' IDAI GULF STANDARD U.A.E, STANDARD NO:641 /1996 NO:641/1997 METHODS OF TEST FOR DRINKING AND MINERAL WATER- PART 5=DETERMINATION OF TOTAL HARDNESS, CALCIUM AND MAGNESIUM a United Arab Emirates21 2A. 2.1. METHODS OF TEST FOR DRINKING AND MINERAL WATER - PART 5: DETERMINATION OF TOTAL HARDNESS, CALCIUM AND MAGNESIUM SCOPE AND FIELD OF APPLICATION This standard is concemed with the determination of total hardness, calcium and magnesium content in drinking and mineral water using the conventional test methods and atomic absorption method. CONVENTIONAL TEST METHODS Determination of total hardness content 1 Method principle Titration using Ethylenediaminetetraacetic acid (EDTA) solution as follows: If a small amount of vegetable dye such as black mordant No. Il or equivalent is added to an aqueous solution containing calcium and magnesium ions at pH of (10 £0.1), the solution becomes wine red, if EDTA is added as a titrant «the: solution: tums to blue at the neutral point. / 2 Apparatus = Conical flasks of 250 mi, 500 ml and 1000 ml capacity. Burette, graduated in division of 0.05 ml or rather than 0,02 and or less, - Volumetric pipettes 10 n'%, 25 ml and 50 ml capacities - Graduated cylinder 100 ml capacity.&y - 2.4.3 Reagents NOTE: All reagents used should be recognized analytical grade. = Buffer solution: Prepare by dissolving 16.9 g of ammonium chloride. in 143 ml of concentrated arumonium hydroxide solution. Then add 1.25 g of the disodium magnesium salt of EDTA and dilute to 250 ml with distilled water and store in a polyethylene bottle or in a resistant glass for no longer than 1 month, Stopper tightly to prevent the loss of ammonia or pick up of carbon dioxide. This solution is considered unfit for using if it fails to give pH value of (10 0.1) at the neutral end point. NOTES a) If the disodium magnesium salt of EDTA is unavailable, dissolve 1.179 g of disodium salt of ethylenediaminetetraacetic acid dihydrate and 780 mg magnesium sulfate or 644 mg magnesium chloride in $0 ml distilled water. Add this solution to 16.9 g ammonium chloride and 143 ml concentrated ammonium hydroxide with mixing and dilute to 250 ml with distilled water. b) Satisfactory altemate odourless buffers also are available commercially. - EDTA standard solution 0.01 mol/L: Prepare by drying disodium salt of EDTA dihydrate at 80°C for 2 hours. Dissolve 3.725 g-of, the dry salt in water and dilute to 1000 ml with distilled water in a volumetric flask and store in a polyethylene bottie and check its concentration at “regular intervals and standardize the solution against the calcium standard reference solution as in item (2.1.4) using 20 ml of the calcium standard reference suiution and dilute to 50 ml and check its concentrarion at regular intervals as follows:cx The concentration of the EDTA solution (mol/L) = Where: C = The concentration. of the calcium standard reference solution.(0.01 maV/L). V_ = The volume of the titrant EDTA solution read from the burette (ml). The volume measured by pipette. f the standard calcium soliition (ml) 1 ml of this solution is equivalent to 1 ml standard calcium solution or 1 mg calcium carbonate. Calcium standard solution (0.01 mo¥L): Prepare by drying an of anhydrous calcium carbonate for 2 amount of analytical grad: hours -at 150°C and allow to cool to room temperature in a desiccator. “Weigh 1.001'g in 500 ml conical flask, and moisten it with water, add dropwise diluted hydrochloric acid (1 + 1) until all the calcium carbonate has dissolved, avoid adding excess acid. Add 200 mi of distilled water and put the funnel in the neck of the flask and boil the solution for a few minutes to expel carbon dioxide. Cool the solution to room temperature and add few drops of methyl red indicator, then 3 mol/L. Ammonium hydroxide solution or diluted hydrochloric acid (1 + 1) until the solution tums orange, Transfer the solution quantitatively to 2 1000 mi volumetric flask and make up to the mark with distilled water. (1 mi of this solution contains 0.4008 mg of calcium or 1 mg calcium carbonate Mordant black No. 11, indicator (Erichrome black - Erichrome black T - solochrome black - omega chrome bleck $): Dissolve 