Você está na página 1de 48

Laboratrio de Metrologia e Ensaio

Planilha de Clculo de incerteza de Medio


Calibrao, Medio, ou Ensaio: Concetrao de Cd na amostra em mg/kg determinada por Absoro Atmica
Tcnico: Welington F. de MAGALHES Servio num.: 190857 Folha 1/1 Rubrica:

Grandezas de entrada ou de influncia Fontes de Funo Densidade de probabilidade Contribuio de incerteza: u(y;xi)
incerteza (uncertainty sources) (Probability density function) (Uncertainty contribution) GL[ui(y;xi)] =
i ou [ui(y)]4/i
meio intevalo incerteza padro Coef. Sens. ui(y) = u(y;xi)
Smbolo Valor
declarado
unidade Tipo Nome Divisor k u(xi) GLef = i,ef
ci ci.u(xi)
mbruta 119.0857 g
Ccalib 0.0 0.00021 g B Normal 2.26 9.29204E-005 -0.00073 6.78398E-008 9.00E+99 2.35E-129
Cresol 0.0 0.0001 g B Retangular 1.7320508 0.000057735 -0.00073 4.21515E-008 9.00E+99 3.51E-130
mbruta 119.0857 g 0.0001093962 -0.00073 7.98685E-008 1.50E+100 2.70E-129

mtara 19.0857 g
Ccalib 0.0 0.00021 g B Normal 2.26 9.29204E-005 0.0007301 6.78398E-008 9.00E+99 2.35E-129
Cresol 0.0 0.0001 g B Retangular 1.7320508 0.000057735 0.0007301 4.21515E-008 9.00E+99 3.51E-130
mtara 19.0857 g 0.0001093962 0.0007301 7.98685E-008 1.50E+100 2.70E-129

Vfabert 100.000 mL
Ccalib 0.000 0.08 mL B Normal 2 0.04 0.0007301 2.92034E-005 9.00E+99 8.08E-119
Cvartemp 0.000 0.063 mL B Retangular 1.7320508 0.036373067 0.0007301 2.65554E-005 9.00E+99 5.53E-119
Crepe 0.00E+00 0.05 mL A Normal 1 0.05 0.0007301 3.65043E-005 9.00E+00 1.97E-19
Cresol 0 0 mL B Retangular 1.7320508 0 0.0007301 0 9.00E+99 0.00E+00
Vfabert 100.000 mL 0.0736410212 0.0007301 5.37642E-005 4.23E+01 1.97E-19

Vidil1 100.000 mL
Ccalib 0.000 0.02 mL B Normal 2 0.01 -0.00073 7.30085E-006 9.00E+99 3.16E-121
Cvartemp 0.000 0.063 mL B Retangular 1.7320508 0.036373067 -0.00073 2.65554E-005 9.00E+99 5.53E-119
Crepe 0.00E+00 0.004 mL A Normal 1 0.004 -0.00073 2.92034E-006 9.00E+00 8.08E-24
Cresol 0 0 mL B Retangular 1.7320508 0 -0.00073 0 9.00E+99 0.00E+00
Vidil1 100.000 mL 0.0379341535 -0.00073 2.76952E-005 7.28E+04 8.08E-24

Vfdil1 10.000 mL
Ccalib 0.000 0.08 mL B Normal 2 0.04 0.0073009 0.0002920341 9.00E+99 8.08E-115
Cvartemp 0.000 0.0063 mL B Retangular 1.7320508 0.0036373067 0.0073009 2.65554E-005 9.00E+99 5.53E-119
Crepe 0.00E+00 0.05 mL A Normal 1 0.05 0.0073009 0.0003650426 9.00E+00 1.97E-15
Cresol 0 0 mL B Retangular 1.7320508 0 0.0073009 0 9.00E+99 0.00E+00
Vfdil1 10.000 mL 0.0641344681 0.0073009 0.0004682363 2.44E+01 1.97E-15

Vidil2 0.000 mL
Ccalib 0.000 0.02 mL B Normal 2 0.01 -0.073009 0.0007300852 9.00E+99 3.16E-113
Cvartemp 0.000 0 mL B Retangular 1.7320508 0 -0.073009 0 9.00E+99 0.00E+00
Crepe 0.00E+00 0.004 mL A Normal 1 0.004 -0.073009 0.0002920341 9.00E+00 8.08E-16
Cresol 0 0 mL B Retangular 1.7320508 0 -0.073009 0 9.00E+99 0.00E+00
Vidil2 0.000 mL 0 -0.073009 0 0.00E+00 0.00E+00

Vfdil2 0.000 mL
Ccalib 0.000 0.08 mL B Normal 2 0.04 0.0730085 0.0029203408 9.00E+99 8.08E-111
Cvartemp 0.000 0 mL B Retangular 1.7320508 0 0.0730085 0 9.00E+99 0.00E+00
Crepe 0.00E+00 0.05 mL A Normal 1 0.05 0.0730085 0.0036504261 9.00E+00 1.97E-11
Cresol 0 0 mL B Retangular 1.7320508 0 0.0730085 0 9.00E+99 0.00E+00
Vfdil2 0.000 mL 0 0.0730085 0 0.00E+00 0.00E+00

Aamostra 0.1900 1
Crep 0.000 3.53E-03 1 A Normal 1.4142136 0.0024940658 3.91E-01 0.0009759645 9.00E+99 1.01E-112
Aamostra 0.190 1 0.0024940658 0.3913147 0.0009759645 9.00E+99 1.01E-112
a 3.43E-03 0.0004090107 1 A Normal 1 0.0004090107 -3.91E-01 0.0001600519 1.30E+01 5.05E-17

b 2.56E-01 0.0013983671 kg/mg A Normal 1 0.0013983671 -2.86E-01 0.0003995038 1.30E+01 1.96E-15

Cov(a,b) -4.1106E-007 kg/mg A Normal 1 -4.11059E-007 2.24E-01 -9.1909E-008 1.30E+01 5.49E-30

FCrecup 1.000 0.1 1 B Retangular 1.7320508 0.0577350269 0.0730085 0.0042151489 9.00E+99 3.51E-110

Creproint 0.000 0.0036504261 mg/kg A Normal 1 0.0036504261 1 0.0036504261 3.00E+00 5.92E-11

Soma 0.0056887442 5.92E-11

Grandeza Incerteza Incerteza Incerteza


Valor Graus de liberdade Probabilidade de Incerteza
Valor
Estimado padro efetivos abrangncia
Fator de abrangncia
expandida
padro expandida
nominal combinada relativa % relativa %

Y y uc(y) ef P/% k U(y) RSD = CV CVE


mg/kg 0.0730 0.005689 1.77E+01 95 2.1098 0.0120 7.7919 16.4395
Observaes: canalCC = 7.30E-01 u(canalCC) = 0.0102265 K= 2
Variao de temperaura do Lab.: +- 3 oC

