Tests of Significance

In this section we deal with two tests used for

comparing two analytical methods, one is a new
or proposed method and the other is a standard
method. The two methods are compared in
terms of whether they provide comparable
precision ( the F test ), based on their standard
deviations or variances. The other test ( t test )
tells whether there is a statistical difference
between results obtained by the two methods.

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 The F Test
The precision of two methods could be compared
based on their standard deviations using the F
test which can be defined as the ratio between
the variances ( the variance is the standard
deviation squared ) of the two methods. The
ratio should always be larger than unity. That is,
the larger variance of either method is placed in
the nominator.

F = S12/S22

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Where, S12 > S22

Values of F ( a statistical factor ) at different

confidence levels which can be obtained
from statistical F tables. When Fcalculated <
Ftabulated this is an indication of no
statistical difference between precision or
variances of the two methods.

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 n1

n2

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 Example
In the analysis of glucose using a new
developed procedure and a standard
procedure, the variances of the two
procedures were 4.8 and 8.3. If the
tabulated F value at 95% confidence level
at the number of degrees of freedom used
was 4.95. Determine whether the variance
of the new procedure differs significantly
from that of the standard method
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F = S12/S22

F = 8.8/4.8 = 1.73 (the subscript is because

the answer is less than the key number)
Since Fcalculated < Ftabulated there is no
significant statistical difference between
the variances of the two methods (i.e.
there is no significant statistical difference
between the precision of the two
methods).
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 The Student t Test
To check whether there is a significant statistical
difference between the results of a new or
proposed procedure and a standard one, the t
test is used. As we did above, we calculate t and
compare it to the tabulated value at the required
confidence level and at the used degrees of
freedom. There is no significant statistical
difference between the results of the two
methods when tcalculated < ttabulated .
There are three situations where the t test is
applied:
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8
a. When an Accepted Value is Known

The tcalc is calculated from the relation below

and compared to ttab

m = x + ts/N1/2 or more conveniently,

+ t = (x - m) N1/2/s

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 Example

A new procedure for determining copper was used

for the determination of copper in a sample. The
procedure was repeated 5 times giving an
average of 10.8 ppm and a standard deviation of
+0.7 ppm. If the true value for this analysis was
11.7 ppm, does the new procedure give a
statistically correct value at the 95% confidence
level? ttab = 2.776
•

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Substitution into equation below, we get:
+ t = (x - m) N1/2/s
+ t = (10.8-11.7) 51/2/0.7
+ t = 2.9
the tcalc is larger than the ttab. Therefore,
there is a significant statistical difference
between the two results which also means
that it is NOT acceptable to use the new
procedure for copper determination.
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b. Comparison between two means

When an accepted value is not known and the

sample is analyzed using the new procedure
and a standard procedure. Here, we have two
sets of data, a standard deviation for each
set of data and a number of data points or
results in each set. Under these conditions,
we use the pooled standard deviation for the
two sets. The same equation in a is used but
with some modifications. The t value is
calculated from the relation
( x1 – xs) (N1 Ns)1/2
+t= *
Sp (N1+ Ns)1/2
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Where, x1 and xs are means of
measurements using the new and
standard methods. N1 and Ns are number
of replicates done using the new and
standard methods, respectively. Sp is the
pooled standard deviation.
In such calculations it is wise to apply the F
test first, and if it passes the t test is then
applied.

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 Example
Nickel in a sample was determined using a
new procedure where six replicate
samples resulted in a mean of 19.65% and
a variance of 0.4524. Five replicate
analyses where conducted using a
standard procedure resulting in a mean of
19.24% and a variance of 0.105. If the
pooled standard deviation was +0.546, is
there a significant difference between the
two methods?
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First, let us find whether there is a significant
difference in precision between the two
procedures, by applying the F test

F = 0.4524/0.105 = 4.31

The tabulated F value is 6.26. Since Fcalculated <

Ftabulated , then there is no significant statistical
difference between the precision of the two
procedures. Therefore, we continue with
calculation of t test.

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 ( x1 – xs) (N1 Ns)1/2
+t=
Sp
* (N1+ Ns)1/2

( 19.65 – 19.24) (6*5)1/2

+t=
0.546
* (6+ 5)1/2

+ t = 1.23

The tabulated t value is 2.262. Since tcalculated <

ttabulated for nine degrees of freedom at 95%
confidence level, we conclude that there is no
significant statistical difference between the
results of the two methods.
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