0.5 g of the indicator in 100 ml of triethanolamine (ethanol may be used) 64)2.1.4 21.41 2.1.4.2 To prepare the indicator in powder form: mix well 0.5 g from the indicator with 100 g powder sodium chloride = Inhibitor: Prepare by dissolving 5 g sodium sulfide nonahydrateot 3.7 g sodium sulfide pentahydrate in 100 mi distilled water ina flask. and shake it to exclude the air, this inhibitor deteriorates with oxidation. It is used when appreciable concentration of heavy metals is present in water sample. Procedure : Transfer 25 ml of the test sample to a 250 ml conical flask, add 1-2 ml of the buffer solution and 3 drops of mordant black 1] indicator or il the colour of solution suitable amount from indicator powder un turns to claret or violet and its pH value should be (10.0 + 0.1). Titrate the solution immediately with EDTA solution under continuous stirring until the colour of the solution changes to blue at neutral point. NOTES: a- In the case of analysis of water samples with hardness content less than 5 ppm, take a large volume from the sample (100 - 1000 ml), add suitable amounts from buffer solution and indicator using microbturet and titrate the blank solution at the same time for comparison. b- In the case of water samples which need more than 10 ml EDTA, solution for titration, take a lower amount from the sample and dilute to 25 ml with distilled water. The time between adding buffer solution to the end of titration shail not exceed 5 minutes be)If the colour of the. solution does not change to blue at neutral point, it means that there are interferring ions, so inhibitor should be added to prevent this interference, 2.1.4.3 Carry out the procedure mentioned in items 2.1.4.1, 2.1.4.2 on distilled water sample (which used in preparation of “samples and reagents). Subtract volume of EDTA used for blank from volume of EDTA used in titration of test samples, 2.1.5 Calculation 1000 Total hardness content as CaCO3 (ppm) Where: VY = volume of the test portion (ml) Cy = mg of calciuar carbonate equivalent to 1 ml EDTA titrant Vy = volume of EDTA solution used in the titration (ml) 2.2 Determination of calcium content 2.2.1 Method principle: Caicium can be determined alone without magnesium with EDTA standard solution and at a pH between 12 and 13 where magnesium ions precipitate as magnesium hydroxide and the indicator combines with caleium only. 2.2.2 Apparatus Burretie, 10 ml capacity, graduated in division of 0.05 ml than 0.02 ml or less. ~ Conical flasks of 250 ml, 500 ml and 1000 mi capacity. = Volumetric pipettes 10 ml, 25 ml and 50 ml capacities = Graduated cylinder 100 ml capacity.22. 3 Reagents = Sodium hydroxide solution 1 N: Prepare by dissolving 4g of sodium hydroxide in 100 ml of freshly distilled water and store ina polyethylene bottle and take precautions to avoid contamination by atmospheric carbon dioxide. EDTA standard solution 0.01 mol/L: Prepare and standardize as in 2.13. ~ Calcium standard solution: Prepare as in 2.1.3, ~ Calcon carboxylic acid indicator: Prepare by mixing 0.2 g of [- hydroxy-1(2-hydroxy-4-sulfo-I-naphthylazo-3-naphthoic acid] and 100 g of sodium chloride. = Murexide (ammonium parpurate) indicator: Prepare by dissolving, 150 mg from the indicator in 100 g absolute ethylene glycol or by mixing 200 mg murexide with 100 g sodium chloride and grinding the mixture to 40 to 50 mesh, This indicator change from pink to purple at the end point Procedure By means of a pipette, transfer 50 ml of the test sample to a 250 ml conical flask, add 2 ml of the sodium hydroxide solution and approximately 0.2 g of calcon carboxylic acid indicator and mix. In the case of using liquid indicator, add one to two drops to the sample, Titrate the solution immediately with EDTA standard solution under continuous stirring during the titration until the end point of titration is reached (the colour of the solution changes to a distinct blue), NOTE: Take into account what has been mentioned in the notes in item 2.1.3 buyby - 2.2.5 Calculation Calculation calcium hardness content as calcium carbonate (p.p.m.) from the equation: to. Content for calcium p.pm. = V2xC2x = ; v Where: . Cz = Calcium