Errors, Random Errors, and

Statistical Data in Chemical

Analysis
Errors, Random Errors, and
Statistical Data in Chemical Analysis
• Impossible: The analytical results are free
of errors or uncertainties.
• Possible: Minimize these errors and
estimate their size with acceptable
accuracy.
• Statistical calculations for use to judge the
quality of experimental measurements are
many.
Errors, Random Errors, and
Statistical Data in Chemical Analysis
• Measurements are always accompanied
by uncertainty. The true value always falls
within a range due to uncertainty.
• The probable magnitude of the error
defines the limit within which the true value
lies.
• Data of unknown quality are worthless.
• The true value of a measurement is never
known exactly.
Reliability Can Be Assessed
In Several Ways
• Standards of known composition can be
analyzed and the results compared with the
known composition.
• Calibrating equipment enhances the
quality of data.
 Content
02
MEASURES OF DISPERSION

04
TYPES OF ERRORS

01
03
MEASURES OF CENTRAL TENDENCY
ACCURACY AND PRECISION
 01

MEASURES OF CENTRAL TENDENCY

 MEAN
 MEDIAN
 MODE

Measures of Central Tendency- is a quantity that

describes the location of the center of a set of data.
The Mean, Median, and Mode
Mean, arithmetic mean, and average
(x) are synonyms.

where xi represents the individual values of x

making up a set of N replicate measurements.
The symbol means to add all the values
xi for the replicates.

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The Mean, Median, and Mode

• The median is the middle result when

replicate data are arranged in order of
size.
• Equal numbers 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.

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The Mean, Median, and Mode

• The mean of two or more measurements

is their average value.
• The median is used advantageously when
a set of data contains an outlier, a result
that differs significantly from others in the
set.

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Example

• Calculate the mean and the median for the

data: 19.4, 19.5, 20.1, 20.3, 19.8.

Because the set contains an even number

of measurements, the median is the
average of the central pair:

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The Mean, Median, and Mode

• The most frequently appearing value in the

set of data.

• Example:
• Data Set A: 1,3,6,6,6,6,7,7,12,12,17
– Mode= 6

• Data Set B: 1,2,2,3,4,7,9

• Mode= 2
–
Try this!
Find the mean, median and mode of the data below:

Masses of Seven Objects Measured using the Analytical

Balance:
Object Mass (g)
1 3.080 g
2 3.094 g
3 3.107 g
4 3.056 g
5 3.112 g
6 3.174 g
7 3.198 g
 02

MEASURES OF DISPERSION
 RANGE
 STANDARD DEVIATION
 VARIANCE

Measures of Dispersion
Is a quantity that describes how widely dispersed or
spread the data are in a given data set.
Range (w)
Is the difference between the largest and smallest
values in the data set.
Example:

Standard Deviation (s)

Describes the spread of individual measurements about the mean.

WHERE:
 Relative Standard Deviation (Sr)

Percent Relative Standard Deviation (Sr)

Variance (s2)
The square of the standard
deviation.
Try this!
Find the range, standard deviation, relative standard
deviation, percent standard deviation, and variance of
the data below:

Masses of Seven Objects Measured using the

Analytical Balance:
Object Mass (g)
1 3.080 g
2 3.094 g
3 3.107 g
4 3.056 g
5 3.112 g
6 3.174 g
7 3.198 g
TRY THIS!
Calculate the:
A. mean
B. median
C. mode
D. standard deviation
E. variance
F. percent standard deviation
G. relative standard deviation
H. range of the following group of sodium values.

144 IU/L; 145 IU/L; 143 IU/L; 139 IU/L; 147 IU/L; 140
IU/L; 144 IU/L; 142 IU/L; 145 IU/L; 147 IU/L
 03
ACCURACY AND PRECISION

 ACCURACY
 PRECISION
 TYPES OF ERRORS
 ACCURACY
The closeness of the measurement to the TRUE OR ACCEPTED
VALUE (µ).
Usually expressed as either an absolute error or relative error.

Absolute Error (e)- the difference between the experimental result

(x) and the true value (µ).

Relative Error (er)- is calculated by finding the difference between the

true value and measured values and dividing this difference by the true
answer. It can be expressed as either a fraction or relative value, such
as by using a percent or parts per million (ppm).
Example:
If you used a balance to measure a sample with a known
mass of 10.000g and the balance gave a reading of 9.9995g,
the absolute and relative error would be?

