Lecture 2

Affects measurements precision

Can be minimized and controlled, but NEVER

ELIMINATED!
Due to small and uncontrollable variables, which are
usually not even known
Inevitably part of every analysis
Accumulative effect causes replicate measurements to
fluctuate randomly around the mean of the set
Generally follow a Gaussian Distribution (random or
normal distribution)
Sometimes positive, sometimes negative
Can be minimized by replicate analyses

 Can be evaluated by the methods of statistics

Is done based on the assumption that random errors in

an analysis follow a Gaussian or normal distribution

Significant departures from Gaussian behaviour can and

do occur, but not often

Gaussian is based on normally distributed random errors

 Defines the distribution of random error in events or

measurements
equal probability of "high" value and "low" value
Can also be used in conjunction with the standard deviation.

 - population mean
- population standard deviation

 A sample of data is a finite number of experimental

observation
The sample is treated as a tiny fraction of an infinite
number of observations
The theoretical infinite number of data is a population
or a universe of data
Statistical laws have been derived assuming a
population data
However, modifications have to be made when applied
to a small sample
N.B. The difference between a statistical sample and a

chemical sample, chemical samples typically make up

a statistical sample of the population of interest

 This is a measure of precision of a population of data

standard deviation, large data set
N

2
(
x

)
i
i 1

where
population mean
N: number of replicate making up the population

The mean occurs at the central

point of maximum frequency
There is a symmetrical
distribution of positive and
negative deviation about the
maximum
There is an exponential decrease
in frequency as the magnitude of
deviation increases
The standard deviation indicates
precision
(i.e. B = 2A, therefore precision
associated with
curve B is half that of curve A.

The curves are

normalized wrt (x
axis shows deviation
from mean in units of
).
Therefore, all
Gaussian
curves plotted in this
way are identical.

# of Standard
Deviations from the
Mean

% of Events Affected
by Random Error that
Occur

+/- 1 STD DEV

68.3 %

+/- 2 STD DEV

95.5 %

+/- 3 STD DEV

99.7 %

 Standard Deviation defines a distribution of results

around the mean.

Smaller standard deviation = greater precision

Values are generally closer to the mean and

themselves

 The standard deviation of each mean is known as the

standard error of the mean and is given the symbol, S m

Sm = S/N

The Standard error is inversely proportional to the square

root of the number of data, N

 For analyses that are time consuming this

is not practical
Samples accumulated over time can be
pooled to provide an estimate of s that is
superior to the value for any individual
subset
We must assume the same random error in
all measurements
Valid when samples have similar
composition and analysed in the same way

 Variance

s2

2
(
x

x
)
i
i 1

N 1

Relative standard deviation

s
%RSD = x 1000ppt
x
Coefficient of variation

s
%CV = x 100%
x

 A sample of saliva is analyzed for NNN (n-

nitrosonornicotine), and it is found to contain 1.0, 2.0,

3.0, 2.4, 2.5 ppm NNN.

USING your calculator, determine the mean, standard

deviation and then %RSD for this analysis.

Calculate the following:

1. Mean
2. Range
3. Standard deviation
4. Relative standard deviation
5.
If the accepted value is 70.30 calculate, Relative error of the mean in ppt

 Alternative equation for standard deviation

Never round a standard deviation calculations until the very end

Never use this equation to calculate the standard deviation of
numbers containing five or more digits

Statistical Data Treatment and

Evaluation
Confidence limits
Confidence interval
Null hypothesis
F-test
Q-test