Errors in Chemical Analysis

Analytical Chemistry-I
CHEM-511
BS 3rd Year Semester V, 2021
Dr. Sana Mustafa

Department of Chemistry, Federal Urdu University of Arts,
Science& Technology, Karachi.
Errors in Chemical Analysis & Sampling
 Analytical Chemistry
 Qualitative Analysis → Does this distilled water sample contain any Boron?
 Quantitative Analysis→ How much lead in the sample of tap water?
 The total chemical analysis involves several steps

Sampling-→ sample preservation(field prtreatment)-→ sample prepration)-→
Chemical Analysis--→ Data treatment --→ Result communication
 Quantitative analysis play a dominant role in analytical lab.

 Example: I can/canot detect boron in this water sample, but quantitative test
gives a sample contain 1 ug/mL boron.
Precision:
 It is impossible to perform a chemical analysis in such a way that the results

are totally free of errors or uncertainties.
 Precision describes the reproducibility of measurements, or the closeness of

the results that have been obtained in exactly the same way.-
 Three terms are widely used to describe the precision of a set of replicate
data-Standard Deviation, Variance, and Coefficient of Variation-
 All above terms are a function of the deviation from the mean
dI = | xi – x |
Accuracy:
 Accuracy indicates the closeness of the measurement to its true or

accepted value and is expressed by the error.
 Note that the basic difference between accuracy and precision is that
accuracy measures agreement between a result and its true value, while
precision describes the agreement among several results that have been
obtained in the same way.
 Accuracy is expressed in terms of either absolute or relative error.
There is a certain amount of error in each step of chemical
analysis .
No quantitative results are of any value unless they signify

that how much errors they have
 Types of Errors:
 Gross Error
 Random Error (Indeterminate Error)
 Systematic Error (Determinate Error)
Gross Error
 Errors w/h are so serious that there is no real alternative to abandoning the
experiment & making a completely fresh start.
 Gross error usually only occur occasionally, are often large, and may cause
a result to be either high or low-Lead to outliers, results that appear to differ
markedly from all other data
 Example:
 accidently dropping or discarding a crucial sample,
 complete instrumental breakdown,
 Discovering during exp. That supposedly pure reagent was in fact badly
contaminated.
Random Error(Indeterminate Error)
 These errors are also called accidental errors.

 Indeterminate errors arise from uncertainties in a measurement that are
unknown and which cannot be controlled by the experimentalist.
 For example: When pipetting out a liquid, the speed of draining, the angle
of holding the pipette, the portion at which the pipette is held, etc, would
introduce indeterminate error in the volume of the liquid pipette out.
Systematic Error (Determinate Error)
 Systematic errors are usually found and corrected by calibration-Most

personal errors can be minimized by care and self-discipline.
 These errors are determinable and are avoided if care is taken.

 Determinate errors are classified into three types.
 Instrumental error
 Operative error
 Methodic errors
Instrumental Error
 Instrumental errors are introduced due to the use of defective instruments.

 For example an error in volumetric analysis will be introduced, when a 20ml
pipette, which actually measures 20.1ml, is used.
 Sometimes an instrument error may arise from the environmental factors on
the instrument.
 For example a pipette calibrated at 20°C, if used at 30°C will introduce error
in volume.
 Instrumental errors may largely be eliminated by periodically calibrating
the instruments.
Personal/Operative Error
 These errors are also called personal errors and are introduced because of
variation of personal judgements.
 For example due to colour blindness a person may arrive at wrong results in
a volumetric or colorimetric analysis.
 Using incorrect mathematical equations and committing arithmetic
mistakes will also cause operative errors.
Methodic Error
 These errors are caused by adopting defective experimental methods.

 For example in volumetric analysis the use of an improper indicator leading
to wrong results is an example for methodic error.
 Proper understanding of the theoretical background of the experiments is a
necessity for avoiding methodic errors.
 Mean, arithmetic mean, and average are synonyms for the quantity.
 A mean value is obtained by dividing the sum of a set of replicate
measurements by the number of individual results in the set.
Example: Calculate the mean and the median for this set of data
[(19.4) , (19.6) , (19.5) , (19.8) , (20.1) , (20.3)]
mean = ( ) = 19.786
median = ( ) = 19.7
 For example, if a titration is repeated four times and the titre values are 10.1,
9.9, 10.0 and 10.2ml
 This mean value is also called arithmetic mean or average.

 The median is the middle result when replicated data are arranged in order
of size

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What are the different types of errors in chemical analysis?

What is the difference between accuracy and precision in chemical analysis?

Analytical Chemistry-I

BS 3rd Year Semester V, 2021

Dr. Sana Mustafa

 The total chemical analysis involves several steps

 Quantitative analysis play a dominant role in analytical lab.

 It is impossible to perform a chemical analysis in such a way that the results

 Precision describes the reproducibility of measurements, or the closeness of

 Accuracy indicates the closeness of the measurement to its true or

No quantitative results are of any value unless they signify

 These errors are also called accidental errors.

 Systematic errors are usually found and corrected by calibration-Most

 These errors are determinable and are avoided if care is taken.

 Instrumental errors are introduced due to the use of defective instruments.

 These errors are caused by adopting defective experimental methods.

 This mean value is also called arithmetic mean or average.

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