Analytical

Quantitation in Analytical Chemistry

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Errors in Chemical Analysis

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FACT

No quantitative results are of any value unless they are accompanied by some estimate of the errors inherent in them

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Error
Difference between a measured value and the true or known value
Estimated uncertainty in a measurement or experiment

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Uncertainty leads to
scatter of results can not be completely eliminated
Mean value True value

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20.0

20.4

ppm of Pb (II)
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Magnitude of Error can be evaluated..

limits of uncertainty can be determined limits can be defined within which true values lies reliability of experimental data can be estimated

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Reliability can be assessed

Experiments designed to reveal presence of errors Use of standards Calibration and validation Statistical tests Literature search

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Quality Assurance is a must to ensure..

reliability of analytical results

accuracy precision
repeatability
reproducibility

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Precision
reproducibility of measurements closeness (agreement) of results obtained in exactly in the same way determined by repeating measurements use of replicate samples describe by deviation from the mean of an individual value

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Precision can also be expressed..

standards deviation variance coefficient of variation

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Accuracy
closeness of measurement to the true or accepted value agreement between result and accepted value more difficult to determine than precision expressed in terms of error

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Absolute Errors
Absolute error, E
could be negative or positive

Relative Error, Er

more useful quantity than E can be expressed in % or ppt

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Uncertainty
range where true value lies

Absolute uncertainty = margin of uncertainty associated with measurement

Relative uncertainty = compare size of absolute uncertainty with actual size of measurement

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Uncertainty
absolute uncertaint y Re lative uncertaint y magnitude of measuremen t

% relative uncertainty = relative uncertainty x 100

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Low accuracy, low precision

Low accuracy, high precision

High accuracy, low precision

High accuracy, high precision

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Types of Errors in a Chemical Analysis

1. Random or Indeterminate
causes data to be scattered more or less symmetrically from the mean affects precision

2. Systematic or Determinate
causes mean of data set to differ from accepted value. too high or low values affects accuracy

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Systematic Errors
definite value assignable cause same magnitude for replicate measurements leads to bias can either be constant or proportional

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Sources of Systematic Errors

1. Instrumental errors 2. Method errors 3. Personal errors

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Instrumental errors
non-ideal instrument behavior faulty calibration use under inappropriate conditions detectable and correctable

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Method errors
non-ideal chemical or physical behavior of analytical systems most difficult to identify and correct most serious error

examples are:
slow and incomplete reactions unstable species side reactions nonspecific reagents

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Personal errors
carelessness or inattention personal limitations of the analyst
prejudices and bias

examples are:
error in reading color of end point

error in reading of scale division

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Instrument and Personal errors

can be detected and minimized through
periodic calibration care and discipline on part of analyst proper maintenance Quality Assurance

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Method errors
can be detected and minimized through
use of standard samples/reference materials use of second independent method use of blank determination
sample matrix

variation of sample size

constant or proportional error

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Systematic Errors
can be minimized..
Foresight: identifying problem areas before starting experiment Careful experimental design, e.g. use of calibration methods Checking instrument performance Use of standard reference materials and other standards Comparison with other methods for the same analyte(s) Participation in proficiency testing schemes
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Effect of Systematic errors on analytical results

1. Constant

2. Proportional

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Constant error
magnitude stays the same regardless of sample size absolute error is constant with sample size relative error varies with sample size
error increases as the sample size decreases

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Examples of Constant errors..

solubility loss in gravimetric analysis
incomplete precipitation excess reagent to reach end point
volume remains regardless of total volume relative error increases as total volume decreases

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Proportional errors
magnitude changes with sample size
absolute error varies with sample size relative error stay constant with changing sample size

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Proportional errors
presence of contamination

matrix effect
example:

2 Cu +2 + KI
Interference :

I2 + 2 CuI + K+

Cu +3

+ I29

CuI

I2
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Random errors
inevitable part of every analysis
major source of uncertainty in a determination can not be totally eliminated accumulated effect of individual uncertainties causes not easily identified Gaussian curve or normal error curve

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Summary
Random Error
Affect precision-repeatability or reproducibility

Systematic Error
Produce bias-an overall deviation of result from true value even when random errors are very small Cause all results to be affected in one sense only- all too high or all too low Cannot be detected simply by using replicate measurements Can be corrected, e.g. using standard methods and materials Cause by both humans and equipment
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Cause replicate results to fall on either side of a mean value Can be estimated using replicated replicate measurements Can be minimized by good technique but not eliminated Cause by both humans and equipment

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Statistical treatment of Random errors

reveals only information that is already present in the data set

aids in categorization and characterization of data aids in objective evaluation and interpretation of results

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Analytical sample vs Statistical sample

Analytical samples refer to samples (subset) tested or analyzed Statistical sample refers to groups or sets of analytical samples tested
four analytical samples can represent a single statistical sample

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Population
universe collection of all measurements of interest hypothetical or conceptual define by population mean and population standard deviation

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Sample

limited sample drawn from population subset of the population

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Properties of Gaussian Curve

1. Population mean, 2. Population standard deviation, 3. Sample mean,
Arithmetic average of limited sample drawn from population Statistical parameter that estimates the population parameter,

4. Sample standard deviation, s

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Gaussian curve Histogram

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Gaussian Curve

Simplifying in terms of variable z,

Where e = 2.71828
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