E XPERIMENT 1

INTRODUCTION TO STATISTICAL TREATMENT OF

DATA

Name: Section:

Pre-Laboratory

Answer the following questions before coming to the laboratory.

The pre-laboratory assignments in this laboratory manual are designed to assist you in
preparing you for the experiments, and the questions are extracted from the material
furnished in the experiment.

1. Briefly define the following terms

Accuracy:

Precision:

Systematic Error:

Random Error:

2. The results of the analysis of iron percentage in a sample are as follow:

19.93, 19.88, 20.00, 19.90, 19.98 and 19.95

Calculate:
A. The mean

B. The median

C. The standard deviation

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D. Coefficient of variation

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E XPERIMENT 1

INTRODUCTION TO STATISTICAL TREATMENT OF

DATA

INTRODUCTION

It is impossible to perform a chemical analysis in such a way that the results are
totally free of errors, or uncertainties. All we hope for is to minimize errors and to
estimate their size with acceptable accuracy. Moreover, every measurement is
influenced by many uncertainties thus causing a scatter of results; thus measurement
uncertainties can never be eliminated.

THE TRUE VALUE OF A MEASUREMENT IS NEVER KNOWN EXACTLY

Therefore, results should always be reported along with some estimation of the
errors involved. Such method of reporting provides hints regarding the accuracy and
precision of the reported data.

DATA OF UNKNOWN PRECISION AND ACCURACY ARE WORTHLESS

ACCURACY and PRECISION

Accuracy is the degree of agreement between the measured value and the true
value. However, an absolute true value is seldom known. Therefore, a more realistic
definition of accuracy would assume it to be agreement between a measured value and
the accepted true value. Moreover, accuracy indicates the closeness of the measurement
to its true or accepted value and is expressed by the error.
Precision is defined as the degree of agreement between replicate measurements
of the same quantity. That is, the closeness of the results that have been obtained
exactly in the same way (i.e., the repeatability of a result). Good precision does not
assure good accuracy. Since all analyses are unknown, the higher the degree of
precision, the greater the chance of obtaining the true value. Figure 1-1 I illustrates the
relationship between accuracy and precision.

high accuracy high accuracy low accuracy low accuracy

high precision low precision low precision high precision

FIGURE 1-1 Accuracy versus precision

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WAYS OF EXPRESSING ACCURACY

There are two ways in which the accuracy of a measurement can be expressed,
an accepted true value for comparison being assumed.

Absolute Error (E)

The difference between the true value and the measured value with regard to the
sign, is the absolute error, and it is reported in the same units as the measurement.
E  xi  xt
xt is the true value or the expected value of the quantity.

Example:

If a 2.62 g sample of material is analyzed to be 2.52 g, in this case the true value is 2.62
g and thus the absolute error is -0.10 g

Relative Error

The relative error is the measured value or mean expressed as a percentage of

the true value. This is a more useful value than the absolute error, since it reflects the
error relative to the size of the true value.
x  xt
Er  i  100%
xt
WAYS OF EXPRESSING PRECISION

Each set of analytical results should be accompanied by an indication of the

precision of the analysis. The precision of a set of replicate data is described by three
terms:
standard deviation,
relative standard deviation
variance, and
coefficient of variation.

All these terms are a function of the deviation of the data from the mean.
Deviation from mean = d i  xi  x

Individual results from a set of measurements are seldom the same, so a central
or ‘best’ value is used to represent the set of measurements. Either the mean or the
median may serve as the central value for a set of replicate measurements.
N

x i
mean = arithmetic mean = average = x  i 1

N
The median is the middle result when replicate data are arranged in an
increasing order. For an odd number of results, the median is the central value of the
arranged set of data. While for an even number of results, the mean of the middle pair is
used

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Example:
Calculate the mean and the median for the following set of data,

19.4, 19.6, 19.5, 20.1, 20.3, 19.8

19.4  19.5  19.6  19.8  201

.  20.3
mean  x   19.78  19.8
6

To determine the median the set of data must be arranged in an increasing order as
follow;

19.4, 19.5, 19.6, 19.8, 20.1, 20.3

Since the data contains an even number of measurements (N=6), the median is the
average of the central pair;

