ERRORS IN CHEMICAL

ANALYSIS
Errors in Chemical Analyses
■ Measurements invariably involve errors and uncertainties.
■ Errors are usually caused by faulty calibrations or by random variations and
uncertainties in results.
■ Measurement data can only give us an estimate of the “true” value.
■ The reliability of experimental data is extremely important.
The Mean and the Median
■ To improve reliability, replicates are often carried through an entire analytical
procedure.
■ Individual results are seldom the same, so the central value of the set is considered
the best estimate.
■ The most widely used measure of central value is the mean, �
■ The median is the middle result when replicate data are arranged in increasing or
decreasing order.
Precision & Accuracy
■ Precision describes the reproducibility of measurements, that is the closeness of
results that have been obtained in exactly the same way
■ The standard deviation, variance and coefficient of variation are used to describe
precision of data
■ Accuracy indicates the closeness of the
measurement to the true or accepted value; it
is expressed by the error
■ Results can be precise without being accurate,
and vice versa; so it’s dangerous to assume
precise results as also accurate
Precision & Accuracy
■ Absolute error: � = �� − �� , where xt is the accepted or true value

�� −��
■ Relative error (Er): �� = × 100%
��

■ Example:
Types of Errors in Chemical Analyses
1. Random (or indeterminate) error: affects measurement precision; causes data to
be scattered
2. Systematic (or determinate) error: affects accuracy of results
3. Gross error: occasional and often large errors; often the product of human errors;
leads to outliers
Systematic Errors
■ Systematic errors have a definite value, an assignable cause, and are of the same
magnitude for replicate measurements made in the same way. They lead to bias in
measurement results.
■ Types of systematic errors:
1. Instrumental errors – caused by nonideal instrument behavior, by faulty calibrations,
or by use under inappropriate conditions. All measuring devices are potential
sources of systematic errors.
Systematic Errors
■ Types of systematic errors:
2. Method errors – arise from nonideal chemical or physical behavior of analytical
systems. Sources of nonideality include the slowness of some reactions, the
incompleteness of others, the instability of some species, the lack of specificity of
most reagents, and the possible occurrence of side reactions that interfere with the
measurement process.
Systematic Errors
■ Types of systematic errors:
3. Personal errors – result from the carelessness, inattention, or personal limitations
of the experimenter; a universal source of personal error is prejudice or bias
■ Many measurements require personal judgments.
■ No matter how honest, most of us have a natural, subconscious tendency to
estimate scale readings in a direction that improves the precision in a set of results.
■ Number bias is another source of personal error.
Random Errors
■ Random errors can never be totally eliminated and are often the major source of
uncertainty in a determination.
■ These errors are caused by many uncontrollable variables that accompany every
measurement.
■ The distribution of replicate data from most quantitative analytical experiments
approaches the Gaussian curve.
Random Errors