207/2 e

Application Bulletin
Of interest to:

General analytical laboratories, Waters, Metals, Foodstuffs, Photographic industry

B 1, 2, 6, 7, 9, 10

Analysis of silver by stripping voltammetry
This Application Bulletin describes the stripping analysis of Ag at the rotating disk electrode (RDE) with glassy carbon tip (GC) or Ultra Trace Graphite tip. In routine operation, the determination limit lies around 10 µg/L Ag, with careful work 5 µg/L Ag. After appropriate digestion, the silver determination is also possible with samples containing a relatively high proportion of organic substances (e.g. wine, foodstuffs etc.). The method has been developed primarily for water samples (well, ground and waste water, desilvering solutions of the photographic industry).

Apparatus and accessories
• 746 VA Trace Analyzer with 747 VA Stand or • 757 VA Computrace Electrodes • Working electrode (WE) Driving axle for RDE GC Tip or Ultra Trace Tip 6.1246.000 6.1204.110 6.1204.100

• Reference Electrode (RE) Ag/AgCl Reference system 6.0728.020 Electrolyte vessel 6.1245.010 with outer electrolyte c(KNO3) = 3 mol/L • Auxiliary electrode (AE) Electrode holder Glassy carbon tip • Stopper for MME • Polishing set • Trim tool (only for Ultra Trace electrode) • Measuring vessel 6.1241.020 6.1247.000 6.2709.040 6.2802.000 6.2827.000 6.1415.210

2 mol/L. CAS 7757-79-1 Nitric acid. guide the tool back and forth.2 mol/L in high purity water Supporting electrolyte: c(KNO3) = 0. then rinsed thoroughly with water and wiped with a soft cloth (Kleenex). The electrode is conditioned for 10 minutes in the polarographic stand in HNO3 (1:1) and rinsed again thoroughly with water. Only high purity water should be used for the preparation of the solutions. c(EDTA) = 0. Continue heating until ca. w(HNO3) = 65% Ag stock solution.p. the glassy carbon electrode is mechanically cleaned with the polishing set and humidified alox powder. 0.. Digestion with the 705 UV Digester Water with a slight to medium contamination with organic matter can be digested using the UV Digester 705. • If the Ultra Trace Electrode has not been used for a longer period or has been contaminated. Wet digestion with nitric acid/perchloric acid Suitable for waters with a relatively high organic content. Sample preparation As traces of organic substances can also influence the silver determination. Add 50 µL hydrogen peroxide solution w(H2O2) = 30% to 10 mL acidified water sample (pH = 2) and irradiate for 60 minutes at 90°C. CAS 6381-92-6 Potassium nitrate. Pipette 25 mL sample solution into a beaker and add 2 mL each of HNO3 and HClO4. putting slight pressure on the electrode tip. it is cleaned off with a special trimming tool. Rinse well with water afterwards and condition with HNO3 1:1. Never evaporate to dryness !! After cooling. puriss. • • • • Ethylenediaminetetraacetic acid disodium salt dihydrate. Mount the electrode in the stand. The beaker is covered with a watch glass and carefully warmed. Allow to cool and transfer directly into the polarographic vessel. Ag standard solution: β(Ag) = 10 mg/L More diluted standard solutions are prepared by diluting with c(HNO3) = 0. turn on the stirrer and. .Application Bulletin Analysis of silver by stripping voltammetry Reagents No. suprapur. the solution is heated to boiling and evaporated until HClO4 vapour appears.1 mol/L. suprapur. 207/2 e Page 2 The reagents should be of the highest analytical quality (suprapur). Add 20 mL c(Na2EDTA) = 0.004 mol/L Dissolve 20.5 mL is left. • Electrode treatment • After a lengthy period of non-use or in daily routine operation before the first analysis. β(Ag ) = 1 g/L (commercially available) + Ready-to-use solutions • • c(Na2EDTA) = 0. After 3 min. socalled pure waters must also be digested.a. rinse the residue into a 25 mL volumetric flask with high purity water and fill up to the mark.2 g KNO3 in high purity water.2 mol/L and fill up to 1 L. • An additional electrolytical cleaning is included in the program.

