ASTM D3831-12(2017)
(Test Method)Standard Test Method for Manganese in Gasoline By Atomic Absorption Spectroscopy
Standard Test Method for Manganese in Gasoline By Atomic Absorption Spectroscopy
SIGNIFICANCE AND USE
4.1 Certain organo-manganese compounds act as antiknock agents when added to gasoline. This test method provides a means for determining the concentration of such a material in a gasoline sample.
SCOPE
1.1 This test method covers the determination of the total manganese content, present as methylcyclopentadienyl manganese tricarbonyl (MMT),2 of gasoline within the concentration range from 0.25 mg/L to 40 mg/L of manganese.
1.2 This test method is applicable to reformulated gasoline containing up to 12 % volume methyl tertiary butylether or up to 10 % volume ethanol. This test method may not be applicable to highly cracked materials containing greater than 18 % by volume olefins as determined by Test Method D1319 (nondepentanized).
1.3 This test method has been developed and tested specifically for the determination of MMT in gasoline over the recommended concentration range. Application of the method to other concentration ranges, to the determination of MMT in other materials, or to the determination of other manganese compounds in gasoline have not been tested
1.4 The values stated in SI units are to be regarded as the standard. The preferred concentration units are mg/L manganese.
1.5 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 and health practices and determine the applicability of regulatory limitations prior to use. For specific warning statements, see Sections 5 and 6.
1.6 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.
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Designation: D3831 − 12 (Reapproved 2017)
Standard Test Method for
Manganese in Gasoline By Atomic Absorption
Spectroscopy
This standard is issued under the fixed designation D3831; 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 2. Referenced Documents
2.1 ASTM Standards:
1.1 This test method covers the determination of the total
D1319 Test Method for Hydrocarbon Types in Liquid Petro-
manganese content, present as methylcyclopentadienyl manga-
leum Products by Fluorescent Indicator Adsorption
nese tricarbonyl (MMT), of gasoline within the concentration
D4057 Practice for Manual Sampling of Petroleum and
range from 0.25 mg⁄L to 40 mg⁄L of manganese.
Petroleum Products
1.2 This test method is applicable to reformulated gasoline
D4177 Practice for Automatic Sampling of Petroleum and
containing up to 12 % volume methyl tertiary butylether or up
Petroleum Products
to 10 % volume ethanol. This test method may not be appli-
D6299 Practice for Applying Statistical Quality Assurance
cable to highly cracked materials containing greater than 18 %
and Control Charting Techniques to Evaluate Analytical
by volume olefins as determined by Test Method D1319
Measurement System Performance
(nondepentanized).
D6300 Practice for Determination of Precision and Bias
Data for Use in Test Methods for Petroleum Products and
1.3 This test method has been developed and tested specifi-
Lubricants
cally for the determination of MMT in gasoline over the
D6792 Practice for Quality Management Systems in Petro-
recommended concentration range. Application of the method
leum Products, Liquid Fuels, and Lubricants Testing
to other concentration ranges, to the determination of MMT in
Laboratories
other materials, or to the determination of other manganese
D7740 Practice for Optimization, Calibration, and Valida-
compounds in gasoline have not been tested
tion ofAtomicAbsorption Spectrometry for MetalAnaly-
1.4 The values stated in SI units are to be regarded as the
sis of Petroleum Products and Lubricants
standard. The preferred concentration units are mg/L manga-
nese.
3. Summary of Test Method
1.5 This standard does not purport to address all of the 3.1 The gasoline sample is treated with bromine solution
safety concerns, if any, associated with its use. It is the and diluted with methyl isobutyl ketone. The manganese
responsibility of the user of this standard to establish appro- content of the sample is determined by atomic absorption
priate safety and health practices and determine the applica- spectrometry using an air-acetylene flame at 279.5 nm and
bility of regulatory limitations prior to use. For specific standards prepared from an organo-manganese standard mate-
warning statements, see Sections 5 and 6. rial.
1.6 This international standard was developed in accor-
3.2 Protocols for using atomic absorption spectrometry are
dance with internationally recognized principles on standard-
given in Practice D7740.
ization established in the Decision on Principles for the
Development of International Standards, Guides and Recom-
4. Significance and Use
mendations issued by the World Trade Organization Technical
4.1 Certain organo-manganese compounds act as antiknock
Barriers to Trade (TBT) Committee.
agents when added to gasoline. This test method provides a
means for determining the concentration of such a material in
a gasoline sample.
This test method is under the jurisdiction of ASTM Committee D02 on
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
Subcommittee D02.03 on Elemental Analysis.
