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: D3227 − 24

Designation: 342/20

Standard Test Method for

(Thiol Mercaptan) Sulfur in Gasoline, Kerosine, Aviation
Turbine, and Distillate Fuels (Potentiometric Method)1,2
This standard is issued under the fixed designation D3227; 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* 2. Referenced Documents

1.1 This test method covers the determination of mercaptan 2.1 ASTM Standards:3
sulfur in gasolines, kerosines, aviation turbine fuels, and D1193 Specification for Reagent Water
distillate fuels containing from 0.0003 % to 0.01 % by mass of D1250 Guide for the Use of the Joint API and ASTM
mercaptan sulfur. Organic sulfur compounds such as sulfides, Adjunct for Temperature and Pressure Volume Correction
disulfides, and thiophene, do not interfere. Elemental sulfur in Factors for Generalized Crude Oils, Refined Products, and
amounts less than 0.0005 % by mass does not interfere. Lubricating Oils: API MPMS Chapter 11.1
Hydrogen sulfide will interfere if not removed, as described in D1298 Test Method for Density, Relative Density, or API
10.2. Gravity of Crude Petroleum and Liquid Petroleum Prod-
ucts by Hydrometer Method
1.2 The values in acceptable SI units are to be regarded as D4052 Test Method for Density, Relative Density, and API
the standard. Gravity of Liquids by Digital Density Meter
1.2.1 Exception—The values in parentheses are for informa- D4057 Practice for Manual Sampling of Petroleum and
tion only. Petroleum Products
1.3 This standard does not purport to address all of the D4175 Terminology Relating to Petroleum Products, Liquid
safety concerns, if any, associated with its use. It is the Fuels, and Lubricants
responsibility of the user of this standard to establish appro- D4177 Practice for Automatic Sampling of Petroleum and
priate safety, health, and environmental practices and deter- Petroleum Products
mine the applicability of regulatory limitations prior to use. D6299 Practice for Applying Statistical Quality Assurance
For specific warning statements, see Sections 7, 9, 10, and and Control Charting Techniques to Evaluate Analytical
Appendix X1. Measurement System Performance
1.4 This international standard was developed in accor-
3. Terminology
dance with internationally recognized principles on standard-
ization established in the Decision on Principles for the 3.1 Definitions:
Development of International Standards, Guides and Recom- 3.1.1 For definitions of terms used in this test method, refer
mendations issued by the World Trade Organization Technical to Terminology D4175.
Barriers to Trade (TBT) Committee.
4. Summary of Test Method
4.1 The hydrogen sulfide-free sample is dissolved in an
1
This test method is under the jurisdiction of ASTM International Committee alcoholic sodium acetate titration solvent and titrated potentio-
D02 on Petroleum Products, Liquid Fuels, and Lubricants and is the direct metrically with silver nitrate solution, using as an indicator the
responsibility of ASTM Subcommittee D02.03 on Elemental Analysis. The techni- potential between a glass reference electrode and a silver/
cally equivalent standard as referenced is under the jurisdiction of the Energy
Institute Subcommittee SC-G-5. silver-sulfide indicating electrode. Under these conditions, the
Current edition approved March 1, 2024. Published March 2024. Originally
approved in 1973. Last previous edition approved in 2023 as D3227 – 23. DOI:
10.1520/D3227-24.
2 3
This test method has been developed through the cooperative effort between For referenced ASTM standards, visit the ASTM website, www.astm.org, or
ASTM and the Energy Institute, London. ASTM and IP standards were approved by contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
ASTM and EI technical committees as being technically equivalent but that does not Standards volume information, refer to the standard’s Document Summary page on
imply both standards are identical. 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

