Analytical Chemistry Lecture 3

INTRODUCTION
The role of analytical chemist is to obtain

results from experiments and know how to
explain data significantly.
Statistics are necessary to understand the
significance of the data that are collected
and therefore to set limitations on each
step of the analysis.
Precision and Accuracy in

Measurements
Precision how closely repeated measurements
approach one another.
Accuracy closeness of measurement to true
(accepted) value.
Ways of expressing Accuracy

There are various ways and unit in which
the accuracy of a measurement can be
expressed:
A) Absolute error
B) Relative error
Absolute error
Recall: Accuracy is expressed as absolute
error or relative error.
Difference between the true value and the
measured value.
Absolute errors: E = O A
O = observed error
A = accepted value
Example:If a 2.62g sample of material is

analyzed to be 2.52g, the absolute error is
-0.10g
The positive and negative sign is assigned
to show whether the errors are high or low.
If the measured value is the average of
several measurements, the error is called
mean error
Relative error
The absolute or mean error expressed as
a percentage of the true value are called
relative error.
Example:(-0.10/2.62) X 100% = -3.8%
For relative accuracy expressed as
measured value as apercentage of true
value.
Example: (2.52/2.62) X 100 = 96.2%
In very accurate work, we are usually

dealing with relative errors of less than
1%.
1% error = 1 part in 100 = 10 part in 1000
Part per thousand (ppt) is often used in
expressing precision of measurement
Example
The result of an analysis are 36.97g,
compared with the accepted value of
37.06g. What is the relative error in part
per thousands?
Solution:
Absolute error =36.97g 37.06g = - 0.09g
Relative error = - 0.09 X 1000%= -2.4
37.06
Ways of expressing precision

Recall: Precision can be expressed as
standard deviation, deviation from the
mean, deviation from the median, and
range or relative precision.
Example 1: The analysis of chloride ion

on samples A, B and C gives the
following result
Sample %Cl-
Deviation from
mean
Deviation
from
median
A
B
24.39
24.20
0.10
0.09
0.11
0.08
24.28
= 24.29
0.01
= 0.07
(d bar)
0.00
0.06
Deviation from mean

Deviation from mean is the difference
between the values measured and the
mean.
For example, deviation from mean for
sample A= 0.10%
Q1: How to get X ?
A1: = 24.39 + 24.20 + 24.28
3
= 24.29
Deviation from median

Deviation from median is the difference
between the values measured and the
median.
Example, deviation from the median for
sample A = 0.11%.
Now, identify median = 24.28
Therefore, deviation from median for
sample A = 24.39- 24.28 = 0.11%
Range is the difference between

the highest and the lowest values.
For example, range = 24.39- 24.20
= 0.19 %.
Sample standard deviation

For N (number of measurement) < 30
For N > 30
Types of errors
1. Determinate errors (Systematic)
2. Indeterminate errors (Random)
Characteristics of determinate errors:

1. Cause of error is known.
2. Consistency, that is the values are almost the
same.
3.Difficult to correct for with statistics
4. Due to poor technique, faulty calibration, poor
experimental design
5.Controls the accuracy of the method
6. Can be avoided
TYPES OF DETERMINATE ERRORS

Types of determinate or systematic errors:
1.Operative errors
2.Instrumental errors
3.Method errors
4.Error of the reagent.
(i) Operative errors

It is also known as observation error and is
caused by carelessness, clumsiness or not using the
right techniques by the operators.
For example, recording wrong burette reading
as 29.38 mL, whereas the correct reading is 29.35 mL.
To avoid this error is by reading
the volume correctly.
Determinate Error
(ii) Instrumental errors

The faulty equipments, uncalibrated
weight and glasswares used may cause
instrumental errors. Example, using
instruments that are not calibrated and this
can be corrected by calibrating the
instruments before using.
(iii) Method errors

Method errors are caused by the nature of the methods
used.
This error cannot be omitted by running the experiments
several times.
It can be recognized and corrected by calculations or by
changing to a different methods or techniques.
This type of error is present in volumetric analysis that is
caused by reagent volume.
An excess of volume used as compared to theory will
result in the change of colours. Example, mistakes made
in determining end point caused by coprecipitation.
(iv) Errors of the reagent

This error will occur if the reagents used
are not pure. Correction is made by using
pure reagents or by doing back-titration.
INDETERMINATE OR RANDOM ERRORS

Also known as accidental or random error.
This represent experimental uncertainty
that occurs in any measurement.
This type does not have specific values
and are unpredictable.
Charateristics of indeterminate errors:

a) Cause of error is unknown.
b) Spreads randomly around the middle value
(follow the normal distribution/Gaussian curve).
c) Usually small.
d) Have effects on precision of measurement
e) cannot be avoided
f) Easily treated with statistical methods
Example of indeterminate errors: change in humidity and
temperature in the room that cannot be controlled.
Normal Distribution
Bell-shapes curve/normal curve
Mean ()= located in the center
The symbols represent the
standard deviation of an infinite
population of measurement, and
this measure of precision defines
the spread of the normal population
distribution
Variation due to indeterminate

error
Assume the same object is weighed
repeatedly without determinate error on
the same balance.
Examine the data on next page for
replicate weighings of a 1990 penny.
Observed mass (g) for 1990

2.505
2.503
2.507
2.506
2.502
2.508
2.504
2.505
2.507
2.504
2.503
2.506
2.507
2.505
2.503
2.504
2.506
2.505
2.506
2.504
2.504
2.507
2.506
2.506
2.505
2.503
2.505
2.504
2.505
2.505
28
The values are not identical, and not all values occur with equal frequency.
Value
2.502
2.503
2.504
2.505
2.506
2.507
2.508
Frequency
1
4
6
8
6
4
1
29
The next slide is a histogram of the

frequency data notice the symmetrical
arrangement of the values around one
which occurs most frequently.
The mode of a data set is the value which
occurs most commonly or frequently.
31
The mean or average of a data set is the

sum of all the values divided by the
number of values in the set.
The median is the value for which half the
data is larger and half the data is smaller.
A large enough data set of replicate values

has the same number for mode, mean,
and frequency.
If the data set is very large it is called a
population. When the data is grouped into
smaller and smaller intervals, the
histogram approaches a shape called a
Gaussian distribution or bell curve.
Frequency of Mass Values

9
8
7
6
5
4
3
2
1
0
2.502
2.503
2.504
2.505
2.506
CHM 3000 Numbers &

Statistics
2.507
2.508
34
Or, closer to the ideal Gaussian shape:
F
r
e
q
u
e
n
c
y
Individual data value

35
In a population of data, the peak

of the Gaussian distribution falls
at the mean value.
36
Thank you for your

attention

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Analytical Chemistry Lecture 3

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INTRODUCTION

The role of analytical chemist is to obtain

Precision and Accuracy in

Ways of expressing Accuracy

Example:If a 2.62g sample of material is

In very accurate work, we are usually

Ways of expressing precision

Example 1: The analysis of chloride ion

Deviation from mean

Deviation from median

Range is the difference between

Sample standard deviation

Characteristics of determinate errors:

TYPES OF DETERMINATE ERRORS

(i) Operative errors

(ii) Instrumental errors

(iii) Method errors

(iv) Errors of the reagent

INDETERMINATE OR RANDOM ERRORS

Charateristics of indeterminate errors:

Variation due to indeterminate

Observed mass (g) for 1990

The next slide is a histogram of the

The mean or average of a data set is the

A large enough data set of replicate values

Frequency of Mass Values

CHM 3000 Numbers &

Or, closer to the ideal Gaussian shape:

Individual data value

In a population of data, the peak

Thank you for your

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