Você está na página 1de 6

Determination of hardness of water using complexometric titration

1. Scope The International Standard ISO 6059 specifies a titrimetric method using ethylenediaminetetraacetic acid (EDTA) for the determination of the sum of calcium and magnesium concentration in ground waters, surface waters and drinking waters. The method is not intended for effluents and waters having a high concentration of salts, such as sea water. The lowest concentration that can be determined by this method is 0.05 mmol/L. 2. Principle This is a complexometric titration of calcium and magnesium with an aqueous solution of disodium salt of EDTA at pH value of 10 and Mordant black 11 as an indicator, which forms a claret or a violet colour in the presence of calcium and magnesium ions. The sodium salt of EDTA dissociates into ions in aqueous solution Na2Y2H2.2H2O(s) 2 Na+(aq) + H2Y2-(aq) + 2H2O(l)

During the titration EDTA reacts first with free calcium and magnesium ions in the solution Me2+(aq) + H2Y2-(aq) MeY2-(aq) + 2 H+(aq)

Me2+ (Ca2+, Mg2+) and at the end/equivalent point EDTA reacts with the calcium and magnesium ions superseded from their complexes, which were created with the indicator molecules, liberating indicator and causing the colour to change from claret or violet to blue. At the equivalence point the amount is: n(Ca2+ + Mg2+) = n(EDTA) The results are given in amount of substance concentration (molarity). 3. Apparatus 3.1. Instruments Calibrated analytical balance Electric oven for drying

3.2. Ordinary laboratory apparatus Weighing vessel Burette, 25 mL capacity, graduated in divisions of 0.05 mL, class A or equivalent 2 x Analytical flasks 1000 ml Polyethylene bottle 1 L 4 x Erlenmeyer flasks 500 mL, 250 mL 3.3. Reagents and materials Ammonia buffer solution (see 3.4.1) EDTA standard solution (see 3.4.2) Materials and their safety codes Name Ammonium chloride NH4Cl Ammonia solution w = 25%, (20 0C) = 0.91 g/mL Disodium magnesium salt of EDTA (C10H12N2O8Na2Mg) Disodium salt of EDTA dihydrate (C10H14N2O8Na2.H2O) Mordant black 11 (C20H12N3O7SNa) Eriochrome black T Hydrochloric acid 4 mol/L Methyl red indicator Triethanolamine (OHCH2CH2)3N) Ethanol CAS No. 12125-02-9 7664-41-7 14402-88-1 6381-92-6 R/S code R 22-26 S 32 R 36/37/38 S 26

1787-61-7 7647-01-0 493-52-7 102-71-6 64 -17 -5 R 11 S 7-16 R 36/38 S 2-28.1

3.4. Reagent solutions 3.4.1. Ammonia buffer solution Dissolve 67.5 g of ammonium chloride in 570 mL of ammonia solution. Then add 5.0 g sodium magnesium salt of EDTA and dilute to 1000 mL with distilled water 3.4.2. EDTA Standard volumetric solution c = 10 mmol/L. Dry a portion of EDTA dihydrate salt for 2 h at 105 0C, dissolve 3.725 g of the dry salt in water and dilute to 1000 mL in the volumetric flask. Store EDTA solution in a polyethylene bottle and check the concentration at regular intervals.

3.4.2.1. Standardisation Standardise the solution (3.4.2.) against the calcium reference standard solution by the procedure described in clause (3.4.3.). Use 20.0 mL of the calcium standard reference solution and dilute to 50 mL. 3.4.2.2. The concentration of the EDTA solution c(EDTA) expressed in millimoles per litre is given by relationship c(EDTA) . V(EDTA) = c(Ca2+) . V(Ca2+) Where c(Ca2+) V(Ca2+) V(EDTA) is the concentration expressed in milimoles per litre of the standard reference solution is the volume in millilitres of the calcium standard reference solution is the volume in millilitres of the EDTA solution used for stadardization c(EDTA) =

c (Ca 2+ ). V(Ca 2+ ) V(EDTA)

