Book of Reference Examples Validation With Statistic

1999-2011
BOOK OF REFERENCE EXAMPLES

EFFIVALIDATION 3
EffiChem
your validation software
Lesn 593, 679 71 Lysice, Czech Republic

http://www.effichem.com
2/56
EffiChem may have patents and/or pending patent applications covering subject matter in this document. The furnishing of
this document does not convey any license to these patents.
Copyright 2008 EffiChem. All rights reserved. All EffiValidation products are trademarks or registered trademarks of
EffiChem. Other brand and product names are trademarks or registered trademarks of their respective holders.
5/2/2011
Book of Reference Examples EffiValidation 3.0
document version: 1.03
3/56
Content:
FOREWORD ......................................................................................................................................................... 5
OUTLIERS AND NORMALITY TESTS ........................................................................................................... 6
1.1 COCHRAN TEST .............................................................................................................................................. 6
1.2 GRUBBS SINGLE TEST .................................................................................................................................... 6
1.3 GRUBBS PAIR TEST ........................................................................................................................................ 7
1.4 DIXON TEST ................................................................................................................................................... 7
1.5 NORMALITY TEST .......................................................................................................................................... 8
VALIDATION ....................................................................................................................................................... 9
2.1 REPEATABILITY.............................................................................................................................................. 9
2.1.1 Level by Level from Multiple Measurements .......................................................................................... 9
2.1.2 From Parallel Measurements ............................................................................................................... 10
2.2 INTERMEDIATE PRECISION ........................................................................................................................... 11
2.3 REPRODUCIBILITY ........................................................................................................................................ 11
2.3.1 Data Available ..................................................................................................................................... 11
2.3.2 Results Available .................................................................................................................................. 12
2.4 ROBUSTNESS ................................................................................................................................................ 12
2.5 ACCURACY................................................................................................................................................... 13
2.5.1 Limited Concentration Range Sample Reconstitution Possible ........................................................ 13
2.5.2 Limited Concentration Range Reference Material Available ........................................................... 14
2.5.3 Large Concentration Range Blank Material Available: T-test ......................................................... 15
2.5.4 Large Concentration Range Blank Material Available: Regression ................................................. 16
2.5.5 Large Concentration Range Blank Material Not Available: T-test ................................................... 16
2.5.6 Large Concentration Range Blank Material Available: Regression ................................................. 17
2.5.7 Comparison of 2 Methods / Laboratories: T-test Level by Level ......................................................... 18
2.5.8 Comparison of 2 Methods / Laboratories: T-test on Difference of Results .......................................... 19
2.6 SELECTIVITY ................................................................................................................................................ 20
2.6.1 Comparison of Calibration Lines ......................................................................................................... 20
2.6.2 Comparison of Results with a Standard ............................................................................................... 20
2.6.3 Comparison of Results with Measurements Without the Interference .................................................. 21
2.7 SENSITIVITY ................................................................................................................................................. 22
2.7.1 From Calibration Line ......................................................................................................................... 22
2.7.2 Minimal Difference in the Validated Property ..................................................................................... 23
2.8 LINEARITY ................................................................................................................................................... 24
2.8.1 Correlation and QC coefficient ............................................................................................................ 24
2.8.2 ANOVA for Lack of Fit ......................................................................................................................... 25
2.8.3 Significance of the Quadratic Term F-test ........................................................................................ 26
2.8.4 Sign test ................................................................................................................................................ 27
2.9 RANGE ......................................................................................................................................................... 28
2.10 LIMIT OF DETECTION AND LIMIT OF QUANTIFICATION .............................................................................. 28
2.10.1 3s - IUPAC ....................................................................................................................................... 28
2.10.2 3s Every Sample Corrected for Blank ........................................................................................... 29
2.10.3 3s Continuously Measured Blank .................................................................................................. 29
2.10.4 From Calibration Line ...................................................................................................................... 30
2.10.5 From Signal of Blank in Chromatography ........................................................................................ 31
2.11 BLANK ....................................................................................................................................................... 31
2.12 REPEATABILITY OF INJECTION FDA ....................................................................................................... 32
2.13 CAPACITY FACTOR - FDA ......................................................................................................................... 33
2.14 RESOLUTION - FDA ................................................................................................................................... 34
2.15 TAILING - FDA .......................................................................................................................................... 34
2.16 THEORETICAL PLATE NUMBER FDA ...................................................................................................... 35
INTERLABORATORY COMPARISON ......................................................................................................... 36
3.1 MANDEL STATISTICS H ................................................................................................................................ 36
3.2 MANDEL STATISTICS K ................................................................................................................................ 37
3.3 COLLABORATIVE STUDY .............................................................................................................................. 38
5/2/2011
4/56
CONTROL CHARTS ......................................................................................................................................... 39

