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error in Chemical Analysis

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Mean, arithmetic mean, and average (x) are synonyms for

the quantity obtained by dividing the sum of replicate

measurements by the number of measurements in the set.

N

xi

i1

N

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

set of N replicate measurements.

The median is the middle result when replicate data are

arranged in order of size. Equal number 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.

Precision

Precision is the closeness of results to others that

have been obtained in exactly the same way.

Precision describes the reproducibility of

measurements. Precision of a measurement is

determined by simply repeating the measurement

on replicate samples.

Three terms are widely used to describe the

precision of a set of replicate data: standard

deviation, variance, and coefficient of variation.

All these terms are functions of the deviation from

the mean di or just the deviation.

di = | x i x |

Accuracy

Accuracy is the closeness of a measurement to the

true or accepted value and is expressed by the

error. Accuracy measures agreement between a

result and its true value but precision describe the

agreement among several measurements. We can

never determine accuracy exactly because the true

value of a measured quantity can never be known

exactly. We need to use an accepted value.

Accuracy is expressed in terms of either absolute

or relative error.

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 - xt

where, xt is the true or accepted value of the

quantity.

The negative sign indicates that the experimental

result is smaller than the accepted value and the

positive sign indicates that the result is larger than

the accepted value.

Relative Error

Relative error of a measurement is the absolute

error divided by the true value.

The percent relative error is given by the

expression,

xi xt

Er

100%

xt

thousand (ppt).

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.

Systematic or Determinate Errors

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. A systematic error

caused the results in a series of replicate

measurements to be all high or all low.

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 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. Bias

has a definite value, an assignable cause and are

about the same magnitude for replicate

measurements. Bias affects all the data in a set in

the same way.

There are three types of systematic errors:1. Instrumental errors are caused by the

imperfections in measuring devices and

instabilities in their components.

2. Method errors arise from nonideal chemical

or physical behavior of analytical systems.

3. Personal errors results from the carelessness,

inattention, or personal limitations of the

experimenter.

i) Constant Errors: Constant Errors does not

depend on the size of the quantity measured

ii) Proportional Errors: Proportional errors

decrease or increase in proportion to the size of

the sample taken for analysis. A common cause of

proportional errors is the presence of interfering

contaminants in the sample.

Systematic instrument errors are usually

corrected by calibration. Periodic calibration

of equipment is always desirable.

Personal errors can be minimized by care and

self-discipline. Errors that result from a known

physical disability can usually be avoided by

carefully choosing the method.

Method errors or bias of an analytical method

is estimated by analyzing standard reference

materials.

sold by the National Institute of Standard and

Technology and Certified to contain specified

concentrations of one or more analytes. The

concentration 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.

3. By analysis by a network of cooperating

laboratories.

Blank Determinations

Blank determinations are useful for detecting

certain types of constant errors. In blank

determination all steps of the analysis are

performed in the absence of a sample. A blank

solution contains the solvent and all the reagents

in an analysis but none of the sample. The results

from the blank are then applied as a correction to

the sample measurements. Blank determinations

reveal errors due to interfering contaminants from

the reagents and vessels employed in analysis.

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