An American National Standard

Designation: D 3227 – 04a

Designation: 342/00

Standard Test Method for

(Thiol Mercaptan) Sulfur in Gasoline, Kerosine, Aviation
Turbine, and Distillate Fuels (Potentiometric Method)1
This standard is issued under the fixed designation D 3227; 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 (e) indicates an editorial change since the last revision or reapproval.

This standard has been approved for use by agencies of the Department of Defense.

1. Scope* D 4177 Practice for Automatic Sampling of Petroleum and

1.1 This test method covers the determination of mercaptan Petroleum Products
sulfur in gasolines, kerosines, aviation turbine fuels, and D 6299 Practice for Applying Statistical Quality Assurance
distillate fuels containing from 0.0003 to 0.01 mass % of Techniques to Evaluate Analytical Measurement System
mercaptan sulfur. Organic sulfur compounds such as sulfides, Performance
disulfides, and thiophene, do not interfere. Elemental sulfur in 3. Summary of Test Method
amounts less than 0.0005 mass % does not interfere. Hydrogen
sulfide will interfere if not removed, as described in 9.2. 3.1 The hydrogen sulfide-free sample is dissolved in an
1.2 The values in acceptable SI units are to be regarded as alcoholic sodium acetate titration solvent and titrated potentio-
the standard. The values in parentheses are for information metrically with silver nitrate solution, using as an indicator the
only. potential between a glass reference electrode and a silver/
1.3 This standard does not purport to address all of the silver-sulfide indicating electrode. Under these conditions, the
safety concerns, if any, associated with its use. It is the mercaptan sulfur is precipitated as silver mercaptide and the
responsibility of the user of this standard to establish appro- end point of the titration is shown by a large change in cell
priate safety and health practices and determine the applica- potential.
bility of regulatory limitations prior to use. For specific 4. Significance and Use
warning statements, see Sections 6, 8, 9, and Appendix X1.
4.1 Mercaptan sulfur has an objectionable odor, an adverse
2. Referenced Documents effect on fuel system elastomers, and is corrosive to fuel
2.1 ASTM Standards: 2 system components.
D 1193 Specification for Reagent Water 5. Apparatus
D 1250 Guide for Use of the Petroleum Measurement
Tables 5.1 As described in 5.2-5.5; alternatively, any automatic
D 1298 Test Method for Density, Relative Density (Specific titration system may be used that, using the same electrode pair
Gravity), or API Gravity of Crude Petroleum and Liquid described in 5.3, is capable of performing the titration as
Petroleum Products by Hydrometer Method described in Section 9 and selecting the endpoint specified in
D 4052 Test Method for Density and Relative Density of 11.1 with a precision that meets or is better than that given in
Liquids by Digital Density Meter Section 14.
D 4057 Practice for Manual Sampling of Petroleum and 5.2 Meter—An electronic voltmeter, operating on an input
Petroleum Products of less than 9 3 10−12 A and having a sensitivity of 62 mV
over a range of at least 61 V. The meter shall be electrostati-
cally shielded, and the shield shall be connected to the ground.3
1
This test method is under the jurisdiction of ASTM Committee D02 on 5.3 Cell System, consisting of a reference and indicating
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee
D02.03 on Elemental Analysis. electrode. The reference electrode should be a sturdy, pencil-
Current edition approved Nov. 1, 2004. Published November 2004. Originally type glass electrode, having a shielded lead connected to
approved in 1973. Last previous edition approved in 2004 as D 3227–04.
2
ground. The indicating electrode shall be made from a silver
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
3
the ASTM website. Any apparatus that will give equal or better precision is acceptable.