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 D3227 − 24
mercaptan sulfur is precipitated as silver mercaptide and the 7.2 Water—Reagent grade, Type I, Specification D1193.
end point of the titration is shown by a large change in cell 7.3 Cadmium Sulfate, Acid Solution (150 g ⁄L)—Dissolve
potential. 150 g of cadmium sulfate (3CdSO4·8H2O) in water.
5. Significance and Use (Warning—Poison. May be fatal if swallowed or inhaled. A
known carcinogen (animal positive).) Add 10 mL of dilute
5.1 Mercaptan sulfur has an objectionable odor, an adverse H2SO4 (Warning—Poison. Causes severe burns. Harmful or
effect on fuel system elastomers, and is corrosive to fuel fatal if swallowed or inhaled) and dilute to 1 L with water.
system components.
7.4 Potassium Iodide, Standard Solution (approximately
6. Apparatus 0.1 mol ⁄L)—Dissolve 17 g of KI (weigh to 0.01 g) in 100 mL
of water in a 1 L volumetric flask and dilute to 1 L. Calculate
6.1 As described in 6.2 – 6.5; alternatively, any automatic
the exact molarity.
titration system may be used that, using the same electrode pair
described in 6.3, is capable of performing the titration as 7.5 Propan-2-ol—(Warning—Flammable. Warning—
described in Section 10 and selecting the endpoint specified in Unless inhibited against it, peroxides can form in propan-2-ol
12.1 with a precision that meets or is better than that given in when stored in the same container that is exposed to air. When
Section 15. this happens and the propan-2-ol evaporates to dryness, an
explosion can occur. When peroxides are suspected, they may
6.2 Meter—An electronic voltmeter, operating on an input
be removed by percolation through an activated alumina
of less than 9 × 10−12 A and having a sensitivity of 62 mV
column.)
over a range of at least 61 V. The meter shall be electrostati-
cally shielded, and the shield shall be connected to the ground.4 7.6 Silver Nitrate, Standard Alcoholic Solution
(0.1 mol ⁄L)—Dissolve 17 g of AgNO3 in 100 mL of water in a
6.3 Cell System, consisting of a reference and indicating
1 L volumetric flask and dilute to 1 L with propan-2-ol (99 %)
electrode. The reference is a glass electrode. The indicating
(see Note 1). Store in a dark bottle and standardize at intervals
electrode shall be a silver wire or billet electrode with a
frequent enough to detect a change of 0.0005 or greater in
silver/silver-sulfide coating. Combination electrodes consisting
molarity.
of a glass and silver electrode pair, where silver is coated with
sulfide (Ag2S), may also be used. Shielded electrode cables NOTE 1—It is important to pass the propan-2-ol through a column of
must be used. activated alumina to remove peroxides that may have formed on storage;
failure to remove peroxides will lead to low results. It is not necessary to
6.4 Buret, 10 mL capacity, graduated in 0.05 mL intervals, perform this step if the alcohol is tested and found free of peroxides.
with a tip that extends approximately 120 mm (5 in.) below the 7.6.1 Standardization—Add six drops of concentrated
stopcock. HNO3 (relative density 1.42) (Warning—Poison. Causes
6.5 Titration Stand, preferably built as an integral part of the severe burns. Harmful or fatal if swallowed or inhaled) to
meter housing and provided with supports for the electrodes 100 mL of water in an appropriately sized beaker (for example,
and electrical stirrer, all connected to ground. No permanent a 200 mL, 250 mL, or 300 mL size beaker is typically large
change in meter reading should be noticeable upon connecting enough). Remove oxides of nitrogen by boiling for 5 min. Cool
or disconnecting the stirring motor. to ambient temperature. Pipet 5 mL of 0.1 mol ⁄L KI solution
into the beaker and titrate with the AgNO3 solution choosing
7. Reagents and Materials the end point at the inflection of the titration curve.
7.1 Purity of Reagents—Reagent grade chemicals shall be 7.7 Silver Nitrate, Standard Alcoholic Solution
used in all tests. Unless otherwise indicated, it is intended that (0.010 mol ⁄L)—Prepare daily when the test is being performed
all reagents shall conform to the specifications of the Commit- by dilution of the 0.1 N standard. Pipet 100 mL of the
tee on Analytical Reagents of the American Chemical Society, 0.1 mol ⁄L standard into a 1 L volumetric flask and dilute to
where such specifications are available.5 Other grades may be volume with propan-2-ol. Calculate the exact molarity.
used, provided it is first ascertained that the reagent is of
7.8 Sodium Sulfide Solution (10 g ⁄L)—Dissolve 10 g of
sufficiently high purity to permit its use without lessening the
Na2S in water and dilute to 1 L with water. Prepare fresh as
accuracy of the determination.
needed.
7.1.1 Commercially available solutions may be used in
place of prepared laboratory solutions, when they are certified NOTE 2—Anhydrous sodium sulfide is not widely available, and is
to meet the required concentrations. expensive. An aqueous solution of hydrated sodium sulfide (Na2S·9H2O)
at 30.6 g ⁄L is satisfactory.
7.1.2 Alternate volumes of solutions and solvents may be
prepared, when an equivalent concentration is maintained. 7.9 Sulfuric Acid, dilute. Cautiously dilute five volumes of
water with one volume of sulfuric acid (relative density 1.84).
4
(Warning—Adding the acid will generate heat: mix well. If
Any apparatus that will give equal or better precision is acceptable.
5
ACS Reagent Chemicals, Specifications and Procedures for Reagents and
water begins to boil, cool before adding more acid.) Note that
Standard-Grade Reference Materials, American Chemical Society, Washington, only limited volumes are required because only 10 mL are
DC. For suggestions on the testing of reagents not listed by the American Chemical needed for each litre of cadmium sulfate solution.
Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma- 7.10 Titration Solvent—Low molecular weight mercaptans,
copeial Convention, Inc. (USPC), Rockville, MD. as usually found in gasoline, are readily lost from the titration