4.1 INDIVIDUAL MEASUREMENTS CHARACTERISTICS DETERMINED ............................................................... 39
4.2 INDIVIDUAL MEASUREMENTS CHARACTERISTICS NOT DETERMINED ....................................................... 41
4.3 REPEATED MEASUREMENTS CHARACTERISTICS NOT DETERMINED ........................................................... 43
4.4 REPEATED MEASUREMENTS CHARACTERISTICS NOT DETERMINED.......................................................... 45
CALIBRATION .................................................................................................................................................. 48
5.1 LINEAR CALIBRATION .................................................................................................................................. 48
5.2 QUADRATIC CALIBRATION ........................................................................................................................... 49
UNCERTAINTIES ............................................................................................................................................. 51
6.1 FROM PRECISION DATA MULTIPLE MEASUREMENTS ................................................................................ 51
6.2 FROM PRECISION DATA PARALLEL MEASUREMENTS ................................................................................ 52
6.3 FROM CONTROL CHART INDIVIDUAL MEASUREMENTS ............................................................................ 53
6.4 FROM CONTROL CHART REPEATED MEASUREMENTS ............................................................................... 54
6.5 EXPERT ESTIMATE ...................................................................................................................................... 55
6.6 FROM PARTIAL UNCERTAINTIES ................................................................................................................. 55
5/2/2011
5/56
FOREWORD
Book of Reference Examples EffiValidation 3.0 presents all main algorithms of the software. The book aims to
prove correct functionality of the software as a part of the software validation life cycle process.
For every important computational method implemented in the software, a reference example is presented,
summarizing the data, results, graphical results and the original data source.
The considered original data sources are international standards and other recognized sources, that can be treated
as reference sources.
Examples presented in this Book originate from the following literature:
- ISO 8466:1 and 2.
- ISO 8258:1991
- ISO 5725-2, 1997
- EURACHEM/CITAC Guide, Quantifying Uncertainty in Analytical Measurement, Second Edition, June 1999
- D.L. Massart et al., Handbook of Chemometrics and Qualimetrics, Part A, Elsevier, Amsterdam, 1997
- 19-th edition, Remington: Practice of The Science and Pharmacy, Mack Publishing Company, Easton, 1995
EffiChem
http://www.effichem.com
5/2/2011
Lysice 5.2. 2011
6/56
CHAPTER
1
OUTLIERS AND NORMALITY TESTS
1.1 COCHRAN TEST
Data source: D.L. Massart et al., Handbook of Chemometrics and Qualimetrics, Part A, Elsevier, Amsterdam,
1997, page 123, tab. 6.1.
Level
1
2
3
4
5
6
7
Measrt 1
5,59
5,67
5,75
4,74
5,52
5,52
5,43
Measrt 2
5,59
5,67
5,47
4,45
5,47
5,62
5,52
Measrt 3
5,37
5,55
5,43
4,65
5,66
5,47
5,43
Measrt 4
5,54
5,57
5,45
4,94
5,52
5,18
5,43
Measrt 5
5,37
5,43
5,24
4,95
5,62
5,43
5,52
Measrt 6
5,42
5,57
5,47
5,06
5,76
5,33
5,52
Window Results in EffiValidation 3.0:
1.2 GRUBBS SINGLE TEST

1997, page 112, chapter 5.5.2.
Measrt 1
22,1
5/2/2011
Measrt 2
22,4
Measrt 3
22,9
Measrt 4
23
Measrt 5
23,5
Measrt 6
23,7
Measrt 7
23,9
Measrt 8
26,5
7/56
1.3 GRUBBS PAIR TEST

1997, page 446, chapter 14.2.4.
Measrt 1
22,1
Measrt 2
22,4
Measrt 3
22,9
Measrt 4
23
Measrt 5
23,5
Measrt 6
23,7
Measrt 7
26,0
Measrt 8
26,5
1.4 DIXON TEST

1997, page 110, chapter 5.5.1.
Measrt 1
22,1
Measrt 2
22,4
Measrt 3
22,9
Measrt 4
23
Measrt 5
23,5
Measrt 6
23,7
Measrt 7
23,9
Measrt 8
26,5
5/2/2011
8/56
1.5 NORMALITY TEST

1997, page 118, Table 5.8.
Measrt
1
2,104
Measrt
2
2,222
Measrt
3
2,247
Measrt
4
2,286
Measrt
5
2,327
Measrt
6
2,367
Measrt
7
2,388
Measrt
8
2,512
Measrt
9
2,707
Measrt
10
2,751
Measrt
11
3,158
Measrt
12
3,172
5/2/2011
9/56
CHAPTER
2
VALIDATION
2.1 REPEATABILITY
2.1.1 LEVEL BY LEVEL FROM MULTIPLE MEASUREMENTS
Data source: 19-th edition, Remington: Practice of The Science and Pharmacy, Mack Publishing Company,
Easton, 1995, page 126, Table 43:
Table 43, formulation A

Table 43, formulation B
Measrt 1
1,431
1,813
Measrt 2
1,74
1,778
Measrt 3
1,519
1,991
Measrt 4
1,839
1,672
Measrt 5
1,556
1,756
Measrt 6
1,591
1,633
5/2/2011
10/56
2.1.2 FROM PARALLEL MEASUREMENTS

