Mixed-salt electrodes

Other useful solid-state electrodes are based on silver compounds (particularly silver sulfide). Silver sulfide is an ionic conductor, in which silver ions are the mobile ions. Mixed pellets containing Ag2S-AgX (where X = Cl, Br, I, SCN) have been successfiilly used for the determination of one of these particular anions. The behavior of these electrodes is determined primarily by the solubility products involved. The relative solubility products of various ions with Ag+ thus dictate the selectivity (i.e., kt] = KSp(Agf)/KSP(Aw)). Consequently, the iodide electrode (membrane of Ag2S/AgI) displays high selectivity over Br- and Cl-. In contrast, die chloride electrode suffers from severe interference from Br- and I-. Similarly, mixtures of silver sulfide with CdS, CuS, or PbS provide membranes that are responsive to Cd2+, Cu2+, or Pb2+, respectively. A limitation of these mixed-salt electrodes is tiiat the solubility of die second salt must be much larger than that of silver sulfide. A silver sulfide membrane by itself responds to either S2- or Ag+ ions, down to die 10-8M level. 

Miniaturization, 128, 163, 193 Minigrid electrode, 41, 52 Mixed-salt electrodes, 159 Modified electrodes, 118, 121 Monensin, 155 Monolayers, 117, 118, 173 Multichannel electrodes, 93, 94 Multipotentiostat, 106, 198 Mutation detection, 185... 

The chief restriction of these mixed-salt electrodes is that the solubility of the second salt must be much larger than that of Ag2S but, on the other hand, it must be sufficiently insoluble that its dissolution does not limit to relatively high values the test ion concentration that can be detected. As long as the membrane contains sufficient silver sulfide to provide silver ion conducting pathways through the membrane, it will function as a silver electrode. The potential, then, is related... 

Tetraphenylarsonium pertechnetate is precipitated in the presence of perchlorate as the carrier. The mixed salts are disolved in concentrated sulfuric acid and the solution is electrolyzed at platinum electrodes. The black deposit (TcOj) obtained is dissolved in perchloric acid, technetium heptoxide is distilled out of the solution... 

These various silver halides are usually precipitated in batch or continuous reactors by mixing aqueous solutions of alkali halide salts and silver nitrate. One, two or more reagents may be pumped into the reactor under programmed or feedback control. Key control variables are reagent mixing and delivery, temperature, and especially silver ion activity. The latter can be electrochemically monitored by using silver or silver salt electrodes, and the relative potentials measured by such electrodes provide a means to impose feedback control... 

If a compound contains more than one cation as in mixed salts, it is possible that both ions will migrate in the electrical field. If the electrode is non-blocking to only one of the ions (e.g. protons), the other ion will pile up at the vicinity of the cathode. If the anion cannot move, as is the case with a fixed anion lattice, the blocking ion will obstruct the passage... 

Current flow at electrode surfaces often involves several simultaneous electrochemical reactions, which differ in character. For instance, upon cathodic polarization of an electrode in a mixed solution of lead and tin salt, lead and tin ions are discharged simultaneously, and from an acidic solution of zinc salt, zinc is deposited, and at the same time hydrogen is evolved. Upon anodic polarization of a nonconsumable electrode in chloride solution, oxygen and chlorine are evolved in parallel reactions. 

From the neutral 1 2 complexes introduced before, two kinds of materials were obtained by electrocrystallization fully oxidized salts where both TTF CH= CH—py moieties are oxidized, and mixed valence salts in which the two ligands are partially oxidized. All oxidized complexes were obtained by oxidation at constant current of a neutral 1 2 complex in an electrolyte containing the anions, and using electrocrystallization technique with platinum wires (0 = 1mm) electrodes. 

Solutions in a conductance cell are often stirred to hasten salt dissolution, to promote solution mixing, or to prevent temperature gradients. Some workers observe an upward drift in measured resistances of unstirred solutions 12-17) while others report a downward drift unless the unstirred solution is mixed by shaking of the cell immediately before the measurement9-18-26>. The magnitude of this change is often 0.1 % or more. The effect has not been observed in other cases 8>10). The source of this problem has been variously attributed to temperature variations, electrode adsorption effects and solvent impurities, although the problem has not been analyzed in detail. In all but one of the above cases 12> the resistance of the stirred solution was taken as the true value. 

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