After cooling. non linearity (flattering) of the curve appears owing to overloading of the electrode.5 µg Ag in the polarographic vessel the standard addition curve is linear. add 0.Application Bulletin Analysis of silver by stripping voltammetry No.1 s 40 mV/s 0.4 mL of the EDTA solution c(Na2EDTA) = 0. Then calcine the residue in a muffle furnace at 650°C for 2h. Rinse the solution into a 50 mL volumetric flask with high purity water and fill up to the mark. It is important to set the foot point of the baseline at the rear side of the peak (rear half) and to evaluate with a slope = 0. add 25 mL high purity water and boil for 1 min. 207/2 e Page 3 Digestion of photographic waste waters and desilvering solutions Pipette 25 mL sample into a quartz dish and add 0. then cool.25 V The concentration is determined by standard addition. After cooling. Above this. After cooling. • The peaks are very asymmetrical.25 g sodium thiosulphate. Analysis Measuring solution: 5 mL (diluted) sample + 10 mL supporting electrolyte The voltammogram is recorded with the following parameters: Working electrode Stirrer/RDE Measurement mode Purge time Pulse amplitude Cleaning potential Cleaning time Deposition potential Deposition time Equilibration time Start potential End potential Voltage step Voltage step time Sweep rate Peak potential (Ag) RDE 2000 DP 300 s 50 mV 0. Remarks • With up to approx.2 mol/L and adjust the pH value to 5.45 V 4 mV 0.4 V 120 s 5s 0V 0.5 with w(NaOH) = 30%.5 .45 V 60 s -0. 2. • In the digestion of photographic waste waters. the solution is heated again and evaporated almost to dryness.6. Heat until sulphuric acid vapour evolves. • All glassware and accessories that come into contact with the solutions must be cleaned for at least 2 h with HNO3 1:1 and then rinsed thoroughly with high purity water. otherwise silver will be lost. it is essential to add thiosulphate. add 5 mL HNO3 and 1 mL H2SO4 together with two glass beads. After a further addition of 5 mL HNO3 . Heat the solution to dryness at 120°C in a drying oven. .

P.5 1. / Stilikova.Application Bulletin Analysis of silver by stripping voltammetry Literature No. / Yoshida.5 4 3 3. 1044-1046 • Pribil.L. 24 (1970).5 Standard addition curve: Ag 50 100 150 200 250 300 350 400 U (mV) 10 20 30 40 50 60 70 80 90 rho(eff) (µg/L) . Acta 299 (1990). Chem. Chim. Applications to silver analysis of rain and snow samples from silver iodide seeded clouds. /Zhao. / Lafontan.5 1 1 0. 35 (1963).5 3 2. 31 (1071). S. H. U. H. Anal. / Mark. Chem.5 2. S. Talanta 36 (1989). M. P. Voltammetry withdisk electrodes and its analytical application. M. 183-189 • Kopanica. Chim. Z. G. 175-181 • Temmermann. Acta 58 (1972). Electroanal. J.B. / Verbeek. 705-708 • Hiroq. 345-355 • Perone. / Vydra. 213-219 • Tanaka. Talanta 34 (1987). Anodic stripping voltammetry of silver in cadmium at the glassy carbon electrode. 207/2 e Page 4 • Gao. / Wang. An electrochemical stripping method for selective determination of traces of silver.5 2 2 1. S. B. F. Chim. Anal. Anodic stripping voltammetry of trace concentrations of silver and copper employing a glassy carbon electrode. Acta 93 (1977). 263-272 • Elsner.5 4. R. Determination of trace amounts of silver with a chemically . Electroanal. Voltammetrie de l’argent par redissolution du carbon vitreux et application au dosage de l’argent dans l’uranium et le plutonium.modified carbon paste electrode. The application of stripping analysis to the determination of siver using graphite electrodes Anal. Stripping voltammetry of silver (I) with a carbon paste electrode modified by thiacrown compounds. Anal.Z. E. 2091-2094 Figures Substance: Ag VR(**) I (µA) I (µA) 3. Chem. The anodic stripping voltammetry of trace silver solutions employing graphite electrodes. F.

