Homework

Fundamentals of
Analytical Chemistry

4, 5, 7, 11, 15

Chapter 7
Statistical Data Treatment and
Evaluation

Only starred (*) parts!

We will only discuss the following sections

from Chapter 7

D Detection of Gross Errors

A Confidence Intervals
B Statistical Aids to Hypothesis Testing

Detection of Gross Errors

Only 100% guaranteed method for

rejecting a point because of gross error is
if you KNOW that you made a mistake!
Q-test

Qexp =

Largest or smallest point in a data set

xq = outlier

xn = nearest value to outlier

w = range

Qexp is then a value for comparison

Statistical test based on Gaussian distribution

of data

xq xn

Assumption that gross error leads to an

outlier
outlier

Q test

Largest or smallest value

Largest smallest

Q test

Q test is a null hypothesis test

Assume point is valid unless shown otherwise

Q test

Trends in Qcrit

To do the Q test we must compare Qexp

to Qcrit

Found in table of Qcrit values (Table 77-5)

Value depends on number of measurements
AND the confidence level
If Qexp > Qcrit then reject the outlier

Treat data as if the point never existed

Do not use for mean, standard deviation, or any
other calculation for the data set!

As number of observations increases, Qcrit

decreases

As confidence level increases, Qcrit increases

More measurements more reliable the data for

comparison
Interval must contain more points to insure that
we do not reject a good
good point (one for which
there was not a gross error

Use extreme caution when rejecting data with

the Q test

Q test Limitations

Statistical test

Goal for sample statistics is to determine

population values

More difficult to determine

90% confidence level for rejection still means

a 10% chance that a good point was rejected

Mathematical limitation

Confidence Intervals

3 data points with 2 points the same value

Q test will always predict rejection

We
Weve seen how can be approximated by s
Impossible would be a better term
We can define a range of values which will
probably
probably include
Probably in a statistical sense
Based on Gaussian distribution of data

Called the confidence interval
interval (ci)
ci)

CI when is known

For a single measurement

CI for = x z
z comes from area under Gaussian curve

Limitations

% confidence level is % area defined by z

Very unusual to use a single measurement

For a series of measurements

= x

We assume no bias (systematic error) in

measurements
Assume that s is a good approximation
of

Symbolized by s >
Not usually true

z
N

CI when is not known

Must have a greater interval

Equation for t in book

We will use tt-table (Table 77-3) to determine

the appropriate value for t

Confidence interval

= x

CI when is not known

Function of % confidence level (like z) and

number of degrees of freedom (unlike z)

Possible from pooled data

Not always!

Note similarity to equation for when is

known

At a given probability level, t is always equal

to or larger than z

t = z ONLY when the degrees of freedom =

ts
N

Comparison of Means

Two possibilities

Only possibility of (significant) error is for

the sample

Calculate

True value is known

Comparison of measured values

The question is if any difference in two

numbers is attributable to random error.

Comparison to a True Value

Are the numbers significantly

significantly different?

When both values for comparison are

measured, then you must account for
random error in both means!
Calculate

x1 x 2
t exp =

s pooled

XX depends on how you chose your t value

F test
Calculate

N1 N 2
N1 + N 2

Again, if texp > ttable there IS a significant

difference at the XX% confidence level.

Comparison of Standard Deviations

If texp > ttable then there IS a demonstrated

difference at the XX% probability level

Comparison of Two Means

t exp =

Fexp =

s22
s12

For this test, s2 > s1

Fcrit from Table 77-4

Note must use degrees of freedom for both

numerator and denominator