ERROR IN
CHEMICAL
ANALYSIS
EXPERIME
NTAL
ERROR Every measurement has some uncertainty, which is called
experimental error.
Conclusions can be expressed with a high or a low degree of
confidence, but never with complete certainty.
Experimental error is classified as either systematic or
random.
CLASSIFICATIONS OF
SYSTEMATIC ERROR RAMDOM ERROR
(DETERMINATE ERROR) (INDETERMINATE ERROR)
effects of uncontrolled (and
maybe uncontrollable) variables
flaw of equipment
in the measurement
design of experiment has an equal chance of being
error is reproducible positive or negative
discoverable and can be from reading instruments
corrected (different reader, different
readings)
electrical noise
SYSTEM
ATIC
ERROR Incorrect standardization of pH meter
Suppose you think that the pH of the buffer used to
standardize the meter is 7.00, but it is really 7.08.
This systematic error could be discovered by using a
second buffer of known pH to test the meter.
7.00
pH
7.8
Disagreement beyond the
estimated random error is
systematic error.
WAYS
TO Analyse a known sample, such as a Standard Reference Material. Your method
should reproduce the known answer.
DETECT Analyze “blank” samples containing none of the analyte being sought. If you observe
SYSTEM a nonzero result, your method responds to more than you intend
ATIC Use different analytical methods to measure the same quantity. If results do not
ERROR
agree, there is error in one (or more) of the methods.
Round robin experiment: Different people in several laboratories analyze identical
samples by the same or different methods.
SOURCE
S OF
SYSTEM
ATIC
ERROR
The magnitude of a constant error stays essentially the same as
EFFECTS the size of the quantity measured is varied.
OF
SYSTEM With constant errors, the absolute error is constant with sample
size, but the relative error varies when the sample size is
ATIC changed.
ERROR
Proportional errors increase or decrease according to the size
of the sample taken for analysis.
With proportional errors, the absolute error varies with sample
size, but the relative error stays constant when the sample size
is changed.
GROSS
They usually occur only occasionally, are often large,
and may cause a result to be either high or low.
They are often the product of human errors.
Gross errors lead to outliers, results that appear to
differ markedly from all other data in a set of replicate
measurements.
Most personal errors can be minimized by careful, disciplined
laboratory work.
It is a good habit to check instrument readings, notebook
DETECTI entries, and calculations systematically.
ON OF
SYSTEMA Errors due to limitations of the experimenter can usually be
avoided by carefully choosing the analytical method or using
TIC an automated procedure
INSTRUM
ENT AND
ERROR
ACCURACY AND
PRECISION
Precision describes the reproducibility of a result.
If you measure a quantity several times and the
values agree closely with one another, your
measurement is precise. If the values vary widely,
your measurement is not precise.
Accuracy describes how close a measured value is to the “true”
value. If a known standard is available, accuracy is how close your
value is to the known value.
ABSOLUTE AND RELATIVE
ERROR
Absolute error is the difference of the measured Relative error is often a more useful quantity than
valued from the “true value”. the absolute error. The percent relative error is given
by the expression:
ABSOLUTE AND RELATIVE
UNCERTAINTY
Absolute uncertainty expresses the margin
of uncertainty associated with a
measurement.
If the estimated uncertainty in reading a
calibrated buret is ± 0.02 mL we say that ±
0.02 mL is the absolute uncertainty
associated with the reading.
ABSOLUTE AND RELATIVE
UNCERTAINTY
Relative uncertainty compares the size of If the estimated uncertainty in reading a
the absolute uncertainty with the size of calibrated buret is ± 0.02 mL we say that ± 0.02
its associated measurement. mL is the absolute uncertainty associated with
the reading.
PROPAGATION OF
UNCERTAINTY FROM
RANDOM ERROR
uncertainty is expressed as the standard deviation or as a confidence
interval,
ADDITIO
N AND
SUBTRA
CTION
MULTIPLICA
TION AND first convert all uncertainties into percent relative
DIVISION uncertainties.
Then calculate the error of the product or quotient as
follow as a confidence interval,
MIXED
OPERATION
S
1.50 0.02 - 0.43 0.02
______________________
1.2 0.02
