NOTICE: This standard has either been superceded and replaced by a new version or discontinued.

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An American National Standard

Designation: D 3227 – 02

Designation: 342/2000

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.
This test method has been approved by the sponsoring committee and accepted by the cooperation societies in accordance with
established procedures.

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

1.1 This test method covers the determination of mercaptan Petroleum Products4
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, Performance5
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 (see Note 1), using as an
only. indicator the potential between a glass reference electrode and
1.3 This standard does not purport to address all of the a silver/silver-sulfide indicating electrode. Under these condi-
safety concerns, if any, associated with its use. It is the tions, the mercaptan sulfur is precipitated as silver mercaptide
responsibility of the user of this standard to establish appro- and the end point of the titration is shown by a large change in
priate safety and health practices and determine the applica- cell potential.
bility of regulatory limitations prior to use. For specific hazard 4. Significance and Use
statements, see Sections 6, 8, and 9.
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: system components.
D 1193 Specification for Reagent Water2 5. Apparatus
D 1250 Guide for Petroleum Measurement Tables3
D 1298 Test Method for Density, Relative Density (Specific 5.1 As described in 5.2-5.5; alternatively, any automatic
Gravity), or API Gravity of Crude Petroleum and Liquid titration system may be used that, using the same electrode pair
Petroleum Products by Hydrometer Method3 described in 5.3, is capable of performing the titration as
D 4052 Test Method for Density and Relative Density of described in Section 9 and selecting the endpoint specified in
Liquids by Digital Density Meter4 11.1 with a precision that meets or is better than that given in
D 4057 Practice for Manual Sampling of Petroleum and Section 13.
Petroleum Products4 5.2 Meter—An electronic voltmeter, operating on an input
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.6
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 electrode. The reference electrode should be a sturdy, pencil-
D02.03 on Elemental Analysis.
Current edition approved April 10, 2002. Published May 2002. Originally type glass electrode, having a shielded lead connected to
published as D 3227 – 73. Last previous edition D 3227 – 00.
2
Annual Book of ASTM Standards, Vol 11.01.
3 5
Annual Book of ASTM Standards, Vol 05.01. Annual Book of ASTM Standards, Vol 05.03.
4 6
Annual Book of ASTM Standards, Vol 05.02. Any apparatus that will give equal or better precision will be 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.

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 NOTICE: This standard has either been superceded and replaced by a new version or discontinued.
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D 3227 – 02
ground. The indicating electrode shall be made from a silver activated alumina to remove peroxides that may have formed on storage;
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 (rel dens 1.42) (Warning—Poison. Causes severe
stopcock. burns. Harmful or fatal if swallowed or inhaled.) to 100 mL of
5.5 Titration Stand, preferably built as an integral part of the water in a 300-mL tall-form beaker. Remove oxides of nitrogen
meter housing and provided with supports for the electrodes by boiling for 5 min. Cool to ambient temperature. Pipet 5 mL
and electrical stirrer, all connected to ground. No permanent of 0.1 mol/L KI solution into the beaker and titrate with the
change in meter reading should be noticeable upon connecting AgNO3 solution choosing the end point at the inflection of the
or disconnecting the stirring motor. titration curve.
6.7 Silver Nitrate, Standard Alcoholic Solution (0.010 mol/
6. Reagents and Materials L)—Prepare daily when the test is being performed by dilution
6.1 Purity of Reagents—Reagent grade chemicals shall be of the 0.1 N standard. Pipet 100 mL of the 0.1 mol/L standard
used in all tests. Unless otherwise indicated, it is intended that into a 1-L volumetric flask and dilute to volume with propan-
all reagents shall conform to the specifications of the Commit- 2-ol. Calculate the exact molarity.
tee on Analytical Reagents of the American Chemical Society, 6.8 Sodium Sulfide Solution (10 g/L)—Dissolve 10 g of
where such specifications are available.7 Other grades may be Na2S in water and dilute to 1 L with water. Prepare fresh as
used, provided it is first ascertained that the reagent is of needed.
sufficiently high purity to permit its use without lessening the 6.9 Sulfuric Acid, dilute. Cautiously dilute five volumes of
accuracy of the determination. water with one volume of sulfuric acid (Sp.Gr.1.84).
6.1.1 Commercially available solutions may be used in (Warning—Adding the acid will generate heat: mix well. If
place of prepared laboratory solutions, when they are certified water begins to boil, cool before adding more acid.) Note that
to meet the required concentrations. only limited volumes are required because only 10 mL are
6.1.2 Alternate volumes of solutions and solvents may be needed for each litre of cadmium sulfate solution.
prepared, when an equivalent concentration is maintained. 6.10 Titration Solvent—Low molecular weight mercaptans,
6.2 Water—Reagent grade, Type I, Specification D 1193. as usually found in gasoline, are readily lost from the titration
6.3 Cadmium Sulfate, Acid Solution (150 g/L)—Dissolve solution if an acidic titration solvent is used. For the determi-
150 g of cadmium sulfate (3CdSO43 8H2O) in water. nation of the higher molecular weight mercaptan as normally
(Warning—Poison. May be fatal if swallowed or inhaled. A encountered in kerosines, aviation turbine fuels, and distillate
known carcinogen (animal positive).) Add 10 mL of dilute fuels, the acidic titration solvent is used to achieve more rapid
H2SO4 (Warning—Poison. Causes severe burns. Harmful or equilibrium between successive additions of the titrant.
fatal if swallowed or inhaled.) and dilute to 1 L with water. 6.10.1 Alkaline Titration Solvent—Dissolve 2.7 g of sodium
6.4 Potassium Iodide, Standard Solution (approximately 0.1 acetate trihydrate (NaC2H3O2·3H2O) or 1.6 g of anhydrous
mol/L)—Dissolve 17 g of KI (weigh to 0.01 g) in 100 mL of sodium acetate (NaC2H3O2) in 25 mL of water free of
water in a 1-L volumetric flask and dilute to 1 L. Calculate the dissolved oxygen and pour into 975 mL of propan-2-ol (99 %)
exact molarity. (Note 1). When necessary, remove dissolved oxygen by purg-
6.5 2-Propanol—(Warning—Flammable.). Warning— ing the solution with a rapid stream of nitrogen for 10 min each
Unless inhibited against it, peroxides can form in 2-propanol day prior to use; keep protected from the atmosphere. To
when stored in the same container that is exposed to air. When minimize oxygen from dissolving in the solution during
this happens and the propan-2-ol evaporates to dryness, an storage, an option exists to nitrogen blanket the solution prior
explosion can occur. When peroxides are suspected, they may to sealing the solvent container.
be removed by percolation through an activated alumina 6.10.2 Acidic Titration Solvent—Dissolve 2.7 g of
column. NaC2H3O2·3H2O or 1.6 g of NaC2H3O2 in 20 mL of water free
6.6 Silver Nitrate, Standard Alcoholic Solution (0.1 mol/ of dissolved oxygen and pour into 975 mL of propan-2-ol
L)—Dissolve 17 g of AgNO3 in 100 mL of water in a 1-L (99 %) (Note 1) and add 4.6 mL of glacial acetic acid. When
volumetric flask and dilute to 1 L with 2-propanol (99 %) (see necessary, remove dissolved oxygen by purging the solution
Note 1). Store in a dark bottle and standardize at intervals with a rapid stream of nitrogen for 10 min each day prior to
frequent enough to detect a change of 0.0005 or greater in use; keep protected from the atmosphere. To minimize oxygen
molarity. from dissolving in the solution during storage, an option exists
NOTE 1—It is important to pass the propan-2-ol through a column of to nitrogen blanket the solution prior to sealing the solvent
container.
6.11 Polishing Paper or Cloth, 6–20 µm average particle
7 size abrasive.
Reagent Chemicals, American Chemical Society Specifications, American
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar 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.