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 D3227 − 24
solution if an acidic titration solvent is used. For the determi- 9.2.2 As triggered by the analysis of a quality control (QC)
nation of the higher molecular weight mercaptan as normally sample (see Section 13), prepare a fresh silver sulfide coating
encountered in kerosines, aviation turbine fuels, and distillate on the electrode by the following method:
fuels, the acidic titration solvent is used to achieve more rapid 9.2.2.1 Burnish electrode with polishing paper or cloth until
equilibrium between successive additions of the titrant. a clean, polished silver surface shows.
7.10.1 Alkaline Titration Solvent—Dissolve 2.7 g of sodium 9.2.2.2 Place electrode in operating position and immerse it
acetate trihydrate (NaC2H3O2·3H2O) or 1.6 g of anhydrous in 100 mL of titration solvent containing 8 mL of Na2S
sodium acetate (NaC2H3O2) in 25 mL of water free of dis- solution.
solved oxygen and pour into 975 mL of propan-2-ol (99 %) 9.2.2.3 Add slowly (for example, from a buret), with
(Note 1). When necessary, remove dissolved oxygen by purg- stirring, 10 mL of 0.1 mol ⁄L AgNO3 solution over a period
ing the solution with a rapid stream of nitrogen for 10 min each from 10 min to 15 min.
day prior to use; keep protected from the atmosphere. To 9.2.2.4 Remove electrode from solution, wash with water,
minimize oxygen from dissolving in the solution during and wipe with a soft, clean tissue.
storage, an option exists to nitrogen blanket the solution prior 9.3 Combination Electrodes—After each titration, rinse
to sealing the solvent container. with a suitable solvent such as toluene or 2-propanol followed
7.10.2 Acidic Titration Solvent—Dissolve 2.7 g of by a rinse with water. Rinse with water before each use.
NaC2H3O2·3H2O or 1.6 g of NaC2H3O2 in 20 mL of water free 9.3.1 When not in use, immerse the glass membrane portion
of dissolved oxygen and pour into 975 mL of propan-2-ol of the combination electrode in distilled water. Rinse with
(99 %) (Note 1) and add 4.6 mL of glacial acetic acid. When water before use.
necessary, remove dissolved oxygen by purging the solution
with a rapid stream of nitrogen for 10 min each day prior to 10. Procedure
use; keep protected from the atmosphere. To minimize oxygen
10.1 Determination of Density—If the sample is to be
from dissolving in the solution during storage, an option exists
measured volumetrically, determine the density by Test
to nitrogen blanket the solution prior to sealing the solvent
Method D1298 or Test Method D4052 at the temperature at
container.
which the test portion will be taken, either directly or from the
7.11 Polishing Paper or Cloth, 6 µm to 20 µm average density determined at a reference temperature and converted to
particle size abrasive. the transfer temperature by use of the Petroleum Measurement
Tables (Guide D1250).
8. Sampling 10.2 Removal of Hydrogen Sulfide—Test the sample quali-
8.1 Take the sample in accordance with Practice D4057 or tatively for hydrogen sulfide (H2S) by mixing 5 mL of the
Practice D4177. sample with 5 mL of the acid CdSO4 solution. If no precipitate
8.2 Methanethiol (methyl mercaptan) has a boiling point of appears, proceed with the analysis of the sample as described
6.2 °C and may be expected to be present in light untreated in 10.3. If a yellow precipitate appears, remove the H2S in the
gasolines. Therefore, when the presence of this low boiling following manner: Place a quantity of the sample, three to four
thiol (mercaptan) is known or expected, specimen to be tested times that required for the analysis, in a separatory funnel
shall be kept below 4 °C to prevent the loss of mercaptan from containing a volume of the acid CdSO4 solution equal to one
such samples. half that of the sample and shake vigorously. Draw off and
discard the aqueous phase containing the yellow precipitate.
8.3 Light naphtha fractions of high thiol content Repeat the extraction with another portion of the CdSO4
(>100 mg ⁄kg) boiling below 85 °C have been shown to be very solution. Again draw off the aqueous phase, and wash the
sensitive to the titration temperatures. sample with three 25 mL to 30 mL portions of water, with-
NOTE 3—Samples with a thiol content above 0.010 % by mass may be drawing the water after each washing. Filter the hydrocarbon
analyzed by an appropriate reduction in test portion mass, ensuring that through a rapid paper. Test a small portion of the washed
the minimum volume of titration solvent plus test portion exceeds sample, such as in a test tube or vial, with a few millilitres of
120 mL. If additional titration solvent is used to maintain this requirement,
the CdSO4 solution as described previously. If no further
a similar volume should be used for the blank titration. No precision has
been determined for thiol contents above 0.01 % by mass. precipitate is formed, proceed as directed in 10.3. If a precipi-
tate appears, repeat the extraction with the CdSO4 solution
9. Preparation of Apparatus until all of the H2S has been removed. (Warning—Certain
straight run gasolines can contain significant amounts of both
9.1 Glass Electrode—After each titration, rinse with a low molecular weight mercaptans and dissolved elemental
suitable solvent such as toluene or 2-propanol followed by a sulfur, which, when heated under total reflux conditions, may
rinse with water. Rinse with water before use. produce H2S by the inter-reaction of both. This phenomenon is
9.1.1 When not in use, keep the glass membrane of the particularly noticed in straight run gasolines produced from
electrode immersed in water. some natural gas condensates. Therefore, it is advisable that
9.2 Silver-Sulfide Electrode—After each titration, rinse with during the removal of H2S (and after all H2S has been
a suitable solvent such as toluene or 2-propanol followed by a extracted), that no heat should be applied to the sample.)
rinse with water. Rinse with water before use. 10.2.1 When the test results obtained are not for referee
9.2.1 When not in use, the silver electrode may be kept dry. purposes and Quality Assurance/Quality Control (QA/QC)

