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Errors in Analysis
Content
• Error
• Types of error
Learning Objectives
At the end of this lecture, the student will be able to
• Define error
• Classify error
• Discuss about the different types of methods for minimizing the errors
Errors
Definition: Error is the difference between the true result (and accepted true result) and the measured result
Expression of Errors
Relative Error: Used in the determination of accuracy of a measurement and is expressed in terms of percentage
Types of Errors:
Determinate or systematic error
Determinate errors
• Determinate errors are caused by faults in the analytical procedure or the instruments used in the analysis
• The name determinate error implies that the cause of this type of error may be found out and then either avoided or
corrected
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• Determinate errors are systematic errors; that is, they are not random
• Sometimes the determinate error is proportional to the true result, giving rise to proportional errors
• Other determinate errors may be variable in both sign and magnitude, such as the change in the volume of a solution
as the temperature changes
• Although this variation can be positive or negative, it can be identified and accounted for
• It depends on the error and how it enters into the calculation of the final result
For example:
• If the balance is set so that the zero point is actually 0.5 mg too high, all masses determined with this balance will be
0.5 mg too high
• If this balance was used to weigh any standard solution used in the laboratory, the standard concentration will be
erroneously high, and all of the results obtained using this standard will be erroneously low
• The error is reported as the absolute error, the absolute value of the difference between the true and measured
values
• Two methods are commonly used to identify the existence of systematic errors
• Standard method: is to analyze the sample by a completely different analytical procedure that is known to involve no
systematic errors
• They have been evaluated extensively by many laboratories and shown to be accurate and precise
• If the results from the two analytical methods agree, it is reasonable to assume that both analytical procedures are
free of determinate errors
• The second method is to run several analyses of a reference material of known, accepted concentration of analyte
• The difference between the known (true) concentration and that measured by analysis should reveal the error
• If the results of analysis of a known reference standard are consistently high (or consistently low), then a determinate
error is involved in the method
• The cause of the error must be identified and either eliminated or controlled if the analytical procedure is to give
accurate results
• Many clinical and analytical laboratories participate in proficiency testing programs, where “unknown” standard
samples are sent to the laboratory on a regular basis
• The results of these samples are sent to the government or professional agency running the program
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• The unknowns are of course known to the agency that sent the test samples; the laboratory receives a report on the
accuracy and precision of its performance
• uncalibrated balances
• Impure chemicals
• Analyst error
c) Errors of method
• They may be the result of inexperience, insufficient training, or being “in a hurry”
• An analyst may use the instrument incorrectly, perhaps by placing the sample in the instrument incorrectly each time
• Consistently misreading a meniscus in a volumetric flask as high (or low) Improper use of pipettes, such as
These are due to factors for which the individual analyst is responsible and are not connected with the method or
procedure
The errors are mostly physical in nature and occur when sound analytical technique is not followed
Examples:
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• Some other analyst-related errors are Carelessness, which is not as common as is generally believed transcription
errors, that is, copying the wrong information into a lab notebook or onto a label Calculation errors
• Proper training, experience, and attention to detail on the part of the analyst can correct these types of errors
1. Instrumental errors:
Incorrect reading of values, and incorrect settings of the readout (i.e., zero signal should read zero)
• Instruments are often calibrated during the day, when electrical power is in high demand. At night, when power
demand is lower, line voltage may increase substantially, completely changing the relationship between concentration
of analyte and measured signal
• Regulated power supplies are highly recommended for analytical instruments. The procedure for unattended analysis
should include sufficient calibration checks during the analytical run to identify such problems
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• These problems can be eliminated by a systematic procedure to check the instrument settings and operation before
use
• Such procedures are called standard operating procedures (SOPs) in many labs
• There should be a written SOP for each instrument and each analytical method used in the laboratory
2. Reagent errors:
• Impurities in the reagents may interfere with the determination of the analyte, especially at the ppm level or below
• The suspect reagent may be tested for purity using a known procedure or the analysis should be redone using a
different set of reagents and the results should be compared
A difference between the observed end point and stoichiometric end point of the reaction
For example:
oss in weight of a crucible in which a precipitate is ignited and errors in weights. The presence of this error is revealed
by taking samples of different weights
Powdered gloves may contain a variety of trace elements and should not be used by analysts performing trace element
determinations
• The absolute value of a proportional error depends upon the amount of the constituents
For example:
Indeterminate Errors
Indeterminate errors are not constant or biased
Are the cause of slight variations in results of replicate samples made by the same analyst under the same conditions
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For example:
A balance that is capable of measuring only to 0.001 g cannot distinguish between two samples with masses of
