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EXPERIMENT 6. DETERMINATION OF HARDNESS OF WATER WITH EDTA

BACKGROUND In this experiment the amount of calcium and magnesium present in a water sample is determined. The determination of the hardness of water is important in water treatment plants. In this experiment a sample of hard water is titrated with EDTA, with calmagite as indicator. In the titration of calcium and magnesium with EDTA the indicator calmagite works in the following way. When a small amount is added to a solution containing magnesium at pH 10, red MgIn forms. As EDTA titrant is added, free magnesium ions in solution react with it. After all the free magnesium is complexed, the next portion of EDTA removes magnesium from the indicator complex, converting the indicator to the blue HIn2 form. The pH must be near 10 because at pH values above 12 or below 8 the free indicator is red like the magnesium complex, and therefore no color change can be observed. The calcium-calmagite complex is too weak to function as an indicator (log K (CaIn) = 3.7 at pH 10). Calcium can, however, be titrated and an end point obtained when a trace of magnesium is present. In this experiment a small amount of magnesium is added to the titrant since the primary standard, pure calcium carbonate, contains none. The optimum pH range for titrations of calcium and magnesium with EDTA is about 9 to 11. In solutions more acidic than pH 9, formation of the metal-EDTA complex is incomplete, whereas in solutions above pH 12, magnesium hydroxide begins to precipitate. A solution of approximate strength of the disodium salt of EDTA, Na2H2Y.2H2O, is prepared and standardized against primary standard calcium carbonate. In addition to having all the properties of a suitable primary standard, calcium carbonate has the added advantage that the element titrated, calcium, is a major component of water hardness and of limestone.

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PROCEDURE Reagent List: Unknown sample - do not dry EDTA , di-sodium salt of - prepare 0.015 M stock soln. magnesium chloride 1%soln. - supplied ammonium hydroxide conc. 15M calcium carbonate - dried HCl conc.12M ascorbic acid Calmagite 0.1 % soln. - indicator

Preparation of EDTA Solution (Must be prepared in advance) Prepare an approximately 0.015 M EDTA solution by adding 2.5 g of the disodium salt,1 10 mL of 1% MgCl2 solution, and 1.5 mL of 6 M NH3 to about 450 mL of water. In this experiment use only distilled water purified by passage through a column containing either a cation-exchange resin or a mixture of cation- and anion-exchange resins. (This water will be provided.) Preparation of Calcium Carbonate Standard2 Weigh to the nearest 0.1 mg approximately 0.5 g of dry primary-standard CaCO3 into a clean, dry 50 mL beaker. Transfer most of the CaCO3 without loss to a dry funnel inserted in the top of a dry 100 mL volumetric flask. Transfer of the last particles is unnecessary. Do not use liquid in this transfer. Weigh the beaker and any remaining calcium carbonate to the nearest 0.1 mg, obtaining the weight of CaCO3 in the flask by difference. Tap the funnel to transfer most of the solid, and then rinse the last particles through the funnel into the flask with a milliliter of 12 M HCl.3 Add 1 mL more of 12 M HCl to the flask by rapid dropwise addition. Warm if necessary to complete the

The disodium salt of EDTA is the most commonly used form, being easier to prepare commercially and more soluble in water than the acid, H4Y. Complete dissolution is somewhat slow, however, requiring 10 to 15 min. Occasional shaking speeds the process. 2 It may be convenient to prepare the limestone sample solution (see next part of experiment for details) at the same time as the CaCO3 standard, since dissolution of the limestone is often slow. 3 The 12 M (concentrated) HCl is stored in the fume hood to minimize exposure to its aggressive vapor. Use of more HCl than the minimum necessary to dissolve the CaCO3 leads to difficulty later with pH adjustment.

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dissolution.4 When dissolution is complete, remove the funnel, rinsing inside and out with demineralized water from a wash bottle as it is being removed. Fill the flask to the mark with distilled water, stopper, and mix well. Sample Preparation Collect an unknown sample from your instructor. Record the number of your unknown and the total mass of the sample in your laboratory notebook. Transfer the unknown sample through a dry funnel into a dry 100 mL volumetric flask. Tap the funnel to ensure that most of the sample has been transferred into the flask. Rinse the sample container with approximately 1 mL of concentrated hydrochloric acid. Transfer this solution into the volumetric flask ensuring that all remaining particles of your unknown are washed into the volumetric flask. Add an additional 1 mL of concentrated HCl(aq) to your flask by rapid drop-wise addition. Gently warm the flask to ensure complete dissolution. Wash the walls of the funnel with distilled water, fill the flask to mark, stopper and mix well. Titration of Standards Using a calibrated 10 mL pipet, measure aliquots of the standard calcium solution into each of three or four 200 or 250 mL conical flasks.8 Titrate the calcium standards and samples in alternation. Immediately before each titration, take a flask containing the aliquot and add about 50 mg of ascorbic acid to the flask, then approximately 10 mL of 6 M NH3,9. Swirl the flask to mix the contents after each addition. Add 4 to 5 drops of 0.1% calmagite indicator solution, and titrate with EDTA solution until the indicator changes from red to blue.10 (As before, use the drop of EDTA that gives the greatest color change as the end point.) Titration of Unknown Follow the same titration procedure for the solution of your unknown as the procedure described above for the titration of the standard samples.

Heating of volumetric flasks to moderate temperatures on a hot plate does not affect calibration, as the original volume is regained upon cooling room temperature. 8 If the sample contains some insoluble silicate material, avoid inclusion of the solids in the pipetted portion insofar as possible. 9 Ammonia alone is added here because the presence of excess HCl from the dissolution must be neutralized. This normally provides sufficient NH4Cl to serve as the HB+ component of the buffer. 10 Some limestones contain heavy metals that slowly bind strongly to calmagite. Therefore solutions should be titrated promptly and not too slowly once indicator has been added, otherwise the color change may be poor.

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CALCULATIONS FOR WATER HARDNESS The concentration of EDTA solution is found by (wt. of CaCO3)(V10/100 mL) M EDTA = ((mol wt CaCO ))(mL EDTA/1000) 3 where V10 is the calibrated volume of the 10 mL pipet. Water hardness, expressed in parts per million or milligrams per liter of CaCO3,11 can be calculated by hardness in ppm =
(mL EDTA/1000)(M EDTA)(mol wt CaCO3)(1000 mg/g) (vol of sample in liters)

The hardness in ppm value represents the CaCO3 concentration in the solution prepared from your unknown sample. Report the result as ppm of CaCO3 in the solid unknown sample that was supplied to you.

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The results could be reported in several ways, such as % CaCO3, % MgCO3, or % Mg. In accordance with common practice the approach employed here assumes that all the material titrated is calcium, and is calculated as calcium carbonate.