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 D3227 − 24
protocol permits, an alternative test for, and a procedure for the 10.3.3 Continue the titration until the meter reading change
removal of, hydrogen sulfide can be used. This process uses of the cell potential per 0.1 mL of 0.01 M AgNO3 solution has
lead acetate paper and sodium hydrogen carbonate and is become relatively constant. Consider the potential constant if it
described in Appendix X1. changes less than 6 mV ⁄min. Remove the titrated solution,
10.2.2 There are available automated instruments that elimi- rinse the electrodes with alcohol, and wipe with a dry tissue. If
nate the necessity to remove H2S when present, prior to an automatic titration system is used, rinse the electrodes well
performing the analysis, since the H2S titration curve does not with alcohol, allow the excess alcohol to drain off the electrode
interfere with the titration curve of the thiol or mercaptan and then proceed with the next sample. Between successive
determination. Such equipment may be used when the test is determinations (or batches of determinations in the case of
not for referee purposes. The precision statement does not automatic titration systems) on the same day, store the elec-
include data obtained from this alternate procedure. trodes in accordance with 9.1.
10.2.3 For referee purposes, the protocol, as detailed in 10.4 As often as is required and preferably, at least daily,
10.2, shall be used. A possible non-referee situation may be the when the test equipment is being used, perform a blank
instance of routine refinery control. titration following 10.3 – 10.3.3 without adding a test sample.
10.3 Measure with a pipet (or other suitable transfer device)
or weigh 20 mL to 50 mL of the original or treated sample into 11. Calculation
an appropriately sized beaker (for example, a 200 mL, 250 mL, 11.1 Calculate the mercaptan sulfur content of the sample as
or 300 mL size beaker is typically large enough) containing follows:
100 mL of the appropriate titration solvent. Place the beaker on
Mercaptan sulfur, mass % 5 ~ DM ~ A 1 2 A 0 ! × 3.206! /W (1)
the titration stand or on the auto-sampler of an automatic or
titration system. If an automatic titration system is used, set up
the system to reproduce the experimental conditions specified Mercaptan sulfur, mass % 5 ~ DM ~ A 1 2 A 0 ! × 3.206! / ~ d × V ! (2)
in 10.3.1 – 10.3.3. Adjust the position of the titration stand so D 5 ~ W1I ! /W (3)
that the electrodes are about half immersed. Fill the buret with D 5 ~ V1J ! /V (4)
0.01 mol ⁄L alcoholic AgNO3 solution and position it in the
titration assembly so that the tip extends approximately 25 mm where:
(1 in.) below the surface of the liquid in the beaker. Adjust the A1 = millilitres of AgNO3 solution required to reach the
speed of the stirrer to give vigorous stirring without spattering. end point in the vicinity of +300 mV (see Fig. 1),
10.3.1 Record the initial buret and cell potential readings. when a sample is being titrated,
The usual meter readings for mercaptan presence are in A0 = mL of AgNO3 solution required to reach the end
the −250 mV to −350 mV range. Add suitable small portions of point in the vicinity of +300mV (see Fig. 1), when
0.01 mol ⁄L AgNO3 solution and, after waiting until a constant only the blank is titrated. (Note, there are no other
potential has been established, record the buret and meter changes to the factors in the equation.)
readings. Consider the potential constant if it changes less than d = density of sample at transfer temperature, g/mL,
6 mV ⁄min. D = dilution factor (if necessary, see Note 5),
I = grams of diluent used,
NOTE 4—If potential readings obtained with freshly prepared electrodes J = mL of diluent used,
are erratic, it is possible that the electrodes are not properly conditioned. M = molarity of the AgNO3 solution,
This difficulty usually disappears in succeeding titrations. W = grams of sample used,
NOTE 5—When analyzing samples with a relatively high mercaptan
concentration, the use of a 20 mL to 50 mL sample size can require an
3.206 = 100 × g meq weight S in mercaptan, and
unreasonably long titration time and a large quantity of the titrant. For V = mL of sample used.
such samples, a smaller sample size may be used or the original sample
may be diluted with a suitable solvent that is miscible with the sample and 12. Interpretation of Results
free of mercaptans into the 20 mL to 50 mL sample size range prior to
titrating the sample. The precision of samples using <20 mL sample sizes
12.1 Treatment of Data—Plot the cumulative volumes of
or samples that have been diluted have not been determined in an 0.01 M AgNO3 solution added against the corresponding cell
interlaboratory study. potentials. Select the end point at the inflection point of the
NOTE 6—With certain instruments, the algebraic sign of the potentials steepest portion of each “break” in the titration curve as shown
may appear reversed. in Fig. 1. The shape of the titration curve may change with
10.3.2 When the potential change is small for each incre- different instruments. However, the above interpretation of the
ment of AgNO3 solution, add volumes as large as 0.5 mL. end point should be followed.
When the change of potential becomes greater than 12.1.1 Mercaptans Only—If mercaptans alone are present in
6 mV ⁄0.1 mL, use 0.05 mL increments of 0.01 mol ⁄L AgNO3 the sample, the titration produces a curve of the first type
solution. Near the end point of the titration, 5 min or 10 min shown in Fig. 1, having an initial plateau at a potential equal to
may elapse before a constant potential is obtained. Although it or more negative than −250 mV, and an end point when a
is important to wait for equilibrium conditions, it is also potential change of less than 6 mV/min is reached and the
important that the duration of the titration be as short as change in mV/min of titrant is reduced with each incremental
possible to avoid oxidation of the sulfur compounds by addition.
atmospheric oxygen. Once started, a titration must never be 12.1.2 Mercaptans and Elemental Sulfur—When elemental
interrupted and resumed later. sulfur and mercaptans are both present in the sample, a

