CHEM 301- EXPERIMENT 2

EDTA DETERMINATION OF TOTAL WATER

HARDNESS AND CALCIUM

LEMANG SEGOMELO

16000419

PURE AND APPLIED CHEMISTRY

EDTA DETERMINATION OF TOTAL WATER HARDNESS AND CALCIUM
1. AIM
To determine the concentrations of Ca2+ (aq) and Mg2+(aq) ions in a sample of tap water as
well as to determine the total harness of tap water.
2. INTRODUCTION
Water hardness is an expression for the sum of the calcium and magnesium ion concentration
in a water sample. Hard water is high in dissolved minerals, largely calcium and magnesium;
additional contributors to the hardness of the water include iron, strontium zinc and other
ions. However their concentrations are usually significantly lower than concentration of
magnesium and calcium. These cations form insoluble salts with a reagent in soap,
decreasing its cleaning effectiveness and this is how hardness is determined (Veríssimo,
Oliveira and Gomes, 2007). The standard way to express water hardness is in ppm CaCO3
which has the formula weight of 100.1 g/mole. Complexometric titration is one of the best
ways of measuring total water hardness using a standard ethylenediaminetetraacetic acid
(EDTA) solution. At pH around 10 and due to steric hindrances, EDTA will complex with
calcium and magnesium in a one-to-one mole ratio(Required et al., 2003). This EDTA
reagent can form edta-metal complexes by the reaction with metal ions except for alkali metal
ions i.e. this reagent can forms a stable complex with the alkaline earth metal like calcium ion
and magnesium ion in alkaline condition, pH above 9.0(Required et al., 2003). In this method
buffer solution is used for attaining suitable condition to ensure that the pH level is above 9
for the titration since the buffer solution preserve pH at a balanced position. In aqueous
solution edta exist as H2Y2- form therefore the edta react with alkaline earth metals as
1:1mole ration so for every mole of alkaline earth metal ion in water sample, one mole of
EDTA will be consumed during titration giving this reaction; H 2Y2- + M2+ → MY2- + 2H+
(Equation, 2004).
Eriochrome Black T is commonly used as indicator for the above titration. At pH 10, Ca2+
(aq) ion first complexes with the indicator as CaIn+(aq) which is wine red so as the stronger
ligand EDTA is added, the CaIn+(aq) complex is replaced by the CaY2-(aq) complex which
is blue. The end point of titration is indicated by a sharp colour change from wine red to blue
therefore titration using Eriochrome Black T as indicator determines total hardness due to
Ca2+(aq) and Mg2+(aq) ions;Now if EDTA (H2Y2–) is added to such a solution Mg2+
preferentially complexes with EDTA (since the metal EDTA complex is more stable than the
metal-indicator complex) and liberates the free indicator HD2– at the end point, thereby
producing a sharp colour change from wine red to blue(Equation, 2004).
The main reaction is
Ca2+ + EDTA4- → [Ca-EDTA]2-
Back titration
EDTA4- + Mg2+ → [Mg-EDTA]2-
Figure 1; Structure of MgY2- chelates

3. EXPERIMENTAL

3.1 Apparatus and materials

 50% w/v NaOH solution (50g in 100cm3 solution)
 Eriochrome Black T indicator pH 10 NH3-NH4Cl buffer , hydroxynaphthol blue
indicator,0.05M EDTA(disodium salt)
 Tap water

3.2 PROCEDURE
Determination of total hardness
50 cm3 of tap water was pipetted into a conical flask, and then 2 cm 3 of buffer solution
followed by 3 drops of Eriochrome Black T indicator solution were added to the conical
flask. The solution was titrated with 0.01M EDTA until it turned from wine red to sky blue
with no hint of red. Titration was repeated so as to obtain two concordant results.

5. DISCUSSION
The degree of hardness of our tap water was found to be soft with a concentration of 43.2
ppm and this value was within the range of soft; 0-60 mg/L set by the world health
organisation (Jircitano, 2016). A water sample is buffered to pH 10 and taken in to a conical
flask. If an indicator dye like Eriochrome Black T is added to a solution containing
Magnesium ions, the colour of the solution turns to wine red. EDTA, the titrant, complexes
with Magnesium ions, removing them from association with the indicator. When all the
Mg+2 are complexed with EDTA, the indicator will turn blue and this is the end point of the
titration. The EDTA reacts with the remaining calcium ion that has not been
complexed(Veríssimo, Oliveira and Gomes, 2007). Errors encountered in this experiment
were difficulty in telling when solution had turned from purple to blue leading to
overshooting. Standardization, which allow for concentration of the titrant to be confirmed is
important when doing a titration because the the result of titration depend upon the accuracy
of the concentration of the titrant. Tap water is safe to drink especially because it contains
fluoride which has added health benefit for the teeth and gums, tap water is an easiest eco-
friendly resource (Veríssimo, Oliveira and Gomes, 2007). Mineral water is safe to drink
however due to handling and packaging process, it is possible to introduce contaminants in
water. Though is sound advantageous to use tap water, tap water sources could be
contaminated from natural disasters or from old piping. To carry out metal cation titrations
using EDTA in determination of metal ion concentration, it is almost always necessary to use
a complexometric indicator / suitable metal to determine when the end point has been
reached, not any other indicator can be used. These complexometric indicators are organic
dyes such as Fast Sulphon Black, Eriochrome Black T, Eriochrome Red B, Patton Reeder, or
Murexide and the colour change shows that the indicator has been displaced (usually by
EDTA) from the metal cations in solution when the end point has been reached. There is also
pH limitation since the pH of an EDTA titration should be adjusted so that one type of metal
ion (e.g. Mg2+) can be titrated without interference from others (Ca2+)(Required et al.,
2003).
6. CONCLUSION
The total hardness of tap water in our experiment was found to be 43.2 mg/L which was soft
and this was acceptable because the hardness of good quality drinking water should not
exceed 250 mg/L measured as calcium carbonate equivalents.

7. REFERENCES
Equation, M. (2004) ‘Determination of total hardness of water by complexonometric titration
( EDTA ) Model Equation : List of Quantities ’:, Workbench, pp. 1–6.
Jircitano, A. J. (2016) ‘Determination of the Hardness of Water’, Penn State Behrend, pp. 2–
5. Available at: http://chemistry.bd.psu.edu/jircitano/Water05.pdf.
Required, D. C. et al. (2003) ‘Determination of Water Hardness using Complexometric
titration’, pp. 259–64. Available at:
http://mccord.cm.utexas.edu/courses/spring2005/ch455/Spr05455Wk4Lab.pdf.
Veríssimo, M. I. S., Oliveira, J. A. B. P. and Gomes, M. T. S. R. (2007) ‘Determination of the
total hardness in tap water using acoustic wave sensors’, Sensors and Actuators, B: Chemical,
127(1), pp. 102–106. doi: 10.1016/j.snb.2007.07.006.