1997, page 30, Table 2.4:
Experiment
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Measrt 1
42,68
42,08
43,39
42,87
42,7
42,93
42,78
42,92
43,34
43,12
42,43
43,05
42,99
43,04
43,41
43,12
42,25
42,96
42,83
42,83
Measrt 2
42,77
42,38
43,33
42,98
42,95
42,95
42,97
43,2
42,89
43,26
42,54
43,15
42,86
42,78
43,14
43,23
42,53
42,78
42,72
43,04
5/2/2011
11/56
2.2 INTERMEDIATE PRECISION

Table 43, formulace A

Table 43, formulace B
Measrt 1
1,431
1,813
Measrt 2
1,74
1,778
Measrt 3
1,519
1,991
Measrt 4
1,839
1,672
Measrt 5
1,556
1,756
Measrt 6
1,591
1,633
2.3 REPRODUCIBILITY
2.3.1 DATA AVAILABLE
Table 43, formulace A

Table 43, formulace B
5/2/2011
Measrt 1
1,431
1,813
Measrt 2
1,74
1,778
Measrt 3
1,519
1,991
Measrt 4
1,839
1,672
Measrt 5
1,556
1,756
Measrt 6
1,591
1,633
12/56
2.3.2 RESULTS AVAILABLE

Data are not evaluated, but only archived in the database of EffiValidation 3.0.
2.4 ROBUSTNESS
Data source: not found. Data obtained by experimental measurements in a laboratory.
Number of factors: 5
Result
Factor 1
25,01
24,92
20,33
20,64
24,58
20,83
24,53
20,34
5/2/2011
Factor 2
1
-1
-1
1
-1
1
1
-1
Factor 3
1
1
-1
-1
1
-1
1
-1
Factor 4
1
1
1
-1
-1
1
-1
-1
Factor 5
-1
1
1
1
-1
-1
1
-1
1
-1
1
1
1
-1
-1
-1
Dummy 1 Dummy 2
-1
-1
1
-1
-1
1
1
-1
1
1
1
1
-1
1
-1
-1
13/56
Dummy factors considered in the calculation:

2.5 ACCURACY
2.5.1 LIMITED CONCENTRATION RANGE SAMPLE RECONSTITUTION POSSIBLE
1997, page 397, chapter 13.5.2.
Reference value
100
5/2/2011
Measrt 1
98,9
Measrt 2
100,3
Measrt 3
99,7
Measrt 4
99
Measrt 5
100,6
Measrt 6
98,6
14/56
2.5.2 LIMITED CONCENTRATION RANGE REFERENCE MATERIAL AVAILABLE

Reference value
50
Reference precision: 0,3
Measrt 1
50,45
Measrt 2
50,35
Measrt 3
50,11
Measrt 4
49,68
Measrt 5
50,01
Measrt 6
49,81
5/2/2011
15/56
2.5.3 LARGE CONCENTRATION RANGE BLANK MATERIAL AVAILABLE: T-TEST

1997, page 397, chapter 13.5.2.
Reference
100
Measrt 1
98,9
Measrt 2
100,3
Measrt 3
99,7
Measrt 4
99
Measrt 5
100,6
Measrt 6
98,6
5/2/2011
16/56
2.5.4 LARGE CONCENTRATION RANGE BLANK MATERIAL AVAILABLE: REGRESSION
1997, page 193, Table 8.6.
Sample
1
2
3
4
5
6
7
8
9
10
Measrt 1
35
75
75
80
125
205
205
215
240
350
Measrt 2
35
70
80
80
120
200
220
200
250
330
2.5.5 LARGE CONCENTRATION RANGE BLANK MATERIAL NOT AVAILABLE: T-TEST

1997, page 405, chapter 13.5.5.
Standard Addition
0
60
5/2/2011
Measrt 1
90
156
Measrt 2
90,8
154,2
Measrt 3
89,7
155,3
Measrt 4
89,2
155,6
Measrt 5
88,6
153,8
Measrt 6
91,2
154,7
17/56
2.5.6 LARGE CONCENTRATION RANGE BLANK MATERIAL AVAILABLE: REGRESSION

1997, page 210, chapter 8.2.9., example 9
Standard
1
2
3
4
5
6
7
Calibration
A*s
0
0,039
0,073
0,149
0,215
0,28
ug/l
0
41
81
162
244
325
Standard addition
ug/l added
A*s
0
0,05
41
0,083
81
0,122
122
0,161
162
0,179
203
0,215
325
0,313
5/2/2011
18/56
2.5.7 COMPARISON OF 2 METHODS / LABORATORIES: T-TEST LEVEL BY LEVEL

Sample
1
2
3
Method 1
Measrt 1
5,33
25,02
50,11
Method 1
Measrt 2
5,01
24,95
50,45
Method 1
Measrt 3
4,97
24,86
50,35
Method 2
Measrt 1
5,31
24,38
49,81
Method 2
Measrt 2
5,08
24,22
49,68
Method 2
Measrt 3
5,12
24,11
50,01
5/2/2011
19/56
2.5.8 COMPARISON OF 2 METHODS / LABORATORIES: T-TEST ON DIFFERENCE OF RESULTS

