unde:

- Ap = absorbanta probei de analizat

- Am = absorbanta probei martor
- f = factor de panta
- d = factor de diluare
- c = concentratia probei citita pe curba de etalonare, mg/l
FISA DE EVALUARE A INCERTITUDINII MASURARE
1. Indicatorul: azot din azotiti
2. Standardul de metoda: SR ISO 6777/1996
4. Diagrama de proces
3. Descrierea metodei: Azotitii reactioneaza, la pH 1.9 cu reactivul 4-aminobenzensulfonamida, in prezenta acidului
ortofosforic si formeaza o sare de diazoniu, care in reactie cu N(1naftil)etilendiaminadiclorhidrat, conduce la un
complex de culoare rosie, a carui absorbanta se masoara la 540 nm.
Pregatire etaloane
Prelevare proba
Pregatire proba
martor
Filtrare proba
Esantionare (diluare) +
Citire absorbanta
Trasarea curbei
de etalonare
Calculul concen -
tratiei de analit
d c d f Am Ap NO mgN C = = ) ( ) 2 (
Masa Volum
liniaritate
temperatura temperatura
etalonare
analit
solutie etalon stoc
masa puritate volum curba de calibrare
dilutie
volum volum conc pe curba
Tipul echipamentuluiCantitate
balon cotat 1000 ml 1
balon cotat 500 ml 0
balon cotat 200 ml 0
balon cotat 100 ml 1
balon cotat 50/40 ml 6
pipeta cotata 1 ml 2
pipeta cotata 2 ml 2
pipeta cotata 5 ml 6
pipeta cotata 10 ml 1
pipeta cotata 20 ml 2
pipeta cotata 25 ml 1
Nr. crt. Abs. Conc.
1 0.019 0.19793
2 0.018 0.16494
3 0.016 0.12536
4 0.017 0.19793
5 0.015 0.16494
6 0.013 0.12536
7 0.014 0.14955
8 0.014 0.10336
9 0.015 0.06378
10 0.014 0.07697
0.13701
0.04656
0.33983
Incert std rel a
repetabilitatii
d. Intervalul de incredere calculat la trasarea curbei de etalonare
Media conc.
Incert std repetab.
Abaterea standard a fost determinata in laborator pentru o valoare medie a N-NO2 de 0.07598 mg/l.
incertitudine certificata
b.Concentratia solutiei standard utilizata pentru etalonare
c. Echipamente pentru masurarea volumelor
6.a. Repetabilitatea
a. Repetabilitatea este determinata in laborator prin efectuarea a 10 experimente pe aceeasi proba, folosind
acelasi executant
Spectrofotometru
5. Surse identificate de incertitudine.Diagrama cauza-efect
incertitudine certificata
6.Cuantificarea incertitudinii. Modelarea matematica
6.b. Incertitudinea solutiei de etalon de azot din azotiti
Certificatul de analiza eliberat de producator indica o valoare a concentratiei de 502 mg/l 2mg/l
Incertitudinea standard asociata va fi: 1.15470054
Incertitudinea standard relativa a solutiei etalon 0.0023094
6.c. Incertitudinea datorata echipamentelor de masurare a volumelor
Valoare,x
unitate
de
masura
Incertitu-
dinea
standard,
u(x)
Incertitu-
dinea
standard
relativa,
u(x) / x
masurarea volumelor
toleranta() rep() temp(su)
V1000 1000 ml 0.04 0.03 0.606 0.607 0.0006 0.0000004 3.68E-07
V500 500 ml 0.25 0.03 0.303 0.336 0.0007 0.0000005 0.00E+00
V100 100 ml 0.1 0.03 0.061 0.085 0.0009 0.0000007 8.55E-04
V50 50 ml 0.06 0.03 0.030 0.049 0.0010 0.0000010 5.81E-06
V1 1 ml 0.006 0.004 0.001 0.005 0.0053 0.0000284 5.67E-05
V2 2 ml 0.01 0.01 0.001 0.012 0.0058 0.0000337 6.74E-05
V5 5 ml 0.03 0.25 0.003 0.251 0.0501 0.0025124 1.51E-02
V10 10 ml 0.05 0.03 0.006 0.042 0.0042 0.0000177 1.77E-05
V20 20 ml 0.1 0.06 0.012 0.084 0.0042 0.0000177 3.54E-05
V25 25 ml 0.1 0.06 0.015 0.085 0.0034 0.0000115 1.15E-05
0.0026238 1.61E-02
1.27E-01
temperatura si coeficientul de dilatare al apei
toleranta()
t 20.0 C 5 2.9
coef.
dilat.
vol.
0.00021 1/C
0.020408
0.001
7. Stabilirea bugetului de incertitudini
Componentele incertitudinii
6.e. Caracteristicile aparatului de masura
Suma patratelor incertitudinilor datorate echipam. de masurare a volumelor
6.d. Intervalul de incredere calculat la trasarea curbei de etalonare
Incertitudinea standard relativa datorata echip de masurare a volumelor
Din certificatul de etalonare al aparatului rezulta o incertitudine de masurare de 0.001 care se foloseste ca atare.
Incertitudinea standard relativa U(e)=u(e)/c
Incertitudinea de masurare a spectrofotometrului
Pentru o concentratie medie a etaloanelor utilizate la trasarea curbei de etalonare, de 0.098 mg/l , incertitudinea
relativa asociata intervalului de incredere a fost de 0.0204.
= =

