An American National Standard

Designation: D 3120 – 06

Standard Test Method for

Trace Quantities of Sulfur in Light Liquid Petroleum
Hydrocarbons by Oxidative Microcoulometry1
This standard is issued under the fixed designation D 3120; 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 sulfur Petroleum Products
concentration in the range from 3.0 to 1000 mg/kg in light D 6299 Practice for Applying Statistical Quality Assurance
liquid hydrocarbons boiling in the range from 26 to 274°C (80 Techniques to Evaluate Analytical Measurement System
to 525°F). Performance
1.2 Other materials falling within the distillation range 2.2 OSHA Regulations:
specified in 1.1, but having sulfur concentrations above 1000 OSHA Regulations 29 CFR, paragraphs 1910.1000 and
mg/kg, may be tested using appropriate dilutions to bring them 1910.12003
within the specified limit. In addition, sample types that may be 3. Summary of Test Method
outside the specified distillation range, such as diesels and
biodiesels, may be analyzed by this test method. 3.1 A liquid sample is introduced into a pyrolysis tube
1.3 The values stated in SI units are to be regarded as the maintained at a temperature between 900-1200°C, having a
standard. The values given in parentheses are provided for flowing stream of gas containing 50-80% oxygen and 20-50%
information only. The preferred units are milligrams per inert gas (for example, argon, helium, etc.) Oxidative pyrolysis
kilogram (mg/kg). converts the sulfur to sulfur dioxide, which then flows into a
1.4 This standard does not purport to address all of the titration cell where it reacts with triiodide ion present in the
safety concerns, if any, associated with its use. It is the electrolyte. The triiodide ion consumed is coulometrically
responsibility of the user of this standard to establish appro- replaced and the total current (I 3 t) required to replace it is a
priate safety and health practices and determine the applica- measure of the sulfur present in the sample.
bility of regulatory limitations prior to use. For specific hazard 3.2 The reaction occurring in the titration cell as sulfur
statements, see Sections 7-9. dioxide enters is:
I32 1 SO2 1 H2O → SO3 1 3I2 1 2H 1 (1)
2. Referenced Documents
The triiodide ion consumed in the above reaction is gener-
2.1 ASTM Standards: 2
ated coulometrically thus:
D 1193 Specification for Reagent Water
D 1298 Test Method for Density, Relative Density (Specific 3I2 → I32 1 2e2 (2)
Gravity), or API Gravity of Crude Petroleum and Liquid 3.3 These microequivalents of triiodide ion (iodine) are
Petroleum Products by Hydrometer Method equal to the number of microequivalents of titratable SO2 ion
D 4052 Test Method for Density and Relative Density of entering the titration cell.
Liquids by Digital Density Meter
D 4057 Practice for Manual Sampling of Petroleum and 4. Significance and Use
Petroleum Products 4.1 This test method is used to determine the concentration
of sulfur in light liquid hydrocarbons, gasoline, and diesels and
1
This test method is under the jurisdiction of ASTM Committee D02 on
their additives, where such concentrations of sulfur can be
Petroleum Products and Lubricants and is the direct responsibility of Subcommittee detrimental to their production, performance, and use. The
D02.03 on Elemental Analysis. measurement of sulfur in the production and final product of
Current edition approved Dec. 1, 2006. Published January 2007. Originally gasoline and diesel is required for both regulatory purposes and
approved in 1972. Last previous edition approved in 2003 as D 3120–03a.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [email protected]. For Annual Book of ASTM
3
Standards volume information, refer to the standard’s Document Summary page on Available from U.S. Government Printing Office, Superintendent of Docu-
the ASTM website. ments, 732 N. Capitol St., NW, Mail Stop: SDE, Washington, DC 20401.

*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 3120 – 06
NOTE 1—Take care not to use excessive stirring and possibly damage
the electrodes with the stir bar. The creation of a slight vortex is adequate.