carbonate content equivalent to 1 ml EDTA titrant (mg) V_ = Volume of the test sample (il) V2 = Volume of EDTA solution used in the titration (ml) 2.3 Determination of magnesium content by calculation method Calculation of magnesium content shall be carried out as follows: 1000 Magnesium content (p.p.m.) = (Vi- V)X C3 x ~ v Where: g ‘Vi, V2 = Asin2.1.5 and 2.2.5 C3. = Magnesium content equivalent to 1 ml from EDTA solution used in titration (mg) = 0.2 432 mg. 3. DETERMINATION OF CALCIUM AND MAGNESIUM CONTENT BY ATOMIC ABSORPITON METHOD Apparatus = Atomic absorpiton spectrometer: Set up and operated according to the manufacturer's instruction and include:a) A device for vaporizing the sample: With bumer for air/acetylene flame. b) A light source: With hollow cathode lamp for calcium and magnesium determination. ¢) Mono-chromiator filter adjustable slit. d) Photo-electric detector with its associated electronic amplifying’and measuring equipments, Reagents NOTE: All reagents use should be recognized analytical grade. - Hydrochloric acid its sp.gr. (1.18). - Hydrochloric acid 0.1 moVL: Prepare by diluting 8 ml of hydrochloric acid (sp.gr. 1.18) to one litre ~ Lanthanum chloride solution containing 20 g of lanthanum per litre: Prepare by dissolving 24 g lanthanum oxide in a1 litre volumetric flask slowly “and cautiously adq150 ml of hydrochloric acid (sp.gr. 1.18) while stiming to dissolve the lanthanum oxide, make up to the Mark with distilled water. - Calcium stock solution 1000 mg/L.: | Dry a portion of calcium carbonate at 180°C fer I hour and allow it to cool in a desiccator. Weigh (2.50 + 0.01) g from it and shake in 100 ml of distilled water, Add slowly the minimum amount of hydrochloric acid (0.1 moV/L.) necessary to dissolve the calciuin carbonate (approximately 250 bg)ml). Boil the solution to expe! dissolved carbon dioxide and cool. Transfer the solution quantitatively to a 1000 ml volumetric flask and make up to the mark with hydrochloric acid (0.1 moV/L.). Store the solution in a polyethylene or polypropylene bottle, = Magnesium stock solution 1000 mg/L:: Dry 2 portion of magnesium oxide at 1800C for 1 hour, weigh (1.66 + 0.01) g and dissolve in hydrochloric acid (0.1 moV/L.), dilute with the same acid to 1000 ml in a volumetric flask or use 4.95 from magnesium sulfate salt initead of magnesium oxide, Store the solution ina polyethylene bottle, ~ Calcium-magnesium stock solution contains 20 mg of calcium and 2 mg of magnesium per litre: with two pipettes, transfer 20 ml of the calcium stock solution and 2 ml of the magnesium stock solution to 2 1000 mi volumetric flask, make up to the mark with hydrochloric acid (0.} mol/L.). Procedure Sample shall be collected in clean polyethylene or polyproplene bottles, as soon as possible add 8 ml hydrochloric acid (sp.gr. 1.18) per litre of sample in order to reduce its pH value and prevent precipitation of calcium carbonate, samples shall be analyzed as soon as possible after collection. Preparation of calibration solutions: To a series of seven 100 ml volumetric flasks, add to each either 10 ml of the lanthanum chloride solusion if an air/acetylene flame is to be With a pipette add 0,2.5, 5; 10, 15, 20 and 25 ml of the calcium drochloric used, sium stock solution and make up to the mark with > mag acid (0.1 mol/L} br3.3.3 3.3.4 3.3.5 & Sis Preparation of test solution To prepare the test solution, add 10 ml of the sample in a 100 ml volumetric flask with a pipette, then add 10 mi of the lanthanum chloride. solution if an air/acetylenee flame is to be used and make up to the mark with hydrochloric acid (0.1 mol/L). Preparation of blank solution as in 3.3.3 using the same reagents and use distilled water instead of the sample. Preparation of calibration curve: By aspiration the calibration solutions and blank solution with hydrochloric acid (0.1 moV/L.) between each, camry out the measurements et the wavelengths shown in the following table: Celefum Magnesium Wavelength (am) 422.7 2352 | Kind of flame’ Air/acetylene | 3 to 50 0.9 toS | Analytical content used flame (p.p.m.) Prepare calibration curve by plotting the absorbance readings against the calcium and magnesium