Part 1: Various metals and transition metals
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1 Polarographic Analyses Half wave potentials of metal ions Of interest to: General analytical chemistry B 1 Summary In the following tables the half-wave potentials or peak potentials of 90 metal ions are listed. The half-wave potentials (listed in Volt) are measured at the dropping mercury electrode (DME) at 25 C unless indicated otherwise. Electrodes WE MME AE Pt or Glassy Carbon RE Ag/AgCl/KCl (3 mol/l) In some cases other electrodes are specified. Legend w i cw Well marked wave or peak Poor wave or evaluation impossible (e.g. in the region of increasing background current of the supporting electrolyte) Catalytic reduction of hydrogen (in some cases suitable for quantitative analysis) No signal of the respective metal ion (polarographic or voltammetric analysis not possible) Formation of precipitate. Attention to solubility product! No information available Part 1: Various metals and transition metals Acetate NH 3 / NH 4Cl KCl HCl NaOH KNO 3 KSCN TEA Tartrate Na 2EDTA c(ch 3COOH) = 2 mol/l + c(ch 3COONH 4) = 2 mol/l ph 4.6 c(nh 3) = 1 mol/l + c(nh 4Cl) = 1 mol/l ph 9.6 c(kcl) = 1 mol/l c(hcl) = 1 mol/l c(naoh) = 1 mol/l c(kno 3) = 0.1 mol/l c(kscn) = 1 mol/l c(triethanolamine) = 0.3 mol/l + c(koh) = 0.1 mol/l c(na 2-tartrate) = 0.5 mol/l ph = 9.0 c(na 2EDTA) = 0.1 mol/l Citrate c(na 3-citrate) = 0.1 mol/l + c(naoh) = 0.1 mol/l Oxalate ph 2 c(ammonium oxalate) = 0.1 mol/l, ph setting with H 2SO 4 Oxalate ph 4 c(ammonium oxalate) = 0.1 mol/l, ph setting with H 2SO 4 Oxalate ph 6 c(ammonium oxalate) = 0.1 mol/l, ph setting with H 2SO 4 Oxalate ph 8 c(ammonium oxalate) = 0.1 mol/l, ph setting with NH 3
2 Page 2/7 Metal Ion Acetate NH3/NH4Cl KCl HCl NaOH KNO3 KSCN TEA Tartrate Na2EDTA Citrate Oxalate ph 2 Oxalate ph 4 Oxalate ph 6 Oxalate ph 8 Al(III) 1.59 i As(III) i 0.07 i 0.38 w w w 0.22 w 1.56 w 1.70 i 1.58 i Bi(III) 0.21 w 0.06 w 0.07 w i 0.87 w 0.31 w cw 0.54 w 0.77 w 0.13 w 0.21 w 0.22 w 0.26 w Cd(II) 0.63 w 0.77 w 0.62 w 0.61 w 0.82 i 0.55 w 0.62 w cw 0.68 i 0.56 w 0.61 w 0.62 w 0.62 w Ce(IV) Co(II) w 1.54 Cr(III) 1.20 i 1.34 w w i 1.01 w 1.58 i 1.20 w 1.73 i Cr(VI) 0.28 w 1.45 w 1.68 Cu(II) 0.25 w 0.20 w 0.46 w w 1.03 i 0.85 w Fe(II) 1.44 w 1.57 i cw i cw 1.55 i i cw Fe(III) w 1.27 w w 0.73 w 0.02 w 1.14 w 1.72 i w 0.26 w 0.41 w 0.05 w 0.15 w 0.18 w 0.18 w 1.59 w 1.02 w i 1.29 i 1.56 w 0.99 w i 0.09 w 0.83 w 1.57 w w 0.11 w 0.85 w 1.59 w 0.02 w w 0.18 w 1.61 i 0.18 w 0.17 w 0.19 w 0.19 w Ge(IV) 1.34 i i cw i cw 1.38 w 1.38 w In(III) 0.67 w w 0.90 i 0.59 w 1.51 w w 0.67 w 0.84 w Mn(II) 1.59 w 1.55 w 1.68 i 1.46 i 1.56 i i 0.68 w 0.87 w 0.70 w w 1.61 i 1.60 i
