AATQA Lecture 14: Statistics

Lecture 3 – t-tests
Presented by:
Dr Sherif Fahmy (Assistant Professor of Chemistry)
s.fahmy@gaf.edu.eg

Based on slides by Dr Eman Mohamed &Dr Mark Scott

 Learning Outcomes: Statistical Treatments
Be able to recognize which test is needed for a particular situation,
calculate, and interpret the results using the null hypothesis.
1. Types of Error
2. Dixon’s Test (Q) – gross errors
3. Standard Deviation (s) – precision (closeness) of a small set of data.
4. Confidence Interval (CI)-how confident are we that we contain the
population mean (μ).
5. Comparison of the precision of measurements-F Test
6. Comparison of an experimental mean with a population mean (μ).
7. Comparison of two experimental means-with pooled s.
8. Using the tables when Comparing: One-tailed vs. Two tailed test- Are
we expecting a change in one direction (more or less).
9. Comparison of two sets of data with varying analyte-The paired T-
Test.
10. Propagation of Error
6. Comparison of an experimental mean with a population
mean (μ).
Population
Experiment
6. Comparison of an experimental mean with a population
mean (μ).
• A common way of testing for bias (systematic error) of an
analytical method.

x
x = mean
=accepted value
t = calculated t value
s = standard deviation t n
n = number of measurements
s
If tcalc < tcrit then there is no significant difference between the
values
Example The researcher suspects the HPLC has
Calculation developed a fault, but must evaluate this
using a statistical method.

Over a 3 month period the standard

solution of methylprednisolone when
analysed by HPLC gave a peak area of
50,000 from counts (n)>50; σ = 555
The same solution is giving an average peak
yesterday with an area of 44,000 from 3
runs, s= 644

What is the Null Hypothesis?

What tests should be performed?
• F-test

Fcalc = ( 644)2 = 1.346

( 555)2

Fcrit [95%, 2/∞] = 4.461

Fcrit is actually 3.18, nearest
to it on the table is 4.461

Fcalc < Fcrit Therefore null hypothesis holds and we can compare
the two results.
 x
t n
s
tcalc = ?

tcrit [n-1=2, 95%] = _______

|tcalc| < or = or >|tcrit|

Null Hypothesis?
 x
t n
s

tcalc = 44000 – 50000 √3

644
tcalc = - 16.1 → |tcalc| = 16.1
tcrit [n-1=2, 95%] = 4.30

|tcalc| > tcrit

Therefore the null hypothesis is rejected and the HPLC

probably has developed a fault.
7. Comparison of two experimental
means – “True” value not known

Experiment 1 Experiment 2
 7. Comparison of two experimental
means – Use pooled standard deviation
• If there is no accepted value for the mean then the two experimental
means are compared, t can be determined with n1+n2-2 degrees of
freedom, i.e. one degree of freedom is lost for each set of results.

x is the mean of n1 determinations

y is the mean of n2 determinations
s* is the pooled standard deviation

If tcalc does not exceed tcrit then there is no significant difference between the
means
 Pooled Standard Deviation

• When several small sets have the same sources of

indeterminate error (i.e. the same type of
measurement but different samples) the standard
deviations of the individual data sets may be pooled
to more accurately determine the standard deviation
of the analysis method.

s
 (x i
 x ) 2   ( x  x ) 2  ............ ( x  x ) 2
1 i 2 i k

N K

s 2

(n 1) s  (n
1
2
1 2
2
1) s 21  .......(n k 1) s k
2
 Where k is the no.
of data sets
n1  n 2  .........n k  k
Pooled Standard Deviation (when you have two data sets)

s2 = (n1-1)s12 + (n2-1)s22 / n1 + n2 -2

s=
 Two Students A & B were asked to titrate
Example the same solution separately to check the
Calculation robustness of a method.

Student A obtained from 3 titrations an average titre of

22.6 cm3 with a standard deviation of 0.5 cm3.
Student B obtained from 6 titrations an average titre
of 24.02 cm3 with a standard deviation of 0.07 cm3.
Do the two students’ results agree within 95%
confidence?
What is the Null Hypothesis?
What tests need to be performed?
x1 = 22.6 cm3 x2 = 24.02 cm3
s1 = 0.5 cm3 s2 = 0.07 cm3
n1 = 3 n2 = 6
1. Carry out F-test first √

2. Calculate Pooled Standard Deviation

s=

S2 = 2 x 0.52 + 5 x 0.072 = 0.5 + 0.0245 = 0.0749

3+6-2 7

Therefore pooled standard deviation s* =

= 0.27 cm3
 3. Now work out tcalc :

x1 = 22.6 cm3 x2 = 24.02 cm3

n1 = 3 n2 = 6

tcalc = 24.02 - 22.6__

0.27 x

= 1.42___ = 1.42_
0.27 x 0.707 0.191

= 7.43
tcrit [n1+n2-2 =7 , 95%] = 2.36

|tcalc| = 7.43 so

tcalc > tcrit

i.e. null hypothesis is

rejected. The students
titration results are
significantly different at
the 95% level, and also at
the 99% confidence level.
 Reading

• Essential Statistics for

the Pharmaceutical
Sciences
– Confidence Interval
(pages 49 – 56)
– Hypothesis Testing
(pages 67 – 75)

• 'Analytical Chemistry',
G. A. Christian, 6th Edn,
Wiley, 2007. Chapter 3
pp 65 – 123.