Current edition approved May 1, 2017. Published June 2017. Originally For referenced ASTM standards, visit the ASTM website, www.astm.org, or
approved in 1979. Last previous edition approved in 2012 as D3831 – 12. DOI: contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
10.1520/D3831-12R17. Standards volume information, refer to the standard’s Document Summary page on
MMT is a registered trademark of Ethyl Corp. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D3831 − 12 (2017)
5. Apparatus 6.7 Quality Control (QC) Sample(s),
preferably are a portion of one or more gasoline materials that
5.1 Atomic Absorption Spectrometer, capable of scale ex-
are stable and representative of the samples of interest.
pansion and equipped with a manganese hollow-cathode lamp
for monitoring manganese absorption at 279.5 nm, a premix
7. Sampling
slot-type burner with rotatable burner head, and an adjustable
7.1 Take samples of gasoline in compliance with the in-
nebulizer. (Warning—Hazardous. Potentially toxic and explo-
structions in Practice D4057 or D4177 where appropriate.
sive. Refer to the manufacturer’s instrument manual for asso-
Analyze as soon as possible after sampling.
ciated safety hazards.)
8. Calibration
5.2 Vials, up to 40 mL size with polyethylene or TFE-
fluorocarbon-lined caps or glass stoppers.
8.1 Preparation of Working Standards —Prepare four work-
ing standards using the 4.0 mg, 10.0 mg, 20.0 mg, and 40.0 mg
5.3 Pipet, Delivery, 1 mL size.
Mn/L standard manganese solutions described in 6.3.
5.4 Micropipet, 100 µL size, Eppendorf type or equivalent.
8.1.1 Usingamicropipet,add100 µLofbrominesolutionto
5.5 Automatic Pipet,orequivalentdeliverypipet,capableof
each of four separate vials.
delivering 9.0 mL quantities.
8.1.2 Pipet 1 mL of each of the four low-manganese stan-
dards into each of the vials. Mix with the bromine solution by
6. Reagents
swirling the vials.
8.1.3 Deliver 9.0 mL of methyl isobutyl ketone to each of
6.1 Purity of Reagents—Reagent grade chemicals shall be
the vials. Mix well.This tenfold dilution of the low-manganese
used in all tests. Unless otherwise indicated, it is intended that
standards is the same as the final dilution of the sample.
all reagents shall conform to the specifications of the Commit-
tee onAnalytical Reagents of theAmerican Chemical Society, 8.2 Preparation of Instrument—Set the atomic absorption
where such specifications are available. Other grades may be
spectrometer operating conditions to those recommended by
used, provided it is first ascertained that the reagent is of the manufacturer for monitoring manganese absorption at
sufficiently high purity to permit its use without lessening the
279.5 nm using an air-acetylene flame. This test method
accuracy of the determination. assumes that good operating procedures are followed. Design
differences between spectrometers make it impractical to
6.2 Bromine Solution—Add reagent grade bromine to an
exactly specify required instrument settings.
equal volume of cyclohexane. (Warning—Bromine can cause
8.2.1 Nebulizemethylisobutylketoneintotheflame.Adjust
severe and painful burns when it contacts the skin. In addition
thenebulizer(sampleflowrate),acetylene,andairflowratesto
to other precautions, wear protective gloves in preparing the
give a lean, nonluminous flame.
solution and prepare, store, and use it in a well-ventilated
8.2.2 With methyl isobutyl ketone as a blank, nebulize, in
hood.)
turn, the four working standards.
6.3 Manganese Standard Solution 400 mg Mn/L—Dissolve
NOTE 1—Record the absorbances and check these data for linearity. If
the appropriate amount of organometallic manganese standard
nonlinear, readjust the sample or acetylene flow rates, or both, slightly to
inmethylisobutylketonetogiveastandardsolutionof400mg
leaner conditions and repeat the calibrations until absorbances are linear.
Mn/
...
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: D3831 − 12 D3831 − 12 (Reapproved 2017)
Standard Test Method for
Manganese in Gasoline By Atomic Absorption
Spectroscopy
This standard is issued under the fixed designation D3831; 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*Scope
1.1 This test method covers the determination of the total manganese content, present as methylcyclopentadienyl manganese
tricarbonyl (MMT), of gasoline within the concentration range from 0.250.25 mg ⁄L to 4040 mg mg/L ⁄L of manganese.
1.2 This test method is applicable to reformulated gasoline containing up to 12 % volume methyl tertiary butylether or up to
10 % volume ethanol. This test method may not be applicable to highly cracked materials containing greater than 18 18 % by
volume % olefins as determined by Test Method D1319 (nondepentanized).
1.3 This test method has been developed and tested specifically for the determination of MMT in gasoline over the
recommended concentration range. Application of the method to other concentration ranges, to the determination of MMT in other
materials, or to the determination of other manganese compounds in gasoline have not been tested
1.4 The values stated in SI units are to be regarded as the standard. The preferred concentration units are mg/L manganese.
1.5 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 and health practices and determine the applicability of regulatory
limitations prior to use. For specific warning statements, see Sections 5 and 6.
1.6 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.
