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III. EVALUATION OF ANALYTICAL DATA
What is ERROR?
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Errors in chemical analysis
Every measurement is influenced by many uncertainties that
combine to produce a scatter of results. Measurement uncertainties
can never be completely eliminated, so the true value for any
quantity is always unknown.
Chemists usually carry 2-5 portions (replicates) of a sample through
an entire analytical procedure.
Individual results from a set of measurements are seldom the same,
so a central or “best” value is used for the set.
The central value of a set should be more reliable than any
individual result
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Mean (arithmetic mean, or average), x
- arithmetic mean or average
- the quantity obtained by dividing the sum of replicate
measurements (xj)
by the number of measurements (n)
Mathematically speaking, x= [(x1 + x2 + x3 + … + xn)] / n
Median, M
- middle value of a sample of results arranged according to
increasing or decreasing value.
For odd number of data → take the middle value
For even number of data → take the mean of 2 middle values
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Mode – the value occurs most frequently in a set of determinations.
High accuracy, high High accuracy, low Low accuracy, high precision Low accuracy, low
precision precision precision
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Accuracy is expressed in terms of either absolute or relative error
Absolute error, E
- the difference between the measured value and the true value
E = xi – xt
sign of absolute error: tells whether the value in question is high or low.
negative sign: measurement result is low
positive sign: measurement result is high
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Sample Problem
1. Calculate the mean, median, absolute error immediately to
the left and to the right of the true value and relative error for
the mean in ppt, for the results from six replicate determinations
for iron in aqueous samples of a standard solution containing
20.00 ppm of iron(III):
19.4, 19.5, 19.6, 19.8, 20.1, 20.3 ppm iron (III)
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Example for absolute Error
Types of errors
Types of Erros
Assignment
1. A method of analysis yields for gold that are low by 0.4 mg. Calculate
the % error caused by this uncertainty if the weight of gold in the
sample is
a) 700 mg b) 450 mg c) 250 mg d) 40 mg
2. The method described in Prob. 1 is to be used for the analysis of
ores that assay about 1.2% gold. What minimum sample weight should
be taken if the relative error resulting from a 0.4 mg loss is not to
exceed
a) -0.2% ? b) - 0.5% ? c) - 0.8% ? d) -1.2 %?
3. The color change of a chemical indicator requires an overtitration of
0.04 mL. Calculate the percent relative error if the total volume of
the titrant is
a) 50.00 mL. b) 25.00 mL. c) 10.0 mL. d) 40.0 mL.