Absolute Error

Relative Error
 PRECISION
Is a measure of the spread of data about a central value and may
be expressed as the range, the standard deviation, or the variance.
It is commonly divided into 2 categories: repeatability and
reproducibility.

Repeatability- is the precision obtained when all measurements are

made by the same analyst during a single period of laboratory work,
using the same solutions and equipment.

Reproducibility- is the precision obtained under any other set of

conditions, including that between analyst, or between laboratory
sessions for a single analyst.
Classifying Experimental Errors

• To determine accuracy, we have to know

the true value, and this value is exactly
what we are seeking in the analysis.
• Do we know the answer precisely, also
know it accurately?

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 04

TYPES OF ERRORS

 SYSTEMATIC/DETERMINATE

 RANDOM ERRORS/INDETERMINATE

 GROSS ERRORS/ BLUNDERS

Classifying Experimental Errors

• Chemical analysis are affected by at least

two types of errors.
• One type, called random (or indeterminate)
error, causes data to be scattered more or
less symmetrically around a mean value.
• A second type of error, called systematic (or
determinate) error, causes the mean of a set
of data to differ from the accepted value.
Classifying Experimental Errors

• A third type of error is gross error. Gross

errors differ from indeterminate and
determinate errors. They usually occur
only occasionally, are often large, and may
cause a result to be either high or low.
• Gross errors lead to outliers, results that
appear to differ markedly from all other
data in a set of replicate measurements.
• Various statistical tests can be done to
determine if a data point is an outlier.
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Classifying Experimental Errors

Systematic or Determinate Errors- affect accuracy. Any systematic

error that causes a measurement or result to always be too high or
too small; can be traced to an identifiable source.

SAMPLING METHOD MEASUREMENT PERSONAL

ERRORS ERRORS ERRORS ERRORS
SYSTEMATIC ERRORS

• Systematic errors have a definite value, an

assignable cause, and are of about the
same magnitude for replicate
measurements made in the same way.
• Systematic errors lead to bias in
measurement technique. Note that bias
affects all the data in a set in
approximately the same way and that it
bears a sign.

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How do Systematic Errors Arise?

• Instrument Errors
– All measuring devices are sources of systematic
errors: pipets, burets, and volumetric flasks.
– These differences arise from using glassware at a
temperature that differs significantly from the
calibration temperature, from distortions in container
walls due to heating while drying, from errors in the
original calibration, or from contaminants or scratches
on the inner surfaces of the containers.
– Instrument Errors are detectable and correctable.

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How do Systematic Errors Arise?

• Method Errors
– The nonideal chemical or physical behavior of the
reagents and reactions upon which an analysis is
based often introduce systematic method errors.
– Such sources of nonideality include the slowness and
incompleteness of reactions, the instability of species,
non-specificity of most reagents, and possible
interference.
– Errors inherent in a method are often difficult to detect
and are thus the most serious of the three types of
systematic error.

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How do Systematic Errors Arise?

• Personal Errors
– Measurements requiring personal judgments.
– Judgments of this type are often subject to
systematic, unidirectional errors.
– An analyst who is insensitive to color changes tends
to use excess reagent in a volumetric analysis.
Physical disabilities are often sources of personal
determinate errors.
– A universal source of personal error is prejudice.

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How do Systematic Errors Arise?
• Personal Errors
– Number bias is another source of personal error that
varies considerably from person to person.
– The most common number bias encountered in
estimating the position of a needle on a scale involves
a preference for the digits 0 and 5. Also prevalent is a
prejudice favoring small digits over large and even
numbers over odd.
– Color blindness amplifies personal errors in a
volumetric analysis.

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What Effects Do Systematic
Errors Have on Analytical Results?
• Systematic errors may be either constant
or proportional.
• The magnitude of a constant error does
not depend on the size of the quantity
measured.
• Proportional errors increase or decrease in
proportion to the size of the sample taken
for analysis.

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Detecting Systematic
Instrument and Personal Errors
• Systematic instrument errors are usually
corrected by periodic calibration of
equipment. The response of most
instruments changes with time.
• Most personal errors can be minimized by
care and self-discipline.

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Detecting Systematic
Method Errors
• Analyzing Standard Samples
– Analyzing standard reference materials, SRM, is the
best way to estimate the bias of an analytical method.
– The SRM Materials contain one or more analytes at
well-known or certified concentration levels.
– Standard materials can sometimes be prepared by
synthesis.
– Standard reference material can be purchased from a
number of governmental and industrial sources.