6.6 Microcoulometer—The apparatus’ microcoulometer,

with variable attenuation and gain control, shall be capable of
measuring the potential of the sensing-reference electrode pair
and compare this potential to a bias potential. By amplifying
this potential difference and applying the difference to a
FIG. 1 Typical Pyrolysis Tube working-auxiliary pair of electrodes (the generator), a titrant is
generated. The microcoulometer integrates the amount of
current used, calculates the equivalent mass of sulfur titrated
to ensure maximum life expectancy of catalytic converters
and calculates the concentration of sulfur in the sample.
used in the automotive industry.
6.7 Strip Chart Recorder (Optional)—To monitor and plot
5. Interferences the mV potential of the titration cell during the analysis.
5.1 This test method is applicable in the presence of total 6.8 Flow Control—The apparatus shall be equipped with
halide concentrations of up to 10 times the sulfur level and total flow controllers capable of maintaining a constant supply of
nitrogen concentrations of up to 1000 times the sulfur level. oxygen and inert carrier gas.
5.1.1 Stringent techniques shall be employed and all pos- 6.9 Dryer Tube—The oxidation of samples produces water
sible sources of sulfur contamination eliminated to attain the vapor which, if allowed to condense between the exit of the
quantitative detectability capable with this test method. pyrolysis tube and the titration cell, will absorb the SO2 formed
5.2 This test method is not applicable in the presence of and result in low recovery. Steps shall be taken to prevent such
total heavy metal concentrations (for example, Ni, V, Pb, etc.) an occurrence. This is easily accomplished by placing a
in excess of 500 mg/kg (ppm). phosphoric acid dehydration tube between the titration cell and
exit of the pyrolysis tube. Other approaches, such as heating
6. Apparatus tape or permeation tubes, can be used if precision and accuracy
6.1 The configuration of the pyrolysis tube and furnace may are not degraded.
be constructed as is desirable as long as the operating param- 6.10 Sampling Syringes—Microlitre syringes able to accu-
eters are met. Fig. 1 is typical of apparatus currently in use. rately deliver 5 to 80 mL of sample are required. The volume
6.2 A typical assembly and oxidative gas flow through a injected should not exceed 80% of a syringe’s capacity.
coulometric apparatus for the determination of trace sulfur is 6.11 Sample Inlet System—Either type of sample inlet
shown in Fig. 2. system described can be used.
6.3 Furnace—Maintained at a temperature sufficient to
6.11.1 Boat Inlet System—The inlet of the pyrolysis tube is
completely pyrolyze the organic matrix, 900-1200°C, and
sealed to the boat inlet system. The system provides a cooled
completely oxidize the organically bound sulfur to SO2.
area before the furnace for the sample boat prior to quantitative
Independently controlled inlet and outlet temperature zones are
introduction of sample into the boat and is purged with the inert
optional. An electrical furnace has been found suitable to use.
carrier gas. The boat driving mechanism then fully inserts the
6.4 Pyrolysis Tube—Fabricated from quartz and constructed
boat into the oxidation zone of the furnace. The drive mecha-
so the sample is vaporized in a heated zone before the furnace
nism shall advance and retract the sample boat into and out of
and swept into the oxidation zone by an inert carrier gas, where
the oxidation zone of the furnace at a controlled and repeatable
the vaporized sample mixes with oxygen and is pyrolyzed. The
rate (see Note 2).
inlet shall be constructed large enough to accommodate a
sample boat completely into the oxidation zone of the pyrolysis 6.11.1.1 Boat Inlet Cooler (Optional)—Sample volatility
tube or allow the direct injection of the sample into the heated and injection volume may require an apparatus capable of
zone before the furnace. The pyrolysis tube shall have side cooling the sample boat prior to sample introduction. Thermo-
arms for the introduction of oxygen and inert carrier gas. electric coolers (peltier) or recirculating refrigerated liquid
6.5 Titration Cell—Consisting of a sensor/reference pair of devices are strongly recommended. Switching sample boats
electrodes to detect changes in triiodide ion concentration, a between each analysis may prove effective, provided sample
generator anode-cathode pair of electrodes to maintain a size is not too large.
constant triiodide ion concentration, an inlet for gaseous 6.11.1.2 Sample Boats—Quartz or other suitable material
sample from the pyrolysis tube, and an outlet to vent the exit which will not react with the sample or sulfur compounds
gases from the titration cell. The reference electrode can be being analyzed and able to withstand the temperatures ex-
either an Ag/AgCl double junction reference electrode or a tremes of the test method.
platinum wire in a saturated triiodide half-cell. The sensor 6.11.2 Syringe Inlet System—The system shall deliver a
electrode and both the anode and cathode electrodes of the quantitative amount of sample from a microlitre syringe into a
generator are made of platinum. The titration cell shall require heated area before the oxidation zone of the pyrolysis tube at
mixing, which can be accomplished with a magnetic stir bar, a controlled and repeatable rate. There the sample is volatilized
stream of gas, or other suitable means. Other sensor and and the inert carrier gas stream purging the heated area
reference electrodes may be used if they meet the performance transports the volatilized sample into the oxidation zone of the
criteria of this test method. pyrolysis furnace. An adjustable drive mechanism capable of

