Statistics and Errors in

Analytical Measurements
 Why do we need statistics in
analytical chemistry?
• Scientists need a standard format to
communicate significance of experimental
numerical data.
• Objective mathematical data analysis
methods needed to get the most information
from finite data sets
• To provide a basis for optimal experimental
design.
 What Does Statistics Involve?
• Defining properties of probability
distributions for infinite populations
• Application of these properties to
treatment of finite (real-world) data sets
• Probabilistic approaches to:
– Reporting data
– Data treatment
– Finite sampling
– Experimental design
 Some Useful Statistics Terms
• Mean – Average of a set of values
• Median – Mid-point of a set of values.
• Population – A collection of an infinite munber of
measurements. N  infinity
• Sample – A finite set of measurements which
represent the population (n)
• True value (true mean)- (m), mean value for the
population.
• Observed Mean –(x), mean value of the sample set
 Accuracy and Precision:
Is There a Difference?
• Accuracy: degree of agreement between
measured value and the true value.
• Absolute true value is seldom known
• Realistic Definition: degree of agreement
between measured value and accepted true
value.
 Precision
• Precision: degree of agreement between
replicate measurements of same quantity.
• Repeatability of a result
• Standard Deviation
• Coefficient of Variation
• Range of Data
• Confidence Interval about Mean Value
 You can’t have accuracy without good precision.
But a precise result can have a determinate or systematic error.

Fig. 3.1. Accuracy and precision.

©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

 ERRORS

- Two classes of experimental errors: systematic and random

Systematic Error
- Also called determinate error
- Repeatable in a series of measurements
- Can be detected and corrected

Examples
uncalibrated buret, pipet, analytical balance, pH meter
power fluctuations, temperature variations
 ERRORS
- Two classes of experimental errors: systematic and random

Randon Error
- Also called indeterminate error
- Always present and cannot be corrected

Examples
Taking readings from an instrument, reading between
markings (interpolation), electrical noise in instruments
 ERRORS

Precision
- Provides information on how closely individual
measurements agree with one another
(measure of reproducibility of a result)

Accuracy
- Refers to how closely individual measurements
agree with the true value (correct value)
(systematic errors reduce the accuracy of a measurement)

- Precise measurements may NOT be accurate

- Our goal is to be accurate and precise

 ERRORS

Absolute Uncertainty
- The margin of uncertainty associated with a measurement

- If estimated uncertainty in a buret reading is ± 0.05 mL

then absolute uncertainty = ± 0.05 mL

- If estimated uncertainty in an analytical balance is ± 0.0001 g

then absolute uncertainty = ± 0.0001g
 ERRORS

Relative Uncertainty
- Compares absolute uncertainty with its associated measurement
- Dimensionless

Absolute Uncertaint y
Relative Uncertaint y 
Magnitude of Measuremen t

Percent Relative Uncertainty = Relative Uncertainty x 100

 ERRORS

For a buret reading of 41.45 ± 0.05 mL

Absolute uncertainty = ± 0.05 mL

0.05 mL
Relative Uncertaint y   0.001
41.45 mL

Percent Relative Uncertainty = 0.001 x 100 = 0.1 %