Principais contribuies d
Equao do mensurando: 0.006

0.005
Aamostra a
V fabert V V 0.004
b
canal fdil 1 fdil 2
FCrecup Crepro int 0.003
mbruta mtara Vidil1 Vidil 2 0.002

0.001

0
0.005
Aamostra a
V fabert V V 0.004
b
fdil 1 fdil 2
canal FCrecup Crepro int 0.003
mbruta mtara Vidil1 Vidil 2 0.002

Canal 0.001
Concentrao do analito na amostra de ensaio analisada. Unidades: mg/kg
0
I emis Intensiade mdia de emisso da amostra de leituras em duplicatas. Unidades: adimensional Aamostra a b FCrecup Creproin

a Intercepto da reta de calibrao obtido do ajuste pelo mtodo dos mnimos quadrados ponderado absoluto. Unidades: adimensional

b Inclino da reta de calibrao, semsibilidade, obtida do ajuste pelo mtodo dos mnimos quadrados ponderado absoluto. Unidades: kg/mg

Covaricia entre o intercepto e a inclinao da reta de calibrao obtida do ajuste pelo mtodo dos mnimos quadrados ponderado absoluto.
cov(a,b)
Unidades: kg/mg

Vfabert Volume final da soluo de abertura da amostra. Unidades: mL

mbruta massa bruta do recipiente de pesagem e da amostra seca. Unidades: g

mtara massa de tara do recipiente de pesagem vazio. Unidades: g

Vidil1 Volume inicial, alquota, da soluo de abertura da amostra para sua primeira diluio diluio. Unidade: mL

Vfdil1 Volume final da primeira diluio da soluo de abertura da amostra. Unidade: mL

Vidil2 Volume inicial, alquota, da soluo de abertura da amostra para sua segunda diluio diluio. Unidade: mL

Vfdil2 Volume final da segunda diluio da soluo de abertura da amostra. Unidade: mL

Creproint Correo nula de reprodutibilidade interna ou de preciso intermediria. Unidades: mg/kg

FCrecup Fator de correo unitrio de recuperao. Unidades: adimensional


Vfabert
Ccalib

Cvartemp Ccalib CResol mamost Ccalib

Crepet mbruta

Cresol

Tempo
a
Analista
s
Aemis b
Ambient
e
Cov(a,b
Abertura
de mostra )
Creproint CEAA Apad FCrecup

Cpad
Calibra
o do EAA
Calibra
o do EAA
contribuies de incerteza
b FCrecup Creproint uc(y)
Ccalib Ccalib

mtara

U(Canal)
Vidil1

Vidil2

Vfdil1
FCrecup
Vfdil2

FCdil
FCdil

Ccalib Crepet

Cvartemp Cresol
Planilha para ajuste de reta de calibrao e clculo de Ccalf, Ccbeta e
Incerteza de calibrao da soluo da amostra de ensaio:
Anlise de Cd Exemplo A5 do Guia Eurachem/Citac QUAM 2000
i j xi = ci yi =resp inst s(yi) s(y)2 wi = 1/si2 wixi
1 0.1 0.028 0.0054856 3.0092E-05 3.3231E+04 3323.108
1 2 0.1 0.029 33231.083845 3323.108
3 0.1 0.029 33231.083845 3323.108
1 0.3 0.084 0.0054856 3.0092E-05 3.3231E+04 9969.325
2 2 0.3 0.083 33231.083845 9969.325
3 0.3 0.081 33231.083845 9969.325
1 0.5 0.135 0.0054856 3.0092E-05 3.3231E+04 16615.54
3 2 0.5 0.131 33231.083845 16615.54
3 0.5 0.133 33231.083845 16615.54
1 0.7 0.18 0.0054856 3.0092E-05 3.3231E+04 23261.76
4 2 0.7 0.181 33231.083845 23261.76
3 0.7 0.183 33231.083845 23261.76
1 0.9 0.215 0.0054856 3.0092E-05 3.3231E+04 29907.98
5 2 0.9 0.23 33231.083845 29907.98
3 0.9 0.216 33231.083845 29907.98
1
6 2
3
1
7 2
3
1
8 2
3
1
9 2
3

somas: 7.5 1.938 0.0274282 0.0001504615 498466.25767 249233.1


Mdias 0.5 0.1292 0.0054856 3.009231E-005 33231.083845 0.5
i xi = ci yi =respinst s(yi) s(y)2 wi = 1/si2 wixi

19877488803 Ver o comentrio da clula em vermelho esquer

Welington F. MAGALHES:
a= 0.0087 Ateno: os valores de CC e de
concentrao do eixo x usadas
b= 0.2410 diferena entre as unidades do
s(a) = 0.0028767 Observao ainda devem ser convertidos p
s(b) = 0.0050077 Se a curva de calibrao no f
correo devido a inexatido d
cov(a,b) = -1.3E-005
sres = 0.0054856
N=IxJ= 15
GL = N-2 = 13 Valores crticos unilaterais
alfa/2 = ? 5 1.9623391 z(1%) = 2.326348
t(alfa,GL) 1.7709334 z(5%) = 1.644854

Valor crtico da concentrao lquida do analito - CC - e concentrao lquida mnim


K= 1 CLPsup(x = 0) = 0.0138708176
CC = 0.0214556747
CD = 0.0429113494

Curvas de Limite de Previso - CLP - para K replicatas da amostra de ensaio


x* y* s(y*) s2(y*) s2LP(y*) Delta(y) lim inf
0 0.0087 0.0005 2.50E-007 8.525385E-006 0.0051708176 0.003529
0.1 0.0328 0.0006534 4.27E-007 6.445400E-006 0.0044960091 0.028304
0.2 0.0569 0.0008539 7.29E-007 4.992184E-006 0.0039568313 0.052943
0.3 0.081 0.0011159 1.25E-006 4.254368E-006 0.0036527483 0.077347
0.4 0.1051 0.0014582 2.13E-006 4.383313E-006 0.0037076904 0.101392
0.5 0.1292 0.0019056 3.63E-006 5.637508E-006 0.0042048046 0.124995
0.6 0.1533 0.0024903 6.20E-006 8.458389E-006 0.0051504603 0.14815
0.7 0.1774 0.0032543 1.06E-005 1.359982E-005 0.006530836 0.170869
0.8 0.2015 0.0042528 1.81E-005 2.234921E-005 0.0083720794 0.193128
0.5 0.1292 <-- Centride

s(y*) = 0,0005*EXP(2,6759*x) 0.0036527483 = mnimo


Curvas de Limite de Previso - CLP - para K replicatas da amostra de ensaio
CV
1.99
1.50
1.38
1.39
1.47
1.62
1.83
2.11
y = r e sp o sta i n stru m e n ta l
alf, Ccbeta e

QUAM 2000
wiyi wixiyi wi(xi)2 wi(yi)2 yicalc res(y) wi*res2(y)
930.47035 93.04703 332.31083845 26.05317 0.0328 -0.0048 0.765644
963.70143 96.37014 332.31083845 27.94734 0.0328 -0.0038 0.479857 0.25

963.70143 96.37014 332.31083845 27.94734 0.0328 -0.0038 0.479857 0.2 f(x) =


R = 0
2791.411 837.4233 2990.797546 234.4785 0.081 0.003 0.29908
0.15
2758.18 827.454 2990.797546 228.9289 0.081 0.002 0.132924
2691.7178 807.5153 2990.797546 218.0291 0.081 0 0 0.1

4486.1963 2243.098 8307.7709611 605.6365 0.1292 0.0058 1.117894 0.05


4353.272 2176.636 8307.7709611 570.2786 0.1292 0.0018 0.107669
0
4419.7342 2209.867 8307.7709611 587.8246 0.1292 0.0038 0.479857 0
x = Con
0.1
5981.5951 4187.117 16283.231084 1076.687 0.1774 0.0026 0.224642

DP (y) = DP (re sp. inst.)


6014.8262 4210.378 16283.231084 1088.684 0.1774 0.0036 0.430675
6081.2883 4256.902 16283.231084 1112.876 0.1774 0.0056 1.042127
7144.683 6430.215 26917.177914 1536.107 0.2256 -0.0106 3.733845
7643.1493 6878.834 26917.177914 1757.924 0.2256 0.0044 0.643354
7177.9141 6460.123 26917.177914 1550.429 0.2256 -0.0096 3.062577 Modelo

0.009

0.008

0.007

0.006

0.005 f(x) = 0.0


R = 0Z
0.004

0.003

0.002
R e s d u o d e M M Q P O

0.001
64401.84 41811.35 164493.86503 10649.83 3.85E-016 13 0 0.1 0.2
0.1292 2.57E-017
wiyi wixiyi wi(xi)2 wi(yi)2 yicalc res(y) wi*res2(y)

rio da clula em vermelho esquerda

Welington F. MAGALHES:
Ateno: os valores de CC e de CD obtidos nessa tabela esto nas mesmas unidades de
concentrao do eixo x usadas na construo da curva de calibrao. Portanto, se houver
diferena entre as unidades do eixo x e o resultado final, e.g. ppm, ppb, etc, CC e CD 0.008
ainda devem ser convertidos para essa unidade final 0.006
Se a curva de calibrao no for feita com MRC, esses valores tambm no incluem a 0.004
correo devido a inexatido do mtodo analtico (recuperao).
0.002
0
-0.002
-0.004
-0.006
t(1%) = 2.650309 ,
-0.008
t(5%) = 1.770933
ns trum e nta l re a d e p ic o

-0.01
-0.012

oncentrao lquida mnima detetvel - CD (ISO 11843) 0 0.1 0.2 0.


R e s p o s ta ins trum e nta l re a d e p ic o
amostra de ensaio
lim sup
0.0138708
0.037296 0.25
0.0608568 Reta de Calibrao MMQO e CLP
0.0846527
0.1088077
0.2 f(x) = 0.0190258108x^2 + 0.2294208251x + 0.0140460725
0.1334048 f(x) = 0.241x + 0.0087
f(x)==1 - 0.0190258108x^2 + 0.2525791749x + 0.0033539275
R
0.1584505
0.1839308
0.2098721 0.15

0.1
amostra de ensaio

0.05

0
0 0.1 0.2 0.3 conc / mg/L
0.4 0.5 0.6 0.7 0.8 0.9
Curva de calibrao
0.25

0.2 f(x) = 0.2410x + 0.0087


R = 0.9944
0.15

0.1

0.05

0
x = Concentrao da soluo de calib
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Modelo para o DP da resposta instrumental

0.009

0.008

0.007

0.006

0.005 f(x) = 0.0055 exp( 0.0000 x )


R = 0ZNaN
0.004

0.003

0.002

0.001
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x = conc

.008
.006
.004
.002
0
.002
.004
.006
.008
0.01
.012
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Conc. mg/l
e CLP

25
9275

Colum n C
Linear (C olum n C )
CLP inf 95%
Poly nom ial (CLP
inf 95%)
CLP s up 95%
Poly nom ial (CLP
sup 95%)
Cent ride

0.7 0.8 0.9


Planilha para ajuste de reta de calibrao e clculo de Ccalf, Ccbeta e
Incerteza de calibrao da soluo da amostra de ensaio:
Anlise de Cd Exemplo A5 do Guia Eurachem/Citac QUAM 2000
i j xi = ci yi =resp inst s(yi) s(y)2 wi = 1/si2 wixi
1 0.1 0.028 0.0005774 3.3333E-07 3.0000E+06 300000
1 2 0.1 0.029 3000000 300000
3 0.1 0.029 3000000 300000
1 0.3 0.084 0.0015275 2.3333E-06 4.2857E+05 128571.4
2 2 0.3 0.083 428571.42857 128571.4
3 0.3 0.081 428571.42857 128571.4
1 0.5 0.135 0.002 4.0000E-06 2.5000E+05 125000
3 2 0.5 0.131 250000 125000
3 0.5 0.133 250000 125000
1 0.7 0.18 0.0015275 2.3333E-06 4.2857E+05 300000
4 2 0.7 0.181 428571.42857 300000
3 0.7 0.183 428571.42857 300000
1 0.9 0.215 0.0083865 7.0333E-05 1.4218E+04 12796.21
5 2 0.9 0.23 14218.009479 12796.21
3 0.9 0.216 14218.009479 12796.21
1
6 2
3
1
7 2
3
1
8 2
3
1
9 2
3

somas: 7.5 1.938 0.0140189 7.933333E-005 12364082.6 2599103


Mdias 0.5 0.1292 0.0028038 1.586667E-005 824272.17332 0.210214
i xi = ci yi =respinst s(yi) s(y)2 wi = 1/si2 wixi

322946126318 Ver o comentrio da clula em vermelho esquer

Welington F. MAGALHES:
a= 0.0034276 Ateno: os valores de CC e de
concentrao do eixo x usadas
b= 0.2555488 diferena entre as unidades do
s(a) = 0.000409 Observao ainda devem ser convertidos p
s(b) = 0.0013984 Se a curva de calibrao no f
correo devido a inexatido d
cov(a,b) = -4.1E-007
sres = 0.0016838
N=IxJ= 15
GL = N-2 = 13 Valores crticos unilaterais
alfa/2 = ? 2.5 z(1%) = 2.326348
t(alfa,GL) 2.1603687 z(5%) = 1.644854