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 D3227 − 24

FIG. 1 Illustrative Potentiometric Titration

chemical interaction occurs which, in the titration solvent used, 13.1.1 When QA/QC protocols are already established in
precipitates silver sulfide (Ag2S) during the titration. the testing facility, these may be used when they confirm the
12.1.3 When mercaptans are present in excess, the end of reliability of test result.
the Ag2S precipitation occurs at about −550 mV to −350 mV, 13.1.2 When there is no QA/QC protocol established in the
and is followed by the precipitation of the silver mercaptide to testing facility, Appendix X2 may be used as the QA/QC
the +300 mV end point. This situation is shown in the middle system.
curve of Fig. 1. Since all of the Ag2S originates from an 13.2 Users of this test method are advised that in contractual
equivalent amount of mercaptan, the total titration to the agreements, one or more of the contracting parties can and may
mercaptide end point must be used to calculate the amount of make Appendix X2 a mandatory practice.
mercaptan sulfur.
12.1.4 When elemental sulfur is present in excess, the end 14. Report
of the Ag2S precipitation is taken in the same region
(+300 mV) as in the case of silver mercaptide, and is calculated 14.1 Report the result to the nearest 0.0001 % (m ⁄m) or to
as mercaptan sulfur. the nearest 1 mg ⁄kg.
12.1.5 When samples of light gasolines containing meth-
anethiol (methyl mercaptan) or heavier thiols (mercaptans) 15. Precision and Bias
appear to give erratic results, it may be necessary to cool and 15.1 Precision—The precision of this test method as deter-
maintain the test apparatus below 4 °C prior to proceeding, as mined by statistical examination of interlaboratory results is as
detailed in 10.2 – 10.4 inclusive. For these samples, this step follows:
may be necessary for more reproducible test results. 15.1.1 Repeatability—The difference between two succes-
sive test results, obtained by the same operator with the same
13. Quality Assurance/Quality Control apparatus under constant operating conditions on identical test
13.1 Confirm the performance of the instrument and the test material, would in the long run, in the normal and correct
procedure by analyzing a control (QC) sample. operation of the test method, exceed the following values only

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 D3227 − 24
in one case in twenty:
Repeatability 0.00007 + 0.027x (see Note 7)
where:
x = average mercaptan sulfur, mass %.
NOTE 7—This amount is shown graphically in Fig. 2.
15.1.2 Reproducibility—The difference between two single
and independent results obtained by different operators work-
ing in different laboratories on identical test material would, in
the long run, in the normal and correct operation of the test
method, exceed the following values only in one case in
twenty:
Reproducibility 0.00031 + 0.042x (see Note 7)
where:
x = average mercaptan sulfur, mass %.
15.2 Bias—The bias for the procedure in this test method
has not been determined.
16. Keywords
16.1 mercaptan; potentiometric; sulfur

FIG. 2 Precision Curve for Mercaptan Sulfur in Gasolines, Kerosines, Aviation Turbine, and Distillate Fuels

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 D3227 − 24

APPENDIXES

(Nonmandatory Information)

