No.

081/2 e

Application Bulletin
Of interest to:

Saltworks, water-analysis and general analytical laboratories

A 1, 7, 11

Potentiometric determination of calcium and hydroxide ions in aqueous solutions (such as drinking water, brine, etc.)
Summary
The method described below enables calcium and hydroxyl ions to be determined in one single operation by potentiometric titration. The determination is not affected by the presence of magnesium salts, nor by large excesses of alkali ions. After the addition of ethylene-glycol tetracetic acid (EGTA), three potential jumps are obtained on back-titration with hydrochloric acid. The first corresponds to the hydroxyl-ion concentration, the second to the excess of EGTA, and the third to the calcium-EGTA complex.

Instruments and accessories

726 Titroprocessor with 685 Dosimat or 700 Dosinos, 751 GPD Titrino, 736 GP Titrino, 716 DMS Titrino or 702 SET/MET Titrino Titration Stand for attachment to above Titrators: 2.728.0040 Magnetic Swing-out Stirrer or 2.727.0100 Titration Stand with built-in magnetic stirrer, rinsing pump and rinsing head or 2.727.0010 Titration Stand with rinsing pump and rinsing head + 2.722.0010 Rod Stirrer with controller and stirrer propeller or 2.703.0010 Titration Stand with integrated pump for rinsing and siphoning off the titration vessel content. + 6.5613.XXX ECO titration equipment. 6.3014.213 Exchange Unit for Titrinos and Dosimats or 6.3031.XXX Dosing Units for Dosinos 6.0232.100 Combined glass electrode with 6.2104.020 electrode cable Printer with suitable 6.2125.0X0 printer cable (except for 2.726.0020 and 2.726.0120)

Application Bulletin

No. 081/2 e

Potentiometric determination of calcium and hydroxyl ions in aqueous solutions (such as drinking water, brine, etc.) Page 2

Reagents
Hydrochloric acid c(HCl) = 0.2 mol/L c(EGTA) = 0.1 mol/L 38.04 g ethylene-glycol-bis-(2-amino-ethyl)-n,n,n,n'-tetracetic acid (Fluka Catalogue No. 03780) are mixed to a slurry with 800 mL distilled water and dissolved by adding a 32 % solution of NaOH. The same caustic soda solution is used to adjust the pH to 11.0. The resulting solution is made up to 1 litre with distilled water

Analysis
Take a 50 mL sample, which should contain 10 to 240 mg Ca/litre (with higher calcium concentrations a correspondingly smaller sample volume is taken), add 5 mL of the EGTA solution and titrate this mixture with 0.2 mol/L hydrochloric acid. When evaluating the results the EGTA stage is discarded. For this purpose a blank value must first be determined (5 mL EGTA solution in distilled water). When hydroxyl ions are present their concentration is shown by the first potential jump, the second corresponds to the excess EGTA, and the third to the calcium-EGTA complex. Calculation: 1 mL 0.2 mol/L HCl corresponds to 1 mL 0.1 mol/L EGTA corresponds to 4.008 mg calcium and 3.401 mg OH4.008 mg Ca+2

Remarks
The determination is not affected by the presence of magnesium or alkali-metal ions. With small calcium concentrations dilute reagents may be used. With 0.01 mol/L HCl and 0.01 mol/L EGTA the limit of determination is 2 mg/L Ca. If no magnesium is present the relatively expensive EGTA may be replaced by the cheaper ethylene-diamine tetracetic acid (EDTA). However, when EDTA is used the potential jumps are not so marked.

Literature
De Groot, D.C. Simultaneous determination of calcium and hydroxyl ion concentration in brine Fresenius, Z. Anal. Chem. 251 (1970), 299-300