Valor crtico da concentrao lquida do analito - CC - e concentrao lquida mnim


K= 1 CLPsup(x = 0) = 0.0048231445
CC = 0.0054610085
CD = 0.010922017

Curvas de Limite de Previso - CLP - para K replicatas da amostra de ensaio


x* y* s(y*) s2(y*) s2LP(y*) Delta(y) lim inf
0 0.00342759 0.0005 2.50E-007 4.172897E-007 0.0013955543 0.002032
0.1 0.02898247 0.0006534 4.27E-007 5.315712E-007 0.0015751016 0.027407
0.2 0.05453735 0.0008539 7.29E-007 8.101907E-007 0.0019445607 0.052593
0.3 0.08009223 0.0011159 1.25E-006 1.341780E-006 0.0025024682 0.07759
0.4 0.10564712 0.0014582 2.13E-006 2.277701E-006 0.0032604404 0.102387
0.5 0.131202 0.0019056 3.63E-006 3.876443E-006 0.0042534816 0.126949
0.6 0.15675688 0.0024903 6.20E-006 6.579440E-006 0.005541436 0.151215
0.7 0.18231176 0.0032543 1.06E-005 1.114056E-005 0.0072107643 0.175101
0.8 0.20786664 0.0042528 1.81E-005 1.884721E-005 0.0093788883 0.198488
0.210214 0.05714752 <-- Centride

s(y*) = 0,0005*EXP(2,6759*x) 0.0013955543 = mnimo


Curvas de Limite de Previso - CLP - para K replicatas da amostra de ensaio
CV
2.25
1.57
1.39
1.38
1.45
1.59
1.79
2.05
alf, Ccbeta e

QUAM 2000
wiyi wixiyi wi(xi)2 wi(yi)2 yicalc res(y) wi*res2(y) raiz(wi)*res(y)
84000 8400 30000 2352 0.028982 -0.000982 2.895752 -1.7017E+00
87000 8700 30000 2523 0.028982 1.75E-005 0.000922 3.0360E-02
87000 8700 30000 2523 0.028982 1.75E-005 0.000922 3.0360E-02
36000 10800 38571.428571 3024 0.080092 0.003908 6.544556 2.5582E+00
35571.429 10671.43 38571.428571 2952.429 0.080092 0.002908 3.623614 1.9036E+00
34714.286 10414.29 38571.428571 2811.857 0.080092 0.000908 0.353159 5.9427E-01
33750 16875 62500 4556.25 0.131202 0.003798 3.606206 1.8990E+00
32750 16375 62500 4290.25 0.131202 -0.000202 0.010201 -1.0100E-01
33250 16625 62500 4422.25 0.131202 0.001798 0.808203 8.9900E-01
77142.857 54000 210000 13885.71 0.182312 -0.002312 2.290386 -1.5134E+00
77571.429 54300 210000 14040.43 0.182312 -0.001312 0.737449 -8.5875E-01
78428.571 54900 210000 14352.43 0.182312 0.000688 0.203003 4.5056E-01
3056.872 2751.185 11516.587678 657.2275 0.233422 -0.018422 4.824917 -2.1966E+00
3270.1422 2943.128 11516.587678 752.1327 0.233422 -0.003422 0.166448 -4.0798E-01
3071.09 2763.981 11516.587678 663.3555 0.233422 -0.017422 4.3153 -2.0773E+00

706576.68 279219 1057764.0487 73806.32 -0.03003 30.38104


0.0571475 -0.002002
wiyi wixiyi wi(xi)2 wi(yi)2 yicalc res(y) wi*res2(y)

rio da clula em vermelho esquerda

Welington F. MAGALHES:
Ateno: os valores de CC e de CD obtidos nessa tabela esto nas mesmas unidades de
concentrao do eixo x usadas na construo da curva de calibrao. Portanto, se houver
diferena entre as unidades do eixo x e o resultado final, e.g. ppm, ppb, etc, CC e CD
ainda devem ser convertidos para essa unidade final
Se a curva de calibrao no for feita com MRC, esses valores tambm no incluem a
correo devido a inexatido do mtodo analtico (recuperao).

t(1%) = 2.650309 ,
t(5%) = 1.770933
s trum e nta l re a d e p ic o

oncentrao lquida mnima detetvel - CD (ISO 11843)


R e s p o s ta ins trum e nta l re a d e p ic o
amostra de ensaio
lim sup
0.0048231
0.0305576 0.25
0.0564819 Reta de Calibrao MMQPA e CLP
0.0825947
0.1089076 f(x) = 0.0133373944x^2 + 0.2545097468x + 0.0049381518
0.2 f(x) = 0.2555488142x + 0.0034275902
0.1354555 f(x)==1 - 0.0133373944x^2 + 0.2565878817x + 0.0019170287
R
0.1622983
0.1895225
0.2172455 0.15

0.1
amostra de ensaio

0.05

0 conc / mg/L
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
y = r e sp o sta i n stru m e n ta l

Curva de calibrao
0.25

0.2 f(x) = 0.241000x + 0.008700


R = 0.994418
0.15

0.1

0.05

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x = Concentrao da soluo de calib
DP (y) = DP (re sp. inst.)

Modelo para o DP da resposta instrumental


0.009

0.008

0.007

0.006

0.005
f(x) = 0.0005 exp( 2.6759 x )
0.004 R = 0.7700
R e s d u o p a d r o n iz a d o d e M M Q P A

0.003

0.002

0.001

0
0 0.1 0.2 0.3 x = 0.4
conc 0.5 0.6 0.7 0.8 0.9 1

3.0000E+00

2.0000E+00

1.0000E+00

0.0000E+00

-1.0000E+00

-2.0000E+00

-3.0000E+00
0 0.1 0.2 0.3 Conc.
0.4 mg/L
0.5 0.6 0.7 0.8 0.9 1
e CLP

49381518

0019170287

Reta
Linear (R et a)
CLP inf
Poly nom ial
(C LP inf )
CLP s up
Poly nom ial
(C LP sup)
baric entro

0.6 0.7 0.8 0.9


8 0.9 1

0.9 1
Planilha para ajuste de reta de calibrao e clculo de Ccalf, Ccbeta e
Incerteza de calibrao da soluo da amostra de ensaio:
Ag 01-02-2008
i j xi = ci yi = resp inst s(yi) s2(yi) wi = s2m/si2 wixi
1 0.1 0.028 0.0005774 3.3333E-07 4.7600E+01 4.76
1 2 0.1 0.029 47.6 4.76
3 0.1 0.029 47.6 4.76
1 0.3 0.084 0.0015275 2.3333E-06 6.8000E+00 2.04
2 2 0.3 0.083 6.8 2.04
3 0.3 0.081 6.8 2.04
1 0.5 0.135 0.002 4.0000E-06 3.9667E+00 1.983333
3 2 0.5 0.131 3.9666666667 1.983333
3 0.5 0.133 3.9666666667 1.983333
1 0.7 0.18 0.0015275 2.3333E-06 6.8000E+00 4.76
4 2 0.7 0.181 6.8 4.76
3 0.7 0.183 6.8 4.76
1 0.9 0.215 0.0083865 7.0333E-05 2.2559E-01 0.203033
5 2 0.9 0.23 0.2255924171 0.203033
3 0.9 0.216 0.2255924171 0.203033
1
6 2
3
1
7 2
3
1
8 2
3
1
9 2
3

somas: 7.5 1.938 0.0140189 7.933333E-005 196.17677725 41.2391


Mdias 0.5 0.1292 0.0028038 1.586667E-005 13.078451817 0.210214
i j xi = ci yi =respinst s(yi) s(y)2 wi = 1/si2 wixi

