Errors in Chemical Analyses

Some important terms

Replicates, Mean, Median, Precision, Accuracy

Replicate measurements
Replicates are samples of about the same size that are carried through an analysis in
exactly the same way

Replicate are seldom the same

Results from six replicate determination of iron in aqueous samples of a standard

solution containing 20.0 ppm iron (III). The mean value of 19.78 has been rounded
To 19.8 pmm

Mean and Median

Central value, mean or average is obtained by dividing the sum of replicate measurements
by the number of measurement
The median is the middle result when replicate data are arranged in increasing or decreasing
order. There are equal number of results that are larger and smaller than the median. For
an odd number of results, the median can be found by arranging the results in order and
locating the middle result. For an even number, the average value of the middle pair is used.

Precision
Precision is the closeness of results/measurements that have been obtained in exactly the
same way.
Precision is determined by repeating the measurement on replicate sample.

Three terms are widely used to describe the precision of a set of replicate data
Standard deviation, variance and coefficient of variation.

These three are functions of how much an individual result xi differs from the mean, called
the deviation from the mean, di

Accuracy
Accuracy indicates the closeness of the measurement to the true or accepted value and is
expressed by the error.
Accuracy measures agreement between a result and the accepted value.
Precision, on the other hand, describes the agreement among the several results obtained
in the same way.

Accuracy is often difficult to determine because the true value is usually unknown. An
accepted value must be used instead. Expressed in terms of absolute or relative error
Precision is determined by measuring replicate samples.

Difference between Accuracy and Precision

Accuracy
Absolute Error
The absolute error E in the measurement of a quantity xi is given by the equation

where xt is the true or accepted value of the quantity.

Accuracy
True value was 20 ppm

Absolute error immediately

to the left side of the true value
- 0.2 ppm, smaller than true value

Absolute error immediately

to the right side of the true value
+ 0.1 ppm, larger than true value

Accuracy
Relative Error
The relative error Er is given by the expression
Relative error is also expressed in
Parts per thousand (ppt). Eg, the
Relative error for the mean data
In the adjacent figure is

The danger of assuming that precision results are also accurate

Absolute Error

Types of Error
Chemical analyses are affected by at least
two types of errors.
Random (or indeterminate error),
causes data to be scattered more or less
symmertically around a mean value
Random error is reflected by its
precision, Analyst 1 and 3 had less random
error than 2 and 4

Types of Error
Chemical analyses are affected by at least
two types of errors.
Systematic (determinate error), causes
the mean of a data set to differ from the
accepted value
Analyst 1 and 2 have little systematic
error, but for 3 (- 0.7%) and 4 (- 1.2%)
This error causes the results to be too
high or too low. Eg. Defects in the
procedure

Types of Error

A third type of error is gross error, differ from indeterminate and determinate errors.
Gross errors lead to outliers, results that appear to differ markedly from all other data
In a set of replicate measurements.
Eg. Loss of precipitate before weighing, human errors.

Systematic Error
Systematic error have definite value, assignable cause, and same magnitude for replicate
measurement. They lead to bias in measurement results. Bias affects the data and it bears a
sign

With constant errors, the absolute error is constant with sample size, but the relative
error varies when the sample size is changed.

With proportional errors, the absolute error varies with sample size, but the relative
Error stays constant when the sample size is changed.
Systematic errors may be either constant or proportional

Random error is reflected by its precision,

Analyst 1 and 3 had less random error than 2
and 4

Analyst 1 is precise and accurate. The results of analyst 3 are precise, but the absolute
error is large. The results of analysts 2 and 4 are imprecise and inaccurate

 Imagine a situation in which just four small random errors combine to give an overall error
We will assume that each error has an equal probability of occurring and that each can
cause the final result to be high or low by a fixed amount U

The most frequent occurrence is zero

from the mean

 In the calibration of a 10 ml pipet, a small flask and stopper were weighed

10 ml of water was transferred to the flask with the pipet, and flask was stoppered
Flask, stopper and water were then weighed again.
Temperature of the water was also measured ( density)
Mass of the water was then calculated by taking the difference between the two masses
Mass of the water divided by its density is the volume delivered by the pipet. 50 times

The data could be rearranged

Into frequency distribution groups

Data points falling into a series of

Adjacent 0.003 ml ranges are noted

- Histogram

The population standard deviation , is a measure of the precision of the population

, is given by the equation where, N is the number of data points making the population

Z is the deviation from the mean relative to the standard deviation

2 is variance

Regardless of its width, 68.3% of the area beneath a Gaussian

curve for a population lies within one standard deviation ( 1) of the mean m. Thus,
roughly 68.3% of the results making up the population will lie within these bounds.
Furthermore, approximately 95.4% of all data points are within ( 2) of the mean and
99.7% within ( 3).