Data Analysis in Analytical

Chemistry

Dr. Kamyar Shameli

E-mail: Kamyar @utm.my
Course: SMJC 2022
Errors in Chemical Analysis
 Chemical analyses are affected by at least two types of errors
1. Random (or indeterminate) error
One type, called random (or indeterminate) error, causes data to be scattered more or less
symmetrically around a mean value. Refer again to Figure 5-3, and notice that the scatter in the data,
and thus the random error, for analysts 1 and 3 is significantly less than that for analysts 2 and 4. In
general, then, the random error in a measurement is reflected by its precision.
 Random, or indeterminate, errors affect measurement precision.

2. Systematic (or determinate) error

Causes the mean of a data set to differ from the accepted value.
For example, the mean of the results in Figure 5-1 has a systematic error of about 20.2 ppm Fe. The
results of analysts 1 and 2 in Figure 5-3 have little systematic error, but the data of analysts 3 and 4 show
systematic errors of about 20.7 and 21.2% nitrogen.
 Systematic, or determinate, errors affect the accuracy of results.

3. A third type of error is gross error.

They usually occur only occasionally, are often large, and may cause a result to be either high or
low. They are often the product of human errors.
An outlier is an occasional result in replicate measurements that differs significantly from the other results.
(Had one of the results shown in Figure 5-1 occurred at, say, 21.2 ppm Fe, it might have been an outlier.)
5B-1 Sources of Systematic Errors
There are three types of systematic errors:
 Instrumental errors are caused by non ideal instrument behaviour, by faulty calibrations, or by use
under inappropriate conditions.
 Method errors arise from non ideal chemical or physical behaviour of analytical systems.
 Personal errors result from the carelessness, inattention, or personal limitations of the experimenter.

Example:
Suppose that 0.50 mg of precipitate is lost as a result of being washed with 200 mL of wash liquid.
If the precipitate weighs 500 mg, the relative error due to solubility loss is -(0.50/500) X100% = -0.1%.
Loss of the same quantity from 50 mg of precipitate results in a relative error of -1.0%.
Example 1: Example 5:

Example 2:

Example 3:

Example 4:
Random errors in chemical analysis
A three-dimensional plot
showing absolute error in
Kjeldahl nitrogen determinations
for four different analysts. Note
that the results of analyst 1 are
both precise and accurate. The
results of analyst 3 are precise,
but the absolute error is large.
The results of analysts 2 and 4
are both imprecise and
inaccurate.
Random Error Sources
Table shows all the possible ways the four errors can combine to
give the indicated deviations from the mean value.

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.
This ratio of 1:4:6:4:1 is
a measure of the
probability for a
deviation of each
magnitude.
If we make a sufficiently large number of measurements, we can expect
a frequency distribution like that shown in Figure 6 a.

Figure 6 b shows the theoretical distribution for ten equal-sized

uncertainties. Again we see that the most frequent occurrence is zero
deviation from the mean.

At the other extreme a maximum deviation of 10 U occurs only about once

in 500 results. When the same procedure is applied to a very large number
of individual errors, a bell-shaped curve like that shown in Figure 6 c results.
Such a plot is called a Gaussian curve or a normal error curve.
 The Population Mean u and The Sample Mean X

Scientists find it useful to differentiate between the sample mean and the population mean. The
sample mean x the arithmetic average of a limited sample drawn from a population of data.
 The Population Standard Deviations
The population standard deviations, which is a measure of the precision of
the population, is given by the equation

Note that z is the relative deviation of a data point from the

mean, that is, the deviation relative to the standard deviation.

The equation for the Gaussian error curve is:

Random errors follow a Gaussian or normal distribution.
We are 95% certain that the true value falls within 2σ (infinite population),
IF there is no systematic error.

©Gary Christian,
Analytical Chemistry,
6th Ed. (Wiley) Fig. 3.2 Normal error curve.
The sample mean x is found from:
Where N is the number of measurements in the sample set.

The same equation is used to calculate the population mean μ.

Where N is now the total number of measurements in the population.

The population standard deviation σ, which is a measure of the precision of the population, is
given by the equation.

Number of measurements
Sample mean
Population mean Population standard deviation
 The sample standard deviation: A measure of precision

Number of degrees of
freedom
Sample standard deviation (N -1)
Where the quantity (xi - x) represents the deviation di of value xi from the mean x.
Thus, the sample standard deviation s is given by the equation.

An alternative expression for sample standard deviation

Example 1:
The following results were obtained in the replicate determination of the lead content of a blood
sample: 0.752, 0.756, 0.752, 0.751, and 0.760 ppm Pb. Find the mean and the standard deviation of this
set of data.

To apply this Equation, we calculate

Standard deviation and

Equation for calculating the pooled standard deviation

 The equation for computing a pooled standard deviation from several sets of data takes the
form
Where N1 is the number of results in set 1, N2 is the number in set 2, and so forth. The term
Nt is the total number of data sets pooled.
Example 2:
Glucose levels are routinely monitored in patients suffering from diabetes. The glucose
concentrations in a patient with mildly elevated glucose levels were determined in different
months by a spectrophotometric analytical method. The patient was placed on a low-sugar
diet to reduce the glucose levels. The following results were obtained during a study to
determine the effectiveness of the diet. Calculate a pooled estimate of the standard
deviation for the method.
The standard error of a mean, sm, is the standard deviation of a set of data
divided by the square root of the number of data points in the set.

Variance (s2)
The variance, s2, is equal to the square of the standard deviation.
Relative Standard Deviation (RSD) and Coefficient of Variation
(CV)
Relative standard deviation by dividing the standard deviation by the mean value of the
data set.

The relative standard deviation, RSD = (sr)

The result is often expressed in parts per thousand (ppt)

The relative standard deviation multiplied by 100% is

called the coefficient of variation (CV).

Spread or range (w)

It is the difference between the largest value in the set and the smallest.
Spread or Range (w)
The spread, or range, w, is another term that is sometimes used to describe the precision of
a set of replicate results. It is the difference between the largest value in the set and the
smallest.
Example 3:
For the set of data in Example 1, calculate (a) the variance, (b) the relative standard
deviation in parts per thousand, (c) the coefficient of variation, and (d) the spread.
Standard deviation of calculated results
Standard deviation of a sum or difference
Consider the summation:

Hence, the standard deviation of the result sy is:

sy = 2.63 (±0.06)
Standard deviation of a product or quotient

y (±)

We can write the answer and its uncertainty as 0.0104 (±0.0003).

Example 4:
Calculate the standard deviation of the result of

y
Example 5:
Example 6:
Example 1: Example 3: Example 5:

Example 6:

Example 2:

Example 4: