Calibration data from Massart et al. (1997), example 3

Sample dataset from p. 188 to test the package.

massart97ex3

Format

A dataframe containing 6 levels of x values with 5 observations of y for each level.

Source

Massart, L.M, Vandenginste, B.G.M., Buydens, L.M.C., De Jong, S., Lewi, P.J., Smeyers-Verbeke, J. (1997) Handbook of Chemometrics and Qualimetrics: Part A, Chapter 8.

Examples

# For reproducing the results for replicate standard measurements in example 8,
# we need to do the calibration on the means when using chemCal > 0.2
weights <- with(massart97ex3, {
  yx <- split(y, x)
  ybar <- sapply(yx, mean)
  s <- round(sapply(yx, sd), digits = 2)
  w <- round(1 / (s^2), digits = 3)
})

massart97ex3.means <- aggregate(y ~ x, massart97ex3, mean)

m3.means <- lm(y ~ x, w = weights, data = massart97ex3.means)

# The following concords with the book p. 200
inverse.predict(m3.means, 15, ws = 1.67)  # 5.9 +- 2.5
#> $Prediction
#> [1] 5.865367
#> 
#> $`Standard Error`
#> [1] 0.8926109
#> 
#> $Confidence
#> [1] 2.478285
#> 
#> $`Confidence Limits`
#> [1] 3.387082 8.343652
#> 
inverse.predict(m3.means, 90, ws = 0.145) # 44.1 +- 7.9
#> $Prediction
#> [1] 44.06025
#> 
#> $`Standard Error`
#> [1] 2.829162
#> 
#> $Confidence
#> [1] 7.855012
#> 
#> $`Confidence Limits`
#> [1] 36.20523 51.91526
#> 

# The LOD is only calculated for models from unweighted regression
# with this version of chemCal
m0 <- lm(y ~ x, data = massart97ex3) 
lod(m0)
#> $x
#> [1] 5.407085
#> 
#> $y
#> [1] 13.63911
#> 

# Limit of quantification from unweighted regression
loq(m0)
#> $x
#> [1] 9.627349
#> 
#> $y
#> [1] 22.00246
#> 

# For calculating the limit of quantification from a model from weighted
# regression, we need to supply weights, internally used for inverse.predict
# If we are not using a variance function, we can use the weight from
# the above example as a first approximation (x = 15 is close to our
# loq approx 14 from above).
loq(m3.means, w.loq = 1.67)
#> $x
#> [1] 7.346195
#> 
#> $y
#> [1] 17.90777
#> 
# The weight for the loq should therefore be derived at x = 7.3 instead
# of 15, but the graphical procedure of Massart (p. 201) to derive the 
# variances on which the weights are based is quite inaccurate anyway.