Titration Errors

Don t bother to rinse out the graduated cylinder. It will be a reproducible error. Titrate that sample with the iodate solution. While you are titrating this sample, another sample will be filling. A drop every 6 to 10 seconds is about right. 

A To rninitnize the effect of buret reading errors, titrations performed using a 50-mL buret are most accurate when titrant volumes are in the range of 35 to 45 mL. Suggest... 

Personal Errors Finally, analytical work is always subject to a variety of personal errors, which can include the ability to see a change in the color of an indicator used to signal the end point of a titration biases, such as consistently overestimating or underestimating the value on an instrument s readout scale failing to calibrate glassware and instrumentation and misinterpreting procedural directions. Personal errors can be minimized with proper care. 

In this experiment the overall variance for the analysis of potassium hydrogen phthalate (KHP) in a mixture of KHP and sucrose is partitioned into that due to sampling and that due to the analytical method (an acid-base titration). By having individuals analyze samples with different % w/w KHP, the relationship between sampling error and concentration of analyte can be explored. 

The determinate error in a titration due to the difference between the end point and the equivalence point. 

Suppose that the only available indicator changes color at a pH of 6.8. Is this end point close enough to the equivalence point that the titration error may be safely ignored To answer this question we need to know how the pH changes during the titration. 

An end point for a titration is determined experimentally and represents the analyst s best estimate of the corresponding equivalence point. Any difference between an equivalence point and its end point is a source of determinate error. As we shall see, it is even possible that an equivalence point will not have an associated end point. 

It has been shown that for most acid-base titrations the inflection point, which corresponds to the greatest slope in the titration curve, very nearly coincides with the equivalence point. The inflection point actually precedes the equivalence point, with the error approaching 0.1% for weak acids or weak bases with dissociation constants smaller than 10 , or for very dilute solutions. Equivalence points determined in this fashion are indicated on the titration curves in figure 9.8. 

The need for the indicator s color transition to occur in the sharply rising portion of the titration curve justifies our earlier statement that not every equivalence point has an end point. For example, trying to use a visual indicator to find the first equivalence point in the titration of succinic acid (see Figure 9.10c) is pointless since any difference between the equivalence point and the end point leads to a large titration error. 

Accuracy When working with macro-major and macro-minor samples, acid-base titrations can be accomplished with relative errors of 0.1-0.2%. The principal limitation to accuracy is the difference between the end point and the equivalence point. 

The equivalence point of a redox titration occurs when stoichiometrically equivalent amounts of analyte and titrant react. As with other titrations, any difference between the equivalence point and the end point is a determinate source of error. 

Dilute solutions of nominally 0.001 M NaOH and HGl are used to demonstrate the effect of an indicator s color transition range on titration error. Potentiometric titration curves are measured, and the indicator s color transition range is noted. Titration errors are calculated using the volume of titrant needed to effect the first color change and for a complete color change. 

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%. 

Although the most sensitive line for cadmium in the arc or spark spectmm is at 228.8 nm, the line at 326.1 nm is more convenient to use for spectroscopic detection. The limit of detection at this wavelength amounts to 0.001% cadmium with ordinary techniques and 0.00001% using specialized methods. Determination in concentrations up to 10% is accompHshed by solubilization of the sample followed by atomic absorption measurement. The range can be extended to still higher cadmium levels provided that a relative error of 0.5% is acceptable. Another quantitative analysis method is by titration at pH 10 with a standard solution of ethylenediarninetetraacetic acid (EDTA) and Eriochrome Black T indicator. Zinc interferes and therefore must first be removed. 

Ghlorophenol Analysis. The chlorophenols can be analy2ed by acidimetric titration of the hydroxyl function (50). This overall method yields only an approximate evaluation for mixtures. To analy2e chlorophenol mixtures, gas chromatography has been the reference method used, as it made it possible to separate and quantify the various chlorophenols (51), but this technique can be a source of errors the gem-chlotinated cyclohexadienones that may be present along with the chlorophenols are broken back down iato lighter chlorophenols under the analysis conditions usually employed. 

From a human factors perspective, the chemistry of the process can be made inherently safer by selecting materials that can better tolerate human error in handling, mixing, and charging. If a concentrated reagent is used in a titration, precision in reading the burette is important. If a dilute reagent is used, less precision is needed. 

Personal errors may arise from the constitutional inability of an individual to make certain observations accurately. Thus some persons are unable to judge colour changes sharply in visual titrations, which may result in a slight overstepping of the end point. 

The comparison of more than two means is a situation that often arises in analytical chemistry. It may be useful, for example, to compare (a) the mean results obtained from different spectrophotometers all using the same analytical sample (b) the performance of a number of analysts using the same titration method. In the latter example assume that three analysts, using the same solutions, each perform four replicate titrations. In this case there are two possible sources of error (a) the random error associated with replicate measurements and (b) the variation that may arise between the individual analysts. These variations may be calculated and their effects estimated by a statistical method known as the Analysis of Variance (ANOVA), where the... 

The reaction with the standard solution should be stoichiometric and practically instantaneous. The titration error should be negligible, or easy to determine accurately by experiment. 

With 1M solutions, it is evident that any indicator with an effective range between pH 3 and 10.5 may be used. The colour change will be sharp and the titration error negligible. 

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