Amperometry precision

The differences between potentiometry and amperometry are summarized in Table 1.1. It will be seen that amperometric measurements are generally more precise and more versatile than those made by using potentiometry, so the majority of this book will therefore be concerned with amperometric measurements. 

More than brief discussion of the numerous ways in which end points can be taken other than by visual methods is beyond our scope. For example, end-point techniques may involve photometry, potentiometry, amperometry, conductometry, and thermal methods. In principle, many physical properties can be used to follow the course of a titration in acid-base titrations, use of the pH meter is common. In terms of speed and cost, visual indicators are usually preferred to instrumental methods when they give adequate precision and accuracy for the purposes at hand. Selected instrumental methods may be used when a suitable indicator is not available, when higher accuracy under unfavorable equilibrium conditions is required, or for the routine analysis of large numbers of samples. 

Kunnecke and Schmid [40] introduced a gas-diffusion separation system combined with an immobilized alcohol oxidase column used for the determination of ethanol in beverages by amperometry. Ethanol vapour from the samples diffused through a silicone-modified polypropylene membrane and was collected in a potassium phosphate buffer acceptor stream before passing through the immobilized enzyme column where the ethanol was transformed into hydrogen peroxide. The peroxide was determined using an amperometric detector with excellent precision (cf. Sec. 8.4). 

The use of amperometry as an endpoint detection method has been widely adopted for the titration of substances at the millimole per liter level, with excellent analytical precision ( 1% RSD at 0.01 mmol 1 level). The majority of these titrations involve the formation of precipitates, while others involve complexometric and redox titrations. At the millimole per liter level, the accuracy of this method is better than that achievable with other electroan-alytical methods and as good as those of spectro-photometric titration. 

This article provides some general remarks on detection requirements for FIA and related techniques and outlines the basic features of the most commonly used detection principles, including optical methods (namely, ultraviolet (UV)-visible spectrophotometry, spectrofluorimetry, chemiluminescence (CL), infrared (IR) spectroscopy, and atomic absorption/emission spectrometry) and electrochemical techniques such as potentiometry, amperometry, voltammetry, and stripping analysis methods. Very few flowing stream applications involve other detection techniques. In this respect, measurement of physical properties such as the refractive index, surface tension, and optical rotation, as well as the a-, //-, or y-emission of radionuclides, should be underlined. Piezoelectric quartz crystal detectors, thermal lens spectroscopy, photoacoustic spectroscopy, surface-enhanced Raman spectroscopy, and conductometric detection have also been coupled to flow systems, with notable advantages in terms of automation, precision, and sampling rate in comparison with the manual counterparts. 

The instrumentation of HPCE is uncomplicated (see the schematic drawing in Figure 1). Briefly, both ends of the narrow-bore fused silica capillary are immersed into reservoirs containing a buffer solution that also fills the capillary. The reservoirs also contain electrodes that provide electrical contact between the high-voltage power supply and the capillary. The sample is loaded onto the capillary by replacing one of the buffer reservoirs by a sample reservoir and applying external pressure (hydrodynamic injection) or an electric field (electrokinetic injection). After the injection, the reservoir is replaced, the electrical field is applied, and the separation starts. The detection is usually performed at the opposite end of the capillary (normal polarity mode). UV/vis detection is by far the most common detection technique in HPCE. Other techniques include fluorescence, amperometry, conductivity, and mass spectrometry. Modem HPCE instruments are fully automated and thereby allow easy operations and precise quantitative analyses. 

The main difficulty in working with amperometry is the need for decoupling of the detection signal to eliminate any interference from the applied electric held, precise electrode positioning, and electrode stability [51]. However, use of decoupler in front of the detector [52,53], or end-column detection [54,55] may resolve these issues. 

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