2
 D 3120 – 06

FIG. 2 Flow Diagram for Typical Coulometric Apparatus for Trace Sulfur Determination

injecting the sample from a microlitre syringe at a constant rate 7.7 Oxygen—High purity grade (HP),5 used as the reactant
between 0.5 to 1.0 mL/s is required (see Note 2). gas. (Warning—Oxygen vigorously accelerates combustion.)
NOTE 2—Take care not to introduce the sample too fast into the
7.8 Gas Regulators—Two-stage gas regulators shall be used
oxidation zone of the furnace and overload the combustion capacity of the for the oxygen and inert carrier gas.
pyrolysis tube. Program the sample inlet system to deliver the sample at 7.9 Cell Electrolyte Solution—Dissolve 0.5 g of potassium
a sufficiently controlled and repeatable rate to prevent any incomplete iodide (KI) and 0.6 g of sodium azide (NaN3) in approximately
combustion by-products (coke or soot) from forming at the exit of the 500 mL of high-purity water, add 6 mL of glacial acetic acid
pyrolysis tube. (CH3COOH), and dilute to 1000 mL or follow the manufac-
6.12 Balance—With a weighing precision of 60.01 mg. turer’s specifications.
NOTE 3—Take care to store bulk quantities of the electrolyte in a dark
7. Reagents and Materials
place. It is recommended to prepare fresh electrolyte at least every three
7.1 Purity of Reagents—Reagent grade chemicals shall be months.
used in all tests. Unless otherwise indicated, it is intended that
7.10 Sodium Azide (NaN3), fine granular. (Warning—
all reagents shall conform to the specifications of the Commit-
Toxic. Causes eye and skin irritation. Explosive.)
tee on Analytical Reagents of the American Chemical Society,
where such specifications are available.4 Other grades may be 7.11 Potassium Iodide (KI), fine granular.
used, provided it is first ascertained that the reagent is of 7.12 Potassium Chloride (KCl), fine granular. Used for the
sufficiently high purity to permit its use without lessening the 1M Ag/AgCl double junction reference electrode.
accuracy of the determination. 7.13 Potassium Nitrate (KNO3), fine granular. Used for the
7.2 Purity of Water—Unless otherwise indicated, references 1M Ag/AgCl double junction reference electrode.
to water shall be understood to mean reagent water conforming 7.14 Iodine (I), 20 mesh or less, for saturated reference
to Specification D 1193, Type II and III. electrode.
7.3 Quartz Wool—Grade fine. 7.15 Toluene, Xylenes, Isooctane—Reagent grade. (Other
7.4 Acetic Acid (CH3COOH)—Glacial acetic acid with solvents similar to those occurring in the samples being
specific gravity = 1.05. (Warning—Poison. Corrosive. Com- analyzed are acceptable.) A solvent blank correction is required
bustible. May be fatal if swallowed. Causes severe burns. due to the inherent sulfur present in the solvents used for
Harmful if inhaled.) standard preparation and sample dilution. (Warning—
7.5 Phosphoric Acid (85 % w/w)—Orthophosphoric acid Flammable solvents. Harmful if inhaled. Vapors may cause
(H3PO4). (Warning—Poison. Corrosive. May be fatal if swal- flash fire.)
lowed. Causes severe burns.) NOTE 4—The use of solvents with non-detectable levels of sulfur
7.6 Inert Gas—Argon or helium, high purity grade (HP),5 relative to the sulfur content in the sample can make the solvent blank
used as carrier gas. (Warning—Compressed gas under high correction unnecessary.
pressure. Gas reduces oxygen available for breathing.)
7.16 Dibenzothiophene—FW 184.26, 17.399 % (mass/
mass) S (see Note 4).
7.17 n-Butyl Sulfide—FW 146.29, 21.92 % (mass/mass) S
4
Reagent Chemicals, American Chemical Society Specifications, American (see Note 4).
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory 7.18 Thionaphthene (Benzothiophene)—FW 134.20,
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia 23.90% (mass/mass) S (see Note 4).
and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
MD. NOTE 5—A correction for chemical impurity can be applied if deemed
5
High-purity grade gas has a minimum purity of 99.995 %. necessary.

3
 D 3120 – 06
TABLE 1 Recommended Preparation of Working Standards
Working Standard Concentration, Stock Standard Concentration, Volume Stock Standard, Total Volume Working Standard,
µg-S/mL µg-S/mL mL mL
500 1000 25 50
50 1000 5 100
10 500A 2 100
A
Working standard.