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D 3227 – 02
7.2 Methanethiol (methyl mercaptan) has a boiling point of formed, proceed as directed in 9.3. If a precipitate appears,
6.2°C and may be expected to be present in light untreated repeat the extraction with the CdSO4 solution until all of the
gasolines. Therefore, when the presence of this low boiling H2S has been removed. (Warning—Certain straight run gaso-
thiol (mercaptan) is known or expected, specimen to be tested lines can contain significant amounts of both low molecular
shall be kept below 4°C to prevent the loss of mercaptan from weight mercaptans and dissolved elemental sulfur, which,
such samples. when heated under total reflux conditions, may produce H2S by
the inter-reaction of both. This phenomenon is particularly
8. Preparation of Apparatus noticed in straight run gasolines produced from some natural
8.1 Glass Electrode—After each manual titration, or batch gas condensates. Therefore, it is advisable that during the
of titrations, in the case of automatic titration systems, wipe the removal of H2S (and after all H2S has been extracted), that no
electrode with a soft, clean tissue and rinse with water. Clean heat should be applied to the sample.)
the electrode at frequent intervals (at least once a week) by 9.2.1 When the test results obtained are not for referee
stirring in cold chromic acid solution (Warning—Causes purposes and Quality Assurance/Quality Control (QA/QC)
severe burns. A recognized carcinogen. Strong oxidizer— protocol permits, an alternative test for, and a procedure for the
contact with other material may cause fire. Hygroscopic. An removal of, hydrogen sulfide can be used. This process uses
equivalent, chromium-free cleaning solution may be used.) for lead acetate paper and sodium hydrogen carbonate and is
a few seconds (10 s maximum). When not in use, keep lower described in Appendix X1.
half of the electrode immersed in water. 9.2.2 For referee purposes, the protocol, as detailed in 9.2,
8.2 Silver/Silver-Sulfide Electrode— Each day prior to use, shall be used. A possible non-referee situation may be the
prepare a fresh silver sulfide coating on the electrode by the instance of routine refinery control.
following method: 9.3 Measure with a pipet or weigh 20 to 50 mL of the
8.2.1 Burnish electrode with polishing paper or cloth until a original or treated sample into an appropriately sized beaker
clean, polished silver surface shows. (for example, a 200, 250, or 300 mL size beaker is typically
8.2.2 Place electrode in operating position and immerse it in large enough) containing 100 mL of the appropriate titration
100 mL of titration solvent containing 8 mL of Na2S solution. solvent. Place the beaker on the titration stand or on the
8.2.3 Add slowly from a buret, with stirring, 10 mL of 0.1 auto-sampler of an automatic titration system. If an automatic
mol/L AgNO3 solution over a period from 10 to 15 min. titration system is used, set up the system to reproduce the
8.2.4 Remove electrode from solution, wash with water, and experimental conditions specified in 9.3.1, 9.3.2, and 9.3.3.
wipe with a soft, clean tissue. Adjust the position of the titration stand so that the electrodes
8.2.5 Between manual titrations, or batches of titrations in are about half immersed. Fill the buret with 0.01 mol/L
the case of automatic titration systems, store the electrode a alcoholic AgNO3 solution and position it in the titration
minimum of 5 min in 100 mL of titration solvent containing 0.5 assembly so that the tip extends approximately 25 mm (1 in.)
mL of the 0.1 mol/L AgNO3 solution. below the surface of the liquid in the beaker. Adjust the speed
of the stirrer to give vigorous stirring without spattering.
9. Procedure
9.3.1 Record the initial buret and cell potential readings.
9.1 Determination of Density—If the sample is to be mea- The usual meter readings for mercaptan presence are in
sured volumetrically, determine the density by Test Method the −250 mV to −350 mV range. Add suitable small portions of
D 1298 or Test Method D 4052 at the temperature at which the 0.01 mol/L AgNO3 solution and, after waiting until a constant
test portion will be taken, either directly or from the density potential has been established, record the buret and meter
determined at a reference temperature and converted to the readings. Consider the potential constant if it changes less than
transfer temperature by use of the Petroleum Measurement 6 mV/min.
Tables (Guide D 1250).
9.2 Removal of Hydrogen Sulfide—Test the sample qualita- NOTE 2—If potential readings obtained with freshly prepared electrodes
tively for hydrogen sulfide (H2S) by mixing 5 mL of the sample are erratic, it is possible that the electrodes are not properly conditioned.
This difficulty usually disappears in succeeding titrations.
with 5 mL of the acid CdSO4 solution. If no precipitate
NOTE 3—With certain instruments, the algebraic sign of the potentials
appears, proceed with the analysis of the sample as described
may appear reversed.
in 9.3. If a yellow precipitate appears, remove the H2S in the
following manner: Place a quantity of the sample, three to four 9.3.2 When the potential change is small for each increment
times that required for the analysis, in a separatory funnel of AgNO3 solution, add volumes as large as 0.5 mL. When the
containing a volume of the acid CdSO4 solution equal to one change of potential becomes greater than 6 mV/0.1 mL, use
half that of the sample and shake vigorously. Draw off and 0.05-mL increments of 0.01 mol/L AgNO3 solution. Near the
discard the aqueous phase containing the yellow precipitate. end point of the titration, 5 or 10 min may elapse before a
Repeat the extraction with another portion of the CdSO4 constant potential is obtained. Although it is important to wait
solution. Again draw off the aqueous phase, and wash the for equilibrium conditions, it is also important that the duration
sample with three 25 to 30-mL portions of water, withdrawing of the titration be as short as possible to avoid oxidation of the
the water after each washing. Filter the hydrocarbon through a sulfur compounds by atmospheric oxygen. Once started, a
rapid paper. Test a small portion of the washed sample, such as titration must never be interrupted and resumed later.
in a test tube or vial, with a few millilitres of the CdSO4 9.3.3 Continue the titration until the meter reading change
solution as described previously. If no further precipitate is of the cell potential per 0.1 mL of 0.01 M AgNO3 solution has