1591.8087128 Ver o comentrio da clula em vermelho esquer

Welington F. MAGALHES:
a= 0.0034276 Ateno: os valores de CC e d
b= 0.2555488 concentrao do eixo x usada
diferena entre as unidades d
s(a) = 0.000409 Observao ainda devem ser convertidos
s(b) = 0.0013984 Se a curva de calibrao no f
cov(a,b) = -4.1E-007 correo devido a inexatido d

sres = 0.0016838
N=IxJ= 15
GL = N-2 = 13 Valores crticos unilaterais
alfa/2 = ? 5 z(1%) = 2.326348
t(alfa,GL) 1.7709334 z(5%) = 1.644854

Valor crtico da concentrao lquida do analito - CC - e concentrao lquida mnim


K= 1 CLPsup(x = 0) = 0.0045715772
CC = 0.0044765889
CD = 0.0089531778

Curvas de Limite de Previso - CLP - para K replicatas da amostra de ensaio


x* y* s(y*) s2(y*) s2LP(y*) Delta(y) lim inf
0 0.00342759 0.0005 2.50E-007 4.172897E-007 0.001143987 0.002284
0.1 0.02898247 0.0006534 4.27E-007 5.315712E-007 0.0012911686 0.027691
0.2 0.05453735 0.0008539 7.29E-007 8.101907E-007 0.0015940277 0.052943
0.3 0.08009223 0.0011159 1.25E-006 1.341780E-006 0.002051365 0.078041
0.4 0.10564712 0.0014582 2.13E-006 2.277701E-006 0.0026727025 0.102974
0.5 0.131202 0.0019056 3.63E-006 3.876443E-006 0.0034867348 0.127715
0.6 0.15675688 0.0024903 6.20E-006 6.579440E-006 0.0045425183 0.152214
0.7 0.18231176 0.0032543 1.06E-005 1.114056E-005 0.0059109279 0.176401
0.8 0.20786664 0.0042528 1.81E-005 1.884721E-005 0.0076882186 0.200178

s(y*) = 0,0005*EXP(2,6759*x) 0.001143987 = mnimo


Curvas de Limite de Previso - CLP - para K replicatas da amostra de ensaio
CV
2.25
1.57
1.39
1.38
1.45
1.59
1.79
2.05
alf, Ccbeta e

y = r e s p o s t a in s t r u m e n t a l
wiyi wixiyi wi(xi)2 wi(yi)2 yicalc res(yi) wi*res2(yi)
1.3328 0.13328 0.476 0.037318 0.028982 -0.000982 4.59E-005
1.3804 0.13804 0.476 0.040032 0.028982 1.75E-005 1.46E-008 0.25
1.3804 0.13804 0.476 0.040032 0.028982 1.75E-005 1.46E-008
0.2 f (x ) = 0.241
0.5712 0.17136 0.612 0.047981 0.080092 0.003908 0.000104 R = 0.9944

0.5644 0.16932 0.612 0.046845 0.080092 0.002908 5.75E-005 0.15

0.5508 0.16524 0.612 0.044615 0.080092 0.000908 5.60E-006 0.1


0.5355 0.26775 0.9916666667 0.072293 0.131202 0.003798 5.72E-005 0.05
0.5196333 0.259817 0.9916666667 0.068072 0.131202 -0.000202 1.62E-007
0
0.5275667 0.263783 0.9916666667 0.070166 0.131202 0.001798 1.28E-005 0 0.1 0.2
x = Conce ntr a
1.224 0.8568 3.332 0.22032 0.182312 -0.002312 3.63E-005

DP (y) = DP (re sp. inst.)


1.2308 0.86156 3.332 0.222775 0.182312 -0.001312 1.17E-005
1.2444 0.87108 3.332 0.227725 0.182312 0.000688 3.22E-006
0.0485024 0.043652 0.1827298578 0.010428 0.233422 -0.018422 7.66E-005
0.0518863 0.046698 0.1827298578 0.011934 0.233422 -0.003422 2.64E-006
0.048728 0.043855 0.1827298578 0.010525 0.233422 -0.017422 6.85E-005
Modelo p
0.009

0.008

0.007

0.006

0.005
f(x) = 0.000
0.004 R = 0.770
0.003

0.002

0.001

11.211017 4.430275 16.783189573 1.17106 -0.03003 0.000482 0 0.1 0.2

0.0571475 -0.002002
wiyi wixiyi wi(xi)2 wi(yi)2 yicalc res(yi) wi*res2(yi)

rio da clula em vermelho esquerda

Welington F. MAGALHES:
Ateno: os valores de CC e de CD obtidos nessa tabela esto nas mesmas unidades de
concentrao do eixo x usadas na construo da curva de calibrao. Portanto, se houver
diferena entre as unidades do eixo x e o resultado final, e.g. ppm, ppb, etc, CC e CD
ainda devem ser convertidos para essa unidade final
Se a curva de calibrao no for feita com MRC, esses valores tambm no incluem a
correo devido a inexatido do mtodo analtico (recuperao).

t(1%) = 2.650309 ,
t(5%) = 1.770933
ns trum e nta l a b s o rv nc ia

oncentrao lquida mnima detetvel - CD (ISO 11843)


R e s p o s ta ins trum e nta l a b s o rv nc ia
amostra de ensaio
lim sup
0.0045716
0.0302736 Reta de Calibrao de MMQPA e CLP
0.0561314 0.25
0.0821436
0.1083198
f(x) = 0.0109331512x^2 + 0.2546970525x + 0.0046658529
0.1346887 0.2
f(x) = - 0.0109331512x^2 + 0.2564005759x + 0.0021893275
0.1612994
0.1882227
0.2155549 0.15

0.1
amostra de ensaio

0.05

0
0 0.1 0.2 0.3 conc
0.4 0.5 0.6 0.7 0.8 0.9
Curva de calibr ao

0.25

0.2 f (x) = 0.2410x + 0.0087


R = 0.9944
0.15

0.1

0.05

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
x = Conce ntr ao da s oluo de calib

