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Errors in

Chemical
Analysis
CHAP 5
Data quality
Measurements invariably involve errors and
uncertainties.
Uncertainties can never be completely eliminated,
measurement data can give us only an estimate of
the true value.
Reliability can be assessed in several ways:
Experiments designed to reveal the presence of
errors
Compared with the known compositions
Consult to the chemical literature
Equipment Calibration
Statistical tests
Representative Data
Chemists usually carry two to five portions
(replicates) of a sample through an entire
analytical procedure.
Replicates are samples of about the same size that
are carried through an analysis in exactly the same way.
One usually considers the best estimate to be
the central value for the set:
Usually, the mean or the median is used as the
central value for a set of replicate measurements.
The variation in data allows us to estimate the
uncertainty associated with the central result
The Mean and Median
The most widely used measure of central value
is the mean, . The mean, also called the
arithmetic mean, or the average,

where xi represents the individual values of x
making
up the set of N replicate measurements.
The median is the middle result when
replicate
data are arranged according to increasing or
decreasing value.
Example for Mean & Median

Precision
Describes the reproducibility of
measurements
Or, the closeness of results that have been
obtained in exactly the same way.
Three terms are widely used to describe the
precision of a set of replicate data:
standard deviation;
variance;
coefficient of variation.
Deviation from the mean:
Accuracy
Indicates the closeness of the measurement to
the true or accepted value
Expressed in terms of either absolute or relative
error.
Absolute error:
where xt is the true or accepted value of the
quantity
We retain the sign in stating the absolute error.
Relative error:
The difference between accuracy and
precision
Types of Errors in Experimental Data
The precision of a measurement is
readily determined by comparing data
from carefully replicated experiments.
To determine the accuracy, we have
to know the true value, which is
usually what we are seeking in the
analysis.
Analyst 1: relatively high precision & high accuracy
Analyst 2: poor precision but good accuracy
Analyst 3: excellent precision & significant error in the
numerical average for the data
Analyst 4: poor precision & poor accuracy
Types of Errors
Random (or indeterminate) error:
Affect measurement precision
Causes data to be scattered more or less
symmetrically around a mean value.
Analysts 1 and 3 is significantly less than that for
analysts 2 and 4.
Systematic (or determinate) error:
Affect the accuracy of results
Causes the mean of a data set to differ from the
accepted value.
Analysts 1 and 2 have little systematic error;
Analysts 3 and 4 show systematic errors of about -
0.7% and -1.2%.
Gross error:
Often the product of human errors.
usually occur only occasionally, are
often large, and may cause a result to
be either high or low.
lead to outliers, results that appear to
differ markedly from all other data in a
set of replicate measurements.
Systematic Errors
Lead to bias in measurement results
Bias affects all of the data in a set in the same
way and that bears a sign
Three types:
Instrumental errors are caused by nonideal
instrument behavior, by faulty calibrations, or by
use under inappropriate conditions.
Method errors arise from nonideal chemical or
physical behavior of analytical systems.
Personal errors result from the carelessness,
inattention, or personal limitations of the
experimenter.
Instrument Errors
All measuring devices are potential
sources of systematic errors.
Calibration eliminates most
instrumental systematic errors.
Electronic instruments are subject to
instrumental systematic errors.
Ex: low battery voltage, noises
In many cases, errors of these types
are detectable and correctable.
Method Errors
The nonideal chemical or physical behavior of
the reagents and reactions on which an analysis
is based
Ex: the slowness of some reactions, the
incompleteness of others, the instability of
some
species
Errors inherent in a method are often difficult
to
detect and are thus the most serious of the
three
types of systematic error.
Personal Errors
Many measurements require personal
judgments. Judgments of this type are often
subject to systematic, undirectional errors.
Analytical procedures should always be
adjusted
so that any known physical limitations of the
analyst cause negligibly small errors.
A universal source of personal error is prejudice,
or bias. Number bias is another source of
personal error that varies considerably from
person to person.
Effect of Systematic Errors on
Analytical Results
Systematic errors may be either constant or
proportional.
Constant errors
Independent of the size of the sample being
analyzed.
The absolute error is constant with sample size,
but
the relative error varies when sample size is
changed.
The excess of reagent required to bring about a
color
change during a titration is an example.
The effect of a constant error becomes more
serious
as the size of the quantity measured decreases.
Proportional errors
- Decrease or increase in proportion to the
size
of the sample.
The absolute error varies with sample
size,
but the relative error stays constant with
changing sample size.
A common cause of proportional errors is
the
presence of interfering contaminants in the
sample
Systematic Instrument and
Personal Errors Detection
Instrument errors
Some systematic instrument errors can be found and
corrected by calibration.
Periodic calibration of equipment is always desirable
because the response of most instruments change with
time as a result of wear, corrosion, or mistreatment.
Personal errors
Most personal errors can be minimized by care and
self-discipline.
It is a good habit to check instrument readings,
notebook entries, and calculations systematically.
Systematic Method Errors Detection
Take one or more of the following
steps to recognise and adjust for a
systematic error:
Analysis of Standard Samples
Independent Analysis
Blank Determinations
Variation in Sample Size
Analysis of Standard Samples
The best way of estimating the bias of an
analytical method is by the analysis of standard
reference materials.
Standard Reference Materials (SRMS):
Materials that contain one or more analytes at
known concentration levels.
Can sometimes be prepared by synthesis.
Can be purchased from a number of
governmental and industrial sources. Ex:
National Institute of Standards and Technology
(NIST); Sigma Cheminal Co.
Independent Analysis & Variation in
Sample Size
Independent Analysis
A second independent and reliable analytical method
can be used in parallel with the method being
evaluated.
A statistical test must be used to determine whether
any difference is a result of random errors in the two
methods or due to bias in the method under study.
Variation in Sample Size
As the size of a measurement increases, the effect of
a constant error decreases. Constant errors can often
be detected by varying the sample size.
Blank Determinations
A blank contains the reagents and solvents used in
a determination, but no analyte.
Many of the sample constituents are added to
simulate the analyte environment, often called the
sample matrix.
In a blank determination:
All steps of the analysis are performed on the blank
material.
Blank determinations reveal errors due to
interfering
contaminants from the reagents and vessels used in
the analysis