delta ------.speed Segm.0100) ================== Determ. 1 Stripping voltammetric analysis of silver at the Ultra Trace RDE Result report and curves at the 746 VA Trace Analyzer ================== METROHM 746 VA TRACE ANALYZER (5.add.96 Comments ------------------ Fig.746.reg/offset 2000 /min 2000 /min Silver std-Ag V. ---------- Mean deviat.sample: 463 ng 250 ng 5 mL Comments ------------------ mL 1 2 3 4 5 6 7 8 9 10 11 12 13 .mean -----1.0233 KNO3EDTA V.3151 mg/L +/.045 1.235 3.mth OPERATION SEQUENCE Title : Determination of Ag with RDE -------------------------------------------------------------------------------Instructions t/s ------------. Y.013 2.000 mL V.005 Std. 92.468 1.04708 0.0 (REP SEGMENT REP)1 ADD>M ADD)2 END Main parameters ------------------------Soln.453e-06 Nonlin.82 ug/L (1. 5 mL used for determination -------------------------------------------------------------------------------Substance : Ag Mass conc.add 10.435 2. 207/2 e Page 5 ================== METROHM 746 VA TRACE ANALYZER (5.1/S1 Ident.784e-08 Final results --------------------------------Ag = 2.249 2.mass : V0.025 mL Auxiliary parameters ------------------------V. : VR --00 01 10 11 20 21 Substance --------Ag U/mV ----244 242 257 256 265 265 I/uA -----1. % Slope ---------0.452 Sample size/S0 (NH4)2S2O3 2 mL -------------------------------------------------------------------------------Method : AB207_Ag Title : Determination of Ag in (NH4)2S2O3 with RDE Remark1 : UTGE Remark2 : 2 mL sample diluted to 50 mL.0102 Soln.0101) ================== Method: AB207 .61 ug/L MC.96%) Cal.997 Mass : Add.Application Bulletin Analysis of silver by stripping voltammetry No.7906 Rot.0 (ADD PURGE STIR 30.----DOS>M SMPL>M PURGE STIR 300. -----------1.add 0.242 3.3/S3 Method. I. : 1.2/S2 Ident. -------std.fraction mL Rot.7631 Comments ------------------ : 06111406 User: Date: 98-06-11 Modified : 98-06-11 14:07:27 Run : 7 Time: 14:06:55 Sample table: -------------------------------------------------------------------------------Pos.

reg 1.half dU.Silver -------------------------------------------------------------------------------Recognition ------------------------U.Application Bulletin Analysis of silver by stripping voltammetry Method: AB207 No.rear 0.end mV Evaluation --------------------------Mode VA Quantity I.speed U.scale auto U.0 ms 40.meas U.begin mV U. 1./cm Method: AB207 Additions -----------------------------------------------------------std-Ag 10 mg/L g/L g/L g/L g/L g/L g/L g/L g/L g/L g/L g/L g/L g/L g/L g/L CALCULATION max.ampl t. A##) ---------------------------------------R1000=MC:Ag Res.453e-06 Slope 0.standby 2000 50 0.pulse 20.conc.784e-08 Soln.start U.peak Sign.unit -------#g/L Sig.0 SUBSTANCES Ag .0 DPMODE MEAS 0STIR MEAS SWEEP PURGE RDE MEAS 0MEAS END Method: AB207 120. Curve type linear Display / Plot --------------------------I.width min 10 mV U. 2 Stripping voltammetric analysis of silver at the Ultra Trace RDE Method at the 746 VA Trace Analyzer .dig.0 11.6 Main parameters ------------------------Rot.front auto S. Range min Range max M.04708 Nonlin.threshold 200 pA Baseline ------------------------Type linear Scope r.step Sweep rate 4 mV 40 mV/s 60.meas U.00 mV/cm ---------Mass conc.div 50.----0PURGE RDE 5.rear auto S.meas U. -------5 Fig.000 Calibration 1998-06-11 14:32:03 --------------------------------Technique std.step U.add.meas t.tol (+/-) 50 mV U.front auto dU.10 -400 /min mV s mV Auxiliary parameters ------------------------t.speed U.verify 250 mV U. 15 lines -------------------------------------------------------------------------------Quantity -----------Ag Formula (R##. C##.end Rot.0 5. 207/2 e Page 6 SEGMENT Silver -------------------------------------------------------------------------------Instructions t/s ------------. Mean dev.0 ms 1 2 3 4 5 6 7 8 9 10 11 12 0 mV 0 mV 450 mV 2000 /min 450 mV mV U. digits 4 Coefficients ------------------------Y.width max 200 mV I.