Homework

4, 5, 7, 11, 15
Fundamentals of
Only starred (*) parts!

Analytical Chemistry

We will only discuss the following sections
Chapter 7 from Chapter 7

D – Detection of Gross Errors
Statistical Data Treatment and
Evaluation
A – Confidence Intervals

B – Statistical Aids to Hypothesis Testing

Detection of Gross Errors Q – test

Only 100% guaranteed method for
xq − xn
rejecting a point because of gross error is
Qexp =
w
if you KNOW that you made a mistake!

Q-test
xq = outlier

Largest or smallest value

Assumption that gross error leads to an
‘outlier’
outlier’
xn = nearest value to outlier

Largest or smallest point in a data set
w = range

Largest – smallest

Statistical test based on Gaussian distribution
of data
Qexp is then a value for comparison

Q – test Q – test

Q – test is a null hypothesis test
Trends in Qcrit

Assume point is valid unless shown otherwise
As number of observations increases, Qcrit

To do the Q – test we must compare Qexp decreases

More measurements – more reliable the data for
to Qcrit comparison

Found in table of Qcrit values (Table 7-7-5)
As confidence level increases, Qcrit increases

Value depends on number of measurements
Interval must contain more points to insure that
AND the confidence level we do not reject a ‘good’
good’ point (one for which

If Qexp > Qcrit then reject the outlier there was not a gross error

Treat data as if the point never existed
Use extreme caution when rejecting data with

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

1
 Q – test Limitations

Statistical test

90% confidence level for rejection still means
a 10% chance that a good point was rejected

Mathematical limitation

3 data points with 2 points the same value

Q – test will always predict rejection
Confidence Intervals

Goal for sample statistics is to determine
population values

We’
We’ve seen how σ can be approximated by s

More difficult to determine µ

Impossible would be a better term

We can define a range of values which will
‘probably’
probably’ include µ

Probably in a statistical sense

Based on Gaussian distribution of data

Called the ‘confidence interval’
interval’ (ci)
ci)

CI when σ is known Limitations

For a single measurement
We assume no bias (systematic error) in

CI for µ = x ± zσ measurements

z comes from area under Gaussian curve
Assume that s is a good approximation

% confidence level is % area defined by ±z of σ

Very unusual to use a single measurement
Symbolized by s –> σ

For a series of measurements
Not usually true

Possible from pooled data
zσ Not always!

µ = x±

CI when σ is not known CI when σ is not known

Must have a greater interval
Note similarity to equation for when σ is

Function of % confidence level (like z) and known
number of degrees of freedom (unlike z)
At a given probability level, t is always equal

Equation for t in book to or larger than z

We will use t-
t-table (Table 7-
7-3) to determine
t = z ONLY when the degrees of freedom = ∞
the appropriate value for t

Confidence interval ts
µ = x±
N

2
 Comparison of Means Comparison to a True Value

Two possibilities
Only possibility of (significant) error is for

True value is known the sample

Comparison of measured values
x−µ

The question is if any difference in two
Calculate t exp = N
s
numbers is attributable to random error.

Are the numbers ‘significantly’
significantly’ different?
If texp > ttable then there IS a demonstrated
difference at the XX% probability level

XX depends on how you chose your t value

Comparison of Two Means Comparison of Standard Deviations

When both values for comparison are
F – test
measured, then you must account for s22

Calculate Fexp =
random error in both means! s12

x1 − x 2
For this test, s2 > s1

N1 N 2

Calculate t exp =
s pooled N1 + N 2

Fcrit from Table 7-
7-4

Again, if texp > ttable there IS a significant
Note must use degrees of freedom for both
difference at the XX% confidence level. numerator and denominator