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 applications, spectra may be measured on a basestock and the PTMR may be measured on the same basestock after constant level additivation.
1.5.1 Biofuel applications will typically fall into three categories.
1.5.1.1 The spectra and the PTM both measure the finished biofuel blend.
1.5.1.2 The spectra are measured on a petroleum derived blendstock, and the PTM measures the same blendstock after a constant level additivation with the biocomponent.
1.5.1.3 The spectra and PTM both measured the petroleum derived blendstock, and the PPTMRs from the multivariate model are used as inputs into a second model which predicts the results obtained when the PTM is applied to the analysis of the finished blended product. The practice described herein only applies to the first of these two models.
1.6 This practice includes a checklist in Annex A2 against which multivariate calibrations can be examined to determine if they conform to the requirements defined herein.
1.7 For some multivariate spectroscopic analyses, interferences and matrix effects are sufficiently small that it is possible to calibrate using mixtures that contain substantially fewer chemical components than the samples that will ultimately be analyzed. While these surrogate methods generally make use of the multivariate mathematics described herein, they do not conform to procedures described herein, specifically with respect to the handling of outliers. Surrogate methods may indicate that they make use of the mathematics described herein, but they should not claim to follow the procedures described herein. Test Methods D5845 and D6277 are examples of surrogate methods.
1.8 Disclaimer of Liability as to Patented Inventions—Neither ASTM International nor an ASTM committee shall be responsible for identifying all patents under which a license is required in using this document. ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned in this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk of infringement of such rights, are entirely their own responsibility.
1.9 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.10 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of regulatory limitations prior to use.
1.11 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
