Determination of Manganese in Brine ( 30% NaCl)

Transcription

1 Application Update 8 Determination of Manganese in Brine ( 0% NaCl INTRODUCTION Sodium chloride brines are used in chlor-alkali cells and must have low concentrations of alkali and alkaline earth metals to prevent membrane poisoning. As discussed in Dionex Application Note 0 (AN 0, manufacturers usually focus on determining single digit µg/l (ppb concentrations of magnesium and calcium. However, these brines are also used to produce crystalline NaCl. When the brines are prepared from seawater, the manganese concentration is also a concern because the presence of Mn limits the size of NaCl crystals. This application update uses the same separation conditions as AN 0, but alters the online sample preparation with the MetPac column to effectively concentrate manganese from 0 times more sample than used in AN 0. This allows accurate determination of 0 ppb manganese in brine. These altered sample preparation conditions do not allow quantification of calcium and magnesium in brine due to the presence of calcium and magnesium in the ammonium acetate and/or acetic acid used for sample preparation. An eluent generator produces the methanesulfonic acid eluent for the cation separation to ensure accurate eluent production, improve retention time precision, simplify operation, and deliver the other recognized benefits of an RFIC system. Equipment Dionex ICS-000 system consisting of DP Dual Pump DC Detector/Chromatography module EG Eluent Generator AS Autosampler AM Automation Manager equipped with a 0-port valve Chromeleon 6.8 Chromatography Workstation Reagents and Standards Deionized water (DI, Type I reagent grade, 8 MΩ-cm resistivity Lithium hydroxide (LiOH Sodium chloride (NaCl Ammonium acetate (CH COONH (See Chelation Ion Chromatography, below. Potassium chloride (KCl Magnesium sulfate (MgSO Calcium chloride (CaCl Manganese sulfate monohydrate (MnSO.H O Ammonia solution 0% (NH OH Glacial acetic acid (CH COOH All compounds were ACS reagent grade or better and from reliable sources. Application Update 8

2 Conditions Guard Column: IonPac CGA 0 mm (P/N 607 Analytical Column: IonPac CSA 0 mm (P/N 607 Flow Rate:.00 ml/min Eluent Source: EluGen II EGC-MSA (P/N 890 Eluent: 0 mm methanesulfonic acid Detection: Suppressed conductivity CSRS ULTRA II mm, recycle mode Suppressor Current: 70 ma Column Temperature: 0 C Noise: < ns Preparation of Solutions and Reagents Eluent Solution Automatically generate 0 mm MSA eluent on-line by pumping DI water through the EluGen II EGC-MSA using DP Pump. M ammonium acetate, ph. ± 0. This reagent can be purchased from Dionex or prepared as follows. Place 600 ml of deionized or high purity water into a clean -L glass container. Tare the bottle. Add g ( ml of ultrapure glacial acetic acid and mix thoroughly. In a fume hood, slowly add g (8 ml of 0% ultrapure ammonium hydroxide and mix thoroughly. Agitate the bottle to thoroughly mix DP Pump in DP Pump in Chelation Ion Chromatography Column: MetPac CC-, 0 mm (P/N 6 Loop: ml Eluents: M Ammonium acetate (P/N 0 00 mm Acetic acid Preconcentration Step: See Table and Figure. Waste EG (DP Pump Column out Waste EG (DP Pump out Column Figure. Left: was pushed onto the MetPac. Right: Mn on MetPac eluted to column. Table. Preconcentration Steps for Mn on the MetPac CC- Column DP Pump %A: M ammonium acetate ph. %B: 00 mm acetic acid %C: DI water Pump and Valve program: Time (min %A %B %C Flow AM_HP Injection Valve Comment (ml/min (0-Port Valve (6-Port Valve Position Position A (0- inject Inject the sample to fill the ml loop B (- load pushed onto the MetPac B (- load A (0- load MetPac washed with acetic acid A (0- load A (0- load MetPac flushed with DI water A (0- inject Mn trapped on MetPac eluted onto the analytical column. Determination of Manganese in Brine ( 0% NaCl

3 the solution. Calibrate a ph meter to ph 7. Pour about 0 ml of this buffer into a small container (scintillation vial, 0-mL disposable beaker and measure the ph. If the ph is below., add about ml of ammonium hydroxide to the buffer solution. If above ph., add g of acetic acid. Adjust the ph of the ammonium acetate to. ± 0. using acetic acid if the ph is greater than., or ammonium hydroxide if the ph is less than.. Once the ph is. ± 0., bring to a volume of.0 L with 8-MΩ deionized water. 00 mm acetic acid Prepare M acetic acid as the stock solution. Place 00 ml of deionized water into a clean -L polyethylene bottle. Add 60.0 g (7. ml of trace metal grade acetic acid and dilute to L. Label.0 M acetic acid. To prepare 00 mm acetic acid, place 900 ml of deionized water into a clean bottle. Add 00 ml of stock M acetic acid and mix thoroughly. Stock Standard Solution Prepare 000 mg/l standards for each of the cations in DI water. Standards should be prepared from the highest purity compounds available. Table provides the amounts needed to prepare 00 ml of each standard. Concentrated standards are stable for at least one month when stored at C. Table. Masses of Compounds Used to Prepare 00 ml of 000 mg/l Cation Standards Cation Compound Amount (g Lithium Lithium hydroxide 0. Sodium Sodium chloride 0. Ammonium Ammonium acetate 0.8 Potassium Potassium chloride 0.9 Magnesium Magnesium sulfate 0.9 Calcium Calcium chloride 0.77 Manganese Manganese sulfate monohydrate 0.07 Results and Discussion Preparation and Separation To determine µg/l concentrations of manganese in sodium chloride brines, manganese must be concentrated while sodium is eliminated. Dionex AN 0 shows how this can be accomplished for magnesium and calcium using a MetPac column to bind them while binding very little sodium, after adjusting the sample ph to.. Unfortunately, these conditions cannot be used to achieve the required sensitivity and recovery for manganese. Therefore, it is necessary to alter the sample preparation conditions on the MetPac column to capture manganese by chelation while excluding most of the sodium. Apply the sample with M ammonium acetate, ph., rinse the majority of the sodium from the MetPac with an acetic acid rinse, remove the acetic acid with a water rinse, and elute the bound manganese to the IonPac CA column set for separation from sodium, magnesium and calcium. This method requires two valves and a second pump for sample preparation, and is easily setup with an ICS-000 equipped with a dual pump and an automation manager. Figure shows a chromatogram of the water blank and chromatograms of four manganese standards of 0, 0, 0, and 00 µg/l, determined using the chelation IC method. These standards were used for method calibration and yielded a correlation coefficient for a linear fit of The chromatogram of the blank indicates there is no manganese in the water nor in any of the reagents used for sample preparation. There are significant concentrations of magnesium and calcium in the blank due to the presence of these cations in either the ammonium acetate and/or the acetic acid. This method cannot be used to determine low µg/l concentrations of magnesium and calcium in brine. If those analytes must be determined, use the method in AN 0. Figure shows that manganese is well resolved from magnesium, calcium, and the remaining sodium. s Analyze liquid samples without dilution. Dissolve approximately g of each solid sample in 00 ml of deionized water prior to analysis. Application Update 8