X1. AN ALTERNATIVE METHOD FOR THE REMOVAL OF HYDROGEN SULFIDE

X1.1 Scope sulfide, it is necessary to dry and store them in a hydrogen

X1.1.1 This test method provides an alternative to using a sulfide free atmosphere.)
cadmium sulfate acid solution. (Warning—Poison. May be X1.3.5 Sodium Hydrogen Carbonate, Aqueous Solution—
fatal if swallowed or inhaled. A known carcinogen (animal Prepare this solution by dissolving 50 g 6 1 g of sodium
positive).) (Warning—Poison. Causes severe burns. Harmful hydrogen carbonate (Na2HCO3) in water; dilute to 1 L in a
or fatal if swallowed or inhaled.) volumetric flask.
X1.1.2 This test method uses lead acetate test paper X1.3.6 Test Paper—Any standard laboratory filter paper,
(Warning—Poison, health hazard, may be toxic by ingestion, capable of absorbing the lead acetate solution may be used.
inhalation, or absorption through the skin) to test for the (Warning—Any paper containing active sulfides will interfere
presence of hydrogen sulfide and sodium hydrogen carbonate with the test.)
for the removal of hydrogen sulfide. X1.4 Procedure, Testing and Removal of Hydrogen Sul-
X1.1.3 This test method shall not be used when the sample fide
is a referee sample or when QA/QC protocols specify the test X1.4.1 Test a small portion of the sample by inserting a
method as written. Instances in which they can be used may be small strip of lead acetate test paper into it. When the test paper
instances of routine refinery control samples. is discolored by turning to a brown or black, the presence of
hydrogen sulfide is indicated.
X1.2 Summary of Test Method
X1.4.2 When the presence of hydrogen sulfide is indicated,
X1.2.1 Hydrogen sulfide is detected by saturating strips of
proceed as follows:
filter paper with lead acetate and drying them prior to use.
X1.4.2.1 Take a portion of the sample that is 3 to 4 times the
When properly prepared and used, they will turn from a white
volume required for the actual test and pour it into a separatory
color to a darker color due to the precipitation of lead sulfide
funnel.
by hydrogen sulfide.
X1.4.2.2 Add a volume of sodium hydrogen carbonate
X1.2.2 The hydrogen sulfide is removed by repeated wash- equal to about half the volume of the test portion and shake
ings with an aqueous solution of sodium hydrogen carbonate thoroughly. (Warning—When the sample is volatile, release
until the sample indicates the absence of hydrogen sulfide in any pressure developed by the shaking, cautiously.)
accordance with the lead acetate test. X1.4.2.3 Allow the two phases to settle, and when settled,
draw off and discard the aqueous phase.
X1.3 Reagents and Materials X1.4.2.4 Test the hydrocarbon phase again with fresh lead
X1.3.1 Purity of Reagents—All reagents shall conform to acetate paper.
the details specified in 7.1 of the main procedure. X1.4.2.5 Continue with the washing process until the
X1.3.2 Commercially prepared solutions and test paper may washed sample tests negative to the presence of hydrogen
be used when it is certain they will conform to the specifica- sulfide. (Warning—When elemental sulfur and mercaptans are
tions detailed in 7.1 of the main procedure. both present, it is possible that upon reheating the washed