Modelo para o DP da resposta instrumental


009

008

007

006

005
f(x) = 0.0005 exp( 2.6759 x )
004 R = 0.7700
003

002

001

0
0 0.1 0.2 0.3 x = 0.4
conc 0.5 0.6 0.7 0.8 0.9 1
A e CLP

29
3275

Reta

Linear (R et a)

CLP inf

Poly nom ial


(C LP inf )

CLP s up

Poly nom ial


(C LP sup)

0.7 0.8 0.9


Planilha para ajuste de reta de calibrao e clculo de Ccalf, Ccbeta e
Incerteza de calibrao da soluo da amostra de ensaio:
ICP OES para Ag 01-02-2008
i j xi = ci yi =resp inst s(yi) s(y)2 wi = 1/si2 wixi
1 0 56.14 3790.8136 1.4370E+07 6.9588E-08 0
1 2 0 7.474 6.958812E-008 0
3 0 28.47 6.958812E-008 0
1 0.2 4633 3790.8136 1.4370E+07 6.9588E-08 1.39E-008
2 2 0.2 4557 6.958812E-008 1.39E-008
3 0.2 4594 6.958812E-008 1.39E-008
1 0.5 9912 3790.8136 1.4370E+07 6.9588E-08 3.48E-008
3 2 0.5 9573 6.958812E-008 3.48E-008
3 0.5 9929 6.958812E-008 3.48E-008
1 1 18930 3790.8136 1.4370E+07 6.9588E-08 6.96E-008
4 2 1 18710 6.958812E-008 6.96E-008
3 1 18600 6.958812E-008 6.96E-008
1 3 74470 3790.8136 1.4370E+07 6.9588E-08 2.09E-007
5 2 3 76010 6.958812E-008 2.09E-007
3 3 75460 6.958812E-008 2.09E-007
1 5 127900 3790.8136 1.4370E+07 6.9588E-08 3.48E-007
6 2 5 129800 6.958812E-008 3.48E-007
3 5 129700 6.958812E-008 3.48E-007
1 10 248500 3790.8136 1.4370E+07 6.9588E-08 6.96E-007
7 2 10 249700 6.958812E-008 6.96E-007
3 10 250200 6.958812E-008 6.96E-007
1 20 497800 3790.8136 1.4370E+07 6.9588E-08 1.39E-006
8 2 20 484400 6.958812E-008 1.39E-006
3 20 493400 6.958812E-008 1.39E-006
1 30 739800 3790.8136 1.4370E+07 6.9588E-08 2.09E-006
9 2 30 743100 6.958812E-008 2.09E-006
3 30 740900 6.958812E-008 2.09E-006

somas: 209.1 5160670 34117.323 129332412.683 1.878879E-006 1.46E-005


Mdias 7.74444444 191135.93 3790.8136 14370268.0759 6.958812E-008 7.744444
i xi = ci yi =respinst s(yi) s(y)2 wi = 1/si2 wixi

3.512545E-010 Ver o comentrio da clula em vermelho esquer

Welington F. MAGALHES:
a= -368.8782 Ateno: os valores de CC e de
b= 24728.024 concentrao do eixo x usadas
diferena entre as unidades do
s(a) = 923.60664 Observao ainda devem ser convertidos p
s(b) = 73.137224 Se a curva de calibrao no fo
correo devido a inexatido d
cov(a,b) = -41425.45
sres = 3790.8136
N=IxJ= 27
GL = N-2 = 25 Valores crticos unilaterais
alfa/2 = ? 5 z(1%) = 2.326348
t(alfa,GL) 1.7081408 z(5%) = 1.644854

Valor crtico da concentrao lquida do analito - CC - e concentrao lquida mnim


K= 1 CLPsup(x = 0) = 6295.7865078
CC = 0.2695186946
CD = 0.5390373893

Curvas de Limite de Previso - CLP - para K replicatas da amostra de ensaio


x* y* s(y*) s2(y*) s2LP(y*) Delta(y) lim inf
0 -368.87821 3790.8136 14370268 15223317.3091 6664.6647203 -7033.543
0.2 4576.72657 3790.8136 14370268 15206961.0919 6661.0834379 -2084.357
0.5 11995.1337 3790.8136 14370268 15183229.1243 6655.8837685 5339.25
1 24359.1457 3790.8136 14370268 15145815.4662 6647.6781835 17711.47
3 73815.1935 3790.8136 14370268 15022906.102 6620.6500485 67194.54
5 123271.241 3790.8136 14370268 14942789.1663 6602.9725342 116668.3
10 246911.361 3790.8136 14370268 14929713.702 6600.0829858 240311.3
20 494191.6 3790.8136 14370268 15705920.8089 6769.4807567 487422.1
30 741471.839 3790.8136 14370268 17551938.6298 7156.2615048 734315.6

6600.0829858 = mnimo
Curvas de Limite de Previso - CLP - para K replicatas da amostra de ensaio
CV
82.83
31.60
15.56
5.14
3.08
1.54
0.77
0.51
y = r e sp o sta i n stru m e n ta l
alf, Ccbeta e

wiyi wixiyi wi(xi)2 wi(yi)2 yicalc res(y) wi*res2(y)


3.907E-006 0 0 0.000219 -368.8782 425.0182 0.01257
5.201E-007 0 0 3.89E-006 -368.8782 376.3522 0.009857 800000
700000
1.981E-006 0 0 5.64E-005 -368.8782 397.3482 0.010987 f(x) = 24,728.0
600000 R = 1.00
0.0003224 6.45E-005 2.783525E-009 1.493687 4576.727 56.27343 0.00022 500000

0.0003171 6.34E-005 2.783525E-009 1.445084 4576.727 -19.72657 2.71E-005 400000


300000
0.0003197 6.39E-005 2.783525E-009 1.468646 4576.727 17.27343 2.08E-005 200000
0.0006898 0.000345 1.739703E-008 6.836876 11995.13 -2083.134 0.301974 100000

0.0006662 0.000333 1.739703E-008 6.377218 11995.13 -2422.134 0.408255 0


0 5
0.0006909 0.000345 1.739703E-008 6.860348 11995.13 -2066.134 0.297065 x = Con

0.0013173 0.001317 6.958812E-008 24.93655 24359.15 -5429.146 2.051153

DP (y) = DP (re sp. inst.)