In one case the measured mass is low, in the other case it is high
These random errors cause variation in results, some of which may be too high and some too low
The average of the replicate determinations is accurate, but each individual determination may vary slightly from the
true value
Indeterminate errors arise from sources that cannot be corrected, avoided, or even identified, in some cases
• Concentration errors
• abeling errors
• Calculation errors
• Using wrong formula in excel Using different location (wrong cell) in the excel sheet
Minimization of Errors
Analyst has no control on random errors but systemic errors can be reduced by following methods:
Calibration of apparatus: By calibrating all the instruments, errors can be minimized and appropriate corrections are
applied to the original measurements
Control determination: Standard substance is used in experiment in identical experimental condition to minimize the
errors
Blank determination: By omitting sample, a determination is carried out in identical condition to minimize the errors
occurs due to impurities present in reagent
For Example: Iron (III) is first determined gravimetrically by precipitation method as iron (III) hydroxide and then
determined titrimetrically by reduction to the iron (II) state
Parallel determination: Instead of single determination, duplicate or triplicate determination is carried out to minimize
the possibilities of accidental errors
Standard addition: This method is generally applied to physico-chemical procedures such as polarography and
spectrophotometry
Amplification methods: It is used when a very small amount of material is to be measured which is beyond the limit of
the apparatus
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Particular care should be taken to avoid contamination of the stopper of the reagent bottle
hen a liquid is poured from a bottle, the stopper should never be placed on the shelf or on the working bench it may
be placed upon a clean watch glass
Many chemists cultivate the habit of holding the stopper between the thumb and fingers of one hand
The stopper should be returned to the bottle immediately after the reagent has been removed, and all reagent bottles
should be kept scrupulously clean, particularly round the neck or mouth of the bottle
• Allow the flask to stand for a while before making the final adjustment to the mark to ensure that the solution is at
room temperature
• It should be noted, however, that for some solutions as, for example, iodine and silver nitrate, glass containers only
may be used, and in both these cases the bottle should be made of dark (brown) glass
• Immediately after the solution has been transferred to the flask, it should be labelled with:
(4)The initials of the person who prepared the solution, together with any other relevant data
• Change in the condition of the containing vessel or of the substance between successive weighing by absorption or
loss of moisture, by electrification of the surface caused by rubbing, by its temperature being different from that of the
balance case
• Effect of the buoyancy of the air upon the object and the weights
• Hygroscopic, efflorescent, and volatile substances must be weighed in completely closed vessels
• Substances which have been heated in an air oven or ignited in a crucible are generally allowed to cool in a desiccator
containing a suitable drying agent
• Substances which have been heated in an air oven or ignited in a crucible are generally allowed to cool in a desiccator
containing a suitable drying agent
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• The time of cooling in a desiccator cannot be exactly specified, since it will depend upon the temperature and upon
the size of the crucible as well as upon the material of which it is composed
• Platinum vessels require a shorter time than those of porcelain, glass, or silica
• It has been customary to leave platinum crucibles in the desiccator for 20-25 minutes, and crucibles of other materials
for 30-35 minutes before being weighed
GENERAL INSTRUCTIONS: For Minimizing Errors for graduated flasks: Vessels intended to contain definite volumes of
liquid
• The neck is made narrow so that a small change in volume will have a large effect upon the height of the meniscus
• To read the position of the meniscus, the eye must be at the same level as the meniscus, in order to avoid errors due
to parallax
The analyst reads the burette from a position above a line perpendicular to the burette and makes a reading of 12.58 m
or 12.67 m
The analyst reads the burette from a position along a line perpendicular to the burette and makes a reading of 12.6 m
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loves resistant to the chemicals in use should be worn at all times in the laboratory
Errors in Assay
• Incorrect weighing and transfer of analyte and standards
• A noticeable difference occurring between the stoichiometric equivalence point of a reaction and the observed end-
point
Accuracy, Precision
• Accuracy
• Precision
Repeatability of measurements
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Example: Determine the accuracy and precision of the mass of a piece of a metal performed by three different students,
where mass of a piece of metal is 0.520gm. Data obtained by each student are recorded as follow.
Significant Figures
• Digit: Any one of the ten numerals, including zero
• Significant figure: A digit which denotes the amount of the quantity in the place in which it stands
For example: 2.7808 g and 1.0032 g → zero is significant, whereas in 0.0050 g → zero is not significant but only to locate
the decimal point, the value can also be written as 5mg
Summary:
• Error: The difference between the true result (or accepted true result) and the measured result
• Classification of errors: Determinate error → which can be determined, indeterminate error → which cannot be
determined
c) Errors of method
• Minimization of error: Calibration of apparatus, Controlled determination, Blank determination, Independent methods
of analysis, Parallel determination, amplification method, standard addition method, internal standard method, isotopic
dilution
• Correct way of using analytical reagents, bottles, samples, weighing, burette, pipette and graduated flasks can
minimize the errors
• Significant figure: A digit which denotes the amount of the quantity in the place in which it stands
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