3
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D 3227 – 02
become relatively constant. Consider the potential constant if it
changes less than 6 mV/min. Remove the titrated solution,
rinse the electrodes with alcohol, and wipe with a dry tissue. If
an automatic titration system is used, rinse the electrodes well
with alcohol, allow the excess alcohol to drain off the electrode
and then proceed with the next sample. Between successive
determinations (or batches of determinations in the case of
automatic titration systems) on the same day, store the elec-
trodes in accordance with 8.1 and 8.2.5.
9.4 As often as is required and preferably, at least daily,
when the test equipment is being used, perform a blank
titration following 9.3-9.3.3 without adding a test sample.

10. Calculation
10.1 Calculate the mercaptan sulfur content of the sample as
follows:
Mercaptan sulfur, mass % 5 ~AM ~A1 – A0!3 3.206!/W (1)

or FIG. 1 Illustrative Potentiometric Titration Curves

Mercaptan sulfur, mass % 5 ~AM ~A1 – A0! 3 3.206!/~d 3 V!
(2)
curve of Fig. 1. Since all of the Ag2S originates from an
where: equivalent amount of mercaptan, the total titration to the
A1 = millilitres of AgNO3 solution required to reach the mercaptide end point must be used to calculate the amount of
end point in the vicinity of +300 mV (see Fig. 1), mercaptan sulfur.
when a sample is being titrated, 11.1.4 When elemental sulfur is present in excess, the end of
A0 = mL of AgNO3 solution required to reach the end the Ag2S precipitation is taken in the same region ( +300 mV)
point in the vicinity of +300mV (see Fig. 1), when as in the case of silver mercaptide, and is calculated as
only the blank is titrated. (Note, there are no other mercaptan sulfur.
changes to the factors in the equation). 11.1.5 When samples of light gasolines containing meth-
d = density of sample at transfer temperature, g/mL,
anethiol (methyl mercaptan) or heavier thiols (mercaptans)
M = molarity of the AgNO3 solution,
W = grams of sample used, appear to give erratic results, it may be necessary to cool and
3.206 = 100 3 g meq weight S in mercaptan, and maintain the test apparatus below 4°C prior to proceeding, as
V = mL of sample used. detailed in 9.2-9.4 inclusive. For these samples, this step may
be necessary for more reproducible test results.
11. Interpretation of Results
12. Quality Assurance/Quality Control
11.1 Treatment of Data—Plot the cumulative volumes of
0.01 M AgNO3 solution added against the corresponding cell 12.1 Confirm the performance of the instrument and the test
potentials. Select the end point at the most positive value of the procedure by analyzing a control (QC) sample.
steepest portion of each “break” in the titration curve as shown 12.1.1 When QA/QC protocols are already established in
in Fig. 1. The shape of the titration curve may change with the testing facility, these may be used when they confirm the
different instruments. However, the above interpretation of the reliability of test result.
end point should be followed. 12.1.2 When there is no QA/QC protocol established in the
11.1.1 Mercaptans Only—If mercaptans alone are present in testing facility, Appendix X2 may be used as the QA/QC
the sample, the titration produces a curve of the first type system.
shown in Fig. 1, having an initial plateau at a potential equal to 12.2 Users of this test method are advised that in contractual
or more negative than −250 mV, and an end point when a agreements, one or more of the contracting parties can and may
potential change of less than 6 mV/min is reached and the make Appendix X2 a mandatory practice.
change in mV/min of titrant is reduced with each incremental
addition. 13. Precision and Bias
11.1.2 Mercaptans and Elemental Sulfur— When elemental 13.1 Precision:
sulfur and mercaptans are both present in the sample, a 13.1.1 The precision of this test method as determined by
chemical interaction occurs which, in the titration solvent used, statistical examination of interlaboratory results is as follows:
precipitates silver sulfide (Ag2S) during the titration. 13.1.1.1 Repeatability—The difference between two suc-
11.1.3 When mercaptans are present in excess, the end of cessive test results, obtained by the same operator with the
the Ag2S precipitation occurs at about −550 to −350 mV, and is same apparatus under constant operating conditions on identi-
followed by the precipitation of the silver mercaptide to cal test material, would in the long run, in the normal and
the +300-mV end point. This situation is shown in the middle correct operation of the test method, exceed the following

