Linear Analytical Calibration Curve (Regression STD Dev LOD STD Add)
Linear Analytical Calibration Curve (Regression STD Dev LOD STD Add)
Determination of unknow x and error estimates and LOD from measured y vs. x data by unweighted linear regression.
Homoscedastic data with normal error distribution is assumed.
Ivano Gutz - IQ-USP * If there is a significant increase in volume
during the addition of standards to the sampl
refer to cell P2 to apply corrections.
Calibration data defining the Analytical Curve
Enter x (Conc.) and y (Signal) data (n <=30, expandable).
Volumes should be first converted to concentrations.
Use new lines for replicates (if any).
0.8
Analytical Calibration Curve or Standard Addition C
0.7
f(x) = 0.268884571428571 x + 0.0110309523809524
R² = 0.999140913233016
0.6
0.5
Signal
0.4
0.3
0.2
0.1
0
0 0.5 1 1.5 2
Concentration
0.01
y residuals
0.005
0
0 0.5 1 1.5 2
-0.005
-0.01
-0.015
0
0 0.5 1 1.5 2
-0.005
-0.01
-0.015
on and Standard Additions*
nweighted linear regression.
28571 x + 0.0110309523809524
3016
1 1.5 2 2.5 3
Concentration
1 1.5 2 2.5 3
1 1.5 2 2.5 3
Standard Addition with variable volume - data preparation
The addition of a volume Vad of standard of concentration Cstd to a certain initial volume Vin of solution containing
xx, to be determined) and, consequently, attenuates its original signal (that is added to the signal due to the stan
colum Signalcorr. of the Data Output, used to find the Result xx (cell W10) by linear regression. To plot the Data
copy Cad std. and Signalcorr. and Paste Special Values in Conc. x and Signal y (columns A and B).
rrection
Some notes, definitions, examples and bibliography, in English and Portuguese, randomly paste
Most of the statistical equations employed here are available, for example, in Harvey's book [1] or in Hughes's spreads
(but not the results uncertainty) can also be obtained with the Analysis ToolPak supplement of Excel, that includes ANO
The parameters values (including the 'results uncertainty') where checked against examples in references [1] and [2] am
References:
[1] David Harvey, 5.4: Linear Regression and Calibration Curves
https://chem.libretexts.org/Bookshelves/Analytical_Chemistry/Analytical_Chemistry_2.1_(Harvey)/05%3A_Standardiz
5.04%3A_Linear_Regression_and_Calibration_Curves
[2] Jeff Hughes's (RMIT University) - Regression Statistics for Analytical Determinations, Excel spreadsheet, 2002 (no lo
Orientação sobre a Validação de Métodos Analíticos DOQ-CGCRE-008 Revisão 05 Agosto 2016 (INMETRO)
Comparar equações de LD e LQ com: Planilha de validação: uma nova ferramenta para estimar figura
Test data set for standard addition (LD = 3,3s) Validação - Uma revisão baseada em documentos e normas (na
http://www.portalaction.com.br/validacao-de-metodologia-analitica
http://www.cnpsa.embrapa.br/met/images/arquivos/14MET/n
Traz a diferenças nas definições adotadas pelas várias normas:
Example of standard addition with variable volume for fluoride ISE by Zellmer
V0 100 mL slope 59.16
Cstd 300 mg F/L Response=(B$61+A64)*10^((B$64-B64)/E$61)
Vstd, mL E, mV Cstd, mg/LResponse Cstd+Cx log (Cstd+Cx)
0 80.3 0.00 #VALUE! 2.12 0.325618
0.3 71.1 0.90 #VALUE! 3.00 0.477248
0.6 64.6 1.79 #VALUE! 3.88 0.588838
0.9 59.7 2.68 #VALUE! 4.75 0.677067
1.2 55.1 3.56 #VALUE! 5.62 0.749969
resultados ao lado desvia da reta, slope 2x59
Ver tb: Metodologia Estatística para Validação de Métodos Analíticos Aplicável à Metrologia em Química
Sônia Maria de Freitas, dissertação de mestrado, PUC-Rio, 2003
https://www.maxwell.vrac.puc-rio.br/4058/4058_1.PDF (e cap. subsequentes _2, _3, etc.)