TABLE 2 Recommended Calibration Standards versus Desired Calibration Range

Calibration Range, mg-S/kg Calibration Standards Concentration
Concentration 1, Concentration 2, Concentration 3,
mg-S/mL mg-S/mL mg-S/mL
Trace–2.5 0.2 1.0 2.5
0.5–50 0.2 5 50
1.0–250 0.5 10 250
2.5–500 1.0 25 500
5.0–1000 2.5 50 1000

7.19 Sulfur, Standard Solution (approximately 1000 mg-S/ 8.2 Consult current OSHA regulations and supplier’s Mate-
mL)—Prepare a stock solution by accurately weighing approxi- rial Safety Data Sheets (MSDS) for materials used in this test
mately 0.5748 g of dibenzothiophene or 0.4652 g of n-butyl method.
sulfide or 0.4184 g of thionaphathene into a tared 100 mL, type
A volumetric flask. Dilute to volume with a selected solvent. 9. Sampling
This stock can then be further diluted to prepare sulfur working 9.1 Obtain a test sample in accordance with Practice D 4057
and calibration standards as outlined in Tables 1-3 (see Notes or Practice D 4177. To preserve volatile components which are
6-8). in some samples, do not uncover samples any longer than
necessary. Samples should be analyzed as soon as possible
A 3 B 3 C 3 106
µg2S/mL 5 (3) after collection from bulk supplies to prevent loss of sulfur, or
100 mL
contamination due to exposure or contact with sample con-
where: tainer.
A = grams of standard. 9.1.1 (Warning—Samples collected at temperatures below
B = weight of fraction sulfur (S) in standard. room temperature can undergo expansion and rupture the
C = weight of fraction standard purity. container. For such samples, do not fill the container to the top;
7.20 Sulfur, Standard Working Solution—Prepare the work- leave sufficient air space above the sample to allow room for
ing standards using standard type A volumetric pipet as expansion.)
outlined in Table 1. 9.2 If the test sample is not used immediately, thoroughly
NOTE 6—Working and calibration standards prepared on a regular basis
mix the container prior to taking a test specimen.
recommended, depending upon frequency of use and age. Stock solutions
10. Preparation of Apparatus
typically have a useful life of about 3 months.
NOTE 7—Calibration standards can be prepared and diluted on a 10.1 Carefully insert the quartz pyrolysis tube into the
mass/mass basis, when calculation results are adjusted to accommodate furnace, and connect the oxygen and inert carrier gas lines.
them. 10.2 Connect the boat drive system or syringe drive system
NOTE 8—Stock, working and calibration standards from commercial to the pyrolysis tube.
sources can be used if checked for accuracy and can meet the performance
criteria of this test method.
10.3 Perform a leak check according to the manufacturer’s
instructions.
7.21 Quality Assurance (QA) Samples—Samples that are 10.4 Assemble the titration cell, and add all required solu-
liquid petroleum materials or standards products of known tions, including cell electrolyte, according to the manufactur-
sulfur content that were not used in the generation of the er’s instructions.
apparatus’ calibration curve. These (QA) samples are to be 10.5 Connect the titration cell to the apparatus according to
used to check the validity of the testing process as described in the manufacturer’s instructions.
Section 11. An ample supply of QA sample material should be 10.6 Adjust the flow of gases and set the furnace tempera-
available for the intended period of use and shall also be tures and instrumental parameters according to the manufac-
homogenous and stable under the anticipated storage time and turer’s instructions.
conditions. 10.7 If using a boat inlet system, pre-bake the sample boats
used for the analysis per the manufacturer’s instructions.
8. Hazards
8.1 High temperature is employed in this test method. Extra 11. Calibration and Standardization
care shall be exercised when using flammable materials near 11.1 Following the manufacturer’s recommended proce-
the furnace. dures, set the operational parameters of the apparatus for

4
 D 3120 – 06
TABLE 3 Recommended Preparation of Calibration Standards
Concentration Working Standard, Volume of Working Standard, Total Volume Calibration Standard, Concentration Calibration Standard,
µg-S/mL mL mL µg-S/mL
10 2 100 0.2
10 5 100 0.5
50 2 100 1.0
50 5 100 2.5
50 10 100 5.0
500 5 100 25
500 10 100 50
1000A 25 100 250
500 ... ... 500
1000A ... ... 1000A
A
Standard stock solution.

