ERRORS

IN MEASUREMENT AND
ANALYSIS
 INTRODUCTION

A. It is impossible to perform a
chemical analysis that is error free or
without uncertainty.
B. Our goals are to minimize errors
and to calculate the size of the errors.
 Types of Errors

Basically Three types of errors are studied:-

1. Gross Errors

2. Systematic Errors

3. Random Errors
 GROSS
ERRORS
may arise from faulty equipment or bad laboratory
practice; proper equipment maintenance and
appropriate training and supervision of personnel should
eliminate these. The Errors mainly covers the human
mistakes in reading instruments, recording&
calculating measurement results. Example:- Due to
oversight, The read ofTemperature as 31.5 while the
actual reading may be 21.5. Gross Errors may be of any
amount.these are avoided by adopting two means:-
 Great care must in reading and recording the data.
 Two , Three or even more reading should be taken for the
quantity under measurement.
 Measurement ERRORS`
The causes of measurement errors are numerous and
their magnitudes are variable. This leads to
uncertainties in reported results. However,
measurement errors can be minimized and some types
eliminated altogether by careful experimental design
and control. Their effects can be assessed by the
application of statistical methods of data analysis and
chemometrics .
Errors must be controlled and assessed so that valid
analytical measurements can be made and reported.
The reliability of such data must be demonstrated so
that an end-user can have an acceptable degree of
 Absolute and relative
errors
THE ABSOLUTE ERROR,
EA, in a measurement or result, xM, is given by the equation.
EA = xM - xT
where xT is the true or accepted value. Examples are shown in
Figure 1 where a 200 mg aspirin standard has been analyzed a
number of times. The absolute errors range from -4 mg to +10 mg.
THE RELATIVE ERROR,
ER, in a measurement or result, xM, is given by the equation
ER = (xM - xT)/xT
Often, ER is expressed as a percentage relative error, 100ER. Thus,
for the aspirin results shown in Figure 1, the relative error ranges
from -2% to +5%. Relative errors are particularly useful for
comparing results of differing magnitude.
Absolute and relative
errors
 DETERMINATE
ERRORS
There are three basic sources of determinate or systematic errors that lead to abias in
measured values or results:
● the analyst or operator;
● the equipment (apparatus and instrumentation) and the laboratory environment;
● the method or procedure.
It should be possible to eliminate errors of this type by careful observation
andrecord keeping, equipment maintenance and training of laboratory
personnel.
Operator errors can arise through carelessness, insufficient training, illness
ordisability. Equipment errors include substandard volumetric glassware, faultyor
worn mechanical components, incorrect electrical signals and a poor
orinsufficiently controlled laboratory environment. Method or procedural errors
are caused by inadequate method validation, the application of a method to
samples or concentration levels for which it is not suitable or unexpected
variations in sample characteristics that affect measurements. Determinate errors
that lead to a higher value or result than a true or accepted one are said to show
a
positive bias; those leading to a lower value or result are said to show a negative
bias. Particularly large errors are described as gross errors; these should be
easily apparent and readily eliminated.
 DETERMINATE
ERRORS
Determinate errors can be proportional to the size of sample taken for analysis. If
so, they will have the same effect on the magnitude of a result regardless of the
size of the sample, and their presence can thus be difficult to detect.
For example,
copper(II) can be determined by titration after reaction with potassium
iodide to release iodine according to the equation
2Cu2+ + 4I - 2CuI + I2
However, the reaction is not specific to copper(II), and any iron(III) present in the
sample will react in the same way. Results for the determination of copper in an
alloy containing 20%, but which also contained 0.2% of iron are shown in Figure 2
for a range of sample sizes. The same absolute error of +0.2% or relative error of
1% (i.e. a positive bias) occurs regardless of sample size, due to the presence of
the iron. This type of error may go undetected unless the constituents of the
sample and the chemistry of the method are known.
 Systematic Errors

It can be classified as into following categories :-

1. Instrumental Errors
2. Environmental Errors
3. Observational Errors
 Instrumental Errors

These errors arises due to three main reasons.

1. Due to inherent shortcoming in the instrument.
Example:- If the spring used in permanent magnet
instrument has become weak then instrument will
always read high. Errors may caused because of
friction , hysteresis , or even gear backlash.
2. Due to misuse of the instruments.
3. Due to Loading effects of instruments.
 Environmental Errors

These errors are due to conditions external to

the measuring Device including conditions in
the are surrounding the instrument.
These may be effects of Temperature, Pressure,
Humidity, Dust, Vibrations or of external
magnetic or electrostatic fields.
 Observational Errors

There are many sources of observational errors:-

-- Parallax, i.e. Apparent displacement when the
line of vision is not normal to the scale.
-- Inaccurate estimate of average reading.
-- Wrong scale reading and wrong recording the
data.
-- Incorrect conversion of units between
consecutive reading.
Here in Graph, Full Line shows the systematic Error in non
Linear Instrument.