3 Page 3/7 Metal Ion Acetate NH3/NH4Cl KCl HCl NaOH KNO3 KSCN TEA Tartrate Na2EDTA Citrate Oxalate ph 2 Oxalate ph 4 Oxalate ph 6 Oxalate ph 8 Mo(VI) 0.63 w i w w 0.74 w Ni(II) 1.09 w 1.07 w w 0.66 w Pb(II) 0.47 w 0.47 w 0.41 w 0.41 w w 0.39 w w 0.69 w 0.40 w 0.45 w 0.56 w 0.57 w Pd(II) Sb(III) w Se(IV) Sn(II) 0.70 w w 0.63 w 0.75 w i cw 1.33 i i cw 1.01 i 0.81 w w 1.54 w w w 0.45 w w 0.19 w 0.58 w w 0.64 w w w 1.20 w 0.35 w 0.45 w 1.59 w 0.75 w 1.15 w w 1.08 w w 0.17 w w 0.46 w 0.41 w 0.57 w 0.12 w 0.51 w 0.68 w w 0.62 w 0.76 w Sn(IV) i 0.51 w Ti(III) 0.31 w 0.41 w Ti(IV) Tl(I) 0.44 w 0.46 w w w 0.50 w 0.45 w 0.45 w 0.44 w 0.47 w U(VI) 0.42 w 0.18 i i w w 0.42 w V(V) i cw i 1.10 i cw 1.11 i 0.40 i 1.03 i 0.50 w i w 0.26 w 0.62 w w W(VI) 0.26 i 1.01 i cw 1.26 i Zn(II) w 0.99 w 0.99 i w w 1.38 w Zr(IV) 1.49 w 0.95 w 1.58 w cw 0.51 i 0.64 i 0.19 w w
4 Page 4/7 Part 2: Alkaline and alkaline earth metals c(teai) = 0.1 mol/l c(tetraethylammonium iodide) = 0.1 mol/l in water c(teai) = 0.1 mol/l, 20% DMF c(tetraethylammonium iodide) = 0.1 mol/l in water:dimethylformamide 80:20 Half-wave potentials Metal Ion Supporting electrolyte Half-wave potential Ba(II) c(teai) = 0.1 mol/l 1.90 Be(II) c(teai) = 0.1 mol/l, ph Ca(II) c(teai) = 0.1 mol/l 2.24 i Cs(I) c(teai) = 0.1 mol/l 2.04 K(I) c(teai) = 0.1 mol/l 2.11 Li(I) c(teai) = 0.1 mol/l 2.31 Mg(II) 1 c(teai) = 0.1 mol/l Na(I) c(teai) = 0.1 mol/l 2.07 Rb(I) c(teai) = 0.1 mol/l 2.06 Sr(II) c(teai) = 0.1 mol/l, 20% DMF Remarks Alkaline and alkaline earth metals usually cannot be determined in real samples because the signals are not well separated from each other. 1 Magnesium is determined indirectly as an oxime or as a complex with solochrome violet RS. 2 Maximum, non exploitable.
5 Page 5/7 Part 3: Rare-earth elements c(tea-clo 4) = 0.1 mol/l in DMF c(tetraethylammonium perchlorate) = 0.1 mol/l in dimethylformamide Half-wave potentials Metal Ion Supporting electrolyte Half-wave potential 3 Ce c(tea-clo 4) = 0.1 mol/l in DMF 2.44 Dy c(tea-clo 4) = 0.1 mol/l in DMF 2.08 Er c(tea-clo 4) = 0.1 mol/l in DMF 2.16 Eu c(tea-clo 4) = 0.1 mol/l in DMF Gd c(tea-clo 4) = 0.1 mol/l in DMF 2.12 Ho c(tea-clo 4) = 0.1 mol/l in DMF 2.20 La c(tea-clo 4) = 0.1 mol/l in DMF 2.16 Lu c(tea-clo 4) = 0.1 mol/l in DMF 2.08 Nd c(tea-clo 4) = 0.1 mol/l in DMF 2.22 Pm c(tea-clo 4) = 0.1 mol/l in DMF (radioactive) Pr c(tea-clo 4) = 0.1 mol/l in DMF 2.24 Sm c(tea-clo 4) = 0.1 mol/l in DMF 1.98 Sc c(tea-clo 4) = 0.1 mol/l in DMF 1.76 Tb c(tea-clo 4) = 0.1 mol/l in DMF 2.16 Tm c(tea-clo 4) = 0.1 mol/l in DMF 2.10 Yb c(tea-clo 4) = 0.1 mol/l in DMF 1.58 Y c(tea-clo 4) = 0.1 mol/l in DMF 2.06 Remarks For preparation of the standard solutions the oxides of the rare-earth elements are first dissolved in aqua regia, dried in a vacuum desiccator, and then dissolved in DMF. With the exception of Ce, Sc, and Yb, the half-wave potentials of all metals become more positive with increasing concentrations. 3 The reference electrode is filled with supporting electrolyte.