3
2
2 NO etN
u
= =
x
x u
u
x
) (
2
) (
(

x
x u
2
) (
(

x
x u
Incert std.
rel [u(x)/x]
A Repetab. u(A) 0.3398 0.11549
B Solutie et. u(B) 0.0023 0.00001
C Mas vol u(C) 0.1270 0.01612
D Curba et u(D) 0.0204 0.00042
E Ap. mas u(E) 0.0000 0.00000
0.13203
Se compun incertitudinile asociate fiecarei componente si se obtine incertitudinea asociata unei valori X a N-NO2
X* 0.363361
X* 0.7267226
8. Calculul incertitudinii combinate
Suma patratelor incertitudinilor
relative
9. Calculul incertitudinii extinse
10. Raportarea rezultatelor
Incertitudinea extinsa se calculeaza cu un factor de acoperire 2, care corespunde unui nivel de incredere de 95%
Se remarca faptul ca cele mai semnificative contributii in calculul incertitudinilor dunt date de: repetabilitate,
de trasarea curbei de etalonare si de sticlaria volumetrica, celelalte doua componente neglijandu-se.
Rezultatele se raporteaza sub forma: X(0.061*X).
Incertitudinea se raporteaza cu acelasi numar de zecimale ca si rezultatul.
Pentru calculul incertitudinii combinate se porneste de la formula de calcul a continutului de azot din azotiti si de la
contributia fiecarei incertitudini
= + + = D
c
A u u u X NO N u
2 2
2 * ) 2 (
= = 2 * 0224 . 0 * ) 2 ( X NO N U
0.00000 0.05000 0.10000 0.15000 0.20000 0.25000 0.30000 0.35000 0.40000
1
Ap. mas u(E)
Curba et u(D)
Mas vol u(C)
Solutie et. u(B)
Repetab. u(A)
d c d f Am Ap NO mgN C = = ) ( ) 2 (
University of Applied Sciences
Department of Physical Chemistry
Prof Dr. R. Kaus
QA-guideline: QA_04_N10
Calibration and process data for the determination of Test data
method
Calibration data measured at
x y_1
mg/100g
abs Process data of a calibration function ... of 1. order ... 2. order
value 1 2.000 0.1010 Testing linearity: regression 2. Ordnung is not significantly better
value 2 4.000 0.1956 correlation coefficient 0.999 c = 0.000
value 3 6.000 0.2820 slope 0.001 b = 0.045 b = 0.042
value 4 8.000 0.3670 intercept 0.006 a = 0.010 a = 0.018
value 5 10.000 0.4700 residual standard deviation s(y) = 0.005 s(y) = 0.029
value 6 process standard deviation s(x0) = 0.119 s(x0) = 0.639
value 7 process variation coefficient V(x0) = 0.020 E = 0.045
value 8 40.000
value 9 auxiliary value for the determination of x_P y_P = 0.029 t(95%, single-sided) 2.35
value 10 testing value to secure the lower range limit x_P = 0.789 t(95%, single-sided) 2.35
number mean MDL = LC XN = 0.783 t(99%, single-sided) 4.54 sums
5 6.000 0.283 detection limit (DIN 32645) XE = 1.566 t(99%, double-sided) 5.84
quantitation limit (DIN 32645) XB = 2.582
k = 3
Calibration function 1.O: y = 0.010 + 0.045 x
Sample
Data Factor of Results
Confidence
interval for
results
Standard uncertainty
no. abs dilution mg/100g mg/L rel. in % e.g. double probe
lowest 0.1010 1.9947 1 1.9947 0.354 0.354 17.8% M = 2
mean 0.2831 6 1 6.0000 0.307 0.307 5.1% Standard relative expanded
highest 0.7160 15.52 1 15.5201 0.521 0.521 3.4% uncertainty S.U. S.U.
1 0.0193 0.1979 1 0.1979 0.400 0.4 202% 0.1478 74.7% 0.296
2 0.0178 0.1649 1 0.1649 0.401 0.401 243% 0.1482 89.9% 0.296
3 0.0160 0.1254 1 0.1254 0.402 0.402 321% 0.1488 118.7% 0.298
4 0.0171 0.1495 1 0.1495 0.402 0.402 269% 0.1484 99.3% 0.297
5 0.0150 0.1034 1 0.1034 0.403 0.403 390% 0.1491 144.2% 0.298
6 0.0132 0.0638 1 0.0638 0.404 0.404 633% 0.1496 234.6% 0.299
7 0.0138 0.077 1 0.0770 0.404 0.404 524% 0.1495 194.2% 0.299
8 0.0139 0.0792 1 0.0792 0.404 0.404 510% 0.1494 188.7% 0.299
9 0.0150 0.1034 1 0.1034 0.403 0.403 390% 0.1491 144.2% 0.298
10 0.0141 0.0836 1 0.0836 0.403 0.403 483% 0.1494 178.7% 0.299
Ka
4/13/2001
Quality Management Manual
Page: 1 von 3 Pages
Part B
Version:
Date :
proved:
released:
2.0
x_P
XB
0.0000
0.0500
0.1000
0.1500
0.2000
0.2500
0.3000
0.3500
0.4000
0.4500
0.5000
0.000 2.000 4.000 6.000 8.000 10.000 12.000
a
b
s