1997, page 411, Table 13.7.
Sample
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
Measrt 1
4,83
6,74
8,46
12,6
13,52
15,72
15,83
18,37
18,9
23,1
32,45
40,89
41,42
43,36
45,96
47,7
50,02
57,2
78,48
Measrt 2
4,63
7,39
8,76
11,85
13,67
15,8
16,05
18,22
18,79
22,8
32,53
41,03
41,52
43,7
45,89
47,81
50,11
57,51
79,38
5/2/2011
20/56
2.6 SELECTIVITY
2.6.1 COMPARISON OF CALIBRATION LINES
1997, page 210, chapter 8.2.9., Example 9
Standard
1
2
3
4
5
6
7
Calibration without interference

ug/l
A*s
0
0
41
0,039
81
0,073
162
0,149
244
0,215
325
0,28
Calibration with interference 1

ug/l added
A*s
0
0,05
41
0,083
81
0,122
122
0,161
162
0,179
203
0,215
325
0,313
2.6.2 COMPARISON OF RESULTS WITH A STANDARD

1997, page 397, chapter 13.5.2.
Reference
(without interference)
100
5/2/2011
With
interf. 1
98,9
With
interf. 2
100,3
With
interf. 3
99,7
With
interf. 4
99
With
interf. 5
100,6
With
interf. 6
98,6
21/56
2.6.3 COMPARISON OF RESULTS WITH MEASUREMENTS WITHOUT THE INTERFERENCE

Sample
1
2
3
Without interf.
Measrt 1
5,33
25,02
50,11
Without interf.
Measrt 2
5,01
24,95
50,45
Without interf.
Measrt 3
4,97
24,86
50,35
With interf.
Measrt 1
5,31
24,38
49,81
With interf.
Measrt 2
5,08
24,22
49,68
With interf.
Measrt 3
5,12
24,11
50,01
5/2/2011
22/56
2.7 SENSITIVITY
2.7.1 FROM CALIBRATION LINE
Data source: NIST, Norris, J, http://www.itl.nist.gov/div898/strd/lls/data/LINKS/DATA/Norris.dat
Sample
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
5/2/2011
Measrt 1
0,2
337,4
118,2
884,6
10,1
226,5
666,3
996,3
448,6
777
558,2
0,4
0,6
775,5
666,9
338
447,5
11,6
556
228,1
995,8
887,6
120,2
0,3
0,3
556,8
339,1
887,2
999
779
Measrt 2
0,1
338,8
118,1
888
9,2
228,1
668,5
998,5
449,1
778,9
559,2
0,3
0,1
778,1
668,8
339,3
448,9
10,8
557,7
228,3
998
888,8
119,6
0,3
0,6
557,6
339,3
888
998,5
778,9
23/56
31
32
33
34
35
36
11,1
118,3
229,2
669,1
448,9
0,5
10,2
117,6
228,9
668,4
449,2
0,2
2.7.2 MINIMAL DIFFERENCE IN THE VALIDATED PROPERTY

5/2/2011
24/56
2.8 LINEARITY
2.8.1 CORRELATION AND QC COEFFICIENT
1997, page 420, chapter 13.6.2., Table 13.9 and 13.10.
Sample
1
2
3
4
5
6
7
8
9
Measrt 1
0
0,4
0,8
1,2
1,6
2
2,4
2,8
3,2
Measrt 2
0
0,173
0,324
0,467
0,61
0,718
0,825
0,938
1,048
5/2/2011
25/56
2.8.2 ANOVA FOR LACK OF FIT

1997, page 185, chapter 8.2.2.2., Example 2, Table 8.3.
Sample
1
2
3
4
5
6
Val. property
0
1
2
3
4
5
Measrt 1
0
0,98
2,1
3,16
3,68
4,15
Measrt 2
0
0,9
2,2
3,22
3,72
4,27
5/2/2011
26/56
2.8.3 SIGNIFICANCE OF THE QUADRATIC TERM F-TEST

1997, page 420, chapter 13.6.2., Table 13.9 and 13.10.
Sample
1
2
3
4
5
6
7
8
9
Measrt 1
0
0,4
0,8
1,2
1,6
2
2,4
2,8
3,2
Measrt 2
0
0,173
0,324
0,467
0,61
0,718
0,825
0,938
1,048
5/2/2011
27/56
2.8.4 SIGN TEST

1997, page 420, chapter 13.6.2., Table 13.9 and 13.10. repeated twice
Sample
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
Measrt 1
0
0,4
0,8
1,2
1,6
2
2,4
2,8
3,2
0
0,4
0,8
1,2
1,6
2
2,4
2,8
3,2
Measrt 2
0
0,173
0,324
0,467
0,61
0,718
0,825
0,938
1,048
0
0,173
0,324
0,467
0,61
0,718
0,825
0,938
1,048
5/2/2011
28/56
2.9 RANGE
Range is not accessed but only archived in the database of EffiValidation 3.0:
2.10 LIMIT OF DETECTION AND LIMIT OF QUANTIFICATION