19.6  19.8
median   19.7
2

The median is used advantageously when a set of data contains an outlier. This
is a result that differs significantly from the rest of the data in the set. An outlier can
have a significant effect on the mean of the set but has no effect on the median, as is
illustrated in the next example

Example:
Calculate the mean and the median for the following set of data,
19.4, 19.6, 19.5, 20.1, 19.8, 22.0
In this set of data there is an outlier (22)

19.4  19.5  19.6  19.8  201

.  22.0
mean  x   20.0
6
To determine the median the set of data must be arranged in an increasing order as
follow;
19.4, 19.5, 19.6, 19.8, 20.1, 22.0
Since the data contains an even number of measurements (N=6), the median is the
average of the central pair;
19.6  19.8
median   19.7
2
Notice the median was the same in the absence and in the presence of the outlier
(compare the median in this example and that of the previous one).

Standard Deviation

The standard deviation  of an infinite set of experimental data (also known as

the population standard deviation) is theoretically given by

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 N 2

  xi   
i 1
 
N
where xi represents the individual measurements and  represents the true value. This
equation holds strictly only as N   , where N is the number of measurements.
However, in practice, only limited numbers of measurements are collected. Therefore,
the sample standard deviation in this case is utilized. The sample standard deviation s
of a finite set of experimental data (generally N<30) is given by
N
  xi  x
2

s i 1
N 1
where x is the mean of the measured values and N-1 is degrees of freedom. Remember,
if N becomes greeter than 30 than s=  .

Variance (s2)

The variance is the square of the standard deviation:

 
N 2
 xi  x
s 2  i 1
N 1
Note that the standard deviation has the same units as the data, whereas the
variance has the units of the data squared

Relative standard deviation (RSD)

Relative standard deviation is just the standard deviation expressed as a

percentage of the mean
 s
RSD     1000 ppt (part per thousand)
 x

Coefficient of variation (%RSD)

Coefficient of variation is the percentage relative standard deviation

 s
CV     100
 x

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 SOURCES OF ERRORS IN EXPERIMENTAL DATA

1 Random (or Indeterminate) Error

Causes data to be scattered more or less symmetrically around a mean value.

This type of error is caused by the many uncontrollable variables that are an
inevitable part of physical or chemical measurement.

2 Systematic (or Determinate) error

Causes the mean of a set of data to differ from the accepted value.
Systematic errors are caused
1. by the instrument errors that result from imperfection in measuring
devices and instabilities in their power supplies,
2. by the method errors which arise from non ideal chemical or physical
behaviour of analytical system, and
3. by the personal errors which result from the carelessness, inattention
or personal limitation of the experimenter.

3 Gross Error

This type of errors occurs only occasionally, is often large, and may cause a
result to be either high or low. Gross errors lead to outliers

DUE TO RANDOM ERRORS EXPERIMENTAL DATA ARE REPRESENTED

BY A GAUSSIAN CURVE OR NORMAL ERROR CURVE

SUMMERY

The proper treatment of error in data is critical in any experimental science. The
mere reporting of numbers without any indication of how reliable the numbers are is
worthless. The application of any of the statistical procedures aforementioned depends,
on acquiring multiple data for any process or phenomenon measured.

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 PROCEDURE

1. Put a very clean and dry 50 ml beaker on an electric balance and tear its weight.
Use the same balance for all weighting.

2. Fill a 500 ml beaker with tape water, and then using a 10 ml pipet transfer 10 ml to
the 50 ml beaker that is mounted on the balance.

3. Record the balance reading on the results and calculations sheet.

4. Drain the water and dry the beaker completely.

5. Repeat steps one through four thirty times, recording the balance reading on the
report sheet after every addition.

6. Clean up.

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RESULTS AND CALCULATIONS

Name: Section:

Assuming the density of tap water at ambient temperature is 1.0 g/ml. The weight of the
10.0 ml pipeted tap water (accepted true value) is 10.0 g.

No. Weight Deviation from Mean Absolute Errors Relative Errors

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30

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CALCULATIONS

Divide the data into three sets of ten readings each, and calculate the standard
deviation for each set.

Calculate the standard deviation for the whole set of data using both expressions
for the sample standard deviation and population standard deviation. Compare
the two values.

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