Using Student’s 

t for Significance Testing

Example of testing literature values with Student’s t.
If you look up the chemical reaction rate constants
of CFCl reacting with nitric oxide, NO, in the literature, you find
two reports

Work # 1 Work #2
k=1.0(0.1)10-14 @ 90% conf. k=1.6(0.2)10-14 @ 95% conf.
Upon reading the experimental section of both papers, both
works used 5 replicate measurements to arrive at the result.
Thus N=5
From that information, we can “back out” the standard
deviations from the Student’s t confidence intervals since

We find s1=1.010-15 and s2=1.610-15

With the two standard deviations, the F-test is used to determine

if the two came from the same parent population.
First, calculate Fcalc
Next, compare to the table value. The table value for 95%
confidence and 4 degrees of freedom for each standard deviation
is Ftable  = 6.39
Since Fcalc is less than Ftable the two standard deviations may
have come from the same parent population. And the pooled
standard deviation may be used for the Student’s t test.
The pooled standard deviation is obtained from

In this case spooled = 1.3310-15

Finally, the Student’s t test for significance is performed. 

1) Invoke the null hypothesis, that both reported rate constants
came from the same population of measurements.
2) Calculate a Student’s t using the joint estimate of the standard
deviation. 
3) Compare the calculated value to the table value. The table
value for 95% confidence and N1+N2-2 = 8 degrees of freedom
is ttable = 2.306
4) Since ttable is less than tcalc the two means did not come from
the same parent population. In this case, a third measurement
should be performed to determine the correct value of the rate
constant.

This page last check Tuesday, August 03, 2004

 
Aim of Statistics in Analytical Chemistry:
Modern analytical chemistry is concerned with the detection, identification, and
measurement of the chemical composition of unknown substances using existing
instrumental techniques, and the development or application of new techniques and
instruments. It is a quantitative science, meaning that the desired result is almost
always numeric. We need to know that there is 55 μg of mercury in a sample of water, or
20 mM glucose in a blood sample.

Quantitative results are obtained using devices or instruments that allow us to

determine the concentration of a chemical in a sample from an observable signal. There
is always some variation in that signal over time due to noise and/or drift within the
instrument. We also need to calibrate the response as a function of analyte
concentration in order to obtain meaningful quantitative data. As a result, there
is always an error, a deviation from the true value, inherent in that measurement. One
of the uses of statistics in analytical chemistry is therefore to provide an estimate of the
likely value of that error; in other words, to establish the uncertainty associated with the
measurement.

Accuracy & Precision:

Two terms of importance in any measurement are accuracy and precision, and it is

important to distinguish between them since these terms have highly specific meanings
when applied to scientific measurement.

Accuracy:

Accuracy is defined as the closeness of a result to the true value. This can be applied
to a single measurement, but is more commonly applied to the mean value of several
repeated measurements, or replicates.

Precision:

Precision is defined as the extent to which results agree with one another. In other
words, it is a measure of consistency, and is usually evaluated in terms of the range
or spread of results. Practically, this means that precision is inherently related to
the standard deviation of the repeated measurements.

When referring to the consistency between individual values amongst a set of replicate
measurements performed by the same person, at the same time on the same sample,
using the same method, this is termed the measurement repeatability.

When referring to the consistency of a method as used by different analysts,

laboratories, and/or over an extended time period, this is termed the reproducibility.

Note that accuracy and precision are separate things: while we would prefer to have
results that are both accurate and precise (left), it is entirely possible to have results that
are accurate but not precise (centre), as well as results that are precise but not accurate
(right).
Common Questions:

One way to demonstrate the importance of statistics in analytical chemistry is to look at

some of the common questions asked about measurement results, and the statistical
techniques we can use to answer them.

When I repeat a measurement, I get different numbers; which do I use?

Calculate the mean and standard deviation of the values; this is the starting point for
any statistical evaluation of your data. Remember that the inherent variation
associated with any real measurement means you would expect to get somewhat
different values for replicate measurements.

One of the values is quite different from the others; can I simply ignore it?

This depends on the range of the values you obtained, how different the suspect
value is from all the others, and how close the remaining results are to one another.
Use either Dixon's Q test or Grubb's test on the data.

Did I get the ‘right’ answer?

It’s almost impossible to answer this question in any meaningful way for real
samples! If you know what the true value is, you can assess whether your result is
significantly different using a t-test. If you don’t know the true value (or an accepted
true value), you have to determine the range either side of your measurement within
which the true value most probably lies. This is called the confidence interval, and is
a measure of the uncertainty associated with your measurement.

One sample gives a value of 2.1, the other gives 2.2; these are different values,
right?

This depends on the uncertainty associated with each measurement. You will need to
perform a significance test in order to determine whether the values can be
considered the same or different. You should test whether there is a significant
difference in the spread (standard deviation) of replicate measurements for each
sample (use the F-test) as well as the mean values themselves (use a pooled t-test).