NMETRO) http://www.inmetro.gov.br/Sidoq/Arquivos/Cgcre/DOQ/DOQ-Cgcre-8_05.pdf
not only be reliably detected but at which some predefined goals for bias and imprecision are met.
hat results in a CV=20% (or some other predetermined % CV)
t of Quantitation (LoQ) are terms used to describe the smallest concentration of a measurand that can be reliably measured by an analytica
ected to be found when replicates of a blank sample containing no analyte are tested.
ably distinguished from the LoB and at which detection is feasible. LoD is determined by utilising both the measured LoB and test replicates
an not only be reliably detected but at which some predefined goals for bias and imprecision are met. The LoQ may be equivalent to the LoD
REGRESSION PARAMETERS
100.2406 a intercept 1.109634
47.36075 b slope 0.508369
0.999654 r2 correlati 0.999827
Relative St 0.006715
Std dev of sy/x 1.429688
3*S(residua3*sy/x 4.289064
Limit of de 0.090562
Limit of qu 0.301872
number of n 5
two-tailed t 3.18
Tipos de soluç
Branco de mé
analito, a ser
Branco para r
todos os proc
Branco de cam
amostragem.
Brancos não n
por traços de
análise, ou do
Química
http://www.ufj
Analytical function – the relation between a measured quantity x and the Curva Analítica é o
concentration c.
Analytical curve – a graphical plot of the analytical function, whatever the Curva analítica de c
UPAC 1997 coordinate axes used. NOMENCLATURE, S
Analytical calibration function – the measured quantity expressed as http://publications.iu
function of c[i.e., x= g(c)].
Analytical calibration curve – a graph of the analytical calibration function.
imites_Sistemas_analiticos.pdf
IUPAC’s Compendium of Analytical Nomenclature [15] (Section 10.3.3.2)
http://www.iupac.org/publications/analytical_compendium/
Pure Appl. Chem., 2008, Vol. 80, No. 1, pp. 85-104
a cromatografia).
Calibration plot – alternative designation of analytical calibration curve of
an ISE (Section 8.3.2.1).
-166-de-24-de-julho-de-2017-19194412
http://dx.doi.org/10.1351/pac200880010085
ANALYTICAL CALIBRATION CURVES (CALIBRATION PLOTS) FOR pH AND
OTHER ION-SELECTIVE ELECTRODES
Colegiada To have unified presentation of the calibration plots of all ISEs, it is
recommended that the cell emf is ascribed to the ordinate (vertical axis)
with more positive potentials at the top, and the pa A or pcA values be
ation, with definitions, see also plotted on the horizontal axis with increasing pa A or pcA values to the right.
cielo.php?script=sci_arttext&pid=S0100-40422019000100099
About LOD, etc. of ISEs see Recommendations for nomenclature of ions-
elective electrodes (IUPAC Recommendations 1994) R. P. Buck, E, Lindner
df/qn/v42n1/0100-4042-qn-42-01-0099-suppl01.pdf
https://publications.iupac.org/pac/66/12/2527/index.html
tcm18-216960.pdf
DATA INPUT
, page 1241 Conc. x Signal y Write only in the whitStandard
0 0.24 A12 to B41; I11 to S1 Addition
5.55 0.437 Determined resulMethod
11.1 0.621 Measureme yx 0.24
16.65 0.809 Number ofm 1
22.2 1.009 Predicted rxx 7.008691
Std dev of sxx 0.178697
Result's un(CI 95%) + 0.568693
REGRESSION PARAMETERS
0.2412 a intercept 0.003763
0.034414 b slope 0.000277
0.999806 r2 correlati 0.999903
Relative St 0.00844
Std dev of sy/x 0.004858
3*S(residua3*sy/x 0.014574
Limit of de 0.423484
Limit of qu 1.411613
number of n 5
two-tailed t 3.182446
ntent/id/19194581/do1-2017-07-25-resolucao-rdc-n-166-de-24-de-julho-de-2017-19194412
No teste de significância da regre
a média quadrática residual (MQr
MQR e MQr a um certo nível de co
maior que o valor de F, conclui-se
O teste de falta de ajuste compara
(MQfaj) com a média quadrática d
valor do ponto de distribuição F, r
confiança, temos um modelo sem
sy / x ( yo y ) 2
s xo { m1 1
}0.5
b n b 2
( xi x ) 2
(ANOVA)
NETO; SCARMINIO; BRUNS, Como Fazer experimentos – Pesquisa e Desenvolvimento na Ciência e na Indústria, 2010
gnificância da regressão, compara-se a razão entre a média quadrática devido à regressão (MQ R) e
ática residual (MQr) com o valor do ponto da distribuição F referente aos graus de liberdade de
um certo nível de confiança estatística, que é em geral, 95% de confiança. Se a referida razão for
alor de F, conclui-seque a regressão é estatisticamente significativa.
a de ajuste compara, para os vários níveis da variável X, a média quadrática da falta de ajuste
média quadrática devida ao erro puro (MQ ep). Assim, se a razão (MQfaj)/(MQep) for menor que o
de distribuição F, referentes aos graus de liberdade de MQ faj e MQep e para um nível de 95% de
mos um modelo sem falta de ajuste.