Chapter 2
Errors in Chemical Analysis
Definition of Basic Terms
For a small number of measurements, the sample standard deviation, s, is
expressed mathematically as follows:
Accuracy is a measure of how close a measurement comes to the
actual or true value of whatever is measured (closest to TRUE
Value).
Accuracy measures agreement between a result and its true value.
Precision is a measure of how close a series of measurements are to
one another (repeated Save Value).
Precision is determined by repeating the measurement on replicate
samples.
• Who is more accurate when measuring a book that has a true
length of 17.0 cm?
Person 1:
17.0 cm, 16.0 cm, 18.0 cm, 15.0 cm
Person 2:
15.5 cm, 15.0 cm, 15.2 cm, 15.3 cm
Answer: Set 1
• Which set is more precise?
Set 1: 18.2 , 18.4 , 18.35
Set 2: 17.9 , 18.3 , 18.85
Set 3: 16.8 , 17.2 , 19.44
Answer: Set 1
Deviation from mean
Sample of an Deviation from mean
S.No % of carbon _
organic compound │xi ‒ X │
1 X1 38.42 0.20
2 X2 38.02 0.20
3 X3 38.22 0.00
_
0 . 4 0 = 0.133
X = 38.22
3 (Average
deviation)
Types of Errors
The error is the difference between the
experimental value and the accepted value.
Absolute Error: The term accuracy is the difference
between the observed value and the expected value.
Absolute Error = Experimental Value - Accepted Value
(measured by student) - (correct value)
Determining Error
The experimental value (EV) is the value
measured in the lab. (by the student)
The accepted value (AV) is the correct value
based on reliable references.
Problem
Relative Error
The relative error denotes the percentage of error compared to the
expected value.
Relative Error = Experimental Value - Accepted Value
x 100%
Accepted Value
The Relative error is an absolute value (there is no
positive or negative value.)
Absolute Error and Relative Error
What is the weight of my car?
Experimental Value (EV) = 3585 kg
Actual Value (AV) = 3580 kg
Absolute Error = EV– AV = 3585 kg – 3580 kg = 5 kg
Relative Error = EV - AV x 100%
AV
= 3585 kg – 3580 kg x 100 % = 0.14%
3580 kg
Errors are of two main types
• Determinate errors or Systematic errors
• Indeterminate errors or Random errors
Two sources of errors in a measurement are
• Limitations in the sensitivity of the instruments
• Imperfections in experimental design or measurement techniques
Determinate
errors:
These errors are determinable and are avoided if care is
taken. Determinate errors are classified into three types.
• Instrumental error
• Operative error
• Methodic errors
1. Instrumental errors
These are due to failure to calibrate, degradation of parts in the
instrument, power fluctuations, variation in temperature, etc.
• Instrumental errors are introduced due to the use of defective
instruments.
• For example an error in volumetric analysis will be introduced, when a
20 ml pipette, which actually measures 20.1 ml, 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.
- Can be corrected by calibration or proper instrumentation maintenance.
2. Personal errors
• These errors are also called personal errors and are introduced
because of variation of personal judgments.
• For example due to color blindness a person may arrive at wrong
results in a volumetric or colorimetric analysis.
• Using incorrect mathematical equations and cause committing
arithmetic mistakes will also operative errors.
- Can be minimized or eliminated with proper training and experience
3. Method errors
These errors occur where measurements using improper methods.
• 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.
- Can be corrected with proper method development.
Random (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 Errors
• Are TYPICALLY present.
• Sources:
– Instrumental, physical and human limitations.
• Example: Device is out-of calibration.
• How to minimize them?
– Careful calibration, proper method development and best training.
– Best possible techniques.
Random Errors
• ALWAYS present.
• Sources:
– Operator errors
– Changes in experimental conditions
• How to minimize them?
– Take repeated measurements and calculate their average.