0.001302 0.001302 6.958812E-008 24.3603 24359.15 -5649.146 2.220755
0.0012943 0.001294 6.958812E-008 24.07471 24359.15 -5759.146 2.308082
0.0051822 0.015547 6.262931E-007 385.9205 73815.19 654.8065 0.029837
0.0052894 0.015868 6.262931E-007 402.0468 73815.19 2194.807 0.335218
0.0052511 0.015753 6.262931E-007 396.2495 73815.19 1644.807 0.188263 Modelo
0.0089003 0.044502 1.739703E-006 1138.351 123271.2 4628.759 1.490954
0.0090325 0.045163 1.739703E-006 1172.424 123271.2 6528.759 2.966172 4000

0.0090256 0.045128 1.739703E-006 1170.618 123271.2 6428.759 2.876003 3500


0.0172926 0.172926 6.958812E-006 4297.223 246911.4 1588.639 0.175625
0.0173762 0.173762 6.958812E-006 4338.826 246911.4 2788.639 0.541153 3000

0.0174109 0.174109 6.958812E-006 4356.219 246911.4 3288.639 0.752606 2500

0.034641 0.692819 2.783525E-005 17244.27 494191.6 3608.4 0.906076


0.0337085 0.67417 2.783525E-005 16328.39 494191.6 -9791.6 6.671791 2000

0.0343348 0.686696 2.783525E-005 16940.78 494191.6 -791.5996 0.043606 1500

0.0514813 1.544439 6.262931E-005 38085.86 741471.8 -1671.839 0.194502


1000
0.0517109 1.551328 6.262931E-005 38426.4 741471.8 1628.161 0.184472
0.0515578 1.546735 6.262931E-005 38199.2 741471.8 -571.8385 0.022755 500

0
0.3591214 7.404074 0.0002996374 182980.6 6.22E-010 25 0 5
191135.93 2.30E-011
wiyi wixiyi wi(xi)2 wi(yi)2 yicalc res(y) wi*res2(y)

rio da clula em vermelho esquerda

Welington F. MAGALHES:
Ateno: os valores de CC e de CD obtidos nessa tabela esto nas mesmas unidades de
concentrao do eixo x usadas na construo da curva de calibrao. Portanto, se houver
diferena entre as unidades do eixo x e o resultado final, e.g. ppm, ppb, etc, CC e CD
ainda devem ser convertidos para essa unidade final
Se a curva de calibrao no for feita com MRC, esses valores tambm no incluem a
correo devido a inexatido do mtodo analtico (recuperao).

t(1%) = 2.485107 ,
t(5%) = 1.708141
s trum e nta l re a d e p ic o

oncentrao lquida mnima detetvel - CD (ISO 11843)


R e s p o s ta ins trum e nta l re a d e p ic o
amostra de ensaio
lim sup
6295.7865
11237.81
18651.018 800000 Reta de Calibrao e CLP
31006.824
f(x)
f(x) =
= 1.1321914731x^2 + 24710.5092901152x
+ 24745.538493144x+- 6294.9554058988
80435.844 700000 - 1.1321914731x^2 7032.7118310656
129874.21
253511.44 600000
500961.08
748628.1 500000

400000

300000
amostra de ensaio
200000

100000

0
0 5 10 15 20 25 30 35
-100000 conc / mg/L
Curva de calibrao
800000
700000
f(x) = 24,728.02x - 368.88
600000 R = 1.00
500000
400000
300000
200000
100000
0
0 5 10 15 20 25 30 35
x = Concentrao da soluo de calib

Modelo para o DP da resposta instrumental

4000

3500

3000

2500

2000

1500

1000

500

0
0 5 10 15 20 25 30 35
x = conc
LP

94.9554058988
32.7118310656

R eta

Linear (R et a)

C LP inf

Poly nom ial (CLP inf )

C LP s up

Poly nom ial (CLP s up)

30 35
Planilha para ajuste de reta de calibrao e clculo de Ccalf, Ccbeta e
Incerteza de calibrao da soluo da amostra de ensaio:
Dados de calibrao de GC/NPD para determinao de chlorfenvinphos do artigo de Souza
i j xi = ci yi =resp inst s(yi) s(y)2 wi = 1/si2 wixi
1 9.952285 196.7616 43.2354 1.8693E+03 5.3496E-04 0.005324
1 2 9.952285 283.2324 0.0005349597 0.005324
3 9.952285 239.997 0.0005349597 0.005324
1 30.25772 732.8805 55.592904 3.0906E+03 3.2356E-04 0.00979
2 2 30.25772 646.4098 0.0003235648 0.00979
3 30.25772 629.1156 0.0003235648 0.00979
1 50.56315 1277.647 139.78726 1.9540E+04 5.1176E-05 0.002588
3 2 50.56315 1173.882 5.117582E-005 0.002588
3 50.56315 1000.94 5.117582E-005 0.002588
1 71.08429 1675.412 154.36637 2.3829E+04 4.1966E-05 0.002983
4 2 71.08429 1571.647 4.196571E-005 0.002983
3 71.08429 1875.346 4.196571E-005 0.002983
1 91.38972 2394.694 175.85537 3.0925E+04 3.2336E-05 0.002955
5 2 91.38972 2081.825 3.233618E-005 0.002955
3 91.38972 2099.119 3.233618E-005 0.002955
1 112.0277 2983.993 375.61224 1.4108E+05 7.0879E-06 0.000794
6 2 112.0277 2375.826 7.087948E-006 0.000794
3 112.0277 2298.002 7.087948E-006 0.000794
1
7 2
3
1
8 2
3
1
9 2
3

somas: 1095.8246 25536.73 944.44955 220338.993742 0.0029732704 0.073303


Mdias 60.8791442 1418.7072 157.40826 36723.1656236 0.0001651817 24.65402
i xi = ci yi =respinst s(yi) s(y)2 wi = 1/si2 wixi

0.0040026197 Ver o comentrio da clula em vermelho esquer

Welington F. MAGALHES:
a= -6.737175 Ateno: os valores de CC e de
concentrao do eixo x usadas
b= 23.376981 diferena entre as unidades do
s(a) = 28.068456 Observao ainda devem ser convertidos p
s(b) = 0.8618765 Se a curva de calibrao no f
correo devido a inexatido d
cov(a,b) = -18.31377
sres = 73.165019
N=IxJ= 18
GL = N-2 = 16 Valores crticos unilaterais
alfa/2 = ? 5 z(1%) = 2.326348
t(alfa,GL) 1.7458837 z(5%) = 1.644854