sample, more hydrogen sulfide will form. Because the forma-
X1.3.3 Lead Acetate, Aqueous Solution—Prepare a 5 % tion of more hydrogen sulfide (after washing) will affect the
(m/m) solution of lead acetate [(CH3COO)2Pb.3H2O] in water. test result, do not reheat the washed portion of the sample.)
X1.3.4 Lead Acetate, Test Paper—Soak to saturation test X1.4.2.6 When the test portion is free of all hydrogen
strips of filter paper in the lead acetate solution and allow to sulfide, the determination of the thiol (mercaptan) content may
dry. (Warning—Since these papers react with hydrogen proceed.

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 D3227 − 24

X2. GENERIC QUALITY CONTROL STATEMENT FOR D02 TEST METHODS

X2.1 Confirm the performance of the instrument and the test criticality of the quality being measured, the demonstrated
procedure by analyzing a QC sample. stability of the testing process, and customer requirements.
Generally, a QC sample should be analyzed on each day of
X2.2 Prior to monitoring the measurement process, the user testing routine samples. The QC frequency should be increased
of the method needs to determine the average value and control when a large number of samples are routinely analyzed.
limits of the QC sample (see Practice D6299 and MNL76). However, when it is demonstrated that the testing is under
X2.3 Record the QC results and analyze by control charts or statistical control, the QC testing frequency may be reduced.
other statistically equivalent techniques to ascertain the statis- The QC sample precision should be periodically checked
tical control status of the total testing process (see Practice against the ASTM method precision to ensure data quality.
D6299 and MNL76). Any out-of-control data should trigger
investigation for root cause(s). The results of this investigation X2.5 It is recommended that, when possible, the type of QC
may, but not necessarily, result in instrument recalibration. sample that is regularly tested be representative of the samples
routinely analyzed. An ample supply of QC sample material
X2.4 In the absence of explicit requirements given in the should be available for the intended period of use and must be
test method, the frequency of QC testing is dependent on the homogeneous and stable under the anticipated storage condi-
tions.
6
ASTM MNL7, Manual of Presentation of Data Control Chart Analysis, 6th ed.,
Section 3: Control Chart for Individuals, ASTM International, W. Conshohocken, X2.6 See Practice D6299 and MNL76 for further guidance
PA. on QC and Control Charting techniques.

SUMMARY OF CHANGES

Subcommittee D02.03 has identified the location of selected changes to this standard since the last issue
(D3227 – 23) that may impact the use of this standard. (Approved March 1, 2024.)

(1) Revised subsections 6.3, 9.1, 9.2, and related subsections. (2) Added subsection 9.3.

Subcommittee D02.03 has identified the location of selected changes to this standard since the last issue
(D3227 – 16) that may impact the use of this standard. (Approved May 1, 2023.)

(1) Added Terminology D4175 to Section 2. (2) Added Section 3.

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