2.10.1 3S - IUPAC
1997, page 430, chapter 13.7.6.
Slope: 1
Measrt 1
0,025
Measrt 2
0,037
Measrt 3
0,012
Measrt 4
0,029
Measrt 5
0,048
Measrt 6
0,026
Measrt 7
0,024
Measrt 8
0,015
Measrt 9
0,041
Measrt 10
0,019
5/2/2011
29/56
2.10.2 3S EVERY SAMPLE CORRECTED FOR BLANK

1997, page 430, chapter 13.7.6.
Measrt 1
0,025
Measrt 2
0,037
Measrt 3
0,012
Measrt 4
0,029
Measrt 5
0,048
Measrt 6
0,026
Measrt 7
0,024
Measrt 8
0,015
Measrt 9
0,041
Measrt 10
0,019
2.10.3 3S CONTINUOUSLY MEASURED BLANK

1997, page 430, chapter 13.7.6.
Measrt 1
0,025
Measrt 2
0,037
Measrt 3
0,012
Measrt 4
0,029
Measrt 5
0,048
Measrt 6
0,026
Measrt 7
0,024
Measrt 8
0,015
Measrt 9
0,041
Measrt 10
0,019
5/2/2011
30/56
2.10.4 FROM CALIBRATION LINE

Data source: M. Meloun. J. Militk, Statistical evaluation of experimental data, Edice PLUS, Praha, 1994, page
498, chapter 6.7.2., Example 6.53
Sample
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
Measrt 1
2,5
5
7,5
10
12,5
15
17,5
20
22,5
25
27,5
30
32,5
35
37,5
40
Measrt 2
0,063
0,12
0,189
0,251
0,316
0,393
0,442
0,502
0,568
0,639
0,694
0,749
0,821
0,884
0,947
1,01
5/2/2011
31/56
2.10.5 FROM SIGNAL OF BLANK IN CHROMATOGRAPHY

2.11 BLANK
1997, page 430, chapter 13.7.6.
Measrt 1
0,025
Measrt 2
0,037
Measrt 3
0,012
Measrt 4
0,029
Measrt 5
0,048
Measrt 6
0,026
Measrt 7
0,024
Measrt 8
0,015
Measrt 9
0,041
Measrt 10
0,019
5/2/2011
32/56
2.12 REPEATABILITY OF INJECTION FDA

Easton, 1995, page 125 and 126, Table 42 and 43:
Table 43, formulation A

Table 43, formulation B
Measrt 1
1,431
1,813
Measrt 2
1,74
1,778
Measrt 3
1,519
1,991
Measrt 4
1,839
1,672
Measrt 5
1,556
1,756
Measrt 6
1,591
1,633
5/2/2011
33/56
2.13 CAPACITY FACTOR - FDA

Data obtained by experimental measurements in a laboratory.
5/2/2011
34/56
2.14 RESOLUTION - FDA

2.15 TAILING - FDA

5/2/2011
35/56
2.16 THEORETICAL PLATE NUMBER FDA

5/2/2011
36/56
CHAPTER
3
INTERLABORATORY COMPARISON
3.1 MANDEL STATISTICS H
Data source: ISO 5725-2, 1997, page 45, Table B.12:
Level:
Laboratory
1
2
3
4
5
6
7
8
9
1
1
4,44
4,03
3,7
4,1
3,97
3,75
3,7
3,91
4,02
2
4,39
4,23
3,7
4,1
4,04
4,03
3,8
3,9
4,07
2
1
9,34
8,42
7,6
8,93
7,89
8,76
8
8,04
8,44
2
9,34
8,33
7,4
8,8
8,12
9,24
8,3
8,07
8,17
3
1
17,4
14,42
13,6
14,6
13,73
13,9
14,1
14,84
14,24
2
16,9
14,5
13,6
14,2
13,92
14,06
14,2
14,84
14,1
4
1
19,23
16,06
14,5
15,6
15,54
16,42
14,9
15,41
15,14
2
19,23
16,22
15,1
15,5
15,78
16,58
16
15,22
15,44
5
1
24,28
20,4
19,3
20,3
20,53
18,56
19,7
21,1
20,71
2
24
19,91
19,7
20,3
20,88
16,58
20,5
20,78
21,66
5/2/2011
37/56
3.2 MANDEL STATISTICS K

Level:
Laboratory
1
2
3
4
5
6
7
8
9
1
1
4,44
4,03
3,7
4,1
3,97
3,75
3,7
3,91
4,02
2
4,39
4,23
3,7
4,1
4,04
4,03
3,8
3,9
4,07
2
1
9,34
8,42
7,6
8,93
7,89
8,76
8
8,04
8,44
2
9,34
8,33
7,4
8,8
8,12
9,24
8,3
8,07
8,17
3
1
17,4
14,42
13,6
14,6
13,73
13,9
14,1
14,84
14,24
2
16,9
14,5
13,6
14,2
13,92
14,06
14,2
14,84
14,1
4
1
19,23
16,06
14,5
15,6
15,54
16,42
14,9
15,41
15,14
2
19,23
16,22
15,1
15,5
15,78
16,58
16
15,22
15,44
5
1
24,28
20,4
19,3
20,3
20,53
18,56
19,7
21,1
20,71
2
24
19,91
19,7
20,3
20,88
16,58
20,5
20,78
21,66
5/2/2011
38/56
3.3 COLLABORATIVE STUDY