2. Referenced Documents
2.1 ASTM Standards:
D1319 Test Method for Hydrocarbon Types in Liquid Petroleum Products by Fluorescent Indicator Adsorption
D4057 Practice for Manual Sampling of Petroleum and Petroleum Products
D4177 Practice for Automatic Sampling of Petroleum and Petroleum Products
D6299 Practice for Applying Statistical Quality Assurance and Control Charting Techniques to Evaluate Analytical Measure-
ment System Performance
D6300 Practice for Determination of Precision and Bias Data for Use in Test Methods for Petroleum Products and Lubricants
D6792 Practice for Quality Management Systems in Petroleum Products, Liquid Fuels, and Lubricants Testing Laboratories
D7740 Practice for Optimization, Calibration, and Validation of Atomic Absorption Spectrometry for Metal Analysis of
Petroleum Products and Lubricants
3. Summary of Test Method
3.1 The gasoline sample is treated with bromine solution and diluted with methyl isobutyl ketone. The manganese content of
the sample is determined by atomic absorption spectrometry using an air-acetylene flame at 279.5 nm 279.5 nm and standards
prepared from an organo-manganese standard material.
3.2 Protocols for using atomic absorption spectrometry are given in Practice D7740.
This test method is under the jurisdiction of ASTM Committee D02 on Petroleum Products Products, Liquid Fuels, and Lubricants and is the direct responsibility of
Subcommittee D02.03 on Elemental Analysis.
Current edition approved June 1, 2012May 1, 2017. Published August 2012June 2017. Originally approved in 1979. Last previous edition approved in 20062012 as
D3831D3831 – 12. –01(2006). DOI: 10.1520/D3831-12.10.1520/D3831-12R17.
MMT is a registered trademark of Ethyl Corp.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
*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
D3831 − 12 (2017)
4. Significance and Use
4.1 Certain organo-manganese compounds act as antiknock agents when added to gasoline. This test method provides a means
for determining the concentration of such a material in a gasoline sample.
5. Apparatus
5.1 Atomic Absorption Spectrometer , Spectrometer, capable of scale expansion and equipped with a manganese hollow-cathode
lamp for monitoring manganese absorption at 279.5 nm, 279.5 nm, a premix slot-type burner with rotatable burner head, and an
adjustable nebulizer. (Warning—Hazardous. Potentially toxic and explosive. Refer to the manufacturer’s instrument manual for
associated safety hazards.)
5.2 Vials, up to 40-mL40 mL size with polyethylene or TFE-fluorocarbon-lined caps or glass stoppers.
5.3 Pipet, Delivery, 1-mL 1 mL size.
5.4 Micropipet, 100-μL100 μL size, Eppendorf type or equivalent.
5.5 Automatic Pipet, or equivalent delivery pipet, capable of delivering 9.0-mL9.0 mL quantities.
6. Reagents
6.1 Purity of Reagents—Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all
reagents shall conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society, where
such specifications are available. Other grades may be used, provided it is first ascertained that the reagent is of sufficiently high
purity to permit its use without lessening the accuracy of the determination.
6.2 Bromine Solution—Add reagent grade bromine to an equal volume of cyclohexane. (Warning—Bromine can cause severe
and painful burns when it contacts the skin. In addition to other precautions, wear protective gloves in preparing the solution and
prepare, store, and use it in a well-ventilated hood.)
6.3 Manganese Standard Solution 400 mg 400 mg Mn/L—Dissolve the appropriate amount of organometallic manganese
standard in methyl isobutyl ketone to give a standard solution of 400 mg Mn/L.
6.4 Manganese, Standard Solution 4.0, 10.0, 20.0,4.0 mg, 10.0 mg, 20.0 mg, and 40.0 mg Mn/L—Dilute the 400400 mg mg/L
⁄L standard manganese solution with methyl isobutyl ketone using volumetric glassware to give the desired lower concentration
manganese standard solutions.
6.5 Organometallic Manganese Standard —Standard—Pre-prepared commercially available organometallic stock solutions
have been found to be satisfactory.
6.6 Methyl Isobutyl Ketone, reagent grade. (Warning—Flammable. Vapor harmful.) (Warning— Solutions of MMT in
gasoline are chemically unstable when exposed to light. Low and erratic results may be obtained if the gasoline sample is exposed
to light prior to stabilization during analysis.)
6.7 Quality Control (QC) Sample(s) , Sample(s),
preferably are a portion of one or more gasoline materials that are stable and representative of the samples of interest.
7. Sampling
7.1 Take samples of gasoline in compliance with the instructions in Practice D4057 or D4177 where appropriate. Analyze as
soon as possible after sampling.
8. Calibration
8.1 Preparation of Working Standards —Prepare four working standards using the 4.0, 10.0, 20.0,4.0 mg, 10.0 mg, 20.0 mg, and
40.0 mg Mn/L standard manganese solutions described in 6.3.
8.1.1 Using a micropipet, add 100 μL 100 μL of bromine solution to each of four separate vials.
8.1.2 Pipet 1 mL 1 mL of each of the four low-manganese standards into each of the vials. Mix with the bromine solution by
swirling the vials.
8.1.3 Deliver 9.0 mL 9.0 mL of methyl isobutyl ketone to each of the vials. Mix well. This tenfold dilution of the
low-manganese standards is the same as the final dilution of the sample.
8.2 Preparation of Instrument—Set the atomic absorption
...
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