TABLE 4 Recommended Sample Size for Expected Sample

internal calibration. If the apparatus is not so equipped, analyze Concentrations
the solvent blank and calibration standards, record their values Sample Concentrations, Injected Volume, Mass Sulfur,
as µg or ng of sulfur, and manually generate a calibration mg-S/kg µL µg-S
curve. Trace–5.0 80 Trace–0.25
11.2 Calibration Standards—Select the desired calibration 0.5–50 60 0.03–1.5
1.0–250 30 0.03–5.0
range from Table 2. Prepare the appropriate calibration stan- 2.5–500 20 0.05–5.0
dards for the range selected as outlined in Table 3. The 5.0–1000 10 0.05–10
calibration standards concentrations are calculated based on the
formula below:
place of the procedure described for the manual syringe injection.
A3B
Calibration Standard Concentration: µg2S/mL 5 100 mL (4) 11.5.2 Mass Measurement—The sample syringe may be
weighed before and after the injection to determine the amount
where: of sample injected. This technique provides greater precision
A = µg-S/mL of working or stock solution. than the volume delivery method, provided a balance with a
B = mL of working or stock solution. precision of 60.01 mg is used.
NOTE 9—A calibration curve with three standards is recommended. It is 11.5.3 Once the appropriate sample size has been measured
recommended to use standards covering the range of sulfur concentrations into the microlitre syringe, promptly and quantitatively deliver
expected in the samples being analyzed. Calibration curves with one or the sample into the apparatus. Again, there are two alternative
two standards can be used if it can be shown the calibration curve is linear techniques available.
over the concentration range being measured and the standards meet the
11.5.4 Boat Inlet System—Add the sample by slowly dis-
performance criteria of this test method. Larger series of standards can
also be used if it can be shown the calibration curve is linear over the charging quantitatively the contents of the syringe into a
concentration range being measured and the standards meet the perfor- sample boat containing quartz wool, being careful to include
mance criteria of this test method. the last drop from the tip of the syringe needle. Remove the
NOTE 10—The use of calibration standards with different concentra- syringe and immediately start the analysis. The apparatus’
tions is possible provided they cover the expected concentration range for baseline should remain stable until the boat approaches the
the samples being analyzed and meet the performance criteria of this test furnace and volatilization of sample begins (see Note 12). The
method.
program of the inlet system should keep the boat completely in
11.3 Select the appropriate syringe based on the recom- the oxidation zone of the furnace a time (residence time)
mended sample size in Table 4 for the concentration of sufficient to totally oxidize the sample before withdrawing the
standards used to calibrate the apparatus. sample boat out of the furnace (see Note 13). Allow at least 2
11.4 Flush the microlitre syringe several times with the min for cooling before the next sample injection after the boat
sample prior to analysis. If bubbles are present in the liquid has reached the fully retracted position (see Note 14).
column, flush the syringe and withdraw a new sample.
NOTE 12—It is recommended, if necessary, to reduce the boat speed, or
11.5 The sample size can be determined volumetrically or
briefly pause the boat, or both, as it is introduced into the oxidation zone
by mass with a syringe. The sample size should be 80% or less of the furnace to ensure complete sample combustion and avoid overload-
of the syringe’s capacity. ing the combustion capacity of the system.
11.5.1 Volumetric Measurement—Obtain the volume of in- NOTE 13—The residence time required to completely oxidize any
jected material by filling the syringe to the selected level, remaining residue in the boat is dependent on the sample matrix. A 120-s
retracting the plunger so the lower meniscus falls on the 10% residence time is usually sufficient. Increase the residence time, if
scale mark, and recording the volume of liquid in the syringe. necessary, to ensure complete oxidation of the sample.
NOTE 14—The level of boat cooling required prior to sample injection
After the sample has been injected, retract the plunger again so is directly related to the volatility and size of sample. The use of a boat
the lower liquid meniscus falls on the 10% scale mark, and cooling device, an increase in boat cooling time, or both, can be used to
record the volume of liquid in the syringe. The difference control the vaporization of sample until the boat approaches the furnace.
between the two readings is the volume of sample injected.
11.5.4.1 Reduce the boat drive introduction rate, sample
NOTE 11—An automatic sampling and injection device can be used in size or both if coke or soot is observed on the exit end of the

