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Recommended textbook:
³Statistics for Analytical Chemistry´ J.C. Miller and J.N. Miller,
Second Edition, 1992, Ellis Horwood Limited
³Fundamentals of Analytical Chemistry´
Skoog, West and Holler, 7th Ed., 1996
(Saunders College Publishing)
!!
O
analysis for quality control, and ³reverse engineering´
(i.e. finding out what your competitors are doing).
v
familiar to those who attended the second year
³Environmental Chemistry´ modules. A very wide range of problems and
types of analyte
Select sample
Extract analyte(s) from matrix
Separate analytes
Impossible to Y Yerrors.
How reliable are our data?
Data of
quality are useless!
he middle result when data are arranged in order of size (for even
numbers the mean of middle two). Median can be preferred when
there is an ³ Y´ - one reading very different from rest. Median
less affected by outlier than is mean.
$
%
$
%
Results of 6 determinations of the Fe(III) content of a solution, known to
contain 20 ppm:
: he
value is 19.78 ppm (i.e. ) - the
value is
#
ð ð
ð ð
v 100%
ð
(latter is more useful in practice)
& $
%
$! %
V V
V V
enzyl isothiourea
hydrochloride
V
Analyst 4: imprecise, inaccurate
Analyst 3: precise, inaccurate Nicotinic acid
Analyst 2: imprecise, accurate
Analyst 1: precise, accurate
ypes of Error in Experimental
Data
hree types:
(1)
! v
Data scattered approx. symmetrically about a mean value.
Affects precision - dealt with statistically (see later).
his is a
A very large number of " or
random uncertainties
curve.
Symmetrical about
the mean.
' !
)
*+#!
% /0 % /0 % /0
A Gaussian curve with the same mean value, the same precision (see later)
and the same area under the curve as for the histogram.
#|v A finite number of observations
#,#-| , A total (infinite) number of observations
Properties of Gaussian curve defined in terms of population.
hen see where modifications needed for small samples of data
Î
±! - defined on next overhead
± : measure of ! of a population of data,
given by:
o ( ð )2
1
±
(ð ) 2 / 2± 2
Y
± 2
wo Gaussian curves with two different
standard deviations, ±A and ± (A2±A)
here are 68.3 chances in 100 that for a single datum the
random error in the measurement will not exceed ±.
he chances are 95.5 in 100 that the error will not exceed ±.
!
) .
/
he equation for ± must be modified for small samples of data, i.e. small
o ( ð ð)2
1
1
wo differences cf. to equation for ±:
( ð ) 2
2 1
( ð )
1
1
0 NEVER round off figures before the end of the calculation
Reproducibility of a method for determining
Î
the of selenium in foods. 9 measurements
were made on a single batch of brown rice.
Sample Selenium content (6g/g) (xI) xi2
1 0.07 0.0049
2 0.07 0.0049
3 0.08 0.0064
4 0.07 0.0049
5 0.07 0.0049
6 0.08 0.0064
7 0.08 0.0064
8 0.09 0.0081
9 0.08 0.0064
0.0533 0.0529
Standard deviation: 0.00707106 0.007
9 1
Coefficient of variance A 9.2 Concentration A 0.077 ± 0.007 6g/g
v
# )
Suppose that there are small sets of data, comprising 1, 2,«.t measurements.
he equation for the resultant sample standard deviation is:
1 2 3
( ð ð1 ) 2 ( ð ð2 ) 2 ( ð ð3 ) 2 ....
1 1 1
Y
1 2 3 ......
Bo t t l e ugar w o . o f o b s. e ia t io n s f r o ean
. . . .
. . 6 . . . 6
. . . . . .
.6 . . . 6 .
. . . .
6 . 6 . 6 . . .
( . ) ( . ) ( . ) .
. .
( ð2 ð)2
2 1
á ( ) 100
ð
â
How can we relate the observed mean value ( ð ) to the true mean (6)?
We can calculate the limits (above and below) around ð that 6 must lie,
,')vv|
interval around the mean that probably contains 6.
,')vv v'1|
the magnitude of the confidence limits
,')vv|v1v|
fixes the level of probability that the mean within the confidence limits
What this means, for example, is that 80 times out of 100 the YY will lie
between 1.29± of any measurement we make.
or ð ±
/
0 3 4
50 0.67
68 1.0
80 1.29
90 1.64
95 1.96
96 2.00
99 2.58
99.7 3.00
99.9 3.29
(164
. )(0.32) (164
. )(0.32)
90 CL 8.53 8.53 0.52 6g / ml 90 CL 8.53 8.53 0.266g / ml
1 4
i.e. 8.5 0.56g / ml i.e. 8.5 0.36g / ml
(164
. )( 0.32)
90 CL 8.53 8.53 0.136g / ml
16
i.e. 8.5 0.16g / ml
(c)
(2.58)(0.32)
99 CL 8.53 8.53 0.216g / ml
16
i.e. 8.5 0.2 6g / ml
If we have no information on ±, and only have a value for s -
the confidence interval is larger,
i.e. there is a greater uncertainty.
Instead of , it is necessary to use the parameter , defined as follows:
A (ð- 6)/
i A 21.72 i2 A 1 7.3742
o i
2172
.
7.24
3
( o ð ) 2 . )2
oð 2
157.3742
(2172
3 90% ð 7.24
(2.92)(0.25)
3
1 2
0.246 0.25% 7.24 0.42%
(164
. )( 0.28)
If repeated analyses showed that s ]± A 0.28 : 90 ð ± 7.24
3
7.24 0.27%
5
ð ð
ut t (from able) A 4.30, s (calc. above) A 0.943 and N A 3
1 2
ð1 ð2
Y
1 2
Only if the difference between the two samples is greater than the term on
the right-hand side can we assume a real difference between the samples.
& &
1 2 1 2 - i. e . ( 3.3 6 )( 0 .2 6 7 ) 1 0 2 5
i.e. ± 0.5674, or ±0.57 6g/g.
u t ð1 ð 2 2 8 .0 2 6 .2 5 1 .7 5 6 g / g
i. e . ð 1 ð 2
Y 1 2 1 2
6Yð ð ð
6 e x p 0 .3 8 0 0 .4 0 0 ( 0 .4 1 3 0 .3 8 0 ) 0 .6 0 6
ut Qcrit A 0.568 (at 95 level) for 7 values
herefore, Qexp > Qcrit, and rejection of 0.380 is recommended.
ut note that 5 times in 100 it will be wrong to reject this suspect value!
Also note that if 0.380 is retained, s A 0.011 mg/l, but if it is rejected,
s A 0.0056 mg/l, i.e. precision appears to be twice as good, just by
rejecting one value.
,
!
.
!
' Y Y
Y Y Y Y
YY Y YY
Y Y
Y
Sample in porous
thimble.
Exhaustive reflux for
up to 1 - 2 days.
Solution of analyte(s)
in volatile solvent
(e.g. CH2Cl2, CHCl3 etc.)
Evaporate to dryness or
suitable concentration,
for separation/analysis.