MAKING DECISIONS

WITH DATA

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Making measurements is critical for

quantitative analysis.
Standards of length were once represented by the distance between
two marks on a solid metal bar. Copies of these standards were
displayed in public places so that people could check the accuracy of
the rules they were using.
In 1588, Elizabeth I issued a new standard yard that remained the legal
British yard for over 300 years.
Every measurement involves three
components:
Object to be measured
Device used to make the measurement
Comparison to a known standard

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This means that there

will be an error
associated with EVERY
measurement! In AChem this is explained
and reported.

General Terms: A-Chem Talk

Sample-Related Terms
SAMPLE representative
of the tested material
MATRIX all substances
in the sample
ANALYTE specific
substance we measure
MAJOR: >1%
MINOR: 0.01% to 1%
TRACE: below 0.01%

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Method-Related Terms
ANALYTICAL TECHNIQUE
an approach to the assay
which involves
- determining what question is
being asked
- using an appropriate sample
- sample preparation
- gathering measurements
- reporting results

Measurements can be accurate or precise

In the lab, the true
value may be an
accepted value (rather
than a known value),
ABSOLUTE ERROR:
ERROR
e=x
RELATIVE ERROR:
ERROR
er = (x )/
This can be
expressed as a
fraction, percent, ppt,
ppm.

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Example:
The results of an analysis are 36.97 g,
compared with the accepted value of
37.06 g. What is the relative error in ppt,
ppm, and percent?

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Living with Uncertainty

EVERY Measurement we make will have some uncertainty
(error). Classify the following pipette errors:
Suppose the tip of a TD pipet has a small chip that
changes the size of the opening. Repeated
measurements with the pipet will always be off, but by
the same amount and in the same direction.
Systematic or Random?
A perfectly good TC pipet is used to deliver 20.0 mL.
Systematic or Random?
Which problem could be eliminated?
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Some Common determinate

errors:
Instrumental errors
Operative Errors
Errors of the method

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Communicating Experimental Results

Suppose you did three trials to determine the
M of a drain cleaner. You could report the
average value (but with a small number of
samples we have the experimental mean
X ).
With a large number of trials random errors
tend to cancel out then X approaches the
true mean

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Describing variation within a set of data that,

in theory, should not vary
Rather than just examine the simple range of
values, we can compare each value to the
experimental mean. This comparison of
variation is called the standard deviation

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The Helpful Relative Standard Deviation

RSD = s/mean
This can be expressed as a percent.
RSD can also be known as the coefficient of variation.
A smaller value indicates better precision.
Median- middle value of the group
Range- difference between largest and smallest value

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Practice: A student found the following values

from three trials for the molarity of his HCL:
0.01005 M; 0.01018 M;
0.00998 M
What is the experimental mean?
What is value of s?
What is the value of RSD?
What is the median?
What is the range?

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Mean = 0.01007 M
s = 0.0001
RSD = 0.0099

How precisely do we know

the mean and s?
We can calculate the standard deviation of
the mean:
Since this depends on n, you should report
the number of values used in the analysis.
The precision of the mean becomes better as
we repeat the experiment. (Closer to )
The variability of a data set (like titration) is
reported as the Confidence Interval (CI).

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Uncertainty of working with small data sets

A correction factor is used with the mean and s
to show the interval around the mean where
values may lie.
What is t?

Ex 4.7

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Example:
A soda ash sample is analyzed in the
analytical chemistry laboratory by titration
with standard hydrochloric acid. The
analysis is performed in triplicate with the
following results: 93.50, 93.58, and 93.43 %
Na2CO3. Within what range are you 95 %
confident that the true value lies?

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Exercise 1 part A
1.

2.

3.

(Accuracy and precision) The content of ATP (adenosine

triphosphate) in a tissue sample is known to be 122 mol/mL. A
new assay for ATP gives the following values for separate
analyses of this tissue: 117, 119, 111, 115, and and 120 mol/mL.
Calculate the absolute error and the relative error (in % and in
ppm) for each of these results.
(Accuracy and precision) Consider the set of data: 86.37,
86.33, 86.37, 86.20, 86.60 % Co Calculate the a) mean b) median
c) range d) standard deviation and e) relative standard deviation
(Confidence limits and intervals) A new herbicide is measured
in water samples by using gas chromatography. The following
results are obtained for the replicate analysis of a single sample:
3.01, 2.92, 3.18, 3.07, and 2.84 g/L. What are the mean result
and the 90% confidence interval for the average herbicide
concentration in this sample?

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