Challenge 9.

2-1
Method performance study according to DIN EN ISO 10304-1 (2009)
Method

Determination of bromide in industrial water

Data set
n k \ ni
1
2
3
4

The number of replicates of each laboratory must be equal for the test!

Laboratories n i

Stage 1:

Replicates n k

2
15.10
15.00
14.90
15.10

3
15.20
15.00
15.10
15.10

4
15.50
15.20
15.40
15.40

5
14.80
14.90
14.80
14.90

6
15.20
15.30
15.00
15.20

4
16

4
16

4
16

4
16

4
16

15.025
0.0957

15.1
0.0816

15.375
0.1258

14.85
0.0577

15.175
0.1258

Preliminary data

xi*
*
si .
Stage 2:

Test for outliers of type 1 by Grubbs

r m (P = 95%, n k )

x max

15.1
0.783
no OL

15.2
1.225
no OL

15.5
0.993
no OL

14.9
0.866
no OL

15.3
0.993
no OL

x min

14.90
1.306
no OL

15.00
1.225
no OL

15.20
1.391
no OL

14.80
0.866
no OL

15.00
1.391
no OL

rm , max
Result
rm ,min
Result

If outliers within the laboratories are checked remove them from the data set table in B10:M17!
Type 1 OL-free data set
n k \ ni
1
2
3
4

Stage 3:

x *L
s*xL
Stage 4:

2
15.1
15
14.9
15.1

3
15.2
15
15.1
15.1

4
15.5
15.2
15.4
15.4

5
14.8
14.9
14.8
14.9

6
15.2
15.3
15
15.2

Recalculation of the laboratory mean values and the standard deviations

15.025
0.0957

15.100
0.0816

Test for outliers of type 2 by Grubbs

15.375
0.1258

14.850
0.0577
r m (P = 95%, n k )

15.175
0.1258

s xL
0.169934482
0.6927
0.2513
1.3669
1.7225
0.1900
no OL
no OL
no OL
no OL
no OL
If oultliers of the mean value of the laboratories are checked remove them from the data set table in B10:M17
15.143

rm, Li

Result

Type 2 OL-free data

n k \ ni
1
2
3
4

xi
Stage 7:

2
15.10
15.00
14.90
15.10

3
15.20
15.00
15.10
15.10

4
15.50
15.20
15.40
15.40

5
14.80
14.90
14.80
14.90

6
15.20
15.30
15.00
15.20

15.03

15.10

15.38

14.85

15.18

Test for reintegration of outliers of type 1

Copy the outlier within the laboratory checked in stage 2 into G74!
x max

15.375

x min

14.850

Result

Reintegration of the outlier of type 1 is not possible!

Stage 8 :

Test for outliers of type 3 by Cochran

si2
2
smax

0.009166667 0.00666667 0.015833333

0.015833333
0.0725
si2
C(P
=
99%,n
,
n
)
0.2184
0.5209
k
i

*
xOL
ik

14.50

0.00333333

0.01583333

Result

The laboratory with the maximal variance must not be rejected!

Stage 9 :

Calculation of parameters on the basis of the data set free of outliers of type 1 - 3

2
i

xi
si
15.143

15.025
15.100
15.375
0.095742711 0.08164966 0.125830574
n total
Laboratories n L
8

SS xx

0.027500

0.020000

0.047500

14.850
0.05773503

15.175
0.12583057

31
0.010000

0.047500

0.34271267

0.00417101

SSS xx

0.214167
Repeatability standard deviation, s r
sr
0.0964966
CV r %
nmean
0.64
Reproducibilitx standard deviation, s R
2
0.055421007 0.00729601
ni xi x

ni xi

sR
CV R %

Stage 10 :
h %

0.8027941
0.1911361
1.26

Recovery rate
99.62

sb2

0.1146849

3.870967742
0.215837674

s L2

0.02722143

Stage 11 :

t
Result

Estimation of bias by an t-test

1.669

t (P = 99%, df = n - 1)

The result is valid!

2.750

Grubbs Table P = 95%

3
4

15.2

7
15.40
15.40
15.20
15.30

8
15.10
15.00
15.10

9
15.30
15.20
15.30
15.10

4
16

3
9

4
16

15.325
0.0957

15.0666667
0.0577

mg/L

15.225
0.0957

1.463
15.4
0.783
no OL

15.1
0.577
no OL

15.3
0.783
no OL

15.20
1.306
no OL

15.00
1.155
no OL

15.10
1.306
no OL

m from the data set table in B10:M17!

7
15.4
15.4
15.2
15.3

8
15.1
15
15.1

9
15.3
15.2
15.3
15.1

15.325
0.0957

15.067
0.0577

15.225
0.0957

2.032

5
6
7
8
9
10
11
12
rm(95%, nk)
rm(95%, ni)
31 Cochran Table P = 99%
121
k
2
3
4
5
6
7
8
9
10

1.0727
0.4475
0.4843
no OL
no OL
no OL
move them from the data set table in B10:M17!

7
15.40
15.40
15.20
15.30

8
15.10
15.00
15.10

9
15.30
15.20
15.30
15.10

15.33

15.07

15.23

0.00916667

0.00333333

0.00916667

15.325
0.09574271

15.067
0.05773503

15.225
0.09574271

0.027500

0.006667

0.027500

0.13292101

0.01734701

0.02708767

of outliers of type 1 - 3

Grubbs Table P = 95%

P=95%
1.153
1.463
1.672
1.822
1.938
2.032
2.11
2.176
2.234
2.285
1.463
2.032
Cochran Table P = 99%
Degrees of freedom
1
2
0.9999
0.995
0.9933
0.9423
0.9676
0.8643
0.9279
0.7885
0.8828
0.7218
0.8376
0.6644
0.7945
0.6152
0.7544
0.5727
0.7175
0.5358
0.5209

3
0.9794
0.8831
0.7814
0.6957
0.6258
0.5685
0.5209
0.481
0.4469

4
0.9582
0.8335
0.7212
0.6329
0.5635
0.508
0.4627
0.4251
0.3934

5
0.9373
0.7933
0.6761
0.5875
0.5195
0.4659
0.4226
0.387
0.3572

6
0.9172
0.7606
0.641
0.5531
0.4866
0.4347
0.3932
0.3592
0.3308

7
0.8988
0.7335
0.6129
0.5259
0.4608
0.4105
0.3704
0.3378
0.3106

8
0.8823
0.7105
0.5897
0.5037
0.4401
0.3911
0.3522
0.3207
0.2945

Data set for Challenge 9.2-1

Method

Determination of bromide in industrial water

Data set
nk

\
1
2
3
4

1
13.80
13.90
14.00
13.70

2
15.10
15.00
14.90
15.10

3
15.20
15.00
15.10
15.10

4
15.50
15.20
15.40
15.40

5
14.80
14.90
14.80
14.90

6
15.20
15.30
15.00
15.20

15.2

7
15.40
15.40
15.20
15.30

8
15.10
15.00
15.10
14.50

mg/L
9
15.30
15.20
15.30
15.10