ASTM D8321-22

SIGNIFICANCE AND USE 5.1 This practice can be used to establish the validity of the results obtained by an infrared (IR) spectrophotometer or Raman spectrometer at the time the calibration is developed. The ongoing validation of PPTMRs produced by analysis of unknown samples using the multivariate model is covered separately (see for example, Practice D6122). 5.2 The multivariate calibration procedures define the range over which measurements are valid and demonstrate whether the accuracy and precision of the analysis outputs meet user requirements. 5.3 This practice describes sampling procedures that must be followed to ensure that the sample which is analyzed by the spectrophotometer or spectrometer is the same as the sample analyzed by the PTM. The sampling procedures apply to analyses done on lab analyzers, at-line analyzers, and online analyzers. SCOPE 1.1 This practice covers a guide for the multivariate calibration of infrared (IR) spectrophotometers and Raman spectrometers used in determining the physical, chemical, and performance properties of petroleum products, liquid fuels including biofuels, and lubricants. This practice is applicable to analyses conducted in the near infrared (NIR) spectral region (roughly 780 nm to 2500 nm) through the mid infrared (MIR) spectral region (roughly 4000 cm-1 to 40 cm-1). For Raman analyses, this practice is generally applied to Stokes shifted bands that occur roughly 400 cm-1 to 4000 cm-1 below the frequency of the excitation. Note 1: While the practice described herein deals specifically with mid-infrared, near-infrared, and Raman analysis, much of the mathematical and procedural detail contained herein is also applicable for multivariate quantitative analysis done using other forms of spectroscopy. The user is cautioned that typical and best practices for multivariate quantitative analysis using other forms of spectroscopy may differ from the practice described herein for mid-infrared, near-infrared, and Raman spectroscopies. 1.2 Procedures for collecting and treating data for developing IR and Raman calibrations are outlined. Definitions, terms, and calibration techniques are described. The calibration establishes a multivariate correlation between the spectral features and the properties to be predicted. This correlation is herein referred to as the multivariate model. Criteria for validating the performance of the multivariate model are described. The properties against which a multivariate model is calibrated and validated are measured by Primary Test Methods (PTMs) and the results of the PTM measurement are herein referred to as Primary Test Method Results (PTMR). The analysis of the spectra using the multivariate model produces a Predicted Primary Test Method Result (PPTMR). 1.3 The implementation of this practice requires that the IR spectrophotometer or Raman spectrometer has been installed in compliance with the manufacturer's specifications. In addition, it assumes that, at the time of calibration, validation, and analysis, the analyzer is operating at the conditions specified by the manufacturer. The practice includes instrument performance tests which define the instrument performance at the time of calibration, and which qualify the instrument by demonstrating comparable performance during validation and analysis. 1.4 This practice covers techniques that are routinely applied for online, at-line, and laboratory quantitative analysis. The practice outlined covers the general cases for liquids and solids that are single phase homogeneous samples when presented to the analyzers. Online application is limited by sample viscosity and the ability to introduce sample to the analyzer. All techniques covered require the use of a computer for data collection and analysis. 1.5 This practice is most typically applied when the spectra and the PTMR against which the analysis is calibrated are measured on the same sample. However, for some applic...