ASTM D4952-12(2017)
(Test Method)Standard Test Method for Qualitative Analysis for Active Sulfur Species in Fuels and Solvents (Doctor Test)
Standard Test Method for Qualitative Analysis for Active Sulfur Species in Fuels and Solvents (Doctor Test)
SIGNIFICANCE AND USE
4.1 Sulfur present as mercaptans or as hydrogen sulfide in distillate fuels and solvents can attack many metallic and non-metallic materials in fuel and other distribution systems. A negative result in the doctor test ensures that the concentration of these compounds is insufficient to cause such problems in normal use.
SCOPE
1.1 This test method covers and is intended primarily for the detection of mercaptans in motor fuel, kerosine, and similar petroleum products. This method may also provide information on hydrogen sulfide and elemental sulfur that may be present in these sample types.
1.2 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.3 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.
1.4 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.
General Information
Buy Standard
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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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
Designation: D4952 − 12 (Reapproved 2017)
Standard Test Method for
Qualitative Analysis for Active Sulfur Species in Fuels and
Solvents (Doctor Test)
This standard is issued under the fixed designation D4952; 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.
This standard has been approved for use by agencies of the U.S. Department of Defense.
1. Scope 3. Summary of Test Method
1.1 This test method covers and is intended primarily for the 3.1 The sample is shaken with sodium plumbite solution, a
detection of mercaptans in motor fuel, kerosine, and similar small quantity of powdered sulfur added, and the mixture
petroleum products. This method may also provide information shaken again. The presence of mercaptans or hydrogen sulfide
on hydrogen sulfide and elemental sulfur that may be present in or both is indicated by discoloration of the sulfur floating at the
these sample types. oil-water interface or by discoloration of either of the phases.
1.2 The values stated in SI units are to be regarded as
4. Significance and Use
standard. No other units of measurement are included in this
4.1 Sulfur present as mercaptans or as hydrogen sulfide in
standard.
distillate fuels and solvents can attack many metallic and
1.3 This standard does not purport to address all of the
non-metallic materials in fuel and other distribution systems. A
safety concerns, if any, associated with its use. It is the
negative result in the doctor test ensures that the concentration
responsibility of the user of this standard to establish appro-
of these compounds is insufficient to cause such problems in
priate safety and health practices and determine the applica-
normal use.
bility of regulatory limitations prior to use.
1.4 This international standard was developed in accor-
5. Interferences
dance with internationally recognized principles on standard-
5.1 This test cannot be used if there are more than trace
ization established in the Decision on Principles for the
amounts of peroxides in the test sample. Peroxides can give a
Development of International Standards, Guides and Recom-
false positive results where mercaptans are at low level or not
mendations issued by the World Trade Organization Technical
even present.
Barriers to Trade (TBT) Committee.
5.2 To check if peroxides are present in sufficient concen-
2. Referenced Documents
tration to invalidate the test, shake 10 mL 6 0.5 mL of a fresh
portion of the sample with approximately 2 mL of the potas-
2.1 ASTM Standards:
sium iodide solution, add two drops of the acetic acid solution,
D1193 Specification for Reagent Water
and two drops of the starch solution. If the aqueous layer turns
D3227 Test Method for (Thiol Mercaptan) Sulfur in
a blue color, this confirms the presence of peroxides in
Gasoline, Kerosine, Aviation Turbine, and Distillate Fuels
sufficient quantity to invalidate the test, and the test on this
(Potentiometric Method)
sample should be discontinued. Proceed in accordance with
2.2 Energy Institute Standards:
5.4.
IP 30 Detection of Mercaptans, Hydrogen Sulfide, Elemental
Sulfur, and Peroxides – Doctor Test Method
5.3 Alternatively, one may choose to perform a preliminary
Doctor Test. If a brown precipitate slowly forms, peroxide is
This test method is under the jurisdiction of ASTM Committee D02 on
probably present. Proceed in accordance with 5.2 to confirm
Petroleum Products, Liquid Fuels, and Lubricants and is the direct responsibility of
presence of peroxides at sufficient quantity to invalidate the
Subcommittee D02.03 on Elemental Analysis.
test.
