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Data analysis

1

Errors In Chemical Analyses

Mean

the quantity obtained by dividing the sum of replicate

measurements by the number of measurements in the set.

N

x

i 1

i

x

N

where, xi represents the individual values of x making up a set

of N replicate measurements.

2

Median

arranged in order of size.

median.

evaluated directly.

3

xm = 19.70

4

Precision

obtained in exactly the same way.

replicate samples.

standard deviation, variance, and coefficient of variation.

All these terms are functions of the deviation from the mean

di or just the deviation.

di = | xi – x |

5

Accuracy

accepted value and is expressed by the error.

value but precision describe the agreement among several

measurements.

value of a measured quantity can never be known exactly.

We need to use an accepted value.

error.

6

Illustration of accuracy and precision 7

Absolute Error

The absolute error of a measurement is the

difference between the measured value and the true

value. The absolute error E in the measurement of

a quantity xi is given by the equation,

E = xi - x t

smaller than the accepted value

– Positive sign indicates that the result is larger than the

accepted value.

8

Relative Error

error divided by the true value.

expression,

xx

i t

E

r 100%

x t

Relative error expressed in parts per thousand (ppt).

9

Absolute error in nitrogen determination 10

Random or Indeterminate Errors

The errors that affect the precision of

measurement. This type of error causes data to be

scattered more or less symmetrically around a

mean value. Random error in a measurement is

reflected by its precision.

The errors that affect the accuracy of a result. This

type of error causes the mean of a set of data to

differ from the accepted value.

11

Gross Errors

They usually occur only occasionally, are often large, and

may cause a result to be either high or low. Gross error leads

to outliers.

This error causes the result differs significantly from the rest

of the results.

Bias Errors

Bias measures the systematic error associated with an

analysis. It has a negative sign if it causes the result to be low

and a positive sign otherwise.

the same magnitude for replicate measurements. Bias affects

all the data in a set in the same way.

12

How do Systematic Errors Arise?

measuring devices and instabilities in their components.

behavior of analytical systems.

or personal limitations of the experimenter.

13

Effects of Systematic Errors

depend on the size of the quantity measured

decrease or increase in proportion to the size of the

sample taken for analysis.

interfering contaminants in the sample.

14

Detecting Systematic Errors

by calibration. Periodic calibration of equipment is

always desirable.

estimated by analyzing standard reference materials.

discipline.

15

Standard reference materials are substances sold or

Certified by the National Institute of Standard and

Technology (NIST) to contain specified concentrations of

one or more analytes.

has been determined in one of three ways:

method.

2. By analysis by two or more independent, reliable

measurement methods.

3. By analysis by a network of cooperating laboratories.

16

Blank Determinations

Blank determinations are useful for detecting certain types

of constant errors.

performed in the absence of a sample.

in an analysis but none of the sample. The results from the

blank are then applied as a correction to the sample

measurements.

contaminants from the reagents and vessels employed in

analysis.

17

Variance

deviation from the mean of a set of

data. It is used to find the standard

deviation.

18

Variance

1. Find the mean of the data.

Hint – mean is the average so add up the

values and divide by the number of items.

2. Subtract the mean from each value – the

result is called the deviation from the mean.

3. Square each deviation of the mean.

4. Find the sum of the squares.

5. Divide the total by the number of items.

19

Variance Formula

Notation, , which represents the sum of all

the items to the right of Sigma.

(x i ) 2

n

Mean is represented by and n is the

number of items.

20

Standard Deviation

Standard Deviation shows the variation in data.

If the data is close together, the standard deviation will be

small. If the data is spread out, the standard deviation will

be large.

by the lowercase Greek letter sigma,

Measures the dispersion of data

further the data tend to be dispersed from the mean.

21

The bell curve which represents a normal

distribution of data shows what standard deviation

represents.

direction on the horizontal axis accounts for around 68

percent of the data.

• Two standard deviations away from the mean accounts for

roughly 95 percent of the data

• Three standard deviations representing about 99 percent of

the data. 22

Standard Deviation

Find the variance.

a) Find the mean of the data.

b) Subtract the mean from each value.

c) Square each deviation of the mean.

d) Find the sum of the squares.

e) Divide the total by the number of items.

f) Take the square root of the variance.

n

i

( x ) 2

i 1

n

23

Standard Deviation

Population Standard Deviation:

n

i

( x ) 2

i 1

i

( x ) 2

s i 1

n 1

24

Correlation Coefficient (r)

between two variables

association.

25

If the sign is +ve this means the relation is

direct (an increase in one variable is

associated with an increase in the

other variable and a decrease in one variable

is associated with a decrease in the other

variable).

or indirect relationship (which means an

increase in one variable is associated with a

decrease in the other).

26

The value of r ranges between ( -1) and ( +1)

The value of r denotes the strength of the association as

illustrated by the following diagram.

indirect Direct

perfect perfect

correlation correlation

no relation

27

Computation of Correlation Coefficient (r)

Covariance

Cov( x, y ) xy x y

1

n

Correlation Coefficient

1

xy x y

r n

x y

28

Example:

Pupil A B C D E F G H I J

Marks 20 23 8 29 14 11 11 20 17 17

X/30

Marks 30 35 21 33 33 26 22 31 33 36

Y/40

xy x y

Find Correlation Coefficient 1

r n

x y

Cov( x, y ) xy x y

1

n 1

1

5313 17 *30

5313 17*30

10 10

(6)(5)

21.3

r 0.71

29

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