ASTM D6122-01

Standard Practice for Validation of Multivariate Process Infrared Spectrophotometers

SCOPE
1.1 This practice covers requirements for the validation of measurements made by on-line, process near- or mid-infrared analyzers, or both, used in the calculation of physical, chemical, or quality parameters of liquid petroleum products. The parameters are calculated from spectroscopic data using multivariate modeling methods. The requirements include verification of adequate instrument performance, verification of the applicability of the calibration model to the spectrum of the sample under test, and verification of equivalence between the result calculated from the infrared measurements and the result produced by the primary method used for the development of the calibration model.
1.2 This practice does not cover procedures for establishing the calibration model used by the analyzer. Calibration procedures are covered in Practices E 1655 and references therein.
1.3 This practice is intended as a review for experienced persons. For novices, this practice will serve as an overview of techniques used to verify instrument performance, to verify model applicability to the spectrum of the sample under test, and to verify equivalence between the parameters calculated from the infrared measurement and the results of the primary method measurement.
1.4 This practice teaches and recommends appropriate statistical tools, outlier detection methods, for determining whether the spectrum of the sample under test is a member of the population of spectra used for the analyzer calibration. The statistical tools are used to determine if the infrared measurement results in a valid property or parameter estimate.
1.5 The outlier detection methods do not define criteria to determine whether the sample, or the instrument is the cause of an outlier measurement. Thus, the operator who is measuring samples on a routine basis will find criteria to determine that a spectral measurement lies outside the calibration, but will not have specific information on the cause of the outlier. This practice does suggest methods by which instrument performance tests can be used to indicate if the outlier methods are responding to changes in the instrument response.
1.6 This practice is not intended as a quantitative performance standard for the comparison of analyzers of different design.
1.7 Although this practice deals primarily with validation of on-line, process infrared analyzers, the procedures and statistical tests described herein are also applicable to at-line and laboratory infrared analyzers which employ multivariate models.
1.8 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 consult and establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

General Information

• Status: Historical
• Publication Date: 09-Dec-2001
• ICS: 17.180.30 - Optical measuring instruments
• Technical Committee: D02 - Petroleum Products, Liquid Fuels, and Lubricants
• Drafting Committee: D02.25 - Performance Assessment and Validation of Process Stream Analyzer Systems

Relations

• Replaces: ASTM D6122-99 - Standard Practice for Validation of Multivariate Process Infrared Spectrophotometers
• Effective Date: 10-Dec-2001
• Replaced By: ASTM D6122-06 - Standard Practice for Validation of the Performance of Multivariate Process Infrared Spectrophotometers
• Effective Date: 01-Jul-2006
• Referred By: ASTM D6624-20 - Standard Practice for Determining a Flow-Proportioned Average Property Value (FPAPV) for a Collected Batch of Process Stream Material Using Stream Analyzer Data
• Effective Date: 10-Dec-2001
• Referred By: ASTM C1307-21 - Standard Test Method for Plutonium Assay by Plutonium (III) Diode Array Spectrophotometry
• Effective Date: 10-Dec-2001
• Referred By: ASTM D7453-22 - Standard Practice for Sampling of Petroleum Products for Analysis by Process Stream Analyzers and for Process Stream Analyzer System Validation
• Effective Date: 10-Dec-2001
• Referred By: ASTM D8340-22 - Standard Practice for Performance-Based Qualification of Spectroscopic Analyzer Systems
• Effective Date: 10-Dec-2001
• Referred By: ASTM D7166-23 - Standard Practice for Total Sulfur Analyzer Based On-line/At-line for Sulfur Content of Gaseous Fuels
• Effective Date: 10-Dec-2001
• Referred By: ASTM D7825-18 - Standard Practice for Generating a Process Stream Property Value through Application of a Process Stream Analyzer
• Effective Date: 10-Dec-2001
• Referred By: ASTM 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 Measurements
• Effective Date: 10-Dec-2001
• Referred By: ASTM D6621-21 - Standard Practice for Performance Testing of Process Analyzers for Aromatic Hydrocarbon Materials
• Effective Date: 10-Dec-2001
• Referred By: ASTM D7314-21 - Standard Practice for Determination of the Heating Value of Gaseous Fuels using Calorimetry and On-line/At-line Sampling
• Effective Date: 10-Dec-2001
• Referred By: ASTM D3764-23 - Standard Practice for Validation of the Performance of Process Stream Analyzer Systems
• Effective Date: 10-Dec-2001
• Referred By: ASTM D7808-22 - Standard Practice for Determining the Site Precision of a Process Stream Analyzer on Process Stream Material
• Effective Date: 10-Dec-2001
• Referred By: ASTM D4814-23 - Standard Specification for Automotive Spark-Ignition Engine Fuel
• Effective Date: 10-Dec-2001
• Referred By: ASTM E1655-17 - Standard Practices for Infrared Multivariate Quantitative Analysis
• Effective Date: 10-Dec-2001