content or cary out manufacturer's method for preparation of calibration curve and measure of the concentrations with direct or indirect method according to equipment use. Test the sample and measure the absorbance and trom which calcium and magnesium content from the calibration curve can be calculated as follows: Calcium content from the calibration curve x ~ bey G @5.1 ous 1 oe FV, Magnesium content from the calibration curve x —~ Where: F = The dilution factor resulting from the addition of hydrochloric acid (1.18 g/L.) to the test sample. V = Volume of the original sample (10 ml) taken for analysis (item 3.3.1) V1 = Volume of the volumetrié flask (100 ml). DETERMINATION OF TOTAL HARDNESS MATHEMATIC- ALLY Total hardness (mg calcium carbonate/L.) = 2.497 (mg calcium/L.) + 4.118 (mg magnesium/L,) DETERMINATION OF CALCIUM AND MAGNESIUM WITH AUTOMATIC ANALYSIS DEVICE Determination of calcium content Apparatus ~ Automatic analysis device. Volumetric flasks with capacity ranged from 100 to 1000 n Reagents - Deionized distilled water. be,-12- - 8-hydroxyquinoline: Prepare by placing approximately 800 ml of deionized distilled water in 1000 ml volumetric flask, add 24.75 ml of concentrated hydrochloric acid and mix, add 2.5 g of hydroxy quinoline and stir unti! coupletely dissolved. Add 1 ml of Brij 30% solution and dilute to 1 lit. with distilled water. Cresolphthaline: ‘Place approximately 800 ml of deionized distilled water in a 1 lit, volumetric flask, add 16.5 ml of concentrated hydrochloric acid, 2.5 g of hydroxyquinoline and stir until completely dissolved. Add 0.07 g of cresolphthaline and stir to dissolve, add 1 ml of Brij 30% solution and dilute to 1 lit with deionized distilled water. - Diethylamine 3.75%: - Prepare by placing 800 ml deionized distilled water in-1 lit, volumetric flask, add 37.5 ml of diethylamine and mix, 0.5 g of potassium cyanide and stir until completely dissolved, and dilute with deionized distilled water. - Stock calcium solution (1 ml = I mg calcium): Prepare by placing 2.4972 g of calcium carbonate in 1 lit, volumetric flask, add approximately 100 ml deionized distilled water, 10 ml hydrochloric acid and stir to dissolve. Dilute to the mark with deionized distilled water. - Standard magnesium solutions: Place 0.0, 0.5, 1, 1.5, 2, 2.5.3, 3. and 4 mi from stock solution in 100 ml volumetric flasks, dilute to the mark with deionized distilled water to obtained standard solutions contains 0.0, 5, 10, 15, 20, 25, 30, 35 and 40 microgram calsium/m. Apparatus warking - Adju - Use 570 nm filter. ~ Connect the chemical solutions according to Fig. (1) apparatus accwardsJ 5.14 5.21 13 Calculation Plat the standard curve from the relation between the peak curve and the concentration of standard solutions, and obtained calcium concentrate of the sample from it Determination of magnesium'content Apparatus Automatic analysis device. Volumetric flasks with capacity ranged from 100 to 1000 ml Reagents Deionized distilled water. Stock xylidil blue solution: prepare by dissolving 0.16 g xylidil blue in 100 ml of ethanol in 200 ml beaker, heat to 40-50°C with mixing until completely dissolving, add ethanol to the mark. Standard xylidil bluesolution: = Solution A: 60 ml stock xylidil solution. Solution B:* prepare by dissolving 8 g sodium tetraborate anhydrous in 400 ml distilled water. Mix 1:1 slution A and soludon B, then add 0.8 ml of 8 nj 30%. sium solution (1 ml = | mg magnesium) Stock m: by dissolving 8.36 g of magnesiuin chloride in L lit deionized distilled water5.23 = Standard magnesium solutions: Place 0.0, 0.5, 1, 1.5, 2, 2.5, 3, 3.5 and 4 mi from stock solution in 100 ml volumetric flasks, dilute to the mark with deionized distilléd water to obtained standard solutions contains 0.0, 5, 10, 15, 20, 25, 30, 35.and 40 microgram magnesium 1 ml Werking of the apparatus ~ Adjust the apparatus according to manufacturer’s instructions. - Use 505 nm filter. - Connect the chemical solutions according to Fig. (2). Calculation Plot the standard curve from the ylation between the peak curve and the concentration of the standard solutions, and obtained magnesium concentration of the sample from it.