Evaluating Analytical Data

Characterizing Measurements and Results

Measure of Central Measure of the spread
Tendency
Mean: the average value of a set of data

Median : the middle value when data are ordered

from the smallest to the largest value, Xmed
What is the mass of penny?
What is the mass of an average United
States penny in circulation?
What is mean and median for
the data in Table 4.1?

Solution
 Measure of the spread
Range : the difference between
the largest and smallest values
in the data set.
Standard Deviation : the spread
of individual measurement about
the mean.
Relative Standard Deviation (RSD, sr)

Coefficient of variation (RSD in %)

The percent of relative standard
deviation
Variance (s2)
Equal to the square of the standard deviation
What are the standard deviation, relative standard deviation,
and percent relative standard deviation for the data in Table
4.1?
Solution
Standard Deviation

Relative standard deviation (Sr)

and % Sr
How to characterize the data?

1. Measure of central Accuracy

tendency

2. Measure of spread Precision

Errors in Chemical Analysis

 Types of Error in Experimental
Data
Three types:
(1) Random (indeterminate) Error
Data scattered approx. symmetrically about a mean value.

(2) Systematic (determinate) Error

systematic deviation from the true value, readings all too
high or too low.

(3) Gross Errors

Usually obvious - give “outlier” readings. Detectable by
carrying out sufficient replicate measurements.
 Sources of Systematic Error
1. Instrument Error
Need frequent calibration - both for apparatus such as
volumetric flasks, burettes etc., but also for electronic
devices such as spectrometers.

2. Method Error
Due to inadequacies in physical or chemical behaviour
of reagents or reactions (e.g. slow or incomplete reactions)

3. Personal Error
e.g. insensitivity to colour changes; tendency to estimate
scale readings to improve precision; preconceived idea of
“true” value.
 How to characterize the data?

1. Measure of central Accuracy

tendency

2. Measure of spread Precision

How to evaluate accuracy and

precision
Accuracy– Systematic/determinate error
Systematic errors can be
constant (e.g. error in burette reading – less important for larger values
of reading) or
proportional (e.g. presence of given proportion of interfering impurity in
sample; equally significant for all values of measurement)
Constant Error
The effect of solubility losses on the results of a gravimetric analysis,
shown in Example 5-2, illustrates this behavior.
Example 5-2
Suppose that 0.50 mg of precipitate is lost as a result of being washed with
200 mL of wash liquid. If the precipitate weighs 500 mg, the error due to
solubility loss is….
The absolute and the relative error?
The absolute error : 0.50 mg
The relative error : (0.50/500) x 100% = 0.1%.
If 50 mg of precipitate? The relative error = 1.0%.
With constant errors, the absolute error is constant with sample size, but
the relative error varies when the sample size is changed.
Proportional Error

A common cause of proportional errors is the presence of interfering

contaminants in the sample.

For example, a widely used method for the determination of copper is

based on the reaction of copper(II) ion with potassium iodide to give
iodine (see Sections 20B-2, 38H-3, and 38H-4.). The quantity of iodine is
then measured and is proportional to the amount of copper. Iron(III), if
present, also liberates iodine from potassium iodide.

2 Cu2+ + 4 I- 2 CuI(s) + I2
I2 + 2 S2O3-2 2 I- + S4O6 -2

High results are observed for the percentage of copper because the iodine
produced will be a measure of the copper(II) and iron(III) in the sample. If
the sample size is doubled, for example, the amount of iodine liberated by
both the copper and the iron contaminant is also doubled.

With proportional errors, the absolute error varies with sample size, but
the relative error stays constant when the sample size is changed.
How to minimize of systematic error?

Minimize instrument errors by careful recalibration and good

maintenance of equipment.

Minimize personal errors by care and self-discipline

Method errors - most difficult. “True” value may not be known.

Three approaches to minimize:
•analysis of certified reference material (CRM)
•use 2 or more independent methods
•analysis of blanks
 Analisa CRM
• Contoh: CRM diketahui mengandung 38.9%
Hg dianalisa dengan AAS. Hasil Uji:
Hasil Uji (%)
38.9 Xtrue-Xmean=1.1%
37.4 Sd= 0.964
37.1
Xmean= 37.8 %
• Asumsi: Ho=tidak ada bias; hanya tertolak bila
• Xmean-Xtrue>± ts/√n dengan t adalah nilai dari tabel t
• Tingkat kepercayaan 95%t= 4.303
• Sehingga ts/ √n= 4.303x0.964/ √3=2.390 %
Precision – indeterminate error
Standard deviation = 0.0024 and 0.051

If RSD < 10%, acceptable result

The Distribution of Measurement and Results

Population

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Sampling Information/est
imator

Sample

Populations and Samples 17

The Population Mean (μ) and the Sample

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 Standard Deviation
Standard deviation population :

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Standard deviation sample :

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Degree of freedom
The distribution of repeated measurement

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Probability Distributions

Measurement Normal Distribution

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Gaussian Curve
Shows the symmetrical distribution of data around
the mean of infinite set of data

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 symmetrical μ
 The greater the
value of σ, the
greater the spread
of curve

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The confidence interval for the
mean is the range of value
within which the population
mean μ is expected to lie with
a certain probability.

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The confidence level is the
probability that the true
mean lies within a certain
interval and is often
expressed as a percentage

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The confidence interval for large sample :

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The confidence interval for small sample :

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Where t :

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The confidence Limit :
The confidence Limit :
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*5-4. Describe at least three systematic errors that might
occur
while weighing a solid on an analytical balance.
*5-5. Describe at least three ways in which a systematic error
might occur while using a pipet to transfer a known
volume of liquid.
5-6. How are systematic method errors detected?
*5-7. What kind of systematic errors are detected by varying
the sample size?
5-8. A method of analysis yields masses of gold that are low
by 0.4 mg. Calculate the percent relative error caused
by this result if the mass of gold in the sample is
*(a) 500 mg. (b) 250 mg.
The color change of a chemical indicator requires an
overtitration of 0.03 mL. Calculate the percent relative
error if the total volume of titrant is
*(a) 50.00 mL. *(b) 10.0 mL.
*(c) 25.0 mL. (d) 30.0 mL.