Pharmaceutical Chemistry/ER20-12T/D.

Pharm/1st year/21-22 Arpita Biswas

ERROR
ERRORS
An errors usually refers to an in advertent mistake which is intimately associated with each
measurement. When numerical data and numerical results are not same value at that condition
error must have occured.
Errors are defined as the difference between the observed or measured value & the true or most
probable value.

CLASSIFICATION OR TYPES OF ERRORS: Errors can be divided in various types are

as follows:-
1. Determinate (Systematic / Constant) errors.

2. Indeterminate (Random) errors.

3. Errors in measurements.

4. Gross errors.

5. Other errors.

Determinate (Systematic/Constant) errors

These types of errors are avoided & their magnitudes are determined, thereby correcting
the measurement.
Determinate errors can be subdivided in various forms like –

 Personal errors: These errors are not connected with the method/ procedure but the
individual analyst is responsible for them.
The reason for coming personal errors is

o Inability in judging color

o Errors in burette reading properly
o Use of impure reagents
o Calculation errors

 Operational errors: Operational errors are physical in nature & occurred when the technique
is not followed properly.

 Instrument and Reagent errors: These errors can be easily avoided by using proper
calibration weights, glass wares & pure reagents.
The reason mainly for these types of errors are –

o Balance arms are not equal lengths.

o The weights are not calibrated properly.
o In correctly graduated burettes.
o Attacking of foreign materials on glass wares.
o The reagent used is not pure.
 Methodic errors: These types of errors may sometime create a serious problem in chemical
analysis.
The reason mainly for these types of errors are –
o Errors in experimental procedure.
o Chosen of incorrect sampling.
o Occurrence of side reaction
Pharmaceutical Chemistry/ER20-12T/D. Pharm/1st year/21-22 Arpita Biswas

ERROR

 Additive & Proportion errors: The absolute value of additive errors is independent of the
amount of constituent present in the determination.
Proportional errors arise for taking incorrect values for calculation the experimental values.

Indeterminate (Random / Accidental) errors:

These errors are very minute errors that can’t be determined & the analyst has no
control over them.
These errors are of divided into two away:-
o Variation within determinate errors: These can’t prevent
from variation.

o Erratic errors: An analyst has no control over such errors.

The reason for coming these type of errors are –

o Vibration in balance while handling.
o Accidental loss of material during analysis

Measurement errors:
The reasons for these errors are –
o Insensitivity of the balance.
o Wrong use of ring – rider
o Placing the weights at the edge of the pan.
o Non – calibrated weights are used.
o Errors in measuring the solution due to in correctness
of glass wares.

Gross errors:
The errors are coming due to –
o Use of incorrect conversion factors
o Method selection is wrong.
o Storage of sample is not a proper away

Other errors:
Some errors are-
o Errors in radiometric analysis.
o Errors in chromatography.
o Photometric errors.

MINIMIZATION OF ERRORS

The errors (mainly determinate errors) can be minimized by adopting any of the following
methods:

1. Calibration of Apparatus and Application of Corrections: All instruments (weight,

balance, burette, pipettes & spectrophotometers etc.) should be calibrated and appropriate
corrections applied to the original measurements.
Pharmaceutical Chemistry/ER20-12T/D. Pharm/1st year/21-22 Arpita Biswas

ERROR
2. Running a blank determination: This consists in carrying out a separate determination, the
sample being omitted under exactly the same experimental conditions as are employed in the
actual analysis of the sample. The object is to find out the effect of the impurities introduced
through the reagents, vessels & solvents.

3. Running a controlled determination: This consists in carrying out a determination under

as nearly as possible identical experimental conditions upon a quality of a standard
substance which contains the same weight of the constituent as is contained in the
unknown sample.
The weight of the constituent in the unknown can then be calculated from the relation –

X = Weight of the constituent in the unknown

4. Running of parallel determination: In some cases the accuracy of a result may be

established by carrying out the analysis in an entirely different manner. These serve as a
check on the result of singly determination and indicate only the precision of the analysis. In
titrimetry, performing duplicate or triplicate titration is a typical example.

5. Standard addition: A known amount of the constituents being determined is added to the
sample, which is then analyzed for the total amount of constituent present. Standard addition
method is usually applied to physico – chemical procedures such as Spectrophotometry &
Polarography.

6. Internal Standard: Internal standard procedure is of particular value in Spectroscopic &

Chromatographic determination. It involves adding a fixed amount of a reference material
(Internal Standard) to a series of known concentrations of the material to be measured.
Any unknown concentration can then be determined by adding the same quantity of internal
standard & finding where the ratio obtained falls on the concentration scale.
7. Isotopic dilution: A known amount of the element can be determined, containing a
radioactive isotope, is mixed with the sample & the element is isolated in a pure form
(usually as a compound), which is then determined.

ACCURACY
Accuracy has been defined as the degree of agreement between a measured value /
observed value and a true value / most probable value / accepted true value. Practically no
measurement is completely accurate, true value is never known except within certain limits.

Accuracy can be expressed in terms of Absolute & Relative error.

Absolute error (d) of a measurement value is a numerical difference between the true
value (µ) and the observed value (x)
Pharmaceutical Chemistry/ER20-12T/D. Pharm/1st year/21-22 Arpita Biswas

ERROR

Relative error (e) is the absolute error divided by the true value.

Accuracy expresses the Correctness of a measurement.

PRECISION
Precision is defined as the concordance of a series or a number of measurements of the
same quantity. The mean deviation is the measure of Precision.

Precision express the Reproducibility of a measurement.

The three terms which are used to describe the precision of a set of replicate data.

o Standard deviation- It is the root mean square deviation from mean.

o Variance = Square of standard deviation

o Co-efficient of variation = Std. deviation/Mean x 100%

Methods of Expressing Precision: The various ways of expressing precision are described
below:

Average Deviation: The average deviation of the measurements of a set is the mean of the
difference of the individual measurements, without regard to sign.

(∑│xi x│)
Average deviation a.d. = =d
N

Where, x = the mean of measurement = ∑xi/N

xi = the individual measurements
N = the number of measurements
Pharmaceutical Chemistry/ER20-12T/D. Pharm/1st year/21-22 Arpita Biswas

ERROR

SIGNIFICANT FIGURE
The term Digit denotes any one of the ten numericals, including Zero (0). A significant figure is
a digit which denotes the amount of the quality in the place in which it stands. The digit
zero is a significant figure except when it is the first figure in a number.

For example, in the quantities 1.3680 & 1.0082 g, the zero is significant but in the
quantity 0.0035 kg, the zeros are not significant figure. They serve only to suitable choice
of units. i.e. 3.5 kg.
The first two numbers contain five significant figures but 0.0035 contains only two significant
figures.

A figure or digit denotes any one of the ten numerals that is 0, 1, 2, 3, 4, 5, 6, 7, 8, and 9. A digit
alone or in combination serves to express a number.

E.g.
100.04 : Five significant figures.
0.004 : One significant figure.
600.0 : Four significant figures.
0.0780 : Three significant figures.
500.00 : Five significant figures.
3.15 x 1012 : Three significant figures.

IMPORTANT AND PROBABLE QUESTION:

1) Write down the various methods of minimizing systematic errors.

2) Define Primary and Secondary standards with examples.
3) What is meant by quantitative analysis? How will you differentiate it from qualitative
analysis?
4) Describe the various types of Errors in analytical chemistry. Write down the effect of systemic
errors on analytical results.
5) What are the requirements that should be meet to be a Primary Standard?
6) Short notes on: Accuracy and Precision.
7) Classify the different types of errors. Differentiate between precision and accuracy with
suitable examples.