12/26/2014

STATISTICAL CALCULATIONS TO ESTIMATE THE UNCERTAINTY OF ANALYTICAL RESULTS

Analysis of Variance (ANOVA)

Sample N03

Test 1
Test 2
B
B

I
100.0
103.9
203.9
41575

II
104.8
104.0
208.8
43597

III
101.9
103.0
204.9
41984

Table I. Tabulation of experimental results

x (g /100g)
BATCH
IV
V
VI
VII
VIII
103.8
100.2
99.5
102.9
203.3
203.1
41331
41250

S Row
IX

SB =
S B =
S X
S B / n
(S B) / mn

Where x = the experimental result

m= 5
n= 2

1024
209737
104890
104869
104858

Table II. Calculation of within-batch and between-batch mean squares

Source of
Sums of Squares
Degrees of
Mean Squares
variability
freedom
Between-Batch SS1 = S B / n -(S B)/mn N1 = m-1
M1 = SS1 / N1
Within-Batch
SSo = S X - S B / n
No = m(n-1)
Mo = SSo / No
Total
SSt = S X - (S B) /mn
Nt = mn-1
Source of
variability

Solution

Between-Batch

Sample N03

Within-Batch
Total

Sums of Squares

Degrees of
freedom

11.0
21.4
32.4

4
5
9

Mean Squares
M1 =
Mo =

2.75
4.28
-

The mean squares, M1 and Mo, are next compared to determine whether M1 is significantly greater that Mo,
That is, whether there is a statistically significant between-batch source of error. For this purpose, the standard
variance-ratio test (F-test) is used.
If Sw, Sb and St are the estimates of the within-batch, between-batch and total standard deviation, respectively then:
Sw = Mo

Sample
Sample N03

Sb = (M1 - Sw) / n

M1
2.75

Mo
4.28

St = (M1 + (n-1) Mo) / n

Table III. Calculation of Variances

F=Mo/M1 F0.05 one-tailed F0.01 one-tailed Signif.
1.56
5.19
11.39
No

Sw
4.28

Sb
0.0

St
4.28

* M1<Mo In this case Mo is divided by M1 to give the variance ratio F.

If F < F0.05 the between batch variance is equated to zero, and Mo is equated to the total variance.
If F > F0.05 the method and technique should be subjected to a critical scrutiny to reveal any abnormal source of error
Table IV. Calculation of Standard Deviations, Mean and expanded uncertainty (U)
Sw
Sb
St
Sample
Mean RSDRI
U
Sample N03
2.07
0.00
2.07
102.4 0.0202
4.1

U = k x RSDRI x Mean
k = a coverage factor 2, corresponds to a confidence level of 95%