4
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D 3227 – 02

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

values only in one case in twenty: the test method, exceed the following values only in one case
Repeatability 0.00007 + 0.027x (see Note 4) in twenty:
Reproducibility 0.00031 + 0.042x (Note 4)
where:
x = average mercaptan sulfur, mass %. where:
x = average mercaptan sulfur, mass %.
NOTE 4—This amount is shown graphically in Fig. 2.
13.2 Bias—The bias for the procedure in this test method
13.1.1.2 Reproducibility—The difference between two has not been determined.
single and independent results obtained by different operators
working in different laboratories on identical test material 14. Keywords
would, in the long run, in the normal and correct operation of 14.1 mercaptan; potentiometric; sulfur

APPENDIXES

(Nonmandatory Information)

X1. AN ALTERNATIVE METHOD FOR THE REMOVAL OF HYDROGEN SULFIDE

X1.1 Scope presence of hydrogen sulfide and sodium hydrogen carbonate

X1.1.1 This test method provides an alternative to using a for the removal of hydrogen sulfide.
cadmium sulfate acid solution. (Warning—Poison. May be X1.1.3 This test method shall not be used when the sample
fatal if swallowed or inhaled. A known carcinogen (animal is a referee sample or when QA/QC protocols specify the test
positive).) (Warning— Poison. Causes severe burns. Harmful method as written. Instances in which they can be used may be
or fatal if swallowed or inhaled.) instances of routine refinery control samples.
X1.1.2 This test method uses lead acetate test paper
(Warning— Poison, health hazard, may be toxic by ingestion,
inhalation, or absorption through the skin.) to test for the