5
 D 3120 – 06
pyrolysis tube. Increase the residence time for the boat in the 12. Quality Assurance (QA)
oxidation zone of the furnace if coke or soot is observed on the 12.1 Confirm the performance of the instrument of the test
boat after the analysis is finished. procedure by analyzing a quality control (QC) sample after
11.5.5 Syringe Inlet System—For direct injection, carefully each calibration and at least each day of use thereafter.
insert the syringe needle into the inlet of the combustion tube 12.2 When QC/QA protocols are already established in the
and attach the syringe to the driving mechanism. Allow time testing facility, these can be used when they confirm the
for the sample residues to be volatilized from the needle reliability of the test result.
(needle blank). Once the baseline has been reestablished, 12.3 When there is not QC/QA protocol established in the
immediately start the analysis. Remove the syringe once the testing facility, Appendix X1 can be used as the QC/QA
sample has been syringe once the sample has been completely system.
injected and the analysis is finished.
NOTE 15—To avoid overloading the combustion capacity of the system, 13. Procedure
injection rates between 0.5-1.0 µL/s are recommended. 13.1 Obtain a test sample using the procedure described in
11.5.5.1 Reduce the sample size, rate of injection, or both, Section 9. The sulfur concentration in the test sample shall be
for the direct injection the test sample into the furnace if coke less than the concentration of the highest standard and greater
or soot is observed on the exit end of the pyrolysis tube. than the concentration of the lowest standard used in the
11.6 Calibrate the instrument using one of the following two calibration. If required, a dilution should be performed on
techniques: either a weight or volume basis.
11.6.1 Automatic Internal Calibration—Measure the cali- 13.1.1 Gravimetric Dilution, (mass/mass)—Record the
bration standards and solvent blank using one of the procedures mass of the test sample and the total mass of the sample and
described in 11.3–11.5.5. Analyze the solvent blank and each solvent.
standard a minimum of three times. Calibrate the apparatus per 13.1.2 Volumetric Dilution, (mass/volume)—Record the
the manufacturer’s instructions. Use either a first or second mass of the test sample and the total volume of the test sample
order linear regression and use this calibration curve to and solvent.
determine the amount of sulfur in the unknown sample. The 13.2 Flush the sampling syringe several times with the
system’s performance shall be checked each day of use. (See unknown sample. Determine the sulfur concentration using one
Section 12.) of the procedures described in 11.3–11.5.5.
11.6.2 Manual Calibration Curve—Measure the solvent 13.3 Inspect the combustion tube and other flow path
blank and calibration standards using one of the procedures components to verify complete oxidation of the test sample.
described in 11.3–11.5.5. Analyze the solvent blank and each 13.3.1 Boat Inlet Systems—Reduce the boat drive introduc-
calibration standard a minimum of three times and record their tion rate, sample size, or both, if coke or soot is observed on the
absolute values in either µg or ng sulfur. Subtract the averaged exit end of the pyrolysis tube. Increase the residence time for
blank value from each calibration standard and construct a the boat in the oxidation zone of the furnace if coke or soot is
curve plotting the mass of sulfur measured for each calibration observed on the boat after the analysis is finished.
standard (y-axis) verses the theoretical mass of sulfur injected. 13.3.2 Syringe Inlet Systems—Reduce the sample size, rate
Perform a first or second order linear regression and use the of injection, or both, for the direct injection the test sample into
calibration curve to determine the amount of sulfur in the the furnace if coke or soot is observed on the exit end of the
unknown sample. The system’s performance shall be checked pyrolysis tube.
each day of use. (See Section 12.) 13.3.3 Cleaning and Recalibration—Clean any coked or
sooted parts per the manufacturer’s instructions. Assemble and
NOTE 16—Not all of the sulfur in the sample exits the oxidation zone of
the furnace as titratable SO2. In the strongly oxidative conditions of the leak check the apparatus per the manufacturer’s instructions
pyrolysis tube, some of the sulfur is also converted to SO3, which does not after any cleaning or adjustment. Repeat instrument calibration
react with the titrant. Accordingly, sulfur standards appropriate to the prior to reanalysis of test samples.
sample’s boiling range and sulfur type is recommended to guarantee 13.4 To obtain one result measure each test sample solution
adequate calibration. Recoveries less than 75% are to be considered three times and calculate the average value.
suspect. If recoveries below 75% are observed, it is recommended the 13.5 If the sample size is determined by volume, density
operator check the coulometric system, measuring parameters, and oper-
ating techniques are in proper order. If the apparatus is being operated
values needed for calculations are to be measured (using Test
properly, recoveries between 75 to 90% are to be expected. Method D 1298, Test Method D 4052, or equivalent) at the
temperature at which the sample was tested. If the sample size
11.7 If the fraction of sulfur converted to SO2(recovery
was determined by weight, density values are not required.
factors) drops below 75% of the standard solutions, prepare
fresh standards to check if the standards have been altered. 14. Calculation
Procedural details should be reviewed if a low recovery factors
persist. 14.1 Calculate the sulfur concentration in the test sample in
11.8 Cleaning and Recalibration—Clean any coked or mg/kg (ppm) as follows:
sooted parts per the manufacturer’s instructions. Assemble and C 3 1000
Sulfur, mg/kg ~ppm! 5 M 3 K or (5)
leak check the apparatus per the manufacturer’s instructions
after any cleaning or adjustment. Repeat instrument calibration C 3 1000
Sulfur, mg/kg ~ppm! 5 V 3 D (6)
prior to reanalysis of test samples.

6
 D 3120 – 06

FIG. 3 Percent Recovery versus Temperature (°C)

where: 1000 = Factor to convert µg/mg to mg/kg (ppm).