Current edition approved May 1, 2017. Published June 2017. Originally
approved in 1989. Last previous edition approved in 2012 as D4952 – 12. DOI:
5.4 If interference from peroxides is confirmed, proceed to
10.1520/D4952-12R17.
2 re-sample and retest. Ensure that sampling and handling
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 procedures for the new sample prevent UV light exposures as
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website.
3 4
Available from Energy Institute, 61 New Cavendish St., London, WIG 7AR, Brooks, B. T., “Sodium Plumbite or Doctor Test of Gasolines,” Industrial and
U.K., http://www.energyinst.org. Engineering Chemistry, Vol 16, No. 6, June 1924, p. 588.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D4952 − 12 (2017)
prescribed in 7.1. None of the normal refinery units or blending 7.2 It is preferable to collect the field samples using dark
processes producing spark ignition motor fuels are known to brown/amber bottles or metal cans, or if using clear glass
create peroxides under normal operating conditions. bottles to wrap them in foil or place in a light-tight box to
prevent UV light exposure.
6. Reagents and Materials
7.3 The samples should be tested without delay upon receipt
6.1 Purity of Reagents—Reagent grade chemicals shall be
in the laboratory before further chemical interactions take
used in all tests. Unless otherwise indicated, it is intended that
place.
all reagents conform to the specifications of the Committee on
Analytical Reagents of the American Chemical Society where
5 8. Procedure
such specifications are available. Other grades may be used,
provided it is first ascertained that the reagent is of sufficiently
8.1 Shake vigorously together in a test tube 10 mL of the
high purity to permit its use without lessening the accuracy of
sample being tested and 5 mL of sodium plumbite solution for
the determination.
about 15 s. Add a small amount of pure, sublimed flowers of
sulfur so that practically all of it floats on the interface between
6.2 Purity of Water—Unless otherwise indicated, references
the sample and the sodium plumbite solution after shaking.
to water shall be understood to mean reagent water as defined
Shake again for 15 s. Allow to settle and observe within 2 min.
by Types II or III of Specification D1193.
NOTE 2—It is important to avoid adding more sulfur than will just cover
6.3 Doctor (Sodium Plumbite) Solution—(Warning—
the interface. About 20 mg to 25 mg is the proper quantity, which can be
Poisonous and suspect carcinogen.) Dissolve approximately
estimated with a little practice. If too much sulfur is added, any possible
discoloration will be masked by the excess of sulfur.
125 g of sodium hydroxide (NaOH) in 1 L of reagent water.
Add 60 g of lea
...
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: D4952 − 12 D4952 − 12 (Reapproved 2017)
Standard Test Method for
Qualitative Analysis for Active Sulfur Species in Fuels and
Solvents (Doctor Test)
This standard is issued under the fixed designation D4952; 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.
This standard has been approved for use by agencies of the U.S. Department of Defense.
1. Scope*Scope
1.1 This test method covers and is intended primarily for the detection of mercaptans in motor fuel, kerosine, and similar
petroleum products. This method may also provide information on hydrogen sulfide and elemental sulfur that may be present in
these sample types.
1.2 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.3 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.
1.4 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:
D1193 Specification for Reagent Water
D3227 Test Method for (Thiol Mercaptan) Sulfur in Gasoline, Kerosine, Aviation Turbine, and Distillate Fuels (Potentiometric
Method)
2.2 Energy Institute Standards:
IP 30 Detection of Mercaptans, Hydrogen Sulfide, Elemental Sulfur, and Peroxides – Doctor Test Method
3. Summary of Test Method
3.1 The sample is shaken with sodium plumbite solution, a small quantity of powdered sulfur added, and the mixture shaken
again. The presence of mercaptans or hydrogen sulfide or both is indicated by discoloration of the sulfur floating at the oil-water
interface or by discoloration of either of the phases.