Level:
Laboratory
1
2
3
4
5
6
7
8
9
1
1
4,44
4,03
3,7
4,1
3,97
3,75
3,7
3,91
4,02
2
4,39
4,23
3,7
4,1
4,04
4,03
3,8
3,9
4,07
2
1
9,34
8,42
7,6
8,93
7,89
8,76
8
8,04
8,44
2
9,34
8,33
7,4
8,8
8,12
9,24
8,3
8,07
8,17
3
1
17,4
14,42
13,6
14,6
13,73
13,9
14,1
14,84
14,24
2
16,9
14,5
13,6
14,2
13,92
14,06
14,2
14,84
14,1
4
1
19,23
16,06
14,5
15,6
15,54
16,42
14,9
15,41
15,14
2
19,23
16,22
15,1
15,5
15,78
16,58
16
15,22
15,44
5
1
24,28
20,4
19,3
20,3
20,53
18,56
19,7
21,1
20,71
2
24
19,91
19,7
20,3
20,88
16,58
20,5
20,78
21,66
5/2/2011
39/56
CHAPTER
4
CONTROL CHARTS
4.1 INDIVIDUAL MEASUREMENTS CHARACTERISTICS DETERMINED
Data source: ISO 8258:1991, 1991, page 22, Table 6: data in the standard are shown for the control chart with
repetitions, number of repetitions n = 5. These data are used here, because other data for individual
measurements are not presented.
Determined Central line of the weight for the control chart of the packaging process is 100,6 g and standard
deviation is 1,4
Measrt N.
[1]
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
5/2/2011
Weight
[g]
100,6
101,3
99,6
100,5
99,9
99,5
100,4
100,5
101,1
100,3
100,1
99,6
99,2
99,4
99,4
99,6
99,3
99,9
100,5
99,5
100,1
100,4
101,1
99,9
99,7
40/56
X-chart (control chart for mean)

R-chart (control chart for range)
5/2/2011
41/56
4.2 INDIVIDUAL MEASUREMENTS CHARACTERISTICS NOT DETERMINED

Data source: ISO 8258:1991, 1991, page 27, Table 8: data shown in the ISO standard are data 1-10. Because the
application of Western-Electric rules requires min. 15 measurements, data in the table are repeated, resulting in
20 values.
Measrt N.
[1]
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
5/2/2011
Weight
[g]
2,9
3,2
3,6
4,3
3,8
3,5
3
3,1
3,6
3,5
2,9
3,2
3,6
4,3
3,8
3,5
3
3,1
3,6
3,5
42/56

5/2/2011
43/56
4.3 REPEATED MEASUREMENTS CHARACTERISTICS NOT DETERMINED

Data source: ISO 8258:1991, 1991, page 22, Table 6.
Determined Central line of the weight for the control chart of the packaging process is 100,6 g and standard
deviation is 1,4
Subgroup N.
[1]
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
5/2/2011
Weight 1
[g]
98,9
99,3
98,5
98,25
97,5
97,6
98,35
99,65
100
98
97,6
96,55
97,45
96,85
97,15
97,55
96,95
97,4
98,55
97,15
97,8
98,2
98,65
97,55
98
Weight 2
[g]
99,75
100,3
99,05
99,375
98,7
98,55
99,375
100,075
100,55
99,15
98,85
98,075
98,325
98,125
98,275
98,575
98,125
98,65
99,525
98,325
98,95
99,3
99,875
98,725
98,85
Weight 3
[g]
100,6
101,3
99,6
100,5
99,9
99,5
100,4
100,5
101,1
100,3
100,1
99,6
99,2
99,4
99,4
99,6
99,3
99,9
100,5
99,5
100,1
100,4
101,1
99,9
99,7
Weight 4
[g]
101,45
102,3
100,15
101,625
101,1
100,45
101,425
100,925
101,65
101,45
101,35
101,125
100,075
100,675
100,525
100,625
100,475
101,15
101,475
100,675
101,25
101,5
102,325
101,075
100,55
Weight 5
[g]
102,3
103,3
100,7
102,75
102,3
101,4
102,45
101,35
102,2
102,6
102,6
102,65
100,95
101,95
101,65
101,65
101,65
102,4
102,45
101,85
102,4
102,6
103,55
102,25
101,4
Average
[g]
100,6
101,3
99,6
100,5
99,9
99,5
100,4
100,5
101,1
100,3
100,1
99,6
99,2
99,4
99,4
99,6
99,3
99,9
100,5
99,5
100,1
100,4
101,1
99,9
99,7
Range
[g]
3,4
4
2,2
4,5
4,8
3,8
4,1
1,7
2,2
4,6
5
6,1
3,5
5,1
4,5
4,1
4,7
5
3,9
4,7
4,6
4,4
4,9
4,7
3,4
44/56