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Detecting Systematic
Method Errors
• Analyzing Standard Samples
– The concentration of one or more of the
components in these materials has been
determined in one of three ways:
• (1) by analysis with a previously validated
reference method;
• (2) by analysis by two or more independent,
reliable measurement methods; or
• (3) by analysis by a network of cooperating
laboratories that are technically competent and
thoroughly knowledgeable with the material being
tested.
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Detecting Systematic
Method Errors

Standard reference
materials from NIST.
(Photo courtesy of the
National Institute of
Standards and
Technology.)

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Detecting Systematic
Method Errors
• Using an Independent Analytical
Method
– If standard samples are not available, 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.
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Detecting Systematic
Method Errors
• Performing Blank Determinations
– Blank determinations are useful for detecting
certain types of constant errors.
– In a blank determination, or blank, all steps of
the analysis are performed in the absence of
a sample.
– The results from the blank are then applied as
a correction to the sample measurements.
– Blank determinations reveal errors and
correct data

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Detecting Systematic
Method Errors

• Varying the Sample Size

– Constant errors can often be detected by
varying the sample size

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The Nature of Random Errors

• All measurements contain random

errors.
– Random, or indeterminate, errors occur
whenever a measurement is made.
– Caused by many small but uncontrollable
variables.
– The errors are accumulative.

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What Are the Sources of
Random Errors?

• Imagine a situation in which just four small

random errors combine to give an overall
error.
• We will assume that each error has an
equal probability of occurring and that
each can cause the final result to be high
or low by a fixed amount.

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A histogram (A)
showing distribution
of 50 results and a
Gaussian curve (B)
for data having the
same mean and
same standard
deviation as the data
in the histogram.

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Sources of random uncertainties

• Many small and uncontrollable variables affect

even the simple process of calibrating a pipet.
• The cumulative effect of random uncertainties is
responsible for the scatter of data points around
the mean.
• Statistics only reveal information that is already
present in a data set.
• Do not confuse the statistical sample with the
analytical sample.

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Sources of random uncertainties
• (1) visual judgments, such as the level of
the water with respect to the marking on
the pipet and the mercury level in the
thermometer
• (2) variations in the drainage time and in
the angle of the pipet as it drains
• (3) temperature fluctuations, which affect
the volume of the pipet, the viscosity of the
liquid, and the performance of the balance
• (4) vibrations and drafts that cause small
variations in the balance readings.
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Treating Random Errors with
Statistics
• The random, or indeterminate, errors in the
results of an analysis can be evaluated by
the methods of statistics.
• Ordinarily, statistical analysis of analytical
data is based on the assumption that
random errors follow a Gaussian, or
normal, distribution.

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Characterizing Gaussian Curves

• Areas under a Gaussian Curve

– Regardless of its width, 68.3% of the data
making up the population will lie within the
bounds bracketed by ±1σ.
– Approximately 95.4% of all data points are
within ±2σ of the mean and 99.7% within ±3σ.
– Because of such area relationships, the
standard deviation of a population of data is a
useful predictive tool.

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For μ = 0, x = ±σ

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For μ = 0, x = ±2σ

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For μ = 0, x = ±3σ

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Example:

The following results were obtained in the

replicate determination of the lead content of a
blood sample: 0.752, 0.756, 0.752, 0.751, and
0.760 ppm Pb. Calculate the mean and the
standard deviation of this set of data.

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Example
To apply Equation, we calculate and

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Example

Substituting into Equation leads to

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Reporting Computed Data

• One of the best ways of indicating reliability

is to give a confidence interval at the 90% or
95% confidence level.
• Another method is to report the absolute
standard deviation or the coefficient of
variation of the data.
• A less satisfactory but more common
indicator of the quality of data is the
significant figure convention.
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The Significant Figure Convention

• A simple way of indicating the probable

uncertainty associated with an experimental
measurement is to round the result so that it
contains only significant figures.
• The significant figures in a number are all
the certain digits plus the first uncertain
digit.

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The Significant Figure Convention

• A zero may or may not be significant

depending on its location in a number.
• A zero that is surrounded by other digits is
always significant (such as in 30.24 mL).
• Zeros that only locate the decimal point for
us are not.

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Rounding Data

• A good guide to follow when rounding a 5

is always to round to the nearest even
number. For example, 0.635 rounds to
0.64 and 0.625 rounds to 0.62.
• We should note that it is seldom justifiable
to keep more than one significant figure in
the standard deviation because the
standard deviation contains error as well.

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 THE END
Prepare for a quiz.