4. Significance and Use
4.1 Sulfur present as mercaptans or as hydrogen sulfide in distillate fuels and solvents can attack many metallic and non-metallic
materials in fuel and other distribution systems. A negative result in the doctor test ensures that the concentration of these
compounds is insufficient to cause such problems in normal use.
5. Interferences
5.1 This test cannot be used if there are more than trace amounts of peroxides in the test sample. Peroxides can give a false
positive results where mercaptans are at low level or not even present.
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 April 15, 2012May 1, 2017. Published June 2012June 2017. Originally approved in 1989. Last previous edition approved in 20092012 as
D4952D4952 – 12.–09. DOI: 10.1520/D4952-12.10.1520/D4952-12R17.
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.
Available from Energy Institute, 61 New Cavendish St., London, WIG 7AR, U.K., http://www.energyinst.org.
Brooks, B. T., “Sodium Plumbite or Doctor Test of Gasolines,” Industrial and Engineering Chemistry, Vol 16, No. 6, June 1924, p. 588.
*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
D4952 − 12 (2017)
5.2 To check if peroxides are present in sufficient concentration to invalidate the test, shake 1010 mL 6 0.5 mL 0.5 mL of a
fresh portion of the sample with approximately 2 mL 2 mL of the potassium iodide solution, add two drops of the acetic acid
solution, and two drops of the starch solution. If the aqueous layer turns a blue color, this confirms the presence of peroxides in
sufficient quantity to invalidate the test, and the test on this sample should be discontinued. Proceed in accordance with 5.4.
5.3 Alternatively, one may choose to perform a preliminary Doctor Test. If a brown precipitate slowly forms, peroxide is
probably present. Proceed in accordance with 5.2 to confirm presence of peroxides at sufficient quantity to invalidate the test.
5.4 If interference from peroxides is confirmed, proceed to re-sample and retest. Ensure that sampling and handling procedures
for the new sample prevent UV light exposures as prescribed in 7.1. None of the normal refinery units or blending processes
producing spark ignition motor fuels are known to create peroxides under normal operating conditions.
6. Reagents and Materials
6.1 Purity of Reagents—Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all
reagents 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 Purity of Water—Unless otherwise indicated, references to water shall be understood to mean reagent water as defined by
Types II or III of Specification D1193.
6.3 Doctor (Sodium Plumbite) Solution—(Warning—Poisonous and suspect carcinogen.) Dissolve approximately 125 g 125 g
of sodium hydroxide (NaOH) in 1 L 1 L of reagent water. Add 60 g 60 g of lead monoxide (PbO) and shake vigorously for 15 min,
15 min, or let stand with occasional shakings for at least one day. Allow to settle and decant or siphon off the clear liquid. If the
solution does not settle clear, filter it through filter paper. Keep the solution in a tightly sealed bottle and refilter before use if not
perfectly clear. As an alternative, the lab may use a commercially prepared solution that meets the requirements of the laboratory
preparation.
NOTE 1—AlternateAlternative volumes of the solution may be prepared or purchased, provided the final solution concentration is equivalent.
6.4 Sulfur—Pure, sublimed, stored in a closed container.
6.5 Potassium Iodide, approximately 100100 g g/L ⁄L Solution—Dissolve approximately 1 g 1 g of potassium iodide in
approximately 10 mL 10 mL of water. Prepare fresh for each test.
6.6 Acetic Acid, approximately 100100 g g/L ⁄L Solution—Add approximately 10 mL 10 mL of glacial acetic acid to
approximately 100 mL 100 mL water.
6.7 Starch Indicator, approximately 55 g g/L ⁄L Indicator Solution—Prepare fresh
...
Questions, Comments and Discussion
Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.