Classification of Errors

Classification of Errors:
Errors are classified in two types – Systemic (Determinate) and Random (Indeterminate) errors

Systemic (Determinate) errors:

Errors which can be avoided or whose magnitude can be determined is called as systemic errors.
It can be determinable and presumably can be either avoided or corrected. Systemic errors
further classified as

 Operational and personal error

 Instrumental error
 Errors of method
 Additive or proportional error

Operational and personal error:

Errors for which the individual analyst is responsible and are not connected with the method or
procedure is called as personal errors e.g. unable to judge color change

When errors occur during operation is called as operational error e.g. transfers of solution,
effervescence, incomplete drying, underweighting of precipitates, overweighing of precipitates,
and insufficient cooling of precipitates. These errors are physical in nature and occur when sound
analytical techniques is not followed

Instrumental and Reagent errors:

Errors occur due to faulty instrument or reagent containing impurities e.g. un-calibrated weights,
un-calibrated burette, pipette and measuring flasks.

Errors of Method:
When errors occur due to method, it is difficult to correct. In gravimetric analysis, error occurs
due to Insolubility of precipitates, co-precipitates, post-precipitates, decomposition, and
volatilization.

In titrimetric analysis errors occur due to failure of reaction, side reaction, reaction of substance
other than the constituent being determined, difference between observed end point and the
stoichiometric equivalence point of a reaction.

Additive or proportional errors:

Additive error does not depend on constituent present in the determination e.g. loss in weight of
a crucible in which a precipitate is ignited.

Proportional error depends on the amount of the constituent e.g. impurities in standard
compound.
Random Errors:
It occurs accidentally or randomly so called as indeterminate or accidental or random error.
Analyst has no control in this error. It follows a random distribution and a mathematical law of
probability can be applied.

Minimization of Errors
Analyst has no control on random errors but systemic errors can be reduced by following methods.

Calibration of apparatus: By calibrating all the instruments, errors can be minimized and appropriate
corrections are applied to the original measurements.

Control determination: standard substance is used in experiment in identical experimental condition to

minimize the errors.

Blank determination: By omitting sample, a determination is carried out in identical condition to minimize
the errors occurs due to impurities present in reagent.

Independent method of analysis: It is carried out to maintain accuracy of the result e. g. Iron (III) is first
determined gravimetrically by precipitation method as iron (III) hydroxide and then determined
titrimetrically by reduction to the iron (II) state.

Parallel determination: Instead of single determination, duplicate or triplicate determination is carried

out to minimize the possibilities of accidental errors.

Standard edition: This method is generally applied to physico-chemical procedures such as polarography
and spectrophotometry.

Internal standards: It is used in spectroscopic and chromatographic determination.

Amplification methods: It is used when a very small amount of material is to be measured which is beyond
the limit of the apparatus.

Isotopic dilution: It is used for the compound containing radio-active isotope.

Accuracy and Precision

Accuracy: It refers to the closeness of a single measurement to its true value. It expresses the correctness
of a measurement and determined by absolute and comparative way.
Precision: It refers to the closeness of the set of values obtained from identical measurements of a
quantity. It represents the reproducibility of a measurement.

Errors in Analysis (Examples)

Example-1: Determine the accuracy and precision of the mass of a piece of a metal performed by three
different students, where mass of a piece of metal is 0.520gm. Data obtained by each student are
recorded as follow.

Student A: 0.521, 0.521, 0.509 Average: 0.515

Student B: 0.516, 0.515, 0.514 Average: 0.515
Student C: 0.521, 0.520, 0.520 Average: 0.520

Result:
Student A: Data are not accurate and not precise because the individual values differ widely from each
other and average value is not matching with true value.

Student B: Data are not accurate but precise because the individual values deviate but little from one
another, however, the average value is still not matching with true value.

Student C: Data are accurate and precise as the individual value is almost same and average value is
matching with true value.

Example-2: Determine the significant figure of 0.230, 0.002, 005.2, and 10.0.
Result:

Values Significant figure

0.230 3

0.002 3

005.2 2

10.0 2

Example-3: Iron samples are analyzed and the values obtained are 7.08, 7.21, 7.12, 7.09, 7.16, 7.14,
7.07, 7.14, 7.18, and 7.11. Calculate the mean and standard deviation.

Value (x) Value – mean (y) [x-y] (x-y)2

7.08 -0.05 0.0025

7.21 0.08 0.0064

7.12 -0.01 0.0001

7.09 -0.04 0.0016

7.16 0.03 0.0009

7.14 0.01 0.0001

7.07 -0.06 0.0036

7.14 0.01 0.0001

7.18 0.05 0.0025

7.11 -0.02 0.0004

Mean value = 7.13 Sum of (x-y)2 = 0.0182

Average mean value (x) = 7.13

No. of value (n) = 10
Standard deviation = square root of: sum of (x-y)2 / (n-1)
Standard deviation = square root of 0.0181/9
Standard deviation = +0.045 %

Error Analysis Example

Error analysis is always a difficult area for students. However, the careful consideration of experimental
error is one of the important skills that we need to learn to be effective scientists. In the following
discussion, the errors in a titration experiment are considered. The first section is a detailed look at how
to determine the most important errors. The second section is an example of the corresponding text
that would be written in a lab report for CH141-142. Determining the Important Errors

The purpose of the error analysis section of the lab report is to determine the most important errors
and the effect that those errors have on the final result.

Random Errors: Random errors cause positive and negative deviations from the average value of a
measurement. Random errors cancel by averaging, if the experiment is repeated many times. Upon
averaging many trials, random errors have an effect only on the precision of a measurement. The effect
of random errors is primarily on the precision. Every non-integer experimental measurement is a source
of random error. The random error is estimated from the readability of the device. A table of typical
measurements and the associated precision, under practical circumstances, is given below. For
instrument readings, to avoid round-off error, report one extra significant figure and then underline the
digit that is not significant.
Types of Analysis

Ultimate (Elemental) Analysis

Ultimate analysis gives the elemental composition of a fuel. Its determination is relatively
difficult and expensive compared to proximate analysis. The following ASTM standards are
available for determination of the ultimate analysis of biomass components:

Carbon, hydrogen: E-777 for refuse-derived fuels (RDF)

Nitrogen: E-778 for RDF

Sulfur: E-775 for RDF

Moisture: E-871 for wood fuels

Ash: D-1102 for wood fuels.

Although no standard for other biomass fuels is specified, we can use the RDF standard with a
reasonable degree of confidence. For determination of the carbon, hydrogen, and nitrogen
components of the ultimate analysis of coal, we may use the ASTM standard D-5373-08. Table
13.1 lists standard methods of ultimate analysis for biomass materials.