6 Page 6/7 Part 4: Actinides and technetium c(liclo 4) = 0.1 mol/l, ph c(liclo 4) = 0.1 mol/l in water. The ph value is adjusted to c(kcl) = 0.5 mol/l, ph 2 c(kcl) = 0.5 mol/l in water. The ph value is adjusted to 2. Half-wave potentials Metal Ion Supporting electrolyte Half-wave potential Literature Ac c(liclo 4) = 0.1 mol/l, ph [1] Am [2] Cf [2] Cm [2] Fm [3] Np [4] Pu Al 2(SO 4) 3 / citric acid, ph [5] Tc c(kcl) = 0.5 mol/l, ph [6] Remarks Since all these elements are highly radioactive, it was not possible to determine them in our laboratory. The following literature references are useful. Literature [1] F. David Polarographie von Actinium C.R. Acad. Sci. (Paris) Ser. C 271 (1970), Ref.: Z.Anal.Chem. 256 (1971), 307 [2] F. David Polarography of radioisotopes 115Eu, 169Yb, 153Gd, 241Am, 244Cm, 252Cf Compt. Rend. 270 C (1970), Ref.: Electroanal. Abstr. 9 (1971), 140 [3] F. David; M. Nussonois Reduction of Fm(II) in acetic solution by electrolysis at controlled electric tension Radiochem. Radioanal. Lett. 11 (1972), 1-5 Ref.: Electroanal. Abstr. 11 (1973), 328 [4] V.F. Peretruhin; D.P. Alekseeva Polarographic behaviour of Np(VII) in alkaline aqueous solutions Izv. Akad. Nauk. SSSR, Ser. Khim. 23 (1974), 1438 Ref.: Electroanal. Abstr. 13 (1975), 45 [5] G.W.C. Milner; A.J. Wood The determination of plutonium by A.C. polarography J. Electroanal. Chem. 7 (1964), Ref.: Z. Anal. Chem. 219 (1965), 70 [6] G.B.S. Salaria; C.L. Rulfs; P.J. Elving Polarographic and coulometric determination of technetium Anal. Chem. 35 (1963), Ref.: Z. Anal. Chem. 219 (1965), 440
7 Page 7/7 Part 5: Miscellaneous c(tbai) = 0.1 mol/l in 80% ethanol c(tetrabutylammonium iodide) = 0.1 mol/l in water:ethanol 80:20 c(hcl) = 0.1 mol/l c(hcl) = 0.1 mol/l in water. c(kscn) = 0.1 mol/l, ph 3 c(kscn) = 0.1 mol/l in water. The ph value is adjusted to 3 c(naoh) = 2 mol/l c(naoh) = 2 mol/l in water. HCl conc. w(hcl) = 32% Ca(OH) 2 sat. c(kno 3) = 0.3 mol/l c(h 2SO 4) = 0.1 mol/l c(na 2-NTA) = 0.1 mol/l c(naoh) = 0.1 mol/l / c(kno 3) = 0.1 mol/l c(edta) = 0.1 mol/l c(tea-clo 4) = 0.1 mol/l in DMF Saturated solution of Ca(OH) 2 in water. c(kno 3) = 0.3 mol/l in water. c(h 2SO 4) = 0.1 mol/l in water. c(nitrilotriacetate disodium salt) = 0.1 mol/l in water. c(naoh) = 0.1 mol/l + c(kno 3) = 0.1 mol/l in water. c(ethylenediaminetetraacetic acid) = 0.1 mol/l in water. c(tetraethylammonium perchlorate) = 0.1 mol/l in dimethylformamide. Metal Ion Supporting electrolyte Half-wave potential Al(III) c(tbai) = 0.1 mol/l in 80% ethanol 1.67 Au(III) c(hcl) = 0.1 mol/l Ga(III) c(kscn) = 0.1 mol/l, ph Hf Ir(IV) c(naoh) = 2 mol/l Nb(V) HCl conc Os(VIII) Ca(OH) 2 sat Pt(IV) c(kno 3) = 0.3 mol/l Re(VII) c(h 2SO 4) = 0.1 mol/l 0.66 Rh(III) c(na 2-NTA) = 0.1 mol/l 0.46 Ru(I) c(naoh) = 0.1 mol/l / c(kno 3) = 0.1 mol/l 0.81 w 7 Ta Ti(IV) c(edta) = 0.1 mol/l 0.34 Th(III) c(tea-clo 4) = 0.1 mol/l in DMF With glassy carbon working electrode. 5 With platinum working electrode. 6 Negative peaks. 7 With respect to the Hg/Hg 2Cl 2/KNO 3 sat. reference electrode.
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