Rank determination of spectroscopic profiles by means of cross validation: The effect of replicate measurements on the effective degrees of freedom

Abstract In the present work the effect of sample replication and ‘true’ instrumental resolution on the number of significant latent variables obtained by cross validation is investigated. Three sample sets containing three and four chemical components were prepared according to mixture design. The samples were analysed by Fourier transform infrared spectroscopy, and cross validation was performed using the predicted residual error sum of squares (PRESS) algorithm with a varying number of degrees of freedom. It was found that the correct number of chemical components could be estimated precisely from the instrumental data (the X matrix) presuming that the degrees of freedom were corrected for the above-mentioned effects. Grung, B. and Kvalheim, O.M., 1994. Rank determination of spectroscopic profiles by means of cross validation. The effect of replicate measurements on the effective degrees of freedom. Chemometrics and Intelligent Laboratory Systems , 22: 115–125.

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