C = sulfur found in test sample (either directly from the
instrument or calculated manually from the calibra- 15. Precision and Bias
tion curve), µg. 15.1 The precision of this test method was determined by
K = gravimetric dilution factor, mass of test sample/ statistical examination of test results obtained in two separate
mass of test sample and solvent, g/g. interlaboratory studies. Details of the first interlaboratory study
M = mass of test sample solution injected, either directly (Case I)6 can be found in RR:D02-1036. The second interlabo-
measured or calculated from measured volume ratory study (Case II)7,8 involved 16 samples each of low level
injected and density, V 3 D, mg.
V = volume of test sample solution injected, either
measured directly or calculated from measured 6
Supporting data have been filed at ASTM International Headquarters and may
mass injected and density, M/D, µL. be obtained by requesting Research Reports RR:D02–1036.
7
Supporting data have been filed at ASTM International Headquarters and may
D = density of sample, g/mL. be obtained by requesting Research Report RR:D02–1546.

7
 D 3120 – 06
sulfur gasoline and diesel sample types analyzed by eight 15.1.2.1 Case I—The difference between two single and
laboratories. A practical limit of quantitation (PLOQ) of '3 independent results obtained by different operators working in
µg/g S, was determined for the gasoline sample types and '5 different laboratories on identical test material would, in the
µg/g S for diesel sample types. long run, in the normal and correct operation of the test
15.1.1 Repeatability: method, exceed the following values in 1 case in 20, where x
15.1.1.1 Case I—The difference between two test results = the average of two test results.
obtained by the same operator with the same apparatus under
R 5 0.5793 X ~0.7901! (8)
constant operating conditions on identical test material would,
in the long run, in the normal and correct operation of the test 15.1.2.2 Case II—Gasoline samples between approximately
method, exceed the following values in only in 1 case in 20, 3 and 100 mg/g and diesel samples between approximately 5
where x = the average of the of two test results. and 40 µg/g were analyzed. The reproducibility values deter-
mined were as follows:
r 5 0.2802 X ~0.7901! (7)
Gasoline: 0.1470(X + 7.4502)1.3226
15.1.1.2 Case II—Gasoline samples between approximately Diesel: 0.5152(X + 0.65758)
where: X is the average of duplicate results in µg/g
3 and 100 µg/g and diesel samples between approximately 5
and 40 µg/g were analyzed. The repeatability values deter- 15.2 Bias—Three National Institute of Standards and Tech-
mined were as follows: nology (NIST) Standard Reference Materials (SRM) were
Gasoline: 0.03194(X + 7.4502)1.3226 analyzed to determine the bias. These samples were gasoline
Diesel: 0.08520 (X + 0.65758) SRMs 2298 (4.6 µg/g S) and 2299 (13.6 µg/g S), and diesel
where: X is the average of duplicate results in µg/g
SRM 2723a (10 µg/g S). There was no significant bias for
15.1.2 Reproducibility: SRMs 2299 and 2723a. However, there was a bias of -1.25 for
SRM 2298. 8

8
16. Keywords
Supporting data have been filed at ASTM International Headquarters and may
be obtained by requesting Research Report RR:D02–1547. 16.1 light hydrocarbons; microcoulometry; sulfur

APPENDIXES

(Nonmandatory Information)

X1. QUALITY CONTROL (QC)

X1.1 Confirm the performance of the instrument or the test test method, the frequency of QC testing is dependent of the
procedure by analyzing a quality control sample. criticality of the quality being measured, the demonstrated
stability of the testing process, and customer requirements.
X1.2 Prior to monitoring the measurement process, the user Generally, a QC sample is analyzed each testing day with
of the test method needs to determine the average value and
routine samples. The QC frequency should be increased if a
control limits of the QC sample (see Practice D 6299 and MNL
large number of samples are routinely analyzed. However,
79).
when it is demonstrated that the testing is under statistical
X1.3 Record the QC results and analyze by control charts control, the QC testing frequency may be reduced. The QC
or other statistically equivalent techniques to ascertain the sample precision should be checked against the ASTM test
statistical control status of the total testing process (see Practice method precision to ensure data quality.
D 6299 and MNL 79). Any out -of-control data should trigger
investigation for root cause(s). The results of this investigation X1.5 It is recommended that, if possible, the type of QC
may, but not necessarily, result in instrument e-calibration. sample that is regularly tested be representative of the material
routinely analyzed. An ample supply of QC sample material
X1.4 In the absence of explicit requirements given in the
should be available for the intended period of use, and shall be
homogeneous and stable under the anticipated storage condi-
9
ASTM MNL 7, Manual on Presentation of Data Control Chart Analysis, 6th tions. See Practice D 6299 and MNL 79 for further guidance on
ed., available from ASTM International, W. Conshohocken, PA 19428. QC and control charting techniques.