*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
 D 3227 – 04a
wire, 2 mm (0.08 in.) in diameter or larger, mounted in an failure to remove peroxides will lead to low results. It is not necessary to
insulated support. Silver billet electrodes can also be used. perform this step if the alcohol is tested and found free of peroxides.
5.4 Buret, 10-mL capacity, graduated in 0.05-mL intervals, 6.6.1 Standardization—Add six drops of concentrated
with a tip that extends approximately 120 mm (5 in.) below the HNO3 (relative density 1.42) (Warning—Poison. Causes se-
stopcock. vere burns. Harmful or fatal if swallowed or inhaled) to 100
5.5 Titration Stand, preferably built as an integral part of the mL of water in an appropriately sized beaker (for example, a
meter housing and provided with supports for the electrodes 200-, 250-, or 300-mL size beaker is typically large enough).
and electrical stirrer, all connected to ground. No permanent Remove oxides of nitrogen by boiling for 5 min. Cool to
change in meter reading should be noticeable upon connecting ambient temperature. Pipet 5 mL of 0.1 mol/L KI solution into
or disconnecting the stirring motor. the beaker and titrate with the AgNO3 solution choosing the
end point at the inflection of the titration curve.
6. Reagents and Materials 6.7 Silver Nitrate, Standard Alcoholic Solution (0.010 mol/
6.1 Purity of Reagents—Reagent grade chemicals shall be L)—Prepare daily when the test is being performed by dilution
used in all tests. Unless otherwise indicated, it is intended that of the 0.1 N standard. Pipet 100 mL of the 0.1 mol/L standard
all reagents shall conform to the specifications of the Commit- into a 1-L volumetric flask and dilute to volume with propan-
tee on Analytical Reagents of the American Chemical Society, 2-ol. Calculate the exact molarity.
where such specifications are available.4 Other grades may be 6.8 Sodium Sulfide Solution (10 g/L)—Dissolve 10 g of
used, provided it is first ascertained that the reagent is of Na2S in water and dilute to 1 L with water. Prepare fresh as
sufficiently high purity to permit its use without lessening the needed.
accuracy of the determination. 6.9 Sulfuric Acid, dilute. Cautiously dilute five volumes of
6.1.1 Commercially available solutions may be used in water with one volume of sulfuric acid (relative density 1.84).
place of prepared laboratory solutions, when they are certified (Warning—Adding the acid will generate heat: mix well. If
to meet the required concentrations. water begins to boil, cool before adding more acid.) Note that
6.1.2 Alternate volumes of solutions and solvents may be only limited volumes are required because only 10 mL are
prepared, when an equivalent concentration is maintained. needed for each litre of cadmium sulfate solution.
6.2 Water—Reagent grade, Type I, Specification D 1193. 6.10 Titration Solvent—Low molecular weight mercaptans,
6.3 Cadmium Sulfate, Acid Solution (150 g/L)—Dissolve as usually found in gasoline, are readily lost from the titration
150 g of cadmium sulfate (3CdSO 4·8H2O) in water. solution if an acidic titration solvent is used. For the determi-
(Warning—Poison. May be fatal if swallowed or inhaled. A nation of the higher molecular weight mercaptan as normally
known carcinogen (animal positive).) Add 10 mL of dilute encountered in kerosines, aviation turbine fuels, and distillate
H2SO4 (Warning—Poison. Causes severe burns. Harmful or fuels, the acidic titration solvent is used to achieve more rapid
fatal if swallowed or inhaled) and dilute to 1 L with water. equilibrium between successive additions of the titrant.
6.4 Potassium Iodide, Standard Solution (approximately 0.1 6.10.1 Alkaline Titration Solvent—Dissolve 2.7 g of sodium
mol/L)—Dissolve 17 g of KI (weigh to 0.01 g) in 100 mL of acetate trihydrate (NaC2H3O2·3H2O) or 1.6 g of anhydrous
water in a 1-L volumetric flask and dilute to 1 L. Calculate the sodium acetate (NaC2H3O2) in 25 mL of water free of
exact molarity. dissolved oxygen and pour into 975 mL of propan-2-ol (99 %)
6.5 Propan-2-ol—(Warning—Flammable. Warning— (Note 1). When necessary, remove dissolved oxygen by purg-
Unless inhibited against it, peroxides can form in propan-2-ol ing the solution with a rapid stream of nitrogen for 10 min each
when stored in the same container that is exposed to air. When day prior to use; keep protected from the atmosphere. To
this happens and the propan-2-ol evaporates to dryness, an minimize oxygen from dissolving in the solution during
explosion can occur. When peroxides are suspected, they may storage, an option exists to nitrogen blanket the solution prior
be removed by percolation through an activated alumina to sealing the solvent container.
column.) 6.10.2 Acidic Titration Solvent—Dissolve 2.7 g of
6.6 Silver Nitrate, Standard Alcoholic Solution (0.1 mol/ NaC2H3O2·3H2O or 1.6 g of NaC2H3O2 in 20 mL of water free
L)—Dissolve 17 g of AgNO3 in 100 mL of water in a 1-L of dissolved oxygen and pour into 975 mL of propan-2-ol
volumetric flask and dilute to 1 L with propan-2-ol (99 %) (see (99 %) (Note 1) and add 4.6 mL of glacial acetic acid. When
Note 1). Store in a dark bottle and standardize at intervals necessary, remove dissolved oxygen by purging the solution
frequent enough to detect a change of 0.0005 or greater in with a rapid stream of nitrogen for 10 min each day prior to
molarity. use; keep protected from the atmosphere. To minimize oxygen
NOTE 1—It is important to pass the propan-2-ol through a column of from dissolving in the solution during storage, an option exists
activated alumina to remove peroxides that may have formed on storage; to nitrogen blanket the solution prior to sealing the solvent
container.
6.11 Polishing Paper or Cloth, 6–20 µm average particle
4
Reagent Chemicals, American Chemical Society Specifications, American
size abrasive.
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Annual Standards for Laboratory 7. Sampling
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, 7.1 Take the sample in accordance with Practice D 4057 or
MD. Practice D 4177.

2
 D 3227 – 04a
7.2 Methanethiol (methyl mercaptan) has a boiling point of solution as described previously. If no further precipitate is
6.2°C and may be expected to be present in light untreated formed, proceed as directed in 9.3. If a precipitate appears,
gasolines. Therefore, when the presence of this low boiling repeat the extraction with the CdSO4 solution until all of the
thiol (mercaptan) is known or expected, specimen to be tested H2S has been removed. (Warning—Certain straight run gaso-
shall be kept below 4°C to prevent the loss of mercaptan from lines can contain significant amounts of both low molecular
such samples. weight mercaptans and dissolved elemental sulfur, which,
when heated under total reflux conditions, may produce H2S by
8. Preparation of Apparatus the inter-reaction of both. This phenomenon is particularly
8.1 Glass Electrode—After each manual titration, or batch noticed in straight run gasolines produced from some natural
of titrations, in the case of automatic titration systems, wipe the gas condensates. Therefore, it is advisable that during the
electrode with a soft, clean tissue and rinse with water. Clean removal of H2S (and after all H2S has been extracted), that no
the electrode at frequent intervals (at least once a week) by heat should be applied to the sample.)
stirring in cold chromic acid solution (Warning—Causes 9.2.1 When the test results obtained are not for referee
severe burns. A recognized carcinogen. Strong oxidizer— purposes and Quality Assurance/Quality Control (QA/QC)
contact with other material may cause fire. Hygroscopic. An protocol permits, an alternative test for, and a procedure for the
equivalent, chromium-free cleaning solution may be used) for removal of, hydrogen sulfide can be used. This process uses
a few seconds (10 s maximum). When not in use, keep lower lead acetate paper and sodium hydrogen carbonate and is
half of the electrode immersed in water. described in Appendix X1.
8.2 Silver/Silver-Sulfide Electrode—Each day prior to use, 9.2.2 There are available automated instruments that elimi-
or as triggered by the analysis of a quality control (QC) sample nate the necessity to remove H2S when present, prior to
(see Section 12), prepare a fresh silver sulfide coating on the performing the analysis, since the H2S titration curve does not
electrode by the following method: interfere with the titration curve of the thiol or mercaptan
8.2.1 Burnish electrode with polishing paper or cloth until a determination. Such equipment may be used when the test is
clean, polished silver surface shows. not for referee purposes. The precision statement does not
8.2.2 Place electrode in operating position and immerse it in include data obtained from this alternate procedure.
100 mL of titration solvent containing 8 mL of Na2S solution. 9.2.3 For referee purposes, the protocol, as detailed in 9.2,
8.2.3 Add slowly from a buret, with stirring, 10 mL of 0.1 shall be used. A possible non-referee situation may be the
mol/L AgNO3 solution over a period from 10 to 15 min. instance of routine refinery control.
8.2.4 Remove electrode from solution, wash with water, and 9.3 Measure with a pipet (or other suitable transfer device)
wipe with a soft, clean tissue. or weigh 20 to 50 mL of the original or treated sample into an
8.2.5 Between manual titrations, or batches of titrations in appropriately sized beaker (for example, a 200, 250, or 300 mL
the case of automatic titration systems, store the electrode a size beaker is typically large enough) containing 100 mL of the
minimum of 5 min in 100 mL of titration solvent containing 0.5 appropriate titration solvent. Place the beaker on the titration
mL of the 0.1 mol/L AgNO3 solution. stand or on the auto-sampler of an automatic titration system.
9. Procedure If an automatic titration system is used, set up the system to
reproduce the experimental conditions specified in 9.3.1-9.3.3.
9.1 Determination of Density—If the sample is to be mea- Adjust the position of the titration stand so that the electrodes
sured volumetrically, determine the density by Test Method are about half immersed. Fill the buret with 0.01 mol/L
D 1298 or Test Method D 4052 at the temperature at which the alcoholic AgNO3 solution and position it in the titration
test portion will be taken, either directly or from the density assembly so that the tip extends approximately 25 mm (1 in.)
determined at a reference temperature and converted to the below the surface of the liquid in the beaker. Adjust the speed
transfer temperature by use of the Petroleum Measurement of the stirrer to give vigorous stirring without spattering.
Tables (Guide D 1250).
9.3.1 Record the initial buret and cell potential readings.
9.2 Removal of Hydrogen Sulfide—Test the sample qualita-
The usual meter readings for mercaptan presence are in
tively for hydrogen sulfide (H2S) by mixing 5 mL of the sample
the −250 mV to −350 mV range. Add suitable small portions of
with 5 mL of the acid CdSO4 solution. If no precipitate
0.01 mol/L AgNO3 solution and, after waiting until a constant
appears, proceed with the analysis of the sample as described
potential has been established, record the buret and meter
in 9.3. If a yellow precipitate appears, remove the H2S in the
readings. Consider the potential constant if it changes less than
following manner: Place a quantity of the sample, three to four
6 mV/min.
times that required for the analysis, in a separatory funnel
containing a volume of the acid CdSO4 solution equal to one NOTE 2—If potential readings obtained with freshly prepared electrodes
half that of the sample and shake vigorously. Draw off and are erratic, it is possible that the electrodes are not properly conditioned.
discard the aqueous phase containing the yellow precipitate. This difficulty usually disappears in succeeding titrations.
Repeat the extraction with another portion of the CdSO4 NOTE 3—When analyzing samples with a relatively high mercaptan
solution. Again draw off the aqueous phase, and wash the concentration, the use of a 20 to 50 mL sample size can require an
unreasonably long titration time and a large quantity of the titrant. For
sample with three 25 to 30-mL portions of water, withdrawing such samples, a smaller sample size may be used or the original sample
the water after each washing. Filter the hydrocarbon through a may be diluted with a suitable solvent that is miscible with the sample and
rapid paper. Test a small portion of the washed sample, such as free of mercaptans into the 20 to 50 mL sample size range prior to titrating
in a test tube or vial, with a few millilitres of the CdSO4 the sample. The precision of samples using <20 mL sample sizes or