4 Column: IonPac CGA, CSA Eluent: 0 mm methanesulfonic acid Temperature: 0 C Flow Rate: ml/min Inj. Volume: ml (preconcentrate to MetPac CC- Detection: Suppressed conductivity, CSRS ULTRA II mm, recycle mode Peaks:. Ammonium. Magnesium. Manganese (overlay 0, 0, 0, 0, 00 µg/l. Calcium.0 Column: IonPac CGA, CSA Eluent: 0 mm methanesulfonic acid Temperature: 0 C Flow Rate: ml/min Inj. Volume: ml (preconcentrate to MetPac CC- Detection: Suppressed conductivity, CSRS ULTRA II mm, recycle mode Peaks:. Ammonium. Magnesium. Manganese 9.0 µg/l. Calcium Figure. Determination of manganese at µg/l concentrations (0, 0, 0, 0, 00 mg/l using chelation IC Figure. Overlay of three injections of liquid sample #. Average amount of manganese (peak : 9.0 µg/l. Analysis Manganese was determined in eight liquid and two solid sodium chloride samples provided by a company specializing in the production of these products (see Acknowledgements. Figures and show chromatograms for three injections each of two liquid samples, # and #. These samples had two of the highest concentrations of manganese of the ten samples tested. The chromatograms in Figures,, and had retention time RSDs of 0. and 0.0. The peak area RSDs were 8.97 and 7.. Tables and show the results for all 0 samples. The results for samples, 7, 9 and 0 represent single analyses. All other results represent the mean of three analyses. Manganese concentrations in the liquid samples ranged from < to 90 µg/l. To judge method recovery, manganese was spiked into four of the liquid samples, and the manganese measured in spiked and unspiked samples (Table. These samples were analyzed separately from those reported in Table. Table shows acceptable recovery, demonstrating that manganese is not lost during sample preparation. Column: IonPac CGA, CSA Eluent: 0 mm methanesulfonic acid Temperature: 0 C Flow Rate: ml/min Inj. Volume: ml (preconcentrate to MetPac CC- Detection: Suppressed conductivity, CSRS ULTRA II mm, recycle mode.0 Peaks:. Ammonium. Magnesium. Manganese. µg/l. Calcium Figure. Overlay of Three Injections of Liquid #. Average amount of manganese (peak :. µg/l. Determination of Manganese in Brine ( 0% NaCl

5 Table. Analysis of Liquid s Number Ret.Time Area Height Amount (min (*min ( (µg/l Table. Analysis of Solid s Ret.Time Area Height Amount Amount Name (min (*min ( (dissolved in Solid sample (µg/g (µg/l #9.09g /00 ml #0.9g /00mL Summary This application determines trace concentrations of manganese in sodium chloride brines, with automated sample preparation. Manganese and alkaline earth cations are selectively preconcentrated on-line, and most of the sodium is removed. The manganese and other cations are eluted from the concentrator column to the cationexchange column, where they are separated and detected by suppressed conductivity. This method exhibited good linearity in the concentration range of interest, and good recovery. References. Determination of Calcium and Magnesium in Brine; Application Note 0, LPN #0990; Dionex Corporation, Sunnyvale, CA, 998. Acknowledgements Dionex would like to thank Keith Hand of Riotinto Corporation for providing the brine samples. Table. The Recovery of Manganese from Liquid s Average* Amount (µg/l Spike Spike + % Recovery Name # # # # * Each sample, including spiked samples, was injected three times. MetPac and RFIC are trademarks and Chromeleon, CSRS, EluGen, and IonPac are registered trademarks of Dionex Corporation. Passion. Power. Productivity. Dionex Corporation North America Europe Asia Pacific 8 Titan Way P.O. Box 60 U.S. ( Canada ( Austria ( 66 Benelux ( ( 9 Denmark ( France ( Germany ( Sunnyvale, CA Ireland ( Italy ( Switzerland ( South America United Kingdom ( Brazil ( 7 0 ( Australia (6 90 China (8 8 8 India (9 767 Japan ( Korea ( Singapore ( LPN 89 09/6 06 Dionex Corporation