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ERRORS IN CHEMICAL
ANALYSES

Error
• Chemical analyses will always have errors or
uncertainties
• Minimize the errors or uncertainty, and estimate
their size

 Causes:  How to Resolve?

Faulty calibrations
Faulty standardizations
Random variations
Uncertainties
Mistakes of the experimenter
Frequent calibration
Frequent standardizations
Analyses of known samples

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Error: meaning

 Difference between a measured value and the “true” or

“acceptable” value

 May denote the estimated uncertainty in a

measurement or experiment

Measurements and Errors

 Measurement data: estimate of the “true” value

 Every measurement is influenced by many uncertainties,
which combine to produce a scatter of results.

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Replicate Analysis
 To improve the reliability
 To obtain information about the variability of results

Mean and Median

 Mean: arithmetic mean or average

divide the sum of replicate measurements by the
number of measurements
𝑁
1
𝑥= 𝑥𝑖
𝑁
𝑖=1

 Median: middle value in a set of data that is arranged in

numerical order
Outlier: value that differs significantly from the others in the
data set
- Significantly affects the mean but not the median

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Precision

 agreement among several results obtained in the same

way

 reproducibility of measurements

 determined by repeat measurements on replicate

samples

Precision

 Measures of precision of a set of measurements:

standard deviation
variance
coefficient of variation

 deviation from mean: how much xi, the individual result,

deviates from the mean,

𝒅𝒊 = 𝒙𝒊 − 𝒙

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Accuracy
 closeness of the measurement to the true or accepted
value
 measures agreement between a result and the
accepted value

 Measures of Accuracy:
absolute error
relative error

Absolute Error
 difference between the measured value, xi, and the true
value, xt
𝑬𝒂 = 𝒙𝒊 − 𝒙𝒕

Relative Error
 the absolute error divided by the true value, expressed
in percent (%), parts per thousand (ppt), or parts per
million (ppm), depending on the magnitude of the result

𝒙𝒊 − 𝒙𝒕
𝑬𝒓 = × 𝟏𝟎𝟎
𝒙𝒕

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Types of Error in Experimental Data

 Systematic (determinate): causes the mean a data set

to differ from the accepted value

 Random (indeterminate): causes data to be scattered

more or less symmetrically around a mean value

 Gross error: usually a product of ‘human error’; leads to

outliers

Systematic or determinate errors

 have a definite value, an assignable cause, and are of

the same magnitude for replicate measurements
 lead to bias in measurement results

Types of Systematic Errors

instrumental
method
personal

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Instrumental Error

 Unreliable value from a measuring device

 usually detectable and correctable

 Causes: non-ideal instrument behavior

faulty calibrations
use of instrument under inappropriate
conditions
 How to resolve?
Calibration

Method Error
 Cause: non-ideal chemical or physical behavior of the
reagents and reactions on which an analysis is based
example of non-ideality:
slowness of reactions,
incomplete reactions
non-specific reagents
side reactions
instability of some species

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Method Error

 Difficult to detect, identify, and correct

 How to resolve?
 Method assessment and/or modification

Personal Error
 Cause: experimenter’s carelessness, inattention,
prejudice or bias, and personal limitations

 Measurements often require judgments.

Judgments that are subject to systematic,
unidirectional errors.

 How to resolve?
Awareness

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Effect of Systematic Errors on Analytical

Results

Constant
the magnitude of the error stays the same even as
the size of the quantity measured is varied
the absolute error is constant with sample size, but the
relative error varies when the sample size is changed
 How to resolve?
Increase the sample size until the error is
acceptable

Effect of Systematic Errors on Analytical

Results

Proportional
the magnitude of the error increases as sample size
increases
Cause: presence of interfering contaminants in the
sample
Cannot be fixed by adjusting the sample size

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Detection and Elimination of

Systematic Errors

Instrumental and Personal Errors

 Periodic calibration of the instruments
 Careful, disciplined lab work
 Systematic checking of instrument readings, data
recordings, and calculations
 Choice of analytical method: use of automated
procedure

Detection and Elimination of

Systematic Errors

Method Errors
 Analysis of Standard Reference Materials (SRMs)
 Independent analysis: a second independent and
reliable analytical method can be used in parallel
 Blank determination
 Variation in sample size

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Reference
Skoog, D.A., et.al. (2004) Fundamentals of Analytical Chemistry, 8th ed.
Brooks/Cole, Cengage Learning. USA

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