3
 D 3227 – 04a
samples that have been diluted have not been determined in an interlabo- 11. Interpretation of Results
ratory study.
11.1 Treatment of Data—Plot the cumulative volumes of
NOTE 4—With certain instruments, the algebraic sign of the potentials 0.01 M AgNO3 solution added against the corresponding cell
may appear reversed.
potentials. Select the end point at the inflection point of the
9.3.2 When the potential change is small for each increment steepest portion of each “break” in the titration curve as shown
of AgNO3 solution, add volumes as large as 0.5 mL. When the in Fig. 1. The shape of the titration curve may change with
change of potential becomes greater than 6 mV/0.1 mL, use different instruments. However, the above interpretation of the
0.05-mL increments of 0.01 mol/L AgNO3 solution. Near the end point should be followed.
end point of the titration, 5 or 10 min may elapse before a 11.1.1 Mercaptans Only—If mercaptans alone are present in
constant potential is obtained. Although it is important to wait the sample, the titration produces a curve of the first type
for equilibrium conditions, it is also important that the duration shown in Fig. 1, having an initial plateau at a potential equal to
of the titration be as short as possible to avoid oxidation of the or more negative than −250 mV, and an end point when a
sulfur compounds by atmospheric oxygen. Once started, a potential change of less than 6 mV/min is reached and the
titration must never be interrupted and resumed later. change in mV/min of titrant is reduced with each incremental
addition.
9.3.3 Continue the titration until the meter reading change 11.1.2 Mercaptans and Elemental Sulfur—When elemental
of the cell potential per 0.1 mL of 0.01 M AgNO3 solution has sulfur and mercaptans are both present in the sample, a
become relatively constant. Consider the potential constant if it chemical interaction occurs which, in the titration solvent used,
changes less than 6 mV/min. Remove the titrated solution, precipitates silver sulfide (Ag2S) during the titration.
rinse the electrodes with alcohol, and wipe with a dry tissue. If 11.1.3 When mercaptans are present in excess, the end of
an automatic titration system is used, rinse the electrodes well the Ag2S precipitation occurs at about −550 to −350 mV, and is
with alcohol, allow the excess alcohol to drain off the electrode followed by the precipitation of the silver mercaptide to
and then proceed with the next sample. Between successive the +300-mV end point. This situation is shown in the middle
determinations (or batches of determinations in the case of curve of Fig. 1. Since all of the Ag2S originates from an
automatic titration systems) on the same day, store the elec- equivalent amount of mercaptan, the total titration to the
trodes in accordance with 8.1 and 8.2.5. mercaptide end point must be used to calculate the amount of
9.4 As often as is required and preferably, at least daily, mercaptan sulfur.
when the test equipment is being used, perform a blank 11.1.4 When elemental sulfur is present in excess, the end of
titration following 9.3-9.3.3 without adding a test sample. the Ag2S precipitation is taken in the same region ( +300 mV)
as in the case of silver mercaptide, and is calculated as
10. Calculation mercaptan sulfur.
11.1.5 When samples of light gasolines containing meth-
10.1 Calculate the mercaptan sulfur content of the sample as anethiol (methyl mercaptan) or heavier thiols (mercaptans)
follows: appear to give erratic results, it may be necessary to cool and
Mercaptan sulfur, mass % 5 ~DM ~A1 – A0! 3 3.206!/W (1) maintain the test apparatus below 4°C prior to proceeding, as
detailed in 9.2-9.4 inclusive. For these samples, this step may
or be necessary for more reproducible test results.
Mercaptan sulfur, mass % 5 ~DM ~A1 – A0! 3 3.206!/~d 3 V!
(2)
12. Quality Assurance/Quality Control
D 5 ~W 1 I!/W (3)
12.1 Confirm the performance of the instrument and the test
procedure by analyzing a control (QC) sample.
D 5 ~V 1 J!/V (4) 12.1.1 When QA/QC protocols are already established in
where: the testing facility, these may be used when they confirm the
A1 = millilitres of AgNO3 solution required to reach the reliability of test result.
end point in the vicinity of +300 mV (see Fig. 1), 12.1.2 When there is no QA/QC protocol established in the
when a sample is being titrated, testing facility, Appendix X2 may be used as the QA/QC
A0 = mL of AgNO3 solution required to reach the end system.
point in the vicinity of +300mV (see Fig. 1), when 12.2 Users of this test method are advised that in contractual
only the blank is titrated. (Note, there are no other agreements, one or more of the contracting parties can and may
changes to the factors in the equation.) make Appendix X2 a mandatory practice.
d = density of sample at transfer temperature, g/mL,
13. Report
D = dilution factor (if necessary, see Note 3),
I = grams of diluent used, 13.1 Report the result to the nearest 0.0001 % (m/m) or to
J = mL of diluent used, the nearest 1 mg/kg.
M = molarity of the AgNO3 solution,
W = grams of sample used, 14. Precision and Bias
3.206 = 100 3 g meq weight S in mercaptan, and 14.1 Precision—The precision of this test method as deter-
V = mL of sample used. mined by statistical examination of interlaboratory results is as
follows:

4
 D 3227 – 04a

FIG. 1 Illustrative Potentiometric Titration

14.1.1 Repeatability—The difference between two succes- ing in different laboratories on identical test material would, in
sive test results, obtained by the same operator with the same the long run, in the normal and correct operation of the test
apparatus under constant operating conditions on identical test method, exceed the following values only in one case in
material, would in the long run, in the normal and correct twenty:
operation of the test method, exceed the following values only Reproducibility 0.00031 + 0.042x (see Note 5)
in one case in twenty:
Repeatability 0.00007 + 0.027x (see Note 5) where:
x = average mercaptan sulfur, mass %.
where: 14.2 Bias—The bias for the procedure in this test method
x = average mercaptan sulfur, mass %. has not been determined.
NOTE 5—This amount is shown graphically in Fig. 2.
15. Keywords
14.1.2 Reproducibility—The difference between two single
and independent results obtained by different operators work- 15.1 mercaptan; potentiometric; sulfur

5
 D 3227 – 04a

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

APPENDIXES

(Nonmandatory Information)

X1. AN ALTERNATIVE METHOD FOR THE REMOVAL OF HYDROGEN SULFIDE

X1.1 Scope X1.2.2 The hydrogen sulfide is removed by repeated wash-

X1.1.1 This test method provides an alternative to using a ings with an aqueous solution of sodium hydrogen carbonate
cadmium sulfate acid solution. (Warning—Poison. May be until the sample indicates the absence of hydrogen sulfide in
fatal if swallowed or inhaled. A known carcinogen (animal accordance with the lead acetate test.
positive).) (Warning—Poison. Causes severe burns. Harmful
X1.3 Reagents and Materials
or fatal if swallowed or inhaled.)
X1.1.2 This test method uses lead acetate test paper X1.3.1 Purity of Reagents—All reagents shall conform to
(Warning—Poison, health hazard, may be toxic by ingestion, the details specified in 6.1 of the main procedure.
inhalation, or absorption through the skin) to test for the X1.3.2 Commercially prepared solutions and test paper may
presence of hydrogen sulfide and sodium hydrogen carbonate be used when it is certain they will conform to the specifica-
for the removal of hydrogen sulfide. tions detailed in 6.1 of the main procedure.
X1.1.3 This test method shall not be used when the sample X1.3.3 Lead Acetate, Aqueous Solution—Prepare a 5 %
is a referee sample or when QA/QC protocols specify the test (m/m) solution of lead acetate [(CH3COO)2Pb.3H2O] in water.
method as written. Instances in which they can be used may be X1.3.4 Lead Acetate, Test Paper—Soak to saturation test
instances of routine refinery control samples. strips of filter paper in the lead acetate solution and allow to
dry. (Warning—Since these papers react with hydrogen sul-
X1.2 Summary of Test Method fide, it is necessary to dry and store them in a hydrogen sulfide
X1.2.1 Hydrogen sulfide is detected by saturating strips of free atmosphere.)
filter paper with lead acetate and drying them prior to use. X1.3.5 Sodium Hydrogen Carbonate, Aqueous Solution—
When properly prepared and used, they will turn from a white Prepare this solution by dissolving 50 6 1 g of sodium
color to a darker color due to the precipitation of lead sulfide hydrogen carbonate (Na2HCO3) in water; dilute to 1 L in a
by hydrogen sulfide. volumetric flask.

6
 D 3227 – 04a
X1.3.6 Test Paper—Any standard laboratory filter paper, thoroughly. (Warning—When the sample is volatile, release
capable of absorbing the lead acetate solution may be used. any pressure developed by the shaking, cautiously.)
(Warning—Any paper containing active sulfides will interfere X1.4.2.3 Allow the two phases to settle, and when settled,
with the test.) draw off and discard the aqueous phase.
X1.4 Procedure, Testing and Removal of Hydrogen X1.4.2.4 Test the hydrocarbon phase again with fresh lead
Sulfide acetate paper.
X1.4.1 Test a small portion of the sample by inserting a X1.4.2.5 Continue with the washing process until the
small strip of lead acetate test paper into it. When the test paper washed sample tests negative to the presence of hydrogen
is discolored by turning to a brown or black, the presence of sulfide. (Warning—When elemental sulfur and mercaptans are
hydrogen sulfide is indicated. both present, it is possible that upon reheating the washed
X1.4.2 When the presence of hydrogen sulfide is indicated, sample, more hydrogen sulfide will form. Because the forma-
proceed as follows: tion of more hydrogen sulfide (after washing) will affect the
X1.4.2.1 Take a portion of the sample that is 3 to 4 times the test result, do not reheat the washed portion of the sample.)
volume required for the actual test and pour it into a separatory X1.4.2.6 When the test portion is free of all hydrogen
funnel. sulfide, the determination of the thiol (mercaptan) content may
X1.4.2.2 Add a volume of sodium hydrogen carbonate proceed.
equal to about half the volume of the test portion and shake

X2. GENERIC QUALITY CONTROL STATEMENT FOR D02 TEST METHODS

X2.1 Confirm the performance of the instrument and the criticality of the quality being measured, the demonstrated
test 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 D 6299 and MNL75). However, when it is demonstrated that the testing is under
X2.3 Record the QC results and analyze by control charts statistical control, the QC testing frequency may be reduced.
or other statistically equivalent techniques to ascertain the The QC sample precision should be periodically checked
statistical control status of the total testing process (see Practice against the ASTM method precision to ensure data quality.
D 6299 and MNL75). 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.
5
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 D 6299 and MNL75 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
(D 3227–04) that may impact the use of this standard. (Approved Nov. 1, 2004.)

(1) Added Section 13, Report, to indicate how results are to be

reported.

Subcommittee D02.03 has identified the location of selected changes to this standard since the last issue
(D 3227-02a) that may impact the use of this standard. (Approved May 1, 2004.)

(1) Updated 6.6.1 to replace the beaker size requirement.

7
 D 3227 – 04a
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