mg/100g
Calibration
regression curve
confidence interval
89283907.xls.ms_office Insert data & presenting result
University of Applied Sciences Version: 2.0
Department of Physical Chemistry Date : 4/13/2001
Prof Dr. R. Kaus Part B proved:
QA-guideline: QA_04_N10 Page: 1 von 3 Pages released: Ka
data sheet with the complete data
x y residuals
mg/100g abs
i_01 2 0.101
i_02 4 0.1956
i_03 6 0.282
i_04 8 0.367
i_05 10 0.47
i_06 0 0
i_07 0 0
i_08 0 0
i_09 0 0
i_10 0 0
number mean
10 3 0.142
Outlier testing data pair with suspected outlier i_06 0 0
F(f1=1,f2=N-2)= 5.317655 no outlier i_09 0 0
F-Test PW = 4.44218 no outlier for testing: line 36 should be eliminated
t-Test VB(yA) = 0.010883 Process data of the new linear calibration function (no outlier)
-0.00771 slope b = 0.047
intercept a = 0.002
residual standard deviation s(y)_a = 0.005
data sheet with the reduced data process standard deviation s(x0) _a= 0.099
x y process variation coefficient V(x0)_a = 3.3 %
i_01 2 0.101
i_02 4 0.1956
i_03 6 0.282
i_04 8 0.367
i_05 10 0.47
i_06 0 0
i_07 0 0
i_08 0 0
i_09 0 0
i_10 0 0
number mean
10 3.00 0.142
test datas: y_P = 0.01 x_P = 0.51919
Relevance: Comparing the slopes -2.61% deviation
Quality Management Manual
-0.012
-0.01
-0.008
-0.006
-0.004
-0.002
0
0.002
0.004
0.006
2 4 6 8 10 0 0 0 0 0
mg/100g
residual analysis

0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
2 4 6 8 10 0 0 0 0 0
mg/100g
residual analysis
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0.5
0.000 2.000 4.000 6.000 8.000 10.000 12.000
a
b
s

mg/100g
x_P
89283907.xls.ms_office / Outlier test
University of Applied Sciences Quality Management Manual Version: 2.0
Department of Physical Chemistry Date : 4/13/2001
Prof Dr. R. Kaus Part B proved:
QA-guideline: QA_04_N10 Page: 1 von 3 Pages released: Ka
Validation of an analytical method
Test data
Principal calibration
Process data of a calibration function of ...1. Order ... 2. Order
number of data N = 5 c = 0.000
slope b = 0.045 b = 0.042
intercept a = 0.010 a = 0.018
residual standard deviation s(y) = 0.005 s(y) = 0.029
process standard deviation s(x0) = 0.119 s(x0) = 0.639
process variation coefficient V(x0) = 1.98% E = 0.045
Calibration function 1.O: y = 0.010 + 0.045 x
Testing linearity: regression 2. order is not significantly better
Securing the lower range limit range statistically secure
auxiliary value for the determination of x_P y_P = 0.0288 t(95%, single-sided) 2.35
testing value to secure the lower range limit x_P = 0.789 t(95%, single-sided) 2.35
capability of detection (DIN 32465) NG = 0.783 t(99%, single-sided) 4.54
quantitation limit BG = 1.566 t(99%, double-sided) 5.84
k = 3
VB_x1 = 0.32
Relative analytical imprecision VB_x1(rel) = 15.95 %
1 1 31.0
2 2 15.9
3 3 11.1
4 4 8.8
5 5 7.6
6 6 6.8
7 7 6.2
8 8 5.8
9 9 5.6
10 10 5.4
11 11 5.2
12 12 5.1
13 13 5.0
14 14 4.9
15 15 4.9
16 16 4.8
17 17 4.8
18 18 4.7
19 19 4.7
20 20 4.7
21 21 4.7
22 22 4.6
23 23 4.6
24 24 4.6
25 25 4.6
0.0
5.0
10.0
15.0
20.0
25.0
30.0
35.0
0 5 10 15 20 25 30
V
B
(
x
)
r
e
l

i
n

%

mg/100g
confidence interval
VB(x)rel in %
89283907.xls.ms_office / Calibration function