CHEM 251

Analytical Chemistry for Biologists

Chapter 5
Errors in Chemical Analyses
 Errors in Chemical Analyses
• The term error has two slightly different
meaning.
1. The difference between a measured value and
the ‘true’ or ‘known’ value.
2. The es:mated uncertainity in a measurement or
experiment.
 Errors in Chemical Analyses
• More commonly, errors caused by;
– Faulty calibration or standardization
– Random variations and uncertainties

• Errors caused by calibration or standardization can be

eliminated to some extent but it is hard to eliminate random
errors and uncertainties.

• It is hard to perform a chemical analysis that is totally free of

errors and uncertanties.

• It can be only minimized and estimated with acceptable

accuracy.
 Errors in Chemical Analyses
• Six equal por=ons of an aqueous solu=on with
a known concentra=on of 20.00 ppm of iron
(III) were analyzed.
– The results range from 19.4 ppm to 20.3 ppm with
a mean value, x̅, of 19.8 ppm.
Because measurement uncertainities can
never be completely eliminated,
measurement
data can only give us an estimate of the
‘true’ value.
 Some Important Terms
• In order to improve the reliability and to
obtain information about the variability of
results, two to five portions (replicates) of a
sample are usually carried through an entire
analytical procedure.
• Replicates are samples of about the same size
that are carried through an analysis in exactly
the same way.
 Some Important Terms
Mean, arithmetic mean, and average (x) are
synonyms for the quantity obtained by dividing the
sum of replicate measurements by the number of
measurements in the set.
N

åx
i =1
i

x =
N
where, xi represents the individual values of x making
up a set of N replicate measurements.
 Some Important Terms
The median is the middle result when replicate
data are arranged in increasing of decreasing
order.

Equal number of results are larger and smaller

than the median.
For an odd number of data points, the median
can be evaluated directly.
For an even number, the mean of the middle
pair is used.
 Some Important Terms
• The median is used when a set of data contain
an outlier.
• An outlier can have a significant effect on the
mean of the set but has no on the median.
 Accuracy and Precision
• Accuracy and precision are two important
factors to consider when taking data
measurements.
• Both accuracy and precision reflect how close
a measurement is to an actual value, but
accuracy reflects how close a measurement is
to a known or accepted value, while precision
reflects how reproducible measurements are,
even if they are far from the accepted value.
 Precision
• Precision; how consistent/close a series of values
are with each other.
• In other words; it describes the reproducibility of
measurements-the closeness of results that have
been obtained in exactly the same way.

• Precision of a measurement is determined by

simply repeating the measurement on replicate
samples.
• Precision is how repeatable a measurement is.
 Precision
Three terms are widely used to describe the
precision of a set of replicate data:

1. standard deviation
2. variance
3. coefficient of variation
 Precision
• All these terms are functions of how much an
individual results xi differs from the mean,
called the deviation from the mean di.

di = | xi – x |
 Accuracy
• Accuracy is the closeness of a measurement
to the true or accepted value (i.e., mostly
what we are seeking in the analysis) and is
expressed by the error.
• Accuracy measures agreement between a
result and the accepted value.
 Accuracy
• Accuracy is more difficult to determine since
the true value is usually unknown. So an
accepted value must be used instead.
 Accuracy
• Accuracy is expressed in terms of either
absolute or relative error.
• The absolute error of a measurement is the
difference between the measured value and
the true value.
E = xi – x t
• The absolute error E in the measurement of a
quantity xi is given by the equation, where, xt
is the true or accepted value of the quantity.
 Accuracy
• The negative sign indicates that the
experimental result is smaller than the
accepted value and the positive sign indicates
that the result is larger than the accepted
value.
Illustration of accuracy and precision
 Relative Error
• Rela%ve error (Er) of a measurement is the
absolute error divided by the true value.

• The percent rela%ve error is given by the

expression,
xi - xt
Er = ´ 100%
xt
• Rela%ve error also expressed in parts per
thousand (ppt).
 Analyst 1: High precision and high accuracy
Analyst 2: Poor precision and good accuracy
Analyst 3: High precision and poor accuracy
Analyst 4: Poor precision and poor accuracy

Absolute error in nitrogen determination

 Errors
Chemical analyses are affected by at least two types
of errors.
1) Random (indeterminate) Error; cause data to be
scaCered more or less symmetrically around a
mean value. Random error affects measurement
precision.
2) Systema4c (determinate) Error; cause the mean
of a data set to differ from the accepted value.
Systema%c error affects the accuracy of results.
Gross Errors
They usually occur only occasionally, are often
large, and may cause a result to be either high or
low. Gross error leads to outliers. This error
causes the result differs significantly from the rest
of the results.
Gross errors lead to outliers, results that appear
to differ markedly from all other data in a set of
replicate measurements.
 Systematic Errors
Ø Systema(c errors have a definite value, an assignable
cause, and are of the same magnitude for replicate
measurements made in the same way.

Ø They lead to bias in measurement results.

Ø Bias measures the systema(c error associated with an

analysis. It has a nega(ve sign if it causes the result to
be low and a posi(ve sign otherwise.
Bias has a definite value, an assignable cause and are
about the same magnitude for replicate measurements.
Bias affects all the data in a set in the same way.
 Types of Systematic Errors
There are three types of systematic errors:
1. Instrumental errors are caused by the
imperfections in measuring devices and
instabilities in their components. (ex: faulty
calibration, use under inappropriate conditions)
2. Method errors arise from non-ideal chemical
or physical behavior of analytical systems.
 Types of Systematic Errors
3.Personal errors results from the carelessness,
inaQen=on, or personal limita=ons of the
experimenter.
 Instrumental Errors
• Voltage decrease
• Incorrect calibration
• Temperature change-electronic components
• Noise induced from AC power lines
 Method Errors
• Nonideal chemical or physical behavior of the
reagents and reac=ons
– Slow or incomplete reac:on, instability of some
species, lack of specificity, side reac:ons
 Personal Errors
• Personal judgments
– Estimating the scale position
– Color of solution
– Level of liquid
 Effects of Systematic Errors

i) Constant Errors: Constant Errors does not

depend on the size of the quan=ty measured

ii) ProporConal Errors: Propor=onal errors

decrease or increase in propor=on to the size
of the sample taken for analysis. A common
cause of propor=onal errors is the presence of
interfering contaminants in the sample.
 Detecting Systematic Errors
Systematic instrument errors are usually
corrected by calibration. Periodic calibration
of equipment is always desirable.
Personal errors can be minimized by care and
self-discipline. Errors that result from a known
physical disability can usually be avoided by
carefully choosing the method.
Method errors or bias of an analytical method
is estimated by analyzing standard reference
materials.
 The Effect of Systematic Errors on
Analytical Results
• Constant
– The magnitude of constant error stays same as the
size of the quan5ty measured is varied.
– The absolute error varies when the sample size is
changed.
• Propor%onal
– The magnitude increase or decrease according to the
size of the sample
– The absolute error varies with sample size but the
rela5ve error stays constant when the sample size is
changed.
 Detection of Systematic Instrument
and Personal Errors
• Calibration
– Component aging, corrosion, or mistreatment
• Careful, disciplined laboratory work
– Check intrument readings, notebook entiries and
calculations
Detection of Systematic Method Errors
• Analysis of standard samples
– Cer5fied and specified concentra5ons of one or more
analytes
• Independent analysis
– A second indipendent and reliable analy5cal method
can be used
• Blank determina%ons
– All the steps of the analysis performed on the blank
material
• Varia%on in sample size