ASTM D8321-22
(Practice)Standard Practice for Development and Validation of Multivariate Analyses for Use in Predicting Properties of Petroleum Products, Liquid Fuels, and Lubricants based on Spectroscopic Measurements
Standard Practice for Development and Validation of Multivariate Analyses for Use in Predicting Properties of Petroleum Products, Liquid Fuels, and Lubricants based on Spectroscopic Measurements
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...
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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.
Designation: D8321 − 22
Standard Practice for
Development and Validation of Multivariate Analyses for Use
in Predicting Properties of Petroleum Products, Liquid
Fuels, and Lubricants based on Spectroscopic
1
Measurements
This standard is issued under the fixed designation D8321; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope* 1.3 The implementation of this practice requires that the IR
spectrophotometerorRamanspectrometerhasbeeninstalledin
1.1 This practice covers a guide for the multivariate cali-
compliancewiththemanufacturer’sspecifications.Inaddition,
bration of infrared (IR) spectrophotometers and Raman spec-
it assumes that, at the time of calibration, validation, and
trometers used in determining the physical, chemical, and
analysis,theanalyzerisoperatingattheconditionsspecifiedby
performance properties of petroleum products, liquid fuels
the manufacturer. The practice includes instrument perfor-
includingbiofuels,andlubricants.Thispracticeisapplicableto
mance tests which define the instrument performance at the
analyses conducted in the near infrared (NIR) spectral region
(roughly 780nm to 2500nm) through the mid infrared (MIR) time of calibration, and which qualify the instrument by
-1 -1
spectral region (roughly 4000cm to 40 cm ). For Raman demonstrating comparable performance during validation and
analyses, this practice is generally applied to Stokes shifted
analysis.
-1 -1
bands that occur roughly 400cm to 4000cm below the
1.4 This practice covers techniques that are routinely ap-
frequency of the excitation.
plied for online, at-line, and laboratory quantitative analysis.
NOTE 1—While the practice described herein deals specifically with
The practice outlined covers the general cases for liquids and
mid-infrared, near-infrared, and Raman analysis, much of the mathemati-
solids that are single phase homogeneous samples when
cal and procedural detail contained herein is also applicable for multivari-
presented to the analyzers. Online application is limited by
ate quantitative analysis done using other forms of spectroscopy.The user
is cautioned that typical and best practices for multivariate quantitative sample viscosity and the ability to introduce sample to the
analysis using other forms of spectroscopy may differ from the practice
analyzer.All techniques covered require the use of a computer
described herein for mid-infrared, near-infrared, and Raman spectrosco-
for data collection and analysis.
pies.
1.2 Procedures for collecting and treating data for develop- 1.5 This practice is most typically applied when the spectra
ing IR and Raman calibrations are outlined. Definitions, terms, and the PTMR against which the analysis is calibrated are
and calibration techniques are described. The calibration es-
measuredonthesamesample.However,forsomeapplications,
tablishes a multivariate correlation between the spectral fea-
spectramaybemeasuredonabasestockandthePTMRmaybe
tures and the properties to be predicted. This correlation is
measured on the same basestock after constant level additiva-
herein referred to as the multivariate model. Criteria for
tion.
validating the performance of the multivariate model are
1.5.1 Biofuel applications will typically fall into three
described.Thepropertiesagainstwhichamultivariatemodelis
categories.
calibrated and validated are measured by Primary Test Meth-
1.5.1.1 The spectra and the PTM both measure the finished
ods(PTMs)andtheresultsofthePTMmeasurementareherein
biofuel blend.
referred to as Primary Test Method Results (PTMR). The
1.5.1.2 The spectra are measured on a petroleum derived
analysis of the spectra using the multivariate model produces a
blendstock, and the PTM measures the same blendstock after a
Predicted Primary Test Method Result (PPTMR).
constant level additivation with the biocomponent.
1.5.1.3 The spectra and PTM both measured the petroleum
1
This practice is under the jurisdiction ofASTM Committee D02 on Petroleum
derived blendstock, and the PPTMRs from the multivariate
Products, Liquid Fuels, and Lubricants and is the direct responsibility of Subcom-
mittee D02.25 on Performance Assessment and Validation of Process Stream
model are used as inputs into a second model which predicts
Analyzer Systems.
the results obtained when the PTM is applied to the analysis of
Current edition approved April 1, 2022. Published June 2022. Originally
the finished blended product. The practice des
...
This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: D8321 − 21 D8321 − 22
Standard Practice for
Development and Validation of Multivariate Analyses for Use
in Predicting Properties of Petroleum Products, Liquid
Fuels, and Lubricants based on Spectroscopic
1
Measurements
This standard is issued under the fixed designation D8321; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. 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)
-1 -1
through the mid infrared (MIR) spectral region (roughly 4000 cm to 40 cm ). For Raman analyses, this practice is generally
-1 -1
applied to Stokes shifted bands that occur roughly 400 cm to 4000 cm 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
This practice is under the jurisdiction of ASTM Committee D02 on Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of Subcommittee
D02.25 on Performance Assessment and Validation of Process Stream Analyzer Systems.
Current edition approved May 1, 2021April 1, 2022. Published July 2021June 2022. Originally approved in 2020. Last previous edition approved in 20202021 as
D8321 – 20.D8321 – 21. DOI: 10.1520/D8321-21.10.1520/D8321-22.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
1
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D8321 − 22
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 B
...
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