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ANALYTICAL

CHEMISTRY
(Error in Chemical
Analysis)
Dr.S.SURESH
Assistant Professor
Email:avitsureshindia@gm
ail.com

Mean value
A mean value is obtained by dividing the sum of a set
of replicate measurements by the number of
individual results in the set. For example, if a
titration is repeated four times and the titre values
are 10.1, 9.9, 10.0 and 10.2ml
Mean = 10.1 + 9.9 + 10 + 10.2
4
= 40.2
4
= 10.05
This mean value is also called arithmetic mean or
average.

The median
This is a value about which all other values in
a set are equally distributed. Half of the
values are greater and the other half smaller
numerically, compared to the median.
For example: If we have a set of values like
1.1, 1.2, 1.3, 1.4 and 1.5 the median value is
1.3.
When a set of data has an even number of
values, then the median is the average of the
middle pair.

Accuracy
Accuracy represents the nearness to a
measurement to its expected value. Any
difference between the measured value
and the expected value is expressed as
error.
For example: The dissociation constant
for acetic acid is 1.75105 at 25 C. In
an experiment, if a student arrives at
exactly this value, his value is said to be
accurate.

Precision
Precision is defined as the agreement
between the numerical value of two
or more measurements of the same
object that have been made in an
identical manner. Thus, a value is said
to
be
precise,
when
there
is
agreement between a set of results
for the same quantity.
However a precise value need not be
accurate.

Methods of expressing precision


Precision can be expressed in an
absolute method. In the absolute way
the Xdeviation from the mean xi
expresses
precision
without
Deviation from mean
Sample of an
considering sign% of carbon
S.No
x
_

organic compound

X1

38.42

0.20

X2

38.02

0.20

X3

38.22

0.00

= 38.22

0.40 = 0.133
3 (Average deviation)

Absolute error
The term accuracy is denoted in terms
of absolute error E, E is the difference
between the observed value (X i) and the
expected value (Xt).
E = X i X t
If a student obtains a value of 1.6910 5
for the dissociation constant of acetic
acid at 25C, the absolute error in this
determination is
E = 1.69 105 1.75105
= 0.06 105

Relative error
Sometimes the term relative error is
used to express the uncertainty in data.
The
relative
error
denotes
the
percentage of error compared to the
expected value. For the dissociation
constant value reported.
Relative error = 0.06 105 100
1.75105
= 3.4%

Problem:
The actual length of a field is 500 feet. A measuring
instrument shows the length to be 508 feet. Find:
a.) the absolute error in the measured length of the
field.
b.) the relative error in the measured length of the
field.
Solution:
(a)The absolute error in the length of the field is 8 feet.
E = Xi Xt = 508-500 = 8 feet.
b.) The relative error in the length of the field is

Relative error = 8 100


500
= 1.6%

Errors
Errors are of two main types
Determinate errors
Indeterminate errors
Determinate errors:
These errors are determinable and are
avoided if care is taken. Determinate
errors are classified into three types
Instrumental error
Operative error
Methodic errors

Instrumental error
Instrumental errors are introduced due to
the use of defective instruments.
For example an error in volumetric analysis
will be introduced, when a 20ml pipette,
which actually measures 20.1ml, is used.
Sometimes an instrument error may arise
from the environmental factors on the
instrument.
For example a pipette calibrated at 20C, if
used at 30C will introduce error in volume.
Instrumental
errors
may
largely
be
eliminated by periodically calibrating the
instruments.

Operative errors
These errors are also called personal
errors and are introduced because of
variation of personal judgements.
For example due to colour blindness a
person may arrive at wrong results in
a volumetric or colorimetric analysis.
Using
incorrect
mathematical
equations and committing arithmetic
mistakes will also cause operative
errors.

Methodic errors
These errors are caused by adopting
defective experimental methods.
For example in volumetric analysis
the use of an improper indicator
leading to wrong results is an
example for methodic error.
Proper
understanding
of
the
theoretical
background
of
the
experiments
is
a
necessity
for
avoiding methodic errors.

Indeterminate errors
These errors are also called accidental
errors. Indeterminate errors arise from
uncertainties in a measurement that are
unknown and which cannot be controlled
by the experimentalist.
For example: When pipetting out a liquid,
the speed of draining, the angle of holding
the pipette, the portion at which the
pipette is held, etc, would introduce
indeterminate error in the volume of the
liquid pipette out.

Significant figure
Data have to be reported with care keeping in
mind reliability about the number of figures
used.
For example, when reporting a value as many as
six decimal numbers can be obtained, when one
uses a calculator.
However, reporting all these decimal numbers is
meaningless because, as is generally true, there
may be uncertainty about the first decimal itself.
Therefore, experimental data should be rounded
off.

Significant figure
A zero is not a significant figure,
when used to locate a decimal.
However, it is significant when it
occurs at the end.
For example 0.00405 has three
significant figures, the two zeros
before the 4 being used to imply only
the magnitude, but 0.04050 has four
significant figures, the zero beyond
the 5 being significant.

Significant figure
The number of significant figures in a given
number is found by counting the number
figures from the left to right in the number
beginning with the first non-zero digit and
continuing until reaching the digit that
contains the uncertainty. Each of the
following has three significant figures.
646 0.317 9.22
0.00149
20.2

Significant
figure

When multiplication and division are


carried out, it is assumed that the number
of significant figures of the result is equal
to the number of significant figures of the
component quantity that contains the
least number of significant figures
11 0.122
Example
= 0.1342
10

= 0.13

Significant Figures
Rules for Counting Significant Figures

2. Zeros
a. Leading zeros - never count
0.0025
2 significant figures
b. Captive zeros - always count
1.008
4 significant figures
c. Trailing zeros - count only if the number is written
with a decimal point
100
1 significant figure
100.
3 significant figures
120.0 4 significant figures

Normal error Curve

The normal error curve was first


studied by Carl Friedrich Gauss
as a curve for the distribution of
errors.
He
found
that
the
distribution of errors could be
closely approximated by a curve
called the normal curve of
errors.

Normal error Curve


This normal distribution curve is a
useful one to measure the extent of
indeterminate error. It is given by

is
the standard deviation
x = value of the continuous random
variable.
= mean of the normal random variable
= constant = 3.14

Normal error Curve


In normal error curve, the frequency
is plotted against mean deviation.
When the frequency is maximum the
error is nil.
When the frequency decreases, the
magnitude of the error increases

Normal error Curve


When
is very large, the curve
obtained is bell shaped.
When
is

very small, then a sharp curve is


obtained.

When frequency increases, the


will decrease sharp curve nil
error.

When frequency decreases the


will
increase bell shaped curve error
increases

Normal error Curve


The normal distributions are
extremely important in statistics
and are often used in science for
real valued random variables
whose distributions are not
known.

How many significant figures are


in:
1.12.548
2.0.00335
3.504.70
4.4000
5. 0.10200

(1) There are 5. All numbers are


significant.
(2) There are 3. The zeros before the
number is not significant.
(3) There are 5 significant figures.
(4) There is 1 significant figure.
(5) There are 5 significant figures.