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 D 3120 – 06

X2. DERIVATION OF COULOMETRIC CALCULATIONS USED IN SECTION 14

X2.1 Derivation of Equations: F = 96 500 C/eq.

X2.1.1 The derivation of the equations used in the calcula- = Faraday’s constant10(electrical equivalence of one
tion section is based on the coulometric replacement of the gram-equivalent mass of any substance).
triiodide (iodine) ions consumed in the microcoulometric A·s/C = conversion of coulombs to ampere-seconds.
titration cell reaction (I3− + 2e−→ 3I−. The quantity of the f = recovery factor (ratio of ppm S determined in
reactant formed (triiodide ions) between the beginning and the standard versus known ppm S in standard).
interruption of current at the end of the titration is directly Therefore,
proportional to the net charge transferred, Qt.. 16 g 10 6 µg
A 3 12 3 10 23 A·s 3 eq 3 g
X2.1.2 In most applications a constant current is used so µg S 5 (X2.4)
that the product of current, i, in amperes (coulombs per 96 500 C A·s
R3 eq 3 C 3f
second), multiplied by the time, T (seconds), required to reach
the end point provides a measure of the charge, Q (coulombs), Therefore,
necessary to generate the iodine equivalent to the reactant; that
A 3 12 3 1023 3 16 3 10 6 µg
is, Q = it. Therefore, the number of equivalents of reactant is µg S 5 R 3 96 500 3 f (X2.5)
equal to Q/F, where F is the Faraday constant, 96 500 C per
equivalent. Therefore,
X2.1.3 Therefore, the expression to be solved to find the µg S 5 ~A 3 1.99!/~R 3 f! (X2.6)
mass of reactant is: Since ppm = µg/g:
Q~C! 16 g A 3 1.99
FC 3 eq ppm S 5 R 3 f 3 volume, µL (X2.7)
mass of sulfur, g eq
Concentration of sulfur 5 mass of sample, g 5 mass of sample, g mL g
3 1023 µL 3 density, mL
(X2.1)
A 3 1.99 3 10 3
0.1 mV 2 min 60 s 10–3 V 16 g 166 µg ppm S 5 R 3 f 3 volume 3 density (X2.8)
in. 3 in. 3 min 3 mV 3 eq 3 g
µg S 5 A in. 2 3 96 500 C A·s
R ~V! 3 eq 3 C 3 f!
Since mass = volume 3 density
(X2.2)
ppm S 5 ~A 3 1.99!/~R 3 f 3 mass, g! (X2.9)
where: X2.1.4 Derivation with Disk Integrator—A in Eq X2.6 is
A in.2 = peak area measured in square inches. expressed as in.2 However, it may also be expressed as counts.
0.1 mV/in. = millivolt span of upscale deflection for the
Therefore, A in.2 = counts 3 10 −3 since 1 in.2 = 1000 counts.
recorder.
Therefore, substituting counts 3 10−3 for A in Eq X2.6 gives:
2 min/in. = chart speed in minutes per inch.
60 s/min = conversion of time in minutes to seconds. µg S 5 ~ counts 3 1.99 3 1023!/~R 3 f ! (X2.10)
10−3 V/mV = conversion of volts to millivolts. Then:
16 g/eq = gram-equivalent of sulfur.
106 µg/g = micrograms per gram conversion factor. ppm S 5
counts 3 1.99
(X2.11)
R(V) = microcoulometer range switch setting in g
R 3 volume, µL 3 density, mL 3 f
ohms.
substituting V/R = 1 (amps) ppm S 5 ~counts 3 1.99 3 10 23!/~R 3 mass, g 3 f !
0.1 mV 2 min 60 s 1023 V NOTE X2.1—Counts = 100 3 number of integrator per full-scale
A in. 2 3 in. 3 in. 3 min 3 mV excursions.
Q~A·s! 5 (X2.3)
R~V!
10
The value of the Faraday has been redetermined in 1960 by the National
Bureau of Standards: the new value is 96 489 6 2 coulombs (chemical scale).

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 D 3120 – 06
SUMMARY OF CHANGES

Subcommittee D02.03 has identified the location of selected changes to this standard since the last issue
(D 3120–03a) that may impact the use of this standard.

(1) Changed Figs. X2.1 and X2.2 to Fig. 1 and Fig. 2, (2) Moved original paragraphs X2.1 and X2.2 to 6.1 and 6.2,
respectively. respectively.

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10