5/2/2011
45/56

4.4 REPEATED MEASUREMENTS CHARACTERISTICS NOT DETERMINED

Subgroup N.
[1]
1
2
3
4
5
6
7
8
5/2/2011
Average 1
[cm]
0,1898
0,2012
0,2217
0,1832
0,1692
0,1621
0,2001
0,2401
Average 2
[cm]
0,1729
0,1913
0,2192
0,1812
0,2263
0,1832
0,1927
0,1825
Average 3
[cm]
0,2067
0,1878
0,2078
0,1963
0,2086
0,1914
0,2169
0,191
Average 4
[cm]
0,1898
0,1921
0,198
0,18
0,2091
0,1783
0,2082
0,2264
Average
[cm]
0,1898
0,2012
0,2217
0,1832
0,1692
0,1621
0,2001
0,2401
Range
[cm]
0,0338
0,0134
0,0237
0,0163
0,0571
0,0293
0,0242
0,0576
46/56
9
10
11
12
13
14
15
16
17
18
19
20
0,1996
0,1783
0,2166
0,1924
0,1768
0,1923
0,1924
0,172
0,1824
0,1812
0,17
0,1698
0,198
0,1715
0,1748
0,1984
0,1986
0,1876
0,1996
0,194
0,179
0,1585
0,1567
0,1664
0,2076
0,1829
0,196
0,2377
0,2241
0,1903
0,212
0,2117
0,1876
0,1699
0,1694
0,17
0,2023
0,1961
0,1923
0,2003
0,2022
0,1986
0,216
0,232
0,1821
0,168
0,1702
0,16
0,1996
0,1783
0,2166
0,1924
0,1768
0,1923
0,1924
0,172
0,1824
0,1812
0,17
0,1698
0,0096
0,0246
0,0418
0,0453
0,0473
0,0110
0,0236
0,0600
0,0086
0,0227
0,0135
0,0100
X-chart (control chart fro mean)

5/2/2011
47/56
R-chart (control chart for Range)

5/2/2011
48/56
CHAPTER
5
CALIBRATION
5.1 LINEAR CALIBRATION
Data source: ISO 8466:1, 1990, page 7, Table 5
Concentration
[ mg / l ]
0,05
0,1
0,15
0,2
0,25
0,3
0,35
0,4
0,45
0,5
Absorbance
[1]
0,14
0,281
0,405
0,535
0,662
0,789
0,916
1,058
1,173
1,303
Unknown samples:
Concentration
[ mg / l ]
?
?
?
?
5/2/2011
Absorbance
[1]
0,0542
0,854
1,123
0,01
49/56
5.2 QUADRATIC CALIBRATION

Data source: ISO 8466:2, 1993, page 8, Table 7
Concentration
[ mg / l ]
12
18
24
30
36
42
48
54
60
66
5/2/2011
Absorbance
[1]
0,083
0,123
0,164
0,203
0,24
0,273
0,303
0,334
0,364
0,393
50/56
Unknown samples:
Concentration
[ mg / l ]
?
?
?
?
Absorbance
[1]
0,084
0,123
0,32
0,024
5/2/2011
51/56
CHAPTER
6
UNCERTAINTIES
6.1 FROM PRECISION DATA MULTIPLE MEASUREMENTS
Data obtained by experimental measurements in a laboratory. Coverage factor: 2.0
Level 1
Level 2
Level 3
Measrt 1
5
25
50,8
Measrt 2
5,2
24,7
50,1
Measrt 3
5,8
24,1
49,2
Measrt 4
4,8
25,8
51
Measrt 5
5,7
24,6
50,4
Measrt 6
5,1
24,3
50,7
5/2/2011
52/56
6.2 FROM PRECISION DATA PARALLEL MEASUREMENTS
1997, page 30, Table 2.4. Coverage factor: 2.0
Experiment
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Measrt 1
42,68
42,08
43,39
42,87
42,7
42,93
42,78
42,92
43,34
43,12
42,43
43,05
42,99
43,04
43,41
43,12
42,25
42,96
42,83
42,83
Measrt 2
42,77
42,38
43,33
42,98
42,95
42,95
42,97
43,2
42,89
43,26
42,54
43,15
42,86
42,78
43,14
43,23
42,53
42,78
42,72
43,04
5/2/2011
53/56
6.3 FROM CONTROL CHART INDIVIDUAL MEASUREMENTS
Data source: ISO 8258:1991, 1991, page 27, Table 8: data presented in the ISO standard are 1-10. Because the
application of the Western-Electric rules requires min. 15 measurements, data in the table are repeated, resulting
in 20 values.
Measrt N.
[1]
Weight
[g]
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
100,6
101,3
99,6
100,5
99,9
99,5
100,4
100,5
101,1
100,3
100,1
99,6
99,2
99,4
99,4
99,6
99,3
99,9
100,5
99,5
5/2/2011
54/56
6.4 FROM CONTROL CHART REPEATED MEASUREMENTS
Subgroup N.
[1]
Average 1
[cm]
Average 2
[cm]
Average 3
[cm]
Average 4
[cm]
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
0,1898
0,2012
0,2217
0,1832
0,1692
0,1621
0,2001
0,2401
0,1996
0,1783
0,2166
0,1924
0,1768
0,1923
0,1924
0,172
0,1824
0,1812
0,17
0,1698
0,1729
0,1913
0,2192
0,1812
0,2263
0,1832
0,1927
0,1825
0,198
0,1715
0,1748
0,1984
0,1986
0,1876
0,1996
0,194
0,179
0,1585
0,1567
0,1664
0,2067
0,1878
0,2078
0,1963
0,2086
0,1914
0,2169
0,191
0,2076
0,1829
0,196
0,2377
0,2241
0,1903
0,212
0,2117
0,1876
0,1699
0,1694
0,17
0,1898
0,1921
0,198
0,18
0,2091
0,1783
0,2082
0,2264
0,2023
0,1961
0,1923
0,2003
0,2022
0,1986
0,216
0,232
0,1821
0,168
0,1702
0,16
5/2/2011
55/56
6.5 EXPERT ESTIMATE

