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Mean, Median, Precision, Accuracy, Absolute and Relative error, Significant Figures, Normal Error Curve

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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.

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

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

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

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.

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

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

When

is very large, the curve

obtained is bell shaped.

When

is

obtained.

will decrease sharp curve nil

error.

will

increase bell shaped curve error

increases

The normal distributions are

extremely important in statistics

and are often used in science for

real valued random variables

whose distributions are not

known.

in:

1.12.548

2.0.00335

3.504.70

4.4000

5. 0.10200

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.

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