Standards Content (Sample)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
An American National Standard
Designation:D6122–01
Standard Practice for
Validation of Multivariate Process Infrared
1
Spectrophotometers
This standard is issued under the fixed designation D6122; 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 (e) indicates an editorial change since the last revision or reapproval.
1. Scope mance tests can be used to indicate if the outlier methods are
responding to changes in the instrument response.
1.1 This practice covers requirements for the validation of
1.6 This practice is not intended as a quantitative perfor-
measurements made by on-line, process near- or mid-infrared
mance standard for the comparison of analyzers of different
analyzers, or both, used in the calculation of physical, chemi-
design.
cal, or quality parameters of liquid petroleum products. The
1.7 Althoughthispracticedealsprimarilywithvalidationof
parameters are calculated from spectroscopic data using mul-
on-line, process infrared analyzers, the procedures and statis-
tivariate modeling methods. The requirements include verifi-
tical tests described herein are also applicable to at-line and
cation of adequate instrument performance, verification of the
laboratory infrared analyzers which employ multivariate mod-
applicability of the calibration model to the spectrum of the
els.
sample under test, and verification of equivalence between the
1.8 This standard does not purport to address all of the
resultcalculatedfromtheinfraredmeasurementsandtheresult
safety concerns, if any associated with its use. It is the
produced by the primary method used for the development of
responsibility of the user of this standard to consult and
the calibration model.
establish appropriate safety and health practices and deter-
1.2 This practice does not cover procedures for establishing
mine the applicability of regulatory limitations prior to use.
the calibration model used by the analyzer. Calibration proce-
dures are covered in Practices E1655 and references therein.
2. Referenced Documents
1.3 This practice is intended as a review for experienced
2.1 ASTM Standards:
persons. For novices, this practice will serve as an overview of
D1265 Practice for Sampling Liquefied Petroleum (LP)
techniques used to verify instrument performance, to verify
2
Gases (Manual Method)
model applicability to the spectrum of the sample under test,
D3764 Practice for Validation of Process Stream Analyz-
and to verify equivalence between the parameters calculated
3
ers
from the infrared measurement and the results of the primary
D4057 Practice for Manual Sampling of Petroleum and
method measurement.
3
Petroleum Products
1.4 This practice teaches and recommends appropriate sta-
D4177 Practice for Automatic Sampling of Petroleum and
tistical tools, outlier detection methods, for determining
3
Petroleum Products
whether the spectrum of the sample under test is a member of
D6299 Practice forApplying Statistical QualityAssurance
the population of spectra used for the analyzer calibration.The
Techniques to Evaluate Analytical Measurement System
statistical tools are used to determine if the infrared measure-
4
Performance
ment results in a valid property or parameter estimate.
5
E131 Terminology Relating to Molecular Spectroscopy
1.5 The outlier detection methods do not define criteria to
E275 Practice for Describing and Measuring Performance
determinewhetherthesample,ortheinstrumentisthecauseof
of Ultraviolet, Visible, and Near-Infrared Spectrophotom-
an outlier measurement. Thus, the operator who is measuring
5
eters
samples on a routine basis will find criteria to determine that a
6
E456 Terminology Relating to Quality and Statistics
spectral measurement lies outside the calibration, but will not
E932 Practice for Describing and Measuring Performance
have specific information on the cause of the outlier. This
5
of Dispersive Infrared Spectrophotometers
practice does suggest methods by which instrument perfor-
E1421 PracticeforDescribingandMeasuringPerformance
1
This practice is under the jurisdiction ofASTM Committee D02 on Petroleum
2
ProductsandLubricantsandisthedirectresponsibilityofSubcommitteeD02.25on Annual Book of ASTM Standards, Vol 05.01.
3
Performance Assessment and Validation of Process Stream Analyzer Systems for Annual Book of ASTM Standards, Vol 05.02.
4
Petroleum and Petroleum Products. Annual Book of ASTM Standards, Vol 05.03.
5
Current edition approved Dec. 10, 2001. Published February 2002. Originally Annual Book of ASTM Standards, Vol 03.06.
6
published as D 6122–97. Last previous edition D 6122–99. Annual Book of ASTM Standards, Vol 14.02.
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