While Broken Line shows response of an ideal instrument

without Error.
 Random Errors

The quantity being measured is affected by many

happenings in the universe. We are aware for
some of the factors influencing
the measurement, but about the
rest we are unaware. The errors caused by
happening or disturbances about which we are
unaware are Random Errors. Its also
known as residual Errors.
 Example of Random Error

The Gaussian normal distribution. m = mean of measurements. s =

standard deviation of measurements. 68% of the measurements lie in
the interval m - s < x < m + s; 95% lie within m - 2s < x < m + 2s; and
99.7% lie within m - 3s < x < m + 3s.
 ACCUMULATED
ERRORS
Errors are associated with every measurement made in an
analytical procedure, and these will be aggregated in the
final calculated result. The accumulation or propagation of
errors is treated similarly for both determinate
(systematic) and indeterminate (random) errors.
Determinate (systematic) errors can be either positive or
negative, hence some cancellation of errors is likely in
computing an overall determinate error, and in some
instances this may be zero. The overall error is calculated
using one of two alternative expressions, that is
●
 Accuracy, Precision, and
Error

Accuracy, Precision, and Error

How do you evaluate accuracy and precision?
 Accuracy, Precision, and
Error

Accuracy and Precision

• In chemistry, the meanings of accuracy and precision are quite different.

• Accuracy is a measure of how close a measurement comes to the actual or

true value of whatever is measured.

• Precision is a measure of how close a series of measurements are to one

another, irrespective of the actual value.
 Accuracy, Precision, and
Error

Accuracy and Precision

To evaluate the accuracy of a measurement, the measured value must be
compared to the correct value.

To evaluate the precision of a measurement, you must compare the values of two
or more repeated measurements.
 Accuracy, Precision, and
Error

Accuracy and Precision

Darts on a dartboard illustrate the difference between accuracy and
precision.

Good Accuracy, Poor Accuracy, Good Poor Accuracy, Poor

Good Precision Precision Precision

The closeness of a dart to the bull’s-eye corresponds to the degree of accuracy. The
closeness of several darts to one another corresponds to the degree of precision.

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 Accuracy, Precision, and
Error

Determining Error
• Suppose you use a thermometer to measure the boiling point of pure water
at standard pressure.

• The thermometer reads 99.1°C.

• You probably know that the true or accepted value of the boiling point of
pure water at these conditions is actually
• 100.0°C.

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 Accuracy, Precision, and
Error

Determining Error
• There is a difference between the accepted value, which is the correct value
for the measurement based on reliable references, and the experimental
value, the value measured in the lab.

• The difference between the experimental value and the accepted value is
called the error.

Error = experimental value – accepted value

 Accuracy, Precision, and
Error

Determining Error
• For the boiling-point measurement, the error is 99.1°C – 100°C, or –0.9°C.

• The percent error of a measurement is the absolute value of the measured

experimental value minus the accepted value divided by the accepted value,
multiplied by 100%.

measured - accepted
x
Percent error = 100%
accepted value

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 Sample
Sample Problem
Problem 3.2
3.2

2 Calculate Solve for the unknown.

Substitute the equation for error, and then plug in
the known values.
|experimental value – accepted value|
_______________________________
Percent error = X 100%
accepted value

|99.1˚C – 100.0˚C |
= X 100%
100.0 ˚C

0.9°C
_______
= X 100 % = 0.9%
100.0°C
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 Statistical Analysis of Data
The Experimental Data is obtained in
Two Forms of the tests:-
1.Multi sample Test
2.Single Sample Test
1. Multi sample Test:- In this test, The
Repeated measurement of a given quantity
using
aredonedifferent conditions such as
employing different
test instruments,
ways of measurement Different
and by
employing different observers.

2. Single Sample Test :- A single measurement

forsuccession of measurement done under
identical conditions excepting for time known
is
as single sample Test.
 Histogram

When The Number of multi sample

observations are taken experimentally, There is a
scatter of the data about some central value.
One method presenting test results in the
form of histogram. It is also
called frequency distribution curve.
A Histogram is a graphical display of data using bars of different heights.
It is similar to a Bar Chart, but a histogram groups numbers into ranges
And you decide what ranges to use.
There are certain terms which must be defined as they
form the basis defining the measure of dispersion of
data:

1. Range
2.Deviation
3.Average deviation
4. Standard
deviation
5. variance
 Range And Deviation

The simplest possible measure of dispersion is

the range which is the difference between
greatest and least values of data.
Deviation:- Deviation is departure of the
observed reading from the arithmetic mean of
the group of readings.
Average And Standard Deviation
Average deviation is defined as the sum of
the absolute values of deviations
divided by the number of readings.
The absolute value of deviation is the value
without respect to its sign.
Standard deviation is defined as the square root
of the sum of the individual derivations squared,
divided by the number of readings. It is the
important term in analysis of random numbers.