3.4.3. Calcium standard reference solution c(CaCO3) = 10 mmol/L Dry a sample of pure calcium carbonate for 2 h at 150 oC, and allow to cool to room temperature in a desiccator. Place 1.001 g of it in a 500 mL conical flask and moisten it with distilled water. Add 4 mol/L hydrochloric acid in drops until all carbonate is dissolved. Avoid adding excess acid. Add 200 mL of water and boil for few minutes to strip out carbon dioxide. Cool to room temperature and add a few drops of methyl red indicator solution. Add 3 mol/L ammonia solution until the solution turns orange. Transfer the solution quantitatively to a 1000 mL volumetric flask and make up to the mark with distilled water. 1 mL of the solution contains 0.4008 mg (0.01 mmol) of calcium. Note - Commercially available solution may be used. 3.4.4. Mordant black 11, indicator Dissolve 0.5 g of mordant black 11, the sodium salt of (1-(1-hydroxi2naphtylazo-6-nitro-2-naphtol-4-sulfonic acid) in 100 mL triethanolamine. Up to 25 mL ethanol may be added instead of triethanolamine to reduce the viscosity of the solution. NOTE- To facilitate the detection of the end point, the indicator may be modified by the solution of 0.17 g methanol salt (4-anilido azobenzene sulfonic acid sodium salt.). The colour will now change from red to pale grey or green.

5. Procedure 5.1. By means of pipette transfer 50.0 mL of the test solution to a 250 mL conical flask. Add 4 mL of buffer solution and 3 drops of Mordant black 11 indicator. The colour of the solution should now turn to claret or violet and the pH value should be 10.0 0.1. Titrate immediately. Add the EDTA solution when the colour of the solution starts to change from claret or violet to blue. The end point is reached when the last shade has disappeared. 5.2. Titrate additional test portion in the following manner. Transfer 50.0 mL of the test solution in to a flask. Add EDTA solution to the sample amounted 0.5 mL less, than it was consumed for the first sample. Add 4 mL of the buffer solution and 3 drops of mordant black 11 indicator. Add EDTA until the end point is reached. 5.3. If the consumption of EDTA is less than 4.5 mL, titrate a smaller sample volume. Add destillated water until reaching a total titrated volume of 50 mL. If the consumption of EDTA solution exceeds 20 mL, titrate using a small test portion. Add destillated water so that the starting volume is 50 mL. 6. Expression of the results The sum of calcium and magnesium contents c(Ca2+ + Mg2+) expressed in millimoles per litre is given by the relationships V(sample) . c(Ca2+ + Mg2+) = V(EDTA) . c(EDTA) c(Ca2+ + Mg2+) = V(EDTA) c(EDTA) solution. V(sample)

V(EDTA).c(EDTA) V(sample)

the volume in millilitres of EDTA used in the titration (see 5.3). is the concentration expressed in millimoles per litre of the EDTA is the volume in millilitres of the test solution (normally 50 mL) For calculation of hardness see the annex.

7. Precision The repeatability of the procedure is 0.04 mmol/L, corresponding to approximately 2 drops of the EDTA solution.

8. Result Average 2+ 2+ c(Ca + Mg ) (mmol/L)

Annex Concept of hardness of water (This annex does not form the part of standard) A.0 Hardness of water is an old concept to describe the content of calcium and magnesium in waters. Different kinds of hardness are defined (total hardness, carbonate hardness and others) and various countries have adopted different definitions of the concept. Some definitions are given in clause A.1 as examples. A.1 Definitions A.1.1 total hardness: The total concentration of calcium and magnesium. A.1.2 carbonate hardness: Part of the total hardness equivalent to the carbonate and hydrogen carbonate contents of the water.

Questions
1. When determining the total calcium and magnesium ion content in water using EDTA, which of the following is 2+ established? a carbonate hardness c(Ca ) 2+ ) b magnesium hardness c(Mg 2+ 2+ c total hardness c(Ca + Mg ) 2. 500 mL of EDTA solution with the concentration of 10 mmol/L is to be prepared. What mass of the disodium salt EDTA dihydrate C10H14N2O8 2H2O is needed? a 1.8625 g b 0.3722 g c 3.722 g 3. 20.00 mL of EDTA solution with an approximate concentration 0.1 mol/L is titrated using a reference solution with calcium content of 0.40 mg/mL. What is the consumption of the reference solution? a 10.0 mL b 50.0 mL c 20.0 ml 4. Total calcium and magnesium ion content in water is at least 0.05 mmol/L. What volume of the EDTA solution with a concentration of 10 mm/L should be added when 50.0 mL of a water sample is titrated? a 2.50 mL b 0.25 mL c 25.0 mL 5. When performing complexometric EDTA titrations, the end point is reached when all metal ions have combined with a EDTA b indicator c indicator and EDTA 6. Ammonia buffer solution contains a ammonia chloride NH4Cl b ammonia solution NH3(aq) c ammonia chloride NH4Cl and ammonia NH3(aq) solution .

Você também pode gostar