Errors reagents

Instrumental and reagent errors. These arise from the faulty construction of balances, the use of uncalibrated or improperly calibrated weights, graduated... 

Figure 6-2a. Larger Allowable Reagent Error on a Flatter Portion of the Titration Curve...

The traditional rule has been that one stage of neutralization is required for every 2 pH units the influent pH is away from the set point. For example, to go from an influent at 1 pH to a set point of 7 pH requires three stages of neutralization. A more exact rule would add another stage of neutralization if the control valve resolution was estimated to be more than half the allowable reagent error for the control band. This means that control valves with very low stick-slip and advanced control strategies that allow manipulation of a trim and a coarse valve on the same stage could eliminate a stage of neutralization. 

A proportional determinate error, in which the error s magnitude depends on the amount of sample, is more difficult to detect since the result of an analysis is independent of the amount of sample. Table 4.6 outlines an example showing the effect of a positive proportional error of 1.0% on the analysis of a sample that is 50.0% w/w in analyte. In terms of equations 4.4 and 4.5, the reagent blank, Sreag, is an example of a constant determinate error, and the sensitivity, k, may be affected by proportional errors. 

In a single-point standardization, we assume that the reagent blank (the first row in Table 5.1) corrects for all constant sources of determinate error. If this is not the case, then the value of k determined by a singlepoint standardization will have a determinate error. 

To correct for all constant method errors, a blank must account for signals due to the reagents and solvent used in the analysis and any bias due to interac-... 

To obtain accurate results we must eliminate determinate errors affecting the measured signal, S ieas the method s sensitivity, k, and any signal due to the reagents, Sjeag-... 

A reagent blank corrects the measured signal for signals due to reagents other than the sample that are used in an analysis. The most common reagent blank is prepared by omitting the sample. When a simple reagent blank does not compensate for all constant sources of determinate error, other types of blanks, such as the total Youden blank, can be used. 

Accuracy Under normal conditions relative errors of 1-5% are easily obtained with UV/Vis absorption. Accuracy is usually limited by the quality of the blank. Examples of the type of problems that may be encountered include the presence of particulates in a sample that scatter radiation and interferents that react with analytical reagents. In the latter case the interferant may react to form an absorbing species, giving rise to a positive determinate error. Interferents also may prevent the analyte from reacting, leading to a negative determinate error. With care, it maybe possible to improve the accuracy of an analysis by as much as an order of magnitude. 

Accuracy The accuracy of a controlled-current coulometric method of analysis is determined by the current efficiency, the accuracy with which current and time can be measured, and the accuracy of the end point. With modern instrumentation the maximum measurement error for current is about +0.01%, and that for time is approximately +0.1%. The maximum end point error for a coulometric titration is at least as good as that for conventional titrations and is often better when using small quantities of reagents. Taken together, these measurement errors suggest that accuracies of 0.1-0.3% are feasible. The limiting factor in many analyses, therefore, is current efficiency. Fortunately current efficiencies of greater than 99.5% are obtained routinely and often exceed 99.9%. 

To verify the method a 1.00-mL aliquot of a standard solution of 40.0-ppm glucose was added to 1.00 ml of the combined reagents, requiring 34.6 s to produce the same extent of reaction. Determine the calculated concentration of glucose in the standard and the percent error for the analysis. 

The analytical uncertainty should be reduced to one-third or less of sampling uncertainty (16). Poor results obtained because of reagent contamination, operator errors ia procedure or data handling, biased methods, and so on, can be controlled by proper use of blanks, standards, and reference samples. 

Separate sample blanking requires an additional analytical channel, and is therefore wasteflil of both reagents and hardware. An alternative approach that is used on several automated systems, eg, Du Pont ACA, BM-Hitachi 704, Technicon RA-1000, is that of bichromatic analysis (5) where absorbance measurements are taken at two, rather than one, wavelength. When the spectral curves for the interference material and the chromogen of the species measured differ sufficiently, this can be an effective technique for reducing blank contributions to assay error. Bichromatic analysis is effective for blanks of both the first and second type. 

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