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D 3227 – 02
X1.2 Summary of Test Method X1.4 Procedure, Testing and Removal of Hydrogen
X1.2.1 Hydrogen sulfide is detected by saturating strips of Sulfide
filter paper with lead acetate and drying them prior to use. X1.4.1 Test a small portion of the sample by inserting a
When properly prepared and used, they will turn from a white small strip of lead acetate test paper into it. When the test paper
color to a darker color due to the precipitation of lead sulfide is discolored by turning to a brown or black, the presence of
by hydrogen sulfide.
hydrogen sulfide is indicated.
X1.2.2 The hydrogen sulfide is removed by repeated wash-
ings with an aqueous solution of sodium hydrogen carbonate X1.4.2 When the presence of hydrogen sulfide is indicated,
until the sample indicates the absence of hydrogen sulfide in proceed as follows:
accordance with the lead acetate test. X1.4.2.1 Take a portion of the sample that is 3 to 4 times the
volume required for the actual test and pour it into a separatory
X1.3 Reagents and Materials
funnel.
X1.3.1 Purity of Reagents—All reagents shall conform to
the details specified in 6.1 of the main procedure. X1.4.2.2 Add a volume of sodium hydrogen carbonate
X1.3.2 Commercially prepared solutions and test paper may equal to about half the volume of the test portion and shake
be used when it is certain they will conform to the specifica- thoroughly. (Warning—When the sample is volatile, release
tions detailed in 6.1 of the main procedure. any pressure developed by the shaking, cautiously.)
X1.3.3 Lead Acetate, Aqueous Solution—Prepare a 5 % X1.4.2.3 Allow the two phases to settle, and when settled,
(m/m) solution of lead acetate [(CH3COO)2Pb.3H2O] in water. draw off and discard the aqueous phase.
X1.3.4 Lead Acetate, Test Paper—Soak to saturation test X1.4.2.4 Test the hydrocarbon phase again with fresh lead
strips of filter paper in the lead acetate solution and allow to acetate paper.
dry. (Warning—Since these papers react with hydrogen sul- X1.4.2.5 Continue with the washing process until the
fide, it is necessary to dry and store them in a hydrogen sulfide
washed sample tests negative to the presence of hydrogen
free atmosphere.)
sulfide. (Warning—When elemental sulfur and mercaptans are
X1.3.5 Sodium Hydrogen Carbonate, Aqueous Solution—
both present, it is possible that upon reheating the washed
Prepare this solution by dissolving 50 6 1 g of sodium
hydrogen carbonate (Na2HCO3) in water; dilute to 1 L in a sample, more hydrogen sulfide will form. Because the forma-
volumetric flask. tion of more hydrogen sulfide (after washing) will affect the
X1.3.6 Test Paper— Any standard laboratory filter paper, test result, do not reheat the washed portion of the sample.)
capable of absorbing the lead acetate solution may be used. X1.4.2.6 When the test portion is free of all hydrogen
(Warning—Any paper containing active sulfides will interfere sulfide, the determination of the thiol (mercaptan) content may
with the test.) proceed.

X2. GENERIC QUALITY CONTROL STATEMENT FOR D2 TEST METHODS

X2.1 Confirm the performance of the instrument and the test method, the frequency of QC testing is dependent on the
test procedure by analyzing a QC sample. criticality of the quality being measured, the demonstrated
stability of the testing process, and customer requirements.
X2.2 Prior to monitoring the measurement process, the user Generally, a QC sample should be analyzed on each day of
of the method needs to determine the average value and control testing routine samples. The QC frequency should be increased
limits of the QC sample.8,9 when a large number of samples are routinely analyzed.
X2.3 Record the QC results and analyze by control charts However, when it is demonstrated that the testing is under
or other statistically equivalent techniques to ascertain the statistical control, the QC testing frequency may be reduced.
statistical control status of the total testing process.7,8 Any The QC sample precision should be periodically checked
out-of-control data should trigger investigation for root against the ASTM method precision to ensure data quality.
cause(s). The results of this investigation may, but not neces- X2.5 It is recommended that, when possible, the type of QC
sarily, 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
homogeneous and stable under the anticipated storage condi-
8
Practice D 6299. tions.
9
ASTM MNL7: Manual of Presentation of Data Control Chart Analysis, 6th ed.,
Section 3: Control Chart for Individuals, available from ASTM International X2.6 See Footnotes 8 and 9 for further guidance on QC and
Headquarters. Control Charting techniques.

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D 3227 – 02
SUMMARY OF CHANGES

Subcommittee D02.03 has identified the location of selected changes to this standard since the last issue
(D 3227 - 00) that may impact the use of this standard.

(1) Updated 9.2 to align the requirements for the initial presence of H2S, to allow laboratories that choose to use
qualitative test for H2S with the requirements for testing the something other than a test tube to be in compliance.
washed samples by removing the prescriptive requirement that (2) Paragraph 6.11 was editorially corrected.
a test tube be used for checking the washed sample for the

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