Data source: not found. Data obtained by experimental measurements in a laboratory. Coverage factor: 2.0
6.6 FROM PARTIAL UNCERTAINTIES

EURACHEM/CITAC Guide, Quantifying Uncertainty in Analytical Measurement, Second Edition, June 1999,
Example 3.
y = (1000*x1*x2*x3)/(x4*(8*x5+5*x6+4*x7+x8)*x9). Coverage factor: 2.0
Source
X1
X2
X3
X4
X5
X6
X7
X8
X9
Value
0,3888
1
14,89
18,64
12,0107
1,00794
15,9994
39,0983
15
St. uncertainty
0,00013
0,00029
0,015
0,016
0,00046
4E-5
0,00017
5,8E-5
0,011
5/2/2011
56/56
5/2/2011

Book of Reference Examples Validation With Statistic

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Book of Reference Examples Validation With Statistic

Uploaded by

Copyright:

Available Formats

1999-2011

BOOK OF REFERENCE EXAMPLES

Lesn 593, 679 71 Lysice, Czech Republic

Book of Reference Examples EffiValidation 3.0

document version: 1.03

Book of Reference Examples EffiValidation 3.0

document version: 1.03

CONTROL CHARTS ......................................................................................................................................... 39

Book of Reference Examples EffiValidation 3.0

document version: 1.03

Lysice 5.2. 2011

Book of Reference Examples EffiValidation 3.0

document version: 1.03

Window Results in EffiValidation 3.0:

1.2 GRUBBS SINGLE TEST

Book of Reference Examples EffiValidation 3.0

document version: 1.03

Window Results in EffiValidation 3.0:

1.3 GRUBBS PAIR TEST

Window Results in EffiValidation 3.0:

1.4 DIXON TEST

Window Results in EffiValidation 3.0:

Book of Reference Examples EffiValidation 3.0

document version: 1.03

1.5 NORMALITY TEST

Window Results in EffiValidation 3.0:

Book of Reference Examples EffiValidation 3.0

document version: 1.03

Table 43, formulation A

Window Results in EffiValidation 3.0:

Book of Reference Examples EffiValidation 3.0

document version: 1.03

2.1.2 FROM PARALLEL MEASUREMENTS

Window Results in EffiValidation 3.0:

Book of Reference Examples EffiValidation 3.0

document version: 1.03

2.2 INTERMEDIATE PRECISION

Table 43, formulace A

Window Results in EffiValidation 3.0:

Table 43, formulace A

Book of Reference Examples EffiValidation 3.0

document version: 1.03

Window Results in EffiValidation 3.0:

2.3.2 RESULTS AVAILABLE

Book of Reference Examples EffiValidation 3.0

document version: 1.03

Dummy factors considered in the calculation:

Book of Reference Examples EffiValidation 3.0

document version: 1.03

Window Results in EffiValidation 3.0:

2.5.2 LIMITED CONCENTRATION RANGE REFERENCE MATERIAL AVAILABLE

Window Results in EffiValidation 3.0:

Book of Reference Examples EffiValidation 3.0

document version: 1.03

2.5.3 LARGE CONCENTRATION RANGE BLANK MATERIAL AVAILABLE: T-TEST

Window Results in EffiValidation 3.0:

Book of Reference Examples EffiValidation 3.0

document version: 1.03

Window Results in EffiValidation 3.0:

2.5.5 LARGE CONCENTRATION RANGE BLANK MATERIAL NOT AVAILABLE: T-TEST

Book of Reference Examples EffiValidation 3.0

document version: 1.03

Window Results in EffiValidation 3.0:

2.5.6 LARGE CONCENTRATION RANGE BLANK MATERIAL AVAILABLE: REGRESSION