Electrode dual-polarized amperometric

Because the generator electrodes must have a significant voltage applied across them to produce a constant current, the placement of the indicator electrodes (especially if a potentiometric detection system is to be used) is critical to avoid induced responses from the generator electrodes. Their placement should be adjusted such that both the indicator electrode and the reference electrode occupy positions on an equal potential contour. When dual-polarized amperometric electrodes are used, similar care is desirable in their placement to avoid interference from the electrolysis electrodes. These two considerations have prompted the use of visual or spectrophotometric endpoint detection in some applications of coulometric titrations. 

Figure 4.6 Dual-polarized electrode amperometric titration curves. Both curves result from the application of a 0.25-V potential across two identical platinum electrodes that are immersed in the titration solution.

Figure 4.9 Coulometric titration cell with generator [II (generator anode, 0.7 x 0.7 cm)] and isolated auxiliary [I (generator cathode, 0.7 x 0.7 cm)] electrodes on the left side and a pair of identical platinum electrodes [III, IV (1.4 x 1.8 cm and 2.5 X 1.8 cm)] on the right for dual-polarized electrode amperometric endpoint detection.

The most common end-point detection method for the Karl Fischer titration for determining water (see Section 20C-5) is the amperometric method with dual polarized electrodes. Several manufacturers offer fully automated instruments for use in performing these titrations. A closely related end-point detection method for Karl Fischer titrations measures the potential difference between two identical electrodes through which a small constant current is passed. 

Cardwell and Christophersen reported a dual channel FI system with amperometric detection for the determination of ascorbic acid and sulfur dioxide in wines and fruit juices (Cardwell and Christophersen, 2000). Here, the ascorbic acid was detected at a glassy carbon electrode polarized at 0.42 V (vs. Ag/AgCl), whereas the sulfur dioxide was detected at a Pt electrode polarized at 0.90 V (vs. Ag/AgCl) after separation of the analytes by a gas diffusion unit. The determination of ascorbic acid showed a linear range between 3 and 50 mg L with an FOD of 1.5 mg L for sulfur dioxide the linear range was between 0.25 and 15 mgF i and an FOD of 0.05 mgF" was obtained. The sample frequency achieved with the system was 30 h b The proposed method showed a good agreement with a reference method in the results obtained for white wines and juice samples, while for red wines and sweet wines an extraction procedure of the analytes by solid-phase extraction was required. 

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