Lab Manual 7 in Text

Experiment 2
Determination of the Hardness of Water

One of the factors that establishes the quality of a water supply is its degree of hardness. The
hardness of water is defined in terms of its content of calcium and magnesium ions. Since the
analysis does not distinguish between Ca2+ and Mg2+, and since most hardness is caused by
carbonate deposits in the earth. hardness is usually reported as total parts per million calcium
carbonate by weight. A water supply with a hardness of 100 parts per million would contain the
equivalent of 100 grams of CaCO3, in 1 million grams of water or 0.1 gram in one liter of water.
In the days when soap was more commonly used for washing clothes, and when people bathed in
tubs instead of using showers, water hardness was more often directly observed than it is now,
since Ca2+ and Mg2+ form insoluble salts with soaps and make a scum that sticks to clothes or
to the bathtub. Detergents have the distinct advantage of being effective in hard water, and this is
really what allowed them to displace soaps for laundry purposes.
Water hardness can be readily determined by titration with the chelating agent EDTA
(ethylenediaminetetrancetic acid). This reagent is a weak acid that can lose four protons on
complete neutralization; its structural formula is
The four acid sites and the two nitrogen atoms all contain unshared electron pairs, so that a
single EDTA ion can for a complex with up to six sites on a given cation. The complex is
typically quite stable, and the conditions of its formation can ordinarily be controlled so that it
contains EDTA and the metal ion in a 1:1 mole ratio. In a titration to establish the concentration
of a metal ion, the EDTA which is added combines quantitatively with the cation to form the
complex. The end point occurs when essentially all of the cation has reacted.
In this experiment we will standardize a solution of EDTA by titration against a standard
solution made from calcium carbonate, CaCO3,. We will then use the EDTA solution to
determine the hardness of an unknown water sample. Since both EDTA and Ca2+ are colorless,
it is necessary to use a rather special indicator to detect the end point of the titration. The
indicator we will use is called Eriochrome Black T, which forms a rather stable wine-red
complex, MgIn-, with the magnesium ion. A tiny amount of this complex will be present in the
solution during the titration. As EDTA is added, it will complex free Ca2+ and Mg²+ leaving the
MgIn complex alone until essentially all of the calcium and magnesium have been converted to
chelates. At this point EDTA concentration will increase sufficiently to displace Mg²+ from the
indicator complex; the indicator reverts to an acid form, which is sky blue, and this establishes
the end point of the titration.
The titration is carried out at a pH of 10, in an NH3 - NH4+, buffer, which keeps the EDTA
(H4Y) mainly in the form, HY3-, where it complexes the Group 2 ions very well but does not
tend to react as readily with other cations such as Fe3+ that might be present as impurities in the
water. Taking H4Y and H3In as the formulas for EDTA and Eriochrome Black T, respectively,
the equations for the reactions which occur during the titration are:
(main reaction) HY3-(aq) + Ca2+ (aq) → CaY2- (aq) + H+(aq) (same for Mg2+)
(at end point) HY3-(aq) + MgIn- (aq) → MgY2- (aq) + HIn2- (aq)
wine red sky blue
Since the indicator requires a trace of Mg2+ to operate properly, we will add a little magnesium
ion to each solution and titrate it as a blank.
Experimental Procedure
Obtain a 50-ml buret, a 250-ml. volumetric flask, and 25- and 50-ml pipets from the stockroom.
Put about a half gram of calcium carbonate in a small 50-ml beaker and weigh the beaker and
contents on the analytical balance. Using a spatula, transfer about 0.4 g of the carbonate to a 250-
ml. beaker and weigh again, determining the mass of the CaCO3, sample by difference.
Add 25 mL of distilled water to the large beaker and then, slowly, about 40 drops of 1 M HCI.
Cover the beaker with a watch glass and allow the reaction to proceed until all of the solid
carbonate has dissolved. Rinse the walls of the beaker down with distilled water from your wash
bottle and heat the solution until it just begins to boil. (Be sure not to be confused by the
evolution of CO2 that occurs with the boiling.) Add 50 mL of distilled water to the beaker and
carefully transfer the solution, using a stirring rod as a pathway, to the volumetric flask. Rinse
the beaker several times with small portions of distilled water and transfer each portion to the
flask. All of the Ca2+ originally in the beaker should then be in the volumetric flask. Fill the
volumetric flask to the horizontal mark with distilled water, adding the last few mL a drop at a
time with your wash bottle. Stopper the flask and mix the solution thoroughly by inverting the
flask at least 20 times over a period of several minutes.
Clean your buret thoroughly and draw about 200 mL of the stock EDTA solution from the
carboy into a dry 250-mL Erlenmeyer flask. Rinse the buret with a few mL of the solution at
least three times. Drain through the stopcock and then fill the buret with the EDTA solution.
Determine a blank by adding 25 mL distilled water and 5 mL of the pH 10 buffer to a 250-mL
Erlenmeyer flask. Add a small amount of solid Eriochrome Black T indicator mixture from the
stock bottle. You need only a small portion, about 25 mg, just enough to cover the end of a small
spatula. The solution should turn blue; if the color is weak, add a bit more indicator. Add 15
drops 0.03 M MgCl2, which should contain enough Mg2+ to turn the solution wine red. Read the
buret to 0.02 mL and add EDTA to the solution until the last tinge of purple just disappears. The
color change is rather slow, so titrate slowly near the end point. Only a few mL will be needed to
titrate the blank. Read the buret again to determine the volume required for the blank. This
volume must be subtracted from the total EDTA volume used in each titration. Save the solution
as a reference for the end point in all your titrations.
Pipet three 25-mL portions of the Ca2+ solution in the volumetric flask into clean 250-mL
Erlenmeyer flasks. To each flask add 5 mL of the pH 10 buffer, a small amount of indicator, and
15 drops of 0.03 M MgCl2. Titrate the solution in one of the flasks until its color matches that of
your reference solution; the end point is a reasonably good one, and you should be able to hit it
within a few drops if you are careful. Read the buret. Refill the buret, read it, and titrate the
second solution, then the third.
Your instructor will furnish you a sample of water for hardness analysis. Since the
concentration of Ca2+ is probably lower than that in the standard calcium solution you prepared,
pipet 50 mL of the water sample for each titration. As before, add some indicator, 5 ml. of pH 10
buffer, and 15 drops of 0.03 M MgCl2, before titrating. Carry out as many titrations as necessary
to obtain two volumes of EDTA that agree within about 3%. If the volume of EDTA required in
the first titration is low due to the fact that the water is not very hard, increase the volume of the
water sample so that in succeeding titrations, it takes at least 20 mL of EDTA to reach the end
point.

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Experiment 2

Determination of the Hardness of Water

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