Ca2+ = 0.023726176g x 1000
Mass of Ca2+= 23.726176mg
1L= 1dm3
Hence the concentration of Ca2+ ions = 23.73 mg/dm3
3. Determination of Mg2+ in water sample
 Mg2+ + H2EDTA2- → MgEDTA2- + 2H+
Moles of EDTA= concentration x volume
Moles of EDTA = 0.01M x 0.00296L
Moles of EDTA = 0.0000296 moles
Mole ratio of Mg2+: EDTA is 1:1
Moles of EDTA: Moles of Mg2+
1 : 1
0.0000296  : x
Moles of Mg2+ = 0.0000296 moles
Concentration of Mg2 + = moles /volume
                                     =0.0000296 moles/ 0.050L
                                     = 0.000592mol/L
1 L of water contains 0.000592 moles Mg 2+
Mass of Mg2+ = moles × molar mass
                        = 0.000592mol × 24.305g/mol
Mass of Mg2+ = 0.0144g
Grams to milligrams
=0.0144g ×1000
 =14.40mg
L=dm-3
Concentration of Mg2+=14.40mg/dm3
Tap water measured is therefore soft
5. DISCUSSION
In this experiment, the main focus is to determine water hardness and this was done
by complexometric titration where the magnesium and calcium ions concentration in
water were determined. It is in this experiment where the Eriochrome black T
indicator is used purposely to show colour change depending on the pH of the water
shown by the red colour change in acidic environment and orange in basic solution. In
the process of titration, the Eriochrome black solution was added after the addition of
2cm3 buffer solution into the pipetted tap water containing the magnesium and
calcium ions inside the conical flask changing the colour of the solution to red wine.
The solution was then titrated with the EDTA where the endpoint was indicated by
the change in colour from red wine to blue. This colour change occurs because with
the addition of the EDTA to the buffered solution, EDTA replaces all the EBT
forming Ca/Mg-complex and the formed EBT is the one indicating the endpoint of the
blue colour, (Waters et al, 2001).

In the first part of the experiment the concentration of the Mg 2+ and Ca2+ were
calculated as 0.00118mol/dm3 in the process to calculate the total hardness of water.
Following the second part of the procedure the concentration of the Ca 2+ ions
calculated in the water sample is 23.73 mg/dm3 and that for the Mg2+ ions is
14.40mg/dm3. According to the scientific study, the Ca2+ and mg2+ ions concentration
in water below 60mg/dm3 is considered soft are acceptable as drinking water,
( Yappert, M.C. and DuPre, D.B., 2009). Any ion concentration level above 180mg/
dm3 is considered hard and should not be used for human consumption. The tap water
ions concentration examined in this experiment is therefore considered soft since its
ion concentration level is below 60mg/dm3. The hard water with calcium and
magnesium ions is generally not a health threat but can be regarded unsuitable for
household uses.

Using of the EDTA as an indicator however has some limitations to a successful

titration because it forms stable complexes with the metal ions and lacks selectivity
when used to measure only one metal from a mixture of metals. Although tap water
may be cost effective and an easy way to keep hydrated, it may however contain
heavy metals such as zinc, aluminum and lead, consuming this water for a prolonged
time may be cause health problems such as brain deformities.

Though the experiment was a success, there are errors that had been encountered
inclusive of the fact that it was not easy detecting the endpoint because of the slight
violet colour change that distracted clear observation. Further error was a slow
 reacting time hence the volumes recorded exceeding the actual volumes of the end
point. With effort to reduce errors in this exercise, several volumes were collected, the
average calculated and used for the concentration calculations.

6. CONCLUSION
The amount of calcium in the laboratory’s tap water was calculated with the
application titration with EDTA and found to be 23.73mg/dm 3, which is below the
defined standard concentration for “hard” water of 180mg/dm 3 calcium. The total
hardness of the water was also calculated as 0.00118mol/dm 3.Tap water in the
laboratory is therefore regarded soft.

7. REFERENCES
I. Bellomo, A., de Robertis, A. and D'Arrigo, C., 2000. Semi-automatic end-
point detection in the determination of total hardness in water. Analytica
Chimica Acta, 149, pp.401-403.

II. Pal, A., Pal, M., Mukherjee, P., Bagchi, A. and Raha, A., 2018. Determination
of the hardness of drinking packaged water of Kalyani area, West
Bengal. Asian Journal of Pharmacy and Pharmacology, 4(2), pp.203-206.

III. Waters, R.S., Bryden, N.A., Patterson, K.Y., Veillon, C. and Anderson, R.A.,
2001. EDTA chelation effects on urinary losses of cadmium, calcium,
chromium, cobalt, copper, lead, magnesium, and zinc. Biological trace
element research, 83(3), pp.207-221.

IV. Yappert, M.C. and DuPre, D.B., 2009. Complexometric titrations: competition
of complexing agents in the determination of water hardness with
EDTA. Journal of Chemical Education, 74(12), p.1422.