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Errors
-Analyst is to obtain a result as near to the true value.
-It is made possible by the correct application of the analytical procedure employed.
-By the application of the analytical procedure a set of quantitative data is collected.
-The data are subject to errors.

Error is defined as a difference between a measured value and true value
E= (Measured - true ), where E= absolute error.
- Error 1/Accuracy.
-Except abosolute error, expression of errors in relative terms:
Percentage = Measured X 100 = % error
True

Per thousand = Measured X 1000 = ppt
True
-The true value of any quantity is never known.

-However, the value of a standard sample certified by institute of standards & regulatory body
may be treated as correct.
e.g,
-National Medicine Laboratory supplies secondary reference substances.
National Bureau of Standards & Metrology calibrates various devices and provides values
Error types:

1)Determinate(Systematic)errors2)Indeterminate(Random)errors
1)Determinate(Systematic)errors(

-These errors are because of definite causes.
-These can be avoided or whose magnitude can be determined.
-These are generally unidirectional W.R.T. the true value
- These are reproducible.
-Sources of errors can be predicted by a person who thoroughly understands all the aspects of
the measurement.
-Sources of the errors may be ,e.g.
i) Incorrectly calibrated instrument,
i.e. burette, balances, or pH meter,
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ii) An impurity in a reagent,

iii)A side reaction in a titration, &

iv)Heating a sample at too high Temp.

Classification

i)Methodic( because of Non-ideal chemical or physical behaviour of analytical system)

ii)Operative(because of Carelessness, inattention, personal limitation of experimenter)

iii)Instrumental(because of Non-ideal instrument behaviour, faulty calibrations, using under
inappropriate conditions)
i)Methodic

-Most serious of analytical errors.
-Inherent in the method applied.
-The sources of the error in the physico- chemical properties of the system.
e.g in the precipitation of aluminium( as aluminium hydroxide) zirconium, titanium & iron are
co-precipitated.
ii)Operative

-These originate from ineptitude of the experimenter.
-Reasons behind:
colour blindness,
incorrect handling of instruments
or
careless weighing.
iii)Instrumental

-These are because of failure of measuring devices to perform in accordance with required
standards.

-These can be minimized by calibration or use of proper blanks in case of spectrophotometric
analysis.
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2)Indeterminate(Random)errors
-Exist in every measurements.
-Caused by uncontrollable variables.
-Never be totally eliminated & major source of uncertainty in analysis.
-The sources of errors are small & show accumulated effect.


Calibration of instrumental methods:
-Calibration determines/fix the relationship between the analytical response & theanalyte
concentration.
-Usually this is determined by the use of chemical standards.
-However, gravimetric & some coulometric methods do not require chemical standards.

Types of calibration
1)Comparison with Standards
i) Direct comparison ii)Titrations
2) External-Standard Calibration
3) Standard-Addition Methods
4) The Internal-Standard Method
1)Comparison with Standards

i) Direct comparison:
-Property of analyte is compared with the standard until the property being tested matches or
nearly matches that of the standard.
e.g in colourimetry, colour produced as the result of a chemical reaction of the analyte is
compared with thecoloured produced by the same reaction of the standard.

The concentration of the standard is varied by dilution until its colour exactly or nearly matches
the sample.

-Colour may be the inherent property of analytes& standards.

-Then ,
the concentration of analyte= Conc. of the Std.

-It is also called the null comparison or isomation method.

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ii)Titrations
-Analyte reacts with a standardized reagent.
-Reaction should be stoichiometric.
-The amount of titrant is added until chemical equivalent is reached.
-The chemical equivalent is ascertained by the colour change of the chemical indicator.
-The amount of standardized reagent needed to achieve the chemical equivalence is related to
the amount of analyte.

2)External-Standard Calibration
-It is used to calibrate instruments & procedures.
-It is assumed that the interference effects from the sample matrix are absent.

-Series of standard solutions of the analyte with increasing order of concentration are prepared.
-At least three solutions should be prepared.
-Sample solution also prepared in such a way that its Conc. Approximately falls at the middle of
the Conc. range of series of standard solutions.
-Instrument response(absorbance, peak height/area) is obtained for each Std. solutions &
Sp.solution.
-The instrument response/signals are taken as a function of the analyte concentration.
-A calibration curve is plotted as signal(intercept) vs. Conc.(abscissa)
(Use Conc. & instrument response of analyte in standard solutions)
or
If data points do not fall exactly on straight line due to random errors ,fitting the data to
mathematical method of linear least square( y=mx+b)
-Then Conc. of analyte is determined either with the help of the curve or best fit equation.

3)Standard-Addition method:
-Useful when likelihood of matrix effects is substantial.
(Used when suitable internal std. is unavailable &analyte present in Sp. is in trace Amt.)
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-Identical volumes of samples are spiked with standard (known) in increasing order of
concentration.
-Each solution is further diluted to a fixed volume.
-Measurement is made on one original & other std. added samples.
-In all samples , sample matrix is nearly identical.
After the blank correction, instrument responses are measured for all the samples.
-Then responses are plotted against the volume of sample
(Conc. added standard in the sample).
-Extrapolation from zero added material determines how much analyte was in the original
sample.(Curve prepared for flame photometry )

3)Internal standard method:
-Internal standard is added in a constant amount to all samples and calibration standards.
-The ratio of the analyte signal to the internal Std. signal is plotted against as a function of the
analyte concentration of the standards.(Use Conc.of Std.solutions & their response)

Eventually,
-This ratio for the sample is calculated then used to obtain analyte concentration in sample
from the calibration curve drawn.

Benefits:
-This method is useful to eliminate several types of both random & systematic errors.
-This happens when the both analyte & internal standard respond proportionally to random
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instrumental & method fluctuation.
-The result of ratio of their signals(Analyte/Int.Std) is independent of such fluctuation.


-The matrix effect can also be compensated if two signals are influenced in the same way.
e.g.
-Lithium for the determination of sodium & potassium in blood serum by flame spectrometry.
-Propan-2-ol for the determination of ethanol in blood sample by GLC.




Requirements for the internal standard:

i)It should provide a signal that is similar to the analyte.

ii)Two signals should be sufficiently distinguishable by the instrument.

iii)It should be chemically similar to but not present in the original sample.

iv)Neither it affects the analyte signal, nor get affected by the analyte signal.