Valor crtico da concentrao lquida do analito - CC - e concentrao lquida mnim


K= 1 CLPsup(x = 0) = 73.094218001
CC = 3.4149573929
CD = 6.8299147857

Curvas de Limite de Previso - CLP - para K replicatas da amostra de ensaio


x* y* s(y*) s2(y*) s2LP(y*) Delta(y) lim inf
0 -6.7371754 36.09685 1302.9826 2090.82079304 79.831393402 -86.56857
10 227.032633 44.132903 1947.7131 2443.55895338 86.30316344 140.7295
20 460.802441 53.95798 2911.4637 3263.88331335 99.743043615 361.0594
30 694.572249 65.970364 4352.0889 4709.64857494 119.81454848 574.7577
40 928.342057 80.657001 6505.5518 7016.8177356 146.2464734 782.0956
50 1162.11186 98.613247 9724.5725 10538.110958 179.22421544 982.8876
60 1395.88167 120.567 14536.401 15800.7783387 219.45958051 1176.422
70 1629.65148 147.4082 21729.177 23592.9592969 268.16772868 1361.484
80 1863.42129 180.22492 32481.02 35092.7735684 327.05752921 1536.364
90 2097.1911 220.34745 48553 52061.2878855 398.35727982 1698.834
10 227.032633 44.132903 1947.7131 2443.55895338 86.30316344 140.7295
110 2564.73071 329.37786 108489.77 114236.838974 590.09018774 1974.641
120 2798.50052 402.70553 162171.75 169261.045138 718.28006538 2080.22
24.65402 569.599445 <-- Centride

s(y*) = 36,09685*EXP(0,0201*x) 79.831393402 = mnimo


Curvas de Limite de Previso - CLP - para K replicatas da amostra de ensaio
CV
19.44
11.71
9.50
8.69
8.49
8.64
9.05
9.67
alf, Ccbeta e

vinphos do artigo de Souza SVC Analytica Chimica Acta 552 (2005) 2535
wiyi wixiyi wi(xi)2 wi(yi)2 yicalc res(y) wi*res2(y) raiz(wi)*res(y)
0.1052595 1.047573 0.0529866723 20.71103 225.9172 -29.1556 0.454742 -6.7435E-01
0.1515179 1.507949 0.0529866723 42.91478 225.9172 57.3152 1.75736 1.3257E+00
0.1283887 1.277761 0.0529866723 30.81291 225.9172 14.0798 0.106051 3.2565E-01
0.2371343 7.175144 0.2962331654 173.7911 700.597 32.28354 0.337228 5.8071E-01
0.2091555 6.328567 0.2962331654 135.2001 700.597 -54.18716 0.950067 -9.7471E-01
0.2035597 6.159251 0.2962331654 128.0626 700.597 -71.48136 1.653282 -1.2858E+00
0.0653846 3.306053 0.1308377409 83.53848 1175.277 102.3704 0.536307 7.3233E-01
0.0600744 3.037549 0.1308377409 70.52022 1175.277 -1.394611 9.95E-005 -9.9767E-03
0.0512239 2.590043 0.1308377409 51.27207 1175.277 -174.3366 1.5554 -1.2472E+00
0.0703099 4.997926 0.2120517502 117.798 1654.999 20.41309 0.017487 1.3224E-01
0.0659553 4.688385 0.2120517502 103.6584 1654.999 -83.35191 0.291558 -5.3996E-01
0.0787002 5.59435 0.2120517502 147.5902 1654.999 220.3471 2.037555 1.4274E+00
0.0774353 7.076786 0.270074392 185.4337 2129.679 265.0154 2.271073 1.5070E+00
0.0673183 6.152198 0.270074392 140.1449 2129.679 -47.85355 0.074049 -2.7212E-01
0.0678775 6.203305 0.270074392 142.4829 2129.679 -30.55955 0.030198 -1.7378E-01
0.0211504 2.369429 0.0889552057 63.11261 2612.132 371.8608 0.980125 9.9001E-01
0.0168397 1.886516 0.0889552057 40.00827 2612.132 -236.3062 0.395795 -6.2912E-01
0.0162881 1.82472 0.0889552057 37.43013 2612.132 -314.1302 0.699423 -8.3632E-01

1.6935732 73.22351 3.1534167798 1714.482 40.92854 14.1478


569.59945 2.273808
wiyi wixiyi wi(xi)2 wi(yi)2 yicalc res(y) wi*res2(y)

rio da clula em vermelho esquerda

Welington F. MAGALHES:
Ateno: os valores de CC e de CD obtidos nessa tabela esto nas mesmas unidades de
concentrao do eixo x usadas na construo da curva de calibrao. Portanto, se houver
diferena entre as unidades do eixo x e o resultado final, e.g. ppm, ppb, etc, CC e CD
ainda devem ser convertidos para essa unidade final
Se a curva de calibrao no for feita com MRC, esses valores tambm no incluem a
correo devido a inexatido do mtodo analtico (recuperao).

t(1%) = 2.583487 ,
t(5%) = 1.745884
ns trum e nta l re a d e p ic o

oncentrao lquida mnima detetvel - CD (ISO 11843)


R e s p o s ta ins trum e nta l re a d e p ic o
amostra de ensaio
lim sup
73.094218
313.3358 4000
560.54548 Reta de Calibrao MMQPA e CLP
814.3868 3500
f(x) = 0.04979811x^2 + 22.4809051257x + 85.0547265679
1074.5885
1341.3361 3000
1615.3413
f(x) = 23.3769807989x - 6.7371754004
1897.8192 2500 R = 1
2190.4788
2495.5484 2000 f(x) = - 0.04979811x^2 + 24.2730564721x - 98.5290773688
313.3358
3154.8209 1500
3516.7806
1000

500

amostra de ensaio 0
0 20 40 60 80 100 120 140
conc / ng/mL
-500
y = re sp o sta in stru m e n ta l

Curva de calibrao
3500

3000

2500
f(x) = 23.360110x - 3.436261
2000 R = 0.961610
1500

1000

500

0
x = Concentrao da soluo de calib / ng/mL
0 20 40 60 80 100 120
DP (y) = DP (re sp . in st.)

Modelo para o DP da resposta instrumental

400

350

f(x) = 36.0968 exp( 0.0201 x )


300
R = 0.9310
250

200
R e s d u o p a d r o n iz a d o d e M M Q P A

150

100

50

0
0 20 40 60 80 100 120
x = conc / ng/mL

2.0000E+00

1.5000E+00

1.0000E+00

5.0000E-01

0.0000E+00

-5.0000E-01

-1.0000E+00

-1.5000E+00
0 20 Conc.
40 ng/mL
60 80 100 120
e CLP

47265679

R et a

Linear (R eta)

C LP inf
5290773688
Poly nom ial
(C LP inf )

C LP sup

Poly nom ial


(C LP s up)

baricent ro

100 120 140


y = r e s p o s t a in s t r u m e n t a l
Conc. rea
1 9.952285 196.7616
2 9.952285 283.2324
3 9.952285 239.997
4 30.25772 732.8805
5 30.25772 646.4098
6 30.25772 629.1156
7 50.56315 1277.647
2500
8 50.56315 1173.882 f(x) = 21.4099923317x + 46.545348685
9 50.56315 1000.94 2000 R = 0.9869876969
10 71.08429 1675.412
1500
11 71.08429 1571.647
100 120 12 1000

13 500
14 91.38972 2081.825
0
15 91.38972 2099.119 0 20 40 60 80 100
16 x = Concentrao da soluo de calib /

17 112.0277 2375.826
18 112.0277 2298.002

120
317x + 46.545348685
9

60 80 100 120
o da soluo de calib / ng/mL