Evaluating Analytical Data

(Statistical Analysis of Data )

The most important aspect of the job of the chemical analyst is to assure that the
data and results that are reported are of the maximum possible quality. This means
that the analyst must be able to recognize when the test instrument is breaking down
and when a human error is suspected. The analyst must be as confident as he or she
can be that the readout from an instrument does in fact indicate a true readout as
much as is humanly possible. The analyst must be familiar with error analysis
schemes that have been developed and be able to use them to the point where
confidence and quality is assured.

Experimental measurements always contain some variability, so no conclusion

can be drawn with certainty. Statistics gives us tools to accept conclusions that have a
high probability of being correct and to reject conclusions that do not. Every
measurement has some uncertainty, which is called experimental error. Conclusions
can be expressed with a high or a low degree of confidence, but never with complete
certainty. Experimental error is classified as either systematic or random.

Type of error:

1- Systematic Error
Systematic error, also called determinate error, arises from a flaw in equipment or
the design of an experiment. If you conduct the experiment again in exactly the same
manner, the error is reproducible. In principle, systematic error can be discovered and
corrected, although this may not be easy. A key feature of systematic error is that it is
reproducible.. Systematic errors include personal, instrumental, and method errors. Is
more significant when analyzing smaller samples, as we increase the size of the
sample the obtained results become closer to the expected result.
Example: suppose washing 500 mg of precipitate with 200 ml of water and the
loss by washing is 0.50 mg.
the relative loss by solubility (for 500 mg) =

the relative loss by solubility (for 50 mg) =

Ways to detect systematic error

1. Analyze a known sample, such as a certified reference material.
2. Analyze blank samples containing no analyte being sought. If you observe a
nonzero result, your method responds to more than you intend.
3. Use different analytical methods to measure the same quantity. If results do
not agree, there is error in one (or more) of the methods
 4. Round robin experiment: Different people in several laboratories analyze
identical samples by the same or different methods. Disagreement beyond the
estimated random error is a systematic error.

2- Random Error
Random error, also called indeterminate error, arises from uncontrolled (and
maybe uncontrollable) variables in the measurement. It arise from several sources,
including collecting samples, manipulating samples during the analysis, and making
measurements. A random error has an equal chance of being positive or negative.
Positive and negative fluctuations occur with approximately equal frequency and
cannot be completely eliminated. It is always present and cannot be corrected.
Therefore, some statistical bases and lows are used to evaluate the analytical results.

Precision and Accuracy

Precision describes the reproducibility of a result. If you measure a quantity

several times and the values agree closely with one another, your measurement is
precise. If the values vary widely, your measurement is not precise.

Accuracy describes how close a measured value is

standard is available, accuracy is how close your value is to the known value.

Statistical method
Term population is used when an infinite sampling occurred or all possible
subjects were analyzed. Obviously we cannot repeat a measurement an infinite
number of times so quite often the idea of a population is theoretical; and in those
cases we take a representative sample of the entire population.

The three main measures in quantitative statistics are the mean variance and
standard deviation. These measures form the basis of any statistical analysis.

Mean
Technically, the mean (denoted ), can be viewed as the most common value
(the outcome) would expect from a measurement (the event) performed repeatedly. It
has the same units as each individual measurement value, which is the sum of all the
measurements Xi, divided by the number of measurements (n). The mean gives the
center of the distribution.
 Variance
The variance (s2 or 2) represents the spread (the dispersion) of the repeated
measurements either side of the mean. As the notation implies, the units of the
variance are the square of the units of the mean value. The greater the variance, the
greater the probability that any given measurement will have a value noticeably
different from the mean.

S=standard deviation,
Xi= absorbed measurement,
= mean,
n= number of measurement,
n-1= degrees of freedom

Standard Deviation
The standard deviation (s) also provides a measure of the spread of repeated
measurements either side of the mean. measures how closely the data are clustered
about the mean. The smaller the standard deviation, the more closely the data are
clustered about the mean. An advantage of the standard deviation over the variance is
that its units are the same as those of the measurement. The standard deviation also
allows you to determine how many significant figures are appropriate when reporting
a mean value. The standard deviation measures the width of the distribution.

S=standard deviation,
Xi= absorbed measurement,
= mean,
n= number of measurement,
n-1= degrees of freedom.
 Figure (2): Gaussian curves for two sets of light bulbs, one having a standard deviation half
as great as the other. The number of bulbs described by each curve is the same.

For an infinite set of data, the mean is designated by the lowercase Greek letter
mu, u (the population mean), and the standard deviation is written as a lowercase
Greek sigma, (the population standard deviation). We can never measure u and
but the values of and s approach u and as the number of measurements
increases.

Example:
 The median ( m)
It is the central value of an odd number of set of measurement or the average of
the central pair for a set containing as even number of measurements.

Example (1) : calculate the median of the two following sets of measurements:
7, 13, 16, 20, 23, 27, 29

m= 20

Example (2): calculate the median of the two following sets of measurements:
7, 12, 13, 16, 18, 20, 25, 29

m=

The Range (R)

The range in statistics for a given data set is the difference between the highest
and lowest values. Thus, the range could also be defined as the difference between
the highest observation and lowest observation. The obtained result is called the
range of observation. The range in statistics represents the spread of observations.

To find the range in statistics, we need to arrange the given values or set of data
or set of observations in ascending order. That means, firstly write the observations
from the lowest to the highest value. Now, we need to use the formula to find the
range of observations.

Example (1) : Find the range of given observations:

32, 41, 28, 54, 35, 26, 23, 33, 38, 40.

arrange the given values in ascending order: 23, 26, 28, 32, 33, 35, 38, 40, 41, 54

R= 54-23= 31

The difference between mean and range is, the mean represents the average value
of a set of data whereas the range denotes the spread of observations. The mean is
equal to the ratio of the sum of all observations and the total number of observations
but the range is the difference between maximum and minimum values in the
observation.
Examples:
1- What are the standard deviation, the relative standard deviation and the
percent relative standard deviation for the data in table 1.1

Table 1.1

To calculate the standard deviation we first calculate the difference between

each measurement and the mean value (3.117), square the resulting differences.

Next, divide this sum of the squares by n 1, where n is the number of

measurements, and take the square root

Finally, the relative standard deviation and percent relative standard deviation are

2- What is the variance for the data in Table 1.1

3- The following numerical results were obtained in a given laboratory
experiment: 0.09376, 0.09358, 0.09385, and 0.09369. Calculate the relative
parts per thousand standard deviation.

must calculate both the mean and the standard

the mean:

Next, the deviations:

Then, the standard deviation:

Finally, to get the relative parts per thousand standard deviation:

4- Calculate the mean and the standard deviation of the following set of
analytical results: 15.67, 15.69, and 16.03 g.
Use another method

5- The following replicate weighings were obtained: 29.8, 30.2, 28.6, and
29.7mg. Calculate the standard deviation of the individual values and the
standard deviation of the mean. Express these as absolute (units of the
measurement) and relative (% of the measurement) values.